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.tom Online Edition

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 MODERN
CHEMISTRY
Raymond E . Davis
Regina Frey
Mickey Sarquis
Jerry L. Sarquis

HOLT, RINEHART AND WINSTON

A Harcourt Education Company
Orlando •Austin •New York •San Diego •Toronto •London
Authors
RAYMOND E. DAVIS, PH.D. MICKEY SARQUIS
University Distinguished Teaching Professor and Director,
Professor Center for Chemistry
Education
Department of Chemistry and
Biochemistry Department of Chemistry and
The University of Texas at Austin Biochemistry
Austin, TX Miami University
Middletown, OH

REGINA FREY, PH.D. JERRY L. SARQUIS, PH.D.

Senior Lecturer and Director of Professor
the Teaching Center Department of Chemistry and
Department of Chemistry Biochemistry
Washington University in St. Louis Miami University
St. Louis, MO Oxford, OH

On the cover: A snow crystal image produced by using a low temperature

scanning electron microscope.

.
Copyright © 2006 by Holt Rinehart and Winston
All rights reserved. No part of this publication may be reproduced or transmitted in any form or by
any means, electronic or mechanical, including photocopy, recording, or any information storage and
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CBL is a trademark of Texas Instruments.

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Acknowledgments appear on page iv, which is an extension of the copyright page.

Printed in the United States of America
ISBN 0- 03- 073546 - 7

3 4 5 6 7 8 048 08 07 06

••
II
Acknowledgments
Contributing Writers George F. Atkinson, Ph.D. Gary E. Mueller, Ph .D.
Professor of Chemistry Associate Professor
Lisa Saunders Baugh, Ph. D.
Department of Chemistry Department of Nuclear Engineering
Senior Chemist
University of Waterloo University of Missouri—Rolla
Chemical Sciences Laboratory
Waterloo, Ontario, Canada Rolla, Missouri
ExxonMobil Research & Engineering
Company
Sonal S. D, Blumenthal, Ph. D. Daniel B. Murphy, Ph. D.
Corporate Strategic Research Life Science Consultant Professor Emeritus of Chemistry
Annandale, New Jersey Austin, Texas Department of Chemistry
Herbert H. Lehman College
Robert Davisson G. Lynn Carlson, Ph . D. City University of New York
Science Writer Senior Lecturer Emeritus Bronx, New York
Albuquerque, New Mexico Department of Chemistry
University of Wisconsin— Parkside R . Thomas Myers, Ph D.
Seth Madej Kenosha, Wisconsin Professor Emeritus of Chemistry
Writer / Producer
Kent State University
Pittsburgh, Pennsylvania Scott A . Darveau, Ph D. Kent, Ohio
Associate Professor
Jim Metzner
Department of Chemistry Keith B. Oldham, Ph. D.
Executive Producer
University of Nebraska at Kearney Professor of Chemistry
Pulse of the Planet Radio Series
Kearney, Nebraska Trent University
Jim Metzner Productions, Inc.
Peterborough, Ontario, Canada
Accord, New York Cassandra T. Eagle, Ph. D.
Professor of Chemistry Brian L. Pagenkopf, Ph . D.
Jay A . Young, Ph . D. Department of Chemistry Assistant Professor
Chemical Safety Consultant
Appalachian State University Department of Chemistry and
Silver Spring, Maryland
Boone, North Carolina Biochemistry
University of Texas at Austin
Inclusion Specialists Linda Gaul, Ph . D., M. P. H. Austin, Texas
Epidemiologist
Joan Altobelli Infectious Disease Epidemiology and Stanford Peppenhorst, Ed . D.
Special Education Director Surveillance Chemistry Teacher
Austin Independent School District
Department of State Health Services Germantown High School
Austin, Texas Austin, Texas Germantown, Tennessee

John A . Solorio Pamela Gollhofer Charles Scaife, Ph. D.

Multiple Technologies Lab Facilitator Science Teacher Professor of Chemistry, Emeritus
Austin Independent School District Princeton High School Union College
Austin, Texas Cincinnati, Ohio Schenectady, New York

Reviewers Hima Joshi, Ph.D. Peter Sheridan, Ph. D.

Department of Chemistry Professor
Eric V. Anslyn , Ph D. University of San Diego Department of Chemistry and
Professor San Diego, California Biochemistry
Department of Chemistry and Colgate University
Biochemistry Doris Ingram Lewis, Ph . D. Hamilton, New York
University of Texas at Austin Professor of Chemistry
Austin, Texas Suffolk University Larry Stookey, P. E .
Boston, Massachusetts Physics and Chemistry Teacher
Antigo High School
Antigo, Wisconsin

•••
ACKNOWLEDGMENTS III
Acknowledgments, continued

David C. Taylor, Ph . D. Joseph E . Vitt, Ph . D. David Wilson, Ph. D.

Professor of Chemistry Associate Professor Professor Emeritus
Department of Chemistry Chemistry Department Chemistry Department
Slippery Rock University University of South Dakota Vanderbilt University
Slippery Rock, Pennsylvania Vermillion, South Dakota Nashville, Tennessee

Richard S. Treptow, Ph . D. Verne Weidler, Ph. D. Candace Woodside

Professor of Chemistry Professor of Chemistry, Retired Science Teacher
Department of Chemistry and Physics Science and Engineering Winton Woods High School
Chicago State University Black Hawk College Forest Park, Ohio
Chicago, Illinois Kewanee, Illinois
Charles M . Wynn, Sr., Ph. D.
Barry Tucker Dale Wheeler, Ph . D. Professor of Chemistry
Chemistry Teacher Associate Professor of Chemistry Department of Physical Sciences
Colerain High School A . R . Smith Department of Chemistry Eastern Connecticut State University
Cincinnati, Ohio Appalachian State University Willimantic, Connecticut
Boone, North Carolina
Martin Van Dyke, Ph . D. continued on page 948
Chemistry Professor; Emeritus
Front Range Community College
Westminster, Colorado

For permission to reprint copyrighted material, grateful acknowledgment is made to the

following sources:
The American Chemical Society: From " Faraday's Contribution to Electrolytic Solution
Theory " by Ollm J. Drennan from Journal of Chemical Education, vol. 42, no. 12,
December, 1965, pp. 679-681. Copyright © 1965 by Division of Chemical
Education, American Chemical Society.
University of California Press: From " Exile in Stockholm " from Lise Meitner: A Life in
Physics by Ruth Lewin Sime. Copyright © 1996 by The Regents of the University of
California.

IV ACKNOWLEDGMENTS
Contents in Brief

CHAPTER
1 Matter and Change 2
2 Measurements and Calculations 28
3 Atoms: The Building Blocks of Matter 6ft

4 Arrangement of Electrons in Atoms 96

5 The Periodic Law 132

6 Chemical Bonding 174
7 Chemical Formulas and
Chemical Compounds 218

8 Chemical Equations and Reactions 260

9 Stoichiometry 298
10 States of Matter 328

11 Cases 360
12 Solutions 400

13 Ions in Aqueous Solutions and

Colligative Properties 434
14 Acids and Bases 466

15 Acid- Base Titration and pH 498

16 Reaction Energy 530

17 Reaction Kinetics 560
18 Chemical Equilibrium 588

19 Oxidation- Reduction Reactions 630

20 Electrochemistry 654
21 Nuclear Chemistry 680

22 Organic Chemistry 710

23 Biological Chemistry 750

CONTENTS V
 Contents

Matter and Change 2

1 Chemistry Is a Physical Science 3
2 Matter and Its Properties 6
3 Elements 16
Cross- Disciplinary Connection Secrets of the Cremona Violins 15
Chemistry in Action Superconductors IS
Math Tutor Significant Figures 24
Standardized Test Prep 25
Experiment Mixture Separation 26

Measurements and Calculations 28

1 Scientific Method 29
2 Units of Measurement 33
3 Using Scientific Measurements 44

Chemistry in Action Breaking Up Is Easy to Do 32

Cross- Disciplinary Connection Some Handy Comparisons of Units 35
Quick Lab Density of Pennies 39
Historical Chemistry Classical Ideas About Matter 43
Math Tutor Scientific Notation 62
Standardized Test Prep 63
Experiment Percentage of Water in Popcorn 64

CHAPTER 3 Atoms: The Building Blocks

of Matter 66
1 The Atom: From Philosophical Idea
to Scientific Theory 67
2 The Structure of the Atom 72
3 Counting Atoms 77
Careers in Chemistry Physical Chemist 70
Quick Lab Constructing a Model 71
Historical Chemistry Discovery of Element 43 81
Math Tutor Conversion Factors 92
Standardized Test Prep 93
Experiment Conservation of Mass 94

VI CONTENTS
Arrangement of Electrons in Atoms 96
1 Tlie Development of a New Atomic Model 97
2 The Quantum Model of the Atom 104
3 Electron Configurations 111
Chemistry in Action Fireflies 102
Quick Lab The Wave Nature of Light: Interference 106
Historical Chemistry The Noble Decade 114
Math Tutor Weighted Averages and Atomic Vlass 128
Standardized Test Prep 129
Experiment Flame Tests 130

The Periodic Law 132

1 I listorv of the Periodic Table 133
2 Electron Configuration and the Periodic Table 138
3 Electron Configuration and Periodic Properties 150
Quick Lab Designing Your Own Periodic Table 137
Careers in Chemistry Materials Scientist 145
Math Tutor Writing Electron Configurations 170
Standardized Test Prep 171
Experiment The Mendeleev Lab of 1869 172

Chemical Bonding 174

1 Introduction to Chemical Bonding 175
2 Covalent Bonding and Molecular Compounds 178
3 Ionic Bonding and Ionic Compounds 190
4 Metallic Bonding 195
5 Molecular Geometry 197
Chemistry in Action Ultrasonic Toxic- Waste Destroyer 180
Careers in Chemistry Computational Chemist 204
Math Tutor Drawing Lewis Structures 214
Standardized Test Prep 215
Experiment Types of Bonding in Solids 216

••
CONTENTS VII
 Chemical Formulas
and Chemical Compounds 218
1 Chemical Names and Formulas 214
2 Oxidation Numbers 232
3 Using Chemical Formulas 237
4 Determining Chemical Formulas 245

Careers in Chemistry Pharmacist 222

Chemistry in Action
Mass Spectrometry: Identifying Molecules 236
Math Tutor Calculating Percentage Composition 256
Standardized Test Prep 257
Experiment Determining the Empirical Formula
of Magnesium Oxide 258

Chemical Equations and Reactions 260

1 Describing Chemical Reactions 261
2 Types of Chemical Reactions 276
3 Activity Series of the Elements 285
Chemistry in Action Carbon Monoxide Catalyst 275
Chemistry in Action Fluoridation and Tooth Decay 283
Quick Lab Balancing Equations Using Models 284
Chemistry in Action Combustion Synthesis 288
Math Tutor Balancing Chemical Equations 294
Standardized Test Prep 295
Experiment Blueprint Paper 296

CHAPTER 9 Stoichiometry 298

1 Introduction to Stoichiometry 299
2 Ideal Stoichiometric Calculations 304

r I
3 Limiting Reactants and Percentage Yield
Careers in Chemistry Chemical Technician
Historical Chemistry The Case of Combustion
312
300
302
k Quick Lab Limiting Reactants in a Recipe 316
Math Tutor Using Mole Ratios 324
Standardized Test Prep 325
Experiment Stoichiometry and Gravimetric Analysis 326

•••
VIII CONTENTS
 States of Matter 328
1 Kinetic Theory of Matter 329
2 Liquids 333
3 Solids 337
4 Changes of State 342
5 Water 349
Chemistry in Action Surface Melting 346
Math Tutor Calculating Using Enthalpies of Fusion 356
Standardized Test Prep 357
Experiment ‘ Wet Dry Ice 358

CHAPTER 11 Gases 360

1 Gas and Pressure 361
2 The Cias Laws 369
3 Gas Volumes and the Ideal Gas Law 378
4 Diffusion and Effusion 386
Chemistry in Action The Gas Laws and Scuba Diving 368
Historical Chemistry Chemistry 's First Law 376
Chemistry in Action Automobile Air Bags 380
Quick Lab Diffusion 387
Math Tutor Algebraic Rearrangements of Gas Laws 396
Standardized Test Prep 397
Experiment Mass and Density of Air at Different Pressures 398

Solutions 400
1 Types of Mixtures 401
2 The Solution Process 407
3 Concentration of Solutions 418
Quick Lab Observing Solutions, Suspensions, and Colloids 405
Careers in Chemistry Environmental Chemist 408
Cross- Disciplinary Connection Artificial Blood 417
Math Tutor Calculating Solution Concentration 430
Standardized Test Prep 431
Experiment Separation of Pen Inks by Paper Chromatography 432

CONTENTS IX
 Ions in Aqueous Solutions and
Colligative Properties 434
1 Compounds in Aqueous Solutions 435
2 Colligative Properties of Solutions 446

Historical Chemistry The Riddle of Electrolysis 444

Chemistry in Action Water Purification by Reverse Osmosis 453
Math Tutor Boiling and Freezing Points of Solutions 462
Standardized Test Prep 463
Experiment Testing Water for Ions 464

CHAPTER 14 Acids and Bases 466

1 Properties of Acids and Bases 467
2 Acid - Base Theories 478
3 Acid - Base Reactions 483
Quick Lab Household Acids and Bases 472
Cross- Disciplinary Connection Acid —
Water A Hidden Menace 477
Cross- Disciplinary Connection It s a Bitter Pill
' 484
Math Tutor Writing Equations for Ionic Reactions 494
Standardized Test Prep 495
Experiment Is It an Acid or a Base? 496

Acid - Base Titration and pH 498

1 Aqueous Solutions and the Concept of pi I 499
2 Determining pH and Titrations 511
Cross- Disciplinary Connection Liming Streams 510
Quick Lab Testing the pH of Rainwater 514
Careers in Chemistry Analytical Chemist 516
Math Tutor Using Logarithms and pH 526
Standardized Test Prep 527
Experiment How Much Calcium Carbonate Is in an Eggshell ? 528

CHAPTER 16 Reaction Energy 530

1 Thermochemistry 531
2 Driving Force of Reactions 546

Chemistry in Action Self - Heating Meals 545

Chemistry in Action Diamonds Are Forever? 549
Math Tutor Hess's Law 556
Standardized Test Prep 557
Experiment Calorimetry and Hess's Law 558

X CONTENTS
Reaction Kinetics 560
1 The Reaction Process 561
2 Reaction Rate 568
Chemistry in Action Explosives 572
Quick Lab Factors Influencing Reaction Rate 578
Chemistry in Action Catalytic Converters 579
Math Tutor Writing Rate Laws 584
Standardized Test Prep 585
Experiment Rate of a Chemical Reaction 586

Chemical Equilibrium 588

1 The Nature of Chemical Equilibrium 589
2 Shifting Equilibrium 598
3 Equilibria of Acids, Bases, and Salts 605
4 Solubility Equilibrium 613
Historical Chemistry Fixing the Nitrogen Problem 596
Cross- Disciplinary Connection Blood Buffers 609
Math Tutor Determining Equilibrium Constants 626
Standardized Test Prep 627
Experiment Measuring K l for Acetic Acid
(
628

Oxidation- Reduction Reactions 630

1 Oxidation and Reduction 631
2 Balancing Redox Equations 637
3 Oxidizing and Reducing Agents 642
Chemistry in Action Photochromic Lenses 634
Chemistry in Action Skunk-Spray Remedy 636
Quick Lab Redox Reactions 644
Math Tutor Balancing Redox Equations 650
Standardized Test Prep 651
Experiment Reduction of Mn in Mn04 652

Electrochemistry 654
1 Introduction to Electrochemistry 655
2 Voltaic Cells 658
3 Electrolytic Cells 667
Chemistry in Action Fuel-Cell Cars 666
Chemistry in Action Sodium Production by Electrolysis 671
Math Tutor Calculating Cell Potentials 676
Standardized Test Prep 677
Experiment Voltaic C ells 678

CONTENTS XI
 CHAPTER 21 Nuclear Chemistry 680
1 The Nucleus 681
2 Radioactive Decay 685
3 Nuclear Radiation 693
4 Nuclear Fission and Nuclear Fusion 697
Cross- Disciplinary Connection Quarks 682
Historical Chemistry An Unexpected Finding 700
-
Math Tutor Calculating with Half Life 706
Standardized Test Prep 707
Experiment
Simulation of Nuclear Decay Using Pennies and Paper 708

Organic Chemistry 710

1 Organic Compounds 7 ll
2 Hydrocarbons 7I6
3 Functional Groups 730
4 Organic Reactions 735
Historical Chemistry The Beginnings of Organic Chemistry 715
Careers in Chemistry Petroleum Engineer 720
Chemistry in Action Carbon Allotropes 725
Math Tutor Calculating Empirical Formulas 746
Standardized Test Prep 747
Experiment Polymers and Toy Balls 748

CHAPTER 23 Biological Chemistry 750

*
1 Carbohydrates and Lipids 751
2 Amino Acids and Proteins 756
3 Metabolism 766
i
4 Nucleic Acids 770

I Historical Chemistry Charles Drew and Blood Transfusions 762

Careers in Chemistry Forensic Chemist 774
Math Tutor Interpretation of the Genetic Code 780
Standardized Test Prep 781
Experiment Casein Glue 782

XII CONTENTS
Elements Handbook 784
GROUP 1 ALKALI METALS 7S6 GROUP 14 CARBON FAMILY 812
APPLICATION Technology APPLICATION Chemical Industry
Sodium Vapor Lighting 788 Carbon and the Reduction of Iron Ore 814
APPLICATION Health Carbon Dioxide 815
Electrolyte Balance in the Body 789
¥ ¥
Carbon Monoxide 815
APPLICATION Biochemistry
GROUP 2 ALKALINE EARTH METALS 792
Carbon Dioxide and Respiration 810
APPLICATION Technology
APPLICATIONThe environment
Fireworks 794
Carbon Monoxide Poisoning 818
APPLICATION Health
APPLICATION Biochemistry
Calcium: An Essential Mineral in the Diet 790
Macromolecules 819
Magnesium: An Essential Mineral in the Diet 790
APPLICATION Chemical Industry
Silicon and Silicates 825
GROUPS 3-12 TRANSITION METALS 798
Silicones 825
APPLICATION Geology
Gemstones and Color 801 APPLICATIONTechnology
Semiconductors 820
APPLICATION Technology
Alloys 802
GROUP IS NITROGEN FAMILY 828
APPLICATION The Environment
APPLICATION Biology
Mercury Poisoning 805
Plants and Nitrogen 830
APPLICATION Health
APPLICATION Chemical Industry
Elements in the Body 800
Fertilizers 831
Role of Iron 807
GROUP 16 OXYGEN FAMILY 832
GROUP 13 BORON FAMILY 808
APPLICATION Chemical Industry
APPLICATION Technology Oxides 834
Aluminum 810
APPLICATION The Environment
Aluminum Alloys 81 1 Ozone 830
APPLICATION Chemical Industry
Sulfuric Acid 837

GROUP 17 HALOGEN FAMILY 838

APPLICATION The Environment
Chlorine in Water Treatment 840
Fluoride and Tooth Decay 841

Preparing for Chemistry Lab 842 Appendix D: Problem Bank 881

Appendix A : Reference Tables 854 Appendix E: Selected Answers 916
Appendix B: Study Skills for Chemistry 864 Glossary 924
Appendix C: Graphing Calculator Technology 879 Index 935

•••
CONTENTS XIII
Sample Problems and Math Tutors
Chapter 1 Matter and Change Chapter 7 Chemical Formulas
Math Tutor Significant Figures 24 and Chemical Compounds
Sample Problems
Chapter 2 Measurements and Calculations A Writing Formulas for Ionic Compounds 223
Sample Problems B Naming Ionic Compounds 225
A
Density 39 C Writing Formulas for Ionic Compounds 227
B
Conversion Factors 41 D Naming Binary Molecular Compounds 229
C
Percentage Error 45 E Oxidation Numbers 233
Significant Figures
D 47 F Formula Mass 238
E
Significant Figures 49 G Molar Mass 239
F
Solving Problems l sing the H Molar Mass as a Conversion Factor 240
Four-Step Approach 54 I Molar Mass as a Conversion Factor 241
Math Tutor Scientific Notation 62 J Percentage Composition 243
K Percentage Composition 243
Chapter 3 Atoms: The Building Blocks of Matter
L Empirical Formulas 240
Sample Problems M Empirical Formulas 247
A Subatomic Particles 79
N Molecular Formulas 24S
B Gram /Mole Conversions N4
C Gram Mole Conversions 85 Math Tutor
Calculating Percentage Composition 256
D Conversions with Avogadro s Number
'
86
E Conversions with Avogadro s Number
’ Kb Chapter 8 Chemical equations and Reactions
Math Tutor C onversion Factors 92 Sample Problems
A Writing Word. Formula.
Chapter 4 Arrangement of Electrons in Atoms and Balanced Chemical Equations 267
Sample Problems B Writing Word. Formula,
A Electron Configurations 113
and Balanced Chemical Equations 268
B Electron Configurations 120
C Writing Word, Formula,
C Electron Configurations 122
272
and Balanced C hemical Equations
Math Tutor D Balancing Chemical Equations 273
Weighted Averages and Atomic Mass 128
E Balancing Chemical Equations 273
Chapter 5 The Periodic Law F Activity Series 286
Sample Problems Math Tutor Balancing Chemical Equations 294
A The Periodic Table and Electron Configurations 143
Chapter 9 Stoichiometry
B Hie Periodic Table and Electron Configurations
'
146
C 1 lie PericxlicTable and Electron Configurations
'

148 Sample Problems

A Stoichiometric Calculations Using Mole Ratios 305
D ’
Ilie Periodic Table and Electron Configurations 148
B Stoichiometric Calculations Using Mole Ratios 306
Atomic Radius
E 152
C Stoichiometric Calculations Using Mole Ratios 307
F
Periodic Trends in Ionization Energy 156
D Stoichiometric Calculations Using Mole Ratios 309
G
Periodic Trends in Electronegativity 162
E Stoichiometric Calculations Using Mole Ratios 310
Math Tutor Writing Electron C onfigurations 170
F Limiting Reactant 313
Chapter 6 Chemical Bonding GLimiting Reactant 314
HPercentage Yield 317
Sample Problems
A Classifying Bonds 177 Math Tutor Using Mole Ratios 324
B Electron - Dot Notation 184
Chapter 10 States of Matter
C Lewis Structures 185
D Lewis Structures 188
Sample Problems
A Using Molar Enthalpy of Vaporization 352
E VSEPR Theory and Molecular Geometry 198
F VSEPR Theory and Molecular Geometry 201 Math Tutor
Calculating Using Enthalpies of Fusion 356
Math Tutor Drawing Lewis Structures 214

XIV CONTENTS
Chapter 11 Gases Chapter 16 Reaction Energy
Sample Problems Sample Problems
AConverting Between Units of Pressure 365 A Specific Heat 533
BCalculating Partial Pressures 367 BEnthalpy of Reaction 541
CUsing Boyle’s Law 370 CEnthalpy of Formation 543
DUsing Charles's Law 372 DCalculating Free-Energy Change 550
EUsing Gay-Lussac’s Law 373 Math Tutor Hess’s Law 556
F Using the Combined Gas Law 375
G Calculating with Avogadro's Law 381 Chapter 17 Reaction Kinetics
H Cias Stoichiometry 382 Sample Problems
I Hie Ideal Gas Law 385 A Energy Diagrams 566
i Graham’s Law of Effusion 385 B Determining Rate Law and Rate Constant 574
C Determining Rate Law and Rate Constant 575
Math Tutor
Algebraic Rearrangements of ( ias Laws 306 D Determining Rate-Determining
Step and Rate Law 577
Chapter 12 Solutions E Determining Effects on Reaction Rate 577
Sample Problems Math Tutor Writing Rate Laws 584
ACalculating with Molarity 420
BCalculating with Molarity 420 Chapter 18 Chemical Equilibrium
CCalculating with Molarity 421 Sample Problems
D( alculating with Molality 423 A Equilibrium Constant 504
ECalculating with Molality 424 B Solubility Product Constant 616
Math Tutor Calculating Solution Concentration 430 C Calculating Solubility 617
D Precipitation Calculations 619
Chapter 13 Ions in Aqueous Solutions and Math Tutor Determining Equilibrium Constants 626
Colligati ve Pro pert ies
Sample Problems Chapter 19 Oxidation - Reduction Reactions
ACalculating Moles of Dissolved Ions 436 Sample Problems
B Writing Net Ionic Equations 440 A Balancing Equations for Redox Reactions
CCalculating Freezing-Point Depression 449 Math Tutor Balancing Redox Equations 650
DCalculating Molal Concentration 449
Chapter 20 Electrochemistry
ECalculating Boiling- Point Elevation 451
FFreezing-Point Depression of Electrolytes 454 Sample Problems
A Calculating Cell Potentials 665
Math Tutor
Boiling and Freezing Points of Solutions 462 Math Tutor Calculating Cell Potentials 676

Chapter 21 Nuclear Chemistry

Chapter 14 Acids and Rases
Sample Problems
Math Tutor A Balancing Nuclear Reactions 686
Writing Equations for Ionic Reactions 494
B Calculating with Half -Life 690
Chapter 15 Acid - Ruse Titration and pH Math Tutor Calculating with Half -Life 706
Sample Problems
A Calculating Hvdronium and
Chapter 22 Organic Chemistry
Hydroxide Concentrations 502 Sample Problems
B Calculating pH 505 A Naming Alkanes 721
C Calculating pH 506 B Naming Alkenes 726
D Calculating Hvdronium Math Tutor Calculating Empirical Formulas 746
Concentration Using pH 507
Chapter 23 Riological Chemistry
E Calculating Hvdronium and
508
Math Tutor Interpretation of the Genetic Code 780
Hydroxide Concentrations
F C alculating the Molarity of an Acid Solution 520
Math Tutor Using Logarithms and pH 526

CONTENTS XV
Labs
PRE- LABS
Extraction and Filtration 844 Volumetric Analysis 850
Gravimetric Analysis 846 Calorimetry 852
Paper Chromatography 848

EXPERIMENTS
Chapter Chapter
1 Mixture Separation INQUIRY 26 12 Separation of Pen Inks by
2 Percentage of Water Paper Chromatography MICRO 432
in Popcorn 64 13 Testing Water for Ions MICRO 464
3 Conservation of Mass MICRO INQUIRY 94 14 Is It an Acid or a Base ? MICRO INQUIRY 496
4 Flame Tests MICRO 130 15 How Much Calcium Carbonate
5 The Mendeleev Lab of 1869 INQUIRY 172 Is in an Eggshell ? MICRO 528
6 Types of Bonding in Solids INQUIRY 216 16 Calorimetry and Hess's Law 558
7 Determining the Empirical 17 Rate of a Chemical Reaction MICRO 586
Formula of Magnesium Oxide 258 18 Measuring Ke for Acetic Acid MICRO
}
628
8 Blueprint Paper 296 19 Reduction of Mn in MnO MICRO 652
9 Stoichiometry and 20 Voltaic Cells
^ 678
Gravimetric Analysis 326 21 Simulation of Nuclear Decay
10 " Wet " Dry Ice MICRO 358 Using Pennies and Paper 708
11 Mass and Density of Air 22 Polymers and Toy Balls 748
at Different Pressures MICRO 398 23 Casein Glue 782

QUICK LABS
Chapter Chapter
2 Density of Pennies 39 15 Testing the pH of Rainwater 514
3 Constructing a Model 71 17 Factors Influencing
4 The Wave Nature of Light: Reaction Rate 578
Interference 106 19 Redox Reactions 644
5 Designing Your Own
Periodic Table 137
8 Balancing Equations <3
Using Models 2S4
9 Limiting Reactants in a Recipe 316
A-
11 Diffusion 387
12 Observing Solutions,
Suspensions, and Colloids 405
14 Household Acids and Bases 472

XVI CONTENTS
Feature Articles
ISTORICAL CHEMISTRY
CAREERS
in Chemistry vwftjn
Chapter
Chapter
3 Physical Chemist 70
2 Classical Ideas About Matter 43
5 Materials Scientist 145
3 Discovery of Element 43 81
6 Computational Chemist 204
4 The Noble Decade 114
7 Pharmacist 222
9 The Case of Combustion 302
9 Chemical Technician 300
11 Chemistry 's First Law 376
12 Environmental Chemist 408
13 The Riddle of Electrolysis 444
15 Analytical Chemist 516
18 Fixing the Nitrogen Problem 596
22 Petroleum Engineer 720
21 An Unexpected Finding 700
23 Forensic Chemist 774
22 The Beginnings of Organic Chemistry 715
23 Charles Drew and Blood Transfusions 762 CVCVA vTftrm
I

rsrrtrTTrifaii 20 Chemical Engineer HC6ELEX

1 A Broken Rule: Chemical Reactions
of the Noble Gases
3 Modern Alchemy
21 Glenn Seaborg
23 Unraveling the Mystery of DNA
HC6 MTXX
HC6 ATMX
HC6 NUCX
HC6 BIOX
Chemistry in Action
Chapter
1 Superconductors
osae 18
2 Breaking Up Is Easy to Do

«
32
4 Fireflies 102

90 CROSS- DISCIPLINARY
CONNECTION
6 Ultrasonic Toxic - Waste Destroyer
7 Mass Spectrometry: Identifying Molecules
8 Carbon Monoxide Catalyst
180
236
275
Chapter Fluoridation and Tooth Decay 283
1 Secrets of the Cremona Violins 15 Combustion Synthesis 288
2 Some Handy Comparisons of Units 35 10 Surface Melting 346
12 Artificial Blood 417 11 The Gas Laws and Scuba Diving 368
14 Acid Water—A Hidden Menace 477 Automobile Air Bags 380
It's a Bitter Pill 484 13 Water Purification by Reverse Osmosis 453
15 Liming Streams 510 16 Self - Heating Meals 545
18 Blood Buffers 609 Diamonds Are Forever ? 549
21 Quarks 682 17 Explosives 572
Catalytic Converters 579
4 Spintronics HC6 ARRX 19 Photochromic Lenses 634
5 Essential Elements HC6 PERX Skunk - Spray Remedy 636
7 Smell-A Chemical Sense HC6 FRMX 20 Fuel -Cell Cars 666
10 Cloud Seeding HC6 STMX Sodium Production by Electrolysis 671
13 Minerals HC6IONX 22 Carbon Allotropes 725
16 Free Energy and the Body HC6 NRGX czrX\ ^31
15 Buffers in the Blood HC6 ABTX 2 Roadside Pollution Detector HC6MEAX
18 Limestone Caves HC6 EQUX 6 Nanoscale Computers HC6 BNDX
19 Oxidation- Reduction 8 How Is Our Public Water Treated ? HC6RXNX
and Photosynthesis HC60XRX 9 Air Bags and Stoichiometry HC6 STCX
10 Phase-Change Materials HC6 STMX
12 Surfactants: Molecules with Two Faces HC6 SLNX
14 Undog That Drain HC6 ACDX
Go to go.hrw.com for 17 Monitoring Reaction Kinetics
full-length articles. with Ultraviolet-Visible Spectroscopy HC6RXKX
22 Synthetic Diamonds HC60RGX
High-Barrier Plastics
& HC60RGX

••
FEATURE ARTICLES XVII
 Safety in the Chemistry Laboratory
Any chemical can be dangerous if it is misused. Always follow the instructions for
the experiment. Pay close attention to the safety notes. Do not do anything differ -
ently unless told to do so by your teacher.
C hemicals, even water, can cause harm. The challenge is to know how to use
chemicals correctly. To make sure you are using chemicals correctly, follow the
rules stated below, pay attention to your teacher 's directions, and follow cautions
on chemical labels and in the experiments.
Specific experiments will use a system of Safety Symbols to highlight specific types
of precautions. No matter what Safety Symbols an experiment may contain, the
following safety rules apply any time you are in the lab.

Before You Begin

1. Read the entire activity before entering the underwater swimming—in the lab. Ask your
lab. Be familiar with the instructions before doctor or your teacher how to use eye -cup safety
beginning an activity. Do not start an activity goggles to protect your eyes.
until you have asked your teacher to explain any
5. Know the location of all safety and emergency
parts of the activ ity that you do not understand.
equipment used in the lab. Know proper
2. Student - designed procedures or inquiry activi- fire -drill procedures and the location of all fire
ties must be approved by your teacher before exits. Ask your teacher where the nearest eyewash
you attempt the procedures or activities. stations, safety blankets, safety shower, fire extin-
guisher. first - aid kit . and chemical spill kit are
3. Wear the right clothing for lab work . Before located. Be sure that you know how to operate
beginning work , tie hack long hair, roll up loose the equipment safely.
sleeves, and put on any required personal protec -
tive equipment as directed by your teacher.
Remove your wristwatch and any necklaces or While You Are Working
jewelry that could gel caught in moving parts. 6. Always wear a lab apron and safety goggles.
Avoid or confine loose clothing that could knock Wear these items even il you are not working on
things over, catch on fire, gel caught in moving an activity. Labs contain chemicals that can damage
parts, contact electrical connections, or absorb your clothing, skin , and eyes. Keep the strings
chemical solutions. Wear pants rather than shorts of your lab apron tied.
or skirts. Nylon and polyester fabrics burn and If your safety goggles
melt more readily than cotton does. Protect your cloud up or are
feel from chemical spills and falling objects. Do uncomfortable, ask
not wear open- toed shoes, sandals, or canvas shoes your teacher for
in the lab. In addition, chemical fumes may react help. Lengthening
with and ruin some jewelry, such as pearl jewelry. the strap slight -
Do not apply cosmetics in the lab. Some hair care ly. washing the
products and nail polish are highly flammable. goggles with
soap and
.
4 Do not wear contact lenses in the lab. Even
warm water,
though you will be wearing safety goggles, chemi -
or using an anti-fog
cals could get between contact lenses and your
spray may help the
eyes and could cause irreparable eye damage. If
problem.
your doctor requires that you wear contact lenses
instead ol glasses, then you should wear eye -cup
safety goggles—similar to goggles worn for

•••
XVIII SAFETY IN THE CHEMISTRY LABORATORY
 matches. Make sure that all heating devices and
gas valves are turned off before you leave the lab.
Never leave a heating device unattended when it
is in use. Metal, ceramic, and glass items do not
necessarily look hot when they are hot. Allow all
items to cool before storing them.

14 . Remember how easily glass can break and

cause a serious cut . Check the condition of any
glassware before and after using it . Inform your
teacher of any broken, chipped, or cracked glass-
ware. because it should not be used. Never force
glass tubing into rubber tubing, stoppers or wooden
corks. To protect your hands, wear heavy cloth
gloves or wrap toweling around the glass and the
7. NEVER work alone in the lab. Work in the lab tubing, stopper, or cork, and gently push in the
only when supervised by your teacher. Do not leave glass. Do not pick up broken glass with your bare
equipment unattended while it is in operation. hands. Dispose of broken glass in a specially
designated disposal container.
8. Perform only activities specifically assigned
by your teacher. Do not attempt any procedure 15. Exercise caution when working with electrical
without your teacher ’s direction. Use only materials equipment. Do not use electrical equipment with
and equipment listed in the activity or authorized frayed or twisted wires. Be sure that your hands
by your teacher. Steps in a procedure should be are dry before using electrical equipment. Do not
performed only as described in the activity or as let electrical cords dangle from work stations.
approved by your teacher. Dangling cords can cause you to trip and can
cause an electrical shock . The area under and
9. Keep your work area neat and uncluttered. around electrical equipment should be dry: cords
Have only books and other materials that are should not lie in puddles of spilled liquid.
needed to conduct the activity in the lab. Keep
backpacks, purses, and other items in your desk , 16. Do not fool around in the lab. Take your lab
locker, or other designated storage areas. work seriously, and behave appropriately in the lab.
Lab equipment and apparatus are not toys: never
.
10 Always heed safety symbols and cautions list - use lab time or equipment for anything other than
ed in activities, listed on handouts, posted in the intended purpose. Be aware of the safety of
the room, provided on chemical labels, and vour classmates as well as vour safety at all times.
given verbally by your teacher. Ik* aware of the
potential hazards of the required materials and
procedures, and follow all precautions indicated.
Working With Chemicals
17. NEVER taste chemicals or allow them to contact
.
11 Be alert, and walk with care in the lab. Be your skin. Keep your hands away from your face
aware of others near you and your equipment.
and mouth, even if you are wearing gloves.
12. Do not take food, drinks, chewing gum, or 18. Do not inhale fumes directly. When instructed
tobacco products into the lab. Do not store
to smell a substance, use your hand to wave the
or eat food in the lab.
fumes toward your nose, and inhale gently.
.
13 Use extreme caution when working with hot
19. Read chemical labels. Follow the instructions
plates and other heating devices. Keep your
and safety precautions stated on the labels.
head, hands, hair, and clothing away from the flame
or heating area. Remember that metal surfaces 20. If you are working with flammable liquids,
connected to the heated area will become hot by use only small amounts. Be sure no one else
conduction. Use tongs when heating containers is using a lit Bunsen burner or is planning to
.
and never hold or touch them Gas burners use one when you are working w i t h flammable
should be lit only with a spark lighter, not with liquids, because the fumes can ignite.

SAFETY IN THE CHEMISTRY LABORATORY XIX

 If you spill a chemical on your skin, wash the
chemical off in the sink and call your teacher.
II you spill a solid chemical onto vour clothing,
brush it off carefully without scattering it onto
somebody else and call your teacher. If you gel
liquid on your clothing, wash it off right away by
using the faucet at the sink and call your teacher.
If the spill is on vour pants or something else that
will not lit under the sink faucet, use the safety
shower. Remove the pants or other affected
clothing while you are under the shower, and call
your teacher. ( It may be temporarily embarrassing
to remove pants or other clothing in front of vour
classmates, but failure to Hush the chemical off
your skin could cause permanent damage. )
27. If you get a chemical in your eyes, walk
21. For all chemicals, take only what you need. immediately to the eyewash station, turn it
I lowever, if you do happen to take too much and on, and lower your head so your eyes are in
have some left over. DO NOT put it back in the the running water. I fold your eyelids open with
bottle. II somebody accidentally puts a chemical your thumbs and lingers, and roll your eyeballs
into the wrong bottle, the next person to use it .
around You have to flush your eyes continuously
w ill have a contaminated sample. Ask your for at least 15 minutes. Call vour teacher while
teacher what to do with any leftover chemicals. you are doing this.

22. NEVER take any chemicals out of the lab.

( This is another one that you should already
When You Are Finished
know. You probably know the remaining rules 28. Clean your work area at the conclusion of
also, but read them anyway. ) each lab period as directed by your teacher.
Broken glass, chemicals, and other waste products
Emergency Procedures should be disposed of in separate, special containers.
Dispose of waste materials as directed by your
23. Follow standard fire - safety procedures. If teacher. Pul away all material and equipment
your clothing catches on fire, do not run: WALK according to your teacher ’s instructions. Report
to the safety shower, stand under it. and turn it any damaged or missing equipment or materials
on. While doing so. call to your teacher. In case to your teacher.
of fire, alert your teacher and leave the lab.
29. Wash your hands with soap and hot water
24. Report any accident, incident, or hazard— after each lab period. To avoid contamination,
no matter how trivial— to your teacher wash your hands at the conclusion of each lab
immediately. Any incident involving bleeding, period, and before you leave the lab.
burns, fainting, nausea, dizziness, chemical expo-
sure. or ingestion should also be reported imme -
diately to the school nurse or to a physician. If A Final Reminder
you have a close call, tell your teacher so that you 30. Whether or not the lab instructions remind
and your teacher can find a way to prevent it you, all of these rules apply all of the time.
from happening again.

25. Report all spills to your teacher immediately.

C all your teacher rather than trying to clean a
spill yourself. Your teacher will tell you whether it
is safe for you to clean up the spill: if it is not safe,
your teacher will know how to clean up the spill.

XX SAFETY IN THE CHEMISTRY LABORATORY

Safety Symbols
To highlight specific types of precautions, the following symbols are used through -
out the lab program. Remember that no matter what safety symbols you see in the
textbook , all 30 of the lab safety rules previously described should be followed at
all times.

EYE PROTECTION CHEMICAL SAFETY

• Wear safety goggles in the lab at all times. Never return unused chemicals to the origi -
nal container. Take only what you need.
• Know how to use the eyewash station. If
chemicals get into vour eyes, flush your Label the beakers and test tubes you use
eyes ( including under the eyelids ) with run - with the chemicals they contain .
ning water at the eyewash station for at Never transfer substances by sucking on a
least 15 minutes. Use your thumb and fin - pi pet or straw ; use a suction bulb.
gers to hold your eyelids open and roll your
eyeball around . While doing so. ask another Do not mix any chemicals unless specifical -
student to notify vour teacher. ly instructed to do so by your teacher.
If a chemical spills on the floor or lab bench ,
tell your teacher, and wait for instructions
CLOTHING PROTECTION before cleaning it up yourself.
• Wear an apron or lab coat at all times in
the lab.
CAUSTIC SUBSTANCE SAFETY
• l ie back long hair, secure loose clothing ,

and remove loose jewelry so that they do • Do not pour water into a strong acid or
base. The mixture can produce heat and can
not knock over equipment or come into
contact with hazardous materials. splatter.

HAND SAFETY HEATING SAFETY

• Wear protective gloves when working with • Avoid using open flames. If possible, work
chemicals. only w ith hot plates having an on /off switch
and an indicator light .
• Use a hot mitt or tongs to handle equip-
ment that may be hot . • When heating a chemical in a test tube,
point the open end of the test tube away
from yourself and others.
GLASSWARE SAFETY
Inspect glassware before use: do not HYGIENE CARE
use chipped or cracked glassware.
• Keep your hands away from your face and
Never place glassware, containers of chemi- mouth while you work in the lab.
cals, or anything else near the edges of a lab
bench or table. • Do not eat or drink any food from labora -
tory containers.
• Wash vour hands thoroughly before you
leave the lab.

WASTE DISPOSAL
• Help protect our environment by follow ing
the instructions for proper disposal .

SAFETY SYMBOLS XXI

 How to Use Your Textbook
Your Roadmap for Success with Modem Chemistry

Get Organized
Keep a science notebook so that you are ready to SECTION 1
take notes when your teacher reviews material in Organic Compounds
class. Keep your assignments in this notebook so OBJECTIVES
that you can review them when studying for the .» *
E»tfan how th uiwtum it d
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chapter test. .A- II compound cunum niNm i
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1 1stirr I shows 4 lew famtkur Hems thit cunum organic cvtnrintreh

a Cnmpare the use of molecuhu
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*
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the book , describes a number of Study Skills that *
can help you succeed in chemistry, including Carbon Bonding and the Diversity . Compart* structural and geo
metre tsomers of organ
of Organic Compounds *
several approaches to note taking. IV drtcmtv oi,<f|fjriK compounds results limn Hu uiifctiKflcvi o< car
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section because they will tell you what you’ll |

need to learn. Key Terms are boldfaced in each

chapter. Use the glossary to locate definitions
quickly. After reading each chapter, turn to the
Chapter Highlights page. Then, review the list
of key terms and read the brief summaries of
the chapter ’s main ideas. You may want to do
this even before you read the chapter.
STUDY TIP If vou don’t understand a definition.
J

reread the page on which the term is introduced. 0 »G A

* rufUMMi 711

The surrounding text should help make the

definition easier to understand.

Be Resourceful Use the Web

SciLinks boxes in your Visit go.hrw.com
textbook take you to Find resources and
«
NSTA
resources that you can use resource materials that
for science projects, reports, go with your textbook at go.hrw com. .
and research papers. Go to scilinks.org. and Enter the keyword HC 6 HOME to access
type in the SciLinks code to get information on the home page for your textbook.
a topic.

XXII HOW TO USE YOUR TEXTBOOK

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password to log onto the Holt Online
Learning site, you ’ll find your complete
textbook on the Web. In addition, you'll find some great
project ideas from

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type in the keywrord
.
Scientific A trier icon

learning tools and practice quizzes. You'll be able to see HC 6SAX .

how well you know the material from your textbook .

•••
HOW TO USE YOUR TEXTBOOK XXIII
 CHAPTER 1

Matter and Change

Chemistry is central to all of the sciences.
 SECTION 1
Chemistry Is a
Physical Science OBJECTIVES
Define chemistry.

w List examples of the branches

of chemistry.
r he natural sciences were once divided into two broad categories:
the biological sciences and the physical sciences. Living things are the
main focus of the biological sciences. The physical sciences focus Compare and contrast
mainly on nonliving things. However, because we now know that both basic research, applied
living and nonliving matter consist of chemical structures, chemistry is research, and technological
development.
central to all the sciences, and there are no longer distinct divisions
between the biological and physical sciences.
Chemistry is the study of the composition, structure, and properties of
matter, the processes that matter undergoes, and the energy changes that
accompany these processes. Chemistry deals with questions such as.
What is a material s makeup? How does a material change when heat -
'

ed , cooled , or mixed with other materials and why does this behavior
occur? Chemists answer these kinds of questions during their work .
Instruments are routinely used in chemistry to extend our ability to
observe and make measurements. Instruments make it possible, for exam -
—
ple. to look at microstructures things too tiny to be seen with the unaid -
ed eve. The scanning electron microscope reveals tiny structures by FIGURE 1 A balance ( a ) is an
beaming particles called electrons at materials. When the electrons hit a instrument used to measure the
mass of materials. A sample of I ) NA
material, they scatter and produce a pattern that shows the material s '

placed in a scanning tunneling micro-

microstructure. Invisible rays called X rays can also be used to scope produces an image ( b ) showing
the contours of the DNA‘s surface.

(a )

MATTER AND CHANGE 3

 determine microstructures. The patterns that appear, called X -ray diffrac-
tion patterns, can be analyzed to reveal the arrangement of atoms, mole -
cules. or other particles that make up the material. By learning about
microslructures. chemists can explain the behavior of macrostructures
the visible things all around you.
—

Branches of Chemistry
Chemistry includes many different branches of study and research . The
following are six main areas, or branches, of study. But like the biologi -
cal and physical sciences, these branches often overlap.
——
1. Organic chemistry the study of most carbon -containing compounds
2. Inorganic chemistry the study of non-organic substances, many of
which have organic fragments bonded to metals ( organometallics )
—
3. Physical chemistry the study of the properties and changes of
matter and their relation to energy
—
4. Analytical chemistry the identification of the components and com -
position of materials
—
5. Biochemistry the study of substances and processes occurring in
living things
—
6. Theoretical chemistry the use of mathematics and computers to
understand the principles behind observed chemical behavior and to
design and predict the properties of new compounds

In all areas of chemistry, scientists work with chemicals. A chemical

is any substance that has a definite composition. For example, consider
the material called sucrose, or cane sugar. It has a definite composition
in terms of the atoms that compose it . It is produced by certain plants in
the chemical process of photosynthesis. Sucrose is a chemical. Carbon
dioxide, water, and countless other substances are chemicals as well .
Knowing the properties of chemicals allows chemists to find suitable
uses for them . For example, researchers have synthesized new sub-
stances. such as artificial sweeteners and synthetic fibers. The reactions
used to make these chemicals can often be carried out on a large scale
to make new consumer products such as flavor enhancers and fabrics.

Basic Research
Basic research is carried out for the sake of increasing knowledge, such
as how and why a specific reaction occurs and what the properties of a
substance are. Chance discoveries can be the result of basic research . The
properties of TeflonrM , for example, were first discovered by accident . A
researcher named Roy Plunkett was puzzled by the fact that a gas cylin -
der used for an experiment appeared to be empty even though the mea -
sured mass of the cylinder clearly indicated there was something inside.
Plunkett cut the cylinder open and found a white solid . Through basic
research . Plunkett ’s research team determined the nonstick properties,
molecular structure, and chemical composition of the new material .

4 CHAPTER 1
Applied Research
Applied research is generally carried
out to solve a problem. For example,
when certain refrigerants escape into
the upper atmosphere, they damage the
ozone layer which helps block harmful
,

ultraviolet rays from reaching the sur -

face of Earth. In response to concerns
that this atmospheric damage could
pose health problems, chemists have
developed new refrigerants. In applied
research, researchers are driven not bv
curiosity or a desire to know but by a
desire to solve a specific problem.

Technological
Development
Technological development typically
FIGURE 2 The chemical structure of the material in an optical fiber
involves the production and use of
gives it the property of total internal reflection. This property, which
products that improve our quality of allows these fibers to carry light , was discovered through basic and
life. Examples include computers, applied research. The use of this property to build networks by sending
catalytic converters for cars, and data on light pulses is the technological development of fiber optics.
biodegradable materials.
Technological applications often lag far behind the discoveries that
arc eventually used in technologies. For example, nonstick cookware, a
technological application, was developed well after the accidental dis-
covery of Teflon. When it was later discovered that the Teflon coating
on cookware often peeled off, a new challenge arose. Using applied
research, scientists were then able to improve the bond between the
Teflon and the metal surface of the cookware so that it did not peel.
Basic research, applied research, and technological development often
overlap. Discoveries made in basic research may lead to applications that
.
can result in new technologies For example, knowledge of crystals and
light that was gained from basic research was used to develop lasers. It
was then discovered that pulses of light from lasers can be sent through
optical fibers. Today, telephone messages and cable television signals are
carried quickly over long distances using fiber optics.

SECTION REVIEW Critical Thinking

1. Define chemistry. 4. INFERRING RELATIONSHIPS Scientific and techno -
2 . Name six branches of study in chemistry. logical advances are constantly changing how
people live and work. Discuss a change that you
3. Compare and contrast basic research, applied have observed in your lifetime and that has made
research, and technological development. life easier or more enjoyable for you.

MATTER AND CHANCE 5

 SECTION 2
Matter and Its
OBJECTIVES Properties
u Distinguish between the
physical properties and
chemical properties of matter.

Classify changes of matter as L ook around you. You can sec a variety of objects— books, desks,
physical or chemical. chairs, and perhaps trees or buildings outside. All those things are made
up of matter, but exactly what is matter ? What characteristics, or prop-
erties. make matter what it is? In this section, you will learn the answers
>j Explain the gas, liquid, to these questions.
and solid states in terms
Explaining what matter is involves finding properties that all matter
of particles.
has in common. That may seem difficult , given that matter takes so
many different forms. For the moment, just consider one example of
Explain how the law of con- matter — a rock . The first thing you might notice is that the rock takes
servation of energy applies to up space. In other words, it has volume . Volume is the amount of three-
changes of matter. dimensional space an object occupies. All matter has volume. All mat -
ter also has a property called mass. Mass is a measure of the amount of

v Distinguish between a mix - matter . Mass is the measurement you make using a balance. Matter can
ture and a pure substance. thus be defined as anything that has mass and takes up space . These two
properties are the general properties of all matter.

Basic Building Blocks of Matter

Matter comes in many forms. The fundamental building blocks of mat -
ter are atoms and molecules. These particles make up elements and
compounds. An atom is the smallest unit of an element that maintains the
chemical identity of that element. An element is a pure substance that
Carbon atom
cannot be broken down into simpler, stable substances and is made of
one type of atom. Carbon is an element and contains one kind of atom.

Hydrogen atom

tJ

Oxygen atom Carbon atom

( b)

FIGURE 3 Both elements and compounds are made of atoms, as shown in

(a ) .
these models of ( a ) diamond and ( b ) sucrose ( table sugar )

6 CHAPTER 1
 A compound is a substance that can be broket ] down into simple sta -
ble substances. Each anti pound is made from the atoms of two or nunc
elements that are chemically bonded. Water is an example of a com -
pound. It is made of two elements, hydrogen and oxygen. The atoms of
hydrogen and oxygen are chemically bonded to form a water molecule.
You will learn more about the particles that make up compounds when
you study chemical bonding in Chapter 6. For now. you can think of a
molecule as the smallest unit of an element or compound that retains all
of the properties of that element or compound.

Properties and Changes in Matter

Every substance, whether it is an element or a compound, has charac -
teristic properties. Chemists use properties to distinguish between sub -
stances and to separate them. Most chemical investigations are related
to or depend on the properties of substances.
A property may be a characteristic that defines an entire set of sub -
stances. That property can be used to classify an unknown substance as
a member of that group. For example, many elements are classified as
metals. The distinguishing property of metals is that they conduct elec -
tricity well. Therefore, if an unknown element is tested and found to
conduct electricity well, it is a metal.
Properties can help reveal the identity of an unknown substance.
However, conclusive identification usually cannot be made based on
only one property. Comparisons of several properties can be used
together to establish the identity of an unknown. Properties are either
intensive or extensive. Extensive properties depend on the amount of
matter that is present . Such properties include volume, mass, and the
amount of energy in a substance. In contrast, intensive properties do not
depend on the amount of matter present . Such properties include the
melting point, boiling point , density, and ability to conduct electricity and
to transfer energy as heat. Intensive properties are the same for a given
substance regardless of how much of the substance is present. Properties
can also be grouped into two general types: physical properties and
chemical properties.

Physical Properties and Physical Changes

A physical property is a characteristic that can be observed or measured
without changing the identity of the substance. Physical properties describe
the substance itself, rather than describing how it can change into other
substances. Examples of physical properties are melting point and boiling
point.Those points are. respectively, the temperature at which a substance
melts from solid to liquid and the temperature at which it boils from liq-
uid to gas. For example, water melts from ice to liquid at 0 C ( 273 k or FIGURE 4 Water boils at 1 ( H ) C
32 F). Liquid water boils to vapor at 100 C (373 k or 212 F ). no matter how much water is in the
A change in a substance that does not involve a change in the identity container. Boiling point is an inten -
of the substance is called a physical change. Examples of physical sive property.

MATTER AND CHANGE 7

 changes include grinding, cutting, melting, and boiling a material. These
types of changes do not change the identity of the substance present .
Melting and boiling are part of an important class of physical
changes called changes of state. As the name suggests, a change of state
is a physical change of a substance from one state to another. The three
common states of matter are solid , liquid , and gas.
Matter in the solid state has definite volume and definite shape. For
example, a piece of quart / or coal keeps its size and its shape, regardless
of the container it is in . Solids have this characteristic because the par -
ticles in them are packed together in relatively fixed positions. The par -
ticles are held close together by the strong attractive forces between
them , and only vibrate about fixed points.
Matter in the liquid state has a definite volume but an indefinite shape;
a liquid assumes the shape of its container. For example, a given quan -
SCllNKS j
aM maMUM»4 fcy the
Nahwwl Mratr feariwn AtuxtaOo
tity of liquid water takes up a definite amount of space, but the water
takes the shape of its container. Liquids have this characteristic because
* the particles in them are close together but can move past one another.
For a variety of links related to this
chapter, go to wow solink.s. org The particles in a liquid move more rapidly than those in a solid. This
Topic: Physical/ Chemicfl! causes them to overcome temporarily the strong attractive forces
Changes between them , allowing the liquid to flow.
SciLinks code: HC6114 b Matter in the gas state has neither definite volume nor definite shape.
For example, a given quantity of helium expands to fill any size contain -
er and takes the shape of the container. All gases have this characteristic
because they are composed of particles that move very rapidly and are
at great distances from one another compared with the particles of liq -
uids and solids. At these great distances, the attractive forces between gas
particles have less of an effect than they do at the small distances
between particles of liquids and solids.
An important fourth state of matter is plasma. Plasma is a
high -temperature physical state of matter in which atoms lose
most of their electrons, particles that make up atoms. Plasma is
found in fluorescent bulbs.
Melting, the change from solid to liquid , is an example of
a change of state. Boiling is a change of state from liquid to
gas. Freezing, the opposite of melting, is the change from a
liquid to a solid . A change ol state does not affect the identi -
ty of the substance. For example, when ice melts to liquid
water or when liquid water boils to form water vapor, the
same substance, water, is still present , as shown in Figure 6.
Hie water has simply changed stale, but it has not turned into
a different compound . Only the distances and interactions
between the particles that make up water have changed .

Chemical Properties and Chemical Changes

FIGURE 5 Because it possesses certain chemical
Physical properties can be observed without changing the
properties, a test strip containing Benedict s solu -
'

tion is used to test for the presence of sugar in identity of the substance, but properties of the second type-
urine. The test strip is dipped into the sample. The
test strip is then matched to a color scale to deter -
—
chemical properties cannot . A chemical property relates to a
substance 's ability to undergo changes that transform it into dif -
mine the sugar level in the urine. ferent substances. Chemical properties are easiest to see when

8 CHAPTER 1
 FIGURE 6 Models for water
in three states. The molecules are
close together in the solid and liquid
states hut far apart in the gas state.
The molecules in the solid state are
relatively fixed in position hut those
,

in the liquid and gas states can flow

around each other.

substances react to form new substances. For example, the ability of

charcoal ( carbon ) to burn in air is a chemical property. When charcoal
burns, it combines with oxygen in air to become a new substance, carbon
dioxide gas. After the chemical change, the amounts of the original sub- Historical Chemistry
stances, carbon and oxygen , are less than before. A different substance Go to go. hrw. com for a full -length
with different properties has been formed . Other examples of chemical article on the chemical reactions of
properties include the ability of iron to rust by combining with oxygen in noble gases.
air and the ability of silver to tarnish by combining with sulfur. o/
Keyword: HC 6 MTXX
A change in w hich one or more substances are converted into different
substances is called a chemical change or chemical reaction. The sidy -
stances that react in a chemical change are called the reactants. The sub -
stances that are formed by the chemical change are called the products. In
the case of burning charcoal , carbon and oxygen are the reactants in a
combustion , or burning, reaction . Carbon dioxide is the product. The
chemical change can be described as follows:

Carbon plus oxygen yields ( or forms ) carbon dioxide.

Arrows and plus signs can be substituted for the words yields and plus,
respectively:

carbon + oxygen » carbon dioxide

MATTER AND CHANGE 9

 Mercury
Physical properties: silver- white,
liquid metal; in the solid state, mercury
is ductile and malleable and can be
cut with a knife
Chemical properties: forms alloys
Oxygen
with most metals except iron; com -
Physical properties: colorless,
bines readily with sulfur at normal odorless gas, soluble in water
temperatures; reacts with nitric acid
Chemical properties: supports
and hot sulfuric acid; oxidizes to combustion; reacts with many
form mercury(ll) oxide upon heating
metals

Mercury ( ll ) oxide
Physical properties: bright red or
orange- red, odorless crystalline solid,
almost insoluble in water
Chemical properties: decomposes
when exposed to light or at 500°C
to form mercury and oxygen gas

FIGURE 7 When mercury!ID

oxide is heated, it decomposes to The decomposition of the mercury compound shown in Figure 7 can
form oxygen gas and mercury
( which can be seen on the side of
be expressed as follows:
.
the test tube ) Decomposition is a
chemical change that can be mercury (II) oxide » mercury + oxygen
observed by comparing the proper -
ties of mercury( 11 ) oxide, mercury, Chemical changes and reactions, such as combustion and decomposi -
and oxygen. tion. form products whose properties differ greatly from those of the
reactants. However, chemical changes do not affect the total amount of
matter present before and after a reaction. The amount of matter, and
therefore the total mass, remains the same.

Energy and Changes in Matter

When physical or chemical changes occur, energy is always involved.
The energy can take several different forms, such as heat or light.
Sometimes heat provides enough energy to cause a physical change, as
in the melting of ice. and sometimes heat provides enough energy to
cause a chemical change, as in the decomposition of water vapor to
form oxygen gas and hydrogen gas. But the boundary between physical
and chemical changes isn' t always so clear. For example, while most
chemists would consider the dissolving of sucrose in water to be a phys -
ical change, many chemists would consider the dissolving of table salt in
water to be a chemical change. As you learn more about the structure
of matter, you will better understand why the boundaries between
chemical and physical changes can be confusing .
10 CHAPTER 1
 Accounting lor all the energy present before and after a change is
not a simple process. But scientists who have done such experimenta -
tion are confident that the total amount of energy remains the same.
Although energy can be absorbed or released in a change, it is not
destroyed or created. It simply assumes a different form. This is the law
of conservation of energy.

Classification of Matter
Matter exists in an enormous variety of forms. Any sample of matter,
however, can be classified either as a pure substance or as a mixture.
The composition of a pure substance is the same throughout and does
not vary from sample to sample. A pure substance can be an element or
a compound. Mixtures, in contrast , contain more than one substance.
They can vary in composition and properties from sample to sample
and sometimes from one part of a sample to another part of the same
sample. All matter, whether it is a pure substance or a mixture, can be
classified in terms of uniformity of composition and properties of a
given sample. Figure 8 illustrates the overall classification of matter into
elements, compounds, and mixtures.

Mixtures
You deal with mixtures every day. Nearly every object around you,
including most things you eat and drink and even the air you breathe, FIGURE 8 This classification
is a mixture. A mixture is a blend of two or more kinds of matter each scheme for matter shows the
relationships among mixtures,
compounds, and elements.

Matter

Yes Can it be separated ? No

Mixtures Pure substances

Is the Can it be decom -

Yes
composition
uniform ? No
l posed by ordinary
chemical means?

d
Homogeneous Heterogeneous
Compounds Elements
mixtures mixtures
( water, sodium (gold, aluminum,
( air, sugar in water, (granite, wood,
chloride, sucrose) oxygen, chlorine )
stainless steel ) blood)

MATTER AND CHANGE 11

(a ) (C)

FIGURE 9 ( a ) Barium chromate can he separated from the solution in the

beaker using filtration ( h ) A centrifuge can he used to separate certain solid
,

components. The centrifuge spins rapidly, which causes the solids to settle to the
bottom of the test tube. ( c ) The components of an ink can be separated using
pa pe r c h roniatography.

of which retains its own identity and properties. The parts, or compo-
nents, of a mixture are simply mixed together physically and can usually
be separated . As a result , the properties of a mixture are a combination
of the properties of its components. Because mixtures can contain vari -
ous amounts of different substances, a mixture’s composition must be
specified. This is often done in terms of percentage by mass or by vol -
ume. For example, a mixture might be 5 % sodium chloride and 95 %
water by mass.
Some mixtures are uniform in composition ; that is, they are said to be
homogeneous. They have the same proportion of components through -
out. Homogeneous mixtures are also called solutions. A salt - water solu -
tion is an example of such a mixture. Other mixtures are not uniform
throughout; that is. they are heterogeneous. For example, in a mixture
of clay and water, heavier clay particles concentrate near the bottom of
the container.
Some mixtures can be separated by filtration or vaporized to sepa -
rate the different components. Filtration can be used to separate a mix -
ture of solid barium chromate from the other substances, as shown in
the beaker in Figure 9a . The yellow barium compound is trapped by the
filter paper , but the solution passes through. If the solid in a liquid -solid
mixture settles to the bottom of the container, the liquid can be care -
fully poured off ( decanted ). A centrifuge ( Figure 9b ) can be used to sep-
arate some solid -liquid mixtures, such as those in blood . Another
technique, called paper chromatography, can be used to separate mix -
tures of dyes or pigments because the different substances move at dif -
ferent rates on the paper ( Figure 9c ).

12 CHAPTER 1
Pure Substances
Any sample of a pure substance is homogeneous. A pure substance has
a fixed composition and differs from a mixture in the following ways:
1 . Every sample o f a given pure substance has exactly the same charac -
teristic properties. All samples of a pure substance have the same
characteristic physical and chemical properties. These properties are
so specific that they can be used to identify the substance. In contrast ,
the properties of a mixture depend on the relative amounts of the
mixtures components.
2. Every sample of a given pure substance has exactly the same compo-
sition. Unlike mixtures, all samples of a pure substance have the
same makeup. For example, pure water is always 11.2 % hydrogen
and 88.8% oxygen by mass.

Pure substances are either compounds or elements. A compound can

be decomposed , or broken down , into two or more simpler compounds
or elements by a chemical change. Water is a compound made of hydro-
gen and oxygen chemically bonded to form a single substance. Water
can be broken down into hydrogen and oxygen through a chemical
reaction called electrolysis, as shown in Figure 10a.
Sucrose is made of carbon , hydrogen , and oxygen . Sucrose breaks
down to form the other substances shown in Figure 10 b. Under intense
heating, sucrose breaks down to produce carbon and water.

FIGURE 10 ( a ) Passing an
electric current through water
causes the compound to break
down into the elements hydrogen
Hydrogen and oxygen , which differ in compo -
molecule , H 2 sition from water, ( b ) When sucrose
is heated. it caramelizes. When it
is heated to a high enough tempera -
ture. it breaks down completely into
V
t * carbon and water.
*
'
-
4
i

(a ) ( b)

MATTER AND CHANGE 13

 Zn( N03)2 # 6H20 F . W . 297.47
Certificate of Actual Lot Analysis
Acidity ( as HN03) 0 008%
Alkalies and Earths 002%
Chloride (Cl) 0005%
Insoluble Matter 0.001%
Iron (Fe) 0 0002%
lead (Pb) 0.001%
Phosphate ( PO<) 0.0002%
Sulfate (S04) 0 002%
Store separately from and avoid contact
with combustible materials. Keep con -
tainer closed and in a cool, dry place.
Avoid contact with skin, eyes and
clothing.
TABLE 1 Some Grades LOT NO . 917356
of Chemical Purity
fL 02 0588 CAS 10196 - 18 6
't'
Primary standard reagents
AC 'S ( American Chemical FIGURE 11 The labeling on a reagent bottle lists the grade of the reagent
Society-specified and the percentages of impurities for that grade. What grade is this chemical?
reagents)
USP (United States
>. Pharmacopoeia Laboratory Chemicals and Purity
o standards ) The chemicals in laboratories are generally treated as if they are pure.
C ~
Mi
C’P (chemically pure;
However, all chemicals have some impurities. Chemical grades of puri -
C
\r.
TZ purer than technical .
ty are listed in Table 1 The purity ranking of the grades can vary when
'J
U grade ) agencies differ in their standards. For some chemicals, the USP grade
c
may specify higher purity than the CP grade. For other chemicals, the
NF ( National Formulary
specifications) opposite may be true. However, the primary standard reagent grade is
always purer than the technical grade for the same chemical. Chemists
FCC (Food Chemical
need to be aware of the kinds of impurities in a reagent because these
Code specifications)
impurities could affect the results of a reaction. For example, the chem -
Technical ( industrial ical label shown in Figure 11 shows the impurities for that grade. The
chemicals) chemical manufacturer must ensure that the standards set for that
reagent bv the American Chemical Society are met.

SECTION REVIEW 3. How do you decide whether a sample of matter is

1. a. What is the main difference between physical a solid, liquid, or gas ?
properties and chemical properties? 4. Contrast mixtures with pure substances.
b. Give an example of each.
Critical Thinking
2. Classify each of the following as either a physical
change or a chemical change. 5. ANALYZING INFORMATION Compare the composi-
a. tearing a sheet of paper tion of sucrose purified from sugar cane with the
b. melting a piece of wax composition of sucrose purified from sugar beets.
c. burning a log Explain your answer.

14 CHAPTER i
 CROSS - DISCIPLINARY CONNECTION j j j j j
*
j Secrets of the Cremona Violins

What are the most beautiful sound- Many new violins made from the
ing of all violins ? Most professionals treated wood and replicated finish
will pick the instruments created have been made, and their sound
in Cremona, Italy, following the has been analyzed by modern signal
Renaissance. At that time, Antonio analyzers. These violins have been
Stradivari, the Guarneri family, and favorably compared with authentic
other designers created instruments Stradivari violins.
of extraordinary sound that have yet A number of expert violinists have
to be matched. The craftsmen were praised the sound of Dr. Nagyvary 's
notoriously secretive about their instruments, but some violin makers
techniques, but, based on 20 years of remain skeptical of the chemist 's
research, Dr. Joseph Nagyvary, a pro- claims. They insist that it takes many
fessor of biochemistry at Texas A & M years to reveal just how good a vio -
University, thinks he has discovered lin is. In the meantime, almost every-
the key to the violins' sound hidden Dr. Nagyvary and his violin one agrees that the art and science
in the chemistry of their materials. of violin making are still epitomized
According to Dr. Nagyvary, by the instruments of Cremona.
Stradivarius instruments are nearly which contains an enzyme called
free of the shrill, high-pitched pectinase. The pectinase softens the Questions
noises produced by modern violins. wood, making it resonate more 1. According to Dr. Nagyvary, what
Generally, violin makers attribute this freely. are two factors that are believed
to the design of the instrument, but " The other key factor in a violin's to have created the unique
Dr. Nagyvary traces it to a different sound," says Dr. Nagyvary, " is the sound of the Stradivari violins?
source. In Stradivari's day, wood for finish, which is the filler and the var -
2. Use the library or Internet
the violins was transported by float - nish covering the instrument. Most
resources to find additional
ing it down a river from the moun - modern finishes are made from rub -
information about the Cremona
tains to Venice, where it was stored bery materials, which limit the vibra -
violin makers. Who were some of
in sea water. Dr. Nagyvary first theo- tions of the wood." Modern analysis
the other instrument makers dur -
rized that the soaking process could has revealed that the Cremona finish
ing the time period in which
have removed ingredients from the was different: it was a brittle mineral
Stradivari was alive? Were other
wood that made it inherently noisy. microcomposite of a very sophisti-
stringed instruments made by
His experiments revealed that cated nature. According to historical
these artisans ? What are the
microbes and minerals also permeat- accounts, all violin makers, including
estimated present -day values of
ed the wood, making their own con - Stradivari, procured their varnishes
instruments made during this
tribution to the mellow musical from the local drugstore chemist,
period in Cremona?
sound. Attempting to reproduce the and they didn't even know what
effects of sea water, Dr. Nagyvary they were using ! Dr. Nagyvary and
soaks all his wood in a " secret " his co-workers have identified most
solution. One of his favorite ingredi - of the key ingredients of the
ents is a cherry - and-plum puree, Cremona finish.

MATTER AND CHANGE 15

 SECTION 3
Elements
OBJECTIVES
J Use a periodic table to name
elements, given their symbols. A s you have read, elements are pure substances that cannot be
decomposed by chemical changes. The elements serve as the building
Use a periodic table to write blocks of matter. Each element has characteristic properties. The ele-
^ ments are organized into groups based on similar chemical properties.
the symbols of elements,
given their names. This organization of elements is the periodic table, which is shown in
Figure 12 on the next page.

sj Describe the arrangement

of the periodic table.
Introduction to the Periodic Table
sj List the characteristics that
distinguish metals, nonmetals, Each small square of the periodic table shows the symbol for the ele -
and metalloids. ment and the atomic number. For example, the first square, at the upper
left, represents element 1 . hydrogen, which has the symbol H. As you
look through the table, you will see many familiar elements, including
iron, sodium, neon, silver, copper, aluminum, sulfur, and lead. You can
often relate the symbols to the English names of the elements. Some
symbols are derived from the element's older name, which was often in
Latin. Still others come from German. For example, wolfram comes
SC from the German name for tungsten. Table 2 lists some elements and
/ lNKS. Dm4»p«4 Md MiaUmed fry t
* their older names.
NtfioMl SOCK* Teuton AiwcutiM

For a variety of links related to this

chapter, go to wmy. sciJinksorg
TABLE 2 Elements with Symbols Based on Older
Topic: Periodic Table
SciLinks code: HC61125
^ Names
Modern name Symbol Older name
Antimony Sb stibium
Copper Cu cuprum
Gold Au aurum
Iron Fe ferrum
Lead Pb plumbum
Mercury Hg hydrargyrum
Potassium K kalium
Silver Ag argentum
Sodium Na natrium
Tin Sn stannum

Tungsten W wolfram

16 CHAPTER 1
Periodic Table
Group 18
1
H 2
Group 1 Group 2 Metals Group 13 Group 14 Group 15 Group 16 Group 17

3 4 5 6 7 8 9 10
Li Be Metalloids B C N 0 F Ne
11 12 Nonmetals 13 14 15 16 17 18
Na Mg Group 3 Group 4 GroupS Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12
Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub Uut Uuq Uup

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 94 95 % 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

FIGURE 12 The periodic table of

elements. The names of the elements
The vertical columns of the periodic table are called groups, or can be found on Table A-6
families. Notice that they are numbered from 1 to 18 from left to right . in the appendix.
Each group contains elements with similar chemical properties. For
example, the elements in Group 2 are beryllium , magnesium , calcium ,
strontium , barium , and radium . All of these elements are reactive met -
als with similar abilities to bond to other kinds of atoms. The two major
categories of elements are metals and nonmetals. Metalloids have prop-
erties intermediate between those of metals and nonmetals.
The horizontal rows of elements in the periodic table are called
periods. Physical and chemical properties change somewhat regularly Develop d Md numUiMd ky tfcc
'
HJCMKUI Some Itocken AIMKIMM
across a period. Elements that are close to each other in the same
For a variety of links related to this
period tend to be more similar than elements that are farther apart . chapter, go to www.scilinks org .
For example, in Period 2, the elements lithium and beryllium , in
Groups 1 and 2. respectively, are somewhat similar in properties. However,
Topic: Element Names
SciLinks code: HC60495
^
their properties are very different from the properties of fluorine, the
Period -2 element in Group 17.
The two sets of elements placed below the periodic table make up
what are called the lanthanide series and the actinide series. These
metallic elements fit into the table just after elements 57 and 89. They
are placed below the table to keep the table from being too wide.
There is a section in the back of this book called the Elements
Handbook which covers some elements in greater detail. You will use
information from the handbook to complete the questions in the Using
the Handbook sections in the chapter reviews.

MATTER AND CHANGE 17

 Chemistry in Action Types of Elements
Superconductors
The periodic table is broadly divided into two main sections: metals
Any metal becomes a better conductor
of electrical energy as its temperature and nonmetals. As you can see in Figure 12, the metals are at the left
decreases. In 1911, scientists discovered and in the center of the table. The nonmetals are toward the right.
that when mercury is cooled to about Some elements such as boron and silicon show characteristics of both
-269°C, it loses all resistance and metals and nonmetals.
becomes a superconductor. Scientists
have long tried to find a material that
would superconduct at temperatures Metals
above -196°C, the boiling point of Some of the properties of metals may be familiar to you. For example,
liquid nitrogen. In 1987, scientists dis- you can recognize metals by their shininess, or metallic luster. Perhaps
covered ceramic materials that became the most important characteristic property of metals is the ease with
superconductors when cooled only to which they conduct electricity and transfer energy. Thus, a metal is an
-183°C. These " high- temperature " element tlini is a good electrical conductor and a good heat conductor .
superconductors are used to build very
powerful electromagnets. Ceramic elec - At room temperature, most metals are solids. Most metals also have
tromagnets are used in medical mag- the property of malleability, that is. they can be hammered or rolled into
netic resonance imaging (MRI) machines thin sheets. Metals also tend to be ductile, which means that they can be
and in high-efficiency electric motors drawn into a line wire. Metals behave this way because they have high
and generators.
tensile strength, the ability to resist breaking when pulled.
Although all metals conduct electricity well, metals also have very
diverse properties. Mercury is a liquid at room temperature, whereas
tungsten has the highest melting point of any element . The metals in
FIGURE 13 ( a ) Gold has a low
Group 1 are so soft that they can be cut with a knife, yet others, such as
reactivity, which is why it may be chromium, are very hard. Some metals, such as manganese and bismuth,
found in nature in relatively pure are very brittle, vet others, such as iron and copper, are very malleable
form, ( b ) Copper is used in wiring and ductile. Most metals have a silvery or grayish white luster. Two
because it is ductile and conducts exceptions are gold and copper, which are yellow and reddish brown,
electrical energy ( c ) Aluminum is respectively. Figure 13 shows examples of metals.
malleable. It can be rolled into foil
that is used for w rapping food.

( a) ( b)

18 CHAPTER 1
(a )

FIGURE 14 Various nonmetallic

elements: ( a ) carbon, ( b ) sulfur.
Copper: A Typical Metal ( c ) phosphorus, and ( d ) iodine
Copper has a characteristic reddish color and a metallic luster, li is
found naturally in minerals such as chalcopyrite and malachite. Pure
copper melts at 1083 C and boils at 2567°C. It can be readily drawn into
'

fine wire, pressed into thin sheets, and formed into tubing. Copper con-
ducts electricity with little loss of energy.
Copper remains unchanged in pure, dry air at room temperature.
When heated, it reacts with oxygen in air. It also reacts with sulfur and
the elements in Group 17 of the periodic table. The green coating on a
piece of weathered copper comes from the reaction of copper with oxy -
gen. carbon dioxide, and sulfur compounds. Copper is an essential min -
eral in the human diet.

Nonmetals
Many nonmetals are gases at room temperature. These include nitro-
gen. oxygen, fluorine, and chlorine. One nonmetal, bromine, is a liquid.
The solid nonmetals include carbon, phosphorus, selenium, sulfur, and
iodine. These solids tend to be brittle rather than malleable and ductile.
Some nonmetals are illustrated in Figure 14.
Low conductivity can be used to define nonmetals. A nonmetal is an
element that is a poor conductor of heat and electricity. If you look at
Figure 12, you will see that there are fewer nonmetals than metals.

Phosphorus: A Typical Nonmetal

Phosphorus is one of five solid nonmetals. Pure phosphorus is known in
two common forms. Red phosphorus is a dark red powder that melts at
597 C. White phosphorus is a waxy solid that melts at 44 C. Because it
ignites in air at room temperature, white phosphorus is stored under water.
Phosphorus is too reactive to exist in pure form in nature. It is pre-
sent in huge quantities in phosphate rock , where it is combined with
oxygen and calcium. All living things contain phosphorus.

Metalloids
As you look from left to right on the periodic table, you can see that the FIGURE 15 Selenium is a non -
metalloids are found between the metals and the nonmetals. A metalloid metal. though it looks metallic.

MATTER AND CHANGE 19

 FIGURE 16 Some noble gases arc
used to make lighted signs of various
is an element that has some characteristics of metals and some character -
istics of nonmetals. All metalloids are solids at room temperature. They
colors.

tend to he less malleable than metals but not as brittle as nonmetals.

Some metalloids, such as antimony, have a somewhat metallic luster.
Metalloids tend to he semiconductors of electricity. That is. their ahil-
ity to conduct electricity is intermediate between that of metals and that
of nonmetals. Metalloids are used in the solid state circuitry found in
desktop computers, digital watches, televisions, and radios.

Noble Gases
Tlie elements in Group 18 of the periodic table are the noble gases.
These elements are generally unreactive. In fact, it was not until l %2
that the first noble gas compound, xenon hexafluoroplatinate, was pre -
pared. Low reactivity makes the noble gases very different from the other
families of elements. Group 18 elements are gases at room temperature.
.
Neon, argon, krypton, and xenon are all used in lighting Helium is used
in party balloons and weather balloons because it is less dense than air.

SECTION REVIEW 4. Describe the main differences between metals,

1. Use the periodic table to write the names for the nonmetals, and metalloids.
following elements: 0, S, Cu, Ag. Critical Thinking
.
2 Use the periodic table to write the symbols for the 5. INFERRING CONCLUSIONS If you find an element
following elements: iron, nitrogen, calcium, mercury. in nature its pure
in elemental state, what can you
3. Which elements are most likely to undergo the infer about the element's chemical reactivity ? How
same kinds of reactions, those in a group or those can you tell whether that element is a metal or a
in a period? nonmetal ?

20 CHAPTER 1
 CHAPTER HIGHLIGHTS
Chemistry Is a Physical Science
I Vocabulary •Chemistry is the study of the composition, structure, and proper-
chemistry ties of matter and the changes that matter undergoes.
chemical •A chemical is any substance that has a definite composition or is
used or produced in a chemical process.
•Basic research is carried out for the sake of increasing knowl-
edge. Applied research is carried out to solve practical problems.
Technological development involves the use of existing knowl-
edge to make life easier or more convenient .

Matter and Its Properties

I Vocabulary •All matter has mass and takes up space. Mass is one measure
mass change of state of the amount of matter.
matter solid •Chemical properties refer to a substance 's ability to undergo
atom liquid changes that alter its composition and identity.
element gas •An element is composed of one kind of atom. Compounds are
compound plasma made from two or more elements in fixed proportions.
extensive property chemical property • All substances have characteristic properties that enable chemists
intensive property chemical change to tell the substances apart and to separate the substances.
physical property chemical reaction •Physical changes do not involve changes in identity of a
physical change reactant substance.
•The three major states of matter are solid liquid, and gas.
,

Changes of state, such as melting and boiling, are physical

changes.
•In a chemical change —or a chemical reaction—the identity of
the substance changes.
•Energy changes accompany physical and chemical changes.
Energy may be released or absorbed, but it is neither created
nor destroyed.
•Matter can be classified into mixtures and pure substances.

Elements
I Vocabulary •Each element has a unique symbol. The periodic table shows the
group elements organized bv their chemical properties. Columns on the
family table represent groups or families of elements that have similar
period chemical properties. Properties vary across the rows, or periods.
metal • Ilie elements can be classified as metals, nonmetals, metalloids,
nonmetal and noble gases. These classes occupy different areas of the
metalloid periodic table. Metals tend to be shiny, malleable, and ductile
and tend to be good conductors. Nonmetals tend to be brittle
and tend to be poor conductors.
•Metalloids are intermediate in properties between metals and
nonmetals, and they tend to be semiconductors of electricity.
The noble gases are generally unreactive elements.

MATTER AND CHANGE 21

 CHAPTER REVIEW
12. a. How does a solid differ from a liquid?
Chemistry Is a b. How does a liquid differ from a gas?
Physical Science c. How is a liquid similar to a gas?
d. What is a plasma?
SECTION 1 REVIEW 13. What is meant by a change in state?
1. What is chemistry ? .
14 Identify the reactants and products in the fol -
2. What branch of chemistry is most concerned lowing reaction:
w ith the study of carbon compounds? potassium + water >
3. What is meant by the word chemical , as used by potassium hydroxide + hydrogen
scientists? 15. Suppose different parts of a sample material
4. In w hich of the six branches of chemistry would have different compositions. What can you con -
a scientist be working if he or she were doing clude about the material ?
the following:
a. investigating energy relationships for various
reactions Elements
b. comparing properties of alcohols with those
SECTION 3 REVIEW
of sugars
c. studying reactions that occur during the .
16 What is the significance of the vertical columns
digestion of food of the periodic table ? What is the significance of
5. Identify each of the following as an example of the horizontal rows?
either basic research, applied research, or tech - .
17 Compare the physical properties of metals, non-
nological development: metals. metalloids, and noble gases, and describe
a. A new type of refrigerant that is less damag- where in the periodic table each of these kinds
ing to the environment is developed. of elements is located.
b. A new element is synthesized in a particle .
18 Suppose element X is a poor conductor of elec-
accelerator. tricitv and breaks when hit with a hammer .
c. A computer chip is redesigned to increase Element Z is a good conductor of electricity
the speed of the computer. .
and heat In what area of the periodic table
does each element most likely belong?
.
19 Use the periodic table to write the names of the
Matter and Its Properties elements that have the following symbols, and
identify each as a metal, nonmetal, metalloid, or
SECTION 2 REVIEW noble gas.
6. a. What is mass? a. K c. Si e. Hg
b. What is volume ? b. Ag d. Na f. He
7. I low does the composition of a pure compound 20. An unknown element is shiny and is found to
differ from that of a mixture ? be a good conductor of electricity. What other
8. a. Define property. properties would you predict for it ?
b. How are properties useful in classifying 21. Use the periodic table to identify the group
materials? numbers and period numbers of the following
9. What is the difference between extensive prop- elements:
erties and intensive properties? a. carbon, C c. chromium. Cr
10. a. Define chemical property. b. argon, Ar d. barium. Ba
b. List two examples of chemical properties.
11. Distinguish between a physical change and a
chemical change.

22 CHAPTER 1
 CHAPTER REVIEW

MIXED REVIEW USING THE HANDBOOK

22. a. Define physical property. 30. Review the information on trace elements in
b. List two examples of physical properties. the Elements Handbook in the hack of this text ,
23. How can you tell the difference between an ele - a. What are the functions of trace elements in
ment and a compound? the body ?
24 . Identify each of the following as either a physi - h. What transition metal plays an important role
cal change or a chemical change. Explain vour in oxygen transport throughout the body?
answers. c. What two Group I elements are part of the
a. A piece of wood is sawed in half. electrolyte balance in the body?
b. Milk turns sour.
c. Melted butter solidifies in the refrigerator.
25. Write a brief paragraph that shows that you RESEARCH & WRITING
understand the following terms and the rela -
31. Research any current technological product of
.
tionships between them: atom, molecule com -
your choosing. Find out about its manufacture
pound , and element.
26. Pick an object you can see right now. List three and uses. Also find out about the basic research
and applied research that made its development
of the object 's physical properties that you can
observe. Can you also observe a chemical prop - possible.
32. Investigate current and proposed technological
erty of the object ? Explain your answer.
applications of superconductors. Find out which
of these applications have been successfully
tested or are already in use.
CRITICAL THINKING
27. Interpreting Concepts One way to make
lemonade is to start by combining lemon juice ALTERNATIVE ASSESSMENT
and water. To make the lemonade taste better
33 . During a l h period, make a list of all the
you could add some sugar. Is your lemonade-
sugar combination classified as a compound or changes that you see around you and that
a mixture ? Explain your answer. involve matter. Note whether each change
seems to be a physical change or a chemical
28. Analyzing Results A pure white, solid materi- change. Give reasons for your answers.
al that looks like table salt releases gas when 34. Make a concept map using at least 15 terms from
heated under certain conditions. There is no the vocabulary lists. An introduction to concept
change in the appearance of the solid, but the mapping is found in Appendix B of this book.
reactivity of the material changes.
a. Did a chemical or physical change occur?
How do you know ? — i i
b. Was the original material an element or a
compound?
29. Interpreting Concepts
i Graphing Calculator
Graphing Tabular Data
Go to go.hrw.com for a graphing calculator
a. Is breaking an egg an example of a physical
exercise that asks you to graph temperature
or chemical change? Explain your answer.
vs. time for a chemical reaction.
b. Is cooking an egg an example of a physical or
chemical change? Explain your answer. Keyw rd : HC6MTXX
°

MATTER AND CHANGE 23

 Math Tutor SIGNIFICANT FIGURES

The certainty of a measurement is expressed by significant figures. Significant figures in

a measurement consist of all the digits known with certainty plus one final digit. Look
at the reading below, which was obtained when measuring the mass of a paper clip.
mass of paperclip

2 3

Balance reading = 2.37 g

You know with certainty that the paper clip has a mass of 2.3 g. You can also estimate
an additional mass of 0.07 g for a total of 2.37 g. Each of the three digits in 2.37 g is
significant because it is either certain or estimated.

Problem-Solving TIPS
• Every nonzero digit is significant. Zeros between nonzero digits are significant.
• Zeros appearing in front of the first nonzero digit are not significant.
• If there is no decimal point, zeros that follow the last nonzero digit are not
significant.
• If there is a decimal point , zeros that follow the last nonzero digit are significant.
• When measurements are added or subtracted, the result must be rounded to the
same number of decimal places that the quantity with the fewest decimal places has.
• When measurements are multiplied or divided, the result must be rounded to the
same number of significant figures that the quantity with the smallest number of
significant figures has.

SAMPLE 1 SAMPLE 2
How many significant figures does 0.007 09 kg Divide 79.7 g by 0.89 cm3.
have? The quantity 79.7 g has 3 significant figures, but
All nonzero digits are significant. The zero 0.89 cm ' has only 2 significant figures. So. the
between the 7 and 9 is significant. The zeros to the product 8.955 056 18 g/cnT must be rounded to 2
left of the decimal point are not significant. The significant figures. The rounded quantity is
quantity 0.007 09 kg has 3 significant figures . 9.0 g/cm \

PRACTICE PROBLEMS
.
1 Determine the number of significant figures. .
2 Perform the following calculations and apply the
a. 42.200 L rules for significant figures.
b. 0.055 00 mol a. 56.05 g -s- 13.3 cm ' b. 1.057 g + 3.02 g + 12.4 g

24 CHAPTER 1
Answer the following items on a separate piece of paper. .
8 Three of the following must contain two or
more kinds of atoms. Which one does not
MULTIPLE CHOICE
contain two or more kinds of atoms?
.
1 Magnesium reacts with hydrochloric acid to A. element
produce magnesium chloride and hydrogen gas. B. compound
The reactants in this reaction are C. homogeneous mixture
A . magnesium and magnesium chloride. D. heterogeneous mixture
B. hydrochloric acid and hydrogen gas. 9. Which of the following symbols does not match
C. magnesium and hydrochloric acid. the element name given?
D. magnesium chloride and hydrogen gas. .
A . Al aluminum
2. Matter that has a definite shape and a definite B. Co. copper
volume is C. K. potassium
A . a liquid. .
C a solid. D. P. phosphorus
B. an element . D . a gas.
SHORT ANSWER
3. We know that air is a mixture and not a
compound because .
10 Give three examples of mixtures, and tell
A. it can be heated to a higher temperature. whether each one is homogeneous or hetero -
B. it can be compressed to a smaller volume. geneous. Give three examples of compounds.
C. it is colorless. .
11 In trying to identify a sample of a pure sub -
D . its composition can vary. stance, we observe the following properties.

4. Matter can be defined as anything that Tell whether each one is a chemical property
or a physical property.
A. has weight .
A. Its mass is 124.3 g.
B. has mass and volume.
B. It is a shiny solid at room temperature.
C. is uniform throughout .
C. It is easily etched by nitric acid.
D. exhibits both chemical and physical properties.
D. It melts when heated to 670 C.
5. Which of the following is best classified as a
homogeneous mixture ?
.
E It is 31.7 centimeters long.
A. pizza .
C hot tea
.
F It is a good heat conductor.
G. It burns in air.
B. blood D. copper wire
H. It is a good conductor of electrical energy.
.
6 A compound differs from a mixture in that a
EXTENDED RESPONSE
compound
A. contains onlv one element . .
12 Describe the difference between a chemical
B. varies in chemical composition depending change and a physical change. Give one
on the sample size. example of each kind of change .
C. has a definite composition by mass of the 13. Describe general properties of metals,
elements that the compound contains. nonmetals, and metalloids.
D. can be classified as either heterogeneous or
homogeneous.
7. Which of the following is not a physical state
of matter ?
A . solid .
C element
B. gas D. liquid
Remember that if you can elimi-
nate two of the four answer choices, your chances of
choosing the correct answer choice will double.

MATTER AND CHANGE 25

 SEE PRE - LAB
EXPERIMENT 1 EXTRACTION AND FILTRATION ?
O
INQUIRY
L A B

Mixture Separation
OBJECTIVES BACKGROUND
The ability to separate and recover pure substances
• Observe the chemical and physical proper-
ties of a mixture. from mixtures is extremely important in scientific
research and industry. Chemists need to work with
j

• Relate knowledge of chemical and physical pure substances, but naturally occurring materials are
properties to the task of purifying the seldom pure. Often, differences in the physical prop -
mixture.
erties of the components in a mixture provide the
• Analyze the success of methods of purifying means for separating them . In this experiment, you
the mixture. will have an opportunity to design , develop, and
implement your own procedure for separating a mix -
MATERIALS ture. The mixture you will work with contains salt ,
aluminum foil • plastic forks -
sand , iron filings, and poppy seeds. All four sub
stances are in dry, granular form .
cotton balls • plastic spoons
distilled water • plastic straws SAFETY
filter funnels • rubber stoppers
filter paper • sample of mixture
and components
forceps For review of safety, please see Safety in the
( sand , iron filings,
magnet salt , poppy seeds ) Chemistry Laboratory in the front of your book .
paper clips • test tubes and rack PREPARATION
paper towels • tissue paper 1. Your task will be to plan and carry out the sepa -
Petri dish • transparent tape ration of a mixture. Before you can plan your
experiment , you will need to investigate the
pipets • wooden splints
properties of each component in the mixture.
The properties will be used to design your mix -
ture separation . Copy the data table on the
following page in your lab notebook , and use
it to record your observations.

PROCEDURE
1 . Obtain separate samples of each of the four
mixture components from your teacher. Use the
equipment you have available to make observa -
tions of the components and determine their
properties. You will need to run several tests with
each substance, so don t use all of your sample
'

26 CHAPTER 1
 EXPERIMENT 1

DATA TABLE
Properties Sand Iron filings Salt Poppy seeds
Dissolves
Floats
Magnetic
Other

on the first test . Look for things like whether 2. Designing Experiments: If you could do the
the substance is magnetic, whether it dissolves, lab over again , what would you do differently?
or whether it floats. Record your observations Be specific.
in your data table.
3. Designing Experiments: Name two materials
2 . Make a plan for what you will do to separate a or tools that weren 't available that might have
mixture that includes the four components from made your separation easier.
step 1 . Review your plan with your teacher.
4. Applying Ideas: For each of the four compo-
3. Obtain a sample of the mixture from your nents. describe a specific physical property that
teacher. Using the equipment you have avail - enabled you to separate the component from
able. run the procedure you have developed . the rest of the mixture.

CLEANUP AND DISPOSAL

EXTENSIONS
4. Clean your lab station . Clean all equip-
1. Evaluating Methods: What methods could be
ment . and return it to its proper place.
used to determine the purity of each of your
Dispose of chemicals and solutions in
recovered components?
the containers designated by your teacher. Do
not pour any chemicals down the drain or throw 2 . Designing Experiments: How could you sepa -
anything in the trash unless your teacher directs rate each of the following two- part mixtures?
you to do so. Wash your hands thoroughly after a . aluminum filings and iron filings
all work is finished and before you leave the lab. b. sand and gravel
c. sand and finely ground polystyrene foam
ANALYSIS AND INTERPRETATION d . salt and sugar
1. Evaluating Methods: On a scale of l to 10. how e. alcohol and water
successful were you in separating and recovering f. nitrogen and oxygen
each of the four components: sand , salt , iron 3. Designing Experiments: One of the components
filings, and poppy seeds? Consider 1 to be the of the mixture in this experiment is in a different
best and 10 to be the worst . Justify your ratings physical state at the completion of this experi -
based on vour observations. ment that it was at the start . Which one? How
would you convert that component back to its
CONCLUSIONS original state ?
1. Evaluating Methods: How did you decide on
the order of your procedural steps? Would any
order have worked ?

MATTER AND CHANGE 27

 CHAPTER 2

Measurements
and Calculations

For advanced project ideas I

from Scientific American,
visit go.hrw.com and type
in the keyword HC6 SAA . I
Scientific Method SECTION 1

OBJECTIVES
Describe the purpose of the
S omctimcs progress in science comes about through accidental dis- scientific method.
coveries. Most scientific advances, however, result from carefully
planned investigations. The process researchers use to carry out their sj Distinguish between
investigations is often called the scientific method. The scientific qualitative and quantitative
method is a logical approach to solving problems by observing and col - observations.
lecting data, formulating hypotheses, testing hypotheses, and formulating
theories that are supported by data.
>J Describe the differences
between hypotheses, theories,
and models.
Observing and Collecting Data
Observing is the use of the senses to obtain information. Observation
often involves making measurements and collecting data. The data may
be descriptive ( qualitative ) or numerical ( quantitative ) in nature.
Numerical information, such as the fact that a sample of copper ore has
a mass of 25.7 grams, is quantitative. Non-numerical information, such as
SC
the fact that the sky is blue, is qualitative. / lNKS.]
Experimenting involves carrying out a procedure under controlled
conditions to make observations and collect data. To learn more about
matter, chemists study systems. A system is a speci fic portion of matter
—
Dewtoftd Md lUMtJMtd by tW
Wito d Sdmt Twkn Afsocutw

For a variety of links related to this

chapter, go to www.scilinks.org
*

in a given region of space that has been selected for study during an Topic: Scientific Methods
experiment or observation. When you observe a reaction in a test tube, SciLinks code: HC 61359
the test tube and its contents form a system.
I -

FIGURE 1 These students have

designed an experiment to deter -
mine how to get the largest volume
of popped corn from a fixed number
of kernels. They think that the
volume is likely to increase as the
moisture in the kernels increases.
ITieir experiment will involve
soaking some kernels in water and
observing whether the volume of the
popped corn is greater than that of
corn popped from kernels that have
not been soaked.

MEASUREMENTS AND CALCULATIONS 29

 FIGURE 2 A graph of data Plant Growth Vs. Time
can show relationships between
30
two variables. In this case the graph
shows data collected during an
experiment to determine the effect 25 50 % phosphorus
of phosphorus fertilizer compounds fertilizer
on plant growth. The following is one-
possible hypothesis: // phosphorus 25 % phosphorus
20
stimulates corn-plant growth, then fertilizer
corn plants treated with a soluble
?
phosphorus compound should grow -C 15
faster, under the same conditions, 1o
than corn plants that are not treated.
10
10% phosphorus
fertilizer
5 no fertilizer

0
0 5 10 15 20 25
Time ( days)

Formulating Hypotheses
As scientists examine and compare the data from their own experiments,
they attempt to find relationships and patterns—in other words, they
make generalizations based on the data. Generalizations are statements
that apply to a range of information. To make generalizations, data are
sometimes organized in tables and analyzed using statistics or other
mathematical techniques, often with the aid of graphs and a computer.
Scientists use generalizations about the data to formulate a
hypothesis, or testable statement . 'The hypothesis serves as a basis for
making predictions and for carrying out further experiments.
I Ivpotheses are often drafted as "if - then ' statements. The " then ' part of
*

the hypothesis is a prediction that is the basis for testing by experiment.

Figure 2 shows data collected to test a hypothesis.

Testing Hypotheses
Testing a hypothesis requires experimentation that provides data to
support or refute a hypothesis or theory. During testing, the experi -
mental conditions that remain constant are called controls, and anv con-
dition that changes is called a variable. Anv change observed is usually
due to the effects of the variable. If testing reveals that the predictions
were not correct, the hypothesis on which the predictions were based
must be discarded or modified .
30 CH APTER 2
 STAGES IN THE SCIENTIFIC METHOD

OBSERVING FORMULATING TESTING THEORIZING PUBLISH

•collecting data HYPOTHESES RESULTS
•predicting •constructing
•measuring •organizing and •experimenting models •communicating
•experimenting analyzing data •communicating •predicting
•communicating * •classifying •collecting data •communicating
•inferring •measuring
•predicting
•communicating

Data do not support

hypothesis—revise Results confirmed by other scientists—
or reject hypothesis validate theory

FIGURE 3 Ihe scientific method is not a single, fixed process. Scientists may
repeat steps many times before there is sufficient evidence to formulate a theo -
ry. You can see that each stage represents a number of different activities.

Theorizing
When the data from experiments show that the predictions of the hypoth -
esis are successful, scientists typically try to explain the phenomena they
are studying by constructing a model. A model in science is more than a
physical object; it is often an explanation of how phenomena occur and
how data or events are related. Models may be visual, verbal, or mathe -
matical. One important model in chemistry is the atomic model of mat -
ter. which states that matter is composed of tiny particles called atoms.
If a model successfully explains many phenomena, it may become part
of a theory. The atomic model is a part of the atomic theory, which you
will study in Chapter 3. A theory is a broad generalization that explains a
body of facts or phenomena. Theories are considered successful if they
can predict the results of many new experiments. Examples of the impor -
tant theories you will study in chemistry are kinetic -molecular theory and
collision theory. Figure 3 shows where theory fits in the scheme of the sci -
entific method.

SECTION REVIEW 4. How are models related to theories and

1. What is the scientific method? hypotheses ?
2 . Which of the following are quantitative? Critical Thinking
a. the liquid floats on water 5. INTERPRETING CONCEPTS Suppose you had to
b. the metal is malleable test how well two types of soap work . Describe
c. the liquid has a temperature of 55.6°C your experiment by using the terms control and
3. How do hypotheses and theories differ ? variable.

MEASUREMENTS AND CALCULATIONS 31

 /

Chemistry in Action M
Breaking Up Is Easy To Do
It may seem obvious that chemistry is Shattering glass undergoes brittle In addition to the type of material
important in the making of materials, failure. Glass shatters when the bonds influencing breakage, the quality of
but chemistry is also vital to the study between the two layers of atoms that the material also influences break -
of how materials break. Everyday are along the initial crack break. This age. All objects contain microscopic
items have to be made to withstand breakage causes the layers to pull defects, such as bubbles in plastic
various types of force and pressure or apart, which separates the material pieces. A material will tend to under -
they cannot be used. For example, sci- into pieces. This type of failure is com- go failure at its defect sites first.
entists and engineers work to ensure mon in materials that do not have a Careful fabrication procedures can
that highway bridges do not collapse. very orderly arrangement of atoms. minimize, but not completely elimi-
When excessive force is applied to When a car bumper crumples, duc - nate, defects in materials.
an object, the material that the object tile failure happens. This type of fail- Even though materials are designed
is made of will break. The object ure tends to happen in materials to withstand a certain amount of
breaks because the force creates such as metals, that have a regular, force, the normal wear and tear that
stress on the bonds between the ordered arrangement of atoms. This materials experience over their life-
atoms of the material and causes the arrangement of atoms is known as a times creates defects in the material.
bonds to break. This creates micro- crystal structure. Ductile failure hap - This process is referred to as fatigue.
scopic cracks in the material. When a pens when the bonds in the material If fatigue were to go undetected, the
material breaks, it is said to have break across many layers of atoms microscopic cracks that form could
undergone failure. Materials typically that are not in the same plane as the then undergo brittle or ductile failure.
break in one of two ways: ductile fail- original crack. Rather than splitting It would be catastrophic if the materi-
ure and brittle failure. Both types of apart, the layers slip past each other als in certain products, such as air-
failure start with microscopic cracks into new positions. The atoms form plane parts, failed. To avoid such a
in the material. However, the way a new chemical bonds, between them failure, people monitor materials that
material eventually breaks depends and the material stays in one piece; are exposed to constant stress for
how its atoms are organized. only the shape has changed. signs of fatigue. The defects in the
metal parts of airplanes can be detect-
microscopic defect
ed with nondestructive techniques,
< A microscopic crack in a material can such as electromagnetic analysis.
develop into brittle or ductile failure.
Questions
1. Can you name some ways in
which metal or plastic parts
might obtain defects caused by
chemical reactions?
2. Does a ceramic dinner plate
undergo brittle or ductile failure
when it is dropped and breaks ?
ductile failure
brittle failure

32 CHAPTER 2
Units of Measurement SECTION 2

OBJECTIVES
* Distinguish between a
M easurements are quantitative information. A measurement is more quantity, a unit, and a
than just a number, even in everyday life. Suppose a chef were to write measurement standard.
.
a recipe listing quantities such as I salt. 3 sugar, and 2 flour The cooks
could not use the recipe without more information. They would need to Name and use SI units for
know whether the number 3 represented teaspoons, tablespoons, cups, length, mass, time, volume,
ounces, grams, or some other unit for sugar. and density.
Measurements represent quantities. A quantity is something that lias
magnitude, size. or amount . A quantity is not the same as a measure -
ment . For example, the quantity represented by a teaspoon is volume.
Distinguish between mass
and weight.
The teaspoon is a unit of measurement, while volume is a quantity. A
teaspoon is a measurement standard in this country. Units of measure -
ment compare what is to be measured with a previously defined size. . j Perform density calculations.
Nearly every measurement is a number plus a unit. The choice of unit
depends on the quantity being measured.
Many centuries ago, people sometimes marked off distances in the ^ Transform a statement of
equality into a conversion
number of foot lengths it took to cover the distance. But this system was factor.
unsatisfactory because the number of foot lengths used to express a dis-
tance varied with the size of the measurer 's foot. Once there was agree -
ment on a standard for foot length, confusion as to the real length was
eliminated. It no longer mattered who made the measurement , as long
as the standard measuring unit was correctly applied.

SI Measurement
Scientists all over the world have agreed on a single measurement sys-
tem called Le Systeme International d Unites , abbreviated SI. This sys-
'

tem was adopted in 1%() by the General Conference on Weights and

Measures. SI now has seven base units, and most other units are derived
from these seven. Some non - SI units are still commonly used by
chemists and are also used in this book .
SI units are defined in terms of standards of measurement . The stan -
dards are objects or natural phenomena that are of constant value, easy
to preserve and reproduce, and practical in size. International organiza -
tions monitor the defining process. In the United States, the National
Institute of Standards and Technology ( NIS I ) plays the main role in
maintaining standards and setting style conventions. For example, num -
bers are written in a form that is agreed upon internationally. The num -
ber seventy-five thousand is written 75 000. not 75,000, because the
comma is used in other countries to represent a decimal point.

MEASUREMENTS AND CALCULATIONS 33

 TABLE 1 SI Base Units
Quantity Unit
Quantity symbol Unit name abbreviation Defined standard
Length / meter m the length of the path traveled by light
in a vacuum during a time interval of
1/299 792 458 of a second
Mass m kilogram kg the unit of mass equal to the mass of the
international prototype of the kilogram
lime t second s the duration of 9 192 631 770 periods of the
radiation corresponding to the transition
between the two hyperfine levels of the
ground state of the cesium - 133 atom
Temperature T kelvin K the fraction 1 /273.16 of the thermodynamic
temperature of the triple point of water
Amount of n mole mol the amount of substance of a system which
substance contains as many elementary entities as there
are atoms in 0.012 kilogram of carbon - 12
Electric / ampere A the constant current which, if maintained in
current two straight parallel conductors of infinite
length, of negligible circular cross section, and
placed 1 meter apart in vacuum, would
produce between these conductors a force
equal to 2 x 10 newton per meter of length
“

Luminous /, candela cd the luminous intensity, in a given direction, of

intensity a source that emits monochromatic radiation
of frequency 540 x 101: hertz and that has a
radiant intensity in that direction of 1/683
watt per steradian

SCllNKS OmloM
ft
auMUtart by tW
NKIMUI M«M TMtfcm AuMutm
SI Base Units
For a variety of links related to this The seven SI base units and their standard abbreviated symbols are
chapter, go to www.seilioks.org
Topic: SI Units
4S .
listed in ruble 1 All the other SI units can be derived from the funda -
mental units.
SciLinks code: HC61390
Prefixes added to the names of SI base units are used to represent
quantities that are larger or smaller than the base units. Table 2 lists SI
prefixes using units of length as examples. For example, the prefix centi- ,
abbreviated c, represents an exponential factor of 10 2, which equals
"

1 / 100. Thus, 1 centimeter. I cm. equals 0.01 m. or 1/100 of a meter.

Mass
As you learned in Chapter 1 . mass is a measure of the quantity of
matter. The SI standard unit for mass is the kilogram. The standard for
mass defined in Table I is used to calibrate balances all over the world.

34 CHAPTER 2
 TABLE 2 SI Prefixes
Unit Exponential
Prefix abbreviation factor Meaning Example
tera T 1012 1 000 000 (MM) ( MM) 1 terameter ( Tm ) = 1 x 1()12 m
y
giga G 109 1 000 000 ( KM ) 1 gigameter (Gm) = 1 x 10 m
mega M 106 1 0(M ) ( KM ) 1 megameter ( Mm ) = 1 x 106 m
kilo k 103 1000 1 kilometer ( km ) = 1000 m
hecto h 1 ()2 100 1 hectometer ( hm ) = 100 m
deka da 101 10 1 dekameter ( dam ) = 10 m
10 °1 1 1 meter ( m )
deci d lO "
1/10 1 decimeter ( dm ) = 0.1 m
centi c 10-2 1 / 100 1 centimeter (cm) = 0.01 m
milli m ur 3 1/1000 1 millimeter ( mm ) = 0.001 m
micro M nr* 1/ 1 ( )( K) 000 1 micrometer ( pm) = 1 x 10"^ m
10“9 1 nanometer ( nm ) = 1 x 10 ' m
l
nano 1/ 1 000 000 000
pico
n

P 10 12
"
1 / 1 ( K )( ) ( )( )() ()( K) ( KK ) 1 picometer ( pm) = 1 x l (r 2 m
,
5 1 femtometer ( fm) = 1 x 1(Jr15 m
,Q '
fernto f K)- 1 / 1 ( KK ) IKK ) 000 000 000
- 18 1
at to a 1 / 1 (MK ) 000 000 (KK ) 000 000 1 attometer ( am) = 1 x 10 '

*m

The mass of a typical textbook is about 1 kg. The gram. g which is.
1 / 1000 of a kilogram, is more useful for measuring masses of small
objects, such as flasks and beakers. For even smaller objects, such as liny
quantities of chemicals, the milligram, mg. is often used. One milligram
is 1 / 1000 of a gram, or 1 / 1 000 000 of a kilogram. CROSS - DISCIPLINARY
Mass is often confused with weight because people often express the * 4 J * w J J J > J w J J J

weight of an object in grams. Mass is determined bv comparing the mass Some Handy
of an object with a set of standard masses that are part of the balance. Comparisons of Units
Weight is a measure of the gravitational pall on matter Unlike weight, To become comfortable with units in
mass does not depend on gravity. Mass is measured on instruments such the SI system, try relating some com -
mon measurements to your experience.
as a balance, and weight is typically measured on a spring scale. Taking
A meter stick is a little longer than a
weight measurements involves reading the amount that an object pulls yardstick . A millimeter is about the
down on a spring. As the force of Earth's gravity on an object increas - diameter of a paper clip wire, and a
.
es. the object 's weight increases The weight of an object on the moon is centimeter is a little more than the
about one-sixth of its weight on Earth. width of a paper clip.
One gram is about the mass of
a paper clip. A kilogram is about
Length 2.2 pounds (think of two pounds plus
The SI standard unit for length is the meter. A distance of 1 m is about one stick of butter). And there are
the width of an average doorway. To express longer distances, the kilo- about five milliliters in a teaspoon.
meter. km. is used. One kilometer equals 1000 m. Road signs in the
l nited States sometimes show distances in kilometers as well as miles.
The kilometer is the unit used to express highway distances in most
other countries of the world. To express shorter distances, the centimeter

MEASUREMENTS AND CALCULATIONS 35

 FIGURE 4 The meter is the
SI unit of length, but the centimeter
is often used to measure smaller
distances. What is the length in cm of
the rectangular piece of aluminum
foil shown?

is often used. From Table 2, you can see that one centimeter equals
1 / 100 of a meter. The width of this book is just over 20 cm.

Derived SI Units
Many SI units are combinations of the quantities shown in Table 1.
Combinations of SI base units form derived units. Some derived units
are shown in Table 3 .
Derived units are produced by multiplying or dividing standard
units. For example, area, a derived unit, is length times width. If both
length and width are expressed in meters, the area unit equals meters
times meters, or square meters, abbreviated nr. The last column of

TABLE 3 Derived SI Units

Quantity Unit
Quantity symbol Unit abbreviation Derivation
Area A square meter nr length x width
Volume V cubic meter nr' length x width x height
kg mass
Density D kilograms per cubic meter
m' volume
kg mass
Molar mass M kilograms per mole
mol amount of substance
m' volume
Molar volume Vm cubic meters per mole
mol amount of substance

Energy E joule J force x length

36 CHAPTER 2
Fable 3 shows the combination of fundamental units
used to obtain derived units.
Some combination units are given their own names. \
V
\v 40
50 60 ,
I I I' //
*'80
'/
'/ /
For example, pressure expressed in base units is the
following.
^^C 20
30 \
x
MPH
90 V
too '
.
X
\ \ ' F

—
'2
kg/ nvs: 10 no tr N

The name pascal. Pa , is given to this combination .

You will learn more about pressure in Chapter 11 .
Prefixes can also be added to express derived units.
0 120
P RN021
- — E
« UNLEADED R£L ON
i

FIGURE 5 The speed that registers on a speedome -

Area can be expressed in cm 2 , square centimeters, ter represents distance traveled per hour and is
or mnr . square millimeters. expressed in the derived units kilometers per hour or
miles per hour.
Volume
Volume is the amount of space occupied by an object . The derived SI unit
of volume is cubic meters, m O n e cubic meter is equal to the volume
of a cube whose edges are 1 m long. Such a large unit is inconvenient for
expressing the volume of materials in a chemistry laboratory. Instead , a
smaller unit , the cubic centimeter, cm \ is often used. There are 1 ( K ) centi -
meters in a meter, so a cubic meter contains 1 000 000 cm \
100 cm 100 cm 100 cm
1 m' x
1 m
x
1 m
x
1 m = 1 000 ( XX ) cm3
When chemists measure the volumes of liquids and gases, they often
use a non -SI unit called the liter. The liter is equivalent to one cubic
decimeter. Thus, a liter. L. is also equivalent to 1000 cm '. Another non -SI
unit , the milliliter, mL, is used for smaller volumes. There are 1000 mL in
—
1 L. Because there are also 1000 cm ' in a liter , the two units milliliter
—
and cubic centimeter are interchangeable.

FIGURE 6 The relationships

between various volumes are shown
here. One liter contains 1000 mL of
1000 * liquid , and 1 mL is equivalent to
1 cm 3. A small perfume bottle con -
tains about 15 mL of liquid . The
15 mL
1000 cm 3 15 mL volumetric flask ( far left ) and gradu -
ated cylinder ( far right ) are used for
measuring liquid volumes in the lab.

MEASUREMENTS AND CALCULATIONS 37

 Density
An object made of cork feels lighter than a lead object of the same size.
What you are actually comparing in such cases is how massive objects
are compared with their size. This property is called density. Density is
the ratio of mass to volume, or mass divided by volume. Mathematically,
the relationship for density can be written in the following way.
mass m
density = or D =
volume V
The quantity m is mass. V is volume, and D is density.
Tlie SI unit for density is derived from the base units for mass and vol-
ume — the kilogram and the cubic meter, respectively — and can be
expressed as kilograms per cubic meter, kg/m '. This unit is inconvenient -
ly large for the density measurements you will make in the laboratory.
You will often see density expressed in grams per cubic centimeter, g/cm '.
or grams per milliliter, g/mLThe densities of gases are generally report -
FIGURE 7 Density is the ratio of
ed either in kilograms per cubic meter, kg/m ', or in grams per liter. g/L.
mass to volume. Both water and
copper shot float on mercury Density is a characteristic physical property of a substance. It does not
because mercury is more dense. depend on the size of the sample because as the sample's mass increases,
its volume increases proportionately, and the ratio of mass to volume is
constanl. Therefore, density can be used as one property to help identify
a substance. Table 4 shows the densities of some common materials. As
you can see. cork has a density of only 0.24 g/cm '. which is less than the
density of liquid water. Because cork is less dense than water, it floats
on water. Lead, on the other hand, has a density of 11.35 g/cm ' /Hie den -
sity of lead is greater than that of water, so lead sinks in water.
Note that Table 4 specifies the temperatures at which the densities
were measured. That is because density varies with temperature. Most
objects expand as temperature increases, thereby increasing in volume.
Because density is mass divided by volume, density usually decreases
with increasing temperature.

TABLE 4 Densities of Some Familiar Materials

Density at Density at
Solids 20°C ( g/ cm3 ) Liquids 20°C ( g/mL)
cork 0.24 * gasoline 0.67*
butter 0.86 ethvl alcohol
9
0.791
ice 0.92+ kerosene 0.82
sucrose 1.59 turpentine 0.87
bone 1.85* water 0.998
diamond 3.26* sea water 1.025 **
copper 8.92 milk 1.031 *
lead 11.35 mercury 13.6
measured at 0 ( * * measured at 15°C
* typical density

38 CHAPTER 2
QuicILAB Wear safety goggles and an apron.

Materials
Density of Pennies • balance
• 100 mL graduated cylinder
Procedure 5. Review your data for any large • 40 pennies dated before
1. Using the balance, determine
the mass of the 40 pennies
differences between trials that
could increase the error of
1982
• 40 pennies dated after 1982
minted prior to 1982. Repeat your results. Repeat those • water
this measurement two more measurements.
times. Average the results of the
three trials to determine the
6. Use the average volume and
average mass to calculate the
average mass of the pennies. average density for each group
2. Repeat step 1 with the 40 pen- of pennies.
nies minted after 1982. 7. Compare the calculated aver -
3. Pour about 50 mL of water into age densities with the density
the 100 mL graduated cylinder. of the copper listed in Table 4.
Record the exact volume of the
water. Add the 40 pennies Discussion
minted before 1982. CAUTION:
Add the pennies carefully so 1. Why is it best to use the results
that no water is splashed out of
of three trials rather than a sin-
the cylinder. Record the exact gle trial for determining the
volume of the water and pen- density ?
.
nies Repeat this process two 2. How did the densities of the
more times. Determine the vol - two groups of pennies com-
ume of the pennies for each pare ? How do you account for
trial. Average the results of any difference?
those trials to determine the
average volume of the pennies. 3. Use the results of this investiga -
tion to formulate a hypothesis
4. Repeat step 3 with the 40 pen- about the composition of the
nies minted after 1982. two groups of pennies. How
could you test your hypothesis?

SAMPLE PROBLEM A
A sample of aluminum metal has a mass of 8.4 g. The volume of the sample is 3.1 cm \ Calculate the den-
sity of aluminum.

SOLUTION Given: mass ( m ) = 8.4 g

volume ( V ) = 3.1 cm3
Unknown: density I P )
mass 8.4 g
density - volume 3.1 cm '
- 2.1 g/ cm '

MEASUREMENTS AND CALCULATIONS 39

 PRACTICE Answers in Appendix E
}
1 . What is the density of a block of marble that occupies 310. cm
and has a mass of 853 g?
2. Diamond has a density of 3.26 g/cm \ What is the mass of a dia -
mond that has a volume of 0.351 cm3?
Go to go. hrw. com for
3. W hat is the volume of a sample of liquid mercury that has a mass more practice problems
of 76.2 g. given that the density of mercury is 13.6 g/ mL? that ask you to calculate
density.
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Conversion Factors
A conversion factor is a ratio derived from the equality between two dif -
ferent units that can be used to convert from one unit to the other. For
example, suppose you want to know how many quarters there arc in a
certain number of dollars. To figure out the answer, you need to know
how quarters and dollars are related. There are four quarters per dollar
and one dollar for every four quarters. Those facts can be expressed as
ratios in four conversion factors.
4 quarters 1 dollar 0.25 dollar 1 quarter
1 dollar 4 quarters l quarter 0.25 dollar
=1
Notice that each conversion factor equals 1 . That is because the two
quantities divided in any conversion factor are equivalent to each
—
other as in this case, where 4 quarters equal 1 dollar. Because conver -
sion factors are equal to I , they can be multiplied by other factors in
equations without changing the validity of the equations. You can use
conversion factors to solve problems through dimensional analysis.
Dimensional analysis is a mathematical technique that allows you to use
units to solve problems involving measurements. When you want to use
a conversion factor to change a unit in a problem , you can set up the
problem in the following way.
quantity sought = quantity given x conversion factor
For example, to determine the number of quarters in 12 dollars, you
would carry out the unit conversion that allows you to change from dol -
lars to quarters.
number of quarters = 12 dollars x conversion factor
Next you would have to decide which conversion factor gives you an
answer in the desired unit. In this case, you have dollars and you want
quarters. To eliminate dollars, you must divide the quantity bv dollars.
Therefore, the conversion factor in this case must have dollars in the
denominator and quarters in the numerator. That factor is 4 quarters/
1 dollar. Thus, you would set up the calculation as follows.

40 CHAPTER 2
 ? quarters = 12 dollars x conversion factor
4 quarters
= 12 dollars x = 48 quarters
I doilttr
Notice that the dollars have divided out . leaving an answer in the
desired unit — quarters.
Suppose you had guessed wrong and used 1 dollar/4 quarters when
choosing which of the two conversion factors to use. You would have an
answer with entirely inappropriate units.
I dollar 3 dollars
? quarters = 12 dollars x =
4 quarters quarter
It is always best to begin with an idea of the units you will need in your
final answer. When working through the Sample Problems, keep track
of the units needed for the unknown quantity. Check your final answer
against what you've written as the unknown quantity .
Deriving Conversion Factors
You can derive conversion factors if you know the relationship between
the unit you have and the unit you want. For example, from the fact that
deci - means “ 1/ 10." you know that there is 1 / 10 of a meter per decimeter
and that each meter must have 10 decimeters. Thus, from the equality
( 1 m = 10 dm ), you can write the following conversion factors relating
meters and decimeters. In this book, when there is no digit shown in the
denominator, vou can assume the value is 1 .
1m 0.1 m 10 dm
and and
10 dm dm m
The following sample problem illustrates an example of deriving
conversion factors to make a unit conversion.

SAMPLE PROBLEM B

Express a mass of 5.712 grams in milligrams and in kilograms .

SOLUTION Given: 5.712 g
Unknown: mass in mg and kg

Tlie expression that relates grams to milligrams is

1 g = 1000 mg

The possible conversion factors that can be written from this expression are
1000 mg lg
and
g 1000 mg

MEASUREMENTS AND CALCULATIONS 41

 To derive an answer in mg, you'll need to multiply 5.712 g by 1000 mg/ g.
1000 mg
5.712 grx = 5712 mg
£
This answer makes sense because milligrams is a smaller unit than grams and. therefore,
there should be more of them.

The kilogram problem is solved similarly.

1 kg = 1000 g

Conversion factors representing this expression are

1000 g
and
1000 g kg
To derive an answer in kg. you'll need to multiply 5.712 g by l kg/ 1000 g.
1 kg
5.712 g- x = 0.005712 kg
1000 g
Hie answer makes sense because kilograms is a larger unit than grams and. therefore, there
should be fewer of them.

PRACTICE Answers in Appendix E — i V- f t O iI

Go to go.hrw.com for
1. Express a length of 16.45 m in centimeters and in kilometers.
more practice problems
2. Express a mass of 0.014 mg in grams. that ask you to perform
unit conversions,
sic
C Keyword: HC 6 MEAX
4
SECTION REVIEW f. 358 cm3 = . m3
1. Why are standards needed for measured quantities? g. 548.6 mL = cm3
2. Label each of the following measurements by the 4. Write conversion factors for each equality.
quantity each represents. For instance, a measure- a. 1 m3 = 1 000 000 cm3
ment of 10.6 kg/m3 represents density.
b. 1 in. = 2.54 cm
a. 5.0 g/ mL f. 325 ms
c. 1 jig = 0.000 001 g
b. 37 s g. 500 m2
d. 1 Mm = 1 000 000 m
c. 47 J h. 30.23 mL
5. a. What is the density of an 84.7 g sample of an
d. 39.56 g i. 2.7 mg unknown substance if the sample occupies
e. 25.3 cm3 j. 0.005 L 49.6 cm3 ?
b. What volume would be occupied by 7.75 g of
3. Complete the following conversions.
this same substance?
a. 10.5 g = _ kg
b. 1.57 km = m Critical Thinking
c. 3.54 pg = g 6. INFERRING CONCLUSIONS A student converts
grams to milligrams by multiplying by the
d. 3.5 mol = pmol
conversion factor 1 9 . Is the student perform-
mg
innnm
1000
e. 1.2 L = mL ing this calculation correctly ?

42 CHAPTER 2
 1
WE ISTORICAL CHEMISTRY
Classical Ideas About Matter
The Greeks were among the many Some Greek philosophers who Aristotle (384-322 BCE), a student
ancient cultures that sought to studied matter between 700 and of Plato, elaborated on the earlier
understand the nature of matter. One 300 BCE described matter in a way ideas about elements. He argued
group of Greek philosophers, called that differed from the way atomists that in addition to the four elements
the atomists, believed that matter described it. They attempted to iden- that make up all matter, there were
could be broken down into pieces of tify and describe a fundamental sub - four basic properties: hot, cold, wet,
a minute size. These pieces, called stance from which all other matter and dry. In Aristotle's view, the four
atoms or atomos which means " indi- was formed. Thales of Miletus elements could each have two of the
visible," possessed intrinsic, unchang- (640-546 BCE ) was among the first basic properties. For example, water
ing qualities. Another group of to suggest the existence of a basic was wet and cold, while air was wet
Greeks believed that matter could be element. He chose water, which and hot. He thought that one ele-
divided an infinite number of times exists as liquid, ice, and steam. He ment could change into another ele-
and could be changed from one type interpreted water 's changeability to ment if its properties were changed.
of matter into another. mean that water could transform into For more than 2,000 years,
Between 500 and 300 BCE, the any other substance. Other philoso - Aristotle's classical ideas dominated
Greek philosophers Leucippus and phers suggested that the basic ele - scientific thought. His ideas were
Democritus formulated the ideas ment was air or fire. Empedokles based on philosophical arguments,
that the atomists held. Leucippus (ca. 490-ca. 430 BCE) focused on four not on the the scientific process. It
and Democritus believed that all elements: earth, air, fire, and water. was not until the 1700s that the exis-
atoms were essentially the same but He thought that these elements com- tence of atoms was shown experi-
that the properties of all substances bined in various proportions to make mentally and that the incredible
arose from the unique characteristics all known matter. intuition of the atomists was realized.
of their atoms. For example, solids,
such as most metals, were thought Questions
to have uneven, jagged atoms. 1. In Aristotle's system of elements,
Because the atoms were rough, they fire opposes water. Why do
could stick together and form solids. you think that he chose this
Similarly, water was thought to have AIR EARTH relationship?
atoms with smooth surfaces, which
2. Use the ideas of the atomists to
would allow the atoms to flow past
describe the atoms of the physi-
one another. Though atomists did
cal phases of matter —solid,
not have the same ideas about mat-
liquid, and gas.
ter that we have today, they did WATER

believe that atoms were constantly This diagram shows Aristotle' s belief
in motion, even in objects that about the relationship between the
appeared to be solid. basic elements and properties.

MEASUREMENTS AND CALCULATIONS 43

 SECTION 3
Using Scientific
OBJECTIVES Measurements
Distinguish between accuracy
and precision.

Determine the number of

significant figures in I 1 you have ever measured something several limes you know that
’
,

measurements. the results can vary. Inscience,for a reported measurement to be use -

ful. there must be some indication of its reliability or uncertainty.

Perform mathematical opera -

tions involving significant
figures.
Accuracy and Precision
^ Convert measurements into The terms accuracy and precision mean the same thing to most people.
scientific notation. However, in science their meanings are quite distinct. Accuracy refers to
the closeness of measurements to the correct or accepted value of the

^ Distinguish between inversely quantity measured . Precision refers to the closeness of a set of measure -
and directly proportional ments of the same quantity made in the same uwv. Thus, measured values
relationships. that are accurate are close to the accepted value. Measured values that
are precise are close to one another but not necessarily close to the
accepted value.
Figure 8 can help you visualize the difference between precision and
FIGURE 8 The sizes and locations accuracy. A set of darts thrown separately at a dartboard may land
of the areas covered by thrown darts in various positions, relative to the bull's-eye and to one another. The
illustrate the difference between
precision and accuracy.

(a)

Darts within small area Darts within small area Darts within large area Darts within large area
= High precision = High precision = Low precision = Low precision

Area centered on bull 's - eye Area far from bull's-eye Area far from bull's - eye Area centered around bull's - eye
= High accuracy = Low accuracy = Low accuracy = High accuracy (on average)

44 CHAPTER 2
closer the darts land to the bull’s-eye, the more accurately they were
thrown. The closer they land to one another, the more precisely they
Chemistry in Action
were thrown . Thus, the set of results shown in Figure 8a is both accurate
Go to go.hrw.com for :i full - length
and precise because the darts are close to the bull ’s-eye and close to article on using measurements to
each other . In Figure 8b, the set of results is inaccurate but precise determine a car's pollution rating.
because the darts are far from the bull 's-eye but close to each other. In
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Figure 8c, the set of results is both inaccurate and imprecise because the
darts are far from the bull ’s-eye and far from each other. Notice also
that the darts are not evenly distributed around the bull’s-eye, so the
.
set . even considered on average, is inaccurate In Figure 8d, the set on
average is accurate compared with the third case, but it is imprecise.
That is because the darts are distributed evenly around the bull’s-eye
but are far from each other.

Percentage Error
The accuracy of an individual value or of an average experimental value
can be compared quantitatively with the correct or accepted value by
calculating the percentage error. Percentage error is calculated by sub -
tracting the accepted value from the experimental value , dividing the dif -
ference by the accepted value , and then multiplying by 100.

\ alaeexperimental - Valueaccepted
Percentage error - x 100
Valueaccepted

Percentage error has a negative value if the accepted value is greater

than the experimental value. It has a positive value if the accepted value
is less than the experimental value. The following sample problem illus -
trates the concept of percentage error.

SAMPLE PROBLEM C
A student measures the mass and volume of a substance and calculates its density as 1.40 g/mL. The
correct, or accepted, value of the density is 1.30 g/mL. What is the percentage error of the student’s
measurement?

SOLUTION Valueexperimental - Valueaccepted

Percentage error = x 100
Valueaccepted

1.40 g/mL - 1.30 g/ mL

x 100 = 7.7 %
1.30 g/ mL

PRACTICE Answers in Appendix E

1 . What is the percentage error for a mass measurement of 17.7 g.

Go to go.hrw.com for
given that the correct value is 21.2 g ? more practice problems
2 . A volume is measured experimentally as 4.2 b mL. What is the that ask you to calculate
percentage error.
percentage error, given that the correct value is 4.15 mL?
Keyword: HC 6 MEAX

MEASUREMENTS AND CALCULATIONS 45

 Error in Measurement
Some error or uncertainty always * m
exists in
any measurement . The skill of the measurer
places limits on the reliability of results The .
conditions of measurement also affect the
.
outcome Tlie measuring instruments them -
selves place limitations on precision. Some
balances can he read more precisely than
others. The same is true of rulers, graduated
cylinders, and other measuring devices.
I
i I i I i I m I i 11 I i I
j 11 11 I i fi
When you use a properly calibrated mea-
suring device, you can be almost certain of a
particular number of digits in a reading. For
example, you can tell that the nail in Figure 9 is definitely between 6.3
and 6.4 cm long. Looking more closely, you can see that the value is
halfway between 6.3 and 6.4 cm. However, it is hard to tell whether the
mf

value should be read as 6.35 cm or 6.36 cm. The hundredths place is thus
somewhat uncertain. Simply leaving it out would be misleading because
you do have some indication of the value’s likely range. Therefore, you
would estimate the value to the final questionable digit, perhaps report -
FIGURE 9 What value should be ing the length of the nail as 6.36 cm. You might include a plus-or -minus
recorded for the length of this nail ? value to express the range, for example. 6.36 cm ± 0.01 cm.

Significant Figures
In science, measured values are reported in terms of significant figures.
Significant figures in n measurement consist of all the digits known with
certainty plus one final digit , which is somewhat uncertain or is estimated .
For example, in the reported nail length of 6.36 cm discussed above, the
last digit, 6, is uncertain. All the digits, including the uncertain one. are
significant, however. All contain information and are included in the
reported value. Thus, the term significant does not mean certain . In any
correctly reported measured value, the final digit is significant but not
.
certain Insignificant digits are never reported. As a chemistry student ,
you will need to use and recognize significant figures when you work
with measured quantities and report your results, and when you evalu-
ate measurements reported by others.

Determining the Number of Significant Figures

SC
/ lNKS. wV r*
Dnctoffd and MiiilaiMd by th«
When you look at a measured quantity, you need to determine which
.
digits are significant That process is very easy if the number has no
Niboul Sflwe Tuchcn AssodatkMi

For a variety of links related to this

zeros because all the digits shown are significant. For example, in a num -
chapter, go to www.sfilinks._Qn} ber reported as 3.95. all three digits are significant. The significance of
b zeros in a number depends on their location, however. You need to
Topic: Significant Figures
Sci Links code: HC61392 learn and follow several rules involving zeros. After you have studied
the rules in Table 5, use them to express the answers in the sample prob -
lem that follows.

46 CHAPTER 2
TABLE 5 Rules for Determining Significant Zeros
Rule Examples
1 . Zeros appearing between nonzero digits a. 40.7 L has three significant figures,
are significant . h. 87 009 km has five significant figures.

2. Zeros appearing in front of all nonzero digits .

a 0.095 897 m has five significant figures,
are not significant . h. 0.0009 kg has one significant figure.

3. Zeros at the end of a number and to the a. 85.( X ) g has four significant figures.
right of a decimal point are significant. b. 9.(KX) (MX) 000 mm has 10 significant figures.

4. Zeros at the end of a number but to the a. 2000 m niav contain from one to four
-

left of a decimal point may or may not be significant figures, depending on how
significant. If a zero has not been measured .
many zeros are placeholders For measurements
or estimated but is just a placeholder, it is not given in this text, assume that 2000 m has one
significant. A decimal point placed after zeros significant figure.
indicates that they are significant. b. 2( M )0. m contains four significant figures,
indicated by the presence of the decimal point.

SAMPLE PROBLEM For more help, go to the Math Tutor at the end of Chapter 1 .

How many significant figures are in each of the following measurements?

a . 28.6 g
b. 3440. cm
c. 910 m
d. 0.046 04 L
e. 0.006 700 0 kg

SOLUTION Determine the number of significant figures in each measurement using the rules listed
in Fable 5 .
a. 28.6 g
Iliere are no zeros, so all three digits are significant.
b. 3440. cm
By rule 4. the zero is significant because it is immediately followed by a decimal point;
there are 4 significant figures.
c. 910 m
By rule 4, the zero is not significant; there are 2 significant figures.
d. 0.046 04 L
By rule 2, the first two zeros are not significant; bv rule 1. the third zero is significant;
there are 4 significant figures.
e. 0.006 700 0 kg
.
By rule 2 the first three zeros are not significant; by rule 3. the last three zeros are
significant; there are 5 significant figures.

MEASUREMENTS AND CALCULATIONS 47

 PRACTICE Answers in Appendix E

1. Determine the number of significant figures in each of the

following.
a. 804.05 g
b. 0.014 403 0 km
c. 1002 m
d. 400 mL
e. 30 000. cm
f. 0.000 625 000 kg
2. Suppose the value “seven thousand centimeters" is reported to
you. How should the number be expressed if it is intended to con-
tain the following? Go to go.hrw.com for
a. 1 significant figure more practice problems
b. 4 significant figures that ask you to
c. 6 significant figures determine significant
figures.
Keyword: HC 6 MEAX

Rounding
When you perform calculations involving measurements, you need to
know how to handle significant figures. This is especially true when you
are using a calculator to carry out mathematical operations.The answers
given on a calculator can be derived results with more digits than are
justified by the measurements.
Suppose you used a calculator to divide a measured value of 154 g by a
measured value of 327 mL. Each of these values has three significant fig-
ures. Hie calculator would show a numerical answer of 0.470948012. The
answer contains digits not justified by the measurements used to calculate
it. Such an answer has to be rounded off to make its degree of certainty
match that in the original measurements.The answer should be 0.471 g/mL.
.
The rules for rounding are shown in ruble 6 The extent of rounding
required in a given case depends on whether the numbers are being
added, subtracted, multiplied, or divided.

TABLE 6 Rules for Rounding Numbers

If the digit following the last digit Example (rounded to three
to be retained is: then the last digit should: significant figures)
greater than 5 be increased by 1 42.68 g 42.7 g
less than 5 stay the same 17.32 m > 17.3 m
5. followed by nonzero digit ( s ) be increased by I 2.7851 cm > 2.79 cm
5, not followed by nonzero digit ( s ), and be increased by 1 4.635 kg > 4.64 kg
preceded by an odd digit (because 3 is odd)
5. not followed bv nonzero digit( s), and the stay the same 78.65 mL > 78.6 mL
preceding significant digit is even (because 6 is even )

48 CHAPTER 2
Addition or Subtraction with Significant Figures
Consider two mass measurements, 25.1 g and 2.03 g. The first measure-
ment , 25.1 g. has one digit to the right of the decimal point , in the tenths
place. There is no information on possible values for the hundredths
place. That place is simply blank and cannot be assumed to be zero. The
other measurement. 2.03 g, has two digits to the right of the decimal
point . It provides information up to and including the hundredths place.
Suppose you were asked to add the two measurements. Simply car -
rying out the addition would result in an answer of 25.1 g + 2.03 g =
27.13 g. That answer suggests there is certainty all the way to the
hundredths place. However, that result is not justified because the hun -
dredths place in 25.1 g is completely unknown. The answer must be
adjusted to reflect the uncertainty in the numbers added .
When lidding nr subtracting decimals, the answer must have the same
number of digits to ( he right of the decimal point as there are in the mea -
surement having the fewest digits to the right of the decimal point .
Comparing the two values 25.1 g and 2.03 g, the measurement with the
fewest digits to the right of the decimal point is 25.1 g. It has only one such
digit . Following the rule, the answer must be rounded so that it has no
more than one digit to the right of the decimal point. The answer should
therefore be rounded to 27.1 g. When working with whole numbers, the
answer should be rounded so that the final significant digit is in the same
place as the leftmost uncertain digit . ( For example, 54( X ) + 365 = 5800. )

Multiplication and Division

with Significant Figures
Suppose you calculated the density of an object that has a mass of 3.05 g
and a volume of 8.47 mL. Hie following division on a calculator will give
a value of 0.360094451 .
mass 3.05 g
density
= volume 8.47 mL
= 0.360094451 g / ml .
The answer must be rounded to the correct number of significant fig-
ures. Hie values of mass and volume used to obtain the answer have
only three significant figures each . The degree of certainty in the calcu -
lated result is not justified . For multiplication or division , the answer can
have no more significant figures than are in the measurement with the
fewest number of significant figures . In the calculation just described , the
answer. 0.360094451 g/ mL. would be rounded to three significant fig -
ures to match the significant figures in 8.47 mL and 3.05 g. The answer
would thus be 0.360 g/ mL.

SAMPLE PROBLEM E For more help, go to the Math Tutor at the end of Chapter 1

Carry out the following calculations. Express each answer to the correct number of
significant figures.
a . 5.44 m - 2.6103 m
b . 2.4 g/mL x 15.82 mL

MEASUREMENTS AND CALCULATIONS 49

 SOLUTION Carry out each mathematical operation. Follow the rules in Table 5 and Table 6 for deter -
mining significant figures and for rounding.
a. The answer is rounded to 2.83 m. because for subtraction there should be two digits to
the right of the decimal point, to match 5.44 m.
b. The answer is rounded to 38 g, because for multiplication there should be two significant
figures in the answer, to match 2.4 g/mL.

PRACTICE Answers in Appendix E

1. What is the sum of 2.099 g and 0.05681 g?

2. Calculate the quantity 87.3 cm - 1.655 cm.
3. Calculate the area of a rectangular crystal surface that measures
1.34 pm by 0.7488 pm. ( Hint : Recall that area = length x width and
is measured in square units. )
4. Polycarbonate plastic has a density of 1.2 g/cnv \ A photo frame is Go to go.hrw.com for
constructed from two 3.0 mm sheets of polycarbonate. Each sheet more practice problems
measures 28 cm by 22 cm. What is the mass of the photo frame? that ask you to calculate
using significant figures.
Keyword: HC 6 MEAX

Conversion Factors and Significant Figures

Earlier in this chapter, you learned how conversion factors are used to
change one unit to another. Such conversion factors are typically exact.That
is. there is no uncertainty in them. For example, there are exactly 100 cm in
a meter. If you were to use the conversion factor 100 cm/m to change meters
to centimeters, the 100 would not limit the degree of certainty in the answer.
'
Hius. 4.608 m could be converted to centimeters as follows.
100 cm
4.608 m x = 46().8 cm
m
The answer still has four significant figures. Because the conversion fac -
tor is considered exact , the answer would not be rounded. Most exact
conversion factors are defined, rather than measured, quantities .
Counted numbers also produce conversion factors of unlimited preci-
sion. For example, if you counted that there are 10 test tubes for every
student , that would produce an exact conversion factor of 10 tesl tubes/
student. There is no uncertainty in that factor.

Scientific Notation
In scientific notation, numbers are written in the form M x ! 0 n. where
the factor M is a number greater than or equal to l hut less than 10 and
n is a whole number. For example, to write the quantity 65 000 km in

50 CHAPTER 2
scientific notation and show the first two digits as significant, you
would write the following.
6.5 x 104 km
Writing the M factor as 6.5 shows that there are exactly two significant
figures. If. instead, you intended the first three digits in 65 000 to he sig-
nificant. you would write 6.50 x 104 km. When numbers are written in
scientific notation, only the significant figures are shown.
Suppose you are expressing a very small quantity, such as the length
of a flu virus. In ordinary notation this length could be 0.000 12 mm. That
length can be expressed in scientific notation as follows.
J
0.000 12 mm = 1.2 x 10 mm
Move the decimal point four places to the
right, and multiply the number by 10 4. '

1 . Determine XI by moving the decimal point in the original number to

the left or the right so that only one nonzero digit remains to the left
of the decimal point.
2 . Determine / / bv counting the number of places that you moved the
decimal point. If you moved it to the left,;? is positive. If you moved
it to the right, /? is negative.

Mathematical Operations
Using Scientific Notation
1. Addition and subtraction These operations can be performed only if
the values have the same exponent ( / / factor ). If they do not . adjust -
ments must be made to the values so that the exponents are equal.
Once the exponents are equal, the XI factors can be added or sub-
tracted. The exponent of the answer can remain the same, or it may
then require adjustment if the M factor of the answer has more than
one digit to the left of the decimal point. Consider the example of the
addition of 4.2 x 104 kg and 7.9 x I03 kg.

We can make both exponents either 3 or 4. The following solutions

are possible.

4.2 x l()J kg
+0.79 x IQ4 kg
4.99 x If)4 kg rounded to 5.0 x 104 kg

or

7.9 x 103 kg
+42 x l(V kg
49.9 x 103 kg = 4.99 x It)4 kg rounded to 5.0 x If)4 kg
Note that the units remain kg throughout.

MEASUREMENTS AND CALCULATIONS 51

 FIGURE 10 When you use a sci-
entific calculator to work problems
in scientific notation, don't forget to 5.44 flJ 7 _2_J 8.1 4 ENTER SOLAR
express the value on the display to
671.6049383
the correct number of significant fig-
ures and show the units when you rounded to 6.7 x 102 q/mol
write the final answer.

671.6049383
rounded to 6.7 x 102 g/mol

2. Multiplication The .1/ factors are multiplied, and the exponents are
added algebraically.

Consider the multiplication of 5.23 x 1(C pm by 7.1 x 10 2 urn.

(5.23 x IQ6|im)( 7.1 x 10”2 pm) = ( 5.23 x 7.1 )( 106 x 1(T 2)
= 37.133 x 104 pnr ( adjust to two
significant digits )
= 3.7 105 pnr
x

Note that when length measurements are multiplied, the result is

area. The unit is now pm2.

3. Division The M factors are divided, and the exponent of the

denominator is subtracted from that of the numerator. The calcula -
tor keystrokes for this problem are shown in Figure 10.

5.44 x 107 g 5.44

x l ( )7 4
g/mol
8.1 x l()4 mol 8.1
= 0.6716040383 x 10 ' (adjust to two significant figures)
= 6.7 x 102 g/mol
Note that the unit for the answer is the ratio of grams to moles.

Using Sample Problems

Learning to analyze and solve such problems requires practice and a
logical approach. In this section, you will review a process that can help
you analyze problems effectively. Most Sample Problems in this book
are organized by four basic steps to guide your thinking in how to work
out the solution to a problem.

52 CHAPTER 2
Analyze
The first step in solving a quantitative word problem is to read the prob -
lem carefully a! least twice and to analyze the information in it . Note any
important descriptive terms that clarify or add meaning to the problem.
Identify and list the data given in the problem. Also identify the
unknown — the quantity you are asked to find.

Plan
The second step is to develop a plan for solving the problem. The plan
should show how the information given is to be used to find the
unknown. In the process, reread the problem to make sure you have
gathered all the necessary information. It is often helpful to draw a pic -
ture that represents the problem. For example, if you were asked to
determine the volume of a crystal given its dimensions, you could draw
a representation of the crystal and label the dimensions. This drawing
would help you visualize the problem .
Decide which conversion factors, mathematical formulas, or chemi -
cal principles you will need to solve the problem. Your plan might
suggest a single calculation or a series of them involving different con-
version factors. Once you understand how you need to proceed, you
may wish to sketch out the route you will take, using arrows to point the
way from one stage of the solution to the next. Sometimes you will need
data that are not actually part of the problem statement . For instance,
you'll often use data from the periodic table.

Compute
The third step involves substituting the data and necessary conversion
factors into the plan you have developed . At this stage you calculate the
answer, cancel units, and round the result to the correct number of sig-
nificant figures. It is very important to have a plan worked out in step 2
before you start using the calculator. All too often, students start multi-
plying or dividing values given in the problem before they really under -
stand what they need to do to get an answer.

Evaluate
Examine your answer to determine whether it is reasonable. Use the fol-
lowing methods, when appropriate, to carry out the evaluation.
1. C heck to see that the units are correct. If they are not. look over the
setup. Are the conversion factors correct ?
2 . Make an estimate ol the expected answer. Use simpler, rounded
numbers to do so. Compare the estimate with your actual result. The
two should be similar.
3. Check the order of magnitude in your answer. Does it seem reasonable
compared with the values given in the problem? If you calculated the
density of vegetable oil and got a value of 54.9 g/mL. you should know
that something is wrong. Oil floats on water; therefore, its density is less
than water, so the value obtained should be less than l.O g/mL.
4. Be sure that the answer given for any problem is expressed using the
correct number of significant figures.

MEASUREMENTS AND CALCULATIONS 53

 Look over the following quantitative Sample Problem. Notice how
the four-step approach is used, and then apply the approach yourself in
solving the practice problems that follow.

SAMPLE PROBLEM F
Calculate the volume of a sample of aluminum that has a mass of 3.057 kg. The density of aluminum is
’
2.70 g/crn .

SOLUTION
1 ANALYZE .
Given: m;iss = 3.057 kg density = 2.70 g/cm '
Unknown: volume of aluminum

2 PLAN The density unit in the problem is g/cm \ and the mass given in the problem is expressed in
kg. Therefore, in addition to using the density equation, you will need a conversion factor
representing the relationship between grams and kilograms.
1000 g = 1 kg
Also, rearrange the density equation to solve for volume.
muss m
density - or D= -
volume V
m
V= —
D
3.057 Tg 1000
3 COMPUTE V=
2.70 g/cm " tg
* = 1132.222 . . . cm ' ( calculator answer )

The answer should be rounded to three significant figures.

V = 1.13 x 103 cm3
4 EVALUATE .
The unit of volume cnr\ is correct. An order- of-niagnitude estimate would put the answer
at over 1000 cm3.
3
x 1000
2
The correct number of significant figures is three, which matches that in 2.70 g/cm \

PRACTICE Answers in Appendix E

1. What is the volume, in milliliters, of a sample of helium that has a

mass of 1.73 x 10 ' g, given that the density is 0.178 47 g/L?
2 . What is the density of a piece of metal that has a mass of
6.25 x 10" g and is 92.5 cm x 47.3 cm x 85.4 cm?
3 . How many millimeters are there in 5.12 x HP kilometers?
Go to go.hrw.com for
.
4 . A clock gains 0.020 second per minute How many seconds will the more practice problems
clock gain in exactly six months, assuming exactly 30 days per month? that ask you to calculate
using scientific notation.
Keyword: HC 6 MEAX

54 CHAPTER 2
 Direct Proportions
Two qmm lilies arc directly proportional to each oilier if dividing one by
the oilier gives a constant value . For example, if the masses and volumes
of different samples of aluminum are measured, the masses and vol -
umes will be directly proportional to each other. As the masses of the
samples increase, their volumes increase by the same factor, as you can
see from the data in Table 7. Doubling the mass doubles the volume.
Halving the mass halves the volume.
When two variables, v and v, are directly proportional to each other,
the relationship can be expressed as y « .v. which is read as *‘y is pro-
portiona / to A . The general equation for a directly proportional rela -
tionship between the two variables can also be written as follows.
v
=A
v
The value of A is a constant called the proportionality constant. Written
in this form, the equation expresses an important fact about direct pro -
portion: the ratio between the variables remains constant. Note that
using the mass and volume values in Table 7 gives a mass-volume ratio
that is constant ( neglecting measurement error ). The equation can be
rearranged into the following form.
V = kx

The equation y = kx may look familiar to you. It is the equation for a

special case of a straight line. If two variables related in this way are
graphed versus one another, a straight line, or linear plot that passes
through the origin ( 0.0 ), results. The data for aluminum from Table 7 are
graphed in Figure 11. The mass and volume of a pure substance are
directly proportional to each other. Consider mass to be y and volume to FIGURE 11 The graph of mass
be v. The constant ratio. A. for the two variables is density. The slope of versus volume shows a relationship
of direct proportion. Notice that the
the line reflects the constant densitv, or mass-volume ratio, of aluminum.
line is extrapolated to pass through
the origin.

TABLE 7 Mass-Volume Data Mass Vs. Volume of Aluminum

for Aluminum at 20°C
120
3) ( g/ cm 3)
Mass (g) Volume (cm 100

54.7 20.1 2.72 80

U)
65.7 24.4 2.60
un 60
83.5 30.9 2.70 m

96.3 35.8 2.69 40 y

/
105.7 39.1 2.70 20
/

0
0 10 20 30 40 50 60
Volume (cm 3)

MEASUREMENTS AND CALCULATIONS 55

 which is 2.70 g/cnT at 20 C. Notice also that the plotted line passes
through the origin. All directly proportional relationships produce linear
graphs that pass through the origin .

Inverse Proportions
Two quantities are inversely proportional to each other if their product is
constant . An example of an inversely proportional relationship is that
between speed of travel and the time required to cover a fixed distance.
The greater the speed, the less time that is needed to go a certain fixed
distance. Doubling the speed cuts the required time in half. Halving the
speed doubles the required time.
When two variables, A and y, are inversely proportional to each other,
the relationship can be expressed as follows.
I
V oc -
X

This is read “y is proportional to 1 divided by A." The general equation

*

for an inversely proportional relationship between the two variables

can be written in the following form.

xy = k
In the equation, k is the proportionality constant. If x increases, v must
decrease by the same factor to keep the product constant.
A graph of variables that are inversely proportional produces a curve
called a hyperbola. Such a graph is illustrated in Figure 12. When the
temperature of the gas is kept constant, the volume ( V ) of the gas sam -
ple decreases as the pressure ( P ) increases. Look at the data shown in
.
Table 8 Note that P x V gives a reasonably constant value. The graph
of this data is shown in Figure 12.

TABLE 8 Pressure -Volume Data for Nitrogen

at Constant Temperature
Pressure (kPa ) Volume (cm 3) Px V
100 500 50 000
150 333 50 000
200 250 50 000
250 200 50 000
300 16b 49 800
350 143 50 100
400 125 50 0( H )
450 110 49 500

56 CHAPTER 2
Volume Vs. Pressure of Nitrogen FIGURE 12 The graph of
volume versus pressure shows an
600
inversely proportional relationship.
550 Note the difference between the
500 shape of this graph and that of the
graph in Figure 11.
450
400
E
U
350

g 300
1
>
250

200
150
100
50

0
0 50 100 150 200 250 300 350 400 450 500 550 600
Pressure (kPa )

SECTION REVIEW c. (8.99 xKT4 m) x (3.57 x 104 m)

3
1. The density of copper is listed as 8.94 g/cm . Two 2.17 x 10~3 g
students each make three density determinations '
5.022 x 104 ml
of samples of the substance. Student A’s results
are 7.3 g/mL, 9.4 g/mL, and 8.3 g/mL. Student B's
.
6 Write the following numbers in scientific notation.
results are 8.4 g/cm3, 8.8 g/cm3, and 8.0 g/cm 3. a. 560 000 .
c 0.000 4120
Compare the two sets of results in terms of preci- b. 33 400
sion and accuracy.
7. A student measures the mass of a beaker filled
2. Determine the number of significant figures. with corn oil. The mass reading averages
a. 6.002 cm d. 7000 kg 215.6 g. The mass of the beaker is 110.4 g.
b. 0.0020 m e. 7000. kg a. What is the mass of the corn oil ?
c. 10.0500 g b. What is the density of the corn oil if its vol -
ume is 114 cm3 ?
3. Round 2.6765 to two significant figures.
8. Calculate the mass of gold that occupies 5.0 x
4. Carry out the following calculations.
10-3 cm3. The density of gold is 19.3 g/cm3.
a. 52.13 g + 1.7502 g
9. What is the difference between a graph repre-
b. 12 m x 6.41 m senting data that are directly proportional and a
16.25 g graph of data that are inversely proportional?
‘
5.1442 mL Critical Thinking
5. Perform the following operations. Express each
10. APPLYING CONCEPTS The mass of a liquid is
answer in scientific notation.
_1 11.50 g and its volume is 9.03 mL. How many
a. (1.54 xIO-2 g) + (2.86 x 10 g) significant figures should its density value have ?
b. (7.023 x 109 g) - (6.62 x 107 g) Explain the reason for your answer.

MEASUREMENTS AND CALCULATIONS 57

 CHAPTER HIGHLIGHTS
Scientific Method
I Vocabulary •The scientific method is a logical approach to solving problems
scientific method that lend themselves to investigation.
system •A hypothesis is a testable statement that serves as the basis for
hypothesis predictions and further experiments.
model •A theory is a broad generalization that explains a body of
theory known facts or phenomena.

Units of Measurement
I Vocabulary •The result of nearly every measurement is a number and a unit.
quantity •The SI system of measurement is used in science. It has seven
SI base units: the meter ( length ), kilogram (mass ), second ( time ),
weight kclvin ( temperature ), mole ( amount of substance ), ampere
derived unit ( electric current ), and candela ( luminous intensity ).
volume •Weight is a measure of the gravitational pull on matter.
density •Derived SI units include the square meter ( area ) and the cubic
conversion factor meter ( volume ).
dimensional analysis • Density is the ratio of mass to volume.
• Conversion factors are used to convert from one unit to another.

Using Scientific Measurements

i Vocabulary •Accuracy refers to the closeness of a measurement to the cor-
accuracy rect or accepted value. Precision refers to the closeness of val -
precision ues for a set of measurements.
percentage error •Percentage error is the difference between the experimental
significant figures and the accepted value that is divided by the accepted value
scientific notation and then multiplied by 100.
directly proportional • significant figures in a number consist of all digits known
The
inversely proportional with certainty plus one final digit , which is uncertain.
•After addition or subtraction, the answer should be rounded so
that it has no more digits to the right of the decimal point than
there are in the measurement that has the smallest number of
digits to the right of the decimal point. Alter multiplication or
division, the answer should be rounded so that it has no more
significant figures than there are in the measurement that has
the fewest number of significant figures.
•Exact conversion factors are completely certain and do not
limit the number of digits in a calculation.
•A number written in scientific notation is of the form M x 10",
in which M is greater than or equal to 1 but less than 10 and n
is an integer.
•Two quantities are directly proportional to each other if divid-
ing one by the other yields a constant value. Two quantities are
inversely proportional to each other if their product has a con -
stant value.

58 CHAPTER 2
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
13 . a. Why are the units used that are to express
Scientific Method the densities of gases different from those used
SECTION 1 REVIEW to express the densities of solids or liquids?
1. How does quantitative information differ from b. Name two units for density.
c. Why is the temperature at which density is
qualitative information ?
2 . What is a hypothesis? measured usually specified?
3 . a. What is a model in the scientific sense? 14. a. Which of the solids listed in Table 4 will float
b. Ilow does a model differ from a theory ? on water ?
b. Which of the liquids will sink in milk ?
15. a. Define conversion factor
Units of Measurement b. Explain how conversion factors are used.

SECTION 2 REVIEW
PRACTICE PROBLEMS
4. Why is it important for a measurement system
16. What is the volume, in cubic meters, of a rectan -
to have an international standard?
gular solid that is 0.25 m long, 6.1 m wide, and
5. How does a quantity differ from a unit ? Use
4.9 m high ?
two examples to explain the difference.
17 . Find the density of a material, given that a
6. List the seven SI base units and the quantities
5.03 g sample occupies 3.24 mL. ( Hint: See
they represent.
Sample Problem A. )
7. What is the numerical equivalent of each of the
18. What is the mass of a sample of material that has
following SI prefixes?
a volume of 55.1 cm3 and a density of 6.72 g/cnT ?
a. kilo- d. micro -
19. A sample of a substance that has a density of
b. centi- e. milli-
0.824 g/mL has a mass of 0.451 g. Calculate the
c. mega-
volume of the sample.
8. Identify the SI unit that would be most appro -
20. How many grams are in 882 ug? (Hint: See
priate for expressing the length of the following.
Sample Problem B. )
a. width of a gymnasium
21. Calculate the number of milliliters in 0.603 L.
b. length of a finger
22. The density of gold is 19.3 g/cm \
c. distance between vour town and the closest
j
a. What is the volume, in cubic centimeters, of a
border of the next state
sample of gold that has a mass of 0.715 kg?
d. length of a bacterial cell
b. If this sample of gold is a cube, what is the
9. Identify the SI unit that would be most appro -
length of each edge in centimeters?
priate for measuring the mass of each of the fol -
23. a. Find the number of kilometers in 92.25 m .
lowing objects.
b. Convert the answer in kilometers to
a. table
centimeters.
b. coin
c. a 250 mL beaker
10. Explain why the second is not defined by the
length of the day. Using Scientific
11. a. What is a derived unit ? Measurements
b. What is the Sl -derived unit for area?
12. a. List two Si -derived units for volume. SECTION 3 REVIEW
b. List two non-SI units for volume, and explain 24. Compare accuracy and precision.
how they relate to the cubic centimeter. 25 . a. Write the equation that is used to calculate
percentage error.

MEASUREMENTS AND CALCULATIONS 59

 CHAPTER REVIEW

b. Under what condition will percentage error 37. What is the percentage error of a length mea -
be negative ? surement of 0.229 cm it the correct value is
26. Itow is the average for a set of values calculated? 0.225 cm?
27. What is meant by a mass measurement 38. How many significant figures are in each of the
expressed in this form: 4.b g ± 0.2 g? following measurements? ( Hint: See Sample
28. Suppose a graduated cylinder were not correct - Problem D.)
ly calibrated. How would this affect the results a. 0.4004 mL
of a measurement ? How would it affect the b. 6000 g
results of a calculation using this measurement ? c. 1.000 30 km
29. Round each of the following measurements to .
d. 400 mm
the number of significant figures indicated. 39. Calculate the sum of 6.078 g and 0.3329 g.
a. 67.029 g to three significant figures 40. Subtract 7.11 cm from 8.2 cm. ( Hint : See
b. 0.15 1. to one significant figure Sample Problem E. )
c. 52.8005 mg to five significant figures 41. What is the product of 0.8102 m and 3.44 m ?
'

d. 3.174 97 mol to three significant figures 42. Divide 94.20 g by 3.167 22 mL.
30. State the rules governing the number of signifi - 43. Write the following numbers in scientific
cant figures that result from each of the follow - notation.
ing operations. a. 0.000 673 0
a. addition and subtraction b. 50 000.0
b. multiplication and division c. 0.000 003 010
31. What is the general form for writing numbers in 44. The following numbers are in scientific nota-
scientific notation? tion. Write them in ordinary notation.
32. a. By using .v and y, state the general equation a. 7.050 x HF g
for quantities that are directly proportional, To
b. 4.000 05 x 7 mg
b. For two directly proportional quantities, what c. 2.350 Ox I04 ml.
happens to one variable when the other vari- 45. Perform the following operation. Express the
able increases? answer in scientific notation and with the cor -
33. a. State the general equation for quantities,.v rect number of significant figures .
and v, that are inversely proportional, 0.002115m x 0.0000405m
b. For two inversely proportional quantities, 46. A sample of a certain material has a mass of
what happens to one variable when the other 2.03 x 10“ ' g. Calculate the volume of the sam -
increases? ple. given that the density is 9.133 x 10 1 g/ cm '.
34. Arrange in the correct order the following four Use the four-step method to solve the problem.
basic steps for finding the solution to a prob- ( Hint : See Sample Problem F ) .
lem: compute, plan, evaluate, and analyze.

PRACTICE PROBLEMS MIXED REVIEW

35. A student measures the mass of a sample as 47 . A man finds that he has a mass of 100.6 kg. I le
9.67 g. Calculate the percentage error, given goes on a diet, and several months later he finds
that the correct mass is 9.82 g. (Hint: See that he has a mass of 96.4 kg. Express each num-
Sample Problem C. ) ber in scientific notation, and calculate the num -
36 . A handbook gives the density of calcium as ber of kilograms the man has lost by dieting.
1.54 g/cm \ Based on lab measurements, what 48. A large office building is 1.07 x 10: m long,
is the percentage error of a density calculation 31 m wide, and 4.25 x 10“ m high. What is its
of l .25 g/cm3 ? volume ?

60 CHARTER 2
 CHAPTER REVIEW

49 . An object has a mass of 57.6 g. Find the object 's of each sample. Calculate the density of each
density, given that its volume is 40.25 cm \ metal from your measurement data. (I lint :
50. A lab worker measures the mass of some Consider using the water displacement tech -
.
sucrose as 0.947 mg Convert that quantity to nique to measure the volume of your samples. )
grams and to kilograms. 58. Use the data from the Nutrition Facts label
51. A student calculates the density of iron as below to answer the following questions:
6.80 g/ cnr by using lab data for mass and vol- a. Use the data given on the label for grams of
ume. A handbook reveals that the correct value fat and Calories from fat to construct a con-
is 7.86 g/cm \ What is the percentage error ? version factor that has the units Calories per
gram.
b. Calculate the mass in kilograms for 20 serv -
u USING THE HANDBOOK ings of the food .
c. Calculate the mass of protein in micrograms
52. Find the table of properties for Group l ele - for one serving of the food .
ments in the Elements Handbook . Calculate the d. What is the correct number of significant fig-
volume of a single atom of each element listed ures for the answer in item a? Whv ?
in the table by using the equation for the vol -
ume of a sphere.
-it
3
.r 3 Nutrition Facts
Serving Size % cup ( 30g)
Servings Per Container About 14
53. Use the radius of a sodium atom from the
Elements Handbook to calculate the number of with
Corn 1/ 2 cup

sodium atoms in a row 5.00 cm long. Assume that Amount Per Serving Crunch skim milk

each sodium atom touches the ones next to it . Calories 120 160
54. a. A block of sodium that has the measurements Calories from Fat 15 20
3.00 cm x 5.00 cm x 5.00 cm has a mass of °b Daily Value * *

75.5 g. Calculate the density of sodium. Total Fat 2g 3% 3%

#

b. Compare your calculated density with the Saturated Fat Og 0% 0%

Cholesterol Omg O° o 1%
value in the properties table for Group l el-
Sodium 160mg 7 9%
ements. Calculate the percentage error for
Potassium 65mg 2% 8%
vour densitv determination. Total
Carbohydrate 25g 8% 10%
Dietary Fiber 3g
RESEARCH & WRITING Sugars 3g
Other Carbohydrate 11 g
55. I low does the metric system, which was once a Protein 2g
standard for measurement , differ from SI ? Why ' Amount in Cereal. A serving of cereal plus skim milk
was it necessary for the United States to change .
provides 2g fal. less 5mg cholesterol 220mg
to SI? .
sodium 270mg potassium. 31g carbohydrate
( 19g sugars ) and 6g protein.
56. What are ISO 9000 standards? How do they “Percent Daily Values are based on a 2,000 calone diet .
Vour daily values may be higher or lower depending on
affect industry on an international level? your calone needs:
Calones 2.000 2.500
Total Fat Less than 65g 80g
Sat Fat Less than 20g 25g
ALTERNATIVE ASSESSMENT Cholesterol
Sodium
Less than
Less than
300mg 300mg
2 400mg 2 ,400mg
Potassium 3.500mg 3.500mg
57. Performance Obtain three metal samples from Total Carbohydrate 300g 375g
Dietary Fiber 25g 30g
vour teacher. Determine the mass and volume

MEASUREMENTS AND CALCULATIONS 61

 Math Tutor SCIENTIFIC NOTATION

Any value expressed in scientific notation, whether large or small, has two parts. The
first part, the first factor; consists of a number greater than or equal to 1 but less than
10, which may have any number of digits after the decimal point. The second part
consists of a power of 10.
exponent
r^i
6.02 x IQ 23
First factor power of ten

To write the first part, move the decimal point to the right or the left so that there is
only one nonzero digit to the left of the decimal point. The second part is written as
an exponent, which is determined by counting the number of places the decimal
point must be moved. If it is moved to the right, the exponent is negative. If it is
moved to the left, the exponent is positive.

-Solving TIPS
r Problem
• In addition and subtraction all values , must first be converted to numbers that
have the same exponent of 10. The result is the sum or the difference of the
first factors, multiplied by the same exponent of 10. Finally, the result should be
rounded to the correct number of significant figures and expressed in scientific
notation.
• In multiplication, the first factors are multiplied and the exponents of 10 are
added.
• In division, the first factors of the numbers are divided and the exponent of 10
in the denominator is subtracted from the exponent of 10 in the numerator.

SAMPLE 1 SAMPLE 2
Write 299 800 000 m/ s in scientific notation. Solve the following equation and write the answer
The decimal must move to the left 8 places, in scientific notation.
which indicates a positive exponent. (3.1 x 103)(5.21 x It )4 )
Multiply the first factors, and then add the expo -
299 800 000. m/s
VAAAAAAA2
K 7 6 5 A 3 2 1
nents of 10 .
( 3.1 x 3.21 ) x 10( 3 + 4 ) = lft x 107 = 1.ft x 10K
The value in scientific notation is 2.998 x l()'s ni/s.

PRACTICE PROBLEMS
.
I Rewrite the following numbers in scientific 2. Solve the follow ing equations, and write the
notation. answers in scientific notation.
a. 0.0000745 g a. 1.017 x 1()3 - 1.013 x 104
b. 5984102 nm 9.27 x l O4
11.24 x 105

62 CHAPTER 2
^ n '2 1
o° /
8
ill
Answer the following items on a separate piece of paper. .
7 The accuracy of a measurement
MULTIPLE CHOICE A . is how close it is to the true value.

1. Which of the following masses is the largest ?

.
B does not depend on the instrument used to
measure the object.
.
A 0.200 g C. 20.0 mg
C. indicates that the measurement is also precise.
B. 0.020 kg D. 2000 |ig
D. is something that scientists rarely achieve.
2. Which of the following measurements contains
8. A measurement of 23 465 mg converted to
three significant figures?
grams equals
A. 200 mL C 20.2 mL . A . 2.3465 g. .
C 234.65 g.
B. 0.02 mL D 200.0 mL. .
B 23.465 g. D. 0.23465 g.
3. A theory differs from a hypothesis in that a theory
A . cannot be disproved.
9. A metal sample has a mass of 45.65 g The vol- .
ume of the sample is 16.9 cm 1. The density of
*

B. always leads to the formation of a law. the sample is

C. has been subjected to experimental testing. A . 2.7 g/cnT. .
C 0.370 g/cnr\
D. represents an educated guess . .
B 2.70 g/cm*\ D. 0.37 g/ cm \
4. All measurements in science SHORT ANSWER
A. must be expressed in scientific notation.
10. A recipe for 18 cookies calls for 1 cup of choco-
.
B have some degree of uncertainly.
late chips. How many cups of chocolate chips
C. are both accurate and precise . are needed for 3 dozen cookies? What kind of
D. must include only those digits that are known
proportion, direct or indirect, did you use to
with certainty. answer this question?
5 . When numbers are multiplied or divided, the .
11 Which of the following statements contain exact
answer can have no more numbers?
A . significant figures than are in the measure - A. There are 12 eggs in a dozen.
ment that has the smallest number of signifi - B. The accident injured 21 people.
cant figures. C. The circumference of the Earth at the equa -
B. significant figures than are in the measure - tor is 40 000 km .
ment that has the largest number of signifi -
EXTENDED RESPONSE
cantfigures.
C. digits to the right of the decimal point than .
12 You have decided to test the effects of five gar -
are in the measurement that has the smallest den fertilizers by applying some of each to sepa -
number of digits to the right of the decimal rate rows of radishes. What is the variable you are
point. testing? What factors should you control? How
will you measure and analyze the results?
D. digits to the right of the decimal point than
are in the measurement that has the largest 13. Around 1150, King David 1 of Scotland defined
number of digits to the right of the decimal the inch as the width of a man's thumb at the
point. base of the nail. Discuss the practical limitations
of this early unit of measurement.
.
6 Which of the following is not part of the scien-
tific method ?
A . making measurements
B. introducing bias
C. making an educated guess Carefully read questions that ask
D. analyzing data for the one choice that is not correct. Often these ques-
tions include words such as is not except or all but.

MEASUREMENTS AND CALCULATIONS 63

 EXPERIMENT 2

Percentage of Water in Popcorn

OBJECTIVES BACKGROUND
Popcorn pops because of the natural moisture inside
• Measure the masses of various combinations
of a beaker, oil , and popcorn kernels. each kernel . When the internal water is heated
above 100°C, the liquid water changes to a gas,
• Determine the percentages of water in pop- which takes up much more space than the liquid ,
corn kernels. so the kernel expands rapidly.
• Compare experimental data. The percentage of water in popcorn can be deter -
mined by the following equation .
MATERIALS
initial mass - final mass
aluminum foil ( 1 sheet ) x 100 = percentage of H:0 in
initial mass unpopped popcorn
beaker, 250 mL
The popping process works best when the kernels
Bunsen burner with gas tubing and striker are first coated with a small amount of vegetable oil .
kernels of popcorn for each of three Make sure you account for the presence of this oil
brands ( 80 ) when measuring masses. In this lab. you will design a
oil to coat the bottom of the beaker procedure for determining the percentage of water
in three samples of popcorn. The popcorn is for test -
ring stand , iron ring, and wire gauze ing only, and must not be eaten .

SAFETY

For review of safety, please see Safety in the

Chemistry Laboratory in the front of your book .

PREPARATION
1. In your notebook prepare a data table like the
,

one your teacher has made on the board. The

table should have three columns, one for each
brand of popcorn.

64 CHAPTER 2
 EXPERIMENT 2

PROCEDURE CLEANUP AND DISPOSAL

1. Measure the mass of a 250 mL beaker. Record 13. Dispose of popped popcorn and aluminum foil
the mass in your data table. in containers as directed by your instructor. Do
not eat the popcorn.
2. Add a small amount of vegetable oil to the
14. Clean beakers. Return beakers and other equip-
beaker to coal the bottom of it. Measure the
ment to the proper place.
mass of the beaker and oil. Record the mass in
15. Clean all work surfaces and personal protective
your data table.
* equipment as directed by your instructor.
3. Add 20 kernels of brand A popcorn to the 16. Wash your hands thoroughly before
beaker. Shake the beaker gently to coat the ker - leaving the laboratory.
nels with oil. Measure the mass of the beaker, oil.
and popcorn. Record the mass in your data table. ANALYSIS AND INTERPRETATION
4. Subtract the mass found in step 2 from the 1. Applying Ideas: Determine the mass of the 20
mass found in step 3 to obtain the mass of 20 unpopped kernels of popcorn for each brand of
unpopped kernels. Record the mass in your popcorn.
data table. 2. Applying Ideas: Determine the mass of the 20
5. Cover the beaker loosely with the aluminum popped kernels of popcorn for each brand of
foil. Punch a few small holes in the aluminum popcorn.
foil to let moisture escape. These holes should 3. Applying Ideas: Determine the mass of the
not be large enough to let the popping corn pass water that was lost when the popcorn popped
through. for each brand.
6. Heat the popcorn until the majority of the ker -
nels have popped. The popcorn pops more effi- CONCLUSIONS
ciently if the beaker is held firmly with tongs 1. Analyzing Data: Determine the percentage by
and gently shaken side to side on the wire gauze. mass of water in each brand of popcorn.

7. Remove the aluminum foil from the beaker and 2. Inferring Relationships: Do all brands of pop -
allow the beaker to cool for 10 minutes. Then, corn contain the same percentage water?
measure the mass of the beaker, oil, and popped
corn. Record the mass in your data table.
EXTENSIONS
8. Subtract the mass in step 7 from the mass in step 3 1. Designing Experiments: What are some likely
to obtain the mass of water that escaped when the areas of imprecision in this experiment ?
corn popped. Record the mass in your data table.
2. Designing Experiments: Do you think that the
9. Calculate the percentage of water in the popcorn. volume of popped corn depends on the percent -
10. Dispose of the popcorn in the designated con - age of water in the unpopped corn? Design an
tainer. Remove the aluminum foil, and set it experiment to find the answer.
aside. Clean the beaker, and dry it well.
Alternatively, if your teacher approves, use a dif -
ferent 250 mL beaker.
.
11 Repeat steps 1-10 for brand B popcorn.
12. Repeat steps l- lO for brand C popcorn.

MEASUREMENTS AND CALCULATIONS 65

 CHAPTER 3

Atoms: The Building

Blocks of Matter
An atom is the smallest particle of an element that
retains the chemical properties of that element.
The Atom: From SECTION 1

Philosophical Idea to OBJECTIVES

Scientific Theory ^ Explain the law of
conservation of mass, the
law of definite proportions,
and the law of multiple
proportions.

^ Summarize the five essential

W hen you crush a lump of sugar , you can see that it is made up of points of Dalton' s atomic
many smaller particles of sugar. You may grind these particles into a very theory.
fine powder, but each tiny piece is still sugar. Now suppose you dissolve
the sugar in water.The tiny particles seem to disappear completely. Even
Explain the relationship
if you look at the sugar- water solution through a powerful microscope, * between Dalton's atomic
you cannot see any sugar particles. Yet if you were to taste the solution, theory and the law of conser -
you 'd know that the sugar is still there. Observations like these led early vation of mass, the law of
philosophers to ponder the fundamental nature of matter. Is it continu- definite proportions, and the
ous and infinitely divisible, or is it divisible only until a basic, invisible law of multiple proportions.
particle that cannot be divided further is reached?
The particle theory of matter was supported as early as 4( H ) B.C. bv
certain Greek thinkers, such as Democritus.I le called nature's basic par -
ticle an atom , based on the Greek word meaning “indivisible." Aristotle
was part of the generation that succeeded Democritus. His ideas had a
lasting impact on Western civilization, and he did not believe in atoms.
Historical Chemistry
He thought that all matter was continuous, and his opinion was accept -
ed for nearly 2000 years. Neither the view of Aristotle nor that of Go it go.hrw.com for a full-length
)

article on the history of atomic

Democritus was supported by experimental evidence, so each remained
theory and transmutation.
.
speculation until the eighteenth century Then scientists began to gather
evidence favoring the atomic theory of matter. Keyword: HC 6 ATMX

Foundations of Atomic Theory

Virtually all chemists in the late 1700s accepted the modern definition
of an element as a substance that cannot be further broken down by
ordinary chemical means. It was also clear that elements combine to
form compounds that have different physical and chemical properties
than those of the elements that form them. There was great controversy,
however, as to whether elements always combine in the same ratio
when forming a particular compound.
The transformation of a substance or substances into one or more
new substances is known as a chemical reaction . In the 1790s. the study
of matter was revolutionized by a new emphasis on the quantitative

ATOMS: THE BUILDING BLOCKS OF MATTER 67

 analysis of chemical reactions. Aided by improved balances, investigators
began to accurately measure the masses of the elements and compounds
they were studying. This led to the discovery of several basic laws. One
of these laws was the law of conservation of mass, w hich stales that mass
is neither created nor destroyed daring ordinary chemical reactions or
physical changes . This discovery was soon followed bv the assertion
that , regardless of where or how a pure chemical compound is prepared ,
it is composed of a fixed proportion of elements. For example, sodium
chloride, also known as ordinary table salt . always consists of 39.34 % by
mass of the element sodium , Na , and 60.66 % by mass of the element
chlorine. Cl. Hie fact that a chemical compound contains the same
elements in exactly the same proportions by mass regardless of the size of
the sample or source of the compound is known as the law of definite
FIGURE 1 Each of the salt crys- proportions.
tals shown here contains exactly It was also known that two elements sometimes combine to form
39.34 % sodium and 60.66 % chlorine more than one compound. For example, the elements carbon and oxygen
bv mass. form two compounds, carbon dioxide and carbon monoxide. Consider
samples of each of these compounds, each containing l .OOg of carbon . In
carbon dioxide. 2.66 g of oxygen combine with 1.00 g of carbon . In
carbon monoxide. 1.33 g of oxygen combine with 1.00 g of carbon . The
ratio of the masses of oxygen in these two compounds is 2.66 to 1.33. or 2
to 1 . This illustrates the law of multiple proportions: If two or more
different compounds are composed of the same two elements, then the
ratio of the masses of the second element combined with a cert ait t mass of
the first element is always a ratio of small whole / lumbers.

Dalton 's Atomic Theory

In ISOS, an English schoolteacher named John Dalton proposed an
explanation for the law of conservation of mass, the law of definite pro-
portions, and the law of multiple proportions. He reasoned that el -
ements were composed of atoms and that only whole numbers of atoms
can combine to form compounds. His theory can be summed up by the
following statements.
1. All matter is composed of extremely small particles called atoms.
2. Atoms of a given element are identical in size, mass, and other prop-
erties; atoms of different elements differ in size, mass, and other
properties.
3. Atoms cannot be subdivided , created , or destroyed .
SC
/lNKS , ] Orvriopttf «W tyito
4. Atoms of different elements combine in simple whole - number ratios
to form chemical compounds.
KitoouJ Some texfcen AuocutMw

For a variety of links related to this 5. In chemical reactions, atoms are combined. separated , or rearranged .
chapter, go to . . . irg

Topic: Atomic Theory

h According to Dalton 's atomic theory, the law of conservation of mass
SciLinks code: HC 60120 is explained by the fact that chemical reactions involve merely the
combination , separation, or rearrangement of atoms and that during
these processes atoms are not subdivided , created or destroyed . This
,

68 CHAPTER 3
 FIGURE 2 ( a ) An atom of
.
carbon. C and an atom of oxygen,
O. can combine chemically to form
Carbon, C Oxygen, O Carbon monoxide, CO
a molecule of carbon monoxide CO. .
Mass x Mass y Mass x + Mass y The mass of the CO molecule is
equal to the mass of the C atom
plus the mass of the O atom.
(b ) The reverse holds true in a
reaction in which a CO molecule
is broken down into its elements.
Carbon monoxide, CO Carbon, C Oxygen, O
Mass x + Mass y Mass x Mass y

idea is illustrated in Figure 2 for the formation of carbon monoxide

from carbon and oxygen.
The law of definite proportions, on the other hand, results from the
fact that a given chemical compound is always composed of the same
combination of atoms ( see Figure 3). As for the law of multiple
proportions, in the case of the carbon oxides, the 2- to- l ratio of oxygen
masses results because carbon dioxide always contains twice as many
atoms of oxygen ( per atom of carbon ) as does carbon monoxide. This
can also be seen in Figure 3 .
( a)
FIGURE 3 ( a ) CO molecules are
always composed of one C atom and
one O atom, ( b) CO *, molecules are
always composed of one C atom and
Carbon, C Oxygen, O Carbon monoxide, CO
two O atoms. Note that a molecule
(b)
of carbon dioxide contains twice as
many oxygen atoms as does a mole -
+ + cule of carbon monoxide.

Carbon, C Oxygen, O Oxygen, O Carbon dioxide, C02

Modern Atomic Theory

By relating atoms to the measurable property of mass. Dalton turned
Democritus's idea into a scientific theory that could be tested by experi -
ment . But not all aspects of Dalton’s atomic theory have proven to be
correct. For example, today we know that atoms are divisible into even
smaller particles ( although the law of conservation of mass still holds
SCllNKS. M ft
DmttH 4 UHiUMtd fey Ox
**
Nlwd Some Tmhtn AIMKMOM
true for chemical reactions). And. as you will see in Section 3, we know For a variety of links related to this
that a given element can have atoms with different masses. Atomic the - chapter, go to wvAv. sdlinks.org
ory has not been discarded, however. Instead, it has been modified to Topic: Carbon
explain the new observations. The important concepts that ( 1 ) all mat - SciLinks code: HC60214
ter is composed of atoms and that ( 2 ) atoms of any one element differ
in properties from atoms of another element remain unchanged.

ATOMS: THE BUILDING BLOCKS OF MATTER 69

 CAREERS
in Chemistry

Physical Chemist
Physical chemists focus on under - Gerd Binnig and
standing the physical properties of Heinrich Rohrer,
atoms and molecules. They are dri- scientists working
ven by a curiosity of what makes for IBM in Zurich,
things work at the level of atoms, Switzerland. They
and they enjoy being challenged. In shared the 1986
addition to chemistry, they study Nobel Prize in
mathematics and physics extensively. physics for their
Laboratory courses involving experi - discovery.
ence with electronics and optics are The basic principle
typically part of their training. Often, of STM is based on A This STM image shows a "corral " of iron atoms on a
they enjoy working with instruments the current that copper surface.
and computers. Physical chemists exists between a
can be experimentalists or theoreti- metallic needle that is sharpened to microelectronics. Usually, STM is used
cians. They use sophisticated instru- a single atom , the probe , and a con - with materials that conduct, but it
ments to make measurements, or ducting sample. As the probe passes has also been used to study biologi-
high- powered computers to perform above the surface of the sample at a cal molecules, such as DNA.
intensive calculations. The instru- distance of one or two atoms, elec - One innovative application of STM
ments used include lasers, electron trons can " tunnel " from the needle is the ability to position individual
microscopes, nuclear magnetic reso - tip to the sample s surface. The
' atoms. The figure shows the result of
nance spectrometers, mass spec - probe moves across, or " scans," the moving individual atoms. First, iron
trometers, and particle accelerators. surface of the sample. When the atoms were placed on a copper sur -
Physical chemists work in industry, probe comes close to the electrons face. Then, individual iron atoms
government laboratories, research of an individual atom, a signal is were picked up by the probe and
institutes, and academic institutions. produced. A weaker signal is pro- placed in position. The result is a
Because physical chemists work on duced between atoms. These signals " quantum corral " of 48 iron atoms
a wide range of problems, taking build a topographical (hill and val - on the surface of copper. The diame-
courses in other science disciplines ley) " map " of conducting and non- ter of the corral is about 14 nm.
is important. conducting regions. The resulting
map shows the position and spacing Questions
Scanning Tunneling
of atoms. 1. In addition to chemistry, what
Microscopy
Surface chemistry is a developing kinds of courses are important
For years, scientists have yearned for
subdiscipline in physical chemistry, for a student interested in a
the ability to " see " individual
and STM is an important tool in the physical chemistry career ?
atoms. Because atoms are so small,
field. Scientists use STM to study sur -
this had been nothing more than a 2. What part of an atom is detect -
face reactions, such as those that
dream. Now, the scanning tunneling ed by STM ?
take place in catalytic converters.
microscope, STM, gives scientists
Other areas of research in which STM
the ability to look at individual
is useful include semiconductors and
atoms. It was invented in 1981 by

70 CHAPTER 3
Quick1AB <* Wear safety goggles and an apron.

Materials
Constructing a Model • can covered by a sock sealed
with tape
Question Then compare your estimates • one or more objects that fit
of these objects with actual in the container
How can you construct a
model of an unknown object measurements using a metric • metric ruler
by ( 1 ) making inferences ruler and a balance. • balance
about an object that is in a
closed container and ( 2)
Discussion
touching the object without
seeing it ? 1. Scientists often use more than
one method to gather data.
How was this illustrated in the
Procedure
investigation?
Record all of your results in a
data table. 2. Of the observations you made,
1. Your teacher will provide you which were qualitative and
which were quantitative?
with a can that is covered by a
sock sealed with tape. Without 3. Using the data you gathered,
unsealing the container, try to draw a model of the unknown
determine the number of object(s) and write a brief sum-
objects inside the can as well as mary of your conclusions.
the mass, shape, size, composi-
tion, and texture of each. To
do this, you may carefully tilt
or shake the can. Record your
observations in a data table .
2. Remove the tape from the top
of the sock. Do not look inside
the can. Put one hand through
the opening, and make the
same observations as in step 1
by handling the objects. To
make more-accurate estima -
tions, practice estimating the
sizes and masses of some
known objects outside the can.

SECTION REVIEW Critical Thinking

1. List the five main points of Dalton's atomic theory. 3. ANALYZING INFORMATION Three compounds
2. What chemical laws can be explained by Dalton's containing potassium and oxygen are compared.
theory ? Analysis shows that for each 1.00 g of 0, the com-
pounds have 1.22 g, 2.44 g, and 4.89 g of K,
respectively. Show how these data support the
law of multiple proportions.

ATOMS: THE BUILDING BLOCKS OF MATTER 71

 SECTION 2
The Structure of
OBJECTIVES the Atom
J Summarize the observed
properties of cathode rays
that led to the discovery of
the electron.
A Ithough John Dalton thought atoms were indivisible, investigators
^ Summarize the experiment
.
in the late 1800s proved otherwise As scientific advances allowed a
carried out by Rutherford and deeper exploration of matter, it became clear that atoms are actually
his co- workers that led to the composed of several basic types of smaller particles and that the num -
discovery of the nucleus. ber and arrangement of these particles within an atom determine that
.
atom's chemical properties Today we define an atom as the smallest par -
tide o f an element that retains the chemical properties o f that element .
^ List the properties of protons, All atoms consist of two regions. The nucleus is a very small region
neutrons, and electrons.
.
located at the center of an atom In every atom, the nucleus is made up of
at least one positively charged particle called a proton and usually one or
j Define atom. more neutral particles called neutrons. Surrounding the nucleus is a region
occupied by negatively charged particles called electrons. Ibis region is
very large compared with the size of the nucleus. Protons, neutrons, and
electrons are often referred to as subatomic particles.

FIGURE 4 A simple cathode ray - Discovery of the Electron

tube. Particles pass through the tube
from the cathode, the metal disk The first discovery of a subatomic particle resulted from investigations
connected to the negative terminal into the relationship between electricity and matter. In the late 1800s .
of the voltage source, to the anode,
many experiments were performed in which electric current was passed
the metal disk connected to the posi -
through various gases at low pressures. ( Gases at atmospheric pressure
tive terminal.
don t conduct electricity well.) These experi-
'

ments were carried out in glass tubes like

the one shown in Figure 4. Such tubes are
Voltage source known as cathode- rav tithes .

Cathode Rays and Electrons

Gas at low pressure Cathode ray
Investigators noticed that when current
was passed through a cathode-ray tube,
the surface of the tube directly opposite
the cathode glowed. They hypothesized
that the glow was caused by a stream of
particles, which they called a cathode ray.
Cathode Anode The ray traveled from the cathode to the
( metal disk ) ( metal disk ) anode when current was passed through
T
Vacuum pump the tube. Experiments devised to test this

72 CHAPTER 3
hypothesis revealed the following
observations.
1. Cathode rays were deflected by a
magnetic field in the same manner
as a wire carrying electric current,
which was known to have a nega -
tive charge ( see Figure 5 ).
2. Hie rays were deflected away from
a negatively charged object.

These observations led to the

hypothesis that the particles that
compose cathode rays are negatively
charged. This hypothesis was strongly
supported bv a series of experiments
carried out in 1897 by the English physicist Joseph John Thomson. In FIGURE 5 A magnet near the
one investigation, he was able to measure the ratio of the charge of cathode-ray tube causes the beam to
cathode - ray particles to their mass. He found that this ratio was always be deflected. The deflection indi -
the same, regardless of the metal used to make the cathode or the cates that the particles in the beam

nature of the gas inside the cathode - ray tube. Thomson concluded that have a negative charge.
all cathode rays are composed of identical negatively charged particles,
which were named electrons.

Charge and Mass of the Electron

CHEMISTRY
*I
Thomson’s experiment revealed that the electron has a very large charge-
to-mass ratio. Because cathode rays have identical properties regardless
of the element used to produce them, it was concluded that electrons are Module 2: Models of the Atom
present in atoms of all elements. Thus, cathode-ray experiments provided
evidence that atoms are divisible and that one of the atom's basic con-
stituents is the negatively charged electron. In 1909. experiments con-
ducted by the American physicist Robert A . Millikan measured the
charge of the electron. Scientists used this information and the charge- to-
mass ratio of the electron to determine that the mass of the electron is
about one two- thousandth the mass of the simplest type of hydrogen
atom, which is the smallest atom known. More -accurate experiments con -
ducted since then indicate that the electron has a mass of 9.109 x 10 kg.
or 1 / 1837 the mass of the simplest type of hydrogen atom.
Based on what was learned about electrons, two other inferences
were made about atomic structure.
1. Because atoms are electrically neutral, they must contain a positive
charge to balance the negative electrons.
2. Because electrons have so much less mass than atoms, atoms must
contain other particles that account for most of their mass. Develop d Md nwnUiaed by die
'
HJIMMUI SdtM feather Auwulioa
*
Thomson proposed a model for the atom that is called the plum pudding For a variety of links related to this
model ( after the English dessert ). He believed that the negative electrons chapter, go to www.scilinks.org
were spread evenly throughout the positive charge of the rest of the atom.
This arrangement is similar to that of seeds in a watermelon: the seeds are
Topic: Subatomic Particles
SciLinks code: HC61473
^
spread throughout the fruit but do not contribute much to the overall
mass. However, shortly thereafter, new experiments disproved this model.

ATOMS: THE BUILDING BLOCKS OF MATTER 73

 Discovery of the Atomic Nucleus
More detail of the atom's structure was provided in 1911 by New
Zealander Ernest Rutherford and his associates Hans Geiger and
Ernest Marsden. The scientists bombarded a thin piece of gold foil with
fast -moving alpha panicles, which are positively charged particles with
about four times the mass of a hydrogen atom. Geiger and Marsden
assumed that mass and charge were uniformly distributed throughout
the atoms of the gold foil. They expected the alpha particles to pass
through with only a slight deflection, and for the vast majority of the
particles, this was the case. 1 lowever. when the scientists checked for the
possibility of wide-angle deflections, they were shocked to find that
roughly 1 in 8000 of the alpha particles had actually been deflected back
toward the source ( see Figure 6 ). As Rutherford later exclaimed, it was
“ as if you had fired a 15-inch [ artillery ] shell at a piece of tissue paper
and it came back and hit you."
After thinking about the startling result for a few months,
Rutherford finally came up with an explanation. He reasoned that the
deflected alpha particles must have experienced some powerful force
within the atom. And he figured that the source of this force must occu -
py a very small amount of space because so few of the total number of
alpha particles had been affected by it. He concluded that the force
must be caused by a very densely packed bundle of matter with a pos -
itive electric charge. Rutherford called this positive bundle of matter
the nucleus ( see Figure 7 ).
Rutherford had discovered that the volume of a nucleus was very
small compared with the total volume of an atom. In fact, if the nucleus
were the size of a marble, then the size of the atom would be about the
size of a football field. But where were the electrons? Tliis question was
not answered until Rutherford's student, Niels Bohr, proposed a model
FIGURE 6 ( a ) Geiger and in which electrons surrounded the positively charged nucleus as the
Marsden bombarded a thin piece
planets surround the sun. Bohr 's model will be discussed in Chapter 4.
of gold foil with a narrow beam
of alpha particles, ( b ) Some of the
particles were deflected by the
gold foil back toward their source.
Screen to detect
deflected
particles

- Thin gold
foil

W — Lead box containing radioactive

source of fast-moving particles

(a) (b)

74 CHAPTER 3
 Small deflection
X

Beam of
Electrons surround
positive (
nucleus
particles Nucleus

Large deflection

FIGURE 7 Rutherford reasoned

that each atom in the gold
foil contained a small, dense, posi -
Composition of the Atomic Nucleus tively charged nucleus surrounded
by electrons. A small number of the
Except for the nucleus of the simplest type of hydrogen atom ( discussed alpha particles directed toward the
in the next section ), all atomic nuclei are made of two kinds of particles, foil were deflected by the tiny nu-
protons and neutrons. A proton has a positive charge equal in magni - cleus ( red arrows ). Most of the parti -
tude to the negative charge of an electron. Atoms are electrically neu - cles passed through undisturbed
tral because they contain equal numbers of protons and electrons. A ( black arrows ).
neutron is electrically neutral.
The simplest hydrogen atom consists of a single-proton nucleus with a
single electron moving about it. A proton has a mass of 1.673 x 10 2 ? kg.
'

which is 1836 times greater than the mass of an electron and 1836/ 1837.
.
or virtually all of the mass of the simplest hydrogen atom. All atoms
besides the simplest hydrogen atom also have neutrons. The mass of a
neutron is 1.675 x Hr 2 kg—slightly larger than that of a proton.
The nuclei of atoms of different elements differ in their number of
protons and therefore in the amount of positive charge they possess.
Tlius. the number of protons determines that atom s identity. Physicists
have identified other subatomic particles, but particles other than elec -
trons. protons, and neutrons have little effect on the chemical properties
of matter. Table 1 on the next page summarizes the properties of elec -
trons. protons, and neutrons.

Forces in the Nucleus

Generally, particles that have the same electric charge repel one another.
Therefore, we would expect a nucleus with more than one proton to
be unstable. However, when two protons are extremely close to each
other, there is a strong attraction between them. In fact, more than 100

ATOMS: THE BUILDING BLOCKS OF MATTER 75

 TABLE 1 Properties of Subatomic Particles
Relative
electric Mass Relative mass Actual mass
Particle Symbols charge number (amu * ) ( kg)
Electron -1 0 0.000 5486 9.109 x 10~M
Proton p\ \ H +1 1 l.007 276 1.673 x 10-27
Neutron n°.In 0 1 1.008 665 1.675 x l(r 27
’ l amu ( atomic mass unit ) = 1.660540 x 10-27 kg
“

protons can exist close together to help form a nucleus. A similar attrac -
tion exists when neutrons are very close to each other or when protons
and neutrons are very close together. These short - range proton-neutron,
.
proton - proton and neutron - neutron forces hold the nuclear particles
together and are referred to as nuclear forces .

The Sizes of Atoms

It is convenient to think of the region occupied by the electrons as an
electron cloud— a cloud of negative charge.The radius of an atom is the
distance from the center of the nucleus to the outer portion of this elec -
tron cloud. Because atomic radii are so small, they are expressed using
a unit that is more convenient for the sizes of atoms. This unit is the
picometer. The abbreviation for the picometer is pm ( 1 pm = UP 12 m =
l (Tln cm ). To get an idea of how small a picometer is. consider that 1 cm
is the same fractional part of HP km ( about 600 mi ) as 100 pm is of 1 cm.
Atomic radii range from about 40 to 270 pm. By contrast, the nuclei of
.
atoms have much smaller radii, about 0.001 pm Nuclei also have incred -
ibly high densities, about 2 x 10s metric tons/cm3.

SECTION REVIEW 3. Compare the three subatomic particles in terms of

.
1 Define each of the following: location in the atom, mass, and relative charge.
a. atom c. nucleus e. neutron 4. Why is the cathode-ray tube in Figure 4 connect-
ed to a vacuum pump ?
b. electron d. proton
2. Describe one conclusion made by each of the fol- Critical Thinking
lowing scientists that led to the development of 5. EVALUATING IDEAS Nuclear forces are said to
the current atomic theory: hold protons and neutrons together. What is it
a. Thomson b. Millikan c. Rutherford about the composition of the nucleus that requires
the concept of nuclear forces?

76 CHAPTER 1
 SECTION 3
Counting Atoms
OBJECTIVES
SJ Explain what isotopes are.
C onsider neon. Ne. the gas used in many illuminated signs. Neon is a
minor component of the atmosphere. In fact , dry air contains only about
^ Define atomic number and
’
0.002 % neon. And yet there are about 5 x 10 atoms of neon present in
each breath you inhale. In most experiments, atoms are much too small
mass number; and describe
how they apply to isotopes.
to be measured individually. Chemists can analyze atoms quantitatively,
however, by knowing fundamental properties of the atoms of each ele-
ment . In this section, you will be introduced to some of the basic prop- u Given the identity of a nuclide,
erties of atoms. You will then discover how to use this information to determine its number of pro-
tons, neutrons, and electrons.
count the number of atoms of an element in a sample with a known
mass. You will also become familiar with the mole, a special unit used by
chemists to express amounts of particles, such as atoms and molecules. ^ Define mole, Avogadros num -
ber, and molar mass, and state
how all three are related.

Atomic Number ^ Solve problems involving

mass in grams, amount in
All atoms are composed of the same basic particles. Yet all atoms are moles, and number of atoms
not the same. Atoms of different elements have different numbers of of an element.
protons. Atoms of the same element all have the same number of pro-
tons. The atomic number ( Z ) of an element is the number of protons of
each mom of that element.
Turn to the inside back cover of this textbook. In the periodic table
shown, an element 's atomic number is indicated above its symbol. Notice
that the elements are placed in order of increasing atomic number. At
the top left of the table is hydrogen, H. which has atomic number 1 . All
atoms of the element hydrogen have one proton. Next in order is heli -
.
um He, which has two protons. Lithium, Li, has three protons ( see
Figure S ); beryllium. Be, has four protons: and so on.
The atomic number identifies an element. If vou want to know which 3
element has atomic number 47, for example, look at the periodic table.
You can see that the element is silver. Ag. All silver atoms have 47 pro - Li
tons. Because atoms are neutral, we know from the atomic number that Lithium
all silver atoms must also have 47 electrons. 6.941
’
[ He ] 2s

FIGURE 8 The atomic number in

Isotopes this periodic table entry reveals that
an atom of lithium has three protons
The simplest atoms are those of hydrogen. All hydrogen atoms have in its nucleus.
.
only one proton However, like many naturally occurring elements,
hydrogen atoms can have different numbers of neutrons.

ATOMS: THE BUILDING BLOCKS OF M ATTE R 77

 1 Neutron 2 Neutrons

1 Proton 1 Proton 1 Proton

Protium Deuterium Tritium

FIGURE 9 The nuclei of different

isotopes of the same element have
rhree types of hydrogen atoms are known. The most common type
the same number of protons but dif -
of hydrogen is sometimes called protium. It accounts for 99.9885 % of
ferent numbers of neutrons. This is
illustrated above by the three the hydrogen atoms found on Earth. The nucleus of a protium atom
isotopes of hydrogen. consists of one proton only, and it has one electron moving about it.
There are two other known forms of hydrogen. One is called deuterium,
which accounts for 0.0115 % of Earth's hydrogen atoms. Each deuteri-
um atom has a nucleus with one proton and one neutron. The third form
of hydrogen is known as tritium which is radioactive. It exists in very
small amounts in nature, but ii can be prepared artificially. Each tritium
atom has one proton, two neutrons, and one electron.
Protium. deuterium and tritium are isotopes of hydrogen. Isotopes
,

tire atoms of the same element that have different masses. The isotopes of
a particular element all have the same number of protons and electrons
but different numbers of neutrons. In all three isotopes of hydrogen, the
positive charge of the single proton is balanced bv the negative charge
of the electron. Most of the elements consist of mixtures of isotopes. Tin
has 11) stable isotopes, for example, the most of any element .

Mass Number
Identifying an isotope requires knowing both the name or atomic num -
ber of the element and the mass of the isotope. The mass number is the
total number of protons and neutrons that make up the nucleus of an iso-
tope. The three isotopes of hydrogen described earlier have mass num -
.
bers 1 , 2. and 3 as shown in Table 2 .

TABLE 2 Mass Numbers of Hydrogen Isotopes

Atomic number
(number of Number of Mass number
protons) neutrons (protons + neutrons)
Protium 1 0 1 +0= 1
Deuterium 1 1 1+ 1=2
Tritium 1 2 1 + 2=3

78 CHAPTER 3
 Designating Isotopes SC
//N/CS. iM r *
DmfcM auMUtoH by IIK
NjboMl ScWncc Tejcbcn ASMCUUON
The isotopes of hydrogen are unusual in that they have distinct names.
For a variety of links related to this
Isotopes are usually identified by specifying their mass number. There chapter, go to .7ww. sc 1links.org I
are two methods for specifying isotopes. In the first method, the mass
number is written with a hyphen after the name of the element. Tritium,
Topic: Isotopes
Sci Links code: HC60820
^
)
.
for example, is written as hydrogen -3 We will refer to this method as
hyphen notation. The uranium isotope used as fuel for nuclear power
plants has a mass number of 235 and is therefore known as uranium-
235. The second method shows the composition of a nucleus as the iso -
tope 's nuclear symbol . For example, uranium -235 is w ritten as U. The
^
superscript indicates the mass number and the subscript indicates the
atomic number. The number of neutrons is found by subtracting the
atomic number from the mass number.

mass number - atomic number = number of neutrons

235 ( protons + neutrons) - 92 protons = 143 neutrons

Thus, a uranium-235 nucleus is made up of 92 protons and 143 neutrons.

Table 3 gives the names, symbols, and compositions of the isotopes of
hydrogen and helium. Nuclide is a general term for a specific isotope of
an element . We could say that Table 3 lists the compositions of five dif -
ferent nuclides, three hydrogen nuclides and two helium nuclides.

TABLE 3 Isotopes of Hydrogen and Helium

Nuclear Number of Number of Number of
Isotope symbol protons electrons neutrons
Hydrogen- 1 ( protium ) !H I l o
1 lydrogen - 2 ( deuterium ) ?i H 1 1 I
Hydrogen-3 ( tritium ) iH I 2
Helium -3 jHe 2 2 1
Helium-4 ] Hc ? 2 2

SAMPLE PROBLEM A
How many protons, electrons, and neutrons are there in an atom of chlorine-37?

SOLUTION
1 ANALYZE Given: name and mass number of chlorine-37
Unknown: numbers of protons, electrons, and neutrons

2 PLAN atomic number = number of protons = number of electrons

mass number = number of neutrons + number of protons

ATOMS: THE BUILDING BLOCKS OF MATTER 79

3 COMPUTE The mass number of chlorine-37 is 37. Consulting the periodic table reveals that chlorine's
atomic number is 17. The number of neutrons can be found by subtracting the atomic
number from the mass number.

mass number of chlorine-37 - atomic number of chlorine =

number of neutrons in chlorine-37

mass number - atomic number - 37 (protons plus neutrons ) - 17 protons

= 20 neutrons

An atom of chlorine-37 is made up of 17 electrons. 17 protons, and 20 neutrons .

4 EVALUATE The number of protons in a neutral atom equals the number of electrons. And the sum
of the protons and neutrons equals the given mass number.

PRACTICE Answers in Appendix E

1 . How many protons, electrons, and neutrons make up an atom of

bromine-80?
Go to go.hrw.com for
2 . Write the nuclear symbol for carbon 13. - more practice problems
3. Write the hyphen notation for the isotope with 15 electrons and that ask you to work
15 neutrons. with numbers of
subatomic particles.
Keyword: HC 6 ATMX

Relative Atomic Masses

.
Masses of atoms expressed in grams are very small As we shall see,
an atom of oxygen-16, for example, has a mass of 2.656 x 10 23 g. For
most chemical calculations it is more convenient to use relative atomic
masses. As you read in Chapter 2. scientists use standards of measure-
ment that are constant and are the same everywhere. In order to set up
a relative scale of atomic mass, one atom has been arbitrarily chosen as
the standard and assigned a relative mass value. The masses of all other
atoms are expressed in relation to this defined standard .
Hie standard used by scientists to compare units of atomic mass is the
carbon-12 atom. It has been arbitrarily assigned a mass of exactly 12 atom-
ic mass units, or 12 amu. One atomic mass unit, or I amu, is exactly 1/ 12 the
mass of a carbon - 12 atom. The atomic mass of any atom is determined bv
comparing it with the mass of the carbon- 12 atom. The hydrogen-1 atom
has an atomic mass of about 1 / 12 that of the carbon- 12 atom, or about
1 amu. The precise value of the atomic mass of a hydrogen - 1 atom is
1.007 825 amu An oxygen-16 atom has about 16/ 12 ( or 4/3) the mass of
a carbon- 12 atom. Careful measurements show the atomic mass of
oxygen-16 to be 15.994 915 amu. The mass of a magnesium-24 atom is
found to be slightly less than twice that of a carbon- 12 atom. Its atomic
mass is 23.985 042 amu.

80 CHAPTER 3
 Some additional examples of the atomic masses of the naturally
occurring isotopes of several elements are given in Table 4 on the next
page. Isotopes of an element may occur naturally, or they may be made
in the laboratory ( artificial isotopes ). Although isotopes have different
musses, they do not differ significantly in their chemical behavior .
The masses of subatomic particles can also be expressed on the atom -
ic mass scale ( see Table l). The mass of the electron is 0.000 5486 amu, HISTORICAL
that of the proton is 1.007 276 amu. and that of the neutron is CHEMISTRY
1.008 665 amu. Note that the proton and neutron masses are close to but
not equal to 1 amu. You have learned that the mass number is the total Discovery of Element 43
I
number of protons and neutrons that make up the nucleus of an atom.
The discovery of element 43, tech-
You can now see that the mass number and relative atomic mass of a netium, is credited to Carlo Perrier and
given nuclide are quite close to each other. They are not identical Emilio Segre, who artificially produced
because the proton and neutron masses deviate slightly from 1 amu and it in 1937. However, in 1925, a German
the atomic masses include electrons. Also, as you will read in Chapter 21 T
chemist named Ida Tacke reported the
a small amount of mass is changed to energy in the creation of a nucleus discovery of element 43, which she
called masurium, in niobium ores. At
from its protons and neutrons. the time, her discovery was not accept -
ed because it was thought technetium
could not occur naturally. Recent stud-
ies confirm that Tacke and coworkers
probably did discover element 43.
Average Atomic Masses of Elements
Most elements occur naturally as mixtures of isotopes, as indicated in
.
Table 4 The percentage of each isotope in the naturally occurring ele -
ment on Earth is nearly always the same, no matter where the element
is found. The percentage at which each of an element 's isotopes occurs
in nature is taken into account when calculating the element 's average
atomic mass. Average atomic mass is the weighted average of the atom -
ic masses of the naturally occurring isotopes of an element.
The following is a simple example of how to calculate a weighted
average. Suppose you have a box containing two sizes of marbles. If
25 % of the marbles have masses of 2.00 g each and 75 % have masses of
3.00 g each, how is the weighted average calculated? You could count
the number of each type of marble, calculate the total mass of the mix -
ture. and divide bv the total number of marbles. If you had 100 marbles,
the calculations would be as follows.
25 marbles x 2.00 g = 50 g
75 marbles x 3.00 g = 225 g
Adding these masses gives the total mass of the marbles.
50 g + 225 g = 275 g
Dividing the total mass by 100 gives an average marble mass of 2.75 g.
A simpler method is to multiply the mass of each marble by the dec -
imal fraction representing its percentage in the mixture. Then add the
products.
25 % = 0.25 75 % = 0.75
( 2.00 g x 0.25 ) + (3.00 g x 0.75) = 2.75 g

ATOMS: THE BUILDING BLOCKS OF M ATTE R 81

 TABLE 4 Atomic Masses and Abundances of Several Naturally Occurring Isotopes
Average
Mass Percentage natural Atomic mass atomic mass
Isotope number abundance (amu) of element ( amu)
Hydrogen- 1 1 99.9885 L.007825 1.007 94
Hydrogen-2 2 0.0115 2.014 102
Carbon- 12 12 98.93 12 ( by definition)
Carbon- 13 13 1.07 13,003 355 12.0107
Oxygen- 16 16 99.757 15.994915
Oxygen- 17 17 0.038 16.999 132 15.9994
Oxygen - 18 18 0.205 17.999 160
Copper-63 63 69.15 62.929 601
63.546
Copper-65 65 30.85 64.927 794
Cesium-133 133 100 132.905 447 132.905
Uranium-234 234 0.0054 234.040 945
-
Uranium 235 235 0.7204 235.043 922 238.029
Uranium-238 238 99.2742 238.050 784

Calculating Average Atomic Mass

The average atomic mass of an element depends on both the mass and
the relative abundance of each of the element s isotopes. For example,
naturally occurring copper consists of 69.15 % copper-63, which has an
atomic mass of 62.929 601 amu, and 30.85 % copper-65, which has an
atomic mass of 64.927 794 amu. The average atomic mass of copper can
be calculated by multiplying the atomic mass of each isotope by its rel -
ative abundance (expressed in decimal form ) and adding the results.
0.6915 x 62.929 601 amu + 0.3085 x 64.927 794 amu = 63.55 amu
The calculated average atomic mass of naturally occurring copper is
63.55 amu.
The average atomic mass is included for the elements listed in
Table 4. As illustrated in the table, most atomic masses are known to
four or more significant figures. In this book , an element 's atomic mass is
usually rounded to two decimal places before it is used in a calculation.

Relating Mass to Numbers of Atoms

The relative atomic mass scale makes it possible to know how many
atoms of an element are present in a sample of the element with a mea -
.
surable mass Three very important concepts the mole. Avogadro s
—
—
number, and molar mass provide the basis for relating masses in
grams to numbers of atoms.

82 CHAPTER 3
The Mole
The mole is the SI unit for amount of substance. A mole ( abbreviated
mol ) is the amount of a substance that contains as many particles as
there are atoms in exactly 12 g of carbon - 12. The mole is a counting
unit , just like a dozen is. We don ’ t usually order 12 or 24 ears of corn :
we order one dozen or two dozen . Similarly, a chemist may want 1 mol
of carbon , or 2 mol of iron , or 2.567 mol of calcium . In the sections that
follow, you will see how the mole relates to masses of atoms and
compounds.

Avogadro 's Number

The number of particles in a mole has been experimentally deter -
mined in a number of ways. The best modern value is 6.022 1415 x
10 “ \ This means that exactly 12 g of carbon - 12 contains 6.022 1415 x
1023 carbon - 12 atoms. The number of particles in a mole is known as
Avogadro's number , named for the nineteenth -century Italian scien -
tist Amedeo Avogadro, whose ideas were crucial in explaining the
relationship between mass and numbers of atoms. Avogadro’s num- (a )
—
ber—6.022 Ml 5 x 1023 is the number of particles in exactly one mole
of a pure substance. For most purposes. Avogadro's number is round -
ed to 6.022 x 1023.
To get a sense of how large Avogadro 's number is. consider the fol -
lowing: If every person living on Earth ( 6 billion people ) worked to
count the atoms in one mole of an element , and if each person counted
continuously at a rate of one atom per second , it would lake about
3 million vears for all the atoms to be counted .

Molar Mass
An alternative definition of mole is the amount of a substance that con -
tains Avogadro's number of particles. Can you figure out the approxi - ( b)
mate mass of one mole of helium atoms? You know that a mole of
carbon -12 atoms has a mass of exactly 12 g and that a carbon- 12 atom
has an atomic mass of 12 amu. The atomic mass of a helium atom is
-
4.00 amu , which is about one third the mass of a carbon - 12 atom . It fol -
lows that a mole of helium atoms will have about one-third the mass of
a mole of carbon - 12 atoms. Thus, one mole of helium has a mass of
about 4.00 g.
The mass of one mole of a pure substance is called the molar mass of
that substance. Molar mass is usually written in units of g/ mol. The molar
mass of an element is numerically equal to the atomic mass of the ele -
ment in atomic mass units ( which can be found in the periodic table ). For
example, the molar mass of lithium . Li . is 6.94 g/mol, while the molar
mass of mercury. Hg. is 200.59 g/mol ( rounding each value to two deci - (c )
mal places ).
FIGURE 10 Shown is approxi -
The molar mass of an element contains one mole of atoms. For exam -
mately one molar mass of each
ple, 4.00 g of helium. 6.94 g of lithium , and 200.59 g of mercury all con - of three elements: ( a ) carbon
tain a mole of atoms. Figure 10 shows molar masses of three common ( graphite ), ( b ) iron ( nails), and
elements. ( c ) copper ( wire ).

ATOMS: THE BUILDING BLOCKS OF MATTER 83

 molar mass 1 mol
- of element x x
1 mol Amount 6.022 x 10" atoms
of element
Mass of element . mol
x molar mass
in moles
x
6.022 x 10" atoms _ Number of atoms
in grams 1 mol of element
of element

FIGURE 11 The diagram shows

the relationship between mass in
grams, amount in moles, and number Gram / Mole Conversions
of atoms of an element in a sample.
Chemists use molar mass as a conversion factor in chemical calcula -
tions. For example, the molar mass of helium is 4.00 g He / mol He. To
find how many grams of helium there are in two moles of helium , mul -
tiply by the molar mass.

4.00 g He
2.00 mol He x = 8.00 g He
l mol He

Figure 11 shows how to use molar mass, moles, and Avogadro's number
to relate mass in grams, amount in moles, and number of atoms of an
element .

SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter.
What is the mass in grams of 3.50 mol of the element copper, Cu?

SOLUTION
1 ANALYZE Given: 3.50 mol Cu
Unknown: mass of Cu in grams

2 PLAN amount of Cu in moles > mass of Cu in grams

According to Figure 11, the mass of an element in grams can be calculated by multiplying
the amount of the element in moles by the element 's molar mass.

grams Cu
moles Cu x
moles Cu
= grams Cu

3 COMPUTE The molar mass of copper from the periodic table is rounded to 63.55 g/ mol.

63.55 g Cu
3.50 moF-Cu x
1 mol Cu
= 222 g Cu

4 EVALUATE Because the amount of copper in moles was given to three significant figures, the answer
was rounded to three significant figures. ITie size of the answer is reasonable because it is
somewhat more than 3.5 times 60.

84 CHAPTER 3
 PRACTICE Answers in Appendix E

1. What is the mass in grams of 2.25 mol of the element iron. Fe?
2. What is the mass in grams of 0375 mol of the element potassium. K ? Go to go.hrw.com for
more practice problems
3. What is the mass in grams of 0.0135 mol of the element sodium, Na? that ask you to convert
4. What is the mass in grams of 16.3 mol of the element nickel, Ni? from amount in moles
to mass.

Keyword: HC 6 ATMX

SAMPLE PROBLEM C For more help, go to the Math tutor at the end of this chapter.

A chemist produced 11.9 g of aluminum, Al. How many moles of aluminum were produced?

SOLUTION
1 ANALYZE Given: l l.9 g A l
Unknown: amount of Al in moles

2 PLAN mass of Al in grams > amount of Al in moles

As shown in Figure 11, amount in moles can he obtained by dividing mass in grams by
molar mass, which is mathematically the same as multiplying mass in grams by the reciprocal
of molar mass.

moles AI
grams Al x = moles Al
grams Al

3 COMPUTE Hie molar mass of aluminum from the periodic table is rounded to 26.98 g/mol.

I mol Al
11.9
^ Aix 26.98 g-Af = 0.441 mol Al
-

4 EVALUATE The answer is correctly given to three significant figures. The answer is reasonable because
11.9 g is somewhat less than half of 26.98 g.

PRACTICE Answers in Appendix E

1. How many moles of calcium. Ca. are in 5.00 g of calcium? Go to go.hrw.com for
more practice problems
2. How many moles of gold. Au. are in 3.60 x 10 '' g of gold?
"

that ask you to convert

3. How many moles of zinc, Zn, are in 0.535 g of zinc ? from mass to amount in
moles.
Keyword: HC 6 ATMX

ATOMS: THE BUILDING BLOCKS OF MATTER 85

 Conversions with Avogadro 's Number
Figure 11 shows that Avogadro's number can be used to find the num-
ber of atoms of an element from the amount in moles or to find the
amount of an element in moles from the number of atoms. While these
types of problems are less common in chemistry than converting
between amount in moles and mass in grams, they are useful in demon-
strating the meaning of Avogadro's number. Note that in these calcula-
tions, Avogadro's number is expressed in units of atoms per mole.

SAMPLE PROBLEM » For more help, go to the Math Tutor at the end of this chapter.

How many moles of silver, Ag, are in 3.01 x 1023 atoms of silver ?

SOLUTION
1 ANALYZE Given: 3.01 x 1 ( ) 2 ' atoms of Ag
Unknown: amount of Ag in moles

2 PLAN number of atoms of Ag amount of Ag in moles

From Figure ll, we know that number of atoms is converted to amount in moles by
dividing by Avogadro's number. This is equivalent to multiplying numbers of atoms
by the reciprocal of Avogadro's number.
moles Ag
Ag atoms x = moles Ag
Avogadro's number of Ag atoms

I mol Ag
3 3.01 x 1022 / g- atoms x = 0.500 mol Ag
COMPUTE
^ * ^g-atoms
6.022 x 10 /

4 EVALUATE The answer is correct —units cancel correctlv and the number of atoms is one-half of
Avogadro 's number.

PRACTICE Answers in Appendix E

1 . How many moles of lead, Pb, are in 1.50 x 1012 atoms of lead? Go to go.hrw.com for
more practice problems
2. How many moles of tin, Sn, are in 2500 atoms of tin ?
that ask you to convert
.
3. I low many atoms of aluminum Al. are in 2.75 mol of aluminum ? between atoms and
moles.
Keyword: HC 6 ATMX

SAMPLE PROBLEM E For more help, go to the Math Tutor at the end of this chapter.

What is the mass in grams of 1.20 x 10s atoms of copper, Cu ?

SOLUTION
1 ANALYZE *
Given: 1.20 x 10 atoms of Cu
Unknown: mass of Cu in grams

86 CHAPTER 3
 » mass of Cu in grams
2 PLAN number of atoms of Cu
* amount of Cu in moles
As indicated in Figure 11, the given number of atoms must first be converted to amount in
moles by dividing by Avogadro’s number. Amount in moles is then multiplied by molar
mass to yield mass in grams.

moles Cu grams Cu
Cu atoms x x = grams Cu
Avogadros number of Cu atoms moles Cu

3 COMPUTE The molar mass of copper from the periodic table is rounded to 63.55 g/mol.

1 mol Cu 63.55 n Cu
1.20 x 10s Cu atoms x x = 1.27 x 1 ()
' 14
g Cu
6.022 x 1023 Customs l nw »10i

4 EVALUATE Units cancel correctly to give the answer in grams. The si /e of the answer is reasonable —
10s has been divided by about 10:4 and multiplied by about 10 . “

PRACTICE Answers in Appendix E

1. What is the mass in grams of 7.5 x U ) > atoms of nickel. Ni ?

]
TETftd iTftdTl
2. How many atoms of sulfur, S. are in 4.00 g of sulfur ? Go to go.hrw.com for
more practice problems
3. What mass of gold. Au. contains the same number of atoms as that ask you to convert
9.0 g of aluminum. Al? among atoms, grams,
and moles.
Keyword: HC 6 ATMX

SECTION REVIEW 4. To two decimal places, what is the relative atomic

1. Define each of the following: mass and the molar mass of the element potas -
sium, K ?
a. atomic number e. mole
5. Determine the mass in grams of the following:
b. mass number f. Avogadro's number
a. 2.00 mol N
c. relative atomic mass g. molar mass
b. 3.01 x 1023 atoms Cl
d. average atomic mass h. isotope
2. Determine the number of protons, electrons, and
.
6 Determine the amount in moles of the following:

neutrons in each of the following isotopes: a. 12.15 g Mg

a. sodium-23 .
C 29CU
b. 1.50 x 1023 atoms F
b. calcium- 40
'
d. S87Ag
3. Write the nuclear symbol and hyphen notation for
Critical Thinking
7. ANALYZING DATA Beaker A contains 2.06 mol of
each of the following isotopes: copper, and Beaker B contains 222 grams of silver.
a. mass number of 28 and atomic number of 14 Which beaker contains the larger mass ? Which
beaker has the larger number of atoms ?
b. 26 protons and 30 neutrons

ATOMS: THE BUILDING BLOCKS OF MATTER 87

 CHAPTER HIGHLIGHTS
The Atom: From Philosophical Idea to Scientific Theory
I Vocabulary •The idea of atoms has been around since the time of the
law of conservation of mass ancient Greeks. In the nineteenth century. John Dalton pro-
law of definite proportions posed a scientific theory of atoms that can still be used to
law of multiple proportions explain properties of most chemicals today.
•Matter and its mass cannot be created or destroyed in chemi-
cal reactions.
•The mass ratios of the elements that make up a given com -
pound are always the same, regardless of how much of the
compound there is or how it was formed.
•If two or more different compounds are composed of the same
two elements, then the ratio of the masses of the second el-
ement combined with a certain mass of the first element can
be expressed as a ratio of small whole numbers.

The Structure of the Atom

I Vocabulary •Cathode-ray tubes supplied evidence of the existence of elec-
atom trons. which are negatively charged subatomic particles that
nuclear forces have relatively little mass.
•Rutherford found evidence for the existence of the atomic
nucleus by bombarding metal foil with a beam of positively
charged particles.
•Atomic nuclei are composed of protons, which have an electric
charge of + 1. and ( in all but one case ) neutrons, which have no
electric charge.
• Atomic nuclei have radii of about 0.001 pm ( pm = picometers;
I pm x 10 12 m ), and atoms have radii of about 40-270 pm.
'

Counting Atoms
I Vocabulary The atomic number of an element is equal to the number of
atomic number protons of an atom of that element.
isotope The mass number is equal to the total number of protons and
mass number neutrons that make up the nucleus of an atom of that element .
nuclide The relative atomic mass unit (amu) is based on the carbon - 12
atomic mass unit atom and is a convenient unit for measuring the mass of atoms.
average atomic mass It equals 1.660 540 x 10~24 g.
mole The average atomic mass of an element is found by calculating
Avogadro's number the weighted average of the atomic masses of the naturally
molar mass occurring isotopes of the element.
Avogadro’s number is equal to approximately 6.022 1415 x 102 \
A sample that contains a number of particles equal to
Avogadro's number contains a mole of those particles.

88 CHAPTER 3
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D .

The Atom: From Philosophical 9. a. What is the atomic number of an element ?

b. What is the mass number of an isotope ?
Idea to Scientific Theory c. In the nuclear symbol for deuterium . yH .
SECTION 1 REVIEW identify the atomic number and the mass
number.
1 . Explain each of the following in terms of
10. What is a nuclide?
Dalton 's atomic theory:
11. Use the periodic table and the information that
a. the law of conservation of mass
follows to write the hyphen notation for each
b. the law of definite proportions
isotope described.
c. the law of multiple proportions
a. atomic number = 2. mass number = 4
2 . According to the law of conservation of mass, if
b. atomic number = K. mass number = 16
element A has an atomic mass of 2 mass units
c. atomic number = 19. mass number = 39
and element B has an atomic mass of 3 mass 12. a. What nuclide is used as the standard in the
units, what mass would be expected for com -
relative scale for atomic masses?
pound AB? for compound A:B /?
b. What is its assigned atomic mass?
13. What is the atomic mass of an atom if its mass is
The Structure of the Atom approximately equal to the following ?

SECTION 2 REVIEW
3. a . What is an atom ?
^
a . that of carbon - 12
b. 4.5 times as much as carbon - 12
14. a. What is the definition of a mole !
b. What two regions make up all atoms? b. What is the abbreviation for motel
4 . Describe at least four properties of electrons c. How many particles are in one mole?
that were determined based on the experiments d . What name is given to the number of parti -
of Thomson and Millikan . cles in a mole ?
5 . Summarize Rutherford s model of the atom and,
15. a. What is the molar mass of an element ?
explain how he developed this model based on b. To two decimal places, write the molar mass-
the results of his famous gold -foil experiment . es of carbon , neon. iron , and uranium .
6. What number uniquely identifies an element ? 16. Suppose you have a sample of an element .
a . How is the mass in grams of the element
converted to amount in moles?
Counting Atoms b. I low is the mass in grams of the element
converted to number of atoms?
SECTION 3 REVIEW
7 . a . What are isotopes?
PRACTICE PROBLEMS
b. How are the isotopes of a particular element
17. What is the mass in grams of each of the follow-
alike?
ing? ( Hint: See Sample Problems B and E . )
c. How are they different ?
8. C opy and complete the following table concern - a . l .OO mol Li d . l .OO molar mass Fe
ing the three isotopes of silicon . Si .
b. 1.00 mol Al e. 6.022 x 1023 atoms C
( Hint : See Sample Problem A . )
c. 1.00 molar mass Ca f. 6.022 x 102 > atoms Ag
18. How many moles of atoms are there in each of
Number Number of Number of the following? ( Hint : See Sample Problems C
Isotope of protons electrons neutrons and D. )
a . 6.022 x 1023 atoms Ne c. 3.25 x 1 (T g Pb
Si - 28
Si -29
,
b. 3.011 x 102 ' atoms Mg d . 4.50 x l (r 2 g O
Si - 30

ATOMS: THE BUILDING BLOCKS OF MATTER 89

 CHAPTER REVIEW

—
19. Three isotopes of argon occur in nature i Ar, 25 . Copy and complete the following table concern-
$Ar. and j* Ar. Calculate the average atomic
*
* ing the properties of subatomic particles.
mass of argon to two decimal places, given the
Mass Actual Relative
following relative atomic masses and abun- charge
Particle Symbol number mass
dances of each of the isotopes: argon-36
( 35.97 a mu: 0.337% ), argon-38 ( 37.96 amu: Electron
0.063% ). and argon- 40 ( 39.96 amu: 99.600% ). Proton
20. Naturally occurring boron is 80.20% boron- 11 Neutron
( atomic mass = 11.01 amu ) and 19.80% of some
other isotopic form of boron. What must the 26. a. How is an atomic mass unit ( amu) related to
atomic mass of this second isotope be in order the mass of one carbon- 12 atom?
to account for the 10.81 amu average atomic b. What is the relative atomic mass of an atom?
mass of boron? ( Write the answer to two deci - 27 . a. What is the nucleus of an atom?
mal places.) b. Who is credited with the discovery of the
.
21 Ilow many atoms are there in each of the atomic nucleus?
following? c. Identify the two kinds of particles that make
.
a 1.50 mol Na c. 7.02 g Si up the nucleus.
b. 6.755 mol Pb 28. How main moles of atoms are there in each of
22. What is the mass in grams of each of the the following?
following? a. 40.1 g Ca e. 2.65 g Fe
a. 3.011 x If)2 ' atoms F e. 25 atoms W b. 11.5 g Na f. 0.007 50 g Ag
g. 2.25 x 102 atoms Zn
>
b. 1.50 x 10~ atoms Mg f. 1 atom Au c. 5.87 gNi
h. 50 atoms Ba
c. 4.50 x 1 ( )
,12 atoms Cl
d. 8.42 x I0 s atoms Br
d. 150 g S
29. State the law of multiple proportions, and give
23. Determine the number of atoms in each of the an example of two compounds that illustrate
following: the law.
a. 5.40 g B d. 0.025 50 g Pt 30. What is the approximate atomic mass of an
b. 0.250 mol S e. 1.00 x 10 111 g Au
*
atom if its mass is
c. 0.0384 mol k a. 12 times that of carbon- 12?
b. ~ that of carbon - 12?
31. What is an electron?
MIXED REVIEW
24. Determine the mass in grams of each of the CRITICAL THINKING
following:
a. 3.00 mol Al 32. Organizing Ideas Using two chemical com-
b. 2.56 x 1024 atoms Li pounds as an example, describe the difference
.
e 1.38 mol N between the law of definite proportions and the
d. 4.86 x 1024 atoms Au law of multiple proportions.
e. 6.50 mol Cu 33. Constructing Models As described in
f. 2.57 x 10* mol S Section 2. the structure of the atom was deter -
g. 1.05 x 10ls atoms Hg mined from observations made in painstaking
experimental research. Suppose a series of
experiments revealed that when an electric cur -
rent is passed through gas at low pressure, the
surface of the cathode-rav tube opposite the

90 CHAPTER 3
 CHAPTER REVIEW

anode glows. In addition, a paddle wheel placed ALTERNATIVE ASSESSMENT

in the tube rolls from the anode toward the
cathode when the current is on. 40. Observe a cathode-ray tube in operation, and
a. In which direction do particles pass through write a description of your observations.
the gas? 41. Performance Assessment Using colored clay,
b. What charge do the particles possess? build a model of the nucleus of each of carbon s
34. Analyzing Data Osmium is the element with three naturally occurring isotopes: carbon- 12.
the greatest density. 22.58 g/cm \ I low does the carbon- 13, and carbon- 14. Specify the number
density of osmium compare to the density of a of electrons that would surround each nucleus.
typical nucleus of 2 x 10s metric tons/cm3?
( I metric ton = 1000 kg)

— i v f l di i

USING THE HANDBOOK

35. Group 14 of the Elements Handbook describes
the reactions that produce CO and COi.
i Graphing Calculator Calculating Numbers
of Protons, Electrons, and Neutrons
Go to go.hrw.com for a graphing calculator
Review this section to answer the following: exercise that asks you to calculate numbers
of protons, electrons, and neutrons.
a. When a fuel burns, what determines whether
CO or COi will be produced? '1C Keyword: HC 6 ATMX
b. What happens in the body if hemoglobin
picks up CO?
c. Why is CO poisoning most likely to occur in
homes that are well sealed during cold winter
months?

RESEARCH & WRITING

36. Prepare a report on the series of experiments
conducted by Sir James Chadw ick that led to
the discovery of the neutron.
37 . Write a report on the contributions of Amedeo
Avogadro that led to the determination of the
value of Avogadro‘s number.
38. Trace the development of the electron micro -
scope. and cite some of its many uses.
39. The study of atomic structure and the nucleus
produced a new field of medicine called nuclear
medicine. Describe the use of radioactive
tracers to detect and treat diseases.

ATOMS: THE BUILDING BLOCKS OF MATTER 91

 Math Tutor CONVERSION FACTORS

Most calculations in chemistry require that all measurements of the same quantity
(mass, length, volume, temperature, and so on) be expressed in the same unit. To
change the units of a quantity, you can multiply the quantity by a conversion factor.
With SI units, such conversions are easy because units of the same quantity are related
by multiples of 10, 100, 1000, or 1 million. Suppose you want to convert a given
amount in milliliters to liters. You can use the relationship 1 L = 1000 mL. From this
relationship, you can derive the following conversion factors.
1000 mL 1L
and
1L 1000 mL
The correct strategy is to multiply the given amount (in mL) by the conversion factor
that allows milliliter units to cancel out and liter units to remain. Using the second
conversion factor will give you the units you want.
These conversion factors are based on an exact definition (1000 mL = 1 L exactly),
so significant figures do not apply to these factors. The number of significant figures in
a converted measurement depends on the certainty of the measurement you start with.

SAMPLE 1 SAMPLE 2
A sample of aluminum has a mass of 0.087 g. A sample of a mineral has 4.08 x 10 ' mol of
“

W hat is the sample s mass in milligrams? vanadium per kilogram of mass. How many micro-
Based on SI prefixes, you know that I g = moles of vanadium per kilogram does the mineral
1000 mg. Therefore, the possible conversion fac- contain?
i
tors are The pref ix micro - specifies 1 I M H I I N N I or 1 x 10 6 of
moo mg 1g the base unit.
and So. I / / mol = l x 10 ° mol.The possible conver -
U 1000 mg
sion factors are
The first conversion factor cancels grams, leav -
1 // mol 1 x 10 mol
ing milligrams. and
1 x 10 * mol 1 / / mol
1000 mg
0.087 grx = 87 mg The first conversion factor will allow moles to
\ jg
cancel and micromoles to remain.
Notice that the values 0.087 g and 87 mg each
1 // mol
have two significant figures. 4.08 x IQ 5 mol x
'
= 40.8 / / mol
*
I x 10“ mol
Notice that the values 4.08 x 10 ^ mol and
40.8 / / mol each have three significant figures.

PRACTICE PROBLEMS
.
1 Express each of the following measurements .
2 Use scientific notation to express each of the
in the units indicated. following measurements in the units indicated.
a. 2250 mg in grams a. 0.000 072 g in micrograms
b. 59.3 kL in liters b. 3.98 x 10 m in kilometers
( 1

92 CHAPTER 3
Answer the following items on a separate piece of paper. 7. How many neutrons are present in an atom of
tin that has an atomic number of 50 and a mass
MULTIPLE CHOICE
number of 119?
1. A chemical compound always has the same el- A . 50
ements in the same proportions by mass regard- B . 69
.
less of the source of the compound This is a .
C 119
statement of
A . the law of multiple proportions.
.
D 169

B. the law of isotopes. .

8 What is the mass of 1.50 mol of sodium, Na?
C. the law of definite proportions. .
A 0.652 g
.
D the law of conservation of mass. B. 0.478 g

2. An important result of Rutherford’s experi-

.
C 11.0 g
ments with gold foil was to establish that
.
D 34.5 g
A . atoms have mass. 9. How many moles of carbon are in a 28.0 g
B. electrons have a negative charge. sample?
C. neutrons are uncharged particles. A . 336 mol
D. the atom is mostly empty space. B. 72.0 mol
C 2.33 mol
3 . Which subatomic particle has a charge of + 1 ?
A. electron
.
D 0.500 mol

B. neutron SHORT ANSWER

C. proton 10. Which atom has more neutrons, potassium-40 or
.
D meson argon-40?
.
4 Which particle has the least mass? .
11 What is the mass of 1.20 x 102 ' atoms of
A . electron phosphorus?
B. neutron EXTENDED RESPONSE
C. proton
.
D All have the same mass.
.
12 Cathode rays emitted by a piece of silver and a
piece of copper illustrate identical properties.
5. Cathode rays are composed of What is the significance of this observation?
A . alpha particles.
13. A student believed that she had discovered a
B. electrons. new element and named it mythium Analysis .
.
C protons. found it contained two isotopes. The composi-
.
D neutrons. tion of the isotopes was 19.9% of atomic mass
.
6 The atomic number of an element is the same 10.013 and 80.1% of atomic mass 11.009. What
as the number of is the average atomic mass, and do you think
A. protons. mythium was a new element ?
B. neutrons.
.
C protons + electrons.
.
D protons + neutrons.

Choose the best possible answer

for each question, even if you think there is another
possible answer that is not given.

ATOMS: THE BUILDING BLOCKS OF M ATTE R 93

 INQUIRY MICRO -
EXPERIMENT 3 L A B L A B

Conservation of Mass
OBJECTIVES BACKGROUND
• Observe the signs of a chemical reaction. The law of conservation of mass states that matter
is neither created nor destroyed during a chemical
• Compare masses of reactants and products. reaction. Therefore, the mass of a system should
• Design experiments. remain constant during any chemical process. In this
• Relate observations to the law of experiment, you will determine whether mass is con-
conservation of mass. served by examining a simple chemical reaction and
comparing the mass of the system before the reac -
MATERIALS tion with its mass after the reaction.

• 2 1. plastic soda bottle

• 5 % acetic acid solution ( vinegar )
• balance
• clear plastic cups, 2
• graduated cylinder
SAFETY

A <$ .^ £ <
For review of safety, please see Safety in the
Chemistry Laboratory in the front of vour book .
• hook-insert cap for bottle
PREPARATION
• microplunger
1. Make two data tables in your lab notebook, one .
• sodium hydrogen carbonate ( baking soda ) for Part I and another for Part II. In each table,
create three columns labeled ‘initial mass ( g )."
“Final mass ( g),” and “Change in mass ( g).’*
Each table should also have space for observa -
tions of the reaction.

PROCEDURE—PART I
1. Obtain a microplunger, and tap it down into
a sample of baking soda until the bulb end is
packed with a plug of the powder ( 4-5 mL of
baking soda should be enough to pack the bulb ).

Baking Soda 2. Hold the microplunger over a plastic cup, and

squeeze the sides of the microplunger to loosen
the plug of baking soda so that it falls into the cup.
3. Use a graduated cylinder to measure 100 mL
of vinegar, and pour it into a second plastic cup.
4 . Place the two cups side by side on the balance
pan, and measure the total mass of the system
FIGURE A Slowly add the vinegar to prevent the
reaction from getting out of control.

94 CHAPTER 3
 EXPERIMENT 3
( before reaction ) to the nearest 0.01 g. Record ANALYSIS AND INTERPRETATION-
the mass in vour data table.
J PART I
5. Add the vinegar to the baking soda a little at 1. Drawing Conclusions: What evidence was there
a time to prevent the reaction from getting out that a chemical reaction occurred ?
of control , as shown in Figure A . Allow the 2. Organizing Data: How did the final mass of the
vinegar to slowly run down the inside of the system compare with the initial mass of the
cup. Observe and record your observations system ?
about the reaction .
3. Resolving Discrepancies: Does your answer
6. When the reaction is complete, place both cups to the previous question show that the law
on the balance, and determine the total final mass of conservation of mass was violated? ( Hint:
of the system to the nearest 0.01 g. Calculate any Another way to express the law of conservation
change in mass. Record both the final mass and of mass is to say that the mass of all of the
any change in mass in your data table. products equals the mass of all of the reactants. )
7. Examine the plastic bottle and the hook -insert What do you think might cause the mass
cap. Try to develop a modified procedure that difference?
will test the law of conservation of mass more
accurately than the procedure in Part I . ANALYSIS AND INTERPRETATION-
8. In your notebook , write the answers to items 1 PART II
—
through 3 in Analysis and Interpretation Part I . 1. Drawing Conclusions: Was there any new
evidence in Part II indicating that a chemical
PROCEDURE—PART II reaction occurred ?
9. Your teacher should approve the procedure you 2. Organizing Ideas: Identify the state of matter
—
designed in Procedure Part I . step 7. Implement for each reactant in Part II . Identify the state
your procedure with the same chemicals and of matter for each product .
quantities you used in Part 1. but use the bottle
and hook -insert cap in place of the two cups.
Record your data in your data table. CONCLUSIONS
1. Relating Ideas: What is the difference between
10. If you were successful in step 9 and your results
the system in Part I and the system in Part II ?
reflect the conservation of mass, proceed to
What change led to the improved results in
complete the experiment. If not , find a lab group
Part II?
that was successful , and discuss with them what
they did and why they did it . Your group should 2. Evaluating Methods: Why did the procedure for
then test the other group's procedure to deter - Part II work better than the procedure for Part I ?
mine whether their results are reproducible.
EXTENSIONS
CLEANUP AND DISPOSAL
1. Applying Models: When a log burns, the result -
11. Clean your lab station . Clean all equip-
ing ash obviously has less mass than the
ment . and return it to its proper place.
unburned log did . Explain whether this loss of
Dispose of chemicals and solutions in
mass violates the law of conservation of mass.
the containers designated by your teacher.
Do not pour any chemicals dowm the drain 2. Designing Experiments: Design a procedure that
or throw anything in the trash unless vour would test the law of conservation of mass for
teacher directs you to do so. Wash your hands the burning log described in Extension item 1.
thoroughly after all work is finished and before
vou leave the lab.

ATOMS: THE BUILDING BLOCKS OF MATTER 95

 CHAPTER 4

Arrangement of
Electrons in Atoms
The emission of light is fundamentally
related to the behavior of electrons.
The Development of a SECTION 1

New Atomic Model OBJECTIVES

^ Explain the mathematical
relationship among the speed,
wavelength, and frequency of
electromagnetic radiation.
T he Rutherford model of the atom was an improvement over previ-
ous models, hut it was incomplete. It did not explain how the atom ' s -J Discuss the dual wave-particle
negatively charged electrons are distributed in the space surrounding its nature of light.
positively charged nucleus. After all, it was well known that oppositely
charged particles attract each other. So what prevented the negative
electrons from being drawn into the positive nucleus? ^ Discuss the significance of
the photoelectric effect and
In the early twentieth century, a new atomic model evolved as a
the line-emission spectrum of
result of investigations into the absorption and emission of light bv mat - hydrogen to the development
ter. The studies revealed an intimate relationship between light and an of the atomic model.
atom 's electrons. This new understanding led directly to a revolutionary
view of the nature of energy, matter, and atomic structure.
Describe the Bohr model
of the hydrogen atom.
Properties of Light
Before 1900, scientists thought light behaved solely as a wave. This
belief changed when it was later discovered that light also has particle-
like characteristics. Still, many of light 's properties can be described in
terms of waves. A quick review of these wavelike properties will help
you understand the basic theory of light as it existed at the beginning of
the twentieth centurv.

The Wave Description of Light

Visible light is a kind of electromagnetic radiation, which is a form of
energy that exhibits wavelike behavior as it travels through space. Other
kinds of electromagnetic radiation include X rays, ultraviolet and
infrared light, microwaves, and radio waves. Together; all the forms of
electromagnetic radiation form the electromagnetic spectrum. The elec -
tromagnetic spectrum is represented in Figure 1 on the next page.
All forms of electromagnetic radiation move at a constant speed of
SCtlNKS.]
3.00 x 10s meters per second (m/s) through a vacuum and at slightly
slower speeds through matter. Because air is mostly space, the value of
3.00 x 10s m /s is also light 's approximate speed through air.
—
Developed nd MtnUined by tbe
Natto I Some Teocben ASMOJUM

For a variety of links related to this

chapter go to www.scilinks.org
,

The significant feature of wave motion is its repetitive nature, which

can be characterized by the measurable properties of wavelength and
Topic: Electromagnetic
Spectrum
^
frequency. Wavelength ( A ) is the distance between corresponding points SciLinks code: HC60482
on adjacent waves. The unit for wavelength is a distance unit. Depending
on the type of electromagnetic radiation, it may be expressed in meters.

ARRANGEMENT OF ELECTRONS IN ATOMS 97

 I Visible spectrum
FIGURE 1 Electromagnetic
Violet Blue Green Yellow Orange Red radiation travels in the form of
400 nm 500 nm 600 nm 700 nm waves covering a wide range of
wavelengths and frequencies.
This range is known as the elec-
tromagnetic spectrum. Only a
small portion of the spectrum ,
from 400 nm to 7( X ) nm . is visi -
ble to the human eye.

y rays X rays Ultraviolet Infrared Microwave Radio waves

Radar TV Short Long
wave wave
FM

; ; ; >
10 nm 10 nm 10° nm 10 ' nm 10 nm tO’ nmlO ’ cm 102 cm 10 cm 10° cm 10 cm 1m 10 ' m 10 m 103 m 104 m
Wavelength, A

1019 Hz 10’8 Hz
,; , , ,
10 HZ 10 6 HZ 10" HZ 10 4 HZ 10 3 HZ 10 2 HZ 10 HZ
, ,
10 0 HZ 109 HZ 100 MHZ 10 MHZ 1 MHZ 100 KHZ
Frequency, v

Electromagnetic spectrum

centimeters, or nanometers, as shown in Figure 1. Frequency ( v ) is

defined as the number of waves that pass a given point in a specific time,
usually one second . Frequency is expressed in waves/second . One
wave /second is called a hertz ( Hz ) , named for Heinrich Hertz, who was
a pioneer in the study of electromagnetic radiation . Figure 2 illustrates
the properties of wavelength and frequency for a familiar kind of wave,
a wave on the surface of water. The wave in Figure 2a has a longer wave -
length and a lower frequency than the wave in Figure 2 I >.

To the beach
x
m
( a)

m
FIGURE 2 The distance between X
any two corresponding points on
one of these water waves, such as
from crest to crest is the wave's
,

wavelength , A. We can measure the

wave’s frequency, v, by observing
how often the water level rises and
mm*
falls at a given point , such as at the
post . ( b)

98 CHAPTER 4
 Frequency and wavelength are mathematically related to each other.
For electromagnetic radiation, this relationship is written as follows.

c= Xv

In the equation, c is the speed of light ( in m/ s ), X is the wavelength of

the electromagnetic wave ( in m ). and v is the frequency of the electro-
magnetic wave ( in s 1 ). Because c* is the same for all electromagnetic
'

radiation, the product Xv is a constant . Consequently, we know that X is

inversely proportional to v. In other words, as the wavelength of light
decreases, its frequency increases, and vice versa. Light
rv
/v ^

Stream of electrons
The Photoelectric Effect
Anode
In the early 1900s, scientists conducted two experiments involving inter - Cathode
ML (metal plate )
actions of light and matter that could not be explained by the wave theory
of light . One experiment involved a phenomenon known as the photo- I Voltage source
electric effect. The photoelectric effect refers to the emission of electrons 1+ I III

from a metal w hen light shines on the metal, as illustrated in Figure 3.

The mystery of the photoelectric effect involved the frequency of the
light striking the metal. For a given metal, no electrons were emitted if FIGURE 3 The photoelectric
the light ’s frequency was below a certain minimum —regardless of the effect: electromagnetic radiation
light s intensity. Light was known to be a form of energy, capable of strikes the surface of the metal,
knocking loose an electron from a metal. But the wave theory of light ejecting electrons from the metal
and causing an electric current .
predicted that light of any frequency could supply enough energy to
eject an electron. Scientists couldn't explain why the light had to be of
a minimum frequency in order for the photoelectric effect to occur.

The Particle Description of Light

Hie explanation of the photoelectric effect dates back to 1900, when
German physicist Max Planck was studying the emission of light by hot
objects. He proposed that a hot object does not emit electromagnetic
energy continuously, as would be expected if the energy emitted were in
. .
the form of waves Instead Planck suggested that the object emits ener -
gy in small, specific packets called quanta. A quantum of energy is the
mini mam quantity of energy that can he lost or gained by an atom .
Planck proposed the following relationship between a quantum of ener -
gy and the frequency of radiation.

SC
E = // v / lNKS. OmtopH and MNUMH by Ik*
NrfMMl SdOKC Vncfcen AiMcultM
In the equation. E is the energy, in joules, of a quantum of radiation, v For a variety of links related to this
is the frequency, in s 1. of the radiation emitted, and h is a fundamental
"
chapter, go to vvww.scilinks.org ^
physical constant now known as Planck ’s constant; h = 6.626 x HP'4 J * s. Topic: Photoelectric Effect
In 1905. Albert Einstein expanded on Planck 's theory by introducing SciLinks code: HC61138
-
the radical idea that electromagnetic radiation has a dual wave particle
nature. While light exhibits many wavelike properties, it can also be

ARRANGEMENT OF ELECTRONS IN ATOMS 99

 thought of as a stream of particles. Each particle of light carries a quan-
tum of energy. Einstein called these particles photons. A photon is a
panicle of electromagnetic radiation having zero mass and carrying a
quantum o f energy. The energy of a particular photon depends on the
frequency of the radiation.

E photon = // v

Einstein explained the photoelectric effect by proposing that elec -

tromagnetic radiation is absorbed by matter only in whole numbers of
.
photons In order for an electron to be ejected from a metal surface, the
electron must be struck by a single photon possessing at least the mini-
mum energy required to knock the electron loose. According to the
equation = /zv, this minimum energy corresponds to a minimum
frequency. If a photon s frequency is below the minimum, then the elec -
tron remains bound to the metal surface. Electrons in different metals
are bound more or less tightly, so different metals require different
minimum frequencies to exhibit the photoelectric effect.

The Hydrogen- Atom

Line- Emission Spectrum
When current is passed through a gas at low pressure, the potential
energy of some of the gas atoms increases. The lowest energy state of an
atom is its ground state. A state in which an atom has a higher potential
energy than it has in its ground state is an excited state. When an excited
atom returns to its ground state, it gives off the energy it gained in the
form of electromagnetic radiation. The production of colored light in
neon signs, as shown in Figure 4, is a familiar example of this process.
When investigators passed electric current through a vacuum tube
containing hydrogen gas at low pressure, they observed the emission of a
characteristic pinkish glow. When a narrow beam of the emitted light was
shined through a prism. it was separated into four speci fic colors of the vis-
ible spectrum . The four bands of light were part of what is known as
FIGURE 4 Excited neon atoms hydrogen's line- emission spectrum. The production of hydrogen's line-
emit light when electrons in higher emission spectrum is illustrated in Figure 5. Additional series of lines
energy levels fall hack to the ground
were discovered in the ultraviolet and infrared regions of hydrogen's line-
state or to a lower-energy excited
emission spectrum. Ilic wavelengths of some of the spectral series are
state.
shown in Figure 6. They are known as the Lyman. Balmer. and Paschen
series, after their discoverers.
Classical theory predicted that the hydrogen atoms would be excited
by whatever amount of energy was added to them. Scientists had thus
expected to observe the emission of a continuous range of frequencies of
electromagnetic radiation that is. a continuous spectrum. Why had the
hydrogen atoms given off only specific frequencies of light ? Attempts to
explain this observation led to an entirely new atomic theory called
quantum theory.

100 CHAPTER 4
 FIGURE 5 Excited hydrogen
atoms emit a pinkish glow, as is
shown in this diagram . When the
visible portion of the emitted light
is passed through a prism it is sepa -
,

rated into specific wavelengths that

are part of hydrogen ’s line -emission
spectrum . The line at 397 nm is in
the ultraviolet and is not visible to
the human eye.

Current is passed through

a glass tube containing
hydrogen at low pressure .
The line at 397 nm
is in the ultraviolet and is
not visible to the human eye.

Lyman series Balmer series Paschen series

(ultraviolet ) (visible) (infrared)
A r

M l
III
III
III
III
III
III
III
III

exd/ | \ bxa dc b a c b a
c
1 1
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Wavelength (nm)

FIGURE 6 A series of specific wavelengths of emitted light makes up hydro -

gen s line-emission spectrum . The letters below the lines label hydrogen ’s vari -
'

ous energy - level transitions. Niels Bohr ’s model of the hydrogen atom
provided an explanation for these transitions.

Whenever an excited hydrogen atom falls to its ground state or to a E2

lower-energy excited state, it emits a photon of radiation . The energy of
this photon ( Ef hoton = // v ) is equal to the difference in energy between
)

the atom 's initial state and its final state, as illustrated in Figure 7 The .
fact that hydrogen atoms emit only specific frequencies of light indicated
Ephoton = E2 - Ej = h\
that the energy differences between the atoms ' energy states were fixed.
This suggested that the electron of a hydrogen atom exists only in very
E,
specific energy states.
In the late nineteenth century, a mathematical formula that related FIGURE 7 When an excited atom
the various wavelengths of hydrogen ’s line-emission spectrum was dis- with energy E 2 falls back to energy
covered . The challenge facing scientists was to provide a model of the Eh it releases a photon that has
hydrogen atom that accounted for this relationship. energy E: - E , = Ephou ,„ = /iv .

ARRANGEMENT OF ELECTRONS IN ATOMS 101

 Bohr Model of the Hydrogen Atom
The puz /le of the hvdrogen-atom spectrum was solved in 1913 by the
Danish physicist Niels Bohr. He proposed a hydrogen - atom model that
linked the atom’s electron to photon emission. According to the model,
the electron can circle the nucleus only in allowed paths, or orbits.
When the electron is in one of these orbits, the atom has a definite, fixed
energy. The electron— and therefore the hydrogen atom —is in its low -
Chemistry in Action est energy state when it is in the orbit closest to the nucleus. This orbit
Fireflies is separated from the nucleus by a large empty space where the electron
What kinds of reactions produce light ? cannot exist.The energy of the electron is higher when the electron is in
In this chapter, you are learning how orbits that are successively farther from the nucleus.
excited atoms can produce light. In The electron orbits, or atomic energy levels, in Bohr 's model can be
parts of the United States, summer is
accompanied by the appearance of fire - compared to the rungs of a ladder. When you are standing on a ladder,
flies, or lightning bugs. What makes your feet are on one rung or another. The amount of potential energy
them glow ? A bioluminescent chemical that you possess corresponds to standing on the first rung, the second
reaction that involves luciferin, rung, and so forth. Your energy cannot correspond to standing between
luciferase (an enzyme), adenosine two rungs because you cannot stand in midair. In the same way. an elec -
triphosphate ( ATP), and oxygen takes
tron can be in one orbit or another, but not in between.
place in the firefly and produces the
characteristic yellow - green glow. I low does Bohr ’s model of the hydrogen atom explain the observed
Unlike most reactions that produce spectral lines? While in a given orbit , the electron is neither gaining nor
light, bioluminescent reactions do not losing energy. It can. however, move to a higher-energy orbit by gaining
generate energy in the form of heat. an amount of energy equal to the difference in energy between the
higher-energy orbit and the initial lower-energy orbit . When a hydrogen
atom is in an excited state, its electron is in one of the higher-energy
orbits. When the electron falls to a lower energy level, a photon is emit -
ted, and the process is called emission. The photon's energy is equal to
the energy difference between the initial higher energy level and the
final lower energy level. Energy must be added to an atom in order to
move an electron from a lower energy level to a higher energy level.
.
This process is called absorption Absorption and emission of radiation
in Bohr 's model of the hydrogen atom are illustrated in Figure S. The
energy of each absorbed or emitted photon corresponds to a particular
,
frequency of emitted radiation, EJ lnltm = / / v.
}

Based on the different wavelengths of the hydrogen line-emission

.
spectrum Bohr calculated the allowed energy levels for the hydrogen

e
_ Ephoton = E3 - Ei

£3 3
FIGURE 8 ( a ) Absorption and ( b ) Ephoton p E2 ~ EI , e~
ft ft
emission of a photon by a hydrogen 1

atom according to Bohr ’s model. The

y
frequencies of light that can be Nucleus
I
Nucleus
r
absorbed and emitted are restricted
because the electron can only be in
orbits corresponding to the energies
F.t , Ej , £ ?, and so forth. (a ) Absorption (b) Emission

102 CHAPTER 4
 * oo
FIGURE 9 This energy-state dia -
* 6
gram for a hydrogen atom shows
*E 5
4
some of the energy transitions for
the Lyman. Balmer, and Paschen
spectral series. Bohr s model of the
atom accounted mathematically for
a b c * 3
the energy of each of the transitions
Paschen series shown.

a b e d
> Balmer series
cn
<v
c
L U

El
a b c d e
Lyman series

. then related the possible energy -level changes to the lines in

atom He
the hydrogen emission spectrum. The five lines in the Lyman series, for
example, were shown to he the result of electrons dropping from ener -
gy levels E(v Es, E4, E3, and E: to the ground-state energy level E . ,
Bohr 's calculated values agreed with the experimentally observed
values for the lines in each series. The origins of three of the series of
lines in hydrogen’s line-emission spectrum are shown in Figure 9.
Bohr's model of the hydrogen atom explained observed spectral lines
so well that many scientists concluded that the model could be applied to
all atoms. It was soon recognized, however, that Bohr 's approach did not
explain the spectra of atoms with more than one electron. Nor did Bohr's
theory explain the chemical behavior of atoms.

SECTION REVIEW 5. Describe the Bohr model of the hydrogen atom.

.
1 What was the major shortcoming of Rutherford's Critical Thinking
model of the atom ?
6. INTERPRETING GRAPHICS Use the diagram in
2. Write and label the equation that relates the speed, Figure 9 to answer the following:
wavelength, and frequency of electromagnetic
radiation. a. Characterize each of the following as absorp-
tion or emission: an electron moves from E2 to
3. Define the following: , ,
E ; an electron moves from E to E3; and an
a. electromagnetic radiation b. wavelength electron moves from E6 to E 3.
c. frequency d. quantum e. photon b. Which energy -level change above emits or
4. What is meant by the dual wave-particle nature absorbs the highest energy ? the lowest energy ?
of light ?

ARRANGEMENT OF ELECTRONS IN ATOMS 103

 SECTION 2
The Quantum Model
OBJECTIVES of the Atom
J Discuss Louis de Broglie's role
in the development of the
quantum model of the atom.

^ Compare and contrast the

T o the scientists of the early twentieth century, Bohr 's model of the
Bohr model and the quantum hydrogen atom contradicted common sense. Why did hydrogen's
model of the atom. electron exist around the nucleus only in certain allowed orbits with
definite energies? Why couldn’t the electron exist in a limitless number
of orbits with slightly different energies? To explain why atomic energy
^ Explain how the Heisenberg states are quantized, scientists had to change the way they viewed the
uncertainty principle and the
nature of the electron.
Schrodinger wave equation
led to the idea of atomic
orbitals.

w List the four quantum Electrons as Waves

numbers and describe
their significance.
The investigations into the photoelectric effect and hydrogen 's line-
emission spectrum revealed that light could behave as both a wave and
^ Relate the number of a particle. Could electrons have a dual wave -particle nature as well ? In
sublevels corresponding 1924, the French scientist Louis de Broglie asked himself this very ques -
to each of an atom's main tion. And the answer that he proposed led to a revolution in our basic
energy levels, the number of understanding of matter.
orbitals per sublevel, and the De Broglie pointed out that in many ways the behavior of electrons
number of orbitals per main in Bohr 's quantized orbits was similar to the known behavior of waves.
energy level.
For example, scientists at the time knew that any wave confined to a
space can have only certain frequencies. De Broglie suggested that elec -
trons be considered waves confined to the space around an atomic
nucleus. It followed that the electron waves could exist only at specific
frequencies. And according to the relationship E = /zv. these frequencies
corresponded to specific energies— the quantized energies of Bohr’s
orbits.
Other aspects of de Broglie's hypothesis that electrons have wave -
like properties were soon confirmed by experiments. Investigators
demonstrated that electrons, like light waves, can be bent , or diffracted.
Diffraction refers to the bending of a wave as it passes by the edge of an
object or through a small opening. Diffraction experiments and other
investigations also showed that electron beams, like waves, can interfere
with each other. Interference occurs when waves overlap ( see the Quick
Lab in this section ). This overlapping results in a reduction of energy in
some areas and an increase of energy in others. The effects of diffrac -
tion and interference can be seen in Figure 10.

104 CHAPTER 4
 FIGURE 10 Diffraction patterns
produced hv ( a ) a beam of electrons
passed through a substance and
( b ) a beam of visible light passed
through a tiny aperture. Each pat -
tern shows the results of bent waves
that have interfered with each other.
The bright areas correspond to areas
of increased energy, while the dark
areas correspond to areas of
decreased energy.

(a ) ( b)

The Heisenberg Uncertainty

Principle
The idea of electrons having a dual wave-particle nature troubled scien -
tists. If electrons are both particles and waves, then where are they in the
atom ? To answer this question, it is important to consider a proposal first
made in 1927 by the German theoretical physicist Werner Heisenberg.
Heisenberg's idea involved the detection of electrons. Electrons are
detected by their interaction with photons. Because photons have about
the same energy as electrons, any attempt to locate a specific electron
with a photon knocks the electron off its course. As a result , there is
always a basic uncertainty in trying to locate an electron ( or any other
particle ) . The Heisenberg uncertainty principle states that it is impossi -
ble to determine simultaneously both the position and velocity of an elec -
tron or any other particle. Although it was difficult for scientists to
accept this fact at the time, it has proven to be one of the fundamental
principles of our present understanding of light and matter.

The Schrodinger Wave Equation

In 1926. the Austrian physicist Erwin Schrodinger used the hypothesis
that electrons have a dual wave- particle nature to develop an equation
that treated electrons in atoms as waves. Unlike Bohr 's theory, which
assumed quantization as a fact , quantization of electron energies was
a natural outcome of Schrodinger 's equation. Only waves of specific
energies, and therefore frequencies, provided solutions to the equa -
tion . Together with the Heisenberg uncertainty principle, the
Schrodinger wave equation laid the foundation for modern quantum
theory. Quantum theory describes mathematically the wave properties
o f electrons and other very small particles.

ARRANGEMENT OF ELECTRONS IN ATOMS 105

 QuidLAB Wear safety goggles and an apron.

Materials
The Wave Nature of Light: Interference • scissors
• manila folders
Question about 50 cm from the projec- • thumbtack
Does light show the wave tion screen, as shown in the • masking tape
property of interference diagram. Adjust the distance to • aluminum foil
when a beam of light is pro- form a sharp image on the pro-
• white poster board or
jected through a pinhole jection screen. cardboard
onto a screen ?
• flashlight
Discussion
Procedure
Record all your observations.
1. Did you observe interference
patterns on the screen ?
1. To make the pinhole screen,
2. As a result of your observa -
cut a 20 cm x 20 cm square
tions, what do you conclude
from a manila folder. In the
about the nature of light ?
center of the square, cut a
2 cm square hole. Cut a
7 cm x 7 cm square of alu-
.
minum foil Using a thumb-
tack, make a pinhole in the
center of the foil square. Tape
the aluminum foil over the
2 cm square hole, making sure
the pinhole is centered as
shown in the diagram.
2. Use white poster board to
make a projection screen
35 cm x 35 cm.
3. In a dark room, center the light
beam from a flashlight on the
pinhole. Hold the flashlight
about 1 cm from the pinhole.
The pinhole screen should be

Solutions to the Schrodinger wave equation are known as wave func-

tions. Based on the Heisenberg uncertainty principle, the early devel -
opers of quantum theory determined that wave functions give only the
probability of finding an electron at a given place around the nucleus.
Thus, electrons do not travel around the nucleus in neat orbits, as Bohr
had postulated. Instead, they exist in certain regions called orbitals. An
orbital is a three- dimensional region around the nucleus that indicates
the probable location of an electron.
Figure 11 illustrates two ways of picturing one type of atomic orbital.
As you will see later in this section, atomic orbitals have different
shapes and si / es.

106 CHAPTER 4
 z 2
FIGURE 11 Two ways of showing
a simple atomic orbital are present -
y ed. In ( a ) the probability of finding
the electron is proportional to the
density of the cloud. Shown in ( b ) is
a surface within which the electron
X
can be found a certain percentage
of the time, conventionally 90%.

(a ) ( b)

Atomic Orbitals and

Quantum Numbers
In the Bohr atomic model, electrons of increasing energy occupy orbits
farther and farther from the nucleus. According to the Schrodinger
equation, electrons in atomic orbitals also have quantized energies An .
electron ’s energy level is not the only characteristic of an orbital that is
indicated by solving the Schrodinger equation.
In order to completely describe orbitals, scientists use quantum num -
bers. Quantum numbers specify the properties of atomic orbitals and the
properties of electrons in orbitals. The first three quantum numbers
result from solutions to the Schrodinger equation. They indicate the
main energy level, the shape, and the orientation of an orbital. The
fourth, the spin quantum number, describes a fundamental state of the
electron that occupies the orbital. As you read the following descrip -
tions of the quantum numbers, refer to the appropriate columns in n=6
n= 5
Table 2. n=4
n=3
Principal Quantum Number
I he principal quantum number, symbolized by n , indicates the main
energy level occupied by the electron. Values of n are positive integers
only — 1. 2. 3. and so on. As / / increases, the electron’s energy and its n =2
>
average distance from the nucleus increase ( see Figure 12 ). For exam - O
'
ple. an electron for which n = 1 occupies the first, or lowest, main ener - O
c
gy level and is located closest to the nucleus. As you will see, more than
UJ

one electron can have the same n value. These electrons are sometimes
said to be in the same electron shell. The total number of orbitals that
exist in a given shell, or main energy level, is equal to /r .

n=1
Angular Momentum Quantum Number
Except at the first main energy level, orbitals of different shapes—
known as sublevels—exist for a given value o f / / . The angular momentum
.
quantum number, symbolized by / indicates the shape of the orbital. For FIGURE 12 ITic main energy lev -
a specific main energy level, the number of orbital shapes possible is els of an atom arc represented by
equal to / /. The values of / allowed are zero and all positive integers less the principal quantum number. / /.

ARRANGEMENT OF ELECTRONS IN ATOMS 107

 TABLE 1 Orbital Letter Designations According to
Values of I
/ Letter
0 s
1 P
2 <1
3 /

than or equal to n - 1 . For example, orbitals for which n = 2 can have

one of two shapes corresponding to / = 0 and / = 1 . Depending on its
value of /. an orbital is assigned a letter , as shown in Table 1.
As shown in Figure 13, s orbitals are spherical. /? orbitals have dumb -
bell shapes, and d orbitals are more complex. ( The / orbital shapes are
too complex to discuss here. ) In the first energy level . / / = 1 . there is only
—
one sublevel possible an s orbital. As mentioned , the second energy

—— —
level , / / = 2. has two sublevels the s and /? orbitals. The third energy
level . / / = 3. has three sublevels the s , p. and d orbitals. The fourth ener -
gy level. / / = 4. has four sublevels the s , / ? , d . and / orbitals. In an / / th
main energy level , there are / / sublevels.
Each atomic orbital is designated by the principal quantum number
followed bv the letter of the sublevel. For example, the l .v sublevel is the
s orbital in the first main energy level, while the 2 p sublevel is the set of
/ / orbitals in the second main energy level. On the other hand , a 4d orbital
is part of the d sublevel in the fourth main energy level. How would you
designate the /? sublevel in the third main energy level ? How many other
sublevels are in the same main energy level with this one?

Magnetic Quantum Number

Atomic orbitals can have the same shape but different orientations
around the nucleus. The magnetic quantum number, symbolized by / / /,
indicates the orientation of an orbital around the nucleus. Values of / / / are
FIGURE 13 The orbitals 5, /;, and whole numbers, including zero, from -/ to + /. Because an .v orbital is
d have different shapes. Each
spherical and is centered around the nucleus, it has only one possible
of the orbitals shown occupies a
different region of space around orientation . This orientation corresponds to a magnetic quantum num -
the nucleus.
z z
y y
y y

s orbital p orbital d orbital

108 CHAPTER 4
 z z
y

X X

px orbital py orbital pz orbital

FIGURE 14 The subscripts jr,

v. anti c indicate the three different
her ol / ? / = 0. There is therefore only one s orbital in each s sublevel. As
orientations of p orbitals. The inter -
shown in Figure 14, the lobes of a p orbital can extend along the A\ y. or section of the v. v, and z axes indi -
r axis of a three-dimensional coordinate system, lliere are therefore cates the location of the center of
three p orbitals in each p sublevel, which are designated as px , pvt and the nucleus.
p: orbitals. The three p orbitals occupy different regions of space and
are related to values of / ? / = - 1, / / / = 0, and / / / = + 1.
There are five different d orbitals in each d sublevel ( see
Figure 15 ). The five different orientations, including one with a differ -
ent shape, correspond to values of / ? / = -2, nt = - 1 , m = 0. m - + 1 , and
/ / / = +2. There are seven different / orbitals in each f sublevel.

z z z

y y

X X

dx 2 _y 2 orbital dxy orbital dyz orbital

FIGURE 15 The five different ori -

x entations of the d orbitals. Four have
the same shape but different orien -
tations. The fifth has a different
shape and a different orientation
than the others. Each orbital occu -
dxz orbital dz2 orbital pies a different region of space.

ARRANGEMENT OF ELECTRONS IN ATOMS 109

 TABLE 2 Quantum Number Relationships in Atomic Structure
Principal Number of Number of
quantum Sublevels in Number of orbitals Number of electrons
number: main energy orbitals per main electrons per main
main energy level per energy level per energy level
level ( n) ( n sublevels) sublevel (n2) sublevel ( 2 n2)
s 1 I i

V 1 2
i 4 8
P 3
s i

3 P 3 9 6 18
d 5 10
A 1 i

P 3 6
4 16 32
(I 5 10
f 7 14

As you can see in Table 2, the total number of orbitals at a main

CROSS- DISCIPLINARY energy level increases with the value of / ? . In fact , the number of orbitals
at each main energy level equals the square of the principal quantum
Go to go.hrw.com for for a full -
length article on spinironies.
number. / ?:. What is the total number of orbitals in the third energy
level ? Specify each of the sublevels using the three quantum numbers
Keyword: HC 6 ARRX you 've learned so far.

Spin Quantum Number

An electron in an orbital behaves in some ways like Earth spinning on
an axis. The electron exists in one of two possible spin states, which cre -
ates a magnetic field. To account for the magnetic properties of the elec-
tron . theoreticians of the early twentieth century created the spin
quantum number. The spin quantum number has only two possible
v a l u e s— —w h i c h indicate the two fundamental spin states of an
electron in an orbital. A single orbital can hold a maximum of two elec-
trons. which must have opposite spin states.

SECTION REVIEW 3. Describe briefly what specific information is given

1. Define the following: by each of the four quantum numbers.
a. main energy levels Critical Thinking
b. quantum numbers 4. INFERRING RELATIONSHIPS What are the possible
2. a. List the four quantum numbers. values of the magnetic quantum number m for f
orbitals ? What is the maximum number of elec -
b. What general information about atomic orbitals trons that can exist in 4 f orbitals?
is provided by the quantum numbers ?

110 CHAPTER 4
 SECTION 3
Electron
Configurations OBJECTIVES
List the total number of elec -
trons needed to fully occupy
each main energy level.

T he quantum model of the atom improves on the Bohr model because w State the Aufbau principle,
it describes the arrangements of electrons in atoms other than hydrogen. the Pauli exclusion principle,
The arrangement of electrons in an atom is known as the atom 's electron and Hund's rule.
configuration. Because atoms of different elements have different num-
bers of electrons, a unique electron configuration exists for the atoms of
Describe the electron
each element. Like all systems in nature, electrons in atoms tend to *
*
configurations for the
assume arrangements that have the lowest possible energies. The lowest -
atoms of any element using
energy arrangement of the electrons for each element is called the ele - orbital notation, electron-
ment 's ground -state electron configuration. A few simple rules, combined configuration notation, and,
with the quantum number relationships discussed in Section 2, allow us to when appropriate, noble - gas
determine these ground-state electron configurations. notation.

Rules Governing Electron

Configurations
To build up electron configurations for the ground state
of any particular atom, first the energy levels of the - 6d
orbitals are determined. Then electrons are added to the
^ ' -0-
5
orbitals one by one according to three basic rules.
( Remember that real atoms are not built up by adding — 6s - r P
5P
protons and electrons one at a time. ) d
The first rule shows the order in which electrons occu-
=^ 5s 5p
4p
py orbitals. According to the Aufbau principle, an elec- >
—-4rs 3d
— 4p
tron occupies the lowest -energy orbital that can receive it . CD
3p'
a>
Figure 16 shows the atomic orbitals in order of increas - c 3s 3P
LLI

ing energy. The orbital with the lowest energy is the

2p
l.v orbital. In a ground-state hydrogen atom, the electron 2s
is in this orbital. The 2s orbital is the next highest in
energy, then the 2p orbitals. Beginning with the third
main energy level, n = 3. the energies of the sublevels in
different main energy levels begin to overlap. -0-
Note in the figure, for example, that the 4.v sublevel is 1s
lower in energy than the 3d sublevel. Therefore, the
4.v orbital is filled before any electrons enter the FIGURE 16 The order of increasing energy for
atomic sublevels is shown on the vertical axis. Each
3cl orbitals. ( Less energy is required for two electrons to
individual box represents an orbital.
pair up in the 4.s orbital than for those two electrons to

ARRANGEMENT OF ELECTRONS IN ATOMS

 A occupy a 3d orbital. ) Once the 3d orbitals are 1 ullv occupied , which
‘

sublevel will be occupied next ?

V The second rule reflects the importance of the spin quantum num -
1 s orbital ber . According to the Pauli exclusion principle, no two electrons in the
same atom can have the same set of four quantum numbers. The princi -
FIGURE 17 According to the pal , angular momentum , and magnetic quantum numbers specify the
Pauli exclusion principle, an orbital energy, shape, and orientation of an orbital. Hie two values of the spin
can hold two electrons of opposite
spin states. In this electron configu -
quantum number reflect the fact that for two electrons to occupy the
ration of a helium atom , each arrow same orbital they must have opposite spin states ( see Figure 17 ) .
,

represents one of the atom ’s two I he third rule requires placing as many unpaired electrons as possible
electrons. The direction of the arrow in separate orbitals in the same sublevel . In this way. electron -electron
indicates the electron ’s spin state . repulsion is minimized so that the electron arrangements have the low -
est energy possible. According to lltind's rule, orbitals of equal energy are
each occupied by one electron before any orbital is occupied by a second
electron , and all electrons in singly occupied orbitals must have the static
spin state . Applying this rule shows, for example, that one electron will
enter each of the three p orbitals in a main energy level before a second
electron enters any of them . This is illustrated in Figure IS. What is the
maximum number of unpaired electrons in a d sublevel ?

FIGURE 18 The figure shows how As As As /K As As As As

( a ) two, ( b ) three , and ( c ) four elec -
trons fill the p sublevel of a given V
main energy level according (a ) ( b) ( c)
to Hund 's rule.

Representing Electron
Configurations
Three methods, or notations, are used to indicate electron configura -
tions. Iwo of these notations will be discussed in the next two sections
for the first - period elements, hydrogen and helium . The third notation
is used mostly with elements of the third period and higher. It will be
discussed in the section on third - period elements.
In a ground -state hydrogen atom , the single electron is in the lowest -
energy orbital , the Is orbital. The electron can be in either one of its
two spin states. Helium has two electrons, which are paired in the
Is orbital.

Orbital Notation
In orbital notation , an unoccupied orbital is represented bv a line. .
with the orbital s name written underneath the line. An orbital containing
'
one electron is represented as _T . An orbital containing two electrons
is represented as 'M , showing the electrons paired and with opposite
spin states. The lines are labeled with the principal quantum number and

112 CHAPTER 4
sublevel letter. For example, the orbital notations for hydrogen and
helium are written as follows.

He
Ti
Is

Electron- Configuration Notation

Electron -configuration notation eliminates the lines and arrows of
orbital notation. Instead, the number of electrons in a sublevel is shown
CHEMISTRY .I
by adding a superscript to the sublevel designation. The hydrogen con- Module 2 : Models of the Atom
figuration is represented by l.v . The superscript indicates that one elec -
'
tron is present in hydrogen’s Is orbital. The helium configuration is
represented by \ s 2 . Here the superscript indicates that there are two
electrons in helium s Is orbital.

SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of Chapter 5 .

The electron configuration of boron is \ s12 s12p\ How many electrons are present in an atom of boron?
What is the atomic number for boron? Write the orbital notation for boron.

SOLUTION The number of electrons in a boron atom is equal to the sum of the superscripts in its
electron-configuration notation: 2 + 2 + 1 = 5 electrons. The number of protons equals the
number of electrons in a neutral atom. So we know that boron has 5 protons and thus has an
atomic number of 5. To write the orbital notation, first draw the lines representing orbitals.

\s 2s
2p
Next, add arrows showing the electron locations. The first two electrons occupy n = I energy
level and fill the Is orbital.
Ti
v
Is Is
2p
The next three electrons occupy the n - 2 main energy level. Two of these occupy the lower-
energv 2s orbital. The third occupies a higher-energy /? orbital.
Ti Ti T
Is Is
2p

PRACTICE Answers in Appendix E

1. The electron configuration of nitrogen is \ s22s: 2 p \ How many

electrons are present in a nitrogen atom ? What is the atomic num -
ber of nitrogen? Write the orbital notation for nitrogen.
Go to go.hrw.com for
2 . The electron configuration of fluorine is ls22c 2/r\ What is the more practice problems
atomic number of fluorine? How many of its p orbitals are filled? that deal with electron
configurations.

jjC Keyword: HC 6 ARRX

ARRANGEMENT OF ELECTRONS IN ATOMS 113

 c —

= 3(
11IlSTORICAL
I
The Noble Decade
CHEMISTRY

By the late nineteenth century, the science of chemistry Rayleigh was at a loss to explain his discovery. Finally, in
had begun to be organized. In 1860, the First International 1892, he published a letter in Nature magazine to appeal
Congress of Chemistry established the field's first stan- to his colleagues for an explanation. A month later, he
dards. And Dmitri Mendeleev 's periodic table of elements received a reply from a Scottish chemist named William
gave chemists across the globe a systematic understand - Ramsay. Ramsay related that he too had been stumped by
|y ing of matter ' s building blocks. But many important the density difference between chemical and atmospheric
findings—including the discovery of a family of rare, nitrogen. Rayleigh decided to report his findings to the
unreactive gases that were unlike any substances known Royal Society.
at the time—were yet to come.
A Chemist's Approach
Cross-Disciplinary Correspondence With Rayleigh's permission, Ramsay attempted to remove
In 1888, the British physicist Lord Rayleigh encountered a all known components from a sample of air and to ana -
small but significant discrepancy in the results of one of lyze what, if anything, remained. Having removed water
his experiments. In an effort to redetermine the atomic vapor, carbon dioxide, and oxygen from the air, Ramsay
mass of nitrogen, he measured the densities of several repeatedly passed the sample over hot magnesium. The
samples of nitrogen gas. Each sample had been prepared nitrogen reacted with the magnesium to form solid mag-
by a different method. All samples that had been isolated nesium nitride. As a result, all of the then-known compo -
from chemical reactions exhibited similar densities. But nents of air were removed. What remained was a
they were about one - tenth of a percent less dense than minuscule portion of a mysterious gas.
the nitrogen isolated from air, which at the time was Ramsay tried to cause the gas to react with chemically
believed to be a mixture of nitrogen, oxygen, water vapor, active substances, such as hydrogen, sodium, and caustic
w and carbon dioxide. soda, but the gas remained unaltered. He decided to name
this new atmospheric component argon (Greek for " inert "
tv A
.
or " idle ")
Periodic Problems
This excerpt from Lord Rayleigh 's letter was originally pub- Rayleigh and Ramsay were sure that they had discovered a
0 W
lished in Nature magazine in 1892.V
new element. But this created a problem. Their calculations
SEPTEMBER 29, 1892 N A TURE indicated that argon had an atomic mass of about 40.
. However, as it appeared in 1894, the periodic table had no
LETTERS TO THE EDITOR
[ The Editor does not hold himself responsible for opinions ex - space for such an element. The elements with atomic masses
.
pressed by his correspondents Neither can he undertake
closest to that of argon were chlorine and potassium.
,
to return or to correspond with the writers of rejected ,
manuscripts intended for this or any other part oj NATURE . Unfortunately, the chemical properties of the families of each
No notice is taken oj anonymous communications ] .
U I AM
Deniity of Nitrogen.
much puzzled by some recent results as to the density of
of these elements were completely dissimilar to those of the
strange gas.
nitrogen , and shall l >e obliged if any of your chemical readers
can offer suggestions as to the cause. According to two methods Ramsay contemplated argon's lack of reactivity. He knew
of preparation I obtain quite distinct values .
The relative
that Mendeleev had created the periodic table on the basis
,
difference, amounting to about Vou part , is small in itself ;
but it lies entirely outside the errors of experiment , and can only
be attributed to a variation in the character of the gas . .. of valence, or the number of atomic partners an element
Is it possible that the difference is independent of impurity,
the nitrogen itself being to some extent in a different (dissociated ) bonds with in forming a compound. Because Ramsay could
state ?... RAYLEIGH . not cause argon to form any compounds, he assigned it a
Tcrling l’lacc, Witham , September 24 . valence of zero. And because the valence of the elements in
 Groups III IV V VI VII VIII I II III IV V VI VII 0 I II
Periods b b b b b b b b a a a a a a a
1 H He
2 Li Be
3 B C N 0 F Ne Na
4 Al Si P S Cl Ar K Ca
5 Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr
6 Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te Xe Cs Ba
7 La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn Fr Ra
8 Ac
1893, Scottish chemist William
A In Transition elements Main- group elements
Ramsay isolated a previously unknown
component of the atmosphere.
A This version of the periodic table shows how it looked after the discovery of the
noble gases. The placement of the Group 1 and 2 elements at the far right of the
table shows clearly how the noble gases fit in between the chlorine family and the
potassium family of elements. The 0 above the noble-gas family indicates the zero
valency of the gases.

the families of both chlorine and potassium was one, Questions

perhaps argon fit in between them. 1. What evidence led Ramsay to report that the mysteri -
Ramsay's insight that argon merited a new spot ous gas was inert ?
between the halogen family and the alkali metal family on
the periodic table was correct. And as Ramsay would soon 2. What property of argon caused Ramsay to propose a
confirm, his newly discovered gas was indeed one of a new column in the periodic table ?
previously unknown family of elements.
New Neighbors
In 1895, Ramsay isolated a light, inert gas from a mineral
SCllNKS. Mft
Dtvttofxd mi mamUimi by the
NMJOMI SOMCC Tttdwn Atuxubon
called cleveite. Physical analysis revealed that the gas was For a variety of links related to this
the same as one that had been identified in the sun in chapter, go to www scilmks. org
1868 —helium. Helium was the second zero - valent ele-
ment found on Earth, and its discovery made chemists
Topic: William Ramsay
SciLinks code: HC61666
^
aware that the periodic table had been missing a whole
column of elements.
Over the next three years, Ramsay and his assistant,
Morris Travers, identified three more inert gases present in
the atmosphere: neon (Greek for " new " ), krypton ( " hid-
den " ), and xenon ( " stranger " ). Finally in 1900, German
chemist Friedrich Ernst Dorn discovered radon, the last of
the new family of elements known today as the noble
gases. For his discovery, Ramsay received the Nobel Prize
in 1904.
 1s Elements of the Second Period
2s 2p In the first -period elements, hydrogen and helium, electrons occupy the
3s 3P 3d orbital of the first main energy level. The ground-state configurations in
Table 3 illustrate how the Aufbau principle, the Pauli exclusion principle,
4s 4p 4d 4f
and Hund's rule are applied to atoms of elements in the second period.
5s 5p 5d 5f Figure 19 shows the order in which orbitals are filled according to the
Aufbau principle.
6s 6P 6d
According to the Aufbau principle, after the l.v orbital is filled, the
7s 7p next electron occupies the s sublevel in the second main energy level.
Thus, lithium. Li, has a configuration of LrZs . The electron occupying
'
FIGURE 19 Follow the diagonal the 2s level of a lithium atom is in the atom s highest, or outermost, occu-
'

arrows from the top to get the order pied level. The highest -occupied energy level is the electron-containing
in which atomic orbitals are filled main energy level with the highest principal quantum number. The two
according to the Aufbau principle. electrons in the 1 s sublevel of lithium arc no longer in the outermost
main energy level. They have become inner-shell electrons, which are
electrons that are not in the highest -occupied energy level.
.
The fourth electron in an atom of beryllium Be, must complete the
pair in the 2s sublevel because this sublevel is of lower energy than the
2 p sublevel. With the 2s sublevel filled, the 2 p sublevel, which has three
vacant orbitals of equal energy, can be occupied. One of the three p
orbitals is occupied bv a single electron in an atom of boron. B. Two of
the three p orbitals are occupied by unpaired electrons in an atom of
carbon, C. And all three p orbitals are occupied by unpaired electrons
in an atom of nitrogen, N. Hund's rule applies here, as is shown in the
orbital notations in Table 3.
According to the Aufbau principle, the next electron must pair with
another electron in one of the 2 p orbitals rather than enter the third main
energy level. The Pauli exclusion principle allows the electron to pair with

TABLE 3 Electron Configurations of Atoms of Second-Period

Elements Showing Two Notations
Orbital notation Electron-
2P configuration
Name Symbol 1s 2s notation
Lithium Li TI T li22s1
Beryllium Be TI TI l.r 2r
Boron B TI TI T 1.V:2V:2 JI
/
Carbon C TI TI T T Lv-lv- 2/r
Nitrogen N TI TI T T T 1S22$22p3
Oxygen o TI TI TI T T \ F 2F 2p *
Fluorine F TI TI TI TI T l?2 2p5
?
Neon Ne TI TI TI TI TI l.r 2r:2//’

116 CHAPTER 4
one of the electrons occupying the 2/7 orbitals as long as the spins of the
paired electrons are opposite. Thus, atoms of oxygen. O. have the config-
uration \ s22s22 p4. Oxygen s orbital notation is shown in Table 3.
Two 2 p orbitals are filled in fluorine, F. and all three are filled in neon.
Ne. Atoms such as those of neon, which have the s and p sublevels of
their highest occupied level filled with eight electrons, are said to have
an octet of electrons. Examine the periodic table inside the back cover
of the text . Notice that neon is the last element in the second period.

Elements of the Third Period

After the outer octet is filled in neon, the next electron enters the s sub -
level in the n = 3 main energy level. Thus, atoms of sodium Na, have.
the configuration 1 s22s 22 pf ' 3s ] . Compare the configuration of a sodium
atom with that of an atom of neon in Table 3. Notice that the first
10 electrons in a sodium atom have the same configuration as a neon
atom. l.v“ 2.v:2// \ In fact , the first 10 electrons in an atom of each of the
third-period elements have the same configuration as neon. This simi -
larity allows us to use a shorthand notation for the electron configura -
tions of the third- period elements.

Noble- Gas Notation

Neon is a member of the Group 18 elements. The Group / <S’ elements
( helium. neon , argon , krypton , xenon , and ration ) are called the noble
gases. To simplify sodium s notation, the symbol for neon, enclosed in
'

square brackets, is used to represent the complete neon configuration:

.
[ Ne ] = \ s22s22 pb This allows us to write sodium s electron configuration
as [ N’ ep.v 1, which is called sodium ’s noble-gas notation. Table 4 shows
the electron configuration of each of the third-period elements using
noble-gas notation.

TABLE 4 Electron Configurations of Atoms of Third-Period Elements

Atomic Number of electrons in sublevels Noble - gas
Name Symbol number 1s 2s 2p 3s 3P notation
Sodium
Magnesium
Na
Mg
ll
12
2
2
2
2
6
6
l
i
*[Ne]3s
[Ne ]3s2
‘
Aluminum Al 13 2 o
— 6 2 1 [Ne ] 3.\:3/ > !
Silicon Si 14 2 2 6 7 iAm [ Ne ]3.v:3/r
Phosphorus P 15 i
W 2 6 i 3 [ Ne ]3.v“3/r'
Sulfur S 16 2 2 6 2 4 [Ne ]3r 3p4
Chlorine Cl 17 2 2 6 i 5 [ Ne ]3s~3/r
Argon Ar 18 2 2 6 2 6 [ Ne ]3.v23p6
*[ Ne ] = lr 2rV

ARRANGEMENT OF ELECTRONS IN ATOMS 117

 .
The last element in the third period is argon. Ar which is a noble gas.
As in neon, the highest -occupied energy level of argon has an octet of
electrons, [ Ne )3.v23/A In fact, each noble gas other than He has an elec -
tron octet in its highest energy level. A noble- gas configuration refers to
an outer main energy level occupied , in most cases, by eight electrons.

Elements of the Fourth Period

The electron configurations of atoms in the fourth-period elements
are shown in Table 5. The period begins by filling the 4s orbital, the
empty orbital of lowest energy. Thus, the first element in the fourth
period is potassium. K , which has the electron configuration [ Ar ) 4.vI.
The next element is calcium, Ca, which has the electron configuration
|Ar|4.v2.
With the 4s sublevel filled, the 4/> and 3d sublevels are the next avail -
able vacant orbitals. Figure 16 shows that the 3d sublevel is lower in

TABLE 5 Electron Configuration of Atoms of Elements in the Fourth Period

Number of electrons
Atomic in sublevels above 2 p Noble- gas
Name Symbol number 3s 3P 3d 4s 4P notation
Potassium K 19 2 6 1 *[ Ar ]45I
Calcium Ca 20 2 6 2 [ Ar ]4.v2
Scandium Sc 21 2 6 1 Am [ Arpr/ U.v2
Titanium Ti 22 2 6 2 i [ Ar ]3</:4s2
Vanadium V 23 2 6 3 2 [ Ar ]3</ '4v2
Chromium Cr 24 2 6 5 1 [ Arpr/ V '

Manganese Mn 25 2 6 5 2 [ Ar ]3d54s2
Iron Fe 26 2 6 6 2 [ Ar ]3 / 64s2
*
Cobalt Co 27 2 6 7 2 .
[ Ar ]3<7 4s 2
Nickel Ni 28 2 6 8 2 [ Ar ) 3f / 4.r
S

Cu 29 2 6 10 1
,,
[ Ar ]3r / 4.vl
|
Copper
Zinc Zn 30 2 6 10 2 | Ar ) 3</ ln4s2
Ga 31 2 6 10 2 1
,
[ Ar ]3r/ ll 4.v24/? i
Gallium
Germanium Ge 32 2 6 10 2 i ( ,
[ Ar ]3< / 1 4.Y24/r
\ Ar ]3dn 4s24p'
)
Arsenic As 33 7 6 10 2 3
Selenium Sc 34 i
Am 6 10 2 4
,
[ Ar ]3r/ I( 4.v:4/? 4
Bromine Br 35 6 10 2 5 [ Ar ]3r/ l04r 4/r
Krypton Kr 36 2 6 10 i 6 [ Ar )3rf 104.Y24p6
* [ Ar ) = IS22S22/A3.Y23
6
/?

118 CHAPTER 4
energy lhan the 4/ 7 sublevel. Therefore, the five 3d orbitals are next to
be filled. A total of 10 electrons can occupy the 3d orbitals. These are
filled successively in the 10 elements from scandium ( atomic number
21 ) to zinc ( atomic number 30 ).
Scandium. Sc. has the electron configuration [ Ar ) 3d ‘ 4 \:. Titanium. Ti.
has the configuration [ Ar|3d24r. And vanadium. V. has the configura-
tion [ Ar ] 3d '4.v2.IJp to this point , three electrons with the same spin have
been added to three separate d orbitals, as required by Hund's rule.
.
Surprisingly, chromium Cr, has the electron configuration| Ar ) 3d'4.vl .
Not only did the added electron go into the fourth 3d orbital, but an
electron also moved from the 4.v orbital into the fifth 3d orbital, leaving
the 4.v orbital with a single electron. Chromium 's electron configuration
is contrary to what is expected according to the Aufbau principle.
I lowever. in reality the [ ArpdHv 1 configuration is of lower energy than
a |Ar ]3d44.v2 configuration. For chromium, having six orbitals, all with
unpaired electrons, is a more stable arrangement than having four
unpaired electrons in the 3d orbitals and forcing two electrons to pair
up in the 4s orbital. On the other hand, for tungsten, W. which is in the
same group as chromium, having four electrons in the 5d orbitals and
two electrons paired in the 6.v orbital is the most stable arrrangement.
Unfortunately, there is no simple explanation for such deviations from
the expected order given in Figure 19 .
Manganese. Mn. has the electron configuration | Ar ) 3d > 4.s:. The
added electron goes to the 4.v orbital, completely filling this orbital
while leaving the 3d orbitals still half - filled. Beginning with the next ele -
ment , electrons continue to pair in the d orbitals. Thus, iron. Fe, has the
configuration [ Ar dHr: cobalt, Co. has the configuration [ Ar ]3d 4s2:
^
'

and nickel. Ni. has the configuration [ Ar ] 3ds4.v:. Next is copper, Cu, in
which an electron moves from the 4s orbital to pair with the electron in
the fifth 3d orbital. The result is an electron configuration of
,
| Ar ]3dll 4.v 1 — the lowest -energy configuration for Cu.
In atoms of zinc. Zn. the 4s sublevel is filled to give the electron con-
.
figuration | Ar ]3d l 04s2 In atoms of the next six elements, electrons add
one by one to the three 4/ 7 orbitals. According to I Iund s rule, one elec -
'

tron is added to each of the three 4/ 7 orbitals before electrons are paired
in any 4/7 orbital.

Elements of the Fifth Period

In the 18 elements of the fifth period, sublevels fill in a similar manner
.
as in elements of the fourth period However, they start at the 5s orbital
instead of the 4v. Successive electrons are added first to the 5s orbital,
then to the 4d orbitals, and finally to the 5/7 orbitals. This can be seen in
Table 6. There are occasional deviations from the predicted configura-
tions here also. The deviations differ from those for fourth-period ele -
ments. but in each case the preferred configuration has the lowest
possible energy.

ARRANGEMENT OF ELECTRONS IN ATOMS 119

 TABLE 6 Electron Configurations of Atoms of Elements in the Fifth Period
Number of electrons
Atomic in sublevels above 3 d Noble- gas
Name Symbol number 4s 4P 4d 5s 5p notation
Rubidium Rb 37 2 6 1 *[Kr ]5sl
Strontium Sr 38 2 6 2 |Kr ]5.v2
Yttrium Y 39 2 6 i
-
<
'
( Kr ] 4c/ 5r ,

Zirconium Zr 40 2 6 2 2 [Kr ]4d25i2

Niobium
Molybdenum
Nb
Mo
41
42
2
2
6
6
4
5
1
1
[Kr ]4d45 j
[ Kr ) 4c/ 55.v 1
'
Technetium Tc 43 i 6 6 1 [ Kr ]4(/ h5.vl
[Kr ]4</ 75 j
Ruthenium Ru 44 2 6 7 1
'
Rhodium
Palladium
Rh
Pd
45
46
i
4m

2
6
6
8
10
1 |Kr ) 4f/ 85.v
(Kr ]4</ 10
'
Silver
Cadmium
Ag
Cd
47
48
2
2
6
6
10
10
1
2
"’
[ Kr ] 4</ 5.s 1
[Kr ]4</ 105 j2
Indium In 49 2 6 10 2 1 [Kr ]4</I05.v25pl
Tin Sn 50 2 6 10 ? 2 [Kr]4d u >5s2Sp2
Antimony Sb 51 2 6 10 2 3 [ Kr |4r/ I05.v25/) ’’
Tellurium Te 52 2 6 10 2 4 [ Kr ] 4c/ 105.v25p4
Iodine 1 53 2 6 10 2 5 [Kr ]4dt 05s25p5
[ Kr ]4rf 5s25/76
Xenon Xe
[Kr ] = 1s22s22 p 3s~3 ph3d 11 ]4s24 p('
(
54 2 6 10 2 6
"’
*

SAMPLE PROBLEM B For more help, go to the Math tutor at the end of Chapter 5

a . Write both Hie complete electron-configuration notation and the noble- gas notation for iron. Fe.
b. How many electron-containing orbitals are in an atom of iron ? How many of these orbitals are com-
pletely tilled ? How many unpaired electrons are there in an atom of iron? In w hich sublevel are the
impaired electrons located ?

SOLUTION a . The complete electron-configuration notation of iron is Is22r 2/?63.v23/A3rf 64s2. The
periodic table inside the back cover of the text reveals that \ s22s22 p(' 3s 23 pt' is the
electron configuration of the noble gas argon, Ar. Therefore, as shown in Table 5.
iron's noble -gas notation is [ Av\3d 4s2.
( )

b. An iron atom has 15 orbitals that contain electrons. They consist of one Is orbital, one
2s orbital, three 2 p orbitals, one 3s orbital, three 3 p orbitals, five 3d orbitals, and one
4.v orbital. Eleven of these orbitals are filled, and there are four unpaired electrons.
They are located in the 3d sublevel. The notation 3d ( represents)

3d U T T T T

120 CHAPTER 4
 PRACTICE Answers in Appendix E

1. a. Write both the complete electron-configuration notation and

the noble-gas notation for iodine,I. How many inner-shell elec-
trons does an iodine atom contain?

b. How many electron-containing orbitals are in an atom of

iodine? How many of these orbitals are filled? How many
unpaired electrons are there in an atom of iodine ?
2. a. Write the noble-gas notation for tin, Sn. How many unpaired
electrons are there in an atom of tin?
b. How many electron-containing d orbitals are there in an atom
of tin ? Name the element in the fourth period whose atoms
have the same number of electrons in their highest energy lev -
els that tin's atoms do.
3. a. Write the complete electron configuration for the element
with atomic number 25. You may use the diagram shown in
Figure 19.
b. Identify the element described in item 3a.
4. a. How many orbitals are completely filled in an atom of the ele -
ment with atomic number 18 ? Write the complete electron con-
figuration for this element.
( 4!
^^ i 11
Go to go.hrw.com for
more practice problems
b. Identify the element described in item 4a. that deal with electron
configurations.
Keyword: HC 6 ARRX

Elements of the Sixth

and Seventh Periods
Hie sixth period consists of 32 elements. It is much longer than the
periods that precede it in the periodic table. To build up electron con -
figurations for elements of this period, electrons are added first to the
b.v orbital in cesium, Cs, and barium. Ba. Then, in lanthanum. La, an
electron is added to the 5d orbital.
With the next element , cerium. Ce. the 4/ orbitals begin to fill,
giving cerium atoms a configuration of [ Xe |4/ ! 5r / l 6s ~. In the next 13
elements, the 4/ orbitals are filled. Next the 5d orbitals are filled and
the period is completed bv filling the 6p orbitals. Because the 4/ and
the 5 d orbitals are very close in energy, numerous deviations from the
simple rules occur as these orbitals are filled. The electron configura-
tions of the sixth-period elements can be found in the periodic table
inside the back cover of the text .
The seventh period is incomplete and consists largely of synthetic
elements, which will be discussed in Chapter 21.

ARRANGEMENT OF ELECTRONS IN ATOMS 121

 SAMPLE PROBLEM C For more help, go to the Math Tutor at the end of Chapter 5.

a. Write both the complete electron-configuration notation and the noble- gas notation
for a rubidium atom.

b. Identify the elements in the second, third, and fourth periods that have the same number of highesl-
energ) -level electrons as rubidium.

,
a. l .v;2.v:2/AV.V 3 </ 4.v:4/A% 1. [ KrJS.v 1
SOLUTION
"’
b. Rubidium has one electron in its highest energy level ( the fifth ). The elements with the
same outermost configuration are. in the second period, lithium. Li; in the third period,
sodium, Na; and in the fourth period, potassium, K.

PRACTICE Answers in Appendix E

1. a. Write both the complete electron-configuration notation and

the noble - gas notation for a barium atom.
b. Identify the elements in the second, third, fourth, and fifth peri-
ods that have the same number of highest -energy -level elec -
trons as barium.
2. a. Write the noble-gas notation for a gold atom.
Go to go.hrw.com for
b. Identify the elements in the sixth period that have one more practice problems
unpaired electron in their 6s sublevel. that deal with electron
configurations.
_ j'c Keyword: HC 6 ARRX
^
SECTION REVIEW 5. Identify the elements having the following
1. a. What is an atom's electron configuration ? electron configurations:
b. What three principles guide the electron a. 1 s 22 s 22p63 s23p3
configuration of an atom? b. [ Ar]4s1
.
2 What three methods are used to represent c. contains four electrons in its third and outer
the arrangement of electrons in atoms ? main energy level
3. What is an octet of electrons ? Which d. contains one set of paired and three unpaired
elements contain an octet of electrons? electrons in its fourth and outer main energy level
4. Write the complete electron-configuration
notation, the noble-gas notation, and the Critical Thinking
orbital notation for the following elements: 6. RELATING IDEAS Write the electron configuration
a. carbon b. neon c. sulfur for the third-period elements Al, Si, P, S, and Cl. Is
there a relationship between the group number of
each element and the number of electrons in the
outermost energy level?

122 CHAPTER 4
 CHAPTER HIGHLIGHTS
The Development of a New Atomic Model
I Vocabulary •In the early twentieth century light was determined to have
,

electromagnetic radiation a dual wave-particle nature.

electromagnetic spectrum •Quantum theory was developed to explain observations such
wavelength as the photoelectric effect and the line-emission spectrum of
frequency hydrogen.
photoelectric effect •Quantum theory states that electrons can exist only at specific
quantum atomic energy levels.
photon •When an electron moves from one main energy level to a main
ground state energy level of lower energy, a photon is emitted. The photon's
excited state energy equals the energy difference between the two levels.
line -emission spectrum •An electron in an atom can move from one main energy level
continuous spectrum to a higher main energy level only by absorbing an amount of
energy exactly equal to the difference between the two levels.

The Quantum Model of the Atom

I Vocabulary •In the early twentieth century electrons were determined
,

Heisenberg uncertainty principle to have a dual wave -particle nature.

quantum theory • Heisenberg uncertainty principle states that it is impossi -
The
orbital ble to determine simultaneously the position and velocity of
quantum number an electron or any other particle.
principal quantum number •Quantization of electron energies is a natural outcome of the
angular momentum quantum number Schrodinger wave equation, which describes the properties of
magnetic quantum number an atom's electrons.
spin quantum number •An orbital, a three-dimensional region around the nucleus,
shows the region in space where an electron is most likely to
be found.
•The four quantum numbers that describe the properties of
electrons in atomic orbitals are the principal quantum number,
the angular momentum quantum number, the magnetic quan -
tum number, and the spin quantum number.

Electron Configurations
I Vocabulary •The ground-state electron configuration of an atom can be
electron configuration written by using the Aufbau principle, Hund's rule, and the
Aufbau principle Pauli exclusion principle.
Pauli exclusion principle •Electron configurations can be depicted by using different
Hund's rule types of notation. In this book, three types of notation are
noble gas used: orbital notation, electron-configuration notation, and
noble- gas configuration noble-gas notation.
•Electron configurations of some atoms, such as chromium,
deviate from the predictions of the Aufbau principle, but the
ground-state configuration that results is the configuration
with the minimum possible energy.

ARRANGEMENT OF ELECTRONS IN ATOMS 123

 CHAPTER REVIEW
12. Using the two equations E = hv and c = X \\
The Development of a New ..
derive an equation expressing E in terms of li c
Atomic Model and X .
13. How long would it take a radio wave whose fre-
SECTION 1 REVIEW quency is 7.25 x UP HZ to travel from Mars to
1. a. List live examples of electromagnetic Earth if the distance between the two planets is
radiation. approximately 8.00 x 10 km?
h. What is the speed of all forms of electro- 14 . Cobalt -60 is an artificial radioisotope that is
magnetic radiation in a vacuum? produced in a nuclear reactor and is used as a
2. Prepare a two-column table. List the properties gamma -ray source in the treatment of certain
of light that can best be explained by the wave types of cancer. If the wavelength of the gamma
.
theory in one column List those best explained radiation from a cobalt -60 source is l.00 x
by the particle theory in the second column. 10 ' nm, calculate the energy of a photon of this
"

You may want to consult a physics textbook for radiation.

reference.
3. What are the frequency and wavelength ranges
of visible light ? The Quantum Model
4. Ust the colors of light in the visible spectrum in
of the Atom
order of increasing frequency.
5 . In the early twentieth century, what two experi- SECTION 2 REVIEW
ments involving light and matter could not be
15. Describe two major shortcomings of Bohr 's
explained bv the wave theory of light?
model of the atom.
6. a. How are the wavelength and frequency of
16. a. What is the principal quantum number ?
electromagnetic radiation related?
b. How is it symbolized?
b. I low are the energy and frequency of elec -
c. What are shells?
tromagnetic radiation related?
d. How does n relate to the number of elec -
c. Ilow are the energy and wavelength of elec -
trons allowed per main energy level ?
tromagnetic radiation related?
17. a. What information is given by the angular
7. Which theory of light — the wave or particle
—
theory best explains the following phenomena?
a. the interference of light
momentum quantum number ?
b. What are sublevels, or subshells?
18. For each of the following values of / /, indicate
b. the photoelectric effect
the numbers and types of sublevels possible for
c. the emission of electromagnetic radiation
that main energy level. ( Hint : See Table 2. )
bv an excited atom
w
a. / / = l
8. Distinguish between the ground state and an
b. / 7 = 2
excited state of an atom.
c. n = 3
9. According to Bohr 's model of the hydrogen
d. / / = 4
atom, how is hydrogen ' s emission spectrum
e. / / = 7 ( number only )
produced?
19. a. What information is given by the magnetic
quantum number ?
PRACTICE PROBLEMS b. How many orbital orientations are possible
10. Determine the frequency of light whose wave- in each of the .v, p, tl , and / sublevels?
length is 4.257 x 10 7 cm.
"
c. Explain and illustrate the notation for distin -
11. Determine the energy in joules of a photon guishing between the different p orbitals in a
whose frequency is 3.55 x 10 1 Hz. sublevel.

124 CHAPTER 4
 CHAPTER REVIEW

20. a. What is the relationship between n and the 31. Write the orbital notation for the following el -
total number of orbitals in a main energy ements. ( Hint: See Sample Problem A . )
level? a. P
b. How many total orbitals are contained in the b. B
third main energy level? in the fifth? c. Na
21. a. What information is given by the spin quan- d. O
tum number? 32. Write the electron-configuration notation for
b. What are the possible values for this quan- the element whose atoms contain the following
tum number ? number of electrons:
22. How many electrons could be contained in the a. 3
following main energy levels with / / equal to the b. 6
number provided? c. 8
a. I d. 13
b. 3 33. Given that the electron configuration for oxy -
c. 4 .
gen is l$22r 2/? 4 answer the following questions:
d. b a. How many electrons are in each oxygen atom?
e. 7 b. What is the atomic number of this element ?
c. Write the orbital notation for oxygen s elec -
tron configuration.
PRACTICE PROBLEMS
d. I low many unpaired electrons does oxygen
23. Sketch the shape of an 5 orbital and a p orbital.
have ?
24 . How does a 2s orbital differ from a l.v orbital ?
e. What is the highest occupied energy level?
25. How do a 2px and a 2pv orbital differ?
.
f How many inner-shell electrons does the
atom contain?

Electron Configurations g. In which orbital( s ) are these inner-shell elec -

trons located?
SECTION 3 REVIEW 34. a. What are the noble gases?
26. a. In your own words, state the Aufbau principle, b. What is a noble-gas configuration?
b. Explain the meaning of this principle in c. I low does noble-gas notation simplify writing
terms of an atom with many electrons. an atom 's electron configuration?
27. a. In your own words, state Hund's rule, 35 . Write the noble-gas notation for the electron
b. What is the basis for this rule? configuration of each of the elements below.
28. a. In your own words, state the Pauli exclusion ( Hint: See Sample Problem B.)
principle. a. Cl
b. What is the significance of the spin quantum b. Ca
number ? c. Se
29. a. What is meant by the highest occupied energy 36. a. What information is given by the noble-gas
level in an atom? notation [ Ne ]3s:?
b. What are inner -shell electrons? b. What element does this represent ?
30. Determine the highest occupied energy level in 37. Write both the complete electron-configuration
the following elements: notation and the noble-gas notation for each
a. He of the elements below. ( Hint: See Sample
.
b Be Problem C. )
a. Na
c. Al
d. Ca b. Sr
e. Sn c. P

ARRANGEMENT OF ELECTRONS IN ATOMS 125

 CHAPTER REVIEW

38. Identify each of the following atoms on the c. Write the orbital notation for this element .
basis of its electron configuration: d. How many unpaired electrons does an atom
a. \ s22s22pl of phosphorus have ?
b. Lv 22.r 2/ rs e. What is its highest occupied energy level ?
c. [ Ne ]3r f. How many inner-shell electrons does the
d. [ Ne|3.v23/r atom contain?
e. [ Ne|3.v23/r g. In which orbital( s ) are these inner-shell elec -
f. [ Ar ]4s
‘
g. [ Ar ]3// 64r 47.
trons located?
What is the frequency of a radio wave whose
energy is 1.55 x 10 4 J per photon?
"

PRACTICE PROBLEMS
48. Write the noble-gas notation for the electron
configurations of each of the following elements:
39. List the order in which orbitals generally fill,
a. Hf d. At
from the I s to the 7p orbital. b. Sc e. Ac
40. Write the noble -gas notation for the electron
c. Fe f. Zn
configurations of each of the following elements: 49. Describe the major similarities and differences
.
a As e. Sn
between Schrodinger s model of the atom and
b. Pb .
f Xe
the model proposed by Bohr.
c. Lr g. La
50. When sodium is heated, a yellow spectral
d. Hg |
line whose energy is 3.37 x 10 ‘ J per photon is
'"
l

41 . I low do the electron configurations of chromi-

produced.
um and copper contradict the Aufbau principle?
a. What is the frequency of this light ?
b. What is the wavelength of this light?
51. a. What is an orbital ?
MIXED REVIEW b. Describe an orbital in terms of an electron
42. a. Which has a longer wavelength: green light cloud.
or yellow light?
b. Which has a higher frequency: an X ray or a
microwave ? CRITICAL THINKING
c. Which travels at a greater speed: ultraviolet
52. Inferring Relationships In the emission spec -
light or infrared light ? trum of hydrogen shown in Figure 5, each col-
43. Write both the complete electron-configuration
ored line is produced by the emission of photons
-
and noble gas notation for each of the following: with specific energies. Substances also produce
a. Ar b. Br c. A 1
absorption spectra when electromagnetic radia -
44. Given the speed lightof as 3.00 x 10s m /s. calcu-
tion passes through them. Certain wavelengths
late the wavelength of the electromagnetic ra-
are absorbed. Using the diagram below, predict
diation whose frequency is 7.500 x 1012 Hz.
what the wavelengths of the absorption lines will
45. a. What is the electromagnetic spectrum?
be when white light ( all of the colors of the visi-
b. What units can be used to express wavelength?
ble spectrum) is passed through hydrogen gas.
c. What unit is used to express frequencies of
eledromagnetic waves?
46. Given that the electron configuration for phos-
phorus is \ s 22 s22 ph?s2 }/ r\ answer the following
questions:
a. How many electrons are in each atom?
b. What is the atomic number of this element ? 300 nm 700 nm
Hydrogen absorption spectrum

126 CHAPTER 4
 CHAPTER REVIEW

53. Applying Models In discussions of the photo- RESEARCH & WRITING

electric effect, the minimum energy needed to
remove an electron from the metal is called the .
57 Neon signs do not always contain neon gas. The
threshold energy and is a characteristic of the various colored lights produced by the signs are
metal. For example, chromium. Cr. will emit due to the emission of a variety of low -pressure
electrons when the wavelength of the radiation gases in different tubes. Research other kinds of
is 2N4 nm or less. Calculate the threshold energy gases used in neon signs, and list the colors that
for chromium. ( Hint: You will need to use the they emit.
two equations that describe the relationships .
58 Prepare a report about the photoelectric effect ,
between wavelength, frequency, speed of light, and cite some of its practical uses. Explain the
and Plancks constant.) basic operation of each device or technique
.
54 Analyzing Information Four electrons in an mentioned.
atom have the four sets of quantum numbers
given below. Which electrons are in the same
orbital ? Explain your answer. ALTERNATIVE ASSESSMENT
a. 1 , 0.0. -
...
b. 1 () () +_
.
59 Performance A spectroscope is a device used

c. 2 1, l +_
. . .
to produce and analyze spectra Construct a
simple spectroscope, and determine the absorp -
d. 2, 1, 0. +_ tion spectra of several elemental gases. ( Your
55. Relating Ideas Which of the sets of quantum teacher will provide you with the gas discharge
numbers below are possible? Which are impos- tubes containing samples of different gases.)
sible ? Explain your choices.
a. 2, 2, 1, +
b. 2.0, 0. - ii
c. 2.0, 1, -

i Graphing Calculator Calculating

Quantum Number Relationships
. .
Go to go hrw com for a graphing calculator
USING THE HANDBOOK
exercise that asks you to calculate quantum
56. Sections I and 2 of the Elements Handbook number relationships.
contain information on an analytical test and a
technological application for Group 1 and 2 el-
-
2'
*JS Keyword: HC6 ARRX
ements. Hie test and application are based on
the emission of light from atoms. Review these
sections to answer the following:
a. What analytical technique utilizes the emis-
sion of light from excited atoms?
b. What elements in Groups 1 and 2 can be
identified by this technique?
c. What types of compounds are used to pro -
vide color in fireworks ?
d. What wavelengths within the visible spec -
trum would most likely contain emission
lines for barium?

ARRANGEMENT OF ELECTRONS IN ATOMS 127

 Math Tutor WEIGHTED AVERAGES AND ATOMIC MASS

You have learned that the mass of a proton is about 1 amu and that a neutron is only
slightly heavier. Because atomic nuclei consist of whole numbers of protons and neu-
trons, you might expect that the atomic mass of an element would be very near a
whole number. However, if you look at the periodic table, you will see that the atomic
masses of many elements lie somewhere between whole numbers. In fact, the atomic
masses listed on the table are overage atomic masses. The atomic masses are averages
because most elements occur in nature as a specific mixture of isotopes. For example,
75.76% of chlorine atoms have a mass of 34.969 amu, and 24.24% have a mass of
36.966 amu. If the isotopes were in a 1 : 1 ratio, you could simply add the masses of
the two isotopes together and divide by 2. However, to account for the differing abun-
dance of the isotopes, you must calculate a weighted overage. For chlorine, the weight -
ed average is 35.45 amu. The following two examples demonstrate how weighted
averages are calculated.

SAMPLE 1 SAMPLE 2
Naturally occurring silver consists of 51.839% Naturally occurring magnesium consists of
Ag-107 ( atomic mass 106.905 093 ) and 48.161 % 78.99% Mg- 24 ( atomic mass 23.985 042 ), 10.00%
Ag- 109 ( atomic mass 108.904 756 ). What is the Mg-25 ( atomic mass 24.985 837 ), and 11.01%
average atomic mass of silver ? Mg- 26 ( atomic mass 25.982 593). What is the
To find average atomic mass, convert each per - average atomic mass of magnesium?
centage to a decimal equivalent and multiply bv Again, convert each percentage to a decimal
the atomic mass of the isotope. and multiply by the atomic mass of the isotope to
0.518 39 x 106.905 093 amu = 55.419 amu get the mass contributed by each isotope.
0.481 61 x 108.904 756 amu = 52.450 amu 0.7899 x 23.985 042 amu = 18.95 amu
107.869 amu 0.1000 x 24.985 837 amu = 2.499 amu
0.1101 x 25.982 593 amu = 2.861 amu
Adding the masses contributed by each isotope
24.31 amu
gives an average atomic mass of 107.869 amu.
Note that this value for the average atomic mass Adding the masses contributed by each isotope
of silver is very near the one given in the periodic gives an average atomic mass of 24.31 amu.
table.

PRACTICE PROBLEMS
.
1 Rubidium occurs naturally as a mixture of 2. The element silicon occurs as a mixture of
two isotopes. 72.17 % Rb- 85 (atomic mass three isotopes: 92.22 % Si-28.4.69% Si - 29, and
84.911 792 amu ) and 27.83 % Rb-87 ( atomic 3.09% Si-30. The atomic masses of these three
mass 86.909 186 amu ). What is the average isotopes are as follows: Si -28 = 27.976 926
atomic mass of rubidium ? amu. Si -29 = 28.976 495 amu. and Si -30 =
29.973 770 amu.
Find the average atomic mass of silicon.

128 CHAPTER 4
Answer the following items on a separate piece of paper. 9. Which element has the noble -gas notation
[ Kr ]5r 4</ 2?
MULTIPLE CHOICE
.
1 Which of the following relationships is true?
A. Se .
C Zr
B. Sr D. Mo
A. Higher-energy light has a higher frequency
than lower-energy light does. SHORT ANSWER
B. Higher-energy light has a longer wavelength 10. When a calcium salt is heated in a flame, a pho -
than lower- energv light does. ton of light with an energy of 3.2 x 10“19 J is
C. Higher-energy light travels at a faster speed emitted. On the basis of this fact and the table
than lower-energy light does. below, what color would be expected for the
D. Higher- frequency light travels at a slower calcium flame?
speed than lower-energy light does.
Frequency, s-i 7.1 x 1014 6.4 x 1014 5.7 x 1014
2. The energy of a photon is greatest for
A . visible light. Wavelength, nm 422 469 526
.
B ultraviolet light . Color violet blue green
.
C infrared light.
D. X - ray radiation. Frequency, s-i 5.2 x 1014 4.8 x 1014 4.3 x 1014
3. What is the wavelength of radio waves that Wavelength, nm 577 625 698
have a frequency of 88.5 MHz ? yellow red
Color orange
A. 3.4 m .
C 0.30 m
B. 8.9 nm .
D 300 nm .
11 The electron configuration of sulfur is
.
4 Which transition in an excited hydrogen atom \ s22s22p ' 3s23pA. Write the orbital notation
(

will emit the longest wavelength of light ? for sulfur.

.
A E5 to E , .
C E3 to E , EXTENDED RESPONSE
.
B E4 to E| D. E to Ej
^ 12. Explain the reason for the hydrogen line -
5. Which of the following quantum numbers is emission spectrum.
often designated by the letters 5, p, iL and /
instead of bv numbers? .
13 When blue light shines on potassium metal in a
A. n .
C m photocell, electrons are emitted. But when yel-
low light shines on the metal, no current is
B. / .
D s
observed. Explain.
6. Which quantum number is related to the shape
of an orbital?
A n. C m .
B. / D s .
7. What is the maximum number of unpaired elec -
trons that can be placed in a 3/; sublevel?
A 1. .
C 3
B 2. D. 4
.
8 What is the maximum number of electrons that
can occupy a 3s orbital?
A. 1 C 6 .
B. 2 D 10 .
CHSlb i l l If time permits, take short mental
breaks during the test to improve your concentration.

ARRANGEMENT OF ELECTRONS IN ATOMS 129

 M I C R O-
EXPERIMENT 4 L A B

Flame Tests
OBJECTIVES BACKGROUND
Identify a set of flame- test color standards The characteristic light emitted by an element is the
for selected metal ions. basis for the chemical test known as a flame test .
To identify an unknown substance, you must first
Relate the colors of a flame test to the
behavior of excited electrons in a metal ion . determine the characteristic colors produced by
different elements. You will do this by performing
Identify an unknown metal ion by using a flame lest on a variety of standard solutions of
a flame test . metal compounds. Then , you will perform a flame
Demonstrate proficiency in performing test with an unknown sample to see if it matches
a flame test and in using a spectroscope. any of the standard solutions. The presence of even
a speck of another substance can interfere with the
MATERIALS identification of the true color of a particular type
250 mL beaker of atom , so be sure to keep vour equipment very-
clean and perform multiple trials to check your work .
Bunsen burner and related equipment
cobalt glass plates SAFETY
crucible tongs
distilled water
flame- test wire For review of safety, please see Safety in the
glass test plate Chemistry Laboratory in the front of your book .
( or a microchemistry
plate with wells ) PREPARATION
spectroscope
1 . Prepare a data table in your lab notebook.
Include rows for each of the solutions of metal
1.0 M IICI solution compounds listed in the materials list and an
CaCh solution unknown solution . The table should have three
wide columns for the three trials you will per -
K 2S(J 4 solution
form with each substance. Each column should
Li 2S04 solution have room to record the colors and wavelengths
Na 2S04 solution of light . Be sure you have plenty of room to
write your observations about each test .
SrCI 2 solution
2. Label a beaker Waste. Thoroughly clean and dry
unknown solution
a well strip. Fill the first well one -fourth full with
1.0 M MCI on the plate. Clean the test wire by
OPTIONAL EQUIPMENT
first dipping it in the HC1 and then holding it
• wooden splints in the colorless flame of the Bunsen burner.
Repeat this procedure until the flame is not col -
ored bv the wire. When the wire is readv, rinse

130 CHAPTER 4
 EXPERIMENT 4

the well with distilled water and collect the rinse CLEANUP AND DISPOSAL
water in the waste beaker. 6. Dispose of the contents of the waste
3. Put 10 drops of each metal ion solution listed beaker in the container designated
in the materials list in a row in each well of the by your teacher. Wash your hands
well strip. Put a row of 1.0 M HCI drops on a thoroughly after cleaning up the area and
glass plate across from the metal ion solutions. equipment.
Record the positions of all of the chemicals
placed in the wells. The wire will need to be ANALYSIS AND INTERPRETATION
cleaned thoroughly between each test solution
1. Organizing Data: Examine your data table,
with HCI to avoid contamination from the
and create a summary of the flame test for
previous test.
each metal ion.
PROCEDURE 2. Analyzing Data: Account for any differences
1. Dip the wire into the CaCI: solution, and then in the individual trials for the flame tests for
hold it in the Bunsen burner flame. Observe the metals ions.
the color of the flame, and record it in the data 3. Organizing Ideas: Explain how viewing the
table. Repeat the procedure again, but this time flame through cobalt glass can make it easier
look through the spectroscope to view the results. to analyze the ions being tested.
Record the wavelengths you see from the flame.
Repeat each test three times. Clean the wire 4. Relating Ideas: For three of the metal ions
with the HCI as you did in Preparation step 2. tested, explain how the flame color you saw
relates to the lines of color you saw' when you
2. Repeat step l with the K:S04 and with each of looked through the spectroscope.
the remaining solutions in the wrell strip.
3. Test another drop of Na:S04. but this time view CONCLUSIONS
the flame through two pieces of cobalt glass. 1. Inferring Conclusions: What metal ions are in
Clean the wire, and repeat the test. Record in the unknown solution?
your data table the colors and wavelengths of
2. Evaluating Methods: How would you character -
the flames as they appear when viewed through
ize the flame test with respect to its sensitivity?
the cobalt glass. Clean the wire and the well
What difficulties could there be when identify -
strip, and rinse the well strip with distilled water.
ing ions by the flame test ?
Pour the rinse water into the waste beaker.
4. Put a drop of K:S04 in a clean well. Add a drop EXTENSIONS
of Na2 S04. Perform a flame test for the mixture. 1. Inferring Conclusions: A student performed
Observe the flame without the cobalt glass. Repeat flame tests on several unknowns and observed
the test again, but this time observe the flame that they all were shades of red. What should
through the cobalt glass. Record in your data table the student do to correctly identify these sub-
the colors and wavelengths of the flames. Clean stances ? Explain your answer.
the wire, and rinse the well strip with distilled
water. Pour the rinse water into the waste beaker. 2. Applying Ideas: During a flood, the labels from
three bottles of chemicals were lost. The three
5. Obtain a sample of the unknown solution. unlabeled bottles of white solids were known to
Perform flame tests for it with and without the contain the following: strontium nitrate, ammo-
cobalt glass. Record your observations. Clean the nium carbonate, and potassium sulfate. Explain
wire, and rinse the well strip with distilled water. how you could easily test the substances and
Pour the rinse water into the waste beaker. relabel the three bottles. ( Hint: Ammonium ions
do not provide a distinctive flame color. )

ARRANGEMENT OF ELECTRONS IN ATOMS 131

 CHAPTER 5

ThePeriodic Law
Atoms of the heavier elements form when stars explode,
such as when a supernova caused this nebula.
History of the SECTION 1

Periodic Table OBJECTIVES

Explain the roles of Mendeleev
and Moseley in the develop-
ment of the periodic table.

I magine the confusion among chemists during the middle of the ^ Describe the modern periodic
nineteenth century. By 1860. more than 60 elements had been discov - table.
ered. Chemists had to learn the properties of these elements as well as
those of the many compounds that they formed— a difficult task . And
to make matters worse, there was no method for accurately determin -
u Explain how the periodic
law can be used to predict
ing an element 's atomic mass or the number of atoms of an element in
the physical and chemical
a particular chemical compound. Different chemists used different
properties of elements.
atomic masses for the same elements, resulting in different composi-
tions being proposed for the same compounds. This made it nearly
impossible for one chemist to understand the results of another.
In September I 860, a group of chemists assembled at the First
- Describe how the elements
belonging to a group of the
International Congress of Chemists in Karlsruhe, Germany, to settle the periodic table are interrelated
issue of atomic mass as well as some other matters that were making in terms of atomic number.
communication difficult. At the Congress, Italian chemist Stanislao
Cannizzaro presented a convincing method for accurately measuring
the relative masses of atoms. Cannizzaro s method enabled chemists to
agree on standard values for atomic mass and initiated a search for rela -
tionships between atomic mass and other properties of the elements. SCllNKS , MfA
Dratoftd Md aumUwwd by tlw
Nitioul SuciKr fotchm Auodibw

For a variety of links related to this

chapter, go to \ . . .. - j

Mendeleev and Chemical Periodicity Topic: Periodic Table

SciLinks code: HC61125
^
When the Russian chemist Dmitri Mendeleev heard about the new
atomic masses discussed at Karlsruhe, he decided to include the new
values in a chemistry textbook that he was writing. In the book,
Mendeleev hoped to organize the elements according to their proper -
ties. He went about this much as you might organize information for a
research paper. He placed the name of each known element on a card,
together with the atomic mass of the element and a list of its observed
physical and chemical properties. He then arranged the cards according
to various properties and looked for trends or patterns.
Mendeleev noticed that when the elements were arranged in order
of increasing atomic mass, certain similarities in their chemical proper -
ties appeared at regular intervals. Such a repeating pattern is referred to
as periodic. The second hand of a watch, for example, passes over any FIGURE 1 ITie regularly
.
given mark at periodic, 60- second intervals The circular waves created spaced water waves represent a
by a drop of water hitting a water surface are also periodic. simple periodic pattern.

THE PERIODIC LAW 133

 FIGURE 2 In his first published HO BI Hell, npiiirbimMocTb BU
KaateTca , yate HCHO nupaataeTca
periodic table, Mendeleev arranged cTaBjaeiiaro MHOB Bceft COBOKVHHOCTH aaeMeHTOBt, nait
Ba ' uua KO
the elements in vertical periods
KOTopuxt H3BtcTeni ci AocroBtpHocTiB. Ha 3TOTI pa3i a a atejiajib
according to relative atomic mass.
The atomic mass for each element is upeHMymecTBeHHO HAFTJ,TH o6 my » cHCTeay ajiejieHTOBi. BOTI BTOTI
indicated by the number following onuTt:
the element 's symbol. The unknown
elements indicated by question
marks at estimated atomic masses
45, 68, and 70 were later identified
.
as scandium Sc. gallium , Ga , and
Ti = 50
V 51
Cr = 52
Mn = 55
— Zr = 90

Mo = 96
? = ISO.
Nb = 94 Ta = 182 .
W = 136.
Rh = 104,4 Pt = 19 7,4

—
*

germanium , Ge. Fe = 56 Ru = 104,4 Jr = 198.

11 1
-
Ni Co = 69
CU = 63,4
-
PI = 1066, Os = 199.
Ag = 108 Hg = 200.
Be = 9,4 Mg = 24 Zn = 65,« Cd = 112
B= l l Al = 27,4 ? = 68 - Ur = ll 6 Au = 197?
C = 12
N = 14
Si = 28
-
P 31
7 70
As = 75
— Su = ll 8
Sb = 122 Bi = 210
0 = 16
F 19
Li = 7 Na =* 23 — — S = 32
Cl = 35,»
K 39
C = 40
«
? = 45
Se = 79,4
Br = S0
Rb = 85,4
Sr = 87,«
Ce = 92
Te = l 28?
-
1 127
Cs = 133
Ba = 137
—
Tl = 204
Pb 207.

?Er = 56 La = 94
?Yt = 60 Di = 95
?ln = 75,« Th = 118?
a noTOny npnxojiHTCj si paanuxi pujoxi HITITI pauitiuoe ujubitcoie paaRoereft ,
Moro .
nin si nssauxi <ncxaxi upe TJaracaoS rattixitu .
me npMjeTC* npeiao -
jar &Ti
-
npu cocras iema cvcTemu oseus moro HexocTanutHXi RICUOSI To H
xpyroe nuo suromo. Mai samerti oparoin , amdoxia
.
ecTecTseunuai COCT&IITB

Mendeleev created a table in which elements with similar properties

—
were grouped together a periodic table of the elements. His first peri -
.
odic table, shown in Figure 2 was published in 1869. Note that
Mendeleev placed iodine. I ( atomic mass 127 ) , after tellurium , Te ( atom -
ic mass 128 ). Although this contradicted the pattern of listing the ele -
ments in order of increasing atomic mass, it allowed Mendeleev to place
tellurium in a group of elements with which it shares similar properties.
Reading horizontally across Mendeleev 's table, this group includes oxy -
gen . O, sulfur. S. and selenium. Se. Iodine could also, ihen , be placed in
the group il resembles chemically, which includes fluorine F. chlorine..
Cl , and bromine. Br.
Mendeleev 's procedure left several empty spaces in his periodic
table ( see Figure 2 ). In 1871. the Russian chemist boldly predicted the
existence and properties of the elements that would fill three of the
spaces. By 1886. all three elements had been discovered. Today these
elements are known as scandium . Sc. gallium. Ga. and germanium . Ge.
Their properties are strikingly similar to those predicted by Mendeleev.

134 CHAPTER 5
 The success of Mendeleev s predictions persuaded most chemists to
accept his periodic table and earned him credit as the discoverer of the
periodic law. Two questions remained, however. ( 1) Why could most of
the elements be arranged in the order of increasing atomic mass but a
few could not? ( 2 ) What was the reason for chemical periodicity ?

Moseley and the Periodic Law

The first question was not answered until more than 40 years after
Mendeleev 's first periodic table was published. In 1911. the English sci -
entist Henry Moseley, who was working with Ernest Rutherford, exam -
ined the spectra of 38 different metals. When analyzing his data,
Moseley discovered a previously unrecognized pattern. The elements in
the periodic table fit into patterns better when they were arranged in

—
increasing order according to nuclear charge, or the number of protons
in the nucleus. Moseley 's work led to both the modern definition of SC
atomic number and the recognition that atomic number, not atomic / lNKS. | mi
Mr*
atiim by MM
*
mass, is the basis for the organization of the periodic table. Nrtoul SdMte iMdMn AUMM<M

Moseley’s discovery was consistent with Mendeleev 's ordering of the For a variety of links related to this
chapter, go to www scilinks. org
periodic table by properties rather than strictly by atomic mass. For K

example, according to Moseley, tellurium, with an atomic number of 52, Topic: Noble Gases
SciLinks code: MC 61038
belongs before iodine, which has an atomic number of 53. Today,
Mendeleev 's principle of chemical periodicity is correctly stated in what
is known as the periodic law: The physical ami chemical properties of the
elements are periodic functions of their atomic numbers. In other words,
when the elements are arranged in order of increasing atomic number,
elements with similar properties appear at regular intervals.
2
He
7 8 9 10

The Modem Periodic Table N O F Ne

15 16 17 18

The periodic table has undergone extensive change since Mendeleev 's P S Cl Ar
time ( see Figure 6 on pages 140- 141 ). Chemists have discovered new 33 34 35 36
elements and. in more recent years, synthesized new ones in the lab- As Se Br Kr
oratory. Each of the more than 40 new elements, however, can be 51 52 53 54
placed in a group of other elements with similar properties. The Sb Te I Xe
periodic table is an arrangement of the elements in order of their atomic
83 84
numbers so that elements with similar properties fall in the same col - Bi Po At
85
Rn
86

umn, or group.

The Noble Gases FIGURE 3 The noble gases, also

known as the Group IS elements,
Perhaps the most significant addition to the periodic table came with
are all rather unreaclive. As you will
the discovery of the noble gases. In 1894, English physicist John William read, the reason for this low reactiv -
Strutt ( Lord Rayleigh ) and Scottish chemist Sir William Ramsay dis- ity also accounts for the special place
covered argon. Ar. a gas in the atmosphere that had previously escaped occupied by the noble gases in the
notice because of its total lack of chemical reactivity. Back in 1868, periodic table.

THE PERIODIC LAW 135

 another noble gas. helium. He, had been discovered as a component of
the sun. based on the emission spectrum of sunlight . In 1 X 95. Ramsay
showed that helium also exists on Earth.
In order to fit argon and helium into the periodic table. Ramsay pro -
posed a new group. He placed this group between the groups now
known as Group 17 ( the fluorine family ) and Group 1 ( the lithium fam -
ily ). In 1898, Ramsay discovered two more noble gases to place in his
new group, krypton, Kr. and xenon. Xe. The final noble gas. radon. Rn,
was discovered in 1900 by the German scientist Friedrich Ernst Dorn.

The Lanthanides
Hie next step in the development of the periodic table was completed
in the early 1900s. It was then that the puzzling chemistry of the lan -
thanides was finally understood. The lanthanides are the 14 elements
with atomic numbers from 5K ( cerium, Ce ) to 7/ ( lutetium, Lu ). Because
these elements are so similar in chemical and physical properties, the
process of separating and identifying them was a tedious task that
required the effort of many chemists.

The Actinides
Another major step in the development of the periodic table was the
discovers of the actinides. The actinides are the 14 elements with atomic
Element Difference numbers from 90 ( thorium. Ih ) to 103 { luwrencium. Lr ). The lan-
and atomic In atomic thanides and actinides belong in Periods 6 and 7. respectively, of the
number numbers periodic table, between the elements of Groups 3 and 4. To save space,
He 2 , the lanthanides and actinides are usually set off below the main portion
8
Ne 10 : of the periodic table, as shown in Figure 6 on pages 140- 141.
co 8
:
a Ar 18 Periodicity
18
2 Kr 36 : Periodicity w ith respect to atomic number can be observed in any group
18
Xe 54
of elements in the periodic table. Consider the noble gases of Group IS.
32 The first noble gas is helium. He. It has an atomic number of 2. The ele -
Rn 86 ments following helium in atomic number have completely different
properties until the next noble gas. neon. Ne, which has an atomic num -
Li ber of 10, is reached. The remaining noble gases in order of increasing

N a 11 .! 8 atomic number are argon ( Ar. atomic number 18), krypton ( Kr. atomic
number 36 ). xenon ( Xe, atomic number 54 ). and radon ( Rn, atomic num -
8
a K 19 ber 86 ) . The differences in atomic number between successive noble
18 gases are shown in Figure 4. Also shown in Figure 4 are atomic -number
$ Rb 37 :
18 differences between the elements of Group 1. w hich are all solid, silvery
Cs 55 metals. As you can see. the differences in atomic number between the
32
Fr 87 Group 1 metals follow the same pattern as the differences in atomic
number between the noble gases.
Starting with the first member of Groups 13- 17. a similar periodic
FIGURE 4 In each of Groups l
pattern is repeated. The atomic number of each successive element is X.
anti IS. the differences between the
atomic numbers of successive ele - IX, IX. and 32 higher than the atomic number of the element above it.
ments are X. X. IX. IX. and 32. respec - In Section 2, you will see that the second mystery presented by
tively. Groups 2 and 13- 17 follow a Mendeleev’s periodic table —the reason for periodicity — is explained
similar pattern. by the arrangement of the electrons around the nucleus.

136 CHAPTER 5
QuickLAB Materials
Designing Your Own Periodic Table • index cards

Question Discussion
Can you design your own
periodic table using informa-
1 . Keeping in mind that the
information you have is similar
tion similar to that available
to that available to Mendeleev
to Mendeleev ?
in 1869, answer the following
questions.
Procedure a . Why are atomic masses
.
1 Write down the information given instead of atomic
numbers?
available for each element on
b. Can you identify each ele-
separate index cards. The fol-
ment by name ?
lowing information is appro-
priate: a letter of the alphabet 2. How many groups of
(A, B, C, etc .) to identify each elements, or families,
element; atomic mass; state; are in your periodic
density; melting point; boiling table ? How many
point; and any other readily periods, or series,
observable physical properties. are in the table ?
Do not write the name of the
element on the index card, but 3. Predict the 4
^*
^
keep a separate list indicating characteristics
the letters you have assigned to of any missing ele-
each element. ments.When you have fin-
ished, check your work using
2. Organize the cards for the ele- your separate list of elements
ments in a logical pattern as and a periodic table.
you think Mendeleev might
have done.

SECTION REVIEW 4. How do the atomic numbers of the elements with-

1. a. Who is credited with developing a method that in each of Groups 1, 2, and 13-18 of the periodic
led to the determination of standard relative table vary ? (Refer to Figure 4 as a guide.)
atomic masses ? Critical Thinking
b. Who discovered the periodic law ? 5. RELATING IDEAS Why are elements' atomic mass-
c. Who established atomic numbers as the basis es not in strict increasing order in the periodic
for organizing the periodic table? table, even though the properties of the elements
.
2 State the periodic law. are similar ? For example, by atomic mass, telluri-
um, Te, should be in group 17 and iodine, I, should
3. Name three sets of elements that have been be in Group 16, but grouping by properties has Te
added to the periodic table after Mendeleev's in Group 16 and I in Group 17.
time.

THE PERIODIC LAW 137

 SECTION 2
Electron
OBJECTIVES Configuration and
Describe the relationship
between electrons in sub -
levels and the length of each
period of the periodic table.
the Periodic Table
v Locate and name the four
blocks of the periodic table.
Explain the reasons for T he Group 18 elements of the periodic table ( the noble gases) under -
these names. go few chemical reactions. This stability results from the gases * special
electron configurations. Helium's highest occupied level, the I s orbital,
is completely filled with electrons. And the highest occupied levels of
^ Discuss the relationship the other noble gases contain stable octets. Generally the electron con-
between group configurations
and group numbers. figuration of an atom ’s highest occupied energy level governs the
atom’s chemical properties.

"J Describe the locations in

the periodic table and the
general properties of the Periods and Blocks of the
alkali metals, the alkaline -
earth metals, the halogens,
Periodic Table
and the noble gases.
While the elements are arranged vertically in the periodic table in
groups that share similar chemical properties, they are also organized
horizontally in rows, or periods. ( As shown in Figure 6, there are a total
of seven periods of elements in the modern periodic table. ) As can be
seen in Table I, the length of each period is determined bv the number
of electrons that can occupy the sublevels being filled in that period.

TABLE 1 Relationship Between Period Length and

Sublevels Being Filled in the Periodic Table
Period Number of Sublevels in
number elements in period order of filling
l 2 Is
2 8 2s 2 p
3 8 3s 3 p
4 18 4s 3d 4 p
5 18 5s 4 d 5 p
6 32 6 s 4 f 5d 6 p
7 32 Is 5 f 6d . etc.

138 CHAPTER 5
 In the first period, the l.v sublevel is being filled. The Is sublevel can
hold a total of two electrons.Therefore, the first period consists of two
elements—hydrogen and helium. In the second period, the 2.v sub -
level. which can hold two electrons, and the 2p sublevel, which can
hold six electrons, are being filled. Consequently, the second period
totals eight elements. Similarly, filling of the 3s and 3p sublevels
accounts for the eight elements of the third period. Filling 3d and 4d
sublevels in addition to the x and p sublevels adds 10 elements to both
.
the fourth and fifth periods Therefore, each of these periods totals
18 elements. Filling 4/ sublevels in addition to s, p, and d sublevels
adds 14 elements to the sixth period, which totals 32 elements. And as
new elements are created, the 2 C) known elements in Period 7 could, in
theory, be extended to 32.
The period of an element can be determined from the element 's
electron configuration. For example, arsenic. As, has the electron
configuration [ Ar ]3rfln4.v:4p \ The 4 in 4/C indicates that arsenic's
highest occupied energy level is the fourth energy level. Arsenic is
therefore in the fourth period in the periodic table. The period and
electron configuration for each element can be found in the periodic
table on pages 140- 141.
Based on the electron configurations of the elements, the periodic
table can be divided into four blocks, the s, p , d. and / blocks. This divi-
.
sion is illustrated in Figure 5 The name of each block is determined
by whether an x, p, < /, or / sublevel is being filled in successive ele -
ments of that block .
FIGURE 5 Based on the electron
configurations of the elements, the
periodic table can be subdivided into
four sublevel blocks.

Group 18
1 s block elements
*

2
H p- block elements
Group 1 Group 2 Group 13 Group 14 Group IS Group 16 Group 17
He
3 4
d-block elements 5 6 7 8 9 10
Li Be f- block elements B C N 0 F Ne
11 12 13 14 15 16 17 18
Na Mg Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12
Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub Uut Uuq Uup

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
90 91 92 93 - 94 95 % 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

THE PERIODIC LAW 139

 Periodic Table of the Elements
l

i
H
Hydrogen
1.007 94
W Atomic number 6
Group 1
3
Group 2
4
Symbol
c
Li Be Name Carbon
2
Lithium
6.94 !
Beryllium
9.012 102
Average atomic mass -12.0107
[He|2 s i (He|2s Electron configuration [He]2s22p2
11 12

3
Na Mg
Sodium Magnesium
22.989 770 24.3050
a
"
[Ne]3s2
o
at
|Ne|3s
' Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9
Q . 20 21 22 23 24 25 26 27
19
K Ca Sc Ti V Cr Mn Fe Co
4 Vanadium Chromium Manganese Iron Cobalt
Potassium Calcium Scandium Titanium
39.0983 40.078 44.955 910 47.867 50.9415 51.9961 54.938 049 55.845 58.933 200
(Ar|4s . (Arjk/ As 2 IAr]3d54 s [Arl5d54 s 2 |Afj3</ 64s 2 [Ar]3d:4s 2
[Ar|4 s ' ' [Ar)3d24s 2 [Ar)3d34 s 2 '
37 38 39 40 41 42 43 44 45

5
Rb Sr Y Zr Nb Mo Tc Ru Rh
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium
85.4678 87.62 88.905 85 91.224 92.906 38 95.94 (98) 101.07 102.905 50
(KrlSs1 [Kr]5s. JKr) 4</ 15 s 2 (Krj4d35s 2 [Kf J4d*5 s' (Kr|AdW (KrHd^Sj1 [Krl4d ?5s ' [Kr]4 c/ B5sI

55 56 57 72 73 74 75 76 77

6
Cs Ba La Hf Ta W Re Os Ir
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium
132.905 43 137.327 138 9055 178.49 180.9479
[Xe|4 / u5dV
183.84 186.207
[Xej4 / u5dW
,
190.23 192.217
(Xe]4 / 45d 6s 2
^'Vfis
2
fXe|6s ' '
[Xe|5£/ 6S 2 [Xe[4 / ' W [Xe]4 /uSd 46s 2 * [Xe

87 88 89 104 105 106 107 108 109

7 Fr Ra Ac Rf Db Sg Bh Hs Mt
Francium Radium Actinium Rutherfordwm Dubmum Seaborgium Bohrium Hassium Meitnerium
(223)
[Rn|7sI
(226)
[Rn] 7 s 2
( 227)
|Rnl6d!7s 2
,
(261)
fRn|5 Z 46£/ 27s2
,
( 262)
|Rnl5 / 46d37s 2
(266)
|Rn|5 fM6d*7s 2
,
( 264)
[Rnl5 / 46flfs7!l2
,
( 277)
(Rn|5/ 46J^7s 2
,
( 268)
[Rn|5 f 46d ? 7j2

• The systematic names and symbols

for elements greater than 110 will
be used until the approval of trivial
names by IUPAC. 61 62
58 59 60

* iTiTCA i iH- Ce Pr Nd Pm Sm
Cerium Praseodymium Neodymium Promethium Samarium
140.116 140.907 65 144.24 (145) 150.36
90 . V Topic: Periodic Table
pceH / Sc/ 'Ss 2 (Xe|4 /J6s2 [Xej4 fV [Xej4 / 56s 2 pCe)4f 6s2
*
hriV G To: go.hrw.com ’
.fcOVll Keyword
° : HOLT PERIODIC
90 91 92 93 94
Visit the HRW Web site for updates Pu
on the periodic table.
Th Pa U Np
Thorium Protactinium Uranium Neptunium Plutonium
232.0381 231.035 88 238.028 91 (237) (244)
[Rn|5 f7s 2
[Rn)6d 27s 2 (Rnj5 / 26d 7s 2
' [Rn|5 / 36d 7s 2
' ^ '
[Rn)5 6c/ 7s 2

FIGURE 6 In the common periodic table, the elements

are arranged in vertical groups and in horizontal periods.

140 CHAPTER 5
 Hydrogen
Semiconductors
(also known as metalloids ) Group 18
2
Metals
Alkali metals
He
Helium
Alkaline- earth metals 4.002 602
Is 2
Transition metals Group 13 Group 14 Group 15 Group 16 Group 17
Other metals 5 6 7 8 9 10
Nonmetals B C N O F Ne
Halogens Boron Carbon Nitrogen Oxygen Fluorine Neon
10.811 12.0107 14.0067 15.9994 18.998 4032 20.1797
Noble gases [Hel2s ‘V (HefesV pfcpsV [He|2sV [He)2stys
Other nonmetals
13 14 15 16 17 18
A1 Si P S Cl Ar
Aluminum Silicon Phosphorus Sulfur Chlorine Argon
26.981 538 28.0855 30.973 761 32.065 35.453 39.948
[Nelis 'V [Ne|3sV (NepsV (Nelis;V‘ MssV |Ne|3$ V
Group 10 Group 11 Group 12
28 29 30 31 32 33 34 35 36
Ni Cu Zn Ga Ge As Se Br Kr
Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
58.6934 63.546 65.409 69.723 72.64 74.921 60 78.96 79.904 83.798
lArWV WSW |Arj3cT4s *y [Ar]Wl44sV (ArJW 'Vy |Ar)3</ ' J4sy (Ar|3rfl04s;4p
[Ar|3d' 34s 2 |Ar|
‘
46 47 48 49 50 51 52 53 54
Pd Ag Cd In Sn Sb Te I Xe
Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
106.42 107.8682 112.411 114.818 118.710 121.760 127.60 126.904 47 131.293
[Kr}4dV [Kr }4<P5sy (Kr|4d'V 5p 2 [KryVSp 1 pcryw |Krj4d P5s;5pi [Krl4</ ’c5sy
[Kr|4<P5s 9
^Ss'
(Krl

78 79 80 81 82 83 84 85 86

Pt Au Hg T1 Pb Bi Po At Rn
Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
195.078 196.966 55 200.59 204.3833 207.2 208.980 38 ( 209) ( 210) ( 222)
, ,
[XeJtf ' V6s (feHWW [Xe]4/ W [Xe|4/ U5d t6s 26p [Xe|4r 5d afoy [XeH/ ' V
^y ^WW
[Xe IpWVW (Xe)4/'*5d*fcy

110 111 112 113 114

Ds Uuu Uub* Uut* Uuq*
Oarmstadtium Ununumum Ununbium Ununtrium Ununquadwm Ununpentium
( 281) ( 272) (285) ( 284) ( 289) ( 288)
. (Rn)sPWsty (Rn|5f 'WWp*
^Wp
1
IRnlST&W (RnlW ' j1
^ |Rn]Sf '

A team at Lawrence Berkeley National Laboratories reported the discovery of elements 116 and 118 in June 1999.
The same team retracted the discovery in July 2001. The discovery of elements 113, 114, and 115 has been reported but not confirmed.

63 64 65 66 67 68 69 70 71
Eu Gd Tb Dy Ho Er Tm Yb Lu
Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
151.964 157.25 158.925 34 162.500 164.930 32 167.259 168.934 21 173.04 174.967
(Xej4/;5d:fe2 [Xej4T6s:
, (Xe|4/n6s 2
[Xe]4I6s‘ |Xe}4/ u65 ' (Xe)4/ ”fo' |Xej4/’V (Xe)4/ V ixenrw
95 96 97 98 99 100 101 102 103
Am Cm Bk Cf Es Fm Md No Lr
Americium Curium Berkefium Californium Einsteinium fermium Mendelevium Nobelium Lawrenaum
( 243) (247) (247) (251) (252) (257) (258) (259) ( 262)
[Rn]5V?sl [Rn|5/ '6d'7s; [Rn)5/! l 7s; [Rnj5/' 27s 2 IRnjsW |Rnj5/ w 7sJ |Rn|5/ *6d 7s:
msTO ‘
The atomic masses listed in this table reflect the precision of current measurements. (Values
listed in parentheses are those of the element's most stable or most common isotope.)

THE PERIODIC LAW 141

 The 5- Block Elements: Groups 1 and 2
The elements of the s block are chemically reactive metals. The Group I
metals are more reactive than those of Group 2. The outermost energy
level in an atom of each Group 1 element contains a single .v electron.
For example, the configurations of lithium and sodium are [ HeJZy 1 and
|Neps 1. respectively. As you will learn in Section 3. the ease with which
the single electron is lost helps to make the Group 1 metals extremely
reactive. Using n for the number of the highest occupied energy level,
the outer, or group, configurations of the Group 1 and 2 elements are
written ns ] and ns 2 , respectively. For example, the configuration of Na is
(Nep.v 1. so the group configuration is written ns 1 . where n = 3.
The elements of Group I of the periodic table ( lithium , sodium , potas -
sium. rubidiutn, cesium , and francium ) are known as the alkali metals. In
their pure state, all of the alkali metals have a silvery appearance and
are soft enough to cut with a knife. However, because they are so reac -
tive, alkali metals are not found in nature as free elements. They com -
bine vigorously with most nonmetals. And they react strongly with
water to produce hydrogen gas and aqueous solutions of substances
known as alkalis. Because of their extreme reactivity with air or mois-
ture. alkali metals are usually stored in kerosene. Proceeding down the
column, the elements of Group I melt at successively lower tempera-
tures.
The elements of Group 2 of the periodic table ( beryllium , magnesium,
POTASSIUM calcium , strontium , barium , and radium ) are called the alkaline-earth
.
metals Atoms of alkaline- earth metals contain a pair of electrons in
their outermost s sublevel. Consequently, the group configuration for
Group 2 is ns 2 . The Group 2 metals are harder, denser, and stronger
than the alkali metals. They also have higher melting points. Although
they are less reactive than the alkali metals, the alkaline-earth metals
are also too reactive to be found in nature as free elements.

Hydrogen and Helium

FIGURE 7 ( a ) Like other alkali Before discussing the other blocks of the periodic table, let ’s consider
metals, potassium reacts so strongly two special cases in the classification of the elements— hydrogen and
with water that ( b ) it must be stored helium. Hydrogen has an electron configuration of 1 A 1 . but despite the
]
m kerosene or oil to prevent it from ns configuration, it does not share the same properties as the elements
reacting with moisture in the air.

FIGURE 8 Calcium, an alkaline -

earth metal is too reactive to be
,

found in nature in its pure stale ( a ).

Instead, it exists in compounds, such
as in the minerals that make up
marble ( b ). ( a) ( b)

142 CHAPTER 5
of Group I . Although it is located above the Group 1 elements in many
periodic tables, hydrogen is a unique element, with properties that do
not closely resemble those of any group.
SCllNKS. 0
Mft
iMtfrtjMwd fry I N
NADMML SdMcc TMCNTI Auocutkm
Like the Group 2 elements, helium has an ns 2 group configuration. Yet For a variety of links related to this
it is part of Group IX. Because its highest occupied energy level is filled chapter, go to vvwvv.scilinks.org
by two electrons, helium possesses special chemical stability, exhibiting
.
the unreactive nature of a Group IX element By contrast, the Group 2
Topic: Alkali Metals
SciLinks code: HC60043
^
metals have no special stability: their highest occupied energy levels are Topic: Alkaline - Earth Metals
not filled because each metal has an empty available p sublevel . Sci Links code: HC60Q44

SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.

a. Without looking at the periodic table, identify the group, period, and block in which the
element that has the electron configuration |Xe|6.r is located .
b. Without looking at the periodic table, write the electron configuration for the Group 1 element in the
third period. Is this element likely to be more reactive or less reactive than the element described in ( a)?

SOLUTION a. The element is in Group 2. as indicated bv the group configuration of ns2. It is in the
sixth period, as indicated by the highest principal quantum number in its configuration,
6. The element is in the s block .

b. In a third-period element, the highest occupied energy level is the third main energy
level, n = 3. The Is, 2s, and 2 p sublevels are completely filled ( see Table 1 ). A Group 1
element has a group configuration of /is 1, which indicates a single electron in its highest
s sublevel. Therefore, this element has the following configuration:

1S22S22/;63SI or ( Ne ]3s !
Because it is in Group 1 ( the alkali metals ), this element is likely to be more reactive
than the element described in ( a ), which is in Group 2 ( the alkaline-earth metals).

PRACTICE Answers in Appendix E

1. Without looking at the periodic table, identify the group, period,

and block in which the element that has the electron configuration
[ KrJ5sj is located.
2. a. Without looking at the periodic table, write the group configura-
tion for the Group 2 elements.
Go to go.hrw.com for
b. Without looking at the periodic table, write the complete elec - more practice problems
tron configuration for the Group 2 element in the fourth period.
that ask you to relate
positions of elements
c. Refer to Figure 6 to identify the element described in ( b ). in the periodic table
Then, write the element 's noble-gas notation. with electron
configurations.
Keyword: HC 6 PERX

THE P E R I O D I C L A W 143
 FIGURE 9 The diagram
shows the electron configuration of ti T
T TI TI TI 2
>* V.
U)
scandium . Sc. the Group 3 element a> | 3d
of the fourth period. In general , the
( / / - 1 )il sublevel in Groups 3-12 is
C
LU

TI - TI TI TI 2 3p

occupied by electrons after the ns

sublevel is filled .
TI *
1s
2p

The d- Block Elements: Groups 3- 12

For energy level / /, there are n possible sublevels, so the d sublevel first
appears when n = 3. This 3d sublevel is slightly higher in energy than the
4s sublevel , so these are filled in the order 4.v3// (see Figure 9 ) . This order
of filling is also seen for higher values of / / . Each d sublevel consists of five
orbitals with a maximum of two electrons each , or up to 10 electrons pos-
sible in each d sublevel. In addition to the two ns electrons of Group 2,
atoms of the Group 3 elements each have one electron in the d sublevel
of the ( / / - 1 ) energy level. The group configuration for Group 3 is there -
fore ( / / - 1 )dlns2 . Atoms of the Group 12 elements have 10 electrons in
the d sublevel plus two electrons in the ns sublevel. The group configura -
tion for Group 12 is ( / / - 1 )dU ns2.
)

As you read in Chapter 4, some deviations from orderly d sublevel

filling occur in Groups 4- 11 . As a result , elements in these / / - block
groups, unlike those in 5- block and // - block groups, do not necessarily
have identical outer electron configurations. For example, in Group 10,
nickel, Ni . has the electron configuration [ Ar|3/ / S4 v2. Palladium. Pd. has
,
the configuration [ Kr ]4/ / 055°. And platinum , Pt . has the configuration
[ Xe ]4/ l 45frW . Notice, however, that in each case the sum of the outer s
and d electrons is equal to the group number.
-
The d block elements are metals with typical metallic properties and
are often referred to as transition elements. They are good conductors of
electricity and have a high luster. They are typically less reactive than
the alkali metals and the alkaline-earth metals. Some are so unreactive
FIGURE 10 Mercury, tungsten ,
that they do not easily form compounds, existing in nature as free ele -
and vanadium are transition elements. ments. Palladium , platinum , and gold are among the least reactive of all
Locate them in the d block of the the elements. Some / /- block elements are shown in Figure 10.
—
periodic table on pages 140 141.

© O
W *o
a a
Mercury Tungsten Vanadium

144 CHAPTER 5
 CAREERS
in Chemistry

Materials Scientist
Almost everything we use or wear is new materials that have the desired
composed of materials. Materials can properties. Typical properties of inter -
include metals, ceramics, polymers, est are mechanical, such as tensile
semiconductors, and composites. strength or hardness; electrical, such
Metals have been used for thousands as conductivity or resistivity; magnet -
of years. Metals are good conductors ic, such as magnetic susceptibility;
of heat and electricity. They are strong optical, such as refractive index; ther -
but deformable. Ceramics are typically mal, such as heat capacity or thermal
compounds made up of both metals conductivity; and environmental, such
and nonmetals. Usually, ceramics are as corrosion behavior. Performance
A Materials scientists study the
insulators and are resistant to high testing and analysis ensures that the
microstructure of materials, testing how
temperatures. Examples of products product has the desired properties. they behave under various conditions.
that contain ceramics are dishes, Because a property or a structural
building materials, bone and tooth characterization of a material closely science. An undergraduate degree in
replacements, and high- speed com- depends on the processing used, materials science and engineering,
munications equipment. Polymers are evaluation often improves the chemistry, physics, or engineering can
generally organic compounds and process used to make the material. lead to a career in this field. Many
have very large molecular structures. materials scientists obtain a more
Careers in Materials Science
Polymer products include toys, stor - advanced degree, such as a master's
Materials scientists go by many dif -
age containers, paints, and biomedical degree in materials science and engi-
ferent titles, such as process or pro -
items; plastics (polymers) are every- neering or a doctorate (Ph.D.) in
duction engineers, research
where. The electrical properties of chemistry, physics, or engineering.
scientists, metallurgists, polymer sci-
semiconductors are between those of The materials field is exciting and
entists, ceramic engineers, plant
conductors and insulators. Computers, expanding. The ability to create mate-
managers, and quality control engi -
calculators, and cell phones are just a rials to meet specific needs is just
neers. Materials scientists are
few examples of products that use starting to be realized. With the devel-
employed in industries such as trans-
semiconductors. Composites, such as oping field of materials science, many
portation, electronics, aerospace, and
ceramics and polymers, are found in say we are living in the Materials Age.
biomedical engineering or work for
flooring, tiles, bicycles, space shuttles,
research laboratories, the govern-
and insulation. Questions
ment, or universities. Materials scien -
Materials science includes the 1. Choose a product you might use
tists help determine what materials
study of the processing, structure, in your daily life. Discuss the ma -
should be used in products based on
properties, and performance of mate- terials that compose the product
desired properties, help synthesize
rials. Processing involves manufactur - and the properties that those
new materials, and help produce
ing the material from its raw materials give the product.
these materials efficiently.
components. Structure refers to the
Because of the interdisciplinary 2. Using the Internet, find a profile of
arrangement of the material's com-
nature of this field, many kinds of pro - a materials scientist or engineer,
ponents from an atomic to a macro
grams, disciplines, or majors can pre - and describe what that scientist or
scale. Understanding the structure
pare a person for a career in materials engineer does in her or his position.
helps materials scientists develop

THE P E R I O D I C L A W 145
 SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter.

An element has the electron configuration | Kr |4^/ ''5 v 1. Without looking at the periodic table, identify the
.
period, block, and group in which this element is located Then, consult the periodic table to identify this
element and the others in its group.

SOLUTION The number of the highest occupied energy level is 5. so the element is in the filth period.
There are five electrons in the il sublevel, which means that it is incompletely filled. The
d sublevel can hold 10 electrons. Therefore, the element is in the il block . For r /- block ele -
ments. the number of electrons in the ns sublevel ( 1 ) plus the number of electrons in the
( n - I )d sublevel ( 5 ) equals the group number. 6. This Group b element is molybdenum.
The others in Group 6 are chromium, tungsten, and seaborgium.

PRACTICE Answers in Appendix E

1. Without looking at the periodic table, identify the period, block,

and group in which the element that has the electron configura- Go to go.hrw.com for
tion [ Ar ).V/ s4.v - is located. more practice problems
that ask you to use the
2 . Without looking at the periodic table, write the outer electron electron configurations
configuration for the Group 12 element in the fifth period. of elements to locate
those elements in the
periodic table.
Keyword: HC 6 PERX

The p- Block Elements: Groups 13- 18

4Tic p-block elements consist of all the elements of Groups 13- 18 except
helium. Electrons add to a p sublevel only after the s sublevel in the same
energy level is filled.Therefore, atoms of all //-block elements contain two
electrons in the ns sublevel. Thep -block elements together with the s- block
.
elements are allied the main-group elements For Group 13 elements the ,

added electron enters the np sublevel, giving a group configuration of

nsrnp\ Atoms of Group 14 elements contain two electrons in the p sub -
level. giving mrnp1 for the group configuration. I his pattern continues in
.
Groups 13- 18. In Group 18 the stable noble-gas configuration of ns2nph
is reached. The relationships among group numbers and electron config-
urations for all the groups are summarized in Table 2 .
For atoms of p-block elements, the total number of electrons in the
highest occupied level is equal to the group number minus 10. For
example, bromine is in Group 17. It has 17 - 10 = 7 electrons in its high -
est energy level. Because atoms of p-block elements contain two elec -
trons in the ns sublevel, we know that bromine has five electrons in
its outer p sublevel. The electron configuration of bromine is
,
| Ar ]3</ 04s24p \
The properties of elements of the p block vary greatly. At its right -
hand end. the p block includes all of the nonmetals except hydrogen and
helium. All six of the metalloids ( boron, silicon, germanium, arsenic .
146 CHAPTER 5
 TABLE 2 Relationships Among Group Numbers, Blocks, and Electron Configurations
Group number Group configuration Block Comments
1, 2 1
ns ' * s One or two electrons in ns sublevel
( n - ! ) </ .. Jr 2
- io
3- 12
' ns ( I Sum of electrons in ns and ( n - 1 )d
levels equals group number
13-18 ns2np 1 6
P Number of electrons in np sublevel equals
group number minus 12

antimony, and tellurium ) are also in the p block. At the left -hand side
and bottom of the block, there are eight p-block metals. The locations
of the nonmetals, metalloids, and metals in the p block are shown with
distinctive colors in Figure 6.
The elements of Group 17 (fluorine, chlorine, bromine. iodine and . L\ir >
.
astatine ) are known as the halogens, shown in Figure 11 The halogens Drolopttf M4 naMAin
* by tlw
RltlMMl SotlKt ItKlKn AtUKklllM

are the most reactive nonmetals. They react vigorously with most metals For a variety of links related to this
to form examples of the type of compound known as salts. As you will chapter, go to WINW.srilinks. org
see later, the reactivity of the halogens is based on the presence of seven
electrons in their outer energy levels—one electron short of the stable
Topic: Halogens
SciLinks code: HC60710
^
noble-gas configuration. Fluorine and chlorine are gases at room tem -
perature. bromine is a reddish liquid, and iodine is a dark purple solid.
Astatine is a synthetic element prepared in only very small quantities.
Most of its properties are estimated, although it is known to be a solid.
The metalloids, or semiconducting elements, are located between
nonmetals and metals in the p block. They are mostly brittle solids with
some properties of metals and some of nonmetals. The metalloid ele-
ments have electrical conductivity intermediate between that of metals,
which are good conductors, and nonmetals, which are nonconductors.
Hie metals of the p block are generally harder and denser than the
FIGURE 11 Fluorine, chlorine,
.v-block alkaline-earth metals, but softer and less dense than the rf-block bromine, and iodine are members
metals. With the exception of bismuth, these metals are sufficiently reac - of Group 17 of the periodic table,
tive to be found in nature only in the form of compounds. Once also known as the halogens. Locate
obtained as free metals, however, they are stable in the presence of air. the halogens in the p block of the
periodic table on pages 140- 141.

Chlorine

Fluorine Bromine Iodine

THE PERIODIC LAW 147

 SAMPLE PROBLEM C For more help, go to the Math tutor at the end of this chapter.

Without looking at the periodic table, write the outer electron configuration for the Group 14 element in
.
the second period Then, name the element, and identify it as a metal, nonmetal, or metalloid.

SOLUTION The group number is higher than 12, so the element is in the p block. The total number of
electrons in the highest occupied s and p sublevels is therefore equal to the group number
minus 10 ( 14 - 10 = 4 ). Two electrons are in the s sublevel, so two electrons must also be
present in the 2p sublevel, which means that the outer electron configuration is 2r 2/r. The
element is carbon, C. which is a nonmetal.

PRACTICE Answers in Appendix E

1. a. Without looking at the periodic table, write the outer electron

configuration for the Group 17 element in the third period.
b. Name the element described in ( a ), and identify it as a metal,
nonmetal, or metalloid.
— iTftrra
2. a. Without looking at the periodic table, identify the period, Go to go.hrw.com for
block, and group of an element that has the electron configura- more practice problems
.
tion ( Ar|3r/ l04v24/;3. that ask you to classify
elements and write their
b. Name the element described in ( a ), and identify it as a metal, electron configurations
nonmetal, or metalloid. based on their period
and group.
Keyword: HC 6 PERX

The f- Block Elements: Lanthanides and Actinides

In the periodic table, the /- block elements are wedged between Groups
3 and 4 in the sixth and seventh periods. Their position reflects the fact
that they involve the filling of the 4/ sublevel. W ith seven 4 / orbitals to
be filled with two electrons each, there are a total of 14 / - block elements
.
between lanthanum La, and hafnium, Hf, in the sixth period. Hie
lanthanides are shiny metals similar in reactivity to the Group 2
alkaline-earth metals.
There are also 14 /-block elements, the actinides, between actinium.
Ac and element 104. Rf, in the seventh period. In these elements the 5/
,
sublevel is being filled with I4 electrons. The actinides are all radioac-
.
tive The first four actinides ( thorium.Th. through neptunium, Np ) have
been found naturally on Earth. The remaining actinides are known only
as laboratory - made elements.

SAMPLE PROBLEM D

Hie electron configurations of atoms of four elements are written at the top of page 149. Name the block
and group in which each of these elements is located in the periodic table. Then, use the periodic table on
pages 140-141 to name each element. Identify each element as a metal, nonmetal, or metalloid .
148 CHAPTER 5
 Finally, describe whether each element has high reactivity or low .
reactivity

a. |\c ]4fu5d 96sl c. [ Ne|3r 3//'

b. |Ne |3 V23/;5 d. [ XeH/W

SOLUTION .
a The 4/ sublevel is filled with 14 electrons. The 5d sublevel is partially filled with nine
electrons. Therefore, this element is in the d block. The element is the transition metal
platinum, Pt . which is in Group 10 and has a low reactivity.

b. The incompletely filled p sublevel shows that this element is in the p block. A total of
seven electrons are in the ns and np sublevels, so this element is in Group 17, the halo-
gens. The element is chlorine. Cl. and is highly reactive.

c. This element has a noble-gas configuration and thus is in Group IS in the p block . The
element is argon, Ar, which is an unreactive nonmetal and a noble gas.

d. Hie incomplete 4/ sublevel shows that the element is in the / block and is a lanthanide.
Group numbers are not assigned to the / block. The element is samarium, Sm. All of the
lanthanides are reactive metals.

PRACTICE Answers in Appendix E TTTTtd iTftd il

Go to go.hrw.com for
1. For each of the following, identify the block, period, group, group more practice problems
name ( where appropriate ), element name, element type ( metal, that ask you to locate
nonmetal, or metalloid), and relative reactivity ( high or low ): elements on the
periodic table and
a. [ He ]2s22/r5 b. [ Ar ]3d104.vl predict their properties
based on their electron
configurations.
Keyword: HC 6 PERX

SECTION REVIEW 5. Without looking at the periodic table, identify the

1. Into what four blocks can the periodic table be period, block, and group of the element that has
divided to illustrate the relationship between the the electron configuration [ Ar ]3 d74s2.
elements ' electron configurations and their place- Critical Thinking
ment in the periodic table?
6. APPLYING MODELS Period 7 contains elements in
2. What name is given to each of the following the s, p, d, and f blocks. Suppose that there were
groups of elements in the periodic table ? a Period 8 and it contained elements in the " g "
a. Group 1 c. Groups 3-12 e. Group 18 block, where " g" had the angular momentum
b. Group 2 d. Group 17 quantum number f = 4. If a hypothetical element
in Period 8 had an atomic number of 120, into
3. What are the relationships between group what group in the periodic table would the ele-
configuration and group number for ment fit, and what properties might it have
elements in the s, p, and d blocks? (assuming it does not radioactively decay) ?
4. Without looking at the periodic table, write the
outer electron configuration for the Group 15
element in the fourth period.

THE PERIODIC LAW 149

 SECTION 3
Electron
OBJECTIVES Configuration and
v Define atomic and ionic radii,
ionization energy, electron
affinity, and electronegativity. Periodic Properties
Compare the periodic trends
* of atomic radii, ionization
energy, and electronegativity,
and state the reasons for S o far, you have learned that the elements are arranged in the peri-
these variations. odic table according to their atomic number and that there is a rough
correlation between the arrangement of the elements and their electron
configurations. In this section, the relationship between the periodic law
J Define valence electrons, and
state how many are present
and electron configurations will be further explored.
in atoms of each main- group
element.

Atomic Radii
Compare the atomic radii,
ionization energies, and
Ideally, the size of an atom is defined by the edge of its orbital. However,
electronegativities of the
d-block elements with those
.
this boundary is fuzzy and varies under different conditions Therefore,
to estimate the size of an atom, the conditions under which the atom
of the main - group elements.
exists must be specified. One way to express an atom's radius is to mea -
sure the distance between the nuclei of two identical atoms that are
chemically bonded together, then divide this distance by two. As illus-
trated in Figure 12, atomic radius may be defined as one- half the distance
between the nuclei of identical atoms that are bonded together .

Period Trends
Figure 13 gives the atomic radii of the elements and Figure 14 presents
.
this information graphically Note that there is a gradual decrease in
atomic radii across the second period from lithium, Li. to neon. Ne. The

Chlorine
nucleus
Atomic

*
FIGURE 12 One method of radius

.
determining atomic radius is to 00 pm
\
measure the distance between the
nuclei of two identical atoms that 200 pm
are bonded together in an element
or compound , then divide this
distance by two. The atomic radius Chlorine
of a chlorine atom, for example, is Distance nucleus
100 picometers ( pm ) . between nuclei

150 CHAPTER 5
Periodic Table of Atomic Radii ( pm )

Atomic Atomic
H 1 symbol number Group 18
1
37
C 6 He 2
1
Group 1 Group l Group 13 Group 14 Group 15 Group 16 Group 17
Atomic radius
Li 3 Be 4 B 5 C 6 N 70 8 F 9 Ne 10
2 Relative 2
152 112
atomic size 77 85 77 75 73 72 71
Na 11 Mg 12 Al 13 Si 14 P 15 S 16 Cl 17 Ar 18
3 3
186 160 Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12 1 -1 ' 118 110 103 100 98
T3
O K 19 Ca 20 Sc 21 Ti 22 V 23 Cr 24 Mn 25 Fe 26 Co 27 Ni 28 Cu 29 Zn 30 Ga 31 Ge 32 As 33 Se 34 Br 35 Kr 36 o
4 4 '
CL o
227 197 162 147 134 128 127 126 125 124 128 134 135 122 120 119 114 112 Q.

Rb 37 Sr 38 Y 39 Zr 40 Nb 41 Mo 42 Tc 43 Ru 44 Rh 45 Pd 46 Ag 47 Cd 48 In 49 Sn 50 Sb 51 Te 52 I 53 Xe 54
5 5
248 215 180 160 146 139 136 134 134 137 144 149 167 140 140 142 133 131
Cs 55 Ba 56 La 57 Hf 72 Ta 73 W 74 Re 75 Os 76 Ir 77 Pt 78 Au 79 Hg 80 TI 81 Pb 82 Bi 83 Po 84 At 85 Rn 86
6 6
265 222 183 159 146 135
139 137
136 139 144 151 170 175 150 168 » 40 141
Fr 87 Ra 88 Ac 89 Rf 104 Db 105 Sg 106 Bh 107 Hs 108 Mt 109 Ds 110 Uuu 111 Uub 112 Uut 113 Dug 114 Uup 115 116 117 118
7 7
270 220 188

Lanthanide series
Ce 58 Pr 59 Nd 60 Pm 61 Sm 62 Eu 63 Gd 64 Tb 65 Dy 66 Ho 67 Er 68 Tm 69 Yb 70 Lu 71

182 182 181 183 180 208 180 177 178 176 176 176 174
Th 90 Pa 91 U 92 Np 93 Pu 94 Am 95 Cm 96 Bk 97 Cf 98 Es 99 Fm 100 MdlOl No 102 Lr 103

179 163 156 155 159 173 174 186 186

Actinide series

FIGURE 13 Atomic radii decrease

from left to right across a period and
increase down a group.
trend to smaller atoms across a period is caused by the increasing posi-
tive charge of the nucleus. As electrons add to s and p sublevels in the
same main energy level, they are gradually pulled closer to the more
highly charged nucleus. This increased pull results in a decrease in atom -
ic radii. The attraction of the nucleus is somewhat offset by repulsion
among the increased number of electrons in the same outer energy
level. As a result , the difference in radii between neighboring atoms in
each period grows smaller, as shown in Figure 13 .
Group Trends
.
Examine ihe atomic radii of the Group I elements in Figure 13 Notice
that the radii of the elements increase as you read down the group. As
electrons occupy sublevels in successively higher main energy levels
located farther from the nucleus, the sizes of the atoms increase. In gen -
CHEMISTRY
Module 3 : Periodic Properties ^
eral, the atomic radii of the main - group elements increase down a group.
Now examine the radii of the Group 13 elements. Although gallium.
Ga . follows aluminum . Al . it has a slightly smaller atomic radius than
does aluminum . This is because gallium , unlike aluminum, is preceded
in its period by the 10 r/- block elements. The expected increase in gal -
lium 's radius caused by the filling of the fourth main -energy level is out -
weighed by a shrinking of the electron cloud caused by a nuclear charge
that is considerably higher than that of aluminum .

THE PERIODIC LAW 151

 Atomic Radius vs. Atomic Number
300
Period Period Period Period Period Period
2 3 4 6

250

^ 200
E Na
a
D
"O Li
2 150
u
E
o
<
100

Ne

50
H
\ He

0
0 10 20 30 40 50 60 70 80 90 100
Atomic number

FIGURE 14 The plot of atomic radius versus atomic number shows period and group trends.

SAMPLE PROBLEM E

.
Of the elements magnesium Mg, chlorine. Cl, sodium, Na, and phosphorus, P, which has the largest
atomic radius? Explain your answer in terms of trends in the periodic table.

SOLUTION All of the elements are in the third period. Of the four, sodium has the lowest atomic num -
ber and is the first element in the period. Therefore, sodium has the largest atomic radius
because atomic radii decrease across a period.

PRACTICE Answers in Appendix E

1. Which of the following elements has the largest atomic radius:

Li, O. C, or F ? Which has the smallest atomic radius?
.
2. Of the elements calcium, Ca, beryllium. Be barium. Ba, and
.
strontium. Sr which has the largest atomic radius? Explain
your answer in terms of trends in the periodic table. Go to go.hrw.com for
3. Of the elements aluminum. Al. magnesium. Mg. silicon Si, . more practice problems
that ask you to use periodic
.
and sodium Na. which has the smallest atomic radius? trends in atomic radius to
Explain your answer in terms of trends in the periodic table. predict relative sizes of
atoms.

Keyword: HC 6 PERX

152 CHAPTER 5
 Ionization Energy
An electron can be removed from an atom if enough energy is supplied.
Using A as a symbol for an atom of any element, the process can be
expressed as follows.

A + energy A* + e

The A represents an ion of element A with a single positive charge,

*

referred to as a 1+ ion. An ion is an atom or group of bonded atoms that

has a positive or negative charge. Sodium, for example, forms an Na+
ion. Any process that results in the formation of an ion is referred to as
ionization.
To compare the ease with which atoms of different elements give up
electrons, chemists compare ionization energies. The energy required to
remove one electron from a neutral atom of an element is the ionization
energy, IF ( or first ionization energy, IE \ ). To avoid the influence of near -
by atoms, measurements of ionization energies are made on isolated
atoms in the gas phase. Figure 15 gives the first ionization energies for
the elements in kilojoules per mole ( kJ/mol). Figure 16 presents this
information graphically.
FIGURE 15 In general, first ion -
ization energies increase across
a period and decrease down a group.

Periodic Table of Ionization Energies ( kJ / mol )

Atomic
1 number Group 18
2
i
H
1112
6 He i

2
Group 1 Group 2
3
Li
4
Be
c
1086
Symbol
Group 13 Group 14 Group 15 Group 16 Group 17
5
B C
6 7
N 0
8 9
F
2372
10
Ne 2
S20 900 801 1086 1402 1314 1681 2081
First ionization
11 12 13 14 15 16 17 18
energy
3
Na Mg Al Si P S Cl Ar 3
4% 738 Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12 787 10( 2 1000 1251 1521
§ 4 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

I
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 4 r
6
a.
419 590 633 659 651 653 717 762 760 737 746 906 579 762 947 941 1140 1351
37 38 39 : 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe ^
403 550 600 640 652 684 702 710 720 804 868 558 709 834 869 1008 H 70
5S 56 57 7i 73 74 75 76 77 78 79 80 81 82 83 84 85 86
6 Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn 6
376 503 538 659 761 770 760 839 878 868 890 111 589 716 703 812 1038
87 5 -3 89 104 05 106 107 108 109 no 111 112 113 114 115 116 117 118
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub Uut Uuq Uup 7
509 490

Lanthanide series
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
534 527 533 536 545 547 592 566 573 581 589 597 603 523
90 91 92 93 94 95 96 91 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
587 570 598 585 578 581 601 608 619 627 635 642
Actinide series

THE PERIODIC LAW 153

 First Ionization Energy vs. Atomic Number
3000
Period Period Period Period Period Period
2 3 4 5 6 7

2500
He
o
Ne
3 2000
2*

QJ
C
CD
c 1500
o
C
N
C
o
Z00 1000
u.

500

°0 10 20 30 40 50 60 70 80 90 100
Atomic number

FIGURE 16 Plot of first ionization

energy, / £, , versus atomic number .
As atomic number increases both , Period Trends
the period and the group trends In Figures 15 and 16, examine the ionization energies for the first and
become less pronounced. last elements in each period. You can see that the Group 1 metals have
the lowest first ionization energies in their respective periods.
Therefore, they lose electrons most easilv. This ease of electron loss is a
major reason for the high reactivity of the Group 1 ( alkali ) metals. The
Group 18 elements, the noble gases, have the highest ionization ener -
gies. They do not lose electrons easily. The low reactivity of the noble
gases is partly based on this difficulty of electron removal .
hi general, ionization energies of the main - group elements increase
across each period . This increase is caused by increasing nuclear charge.
A higher charge more strongly attracts electrons in the same energy level .
Increasing nuclear charge is responsible for both increasing ionization
energy and decreasing radii across the periods. Note that , in general ,
nonmetals have higher ionization energies than metals do. In each pe -
riod . the element of Group I has the lowest ionization energy and the
element of Group 18 has the highest ionization energy.

Group Trends
Among the main - group elements, ionization energies generally decrease
down the groups. Electrons removed from atoms of each succeeding
element in a group are in higher energy levels, farther from the nucleus.
Therefore, thev* are removed more easily. Also, as atomic number
J

154 CHAPTER 5
increases going down a group, more electrons lie between the nucleus
and the electrons in the highest occupied energy levels. This partially
CROSS- DISCIPLINARY
shields the outer electrons from the effect of the nuclear charge.
Go to go. hrw.com for a full - length
Together, these influences overcome the attraction of the electrons to
article on elements and nutrition .
the increasing nuclear charge.
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Removing Electrons from Positive Ions

With sufficient energy, electrons can be removed from positive ions as
w ell as from neutral atoms. The energies for removal of additional elec-
trons from an atom are referred to as the second ionization energy ( I E 2 ),
,
third ionization energy ( I E ), and so on .
Table 3 shows the first five ionization energies for the elements of
the first , second , and third periods. You can see that the second ioniza -
tion energy is always higher than the first , the third is always higher than
the second , and so on . This is because as electrons are removed in suc-
cessive ionizations, fewer electrons remain within the atom to shield the
attractive force of the nucleus. Thus, each successive electron removed
from an ion feels an increasingly stronger effective nuclear charge ( the
nuclear charge minus the electron shielding ) .
The first ionization energies in Table 3 show that removing a single
electron from an atom of a Group 18 element is more difficult than
removing an electron from atoms of other elements in the same period.
This special stability of the noble -gas configuration also applies to ions
that have noble -gas configurations. Notice in Table 3 the large increases
between the first and second ionization energies of lithium , Li , and
between the second and third ionization energies of beryllium . Be. Even
larger increases in ionization energy exist between the third and fourth

TABLE 3 Ionization Energies ( in kJImol ) for Elements of Periods 1-3

Period 1 Period 2
H He Li Be B C N O F Ne
/ £, 1312 2372 520 900 801 1086 1402 1314 1681 2081
IE 2 5250 7298 1757 2427 2353 2856 3388 3374 3952
IE , 11 815 14 849 3660 4621 4578 5300 6050 6122
I E4 21 007 25 026 6223 7475 7469 8408 9370
IE , 32 827 37 830 9445 10 990 11 023 12 178
Period 3
Na Mg A1 Si P S Cl Ar
/£ , 496 738 578 787 1012 1000 1251 1521
IE 2 4562 1451 1817 1577 1903 2251 2297 2666
IE , 6912 7733 2745 3232 2912 3361 3822 3931
IE 4 9544 10 540 11 578 4356 4957 4564 5158 5771
IE , 13 353 13 628 14 831 16 091 6274 7013 6540 7238

THE PERIODIC LAW 155

 ionization energies of boron, B, and between the fourth and fifth ion-
ization energies of carbon, C. In each case, the jump in ionization ener-
gy occurs when an ion assumes a noble-gas configuration. For example,
the removal of one electron from a lithium atom ( [ Hells 1 ) leaves the
helium noble -gas configuration. The removal of four electrons from a
carbon atom ( [ He ] Zv:2/r ) also leaves the helium configuration. A big-
ger table would show that this trend continues across the entire period -
ic system.

SAMPLE PROBLEM F
Consider two main-group elements, A and B. I . lenient V lias a first ionization energy of 419 kJ/mol.
Element B has a first ionization energy of 1000 kJ/mol. Decide if each element is more likely to he in the
s block or p block. Which element is more likely to form a positive ion?

SOLUTION Element A has a very low ionization energy, which means that atoms of A lose electrons
easily. Therefore, element A is most likely to be an .v - block metal because ionization ener -
gies increase across the periods.

Element B has a very high ionization energy which means that atoms of B have difficulty
losing electrons. Element B would most likely lie at the end of a period in the p block.

Element A is more likely to form a positive ion because it has a much lower ionization
energy than element B does.

PRACTICE Answers in Appendix E

1. Consider four hypothetical main-group elements, Q, R. T. and X.

that have the outer electron configurations indicated below. Then,
answer the questions that follow.

0: 3r 3p5 R: 3J * T: 4c/ l l5rV X: 4</ 105.r 5/> l

(

a . Identify the block location of each hypothetical main-group

element.
b. Which of these elements are in the same period? Which are in
the same group?
c. Which element would you expect to have the highest first
ionization energy ? Which would have the lowest first ionization
energy?
d . Which element would you expect to have the highest second —
^rffcrTvftdii
Go to go.hrw.com for
ionization energy?
more practice problems
e. Which of the elements is most likelv to form a 1 + ion ? that ask you to use
periodic trends in
ionization energy.
Keyword: HC 6 PERX

156 CHAPTER 5
 o
Electron Affinity CHEMISTRY LJI
Neutral atoms can also acquire electrons. The energy change that occurs ' *'
Module 3 : Periodic Properties
(STO

when an electron is acquired by a neutral atom is called the atom 's elec-
tron admit). Most atoms release energy when they acquire an electron.

A +e » A- + energy
On the other hand, some atoms must be “’ forced * ’ to gain an electron h\
the addition of energy.
A + e~ + energy
*A
“

The quantity of energy absorbed would be represented by a positive num-

ber. but ions produced in this way are very unstable and hence the elec -
tron affinity for them is very difficult to determine. An ion produced in this
way will be unstable and will lose the added electron spontaneously.
Figure 17 shows the electron affinity in kilojoules per mole for the ele -
ments. Positive electron affinities, because they are so difficult to deter -
mine with any accuracy, are denoted in Figure 17 by ** ( ( ) )." Figure 18, on
the next page, presents these data graphically.

Period Trends
Among the elements of each period, the halogens (Group 17 ) gain elec -
trons most readily. Tliis is indicated in Figure 17 by the large negative
values of halogens’ electron affinities. The ease with which halogen atoms
gain electrons is a major reason for the high reactivities of the Group 17
FIGURE 17 The values listed in
elements. In general, as electrons add to the same p sublevel of atoms
parentheses in this periodic table of
with increasing nuclear charge, electron affinities become more nega- electron affinities are approximate.
tive across each period within the p block. An exception to this trend Electron affinity is estimated to be
occurs between Groups 14 and 15. Compare the electron affinities of -50 kJ/mol for each of the lantha-
carbon (|He|2r 2/r ) and nitrogen (|He ]2s22/?3 ). Adding an electron to a nides and 0 kJ / mol for each of the
carbon atom gives a half- filled p sublevel. This occurs much more easily actinides.

Periodic Table of Electron Affinities ( kJ/ mol )

Atomic
.^""number Group 18
1
2
1
ISA
H 6 He i

2
Group 1
3
Li
Group 2

Be
4 C — Symbol
Group 13 Group 14 Group 15 Group 16 Group 17
rj
B
b
C N
7
0
3 9
F Ne
10
2
61 i -126.3 -27 1 -1761 (01 *1461 - 339 9 ( 01
Electron 13 14 15 16 17 18
11 12 affinity
3
Na Mg Al Si P S Cl Ar ^
54 8 ' 01 Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12
- 44 1 138 5 - 74 6 * 207 7 - 361.7 ) 0

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
§ 4 5
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 4
2.
i - 50.1 cm -11.(1 - 7.9 - 52.5 - 66 6 (0) - 16 3 - 661 -1156 - 122 8 <0> - 30 - 135 81 202 1 -336.5 (III

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 5
48 6 (0) - 10.7 -42 6 - 89.3 74.6 -55 -105 -113 7 - 55 7 -13<T2 (0) - 30 -120
n
- * 07
83
197 1
84
- 305 9
E
(0)

-V
55 56 57 72 73 74 75 76 77 78 79 80 E
6
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn 6

- 156 5 -212.8 10»

47.2 (0) 50 -122 B1 5 15 -110 - 230 9 (OS 20 36
114
946
115
- 190
116
280
117 118
87 88 89 104 105 106 107 108 109 110 111 112 113
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub Uut Uuq Uup 7
• 47 U

THE PERIODIC LAW 157

 Electron Affinity vs. Atomic Number

°He K Kr Xe Rn Ra

Rb Cs Fr
Na
Li
H
- TOO
o
E

&
£ -200
r
m
c
o
-
«
u
o
LLJ

300

Period Period Period Period Period Period

2 3 4 5 6 7
-400
0 10 20 30 40 50 60 70 80 90 100
Atomic number

FIGURE 18 The plot of electron

affinity versus atomic number shows
that most atoms release energy than forcing an electron to pair with another electron in an orbital of
when they acquire an electron, as the already half - filled p sublevel of a nitrogen atom.
indicated b \ negative values.
Group Trends
Trends for electron affinities within groups are not as regular as trends
for ionization energies. As a general rule, electrons add with greater
difficulty down a group. This pattern is a result of two competing fac -
tors. The first is a slight increase in effective nuclear charge down a
group, which increases electron affinities. The second is an increase in
atomic radius down a group, which decreases electron affinities. In gen -
eral. the size effect predominates. Hut there arc exceptions, especially
among the heavy transition metals, which tend to be the same size or
even decrease in radius down a group.

Adding Electrons to Negative Ions

For an isolated ion in the gas phase, it is always more difficult to add a
second electron to an already negatively charged ion. Therefore, second
.
electron affinities are all positive Certain /7-block nonmetals tend to
form negative ions that have noble gas configurations. The halogens do
so by adding one electron. For example, chlorine has the configuration
|Ne ]3.v 23/> \ An atom of chlorine achieves the configuration of the noble
gas argon by adding an electron to form the ion Cl ( [ Ne ) 3v:3/C ). *

Adding another electron is so difficult that Cl 2 never occurs. Atoms of

"

158 CHAPTER 5
Group lb elements are present in many compounds as 2- ions. For
example, oxygen ( [ HC ] 2.Y:2/J4 ) achieves the configuration of the noble
gas neon by adding two electrons to form the ion 0 ( [ He ]2v ~2/)h).
"

Ionic Radii
CHEMISTRY
Figure 19 shows the radii of some of the most common ions of the ele -
Module 3 : Periodic Properties
ments. Positive and negative ions have specific names.
A positive ion is known as a cation The formation of a cation by the .
loss of one or more electrons always leads to a decrease in atomic radius
because the removal of the highest -energy-level electrons results in a
smaller electron cloud. Also, the remaining electrons are drawn closer to
the nucleus by its unbalanced positive charge.
A negative ion is known as an union The formation of an anion by the .
addition of one or more electrons always leads to an increase in atomic
radius. This is because the total positive charge of the nucleus remains
unchanged when an electron is added to an atom or an ion. So the elec -
trons are not drawn to the nucleus as strongly as they were before the
addition of the extra electron. The electron cloud also spreads out
because of greater repulsion between the increased number of electrons.

Period Trends
Within each period of the periodic table, the metals at the left tend to
form cations and the nonmetals at the upper right tend to form anions.
Cationic radii decrease across a period because the electron cloud
FIGURE 19 The ionic radii of the
shrinks due to the increasing nuclear charge acting on the electrons in
ions most common in chemical com-
the same main energy level. Starting with Group 15. in which atoms pounds are shown. Cations are
assume stable noble-gas configurations by gaining three electrons . smaller and anions are larger than
the atoms from which they are
formed.

Periodic Table of Ionic Radii ( pm )

Atomic
1 number Group 18
1 o 6 2
1
H tW
"

Relative Relative
Group 1 Group 2 atomic size ionic size Group 13 Group 14 Group IS Group 16 Group 17 M *
3 4 S 6 7 8 9 10
2 o
U* Bo" 4S
Ionic symbol C
4 ^

260 Ionic radius ( pm)

6 C«-
Ono N»
O
O5
O
'• »
Q
HI Nf
2

11 12 13 14 15 16 17 18
3 O o
* • - PV
OJU 5 © M C! o»8» 3
NB*
**20***
Group 3 Group 4 GroupS Group 6 Group 7 Group 8 Group 1} Group K) Group 11 Group 12 Al
' »4 Si * ‘ At
D
19 21 22 23 24 25 26 27 28 29 30 31 32 33 34 36 36 5
4 o o o o o O o o e o o 0 o 4 :
1J
.
Q
<*
37
Cv
38
sc*
39
n ip

40
- « V*
41
CH*
42
K Mo ’ b
43
- 44
*
Ft * - CV
45
• Nr
46
* Cu
47
* Zrv’*
48
'4 G« *
49
‘ •. > Qt
50
A
51
* ^
5
52
Br
53
> •
* Kr
54
o.

5 o o ,
o O Obh Ag OIlr, Cd O96 In *OMi Vi O116 Sb P v TVO:?1 I ©»0 Xe 5
Rb * iJ Sr * ti8 Y1 Zr Nb Mo Tt - Ru
’
Ah * Pd * * * 3
* *
55 56 57 72 73 74 7S 76 77 78 79 80 81 82 83 84 85 86
& O o o
. Pi’*
o o
r »« Tf *•
o o O
119 Bru < 01 Po
6
Mg*
Cl * BB L B
* 111 M f TB VJ Ht Cn Ir B0 Au* tj t* At Br

87 88 89 104 105 106 107 108 > 09 110 111 112 113 114 115 116 117 118
7 O «o O 7
Fr *
'• **• «“
< ) Ac 1* ftf DO - Sg B h Ml Mt Di Uuu U u b Out Ouo Uup

THE PERIODIC LAW 159

 anions are more common than cations. Anionic radii decrease across
each period for the elements in Groups 15-18. The reasons for this
trend are the same as the reasons that cationic radii decrease from left
to right across a period .

Croup Trends
As they are in atoms, the outer electrons in both cations and anions are
in higher energy levels as one reads down a group. Therefore, just as
there is a gradual increase of atomic radii down a group, there is also a
gradual increase of ionic radii.

Valence Electrons
Chemical compounds form because electrons are lost gained, or
,

shared between atoms. The electrons that interact in this manner are
those in the highest energy levels. These are the electrons most subject
to the influence of nearby atoms or ions. The electrons available to be
lost , gained . or shared in the formation of chemical compounds are
referred to as valence electrons. Valence electrons are often located in
incompletely filled main -energy levels. For example, the electron lost
from the 3.v sublevel of Na to form Na + is a valence electron .
For main -group elements, the valence electrons are the electrons in
the outermost 5 and p sublevels. The inner electrons are in filled energy
levels and are held too tightly by the nucleus to be involved in com -
pound formation . The Group 1 and Group 2 elements have one and two
valence electrons, respectively, as shown in Table 4. Hie elements of
Groups 13- IS have a number of valence electrons equal to the group
number minus 10. In some cases, both the $ and p sublevel valence elec-
trons of the /7- block elements are involved in compound formation . In
other cases, only the electrons from the p sublevel are involved.

TABLE 4 Valence Electrons in Main-Group Elements

Group number Group configuration Number of valence electrons
1 ns 1
2 ns - 1

13 ns2 .pJ 3
14 nrp~ 4
15 ns2- p I 5
2
/ is pA
16 6
2 s
17 /0 *
77 - 7
IS / J.V 776 8

160 CHAPTER 5
 Electronegativity
Valence electrons hold atoms together in chemical compounds. In many
compounds, the negative charge of the valence electrons is concentrated
closer to one atom than to another. This uneven concentration of charge
has a significant effect on the chemical properties of a compound. It is
therefore useful to have a measure of how strongly one atom attracts
the electrons of another atom within a compound.
Linus Pauling, one of Americas most famous chemists, devised a scale
of numerical values reflecting the tendency of an atom to attract elec -
trons. Electronegativity is a measure of the ability of an atom in a chem -
ical compound to attract electrons from another atom in the compound.
The most electronegative element, fluorine, is arbitrarily assigned an
electronegativity value of four. Values for the other elements are then
calculated in relation to this value.

Period Trends
As shown in Figure 20, electronegativities tend to increase across each
FIGURE 20 Shown are the elec-
period, although there are exceptions . The alkali and alkaline-earth metals
tronegativities of the elements
are the least electronegative elements. In compounds, their atoms have a according to the Pauling scale. The
low attraction for electrons. Nitrogen, oxygen, and the halogens are the most - electronegative elements are
most electronegative elements. Their atoms attract electrons strongly in located in the upper right of the
compounds. Electronegativities tend to either decrease down a group or p block. The least- electronegative
remain about the same. The noble gases are unusual in that some of them elements are located in the lower
left of the s block .

Periodic Table of Electronegativities

Atomic
number Group 18
1
2
I
H 6 He
J \
'
2
Group 1
3
Li
Group J

Be
4 c
2.5
Symbol
Group 13 Group 14 Group IS Group 16

B
5 6
C
7
N
8
0
Group 17
9
F Ne
10
2
10 i .S 70 25 3.0 35 40
Elec troncreativity 13 14 IS 16 17 18
11 12
3
Na Mg Al Si P S Cl Ar 3
09 12 Group 3 Group 4 GroupS Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12 IS 18 21 25 30
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
§ 4
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr «
I 08 I0 1.3 15 16 1.6 15 1R 18 18 19 16 16 18 2.0 24 28 3.0
I

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe ^
08 10 12 14 16 18 19 22 12 i l »' 17 • 1
18 1l
‘ 3.1 75 26
55 56 57 72 73 74 75 76 77 78 79 1 81 82 83 84 85 86
Hf Os Ir Pt Au Hg TI Pb Bi Po At Rn
6 Cs
I11
Ba
09
La
11 13
Ta
15
W
17
Re
I9 2.2 11 n 74 19 18 IB 19 70 72 74 ‘
87 88 89 104 05 106 107 108 109 110 111 112 113 114 115 116 117 118
7 Fr Ra Ac Rf Db Sg Bh Hs Mt Ds Uuu Uub (Jut Uuq Uup 7
0.7 09 11

Lanthanide series
58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
'i 11 U
1i I1 11 11 11 12 iI 12 12 1J

SO 91 92 93 94 95 96 97 98 99 100 101 102 103

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1J 15 14 u 13 1J »3 13 1J t 3 u 1J
Actinide series

THE PERIODIC LAW 161

 Electronegativity vs. Atomic Number
F
4.0 Period
Period Period Period Period
2 6
3.5

3.0

& 2.5
>
fU
CJi H
c 2.0
o
O'
a>
1.5

1.0 Li

Cs
0.5

0 10 20 30 40 50 60 70 80
Atomic number

FIGURE 21 The plot shows elec-

tronegativity versus atomic number
for Periods l -6. do not form compounds and therefore cannot be assigned electronega -
tivities. When a noble gas does form a compound , its electronegativity is
rather high , similar to the values for the halogens. The combination of the
period and group trends in electronegativity results in the highest values
belonging to the elements in the upper right of the periodic table. The
lowest values belong to the elements in the lower left of the table. These
trends are shown graphically in Figure 21.

SAMPLE PROBLEM G
.
Of the elements gallium , Ga , bromine , Br, and calcium Ca , which has the highest electronegativity?
Explain your answer in terms of periodic trends.

SOLUTION All of these elements are in the fourth period. Bromine has the highest atomic number and
is farthest to the right in the period . Therefore, bromine should have the highest electroneg-
ativity because electronegativity increases across the periods.

PRACTICE Answers in Appendix E

1 . Consider five hypothetical main group elements. E , G. J. L. and

-
M , that have the outer electron configurations shown at the top
of the next page.

162 CHAPTER 5
 E = lsz2fP G = 4d { )5s25p5 J = 2s:2 / r
'
L = 5d ln6 <
r 6/T M = 2 s :2 p 4
a. Identity the block location for each element. Then, determine
which elements are in the same period and which are in the same
group.
b. Which element would you expect to have the highest electron
affinity? Which would you expect to form a I- ion ? Which should
have the highest electronegativity ?
c. Compare the ionic radius of the typical ion formed by the element — i T f b i11
Go to go.hrw.com for
G with the radius of the atom from which the ion was formed.
more practice problems
d. Which element ( s ) contain seven valence electrons? that ask you to predict
periodic properties.
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Periodic Properties of the d- and

f- Block Elements
The properties of the (/ - block elements ( which are all metals ) vary less
and with less regularity than those of the main-group elements. This
trend is indicated by the curves in Figures 14 and 16, which flatten where
the ( /-block elements fall in the middle of Periods 4-6.
Recall that atoms of the ( /- block elements contain from zero to two
electrons in the v orbital of their highest occupied energy level and one
to ten electrons in the d sublevel of the next -lower energy level .
Therefore, electrons in both the ns sublevel and the ( / / - 1 )d sublevel
are available to interact with their surroundings. As a result , electrons in
the incompletely filled d sublevels are responsible for many character -
istic properties of the (/-block elements.

Atomic Radii
Hie atomic radii of the (/ -block elements generally decrease across the
periods. However, this decrease is less than that for the main-group
elements because the electrons added to the ( / / - 1 )d sublevel shield the
outer electrons from the nucleus. Also, note in Figure 14 that the radii dip
to a low and then increase slightly across each of the four periods that
contain (/-block elements. As the number of electrons in the d sublevel
increases, the radii increase because of repulsion among the electrons.
In the sixth period, the /-block elements fall between lanthanum
( Group 3 ) and hafnium ( Group 4 ). Because of the increase in atomic
number that occurs from lanthanum to hafnium, the atomic radius of
hafnium is actually slightly less than that of zirconium, Zr. the element
immediately above it . The radii of elements following hafnium in the
sixth period vary with increasing atomic number in the usual manner.

THE PERIODIC LAW 163

 Ionization Energy
As they do for the main-group elements, ionization energies of the
// - block and / -block elements generally increase across the periods. In
'

contrast to the decrease down the main groups, however, the first ion -
ization energies of the / / - block elements generally increase down each
group.This is because the electrons available for ionization in the outer
s sublevels are less shielded from the increasing nuclear charge bv elec -
trons in the incomplete ( / / - 1 ) / / sublevels.

Ion Formation and Ionic Radii

-
Among all atoms of the / / - block and / block elements, electrons in the
highest occupied sublevel are always removed first . For the / / - block ele -
ments. this means that although newly added electrons occupy the / /
sublevels, the first electrons to be removed are those in the outermost .v
.
sublevels For example, iron. Fe, has the electron configuration
|Ar ]3 / / h4.v2. First, it loses two 4v electrons to form Fe 2" ( [ Ar |3/ / M ). Fe2+
can then lose a 3 / / electron to form Fe ' * (| Ar|3// > ).
Most / / -block elements commonly form 2+ ions in compounds Some, .
such as iron and chromium, also commonly form 3+ ions. The Group 3
elements form only ions with a 3+ charge. Copper forms 1 + and 2+ ions,
and silver usually forms only 1 + ions. As expected, the cations have
smaller radii than the atoms do. Comparing 2-t- ions across the periods
shows a decrease in size that parallels the decrease in atomic radii.

Electronegativity
The //-block elements all have electronegativities between 1.1 and 2.54.
Only the active metals of Groups 1 and 2 have lower electronegativities.
The / / -block elements also follow the general trend for electronegativity
values to increase as radii decrease, and vice versa. The /- block elements
all have similar electronegativities, which range from 1.1 to 1.5.

SECTION REVIEW 3. For each main- group element, what is the relation-
1. State the general period and group trends among ship between its group number and the number of
main-group elements with respect to each of the valence electrons that the group members have ?
following properties: Critical Thinking
a. atomic radii d. ionic radii 4. RELATING IDEAS Graph the general trends (left to
b. first ionization energy e. electronegativity right and top to bottom) in the second ionization
c. electron affinity energy [ IE2 ) of an element as a function of its
atomic number, over the range Z = 1-20. Label the
2 . a . In general, how do the periodic properties of minima and maxima on the graph with the appro -
the cf-block elements compare with those of the priate element symbol.
main-group elements ?
b. Explain the comparisons made in (a).

164 CHAPTER s
 CHAPTER HIGHLIGHTS
History of the Periodic Table
I Vocabulary •The periodic law states that the physical and chemical proper -
periodic law ties of the elements are periodic functions of their atomic
periodic table numbers.
lanthanide •The periodic table is an arrangement of the elements in order
actinide of their atomic numbers so that elements with similar proper -
ties fall in the same column.
•The columns in the periodic table are referred to as groups .
Electron Configuration and the Periodic Table
I Vocabulary •The rows in the periodic table are called periods.
alkali metals •Many chemical properties of the elements can be explained by
alkaline-earth metals the configurations of the elements * outermost electrons.
transition elements •The noble gases exhibit unique chemical stability because their
main - group elements highest occupied levels have an octet of electrons, ns^np*' (with
halogens the exception of helium, whose stability arises from its highest
occupied level being completely filled with two electrons. 1s2 ) .
•Based on the electron configurations of the elements, the peri-
odic table can be divided into four blocks: the s block, the p
block, the d block, and the / block.

Electron Configuration and Periodic Properties

I Vocabulary • Hie groups and periods of the periodic table display general
atomic radius trends in the following properties of the elements: electron
ion affinity, electronegativity, ionization energy, atomic radius, and
ionization ionic radius.
ionization energy •The electrons in an atom that are available to be lost, gained,
electron affinity or shared in the formation of chemical compounds are
cation referred to as valence electrons.
anion •In determining the electron configuration of an ion. the order
valence electrons in which electrons are removed from the atom is the reverse of
electronegativity the order given by the atom's electron-configuration notation.

THE PERIODIC LAW 165

 CHAPTER REVIEW
11. What name is sometimes used to refer to the
History of the Periodic Table entire set of rf -block elements?
12. a. What types of elements make up the p block ?
SECTION 1 REVIEW
b. How do the properties of the /7-block metals
1. Describe the contributions made by the follow -
compare with those of the metals in the s and
ing scientists to the development of the periodic ( I blocks?

table: .
13 a. Which elements are designated as the
a. Stanislao Cannizzaro halogens?
b. Dmitri Mendeleev .
b. List three of their characteristic properties
c. Henrv Moseley 14. a. Which elements are metalloids?
2. State the periodic law. b. Describe their characteristic properties.
3. I low is the periodic law demonstrated within 15. Which elements make up the / block in the
the groups of the periodic table ? periodic table?
.
16 a. What are the main-group elements?
b. What trends can be observed across the vari -
Electron Configuration ous periods within the main-group elements?
and the Periodic Table
PRACTICE PROBLEMS
SECTION 2 REVIEW
17. Write the noble -gas notation for the electron
4. a. 1 low do the electron configurations within
configuration of each of the following elements,
the same group of elements compare?
and indicate the period in which each belongs.
b. Why are the noble gases relatively unreac -
a. Li c. Cu e. Sn
tive?
b. O d. Br
5. What determines the length of each period in
18. Without looking at the periodic table, identify
the periodic table?
the period, block, and group in which the ele-
6. What is the relationship between the electron
ments with the following electron configurations
configuration of an element and the period in
are located. ( Hint : See Sample Problem A . )
which that element appears in the periodic
a. [Ne ]3s23/J4
table?
b. [ Kr ]4f / 105 j25p:
7. a. What information is provided by the specific
c. [ Xe ]4/l45</ l06s26/>5
block location of an element ?
19. Based on the information given below, give the
b. Identify, by number, the groups located with -
group, period, block, and identity of each ele -
in each of the four block areas.
ment described. ( Hint: See Sample Problem B. )
8. a. Which elements are designated as the alkali
a. [ He|2r
metals?
b. [ NCJ3.V 1
b. List four of their characteristic properties.
c. [Kr ]5r
9. a. Which elements are designated as the
d. [ Ar ] 4r
alkaline-earth metals? Arjjr
e. [ / M.v 1
b. 1 low do their characteristic properties com -
20. Without looking at the periodic table, write the
pare with those of the alkali metals?
expected outer electron configuration for each
.
10 a. Write the group configuration notation for
of the following elements. ( Hint: See Sample
each J-block group . Problem C. )
b. How do the group numbers of those groups
relate to the number of outer s and d
.
a. Group 7 fourth period
b. Group 3, fifth period
electrons?
c. Group 12. sixth period

166 CHAPTER 5
 CHAPTER REVIEW

21. Identify the block, period, group, group name 29. For each of the following groups, indicate
( where appropriate ), element name, element whether electrons are more likely to he lost or
type, and relative reactivity for the elements gained in compound formation and give the
with the following electron configurations. number of such electrons typically involved.
( Hint : See Sample Problem D.) a. Group I d. Group lb
a. [Nepr /? 1
b. [ Arj ^"
3dl 4sr 4p*
h. Group 2
c. Group 13
e. Group 17
f. Group IS
c. [ Kr ]4f / ln.\yl 30. a. What is electronegativity ?
,
d. [ Xe ]4/ 5rfl6s2 b. Why is fluorine special in terms of elec -
tronegativity ?
31. Identify the most - and least -electronegative
Electron Configuration groups of elements in the periodic table.

and Periodic Properties

PRACTICE PROBLEMS
SECTION 3 REVIEW 32. Of cesium. Cs. hafnium. 1 If. and gold, Au. which
22. a. What is meant by atomic radius? element has the smallest atomic radius? Explain
b. What trend is observed among the atomic your answer in terms of trends in the periodic
radii of main-group elements across a period? table. ( Hint: see Sample Problem E. )
c. Explain this trend. 33 . a. Distinguish between the first, second, and
23 . a. What trend is observed among the atomic third ionization energies of an atom.
radii of main-group elements down a group? b. How do the values of successive ionization
b. Explain this trend. energies compare?
24. Define each of the following terms: c. Why does this occur ?
a. ion 34 . Without looking at the electron affinity table,
b. ionization arrange the following elements in order of
c. first ionization energy decreasing electron affinities: C. O. Li. Na. Rb.
d. second ionization energy and F.
25 . a. How do the first ionization energies of main- 35 . a. Without looking at the ionization energy
group elements vary across a period and table, arrange the following elements in
down a group? order of decreasing first ionization energies:
b. Explain the basis for each trend. Li. o. r. K,Ne* and F.
26. a. What is electron affinity? b. Which of the elements listed in ( a ) would
b. What signs are associated with electron affin- you expect to have the highest second ioniza-
ity values, and what is the significance of tion energy ? Why ?
each sign ? 36 . a. Which of the following cations is least likely
27. a. Distinguish between a cation and an anion, to form: Sr 2+, AIV. K 2+?
b. How does the size of each compare with the b. Which of the following anions is least likely
size of the neutral atom from which it is to form: I , CL, 0: ?
" ~

formed? 37. Which element is the most electronegative

.
28. a What are valence electrons? among C, N, O. Br. and S? Which group does it
b. Where are such electrons located? belong to? ( Hint: See Sample Problem G. )
38. Hie two ions k and Ca2 each have IS elec -
trons surrounding the nucleus. Which would you
expect to have the smaller radius? Why ?

THE PERIODIC LAW 167

 CHAPTER REVIEW

48. Identify which trends in the diagrams below

MIXED REVIEW
describe atomic radius, ionization energy, elec -
39. Without looking at the periodic table, identify tron affinity, and electronegativity.
the period, block , and group in which each of Increases
the following elements is located . *
a. [ Rn ) 7.vl
b. [ Ar ]3r/ “452
c. [ Kr|4r / I 5.y
, l/l

'
( ai

d. [ Xe ]4/l45</96sl <u

.
40 a. Which elements are designated as the noble c

gases?
b. What is the most significant property of
these elements? a.
.
. _
41 Which of the following does not have a noble-gas
Increases
configuration: Na +. Rb+, O2 . Br Ca +, Al3+ S2 ?
’ "

.
42 a. How many groups are in the periodic table?
b. How many periods are in the periodic table?
.
c Which two blocks of the periodic table make i/>
<«D»
up the main-group elements? a)
.
43 Write the noble-gas notation for the electron
u
c
configuration of each of the following elements,
and indicate the period and group in which each
belongs. b.
a. Mg
b. P Increases
c. Sc
d. Y
44. Use the periodic table to describe the chemical <D
properties of the following elements: TO
<D
a. fluorine, F u
C
b. xenon. Xe
c. sodium, Na
d. gold. Au c.
45. For each element listed below, determine the
charge of the ion that is most likely to be 49. The electron configuration of argon differs from
formed and the identity of the noble gas whose those of chlorine and potassium by one electron
electron configuration is thus achieved. each. Compare the reactivity of these three
a. Li e. Mg i. Br elements.
b. Rb f. AI j. Ba
c. O £. P
d. F h. S
46. Describe some differences between the 5 -block
metals and the r /-block metals.
.
47 Why do the halogens readily form 1 - ions?

168 CHAPTER 5
 CHAPTER REVIEW

55. Because transition metals have vacant d orbitals,

CRITICAL THINKING
they form a greater variety of colored com -
As a member on the newly - inhabited space station pounds than do the metals of Groups 1 and 2.
Alpha, you are given the task of organizing informa- Review the section of the Elements Handbook
tion on newly discovered elements as it comes in on transition metals (pages 798-807 ) and answer
from the laboratory. To date, five elements have the following:
been discovered and have been assigned names and a. What colors are exhibited by chromium in its
symbols from the Greek alphabet. An analysis of the common oxidation states?
new elements has yielded the following data: b. What gems contain chromium impurities?
c. What colors are often associated with the fol -
Element Atomic Atomic lowing metal ions: copper, cadmium, cobalt ,
name no. mass Properties
zinc, and nickel?
Epsilon 23 47.33 nonmetal, very reactive, d. What transition elements are considered
e produces a salt when noble metals ? What are the characteristics of
combined with a metal, a noble metal?
gaseous state
Beta 13 27.01 metal, very reactive, soft
P solid, low melting point
Gamma 12 25.35 nonmetal, gaseous element,
RESEARCH & WRITING
Y extremely unreactive 56. Prepare a report tracing the evolution of the
Delta 4 7.98 nonmetal, very abundant, current periodic table since 1900. Cite the
A forms compounds with chemists involved and their major contributions.
most other elements
57. Write a report describing the contributions of
Lambda 9 16.17 metal, solid state, good
Glenn Seaborg toward the discovery of many of
A conductor, high luster,
the actinide elements.
hard and dense

50. Applying Models Create a periodic table

based on the properties of the five new elements. ALTERNATIVE ASSESSMENT
51. Predicting Outcomes Using your newly creat - 58. Construct your own periodic table or obtain a
ed periodic table, predict the atomic number of poster that shows related objects, such as fruits
an element w ith an atomic mass of 11.29 that or vegetables, in periodic arrangement. Describe
has nonmetallic properties and is very reactive. the organization of the table and the trends it
52. Predicting Outcomes Predict the atomic num - illustrates. Use this table to make predictions
ber of an element having an atomic mass of about your subject matter.
15.02 that exhibits metallic properties but is
softer than lambda and harder than beta.
53 . Analyzing Information Analyze vour periodic — f t o >1
table for trends, and describe those trends.
i Graphing Calculator
Graphing Atomic Radii
Go to go.hnv.com for a graphing calculator
USING THE HANDBOOK exercise that asks you to graph atomic radii
versus atomic number for the Period 2
54 . Review the boiling point and melting point data elements.
in the tables of the Elements Handbook . Make
a list of the elements that exist as liquids or Keyword: HC 6 PERX
gases at the boiling point of water. 100 C.

THE PERIODIC LAW 169

 Math Tutor WRITING ELECTRON CONFIGURATIONS

The arrangement of elements in the periodic table reflects the arrangement of electrons
in an atom. Each period begins with an atom that has an electron in a new energy level
and, with the exception of the first period, ends with an atom that has a filled set of p
orbitals. To write the electron configuration of an element, you must fill the sublevels in
order of increasing energy. If you follow the arrows in either of the two types of
mnemonics shown below, you will get correct configurations for most elements.
4 4 4 A A A A
1s ' 1s
2s ' 2p / 2s 2p
3s ' 3P 3d
i
: ;
i i i
3s 3P 3d
As - Ap ! Ad ! Af ! 4s 4p 4c/ 4f
i i i

p ! 5d ’> 5 f
5s ' 5^ I I
5s 5p 5d 5f
I I
6s 1
6p; 6d 6f 6s 6P 6d
7s' Ip Id 7s 7p

You also need to know how many orbitals are in each sublevel and that each orbital
can contain two electrons of opposite spins. As shown in the following table, the sub-
levels s, p, d, and f have 1, 3, 5, and 7 available orbitals, respectively.

Sublevel s p d f
No. of orbitals 1 3 5 7
No. of electrons 2 6 10 14

SAMPLE
Write the full electron configuration for phosphorus.
The atomic number of phosphorus is 15, so a phosphorus atom has 15 protons and elec -
trons. Assign each of the 15 electrons to the appropriate sublevels. The final sublevel can be
unfilled and will contain the number of valence electrons.
Is2, , 2s-2, ,2p6, ,3,r , ,3/ r\
2 c + 2c 4* 6e -f 2c 4- 3c = 15e~
So. the full electron configuration of phosphorus is \ s22s22p(' 3sr?>p:\

PRACTICE PROBLEMS
.
1 Write full electron configurations for the fol- 2. Use noble gas symbols to write shorthand elec -
lowing elements. tron configurations for the following elements.

a. aluminum c. tin a. silicon c. antimony

b. neon d. potassium b. rubidium d. arsenic

170 CHAPTER 5
,
ni «
0
i
9
(
8
71 *
Answer the following items on a separate piece of paper. .
7 Which electron configuration is not correct?
MULTIPLE CHOICE A . O2- [ He ]2s 22/>6
B. Mg2* \ Hz ] 2s 22pb
.
1 In the modern periodic table, elements are
arranged according to ^
C. V + [ Ar ]3rf 2
D . Alu | Ar|lr 2/»h
A. decreasing atomic mass.
B. Mendeleev's original model. .
8 Which two elements are more likely to have the
C. increasing atomic number. same charge on their ions?
D. when they were discovered. A . Se and As
B. Sn and Si
2. Group 17 elements, the halogens, are the most
C. Ca and Rb
reactive of the nonmetal elements because they
D. 1 and Xe
A . require only one electron to till their outer
energy level. 9. Using only the periodic table, choose the list
B. have the highest ioni/ ation energies. that ranks the elements Sr. Te. Kr. Ru. and Cs in
C. have the largest atomic radii. order of increasing ionization energy.
D. are the farthest to the right in the periodic A . Sr < Te < Ru < Cs < Kr
B. Te < Ru < Sr < Cs < Kr
table.
C. Cs < Sr < Ru < Te < Kr
3. The periodic law states that D. Kr < Cs < Sr < Ru < Te
A . the chemical properties of elements can be
grouped according to periodicity. SHORT ANSWER
B. the properties of the elements are functions 10. The second ionization energies for the elements
of atomic mass. S-Ti are listed in a scrambled order below.
C . all elements in the same group have the same Assign the correct IE: value to each element.
( Hint: S has IH 2 - 2251 kJ / rnol. and Ti has
number of valence electrons.
D. all elements with the same number of occu- IE 2 - 1310 kJ /mol. ) Explain your reasoning.
pied energy levels must be in the same group. / /i- values ( kJ /mol ): 2666, 2207.3051. 1235
i .
4. As you move left to right across Period 3 from
.
2251. 1310 and 1145
Mg to Cl, the energy needed to remove an elec - .
11 What group most commonK forms 2- ions?
tron from an atom Explain your reasoning.
A . generally increases. EXTENDED RESPONSE
B. generally decreases.
C. does not change.
.
12 An ordered list of atomic radii for 14 consecu-
tive elements is shown below. Without using
D. varies unpredictable.
Figure 13 on page 151. make a graph of these
5. Which of the following elements has the highest atomic radii versus the element 's atomic num -
electronegativity ? ber. Explain your reasoning.
A . oxygen Atomic radii ( pm ) : 75.73. 72.71. 1 S6, 160 143..
B. hydrogen 118. 110, 103.100. 98.227. and 197
C. fluorine
D. carbon
.
6 The noble gases have
A . high ionization energies.
B. high electron affinities.
If you are short on time, quickly
C. large atomic radii. scan the unanswered questions to see which might
D. a tendency to form both cations and anions. be easiest to answer.

THE PERIODIC LAW 171

 INQUIRY
EXPERIMENT 5 o L A B

The Mendeleev Lab of 1869

OBJECTIVES BACKGROUND
• Observe the physical properties of common Russian chemist Dmitri Mendeleev is generally cred -
elements. ited with being the first chemist to observe that pat -
terns emerge when the elements are arranged
• Observe the properties and trends in the
elements on the periodic table. according to their properties. Mendeleev’s arrange -
ment of the elements was unique because he left
• Draw conclusions and identify unknown blank spaces for elements that he claimed were
elements based on observed trends in undiscovered as of 1869. Mendeleev was so confi -
properties. dent that he even predicted the properties of these
undiscovered elements. His predictions were eventu -
MATERIALS ally proven to be quite accurate, and these new el -
• blank periodic table ements fill the spaces that originally were blank
in his table. Use your knowledge of the periodic
• elemental samples: Ar, C, Sn , and Pb
table to determine the identity of each of the nine
• note cards, 3 in . x 5 in . unknown elements in this activity. These unknown
• periodic table elements are from the periodic table 's groups that
are listed below. Each of these groups contains at
least one unknown element .

1 2 11 13 14 17 18

None of the known elements serves as one of the

nine unknown elements. No radioactive elements are
used during this experiment. The relevant radioac-
tive elements include Fr. Ra , At , and Rn . You may
not use your textbook or other reference materials.
You have been provided with enough information to
determine each of the unknown elements.

SAFETY

For review of safety, please see Safety in the

Chemistry Laboratory in the front of your book .

172 CHAPTER 5
 EXPERIMENT 5
PREPARATION CONCLUSIONS
1. Make a data table to record the properties of 1. Interpreting Information: Summarize your
each unknown that *vou test . group’s reasoning for the assignment of each
unknown. Explain in a few sentences exactly
2. Use the note cards to copy the information list -
how you predicted the identity of the nine
ed on each of the sample cards. If the word unknown elements.
observe is listed , you will need to visually inspect
the sample and then write the observation in the
appropriate space. EXTENSIONS
1. Predicting Outcomes: Use only the data from
your group 's experiment to predict the proper -
PROCEDURE
ties of the not yet discovered element , which has
1. Arrange the note cards of the known elements an atomic number of 120 ( assuming it does not
in a rough representation of the periodic table. radioactively decay ).
In other words, all of the known elements from
Group l should be arranged in the appropriate
order. Arrange all of the other cards accordingly.
2. Inspect the properties of the unknowns to see
where properties would best “ fit ” the trends of
the elements of each group.
3. Assign the proper element name to each of the
unknowns. Add the symbol for each one of the
unknown elements to vour data table.

CLEANUP AND DISPOSAL

4. Clean up your lab station , and return
the leftover note cards and samples of
the elements to vour teacher. Do not
pour any of the samples down the drain or place
them in the trash unless your teacher directs you
to do so. Wash your hands thoroughly before you
leave the lab and after all your work is finished.

ANALYSIS AND INTERPRETATION

1. Organizing Ideas: In what order did your
group arrange the properties to determine the
unknowns? Explain your reasoning. Would a dif -
ferent order have been better ? If so. what is the
better order and why ?
2. Evaluating Methods: What properties were the
most useful in sorting the unknowns? What
properties were the least useful ? Explain your
answer.

THE PERIODIC LAW 173

 CHAPTER 6

Chemical Bonding
In nature, most atoms are joined
to other atoms by chemical bonds.

SCJENTffTC
AMERICAN For advanced project ideas
from Scientific American,
visit go.hryy.cgm and type
in the keyword HC6 SAC. Computer Graphic Representation of a
Molecule of Adenosine Monophosphate
Introduction to SECTION 1

Chemical Bonding OBJECTIVES

J Define chemical bond.

w Explain why most atoms

form chemical bonds.
A toms seldom exist as independent particles in nature. Hie oxygen
you breathe, the water you drink, and nearly all other substances con -
sists of combinations of atoms that are held together by chemical bonds. w Describe ionic and covalent
A chemical bond is a mutual electrical attraction between the nuclei and bonding.
valence electrons of different atoms that binds the atoms together.
Why are most atoms chemically bonded to each other? As indepen- u Explain why most chemical
dent particles, most atoms are at relatively high potential energy. bonding is neither purely
Nature, however, favors arrangements in which potential energy is min- ionic nor purely covalent.
imized. This means that most atoms are less stable existing by them -
selves than when they are combined. By bonding with each other, atoms
j Classify bonding type
decrease in potential energy, thereby creating more stable arrange -
according to electronegativity
ments of matter.
differences.

Types of Chemical Bonding

CHEMISTRY - •

When atoms bond, their valence electrons are redistributed in ways that
make the atoms more stable. The way in which the electrons are redis- Module 4 : Chemical Bonding
tributed determines the type of bonding. In Chapter 5. you read that
main-group metals tend to lose electrons to form positive ions, or
cations, and nonmetals tend to gain electrons to form negative ions, or
anions. Chemical bonding that results from the electrical attraction
between cations and anions is called ionic bonding. In purely ionic bond -
ing. atoms completely give up electrons to other atoms, as illustrated in
.
Figure 1 on the next page In contrast to atoms joined by ionic bonding,
atoms joined by covalent bonding share electrons. Covalent bonding
results from the sharing of electron pairs between two atoms ( see
Figure 1 ). In a purely covalent bond, the shared electrons are “owned"
equally bv the two bonded atoms.

Ionic or Covalent ?
Bonding between atoms of different elements is rarely purely ionic or
purely covalent. It usually falls somewhere between these two extremes,
depending on how strongly the atoms of each element attract electrons.
Recall that electronegativity is a measure of an atom's ability to attract
electrons. The degree to which bonding between atoms of two elements
is ionic or covalent can be estimated by calculating the difference in

CHEMICAL BONDING 175

 IONIC BONDING Anion B
FIGURE 1 In ionic bonding, Cation A
many atoms transfer electrons. Die Many atoms
Electrons transferred
resulting positive and negative ions from atoms A to
combine due to mutual electrical atoms B
attraction. In covalent bonding,
+ j
atoms share electron pairs to form
Atoms A Atoms B
independent molecules.

COVALENT BONDING

Atom C
+

Two atoms
Atom D
Electron pair shared
between atom C and
atom D
n
Atom C Atom D

SC
/ lNKS. kW *
Developed Md munUined by tbe the elements * electronegativities (see Figure 2 ). For example, the
electronegativity difference between fluorine. F, and cesium, Cs, is 4.0 -
HJIKMUI Soncr Trubm MUXUIMM

For a variety of links related to this

chapter, go to wwvyscjlink org 0.7 = 3.3. ( See Figure 20 on page 161 for a periodic table of electroneg-
^
Topic: Covalent Bonding
SciLinks code: HC60363 * ativity values.) So. according to Figure 2, cesium- fluorine bonding is ionic.
Fluorine atoms, which are highly electronegative, gain valence electrons,
causing the atoms to become anions. Cesium atoms, which are less elec-
4^ tronegative. lose valence electrons, causing the atoms to become cations.
Bonding between atoms with an electronegativity difference of 1.7
or less has an ionic character of 50% or less. These compounds are typ -
ically classified as covalent . Bonding between two atoms of the same
element is completely covalent. Hydrogen, for example, exists in
nature not as isolated atoms, but as pairs of atoms held together by
3.3 100 %
covalent bonds. The hydrogen -hydrogen bond is a nonpolar-covalent
bond, a covalent bond in which the bonding electrons are shared equal -
VA
0» ly by the bonded atoms, resulting in a balanced distribution of electrical
O
> Ionic tD charge. Bonds having 0% to 5 % ionic character, corresponding to elec -
0
rf
(t

a; 3 tronegativity differences of roughly 0 to 0.3, are generally considered

c nonpolar-covalent bonds. In bonds with significantly different
o lO
rt>

S 1.7
electronegativities, the electrons are more strontdv attracted bv the
50 % 3
2
a> n more-electronegative atom. Such bonds are polar, meatiing that they
c r>
QJ 3 - have an uneven distribution of charge. Covalent bonds having 5 % to
c
u Polar-covalent CJ 50% ionic character, corresponding to electronegativity differences of
n
01 Q 0.3 to 1.7. are classified as polar. A polar-covalent bond is a covalent
a bond in which the bonded atoms have an unequal attraction for the
0.3 5% shared electrons.
Nonpolar-covalent
0% Nonpolar- and polar-covalent bonds are compared in Figure 3, which
^ illustrates the electron density distribution in hydrogen -hydrogen and
FIGURE 2 Differences in elec- hydrogen-chlorine bonds. The electronegativity difference between
tronegativities reflect the character of chlorine and hydrogen is 3.0 - 2.1 = 0.9, indicating a polar-covalent
bonding between elements. The elec-
bond. The electrons in this bond are closer to the more-electronegative
tronegativity of the less- electronega -
tive element is subtracted from that of chlorine atom than to the hydrogen atom, as indicated in Figure 3b.
the more -electronegative element . The Consequently, the chlorine end of the bond has a partial negative
greater the electronegativity differ - charge, indicated by the symbol 8-. The hydrogen end of the bond then
ence. the more ionic is the bonding. has an equal partial positive charge. 8+.

176 CHAPTER 6
 Chlorine
Hydrogen nucleus FIGURE 3 Comparison of the
Hydrogen nuclei nucleus electron density in ( a ) a nonpolar,
hydrogen-hydrogen bond and ( b ) a
polar, hydrogen- chlorine bond.
Because chlorine is more electroneg-
8+ 8- ative than hydrogen, the electron
density in the hydrogen-chlorine
(a ) Nonpolar - covalent bond (b) Polar - covalent bond bond is greater around the chlorine
atom.

SAMPLE PROBLEM A
Use electronegativity differences and Figure 2 to classify bonding between sulfur, S, and the following
elements: hydrogen, II; cesium, Cs; and chlorine, Cl. In each pair, which atom will be more negative?

SOLUTION .
From Figure 20 on page 161 we know that the electronegativity of sulfur is 2.5. The elec -
tronegativities of hydrogen, cesium, and chlorine are 2.1, 0.7. and 3.0, respectively. In each
pair, the atom with the larger electronegativity will be the more-negative atom.

Bonding between Electronegativity More-negative

sulfur and difference Bond type atom
hydrogen 2.5 - 2.1 = 0.4 polar-covalent sulfur
cesium 2.5 - 0.7 = 1.8 ionic sulfur
chlorine 3.0 - 2.5 = 0.5 polar-covalent chlorine

PRACTICE Answers in Appendix E

Go to go.hrw.com for
Use electronegativity differences and Figure 2 to classify bonding more practice problems
.
between chlorine. Cl. and the following elements: calcium Ca; oxygen. that ask you to classify
O: and bromine, Br. Indicate the more-negative atom in each pair. bonds.

Jv Keyword: HC 6 BNDX

SECTION REVIEW Critical Thinking

1. What is the main distinction between ionic and 5. INTERPRETING CONCEPTS Compare the following
covalent bonding? two pairs of atoms: Cu and Cl; I and Cl.
2. How is electronegativity used in determining the a. Which pair would have a bond with a greater
ionic or covalent character of the bonding percent ionic character ?
between two elements ? b. In which pair would Cl have the greater
negative charge?
3. What type of bonding would be expected between
the following atoms ? 6. INFERRING RELATIONSHIPS The isolated K atom
a. Li and F is larger than the isolated Br atom.
b. Cu and S a. What type of bond is expected between K
c. I and Br and Br ?
b. Which ion in the compound KBr is larger ?
4. List the three pairs of atoms referred to in the
previous question in order of increasing ionic
character of the bonding between them.

CHEMICAL BONDING 177

 SECTION 2
Covalent Bonding and
OBJECTIVES
Define molecule and
Molecular Compounds
"J
molecular formula.

^ Explain the relationships M any chemical compounds, including most of the chemicals that are in
among potential energy,
distance between approach- living things and are produced by living things, are composed of mol -
ing atoms, bond length, and ecules. A molecule is u neutral group of atoms that arc held together by
bond energy. covalent bonds. A single molecule of a chemical compound is an indi -
vidual unit capable of existing on its own. It may consist of two or more
atoms of the same element, as in oxygen, or of two or more different
State the octet rule.
.
atoms, as in water or sugar ( see Figure 4 below ) A chemical compound
whose simplest units are molecules is called a molecular compound.
^ List the six basic steps used The composition of a compound is given by its chemical formula. A
in writing Lewis structures. chemical formula indicates the relative Handlers of atoms of each kind in
a chemical compound by using atomic symbols and numerical subscripts.
The chemical formula of a molecular compound is referred to as a mo-
^ Explain how to determine
Lewis structures for molecules lecular formula. A molecular formula shows the types and numbers of
containing single bonds, atoms combined in a single molecule of a molecular compound . The
multiple bonds, or both. molecular formula for water, for example, is H:0. which reflects the fact
that a single water molecule consists of one oxygen atom joined by sep -
arate covalent bonds to two hydrogen atoms. A molecule of oxygen. 02,
^ Explain why scientists use is an example of a diatomic molecule. A diatomic molecule is a molecule
resonance structures to
represent some molecules.
containing only two atoms.

( a) Water molecule,
H2O

( b ) Oxygen molecule,
02

( c) Sucrose molecule,
C 12H22 11
°
FIGURE 4 The models for ( a ) water, ( b ) oxygen, and ( c ) sucrose, or table
sugar, represent a few examples of the many molecular compounds in and
around us. Atoms within molecules mav form one or more covalent bonds.

178 CHAPTER 6
 FIGURE 5 Potential energy
o 0 changes during the formation of a
£ -
hydrogen hydrogen bond , ( a ) The
-X separated hydrogen atoms do not
U) affect each other, ( b ) Potential
Q)
c energy decreases as the atoms are
CD
drawn together bv attractive forces,
OJ
ac ( c ) Potential energy is at a minimum
2o -436 when attractive forces are balanced
CL by repulsive forces, ( d ) Potential
75 energy increases when repulsion
between like charges outweighs
Distance between hydrogen nuclei (pm)
attraction between opposite charges.

Formation of a Covalent Bond

As you read in Section 1 . nature favors chemical bonding because most
atoms have lower potential energy when they are bonded to other
atoms than they have as they are independent particles. In the case of
covalent bond formation , this idea is illustrated by a simple example, the
formation of a hydrogen - hydrogen bond .
Picture two isolated hydrogen atoms separated by a distance large
enough to prevent them from influencing each other. At this distance,
the overall potential energy of the atoms is arbitrarily set at zero, as
shown in part ( a ) of Figure 5.
Now consider what happens if the hydrogen atoms approach each
other. Each atom has a nucleus containing a single positively charged
proton . Hie nucleus of each atom is surrounded by a negatively charged
electron in a spherical 1 s orbital. As the atoms near each other, their
charged particles begin to interact . As shown in Figure 6, the approach - Both nuclei repel
each other, as do both
ing nuclei and electrons are attracted to each other , which corresponds electron clouds.
to a decrease in the total potential energy of the atoms. At the same
time, the two nuclei repel each other and the two electrons repel each
other, which results in an increase in potential energy. «
The relative strength of attraction and repulsion between the
charged particles depends on the distance separating the atoms. When
the atoms first “sense each other , the electron - proton attraction is
”

stronger than the electron -electron and proton-proton repulsions. Thus,

the atoms are drawn to each other and their potential energy is lowered ,
as shown in part ( b ) of Figure 5.
—— The nucleus of one atom
attracts the electron cloud of
the other atom, and vice versa.
The attractive force continues to dominate and the total potential
energy continues to decrease until , eventually, a distance is reached at FIGURE 6 The arrows indicate
which the repulsion between the like charges equals the attraction of the attractive and repulsive forces
the opposite charges. This is shown in part ( c ) of Figure 5. At this point , between the electrons (shown as
electron clouds ) and nuclei of two
which is represented by the bottom of the valley in the curve, potential
hydrogen atoms. Attraction between
energy is ai a minimum and a stable hydrogen molecule forms. A closer particles corresponds to a decrease
approach of the atoms, shown in part ( d ) of Figure 5, results in a sharp in potential energy of the atoms,
rise in potential energy as repulsion becomes increasingly greater than while repulsion corresponds to
attraction. an increase.

CHEMICAL BONDING 179

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180 CHAPTER 6
 Characteristics of the Covalent Bond
In Figure 5, the bottom of the valley in the curve represents the balance
between attraction and repulsion in a stable covalent bond. At this
point, the electrons of each hydrogen atom of the hydrogen molecule
are shared between the nuclei. As shown below in Figure 7, the mole -
cule 's electrons can be pictured as occupying overlapping orbitals, mov -
ing about freely in either orbital.
The bonded atoms vibrate a bit. but as long as their potential energy
remains close to the minimum, they are covalently bonded to each other.
The distance between two bonded atoms at their minimum potential
energy, that is. the average distance between two bonded atoms, is the
bond length. The bond length of a hydrogen-hydrogen bond is 75 pm.
In forming a covalent bond, the hydrogen atoms release energy as
they change from isolated individual atoms to parts of a molecule. The
amount of energy released equals the difference between the potential
energy at the zero level ( separated atoms ) and that at the bottom of the
.
valley ( bonded atoms ) in Figure 5 The same amount of energy must be
added to separate the bonded atoms. Bond energy is the energy required
to break a chemical bond and form neutral isolated atoms. Scientists usu -
ally report bond energies in kilojoules per mole ( kJ/mol ). which indi-
cates the energy required to break one mole of bonds in isolated
molecules. For example, 436 kJ of energy is needed to break the hydrogen -
hydrogen bonds in one mole of hydrogen molecules and form two moles
of separated hydrogen atoms.
The energy relationships described here for the formation of a
hydrogen -hydrogen bond apply generally to all covalent bonds.
However, bond lengths and bond energies vary with the types of atoms
that have combined. Even the energy of a bond between the same two
types of atoms varies somewhat , depending on what other bonds the
atoms have formed. These facts should be considered when examining
the data in Table 1 on the next page. The first three columns in the table
list bonds, bond lengths, and bond energies of atoms in specific diatom -
ic molecules. The last three columns give average values of specified
bonds in many different compounds.

Region of orbital
Electron clouds
overlap

FIGURE 7 The orbitals of the

hydrogen atoms in a hydrogen mol-
ecule overlap, allowing each electron
Nuclei to feet the attraction of both nuclei.
The result is an increase in electron
Hydrogen atoms Hydrogen molecule densit \ between the nuclei.

CHEMICAL BONDING 181

 TABLE 1 Bond Lengths and Bond Energies for Selected Covalent Bonds
Average bond Average bond Average bond Average bond
Bond length (pm) energy ( kJ/ mol) Bond length (pm) energy ( kJ / mol)
H H 75 436 c-c 154 346
F- F 142 159 C-N 147 305
Cl Cl
- 190 243 OO 143 358
Br- Br 220 193 C-H 109 4I 8
I- l 266 151 C-Cl 177 327
H- F 92 569 C- Br 194 285
H-CI 127 432 N-N 145 163
II- Br 141 366 N- H 101 386
H 1 161 299 O-H 96 459

All individual hydrogen atoms contain a single, unpaired electron in a

I s atomic orbital. When two hydrogen atoms form a molecule, they share
electrons in a covalent bond. As Figure 8 shows, sharing electrons allows
each atom to have the stable electron configuration of helium Is2. This.
tendency for atoms to achieve noble-gas configurations by bonding cova-
lently extends beyond the simple case of a hydrogen molecule.
Bonding electron pair in overlapping orbitals
FIGURE 8 B y sharing electrons in
overlapping orbitals, each hydrogen
atom in a hydrogen molecule experi -
11
T 11
T
ences the effect of a stable l.V Is
\ s~ configuration .

H i II
.
Is Is
.
• i

Hydrogen Hydrogen
atoms molecule

The Octet Rule

Unlike other atoms, the noble-gas atoms exist independently in nature.
They possess a minimum of energy existing on their own because of the
special stability of their electron configurations. This stability results
from the fact that, with the exception of helium and its two electrons in
a completely filled outer shell, the noble-gas atoms outer v and / >
'

orbitals are completely filled by a total of eight electrons. Other main -

group atoms can effectively fill their outermost s and /; orbitals with
electrons by sharing electrons through covalent bonding. Such bond

182 CHAPTER 6
formation follows the octet rule: Chemical compounds tend to form so
I hat each atom , by gaining, losing, or sharing electrons, has an octet of
electrons in its highest occupied energy level.
Let s examine how the bonding in a fluorine molecule illustrates the
'
w*

octet rule. An independent fluorine atom has seven electrons in its high -
rs
est energy level ( [ He ]2r 2/ ). Like hydrogen atoms, fluorine atoms
bond covalently with each other to form diatomic molecules. F 2 . When
two fluorine atoms bond , each atom shares one of its valence electrons
with its partner. The shared electron pair effectively tills each atom 's
outermost energy level with an octet of electrons, as illustrated in
Figure 9a. Figure 9b shows another example of the octet rule, in which
the chlorine atom in a molecule of hydrogen chloride. 11C1. achieves an
outermost octet bv sharing an electron pair with an atom of hydrogen .
FIGURE 9 (a ) By sharing
valence electrons in overlapping
(a) orbitals, each atom in a fluorine
n u u Ti T _ n ns n n t _ Bonding molecule feels the effect of
neon 's stable configuration.
l .v 2s V Is 2 V ’ electron
2p 2p pair in [ He ]2v:2/A ( b ) In a hydrogen
overlapping chloride molecule, the hydrogen

F unun
Is 2s "
i F n n n n: orbitals
atom effectively fills its 1 s
orbital with two electrons, while
2p 2P the chlorine atom experiences
Fluorine atoms Fluorine molecule the stability of an outermost
octet of electrons.

Bonding electron pair

in overlapping orbitals
( b) i
H T H T
Is l .s

Cl Ti U Ti Ti Ti Ti sTi Ti i C| Ti Ti Ti Ti Ti Ti Ti Ti . i
1 s 2s 3.v "
V I s 2v 3.v v
2P 3p 2P 3P
Hydrogen and chlorine atoms Hydrogen chloride molecule

Exceptions to the Octet Rule

Most main -group elements tend to form covalent bonds according to
the octet rule. I lowever. there are exceptions. As you have seen , hydro -
gen forms bonds in which it is surrounded by only two electrons. Boron ,
B, has just three valence electrons ( [ I Ic|2.v:2/ > 1 ). Because electron pairs
are shared in covalent bonds, boron tends to form bonds in which it is
surrounded by six electrons. In boron trifluoride, BF3, lor example, the
boron atom is surrounded by its own three valence electrons plus one
from each of the three fluorine atoms bonded to it . Other elements can
be surrounded by more than eight electrons when they combine with
the highly electronegative elements fluorine, oxygen , and chlorine. In
these cases of expanded valence, bonding involves electrons in d orbitals
as well as in s and p orbitals. Examples of compounds lhal have an
expanded valence include PFS and SF6, as shown in Table 5 .
CHEMICAL BONDING 183
 Number of
valence electrons
Electron- dot
notation Example
Electron- Dot Notation
1 X Na * Covalent bond formation usually involves only the
electrons in an atom 's outermost energy levels, or the
2 X *
Mg- atom's valence electrons. To keep track of these elec-
trons, it is helpful to use electron- dot notation.
3 X- B-
Electron-dot notation is an electron-configuration no -
4 X c tation in which only the valence electrons of an atom
of a particular element are shown , indicated by dots
5 X: • N: placed around the element 's symbol . The inner-shell
electrons are not shown. For example, the electron-
6 X: O:
dot notation for a fluorine atom ( electron configura -
7 X: : F: tion [ He ] 2r 2p>) may be written as follows.
:F:
8 X : Ne :

In general, an element 's number of valence electrons

FIGURE 10 To write an element 's electron - dot can be determined by adding the superscripts of the
notation, determine the element 's number of valence element 's noble -gas notation. In this book, the
elect runs. Then place a corresponding number of dots electron-dot notations for elements with l-8 valence
around the element 's symbol, as shown. electrons are written as shown in Figure 10.

SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter.

a . Write the electron-dot notation for hydrogen.

b. Write the electron-dot notation lor nitrogen.

SOLUTION a . A hydrogen atom has only one occupied energy level, the n = l level, which contains a
single electron. Therefore, the electron-dot notation for hydrogen is written as follows.
IT *

b. The group notation for nitrogen's family of elements is ns:np\ which indicates that nitro-
gen has five valence electrons. Therefore, the electron-dot notation for nitrogen is writ -
ten as follows.

• N:

Lewis Structures
Electron-dot notation can also be used to represent molecules. For
example, a hydrogen molecule. IT, is represented by combining the
notations of two individual hydrogen atoms, as follows.
11 11

184 CHAPTER 6
Hie pair of dots represents the shared electron pair of the hydrogen -
hydrogen covalent bond. For a molecule of fluorine, F2. the electron-dot
notations of two fluorine atoms are combined.

'
• F:F :

Here also the pair of dots between the two symbols represents the
shared pair of a covalent bond. In addition, each fluorine atom is sur -
rounded by three pairs of electrons that are not shared in bonds. An
unshared pair, also called a lone pair, is a pair of electrons that is not
involved in bonding and that belongs exclusively to one atom.
The pair of dots representing a shared pair of electrons in a covalent
bond is often replaced by a long dash. According to this convention,
hydrogen and fluorine molecules are represented as follows.

H-H : F — F:

These representations are all Lewis structures, formulas in w hich atomic

symbols represent nuclei and inner - shell electrons, dot - pairs or dashes
betw een two atomic sytnbols represent electron pairs in covalent bonds,
ami dots adjacent to only one atomic symbol represent unshared elec -
trons. It is common to write Lewis structures that show only the elec -
trons that are shared, using dashes to represent the bonds. A structural
formula indicates the kind , number, arrangement , and bonds but not the
unshared pairs of the atoms in a molecule. For example. F F and II Cl
are structural formulas.
The Lewis structures ( and therefore the structural formulas ) for
many molecules can be drawn if one knows the composition of the
molecule and which atoms are bonded to each other. The following
sample problem illustrates the basic steps for writing Lewis structures.
The molecule described in this problem contains bonds with single
shared electron pairs. A single covalent bond or a single bond , is a
,

covalent bond in w hich one pair of electrons is shared between two

atoms.

SAMPLE PROBLEM C For more help, go to tne Math Tutor a t the end of this chapter

Draw the Lewis structure of iodomethane, CH3L

SOLUTION of atoms in the molecule.

1 . Determine the type and number
The formula shows one carbon atom, one iodine atom, and three hydrogen atoms.

2. Write the electron -dot notation for each type of atom in the molecule.
Carbon is from Group 14 and has four valence electrons. Iodine is from Group 17 and
has seven valence electrons. Hydrogen has one valence electron.

C ;I = H

CHEMICAL BONDING 185

 3. Determine the ( oinl number of valence electrons available in the atoms to be combined.

C 1 x 4e~ = 4e~
I 1 x le~ = le~
3H 3 x \ e~ = 3e~
I 4e~
4 . Arrange the atoms to form a skeleton structure for the molecule. If carbon is present , it is
.
the central atom. Otherwise the least -electronegative atom is central ( except for hydrogen ,
which is never central ). Then connect the atoms by electron - pair bonds.
H
H :C : 1
H

5. Add unshared pairs of electrons to each nonmetal atom ( except hydrogen ) such that each
is surrounded by eight electrons.

II H
H CA or H- C-I:
H II
6. Count the electrons in the structure to be sure that the number o f valence electrons used
equals the number available. He sure the centra! atom and other atoms besides hydrogen
have an octet.
I here are eight electrons in the four covalent bonds and six electrons in the three
unshared pairs, giving the correct total of 14 valence electrons.

PRACTICE Answers in Appendix E

1. Draw the Lewis structure of ammonia. NHV

2. Draw the Lewis structure for hydrogen sulfide. H:S.

— ir-T t * j 1 1
Go to go.hrw.com for
3. Draw the Lewis structure for silane. SiH4.
more practice problems
4 . Draw the Lewis structure for phosphorus trifluoride. PFV that ask you to draw
Lewis structures .
Keyword: HC 6 BNDX

Multiple Covalent Bonds

Atoms of some elements, especially carbon, nitrogen, and oxygen, can
share more than one electron pair. A double covalent bond, or simply a
double bond , is a covalent bond in which two pairs of electrons are
shared between two atoms. A double bond is shown either by two side -
by -side pairs of dots or by two parallel dashes. All four electrons in a
double bond “belong' to both atoms. In ethene. C \ H 4. for example, two
*

electron pairs are simultaneously shared by two carbon atoms.

H H 11 H
C :: C or C=C
\
H II 11 H

186 CHAPTER 6
 A triple covalent bond, or simply a triple bond , is a covalent bond in n ua J A
which three pairs of electrons are shared between two atoms. For exam -
ple. elemental nitrogen. N:, like hydrogen and the halogens, normally
N
Is —^
2s *' ! v !r ' !
2P
exists as diatomic molecules. In this case, however, each nitrogen atom,
which has five valence electrons, acquires three electrons to complete N U u :t ; 1T
l.v 2s
an octet by sharing three pairs of electrons with its partner. This is illus- 2p
trated in the Lewis structure and the formula structure for N\. as shown
below. Nitrogen molecule
FIGURE 11 In a molecule of nitro-
: N::: N: or N=N .
gen . N: each nitrogen atom is sur -
rounded by six shared electrons plus
Figure II represents nitrogen ’s triple bond through orbital notation. one unshared pair of electrons. Thus,
Like the single bonds in hydrogen and halogen molecules, the triple each nitrogen atom follows the octet
bond in nitrogen molecules is nonpolar. rule in forming a triple covalent bond .

Carbon forms a number of compounds containing triple bonds. For

example, the compound ethyne. C ^ l L. contains a carbon -carbon triple
bond.

H : C ::: C : H or H - C=C — H

Double and triple bonds are referred to as multiple bonds, or multi -

ple covalent bonds. Double bonds in general have greater bond ener -
gies and are shorter than single bonds. Triple bonds are even stronger
and shorter Table 2 compares average bond lengths and bond energies
for some single, double, and triple bonds.
In writing Lewis structures for molecules that contain carbon, nitro-
gen. or oxygen, one must remember that multiple bonds between pairs
of these atoms are possible. ( A hydrogen atom, on the other hand, has
only one electron and therefore always forms a single covalent bond. )
The need for a multiple bond becomes obvious if there are not enough
valence electrons to complete octets by adding unshared pairs. Sample
Problem D on the next page shows how to deal with this situation.

TABLE 2 Bond Lengths and Bond Energies for Single and Multiple
Covalent Bonds
Average bond Average bond Average bond Average bond
Bond length (pm) energy ( kJ / mol) Bond length (pm) energy (kJ/ mol)
C- C 154 346 C- O 143 358
C=C 134 612 0=0 120 732
C=C 120 835 C=Q 113 1072
C-N 147 305 N-N 145 163
C=N 132 615 N=N 125 418
C=N 116 887 N=N 110 945

CHEMICAL BONDING 187

 SAMPLE PROBLEM D For more help, go to the Math Tutor at the end of this chapter.

Draw the Lewis structure for methanal, CH 2(), which is also known as formaldehyde.

SOLUTION 1 . Determine the number of atoms of each element present in the molecule.
The formula shows one carbon atom , two hydrogen atoms, and one oxygen atom.

2. Write the electron -dot notation for each type of atom.

Carbon is from Group 14 and has four valence electrons. Oxygen , which is in Group 16,
has six valence electrons. Hydrogen has only one electron .
C *
:Q : H
3 . Determine the total number of valence electrons available in the atoms to be combined.
C 1 x 4C = 4c '

O 1 x 6c "

= 6c "

2H 2 x lc "

= 2e~
12c "

4. Arrange the atoms to form a skeleton structure for the molecule, and connect the atoms
by electron - pair bonds.
II
H :C •O
5. Add un\hared pairs of electrons to each nonmetal atom ( except hydrogen I such that each
is surrounded by eight electrons.
H
H :C : Q :

6a . Count the electrons in the Lewis structure to be sure that the number of valence electrons
used equals the number available.
The structure above has six electrons in covalent bonds and eight electrons in four
lone pairs, for a total of 14 electrons. The structure has two valence electrons too many.
6 b . If too manv electrons have been used , subtract one or more lone pairs mail the total number
of valence electrons is correct. Then move one or more lone electron pairs to existing bonds
between non - hydrogen atoms until the outer shells of all atoms are completely filled .
Subtract the lone pair of electrons from the carbon atom. Then move one lone pair of
electrons from the oxygen to the bond between carbon and oxygen to form a double bond .
H II
HOO or H - C=O
There are eight electrons in covalent bonds and four electrons in lone pairs, for a total
of 12 valence electrons.

PRACTICE Answers in Appendix E

1 . Draw the Lewis structure for carbon dioxide, CO - . . Go to go. hrw.com for
more practice problems
2 . Draw the Lewis structure for hydrogen cyanide, which contains that ask you to draw
Lewis structures.
one hydrogen atom , one carbon atom , and one nitrogen atom.
Keyword: HC 6 BNDX

188 CHAPTER 6
 Resonance Structures
Some molecules and ions cannot be represented adequately by a single
Lewis structure. One such molecule is ozone. Ov which can be repre-
sented by either of the following Lewis structures.

0=0-0 : or —
: 0 0=0

Notice that each structure indicates that the ozone molecule has two
types of 0 -0 bonds, one single and one double. Chemists once specu -
lated that ozone split its time existing as one ol these two structures. con-
stantly alternating, or “resonating." from one to the other. Experiments,
however, revealed that the oxygen-oxygen bonds in ozone are identical .
Therefore, scientists now say that ozone has a single structure that is the
average of these two structures. Together the structures are referred to
as resonance structures or resonance hybrids . Resonance refers to bond-
ing in molecules or ions that cannot be correctly represented by a single
Lewis structure.To indicate resonance, a double-headed arrow is placed
between a molecule's resonance structures.

0=0-0 : f » :0 — 0=0

Covalent - Network Bonding

All the covalent compounds that you have read about so far are mole -
cular. They consist of many identical molecules held together by forces
acting between the molecules. ( You will read more about these inter -
molecular forces in Section 5.) There are many covalently bonded com -
pounds that do not contain individual molecules, but instead can be
pictured as continuous, three-dimensional networks of bonded atoms.
You will read more about covalently bonded networks in Chapter 7.

SECTION REVIEW 4. Draw the Lewis structures for the following

1. Define the following: molecules:
a . bond length b. bond energy a. IBr d. SiCI4

2. State the octet rule. b. CH 3Br e. F 20

3. How many pairs of electrons are shared in the c. C2HCI

following types of covalent bonds ? Critical Thinking
a. a single bond 5 . APPLYING MODELS Compare the molecules
b. a double bond H 2 NNH 2 and HNNH. Which molecule has the
c. a triple bond stronger N- N bond?

CHEMICAL BONDING 189

 SECTION 3
Ionic Bonding and
OBJECTIVES Ionic Compounds
J Compare and contrast a
chemical formula for a
molecular compound with
one for an ionic compound.
Most of the rocks and minerals that make up Earth s crust consist of
'

positive and negative ions held together by ionic bonding. A familiar

^ Discuss the arrangements
of ions in crystals. example of an ionically bonded compound is sodium chloride, or com -
mon table salt , which is found in nature as rock salt. A sodium ion. Na\
has a charge of l+. A chloride ion. Cl , has a charge of 1- There is an
"

j Define lattice energy and

electrical force of attraction between oppositely charged ions. In sodi-
explain its significance.
um chloride, these ions combine in a one - to- one ratio—NaXl —so
that each positive charge is balanced by a negative charge. The chemi-
J
> List and compare the distinc- cal formula for sodium chloride is usually written simply as NaCI.
tive properties of ionic and An ionic compound is composed of positive and negative ions that are
molecular compounds. combined so that the numbers of positive and negative charges are equal.
Most ionic compounds exist as crystalline solids ( see Figure 12 ) . A crys -
tal of any ionic compound is a three -dimensional network of positive
^ Write the Lewis structure for
a polyatomic ion given the and negative ions mutually attracted to one another. As a result , in con-
identity of the atoms com- trast to a molecular compound, an ionic compound is not composed of
bined and other appropriate independent, neutral units that can be isolated and examined. The
information. chemical formula of an ionic compound merely represents the simplest
ratio of the compound’s combined ions that gives electrical neutrality.
The chemical formula of an ionic compound shows the ratio of
the ions present in a sample of any size. A formula unit is the simplest
collection of atoms from which an ionic compound 's formula can be
established. For example, one formula unit of sodium chloride, NaCI is .
one sodium cation plus one chloride anion. ( In the naming of a
monatomic anion, the ending of the element ’s name is replaced with
- ide. See Chapter 7 for more details.)
The ratio of ions in a formula unit depends on the charges of the ions
combined. For example, to achieve electrical neutrality in the ionic com -
pound calcium fluoride, two fluoride anions, F , each with a charge of
"

1 -. must balance the 2+ charge of each calcium cation. Ca2^. Therefore,

the formula of calcium fluoride is CaF -,.

Formation of Ionic Compounds

FIGURE 12 Like most ionic com- Electron -dot notation can be used to demonstrate the changes that
pounds. sodium chloride is a crys- take place in ionic bonding. Ionic compounds do not ordinarily form by
talline solid. the combination of isolated ions, but consider for a moment a sodium

190 CHAPTER 6
atom and a chlorine atom approaching each other. The two atoms are
neutral and have one and seven valence electrons, respectively.
Na ’ • Cl :
Sodium atom Chlorine atom

We have already seen that atoms of sodium and the other alkali met -
als readily lose one electron to form cations. And we have seen that
atoms of chlorine and the other halogens readily gain one electron to
form anions. The combination of sodium and chlorine atoms to produce
one formula unit of sodium chloride can thus be represented as follows.

Na - + : C1 : -> Na" + : CI :“

Sodium atom Chlorine atom Sodium cation Chloride anion

FIGURE 13 The ions in an ionic
The transfer of an electron from the sodium atom to the chlorine atom compound lower their potential
transforms each atom into an ion with a noble -gas configuration. In the energy by forming an orderly, three -
combination of calcium with fluorine, two fluorine atoms are needed to dimensional array in which the
positive and negative charges are
accept the two valence electrons given up by one calcium atom . balanced . The electrical forces
of attraction between oppositely
Ca *
+ : F: + : F: Ca 2" + : F:“ + '
F charged ions extend over long dis-
Calcium atom Fluorine atoms Calcium cation Fluoride anions tances. causing a large decrease
in potential energy.

Characteristics of Ionic Bonding

Recall that nature favors arrangements in which potential energy is
minimized . In an ionic crystal, ions minimize their potential energy by
S(
7INKS, Mf*
Dmtoprt MKJ aunteM by Uw
*
combining in an orderly arrangement known as a crystal lattice ( see Wtntt ftidwn AHMIMM

For a variety of links related to this

Figure 13 ). The attractive forces at work within an ionic crystal include
.
chapter, go to www.scilinks org
those between oppositely charged ions and those between the nuclei
and electrons of adjacent ions. The repulsive forces include those
Topic: Ionic Bonding
SciLinks code: HC 60815
^
between like -charged ions and those between electrons of adjacent
ions. The distances between ions and their arrangement in a crystal rep-
resent a balance among all these forces. Sodium chloride s crystal struc-
ture is shown in Figure 14 below.

FIGURE 14 Two models of the

crystal structure of sodium chloride
are shown , ( a ) To illustrate the ions *

actual arrangement, the sodium and

chloride ions are shown with their
electron clouds just touching.
( b ) In an expanded view, ihe distances
between ions have been exaggerated
in order to clarify the positioning of
(a ) the ions in the structure.

CHEMICAL BONDING 191

 FIGURE 15 The figure shows the
ions that most closely surround
a chloride anion and a sodium cation Na +
within the crystal structure of NaCI .
The structure is composed such
that ( a ) six NV ions surround each
Cl ion. At the same time ( b ) six CT
,

ions surround each Na + ion ( which

cannot he seen hut whose location is
indicated by the dashed outline ) .

Figure 15 shows the crystal structure of sodium chloride in greater

detail. Within the arrangement , each sodium cation is surrounded by six
chloride anions. At the same time, each chloride anion is surrounded by
six sodium cations. Attraction between the adjacent oppositely charged
ions is much stronger than repulsion by other ions of the same charge,
which are farther away.
The three-dimensional arrangements of ions and the strengths of
attraction between them vary with the sizes and charges of the ions and
the numbers of ions of different charges. For example, in calcium fluo-
ride. there are two anions for each cation . Each calcium cation is sur -
rounded by eight fluoride anions. At the same time, each fluoride ion is
surrounded by four calcium cations, as shown in Figure 16.
To compare bond strengths in ionic compounds, chemists compare
the amounts of energy released when separated ions in a gas come
together to form a crystalline solid . Lattice energy is the energy released
when one nude of an unite crystalline compound is formed from gaseous
ions. Lattice energy values for a few common ionic compounds are
shown in Table 3. The negative energy values indicate that energy is
released when the crystals are formed .

Calcium ion , Ca 2 4

FIGURE 16 In the crystal

structure of calcium fluoride. CaF:.
each calcium cation is surrounded
by eight fluoride anions and each
fluoride ion is surrounded by four
calcium cations. This is the closest
possible packing of the ions in
which the positive and negative
charges are balanced . Fluoride ion, F

192 CHAPTER 6
 A Comparison of Ionic TABLE 3 Lattice
Energies of Some Common
and Molecular Compounds Ionic Compounds
Lattice energy
The force that holds ions together in ionic compounds is a very strong over-
Compound ( kJ / mol )
all attraction between positive and negative charges. In a molecular com -
pound , the covalent bonds of the atoms making up each molecule are also NaCl -787.5
strong. But the forces of attraction between molecules are much weaker NaBr -751.4
than the forces among formula units in ionic bonding.This difference in the CaF: -2634.7
strength of attraction between the basic units of molecular and ionic com - LiCI -861.3
pounds gives rise to different properties in the two types of compounds.
The melting point , boiling point , and hardness of a compound depend LiF -1032
on how strongly its basic units are attracted to each other. Because the MgO -3760
forces of attraction between individual molecules are not very strong, KC1 -715
many molecular compounds melt at low temperatures. In fact , many mol -
ecular compounds are already completely gaseous at room temperature.
In contrast , the ions in ionic compounds are held together by strong
attractive forces, so ionic compounds generally have higher melting and
boiling points than do molecular compounds.
Ionic compounds are hard but brittle. Why ? In an ionic crystal , even
a slight shift of one row of ions relative to another causes a large buildup
of repulsive forces, as shown in Figure 17. These forces make it difficult
for one layer to move relative to another, causing ionic compounds to
be hard . If one layer is moved , however, the repulsive forces make the
layers part completely, causing ionic compounds to be brittle.
In the solid state, the ions cannot move, so the compounds are not
electrical conductors. In the molten state, ionic compounds are electri -
cal conductors because the ions can move freely to carry electrical cur -
rent . Many ionic compounds can dissolve in water. When they dissolve,
their ions separate from each other and become surrounded by water
molecules. These ions are free to move through the solution, so such
solutions are electrical conductors. Other ionic compounds do not dis-
solve in water, however, because the attractions between the water mol -
ecules and the ions cannot overcome the attractions between the ions.

—-
4 a Strong repulsion

c
' 4 0 * 4

* 4
• •- T

Attraction
4
Attraction
0
4 FIGURE 17 ( a ) The attraction
between positive and negative ions
in a crystalline ionic compound
causes layers of ions to resist motion ,
( b ) When struck with sufficient
force, the layers shift so that ions of
Force the same charge approach each
dislocates crystal plane other, causing repulsion . As a result ,
( a) ( b) the crystal shatters along the planes.

CHEMICAL BONDING 193

 Polyatomic Ions
Certain atoms bond covalently with each other to form a group of
atoms that has both molecular and ionic characteristics. A charged
group of covalently bonded atoms is known as a polyatomic ion.
Polyatomic ions combine with ions of opposite charge to form ionic
compounds. The charge of a polyatomic ion results from an excess of
electrons ( negative charge) or a shortage of electrons ( positive
charge ). For example, an ammonium ion, a common positively charged
polyatomic ion, contains one nitrogen atom and four hydrogen atoms
Chemistry in Action and has a single positive charge. Its formula is NH4, sometimes written
(io to go.hrw.com lor a full-length as |NH 4| * to show that the group of atoms as a whole has a charge of
article on nanoscale computers. l +. The seven protons in the nitrogen atom plus the four protons in the
four hydrogen atoms give the ammonium ion a total positive charge of
Keyword: HC 6 BNDX
11+. An independent nitrogen atom has seven electrons, and four inde -
pendent hydrogen atoms have a total of four electrons. When these
atoms combine to form an ammonium ion. one of their electrons is lost ,
giving the polyatomic ion a total negative charge of 10-.
Lewis structures for the ammonium ion and some common negative
polyatomic ions — the nitrate, sulfate, and phosphate ions—are shown
below. To find the Lewis structure for a polyatomic ion. follow the steps
.
of Sample Problem D with the following exception. If the ion is nega -
tively charged, add to the total number of valence electrons a number
of electrons corresponding to the ion's negative charge. If the ion is pos-
itively charged, subtract from the total number of valence electrons a
number of electrons corresponding to the ion's positive charge.

+ 2- 3-
II o o o
H : N: H N "O O S O: : O P Q:
H O o o
Ammonium ion Nitrate ion Sulfate ion Phosphate ion

SECTION REVIEW 4. Compound B has lower melting and boiling

1. Give two examples of an ionic compound. points than compound A . At the same tempera -
ture, compound B vaporizes faster than compound
2. Use electron- dot notation to demonstrate the A. If one of these compounds is ionic and the
formation of ionic compounds involving the other is molecular, which would you expect to be
following: molecular ? ionic ? Explain your reasoning.
a. Li and Cl
Critical Thinking
b. Ca and I
5. ANALYZING DATA The melting points for the com-
3. Distinguish between ionic and molecular pounds Li2 S, Rb2 S, and K 2 S are 900°C, 530°C, and
compounds in terms of the basic units that 840°C, respectively. List these three compounds in
each is composed of. order of increasing lattice energy.

194 CHAPTER 6
Metallic Bonding SECTION 4

OBJECTIVES
sj Describe the electron- sea
C hemical bonding is different in metals than it is in ionic molecular or
, , model of metallic bonding,
covalent -network compounds. litis difference is reflected in the unique and explain why metals are
properties of metals. They are excellent electrical conductors in the solid good electrical conductors.
state—much better conductors than even molten ionic compounds. This
property is due to the highly mobile valence electrons of the atoms that Explain why metal surfaces
make up a metal. Such mobility is not possible in molecular compounds, in are shiny.
which valence electrons are localized in electron-pair bonds between neu-
tral atoms. Nor is it possible in solid ionic compounds, in which electrons
are bound to individual ions that are held in place in crystal structures. ^ Explain why metals are mal-
leable and ductile but ionic -
crystalline compounds are not.

The Metallic- Bond Model

The highest energy levels of most metal atoms are occupied by very few Dmtoprt Md iMMrtMurd by to

electrons. In s-block metals, for example, one or two valence electrons

NMMMUI SOMU Teicbm AMooJtim

For a variety of links related to this

occupy the outermost orbital, and all three outermost / > orbitals, which chapter, go to www.scilinks.orci
can hold a total of six electrons, are vacant. In addition to completely Topic: Metallic Bonding
vacant outer / > orbitals, d-block metals also possess many vacant d SciLinks code: HC 60944
orbitals in the energy level just below their highest energy level.
Within a metal, the vacant orbitals in the atoms* outer energy levels
overlap. This overlapping of orbitals allows the outer electrons of the
atoms to roam freely throughout the entire metal. The electrons are
delocalized, which means that they do not belong to any one atom but
move freely about the metal's network of empty atomic orbitals. These
mobile electrons form a sea of electrons around the metal atoms, which
are packed together in a crystal lattice ( see Figure IS ) . The chemical
bonding that results from the attraction between metal atoms and the sur -
rounding sea rtf electrons is called metallic bonding.

Metallic Properties
The freedom of electrons to move in a network of metal atoms accounts
for the high electrical and thermal conductivity characteristic of all met -
als. In addition, metals are both strong absorbers and reflectors of light. FIGURE 18 Tlie model shows
Because they contain many orbitals separated by extremely small energy a portion of the crystal structure of
differences, metals can absorb a wide range of light frequencies. This solid sodium. The atoms are arranged
so that each sodium atom is sur-
absorption of light results in the excitation of the metal atoms' electrons
rounded by eight other sodium
to higher energy levels. However, in metals the electrons immediately fall atoms. The atoms are relatively fixed
back down to lower levels, emitting energy in the form of light at a fre- in position, while the electrons are
quency similar to the absorbed frequency. This re-radiated ( or reflected ) free to move throughout the crystal,
light is responsible for the metallic appearance or luster of metal surfaces. forming an electron sea.

CHEMICAL BONDING 195

 Most metals are also easy to form into desired shapes. Two important
properties related to this characteristic are malleability and ductility.
Malleability is the ability of a substance to be hammered or beaten into
thin sheets . Ductility is the ability of a substance to be drawn, pulled , or
extruded through a small opening to produce a wire. The malleability and
ductility of metals are possible because metallic bonding is the same in
all directions throughout the solid. When struck, one plane of atoms in a
metal can slide past another without encountering resistance or break -
ing bonds. By contrast, recall from Section 3 that shifting the layers of an
ionic crystal causes the bonds to break and the crystal to shatter.

Metallic Bond Strength

Metallic bond strength varies with the nuclear charge of the metal
atoms and the number of electrons in the metal's electron sea. Both of
these factors are reflected in a metal s enthalpy of vaporization . The
amount of energy as heat required to vaporize the metal is a measure of
the strength of the bonds that hold the metal together. The enthalpy of
vaporization is defined as the amount of energy absorbed as heat when
a specified amount of a substance vaporizes at constant pressure. Some
enthalpies of vaporization for metals are given in Tabic 4.

FIGURE 19 Unlike ionic

TABLE 4 Enthalpies of Vaporization of Some Metals (kJImol )
crystalline compounds, most metals
are malleable. TTiis properly allows Period Element
iron , for example, to he shaped into Second Li Be
useful tools.
147 297
Third Na Mg Al
97 128 294
Fourth K Ca Sc
77 155 333
Fifth Rb Sr Y
76 137 365
Sixth Cs Ba La
64 140 402

SECTION REVIEW 3. Explain why most metals are malleable and ductile
.
1 Describe the electron-sea model of metallic but ionic crystals are not.
bonding. Critical Thinking
2. What is the relationship between metallic bond 4. ORGANIZING IDEAS Explain why metals are good
strength and enthalpy of vaporization? electrical conductors.

196 CHAPTER 6
Molecular Geometry SECTION 5

OBJECTIVES
J
> Explain VSEPR theory.
1 he properties of molecules depend not only on the bonding of
atoms but also on molecular geometry — the three-dimensional
arrangement of a molecule 's atoms in space. The polarity of each ^ Predict the shapes of
molecules or polyatomic
bond, along with the geometry of the molecule, determines molecular ions using VSEPR theory.
polarity, or the uneven distribution of molecular charge. As you will
read, molecular polarity strongly influences the forces that act between
molecules in liquids and solids. Explain how the shapes of
A chemical formula reveals little information about a molecule's molecules are accounted
for by hybridization theory.
geometry. After performing many tests designed to reveal the shapes of
various molecules, chemists developed two different, equally successful
theories to explain certain aspects of their findings. One theory accounts ^ Describe dipole -dipole
for molecular bond angles.The other is used to describe the orbitals that forces, hydrogen bonding,
contain the valence electrons of a molecule 's atoms. induced dipoles, and London
dispersion forces and their
effects on properties such as
boiling and melting points.
VSEPR Theory
J Explain what determines
As shown in Figure 20, diatomic molecules, like those of hydrogen, 1 L , molecular polarity.
and hydrogen chloride. HC1. must be linear because they consist of only
two atoms. To predict the geometries of more complicated molecules,
-
one must consider the locations of all electron pairs surrounding the
bonded atoms. This is the basis of VSEPR theory.
Hie abbreviation VSEPR stands for “ valence-shell, electron-pair
repulsion.*' referring to the repulsion between pairs of valence electrons
of the atoms in a molecule. VSEPR theory states that repulsion between (a ) Hydrogen, H 2
the sets of valence -level electrons surrounding an atom causes these sets
to be oriented as far apart as possible. How does the assumption that
electrons in molecules repel each other account for molecular shapes?
For now let us consider only molecules with no unshared valence elec -
tron pairs on the central atom.
Let 's examine the simple molecule BeF:. The beryllium atom forms ( b) Hydrogen chloride, HCI
a covalent bond w ith each fluorine atom and does not follow the octet
rule. It is surrounded by only the two electron pairs that it shares with FIGURE 20 Ball-and- stick models
the fluorine atoms. illustrate the linearity of diatomic
molecules, ( a ) A hydrogen molecule
: F B e : F:
is represented by two identical halls
( the hydrogen atoms ) joined by a
solid bar ( the covalent bond ), ( b ) A
According to VSEPR theory, the shared pairs w ill be as far away from hydrogen chloride molecule is com-
each other as possible. As shown in Figure 21 a on the next page, the dis- posed of dissimilar atoms, but it is
tance between electron pairs is maximized if the bonds to fluorine are still linear.

CHEMICAL BONDING 197

 on opposite sides of the beryllium atom. ISO apart. Thus, all
three atoms lie on a straight line. The molecule is linear.
If we represent the central atom in a molecule by the let -
ter A and we represent the atoms bonded to the central
atom by .
the letter B, then according to VSEPR theory BeF:
(a) .
Beryllium fluoride BeF 2 is an example of an AB: molecule, which is linear. Can von
determine what an AB3 molecule looks like? The three
A — B bonds stay farthest apart by pointing to the corners of
an equilateral triangle, giving 120 angles between the
bonds. This trigonal-planar geometry is shown in Figure 21h
for the AIT, molecule boron trifluoride. 8F3.
The central atoms in AB 4 molecules follow the octet rule
by sharing four electron pairs with B atoms. The distance
( b) .
Boron trifluoride BF 3
between electron pairs is maximized if each A — B bond
points to one of four corners of a tetrahedron. This geome-
try is shown in Figure 21c for the AB 4 molecule methane.

r£
CH 4. The same figure shows that in a tetrahedral molecule,
109.5
each of the bond angles formed by the A atom and any two
of the B atoms is equal to 109.5 .
i Hie shapes of various molecules are summarized in
.
Table 5 B can represent a single type of atom, a group of
AB4 identical atoms, or a group of different atoms on the same
( c) Methane CH 4 . molecule. Hie shape of the molecule will still be based on
the forms given in the table. However, different sizes of B
FIGURE 21 Ball -and -stick models show groups distort the bond angles, making some bond angles
the shapes of ( a ) AB:, ( b ) AB3. and ( c ) AB4 larger or smaller than those given in the table.
molecules according to VSEPR theory.

SAMPLE PROBLEM E
Use VSEPR theory to predict the molecular geometry of boron trichloride, BCIV

SOLUTION First write the Lewis structure for BCl3. Boron is in Group 13 and has three valence
electrons.
• B*

Chlorine is in Group 17, so each chlorine atom has seven valence electrons.
:Q :

The total number of available valence electrons is therefore 24c ( 3c from boron and 2 lc
from chlorine ). The following Lewis structure uses all 24c .
: Cl
: Cl : B:Cl :

This molecule is an exception to the octet rule because in this case B forms only three
bonds. Boron trichloride is an AB3 type of molecule. Therefore, according to VSEPR theo -
ry, it should have trigonal- planar geometry.

198 CHAPTER 6
 PRACTICE Answers in Appendix E

1. Use VSEPR theory to predict the molecular geometry of the Go to go.hrw.com for
following molecules: more practice problems
a . Ill b. CBr 4 c. CHXL that ask you to predict
molecular geometry.
Keyword: HC 6 BNDX

VSEPR Theory and Unshared Electron Pairs

Ammonia. NHV and water. U:0. are examples of molecules in
which the central atom has both shared and unshared electron pairs SCllNKS . wi r >
Otvttopri tn4 mato*m4 by Ikt
( see Table 5 on the next page for their Lewis structures ). How does
HtftoMl Sd«Mr Tudwn AiMcutwa

For a variety of links related to this

VSEPR theory account for the geometries of these molecules? chapter, go to wwvv. scilinks.org
The Lewis structure of ammonia shows that in addition to the
Topic: VSEPR Theory
three electron pairs it shares with the three hydrogen atoms, the Sci Links code: HC61621
central nitrogen atom has one unshared pair of electrons.
f
H •N H
H
VSEPR theory postulates that the lone pair occupies space around
the nitrogen atom just as the bonding pairs do. Thus, as in an AB4
molecule, the electron pairs maximize their separation bv assuming
the four corners of a tetrahedron . Lone pairs do occupy space, but our
description of the observed shape of a molecule refers to the positions
of atoms only. Consequently, as show n in Figure 22a. the molecular
geometry of an ammonia molecule is that of a pyramid with a trian -
gular base. The general VSEPR formula for molecules such as ammo-
nia is AB3E, where E represents the unshared electron pair. FIGURE 22 The locations ot
A water molecule has two unshared electron pairs. It is an AB:E: bonds and unshared electrons are
molecule. Here, the oxygen atom is at the center of a tetrahedron , shown for molecules of ( a ) ammonia
and ( b ) water. Although unshared
with two corners occupied by hydrogen atoms and two by the
electrons occupy space around the
unshared pairs ( Figure 22b ). Again , VSEPR theory states that the central atoms, the shapes of the mole -
lone pairs occupy space around the central atom but that the actual cules depend onI \ on the position
shape of the molecule is determined by the positions of the atoms of the molecules atoms, as clearly '

only. In the case of water, this results in a “ bent ." or angular, molecule. shown bv the ball -and -stick models.

t i v / i >\
% /
/ ' i
l
\ / /
t \ / \
/ i \ /
l \
/ l V / l V
/ I \ f t \
/ I \ / / s
t I \ t I \
t I \ t I \

f
/
*
; N \
s
> /
/
t

I
i o K
\
\
/ I \ / » %
/ I \ I \
f
i s i \
H \
.^ H
\ / \
N
/
i H \ i
/

\ i i

••
\ » \V
\
‘ V

H H

(a) Ammonia, NH 3 ( b) Water, H 20

CHEMICAL BONDING 199

 In Figure 22b, note that the bond angles in ammonia and water are
somewhat less than the 109.5 bond angles of a perfectly tetrahedral
molecule. These angles are smaller because the unshared electron pairs
repel electrons more strongly than do bonding electron pairs .
Table 5 also includes an example of an AB2E type molecule. This
type of molecule results when a central atom forms two bonds and
retains one unshared electron pair.
Finally, in VSEPR theory, double and triple bonds are treated in the
same way as single bonds. And polyatomic ions are treated similarly to
molecules. ( Remember to consider all of the electron pairs present in
any ion or molecule.) Thus, Lewis structures and Table 5 can be used
together to predict the shapes of polyatomic ions as well as molecules
with double or triple bonds.

TABLE 5 VSEPR Theory and Molecular Geometry

Atoms Lone
bonded to pairs of Type of Formula Lewis
Molecular shape central atom electrons molecule example structure

Linear 2 0 AEL BeF: • F- Be- F -

; F\ / F
Trigonal- B
3 0 A B3 BF3
planar
: F:

N
Bent or Angular 2 1 AB -»E ONF ..OS. V
F:
-

H
Tetrahedral 4 0 AB4 CH4 H-C- H
H

Trigonal- N
3 AB3E NH3 /l\
pyramidal H FI H

O
Bent or Angular AB,E, FLO
\A H

C
Trigonal-
bipvramidal
5 0 AB5 PC15 :CI — P/ 'a
|:
••
:

:CIC

;F
:F F:
Octahedral 6 0 A B6 SF(, s
:F

^ F:

200 CHAPTER 6
 SAMPLE PROBLEM F
a. Use VSEPR theory to predict the shape of a molecule of carbon dioxide, C( ):.
b. Use VSEPR theory to predict the shape of a chlorate ion, ClOj.

SOLUTION a . The Lewis structure of carbon dioxide shows two carbon-oxygen double bonds and no
unshared electron pairs on the carbon atom. To simplify the molecule's Lewis structure,
we represent the covalent bonds with lines instead of dots.
o=c=o
Iliis is an AB -> molecule, which is linear.

b. The Lewis structure of a chlorate ion shows three oxygen atoms and an unshared pair of
electrons surrounding a central chlorine atom. Again, lines are used to represent the
covalent bonds.
Cl
O Q 6:

.
The chlorate ion is an AB;E type It has trigonal-pyramidal geometry, with the three oxy -
gen atoms at the base of the pyramid and the chlorine atom at the top.

PRACTICE Answers in Appendix E

1. Use VSEPR theory to predict the molecular geometries of the

molecules whose Lewis structures are given below'. sSTtfaiVfLdii
Go to go.hrw.com for
a. : F- S - F: b. CT- P-CT more practice problems
:Cb that ask you to use
VSEPR theory.
Keyword: HC 6 BNDX

Hybridization
VSEPR theory is useful for explaining the shapes of molecules. I lowever,
it does not reveal the relationship between a molecule ’s geometry and the
.
orbitals occupied by its bonding electrons To explain how the orbitals of
an atom become rearranged when the atom forms covalent bonds, a dif -
ferent model is used. Iliis model is called hybridization, which is the tttix -
ing of two or more atomic orbitals of similar energies on the same atom to
produce new hybrid atomic orbitals of equal energies.
Methane, CH4, provides a good example of how hybridization is used
to explain the geometry of molecular orbitals.The orbital notation for a
carbon atom shows that it has four valence electrons, two in the Is
orbital and two in 2p orbitals.

C UU T T
v
Is 2s
2p

CHEMICAL BONDING 201

 We know from experiments that a methane molecule has tetrahedral
geometry. How does carbon form four equivalent , tetrahedrally
arranged covalent bonds by orbital overlap with four other atoms?
Two of carbon's valence electrons occupy the 2v orbital, and two
occupy the 2/; orbitals. Recall that the 2v orbital and the 2 p orbitals have
different shapes. To achieve four equivalent bonds, carbon's 2s and
three 2p orbitals hybridize to form four new. identical orbitals called sp '
orbitals. The superscript 3 indicates that three p orbitals were included
in the hybridization; the superscript I on the .v is understood. TTie sp '
orbitals all have the same energy, which is greater than that of the 2v
orbital but less than that of the 2p orbitals, as shown in Figure 23.

FIGURE 23 The \ /T hybridization

11
T T
of carbon's outer orbitals combines I Ivbridi / ation T T T T
one v and three p orbitals to form Si -P •

U
"
^
sr
T
lour s / » hybrid orbitals. \\ henever C /
hy bridization occurs, the resulting u 2.v
hybrid orbitals are at an energy level Ti n
between the levels of the orbitals Is Is
that have combined. C arbon orbitals ’s C arbon s orbitals after '

before hybridization sp' hybridization

Hybrid orbitals are orhinds of equal energy produced by the combina -

tion of two or more orbitals on the same atom. The number of hybrid
orbitals produced equals the number of orbitals that have combined.
Bonding with carbon sp ' orbitals is illustrated in Figure 24a for a mol -
ecule of methane.
Hybridization also explains the bonding and geometry of many
molecules formed by Group 15 and 16 elements. The sp:' hybridization
of a nitrogen atom ( [ He ]2r 2/ ) yields four hybrid orbitals —one rv
orbital containing a pair of electrons and three orbitals that each con -
FIGURE 24 Bonds formed lain an unpaired electron. Each unpaired electron is capable of form-
by t he overlap ol the 1 \ orbitals of
ing a single bond, as shown for ammonia in Figure 24b. Similarly, two
hydrogen atoms and the orbitals
of the four sp ' hybrid orbitals on an oxygen atom (|He|2r 2/ j4 ) are
ol ( a ) carbon, ( h ) nitrogen, and
( e ) oxygen. For the sake of clarity, occupied by two electron pairs and two are occupied by unpaired elec -
only the hybrid orbitals of the cen - trons. Each unpaired electron can form a single bond, as shown for
tral atoms are shown. water in Figure 24c.

H
/ ! s

/
t ' I '* >
i
k t I r ' ttI ' \
/ I I N / \
I \ / I \ / I \
I i \ f \
/
I /
l
« t I \
/ v / V
I t

/
t I'
c s
\ /
/
t

; N
N
V
\
/
/
/

; o
\
i
\
I \ i t
I \ \
I V / \ /
i
H \\ » \ / 4
H\ i \ H \\ i
'i
i H .
.
V
s i i
i
I V r
\\
-'
i
\ I
i
V
\ \ *

H H H

( a) Methane CH 4 . (b) Ammonia NH 3 . (c ) Water H20 .

202 CHAPTER 6
 TABLE 6 Geometry of Hybrid Orbitals
Atomic Type of Number of
orbitals hybridization hybrid orbitals Geometry

J. p sp 2

Linear

.
s, p p sp ~ 3
120
Trigonal- planar

109.5

.
s, p p p < sp'- 4
'/
Tetrahedral

The linear geometry of molecules such as beryllium fluoride. BeF->,

( see Table 5 ) is made possible by hybridization invoking the s orbital
and one available empty p orbital to yield sp hybrid orbitals. The
trigonal-planar geometry of molecules such as boron fluoride, BF; is .
made possible by hybridization involving the s orbital, one singly occu -
pied p orbital, and one empty p orbital to yield sp2 hybrid orbitals. The
geometries of sp .sp 2. and sp' hybrid orbitals are summarized in Table 6.

Intermolecular Forces
CHEMISTRY
As a liquid is heated, the kinetic energy of its particles increases. At the
Module 4 : Chemical Bonding
boiling point, the energy is sufficient to overcome the force of attraction
between the liquid's particles. The particles pull away from each other
and enter the gas phase. Boiling point is therefore a good measure of
the force of attraction between particles of a liquid. The higher the boil -
ing point , the stronger the forces between particles.
Hie forces of attraction between molecules are known as intermolec -
ultir forces. Intermolecular forces vary in strength but are generally
weaker than bonds that join atoms in molecules, ions in ionic com -
pounds, or metal atoms in solid metals. Compare the boiling points of the
metals and ionic compounds in Table 7 on the next page with those of
the molecular substances listed. Note that the values for ionic com -
pounds and metals are much higher than those for molecular substances.

CHEMICAL BONDING 203

 TABLE 7 Boiling Points and Bonding Types
Bonding type Substance bp (1 atm, °C)
Nonpolar-covalent -253
( molecular ) O, - 183
ci2 -34
Br2 59
CH4 - 164
ca4 77
QH, 80
Polar-covalent PH3 -88
( molecular ) NH3 -33
H->S -61
H:0 100
HF 20
HC1 -85
ICl 97
Ionic NaCI 1413
MgF: 2239
Metallic Cu 2567
Fe 2750
W 5660

Molecular Polarity and Dipole-Dipole Forces

The strongest intermolecular forces exist between polar molecules.
CAREERS in Chemistry Polar molecules act as tiny dipoles because of their uneven charge dis -
tribution. A dipole is created by equal but opposite charges that are sep -
Computational Chemist arated by a short distance. The direction of a dipole is from the dipole's
Computational chemistry is the study of positive pole to its negative pole. A dipole is represented by an arrow
molecules, their properties, and the inter - . with a head pointing toward the negative pole and a crossed tail situ -
action between molecules using mathe- ated at the positive pole. The dipole created by a hydrogen chloride
matical equations that are based on the molecule, which has its negative end at the more electronegative chlo-
laws of quantum mechanics and which
describe the motion of the electrons.
rine atom, is indicated as follows.
Today, widely-available software pack- ->
ages exist that allow chemists to solve H-CI
these equations for molecules under
study. The negative region in one polar molecule attracts the positive
Computational chemists combine
region in adjacent molecules, and so on throughout a liquid or solid. The
their expertise in mathematics, their
computer skills, and their love of chem -
forces of attraction between polar molecules are known as dipole -dipole
istry. Computational chemistry has been forces. These forces are short -range forces, acting only between nearby
used in industry to aid in the discovery molecules. The effect of dipole-dipole forces is reflected, for example, by
of new pharmaceutical drugs and of the significant difference between the boiling points of iodine chloride .
new catalysts. Computational chemists I— Cl, and bromine. Br -Br. The boiling point of polar iodine chloride is
are employed in all areas of chemistry
97 C. whereas that of nonpolar bromine is only 59 C. The dipole-dipole
and work closely with experimental
chemists. forces responsible for the relatively high boiling point of ICI are illus-
trated schematically in Figure 25.

204 CHAPTER 6
 Key: FIGURE 25 Ball-and-stick models
illustrate the dipole -dipole forces
I between molecules of iodine chlo-
ride. ICI. In each molecule, the high -
ly electronegative chlorine atom has
a partial negative charge, leaving
each iodine atom with a partial posi-
tive charge. Consequently, the nega -
Dipole - dipole tive and positive ends of neighboring
h-
forces molecules attract each other.

Hie polarity of diatomic molecules such as ICI is determined hv just

one bond. For molecules containing more than two atoms, molecular
polarity depends on both the polarity and the orientation of each bond.
A molecule of water, for example, has two hydrogen-oxygen bonds
in which the more-electronegative oxygen atom is the negative pole
of each bond. Because the molecule is bent , the polarities of these
two bonds combine to make the molecule highly polar, as shown in
.
Figure 26 An ammonia molecule is also highly polar because the dipoles
of the three nitrogen-hydrogen bonds are additive, combining to create
a net molecular dipole. In some molecules, individual bond dipoles can -
cel one another, causing the resulting molecular polarity to be zero.
Carbon dioxide and carbon tetrachloride are molecules of this type.
A polar molecule can induce a dipole in a nonpolar molecule by tem -
porarily attracting its electrons. The result is a short -range intermolecu-
lar force that is somewhat weaker than the dipole-dipole force. The
force of an induced dipole accounts for the solubility of nonpolar 02 in
water. The positive pole of a water molecule attracts the outer electrons

.-
s
A

o
( a) Water, H 20 Ammonia, NH 3

FIGURE 26 ( a ) The bond polari-

ties in a water or an ammonia mole -
cule are additive, causing the
molecule as a whole to be polar.
(b ) In molecules of carbon tetrachlo-
ride and carbon dioxide, the bond
polarities extend equally and sym -
metrically in different directions,
canceling each other s effect and
( b) Carbon tetrachloride, CCI4 Carbon dioxide, C 02 causing each molecule as a whole
(no molecular dipole) (no molecular dipole) to be nonpolar.

CHEMICAL BONDING 205

 o •

Water, H 20 Oxygen, 02

FIGURE 27 Dipole- induced of art adjacent oxygen molecule. The oxygen molecule, then, has an
dipole interaction. The positive pole induced negative pole on the side toward the water molecule and
of a water molecule causes a tempo- an induced positive pole on the opposite side. The result is an attraction
rary change in the electron distribu-
to the water molecule, as shown in Figure 27.
tion of an oxygen molecule. The
negative pole induced in the oxygen
molecule is then attracted to the Hydrogen Bonding
positive pole of the water molecule. Some hydrogen-containing compounds, such as hydrogen fluoride
.
( HF) water ( IDO ), and ammonia (NHV). have unusually high boiling
points. This is explained bv the presence of a particularly strong type of
—.
dipole-dipole force. In compounds containing H F H-O. or l l - N
bonds, the large electronegativity differences between hydrogen atoms
SC
/ lNKS. i\V ‘
wd jitwd try Uw
and fluorine, oxygen, or nitrogen atoms make the bonds connecting
them highly polar. This gives the hydrogen atom a positive charge that
NMMil SOM<« TMd n AIMKMIMM
*
is almost half as large as that of a proton. Moreover, the small size of the
For a variety of links related to this
chapter, go to wmy . scilinks .org hydrogen atom allows the atom to come very close to an unshared pair
Topic: Hydrogen Bonding of electrons on an adjacent molecule. The intermolecidar force in which
SciLinks code: HC60777 a hydrogen atom that is bonded to a highly electronegative atom is
attracted to an unshared pair of electrons of an electronegative atom in a
nearby molecule is known as hydrogen bonding.
Hydrogen bonds are usually represented by dotted lines connecting
the hydrogen-bonded hydrogen to the unshared electron pair of the
electronegative atom to which it is attracted, as illustrated for water in
Figure 28. The effect of hydrogen bonding can be seen by comparing the
.
boiling points in Fable 7. Look at phosphine PHV compared with
hydrogen-bonded ammonia . NHV How does hydrogen sulfide I LS. .
compare with hydrogen-bonded water. H20?

'i

FIGURE 28 Space - filling

models illustrate hydrogen bonding
between water molecules. The
dotted lines indicate the attraction
between electronegative oxygen
atoms and electropositive hydrogen
atoms of neighboring molecules.

206 CHAPTER 6
 f

-
v+2 2 2
Weak
4
attractive
force
Momentary dipole Dipole induced in
in one helium atom neighboring atom

FIGURE 29 When an instanta-

neous. temporary dipole develops
London Dispersion Forces in a helium atom it induces a dipole
,

in a neighboring atom .
Even noble-gas atoms and molecules that are nonpolar experience a
weak intermolecular attraction. In any atom or molecule — polar or
nonpolar — the electrons are in continuous motion. As a result, at any
instant the electron distribution may be slightly uneven. The momen-
tary, uneven charge creates a positive pole in one part of the atom or
molecule and a negative pole in another. This temporary dipole can
then induce a dipole in an adjacent atom or molecule. The two are held
together for an instant bv the weak attraction between the temporary
dipoles, as illustrated in Figure 29. The intermolecular attractions result -
ing [mm the constant motion of electrons and the creation of instanta-
neous dipoles are called London dispersion forces, after Fritz London,
who first proposed their existence in 1930.
London forces act between all atoms and molecules. But they are the
only intermolecular forces acting among noble-gas atoms and nonpolar
molecules. This fact is reflected in the low boiling points of the noble
gases and nonpolar molecular compounds listed in Table 7. Because
London forces are dependent on the motion of electrons, their strength
increases with the number of electrons in the interacting atoms or mol -
ecules. In other words, London forces increase with increasing atomic or
.
molar mass This trend can be seen by comparing the boiling points of
.
the gases helium I le. and argon, Ar; hydrogen, 1L, and oxygen. ():; and
chlorine, CL. and bromine. Br 2.

SECTION REVIEW 5. What type of intermolecular force contributes to

1. What two theories can be used to predict molecu- the high boiling point of water ? Explain.
lar geometry ? Critical Thinking
2. Draw the Lewis structure and predict the molecu- 6. INFERRING RELATIONSHIPS What experimental
lar geometry of the following molecules: property directly correlates with the strength of
a. S02 b. CI4 c. BCI3 the intermolecular forces ? Briefly explain your
3. What factors affect the geometry of a molecule? answer.
4. Explain what is meant by sp 3 hybridization.

CHEMICAL BONDING 207

 CHAPTER HIGHLIGHTS
Introduction to Chemical Bonding
I Vocabulary •Most atoms are chemically bonded to other atoms. The three
chemical bond major types of chemical bonding are ionic, covalent, and
ionic bonding metallic.
covalent bonding •In general, atoms of metals bond ionically with atoms of non -
nonpolar-covalent bond .
metals atoms of metals bond metallically with each other, and
polar atoms of nonmetals bond covalently with each other.
polar -covalent bond

Covalent Bonding and Molecular Compounds

I Vocabulary •Atoms in molecules are joined by covalent bonds. In a cova-
molecule Lewis structure lent bond, two atoms share one or more pairs of electrons.
molecular compound structural formula •The octet rule states that many chemical compounds tend to
chemical formula single bond form bonds so that each atom shares or has eight electrons in
molecular formula multiple bond its highest occupied energy level.
bond energy resonance •Bonding within many molecules and ions can be indicated by a
electron - dot notation Lewis structure. Molecules or ions that cannot be correctly
represented by a single Lewis structure are represented by res-
onance structures.

Ionic Bonding and Ionic Compounds

I Vocabulary •An ionic compound is a three-dimensional network of positive
ionic compound and negative ions mutually attracted to one another.
formula unit •Ionic compounds tend to be harder and more brittle and to
lattice energy have higher boiling points than materials containing only cova-
polyatomic ion lently bonded atoms.

Metallic Bonding
I Vocabulary •The “electron sea ”
formed in metallic bonding gives metals their
metallic bonding properties of high electrical and thermal conductivity, malleabili -
malleability .
ty ductility, and luster.
ductility

Molecular Geometry
I Vocabulary •VSEPR theory is used to predict the shapes of molecules based
VSEPR theory on the fact that electron pairs strongly repel each other.
hybridization •I tybridization theory is used to predict the shapes of molecules
hybrid orbitals based on the fact that orbitals within an atom can mix to form
dipole orbitals of equal energy.
hydrogen bonding •Intermolecular forces include dipole-dipole forces and London
London dispersion forces dispersion forces. Hydrogen bonding is a special case of dipole-
dipole forces.

208 CHAPTER 6
 CHAPTER REVIEW

Introduction to Chemical Covalent Bonding and Molecular

Bonding Compounds
SECTION 1 REVIEW SECTION 2 REVIEW
1. What is a chemical bond? 10. What is a molecule ?
2. Identify and define the three major types 11. a. What determines bond length ?
of chemical bonding. b. In general, how are bond energies and bond
3. What is the relationship between electronegativ - lengths related?
ity and the ionic character of a chemical bond? 12. Describe the general location of the electrons in
4. a. What is the meaning of the term polar, as a covalent bond.
applied to chemical bonding? 13. As applied to covalent bonding, what is meant
b. Distinguish between polar-covalent and by an unshared or lone pair of electrons?
nonpolar-covalent bonds. 14. Describe the octet rule in terms of noble -gas
5 . In general, what determines whether atoms will configurations and potential energy.
form chemical bonds? 15. Determine the number of valence electrons in
an atom of each of the following elements:
a. H
PRACTICE PROBLEMS
b. F
6. Determine the electronegativity difference,
c. Mg
the probable bond type, and the more - d. O
electronegative atom with respect to bonds e. A 1
formed between the following pairs of atoms.
f. N
(Hint: See Sample Problem A .)
g- c
a. H and I
b. S and O
.
16 When drawing Lewis structures, which atom is
usually the central atom?
c. k and Br
17. Distinguish between single, double, and triple
.
d Si and Ci
covalent bonds by defining each and providing
e. k and Cl
an illustration of each type.
f. Se and S 18. In writing Lewis structures, how is the need for
g. C and H
multiple bonds generally determined ?
7. List the bonding pairs described in item 6 in
order of increasing covalent character.
8. Use orbital notation to illustrate the bonding PRACTICE PROBLEMS
in each of the following molecules: 19. Use electron-dot notation to illustrate the num -
a. chlorine, CL ber of valence electrons present in one atom of
b. oxygen, Q2 each of the following elements. ( Hint : See
c. hydrogen fluoride, HF Sample Problem B. )
9. The lattice energy of sodium chloride, NaCl. is a. Li
-7X7.5 kJ/mol. The lattice energy of potassium b. Ca
.
chloride kCl. is -715 kJ /mol. In which com - c. Cl
pound is the bonding between ions stronger? d. O
Whv ? e. C
f. P
g. AI
h. S

CHEMICAL BONDING 209

 CHAPTER REVIEW

20. Use electron -dot structures to demonstrate the 28. a. In general , how do ionic and molecular com -
formation of ionic compounds involving the fol - pounds compare in terms of melting points,
lowing elements: boiling points, and ease of vaporization ?
a . Na and S b. What accounts for the observed differences
b. Ca and O in the properties of ionic and molecular
c. Al and S compounds?
21. Draw Lewis structures for each of the following c. C ite three physical properties of ionic
molecules. ( Hint: See Sample Problem D.) compounds.
a . contains one C and four F atoms 29. a . What is a polyatomic ion ?
b. contains two II and one Se atom b. Give two examples of polyatomic ions.
c. contains one N and three I atoms c. In what form do such ions often occur
d . contains one Si and four Br atoms in nature ?
e. contains one C, one Cl. and three H atoms
22. Determine the type of hybrid orbitals formed
bv the boron atom in a molecule of boron fluo- Metallic Bonding
ride. BF . >
SECTION 4 REVIEW
23. Draw Lewis structures for each of the following
molecules. Show resonance structures, if they 30. a . I low do the properties of metals differ from
exist . those of both ionic and molecular compounds?
a . 0: b. What specific property of metals accounts
b. !SL for their unusual electrical conductivity ?
c. CO 31. What properties of metals contribute to their
d . SO, tendency to form metallic bonds?
24. Draw Lewis structures for each of the following 32. a . What is metallic bonding ?
polyatomic ions. Show resonance structures, if b. How can the strength of metallic bonding
they exist . be measured ?
a . OH "

b. H 3C:0:
Molecular Geometry
c. BrO
^ SECTION 5 REVIEW
33. a . How is the VSEPR theory used to classify
Ionic Bonding and Ionic molecules?
Compounds b. What molecular geometry would be expected
for F\ and HF?
SECTION 3 REVIEW 34. According to the VSEPR theory, what molecular
25. a . What is an ionic compound ? geometries are associated with the following
b. In what form do most ionic compounds types of molecules?
occur ? a. AB:
26. a . What is a formula unit ? b. AB:,
b. What are the components of one formula c. AB4
unit of CaF:? d. AB5
27. a. What is lattice energy? e. AB6
b. In general , what is the relationship between 35. Describe the role of each of the following in pre -
lattice energy and the strength of ionic dicting molecular geometries:
bonding? a. unshared electron pairs
b. double bonds

210 CHAPTER 6
 CHAPTER REVIEW

36. a. What arc hybrid orbitals? 47. On the basis of individual bond polarity and ori -
b. What determines the number of hybrid entation . determine whether each of the follow -
orbitals produced by the hybridization of ing molecules would be polar or nonpolar:
an atom ? a. H20
37. a. What are intermolecular forces? b. U
b. In general , how do these forces compare in c. CF4
strength with those in ionic and metallic d . NH ,
bonding? e. CO:
c. What types of molecules have the strongest 48. Draw a Lewis structure for each of the following
intermolecular forces? molecules, and then use the VSEPR theory to
38. What is the relationship between electronegativi - predict the molecular geometry of each:
ty and the polarity of a chemical bond ? a . SCI 2
39. a. What are dipole-dipole forces? b. PI3
b. What determines the polarity of a molecule? c. CLO
.
40 a. What is meant by an induced dipole? d. NH:Cl
b. What is the everyday importance of this type e. SiCljBr
of intermolecular force? f. ONCI
41. a. What is hydrogen bonding? 49. Draw a Lewis structure for each of the following
b. What accounts for its extraordinary strength ? polyatomic ions, and then use VSEPR theory to
42. What are London dispersion forces? determine the geometry of each:
a . N 03
PRACTICE PROBLEMS b. NH 4
c. SO -
43. According to the VSEPR theory, what molecular
geometries are associated with the following d. CIO;^
types of molecules?
a . AB3E
b. AB2E2 MIXED REVIEW
c. AB:E
50. Arrange the following pairs from strongest to
44. Use hybridization to explain the bonding in
weakest attraction:
methane. CH 4.
a . polar molecule and polar molecule
45. For each of the following polar molecules, indi -
b. nonpolar molecule and nonpolar molecule
cate the direction of the resulting dipole:
c. polar molecule and ion
a. H-F
d . ion and ion
b. H -CI
51. Determine the geometry of the following
c. H - Br
d. H - I
molecules:
a . CCl 4
46. Determine whether each of the following bonds
b. BeCL~
would be polar or nonpolar:
c. PH3
a. H - H
52. What types of atoms tend to form the following
b. H-O
types of bonding ?
c. H - F
d. Br- Br a. ionic
b. covalent
e. H -CI
f. H - N c. metallic

CHEMICAL BONDING 211

 CHAPTER REVIEW

53 . What happens to the energy level and stability .

66 Draw a Lewis structure for each of the following
of two bonded atoms when they are separated polyatomic ions and determine their geometries:
and become individual atoms ? .
a NO; c. NHJ
54. Draw the three resonance structures for sulfur b. NOj
.
trioxide SO3. 67. Why do most atoms tend to chemically bonded
55. a. How do ionic and covalent bonding differ? to other atoms ?
b. How does an ionic compound differ from a
molecular compound?
c. How does an ionic compound differ from a CRITICAL THINKING
metal?
56. Write the electron - dot notation for each of the .
68 Inferring Relationships ITie length of a bond
following elements: varies depending tin the type of bond formed.
a. He d. P Predict and compare the lengths of the carbon-
b. Cl e. B carbon bonds in the following molecules.
c. O Explain your answer. ( Hint: See Table 2. )
57. Write the structural formula for methanol . H H H H
CH3OH . H-C-C H
I I
H - C=C - H -
H CsC-H
58. How many K and S2 ions would be in one for -
4 "

mula unit of the ionic compound formed by H H

these ions ? c 2\
\ C2H4
59. Explain metallic bonding in terms of the sparse - 69. Why does F generally form covalent bonds with
ly populated outermost orbitals of metal atoms. great polarity?
60. Explain the role of molecular geometry in 70. Explain what is wrong with the following Lewis
determining molecular polarity. structures, and then correct each one.
61. How does the energy level of a hybrid orbital
a. H -H -S:
compare with the energy levels of the orbitals it
:Q:
was formed from?
62. Aluminum's enthalpy of vaporization is b. H - C=Q- H
2N4 kJ/mol. Beryllium’s enthalpy of vaporiza- CL
tion is 224 kJ/mol. In which element is the
N
bonding stronger between atoms?
63. Determine the electronegativity difference, c. - Cl CL
the probable bonding type, and the more- 71. Ionic compounds tend to have higher boiling
electronegative atom for each of the following points than covalent substances do. Both ammo -
pairs of atoms: nia. NH3, and methane, C'H4, are covalent com -
a. Zn and O c. S and Cl pounds. vet the boiling point of ammonia is
b. Br and 1 130°C higher than that of methane. What might
64. Draw the Lewis structure for each of the account for this large difference?
following molecules:
a. PC13 c. CH3NH2
b. CC12F2 USING THE HANDBOOK
65 . Write the Lewis structure for BeCl2. ( Hint:
72. Figure 18 shows a model for a body-centered
Beryllium atoms do not follow the octet rule. )
cubic crystal. Review the Properties tables for all
of the metals in the Elements Handbook . What
metals exist in bodv -centered cubic structures?

212 CHAPTER 6
 CHAPTER REVIEW

.
73 Group 14 of the Elements Handbook contains a .
77 Searching for the perfect artificial sweetener-
discussion of semiconductors and the hand the- great taste with no Calories—has been the focus
ory of metals. How does this model explain the of chemical research for some time. Molecules
electrical conductivity of metals? such as sucralose. aspartamine, and saccharine
owe their sweetness to their size and shape. One
theory holds that any sweetener must have
RESEARCH & WRITING three sites that fit into the proper taste buds on
the tongue. This theory is appropriately known
.
74 Prepare a report on the work of Linus Pauling. as the “ triangle theory.*' Research artificial
a. Discuss his work on the nature of the chemi - sweeteners to develop a model to show how the
cal bond. triangle theory operates.
b. Linus Pauling was an advocate of the use of
vitamin C as a preventative for colds.
Evaluate Pauling's claims. Determine if there ALTERNATIVE ASSESSMENT
is any scientific evidence that indicates
whether vitamin C helps prevent colds. .
78 Devise a set of criteria that will allow' you to
75. Covalently bonded solids, such as silicon, an ele- classify the following substances as ionic or non-
ment used in computer components, are harder ionic: CaCOj, Cu. H:0. NaBr, and C (graphite).
than pure metals. Research theories that explain Show your criteria to your instructor.
the hardness of covalently bonded solids and 79. Performance Assessment Identify 10 common
their usefulness in the computer industry. substances in and around your home, and indi-
Present your findings to the class. cate whether you would expect these substances
.
76 Natural rubber consists of long chains of carbon to contain ionic, covalent , or metallic bonds.
and hydrogen atoms covalently bonded togeth-
er. When Goodyear accidentally dropped a mix -
ture of sulfur and rubber on a hot stove, the 11
energy from the stove joined these chains
together to make vulcanized rubber. Vulcan was
the Roman god of fire. Hie carbon-hvdrogen
chains in vulcanized rubber are held together
i Graphing Calculator
Classifying Bonding Type
. .
Go to go hnv com for a graphing calculator
bv two sulfur atoms that form covalent bonds exercise that asks you to classify bonding
between the chains. These covalent bonds are type based on electronegativities of atoms.
commonly called disulfide bridges. Explore
Keyword: HC 6BNDX
other molecules that have such disulfide
bridges. Present vour findings to the class.

CHEMICAL BONDING 213

 Math Tutor DRAWING LEWIS STRUCTURES

Drawing Lewis dot structures can help you understand how valence electrons partici-
pate in bonding. Dots are placed around the symbol of an element to represent the
element's valence electrons. For example, carbon has four valence electrons, and its
.
Lewis dot structure is usually written as * C * An atom of fluorine has seven valence
electrons. Fluorine's Lewis dot structure can be written as - F W h e n Lewis structures
for covalently bonded atoms are written, the dots may be placed as needed to show
the electrons shared in each bond. Most atoms bond in a way that gives them a stable
octet of s and p electrons in the highest energy level. So, whenever possible, dots
should be arranged in a way that represents a stable octet around each atom.

/1 Problem-Solving TIPS
• Hydrogen is an exception to the octet rule because hydrogen has only one
electron and becomes stable with two electrons.
• Some elements, such as boron , can bond without achieving an octet because they

have three or fewer electrons to share.

SAMPLE
Draw the Lewis dot structure for a molecule of sulfur dichloride, SC12.
First, write the electron dot notation for each atom.
:CP - •CP s
Next, determine the total number of valence electrons in the atoms.
S 1 x 6e "
be
2CI 2 x 7c "
14c
Total c "
20c "

Arrange the atoms to form a skeleton structure for the molecule, and place electron pairs
between atoms to represent covalent bonds. You can predict the arrangement of atoms bv
figuring out how many covalent bonds each atom must form in order to achieve a stable
.
octet Each chlorine atom, which has 7 valence electrons, must form a single covalent bond.
.
Sulfur, which has 6 valence electrons, must form two covalent bonds The only possible struc -
—
ture is Cl S-Cl.
Finally, insert dots representing the remaining electrons ( lb in this case ), in order to give
each atom an octet.
: Cl : S : Cl :

PRACTICE PROBLEMS
.
1 Draw the electron dot notations for a silicon 2. Draw Lewis structures for hydrogen sulfide.
atom and a strontium atom. ITS, and for formic acid. HCCTH.

214 CHAPTER 6
Answer the following items on a separate piece of paper. 8. Which of the following compounds is predicted
.
1 A chemical bond results from the mutual attrac - to have the highest boiling point ?
tion of the nuclei for A . HCI
A . electrons. .
B CH3COOH ( Note: The two oxygen atoms
B. neutrons. bond to the carbon.)
C . protons. C. CL
D. dipoles. D. SO:

2. A polar covalent bond is likely to form between 9. An unknown substance is an excellent electrical
two atoms that conductor in the solid state and is malleable.
A. are similar in electronegativity. What type of chemical bonding does this sub -
stance exhibit ?
B. are of similar size.
A . ionic bonding
.
C. differ in electronegativity
.
B molecular bonding
.
D have the same number of electrons . C. metallic bonding
3. The Lewis structure of HCN contains
A . one double bond and one single bond.
.
D cannot determine from the information given

.
B one triple bond and one single bond.
SHORT ANSWER

C. two single bonds. 10. What does the hybridization model help
D. two double bonds. explain ?
.
4 According to VSEPR theory, the molecular .
11 Explain why ionic crystals are brittle.
geometry for CH\ is EXTENDED RESPONSE
A . tetrahedral . . .
12. Naphthalene C1(IHK is a nonpolar molecule
.
B trigonal-pyramidal.
and has a boiling point of 218 C. Acetic acid.
C . bent or angular.
CHjCCLH, is a polar molecule and has a boiling
D. None of the above point of 118 C. Which substance has the
.
5 Which molecule contains a double bond? stronger intermolecular forces ? Briefly explain
A. COCL your answer.
B. C:H , "

.
13 Describe and explain the potential energy
c. CF4 changes that occur during the formation of a
.
D SF: covalent bond.
6. Which molecule is polar ?
A . CC14
B. CO:
"
C. so3
D. none of these
7. What is the hybridization of the carbon atoms
in C\ FL?
A . sp
.
B sp2
When several questions refer to
the same graph, table, drawing, or passage, answer
C. sp ' the questions you are sure of first.
.
D The carbon atoms do not hybridize in C2H:.

CHEMICAL BONDING 215

 INQUIRY
EXPERIMENT 6 o L A B

Types of Bonding in Solids

OBJECTIVES BACKGROUND
The purpose of this experiment is to relate certain
• Observe the physical properties of different
solids. properties of solids to the type of bonding the solids
have. These observable properties depend on the
• Relate knowledge of these properties to the type of bonding that holds the molecules, atoms, or
type of bonding in each solid . ions together in each solid. Depending on the type
• Identify the type of bonding in an unknown of bonding, solids may be described as ionic, molecu -
solid . lar. metallic, or covalent network solids. The proper -
ties to be studied are relative melting point , solubility
MATERIALS in aqueous solution, and electrical conductivity.
beakers, 50 niL ( 6 )
SAFETY
Bunsen burner
copper wire
deionized water O
For review of safety, please see the Safety in the
evaporating dishes or crucibles ( 6 )
Chemistry Laboratory in the front of your book.
graduated cylinder, 10 mL
aluminum shot PREPARATION
1 . Make a data table in which to record the results
LEI ) conductivity tester
of melting, water solubility, solid conductivity,
silicon dioxide ( sand ) aqueous solution conductivity, and type of bond -
sodium chloride ( NaCI ) ing of each substance tested.
spatula PROCEDURE
sucrose 1 . Place l g samples of each substance into sepa -
test tubes, small , with solid rubber rate evaporating dishes.
stoppers ( 6 )
2. Touch the electrodes of the conductivity tester
test - tube rack to each solid. After each test , rinse with distilled
tongs water and carefully dry the electrodes. Note

unknown substance
which substances conducted electricity .
3 . Place one evaporating dish on a triangle, and
wire gauze, support stand, iron ring , and
heat with a Bunsen burner. As soon as a solid
clay triangle
melts, remove the flame.
4. Repeat this procedure for every substance. Do
not heat any substance for more than 5 min .
There may be some substances that will not
melt .

216 CHAPTER 6
 EXPERIMENT 6

5 . Note which substances melted and how long the CONCLUSIONS

substances took to melt. 1. Inferring Conclusions: What type of bonding
6. Place five test tubes in the test-tube rack. Place describes each substance? Explain your
0.5 g of each solid into its own individual test reasoning.
tube. Add 5 mL of deionized water to each test 2. Inferring Conclusions: Comparing the proper -
tube. Stopper and shake each test tube in an ties of your unknown solid with the properties
attempt to dissolve the solid . of the known solids, determine the type of bond-
7. Note which substances dissolved in the water. ing present in your unknown solid.

8. Place the solutions or mixtures into separate EXTENSIONS

50 mL beakers, and immerse the electrodes of
1. Evaluating Methods: Is it possible, for a specific
the conductivity tester. Rinse the electrodes with
type of bonding, for these properties to vary
the solvent ( deionized water ) before and after
from what was observed in this experiment ? If
each test. Note which substances conduct
so. give an example of such a variance.
electricitv.
2. Applying Conclusions: Think about diamond.
What would you predict to be the results of this
CLEANUP AND DISPOSAL
experiment performed on diamond, and what
9. Dispose of solids and solutions in containers would you predict the bond type to be ?
designated by your teacher.
10. Clean all equipment and return it to its proper
place.
11. Wash your hands thoroughly after
cleaning up your area and equipment.

ANALYSIS AND INTERPRETATION

1. Analyzing Methods: Why did you rinse the elec -
trodes before each conductivity test ?
2. Analyzing Methods: Why did you use deionized
water in making the solutions?
3. Organizing Data: List the results that each type
of bonding should show.

CHEMICAL BONDING 217

 CHAPTER 7

Chemical Formulas
and Chemical Compounds
Chemists use chemical names and formulas
to describe the atomic composition of compounds.
Chemical Names SECTION 1

and Formulas OBJECTIVES

Explain the significance
* of a chemical formula.

T he total number of natural and synthetic chemical compounds runs ^ Determine the formula of
an ionic compound formed
in the millions. For some of these substances, certain common names between two given ions .
remain in everyday use. For example, calcium carbonate is better
known as limestone, and sodium chloride is usually referred to simply
Name an ionic compound
as table salt. And everyone recognizes dihvdrogen monoxide by its * given its formula.
popular name, water.
Unfortunately, common names usually give no information about
chemical composition. To describe the atomic makeup of compounds, sj Using prefixes, name a binary
chemists use systematic methods for naming compounds and for writing molecular compound from its
chemical formulas. In this chapter, you will be introduced to some of the formula.
rules used to identify simple chemical compounds.
w Write the formula of a binary
molecular compound given its
name.
Significance of a Chemical Formula
Recall that a chemical formula indicates the relative number of atoms
of each kind in a chemical compound. For a molecular compound, the
chemical formula reveals the number of atoms of each element con -
tained in a single molecule of the compound, as shown below for the
hydrocarbon octane. ( Hydrocarbons are molecular compounds com -
posed solely of carbon and hydrogen.)

Subscript indicates that Subscript indicates that

there are 8 carbon atoms there are 18 hydrogen atoms
in a molecule of octane. in a molecule of octane.

Unlike a molecular compound, an ionic compound consists of a

SCllNKS. Owrtftd Md AJiiUHttd fry tfr
HrtHMui Soewe Teadwo AU*O*UM *
lattice of positive and negative ions held together by mutual attraction. For a variety of links related to this
The chemical formula for an ionic compound represents one formula chapter, go to vvww. scilinls.org
unit — the simplest ratio of the compound's positive ions ( cations) and
its negative ions ( anions ). The chemical formula for aluminum sulfate,
Topic: Chemical Formulas
SciLinks code: HC60271
^
an ionic compound consisting of aluminum cations and polyatomic sul-
fate anions, is written as shown on the next page.

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 219

 AI2( S04 )3

Subscript 2 Subscript 4 Subscript 3 refers to

refers to refers to everything inside parentheses,
2 aluminum 4 oxygen giving 3 sulfate ions, with
atoms. atoms in a total of 3 sulfur atoms
sulfate ion. and 12 oxygen atoms.

Note how the parentheses are used. They surround the polyatomic
anion to identify it as a unit. The subscript 3 refers to the entire unit .
Notice also that there is no subscript written next to the symbol for sul -
fur. When there is no subscript written next to an atom’s symbol, the
value of the subscript is understood to be 1.

Monatomic Ions
Bv gaining or losing electrons, many main-group elements form ions
with noble-gas configurations. For example. Group 1 metals lose one
electron to give 14- cations, such as Na" . Group 2 metals lose two elec -
trons to give 2+ cations, such as Mg:\ Ions formed from a single atom
.
are known as monatomic ions The nonmetals of Groups 15, 16, and 17
gain electrons to form anions. For example, in ionic compounds nitro-
gen forms the 3- anion,N ' . The three added electrons plus the five out -
ermost electrons in nitrogen atoms give a completed outermost octet.
Similarly, the Group 16 elements oxygen and sulfur form 2- anions, and
the Group 17 halogens form 1 - anions.
Not all main-group elements readily form ions, however. Rather than
gain or lose electrons, atoms of carbon and silicon form covalent bonds
in which they share electrons with other atoms. Other elements tend to
form ions that do not have noble -gas configurations. For instance, il is
difficult for the Group 14 metals tin and lead to lose four electrons to
achieve a noble -ga.s configuration. Instead. the \ tend to lose the two
electrons in their outer / > orbitals but retain the two electrons in their
outer .v orbitals to form 2+ cations. ( Tin and lead can also form molecu -
lar compounds in which all four valence electrons are involved in cova -
lent bonding.)
Elements from the d-block form 2+. 3+, or, in a few cases. 1 + or 4+
cations. Many rf -block elements form two ions of different charges. For
Examples of Cations example, copper forms 1+ and 2+ cations. Iron and chromium each form
K 2+ cations as well as 3+ cations. And vanadium forms 2+. 34-, and
Potassium cation 44- cations.

Mg2" Naming Monatomic Ions

Magnesium cation Monatomic cations are identified simply by the element ’s name, as illus-
trated by the examples at left. Naming monatomic anions is slightly more

220 CHAPTER 7
complicated. First, the ending of the element 's name is dropped. Then
-
the ending ide is added to the root name, as illustrated by the examples Examples of Anions
at right .
The names and symbols of the common monatomic cations and Element Anion
anions are organized according to their charges in Table 1. The names F F
of many of the ions in the table include Roman numerals. These numer - Fluor / / / e Fluoride anion
als are part of the Stock system of naming chemical ions and elements.
You will read more about the Stock system and other systems of nam - N N3
ing chemicals later in this chapter. Nitrogen Nitride anion

TABLE 1 Some Common Monatomic Ions

Main- group elements

1+ 2+ 3+
lithium Li* beryllium
w
Be2 * aluminum Al3*
sodium Na* magnesium Mg2+
potassium K* calcium Ca2+
'

rubidium Rb* strontium Sr

'

cesium Cs* barium Ba 2*

1- 2- 3-
fluoride F~ oxide O 2- nitride N3-
chloride or sulfide s2- phosphide P3
bromide Br
iodide r

d- Block elements and others with multiple ions

1+ 2+ 3+ 4+
copper ( l ) ( YT vanadium(II) V2 * vanadium(III) V3 * vanadium( IV ) V 4*
silver Ag+ chromium(II) Cr * chromium(III) Cr3* tin( IV ) Sn 4-F
manganese(II) Mn 2 * iron(III) -
FeU lead( IV ) Pb4*
iron(II) Fe2* cobalt (III) Co3+
cobalt (II) Co2*
nickel( II) Ni2*
copper (II) Cu2*
zinc Zn2*
cadmium Cd2*
tin( ll) Sn2*
mercury( ll) Hg2+
lead(Il) Pb2+

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 221

 Binary Ionic Compounds
Compounds composed of two dements are known us hinan compounds .
In a binary ionic compound, the total numbers of positive charges and
negative charges must be equal. Therefore, the formula for such a com-
CAREERS in Chemistry pound can be written given the identities of the compound’s ions. For
example, magnesium and bromine combine to form the ionic compound
Pharmacist
magnesium bromide. Magnesium, a Group 2 metal, forms the Mg:~
Pharmacists work in many areas of cation. Note that the 2 * in Mg2+ is written as a superscript . Bromine, a
healthcare. Traditionally, they have dis-
pensed medications in pharmacies. halogen, forms the Br anion when combined with a metal. In each for -
Today, pharmacists work with other mula unit of magnesium bromide, two Br ~ anions are required to bal -
health professionals to develop and ance the 2 -»- charge of the Mg2 * cation, The compound’s formula must
implement customized drug treatment therefore indicate one Mg2 ’ cation and two Br anions. The symbol for
plans. They advise medical profession- the cation is written first.
als on the side effects of and interac -
tions between medicines. Increasingly, Ions combined: Mg2 \ Br Ik . Chemical formula: MgBr:
pharmacists are working in nontradi-
tional settings, such as in managed- Note that the : in Br: is written as a subscript. The charges of the ions
care companies, pharmaceutical are not included in the formula. This is usually the case when writing
companies, and governmental agencies.
In these settings, pharmacists establish
formulas for binary ionic compounds .
drug guidelines, conduct drug reviews, As an aid to determining subscripts in formulas for ionic compounds,
and assist in the research and develop - the positive and negative charges can be “crossed over." Crossing over is
ment of new drugs. a method of balancing the charges between ions in an ionic compound.
For example, the formula for the compound formed by the aluminum
ion. AF‘. and the oxide ion. O 2-. is determined as follows.
1. Write the symbols for the ions side by side. Write the anion first.

Al '+ O-
2. Cross over the charges by using the absolute value of each ion s charge
as the subscript for the other ion.

Alf * O5-
3. Check the subscripts and divide them by their largest common factor
to give the smallest possible whole- number ratio of ions. Then write
the formula.
Multiplying the charge by the subscript shows that the charge on two
AFU cations ( 2 x 3+ = 6+ ) equals the charge on three O2- anions
( 3 x 2- = 6- ). The largest common factor of the subscripts is l. The
correct formula is therefore written as follows.

Al203

Naming Binary Ionic Compounds

The nomenclature, or naming system , of binary ionic compounds
involves combining the names of the compound’s positive and negative
ions. The name of the cation is given first , followed by the name of

222 CHAPTER 7
the anion. For most simple ionic compounds, the ratio of the ions is not
indicated in the compound's name because it is understood based on
the relative charges of the compound 's ions. The naming of a simple
binary ionic compound is illustrated below.

AI2 O

Name of cation Name of anion

aluminum oxide

SAMPLE PROBLEM A
Write the formulas for the binary ionic compounds formed between the following elements:
a . zinc and iodine b. zinc and sulfur

SOLUTION Write the symbols for the ions side by side. Write the cation first.
a . Zrr" I*

b. Ztr + S:"

Cross over the charges to give subscripts.

a. Znf I2
b. Zm+ S3-
Check the subscripts and divide them by their largest common factor to give the smallest
possible whole- number ratio of ions. Then write the formula.
a . The subscripts are mathematically correct because they give equal total charges ol
1 x 2+ = 2+ and 2 x l - = 2-. The largest common factor of the subscripts is 1.
The smallest possible whole- number ratio of ions in the compound is therefore 1:2.
The subscript I is not written , so the formula is Znl:.
b. The subscripts are mathematically correct because they give equal total charges of
2 x 2+ = 4+ and 2 x 2- = 4- The largest common factor of the subscripts is 2.
-
The smallest whole number ratio of ions in the compound is therefore 1:1 . The correct
formula is ZnS.

PRACTICE Answers in Appendix E

1 . Write formulas for the binary ionic compounds formed between

the following elements:
a . potassium and iodine d . aluminum and sulfur
b. magnesium and chlorine e. aluminum and nitrogen
c. sodium and sulfur
2 . Name the binary ionic compounds indicated by the
following formulas: Go to go.hrw.com for
a . AgCI e. BaO more practice problems
b. ZnO f. CaCF that ask you to write
.
c. CaBr -
‘
formulas for binary ionic
d. SrF, compounds.

LjjC Keyword: HC 6 FRMX

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 223
 The Stock System of Nomenclature
Some elements, such as iron , form two or more cations with different
charges. To distinguish the ions formed by such elements, scientists use
the Stock system of nomenclature. This system uses a Roman numeral
to indicate an ion 's charge. The numeral is enclosed in parentheses and
placed immediately after the metal name.
,
Fe2+ Fe +
iron ( II ) iron ( III )

Names of metals that commonly form only one cation do not include a
Roman numeral.

Na Baz2+ AI3+
sodium barium aluminum

There is no element that commonly forms more than one monatomic

anion .
Naming a binary ionic compound according to the Stock system is
illustrated below.

CuCI2

Name of Roman Name of anion

+
cation numeral
indicating
charge

copper(ll) chloride

FIGURE 1 Different cations of the same metal form different compounds

even when they combine with the same anion. Compare ( a ) lead ( IV ) oxide,
PbO>. with ( b ) lead( II ) oxide, PbO.

224 CHAPTER 7
 SAMPLE PROBLEM B
Write the formula and give the name for the compound formed by the ions Cru and F ”
.
SOLUTION Write the symbols for the ions side by side. Write the cation first.
Cr 3* F-

Cross over the charges to give subscripts.

Cr ?+ F,
Check the subscripts and write the formula.
The subscripts arc correct because they give charges of 1 x 3+ = 3+ a n d 3 x l - = 3-. The
largest common factor of the subscripts is 1 , so the smallest whole-number ratio of the ions
is 1 :3. The formula is therefore CrF,. As Fable 1 shows, chromium forms more than one
ion. Tliere fore, the name of the 3+ chromium ion must be followed by a Roman numeral
indicating its charge. The compound's name is chromium( lll ) fluoride.

PRACTICE Answers in Appendix E

1. Write the formula and give the name for the

compounds formed between the following ions:
a. Cu2+ and Br d. Flg2+ and S 2 ~

2+
b. Fe and O 2 e. Sn2* and F *

2 +
c. Pb and Cl "
f. Fev and O2 *

— i 1 1
Go to go.hrw.com for
2. Give the names for the following compounds: more practice problems
a. CuO c. Snl4 that ask you to write
b. CoF3 d. FeS formulas for ionic
compounds.
Keyword: HC 6 FRMX

Compounds Containing Polyatomic Ions

Table 2 on the next page lists some common polyatomic ions. Most are
negatively charged and most are oxyanions— polyatomic ions that con -
tain oxygen. Some elements can combine with oxygen to form more
than one type of oxyanion. For example, nitrogen can form N03 or
NOT. The name given a compound containing such an oxyanion
depends on the number of oxygen atoms in the oxyanion. The name of
the ion with the greater number of oxygen atoms ends in -ate. The name
of the ion with the smaller number of oxygen atoms ends in - he.

NOT NO-
nitrite nitrate
Sometimes, an element can form more than two types of oxyanions.
In this case, an anion that has one fewer oxygen atom than the - he anion

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 225

 TABLE 2 Some Polyatomic Ions
1+ 2+
ammonium NHj dimercury* Hg ?

1- 2- 3-
acetate CH 3COO- carbonate CO - arsenate AsOj '

^
broinate
chlorate
Br 03
CIO3
chromate
dichromate
CrOj-
Cr 2Ol -
phosphate PO
^-
chlorite CIO; hydrogen phosphate HPOf
cyanide CN '
oxalate C 2Oj ~

dihydrogen phosphate H:PO4- peroxide o?-

hydrogen carbonate HCOJ sulfate SOi
"

( bicarbonate )
hydrogen sulfate HS04 sulfite SOf
hydroxide OH
hypochlorite CIO '

nitrate NO3
nitrite NO;
perchlorate CIO4
permanganate Mn 04
*The mercury ( l ) cation exists as two Hg+ ions joined together by a covalent bond and is written as HgT.

has is given the prefix hypo - . An anion that has one more oxygen atom
than the -me anion has is given the prefix per- . This nomenclature is
illustrated bv the four oxyanions formed bv chlorine.

cio- cio; Cl 03 CIO4

hypochlorite chlorite chlorate perchlorate

Compounds containing polyatomic ions are named in the same man -

ner as binary ionic compounds. The name of the cation is given first ,
followed by the name of the anion. For example, the two compounds
formed with silver by the nitrate and nitrite anions are named silver
nitrate, AgNG3. and silver nitrite , AgN 02. respectively. When multiples of
a polyatomic ion are present in a compound , the formula for the poly -
atomic ion is enclosed in parentheses, as shown on page 220 for aluminum
sulfate, Al 2(S04 )3. The formula indicates that an aluminum sulfate for -
mula unit has two aluminum cations and three sulfate anions.

226 CHAPTER 7
 SAMPLE PROBLEM C
Write the formula for tintIV ) sulfate .
SOLUTION Write the symbols for the ions side by side. Write the cut ion first .
Sn4+ SO} ‘

Cross over the charges to give subscripts . Add parentheses around the polyatomic ion
if necessary.
Snf (S 04 ) 5
Check the subscripts and write the formula.
The total positive charge is 2 x 4+ = 8+. The total negative charge is 4 x 2- = 8-.
The charges are equal. The largest common factor of the subscripts is 2. so the
smallest whole-number ratio of ions in the compound is 1:2. The correct formula
is therefore Sn( S04 ) 2.

PRACTICE Answers in Appendix E

1. Write formulas for the following ionic compounds:

a. sodium iodide e. copper!II ) sulfate
b. calcium chloride f. sodium carbonate
c. potassium sulfide g. calcium nitrite
d. lithium nitrate h. potassium perchlorate
2. Give the names for the following compounds:
a. Ag20
b. Ca(OH)2
c. KCI03
d. NH4OH Go to go.hrw.com for
e. Fe 2( Cr04)3 more practice problems
f. K.CIO that ask you to name
ionic compounds.
Keyword: HC 6 FRMX

Naming Binary Molecular

Compounds
lInlike ionic compounds, molecular compounds are composed of individ -
ual covalently bonded units, or molecules. Chemists use two nomencla -
ture systems to name binary molecules. The newer system is the Stock
system for naming molecular compounds, which requires an understand -
ing of oxidation numbers. This system will be discussed in Section 2 .
The old system of naming molecular compounds is based on the use
of prefixes. For example, the molecular compound CCl4 is named carbon
/em/chloride. The prefix tetra- indicates that four chloride atoms are pres-
ent in a single molecule of the compound. The two oxides of carbon. CO
and CO:. are named carbon monoxide and carbon dioxide. respectively.

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 227

 TABLE 3 Numerical Prefixes
Number Prefix
1 mono-
2 di-
3 tri-
4 letra -

5 penta -
6 hexa-
7 hepta -
X octa -
9 nona-
10 deca -

In these names, the prefix mon- ( from mono - ) indicates one oxygen atom ,
-
and the prefix di indicates two oxygen atoms. The prefixes used to spec-
ify the number of atoms in a molecule are listed in Table 3.
The rules for the prefix system of nomenclature of binary molecular
compounds are as follows.
1. The element that has the smaller group number is usually given first .
If both elements are in the same group, the element whose period
number is greater is given first . Hie element is given a prefix only if it
contributes more than one atom to a molecule of the compound .
2 . The second element is named by combining ( a ) a prefix indicating the
number of atoms contributed by the element , ( b ) the root of the name
of the element , and ( c ) the ending -ide. With few exceptions, the end -
-
ing ide indicates that a compound contains only two elements.
3. The o or a at the end of a prefix is usually dropped when the word fol -
lowing the prefix begins with another vowel . For example, one would
-
write monoxide and pentoxide instead of mono oxide and penia-oxide.

The prefix system is illustrated below.

P4
^ 10

Prefix needed if first Name of Prefix indicating number Root name

element contributes + first element of atoms contributed of second
more than one atom by second element element + ide

tetraphosphorus decoxide

In general, the order of nonmetals in binary compound names and

formulas is C. P. N, H . S, I , Br, Cl , O, and F.

228 CHAPTER 7
 TABLE 4 Binary Compounds of Nitrogen and Oxygen
Formula Prefix- system name
N,0 dinitrogen monoxide
NU nitrogen monoxide
NQ 2 nitrogen dioxide
N2O3 dinitrogen trioxide
N2O4 dinitrogen tetroxide
N,O5 dinitrogen pentoxide

The prefix system is illustrated further in Table 4, which lists the

names of the six oxides of nitrogen. Note the application of rule 1, for
example, in the name nitrogen dioxide for N02. No prefix is needed with
nitrogen because only one atom of nitrogen is present in a molecule of
N()2. On the other hand, according to rule 2, the prefix di - in dioxide is
needed to indicate the presence of two atoms of oxygen /Fake a moment
to review the prefixes in the other names in Table 4.

SAMPLE PROBLEM
a . Give the name for As205.
b. Write the formulu for oxygen ditluoride.

SOLUTION a. A molecule of the compound contains two arsenic atoms, so the first word in the name is
diarsenic. The five oxygen atoms are indicated by adding the prefix pent - to the word
oxide. The complete name is diarsenic pentoxide.

b. The first symbol in the formula is that for oxygen. Oxygen is first in the name because
it is less electronegative than fluorine. Since there is no prefix, there must be only one
oxygen atom. The prefix di - in diflnoride shows that there are two fluorine atoms in
the molecule. The formula is OF2.

PRACTICE Answers in Appendix E

1. Name the following binary molecular compounds:

a. SO ,
b. ICI3
c. PBr5
Go to go.hrw.com for
2. Write formulas for the following compounds: more practice problems
a. carbon tetraiodide that ask you to write
b. phosphorus trichloride names and formulas for
c. dinitrogen trioxide binary molecular
compounds.
N
'c Keyword: HC 6FRMX
CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 229
 Covalent - Network Compounds
As you read in Chapter 6, some covalent compounds do not consist
of individual molecules. Instead, each atom is joined to all its neighbors
in a covalently bonded, three -dimensional network . There are no dis-
tinct units in these compounds, just as there are no such units in ionic
compounds. The subscripts in a formula for a covalent -network com -
pound indicate the smallest whole-number ratio of the atoms in the
compound. Naming such compounds is similar to naming molecular
compounds. Some common examples are given below.
SiC Si02 ,
Si N4
silicon carbide silicon dioxide trisilicon tetranitride

Acids and Salts

SCllNKS. Developed Md numbed by tbe

tottoMi S6MK » TcMten AMMUOM
An acid is a distinct type of molecular compound about which you will
read in detail in Chapter 14. Most acids used in the laboratory can
be classified as either binary acids or oxyacids. Binary acids are acids
For a variety of links related to this
chapter, go to wvAV. scilinks.Qrg
that consist of two elements, usually hydrogen and one of the halogens—
fluorine, chlorine, bromine, iodine. Oxyacids arc acids that contain
Topic: Acids
SciLinks code: HC 60012 hydrogen. oxygen, and a third element ( usually a nonmetal ).
Acids were first recognized as a specific class of compounds based on
AT their properties in solutions of water. Consequently, in chemical nomen -
clature. the term acid usually refers to a solution in water of one of these
special compounds rather than to the compound itself. For example,
hydrochloric acid refers to a water solution of the molecular compound
.
hydrogen chloride HCL Some common binary and oxyacids are listed
in lable 5.
Many polyatomic ions are produced by the loss of hydrogen ions
from oxyacids. A few examples of the relationship between oxyacids
and oxyanions are shown below.
sulfuric acid H2SO4 sulfate sov
nitric acid UNO , nitrate NO3
,
phosphoric acid H PO4 phosphate PO
^
TABLE 5 Common Binary Acids and Oxyacids
HF hydrofluoric acid HNO: nitrous acid HCIO hypochlorous acid
HC1 hydrochloric acid HN03 nitric acid HCIO chlorous acid
1 IBr hvdrobromic acid H:SO3 sulfurous acid HCIO , chloric acid
HI hvdriodic acid H2SO4 sulfuric acid HCIO4 perchloric acid
IF,PO4 phosphoric acid CH3COOH acetic acid H:CQ , carbonic acid

230 CHAPTER 7
 FIGURE 2 Some common labora-
tory acids. Acids should always be
handled with care and according to
instructions. They can burn the skin,
and they burn holes in clothing.

An ionic compound composed of a cation and the anion from an acid

.
is often referred to as a salt. Table salt , NaCI contains the anion from
hydrochloric acid. Calcium sulfate, CaS04. is a salt containing an anion
from sulfuric acid. Some salts contain anions in which one or more
hydrogen atoms from the acid are retained. Such anions are named by
adding the word hydrogen or the prefix bi - to the anion name. The best
known such anion comes from carbonic acid. H2COv
HCO3
hydrogen carbonate ion
bicarbonate ion

SECTION REVIEW 3. Name the following compounds by using the

1. What is the significance of a chemical formula ? Stock system:
2. Write formulas for the compounds formed a. Nal c. CaO e. CuBr
between the following: b. MgS ,
d. K S f. FeCI2
a. aluminum and bromine 4. Write formulas for each of the following compounds:
b. sodium and oxygen a. sodium hydroxide e. carbon diselenide
c. magnesium and iodine b. lead(ll) nitrate f. acetic acid
_
d. Pb2+ and 02 c. iron ll sulfate
( ) g. chloric acid
e. Sn2 " and I- d. diphosphorus trioxide h. sulfurous acid
f. Fe3+ and S2- Critical Thinking
g. Cu2+ and NOj 5. RELATING IDEAS Draw the Lewis structure, give
the name, and predict VSEPR geometry of SCI2.
h. NHJ and SO
^
CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 231
 SECTION 2
Oxidation Numbers
OBJECTIVES
^ List the rules for assigning
oxidation numbers. T he charges on the ions composing an ionic compound reflect the
electron distribution of the compound. In order to indicate the general
>J Give the oxidation number for distribution of electrons among the bonded atoms in a molecular com -
each element in the formula of pound or a polyatomic ion, oxidation numbers, also called oxidation
a chemical compound. states, are assigned to the atoms composing the compound or ion. Unlike
ionic charges, oxidation numbers do not have an exact physical meaning.
In fact, in some cases they are quite arbitrary. However, oxidation num -
Name binary molecular bers are useful in naming compounds, in writing formulas, and in bal-
compounds using oxidation
ancing chemical equations. And, as will be discussed in Chapter 19, they
numbers and the Stock
are helpful in studying certain types of chemical reactions.
system.

Assigning Oxidation Numbers

As a general rule in assigning oxidation numbers, shared electrons are
assumed to belong to the more electronegative atom in each bond.
More specific rules for determining oxidation numbers are provided by
the following guidelines.
1. The atoms in a pure element have an oxidation number of zero. For
example, the atoms in pure sodium, Na, oxygen. 02. phosphorus, P4,
.
and sulfur, Ss all have oxidation numbers of zero.
2. The more -electronegative element in a binary molecular compound
is assigned the number equal to the negative charge it would have as
an anion. The less-electronegative atom is assigned the number equal
to the positive charge it would have as a cation.
3. Fluorine has an oxidation number of - l in all of its compounds
because it is the most electronegative element.
4. Oxygen has an oxidation number of -2 in almost all compounds.
Exceptions include when it is in peroxides, such as H202. in which its
oxidation number is - l, and when it is in compounds with fluorine,
such as OF2, in which its oxidation number is +2.
5 . Hydrogen has an oxidation number of +1 in all compounds contain -
ing elements that are more electronegative than it: it has an oxida-
tion number of -1 in compounds with metals.
6. Hie algebraic sum of the oxidation numbers of all atoms in a neutral
compound is equal to zero.
7 . The algebraic sum of the oxidation numbers of all atoms in a poly -
atomic ion is equal to the charge of the ion.
8. Although rules I through 7 apply to covalently bonded atoms, oxi -
dation numbers can also be assigned to atoms in ionic compounds.

232 CHAPTER 7
 A monatomic ion has an oxidation number equal to the charge of the
ion. For example, the ions Na \ Or \ and Cl have oxidation numbers
of +1. +2, and - 1 . respectively.

Let ' s examine the assignment of oxidation numbers to the atoms in

two molecular compounds, hydrogen fluoride, HF. and water. 11:0. Both
compounds have polar-covalent bonds. In HF, the fluorine atom should
have an oxidation number of - 1 ( see Rule 3 on the previous page ).
Rule 5 tells us that hydrogen should have an oxidation number of + 1 .
This makes sense because fluorine is more electronegative than hydro-
gen. and in a polar-covalent bond , shared electrons are assumed to
belong to the more- electronegative element. For water. Rules 4 and 5
tell us that the oxidation number of oxygen should be -2 and the oxi -
dation number of each hydrogen atom should be + 1. Again, oxygen is
more electronegative than hydrogen, so the shared electrons are
assumed to belong to oxygen.
Because the sum of the oxidation numbers of the atoms in a com-
pound must satisfy Rule 6 or 7 of the guidelines on the previous page, it
is often possible to assign oxidation numbers when they are not known.
1 his is illustrated in Sample Problem E.

SAMPLE PROBLEM E
Assign oxidation numbers to each atom in the following compounds or ions:
a. UKh
b. H,S04
c. CIO3

SOLUTION a . Start by placing known oxidation numbers above the appropriate elements. From the
guidelines, we know that fluorine always has an oxidation number of - 1 .

UF ,
Multiply known oxidation numbers by the appropriate number of atoms and place the
totals underneath the corresponding elements. There are six fluorine atoms, b x - 1 = -6.

Hie compound UFh is molecular. According to the guidelines, the sum of the oxidation
numbers must equal zero. The total of positive oxidation numbers is therefore +6.

1
UF(,
- (1

Divide the total calculated oxidation number by the appropriate number of atoms. There
is only one uranium atom in the molecule, so it must have an oxidation number of +6.

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 233

 UFh
11 h

b. Oxygen and sulfur are each more cleclronegalive than hydrogen, so hydrogen has an oxi-
dation number of + 1. Oxygen is not combined with a halogen, nor is FFS04 a peroxide.
Therefore, the oxidation number of oxygen is -2. Place these known oxidation numbers
above the appropriate symbols. Place the total of the oxidation numbers underneath.

Ii2so4

The sum of the oxidation numbers must equal zero, and there is only one sulfur atom in
each molecule of li:S04. Because ( +2 ) + ( -8) = -h. the oxidation number of each sulfur
atom must be +6.

c. To assign oxidation numbers to the elements in ClOj. proceed as in parts ( a) and ( b ).

Remember, however, that the total of the oxidation numbers should equal the overall
charge of the anion, 1- The oxidation number of a single oxygen atom in the ion is -2.
I he total oxidation number due to the three oxygen atoms is -6. For the chlorate ion to
'

have a I - charge, chlorine must be assigned an oxidation number of +5.

-5 -2

CIO}
-f»

PRACTICE Answers in Appendix E

.
1 Assign oxidation numbers to each atom in the following com -
pounds or ions:
a. HCI e. HN03 h HCIO3 .
b. CF4 f. KH i. N205 Go to go.hrw.com for
c. PC13
d. SO .
*
9 - P4O10 j. GeCl more practice problems
that ask you to assign
oxidation numbers.
_

Using Oxidation Numbers

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for Formulas and Names

.
As shown in Table 6 many nonmetals can have more than one oxidation
number. (A more extensive list of oxidation numbers is given in
Appendix Table A - 15. ) These numbers can sometimes be used in the
same manner as ionic charges to determine formulas. Suppose, for exam -
ple. you want to know the formula of a binary compound formed
between sulfur and oxygen. From the common +4 and +b oxidation states
of sulfur, you could expect that sulfur might form SO: or SO ;. Both are
known compounds. Of course, a formula must represent facts. Oxidation
numbers alone cannot be used to prove the existence of a compound.

234 CHAPTER 7
 TABLE 6 Common Oxidation Numbers of Some
Nonmetals That Have Variable Oxidation
States *
Ci roup 14 carbon -4. +2. +4
Group 15 nitrogen “ .
3. + 1. +2. +3 +4,+5
phosphorus -3. +3,+3
Group 16 sulfur -2.+4, +6
Group 17 chlorine —1, 4 1,+3. -f 5. +7
*

bromine —1,+L +3.+5. +7

iodine —1, +1,+3, 4-5, -f 7
*In addition to the values shown , atoms of each element in its pure state
are assigned an oxidation number of zero.

In Section 1 we introduced the use of Roman numerals to denote

ionic charges in the Stock system of naming ionic compounds.The Stock
system is actually based on oxidation numbers, and it can be used as an
alternative to the prefix system for naming binary molecular com-
pounds. In the prefix system, for example, SO: and SO; are named sul-
fur dioxide and sulfur trioxide, respectively. Their names according to
the Stock system are suIfur ( IV ) oxide and sulfur!VI ) oxide. The inter -
national body that governs nomenclature has endorsed the Stock sys -
tem. which is more practical for complicated compounds. Prefix -based
names and Stock -system names are still used interchangeably for many-
simple compounds, however. A few additional examples of names in
both systems are given below.

Prefix system Stock system

PCI; phosphorus trichloride phosphorus( III ) chloride

PCI , phosphorus pentachloride phosphorus!V ) chloride
NT ) dinitrogen monoxide nitrogen) I ) oxide
NO nitrogen monoxide nitrogen!II) oxide
PbO: lead dioxide lead!IV ) oxide
Mo:Q; dimolvbdenum trioxide molybdenum!HD oxide

SECTION REVIEW 2. Name each of the following binary molecular

1. Assign oxidation numbers to each atom in the compounds according to the Stock system:
following compounds or ions: a. CI4 c. AS2 S3
i. SO
^
-
a. HF e. CS2 b. SO 3 d. NCI3
b. CI4 f. Na 202 Critical Thinking
c. H20 g. H2 C 03 3. DRAWING CONCLUSIONS Determine the oxidation
d. Pl3 h. N02 numbers for iron oxide, Fe304. (Recall that oxida -
tion numbers are integers.)

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 235

 Chemistry in Action
Mass Spectrometry: Identifying Molecules
Tests for locating oil deposits in the molecular mass of the molecular ion. mass spectrometry, and Koichi Tanaka
ground and detecting dioxins in our By analyzing the peaks, scientists (Shimadzu Corporation, Japan)
food supply are commonly per - can determine the identity and struc - developed matrix -assisted laser
formed today. These tests can be ture of a compound. Computers are desorption ionization (MALDI) mass
performed by using a technique used to help interpret the spectrum spectrometry. In 2002, both scientists
known as mass spectrometry. Mass and identify the molecule by using received the Nobel Prize in chemistry
spectrometry is now used in many online spectral database libraries. for their work. Their methods opened
fields, such as medicine, chemistry, Mass spectrometry has been an the field to the study of large mol -
forensic science, and astronomy. essential tool for scientists since its ecules, allowing scientists to use mass
What is mass spectrometry ? It is invention in the early 1900s. But its spectrometry to study the structure of
the most accurate technique avail - use was limited to small molecules macromolecules such as nucleic acids
able to measure the mass of an indi- from which ion creation was easy. and steroids and to identify the
vidual molecule or atom. Knowing Large biological molecules could not sequence of proteins.
the molecular mass is an essential be studied because they would
part of identifying an unknown com- break down or decompose during Questions
pound and determining the structure conventional ion- formation tech- 1. Why is it necessary to convert
of a molecule of the compound. As niques. In the late 1980s, two groups the sample into ions in the mass
the diagram of a mass spectrometer developed ion- formation methods spectrometer ?
shows, the molecules in a gaseous that are used today in commercial
2. How have recent developments
sample are converted into ions. The mass spectrometers. John Fenn
in mass spectrometry con-
ions then are separated and sorted (Virginia Commonwealth University)
tributed to the field of medicine ?
according to their mass-to-charge developed electrospray ionization
ratio by a combination of electric
and magnetic fields. The fields cause Scientists use mass spectrometers to
the ions' trajectories to change identify and study the structure of
Ion separation
molecules.
based on the ions ' masses and and sorting
charges. Then, the sorted ions are
detected, and a mass spectrum is Ion detection
obtained. The mass spectrum is a
graph of relative intensity (related to Ion creation
heated
the number of ions detected) versus filament
mass- to-charge ratio. Mass spec -
trometry uses a very small sample
size (10- 12 g) to obtain results. detector
The resulting spectrum is like a
puzzle. It contains numerous peaks
that correspond to fragments of the
gaseous
initial molecule. The largest peak
sample pump
(parent peak ) corresponds to the mass spectrum

236 CHAPTER 7
 SECTION 3
Using Chemical
Formulas OBJECTIVES
v Calculate the formula mass
or molar mass of any given
compound.

A s you have seen a chemical formula indicates the elements as well as

, sj Use molar mass to convert
the relative number of atoms or ions of each element present in a com - between mass in grams
pound. Chemical formulas also allow chemists to calculate a number of and amount in moles of
characteristic values for a given compound. In this section, you will learn a chemical compound.
how to use chemical formulas to calculate the formula muss, the molar
muss, and the percentage composition by mass of a compound.
Calculate the number of
molecules, formula units, or
ions in a given molar amount
of a chemical compound.
Formula Masses
In Chapter 3, we saw that hydrogen atoms have an average atomic mass ^ Calculate the percentage
of 1.007 94 amu and that oxygen atoms have an average atomic mass of composition of a given
chemical compound.
15.9994 amu. Like individual atoms, molecules, formula units, or ions
have characteristic average masses. For example, we know from the
chemical formula ILO that a single water molecule is composed of
exactly two hydrogen atoms and one oxygen atom. The mass of a water
molecule is found by adding the masses of the three atoms in the
molecule. (In the calculation, the average atomic masses have been
rounded to two decimal places.)

average atomic mass of H: 1.01 amu

average atomic mass of O: 16.00 amu
1.01 amu
2 H atoms x = 2.02 amu
H atom

16.00 amu
1 O atom x = 16.00 amu
Q atom
average mass of 1LO molecule = 18.02 amu

The mass of a water molecule can be correctly referred to as a

5C
7INKS. Dfw%t< mi
wV ft
by the
NUiwul SOCMC le*trn AiWiMtw*
molecular mass . Hie mass of one NaCI formula unit , on the other hand, For a variety of links related to this
is not a molecular mass because NaCI is an ionic compound. The mass chapter, go to .WA7.scilinks.org
of any unit represented by a chemical formula, whether the unit is a Topic: Photochemical Reaction ^
molecule, a formula unit , or an ion, is known as the formula mass. The SciLinks code: HC 61137
formula mass of any molecule, formula unit , or ion is the sum of the
average atomic masses of all atoms represented in its formula.

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 237

 The procedure illustrated for calculating the formula mass of a water
molecule can be used to calculate the mass of any unit represented by a
chemical formula. In each of the problems that follow, the atomic
masses from the periodic table in the back of the book have been
rounded to two decimal places,

SAMPLE PROBLEM F
Find the formula mass of potassium chlorate* KCIOj.

SOLUTION The mass of a formula unit of KCI03 is found by summing the masses of one K atom,
one Cl atom and three O atoms. The required atomic masses can be found in the
,

periodic table in the back of the book. In the calculation, each atomic mass has been
rounded to two decimal places.
39.10 amu
I k atom x = 39.10 amu
K atom
35.45 amu
I Cl atom x = 35.45 amu
Cl atom
16.00 amu
3 O atoms x = 48.00 amu
O atom
formula mass of KCI03 = 122.55 amu

PRACTICE Answers in Appendix E

1. Find the formula mass of each of the following:

a. H2 S04
b. Ca(N03)i Go to go.hrw.com for
c. PO4- more practice problems
d. MgCIi that ask you to calculate
formula mass.
Keyword: HC 6 FRMX

Molar Masses
In Chapter 3 you learned that the molar mass of a substance is equal to
the mass in grams of one mole, or approximately 6.022 x 10" ' particles,
of the substance. For example, the molar mass of pure calcium, Ca, is
40.08 g/mol because one mole of calcium atoms has a mass of 40.08 g.
The molar mass of a compound is calculated by summing the
masses of the elements present in a mole of the molecules or formula
units that make up the compound. For example, one mole of water
molecules contains exactly two moles of H atoms and one mole of O
atoms. Rounded to two decimal places, a mole of hydrogen atoms has a

238 CHAPTER 7
mass of 1.01 g. and a mole of oxygen atoms has a mass of 16.00 g. The
molar mass of water is calculated as follows.

1.01 g I I
2 mot fT x = 2.02 g H
mol H
16.00 g O
1 moFO x
mol O
= 16.00 gO
molar mass of H20 = 18.02 g/ mol

Figure 3 shows a mole of water as well as a mole of several other

substances.
You may have noticed that a compound ' s molar mass is numeri-
cally equal to its formula mass. For instance, in Sample Problem F the
formula mass of KCIO3 was found to be 122.55 amu . Therefore, because
molar mass is numerically equal to formula mass, we know that the FIGURE 3 Every compound has a
molar mass of KCIO3 is 122.55 g/ mol. characteristic molar mass. Shown
here are one mole each of nitrogen
( in balloon ), water ( in graduated
cylinder ), cadmium sulfide, CdS ( yel -
low substance ), and sodium chloride.
NaCl ( white substance ).

SAMPLE PROBLEM G
What is the molar mass of barium nitrate, Ba ( NOv) 2?

SOLUTION One mole of barium nitrate contains exactly one mole of Ba:~ ions and two moles of NO7
ions. The two moles of NO3 ions contain two moles of N atoms and six moles of O atoms.
Therefore, the molar mass of BafNO F is calculated as follows.
^
137.33 g Ba
1 mo! Bn x
mol Bn
= 137.33 g Ba
14.01 gN
2 meWx
molN
= 28.02 g N
16.00 g O
6 moFO x
moK)—= 96.00 g O

molar mass of BafNCVF = 261.35 g/ mol

PRACTICE Answers in Appendix E

1 . How many moles of atoms of each element are there in one mole
of the following compounds?
a . AI 2S3
b. NaN 03
Go to go. hrw.com for
c. Ba ( OH ) 2 more practice problems
2 . Find the molar mass of each of the compounds listed in item l . that ask you to calculate
molar mass.
Keyword: HC 6FRMX

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 239

 x
1
molar mass of compound Amount of
X 6.022 x 10« AV
Number of
Mass of compound
( moles) molecules or
compound 1 formula units
= molar mass of compound x X
( grams) 6.022 X 10« of compound

(a)

2
A
—
X 1
mmm
X
molar mass of element
Amount of
element
x 6.022 x 10« A
Number
Mass of element in compound of atoms
in compound (moles) 1 of element
( grams) = molar mass of element x 6.022 x 10«
X in compound

( b)

FIGURE 4 ( a ) The diagram shows the relationships between mass in grams,

amount in moles, and number of molecules or atoms for a given compound,
( b ) Similar relationships exist for an element within a compound.

Molar Mass as a Conversion Factor

The molar mass of a compound can be used as a conversion factor to
relate an amount in moles to a mass in grams for a given substance.
Recall that molar mass usually has the units of grams per mole. To con-
vert a known amount of a compound in moles to a mass in grams, mul-
tiply the amount in moles by the molar mass.

amount in moles x molar mass ( g/mol ) = mass in grams

Conversions of this type for elements and compounds are summarized

above in Figure 4.

SAMPLE PROBLEM H
W hat is the mass in grams of 2.50 mol of oxygen gas?

SOLUTION
1 ANALYZE Given: 2.50 mol O- .
Unknown: mass of O? in grams

2 PLAN moles 02 > grams Q2

To convert amount of 0: in moles to mass of 02 in grams, multiply by the molar mass of 02.

amount of 02 ( mol ) x molar mass of 02 ( g/mol ) = mass of Q: ( g )

240 CHAPTER 7
3 COMPUTE First the molar mass of 0-> must he calculated.
16.00 g O
2 mo! O x = 32.00 g ( mass of one mole of Q:)
meFQ
The molar mass of 02 is therefore 32.00 g/mol. Now do the calculation shown in step 2.
32.00 g 02
2.50 moFOi x = 80.0 g Q:
mol Os
4 EVALUATE The answer is correctly given to three significant figures and is close to an estimated value
of 75 g ( 2.50 mol x 30 g/mol ).

To convert a known mass of a compound in grams to an amount in

moles, the mass must he divided by the molar mass. Or you can invert
the molar mass and multiply so that units are easily canceled.
1
mass in grams x = amount in moles
molar mass ( g/mol )

SAMPLE PROBLEM I
Ihuprofen. CI3H 18()2, is the active ingredient in many nonprescription pain relievers.
Its molar mass is 206.31 g/mol.
a . If the tablets in a hottle contain a total of 33 g of ihuprofen, how many moles of
ihuprofen are in the hottle ?
b. How many molecules of ihuprofen are in the bottle?
c. What is the total mass in grams of carbon in 33 g of ihuprofen?

SOLUTION
1 ANALYZE ,
Given: 33 g of C d I|sO> molar mass 206.31 g/mol
Unknown: a. moles Cl 3II ) s02
b. molecules C|3 HJIS02
c. total mass of C

2 PLAN a. grams » moles

To convert mass of ihuprofen in grams to amount of ihuprofen in moles, multiply by the
inverted molar mass of C! 3H s02.
'

,
g C |3HJS02 x
I mol Ci 3HIS02
206.31 gCl3Hl8Q 2
, , 02
= mol C 3 H S

b. moles
* molecules ,-
To find the number of molecules of ihuprofen. multiply amount ofC H|80 ? in moles hy
Avogadro’s number.
6.022 x 10: molecules
,
mol C d l|S0 -> x
mol
= molecules Ci3H K02 ,
CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 241
 c. moles CpH sO:, » moles C > grams C
To find the mass of carbon present in the ibuprofen. the two conversion factors needed
are the amount of carbon in moles per mole of CrJ 1 is< : and the molar mass of carbon.
^
13 mol C 12.01 gC
=gc
mol ( |',11 x
mol C , dI,sO: x mol C

1 mol CL;H |IS0 ->

3 COMPUTE a. 33 g, Cr,HlsG: x = 0.16 mol C|;H|S0:
206.31 ££ HTS©-2
^102 molecules
b. 0.16 mol C ;H, , 02 x
iS
6.022 x '

mol
-
= 9.6 x 10 molecules Cj 3H1802

13 mol C 12.01 gC
c. 0.16 mol ( H 1 s02 X x = 23 g C
^ mol -C H jsO:
^ mol C
The bottle contains 0.16 mol of ibuprofen. which is 9.6 x I 022 molecules of ibuprofen.
The sample of ibuprofen contains 23 g of carbon.

4 EVALUATE Checking each step shows that the arithmetic is correct, significant figures have been used
canceled as desired.
correctly, and units have

PRACTICE Answers in Appendix E

1. How many moles of compound are there in the following?

a. 6.60 g ( NH4 ):SO4
b. 4.3 kg Ca( OH 2 >
2. How many molecules are there in the following?
a. 23.0 g H:S04 Go to go.hrw.com for
b. 123 g of sugar, C12H22O 1 , more practice problems
that ask you to use
3. What is the mass in grams of 6.23 mol of copper ( ll ) nitrate? molar mass as a
conversion factor.
C Keyword: HC 6FRMX

Percentage Composition
It is often useful to know the percentage by mass of a particular element
in a chemical compound. For example, suppose the compound potas -
.
sium chlorate, KCI04 were to be used as a source of oxygen. It would
be helpful to know the percentage of oxygen in the compound. To find
the mass percentage of an element in a compound, one can divide the
mass of the element in a sample of the compound by the total mass of
the sample, then multiply this value by 100.

mass of element in sample of compound % element in

x 100 =
mass of sample of compound compound

242 CHAPTER 7
The mass percentage of an element in a compound is the same regard -
less of the sample’s si /e. Therefore, a simpler way to calculate the per -
centage of an element in a compound is to determine how many grams
of the element are present in one mole of the compound. Then divide
this value by the molar mass of the compound and multiply by 100.

mass of element in 1 mol of compound % element in

x 100 =
molar mass of compound compound

The percentage by mass of each element in a compound is known as the

percentage composition of the compound .

SAMPLE PROBLEM i For more help, go to the Math Itilor at the end of this chapter.

Find the percentage composition of copper ) I ) sulfide. Cu2S.

SOLUTION
1 ANALYZE Given: formula. CihS
Unknown: percentage composition of Cu 2S

2 PLAN formula » molar mass > mass percentage of each element

ITie molar mass of the compound must be found . Then the mass of each element present
in one mole of the compound is used to calculate the mass percentage of each element .
63.55 g Cu
3 COMPUTE 2 mol ( u x
'
= 127.1 g Cu
mol Cu
32.07 g S
1 mol-S x = 32.07 g S
mol S
.
molar mass of Cu S = 159.2 g
127.1 g Cu
x 100 = 79.85 % Cu
159.2 g Cu:S
32.07 g S
x 1 (X ) = 20.15 % S
159.2 g Cu:S
4 EVALUATE A good check is to see if the results add up to about 100%. ( Because of rounding, the total
may not always be exactly 100 %. )

SAMPLE PROBLEM K For more help, go to the Math Tutor at the end of this chapter.
As some salts crystallize from a water solution , they hind water molecules in their
crystal structure. Sodium carbonate forms such a hydrate, in which 10 water molecules
are present for every formula unit of sodium carbonate. Find the mass percentage of
water in sodium carbonate decahydrate, Na 2COj* 1011 ,0, which has a molar mass of
286.19 g/ mol .

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 243

 SOLUTION
1 ANALYZE Given: chemical formula. Na:CO l0H -> O
molar mass of Na 2C03* l ()H20
^
Unknown: mass percentage of H20

2 PLAN chemical formula mass H2Q per mole of Na ^CO MOH^O % water
^ *
The mass of water per mole of sodium carbonate decahvdrate must first be found.
This value is then divided by the mass of one mole of Na 2CO l 0H:O.
^
3 COMPUTE One mole of Na 2CO / l 0H 2 O contains 10 mol H:0. Recall from page 239 that the molar
>

mass of H 2Q is 18.02 g/mol. The mass of l ( ) mol H:0 is calculated as follows.

18.02 g H20
10 mol HsG x mol HsO = 180.2 g H20

mass of U20 per mole of Na2C03* l ( )H20 = 180.2 g

.
The molar mass of Na 2CO l0H 2O is 286.19 g/mol so we know that l mol of the hydrate
^
has a mass of 286.l9g. The mass percentage of 10 mol H20 in l mol Na 2 CO3M 0H 2O can
now be calculated.

180.2 g H:0
.
mass percentage of H:0 in Na2CO 3 * 10H:O =
-
286.19 gNa2CO3 10H2O
x UK ) = 62.97% H O

4 EVALUATE Checking shows that the arithmetic is correct and that units cancel as desired.

PRACTICE Answers in Appendix E

1. Find the percentage compositions of the following:
a. PbCU b. Ba(NQ3 )2
irTTiii
2. Find the mass percentage of water in ZnS04* 7 H20. Go to go.hrw.com for
more practice problems
3. Magnesium hydroxide is 54.87 % oxygen by mass. How many that ask you to calculate
grams of oxygen are in 175 g of the compound? How many moles percentage
of oxygen is this? composition .
Keyword: HC 6 FRMX

SECTION REVIEW 5. Calculate the percentage composition of (NH4)2C03.

1. Determine both the formula mass and molar mass Critical Thinking
of ammonium carbonate, (NH4) 2 C03 . 6. RELATING IDEAS A sample of hydrated copper(ll)
2. How many moles of atoms of each element are sulfate (CuS04 * r?H20) is heated to 150°C and pro-
there in one mole of (NH4)2 C03 ? duces 103.74 g anhydrous copper (ll) sulfate and
3. What is the mass in grams of 3.25 mol Fe2 (S04) 3 ? 58.55 g water. How many moles of water mol-
4. How many molecules of aspirin, C9H804, are there ecules are present in 1.0 mol of hydrated
in a 100.0 mg tablet of aspirin? copper(ll) sulfate?

244 CHAPTER 7
 SECTION 4
Determining
Chemical Formulas OBJECTIVES
Define empirical formula,
* and explain how the term
applies to ionic and molecular
compounds.
W hen a new substance is synthesized or is discovered , it is analyzed
quantitatively to reveal its percentage composition . From these data , Determine an empirical formula
the empirical formula is then determined . An empirical formula consists from either a percentage or a
of the symbols for the elements combined in a compound , with subscripts mass composition.
-
showing the smallest whole number mole ratio of the different atoms in
the compound . Foe an ionic compound , the formula unit is usually the
Explain the relationship between
compound 's empirical formula . For a molecular compound , however, the empirical formula and the
the empirical formula does not necessarily indicate the actual numbers molecular formula of a given
of atoms present in each molecule. For example, the empirical formula compound.
of the gas diborane is BH ;. but the molecular formula is B:Hh. In this
case, the number of atoms given by the molecular formula corre -
sponds to the empirical ratio multiplied by two. w Determine a molecular formula
from an empirical formula.

Calculation of Empirical Formulas

To determine a compound 's empirical formula from its percentage com -
position , begin by converting percentage composition to a mass compo-
sition . Assume that you have a 100.0 g sample of the compound . Then
calculate the amount of each element in the sample. For example, the
percentage composition of diborane is 78.1 % B and 21.9 % H .
Therefore, 100.0 g of diborane contains 78.1 g of B and 21.9 g of H .
Next the mass composition of each element is converted to a com -
,

position in moles by dividing by the appropriate molar mass.

1 mol B
78.1 gtfx
10.81 gB
= 7.22 mol B
1 mol H
21.9 gH x
1.01 gH
= 21.7 mol H

These values give a mole ratio of 7.22 mol B to 21.7 mol H. However,
this is not a ratio of smallest whole numbers. To find such a ratio, divide
each number of moles by the smallest number in the existing ratio.
7.22 mol B 21.7 mol H
7.22 7.22
= 1 mol B: 3.01 mol H

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 245

 Because of rounding or experimental error, a compound's mole ratio
sometimes consists of numbers close to whole numbers instead of exact
whole numbers. In this case, the differences from whole numbers may be
ignored and the nearest whole number taken. Thus, diborane contains
atoms in the ratio 1 B : 3 H. The compound’s empirical formula is BHV
Sometimes mass composition is known instead of percentage
composition. To determine the empirical formula in this case, convert
mass composition to composition in moles. Then calculate the smallest
whole-number mole ratio of atoms. This process is shown in Sample
Problem M.

SAMPLE PROBLEM L For more help, go to the Moth Tutor at the end of Chapter 22 .

Quantitative analysis shows that a compound contains 32.38 % sodium, 22.65 % sulfur, and 44.99 % oxygen,
f ind the empirical formula of this compound.

SOLUTION
1 ANALYZE .
Given: percentage composition: 32.38% Na 22 65 % S. and 44.99% O
Unknown: empirical formula

2 PLAN percentage composition » mass composition » composition in moles

» smallest whole -number mole ratio of atoms

3 COMPUTE .
Mass composition ( mass of each element in 100.0 g sample): 32.38 g Na. 22.65 g S 44.99 g O
l mol Na
Composition in moles: 32.38 g-Na x = l.408 mol Na
22.99 g- Na
I mol S
22.65 g-5 x = 0.7063 mol S
32.07
1 mol O
44.99 g-Ox = 2.812 mol O
i6.oo g-e-
Smallest whole - number mole ratio of atoms:
The compound contains atoms in the ratio 1.408 mol Na:0.7063 mol S:2.8 I 2 mol O. To find the
smallest whole - number mole ratio, divide each value by the smallest number in the ratio.

1.408 mol Na 0.7063 mol S 2.812 mol O

= 1.993 mol Na:l mol S:3.98l mol O
0.7063 0.7063 0.7063

Rounding each number in the ratio to the nearest whole number yields a mole ratio
of 2 mol Na:l mol S:4 mol O. The empirical formula of the compound is Na:SC)4.

4 EVALUATE Calculating the percentage composition of the compound based on the empirical formula
determined in the problem reveals a percentage composition of 32.37 % Na. 22.58% S. and
45.05% O. These values agree reasonably well with the given percentage composition.

246 CHAPTER 7
 SAMPLE PROBLEM M For more help, go to the Math Tutor at the end of Chapter 22

Analysis of a 10.150 g sample of a compound known to contain only phosphorus and oxygen indicates a
phosphorus content of 4.433 g. What is the empirical formula of this compound?

SOLUTION
1 ANALYZE Given: sample mass = I0.l50 g
phosphorus mass = 4.433 g
Unknown: empirical formula

2 PLAN Mass composition » composition in moles » smallest whole - number ratio of atoms

3 COMPUTE The mass of oxygen is found by subtracting the phosphorus mass from the sample mass.
sample mass - phosphorus mass = 10.150 g - 4.433 g = 5.717 g
Mass composition: 4.433 g P. 3.717 g ( )

Composition in moles:
I mol P
4.433 gT* x = 0.1431 mol P
30.97 g P
1 mol O
5.717 g-f> x = 0.3573 mol O
16.OOg 0

Smallest whole-number mole ratio of atoms:

0.1431 mol P 0.3573 mol O
0.1431 0.1431
1 mol P : 2.497 mol O

The number of O atoms is not close to a whole number. But if we multiply each number
.
in the ratio by 2. then the number of O atoms becomes 4.994 mol which is close to 5 mol .
I he simplest whole - number mole ratio of P atoms to O atoms is 2:5. The compound 's
empirical formula is P Os.
^
4 EVALUATE The arithmetic is correct , significant figures have been used correctly, and units cancel as
desired. The formula is reasonable because +5 is a common oxidation state of phosphorus.

PRACTICE Answers in Appendix E

1. A compound is found to contain 63.52 % iron and 36.48% sulfur.

Find its empirical formula.
2. Find the empirical formula of a compound found to contain
26.56% potassium. 35.41 % chromium, and the remainder oxygen. Go to go.hrw.com
for more practice
3. Analysis of 20.0 g of a compound containing only calcium and problems that ask you
bromine indicates that 4.00 g of calcium are present. What is the to determine empirical
empirical formula of the compound formed? formulas.
Keyword: HC 6 FRMX

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 247

 Calculation of Molecular Formulas
TTTJ Remember that the empirical formula contains the smallest possible
CROSS- DISCIPLINARY whole numbers that describe the atomic ratio. The molecular formula is
-
Go to go.hrw.com lor a full length the actual formula of a molecular compound. An empirical formula may
article on the importance of molecu- or may not be a correct molecular formula. For example, diborane's
lar shape in odors. empirical formula is 8H3. Any multiple of BH3, such as B:H(V B 3Hg,
' LL B4H 1:, and so on. represents the same ratio of B atoms to H atoms. The
PN Keyword: HC 6 FRMX molecular compounds ethene. C:H4. and cyclopropane. C3H6, also share
an identical atomic ratio ( 2 H:1 C ). yet they are very different sub-
stances. How is the correct formula of a molecular compound found
from an empirical formula?
The relationship between a compound 's empirical formula and its
molecular formula can be written as follows.

.v ( empirical formula) = molecular formula

The number represented bv .v is a whole-number multiple indicating ihe

factor by which the subscripts in the empirical formula must be multi-
plied to obtain the molecular formula. ( The value of x is sometimes 1 . )
The formula masses have a similar relationship.

v( empirical formula mass) = molecular formula mass

To determine the molecular formula of a compound, you must know

the compound's formula mass. For example, experimentation shows the
formula mass of diborane to be 27.67 amu. The formula mass for the
empirical formula. BH3. is 13.84 amu. Dividing the experimental formula
mass by the empirical formula mass gives the value of x for diborane.
27.67 amu
.v = = 2.000
13.84 amu
The molecular formula of diborane is therefore B2Hft.

<
2 BH3) = B2H6

Recall that a compound's molecular formula mass is numerically

equal to its molar mass, so a compound's molecular formula can also be
found given the compound's empirical formula and its molar mass.

SAMPLE PROBLEM N For more help, go to the Math Tutor at the end of Chapter 22

In Sample Problem \1, the empirical formula of a compound of phosphorus and oxygen was found to be
P1O 5. Experimentation shows that the molar mass of this compound is 283.89 g/mol. What is the com-
pound's molecular formula?

SOLUTION
1 ANALYZE Given: empirical formula
Unknown: molecular formula

248 CHAPTER 7
2 PLAN .r ( empirical formula ) = molecular formula
molecular formula mass
A =
empirical formula mass
3 COMPUTE Molecular formula mass is numerically equal to molar mass. Thus, changing the g/mol unit
of the compound's molar mass to amu yields the compound’s molecular formula mass.

molecular molar mass = 283.89 g/mol

molecular formula mass = 283.89 amu

The empirical formula mass is found by adding the masses of each of the atoms indicated in
the empirical formula.

mass of phosphorus atom = 303)7 amu

mass of oxygen atom = 16.00 amu
empirical formula mass of P:Os = 2 x 30.97 amu + 5 x 16.00 amu = 141.94 amu

Dividing the experimental formula mass by the empirical formula mass gives the value of x.
The formula mass is numerically equal to the molar mass.
283.89 amu
v= = 2.0001
141.94 amu
The compound’s molecular formula is therefore P40 ,.
()

2 x ( P205) - P4Oin

4 EVALUATE Checking the arithmetic shows that it is correct.

PRACTICE Answers in Appendix E

1. Determine the molecular formula of the compound with an

empirical formula of CH and a formula mass of 78.110 amu.
Go to go.hrw.com
2. A sample of a compound with a formula mass of 34.00 amu is for more practice
found to consist of 0.44 g H and 6.92 g O. Find its molecular problems that ask you
formula. to determine molecular
formulas.
Keyword: HC 6FRMX

SECTION REVIEW 4. If 4.04 g of N combine with 11.46 g 0 to produce

.
1 A compound contains 36.48% Na, 25.41% S, and a compound with a formula mass of 108.0 amu,
38.11% 0. Find its empirical formula. what is the molecular formula of this compound ?
2. Find the empirical formula of a compound that Critical Thinking
contains 53.70% iron and 46.30% sulfur. 5 . RELATING IDEAS A compound containing sodium,
3. Analysis of a compound indicates that it contains chlorine, and oxygen is 25.42 % sodium by mass. A
1.04 g K, 0.70 g Cr, and 0.86 g 0. Find its empiri- 3.25 g sample gives 4.33 x 1022 atoms of oxygen.
cal formula. What is the empirical formula ?

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 249

 CHAPTER HIGHLIGHTS
Chemical Names and Formulas
1 Vocabulary •A positive monatomic ion is identified simply by the name of
monatomic ion the appropriate element. A negative monatomic ion is named
binary compound by dropping parts of the ending of the element 's name and
nomenclature adding - ide to the root .
oxyanion • charge of each ion in an ionic compound may be used to
The
salt determine the simplest chemical formula for the compound.
•Binary compounds are composed of two elements.
•Binary ionic compounds are named by combining the names
of the positive and negative ions.
•The old system of naming binary molecular compounds uses
prefixes. The new system, known as the Stock system , uses oxi -
dation numbers.

Oxidation Numbers
I Vocabulary •Oxidation numbers are useful in naming compounds, in writing
oxidation number formulas, and in balancing chemical equations .
oxidation state •Compounds containing elements that have more than one oxi-
dation state are named by using the Stock system.
•Stock -system names and prefix-system names are used inter-
changeably for many molecular compounds.
•Oxidation numbers of each element in a compound may be
used to determine the compound's simplest chemical formula.
•By knowing oxidation numbers, we can name compounds with-
out knowing whether they are ionic or molecular.

Using Chemical Formulas

i Vocabulary •Formula mass molar mass, and percentage composition can be
,

formula mass calculated from the chemical formula for a compound.

percentage composition •The percentage composition of a compound is the percentage
by mass of each element in the compound.
•Molar mass is used as a conversion factor between amount in
moles and mass in grams of a given compound or element .

Determining Chemical Formulas

I Vocabulary •An empirical formula shows the simplest whole-number ratio
empirical formula of atoms in a given compound.
•Empirical formulas indicate how many atoms of each element
are combined in the simplest unit of a chemical compound.
•A molecular formula can be found from the empirical formula
if the molar mass is measured.

250 CHAPTER 7
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
9. What determines the order in which the compo -
Chemical Names nent elements of binary molecular compounds
and Formulas are written?
10. Name the following binary molecular com -
SECTION 1 REVIEW
pounds according to the prefix system. ( Hint:
.
1. a What are monatomic ions? See Sample Problem D. )
b. Give three examples of monatomic ions. .
a CO: „
d. SeF
2. How does the chemical formula for the nitrite b. CCf4 e. As -,0 ^
ion differ from the chemical formula for the c. PCI5
nitrate ion ? .
11 Write formulas for each of the following binary
3. Using only the periodic table, write the symbol .
molecular compounds ( Hint: See Sample
of the ion most typically formed by each of the Problem D.)
following elements: a. carbon tetrabromide
.
a K d. Cl b. silicon dioxide
b. Ca e. Ba c. tetraphosphorus decoxide
c. S f. Br d. diarsenic trisulfide
4. Write the formula for and indicate the charge 12 . Distinguish between binary acids and oxvacids .
on each of the following ions: and give two examples of each.
a. sodium ion 13. a. What is a salt ?
b. aluminum ion b. Give two examples of salts.
.
c chloride ion 14. Name each of the following acids:
d. nitride ion a. HF d. H,S04
e. iron(ll) ion
f. iron(lll ) ion
b. HBr
c. HNO3
>
e. H Q4

5 . Name each of the following monatomic ions: 15. Give the molecular formula for each of the fol -
.
a K* d. cr lowing acids:
b. Mg * 2 e. 02~
a. sulfurous acid
c. Al' v f. Ca 2* b. chloric acid
6. Write formulas for the binary ionic compounds
c. hydrochloric acid
formed between the following elements. ( Hint : d. hvpochlorous acid
See Sample Problem A . ) e. perchloric acid
a. sodium and iodine f. carbonic acid
b. calcium and sulfur
g. acetic acid
c. zinc and chlorine
d. barium and fluorine
e. lithium and oxygen PRACTICE PROBLEMS
7. Give the name of each of the following binary 16. Write formulas for each of the following
ionic compounds. ( Hint: See Sample Problem B.) compounds:
a. KCl c. LbO a. sodium fluoride
b. CaBr: d. MgCli b. calcium oxide
8. Write the formulas for and give the names of c. potassium sulfide
the compounds formed by the following ions: d. magnesium chloride
a. Cr 2* and P e. aluminum bromide
b. Ni:~ and O2- f. lithium nitride
c. Fe ' andO2
*
g. iron( II ) oxide

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 251

 CHAPTER REVIEW

17. Name each of the following ions: 24. Assign oxidation numbers to each atom in the
a NHJ. f. cor- following compounds. (Hint: See Sample
g. PO4 Problem E. )
U
b. CIO;
c. OH '
.
h CH3COO- a. HI
d. SOj - i. HCO5 b. PBr3
e. NO; CYO~
: c. GeS:
"
18. Write the formula and charge for each of the d. KH
following ions: e. AS2OS
a. ammonium ion g. copper ( ll ) ion .
f H3P04
h. acetate ion h. tin( 11 ) ion 25. Assign oxidation numbers to each atom in the
c. hydroxide ion i. iron(III) ion following ions. ( Hint: See Sample Problem E. )
d . carbonate ion j. copper ( I ) ion a. NO;
e. sulfate ion k . mercury!I ) ion b. CIOT
f. phosphate ion L. mercury!II ) ion c. PO -

e. co:
^^
d. Cr:0
r
Oxidation Numbers
SECTION 2 REVIEW Using Chemical Formulas
.
19 Name each of the following ions according to
the Stock system: SECTION 3 REVIEW
a Fe2*. d. Pb u 26. a. Define formula mass.
b. Feu e. Sn:+ b. In what unit is formula mass expressed?
c. Pb2+ L Sn4* 27. What is meant by the molar mass of a
20. Name each of the binary molecular compounds compound?
in item 11 by using the Stock system.
21. Write formulas for each of the following PRACTICE PROBLEMS
compounds:
28. Determine the formula mass of each of the fol -
a. phosphorus!I l l ) iodide
b. sulfur! 11) chloride
.
lowing compounds or ions ( Hint: See Sample
Problem F. )
c. carbon!IV ) sulfide
d. nitrogen! V ) oxide
.
a. glucose ChH |:Oh
b. calcium acetate. Ca ( CH;COO ) 2
22. a. What are oxidation numbers?
c. the ammonium ion. NH4
b. What useful functions do oxidation numbers
d. the chlorate ion, CIO;
serve /
29. Determine the number of moles of each type of
monatomic or polyatomic ion in one mole of
PRACTICE PROBLEMS the following compounds. For each polyatomic
23. Name each of the following ionic compounds by ion, determine the number of moles of each
using the Stock system: atom present in one mole of the ion.
a. NaCl a. KNO;
b. KF b. Na 2S 04
c. CaS c. Ca( OH)2
d. Co( NO;): d. (NH4)2S03
e. FeP04 e. Ca3( P04)2
f. Hg2S04 f. AI2( Cr04);
g. Hg?( PQ4 )2

252 CHAPTER 7
 CHAPTER REVIEW

30. Determine the molar mass of each compound MIXED REVIEW

.
listed in item 29. ( Hint: See Sample Problem G )
31. Determine the number of moles of compound 40. Chemical analysis shows that citric acid contains
in each of the following samples. ( Hint : See 37.51% C. 4.20% H. and 58.29% O. What is the
Sample Problem I. ) empirical formula for citric acid?
a. 4.50 g H:0 41. Name each of the following compounds by
b. 471.6 gBa( OH)2~ using the Stock system:
c. 129.68 gFe3( PO4)2 a. LiBr f. Fe 203
32. Determine the percentage composition of each b. Sn(N03)2 g. AgN03
of the following compounds. ( Hint: See Sample c. FeCI: h. Fe( OH ) 2
Problem J.) d. MgO i. CrF,
a. NaCI e. KOH
b. AgN03 42. What is the mass in grams of each of the follow -
.
c Mg( OH)2 ing samples?
33. Determine the percentage by mass of water in a. 1.000 mol NaCI
the hydrate CuS04 * 5H20. ( Hint: See Sample b. 2.000 mol H20
Problem K. ) .
c 3.500 mol Ca( OH)2
d. 0.625 mol Ba(N03)2
43. Determine the formula mass and molar mass of
Determining Chemical each of the following compounds:
a. XeF4
Formulas b. C
SECTION 4 REVIEW c. Hg2I2
d. CuCN
34. What three types of information are used to
44. Write the chemical formulas for the following
find an empirical formula from percentage
compounds:
composition data?
a. aluminum fluoride
35 . What is the relationship between the empirical
b. magnesium oxide
formula and the molecular formula of a
c. vanadium( V ) oxide
compound?
d. cobalt ( ll) sulfide
e. strontium bromide
PRACTICE PROBLEMS f. sulfur trioxide
36. Determine the empirical formula of a com - 45. How many atoms of each element are con -
pound containing 63.50% silver. 8.25 % nitro- tained in a single formula unit of iron( lll ) for -
gen. and 28.25 % oxygen. ( Hint : See Sample mate, Fe ( CH02 )3 * H20? What percentage by
Problem L. ) mass of the compound is water ?
37. Determine the empirical formula of a com- 46. Name each of the following acids, and assign
pound found to contain 52.11 % carbon. 13.14 % oxidation numbers to the atoms in each:
hydrogen, and 34.75% oxygen. a. HNO: c. H 2C03
38. What is the molecular formula of the molecule b. H:SO; d. HI
that has an empirical formula of CI FO and a 47 . Determine the percentage composition of the
molar mass of 120.12 g/mol? following compounds:
39. A compound with a formula mass of 42.08 aniu a. NaCIO
is found to be 85.64 % carbon and 14.36% b. H2S03
hydrogen by mass. Find its molecular formula. c. C2H5COOH
d. BeCli

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 253

 CHAPTER REVIEW

48. Name each of the following binary compounds: USING THE HANDBOOK
a . Mgl ? e. SO,
b. NaF f. PBr 3 53. Review the common reactions of Group 1
c. CS , g. CaCl 2 metals in the Elements Handbook , and answer
d . N 2O4 h . Agl the following questions:
49. Assign oxidation numbers to each atom in the a . Some of the Group 1 metals react with oxy -
following molecules and ions: gen to form superoxides. Write the formulas
a. CO, e. IFO-, for these compounds.
b. NHj „
I - P4o , b. What is the charge on each cation for the
c. Mn 04 g. OF, formulas that you wrote in ( a ) ?
d . s2o\- c. I low does the charge on the anion vary for
50. A 175.0 g sample of a compound contains oxides, peroxides, and superoxides?
56.15 g C. 0.43 g 11.74.81 g O. 13.11 g N. and 54. Review the common reactions of Group 2
21.40 g Na . What is the compound 's empirical metals in the Elements Handbook , and answer
formula ? the following questions:
a. Some of the Group 2 metals react with oxy -
gen to form oxides. Write the formulas for
CRITICAL THINKING these compounds.
b. Some of the Group 2 metals react with oxy -
51. Analyzing Information Sulfur trioxide is pro- gen to form peroxides. Write the formulas for
duced in the atmosphere through a reaction of these compounds.
sulfur dioxide and oxygen . Sulfur dioxide is a c. Some of the Group 2 metals react with nitro-
primary air pollutant . Analyze the formula for gen to form nitrides. Write the formulas for
sulfur trioxide. Then , list all of the chemical these compounds.
information from the analysis that you can. d . Most Group 2 elements form hydrides.
52. Analyzing Data In the laboratory, a sample of What is hydrogen 's oxidation state in these
pure nickel was placed in a clean , dry. weighed compounds?
crucible. The crucible was heated so that the 55. Review the analytical tests for transition metals
nickel would react with the oxygen in the air . in the Elements Handbook , and answer the
After the reaction appeared complete, the cru - following questions:
cible was allowed to cool and the mass was a . Determine the oxidation state of each metal
determined . The crucible was reheated and in the precipitates shown for cadmium , zinc,
allowed to cool . Its mass was then determined and lead.
again to be certain that the reaction was com - b. Determine the oxidation stale ot each metal
plete. The following data were collected: in the complex ions shown for iron , man -
ganese. and cobalt .
Mass of crucible = 30.02 g c. The copper compound shown is called a
Mass of nickel and crucible = 31.07 g coordination compound. Hie ammonia
Mass of nickel oxide and crucible = 31.36 g shown in the formula exists as molecules that
Determine the following information based on do not have a charge. Determine copper 's
the data given above:
oxidation state in this compound .
Mass of nickel =
Mass of nickel oxide =
Mass of oxygen =
Based on your calculations, what is the empiri-
cal formula for the nickel oxide?

254 CHAPTER 7
 CHAPTER REVIEW

56. Review the common reactions of Group 15 ele -

ALTERNATIVE ASSESSMENT
ments in the Elements Handbook , and answer
the following questions: 59. Performance Assessment Your teacher will
a. Write formulas for each of the oxides listed supply you with a note card that has one of the
for the Group 15 elements. following formulas on it: NaCH3C0(>3H?0,
b. Determine nitrogen's oxidation state in the
oxides listed in ( a ).
- .
MgCV 6H20. LiC2H >0: 2H:0 or MgS04 * 7H:0.
Design an experiment to determine the percent -
age of water by mass in the hydrated salt
assigned to you. Be sure to explain what steps
RESEARCH & WRITING you will take to ensure that the salt is com-
pletely dry. If your teacher approves your
57. Nomenclature Biologists who name newly dis- design, obtain the salt and perform the experi -
covered organisms use a system that is struc - ment . What percentage of water does the salt
tured very much like the one used by chemists contain?
in naming compounds. The system used by bi-
ologists is called the Linnaeus system, after its 60. Both ammonia, NH3, and ammonium nitrate,
creator, Carolus Linnaeus. Research this system
NH4N03, are used in fertilizers as a source of
in a biology textbook, and then note similarities nitrogen. Which compound has the higher per -
and differences between the Linnaeus system centage of nitrogen? Research the physical
and chemical nomenclature. properties of both compounds, and find out how
each compound is manufactured and used.
58. Common Chemicals Find out the systematic
Explain why each compound has its own partic -
chemical name and write the chemical formula ular application. ( Consider factors such as the
for each of the following common compounds: cost of raw ingredients, the ease of manufacture,
a. baking soda d. limestone and shipping costs. )
b. milk of magnesia e. Ive
c. Epsom salts f. wood alcohol

i Graphing Calculator Calculating Molar

Mass
Go to go.hrw.com for a graphing calculator
exercise that asks you to calculate the molar
mass of a compound.

Keyword: HC 6 FRMX

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 255

 Math Tutor CALCULATING PERCENTAGE COMPOSITION

Chemists can analyze an unknown substance by determining its percentage composi-

tion by mass. Percentage composition is determined by finding the mass of each ele-
ment in a sample of the substance as a percentage of the mass of the whole sample.
The results of this analysis can then be compared with the percentage composition of
known compounds to determine the probable identity of the unknown substance.
Once you know a compound's formula, you can determine its percentage composition
by mass.

SAMPLE 1 SAMPLE 2
Determine the percentage composition of potas- Determine the percentage of nitrogen in ammo -
sium chlorate, KCIO3. nium sulfate, ( NH4 ) 2S04.
First , calculate the molar mass of KCIO3. The Even though you want to find the percentage of
formula shows you that one mole of KCIO3 con * only one element , you must calculate the molar
# 7 j

sists of l mol K atoms, l mol Cl atoms, and 3 mol mass of ( NH 4) 2S04. To do that , examine the for-
O atoms. Thus, the molar mass of KCIO3 is molar mula to find the number of moles of each element
mass K + molar mass Cl + 3( molar mass O ) = in the compound . The two ammonium groups, indi-
39 10 gK + 35.45 g Cl + 3( 16.00 g O ).
* cated by ( NH4)2, contain 2 mol N and 8 mol H per
molar mass KCIO3 = 122.55 g mole of ( NH 4 )2S04. The sulfate group, S04, con -
tains 1 mol S and 4 mol O per mole of ( NH 4)2S04.
The percentage composition of KCIO3 is deter-
mined by calculating the percentage of the total 2 mol N = 2 x 14.01 g = 28.02 g
molar mass contributed bv each element *
8 mol H = 8 1.01 g =
x 8.08 g
1 mol S = 1 x 32.07 = 32.07 g
mass of element in 1 mol of compound 4 mol 0 = 4 x 16.00 = 64.00 g
x 100 molar mass ( NH 4 ) 2S04 = 132.17 g
molar mass of compound
Now. you can determine the percentage of
= % element in compound
nitrogen in the compound as follows.
39.10 gK
% K in KCIO , = 122.55 g KCIO,
x 100 = 31.91 %
% N in ( NH 4 ) 2S04 =
28.02 g N
132.17 g ( NH 4 )2S04
35.45 g Cl
% Cl in KCIO , = 122.55 g KCIO,
x 100 = 28.93% x 100 = 21.20%

48.00 g O
% O in KCIO , = 122.55 g KCIO,
x 100 = 39.17%

PRACTICE PROBLEMS
1 . What is the percentage composition of sodium 2. What is the percentage of iodine in zinc iodate.
,
carbonate. Na 2CO 7 ,
Zn ( 10 )2?

256 CHAPTER 7
Answer the following items on a separate piece of paper. 7. Which of the following shows the percentage
MULTIPLE CHOICE
composition of H:S04?
A . 2.5 % H, 39.1% S, 58.5 % O
.
1 Which of the following compounds does not B. 2.1 % H, 32.7 % S, 65.2 % O
contain a polyatomic ion ?
C. 28.6 % H . 14.3% S. 57.1 % O
A. sodium carbonate
B. sodium sulfate
.
D 33.3% H . 16.7 % S, 50 % O
C . sodium sulfite 8. Which of the following compounds has the
D. sodium sulfide highest percentage of oxygen ?
A . CH 40
2. The correct formula for ammonium phosphate B. C02
IS
C. H:O
A . ( NH 4 )3 P04.
D . Na 2C03
B . ( NH4 )2P04.
c . NH4 PO4. 9. The empirical formula for a compound that is
.
D NH 4 ( P04 )2. 1.2 % H . 42.0% Cl , and 56.8% O is
A . HCIO.
3. When writing the formula for a compound that B. HC102.
contains a polyatomic ion .
C . HClOv
A . write the anion 's formula first .
D . HC104.
B. use superscripts to show the number of poly -
atomic ions present . SHORT ANSWER
C . use parentheses if the number of polyatomic 10. When a new substance is synthesized or is dis-
ions is greater than 1. covered experimentally, the substance is ana-
.
D always place the polyatomic ion in lyzed quantitatively. What information is
parentheses. obtained from this typical analysis, and how is
this information used ?
.
4 The correct name for NH 4CH COO is
^
A . ammonium carbonate. 11. An oxide of selenium is 28.8 % O. Find the
B. ammonium hydroxide. empirical formula. Assuming that the empirical
C . ammonium acetate. formula is also the molecular formula , name the
oxide.
.
D ammonium nitrate.
EXTENDED RESPONSE
5. Which of the following is the correct formula
for iron ( IIl ) sulfate ? 12. What is an empirical formula , and how does it
A . Fe3S04 differ from a molecular formula ?
B. Fe 3(S04)2 13. What are Stock system names based on ?
«r

C . Fe 2( S04 )3
D . 3FeSG 4
6. The molecular formula for acetylene is C2 H 2.
ITe molecular formula for benzene is C6H6.
The empirical formula for both is
A . CH.
B . C\ H 2.
c. QH6.
D. ( CH ),.
Whenever possible, highlight or
underline numbers or words critical to answering a
question correctly.

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 257

 SEE P R E- L A B
EXPERIMENT 7 GRAVIMETRIC ANALYSIS

Determining the Empirical

Formula of Magnesium Oxide
OBJECTIVES BACKGROUND
• Measure the mass of magnesium oxide. This gravimetric analysis involves the combustion
of magnesium metal in air to synthesize magnesium
• Perform a synthesis reaction by using
oxide. Hie mass of the product is greater than the
gravimetric techniques.
mass of magnesium used because oxygen reacts with
• Determine the empirical formula of the magnesium metal. As in all gravimetric analyses,
magnesium oxide. success depends on attaining a product yield near
• Calculate the class average and standard 100%. Therefore, the product will be heated and
deviation for moles of oxygen used. cooled and have its mass measured until two of these
mass measurements are within 0.02 % of one another.
MATERIALS When the masses of the reactant and product have
been carefully measured, the amount of oxygen used
• 15 cm magnesium • crucible and lid.
ribbon, 2 metal or ceramic in the reaction can be calculated. The ratio of oxygen
to magnesium can then be established, and the empir -
• 25 niL beaker • crucible tongs ical formula of magnesium oxide can be determined.
• Bunsen burner • distilled water
assenthi v SAFETY
• eyedropper or
• day triangle micropipet
• ring stand
For review of safety, please see Safety in the
Chemistry Laboratory in the front of your book.

PREPARATION
1. Copy the following data table in your lab
notebook.

DATA TABLE
Trial 1 Trial 2
1. Mass of crucible, lid, and metal (g)
2. Mass of crucible, lid, and product (g)
3. Mass of crucible and lid (g)

FIGURE A

258 CHAPTER 7
 EXPERIMENT 7

PROCEDURE 10. Turn off the burner. Cool the crucible, lid , and
1. Construct a setup for heating a crucible as contents to room temperature. Measure the mass
shown in Figure A and as demonstrated in the of the crucible, lid , and product . Record the
Pre- Laboratorv Procedure “Gravimetric measurement in the margin of your data table.
Analysis." 11. Replace the crucible, lid. and contents on the
2. Heat the crucible and lid for 5 min to burn off clay triangle, and reheat for another 2 min.
any impurities. Cool to room temperature, and remeasure the
mass of the crucible, lid. and contents. Compare
3. Cool the crucible and lid to room temperature. this mass measurement with the measurement
Measure their combined mass, and record the obtained in step 10. If the new mass is ± 0.02 %
measurement on line 3 of your data table. of the mass in step 10, record the new mass on
NOTE: Handle the crucible and lid with crucible line 2 of your data table and go on to step 12. If
tongs at all times during this experiment. Such not. your reaction is still incomplete, and you
handling prevents burns and the transfer of dirt should repeal step 11.
and oil from your hands to the crucible and lid . 12. Clean the crucible, and repeat steps 2-11 with a
4. Polish a 13 cm strip of magnesium w ith steel second strip of magnesium ribbon. Record your
wool . Hie magnesium should be shiny. Cut the measurements under Trial 2 in vour data table.
strip into small pieces to make the reaction pro-
ceed faster , and place the pieces in the crucible. CLEANUP AND DISPOSAL
13. Put the solid magnesium oxide in the
5. Cover the crucible with the lid , and measure
designated w'aste container. Return
the mass of the crucible, lid. and metal. Record
any unused magnesium ribbon to your
the measurement on line 1 of your data table.
teacher. Clean your equipment and lab station .
6. Use tongs to replace the crucible on the clay Thoroughly w ash your hands after completing
triangle. Heat the covered crucible gently. Lift the lab session and cleanup.
the lid occasionally to allow' air in .
ANALYSIS AND INTERPRETATION
CAUTION : Do not look directly at the burning
magnesium metal. The brightness of the light 1. Applying Ideas: Calculate the mass of the
can blind vou . magnesium metal and the mass of the product .

7. When the magnesium appears to be fully re - 2. Evaluating Data: Determine the mass of the
acted . partially remove the crucible lid and oxygen consumed.
continue heating for 1 min . 3. Applying Ideas: Calculate the number of
8. Remove the burner from under the crucible. moles of magnesium and the number of moles
After the crucible has cooled , use an eyedropper of oxygen in the product .
to carefully add a few drops of water to decom -
pose any nitrides that may have formed. CONCLUSIONS
CAUTION : Use care when adding water. Using 1. Inferring Relationships: Determine the
too much water can cause the crucible to crack. empirical formula for magnesium oxide, MgxOy.
9. Cover the crucible completely. Replace the
burner under the crucible, and continue heating
for about 30 to 60 s.

CHEMICAL FORMULAS AND CHEMICAL COMPOUNDS 259

 CHAPTER 8

and Reactions
The evolution of energy as light and heat is an indication
that a chemical reaction is taking place.
 SECTION 1
Describing Chemical
Reactions OBJECTIVES
sj List three observations that
suggest that a chemical
reaction has taken place.

A chemical reaction is the process by which one or more substances J List three requirements for
are changed into one or more different substances. In any chemical a correctly written chemical
reaction, the original substances are known as the reactants and the equation.
resulting substances are known as the products. According to the law of
conservation of mass, the total mass of reactants must equal the total
mass of products for any given chemical reaction. ^ Write a word equation and a
formula equation for a given
Chemical reactions are described by chemical equations. A chemical
chemical reaction.
equation represents, with symbols and formulas, the identities and
relative molecular or molar amounts of the reactants and products in a
chemical reaction. For example, the following chemical equation shows sj Balance a formula equation
that the reactant ammonium dichromate yields the products nitrogen, by inspection.
chromiumf III ) oxide, and water.

( NH4 ) 2Cr 207(.s ) > N2(g) + Cr203( 5 ) + 4H20( s)

This strongly exothermic reaction is shown in Figure I.

Indications of a Chemical Reaction

To know for certain that a chemical reaction has taken place requires
evidence that one or more substances have undergone a change in iden -
tity. Absolute proof of such a change can be provided only by chemical
analysis of the products. However, certain easily observed changes usu-
ally indicate that a chemical reaction has occurred.
1. Involution of energy as heat and light . A change in matter that re -
leases energy as both heat and light is strong evidence that a chemi-
cal reaction has taken place. For example, you can see in Figure 1 that
the decomposition of ammonium dichromate is accompanied by the
evolution of energy as heat and light. And you can see evidence that
a chemical reaction occurs between natural gas and oxygen if you
burn gas for cooking in your house. Some reactions involve only heat
or only light . But heat or light by itself is not necessarily a sign of
FIGURE 1 The decomposition
chemical change, because many physical changes also involve either of ammonium dichromate proceeds
heat or light . rapidly, releasing energy in the form
of light and heat .

CHEMICAL EQUATIONS AND REACTIONS 261

 FIGURE 2 (a ) The reaction of
vinegar and baking soda is evidenced
by the production of bubbles of car -
bon dioxide gas. ( b ) When water
solutions of ammonium sulfide
and cadmium nitrate are combined,
the yellow precipitate cadmium
sulfide forms.

2. Production of a gas. The evolution of gas hubbies when two sub -

stances are mixed is often evidence of a chemical reaction. For exam -
ple, bubbles of carbon dioxide gas form immediately when baking
soda is mixed with vinegar, in the vigorous reaction that is shown in
Figure 2a.
3. Formation of a precipitate. Many chemical reactions lake place
between substances that are dissolved in liquids. If a solid appears
after two solutions are mixed, a reaction has likely occurred. A solid
Orveleptd nd mtilwfd fey tkr
KjhofudSome Jftfhm Aiwylwi

For a variety of links related to this that is produced as a result of a chemical reaction in solution and that
chapter, go to www.sdlrnks.org «
separates from the solution is known as a precipitate. A precipitate -
Topic: Chemical Reactions forming reaction is shown in Figure 2b.
SciLinks code: HC60274 4. Color change. A change in color is often an indication of a chemical
reaction.

Characteristics of Chemical Equations

A properly written chemical equation can summarize any chemical
change. The following requirements will aid you in writing and reading
chemical equations correctly.
1. The equation must represent known facts. All reactants and products
must be identified, either through chemical analysis in the labora -
tory or from sources that give the results of experiments.
2. The equation must contain the correct formulas for the reactants and
products. Remember what you learned in Chapter 7 about symbols
and formulas. Knowledge of the common oxidation states of the ele -
ments and of methods of writing formulas will enable you to supply
formulas for reactants and products if they are not available. Recall
that the elements listed in Table 1 exist primarily as diatomic mol-
ecules, such as H:and 02. Each of these elements is represented in an
equation by its molecular formula. Other elements in the elemental
state are usually represented simply by their atomic symbols. For
example, iron is represented as Fe and carbon is represented as ( . The
’

symbols are not given any subscripts because the elements do not

262 CHAPTER 8
 TABLE 1 Elements That Normally Exist as Diatomic
Molecules
Physical state at
Element Symbol Molecular formula room temperature
Hydrogen H Hi gas
Nitrogen N N» * gas
Oxygen O O . gas
Fluorine F F2 gas
Chlorine Cl Cl 2 gas
Bromine Br Br, liquid
Iodine I h solid

form definite molecular structures. Two exceptions to this rule are

sulfur, which is usually written Ss, and phosphorus, which is usually Chemistry in Action
written P4. In these cases, the formulas reflect each element s unique Go to go. hrw. com for a lull length
atomic arrangement in its natural state. article on water treatment and our
3 . The law of conservation of mass mast he satisfied . Atoms are neither public water supply.
created nor destroyed in ordinary chemical reactions. Therefore, the Keyword : HC 6 RXNX
same number of atoms of each element must appear on each side of
a correct chemical equation . To balance numbers of atoms, add coef -
ficients where necessary. A coefficient is a small whole number that
appears in front of a formula in a chemical equation. Placing a coef -
ficient in front of a formula specifies the relative number of moles of
the substance: if no coefficient is written , the coefficient is assumed
to be l . For example, the coefficient 4 in the equation on page 261
indicates that 4 mol of water are produced for each mole of nitrogen
and chromium! Ill ) oxide that is produced .

Word and Formula Equations

The first step in writing a chemical equation is to identify the facts to be
represented . It is often helpful to write a word equation , an equation in
which the reactants and products in a chemical reaction are represented
by words. A word equation has only qualitative ( descriptive ) meaning.
It does not give the whole story because it does not give the quantities
of reactants used or products formed.
Consider the reaction of methane, the principal component of natu -
ral gas. with oxygen. When methane burns in air. it combines with oxy -
gen to produce carbon dioxide and water vapor. In the reaction ,
methane and oxygen are the reactants, and carbon dioxide and water
are the products. The word equation for the reaction of methane and
oxygen is written as follows.
methane + oxygen * carbon dioxide + water
I he arrow. ». is read as react to yield or yield ( also produce or form ).
So the equation above is read , “ methane and oxygen react to yield

CHEMICAL EQUATIONS AND REACTIONS 263

 carbon dioxide and water.' or simply, “methane and oxygen yield car -
bon dioxide and water."
The next step in writing a correct chemical equation is to replace the
names of the reactants and products with appropriate symbols and for -
mulas. Methane is a molecular compound composed of one carbon
atom and four hydrogen atoms. Its chemical formula is CH4. Recall that
oxygen exists in nature as diatomic molecules: it is therefore represented
as O -,. The correct formulas for carbon dioxide and water are C02 and
1 LO. respectively.
A formula equation represents the reactants anil products of a chemi -
cal reaction by their symbols or formulas. The formula equation for the
reaction of methane and oxygen is written as follows.

( not balanced )
CH40J) + 02(g)
* C02(g) + H20( g)
The g in parentheses after each formula indicates that the correspond -
ing substance is in the gaseous state. Like a word equation, a formula
equation is a qualitative statement. It gives no information about the
amounts of reactants or products.
A formula equation meets two of the three requirements for a cor -
rect chemical equation. It represents the facts and shows the correct
symbols and formulas for the reactants and products. To complete the
process of writing a correct equation, the law of conservation of mass
must be taken into account. The relative amounts of reactants and prod -
ucts represented in the equation must be adjusted so that the numbers
and types of atoms are the same on both sides of the equation. This
process is called balancing an equation and is carried out by inserting
coefficients. Once it is balanced, a formula equation is a correctly writ -
ten chemical equation.
Look again at the formula equation for the reaction of methane and
oxygen.

CHA( 8 ) + 02 ( g ) C02(g) + H:Q(.0 (not balanced )

To balance the equation, begin by counting atoms of elements that arc

CHEMISTRY
m
.
•Y/ ro
LVA

combined with atoms of other elements and that appear only once on
Module 5 : Equations and
* each side of the equation. In this case, we could begin by counting either
Stoichiometry
carbon or hydrogen atoms. Usually, the elements hydrogen and oxygen
are balanced only after balancing all other elements in an equation.
( You will read more about the rules of balancing equations later in the
chapter. ) Thus, we begin by counting carbon atoms.
Inspecting the formula equation reveals that there is one carbon atom
on each side of the arrow. Therefore, carbon is already balanced in the
equation. Counting hydrogen atoms reveals that there are four hydrogen
atoms in the reactants but only two in the products.Two additional hydro-
gen atoms arc needed on the right side of the equation. They can be
added bv placing the coefficient 2 in front of the chemical formula 1 LO.

CH40;) + o2( g ) » C02( g ) + 21LO( # ) ( partially balanced )

264 CHAPTER 8
 A coefficient multiplies the number of atoms of each element indi-
cated in a chemical formula. Thus. 2 H:0 represents four H atoms and
two O atoms. To add two more hydrogen atoms to the right side of the
equation, one may be tempted to change the subscript in the formula of
water so that H:0 becomes H40. However, this would be a mistake
because changing the subscripts of a chemical formula changes the
identity of the compound. H40 is not a product in the combustion of
methane. In fact, there is no such compound. One must use only coeffi -
cients to change the relative number of atoms in a chemical equation
because coefficients change the numbers of atoms without changing the
identities of the reactants or products.
Now consider the number of oxygen atoms. There are four oxygen
atoms on the right side of the arrow in the partially balanced equation.
Yet there are only two oxygen atoms on the left side of the arrow. One
can increase the number of oxygen atoms on the left side to four by
placing the coefficient 2 in front of the molecular formula for oxygen.
This results in a correct chemical equation, or balanced formula equa -
tion. for the burning of methane in oxygen.

CH4( g) + 202( g) C02(g) + 2H:Q(g)

This reaction is further illustrated in Figure 3 .

Additional Symbols Used in Chemical Equations
Fable 2 on the next page summarizes the symbols commonly used in
chemical equations. Sometimes a gaseous product is indicated by an
arrow pointing upward. T, instead of ( g ). as shown in the table. A down-
ward arrow, i . is often used to show the formation of a precipitate dur -
ing a reaction in solution.
The conditions under which a reaction takes place are often indicated
by placing information above or below the reaction arrow.The word heat,

(a )
(b)

Molecules CH 4 + 2H20

Atoms ( 1C, 4H) + ( 40) (4H, 20)

FIGURE 3 ( a ) In a Bunsen burner, methane combines with oxygen in the air to form
carbon dioxide and water vapor, ( b ) The reaction is represented by both a molecular
model and a balanced equation. Each shows that the number of atoms of each element in
the reactants equals the number of atoms of each element in the products.

CHEMICAL EQUATIONS AND REACTIONS 265

 TABLE 2 Symbols Used in Chemical Equations
Symbol Explanation
> : indicates result of reaction
‘' Yields*'

Used in place of a single arrow to indicate a

f
reversible reaction
(s) A reactant or product in the solid state: also
used to indicate a precipitate

Alternative to (.? ), but used only to indicate a

I precipitate

</) A reactant or product in the liquid state

A reactant or product in an aqueous solution
< <I <I ) ( dissolved in water )

(g ) A reactant or product in the gaseous state

Alternative to (g ), but used only to indicate a

T gaseous product
A » or heat Reactants are heated
>

2 atm Pressure at which reaction is carried out . in

-» this case 2 atm

pressure Pressure at which reaction is carried out

* exceeds normal atmospheric pressure

IIC Temperature at which reaction is carried out.

-> in this case 0 C

VI nO, Formula of catalyst , in this case manganese

* dioxide, used to alter the rate of the reaction

symbolized by a Greek capital delta. A. indicates that the reactants must

be heated . The specific temperature at which a reaction occurs may also
be written over the arrow. For some reactions, it is important to specify
the pressure at which the reaction occurs or to specify that the pressure
must be above normal. Many reactions are speeded up and can take
place at lower temperatures in the presence of a catalyst . A catalyst is a
substance that changes the rate of a chemical reaction but can be recov -
ered unchanged . To show that a catalyst is present , the formula for the
catalyst or the word catalyst is written over the reaction arrow.
In many reactions, as soon as the products begin to form , they imme-
diately begin to react with each other and re - form the reactants. In
other words, the reverse reaction also occurs. The reverse reaction may
occur to a greater or lesser degree than the original reaction , depend -
ing on the specific reaction and the conditions. A reversible
reaction is a chemical reaction in w hich the products re - form the original

266 CHAPTER 8
reactants.The reversibility of a reaction is indicated by writing two
arrows pointing in opposite directions. For example, the reversible reac -
lion between iron and water vapor is written as follows.

3Fe ( s ) + 4H20(g) f Fe304(.s ) + 4H2(£ )

With an understanding of all the symbols and formulas used, it is pos-

sible to translate a chemical equation into a sentence. Consider the fol -
lowing equation.

21 lgO ( .\ ) —-—> 2Hg( / ) + 0:(g)

Translated into a sentence, this equation reads. “ When heated, solid
mercury ( II) oxide yields liquid mercury and gaseous oxygen.' *

It is also possible to write a chemical equation from a sentence describ-

ing a reaction. Consider the sentence. "Under pressure and in the pres-
ence of a platinum catalyst, gaseous ethene and hydrogen form gaseous
ethane.* ' This sentence can be translated into the following equation.

C:H 4( £ ) + H 2 ( .^ ) pressure
, l* t

Throughout this chapter we will often include the symbols for physi -
cal states ( s, /. ft and aq ) in balanced formula equations. You should be
able to interpret these symbols when they are used and to supply them
when the necessarv information is available.

SAMPLE PROBLEM A For more help, go to the Mat / l tutor at the end of this chapter.

Write word and formula equations for the chemical reaction that occurs when solid sodium oxide is added to
water at room temperature and forms sodium hydroxide ( dissolved in the water ). Include symbols for physi-
cal states in the formula equation. Then balance the formula equation to give a balanced chemical equation.

SOLUTION The word equation must show the reactants, sodium oxide and water, to the left of the
arrow. The product , sodium hydroxide, must appear to the right of the arrow.

sodium oxide + water sodium Indroxide

The word equation is converted to a formula equation bv replacing the name of each com -
pound with the appropriate chemical formula. To do this requires knowing that sodium has
an oxidation stale of + 1, that oxygen usually has an oxidation state of -2. and that a hydrox -
ide ion has a charge of 1-.

Na:G + H20 » NaOH ( not balanced )

Adding symbols for the physical states of the reactants and products and the coefficient 2 in
front of NaOH produces a balanced chemical equation.

Na20(5 ) + H20( / )
* 2NaOH( aq )
CHEMICAL EQUATIONS AND REACTIONS 267
 SAMPLE PROBLEM B
Translate the following chemical equation into a sentence:

BaCI:k/ </ ) + Na 2Cr()4k/ </ ) > BaCr 04( s ) + 2NaCl(<i<jr )

SOLUTION Each reactant is an ionic compound and is named according to the rules for such com -
pounds. Both reactants are in aqueous solution. One product is a precipitate and the other
remains in solution. The equation is translated as follows: Aqueous solutions of barium
chloride and sodium chromate react to produce a precipitate of barium chromate plus sodi -
um chloride in aqueous solution.

PRACTICE Answers in Appendix E

1 . Write word and balanced chemical equations for the following

reactions. Include symbols for physical states when indicated.
a. Solid calcium reacts with solid sulfur to produce solid calcium
sulfide.
b. Hydrogen gas reacts with fluorine gas to produce hydrogen flu-
oride gas. ( Hint: See Table 1. )
c. Solid aluminum metal reacts with aqueous zinc chloride to pro -
duce solid zinc metal and aqueous aluminum chloride.
2. Translate the following chemical equations into sentences:
a. CS (/ ) + 302
(g) > C( ):( e ) - 2S02($)
*
,

b NaCl
. ( fi<7 ) + AgNO$( aq ) > NaNO$ ( aq ) + AgCl(s)
.
3. Hydrazine. N 2H4 is used as rocket fuel. Hydrazine reacts violently
with oxygen to produce gaseous nitrogen and water. Write the Go to go.hrw.com for
balanced chemical equation. more practice problems
that ask you to write
balanced chemical
equations.
Keyword: HC 6 RXNX

Significance of a Chemical Equation

Chemical equations are very useful in doing quantitative chemical
work. The arrow in a balanced chemical equation is like an equal sign.
And the chemical equation as a whole is similar to an algebraic equa -
tion in that it expresses an equality. Let 's examine some of the quanti -
tative information revealed by a chemical equation.
1. The coefficients of a chemical reaction indicate relative, not absolute;
amounts of reactants and products. A chemical equation usually
shows the smallest numbers of atoms, molecules, or ions that will sat -
isfy the law of conservation of mass in a given chemical reaction.

268 CHAPTER 8
 Consider the equation for the formation of hydrogen chloride from
hydrogen and chlorine.

H2(g) + Cl2(g) > 2HC1(# )

The equation indicates that I molecule of hydrogen reacts with 1

molecule of chlorine to produce 2 molecules of hydrogen chloride,
giving the following molecular ratio of reactants and products.

1 molecule IH : 1 molecule CU : 2 molecules HC1

This ratio shows the smallest possible relative amounts of the reac -
tion's reactants and products. To obtain larger relative amounts, we
simply multiply each coefficient by the same number. Thus. 20 mol-
ecules of hydrogen would react with 20 molecules of chlorine to yield
40 molecules of hydrogen chloride. The reaction can also be consid -
ered in terms of amounts in moles: 1 mol of hydrogen molecules
reacts with 1 mol of chlorine molecules to yield 2 mol of hydrogen
chloride molecules.
2. The relative masses of the reactants anil products of a chemical reac -
tion can he determined from the reaction 's coefficients. Recall from
Figure 4 in Chapter 7 that an amount of an element or compound in
moles can be converted to a mass in grams by multiplying by the
CHEMISTRY Ji
appropriate molar mass. We know that 1 mol of hydrogen reacts with Module S: Equations and
Stoichiometry
1 mol of chlorine to yield 2 mol of hydrogen chloride. The relative
masses of the reactants and products are calculated as follows.

2.02 gll:
i mol H: x
moWT = 2 02 «
70.90 g Cl2
l mol CT x = 70.90 g Cl2
mol C1-*
36.4b g HCI
2-mo1 HCI x
mol HQ
= 72.92 g HCI
FIGURE 4 This representation
of the reaction of hydrogen and
The chemical equation shows that 2.02 g of hydrogen will react with
chlorine to yield hydrogen chloride
70.90 g of chlorine to yield 72.92 g of hydrogen chloride.
shows several ways to interpret the
quantitative information of a chemi-
cal reaction.

H2 2 HCI

& +

1 molecule H 2 1 molecule Cl 2 2 molecules HCI

1 mol H2 1 mol Cl 2 2 mol HCI
2.02 g H 2 70.90 g Cl2 2 x 36.46 g = 72.92 g HCI

CHEMICAL EQUATIONS AND REACTIONS 269

 3 . The reverse reaction for a chemical equation has the same relative
amounts of substances as the forward reaction. Because a chemical
equation is like an algebraic equation , the equality can be read in
either direction . Reading the hydrogen chloride formation equation
on the previous page from right to left , we can see that 2 molecules of
hydrogen chloride break down to form 1 molecule of hydrogen plus
1 molecule of chlorine. Similarly, 2 mol ( 72.92 g ) of hydrogen chlo-
ride yield 1 mol ( 2.02 g ) of hydrogen and 1 mol ( 70.90 g ) of chlorine.

We have seen that a chemical equation provides useful quantitative

information about a chemical reaction . However, there is also impor-
tant information that is not provided by a chemical equation . For
instance, an equation gives no indication of whether a reaction will actu -
ally occur. A chemical equation can be written for a reaction that may
not even take place. Some guidelines about the types of simple reac-
tions that can be expected to occur are given in Sections 2 and 3. And
later chapters provide additional guidelines for other types of reactions.
In all these guidelines, it is important to remember that experimenta -
tion forms the basis for confirming that a particular chemical reaction
will occur.
In addition, chemical equations give no information about the speed
at which reactions occur or about how the bonding between atoms or
ions changes during the reaction. These aspects of chemical reactions
are discussed in Chapter 17.

Balancing Chemical Equations

Most of the equations in the remainder of this chapter can be balanced
by inspection . The following procedure demonstrates how to master
balancing equations by inspection using a step- bv -step approach . Hie
equation for the decomposition of water (see Figure 5 ) will be used as
an example.
FIGURE 5 When an electric cur - 1 . Identify the names of the reactants and the products, and write a won /
rent is passed through water that has equation. The word equation for the reaction shown in Figure 5 is
been made slightly conductive, the written as follows.
water molecules break down to yield
hydrogen ( in tube at right ) and oxy - water hydrogen + oxygen
.
gen ( in tube at left ) Bubbles
of each gas are evidence of the
reaction. Note that twice as much
2. Write a formula equation hv substituting correct formulas for the
hydrogen as oxygen is produced . names of the reactants and the products. We know that the formula
for water is H:0. And recall that both hydrogen and oxygen exist as
diatomic molecules. Therefore, their correct formulas are H: and 0:.
respectively.

H 7Q( / ) » H:( g ) + 02 (g ) ( not balanced )

270 CHAPTER 8
3. Balance the formula equation according to the law of conservation
of mass. This last step is done by trial and error. Coefficients are
changed and the numbers of atoms are counted on both sides of the
equation. When the numbers of each type of atom are the same for
both the products and the reactants, the equation is balanced. The
trial-and-error method of balancing equations is made easier by the
use of the following guidelines .
• Balance the different types of atoms one at a time.
• First balance the atoms of elements that are combined and that
appear only once on each side of the equation.
• Balance polyatomic ions that appear on both sides of the equa -
tion as single units.
• Balance H atoms and O atoms after atoms of all other elements
have been balanced.
The formula equation in our example shows that there are two oxygen
.
atoms on the right and only one on the left To balance oxygen atoms,
.
the number of ICO molecules must be increased Placing the coefficient
2 before H:0 gives the necessary two oxygen atoms on the left.

2H:0( / ) H:( g) + 0:(g ) ( partially balanced )

Hie coefficient 2 in front of H:0 has upset the balance of hydrogen atoms.
Placing the coefficient 2 in front of hydrogen, PC, on the right, gives an
equal number of hydrogen atoms ( 4 ) on both sides of the equation.

2H:0( / )
* 2H2( g) + 02(g)
4. Count he sure that the equation is balanced. Make sure that
atoms to
equal numbers atoms of each element appear on both sides of the
of
arrow.

2 H:0( / ) — » 2H2(g) + 02( g )

( 4H + 20) = ( 4K) + ( 20)

Occasionally at this point , the coefficients do not represent the smallest

possible whole-number ratio of reactants and products. When this hap-
pens. the coefficients should be divided by their greatest common fac -
tor in order to obtain the smallest possible whole-number coefficients.
Balancing chemical equations by inspection becomes easier as
you gain experience. Learn to avoid the most common mistakes:
( 1 ) writing incorrect chemical formulas for reactants or products and
( 2 ) trying to balance an equation bv changing subscripts. Remember
that subscripts cannot be added deleted, or changed. Eventually, you
,

will probably be able to skip writing the word equation and each sep -
arate step. I lowever. do not leave out the final step of counting atoms
to be sure the equation is balanced.

CHEMICAL EQUATIONS AND REACTIONS 271

 SAMPLE PROBLEM C For more help, go to the Math Tutor at the end of this chapter.

The reaction of zinc with aqueous hydrochloric acid produces a solution of zinc
chloride and hydrogen gas. This reaction is shown at right in f igure 6. Write a -
A

>
balanced chemical equation for the reaction. Jtfu

SOLUTION ' ??

1 ANALYZE Write the won! equation. * j*

zinc 4 hydrochloric acid 4 zinc chloride + hydrogen

ft .
2 PLAAf Wr/ fe the formula equation.

Zn( s ) + HCI( aq ) > ZnO:( w/ ) + H2(g) ( not balanced )

*
iSSTH
3 COMPUTE Adjust the coefficients. Note that chlorine and hydrogen each
appear only once on each side of the equation. We balance
chlorine first because it is combined on both sides of the equa -
tion. Also, recall from the guidelines on the previous page that FIGURE 6 Solid zinc
hydrogen and oxygen are balanced only after all other elements reacts with hydrochloric
acid to form aqueous zinc
in the reaction are balanced. To balance chlorine, we place the
chloride and hydrogen gas.
coefficient 2 before I ICl. Two molecules of hydrogen chloride
also yield the required two hydrogen atoms on the right. Finally,
note that there is one zinc atom on each side in the formula
equation. Therefore, no further coefficients are needed.

Zn(s) + 21 \ C\ ( aq ) 4 ZnCI2( < / </ ) + H2( g )

4 EVALUATE ( Ount atoms to check balance.

Zn( .v ) 4- 2HCI( aq ) 4 ZnG:( aq ) 4 H:( g )

( IZn ) 4- ( 2H 4- 2CI) = ( IZn 4 20) 4 ( 2H)

The equation is balanced.

PRACTICE Answers in Appendix E

.
1 Write word, formula, and balanced chemical equations for each of
the following reactions:
a. Magnesium and hydrochloric acid react to produce magnesium
chloride and hydrogen.
b. Aqueous nitric acid reacts with solid magnesium hydroxide to
produce aqueous magnesium nitrate and water.
2. Solid calcium metal reacts with water to form aqueous calcium Go to go.hrw.com for
hydroxide and hydrogen gas. Write a balanced chemical equation more practice problems
that ask you to write
for this reaction.
balanced chemical
equations.
Keyword: HC 6RXNX

272 CHAPTER 8
SAMPLE PROBLEM For more help, go to the Math 71itor at the end of this chapter.
Solid aluminum carbide, AI4C3, reacts with water to produce methane gas and solid aluminum hydroxide.
Write a balanced chemical ecpiation for this reaction.

SOLUTION The reactants are aluminum carbide and water. Hie products are methane and aluminum
hydroxide. The formula equation is written as follows.

Ai4Cds ) + H:D( / ) » CH4 ( g ) + Al( OH )3( s ) ( not balanced )

Begin balancing the formula equation by counting either aluminum atoms or carbon atoms.
( Remember that hydrogen and oxygen atoms are balanced last . ) There are four A1 atoms
on the left. To balance Al atoms, place the coefficient 4 before AI( OH)3 on the right.

,
AI4C (5) + H 2Q ( / ) » CH4(g ) + 4 AI( OH )3( s ) ( partially balanced )

Now balance the carbon atoms. With three C atoms on the left, the coefficient 3 must be
placed before CH4 on the right .

Al4C3(s) + H20( / )
* 3CH4(g) + 4 AI( OH ) 3(.s ) ( partially balanced )

Balance oxygen atoms next because oxygen, unlike hydrogen, appears only once on each
side of the equation. There is one O atom on the left and 12 O atoms in the four Al( OH)3
formula units on the right. Placing the coefficient 12 before H2Q balances the O atoms.

<
Al4C3( s ) + 12H:0 / ) > 3CH4(g) + 4AI( OH )3($ )

This leaves the hydrogen atoms to be balanced. There are 24 H atoms on the left. On the
right , there are 12 H atoms in the methane molecules and 12 in the aluminum hydroxide
formula units, totaling 24 H atoms. The II atoms are balanced.

AI4C3(5) + 12H:0( / ) 3CH4(g) + 4 Al( OH );(.v )

( 4 AI + 3C ) + ( 24M + T20 )
* (SC + I2H ) + ( 4A 1 + 12H + 120 )

Tlie equation is balanced.

SAMPLE PROBLEM E For more help, go to the Math Tutor at the end of this chapter.

Aluminum sulfate and calcium hydroxide are used in a water-purification process. When added to water, they
dissolve and react to produce two insoluble products, aluminum hydroxide and calcium sulfate. These products
settle out, taking suspended solid impurities with them. Write a balanced chemical equation for the reaction.

SOLUTION Each of the reactants and products is an ionic compound. Recall from Chapter 7 that the
formulas of ionic compounds are determined by the charges of the ions composing each
compound. The formula reaction is thus written as follows.

Al2( S04)3 + Ca(0H )2 » Al( OH ) ? + CaSOj ( not balanced )

CHEMICAL EQUATIONS AND REACTIONS 273

 There is one Ca atom on each side of the equation, so the calcium atoms are already balanced.
There are two Al atoms on the left and one A1 atom on the right. Placing the coefficient 2 in
front of AI( OH )3 produces the same number of Al atoms on each side of the equation.

AI2( S04) 3 + Ca( 0H)2 2 AI( OH) ? + CaS04 (partially balanced )

Next, checking SO} ions shows that there are three SO3 ions on the left side of the equa -
*

tion and only one on the right side. Placing the coefficient 3 before CaS04 gives an equal
number of SO } ions on each side.

AI2( S04)3 + Ca( OH )2 » 2 Al( OH ) 3 + 3CaS04 ( partially balanced)

There are now three Ca atoms on the right , however. By placing the coefficient 3 in front of
.
Ca ( OH)2. we once again have an equal number of Ca atoms on each side This last step also
gives six OH ions on both sides of the equation.

AI2( SO4)3( <W / ) + 3Ca( OH )2( £if/ ) > 2 A 1(OH)3(J) + 3CaS04(.v )

(2AI + 3S0f ) + ( 3Ca + 60fT ) = ( 2 AI + 60H ) + (3Ca + 35 >f )

The equation is balanced.

PRACTICE Answers in Appendix E

1. Write balanced chemical equations for each of the following

reactions:
a. Solid sodium combines with chlorine gas to produce solid sodi -
um chloride.

b. When solid copper reacts with aqueous silver nitrate, the prod-
ucts are aqueous copper( U) nitrate and solid silver.
Go to go.hrw.com for
c. In a blast furnace, the reaction between solid iron(III) oxide more practice problems
and carbon monoxide gas produces solid iron and carbon diox - that ask you to write
ide gas. balanced chemical
equations.
Keyword: HC 6RXNX

SECTION REVIEW 4. Write the word, formula, and chemical equations

1. Describe the differences between word equations, for the reaction between hydrogen sulfide gas and
formula equations, and chemical equations. oxygen gas that produces sulfur dioxide gas and
water vapor.
2. Write word and formula equations for the reaction
in which aqueous solutions of sulfuric acid and Critical Thinking
sodium hydroxide react to form aqueous sodium 5. INTEGRATING CONCEPTS The reaction of vanadi -
sulfate and water. um(ll) oxide with iron(lll) oxide results in the for-
3. Translate the following chemical equations into mation of vanadium(V) oxide and iron(ll) oxide.
sentences: Write the balanced chemical equation.
a. 2 K(s) + 2 H20( /) -> 2 K0H( ag) + H2(g)
b. 2 Fe( s) + 3CI2(g) 2 FeCI3(s)

274 CHAPTER 8
Chemistiy in Action
Carbon Monoxide Catalyst
Colorless, odorless, and deadly— NASA's space-based carbon dioxide converters in cars oxidize carbon
carbon monoxide, " the silent killer," laser needed to be fed a continuous monoxide and unburned hydrocar -
causes the deaths of hundreds of supply of C 02. This was necessary bons to minimize pollution. Many
Americans every year. When fuel because as a byproduct of its opera - substances are oxidized into new
does not burn completely in a com- tion, the laser degraded some of the materials for manufacturing purposes.
bustion process, carbon monoxide is C 02 into carbon monoxide and oxy- But both of these types of catalytic
produced. Often this occurs in a mal - gen. To address this problem, NASA reactions occur at very high tempera -
functioning heater, furnace, or fire- scientists developed a catalyst made tures. NASA's catalyst is special,
place. When the carbon monoxide is of tin oxide and platinum that oxi - because it's able to eliminate carbon
inhaled, it bonds to the hemoglobin dized the waste carbon monoxide monoxide at room temperature.
in the blood, leaving the body oxy - back into carbon dioxide. The NASA According to David Schryer, low-
gen starved. Before people realize a scientists then realized that this cat- temperature catalysts constitute a
combustion device is malfunctioning, alyst had the potential to be used in whole new class of catalysts with
it 's often too late. many applications here on Earth, abundant applications for the future.
including removing carbon monoxide
02Hb + CO — COHb + 02 from houses and other buildings. Questions
Carbon monoxide, CO, has almost Typically, a malfunctioning heater 1. How did NASA's research on the
200 times the affinity to bind with circulates the carbon monoxide it space-based carbon dioxide laser
the hemoglobin, Hb, in the blood as produces through its air intake sys- result in a benefit for consumers ?
oxygen. This means that hemoglobin tem back into a dwelling space.
will bind to carbon monoxide rather 2. According to the chemical reac -
Installing the catalyst in the air
than oxygen in the body. If enough tion, if there are 4.5 mol of oxy -
carbon monoxide is present in the intake would oxidize any carbon
genated hemoglobin present in
blood, it can be fatal. monoxide to nontoxic carbon dioxide
an excess of carbon monoxide,
before it reentered the room.
Carbon monoxide poisoning can " The form of our catalyst is a very
how many moles of hemoglobin
be prevented by installing filters that would release oxygen and bind
thin coating on some sort of a sup -
absorb the gas. After a time, howev- to carbon monoxide ? Explain
port, or substrate as we call it, " says
er, filters become saturated, and then your answer.
NASA chemist David Schryer. "And
carbon monoxide can pass freely that support, or substrate, can be
into the air. The best way to prevent any one of a number of things. The
carbon monoxide poisoning is not
just to filter out the gas, but to elimi -
great thing about a catalyst is that
the only thing that matters about it
SC
/lNKS. Dmtap md MMUiMd by U
* *
NJIMMI Suemc TMCIMVI Austutwii

nate it completely. is its surface. So a catalyst can be For a variety of links related to this
The solution came to research incredibly thin and still be very chapter, go to www.scilinks.org
chemists at NASA who were working effective." Topic: Carbon Monoxide
on a problem with a space-based The idea of using catalysts to oxi- Sci Links code: HC60219
laser. In order to operate properly, dize gases is not a new one. Catalytic

CHEMICAL EQUATIONS AND REACTIONS 275

 SECTION 2
Types ofChemical
OBJECTIVES Reactions
Define and give general equa -
tions for synthesis, decomposi-
tion, single-displacement, and
double-displacement
reactions. T housands of known chemical reactions occur in living systems, in
industrial processes, and in chemical laboratories. Often it is necessary
Classify a reaction as a to predict the products formed in one of these reactions. Memorizing
synthesis, decomposition, the equations for so many chemical reactions would be a difficult task .
single-displacement, double- It is therefore more useful and realistic to classify reactions according to
displacement, or combustion various similarities and regularities. This general information about
reaction. reaction types can then be used to predict the products of specific
reactions.
There are several ways to classify chemical reactions, and none are
^ List three kinds of synthesis
reactions and six kinds of entirely satisfactory. The classification scheme described in this section
decomposition reactions. provides an introduction to five basic types of reactions: synthesis,
decomposition, single-displacement, double-displacement, and combus-
tion reactions. In later chapters, you will be introduced to categories
List four kinds of single-
that are useful in classifying other types of chemical reactions.
sj

displacement reactions and

three kinds of double-
displacement reactions.

Synthesis Reactions
Predict the products of simple
reactions given the reactants. In a synthesis reaction, also known as a composition traction, two or
more substances combine to form a new compound. This type of reac -
tion is represented by the following general equation.

A+X » AX

A and X can be elements or compounds. AX is a compound. The fol-

lowing examples illustrate several kinds of synthesis reactions.

Reactions of Elements with Oxygen and Sulfur

One simple type of synthesis reaction is the combination of an element
with oxygen to produce an oxide of the element. Almost all metals react
with oxygen to form oxides. For example, when a thin strip of magne -
sium metal is placed in an open flame, it burns with bright while light .
When the metal strip is completely burned, only a fine white powder of
magnesium oxide is left. This chemical reaction, shown in Figure 7 on
the next page, is represented by the following equation.

2Mg(.v ) + 02(g) > 2MgO( s )

276 CHAPTER 8
The other Group 2 elements react in a similar manner, forming oxides
with the formula MO, where M represents the metal. The Group I met -
als form oxides with the formula M20. for example, LbO. The Group 1
and Group 2 elements react similarly with sulfur, forming sulfides with
the formulas M2 $ and MS. respectively. Examples of these types of syn -
thesis reactions are shown below.

16Rb($) + S S( A )
(
^ 8Rb2S($)
NBa( .v ) + SK( .v )
* SBaS(.s )
Some metals, such as iron, combine with oxygen to produce two dif -
ferent oxides.

2Fe(.v ) + 02(g) -> 2FeO( s)

4Fe(s) + 302(#) > 2Fe:03(.v )

In the product of the first reaction, iron is in an oxidation state of +2. In

the product of the second reaction, iron is in an oxidation state of +3.
The particular oxide formed depends on the conditions surrounding the
reactants. Both oxides are shown below in Figure 8 .
Nonmetals also undergo synthesis reactions with oxygen to form
oxides. Sulfur, for example, reacts with oxygen to form sulfur dioxide.
And when carbon is burned in air. carbon dioxide is produced.

Ss(s ) + 802(g) -> 8S02(g)

C(5) + 02(g) » C02 ( g )
In a limited supply of oxygen, carbon monoxide is formed.
( b)

2C(s) + 02(g) > 2CO(g) FIGURE 7 Magnesium, Mg.

pictured in ( a ), undergoes a synthe-
Hydrogen reacts with oxygen to form dihydrogen monoxide, better .
sis reaction with oxygen 02, in the
known as water. air to produce magnesium oxide.
MgO, as shown in (b).
2H:( g) + 02( jtf )
* 2H:OG?)

FIGURE 8 Iron, Fe, and oxygen, 02, combine to form two different oxides:
. 203.
( a ) iron(II ) oxide. FeO and ( b ) iron( III ) oxide, Fe

CHEMICAL EQUATIONS AND REACTIONS 277

 Reactions of Metals with Halogens
Most metals react with the Group 17 elements, the halogens, to form
either ionic or covalent compounds. For example. Group 1 metals react
with halogens to form ionic compounds with the formula MX , where M
is the metal and X is the halogen . Examples of this type of synthesis
reaction include the reactions of sodium with chlorine and potassium
with iodine.

2 Na ( .v ) + C\2 ( g ) > 2 NaCI ( x )

2 K (.v ) + 12( g ) » 2 KI ( s )

Group 2 metals react with the halogens to form ionic compounds with
the formula MX:.

Mg( x ) + F2 (g ) > MgF2 (s)

Sr (.v ) + Br 2 ( / ) > SrBr2(s )

Tlie halogens undergo synthesis reactions with many different met -

als. Fluorine in particular is so reactive that it combines with almost all
metals. For example, fluorine reacts with sodium to produce sodium fluo-
ride. Similarly, it reacts with cobalt to form cobalt ( IH ) fluoride and with
uranium to form uramum ( VI ) fluoride.

2Na (s ) + F2(g ) » 2 NaF( x )

2Co(s) + 3F2(g) 2CoF3(.v )
U (.v ) + 3F2( g ) UF6( )
^
Sodium fluoride, NaF. is added to municipal water supplies in trace
amounts to provide fluoride ions, which help to prevent tooth decay in
the people who drink the water. Cobalt ( III ) fluoride, CoF> is a strong
lluorinating agent. And natural uranium is converted to uranium ) VI )
fluoride, UF6, as the first step in the production of uranium for use in
nuclear power plants.

Synthesis Reactions with Oxides

._
ANTACID TABLETS
» . * » •< > .
“*-**»****-“•
“ •»« W
Active metals are highly reactive metals. Oxides of active metals react
with water to produce metal hydroxides. For example, calcium oxide
..... « n • """
Mnm I !

'. •» •' * •'

i n «
Iflr
fiur . * •X .
it
MI
M
l'
H ««*
'
> •
"
reacts with water to form calcium hydroxide, an ingredient in some
• mC kvJm - - stomach antacids, as shown in Figure 9.
W VKTCiior^
* NESCIENTS Eachtablttcontainsa 6il«uc c
_ T'lton 200 mg Aluminum hydros # l»du» 59 7 '
* CaO ( s ) + H 20( / ) > Ca ( OH )2 (s )
Calcium Hydroxid # and 20 mg
*
NGKEOIESTS Colloidal Silicon DwvJ Dtr*
* 5 Calcium oxide, CaO. also known as lime or quicklime, is manufactured
^ jrtiiumSttaratt Mannitol. Sodium SsccftJ
* in large quantities. The addition of water to lime to produce Ca ( OH )2,
which is also known as slaked lime, is a crucial step in the setting of
FIGURE 9 Calcium hydroxide,
a base, can he used to neutralize cement.
hydrochloric acid in your stomach . Many oxides of nonmetals in the upper right portion of the periodic
You will read more about acids, bases, table react with water to produce oxyacids. For example, sulfur dioxide,
and neutralization in C hapter 14. SQ . reacts with water to produce sulfurous acid .
2

278 CHAPTER 8
 S02(g) + H20( / ) H2S03( aq )

In air polluted with S02. sulfurous acid further reacts with oxygen to
form sulfuric acid, one of the main ingredients in acid rain .

2H2S03( fl</ ) + 02(g) 2H2S04(<K/ )

Certain metal oxides and nonmetal oxides react with each other in
synthesis reactions to form salts. For example, calcium sulfite is formed
In the reaction of calcium oxide and sulfur dioxide.

CaO( s ) + SC)2( g) > CaS03( s )

Decomposition Reactions
In a decomposition reaction, a single compound undergoes a reaction
that produces two or more simpler substances. Decomposition reactions
are the opposite of synthesis reactions and are represented by the fol -
lowing general equation.

AX >A+X

AX is a compound. A and X can be elements or compounds.

Most decomposition reactions take place only when energy in the
form of electricity or heat is added. Examples of several types of decom -
position reactions are given in the following sections .
Decomposition of Binary Compounds
The simplest kind of decomposition reaction is the decomposition of a
binary compound into its elements. We have already examined one
example of a decomposition reaction. Figure 5 on page 270 shows that
passing an electric current through water will decompose the water
into its constituent elements, hydrogen and oxygen.

2H,0( / ) electricity
* 2H:( g) + 0:(,;) i

/ he decomposition of a substance by an electric current is called

electrolysis.
-
Oxides of the less active metals, which are located in the lower center
of the periodic table, decompose into their elements when heated. Joseph
Priestley discovered oxygen through such a decomposition reaction in
1774. when he heated mercury! 11 ) oxide to produce mercury and oxygen.

A
2HgO(.v ) > 2Hg( / ) + 02(g)

This reaction is shown in Figure 10 on the following page.

CHEMICAL EQUATIONS AND REACTIONS 279

 FIGURE 10 When mercury! 11 )
oxide ( the red-orange substance in
the bottom of the test tube ) is heat -
ed. it decomposes into oxygen and
metallic mercury, which can be seen
as droplets on the inside wall of the
test tube.

Decomposition of Metal Carbonates

When a metal carbonate is heated, it breaks down to produce a metal
oxide and carbon dioxide gas. For example, calcium carbonate decom -
poses to produce calcium oxide and carbon dioxide.

.
CaCO ( s ) A
> CaO( s ) + CO2( g )

Decomposition of Metal Hydroxides

All metal hydroxides except those containing Group I metals decom -
pose when heated to yield metal oxides and water. For example, cal -
cium hydroxide decomposes to produce calcium oxide and water.

A
Ca( OH)i(i) > CaO(i) + H-,0(g)

Decomposition of Metal Chlorates

When a metal chlorate is heated, it decomposes to produce a metal
chloride and oxygen. For example, potassium chlorate, KCIO3, decom -
poses in the presence of the catalyst Mn02(.v ) to produce potassium
chloride and oxygen.
A
2 KCl0 .v ) 2 KCI(.v ) + 30:(s )
^ Mn():( v )

Decomposition of Acids
Certain acids decompose into nonmetal oxides and water. Carbonic
acid is unstable and decomposes readily at room temperature to pro-
duce carbon dioxide and water.

H2C03(M/ ) > C02( s ) + II20( / )

When heated, sulfuric acid decomposes into sulfur trioxide and water.

H2S04M soy ( g ) + H20( / )

Sulfurous acid. H2 S03, decomposes similarly.

280 CHAPTER 8
 Single - Displacement Reactions
In a single-displacement reaction, also know n as a replacement reaction ,
one element replaces a similar element in a compound. Many single -
displacement reactions take place in aqueous solution. The amount of
energy involved in this type of reaction is usually smaller than the amount
involved in synthesis or decomposition reactions. Single-displacement
reactions can he represented by the following general equations.

A + BX > AX + B
or
Y + BX * BY + X
A . B, X . and Y are elements. AX , BX. and BY are compounds.

Displacement of a Metal in a Compound

by Another Metal
Aluminum is more active than lead . When solid aluminum is placed in
aqueous lead ( II ) nitrate. Pb ( NOv)2 ( aq ) , the aluminum replaces the
lead. Solid lead and aqueous aluminum nitrate are formed.

2 AI (*) + 3Pb( NO3 )2( 0<7 ) » 3Pb(s ) + 2 A\{ NO $ ) y( aq )

Displacement of Hydrogen in Water by a Metal

The most -active metals, such as those in Group 1 . react vigorously with
water to produce metal hydroxides and hydrogen . For example, sodium
reacts with water to form sodium hydroxide and hydrogen gas.

2 Na ( .v ) + 2 H:Q( / ) 2 NaOH ( */ r/ ) + H 2 ( g )

-
Less active metals, such as iron , react with steam to form a metal oxide
and hydrogen gas.

3Fe(s) + 4 H 20( g ) > Fe 304(.v ) + 4 H 2 ( g )

Displacement of Hydrogen in an Acid by a Metal

-
The more active metals react with certain acidic solutions, such as
hydrochloric acid and dilute sulfuric acid , replacing the hydrogen in the
acid . The reaction products are a metal compound ( a salt ) and hydrogen
gas. For example, when solid magnesium reacts with hydrochloric acid ,
as shown in Figure 11 , the reaction products are hydrogen gas and aque -
ous magnesium chloride.

Mg(s) + 2 HCI ( w/ ) H 2(J? ) + MgCI 2( tf <7 )

FIGURE 11 In this single -
Displacement of Halogens displacement reaction , the hydrogen
In another type of single-displacement reaction , one halogen replaces in hydrochloric acid , HCl. is replaced
another halogen in a compound . Fluorine is the most -active halogen . As by magnesium . Mg.

CHEMICAL EQUATIONS AND REACTIONS 281

 such , it can replace any of the other halogens in their compounds. Each
halogen is less active than the one above it in the periodic table.
Therefore, in Group 17 each element can replace any element below it .
but not any element above it . For example, while chlorine can replace
bromine in potassium bromide, it cannot replace fluorine in potassium
fluoride. The reaction of chlorine with potassium bromide produces
bromine and potassium chloride, whereas the combination of fluorine
and sodium chloride produces sodium fluoride and solid chlorine.

Cl2( £ ) + 2 KBr ( aq ) * 2 KCI ( ar/ ) + Br2( / )

F2( g ) + 2 NaCI ( aq ) 2 NaF( (/ r/ ) + CU ( g )
Br:( / ) -i- KC\( aq ) -> no reaction

SC
/ lNKS DtrtlwpH mi autiUlart h
NidtAil Sonic Tncbm AwooAto*
Double- Displacement Reactions
For a variety of links related to this In double -displacement reactions, the ions of two compounds exchange
-
chapter, go to w .vw scilmks. orcj
b places in an aqueous solution to form two new compounds. One of the
Topic: Precipitate
compounds formed is usually a precipitate, an insoluble gas that bub-
SciLinks code: HC61201
bles out of the solution , or a molecular compound , usually water. The
other compound is often soluble and remains dissolved in solution. A
double -displacement reaction is represented by the following general
equation .

AX + BY > AY + BX

A . X. B, and V in the reactants represent ions. AY and BX represent

ionic or molecular compounds.

Formation of a Precipitate
The formation of a precipitate occurs when the cations of one reactant
combine with the anions of another reactant to form an insoluble or
slightly soluble compound . For example, when an aqueous solution of
potassium iodide is added to an aqueous solution of lead ( ll ) nitrate, the
yellow precipitate lead! II ) iodide forms. This is shown in F i g u r e 12.

2 K 1 ( a q ) + Pb( NO f )i( aq ) Pbl 2(s ) + 2 KNO ( a q )

^
The precipitate forms as a result of the very strong attractive forces
between the Pb:" cations and the I anions. The other product is the
water-soluble salt potassium nitrate. KNO3. The potassium and nitrate
ions do not take part in the reaction . They remain in solution as aque-
ous ions. The guidelines that help identify which ions form a precipitate
FIGURE 12 The double - and w hich ions remain in solution are developed in Chapter 13.
displacement reaction between
aqueous lead ( II ) nitrate.
Pb( N ( ), H < / < / ). and aqueous potas- Formation of a Gas
.
sium iodide, k I ( aq ) yields the pre - In some double-displacement reactions, one of the products is an insol -
cipitate lcad ( II ) iodide. Pblq .v ). uble gas that bubbles out of the mixture. For example, iron ( ll ) sulfide

282 CHAPTER 8
reacts with hydrochloric acid to form hydrogen sulfide gas and iron( ll )
chloride.

FeS(s ) + 2 HCl ( aq ) » H2S( g) + FeCI2(r/r/ )

Formation of Water
Chemistry in Action
In some double-displacement reactions, a very stable molecular com -
Fluoridation and
Tooth Decay
pound. such as water, is one of the products. For example, hydrochloric
The main component of tooth enamel
acid reacts with an aqueous solution of sodium hydroxide to yield aque-
is a mineral called hydroxyapatite,
ous sodium chloride and water. Ca5(P04) 30H. Some foods contain acids
or produce acids in the mouth, and acid
HCl( <w/ ) + NaOHM > NaCI( flg ) + H2Q( / ) dissolves tooth enamel, which leads to
tooth decay. One way to help prevent
tooth decay is by using fluoride.
Fluoride reacts with hydroxyapatite in a
double-displacement reaction. It dis-
Combustion Reactions places the OFT group in hydroxyapatite
to produce fluorapatite, Ca5(P04) 3 F.
In a combustion reaction, a substance combines with oxygen, releasing a Studies show that calcium fluorapatite
large amount of energy in the form of light and heat. The combustion of is about 20% less soluble than hydrox -
yapatite in acid. Therefore, fluoride low-
hydrogen is shown below in Figure 13. The reaction’s product is water ers the incidence of tooth decay.
vapor.

2H2(g) + 02(g) » 2H2Q(g)

The burning of natural gas, propane, gasoline, and wood are also exam -
ples of combustion reactions. For example, the burning of propane,
C3H8, results in the production of carbon dioxide and water vapor.

C3Hg( g ) + 5Q2(g) > 3C02(g) + 4H 2Q( g)

( a) (b)

FIGURE 13 ( a ) The candle supplies heal to the hydrogen and oxygen in

the balloon, triggering the explosive combustion reaction shown in (b ).

CHEMICAL EQUATIONS AND REACTIONS 283

 QuickIAB Wear safety goggles and an apron.

Materials
Balancing Equations Using Models • large and small gumdrops in
at least four different colors

Question Group A • toothpicks

How can molecular models a. H 2 + CI 2 - HCI
and formula - unit ionic mod- b. Mg + 02 - MgO
els be used to balance chemi- c. BaO + H20
cal equations and classify Group B
chemical reactions ? a. H 2C 03 -> co2 + H2O
b. KCI03
* KCI + 02
electricity
Procedure c. H20 »
Examine the partial equations in Group C
Groups A-E. Using different- a. Ca + H20 —-> Ca(OH)2 4- H2
colored gumdrops to represent b. Kl + Br 2 » KBr + l2
-

atoms of different elements, make c. Zn + HCI

models of the reactions by con -
Group D
necting the appropriate "atoms " a. AgN03 + NaCI
with toothpicks. Use your models
AgCI + NaN03
to ( 1 ) balance equations (a) and
b. FeS + HCI » FeCI2 + H 2 S
(b) in each group, ( 2) determine
c. H 2 SQ 4 + KOH > __
the products for reaction (c ) in
each group, and ( 3) complete Group E
and balance each equation (c ). a. CH4 + 02 -4 co2 + H2O
Finally, ( 4) classify each group of b. CO + 02 -
c . C 3H8 + 02
* co2
reactions by type.

SECTION REVIEW c. double displacement:

.
1 List five types of chemical reactions. HN03 + Ca (0H)2 »
2. Classify each of the following reactions as a syn- ,
d. combustion: C 5H 2 + 02
thesis, decomposition, single - displacement, dou- 4. For each of the following reactions, write the
ble-displacement, or combustion reaction: missing product(s) and then balance the resulting
a. N 2 ( g) + 3 H2 (g) - » 2 NH 3(g) equation. Identify each reaction by type.

b. 2Li(s) + 2 H20( / ) > 2 LiOH( acjf) + H2(g)

a. Br2 + Kl — »
c. 2 NaN 03(s) » 2 NaN02(s) + 02( g ) b. NaCI03 —
d. 2 C6H14(/ ) + 1902(g) c. C7H14 + 02 »
* 12C02(g) + 14H20( / ) d. CuCI2 + Na2 S
3. For each of the following reactions, identify the
missing reactant(s) or products(s) and then bal- Critical Thinking
ance the resulting equation. Note that each empty
slot may require one or more substances. 5. INFERRING RELATIONSHIPS In an experiment, an
iron sample is oxidized to iron(lll) oxide by oxy -
a. synthesis: > Li,0 gen, which is generated in the thermal decomposi -
b. decomposition: Mg(CI03) 2 » tion of potassium chlorate. Write the two chemical
reactions in the correct sequence.

284 CHAPTER 8
Activity Series of the SECTION 3

Elements OBJECTIVES
^ Explain the significance of
an activity series.

Use an activity series to

I he ability of an element to react is referred to as the element 's activ - predict whether a given
ity . The more readily an element reacts with other substances, the greater reaction will occur and
its activity is. An activity series is a list of elements organized according to what the products will be.
the ease with which the elements undergo certain chemical reactions . For
metals, greater activity means a greater ease of loss of electrons, to form
positive ions. For nonmetals, greater activity means a greater ease of gain
of electrons, to form negative ions.
The order in which the elements are listed is usually determined by
single-displacement reactions. The most -active element, placed at the
lop in the series, can replace each of the elements below ii from a com -
pound in a single-displacement reaction. An element farther down can
replace anv element below it but not any above it. For example, in the
discussion of single-displacement reactions in Section 2, it was noted SCtlNKS. Drwtfftd mi unUwd fry Ike
MJOWUI fctaMt If hen AMMUIIM
that each halogen will react to replace any halogen listed below it in the *
For a variety of links related to this
periodic table. Therefore, an activity series for the Group 17 elements chapter, go to www scilinks.org
lists them in the same order, from top to bottom, as they appear in the
periodic table. This is shown in Table 3 on the next page.
Topic: Activity Series
SciLinks code: HC60019
^
.
As mentioned in Section 1 the fact that a chemical equation can be
written does not necessarily mean that the reaction it represents will actu-
ally take place. Activity series are used to help predict whether certain
chemical reactions will occur. For example, according to the activity series
for metals in Table 3, aluminum replaces zinc.Therefore, we could predict
that the following reaction does occur.

2 Al(.v ) + 3 ZnCl:( </ </ ) > 3 Zn( .v ) + 2 AICI3( ^/ )

Cobalt, however, cannot replace sodium. Therefore, we write the

following.

Co( s ) + 2NaCl( aq )
* no reaction
It is important to remember that like many other aids used to predict
the products of chemical reactions, activity series are based on experi-
ment . The information that they contain is used as a general guide for
predicting reaction outcomes. For example, the activity series reflects
the fact that some metals ( potassium, for example) react vigorously
with water and acids, replacing hydrogen to form new compounds.
Other metals, such as iron or zinc, replace hydrogen in acids such as
hvdrochloric acid but react with water only when the water is hot

CHEMICAL EQUATIONS AND REACTIONS 285

 enough to become steam. Nickel, however, will replace hydrogen in acids
but will not react with steam at all. And gold will not react with individ-
ual acids or water, either as a liquid or as steam. Such experimental
observations are the basis for the activity series shown in Table 3.

TABLE 3 Activity Series of the Elements

Activity of metals Activity of halogen nonmetals
Li F2
Rb React with cold H:0 and CL
K acids, replacing hydrogen. Br 2
Ba React with oxygen, I2
Sr forming oxides.
Ca
Na
Mg
Al React with steam ( but not
Mn cold water ) and acids,
Zn replacing hydrogen.
Cr React with oxygen,
Fe forming oxides.
Cd

Co Do not react with water.

Ni React with acids .
Sn replacing hydrogen.
Pb React with oxygen,
forming oxides.

H2
Sb React with oxygen,
Bi forming oxides.
Cu
Hg

Ac Fairlv unreactive .
Pt forming oxides only
Au indirectlv.

SAMPLE PROBLEM F
Using the activity series shown in Table 3, explain whether each of the possible reactions listed below will
occur. For those reactions that will occur, predict what the products will be.

50 (
a . Zn(s) + 1I20 ( / ) ->
b. Sn is ) + ( > 2( £ ) —
,
c. Cd(s ) + l b ( N( ) 3 ) 2 ( r/r/ ) »
d . Cu(s) + 11CI( a q ) >

286 CHAPTER 8
 SOLUTION a. This is a reaction between a metal and water at 50 ' C. Zinc reacts with
water only when it is hot enough to be steam. Therefore, no reaction
will occur.
b. Any metal more active than silver will react with oxygen to form an oxide.
Tin is above silver in the activity series. Therefore, a reaction will occur, and
the product will be a tin oxide, either SnO or Sn02.
c. An element will replace any element below it in the activity series from
a compound in aqueous solution. Cadmium is above lead, and therefore
a reaction will occur to produce lead. Pb. and cadmium nitrate, CdfNO .
^
d. Any metal more active than hydrogen will replace hydrogen from an acid.
Copper is not above hydrogen in the series. Therefore, no reaction will occur.

PRACTICE Answers in Appendix E

1. Using the activity series shown in Table 3, predict whether each of

the possible reactions listed below will occur. For the reactions
that will occur, write the products and balance the equation.
a. Cr(s) + H2O( 0

b. Pt(s) + 02(g)
c. Cd(s) + 2HBr ( a q )
d. Mg(s) + steam —
2. Identify the element that replaces hydrogen from acids but cannot
replace tin from its compounds. . .
Go to go hrw com for
3. According to Table 3, what is the most -active transition metal? more practice problems
that deal with activity
series.
Keyword: HC 6 RXNX

SECTION REVIEW .
3 For each of the reactions in item 2 that will occur,
.
1 How is the activity series useful in predicting write the products and balance the equation.
chemical behavior ? Critical Thinking
2. Based on the activity series, predict whether 4. PREDICTING OUTCOMES A mixture contains
each of the following possible reactions will occur: cobalt metal, copper metal, and tin metal. This
a. Ni(s) + H20( / ) - mixture is mixed with nickel nitrate. Which metals,
b. Br2 ( /) + Kl( aqr) - if any, will react ? Write the chemical equation for
* any reaction.
c. Au(s) + HCI( aq) »
d. Cd(s) + HCI( ag)
e. Mg(s) + Co(N03) 2 ( ag)

CHEMICAL EQUATIONS AND REACTIONS 287

Chemistry in Action
Combustion Synthesis
What do aerospace materials, cutting through the sample, producing the type of self-propagation is called a
tools, catalytic materials, ceramic solid-state product. The mixture can reaction wave, in which the reaction
engine parts, ball bearings, high- reach temperatures up to 4000°C, propagates through the starting mate-
temperature superconductors, hydro- twice what is possible with conven- rial in a self-sustained manner.
gen storage, and fuel cells have in tional high-temperature furnaces. Therefore, compared with convention-
common ? They are made of ceramics, Combustion synthesis also allows al high-temperature methods, this
composites, and other advanced reactions to be completed in just sec- technique is an energy -saving process.
materials. onds. Hence, this technique produces In addition, the high temperatures and
Conventional techniques used to the desired material faster and short reaction times can produce
make these materials consist of a requires less supplied energy than materials that would not be synthe-
high - temperature furnace, with tem- conventional techniques do. In addi- sized under conventional conditions.
peratures ranging from 500°C to tion, the intense and quick heating Currently, scientists are studying reac -
2000°C, to supply the energy needed produces materials that are chemically tion waves, including how they move
for the reaction to take place. homogeneous. More than 500 com- through the initial mixtures. As scien-
Because these furnaces may reach pounds, such as lightweight and heat- tists better understand the characteris-
only 2000°C, it may take minutes to resistant aerospace materials, are tics of combustion synthesis, they can
hours to convert reactants to solid- created by combustion synthesis. refine the technique to be more useful
state products, and the mixtures are In a typical combustion synthesis in advanced materials production.
heated unevenly. As a result, flaws procedure, the reactant powders are
can be introduced into the struc- mixed and then pressed into a cylin- Questions
tures, which can cause stress points drical pellet. The pellet is ignited by an 1. Why is this technique called
in the materials. intense heat source, such as an electri- combustion synthesis ?
A different high-temperature tech- cally heated coil or a laser. Because
2. Why might this technique result
nique is combustion synthesis, which the combustion-synthesis reaction is
in a more chemically homoge-
generates its own energy to keep the very exothermic, the reaction is self -
neous material?
reaction continuing. Once the reactant propagating, and the process does not
mixture is ignited, a heat wave moves need any further input of energy. This

Once the reactant mixture is ignited, the combustion wave moves through
the sample, synthesizing the solid-state product.

CHAPTER 8
r i
i
 CHAPTER HIGHLIGHTS
Describing Chemical Reactions
I Vocabulary •Four observations that suggest a chemical reaction is taking
chemical equation place are the evolution of energy as heat and light, the produc -
precipitate tion of gas. a change in color, and the formation of a precipitate.
coefficient • balanced chemical equation represents, with symbols and
A
word equation formulas, the identities and relative amounts of reactants and
formula equation products in a chemical reaction.
reversible reaction

Types of Chemical Reactions

I Vocabulary •Synthesis reactions are represented bv the general equation
synthesis reaction A+X > AX.
decomposition reaction •Decomposition reactions are represented by the general equa -
electrolysis tion AX > A + X.
single- displacement reaction •Single-displacement reactions are represented by the general
double - displacement reaction equations A + BX > AX + B and Y + BX > BY + X.
combustion reaction •Double -displacement reactions are represented the general
by
equation AX + BY > AY + BX.
•In a combustion reaction, a substance combines with oxygen,
releasing energy in the form of heal and light.

Activity Series of the Elements

I Vocabulary • Activity series list the elements in order of their chemical reac-
activity series tivity and are useful in predicting whether a chemical reaction
will occur.
•Chemists determine activity series through experiments.

CHEMICAL EQUATIONS AND REACTIONS 289

 CHAPTER REVIEW
a . solid zinc sulfide + oxygen gas >
Describing Chemical solid zinc oxide 4- sulfur dioxide gas
Reactions b. aqueous hydrochloric acid 4 aqueous barium
hydroxide > aqueous barium chloride
SECTION 1 REVIEW 4 water
1. List four observations that indicate that a chem - c. aqueous nitric acid 4 aqueous calcium
ical reaction may be taking place. hydroxide > aqueous calcium nitrate
2. List the three requirements for a correctly writ - 4 water
ten chemical equation . 12. Translate each of the following chemical equa -
3. a . What is meant by the term coefficient in rela - tions into a sentence.
tion to a chemical equation ? a . 2ZnS(.v ) 4 302( g ) - » 2ZnO( .v ) 4 2SO 2(g )
b. How does the presence of a coefficient affect b. Cal \:( s ) 4 2 H 2Q( / ) >
the number of atoms of each type in the for - Ca ( OH ) 2 ( w7 ) 4 2 H 2(g )
mula that the coefficient precedes? c. AgN 03( w/ ) 4 KI ( tiq ) > Agl ( .v ) 4
4. Give an example of a word equation , a formula KN 03(w/ )
equation , and a chemical equation. 13. Balance each of the following:
5. What quantitative information is revealed bv a . H2 4 Cl 2 MCI
a chemical equation ? b. Al 4 Fe203 > AL03 4 Fe
6. What limitations are associated with the use c. Pb( CH 3COO )2 4 H:S > PbS 4
of both word and formula equations? CH3COOH
7. Define each of the following terms: 14. Identify and correct each error in the following
a. aqueous solution equations, and then balance each equation.
b. catalyst a . Li 4 CL > LiO ->
c. reversible reaction b. H: 4 Cl 2 * H 2Cl 2
8. Write formulas for each of the following c. MgC03 MgO: 4 CO:
compounds: d . Nal 4 CL -» NaCI 4 I
a. potassium hydroxide 15. Write chemical equations for each of the fol -
b. calcium nitrate lowing sentences:
e. sodium carbonate a . Aluminum reacts with oxygen to produce
d . carbon tetrachloride aluminum oxide.
e. magnesium bromide b. Phosphoric acid . H 3P04, is produced through
9. What four guidelines are useful in balancing an the reaction between tetraphosphorus decox-
equation ? ide and water.
10. How many atoms of each type are represented c. Iron ( III ) oxide reacts with carbon monoxide
in each of the following? to produce iron and carbon dioxide.
a . 3N 2 f . 5Fe ( NC> 3 ): 16. Carbon tetrachloride is used as an intermediate
.
b 21TO g. 4Mg3( P04 )2 chemical in the manufacture of other chemicals.
c. 4 HN03 h . 2 ( NH 4 ):S04 It is prepared in liquid form by reacting chlo -
d . 2Ca ( OH ): i. 6AL ( Se04 h rine gas with methane gas. Hydrogen chloride
e. 3Ba ( CI03)2 j. 4C3H 8 gas is also formed in this reaction . Write the
balanced chemical equation for the production
PRACTICE PROBLEMS of carbon tetrachloride. ( H i n t: See Sample
11. Write the chemical equation that relates to each Problems C and D. )
of the following word equations. Include sym -
bols for physical states in the equation .

290 CHAPTER 8
 CHAPTER REVIEW

.
17 For each of the following synthesis reactions, a. AgN03( w/ ) + NaCl( tf </ )
identify the missing reactant ( s ) or product ( s ). b. MgtNC Ma?) + KOH( A )
and then balance the resulting equation, ^ ^
c. LiOH( a q ) + Fe( N03)3( rt <7 )
.
a Mg + » MgO 26. Complete and balance the equations for the fol-
b. + > Fe203 lowing combustion reactions:
c. Li + Cl2 a. CH4 + 02
d. Ca + _ 1 > Cal? b. C3HA 4- 6,
,
c. C5H :+ 02
*>
Types of Chemical Reactions ( 27 Write and balance each of the following equa -
.
tions and then identify each by type.
a. hydrogen + iodine > hydrogen iodide
SECTION 2 REVIEW
b. lithium + hydrochloric acid >
18. Define and give general equations for the five
lithium chloride + hydrogen
basic types of chemical reactions introduced in c. sodium carbonate
Chapter 8. sodium oxide + carbon dioxide
19. How are most decomposition reactions initiated?
d. mercury (II) oxide » mercury + oxygen
20. A substance is decomposed by an electric cur -
e. magnesium hydroxide >
rent . What is the name of this type of reaction?
magnesium oxide + water
21. a. In what environment do many single -
28. Identify the compound that could undergo
displacement reactions commonly occur ?
decomposition to produce the following prod-
b. In general, how do single -displacement reac -
ucts, and then balance the final equation.
tions compare with synthesis and decomposi-
a. magnesium oxide and water
tion reactions in terms of the amount of
b. lead( II) oxide and water
energy involved? c. lithium chloride and oxygen
d. barium chloride and oxygen
PRACTICE PROBLEMS e. nickel chloride and oxygen
22. Complete each of the following synthesis reac - 29. In each of the following combustion reactions,
tions by writing both a word equation and a identify the missing reactant( s ). product ( s ). or
chemical equation. both, and then balance the resulting equation.
a. sodium + oxygen > a. C3HH + » + H:0
b. magnesium + fluorine > b. + 802 > 5CO:+ 6H20
23 . Complete and balance the equations for the fol- c. C2H5OH' + +
lowing decomposition reactions: 30. Complete and balance the equations for the fol-
a. HgO lowing reactions, and then identify each by type,
b. H20( / )
electricity a. zinc + sulfur
b. silver nitrate + potassium iodide ->
c. Ag20 — c. toluene, C7 HS + oxygen •
>
d. CuCI2 electricity
d. nonane. C9H20 + oxygen
* *
24. Complete and balance the equations for the fol-
lowing single-displacement reactions: Activity Series of the
a. Zn + Pb(N03)2 » Elements
b. Al + Hg(CH3COO)2
c. AI + NiS04 SECTION 3 REVIEW
d. Na + H20 - 31. a. What is meant by the activity of an element ?
25. Complete and balance the equations for the fol- b. How does this description differ for metals
lowing double -displacement reactions: and nonmetals?

CHEMICAL EQUATIONS AND REACTIONS 291

 CHAPTER REVIEW

32. a. What is an activity series of elements? 38. Complete the following synthesis reactions by
b. What is the basis for the ordering of the el- writing both the word and chemical equation
ements in the activity series ? for each:
33 . a. What chemical principle is the basis for the a. potassium + chlorine >
activity series of metals? b. hydrogen + iodine —
b. What is the significance of the distance c. magnesium + oxygen 4

between two metals in the activity series? 39. Use the activity series to predict which metal—
Sn. Mil, or Pt — would be the best choice as a
PRACTICE PROBLEMS container for an acid.
40. Aqueous sodium hydroxide is produced com-
34. Based on the activity series of metals and halo -
mercially by the electrolysis of aqueous sodium
.
gens which element within each pair is more
chloride. Hydrogen and chlorine gases are also
likely to replace the other in a compound?
a. k and Na e. Au and Ag
.
produced Write the balanced chemical equation
for the production of sodium hydroxide. Include
b. AI and Ni f. Cl and I
the physical states of the reactants and products.
c. Bi and Cr g. Fe and Sr
41. Balance each of the following:
d. Cl and F h. I and F
a. Ca( 0H ) 2 + (NH4 )2S04 4
35, Using the activity series in Table 3 on page 2N6.
J
predict whether each of the possible reactions
,
CaSC>4 + NH + H20
b. C\H6 + 0: > CO: + H20
listed below will occur. For the reactions that will
c. Cu2S + 02 > Cu20 + S02~
occur, write the products and balance the equation.
a. Ni( s ) + CuCU ( aq ) >
V
d. Al H 2SO4 12
> A (S04)3 + H2
42. Use the activity series to predict whether each
b. Zn( $) + Pb( NOv) 2(tfr/ )
of the following reactions will occur, and write
c. Cl2(g ) + Kl( <«7 ) >_
the balanced chemical equations for those pre -
d. Cu s) + FeSO4 <w/ —
( ( )
dicted to occur.
e. Ba( s ) + H20( / ) 4
a. Al(s ) + 02(g) — 4
36. Use the activity series to predict whether each
b. Pb(.v ) + ZnCI 2(.v ) 4
of the following synthesis reactions will occur,
43. Complete and balance the equations for the fol -
and write the chemical equations for those pre -
lowing reactions, and identify the type of reac -
dicted to occur.
tion that each equation represents.
a. Ca(.v ) + CMg ) 4
a. (NH4)2S( A</ ) + ZnCUiuq ) 4
b. Ni(5) + 02(g) 4
+ ZnS(.v )
c. Au(.v ) + 02(g)
b. AI( j) + Pb(NO3 )2( aq ) 4

c. Ba (.v ) + H:0( / ) — 4
d. Cl2(g) + KBr ( aq )
MIXED REVIEW c. NH3(g) + 02( g ) -5-» NO( g) + H:0( / )
f. HiO( / )
37 . Ammonia reacts with oxygen to yield nitrogen * H:(g ) + 0:(g)
44. Write and balance each of the following equa-
and water.
4NH3(g) + 302(g ) 4 2N2 ( g ) + 6H20( / ) tions, and then identify each by type.
Given this chemical equation, as well as the a. copper + chlorine 4 copper ( ll ) chloride

number of moles of the reactant or product b. calcium chlorate -

indicated below, determine the number of moles calcium chloride + oxygen
of all remaining reactants and products . c. lithium 4- water
.
a 3.0 mol Ck c. l.() molN2 lithium hydroxide + hydrogen
b. 8.0 mol NH , .
d. 0.40 mol H O d. Iead( II) carbonate
lead( II ) oxide + carbon dioxide

292 CHAPTER S
 CHAPTER REVIEW

45 . How many moles of HC1 can be made from c. Classify the reactions you wrote in ( a ) and ( h ).
6.15 mol Hi and an excess of CIV? d . Write word equations for the reactions you
46 . What product is missing in the following wrote in ( a ) and ( b ).
equation ? 51 . Find the common-reactions section for Group
MgO 4- 2 HCI > MgCI: + 13 in the Elements Handbook . Use this infor-
47 . Balance the following equations: mation to answer the following:
a . Pb ( NO 0:( ^/ ) + NaOH ( a q ) » a. Write a balanced chemical equation for the
Pb 0H )2(s ) + NaN 03( w/ )
( formation of gallium bromide prepared from
<
b. C12 H 22Q 11 ( / ) 4 02 g ) > C02( g) 4 H 20( / ) hydrobromic acid .
.
c Al OH 3(s ) H 2SO
( ) 4 4 b. Write a balanced chemical equation for the
AI:( S04 )3( «<7 ) + H:0( / ) formation of gallium oxide.
c. Classify the reactions you wrote in ( a ) and ( b ).
d . Write word equations for the reactions you
wrote in ( a ) and ( b ).
CRITICAL THINKING
48. Inferring Relationships Activity series are pre-
pared by comparing single-displacement reactions RESEARCH & WRITING
between metals. Based on observations, the
52 . Trace the evolution of municipal water fluorida -
metals can be ranked bv their ability to react .
tion . What advantages and disadvantages are
However, reactivity can be explained by the ease
associated with this practice ?
with which atoms of metals lose electrons. Using
53. Research how a soda -acid fire extinguisher
information from the activity series identify the
,
works, and write the chemical equation for the
locations in the periodic table of the most reactive
reaction . Check your house and other structures
metals and the least reactive metals. Using your
for different types of fire extinguishers, and ask
knowledge of electron configurations and period -
your local fire department to verify the effec-
ic trends infer possible explanations for the met -
,
tiveness of each type of extinguisher.
als reactivity and position in the periodic table.
'

49. Analyzing Results Formulate an activity series

for the hypothetical elements A . J . Q. and Z by ALTERNATIVE ASSESSMENT
using the following reaction information:
A 4 ZX
.I 4 ZX-
—no reaction
> AX 4 Z
4
54. Performance Assessment For one day. record
situations that show evidence of a chemical
change. Identify the reactants and the products,
0 4 AX —> OX 4 A and determine whether there is proof of a
chemical reaction. Classify each of the chemical
reactions according to the common reaction
USING THE HANDBOOK types discussed in the chapter.
-
50. Find the common reactions section for Group I
metals in the Elements Handbook . Use this
information to answer the following:
a . Write a balanced chemical equation for the
formation of rubidium hvdroxide from
0

rubidum oxide.
b. Write a balanced chemical equation for the
formation of cesium iodide.

CHEMICAL EQUATIONS AND REACTIONS 293

 Math Tutor BALANCING CHEMICAL EQUATIONS

A chemical equation is a written expression of an actual chemical reaction in which cer -

tain atoms, ions, or molecules become rearranged in a specific way. Therefore, the equa-
tion must represent exactly what happens in the reaction. Recall that atoms are never
created or destroyed in chemical reactions. A balanced chemical equation shows that all
of the atoms present in reactants are still present in products.

Problem-Solving TIPS
• First , identify reactants and products. ( You may find it helpful to write a word
equation first.)
• Using correct formulas and symbols, write an unbalanced equation for the reaction.
• Balance atoms one element at a time by inserting coefficients.
• Identify elements that appear in only one reactant and one product, and balance
the atoms of those elements first .
• If a polyatomic ion appears on both sides of the equation, treat it as a single unit.
• Double-check to be sure that the number of atoms of each element is the same on
both sides of the equation.

SAMPLE
When an aqueous solution of ammonium sulfate, (NH4 )2S04(my ), is combined with an aque-
ous solution of silver nitrate, AgNOjUi / ), a precipitate of solid silver sulfate, Ag2S04(s), forms,
*
leaving ammonium nitrate. !MI4N( ) a q ) < in solution. Balance the equation for this reaction.
^
As before, first write an equation with correct formulas for all reactants and products.
( NH4 ) 2S04(m/ ) + AgN03(tf <7 ) NH4N03( tf <7 ) 4 Ag2SQ 4( .v )
If you compare the number of silver atoms on each side, you can see that the equation is
not balanced. This equation may look very complex, but it is really fairly simple. In many
reactions involving polyatomic ions such as sulfate, nitrate, and ammonium, the ions do not
.
change In the equation above, you can see that NO3 is present on both sides, as are S( )4 and
NH4. YOU can balance the equation by treating the groups as if they were single atoms. To
balance the NH4 groups, place a 2 in front of NH 4NOv This gives you two ammonium
groups on the left and two on the right. Now, because you have two nitrate groups on the
right , place a 2 in front of AgN03 to give two nitrate groups on the left. Finally, check silver
atoms and sulfate groups, and you find that they balance.
( NH4 )2SQ4( / ) + 2 AgN03( <w/ ) —-> 2NH4N03( </r/ ) + Ag2S04(s)
^
PRACTICE PROBLEMS
1. When propane burns completely in air. the 2. Balance the following chemical equations:
reaction forms carbon dioxide and water vapor. a. Kl ( aq ) 4 Cl2(g) — » KC\ ( aq ) 4 \ 2( s )
•

Balance the equation for this reaction.

,
C H8 + O , > CO, 4- H - O . b. Al( s) + H2SOJaq ) »
AI:( SO4 )$ ( aq ) 4 H2(g)

294 CHAPTER 8
Answer the following items on a separate piece of paper. 7, Which of the following statements is true about
MULTIPLE CHOICE
the reaction 2F-* + 2H - Q. 4HF + 02?
*
A . Two grams of 0: are produced when 2 g F2
.
1 According to the law of conservation of mass, reacts with 2 g H:0.
the total mass of the reacting substances is
B. Two moles of HF are produced when 1 mol
A . always more than the total mass of the
FT reacts with 1 mol H*>0.
products. C. For every 2 mol 02 produced. 6 mol HF are
B. always less than the total mass of the products.
produced.
C. sometimes more and sometimes less than the
total mass of the products.
.
D. For every 1 mol H20 that reacts 2 mol ()2
are produced.
D. always equal to the total mass of the products.
SHORT ANSWER
2. To balance a chemical equation, you may adjust
the 8. Determine the products and write a balanced
.
A coefficients. equation for the reaction of solid magnesium
and water.
B. subscripts.
C. formulas of the products. 9. A precipitation of iron(lll) hydroxide is produced
D. either the coefficients or the subscripts. by reacting an aqueous solution of iron!Ill ) chlo-
ride with an aqueous solution of sodium hydrox -
3. Which is the correct chemical equation for the
ide. Write a balanced chemical equation.
following formula equation: ( NH4 ) TS »
NH3 + H2 S? EXTENDED RESPONSE
A . 2(NH4 ) 2 S —> 2NH3 + H:S2 10. List the hypothetical metals A. E. M. and R in
B. 2( NH4 ) 2 S -> 2NH3 + H 2 S increasing order of reactivity by using the reac -
C. ( NH4 ) 2S - 2NH3 + H2S tion data in the table below. The reaction of
*
D. None of the above interest is of the form C + ZX CX + Z.
Explain your reasoning.
*
4. Select the missing reactant ( s ) for the double -
displacement reaction that produces PFS and
AX EX MX RX
AsClv
A . PCI5 and AsF3 no no
A reaction reaction reaction
B. PCI3 and AsFs
C. PCI; and AsF3 F; reaction reaction reaction
D. None of the above no no no
M reaction reaction reaction
5. Select the missing reactant for the following
combustion reaction: 2 -f 15 QT no
> R reaction reaction
14CO:+ 6H20. reaction
.
A C J 4H|2
.
11 Calcium hypochlorite. Ca( OCl )2. is a bleaching
B. C14H12O4
.
c C7H6 agent produced from sodium hydroxide, calcium
hydroxide, and chlorine. Sodium chloride and
D. C7H602
water are also produced in the reaction. Write
.
6 A mixture consists of Ag. Pb. and Fe metals. the balanced chemical equation. If 2 mol NaOH
Which of these metals will react with ZnCl2? calcium hypochlorite
react , how many moles of
A . Ag( s ) can be produced?
B. Pb( s )
C. Fe ( s )
Focus on one question at a time
D. None of these metals
unless you are asked to refer to previous answers.

CHEMICAL EQUATIONS AND REACTIONS 295

 EXPERIMENT 8

Blueprint Paper
OBJECTIVES BACKGROUND
• Prepare blueprint paper and create a Blueprint paper is prepared by coating paper with
blueprint. —
a solution of two soluble iron ( III ) salts potassium
hexacyanoferrate( III ), commonly called potassium
MATERIALS ferricyanide, and iron ( lll ) ammonium citrate. These
two salts do not react with each other in the dark .
• 10% iron ( IH ) ammonium citrate solution
However, when exposed to UV light , the iron ( III )
• 10 % potassium hexacvanof errate ( III )
’
ammonium citrate is converted to an iron ( II ) salt .
solution Potassium hexacyanoferrate( III ), KjFe ( CN )6, reacts
• 25 mL graduated cylinders, 2 with iron ( II ) ion. Fe:\ to produce an insoluble blue
compound , KFeFe ( CN )6 * H:0. In this compound , iron
• corrugated cardboard , appears to exist in both the +2 and +3 oxidation states.
20 cm x 30 cm , 2 pieces
A blueprint is made by using black ink to make a
• glass stirring rod sketch on a piece of tracing paper or clear, colorless
• Petri dish plastic. This sketch is placed on top of a piece of
blueprint paper and exposed to ultraviolet light .
• thumbtacks, 4 Wherever the light strikes the paper, the paper turns
• tongs blue. The paper is then washed to remove the solu -
white paper, 8 cm x 15 cm, 1 piece ble unexposed chemical and is allowed to dry. The
•
—
result is a blueprint a blue sheet of paper with
white lines.

SAFETY

«V <
-
$
^
For review of safety, please see Safety in the
Chemistry Laboratory in the front of your book .

PROCEDURE
1 . Pour 15 mL of a 10% solution of potassium
hexacyanoferrate( III ) solution into a Petri dish .
With most of the classroom lights off or dimmed ,
add 15 mL of 10% iron ( III ) ammonium citrate
solution . Stir the mixture.
2. Write your name on an 8 cm x 15 cm piece of
white paper. Carefully coat one side of the piece
of paper by using tongs to drag it over the top of
the solution in the Petri dish .

296 CHAPTER 8
-.y
y -
EXPERIMENTS

3. With the coated side up. tack your wet paper to CLEANUP AND DISPOSAL
a piece of corrugated cardboard , and cover the 6. Clean all equipment and your lab
paper with another piece of cardboard. Wash station . Return equipment to its proper
your hands before proceeding to step 4 . place. Dispose of chemicals and solu -
4. Take your paper and cardboard assembly out - tions in the containers designated by your
side into the direct sunlight . Remove the top teacher. Do not pour any chemicals down the
piece of cardboard so that the paper is exposed . drain or in the trash unless your teacher directs
Quickly place an object such as a fern , a leaf, or you to do so. Wash your hands thoroughly before
a key on the paper. If it is windy, you may need you leave the lab and after all work is finished .
to put small weights, such as coins, on the object
to keep it in place, as shown in Figure A . ANALYSIS AND INTERPRETATION
5. After about 20 min , remove the object and again 1. Relating Ideas: Why is the iron ( III ) ammonium
cover the paper with the cardboard . Return to citrate solution stored in a brown bottle?
the lab. remove the tacks, and thoroughly rinse
2. Organizing Ideas: When iron ( lll ) ammonium
the blueprint paper under cold running water.
citrate is exposed to light , the oxidation state
Allow the paper to dry. In your notebook ,
of the iron changes. What is the new oxidation
record the amount of time that the paper was
state of the iron ?
exposed to sunlight .
3. Analyzing Methods: What substances were
washed away when you rinsed the blueprint in
water after it had been exposed to sunlight ?
( Hint: Compare the solubilities of the two
ammonium salts that you used to coat the paper
and of the blue product that formed .)

CONCLUSIONS
1. Applying Ideas: Insufficient washing of the
exposed blueprints results in a slow deterioration
of images. Suggest a reason for this deterioration .
2. Relating Ideas: Photographic paper can be safely
exposed to red light in a darkroom . Do you
think the same would be true of blueprint paper?
Explain your answer.

EXTENSIONS
1. Applying Ideas: How could you use this blue -
print paper to test the effectiveness of a brand
of sunscreen lotion ?
2. Designing Experiments: Can you think of
ways to improve this procedure ? If so. ask your
teacher to approve your plan , and create a new
FIGURE A To produce a sharp image, the object must be flat, blueprint. Evaluate both the efficiency of the
with its edges on the blueprint paper, and it must not move. procedure and the quality of blueprint .

CHEMICAL EQUATIONS AND REACTIONS 297

 m
CHAPTER 9

Stoichiometry comes from the Greek words stoicheion ,

meaning “element, ” and metron , meaning “measure.
Introduction to SECTION 1

Stoichiometry OBJECTIVES
sj Define stoichiometry.

Describe the importance of

* the mole ratio in stoichio-
M uch of our knowledge of chemistry is based on the careful quantita - metric calculations.
tive analysis of substances involved in chemical reactions. Composition
stoichiometry ( which you studied in Chapter 3) deals with the mass rela -
tionships of elements in compounds . Reaction stoichiometry involves the Write a mole ratio relating
* two substances in a chemical
mass relationships between reactants and products in a chemical reaction.
Reaction stoichiometry is the subject of this chapter and it is based on
equation.
chemical equations and the law of conservation of mass. All reaction
stoichiometry calculations start with a balanced chemical equation . This
equation gives the relative numbers of moles of reactants and products.

Reaction Stoichiometry Problems

The reaction stoichiometry problems in this chapter can be classified
according to the information given in the problem and the information
you are expected to find , the unknown . The given and the unknown may
CHEMISTRY
^
'Sro*'
Module S : Equations and
Stoichiometry

both be reactants, they may both be products, or one may be a reactant

and the other a product . TTie masses are generally expressed in grams,
but you will encounter both large-scale and microscale problems with
other mass units, such as kg or mg. Stoichiometric problems are solved
by using ratios from the balanced equation to convert the given quanti -
ty using the methods described here.

Problem Type 1 : Given and unknown quantities are amounts in moles.

When you are given the amount of a substance in moles and asked to
calculate the amount in moles of another substance in the chemical
reaction , the general plan is
amount of amount of
->
given substance ( mol ) unknown substance ( mol )

Problem Type 2: Given is an amount in moles and unknown is a mass

that is often expressed in grams.
When you are given the amount in moles of one substance and asked to
calculate the mass of another substance in the chemical reaction , the
general plan is
amount of amount of mass of
given substance * unknown substance » unknown substance
( mol ) ( mol ) (g)
STOICHIOMETRY 299
 Problem Type 3: Given is a mass in grains and unknown is an amount
in moles .
When you are given the mass of one substance and asked to calculate
the amount in moles of another substance in the chemical reaction, the
general plan is

mass of amount ol amount of

given substance given substance unknow n substance
*
< g) ( mo! ) ( mol )

Problem Type 4: Given is a mass in grams and unknown is a mass in

grams.
When you are given the mass of one substance and asked to calculate the
mass of another substance in the chemical reaction, the general plan is

mass of amount of amount of mass of

given substance » given substance -> unknown substance » unknow n substance
( g) ( mol ) ( mol ) ( g)

Mole Ratio
Solving any reaction stoichiometry problem requires the use ot a mole
CAREERS in Chemistry ratio to convert from moles or grams of one substance in a reaction to
moles or grams of another substance. A mole ratio is a conversion
Chemical Technician
factor that relates the amounts in moles of any two substances involved
Chemical technicians are highly skilled in a chemical reaction. This information is obtained directly from the
scientific professionals who bring valu- balanced chemical equation. Consider, for example, the chemical
able skills to the development of new
products, the processing of materials, equation for the electrolysis of melted aluminum oxide to produce
the management of hazardous waste, aluminum and oxygen.
regulatory compliance, and many other
aspects of getting products and ser - 2 AUOi( / ) > 4Al( .v ) + 302( g )
vices to the consumer. Chemical techni -
cians must have a solid background in
applied chemistry and mathematics and
Recall from Chapter S that the coefficients in a chemical equation satis -
be highly skilled in laboratory methods. | fy the law of conservation of matter and represent the relative amounts
Earning an associate's degree in in moles of reactants and products. Therefore, 2 mol of aluminum oxide
applied science or chemical technology decompose to produce 4 mol of aluminum and 3 mol of oxygen gas.
is one good way to prepare for this These relationships can be expressed in the following mole ratios.
career. Many chemical technicians have
a bachelor 's degree in chemical tech- 2 mol AI:03 4 mol A 1
nology, chemistry, or other sciences. or
4 mol AI 2 mol A 1:03
2 mol A12Q3 3 mol OT
or
3 mol CT 2 mol Al:03
4 mol AI 3 mol G >
or
3 mol CT 4 mol Al

For the decomposition of aluminum oxide, the appropriate mole ratio

would be used as a conversion factor to convert a given amount in moles
of one substance to the corresponding amount in moles of another

300 CHAPTER 9
substance. To determine the amount in moles of aluminum that can be
produced from 13.0 mol of aluminum oxide, the mole ratio needed is
that of Al to Al203.
4 mol AI
13.0 mol ATQyx = 26.0 mol Al
2 mol AI2O3
Mole ratios are exact , so they do not limit the number of significant fig-
ures in a calculation. The number of significant figures in the answer is
— 1 11

Chemistry in Action
therefore determined only by the number of significant figures of any Go to go.hrw.com for a full -length
measured quantities in a particular problem.
UA
.
article on stoichiometry and air bags
Keyword: HC 6 STCX

Molar Mass
Recall from Chapter 7 that the molar mass is the mass, in grams, of one
mole of a substance. The molar mass is the conversion factor that relates
the mass of a substance to the amount in moles of that substance. To
solve reaction stoichiometry problems, you will need to determine molar
masses using the periodic table.
Returning to the previous example, the decomposition of aluminum
oxide, the rounded masses from the periodic table are the following .
1 mol A1203 = 101.96 g 1 mol Al = 26.98 g 1 mol O; = 32.00 g

These molar masses can be expressed by the following conversion factors.

101.96 g AbO 1 mol A 1203

—-—- ^ or
1 mol A 1:03 101.96 gAl203
26.98 g Al 1 mol AI
or
1 mol Al 26.98 g AI
32.00 g 02 1 mol 0 ->
or
1 mol 02 32.00 g Q 2

To find the number of grams of aluminum equivalent to 26.0 mol of alu -

minum, the calculation would be as follows.
26.98 g Al
26.0 mol Af x = 701 g Al
1 mol Al

SECTION REVIEW 3. How is a mole ratio used in stoichiometry ?

1. What is stoichiometry ? Critical Thinking
2. For each equation, write all possible mole ratios. 4. RELATING IDEAS What step must be performed
a. 2 Hg0( s) 2 Hg( / ) + 02 ( g ) before any stoichiometry problem is solved ?
* Explain.
b. 4NH3(g) + 6N0(g) > 5N2 (g) + 6H20( / )

STOICHIOMETRY 301
 ISTORICAL CHEMISTRY

The Case of Combustion

People throughout history have transformed sub -
stances by burning them in air . Yet at the dawn of the
scientific revolution, very little was known about the
process of combustion . In attempting to explain this
common phenomenon, chemists of the 18th century
developed one of the first universally accepted theo -
ries in their field. But as one man would show, scien-
tific theories do not always stand the test of time.
Changing Attitudes
Shunning the ancient Greek approach of logical argument
based on untested premises, investigators of the 17th cen-
tury began to understand the laws of nature by observing,
measuring, and performing experiments on the world
around them. However, this scientific method was incorpo-
rated into chemistry slowly. Although early chemists exper -
imented extensively, most considered measurement to be
unimportant. This viewpoint hindered the progress of
chemistry for nearly a century.
A Flawed Theory
By 1700, combustion was assumed to be the decomposi-
tion of a material into simpler substances. People saw
burning substances emitting smoke and energy as heat
and light. To account for this emission, scientists proposed A Antoine Laurent Lavoisier helped establish
a theory that combustion depended on the emission of a chemistry as a science.
& substance called phlogiston, which appeared as a combi -
nation of energy as heat and light while the material was
results based on the phlogiston theory. Like a burning can -
burning but which could not be detected beforehand.
dle, the mouse emitted phlogiston; when the air could
The phlogiston theory was used to explain many chemi -
hold no more phlogiston, the mouse died. Thus, Rutherford
cal observations of the day. For example, a lit candle under
a glass jar burned until the surrounding air became satu-
figured that the air in the container had become " phlogis-
ticated air."
rated with phlogiston, at which time the flame died
A couple of years later, Joseph Priestley obtained a red-
because the air inside could not absorb more phlogiston.
dish powder when he heated mercury in the air. He
A New Phase of Study assumed that the powder was mercury devoid of phlogis-
By the 1770 s, the phlogiston theory had gained universal ton. But when he heated the powder, an unexpected
acceptance. At that time, chemists also began to experiment result occurred: Metallic mercury, along with a gas that
with air, which was generally believed to be an element. allowed a candle to burn, formed. Following the phlogis-
In 1772, when Daniel Rutherford found that a mouse ton theory, he believed this gas that supports combustion
kept in a closed container soon died, he explained the to be " dephlogisticated air."
23!KffS9E3Bi9

Nice Try, B u t . . . After obtaining similar results by using various sub -

Antoine Laurent Lavoisier was a meticulous scientist He . stances, Lavoisier concluded that air was not an element
realized that Rutherford and Priestley had carefully but a mixture composed principally of two gases,
observed and described their experiments but had not Priestley 's " dephlogisticated air ” (which Lavoisier
measured the mass of anything. Unlike his colleagues, renamed oxygen ) and Rutherford's " phlogisticated air ”
Lavoisier knew the importance of using a balance. He ( which was mostly nitrogen but had traces of other non-
measured the masses of reactants and products and com- flammable atmospheric gases). When a substance burned,
pared them. He observed that the total mass of the reac- it chemically combined with oxygen, resulting in a prod-
tants equaled the total mass of the products. Based on uct Lavoisier named an oxide. Lavoisier 's theory of com-
these observations, which supported what would become bustion persists today. He used the name oxygen because
known as the law of conservation of mass, Lavoisier he thought that all acids contained oxygen. Oxygen
endeavored to explain the results of Rutherford and means '' acid former.”
Priestley.
The Father of Chemistry
Lavoisier put some tin in a closed vessel and weighed
By emphasizing the importance of quantitative analysis,
the entire system. He then burned the tin. When he
Lavoisier helped establish chemistry as a science. His
opened the vessel, air rushed into it as if something had
work on combustion laid to rest the phlogiston theory
been removed from the air in the vessel during combus-
and the theory that air is an element. He also explained
tion. He then measured the mass of the burned metal and
why hydrogen burned in oxygen to form water, or hydro -
observed that this mass was greater than the mass of the
gen oxide. He later published one of the first chemistry
original tin. Curiously, this increase in mass equaled the
textbooks, which established a common naming system
mass of the air that had rushed into the vessel. To
of compounds and elements and helped unify chemistry
Lavoisier, this change in mass did not support the idea of
worldwide. These accomplishments earned Lavoisier the
phlogiston escaping the burning material. Instead, it indi -
reputation of being the father of chemistry.
cated that during combustion, part of the air reacted with
the tin.
Questions
1. Why does the mass of tin increase when tin is heated
in air ?
2. What was the composition of Priestley's " dephlogisti -
TABLE OF SIMPLE SUBSTANCES. cated air " and Rutherford's " phlogisticated air " ?
Simple fubftances belonging to all the kingdoms of
nature , which may be confidered as the elements of
bodies .
New Names . Correfpondent old Names .
Light Light .
Heat .
Principle or element of heat . SC
Caloric • • Fire. Igneous fluid .
Matter of fire and of heat .
/ lNKS. PfT«tapt < Md MMMUMMd tv tfcf
Dephlogifticutcd air. NJUMUI Satin iMctm AiiMiillti

Oxygen

Azote
$ Empyreal air.
Vital air, or
Ba/e of vital air .
$ Phlogifticated air or gas .
For a variety of links related to this
chapter, go to wvAv.scilmks.org
Topic: Lavoisier ^
( Mephitis , or its bafe .
Hydrogen S Inflammable air or gas , Sci Links code: HC60855
( or the bafe of inflammable air .
Lavoisier's concept of simple substances was published in his book
Elements of Chemistry in 1789.
 SECTION 2
Ideal Stoichiometric
OBJECTIVES
Calculate the amount in moles
Calculations
of a reactant or product from
the amount in moles of a dif -
ferent reactant or product.
T he chemical equation plays a very important part in all stoichio-
J Calculate the mass of a reac - metric calculations because the mole ratio is obtained directly from it .
tant or product from the Solving any reaction stoichiometry problem must begin with a balanced
amount in moles of a differ - equation.
ent reactant or product. Chemical equations help us make predictions about chemical reac-
tions without having to run the reactions in the laboratory. The
J Calculate the amount in reaction stoichiometry calculations described in this chapter are theo-
moles of a reactant or product retical . They tell us the amounts of reactants and products for a given
from the mass of a different chemical reaction under ideal conditions. in which all reactants are
reactant or product. completely converted into products. However many reactions do not
,

proceed such that all reactants are completely converted into products.
Theoretical stoichiometric calculations allow us to determine the maxi -
^ Calculate the mass of a reac - mum amount of product that could be obtained in a reaction but do not
tant or product from the mass
require that the reaction be carried out .
of a different reactant or
product. Solving stoichiometric problems requires practice. These problems
are extensions of the composition stoichiometry problems that you
solved in Chapters 3 and 7 . Practice by working the sample problems in
the rest of this chapter. Using a logical, systematic approach will help
you successfully solve these problems.

Conversions of Quantities in Moles

In these stoichiometric problems, you are asked to calculate the amount
in moles of one substance that will react with or be produced from the
given amount in moles of another substance. The plan for a simple mole
conversion problem is

amount of amountof
given substance ( mol ) unknown substance ( mol)

This plan requires one conversion factor — the stoichiometric mole ratio
of the unknown substance to the given substance from the balanced
equation. To solve this type of problem, simply multiply the known
quantity by the appropriate conversion factor.

given quantity x conversion factor = unknown quantity

304 CHAPTER 9
 Mole ratio
( Balanced equation)
Amount of Amount of
given x mol unknown unknown
substance mol given substance
(mol) (mol)
CONVERSION FACTOR
GIVEN IN CALCULATED
THE PROBLEM

FIGURE 1 This is a solution plan for problems in which the given and
unknown quantities are expressed in moles.

SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.

In a spacecraft, the carbon dioxide exhaled by astronauts can be removed by its reaction with lithium
hydroxide, LiOH, according to the following chemical equation .
C( ) 2(£ ) + 2LiOH( s) Li2C03(s) + H20( / )

Mow many moles of lithium hydroxide are required to react with 20 mol C02, the average amount
exhaled by a person each day ?

SOLUTION
1 ANALYZE Given: amount of C02 = 20 mol
Unknown: amount of LiOH ( mol )

2 PLAN amount of CO: ( mol ) » amount of LiOH ( mol )

This problem requires one conversion factor— the mole ratio of LiOH to CO% The mole
ratio is obtained from the balanced chemical equation. Because you are given moles of
C02, select a mole ratio that will cancel mol C02 and give you mol LiOH in your final
answer. The correct ratio has the following units.
mol LiOH
mol CO - .
This ratio cancels mol CO: and gives the units mol LiOH in the answer.
mol ratio
mol LiOH
mol CO-> x = mol LiOH
mol CO *>
3 COMPUTE Substitute the values in the equation in step 2. and compute the answer.
2 mol LiOH
20 mol COi x = 40 mol LiOH
l moLCO ^
4 EVALUATE The answer is written correctly with one significant figure to match the number of signifi -
cant figures in the given 20 mol CO:, and the units cancel to leave mol LiOH. which is the
unknown. The equation shows that twice the amount in moles of LiOH reacts with C02.
Therefore, the answer should be 2 x 20 = 40.

STOICHIOMETRY 305
 PRACTICE Answers in Appendix E

1 . Ammonia. NHV is widely used as a fertilizer and in many house -

hold cleaners. How many moles of ammonia are produced when
6 mol of hydrogen gas react with an excess of nitrogen gas? fyrtdiTrfld il
Go to go.hrw.com for
2. The decomposition of potassium chlorate, KCIO3, is used as a more practice problems
source of oxygen in the laboratory. How many moles of potassium that ask you to calculate
chlorate are needed to produce 15 mol of oxygen gas? unknown quantities by
using mole ratios.
Keyword: HC 6 STCX
4
Conversions of Amounts
in Moles to Mass
In these stoichiometric calculations, you are asked to calculate the mass
( usually in grams ) of a substance that will react with or be produced
from a given amount in moles of a second substance. The plan for these
mole- to - gram conversions is
amount of amount of mass of
given substance » unknown substance unknown substance
( mol) ( mol ) ( g)

This plan requires two conversion factors— the mole ratio of the
unknown substance to the given substance and the molar mass of the
FIGURE 2 This is a solution plan unknown substance for the mass conversion. To solve this kind of prob-
for problems in which the given lem. you simply multiply the known quantity, which is the amount in
quantity is expressed in moles and moles, by the appropriate conversion factors.
the unknown quantity is expressed
in grams.
Mole ratio Molar mass factor
(Balanced equation) ( Periodic table)
Amount of Mass of
given mol unknown Molar mass of unknown (in g) unknown
x x
substance mol given 1 mol unknown substance
( mol) ( g)
CONVERSION FACTORS
GIVEN IN CALCULATED
THE PROBLEM

SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter .

,
In photosynthesis, plants use energy from the sun to produce glucose, C6H 206, and oxygen from the
reaction of carbon dioxide and water. What mass, in grams, of glucose is produced when 3.00 mol of water
react with carbon dioxide ?

SOLUTION
1 ANALYZE Given: amount of H:0 = 3.00 mol
Unknown: mass of Cf Hi:Oh produced ( g)
1

306 CHAPTER 9
2 PLAN You must start with a balanced equation.

ACOi( g ) + 6H:0( / ) ,
* C H :06(.S) + 602(g)
Given the amount in mol of H2G. you need to get the mass of ChH 120 in grams Two
*
.
conversion factors are needed— the mole ratio of ChH|206 to H:0 and the molar mass
„
ofC H1206.
mol ratio
,
molar mass factor

mol HiO x
mol
mol H-,0
x
gChH :06
mol ChH|:0„ - gQ,Hl 20(l

3 COMPUTE Use the periodic table to compute the molar mass of CftH1206.
= 180.18 g/ mol
-
3.00 mol TUO x
1 mol
^++nO
6 mol fr©
1 X0.18 gC0H 12Q6
1 mo
= W.lgChHi:Oh

4 EVALUATE The answer is correctly rounded to three significant figures, to match those in 3.00 mol
. ,
H O. The units cancel in the problem, leaving g C6H :Oh as the units for the answer, which
matches the unknown. The answer is reasonable because it is one - half of ISO.

SAMPLE PROBLEM C For more help, go to the Math Tutor at the end of this chapter.
What mass of carbon dioxide, in grams, is needed to react with 3.00 mol H20 in the photosynthetic reac-
tion described in Sample Problem B?

SOLUTION
1 ANALYZE Given: amount of H 20 = 3.00 mol
Unknown: mass of CO, ( g )

Ilie chemical equation from Sample Problem B is

2 bO:( g).
^ li:Of,U +
PLAN bCCMtf ) + bH20( / ) >C )

Two conversion factors are needed—the mole ratio of CO: to H:0 and the molar mass
factor of CO:.
mol ratio molar mass factor
mol CO, gCP 2
3 COMPUTE mol I f x
mol H- Q . mol CO -»
= g co2

Use the periodic table to compute the molar mass of C02.

,
CO = 44.01 g/ mol
4 EVALUATE 6 mol-COs 44.01 g CCT
3.00 moW4s0 x x = 132 s CO,
bmoTHsO 1 moK'02
Tlie answer is rounded correctly to three significant figures to match those in 3.00 mol H:0.
Ilie units cancel to leave g C02. which is the unknown. The answer is close to an estimate
of 120, which is 3 x 40.

STOICHIOMETRY 307
 PRACTICE Answers in Appendix E

1. When magnesium burns in air. it combines with oxygen to

form magnesium oxide according to the following equation.
2Mg(5) + 02(g) > 2MgO(.s )
What mass in grams of magnesium oxide is produced from
2.00 mol of magnesium?
2. What mass of glucose can be produced from a photosynthesis . .
Go to go hrw com for
reaction that occurs using 10 mol CO - ? . more practice problems
that ask you to calculate
6C02(g) + 6H20( / ) 4 C6H ,206 ( W/ ) + 602(g) unknown quantities by
using mole ratios.
Keyword: HC 6 STCX

Conversions of Mass
to Amounts in Moles
In these stoichiometric calculations, you are asked to calculate the
amount in moles of one substance that will react with or be produced
.
from a given mass of another substance. In this type of problem you are
starling with a mass ( probably in grams ) of some substance. The plan for
this conversion is

mass of amount of amount of

given substance unknown substance
( g)
* given( substance
mol ) ( mol )

This route requires two additional pieces of data: the molar mass of the
given substance and the mole ratio. The molar mass is determined by
using masses from the periodic table. We will follow a procedure much
like the one used previously by using the units of the molar mass con-
version factor to guide our mathematical operations. Because the known
quantity is a mass, the conversion factor will need to be 1 mol divided by
molar mass. This conversion factor cancels units of grams and leaves
units of moles.

Molar mass factor Mole ratio

( Periodic table) ( Balanced equation)
Mass of Amount of
1 mol given mol unknown
given X unknown
substance * Molar mass of
given (g)
mol given
substance
(g) ( mol)
CONVERSION FACTORS
GIVEN IN CALCULATED
THE PROBLEM

FIGURE 3 This is a solution plan for problems in which the given quantity
isexpressed in grams and the unknown quantity is expressed in moles.

308 CHAPTER 9
 SAMPLE PROBLEM more help, go to theMilth Tutor at the end of this chapter.

The firs! step in the industrial manufacture of nitric acid is the catalytic oxidation of ammonia.
NH 3(g ) + O2 ( g ) NO(g ) + H 20 (g ) ( unbalanced )
The reaction is run using 824 g NH 3 and excess oxygen.
a . How many moles of NO are formed?
b. How many moles of H 20 are formed?

SOLUTION
1 ANALYZE -
Given: mass of NH = 824 g
Unknown: a . amount of NO produced ( mol )
b. amount of H 20 produced ( mol )

2 PLAN First , write the balanced chemical equation .

,
4 NH ( g ) + 502( g ) > 4NO(g ) + 6 H:0( g )

—
Two conversion factors are needed to solve part ( a ) the molar mass factor for NH 3 and
the mole ratio of NO to NHV Part ( b ) starts with the same conversion factor as part ( a ) , but
then the mole ratio of H:0 to NH 3 is used to convert to the amount in moles of H 2O. The
first conversion factor in each part is the molar mass factor of NH 3.
molar mass factor mol ratio
1 mol NH , mol NO
a . g NH , x = mol NO
g NH , X
mol NH ,
molar mass factor mol ratio
1 mol NH , mol H:0
b. g NH 3 x
gNH ; mol NH 3
= mol H->0
3 COMPUTE Use the periodic table to compute the molar mass of NH3.
1 mol NH3 = 17.04 g/ mol
1 moFNH ; 4 mol NO
a . 824 gNH ; x
17.04 gJMH3
X
4 mol NH,
= 48.4 mol NO

1 mol NH ; b mol H 20
b. 824 g N41; x
i 7.04 g.NH 3
X
4 mol NH ;
= 72.5 mol HiO
4 EVALUATE The answers are correctly given to three significant figures. The units cancel in the
two problems to leave mol NO and mol H 20, respectively, which are the unknowns.

PRACTICE Answers in Appendix E

Oxygen was discovered by Joseph Priestley in 1774 when he heated

mercury( II ) oxide to decompose it to form its constituent elements. iTfbvn
1 . How many moles of mercury ( ll ) oxide, HgO, are needed to pro- Go to go.hrw.com for
more practice problems
duce 125 g of oxygen. 02? that ask you to calculate
2. How many moles of mercury are produced ? unknown quantities by
using mole ratios.
Keyword: HC 6 STCX

STOICHIOMETRY 309
 Molar mass factor Mole ratio Molar mass factor
( Periodic table) ( Balanced equation) (Periodic table)
Mass of Mass of
1 mol given mol unknown Molar mass
given x = unknown
Molar mass of mol given of unknown (g)
substance substance
given (g) 1 mol unknown
( g) (g )
CONVERSION FACTORS
GIVEN IN CALCULATED
THE PROBLEM

FIGURE 4 This is a solution plan

for problems in which the given
quantity is expressed in grams and
Mass- Mass Calculations
the unknown quantity is also
expressed in grams. Mass- mass calculations arc more practical than other mole calculations
you have studied. You can never measure moles directly. You are gen-
erally required to calculate the amount in moles of a substance from its
mass, which you can measure in the lab. Mass-mass problems can be
viewed as the combination of the other types of problems The plan for .
solving mass -mass problems is

mass of amount of amount of mass of

given substance given substance unknown substance > unknown substance
( g) ( mol )
* ( mol ) ( g)

Three additional pieces of data are needed to solve mass-mass prob -

lems: the molar mass of the given substance, the mole ratio, and the
molar mass of the unknown substance.

SAMPLE PROBLEM E For more help, go to the Math iutor at the end of this chapter

Tint II ) fluoride, SnF2, used in some toothpastes. It is made by the reaction of tin with hydrogen fluoride
according to the following equation.

» Snl 2 ( .v ) + H2<
Sn(s ) + 2HF(£ )
*>
How man> grams of SnF2 are produced from the reaction of 30.00 g HF with Sn ?

SOLUTION
1 ANALYZE Given: amount of HF = 30.00 g
Unknown: mass of SnF: produced ( g)

2 PLAN Hie conversion factors needed are the molar masses of HF and SnF: and the mole ratio
of SnFi to HF.

molar mass factor mol ratio molar mass factor

mol HF mol SnF . e SnF-
— x — r = g SnF >
g HF x
g HF
x
mol 111 mol SnF -
-'
~
. 2

310 CHAPTER 9
3 COMPUTE Use the periodic table to compute the molar masses of HF and SnF2 .
1 mol HF = 20.01 g
1 mol SnF: = 156.71 g
1 mol HP 1 mol 5rrF% 156.71 g SnF2
30.00 g-HFx
20.01 g HF 2 mol- HF
- x
1 mol SnF - . = 117.5 g SnF2

4 EVALUATE The answer is correctly rounded to four significant figures. The units cancel to leave g SnF2 .
which matches the unknown. The answer is close to an estimated value of 120.

PRACTICE Answers in Appendix E

1 . Laughing gas ( nitrous oxide, N20 ) is sometimes used as an anes-

thetic in dentistry. It is produced when ammonium nitrate is
decomposed according to the following reaction.
NH 4N02(,V ) > N:0(g) + 2H:0( / )
a. How many grams of NH4N03 are required to produce
33.0 g N20?
b. How many grams of water are produced in this reaction?
2. When copper metal is added to silver nitrate in solution .
silver metal and copper!II ) nitrate are produced. What mass of sil- — irTl j 11

Go to go
^.hrw *
.com for
ver is produced from 100. g Cu?
more practice problems
3. What mass of aluminum is produced by the decomposition that ask you to calculate
of 5.0 kg ALOV? unknown quantities by
using mole ratios.
Keyword: HC 6 STCX

SECTION REVIEW 3. Acetylene gas, C2H2, is produced as a result

1. Balance the following equation. Then, given the of the following reaction:
moles of reactant or product below, determine the CaC2( s) + 2 H20( / ) > C 2H2 (g) + Ca(0H)2(ag)
corresponding amount in moles of each of the a. If 32.0 g CaC2 are consumed in this reaction,
other reactants and products. how many moles of H20 are needed?
NH3 + 02 » N2 + H20 b. How many moles of each product would form ?
a. 4 mol NH 3 b. 4 mol N 2 c. 4.5 mol 02 4. When sodium chloride reacts with silver nitrate,
2. One reaction that produces hydrogen gas can be silver chloride precipitates. What mass of AgCI
represented by the following unbalanced chemical is produced from 75.0 g AgN03 ?
equation:
Critical Thinking
Mg(s) + HCI( ag) MgCI2 ( ag) + H2 ( g )
5. RELATING IDEAS Carbon and oxygen react to form
a. What mass of HCI is consumed by the reaction carbon monoxide: 2 C + 02 > 2 C0. What mass-
of 2.50 moles of magnesium ? es of carbon and oxygen are needed to make
b. What mass of each product is produced in part (a)? 56.0 g CO ? Which law does this illustrate?

STOICHIOMETRY 311
 SECTION 3
Limiting Reactants
OBJECTIVES
J Describe a method for deter-
and Percentage Yield
mining which of two reac -
tants is a limiting reactant.

> j Calculate the amount in I n the laboratory, a reaction is rarely carried out with exactly the
moles or mass in grams of a required amount of each of the reactants. In many cases, one or more
product, given the amounts in reactants is present in excess; that is. there is more than the exact
moles or masses in grams of amount required to react .
two reactants, one of which is Once one of the reactants is used up, no more product can be
in excess. formed . The substance that is completely used up first in a reaction is
called the limiting reactant. The limiting reactant is the reactant that
limits the amount of the other reactant that can combine and the amount
^ Distinguish between theoreti-
cal yield, actual yield, and of product that can form in a chemical reaction. The substance that is not
percentage yield. used up completely in a reaction is called the excess reactant . A limiting
reactant may also be referred to as a limiting reagent .
The concept of the limiting reactant is analogous to the relationship
Calculate percentage yield between the number of people who want to take a certain airplane
given the actual yield and
llight and the number of seats available in the airplane. If 400 people
quantity of a reactant.
want to travel on the flight and only 350 seats are available, then only
350 people can go on the flight . The number of seats on the airplane lim -
its the number of people who can travel . There are 50 people in excess.
The same reasoning can be applied to chemical reactions. Consider
the reaction between carbon and oxygen to form carbon dioxide.
C ( s ) + O2( g ) > C02(g )
According to the equation , one mole of carbon reacts with one mole of
.
oxygen to form one mole of carbon dioxide Suppose you could mix
5 mol C with 10 mol 02 and allow the reaction to take place.
Figure 5 shows that there is more oxygen than is needed to react
with the carbon . Carbon is the limiting reactant in this situation , and
FIGURE 5 If you think of a mole it limits the amount of CO: that is formed . Oxygen is the excess reac-
as a multiple of molecules and tant. and 5 mol O ? will be left over at the end of the reaction .
atoms, you can see why the amount
of O, is in excess.

+ *
5 carbon 10 oxygen 5 carbon dioxide
*
5 oxygen molecules
atoms molecules molecules in EXCESS

312 CHAPTER 9
 SAMPLE PROBLEM F
Silicon dioxide ( quartz ) is usually quite unreactive but reacts readily with hydrogen fluoride according to
the following equation .
SiO 2(s) + 4HF(g) » SiF4(g) + 2H20 < / )

If 6.0 mol HF is added to 4.5 mol Si02« which is the limiting reactant ?

SOLUTION
1 ANALYZE Given: amount of HF = 6.0 mol
amount of Si02 = 4.5 mol
Unknown: limiting rcactanl

2 PLAN For one of the products, the given amounts of reactants are used to calculate the amount of
product that could be produced under ideal conditions. The lesser amount of product repre-
sents the maximum amount that could be formed, and the reactant that gives the lesser
amount of product is the limiting reactant .

mol SiF4 mol SiF4

mol HF x = mol SiF4 produced mol Si02 x = mol SiF4 produced
mol HF mol SiCT

l mol SiF4
3 COMPUTE 6.0 mol HF x = 1.5 mol SiF4 produced
4 mol HF

4.5 mol SiO- x . 1 mol SiF4

1 mol SiO- . = 4.5 mol SiF4 produced

.
Under ideal conditions, the 6.0 mol HF present can make 1.5 mol SiF4 and the 4.5 mol SiO .
.
present can make 4.5 mol SiF4 Because 6.0 mol HF can make only 1.5 mol SiF4. HF is the
limiting reactant.

4 EVALUATE From the balanced equation, we can see that the reaction requires four limes the number
of moles of HF as it does moles of Si 02. Because the molar amount of HF that we have is
less than four times the moles of Si02, our calculations clearly show that HF is the limiting
reactant.

PRACTICE Answers in Appendix E

.
1 Some rocket engines use a mixture of hydrazine. N2H4, and
hydrogen peroxide, H202, as the propellant. The reaction is given
by the following equation.
N2H4( / ) + 2H202( / )
* N2( g ) + 4H:0(g)
a. Which is the limiting reactant in this reaction when 0.750 mol Go to go.hrw.com for
N:H4 is mixed with 0.500 mol H202? more practice problems
that ask you to
b. How much of the excess reactant in moles, remains unchanged?
,
determine the limiting
reactant.
c. How much of each product, in moles, is formed?
Keyword: HC 6 STCX

STOICHIOMETRY 313
 SAMPLE PROBLEM G
The black oxide of iron, Fe304, occurs in nature as the mineral magnetite. This substance can also
be made in the laboratory by the reaction between red- hot iron and steam according to the following
equation.
3Fe(.y) + 4H2()( # ) > Fe304( s) + 4H2( £ )
a . When 36.0 g H20 is mixed with 67.0 g Fe, which is the limiting reactant ?
b. What mass in grams of black iron oxide is produced ?
c. What mass in grams of excess reactant remains when the reaction is completed ?

SOLUTION
1 ANALYZE Given: mass of 11:() = 36.0 g
mass of Fe = 67.0 g
Unknown: limiting reactant
mass of Fe304, in grams
mass of excess reactant remaining

2 PLAN a . First , convert both given masses in grams to amounts in moles. Then, calculate the num -
ber of moles of one of the products. Because the problem asks for the mass of Fe304
formed, we will calculate moles of Fe 3()4. The reactant yielding the smaller number of
moles of product is the limiting reactant.
molar mass factor mol ratio
mol Fe mol Fe304
g Fe x x = mol Fe304
g Fe mol Fe

molar mass factor mol ratio

mol ITO mol Fe304
g H2Q x
g n:o mol H - 0 . = mol FC 3C)4

b. To find the maximum mass of Fe304 that can be produced, we must use the amount ol
Fe;04 in moles from the limiting reactant in a simple stoichiometric problem.
molar mass factor
g Fe3o4
mole FC304 from limiting reactant x = g Fe 3U4 produced
mol Fe 3Q 4
c . To find the amount of excess reactant remaining, we must first determine the amount of
the excess reactant that is consumed. Tile calculated moles of the product ( from the lim -
iting reactant ) is used to determine the amount of excess reactant that is consumed.
mol excess reactant g excess reactant
mol product x x = g excess reactant consumed
mol product mol excess reactant
The amount of excess reactant remaining can then be found by subtracting the amount
consumed from the amount originally present.
original g excess reactant - g excess reactant consumed - g excess reactant remaining

314 CHAPTER 9
3 COMPUTE a. Use the periodic table to determine the molar masses of H:0. Fe. and Fe304. Then.
determine how many mol Fe304 can be produced from each reactant .
1 mol H:0 = 18.02 g
"
1 mol Fe = 55.85 g
1 mol Fe304 = 231.55 g
1 moUFc 1 mol Fe304
67.0 g -Fe- x = 0.400 mol Fe304
55.85 g Fe 3 woFFe
^
1 mol HvO 1 mol Fe3Q4
36.0 giTFO x x = 0.499 mol Fe 304
18.02 g, FhO 4 mol+FiO
Fe is the limiting reactant because the given amount of Fe can make only 0.400 mol Fe304.
which is less than the 0.499 mol Fe3Q4 that the given amount of H:Q would produce.

b. 0.400 mol FC 3Q 4 X
231.55 gFe3Q4
1 mol Fe3Q4
= 92.6 g Fe Q4 ,
c. 0.400 mol Fe 3Q4 x
4 mol H O. x
18.02 g H2Q
= 28.8 g H20 consumed
1 mol Fe3Q4 1 mol HT)

36.0 g H20 - 28.8 g ITO consumed = 7.2 g H:Q remaining

4 EVALUATE
The mass of original reactants is 67.0 + 36.0 = 103.0 g: the mass of Fe304 + unreacted water
is 92.6 g + 7.2 g = 99.8 g. The difference of 3.2 g is the mass of hydrogen that is produced
with the Fe 3Q4.

PRACTICE Answers in Appendix E v TE

* %
1. Zinc and sulfur react to form zinc sulfide accord- CHEMISTRY I
ing to the following equation.
Module 5 : Equations and
8Zn(5 ) + Ss(.v ) > 8 ZnS(.v ) Stoichiometry

a. If 2.00 mol of Zn are heated with 1.00 mol of

SK, identify the limiting reactant.
b. How many moles of excess reactant remain ?
c. How many moles of the product are formed ?

2. Carbon reacts with steam. H:0. at high temperatures to produce

hydrogen and carbon monoxide.
a. If 2.40 mol of carbon are exposed to 3.10 mol of steam, identify
. .
Go to go hrw com for
more practice problems
the limiting reactant. that ask you to calculate
the amount of excess
b. How many moles o! each product are formed? reactant and the
c. What mass of each product is formed? amount of product
formed.
Keyword: HC 6 STCX

STOICHIOMETRY 315
 Quic/LkB O Wear oven mitts when handling heated items.

Materials
Limiting Reactants in a Recipe • 1 / 2 cup sugar
• 1 / 2 cup brown sugar
Procedure that ingredient were con- • 1 1 / 3 stick margarine
1 . In the mixing bowl, combine sumed. (For example, the
recipe shows that using
( at room temperature )
• 1 egg
the sugars and margarine
1 egg —with the right • 1 / 2 tsp. salt
together until smooth. (An
amounts of the other • 1 tsp. vanilla
electric mixer will make this
ingredients—yields 24 cook-
process go much faster.) • 1 / 2 tsp. baking soda
ies. How many cookies can
2. Add the egg, salt, and vanilla. you make if the recipe is • 1 1 / 2 cup flour
Mix well. increased proportionately • 1 1 / 3 cup chocolate chips
for 12 eggs?) • mixing bowl
3. Stir in the baking soda, flour,
• mixing spoon
and chocolate chips. Chill the b. To determine the limiting
dough for an hour in the refrig - reactant for the new ingredi-
• measuring spoons and cups
erator for best results. ents list, identify which • cookie sheet
ingredient will result in the • oven preheated to 350° F
4. Divide the dough into 24 small fewest number of cookies.
balls about 3 cm in diameter.
Place the balls on an ungreased c . What is the maximum num-
cookie sheet. ber of cookies that can be
produced from the new
5. Bake at 350°F for about
amounts of ingredients ?
10 minutes, or until the
cookies are light brown.
Yield: 24 cookies

Discussion
1. Suppose you are given the fol-
lowing amounts of ingredients:
1 dozen eggs
24 tsp. of vanilla
1 lb. ( 82 tsp.) of salt
1 lb. (84 tsp.) of baking soda
3 cups of chocolate chips
5 lb. (11 cups) of sugar
2 lb. (4 cups) of brown sugar
1 lb. (4 sticks) of margarine

a . For eachingredient, calcu-

late how many cookies
could be prepared if all of

316 CHAPTER 9
 Percentage Yield
The amounts of products calculated in the ideal stoichiometry problems
in this chapter so far represent theoretical yields. The theoretical yield is
the maximum amount of product that can be produced from a given
amount of reactant . In most chemical reactions, the amount of product
obtained is less than the theoretical yield . There are many reasons for
this result . Reactants may contain impurities or may form byproducts in
competing side reactions. Also, many reactions do not go to completion.
As a result , less product is produced than ideal stoichiometric calcula -
tions predict . The measured amount of a product obtained from a reac -
tion is called the actual yield of that product.
Chemists are usually interested in the efficiency of a reaction. The
efficiency is expressed by comparing the actual and theoretical yields.
The percentage yield is the ratio of the actual yield to the theoretical
yield , multiplied by 100.
actual yield
percentage yield = x 100
theoretical yield

SAMPLE PROBLEM H
Chlorobenzene, C6H5CI , is used in the production of many important chemicals, such as aspirin, dyes, and
disinfectants. One industrial method of preparing chlorobenzene is to react benzene, C6 H 6, with chlorine,
as represented by the following equation.

C6H < / ) + Cl2 (

*> C6H5CI ( / ) + HCI (g )

When 36.8 g C6H6 react with an excess of Cl 2, the actual yield of C6H 5CI is 38.8 g.
What is the percentage yield of C6 H 5CI ?

SOLUTION
1 ANALYZE Given: mass of C6 H 6 = 36.8 g
mass of Cl 2 = excess
actual yield of C6HsCl = 38.8 g
Unknown: percentage yield of C( HSCI 1

2 PLAN First do a mass- mass calculation to find the theoretical yield of C6H5CI,
molar mass factor mol ratio molar mass
mol C6H6 mol C6H CI ,
g C6H,Cl
g Q,Hh x x x - = g C6H5Cl ( theoretical yield )
g QHfi mol C6 H6 mol C6H5CI
Then the percentage yield can be found .
actual yield
percentage yield C6 H5Cl = x ion
theoretical yield

STOICHIOMETRY 317
3 COMPUTE Use the periodic table to determine the molar masses of ChH6 and C' H?C1. „
1 mol C6H( = 78.12 g )

1 mol CftHsCl = 112.56 g

«
36.8 gXyif, x
I mo -Y,H(1
X
1 moLC
^e 112.56
X
C H C1g 6 5
,
= 53.0 g C YUC \
78.12 _gjCRHj; 1 mof-G
^ 38.8 1gmoi-QH^e ( theoretical yield )

percentage vield = x 100 = 73.2 %

'
53.0 g
4 EVALUATE Tlie answer is correctly rounded to three significant figures to match those in 36.8 g C6Ilf . )

The units have canceled correctly. The theoretical yield is close to an estimated value of 50 g,
( one-half of 100 g ) . The percentage yield is close to an estimated value of 80%. ( 40/50 x 100) .
PRACTICE Answers in Appendix E

1. Methanol can be produced through the reaction of CO and IT in

the presence of a catalyst.

* CH,OH( / )
catalyst
CO( g ) + 2H2(g)
If 75.0 g of CO reacts to produce 68.4 g (TCOH. what is the per -
centage yield of CH ,OH?

2. Aluminum reacts with excess copper( 11 ) sulfate according to the

reaction given below. If 1.85 g of A 1 react and the percentage yield — crX'i -i , vTTi 11
Go to go.hrw.com for
of Cu is 56.6%. what mass of Cu is produced?
more practice problems
Al(.V ) + CuS04( fl<7 ) that ask you to calculate
* M 2( S04 )$( aq ) + Cu(s) ( unbalanced) percentage yield.
Keyword: HC 6 STCX

SECTION REVIEW 3. Quicklime, CaO, can be prepared by roasting lime-

1. Carbon disulfide burns in oxygen to yield carbon stone, CaC 03, according to the following reaction.
dioxide and sulfur dioxide according to the follow- CaCOj(s) CaO(s) + C02(g).
ing chemical equation. When 2.00 x 103 g CaC03 are heated, the actual
CS2 ( / ) + 302(g) C 02(g) + 2 SO2 (g) yield of CaO is 1.05 x 103 g. What is the percentage
yield?
a. If 1.00 mol CS2 is combined with 1.00 mol 02
identify the limiting reactant.
- Critical Thinking
b. How many moles of excess reactant remain? 4. ANALYZING DATA A chemical engineer calculated
c. How many moles of each product are formed? that 15.0 mol H2 was needed to react with excess
2. Metallic magnesium reacts with steam to produce N2 to prepare 10.0 mol NH3. But the actual yield is
magnesium hydroxide and hydrogen gas. 60.0%. Write a balanced chemical equation for the
a. If 16.2 g Mg are heated with 12.0 g H20, what reaction. Is the amount of H2 needed to make
is the limiting reactant ? 10.0 mol NH3 more, the same, or less than
15 mol ? How many moles of H2 are needed?
b. How many moles of the excess reactant are left ?
c. How many grams of each product are formed?

318 CHAPTER 9
 CHAPTER HIGHLIGHTS
Introduction to Stoichiometry
I Vocabulary •Reaction stoichiometry involves the mass relationships
composition stoichiometry between reactants and products in a chemical reaction .
reaction stoichiometry • Relating one substance to another requires expressing the
mole ratio amount of each substance in moles.
• A mole ratio is the conversion factor that relates the amount
in moles of any two substances in a chemical reaction . The
mole ratio is derived from the balanced equation .
•Amount of a substance is expressed in moles, and mass of a
substance is expressed by using mass units such as grams, kilo-
grams. or milligrams.
•Mass and amount of substance are quantities, whereas moles
and grams are units.
•A balanced chemical equation is necessary to solve any stoi -
chiometric problem .

Ideal Stoichiometric Calculations

•In an ideal stoichiometric calculationthe mass or the amount
,

of any reactant or product can be calculated if the balanced

chemical equation and the mass or amount of any other reac-
tant or product is known .

Limiting Reactants and Percentage Yield

I Vocabulary •In actual reactions, the reactants may be present in proportions
limiting reactant that differ from the stoichiometric proportions required for a
excess reactant complete reaction in which all of each reactant is converted to
theoretical yield product.
actual yield •The limiting reactant controls the maximum possible amount
percentage yield of product formed.
•For many reactions, the quantity of a product is less than the
theoretical maximum for that product . Percentage yield shows
the relationship between the theoretical yield and actual yield
for the product of a reaction .

STOICHIOMETRY 319
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
8. In a blast furnace, iron ( lll ) oxide is used to pro-
Introduction to Stoichiometry duce iron by the following ( unbalanced ) reaction:
Fe203( s ) + CO(g ) > Fe ( s ) + CO2(g)
SECTION 1 REVIEW
a. If 4.00 kg Fe:03 are available to react , how
1. a . Explain the concept of mole ratio as used in many moles of CO are needed ?
reaction stoichiometry problems, b. How many moles of each product are formed?
b. What is the source of this ratio? 9. Methanol. CH3OH. is an important industrial
2. For each of the following balanced chemical compound that is produced from the following
equations, write all possible mole ratios: ( unbalanced ) reaction: CO( g ) + H 2(g ) >
a. 2Ca + 02 - * 2CaO CH 3OH ( g ) . What mass of each reactant would
b. Mg + 2 HF * MgF2 + H 2 be needed to produce 100.0 kg of methanol ?
( Hint : See Sample Problem E.)
PRACTICE PROBLEMS 10. Nitrogen combines with oxygen in the atmos-
3. Given the chemical equation Na 2CO$( aq ) + phere during lightning Hashes to form nitrogen
Ca ( OH )2 > 2 NaOH ( <i <7 ) + CaC03(s ). deter - monoxide. NO. which then reacts further with
mine to two decimal places the molar masses of 02 to produce nitrogen dioxide, N02.
all substances involved. Then , write the molar a. What mass of N 02 is formed when NO
masses as conversion factors. reacts with 384 g 02?
b. How many grams of NO are required to
react with this amount of 02?
11. As early as 1938, the use of NaOH was sug-
Ideal Stoichiometric gested as a means of removing CO: from the
Calculations cabin of a spacecraft according to the following
( unbalanced ) reaction: NaOH + CO: »
SECTION 2 REVIEW
Na 2C03 + H:0.
4. a . What is molar mass? a. If the average human body discharges 925.0 g
b. What is its role in reaction stoichiometry? C02 per day, how many moles of NaOl 1 are
needed each day for each person in the
PRACTICE PROBLEMS spacecraft ?
5. Hydrogen and oxygen react under a specific set b. I low many moles of each product are formed ?
of conditions to produce water according to the 12. The double-replacement reaction between sil -
following: 2 H 2(g) + 02(g ) 2 H 20(g ). ver nitrate and sodium bromide produces silver
a. How many moles of hydrogen would be bromide, a component of photographic film .
required to produce 5.0 mol of water ? a . If 4.50 mol of silver nitrate react , what mass
b. How many moles of oxygen would be of sodium bromide is required ?
required ? ( Hint: See Sample Problem A . ) b. What mass of silver bromide is formed ?
6. a. If 4.50 mol of ethane. C2 H ( , undergo com -
)
.
13 In a soda -acid fire extinguisher, concentrated
bustion according to the unbalanced equa - sulfuric acid reacts with sodium hydrogen car -
tion C2 H 6 + 0: > C02 + H 20, how many bonate to produce carbon dioxide, sodium sul -
moles of oxygen are required ? fate. and water.
.
b 1 low many moles of each product are formed ? a . How many moles of sodium hydrogen car -
7. Sodium chloride is produced from its elements bonate would be needed to react with 150.0 g
through a synthesis reaction . What mass of each of sulfuric acid ?
reactant would be required to produce 25.0 mol b. How many moles of each product would be
of sodium chloride? formed ?

320 CHAPTER 9
 CHAPTER REVIEW

14. Sulfuric acid reacts with sodium hydroxide PRACTICE PROBLEMS

according to the following: 22 . Given the reactant amounts specified in each
H 2 S04 + NaOH > Na2 S04 + H20. chemical equation, determine the limiting reac -
a. Balance the equation for this reaction. tant in each case:
b. What mass of H ^ S04 would be required to a. HCI 4 NaOH 4 NaCI + H
20
react with 0.75 mol NaOH? 2.0 mol 2.5 mol
c. What mass of each product is formed by this b. Zn 4 2HCI » ZnCl2 + H2
reaction? ( Hint: See Sample B. ) 2.5 mol 6.0 mol
15. Copper reacts with silver nitrate through single c. 2Fe( 0H)3 + 3H:S04 Fe 2 ( S04 ) 3 + 6H 20
replacement. 4.0 mol 6.5 mol
a. If 2.25 g of silver are produced from the (Hint: See Sample Problem F. )
reaction, how many moles of copper! 11 ) 23. For each reaction specified in Problem 22, deter -
nitrate are also produced? mine the amount in moles of excess reactant
b. How many moles of each reactant are that remains. ( Hint: See Sample Problem G. )
required in this reaction? ( Hint: See Sample 24. For each reaction specified in Problem 22, calcu-
Problem D.) late the amount in moles of each product formed.
16. Aspirin, CgHs04, is produced through the fol- 25. a. If 2.50 mol of copper and 5.50 mol of silver
lowing reaction of salicylic acid. OjHhO and nitrate are available to react by single
^
acetic anhydride, C4H603: C7H603( s ) + replacement, identify the limiting reactant.
C4Hft03( / ) > G>H804(5) + HC2H302( / ). b. Determine the amount in moles of excess
a. What mass of aspirin ( kg) could be produced reactant remaining.
from 75.0 mol of salicylic acid? c. Determine the amount in moles of each
b. What mass of acetic anhydride ( kg ) would product formed.
be required? d. Determine the mass of each product formed.
c. At 20°C. how many liters of acetic acid, 26. Sulfuric acid reacts with aluminum hydroxide
HC\ H302. would be formed? Hie density of bv double replacement.
HC2H302 is l.05 g/mL. a. If 30.0 g of sulfuric acid react with 25.0 g of
aluminum hydroxide, identify the limiting
reactant .
Limiting Reactants and b. Determine the mass of excess reactant
remaining.
Percentage Yield c. Determine the mass of each product formed.
SECTION 3 REVIEW Assume 100% yield.
17 . Distinguish between ideal and real stoichiomet - 27. The energy used to power one of the Apollo lunar
ric calculations. missions was supplied by the following overall
18 . Distinguish between the limiting reactant and reaction: 2N2H4 + (CH3)2N2H2 4- 3N204 >
.
the excess reactant in a chemical reaction 6N2 + 2CQ2 + 8H20. For the phase of the mission
19. a. Distinguish between the theoretical yield and when the lunar module ascended from the surface
of the moon, a total of 1200. kg N2H4 was avail -
actual yield in stoichiometric calculations,
b. I low does the value of the theoretical yield .
able to react with 1000. kg (CH3)->N- H ^ and
generally compare with the value of the 4500. kg N204.
actual yield? a. For this portion of the flight , which of the
20. What is the percentage yield of a reaction ? allocated components was used up first ?
21. Why are actual yields usually less than calculat - b. I low much water, in kilograms, was put into
ed theoretical yields? the lunar atmosphere through this reaction?

STOICHIOMETRY 321
 CHAPTER REVIEW

28 . Calculate the indicated quantity for each of the 33. Coal gasification is a process that converts coal
various chemical reactions given: into methane gas. It this reaction has a percent -
a . theoretical yield = 20.0 g. actual yield = age yield of 85.0%. what mass of methane can
15.0 g, percentage yield = ? be obtained from 1250 g of carbon ?
b. theoretical yield = 1.0 g. percentage yield = 2C(s) + 2 H:0 ( / ) > CH4(g ) + CO:( £ )
.
90.0 % actual yield = ? 34. If the percentage yield for the coal gasification
c. theoretical yield = 5.00 g. actual yield = process is increased to 95 %. what mass of
4.75 g. percentage yield = ? methane can be obtained from 2750 g of carbon ?
d theoretical yield = 3.45 g. percentage yield =
. 35 . Builders and dentists must store plaster of Paris.
48.0 % . actual yield = ?
29. The percentage "
yield for the reaction
PCI3 + Cl 2 » PCI5
^
CaS04 * H 20, in airtight containers to prevent
it from absorbing water vapor from the air and
changing to gypsum , CaS04 * 2 H 20. How many
is 83.2 %. What mass of PC1S is expected from the liters of water vapor evolve when 2.00 kg of
reaction of 73.7 g PCI3 with excess chlorine? gypsum are heated at 110°C to produce plaster
30. The Ostwald process for producing nitric acid of Paris? At 110°C, the density of water vapor is
from ammonia consists of the following steps: 0.574 g/ L.
4N H d g ) + 502(g) —> 4 N ( ) ( g ) + 6H20(g ) 36. Gold can be recovered from sea water by react -
2 NO(g ) + O2( g ) > 2 N 02(g ) ing the water with zinc, which is refined from
3 NO:( g ) + HiO(g ) > 2 HNO ( ctq ) + NO(g ) zinc oxide. The zinc displaces the gold in the
If the yield in each step is 94.0 %^ , how many water. What mass of gold can be recovered if
grams of nitric acid can be produced from 2.00 g of ZnO and an excess of sea water are
5.00 kg of ammonia? available?
2 ZnO(s) + C( s ) > 2 Zn ( x ) + C02(g )
l A u ^ U u f ) + 3Zn (s ) > 3Zn 2* ( aq ) + 2Au (.v )
MIXED REVIEW
31 . Magnesium is obtained from sea water. Ca ( OH )2 CRITICAL THINKING
is added to sea water to precipitate Mg( OH )2.
Hie precipitate is filtered and reacted with HCI 37 . Relating Ideas Hie chemical equation is a
to produce MgCk The MgCI 2 is electrolyzed to good source of information concerning a reac-
produce Mg and Ck If 185.0 g of magnesium are tion . Explain the relationship between the actu -
recovered from 1000. g MgCk what is the per- al yield of a reaction product and the chemical
centage yield for this reaction ? equation of the product.
32 . Phosphate baking powder is a mixture of starch , 38 . Analyzing Results Very seldom are chemists
sodium hydrogen carbonate, and calcium dihv - able to achieve a 100% yield of a product from
drogen phosphate. When mixed with water, phos- a chemical reaction . However, the yield of a
phate baking powder releases carbon dioxide reaction is usually important because of the
gas. causing a dough or batter to bubble and rise. expense involved in producing less product. For
2 NaHC03( M/ ) + Ca ( H 2 P04 )2( r/ r/ ) > example, when magnesium metal is heated in a
V
Na:llPO40 / < / ) + CaIIP04 ( ) + crucible at high temperatures, the product mag -
2C02(S ) + 2 H 20( / ) nesium oxide. MgO. is formed. Based on your
If 0.750 L CCk is needed for a cake and each analysis of the reaction , describe some of the
kilogram of baking powder contains 168 g of actions that you would take to increase your
NaHCOj. how many grams of baking powder percentage yield . The reaction is as follows:
must be used to generate this amount C02? The 2 Mg( .v ) + 02( # ) > 2 MgO(s )
density of CO: at baking temperature is about
1.20 g/ L.

322 CHAPTER 9
 CHAPTER REVIEW

39. Analyzing Results In the lab. you run an

RESEARCH & WRITING
experiment that appears to have a percentage
yield of 115 %. Propose reasons for this result. .
44 Research the history of the Haber process for
Can an actual yield ever exceed a theoretical the production of ammonia. What was the sig-
yield? Explain your answer. nificance of this process in history ? How is this
40. Relating Ideas Explain the stoichiometry of process related to the discussion of reaction
blowing air on a smoldering campfire to keep yields in this chapter?
the coals burning.

ALTERNATIVE ASSESSMENT
1J USING THE HANDBOOK
’
.
45 Performance Just as reactants combine in cer -
.
41 The steel- making process described in the tain proportions to form a product, colors can
Transition Metal section of the Elements be combined to create other colors. Artists do
Handbook shows the equation for the forma - this all the time to find just the right color for
tion of iron carbide. Use this equation to answer their paintings. Using poster paint , determine
the following questions: the proportions of primary pigments used to
a. If 3.65 x 10 ' kg of iron is used in a steel - create the following colors. Your proportions
making process, what is the minimum mass of should be such that anyone could mix the color
carbon needed to react with all of the iron? perfectly.
b. What is the theoretical mass of iron carbide
that is formed?
42. The reaction of aluminum with oxygen to pro-
duce a protective coating for the metal's surface
is described in the discussion of aluminum in .
46 Performance Write two of your ow n sample
Group 13 of the Elements Handbook . Use this problems that are descriptions of how to solve a
mass-mass problem. Assume that your sample
equation to answer the following questions:
a. What mass of aluminum oxide would theo-
problems will be used by other students to learn
how to solve mass-mass problems.
retically be formed if a 30.0 g piece of alu-
minum foil reacted with excess oxygen?
b. Why would you expect the actual yield from
this reaction to be far less than the mass you
calculated in item ( a )?
43. The reactions of oxide compounds to produce ITTIO ii
carbonates, phosphates, and sulfates are
described in the section on oxides in Group 16
of the Elements Handbook . Lise those equa-
tions to answer the follow ing questions:
s Graphing Calculator Limiting Reactants
and Percentage Meld
. .
Go to go hrw com for a graphing calculator
a. What mass of CO ? is needed to react w ith
exercise that asks you to use a theoretical
154.6 gMgO? yield graph to make predictions about limit -
b. What mass of magnesium carbonate is ing reactants and percentage yield.
produced? Keyword: HC 6 STCX
c. When 45.7 g P4Oln is reacted with an excess
of calcium oxide, what mass of calcium phos-
phate is produced?

STOICHIOMETRY 323
 Math Tutor USING MOLE RATIOS

An unbalanced chemical equation tells you what substances react and what products
are produced. A balanced chemical equation gives you even more information. It tells
you how many atoms, molecules, or ions react and how many atoms, molecules, or
ions are produced. The coefficients in a balanced equation represent the relative
amounts in moles of reactants and products. Using this information, you can set up a
mole ratio. A mole ratio is a conversion factor that relates the amounts in moles of any
two substances involved in a chemical reaction.

Problem-Solving TIPS
• When solving stoichiometric problems, always start with a balanced chemical
equation.
• Identify the amount known from the problem ( in moles or mass ).
• If you are given the mass of a substance, use the molar mass factor as a conver-
sion factor to find the amount in moles. If you are given the amount in moles of a
substance, use the molar mass factor as a conversion factor to find the mass.

SAMPLE
If 3.61 g of aluminum reacts completely with excess CuCI2, what mass of copper metal is
produced? Use the balanced ecpiation below.
2 AI( s) + 3CUC12(#9) 2 AICI3( fl ) + 3Cu(.v )
^
You know the mass of aluminum that reacts. If you convert that mass to moles, you can apply
the mole ratio of aluminum to copper in this reaction to find the moles of copper produced .
1 mol Al
mol Al = 3.61 g Al x = 0.134 mol AI
26.08 g Al
3 mol Cu
mol Al x mol Cu
2 mol Al
3 mol Cu
0.134 mol AI x 0.201 mol Cu
2 mol Al
Then, convert moles of Cu to mass of Cu by applying the following factor:
molar mass Cu 63.55 g Cu
mol Cu x = mass Cu. or 0.201 mol Cu x = 12.8 gCu
I mol Cu 1 mol Cu

PRACTICE PROBLEMS
. -
1 If 12.24 moles of C) -> react with excess SO >, how 2. If 78.50 g KC103 decomposes, what mass of 02
many moles of S03 are formed? Use the bal- is produced? Use the balanced equation below.
anced equation below. 2KCIC>3( <r ) 2KCI(.v ) + 3CMs )
2SO:( tf ) + 0:( £ )
* 2SO,(s )

324 CHAPTER 9
Answer the following items on a separate piece of paper. 7. If a chemical reaction involving substances A
MULTIPLE CHOICE
and B stops when B is completely used up,
then B is referred to as the
.
1 In stoichiometry, chemists are mainly concerned .
A excess reactant . C. limiting reactant .
with
A. the types of bonds found in compounds.
. .
B primary reactant. D primary product .

.
B mass relationships in chemical reactions. .
8 If a chemist calculates the maximum amount of
.
C energy changes occurring in chemical product that could be obtained in a chemical
reaction, he or she is calculating the
reactions.
D. the speed with which chemical reactions
.
A percentage yield.

occur.
.
B mole ratio.
.
C theoretical yield.
2. Assume ideal stoichiometry in the reaction .
D actual yield.
CHj + 2CL > CCL + 21LO. If you know the
9. What is the maximum number of moles of
mass of CH4. you can calculate
.
A only the mass of CO: produced . ,
A1C1 that can be produced from 5.0 mol A!
and 6.0 mol CL?
.
B only the mass of CL reacting.
2 A 1 + 3CL -4 2 AIC13
.
C only the mass of CCL + H20 produced.
A. 2.0 mol AICI3 .
C 5.0 mol AICI3
D. the mass of CL reacting and CO ? + FLO
produced.
.
B 4.0 mol AICI3 .
D 6.0 mol A1C1 ,
SHORT ANSWER
3. Which mole ratio for the equation
6Li -t- N\ ,
> 2Li N is incorrect ? 10. Why is a balanced equation necessary to solve a
mass-mass stoichiometry problem?
6 mol Li 2 mol Li3N
A. 2 mol NL C .
1 mol N ?
.
11 What data are necessary to calculate the per -
centage yield of a reaction ?

B. 61 mol N
mol Li
>
* _
D . 2 6mol LL,N
—
mol Li
EXTENDED RESPONSE
12. A student makes a compound in the laboratory
4. For the reaction below, how many moles of NL and reports an actual yield of 120%. Is this
result possible? Assuming that all masses were

.
A 4.5
.
are required to produce 18 mol NH ?
N + 3FL 2NH3
C. 18
^ measured correctly, give an explanation.
13. Benzene, C6Hft, is reacted with bromine Br: to. .
.
B 9.0 D 36. .
produce bromobenzene. QH Br and hydrogen
^
bromide, HBr, as shown below. When 40.0 g of
5 . What mass of NaCl can be produced bv the
benzene are reacted with 95.0 g of bromine,
reaction of 0.75 mol CL ? 65.0 g of bromobenzene is produced .
2Na + CL -4 2NaCl
A. 0.75 g C. 44 g C6H6 + Br2 C6H5Br + HBr
B. 1.5 g .
D SSg a. Which compound is the limiting reactant ?
.
6 What mass of CCL can be produced from 25.0 g b. What is the theoretical yield of bromobenzene?
CaC03 given the decomposition reaction c. What is the reactant in excess, and how much
CaC03 4 C aO + CCL remains after the reaction is completed?
A. 11.0 g C 25.0 g. d. What is the percentage yield?
.
B 22.0 g D 56.0 g.
Choose an answer to a question
based on both information that you already know
and information that is presented in the question.

STOICHIOMETRY 325
 SEE PRE - LAB
EXPERIMENT 9 EXTRACTION AND FILTRATION

Stoichiometry and
Gravimetric Analysis
OBJECTIVES BACKGROUND
• Observe the double -displacement reaction ITiis gravimetric analysis involves a double -
between solutions of strontium chloride displacement reaction between strontium chloride.
and sodium carbonate. SrCL, and sodium carbonate, Na:C03. This type of
reaction can be used to determine the amount of a
• Demonstrate proficiency with gravimetric
methods. carbonate compound in a solution. For accurate
results, essentially all of the reactant of unknown
• Measure the mass of the precipitate that amount must be converted into product. If the mass
forms. of the product is carefully measured , you can use
• Relate the mass of the precipitate that stoichiometric calculations to determine how much
forms to the mass of the reactants before of the reactant of unknown amount was involved
the reaction. in the reaction .
• Calculate the mass of sodium carbonate
in a solution of unknown concentration . SAFETY

MATERIALS
• 15 mL Na 2C03 • glass stirring
solution of unknown rod For review of safety, please see Safety in the
concentration Chemistry Laboratory in the front of your book.
• paper towels
• 50 mL 0.30 M SrCI2
solution
• ring and ring PREPARATION
stand 1. Make a data table that has 2 columns and 5 rows.
• 50 mL graduated cylinder spatula In the first column write each of the following
• 250 mL beakers, 2 phrases in a separate row: "Volume of Na2C03
• water bottle
• balance solution added '; “ Volume of SrCl 2 solution
*

added ": “ Mass of dry filter paper"; “ Mass of

• beaker tongs beaker with paper towel ”; “ Mass of beaker w ith
• distilled water paper towel , filter paper, and precipitate."
• drying oven 2 . Clean all of the necessary lab equipment with
• filter paper soap and water, and rinse with distilled water.

• glass funnel or Buchner 3 . Measure the mass of a piece of filter paper to

funnel with related the nearest 0.01 g. and record it in your table.
equipment
4. Set up a filtering apparatus. Use the Pre-
Laboratory Procedure “ Extraction and
Filtration ."

326 CHAPTER 9
 EXPERIMENT 9

5. Label a paper towel with your name and the

date. Place the towel in a clean , drv 250 mL
beaker, and measure and record the mass of the
paper towel and beaker to the nearest 0.01 g.

PROCEDURE
1. Measure about 15 mL of the Na 2C03 solution into
the graduated cylinder. Record this volume to the
nearest 0.5 mL. Pour the Na 2C03 solution into an
empty 250 mL beaker. Carefully wash the gradu -
ated cylinder, and rinse it with distilled water.
2. Measure about 25 mL of the 0.30 M SrCl2
solution into the graduated cylinder. Record this
volume to the nearest 0.5 mL. Pour the SrCL
solution into the beaker with the Na2C03 solu -
tion . as shown in Figure A. Gently stir with a
glass stirring rod .
FIGURE A The precipitate is a product of the
3. Measure another 10 mL of the SrCL solution reaction between Na2C03 and SrCI2. Add enough
into the graduated cylinder. Record the volume SrCI2 to react with all of the Na 2C03 present.
to the nearest 0.5 mL. Slowlv add the solution to
9

the beaker, and stir gently. Repeat this step until

no more precipitate forms. CLEANUP AND DISPOSAL
9. Dispose of the precipitate and the fil -
4. Slowly pour the mixture into the funnel. Do not
trate in designated waste containers.
—
overfill the funnel some of the precipitate could
Clean up all equipment after use, and
be lost between the filter paper and the funnel.
dispose of substances according to your
5. Rinse the beaker several more times with dis - teacher 's instructions. Wash your hands thor -
tilled water. Pour the rinse water into the funnel oughly after all lab work is finished .
each time.
ANALYSIS AND INTERPRETATION
6. After all of the solution and rinses have drained
through the funnel , use distilled water to slowly 1. Organizing Ideas: Write a balanced equation for
rinse the precipitate on the filter paper in the the reaction. What is the precipitate?
funnel to remove any soluble impurities. 2. Applying Ideas: Calculate the mass of the drv
7. Carefully remove the filter paper from the precipitate. Calculate the number of moles of
funnel, and place it on the paper towel that you precipitate produced in the reaction .
labeled with your name. Unfold the filter paper , 3. Applying Ideas: How many moles of Na 2 C03
and place the paper towel , filter paper, and were present in the 15 mL sample ? How many
precipitate in the rinsed beaker. Then , place grams of Na 2C03 were present ?
the beaker in the dry ing oven . For best results,
allow the precipitate to drv overnight. CONCLUSIONS
8. Using beaker tongs, remove your sample 1. Applying Conclusions: There are 0.30 mol SrCL
from the oven , and let it cool. Record the total in every liter of solution . Calculate the number
mass of the beaker, paper towel , filter paper, and of moles of SrCL that were added . What is the
precipitate to the nearest 0.01 g. limiting reactant ?

STOICHIOMETRY 327
 CHAPTER 10

States of Matter
The total three-dimensional arrangement
of particles of a crystal is its crystal structure.

For advanced project ideas

from Scientific American,
visit go.hrw.com and type
in the keyword HC6 SAD.
Icicle Sculpture
The Kinetic-Molecular SECTION 1

Theory of Matter OBJECTIVES

State the kinetic -molecular
theory of matter, and describe
how it explains certain prop-
erties of matter.
I n Chapter I, you read that matter exists on Earth in the forms of
solids, liquids, and gases. Although it is not usually possible to observe J List the five assumptions of
individual particles directly, scientists have studied large groups of these the kinetic -molecular theory
particles as they occur in solids, liquids, and gases. of gases. Define the terms
In the late nineteenth century, scientists developed the kinetic - ideal gas and real gas.
molecular theory of matter to account for the behavior of the atoms and
molecules that make up matter. The kinetic-molecular theory is bused
on the idea that panicles of matter are always in motion . The theory can ^ Describe each of the following
characteristic properties of
be used to explain the properties of solids, liquids, and gases in terms of gases: expansion, density, flu -
the energy of particles and the forces that act between them. In this sec - idity, compressibility, diffusion,
tion, you will study the theory as it applies to gas molecules. and effusion.

J Describe the conditions under

The Kinetic- Molecular which a real gas deviates
from " ideal " behavior.
Theory of Gases
The kinetic-molecular theory can help you understand the behavior of
gas molecules and the physical properties of gases. The theory provides
a model of what is called an ideal gas. An ideal gas is a hypothetical gas
that perfectly fits all the assumptions of the kinetic - molecular theory. CHEMISTRY
Module 1 : States of Matter /Classes
The kinetic -molecular theory of gases is based on the following five of Matter
assumptions:
1. Gases consist of large numbers of tiny particles that are far apart rela -
tive to their size. These particles, usually molecules or atoms, typically
occupy a volume that is about 1000 times greater than the volume
occupied by an equal number of particles in the liquid or solid state.
Thus, molecules of gases are much farther apart than molecules of liq -
uids or solids. Most of the volume occupied by a gas is empty space,
which is the reason that gases have a lower density than liquids and
solids do. This also explains the fact that gases are easily compressed.
SCllNKS. Mft
Omtoffd Md NMMtfMffd fey it*
Mjtiwul ScMMf TMthtn AVMMUIMMI
2. Collisions between gas particles and between particles and container For a variety of links related to this
walls are elastic collisions. An elastic collision is one in which there is chapter, go to www.scilinks.org I
no net loss of total kinetic energy. Kinetic energy is transferred
between two particles during collisions. However, the total kinetic
Topic: Gases
SciLinks code: HC60638
^
energy of the two particles remains the same as long as temperature
is constant.

STATES OF MATTER 329

 3 . Gas particles are in continuous, rapid , random motion , 1 hey there -
'

fore possess kinetic energy, which is energy of motion. Gas particles

move in all directions, as shown in Figure 1. The kinetic energy of
the particles overcomes the attractive forces between them , except
near the temperature at which the gas condenses and becomes a
liquid .
4. There are no forces of attraction betw een gas particles. You can think
of ideal gas molecules as behaving like small billiard balls. When they
collide, they do not stick together but immediately bounce apart .
5 . The temperature of a gas depends on the average kinetic energy of the
particles of the gas. The kinetic energy of any moving object , includ -
ing a particle, is given by the following equation:
1
KE = - mtr
i

In the equation , m is the mass of the particle and v is its speed. Because
all the particles of a specific gas have the same mass, their kinetic energies
depend only on their speeds. The average speeds and kinetic energies of
gas particles increase with an increase in temperature and decrease with
a decrease in temperature.
All gases at the same temperature have the same average kinetic
energy. Therefore, at the same temperature, lighter gas particles, such
FIGURE 1 Gas particles travel in as hydrogen molecules, have higher average speeds than do heavier
-
a straight line motion until they col - gas particles, such as oxygen molecules.
lide with each other or the walls of
their container.

The Kinetic - Molecular Theory

and the Nature of Gases
The kinetic- molecular theory applies only to ideal gases. Although ideal
gases do not actually exist , many gases behave nearly ideally if pressure
is not very high and temperature is not very low. In the following sec-
tions. you will see how the kinetic- molecular theory accounts for the
physical properties of gases.

Chemical Content Expansion

Go to go. hrw.com lor another ver - Gases do not have a definite shape or a definite volume. They com -
sion of this content . See the chapters pletely fill any container in which they are enclosed , and they take its
“ Physical Characteristics of Gases. shape. A gas transferred from a one-liter vessel to a two-liter vessel will
'

“Molecular Composition of Gases. ’ *

quickly expand to fill the entire two- liter volume. The kinetic- molecular
and “ Liquids and Solids. '

o /. theory explains these facts. According to the theory, gas particles move
Keyword: HC 6 STMX rapidly in all directions ( assumption 3 ) without significant attraction
between them ( assumption 4 ).

Fluidity
Because the attractive forces between gas particles are insignificant
particles glide easily past one another. This ability to
( assumption 4 ). gas

330 CHAPTER 10
flow causes gases lo behave as liquids do. Because liquids and gases
How. they are both referred to as fluids.

Low Density
The density of a gaseous substance at atmospheric pressure is about
1/ 1000 the density of the same substance in the liquid or solid state. The
reason is that the particles are so much farther apart in the gaseous state
( assumption 1 ).

Compressibility
During compression, the gas particles, which are initially very far apart
( assumption 1 ). are crowded closer together. The volume of a given
sample of a gas can be greatly decreased. Steel cylinders containing
gases under pressure are widely used in industry. When they are full,
such cylinders may contain more than 100 times as many particles of gas
as nonpressurized containers of the same size could contain.
SC
Diffusion and Effusion
/ lNKS. Omtoyid mi Ukitd Ivy Ike
NalMMi SdNte AiiMkJttM
Gases spread out and mix with one another, even without being stirred.
For a variety of links related to this
If the stopper is removed from a container of ammonia in a room, chapter, go to :
ammonia gas will mix uniformly with the air and spread throughout the
room. The random and continuous motion of the ammonia molecules
Topic: Diffusion/Effusion
SciLinks code: HC60407
^
( assumption 3 ) carries them throughout the available space. Such spon -
taneous mixing of the panicles of two substances caused by their random
motion is called diffusion.
Gases diffuse readily into one another and mix together due to the
rapid motion of the molecules and the empty space between the mole -
.
cules The gas molecules in each of the two flasks in Figure 2a continu-
ously move about in separate flasks because the stopcock is closed.
When the stopcock is open, the gas molecules continuously diffuse back
and forth from one flask to the other through the opening in the stop-
cock . as shown in Figure 2 b.

e v ll _ _ V at v
H2
Stopcock Stopcock

.-
a?
*
closed
# •* open V.
«*
Ur
o>
JJ
ct y C£5
i .

* **
-•
, w
» i AX J*
S
.
V

(a) (b)

FIGURE 2 Gases diffuse readily into one another. The space between the
molecules allows different gases to mix together easily.

STATES OF MATTER 331

 Diffusion is a process by which particles of a gas spread out sponta -
neously and mix with other gases. In contrast, effusion is a process by
which gas panicles pass through u tiny opening. The rates of effusion of

f different gases are directly proportional to the velocities of their parti-

cles. Because of this proportionality, molecules of low mass effuse faster
than molecules of high mass.

*
Deviations of Real Gases
w *
a
* *e 9 from Ideal Behavior
(a )
Because particles of gases occupy space and exert attractive forces on
each other, all real gases deviate to some degree from ideal gas behav -
« ior. A real gas is a gus that does not behave completely according to the

v assumptions of the kinetic - molecular theory . At very high pressures and

low temperatures, the gas particles will be closer together and their
kinetic energy will be insufficient to overcome completely the attractive
forces. At such conditions, the gas is most likely to behave like a non -
ideal gas. These conditions are illustrated in Figure 3.
The kinetic -molecular theory is more likely to hold true for gases
whose particles have little attraction for each other. The noble gases,
( b)
such as helium. He. and neon, Ne, show essentially ideal gas behavior
over a wide range of temperatures and pressures. The particles of these
FIGURE 3 ( a ) Gas molecules in a gases are monatomic and thus nonpolar. The particles of gases, such as
car engine cylinder expand to fill the nitrogen. N:. and hydrogen. H:. are nonpolar diatomic molecules. The
cylinder, ( b ) As pressure is exerted behavior of these gases most closely approximates that of the ideal gas
on them, the gas molecules move under certain conditions. The more polar the molecules of a gas are. the
closer together, reducing their
greater the attractive forces between them and the more the gas will
volume.
deviate from ideal gas behavior. For example, highly polar gases, such as
ammonia. NHV and water vapor , deviate from ideal behavior to a larger
degree than nonpolar gases.

SECTION REVIEW 5. What happens to gas particles when a gas is

1. Use the kinetic -molecular theory to explain each compressed ?
of the following properties of gases: expansion, 6. What happens to gas particles when a gas is
fluidity, low density, compressibility, and diffusion. heated?
2. Describe the conditions under which a real gas is Critical Thinking
most likely to behave ideally.
7. DRAWING CONCLUSIONS Molecules of hydrogen
3. Which of the following gases would you expect to escape from Earth, but molecules of oxygen and
deviate significantly from ideal behavior: He, 02, nitrogen are held to the surface and remain in the
H 2, H20, N2, HCI, or NH 3 ? atmosphere. Explain.
4. How does the kinetic -molecular theory explain the
pressure exerted by gases ?

332 CHAPTER 10
Liquids SECTION 2

OBJECTIVES
^ Describe the motion of
I he water in the waves crashing on a beach and the molten lava particles in liquids and the
rushing down the sides of a volcano are examples of matter in the liq - properties of liquids according
uid state. When you think of Earth 's oceans, lakes, and rivers and the to the kinetic-molecular theory.
.
many liquids you use every day it is hard to believe that liquids are the
least common state of matter in the universe. Liquids are less common Discuss the process by which
than solids and gases because a substance can exist in the liquid state liquids can change into a gas.
only within a relatively narrow range of temperatures and pressures. Define vaporization.
In this section, you will examine the properties of the liquid state.
You will also compare them with those of the solid state and the
gas state. These properties will be discussed in terms of the kinetic - ^ Discuss the process by which
liquids can change into a
molecular theory. solid. Define freezing.

Properties of Liquids and the

Kinetic - Molecular Theory CHEMISTRY
Module 1 : States of Matter /Classes
A liquid can be described as a form of matter that has a definite vol- of Matter
ume and takes the shape of its container. The properties of liquids can
be understood by applying the kinetic -molecular theory, considering
the motion and arrangement of molecules and the attractive forces
between them.
As in a gas, particles in a liquid are in constant motion. However, the
particles in a liquid are closer together than the particles in a gas are.
Therefore, the attractive forces between particles in a liquid are more
effective than those between particles in a gas. This attraction between
liquid particles is caused by the intermolecular forces discussed in
Chapter 6: dipole-dipole forces, London dispersion forces, and hydro-
gen bonding. Some molecules at the surface of a liquid can have enough
kinetic energy to overcome these forces, and enter the gas state.
Liquids are more ordered than gases because of the stronger inter -
molecular forces and the lower mobility of the liquid particles.
According to the kinetic -molecular theory of liquids, the particles are
.
not bound together in fixed positions Instead, they move about con -
SCllNKS. Pwetoprd tmd mm by 0
*
«
N MMI Wim
* AiMcirtMM
stantly. Iliis particle mobility explains why liquids and gases are For a variety of links related to this
referred to as fluids. A fluid is a substance that can flow and therefore chapter, go to www.scilinlcs.org
take the shape of its container. Most liquids naturally flow downhill
because of gravity. However, some liquids can flow in other directions
Topic: Properties of Liquids
SciLinks code: HC61228
^
as well. For example, liquid helium near absolute zero has the unusual
property of being able to flow uphill.

STATES OF MATTER 333

 Relatively High Density
At normal atmospheric pressure, most substances are hundreds of times
denser in a liquid state than in a gaseous state. This higher density is a
Solid cork result of the close arrangement of liquid particles. Most substances are
only slightly less dense ( about 10% ) in a liquid state than in a solid state,
Liquid alcohol however. Water is one of the few substances that becomes less dense
when it solidifies, as will be discussed further in Section 5.
At the same temperature and pressure, different liquids can differ
Solid paraffin greatly in density. Figure 4 shows some liquids and solids with different
> N

</1
c densities. The densities differ to such an extent that the liquids form
Liquid oil -0O
)
layers.
CJ)
c
l/l
TO
0> Relative Incompressibility
Liquid water
When liquid water at 20 C is compressed by a pressure of 1000 atm. its
u
C

volume decreases by only 4 %. Such behavior is typical of all liquids and

Solid rubber is similar to the behavior of solids. In contrast, a gas under a pressure of
1000 atm would have only about 1/ 1000 of its volume at normal atmos-
Liquid glycerin
pheric pressure. Liquids are much less compressible than gases because
liquid particles are more closely packed together. Like gases, liquids can
transmit pressure equally in all directions .
FIGURE 4 Solids and liquids of Ability to Diffuse
different densities are shown. The As described in Section 1. gases diffuse and mix with other gas particles.
densest materials are at the bottom.
The least dense are at the top. ( Dyes
Liquids also diffuse and mix with other liquids, as shown in Figure 5 .
Any liquid gradually diffuses throughout any other liquid in which it
have been added to the liquids to
can dissolve. The constant, random motion of particles causes diffusion
make the layers more visible. )
in liquids, as it does in gases. Yet diffusion is much slower in liquids than
in gases because liquid particles are closer together. Also, the attractive
forces between the particles of a liquid slow their movement. As the
FIGURE 5 Like gases, the two liq - temperature of a liquid is increased, diffusion occurs more rapidly. The
uids in this beaker diffuse over time. reason is that the average kinetic energy, and therefore the average
The green liquid food coloring from speed of the particles, is increased.
the drop will eventually form
a uniform solution with the water .
Water
molecule -

334 CHAPTER 10
Surface Tension Attractions on a Attractions on a
A property common to all liquids is surface tension, a force that lends to typical molecule surface molecule
in a liquid
pull adjacent parts of a liquid 's surface together, thereby decreasing surface
area to the smallest possible size. Surface tension results from the attrac-
tive forces between particles of a liquid . The higher the force of attraction ,
the higher the surface tension . Water has a higher surface tension than
most liquids. This is due in large part to the hydrogen bonds water mole-
cules can form with each other. The molecules at the surface of the water
are a special case. They can form hydrogen bonds with the other water
molecules beneath them and beside them , but not with the molecules in
the air above them . As a result , the surface water molecules are drawn
together and toward the body of the liquid , creating a high surface ten -
sion . Surface tension causes liquid droplets to take on a spherical shape
because a sphere has the smallest possible surface area for a given vol -
ume. An example of this phenomenon is shown in Figure 6.
Capillary action, the attraction of the surface of a liquid to the surface
of a solid , is a property closely related to surface tension . A liquid will
rise quite high in a very narrow tube and will wet the tube if a strong w
attraction exists between the liquid molecules and the molecules that
make up the surface of the tube, lliis attraction tends to pull the liquid
molecules upward along the surface and against the pull of gravity. This
process continues until the attractive forces between the liquid mol -
ecules and the surface of the tube are balanced by the weight of the liq -
uid . Capillary action can occur between water molecules and paper
fibers, as shown in Figure 7. Capillary action is at least partly responsi- FIGURE 6 Asa result of surface
ble for the transportation of water from the roots of a plant to its leaves. tension , liquids form roughly spheri -
The same process is responsible for the concave liquid surface, called a cal drops. The net attractive forces
between the particles pull the mole -
meniscus, that forms in a test tube or graduated cylinder.
cules on the surface of the drop
inward. The molecules are pulled
Evaporation and Boiling very close together , which minimizes
The process by which a liquid or solid changes to a gas is vaporization. the surface area.
Evaporation is a form of vaporization . Evaporation is the process by
which particles escape from the surface of a nonboiling liquid and enter
the gas state.

FIGURE 7 ITie attraction between polar

water molecules and polar cellulose molecules

ip in paper fibers causes the water to move up in

the paper. The water-soluble ink placed near
the bottom of the paper in ( a ) rises up the
paper along with the water as seen in ( b ). As
,

the ink moves up the paper, it is separated into

its various components producing the different
,

bands of color. This separation occurs because

the water and the paper attract the molecules
of the ink components differently. These phe -
nomena are used in the separation process of
(a) paper chromatography seen here.

STATES OF MATTER 335

 Evaporated Br 2(g) A small amount of liquid bromine was added to the bottle shown in
molecule diffusing into air Figure 8. Within a few minutes, the air above the liquid bromine turned
N 2 (g) molecule \ O2(g) molecule brownish-red because some bromine molecules escaped from the sur -
face of the liquid. These molecules became gas molecules, or bromine
vapor, which mixed with the air. A similar phenomenon occurs if you
apply perfume to your wrist. Within seconds, you become aware of the
perfume's fragrance. Scent molecules evaporate from your skin and dif -
fuse through the air. where your nose detects them.
Evaporation occurs because the particles of a liquid have different
kinetic energies. Particles with higher-than-average energies move
faster. Some surface particles with higher- than-average energies can
overcome the intermolecular forces that bind them to the liquid. They
can then escape into the gas state.
Evaporation is a crucial process in nature. Evaporation removes
fresh water from the surface of the ocean, leaving behind a higher con -
centration of salts. In tropical areas, evaporation occurs at a higher rate,
causing the surface water to be saltier. All water that falls to Earth in
the form of rain and snow previously evaporated from oceans, lakes,
molecule and rivers. Evaporation of perspiration plays an important role in keep -
ing you cool. Perspiration, which is mostly water, cools you by absorb -
ing body heat when it evaporates. Energy as heat is absorbed from the
skin, causing the cooling effect.
Boiling is the change of a liquid to bubbles of vapor that appear
throughout the liquid. Boiling differs from evaporation, as you will see
in Section 4.

Formation of Solids
When a liquid is cooled, the average energy of its particles decreases.
If the energy is low enough, attractive forces pull the particles into an
even more orderly arrangement. The substance then becomes a solid.
/ lie physical change of a liquid to a solid by removal of energy as heat
is called freezing or solidification. Perhaps the best -known example of
FIGURE 8 Liquid bromine. Bn,
evaporates near room temperature. freezing is the change of liquid water to solid water, or ice, at 0°C.
The resulting brownish red gas Another familiar example is the solidification of paraffin at room tem -
diffuses into the air above the perature. All liquids freeze, although not necessarily at temperatures
surface of the liquid. you normally encounter. Ethanol, for example, freezes near - 114 C.

SECTION REVIEW .
4 Explain why liquids in a test tube form a meniscus.
.
1 Describe the liquid state according to the kinetic- .
5 Compare vaporization and evaporation.
molecular theory.
Critical Thinking
2. List the properties of liquids.
6. INTERPRETING CONCEPTS The evaporation of
3. How does the kinetic -molecular theory explain the liquid water from the surface of Earth is an impor-
following properties of liquids: (a) relatively high tant step in the water cycle. How do water mol-
density, (b) ability to diffuse, and (c) ability to ecules obtain enough kinetic energy to escape
evaporate? into the gas state?

336 CHAPTER 10
Solids SECTION 3

OBJECTIVES
Describe the motion of
T he common expression "solid as a rock ” suggests that something is particles in solids and the
hard or unyielding and has a definite shape and volume. In this section properties of solids according
you will examine the properties of solids and compare them with those to the kinetic -molecular theory.
of liquids and gases. The properties of solids are explained in terms of
the kinetic- molecular theory, as the other states of matter are. J Distinguish between the two
types of solids.

Properties of Solids and the >J Describe the different types

of crystal symmetry. Define
Kinetic - Molecular Theory crystal structure and unit cell.
The particles of a solid are more closely packed than those of a liquid or
gas. Intermolecular forces between particles are therefore much more
effective in solids. All interparticle attractions such as dipole-dipole
attractions. London dispersion forces, and hydrogen bonding exert C H E M I S T R Y a'f
stronger effects in solids than in the corresponding liquids or gases. 'OTO*
Attractive forces tend to hold the particles of a solid in relatively fixed Module 1 : States of Matter /Classes
of Matter
positions, with only vibrational movement around fixed points. Because
the motions of the particles are restricted in this way. solids are more
ordered than liquids and are much more ordered than gases. The impor -
tance of order and disorder in physical and chemical changes will be dis-
cussed in Chapter 16. Compare the physical appearance and molecular
arrangement of the element in Figure 9 in solid , liquid , and gas form. FIGURE 9 Particles of sodium
metal in three different states are
shown. Sodium exists in a gaseous
state in a sodium -vapor lamp.
Arrangement of Arrangement of Arrangement of
particles in a solid particles in a liquid particles in a gas

OOOOJO
6 °
J J j J J J J J

o
a o

STATES OF MATTER 337

 There are two types of solids: crystalline solids and amorphous solids.
Most solids are crystalline solids —they consist of crystals. A crystal is a
substance in w hich the particles are arranged in an orderly, geometric,
repeating pattern. Noncrystalline solids, including glass and plastics, are
called amorphous solids. An amorphous solid is one in which the parti-
cles are arranged randomly. The two types of solids will he discussed in
more detail later in this section .

Definite Shape and Volume

Unlike liquids and gases, solids can maintain a definite shape without a
container. In addition , crystalline solids are geometrically regular. Even
the fragments of a shattered crystalline solid have distinct geometric
shapes that reflect their internal structure. Amorphous solids maintain
a definite shape, hut they do not have the distinct geometric shapes of
crystalline solids. For example, glass can he molded into any shape. If it
is shattered , glass fragments can have a wide variety of irregular shapes.
The volume of a solid changes only slightly with a change in tempera -
ture or pressure. Solids have definite volume because their particles are
packed closely together. There is very little empty space into which the
particles can he compressed . Crystalline solids generally do not flow
because their particles are held in relatively fixed positions.

Definite Melting Point

Melting is the physical change of a solid to a liquid by the addition of
energy as heat. The temperature at which a solid becomes a liquid is its
melting point . At this temperature, the kinetic energies of the particles
within the solid overcome the attractive forces holding them together.
The particles can then break out of their positions in crystalline solids,
Sodium ion, Chloride ion,
Na + cr which have definite melting points. In contrast , amorphous solids, such
as glass and plastics, have no definite melting point . They have the abil -
— ity to flow over a range of temperatures. Therefore, amorphous solids
are sometimes classified as supercooled liquids, which are substances
that retain certain liquid properties even at temperatures at which they
appear to be solid . These properties exist because the particles in amor -
phous solids are arranged randomly, much like the particles in a liquid .
Unlike the particles in a true liquid , however, the particles in amor -
phous solids are not constantly changing their positions.

High Density and Incompressibility

( b) In general , substances are most dense in the solid state. Solids lend to be
slightly denser than liquids and much denser than gases. The higher den -
FIGURE 10 ( a ) This is a scanning sity results from the fact that the particles of a solid are more closely
electron micrograph ( SEN! ) of a packed than those of a liquid or a gas. Solid hydrogen is the least dense
sodium chloride crystal . A sodium
chloride crystal can he represented
.
solid ; it has a density of about 1/320 of the densest element , osmium Os.
Solids are generally less compressible than liquids. For practical pur -
by its crystal structure ( b ). which is
made up of individual unit cells poses, solids can be considered incompressible. Some solids, such as
represented regularly in three wood and cork , may seem compressible, but they are not . They contain
dimensions. Here, one unit cell is pores that are filled with air. When subjected to intense pressure, the
outlined in red. pores are compressed , not the solid matter in the wood or cork itself.

338 CHAPTER 10
 I

Fluorite Emerald
Cubic Tetragonal Hexagonal

A •
*1
L
VA .V
•u •
•/
r ' ijU*
;•
8,
KvSfi
. ; .v
m
v
V m XJ
i
i
.'
«

/
1.

Calcite
Trigonal
Ax Aragonite
Orthorhombic
Azurite
Monoclinic
*

Low Rate of Diffusion

II a zinc plate and a copper plate are clamped together for a long time,
a few atoms of each metal will diffuse into the other. This observation
shows that diffusion does occur in solids. The rate of diffusion is millions
of times slower in solids than in liquids, however.

Crystalline Solids
Rhodonite
Crystalline solids exist either as single crystals or as groups of crystals Triclinic
fused together. The total three -dimensional arrangement of particles of
a crystal is called a crystal structure. The arrangement of particles in the FIGURE 11 Shown are the seven
crystal can be represented by a coordinate system called a lattice. The basic crystalline systems and repre -
smallest portion of a cry slid lattice that shows the three - dimensional pat - sentative minerals of each .
tern of the entire lattice is called a unit cell . Each crystal lattice contains
many unit cells packed together. Figure 10 shows the relationship
between a crystal lattice and its unit cell . A crystal and its unit cells can
have any one of seven types of symmetry. This fact enables scientists to
classify crystals by their shape. Diagrams and examples of each type of
crystal symmetry are shown in Figure 11.

Binding Forces in Crystals

Crystal structures can also be described in terms of the types of parti -
cles in them and the types of chemical bonding between the particles.

STATES OF MATTER 339

 TABLE 1 Melting and Boiling Points of
Representative Crystalline Solids
Type of Melting Boiling point
substance Formula point (°C) at 1 atm (°C)
Ionic NaCl 801 1413
MgF2 126h 2239
Covalent network ( SiOi) , 1610 2230
Cv (diamond) 3500 3930
Metallic Hg -39 357
Cu 1083 2567
Fe 1535 2750
W 3410 5660
Covalent molecular Hi -259 -253
(nonpolar ) o2 -218 -183
CH4 - 182 -164
CCI4 -23 77
Q>H6 6 80
Covalent molecular NR* -78 -33
( polar ) HO . (I 100

According to this method of classification, there are four types of crys-

0fYtk>9*d Md MMtMwd by Ike tals. These types are listed in Table 1. Refer to this table as you read the
NattoMl SCMM* TMdwn AtuKutm
following discussion.
For a variety of links related to this
chapter, go to www.scilmks.org I 1. Ionic crystals. The ionic crystal structure consists of positive and neg-
Topic: Crystalline Solids
SciLinks code: HC60369
^ ative ions arranged in a regular pattern. The ions can be monatomic
or polyatomic. Generally, ionic crystals form when Group I or
Group 2 metals combine with Group 16 or Group 17 nonmetals or
nonmetallic polyatomic ions. The strong binding forces between the
positive and negative ions in the crystal structure give the ionic crys-
.
tals certain properties For example, these crystals are hard and brit -
tle. have high melting points, and are good insulators.
.
2 Covalent network crystals. In covalent network crystals, each atom is
covalently bonded to its nearest neighboring atoms. The covalent
bonding extends throughout a network that includes a very large num -
ber of atoms. Three-dimensional covalent network solids include dia -
mond. Cv. quartz, ( SiO:) v —shown in Figure 12—silicon carbide .
( SiC ) v , and many oxides of transition metals. Such solids are essential -
.
ly giant molecules The subscript x in these formulas indicates that the
component within the parentheses extends indefinitely. The network
solids are nearly always very hard and brittle. They have rather high
melting points and are usually nonconductors or semiconductors.
3. Metallic crystals. The metallic crystal structure consists of metal
cations surrounded by a sea of delocalized valence electrons. The
electrons come from the metal atoms and belong to the crystal as a
whole. The freedom of these delocalized electrons to move through -
out the crystal explains the high electric conductivity of metals.

340 CHAPTER 10
4. Covalent molecular crystals. The crystal structure of a covalent mo -
lecular substance consists of covalently bonded molecules held
.
together by intermolecular forces If the molecules are nonpolar—
for example, hydrogen, H2, methane, CH4 , and benzene, CftI \(,— then
there are only weak London dispersion forces between molecules.
In a polar covalent molecular crystal— for example, water, LUO, and
ammonia. NH3—molecules are held together by dispersion forces,
by somewhat stronger dipole-dipole forces, and sometimes by even
stronger hydrogen bonding. The forces that hold polar or nonpolar
molecules together in the structure are much weaker than the
covalent chemical bonds between the atoms within each molecule.
Covalent molecular crystals thus have low melting points. They are
easily vaporized, are relatively soft, and are good insulators.
Ice crystals, the most familiar molecular crystals, are discussed in
Section 5.

Amorphous Solids
The word amorphous comes from the Greek for “ without shape."
Unlike the atoms that form crystals, the atoms that make up amorphous
FIGURE 12 Covalent network
solids, such as glasses and plastics, are not arranged in a regular pattern.
crystals include three -dimensional
Glasses are made by cooling certain molten materials in a way that network solids, such as this quart / .
prevents them from crystallizing. The properties that result make ( Si02 ) t , shown here with its three -
glasses suitable for many uses, including windows, light bulbs, trans- dimensional atomic structure.
former cores, and optical fibers that carry telephone conversations .
Plastics, another type of amorphous solid, are easily molded at high
temperatures and pressures. They are used in many structural materials .
Other, more recently created amorphous solids have been placed in
.
many important applications Amorphous semiconductors are used in
.
electronic devices, including solar cells, copiers laser printers, and flat -
panel displays for computer monitors and television screens.

SECTION REVIEW 4. Compare and contrast the four types of crystals.

1. Describe the solid state according to the kinetic - 5. Why do crystalline solids shatter into regularly
molecular theory. shaped fragments when broken?
2. What is the difference between an amorphous Critical Thinking
solid and a crystalline solid?
6. RELATING IDEAS Explain why ionic crystals melt
3. Account for each of the following properties at much higher temperatures than typical covalent
of solids: (a) the definite volume, (b) the relatively molecular crystals?
high density of solids, (c) the extremely low rate
of diffusion.

STATES OF MATTER 341

 SECTION 4
Changes of State
OBJECTIVES
sj Explain the relationship M alter on Earth can exist in any of these states—gas. liquid or solid—
,

between equilibrium and and can change from one state to another. Table 2 lists the possible
changes of state. changes of stale. In this section, you will examine these changes of state
and the factors that determine them.
J Interpret phase diagrams.

a Explain what is meant by Changes of State and Equilibrium

equilibrium vapor pressure.
Some liquid chemical substances, such as rubbing alcohol, have an odor
^ Describe the processes of that is very easily detected. This is because some molecules at the upper
boiling, freezing, melting, and surface of the liquid have enough energy to overcome the attraction of
sublimation. neighboring molecules. These molecules leave the liquid phase and
evaporate. A phase is any pan of a system that has uniform composition
and properties. In a closed bottle of rubbing alcohol, the gas molecules
are confined to the area under the cap. Some of the gas molecules strike
the liquid surface and reenter the liquid phase through condensation.
CHEMISTRY I Condensation is the process by which a gas changes to a liquid. A gas in

Module 1 : States of Matter/Classes

of Matter
^ contact with its liquid or solid phase is often called a vapor.
If the temperature of the liquid remains constant and the cap
remains closed, the rate at which molecules move from the liquid phase
to the vapor phase remains constant. Near the beginning of the evapo -
ration process, very few molecules are in the gas phase, so the rate of
condensation is very low. But as more liquid evaporates, the increasing
number of gas molecules causes the rate of condensation to increase.
Eventually, the rate of condensation equals the rate of evaporation, and
a state of equilibrium is established, as shown in Figure 13. Equilibrium
is a dynamic condition in which two opposing changes occur at equal
rates in a closed system . Even though molecules are constantly moving

TABLE 2 Possible Changes of State

Change of state Process Example
SCllNKS. Of lop d mi
" '
M r>
iwliitd fry It
"
Solid > liquid melting ice > water
NjtioMl ktewr TMthm AuocutiM
Solid > gas sublimation dry ice » CO: gas
For a variety of links related to this
chapter, go to wmscilmks.org Liquid > solid freezing water > ice
Topic: Factors Affecting
Equilibrium
^ Liquid > gas vaporization liquid bromine > bromine vapor
Gas » liquid condensation water vapor > water
SciLinks code: HC60561
Gas > solid deposition water vapor ice

342 CHAPTER 10
 I*

#
•i %

* /
» 4 9 \
* *
i »
•m»•«« « 3 J
i
>
•• • »i
J J J

(0
• »
( b)

FIGURE 13 A liquid -vapor equilibrium develops in a closed system , ( a ) At

first there is only liquid present , hut molecules are beginning to evaporate,
( b ) Evaporation continues at a constant rate. Some vapor molecules are
beginning to condense to liquid ( c ) Equilibrium has been reached between
,

the rate of condensation and the rate of evaporation.

between liquid and gas phases, there is no net change in the amount of
substance in either phase.

Equilibrium Vapor Pressure of a Liquid

Vapor molecules in equilibrium with a liquid tn a closed system exert a
pressure proportional to the concentration of molecules in the vapor
phase. The pressure exerted by a vapor in equilibrium with its corre -
sponding liquid at a given temperature is called the equilibrium vapor
pressure of the liquid .
The increase in equilibrium vapor pressure with increasing tempera -
ture can be explained in terms of the kinetic- molecular theory for the
liquid and gaseous states. Increasing the temperature of a liquid increas-
Chemical Content
es the average kinetic energy of the liquid 's molecules. This energy
change increases the number of molecules that have enough energy to Go to go. hrw. com for more infor-
mation on equilibrium and changes
escape from the liquid phase into the vapor phase. The resulting
of state.
increased evaporation rate increases the number of molecules in the o /.
vapor phase, which in turn increases the equilibrium vapor pressure. Keyword: HC 6 STMX

Because all liquids have characteristic forces of attraction between

their particles, every liquid has a specific equilibrium vapor pressure at a
given temperature. The stronger these attractive forces are. the smaller
the percentage of liquid particles that can evaporate at any given tem -
perature is. A low percentage of evaporation results in a low equilibrium
vapor pressure is. Volatile liquids, which are liquids that evaporate readi -
ly, have relatively weak forces of attraction between their particles.
Ether is a typical volatile liquid. Nonvolatile liquids do not evaporate
readily, and have relatively strong attractive forces between their parti -
cles. Molten ionic compounds are examples of nonvolatile liquids.

STATES OF MATTER 343

 Boiling
Equilibrium vapor pressures can be used to explain and define the con -
cept of boiling, which you read about in Section 3. Moiling is the con -
version of a liquid to a vapor within the liquid as well as at its surface.
If the temperature of the liquid is increased, the equilibrium vapor
pressure also increases. The boiling point of a liquid is the temperature at
which the equilibrium vapor pressure of the liquid equals the atmospheric
pressure. The lower the atmospheric pressure is. the lower the boiling
point is.
At the boiling point , all of the ener -
Vapor Pressures of Diethyl Ether, Ethanol,
gy absorbed is used to evaporate the
and Water at Various Temperatures
liquid, and the temperature remains
760 torr = 101.3 kPa constant as long as the pressure does
800
= 1 atm not change. If the pressure above the
liquid being heated is increased, the
temperature of the liquid will rise
600 until the vapor pressure equals the
^o Diethyl ether / Ethanol
Normal Normal
Water
Normal
new pressure and the liquid boils once
a;
b , p. 34.6°C / b. p . 78.5°C b.p . 100.°C again. This is the principle behind the
S 400 operation of a pressure cooker. The
a. cooker is sealed so that steam pres-
sure builds up over the surface of the
200
boiling water inside. The pressure
increases the boiling temperature of
0 the water, resulting in shorter cooking
- 20 0 20 40 60 80 100 120 140 160 times. Conversely, a device called a
Temperature (°C) vacuum evaporator causes boiling
at lower- than - normal temperatures.
FIGURE 14 Hie vapor pressure of Vacuum evaporators are used to remove water from milk and sugar solu-
unv liquid increases ns its tempera - tions. Under reduced pressure, the water boils away at a temperature low
ture increases. A liquid boils when
enough to avoid scorching the milk or sugar. This process is used to pre -
its vapor pressure equals the pres-
pare evaporated milk and sweetened condensed milk .
sure ol the atmosphere.
At normal atmospheric pressure ( 1 atm, 760 torr, or 101.3 kPa), the
boiling point of water is exactly 100 C.This temperature is known as the
.
normal boiling point of water Figure 14 shows that the normal boiling
point of each liquid is the temperature at w hich the liquid's equilibrium
vapor pressure equals 760 torr .
Energy and Boiling
Energy must be added continuously in order to keep a liquid boiling. A
pot of boiling w ater stops boiling almost immediately after it is removed
from the stove. If you were to carefully measure the temperature of a
boiling liquid and its vapor you would find that they are at the same con-
stant temperature. The temperature at the boiling point remains constant
despite the continuous addition of energy. The added energy is used to
overcome the attractive forces between molecules of the liquid during the
liquid-to-gas change and is stored in the vapor as potential energy.

344 CHAPTER 10
 Energy Distribution of Molecules in a Liquid FIGURE 15 The number of mol-
at Different Temperatures ecules in a liquid with various kinetic
energies is represented at two differ -
Lower temperature ent temperatures. Notice the shaded
Higher temperature area, which shows the fraction of the
molecules that have at least the mini-
i/i
mum amount of kinetic energy
<D Minimum kinetic energy
3 required for evaporation to take
u required for escape of
CD place.
O molecules from surface
E of liquid
o
<D
-ED
3
z •% ••
••

Kinetic energy

Molar Enthalpy of Vaporization

The amount of energy as heat that is needed to vaporize one mole of liq -
uid at the liquid 's boiling point at constant pressure is called the liquid ' s
molar enthalpy of vaporization, A / /r The magnitude of the molar
enthalpy of vaporization is a measure of the attraction between parti -
cles of the liquid. The stronger this attraction is. the more energy that is
required to overcome it. which results in a higher molar enthalpy of
vaporization. Each liquid has a characteristic molar enthalpy of vapor -
ization. Compared w ith other liquids, water has an unusually high molar
enthalpy of vaporization due to the extensive hydrogen bonding in liq-
uid water. This property makes water a very effective cooling agent.
When water evaporates from your skin the escaping molecules carry a
,

great deal of energy as heat away with them. Figure 15 shows the dis -
tribution of the kinetic energies of molecules in a liquid at two different
temperatures. You can see that at the higher temperature, a greater por -
tion of the molecules have the kinetic energy required to escape from
the liquid surface and become vapor.

Freezing and Melting

As you learned in Section 2 . the physical change of a liquid to a solid is
called freezing. Freezing involves a loss of energy in the form of heal by
the liquid and can be represented bv the following reaction.
liquid
* solid + energy
In the case of a pure crystalline substance, this change occurs at constant
temperature. The normal freezing point is the temperature at which the
solid and liquid are in equilibrium at / atm ( 760 torn or 101.3 kPa ) pres -
sure. At the freezing point, particles of the liquid and the solid have the
same average kinetic energy. Therefore, the energy loss during freezing

STATES OF MATTER 345

 is a loss of potential energy that was present in the liquid. At the same
time energy decreases, there is a significant increase in particle order
because the solid stale of a substance is much more ordered than the liq -
uid state, even at the same temperature.
Melting, the reverse of freezing, also occurs at constant temperature.
As a solid melts, it continuously absorbs energy as heat, as represented
by the following equation.
Chemistry
J
in Action solid + energy » liquid
Surface Melting
Freezing of water and melting of ice For pure crystalline solids, the melting point and freezing point are
are phase changes that are familiar to the same. At equilibrium, melting and freezing proceed at equal rates,
all of us. Yet physicists and chemists rhe following general equilibrium equation can be used to represent
have only recently begun to understand these states.
the basic aspects of these phase
changes, with experimental and theo- solid + energy < > liquid
retical studies of a phenomenon known
as surface melting. Experimental stud-
ies in the mid- 1980s confirmed that the
At normal atmospheric pressure, the temperature of a system contain -
rigid surface arrangements of metals ing ice and liquid water will remain at 0. C as long as both ice and
can become increasingly disordered water are present. That temperature will persist no matter what the
several degrees below the melting surrounding temperature. Adding energy in the form of heat to such a
point of the metal, forming a " quasi- system shifts the equilibrium to the right . That shift increases the pro -
liquid layer." Many different techniques
portion of liquid water and decreases that of ice. Only after all the ice
have now shown that ice also has such
a fluid surface layer just a few mole - has melted will the addition of energy increase the temperature of the
cules thick. This surface melting of ice system.

might explain observations as diverse

as the origin of lightning, the unique Molar Enthalpy of Fusion
shapes of snowflakes, and ice skating. The amount of energy as heat required to melt one mole of solid at the
solid 's melting point is the solid 's molar enthalpy of fusion, A / /;. The
energy absorbed increases the solid’s potential energy as its particles
are pulled apart, overcoming the attractive forces holding them togeth -
er. At the same time, there is a significant decrease in particle order as
the substance makes the transformation from solid to liquid. Similar to
the molar enthalpy of vaporization the magnitude of the molar
,

enthalpy ol fusion depends on the attraction between the solid particles.

Sublimation and Deposition

At sufficiently low temperature and pressure conditions, a liquid cannot
exist . Under such conditions, a solid substance exists in equilibrium with
its vapor instead of its liquid, as represented by the following equation.

solid + energy -> vapor

I he change of state from a solid directly to a gas is known as sublima-

tion. The reverse process is called deposition, the change of state front a
gas directly to a solid . Among the common substances that sublime at
ordinary temperatures are dry ice ( solid CQ:) and iodine. Ordinary ice
sublimes slowly at temperatures lower than its melting point ( 0. C ).
This explains how a thin layer of snow can eventually disappear, even
if the temperature remains below 0. C. Sublimation occurs in frost - free

346 CHAPTER 10
refrigerators when the temperature in the freezer compartment is peri -
odically raised to cause any ice that has formed to sublime. A blower
then removes the water vapor that has formed. The formation of frost
on a cold surface is a familiar example of deposition .

Phase Diagrams
A phase diagram is a graph of pressure versus temperature that slums the
conditions under which the phases of a substance exist . A phase diagram
also reveals how the states of a system change with changing tempera -
ture or pressure.
Figure 16 shows the phase diagram for water over a range of tem -
peratures and pressures. Note the three curves. AB. AC. and AD. Curve
AB indicates the temperature and pressure conditions at which ice and CROSS - DISCIPLINARY
water vapor can coexist at equilibrium . Curve AC indicates the temper- Go to go.hrw.com for a full - length
ature and pressure conditions at which liquid water and water vapor article on how cloud seeding is used
to produce precipitation .
coexist at equilibrium. Similarly, curve AD indicates the temperature
and pressure conditions at which ice and liquid water coexist at equilib- $ Keyword: HC 6 STMX
rium . Because ice is less dense than liquid water, an increase in pressure
lowers the melting point. ( Most substances have a positive slope for this
curve.) Point A is the triple point of water. The triple point of a sub -
stance indicates the temperature and pressure conditions at which the
solid , liquid . and vapor of the substance can coexist at equilibrium. Point
C is the critical point of water. The critical point of a substance indicates
the critical temperature and critical pressure. The critical temperature
i t . ) is the temperature above which the substance cannot exist in the liq -
uid state. The critical temperature of water is 373.99 C. Above this

Phase Diagram for H20

D Critical point
217.75
Critical
^
pressure

Liquid
E
<T5 Normal
<U freezing
3 point
\A
V"l 1.00
cu Normal
CL boiling
Solid
point
A
0.0060
Triple Vapor
B point FIGURE 16 This phase
0.00 0.01 100.00 373.99 diagram shows the relationships
Critical between the physical states of water
Temperature (°C) temperature and its pressure and temperature.

STATES OF MATTER 347

 FIGURE 17 Solids, liquids, and
gases can undergo various changes
of state. The changes shown in green
are exothermic, and those shown in
blue are endothermic.

temperature, water cannot be liquefied, no matter how much pressure

is applied. The critical pressure ( !\ ) is the lowest pressure tit which the
Chemistry' in Action substance can exist as a lie/ aid at the critical temperature. Ilic critical
Go to go.hrw. com for a full- length pressure of water is 217.75 atm.
article on phase - change materials. The phase diagram in Figure 16 indicates the normal boiling point and
Keyword: HC 6 STMX the normal freezing point of water. It also shows how boiling point and
freezing point change with pressure. As shown by the slope of line AD ice.
melts at a higher temperature with decreasing pressure. Below the triple
point, the temperature of sublimation decreases with decreasing pressure.
Foods are freeze-dried by freezing the food and then lowering the pres-
sure to cause the ice in the food to sublime rather than melt. Figure 17
summarizes the changes of state of solids, liquids, and gases.

SECTION REVIEW Critical Thinking

1. What is equilibrium ? 7. INTERPRETING GRAPHICS Refer to the phase dia -
2. What happens when a liquid-vapor system at gram for water on page 347 to answer the follow -
equilibrium experiences an increase in tempera- ing questions.
ture ? What happens when it experiences a a. Describe all the changes a sample of solid water
decrease in temperature ? would undergo when heated from -10°C to its
3. What would be an example of deposition ? critical temperature at a pressure of 1.00 atm.
4. What is the equilibrium vapor pressure of a liquid? b. Describe all the changes a sample of water
How is it measured ? vapor would undergo when cooled from 110°C
to 5°C at a pressure of 1.00 atm.
5. What is the boiling point of a liquid?
c. At approximately what pressure will water
6. In the phase diagram for water, what is meant be a vapor at 0°C ?
by the triple point and the critical point ?
d. Within what range of pressures will water
be a liquid at temperatures above its normal
boiling point ?

348 CHAPTER 10
 SECTION 5
Water
OBJECTIVES
«J Describe the structure of a
W ater is a familiar substance in all three physical states: solid , liquid , water molecule.
and gas. On Earth , water is by far the most abundant liquid . Oceans,
rivers, and lakes cover about 75 % of Earth 's surface. Significant quanti - j Discuss the physical properties
ties of water are also frozen in glaciers. Water is an essential component of water. Explain how they
of all organisms: 70% to 90% of the mass of living things is water. The are determined by the
chemical reactions of most life processes take place in water, and water structure of water.
is frequently a reactant or product in such reactions. In order to better
understand the importance of water , let us take a closer look at its struc-
Calculate the amount of
ture and its properties.
energy absorbed or released
when a quantity of water
changes state.

Structure of Water
As discussed in Chapter 6, water molecules consist of two atoms of
hydrogen and one atom of oxygen united by polar-covalent bonds.
Research shows that a water molecule is bent . The structure can be rep- A Hydrogen
\
resented as follows. bond

•
O'
m 4 *
%

s*
H ^H
105°
#
* I

The angle between the two hydrogen -oxygen bonds is about 105 . This
is close to the angle expected for sp ' hybridization of the oxygen atom - #
orbitals. / i

The molecules in solid or liquid water are linked by hydrogen bond - 3

ing. The number of linked molecules decreases with increasing tempera -
ture because increases in kinetic energy make hydrogen bond
* 4 4
formation difficult. Nevertheless, there are usually from four to eight
4 *
molecules per group in liquid water, as shown in Figure 18. If it were not
for these molecular groups, water would be a gas at room temperature.
4
Nonpolar molecules, such as methane. CH 4. that are similar in size and Liquid water
mass to water molecules do not undergo hydrogen bonding. Such sub-
stances are gases at room temperature. FIGURE 18 The structure of
liquid water shows that within the
Ice consists of water molecules in the hexagonal arrangement show n
water molecule, oxygen and hydro-
in Figure 19. The empty spaces between molecules in this pattern gen are covalently bonded to each
account for the relatively low density of ice. As ice is heated , the other, while the molecules are held
increased energy of the molecules causes them to move and vibrate together in groups by hydrogen
more vigorously. W hen the melting point is reached , the energy of the bonds.

STATES OF MATTER 349

 molecules is so great that the rigid open structure of the ice crystals
breaks down, and ice turns into liquid water.
Figures IS and 19 also show that the hydrogen bonds between mole -
cules of liquid water at 0. C are fewer and more disordered than those
between molecules of ice at the same temperature. Because the rigid
open structure of ice has broken down, water molecules can crowd clos-
•
• » er together. Thus, liquid water is denser than ice.
As the liquid water is warmed from 0. C. the water molecules crowd
still closer together. Water molecules are as tightly packed as possible at
3.98 'C. At temperatures above 3.98 C. the increasing kinetic energy of
the water molecules causes them to overcome molecular attractions.
Hydrogen The molecules move farther apart as the temperature continues to rise.
bond
As the temperature approaches the boiling point, groups of liquid water
molecules absorb enough energy to break up into separate molecules.
-
* Because of hydrogen bonding between water molecules, a high kinetic
energy is needed, causing water 's boiling point to be relatively high
( 100. ( ) compared to other liquids that have similar molar masses.
'

Ice * Physical Properties of Water

FIGURE 19 Ice contains the same
types of bonding as liquid water.
However, the structure of the hydro- At room temperature, pure liquid water is transparent, odorless, taste -
gen bonding is much more rigid and less. and almost colorless. Any observable odor or taste is caused bv
.
open than it is in liquid water impurities, such as dissolved minerals, liquids, or gases.
As shown by its phase diagram in Figure 16, water freezes and ice
melts at 0. C at a pressure of 1 atm ( 101.3 kPa). The molar enthalpy of
fusion of ice is 6.009 kJ mol. That value is relatively large compared with
the molar enthalpy of fusion of other solids. As you have read, water has
the unusual property of expanding in volume as it freezes, because its
molecules form an open rigid structure. As a result, ice at 0. C has a den-
sity of only about 0.917 g/cnr\ but liquid water at 0. C has a density of
0.999 S4 g/env\
This lower density explains why ice floats in liquid water. The insu-
lating effect of floating ice is particularly important in the case of large
bodies of water. If ice were more dense than liquid water, it would sink
to the bottom of lakes and ponds, where it would be less likely to melt
completely. The water of such bodies of water in temperate climates
would eventually freeze solid, killing nearly all the living things in it .
Under a pressure of 1 atm ( 101.3 kPa ). water boils at 100. C. At this
temperature, water 's molar enthalpy of vaporization is 40.70 kJ / mol.
Both the boiling point and the molar enthalpy of vaporization of water
are quite high compared with those of nonpolar substances of compa -
rable molecular mass, such as methane. The values are high because of
the strong hydrogen bonding that must be overcome for boiling to
occur. The high molar enthalpy of vaporization makes water useful for
household steam-heating systems. The steam ( vaporized water ) stores
a great deal o! energy as heat. When the steam condenses in radiators,
great quantities of energy are released.

350 CHAPTER 10
 SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.

How much energy is absorbed when 47.0 g of ice melts at STP? How much energy is absorbed when this
same mass of liquid water boils?

SOLUTION
1 ANALYZE Given: mass of H:Q ( .v ) = 47.0 g; mass of H:0( / ) = 47.0 g; molar enthalpy of fusion of
ice = 6.009 kJ/mol; molar enthalpy of vaporization = 40.79 kJ/mol
Unknown: energy absorbed when ice melts; energy absorbed when liquid water boils

2 PLAN First , convert the mass of water from grams to moles.

I mol H:Q
47.0 H:Ox = 2.61 mol H:0
^ IS.02 g \ \ : O
Then, use the molar enthalpy of fusion of a solid to calculate the amount of energy
absorbed when the solid melts. Multiply the number of moles by the amount of energy
needed to melt one mole of ice at its melting point ( the molar enthalpy of fusion of ice ) .
I sing the same method, calculate the amount of energy absorbed when water boils bv
using the molar enthalpy of vaporization.
amount of substance ( mol ) x molar enthalpy of fusion or vaporization ( kJ/ mol ) = energy ( kJ )

3 COMPUTE 2.61 mot x 6.009 kJ / mof = 15.7 kJ ( on melting)

2.61 tfkvTx 40.79 kJ / nxTt = 106 kJ ( on vaporizing or boiling)

4 EVALUATE Units have canceled correctly. The answers have the proper number of significant digits and
are reasonably close to estimated values of IS ( 3 x 6 ) and 120 (3 x 40 ). respectively.

PRACTICE Answers in Appendix E

1. What quantity of energy is released when 506 g of liquid water Go to go.hrw.com for
freezes? more practice problems
that ask you to use
2. What mass of steam is required to release 4.97 x HP kJ of energy enthalpies to calculate
on condensation ? energies absorbed or
released.
Keyword: HC 6 STMX

SECTION REVIEW 5. Why is ice less dense than liquid water ?

1. Why is a water molecule polar ? 6. Is more energy required to melt one gram of ice at
2. How is the structure of water responsible for 0°C or to boil one gram of water at 100°C ? How
some of water's unique characteristics? do you know ?
3. Describe the arrangement of molecules in Critical Thinking
liquid water and in ice. 7. RELATING IDEAS Why is exposure to steam
4. Why does ice float ? Why is this phenomenon dangerous ?
important ?

STATES OF MATTER 351

 CHAPTER HIGHLIGHTS
The Kinetic- Molecular Theory of Matter
I Vocabulary •The kinetic-molecular theory of matter can he used to explain
kinetic - molecular diffusion the properties of gases, liquids, and solids.
theory effusion •The kinetic-molecular theory of gases describes a model of an
ideal gas real gas ideal gas.
elastic collision •Gases consist of large numbers of tiny, fast-moving particles that
are far apart relative to their size.

Liquids
I Vocabulary •The particles of a liquid arc closer together and more ordered
fluid vaporization than those of a gas and are less ordered than those of a solid.
surface tension evaporation •Liquids have a definite volume and a fairly high density, and
capillary action freezing they are relatively incompressible. Like gases, liquids can flow
and thus are considered to be fluids.

Solids
I Vocabulary •The particles of a solid are not nearly as free to move about as
crystalline solids melting point those of a liquid or a gas are.
crystal supercooled liquids •Solids have a definite shape and may be crystalline or amor-
amorphous solids crystal structure phous. They have a definite volume and are generally nonfluid.
melting unit cell •A crystal structure is the total three-dimensional array of points
that describes the arrangement of the particles of a crystal.
•Unlike crystalline solids, amorphous solids do not have a highly
ordered structure or a regular shape.

Changes of State
I Vocabulary •A liquid in a closed system will gradually reach a liquid-vapor
phase freezing point equilibrium as the rate at which molecules condense equals the
condensation molar enthalpy of rate at which they evaporate.
equilibrium fusion •When two opposing changes occur at equal rates in the same
equilibrium vapor sublimation closed system, the system is said to be in dynamic equilibrium.
pressure deposition
volatile liquids phase diagram
boiling triple point
boiling point critical point
molar enthalpy of critical temperature
vaporization critical pressure

Water
•Water is a polar covalent compound.
•The structure and the hydrogen bonding in water are responsi-
ble for its relatively high melting point, molar enthalpy of
fusion, boiling point, and molar enthalpy of vaporization.

352 CHAPTER 10
 CHAPTER REVIEW

The Kinetic-Molecular Changes of State

Theory of Matter SECTION 4 REVIEW
13 . Using Figure 14, estimate the approximate
SECTION 1 REVIEW
equilibrium vapor pressure of each of the fol-
1. What idea is the kinetic - molecular theory
lowing at the specified temperature.
based on ? a. water at 80 C
2. What is an ideal gas?
b. diethyl ether at 20 C
3. State the five basic assumptions of the kinetic -
c. ethanol at 60 C
molecular theory. 14 . a. What is sublimation?
4. How do gases compare with liquids and solids in b. Give two examples of common substances
terms of the distance between their molecules?
that sublime at ordinary temperatures.
5 . What is the relationship between the tem - .
15 What is meant by the normal freezing point of a
perature. speed, and kinetic energy of gas substance ?
molecules? 16. Explain how the attractive forces between the
6. a. What is diffusion? particles in a liquid are related to the equilibri-
b. What factors affect the rate of diffusion of um vapor pressure of that liquid.
one gas through another? 17. Explain the relationship between atmospheric
pressure and the actual boiling point of a liquid.
18. Explain the relationship between the molar
Liquids enthalpy of fusion of a solid and the strength of
SECTION 2 REVIEW attraction between that solid s particles.
'

7. What is a fluid?
8. What is surface tension? PRACTICE PROBLEMS
9 . Give two reasons why evaporation is a crucial 19. a. The molar enthalpy of vaporization for water
process in nature. is 40.79 kJ/mol. Express this enthalpy of
vaporization in joules per gram,
b. The molar enthalpy of fusion for water is
Solids 6.( X)9 kJ/mol. Express this enthalpy of fusion
SECTION 3 REVIEW in joules per gram.
20. Calculate the molar enthalpy of vaporization of a
10. List six properties of solids, and explain each in
substance given that 0.433 mol of the substance
terms of the kinetic -molecular theory of solids.
absorbs 36.5 kJ of energy when it is vaporized.
.
11 List four common examples of amorphous
21. Given that a substance has a molar mass of
solids.
259.0 g/mol and a 71.8 g sample of the sub -
12. List and describe the four types of crystals in
stance absorbs 4.307 kJ when it melts,
terms of the nature of their component particles
and the type of bonding between them.
.
a calculate the number of moles in the sample.
b. calculate the molar enthalpy of fusion.
22. a. Calculate the number of moles in a liquid
sample of a substance that has a molar
.
enthalpy of fusion of 3.811 kJ/mol given that
the sample releases 83.2 kJ when it freezes,
b. Calculate the molar mass of this substance if
the mass of the sample is 5519 g.

STATES OF MATTER 353

 CHAPTER REVIEW

32 . What volume and mass of steam at 100. C and

Water 760. torr would release the same amount of
SECTION 5 REVIEW energy as heat during condensation as 65.5 cm '
23. Describe the structure of a water molecule. of liquid water would release during freezing?
24 . List at least eight physical properties of water. 33. The following liquid-vapor system is at equilib-
rium at a given temperature in a closed system.
liquid + energy; > vapor
PRACTICE PROBLEMS
Suppose the temperature is increased and equi -
25 . Which contains more molecules of water: librium is established at the higher temperature.
5.00 cm ' of ice at 0 C or 5.00 cm ' of liquid How does the final value of each of the follow -
water at 0. C? How many more ? What is the ing compare with its initial value? ( In each case,
ratio of the numbers of molecules in these two answer either higher, lower, or the same.)
samples? a. the rate of evaporation
26. a. What volume and mass of steam at 100. C b. the rate of condensation
and 1.00 atm would release the same amount c. the final concentration of vapor molecules
of energy during condensation as 100. cm ' of d. the final number of liquid molecules
liquid water would release during freezing? 34. Given a sample of water at any point on curve
b. What do you note, qualitatively, about the rel - AH in Figure 16, what effect would each of the
ative volumes and masses of steam and liquid following changes have on that sample ?
water required to release the same amount of a. adding energy at constant pressure
heat ? ( Hint: See Sample Problem A ) b. decreasing the volume at constant temperature
c. removing energy at constant pressure
d. increasing the volume at constant temperature
MIXED REVIEW 35. Using the phase diagram for CO: describe all.
the phase changes that would occur when CCL
27. Find the molar enthalpy of vaporization for a
is heated from - 100 C to - 10 C at a constant
substance, given that 3.21 mol of the substance
pressure of 6 atm.
absorbs 2S.4 kJ of energy as heat when the sub -
stance changes from a liquid to a gas.
28. Water 's molar enthalpy of fusion is 6.009 kJ / mol.
C02 Phase Diagram
Calculate the amount of energy as heat required
to melt 7.95 x HP g of ice. 16
29. A certain substance has a molar enthalpy of Liquid
14
vaporization of 31.6 kJ/mol. How much of the Solid
substance is in a sample that requires 57.0 kJ to ? 12
vaporize ? fz
10
30. Given that water has a molar enthalpy of vapor - 0J
a 8
ization of 40.79 kJ /mol. how many grams of ISI
\A
<u Gas
water could be vaporized by 0.545 kJ? CL 6
31 . Calculate the amount of energy released as heat
4
by the freezing of 13.3 g of a liquid substance,
given that the substance has a molar mass of 2
82.9 g/mol and a molar enthalpy of fusion of 0
4.60 kJ/mol. -100 - 80 - 60 - 40 - 20 0 + 20 +40 +60
Temperature (°C)

354 CHAPTER 10
 CHAPTER REVIEW

c. The body-centered cubic lattice is the least -

CRITICAL THINKING
efficient packing structure of the metals.
36. Interpreting Concepts During the freezing of a What elements in Groups 1 and 2 show this
substance, energy is being removed from that sub- arrangement ?
stance. Yet the temperature of the liquid-solid sys-
tem remains constant. Explain this phenomenon.

37. Applying Models At normal atmospheric pres- RESEARCH & WRITING

sure. the temperature of an ice- water system 41. Ceramics are formed from silicates found in the
remains at 0 C as long as both ice and liquid soil. Artists use them to create pottery, but engi-
water are present, regardless of the surrounding neers and scientists have created ceramics with
temperature. Explain why this occurs . superconductive properties. Investigate the
38. Predicting Outcomes Given a sample of water growing field of superconductive ceramics.
at any point on curve AD in Figure 16, how 42. Liquid crystals are substances that possess the
could more of the liquid water in that sample be combined properties of both liquids and crys-
converted into a solid without changing the tals. Write a report on these substances and the
temperature? Explain your reasoning. various uses we are finding for them.
39. Interpreting Diagrams Refer to the phase dia-
gram in question 44.
a. Explain what happens when solid CO: ( “dry ALTERNATIVE ASSESSMENT
ice ' ) warms up to room temperature at nor -
*

43 . Compile separate lists of crystalline and amor -

mal atmospheric pressure.
phous solids found in your home. Compare your
b. Is there a pressure below which liquid C02
lists w ith those of your classmates.
cannot exist ? Estimate that pressure from
44. Design an experiment to grow crystals of vari-
the graph. .
ous safe, common household materials Record
the conditions under which each type of crystal
is best grown.
USING THE HANDBOOK
40. The Elements Handbook contains a table of
properties for each group that includes informa-
tion on the crystal structures of the elements.
Most metals crystallize in one of three lattice
arrangements: body -centered cubic, lace-
centered cubic, or hexagonal close-packed.
Figure 10 shows a model of the face -centered
cubic lattice for sodium chloride. Use this figure —ryrtTrTEftaTi
and the information in the Elements Handbook
to answer the following.
a. What elements in Group 2 have the same lat -
s Graphing Calculator
Vapor Pressure
Go to go.hrw.com for a graphing calculator
tice structure as sodium chloride? exercise that asks you to create a graph of
b. How would the model of an element in a the vapor pressure of water as a function
face -centered cubic lattice differ from the of temperature.
compound shown in Figure 10?
Keyword: HC 6 STMX

STATES OF MATTER 355

 Math Tutor CALCULATIONS USING ENTHALPIES OF FUSION

When one mole of a liquid freezes to a solid, energy is released as attractive forces
between particles pull the disordered particles of the liquid into a more orderly crys-
talline solid. When the solid melts to a liquid, the solid must absorb the same quantity
of energy in order to separate the particles of the crystal and overcome the attractive
forces opposing separation. This quantity of energy used to melt or freeze one mole of
a substance at its melting point is called its molar enthalpy of fusion, AH .,
Problem-Solving TIPS
• The enthalpy of fusion of a substance can he given as either joules per gram
or kilojoules per mole.
• Molar enthalpy of fusion is most commonly used in calculations.
• The enthalpy of fusion is the energy absorbed or given off as heat when a
substance melts or freezes at the melting point of the substance.
• No net change in temperature occurs as the stale change occurs.

SAMPLE 1 SAMPLE 2
7.30 kJ of energ) is required to melt 0.650 mol of Determine the* quantity of energy that will he
ethylene glycol ( C2H6(> 2 ) at its melting point . needed to melt 2.50 x 10 kg of iron at its melting
'

Calculate the molar enthalpy of fusion, AH of eth- point , 1536°C. The AHjoiiron is 13.807 kJ/mol.
ylene glycol and the energy absorbed. ^ To calculate the number of moles of iron, use
the equation below.
molar enthalpy of fusion = AHf =
mass of substance
moles of substance =
energy absorbed molar mass of substance
moles of substance Next , use the following equation for energy as
heat absorbed.
7.30 kJ kJ
A / 1 f .eihvlcne glycol
0.065 mol
= 11.2
mol ,
energy absorbed = AH x moles of substance
Now. substitute the calculation for moles of
substance, and solve.
energy absorbed =
grams of substance
AHff x
molar mass of substance
kJ 2.50 x 10x g Fe
13.807 — x
mol 55.847 g Fe /mol Fe
energy absorbed = 6.18 x 10 kJ
PRACTICE PROBLEMS
.
1 Calculate the molar enthalpy of fusion of sil - .
2 What quantity of energy in kJ must be
ver if 1.940 mol of silver requires 22.60 kJ of absorbed by 6.47 mol of solid acetic acid.
energy to change from a solid to a liquid at its .
C:Il40: to melt it at its melting point. 16.7 C?
melting point 961 C. . Hie AHf [ ox acetic acid is 11.54 kJ/mol.

356 CHAPTER 10
Answer the following items on a separate piece of paper. 7 . The kinetic- molecular theory slates that ideal
MULTIPLE CHOICE
gas molecules
A . are in constant , rapid random motion.
1. Surface tension is
,

A. skin on the surface of a liquid.

.
B have mass and take up space.
C. exert forces of attraction and repulsion on
B. the tendency of the surface of liquids to
each other.
decrease the area . D. have high densities compared with liquids
C. the spontaneous mixing of two substances.
and solids.
D. the same as vapor pressure.
SHORT ANSWER
2. Pure liquids boil at higher temperatures under
high pressures than they do under low pres- 8. Using this graph of vapor pressures of sub -
sures. because stances at various temperatures, estimate the
A . the molecules of liquid are closer together boiling point of ethanol at an applied ( external )
under higher pressures. pressure of 300 torr.
.
B it takes a higher temperature for the vapor
pressure to equal the higher external pressure.
800
C. the molecules of vapor are farther apart
under higher pressures.
D. the vapor diffuses more rapidly at higher 600
pressures. Diethyl ether Ethanol

3. The formation of frost is an example of

A . condensation . 400
B. evaporation. -
Q
Water
C. deposition.
200
D. melting point .
.
4 The graph that shows the pressure and temper -
ature conditions under which the phases of a 0
substance exist is called -20 0 20 40 60 80 100

A . a phase diagram. Temperature (°C)

B. a vapor pressure curve. 9 . It is found that 60.0 J of energy are required to
C. a unit cell . melt 15 g of a substance. 'Hie molar mass of the
D. the kinetic- molecular theory of matter. substance is 120 g/mol. Calculate the enthalpy of
5 . Water boils at 100 C. Ethanol boils at 78.5 C. fusion of the substance in kilojoules per mole.
Which of the following statements is true? EXTENDED RESPONSE
A . Water has the higher vapor pressure at 78.5 C.
10. Describe how a pressure cooker works.
B. Ethanol has the higher vapor pressure at
78.5*0. 11 . What is meant by the statement that a liquid
C. Both have the same vapor pressure at 78.5 C. and its vapor in a closed container are in a state
D. Vapor pressure is not related to boiling point . of dynamic equilibrium ?
6. Which of the following is not a property of typi -
cal solids?
A . definite melting point Test questions are not necessari-
ly arranged in order of increasing difficulty. If you are
B. high density
unable to answer a question, mark it and move on to
C. easily compressible other questions.
D. low rate of diffusion

STATES OF MATTER 357

 MICRO -
EXPERIMENT 10 L A B

ii
Wet” Dry Ice
OBJECTIVES
• Interpret a phase diagram. rN
o
u Solid
• Observe the melting of C02 while varying Liquid
pressure. o
?
*- > X
• Relate observations of C02 to its phase 03 Normal Triple
diagram. <D boiling, point
3
v/l point Gas
v/1
<D 1.0
MATERIALS CL

• 4-5 g C( ) 2 as dry ice, broken into -78 - 56

rice-sized pieces Temperature (°C) of C02

• forceps
FIGURE A The phase diagram for C02 shows the temperatures and
• metric ruler pressures at which C02 can undergo phase changes.
• plastic pipets. 5 mL, shatterproof
BACKGROUND
• pliers
The phase diagram for carbon dioxide in Figure A
• scissors shows that C02 can exist only as a gas at ordinary
• transparent plastic cup room temperature and pressure. To observe the tran -
sition of solid CO: to liquid CO:, you must increase
the pressure until it is at or above the triple point
pressure, which is labeled X in the diagram .

SAFETY

For review of safety, please see Safety in the

Chemistry Laboratory in the front of your book .

PREPARATION
1 . Organize a place in vour lab notebook for
recording your observations.

PROCEDURE
1 . Use forceps to place 2-3 very small pieces of dry
ice on the table, and observe them until they
have completely sublimed . Caution: Dry ice will
freeze skin very quickly. Do not attempt to pick
up the dry ice with your fingers.

358 CHAPTER 10
 EXPERIMENT 10

2. Fill a plastic cup with tap water to a depth of CLEANUP AND DISPOSAL
4-5 cm. 9. Clean all apparatus and your lab station .
3. Cut the tapered end ( tip ) off the graduated pipet . Return equipment to its proper place.
Dispose of chemicals and solutions in
4. Use forceps to carefully slide 8-10 pieces of dry the containers designated by your teacher. Do
ice down the stem and into the bulb of the pipet . not pour any chemicals down the drain or place
5 . Use a pair of pliers to clamp the opening of them in the trash unless your teacher directs you
the pipet stem securely shut so that no gas can to do so. Wash your hands thoroughly before you
escape. Use the pliers to hold the tube and to leave the lab and after all work is finished .
lower the pipet into the cup just until the bulb is
submerged , as shown in Figure B. From the side ANALYSIS AND INTERPRETATION
of the cup. observe the behavior of the dry ice. 1. Analyzing Results: What differences did you
observe between the subliming and the
6. As soon as the dry ice has begun to melt , quick -
melting of C02?
ly loosen the pliers while still holding the bulb
in the water. Observe the C02. 2. Analyzing Methods: As you melted the CO:
sample over and over, why did it eventually
7. Tighten the pliers again , and observe.
disappear? What could you have done to make
8. Repeat Procedure steps 6 and 7 as many times the sample last longer ?
as possible.
3. Analyzing Methods: What purpose ( s ) do you
suppose the water in the cup served?
Pliers
/ EXTENSIONS
K
1. Predicting Outcomes: What would have hap-
pened if fewer pieces of dry ice ( only 1 or 2 )
n had been placed inside the pipet bulb? If time
permits, test your prediction .
2. Predicting Outcomes: What might have hap-
pened if too much dry ice ( 20 or 30 pieces, for
example ) had been placed inside the pipet bulb ?
How quickly would the process have occurred ?
If time permits, test your prediction .
Water
3. Predicting Outcomes: What would have
happened if the pliers had not been released
once the dry ice melted ? If time permits, test
your prediction .

FIGURE B Clamp the end of the pipet shut with the pliers.
Submerge the bulb in water in a transparent cup.

STATES OF MATTER 359

 CHAPTER 11

The density of a gas decreases

as the temperature of the gas increases.
Gases and Pressure SECTION 1

OBJECTIVES
sj Define pressure, give units of
In the chapter “ States of Matter. you read about the kinetic -
'*
pressure, and describe how
molecular theory, which is based on the idea that particles of matter are pressure is measured.
always in motion. In this section, you will study the implications of the
kinetic -molecular theory of gases. State the standard conditions
‘j
You have learned that the temperature of a gas is related to the of temperature and pressure
kinetic energy of the gas molecules. In this chapter, you will learn about and convert units of pressure.
other properties of gases, including pressure, volume, and amount of gas
present, and the relationship between these properties.
SJ Use Dalton 's law of partial
pressures to calculate partial
pressures and total pressures.

Pressure and Force

If you pump air into an automobile tire, the pressure in the tire will
increase. The pressure increase is caused bv the increase in the number
of collisions of molecules of air with the inside walls of the tire. Hie col-
lisions cause an outward push, or force, against the inside walls. Gas
molecules exert pressure on any surface with which they collide. The FIGURE 1 The pressure the bal-
pressure exerted by a gas depends on volume, temperature, and the let dancer exerts against the floor
number of molecules present. Pressure IP ) is defined us the force pet- depends on the area of contact.
unit urea on it surface. The equation defining pressure is shown in The smaller the area of contact, the
Figure 1. greater the pressure.

Force = 500 N Force = 500 N Force = 500 N

\
%
(a) Area of contact = 325 cm * (b) Area of contact = 13 cm2 (c) Area of contact = 6.5 cnV
Pressure = force Pressure = force Pressure = force
area area area
= 500 N = 1.5 N/cm2 = 500 N = 38 N/cm2 = 500 N = 77 N/cm2
325 cm 2 13 cm2 6.5 cm

GASES 361
 The SI unit for force is the newton, ( N ). It is the force that will
increase the speed of a one - kilogram mass by one meter per second each
second that the force is applied . At Earth 's surface, gravity has an accel -
eration of 9.8 m /s2. Consider a ballet dancer with a mass of 51 kg, as
shown in Figure 1. A mass of 51 kg exerts a force of 500 N ( 51 kg x
9.8 m/s2 ) on Earth 's surface. No matter how the dancer stands, she
CHEMISTRY A . exerts that much force against the floor. But the pressure exerted
against the floor depends on the area of contact. When the dancer rests
Module 6 : Gas Laws
her weight on the soles of both feet, as shown in Figure la, the area of
contact with the floor is about 325 cm2. The pressure, or force per unit
area, when she stands in this manner is 500 N/325 cm 2, or roughly
1.5 N/cm2. When she stands on her toes, as in Figure lb, the total area of
contact with the floor is only 13 cm2. The pressure exerted is then equal

SCllNKS Dmtoptd
kM r *
iMiaUMtd fey ri»
to 500 N/ 13 cm2 —roughly 38 N/cm2. And when she stands on one toe. as
in Figure 1c, the pressure exerted is twice that, or about 77 N/cm2. Thus,
NJhwul Stimu iMriwn AIMCMUM

For a variety of links related to this

the same force applied to a smaller area results in a greater pressure .
chapter, go to . . . , Q! rg * .
The atmosphere — the shell of air surrounding Earth —exerts pres -
Topic: Gases sure. Figure 2 shows that atmospheric pressure at sea level is about
SciLinks code: HC60638 equal to the weight of a 1.03 kg mass per square centimeter of surface,
or 10.1 N /cm 2. The pressure of the atmosphere can be thought of as
caused by the weight of the gases that compose the atmosphere. The
.
atmosphere contains about 78 % nitrogen 21 % oxygen, and 1 % other
.
gases, including argon and carbon dioxide Atmospheric pressure is the
sum of the individual pressures of the various gases in the atmosphere.
Your ears “pop" when you flv in an airplane because the density—
and therefore the pressure—of the air is lower at higher altitudes The .
FIGURE 2 Air molecules— most
popping happens when the air pressure inside your ears changes to
of which are nitrogen or oxygen— reach the same pressure as the air inside the cabin.
collide with Earth's surface, creating
a pressure of 10.1 N/cnr .

Oxygen molecule, 02 Nitrogen molecule, N2

Force

1 atm of
pressure is
the force of
10.1 N
on 1 cm ?

Pressure

362 CHAPTER ! 1
Measuring Pressure Vacuum
Nitrogen molecule, N 2
A barometer is a device used to measure atmospheric Oxygen molecule, 02
pressure. The first ivpe of barometer, illustrated in Pressure exerted
Figure 3, was introduced by Evangelista Torricelli during by the column
of mercury
the early 1600s. Torricelli wondered why water pumps
could raise water to a maximum height of only about
34 feet. He thought that the height must depend some -
how on the weight of water compared with the weight of
air. He reasoned that liquid mercury, which is about Atmospheric
14 times as dense as water, could be raised only 1 / 14 as pressure
high water.
as To test this idea. Torricelli sealed a long
glass tube at one end and filled it with mercury. Holding
the open end with his thumb, he inverted the tube into a
dish of mercury without allowing any air to enter the
tube. When he removed his thumb, the mercury column
in the tube dropped to a height of about 30 in. ( 760 mm )
Surface of
above the surface of the mercury in the dish. He repeat - mercury
ed the experiment with tubes of different diameters and
lengths longer than 760 mm. In every case, the mercury
dropped to a height of about 760 mm. FIGURE 3 Torricelli discovered
The space above the mercury in such a tube is nearly a vacuum. The that the pressure of the atmosphere
mercury in the tube pushes downward because of gravitational force. supports a column of mercury about
760 mm above the surface of the
The column of mercury in the tube is stopped from falling beyond a cer - mercurv in the dish.
tain point because the atmosphere exerts a pressure on the surface of
the mercury outside the tube. This pressure is transmitted through the
fluid mercury and is exerted upward on the column of mercury. The
mercury in the tube falls only until the pressure exerted by its weight is
equal to the pressure exerted by the atmosphere.
The exact height of the mercury in the tube depends on the atmos - Vacuum
pheric pressure, or force per unit area. The pressure is measured in
terms of the mercury column's height in the barometer tube. •f
From experiments like Torricelli's, it is known that at sea level and at
0 C. the average pressure of the atmosphere can support a 760 mm col -
:w t Pressure
of oxygen
gas in
*
umn of mercury. The atmospheric pressure at any given place depends
on the elevation and the weather conditions. If the atmospheric pressure
/
Oxygen gas
mm Hg

is greater than the average at sea level, the height of the mercury column
in a barometer will be greater than 760 mm. If the atmospheric pressure
molecules exert
a force o
is less, the height of the mercury column will be less than 760 mm.
%
All gases, not only those in the atmosphere, exert pressure. A device
called a manometer can be used to measure the pressure of an enclosed
gas sample, as shown in Figure 4. The difference in the height of mer -
'
0
Oxygen
molecules

cury in the two arms of the U - tube is a measure of the oxygen gas pres- Mercury
sure in the container.
FIGURE 4 In the manometer
To understand gas pressure, consider a can that is filled with air. The
above, the pressure of the oxygen
atmosphere exerts a pressure against the outside of the can. The air gas in the flask pushes on the mer -
inside the can pushes outward and balances the atmosphere’s inward- cury column. The difference in the
.
pushing force If a vacuum pump is used to remove the air from the can, height of the mercury in the two
the balancing outward force is removed. As a result, the unbalanced arms of the U - tube indicates the
force due to atmospheric pressure immediately crushes the can. oxygen gas pressure.

GASES 363
 Units of Pressure
A number of different units are used to measure pressure. Because
atmospheric pressure is often measured by a mercury barometer, pres-
sure can be expressed in terms of the height of a mercury column . Thus,
the common unit of pressure is millimeters of mercury, symbolized
mm Hg. A pressure of 1 mm Hg is also called 1 torr in honor of Torricelli
for his invention of the barometer. The average atmospheric pressure at
sea level at 0 C is 760 mm Hg.
Pressures are often measured in units of atmospheres. One atmosphere
of pressure ( atm ) is defined as being exactly equivalent to 760 mm Hg.
In SI . pressure is expressed in derived units called pascals. The unit is
pTTt ti named for Blaise Pascal, a French mathematician and philosopher who
Chemical Content studied pressure during the seventeenth century. One pascal ( Pa ) is
defined as the pressure exerted by a force of one newton ( 1 N ) acting on
Go to go. hrw. com for another
version of this content . See the an area of one square meter.
chapters " Physical Characteristics of In many cases, it is more convenient to express pressure in kilopascals
Gases and "Molecular Composition
'
( kPa ) . The standard atmosphere ( 1 atm ) is equal to 1.013 25 x 105 Pa , or
of Gases. "
101.325 kPa . The pressure units used in this book are summarized in
O/
Keyword: HC 6 GASX Table 1.

Standard Temperature and Pressure

To compare volumes of gases, one must know the temperature and
pressure at which the volumes are measured . For purposes of compari -
son, scientists have agreed on standard conditions of exactly I atm pres -
sure and (VC. These conditions are called standard temperature and
pressure and are commonly abbreviated STP

TABLE 1 Units of Pressure

Unit Symbol Definition/relationship
pascal Pa SI pressure unit
l N
—
I Pa = r
nr
millimeter of mercury mm Hg pressure that supports a
l mm mercury column in a
barometer
torr torr l torr = l mm Hg
atmosphere atm average atmospheric
pressure at sea level and 0 C
I atm = 760 mm Hg
= 760 torr
= 1.013 23 x 10s Pa
= 101.323 kPa
pounds per psi 1 psi = 6.892 86 x lO3 Pa
square inch 1 atm = 14.700 psi

364 CHAPTER 1 l
 SAMPLE PROBLEM A
The average atmospheric pressure in Denver, Colorado, is 0.830 atm. Express this pressure
in ( a ) millimeters of mercury (mm Hg) and (b ) kilopascals ( kPa ).

SOLUTION
1 ANALYZE Given: P of atmosphere = 0.830 aim

760 mm Hg = I atm ( definition ); 101.325 kPa = 1 aim ( definilion )

Unknown: a. P of atmosphere in mm Hg; b. P of atmosphere in kPa

760 mm Hg
2 PLAN a. atm » mm Hg; aim x = mm Hg
aim
101.325 kPa
b. atm
* kPa; atm x
aim
= kPa

760 mm Hg
3 COMPUTE a. 0.830 aim x = 631 mm Hg
atm

101325 kPa
b. 0.830 atm x = 84.1 kPa
atm
4 EVALUATE Units have canceled to give the desired units, and answers are expressed to the correct
.
number of significant figures The known pressure and the calculated pressures are about
80% of the atmospheric pressure, as expressed in the new units.

PRACTICE Answers in Appendix E

—rrftefreffcivi
1. Convert a pressure of 1.75 atm to kPa and to mm 1 Ig. Go to go.hrw.com
for more practice
2. The critical pressure of carbon dioxide is 72.7 atm. What is this problems that ask you
value in units of pascals? to convert between
units of pressure.
Keyword: HC 6 GASX

Dalton 's Law of Partial Pressures

John Dalton, the English chemist who proposed the atomic theory, also
studied gas mixtures. The pressure exerted by each gas in an unreactive
mixture is independent of that exerted by other gases present. The pres -
sure of each gas in a mixture is called the partial pressure of that gas.
Dalton's law of partial pressures states that the total pressure of a gas
mixture is the sum of the partial pressures of the component gases. The
law is true regardless of the number of different gases that are present.
Dalton's law may be expressed as follows.

PT = P\ + Pi + Ps + - . •
PTis the total pressure of the mixture. Pj. P2, Py and so on are the
partial pressures of component gases 1, 2.3, and so on.

GASES 365
 FIGURE 5 Hydrogen can be Water vapor,
collected by water displacement b \ molecule, H20
reacting zinc with sulfuric acid. The
hydrogen gas produced displaces
the water in the gas collecting
bottle. It now contains some
water vapor.

Hydrogen gas
molecule, H 2

You can understand Dalton s law in terms of the kinetic-molecular

theory. Each of the rapidly moving particles of gases in a mixture has an
equal chance to collide with the container walls. Therefore, each gas
exerts a pressure independent of that exerted by the other gases pre-
sent. The total pressure is the result of the total number of collisions per
unit of wall area in a given time.

Gases Collected by Water Displacement

Gases produced in the laboratory are often collected over water, as
.
shown in Figure 5 The gas produced bv the reaction displaces the water,
which is more dense,in the collection bottle. You can apply Dalton 's law
of partial pressures in calculating the pressures of gases collected in this
way. A gas collected by water displacement is not pure but is always
mixed with water vapor. That is because water molecules at the liquid
surface evaporate and mix with the gas molecules. Water vapor, like
other gases, exerts a pressure known as vapor pressure.
Suppose you wished to determine the total pressure of the gas and
water vapor inside a collection bottle. You would raise the bottle until
the water levels inside and outside the bottle were the same. At that
point, the total pressure inside the bottle would be the same as the
atmospheric pressure, Plimr According to Dalton s law of partial pres -
’

sures. the following is true.

I ....+ P!U)
PlUm = IPgasT #

Suppose you then needed to calculate the partial pressure of the dry
gas collected. You would read the atmospheric pressure, Patm * from a
barometer in the laboratory.To make the calculation, subtract the vapor
pressure of the water at the given temperature from the total pressure.
The vapor pressure of water varies with temperature. You need to look
up the value of PH,0 at the temperature of the experiment in a standard
reference table, such as Table A -8 in Appendix A of this book.

366 CH A PTER 11
 SAMPLE PROBLEM B
Oxygen gas from the decomposition of potassium chlorate, KCIOv was collected by water
displacement. The barometric pressure and the temperature during the experiment were
731.0 torr and 20.0°C, respectively. W hat was the partial pressure of the oxygen collected?

SOLUTION
1 ANALYZE Given: PT = Pl tm = 731.0 torr
(

P Q = 17.5 torr ( vapor pressure of water at 20.0 C. from Table A -8 )

^
P =
Unknown:
(itm

Pn
+ ^H 0
in torr
?

2 PLAN The partial pressure of the collected oxygen is found bv subtracting the partial pressure of
water vapor from the atmospheric pressure, according to Dalton's law of partial pressures.

Po , = Patm - />H-.C )

3 COMPUTE Substituting values for Pmm and P [U1 gives P(V

PC ) = 731.0 torr - 17.5 torr = 713.5 torr

4 EVALUATE As expected, the oxygen partial pressure is less than atmospheric pressure. It is reasonably
close to an estimated value of 713. calculated as 730 - 17.

PRACTICE Answers in Appendix E

1 . Some hydrogen gas is collected over water at 20.0 C. The levels of Go to go.hrw.com
water inside and outside the gas-collection bottle are the same. for more practice
problems that ask you
The partial pressure of hydrogen is 742.3 torr. What is the baro- to calculate partial
metric pressure at the time the gas is collected? pressure.
Keyword: HC 6GASX

SECTION REVIEW .
6 Why can you calculate the total pressure of a mix -
1. Define pressure. ture of gases by adding together the partial pres -
sures of the component gases ?
2. What units are used to express pressure
measurements ? Critical Thinking
3. What are standard conditions for gas 7 . EVALUATING METHODS Clean rooms used for
measurements ? sterile biological research are sealed and operate
4. Convert the following pressures to pressures in at slightly above atmospheric pressure. Explain
standard atmospheres: why.
a. 151.98 kPa b. 456 torr 8. INFERRING RELATIONSHIPS Explain why helium-
filled balloons deflate over time faster than air-
5. A sample of nitrogen gas is collected over water filled balloons do.
at a temperature of 23.0°C. What is the pressure
of the nitrogen gas if atmospheric pressure is
785 mm Hg ?

GASES 367
Chemistry in Action
The Gas Laws and Scuba Diving
W
s

t
c r>
/* 3123
%

. ^

An understanding of Dalton's law and increase in the air pressure leads to the excess nitrogen is discharged
Henry's law is essential to safe scuba an increase in the partial pressures through the lungs. However, if the
diving. Dalton's law states that the of the nitrogen and oxygen in air, as diver comes up too rapidly, the nitro -
total pressure of a gas mixture is predicted by Dalton's law. Henry's gen will form bubbles in the tissues
equal to the sum of the partial pres- law predicts that this increase in par - and veins. This condition is known as
sures of the component gases. Henry's tial pressures will increase the solu- decompression sickness, or " the
law predicts that the solubility of a bility of nitrogen and oxygen in the bends. " If the bubbles block blood
gas in a liquid is a direct function of diver 's bloodstream. flow, a wide range of effects, includ-
the partial pressure of that gas. The increase in the partial pressure ing severe joint pain, may occur. For
For every 33 ft of sea water that a of oxygen is not problematic under this reason, divers are very careful to
diver descends, he or she feels one typical diving conditions because a ascend slowly after diving.
additional atmosphere of pressure diver's body can metabolize the extra At extreme depths, even the
because of the increasing weight of oxygen that is present in the blood- increased pressure of oxygen
water overhead. Most divers use stream. The body does not metabolize becomes a problem for scuba divers.
compressed air tanks to breathe nitrogen, however, so it can accumu- Although oxygen is necessary for life,
underwater. The air in these tanks, late in a diver's body during a dive. extended exposure to large concen-
which contains approximately 78% The extra nitrogen can affect the nerve trations of oxygen can result in oxy -
nitrogen and 21 % oxygen, is the cells of the diver, causing nitrogen nar - gen toxicity. This condition can cause
same as the air that we breathe. cosis. Divers suffering from nitrogen damage to the lungs and nervous
Once the compressed air enters the narcosis become disoriented and expe- system. Divers can avoid oxygen toxi-
diver 's lungs, it is subjected to the rience symptoms similar to intoxica - city by breathing gas mixtures that
pressure caused by the water. The tion. This impairment of a diver's contain more helium and less oxygen
judgment can be very danger - than compressed air does.
ous. To decrease the probability
of contracting nitrogen narco- Questions
sis, divers can use gas mixtures 1. Why is the concentration of
that contain less nitrogen than helium increased in some gas
compressed air does. mixtures that divers breathe in
Dissolved nitrogen can also order to reduce the partial pres -
be harmful if a diver ascends sure of oxygen?
too quickly. As Henry's law
2. Although carbon monoxide, CO,
predicts, nitrogen becomes
is normally present in trace
less soluble in the blood as
quantities in air, compressed air
the pressure decreases. This
scuba tanks that are filled
decrease in solubility causes
improperly can contain elevated
nitrogen to leave the diver's
levels of CO. Why is this particu-
tissues and blood. Normally,
larly dangerous for divers?
4 In order to dive safely, scuba divers must be
aware of some of the basic gas laws.

CHAPTER 11
The Gas Laws SECTION 2

OBJECTIVES
w Use the kinetic -molecular the -
S dentists have been studying physical properties of gases for hundreds ory to explain the relation-
of years. In 1662, Robert Boyle discovered that gas pressure and volume ships between gas volume,
are related mathematically. The observations of Boyle and others led to the temperature, and pressure.
development of the gas laws. The gas laws are simple mathematical rela -
tionships between the volume, temperature, pressure, and amount of a gas. J Use Boyle's law to calculate
volume-pressure changes at
constant temperature.

Boyle 's Law: Pressure- Volume

Use Charles's law to calculate
Relationship volume- temperature changes
at constant pressure.
Robert Boyle discovered that doubling the pressure on a sample of gas
at constant temperature reduces its volume by one-half. Reducing the
pressure on a gas bv one-half allows the volume of the gas to double. As ^ Use Gay- Lussac's law to cal-
one variable increases, the other decreases. Figure 6 shows that as the culate pressure- temperature
volume of gas in the syringe decreases, the pressure of the gas increases. changes at constant volume.
You can use the kinetic- molecular theory to understand why this
pressure-volume relationship holds. The pressure of a gas is caused by ^ Use the combined gas law to
moving molecules hitting the container walls. Suppose the volume of a calculate volume-tempera-
container is decreased but the same number of gas molecules is present ture -pressure changes.
at the same temperature. There will be more molecules per unit volume.
The number of collisions with a given unit of wall area per unit time will
increase as a result . Therefore, pressure will also increase.
Lower pressure Higher pressure CHEMISTRY I
Module 6 : Gas Laws ^

FIGURE 6 The volume of gas in

the syringe shown in the photo is
reduced when the plunger is pushed
down . The gas pressure increases as
9 the volume is reduced because the
molecules collide more frequently
3 w i t h the walls of the container in a
smaller volume.

* GASES 369
 Volume Vs. Pressure Plotting the values of volume versus pressure for a gas at constant
for a Gas at Constant temperature gives a curve like that in Figure 7. The general volume -
Temperature pressure relationship that is illustrated is called Boyles law. Boyle's law
states that the volume of a fixed muss of gas varies inversely with the pres-
1200
sure at constant temperature.
Mathematically, Boyle’s law can he expressed as follows:
PV = k
In the equation above. P is the pressure. V is the volume, and k is a
constant . Since P and V vary inversely, their product remains the same.
Because two quantities that are equal to the same thing are equal to
each other, the relationship between changes of pressure and volume
can he expressed as shown below.
Pressure ( atm) p , v , = p2v2
FIGURE 7 This graph shows that Pj and Vi represent initial conditions. P2 and \' j represent a differ-
there is an inverse relationship ent set of conditions. Given three of the four values Pf , / \ and Is,
between volume and pressure. you can use this equation to calculate the fourth value for a system at
constant temperature.

SAMPLE PROBLEM C For more help, go to the Math T u t o r at the end of this chapter .

A sample of oxygen gas has a volume of 150.0 inL w hen its pressure is 0.947 atm. What will
the volume of the gas be at a pressure of 0.987 atm if the temperature remains constant ?

SOLUTION
1 ANALYZE Given: Vt of C): = 150.0 mL; Pj of Q: = 0.947 atm ; P i of 0- . = U.987 atm
Unknown: V •> of ( ) -» in mL

2 PLAN Rearrange the equation for Boyle ’s law ( If Vf = /MT ) to obtain V2 .

v , = I fpV. ,
3 COMPUTE Substitute values for P , . V' / . and P2 to obtain the new volume. l \ .

V ,=
,
P V, ( 0.947 alm)( 150.0 mLO:)
= 144 m L O i
l
\ 0.987 atm
4 EVALUATE When the pressure is increased slightly at constant temperature , the volume decreases
slightly, as expected . Units cancel to give milliliters, a volume unit .

PRACTICE Answers m Appendix E

1 . A balloon filled with helium gas has a volume of 500 mL at a

pressure of I atm . The balloon is released and reaches an Go to go.hrw.com
altitude of 0.5 km. w here the pressure is 0.5 atm. If the for more practice
temperature has remained the same, what volume does the gas problems that ask you
occupy at this height ? to use Boyle 's Law.
_

370 CHAPTER 11 ^JC Keyword: HC 6GA 5 X

 Charles's Law: Volume-
Temperature Relationship
Balloonists, such as those in the photo at the beginning of this chapter ,

are making use of a physical property of gases: if pressure is constant ,

gases expand when heated . When the temperature increases, the vol -
ume of a fixed number of gas molecules must increase if the pressure is
to stay constant . At the higher temperature, the gas molecules move
CHEMISTRY
faster. They collide with the walls of the container more frequently and Module 6 : Gas Laws
with more force. The volume of a flexible container must then increase
in order for the pressure to remain the same.
The quantitative relationship between volume and temperature was
discovered by the French scientist Jacques Charles in 17S7. Charles's
experiments showed that all gases expand to the same extent when
heated through the same temperature interval . Charles found that the
volume changes by 1 /273 of the original volume for each Celsius degree,
at constant pressure and an initial temperature of 0 C. For example,
raising the temperature to 1 C causes the gas volume to increase by
1 /273 of the volume it had at 0 C. If the temperature is increased by
273 C, the volume increases by 273/273 of the original , that is. the vol -
ume doubles. The same regularity of volume change occurs if a gas is
cooled at constant pressure, as the balloons in Figure 8 show.
The Kelvin temperature scale is a scale that starts at a temperature
corresponding to -273.15 C. That temperature is the lowest one possi -
ble. The temperature -273.15 C is referred to as absolute zero and is
given a value of zero in the Kelvin scale. This fact gives the following FIGURE 8 As air- filled balloons
are exposed to liquid nitrogen , they
relationship between the two temperature scales.
shrink greatly in volume because the
K = 273.15 + °C -
air molecules in the balloon get clos
er together. When the balloons are
For calculations in this book , 273.15 is rounded off to 273. removed from the liquid nitrogen
and the air inside them is warmed to
room temperature , they expand to
their original volume.

GASES
 Gas volume and Kelvin temperature are directly proportional to
Volume Vs.
each other at constant pressure as shown in Figure 9.
Temperature for a Gas
The relationship between Kelvin temperature and gas volume is
at Constant Pressure
known as Charles's law. Charles's law slates that the volume of a fixed
1100
mass of gas at constant pressure varies directly with the Kelvin tempera -
900 ture . Charles’s law may be expressed as follows:
l
E 700 V = kT or -= k
Ol i
T
| 500
The value of T is the Kelvin temperature, and k is a constant. The
5
"

> 300 ratio V71 for any set of volume - temperature values always equals the
same k . The form of Charles's law that can be applied directly to most
100 volume -temperature problems involving gases is as follows:
0 200 400 600
Vi VJ
Temperature ( K ) T/ h
FIGURE 9 This graph shows ihe and Tf represent initial conditions. V\ and T2 represent a differ -
Vi
plot of the volume versus the Kelvin ent set of conditions. When three of the four values T ) , V / T2 , and V 2
f

temperature data of a sample of gas are known, you can use this equation to calculate the fourth value for a
at constant pressure.
system at constant pressure.

SAMPLE PROBLEM For more help, go to the Math Tutor at the end of this chapter.
.
A sample of neon gas occupies a volume of 752 mL at 25CC What volume w ill the gas
occupy at 50°C if the pressure remains constant ?

SOLUTION
1 ANALYZE ,
Given: Vj of Ne = 752 mL: T of Ne = 25°C + 273 = 298 K: T2 of Ne = 50°C + 273 = 323 K
Unknown: V ? of Ne in mL

2 PLAN Because the gas remains at constant pressure, an increase in temperature will cause an
increase in volume. To obtain V 2 . rearrange the equation for Charles's law.

3 COMPUTE ,
Substitute values for V , Tj, and T: to obtain the new volume. V 2.
(752 mL Ne)(323 K )
T , 298 K
= 815 mL Ne

4 EVALUATE As expected, the volume of the gas increases as the temperature increases. Units cancel to
yield milliliters, as desired. The answer contains the appropriate number of significant figures.

PRACTICE Answers in Appendix E

1. A sample of neon gas has a volume of 752 mL at 25.0 C. What will

the volume at 100.0 C be if pressure is constant ?
' — CTTTteiTTftTTl
Go to go.hrw.com
2 . A sample of nitrogen gas is contained in a piston with a freely mov- for more practice
ing cylinder. At 0.0 C. the volume of the gas is 375 mL.To what tem - problems that ask you
to use Charles 's law.
perature must the gas be heated to occupy a volume of 500.0 mL?
Keyword: HC 6 GASX

372 CHAPTER 1 1
 Pressure Vs.
Gay - Lussac ' s Law: Pressure- Temperature for a Gas
Temperature Relationship at Constant Volume
6.0
You have just learned about the quantitative relationship between vol -
ume and temperature at constant pressure. What would you predict about 5.0
the relationship between pressure and temperature at constant volume? ?
You have seen that pressure is the result of collisions of molecules with £ 4.0

container walls. The energy and frequency of collisions depend on the SI3 3.0
average kinetic energy of molecules. For a fixed quantity of gas at con - wi
SA
£ 2.0
stant volume, the pressure should be directly proportional to the Kelvin CL

temperature, which depends directly on average kinetic energy. 1.0

That prediction turns out to be correct . For every kclvin of tempera -
ture change, the pressure of a confined gas changes by 1 /273 of the pres-
sure at 0 C. Joseph Gay - Lussac is given credit for recognizing this in 1802.
0 -
0 100 200 300 400 500
Temperature ( K )
-
The data plotted in Figure 10 illustrate Gay Lussac’s law: The pressure of
a fixed muss of gas at constant volume varies directly with the Kelvin tem - FIGURE 10 A graph of pressure
perature. Mathematically. Gay - Lussacs law is expressed as follows. versus temperature of a sample of
p gas at constant volume is a straight
P = kT or =k line, indicating a direct relationship
r between pressure and temperature.
The value of 7 is the temperature in kelvins. and k is a constant that
depends on the quantity of gas and the volume. For a given mass of gas
at constant volume, the ratio PIT is the same for any set of pressure -
temperature values. Unknown values can be found using the following
form of Gay- Lussac's law.
Pi PI
7I T2
Pi and 7/ represent initial conditions. P2 and T2 represent a different set
of conditions. When values are known for three of the four quantities,
the fourth value can be calculated for a svstem at constant volume.

SAMPLE PROBLEM E For more help, go to the Math Tutor at the end of this chapter

The gas in a container is at a pressure of 3.00 atm at 25°C. Directions on the container warn
the user not to keep it in a place where the temperature exceeds 52° C. What would the gas
pressure in the container be at 52°C?

SOLUTION
1 ANALYZE Given: Pj of gas = 3.00 atm
Tj of gas = 25°C + 273 = 298 K: T2 of gas = 52°C + 273 = 325 K
Unknown: P2 of gas in atm

2 PLAN Because the gaseous contents remain at the constant volume of the container, an increase
in temperature will cause an increase in pressure. Rearrange Gay- Lussac’s law to obtain P2 .
,
p ,= P T2
I

GASES 373
 3 COMPUTE Substitute values for Ph T2 . and
'
,
/ to obtain the new pressure. / Y
( 3.00 atm )(325 K )
P2 = = 3.27 atm
298 K
4 EVALUATE As expected, a temperature increase at constant volume causes the pressure of the contents
in the container to increase. Units cancel correctly. The answer contains the proper number of
significant figures. It is close to an estimated value of 3.25, calculated as ( 3 x 325 ) /3( K ).

PRACTICE Answers m Appendix E

1. At 120.0 C. the pressure of a sample of nitrogen is 1.07 atm. What

will the pressure be at 205 C assuming constant volume?
2. At 122 C the pressure of a sample of nitrogen gas is 1.07 atm.
What will the pressure be at 205 C. assuming constant volume?
3. A sample of helium gas has a pressure of 1.20 atm at 22 C. At w hat Go to go.hrw.com
for more practice prob -
Celsius temperature will the helium reach a pressure of 2.00 atm.
lems that ask you to
assuming constant volume ? use Gay - Lussac's law.
Keyword: HC 6GASX

The Combined Gas Law

SC
/,NKS Dm Md by t «
*
A gas sample often undergoes changes in temperature, pressure, and
volume all at the same time. When this happens, three variables must be
fc4tkMU< SritM# tMrittf1 AuocUttoa
dealt with at once. Boyle s law. Charles's law. and Gav -Lussac's law can
For a variety of links related to this
be combined into a single expression that is useful in such situations.
-
chapter, go to vvww. ilmks. org
h The combined gas law expresses the relationship between pressure, vol -
Topic: Gas Laws
Sci Links code: HC60637 ume, and temperature of a fixed amount off as. The combined gas law
can be expressed as follows.
A
T
In the equation, k is constant and depends tin the amount of gas The .
combined gas law can also be written as follows .
P Vj , / WA
/i 7\
The subscripts in the equation above indicate two different sets of
conditions, and T represents Kelvin temperature.
Chemical Content From this expression, any value can be calculated if the other five are
known. Note that each of the gas laws can be obtained from the com -
Go to go.hrw.com for more infor -
mation on how the combined
bined gas law when the proper variable is constant. For example.
gas law can be derived from Boyle 's law is obtained when the temperature is constant Because .
Boyle s law . C harles’s law and . / / = /’>, / ; and T2 w ill cancel out on both sides of the combined gas law
Gav -Lussac’s law. equation, giving Boyle 's law.

PJVJ = P j V,
Keyword: HC 6 GASX

374 CHAPTER 1 1
 SAMPLE PROBLEM F For more help, go to the Math Tutor at the end of this chapter .
A helium- filled balloon has a volume of 50.(11. at 25 °C and 1.08 atm. What volume will it
have at 0.855 atm and 10.0 °C?

SOLUTION
1 ANALYZE Given: Vt of He = 50.0 L: ,
T of He = 25 C + 273 = 298 K: 7, of He = 10 C + 273 = 283 K
,
P of He = 1.08 atm; P2 of He = 0.855 atm
,
Unknown: V of He in L

2 PLAN Because the gas changes in both temperature and pressure, the combined gas law is needed.
Rearrange the combined gas law to solve for the final volume. V2 .
PiV , ,
P V2
Tt T , » Vl = p
2r ,
3 COMPUTE Substitute the known values into the equation to obtain a value for Is.
( 1.08 atm ) ( 50.0 L He )( 283 K )
= 60.0 L He
( 0.855 atm)( 298 K )
4 EVALUATE Here the pressure decreases much more than the temperature decreases. As expected, the
net result of the two changes gives an increase in the volume, from 50.0 L to 60.0 L. Units
cancel appropriately. The answer is correctly expressed to three significant figures. It is also
reasonably close to an estimated value of 50. calculated as ( 50 x 300) /300.

PRACTICE Answers in Appendix E

1. The volume of a gas is 27.5 mL at 22.0 C and 0.974 atm. What

will the volume be at 15.0 C and 0.993 atm ? Go to go.hrw.com
2. A 700.0 mL gas sample at STP is compressed to a volume of for more practice
problems that ask
200.0 mL, and the temperature is increased to 30.0 C. What is
you to use the
the new pressure of the gas in Pa? combined gas law.
Keyword: HC 6GASX

SECTION REVIEW 4. A gas occupies 2.0 m3 at 100.0 K and exerts a

1. Relate the effect of temperature and pressure on pressure of 100.0 kPa. What volume will the gas
a gas to the model of a gas given by the kinetic- occupy if the temperature is increased to 400.0 K
molecular theory. and the pressure is increased to 200.0 kPa ?
2. A sample of helium gas has a volume of 200.0 mL Critical Thinking
at 0.960 atm. What pressure, in atmospheres, is
5. ANALYZING RESULTS A student has the following
needed to reduce the volume at constant tempera -
ture to 50.0 mL ?
, ,
data: V = 822 mL, T = 75°C, and T2 = -25°C. He
calculates V2 and gets -274 mL. Is this value cor -
3. A sample of nitrogen gas occupies 1.55 L at rect ? Explain why or why not.
27.0°C and 1.00 atm. What will the volume be at
6. APPLYING MODELS Explain Charles's law in terms
-100.0°C and the same pressure? of the kinetic -molecular theory.

GASES 375
 MgaaiEEgBa N« *Z3KS£I Kb fcS,4 -
ISTORICAL CHEMISTRY

Chemistry 's First Law

Historical Perspective further hypothesized that the air exerted pressure on the mer -
The notion that " nature abhors a vacuum " —meaning that cury in the container and thus supported the mercury in the
there is no such thing as " empty space " — was proposed column.
|by the Greek philosopher Aristotle, whose word was
Support for the New Theory
unchallenged for nearly 2000 years. Then, in the
Although the idea of an atmosphere that has weight and
mid-1600s, a new breed of thinkers known as natural
exerts a pressure on the objects within it seems obvious
—
philosophers what we now know as " scientists " —
today, it was a radical theory at the time.
began testing the long - held assumption that all space
To test the effects of the atmosphere, Robert Boyle, one
must contain matter. These investigations were some of
of the period's great scientists, had his talented assistant,
the earliest experiments with gases, and they led to the
Robert Hooke, create a piece of equipment that would rev -
discovery of the first empirical principle of chemistry,
olutionize the study of air. The apparatus was
Boyle's law.
an improved version of a pump designed by the German
Overturning an Ancient Assumption experimenter Otto von Guericke; the pump had a large
The first scientist to demonstrate the existence of a receptacle in which a partial vacuum could be created.
vacuum was Evangelista Torricelli. In 1643, he showed that Boyle placed Torricelli's setup, known today as a barom-
when a glass tube that was 3 ft. long and about 1 in. in eter, in the receptacle of the pump and observed the mer -
diameter was sealed cury column as he reduced the pressure around it. The
at one end, filled height of the mercury decreased as the pressure surround-
with mercury, and ing the mercury in the container dropped, strongly support -
inverted in a con- ing Torricelli 's atmospheric theory.
tainer full of mer - Using Hooke's pump, Boyle performed additional studies
cury, the mercury in that verified the idea that air exerted pressure and had
the tube fell to a weight. Boyle's experiments also led to the important con-
height of about elusion that air was elastic: that is, it could expand and con-
30 in. above the tract. Boyle discovered the fundamental law that bears his
level of mercury in name during an investigation into air 's elasticity.
the container. Some
An Ingenious Experiment
thinkers remained
In response to a criticism of his findings, Boyle performed
skeptical, but it was
an experiment to show that air could be compressed to a
generally accepted
pressure greater than that of the atmosphere. First, he pre-
that the space
pared a glass J - tube with the short end sealed off and the
between the mercury
A Evangelista Torricelli invented the long end left open. Then, he poured mercury into the tube,
and the sealed end
mercury barometer . making sure that the levels in the two ends were the same
of the tube was
and letting air travel freely between the ends, to ensure
indeed a vacuum.
that each column was at atmospheric pressure.
Torricelli then turned his attention to how the mercury in
Then, by pouring more mercury into the long end of the
the glass tube of his apparatus was supported. The fact that
tube until it was about 30 in. above the level of mercury in
liquids exert a pressure on objects immersed in them inspired
the short end, Boyle exposed the trapped air to about
him to hypothesize that a " sea of air " surrounded Earth. He
twice as much atmospheric pressure. He observed that the
 We can measure the
difference between the
atmospheric pressure on
a mountaintop and the
atmospheric pressure at
sea level thanks to the
work of Torricelli and

volume of the trapped air was halved. He continued to Questions

add mercury until the total pressure on the trapped air 1. Why was it necessary for Boyle to seal one end of his
was about 4 times that of the atmosphere. Noting that the J-tube?
air had been compressed to a volume about one- fourth of
what it originally was, Boyle discovered the inverse rela - 2. What would have happened if Boyle had allowed the
tionship between air 's pressure and volume. temperature of the trapped air sample to change as
he added mercury to the tube?
A Long- Standing Contribution
Boyle went on to show that the relationship between air
pressure and volume, W (at constant temperature), SClINKS. MrA
Dtvrtoptd JM) nuinUtnrd by tl
*
NJOOMI SdtMt iNdwn AUMUUM
held not only when the gas was compressed but also
For a variety of links related to this
when it was allowed to expand. Future investigators iks . org
chapter, go to
would show that the law is a principle that applies to
Topic: Torricelli
gases in general. Along with the findings of other SciLinks code: HC61539
researchers, such as Jacques Charles, Joseph Gay- Lussac, Topic: Robert Boyle
and Amadeo Avogadro, Boyle's discovery led chemists to Sci Links code: HC61317
the famous ideal gas law, PV = nRT; which serves as a
starting point in the study of chemistry today. r
.
GASES
 SECTION 3
Gas Volumes and the
OBJECTIVES Ideal Gas Law
sj State the law of combining
volumes.

- i State Avogadro's law and

explain its significance. 1 n this section, you will study the relationships between the volumes
of gases that react with each other. You will also learn about the rela -
tionship between molar amount of gas and volume, and a single gas law
J Define standard molar volume that unifies all the basic gas laws into a single equation.
of a gas and use it to calcu-
late gas masses and volumes.

>J State the ideal gas law. Measuring and Comparing the
Volumes of Reacting Gases
^ Using the ideal gas law, .
In the early 1800s French chemist Joseph Gay-Lussac studied gas vol -
calculate pressure, volume,
ume relationships involving a chemical reaction between hydrogen and
temperature, or amount of
gas when the other three oxygen. He observed that 2 L of hydrogen can react with 1 L of oxygen
quantities are known. to form 2 L of water vapor at constant temperature and pressure.

hydrogen gas + oxygen gas water vapor

2 L ( 2 volumes ) 1 L ( 1 volume ) 2 L ( 2 volumes)

In other words, this reaction shows a simple and definite 2 : 1 : 2 rela -

tionship between the volumes of the reactants and the product.Two vol -
umes of hydrogen react with 1 volume of oxygen to produce 2 volumes
of water vapor. The 2 : 1 : 2 relationship for this reaction applies to any
proportions for volume — for example, 2 mL, 1 mL, and 2 mL; 600 L.
300 L. and 600 L: or 400 cm \ 200 cm \ and 400 cm '.
Gay - Lussac also noticed simple and definite proportions by volume
in other reactions of gases, such as in the reaction between hydrogen gas
and chlorine gas.

hydrogen gas + chlorine gas

1 L ( I volume) 1 L (1 volume )
* hydrogen choloride gas
2 L ( 2 volumes )

.
In 1808 Gav-Lussac summarized the results of his experiments in a
statement known today as Gay- Lussac's law of combining volumes of
gases. Hie law states that at constant temperature and pressure, the vol -
umes of gaseous reactants and products can be expressed as ratios of
small whole numbers. This simple observation, combined with the
insight of Avogadro. provided more understanding of how gases react
and combine with each other.

378 CHAPTER 1 1
 Hydrogen
Avogadro's Law molecule
J
Recall an important point of Dalton s atomic theory: atoms are indivis-
'
j
ible. Dalton also thought that the particles of gaseous elements exist in
the form of isolated single atoms. He believed that one atom of one
* j
*
j j
element always combines with one atom of another element to form a
single particle of the product. However , some of the volume relation - o
ships observed by Gay- Lussac could not be accounted for by Dalton 's
theory. For example, in reactions such as the formation of water vapor,
mentioned on the preceding page, it would seem that the oxygen atoms
involved would have to divide into two parts. 1 mol H2 at
In LSI 1 . Avogadro found a way to explain Gay- Lussac's simple ratios STP = 22.4 L
of combining volumes without violating Dalton 's idea of indivisible
atoms. He did this bv rejecting Dalton 's idea that reactant elements are
always in monatomic form when they combine to form products. 1 le rea - -Oxygen
soned that these molecules could contain more than one atom . Avogadro
# molecule

also pul forth an idea known today as Avogadro's law. The law states that #
equal volumes of gases at the same temperature ami pressure contain equal %
numbers of molecules. Figure 11 illustrates Avogadro's law. It follows that
at the same temperature and pressure, the volume of any given gas varies
# %
directly with the number of molecules. Avogadro's law also indicates that
gas volume is directly proportional to the amount of gas. at a given tem -
o
perature and pressure. Note the equation for this relationship.

V = kn
1 mol 02 at
STP = 22.4 L
I lere. n is the amount of gas. in moles, and A is a constant .
Avogadro 's reasoning applies to the combining volumes for the reac-
tion of hydrogen and oxygen to form water vapor. Dalton had guessed
Carbon dioxide
that the formula of water was HO. because this formula seemed to be
the most likely formula for such a common compound . But Avogadro's
. molecule

reasoning established that water must contain twice as many H atoms

as O atoms, consistent with the formula ILO. As shown below, the coef - i *
ficients in a chemical reaction involving gases indicate the relative
numbers of molecules, the relative numbers of moles, and the relative
volumes. o
2 H:( g ) * 2 H 20(g )

WM
2 molecules I molecule 2 molecules
2 mol 1 mol 2 mol
2 volumes 1 volume 2 volumes
STP = 22.4 L J
The simplest hypothetical formula for oxygen indicated two oxygen
FIGURE 11 At the same
atoms, which turns out to be correct. The simplest possible molecule of
temperature and pressure, balloons
water indicated two hydrogen atoms and one oxygen atom per mole-
of equal volume have equal numbers
cule. which is also correct . Experiments eventually showed that all ele - of molecules, regardless of which gas
ments that are gases near room temperature, except the noble gases, they contain .
normally exist as diatomic molecules.

GASES 379
 FIGURE 12 Hydrogen
molecules combine with chlorine
molecules in a l:l volume ratio to
produce 2 volumes of hydrogen
chloride. Avogadro's law thus
demonstrates that hydrogen and
chlorine gases are diatomic. Hydrogen gas Chlorine gas Hydrogen chloride gas
1 Volume --
j 1 Volume 2 Volumes
1 Molecule 1 Molecule 2 Molecules

Consider the reaction of hydrogen and chlorine to produce hydrogen

SCflNKS. .
chloride, illustrated in Figure 12 According to Avogadro 's law, equal
Dm4f fd Md iMlatotMd fey ito
iMwul Socwf AHKMM
volumes of hydrogen and chlorine contain the same number of mole-
*
For a variety of links related to this
cules. Avogadro’s idea of diatomic gases applies to this reaction also. He
chapter, go to . . .* tlinks.org concluded that the hydrogen and chlorine components must each con -
Topic: Avogadro s Law
h sist of two or more atoms joined together. The simplest assumption was
SciLinks code: HC60131 that hydrogen and chlorine molecules are composed of two atoms each.
That assumption leads to the following balanced equation for the reac -
tion of hydrogen with chlorine.

H2(g) + Cl2( g ) 2HCl(g)

*
l volume l volume 2 volumes
l molecule l molecule 2 molecules

The simplest hypothetical formula for hydrogen chloride. HCI, indicates

Chemistry in Action that the molecule contains one hydrogen atom and one chlorine atom.
Automobile Air Bags Given the ratios of the combined volumes, the simplest formulas for
Since the late 1980s, air bags have been hydrogen and chlorine must be H2 and Ck respectively.
offered as a safety feature in cars to
minimize injuries in the event of a high-
speed collision. Modern automobile air
bags use a series of very rapid chemical
reactions to inflate the bag. When a colli-
Molar Volume of a Gas
sion is detected by sensors, an igniter
triggers decomposition of solid sodium Recall that one mole of a molecular substance contains a number ol
azide, Na3N, to form N2 gas. The haz - molecules equal to Avogadro's constant ( 6.022 x 102 '). One mole of
ardous sodium metal that also forms
reacts with KN03 to form Na20, also pro -
oxygen, Ck contains b.022 x diatomic oxygen molecules and has a
ducing additional N2. Finally, the highly mass of 31.9988 g. One mole of helium, a monatomic gas. contains the
reactive Na20 is removed by reaction same number of helium atoms and has a mass of 4.002 602 g.
with Si02 to form harmless silicate glass. According to Avogadro’s law, one mole of any gas will occupy the
This entire sequence of reactions occurs same volume as one mole of any other gas at the same temperature and
to inflate the air bag with nitrogen gas in
as few as 40 milliseconds (0.04 s) after a
pressure, despite mass differences. The volume occupied by one mole of
collision is detected by sensors. .
a gas at SIT is known as the standard molar volume of a gas h bus been
found to be 22.414 10 L. For calculations in this book, we use 22.4 L. as
the standard molar volume.
Knowing the volume of a gas, you can use I mol/22.4 L as a conver -
sion factor to find the number of moles, and therefore the mass, of a
given volume of a given gas at S I P. You can also use the molar volume
of a gas to find the volume, at SI P. of a known number of moles or a
known mass of a gas.

380 CHAPTER 1 1
 SAMPLE PROBLEM G
a . What volume does 0.0685 mol of gas occupy at STP?
I ). What quantity of gas. in moles, is contained in 2.21 L at STP?

SOLUTION 22.4 L
a . Multiply the amount in moles by the conversion factor.
1 mol
22.4 L
0.0685 mot x
1 mol
= 1.53 L
1 mol
b . Multiply the volume in liters by the conversion factor.
22.4 L
I mol
2.21 L x = 0.0987 mo
22.4 L

PRACTICE Answers in Appendix E

1 . At STP. what is the volume of 7.08 mol of nitrogen gas? I vfbrn

Go to go.hrw.com for
2 . A sample of hydrogen gas occupies 14.1 L at SrI'P. How many more practice problems
moles of the gas are present ? that ask you to calculate
molar volume.
Keyword: HC 6 GASX

Gas Stoichiometry
You can apply the discoveries of Gay - Lussac and Avogadro to calculate
the stoichiometry of reactions involving gases. For gaseous reactants or
products, the coefficients in chemical equations not only indicate molar
amounts and mole ratios but also reveal volume ratios, assuming condi -
tions remain the same. For example, consider the reaction of carbon
monoxide with oxygen to give carbon dioxide.

2CO(g) + 02( £ ) 2CO,( g ) - fld

il i\

2 molecules 1 molecule 2 molecules Chemical Content

2 mol 1 mol 2 mol Go to go.hrw. com for more infor-
2 volumes 1 volume 2 volumes mation on gas stoichiometry.
Keyword: HC 6 GASX
The possible volume ratios can be expressed in the following ways.
2 volumes CO 1 volume O ?
a. or
1 volume 02 2 volumes CO

2 volumes CO 2 volumes C02

b. or
2 volumes CO? 2 volumes CO

c.
1 volume O ?
or
2 volumes CO .
*

2 volumes CO ? 1 volume O ?

GASES 381
 SAMPLE PROBLEM H
Propane, C3Hh, is a gas that is sometimes used as a fuel for cooking and heating. The complete combus-
tion of propane occurs according to the following balanced equation.
C ,Hs(£ ) + 50,(g ) » iCOz ( g ) + 4H20(g)
W hat will he the volume , in liters, of oxygen required for the complete combustion of 0.350 L of
(a )
propane? ( b ) What will he the volume of carbon dioxide produced in the reaction? Assume that all vol -
ume measurements are made at the same temperature and pressure .

SOLUTION
1 ANALYZE Given: balanced chemical equation
V of propane = 0.350 L
Unknown: a . V of O, in L
b. V of CO in L ,
2 PLAN
a . V of C,HS * V of O-,
b. I/ of C;HS * V of CO,
All volumes are to be compared at the same temperature and pressure. Therefore, volume
ratios can be used like mole ratios to find the unknowns.
5 L O,
3 COMPUTE a . 0.350 L-%HS x
I -LCTHS
= 1.75 L. O,
3 L CO,
b. 0.350 LA THS x '

= 1.05 L CO,
4 EVALUATE Each result is correctly given to three significant figures. The answers are reasonably close
to estimated values of 2. calculated as 0.4 x 5. and 1.2, calculated as 0.4 x 3, respectively.

PRACTICE Answers in Appendix E

1 . Assuming all volume measurements are made at the same tempera -

ture and pressure, what volume of hydrogen gas is needed to react
completely with 4.55 L of oxygen gas to produce water vapor ?
2 . What volume of oxygen gas is needed to react completely with
0.626 L of carbon monoxide gas. CO. to form gaseous carbon
dioxide ? Assume all volume measurements are made at the same
temperature and pressure.
3. Nitric acid can be produced by the reaction of gaseous nitrogen diox-
ide with water, according to the following balanced chemical equation.
3NO:(s ) + H:0( / ) » 2 HN03( / ) + N0(g )
Go to go.hrw.com
If 70S L of NOi gas react with water, what volume of NO gas will for more practice
he produced ? Assume the gases are measured under the same con - problems that ask you
ditions before and after the reaction. to use mole ratios in
stoichiometry.
Keyword: HC 6 GASX
4
382 CHAPTER 11
 The Ideal Gas Law
You have learned about equations describing the relationships between
Chemical Content
two or three of the four variables— pressure, volume, temperature, and
Go to go.hrw.com for more infor -
moles—needed to describe a gas sample. All the gas laws you have mation on how the ideal gas law can
learned thus far can be combined into a single equation. The ideal gas be derived from Boyle’s law.
law is the mathematical relationship among pressure, volume, tempera - Charles's law. and Avogadro's law.
ture, ami the number of moles of a gas. It is the equation of state for an
Keyword: HC6 GASX
ideal gas. because the state of a gas can be defined by its pressure, vol-
ume. temperature, and number of moles. It is stated as shown below,
where R is a constant.

PV = nRT

The ideal gas law reduces to Boyle's law, Charles's law, Gay-Lussac's
law. or Avogadro 's law when the appropriate variables are held constant.
The number of molecules or moles present will always affect at least
one of the other three quantities. The collision rate of molecules per
unit area of container wall depends on the number of molecules pre-
sent . If the number of molecules is increased for a sample at constant
volume and temperature, the collision rate increases. Therefore, the
pressure increases, as shown by the model in Figure 13a. C onsider what
would happen if the pressure and temperature were kept constant while
the number of molecules increased. According to Avogadro's law. the
volume would increase. As Figure 13b shows, an increase in volume
keeps the pressure constant at constant temperature. Increasing the vol-
ume keeps the collision rate per unit of wall area constant .

Temperature Temperature

Pressure wl
Pressure

0 >K - - 1?
0

Gas Gas
molecules molecules
added added

(a ) ( b)

FIGURE 13 ( a ) When volume and temperature are constant, gas pressure

increases as the number of molecules increases. ( b ) When pressure and temper -
ature are constant, gas volume increases as the number of molecules increases.

GASES 383
 —rrrtareffrrn The Ideal Gas Constant
Chemical Content
Cio to go.hrw.com lor information In the equation representing the ideal gas law, the constant R is known
on how the ideal gas law can he
as the ideal gas constant. Its value depends on the units chosen for pres-
formulated in terms of molar mass
and density . .
sure. volume, and temperature. Measured values of R V I ] and n for a
gas at near-ideal conditions can be used to calculate R. Recall that the
Keyword: HC 6 GASX
volume of one mole of an ideal gas at STP ( 1 atm and 273.15 K ) is
22.414 10 L. Substituting these values and solving the ideal gas law
equation for R gives the following.
_ PV _ ( 1 atm)(22.414 10 L) L * atm
= 0.082 058
fj
” "

nT ( 1 mol )( 273.15 K ) mol •K

litis calculated value of R is usually rounded to 0.0821 L •atm/(moI»K ) .
Use this value in ideal gas law calculations when the volume is in liters,
the pressure is in atmospheres, and the temperature is in kelvins See .
.
Table 2 for the value of R when other units for / / R V and T are used.

Finding P, V, T, or n from the Ideal Gas Law

The ideal gas law can be applied to determine the existing conditions of
a gas sample when three of the four variables. R K I and / /. are known.
It can also be used to calculate the molar mass or density of a gas sample.
Be sure to match the units of the known quantities and the units of
R. In this book, you will be using R = 0.0821 L * atm / ( mol « K ). Your first
step in solving any ideal gas law problem should be to check the known
values to be sure vou are working with the correct units. If necessarv.
you must convert volumes to liters, pressures to atmospheres, tempera -
tures to kelvins. and masses to numbers of moles before using the ideal
gas law.

TABLE 2 Numerical Values of Gas Constant, R

Numerical Unit
Unit of R value of R Unit of P Unit of V Unit of T of n
L * mm Hg
62.4 mm Hg L K mol
mol •K
L * atm
0.0821 atm L K mol
mol • K
J
8.314 Pa nv K mol
mol •K
-
L kPa
mol •K
8.314 kPa L K mol

;
Note: 1 L * atm = 101.325 J; I .1 = I Pa* m
* SI units

384 CHAPTER 1 1
 SAMPLE PROBLEM I
What is the pressure in atmospheres exerted by a 0.500 mol sample of nitrogen gas in a 10.0 L container
at 298 K ?

SOLUTION
1 ANALYZE Given: V of N2 = 10.0 L
n of N:= 0.500 mol
T of N:= 29S K
Unknown: V of in atm

2 PLAN n, K T

Hie gas sample undergoes no change in conditions. Therefore, the ideal gas law can be
rearranged and used to find the pressure as follows.
nRT
r=
v
3 COMPUTE 0.0821 h • atm
( 0.500 mot ) mot • K ( 298 K )
= 1.22 atm
10.0 b

4 EVALUATE All units cancel correctly to give the result in atmospheres. The answer is properly limited
to three significant figures. It is also close to an estimated value of 1.5, computed as
(0.5 x 0.1 x 300 J/10.

PRACTICE Answers in Appendix E

1 . What pressure, in atmospheres, is exerted by 0.325 mol of hydro-

Go to go.hrw.com for
gen gas in a 4.08 L container at 35 C?
more practice problems
2. A gas sample occupies 8.77 L at 20 C. What is the pressure, in that ask you to use the
atmospheres, given that there are l .45 mol of gas in the sample ? ideal gas law.
Keyword: HC 6 GASX

SECTION REVIEW .
6 A tank of hydrogen gas has a volume of 22.9 L and
1. State Avogadro's law, and explain its significance. holds 14.0 mol of the gas at 12°C. What is the pres-
sure of the gas in atmospheres ?
2. What volume (in milliliters) at STP will be occu -
pied by 0.0035 mol of methane, CH4? Critical Thinking
3. State the ideal gas law equation, and tell what 7. ANALYZING DATA Nitrous oxide is sometimes
each term means. used as a source of oxygen gas:
.
4 What would be the units for /? if P is in pascals, 2 N20(g) » 2 N2(g) + 02( g)
y is in kelvins, V is in liters, and n is in moles ?
' What volume of each product will be formed from
5. A 4.44 L container holds 15.4 g of oxygen at 2.22 L N20? At STP, what is the density of the
22.55°C. What is the pressure? product gases when they are mixed ?

GASES 385
 SECTION 4
Diffusion and Effusion
OBJECTIVES
v Describe the process of
diffusion. T he constant motion of gas molecules causes them to spread out to
lill any container in which they are placed. The gradual mixing of two or
State Graham's law of more gases due to their spontaneous, random motion is known as diffu -
effusion. sion, illustrated in Figure 14. Effusion is the process whereby the mole -
cules of a gas confined in a container randomly pass through a tiny
opening in the container. In this section, you will learn how effusion can
State the relationship be used to estimate the molar mass of a gas.
between the average molecu-
lar velocities of two gases and
their molar masses.
Graham's Law of Effusion
The rates of effusion and diffusion depend on the relative velocities of
gas molecules. The velocity of a gas varies inversely with the square root
of its molar mass. Lighter molecules move faster than heavier molecules
at the same temperature.
Recall that the average kinetic energy of the molecules in any gas
depends only on the temperature and equals -> / / / / -. For two different
gases. A and B. at the same temperature, the following relationship is true.

Chemical Content 1 M.4> = |MHVH2

A
Go to go.hrw.com for more infor-
mation on how Graham 's law can he
derived from the equality of the Gas molecule from
kinetic energy of two gases. perfume

jT -
•j/
Keyword: HC 6 GASX

& J
9 0
9

FIGURE 14 When a bottle of per -

fume is opened, some of its mole- 9 9
9 9
9
•J 0 J>
9
cules diffuse into the air and mix 9
with the molecules in the air. At the 9 9
same time, molecules from the air.
such as nitrogen and oxygen, diffuse Oxygen molecule
into the bottle and mix with the Nitrogen molecule from the air
gaseous scent molecules. from the air

386 CHAPTER 7 7
From the equation relating the kinetic energy of two different gases at the
same conditions,one can derive an equation relating the rates of effusion
of two gases with their molecular mass. This equation is shown below.
rate of effusion of A V\tB
rate of effusion of B \ 1/ ,

In the mid- 1800s, the Scottish chemist Thomas Graham studied the
OwtapH md MMMMtf by Ifc
effusion and diffusion of gases. The above equation is a mathematical *
NlfaMlt SCMKt iMckm AlMKtatMM

statement of some of Graham 's discoveries. It describes the rates of For a variety of links related to this
effusion. It can also be used to find the molar mass of an unknown gas. chapter, go to ww
Graham's law of effusion states that the rates of effusion of gases at the Topic: Thomas Graham
same temperature and pressure are inversely proportional to the square SciLinks code: HC61517
roots of their molar masses.

QuickLAB Wear safety goggles and an apron.

Materials
Diffusion • household ammonia
• perfume or cologne
Question as the observer midway • two 250 mL beakers
Do different gases diffuse between the two beakers. • two watch glasses
at different rates ? Remove both watch glass • 10 mL graduated cylinder
covers at the same time.
• clock or watch with
Procedure 3. Note whether the observer second hand
Record all of your results in a smells the ammonia or the
data table. perfume first. Record how
1. Outdoors or in a room sepa -
long this takes. Also, record
how long it takes the vapor of
rate from the one in which
the other substance to reach
you will carry out the rest the observer. Air the room after
of the investigation, pour
you have finished.
approximately 10 mL of the
household ammonia into one
of the 250 mL beakers, and Discussion
cover it with a watch glass. 1. What do the times that the
Pour roughly the same amount two vapors took to reach the
of perfume or cologne into the observer show about the two
second beaker. Cover it with a gases ?
watch glass also.
2. What factors other than molec -
2. Take the two samples you just ular mass (which determines
prepared into a large, draft-free diffusion rate) could affect how
room. Place the samples about quickly the observer smells
12 to 15 ft apart and at the each vapor ?
same height. Position someone

GASES 387
 SAMPLE PROBLEM J
Compare the rates of eff usion of hydrogen and oxygen at the same temperature and pressure .
SOLUTION
1 ANALYZE Given: identities of two gases, 11: and 02
Unknown: relative rates of effusion

2 PLAN molar mass ratio > ratio of rates of effusion

Hie ratio of the rates of effusion of two gases at the same temperature and pressure
can be found from Graham s law.
rate of effusion of A V MH
rate of effusion of B \ M,
rate of effusion of H2 _ V v/o: V 32.00 g /mol _ 32.00 g /mol
3 = 3.98
COMPUTE
rate of effusion of Q 2 X M ,, \ 2.02 g /mol 2.02 g / mol

Hydrogen effuses 3.98 times faster than oxygen.

4 EVALUATE The result is correctly reported to three significant figures. It is also approximately equiva -
lent to an estimated value of 4. calculated as V 32 / V 2 .

PRACTICE Answers in Appendix E

1 . Compare the rate of effusion of carbon dioxide with that of

hydrogen chloride at the same temperature and pressure.
2. A sample of hydrogen effuses through a porous container about
9 times faster than an unknown gas. Estimate the molar mass of
the unknown gas.
—
crTVi i' Tftd n
3. If a molecule of neon gas travels at an average of 400 m/s at a . Go to go.hrw.com for
given temperature, estimate the average speed of a molecule of additional problems
. ,.
butane gas C4H 0 at the same temperature. that ask you to compare
rates of effusion.
Keyword: HC 6 GASX

SECTION REVIEW 5. List the following gases in order of increasing

1. Compare diffusion with effusion . average molecular velocity at 25°C: H20, He, HCI,
BrF, and N02 .
2. State Graham's law of effusion.
3. Estimate the molar mass of a gas that effuses at 1.6 Critical Thinking
times the effusion rate of carbon dioxide. 6. ANALYZING INFORMATION An unknown gas
4. Determine the molecular mass ratio of two gases effuses at one-half the speed of oxygen. What is
whose rates of effusion have a ratio of 16 : 1. the molar mass of the unknown ? The gas is
known to be either HBr or HI. Which gas is it ?

388 CHAPTER 11
 CHAPTER HIGHLIGHTS
Gases and Pressure
I Vocabulary •The kinetic-molecular theory of gases describes an ideal gas.
pressure atmosphere of The behavior of most gases is nearly ideal except at very high
newton pressure pressures and low temperatures.
barometer pascal •A barometer measures atmospheric pressure.
millimeters of partial pressure •Dalton's law of partial pressure states that in a mixture of unre-
mercury Dalton 's law of par - acting gases, the total pressure equals the sum of the partial
tial pressures
pressures of each gas.

The Gas Laws

I Vocabulary •Boyle s law states the inverse relationship between the volume
'

Boyle's law and the pressure of a gas:

absolute zero rv = k
Charles's law •Charles's law illustrates the direct relationship between a gas s
'

Gay - Lussac ' s law volume and its temperature in kelvins:

combined gas law V = kT
•Gay- Lussac 's law represents the direct relationship between a
gas s pressure and its temperature in kelvins:
'

P = kT
•The combined gas law. as its name implies, combines the previ-
ous relationships into the following mathematical expression:
r\
— =k
T

Gas Volumes and the Ideal Gas Law

i Vocabulary •Gay-Lussac s law of combining volumes states that the volumes
'

law of combining volumes of

Gay - Lussac ' s of reacting gases and their products at the same temperature
gases and pressure can be expressed as ratios of whole numbers.
Avogadro's law
standard molar volume of a gas
•Avogadro 's law states that equal volumes of gases at the same
temperature and pressure contain equal numbers of molecules.
ideal gas law
•The volume occupied by one mole of an ideal gas at STP is
ideal gas constant called the standard molar volume, which is 22.414 10 L.
•Charles's law. Boyle’s law. and Avogadro’s law can be com-
bined to create the ideal gas law:
PV = nRT

Diffusion and Effusion

I Vocabulary •Gases diffuse, or become more spread out , due to their con -

Graham's law of effusion random molecular motion.

stant
•Graham's law of effusion states that the relative rates of effu-
sion of gases at the same temperature and pressure are inverse -
ly proportional to the square roots of their molar masses .

GASES 389
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
9. Convert each of the following into the unit
Gases and Pressure specified.
a. 125 mm Hg into atmospheres
SECTION 1 REVIEW
h. 3.20 atm into pascals
1. State the assumptions that the kinetic - molecular c. 5.38 kPa into millimeters of mercury
theory makes about the characteristics of gas .
10 Three of the primary components of air are
particles. carbon dioxide, nitrogen, and oxygen. In a sam -
2. What is an ideal gas? ple containing a mixture of only these gases at
3. a. Why does a gas in a closed container exert exactly l atm, the partial pressures of carbon
pressure ? dioxide and nitrogen are given as P( o -> = 0.285
b. What is the relationship between the area a torr and /JVi = 593.525 torr. What is the partial
force is applied to and the resulting pressure ? pressure of oxygen ?
4. a. Win does a column of mercury in a tube that .
11 A sample of gas is collected over water at a
is inverted in a dish of mercury have a height temperature of 35.0 C when the barometric
of about 760 mm at sea level? pressure reading is 742.0 torr. What is the par -
b. The density of water is approximately 1/ 13.5 tial pressure of the dry gas ?
the density of mercury. What height would be
maintained by a column of water inverted in
a dish of water at sea level?
c. What accounts for the difference in the
The Gas Laws
heights of the mercury and water columns? SECTION 2 REVIEW
5. a. Identify three units used to express pressure. 12. How are the volume and pressure of a gas at
b. Convert one atmosphere to millimeters of constant temperature related?
mercury. 13. Explain why pressure increases as a gas is com -
c. What is a pascal?
pressed into a smaller volume.
d. What is the SI equivalent of one standard 14. How are the absolute temperature and volume
atmosphere of pressure? of a gas at constant pressure related?
6. a. Explain what is meant by the partial pressure 15. How are the pressure and absolute temperature
of each gas within a mixture of gases, of a gas at constant volume related?
b. How do the partial pressures of gases in a 16. Explain Gay - Lussac 's law in terms of the kinetic -
mixture affect each other ? molecular theory.
17. State the combined gas law.
PRACTICE PROBLEMS
7. If the atmosphere can support a column of PRACTICE PROBLEMS
mercury 760 mm high at sea level, what height 18. Use Boyle's law to solve for the missing value
of a hypothetical liquid whose density is 1.40
in each of the following:
times the density of mercury could be support -
ed?
, ,
a. 7 = 350.0 torr. U = 200.0 mL.

8. Convert each of the following into a pressure

.
/\ = 700.0 torr V 2 = ?
. -
b. Vx = 2.4 x 10s L P2 180 mm Hg,
reading expressed in torrs.
a. 1.25 atm
V2 = 1.8 x If)3 L 7 o. ,
_
19. Use Charles's law to solve for the missing value
b. 2.48 x 10-3 atm in each of the following:
c. 4.75 x 1()4 atm , . ,
a. V = 80.0 mL 7 = 27°C, 7\ = 77CC, V 2 = ?
d. 7.60 x 106 atm , .
b. V = 125 L V 2 = 85.0 L. T2 = 127°C .=?
,
c. 7 = -33 C. V2 = 54.0 mL. 73 = 160.0 C. V = ? ,
390 CHAPTER 11
 CHAPTER REVIEW

20. A sample of air has a volume of 140.0 mL at 32. The balloon in the previous problem will burst
67 C. At what temperature would its volume be if its volume reaches 400.0 L. Given the initial
50.0 mL at constant pressure? conditions specified in that problem, determine
21. The pressure exerted on a 240.0 mL sample of at what temperature, in degrees Celsius, the bal -
hydrogen gas at constant temperature is loon will burst if its pressure at that bursting
increased from 0.428 atm to 0.724 atm. What point is 0.475 atm.
will the final volume of the sample be? 33. The normal respiratory rate for a human being
22 . A sample of hydrogen at 47 C exerts a pressure is 15.0 breaths per minute. The average volume
of 0.329 atm. The gas is heated to 77°C at con- of air for each breath is 505 cm3 at 20.0 C and
stant volume. What will its new pressure be? 9.95 x ID4 Pa. What is the volume of air at STP
23 . A sample of gas at 47 C and 1.03 atm occupies that an individual breathes in one day? Give
a volume of 2.20 L. What volume would this gas vour answer in cubic meters.
occupy at 107 C and 0-789 atm?
24 . The pressure on a gas at -73 C is doubled, but
.
its volume is held constant What will the final
Gas Volumes and the
temperature be in degrees Celsius?
25 . A flask containing 155 cm ' of hydrogen was col - Ideal Gas Law
lected under a pressure of 22.5 kPa. What pres -
SECTION 3 REVIEW
sure would have been required for the volume
.
of the gas to have been 90.0 cnT assuming the 34. a. What are the restrictions on the use of
same temperature? Gav -Lussacs law of combining volumes?
26. A gas has a volume of 450.0 mL. If the tempera - b. At the same temperature and pressure, what
ture is held constant , what volume would the is the relationship between the volume of a
gas occupy if the pressure were gas and the number of molecules present 0
,
a. doubled? ( Hint : Express P2 in terms of /J . ) 35 . a. In a balanced chemical equation, what is the
relationship between the molar ratios and
b. reduced to one-fourth of its original value ?
27. A sample of oxygen that occupies LOO x MV ’ mL the volume ratios of gaseous reactants and
at 575 mm 1 Ig is subjected to a pressure of products?
1.25 atm. What will the final volume of the sam - b. What restriction applies to the use of the vol-
ple be if the temperature is held constant ? ume ratios in solving stoichiometry problems?
28. To what temperature must a sample of nitrogen 36. According to Avogadro.
at 27 C and 0.625 atm be taken so that its pres- a. what is the relationship between gas volume
sure becomes 1.125 atm at constant volume? and number of moles at constant temperature
29. A gas has a volume of 1.75 L at -23 C and and pressure ?
150.0 kPa. At what temperature would the gas b. w hat is the mathematical expression denoting
occupy 1.30 L at 210.0 kPa ? this relationship?
30. A gas at 7.75 x I 04 Pa and 17 C occupies a vol - 37. What is the relationship between the number ol
ume of 850.0 cm3. At what temperature, in molecules and the mass of 22.4 L of different
degrees Celsius, would the gas occupy 720.0 cm ’ gases at STP?
at 8.10 x 104 Pa ? 38 . a. In what situations is the ideal gas law most
31 . A meteorological balloon contains 250.0 L He suitable for calculations?
at 22 C and 740.0 mm Hg. If the volume of the b. When using this law, why do you have to pay
balloon can van according to external condi- particular attention to units?
tions. what volume would it occupy at an alti- 39. a. Write the equation for the ideal gas law;
tude at which the temperature is -52 C and the b. What relationship is expressed in the ideal
pressure is 0.750 atm? gas law?

GASES 391
 CHAPTER REVIEW

PRACTICE PROBLEMS 47. If air is 20.9% oxygen by volume .

40. Suppose a 5.00 L sample of O, at a given a. how many liters of air are needed for
temperature and pressure contains 1.08 x 102 ' complete combustion of 25.0 L of octane
molecules. How many molecules would be con - . ,
vapor CSH k?
tained in each of the following at the same tem - h. what volume of each product is produced?
perature and pressure? 48. Methanol. Cl 1;OH, is made bv causing carbon
a. 5.0 L H, monoxide and hydrogen gases to react at high
b. 5.0 L CO, temperature and pressure. If 4.50 x 102 mL CO
c. 10.0 LNH , and 8.25 x 10:mL H, are mixed.
41. How many moles are contained in each of the a. which reactant is present in excess?
following at STP? b. how much of that reactant remains after the
a. 22.4 LN, reaction ?
b. 5.60 L Cl2 c. w hat volume of CH OH is produced, assum -
^
c. 0.115 LNe ing the same pressure?
d. 70.0 mL NH3 49. Calculate the pressure, in atmospheres, exerted
42. Find the mass, in grants, of each of the following by each of the following:
at Sl’P. a. 2.50 L HF containing 1.35 mol at 320.0 K
a. 11.2 LH, b. 4.75 L NO, containing 0.86 mol at 300.0 K
.
b 2.80 L CO, c. 5.50 x 104 mL CO, containing 2.15 mol at
c. 15.0 mL SO, 57°C
d. 3.40 cm ' F, 50. Calculate the volume, in liters, occupied by each
43 . Find the volume, in liters, of each of the of the following:
following at STP. a. 2.00 mol H: at 300.0 K and 1.25 atm
a. 8.00 g O, b. 0.425 mol NH3 at 37 C and 0.724 atm
b. 3.50 g CO c. 4.00 g O, at 57 C and 0.888 atm
c. 0.0170 gH,S 51. Determine the number of moles of gas
d. 2.25 x 105 kgNH , contained in each of the following:
44 . Acetylene gas. C,H,. undergoes combustion to a. 1.25 L at 250.0 K and 1.06 atm
produce carbon dioxide and water vapor. If b. 0.80 L at 27 C and 0.925 atm
75.0 L CO, is produced. c. 7.50 x 102 mL at -50.0 C and 0.921 atm
a. how many liters of C,H, are required? 52. Find the mass of each of the following.
b. what volume of H,0 vapor is produced? a. 5.60 L O, at 1.75 atm and 250.0 K
c. what volume of O, is required? b. 3.50 L NH3 at 0.921 atm and 2TC
45. Assume that 5.60 L II2 at S I P reacts with c. 125 mL SO> at 0.822 atm and -5 C
excess CuO according to the following
equation:
CuO ( x ) + H2(g) Cu( .v ) + H2Q(£) Diffusion and Effusion
*
Make sure the equation is balanced before SECTION 4 REVIEW
beginning your calculations. 53. Describe in your ow n words the process of
a. How many moles of H, react ? diffusion.
b. I low many moles of Cu are produced ? 54. At a given temperature, what factor determines
c. How many grams of Cu are produced ? the rates at which different molecules undergo
.
46. If 29.0 L of methane, CH4 undergoes complete diffusion and effusion?
combustion at 0.961 atm and 140 C. how' many 55 . Ammonia. NH 3. and alcohol. C,HhO. are
liters of each product would be present at the released together across a room. Which will you
same temperature and pressure? smell first ?

392 CHAPTER ? 1
 CHAPTER REVIEW

PRACTICE PROBLEMS 66. At a deep-sea station that is 200. m below the

56. Quantitatively compare the rates of effusion surface of the Pacific Ocean, workers live in a
for the following pairs of gases at the same highly pressurized environment. How many
temperature and pressure: liters of gas at STP must be compressed on the
a. hydrogen and nitrogen surface to fill the underwater environment with
b. fluorine and chlorine 2.00 x 10 L of gas at 20.0 atm? Assume that
57. What is the ratio of the average velocity of temperature remains constant.
hydrogen molecules to that of neon atoms at 67. An unknown gas effuses at 0.850 times the effu-
the same temperature and pressure? sion rate of nitrogen dioxide, N02. Estimate the
58. At a certain temperature and pressure, chlorine molar mass of the unknown gas.
molecules have an average velocity of 324 m/s. 68. A container holds 265 mL of chlorine gas, CL.
What is the average velocity of sulfur dioxide If the gas sample is at STP. what is its mass?
molecules under the same conditions? 69. Suppose that 3.11 mol of carbon dioxide is
at a pressure of 0.820 atm and a temperature
.
of 39°C What is the volume of the sample,
MIXED REVIEW in liters?
70. Compare the rates of diffusion of carbon
59. A mixture of three gases. A . B. and C, is at a .
monoxide, CO. and sulfur trioxide S03 .
total pressure of 6.11 atm. The partial pressure 71. A gas sample that has a mass of 0.993 g occu-
of gas A is 1.68 atm: that of gas B is 3.89 atm. pies 0.570 L. Given that the temperature is
What is the partial pressure of gas C? 281 K and the pressure is 1.44 atm. what is the
60. A child receives a balloon filled with 2.30 L of molar mass of the gas?
helium from a vendor at an amusement park. 72. How many moles of helium gas would it take to
The temperature outside is 311 K. What will the fill a balloon with a volume of 1000.0 cnT when
volume of the balloon be when the child brings the temperature is 32 C and the atmospheric
it home to an air -conditioned house at 295 K ? pressure is 752 mm Hg?
Assume that the pressure stays the same. 73. A gas sample is collected at 16 C and 0.982 atm.
61. A sample of argon gas occupies a volume of If the sample has a mass of 7.40 g and a volume
.
295 mL at 36 C What volume will the gas occu- of 3.96 L. find the volume of the gas at S I P and
py at 55 C. assuming constant pressure? the molar mass.
62 . A sample of carbon dioxide gas occupies
638 mL at 0.893 atm and 12 C. What will the
pressure be at a volume of 881 mL and a tem - CRITICAL THINKING
perature of 18 C?
63. At 84 C. a gas in a container exerts a pressure 74. Applying (Models
of 0.503 atm. Assuming the size of the container a. Why do we say the graph in Figure 7 illus -
has not changed, at what temperature in C elsius trates an inverse relationship?

degrees would the pressure be 1.20 atm? b. Why do we say the data plotted in Figure 9
64. A weather balloon at Earth's surface has a vol- indicates a direct relationship?
ume of 4.00 I. at 304 K and 755 mm Hg. If the 75. Inferring Conclusions If all gases behaved as
balloon is released and the volume reaches ideal gases under all conditions of temperature
4.08 L at 728 mm Hg. what is the temperature? and pressure, solid or liquid forms of these sub-
65. A gas has a pressure of 4.62 atm when its stances would not exist . Explain.
volume is 2.33 L. If the temperature remains
constant, what will the pressure be when the
volume is changed to 1.03 L? Express the final
pressure in torrs.

GASES 393
 CHAPTER REVIEW

76 . Relating Ideas Pressure is defined as force per 80 . Interpreting Concepts The diagrams below
unit area . Yet Torricelli found that the diameter represent equal volumes of four different gases.
of the barometer dish and the surface area of
contact between the mercury in the tube and in
the dish did not affect the height of mercury
that was supported . Explain this seemingly
inconsistent observation in view of the relation - A B
ship between pressure and surface area.
77 . Evaluating Methods In solving a problem ,
what types of conditions involving temperature,
pressure, volume, or number of moles would
allow you to use c D
a . the combined gas law ?
Use the diagrams to answer the following
b. the ideal gas law ?
questions:
-
78. Evaluating Ideas Gay Lussac’s law of combin - a. Are these gases at the same temperature and
ing volumes holds true for relative volumes at pressure ? How do you know ?
any proportionate si /e. Use Avogadro’s law to b. If the molar mass of gas B is 38 g/ mol and
explain why this proportionality exists. that of gas C is 46 g/ mol , which gas sample is
79. Interpreting Graphics The graph below denser ?
shows velocity distribution curves for the c. To make the densities of gas samples B and C
same gas under two different conditions. A and equal, which gas should expand in volume ?
B. Compare the behavior of the gas under d . If the densities of gas samples A and C are
conditions A and B in relation to each of the equal , what is the relationship between their
following: molar masses?
a . temperature
b. average kinetic energy
c. average molecular velocity RESEARCH & WRITING
d . gas volume
81 . Design and conduct a meteorological study to
e. gas pressure
examine the interrelationships between baro-
metric pressure, temperature, humidity, and
other weather variables. Prepare a report
explaining your results.
82 . Conduct library research on attempts made to
Condition A
approach absolute zero and on the interesting
<U properties that materials exhibit near that tem -
perature. Write a report on your findings.
3
U
01
o 83. How do scuba divers use the laws and principles
E
o that describe the behavior of gases to their
c Condition B advantage? What precautions do they take to
o
u
3
prevent the bends ?
U . 84. Explain the processes involved in the liquefac-
tion of gases. Name some substances that are
gases under normal room conditions and that
are typically used in the liquid form . Explain
Velocity
whv this is so.

394 CHAPTER 11
 CHAPTER REVIEW

85 . Write a summary describing how Gay- Lussac 's

ALTERNATIVE ASSESSMENT
work on combining volumes relates to
Avogadro's study of gases. Explain how certain 90. The air pressure of car tires should be checked
conclusions about gases followed logically from regularly for safety reasons and for prevention of
consideration of the work of both scientists. uneven tire wear. Find out the units of measure-
ment on a typical tire gauge, and determine how
gauge pressure relates to atmospheric pressure.
USING THE HANDBOOK 91 . During a typical day. record every instance in
which you encounter the diffusion or effusion of
86. Review the melting point data in the properties gases ( for example, when smelling perfume ).
tables for each group of the Elements
Handbook . What elements on the periodic table 92 . Performance Qualitatively compare the
exist as gases at room temperature ? molecular masses of various gases by noting
87 . Review in the Elements Handbook the listing of how long it lakes you to smell them from a
the top 10 chemicals produced in the United fixed distance. Work only with materials that
States. Which of the top 10 chemicals are gases? are not dangerous, such as flavor extracts, fruit
88. Most elements from Groups 1.2. and 13 will peels, and onions.
react with water, acids, or bases to produce 93. Performance Design an experiment to gather
hydrogen gas. Review the common reactions data to verify the ideal gas law. If your teacher
information in the Elements Handbook and approves of your plan , carry it out. Illustrate
answer the following questions: your data with a graph , and determine if the
a . What is the equation for the reaction of bari - data are consistent with the ideal gas law.
um with water?
b. What is the equation for the reaction
between cesium and hydrochloric acid ?
c. What is the equation for the reaction of galli -
um with hydrofluoric acid ?
d . What mass of barium would be needed to
react with excess water to produce 10.1 L IT
i Graphing Calculator
Using the Ideal Gas Law
Go to go.hrw.com for a graphing calculator
at STP? exercise that asks you to use the ideal
e. What masses of cesium and hydrochloric acid gas law.
would be required to produce 10.1 L FT at
Keyword: HC 6 GASX
STP?
89 . Group 1 metals react with oxygen to produce
oxides, peroxides, or superoxides. Review the
equations for these common reactions in the
Elements Handbook , and answer the following:
a . How do oxides, peroxides, and superoxides
differ?
b. What mass of product will be formed from a
reaction of 5.00 I. 02 with excess sodium ?
The reaction occurs at 27 C and 1 atm .

GASES 395
 Math Tutor ALGEBRAIC REARRANGEMENTS OF GAS LAWS

When you solve problems in chemistry, it's usually a bad idea to just start entering
numbers into a calculator. Instead, doing a little pencil- and- paper work beforehand
will help you eliminate errors. When using the gas laws, you do not need to
memorize all of the equations because they are easily derived from the equation for
the combined gas law, y - =
-
Study the table below. In each of Boyle's, Charles's,
and Gay-Lussac's laws, one of the quantities — Tf P, or V— does not change. By simply
eliminating that factor from the equation, you obtain the equation for one particular
gas law.

Gas law Held constant Cancellation Result

P \ Vx PiVi P ,V P2 V2
Combined gas law none
7', 7\ T r,
P ,V ->
p V
,
'
1r i
Bovle s law- tempera ture P V \ = P2 V 2

Charles's law pressure rx\\ JKVZ V' l vs

T T, h 7\
p,
Gay - Lussac's law volume
r,
"
T -, Ty T2

The conditions stated in the problem should make clear which factors change and
which are held constant . This information will tell you which law's equation you need
to use .
SAMPLE
A cylinder of nitrogen gas has a volume of 35.00 L at a pressure of 11.50 atm. What
pressure will the nitrogen have if the contents of the cylinder are allowed to flow into a
sealed reaction chamber whose volume is 140.0 L, and if the temperature remains constant ?
Start with the combined gas law , and cancel the temperature, which does not change.

You want to know the new pressure in the chamber, so solve for P2.
P\ V
_ •
1 he resulting equation to use in
V ,
, • the
solving u
= Pl
„ P — = ( 11 50 atm)(35.00 L )
problem is P2 = —\Vi -
140.0 L
= 2.875 atm.

PRACTICE PROBLEMS
,
1 . A sample of gas has a pressure P at a tempera - 2. An ideal gas occupies a volume of 785 mL at a
ture Pj . Write the equation that you would use pressure of 0.879 atm. What volume will the gas
.
to find the temperature 72 at which the gas has occupy at a pressure of 0.994 atm?
a pressure of P2.

396 CHAPTER 11
Answer the following items on a separate piece of paper. SHORT ANSWER

MULTIPLE CHOICE 8. Give a molecular explanation for the observa -

.
1 Pressure can be measured in
tion that the pressure of a gas increases when
the gas volume is decreased.
A . grams . C. pascals.
B. meters. D. liters. 9. The graph below shows a plot of volume versus
pressure for a particular gas sample at constant
2. A sample of oxygen gas has a volume of temperature. Answer the following questions by
150 mL when its pressure is 0.923 atm. If the referring to the graph. No calculation is necessary.
pressure is increased to 0.987 atm and the tem - .
a What is the volume of this gas sample at
perature remains constant , what will the new standard pressure?
volume be? b. What is the volume of this gas sample at
A . 140 mL C. 200 mL 4.0 atm pressure?
B. 160 mL D. 240 mL c. At what pressure would this gas sample
3. What is the pressure exerted by a 0.500 mol occupy a volume of 5.0 L?
sample of nitrogen in a 10.0 L. container at V Vs. P for a Gas at Constant Temperature
20°C? 10.0
A. 1.2 kPa C. 0.10 k Pa
B. lOkPa D. 120 kPa 9.0

.
4 A sample of gas in a closed container at a tem - 8.0
perature of 100.0°C and 3.0 atm is heated to 7.0
300.0°C What is the pressure of the gas at the
higher temperature? 6.0
A . 35 atm C. 59 atm E 5.0
B. 4.6 atm D. 9.0 atm D
O
> 4.0
.
5 An unknown gas effuses twice as fast as CII4.
What is the molar mass of the gas? 3.0
A. 64 g/mol C. 8 g/mol 2.0
B. 32 g/ mol D. 4 g/mol
.
6 If 3 L N2 and 3 L H: are mixed and react
1.0

according to the equation below, how many 0.0

0.0
liters of unreacted gas remain? Assume temper -
ature and pressure remain constant. Pressure ( atm )
N2 ( £) + 3H2(g) -> 2NH3(J)
A. 4 L C. 2 L EXTENDED RESPONSE
B. 3 L D. 1 L 10. Refer to the plot in question 9. Suppose the
7. Avogadro s law states that same gas sample were heated to a higher tem -
A . equal numbers of moles of gases at the same perature and a new graph of V versus P were
plotted. Would the new plot be identical to this
conditions occupy equal volumes, regardless
one? If not. how would it differ ?
of the identity of the gases.
B. at constant pressure, gas volume is directly
proportional to absolute temperature.
C . the volume of a gas is inversely proportional
to its amount in moles. If you are permitted to. draw a
line through each incorrect answer choice as you
D. at constant temperature, gas volume is
eliminate it.
inversely proportional to pressure.

GASES 397
 EXPERIMENT 11

Mass and Density of Air

at Different Pressures
OBJECTIVES BACKGROUND
You have learned that the amount of gas present ,
• Measure the pressure exerted by a gas.
the volume of the gas, the temperature of the gas
• Measure the mass of a gas sample at differ- sample, and the gas pressure are related to one
ent pressures. another. If the volume and temperature of a gas
• Graph the relationship between the mass sample are held constant , the mass of the gas and
and pressure of a gas sample. the pressure that the gas exerts are related in a
simple way.
• Calculate the mass of an evacuated bottle.
In this investigation , you will use an automobile
• Calculate the volume of a bottle. tire pressure gauge to measure the mass of a bottle
• Calculate the density of air at different
W
and the air that the bottle contains for several air
pressures. pressures. A tire pressure gauge measures “ gauge
pressure.” meaning the added pressure in the tire in
MATERIALS addition to normal atmospheric air pressure. Gauge
pressure is often expressed in the units pounds per
automobile tire valve
square inch , gauge ( psig ) to distinguish them from
balance, centigram absolute pressures in pounds per square inch ( psi ).
barometer You will graph the mass of the bottle plus air against
the gas pressure and observe what kind of plot
cloth towel results. Extrapolating this plot in the proper way will
plastic soda let you determine both the mass and the volume of
bottle ( 2 or the empty bottle. This information will also allow you
3 L ) or other to calculate the density of air at various pressures.
heavy plastic
bottle SAFETY
tire pressure
gauge

For review of safety, please see Safety in the

Chemistry Laboratory in the front of your book .

PREPARATION
1 . Make a data table with five columns labeled
“ Gauge pressure ( psig ).” “ Mass of bottle +
air ( g ). “Corrected gas pressure ( psi ) ,” “ Mass of
M

air ( g ).” and “ Density of air ( g/cnT ).”

398 CHAPTER 7 7
 EXPERIMENT 11

PROCEDURE measured gauge pressure. Enter these results in

Your teacher will provide you with a bottle. This bot - the column “ Corrected gas pressure. **

tle contains air under considerable pressure, so han - 2. Analyzing Data: Make a graph of vour data .
dle it carefully. Do not unscrew the cap of the bottle. Plot corrected gas pressure on the .v-axis and
1. Use the tire pressure gauge to measure the mass of bottle plus air on the y-axis. The .v-axis
gauge pressure of the air in the bottle, as accu - should run from 10 psi to at least 80 psi. The
rately as you can read the gauge. It might be v-axis scale should allow extrapolation to cor -
convenient for one student to hold the bottle rected gas pressure of zero.
securely, wrapped in a cloth towel , while another
student makes the pressure measurement . 3. Analyzing Data: If your graph is a straight line,
Record this pressure in your data table. write an equation for the line in the form
v = ntx + b. If the graph is not a straight line,
2. Measure the mass of the bottle plus the air it explain why, and draw the straight line that
contains, to the nearest 0.01 g. Record this mass comes closest to including all of your data
in vour data table.
¥ points. Give the equation of this line.
3. With one student holding the wrapped bottle, 4. Interpreting Data: What is the mass of the
depress the tire stem valve carefully to allow some empty bottle ? ( Hint: When no more air escapes
air to escape from the bottle until the observed from the bottle in steps 4 and 5. the bottle is not
gauge pressure has decreased by 5 to 10 psig. empty; it still contains air at 1 atm .)
Then , repeat the measurements in steps 1 and 2.
5 . Analyzing Data: For each of your readings, cal -
4. Repeat the steps of releasing some pressure culate the mass of air in the bottle. Enter these
( step 3) and then measuring gauge pressure masses in vour data table.
¥

( step 1 ) and measuring the mass ( step 2 ) until

no more air comes out . 6. Interpreting Data: The density of air at typical
laboratory conditions is 1.19 g/L. Find the vol -
5. Now' repeat steps 1 and 2 one last time. The gauge ume of the bottle.
pressure should be zero: if it is not , then you prob-
ably have not released enough air , and you should 7. Interpreting Data: Calculate the density of air at
depress the valve for a longer time. You should each pressure for which you made measurements.
have at least five measurements of gauge pressure Enter these density values in your data table.
and mass, including this final set.
6. Read the atmospheric pressure in the room CONCLUSIONS
from the barometer, and record the reading in 1. Inferring Relationships: Based on your results
vour notebook . in this experiment , state the relationship
between the mass of a gas sample and the gas
pressure. Be sure to include limitations ( that is,
CLEANUP AND DISPOSAL
the quantities that must be kept constant ).
7. Return all equipment to its proper
place. Wash your hands thoroughly 2. Interpreting Graphics: Using your graph from
before you leave the lab and after all item 2 of Analysis and Interpretation , predict
work is finished . the mass of the bottle plus air at a gauge reading
of 60.0 psig. Estimate the mass of the gas in the
ANALYSIS AND INTERPRETATION bottle at that pressure.
1. Organizing Data: Correct each gauge pressure in
your data table to the actual gas pressure in psi,
by adding the barometric pressure ( in psi ) to each

GASES 399
 Solutions
Solutions are homogeneous mixtures of two
or more substances in a single phase.
Types of Mixtures SECTION 1

OBJECTIVES
J Distinguish between hetero-
I l is easvJ to determine that some materials are mixtures because Jvou geneous and homogeneous
can see their component parts. For example, soil is a mixture of sub- mixtures.
stances. including small rocks and decomposed animal and plant
matter. You can see this by picking up some soil in your hand and look -
^ List three different solute-
ing at it closely. Milk, on the other hand, does not appear to be a mixture, solvent combinations.
but in fact it is. Milk is composed principally of fats, proteins, milk sugar,
.
and water If you look at milk under a microscope. it will look something
w Compare the properties of
like Figure la . You can see round lipid ( fat ) droplets that measure from
suspensions, colloids, and
I to 10 / / m in diameter. Irregularly shaped casein ( protein ) particles that
solutions.
are about 0.2 / / m wide can also be seen. Both milk and soil are examples
of heterogeneous mixtures because their composition is not uniform.
Salt ( sodium chloride ) and water form a homogeneous mixture. The ^ Distinguish between electro-
sodium and chloride ions are interspersed among the water molecules, lytes and nonelectrolytes.
and the mixture appears uniform throughout. A model for a homoge -
neous mixture such as salt water is shown in Figure lb.

CHEMISTRY uI
Solutions *2TO*
Module 1 : States of Matter /Classes
of Matter
Suppose a sugar cube is dropped into a glass of water. You know from
experience that the sugar will dissolve. Sugar is described as “ soluble in
water.' By soluble we mean capable of being dissolved .
What happens as sugar dissolves? The lump gradually disappears as
sugar molecules leave the surface of their crystals and mix with water
molecules. Eventually all the sugar molecules become uniformly dis- FIGURE 1 ( a ) Milk
tributed among the water molecules, as indicated by the equally sweet consists of visible parti -
cles in a nonuniform
taste of any part of the mixture. All visible traces of the solid sugar are
arrangement, ( b ) Salt
water is an example of a
homogeneous mixture.
Water
Ions and water mol-
Sodium molecule
ecules are in a random
ion, Na '
••• * i arrangement .

* •*
•
V;
o Chloride ion, Cl
( a) Heterogeneous mixture—milk ( b) Homogeneous mixture —salt solution

SOLUTIONS 401
 Water Ethanol molecule, gone. Such a mixture is called a solution . A solution is a homogeneous
molecule, C 2H 5OH mixture of two or more substances in a single phase. In a solution , atoms,
H 20
molecules, or ions are thoroughly mixed, resulting in a mixture that has

• the same composition and properties throughout .

Components of Solutions
-
In the simplest type of solution , such as a sugar water solution , the par -
ticles of one substance are randomly mixed with the particles of anoth -
er substance. The dissolving mediani in a solution is called the solvent ,
and the substance dissolved in a solution is called the solute. The solute
is generally designated as that component of a solution that is of lesser
quantity. In the ethanol -water solution shown in Figure 2, ethanol is the
solute and water is the solvent . Occasionally, these terms have little
meaning. For example, in a 50% -50 % solution of ethanol and water, it
would be difficult , and in fact unnecessary, to say which is the solvent
and which is the solute.
In a solution , the dissolved solute particles are so small that they can -
not be seen . They remain mixed with the solvent indefinitely, so long as
(a )
the existing conditions remain unchanged . If the solutions in Figure 2 are
Water Copper ion, Cu2
poured through filter paper, both the solute and the solvent will pass
molecule, through the paper. The solute- particle dimensions are those of atoms,
H 20 —
a Chloride
ion, Cl —
molecules, and ions which range from about 0.01 to 1 nm in diameter.

* Types of Solutions
Solutions may exist as gases, liquids, or solids. Some possible solute -
w *
«
• solvent combinations of gases, liquids, and solids in solutions are sum -
marized in Table 1 . In each example, one component is designated as
the solvent and one as the solute.
Many alloys, such as brass ( made from zinc and copper ) and sterling
silver ( made from silver and copper ), are solid solutions in which the
atoms of two or more metals are uniformly mixed . By properly choosing
the proportions of each metal in the alloy, many desirable properties
can be obtained. For example, alloys can have higher strength and

TABLE 1 Some Solute-Solvent Combinations

for Solutions
(b)
Solute state Solvent state Example
FIGURE 2 The solute in a solu - Gas gas oxygen in nitrogen
tion can he a solid liquid , or
,

gas. ( a ) The ethanol - water solution Gas liquid carbon dioxide in water
is made from a liquid solute in a Liquid liquid alcohol in water
liquid solvent ( b ) The copper( II )
,
Liquid solid mercurv in silver and tin
J
chloride-water solution is made ( dental amalgam )
from a solid solute in a liquid solvent .
Note that the composition of each Solid liquid sugar in water
solution is uniform . Solid solid copper in nickel
( Monel 1 Nl alloy )

402 CHAPTER 12
( a ) 24 karat ( b ) 14 karat Silver Copper

FIGURE 3 ( a ) 24 karat gold-

-
is pure gold ( b ) 14 karat gold is an
,

greater resistance to corrosion than the pure metals. Pure gold ( 24 K ). alloy of gold with silver and
for instance, is too soft to use in jewelry. Alloying it with silver and cop- -
copper. 14 karat gold is 14/24. or
per greatly increases its strength and hardness while retaining its 58.3% , gold.
appearance and corrosion resistance. Figure 3 shows a comparison
between pure gold and a gold alloy. 14 - karat gold is a solution because
the gold , silver, and copper are evenly mixed at the atomic level .

Suspensions
If the particles in a solvent are so large that they settle out unless the
mixture is constantly stirred or agitated , the mixture is called a suspen -
sion . Think of a jar of muddy water. If left undisturbed , particles of soil
collect on the bottom of the jar . The soil particles are denser than the
solvent , water. Gravity pulls them to the bottom of the container.

—
—
Particles over 1000 nm in diameter 1000 times as large as atoms,
molecules, or ions form suspensions. The particles in suspension can
be separated from heterogeneous mixtures by passing the mixture
through a filter .

Colloids
Particles that are intermediate in size between those in solutions and
suspensions form mixtures known as colloidal dispersions, or simply
colloids. Particles between 1 nm and 1000 nm in diameter may form col -
loids. After large soil particles settle out of muddy water, the water is
often still cloudy because colloidal particles remain dispersed in the
SCllNKS. wr>
Otvttofrd mi msMmri fcy HN
NatMMl Some Twchm AIMKIMMA
water. If the cloudy mixture is poured through a filter, the colloidal par - For a variety of links related to this
ticles will pass through , and the mixture will remain cloudy. The parti -
cles in a colloid are small enough to be suspended throughout the Topic : Solutions
solvent bv the constant movement of the surrounding molecules. The SciLinks code: HC61422
colloidal particles make up the dispersed phase, and water is the dis - Topic: Colloids
persing medium . Examples of the various types of colloids are given in SciLinks code: HC60312
T able 2. Note that some familiar terms, such as emulsion and foam, refer
to specific types of colloids. For example, mayonnaise is an emulsion of oil

SOLUTIONS 403
 TABLE 2 Classes of Colloids
Class of colloid Phases Example
Sol solid dispersed in liquid paints, mud
Gel solid network extending throughout liquid gelatin
Liquid emulsion liquid dispersed in a liquid milk , mayonnaise
Foam gas dispersed in liquid shaving cream , whipped cream
Solid aerosol solid dispersed in gas smoke, airborne particulate
matter, auto exhaust
Liquid aerosol liquid dispersed in gas fog. mist , clouds, aerosol spray
Solid emulsion liquid dispersed in solid cheese, butter

droplets in water: the egg yolk in it acts as an emulsifying agent , which

helps to keep the oil droplets dispersed .

Tyndall Effect
Many colloids appear homogeneous because the individual particles
cannot be seen. The particles are, however , large enough to scatter light .
You have probably noticed that a headlight beam is visible from the
side on a foggy night , This effect , known as the Tyndall effect. occurs
when light is scattered by colloidal particles dispersed in a transparent
medium . The Tyndall effect is a property that can be used to distinguish
FIGURE 4 A beam of light between a solution and a colloid , as demonstrated in Figure 4.
distinguishes a colloid from a The distinctive properties of solutions, colloids, and suspensions are
solution . The particles in a colloid summarized in Table 3. The individual particles of a colloid can be
will scatter light , making the beam detected under a microscope if a bright light is cast on the specimen at
visible. The mixture of gelatin and
a right angle. The particles, which appear as tinv specks of light , are seen
water in the jar on the right is a
to move rapidly in a random motion . This motion is due to collisions of
colloid . The mixture of water and
sodium chloride in the jar on the rapidly moving molecules and is called Brownian motion , after its dis-
left is a true solution . coverer. Robert Brown.

TABLE 3 Properties of Solutions, Colloids, and Suspensions

Solutions Colloids Suspensions
Homogeneous Heterogeneous Heterogeneous
Particle size: 0.01-1 nm ; can be
atoms, ions, molecules
—
Particle size: 1 1 ( XK ) nm.
dispersed: can be aggregates or
Particle size: over 1000 nm .
suspended: can be large particles
large molecules or aggregates
Do not separate on standing Do not separate on standing Particles settle out
Cannot be separated by filtration Cannot be separated by filtration Can be separated by filtration
Do not scatter light Scatter light ( Tyndall effect ) May scatter light , but are not
transparent

404 CHAPTER 12
 QuidLAB <* Wear safety goggles and an apron.

Materials
Observing Solutions, • balance
Suspensions, and Colloids • 7 beakers, 400 mL
• clay
• cooking oil
Procedure 3. Transfer to individual test tubes • flashlight
1 . Prepare seven mixtures, each 10 mL of each mixture that
does not separate after stirring . • gelatin, plain
containing 250 mL of water • hot plate ( to boil H20)
and one of the following Shine a flashlight on each mix-
ture in a dark room. Make note • red food coloring
substances.
a. 12 g of sucrose of the mixtures in which the • sodium borate
path of the light beam is (Na 2B 407 * 10H 2 O)
b. 3 g of soluble starch
c. 5 g of clay visible. • soluble starch
d. 2 mL of food coloring • stirring rod
e. 2 g of sodium borate Discussion • sucrose
f . 50 mL of cooking oil
g. 3 g of gelatin 1 . Using your observations, classi- • test- tube rack
• water
fy each mixture as a solution,
Making the gelatin mixture: suspension, or colloid.
Soften the gelatin in 65 mL of cold
water, and then add 185 mL of 2. What characteristics did you
use to classify each mixture?
boiling water.
2. Observe the seven mixtures
and their characteristics.
Record the appearance of each
mixture after stirring.

Solutes: Electrolytes Versus

Nonelectrolytes Module 8: Strong and Weakly
Ionized Species, pH, and Titrations

Substances that dissolve in water are classified according to whether

they yield molecules or ions in solution. When an ionic compound dis-
.
solves the positive and negative ions separate from each other and are
surrounded by water molecules. These solute ions are free to move, mak -
ing it possible for an electric current to pass through the solution. A sub - FWW
stance that dissolves in water to give a solution that conducts electric
I For a variety of links related to this
current is called an electrolyte. Sodium chloride. NaCI. is an electrolyte, chapter, go to w
^lMi-erg
as is any soluble ionic compound. Certain highly polar molecular com -
pounds. such as hydrogen chloride, MCI, are also electrolytes because .
Topic: Llecirolytos /
Nonolcctrolytes
^
MCI molecules form the ions H30+ and Cl when dissolved in water. I SciLinks code: HCbQ .’ HO
By contrast, a solution containing neutral solute molecules does not
conduct electric current because it does not contain mobile charged

SOLUTIONS 405
 Chloride ion, Water molecule, Sugar molecule, Water molecule, Hydronium ion, Water molecule ,
cr Cl 2H 22 H20 H 20
H ?0
° n H30+

Sodium
ion, Na * 9 * *
Chloride
ion, Cl

* * 9* 9
9
9
9 9 9 9 9
9

( a ) Salt solution — ( b ) Sugar solution— (c ) Hydrochloric acid solution-

electrolyte solute nonelectrolyte solute electrolyte solute

FIGURE 5 ( a ) Sodium chloride

dissolves in water to produce
particles. A substance that dissolves in water to give a solution that does
a salt solution that conducts electric
not conduct an electric current is called a nonelectrolyte. Sugar is a non-
current . NaCl is an electrolyte.
( b ) Sucrose dissolves in water to electrolvte. Figure 5 shows an apparatus lor testing the conductivity of
produce a sugar solution that does solutions. The electrodes are conductors that are attached to a power
not conduct electricity. Sucrose supply and that make electric contact with the test solution. For a cur -
is a nonelectrolyte, ( c ) Hydrogen rent to pass through the light -bulb filament, the test solution must pro-
chloride dissolves in water to vide a conducting path between the two electrodes. A nonconducting
produce a solution that conducts solution is like an open switch between the electrodes, and there is no
current . HCI is an electrolyte.
current in the circuit .
The light bulb glows brightly if a solution that is a good conductor is
tested. Such solutions contain solutes that are electrolytes. For a mod-
erately conductive solution, however, the light bulb is dim. If a solution
is a poor conductor, the light bulb does not glow at all. Such solutions
contain solutes that are nonelectrolytes. You will learn more about the
strengths and behavior of electrolytes in Chapter 13.

SECTION REVIEW 4. Describe one way to prove that a mixture of sugar

1. Classify the following as either a heterogeneous or and water is a solution and that a mixture of sand
homogeneous mixture, and explain your answers. and water is not a solution.
a. orange juice b. tap water 5. Name the solute and solvent in the following:
2. a. What are substances called whose water solu- a. 14-karat gold
tions conduct electricity ? b. Why does a salt b. corn syrup
solution conduct electricity ? c. Why does a sugar- c. carbonated, or sparkling, water
water solution not conduct electricity ? Critical Thinking
3. Make a drawing of the particles in an NaCl solu-
tion to show why this solution conducts electricity.
6. ANALYZING INFORMATION If you allow a con -
tainer of sea water to sit in the sun, the liquid
Make a drawing of the particles in an NaCl crystal level gets lower and lower, and finally crystals
to show why pure salt does not conduct. appear. What is happening?

406 CHAPTER 12
 SECTION 2
The Solution Process
OBJECTIVES
yj List and explain three factors
Factors Affecting that affect the rate at which
a solid solute dissolves in a
the Rate of Dissolution liquid solvent.
If you have ever tried to dissolve sugar in iced tea. you know that tem -
perature has something to do with how quickly a solute dissolves. What Explain solution equilibrium,
other factors affect how quickly you can dissolve sugar in iced tea? and distinguish among
saturated, unsaturated, and
Increasing the Surface Area of the Solute supersaturated solutions.
Sugar dissolves as sugar molecules leave the crystal surface and mix
with water molecules. The same is true for any solid solute in a liquid sj Explain the meaning of
solvent: molecules or ions of the solute are attracted by the solvent. " like dissolves like " in terms
Because the dissolution process occurs at the surface of the solute, it of polar and nonpolar
.
can be speeded up if the surface area of the solute is increased Crushing substances.
sugar that is in cubes or large crystals increases its surface area. In gen -
eral. the more finely divided a substance is. the greater the surface area
per unit mass and the more quickly it dissolves. Figure 6 shows a model ^ List the three interactions that
contribute to the enthalpy of
of solutions that are made from the same solute but have a different solution, and explain how
amount of surface area exposed to the solvent . they combine to cause disso -
lution to be exothermic or
Agitating a Solution endothermic.
Very close to the surface of a solute, the concentration of dissolved
solute is high. Stirring or shaking helps to disperse the solute particles
Compare the effects of
temperature and pressure
on solubility.
Small surface area exposed Large surface area exposed
to solvent —slow rate to solvent —faster rate
\

Solvent
particle
Solute %
*
* 4 *
** * * FIGURE 6 The rate at which
a solid solute dissolves can be
increased by increasing the surface
area. A powdered solute has a
greater surface area exposed to
solvent particles and therefore
CuS04 * 5 H20 large crystals CuS04 * 5 H 20 powdered dissolves faster than a solute in
Increased surface area large crystals .
SOLUTIONS 407
 and bring fresh solvent into contact with the solute surface. Thus, the
CAREERS in Chemistry effect of stirring is similar to that of crushing a solid — contact between
the solvent and the solute surface is increased.
Environmental Chemist
What happens to all of our chemical Heating a Solvent
waste, such as household cleaners and You have probably noticed that sugar and many other materials dis-
shampoos that we rinse down the
solve more quickly in warm water than in cold water. As the tempera-
drain, industrial smoke, and materials
that have not been removed in water ture of the solvent increases, solvent molecules move faster, and their
treatment plants ? Environmental average kinetic energy increases.Therefore, at higher temperatures, col -
chemists investigate the sources and lisions between the solvent molecules and the solute are more frequent
effects of chemicals in all parts of the and are of higher energy than at lower temperatures. This helps to sepa-
environment. Then, chemists also devise rate solute molecules from one another and to disperse them among the
acceptable ways to dispose of chemi-
cals. This may involve conducting tests
solvent molecules .
to determine whether the air, water, or
soil is contaminated; developing pro-
grams to help remove contamination;
designing new production processes
to reduce the amounts of waste pro -
Solubility
duced; handling regulation and compli-
ance issues; and advising on safety and If you add spoonful after spoonful of sugar to tea. eventually no more
emergency responses. Environmental sugar will dissolve. For every combination of solvent with a solid solute at
chemists must understand and use many a given temperature, there is a limit to the amount of solute that can be
other disciplines, including biology, geol- dissolved. The point at which this limit is reached for any solute-solvent
ogy and ecology. combination is difficult to predict precisely and depends on the nature
of the solute, the nature of the solvent, and the temperature.
The following model describes why there is a limit. When solid sugar is
first added to water, sugar molecules leave the solid surface and move
about at random in the solvent. Some of these dissolved molecules may
collide with the crystal and remain there (recrystallize ). As more solid
dissolves and the concentration of dissolved molecules increases, these
SC collisions become more frequent. Eventually, molecules are returning to
/ lNKS. M ft
Developed nd mjinUined try Ike
the crystal at the same rate at which they are going into solution, and a
NJtMMui SoeMe TrMken A110<14<M<1 dynamic equilibrium is established between dissolution and
For a variety of links related to this crystallization. Ionic solids behave similarly, as shown in Figure 7.
chapter, go to viv.v,s:111 nks org Solution equilibrium is the physical slate in which the opposing pro -
Topic: Solubility
SciLinks code: HC61421
^ cesses of dissolution and crystallization of a solute occur at equal rates.

Recrystallizing Dissolving

FIGURE 7 A saturated solution in

a closed system is at equilibrium.
The solute is recrystallizing at the
same rate that it is dissolving, even
though it appears that there
is no activity in the system .

408 CHAPTER 12
 Mass of Solute Added Vs. Mass of Solute Dissolved FIGURE 8 The graph
shows the range of solute
60
o
'
A. Unsaturated TS
masses that will produce
an unsaturated solution.
Qj
If a solution is unsaturated,
O more solute can dissolve. Once the saturation point

O ©
No undissolved solute
remains.
-
»
is exceeded , the system
will contain undissolved
O
urr n
i
\ ~ 40
B. Saturated solute.
u<T3 01 If the amount of solute added
2 5 exceeds the solubility, some
o CTt solute remains undissolved.
v/> O
E<TJ 2 20

C
^
CD
C

to Solubility = 46 4 g/ 100 g
n:
2
0
0 20 40 60 80 100
Mass in grams of NaCH 3 COO added to 100 g water at 20°C

Saturated Versus Unsaturated Solutions

/ 1 solution that contains the maximum amount of dissolved solute is
described as a saturated solution. How can you tell that the
NaCH COO solution pictured in Figure S is saturated ? If more sodium
^
acetate is added to the solution, it falls to the bottom and does not dis-
solve because an equilibrium has been established between ions leaving
and entering the solid phase. If more water is added to the saturated
solution , then more sodium acetate will dissolve in it . At 20 C. 46.4 g of
NaCH 3COO is the maximum amount that will dissolve in
I 00. g of water. A solution that contains less solute than a saturated solu -
lion under the existing conditions is an imsaf urated solution.

Supersaturated Solutions
When a saturated solution of a solute whose solubility increases with
temperature is cooled , the excess solute usually comes out of solution ,
leaving the solution saturated at the lower temperature. But sometimes,
if the solution is left to cool undisturbed , the excess solute does not
separate and a supersaturated solution is produced . A supersaturated
solution is a solution that contains more dissolved solute than a satu -
rated solution contains under the same conditions. A supersaturated
solution may remain unchanged for a long time if it is not disturbed ,
but once crystals begin to form , the process continues until equilibrium
is reestablished at the lower temperature. An example of a supersatu -
rated solution is one prepared from a saturated solution of sodium
thiosulfate. Na:S:03. or sodium acetate. NaCH 3COO. Solute is added
to hot water until the solution is saturated , and the hot solution is fil -
tered . The filtrate is left to stand undisturbed as it cools. Dropping a
small crystal of the solute into the supersaturated solution ( “seeding" )
or disturbing the solution causes a rapid formation of crystals by the
excess solute.

SOLUTIONS 409
 —ryrtTreffrrn Solubility Values
The solubility of a substance is the amount of that substance required to
Chemistry in Action
form a saturated solution with a specific amount of solvent at a specified
Go to go. hrw. com for a full - length
feature on how surfactants make temperature . The solubility of sugar, for example, is 204 g per 100. g of
nonpolar and polar compounds water at 20. C. The temperature must he specified because solubility
soluble . varies with temperature. For gases, the pressure must also be specified .
Solubilities must be determined experimentally, and they vary widely, as
Keyword: HC 6 SLNX
illustrated in Table 4. Solubility values can be found in chemical hand -
books and are usually given as grams of solute per 100. g of solvent or
per 100. mL of solvent at a given temperature.
The rate at which a solid dissolves is unrelated to its solubility at that
temperature. The maximum amount of a given solute that dissolves and
reaches equilibrium is always the same under the same conditions.

Solute- Solvent Interactions

Lithium chloride is highly soluble in water, but gasoline is not . On the
other hand. gasoline mixes readily with benzene, C6 H 6, but lithium chlo-
ride does not . Why are there such differences in solubility?
“ Like dissolves like’ is a rough but useful rule for predicting whether
*

one substance will dissolve in another. What makes substances similar

depends on the type of bonding, the polarity or nonpolarity of mol -
ecules. and the intermolecular forces between the solute and solvent .

TABLE 4 Solubility of Solutes as a Function of Temperature (in g solutelWO. g H20 )

Temperature (°C)
Substance 0 20 40 60 80 100
AgN 03 122 216 311 440 585 733
Ba ( OH )2 1.67 3.89 8.22 20.94 101.4

^12 ^ ^
Ca OH )
(
22 11 179
0.189
204
0.173
238
0.141
287
0.121
362 487
0.07
2
Ce 2( S04 )3 20.8 10.1 3.87
KC1 28.0 34.2 40.1 45.8 51.3 56.3
KI 128 144 162 176 192 206
KNO3 13.9 31.6 61.3 106 167 245
LiCl 69.2 83.5 89.8 98.4 112 128
LHCO 1.54 1.33 1.17 1.01 0.85 0.72
NaCl 35.7 35.9 36.4 37.1 38.0 39.2
NaN 03 73 87.6 102 122 148 180
C02 ( gas at SP ) 0.335 0.169 0.0973 0.058
Q: ( gas at SP ) 0.00694 0.00537 0.00308 0.00227 0.00138 0.00

410 CHAPTER 12
 Hydrated Li +
FIGURE 9 When LiCI dissolves,
the ions are hydrated. The attraction

e between ions and water molecules

is strong enough that each ion in
solution is surrounded by water
LiCI crystal molecules.
Water molecule

Hydrated Cl

Dissolving Ionic Compounds in Aqueous Solution

The polarity of water molecules plays an important role in the forma -
tion of solutions of ionic compounds in water. The slightly charged parts
of water molecules attract the ions in the ionic compounds and sur -
round them to keep them separated from the other ions in the solution .
Suppose we drop a few crystals of lithium chloride into a beaker of
water. At the crystal surfaces water molecules come into contact with
,

Li and Cl ions. The positive ends of the water molecules are attracted
to Cl ions while the negative ends are attracted to Li ions. The attrac -
'

tion between water molecules and the ions is strong enough to draw the
ions away from the crystal surface and into solution as illustrated in
,

Figure 9. This solution process w ith wetter as the solvent is referred to as

hydration. The ions are said to be hydrated . As hydrated ions diffuse
into the solution other ions are exposed and are drawn awav from the
,

crystal surface bv the solvent . The entire crystal gradually dissolves, and
hydrated ions become uniformly distributed in the solution .
sof
When crystallized from aqueous solutions some ionic substances
,

form crystals that incorporate water molecules. These crystalline com - /

/
\N
/
pounds. known as hydrates, retain specific ratios of water molecules /
/ / S
and are represented by formulas such as CuS04*5 H:0. Heating the
H2O / H 2O
crystals of a hydrate can drive off the water of hydration and leave the
anhvdrous salt . When a crystalline hvdrate dissolves in water, the H 2O
water of hydration returns to the solvent . The behavior of a solution
made from a hydrate is no different from the behavior of one made H 2O H 2O
/
from the anhydrous form . Dissolving either form results in a system 0
containing hydrated ions and water. 0 \
\ /
/
V /
Nonpolar Solvents
Ionic compounds are generally not soluble in nonpolar solvents such as *2-
soa
carbon tetrachloride. CC14. and toluene, QH 5CH 3. The nonpolar sol -
FIGURE 10 Hydrated
vent molecules do not attract the ions of the crystal strongly enough to
copper( II ) sulfate has water as part
overcome the forces holding the crystal together. of its crystal structure. Heating
Would you expect lithium chloride to dissolve in toluene? No. LiCI is releases the water and produces the
not soluble in toluene. LiCI and QH 5CH 3 differ widely in bonding, anhydrous form of the substance,
polarity, and intermolecular forces. which has the formula CuSQ4.

SOLUTIONS 411
 Liquid Solutes and Solvents
When you shake a bottle of salad dressing, oil droplets become dis-
persed in the water. As soon as you stop shaking the bottle, the strong
attraction of hydrogen bonding between the water molecules squeezes
out the oil droplets, forming separate layers. Liquids dial arc not soluble
in each oilier are immiscible. Toluene and water , shown in Figure 11 , are
another example of immiscible substances.
Nonpolar substances, such as fats. oils, and greases, are generally
quite soluble in nonpolar liquids, such as carbon tetrachloride, toluene,
and gasoline. The only attractions between the nonpolar molecules are
London forces, which are quite weak . The intermolecular forces existing
NO
' in the solution are therefore very similar to those in pure substances.
Toluene Thus, the molecules can mix freely with one another.
Liquids dial dissolve freely in one another in any proportion are said to
« •• Water be miscible. Benzene and carbon tetrachloride are miscible. The nonpolar
molecules of these substances exert no strong forces of attraction or
repulsion , so the molecules mix freely. Ethanol and water , shown in
Insoluble and immiscible

FIGURE 11 Toluene and water

—
Figure 12, also mix freely, but for a different reason. The Ol I group on
an ethanol molecule is somewhat polar. This group can form hydrogen
are immiscible. The components of bonds with water as well as with other ethanol molecules. The inter-
this system exist in two distinct molecular forces in the mixture are so similar to those in the pure liquids
phases. that the liquids are mutually soluble in all proportions.
II ll
H-C-C-OH ethanol
H II
Gasoline is a solution composed mainly of nonpolar hydrocarbons
and is also an excellent solvent for fats. oils, and greases. The major
intermolecular forces acting between the nonpolar molecules are weak
London forces.
FIGURE 12 ( a ) Water and ethanol Ethanol is intermediate in polarity between water and carbon tetra -
are miscible . The components of this chloride. It is not as good a solvent for polar or ionic substances as water
system exist in a single phase w i t h a is. Sodium chloride is only slightly soluble in ethanol. On the other
uniform arrangement ( b ) Hydrogen
,
-
hand , ethanol is a better solvent than water is for less polar substances
bonding between the solute and sol - because the molecule has a nonpolar region .
vent enhances the solubility ol
ethanol in water.
Hydrogen bond
Water molecule,
H 0 ,

£
* ** * **
*
Ethanol molecule,
C2 H 5 OH
( a ) Miscible

412 CHAPTER 12
Effects of Pressure on Solubility
Changes in pressure have very little effect on the solubilities of liquids
or solids in liquid solvents. However , increases in pressure increase gas
solubilities in liquids.
When a gas is in contact with the surface of a liquid , gas molecules
can enter the liquid . As the amount of dissolved gas increases, some
molecules begin to escape and reenter the gas phase. An equilibrium is
eventually established between the rates at which gas molecules enter
and leave the liquid phase. As long as this equilibrium is undisturbed ,
the solubility of the gas in the liquid is unchanged at a given pressure.

gas + solvent solution

FIGURE 13 ( a ) There are no gas
Increasing the pressure of the solute gas above the solution puts
bubbles in the unopened bottle of
stress on the equilibrium . Molecules collide with the liquid surface more
soda because the pressure of CO:
often. The increase in pressure is partially offset by an increase in the applied during bottling keeps the
rate of gas molecules entering the solution . In turn , the increase in the carbon dioxide gas dissolved in the
amount of dissolved gas causes an increase in the rate at which mol - liquid , ( b ) When the cap on the bot -
ecules escape from the liquid surface and become vapor. Eventually, tle is removed , the pressure of C02
equilibrium is restored at a higher gas solubility. An increase in gas pres- on the liquid is reduced , and CO >
sure causes the equilibrium to shift so that more molecules are in the can escape from the liquid.The
soda effervesces when the bottle is
liquid phase.
opened and the pressure is reduced.

Henry 's Law C02 under high

The solubility of a gas in a liquid is directly pressure above solvent
proportional to the partial pressure o f that gas
on the surface of the liquid . This is a statement
of Henry’s law, named after the English
chemist William Henry. Henry s law applies to
'

gas- liquid solutions at constant temperature.

Recall that when a mixture of ideal gases is
confined in a constant volume at a constant
temperature, each gas exerts the same pres-
sure it would exert if it occupied the space
alone. Assuming that the gases do not react in Soluble C02
any way, each gas dissolves to the extent it molecules
would dissolve if no other gases were present .
Air at atmospheric
In carbonated beverages, the solubility of pressure
COi is increased by increasing the pressure.
At the bottling plant , carbon dioxide gas is
forced into the solution of flavored water at
a pressure of 5-10 atm . The gas-in -liquid
solution is then sealed in bottles or cans.
When the cap is removed , the pressure is
reduced to 1 atm. and some of the carbon
dioxide escapes as gas bubbles. The rapid
escape o f a gas from a liquid in which it is dis- Soluble C 02 C 02 gas
solved is known as effervescence and is molecules bubble
shown in Figure 13. ( b)

SOLUTIONS 413
 Solubility Vs. Temperature Data for Some Gases 80
70
5 60 S02 volume
5.4
x H 2 S volume £ 50

S E
® 3 I' D 40

3
|
3 E 30
un 2
o ro C 02 volume o 03
un O cn 20
' 03
1
E E 10
02 volume
0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

Temperature (°C ) Temperature (° C)

FIGURE 14 The solubility

ol gases in water decreases with
increasing temperature. Which
Effects of Temperature on Solubility
gas has the greater solubility at
First , let ’s consider gas solubility. Increasing the temperature usually
30 C—C O, or SO,? decreases gas solubility. As the temperature increases, the average
kinetic energy of the molecules in solution increases. A greater number
ol solute molecules are able to escape from the attraction of solvent
molecules and return to the gas phase. At higher temperatures, there-
fore. equilibrium is reached with fewer gas molecules in solution, and
gases are generally less soluble, as shown in Figure 14 .
Tlie effect of temperature on the solubility of solids in liquids is more
difficult to predict. Often, increasing the temperature increases the solu-
.
bility of solids However, an equivalent temperature increase can result

Solubility Vs. Temperature for Some Solid Solutes

260
KN03
240
2fU 220
*
O
200
NaNOj
180
o
2 160
<u RbCI
i 140
<SlJ
LiCI
120
*O.'
k

C 100
80 NH4 CI
-3Q 60 KCI
FIGURE 15 Solubility curves for o
<y>
various solid solutes generally show 40 NaCI
Li,SO,
increasing solubility with increases 20
.
in temperature From the graph, you
0
can see that the solubility of NaN( ) 3 0 10 20 30 40 50 60 70 80 90 100
is affected more by temperature
than is Nat l. Temperature (°C)

414 CHAPTER 12
in a large increase in solubility for some solvents and only a slight
change for others.
In Table 4 and Figure 15, compare the effect of temperature on the
solubilities of potassium nitrate. KNO3, and sodium chloride. NaCI .
About 14 g of potassium nitrate will dissolve in 100. g of water at 0. C.
The solubility of potassium nitrate increases by more than 150 g KNO ;
per 100. g H 20 when the temperature is raised to 80. C. I ’ nder similar
circumstances, the solubility of sodium chloride increases by only about
2 g NaCI per 100. g fCO. In some cases, solubility of a solid decreases
with an increase in temperature. For example, between 0. C and 60. C the
solubility of cerium sulfate. C e:( S04 h. decreases by about 17 g/100 g.
'

Enthalpies of Solution
The formation of a solution is accompanied by an energy change. If you
dissolve some potassium iodide, KI , in water , you will find that the out -
side of the container feels cold to the touch. But if you dissolve some
sodium hydroxide. NaOH , in the same way, the outside of the container
feels hot. The formation of a solid-liquid solution can apparently either
absorb energy ( KI in water ) or release energy as heat ( NaOH in water ).
During the formation of a solution , solvent and solute particles expe -
rience changes in the forces attracting them to other particles. Before
dissolving begins, solvent molecules are held together by intermolecu -
-
lar forces ( solvent solvent attraction ) . In the solute, molecules are held
-
together by intermolecular forces ( solute solute attraction ). Energy is
required to separate solute molecules and solvent molecules from their
neighbors. A solute panicle that is surrounded by solvent molecules, as FIGURE 16 The graph shows the
shown by the model in Figure 9, is said to be solvated. changes in the enthalpy that occur
during the formation of a solution.
Solution formation can be pictured as the result of the three interac-
How would the graph differ for a
tions summarized in Figure 16. system with an endothermic heat of
solution ?

Components
Step 2

' • % •*
4

Solute Solvent Solvent particles being

>
a moved apart to allow
Step 1
_c solute particles to Solvent particles being
c
LU
% % 0 •- enter liquid. attracted to and
Energy absorbed solvating solute particles.
* *
Energy released

Solute particles becoming

separated from solid.
Energy absorbed
\ AH solution Exothermic

SOLUTIONS 415
 TABLE 5 Enthalpies of Solution (kJImol solute at 25°C )
Enthalpy of Enthalpy of
Substance solution Substance solution
AgN03(5) +22.59 KOH( s ) -57.61
CH3COOH( /) - 1.51 MgS04(.v) +15.9
HCl(g) -74.84 NaCl(.v) +3.8S
HI(g) -81.67 NaN03( s) +20.50
KCl( .v ) +17.22 NaOH(.v) -44.51

KC103(.v ) +41.38 NH3(g) -30.50

KI( s) +20.33 NH4CI(S) +14.7S
KNQ3(5) +34.89 NH4N03( s) +25.69

The net amount of energy absorbed as heat by the solution when a

specific amount of solute dissolves in a solvent is the enthalpy of solu-
tion. From the model in Figure 16, you can see that the enthalpy of solu-
tion is negative ( energy is released) when the sum of attractions from
Steps 1 and 2 is less than Step 3. The enthalpy of solution is positive
( energy is absorbed ) when the sum of attractions from Steps 1 and 2 is
greater than Step 3.
You know that heating decreases the solubility of a gas. so dissolu-
tion of gases is exothermic. How do the values for the enthalpies of
solution in Table 5 support this idea of exothermic solution processes
for gaseous solutes?
In the gaseous state, molecules are so far apart that there are virtu-
ally no intcrmolecular forces of attraction between them. Therefore, the
solute-solute interaction has little effect on the enthalpy of a solution of
a gas. Energy is released when a gas dissolves in a liquid because attrac -
tion between solute gas and solvent molecules outweighs the energy
needed to separate solvent molecules.

SECTION REVIEW 5. If a warm bottle of soda and a cold bottle of soda

1. Why would you expect a packet of sugar to dis- are opened, which will effervesce more and why ?
solve faster in hot tea than in iced tea ? Critical Thinking
2. a. Explain how you would prepare a saturated 6. PREDICTING OUTCOMES You get a small amount
solution of sugar in water b. How would you then
,
of lubricating oil on your clothing. Which would
make it a supersaturated solution? work better to remove the oil—water or toluene?
3. Explain why ethanol will dissolve in water and Explain your answer.
carbon tetrachloride will not. 7. INTERPRETING CONCEPTS A commercial " fizz
4. When a solute molecule is solvated, is energy saver " pumps helium under pressure into a soda
released or absorbed? bottle to keep gas from escaping. Will this keep
C0? in the soda bottle ? Explain your answer.

416 CHAPTER 12
 CROSS - DISCIPLINARY CONNECTION
- > V J > J > J J
i J 4
*
Artificial Blood

A patient lies bleeding on a stretcher. chemical called a surfactant is added the mixture are needed.
The doctor leans over to check the to hold the mixture together. The Oxygent is currently being tested
patient's wounds and barks an order perfluorocarbons are sheared into in surgical patients.
to a nearby nurse: " Get him a unit of tiny droplets and then coated with " Once this product is approved
artificial blood, stat! " According to the bonding molecules. One end of and has been demonstrated to be
Dr. Peter Keipert, Program Director of these molecules attaches to the per - safe and effective in elective surgery,
Oxygen Carriers Development at fluorocarbon, and the other end I think you will see its use spread
Alliance Pharmaceutical Corp., this attaches to the water, creating a into the emergency critical- care
scenario may soon be commonplace milky emulsion. The blood- substitute arena," says Dr. Keipert. "A patient
thanks to a synthetic mixture that mixture, called Oxygent , is admin - who has lost a lot of blood and who
can perform one of the main func - istered to a patient in the same way is currently being resuscitated with
tions of human blood— transporting regular blood is. The perfluorocar - normal fluids like saline solutions
oxygen. bons are eventually exhaled through would be given Oxygent as an addi-
The hemoglobin inside red blood the lungs. tional oxygen-delivery agent in the
cells collects oxygen in our lungs, Oxygent only functions to carry emergency room."
transports it to all the tissues of the gases to and from tissues; it cannot
body, and then takes carbon dioxide clot or perform any of the immune- Questions
back to the lungs. Dr. Keipert's blood system functions that blood does. 1. How would the approval of
substitute accomplishes the same Still, the substitute has several Oxygent benefit the medical
task, but it uses nonpolar chemicals advantages over real blood. Oxygent community ?
called perfluorocarbons instead of has a shelf life of more than a year.
2 . How do scientists prevent the
hemoglobin to transport the oxygen. Oxygent also eliminates many of the
nonpolar perfluorocarbons in
The perfluorocarbons are carried in a risks associated with blood transfu-
Oxygent from separating from
water-based saline solution, but sions. Because the substitute can dis-
the water ?
because nonpolar substances and solve larger amounts of oxygen than
water do not mix well, a bonding real blood can, smaller amounts of

I For a variety of links related to this

I Topic : Perfluorocarbons I
I SciLinks code: HC61123
A C8F17 Brbelongs to a class of compounds
called perfluorocarbons.

SOLUTIONS 417
 SECTION 3
Concentration
OBJECTIVES
SJ Given the mass of solute and
of Solutions
volume of solvent, calculate
the concentration of a
solution.
T he concentration of a solution is a measure o f the amount of solute
j Given the concentration of in a given amount of solvent or solution . Some medications are solutions
a solution, determine the of drugs — a one- teaspoon dose at the correct concentration might cure
amount of solute in a given the patient, while the same dose in the wrong concentration might kill
amount of solution. the patient.
In this section, we introduce two different ways of expressing the
Given the concentration of
concentrations of solutions: molarity and molality.
^ Sometimes, solutions are referred to as ‘'dilute" or “concentrated."
a solution, determine the
amount of solution that hut these are not very definite terms. “Dilute " just means that there is a
contains a given amount relatively small amount of solute in a solvent. “Concentrated," on the
of solute. other hand, means that there is a relatively large amount of solute in a
solvent . Note that these terms are unrelated to the degree to which a
solution is saturated. A saturated solution of a substance that is not very
soluble might be very dilute.

Molarity
Molarity is the number of moles of solute in one liter of solution. To
relate the molarity of a solution to the mass of solute present, you must
.
know the molar mass of the solute For example, a “one molar " solution
of sodium hvdroxide, NaOH, contains one mole of NaOII in everv liter •

of solution. The symbol for molarity is M. and the concentration of a

one molar solution of sodium hydroxide is written as 1 M NaOI I.
One mole of NaOH has a mass of 40.0 g. If this quantity of NaOII is
dissolved in enough water to make exactly 1.00 L of solution, the solu-
tion is a 1 M solution. If 20.0 g of NaOII. which is 0.500 mol. is dissolved
in enough water to make 1.00 L of solution, a 0.500 M NaOH solution
is produced. This relationship between molarity, moles, and volume may
be expressed in the following ways.
amount of solute ( mol )
molarity ( M ) =
volume of solution ( L )
0.500 mol NaOH
1.00 L
= 0.500 M NaOH

418 CHAPTER ;2
If twice the molar mass of NaOH. 80.0 g. is dissolved in enough water to
make 1 L of solution, a 2 M solution is produced. The molarity of any
solution can be calculated by dividing the number of moles of solute by
the number of liters of solution.
Note that a 1 M solution is not made by adding 1 mol of solute to
1 L of solvent . In such a case, the final total volume of the solution might
not be 1 L. Instead. 1 mol of solute is first dissolved in less than 1 L of
solvent. Then, the resulting solution is carefully diluted with more sol-
.
vent to bring the total volume to 1 L. as shown in Figure 17 The follow - FIGURE 17 The preparation of a
ing sample problem will show you how molarity is often used. 0.5000 M solution of CuS04 5H:0 #

starts with calculating the mass of

solute needed.

Start by calculating the mass

of CuS04 * 5 H20 needed.
Making a liter of this solution
requires 0.5000 mol of solute.
Convert the moles to mass by
multiplying by the molar mass Add some solvent to the Rinse the weighing beaker Put the stopper in the flask ,
of CuS 04 •5 H20. This mass is solute to dissolve it, and with more solvent to remove and swirl the solution
calculated to be 124.8 g. then pour it into a 1.0 L all the solute, and pour the thoroughly.
volumetric flask . rinse into the flask . Add
water until the volume of
the solution nears the neck
of the flask.

Carefully fill the flask to the Restopper the flask, and The resulting solution has
1.0 L mark with water. invert it at least 10 times to 0.5000 mol of solute dissolved
ensure complete mixing. in 1.000 L of solution, which is
a 0.5000 M concentration.

SOLUTIONS 419
 SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.

You have 3.50 I of solution that contains 90.0 g of sodium chloride. NaCL
,

What is the molarity of that solution?

SOLUTION
1 ANALYZE Given: solute mass = 90.0 g NaCl
solution volume = 3.50 L
Unknown: molarity of NaCl solution

2 PLAN Molarity is the number of moles of solute per liter of solution. The solute is described
in the problem by mass, not the amount in moles. You need one conversion ( grams to moles
of solute ) using the inverted molar mass of NaCl to arrive at your answer.
grams of solute > number of moles of solute » molarity
l mol NaCl
g NaCl x = mol NaCl
g NaCl
amount of solute ( mol)
= molarity of solution ( M )
V solution (L )

3 COMPUTE You will need the molar mass of NaCl.

NaCl = 58.44 g/mol
l mol NaCl
90.0 g NaCl x = 1.54 mol NaCl
58.44 g NaCl
1.54 mol NaCl
= 0.440 M NaCl
3.50 L of solution
4 EVALUATE Because each factor involved is limited to three significant digits, the answer should
have three significant digits, which it does. The units cancel correctly to give the desired
moles of solute per liter of solution, which is molarity .

SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter

You have 0.8 l. of a 0.5 M HCI solution. How many moles of IICI does this solution contain?

SOLUTION
1 ANALYZE Given: volume of solution = 0.8 L
concentration of solution = 0.5 M HCI
Unknown: moles of HCI in a given volume

2 PLAN The molarity indicates the moles of solute that are in one liter of solution.
Given the volume of the solution, the number of moles of solute
can then be found.

concentration (mol of HCI/L of solution ) x volume ( L of solution ) = mol of HCI

420 CHAPTER 12
3 COMPUTE
0.5 mol HCI
x 0.8 L ul-soltttirm = 0.4 mol MCI
1.0 Lof-sokrtton
4 EVALUATE The answer is correctly given to one significant digit. The units cancel correctly to give the
.
desired unit. mol. There should be less than 0.5 mol HCI because less than 1 L of solution
was used.

SAMPLE PROBLEM C For more help, go to the Mat / l Tutor at the end of this chapter.

To produce 40.0 g of silver chromate, you will need at least 23.4 g of potassium chromate in solution as a
reactant. All you have on hand is 5 L of a 6.0 M K ?Cr 04 solution. What volume of the solution is needed
to give you the 23.4 g K 2Cr ()4 needed for the reaction?

SOLUTION
1 ANALYZE Given: volume of solution = 5 L
concentration of solution = 6.0 M KT 'rO ,
mass of solute = 23.4 g K:Cr 04
mass of product = 40.0 g Ag:Cr() 4
Unknown: volume of K 2Cr() 4 solution in L

2 PLAN The molarity indicates the moles of solute that are in I L of solution. Given the mass
of solute needed, the amount in moles of solute can then be found. Use the molaritv and the w

amount in moles of K 2CI 04 to determine the volume of k:Cr04 that will provide 23.4 g.

grams of solute > moles solute

moles solute and molarity - of solution needed
• liters

3 COMPUTE To get the moles of solute, you'll need to calculate the molar mass of k:Cr 04.
I mol K:Cr()4 = 104.2 g k:Cr 04
I mol K:CK )4
23.4 g k?Cr04 x = 0.120 mol K:CrQ4
104.2 gK?CrG4
0.120 mol KGCr 04
6.0 M K:CrQ4 =
x L K:Cr 04 soln
.v = 0.020 L K 2CrQ4 soln

4 EVALUATE The answer is correctly given to two significant digits. Hie units cancel correctly
to give the desired unit, liters of solution.

PRACTICE Answers in Appendix E

1. What is the molarity of a solution composed of 5 , 85 g of potassium

.
iodide KI, dissolved in enough water to make 0.125 L of solution?
— crfidii-TTfTi
2. How many moles of H:S04 are present in 0.500 L. of a 0.150 M Go to go.hrw.com for
H:S04 solution? more practice problems
that ask you to calculate
3. What volume of 3.00 M NaCI is needed for a reaction that molarity.
requires 146.3 g of NaCI? Keyword: HC 6 SLNX

SOLUTIONS 421
 Molality
Molality is the concentration of a solution expressed in moles of solute
per kilogram of solvent. A solution that contains 1 mol of solute, sodium
hydroxide, NaOH . for example, dissolved in exactly 1 kg of solvent is a
“ one molar ' solution . The symbol for molality is m , and the concentra -

tion of this solution is written as 1 m NaOH.

One mole of NaOH has a molar mass of 40.0 g. so 40.0 g of NaOH
dissolved in 1 kg of water results in a one molal NaOH solution . If
20.0 g of NaOH , which is 0.500 mol of NaOH . is dissolved in exactly
1 kg of water , the concentration of the solution is 0.500 m NaOH .

moles solute
molality = mass of solvent ( kg )

0.500 mol NaOH

1 kg H:Q
= 0.5( H ) m NaOH

If 80.0 g of sodium hydroxide, which is 2 mol . is dissolved in I kg of water,

a 2.00 m solution of NaOH is produced. The molality of any solution can
be found by dividing the number of moles of solute by the mass in kilo-
grams of the solvent in which it is dissolved. Note that if the amount of
solvent is expressed in grams, the mass of solvent must be converted to
kilograms by multiplying by the following conversion factor.
1 kg/ 10( H ) g

FIGURE 18 The preparation of a Figure 18 shows how a 0.5000 m solution of CuS04*5 H:0 is prepared ,
0.50( H ) n\ solution of CuS04 5 H:0
# in contrast with the 0.5000 M solution in Figure 17.
also starts with the calculation of the
mass ol solute needed .

? '

l V

Calculate the mass of

CUS04 * 5H ? 0 needed. Making
this solution will require Add 1.000 kg of solvent to
-
0.5000 mol of CUS04 5 H20
per kilogram of solvent
the solute in the beaker.
Because the solvent is water,
( 1000 g). This mass is
1.000 kg will equal 1000 mL.
calculated to be 124.8 g. Mix thoroughly. The resulting solution has
0.5000 mol of solute dis-
solved in 1.000 kg of solvent.

422 CHAPTER 12
 Concentrations are expressed as molalities when studying proper -
ties of solutions related to vapor pressure and temperature changes.
Molality is used because it does not change with changes in tempera -
ture. Below is a comparison of the equations for molarity and molality.

amount of A ( mol)
molarity;M =
volume of solution ( L )

amount of A ( mol )
molality, m =
mass of solvent ( kg )

SAMPLE PROBLEM »
A solution was prepared by dissolving 17.1 g of sucrose ( table sugar, C|2H22 in 125 g of water. Find
the molal concentration of this solution.
^^ Ii )

SOLUTION
1 ANALYZE Given: solute mass = 17.1 gCi 2H22On
solvent mass = 125 g H:0
Unknown: molal concentration

2 PLAN To find molality, you need moles of solute and kilograms of solvent. The given grams of
sucrose must be converted to moles. The mass in grams of solvent must be converted to
kilograms.

, ,
g C 2H220 ] i
mol C|:H2:Q| =
,
molar mass C 2H220 , i

ikg
kg H:0 = g H20 x
1000 g
mol C|2 H220 ]|
molality C p H
^O u - kg H:0
3 COMPUTE Use the periodic table to compute the molar mass of C|2H220 j |.
ci 2H:Ai = 342.34 g/mol
1 mol Cpl-I On
^
17.1 g C12HrO]-p<
342.34 tC7:H::07 , = 0.0500 mol C 12H 22 Ou
125 g 1 UO
= 0.125 kg H20
10( H ) g/ kg

0.0500 mol C12H22On

= 0.400 m CI2H22OU
0.125 kg H20
4 EVALUATE Tlie answer is correctly given to three significant digits. The unit mol solute /kg solvent is
correct for molality .
SOLUTIONS 423
 SAMPLE PROBLEM E
A solution of iodine. I 2, in carbon tetrachloride, CCI4, is used when iodine is needed for certain chemical
tests. How much iodine must be added to prepare a 0.48( 1 m solution of iodine in CCI4 if 100.0 g of CCI4
is used ?

SOLUTION
1 ANALYZE Given: molality of solution = 0.480 /;/ I 2
mass of solvent = 100.0 g CCI4
Unknown: mass of solute

2 PLAN Your first step should be to convert the grams of solvent to kilograms.The molality gives you
the moles of solute, which can be converted to the grams of solute using the molar mass of I2.

3 COMPUTE l sc the periodic table to compute the molar mass of l 2.

12 = 253.8 g/mol
l kg
100.0 g-GGfcj x = 0.100 kg CCI4
lOOOfrGGJj
x mol U
0.4S0 m = x = 0.0480 mol 1,
0.1 kgH2Q
253.8 g U
0.0480 niofb x - = 12.2 gl2
mol t ->
4 EVALUATE The answer has three significant digits and the units for mass of I2.

PRACTICE Answers in Appendix E

.
1 What is the molality of acetone in a solution composed of 255 g of
acetone, ( Cl i;):CO. dissolved in 200. g of water?
Go to go.hrw.com for
2. What quantity, in grams, of methanol. CH3OH, is required to pre - more practice problems
pare a 0.244 m solution in 400. g of water ? that ask you to calculate
molality.
Keyword: HC 6 SLNX

SECTION REVIEW Critical Thinking

1. What quantity represents the ratio of the number 3. ANALYZING DATA You evaporate all of the water
of moles of solute for a given volume of solution ? from 100. mL of NaCI solution and obtain
.
2 We dissolve 5.00 grams of sugar, in 11.3 grams of NaCI. What was the molarity of the
water to make 1.000 L of solution. What is the NaCI solution ?
concentration of this solution expressed as a 4. RELATING IDEAS Suppose you know the molarity
molarity ? of a solution. What additional information would
you need to calculate the molality of the solution?

424 CHAPTER 12
 CHAPTER HIGHLIGHTS
Types of Mixtures
I Vocabulary •Solutions arc homogeneous mixtures.
soluble • Mixtures are classified as solutions, suspensions, or colloids,
solution depending on the size of the solute particles in the mixture.
solvent •The dissolved substance is the solute. Solutions that have water
solute as a solvent are aqueous solutions.
suspension •Solutions can consist of solutes and solvents that are solids,
colloid liquids, or gases.
electrolyte • Suspensions settle out upon standing. Colloids do not settle
nonelectrolyte out . and they scatter light that is shined through them ,
• Most ionic solutes and some molecular solutes form aqueous
solutions that conduct an electric current . These solutes are
called electrolytes.
• Nonelectrolytes are solutes that dissolve in water to form solu -
tions that do not conduct .

The Solution Process

I Vocabulary • A solute dissolves at a rate that depends on the surface area of
solution equilibrium the solute, how vigorously the solution is mixed , and the tem -
saturated solution perature of the solvent .
unsaturated solution •The solubility of a substance indicates how much of that sub-
supersaturated solution stance w ill dissolve in a specified amount of solvent under cer -
solubility tain conditions.
hydration •The solubility of a substance depends on the temperature.
immiscible •The solubility of gases in liquids increases with increases in
miscible pressure.
Henry ' s law •The solubility of gases in liquids decreases with increases in
effervescence temperature.
solvated • Hie overall energy absorbed as heat by the system when a
enthalpy of solution specified amount of solute dissolved during solution formation
is called the enthalpy of solution.

Concentration of Solutions
I Vocabulary •Two useful expressions of concentration are molarity and
concentration molalitv.
molarity • Ilie molar concentration of a solution represents the ratio of
molality moles of solute to liters of solution .
•The molal concentration of a solution represents the ratio of
moles of solute to kilograms of solvent .

SOLUTIONS 425
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D .
d. Two bottles of soda are opened. One is a
Types of Mixtures cold bottle and the other is at room tempera -
ture. Which system would show more effer -
SECTION 1 REVIEW
vescence and why?
1. a. What is the Tyndall effect ? 11. Based on Figure 15, determine the solubility of
b. Identify one example of this effect. each of the following in grams of solute per
2. Given an unknow n mixture consisting of two or
more substances, explain how we could deter -
100. g H:0.
a. NaN03 at IO C
mine whether that mixture is a true solution, a b. KN03 at 60°C
colloid, or a suspension. c. NaCl at 50°C
3 . Explain why a suspension is considered a 12. Based on Figure 15, at what temperature would
heterogeneous mixture. each of the following solubility levels be
4. Does a solution have to involve a liquid? observed?
Explain your answer. a. 50 g KC1 in KM) gH:0
5 . What is the difference between an electrolyte b. 100 g NaN03 in 100 g H:0
and a nonelectrolvte ? c. 60 g KNO3 in 100 g IDO
13. Tlie enthalpy of solution for AgNO < is
+22.8 kJ /mol.
The Solution Process a. Write the equation that represents the disso -
SECTION 2 REVIEW lution of AgN03 in water.
6. a. What is solution equilibrium ? b. Is the dissolution process endothermic or
b. What factors determine the point at which a exothermic? Is the crystallization process
given solute -solvent combination reaches endothermic or exothermic?
equilibrium ? .
c As AgNO dissolves, what change occurs in
>

7. a. What is a saturated solution ? the temperature of the solution?

b. What visible evidence indicates that a solu - d. When the system is at equilibrium, how do
tion is saturated? the rates of dissolution and crystallization
c. What is an unsaturated solution? compare ?
8. a . What is meant bv the solubility of a e. If the solution is then heated, how will the
rales of dissolution and crystallization be
substance ?
b. What condition! s ) must be specified when affected? Why ?
expressing the solubility of a substance ? .
f How will the increased temperature affect
9 . a. What rule of thumb is useful for predicting the amount oi solute that can be dissolved?
whether one substance will dissolve in g. If the solution is allowed to reach equilibri-
um and is then cooled, how will the system
another ?
b. Describe what the rule means in terms of be affected?
14. What opposing forces are at equilibrium in the
various combinations of polar and nonpolar
solutes and solvents. sodium chloride system shown in Figure 7?
10, a. How does pressure affect the solubility of a
gas in a liquid?
b. What law is a statement of this relationship?
Concentration of Solutions
c. If the pressure of a gas above a liquid is SECTION 3 REVIEW
increased, what happens to the amount of 15. On w hich property of solutions does the con-
the gas that w ill dissolve in the liquid, if all
cept of concentration rely ?
other conditions remain constant ?

426 CHAPTER 12
 CHAPTER REVIEW

16. In what units is molarity expressed? 25. How many milliliters of 0.750 M H3P04
17. Under what circumstances might we prefer to are required to react with 250. mL of
express solution concentrations in terms of >
0.150 M Ba( OH 2 if the products are barium
a. molarity? phosphate and water?
b. molality ? 26. 75.0 mL of an AgN03 solution reacts with
.
18 If you dissolve 2.00 mol KI in 1.00 L of water, enough Cu to produce 0.250 g of Ag by single
will you gel a 2.00 M solution ? Explain. displacement. What is the molarity of the initial
AgNOj solution if Cu( NQ3 ) 2 is the other
PRACTICE PROBLEMS product ?
27. Determine the number of grams of solute need-
19. a. Suppose you wanted to dissolve 106 g of
ed to make each of the following molal solutions:
Na2C03 in enough H:0 to make 6.00 L of
a. a 4.50 nt solution of H2S04 in 1.00 kg H20
solution.
b. a 1.00 m solution of HN03 in 2.00 kg H20
( 1 ) What is the molar mass of Na 2C03?
28. A solution is prepared by dissolving 17.1 g of
( 2 ) What is the molarity of this solution?
sucrose. Ci:H22On. in 275 g of H:0.
b. What is the molarity of a solution of
a. What is the molar mass of sucrose?
14.0 g NH4 Br in enough ILO to make
b. What is the molality of that solution?
150 mL of solution ?
29. How many kilograms of FLO must be added to
20. a. Suppose you wanted to produce LOO L. of a
75.5 g of Ca ( NCL ): to form a 0.500 m solution ?
3.50 M aqueous solution of H 2 S04.
30. A solution made from ethanol. C\ HsOH. and
( 1 ) What is the solute?
water is 1.75 m in ethanol. How manv grams of
( 2 ) What is the solvent ?
C\H5OH are contained per 250. g of water ?
( 3 ) How many grams of solute are needed to
make this solution ?
b. How many grams of solute are needed to
MIXED REVIEW
make 2.50 L of a 1.75 M solution of
Ba(N03)2? 31. Na 2 S04 is dissolved in water to make 450. mL
21. How many moles of NaOH are contained in of a 0.250 M solution.
65.0 mL of a 2.20 M solution of NaOH in H:0? a. What is the molar mass of Na 2 S04 ?
(Hint: See Sample Problem B. ) b. How many moles of Na:S04 are needed?
22. A solution is made by dissolving 26.42 g of 32. Citric acid is one component of some soft
(NH4)2S04 in enough H:( ) to make 50.00 mL drinks. Suppose that 2.00 L of solution are made
of solution. from 150. mg of citric acid, QHIS07.
.
a What is the molar mass of ( NH4 ):S04 ? a. What is the molar mass of citric acid ?
b. What is the molarity of this solution ? b. What is the molarity of citric acid in the
23 . Suppose you wanted to find out how many solution ?
milliliters of l.O M AgN03 are needed to 33. Suppose you wanted to know how many grams
provide 169.9 g of pure AgNO v of KCI would be left if 350 mL of a 2.0 M KCI
a. What is step l in solving the problem? solution were evaporated to dryness.
b. What is the molar mass of AgN03? a. What is the molar mass of KCI?
c. How many milliliters of solution are needed ? b. How would heating the solution affect the
24. a. Balance the equation: mass of KCI remaining ?
H3P04 + Ca( OH)2 > Ca 3( P04 ): + H:0 c. How many grams of KCI would remain ?
b. What mass of each product results if 750 mL
of 6.00 M 1I3P04 reacts according to the
equation ?

SOLUTIONS 427
 CHAPTER REVIEW

34. Sodium metal reacts violently with water to 38. a . Suppose you wanted to dissolve 294.3 g of
form NaOH and release hydrogen gas. Suppose H 2S04 in 1.000 kg of H20 .
that 10.0 g of Na react completely with 1.00 L of ( 1 ) What is the solute?
water and the final solution volume is 1.00 L. ( 2 ) What is the solvent ?
a . What is the molar mass of NaOH ? ( 3) What is the molality of this solution ?
b. Write a balanced equation for the reaction. b. What is the molality of a solution of
c. What is the molarity of the NaOH solution 63.0 g HN03 in 0.250 kg H:0?
formed by the reaction ?
35 . In cars, ethylene glycol. C2 H 602, is used as a
coolant and antifreeze. A mechanic fills a radia - CRITICAL THINKING
tor with 6.5 kg of ethylene glycol and 1.5 kg of
water. 39 . Predicting Outcomes You have been investi -
a . What is the molar mass of ethylene glycol? gating the nature of suspensions, colloids, and
b. What is the molality of the water in the solutions and have collected the following
solution ? observational data on four unknown samples.
36. Plot a solubility graph for AgN 03 from the fol - From the data , infer whether each sample is a
lowing data , with grams of solute ( by incre- solution , suspension , or colloid.
ments of 50 ) per 100 g of 11:Q on the
DATA TABLE 1 Samples
vertical axis and with temperature in C on
the horizontal axis. Clarity ( clear Settle Tyndall
Sample Color or cloudy) out effect
Grams solute per 100 g H 20 Temperature ( ° C ) 1 green clear no no
122 0 2 blue cloudy yes no
216 30 3 colorless clear no yes
311 40 4 white cloudy no yes
440 60
585 80 Based on your inferences in Data Table I . you
100 decide to conduct one more test of the particles.
733
You filter the samples and then reexamine the
a. How does the solubility of AgN 03 vary with filtrate. You obtain the data found in Data
the temperature of the water? Table 2. Infer the classifications of the filtrate
b. Estimate the solubility of AgNO at 35 C. based on the data in Data Table 2.
^
55°C and 75°C.
DATA TABLE 2 Filtrate of Samples
c. At what temperature would the solubility of
AgNO . be 275 g per L00 gofH2O? Clarity ( clear On filter Tyndall
d . If 100 g of AgN 03 were added to 100 g of Sample Color or cloudy ) paper effect
H 20 at 10°C. would the resulting solution be 1 green clear nothing no
saturated or unsaturated ? What would occur 2 blue cloudy gray solid yes
if 325 g of AgN 03 were added to 100 g of 3 colorless clear none yes
.
H O at 35°C?
37 . If a saturated solution of KN 03 in 100. g of
4 colorless clear white solid no

.
H O at 60 C is cooled to 20°C, approximately
'

how many grams of the solute will precipitate

out of the solution ? ( Use Table 4. )

428 CHAPTER 12
 CHAPTER REVIEW

USING THE HANDBOOK ALTERNATIVE ASSESSMENT

40. Review the information on alloys in the 43. Make a comparison of the electrolyte concen -
Elements Handbook . tration in various brands of sports drinks. Using
a. Why is aluminum such an important compo- the labeling information for sugar, calculate the
nent of alloys? molarity of sugar in each product or brand .
b. What metals make up bronze? Construct a poster to show the results of your
c. What metals make up brass? analysis of the product labels.
d . What is steel? 44. Write a set of instructions on how to prepare a
e. What is the composition of the mixture solution that is 1 M CuS04 using CuS04 *5 H 20
called cast iron? as the solute. How do the instructions differ if
41 . Table 5 A of the Elements I hunt book contains the solute is anhydrous CuS04? Your instruc-
carbon monoxide concentration data expressed tions should include a list of all materials needed.
as parts per million ( ppm (. Hie OSH A
'

( Occupational Safety and Health

Administration ) limit for worker exposure to
CO is 200 ppm for an eight - hour period .
a. At what concentration do harmful effects
occur in less than one hour?
b. By what factor does the concentration in
i Graphing Calculator
Solubility vs. Temperature
Go to go.hrw.com for a graphing calculator
item ( a ) exceed the maximum limit set exercise that asks you to graph the solubility
bv OSHA ? versus temperatures for NaCI and KN 03.
Keyword: HC 6 SLNX

RESEARCH & WRITING

42 . Find out about the chemistry of emulsifying
agents. How do these substances affect the dis-
solution of immiscible substances such as oil
and water? As part of your research on this
topic, find out why eggs are an emulsifying
agent for baking mixtures.

SOLUTIONS 429
 Math Tutor CALCULATING SOLUTION CONCENTRATION

You can use the relationship below to calculate the concentration in molarity of any
solution.
moles of solute (mol)
molarity of solution (M) =
volume of solution (L)
Suppose you dissolve 20.00 g of NaOH in some water and dilute the solution to a vol-
ume of 250.0 mL (0.2500 L). You don' t know the molarity of this solution until you
know how many moles of NaOH were dissolved. You know that the number of moles
of a substance can be found by dividing the mass of the substance by the mass of
1 mol (molar mass) of the substance. The molar mass of NaOH is 40.00, so the num -
ber of moles of NaOH dissolved is
1 mol NaOH
20.00 g NaOH x = 0.5000 mol NaOH
40.00 g NaOH
Now you know that the solution has 0.5000 mol NaOH dissolved in 0.2500 L of solu -
tion, so you can calculate molarity.
mol NaOH 0.5000 mol NaOH
molarity of NaOH x = 2.000 mol/ L = 2.000 M NaOH
L solution 0.2500 L solution

Problem-Solving TIPS
• Remember that balances measure mass, not moles so you often have to
,

convert between mass and moles of solute when making or using solutions.

SAMPLE
A 0.5000 I. volume of a solution contains 36.49 g of magnesium chloride, MgCI2. What is the
molarity of the solution ?
You know the volume of the solution , but you need to find the number of moles of the
solute MgCU by the following conversion .
I mol \1gCl 2
mass MgCU x
molar mass MgC U
= mol MgCU
l mol MgCU
36.49 j MgCU x
^ 95.20 g.MgC U
= 0.3833 mol MgCU
Now you can calculate mol MgCU per liter of solution ( molarity ).
0.3833 mol MgCU
0.5000 L solution
= 0.7666 M MgCU

PRACTICE PROBLEMS
I . What is the molarity of a solution that contains 2 . What is the molarity of a solution that contains
0.0350 mol of sodium sulfate. Na:S04. dissolved 45.00 g of cadmium nitrate, Cd ( NOv) 2. dissolved
in 50.0 mL of solution ? in 400.0 mL of solution ?

430 CHAPTER 12
Answer the following items on a separate piece of 8. Which one of the following statements is false ?
paper. A. Gases are generally more soluble in water
MULTIPLE CHOICE under high pressures than under low pressures.
B. As temperature increases, the solubilities of
.
1 Water is an excellent solvent because
some solids in water increase and the solubil-
A . it is a covalent compound.
B. it is a nonconductor of electricity.
ities of other solids in water decrease.
C. Water dissolves many ionic solutes because
C. its molecules are quite polar.
of its ability to hydrate ions in solution.
D. it is a clear, colorless liquid.
D. Many solids dissolve more quickly in a cold
2. Two liquids are likely to be immiscible if solvent than in a warm solvent .
A . both have polar molecules .
B. both have nonpolar molecules . SHORT ANSWER

C. one is polar and the other is nonpolar. 9. Several experiments are carried out to deter -
D. one is water and the other is methyl alcohol . mine the solubility of cadmium iodide. Cdl: in .
CH3OH, water. In each experiment, a measured mass of
Cdl 2 is added to 100 g of water at 25°C and the
.
3 The solubility of a gas in a liquid would be mixture is stirred. Any undissolved Cdl2 is then
increased by an filtered off and dried, and its mass is deter -
A . addition of an electrolyte. mined. Results for several such experiments are
B . addition of an emulsifier. shown in the table below. What is the solubility
C. agitation of the solution. of Cdl 2 in water at this temperature?
D . increase in its partial pressure.
4. Which of the following types of compounds is Mass of Cdl2 Mass of undissolved
most likely to be a strong electrolyte ? added, g Cdl2 recovered, g
A . a polar compound 17.9 0.0
B. a nonpolar compound 38.2 0.0
C. a covalent compound 53.6 0.0
D. an ionic compound 79.3 0.0
.
5 A saturated solution can become supersaturat - 93.6 7.4
ed under which of the following conditions? 104.3 18.1
A . It contains electrolytes.
B. The solution is heated and then allowed EXTENDED RESPONSE
to cool. .
10 Explain why oil and water do not mix.
C. More solvent is added.
D. More solute is added.
.
11 Write a set of instructions on how to prepare a
solution that is 0.100 M KBr. using solid KBr
6. Molarity is expressed in units of ( molar mass 119 g/mol) as the solute. Your
A . moles of solute per liter of solution. instructions should include a list of all materials
B. liters of solution per mole of solute. and equipment needed.
C. moles of solute per liter of solvent .
D. liters of solvent per mole of solute.
7. What mass of NaOH is contained in 2.5 l. of a
0.010 M solution?
A . 0.010 g c . 2.5 g Allow a few minutes at the end
B. 1.0 g
^
D 0.40 g . of the test - taking period to check for careless mistakes,
such as marking two answers for a single question.

SOLUTIONS 431
 SEE PRE- LAB MICRO
EXPERIMENT 12 PAPER CHROMATOGRAPHY L A B

Separation of Pen Inks by

Paper Chromatography
OBJECTIVES BACKGROUND
• Demonstrate proficiency in qualitatively Paper Chromatography
separating mixtures using paper Details on this technique can be found in the
chromatography. -
Pre Laboratory Procedure “ Paper Chromatography"
on page 848.
• Determine the Rr factor ( s ) for each
component of each tested ink .
Writing Inks
• Explain how the inks are separated Most ballpoint pen inks are complex mixtures, con -
In paper chromatography. taining pigments or dyes that can be separated by
• Observe the separation of a mixture paper chromatography, as shown in Figure A .
by the method of paper chromatography. Black inks can contain three or more colors; the
number of colors depends on the manufacturer.
MATERIALS Each ink formulation has a characteristic pattern that
• 12 cm circular chromatography paper uniquely identifies it .
or filter paper In this experiment you will develop radial paper
chromatograms for four black ballpoint pen inks,
• distilled water using water as solvent . You will then repeat this
• filter paper wick, 2 cm equilateral triangle process using isopropanol as the solvent. You will then
• isopropanol measure the distance traveled by each of the individ -
ual ink components and the distance traveled by the
• numbered pens, solvent front. Finally, you will use these measurements
each with a different to calculate the R f factor for each component .
black ink . 4
• pencil SAFETY
• petri dish with lid
• scissors
For review of safety, please see Safety in the
Chemistry Laboratory in the front of your book .

PREPARATION
1 . Determine the formula, structure, polarity,
density, and volatility at room temperature for
water and isopropanol. The following titles are
sources that provide general information on spe -
FIGURE A Paper chromatog-
cific elements and compounds: CRC Handbook
raphy reveals the different col- -
of Chemistry and Physics, McGraw Hill
ored dyes that black ink contains. Dictionary of Chemical Terms, and Merck Index.

432 CHAPTER 12
 EXPERIMENT 12

2. Prepare two data tables, one for the chro- CLEANUP AND DISPOSAL
matogram made with water and one for the 9. The water may be poured down the
chromatogram made with isopropanol . Record sink . Chromatograms and other pieces
the pen number you are testing. In your data of filter paper may be discarded in the
tables, create columns for each color in which to trash. The isopropanol solution should be placed
record the distance and R f value. Your teacher in the waste disposal container designated by
can provide you with sample data tables. Leave your teacher. Clean up your equipment and
room below each data table to record the dis- lab station . Thoroughly wash your hands after
tance that the solvent reaches. completing the lab session and cleanup.

PROCEDURE ANALYSIS AND INTERPRETATION

Part A: Prepare a chromatogram using 1. Evaluating Conclusions: Is the color in each
water as the solvent pen the result of a single dye or multiple dyes?
.
1 Construct an apparatus for paper chromatog- Justify your answer.
raphy as described in the Pre - Laboratory 2. Relating Ideas: What can be said about the
Procedure on page 848. You will make only four properties of a component ink that has an Re-
dots. You will use ballpoint pens rather than value of 0.50?
micropipets to spot your paper.
3. Analyzing Methods: Suggest a reason for stop-
2. After 15 min or when the water is about 1 cm ping the process when the solvent front is 1 cm
from the outside edge of the paper, remove the from the edge of the filter paper rather than
paper from the Petri dish and allow the chro- when it is even with the edge of the paper.
matogram to dry. Record in the data table the
colors that have separated from each of the four 4. Predicting Outcomes: Predict the results of
different black inks. forgetting to remove the chromatogram from
the water in the petri dish until the next day.
Part B: Prepare a chromatogram using
isopropanol as the solvent CONCLUSIONS
.
3. Repeat Procedure steps 1 to 2 replacing the
1. Analyzing Results: Compare the R f values
water in the Petri dish with isopropanol.
for the colors from pen number 2 when water
Part C: Determine Rf values for each component was the solvent and the R f values obtained
4. After the chromatogram is dry. use a pencil to when isopropanol was the solvent . Explain
mark the point where the solvent front stopped . why they differ.
5. With a ruler, measure the distance from the 2. Evaluating Methods: Would you consider iso -
initial ink spot to your mark , and record this propanol a better choice for the solvent than
distance on your data table. water ? Why or why not ?
6. Make a small dot with your pencil in the center 3. Analyzing Conclusions: Are the properties of
of each color band. the component that traveled the farthest in the
water chromatogram likely to be similar to the
7. With a ruler, measure the distance from the properties of the component that traveled the
initial ink spot to each dot separately, and farthest in the isopropanol chromatogram ?
record each distance on your data table. Explain your reasoning.
8. Divide each value recorded in Procedure step 7 4. Inferring Conclusions: What can you conclude
by the value recorded in Procedure step 5. The about the composition of the inks in ballpoint
result is the R f value for that component. pens from your chromatogram ?
Record the R f values in your data table. Tape
or staple the chromatogram to your data table.
SOLUTIONS 433
 CHAPTER 1 3

Ions in Aqueous
Solutions and
Colligative Properties
These formations were made by the precipitation
of ionic compounds from an aqueous solution.
Compounds in SECTION 1

Aqueous Solutions OBJECTIVES

>J Write equations for the
dissolution of soluble ionic
compounds in water.

A. s you have learned, solid compounds can be ionic or molecular. In sj Predict whether a precipitate
an ionic solid, a crystal structure is made up of charged particles held will form when solutions of
together by ionic attractions. In a molecular solid, molecules are com - soluble ionic compounds are
posed of covalently bonded atoms. The solid is held together by non- combined, and write net ionic
covalent. intermolecular forces. When they dissolve in water, ionic equations for precipitation
compounds and molecular compounds behave differently. reactions.

** Compare dissociation of ionic

compounds with ionization of
Dissociation molecular compounds.

When a compound that is made of ions dissolves in water, the ions sep -
arate from one another, as shown in Figure 1. This separation of ions Draw the structure of the
hydronium ion, and explain
that occurs when an ionic compound dissolves is called dissociation. For
why it is used to represent
example, dissociation of sodium chloride and calcium chloride in water the hydrogen ion in solution.
.
can be represented by the following equations ( As usual, ( s ) indicates a
solid species, and ( aq ) indicates a species in an aqueous solution. Note
that each equation is balanced for charge as well as for atoms.) w Distinguish between strong
electrolytes and weak
H:O electrolytes.
NaCI(.v ) Na+( aq ) + Cl ( aq )
*
H X) +( aq )
CaCI:(.v )
* Cdr + 2C1 ( aq )

Notice the number of ions produced per formula unit in the equations
above. One formula unit of sodium chloride gives two ions in solution,
whereas one formula unit of calcium chloride gives three ions in solution.

Na +
ci-

FIGURE 1 When NaCl dissolves

in water, the ions separate
as they leave the crystal.

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 435

 Assuming 1 ( K ) % dissociation, a solution that contains 1 mol of so -
dium chloride contains 1 mol of Na ~ ions and 1 mol of Cl ions. In this '

hook, you can assume 100% dissociation for all soluble ionic com-
pounds. The dissociation of NaCI can he represented as follows.
H »0
NaCl( $) -> Na ~ ( aq ) + Cl ( aq )
1 mol 1 mol 1 mol

A solution that contains 1 mol of calcium chloride contains 1 mol of

Ca2~ ions and 2 mol of Cl ions — a total of 3 mol of ions.
1U )
CaCI:(.v ) > Ca^( aq ) + 2C\ ~( uq )
1 mol 1 mol 2 mol

SAMPLE PROBLEM A
Write the equation for the dissolution of aluminum sulfate, AMS()4 ) V in water. How many moles of alu-
minum ions and sulfate ions are produced by dissolving 1 mol of aluminum sulfate? What is the total
number of moles of ions produced by dissolving 1 mol of aluminum sulfate ?

SOLUTION
1 ANALYZE Given: amount of solute = I mol AT( S04h
solvent identity = water
Unknown: a . moles of aluminum ions and sulfate ions
b. total number of moles of solute ions produced

2 PLAN The coefficients in the balanced dissociation equation will reveal the mole relationships,
so you can use the equation to determine the number of moles of solute ions produced .
H,O
AI2( S04 )3( J) » 2 A\ *+( aq ) + 3SO ] ~( aq )

3 COMPUTE —
a . I mol AI2( S04 )3 > 2 mol Al 3+ + 3 mol SOj
b. 2 mol Al '+ + 3 mol SO ] ~ = 5 mol of solute ions

4 EVALUATE The equation is correctly balanced. Because one formula unit of AU( S04 ) 3 produces 5 ions.
I mol of AI:( SQ4 )3 produces 5 mol of ions.

PRACTICE Answers in Appendix E

1 . Write the equation for the dissolution of each of the following in

water, and then determine the number of moles of each ion pro-
duced as well as the total number of moles of ions produced. Go to go.hrw.com for
a . 1 mol ammonium chloride more practice problems
b. 1 mol sodium sulfide that ask you to calculate
c. 0.5 mol barium nitrate moles of ions produced
in dissociation.
Keyword: HC 6 I0NX

436 CHAPTER 13
 FIGURE 2 Ionic compounds
can be soluble or insoluble in
water. NiCk KMn 04. CuS04. and
Pb( NO?)2 are soluble in water. AgCI
and CdS are insoluble in water.

Precipitation Reactions
Although no ionic compound is completely insoluble, compounds of
SCllNKS. DmtoH
Njtwd
Ih*
Samf k«km AHMUIIM
very low solubility can be considered insoluble for most practical pur -
For a variety of links related to this
poses. Some examples of ionic compounds that are soluble and insolu - chapter, go to www.scilinks. org
ble in water are shown in Figure 2. It is difficult to write solubility rules
that cover all possible conditions. However, we can w rite some general
Topic: Precipitation Reactions
SciLinks code: HC61203
^
guidelines to help predict whether a compound made of a certain com -
bination of ions is soluble. These general solubility guidelines are given
in Table 1 .
By looking at the table you can tell that most sodium compounds are
soluble. Sodium carbonate. Na:C03, is soluble because it contains so-
dium . Its dissociation equation is as follows.
H >0
Na:C03(s ) *

^
> 2 Na"( w/ ) 4 CO ( a q )

TABLE 1 General Solubility Guidelines

.
1 Sodium , potassium , and ammonium compounds are soluble
in water.
2. Nitrates, acetates, and chlorates are soluble.
3. Most chlorides are soluble, except those of silver, mercurvf I ).
and lead . Lead ( II ) chloride is soluble in hot water.
4. Most sulfates are soluble, except those of barium , strontium ,

lead , calcium , and mercury.

5. Most carbonates, phosphates, and silicates are insoluble, except
those of sodium , potassium , and ammonium .
6. Most sulfides are insoluble, except those of calcium strontium ,
,

sodium , potassium and ammonium.

,

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 437

 Is calcium phosphate, Ca 3( P04) 2, soluble or insoluble? According to
Table 1, most phosphates are insoluble. Calcium phosphate is not one of
the exceptions listed, so it is insoluble. Dissociation equations cannot be
written for insoluble compounds.
The information in Table 1 is also useful in predicting what will hap -
pen if solutions of two different soluble compounds are mixed. If the
mixing results in a combination of ions that forms an insoluble com -
pound, a double-displacement reaction and precipitation will occur.
Precipitation occurs when the attraction between the ions is greater
than the attraction between the ions and surrounding water molecules.
Will a precipitate form when solutions of ammonium sulfide and
cadmium nitrate are combined? By using the table, you can tell that
cadmium nitrate, Cd( N03 ) 2 , is soluble because it is a nitrate and all
nitrates are soluble. You can also tell that ammonium sulfide. (NH4 ) 2S .
is soluble. It is one of the sulfides listed in the table as being soluble.
Their dissociation equations are as follows.
FIGURE 3 Ammonium sulfide is a 1U)
soluble compound that dissociates in
(NH4)2S(i) > 2NH 4( aq ) + S2 ( aq )
water to form NH 4 and S 2 ions.
‘

Cadmium nitrate is a soluble com - Cd(N03)2( j)

HO. Cd 2+( aq ) + 2NO3 ( o</ )
pound that dissociates in water to
form NO:; and Cd 2+ ions. Precipi-
tation of cadmium sulfide occurs
when the two solutions are mixed.

Before reaction

After reaction

%
«<
( NH4 ) 2S(aq)
*% **
*

Cd( N 03)2(aqf )

CHAPTER 13
 The two possible products of a double-displacement reaction between
( NH4)2S and Cd(N03 )2 are ammonium nitrate, NH4N03. and cadmium
sulfide. CdS. The question marks indicate that the states are unknown.

(NH4 ):S( fl9 ) + Cd(N03 )2( fl9 )

* 2NH N03( ? ) + CdS( ? )
4

To decide whether a precipitate can form, you must know the solubil -
ities of these two compounds. Consulting Table 1, you can see that
NH4NO3 is soluble in water. However, CdS is insoluble You can there - .
fore predict that when solutions of ammonium sulfide and cadmium
nitrate are combined, ammonium nitrate will not precipitate and cadmi -
um sulfide will. As illustrated in Figure 3, crystals of CdS form when the
solutions are mixed. In the following equation, the designations ( aq ) and
( 5 ) show that NH4N03( tf 7 ) remains in solution and CdS( s ) precipitates.
*
( NH4 )2S( dr/ ) + Cd(N03 )2( <i</ ) > 2NH4N03(fl<y ) + CdS( s)

Net Ionic Equations

Reactions of ions in aqueous solution are usually represented by net ionic
equations rather than formula equations. A net ionic equation includes
only those compounds and ions dint undergo a chemical change in a reac-
tion in an aqueous solution. To write a net ionic equation, you first con -
CROSS- DISCIPLINARY
vert the chemical equation into an overall ionic equation. All soluble
Go to go.hrw.com for a full- length
ionic compounds are shown as dissociated ions in solution. The precipi- article on minerals.
tates are shown as solids. The precipitation of cadmium sulfide described
' Ll. Keyword: HC 6 I 0 NX
previously can be shown by the following overall ionic equation.

Cd: ( aq ) + 2N03( <7r/ ) + 2NH4 ( tfq ) + S- ( aq )

CdS( v ) 4- 2NOy ( aq ) + 2NH%( aq )

Notice that the aqueous ammonium ion. NH } ( aq ), and the aqueous

nitrate ion, NOJ( aq ) , appear on both sides of this equation. Therefore,
they have not undergone any chemical change and are still present in
their original form. Ions that do not take pan in a chemical reaction and
are found in solution both before and after the reaction are spectator
ions.
To convert an ionic equation into a net ionic equation, the spectator
ions are canceled on both sides of the equation. Eliminating the NH 4
and NO5 ions from the overall ionic equation above gives the following
net ionic equation.

Cd2~ ( tfqr ) -t S2 ( aq ) 4 CdS( s)

'
Tins net ionic equation applies not only to the reaction between
( NH4) 2S and Cd( N03 ) 2 but also to any reaction in which a precipitate
of cadmium sulfide forms when the ions are combined in solution. For
example, it is also the net ionic equation for the precipitation of CdS
when CdSQ 4 and H2S react.

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 439

 SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of Chapter 14

Identify the precipitate that forms when aqueous solutions of zinc nitrate and ammonium sulfide are com-
bined. Write the equation for the possible double- displacement reaction. Then write the formula equation,
overall ionic equation, and net ionic equation for the reaction.

SOLUTION
1 ANALYZE Given: identity of reactants: zinc nitrate and ammonium sulfide
reaction medium: aqueous solution
Unknown: a . equation for the possible double -displacement reaction b. identity of the
.
precipitate c. formula equation d overall ionic equation e. net ionic equation

2 PLAN Write the possible double- displacement reaction between Zn(N03 )2 and ( NH 4 ) 2S. Use
Table I to determine if any of the products are insoluble and will precipitate Write a for - .
mula equation and an overall ionic equation, and then cancel the spectator ions to produce
a net ionic equation.

3 COMPUTE a . The equation for the possible double-displacement reaction is as follows.

Zn( NO3 ) 2 ( w/ ) + ( NH4 ) 2 S( M/ ) » ZnS( ?) + 2NH4N03( ? )
b. Table l reveals that zinc sulfide is not a soluble sulfide and is therefore a precipitate.
Ammonium nitrate is soluble according to the table.
c. The formula equation is as follows.
Zn( N03 )2( </r/ ) + (NH4)2S( <K/ ) ZnS( .v ) + 2NH4N03(W/ )
d. The overall ionic equation is as follows .
Z n: ( < / </ ) + 2NO$ ( aq ) + 2NH+( aq ) + S: ( iuf )
“ ~
» ZnS( s) + 2NH 4 ( M/ ) + 2NO3 («r/ )
e. The ammonium and nitrate ions appear on both sides of the equation as spectator ions.
The net ionic equation is as follows.
Zn2+( tf </ ) + S: ( aq ) » ZnS( .v )

PRACTICE Answers m Appendix E

1. Will a precipitate form if solutions of potassium sulfate and bar -

ium nitrate are combined? If so. write the net ionic equation for
the reaction.
2 . Will a precipitate form if solutions of potassium nitrate and mag-
nesium sulfate are combined? If so, write the net ionic equation
for the reaction.
3 . Will a precipitate form if solutions of barium chloride and sodium
sulfate are combined? If so. identify the spectator ions and write Go to go.hrw.com for
the net ionic equation. more practice problems
that ask you to identify
4. Write the net ionic equation for the precipitation of nickel( II) precipitates that form
sulfide. when solutions are
combined.
C Keyword: HC 6I0NX

440 CHAPTER 13
 Ionization
Some molecular compounds can also form ions in solution . Usually such
compounds are polar. Ions arc formed from solute molecules by the
action of the solvent in a process called ionization. The more general
meaning of this term is the creation of ions where there were none. Note
that ionization is different from dissociation . When an ionic compound
dissolves, the ions that were already present separate from one another.
When a molecular compound dissolves and ionizes in a polar solvent ,
ions are formed where none existed in the undissolved compound. Like
all ions in aqueous solution, the ions formed by such a molecular solute
are hydrated . The energy released as heat during the hydration of the
ions provides the energy needed to break the covalent bonds.
In general , the extent to which a solute ionizes in solution depends
on the strength of the bonds within the molecules of the solute and the
strength of attraction between the solute and solvent molecules. If the
strength of a bond within the solute molecule is weaker than the attrac-
tive forces of the solvent molecules, then the covalent bond of the solute
breaks and the molecule is separated into ions. Hydrogen chloride, HCI ,
is a molecular compound that ionizes in aqueous solution . It contains a
highly polar bond . The attraction between a polar HCI molecule and the
polar water molecules is strong enough to break the 11CI bond , forming
hydrogen ions and chloride ions.
H ,< >
HCI -> H ( an ) + Cl ~ ( a q )

The Hydronium Ion

Many molecular compounds contain a hydrogen atom bonded by a SCllNKS Matiwul SocMe Te*tbm MMUIUWI
polar covalent bond. Some of these compounds ionize in an aqueous
For a variety of links related to this
solution to release IT . The 1 L ion attracts other molecules or ions so chapter, go to wwyv. sdlinks.org I
strongly that it does not normally exist alone. Hie ionization of hydro-
gen chloride in water is better described as a chemical reaction in which
Topic: Hydronium Ion
SciLinks code: HC 60778
^
a proton is transferred directly from HCI to a water molecule, where it
becomes covalently bonded to oxygen and forms 1 LO \

H 20( / ) + HCl (g ) * H j C y ( a( / ) + Cl ( a q )

This process is represented in Figure 4. T h e I l f ) ion is known as the

hydronium ion . The reaction of the H ion to form the hydronium ion
produces much of the energy needed to ionize a molecular solute.

FIGURE 4 When hydrogen chlo-

ride gas dissolves in water, it ionizes
to form an H ' ion and a Cl ion . The
"

f H ' ion immediately bonds to a water

+ + molecule, forming a hydronium ion .
The aqueous solution of hydrogen
chloride is called hydrochloric acid.

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 441

 r0
HF
Nat
4* * *\ **
a * > * •i
> • 4

t
Cl -

H 2O «
* J NaCI (aqf )
H 3O+

r ,* # HF (ag )
j
C12 H 220

r t
b
12 22 1 1 (
^ ^ ^ ^9)
FIGURE 5 Strong electrolytes,
such as NaCl. yield onl \ ions when
they dissolve in aqueous solution .
Weak electrolytes such as HF.
Strong and Weak Electrolytes
,

exist as both ions and unionized

molecules in aqueous solution.
Nonelectrolytes, such as sucrose, As discussed in Chapter 12. substances that yield ions and conduct
i
*

: i ,
( ; l l iO . do not form any ions in an electric current in solution are electrolytes. Substances that do not yield
aqueous solution . ions and do not conduct an electric current in solution are non -
electrolytes. Hydrogen chloride is one of a series of compounds
composed of hydrogen and the members of Group 17 ( known as the halo-
gens ). The hydrogen halides are all molecular compounds with single
polar-covalent bonds. All are gases, all are very soluble in water, and all are
electrolytes. Hydrogen chloride, hydrogen bromide, and hydrogen iodide
strongly conduct an electric current in an aqueous solution . However,
hydrogen fluoride only weakly conducts an electric current at the same
concentration . The strength with which substances conduct an electric cur -
rent is related to their ability to form ions in solution , as shown in Figure 5.

Strong Electrolytes
*TCV. -s
A
Hydrogen chloride, hydrogen bromide, and hydrogen iodide are 100%
CHEMISTRY ionized in dilute aqueous solution . A strong electrolyte is any com -
A/ TO* pound whose dilute aqueous solutions conduct electricity well; this is due
Module 8 : Strong and Weakly to the presence of all or almost all of the dissolved compound in the form
Ionized Species, pH , and Titrations of ions. Hydrogen chloride, hydrogen bromide, and hydrogen iodide are
all acids in aqueous solution . These acids, several other acids, and all sol -
uble ionic compounds are strong electrolytes.
The distinguishing feature of strong electrolytes is that to whatever
extent they dissolve in water , they yield only ions. For example, some
strong electrolytes, such as NaCl , may be highly soluble in water and
form ions in solution . Others may not dissolve much, but the amount
that does dissolve exists solely as ions in solution .

442 CHAPTER 13
Weak Electrolytes
Some molecular compounds form aqueous solutions that contain not
only dissolved ions hut also some dissolved molecules that are not ion-
.
ized. Hydrogen fluoride HF. dissolves in water to give an acidic solution
known as hydrofluoric acid. However, the hydrogen- fluorine bond is
much stronger than the bonds between hydrogen and the other halo -
gens. When hydrogen fluoride dissolves, some molecules ionize. But the
reverse reaction— the transfer of IP ions back to F ions to form hydro -
'

—
gen fluoride molecules also takes place.

HF ( a q ) + H:Q( / ) H3CT( wy ) + F ( a q )

Thus, the concentration of dissolved intact HF is much greater than the

concentration of H;0 and F“ ions.
T

Hydrogen fluoride is an example of a weak electrolyte. A weak

electrolyte is any compound whose dilute aqueous solutions conduct
electricity poorly; this is due to the presence of a small amount of the
dissolved compound in the form of ions. This is in contrast to a non -
electrolyte. such as the molecular compound sucrose, which dissolves
but does not produce any ions in solution. Another example of a weak
electrolyte is acetic acid. CH3COOH. Only a small percentage of the
acetic acid molecules ionize in aqueous solution.

=
C U y C O O H ( a q ) + H:0( / ); ± CH3C00-( ^/ ) + H30+( aq )

The description of an electrolyte as strong or weak must not be con-

fused with the description of a solution as concentrated or dilute. Strong
and weak electrolytes differ in the degree of ionization or dissociation.
Concentrated and dilute solutions differ in the amount of solute dis -
solved in a given quantity of a solvent. Hydrochloric acid is always a
strong electrolyte. This is true even in a solution that is 0.000 01 M—a
very dilute solution. By contrast, acetic acid is always considered a weak
electrolyte, even in a 10 M solution—a very concentrated solution.

SECTION REVIEW 4. Explain why HCI is a strong electrolyte and HF is a

1. Write the equation for the dissolution of Sr(N03)2 weak electrolyte.
in water. How many moles of strontium ions and Critical Thinking
nitrate ions are produced by dissolving 0.5 mol of
strontium nitrate? 5. PREDICTING OUTCOMES For each of the following
pairs, tell which solution contains the larger total
2. Will a precipitate form if solutions of magnesium concentration of ions.
acetate and strontium chloride are combined ?
a. 0.10 M HCI and 0.05 M HCI
3. What determines whether a molecular compound
will be ionized in a polar solvent ? b. 0.10 M HCI and 0.10 MHF
c. 0.10 M HCI and 0.10 MCaCI2

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 443

 1STORICAL CHEMISTRY

The Riddle of Electrolysis

Historical Perspective position of the solids, with the two products of the
When Michael Faraday performed his electrochemical solids ' breakdown also evolving at opposite poles of the
experiments, little was known about the relationship battery. This electrochemical decomposition was later
H between matter and electricity. Chemists were still debat - named electrolysis.
ing the existence of atoms, and the discovery of the elec -
The Roots of Electrolytic Theory
H
| tron was more than 50 years in the future. Combining his
The discovery of electrolysis led two pioneering chemists
talents in electrical and chemical investigation, Faraday
to ponder the connection between chemical forces and
pointed researchers to the intimate connection between
electricity. One of the chemists was Humphry Davy, who
chemical reactions and electricity while setting the stage
thought that chemical bonding must be driven by the
for the development of a new branch of chemistry.
same forces that drive electrical attractions.
Electrifying Experiments The Swedish chemist Jons Jacob Berzelius took Davy 's
In 1800, Italian physicist Alessandro Volta introduced his idea a step further. He postulated that matter consisted of
voltaic pile, better known as the battery. The stack of alter - combinations of " electropositive " and " electronegative "
nating zinc and silver disks provided scientists with a substances, classifying the parts by the pole at which they
source of electric current for the first time. accumulated during electrolysis.
That same year, chemists discovered a new phenome - These ideas inspired two early electrolytic theories, each
non using Volta ' s device. They immersed the two poles of which ultimately proved incorrect but contributed to
of a battery at different locations in a container of our present understanding of the phenomenon. The con-
water. The current caused the water to decompose into tact theory proposed that electrolytic current was due
its elemental components, with hydrogen evolving at the merely to the contact of the battery 's metals with the elec -
positive pole of the battery and oxygen evolving at the trolytic solution. The chemical theory, on the other hand,
negative pole. Similar experiments using solutions of attributed the current to undefined changes in the solu-
certain solids dissolved in water resulted in the decom - tion's components.

Chlorine being produced by electrolysis.

» I

t? .
44
CHAPTER 13
 Faraday Provides a Spark
Although Michael Faraday is best remembered for his
work in electromagnetism, he began his career as
Humphry Davy's laboratory assistant at the Royal
Institution in London and went on to be the professor of
chemistry there for over 30 years. In the 1830s, Faraday
devised several ingenious experiments to determine
whether the current in an electrolytic solution is depend-
ent solely on the contact of the battery 's poles with the
solution. In a typical setup, one of the poles was separated
from the solution, and electricity was permitted to enter
the solution by way of a spark. In all cases, Faraday
observed current in the electrolytic cell despite one or both
of the poles not being in direct contact with the electrolyt-
ic solution. In 1833, he made the hypothesis that the
process of electrolysis was due to the intrinsic properties
of the metals in solution and the effect of current on these
properties.
Although the battery 's poles were, in fact, later shown
to play a part in the current, Faraday had established the
active role of the electrolytic solution in electrolysis. And in
Michael Faraday used this instrument in his
realizing that electricity affected the chemical nature of studies of electrolysis.
the solution, he anticipated the ideas of oxidation and
reduction despite that the concepts of electrons and ions
were unknown at the time. Questions
1. To which scientist does this feature give the most
Faraday 's Legacy credit for the initial understanding of the basic nature
Faraday continued to study the role of the electrolytic of electrolysis ? Briefly summarize his contributions in
solution, or electrolyte, as he named it, in electrolysis. He this area.
also coined most of the other modern terms of electrolysis
including electrode, ion, anode, cathode, anion, and 2. How are amounts of hydrogen and oxygen gas made
cation. These investigations culminated in the discovery of from the electrolytic decomposition of water related
to the chemical formula of water ?
his basic laws of electrolysis.
Still valid today, these principles put electrolysis on a
quantitative footing, leading to our current understanding
of the phenomenon. They also bolstered the atomic theory,
which was still seriously contested by many chemists at
the time. And perhaps most important, Faraday 's experi-
ments inspired his successors to further clarify the chemi- SClINKS. ] Drwtopfd «4 kytfc
*
cal nature of solutions. This ultimately led to Svante Hjbwl Some fe chm AtwulNt
*
Arrhenius's theory of electrolytic dissociation and the evo - For a variety of links related to this
chapter, go to g
lution of a new division in the chemical field, known today
as physical chemistry. Topic: Electrolysis
SciLinks code: HC60479
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•

^
IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES
* 0 9

' s ,
, «4 — c :
r )
 SECTION 2
Colligative Properties
OBJECTIVES of Solutions
^ List four colligative properties,
and explain why they are
classified as colligative
properties.
T he presence of solutes affects the properties of the solutions. Some
Calculate freezing-point of these properties are not dependent on the nature of the dissolved
depression, boiling-point substance but only on how many dissolved particles are present . Prop -
elevation, and solution molal- erties that depend on the concentration of solute particles hut not on their
ity of nonelectrolyte solutions. identity are called colligative properties. In calculations involving some
colligative properties, the concentration is given in terms of molality, m.
>J Calculate the expected
changes in freezing point and
boiling point of an electrolyte
solution. Vapor- Pressure Lowering
The boiling point and freezing point of a solution differ from those of
^ Discuss causes of the differ - the pure solvent . The graph in Figure 6 shows that a nonvolatile solute
ences between expected and
raises the boiling point and lowers the freezing point . A nonvolatile
experimentally observed
substance is one that has little tendency to become a gas under existing
colligative properties of
electrolyte solutions. conditions.

Vapor Pressure vs. Temperature for a Pure Solvent

and a Solution with a Nonvolatile Solute

1.0

solvent
at bp of
pure solvent
e
<u
>
FIGURE 6 Vapor pressure as a o
cn
function of temperature is shown for
O
a pure solvent and for a solution of 0>
a nonvolatile solute in that solvent . 3

The vapor pressure of the solution is 0)

lower than the vapor pressure of the a

o_
pure solvent . This can he seen by c

—
fz
noting the decrease in pressure >
between the pure solvent and the
solution at the temperature that is
the boiling point of the pure solvent.
The solute thus reduces the freezing
solution
A/ f
pure
solvent
'b
pure
solvent A b
'
- ' b
solution

point and elevates the boiling point . Temperature (°C )

446 CHAPTER 13
 < >

t\
*t
V
3

>V
T
) **
V

.
9 &

W /v
V
9

f \
V

J3
l*
V
s>
t
*w
<

^*
^
.'
V V
*
4 « i
'
9 V ® ^ o 3
3
^ ^ ^ V w> ®
3 * %>
*
<
*> ** tf * *® v * ® V® V

Pure water Aqueous solution of nonvolatile solute

<9 Used to represent C 12H22On, sucrose

&
s Used to represent H20, water

FIGURE 7 At a given tempera -

.
ture the vapor pressure of water
over pure water is greater than the
vapor pressure of water over an
To understand whv a nonvolatile solute changes the boiling point and aqueous solution containing a non -
freezing point , you must consider equilibrium vapor pressure, which volatile solute , such as sucrose.
was discussed in Chapter 10. Vapor pressure is the pressure caused bv
molecules in the gas phase that are in equilibrium with the liquid phase.
Experiments show that the vapor pressure of a solvent containing a
nonvolatile solute is lower than the vapor pressure of the pure solvent
at the same temperature, as shown in Figure 7. As the number of solute
particles increases in a given volume of solution , the proportion of solvent
( water ) molecules decreases. Fewer water molecules will be available to
escape from the liquid. As a result , the tendency of water molecules to
leave the solution and enter the vapor phase decreases. Thus, the vapor
pressure of the solution is less than the vapor pressure of pure water.
Nonelectrolyte solutions of the same molality have the same concen -
tration of particles. Equally dilute molal solutions of any nonelectrolyte
solutes in the same solvent lower the vapor pressure equally. For exam -
ple. a l m aqueous solution of the nonelectrolyte glucose. C(, l 1 j low -
4
ers the vapor pressure of water by 5.5 x 10 atm at 25 C. A 1 m solution
,
of sucrose, C FE Oj . another nonelectrolyte, also lowers the vapor
pressure by 5.5^ x 10^ -4 atm . Because vapor-pressure lowering depends on
the concentration of a nonelectrolyte solute and is independent of
solute identity, it is a colligative property.
Refer to the graph in Figure 6. Because the vapor pressure has been
lowered , the solution remains liquid over a larger temperature range.
This lowers the freezing point and raises the boiling point . It follows
that changes in boiling point and freezing point also depend on the con -
centration of solute and are therefore colligative properties.

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 447

 Freezing- Point Depression
The freezing point of a 1 m solution of any nonelectrolyte solute in
water is found by experiment to be 1.86°C lower than the freezing point
of water. That is, when 1 mol of a nonelectrolyte solute is dissolved in
1 kg of water , the freezing point of the solution is -1.86 C instead of
0.00° C. When 2 mol of a nonelectrolyte solute is dissolved in 1 kg of
water , the freezing point of the solution is -3.72°C. This is 2 x (-1.86 C ).
In fact , for any concentration of a nonelectrolvte solute in water, the
decrease in freezing point can be estimated by using the value of
— 1.86 C / m . This value, called the molal freezing- point constant ( KA is
the freezing - point depression of the solvent in a I - molal solution of a
nonvolatile, nonelectrolyte solute.
Each solvent has its own characteristic molal freezing- point constant .
The values of Kf for some common solvents are given in Table 2. These
values are most accurate for dilute solutions at 1 atmosphere of pres-
sure. Some variations are introduced in the value of K ( at other pres-
sures and with more -concentrated solutions. The table also shows the
values of a related quantity called Khr which you will study next .
As stated earlier, the freezing point of a solution containing 1 mol of a
nonelectrolyte solute in 1 kg water is 1.86°C lower than the normal freez-
ing point of water. The freezing- point depression , Atf , is the difference
between the freezing points of the pure solvent and a solution of a non -
electrolyte in that solvent, and it is directly proportional to the molal con -
centration of the solution. As shown by the previous example, if the molal
concentration is doubled , the freezing- point depression is doubled .
Freezing- point depression can be calculated by the following equation .

A/ , = Kfm
1

Kf is expressed as C / m, m is expressed in mol solute / kg solvent ( molal -

ity ) , and At ( is expressed in °C. Sample Problems C and D show how this
relationship can be used to determine the freezing- point depression and
molal concentration of a solution .

TABLE 2 Molal Freezing-Point and Boiling-Point Constants

Normal f.p. Molal f.p. constant Normal b.p. Molal b.p. constant
Solvent ( ° C) Kf (°CIm ) ( ° C) Kb (°CIm )
Acetic acid 16.6 -3.90 117.9 3.07
Camphor 178.8 -39.7 207.4 5.61
Ether -116.3 -1.79 34.6 2.02
Naphthalene 80.2 - 6.94 217.7 5.80
Phenol 40.9 -7.40 181.8 3.60
Water 0.00 -1.86 100.0 0.51

448 CHAPTER 13
 SAMPLE PROBLEM C For more help, go to the Math Tutor a t the end of this chapter.

What is the freezing-point depression of water in a solution of 17.1 g of sucrose, C12H22On , in 200. g of
water? What is the actual freezing point of the solution?

SOLUTION
1 ANALYZE Given: solute mass and chemical formula = 17.1 g C L
solvent mass and identity = 200. g water
^ ^O,,
Unknown: a . freezing-point depression
b. freezing point of the solution

2 PLAN Find the molal freezing-point constant . Kf . for water in Table 2. To use the equation for
freezing-point depression. A /; = Kfm , you need to determine the molality of the solution.
I mol solute
mass of solute ( g ) x = amount of solute ( mol )
molar mass of solute ( g)
amount of solute ( mol ) 1000 g water
x = molality
mass of solvent ( g) 1 kg water
,
AIf = K m
f.p. solution = f.p. solvent + A / ,
3 COMPUTE 17.1
1 mol ( 12 ^22^ 11 = 0.0500 mol
342.34
0.0500 mol UXXLg water 0.250 mol C12H220n
= 0.250 m
200. gwater kg water kg water
,
a. A/ = 0.250 m x ( -1.86°C7wr) = -0.465 X
b. f.p. solution = 0.000 C 4- ( - 0.465 C ) = - 0.465 C

SAMPLE PROBLEM For more help, go to the Math Tutor a t the end of this chapter.
A water solution containing an unknown quantity of a nonelectrolyte solute is found to have a freezing
point of - 0.23° C. What is the molal concentration of the solution?

SOLUTION
1 ANALYZE Given: freezing point of solution = — 0.23 C
Unknown: molality of the solution

2 PLAN Water is the solvent, so you will need the value of Kf , the molal- freezing-point constant for
water, from Table 2. The Aif for this solution is the difference between the f.p. of water and
-
the f.p. of the solution. Use the equation for freezing point depression to calculate molality.
Atj = f.p. of solution - f.p. of pure solvent
Ai c - K f m Solve for molality, m .
At ,
m=—

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 449

3 COMPUTE Mf = - 0.23°C - 0.00 C = -0.23°C
-0.23 C
m= = 0.12 m
-1.86°£lm
4 EVALUATE As shown by the unit cancellation, the answer gives the molality, as desired. The answer is
properly limited to two significant digits.

PRACTICE Answers in Appendix E

1. A solution consists of 10.3 g of the nonelcctrolyte glucose .

,
C0H :O(v dissolved in 250. g of water. What is the freezing-point
depression of the solution?
2 . In a laboratory experiment , the freezing point of an aqueous solu -
tion of glucose is found to be - 0.325 C. What is the rnolal concen -
tration of this solution ?
3. If 0.500 mol of a nonelectrolyte solute are dissolved in 500.0 g of
ether , what is the freezing point of the solution ?
— i T C L*I '0
4 . The freezing point of an aqueous solution that contains a non - Go to go hrw.com for
.
electrolyte is -9.0 C. more practice problems
a . What is the freezing-point depression of the solution? that ask you to calculate
b. What is the rnolal concentration of the solution? the freezing - point
depression.
Keyword: HC 6I0 NX

Boiling- Point Elevation

As discussed in Chapter 12. the boiling point of a liquid is the tempera -
ture at which the vapor pressure of the liquid is equal to the prevailing
atmospheric pressure. Ilierefore, a change in the vapor pressure of the
liquid will cause a corresponding change in the boiling point. As stated
earlier, the vapor pressure of a solution containing a nonvolatile solute
is lower than the vapor pressure of the pure solvent. This means that
more energy as heat will be required to raise the vapor pressure of the
solution to equal the atmospheric pressure. Thus, the boiling point of a
solution is higher than the boiling point of the pure solvent .
The rnolal boiling- point constant ( Kh ) is the boiling - point elevation of
-
the solvent in a / rnolal solution of a nonvolatile, nonelectrolyte solute.
The boiling-point elevation of a 1 - rnolal solution of any nonelectrolyte
solute in water has been found by experiment to be 0.51 C. Thus, the
-
rnolal boiling point constant for water is 0.51 C / m.
For different solvents, the rnolal boiling-point constants have differ -
ent values. Some other values for Kh are included in Table 2. Like the
-
freezing point constants, these values are most accurate for dilute
solutions.
The boiling- point elevation, Ais the difference between the boiling
points of the pure solvent and a nonelectrolyte solution of that solvent,

450 CHAPTER 13
and it is directly proportional to the molal concentration o f the solution.
Boiling-point elevation can be calculated by the following equation.
\tb = Khm

When Kh is expressed in °C / m and m is expressed in mol of solute/kg of

solvent. Ath is the boiling-point elevation in C.

SAMPLE PROBLEM E For more help, go to the Math Tutor at the end of this chapter.

What is the boiling- point elevation of a solution made from 20.1 g of a nonelectrolyte solute and 400.0 g
of water ? The molar mass of the solute is 62.0 g.

SOLUTION
1 ANALYZE Given: solute mass = 20.1 g
solute molar mass = 62.0 g
solvent mass and identity = 400.0 g of water
Unknown: boiling-point elevation

2 PLAN Find the molal boiling-point constant. Kh, for water in Table 2. To use the equation for
boiling-point elevation. Ath = Khni, you need to determine the molality of the solution.
1 mol solute
mass of solute ( g ) x = amount of solute ( mol )
molar mass of solute (g)
amount of solute ( mol ) 1000 g water
x = molalitv
mass of solvent ( g ) 1 kg water

Mh = Khm
1 mol solute
3 COMPUTE 20.1 g._ol okrte- x = 0.324 mol of solute
* 62.0 gof solute
0.324 mol of solute 1000 gwater mol solute
x = 0.810 = 0.810 / 7 ?
400.0 gWiUer 1 kg water kg water
Ath = 0.5 TC/wx 0.810 m = 0.41 C

PRACTICE Answers in Appendix E

1. A solution contains 50.0 g of sucrose. C F On, a nonelectrolyte,

^ ^
dissolved in 500.0 g of water. What is the boiling-point elevation ?
,,
2. A solution contains 450.0 g of sucrose, C H O . a nonelectrolyte,
^ ^
dissolved in 250.0 g of water. What is the boiling point of the solution?
3. If the boiling-point elevation of an aqueous solution containing a
nonvolatile electrolyte is 1.02 C. what is the molality of the solution? —Go to go.hrw.com for
4. The boiling point of an aqueous solution containing a nonvolatile more practice problems
electrolyte is 100.75°C . that ask you to calculate
a . What is the boiling-point elevation? the boiling-point
b. What is the molality of the solution? elevation.

^
_
JC Keyword: HC6I0NX
IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 451
 (a ) ( b)

0s
3
* •* 3 * 4

D j
>> 3 O
*
Vjj J ST S
3 J
*
«9 ^ <* * V
3*
•
-* > 3 * * ** Pure water v
J : * 91
Sucrose solution
^
9 <9 9

Semipermeable membrane

Used to represent Cl 2H22Ol 1 sucrose (

,3 Used to represent H20, water

FIGURE 8 ( a ) When pure water Osmotic Pressure

and an aqueous sucrose solulion are
separated by a semipermeable mem - Figure 8 illustrates another colligative property. In the figure, an aque -
brane. the net movement of water
ous sucrose solution is separated from pure water by a semipermeable
molecules through the membrane is
from the pure water side into the
membrane. A semipermeable membrane allows the passage of some
aqueous solution , ( b ) The level of particles while blocking the passage of others. The level of the sucrose
the solution rises until pressure solution will rise until a certain height is reached. What causes the level
exerted by the height of the solution of the solution to rise?
equals the osmotic pressure, at The semipermeable membrane allows water molecules, but not
which point no net movement of sucrose molecules, to pass through . The sucrose molecules on the solu -
water molecules occurs. tion side allow fewer water molecules to strike the membrane than
strike on the pure water side in the same amount of time. Thus, the rate
at which water molecules leave the pure water side is greater than the
rate at which they leave the solution. This causes the level of the solu -
tion to rise. The level rises until the pressure exerted by the height of the
solution is large enough to force water molecules back through the
membrane from the solution at a rate equal to that at which they enter
from the pure water side.
M r> The movement of solvent through a semipermeable membrane from
Developed Md maintained by !t»
NabmuJ Science leackm AMKUMM
the side of lower solute concentration to the side of higher solute concen -
For a variety of links related to this tration is osmosis. Osmosis occurs whenever two solutions of different
concentrations are separated by a semipermeable membrane. Osmotic
Topic : Osmosis
SciLinks code: HC61090
* pressure is the external pressure that mast be applied to stop osmosis. In
the example given above, osmosis caused the level of the solution to rise
until the height of the solution provided the pressure necessary to stop
osmosis. Because osmotic pressure is dependent on the concentration of

452 CHAPTER 13
solute particles and not on the type of solute particles, it is a colligative
property. The greater the concentration of a solution , the greater the Chemistry in Action
osmotic pressure of the solution . Water Purification
Regulation of osmosis is vital to the life of a cell because cell mem - by Reverse Osmosis
branes are semipermeable. Cells lose water and shrink when placed in a The process of reverse osmosis is used
solution of higher concentration . They gain water and swell when placed to purify water because it removes many
in a solution of lower concentration . In vertebrates, cells are protected contaminants at relatively low cost. The
from swelling and shrinking by blood and lymph that surround the cells. osmosis process can be reversed by
applying a pressure greater than the
Blood and lymph are equal in concentration to the concentration inside osmotic pressure to an aqueous solu-
the cell. tion. This causes the water, but not the
dissolved solutes, to flow from the solu-
tion through the semipermeable mem -
brane. The largest municipal desalination
plant in the United States is in Sarasota,
Electrolytes and Colligative Properties Florida. It treats salt water by reverse
osmosis to produce more than 12 mil-
Early investigators were puzzled by experiments in which certain sub- lion gallons of fresh water per day. Other
stances depressed the freezing point or elevated the boiling point of a applications include the desalination of
solvent more than expected . For example, a 0.1 m solution of sodium sea water on ocean-going vessels and
wastewater purification.
chloride. NaCl. lowers the freezing point of the solvent nearly twice as
much as a 0.1 m solution of sucrose. A 0.1 m solution of calcium chloride,
CaCl2 , lowers the freezing point of the solvent nearly three times as much
as a 0.1 m solution of sucrose. The effect on boiling points is similar.
To understand why this is so, contrast the behavior of sucrose with that
of sodium chloride in aqueous solutions. Sugar is a nonelectrolyte. Each
sucrose molecule dissolves to produce only one particle in solution , so
1 mol of sucrose dissolves to produce only 1 mol of particles in solution .
NaCl , however, is a strong electrolyte. Each mole of NaCl dissolves to
produce 2 mol of particles in solution: 1 mol of sodium ions and 1 mol
of chloride ions. Figure 9 compares the production of particles in solu -
FIGURE 9 Compare the
tion for three different solutes. As you can see, electrolytes produce number of particles produced per
more than 1 mol of solute particles for each mole of compound dissolved. formula unit for these three solutes.
Colligative properties depend on
the total concentration of particles.
H 20

C 12 H 22
° 11 V * Cl"
%
*
9>
*

Sucrose solution Sodium chloride solution Calcium chloride solution

H 2O HJO H 20
C12 H 22 Ca 2 *(aq) + 2CI (aq)
° NaCl Na* ( aq ) + Cl (aq) CaCI 2 "
11

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 453

 Calculated Values for Electrolyte Solutions
Remember that colligative properties depend on the total concentra-
tion of solute particles regardless of their identity. The changes in col-
ligative properties caused by electrolytes will be proportional to the
total molality of all dissolved particles, not to formula units. For the
same molal concentrations of sucrose and sodium chloride, you would
expect the effect on colligative properties to be twice as large for sodi -
um chloride as for sucrose. What about barium nitrate. Ba(N03 )2 ? Each
mole of barium nitrate yields 3 mol of ions in solution.

Ba( NO;MV) > Ba 2* ( aq ) + 2NOJ ( aq )

You would expect a Ba(N03 ) 2 solution of a given molality to lower the

freezing point of its solvent three times as much as a nonelectrolytic
solution of the same molalitv.

SAMPLE PROBLEM F For more help, go to the Math Tutor at the end of this chapter.
What is the expected change in the freezing point of water in a solution of 62.5 g of barium nitrate,
Ba ( N()3 ) 2 , in 1.00 kg of water?

SOLUTION
1 ANALYZE Given: solute mass and formula = 62.5 g Ba(N03 )2
solvent mass and identity = 1.00 kg water
A if = Kfm
Unknown: expected freezing-point depression

2 PLAN The molality can be calculated by converting the solute mass to moles and then dividing by
the number of kilograms of solvent. That molality is in terms of formula units of Ba ( N03 )2
and must be converted to molality in terms of dissociated ions in solution. It must be multi -
plied by the number of moles of ions produced per mole of formula unit. This adjusted
molality can then be used to calculate the freezing-point depression.
mass of solute (g) 1 mol solute mol
— x = molalitv of solution
mass of solvent ( kg ) molar mass of solute ( g ) kg

mol mol ions °C • kg H:0

molalitv
*
of solution x molalitv conversion xA't
kg mol mol ions
= expected freezing-point depression ( C )

This problem is similar to Sample Problem E. except that the solute is ionic rather than a
nonionizing molecular solute. The number of particles in solution will therefore equal the
number of ions of the solute.
3 COMPUTE 62.5 guBafNOvT mol Ba(NO )2 0.239 mol Ba(N03 )2
~ X ^
TOO kg H:Q 261.35 £ kg H2Q

454 CHAPTER 13
 Ba(N03)2( s) -> Bi\ 2+( aq ) + 2N03( aq )
Each formula unit of barium nitrate yields three ions in solution.
0.239 mof BafNOy)2
Tg-H5
3 rook ions
<
mol Ba N03 ) 2
x -
-1.86°C kg4be-
mol ions
— = -1.33°C
^
4 EVALUATE The units cancel properly to give the desired answer in C. The answer is correctly given
to three significant digits. The mass of the solute is approximately one - fourth its molar
mass and would give 0.75 mol of ions in the 1 kg of solvent, so the estimated answer of
0.75 x ( -1.86 C ) = -1.4 C supports our computation.

PRACTICE Answers in Appendix E

1 . What is the expected freezing-point depression for a solution that

contains 2.0 mol of magnesium sulfate dissolved in 1.0 kg of water? — VT f l d « I
Go to go.hrw.com for
2. What is the expected boiling-point elevation of water for a solution more practice problems
that contains 150 g of sodium chloride dissolved in 1.0 kg of water ? that ask you to calculate
the freezing - point
3. The freezing point of an aqueous sodium chloride solution is depression and boiling-
-0.20 C. What is the molality of the solution? point elevation for
electrolyte solutions.
Keyword: HC 6I0NX

Actual Values for Electrolyte Solutions

It is important to remember that the values just calculated are only
expected values. As stated earlier, a 0.1 m solution of sodium chloride
lowers the freezing point nearly twice as much as a 0.1 m solution of
sucrose. The actual values of the colligative properties for all strong elec -
trolytes are almost what would be expected based on the number of
particles they produce in solution. Some specific examples are given in
Table 3. The freezing-point depression of a compound that produces two
ions per formula unit is almost twice that of a nonelectrolytic solution.
The freezing-point depression of a compound that produces three ions
per formula unit is almost three times that of a nonelectrolytic solution.

TABLE 3 Molal Freezing-Point Depressions for Aqueous Solutions of Ionic Solutes

Concentration Afy observed Atf , nonelectrolyte Atfl observed
Solute (ro) (°C) solution (°C) Atf , nonelectrolyte solution
KCI 0.1 -0.345 -0.186 1.85
0.01 -0.0361 -0.0186 1.94
0.001 -0.00366 - 0.00186 1.97
MgS04 0.1 -0.225 -0.186 1.21
0.01 -0.0285 - 0.0186 1.53
0.001 -0.00338 - 0.00186 1.82
BaCl2 0.1 - 0.470 -0.186 2.53
0.01 - 0.0503 - 0.0186 2.70
0.001 - 0.00530 -0.00186 2.84

IONS IN AQUEOUS SOLUTIONS AND COLLIG ATIVE PROPERTIES 455

 .
Look at the values given for KCI solutions in Table 3 The freezing-
point depression of a 0.1 m KCI solution is only 1.85 times greater than
that of a nonelectrolyte solution . However, as the concentration de-
creases, the freezing-point depression comes closer to the value that is
twice that of a nonelectrolyte solution .
The differences between the expected and calculated values are
caused by the attractive forces that exist between dissociated ions in
aqueous solution. The attraction between the hydrated ions in the solu -
tion is small compared with those in the crystalline solid . However,
forces of attraction do interfere with the movements of the aqueous
ions. Only in very dilute solutions is the average distance between the
ions large enough and the attraction between ions small enough for the
solute ions to move about almost completely freely.
Peter Debye and Erich Huckel introduced a theory in 1923 to account
for this attraction between ions in dilute aqueous solutions. According to
this theory, the attraction between dissociated ions of ionic solids in dilute
aqueous solutions is caused by an ionic atmosphere that surrounds each
FIGURE 10 The salts applied to ion. This means that each ion is, on average, surrounded by more ions of
icy roads are electrolytes. They lower
opposite charge than of like charge. A cluster of hydrated ions can act as
the freezing point of water and melt
the ice.
a single unit rather than as individual ions. Thus, the effective total con -
centration is less than expected , based on the number of ions known to
be present .
Ions of higher charge attract other ions very strongly. They therefore
cluster more and have lower effective concentrations than ions with
smaller charge. For example, ions formed by MgS04 have charges of 2 +
and 2-. Ions formed by KCI have charges of 1 + and 1 -. Note in Table 3
that MgS04 in a solution does not depress the freezing point as much as
the same concentration of KCI .

SECTION REVIEW level of the more-concentrated solution or the

1. What colligative properties are displayed by each less- concentrated solution rise?
of the following situations ? 4. a. Calculate the expected freezing-point depres-
a. Antifreeze is added to a car's cooling system to sion of a 0.200 m KN03 solution.
prevent freezing when the air temperature is b. Will the value you calculated match the actual
below 0°C. freezing-point depression for this solution?
b. Ice melts on sidewalks after salt has been Why or why not ?
spread on them. Critical Thinking
2. Two moles of a nonelectrolyte solute are dissolved 5. INFERRING RELATIONSHIPS The freezing-point
in 1 kg of an unknown solvent. The solution freezes depressions of aqueous solutions A, B, and C are
at 7.8°C below its normal freezing point. What is -2.3°C, -1.2°C, and -4.1°C, respectively. Predict
the molal freezing-point constant of the unknown the order of the boiling-point elevations of these
solvent ? Suggest a possible identity of the solvent. solutions, from lowest to highest. Explain your
3. If two solutions of equal amounts in a U- tube are ranking.
separated by a semipermeable membrane, will the

456 CHAPTER 1 3
 CHAPTER HIGHLIGHTS
Compounds in Aqueous Solutions
I Vocabulary •The separation of ions that occurs when an ionic solid dis-
dissociation solves is called dissociation.
net ionic equation •When two different ionic solutions are mixed, a precipitate may
spectator ions form if ions from the two solutions react to form an insoluble
ionization compound.
hydronium ion • A net ionic equation for a reaction in aqueous solution
strong electrolyte includes only compounds and ions that change chemically in
weak electrolyte the reaction. Spectator ions are ions that do not take part in
such a reaction.
•Formation of ions from molecular compounds is called ioniza-
tion. A molecular compound may ionize in an aqueous solution
if the attraction of the polar water molecules is strong enough
to break the polar-covalent bonds of the solute molecules.
•An H;0’ ion is called a hyilronium ion.
•All. or almost all. of a dissolved strong electrolyte exists as ions
in an aqueous solution, whereas a relatively small amount of a
dissolved weak electrolyte exists as ions in an aqueous solution.

Colligative Properties of Solutions

I Vocabulary •Colligative properties of solutions depend only on the total num-
colligative properties ber of solute particles present. Boiling-point elevation, freezing-
nonvolatile substance point depression, vapor-pressure lowering, and osmotic pressure
molal freezing- point constant, Kf are colligative properties.
freezing- point depression, Atf • molal boiling-point and freezing-point constants are used
The
molal boiling- point constant, Kb to calculate boiling-point elevations and freezing- point depres -
boiling- point elevation, & tb sions of solvents containing nonvolatile solutes.
semipermeable membrane •Electrolytes have a greater effect on the freezing and boiling
osmosis points of solvents than nonelectrolytes do .
osmotic pressure •Except in very dilute solutions, the values of colligative proper -
ties of electrolyte solutions are less than expected because of
the attraction between ions in solution.

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 457

 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
10. Write the equation for the dissolution of each
Compounds in Aqueous of the following in water, and then indicate the
Solutions total number of moles of solute ions formed,
a. 0.50 mol strontium nitrate
SECTION 1 REVIEW h. 0.50 mol sodium phosphate
1. How many moles of ions are contained in l L of 11. Using Table 1, write the balanced chemical equa-
a l M solution of KCI? of Mg(N )2?03 tion. write the overall ionic equation, identify
.
2 Use Table 1 to predict whether each of the follow - the spectator ions and possible precipitates, and
ing compounds is considered soluble or insoluble: write the net ionic equation for each of the fol-
a. KCI .
lowing reactions ( Hint: See Sample Problem B.)
b. NaN03 a. mercury( Il) chloride ( a q ) + potassium sul-
c. AgCl fide ( a q ) >
d. BaS04 b. sodium carbonate ( a q ) + calcium chloride
e. Ca3( P04) 2 {aq ) ->
f. Pb( CI03)2~ .
c copper (ll) chloride ( a q ) + ammonium phos -
g. ( NH4 )2S phate ( ( K j ) >
h. PbCI2 ( in cold water )
*
.
12 Identify the spectator ions in the reaction
i. FeS between KCI and AgN03 in an aqueous solution.
j. AI2(S04)3 13. Copper ) II ) chloride and lead(Il) nitrate react in
3 . What is a net ionic equation? aqueous solutions by double displacement .
4. a. What is ionization? Write the balanced chemical equation, the over -
b. Distinguish between ionization and all ionic equation, and the net ionic equation for
dissociation. this reaction. If 13.45 g of copper!II ) chloride
.
5 a. Define and distinguish between strong react, what is the maximum amount of precipi -
electrolytes and weak electrolytes, tate that could be formed?
b. Give two examples of each type.
6. What determines the strength of a solute as an
electrolyte ? Colligative Properties
7. Distinguish between the use of the terms strong
and weak and the use of the terms dilute and of Solutions
concentrated when describing electrolyte SECTION 2 REVIEW
solutions.
14. I low does the presence of a nonvolatile solute
affect each of the following properties of the
PRACTICE PROBLEMS solvent in which the solute is dissolved?
8. Write the equation for the dissolution of each a. vapor pressure
of the following ionic compounds in water. b. freezing point
( Hint: See Sample Problem A . ) c. boiling point
a. Kl c. MgCl: d. osmotic pressure
b. NaN03 d. Na2S04 15. Using Figure 6 as a guide, make a graph of
9. For the compounds listed in the previous prob - vapor pressure versus temperature that shows
lem, determine the number of moles of each ion the comparison of pure water, a solution with
produced as well as the total number of moles x concentration of solute, and a solution with
of ions produced when l mol of each compound 2x concentration of solute. What is the relation-
dissolves in water. ship between &tf for the A solution and Atf for
the Zx solution ?

458 CHAPTER 1 3
 CHAPTER REVIEW

16. a. Why does the level of the more-concentrated 24. If 1.500 g of a solute that has a molar mass of
solution rise when two solutions of different 125.0 g were dissolved in 35.00 g of camphor,
concentrations are separated by a semiper- what would be the resulting freezing point of
meable membrane ? the solution ?
b. When does the level of the solution stop rising?
c. W' hen the level stops rising, what is the net
25. .
Determine the boiling- point elevation of H - 0
in each of the following solutions. ( Hint: See
movement of water molecules across the Sample Problem E. )
membrane ? a . 2.5 m solution of C6H 12Oft ( glucose ) in H 20
17. a . Compare the effects of nonvolatile elec- b. 3.20 g C6 HI:06 in 1.00 kg H:0
trolytes with the effects of nonvolatile non - c. 20.0 g , ( sucrose ) in 500. g H20
electrolvtes on the freezing and boiling points 26. Given the following boiling points, determine
of solvents in which they are dissolved , the molality of each water solution.
b. Why are such differences observed ? a. 100.25°C
18. Why does the actual freezing- point depression of b. 101.53°C
an electrolytic solution differ from the freezing - c. 102.805°C
point depression calculated on the basis of the 27. Given 1.00 m aqueous solutions of each of the
concentration of particles? following electrolytic substances, determine the
expected change in the freezing point of the
PRACTICE PROBLEMS solvent . ( Hint : See Sample Problem F. )
a . Kl
19. Determine the freezing- point depression of
b. CaCli
H 20 in each of the following solutions. ( Hint :
c. Ba ( NOv)2
See Sample Problem C. )
28 . What is the expected change in the freezing
a . 1.50 // ? solution of C H On ( sucrose ) in H 20
^
b. 171 gofCi:H 22On ^in 1.00 kgH 2O
point of water for a 0.015 m aqueous solution
,
c. 77.0 g of C 2 H 22On in 400. g H:0
29.
of AICI3?
What is the expected freezing point of a solu -
-
20. Given the following freezing point depressions,
tion containing 85.0 g NaCI dissolved in 450. g
determine the molality of each solution of an
of water?
unknown nonelectrolyte in water. ( Hint: See
30. Determine the expected boiling point of a solu -
Sample Problem D. )
tion made by dissolving 25.0 g of barium chlo-
a. -0.930°C
ride in 0.150 kg of water .
b. -3.72°C
31 . The change in the boiling point of water for an
c. -8.37T
aqueous solution of potassium iodide is 0.65 C.
21 . A solution contains 20.0 g of Q, H ] 2( )(> (glucose )
Determine the molal concentration of potas-
in 250. g of water.
sium iodide.
a. What is the freezing- point depression of the
32. The freezing point of an aqueous solution of
solvent ?
barium nitrate is -2.65 C. Determine the molal
b. What is the freezing point of the solution ?
concentration of barium nitrate.
22 . How many grams of antifreeze. C2 Fl 4 ( OH ) 2,
33. Calculate the expected freezing point of a solu -
would be required per 500. g of water to pre -
tion containing l .OO kg H:0 and 0.250 mol
vent the water from freezing at a temperature
NaCI .
of -20.0°C?
34. Experimental data for a l .OO m Mgl 2 aqueous
23 . Pure benzene. ChHh. freezes at 5.45°C. A solu -
solution indicate an actual change in the freezing
tion containing 7.24 g C:Cl 4 H 2 in 115 g of ben -
point of water of -4.78 C. Find the expected
zene (specific gravity = 0.879 ) freezes at 3.55 C.
change in the freezing point of water. Suggest a
Based on these data , what is the molal freezing-
possible reason for the discrepancy between the
point constant for benzene?
experimental and expected values.

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 459

 CHAPTER REVIEW

MIXED REVIEW 45. Find the expected freezing point of a water

solution that contains 268 g of aluminum
35. Ciiven 0.01 m aqueous solutions of each of the .
nitrate AKNO ) in 8.50 kg of water.
^^
following, arrange the solutions in order of
increasing change in the freezing point of the
solution. CRITICAL THINKING
a. Nal
b. CaCI: 46. Applying Models
c. K 3PO4 a. You are conducting a freezing-point determi-
d. ChHj:Oh ( glucose ) nation in the laboratory by using an aqueous
36. What is the mnlal concentration of an aqueous solution of KNOj. The observed freezing
calcium chloride solution that freezes at -2.43 C? point of the solution is — 1.15 C. Using a pure
37. a. Write the balanced formula equation that water sample, you recorded the freezing
shows the possible products of a double - point of the pure solvent on the same ther -
mometer as 0.25 C. Determine the molal
displacement reaction between calcium
nitrate and sodium chloride. concentration of KNOv Assume that there
b. Using Table 1, determine whether there is a are no forces of attraction between ions .
precipitate. b. You are not satisfied with the result in part
c. Does this reaction occur ? ( a ) because you suspect that you should not
38. Write a balanced equation to show what occurs ignore the effect of ion interaction. You take
when hydrogen bromide dissolves and reacts .
a 10.00 mL sample of the solution After
with water. Include a hydronium ion in the carefully evaporating the water from the
equation. solution, vou obtain 0.415 g KN03. Deter -
39. Write the equation for the dissolution of each mine the actual molal concentration of
of the following in water, and then indicate the KN03 and the percentage difference
total number of moles of solute ions formed. between the concentration observed in the
a. 0.275 mol of potassium sulfide freezing-point determination and the actual
b. 0.15 mol of aluminum sulfate concentration of KN03. Assume that the
40. Calculate the expected change in the boiling solution's density is 1.00 g/ mL.
point of water in a solution made up of 131.2 g 47. Analyzing Information The observed freezing-
of silver nitrate. AgN03, in 2.00 kg of water. point depression for electrolyte solutions is
41. Nitrous acid. HNCT. is a weak electrolyte. Nitric sometimes less than the calculated value. Why
acid, IINOv is a strong electrolyte. Write equa - does this occur ? Is the difference greater for
tions to represent the ionization of each in concentrated solutions or dilute solutions?
water. Include the hydronium ion, and show the 48. Analyzing Information The osmotic pressure
appropriate kind of arrow in each equation. of a dilute solution can be calculated as follows:
42. Find the boiling point of an aqueous solution con -
taining a nonelectrolyte that freezes at -6.51°C. K = MRT
K = osmotic pressure
43. Write a balanced equation for the dissolution of
sodium carbonate. Na:COv in water. Find the M = concentration in moles per liter
number of moles of each ion produced when R = ideal gas constant
T = absolute temperature of the solution
0.20 mol of sodium carbonate dissolves. Then,
find the total number of moles of ions. How does the osmotic-pressure equation com -
44 . Given the reaction below and the information pare with the ideal gas law?
in Table I , write the net ionic equation for the
reaction.
potassium phosphate ( aq ) + lead ( II ) nitrate ( aq )
460 CHAPTER 1 3
 CHAPTER REVIEW

USING THE HANDBOOK ALTERNATIVE ASSESSMENT

49. Common reactions for Group 13 elements are 53. Performance Determine the freezing point of
found in the Elements Handbook . Review this four different mixtures of water and ethylene
material, and answer the following: glycol ( use commercial antifreeze). What mix -
a. Write net ionic equations for each of the ture has the lowest freezing point ?
example reactions shown on page 809. 54. Performance Find the optimum mixture of
b. Which reactions did not change when written salt and ice for reducing the temperature of the
in net ionic form? Why ? chilling bath for an ice-cream freezer. Use your
50. Common reactions for Group 14 elements are data to write a set of instructions on how to pre -
found in the Elements Handbook . Review this pare the chilling bath for making ice cream.
material, and answer the following:
55 . Performance Using a low - voltage dry cell,
a. Write net ionic equations for each of the
assemble a conductivity apparatus. Secure sev -
example reactions shown on page SI 3.
eral unknown aqueous solutions of equal molal-
.
b Which reactions did not change when written
ity from your instructor, and use the apparatus
in net ionic form? Why?
to distinguish the electrolytes from the non-
electrolytes. Among those identified as electro-
lytes. rank their relative strengths as conductors
RESEARCH & WRITING
from good to poor.
51. Find out how much salt a large northern city, 56. Performance Using equal volumes of the
such as New York City or Chicago, uses on its unknown solutions from the preceding activity,
streets in a typical winter. What environmental explain how you could use the freezing-point
problems result from this use of salt ? What depression concept to distinguish the electro-
substitutes for salt are being used to melt ice lytes from the nonelectrolytes. Explain how you
and snow? could determine the number of ions contained
52. Research the role of electrolytes and electro - per molecule among the solutes identified as
lytic solutions in your body. Find out how electrolytes. Design and conduct an experiment
electrolytes work in the functioning of nerves to test your theories.
and muscles. What are some of the health prob-
lems that can arise from an imbalance of elec -
trolytes in body fluids?

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 461

 Math Tutor BOILING AND FREEZING POINTS OF SOLUTIONS

The presence of a nonvolatile solute causes the freezing point of a solution to be lower
and the boiling point to be higher than those of the pure solvent. The freezing -point
depression, Mt , is the amount that the freezing point is lowered. It is calculated by using
the formula Atf = Kfm. The boiling -point elevation, Atb, is the amount that the boiling
point is elevated. It is found by using the equation Atb = Kbm. To determine Atf or Atb,
you need to know its molal concentration, m (moles of solute per kilogram of solvent).
You also need to know the molal freezing-point constant, K{ , or the molal boiling-point
constant, Kb. The values for Kf and Kb depend on the solvent and are given in Table 2.
When these equations are used for electrolytes, the molality represents the total number
of moles of ions in solution.

Problem-Solving TIPS
• Make sure that you find the molal concentration, not the molar concentration.
• For electrolytes, calculate the total number of moles of ions in solution.

SAMPLE
What is the theoretical boiling point of a solution of 247 g of potassium chloride. KCI. dis-
solved in 2.90 kg of water ? Potassium chloride is a strong electrolyte.
First , determine the molality of the KCI that dissolved.
1 mol solute
mass of solute ( g ) x = amount of solute (mol )
molar mass of solute ( g)
1 mol KCI
247 jHtCTx = 3.31 mol KCI
74.55 g CT
^
mol solute particles 3.31 mol KCI
molality KCI( / / ? ) = = 1.14 /;/ KCI
mass of solvent ( kg) 2.90 kg H:0
Because KCI is an electrolyte, the total moles of ions in solution must now be determined.
The equation KCl( s) » K' ( t u / ) + Cl ( i u/ ) shows that 1 mol KCI will yield 2 mol of ions.
To find the total molality of particles in solution, multiply the molality of the solute by
the moles of ions produced by the dissociation: 2 x 1.14 m KCI = 2.28 / / /.
Next, use the equation Aih = where Kh for water is 0.51 Clm and the value for m is 2.28.
Ath = (0.5i°C/m)( 2.28 m ) = 1.16°C
The new boiling point is equal to the sum of the boiling point of the solvent and Atfr
boiling point of solution = 100 C + 1.16 C = 101.16 C

PRACTICE PROBLEMS
.
1 What is the freezing point of a solution contain - 2. What is the boiling point of a solution com -
ing 28.0 g of the strong electrolyte calcium chlo - posed of 850 g of ethylene glycol. C:H 6()2,
.
ride CaCU. dissolved in 295 g of water? mixed with 1100 g of water?

462 CHAPTER 13
Answer the following items on a separate piece of paper. The table below shows the freezing points of solu -
tions of three nonvolatile solutes, X , Y. and Z, in
MULTIPLE CHOICE
water. Refer to the table to answer items 6 and 7.
1. Acetic acid is a weak electrolyte because it The Kr for water is -1.86°Clm.
A . is miscible with water.
B. forms hydronium and hydroxide ions in Solute Water Freezing
aqueous solution . Solute ( mol ) (g ) point ( ° C )
C . lowers the freezing point of water.
D . ionizes only slightly in aqueous solution.
X 1.00 1000 -5.58
Y 1.00 1000 -1.86
2. Which of the following solutions would contain Z 1.00 1000 -3.72
the highest concentration of hydronium ions.
,
H CR ? .
6 Which of the following statements is not true ?
A . 0.10 M HC1 A . All three solutes are nonelectrolytes.
B . 0.10 M HF B. Solute X could be Ca ( N 03) 2.
C. 0.10 M CH ,COOH C. Solute Y could be sucrose.
D. 0.10 M NaCl D . Solute Z could be KCI.
3. Which of the following is the best representa - 7. Which of the solutions described in the table
tion of the precipitation reaction that occurs would have the highest boiling point ?
when aqueous solutions of sodium carbonate A . the solution of solute X
and calcium chloride are mixed ?
B . the solution of solute Y
A . Na +( aq ) + Cr ( aq ) 2 NaCl (s) C. the solution of solute Z
COl
B . 2 Na + ( w/ ) + ~
( aq ) +
D . All three solutions would have the same
Ca2 ( w/ ) + 20T { aq )
*

* CaCO3(5) + 2 NaCl (.v )

——
C. Ca ~~ ( aq ) + CO ] ~( aq ) > CaC03( .v )
boiling point .
.
D No precipitation reaction occurs. SHORT ANSWER

4. Which of the following is not a colligative 8. An aqueous solution of an unknown quantity of

property? a nonelectrolyte solute is found to have a freez -
A . molality ing point of -0.58' C. What is the molal concen -
B. vapor- pressure lowering tration of the solution ?
-
C. boiling point elevation 9. Give the names and formulas of two strong
D . osmotic pressure electrolytes.

5. Solution A contains 0.1 mol of sucrose. EXTENDED RESPONSE

,
C|2 Il Gj . dissolved in 500 g of water. Solution
^ 0.1 mol of sodium chloride. NaCl, in 10. Write the formula equation , the overall ionic
B contains equation , and the net ionic equation for the pre-
500 g of water. Which of the following state- cipitation reaction that occurs when solutions of
ments about these solutions is true ? zinc chloride, ZnCT. and sodium sulfide. Na:S,
A . Both solutions have the same vapor pressure. are mixed .
B . Solution A would boil at a higher tempera -
ture than solution B would .
.
11 Distinguish between dissociation and ionization .
Write one chemical equation to illustrate each
C. Solution A would freeze at a higher tempera - of these terms.
ture than solution B would.
.
D Both solutions would boil at the same
temperature. Before choosing an answer to a
question, try to answer the question without looking
at the answer choices on the test.

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 463

 M I C R O-
EXPERIMENT 13 L A B

Testing Water for Ions

OBJECTIVES BACKGROUND
• Observe chemical reactions involving aque - The physical and chemical properties of aqueous
ous solutions of ions. solutions are affected by small amounts of dissolved
ions. For example, if a water sample has enough Mg2*
• Relate observations of chemical properties
to the presence of ions. or Ca 2 ^ ions, it does not create lather when soap is
added. This is common in places where there are
• Infer whether an ion is present in a water many minerals in the water ( hard water ). Other ions,
sample. such as Pb2 + and Co , can accumulate in body tis
*
-
• Apply concepts concerning aqueous solu- sues; therefore, solutions of these ions are poisonous.
tions of ions. Because some sources of water may contain
harmful or unwanted substances, it is important to
MATERIALS find out what ions are present . In this experiment ,
24- well microplnte lid you will test various water samples for the presence
of four common , nontoxic ions: Fe ^ , Ca \ Cl , and
"

line - tipped dropper bulbs, labeled , with

^
SO . Some of the samples may contain these ions
'

solutions, 10 in very small concentrations, so make very careful

overhead projector ( optional ) observations.
paper towels
SAFETY
solution I : reference ( all ions )
solution 2: distilled water ( no ions )
solution 3: tap water ( may have ions )
For review of safety, please see Safety in the
solution 4: bottled spring water ( may have Chemistry Laboratory in the front of your book .
ions )
solution 5: local river or lake water ( may PREPARATION
have ions ) 1 . Create a data table in your lab notebook follow -
solution 6: solution X , prepared by your ing your teacher s instructions. Record all of
’

teacher ( may have ions ) vour observations in your data table.

solution A: NaSCN solution ( test for Feu ) 2 . Place the 24 - well microplate lid in front of you
on a white background . Label the columns and
solution B: Na 2C2( )4 solution ( test for Ca 2 + ) rows as instructed by your teacher. The coordi -
solution C: AgN ( )3 solution ( test for Cl ) "
nates will designate the individual circles. For
example, the circle in the top right corner would
solution I ): Sr ( \ ( ) * L solution ( test for
be l - D.
sof )
white paper PROCEDURE
1 . Obtain labeled dropper bulbs containing the six
different solutions from your teacher.

464 CHAPTER 13
 EXPERIMENT 13

2 . Place a drop of the solution from bulb I into 8. Follow the procedure used for bulb A with bulbs
circles 1 - A , 1 - B, 1 -C, and 1 - D ( the top row ). B, C, and D to test for the other ions. Record
Solution 1 contains all four of the dissolved ions, your observations about the test results. Specify
so these drops will show what a positive test for whether the solutions contained Ca:+, Cl , or S04
" "

each ion looks like. Be careful to keep the solu- and whether the ions seemed to be present at a
tions in the appropriate circles. Any spills will high , moderate, or low concentration . A black
cause poor results. background may be useful for these three tests.
3 . Place a drop of the solution from bulb 2 into 9. If some of the results are difficult to discern ,
each of the circles in row 2. This solution is dis- place your microplate on an overhead projector.
tilled water and should not contain any of the Examine the drops for signs of cloudiness.
ions. It will show what a negative test looks like. Looking at the drops from the side, keep your
line of vision 10° to 15' above the plane of the
4. Place a drop from bulb 3 into each of the circles
lid . Compare each drop tested with the control
in row 3 and a drop from bulb 4 into each of the
drops in row 2. If any sign of cloudiness is
circles in row 4. Follow the same procedure for
detected in a test sample, it is due to the Tyndall
bulb 5 ( into row 5) and bulb 6 ( into row 6 ).
effect and is a positive test result . Record your
These solutions mav or may not contain ions.
results.
The materials list gives contents of each bulb.
5 . Now that each circle contains a solution to be CLEANUP AND DISPOSAL
analyzed , use the solutions in bulbs A-D to test 10. Clean all equipment and your lab sta -
for the presence of the ions. Bulb A contains tion . Return equipment to its proper
NaSCN, sodium thiocyanate, which reacts with place. Dispose of chemicals and solu -
any Fe34 to form the complex ion Fe(SCN )2+, tions in the containers designated by your
which results in a deep red solution . Bulb B con - teacher. Do not pour any chemicals down the
tains Na:C204. sodium oxalate, which reacts with drain or in the trash unless your teacher directs
Ca2+ ions. Bulb C contains AgN 03, silver nitrate, you to do so. Wash your hands thoroughly before
which reacts with Cl ions. Bulb D contains
"

you leave the lab and after all work is finished .

Sr( N 03)2, strontium nitrate, which reacts with
SOj ions. The contents of bulbs B-D react with
"

ANALYSIS AND INTERPRETATION

the specified ion to yield insoluble precipitates.
1. Organizing Ideas: Describe what each positive
6. Holding the tip of hull A 1 to 2 cm above the
) test looked like. Write the balanced chemical
drop of water to be tested , add one drop of solu - equations and net ionic equations for each of
tion A to the drop of reference solution in circle the positive tests.
1 - A and one drop to the distilled water in circle
2- A . Circle 1 - A should show a positive test , and CONCLUSIONS
circle 2- A should show a negative test . In your
1 . Organizing Conclusions: List the solutions that
data table, record your observations about what
the positive and negative tests look like. you tested and the ions that you found in each
solution . Include notes on whether the concen -
7 . Use the NaSCN solution in bulb A to test the tration of each ion w'as high , moderate, or low
rest of the water drops in column A to deter- based on your observations.
mine whether they contain the Feu ion . Record
your observations in your data table. For each of 2. Predicting Outcomes: Using your test results,
the tests in which the ion was present , specify predict which water sample would be the
whether it seemed to be at a high, moderate, or ‘‘hardest . Explain your reasoning.
**

low concentration .

IONS IN AQUEOUS SOLUTIONS AND COLLIGATIVE PROPERTIES 465

 CHAPTER 1 4

Acids and bases change the color

of compounds called indicators.
 SECTION 1
Properties of Acids
and Bases OBJECTIVES
^ List five general properties
of aqueous acids and bases.

Name common binary acids

H ow many foods can you think of that are sour? Chances are that and oxyacids, given their
almost all the foods you thought of, like those in Figure la, owe their chemical formulas.
sour taste to an acid. Sour milk contains lactic acid. Vinegar, which can
be produced by fermenting juices, contains acetic acid. Phosphoric acid
List five acids commonly used
gives a tart flavor to many carbonated beverages. Most fruits contain
in industry and the laboratory,
some kind of acid. Lemons, oranges, grapefruits, and other citrus fruits
and give two properties of
contain citric acid. Apples contain malic acid, and grape juice contains each.
tartaric acid .
Many substances known as bases are commonly found in household
.
products, such as those in Figure lb Household ammonia is an ammo- SJ Define acidsnd base accord-
nia- water solution that is useful for all types of general cleaning. Sodium ing to Arrhenius's theory of
hydroxide, NaOH, known by the common name lye, is present in some ionization.
commercial cleaners. Milk of magnesia is a suspension in water of mag-
nesium hydroxide, Mg( OH)2, which is not very water-soluble. It is used Explain the differences
as an antacid to relieve discomfort caused by excess hydrochloric acid
^
between strong and weak
in the stomach. Aluminum hydroxide, AlfOIl ) , and sodium hydrogen acids and bases.
^
carbonate, NaHC() 3, are also bases commonly found in antacids.

Benzoic acid, HC 7 H502

Sorbic acid, HC6H702
Phosphoric acid, H 3 P04 |Citric acid,
H 3C6 H507
Carbonic acid,
Ascorbic acid,
H 2C6H 6O6

(a) (b )

FIGURE 1 ( a ) Fruits and fruit juices contain acids such as citric acid
and ascorbic acid. Carbonated beverages contain benzoic acid, phosphoric acid,
and carbonic acid, ( b ) Many household cleaners contain bases such as ammonia
and sodium hydroxide. Antacids contain bases such as aluminum hydroxide.

ACIDS AND BASES 467

 Acids
Acids were first recognized as a distinct class of compounds because of
the common properties of their aqueous solutions. These properties are
listed below.
1. Aqueous solutions of acids have a sour taste. Taste, however, should
NEVER be used as a lest to evaluate any chemical substance. Many
acids, especially in concentrated solutions, are corrosive; that is. they
destroy body tissue and clothing. Many are also poisons.
2. Acids change the color of acid - base indicators. When pH paper is
used as an indicator , the paper turns certain colors in acidic solution .
This reaction is demonstrated in Figure 2.
3. Some acids react with active metals and release hydrogen gas, / / >. _
Recall that metals can be ordered in terms of an activity series.
Metals above hydrogen in the series undergo single -displacement
FIGURE 2 A strip of pi I paper
reactions with certain acids. Hydrogen gas is formed as a product , as
dipped into vinegar turns red . show -
ing that vinegar is an acid. shown by the reaction of barium with sulfuric acid .
Ba (s) + IESO4 ( fl <y ) * BaS04( s ) + H 2(g )
4. Acids react with bases to produce salts and water. When chemically
equivalent amounts of acids and bases react , the three properties just
described disappear because the acid is '‘ neutralized . The reaction
*'

products are water and an ionic compound called a salt.

5. Acids conduct electric current. Some acids form many ions in aqueous
solution and are strong electrolytes. Other acids are weak electrolytes.

Acid Nomenclature
A binary acid is an acid that contains only two different elements: hydro -
gen and one of the more electronegative elements. Many common inor -

—
HI are all binary acids.
—
ganic acids are binary acids. The hydrogen halides HF, HO , HBr, and

The procedure used to name binary acids is illustrated by the exam -

ples given in Table 1. In pure form , each acid listed in the table is a gas.
Aqueous solutions of these compounds are known by the acid names.
From the table you can see that naming binary compounds can be sum -
marized as follows.

TABLE 1 Names of Binary Acids

Formula Acid name
HF hydrofluoric acid
HO hydrochloric acid
HBr hydrobromic acid
HI hydriodic acid
H ,S hydrosulfuric acid

468 CHAPTER 14
 FIGURE 3 Structures of ( a ) phos-
phoric acid and ( b ) sulfuric acid

,
( a) H 3 PO

Binary Acid Nomenclature

1. Hie name of a binary acid begins with the prefix hydro-.
.
2 The root of the name of the second element follows this prefix.
3. The name then ends with the suffix - ic.

An oxyacid is an acid dial is a compound of hydrogen, oxygen, and a

third element , usually a nonmetal. Nitric acid, HNO3, is an oxyacid. The
structures of two other oxyacids are shown in Figure 3. Oxyacids are
one class of ternary acids, which are acids that contain three different
elements. Usually, the elements in an oxyacid formula are written as one
or more hydrogen atoms followed by a polyatomic anion. But as you
can see from the structures, the II atoms are bonded to O atoms. The
names of oxyacids follow a pattern, and the names of their anions are
based on the names of the acids. Some common oxyacids and their
anions are given in Table 2.

TABLE 2 Names of Common Oxyacids and Oxyanions

Formula Acid name Anion
CH3COOH acetic acid CH 3COO , acetate
*

H:C03 carbonic acid COy , carbonate

'

HIO3 iodic acid IO3, iodate

HCIO hypochlorous acid CIO , hypochlorite
"

HCIO2 chlorous acid CI02, chlorite

HC103 chloric acid CIO3, chlorate
HCIO4 perchloric acid ClOj, perchlorate
HNO 2 nitrous acid N02,nitrite
HNO3 nitric acid NO3, nitrate
~
H3P03 phosphorous acid PO3 , phosphite
"

H3P 64 phosphoric acid PO4-. phosphate

. sulfite
H2SO3
11 so4
sulfurous acid
sulfuric acid
SO
^
SO} . sulfate

ACIDS AND BASES 469

 Some Common Industrial Acids
The properties of acids make them important chemicals both in the lab-
oratory and in industry. Sulfuric acid, nitric acid, phosphoric acid,
hydrochloric acid, and acetic acid are all common industrial acids.

Sulfuric Acid
SCllNKS. Dwridyri and HMUIMI bn Ibt Sulfuric acid is the most commonly produced industrial chemical in the
KJIHXWI kimt Te*d*n AVMO«(M«
world. More than 47 million tons of it are made each year in the United
For a variety of links related to this
States alone. Sulfuric acid is used in large quantities in petroleum refin-
chapter, go to www.scilinks.org
Topic: Acids
SciLinks code: HC60012
^ ing and metallurgy as well as in the manufacture of fertilizer. It is also
essential to a vast number of industrial processes, including the produc -
tion of metals, paper, paint, dyes, detergents, and many chemical raw
materials. Sulfuric acid is the acid used in automobile batteries.
Because it attracts water, concentrated sulfuric acid is an effective
dehydrating ( water-removing) agent. It can be used to remove water
from gases with which it does not react. Sugar and certain other organic
compounds are also dehydrated by sulfuric acid. Skin contains organic
compounds that are attacked by concentrated sulfuric acid, which can
cause serious burns.

Nitric Acid
Pure nitric acid is a volatile, unstable liquid. Dissolving the acid in water
makes the acid more stable. Solutions of nitric acid are widely used in
industry. Nitric acid also stains proteins yellow. The feather in Figure 4
was stained by nitric acid. The acid has a suffocating odor, stains skin, and
can cause serious burns. It is used in making explosives, many of which
are nitrogen-containing compounds. It is also used to make rubber.

FIGURE 4 Concentrated nitric

acid stains a feather yellow.

470 CHAPTER 14
plastics, dyes, and pharmaceuticals. Initially, nitric acid solutions are col -
orless: however, upon standing, they gradually become yellow because
of slight decomposition to brown nitrogen dioxide gas.

Phosphoric Acid
Phosphorus, along with nitrogen and potassium , is an essential element
for plants and animals. The bulk of phosphoric acid produced each year
is used directly for manufacturing fertilizers and animal feed . Dilute
phosphoric acid has a pleasant but sour taste and is not toxic. It is used
as a flavoring agent in beverages and as a cleaning agent for dairy
equipment. Phosphoric acid is also important in the manufacture of
detergents and ceramics.

Hydrochloric Acid
T he stomach produces HC1 to aid in digestion . Industrially, hydrochloric
acid is important for “ pickling iron and steel. Pickling is the immersion
”

of metals in acid solutions to remove surface impurities. This acid is also

used in industry as a general cleaning agent , in food processing, in the
activation of oil wells, in the recovery of magnesium from sea water, and
in the production of other chemicals.
Concentrated solutions of hydrochloric acid . commonh referred to as
muriatic acid , can be found in hardware stores. It is used to maintain the
correct acidity in swimming pools and to clean masonry.
JO fA
tort09*4 u4 fry Ik*
Acetic Acid IMWMI Stumr IcMfcen Aiwxulw*

Pure acetic acid is a clear , colorless, and pungent -smelling liquid known For a variety of links related to this
as glacial acetic acid. This name is derived from the fact that pure acetic .
chapter, go to ' yww.5al 1nks.org

acid has a freezing point of 17° C. It can form crystals in a cold room. The Topic: Bases
Sci Links code: HC60137
^
fermentation of certain plants produces vinegars containing acetic acid.
White vinegar contains 4 % to 8% acetic acid .
Acetic acid is important industrially in synthesizing chemicals used
in the manufacture of plastics. It is a raw material in the production of
—
food supplements for example, lysine, an essential amino acid . Acetic
acid is also used as a fungicide.

Bases
Sodium Hydroxide
I low do bases differ from acids? You can answer this question by com -
paring the following properties of bases with those of acids.
1 . Aqueous solutions of bases taste bitter. You may have noticed this fact
if you have ever gotten soap, a basic substance, in your mouth . As
with acids, taste should NEVER be used to test a substance to see if
it is a base. Many bases are caustic: they attack the skin and tissues,
causing severe burns.
2. Bases change the color of acid - base indicators. As Figure 5 shows, an FIGURE 5 pH paper turns blue
indicator w ill be a different color in a basic solution than it would be in the presence of this solution of
in an acidic solution . sodium hydroxide.

ACIDS AND BASES 471

 QuickLAB A Wear safety goggles , gloves and an apron.

Materials
Household Acids and Bases • dishwashing liquid, dishwash-
er detergent, laundry deter-
gent, laundry stain remover,
Question fabric softener, and bleach
Which of the household sub- • mayonnaise, baking powder,
stances are acids, and which baking soda, white vinegar,
are bases ? cider vinegar, lemon juice,
soft drinks, mineral water,
and milk
Procedure 4. Add a drop or two of the red
Record all your results in a data • fresh red cabbage
cabbage juice to the solution
table. being tested, and note the • hot plate
color. The solution will turn • beaker, 500 mL or larger
1. To make an acid-base indica -
red if it is acidic and green if • beakers, 50 mL
tor, extract juice from red cab-
it is basic. • spatula
bage. First, cut up some red
cabbage and place it in a • tap water
large beaker. Add enough Discussion • tongs
water so that the beaker is
half full. Then, bring the mix -
1. Are the cleaning products
acids, bases, or neither ?
ture to a boil. Let it cool, and
then pour off and save the 2. What are acid/ base character-
cabbage juice. This solution is istics of foods and beverages ?
an acid-base indicator.
3. Did you find consumer warn-
2. Assemble foods, beverages, ing labels on basic or acidic
and cleaning products to be products ?
tested.
3. If the substance being tested
is a liquid, pour about 5 mL
into a small beaker. If it is a
solid, place a small amount
into a beaker, and moisten it Red cabbage, which contains an
with about 5 mL of water. anthocyanin pigment, can be made
into an acid-base indicator.

SCllNKSJ Dtvctopcd Md
Niitoul kkacr iNckm AiwtUttw
3. Dilute aqueous solutions of bases feel slippery. You encounter this
property of aqueous bases whenever you wash with soap.
For a variety of links related to this
chapter, go to vvww.scilink.s org 4. Bases react with acids to produce salts and water ; The properties of a
(S
•
Topic: Household Acids base disappear with the addition of an equivalent amount of an acid.
and Bases It could also be said that “neutralization" of the base occurs when
SciLinks code: HC60762 these two substances react to produce a salt and water.
5. Bases conduct electric current . Like acids, bases form ions in aqueous
solutions and are thus electrolytes.

472 CHAPTER 1 4
 Arrhenius Acids and Bases
Svante Arrhenius, a Swedish chemist who lived from IS59 to 1927.
understood that aqueous solutions of acids and bases conducted electric
current . Arrhenius therefore theorized that acids and bases must pro-
duce ions in solution. An Arrhenius acid is a chemical compound that
increases ( he concentration of hydrogen ions, II\ in aqueous solution. In
other words, an acid will ionize in solution, increasing the number of
hydrogen ions present. An Arrhenius base is a substance that increases
the concentration of hydroxide ions, OH . in aqueous solution. Some
bases are ionic hydroxides. These bases dissociate in solution to release
hydroxide ions into the solution. Other bases are substances that react
with water to remove a hydrogen ion, leaving hydroxide ions in
the solution.

Aqueous Solutions of Acids

The acids described by Arrhenius are molecular compounds with ioniz -
able hydrogen atoms. Their water solutions are known as aqueous acids .
All aqueous acids are electrolytes.
Because acid molecules are sufficiently polar, water molecules
attract one or more of their hydrogen ions. Negatively charged anions
are left behind. As explained in Chapter 13. the hydrogen ion in aque -
ous solution is best represented as H;0+. the hydronium ion. The ion-
ization of an HN03 molecule is shown by the following equation.
Figure 6 also shows how the hydronium ion forms when nitric acid
reacts with water.

HN0;(/ ) + H:0( / ) ICO '

{ aq ) + NO } ( aq )

Similarly, ionization of a hydrogen chloride molecule in hydrochloric

acid can be represented in the following way.

HCl(g) + H?0( / ) > \ \ }0+( aq ) + C\ - ( aq )

H 3 O+
Nitric acid Water Hydronium ion Nitrate ion

FIGURE 6 Arrhenius's observations form the basis of a definition of

acids. Arrhenius acids, such as the nitric acid shown here, produce hydroni-
um ions in aqueous solution.

ACIDS AND BASES 473

 TABLE 3 Common Aqueous Acids
Strong acids Weak acids
H 1 + H:0 ^ H, 0+ 4 l HSO4 + H2O H30* 4 SO5
' "

HCIO4 + H2O > H3O -t- abj

4
H 3 PO4 + H2O ? H3CT 4 H 2 PO4
HBr + H20 > H30+ 4 Br HF + H2O H;( ) -
F
.
HCl + H O ^ H3O
+
4 CI
*
CH3COOH + H:0
*
t H30 CH COO
*4 3
H2SO4 + H2O > H30 +4 HS0J H2CO3 + H2O t H3O+ 4 HCO3
HCIO3 + H2O > H;0^ 4 CI03 H2 S 4- H:0 !H304 - HS -
HCN 4 H20 H3cr 4 CN "

HCOJ 4 H:0 =* H30

+
+4
CO“-

Strength of Acids
A strong acid is one ilun ionizes completely in aqueous solution . A strong
.
acid is a strong electrolyte. Perchloric acid HC104 hydrochloric acid. .
.
I ICl. and nitric acid HN03, are examples of strong acids. In water,
100% of the acid molecules are ionized. The strength of an acid depends
on the polarity of the bond between hydrogen and the element to which
it is bonded and the ease with which that bond can be broken. Acid
strength increases with increasing polarity and decreasing bond energy.
An acid that releases few hydrogen ions in aqueous solution is a weak
acid. The aqueous solution of a weak acid contains hydronium ions,
anions, and dissolved acid molecules. 1 lydrocyanic acid is an example of
a weak acid. In aqueous solution, both the ionization of HCN and the
reverse reaction occur simultaneously. In a 1 M solution of HCN there
will be only two II ions and two CN ions out of lOO.OOO molecules
*

.
'
The other 99,998 molecules remain as IICN.

HCN( fl</ ) 4 H20( / ) < 11130 ( */ </ ) 4 CN

r
( i u/ )
'

.
Common aqueous acids are listed in Table 3 Each strong acid ionizes
completely in aqueous solution to give up one hydrogen ion per mol-
ecule. Notice that the number of hydrogen atoms in the formula does not
indicate acid strength. Molecules with multiple hydrogen atoms may not
readily give up each hydrogen. The fact that phosphoric acid has three
hydrogen atoms per molecule does not mean that it is a strong acid.
None of these ionize completely in solution, so phosphoric acid is weak .
Organic acids, which contain the acidic carboxyl group —COOll. are
generally weak acids. For example, acetic acid. CH 3COOH. ionizes
slightly in water to give hydronium ions and acetate ions. CH 3COO .

Cl I3C00H ( ( / (/ ) 4 112()( / ) H30^( w/ ) + CH3C00 (m/ ) “

A molecule of acetic acid contains four hydrogen atoms. I lowever. only

one of the hydrogen atoms is ionizable. The hydrogen atom in the

474 CHAPTER 14
carboxyl group in acetic acid is the one that is “acidic and forms the *'
H O
hydronium ion. This acidic hydrogen can be seen in the structural dia - H-C-C - O - H
gram in Figure 7. H acidic hydrogen

Aqueous Solutions of Bases FIGURE 7 Acetic acid contains

Most bases are ionic compounds containing metal cations and the four hydrogen atoms, but only one
hydroxide anion, OH . Because these bases are ionic, they dissociate
" of them is “acidic " and forms the
hvdronium ion in solution.
when dissolved in water. When a base completely dissociates in water to
yield aqueous OH ions, the solution is referred to as strongly basic.
"

Sodium hydroxide. NaOH. is a common laboratory base. It is water-sol -

uble and dissociates as shown bv the equation below.

HiO
( aq )
NaOH( s )
* Na ( iuj ) + OH
You will remember from Chapter 5 that Group 1 elements are the alkali
metals. This group gets its name from the fact that the hydroxides of Li,
Na. K . Rb. and Cs all form alkaline ( basic ) solutions.
Not all bases are ionic compounds. A base commonly used in house -
hold cleaners is ammonia, NH <, which is molecular. Ammonia is a base
because it produces hydroxide ions when it reacts w ith water molecules,
as shown in the equation below.

NH }( aq ) + H,0( / ) < =t NHJ ( aq ) + OH ( aq )

'

Strength of Bases Chemistry in Action

As w ith acids, the strength of a base also depends on the extent to which Go to go.hrw.com for a full-length
article on drain cleaners.
the base dissociates, or adds hydroxide ions to the solution. For exam -
ple, potassium hydroxide. KOH, is a strong base because it completely Keyword: HC 6 ACDX
dissociates into its ions in dilute aqueous solutions.
f U)
KOH(s) » K?( aq ) + OH ~( aq )

Strong buses are strong electrolytes, just as strong acids are strong elec-
trolytes. Table 4 lists some strong bases.

TABLE 4 Common Aqueous Bases

Strong bases Weak bases
2+
Ca( OH )2 Ca + 20H "
NH3 + H7O iNHJ -f OH
Sr( OH ):
* Sr:+ + 20H "
QH5NH:+ H:O; !C6H5NH5+ OH-
Ba( OH)2 » Ba2* + 20H
•
"

NaOH * + OH
* Na
~

KOH K OH"+ "

+
RbOH
* Rb + OH "

CsOH Cs~ + OH"

ACIDS AND BASES 475

 Chloride ion,
cr

<
* *
Chloride ion, Cl
*
Sodium ion,
Na

CU(OH) 2(S)

Copper (ll) ion,

Cu2+
Water molecule,
Cu24 (aq) + 20H (aq) > Cu(OH)2(s)
H 2O
FIGURE 8 The hydroxides of
mosl (/- block metals are nearly insol-
uble in water, as is shown by the Bases that are not very soluble do not produce a large number of
gelatinous precipitate. copper( II ) hydroxide ions when added to water. Some metal hydroxides, such as
hydroxide, Cu(OH):. in the beaker CufOHB, are not very soluble in water, as seen in Figure 8. They
on the right . cannot produce strongly alkaline solutions. The alkalinity of aqueous
solutions depends on the concentration of OH ions in solution. It is unre-
"

lated to the number of hydroxide ions in the undissolved compound.

Now consider ammonia, which is highly soluble but is a weak elec -
trolyte. The concentration of OH ions in an ammonia solution is rela-
tively low. Ammonia is therefore a weak base. Many organic compounds
that contain nitrogen atoms are also weak bases. For example, codeine.
C|8H:|N03, a pain reliever and common cough suppressant found in
prescription cough medicine, is a weak base.

SECTION REVIEW 4. a. Why are strong acids also strong electrolytes ?

1. a. What are five general properties of aqueous b. Is every strong electrolyte also a strong acid?
acids ?
Critical Thinking
b. Name some common substances that have
one or more of these properties. 5. RELATING IDEAS A classmate states, "All com-
pounds containing H atoms are acids, and all com -
2. Name the following acids: a. HBrO b. HBr03. pounds containing OH groups are bases." Do you
3. a. What are five general properties of aqueous agree? Give examples.
bases?
b. Name some common substances that have
one or more of these properties.

476 CHAPTER 14
 CROSS - DISCIPLINARY CONNECTION J 4 V J J
0
*
Acid Water— A Hidden Menace

Many people are unaware of the pH awhile first could be adding copper 2. In the morning, let your water tap
of the tap water in their home until and lead ions to their tea or coffee. run for about half a minute
they are confronted with such phe - Lead poisoning is of particular before you fill your kettle or drink
nomena as a blue ring materializing concern in young children. The the water. If the water is acidic,
around a porcelain sink drain, a absorption rate of lead in the intesti- the first flush of water will have
water heater suddenly giving out, or nal tract of a child is much higher the highest concentration of lead
tropical fish that keep dying. Each of than in that of an adult, and lead and copper ions.
these events could be due to acidic poisoning can permanently impair a 3. Install an alkali -injection pump, a
water. Acidic water can also cause child's rapidly growing nervous sys - low - cost, low - maintenance solu -
the amount of lead in the water tem. The good news is that lead poi - tion that can save your plumbing
to rise. soning and other effects of acidic and lessen the risk of lead poi-
The possibility of lead poisoning water in the home can be easily pre - soning from your own water sup-
from home water supplies is a con - vented by following these tips: ply. The pump injects a small
cern. Many older homes still have 1. Monitor the pH of your water on amount of an alkali (usually
lead pipes in their plumbing, while a regular basis, especially if you potassium carbonate or
most modern homes use copper pip- have well water. This can easily sodium carbonate) into your
ing. Copper pipe joints, however, are be done with pH test kits (see water-pressure tank each time
often sealed with lead-containing photograph) that are sold in your well's pump starts. This
solder. Highly acidic water can leach hardware or pet stores—many effectively neutralizes the acidity
out both the lead from the solder tropical fish are intolerant of of your water.
joints and copper from the pipes water with a pH that is either too
themselves, which turns the sink high (basic) or too low (acidic). Questions
drain blue. In addition, people who The pH of municipal water sup - 1. What is the source of lead conta -
are in the habit of filling their tea plies is already regulated, but mination in water in the home?
kettles and coffee pots in the morn- regularly checking your water's
2. Does the use of copper water
ing without letting the tap run pH yourself is a good idea.
pipes ensure that your household
water is free from lead ?

3. Why does lead poisoning affect

children more severely than it
affects adults?

SCtlNKS. Otvriefwd aai by the

IWNUI Somt Tudtn AtwdUlN

For a variety of links related to this

The pH of your home's
chapter, go to www.scilinks.ofg
water supply can be easily
monitored using a test Topic: Acid Water
SciLinks code: HC60011
^
kit; such as the one
shown here.

ACIDS AND BASES 477

 SECTION 2
Acid-Base Theories
OBJECTIVES
J Define and recognize
Bronsted- Lowry acids F or most uses, scientists found the Arrhenius definition of acids and
and bases. bases to be adequate. However, as scientists further investigated acid -
base behavior, they found that some substances acted as acids or bases
w Define a Lewis acid and a when they were not in a water solution. Because the Arrhenius defini-
Lewis base. tion requires that the substances be aqueous, the definitions of acids
and bases had to be revised.
j Name compounds that are
acids under the Lewis defini -
tion but are not acids under
Brensted- Lowry Acids and Bases
the Bronsted- Lowry definition.
.
In 1923. the Danish chemist 1. N. Bronsted and the English chemist
T. M. Lowry independently expanded the Arrhenius acid definition. A
Bronsted-Lowry acid is a molecule or ion iluu is a proton donor. Because
H is a proton, all acids as defined by Arrhenius donate protons to water
and are Bronsted- Lowry acids as well. Substances other than molecules,
such as certain ions, can also donate protons. Such substances are not
Arrhenius acids but are included in the category of Bronsted- Low rv acids.
Hydrogen chloride acts as a Bronsted-Lowry acid when it reacts with
ammonia. The HCI transfers protons to NH3 much as it does in water.
HCI + NH3 NHJ + Cr
c
CHEMISTRY : S
(
A proton is transferred from the hydrogen chloride molecule. HCI, to
Vro ’
* the ammonia molecule, NH3. The ammonium ion. NH}, is formed.
Module 8 : Strong and Weakly Electron- dot formulas show the similarity of this reaction to the reac -
Ionized Species, pH, and Titrations
tion of HCI with water.

H:CI: + H :Q : H :0: H + :CI:~

II 11

H
HCI- H •N H H : N H + - Cl :-
H H

In both reactions, hydrogen chloride is a Bronsted- Lowry acid.

Water can also act as a Bronsted - Low ry acid. Consider, for example,
the following reaction, in w hich the water molecule donates a proton to
the ammonia molecule.
H20( / ) + NH3(tf </ ) <r N\ \ ] ( i u/ ) + OH ( a q )
1

H
H O ; + H N 11 f * HNH + O
H H H II

478 CHAPTER 14
 FIGURE 9 Hydrogen chloride gas
escapes from a hydrochloric acid
solution and combines with ammo-
nia gas that has escaped from an
.
aqueous ammonia solution The
resulting cloud is solid ammonium
chloride that is dispersed in air.

A Bronsted- Lowry base is a molecule or ion ilmt is a proion acceptor.

In the reaction between hydrochloric acid and ammonia, ammonia
accepts a proton from the hydrochloric acid. It is a Br0nsted-Lowrv
base. The Arrhenius hydroxide bases, such as NaOH, are not. strictly
speaking. Bronsted- Lowry bases. Instead, it is the OH ion produced in
"

solution that is the Bronsted-Lowry base. It is the species that can

accept a proton.
In a Bronsted- Lowry acid- base reaction, protons are transferred front
one reactant ( the acid ) to another ( the base ). Figure 9 shows the reaction
-
between the Bronsted Lowry acid HCI and the Bronsted- Lowrv base
NHV
Monoprotic and Polyprotic Acids
An acid that can donate only one proton ( hydrogen ion ) per molecule is
known as a monoprotic acid. Perchloric acid. HCI04. hydrochloric acid.
.
11( 1. and nitric acid. HNO;. are all monoprotic The following equation
shows how a molecule of the monoprotic acid HCI donates a proton to
a water molecule. The HCI ionizes to form H CT ions and Cl ions. The
"

( I has no hydrogens to lose, so HCI has only ^ one ionization step.

HCl( g) + H:0( / ) > H3O* ( aq ) + Cl ( a q )

A polyprotic acid is an acid that can donate more than one proton per
molecule. Sulfuric acid. H:S04. and phosphoric acid. H;P04. are exam -
ples of polyprotic acids. The ionization of a polyprotic acid occurs in
stages. The acid loses its hydrogen ions one at a time. Sulfuric acid

ACIDS AND BASES 479

 ionizes in two stages. In its first ionization, sulfuric acid is a strong acid.
It is completely converted to hydrogen sulfate ions, HSOj.

H2S04( / ) + H20( / ) > \ \ }0 ( aq ) + HSO4 ( aq )

The hydrogen sulfate ion is itself a weak acid. It establishes the follow -
ing equilibrium in solution.

USO ( aq ) + H20( / ) ,
H CY ( aq ) + SO} ( aq )
^
All stages of ionization of a polyprotic acid occur in the same
solution. Sulfuric acid solutions therefore contain H O IiS( )4. and
^
*
.
SO} ions. Note that in sulfuric acid solutions, there are many more
hydrogen sulfate and hydronium ions than there are sulfate ions.
Sulfuric acid is the type of polyprotic acid that can donate two pro -
tons per molecule, and it is therefore known as a diprotic acid. Ioniza -
tions of a monoprotic acid and a diprotic acid are shown in Figure 10.
Phosphoric acid is the type of polyprotic acid known as a triprotic
FIGURE 10 Hydrochloric acid . acid— an acid able to donate three protons per molecule. The equations
.
HO is a strong monoprotic acid . for these reactions are shown below.
A dilute HO solution contains
hydronium ions and chloride ions.
.
Sulfuric acid. H:S04 is a strong
H ,POA( aq ) + H:0( / ) ^ ZZ? H }0* ( a t/ ) + H 2P04 ( fl</ )
diprotic acid. A dilute H:S()4 solu -
tion contains hydrogen sulfate ions
H:P04(«4 ) + H20( / )
^H,,Cr «
H 0+( ^/ ) + HPOftfl*/ )
from the first ionization, sulfate
ions from the second ionization,
HPOj ( flr/ ) + H:0( / )
^ ( </ ) + PC 4 («</ )
)

and hydronium ions from both

ionizations.

Hydronium
ion, H 30 ‘
Water Hydronium
molecule, ion, H30 '
H 20

» «9
9 9
9
v 9
9 I
I SULFURIC
ACID
»29
9 I HC \ j

99 o o Hydrogen Sulfate
«.

sulfate ion, ion, SO|

Chloride ion, Cl HSO4

HCI + H 20 > H3O+ + cr H2S04 + H20

* HH30+* + SHS004
+ H2O ^ 30 +
^
"
HSO 4

480 CHAPTER 14
A solution of phosphoric acid contains WfV. H 3P04, H 2 P04, HPOj ,
"

and P04~. As with most polyprotic acids, the concentration of ions

formed in the first ionization is the greatest . There are lesser concentra -
tions of the respective ions from each succeeding ionization . Phospho-
ric acid is a weak acid in each step of its ionization .

Lewis Acids and Bases

The Arrhenius and Bronsted - I .owry definitions describe most acids and
bases. Both definitions assume that the acid contains or produces
hydrogen ions. A third acid classification , based on bonding and struc-
ture, includes, as acids, substances that do not contain hydrogen at all .
This definition of acids was introduced in 1923 by G. N. Lewis, the
American chemist whose name was given to electron -dot structures.
Lewis's definition emphasizes the role of electron pairs in acid - base
reactions. A Lewis acid is an atom, ion, or molecule that accepts an
electron pair to form a covalent bond
The Lewis definition is the broadest of the three acid definitions you
have read about so far. It applies to any species that can accept an elec-
tron pair to form a covalent bond with another species. A bare proton
( hydrogen ion ) is a Lewis acid in reactions in which it forms a covalent
bond , as shown below.

H ( a q ) + : NH ;( < / </ ) -
[ H NH 3]+ ( <I</ ) or [NH 4 ]*( fl < / )

The formula for a Lewis acid need not include hydrogen . Even a sil -
ver ion can be a Lewis acid , accepting electron pairs from ammonia to
form covalent bonds.

At
) ( aq ) + 2: NH 3( a q ) ( H 3N Ag- NH ,|+( a q ) or |Ag( NH 3 ):| +

Any compound in which the central atom has three valence electrons
and forms three covalent bonds can react as a Lewis acid. It does so by
accepting a pair of electrons to form a fourth covalent bond , complet -
ing an electron octet . Boron trifluoride, for example, is an excellent
Lewis acid . It forms a fourth covalent bond with many molecules and
ions. Its reaction with a fluoride ion is shown below.

F F
:F * B + *
F:
“ *
• F: B: F
I F
BF }( a q ) + F ( a q )
‘
» BFA( a q )

ACIDS AND BASES 481

 TABLE 5 Acid-Base Definitions
Type Acid Base
Arrhenius H‘ or H3CT producer OH producer
Bronsted- Lowry proton ( H+) donor proton ( H+) acceptor
Lewis electron-pair acceptor electron-pair donor

The Lewis definition of acids can apply to species in any phase. For
example, boron trifluoride is a Lewis acid in the gas- phase combination
with ammonia.

:F : H :F: H
• F - B 4- : N : H > F :
• B : N:H
’
:F : H :F : hi

A Lew is base is tin atom , ion , or molecule that donates an electron pair
to form a covalent bond. An anion is a Lewis base in a reaction in which
it forms a covalent bond by donating an electron pair. In the example of
boron trifluoride reacting with the fluoride anion. F donates an elec -
~

tron pair to boron trifluoride. F acts as a Lewis base.

"

BF3( fl</ ) + : F : ( aq ) BF 4 ( </r/ )

A Lewis acid-base reaction is the formation of one or more covalent

bonds between an electron - pair donor and an electron - pair acceptor
Note that although the three acid-base definitions differ, many com -
pounds may be categorized as acids or bases according to all three
.
descriptions For example, ammonia is an Arrhenius base because OH
ions are created when ammonia is in solution, it is a Bronsied-Lowrv base
because it accepts a proton in an acid- base reaction, and it is a Lewis base
in all reactions in which it donates its lone pair to form a covalent bond.
A comparison of the three acid-base definitions is given in Table 5.

SECTION REVIEW Critical Thinking

1. Label each reactant in the reaction below as a 3. ANALYZING INFORMATION For the following three
proton donor or a proton acceptor and as acidic or reactions, identify the reactants that are Arrhenius
basic. bases, Bronsted- Lowry bases, and/or Lewis bases.
H2C 03 + H20 HC03 + H30+ State which type(s) of bases each reactant is.
Explain your answers.
2. For the reaction below, label each reactant as an
electron pair acceptor or electron pair donor and a. NaOH(s) Na+(ag) + OH ( aq )
as a Lewis acid or a Lewis base. b. HF(ag) + H20( /) - » F~( aq ) + H30+( ag)
AICI3 + Cr » AICI4 c. FT ( ag) + NH 3( ag) > NH+A( aq )

482 CHAPTER 14
 SECTION 3
Add-Base Readions
OBJECTIVES
Describe a conjugate acid, a
I n the previous sections, you learned about three acid-base theories: conjugate base, and an
. .
Arrhenius Bronsted- Lowry. and Lewis The Bronsted- Lowry theory is amphoteric compound.
especially useful for describing acid-base reactions that take place in
aqueous solutions. This section will use the Bronsted- Lowry description
^ Explain the process of
to explore reactions between acids and bases. neutralization.

^ Define acid rain, give exam -

ples of compounds that can
cause acid rain, and describe
Conjugate Acids and Bases effects of acid rain.

The Bronsted-Lowry definitions of acids and bases provide a basis for

studying proton- transfer reactions. Suppose that a Bronsted-Lowry acid
gives up a proton: the remaining ion or molecule can re-accept that pro -
ton and can act as a base. Such a base is known as a conjugate base.
Thus, the species dun remains after a Bronsted - Lowry acid has given up
a proton is the conjugate base of that acid. For example, the fluoride ion
is the conjugate base of hydrofluoric acid.

HF( tf <7) + H20( / ) < > F ( aq ) + ( aq )

acid conjugate base

In this reaction, the water molecule is a Bronsted- Lowry base It .

accepts a proton from IIF to form H 3( ) \ which is an acid. The hydro-
nium ion is the conjugate acid of water. The species that is formed
when a Bronsted - Lowry base gains a proton is the conjugate acid of
that base.

HF( aq ) + H20( / ) f *F ( aq ) + HyO* ( aq )

base conjugate acid

In general. Bronsted- Lowry acid-base reactions are equilibrium sys-

tems meaning that both the forward and reverse reactions occur. They
involve two acid-base pairs, known as conjugate acid-base pairs.

( aq ) + H CY ( aq )
HF ( aq ) + H:0(/ ) <
^ Fbase
~

3
acidi1 base*)
1 acidi

-
The subscripts designate the two conjugate acid base pairs: ( 1 ) HF and
F and ( 2 ) H O* and H:0. In every conjugate acid-base pair, the acid
"

^
has one more proton than its conjugate base.

ACIDS AND BASES 483

 Strength of Conjugate Acids and Bases
The extent of the reaction between a Brousted-Lowry acid and base
depends on the relative strengths of the acids and bases involved.
C onsider the following example. Hydrochloric acid is a strong acid. It gives
up protons readily.Therefore, the CT ion has little tendency to attract and
retain a proton. Consequently, the CT ion is an extremely weak base.

HCI(g) + H:0( / ) » H3CY ( aq ) + Cl ( aq )

strong acid base acid weak base

This observation leads to an important conclusion: the stronger an acid

CROSS - DISCIPLINARY is, the weaker its conjugate base; the stronger a base is, the weaker its con -
jugate acid.
"It 's a Bitter Pill" This concept allows strengths of different acids and bases to be com-
Have you ever wondered about the ori- pared to predict the outcome of a reaction. As an example, consider the
gin of the saying, " It's a bitter pill to
swallow " ? This saying is used to
.
reaction of perchloric acid IiCI04, and water .
describe a situation that is difficult to
HCIO A( aq ) + H20( / ) - H jO' ( aq ) + ClOA( aq )
accept . Many medications contain bases,
and a bitter taste is a property of bases. stronger acid stronger base weaker acid weaker base
So, many medications actually have a
bitter taste. If you look at the chemical The hydronium ion is too weak an acid to compete successfully with
formulas of the components of medica - perchloric acid in donating a proton: IICI04 is the stronger acid. In this
tions, you will see that they often con- reaction, the perchlorate ion, CIQ4, and IIT) are both bases. Because
tain nitrogen. One such component is l iCI()4 is a very strong acid, CIQ4 is an extremely weak base.Therefore,
caffeine, which acts as a stimulant on
I l:Q competes more strongly than Cl( )4 to acquire a proton. The reac -
the central nervous and respiratory sys-
tems. Its molecular formula is tion proceeds such that the stronger acid reacts with the stronger base
C8H10O2N4. Like ammonia, caffeine has to produce the weaker acid and base.
basic properties because it has a nitro- Now consider a comparable reaction between water and acetic acid.
gen that can accept a proton.
CH3COOH( aq ) + H,0( / ) *r H3Cr ( aq ) + CH3COO -( <fc/ )
weaker acid weaker base stronger acid stronger base

The H 3() ‘ ion concentration in this solution is much lower than it was in
the HCI04 solution because acetic acid is a weak acid. The ClI3COOII
molecule does not compete successfully with the IT,O ion in donating
'

protons to a base. The acetate ion. CH3COO . is a stronger base than

IIT ). Therefore. the ITO molecule does not compete successfully with
the OH3COO ion in accepting a proton. The IC,0 ion is the stronger
"

-
acid, and the CH COO ion is the stronger base. Thus, the reaction to
the left is more favorable.
Note that in the reactions for both perchloric acid and acetic acid, the
favored direction is toward the weaker acid and the weaker base. This
observation leads to a second important general conclusion: proton-
transfer reactions favor the production of the weaker acid and the weaker
base. For a reaction to approach completion, the reactants must be
much stronger as an acid and as a base than the products .
By comparing many different acids and bases, a table of relative
strengths, such as Table 6, can be assembled. Note that a very strong
acid, such as HC104. has a very weak conjugate base, CI04 . The
strongest base listed in the table, the hydride ion. II . has the weakest

484 CHAPTER 14
 TABLE 6 Relative Strengths of Acids and Bases
Conjugate acid Formula Conjugate base Formula
hydriodic acid* HI iodide ion r
perchloric acid* HCIO4 perchlorate ion CIO 4
hydrobromic acid* HBr bromide ion Br
hydrochloric acid* HC! chloride ion Cl
sulfuric acid*
chloric acid*
nitric acid*
n 2so4
HCIO
HN03
+
,
hydrogen sulfate ion
chlorate ion
nitrate ion
HSO 4
CIO
NO;
.
,
s
ft
C
y
a
.
hydronium ion H3O water H2O /
-
chlorous acid HCIO2 chlorite ion CIO; ti
y .
ft
hydrogen sulfate ion HSO 4 sulfate ion SO} - y.
n
ft
S
phosphoric acid H;,PQ 4 dihydrogen phosphate ion H;P04 M

hydrofluoric acid HF fluoride ion F-

04 acetic acid CH3COOH acetate ion CH3COO-

s
carbonic acid H2C03 hydrogen carbonate ion HCO5
“3
hydrosulfuric acid H2S hydrosulfide ion HS "

r:
04
a dihydrogen phosphate ion H2PO4 hydrogen phosphate ion HPOJ-
y.
a
ZJ
hypochlorous acid HCIO hypochlorite ion CIO
a•
*
«
ammonium ion NH 4 ammonia NH3
hydrogen carbonate ion HCOj carbonate ion coj-
hydrogen phosphate ion HPOj- phosphate ion PO]
water H->0 hydroxide ion OH
ammonia NH, amide iont NH 2
hydrogen H2 hydride iont H~

* Strong acids
t Strong bases
conjugate acid. H2. In aqueous solutions, all of the strong acids are
100% ionized, forming hydronium ions along with their anion. The acids
below hvdronium ion in Table 6 do not ionize 100% in water. Acid
J

strength alone does not predict reactivity. Although water is a weak

acid, the hydride ion is a strong enough base to pull a proton from
water. Such a reaction is illustrated in Figure II.

Amphoteric Compounds
You have probably noticed that water can be either an acid or a base.
Any species that can react as either an acid or a base is described as
amphoteric. For example, consider the first ionization of sulfuric acid, in
which water acts as a base.

ACIDS AND BASES 485

 FIGURE 11 Calcium hydride.
( alK reacts vigorously with water
to produce hydrogen gas.

CaH2(s) + 2H 20( /) Ca (OH )2 ( aq ) + 2H2 ( g )

H 2SOA( aq ) + H:0( / )
acid| base2
>
» H30 9 ) +
acid -)
HSOA( aq )
base ,
However, water acts as an acid in the following reaction .

NH 3(g ) + H 20( / ) f > NHA( aq ) + OH ( aq )

baseil acid 2 acid i base2

Thus, water can act as either an acid or a base and is amphoteric.

FIGURE 12 Each oxyacid of chlo- Such a substance acts as either an acid or a base depending on the
rine contains one chlorine atom and strength of the acid or base with which it is reacting. For example, if
one hydrogen atom . They differ in water reacts with a compound that is a stronger acid than water, water
the number of oxygen atoms they
acts as a base. If water reacts with a molecule that is a weaker acid than
contain . The effect of the changing
( ) 11 bond polarity can be seen in water, water will act as an acid and the other molecule will act as a base.
the increasing acid strength from
hypochlorous acid to perchloric acid.

1
f
H O C I: IIOCIO H : Q :CI : O : H :0:C1: 0 :
o o
Hypochlorous add Chlorous acid Chloric acid Perchloric acid
Acidity increases

486 CHAPTER 14
- OH in a Molecule
Molecular compounds containing Oi l groups can he acidic or ampho-
teric. The covalently bonded - OH group in an acid is referred to as a
hydroxyl group. For the compound to be acidic, a water molecule must
be able to attract a hydrogen atom from a hydroxyl group. This occurs
more easily when the O- H bond is very polar . Any feature of a mole-
cule that increases the polarity of the O- H bond increases the acidity
ol a molecular compound . Hie small , more-electronegative atoms of
nonmetals at the upper right in the periodic table form compounds with
acidic hydroxyl groups. All oxyacids are molecular electrolytes that con -
—
tain one or more of these O l l bonds. Such compounds include chloric
and perchloric acids.
Figure 12 shows the electron -dot formulas of the four oxyacids of
chlorine. Notice that all of the oxygen atoms are bonded to the chlorine
atom . Each hydrogen atom is bonded to an oxygen atom . Aqueous solu -
tions of these molecules are acids because the O- H bonds are broken
as the hydrogen is pulled away by water molecules.
The behavior of a compound is affected by the number of oxygen
atoms bonded to the atom connected to the - Ol I group. The larger the
number of such oxygen atoms is. the more acidic the compound is. The
electronegative oxygen atoms draw electron density away from the
O- H bond and make it more polar. For example, chromium forms
three different compounds containing - OH groups, as shown below. H:C:C
H : OH
basic
( i <OH )
:
chromium ( II )
.
amphoteric
( ’ ( OH ) ,
chromium ) I I I )
acidic
H:Cr04
chromic acid
(a ) CH 3COOH
Acetic acid

hvdroxide hvdroxide

Notice that as the number of oxygen atoms increases, so does the acid -
ity of the compound .
Consider also the compounds shown in Figure 13. In acetic acid , but
not in ethanol , a second oxygen atom is bonded to the carbon atom
connected to the -OH group. That explains why acetic acid is acidic
but ethanol is not , even though the same elements form each
compound. H : C : C :0:H
H H
(b) C 2 H 5 OH
Ethanol
Neutralization Reactions
FIGURE 13 ( a ) Acetic acid is
There are many common examples of acidic compounds reacting with acidic. The second oxygen atom on
basic compounds, each neutralizing the other. Sodium bicarbonate. the carbon draws electron density
,
NaHCO . and tartaric acid , H:C4 H 4Of „ are two components in baking —
away from the OH group, making
the O- H bond more polar.
powder. When allowed to react in solution , the two compounds produce ( b ) Ethanol is essentially neutral .
carbon dioxide. The escaping carbon dioxide causes foods, such as bis- It has no second oxygen atom , so
cuits, to rise. Another example is an antacid soothing an overly acidic ethanol is less polar than acetic acid ,
stomach by neutralizing the stomach acid . and is a much weaker acid .

ACIDS AND BASES 487

 Strong Acid- Strong Base Neutralization
SC
/ lNKS. Dmtoftd <ad msmUwtl h *
*
An acid-base reaction occurs in aqueous solution between hydro -
chloric acid, a strong acid that completely ionizes to produce II30+,
MJCOAJI SOM« Tucbm Auoojtwxi

For a variety of links related to this and sodium hydroxide, a strong base that completely dissociates to pro-
chapter, go to • duce OH . The formula equation for this reaction is written as follows.
'

Topic: Salts
SciLinks code: HC61347 HC\ ( aq ) + NaOH(«r/ ) > NaCl( ) + H2Q( / )
^
In an aqueous solution containing l mol of sodium hydroxide. NaOH
dissociates as represented by the following equation.

NaOH ( </ </ ) » Na * ( <? </ ) + OH ( aq )

A solution containing I mol of hydrochloric acid ionizes as represented

by the following equation.

HCI(a</ ) + H:0( / )
* H ^O^( aq ) + Cl ( aq )
“

II the two solutions are mixed, as in Figure 14, a reaction occurs

between the aqueous II 0 and OH ions. Notice that sodium chloride,
>
'

FIGURE 14 When aqueous NaCI, and water are produced. The overall ionic equation is shown
hydrochloric acid. HCI. reacts with below.
aqueous sodium hydroxide. NaOH.
the reaction produces aqueous so - HyO* ( aq ) + Cl ( t/t/ ) + Na+(«r/ ) + OH ( aq ) >
dium chloride. NaCI. Ions that are Nd+( aq ) + C\ ~( aq ) + 2H20( / )
present in each solution are repre -
sented bv the models.

Hydronium
ions, H 30 '
Chloride ions Cl . Sodium
ions, Na
Hydroxide
ions, OH

Water •*•# * *
^ V *» ©
«
»1
3
3

•V
.
;v
**
*••
molecule,
»
H20

••
© * * i& V •
* *^ /
/

water

%i

o
evaporation
+

488 CHAPTER 14
 Because they appear on both sides of the overall ionic equation. Na *

and Cl are spectator ions. The only participants in the reaction are the
hydronium ion and the hydroxide ion. as shown in the following net
ionic equation.

I\ yO+( aq ) + OHI.m/ ) > 2H20( / )

There are equal numbers of H;0+ and OH ions in this reaction, and
they are fully converted to water. In aqueous solutions, neutralization is
the reaction of hydronium ions and hydroxide ions to form water
molecules.
Notice that water is not the only product of a neutralization. A salt is
also produced. A salt is an ionic compound composed of a cation from
a base and an anion from an acid .

Acid Rain
Many industrial processes produce gases such as NO, N02, CO?, S()2.
and SO;. These compounds can dissolve in atmospheric water to pro-
duce acidic solutions that fall to the ground in the form of rain or snow.
For example, sulfur from the burning of oil and coal forms sulfur diox -
ide, SO ?. The S02 is then converted to SO3, sulfur trioxide, which reacts
with water in the atmosphere to produce sulfuric acid, as shown below.

SO3(g) + H2Q( / ) > H2SOA( aq )

Rainwater is normally slightly acidic, but sometimes rain is very acidic

and is called acid rain. Figure 15 shows a forest that was damaged by
severe acid rain. Acid rain can erode statues and affect ecosystems, such
as water environments and forests. In the 1970s. scientists found that
acid rain was causing the fish populations in some lakes and streams to
decline. When fish are completely eliminated from lakes and streams
because of acid rain the biodiversity of the ecosystem decreases.
,

Because of amendments to the Clean Air Act in 1990. a limit was set on FIGURE 15 Acid precipitation
the amount of SO: that power plants are permitted to emit. This limit causes extensive environmental
has decreased but not eliminated acid rain in the United States. damage.

SECTION REVIEW a. Refer to Table 6 to compare the strengths of

1. Complete and balance the equations for the the two acids in the equation. Do the same for
following acid-base reactions: the two bases.
a. H2 C 03 + Sr(0H)2 —> —
b. Determine which direction forward or
reverse is favored in the reaction.
b. HCI04 + NaOH -
c. HBr + Ba (0H)2 — Critical Thinking
* 3. INFERRING RELATIONSHIPS Explain how the pres-
d. NaHCOj + H2 S04
ence of several oxygen atoms in a compound con-
2. Consider the equation for acetic acid plus water. taining an -OH group can make the compound
CHjCOOH + H20 » CH3C0Cr + H30+ acidic.

ACIDS AND BASES 489

 CHAPTER HIGHLIGHTS
Properties of Acids and Bases
I Vocabulary •Acids have a sour taste and react with active metals. Acids
binary acid change the colors of acid-base indicators, react with bases to
oxyacid produce salts and water , and conduct electricity in aqueous
Arrhenius acid solutions.
Arrhenius base •Bases have a bitter taste, feel slippery to the skin in dilute
strong acid aqueous solutions, change the colors of acid-base indicators,
weak acid react with acids to produce salts and water, and conduct elec -
tricity in aqueous solution.
•An Arrhenius acid contains hydrogen and ionizes in aqueous
solution to form hydrogen ions. An Arrhenius base produces
hydroxide ions in aqueous solution.
•The strength of an Arrhenius acid or base is determined by the
extent to which the acid or base ionizes or dissociates in aque -
ous solutions.

Acid-Base Theories
I Vocabulary •A Bronsted-Lowry acid is a proton donor. A Bronsted - Lowry
Bronsted - Lowry acid triprotic acid base is a proton acceptor.
Bronsted - Lowry base Lewis acid •A Lewis acid is an electron-pair acceptor. A Lewis base is an
Bronsted- Lowry acid - Lewis base electron-pair donor.
base reaction Lewis acid -base •Acids are described as monoprotic. diprotic. or triprotic
monoprotic acid reaction depending on whether they can donate one. two, or three pro-
polyprotic acid tons per molecule, respectively, in aqueous solutions. Polyprotic
diprotic acid acids include both diprotic and triprotic acids.

Acid-Base Reactions
I Vocabulary •In every Bronsted - Lowry acid-base reaction, there are two
conjugate base conjugate acid-base pairs.
conjugate acid •A strong acid has a weak conjugate base: a strong base has a
amphoteric weak conjugate acid.
neutralization •Proton- transfer reactions favor the production of the weaker
salt acid and base.
•The acidic or basic behavior of a molecule containing - OH
groups depends on the electronegativity of other atoms in the
molecule and on the number of oxygen atoms bonded to the
atom that is connected to the - OH group.
•A neutralization reaction produces water and an ionic com-
pound called a salt .
•Acid rain can create severe ecological problems.

490 CHAPTER 1 4
 CHAPTER REVIEW

Properties of Acids and Bases Acid-Base Theories

SECTION 1 REVIEW SECTION 2 REVIEW
1. Compare the general properties of acids with 12. Distinguish between a monoprotic, a diprotic.
the general properties of bases. and a triprotic acid. Give an example of each.
2. a. Distinguish between binary acids and oxy - 13. Which of the three acid definitions is the
acids in terms of their component elements broadest ? Explain.
and the systems used in naming them,
b. Give three examples of each type of acid. PRACTICE PROBLEMS
3. Identify and describe the characteristic proper -
14. a. Write the balanced equations that describe
ties of five common acids used in industry. Give
some examples of the typical uses of each. -
the two step ionization of sulfuric acid in a
dilute aqueous solution,
4. Although HCl( w/ ) exhibits properties of an
b. I low do the degrees of ionization in the two
Arrhenius acid, pure HCI gas and HCl dissolved
steps compare?
in a nonpolar solvent exhibit none of the prop -
15. Dilute HCI( aq ) and K O H ( aq ) are mixed in
erties of an Arrhenius acid. Explain why.
chemically equivalent quantities. Write the
5. a . What distinguishes strong acids from weak
following:
acids?
a. formula equation for the reaction
b. Give two examples each of strong acids and
b. overall ionic equation
weak acids.
c. net ionic equation
-
6. H P04. which contains three hydrogen atoms
16. Repeat item 15. but mix H 4PO4( w/ ) and
per molecule, is a weak acid, whereas HCI.
NaOH( w/ ).
which contains only one hydrogen atom per
17. Write the formula equation and net ionic equa -
molecule, is a strong acid. Explain why.
tion for each of the following reactions:
7. a. What determines the strength of an
a. Zn (.v ) + HC\ ( aq )
Arrhenius base?
b. Al( .v ) + H:S04(M/ ) >
b. Give one example each of an aqueous solu-
18. Write the formula equation and net ionic equa -
tion of a strong base and an aqueous solution
tion for the reaction between Ca ( .v ) and HClU/r/ ).
of a weak base.

PRACTICE PROBLEMS Acid-Base Reactions

8. Name each of the following binary acids:
SECTION 3 REVIEW
a. HCI
b. H2S 19. Define and give an equation to illustrate each
9. Name each of the following oxyacids: of the following substances:
a. HN03 c. HCIO , a. a conjugate base
b. a conjugate acid
b. H:S03 d. HNO,
10. Write formulas for the following binary acids: 20. a. What is the relationship between the
a. hydrofluoric acid strength of an acid and the strength of its
b. hydriodic acid conjugate base?
11. Write formulas for the following oxyacids: b. What is the relationship between the
a. perbromic acid strength of a base and the strength of its con -
b. chlorous acid jugate acid?
c. phosphoric acid
d. hypochlorous acid

ACIDS AND BASES 491

 CHAPTER REVIEW

21 . a. Whal trend is there in the favored direction a. C02( g) + H:0( / ) -

of proton- transfer reactions?
b. What determines the extent to which a
proton- transfer reaction occurs? 29.
^
b. SO g) + H,0( / ) -
c. N:05(g) + H:0( / )
*
Write the formula equation, the overall ionic
22. a. What is meant by the term amphoteric? equation, and the net ionic equation for a neu-
b. Give an example of a substance or ion that tralization reaction that would form each of the
has amphoteric characteristics. following salts.
23. For each reaction listed, identify the proton a. RbCl04 c. CaCL
donor or acid and the proton acceptor or base. b. BaS04 d. K 2S04
Label each conjugate acid -base pair. 30. Zinc reacts with 100.0 mL of 6.00 M cold, aque-
a. CH3COOH(M/ ) + H:0( / ) < >
_ ous sulfuric acid through single replacement .
,
H y(Y ( aq ) + CH COO (<i<7 ) a. How many grams of zinc sulfate can be
b. HCOj( tf </ ) + H2Q( / ) produced?
H2C03(tff/ ) + OH ( at / ) b. How many liters of hydrogen gas could be
c. HN03 4- SO} '
> HSOj + NOJ released at STP?
24. Using the information given in Table 6, deter - 31. A 211 g sample of barium carbonate. BaC03,
mine the following relative to HF, H? S. HN03, reacts with a solution of nitric acid to give bar -
and CHiCOOH: ium nitrate, carbon dioxide and water. If the acid
a. strongest acid is present in excess, what mass and volume of
b. weakest acid dry carbon dioxide gas at STP will be produced?
c. strongest conjugate base among the four 32. A seashell that is composed largely of calcium
conjugate bases produced by the acids listed carbonate reacts with a solution of HC1. As a
d. weakest conjugate base among the four .
result 1500 mL of dry C02 gas at STP is pro-
conjugate bases produced by the acids listed duced. The other products are CaCL and H:0.
25. Explain why the conjugate base of a strong acid .
a How many grams of CaC03 are consumed in
is a weak base and the conjugate acid of a the reaction ?
strong base is a weak acid. b. What volume of 2.00 M HCI solution is used
in this reaction ?
33. Acid precipitation is the term generally used to
PRACTICE PROBLEMS
describe rain or snow that is more acidic than it
26. Complete the following neutralization reactions.
normally is. One cause of acid precipitation is
Balance each reaction, and then write the over - the formation of sulfuric and nitric acids from
all ionic and net ionic equation for each.
various sulfur and nitrogen oxides produced in
a. HCI( w/ ) + NaOH(u<7 ) > volcanic eruptions, forest fires, and thunder -
b. HNOy ( aq ) + KOH( wy ) — >
storms. In a typical volcanic eruption, for exam -
c. Ca(0H )2(flg) + HN03( £i</ )
ple. 3.50 x 10s kg S02 may be produced. If this
d. Mg( OH ) 2(ar/ ) + HCI( a q ) -
amount of S02 were converted to H2 S04
27. Write the formula equation, the overall ionic
according to the two-step process given below,
equation, and the net ionic equation for the
how many kilograms of H2S04 would be pro -
neutralization reaction involving aqueous solu-
duced from such an eruption?
.
tions of H P04 and Mg( OH ) 2 Assume that the
^
solutions are sufficiently dilute so that no pre- SCL + - CL > SO;
1
cipitates form. ,
Am

28. Write the balanced chemical equation for each

SO + H:Q
* H2S04
of the following reactions between water and
the non - metallie oxide to form an acid.

492 CHAPTER 74
 CHAPTER REVIEW

40. a. Look at Table 7 A in the Elements Handbook .

MIXED REVIEW
What periodic trends regarding the acid -base
34. Suppose that dilute HNC)$( aq ) and LiOH ( </ r/ ) character of oxides do you notice ?
are mixed in chemically equivalent quantities. b. How is the nature of the product affected
Write the following for the resulting reaction: bv the concentrations of the reactants?
a . formula equation
b. overall ionic equation
c. net ionic equation RESEARCH & WRITING
35 . Write the balanced chemical equation for the
reaction between hydrochloric acid and magne - 41 . Explain how sulfuric acid production serves as a
sium metal. measure of a country 's economy. Write a report
36 . Write equations for the three-step ionization of on your findings.
phosphoric acid. H3P04. Compare the degree of 42 . Performance Conduct library research to find
ionization for the three steps. out about the buffering of solutions. Include
37 . Name or give the molecular formula for each of information on why solutions are buffered and
the following acids: what kinds of materials used as buffers. Write a
a. HF f. hydrobromic add brief report on your findings.
b. acetic acid g. HCIO 43. Obtain some pH paper from your teacher.
c. phosphorous acid h. H:C03 Determine whether the soil around your house
d . HCI 04 i. sulfuric acid is acidic or basic. Find one type of plant that
e. H 3PO4 would grow well in the type of soil around your
home and one that would not grow well.

CRITICAL THINKING
38 . Analyzing Conclusions In the 18th century . ALTERNATIVE ASSESSMENT
Antoine Lavoisier experimented with oxides, 44. Antacids are designed to neutralize excess
such as CO: and SO:. He observed that they hydrochloric acid secreted by the stomach dur -
formed acidic solutions. His observations led him ing digestion. Carbonates, bicarbonates, and
to infer that to exhibit acidic behavior, a sub- hydroxides are the active ingredients in the
stance must contain oxygen . I lowever. today that most widely used antacids. These ingredients act
inference is known to be incorrect . Provide evi - to drive the neutralization reactions. Examine
dence to refute Lavoisier 's conclusion . the labels of several common antacids, and
identify the active ingredients.
45. Design an experiment that compares three
USING THE HANDBOOK brands of antacids in terms of the speed of
symptom relief and amount of acid neutralized.
39. Group 16 of the Elements Handbook contains
a section covering the acid - base chemistry of
oxides. Review this material , and answer the
following questions:
a . What types of compounds form acidic oxides?
b. W hat is an acid anhvdride ?
r

c. What are three examples of compounds that

are classified as acid anhydrides?
d . What types of compounds form basic oxides?
Why are they basic oxides?

ACIDS AND BASES 493

 Math Tutor WRITING EQUATIONS FOR IONIC REACTIONS

Many chemical reactions that occur in water solutions are reactions involving ions.
Soluble ionic compounds dissociate into ions when they dissolve, and some molecular
compounds, including acids, ionize when they dissolve. An ionic equation represents
the species actually present more accurately than an equation that uses full formulas.

Problem-Solving TIPS
• All dissolved substances in ionic reactions are dissociated into ions. Therefore,
soluble ionic compounds are shown as the separated ions in the full ionic equa -
tion . Strong acids and bases are also shown as the separated ions in the full ionic
equation because they are 100% ionized .
• Ions that do not take part in the reaction are called spectator ions. In other words,
spectator ions stay in solution and will be labeled "( aq )" on both sides of the equa -
tion . Eliminating spectator ions reduces the ‘‘clutter" of the full ionic equation and
produces a net ionic equation that shows only the species that actually react.

SAMPLE 1 SAMPLE 2
Write the net ionic equation for the reaction of Write full and net ionic equations for the reaction
aqueous ammonium sulfate and aqueous barium that occurs when hydrochloric acid solution is com -
nitrate to produce a precipitate of barium sulfate. bined with silver nitrate solution.
The balanced formula equation is Hydrochloric acid is a strong acid , so it is com -
( NH 4 ) 2S04U/ <7 ) + Ba( NO , ) 2( tf <7 ) 4 pletely ionized in solution . Silver nitrate is a solu -
2NH 4N03( *H7 ) + BaS( )4( .v ) ble ionic compound , so its ions are separated in
Rewrite the equation in full ionic form: solution . Although most chlorides are soluble, sil -
because ammonium sulfate and barium nitrate ver chloride is not . so silver chloride will precipi -
are soluble, they are written as separated ions: tate. The balanced formula equation is
2 NH 4 ( W/ ) -f- SOj ( aq ) 4- Ba2* ( aq ) 4- 2 NO\ ( aq ) — 4 HCIffny ) + AgNO$ ( aq ) 4
2 NH\ ( aq ) + 2 NO j( < w/ ) 4 BaS04 (.v ) AgCI ( .v ) 4- 1 IN0$( aq )
Eliminating spectator ions, NH 4 and NOj. The full ionic equation is
yields the net ionic equation : ll 30 ( < / */ ) 4- Cl ( aq ) 4 Ag ( aq ) 4 NO\ ( aq )
'

H 30* ( aq ) 4- N 03( <I <7) 4 AgCI ( .v )

SO ] { aq ) + Ba: ( < / </ )
’
4 BaS04(.v )
Eliminate spectator ions to obtain the net ionic-
equation :
C\ ~( aq ) 4 AfC ( aq ) 4 AgCI ( .v )

PRACTICE P R O B L E M S
1. Aqueous copper ( II ) sulfate reacts with aqueous 2. Write full and net ionic equations for the reac-
sodium sulfide to produce a black precipitate of tion that occurs when a solution of cadmium
copper( II ) sulfide. Write the formula equation , chloride. CdCU. is mixed with a solution of sodi -
the full ionic equation , and the net ionic equa - um carbonate, Na:COv Cadmium carbonate is
tion for this reaction . insoluble.

494 CHAPTER 14
7 5

Answer the following items on a separate piece of paper. 8. Identify the salt that forms when a solution of
H:S04 is titrated with a solution of Ca ( OH ):.
MULTIPLE CHOICE
A . calcium sulfate
.
1 Which of the following is n o t a characteristic of .
B calcium hydroxide
an acid?
C. calcium oxide
A . An acid changes the color of an indicator.
D. calcium phosphate
B. An acid has a hitler taste.
C. An acid ionizes in water. 9. Which of the following statements is true for
D. An acid produces hydronium ions in water. the reaction below?
HF( aq ) + HPC>f ( < / </ ); _ F ( aq ) + H:P04 ( </ < / )
=
2. When an acid reacts with an active metal. A . HF is the base.
A . the hvdronium ion concentration increases.
B. the metal forms anions.
.
B HP04" is the acid.
C. F is the conjugate base.
C. hydrogen gas is produced. .
D 11 yPO4 is the conjugate base .
D. carbon dioxide gas is produced.
SHORT ANSWER
3. Which of the following is a Bronsled-Lowry
base? 10.1 low does a strong acid differ from a weak
acid? Give one example of each.
A . an electron pair donor
B. an electron pair acceptor
.
11 Identify the conjugate acid-base pairs in the fol -
lowing reaction:
C. a proton donor t C\0 : ( (U / ) + NH4L/ 4 )
HCIO + NH y ( aq )
D. a proton acceptor
EXTENDED RESPONSE
4. Which acid is the most commonly produced
industrial chemical? 12. Phosphoric acid, I F,P04, has three hydrogen
atoms and is classified as a triprotic acid. Acetic
A . hydrochloric acid
.
B acetic acid
.
acid CH3COOH, has four hydrogen atoms and
is classified as a monoprotic acid. Explain the
C. nitric acid
difference, and justify your explanation by
.
D sulfuric acid drawing the Lewis structure for both acids .
5 . Which of the following is a conjugate pair? 13. Write the full equation, ionic equation, and net
A . H+ and OH '
ionic equation for the neutralization reaction
B. NH 2 and NH4 between ammonia and sulfuric acid. Identify the
C. HCf
and CT spectator ion( s) .
D. H2S04 and SOj‘
6. What is the formula for acetic acid?
A . CH3COOH
B. HNO3
C . HCIO4
.
D HCN
7. Which of the following species is the conjugate
acid of another species in the list ?
A . PO
B. H P04
C. H:0
, ^
.
D H P04 . Double check (with a calculator,
if permitted) all mathematical computations involved
in answering a question.

ACIDS AND BASES 495

 EXPERIMENT 14 9o INQUIRY
L A B

Is It an Acid or a Base?
OBJECTIVES BACKGROUND
• Design an experiment to solve a chemical When scientists uncover a problem that they need to
problem. solve, they think carefully about the problem and then
use their knowledge and experience to develop a plan
• Relate observations of chemical properties
to identify unknowns.
for solving it . In this experiment , you will be given a
set of eight colorless solutions. Four of them are acidic
• Infer a conclusion from experimental data . solutions ( dilute hydrochloric acid ), and four are basic
• Apply acid - base concepts. solutions ( dilute sodium hydroxide). The concentra -
tions of both the acidic and the basic solutions are
MATERIALS 0.1 M, 0.2 M, 0.4 M , and 0.8 M . Phenolphthalein has
been added to the acidic solutions.
• 24- well microplate or 24 small test tubes First , write a procedure to determine which solu -
• labeled pipets containing solutions tions are acidic and which are basic. Then, carry out
numbered 1 - 8 your procedure. Next , develop and carry out proce-
• toothpicks dure that allows you to list the acidic and basic solu -
tions in order from lowest to highest concentration .
For other supplies, check with your teacher. As you plan your procedures, consider the proper -
ties of acids and bases that are discussed in Chapter
14. Predict what will happen to a solution of each
type and concentration when you do each test . Then ,
compare your predictions with what actually hap-
pens. You will have limited amounts of the unknown
solutions to work with, so use them carefully. Ask
your teacher what additional supplies ( if any ) will be
available to you .

SAFETY

For review of safety, please see Safety in the

Chemistry Laboratory in the front of your book .

PREPARATION
1 . Make two data tables in your lab notebook . For
Data Table 1. make two columns, one labeled
“Acids ’ and the other labeled “ Bases.”
*

CHAPTER 14
 EXPERIMENT 14

2. In your lab notebook , write your procedure for

determining the concentrations of the solutions.
Ask your teacher to approve your plan and
,

request any additional supplies that you will need.

3. Carry out your procedure for determining the
concentrations of the solutions. Record all
observations in your lab notebook , and record
your results in the second data table.

CLEANUP AND DISPOSAL

4. Clean all equipment and your lab
station . Return equipment to its proper
place. Dispose of chemicals and solu -
tions in the containers designated by your
teacher. Do not pour any chemicals down
the drain or in the trash unless your teacher
directs you to do so. Wash your hands
FIGURE A After adding phenolphthalein indicator, you can more
easily determine which solution is acidic and which solution thoroughly before you leave the lab and
is basic. after all work is finished .

CONCLUSIONS
You will record the numbers of the unknown
solutions in the proper column as you identify 1. Analyzing Conclusions: List the numbers of the
them . solutions and their concentrations.
.
For Data Table 2 make three columns, with 2. Analyzing Conclusions: Describe the test results
the headings “ Concentration. “ HCl , and
** **

that led you to identify some solutions as acids

“ NaOH ." Record the concentration of each solu -
and others as bases. Explain how you deter -
tion as you test it , and then record the concentra - mined the concentrations of the unknown
tions of HCl and NaOH present in the solution . solutions.
2. In your lab notebook , write the steps that you will
use to determine which solutions are acids and EXTENSIONS
which solutions are bases. Figure A shows one test 1. Evaluating Methods: Compare your results with
that you can use to make this determination. those of another lab group. Do you think that
your teacher gave both groups the same set of
3. Ask your teacher to approve your plan and to
solutions? ( For example, is your solution 1 the
give you any additional supplies that you will
same as the other group 's solution 1 ? ) Explain
need .
your reasoning.
PROCEDURE 2. Applying Conclusions: Imagine that you are
1. Carry out your plan for determining which helping clean out the school 's chemical store-
solutions are acids and which are bases. As you room . You find a spill of a clear liquid coming
perform your tests, avoid letting the tips of the from a large, unlabeled reagent bottle. What
storage pipets come into contact with other tests would you do to quickly determine
chemicals. Squeeze drops out of the pipets onto if the substance is acidic or basic?
-
the 24 well plate, and then use these drops for
your tests. Record all observations in your lab
notebook , and then record your results in your
first data table.
ACIDS AND BASES 497
 CHAPTER 1 5

Add-Base Titration
and pH
Marty of the foods we eat , such as tomatoes, are acidic.
Aqueous Solutions SECTION 1

and the Concept of pH OBJECTIVES

w Describe the self -ionization
of water.

J Define pH, and give the pH

of a neutral solution at 25°C.
Hydronium Ions and Hydroxide Ions
You have already seen that acids and bases form hydronium ions and Explain and use the pH scale.
hydroxide ions, respectively, in aqueous solutions. However, these ions
formed from the solute are not the only such ions present in an aque -
^ Given [H30 ] or [ OH ] find pH.
+
ous solution. Hydronium ions and hydroxide ions are also provided by
(

the solvent, water.

sj Given pH, find [H30~] or [ OH"].
Self- Ionization of Water
Careful electrical conductivity experiments have shown that pure water
is an extremely weak electrolyte. Water undergoes self-ionization, as
-
shown in the model in Figure 1. In the self ionization of water, two water
molecules produce a hydronium ion and a hydroxide ion by transfer of a
Mr>
proton. The following equilibrium takes place. Dmtaptd Md WMUiMd by ttw
NriowJ S«c« If hm AnooatM
* * *
For a variety of links related to this
H20( / ) + H20( / ) t H $0+( aq ) + OH ( ^/ )
"

chapter, go to www.scilinks. org I

Conductivity measurements show that concentrations of H3CT and
Topic: pH
SciLinks code: HC 61129
^
OH in pure water are each only 1.0 x 10 mol/L of water at 25 C.
' "

There is a standard notation to represent concentration in moles per

liter. Tlie formula of the particular ion or molecule is enclosed in brack -
ets. | ]. For example, the symbol [H30+] means “hydronium ion concen-
tration in moles per liter. or “molar hydronium ion concentration.” In
”
FIGURE 1 Water undergoes self -
water at 25°C. [H30+] = 1.0 x 1(T7 M and [ OH ] = 1.0 x 1(T7 M.
“ ionization to a slight extent . A pro -
The mathematical product of |H3CT ] and [ OH ] remains constant in
* ton is transferred from one water
water and dilute aqueous solutions at constant temperature. This
molecule to another. A hydronium
ion . H3O*, and a hydroxide ion,
OH , are produced .
"

+ +

H 2O + H2 O H 3 cr + OH "

ACID - BASE TITRATION AND pH 499

 TABLE 1 Kw at Selected constant mathematical product is called the ionization constant o f water .
Temperatures Kw % and is expressed by the following equation.

Temperature K,,= [H3OI[OH-]

(°C) Kw For example, in water and dilute aqueous solutions at 25 C the follow -.
0 1.2 x 10- 15 ing relationship is valid.
10 3.o x i trls
KB. = IH3(r ||OH | = (l.() x I0 7 )( 1.0 x 1(r 7 ) = 1.0 x 10 14
- " “

14
25 1.0 x 10 “

The ionization of water increases as temperature increases.

50 5.3 x ur 14
Therefore, the ion product, Kw , also increases as temperature increases,
as shown in Table 1.1 lowever. at any given temperature Kw is always a
constant value. The value 1.0 x 10 14 is assumed to be constant within
the ordinary range of room temperatures. In this chapter, you can
assume that these conditions are present unless otherwise stated.

Neutral, Acidic, and Basic Solutions

Because the hydronium ion and hydroxide ion concentrations are the
same in pure water, it is neutral. In fact, any solution in which [ H O ] =
^
|OH ] is neutral. Recall from Chapter 14 that acids increase the con -
-
centration of H CT in aqueous solutions, as shown in Figure 2a .
Solutions in which the [ HjCV ] is greater than the [ OH | are acidic.
Bases increase the concentration of OH in aqueous solutions, as shown
in Figure 2b. In basic solutions, the [ OH ] is greater than the [ HjCT ].
As stated earlier, the [ HjO ] and the [ OH ] of a neutral solution at
' “

25°C both equal 1.0 x 10 M. Therefore, if the [ H O* ] is increased to

^
greater than 1.0 x 10 7 M. the solution becomes acidic. A solution contain -
ing 1.0 x 10° mol H ’O ion/L at 25 ' C is acidic because 1.0 x 10 5 is greater
” “

than 1.0 x 10 . If the [ OH | is increased to greater than 1.0 x 10 M. the

" "

solution becomes basic. A solution containing 1.0 x 10 4 mol OH ions/L "

“

at 25°C is basic because 1.0 x 10 4 is greater than 1.0 x 10 . "

"

*5

FIGURE 2 ( a ) Addition of
dry ice. carbon dioxide, to water in
?Tz
increases the [ H -O" |. which is shown
by the color change of the indicator f O
bromthymol blue to yellow.The
white mist is formed by condensation O
of water vapor because the dry ice is
cold, ( b ) Addition of sodium perox -
ide to water increases the [ OH ).
which is shown by the color change
ol the indicator phenolphthalein
to pink .

500 CHAPTER 15
Calculating [H30+] and [OH ] ~

TABLE 2 Common Strong

Recall that strong acids and bases are considered completely ionized or
Acids and Bases
dissociated in weak aqueous solutions. A review of strong acids and
.
bases is given in Table 2 Because NaOH is a strong base. 1 mol of it will Strong Strong
yield I mol of OH in an aqueous solution. Acids Bases

n,o HC1 LiOH

NaOH( s) Na* ( aq ) + OH ( uq )
I mol
* 1 mol 1 mol
HBr NaOH
HI KOH
Therefore, a 1.0 x 10 2 M NaOH solution has an [ OH ) of 1.0 x 10 : M.
“ '

HCIO4 RbOH
as shown by the following.
HC103 CsOH
1.0 x 10 - muUNaOH I mol OH I .Ox 10 - mol OH HNO; Ca( OH ) 2
X
1 L solution I mol NaOH 1 L solution H2SO4 Sr ( OH ) ?
Ba(OH)2
= 1.0 x KT2 M OH "

Notice that the [ OH ) is greater than 1.0 x 10 M. This solution is basic.

Because the Kw of an aqueous solution is a relatively constant
1.0 x 10 14 at ordinary room temperatures, the concentration of either
ion can be determined if the concentration of the other ion is known.
The [ H30*| of this solution is calculated as follows.

Kw = [HjO^ JJOH ] = 1.0 x 10 14 " “

,
[H 0+ ] =
1.0 x 10
JoH
"

'
]
14
"
1.0 x It )- 14
l.O x i0
~

" 2 = 1.0 x lO'12 M

'

.
Hie [ OH ]. 1.0 x 10 2 VI is greater than the [ H30+ ], 1.0 x 10 12 M, as is '

true for all basic solutions.

Now consider a 2.0 x 10 4 M HC1 solution. Because HCI is a strong
-
acid, the [ 11 0 ‘ ] is 2.0 x 1 ( L 4 M, as shown by the following .
HCI(g) + HiO( / ) > H3O4 ( <?</ ) + Cl ( aq )
1 mol 1 mol 1 mol 1 mol
2.0 X in-4 .null net 1 mol H30 _ 2.0 x 10 4 mol H3O+ "

X
1 L solution 1 mol HCI 1 L solution

= 2.0 x Hr4 M H30*

Notice that the [ H3OC is greater than 1.0 x 10 "

M. This solution is
acidic. The [ OH | of this solution is calculated as follows.
14
AV = [H30+](OH "
] = 1.0 xlO '

1.0 x 10 14 14
"
1.0 x 10 ’

[ OH ] = = 5.U x Kr 10 M
2.0 x 10-4
~

[ H30+ ]
The [ H30+ ] is greater than the [ OH ] for all acidic solutions.
"

You may have realized that in order for KH to remain constant an ,

increase in either the | H;0+ ] or the [ OH ] in an aqueous solution caus-

"

es a decrease in the concentration of the other ion. Sample Problem A

also shows calculation of the [ ICO" ] and [ OH | of an acidic solution.

ACID - BASE TITRATION AND pH 501

 SAMPLE PROBLEM A
A 1.0 x 10 4 M solution of HN03 has been prepared for a laboratory experiment,
a . Calculate the | H 3() + | of this solution, b. Calculate the | ( > H~ |.

SOLUTION
4
1 ANALYZE Given: Concentration of the solution = 1.0 x 10 M HNO3
Unknown: a . | ICO | b. [ OH ~]

2 PLAN l INO is a strong acid, which means that it is essentially 100% ionized in dilute solutions.
>

One molecule of acid produces one hvdronium ion. The concentration of the hydronium
ions thus equals the concentration of the acid. Because the ion product, [ H3O4 ] ( OH |. is
a constant . [ OH | can easily he determined by using the value for [ HjO4 ].

a. HNO ’( / ) + H20( / ) » H O"( #</ ) + NOy ( aq ) ( assuming 100% ionization )

1 mol 1 mol
^1 mol 1 mol
mol HNO3
molarity of 1 INC);=
1 L solution
uiol HNO , 1 mol H3O" mol H3O 4

= molarity of l HO"
L solution I mol HNO ; L solution
b. [ H O*] ( OH | = 1.0 x 1014
^
1.0 xlO " 14
[ OH ] =

3 a.
1.0 x 10 4 uu>lHNO
- , 1 mol H CT
^ 1.0 x 10 4
mol H O*
^ 4 ,
COMPUTE
1 L solution
X
1 moHHNO , 1 L solution
= 1.0 x 10 VI H 0

1.0 xur 14 1.0 xur 14

b. [ OH - ] = = 1.0 x 10-loM
,
[ H 0+] 1.0 x 10 " 4

4 EVALUATE ,
Because the [ H 0+ ], 1.0 x 10-4. is greater than 1.0 x 10 . the [ OH ] must be less than
1.0 x Hr . The answers are correctly expressed to two significant digits.

PRACTICE Answers in Appendix E

1 . Determine the hvdronium and hydroxide ion concentrations in a

solution that is 1 x 1(T4 M HCI.
2 . Determine the hvdronium and hydroxide ion concentrations in a
solution that is 1.0 x 10~3 M HN03.
3. Determine the hvdronium and hydroxide ion concentrations in a Go to go.hrw.com for
solution that is 3.0 x 10~2 M NaOH. more practice problems
that ask you to calculate
4 . Determine the hvdronium and hydroxide ion concentrations in a concentration of
solution that is 1.0 x 10~ 4 M Ca( OH):. hydronium and
hydroxide ions.
Keyword: HC 6 ABTX

502 CHAPTER 15
 ,-6 KT7

Increasing acidity
t
NEUTRAL Increasing basicity
pH<7 pH>7

FIGURE 3 As the concentration

of hydronium ions increases,
The pH Scale the solution becomes more acidic
and the pH decreases. As the
Expressing acidity or basicity in terms of the concentration of H3CT or concentration of hydronium ions
OH can be cumbersome because the values tend to be very small A
"
. decreases, the solution becomes
more convenient quantity, called pH, also indicates the hydronium ion more basic and the pH increases.
concentration of a solution. The letters pi I stand for the French words
pouvoir hydrogene, meaning "hydrogen power.* The pH of a solution is
defined as the negative of the common logarithm of the hydronium ion
concentration, [ H;Q' ]. The pH is expressed by the following equation.

pH = -log [H30+]

The common logarithm of a number is the power to which 10 must

be raised to equal the number. A neutral solution at 25 C has a [ H30+ ]
of 1 x 10 M. The logarithm of 1 x 10 is -7.0. The pH is determined as
“ '

follows.

pH = -log [ H;CT ] = -log ( I x Hr7) = -( -7.0) = 7.0

Fhe relationship between pH and [ H30+ ] is shown on the scale in

Figure 3.
Likewise, the pOH of a solution is defined as the negative of the com -
mon logarithm of the hydroxide ion concentration, ( O H ).

pOH = -log[OH ] "

A neutral solution at 25 C has a [ OH ] of 1 x 10 M. Therefore, the

pOH is 7.0.
Remember that the values of [ H30+] and [ OH ] are related by Kw ,
The negative logarithm of Kw at 25°C, 1 x 10 14, is 14.0. You may have
"

noticed that the sum of the pH and the pOH of a neutral solution at
25 C is also equal to 14.0. The following relationship is true at 25 C.

pH + pOH = 14.0

At 25°C the range of pH values of aqueous solutions generally falls

between 0 and 14. as shown in Table 3 .
ACID - BASE TITRATION AND pH 503
 TABLE 3 Approximate pH Range of Some Common Materials (at 25°C )
Material pH Material pH
Gastric juice 1.0-3.0 Bread 5.0-6.0
Lemons 1.8-2.4 Rainwater 5.5-5.8
Vinegar 2.4-3.4 Potatoes 5.6-6.0
Soft drinks 2.0-4.0 Milk 63-6.6
Apples 2.9-33 Saliva 6.5-7.5
Grapefruit 2.9-34 Pure water 7.0
Oranges 3.0-4.0 Blood 73-7.5
Cherries 3.2-4.7 Eggs 7.6-8.0
Tomatoes 4.0-4.4 Sea water 8.0-8.5
Bananas 4.5-5.7 Milk of magnesia 10.5

Suppose the |H30^| in a solution is greater than the [ OH ]. as is true

.
for acidic solutions For example, the pH of an acidic solution at 25 C
,
with a |H 0*| of 1 x KT6 M is 6.0.
,
pH = -log [H 0+ ] = -log ( 1 x Hr6) = -(-6.0 ) = 6.0
The pi I of this solution is less than 7. Tliis is the case for all acidic solu-
tions at 25 ’C. The following calculation shows that the pOH is greater
than 7.0. as is true for all acidic solutions at 25 C.
pOH = 14.0 - pH = 14.0 - 6.0 = 8.0

c Similar calculations show that the pH of a basic solution at 25 C is

CHEMISTRY < .
more than 7.0 and the pOH is less than 7.0 These and other relation -
' *
“(/
TO ships are listed in Table 4. Remember that as the temperature changes,
Module 8 : Strong and Weakly the exact values will change because the value of Kw changes. Ilowever.
.
Ionized Species pH, and Titrations
the relationship pH + pOH = p /C,v will remain the same.

TABLE 4 [ H30* ], [OH ~], pH, and pOH of Solutions

Solution General condition At 25°C
Neutral |H,0+] = [ OH | -
,
|H 0+ ] = [ OH ] = 1 x Hr 7 M
'

pH = pOH pH = pOH = 7.0

Acidic [H3O+| > [ OH -| ,
H 0+] > 1 x 10 7 M"

SC
/ lNKS Develop d Mid MntMMd by tbf
'
NjtioMi Some Twkm Astotubo
pH < pOH OH ] < 1 x 1(T7 M
pH < 7.0
* pOH > 7.0
For a variety of links related to this
chapter, go to www.scilinks.org Basic [ H3oi < [ OH ] ,
H 0+] < 1 x ur7 M
Topic: Acid Rain
& pH > pOH OH ] > 1 X 10 7 M
" "

SciLinks code: HC60008 pH > 7.0

pOH < 7.0
Fy

504 CHAPTER 1 5
 Calculations Involving pH
If either the |H3CT ] or pH of a solution is known, the other can he
calculated. Significant figures involving pH must be handled carefully.
Because pH represents a logarithm, the number to the left of the decimal
only locates the decimal point. It is not included when counting
significant figures. So there must be as many significant figures to the
right of the decimal as there are in the number whose logarithm was
found. For example, a [H30 ] value of 1 x 10 has one significant figure.
’

Therefore, the pH,or -log, of this value must have one digit to the right of
the decimal. Thus. pH = 7.0 has the correct number of significant figures.

Calculating pH from [H30+]

You have already seen the simplest pH problems. In these problems, the
| H3Q | of the solution is an integral power of 10, such as 1 M or 0.01 M.
The pH of this type of solution is the exponent of the hydronium ion
.
concentration with the sign changed For example, the pi I of a solution
in which [ H3CT ] is 1 x 10 " M is 5.0.
“

SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter

What is the pH of a 1.0 x 10 3 M NaOH solution?

SOLUTION
1 ANALYZE Given: Identity and concentration of solution = 1.0 x 10 ’ M NaOH '

Unknown: pH of solution

2 PLAN concentration of base » concentration of OH ~

,
» concentration of H 0+ » pH
.
NaOH is completely dissociated when it is dissolved in water A 1.0 x 10 ? M NaOH solution
therefore produces a [ OH ] equal to 1.0 x 10 ' M. The ion product of [H30+ ] and ( OH ] is
'

. ,
a constant 1.0 x If) 14. By substitution, the [ H 0+ ] can be determined. The pH can then be
calculated.

3 COMPUTE |H30+] [ OH ] = I .0 X I 0 1 4
I .O x io-14 l .Oxitr 14
[ H,0+ ] = ~ = 1.0 x 10- 11 M
[ OH- ] i .ox ur 4
pH = -log [ H,0+] = -log ( 1.0 x IO-11) = 11.00

4 EVALUATE The answer correctly indicates that NaOH forms a solution with pH > 7. which is basic.

PRACTICE Answers in Appendix E

1. Determine the pH of the following solutions:

—rr’TV-TTrfHTTi
a. 1 x IO’-' M HC1 Go to go.hrw. com for
b. 1.0 x 10-5 M UNO , more practice problems
c. 1 x 10^ M NaOH that ask you to calculate
1
d. 1.0 x Hr - M KOH pH.
Keyword: HC 6 ABTX

ACID - BASE TITRATION AND pH 505

 Using a Calculator to Calculate pH from [HsO + ]
Most problems involve hydronium ion concentrations that are not
equal to integral powers of 10. These problems require a calculator.
Most scientific calculators have a “log" key. Consult the instructions for
your particular calculator.
An estimate of pH can be used to check your calculations. For exam-
ple. suppose the [ H;CT| of a solution is 3.4 x 10 '' M. Because 3.4 x If)^
"

lies between 10 4 and 10 \ the pH of the solution must be between 4

“

and 5. Sample Problem C continues the actual calculation of the pH

value for a solution with [ H O+ ] = 3.4 x 10 r' M.
“

SAMPLE PROBLEM C For more help, go to the Math '1'1/ tor at the end of this chapter.

What is the pH of a solution if the |H30+| is 3.4 x 10 5 M?

SOLUTION
1 ANALYZE ,
Given: [ H CT ] = 3.4 x 10 s M
Unknown: pH of solution

2 PLAN [H3CT ] pH

The only difference between this problem and previous pH problems is that you will
determine the logarithm of 3.4 x lO '' using your calculator. You can convert numbers
"

to logarithms on most calculators by using the “ log" key.

3 COMPUTE
pH = -log [ H3cr ]
= -log ( 3.4 x 10~5)
= 4.47
On most calculators, this problem is entered in the following steps.

EE +/- LOQ
-
+/

4 EVALUATE The pi l of a I x 10 " M I HO solution is 5.0. A solution that has a greater concentration of
hydronium ions will be more acidic and will have a pH less than 5. Because the concentra -
tion has two significant figures, the pH will have two figures following the decimal point.

PRACTICE Answers in Appendix E

1. What is the pH of a solution if the [ H30+| is 6.7 x 10-4 M?

2. What is the pi I of a solution with a hydronium ion concentration
of 2.5 x 10 2 M?
“

— it
Go to go.hrw.com for
3. Determine the pH of a 2.5 x 10~6 M HNO; solution.
more practice problems
4. Determine the pH of a 2.0 x 1 ( ) : M Sr ( OH )2 solution.
'
that ask you to calculate
pH-
Keyword: HC 6 A 8 TX

506 CHAPTER 15
Calculating [H30 * ] and [0H ] from pH ~

You have now learned to calculate the pH of a solution, given its

[ 11;() ). Suppose that you are given the pH of a solution instead. How
'

can you determine its hydronium ion concentration?

You already know the following equation.

pH = -log |H3CT )

Remember that the base of common logarithms is 10. Therefore, the

antilog of a common logarithm is 10 raised to that number.

log [ H3CT ] = -pH

[ H3CT ] = antilog (-pH )
[ H}Cr ] = i0 pH
"

The simplest cases are those in which pH values are integers. The
exponent of 10 that gives the [ H30 | is the negative of the pH. For an
aqueous solution that has a pH of 2, for example, the [H3CT ] is equal to
10’2 M. Likewise, when the pH is 0. the [ H30+ ] is 1 M because 10 = 1 .
°
Sample Problem D shows how to convert a pH value that is a positive
integer. Sample Problem E shows how to use a calculator to convert a
pH that is not an integral number.

SAMPLE PROBLEM For more help, go to the Math Tutor at the end of this chapter.

Determine the hydronium ion concentration of an aqueous solution that has a pH of 4.0.

SOLUTION
1 ANALYZE Given: pH = 4.0
Unknown: [ H 30 )

2 PLAN pH ,
|H 0+]

This problem requires that you rearrange the pH equation and solve for the [ H?CT ]. Because
4.0 has one digit to the right of the decimal, the answer must have one significant figure .
,
pH = -log [ H 0‘]
,
log |H 0+ ] = -pH
,
( H 0+ ] = antilog ( —pH )
[ H 3cr ] = 1 x IO-PH

3 COMPUTE ,
[ H 0+ ] = 1 x 10-fH
[H-<0+|= 1 x 10-4 M

4 EVALUATE .
A solution with a pH of 4.0 is acidic The answer. I x 10 4
M. is greater than 1.0 x 10 7
M .
which is correct for an acidic solution.

ACID - BASE TITRATION AND pH 507

 SAMPLE PROBLEM E For more help, go to the Moth Tutor at the end of this chapter.

The pH of a solution is measured and determined to be 7.52.

a . What is the hydronium ion concentration? c. Is the solution acidic or basic?
b. What is the hydroxide ion concentration?

SOLUTION
1 ANALYZE Given: pH of the solution = 7.52
Unknown: a . |H;CT | b. [ OH ] '
c. Is the solution acidic or basic?

2 PLAN PH [H3O+ ] > [OH ]

.
This problem is very similar to previous pH problems You will need to substitute values into
the pH = -log [ H}0+ ] equation and use a calculator. Once the [ H O ) is determined, the -
ion- product constant [ H3CT ] [ OH- ] = l.O x I(TI 4 may be used to calculate [ OH ].

3 COMPUTE a. pH = -log [ H30+]

log [H3CT ] = -pH
752
[ H3CT ] = antilog ( -pH ) = antilog ( -7.52 ) = 1.0 xl0 "
= 3.0 x l ( r s M H3Q+

On most calculators, this is entered in one of the following two ways.

5 2 +/- 2 nd 10 X /- 2nd LOG

,
b. [H 0+ j [ OH~] = 1.0 x IQ-
' 4

1.0 x IQ 14
"

|OH -] =
[H3O+]

1.0 x 10 ' 14
7
= 3.3 x HP M OH
3.0 x l ( rx
c. A pi I of 7.52 is slightly greater than a pi I of 7. This means that the solution is slightly basic.

4 EVALUATE Because the solution is slightly basic, a hydroxide ion concentration slightly larger than
10 M is predicted. A hydronium ion concentration slightly less than 10 VI is also pre -
dicted. Hie answers agree with these predictions.
'

PRACTICE Answers in Appendix E

1. The pi I of a solution is determined to be 5.0. What is the

hydronium ion concentration of this solution ?

2. The pH of a solution is determined to be 12.0. What is the

hydronium ion concentration of this solution?
3. The pH of an aqueous solution is measured as 1.50. Calculate the Go to go.hrw.com for
more practice problems
[ H3CT] and the [ OH ]. ’
that ask you to calculate
4. The pH of an aqueous solution is 3.07. Determine | H30+ ], hydronium ion
concentration.

C Keyword: HC 6 ABTX

508 C H A P T E R IS
 TABLE 5 Relationship of [ H30* ] to [ OH' ] and pH (at 25°C)
Solution [H30+] [O H ] pH
2
1.0 x lO M KOH
'
1.0 x 10-12 1.0 x 10-2 12.00
1.0 xl 0-2 MNH , 2.4 Xir
" 4.2 x 10-4 10.63
Pure H:0 1.0 x 10~7 1.0 x 10 ' 7 7.00
1.0 x lO-’ M HC1 l .Oxlflr3 l.Ox 1Q-
1
1.0 x 10 M CH3COOH
'
1.3 x lO-3 7.5 xlO
"' 12
3.00
2.S7

pH Calculations and the Strength

of Acids and Bases
So far. we have discussed the pH of solutions that contain only strong
acids or strong bases. We must also consider weak acids and weak bases . CROSS- DISCIPLINARY
.
Table 5 lists the |H3CT ] the [ OH [. and the pH for several solutions. Go to go.hrw.com for a full-length
article on how buffers maintain the
KOH, the solute in the first solution listed, is a soluble ionic com -
acid - base balance in blood.
pound and a strong base. The molarity of a KOH solution directly
indicates the [ OH ], and the [ H30 +| can be calculated. Once the Keyword: HC 6 ABTX
|H30+ ] is known, the pH can be calculated as in Sample Problem
C. If the pH of this solution is measured experimentally, it will be the
same as this calculated value. Methods for experimentally determin -
ing the pH of solutions will be presented in Section 2. Hydrochloric
.
acid. HC1 is a strong acid, and similar calculations can be made for
solutions that contain HC1.
Solutions of weak acids, such as acetic acid. CH 3COOH. present a
different problem. The |H;0 | cannot be calculated directly from the
molar concentration because not all of the acetic acid molecules are
ionized. The same problem occurs for weak bases such as ammonia,
NHj. The pH of these solutions must be measured experimentally The .
111,CT ] and [ OH | can then be calculated from the measured pi I values.

SECTION REVIEW 5. A Ca (0H)2 solution has a pH of 8.0. Determine the

1. What is the concentration of hydronium and following for the solution:
hydroxide ions in pure water at 25°C ? a. [ H30+ ] b. [ OH ] c. [ Ca (0H)2 [
2. Why does the pH scale generally range from 0 to Critical Thinking
14 in aqueous solutions ?
6. PREDICTING OUTCOMES Arrange the following
3. Why does a pH of 7 represent a neutral solution at solutions in order from lowest to highest pH: 0.10
25°C ? M HCI, 0.10 M H2 S04, and 0.10 M HF.
4. A solution contains 4.5 x 10~3 M HCI. Determine
the following for the solution:
a. [H 301 b. [ 0H1 c. pH

ACID - BASE TITRATION AND pH 509

 CROSS - DISCIPLINARY CONNECTION
Liming Streams

In 1987, Dr. Ken Simmons year. The population of all the trout At the same time, the concentration
tested some rainbow trout in dropped significantly. In 1989, of aluminum ion, which is toxic to
the waters of north -central Dr. Simmons and other researchers trout, in the limed area decreased,
Massachusetts Whetstone
' Brook . instituted an experiment to decrease while it increased in untreated parts
He placed the trout in cages in the the acidity of the stream. They creat - of the brook.
brook so that their behavior and sur - ed a system to continuously add cal - The success of the project was
vival could be monitored. Three days cium carbonate, or limestone, in most convincingly demonstrated by
later, they were dead. Acid rain had measured amounts to part of the the stream's residents. The popula -
lowered the pH level of the water to brook. The limestone, which was tion of brook trout increased; the
a point at which the trout simply ground into a powder, immediately mortality rate of brown trout
could not survive. reacted with the acid, which raised decreased, and for the first time in
Acid rain begins with the fossil the pH level of the water. years, fish actually began to move
fuels that we burn to power our cars The experiment lasted three years into the stream from its source, the
and factories. Those fuels release and managed to raise the average Millers River. In 1991, Dr. Simmons
combustion products that contain sul - pH level of the stream from 5.97 to again tested rainbow trout in the
fur and nitrogen that combine with 6.54, which met the scientists' goal. waters of the Whetstone. This time,
the water vapor in the they all survived.
atmosphere and turn " We clearly don't view it as a
the vapor acidic. The solution, " says Dr. Simmons. " It 's a
pH level of normal band- aid approach, but we need
rainwater is about 5.5, data to make intelligent manage -
but levels as low as 4.3 ment decisions as to how useful or
have been recorded. harmful liming could be. And I think
Acid rain lowers the that is the key thing this study has
brook 's pH level, shown. It has provided us with infor -
which significantly mation that we can use."
affects most of the
organisms living in the
Questions
brook . Some fish, such
1. Describe two possible benefits
as the rainbow trout,
of adding measured amounts of
simply die. Other
CaC03 , a base, to an acidified
species, such as Whet -
stream.
stone's brown trout,
will not spawn in 2. What elements are responsible
acidic waters. for acid rain? How do they get
In 1987, brown into rainwater?
trout did not spawn in
Whetstone Brook. The
pH level of the brook Biologists studied trout to determine the effectiveness
averaged 5.97 that of liming Whetstone Brook to raise the pH.

510 CHAPTER 15
 SECTION 2
Determining pH
and Titrations OBJECTIVES
* Describe how an acid-base
indicator functions.

* Explain how to carry out

an acid-base titration.
Indicators and pH Meters
An approximate value for the pH of a solution can be obtained using >J Calculate the molarity of a
acid - base indicators. Acid -base indicators are compounds whose colors solution from titration data.
are sensitive to pH . In other words, the color of an indicator changes as
the pH of a solution changes.
Indicators change colors because they are either weak acids or weak
bases. In solution , the equilibrium of an indicator that is a weak acid can
be represented by the equation below, which is modeled in Figure 4.
Win f » H + + // T

( hi is the symbol of the anion part of the indicator. ) The colors that an
indicator displays result from the fact that II // / and hr are different
colors.
In acidic solutions, any hr ions that are present act as Bronsted bases
and accept protons from the acid . The indicator is then present in large-
ly nonionized form. H //z. The indicator has its acid - indicating color, as
shown for litmus in Figure 4.
In basic solutions, the OH ions from the base combine with the H
' '

ions produced by the indicator. The indicator molecules further ionize

to offset the loss of H" ions. The indicator is thus present largely in the
form of its anion , hr . The solution now displays the base - indicating
color, which for litmus is blue.

In basic solution

In acidic solution

FIGURE 4 Basic solutions

shift the equilibrium of litmus to
/ the right. The ionized form . hr.
then predominates, and the litmus
turns blue. Acidic solutions shift the
equilibrium of the indicator litmus
to the left. The nonionized form ,
Hln. predominates, and the
Nonionized form Ionized form litmus turns red .

ACID - BASE TITRATION AND pH 511

 1,' kW.tiliHH'BH
i
^
Hit l AMMONIA
ilium

3 4 5 6 7 8 9 10 11 12 13 14

Stomach Black Drain

acid coffee Antacid Hand soap cleaner
Battery Apple Pure Baking Household
acid juice water soda ammonia

NEUTRAL
more acidic more basic

FIGURE 5 The pH of a solution can be determined by comparing the color

it turns pH paper with the scale of the paper. The colors of pH paper at vari -
ous pH values are shown , as are the pH values for some common materials.

Indicators come in many different colors. The exact pH range over

which an indicator changes color also varies. The pH range over which
an indicator changes color is called its transition interval. Table 6 gives
the color changes and transition intervals for a number of common

rk
1 nrr
H
-
acid base indicators.
Indicators that change color at pH lower than 7. such as methyl
orange, are simply stronger acids than the other types of indicators. They
tend to ionize more than the others. The hf anions that these indicators
produce are weaker Bronsted bases and have less tendency to accept
protons from any acid being tested . These indicators therefore do not
shift to their nonionized ( H // i ) form unless the concentration of IT is
fairly high . The color transition of these indicators occurs at rather low
" O pH . In contrast , indicators that undergo transition in the higher pH
O
•" ©
-
P9W
range, such as phenolphthalein. are weaker acids.
Universal indicators are made by mixing several different indicators.
Paper soaked in universal indicator solution is called pH paper . This
paper can turn almost any color of the rainbow and provides a fairly accu -
rate wav of distinguishing the pi I of solutions, as shown in Figure 5.
If a more precise value for the pH of a solution is needed , a pH
meter, shown in Figure 6, should be used . A pH meter determines the
pH of a solution by measuring the voltage between the two electrodes that
FIGURE 6 A pH meter precisely are placed in the solution. The voltage changes as the hydronium ion
measures the pH of a solution. concentration in the solution changes.

512 CHAPTER 1 5
TABLE 6 Color Ranges of Various Indicators Used in Titrations
Titration type Indicator Acid color Transition color Base color

Strong acid/ methyl red

strong base ( 4.4—6.2)

bromthymol blue
(6.2-7.6)

Strong acid/ methyl orange

weak base (3.1-4.4)

bromphenol blue
(3.0-4.6)

Weak acid/ phenolphthalein

strong base ( 8.0- 10.0 )

phenol red
(6.4-8.0)

ACID- BASE TITRATION AND pH 513

 QuickLAB Wear safety goggles and an apron.

Materials
Testing the pH of Rainwater • rainwater
• distilled water
Question 4. Find the average pH of each • 500 mL jars
Do you have acid precipita collection that you have made • thin, transparent metric
tion in your area ? for each rainfall, and record it ruler (± 0.1 cm)
in the data table. • pH test paper: narrow range,
± 0.2-0.3, or pH meter
Procedure 5 . Collect samples on at least five
Record all of your results in a different days. The more sam-
data table. ples you collect, the more
1. Each time it rains, set out five informative your data will be.
clean jars to collect the rain- 6. For comparison, determine the
water. If the rain continues for pH of pure water by testing
more than 24 hours, put out five samples of distilled water
new containers at the end of with pH paper. Record your
each 24 -hour period until the results in a separate data table,
rain stops. (The same pro- and then calculate an average
cedure can be used with snow pH for distilled water.
if the snow is allowed to melt
before measurements are
taken. You may need to use
Discussion
larger containers if a heavy 1. What is the pH of distilled
snowfall is expected.) water ?

2. After the rain stops or at the 2. What is the pH of normal rain-

end of each 24 -hour period, water ? How do you explain
use a thin, plastic ruler to any differences between the
measure the depth of the pH readings?
water to the nearest 0.1 cm
with a thin plastic ruler. Using
3. What are the drawbacks of
the pH paper, test the water using a ruler to measure the
to determine its pH to the
depth of collected water ? How
could you increase the preci-
nearest 0.2 to 0.3.
sion of your measurement ?
3. Record the following
information:
4. Does the amount of
rainfall or the time of
a. the date and time the collec - day the sample is
tion started taken have an effect
b. the date and time the col- on its pH? Try to
lection ended explain any variability
c . the location where the col- among samples.
lection was made (town 5. What conclusion can
and state) you draw from this
d. the amount of rainfall in investigation? Explain
centimeters how your data sup-
e. the pH of the rainwater port your conclusion.

514 CHAPTER 15
 Titration
As you know, neutralization reactions occur between acids and bases.
The OH ion acquires a proton from the H3CT ion, forming two mol -
ecules of water. The following equation summarizes this reaction.

H3 0 + OH ( r/r/ )
*

» 2H->0( /)
This equation shows that one mol of hydronium ions and one mol of
hydroxide ions are chemically equivalent amounts. They combine in a
one - to-one mole ratio. Neutralization occurs when hydronium ions and
hydroxide ions are supplied in equal numbers by reactants, as shown in
Figure 7.
One liter of a 0.10 M HC1 solution contains 0.10 mol of hydronium
ions. Now suppose that 0.10 mol of solid NaOH is added to 1 L of
.
0.10 M HCI solution The NaOII dissolves and supplies 0.10 mol of
hydroxide ions to the solution. HCI and NaOH are present in chemi -
cally equivalent amounts. Hydronium and hydroxide ions, which are
present in equal numbers, combine until the product [ H3CT ] [ OH )
"

returns to the value of 1 x 10~14. NaCk the salt produced in the reac -
tion. is the product of this neutralization of a strong acid and a strong
base. The resulting solution is neutral.
Because acids and bases react the progressive addition of an acid to
,

a base ( or a base to an acid ) can be used to compare the concentrations

of the acid and the base. Titration is the controlled addition and mea-
surement of the amount of a solution of known concentration required to
react completely with a measured amount of a solution of unknown con -
CHEMISTRY A
centration. Titration provides a sensitive means of determining the Module 8 : Strong and Weakly
chemically equivalent volumes of acidic and basic solutions. Ionized Species, pH, and Titrations

FIGURE 7 The solution on the

left lums pH paper red because it is
acidic. The solution on the right
turns pH paper blue because it is
basic. When equal numbers of H 0" ,
and OH from the acidic and basic
"

solutions react, the resulting solution

.
is neutral The neutral solution turns
pH paper green.

ACID- BASE TITRATION AND pH 515

 Equivalence Point
The point at w hich the two solutions used in u titration are present in
chemically equivalent amounts is the equivalence point. Indicators and
pH meters can be used to determine the equivalence point. A pi I meter
will show a large piI change occurring at the equivalence point. If an indi -
cator is used, it must change color over a range that includes the pH of
the equivalence point, as shown in Figure 8. Hie point in a titration at
CAREERS in Chemistry which an indicator changes color is called the end point of the indicator.
Some indicators, such as litmus, change color at about pH 7. How -
Analytical Chemist
ever. the color-change interval for litmus is broad. pH 5.5-8.0. This
The primary job of an analytical
broad range makes it difficult to determine an accurate pH.
chemist is to obtain information by
making precise measurements. Bromthymol blue is better because it has a limited transition interval,
Analytical chemists often use sophisti - pi 1 62-7.6 ( see Table 6 ). Indicators that undergo transition at about pi I
cated, state-of - the -art instruments to 7 are used to determine the equivalence point of strong- acid/strong-
analyze for barely detectable amounts base titrations because the neutralization of strong acids with strong
of materials. In addition to collecting bases produces a salt solution with a pi I of 7.
data, analytical chemists must process
the data and communicate their find-
Indicators that change color at pH lower than 7 are useful in deter -
ings with others. These findings must mining the equivalence point of strong-acid/ weak -base titrations. Methyl
be the result of careful and repro- orange is an example of this type. The equivalence point of a strong-
ducible work, strict accountability, and acid/ weak - base titration is acidic because the salt formed is itself a weak
control of the samples. Although ana - acid. Thus the salt solution has a pH lower than 7.
lytical chemists work in all areas of
Indicators that change color at pH higher than 7 are useful in deter-
chemistry, one important area is envi-
ronmental chemistry, which involves mining the equivalence point of weak -acid/strong-base titrations. Phenol-
analyzing air, water, and soil samples. phthalein is an example. These reactions produce salt solutions whose pH
The results of these tests are used by is greater than 7. This occurs because the salt formed is a weak base.
regulatory agencies such as the You may be wondering what type of indicator is used to determine
Environmental Protection Agency. the equivalence point of weak - acid/ weak - base titrations.The surprising
answer is “none at all. ‘ The pH of the equivalence point of weak acids
and weak bases may be almost any value, depending on the relative
.
strengths of the reactants The color transition of an indicator helps

_ ur

FIGURE 8 Indicators change

color at the end point of a titration.
Phenolphthalein ( a ) turns pink and
methyl red ( b ) turns red at the end
point of these titrations with a base. (a) (b)

516 CHAPTER 1 5
 Strong Acid Titrated with Strong Base Weak Acid Titrated with Strong Base
14 14

12 12

10
Equivalence
10
point
Equivalence
8 8
point i
•< i
a. a
6 6
1 ;
4 4

2 j 2

0 0
0 25 50 75 100 0 25 50 75 100
NaOH added ( mL) NaOH added (mL)
(a ) ( b)

FIGURE 9 ( a ) When a strong acid ,

such as 50.0 mL of 1.00 M HCI, is
very little in determining whether reactions between such acids and
titrated with a strong base, such as
bases are complete. 1.00 M NaOH , the equivalence point
In a titration , successive additions of an aqueous base can be made occurs at pH 7.00. ( b ) When a weak
to a measured volume of an aqueous acid . As base is added , the pH acid , such as 50.0 mL of 1.00 M
changes from a low numerical value to a high one. The change in pH CH 3COOH, is titrated with a strong
occurs slowly at first , then rapidly through the equivalence point , and base, such as 1.00 M NaOH . the ini -
then slowly again as the solution becomes more basic. Typical pH tial pH is higher and the equivalence
curves for strong-acid /strong- base and weak - acid /strong - base titra - point occurs at a pH above 7.00.
tions are shown in Figure 9.

Molarity and Titration SC

// N /C5. Pwldft< and nuiatatntd by (h*
NahMui Ideate TMdKn AIMMUHM
Figure 10 shows the proper method of carrying out a titration . If the
For a variety of links related to this
concentration of one solution is known precisely, the concentration of chapter, go to www.scilinks.org „
the other solution in a titration can be calculated from the chemically Topic: Titration/Indicators
equivalent volumes. The solution that contains the precisely known con - SciLinks code: HC61533
centration of a solute is known as a standard solution. It is often called
simply the “ known " solution.
To be certain of the concentration of the known solution , that solu -
tion must first be compared with a solution of a primary standard. A
primary standard is a highly purified solid compound used to check the
concentration of the known solution in a titration. The known solution is
prepared first , and its volume is adjusted to give roughly the desired
concentration . The concentration is then determined more precisely by
titrating the solution with a carefully measured quantity of a solution of
the primary standard .

ACID - BASE TITRATION AND pH 517

 First set up two clean burets as
FIGURE 10 Following is the prop- shown. Decide which buret to use for
er method for carrying out an acid- the acid and which to use for the
base titration. To be sure you have an base. Rinse the acid buret three times
accurate value, you should repeat the with the acid that will be used in the
titration until you have three results titration. Then, rinse the base buret
that agree within 0.05 mL. A stan- with the base solution to be used.
dardized base solution is used in this
procedure to determine the unknown
concentration of an acid.

v czrnm
I

Fill the first buret to a point above the Release some acid from the buret to remove Record the volume of the acid in the buret
0 mL calibration mark with the acid of any air bubbles and to lower the volume to to the nearest 0.01 mL as the initial volume,
unknown concentration. the calibrated portion of the buret. Remember to read the volume at the bot -
tom of the meniscus.

Allow approximately the volume of acid Subtract the initial volume reading on the Add three drops of the appropriate indicator
that was determined by your teacher or lab buret from the final reading. This is the (in this case phenolphthalein) to the flask,
procedure to flow into a clean Erlenmeyer exact volume of the acid released into the
flask. flask. Record it to the nearest 0.01 mL.

518 CHAPTER 15
Fill the other buret with the standard
base solution to a point above the
calibration mark. The concentration
of the standard base is known to a
certain degree of precision because
the base was previously titrated with
an exact mass of solid acid, which is
the primary standard.

Release some base from the buret to remove

any air bubbles and to lower the volume to
the calibrated portion of the buret.

Record the volume of the base to the Place the Erlenmeyer flask under the base Slowly release base from the buret into the
nearest 0.01 mL as your initial volume. buret as shown. Notice that the tip of the flask while constantly swirling the contents
Remember to read the volume at the bot - buret extends into the mouth of the flask. of the flask. The pink color of the indicator
tom of the meniscus. should fade with swirling.

The titration is nearing the end point when The equivalence point is reached when Subtract the initial volume reading on the
the pink color stays for longer periods of a very light pink color remains after 30 buret from the final reading. This is the
time. At this point, add base drop by drop. seconds of swirling. exact volume of the base released into the
flask. Record it to the nearest 0.01 mL.

ACID - BASE TITRATION AND pH 519

 The known solution can he used to determine the molarity of another
solution by titration. Suppose 20.0 ml . of 5.0 x 10 ' M NaOH is required
‘

to reach the end point in the titration of 10.0 mL Of HO of unknown

concentration. How can these titration data he used to determine the
molarity of the acidic solution?
Begin with the balanced neutralization reaction equation. From the
equation, determine the chemically equivalent amounts of HO and
NaOH .
HC\ ( aq ) + NaOH( uq ) > NaO(r/<7 ) + H:0( / )
1 mol 1 mol I mol 1 mol

Calculate the number of moles of NaOl I used in the titration.

5.0 x 10 ’ mol NaOH

'
1L
x x 20.0 ml = 1.0 x 10 4 mol NaOl 1 used
1L 1000 mL

Because 1 mol of NaOH is needed to neutralize 1 mol of HC1, the

4
amount of HCI in the titration must be 1.0 x 10 mol. This is confirmed
by the following equation.

1 mol HCI
l.Ox 10 4 mol NaOH x 4
= 1.0 x It )" mol HCI
1 mol NaOH

This amount of acid must be in the 10.0 ml. of the HCI solution used for
the titration. The molarity of the HCI solution can now be calculated.

1 x 10~ 4 mol HCI 1000 mL 1.0 x i0 2 mol 1 IC1

”

x
10.0 mT 1L 1L
= l.Ox ur 2 M HCI
Sample Problem F illustrates the following four steps.
1. Start with the balanced equation for the neutralization reaction, and
determine the chemically equivalent amounts of the acid and base.
2. Determine the moles of acid (or base ) from the known solution used
during the titration.
.
3 Determine the moles of solute of the unknown solution used during
the titration.
4. Determine the molaritv of the unknown solution.

SAMPLE PROBLEM F
.
In a titration 27.4 mL of 0.0154 M Ba( OH)2 is added to a 20.0 mL sample of HCI solution of unknown
.
concentration until the equivalence point is reached What is the molaritv of the acid solution?

SOLUTION
1 ANALYZE Given: volume and concentration of known solution = 27.4 mL of 0.0154 M Ba ( OH ) 2
volume of unknown HCI solution = 20.0 mL
Unknown: molaritv of acid solution

520 CHAPTER 1 5
2 PLAN 1. balanced neutralization equation > chemically equivalent amounts

Ba( OH)2 + 2HCI » BaCI2 + 2H:0

1 mol 2 mol 1 mol 2 mol
2. volume of known basic solution used ( nil. ) » amount of base used ( mol )
mol Ba(OH)2 1L
x mL of Ba( OH ) *, solution x = mol Ba ( OH ):
1L 1000 mL
3. mole ratio, moles of base used » moles of acid used from unknown solution

2 mol HC1
x mol Ba ( OH ) -> in known solution = mol HC1 in unknown solution
1 mol Ba( OH ),
4. volume of unknown, moles of solute in unknown
* molaritv of unknown
amount of solute in unknown solution ( mol ) 1000 ml.
x — = molaritv of unknown solution
volume of unknown solution ( mL ) 1L
3 COMPUTE 1 . The mole ratio from the equation is l mol Ba( OH )2 for every 2 mol HCI.
0.0154 mol Ba( OH )2 IL
-x x 27.4 mL = 4.22 x IIP 4 mol Ba ( OH ):
1L 1000 mL

2 mol HCI
3. x 4.22 x HP 4 mol Ba( OHL = 8.44 x Hr 4 mol HCI
1 mol Ba ( OH) 2

8.44 x 10 4
mol HCI IOIK) mL 4.22 x HP 2 mol HCI
4. = 4.22 x 10 - M HCI
~
x
20.0 mL 1L 1L

PRACTICE Answers in Appendix E

1 . A 15.5 mL sample of 0.215 M KOH solution required 21.2 mL of

aqueous acetic acid solution in a titration experiment Calculate.
the molarity of the acetic acid solution.
Go to go.hrw.com for
2. By titration, 17.6 mL of aqueous H2S04 neutralized 27.4 niL of more practice problems
.
0.0165 M LiOH solution What was the molarity of the aqueous that ask you to calculate
acid solution? molarities of acidic or
basic solutions.
Keyword: HC 6 ABTX

SECTION REVIEW 3. Suppose that 20.0 mL of 0.010 M Ca(0H) 2 is

.
1 Name an appropriate indicator for titrating the required to neutralize 12.0 mL of aqueous HCI solu-
following: tion. What is the molarity of the HCI solution ?
a. a strong acid and a weak base Critical Thinking
b. a strong base and a weak acid 4. PREDICTING OUTCOMES Sketch the titration curve
2. If 20.0 mL of 0.0100 M aqueous HCI is required for 50.0 mL of 0.10 M NH 3 that is titrated with
to neutralize 30.0 mL of an aqueous solution of 0.10 M HCI.
NaOH, determine the molarity of the NaOH solution.

ACID-BASE TITRATION AND pH 521

 CHAPTER HIGHLIGHTS
Aqueous Solutions and the Concept of pH
I Vocabulary •Pure water undergoes self -ionization to give 1.0 x 10 7
M
self -ionization of water ,
H 0+ and 1.0 x 10 7 M OH at 25 C.
~ '

pH •pH = -log[Ii30+J:pOI 1 = -log|OH |: at 25 C. pH + pOH = 14.0.

pOH .
•At 25 C acids have a pi I of less than 7. bases have a pH of
greater than 7. and neutral solutions have a pH of 7.
•If a solution contains a strong acid or a strong base, the
[ H /y ). [ OH ), and pH can be calculated from the molarity of
the solution. If a solution contains a weak acid or a weak base,
the [ l i y y ] and the [ OH | must be calculated from an experi-
mentally measured pH.

Determining pH and Titrations

I Vocabulary •The pi I of a solution can be measured using either a pH meter
acid- base indicators or acid-base indicators.
transition interval •Titration uses a solution of known concentration to determine
pH meter the concentration of a solution of unknown concentration.
titration •To determine the end point of a titration, one should choose
equivalence point indicators that change color over ranges that include the pi I of
end point the equivalence point.
standard solution •When the molarity and volume of a known solution used in a
primary standard titration are known, then the molarity of a given volume of an
unknown solution can be found.

522 CHAPTER 15
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D

Aqueous Solutions and the 9. Determine the piI of each of the following solu-
tions. ( Hint: See Sample Problem B.)
Concept of pH a. 1.0 x lO 2 M HC1
’

c. 1.0 xlO-5 M HI
~3
SECTION 1 REVIEW b. 1.0 X 10 MHN03 d. 1.0 x 10 4 M HBr
10. Given the following [ OH | values, determine
1. Why is pure water a very weak electric
the pH of each solution.
conductor ?
a. 1.0 x 10 6 M'
c. 1.0 x 10 : M
"

2. What does it mean when the formula of a par - -9

b. 1.0 x l() M d. 1.0 x 10-7 M
ticular ion or molecule is enclosed in brackets?
11. Determine the pH of each solution.
3 . a. What is the [ H3CT | of pure water at 25 C?
a. 1.0 x 10 2 M NaOH
“

b. Is this true at all temperatures? Why or why

b. 1.0 x 10“3 M KOH
not ?
c. 1.0 x lO 4 M LiOH
"

4. a. What is always true about the [ H30 | value

of acidic solutions?
.
12 Determine the piI of solutions with each of the

b. What is true about the [ H3CT| value of acidic

.
following [ H3O^ J. ( Hint: See Sample Problem C )
a. 2.0 x 10 5 M"

solutions at 25 C? b. 4.7 x l()"7 M

5 . a. Describe what is meant by the pi I of a 3
Cf 3.8 x 10“ M
solution. 13. Given the following pH values, determine the
b. Write the equation for determining pH.
[ HiO ] for each solution. ( Hint: See Sample
^

c. Explain and illustrate what is meant by the

Problem D.)
common logarithm of a number.
a. 3.0 c. 11.0
6. Identify each of the following solutions that are
b. 7.00 d. 5.0
at 25 C as acidic, basic, or neutral:
14. Given the following pH values, determine the
a. [H30+1= 1.0 x 1() 7 M
'

[ OH ) for each solution.

,
b. [ H CT ] = 1.0 x 10-1 M
° a. 7.00 c. 4.00
c. [OH -] = 1.0 x 10-7 M b. 11.00 d. 6.00
d. [ OH - ] = 1.0 x 10- 11 M 15 . Determine [H30+ ] for solutions with the follow -
,
e. [ H 01= [ OH - ]
.
ing pH values (Hint: See Sample Problem E. )
f. pH = 3.0 a. 4.23
g. pH = 13.0 b. 7.65
7. Arrange the following common substances in
order of increasing pH:
.
c 9.48
16. A nitric acid solution is found to have a pH of
a. eggs f. potatoes
b. apples g. lemons
.
2.70 Determine each of the following:
a. [H3Ol
c. tomatoes h. milk of magnesia b. [ OH”)
d. milk i. sea water c. the number of moles of HN03 required to
e. bananas
prepare 5.50 L of this solution
d. the mass of HN03 in the solution in part ( c )
PRACTICE PROBLEMS e. the milliliters of concentrated acid needed to
8. Calculate the [ IECT ) and [ OH ] for each of the
"
prepare the solution in part ( c )
following. ( Hint: See Sample Problem A . ) ( Concentrated nitric acid is 69.5 % HNO; by
a. 0.030 M HCI mass and has a density of 1.42 g/mL.)
b. 1.0 x 10-4 M NaOH
c. 3.0 X 10- 4 M HNO ,
d. 0.010 MCa( OH),
'

ACID - BASE TITRATION AND pH 523

 CHAPTER REVIEW

26. In a titration experiment, a 12.5 mL sample of

Determining pH and Titrations 1.75 x lO 2 M Ba( OH )2 just neutralized 14.5 mL
"

SECTION 2 REVIEW .
of IIN03 solution Calculate the molarity of the
17. What is meant by the transition interval of an HN03 solution.
indicator ?
18. Explain how changes in pH affect the color of
an indicator. MIXED REVIEW
19. a. Without using an indicator, how can you
27 . a. What is the [ OH ] of a 4.0 x 10 4 M solution
determine the equivalence point of a titra-
of Ca ( OH )2?
tion experiment or the pH of a solution ?
b. What is the |H30" ) of the solution?
h. What can be observed about the rate of
28. Given the following | H;0 ‘ | values, determine
change of the pi l of a solution near the end
the pH of each solution.
point of a titration?
a. 1.0 x 10“7 M c. 1.0 x nr 12 M
20. a. What is meant by the end point of a titration? -3
b. 1.0 xl 0 M d. 1.0 X Hr5 M
b. What is the role of an indicator in the titra-
tion process? -
29. What is the [ H O ) for a solution that has a pi 1
*

of 6.0?
c. On w hat basis is an indicator selected for a
30. Suppose that a 5.0 x 10“5 M solution of
particular titration experiment ?
Ba( OH ) 2 is prepared. What is the pH of the
.
21 For each of the four possible types of acid-base
solution?
titration combinations ( strong-strong, strong-
31. a. Calculate the pH of a solution that has an
weak, etc. ). indicate the approximate pH at the
[ H30* ] of 8.4 x 10~ n M.
end point. Also name a suitable indicator for
b. Calculate the [ H;CT ] of a solution that has a
detecting that end point.
pH of 2.50.
22. Use Figures 9( a ) and 9( h ) to sketch the pH
32. a. What is the concentration of OH~ in a 5.4 x
curve of a strong acid being titrated by a weak
U r - M solution of magnesium hydroxide,
base.
Mg(OH)2?
23. An unknown solution is colorless when tested
b. Calculate the concentration of H30+ for this
with phenolphthalein but causes the indicator
solution.
phenol red to turn red. Use this information to
33. a. Calculate the molarity of H30 ' in a solution
find the approximate pH of this solution.
that has a pH of 8.90.
.
b Calculate the concentration of OH for this
PRACTICE PROBLEMS solution.
24. For each of the following acid-base titration
combinations, determine the number of moles equals 6.9 x 10 n M ?
“
,
34. What is the pi 1 ot a solution in which [ Ol 1 |

of the first substance listed that would be the 35. In a titration. 25.9 mL of 3.4 x K ) 3 M Ba ( OH ):
”

chemically equivalent amount of the second neutralized 16.6 mL of IIC1 solution. What is
substance. the molarity of the HCI solution?
a. NaOH with 1.0 mol HCI 36. Find the molarity of a Ca( Oi 1 ): solution given
,
b. HNO with 0.75 mol KOH that 428 mL of the solution is neutralized in a
c. Ba( OH )2 with 0.20 mol FIF titration by 115 mL of 6.7 x 10 " M HN03.
“*

d. II:S04 with 0.90 mol Mg( OH ): 37. Suppose that 10.1 mL of HN03 is neutralized
25 . Suppose that 15.0 mL of 2.50 x 10 2 M aqueous
'
by 71.4 mL of a 4.2 x 10 3 M solution of KOH
“

I LS04 is required to neutralize 10.0 mL of an in a titration. Calculate the concentration of the

aqueous solution of KOH. What is the molarity HNQ3 solution.
of the KOH solution ? ( Hint: See Sample
Problem F. )

524 CHAPTER IS
 CHAPTER REVIEW

CRITICAL THINKING RESEARCH & WRITING

38. Interpreting Graphics The following titration 40. Examine the labels of at least five brands of
curve resulted from the titration of an unknown .
shampoo Note what is written there, if any -
acid with 0.10 M NaOH. Analyze the curve. thing, regarding the pi I of the shampoo. Do
Make inferences related to the type of acidic library research to find out why such pH ranges
solution titrated. are chosen and why other ranges might be
harmful to hair or eyes.
Titration of an Unknown Acid 41 . Acid rain is an environmental issue that crosses
14 state and national boundaries. Conduct library
research on this topic and write a brief report.
12
Include a description of the areas in the United
10 States affected by acid rain, and the geographi -
cal source of the sulfur and nitrogen oxides that
8 are responsible for acid rain in each region.
x
Q.
6

4
ALTERNATIVE ASSESSMENT
42. Performance Use pH paper to determine the
2
approximate pi l of various brands of orange
0 juice, which contains citric acid.
0 10 20 30 40 50 60 70
43. Performance Design and conduct an experi-
Volume of NaOH added (mL)
ment to extract possible acid-base indicators
from sources such as red cabbage, berries, and
USING THE HANDBOOK .
flower petals Use known acidic, basic, and neu-
tral solutions to test the action of each indicator
.
39 The normal pH of blood is about 7.4. When the that vou are able to isolate.
pH shifts above or below that level, the results
are acidosis or alkalosis. Review the section on
blood pH in Group 14 of the Elements
Handbook, and answer the following.
.
a What chemical species keep H3CT in blood
at the appropriate pH ?
i Graphing Calculator
Acid- Base Titration
Go to go.hrw.com for a graphing calculator
b. What condition results when there is an
exercise that asks you to graph acid-base
excess of C02 in the blood ?
c. What is hyperventilation and how does it
titration curves.
affect blood pH? - Keyword: HC6 ABTX
si<

ACID - BASE TITRATION AND pH 525

 Math Tutor USING LOGARITHMS AND pH

When you work with acids and bases, you often need to state the hydronium ion concen-
tration, [ H O ], of a solution. One simple way is to use the negative logarithm of [ H 30 ].
'

^
This quantity is called pH. For example, pure water has a [H 3 CT ] of 1.00 x 10 7 M. So,
the pH of pure water is -log (1.00 x 10 7 M) = 7.00. A solution of 0.1 M HCI has a pH of
'
1.00 or pH = — log(1 x 10 ) = 1.00. The term pOH is also used for the negative logarithm
of the hydroxide ion concentration, [ OH ]. The pOH of pure water is also 7.00.

Problem-Solving TIPS
• For pure water at 25 C.|H ^O "|= [ OH ] = 1.00 x 10 M .
• The ionization constant of water. is the product of [ H30+] and [OH ], so '

" “ '
,
Kw = [ H 30+ ]|OH ~ ] = ( 1.00 x 10 7 )( 1.00 x 10 7 ) = 1.00 xl 0 4 at 25°C.
• If you know either [ H 3CT|or |OH ], you can determine the other concentration.
'

• In terms of pH and pOH. pH + pOH = 14.00 for an aqueous solution at 25 C.

• Because pH calculations involve scientific notation and changes in signs you ,

should always check to see if answers make sense.

SAMPLE 1 SAMPLE 2
What is the pll of a 0.0046 M solution of KOH? What is the hydronium ion concentration. | HjO |, "

KOH is completely dissociated into equal num - of a solution with a pll of 4.08? What is the pOH
bers of K ( i n f ) and OH ( a q ). The concentration of of the solution?
OH is the same as the concentration of dissolved
'
In this solution ,
KOH , 0.0046 M. So. ( OH ) = 4.6 x l (T3 M and . log [ H /r ] = -4.08
pOH = -log ( 4.6 x i (T3 M ) = 2.34. | H ,0+ ] = antilog (-4.08 ) = 0.000 083 M =
For an aqueous solution at 25 C. pH + pOH = 8.3 x i 0~5 M
.
l 4.00 sopH + 2.34 = 14.00. The pOH of the solution is 14.00 - pH =
Therefore, the pH of 0.( M >46 M KOH solution = 14.00 - 4.08 = 9.92.
14.00 - 2.3 = 11.66.

PRACTICE PROBLEMS
1. What is the pll of a 0.000 85 M solution of 2. What is the hydroxide ion concentration of an
nitric acid. 1 fNOv which is a strong acid ? aqueous solution that has a pH of 9.95?

526 CHAPTER 15
Answer the following items on a separate piece of paper. .
8 The Kw value for water can be affected by
MULTIPLE CHOICE
A . dissolving a salt in the solution.
B. changes in temperature.
.
1 Distilled water contains
.
C changes in the hydroxide ion concentration.
A. H:0.
D. the presence of a strong acid.
,
B. H 0 \
C. OH . “ 9. Which of the pH levels listed below is the most
D. All of the above acidic?
A . pH = I
2. What is the pH of a 0.0010 M I INC)/? B. pH = 5
A . 1.0
B. 3.0
.
C pH = 9
D. pH = 13
C. 4.0
D. 5.0 SHORT ANSWER

3. Which of the following solutions would have a .

10. A solution has a pH of 4.75 What is the hydro-
pH value greater than 7? nium ion concentration? Is the solution acidic
or basic?
A . |OH- ] = 2.4 x 10-: M
,
B. [ H 0+ ] = 1.53 X 10~2 M .
11 A weak acid that is used as an indicator is added
C. 0.0001 M HC1 to a strong acid solution before titration of the
D. [ OH- ] = 4.4 x lfr9 M strong acid with a strong base. Why doesn 't the
weak acid affect the value calculated for the
4.11 the pH of a solution of the strong base NaOH concentration of the acid?
is known, which property of the solution can be
calculated? EXTENDED RESPONSE
A. molar concentration .
12 The hydroxide ion concentration in a solution is
B. [ OH ] 1.6 x i(r 11 M. What are the [ H CT ], the pH, and
, ^
C. [ H 0+ ] the pOH of the solution?
D. All of the above .
13 Write the balanced equation and the net ionic
5 . A neutral aqueous solution equation that represent the reaction that takes
A . has a 7.0 M H O* concentration
^
. place when milk of magnesia ( magnesium
B. contains neither hydronium ions nor hydrox - hydroxide ) reacts with hydrochloric acid in
your stomach.
ide ions.
C. has an equal number of hydronium ions and
hydroxide ions.
D. None of the above
6. Identify the salt that forms when a solution of
ITS( )4 is titrated with a solution of CafOH) ^.
A . calcium sulfate
B. calcium hydroxide
C. calcium oxide
D. calcium phosphate
7.The pH of a solution is 6.32. What is the pOH?
A . 6.32 _
B. 4.8 x 10 7 If you do not understand a ques-
C. 7.68 tion, try to reword it. But be careful not to change its
D. 2.1 x urs meaning.

ACID-BASE TITRATION AND pH 527

 SEE PRE- LAB MICRO
EXPERIMENT 15 VOLUMETRIC ANALYSIS L A B

How Much Calcium Carbonate

Is in an Eggshell?
OBJECTIVES BACKGROUND
• Determine the amount of calcium carbon - The calcium carbonate content of eggshells can be
ate present in an eggshell . easily determined by means of an acid / base back -
titration. In this experiment , a strong acid will react
• Relate experimental titration measurements
to a balanced chemical equation.
with calcium carbonate in eggshells. Then, the amount
of unreacted acid will be determined by titration with
• Infer a conclusion from experimental data. a strong base.
• Apply reaction stoichiometry concepts.
SAFETY
MATERIALS
• 1.00 MHCI • drying oven
• 1.00 M NaOH • eggshell For review of safety, please see Safety in the
• 10 mL graduated • forceps Chemistry Laboratory in the front of your book .
cylinder
• mortar and pestle
• 50 ml . micro solution • PREPARATION
phenolphthalein
bottle or small 1. Wash an empty eggshell with distilled water and
solution
Erlenmeyer flask carefully peel all the membranes from its inside.
• 100 mL beaker • thin - stemmed Place all of the shell in a premassed beaker and
pipets or medicine dry the shell in the drying oven at l IO C for
• balance droppers, 3 about 15 min .
• desiccator ( optional ) • weighing paper 2 . Copy data and calculations tables from your
• distilled water teacher.
3. Put exactly 5.0 mL of water in the 10.0 mL
graduated cylinder. Record this volume in your
data table. Label the first pipet “Acid. To cali -
1*

brate the pipet , fill it with water. Do not use this

pipet for the base solution. Holding the pipet ver-
tically. add 20 drops of water to the cylinder.
Record the new volume of water in the graduated
cylinder in the first data table under Trial 1 .
4. Without emptying the graduated cylinder, add
an additional 20 drops from the pipet . Record
the new volume for Trial 2. Repeat this proce -
dure once more for Trial 3.

528 CHAPTER 15
 EXPERIMENT 15

5. Repeat Preparation steps 3 and 4 for the second CLEANUP AND DISPOSAL
pipet. Label this pipet “ Base." Do not use this 5 . Clean all equipment and your lab
pipet for the acid solution. station. Dispose of chemicals and solu-
6. Make sure that the three trials produce data that tions as directed by your teacher. Wash
are similar to one another. If one is greatly dif - your hands thoroughly before you leave the lab.
ferent from the others, perform Preparation
steps 3-5 again. ANALYSIS AND INTERPRETATION
1. Organizing Ideas: The calcium carbonate in the
7. Remove the beaker containing the eggshell from
eggshell sample undergoes a double-displacement
.
the oven Cool them in a desiccator. Record the
reaction with the HCI in step 3. Write a balanced
mass of the entire eggshell in the second table.
chemical equation for this reaction. (Hint: The gas
Place half of the shell into the clean mortar, and
evolved was CO:.)
grind the shell into a very' fine powder.
2. Organizing Ideas: Write the balanced chemical
PROCEDURE equation for the acid/basc neutralization of the
excess unreacted HCI with the NaOH.
1. Measure the mass of a piece of weighing paper.
Transfer about 0.1 g of ground eggshell to a piece 3. Organizing Data: Calculate the volume of each
of weighing paper, and measure the eggshell's drop in milliliters. Then convert the number of
mass as accurately as possible. Record the mass drops of HCI into volume in milliliters. Record
in the second data table. Place this eggshell this volume in your data table. Repeat this step
sample into a clean, 50 mL micro solution bottle for the drops of NaOH.
( or Erlenmeyer flask ). 4. Organizing Data: Using the relationship between
2. Fill the acid pipet with 1.00 M HCI acid solution, the molarity and volume of acid and the molarity
and then empty the pipet into an extra 100 mL and volume of base needed to neutralize it .
beaker. Label the beaker “ Waste." Fill the base calculate the number of moles of the HCI solu-
pipet with the 1.00 M NaOH base solution, and tion that was neutralized by the NaOH. and
then empty the pipet into the waste beaker. record it in your table. ( Hint: This relationship
was discussed in Section 2.)
3. Fill the acid pipet once more with 1.00 M HCI.
Holding the acid pipet vertically, add exactly 5. Analyzing Results: Calculate the number of
150 drops of 1.00 M HCI to the bottle or flask moles of HCI that reacted with the CaC03 and
that contains the eggshell. Swirl the flask gently record both in your table.
for 3 to 4 min. Observe the reaction taking
place. Wash down the sides of the flask with CONCLUSIONS
about 10 mL of distilled water. Using a third 1. Organizing Data: Use the balanced equation for
pipet, add two drops of phenolphthalein solu- the reaction to calculate the number of moles of
tion. CaC'03 that reacted with the HCI, and record
4. Fill the base pipet with the 1.00 M NaOH. Slowly this number in your table.
add NaOH from the base pipet into the bottle or 2. Organizing Data: Use the periodic table to
flask that contains the eggshell reaction mixture, calculate the molar mass of CaC03. Then, use
counting and recording the drops added. Stop the number of moles of CaC03 to calculate the
adding base when the mixture remains a faint mass of CaC03 in your eggshell sample. Record
pink color, even after it is swirled gently. Be sure this mass in your data table. Using the mass of
to add the base drop by drop, and be certain the CaC03, calculate the percentage of CaC03 in
drops end up in the reaction mixture and not on your eggshell and record it in your data table.
the walls of the bottle or flask. Record in the sec-
ond data table the number of drops of base used.

ACID - BASE TITRATION AND pH 529

 CHAPTER 1 6

Reaction Energy
Many chemical reactions give
off or take in energy as heat.
Thermochemistry SECTION 1

OBJECTIVES
w Define temperature and state
V irtually every chemical reaction is accompanied bv a change in the units in which it is
energy* Chemical reactions usually absorb or release energy as heat. measured.
You learned in Chapter 10 that energy is also absorbed or released in
physical changes, such as melting a solid or condensing a vapor.
^ Define heat and state its units.
Thermochemistry is the study of the transfers of energy us hem that
accompany chemical reactions and physical changes.
^ Perform specific -heat
calculations.

^ Explain enthalpy change,

Heat and Temperature enthalpy of reaction, enthalpy
of formation, and enthalpy of
The energy absorbed or released as heat in a chemical or physical change combustion.
is measured in a calorimeter. In one kind of calorimeter, known quanti-
ties of reactants are sealed in a reaction chamber, which is immersed in
^ Solve problems involving
a known quantity of water in an insulated vessel. Therefore, the energy enthalpies of reaction,
given off ( or absorbed) during the reaction is equal to the energy enthalpies of formation, and
absorbed ( or given off ) by the known quantity of water. The amount of enthalpies of combustion.
energy is determined from the temperature change of the known mass
of surrounding water. The data collected from calorimetry experiments
are temperature changes because energy cannot be measured directly;
but temperature, which is affected by the transfer of energy as heat, is
directly measurable. To see why this is so. let us look at the definitions
of heat and temperature and at how temperature is measured.
Temperature is a measure of the average kinetic energy of the parti -
cles in a sample of matter The greater the kinetic energy of the particles SCllNKS. Dewtoptd M4
N4MM<
Mr *
by MM
TMcbtrt AiMfUtMtft
in a sample, the higher the temperature is and the hotter it feels. To
For a variety of links related to this
assign a numerical value to temperature, it is necessary to define a tem - chapter, go to www.scilinks.org
perature scale. For calculations in thermochemistry, we use the Celsius
and Kelvin scales. Celsius and Kelvin temperatures are related by the
Topic: Heat/Temperature
SciLinks code: HC60726
^
following equation.
K = 273.15 + °C
For most calculations in this book . 273.15 is rounded to 273.
The ability to measure temperature is thus based on energy transfer.
The amount of energy transferred as heat is usually measured in joules.
A joule is the SI unit of heat as well as all other forms of energy . The
joule, abbreviated J. is derived from the units for force and length.
kg x nr
Nxm=
S"

REACTION ENERGY 531

 FIGURE 1 The direction
of energy transfer is determined hv
the temperature differences between Heat can be tlwnglu of as the energy transferred betw een samples o f
the objects within a system. The
matter because of a difference in their temperatures. Energy transferred as
energy is transferred as heat from
the hotter brass bar to the cooler heat always moves spontaneously from matter at a higher temperature to
water. Illis energy transfer will matter at a lower temperature, as shown in Figure 1. The temperature of
continue until the bar and the water the cool water in the beaker increases as energy Hows into it . Likewise,
reach the same temperature. the temperature of the hot brass bar decreases as energy flows away from
it. When the temperature of the water equals the temperature of the brass
bar, energy is no longer transferred as heat within the system.

Specific Heat
Lhe quantity of energy transferred as heat during a temperature change
depends on the nature of the material changing temperature, the mass
of the material changing temperature, and the size of the temperature
change. One gram of iron heated to 100.0 C and cooled to 50.0 C in a
calorimeter transfers 22.5 J of energy to the surrounding water. But one
gram of silver transfers 1 1 . 8 J of energy under the same conditions.
The difference depends on the metals' differing capacities for absorb -
ing this energy. A quantity called specific heat can be used to compare
heat absorption capacities for different materials. Specific heat is the
amount of energy required to raise the temperature o f one gram of a
substance by one Celsius degree ( I C ) or one kelvin ( I K ) ( because the
sizes of the degree divisions on both scales are equal ). Values of spe -
cific heat can be given in units of joules per gram per Celsius degree,
J/(g* C ), joules per gram per kelvin, J / ( g* K ). or calories per gram per
Celsius degree, cal/ ( g* C ). Table 1 gives the specific heats of some
common substances. Notice the extremely high specific heat of water,
one of the highest of most common substances.
Specific heat is usually measured under constant pressure conditions,
so its symbol, cfV contains a subscripted p as a reminder to the reader.

532 CHAPTER 16
 TABLE 1 Specific Heats of Some Common
Substances at 298.15 K
Substance Specific heat J / (g K )
#

Water ( / ) 4.18
Water (.s ) 2.06
Water ( g ) 1.87
Ammonia ( g ) 2.09
Benzene ( / ) l .74
Ethanol ( / ) 2.44
Ethanol (g) 1.42
Aluminum (5) 0.897
Calcium ( s ) 0.647
Carbon, graphite ( s) 0.709
Copper ( s ) 0.385
Gold ( s ) 0.129
Iron ( s ) 0.449
Mercury ( / ) 0.140
Lead ( 5 ) 0.129

In the following mathematical equation, is the specific heat at a given

pressure, ( j is the energy lost or gained, m is the mass of the sample, and
AT represents the difference between the initial and final temperatures.
9
r m x AT
This equation can be rearranged to give an equation that can be used to
find the quantity of energy gained or lost with a change in temperature.
q = c x m x AT

SAMPLE PROBLEM A
A 4.0 g sample of glass was heated from 274 K to 314 K, a temperature increase of 40. K, and was found
to have absorbed 32 J of energy as heat .
a . What is the specific heat of this type of glass?
b. How much energy will the same glass sample gain when it is heated from 314 K to 344 K ?

SOLUTION
1 ANALYZE Given: m = 4.0 g
AT = 40. K
q = 32 J
Unknown: cp in J/( g* K )

REACTION ENERG Y 533

2 PLAN a . The specific heat . c/r of the glass is calculated using the equation given for specific heat.
</
r m x AT
b. The rearranged specific heat equation is used to find the energy gained when the glass
was heated.
q = cp x m x AT

32 J
3 COMPUTE a. = 0.20 J / ( g* K )
(4.0 g )( 4< ). K )

0.20 J
b.
( g* K )
( 4.0 g ) ( 344 K - 314 K )
0.20 J
( 4.0 g )( 30 K ) = 24 J
( g* K )

4 EVALUATE Hie units combine or cancel correctly to give the specific heat in J / ( g* K ) and the energy in J.

PRACTICE Answers in Appendix E

1 . Determine the specific heat of a material if a 35 g sample

absorbed % J as it was heated from 293 K to 313 K .
Go to go.hrw.com for
2 . If 980 kJ of energy are added to 6.2 L of water at 291 k . what will more practice problems
the final temperature of the water be ? that ask you to calculate
using specific heat.
__
^ JC Keyword: HC 6 NRGX

Enthalpy of Reaction
The energy absorbed as heat during a chemical reaction at constant
pressure is represented by A //. The / / is the symbol for a quantity called
enthalpy: It is not practical to talk just about enthalpy as a quantity,
because we have no way to directly measure the enthalpy of a system.
Only changes in enthalpy can be measured . The Greek letter A ( ‘ delta ' )
stands for “change in .” Therefore. AH is read as "change in enthalpy.”
An enthalpy change is the amount of energy absorbed by a system as
heat during a process at constant pressure. The enthalpy change is always
the difference between the enthalpies of the products and the reactants.
The following equation expresses an enthalpy change for a reaction .

AH = // products - H reactants

The enthalpy of reaction is the quantity of energy transferred as heat dur -

ing a chemical reaction. You can think of enthalpy of reaction as the dif -
ference between the stored energy of the reactants and the products.
Enthalpy of reaction is sometimes called "heat of reaction .”

534 CHAPTER 16
 It a mixture of hydrogen and oxygen is ignited , water will form and
SC
energy will he released explosively. The energy that is released comes
from the reactants as they form products. Because energy is released ,
/lNKS . r*
vMiUwrt fry Hw
NalMMi SCMMt TMCfem AwotubM
the reaction is exothermic, and the energy of the product , water must he ,
For a variety of links related to this
less than the energy of the reactants. The following chemical equation chapter, go to vvww.scil inb.org *
for this reaction indicates that when 2 mol of hydrogen gas at room tem - Topic: Thermochemistry
perature are burned. 1 mol of oxygen gas is consumed and 2 mol of SciLinks code: HC61513
water vapor are formed.
S'
- Hi ( g ) + O Ag ) * 2H . O( g )

[lie equation does not tell you that energy is evolved as heat during the
reaction . Experiments have shown that 483.6 kJ of energy are evolved
w hen 2 mol of gaseous water are formed from its elements at 298.15 k .
Modifying the chemical equation to show the amount of energy as
heat released during the reaction gives the following expression .

2 H ,(g ) + 02(g) 2 H:0(g ) + 483.6 kJ

This expression is an example of a thermochemical equation , an CHEMISTRY

equation that includes the quantity of energy released or absorbed as beta 'Sro*
during the reaction as written. In any thermochemical equation , we must Module 9: Thermochemistry
always interpret the coefficients as numbers of moles and never as
Handlers of molecules. The quantity of energy released as heat in this or
any other reaction depends on the amounts of reactants and products.
The quantity of energy as heat released during the formation of water
from H 2 and 02 is proportional to the quantity of water formed .
Producing twice as much water vapor would require twice as many
moles of reactants and would release 2 x 483.6 kJ of energy as heat , as
shown in the following thermochemical equation ( which is simply the
previous thermochemical equation , multiplied by two).

4 H 2( ) + 202( S )
* * 4 H 2Q(g ) + 967.2 kJ
Producing one- half as much water would require one- half as many moles
would release only one-half as much energy, or ' x 483.6 kJ.
< > f reactants and
The thermochemical equation for this reaction would he as follows.

H:(g ) + ,i 02( g )
* H:0(g ) + 241.8 kJ
The situation is reversed in an endothermic reaction because products
have a larger enthalpy than reactants. The decomposition of water vapor
is endothermic: it is the reverse of the reaction that forms water vapor. The
amount of energy as heat absorbed by water molecules to form hydrogen
and oxygen equals the amount of energy as heat released when the ele -
ments combine to form the water. This is to be expected because the dif -
ference between the energy of reactants and products is unchanged.
Enthalpy now appears on the reactant side of the thermochemical equa -
tion that follows, indicating that it is an endothermic reaction .

REACTION ENERGY 535

 FIGURE 2 In an exothermic Exothermic Reaction Pathway
chemical reaction, the enthalpy
change is negative, meaning energy
is released from the system as heat. Reactants Initial enthalpy

AH
a
-
Energy as """
heat is evolved
-C AH is
UJ negative

Final enthalpy
Products

Course of reaction -

2H20( g ) + 483.6 kJ 2Hi( # ) + 0:(g)

SCllNKS. ] DmlapfO by (V
Nittoul SaMCt TMCfcen ASMXI*OO«
The physical states of reactants and products must always he included
in thermochcmical equations because they influence the overall
For a variety of links related to this amount of energy as heat gained or lost . For example, the energy
chapter, go to wwv. sciHnks « ry needed for the decomposition of water would be greater than 483.6 kJ
Topic: Enthalpy ^ if we started with ice. because extra energy would be needed to melt the
Sci Links code: HC60522 ice and to change the liquid into a vapor.
Thermochemical equations are usually written by designating the
value of A / / rather than writing the energy as a reactant or product.
For an exothermic reaction . A / / is always negative because the system
loses energy. So. the thermochemical equation for the exothermic for -
mation of 2 mol of gaseous water from its elements now has the fol -
lowing form.

2H2(g) + Q 2( g) 2H 2Q(g ) M i = -483.6 kJ

Figure 2 graphically shows the course of an exothermic reaction. The

initial enthalpy of the reactants is greater than the final enthalpy of the
products. This means energy as heat is evolved, or given off. during the
reaction; this is described as a negative enthalpy change.
For an endothermic reaction. A / / is always positive because the sys -
tem gains energy. T hus, the endothermic decomposition of 2 mol of
gaseous water has the following thermochemical equation.

2H:Q(g ) > 2H:( g ) + 02(g) M l = 4483.6 kJ

The course of an endothermic reaction is illustrated in Figure 3. Energy

as heat is absorbed in this reaction, meaning that the initial enthalpy of

536 CHAPTER 16
 Endothermic Reaction Pathway FIGURE 3 In an endothermic
chemical reaction, the enthalpy
change is positive because energy is
Final enthalpy Products absorbed into the system as heat.

Energy as """" AH is
CL heat is absorbed positive
C
-C AH
c
LU

Reactants Initial enthalpy

Course of reaction

the reactants is lower than the final enthalpy of the products. In this
case, AH is designated as positive.
Keep in mind the following when using thermochemical equations.
1. The coefficients in a balanced thermochemical equation represent
the numbers of moles of reactants and products and never the num -
bers of molecules. This allows us to write these coefficients as frac -
tions rather than whole numbers when necessary.
2. The physical state of the product or reactant involved in a reaction
is an important factor and therefore must be included in the ther -
mochemical equation.
3. The change in enthalpy represented by a thermochemical equation is
directly proportional to the number of moles of substances undergo -
ing a change. For example, if 2 mol of water are decomposed, twice
as much enthalpy. 483.6 kJ. is needed than for the decomposition of
I mol of water.
4. The value of the enthalpy change. All . is usually not significantly
influenced by changing temperature.

Enthalpy of Formation
The formation of water from hydrogen and oxygen is a composition reac-
—
tion the formation of a compound from its elements in their standard
form. Thermochemical data are often recorded as the enthalpies of such
composition reactions. The molar enthalpy of formation is the enthalpy
change that occurs w hen one mole of a compound is formed from its
elements in their standard state at 25°C and I atm.

REACTION ENERGY 537

 To make comparisons meaningful, enthalpies of formation are given
for the standard states of reactants and products— these are the states
found at atmospheric pressure and,usually, room temperature ( 298.15 k ).
Thus, the standard state of water is liquid, not gas or solid.Hie standard
state of iron is solid, not a molten liquid. To signify that a value represents
measurements on substances in their standard states, a " sign is added to
the enthalpy symbol, giving AII" for the standard enthalpy of a reaction.
Adding a subscript /, as in A / / '/, further indicates a standard enthalpy of
formation.
Some standard enthalpies of formation are given in Appendix
Table A - 14. Each entry in the table is the enthalpy of formation for the
synthesis of one mole of the compound listed from its elements in their
standard slates. The thermochemical equation to accompany each
enthalpy of formation shows the formation of one mole of the compound
from its elements in their standard states.

Stability and Enthalpy of Formation

If a large amount of energy as heat is released when a compound is
formed, the compound has a large negative enthalpy of formation. Such
compounds are very stable.
,
Elements in their standard states are defined as having AH 1 = 0. The
A // '/ of carbon dioxide is -393.5 kJ/mol of gas produced.Therefore, car -
bon dioxide is more stable than the elements from which it was formed.
You can see in Appendix Table A - 14 that the majority of the enthalpies
of formation are negative.
Compounds with relatively positive values of enthalpies of forma-
tion. or only slightly negative values, are typically unstable. For example,
hydrogen iodide, HI. is a colorless gas that decomposes somewhat when
.
stored at room temperature It has a relatively high positive enthalpy of
formation of +26.5 kJ/mol. As it decomposes, violet iodine vapor. F,
becomes visible throughout the container of the gas.
Compounds with a high positive enthalpy of formation are sometimes
very unstable and may react or decompose violently. For example, ethyne
( acetylene ). CMC ( A// '/ = +226.7 kJ / mol ). reacts violently with oxygen
and must be stored in cylinders as a solution in acetone. Mercury fulmi-
nate, HgC:N:02. has a very large enthalpy of formation of +270 kJ/ mol.
Its instability makes it useful as a detonator for explosives .

Enthalpy of Combustion
Combustion reactions produce a considerable amount of energy in the
form of light and heat when a substance is combined with oxygen. The
enthalpy change that occurs during the complete combustion of one
mole of a substance is call the enthalpy of * combustion of the substance.

538 CHAPTER 16
 Stirrer Ignition wires
FIGURE 4 This is a diagram of a

L
Thermometer
simple combustion calorimeter. A
weighed sample is ignited by
an electric spark and burned in the
Insulated
outside
sample dish in an atmosphere of
J^
|
Water
Steel bomb
pure oxygen . The energy generated
container
by the combustion reaction warms
the steel bomb and the water
surrounding it . The thermometer
Sample dish measures the initial and final
Steel
container temperatures of the water and this
,

temperature change is then used to

calculate the energy evolved by the
reaction as heat .

Li
Enthalpy of combustion is defined in terms of one mole of reactant ,
whereas the enthalpy of formation is defined in terms of one mole of
product . All substances are in their standard states. The general
enthalpy notation, AH , applies to enthalpies of reaction , but the addi -
tion of a subscripted c. All , refers specifically to enthalpy of combus-
tion . A list of enthalpies of combustion can be found in Appendix
Table A -5. A combustion calorimeter is a common instrument used to
determine enthalpies of combustion . Figure 4 shows a fixed -volume
calorimeter. A similar apparatus under constant pressure is used to
obtain enthalpy measurements.

Calculating Enthalpies of Reaction

ITiermochemical equations can be rearranged and added to give enthalpy
changes for reactions not included in the data tables. The basis for cal -
culating enthalpies of reaction is known as Hess's law: The overall
enthalpy change in a reaction is ecjual to the sum of enthalpy changes for
the individual steps in the process. The energy difference between reac-
tants and products is independent of the route taken to get from one to
the other. In fact , measured enthalpies of reaction can be combined to
calculate enthalpies of reaction that are difficult or impossible to actu -
ally measure.
To demonstrate how to apply Hess's law, we will work through the
calculation of the enthalpy of formation for the formation of methane
gas, CH 4. from its elements, hydrogen gas and solid carbon ( graphite ),
at 298.15 K ( 25°C ).

C ( s ) + 2 H:(s ) * CH 4( g ) A H' f = - y

REACTION ENERGY 539

 In order to calculate the change in enthalpy for this reaction, we can use
the combustion reactions of the elements, carbon and hydrogen, and of
methane.

C(.v ) + 02(g) "

A / / = -393.5 kJ
* C02(g)
, A //;' = -285.8 kJ
H (g) +
^
02(g)
CH4(g) + 202(g)
» H20( / )
C02( g ) + m20( l ) A //;' = -890.8 kJ

Ihe general principles for combining thermochemical equations follow.

1. If a reaction is reversed, the sign of A / / is also reversed.
2. Multiply the coefficients of the known equations so that when added
together they give the desired thermochemical equation. Multiply
the A7 / by the same factor as the corresponding equation.
In this case, reverse the combustion equation for methane, and remem -
ber to change the sign of AH from negative to positive. This will change
the exothermic reaction to an endothermic one.

CO:(g ) + 2H,0( / ) > CH4(g) + 20:( g)

°
AH = +890.8 kJ

Now we notice that 2 moles of water are used as a reactant: therefore,

2 moles of water will be needed as a product. In the combustion reac -
tion for hydrogen as it is written, it only produces one mole of water. We
must multiply the coefficients of this combustion reaction and the value
of A / / by 2 in order to obtain the desired quantity of water.

2H2(g) + 02(g) 2H:C)( / ) A// = 2( -285.8 kJ )

"
We are now ready to add the three equations together using Hess's law
to give the enthalpy of formation for methane and the balanced equation.

C(.v) + CO A // t = -393.5 kJ
''
^ )

2 H2( g ) + 02tsr) 2H20 7 ( )

"
A // = 2(-285.8 kJ )

cchts) + 2n:otn CH4(J?) + 2Q? fr ) °

AH = +890.8 k.I
C(5 ) + 2 H2(g) » CH4(g) AH )1 = -74.3 kJ

Hess 's law says that the enthalpy difference between reactants and
products is independent of pathway. Therefore, any enthalpy of reaction
may be calculated using enthalpies of formation for all the substances
in the reaction of interest, w ithout knowing anything else about how the
reaction occurs. Mathematically, the overall equation for enthalpy
change will be in the form of the equation shown below .

'/
AIf = sum of |( A / / of products) x ( mol of products ) | -
sum of [ ( A / / '/ of reactants ) x ( mol of reactants ) )

An example using Hess's law is shown in Sample Problem B .

540 CHAPTER 1 6
 SAMPLE PROBLEM B For more help, go to the Mut / l Tutor af the end of this chapter.

Calculate the enthalpy of reaction for the combustion of nitrogen monoxide gas, NO, to form nitrogen
dioxide gas, N( )2. as given in the following thermochemical equation.

’
NO (g ) + 0,<g ) > NO,( g )

Use the enthalpy-of- formation data in Appendix Table A - 14. Solve by combining the known thermochem-
ical equations. Verify the result by using the general equation for finding enthalpies of reaction from
enthalpies of formation.

SOLUTION
1 ANALYZE Given:
‘ N (g) + |02(g)
2 > NO( g ) A / / ? = +90.29 kJ
'

' N (g) + CMg ) > NO,(g)

2 ”
A // = +33.2 kJ

”
Unknown: AH for NO(g) + ' o:(g) NO2( g )

2 PLAN AII can be found by adding the A / / s of the component reactions as specified in Uess s law.
The desired equation has NO(g) and 02(g) as reactants and NO:(g) as the product.
*
NO( g) + iQ2(g) > N02(g)

We need an equation with NO as a reactant. Reversing the first reaction for the formation
of NO from its elements and the sign of A / / yields the following thermochemical equation.

NO(g) ,[ H 2( g ) + \ 02( g ) °
AH = -90.29 kJ

The other equation should have NO? as a product, so we can retain the second equation for
the formation of NO? from its elements as it stands .
' N te) + °:te)
2 » N02(g) '
AH l! = +33.2 LI

3 COMPUTE
NOte) 'j^te) + ]£Ute) AH = -90.29 kJ
”
!N>M) + o2te) NO:( g)
”
AH = +33.2 kJ

NO(g) + ;o2(g) .
> NO (g ) ”
A // = -57.1 kJ

4 EVALUATE
^
Note the cancellation of the N2(g) an(J pHrtial cancellation of the 02(g).

The unnecessary reactants and products cancel to give the desired equation.
The general relationship between the enthalpy of a reaction and the enthalpies of forma-
tion of the reactants and products is described in the following word equation.

°
AH = sum of |( A / / '/ of products) x ( mol of products ) ) -
sum of [( AH°f of reactants ) x ( mol of reactants) )

REACTION ENERGY 541

 To find the necessary sums, the A / / '/ value for each reactant and each product must be mul -
tiplied by its respective coefficient in the desired equation. For the reaction of NO with 02.
applying this equation gives the following value for All 0.

'
All 0 = AW / ( NO:) - [ A / / '/ ( NO ) 4- 0|
= +33.2 kJ/mol - 9029 kJ/mol = -57.1 kJ
Note that zero is the assigned value for the enthalpies of formation of elements in their
standard slates.

PRACTICE Answers in Appendix E

1. Calculate the enthalpy of reaction for the combustion of methane

gas. ( 11 . . to form C( ):( g ) f H -,( ) ( / ) .

2. Carbon occurs in two distinct forms. It can be the soft, black mate -
rial found in pencils and lock lubricants, called graphite, or it can
be the hard, brilliant gem we know as diamond. Calculate AH " for
the conversion of graphite to diamond for the following reaction.

^ graphite^ ) * ^ diamond
The combustion reactions you will need follow.
Go to go.hrw.com for
%raphiiA
+ (§) > C02(g) A // ® = -394 kJ more practice problems
-> C02 ( g ) All 0 = -396 kJ that ask you to use
diamond
^}+ Hess's law.
Keyword: HC 6 NRGX

Determining Enthalpy of Formation

When carbon is burned in a limited supply of oxygen, carbon monoxide
is produced. In this reaction, carbon is probably first oxidized to carbon
dioxide. Then part of the carbon dioxide is reduced with carbon to give
.
some carbon monoxide Because these two reactions occur simultane-
.
ously and we get a mixture of CO and C02 it is not possible to directly
measure the enthalpy of formation of CO( g) from C(.v ) and 02(g).

.
C( v) + tO,( ) > CO( g ) '/
A // = ?
*
I lowever, we do know the enthalpy of formation of carbon dioxide and
the enthalpy of combustion of carbon monoxide.

C(s) + 0:(g) — C02( g )

* °
AH f = -393.5 kJ/mol
CO( g ) + \ 02( g ) > COi(g) AH" = -283.0 kJ / mol

We reverse the second equation because we need CO as a product.

Adding gives the desired enthalpy of formation of carbon monoxide.

542 CHAPTER 16
 Enthalpies of Reaction FIGURE 5 This diagram shows the
enthalpy of reaction for carbon diox -
ide. CO:. and carbon monoxide, CO.
C(s) + O2 ( g ) 0 kJ

AH = -110.5 kJ

CO (g) + lQ2 ( g)

AH = -283.0 kJ
AH = +283.0 kJ
CO 2 ( g )
-393.5 kJ

C(.v ) + 02(g ) AH " = -393.5 kJ

CCKQJ CO( g ) + 'JMK ) AH " = +283.0 kJ
C( s ) + l 02(g ) » CO(g) AH 11 = -110.5 kJ

Figure 5 is a model for the process described in this section. If we plot

the reactions based on their relative energy, you can see the relationship
among the values obtained for the enthalpy of formation of carbon
monoxide. The formation of C02 is plotted at a level corresponding to
- 393.5 kJ / mol. The diagram shows the reverse of the combustion reaction
( + 283.0 kJ /mol ) is added to that level. From the diagram , you see the dif -
ference. which represents the formation of CO.This value is -110.5 kJ / mol.

SAMPLE PROBLEM C For more help, go to the Math Tutor at the end of this chapter.
Calculate the enthalpy of formation of pentane. C5H 12, using the information on enthalpies of formation in
Appendix Table A - 14 and the information on enthalpies of combustion in Appendix Table A 5. Solve by -
combining the known thermochemical equations.

SOLUTION
1 ANALYZE Given: C ( s ) + O2( g ) » CO:( £ ) AH" = -393.5 kJ
H 2(g) + i 02(g) * H,0( / ) AH" = -285.8 kJ
f

C5 H 12(g ) + 802(g) * 5CO:(g) + 6 H 20( / ) AH" = -3535.6 kJ

Unknown: AH " for 5C(.v ) + 6H 2(g ) * CsH 12(g )
REACTION ENERGY 543
2 PLAN Combine the given equations according to Hess's law. We need C>H| as a product, so we i

reverse the equation for combustion of C2Ht 2 and the sign for AH ' . Multiply the equation
1

for formation of CCT by 5 to give 5C as a reactant. Multiply the equation for formation of
H:Q by 6 to give 6H2 as a reactant.

3 COMPUTE .
5C( v ) + 5():( ") 5CCM,g) AH 0 = 5(-393.5 kJ )

6H:0? ) + 3CM,g ) .
6B Off ) AH 0 = 6( -285.X kJ )

SGOjf#) + ,
» C,H ,( # ) + fiOytgf AH 11 = +3535.6 kJ

5C(.v) + 6H:(g) CsH 12(g) '/

A // = - 146.7 kJ

4 EVALUATE The unnecessary reactants and products cancel to give the correct equation.

PRACTICE Answers in Appendix E

1. Calculate the enthalpy of formation of butane, C4I ll( ). using the bal-
anced chemical equation and information in Appendix Table A -5 and
Table A - 14. Write out the solution according to Hess’s law.
2. Calculate the enthalpy of combustion of 1 mol of nitrogen. N2, to
form NG: using the balanced chemical equation and Appendix
Table A - 14.
3. Calculate the enthalpy of formation for sulfur dioxide, SO:, from
its elements, sulfur and oxygen. Use the balanced chemical equa-
tion and the following information. Go to go.hrw.com for
more problems that ask

^
S(.v ) + 02 (g) S03(g) "
A // = -395.2 kJ you to calculate
enthalpies of formation
and combustion.
2S 02 02
(£) + (g) > 2SQ3( g) °
AH = -198.2 kJ
Keyword: HC 6 NRGX

SECTION REVIEW Critical Thinking

.
1 What is meant by enthalpy change ? 6. INTEGRATING CONCEPTS Isooctane (C 8 H18) is a
2. What is meant by enthalpy of reaction? major component of gasoline.
3. Describe the relationship between a compound's a. Using the following thermodynamic data, calcu -
stability and its enthalpy of formation. late the change in enthalpy for the combustion
of 1.0 mol of isooctane.
4. What is the importance of Hess's law to thermo -
dynamic calculations? \
H2(g) + 02 { g ) + H20(g) AH0 = -241.8 kJ;
5. How much energy would be absorbed as heat by
C( s ) + 02 ( g ) - °
CO2 ( g ) AH = -393.5 kJ;
75 g of iron when heated from 295 K to 301 K ?
8C(s) + 9H2(g)
°
C8H18( / ) AW = -224.13 kJ.
b. One gallon of isooctane has a mass of 2.6 kg.
What is the change in enthalpy for the combus-
tion of one gallon of this compound?

544 CHAPTER 16
Chemistry in Action
Self-Heating Meals
Who would have thought that
corrosion could be useful? The
" We' ve made about 80 million
heaters for the military in the last 10
^
HeaterMeals Company did. years. Lately we' ve been successfully
This company uses the prop - marketing them to long-distance
erties of saltwater corrosion truck drivers. The product is in about
to heat TV- type dinners, and 800 truck stops in 48 states."
now it is taking packaged The company has plans to develop
foods to a new level of other products using the
convenience. controlled use of
HeaterMeals' products, as " supercorrosion." "A beverage
their name implies, come with could be heated," says
a self - contained heat source. Each McLandrich, " and we do have
meal contains a package of food, a prototypes for a baby-bottle
tray that holds a porous pouch con - warmer. We're also working
taining Mg and Fe alloy, and a 2 oz on making a portable hot cup
pouch filled with salt water. When of coffee or a hot cup of tea
the salt water is poured into the tray or cocoa."
with the porous pouch, it
begins to vigorously corrode
the metals. The sealed, pre-
cooked food package is then Questions
placed on top of the tray and 1. How did the development of
returned to its box, where the self -heating metallic alloy pow -
temperature of the food pack - ders benefit the military ?
age is raised by 100°F, heating
2. If the temperature of 50.0 mL
the meal in 14 min.
of water is raised from 25.0°C to
Corrosion, the process by
100.°C using the self -heating
which a metal reacts with air
meal package, what is the change
or water, is usually an undesir - A This product uses supercorrosion to in the enthalpy of the magnesium
able event, such as when iron cor - give you a hot meal. reaction in this package?
rodes to form rust. With
HeaterMeals, however, the corrosion
1930s. " But," says McLandrich, "there
process is speeded up to produce an
exothermic reaction—with the really have been no significant uses
NKS . Dtvrloptd BJiaUottd fry Ifrt
NatooMi Some TcMfccn AvmMm
excess energy as the desired result. of the product until the Desert Storm For a variety of links related to this
According to Drew McLandrich, of conflict, which led to the military's chapter, go to www.scilinks.org
the HeaterMeals Company, the idea
for using self -heating metallic alloy
taking this technology and adopting
it for field use so that soldiers could
Topic: Supercorrosion
SciLinks code: HC61479
^
powders has been around since the heat a meal-ready-to-eat.
/

REACTION ENERGY 545

 SECTION 2
Driving Force
OBJECTIVES of Reactions
SJ Explain the relationship
between enthalpy change
and the tendency of a
reaction to occur.
T he change in energy of a reaction system is one of two factors that
rj Explain the relationship allow chemists to predict whether a reaction will occur spontaneously
between entropy change and to explain how it occurs. The randomness of the particles in a
and the tendency of a system is the second factor affecting w hether a reaction will occur spon -
reaction to occur. taneously.

a Discuss the concept of free

energy, and explain how the
value of this quantity is calcu- Enthalpy and Reaction Tendency
lated and interpreted.
The great majority of chemical reactions in nature are exothermic. As
these reactions proceed, energy is liberated and the products have less
^ Describe the use of free energy than the original reactants. The products are also more resistant
energy change to determine
to change, more stable, than the original reactants. The tendency
the tendency of a reaction
to occur.
throughout nature is for a reaction to proceed in a direction that leads
to a lower energy state.
We might think that endothermic reactions, in which energy is
absorbed, cannot occur spontaneously because the products are at
higher potential energy and are less stable than the original reactants.
They would be expected to proceed only with the assistance of an out -
side influence, such as continued heating. However, some endothermic
.
reactions do occur spontaneously We conclude that something other
than enthalpy change must help determine whether a reaction w ill occur.

CHEMISTRY £ 1
Module 9: Thermochemistry Entropy and Reaction Tendency
A naturally occurring endothermic process is melting. An ice cube melts
spontaneously at room temperature as energy is transferred from the
SC
/ lNKS.) Developed Md nuinUiBtd by tttt
warm air to the ice. The well-ordered arrangement of water molecules
in the ice crystal is lost, and the less-ordered liquid phase of higher ener -
NJIKMUI Sotn< « Ttatbm Aivxutic*

For a variety of links related to this gy content is formed. A system that can go from one state to another
chapter, go to www.scilinks.org without an enthalpy change does so with an increase in entropy.
Topic: Entropy Look at the physical states of the reactants in the chemical equation
SciLinks code: HC60523 for the decomposition of ammonium nitrate.

,
2NH4NO ( .V )
* 2N2( iI?) + 4H:0( / ) + 0:(K )
546 CHAPTER 16
On the left side are 2 mol of solid ammonium nitrate. The
right - hand side of the equation shows 3 mol of gaseous
molecules plus 4 mol of a liquid. The arrangement of par -
ticles on the right - hand side of the equation is more ran -
dom than the arrangement on the left side of the
equation and hence is less ordered . Figures 6a and 6b
show the reactant and products of this decomposition
reaction .
These examples illustrate that there is a tendency in
nature to proceed in a direction that increases the ran -
domness of a system . A random system is one that lacks a
regular arrangement of its parts. This tendency toward
randomness is called entropy. Entropy, S, can he defined
in a simple qualitative way as a measure of the degree of
randomness of the particles, such as molecules, in a system.
To understand the concept of entropy, consider solids, liq -
uids, and gases. In a solid , the particles are fixed in posi -
tion in their small regions of space, but they are vibrating (a)
back and forth . Even so. we can determine with fair pre -
cision the location of the particles. The degree of ran -
domness is low, so the entropy is low. When the solid
melts, the particles are still very close together, but they
can move about somewhat . The system is more random ,
and it is more difficult to describe the location of the par-
ticles, The entropy is higher. When the liquid evaporates,
the particles are moving rapidly and are also much farther
apart. Locating an individual particle is much more diffi -
cult . and the system is much more random. The entropy of
the gas is still higher than that of the liquid . A general but
not absolute rule is that the entropy of liquids is larger
than that of solids and the entropy of gases is larger than
that of liquids. But this rule must be used with caution .
For example, the entropy of liquid mercury is much less
than that of some solids.
The entropy of a pure crystalline solid is zero at
absolute zero. As energy is added , the randomness of the ( b)
molecular motion increases. Measurements of energy
absorbed and calculations are used to determine the FIGURE 6 When ammonium nitrate.
NH 4NO 3 , decomposes, the entropy of the reaction
absolute entropy or standard molar entropy, and values
system increases as ( a ) one solid reactant becomes
are then recorded in tables. These molar values are ( b ) two gaseous products and one liquid product .
reported as kJ / ( mol* K ). Entropy change, which can also
be measured , is defined as the difference between the
entropy of the products and the reactants. Therefore, an increase in
entropy is represented by a positive value for AS, and a decrease in
entropy is represented by a negative value for AS.
The process of forming a solution almost always involves an increase
in entropy because there is an increase in randomness. This is true for
mixing gases, dissolving a liquid in another liquid , and dissolving a solid
in a liquid .

REACTION ENERGY 547

 ^
Water molecule Figure 7 illustrates the entropy change that lakes
* place when solid sugar is dissolved in tea ( an aqueous
•••% » solution ) . In the sugar- water system shown in
Figure 7a , the solid sugar has just been added to the
Sugar tea . but most of it has not yet dissolved . Hie entropy
molecules is low because the majority of the sugar molecules are
in one region at the bottom of the pitcher and the
majority of the water molecules can be found every -
Low entropy where else in the pitcher. After the sugar dissolves in
the tea. shown in Figure 7b, the sugar molecules are
Sugar molecules
thoroughly mixed throughout the tea solution . Sugar
molecules and water molecules might be found any -
where in the solution . so the entropy, the randomness,
of the system increases. This would give AS a positive
value for this solid -liquid system. You can imagine the
Water ^ same series of events happening for a system of gases
molecule
•« mixing with each other or a system of liquids mixing.
In each case, AS would have a positive value once the
High entropy solution was formed.

FIGURE 7 When a solid

dissolves in a liquid.!he entropy Free Energy
of the system increases.
Processes in nature are driven in two directions: toward least enthalpy
and toward largest entropy. When these two oppose each other , the
CHEMISTRY t )

* dominant factor determines the direction of change. As a way to predict

VTO* which factor will dominate for a given system , a function has been
Module 9: Thermochemistry defined to relate the enthalpy and entropy factors at a given tempera -
ture and constant pressure. This combined enthalpy-entropy function is
called the free energy, G , of the system; it is also called Gibbs free ener -
TFjftslY£ft » j 11 gy. This function simultaneously assesses the tendencies for enthalpy
and entropy to change. Natural processes proceed in the direction that
CROSS- DISCIPLINARY
lowers the free energy of a system.
Go to go. hrw. com for a full- length
Only the change in free energy can be measured. It can be defined in
article on free -energy changes
related to ATP in the body. terms of changes in enthalpy and entropy. At a constant pressure and
temperature, the free -energy change, AG . of a system is defined as the
Keyword: HC 6 NRGX
.
difference betw een the change in enthalpy AH , and the product of the
Kelvin temperature and the entropy change , which is defined as TAS.
AC," = AH" - TAS"
Note that this expression is for substances in their standard states. The
product TAS and the quantities AG and AH have the same units, usually
kJ . The units of AS for use in this equation are usually kJ / K. If AG < 0.
the reaction is spontaneous.
AH and AS in the free-energv equation can have positive or negative
values. This leads to four possible combinations of terms.
'
I able 2 on the next page shows that if AH is negative and AS is
positive, then both terms on the right in the free energy equation are

548 CHAPTER 16
negative. Both factors contribute to the process's being spontaneous.
Therefore, AG will always be negative, and the reaction is definitely
spontaneous. On the other hand,if AH is positive ( endothermic process)
and AS is negative (decrease in randomness ), then the reaction as writ -
ten is not spontaneous. When the enthalpy and entropy changes are
operating in different directions, sometimes one will predominate and
sometimes the other will predominate. There are reactions in which the
enthalpy change is negative and the entropy change is negative. Hie
enthalpy factor leads to a spontaneous process,but the negative entropy Chemistry in Action
change opposes this. This is true in the following reaction. The entropy Diamonds Are Forever ?
decreases because there is a decrease in moles of gas. Carbon occurs in different forms, two of
which are graphite and diamond. Using
C2H4(g) + H2(g) > C2H6(g) thermodynamic data, the change in
free energy for diamond converting to
There is a fairly large decrease in entropy, AS = -0.1207 kJ /( mobK ).
" graphite under standard thermodynam-
However, the reaction is strongly exothermic, with a AH " = -136.9 kJ/mol. ic conditions is -3 kJ/mol. That is, since
AG is negative for this reaction, dia -
The reaction proceeds because the enthalpy term predominates.
mond should spontaneously change to

"
AG = AH ° - TAS
= -100.9 kJ / mol
-
° = -136.9 kJ/mol - 298 K[-0.1207 kJ/(mol K ) ]
graphite at 25°C and 1 atm. So, why
doesn't all of our diamond jewelry
change to graphite ? The reaction rate is
too slow for this spontaneous change
We can contrast this with the common commercial process for the to be observed. Therefore, at 25°C and
manufacture of syngas, a mixture of CO and H2. ( This gas mixture is the 1 atm, although diamonds are not " for -
starting point for the synthesis of a number of large - volume commercial ever," they will last a very long time.
chemicals, such as methanol. CH;OH. )

CH4(g) + H20(g) » CO(g) + 3H2(g)

This reaction is endothermic, with AH " = +206.1 kJ / mol and AS" =

+0.215 kJ /( mol* K ). at standard conditions. The resulting AG is positive
at room temperature. This tells us that the reaction will not occur at
room temperature even though the entropy change is favorable.

AG = AH - TAS°
" ° = +206.1 kJ/mol - 298 K [+0.215 kJ/(mol K )|
= + 142.0 kJ / mol
-
TABLE 2 Relating Enthalpy, Entropy, and Free-
Energy Changes to Reaction Occurrence
AH A5 AO
- value + value always negative
( exothermic) ( more random )
- value - value negative at lower
( exothermic ) ( less random) temperatures
+ value + value negative at higher
( endothermic) (more random ) temperatures
+ value - value never negative
( endothermic ) ( less random )

REACTION ENERGY 549

 SAMPLE PROBLEM D
For the reaction NH4CI( s) ,
NH (g) + HCI( j? ), at 298.15 K. AH = 176 kJ/mol and
°
AS = 0.285 kJ/( mol* K ). Calculate AG\ and tell whether this reaction is spontaneous in
(
°
the forward direction at 208.15 K.

SOLUTION
1 ANALYZE Given: A / / " = 176 kJ/ mol at 298.15 K
"
AS = 0.285 kJ/( mol*K ) at 298.15 K
Unknown: AG" at 298.15 K

2 PLAN A A. AII . T AG

The value of AG can he calculated according to the following equation.

3 COMPUTE
" "
AG = A / / - TAS
°
" -
AG = 176 kJ /mol - 298 k [0.285 kJ/( mol K ) ]
= 176 kJ/mol - 84.9 kJ/mol
= 91 kJ /mol

4 EVALUATE The answer is reasonably close to an estimated value of 110. calculated as 200 - ( 300 x 0.3 ).
The positive value ol AG shows that this reaction does not occur naturally at 298.15 k.

PRACTICE Answers in Appendix E

Go to go.hrw.com for
1 . For the vaporization reaction Br> ( / ) "
Br2(g), A / / = 31.0 kJ/mol more practice problems
and AS* 1 = 93.0 J/(mol*K ). At what temperature will this process be that ask you to
spontaneous? determine spontaneity
based on tree-energy
changes.
Keyword: HC 6 NRGX

SECTION REVIEW .
6 In the reaction in Sample Problem D, why does the
.
1 What kind of enthalpy change favors a sponta - entropy increase ?
neous reaction? Critical Thinking
2. What is entropy, and how does it relate to spon- 7. APPLYING MODELS Most biological enzymes
taneity of reactions? become denatured when they are heated and lose
3. List several changes that result in an entropy their ability to catalyze reactions. This process
increase. (original enzyme > denatured enzyme) is
4. Define free energy, and explain how its change endothermic and spontaneous. Which structure,
is calculated. the original enzyme or the denatured enzyme, is
more ordered? Explain your reasoning using ther -
5. Explain the relationship between free-energy modynamic concepts.
change and spontaneity of reactions.

550 CHAPTER 1 6
 CHAPTER HIGHLIGHTS
Thermochemistry
I Vocabulary •Thermochemistry is the study of the changes in energy that
thermochemistry accompany chemical reactions and physical changes.
calorimeter •A thermochemical equation is an equation that includes the
temperature quantity of energy released or absorbed as heat during the
joule reaction as written.
heat •An enthalpy change is the amount of energy absorbed as heat
specific heat by a system in a process carried out at constant pressure.
enthalpy change •The enthalpy of reaction is the enthalpy change that occurs
enthalpy of reaction during a chemical reaction.
thermochemical equation •The enthalpy change is negative for exothermic reactions and
molar enthalpy of formation positive for endothermic reactions.
enthalpy of combustion •Compounds with highly negative enthalpies of formation tend
Hess' s law to be stable; compounds with highly positive or only slightly
negative enthalpies of formation tend to be unstable.
•The standard molar enthalpy of formation is the enthalpy
change that occurs when one mole of a compound is formed
from its elements in their standard states at 25 C and 1 atm.
• The enthalpy change that occurs in a combustion reaction is
called the enthalpy of combustion.
•Enthalpies of reaction can be calculated by using enthalpies of
formation of reactants and products.

Driving Force of Reactions

I Vocabulary •The tendency throughout nature is for a reaction to proceed
entropy in the direction that leads to a lower energy state.
free energy •Entropy is a measure of the randomness of a system.
free- energy change •Free-energy change combines the effects of entropy and
enthalpy changes and temperature of a system, and it is a mea -
sure of the overall tendency toward natural change.
• A reaction is spontaneous if it is accompanied by a decrease in
free energy. It is not spontaneous if there is an increase in free
energy.

REACTION ENERGY 551

 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D.
12. Rewrite each equation below with the A /7 value
Thermochemistry included with either the reactants or the prod-
ucts. and identify the reaction as endothermic or
SECTION 1 REVIEW
exothermic.
1. How does the enthalpy of the products of a
reaction system compare with the enthalpy of
a. H2( g) + 02(g) — H O( / );
* .
the reactants when the reaction is °
AH = -285.83 kJ
b. 2Mg(s) + 02(g) — » 2MgO(s):
a. endothermic?
b. exothermic ? °
AH = -1200 kJ
2. a. Distinguish between enthalpies of reaction.
c. l 2( s )
d. 3CO(g) + Fe203(.v)
"
U( g ): A / / = +62.4 kJ
2Fe (.v ) + 3C02(g);
formation, and combustion,
b. On what basis are enthalpies of formation °
AH = -24.7 kJ
13. Use Appendix Table A - 14 to write the reaction
and combustion defined ?
illustrating the formation of each of the follow -
3. Write the equation that can be used to calculate
ing compounds from its elements. Write the A / /
the enthalpy of reaction from enthalpies of
as part of each equation, and indicate the A / /
formation.
for the reverse reaction.
4. What factors affect the value of All in a reac -
a. CaCl2(s)
tion system?
b. C2H2(g) ( ethyne, or acetylene )
5 . State Hess’s law. How is it used?
c. S02(g)
6. Describe a combustion calorimeter. What infor -
14. The reaction 2Fe203( j) + 3C(s)
mation can it give? *
4Fe(s ) + 3C02(g) is involved in the smelting
of iron. Use A / / , values given in Appendix
PRACTICE PROBLEMS Table A - 14 to calculate the enthalpy change
7. How much energy is needed to raise the temper - during the production of l mol of iron.
ature of a 55 g sample of aluminum from 22.4°C 15. Use enthalpy-of- formation data given in
to 94.6°C? Refer to Table 1 for the specific heat Appendix Table A - 14 to calculate the enthalpy
of aluminum. ( Hint: See Sample Problem A.) of reaction for each of the following. Solve each
8. If 3.5 kJ of energy are added to a 28.2 g sample by combining the known thermochemical equa -
of iron at 2()°C, what is the final temperature of tions. Verify each result by using the general
the iron in kelvins? Refer to Table 1 for the equation for finding enthalpies of reaction from
specific heat of iron. enthalpies of formation. ( I lint: See Sample
.
9 You need 70.2 J to raise the temperature of 34.0 g Problem B. )
of ammonia. NH3(g). from 23.0°C to 24.0°C. a. CaC03(s) — CaO(.v ) + C02( g)
Calculate the specific heat of ammonia.
*
b. Ca(OH) 2(s) —> CaO(.v ) + H20(g)
10. Calculate cp for indium metal, given that c. Fe203(s) + 3CO(g) 2Fe (.v ) + 3C02(g)
I.O mol In absorbs 53 J while increasing in . ,
16. For glucose C(>Hl 2Q6(.v ). AH = -1263 kJ/ moI
• .
temperature from 297.5 K to 299.5 K . Calculate the enthalpy change when 1 mol of
11. For each equation listed below, determine the ChHj2Oft( jp) combusts to form C02(g) and
A / / and type of reaction ( endothermic or H20( / ).
exothermic). 17. Calculate the standard enthalpies of reaction
a. C(.v ) + CMg) for combustion reactions in which ethane, C2H6,
b. CH4(g) + 2Q2(g)
* C02(g) + 393.51 kJ and benzene, C6H6, are the respective reactants
C'02(g) + 2HiO( / ) + 890.31 kJ and C02(g) and H20( / ) are the products in
,
c. CaCO (.v ) + 17b kJ CaO(.v ) + CO,(g) each. Solve each bv combining the known ther -
d. H20(g) HiO( / ) + 44.02 kJ
*
,
mochemical equations using the All values in

552 CHAPTER 16
 CHAPTER REVIEW

Appendix Table A - 14. Verify the result by using reaction will occur spontaneously. ( Hint: See
the general equation for finding enthalpies of Sample Problem D.)
reaction from enthalpies of formation. a. AH = +125 kJ. T = 293 K.
,
a. C:H ,(g) + 02(g) AS = 0.0350 kJ/ K
b. CftH6(/ ) + 02( g ) b. AH = -85.2 kJ. T = 127°C.
*
.
18. The enthalpy of formation of ethanol (\ HsOH. AS = 0.125 kJ/K
is -277.0 kJ/mol at 298.15 K. Calculate the c. AH = -275kJ, T = 773 K.
enthalpy of combustion of one mole of ethanol, AS = 0.450 kJ / K
assuming that the products are C02(g) and 28. The AS" for the reaction shown, at 298.15 K , is
11:Q( / ). ( Hint: See Sample Problem C.) 0.003 00 kJ /( mol * K ). Calculate the AG" for this
reaction, and determine whether it will occur
spontaneously at 298.15 K .
Driving Force of Reactions C( s ) + 02( g ) -—» C02( g) + 393.51 kJ

SECTION 2 REVIEW
19. Would entropy increase or decrease for changes MIXED REVIEW
in state in which the reactant is a gas or liquid
and the product is a solid? What sign would the
.
29 When graphite reacts with hydrogen at 300 K. A / /
is -74.8 kJ and AS is -0.0809 kJ / K . Will this reac -
entropy change have ?
tion occur spontaneously?
20. How does an increase in temperature affect the
30. How might you change reaction conditions to
entropy of a system?
induce an endothermic reaction that does not
21. What combination of A /7 and AS values always
occur naturally?
produces a negative free-energy change ?
31. The diagram below represents an interpretation
22. Explain the relationship between temperature
of Hess ' s law for the following reaction.
and the tendency for reactions to occur
Sn( s ) + 2Cl2(g) > SnCI4( / )
spontaneously.
Use the diagram to determine AH for each step
and the net reaction.
PRACTICE PROBLEMS Sn(s ) + Cl2( g ) > SnCl2(s) AH = ?
23. A reaction has AH = -356 kJ and AS = -36 J / K . SnCl 2( / ) + Cl2(g) > SnCl 4 ( s ) AH = ?
Calculate AG at 25°C to confirm that the reac - Sn ( s ) + 2CI2( g) > SnCI 4( / ) AH = ?
tion is spontaneous.
24. A reaction has AH = 98 kJ and AS = 292 J/K. 0
Sn(s), Cl 2 (g)
Investigate the spontaneity of the reaction at -100
room temperature. Would increasing the tem - - 325.1 kJ
- 200
perature have any effect on the spontaneity of ?
the reaction? - 300

25 . A reaction has AH = -76 kJ and AS = -117 J / K . SnCI 2 (s)

- 400 - - 186.2 kJ
Calculate AG for the reaction at 298.15 K . Is the
- 500
reaction spontaneous?
SnCI 4( / )
26. Hie gas-phase reaction of H 2 with C02 to - 600
produce H:0 and CO has AH = 11 kJ and
AS = 41 J /K . Is the reaction spontaneous at 32. The standard enthalpy of formation for sulfur
298.15 R? What is AG? dioxide gas is -296.8 kJ /mol. Calculate the
27. Based on the following values, compute AG val - amount of energy given off in kJ when 30.0 g
ues for each reaction and predict whether the of S02( g) is formed from its elements.

REACTION ENERGY 553

 CHAPTER REVIEW

33 . The thermite reaction used in some welding 39. Interpreting Concepts Look at the two pic -
applications has the following enthalpy and tures below. Which picture appears to have
entropy changes at 298.15 k. Assuming AS and more order? Why ? Are there any similarities
All are constant, calculate AG at 448 k. between the amount of order the marbles have
Fe203 + 2 Al(.v ) > 2Fe( s ) + Al203(.v ) and the entropy of particles?
All = -851.5 kJ ASf1 = -38.5 J /k
11

34 . Rewrite each equation below with the All value

included in either the reactants or products,
and identify the reaction as endothermic or
exothermic.
a. 2S02(g) + 02( g ) > 2S03(g);
All = - 197.8 kJ
b. 2NO:( g) > 2NO(g) + 0:(s); 1 o
All = ^ 114.2 kJ
c. C:H4(g) + 302( g) > 2C02(g) + 2 H:Q( / );
All = -1411.0 kJ
35 . Calculate the change in enthalpy for the follow - o
o
ing reaction. o
4FeO( v ) + 0:( g ) > 2Fe:() 3( x ) (a ) ( b)
Use the cnthalpv -of - formation data listed in
Appendix Table A - 14. 40. Inferring Conclusions A reaction is endother -
36. The reaction to synthesize methanol ( CH OH ) mic and has a All = 8 kJ. This reaction occurs
^
industrially is spontaneously at 25°C. What must be true about
CO( # ) + 2H2(g) CH3OH(g). the entropy change?
41. Inferring Conclusions If both All and A.S
'. ion = -90.7 kJ and the AS"reaction
The All 1read are negative, how does temperature affect
-220.8 J / k . At what temperatures is the reaction
spontaneity?
nonspontaneous?
37 . What is the main characteristic of a calorimeter 42. Inferring Relationships If the reaction
in a bomb calorimeter experiment, and why is X » Y is spontaneous, what can be said
this characteristic essential ? about the reaction Y > X?
43. Interpreting Concepts Absolute enthalpy can -
not be determined: only change in energy can
CRITICAL THINKING be measured. However, absolute entropy can be
determined. Explain why an absolute entropy
38. Relating Idea Given the entropy change for can be determined.
*
the first two reactions below, calculate the
entropy change for the third reaction below .
SH( v ) + 802(S ) > XSCMg) AS' = 89 J /K
/
2 SO:( v ) + o (,v ) ,
» 2SO ( g) AS = - 188 J /K
Ss .v + 120i .v
( ) ( ) > 8SOj(g) AS = ?

554 CHAPTER 16
 CHAPTER REVIEW

46. Performance Design an experiment to mea -

RESEARCH & WRITING
sure the molar heat capacities of zinc and cop -
44. Obtain information on alternative units of mea - per. If your teacher approves the design, obtain
sure used to express values of energy as heat and the materials needed and conduct the experi -
other forms of energy. Also, find out how the ment. When you are finished, compare your
quantities relate to SI units. Include information experimental values with those from a chemical
specifically on English units, such as the British handbook or other reference source .
thermal unit ( BTU). and on typical BTU ratings 47. Performance Develop a procedure to measure
of household appliances. Calculate how these rat - the A / / of the reaction shown below. If your
ings would be expressed in joules instead. teacher approves your procedure, test your pro-
cedure by measuring the A / / value of the reac -
tion. Determine the accuracy of your method by
ALTERNATIVE ASSESSMENT comparing your A / / with the accepted A / / value.
45. Performance Design a simple calorimeter CH3COONa( v ) Na~( aq ) + CH ^COO~( aq )
investigation to determine the molar enthalpy
of fusion of water. Use the following materials:
a large plastic- foam cup with cover , a ther -
mometer. a balance, water at room temperature,
and an ice cube. Allow your teacher to review
your design. Then carry out the investigation,
and write a laboratory report including your
i Graphing Calculator
Free- Energy Changes
Go to go.hrw.com for a graphing calculator
calculations and a comparison of vour quantita - exercise that asks you to calculate and graph
.
tive results with known values Try to account free - energy ( AG ) changes.
for any disagreements between the experimen-
tal and actual values. Keyword: HC 6 NRGX

REACTION ENERGY 555

 Math Tutor HESS' S LAW

You may have seen a popular comic strip in which a little boy takes a long, twisting path
between the school-bus stop and home. No matter which path the boy takes, the result
.
is always the same: He goes from the bus stop to the door of his house Hess ' s law covers
a similar situation in thermochemistry. No matter which or how many steps occur in the
process of changing one or more substances into one or more other substances, the over -
all change in enthalpy is always the same. Hess's law can be used, for example, to predict
the enthalpy change, AH 0, of a reaction without actually carrying out the reaction.

SAMPLE
Determine AH for the burning of carbon disulfide in oxygen.
CS2(/ ) + 302(g) C02(g) + 2S02(g) AH 11 = ?
Use the following information:
{
C ( s ) + 02(g)
(
\
> C02( g) AH = -393.5 kJ/mol
S(.v ) + 02(&) > SO2 ( g ) AH f = -296.8 kJ/mol
C(J) + 2S( s ) > CS2( / ) °
AH f = 87.9 kJ/mol
Rearrange the given equations in a way that will pul the reactants of the above equation
on the left and the products on the right.
1. CM + O2( g ) > CO2( g) '
AH f = -393.5 kJ/mol
.
2 2S t f + 202( g ) > 2S02(g) °
AH = 2( —296.8 kJ )
3. CS 2 I )
( AH = -87.9 kJ °
SUM: CS2( / ) + 302(g) CO:( g ) + 2 SQ 2(g)
Notice that equation 2 is double the original equation S(s ) + Q2(g) > SO:(g). The rea -
son for this is that 2S02 are needed on the product side to match the 2S02 in CS2( / ) +
302( g ) CQ2(g) + 2SO:(g). The third equation is the reverse of the original, putting CS2
on the reactant side of the final equation. The sign of AH is likewise reversed. The value of
All" is the sum of the AH " values for the three added equations.
AII " = -393.5 kJ + 2( -296.8 kJ ) + (-87.9 kJ )
AH = —1075.0 kJ
°
PRACTICE PROBLEMS
.
1 Calculate A / / " for the complete oxidation 2. Calculate A / / " for the reaction in which zinc
of sulfur to sulfur trioxide. sulfide ore is roasted to obtain zinc oxide.
]
S( s ) + - 0;( g) SO y ( g ) ZnS ( s ) +\02( g ) > ZnO( 5 ) + SO2( g)
Use the following information. Use the following information.
S(.v ) + O2( g ) * S02(g) A/7? = -296.8 kJ/mol
'
Zn( j) + 02(g) ZnO(i) A / / / = -348.0 kJ/mol
'
A H °, = -203.0 kJ/mol
S02(g) + lo2(g ) SQ3(g) AH °f = -99.2 kJ/mol Zn( ^ ) + S(.v ) > ZnS ( .v )
S(s) + O20? ) » SO:(,i,') AH'f = -296.8 kJ /mol

556 CHAPTER 16
Answer the following items on a separate piece of paper. 5. At a constant pressure, the following reaction is
MULTIPLE CHOICE
exothermic: 2N02(g) .
» N204(g) Which of
the following statements is true about the reac -
.
1 Which of the following two conditions will favor tion ( as written ) ?
a spontaneous reaction? A . The reaction is always spontaneous.
A . an increase in entropy and a decrease in B. The reaction is spontaneous at low tempera-
enthalpy tures. but not at high temperatures.
B. an increase in entropy and an increase in C. The reaction is spontaneous at high tempera -
enthalpy .
tures but not at low temperatures.
C. a decrease in entropy and a decrease in D. The reaction is never spontaneous.
enthalpy
SHORT ANSWER
D . a decrease in entropy and an increase in
enthalpy .
6 For a reaction in which a diatomic molecule dis -
sociates into atoms, what are the signs of AS and
2. The gasification of coal is a method of produc -
A / / ? Explain your answer. You may use the
ing methane by the following reaction.
reaction N2(g) > 2N( g) as an example of
C ( s ) + 2H2(g) > CH4(g) A /7 = ? such a reaction.
Find AH by using the enthalpy changes in the EXTENDED RESPONSE
following combustion reactions 7. For certain molecules, enthalpies of formation
C( s ) + 02(g) » CO2(g) AH = -394 kJ can be determined from combustion data. Using
the diagram below, calculate the enthalpy of
'
H2( g) + o2(g)
CH4( g);202(g )
H
> 20 ( / ) AH = -286 kJ
formation of methane gas, CH4(g), and the
> C02(g) + 2H:0( / )
AH = -891 kJ
enthalpies for two of the combustion reactions
listed below .
A . 75 kJ C. 1856 kJ
Combustion reactions:
B. -75 kJ .
D -1856 kJ C( J) + o2(g) » C02(g) AH = -393.5 kJ
3. Two metals of equal mass but different lc
H2( g) + >2(g) > H20( / ) AH = ?
specific heats absorb the same amount of heat. AH = ?
CH4( J? ) + 202( g ) > C02(g) + 2 H20( / )
Which metal undergoes the smaller change in
temperature?
A. The metal with the higher specific heat . C ( s) + 2H2(g) + 20,(g)

B. The metal with the lower specific heat .

C. Both undergo the same change in temperature. CH4(g) + 202(g)
D. Cannot determine from the information given.
.
4 Which of the following processes has a
negative A5?
Enthalpy
(kJ) -965.1 kJ 890.2 kJ

A . evaporating 1 mol of a liquid

B. raising the temperature of 1 L of water from
295 K to 350 K
C. freezing of 1 mol of a liquid C02(g) 2H20( /)
D. None of the above

J Always read the question before

looking at the answer choices.

REACTION ENERGY 557

 SEE PRE - LAB
EXPERIMENT 16 CALORIMETRY

Calorimetry and Hess’s Law

OBJECTIVES BACKGROUND
• Demonstrate proficiency in the use of Hess’s law states that the overall enthalpy change in
calorimeters and related equipment. a reaction is equal to the sum of the enthalpy changes
in the individual steps in the process. In this experi -
• Relate temperature changes to enthalpy
ment , vou will use a calorimeter to measure the
changes.
energy released in three chemical reactions. From
• Determine enthalpies of reaction for several your experimental data, you will verify Hess’s law.
reactions.
• Demonstrate that enthalpies of reactions SAFETY
can he additive.

MATERIALS
4 g NaOH pellets
50 mL 1.0 M MCI acid solution
50 mL 1.0 M NaOH solution
100 mL 0.50 M MCI solution
A
^ ^
For review of safety, please see Safety in the
Chemistry Laboratory
w

PREPARATION
in the front of your hook.

1 . Prepare a data table in which to record the total

100 ml . graduated cylinder volumes of liquid , initial temperature, and final
temperature of the three reactions you will carry
balance out. as well as the mass of the empty watch glass
distilled water and the watch glass plus NaOH pellets.
forceps 2 . Gently insert the thermometer into the plastic
glass stirring rod foam cup held upside down. Thermometers
break easily, so be careful with them , and do not
gloves use them to stir a solution .
plastic -foam cups ( or calorimeter )
PROCEDURE
spatula
Reaction 1 : Dissolving NaOH
thermometer 1 . Pour 100 mL of distilled water into your
watch glass calorimeter. Record the water temperature to
the nearest 0. l °C.
2 . Weigh a clean and dry watch glass to the nearest
0.01 g. Wearing gloves and using forceps, place
about 2 g of NaOH pellets on the watch glass.
Measure and record the mass of the watch glass
and the pellets to the nearest 0.01 g. It is impor-
tant that this step be done quickly: NaOll
absorbs moisture from the air.

558 CH A PTER 16
 EXPERIMENT 16

3. Immediately place the NaOH pellets in the CLEANUP AND DISPOSAL

calorimeter cup. and gently stir the solution 12. Check with vour teacher for the proper
with a stirring rod . Do not stir with a ther - disposal procedures. Always wash your
mometer. Place the lid on the calorimeter. hands thoroughly after cleaning up the
Watch the thermometer, and record the highest lab area and equipment.
temperature in vour data table.
4. Be sure to clean all equipment and rinse it with ANALYSIS AND INTERPRETATION
distilled water before continuing. 1. Organizing Ideas: Write a balanced chemical
equation for each of the three reactions that
Reaction 2: NaOH and HCI in Solution you performed . ( Hint: Be sure to include the
5. Pour 50 mL of 1.0 M HCI into your calorimeter. physical stales of matter for all substances. )
Record the temperature of the HCI solution to 2 . Organizing Ideas: Write the equation for the
the nearest 0.1 ° C. total reaction by adding two of the equations
6. Pour 50 mL of 1.0 M NaOH into a graduated from item 1 and then canceling out substances
cylinder. For this step only, rinse the thermome- that appear in the same form on both sides of
ter, and measure the temperature of the NaOH the new equation .
solution in the graduated cylinder to the nearest 3. Organizing Data: Calculate the change in
0.1 ° C. Record the temperature, and then replace temperature for each of the reactions.
the thermometer in the calorimeter.
4. Organizing Data: Assuming that the density of
7. Pour the NaOH solution into the calorimeter the water and the solutions is 1.00 g/ mL, calcu -
cup, and stir gently. Place the lid on the calorim - late the mass of liquid present for each of the
eter. Watch the thermometer and record the reactions.
highest temperature.
5 . Analyzing Results: Using the calorimeter equa -
8. Pour the solution in the container designated bv tion , calculate the energy as heat released by
your teacher. Clean and rinse all equipment each reaction. ( Hint: Use the specific heat of
before continuing with the procedure. water in your calculations. )

Reaction 3: Solid NaOH and HCI in Solution H:O = 4.184 J /g . °C

9. Pour 100 mL of 0.50 M HCI into your calorime- heat = m x At x cp H ,O
ter. Record the temperature of the HCI solution 6. Organizing Data: Calculate the moles of NaOH
to the nearest 0.1 °C. used in each of the reactions.
10. Measure the mass of a clean and dry watch 7. Analyzing Results: Calculate the A // value in
glass, and record the mass. Wear gloves, and kJ / mol of NaOH for each of the three reactions.
using forceps, obtain approximately 2 g of
NaOH pellets. Place them on the watch glass, 8. Organizing Ideas: Using your answer to
and record the total mass. As in step 2, it is Analysis and Interpretation item 2 and vour
important that this step he done quickly. knowledge of Hess’s law, explain how the
enthalpies for the three reactions should be
11. Immediately place the NaOH pellets in the mathematically related .
calorimeter, and gently stir the solution . Place
the lid on the calorimeter. Watch the thermome-
ter, and record the highest temperature. When
finished with this reaction , pour the solution into
the container designated by your teacher for dis-
posal of basic solutions.

REACTION ENERGY 559

 CHAPTER 1 7

Chemists can determine the rates

at which chemical reactions occur.
 SECTION 1
The Reaction Process
OBJECTIVES
Explain the concept of
B y studying many types of experiments, chemists have found that reaction mechanism.
chemical reactions occur at widely differing rates. For example, in the
presence of air. iron rusts very slowly, whereas the methane in natural sj Use the collision theory to
gas burns rapidly. The speed of a chemical reaction depends on the interpret chemical reactions.
energy pathway that a reaction follows and the changes that take place
on the molecular level when substances interact . In this chapter, you
will study the factors that affect how fast chemical reactions take place. Define activated complex.
*
Relate activation energy
to enthalpy of reaction .
Reaction Mechanisms
If you mix aqueous solutions of HC1 and NaOH . an extremely rapid
neutralization reaction occurs, as shown in Figure 1.
HjO*( aq ) + C\ ~( aq ) + Na + ( n</ ) + OH ( aq ) > 2 H:0( / ) + Na ~ ( w/ ) + C\~( aq )
The reaction is practically instantaneous; the rate is limited only by the
speed with which the HjO * and OH ions can diffuse through the water
'' ’

to meet each other. On the other hand , reactions between ions of the
same charge and between molecular substances are not instantaneous.
Negative ions repel each other , as do positive ions. The electron clouds
of molecules also repel each other strongly at very short distances.
Therefore, only ions or molecules with very high kinetic energy can
overcome repulsive forces and get close enough to react . In this section ,
we will limit our discussion to reactions between molecules.
Colorless hydrogen gas consists of pairs of hydrogen atoms bonded
together as diatomic molecules. H 2. Violet-colored iodine vapor is also
diatomic, consisting of pairs of iodine atoms bonded together as H mol -
ecules. A chemical reaction between these two gases at elevated tem -
peratures produces hydrogen iodide. HI , a colorless gas. Hydrogen
iodide molecules, in turn , tend to decompose and re -form hydrogen
and iodine molecules, producing the violet gas shown in Figure 2. The
following chemical equations describe these two reactions.
H 2( g ) + I 2 ( g ) * 2 HI (s )
2HI (s ) H 2 ( g ) + I,( g )
Such equations indicate only which molecular species disappear as a FIGURE 1 As NaOH solution is
poured into HCl solution , a very
result of the reactions and which species are produced . They do not
rapid neutralization reaction occurs.
-
show the reaction mechanism, the step - by step sequence of reactions by Excess NaOH turns the phenolph -
which the overall chemical change occurs . thalein indicator pink .

REACTION KINETICS 561

 Although only the net chemical change is directly observable for
most chemical reactions, experiments can often be designed that sug-
gest the probable sequence of steps in a reaction mechanism . Each reac-
tion step is usually a simple process. The equation for each step
represents the actual atoms, ions, or molecules that participate in that
step. Even a reaction that appears from its balanced equation to be a
simple process may actually be the result of several simple steps.
For many years, the formation of hydrogen iodide, as shown in Figure
2, was considered a simple one-step process. It was thought to involve the
interaction of two molecules, H: and U. in the forward reaction and two
HI molecules in the reverse reaction. Experiments eventually showed ,
however , that a direct reaction between Hi and H does not take place.
Alternative mechanisms for the reaction were proposed based on
the experimental results. The steps in each reaction mechanism had to
add together to give the overall equation . Note that two of the species

FIGURE 2 Colorless hydrogen

— —
in the mechanism steps 1 and H:I do not appear in the net equation.
Species that appear in some steps but not in the net equation are known
iodide gas. HI. decomposes into col - as intermediates. ( Notice that they cancel each other out in the follow -
orless hydrogen gas and violet ing mechanisms. ) The first possible mechanism has the following two-
iodine gas. Some of the hydrogen gas step pathway.
and iodine gas will reform I I I .
Step 1 : I2 + ± 2f
Step 2: 2\+ H 2 <r ? 2HI
Ii + Hi ? 2 HI

The second possible mechanism has a three -step pathway.

» 2T
Step 1 : h*
Step 2: F + H 24 HT
Step 3: HiT+ F 2111
12 + Hi 2 HI

The reaction between hydrogen gas and iodine vapor to produce hydro-
gen iodide gas is an example of a homogeneous reaction, a reaction
—
whose reactants ami products exist in a single phase in this case, the gas
phase. This reaction system is also an example of a homogeneous chemi -
cal system because all reactants and products in all intermediate steps
are in the same phase.

Collision Theory
In order for reactions to occur between substances, their particles ( mol -
ecules. atoms, or ions ) must collide. Furthermore, these collisions must
result in interactions. The set of assumptions regarding collisions and
reactions is known as collision theory. Chemists use this theory to inter -
pret many of their observations about chemical reactions.

562 CHAPTER 17
( a) Effective collision, ( b ) Collision ( c) Collision that has
favorable orientation and energy too gentle poor orientation

Consider what might happen on a molecular scale in one step of a

FIGURE 3 Three possible colli -
sion patterns for AB molecules are
homogeneous reaction system. We will analyze a proposed first step in shown. Not even collision produces
a hypothetical decomposition reaction . a chemical reaction.

AB + AB
* * A: + 2 B
According to the collision theory, the two AB molecules must collide in
order to react . Furthermore, they must collide with a favorable orienta -
tion and with enough energy to merge the valence electrons and disrupt
the bonds of the AB molecules. If they do so. a reshuffling of bonds
leads to the formation of the products, one A 2 molecule and two B
atoms. An effective collision is modeled in Figure 3a .
If a collision is too gentle, the two molecules simply rebound from each
other unchanged. This effect is illustrated in Figure 3b. Similarly, a col -
lision in which the reactant molecules have an unfavorable orientation
has little effect . The colliding molecules rebound without reacting. A
collision that has poor orientation is shown in Figure 3c.
A chemical reaction produces new bonds which are formed between
specific atoms in the colliding molecules. Unless the collision brings the
correct atoms close together and in the proper orientation the molecules
,

will not react . For example, if a chlorine molecule collides with the oxygen
end of a nitrogen monoxide molecule, the following reaction may occur.
NO( g ) T Cl 2( g ) > NOCI ( g ) + CI(g )
This reaction will not occur if the chlorine molecule strikes the nitro-
gen end of the molecule.
Thus, collision theory provides two reasons why a collision between
reactant molecules may fail to produce a new chemical species: the col -
lision is not energetic enough to supply the required energy, or the col -
liding molecules are not oriented in a way that enables them to react
with each other.

REACTION KINETICS 563

 Activation Energy
Consider the reaction for the formation of water from the diatomic
gases oxygen and hydrogen according to the following equation .
2H2( g ) + 02(g ) > 2 H:0 ( / )
The enthalpy of formation is quite high: All" = -285.8 kJ / mol at
298.15 k . The free-energy change is also large: AG" = -237.1 kJ / mol.
Why. then , don t oxygen and hydrogen combine spontaneously and
'

immediately to form water when they are mixed at room temperature?

Hydrogen and oxygen gases exist as diatomic molecules. When the
molecules approach each other, the electron clouds repel each other, so
the molecules might not meet. For a reaction to occur , the colliding mol -
ecules must have enough kinetic energy to intermingle the valence elec-
trons. In other words, the bonds of these molecular species must be
broken in order for new bonds to be formed between oxygen and hydro-
gen atoms. Bond breaking is an endothermic process, and bond forming
is exothermic. Even though the net process for forming water is exother -
mic. an initial input of energy is needed to overcome the repulsion forces
that occur between reactant molecules when they are brought very close
together. This initial energy input activates the reaction.
Once an exothermic reaction is started , the energy released is
enough to sustain the reaction by activating other molecules. Thus, the
reaction rate keeps increasing. It is limited only by the time required for
reactant particles to acquire the energy and make
contact . Energy from an outside source may start
Reaction Pathways for Forward exothermic reactants along the pathway of reac-
and Reverse Reactions tion . A generalized reaction pathway for an
exothermic reaction is shown as the forward reac-
Activated complex tion in Figure 4. The minimum amount of energy
needed to activate this reaction is the activation
f energy represented by Eir Activation energy is the
minimum energy required to transform the reactants
.1 Reactants
into an activated complex.
The reverse reaction , decomposition o! water
ci
Products molecules, is endothermic because the water mole -
AE
LU
cules lie at an energy level lower than that of the
i hydrogen and oxygen molecules. The water mole-
Forward Reverse
reaction reaction cules require a larger activation energy before they
(exothermic ) (endothermic) can decompose to re - form oxygen and hydrogen .
The energy needed to activate an endothermic
Course of reaction reaction is greater than that required for the origi -
nal exothermic change and is represented by £,/ in
FIGURE 4 The difference between the activation energies Figure 4. The difference between Ea' and Eu is
for the reverse and forward reactions of a reversible reaction equal to the energy change in the reaction , AE. Ibis
.
equals the energy change in the reaction. AE The quantity for
energy change has the same numerical value for the
AE is the same for both directions, hut is negative for the
exothermic direction and positive lor the endothermic forward reaction as it has for the reverse reaction
direction . but with the opposite sign .

564 CHAPTER 1 7
 The Activated Complex
When molecules collide , some of their high kinetic energy is converted
into internal potential energy within the colliding molecules. If enough
energy is converted , molecules with suitable orientation become acti -
vated . New bonds can then form. In this brief interval of bond breakage
and bond formation , the collision complex is in a transition state. Some
partial bonding exists in this transitional structure. A transitional struc -
ture that results from an effective collision and that persists while old
bonds arc breaking and new bonds are forming is called an activated
complex.
Figure 5 graphically breaks down the reaction pathway of the for -
mation of hydrogen iodide gas into three steps. Beginning with the reac -
tants, Hi and H. a certain amount of activation energy, Eil / t is needed to
form the activated complex that leads to the formation of the interme-
.
diates H: and 21. Then more activation energy. Ea2 is needed to form
the activated complex leading to the intermediates I Id and I . In order
to arrive at the final product , 2 HI . another increase in activation energy
is necessary, as seen bv the highest peak labeled £ , ?.
(

An activated complex is formed when an effective collision raises the

internal energies of the reactants to their minimum level for reaction , as
in Figure 4. Both forward and reverse reactions go through the same acti -
vated complex. A bond that is broken in the activated complex for the
forward reaction must be re-formed in the activated complex for the
reverse reaction . Observe that an activated complex occurs at a high -
energy position along the reaction pathway.
The kinetic-molecular theory states that the speeds and therefore the
kinetic energies of the molecules increase as the
temperature increases. An increase in speed causes
more collisions, which can cause an increase in the Activation Energy Peaks
.
number of reactions However , an increase in the in the Formation of Activated Complexes
reaction rale depends on more than simply the num -
ber of collisions, as Figure 3 illustrates. Hie collisions
between molecules must possess sufficient energy to
form an activated complex or a reaction will not £*3
take place. Raising the temperature of a reaction
provides more molecules that have this activation
energy and causes an increase in the reaction rate. >.
CJi
In its brief existence, the activated complex
has partial bonding that is characteristic of both LU Hjl
reactant and product . It may then re - form the C 21 +I

original bonds and separate back into the reac-

tant particles, or it may form new bonds and sep-
H2 + I2 UE
2 H!
arate into product particles. The activated
complex unlike the relatively stable intermediate
, Course of reaction
products, is a very short - lived molecular complex FIGURE 5 This energy profile graphically shows the forma -
in which bonds are in the process of being broken
-
tion of three activated complexes ( ) during the gas phase
and formed . -
reaction Hi U 2 HI .

REACTION KINETICS 565

 SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.

„ „.
Copy (he energy diagram below, mid label the reactants, products, A £, E , and E ' Determine the value
.
of A£ forward * A /:reverse ' Ea , and Ea'

80

o
E 50

01
<u
c
LU
0

Forward Reverse

SOLUTION The energy level of reactants is always at the left -hand end of such a curve, and the energy
level of products is always at the right -hand end. The energy change in the reaction, A £, is the
difference between these two energy levels. The activation energy differs in the forward and
reverse directions. It is the minimum energy needed to achieve effective reaction in either
direction. As Eir it is the difference between the reactant energy level and the peak in the
curve. As Etl\ it is the difference between the product energy level and the peak in the curve.

80

O
E 50
Products n
>
U) A£
<u
c
LU
0
Reactants

Forward Reverse

AEfonuinl = energy of products - energy of reactants

A /;
“ forward = 50
kJ/mol - 0 kJ/mol = +50 kJ/mol

A E reverse = energy of reactants - energy of products

A E reverse = 0 kJ /mol - 50 kJ/mol = - 50 kJ /mol

Ea - energy of activated complex - energy of reactants

Ea 80 kJ/mol - 0 kJ/mol = 80 kJ / mol
~

£,/ = energy of activated complex - energy of products

E ; = 80 kJ / mol - 50 kJ /mol = 30 kJ/mol
(

566 CHAPTER 1 7
 PRACTICE Answers in Appendix E

1. a. Use the method shown in the sample problem to redraw and

label the following energy diagram. Determine the value of
A E forward A E reverse' £„. and £„'.
'
b. Is the forward reaction shown in the diagram exothermic or
endothermic? Explain your answer.

100

50
o
I-
X
0

t
&
“50

g - 100
LU

-150

Forward Reverse

2. a. Draw and label an energy diagram similar to the one shown in

the sample problem for a reaction in which E l = 125 kJ /mol and
(

EJ = 86 kJ/mol. Place the reactants at energy level zero.

b. Calculate the values of A £forward and AE re\ ersr
c. Is this reaction endothermic or exothermic? Explain your
answer .
3 . a. Draw and label an energy diagram for a reaction in which
Go to go.hrw.com for
Ea = 154 kJ/mol and AE = 136 kJ /mol. more practice problems
b. Calculate the activation energy, £ ,\ for the reverse reaction. that ask you to
determine Ed and A £.
Keyword: HC 6 RXKX

SECTION REVIEW .
6 What is the difference between an activated com-
1. What is meant by reaction mechanism ? plex and an intermediate?
2. What factors determine whether a molecular colli- .
7 Explain why, even though a collision may have
sion produces a reaction? energy in excess of the activation energy, reaction
may not occur.
3. What is activation energy ?
4. What is an activated complex ? Critical Thinking

.
5 How is activation energy related to the energy 8. ANALYZING INFORMATION Which corresponds to
of reaction? the faster rate: a mechanism with a small activa-
tion energy or one with a large activation energy ?
Explain your answer.

REACTION KINETICS 567

 SECTION 2
Reaction Rate
OBJECTIVES
Define chemical kinetics, and
explain the two conditions I he change in concentration of reactants per unit time as a reaction
necessary for chemical proceeds is called the reaction rate. The study of reaction rates is con-
reactions to occur. cerned with the factors that affect the rate and with the mathematical
expressions that reveal the specific dependencies of the rate on concen-
Discuss the factors that influ- tration. The area of chemistry that is concerned with reaction rates and
ence reaction rate. reaction mechanisms is called chemical kinetics.

j Define catalyst, and discuss

two different types.
Rate- Influencing Factors
Relate the order of a reaction For reactions other than simple decompositions to occur, particles must
to the rate law for the come into contact in a favorable orientation and with enough energy for
reaction. .
activation Thus, the rate of a reaction depends on the collision fre -
quency of the reactants and on the collision efficiency. Any change in
Explain and write rate laws reaction conditions that affects the collision frequency, the collision effi-
for chemical reactions. ciency. or the collision energy affects the reaction rate. At least five
important factors influence the rate of a chemical reaction.

Nature of Reactants
Substances vary greatly in their tendencies to react . For example, hydro -
gen combines vigorously with chlorine under certain conditions Under.
SC the same conditions, it may react only weakly with nitrogen. Sodium
/ lNKS. Dftloytd J«d MintMwd fry I Hr and oxygen combine much more rapidly than iron and oxygen under
National kicncr TMcken AuoctttoM
similar conditions. Bonds are broken and other bonds are formed in
For a variety of links related to this
reactions. The rate of reaction depends on the particular reactants and
-
chapter, go to vww. s iimk oiu
bonds involved.
Topic : I actors Affecting
Reaction Rates
SciLinks code: HC60564
* Surface Area
Gaseous mixtures and dissolved particles can mix and collide freely;
w therefore, reactions involving them can occur rapidly. In heterogeneous
reactions, the reaction rate depends on the area of contact of the reac -
tion substances. Heterogeneous reactions involve reactants in two dif -
ferent phases. These reactions can occur only when the two phases are
in contact. Thus, the surface area of a solid reactant is an important fac -
tor in determining rate. An increase in surface area increases the rate of
heterogeneous reactions.
Solid zinc reacts with aqueous hydrochloric acid to produce zinc
chloride and hydrogen gas according to the following equation.

Zn(s) + 2 Y\C\ ( aq ) > ZnCl:( r/</ ) + H2(g)

568 CHAPTER 17
Iliis reaction occurs at the surface of the zinc solid. A cube of zinc mea -
suring 1 cm on each edge presents only 6 cnr of contact area. The same
amount of zinc in the form of a fine powder might provide a contact
area thousands of times greater than the original area. Consequently,
the reaction rate of the powdered solid is much faster.
A lump of coal burns slowly when kindled in air. The rate of burning
can be increased by breaking the lump into smaller pieces, exposing
more surface area. If the piece of coal is powdered and then ignited
while suspended in air. it burns explosively. 1 his is the cause of some
'

explosions in coal mines.

Temperature
An increase in temperature increases the average kinetic energy of the
particles in a substance: this can result in a greater number of effective
collisions when the substance is allowed to react with another sub -
stance. If the number of effective collisions increases, the reaction rate
will increase.
To be effective, the energy of the collisions must be equal to or
greater than the activation energy. At higher temperatures, more parti-
cles possess enough energy to form the activated complex when colli-
sions occur. Thus, a rise in temperature produces an increase in collision
energy as well as in collision frequency.
Decreasing the temperature of a reaction system has the opposite
effect. The average kinetic energy of the particles decreases, so they col-
lide less frequently and with less energy, producing fewer effective col -
lisions. Beginning near room temperature, the reaction rates of many
common reactions roughly double with each 10 K ( 10 C ) rise in tem -
perature. This rule of thumb should be used with caution, however. The
'

actual rate increase with a given rise in temperature must be deter -

mined experimentally.

Concentration
Pure oxygen has five times the concentration of oxygen molecules that
FIGURE 6 Carbon burns faster in
air has at the same pressure: consequently, a substance that oxidizes in pure oxygen ( a ) than in air ( b )
air oxidizes more vigorously in pure oxygen. For example, in Figure 6, because the concentration of the
the light produced when the lump of charcoal is burned in pure oxygen reacting species. G:. is greater.
is much more intense than the light produced when the charcoal lump
is heated in air until combustion begins. The oxidation of charcoal is a
heterogeneous reaction system in which one reactant is a gas. The reac -
tion rate depends not only on the amount of exposed charcoal surface
but also on the concentration of the reacting species, 0:
In homogeneous reaction systems, reaction rates depend on the con-
centration of the reactants. Predicting the mathematical relationship
between rate and concentration is difficult because most chemical reac -
tions occur in a series of steps, and only one of these steps determines
the reaction rate. If the number of effective collisions increases, the rate

REACTION KINETICS 569

 •1 *
\
/

( a) (b )

FIGURE 7 The number of mole -

cules of reading species affects the
( c)
#
* (d)

number of possible collisions and increases as well. In general, an increase in rate is expected if the con-
therefore the reaction rate. centration of one or more of the reactants is increased, as depicted by
the model in Figure 7. In the system with only two molecules, shown in
Figure 7a, only one collision can possibly occur. When there are four
molecules in the system, as in Figure 7b, there can be four possible col -
lisions. Under constant conditions, as the number of molecules in the
system increases, so does the total number of possible collisions
between them. Figure 7c and d show a five- and eight -molecule system,
allowing six and sixteen possible collisions, respectively. Lowering the
concentration should have the opposite effect. The actual effect of con-
centration changes on reaction rate, however, must be determined
experimentally.

Presence of Catalysts
Some chemical reactions proceed quite slowly. Sometimes their reac -
tion rates can be increased dramatically by the presence of a catalyst. A
catalyst is a substance that changes the rate of a chemical reaction w ith -
out itself being permanently consumed. The action of a catalyst is adled
catalysis. The catalysis of the decomposition reaction of hydrogen per -
oxide bv manganese dioxide is shown in Figure 8. A catalyst provides an
alternative energy pathway or reaction mechanism in which the
potential-energy barrier between reactants and products is lowered.
NfflroqenPwnidetfi
****••ci
AJ The catalyst may be effective in forming an alternative activated com -
- ilvr ~ =r» plex that requires a lower activation energy — as suggested in the ener -
gy profiles of the decomposition of hydrogen peroxide, ICO:, shown in
gig
* Figure 9— according to the following equation.

2H:0:( / » > 02( g) + 2 H:0( / )

FIGURE 8 The reaction rate of
the decomposition of hydrogen per - Catalysts do not appear among the final products of reactions they
oxide. HTCKcan be increased by accelerate. They may participate in one step along a reaction pathway
using a catalyst. The catalyst used and be regenerated in a later step. In large-scale and cost -sensitive reac -
here is manganese dioxide, MnCKa tion systems, catalysts are recovered and reused. A catalyst that is in the
black solid. A 30% H:C): solution is same phase as all the reactants and products in a reaction system is called
added dropwise onto the MnO:in
a homogeneous catalyst. When its phase is different from that of the reac -
the beaker and rapidly decomposes
tants. it is called a heterogeneous catalyst. Metals are often used as
to 0: and H:C). Both the oxygen and
water appear as gases because the heterogeneous catalysts. The catalysis of many reactions is promoted by
energy released by the reaction caus- adsorption of reactants on the metal surfaces, which has the effect of
es much of the water to vaporize. increasing the concentration of the reactants.

570 CHAPTER 1 7
 Comparison of Pathways for the Decomposition FIGURE 9 The activation energy
of H202 by Various Catalysts lor a chemical reaction can he
reduced by adding an appropriate
catalvst.

£, = 75 Uncatalyzed -

Chemically Homogeneous
£,= 58
catalyzed (I') processes
o
§ f,= 4 Enzyme
catalyzed

Q)
C
LU

Heterogeneous
process (Mn02)

Course of reaction

Rate Laws for Reactions

Chemistry in Action
The relationship between the rate of a reaction and the concentration Go to go.hrw.com lor a full -length
of one reactant is determined experimentally by first keeping the con - article on using spectroscopy to
centrations of other reactants and the temperature of the system con- measure reaction kinetics.
stant . Then the reaction rate is measured for various concentrations of Keyword: HC 6 RXKX
the reactant in question. A series of such experiments reveals how the
concentration of each reactant affects the reaction rate.
I lydrogen gas reacts with nitrogen monoxide gas at constant volume
and at an elevated constant temperature, according to the following
equation.

2H2(g) + 2NO(g) N 2(U ) + 2 H:0(g )

Four moles of reactant gases produce three moles of product gases:

thus, the pressure of the system diminishes as the reaction proceeds. The
rate of the reaction can. therefore, be determined by measuring the
change of pressure in the vessel with time.
Suppose a series of experiments is conducted using the same initial
concentration of nitrogen monoxide but different initial concentrations
of hydrogen. The initial reaction rate is found to vary directly with the
hydrogen concentration: doubling the concentration of H2 doubles the
rale, and tripling the concentration of H2 triples the rate. If R represents
the reaction rate and |H:] is the concentration of hydrogen in moles per

REACTION KINETICS 571

 liter, the mathematical relationship between rate and concentration can
be expressed as follows.

[ H:]
* «

The is a symbol that is read “is proportional to."

Chemistry in Action Now suppose the same initial concentration of hydrogen is used but
Explosives the initial concentration of nitrogen monoxide is varied. The initial reac -
In a tiny fraction of a second, the reac- tion rate is found to increase fourfold when the NO concentration is
tions of explosives such as nitroglyc -
erin, trinitrotoluene (TNT), and
.
doubled and ninefold when the concentration of NO is tripled Thus, the
reaction rate varies directly with the square of the nitrogen monoxide
dynamite are over. These materials are
primarily organic substances containing concentration, as described by the following proportion.
mostly carbon, hydrogen, oxygen, and
nitrogen atoms held together by rela - Roc [ NO ] 2
tively weak bonds. When " set off,"
explosive materials experience rapid Because K is proportional to \ U 2 ] and to [ NO ] 2, it is proportional to
decomposition. The released elements
immediately react to form gaseous N2,
their product.
CO, C 02, and N02. The bonds in these
small molecules are much stronger Roc [ H:][NO ]2
than those in the original explosive
material, and so an enormous amount
of energy is released. In addition, the
By introduction of an appropriate proportionality constant A , the .
expression becomes an equality.
sudden formation of gaseous material
causes a tremendous increase in pres-
sure that provides the force to demol- R = A|H:] [ NO ] 2
ish an unwanted building or break
rocks for building roads. An equation that relates reaction rate ami concentrations of reactants is
called the rate law for the reaction. It is applicable for a specific reaction
at a given temperature. A rise in temperature increases the reaction
rates of most reactions. The value of A usually increases as the tempera -
ture increases, but the relationship between reaction rate and concen -
tration almost always remains unchanged.

Using (he Rate Law

The general form for the rate law is given by the following equation

R = A[ A ]"[B|"'

.
The reaction rate is represented by R A is the specific rate constant,
and |A ] and [ B| represent the molar concentrations of reactants. The
respective powers to which the concentrations are raised are represented
bv n and in. The rate law is applicable for a specific reaction at a given set
oi conditions and must be determined from experimental data.
The / lower to which a reactant concentration is raised is called the
order in that reactant . The value of n is said to be the order of the reac -
,
tion with respect to [ A ], so the reaction is said to be “/ j h order in A .’*
Similarly, for the value of in , the reaction is said to be order in B. ‘
The orders, or powers, n and in , are usually small integers or zero. An
order of one for a reactant means that the reaction rate is directly pro-
portional to the concentration of that reactant. An order of two means

572 CHAPTER 17
that the reaction rate is directly proportional to the square of the reac-
tant . An order of zero means that the rate does not depend on the con -
centration of the reactant , as long as some of the reactant is present . The
sum of all of the reactant orders is called the order of the reaction , or
overall order. The overall order of the reaction is equal to the sum of the
reactant orders, or n + m. Some examples of observed rate laws that
have been derived experimentally are shown below.Some of these reac-
tions involve nitrogen oxides, which are highly reactive gases that con -
tribute to the formation of smog that can blanket an entire city, as
shown in Figure 10.

3NO(g ) » N 20( g ) + NO:( # ) R = k [ NO|2

second order in NO.
second order overall

NO:(#) + CO( g ) NO(g ) + C02( g ) R = Jt [ NOj2

second order in NO:,
zero order in CO,
second order overall

2 N 02(g ) > 2NO( g ) + 02( g ) R = Jt [ NO:]2

second order in N 02.
second order overall

2H 2O2( 0<7 ) » 2 H 20( / ) + 02( g ) R = A [ H:02 )

'

first order in H 202,

first order overall

It is important to understand that the orders in the rate law may or may
not match the coefficients in the balanced equation . These orders must
be determined from experimental data .

Specific Rate Constant

The specific rate constant ( A: ) is the proportionality constant relating the
rate of the reaction to the concentrations of reactants. It is important to
remember the following about the value of A;:

1 . Once the reaction orders ( powers ) arc known , the value of A. must be
determined from experimental data.
2. The value of k is for a specific reaction; k has a different value for
other reactions, even at the same conditions.
3. TIK* units of k depend on the overall order of the reaction. FIGURE 10 A cloud of polluted
4. The value of k does not change for different concentrations of reac- air. commonly known as smog, set -
tles over a city. Smog is common in
tants or products. So, the value of k for a reaction remains the same
industrialized areas, where highly
throughout the reaction and does not change with time. reactive gases and particulate matter
5. The value of k is for the reaction at a specific temperature : if we are released into the air.
increase the temperature of the reaction , the value of k increases.
6. The value of k changes ( becomes larger ) if a catalyst is present .

REACTION KINETICS 573

 SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of this chapter.

Three experiments that have identical conditions were performed to measure the initial rate of
the reaction
2HI(g) «
H2< ) + l2( g )
The results for the three experiments in which only the HI concentration was varied are as follows:

Experiment I HI | (M ) Kate ( M/s )

0.015 l.l x If)-1-
0.030 4.4 x 10 1
- '

3 0.045 9.9 x nr -1
W rite the rate law for the reaction. Find the value and units of the specific rate constant.

SOLUTION
1 ANALYZE The general rate law for this reaction has the form /< = A [ HI|". We need to deduce the value
of the power n.

2 PLAN k
Find the ratio of the reactant concentrations between two experiments,such as 1 and i2' 1111
[m I , *
Then see how the ratio of concentration affects the ratio of rates, .
, £*

„ . . [HI ],11 0.030 M R, 1

4.4 x IQ - M/ s
'

3 COMPUTE C oncentration ratio:

, =
|HI ] 0.015 M
= 2.0: rate ratio: —
/? , 1.1 x 10-3 M/s
= 4.0
.
Thus, when the concentration changes bv a factor of 2 the rate changes by a factor of 4, or
22, so the rate law is R = A:[ HI ] 2.
To find the value of A', we can rearrange the rate law and substitute known values for any
one experiment. Do the following for Experiment I:
R 1.1 x IQ-1 M/s
" " = 4.9 M-Is- 1
(H i p ( 0.015 M )2

4 EVALUATE By comparing items I and 3 in the table, we see that when [ M l ] is tripled, the rate changes
.
by a factor of 9 or 32. This rate change confirms that the order is 2. The same value of A can
be calculated from any other experiment. Thus, the rate law and A are correct .

PRACTICE Answers in Appendix E

1 . For the reaction 3 A > C, the initial concentration of A was 0.2

M and the reaction rate was 1.0 M /s. When [ A ] was doubled, the
reaction rate increased to 4.0 M/s. Determine the rate law for the
reaction.
Go to go.hrw.com for
2. The rate law for a reaction is found to be rate = A [ X ] \ By what more practice problems
factor does the rate increase if |X ] is tripled? that ask you to
determine rate law and
rate constant.
Keyword: HC 6 RXKX

574 CHAPTER 1 7
 SAMPLE PROBLEM C For more help, go to the Math Tutor at the end of this chapter.
Three experiments were performed to measure the initial rate of the reaction
A+B C
Conditions were identical in the three experiments, except that the concentrations of reactants varied. The
results are as follows:

Experiment IA 1 ( M ) IB| < M ) Rate ( M /s )

1.2 2.4 8.0 x 108
2 1.2 1.2 4.0 x ur8
3 3.6 2.4 7.2 x IQ-7

Write the rate law for the reaction. Find the value and units of the specific rate constant .

SOLUTION
1 ANALYZE The general rate law for this reaction has the form R = k [ A|"[ B ]"'. We need to calculate the
values of the powers n and / / / .

2 PLAN Find the ratio of the reactant concentrations between two experiments that have the same
[ A ] but different [ B ]. Then, see how this ratio affects the ratio of rates, this ratio of rates
lets us find the value of in. A similar approach of comparing two experiments that have the
same [ B ] but a different [ A ] lets us find the value of n.

3 COMPUTE First compare Experiments 1 and 2, which have the same [ A ] , to find m:
, 8.0 x l (r8 M /s
„
Concentration
.
ratio:
——
[ B ] 2.4 M
[ B]2 = 1.2 M
= 2.0; rate ratio: *1
Rl — 4.0 x 10-8 M /s
= 2.0
Thus. when the concentration of B changes by a factor of 2. the rate changes by a factor of
2. or 2 l . So, m is 1 . and the reaction is first order in B.
Then . compare Experiments 1 and 3. which have the same [ B|, to find n:

— ,,
[ Al 3.6 M
Concentration ratio: 7- =
[ A ) 1.2 M
= 3.0: rate ratio:
7.2 x 10-7 M/s
8.0 x 10-8 M/s
= 9.0—
Thus, when the concentration of A changes by a factor of 3, the rate changes by a factor of
9. or 3 . So, n is 2, and the reaction is second order in A .
*

The rate law is R = A. [ A ):[ B|.

To find the value of A:, we can rearrange the rate law and substitute known values for any
one experiment . Do the following for Experiment 1 :
R 8.0 x 10~8M /s
~ ~
- = 2.3 x 10 s M V1
" '

[ A ]-[ B ] ( 1.2 M ) ( 2.4 M)

4 EVALUATE The same value of k can be calculated from the data for any other experiment. So. the rale
law and the calculation of k are correct .

REACTION KINETICS 575

 Rate Laws and Reaction Pathway
The form of ihe rate law depends on the reaction mechanism . For a
reaction that occurs in a single step, the reaction rate of that step is
proportional to the product of the reactant concentrations, each of
which is raised to its stoichiometric coefficient. For example, suppose
one molecule of gas A collides with one molecule of gas B to form two
molecules of substance C, according to the following equation.
A+B > 2C
One particle of each reactant is involved in each collision . Thus, dou -
bling the concentration of either reactant will double the collision fre-
quency. It will also double the reaction rate for this step. Therefore, the
rate for this step is directly proportional to the concentration of A and
B. The rate law for this one-step forward reaction follows.

^ forward ~
^ fnnxnhi\^ II ® 1
Now suppose the reaction is reversible. In the reverse step, two mol -
ecules of C must decompose to form one molecule of A and one of B or
2C » A + B.
Thus, the reaction rate for this reverse step is directly proportional to
[ C| x ( C ) . The rate law for the reverse step is Rreverse = k reverse in 2.
The pow er to which the molar concentration of each reactant is raised
in the rate laws above corresponds to the coefficient for the reactant in
the balanced chemical equation. Such a relationship holds only if the
reaction follows a simple one-step path , that is, if the reaction occurs at
the molecular level exactly as written in the chemical equation .
If a chemical reaction proceeds in a sequence of steps, the rate law is
determined from the slowest step because it has the lowest rate. This
-
slowest rate step is called the rate-determining step for the chemical
reaction .
Consider the reaction of nitrogen dioxide and carbon monoxide.

FIGURE 11 This diagram is a

N 02(g ) + CO( g ) * NO(g ) + C02(g )
representation of Step l in the reac - The reaction is believed to be a two-step process represented by the fol -
tion of nitrogen dioxide and carbon lowing mechanism .
monoxide. Notice the formation of
Ihe intermediate species NO , alter Step 1 : N 02 + N 02 -> NO, 4- NO slow
two molecules of NCT collide. Step 2: ,
NO + CO - 4NO 2 + co2 fast
In the first step shown in Figure 11, two molecules of N 02

a
,

,
collide, forming the intermediate species NO . This molecule
then collides with one molecule of CO and reacts quickly to
produce one molecule each of NO: and CO ?. The first step is
the slower of the two and is therefore the rate-determining
step. We can write the rate law from this rate-determining
step, which has two molecules of N 02 as the reactants.
R = k \ NO:]2
Hie rate law does not include [ CO ] because CO reacts after
-
the rate determining step and does not affect the rate.

576 CHAPTER 17
SAMPLE PROBLEM For more help, go to the Math Tutor at the end of this chapter.

Nitrogen dioxide and fluorine react in the gas phase according to the following equation.
2NO z ( g ) + F2(J? ) » 2N02F(£ )
A proposed mechanism for this reaction follows.
Step I: N02 + F2 -> NO 2 F + F ( slow )
Step 2: F + N02 - * NO2F ( fast )

Identify the rate-determining step, and write an acceptable rate law.

SOLUTION If we combine these two steps, the intermediate, F. cancels out and we are left with
.
the original equation The first step is the slower step, and is considered the rate-
determining step. We can write the rate law from this rate-determining step.
R = k [NOjfFj

SAMPLE PROBLEM E
A reaction involving reactants X and V was found to occur by a one-step mechanism:
X + 2Y XY 2. Write the rate law for this reaction, and then determine the effect
of each of the follow ing on the reaction rate:
a . doubling the concentration of X
b. doubling the concentration of Y
c. using one- third the concentration of Y

SOLUTION Because the equation represents a single -step mechanism, the rate law can be written
from the equation (otherwise, it could not be). The rate will vary directly with the concentra-
tion of X. which has an implied coefficient of 1 in the equation. And the rate will vary direct -
ly with the square of the concentration of Y, which has the coefficient of 2: R = fc [ X ][ Y ]2.
a. Doubling the concentration of X will double the rate ( R = A [ 2Xj[ Yp ).
b. Doubling the concentration of Y will increase the rate fourfold ( R = A [ X ] ( 2 Y ]:).
c. Using one - third the concentration of Y will reduce the rate to one -ninth of its original
jY .
value ( /? = Jt[X ][ ]2 )

PRACTICE Answers in Appendix E

1 . The rate of a hypothetical reaction involving L and M is found to

double when the concentration of L is doubled and to increase
fourfold when the concentration of M is doubled. Write the rate
law for this reaction.

.
2. At temperatures below 498 K the following reaction takes place.
NO:U) + CO( g) > C02(g) + NO(g) —( I ji i
Go to go.hrw.com for
Doubling the concentration of N02 quadruples the rate of CO: more practice problems
formed if the CO concentration is held constant. However, dou- that ask you to
bling the concentration of CO has no effect on the rate of C02 determine rate laws and
formation. Write a rate -law expression for this reaction. effects on reaction rates.
Keyword: HC 6 RXKX

REACTION KINETICS 577

 QuidiAB <$> < ! Wear safety goggles and an apron.

Materials
Factors Influencing Reaction Rate • Bunsen burner
• paper ash
Question 3. To one test tube, add 10 mL of • copper foil strip
How do the type of reactants, vinegar; to a second, add 5 mL • graduated cylinder, 10 mL
surface area of reactants, of vinegar plus 5 mL of water; • magnesium ribbon
concentration of reactants, and to a third, add 2.5 mL of • matches
and catalysts affect the rates vinegar plus 7.5 mL of water. • paper clip
of chemical reactions ? To each of the three test tubes,
• sandpaper
add a 3 cm piece of magne-
sium ribbon. • steel wool
Procedure • 2 sugar cubes
Remove all combustible material 4. Using tongs, hold a sugar cube • white vinegar
from the work area . Wear safety and try to ignite it with a
goggles and an apron. Record all • zinc strip
match. Then try to ignite it in a
your results in a data table. burner flame. Rub paper ash • 6 test tubes, 16 x 150 mm
on a second cube, and try to • tongs
1. Add 10 mL of vinegar to each
of three test tubes. To one test ignite it with a match.
tube, add a 3 cm piece of
magnesium ribbon; to a sec - Discussion
ond, add a 3 cm zinc strip; and
to a third, add a 3 cm copper
1. What are the rate-influencing
strip. (All metals should be the factors in each step of the
same width.) If necessary, pol - procedure ?
ish the metals with sandpaper 2. What were the results from
until they are shiny. each step of the procedure?
2. Using tongs, hold a paper clip How do you interpret each
in the hottest part of the burn- result ?
er flame for 30 s. Repeat with a
ball of steel wool 2 cm in
diameter.

SECTION REVIEW 4. What is meant by a rate law for a chemical

1. What is studied in the branch of chemistry that is reaction? Explain the conditions under which
known as chemical kinetics? a rate law can be written from a chemical
equation. When can a rate law not be written
2. List five important factors that influence the rate from a single step?
of chemical reactions.
Critical Thinking
3. What is a catalyst ? Explain the effect of a catalyst 5. RELATING IDEAS Using the ideas of reaction ki-
on the rate of chemical reactions. How does a netics, explain the purpose of food refrigeration.
catalyst influence the activation energy required
by a particular reaction?

578 CHAPTER f 7
Chemistry in Action
Catalytic Converters
To see an important example of het- Catalytic converters use pre-
erogeneous catalysis, you do not cious metal catalysts to change
need to look any farther than the the gases coming from the
streets near your home. The catalytic engine into less harmful gases.
converter; an important part of a A combination of rhodium and
vehicle's exhaust system, uses metal platinum, and sometimes palla -
catalysts to reduce harmful gaseous dium, is used to convert nitro-
pollutants. gen compounds back into N2 and 02. The ceramic honeycomb inside a cat -
In an automobile engine, hydrocar - This combination also converts CO alytic converter is coated with a metal
bon molecules in gasoline or diesel into C 02 and converts VOCs into C 02 catalyst.
fuel undergo a combustion reaction and water. The catalysts need 02
with oxygen from air to make carbon from the air and temperatures above Catalysts that work at lower temper -
dioxide, C 02, and water. The correct approximately 500°F to work proper - atures would reduce an automobile's
stoichiometric ratio of fuel to oxygen ly. The temperatures are achieved emission during the first few minutes
is required for the fuel to be com- from the normal operation of the car of operation. Other gases that are
pletely burned in the reaction. engine. However, until the car engine emitted by cars may also pose prob-
Additional reaction products are reaches the temperatures needed for lems for the environment. Nitrous
formed when not enough oxygen or the catalysts to work, CO, NOx, and oxide, N20, can be formed from the
excess oxygen is present. These prod- VOCs will be released into the air by incomplete reduction of NOx in cat-
ucts include carbon monoxide, CO, the automobile. alytic converters. Unlike the NOx
and NOx compounds, such as nitric The interior structure of a catalytic gases, N20 can travel to the upper
oxide, NO, and nitrogen dioxide, N02. converter is usually made of a atmosphere, where it can destroy
There is also leftover unburned fuel, ceramic honeycomb with a surface ozone. As a greenhouse gas, N20 is
which is called a volatile organic coating of metal catalyst particles. more that 300 times more potent
compound (VOC). The honeycomb has many holes for than C 02.
The Clean Air Act, enacted in the gases to pass through and pro-
1990, regulates automobile emis- vides a large surface area for the Questions
sions of CO, NOx, and VOCs. Without metal to be deposited on. A large 1. Why do you think a heteroge-
a catalytic converter, a car would surface area is needed to maximize neous catalyst is used instead of
release all of the byproducts of the reactions that occur during het- homogeneous catalyst in a cat-
incomplete combustion into the erogeneous catalysis because the alytic converter ?
atmosphere. In addition to being transformation of the gas molecules
harmful themselves, NOx com - occurs at the surface of the metal. 2. Nitrous oxide, N20, actually has
pounds, CO, and VOCs react with Up to 90% of CO, NOx, and VOCs beneficial uses, despite its role as
sunlight to make ozone, 03. In the are typically eliminated from auto- a greenhouse gas. Can you name
lower atmosphere, ozone is a major mobile exhaust by a catalytic con - ,
a beneficial use of N 0 ?
part of photochemical smog. NOx verter. Although catalytic converters
gases can also mix with rainwater to are beneficial to our environment,
produce acid rain. they could still be improved.

REACTION KINETICS 579

 CHAPTER HIGHLIGHTS
The Reaction Process
I Vocabulary •The step-by -step process hv which an overall chemical reaction
reaction mechanism occurs is called the reaction mechanism.
intermediate •In order for chemical reactions to occur, the particles of the
homogenous reaction reactants mustcollide.
collision theory •Activation energy is needed to merge valence electrons and to
activation energy loosen bonds sufficiently for molecules to react.
activated complex •An activated complex is formed when an effective collision
between molecules of reactants raises the internal energy to
the minimum level necessary for a reaction to occur.

Reaction Rate
I Vocabulary • Ilie rate of reaction is influenced by the following factors:
reaction rate heterogeneous nature of reactants, surface area, temperature, concentration of
chemical kinetics catalyst reactants, and the presence of catalysts .
rate law
heterogeneous
reactions order
•The rates at which chemical reactions occur can sometimes be
experimentally measured and expressed in terms of math-
catalyst rate - determining step ematical equations called rate laws.
catalysis •Rate laws are determined by studying how reaction rate
homogeneous depends on concentration.
catalyst

580 CHAPTER 11
 CHAPTER REVIEW

The Reaction Process PRACTICE PROBLEMS

SECTION 1 REVIEW 6. For each of the energy diagrams provided
1. a. What is the collision theory? helow. label the reactants, products, A£, Etp and
b. According to this theory, what two conditions Ea\ Also determine the values of AE for the
must be met for a collision between reactant forward and reverse reactions, and determine
molecules to be effective in producing new the values of E l and Etl' . ( Hint: See Sample
(

chemical species? Problem A . )

2. a. What condition must be met for an activated a.
complex to result from the collision of reac -
tant particles?
b. Where, in terms of energy, does the activated
complex occur along a typical reaction
_
o
80

60

pathway ? | 40
.
3 In a reversible reaction, how does the activation
energy required for the exothermic change ^
&
a»
c
20

0
compare with the activation energy required LU

for the endothermic change ? -20

4. Would you expect the following equation to
represent the mechanism bv which propane, <
Forward Reverse
C3Hs, burns? Why or why not ?
b.
*

C3H8( ) + 502(g) > 3C02(g) + 4H:0( g )

*
5. The decomposition of nitrogen dioxide
20
2N02 -
> 2NO + 02 occurs in a two step
sequence at elevated temperatures. The first ? 0
step is NO: > NO + O. Predict a possible E
second step that, when combined with the first 3 - 20
>>
step, gives the complete reaction.
Sc -4 0
LU

-60

>
Forward Reverse

c.

70 L
60
o 50 -

! «-
-S. ^>
30
' 0)
20
c 10
LU
0

-
Forward Reverse

REACTION KINETICS 581

 CHAPTER REVIEW

7. Draw and label energy diagrams that depict the c. If the initial concentrations of both A and B
following reactions, and determine all remaining are 0.30 M, at what initial rate is C formed?
values. Place the reactants at energy level zero. d. What is the order of the reaction with
a. AEtonvard = -10 kJ/mol Ea’ = 40 kJ/mol respect to A ?
b. nvanl = -95 kJ /mol E l = 20 kJ/mol e. What is the order of the reaction with
AEf () (

c. A E reverse = -40 kJ / mol £ / = 30 kJ /mol respect to B ?

Reaction Rate MIXED REVIEW

SECTION 2 REVIEW .
13 Draw' and label energy diagrams that depict the
8. Define the rate-determining step for a chemical following reactions, and determine all remaining
reaction. values. Place the reactants at energy level zero,
9. Write the general equation for the rate law, and a. AE = +30 kJ/mol E ; = 20 kJ /mol
(

label the various factors. b. AE = -30 kJ/mol En = 20 kJ/mol

14. A particular reaction is found to have the fol -
PRACTICE PROBLEMS lowing rate law.
K = k [ A ] [ B }2
10. a. Determine the overall balanced equation for
How is the rate affected bv each of the follow -
a reaction that has the following proposed
ing changes ?
mechanism, and write an acceptable rate law.
a. The initial concentration of A is cut in half.
(Hint: See Sample Problem C.)
b. The initial concentration of B is tripled.
Step 1: Bi + B2 E3 + D slow
c. The concentration of A is doubled, but the
Step 2: E 3+ A » B 2 + C2 fast concentration of B is cut in half.
b. Give the order of the reaction with respect to
d. A catalvst is added.
each reactant. J

c. What is the overall order of the reaction?

.
15 For each of the following pairs, choose the sub -
stance or process that you would expect to react
.
11 A reaction that involves reactants A and B is
more rapidly.
found to occur in the one -step mechanism:
a. granulated sugar or powdered sugar
2A + B » A -> B. Write the rate law for this
b. zinc in HCI at 298.15 K or zinc in HCI at
reaction, and predict the effect of doubling the
320 K
concentration of either reactant on the overall
c. 5 g of thick platinum wire or 5 g of thin plati-
.
reaction rate ( Hint: See Sample Problem C ) . num wire
12. A chemical reaction is expressed by the bal -
16. The following data relate to the reaction
anced chemical equation A + 2B C. Three
'

A+B C. Find the order with respect

reaction-rate experiments yield the following
data.
to each reactant .
[ A ] (M) [ B ] (M ) Rate (M/ s)
Experiment Initial Initial Initial rate of
number [A] [B] formation of C 0.08 0.06 0.012
0.08 0.03 0.006
1 0.20 M 0.20 M 2.0 x 10-4 M/min
0.04 0.06 0.003
2 0.20 M 0.40 M 8.0 x 10^ M/ min
3 0.40 M 0.40 M 1.6 x 10 3 M/min

a. Determine the rate law for the reaction.

b. Calculate the value of the specific rate
constant .

582 CHAPTER 1 7
 CHAPTER REVIEW

CRITICAL THINKING ALTERNATIVE ASSESSMENT

17. Predicting Outcomes The balanced equation 22. Boilers are sometimes used to heal large build-
for a rapid homogeneous reaction between two ings. Deposits of CaCOv MgC03, and FeC03
gases is as follows: 4A + B 2C + 2D. can hinder the boiler operation. Aqueous solu-
Because the simultaneous collision of four mol - tions of hydrochloric acid are commonly used to
ecules of one reactant with one molecule of the remove these deposits.Hie general equation for
other reactant is extremely improbable, what the reaction is written below.
would you predict about the nature of the reac- \1C03(.s ) + 2H30*( fl</ )
tion mechanism for this reaction system ?
*
M2+(«f/ ) + 3H:0( / ) + C02U)
18. Evaluating Ideas In the equation. VI stands for Ca. Mg, or Fe.
a. I low can you justify calling the reaction Design an experiment to determine the effect of
pathway that is shown in Figure 4 the various HCI concentrations on the rates of this
minimum-energy pathway for reaction? reaction. Present your design to the class.
.
b What significance is associated with the
maximum-energy region of this minimum-
energy pathway ?
19. Applying Models Explain why there is a dan-
ger of explosion in places such as coal mines,
sawmills, and grain elevators, where large
i Graphing Calculator
Reaction Orders
Go to go.hrw.com for a graphing calculator
amounts of dry. powdered combustible materi - exercise that asks you to calculate the order
als are present. of a reaction from the reaction rates and
concentrations.
20. Evaluating Methods What property would
you measure to determine the reaction rate for 'K. Keyword: HC6 RXKX
the following reaction ? Justify your choice.
2N02(g) 264
» N (g)

RESEARCH & WRITING

21. Look for situations around your house in which
processes are speeded up by an increase in
temperature or slowed down by a decrease in
temperature. Make a list , and discuss the differ -
ent processes.

REACTION KINETICS 583

nrI
Math Tutor WRITING RATE LAWS

Factors such as surface area and temperature affect the rate of reactions because they
affect the frequency and energy of collisions between particles. The concentrations of
reactants can also affect the frequency of collisions. If other factors are kept constant,
the rates of most chemical reactions will be determined by the concentrations of reac -
tants. Thus, it is possible to write an equation called a rote law that relates the rate of a
reaction to the concentrations of reactants.

SAMPLE
Fluorine gas reacts with chlorine dioxide according to the following equation.
F2 < £ ) + 2CI02< ) «
> 2FCI02(g)
Use the following experimental data to write a rate law for this reaction.

Trial Concentration of F 2 Concentration of CI02 Rate (mol / L * s)

0.10 A# 0.10 M 1.1 x 5 ur
0.20 M 0.10 XI 2.2 x 10- ?
3 0.10 M 0.20 Xi 2.2 x KT3
4 0.20 XI 0.20 Xi 4.4 x 1(T3

To write the rate law. first examine the data to see how the rate of reaction changes as the
concentrations of the reactants change.
• When [ F:| doubles and [ CI02] remains constant, the rate of reaction doubles from 1.1 x
10 ' mol/ L * s to 2.2 x 10 ' mol/L * s. So. the rate is directly proportional to [F2 ]. or R a [F2].
“

• When [ C102 ] doubles and [F2 ] remains constant, the rate of reaction also doubles from
1.1 x 10 ' mol/L * s to 2.2 x 10 3 mol / L * s. So. the rate is directly proportional to [ C102], or
* "

R a [ CIO:|.
• Because rate is proportional to both |F:| and |CIO:]. you can write the rate law
R = [ F2 ][ C102 ]. The data from Trial 4 help confirm the rate law because when both |F:]
*
and |C'I02| double, the rate increases by a factor of four, from 1.1 x 10~3 mol/L « s to
4.4 x 10 3 mol/L * s.
“

PRACTICE PROBLEMS
I. Nitrogen monoxide and oxygen react to .
2 Hydrogen reacts with ethvne. C2H 2. to pro-
produce nitrogen dioxide according to the . .
duce ethane G>H6 as shown below:
following equation: 2U2(g ) + C2H2( g ) > C: ( ) «
02(g) + 2NO(g) > 2NO2 ( g ) Use the data in the following table to write a **
Use the data in the following table to write a rate law for this reaction.
rate law for this reaction.

Trial [02] [NO ] Reaction Rate Trial [H2] [ C 2H 2 ] Reaction Rate

(mol / L * s) (mol / L * min)
1 i .2ox 2 xi 1.40 x U ) 2 XI
~
330 x ltr 3 1 0.20 XI 0.20 XI 1.5 x 10 4
"

i 2.40 x Hr 2 XI 1.40 x l(r 2 XI 6.60 x 10“3 2 0.40 Xi 0.20 XI 3.0 x KT4

3 1.20 X 10 2 XI 2.80 x lfr 2 M 1.32 x lO 2
"
3 0.20 XI 0.40 M 1.5 x Hr 4

584 CHAPTER 17
Answer the following items on a separate piece of paper. 7. In a graph of how energy changes with reaction
MULTIPLE CHOICE
progress, the activated complex appears at the
A . left end of the curve.
.
1 The sequence of steps that occurs in a reaction B. right end of the curve.
process is called the C . bottom of the curve.
A . order of the reaction .
D. peak of the curve.
B. rate law.
C . overall reaction . 8. Ilie slowest step in a mechanism is called
D. reaction mechanism. A. the rate -determining step.
B. the uncatalyzed reaction.
2. To be effective, a collision requires
C. the activation step.
A . enough energy only.
D . None of the above
B . favorable orientation only.
C. enough energy and a favorable orientation . 9. A certain reaction is zero order in reactant A
D . a reaction mechanism . and second order in reactant B. What happens
to the reaction rate when the concentrations of
3. How does the energy of the activated complex both reactants are doubled ?
compare with the energies of the reactants and A . The reaction rate remains the same.
products? B. The reaction increases by a factor of two.
A . It is lower than both the energy of the reac- C. flic reaction rate increases by a factor of lour.
tants and the energy of the products. .
D The reaction rate increases by a factor of eight.
B. It is lower than the energy of the reactants
but higher than the energy of the products. SHORT ANSWER
C . It is higher than the energy of the reactants 1 0. Two molecules collide but bounce apart
but lower than the energy of the products. unchanged. What two reasons could account for
D. It is higher than both the energy of the reac - their failure to react ?
tants and the energy of the products. 11 . Sketch a diagram that shows how the energy
4. If a collision between molecules is very gentle, changes with the progress of an endothermic
the molecules are reaction . Label the curve “ Reactants,”
“ Products,” and "Activated complex.” On the
A . more likely to be oriented favorably.
B. less likely to be oriented favorably.
same diagram , sketch a second curve to show
the change caused bv a catalyst .
C . likely to react .
D. likely to rebound without reacting. EXTENDED RESPONSE

5. A species that changes the rate of a reaction but 12. Suggest ways of measuring the concentration of
is neither consumed nor changed is a reactant or product in a reaction mixture.
A . a catalyst . 13. Why are reaction orders not always equal to the
B. an activated complex. coefficients in a balanced chemical equation ?
C. an intermediate.
D. a reactant .
.
6 A rate law relates
A . reaction rate and temperature.
B. reaction rate and concentration.
C. temperature and concentration.
D . energy and concentration . Sometimes, only one part of a
graph or table is needed to answer a question. In
such cases, focus on only the information that is
required to answer the question.

REACTION KINETICS 585

 I M I C R O-
EXPERIMENT 17 L A B

Rate of a Chemical Reaction

OBJECTIVES BACKGROUND
• Prepare and observe several different In this experiment , you will determine the rate of the
reaction mixtures. reaction whose net equation is written as follows:
• Demonstrate proficiency in measuring
reaction rates.
3Na2S205(fl<7) + 2 KIO,( «<7 ) + 3 H 20( / ) — >
2 KI ( a <y ) + 6 NaHS04( «f/ )
• Relate experimental results to a rate law One way to study the rate of this reaction is to
that can be used to predict the results of observe how fast Na 2S205 is used up. After all the
various combinations of reactants. Na2S205 solution has reacted , the concentration of
iodine, 1:, an intermediate in the reaction , increases.
MATERIALS A starch indicator solution , added to the reaction
• S - well microscale reaction strips, 2 mixture, will change from clear to a blue-black color
in the presence of 12.
• distilled or deionized water
In the procedure, the concentrations of the reac-
• fine - tipped dropper bulbs or small tants are given in terms of drops of solution A and
microtip pipets, 3 drops of solution B. Solution A contains Na 2S2 Ov
• solution A the starch indicator solution , and dilute sulfuric acid
to supply the hydrogen ions needed to catalyze the
• solution B
reaction. Solution B contains KIOv You will run the
• stopwatch or clock with second hand reaction with several different concentrations of the
reactants and record the time it takes for the
blue - black color to appear.

SAFETY

For review of safety, please see the Safety in the

Chemistry Laboratory in the front of your book.

PREPARATION
1 . Prepare a data table with six rows and six
columns. Label the boxes in the first row of the
second through sixth columns “ Well l , ' “ Well 2.“
*

“ Well 3,” “ Well 4.” and “ Well 5. In the first col -

**

umn. label the boxes in the second through sixth

rows “Time reaction began , ' “Time reaction
*

stopped .” “ Drops of solution A . “ Drops of solu -

*'

tion B. and “ Drops of FLO."

"

586 CHAPTER 1 7
 EXPERIMENT 17

2. Obtain three dropper bulbs or small microtip 6. Observe the lower wells. Note the sequence in
pipets, and label them “A.” “ B.“ and “ H:0.‘ *
which the solutions react , and record the number
of seconds it takes for each solution to turn a
3. F ill the bulb or pipet A with solution A. the
blue - black color.
bulb or pipet B with solution B, and the bulb
or pipet for H:0 with distilled water.
CLEANUP AND DISPOSAL
PROCEDURE 7. Dispose of the solutions in the container
designated by your teacher. Wash your
1. Using the first 8- well strip, place five drops of
hands thoroughly after cleaning up the
solution A into each of the first five wells.
area and equipment .
Record the number of drops in the appropriate
places in your data table. For the best results, try
ANALYSIS AND INTERPRETATION
to make all drops about the same si / e.
1. Organizing Data: Calculate the time elapsed for
2. In the second 8-well reaction strip, place one the complete reaction of each combination of
drop of solution B in the first well , two drops in solutions A and B.
the second well , three drops in the third well , four
drops in the fourth well , and five drops in the 2. Evaluating Data: Make a graph of your results.
fifth well . Record the number of drops in your Label the .v -axis “ Number of drops of solution
data table. B." Label the y-axis “Time elapsed . Make a
**

similar graph for drops of solution B versus rate

3. In the second 8- well strip that contains drops of ( 1/time elapsed ).
solution B. add four drops of water to the first
well , three drops to the second well , two drops 3. Analyzing Information: Which mixture reacted
to the third well, and one drop to the fourth the fastest ? Which mixture reacted the slowest ?
well . Do not add any water to the fifth well . 4. Evaluating Methods: Why was it important to
4. Carefully invert the second strip. The surface add the drops of water to the wells that contained
tension should keep the solutions from falling fewer than five drops of solution B? ( Hint: Figure
out of the wells. Place the strip well - to-well out the total number of drops in each of the
on top of the first strip, as shown in Figure A . reaction wells. )

5 . Hold the strips lightly together as shown in CONCLUSIONS

Figure A , and record the exact time, or set the 1. Evaluating Conclusions: Which of the following
stopwatch , as you shake the strips once. This variables that can affect the rate of a reaction
procedure should mix the upper solutions with is tested in this experiment: temperature,
each of the corresponding lower ones.
catalyst , concentration , surface area , or nature
of reactants? Explain your answer .
2. Applying Ideas: Use your data and graphs to
determine the relationship between the concen -
tration of solution B and the rate of the reaction .
Describe this relationship in terms of a rate law.

EXTENSIONS
1. Predicting Outcomes: What combination of
drops of solutions A and B would you use if
vou wanted the reaction to last exactly 2.5 min ?

FIGURE A

REACTION KINETICS 587

WMaWMMtl " - VXj
.- Hi 3
•

ilL
»V
>.
• *1*
\ V 4
*

The creation of stalactites and stalagmites

—
rnmr n O,

HHHI

is the result of a reversible chemical reaction.

The Nature of SECTION 1

Chemical Equilibrium OBJECTIVES

SJ Define chemical equilibrium.

Explain the nature of the

equilibrium constant.
1 n systems that are in equilibrium, opposing processes occur at the
same time and at the same rate. For example, when an excess of sugar is
placed in water, some sugar molecules go into solution, and others remain ^ Write chemical equilibrium
undissolved. At equilibrium molecules of sugar are crystallizing at the
,
expressions and carry out
same rate that molecules from the crystal are dissolving.The rate of evap- calculations involving them.
oration of a liquid in a closed vessel can eventually be equaled by the rate
of condensation of its vapor. The resulting equilibrium vapor pressure is
a characteristic of the liquid at the prevailing temperature. The preceding
examples are physical equilibria. In this chapter, we will expand on the
concept of equilibrium to include chemical reactions. You will learn how
a system at equilibrium responds when equilibrium conditions are altered
bv changing concentration, pressure, and temperature.

Reversible Reactions
Theoretically, every reaction can proceed in two directions, forward and
reverse. Thus, essentially all chemical reactions are considered to be
reversible under suitable conditions. A chemical reaction in which the
products can react to re- form the reactants is called a reversible reaction.

Mercury!11 ) oxide decomposes when heated.

2HgO( s) -£-> 2Hg(/ ) + 02(g)

Mercury and oxygen combine to form mercury!II ) oxide when heated

gently.

2Hg( / ) + 02( g) 2HgO(s)

Figure 1 shows both of these reactions taking place. Suppose

FIGURE 1 When heated, mer -
mercury!!I) oxide is heated in a closed container from which neither the
cury! II ) oxide decomposes into its
.
mercury nor the oxygen can escape Once decomposition has begun, the
elements, mercury and oxygen.
mercury and oxygen released can recombine to form mercury!II) oxide Liquid mercury reacts with oxygen
again. Thus, both reactions can proceed at the same time. Under these to re - form mercury!II ) oxide.
conditions, the rate of the synthesis reaction will eventually equal that of Together these reactions represent
the decomposition reaction. At equilibrium, mercury and oxygen will a reversible chemical process.

CHEMICAL EQUILIBRIUM 589

 combine to form mercury!II ) oxide at the same rate that mercury( ll )
oxide decomposes into mercury and oxygen. The amounts of mercury!11 )
oxide, mercury, and oxygen can then be expected to remain constant as
long as these conditions persist . At this point , a state of dynamic equilib-
rium has been reached between the two chemical reactions. Both reac-
tions continue, hut there is no net change in the composition of the
system . A reversible chemical reaction is in chemical equilibrium when
the rate of its forward reaction equals the rate of its reverse reaction and
the concentrations of its products and reactants remain unchanged The
chemical equation for the reaction at equilibrium is written using double
arrows to indicate the overall reversibility of the reaction .

2 HgO( .s ) > 2 Hg( / ) + (g )

02

-
A Equilibrium, a Dynamic State
CHEMISTRY
M

Many chemical reactions are reversible under ordinary conditions of

Module 7 : Equilibrium
temperature and concentration . They will reach a slate of equilibrium
unless at least one of the substances involved escapes or is removed
from the reaction system . In some cases, however, the forward reaction
is nearly completed before the rate of the reverse reaction becomes
large enough to establish equilibrium . Here, the products of the forward
reaction are favored , meaning that at equilibrium there is a higher con -
centration of products than of reactants. Hence, we can say that the
equilibrium “ lies to the right ." because products predominate, and prod -
uets conventionally are written on the right - hand side of a chemical
equation . An example of such a system is the formation of sulfur triox -
ide from sulfur dioxide and oxygen .

2SO2( g ) + O2( g ) <r- 2SO3(g )

Notice that the equation is written showing an inequality of the two

arrow lengths. The forward reaction is represented bv the longer arrow
to imply that the product is favored in this reaction .
In other cases, the forward reaction is barely under way when the
rate of the reverse reaction becomes equal to that of the forward reac-
tion . and equilibrium is established. In these cases, the amounts of reac-
tants remain high and the amounts of products are low. Here we sav
that the equilibrium lies to the left ." because the reactants are the pre -
"

dominant species. An example of such a system is the acid - base reaction

between carbonic acid and water.

H :COj,( aq ) + HzO( l ) H '

(aq ) + HCOi ( a q )

In still other cases, both forward and reverse reactions occur to near -
ly the same extent before chemical equilibrium is established. Neither
reaction is favored , and considerable concentrations of both reactants

590 CHAPTER 18
and products are present at equilibrium. An example is the dissociation
of sulfurous acid in water.

H:S03( ,
> H tr ( <K/ ) + HS03( aq )
^) + H20( / )
Chemical reactions ordinarily are used to convert available reactants
into more desirable products. Chemists try to convert as much of these
reactants as possible into products. The extent to which reactants are
converted to products is indicated by the numerical value of the equi -
librium constant .

The Equilibrium Expression

Suppose two substances, A and B, react to form products C and D. In
turn. C and D react to produce A and B. Under appropriate conditions,
equilibrium occurs for this reversible reaction. This hypothetical equi-
librium reaction is described by the following general equation.

n A + m B <r t xC + vD

Initially, the concentrations of C and D are zero and those of A and

B are maximum. Figure 2 shows that over time the rate of the forward
reaction decreases as A and B are used up. Meanwhile, the rate of the
reverse reaction increases as C and D are formed. When these two reac -
tion rates become equal, equilibrium is established. The individual con -
centrations of A . B. C, and D undergo no further change if conditions
remain the same.
After equilibrium is attained, the concentrations of products and
reactants remain constant, so a ratio of their concentrations should also

Rate Comparison for the Reaction System

A + B <=l C + D

A+B *C+D
( forward reaction)
Q>
FIGURE 2 Shown are
c reaction rales for the hypothetical
o Equilibrium
••- equilibrium reaction system
u ( forward rate = reverse rate)
03
<U
cc
A +B
^ C + D. From the time
A and B are mixed together at t0.
the rate of the forward reaction
C+D -> A+B declines and the rate of the reverse
( reverse reaction)
reaction increases until both forward
and reverse reaction rates are equal

to t
,
at i . when the equilibrium condition
Time begins.

CHEMICAL EQUILIBRIUM 591

 remain constant. The ratio of the mathematical product [C] v x |I )|' to
the mathematical product [ A|;f x [ B ) " for this reaction has a definite
'

value at a given temperature. It is the equilibrium constant of the reac-

tion and is designated by the letter K. The following equation describes
the equilibrium constant for the hypothetical equilibrium system.
The brackets ( [ ] ) indicate the concentration of each substance in mol / L.
The superscripts are the coefficients of each substance in the balanced
chemical equation .
[C ) V|D ) '
"

|A ]"[ B]"'
The concentrations of substances on the right side of the chemical
equation appear in the numerator of the ratio, with each concentra -
tion raised to a power equal to the coefficient of that substance in the
balanced chemical equation . These substances are the products of the
forward reaction . The concentrations of substances on the left side of
the chemical equation are in the denominator of the ratio, with each
concentration raised to a power equal to the coefficient of that sub-
stance in the balanced chemical equation. These substances are the
reactants of the forward reaction . The constant K is independent of
the initial concentrations. It is, however , dependent on the tempera -
ture of the system .

The Equilibrium Constant

The numerical value of K for a particular equilibrium system is
obtained experimentally. The chemist must analyze the equilibrium
mixture and determine the concentrations of all substances. The value
of K for a given equilibrium reaction at a given temperature shows the
extent to which the reactants are converted into the products of the
reaction . If the value of K is small , the forward reaction occurs only
very slightly before equilibrium is established , and the reactants are
favored. A large value of K indicates an equilibrium in which the orig-
inal reactants are largely converted to products. Only the concentra -
tions of substances that can actually change are included in K . This
means that pure solids and liquids are omitted because their concen -
trations cannot change.
In general , then , the equilibrium constant, K , is the ratio of the math-
ematical product of the concentrations of substances formed at equilib -
rium to the mathematical product of the concentrations of reacting
substances. Each concentration is raised to a power equal to the coeffi-
cient of that substance in the chemical equation. The equation for K is
sometimes referred to as the chemical equilibrium expression .
The H 2, l 2 , HI Equilibrium System
Consider the reaction between H: and 1: vapor in a sealed flask at an
elevated temperature. The rate of reaction can be followed by observ -
ing the rate at which the violet color of the iodine vapor diminishes, as
.
shown in Figure 3 If colorless H 2 gas is present in excess, we might

592 CHAPTER 7 8
expect that the reaction would continue until all of the 12 is used up. The
violet color of the tube would decrease in intensity until all of the iodine
reacts. At that time, the tube would be colorless, because both HI and
the excess IT are colorless gases.
In actuality, the color fades to a constant intensity but does not dis-
appear completely because the reaction is reversible. Hydrogen iodide
decomposes to re-form hydrogen and iodine. The rate of this reverse
reaction increases as the concentration of hydrogen iodide increases.
The rate of the forward reaction decreases accordingly. The concentra -
tions of hydrogen and iodine decrease as they react . As the rates of the
opposing reactions become equal , equilibrium is established. The con -
stant color achieved indicates that equilibrium exists among hydrogen ,
iodine, and hydrogen iodide. The net chemical equation for the reaction
system at equilibrium follows.

H:(s ) + I 20? ) > 2111 ( g )

From this chemical equation , the following chemical equilibrium expres-

sion can be written. The concentration of HI is raised to the power of 2
because the coefficient of HI in the balanced chemical equation is 2.
[ HI]2
FIGURE 3 Hydrogen iodide gas is
'

|H 2 ][ I 2]
produced from gaseous hydrogen
Chemists have carefully measured the concentrations of IT. I 2. and and iodine. The violet color of iodine
HI in equilibrium mixtures at various temperatures. In some experi - gas ( a ) becomes fainter as the reac -
ments. the flasks were filled with hydrogen iodide at known pressure. tion consumes the iodine ( b ). The
The flasks were held at fixed temperatures until equilibrium was estab- violet does not disappear hut reach -
lished . In other experiments, hydrogen and iodine were the original sub- es a constant intensity when the
reaction reaches equilibrium ( c ).
stances. Experimental data , together with the calculated values for K ,
are listed in Table 1 . Experiments 1 and 2 began with hydrogen iodide.
Experiments 3 and 4 began with hydrogen and iodine. Note the close
agreement obtained for the numerical values of the equilibrium con -
stant in all cases.
At 425 C. the equilibrium constant for this equilibrium reaction sys-
tem has the average value of 54.34. Ibis value for K is constant for
any system of IT. I 2. and HI at equilibrium at this temperature. If the

TABLE 1 Typical Equilibrium Concentrations of H Ij, and HI in mollL at 42S°C

*
[HI ] 2
K~
Experiment [H2 ] [l 2l [HI] [ H2][l2]
0.4953 X nr 3 0.4953 x 10 ' 3 3.655 x 10'3 54.46
2 1.141 x 10 ' 3 1.141 x lO 3 '
8.410 x 10 3'
54.33
3 3.560 x 10 ~ 3 1.250 x Hr3 15.59 x lO ' 3 54.62
4 2.252 x lO ’ 3 2.336 x 10~3 16.85 x 10~3 53.97

CHEMICAL EQUILIBRIUM 593

 calculation for K yields a different result , there must be a reason. Either
the Hi. I 2. and HI system has not reached equilibrium or the system is
not at 425 C.
The balanced chemical equation for an equilibrium system is neces-
sary to write the expression for the equilibrium constant. The data in
Table 1 show that the validity of this expression is confirmed when the
actual values of the equilibrium concentrations of reactants and prod -
ucts are determined experimentally.The values of K are calculated from
these concentrations. No information concerning the kinetics of the
reacting systems is required.
Once the value of the equilibrium constant is known , the equilibrium -
constant expression can be used to calculate concentrations of reactants
or products at equilibrium . Suppose an equilibrium system at 425 C is
found to contain 0.015 mol / L each of IT and L. To find the concentra -
tion of HI in this system , rearrange the chemical equilibrium expression
as shown in the two equations that follow.
[ HI ]2
= [ H2][ I 2]
[HI ] = VK[ H 2][ I;]

Using the known K value and the given concentrations for H 2 and L ,
solve the equation for [ HI ].

[HI ] = V0.015 x 0.015 x 54.34

[ HI ] = 0.11 mol/L

SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.

An equilibrium mixture of N2 , 02, and NO gases at 1500 K is determined to consist of 6.4 x 10 ' mol/1, "

of N 2, 1.7 x 10 ' mol/ L of 02, and 1.1 x 10 5 mol/ L of NO. What is the equilibrium constant for the sys-
" "

tem at this temperature?

SOLUTION
1 ANALYZE Given : |N 2 ] = 6.4 x 10 ' mol / L
[ 02] = 1.7 x 10 ' mol / L
"
*

[ NO ] = 1.1 x 10 5 mol / L
“

Unknown : K

2 PLAN The balanced chemical equation is N 2 (g ) + Q2(g ) 2 NO(g ).

[ NOf
Hie chemical equilibrium expression is K = [ N ][ 0 ]
2 :

3 COMPUTE Substitute the given values lor the concentrations into the equilibrium expression .
( 1.1 x 10-5 mol/ L)2
K=
( 6.4 x 10 ’ mol / L ) ( 1.7 x 10 3 mol / L )
= 1.1 x 10 5
‘

594 CHAPTER 18
4 EVALUATE Hie value of K is small, which is consistent with more N2 and 0: being present at equilibri-
um than NO. The answer has the correct number of significant figures and is close to an
estimated value of
( lx 10--s )2
8 x 10 . calculated as ( 6 x 10 3)(2 x Hr3)
h
"
'

PRACTICE Answers in Appendix E

1. At equilibrium a mixture of N2. H:. and NH; gas at 500°C is deter -

mined to consist of 0.602 mol/ L of N:, 0.420 moI/L of H:. and
0.113 mol/ L of NH v What is the equilibrium constant for the reac -
tion N2( g) + 3H2(g) ,
> 2NH (g) at this temperature?

2. The reaction AB2C(g) <- B2( g ) + AC( # ) reached equilibrium

at 900 K in a 5.00 L vessel. At equilibrium 0.084 mol of AB:C.
0.035 mol of B 2, and 0.059 mol of AC were detected What is the .
equilibrium constant at this temperature for this system? ( Don 't
forget to convert amounts to concentrations ) .
3. A reaction between gaseous sulfur dioxide and oxygen gas to pro-
duce gaseous sulfur trioxide takes place at 600 C. At that temper -
ature. the concentration of S02 is found to be 1.50 mol /L. the — i Lfblil
concentration of 02 is 1.25 mol/L. and the concentration of SO is Go to go.hrw.com for
3.50 mol/L. Using the balanced chemical equation, calculate the
* more practice problems
equilibrium constant for this system. that ask you to calculate
equilibrium constants.
Keyword: HC 6 EQUX

SECTION REVIEW 7. At equilibrium at 2500 K, [ HCI] = 0.0625 mol/L

1. What is meant by chemical equilibrium? and [ H2 ] = [Cl2 ] = 0.00450 mol / L for the reaction
H2(g) + Cl2 ( g ) <r 2 HCI(g). Find the value of K.
2. What is an equilibrium constant ?
8. An equilibrium mixture at 425°C is found to con-
3. How does the value of an equilibrium constant sist of 1.83 x 10 3 mol/L of H2, 3.13 x 10 3
“ ‘

relate to the relative quantities of reactants and mol / L of l2, and 1.77 x 10 2 mol/L of HI.
products at equilibrium? Calculate the equilibrium constant, K, for the
4. What is meant by a chemical equilibrium reaction H2 ( g ) + l2 (g) 2 HI(g).
expression? 9. For the reaction H2(g) + l2 (g) ; 2 HI( g )
5. Hydrochloric acid, HCI, is a strong acid that disso- at 425°C, calculate [ HI ], given [H2 ] = [ l 2 ] =
ciates completely in water to form H30+ and Cl . 4.79 x 10 4 mol/ L and K = 54.3.
“

Would you expect the value of K for the reaction

HCI(ag) + H20( /) £ H30+( aq ) + Cl ( aq ) to be Critical Thinking
1 x 10 2, 1 xKT5, or " very large " ? Justify your
“
10. INFERRING RELATIONSHIPS Use the data from
answer. Experiment 1 in Table 1 to calculate the value
6. Write the chemical equilibrium expression for the of K for the reaction 2 HI(g) H2(g) + hte) -
2 CI2 (g) + 2 H 20(g). Do you see a relationship between the value you
reaction 4HCI(g) + 02 ( g ) * obtained and the value in the table?

CHEMICAL EQUILIBRIUM 595

 Afrfpft I »%- 2D0.1 L i - 7 I Ng.= Z3
iDRSiEsisnmRn
ISTORICAL CHEMISTRY

Fixing the Nitrogen Problem

Historical Perspective
Malthus's warning seemed to be echoed in the 1840 s by
Each year, the chemical industry synthesizes tons of
the great Irish potato famine. In fact, the rest of Europe
nitrogenous fertilizers, increasing agricultural production
likely would have suffered serious food shortages as well
J around the globe. But prior to 1915, humans had to rely
had crop yields per acre not been increased through the
solely on natural resources for fertilizer, and the dwindling
use of fertilizers containing nitrogen.
supply of these materials caused widespread fear of world
Few living things can utilize the gas that forms 78% of
starvation. A crisis was averted, however, through the dis-
the atmosphere; they need nitrogen that has been com-
covery of an answer to the " nitrogen problem," a term
bined with other elements, or " fixed, " to survive.
used at the time to describe the shortage of useful nitro -
But soil often lacks sufficient amounts of the organisms
gen despite its abundance in the atmosphere.
that fix nitrogen for plants, so fertilizers containing usable
The Malthusian Threat nitrogen compounds are added. In 1898, two-thirds of the
In 1798, Thomas Malthus published his famous " Essay on world's supply of these compounds came from Chile, where
Population," a report predicting that the world's food sup- beds of sodium nitrate, or Chile saltpeter, were abundant,
plies could not keep up with the growing human popula - But, as the chemist William Crookes emphasized in his
tion and that famine, death, and misery were inevitable. speech to the British Association that year, these reserves

Amma s

< Nitrogen is released when living

things die and also from animal
wastes and plant material. Some
bacteria are able to break the bond
holding the nitrogen molecule
together; freeing the nitrogen
atoms to combine with hydrogen to
form ammonia. Plants can absorb
Decomposition the nitrogen in this form from the
soil. Animals then benefit from the
nitrogen by eating the plants.
m
Wl
Ti - Sol Zr - 9°
' '
BWI 5
-

were limited; it was up to his colleagues to dis-

cover alternatives and prevent Malthus's dire
forecast from coming true.
The Haber- Nernst Controversy
As early as the 1890s, chemists had shown that
ammonia, a practical source of fixed nitrogen,
could be synthesized at high temperatures and
at atmospheric pressure from elemental hydro-
gen and nitrogen. The problem was that the end
product was present in such minute amounts
that the process was not industrially practical.
In 1904, the German chemist Fritz Haber
seemed to confirm this assessment. He tried react-
ing hydrogen and nitrogen at temperatures of up A Today, ammonia is produced on an industrial scale in plants
to 1020°C using pure iron as well as other metals like this one.
as a catalyst. He found that the amount of ammo-
nia was a mere 0.005% to 0.012% at equilibrium. sures. They also discovered that a catalyst of iron contain-
Haber had apparently closed the door on the synthesis ing small amounts of impurities was an effective replace -
of ammonia from its elements. But in 1906, Walther ment for the rare metals used by Haber.
Nernst, using his new heat theorem, calculated the reac- An Eerie Epilogue
tion's theoretical ammonia concentration at equilibria cor - By September 1913, BASF was producing 20 metric tons of
responding to several pressures. He found that his value at ammonia a day using the Haber- Bosch process. Eventually,
atmospheric pressure disagreed significantly with Haber's, enough ammonia was produced by the chemical industry
and he publicly challenged Haber's values. to free Germany and the world of dependence on Chile
Haber was convinced that he was right. He ran the reac- saltpeter for fertilizer. Chemists had thwarted the
tion at increased pressure to attain an amount of ammo - Malthusian threat. Yet, the victory proved bittersweet; the
nia that could be measured more accurately. new ammonia synthesis also became the basis of the pro-
Haber and his assistants confirmed their original find- duction of nitric acid, used to make many of the explosives
ings, and Nernst later conceded a mathematical error. But employed in the wars that rocked Europe and the rest of
more important, the new round of experiments indicated the globe in the first half of the twentieth century.
that a reasonable amount of ammonia might be attained
at pressures of 200 atm ( 402 kPa) using a uranium or Questions
osmium catalyst.
1. What is the major use for ammonia ?
Scaling Up 2. What did Haber find when he tried to synthesize
Large-scale equipment that could withstand such high ammonia at increased pressure?
pressures was unheard of at the time, and osmium and
uranium were far too scarce to be cost-effective for indus-
try. Nevertheless, in 1909, the German firm BASF bought
the rights to Haber's findings and put its gifted chemical
SCilNKS.] Developed MMI tytfce
KrtttMl Science feAcken Auction

engineer Karl Bosch in charge of creating an industrial- For a variety of links related to this
scale system that would make the process profitable. chapter, go to www.sdlinks Ofg .
After nearly five years, Bosch and the company's chief
chemist, Alwin Mittasch, succeeded in developing a suit-
Topic: Nitrogen
SciLinks code: HC61035
^
able reactor that could handle the reaction's high pres-

597
 SECTION 2
Shifting Equilibrium
OBJECTIVES
sj Discuss the factors that
disturb equilibrium. In systems that have attained chemical equilibrium, the relative
amounts of reactants and products stay the same. But changes in pres -
sure. concentration, or temperature can alter the equilibrium position
^ Discuss conditions under which and thereby change the relative amounts of reactants and products. By
reactions go to completion .
shifting an equilibrium in the desired direction, chemists can often
improve the yield of the product they are seeking.
sj Describe the common- ion
effect.

Predicting the Direction of Shift

In 1888, the French chemist Henri Louis Le Chatelier developed a prin-
CHEMISTRY ciple that provides a means of predicting the influence of stress factors on
Module 7 : Equilibrium equilibrium systems. Le Chatelier s principle states that if a system at
equilibrium is subjected to a stress, the equilibrium is shifted in the direc-
tion that tends to relieve the stress. This principle is true for all dynamic
equilibria, chemical as well as physical. Changes in pressure, concentra-
tion, and temperature illustrate Le Chatelier s principle.

Changes in Pressure
A change in pressure affects only equilibrium systems in which gases
are involved. For changes in pressure to affect the system, the total
number of moles of gas on the left side of the equation must be different
from the total number of moles of gas on the right side of the equation.
Let us consider the Haber process for the synthesis of ammonia. Note
that there is a total of four molecules of gas on the reactant side of the
equation and two molecules of gas on the product side of the equation .
N2(g) + 3H2(g) 2NH3(£)
First, consider an increase in pressure as the applied stress. Can the sys -
tem shift in a way that reduces the stress ? Yes. An increase in pressure
causes increases in the concentrations of all species. The system can
reduce the number of molecules, and hence the total pressure, by shift -
ing the equilibrium to the right . For each four molecules of reactants,
nitrogen and hydrogen, there are two molecules of product, ammonia.
By producing more NH3. and using up N 2 and 1L. the system can reduce
the total number of molecules. This leads to a decrease in pressure.
Although the new equilibrium pressure is still higher than before, it is
not as high as the pressure caused by the initial stress.
An increase in pressure on confined gases causes an increase in the
concentrations of these gases. Even though changes in pressure may

598 CHAPTER 18
shift the equilibrium position, they do not affect the value of the equi - (a )
librium constant.
Ammonia produced in the Haber process is continuously removed by
condensing it to liquid ammonia.This condensation removes most of the
product from the gas phase in which the reaction occurs. The resulting
decrease in the partial pressure of NH; gas in the reaction vessel is a
stress and is the same as a decrease in product concentration, which
shifts the equilibrium to the right .
The introduction of an inert gas. such as helium, into the reaction ves - N ? added
( b)
sel for the synthesis of ammonia increases the total pressure in the vessel.
Hut it does not change the partial pressures of the reaction gases present.
Therefore, increasing pressure by adding a gas that is not a reactant or
a product cannot affect the equilibrium position of the reaction system.

Changes in Concentration
An increase in the concentration of a reactant is a stress on the equilib -
rium system. Consider the following hypothetical reaction.
A+B C+ D ( c)

An increase in the concentration of A creates a stress. To relieve the

stress, some of the added A reacts with B to form products C and D. The
equilibrium is reestablished w ith a higher concentration of A than before
the addition and a lower concentration of B. Figure 4 illustrates the effect
on a system in equilibrium produced by increasing the concentration of a
reactant. Similarly, an increase in the concentration of B drives the reac -
tion to the right. An increase in the concentration of either C or D shifts
the equilibrium to the left . A decrease in the concentration of C or D has N 2(9) + 3 H2 ( g ) 2 NH 3 (g)
the same effect on the position of the equilibrium as does an increase in
the concentration of A or B: the equilibrium shifts to the right. FIGURE 4 ( a ) N:. H:. and NH ,
Changes in concentration have no effect on the value of the equilib- are in equilibrium within a closed
rium constant . Because of this, such changes have an equal effect on the system, ( b) Addition of more N:
numerator and the denominator of the chemical equilibrium expression, causes a stress on the initial equilib-
riius, the new concentrations give the same value or numerical ratio for rium. ( c ) The new equilibrium posi-
the equilibrium constant when equilibrium is reestablished. tion for ihis system has a higher
concentration of N:, a lower concen -
Many chemical processes involve heterogeneous reactions in which
tration of H:. and a higher concen -
reactants or products are in different phases, The concentrations of pure
tration of NH: than initially.
solids and liquids do not change, and by convention are not w ritten in the
equilibrium expression. Also, when a solvent such as water, in a system
involving acids and bases, is in an equilibrium equation, it is not includ-
ed in the equilibrium expression. In Chapter 15. the expression for Kix
used this convention. The reaction representing the self-ionization of
water is

2H-»Q( / ) f HyQ* ( aq ) + OH~(tf </) I For a variety of links related to this

I chapter, 9 fjl
and the equation for Ku is Kw = [ H;,0 ] [ OH ].
~
° to
I Topic: Haber Process
The following equation describes the equilibrium system established
by the decomposition of solid calcium carbonate.
I Sci Links code: HC60704

CaC03(s) i -» .
CaO( 9) + CO:(s )

CHEMICAL EQUILIBRIUM 599

 The products are a solid and a gas. Because both CaC03 and CaO are
solids, they are not in the equilibrium constant expression. This leads to
the following expression for the equilibrium constant .
K = [C02]
Carbon dioxide is the only substance in the system that appears in the
equilibrium expression . Because the total number of moles of gas on
the left side of the equation is different from the total number of moles
on the right side of the equation pressure changes will affect the equi -
,

librium . High pressure favors the reverse reaction , which causes CO:
molecules to react with the solid CaO to form solid Ca ( Ov Low pres-
sure favors the formation of C02 from the decomposition of CaCOv
Because both CaO and CaCO arc solids, changing their amounts will
>

not change the equilibrium concentration of C02.

Changes in Temperature
Reversible reactions are exothermic in one direction and endothermic
in the other. The effect of changing the temperature of an equilibrium
mixture depends on which of the opposing reactions is endothermic and
which is exothermic.
According to Le Chatelier s principle, the addition of energy in the
form of heat shifts the equilibrium so that energy is absorbed . This
favors the endothermic reaction. The removal of energy favors the
exothermic reaction . A rise in temperature increases the rate of any
reaction . In an equilibrium system , however , the rates of the opposing
reactions are raised unequally. Thus, the value of the equilibrium con -
stant for a given system is affected by the temperature.
The synthesis of ammonia by the Haber process is exothermic, as indi-
cated by the energy as heat shown on the product side of the equation .

=
N 2( £ ) + 3 H 2( g ) < ? 2NH 3(g ) + 92 kJ
A high temperature favors the decomposition of ammonia , the
endothermic reaction . But at low temperatures, the forward reaction is
too slow to be commercially useful. The temperature used represents a
compromise between kinetic and equilibrium requirements. It is high
enough that equilibrium is established rapidly but low enough that the
equilibrium concentration of ammonia is significant . Moderate temper -
ature ( about 500 C ) and very high pressure ( 700-1000 atm ) produce a
satisfactory yield of ammonia.
The production of colorless dinitrogen letroxide gas. N\ 04. from dark
brown NO: gas is also an exothermic reaction . Figure 5 shows how tem -
perature affects the equilibrium of this system. Figure 5b shows the
NO:/ N:04 equilibrium mixture at 25 C. When the temperature of the
system is lowered to 0 C. the system experiences a stress ( removal of
energy as heat ). To counteract this stress, the system shifts to the right , or
in the direction of the exothermic reaction . This shift increases the
amount of colorless N:04 gas and decreases the amount of brown NO:
gas. as shown in Figure 5a. Because more N 204 is present. K is increased.
When the system is heated to 100 C, the added energy is the stress, and

600 CHAPTER 18
( a) (c )
FIGURE 5 Different temperatures

i
A

1 r
can cause an equilibrium system to
shift and seek a new equilibrium
position.

0°C 100°C
Very light brown Medium brown Dark brown

2 N02(g) j - N204(g) + energy as heat

(brown) (colorless)

the equilibrium shifts to the left, or in the direction of the endothermic

reaction. litis shift decreases the amount of colorless N2Q4 gas and
'

increases the amount of brown NO: gas, as shown in Figure 5c Because .

.
less N:04 gas is present. K is decreased The change in temperature
changes the value of K . For a system in which the forward reaction is an
exothermic reaction, increasing the temperature decreases the value of K.
For an endothermic reaction, such as the decomposition of calcium
carbonate, energy as heat shows up on the reactant side of the equation.
CaO . + C02
An increase in temperature
^
556 k J + CaC03(5) ( v)

caused by adding energy

( g)

to the system
causes the value of K to increase and the equilibrium to shift to the right .
The reactions of the system are also accelerated by a suitable cata -
lyst. I lowever. catalysts have no effect on relative equilibrium amounts.
They only affect the rates at which equilibrium is reached. The reason is
that catalysts increase the rates of forward and reverse reactions in a
system by equal factors. Therefore, they do not affect K .

Reactions That Co to Completion

Some reactions involving compounds formed by the chemical interac -
tion of ions in solutions appear to go to completion in the sense that the
ions are almost completely removed from solution. The extent to which
reacting ions are removed from solution depends on the solubility of
the compound formed and. if the compound is soluble, on the degree of
ionization. Thus, a product that escapes as a gas. precipitates as a solid ,

or is only slightly ionized effectively removes from solution the bulk of

the reacting ions that compose it . Consider some specific examples of
situations in which such ionic reactions go to completion.

CHEMICAL EQUILIBRIUM 601

 Formation of a Gas
Unstable substances formed as products of ionic reactions decompose
spontaneously. An example is carbonic acid , hUCO the acid in carbon -
^
ated beverages, which yields a gas as a decomposition product.

,
H:CO ( </ </ ) > H:0( / ) + CCM £ )

This reaction goes practically to completion because one of the prod -

ucts, C02, escapes as a gas if the container is open to the air.

Formation of a Precipitate
When solutions of sodium chloride and silver nitrate are mixed , a white
precipitate of silver chloride immediately forms, as shown in Figure 6.
The overall ionic equation for this reaction follows.

Na*( aq ) + Cl ( uq ) + Ag*( aq ) + NO$ ( aq ) * Na ( aq ) + NO$ ( aq ) + AgO ( .v )

*

If chemically equivalent amounts of the two solutes are mixed , only Na '

ions and NO ions remain in solution in appreciable quantities. Almost

>

all of the Ag ions and Cl ions combine and separate from the solution
* "

as a precipitate of AgCl. The reason is that AgCl is only very sparingly

soluble in water. It separates by precipitation from what has become a
supersaturated solution of AgCl. The reaction thus effectively goes to
completion because an essentially insoluble product is formed .

9
9

9
«
mo* to**»* 9
IT V ..
•o**

9
9
Cl
9
Na *
o H 20
H 2O NO 3-
Ag *

FIGURE 6 When a clear sodium

chloride solution is combined with
a clear solution of silver nitrate, an
Ag '

Na + 4
9
1
« » *o *
» *4
•
9

.
9
«
NO 3

Cl

H 20

insoluble white precipitate of silver

chloride is formed . AgCl

602 CHAPTER 18
Formation of a Slightly Ionized Product
Neutralization reactions between ITO" ions from aqueous adds and
OH ions from aqueous bases result in the formation of water molecules,
.
which are only slightly ionized A reaction between HCI and NaOH
-
illustrates this process. Aqueous HCI supplies Il O" ions and Cl ions to
the solution, and aqueous NaOH supplies Na+ ions and OH ions, as "
'

shown in the following overall ionic equation.

H 3O ( aq ) + Cl ( aq ) + Na ( aq ) + OH ( m/|
‘ '
» Na* ( aq ) + C\ ( aq ) + 2 H:Q( / )

Neglecting the spectator ions, the net ionic equation is as follows.

H 3O "( /</ ) + OH“( fl{/ ) 2H:0( / )

*
Because it is only slightly ionized, the water exists almost entirely as CROSS- DISCIPLINARY
covalently bonded molecules. Thus, insofar as they are initially present Go to go.hrw.com for a full - length
in equal amounts, hydronium ions and hydroxide ions are almost en - article on equilibrium reactions and
caves.
tirely removed from the solution. The reaction effectively runs to com -
pletion because the product is only slightly ionized.
'J
' - Keyword: HC 6EQUX

Common- Ion Effect

An equilibrium reaction may be driven in the desired direction by
applying Le Chatelier ’s principle. Suppose hydrogen chloride gas is
bubbled into a saturated solution of sodium chloride. Hydrogen chlo-
ride is extremely soluble in water, and it is completely ionized.

HCl( g) + H:0( / ) » H30* ( aq ) + C \ ( aq )

'

The equilibrium for a saturated solution of sodium chloride is described

by the following equation.

NaCI( 5 ) ; Na " ( w/ ) + CI ( aq )

As the hydrogen chloride dissolves in sufficient quantity, it increases the

concentration of Cl ions in the solution, which is a stress on the equi -
librium system. The system can compensate, according to Le Chatelier 's
principle, by combining some of the added Cl ions with an equivalent
amount of Na" ions. This causes some solid NaCl to precipitate out .
relieving the stress of added chloride.The new equilibrium has a greater
concentration of Cl ions but a decreased concentration of Na" ions.
"

However, the product of [ Na"] and [ Cl ] still has the same value as
'

before. This phenomenon, in which the addition of an ion common to

two solutes brings about precipitation or reduced ionization , is an exam -
ple o f the common-ion effect.
The common -ion effect is also observed when one ion species of a
weak electrolyte is added in excess to a solution. Acetic acid, CH3COOH .
CHEMICAL EQUILIBRIUM 603
 is such an electrolyte. A 0.1 M CH3COOH solution is only about 1.3 %
ionized to produce hydronium ions and acetate ions. CH3COCT. Hie
ionic equilibrium is shown by the following equation.

CH3C00H( W/ ) + H20( / ) H30+(fl</ ) + CH3COO ( aq )

Small additions of sodium acetate. NaCI l3COO ( an ionic salt that is com -
FIGURE 7 The solution of
CHjCOOH on the left is combined pletely dissociated in water), to a solution containing acetic acid increase
with the solution of NaCH COO in the acetate ion concentration. The equilibrium then shifts in the direction
^
the center. Both contain the com - that uses up some of the acetate ions in accordance with Le Chatelier s
mon ion. CH ;COO . The \ produce principle. More molecules of acetic acid are formed, and the concentra -
'

the solution on the right, which tion of hydronium ions is reduced. In general, the addition of a salt with
is only slightly acidic due to the an ion common to the solution of a weak electrolyte reduces the ioniza -
decreased ionization of the acid.The
tion of the electrolyte. Figure 7 shows a 0.25 M CH3COOH solution on
colors of the solutions are due to the
addition of an acid-base indicator. the left that has a pH of
about 2.7. Mixing that
with the 0.10 M
NaCH3COO solution
in the center produces
the solution on the
right, which has a pH of
4.4 £rH about 4.5, indicating
; s. w -c lower [ H3Ot ] and thus
lowered acetic acid

PTT=!
ionization.

gSSlfx

SECTION REVIEW 5. Predict the effect that decreasing pressure would

1. Name three ways the chemical equilibrium can be have on each of the following reaction systems at
disturbed. equilibrium.
2. Describe three situations in which ionic reactions a. H 2 ( g ) + Cl2 (g) 2HCI( g )
go to completion. b. NH4CI(S) f t NH3(g) + HCI(flr)
3. Describe the common-ion effect. c. 2 H202 ( ag) « 2 H20( /) + 02 ( g )
4. Identify the common ion in each of the following d. 302(g) * 203(g)
situations.
Critical Thinking
a. 5 g of NaCI is added to a 2.0 M solution of HCI
6. PREDICTING OUTCOMES Carbon dioxide and water
b. 50 mL of 1.0 M NaCH 3 COO is added to 1.0 M react to form bicarbonate ion and hydronium ion.
CHjCOOH Hyperventilation (rapid breathing) causes more car -
c. 10 pellets of NaOH are added to 100 mL of water bon dioxide to be exhaled than normal. How will
hyperventilation affect the pH of blood? Explain.

604 CHAPTER 18
Equilibria of Acids, SECTION Z

Bases, and Salts OBJECTIVES

^ Explain the concept of
acid ionization constants,
and write acid ionization
equilibrium expressions.

Ionization Constant of a Weak Acid Review the ionization

constant of water.
About 1.3% of the solute molecules in a 0.1 M acetic acid solution are
ionized at room temperature. The remaining 98.7% of the acetic acid
u Explain buffering.
.
molecules CH3COOH, remain nonionized. Thus, the solution contains
three species of particles in equilibrium: CH3COOH molecules, II3O
"
.
ions, and acetate ions. CH3COO From the equilibrium equation for Compare cation and anion
the ionization of acetic acid, the equilibrium constant equation can be hydrolysis.
written.

CH3COOH + H2O , ,
H (T + CH COO-
, ,
[ H Q- ] [ CH COO 1
-

[CH3COOH][H20]
Notice that the concentration of water is not included in the equilib -
rium expression. The reason is that water is the solvent, and water mol-
ecules greatly exceed the number of acetic acid molecules. Without
introducing a measurable error, one can assume that the molar concen-
tration of H:0 molecules remains constant in such a solution. Thus,
because both K and [ H:0| are constant, the product /C [ H 2Q ] is constant.
|H30+][CH3C00- ]
MH:0 ] = [ CH3COOHI
The left side of the equation can be simplified by setting A. |H:Q ] = Kir
[H +][CH C00-|
30 3
a’
[CH3COOHI
The term is called the acid ionization constant. The acid ionization
Ktl
constant . Kr like the equilibrium constant , K , is constant for a specified
temperature but has a new value for each new temperature.
The acid ionization constant for a weak acid represents a small value.
To determine the numerical value of the ionization constant for acetic
acid at a specific temperature, the equilibrium concentrations of H30+
ions, CH3COO ions, and CH3COOH molecules must be known. The
"

ionization of a molecule of CH3COOH in water yields one H3CT ion

and one CH 3COO ion. These concentrations can, therefore, be found
"

experimentally by measuring the pH of the solution.

CHEMICAL EQUILIBRIUM 605

 TABLE 2 Ionization of Acetic Acid
Molarity % ionized [ H3o+] [ CH3COOH ] Ka
s
0.100 1.33 0.00133 0.0987 1.79 x 10
0.0500 1.89 0.000945 0.0491 1.82 x Hr 5
0.0100 4.17 0.000417 0.00958 1.81 x 10 "5

1.82 x 1O 5
0.00500 5.86 0.000293 0.00471 '

0.00100 12.6 0.000126 0.000874 1.82 x nr 5

CHEMISTRY , «-
nA
nr

*OTO+'
Module 8 : Strong and Weakly
Ionized Species, pH, and Titrations
Ionization data and constants for some dilute acetic acid solutions at
25 C are given in Table 2. Notice that the numerical value of Ktl is
almost identical for each solution molarity shown. The numerical value
of Ktl for CH3COOH at 25 C can he determined by substituting numer -
ical values for concentration into the equilibrium equation.

|H30+ ][CH3COO-]

i
i
( CH3COOH|

At constant temperature, an increase in the concentration of CH3COO

ions through the addition of sodium acetate, NaCH COO, disturbs the
^
equilibrium, as predicted bv Le Chateliers principle. This disturbance
causes a decrease in [H3CT ] and an increase in [CH3COOH). Eventually,
the equilibrium is reestablished with the same value of Kir But there is a
higher concentration of nonionized acetic acid molecules and a lower con -
centration of H;CT ions than before the extra CH3COO“ was added.
Changes in the hydronium ion concentration affect pH. In this example,
the reduction in [ H30+ 1 means an increase in the piI of the solution.

Buffers
FIGURE 8 ( a ) The beaker on the
The solution just described contains both a weak acid. CH3COOH. and
left contains a buffered solution and
an indicator with a pH of about 5. .
a salt of the weak acid NaCTI COO. The solution can react with either
>

The beaker on the right contains an acid or a base. When small amounts of acids or bases are added, the
mostly water with a trace amount of pH of the solution remains nearly constant. The weak acid and the com -
acid and an indicator. The pH meter mon ion. CH3COOA act as a “buffer " against significant changes in the
shows a pH of 5.00 for this solution, pH of the solution. Because it can resist changes in pH. this solution is a
( b ) After 5 mL of 0.10 M HC1 is buffered solution. Figure 8 shows how a buffered and a nonbuffered
added to both beakers, the beaker
on the left does not change color,
solution react to the addition of an acid .
Suppose a small amount of acid is added to the acetic acid-sodium
indicating no substantial change in
acetate solution. Acetate ions react with most of the added hydronium
its pH. However, the beaker on the
right undergoes a definite color ions to form nonionized acetic acid molecules.
change, and the pi I meter shows
a pH of 2.17. CU 3COO ( a q ) + H3C V ( a q )
* ClECOOHU/r/ ) + H:0( / )
606 CHAPTER 18
The hydronium ion concentration and the pH of the solution remain
practically unchanged.
Suppose a small amount of a base is added to the original solution.
The OH ions of the base react with and remove hydronium ions to form
nonionized water molecules. Acetic acid molecules then ionize and
mostly replace the hydronium ions neutralized by the added OH ions. "

,
C \ \ C0 0 H ( aq ) + H 20 ( l ) » H30+(a<7 ) + CH3COO ( aq )

The pH of the solution again remains practically unchanged.

A solution of a weak base containing a salt of the base behaves in a
similar manner. The hydroxide ion concentration and the pH of the
$ TRENGtH
Buffered Aspir''1
solution remain essentially constant with small additions of acids or 500 mg each
bases. Suppose a base is added to an aqueous solution of ammonia that
also contains ammonium chloride. Ammonium ions donate a proton to
the added hvdroxide ions to form nonionized water molecules.

NH
^ / + Oi l
/r ) ( aq )
* NH3( W7) + H:0( / )
'

If a small amount of an acid is added to the solution instead, hydrox - FIGURE 9 Many consumer prod-
ucts are buffered to protect the body
ide ions from the solution accept protons from the added hydronium
ions to form nonionized water molecules. Ammonia molecules in the from potentially harmful pH changes .
solution then ionize and mostly replace the hydroxide ions neutralized
by added H30+.

NH3( r /r/ ) + H:0( / ) NH;jU/r/ ) + OH -( w/ )

SC
Buffer action has many important applications in chemistry and
.
physiology Human blood is naturally buffered to maintain a pH of
/ lNKS. MT *
Dmtopcd mi MtaUintd by lb
NJUOMI SdM 1e«bm Aiwuiwa*
(

between 7.3 and 7.5. This is essential because large changes in pH would For a variety of links related to this
lead to serious disturbances of normal body functions. Figure 9 shows chapter, go to www. scilinks org
an example of one of the many medicines buffered to prevent large and Topic: Buffers
potentially damaging changes in pH. SciLinks code: HC60195

Ionization Constant of Water

Recall from Chapter 15 that the self -ionization of water is an equilib-
rium reaction.

H:0( / ) + H:Q( / ) l H;,0 ’(«r / ) + 0H ( aq )

Equilibrium is established with a very low concentration of H30+

and OH ions. The expression for the equilibrium constant, Kw =
”

[ H30~|[ OH ], is derived from the balanced chemical equation. The

“

numerical value of Kw , obtained experimentally, is 1.0 x 10 14 at 25°G ‘

CHEMICAL EQUILIBRIUM 607

 Hydrolysis of Salts
Salts are formed during neutralization reactions between acids and
bases. When a salt dissolves in water, it produces positive ions ( cations )
of the base from which it was formed and negative ions ( anions ) of the
acid from which it was formed. Therefore, the solution might be expect -
ed to be neutral . The aqueous solutions of some salts, such as NaCI and
KNO3, are neutral , having a pi 1 of 7. However , when sodium carbonate
dissolves in water , the resulting solution turns red litmus paper blue,
indicating a pH greater than 7. Ammonium chloride produces an aque-
ous solution that turns blue litmus paper red . indicating a pH less than
7. Salts formed from the combination of strong or weak acids and bases
are shown in Figure 10.
The variation in pH values can be accounted for by examining the
ions formed when each of these salts dissociates. If the ions formed are
from weak acids or bases, they react chemically with the water mole-
cules, and the pH of the solution will have a value other than 7. A reac-
tion between water molecules and ions of a dissolved salt is hydrolysis. If
the anions react with water , the process is anion hydrolysis and results
in a more basic solution . If the cations react with water molecules, the
process is cation hydrolysis and results in a more acidic solution .

Anion Hydrolysis
In the Bronsted sense, the anion of the salt is the conjugate base of the
acid from which it was formed . It is also a proton acceptor. If the acid is
weak , its conjugate base ( the anion ) will be strong enough to remove pro-

NaCI ( aq
**OH ( X.
i *teOH U3
hCt iiJU
.
SH , H O * "CJHJO.
i
tovfyo a

( b) ( c) (d )

FIGURE 10 The universal indicator shows that the pH of salt solutions

varies, depending on the strength of the acid and the base that formed the salt ,
( a ) NaCI is formed from a strong acid and a strong base: the color of the indi -
cator shows the pH is neutral. ( b ) The indicator shows the pH of the sodium
acetate solution is basic. This was formed from a strong base and a weak acid,
( c ) The strong acid and weak base combination in ammonium chloride pro-
duces an acidic solution , as shown by the reddish lint of the indicator ( d ) The
,

weak acid and weak base that form ammonium acetate are of comparable
strength. A solution of ammonium acetate is essentially neutral .

608 CHAPTER 18
tons from some water molecules, proton donors, to form OH ions. An '

equilibrium is established in which the net effect of the anion hydrolysis

is an increase in the hydroxide ion concentration. [ OH ). of the solution.
'

The equilibrium equation for a typical weak acid in water, 11 A. form -

ing hydronium ion and an anion. A , is as follows.
'

UM ( i( ] ) + H20(/ ) ? H3O~( aq ) + A ( aq )

From this equation, the generalized expression for K l can be written.

(
CROSS - DISCIPLINARY
Note that as before, water does not appear in the general equilibrium
4
•
equation. Blood Buffers
Blood normally has a pH of 7.4. If the
IH^crjlA | pH of blood in a human rises above 7.8
" IHA ] or falls below 7.0, this change in pH is
usually fatal. The primary buffer in blood
The hydrolysis reaction between water and the anion. A . that is pro- is the carbonic acid-bicarbonate ion sys-
duced by the dissociation of the weak acid. HA. is represented by the tern, C02( g) + H20( / ) H2C03(ag) +
general equilibrium equation that follows. HC03 (ag). A condition called respiratory
acidosis causes the pH to drop. It is the
result of hypoventilation, or slowed
A~( oq ) + H20( / ) HA (m/ ) + Oll ( aq ) breathing, the opposite of hyperventila -
tion. Hypoventilation can be caused by
In the forward reaction, the anion. A , acquires a proton from the water congestive heart failure, pneumonia, or
.
molecule to form the weak acid HA . and hydroxide ion. OH . The extent '
narcotics. Because breathing is slowed,
of OH ion formation and the position of the equilibrium depends on the carbon dioxide accumulates and its
concentration rises. This change causes a
relative strength of the anion. A”. The lower the K , value of HA , the
shift in the equilibrium to the right due
stronger the attraction for protons that A will have compared with Ol 1 ,
"

to Le Chatelier 's principle, and the blood

and the greater the production of OH ion will be. In other words, the
'

becomes more acidic because of the

. .
weaker the acid HA the stronger its conjugate base. A . '
higher concentration of carbonic acid.
Aqueous solutions of sodium carbonate are strongly basic. The so-
dium ions, Na ~. in sodium carbonate do not undergo hydrolysis in aque -
. .
ous solution, but the carbonate ions CO3 react as a Bronsted base A .
COT anion acquires a proton from a water molecule to form the weak
Bronsted acid. HCO 3, and the OH ion. '

CO\~( aq ) + H20( / ) HC03( ^/ ) 4- OH ( a q )

The OH ion concentration increases until equilibrium is established.

Consequently, the H3O* ion concentration decreases so that the prod -
uct [ II3O |[ O H | remains equal to the ionization constant, Kn of water
'
.
at the temperature ol the solution. Thus, the pi 1 is higher than 7. and the
solution is basic.

Cation Hydrolysis
In the Bronsted sense, the cation of the salt is the conjugate acid of the
base from which it was formed. It is also a proton donor. If the base is
weak, the cation is an acid strong enough to donate a proton to a water
molecule, a proton acceptor, to form H3O ions. An equilibrium is
established in w hich the net effect of the cation hydrolysis is an increase
in the hydronium ion concentration, [ H 3CT|, of the solution.

CHEMICAL EQUILIBRIUM 609

 The following equilibrium equation for a typical weak base , B. is used
to derive the generalized expression for Kh . the base dissociation
constant.
B ( a q ) + H:0( / ) <r * BH ( w/ ) + OH ( a q )
'

[ BH +][OM ~ ]
Kh = [ B|

The hydrolysis reaction between water and the cation. BIT. produced
by the dissociation of the weak base. B. is represented by the general
equilibrium equation that follows.

BH + ( a q ) + H 2Q ( l ) <r ? H 3CT ( a q ) + B ( a q )

In the forward reaction , the cation BIT donates a proton to the water
molecule to form the hydronium ion and the weak base, B. The extent
of H3CT ion formation and the position of the equilibrium depend on
the relative strength of the cation , BIT. The lower the Kh value of B. the
stronger the donation of protons that BIT will have compared with
H 3CT and the greater the production of H 3CT ions will be. Therefore,
the weaker the base, the stronger its conjugate acid will be.
Ammonium chloride. NH 4C1, dissociates in water to produce NH 4
ions. Cl ions, and an acidic solution . Chloride ions are the conjugate
base of a strong acid. HC1. so they show no noticeable tendency to
hydrolyze in aqueous solution . Ammonium ions, however, are the con -
jugate acid of a weak base. NH3. Ammonium ions donate protons to
water molecules. Equilibrium is established with an increased [ H O ],
^
so the pH is lower than 7.

Neutralization Curve for 100 mL

of 0.100 M CH .COOH Titrated with 0.100 M NaOH
13
12
11
10
9 Equivalence point 3
8
7
FIGURE 11 At point / on the X
a
6 2
titration curve, only acetic acid is
present. The pH depends on the weak 5
acid alone. At 2 there is a mixture of 4 1 l
V
CH COOH and CH3COO Adding *

Buffer region
NaOH ^ changes the pH slowly. At 3
2
point 3 all acid has been converted
to Cl I TOO . This hydrolyzes to 1
produce a slightly basic solution . 0
At 4 the pH is due to the excess 0 10 20 30 40 50 60 70 80 90 100 110120130140150160
OH that has been added .
"
mL NaOH added

610 CHAPTER 18
Hydrolysis in Acid- Base Reactions
Hydrolysis can help explain why the end point of a neutralization reac-
tion can occur at a pH other than 7. The hydrolysis properties of salts
are determined by the relative strengths of the acids and bases from
which the salts were formed . Salts can be placed in four general cate -
gories. depending on their hydrolysis properties: strong acid-strong
base, strong acid-weak base, weak acid-strong base, and weak acid -
weak base.
Salts of strong acids and strong bases produce neutral solutions
because neither the cation of a strong base nor the anion of a strong
acid hydrolyzes appreciably in aqueous solutions. HC1( a q ) is a strong
acid , and NaOH ( n ) is a strong base. Neither the Na ~ cation of the
^
strong base nor the Cl anion of the strong acid undergoes hydrolysis in
water solutions. Therefore, aqueous solutions of NaCI are neutral.
Similarly, KN03 is the salt of the strong acid HN 03 and the strong base
KOH . Measurements show that the pH of an aqueous KN 03 solution is
always very close to 7.
The aqueous solutions of salts formed from reactions between weak
acids and strong bases are basic, as Figure 11 shows. Anions of the dis-
solved salt are hydrolyzed by the water molecules, and the pH of the
solution is raised indicating that the hvdroxide-ion concentration has
,

increased. Aqueous solutions of sodium acetate. NaCH 3COO, are

.
basic. The acetate ions. CH3COO undergo hydrolysis because they
"

are the anions of the weak acid-acetic acid . The cations of the salt are
the positive ions from a strong base. NaOH. and do not hydrolyze,
because NaOH is 100 % dissociated.
Figure 12 shows that salts of strong acids and weak bases produce
acidic aqueous solutions. Cations of the dissolved salt are hydrolyzed in

Neutralization Curve for 100 mL

of 0.100 M NH 3 Titrated with 0.100 M HCI
13
12
11 1 Buffer region
A
10
9
2
8

X
7
a
6 FIGURE 12 At point / on the
Equivalence point 3
5 titration curve, only aqueous ammo -
4 nia is present . The pH is determined
3
by the base alone. At 2 there is a
mixture of NH ? and NHJ. Adding
2 4 HCI changes the pH slowly. At
1 point 2 all aqueous ammonia has
0 been converted to NH }. At 4 the
0 10 20 30 40 50 60 70 80 90 100110120130140150160
pH is determined by the excess
mL HCI added H ;Or that is being added.

CHEMICAL EQUILIBRIUM 611

 the water solvent, and the pH of the solution is lowered indicating that
,

the hydronium ion concentration has increased. In this case, the cations
of the salt undergo hydrolysis because they are the positive ions from a
weak base. The anions of the salt are the negative ions from a strong
acid and do not hydrolyze appreciably. Ammonium chloride. NH 4CI. is
a salt that produces an acidic solution.
Salts of weak acids and weak bases can produce either acidic, neu-
tral. or basic aqueous solutions, depending on the salt dissolved. This is
because both ions of the dissolved salt are hydrolyzed extensively. If
both ions are hydrolyzed equally, the solution remains neutral. The ions
in ammonium acetate. NH4CH;COO. hydrolyze equally, producing a
neutral solution, as shown in Figure lOd on page 608.
In cases in which both the acid and the base are very weak , the salt
may undergo essentially complete decomposition to the products of
hydrolysis. For example, when aluminum sulfide is placed in water, both
a precipitate and a gas are formed. The reaction is symbolized by the
following chemical equation.

AI2S3( S ) + 6H20( / ) 2 Al( OHh(5 ) + 3H 2S(g)

Both products are sparingly soluble in water and are removed from
solution.

SECTION REVIEW 7. What is hydrolysis ? Compare cation and anion

1. What is meant by an acid ionization constant? hydrolysis.
2. How is an acid ionization equilibrium expression 8. Which of the following ions hydrolyze in aqueous
written ? solution ?
.
3 What is meant by the term buffered solution! a. N03 d. K g. CO
b. F e. CH 3 COO h. PO
^
* '
4. Which of the following combinations of solutions
f. so
^
-
would form buffers when they are mixed? c. NH4
a. 50 mL of 1.0 M HCI and 50 mL of 1.0 M NaCI 9. Identify the following solutions as acidic, basic,
b. 25 mL of 0.5 M HN02 and 50 mL of 1.0 M or neutral.
NaNO 2 a. 0.5 M Kl c. 0.25 M NH4N03
c. 25 mL of 1.0 M HN 02 and 25 mL of 1.0 M NaCI b. 0.10 M Ba(0H)2 d. 0.05 M K 2 C 03
5. What is meant by the ion product constant for 10. Identify the acid and base from which each
water ? What is the value of this constant ? of the following salts was formed.
6. For each of the following reactions, identify each a. K 2Cr04 c. CaF2
conjugate acid -base pair. b. Ca(CH 3COO)2 d. (NH4)2 S04
a. H2 C 03 + H20 =? HC03 + H30^
Critical Thinking
b. H20 + H20 - ? H30+ + 0H “

11. RELATING IDEAS Describe how to make a buffer

c. H2 S + NH3 < •
HS- + NHJ solution using a strong base and one other
d. H 2 P04 + H20 i H 3 PO 4 + OH reagent.
~

612 CHAPTER 18
Solubility Equilibrium SECTION 4

OBJECTIVES
Explain what is meant by
1 onic solids dissolve in water until they are in equilibrium with their solubility product constants,
ions. An equilibrium expression can be written from the balanced chemi - and calculate their values.
cal equation of the solid's dissociation. Concentrations of the ions can
he determined from the balanced chemical equation and solubility data. Calculate solubilities using
*J
The ion concentrations can then be used to determine the value of the solubility product constants.
equilibrium constant. The numerical value for the equilibrium constant
can be used to predict whether precipitation occurs when solutions of
o Carry out calculations to
various concentrations are combined.
predict whether precipitates
will form when solutions
are combined.

Solubility Product
A saturated solution contains the maximum amount of solute possible
at a given temperature in equilibrium with an undissolved excess of the
substance. A saturated solution is not necessarily a concentrated solu -
tion. The concentration may be high or low. depending on the solubility
of the solute.
A general rule is often used to express solubilities qualitatively By .
this rule, a substance is said to be soluble if the solubility is greater than
1 g per 100 g of water. It is said to be insoluble if the solubility is less than
0.1 g per 100 g of water. Substances whose solubilities fall between these
limits are described as sliglulv soluble.
The equilibrium principles developed in this chapter apply to all satu -
rated solutions of sparingly soluble salts. Silver chloride is so sparingly
soluble in water that it is sometimes described as insoluble. Its solution
reaches saturation at a very low concentration of its ions. All Ag ’ and
Cl ions in excess of this concentration eventually precipitate as AgCI.
'

Consider the equilibrium system in a saturated solution of silver

chloride containing an excess of the solid salt. This system is repre -
sented by the following equilibrium equation and equilibrium-constant
expression.

AgCl(s) i Ag* ( aq ) + Cl ( aq )

The equation represents a heterogeneous reaction, as described on

page 599. Once again, we follow the convention of writing the equilibri-
um expression without including the solid species. Therefore [ AgCI ] .
does not appear in the final expression. The resulting equilibrium
expression gives the solubility product constant Ksp. The solubility prod-
uct constant of a substance is the product of the molar concentrations of

CHEMICAL EQUILIBRIUM 613

 .
its ions in a saturated solution each raised to the power that is the coeffi -
cient of that ion in the balanced chemical equation.

Kv = [ Ag1[cri
This equation is the solubility equilibrium expression for the reaction. It
.
expresses the fact that the solubility product constant Ks / „ of AgCI is the
product of the molar concentrations of its ions in a saturated solution.
Calcium fluoride is another sparingly soluble salt. The equilibrium in
a saturated CaF2 solution is described by the following equation.

CaF2(i) < =* Ca 2+(

uq ) + 2F ( o</ )
“

The solubility product constant has the following form.

Ksp ~ [ Ca2+][F ]2 “

Notice that this constant is the product of the molar concentration of

Ca2* ions and the molar concentration of F ions squared, as required
"

bv the general chemical equilibrium expression.

The numerical value of Ksp can be determined from solubility data.
Ihese data indicate that a maximum of 1.9 x 10- 4 g of AgCI can dissolve
in 1U0. g of water at 25 C. One mole of AgCI has a mass of 143.32 g. The
saturation concentration, or solubility, of AgCI can therefore be
expressed in moles per liter of water, which is very nearly equal to
moles per liter of solution.

1.9 x HP* gAcCI I lOOOjnt 1 mol AeCI

X X X
UK). r 1 ml. H:0 1F 143.32 _g-AgCT
= 1.3 X 10“ niol/L
~

Silver chloride dissociates in solution, contributing equal numbers of

Ag+ and Cl ions. The ion concentrations in the saturated solution are
therefore 1.3 x 10 '' mol/L.
“

[ Ag* ] = 1.3 x 10 5 “

[Cl | = 1.3 x 10 5
and
= [ Ag1[Cl |
^
“

Ksp = ( 1.3 x l() s)( 1.3 x lir5)

“

As/, = ( 1.3 x 10 5)2

”

Ksp = 1.7 x 10 10
This result is the solubility product constant of AgCI at 25 C.
Hie solubility of CaF: is <S.6 x 10 ' g/ U )( ) g of water at 25 C. Expressed
"

in moles per liter, as before, this concentration becomes 1.1 x Ur '

mol/ L. CaF-» dissociates in solution to yield twice as many F ions as

614 CHAPTER 18
Ca:+ ions. The ion concentrations in the saturated solution are 1.1 x 10~ *
for the calcium ion and 2( 1.1 x 10 * ) « or 2.2 x 10 *, for the fluoride ion .
“ “

Note that at equilibrium at 25 C, [ Ca:+] equals the solubility of 1.1 x

10 3 mol /L but [ F ] equals twice the solubility, or 2.2 x 10 * mol/L. The
“ “ '

number of moles of positive and negative ions per mole of compound

must always be accounted for when using A. / , and solubilities.
'

Ksp = [ C a 21[ F-]2

Ksp = ( 1.1 x 10~3)(2.2 x JO 3)2 "

Ksp = 5.3 x l (Ty

Thus, the solubility product constant of CaFi is 5.3 x HP9 at 25 C.

It is difficult to measure very small concentrations of a solute with
precision . For this reason , solubility data from different sources may
report different values of Ktp for a substance. Thus, calculations of Ksp
ordinarily should be limited to two significant figures. Representative
values of Ksp at 25 C for some sparingly soluble compounds are listed
.
in Table 3 Assume that all data used in Ksp calculations have been
taken at 25 C unless otherwise specified.
At this point , you should note the difference between the solubility of
a given solid and its solubility product constant. Remember that the
solubility product constant is an equilibrium constant representing the
product of the molar concentrations of its ions in a saturated solution . It

TABLE 3 Solubility Product Constants, Kw , at 25°C

Salt Ion product KSP Salt Ion product «sp
AgCH ,COO [ Ag ][ CH ,COO ]
+
l.
9 xl (T3 CuCI [ Cu ][cr ]
+
1.2 x 10 6
"

AgBr [ Ag+ ] [ Br -] 5.0 x 10 13 “

CuS [Cu2+][S21 6.3 x UP36
Ag:CO , [ Agi 2[ con 8.1 x 10 12 “

FeS [ Fe 2+][ S2-] 6.3 x 1( P S

,
AgC’l |Ag+ l[C|-] 1.8 x 10-10 Fc ( OH ): [ Fe2+][ OH ]2 8.0 x lO’ 16

8.3 x 10- 7 Fe ( OH ),
,
Agl [ Ag+][ I1 ' [ Fe +][ OH -]3 4 x HP38
Ag:S [ Ag+]-[S21 6.3 x 10-?" HgS [ Hg2+][S2-] 1.6 xlO 52
*

AI ( OHh [ Al3+][OH ]3 ~
1.3 x HP33 MgCO , [ Mg21[COT ] 3.5 x 10~s
BaCO , [ Ba 2+ J [C02f ] 5.1 x 10-9 Mg( OH ) i [ Mg2+ ] [ OH -]2 1.8 x l O n
BaSOj [ Ba 2+l [SOr ] 1.1 x 1(P10 MnS [ Mrr + )[S2-] 2.5 x 10 13
CdS [Cd2+][S2-] 8.0 x 10 ' 27 PbCP [ Pb2 + ][ C1 ]:
"
1.6 x 10- -

CaCO , [Ca 2+][COf ] 2.8 x 10-9 PbCr 04 [ Pb2+][Cr021 2.8 x lO’ 13

CaF: [Ca:+][ F ]2
'
5.3 x 10-9 PbS04 [ Pb2+][S02- ] 1.6 xlO 8
"

Ca ( OH ); [Ca:"] [ OH ]:'
5.5 x lO-6 PbS -
[ Pb- ][S 2 - ] 8.0 x lO" 28

CaS04 [ Ca 2+][S02 ]'

9.1 x lO 6 "
SnS [Sn 2+][S21 1.0 x 10 25
'

CoCO, [ Co 2 ] [ COT ]
*
_ 1.4 xlO-13 SrS04 [Sr2+][S02-] 3.2 xlO ' 7

CoS [Co2+ ][S21 4.0 x HP21 ZnS [ Zn 2+][S21 1.6 x 1 O

’ 24

CHEMICAL EQUILIBRIUM 615

 has only one value for a given solid at a given temperature. The solubility
of a solid is an equilibrium position that represents the amount of the solid
required to form a saturated solution with a specific amount of solvent. It
has an infinite number of possible values at a given temperature and is
dependent on other conditions, such as the presence of a common ion.

SAMPLE PROBLEM B
Calculate the solubility product constant, Kspy for copper ( l ) chloride, CuCI, given that the solubility of
this compound at 25°C is 1.08 x 10 2 g/ 100. g H20.
"

SOLUTION
1 ANALYZE Given: solubility of CuCI = 1.08 x 10“2 g CuCI/ IOO. g H20
Unknown: Ksp

2 PLAN Start bv converting the solubility of Cud in g/ 100. g H:0 to mol/ L. You will need the molar
mass of CuCI to get moles CuCI from grams CuCI. Then use the solubility of the [ Cu ] and 4

|CT] ions in the Ksp expression and solve for Ksp.

g CuCI l gH2Q 1000 mL I mol CuCI

X - x x = solubility in mol/L
lOO. g H,0 ^ l mL H:Q lL g CuCI
CuCI(.v ) ; Cu ~ ( uq ) + Cl ~ ( aq )
,
Ks > = [Cu+][cr ]
[ Cu ' | = [ Cl ~] = solubility in mol/ L

3 COMPUTE The molar mass of CuCI is 99.0 g/mol.

1.08 x Hr3 gjCuC1 LgHsO 1000 mL 1 mol CuCI
solubility = x x x
100. gUsO I mL 1L 99.0 gT?uCI

1.09 X nr -’ mol/L CuCI

|Cu+ ] = |C1 | = 1.09 X I0"3 mol/L
Ks[ ) = ( 1.09 x l(r ’) ( 1.09 x nr3) = 1.19 x 10 6 '

4 EVALUATE The answer contains the proper number of significant figures and is close to the Ksp value
given in Table 3.

PRACTICE Answers in Appendix E

1 . Calculate the solubility product constant, Kspy of lead(II) chloride,

PbCI 2. which has a solubility of 1.0 g/ 100. g H:0 at 20 C. Go to go.hrw.com for
more practice problems
2. A 5.0 gram sample of Ag:S04 will dissolve in 1.0 L of water. that ask you to calculate
Calculate the solubility product constant for this salt. solubility product
constants.
Keywofd ; HC6EQUX

616 CHAPTER 1 8
 Calculating Solubilities
Once known, the solubility product constant can be used to determine
the solubility of a sparingly soluble salt . Suppose you wish to know how
many moles of barium carbonate. BaC03. can be dissolved in 1 L of
water at 25 C. From Table 3, Ky [ for BaC03 has the numerical value
)

5.1 x 10 The equilibrium equation is written as follows.

BaC()3( s) f Ba2+(aq) + CO\ ( aq )

~

Given the value for Ks[ r we can write the solubility equilibrium expres-
.
sion as follows
/CJ/, = [Ba2+][CO ] = 5.1 x |(Ty
^
Therefore, BaC03 dissolves until the product of the molar concentra-
tions of Ba ions and CO ions equals 5.1 x 10 . The solubility
g

^
* "

equilibrium equation shows that Ba2* ions and CO5 ions enter the "

solution in equal numbers as the salt dissolves. Thus, they have the same
concentration. Let |Ba ~ ] =.v. Then [ CO ] = .v also.
^
“

|Ba2*][C02'] = Ksp = 5.1 x 10^

g
(.v )(.v) = .v2 = 5.1 x IO-

x = V 5.1 x urv
Tlie molar solubility of BaC03 is 7.1 x 1 mol/L.
Thus. the solution concentration is 7.1 x 10° M for Ba2" ions and
7.1 x 1(T5 M for CO5 ions.
*

SAMPLE PROBLEM C
Calculate the solubility of silver bromide, AgBr, in mol/L, using the Ksp value for this compound listed
.
in ( able 3

SOLUTION
1 ANALYZE Given: A' v /, = 5.0 x 10 13
Unknown: solubility of AgBr

2 PLAN AgBr < > Ag+( aq ) + Br ( aq )

Ksp = [ Ag+][Br ] “

|Ag | = [ Br ], so let [ Ag* ] =.v and [ Br | = x

* '

3 COMPUTE Ksp = [ AglfBr ] *

= XT
= 5.0 x 10 13
jr
"

x = V 5.0 x 10- 13
Solubility of AgBr = V5.0 x KT11- = 7.1 x 10 7 mol/L *

CHEMICAL EQUILIBRIUM 617

4 EVALUATE The answer has the proper number of significant figures and is close to an estimated value
of 7.0 x 10 calculated as V 49 x 10 i 4.
" “

PRACTICE Answers in Appendix E

1 . Calculate the solubility of cadmium sulfide, CdS. in mol/ L, given

the Ksp value listed in Table 3.
t\
2 . Determine the concentration of strontium ions in a saturated Go to go.hrw.com for
solution of strontium sulfate, SrS04. if the Ksp for SrS04 is more practice problems
3.2 x nr7. that ask you to calculate
solubilities.
Keyword: HC 6 EQUX

Precipitation Calculations
In an earlier example. BaC03 served as the source of both Ba2+ and CO\~
ions. Because each_ mole of BaC03 yields one mole of Ba:~ ions and one
mole of CO ions, the concentrations of the two ions were equal.
^
However , the equilibrium condition does not require that the two ion
concentrations be equal . Equilibrium will still be established so that the

^
ion product | Ba 2“|[ CO ] does not exceed the value of K > p for the system.
~

Similarly, if the ion product [ Ca 2 + ]|F ]2 is less than the value of Ksp
“

at a particular temperature, the solution is unsaturated. If the ion product

is greater than the value for KSfV CaF: precipitates. This precipitation
reduces the concentrations of Ca 2+ and F ions until equilibrium is
established .
Suppose that unequal quantities of BaCN and Na:CG 3 are dissolved
in water and that the solutions are mixed . If the ion product
[ Ba 2+ ][ COi| ] exceeds the Ksp of BaC03, a precipitate of BaC03 forms.
“

Precipitation continues until the ion concentrations decrease to the

point at which [ Ba 2* ][CQ5 ] equals the Ksp.
‘

r
FIGURE 1 3 Nitrate salts of Ag"
( a ) and Pb: ( b ) are soluble. When
'

^
chromate ions. CrO . combine with
"

Ag ( c ) or Pb:" ( d ). an insoluble salt

*

forms. Thiocyanate ions. SCN . can

form an insoluble salt with Ag* ( e )
or a soluble salt with Fe ( f ).
*

(d)

618 CHAPTER IS
 Substances differ greatly in their tendencies to form precipitates
when mixed in moderate concentrations. The photos in Figure 13 show
the behavior of some anions in the presence of certain cations. Note that
some of the combinations have produced precipitates and some have
not . The solubility product can be used to predict whether a precipitate
forms when two solutions are mixed.

SAMPLE PROBLEM
Will a precipitate form if 20.0 mL of 0.010 M BaCI2 is mixed with 20.0 mL of 0.0050 M Na 2S() 4 ?

SOLUTION
1 ANALYZE Given: concentration of
BaCL = 0.010 M
volume of BaCL = 20.0 mL
concentration of Na2S04 = 0.0050 M
volume of Na2S04 = 20.0 mL
Unknown: whether a precipitate forms

2 PLAN Tine two possible new pairings of ions are NaCI and BaS 04. Of these. BaS04 is a sparingly
soluble salt . It will precipitate if the ion product [ Ba2 ] [ SO;j ] in the combined solution
* '

.
exceeds A \; for BaS04. From the list of solubility products in Table 3, the Ksf is found
) )

to be l.l x IO~ln. The solubility equilibrium equation follows.

BaSQ4(s ) Ba2+( aq ) + SO ] ~( aq )

The solubility equilibrium expression is written as follows.

= | Ba>][ S05 ] = l . l x l (r l°
^
"

First [ Ba:+| and |SOj ) in the above solution must be found. Then the ion product is
"

calculated and compared with the Ksp,

3 COMPUTE Calculate the mole quantities of Ba2 and SOj ions.

0.010 mol Ba 2 '
0.020 Lx = 0.000 20 mol Ba 2"
lL

0.0050 mol SO3

"

0.020 L x = 0.000 10 mol SO

IL
Calculate the total volume of solution containing Ba 2" and SO3 ions.
0.020 L 4- 0.020 L = 0.040 L
Calculate the Ba 2 + and SO5 ion concentrations in the combined solution.
'

0.000 20 mol Ba2*

= 5.0 x 10 -' mol/ L Ba:*
*

0.040 L

0.000 10 mol S( >C

= 2.5 x 10 ' mol/L SO 3
“

0.040 L

CHEMICAL EQUILIBRIUM 619

 Calculate the ion product.
[Ba2+][SO$ ] = ( 5.0 x 10 3)( 2.5 x 10 3)
“ " "

5
= 1.2 x 10'

.
The ion product . 1.2 x 10'5. is greater than the value of K ^ p 1.1 x 10~ 10. so precipitation
occurs.

4 EVALUATE The answer contains the appropriate number of significant figures and is close to an esti -
mated value of 1 x 10~ \ calculated as ( 5 x 1(T3) ( 2 x 10 ): because 10 5 > 10 m , precipitation
v ' "

should occur.

PRACTICE Answers in Appendix E

1. Does a precipitate form when 100. mL of 0.0025 M AgNO {T’ Pd ifcfldil

^ Go to go. hrw. com for
and 150. mL of 0.0020 M NaBr solutions are mixed ?
more practice problems
2 . Does a precipitate form when 20. mL of 0,038 M that ask you to perform
and 30. mL of 0.018 M KC1 solutions are mixed ?
PblNO
^ precipitation
calculations.
Keyword: HC 6 EQUX

Limitations on the Use of K

Hie solubility product principle can be very useful when applied to solu -
tions of sparingly soluble substances. It cannot be applied very successfully
to solutions of moderately soluble or very soluble substances. This is
because the positive and negative ions attract each other, and this attraction
becomes appreciable when the ions are close together. Sometimes it is nec -
essary to consider two equilibria simultaneously. For example, if either ion
hydrolyzes, the salt will be more soluble than predicted when only the sol -
ubility product constant is used . The solubility product is also sensitive to
changes in solution temperature to the extent that the solubility of the dis-
solved substance is affected by such changes. All of these factors limit the
conditions under which the solubility product principle can be applied .

SECTION REVIEW .
6 Determine whether a precipitate will form if
1. What is a solubility product constant ? How are 20.0 mL of 1.00 x 10 7 M AgN03 is mixed
'

such constants determined? with 20.0 mL of 2.00 x 10~ 9 M NaCI at 25°C.

.
2 How are solubility product constants used to Critical Thinking
calculate solubilities ? 7. ANALYZING DATA A solution is 0.20 M in each of
3. What is an ion product ? the following: Ca(N03)2, Cr(N03)3, and La(N03) 3.
4. How are calculations to predict possible precipita - Solid NaF is added to the solution until the [ F~]
tion carried out ? of the solution is 1.0 x 10- 4 M. Given the values
of Ksp below, describe what will happen.
5. What is the value of Ksp for Ag2 S04 if 5.40 g CaF2 = 3.9 x 10 ; CrF3 = 6.6 x 1(Tn; and
is soluble in 1.00 L of water ? "
‘

LaF 3 = 4.0 x 10-17

620 CHAPTER 18
 CHAPTER HIGHLIGHTS
The Nature of Chemical Equilibrium
I Vocabulary •A reaction system in which the forward and reverse reactions
reversible reaction occur simultaneously and at the same rate is said to be at equi -
chemical equilibrium librium. Both reactions continue, but there is no net change in
equilibrium constant the composition of the system.
chemical equilibrium expression • At equilibrium, the ratio of the product of the molar concen-
trations of substances formed to the product of the molar con-
centrations of reactants, each raised to the appropriate power,
.
has a definite numerical value, K which is the equilibrium con-
stant at a given temperature.

Shifting Equilibrium
I Vocabulary •According to Le Chateliers principle, when a stress ( a change
common - ion effect in concentration, pressure, or temperature) is applied to a sys -
tem at equilibrium, the equilibrium is shifted in the direction
that relieves the stress.
•The common-ion effect is recognized when a solution contain-
ing ions such as those of a reactant or a product in an equilibri-
um system is added to the system. Le Chateliers principle
explains the response of the system to the stress.

Equilibria of Acids , Bases , and Salts

Vocabulary
> •The equilibrium expression for the ionization constant of the
acid ionization constant weak acid HA follows.
buffered solution IH3OJAJ
hydrolysis ° [ HA ]
•Salts formed from strong bases and weak acids produce aque -
ous solutions that are basic because of anion hydrolysis.
•Salts formed from strong acids and weak bases produce aque -
ous solutions that are acidic because of cation hydrolysis.
•Salts formed from strong acids and strong bases do not
hydrolvze in water, and their solutions are neutral.
•Salts formed from weak acids and weak bases may produce
neutral, acidic, or basic solutions, depending on the relative
amounts of cation and anion hydrolysis.

Solubility Equilibrium
I Vocabulary •Ions of salts that are very sparingly soluble form saturated aque-
solubility product constant ous solutions at low concentrations. The solubility equilibrium
expression for such salts yields a constant — the solubility product
constant . Ksp.

CHEMICAL EQUILIBRIUM 621

 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D .
atequilibrium, determine the concentration of
The Nature of Chemical N: at that point.
Equilibrium N2(g) + 3H2(g) « » 2NH ( )
= ,
*
7. The value of the equilibrium constant for the
SECTION 1 REVIEW reaction below is 40.0 at a specified temperature.
1. Describe and explain how the concentrations of What would be the value of that constant for the
.
A . B C. and D change from the time when A reverse reaction under the same conditions?
and B are first combined to the point at which H2( jf ) + I2(i? ) I 2HI(g)
equilibrium is established for the reaction
A+B C + D.
2. a. Write the general expression for an equilibri - Shifting Equilibrium
um constant based on the equation / / A +
SECTION 2 REVIEW
/ /iB + . . • f .vC + vD + . ..
b. What information is provided by the value of 8. Predict whether each of the following pressure
K for a given equilibrium system at a speci - changes would favor the forward or reverse
fied temperature ? reaction.
3 . In general, which reaction is favored ( forward 2NO(g) + 02(g) 2NO,(s)
or reverse ) if the value of K at a specified tem - a. increased pressure
perature is b. decreased pressure
a. very small? 9. In heterogeneous reaction systems, what types
b. very large ? of substances do not appear in the equilibrium
constant expression? Why ?
10. Explain the effect of a catalyst on an equilibri -
PRACTICE PROBLEMS
urn system.
4. Determine the value of the equilibrium con- 11. Predict the effect of each of the following on
stant for each reaction given, assuming that the the indicated equilibrium system in terms of the
equilibrium concentrations are found to be direction of equilibrium shift ( forward, reverse,
those specified. ( Concentrations are in mol/L. ) or neither ).
( Ilint: See Sample Problem A . ) 2HCI(g) + 184 Id
H:( g) + Cl2(g)
a. A 4- B 4
C: | A ] = 2.0; [ B| = 3.0: [ C] = 4.0 a. addition of CL
b. D + 2E ? F + 3G; [ D] = 1.5; [E] = 2.0; .
b removal of HCI
[F] = 1.8: [G] = 1.2 c. increased pressure
c. N2(g) + 3H2(g) * 2NHj(g): [ N:] = 0.45: d. decreased temperature
[ H2 ] = 0.14: [ NH3 ] = 0.62 e. removal of H:
5 . An equilibrium mixture at a specific tempera- f. decreased pressure
ture is found to consist of 1.2 x It )- mol / L HCI.
1

e. addition of a catalyst
3.8 x l() 4 mol/L G:, 5.8 x 10 2 mol/L H:0 and
" "
. h. increased temperature
5.8 x H )-2 mol/L CL according to the following: i. decreased system volume
4HCl( g) 4- 02 ( g ) f 2 H:0(g) + 2CL(g). 12. How would the changes in ( a ) through ( i ) of
Determine the value of the equilibrium con- item 11 affect the new equilibrium concentra -
stant for this system. tion of HCI and the value of K at the new
6. At 450 C, the value of the equilibrium constant equilibrium?
for the following system is 6.59 x 10 \ If
"
13. Explain why changes in the concentrations of the
[ NIL ) = l .23 x Hr4 M and [H:] = 2.75 x 10 2 M ~

reactants and products at equilibrium have no

impact on the value of the equilibrium constant.

622 CHAPTER 18
 CHAPTER REVIEW

14. What relative pressure ( high or low ) would 21. Explain why the pH of a solution containing
result in the production of the maximum level both acetic acid and sodium acetate is higher
of CC>2 according to the following equation? than that of a solution containing the same con-
Why ? centration of acetic acid alone.
=
2CO(g) + O2( g ) ; ? 2CO:( g)
15. What relative conditions ( reactant concentra-
22. The ionization constant. Kr for acetic acid is
1.8 x \ Q~ - at 25 C. Explain the significance of
tions. pressure, and temperature ) would favor a this value.
high equilibrium concentration of the under - 23. a. From the development of Ktl described in
lined substance in each of the following equilib- Section 3. show how you would express an ion-
rium systems? ization constant. Kh, for the weak base NH v
a. 2CO(g) + 02( g ) * 2CO:(g) + 167 kJ b. In this case. Kh = 1.8 x 10~ \ What is the signifi-
b. Cu 2+( aq ) + 4NH }( uq ) cance of this numerical value to equilibrium?
*
CU(NH3)5+(^/ ) + 42 kJ
c. 2HI( g ) + 12.6 kJ H:( £ ) + Solubility Equilibrium
il. 4HCl(g) + 02 {g) * SECTION 4 REVIEW
2 H:Q( g) + 2CU( g ) + 113 kJ
24. Explain why a saturated solution is not neces-
e. PCIs(g ) + 88 kJ * PCI3(g) + Cl2(g) sarilv a concentrated solution.
.
w

16. The reaction between hemoglobin Mb, and oxy - 25 . What rule of thumb is used to distinguish
gen, 02. in red blood cells is responsible for between soluble, insoluble, and slightly soluble
transporting 02 to body tissues. This process can substances?
be represented by the following equilibrium 26. What is the relative ion concentration of an
reaction: ionic substance typically involved in solubility
Hb( aq ) + 02(g) HbO:( w/ ) equilibrium systems?
What will happen to the concentration of oxy - 27. What is the relationship between A s / and the
'
)

.
genated hemoglobin. HbO: at high altitude, product of the ion concentrations in terms of
where the pressure of oxygen is 0.1 atm instead determining whether a solution of those ions
of 0.2 atm. as it is at sea level? is saturated?
17. What two factors determine the extent to which
reacting ions are removed from solution ?
PRACTICE PROBLEMS
18. Identify the three conditions under which ionic
reactions can run to completion, and write an 28. The ionic substance EJ dissociates to form
equation for each. E:~ and J:~ ions. The solubility of EJ is 8.45 x
10""6 mol/L. What is the value of the solubility
product constant ? ( Hint: See Sample Problem B. )
29. Calculate the solubility product constant Kyp for
Equilibria of Acids , Bases, each of the following, based on the solubility
and Salts information provided:
a. BaS04 = 2.4 x HT4 g/ 100. g H:0 at 20°C
SECTION 3 REVIEW b. Ca( OH)2 = 0.173 g/100. g H:0 at 20°C
19. a. Write the ion product constant expression 30. Calculate the molar solubility of a substance
for water. MN that ionizes to form M:~ and N2 ions,
_
b. What is the value of this constant at 25 C? given that Ksp = 8.1 x 10 h. ( Hint: See Sample
20. List and distinguish between the four general Problem C. )
categories of salts, based on their hydrolysis
properties, and give an example of each.

CHEMICAL EQUILIBRIUM 623

 CHAPTER REVIEW

31 . Use ihe Ksp values given in Table 3 to evaluate 40 . Calculate the equilibrium constant. K , for the
the solubility of each of the following in moles following reaction at 900°C.
per liter. H 2( g ) + C02(g) H 20( g ) + CO(g )
a . AgBr The components were analyzed , and it was found
b. CoS =
that [ H 2 ] = 0.061 mol / L. [ CO:] 0,16 mol/ L.
[ H:0|= 0.11 mol / L. and [ CO ] = 0.14 mol / L.
32 . Complete each of the following relative to
the reaction that occurs when 25.0 mL of 41 . A solution in equilibrium with solid barium
0.0500 M Pb( NOv) 2 is combined with 25.0 mL phosphate is found to have a barium ion concen -
of 0.0400 M Na ^ SO , if equilibrium is reached tration of 5.0 x 10 4 M and a Ksp of 3.4 x 10"®
'
.
at 25°C. Calculate the concentration of phosphate ion.
a . Write the solubility equilibrium equation at 42. At 25°C. the value of K is 1.7 x 10~ 13 for the fol -
25°C. lowing reaction .
b. Write the solubility equilibrium expression 2 N 20( g ) + 02 (g ) 4 NO( g )
for the net reaction . It is determined that [ N 20 ] = 0.0035 mol/ L and
33. The ionic substance T3U 2 ionizes to form T:" [ 02 ] = 0.0027 mol / L. Using this information , what
and U ' ions. The solubility of T3U 2 is 3.8 x is the concentration of NO(g ) at equilibrium ?
I 0 ln mol / L . What is the value of the solubility
"
43. Tooth enamel is composed of the mineral
product constant ? hydroxyapatite. Ca5( P04 )30 H. which has a Ksp
34. A solution of Agl contains 2.7 x 10 ln mol/ L AgT
“
of 6.8 x 1 O 37. The molar solubility of hydroxy -
'

What is the maximum I concentration that can apatite is 2.7 x 10 5 mol / L . When hydroxyap-
“

exist in this solution ? atite is reacted with fluoride, the OH is

35 . Calculate whether a precipitate will form if replaced with the F ion on the mineral , form -
0.35 L of 0.0044 M Ca ( N03)2 and 0.17 L of ing fluorapatite. Ca5 ( P04 )3F. ( The latter is hard -
0.000 39 M NaOH are mixed at 25°C. (See Table 3 er and less susceptible to cavities. ) Hie Ksp of
'

for Ksp values. ) ( Hint: See Sample Problem D. ) fluorapatite is 1 x 10 * . Calculate the molar sol -
"

°
36. Determine whether a precipitate will form if ubility of fluorapatite in water. Given your cal -
1.70 g of solid AgN03 and 14.5 g of solid NaCI culations, can you support the fluoridation of
are dissolved in 200. mL of water to form a drinking water ?
solution at 25°C. 44. Determine if a precipitate will form when
37 . If 2.50 x 1 (T: g of solid Fe ( N 03)3 is added to 0.96 g Na 2C03 is combined with 0.20 g BaBr:
100. mL of a 1.0 x 1 (T4 M NaOH solution , will a in a 10. L solution ( Ksp = 2.8 X 10 Y .
precipitate form ? 45 . For the formation of ammonia , the equilibrium
constant is calculated to be 5.2 x 10 5 at 25 C .
“

After analysis, it is determined that [ N 2 ] = 2.00 M

MIXED REVIEW and [ H 2] = 0.80 M. How many grams of ammonia
are in the 10. L reaction vessel at equilibrium ?
38 . Calcium carbonate is only slightly soluble in Use the following equilibrium equation .
water. N2(g) + 3H2(g) <r ? 2 NH3(g )
a . Write the equilibrium equation for calcium
carbonate in solution .
b. Write the solubility product constant expres- CRITICAL THINKING
sion . Ksp , for the equilibrium in a saturated
solution of CaC03. 46 . Relating Ideas Let s equal the solubility, in
39 . Calculate the concentration of Hg2+ :ions in a mol / L. of AB2. In terms of 5, what is the molar
saturated solution of HgS( s ). How many Hg 2^ concentration of A ? of B ? What is the Ksp of
ions are in 1000 L of the solution ? AB2?

624 CHAPTER 18
 CHAPTER REVIEW

47 . Predicting Outcomes When gasoline burns in 51 . Carry out library research on the use of cata -
an automobile engine, nitric oxide is formed lysts in industrial processes. Explain what types
from oxygen and nitrogen . Nitric oxide is a of catalysts are used for specific processes, such
major air pollutant . High temperatures such as as the Haber process.
those found in a combustion engine are needed
for the following reaction :
N2( g ) + Ojte) f > 2 NO ( g ) ALTERNATIVE ASSESSMENT
K for the reaction is 0.01 at 2000°C. If 4.0 mol
of Ni. 0.1 mol of 0% and 0.08 mol of NO are 52 . Research nitrogen narcosis in the library. What
placed in a 1.0 L vessel at 2000°C, predict which causes nitrogen narcosis, and how does it relate
reaction will be favored . to Le Chatelier 's principle?

USING THE HANDBOOK

48. An equilibrium system helps maintain the pH
of the blood . Review the material on the carbon
i Graphing Calculator Chemical
Equilibrium
Go to go.hrw.com for a graphing calculator
-
dioxide bicarbonate ion equilibrium system in
exercise that asks you to calculate the per -
Group 14 of the Elements Handbook , and
cent ionization for an acid equilibrium .
answer the following.
a . Write the equation for the equilibrium Keyword: HC 6 EQUX
system that responds to changes in H 30
concentration .
b. Use Le Chatelier’s principle to explain how
hyperventilation affects this system .
c. How does this system maintain pH when
acid is added ?
49. Hie reactions used to confirm the presence of
transition metal ions often involve the formation
of precipitates. Review the analytical tests for the
transition metals in the Elements Handbook . Use
that information and Table 3 to determine the
minimum concentration of Zn:‘ needed to pro-
duce a precipitate that confirms the presence of
Zn . Assume enough sulfide ion reagent is added
to the unknown solution in the test tube to pro-
duce a sulfide ion concentration of 1.4 x 1 ( ) 2" M .
~

RESEARCH & WRITING

50 . Find photos of several examples of stalagmites
and stalactites in various caves. Investigate the
equilibrium processes involved in the formation
of stalagmites and stalactites.

CHEMICAL EQUILIBRIUM 625

 Math Tutor DETERMINING EQUILIBRIUM CONSTANTS

For a given temperature, you can write a mathematical equation that describes the equi -
librium of a reaction in terms of concentration. The equation defines an equilibrium con-
stant, K, as a function of the concentrations of products and reactants at equilibrium.
Consider an equilibrium process in which reactants A and B form products C and D.
r?A + mB xC + y D
The terms n, m, x, and y are the coefficients of the balanced equation.
[ C ]1DF
K^
[ A ]n[ B ]m

Problem-Solving TIPS
• Always use a balanced chemical equation to write an equilibrium-constant equation.
• To write an equation, place the product concentrations in the numerator and the
reactant concentrations in the denominator. Raise each substance s concentration
'

to the power equal to the substance's coefficient in the balanced chemical equation.
• The concentration of any solid or pure liquid that takes part in the reaction is left
out because these concentrations never change.

SAMPLE
Write an equation for the equilibrium constant of the reaction in which nitrogen monoxide
changes to dinitrogen monoxide and nitrogen dioxide.
To write an equation for an equilibrium constant , you must start with a balanced chemical
equation for the equilibrium reaction. By writing the formulas of the compounds mentioned in
the description, you get the unbalanced equilibrium equation NO(g) » N (g) + N (g).
* 20 02
Balancing the equation requires a coefficient of 3 in front of NO, giving 3NO(g) <
N20( g) + N02(g). Next, write an equilibrium equation. Remember, each concentration in the
equilibrium equation is raised to a power equal to its coefficient in the balanced chemical equa -
tion. The product concentrations. [ N:0 ] and [ NO:]. are placed in the numerator. The coefficient
of each of the products is 1 . so the exponent of each concentration is 1. There is only one reac -
tant, so its concentration, [ NO ], is written in the denominator. Its coefficient is 3 in the balanced
chemical equation, so the concentration of NO is raised to the third power. The exponents with
a value of I do not have to be written. The resulting equation is

' .
INSOj INO ] 1
"
[N20 ][ N0:]
|NO]3 [NO ] 3

PRACTICE PROBLEMS
.
1 Write equations for the equilibrium constant of 2. Use the equilibrium concentrations below to cal-
each of the following hypothetical reactions: culate the equilibrium constant for the following
a. A( aq ) + 2 B ( aq ) ? AB2(nr/ ) decomposition reaction:
b. 2DE2(g) > D ( # ) + 2E ( g)
: : 2BrF5(g) <r - Br2(g) + 5F:(g)
[BrF5 ] = 0.000137 mol/L. [ Br:] = 0.00050 mol/L.
and [ F:] = 0.0025 mol/L

626 CHAPTER 18
Answer the following items on a separate piece of paper. 7. Le Chateliers principle states that
MULTIPLE CHOICE A . at equilibrium, the forward and reverse reac -
tion rates are equal.
.
1 A chemical reaction is in equilibrium when
B. stresses include changes in concentrations,
A. forward and reverse reactions have ceased.
pressure, and temperature.
B. the equilibrium constant equals 1.
C. to relieve stress, solids and solvents are omit -
C. forward and reverse reaction rates are equal.
ted from equilibrium constant expressions.
D. No reactants remain.
D. chemical equilibria respond to reduce
2. Which change can cause the value of the equi- applied stress.
librium constant to change?
SHORT ANSWER
A . temperature
B. concentration of a reactant .
8 Describe the conditions that would allow you to
C. concentration of a product conclusively determine that a solution is satu -
D. None of the above rated. You can use only visual observation and
cannot add anything to the solution.
3. Consider the following reaction:
2C( s ) + 02(g ) 2CO(g) 9. The graph below shows the neutralization curve
The equilibrium constant expression for this for 100 mL of 0.100 M acid with 0.100 M base.
reaction is Which letter represents the equivalence point?
What type of acid and base produced this
l
^
2[CO ]
A. , c* curve ?
[ o:] [ 02][ 2C ]
[ COp
B.
[ 02 ] [cf [o2 ]2 13

.
4 The solubility product of cadmium carbonate. 11 d
.
CdC03. is 1.0 x 10 12 In a saturated solution of
"

this salt, the concentration of Cd2+( aq ) ions is 9 c

A . 5.0 x 10 13 mol/L
"
.C. 1.0 x 10 '' mol/ L.
i 7
~ 12
B . 1.0 x 10 mol/L. D. 5.0 x 10" ' mol/L. o. b
5
5. Consider the following equation for an equilib- a
rium system: 3
2 PbS( s ) + 302(g) + C(s) ; *
2Pb(.v ) + CO:(g) + 2SO:(g ) 1
Which concentration( s ) would be included in o
0 10 30 50 70 90 110 130 150
the denominator of the equilibrium constant
mL base added
expression?
.
A. Pb( s ) C02(g), and S02( g)
B. PbS(s), 02(g), and C( s )
EXTENDED RESPONSE
C. 02(g), Pb( s ), CO:( g). and S02(g)
D. O:( g) .
10 Explain how the same buffer can resist a change
in pH when either an acid or a base is added.
.
6 If an exothermic reaction has reached equilib -
Give an example.
rium, then increasing the temperature will
.
A favor the forward reaction .
B. favor the reverse reaction.
C. favor both the forward and reverse reactions. Keeping a positive attitude dur-
ing any test will help you focus on the test and likely
D. have no effect on the equilibrium. improve your score.

CHEMICAL EQUILIBRIUM 627

 MICRO
EXPERIMENT 18 L A B

Measuring Ka for Acetic Acid

OBJECTIVES BACKGROUND
• Compare the conductivities of solutions The acid dissociation constant , KIV is a measure
of known and unknown hvdronium ion of the strength of an acid . Strong acids are complete-
concentrations. ly ionized in water. Because weak acids are only
partly ionized , they have a characteristic Ka value.
• Relate conductivity to the concentration
Properties that depend on the ability of a substance
of ions in solution.
to ionize, such as conductivity and colligative proper -
• Explain the validity of the procedure ties, can be used to measure Ka . In this experiment ,
on the basis of the definitions of strong you will compare the conductivity of a 1.0 M solu -
and weak acids.
tion of acetic acid , CH3COOH, a weak acid , with the
• Compute the numerical value of Ka for conductivities of solutions of varying concentrations
acetic acid . of hydrochloric acid. HC1, a strong acid . From the
comparisons you make, you will be able to estimate
MATERIALS the concentration of hydronium ions in the acetic
• 1.0 M acetic acid , CH 3COOH acid solution and calculate its Kir
• 1.0 M hydrochloric
• f
acid , HCI
SAFETY
• 24- well plate
• distilled or deionized water
• LED conductivity testers
For review of safety, please see Safety in the
• paper towels Chemistry Laboratory in the front of your book.
• thin -stemmed pipets
PREPARATION
1 . Create a table with two columns for recording
your observations. Head the first column “ HCI
concentration .' A wide second column can be
*

headed “ Observations and comparisons."

PROCEDURE
Film canister ^ LED
cap 1. Obtain samples of 1.0 M HCI solution and 1.0 M
1

— 20 cm
wire
10 cm
CH 3COOH solution .
2 . Place 20 drops of HCI in one well of a 24 - well
wire plate. Place 20 drops of CH 3COOH in an adja -
cent well . Label the location of each sample.
Film
canister -
3. Test the HCI and CH ,COOH with the conduc-
tivity tester . Note the relative intensity of the
Teacher- made LED conductivity tester

628 CHAPTER 18
 EXPERIMENT 18

tester light for each solution . After testing, rinse CLEANUP AND DISPOSAL
the tester probes with distilled water. Remove 9. Clean your lab station . Clean all equip-
any excess moisture with a paper towel . ment , and return it to its proper place .
4. Place 18 drops of distilled water in each of six Dispose of chemicals and solutions in
wells in your 24 - well plate. Add 2 drops of containers designated by your teacher. Do not
1.0 M HC1 to the first well to make a total of pour any chemicals down the drain or throw any-
20 drops of solution . Mix the contents of this thing in the trash unless vour teacher directs you
well thoroughly by picking the contents up in a to do so. Wash your hands thoroughly after all
pipet and returning them to the well . work is finished and before vou leave the lab.
5. Repeat this procedure by taking 2 drops of the ANALYSIS AND INTERPRETATION
previous dilution and placing it in the next well
1. Resolving Discrepancies: How did the conduc-
containing 18 drops of water. Return any unused
tivity of the 1.0 M HCI solution compare with
solution in the pipet to the well from which it
that of the 1.0 M CH 3COOH solution ? Why do
was taken . Mix the new solution with a new
you think this was so?
pipet . ( You now have 1.0 M HCI in the well from
Procedure step 2, 0.10 M HCI in the first dilution 2. Organizing Data: What is the H 3CT concentra -
well , and 0.010 M HCI in the second dilution . ) tion of the HCI solution that most closely
matched the conductivity of the acetic acid ?
6 . Continue diluting in this manner until you have
six successive dilutions. The [ H 3CT ] should now 3. Drawing Conclusions: What was the H 30+
range from 1.0 M to 1.0 x 10-6 M . Write the con - concentration of the 1.0 M CH 3COOH
centrations in the first column of your data table. solution? Why?
7. Using the conductivity tester, test the cells con -
CONCLUSIONS
taining HCI in order from most concentrated to
least concentrated . Note the brightness of the .
1 Applying Models: The acid ionization expression
tester bulb, and compare it with the brightness of for CH 3COOH is the following:
the bulb when it was placed in the acetic acid
solution . ( Retest the acetic acid well any time for
-
[ H3O HCH3COO-]
Ka = [CH COOH ]
3
comparison . ) After each test , rinse the tester Use your answer to Analysis and Interpretation
probes with distilled water , and use a paper towel item 3 to calculate Ka for the acetic acid solution .
to remove any excess moisture. When the bright -
ness produced by one of the HCI solutions is 2. Applying Models: Explain howr it is possible
about the same as that produced by the acetic for solutions of HCI and CH 3COOH to show
acid you can infer that the two solutions have
,
the same conductivity but have different
about the same hvdronium ion concentration and concentrations.
that the pH of the HCI solution is equal to the
pH of the acetic acid . If the glow from the bulb is EXTENSIONS
loo faint to see, turn off the lights or build a light 1. Evaluating Methods: Compare the Ka value
shield around your conductivity tester bulb. that you calculated with the value found on
8. Record the results of your observations by noting page 606 of your text . Calculate the percent
which HCI concentration causes the intensity of error for this experiment .
the bulb to most closely match that of the bulb 2. Predicting Outcomes: Lactic acid
when it is in acetic acid . ( Hint: If the conductivity ( HOOCCHOHCH3) has a Ka of 1.4 x 10~ 4. Predict
of no single HCI concentration matches that of whether a solution of lactic acid would cause the
the acetic acid , then estimate the value between conductivity tester to glow brighter or dimmer than
the two concentrations that match the best . ) a solution of acetic acid with the same concentra-
tion . How noticeable would the difference be?
CHEMICAL EQUILIBRIUM 629
 CHAPTER 1 9

Reactions
Copper oxidizes in air to form the
green patina you see on this building.
Oxidation and SECTION 1

Reduction OBJECTIVES
w Assign oxidation numbers to
reactant and product species.

Define oxidation and

O xidation-reduction reactions involve a transfer of electrons. Oxida - reduction.
tion involves the loss of electrons, whereas reduction involves the gain
of electrons. Reduction and oxidation half -reactions must occur simul-
taneously. These processes can be identified through the understanding w Explain what an oxidation-
reduction reaction (redox
and use of oxidation numbers (oxidation states) . reaction) is.

Oxidation States
Oxidation states were defined in Chapter 7. The oxidation number
assigned to an element in a molecule is based on the distribution of elec -
trons in that molecule. The rules by which oxidation numbers are assigned
were given in Chapter 7. These rules are summarized in Table 1.

TABLE 1 Rules for Assigning Oxidation Numbers

Rule Example
1. rhe oxidation number of any uncombined element is 0. The oxidation number of Na(s) is 0.
2. The oxidation number of a monatomic ion equals the The oxidation number of
charge on the ion. .
Cl“ is -1
3. rhe more electronegative element in a binary compound is assigned The oxidation number
the number equal to the charge it would have if it were an ion. of O in NO is -2.
4. The oxidation number of fluorine in a compound is always -1. The oxidation number of
F in LiF is - 1 .
5. Oxygen has an oxidation number of -2 unless it is combined with F, The oxidation number
in which it is +1 or +2. or it is in a peroxide, in which it is - 1. of O in N02 is -2 .
6. Hydrogen s oxidation state in most of its compounds is +1 The oxidation number
unless it is combined with a metal, in w hich case it is -1. of FI in LiH is - 1.
7. In compounds. Group 1 and 2 elements and aluminum have The oxidation number
.
oxidation numbers of + 1. +2 and +3. respectively. of Ca in CaC03 is +2.
8. The sum of the oxidation numbers of all atoms The oxidation number of
in a neutral compound is 0. C in CaC03 is +4.
9. The sum of the oxidation numbers of all atoms in a The oxidation number of
polyatomic ion equals the charge of the ion. P in PCPO4 is +5.

OXIDATION -REDUCTION REACTIONS 631

 FIGURE 1 The color of solutions
containing chromium compounds
changes with the oxidation state of
chromium.

Oxidation state

Chromium provides a very visual example of different oxidation num -

bers. Different oxidation states of chromium have dramatically differ -
.
ent colors, as can be seen in Figure 1 The chromium ( II ) chloride
solution is blue, chromium! Ill ) chloride solution is green , potassium
chromate solution is yellow , and potassium dichromate solution is
orange.

Oxidation
Processes in which the atoms or ions of an element experience an
increase in oxidation state are oxidation processes. The combustion of
metallic sodium in an atmosphere of chlorine gas is show n in Figure 2.
The sodium ions and chloride ions produced during this strongly
exothermic reaction form a cubic crystal lattice in which sodium cations
are ionically bonded to chloride anions. The chemical equation for this
reaction is written as follows.

2 Na ( .v ) + Cl 2(g ) 2 NaCl ( .v )

The formation of sodium ions illustrates an oxidation process because

each sodium atom loses an electron to become a sodium ion . The oxi -
dation state is represented by placing an oxidation number above the
symbol of the atom and the ion.
o
Na > Na ^ + e
FIGURE 2 Sodium and chlorine
react violently to form NaCl. The The oxidation state of sodium has changed from 0. its elemental
synthesis of NaCl from its elements state, to the + 1 state of the ion ( Rules 1 and 7. Table 1 ). A species whose
illustrates the oxidation - reduction .
oxidation number increases is oxidized The sodium atom is oxidized to
process. a sodium ion .

632 CHAPTER 19
 Reduction
Processes in which the oxidation state of an element decreases are reduc-
tion processes. Consider the behavior of chlorine in its reaction with
sodium . Each chlorine atom accepts an electron and becomes a chloride
ion . The oxidation slate of chlorine decreases from 0 to -1 for the chlo-
ride ion ( Rules 1 and 2. Table 1 ) .

Cl, + 2e~ > 2cr

A species that undergoes a decrease in oxidation state is reduced. The

chlorine atom is reduced to the chloride ion .

Oxidation and Reduction as a Process FIGURE 3 Copper is oxidized and

nitrogen dioxide is produced when
this penny is placed in a concentrat -
Electrons are released in oxidation and acquired in reduction . There-
ed nitric acid solution .
fore. for oxidation to occur during a chemical reaction , reduction must
also occur. Furthermore, the number of electrons produced in oxidation
must equal the number of electrons acquired in reduction. This makes
sense when you recall that electrons are negatively charged and that for
charge to be conserved , the number of electrons lost must equal the
number of electrons gained . You learned in Chapter 8 that mass is con -
served in any chemical reaction . Therefore, the masses of the elements w r>
Developed nd MHM l e
*
that undergo oxidation and reduction and the electrons that are tartowl to*** iMrhm AIMOJIMM

exchanged are conserved. For a variety of links related to this

A transfer of electrons causes changes in the oxidation states of one or chapter, go to . . ks.org
more elements. Any chemical process in which elements undergo changes
in oxidation number is an oxidation-reduction reaction. Iliis name is
Topic: Redox Reactions
Sci Links code: HC61281
^
often shortened to redox reaction. An example of a redox reaction can be
seen in Figure 3, in which copper is being oxidized and NOj from nitric
acid is being reduced . The part of the reaction involving oxidation or
reduction alone can be written as a half- reaction. The overall equation for
a redox reaction is the sum of two half-reactions. Because the number of
electrons involved is the same for oxidation and reduction , they cancel
each other out and do not appear in the overall chemical equation.
Equations for the reaction between nitric acid and copper illustrate the
relationship between half - reactions and the overall redox reaction.

Cu » Cu 2+ + 2e~ -
( oxidation half reaction )
.s - -: -:
2 NOJ + 2e~ 4- 4 H +
l +4
.
* 2 NO - + 2 H:0
ri
( reduction half -reaction )
H
Cu 2 NOJ -f- 4 FT
*
»
-4
CU2+ + 2 NOT + 2 H O . ( redox reaction )

Notice that electrons lost in oxidation appear on the product side of

the oxidation half - reaction. Electrons are gained in reduction and

OXIDATION-REDUCTION REACTIONS 633

 appear as reactants in the reduction hall -reaction. When metallic copper
Chemistry in Action 0
reacts in nitric acid, one copper atom is oxidized to CiK as two nitro-
Photochromic Lenses gen atoms are reduced from a +5 oxidation stale to a +4 oxidation state.
Photochromic eyeglasses darken when Atoms are conserved. This is illustrated by the balanced chemical equa -
exposed to ultraviolet light and become tion for the reaction between copper and nitric acid.
transparent again in the absence of If none of the atoms in a reaction change oxidation state, the reaction
ultraviolet light. This process is the result is not a redox reaction. For example, sulfur dioxide gas. SO:. dissolves in
of oxidation-reduction reactions. Silver
water to form an acidic solution containing a low concentration of sul -
chloride and copper(l) chloride are
embedded in the lenses. The chloride furous acid. H:SOv
ions absorb photons, and the silver chlo- : *1 *4 -2
ride dissociates and forms chlorine
atoms and silver atoms. The elemental
.
SO > + H - Q
* H:SO;
silver darkens the lenses. Note that the
The oxidation states of all elemental species remain unchanged in this
chlorine ions are oxidized and the silver
atoms are reduced. Then, the copper (l)
composition reaction. Therefore, it is not a redox reaction.
ions reduce the chlorine atoms and When a solution of sodium chloride is added to a solution of silver
form copper(ll) ions. In the reverse nitrate, an ion-exchange reaction occurs and white silver chloride
process, the copper (ll) ions oxidize precipitates.
the silver atoms back to the transpar -
-2
ent silver ions.
Na+ + C1‘ -t- Ag~ + NO3 > Na" + NO 3 4- AgCI

The oxidation state of each monatomic ion remains unchanged. Again,

this reaction is not an oxidation-reduction reaction.

Redox Reactions and Covalent Bonds

Both the synthesis of NaCl from its elements and the reaction between
copper and nitric acid involve ionic bonding. Substances with covalent
bonds also undergo redox reactions. An oxidation number , unlike an
ionic charge, has no physical meaning. That is. the oxidation number
assigned to a particular atom is based on its electronegativity relative to
the other atoms to which it is bonded in a given molecule: it is not based
on any real charge on the atom. For example, an ionic charge of 1-
results from the complete gain of one electron by an atom or other neu-
tral species, whereas an oxidation state of — 1 means an increased attrac -
.
tion for a bonding electron A change in oxidation number does not
require a change in actual charge.
When hydrogen burns in chlorine, a covalent bond forms from the
sharing of two electrons. The two bonding electrons in the hydrogen
chloride molecule are not shared equally. Rather, the pair of electrons
is more strongly attracted to the chlorine atom because of its higher
electronegativity.
-i
FT -f CI7 4 2HCI

As specified by Rule 3 in Table 1, chlorine in HC1 is assigned an oxida -

tion number of - 1. Thus, the oxidation number for the chlorine atoms
changes from 0, its oxidation number in the elemental state, to -1; chlo-
.
rine atoms are reduced. As specified by Rule 1 the oxidation number of
each hydrogen atom in the hydrogen molecule is 0. As specified by Rule
6, the oxidation state of the hydrogen atom in the IIC1 molecule is + 1: the

634 CHAPTER ) 9
hydrogen atom is oxidized. Neither atom has totally lost or totally gained
any electrons. Hydrogen has donated a share of its bonding electron to
the chlorine but has not completely transferred that electron . The assign -
ment of oxidation numbers allows an approximation of the electron dis-
tribution of a molecule. An element can have different oxidation numbers
in different compounds. This difference in oxidation numbers can reveal
the difference in electron distribution of the compounds.
Reactants and products in redox reactions are not limited to monatom -
ic ions and uncombined elements. Elements in molecular compounds or
polyatomic ions can also be oxidized and reduced if they have more than
one nonzero oxidation state. An example of this is provided in the reaction
between the copper penny and nitric acid in which the nitrate ion . NOj, is
converted to nitrogen dioxide. NCK Nitrogen is reduced in this reaction .
Usually, we refer to the oxidation or reduction of the entire molecule or
ion . Instead of saying that the nitrogen atom is reduced , we say the nitrate
ion is reduced to nitrogen dioxide.
-4
r

- + N O3 * NO -* + • • •

SECTION REVIEW c. NaOH( aq) + HCI( aq ) » NaCI( aq ) + H20(/ )

1. How are oxidation numbers assigned? d. H2 (flf ) + Cl2 (0) - » 2 HCI(g)
.
2 Label each of the following half -reactions as either e. SO 3( g ) + H 20( / ) -> H2 S04(aq)
an oxidation or a reduction half-reaction: 4. For each redox equation identified in the previous
0 -1 question, determine which element is oxidized and
a. Br2 + 2 e 2Br "
which is reduced.
*
0 +1
b. Na » Na+ + e Critical Thinking
-1 0 .
5 ANALYZING INFORMATION Use the following
c. 2 Cl - » Cl2 + 2 e *
equations for the redox reaction between Al 3 "- and
0 -1 Na to answer the questions below.
d. Cl2 + 2 e “

2 C|-
* 0
+
3 Na + 3 e~ (oxidation)
e.
+1

Na+ +e ~
> Na
0
+3
* 30Na
0 +2 Al3+ + 3 e "

* Al (reduction)
f. Fe > Fe2 + + 2e 0 +3 +1 0
,
+ 2 0 3 Na + Al3 » 3 Na+ + Al (redox reaction)
g. Cu2+ + 2 e » Cu
-.33+ » 2 a. Explain how this reaction illustrates that charge
is conserved in a redox reaction.
h. Fe +e ~
Fe2+
b. Explain how this reaction illustrates that mass
3. Which of the following equations represent redox is conserved in a redox reaction.
reactions ?
c. Explain why electrons do not appear as react -
a. 2 KN03(S) 2KN02(S) + 02 (g)
* ants or products in the combined equation.
b. H 2 (g) + CuO s ( ) » Cu(s) + H20( / )

OXIDATION-REDUCTION REACTIONS 635

 Chemistry in Action
Skunk - Spray Remedy
;V
SSSfa
Have you ever given your pet a sulfur- containing compound that is
tomato juice bath to get rid of the in skunk spray.
smell of skunk spray on its coat ?
RSH + 3 H202 + NaHC03 »
Chemistry has a much better way of
RS03Na + 4H 20 + C 02
conquering skunk spray.
Paul Krebaum, the inventor of a The pet should be thoroughly
new " deskunking " formula, says washed with the mixture, and care
that while working as a materials should be taken to avoid the eyes. If
engineer, he constantly had to deal the mixture is left on for a few min -
with the less- than-pleasant smell of utes—long enough for the reaction
the hydrogen sulfide gas that was to occur—and then rinsed away with
released from one of his experi - tap water, the smell will disappear.
ments. Venting off the gas only par - The formula does not bleach or
tially solved the problem. A better cause any other negative side
solution would be to eliminate the effects. Mr. Krebaum does have one
smell entirely. A Skunk spray gets its odor from chemi - warning: Mix the formula just before
Mr. Krebaum rifled through his old cals called mercaptans.
using it, because the mixture breaks
chemistry books and found that Because the odor in a skunk 's spray down quickly. The reaction releases
hydrogen peroxide could oxidize also comes from compounds con- oxygen, so the formula should not
these sulfur-containing compounds taining sulfur in a low oxidation be kept in a sealed container.
to much less smelly components. He Pressure will build up, and the lid
state, Mr. Krebaum thought his
immediately whipped up a hydrogen solution might also work on this could eventually blow off. For this
peroxide mixture, and it worked like
age - old problem. He mixed up a reason, bottles of " Krebaum's
a charm. Skunkinator " will not be appearing
milder version to try out on the
The equation below shows that on drugstore shelves any time soon.
pet: 1 qt of a 3% hydrogen peroxide
hydrogen sulfide reacts with H 202 to solution, 1 / 4 cup of baking soda, and
form sulfate compounds that do not 1 tsp of liquid soap. His friend tried it
Questions
have a bad odor.
out, and the result was one wet and 1. How did Paul Krebaum 's
unhappy—but much less smelly — research into the properties of
2 NaOH + 4H202 + H 2 S ->
Na2 S04 + 6H 20 pet. H2 S result in a benefit to dog
Mr. Krebaum says that the hydro- owners?
" The receptors that are in your
gen peroxide in the remedy actually 2. What are some possible packag-
nose are sensitive to sulfur in its low
oxidizes the compounds, while the ing designs that Paul Krebaum
oxidation state," says Mr. Krebaum . baking soda reduces the acidity of could have used if he had
" However, they are not sensitive to
the mixture and the soap helps to wanted to sell his formula ?
sulfur in its high oxidation state."
wash out the greasy skunk spray.
Some time later, a friend of
This reaction can be seen in the fol-
Mr. Krebaum's complained to him
lowing equation. The symbol R repre-
that a skunk had sprayed his pet.
sents all the other elements in the

636 CHAPTER 1 9
Balancing Redox SECTION 2

Equations OBJECTIVES
sj Explain what must be con-
served in redox equations.

Balance redox equations

Ill quations for simple redox reactions can he balanced by inspection , by using the half- reaction
which you learned to do in Chapter 8. Most redox equations, however, method.
require more systematic methods. The equation-balancing process
requires the use of oxidation numbers. In a balanced equation , both
charge and mass are conserved . Although oxidation and reduction hall -
reactions occur together , their reaction equations are balanced sepa -
rately and then combined to give the balanced redox-reaction equation .

Half - Reaction Method

— 1 i I

The half - reaction method , or ion -electron method , for balancing redox CROSS- DISCIPLINARY
equations consists of seven steps. Oxidation numbers are assigned to all Go to go. hrw. com tor a full - length
atoms and polyatomic ions to determine which species are part of the article on redox reactions in photo-
redox process. The oxidation and reduction equations are balanced sep- synthesis.
arately for mass and charge. They are then added together to produce a Keyword: HC 60 XRX
complete balanced equation . These seven steps are applied to balance
the reaction of hydrogen sulfide and nitric acid . Sulfuric acid , nitrogen
dioxide, and water are the products of the reaction .
1 . Write the formula equation if it is not given in the problem. Then
write the ionic equation.
Formula equation: H:S + HN 03 * H 2S04 + NO: 4- H:0
+
Ionic equation : H 2S + H + N 03 -> 2 ir + SOj- + NO: + H:0
2 . iSSigtl oxidation numbers. Delete substances containing only el -
ements that do not change oxidation state.
*1 as -2 . 4 -2
H 2S + H* 4- N 03 * 2 hT + SOj - + NO: + H:0

The sulfur changes oxidation state from -2 to +6. The nitrogen

changes oxidation state from 4-5 to 4-4. The other substances are
deleted .
-s -r so
.4 :
+ NO,
H S + NO:
: 4

The remaining species are used in step 3.

^
OXIDATION-REDUCTION REACTIONS 637
 -
3. Write the half reaction for oxidation. In this example* the sulfur is
being oxidized .
H .S » S0 5-
• Balance the atoms . To balance the oxygen in this half - reaction , H:0
must be added to the left side. This gives 10 extra hydrogen atoms on
that side of the equation . Therefore 10 hydrogen ions are added to
,

the right side. In basic solution , OH ions and water may be used to
“

balance atoms.
»h

H,S .
+ 4H O > SO 5- + 10 H *
• Balance the charge. Electrons are added to the side having the
greater positive net charge. The left side of the equation has no net
charge: the right side has a net charge of 8+ . For the charges to bal -
ance each side must have the same net charge. Therefore , 8 electrons
,

are added to the product side so that it has no charge and balances
with the reactant side of the equation . Notice that the oxidation of
sulfur from a state of -2 to +6 indicates a loss of 8 electrons.
*6

H .S + 4 H -. 0 > SO } + 10 H + 8e
* *
'

The oxidation half - reaction is now balanced .

4. for reduction . In this example, nitrogen

Wtite the hull - reaction is

being reduced from a +5 state to a -+-4 state .

.5 -4
NO } > NO ,

• Balance the atoms. H ,0 must be added to the product side of the

reaction to balance the oxygen atoms. Therefore, two hydrogen ions
must be added to the reactant side to balance the hydrogen atoms.
4

NOJ + 2H NO. + H .O

• Balance the charge . Electrons are added to the side having the
greater positive net charge. The left side of the equation has a net
charge of 1+. Therefore. 1 electron must be added to this side to bal -
ance the charge .
-4
NO } + 2 H + + * NO , + H .O
The reduction half - reaction is now balanced .

5. Conserve charge hy adjusting the coefficients in front of the elec-

trons so that the number lost in oxidation equals the number gained
in reduction. Write the ratio of the number of electrons lost to the
number of electrons gained .
e lost in oxidation 8
e gained in reduction 1

638 CHAPTER 19
 This ratio is already in its lowest terms. If it were not , it would need
to he reduced. Multiply the oxidation half - reaction bv 1 ( it remains KMn04
unchanged ) and the reduction half - reaction by 8. The number of
electrons lost now equals the number of electrons gained .

-
ft
I H S + 4 HiO sof + 10 H * + 8e-
T?

81 NOj + 2 H + + e~
- 4
NO: + H:0

6 . Combine the half - reactions\ and cancel out anything common to

both sides of the equation.
-S ft
H 2S + 4 H:0 042- + 10H +
+ Se~
•5 4 FeS04
8 NO 3 + 16 H* + 8<' 8 N 02 + 8H 20 in H 2S04
6,
8 NO} + KiH * +»~ + H:S + 4bKO
4 4 -fft
FIGURE 4 As a KMn 04 solution
8N 02 + 8H 20 + SO 5- + K)H+ +,8r
is titrated into an acidic solution of
FeS04, deep purple Mn04 ions are
Each side of the above equation has 10 H \ 8e , and 4 H:0. These can - reduced to colorless Mn:+ ions.
cel each other out and do not appear in the balanced equation. When all Fe:" ions are oxidized ,
*4 -n Mn 04 ions are no longer reduced
8 N 02 + H:S + 6 H" 4 8NO, + 4 H 20 + SO 5- to colorless Mn 2* ions. Thus, the first
faint appearance of the \ ln 04 color
7 . Combine ions to form the compounds shown in the original formu
.
la equation Check to ensure that all other ions balance. The NO5
- indicates the end point of the
titration .
ion appeared as nitric acid in the original equation . There are only
6 hydrogen ions to pair with the 8 nitrate ions. Therefore, 2 hydrogen
ions must be added to complete this formula . If 2 hydrogen ions are
added to the left side of the equation . 2 hydrogen ions must also be
added to the right side of the equation .
8HNO3 4- H:S 4 8NO: + 4 H:0 4- SO3 "
- 2H+
4

Hie sulfate ion appeared as sulfuric acid in the original equation. The
hydrogen ions added to the right side are used to complete the form -
ula for sulfuric acid .
8HNO3 4- H:S 4 8 N 02 + 4 H 20 + H:S04
A final check must be made to ensure that all elements are correctly
balanced .

SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.

Write a balanced equation for the reaction shown in Figure 4. A deep purple solution of potassium per -
manganate is titrated with a colorless solution of iron ( II ) sulfate and sulfuric acid . The products are
iron ! Ill ) sulfate, manganese! II ) sulfate, potassium sulfate, and water— ail of which are colorless.

-
OXIDATION REDUCTION REACTIONS 639
 SOLUTION 1 . Write the formula equation if it is not given in the problem. Then write the ionic equation.

KMn 04 + FeS04 + H 2S04 4 Fe2( S04)3 + MnS04 + K 2S04 + H 20

K + MnOj + Fe2+ + SO3- + 2 H + 4- SO$
+ "
4
2Fe3+ + 3S04 4- Mn2+ + SOj 4- 2K + 4- SO3- 4- H:0
" '

2. Assign oxidation numbers to each element and ion. Delete substances containing an ele -
ment that does not change oxidation state.
-h -
K + + MnO; + Fe2+ + SOf + 2 H + + SO
^ >
2
- +2 +1» - 2
2Fe3* + 3SC>4- + Mn 2+ + SO} + 2 K + SO5- + H 20 '
- 1
*
+r > -i -2

Only ions or molecules whose oxidation numbers change are retained .

» 3
Mn 04 4- Fe:‘ 4 Fe3* 4- Mn 2+

3. Write the half - reaction for oxidation. The iron shows the increase in oxidation number.
Therefore, it is oxidized .
3
Fe 2+ > Fe 3+

• Balance the mass. The mass is already balanced.

• Balance the charge.

Fe 2+ 4 Fe3+ 4- r

4. Write the half - reaction for reduction. Manganese shows a change in oxidation number
from 4-7 to 4-2. It is reduced .

Mn 04 4 Mn 2 +

• Balance the mass. Water and hydrogen ions must be added to balance the oxygen atoms
in the permanganate ion .

MnC>4 + 8FT » Mn2+ + 4H20

• Balance the charge.

MnO; + 8H + + 5e~ 4 Mn 2+ + 4 H 20

5. Adjust the coefficients to conserve charge.

e lost in oxidation 1
e gained in reduction 5
5( Fe2+ » Fe3+ + e~ )
l ( Mn 04 + 8H + + 5e~ > Mn 2+ + 4 H 20 )

640 CHAPTER 19
 6 . Combine the half - reactions ami cancel.

5Fe2+ 3+
* 5Fe + 5e
~

MnO; + 8H + 5e~ 2+
* Mn + 4 HiO
*

MnO; + 5Fe 2+ + 8H + + 5>e~ 2+

* Mn + 5Fe^ + 4 H:0 + 5r
7. Combine ions to form compounds from the original equation. The iron ( III ) product
appears in the original equation as Fe2(S04 )3. Every iron ( lll ) sulfate molecule requires
two iron ions. Therefore, the entire equation must be multiplied by 2 to provide an even
number of iron ions.

2( 5 Fe 2+ + Mn 04 + 8H +
,
5 Fe + + Mn 2 + + 4H,0 )
l 0Fe2+ + 2 MnO4 + 16 H + 10Fe -v + 2 Mn 2+ + 8H:0

Hie iron ( II ). iron ( III ), manganese ( Il ), and 2 hydrogen ions in the original equation are
paired with sulfate ions. Iron ( II ) sulfate requires 10 sulfate ions, and sulfuric acid
requires 8 sulfate ions. To balance the equation , 18 sulfate ions must be added to each
side. On the product side, 15 of these ions form iron ( lll ) sulfate, and 2 of them form man-
ganese ( II ) sulfate. That leaves 1 sulfate ion unaccounted for. The permanganate ion
requires the addition of 2 potassium ions to each side. These 2 potassium ions form
potassium sulfate on the product side of the reaction .

10 FeSQ4 + 2KMnQ4 + 8H 2SQ4 5Fe2( S04 )3 + 2 MnS04 + K 2S04 + 8 H:0

Final inspection shows that atoms and charges are balanced .

PRACTICE Answers in Appendix E

1. Copper reacts with hot . concentrated sulfuric acid to form cop-

per ( II ) sulfate, sulfur dioxide, and water. Write and balance the
equation for this reaction .
— CVCnTEft? T7)
2. Write and balance the equation for the reaction between nitric Go to go. hrw.com for
acid and potassium iodide. The products are potassium nitrate, more practice problems
iodine, nitrogen monoxide, and water. that ask you to balance
redox equations.
Keyword: HC 60 XRX

SECTION REVIEW Critical Thinking

1. What two quantities are conserved in redox 4. RELATING IDEAS When heated, elemental phos-
equations ? phorus, P4, produces phosphine, PH 3, and phos-
2. Why do we add H+ and H 20 to some half- phoric acid, H3PO4. How many grams of phosphine
reactions and 0H~ and H20 to others? are produced if 56 g P4 have reacted?
.
3 Balance the following redox reaction:
Na 2 Sn02 + Bi(OH) 3 > Bi + Na2 Sn03 + H20

OXIDATION-REDUCTION REACTIONS 641

 SECTION 3
Oxidizing and
OBJECTIVES Reducing Agents
^ Relate chemical activity to
oxidizing and reducing
strength.

^ Explain the concept of

A reducing agent is a substance that has the potential to cause another
disproportionation. substance to be reduced . Reducing agents lose electrons; they attain a
more positive oxidation state during an oxidation - reduction reaction.
Therefore, the reducing agent is the oxidized substance.
An oxidizing agent is a substance that has the potential to cause an -
other substance to be oxidized . Oxidizing agents gain electrons and
attain a more negative oxidation state during an oxidation -reduction
reaction . The oxidizing agent is the reduced substance. Table 2 helps
clarify the terms describing the oxidation -reduction process.

Strengths of Oxidizing
and Reducing Agents
Different substances can be compared and rated by their relative
potential as reducing and oxidizing agents. For example, the order of the
elements in the activity series ( see Table 3 on page 286 ) is related to each
element s tendency to lose electrons. Elements in this series lose elec-
'

trons to the positively charged ions of any element below them in the
series. The more active an element is. the greater its tendency to lose
electrons and the better a reducing agent it is. Tlie greater the distance
is between two elements in the list , the more likely it is that a redox
reaction will take place between them .
These elements and some other familiar substances are arranged in
Table 3 according to their activity as oxidizing and reducing agents. The
fluorine atom is the most highly electronegative atom. It is also the most

TABLE 2 Oxidation-Reduction Terminology

Change in Change in
Term oxidation number electron population
Oxidation in a positive direction loss of electrons
Reduction in a negative direction gain of electrons
Oxidizing agent in a negative direction gains electrons
Reducing agent in a positive direction loses electrons

642 CHAPTER 1 9
active oxidizing agent . Because of its strong attraction for its own elec- TABLE 3 Relative Strength
trons, the fluoride ion is the weakest reducing agent. The negative ion of of Oxidizing and Reducing
a strong oxidizing agent is a weak reducing agent . Agents
The positive ion of a strong reducing agent is a weak oxidizing agent .
As shown in Table 3, Li atoms are strong reducing agents because Li is Reducing Oxidizing
agents agents
a very active metal . When Li atoms oxidize, they produce Li* ions, which
are unlikely to reacquire electrons, so Li* ions are weak oxidizing T Li Li +
agents.
The left column of each pair also shows the relative abilities of met -
K K -
Ca Ca 2+
als listed in the table to displace other metals from their compounds.
Na Na +
Zinc, for example, appears above copper. Tlius. zinc is the more active
reducing agent , and it displaces copper ions from solutions of copper Mg Mg2 +
,
.
compounds, as illustrated in Figure 5 The copper ( II ) ion . on the other A1 A! +
hand , is a more active oxidizing agent than the zinc ion . Zn Zn 2+
Nonmetals and some important ions also are included in the series in Cr Cr3+
Table 3. Any reducing agent is oxidized bv the oxidizing agents below
it . Observe that F: displaces Cl . Br , and 1 ions from their solutions.
" “ Fe Fe2+
Cl2 displaces Br and I ions, and Br: displaces I ions. The equation for
"
Ni Ni 2+
the displacement of Br by CL is as follows. Sn Sn 2+
Pb Pb2 +
-E
CL + 2 Br ( iaq )
I
* 2CI ( aq ) + Br 2
(I
c H - ) H0 , n
a
2 Br » Br: + 2e ( oxidation ) Zb
H 2S s tA
3
c
(I Cu Cu 2+ y.
3
> 2 CI -
- rc
CL + 2e ( reduction )
o I *

h
- -
MnOj-
3
MnOj
In every redox reaction , there is one reducing agent and one oxi -
dizing agent . In the preceding example, Br is the reducing agent and
“ Fe2* Fe3*
CL is the oxidizing agent . Hg Hgr
Ag Ag"
NO; NO;
Br Br,
Mn 2+ Mn 02
SO H 2S04 ( cone. )
Cr* Cr O .^
cr Cl2
Mn:+ MnO
F "
F2
^

FIGURE 5 Zinc displaces copper ions from a copper ( II ) sulfate solution .

Metallic copper precipitates.

OXIDATION - REDUCTION REACTIONS 643

 QuicILkB Wear safety goggles and an apron.

Materials
Redox Reactions • aluminum foil
• beaker, 250 mL
Procedure • 1 M copper(ll) chloride solu-
Record all of your results in a tion, CuCI2
data table. • 3% hydrogen peroxide
1• Put 10 mL of hydrogen perox - Discussion • manganese dioxide
ide in a test tube, and add a
small amount of manganese
1. Write balanced equations • metric ruler
• scissors
showing what happened in
dioxide (equal to the size of
each of the reactions. • test -tube clamp
about half a pea). What is the • test tube, 16 x 150 mm
result? 2. Write a conclusion for the two • wooden splint
experiments.
2. Insert a glowing wooden splint
into the test tube (see dia -
Wooden
gram). What is the result ? If splint
oxygen is produced, a glowing
wooden splint inserted into the
test tube will glow brighter.

3. Pill the 250 mL beaker halfway

41
•

with the copper(ll) chloride

{ A 1
solution.
Clamp
4. Cut foil into 2 cm x 12 cm
strips.
5. Add the aluminum strips to the
copper(ll) chloride solution. H 2O 2
Use a glass rod to stir the mix-
ture, and observe for 12 to
15 minutes. What is the result ?

Disproportionation
Some substances can be both reduced and oxidized easily. For example,
peroxide ions, 03 . have a relatively unstable covalent bond between
“

the two oxygen atoms. The electron- dot formula is written as follows .
i#°r
Each oxygen atom has an oxidation number of -1. The peroxide ion
structure represents an intermediate oxidation state between 0: and
O 2 . Therefore, the peroxide ion is highly reactive.
.
Hydrogen peroxide, H:02 is a covalent compound. It decomposes
into water and molecular oxygen, as shown in the equation below.
i
2H202 > 2H20 + 02

644 CHAPTER 19
 FIGURE 6 A bombardier beetle
can repel large predators such as
frogs with a chemical defense mech -
anism that uses the disproportiona -
tion of hydrogen peroxide.

Notice that in this reaction , hydrogen peroxide is both oxidized and

reduced . Oxygen atoms that become part of gaseous oxygen molecules
are oxidized . The oxidation number of these oxygen atoms increases
from -1 to 0. Oxygen atoms that become part of water are reduced . The
oxidation number of these oxygen atoms decreases from -1 to -2. A
process in which a substance acts as both an oxidizing agent and a reduc-
ing agent is called disproportionation. A substance that undergoes dis-
proportionation is both self -oxidizing and self - reducing.
The bombardier beetle defends itself by spraying its enemies with an
unpleasant hot chemical mixture, as shown in Figure 6. The catalyzed
disproportionation of hydrogen peroxide produces hot oxygen gas. This
gas gives the insect an ability to eject irritating chemicals from its
abdomen with explosive force.

SECTION REVIEW .
2 The photo on the left depicts two redox reactions.
.
1 Describe the chemical activity of the alkali metals Both nails are in a sulfuric acid solution. Answer
the following questions:
and of the halogens on the basis of oxidizing and
reducing strength. a. When zinc is wrapped around an iron nail,
is the iron or zinc oxidized?
b. When copper is wrapped around an iron
nail, is the iron or copper oxidized ?
.
3 Would Cl2 be reduced byI ? Explain
“
.
.
4 Which is the stronger oxidizing agent in each of
the following pairs: Cu2+ or Al ,I2 or 5, F2 or Li+?
.
5 What is meant by disproportionation1
Critical Thinking
6. ORGANIZING IDEAS In general, where in the
\
\ periodic table are the elements found that in
elemental form are the strongest oxidizing
agents ? Explain.

OXIDATION- REDUCTION REACTIONS 645

 CHAPTER HIGHLIGHTS
Oxidation and Reduction
I Vocabulary •Oxidation numbers are assigned by the set of rules listed in
oxidation Table 1. Oxidation numbers are based on the distribution of
oxidized electrons in a molecule.
reduction •Oxidation-reduction reactions consist of two half-reactions
reduced that must occur simultaneously.
oxidation -reduction reaction •Oxidation- reduction reactions are identified by examining the
redox reaction changes in the oxidation numbers of atoms in the reactants
half -reaction and products.
•Oxidation involves the loss of electrons, and reduction involves
the gain of electrons.
•A species whose oxidation number increases is oxidized. A
species whose oxidation number decreases is reduced.

Balancing Redox Equations

I •Charge and mass are conserved in a balanced redox equation.
•In the half-reaction method for balancing equations the atoms
,

and charge of oxidation and reduction equations are balanced

separately.Then, they are combined to give a complete balanced
equation.
•In a half-reaction, the charge on the reactant side must equal
the charge on the product side, but these charges do not need
to be zero.
•For the half-reaction method , the atoms in each half-reaction

are balanced by adding H+ ions and H:C) molecules in acidic

solutions. If the solution is basic. Oil ions and H:0 molecules
'

are added to balance the atoms in each half-reaction.

•The number of electrons lost in the oxidation half -reaction
must equal the number of electrons gained in the reduction
half-reaction. The two half -reactions must be multiplied by
appropriate factors to ensure that the same number of elec -
trons are transferred.

Oxidizing and Reducing Agents

I Vocabulary •The substance that is reduced in redox reactions is the oxidiz -
reducing agent ing agent because it acquires electrons from the substance that
oxidizing agent is oxidized.
disproportionation •The substance that is oxidized in a redox reaction is the reducing
agent because it supplies the electrons to the substance that is
reduced.
•Strong reducing agents are substances that easily give up elec -
trons.
•Disproportionation is a process in which a substance is both an
oxidizing agent and a reducing agent.

646 CHAPTER 1 9
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D .
7. Determine the oxidation number of each atom
Oxidation and Reduction indicated in the following:
SECTION 1 REVIEW a. f. HNO,
1. a . Distinguish between the processes of oxida - b. H:0 g. H 2SO4
tion and reduction . c. Al h . Ca(OH )2
h. Write an equation to illustrate each process. d . MgO i. Fe ( N 03),
2. Which of the following are redox reactions? c. AI:S, j. 02
a . 2 Na + Cl 2 2 NaCl

——
b. C + O, * ,
CO
Balancing Redox Equations
c. 2 FLO * 2 H: + 02
d . NaCl + AgNO , * AgCI + NaNO, SECTION 2 REVIEW
e. NH ? + HCl
,
— * NH 4 + cr 8. Label the following half -reactions as either
f. 2 KCIO 2 KCI + 30, reduction or oxidation half -reactions.
g. H 2 + ci2 2 HCl a. H 2S > S + 2e + 2 H"
‘

h . H 2S04 + 2 KOH > K:S04 + 2 H:0 b. SO, + 4e~ + 2 H ,0 > S + 40 H

—
"

i . Zn + CuS04 > ZnS04 + Cu

3. For each oxidation - reduction reaction in the
,
c. CIO + 6H + be
+ '
» CL + 3H 20
d. Mn( CN ) " £ > Mn ( CN )ft + e
previous question , identify what is oxidized and 9. What are the oxidation states of the elements
what is reduced . that changed oxidation states in the half -
reactions in the above question ?
PRACTICE PROBLEMS 10. Balance the equation for the following reaction
4. Each of the following atom /ion pairs undergoes in a basic solution . Give balanced equations for
the oxidation number change indicated below. -
both half reactions and the balanced equation
For each pair, determine whether oxidation or for the overall reaction .
reduction has occurred , and then write the elec- KMn 04 + NaIQ3 > MnO: + NaIQ4
tronic equation indicating the corresponding
number of electrons lost or gained , PRACTICE PROBLEMS
a. K -» K *
e. IL » H+ 11. For each requested step, use the half - reaction
;-
b. S »s f. O , O2 method to balance the oxidation - reduction
c. Mg
d. F "
—
> Mg
-> F2
2" g. Fe3
h . Mn
+

2 +
Fe 2*
» Mn 04
equation below. ( Hint: See Sample Problem A. )
K + FLO * KOH + H 2
5. Identify the following reactions as redox or a . Write the ionic equation, and assign oxida -
nonredox: tion numbers to all atoms to determine what
a . 2 NH 4C!( <J <7 ) + Ca ( 0 H )2 ( rt<7) is oxidized and what is reduced .
,
2 NH ( «(/ ) + 21120 ( / ) + CaCl 2 ( < / </ ) b. Write the equation for the reduction , and
,
b. 2 HNO ( fl <7 ) + 3 H:S ( g ) balance it for both atoms and charge.
2 NO(g) + 4 H;0( / ) + 3S(s) c. Write the equation for the oxidation , and
c. [ Be( H20)4 ]2+(fl9) + H20( / ) » •

balance it for both atoms and charge.

.
H O ( a q + [Be ( H:0 )30 H ]+ ( tf <7 )
* )
d . Multiply the coefficients of the oxidation and
6. Arrange the following in order of increasing reduction equations so that the number of
oxidation number of the xenon atom: CsXeF . electrons lost equals the number of electrons
*
Xe, XeF:. XeOF2. Xe03, and XeF. gained . Add the two equations.
e. Add species as necessary to balance the
overall formula equation.

OXIDATION-REDUCTION REACTIONS 647

 CHAPTER REVIEW

12. Use the method in the previous problem to bal - 18. Arrange the following in order of decreasing
ance each of the reactions below. oxidation number of the nitrogen atom: N\
a . HI + HNO: •> NO + I + H
2 20 NH3I N 204, N:0. N:H 4. and NOj .
b. FeCl3 + H:S 4 FeCU + HCf + S 19. Balance the following redox equations:
13. Balance the equation for the reaction in a; SbCl5 + K I —> KC14- 1: SbCl3
which hot . concentrated sulfuric acid reacts with b. Ca ( OH ) 2 + NaOH + ClO: + C »
zinc to form zinc sulfate, hydrogen sulfide, NaClO: + CaC03 + H20
and water. 20. Balance the following equations in basic
solution :
a . PbO-> 4 KCI > KCIO -t- KPb( OH )3
Oxidizing and Reducing h. KMn 04 + KI 03 > Mn 02 + KI04
c. K 2 Mn 04 Mn02 + KMn 04
Agents 21. Balance the following equations in acidic
SECTION 3 REVIEW solution:
14. a . Identify the most active reducing agent
a . Mn 04 + CT ’
Mn + + HCIO
among all common elements.
b. NOj + 12 * IO5 + NO,
c. NO; * NO + N 03
b. Why are all of the elements in its group in the
periodic table very active reducing agents?
c. Identify the most active oxidizing agent
among the common elements. CRITICAL THINKING
15. Use Table 3 to identify the strongest and weak - 22. Interpreting Graphics Given the activity table
est reducing agents among the substances listed below, determine whether a reaction will occur or
within each of the following groupings: not . If the reaction will occur , give the products.
a. Ca. Ag, Sn , Cl "

Reducing
b. Fe. Hg. Al. Br "

Agents
c. F , Pb. Mn 2*, Na
"

L U
16. Use Table 3 to respond to each of the following: M M+
a. Would Al be oxidized by Ni:+? P P*
b. Would Cu be oxidized by Ag"? T r
c. Would Pb be oxidized by Na + ?
Oxidizing
d . Would F2 be reduced by Cl ~? Agents
e. Would BP> be reduced bv CU?
a . L and M"
b. P and IVU
MIXED REVIEW c. P and T '
23. Drawing Conclusions A substance has an ele -
17. Identify the following reactions as redox or ment in one of its highest possible oxidation
nonredox: states. Is this substance more likely to be an oxi -
a . Mg(s ) + ZnCl 2( fl<7 ) -4 Zn ( x ) + MgCI 2 ( «</ ) dizing agent or a reducing agent? Explain your
b. 2 H 2 ( £ ) + OF2 (g ) H:0 ( g ) + 2 HF( g ) reasoning.
c. 2 K1( A <7 ) + Pb( N03)2 ( fl<7 )
Pbl;( j) + 2KN03( flr/ )
.
d . CaO( s ) + H O( / ) » Ca ( OH )2 ( <«7 )
e. 3CuCl 2( a <7 ) + 2( NH 4 ) ,P04( « </ )
‘

,
6 NH 4Cl (flr/ ) + Cu ( P04 )‘2(.s )
f. CH 4 ( g ) + 20,( g ) CO,( g ) + 2 H20(g )

648 CHAPTER 1 9
 CHAPTER REVIEW

24. Drawing Conclusions Use Table 3 to decide if

RESEARCH & WRITING
a redox reaction would occur between the two
species, and if so, write the balanced equation. 28. Oxidizing agents are used in the cleaning indus-
Explain your reasoning. try. Research three different oxidizing agents
a. C> 2 and Br: used in this area, and write a report on the advan-
b. Sn:+ and Zn tages and disadvantages of these compounds.
25. Drawing Conclusions An element that dispro- 29. Oxidizing and reducing agents play important
portionates must have at least how many differ - roles in biological systems. Research the role of
ent oxidation states? Explain your reasoning. one of these agents in a biological process.
Write a report describing the process and the
role of oxidation and reduction.
USING THE HANDBOOK
26. Several reactions of aluminum are shown in the ALTERNATIVE ASSESSMENT
common reactions section for Group 13 of the
Elements Handbook . Use these reactions to 30. Boilers are used to convert water to steam in
answer the following: electric power plants. Dissolved oxygen in the
a. Which of the five reactions shown are water promotes corrosion of the steel used in
oxidation-reduction reactions? How' do boiler parts. Explain how dissolved oxygen is
you know ? removed from the water in boilers.
b. For each redox reaction you listed in item a, 31. Performance For one dav•. record situations
r

identify what is oxidized and what is reduced. that show' evidence of oxidation-reduction reac -
c. Write half-reactions for each equation you tions. Identify the reactants and the products,
listed in item a. and determine whether there is proof that a
27. Aluminum is described in Group 13 of the chemical reaction has taken place.
Elements Handbook as a self -protecting metal.
This property of aluminum results from a redox
reaction.
a. Write the redox equation for the oxidation of
aluminum.
b. W rite the half - reactions for this reaction, and
show the number of electrons transferred.
c. What problems are associated with the
buildup of aluminum oxide on electrical
wiring made of aluminum ?

OXIDATION-REDUCTION REACTIONS 649

 Math Tutor BALANCING REDOX EQUATIONS

A redox equation must conserve both mass and charge. So, to balance a redox equation,
you must balance both atoms and charge (electrons). The problem - solving tips and sam-
ple below show how to balance an equation for a redox reaction in basic solution.

Problem-Solving TIPS
To balance redox equations for reactions in basic solution:
• Add OH and H20 to balance oxygen and hydrogen in the redox half - reactions.
• Add OH ions to the side of the equation that needs oxygen atoms. Make sure
you add enough OH ions so that the number of oxygen atoms added is twice the
number needed.
• Then, add enough FHO molecules to the other side of the equation to balance the
hydrogen atoms.

SAMPLE
The following unbalanced equation represents a redox reaction that takes place in a basic
solution containing kOH. Balance the redox equation.
Bn( / ) KOH( aq ) KBr( aq ) 4- KBrOy ( aq )
Write the full ionic equation, assign oxidation numbers, and eliminate species whose oxi -
dation numbers do not change. The result is the following equation:
Br: Br 4- BrO }
"

Divide this equation into half- reactions. Note that Br 2 is the reactant in both half -reactions.
Reduction: Bn Br Oxidation: Bn 4 Br03
Add 1HO and OFI to balance atoms in basic solution. Then, add electrons to balance charge.
Reduction: Bn 4- 2c -> 2Br ( no need to add H->0 or OH )
Oxidation: 12011 4- Bn
'
4 2BrO 4- 6H:0 4- 10r
^
To balance transferred electrons, you must multiply the reduction half-reaction by 5 so that
both reactions have 10<f.
5 x ( Bn 4- 2e~ — 4 2Br') = 5 Bn 4- l ( )e 4 lOBr"
( ombining the two hall - reactions gives

5Bn 4- !20H 4- Bn -f 10e“

'
4 l()Br” 4- 2Br03 4- 6H20 4- l( )r

C anceling common species gives

6Bn 4- 12011 4 l( )Br 4- 2Br03 4- 61 HO
' "

Returning the potassium ions to the equation gives

6Bn 4- 12KOH 4 lOKBr 4- 2KBr .
03 4- 61HO or 3Bn 4- 6KO!I
5KBr 4- KBrO; 4- 3H -*0

PRACTICE PROBLEMS
1. Balance the following equation for a redox 2 . Balance the following equation for a redox
reaction that takes place in basic solution: reaction that takes place in basic solution:
Mn02(s ) 4- NaCIO3(n</ ) 4- NaOH( w/ ) 4 NT )( g ) 4- KClO( aq ) 4- KOH( aq ) >
NaMnO±( aq ) 4- NaCI( aq ) 4- H20( / ) KCI( aq ) 4- KN02( <?r/ ) 4- H20( / )

650 CHAPTER 19
Answer the following items on a separate piece of paper. 7. Arrange the following in order of increasing
oxidation number of the sulfur atom: S 03~,
MULTIPLE CHOICE *
S4Oj|“, HSO4. and H:S.
1. In the following reaction, which species is
A. H:S, S20:f, S40
reduced?
2K + Br -» > 2 K * + 2Br
^
B. S20|- H 2S. S4O;-. HSO4
. HS04

C. H2S. SJO?-. HSO4. S4O -

^ ^
A. K
B . Br: D . HS04. S4O . H2S
C. All of the above 8. Which answer contains the correct information
D . None of the above about the following reaction:
2. The oxidation number of the sulfur atom in the 2Pb(N03)2 2PbO + 4NO > + Oi
SO ] ion is A. This reaction is a decomposition reaction and
A . +2. not a redox reaction.
B. -2. B. This reaction is a redox reaction in which the
C. +6. lead is reduced and the oxygen is oxidized .
D. +4. .
C This reaction is a disproportionation reaction.
3. A half - reaction D. This reaction is a redox reaction in which the
A. involves a change in the oxidation stale of an nitrogen is reduced and the oxygen is oxidized.
element. SHORT ANSWER
B. always contains H:0 molecules . 9. Determine the oxidation numbers for Cu in the
C . always contains H ions.
*

superconductor YBa2Cu307. Yttrium ( Y) has an

D. All of the above oxidation number of +3. ( Cu does not have oxi-
4. In the following reaction, which is the oxidizing dation numbers greater than +3. ) Give only
agent ? integer oxidation numbers.
AgNO:+ Cl2 + 2KOH 10. What is an oxidizing agent ?
AgN03 + 2KCI + H:0
.
A AgNO:
EXTENDED RESPONSE

.
B Cl: . .
11 B. F K . and L are four unknown reducing
.
C KOH agents that oxidize to singly charged cations.
.
D KC1 Using the following information, construct a
table showing the relative strengths of the oxi-
5 . What are the oxidation states ( in increasing dizing and reducing agents. Data: F reduces K \
order ) of the element that undergoes dispropor - .
BY and L B‘ oxidizes K and F. but not L.
*

tionation in the following reaction:

CU + H >0
* > HCI + HOCI
.
12 Balance the equation for the following reaction
.
A -1.0. +2
in basic solution:
.
B -1, 0,+1 cio: > KCIO3 + KC10:
.
C -2, -1.0 Give the balanced equation for each half -
D. None of the above reaction and for the overall reaction. Give the
.
6 Which reaction is a redox reaction ? oxidizing agent and the reducing agent.
.
A AUO3 + 6HC1 > 2 AICI3 + 3H20
B. 2HCO3 > CO: + CO5- + H20
.
C SiBr4 + 3H20 % ,Sib
H 3 + 4HBr
D. H:Q 4- PbO:+ NaOH + KC1 If you are short on time, quickly
KCIO + NaPb( OH)3 scan the unanswered questions to see which might
be easiest to answer.

OXIDATION -REDUCTION REACTIONS 651

 SEE PRE- LAB MICRO
EXPERIMENT 19 VOLUMETRIC ANALYSIS L A B

Reduction of Manganese
in Permanganate Ion
OBJECTIVES BACKGROUND
• Demonstrate proficiency in performing In Chapter 15, you studied acid - base titrations in
redox titrations and recognizing end points which an unknown amount of acid is titrated with a
of a redox reaction. carefully measured amount of base. In this procedure,
a similar approach called a redox titration is used . In a
• W rite a balanced oxidation - reduction
equation tor a redox reaction. redox titration , the reducing agent. Fe:*. is oxidized to
Fe3* bv the oxidizing agent , Mn 04. When this process
• Determine the concentration of a solution occurs, the Mn in Mn 04 changes from a 4-7 to a +2
by using stoichiometry and volume data oxidation state and has a noticeably different color.
from a titration . ••

You can use this color change to signify a redox reac-

tion “end point .' When the reaction is complete, any
*

MATERIALS
excess Mn04 added to the reaction mixture will give
• 0.0200 M KMn04 the solution a pink or purple color. The volume data
• 1.0 M H2S04 from the titration , the known molarity of the KMn 04
solution , and the mole ratio from the balanced redox
• 100 mL graduated cylinder equation will give you the information you need to
• 125 mL Erlenmever flasks, 4 calculate the molarity of the FeS04 solution .
250 mL beakers, 2
SAFETY
400 mL beaker
burets, 2
distilled water
For review of safety, please see Safety in the
• double buret damp Chemistry Laboratory in the front of vour book .
• FeS( )4 solution
PREPARATION
• ring stand
1 . In your lab notebook , prepare a data table like
• wash bottle the one shown on the next page.
2 . Clean two 50 mL burets with a buret brush and
distilled water. Rinse each buret at least three
times with distilled water to remove contaminants.
3. Label one 250 mL beaker “0.0200 M KMn 04"
and the other “ FeS04.” Label three of the flasks
“ 1 ” “2 ” and “3/* Label the 400 mL beaker
“ Waste / Label one buret “ KMn 04" and the other
*

“ FeS04 ”

652 CHAPTER 19
 EXPERIMENT 19

DATA TABLE
Trial Initial KMn04 Final KMn04 Initial FeS 04 Final FeS 04
volume (mL) volume (mL) volume (mL) volume (mL)
1
2
3

4. Measure approximately 75 mL of 0.0200 M 2. Slowly add KMn04 from the buret to the FeS04
KMn04, and pour it into the appropriately in the flask while swirling the flask . When the
labeled beaker. Obtain approximately 75 mL color of the solution matches the color standard
of FeS04 solution, and pour it into the appro - .
you prepared in Preparation step 8 record in
priately labeled beaker. your data table the final readings of the burets.
5 . Rinse one buret three times with a few milliliters 3. Empty the titration flask into the waste beaker.
of 0.0200 M KMn04 from the appropriately Repeat the titration procedure in steps 1 and 2
labeled beaker. Collect these rinses in the waste with the flasks labeled * 2" and u3.”
%

beaker. Rinse the other buret three times with

small amounts of FeS04 solution from the CLEANUP AND DISPOSAL
appropriately labeled beaker. Collect these 4. Dispose of the contents of the waste
rinses in the waste beaker. beaker in the container designated by
.
6 Set up the burets as instructed by your teacher. your teacher. Also, pour the color-
Fill one buret with approximately 50 mL of standard flask into this container. Wash your
0.0200 M KMn04 from the beaker, and fill the hands thoroughly after cleaning up the area
other buret with approximately 50 mL of the and equipment.
FcS04 solution from the other beaker.
ANALYSIS AND INTERPRETATION
7. With the waste beaker underneath its tip. open
1. Organizing Ideas: Write the balanced equation
the KMn04 buret long enough to be sure the
for the redox reaction of FeS04 and KMn04.
buret tip is filled. Repeat the process for the
FeS04 buret. 2. Evaluating Data: Calculate the number of moles
of Mn04 reduced in each trial.
.
8 Add 50 mL of distilled water to one of the
125 mL Erlenmeyer flasks, and add one drop 3. Analyzing Information: Calculate the number
.
of 0.0200 M KMn04 to the flask Set this mix - of moles of Fe 2* oxidized in each trial.
ture aside to use as a color standard. It can be
4. Applying Conclusions: Calculate the average
compared with the titration mixture to deter - concentration ( molarity ) of the iron( II )
mine the end point.
sulfate solution.

PROCEDURE
1. Record in your data table the initial buret read- EXTENSIONS
ings for both solutions. Add 10 mL of the 1. Designing Experiments: What possible sources
hydrated iron(ll) sulfate solution. FeS 04»7H20, of error can you identify with this procedure ?
to the flask labeled “1.” Add 5 mL of If you can think of ways to eliminate them, ask
1 M H:S04 to the FeS04 solution in this flask . your teacher to approve your plan, and run the
The acid will help keep the Fe 2 ions in the
^
procedure again.
reduced state, which will allow vou time to
titrate.

OXIDATION -REDUCTION REACTIONS 653

 .. ,

>*
vX7 -
' wig , aa&aMfck. Pro
A V J ft

CHAPTER 20

Electrochemistry
Electrochemical reactions provide
energy in all kinds of applications.
Introduction to SECTION 1

Electrochemistry OBJECTIVES
Identify parts of an electro-
chemical cell and their
functions.

O xidation-reduction reactions involve energy changes. Because these ^ Write electrode half reactions
reactions involve electron transfer, the net release or net absorption of for cathodes and anodes.
energy can occur in the form of electrical energy rather than as heat .
This property allows for a great many practical applications of redox
reactions. The branch of chemistry that deals with electricity - related
applications of oxidation - reduction reactions is called electrochemistry.

PfYfWprd «MJ mmliwrt by lh<

MNUI SttriKt Tutfcm AuocuUoa

Electrochemical Cells For a variety of links related to this

chapter, go to www.scilinks. org I
Oxidation - reduction reactions involve a transfer of electrons. If the two Topic: Electrochemical Cells
SciLinks code: HC60478
^I
substances are in contact with one another, a transfer of energy as heat
accompanies the electron transfer. In Figure 1 a zinc strip is in contact
with a copper ( Il ) sulfate solution . The zinc strip loses electrons to the
copper! II ) ions in solution . Copper ( II ) ions accept the electrons and fall
out of solution as copper atoms. As electrons are transferred between
zinc atoms and copper!II ) ions, energy is released as heat , as indicated
by the rise in temperature.

Before After

Zinc strip

FIGURE 1 Energy as heat given

off when electrons are transferred
CuS04 directly from Zn atoms to Cu 2 + ions
causes the temperature of the aque -
ous CuS04 solution to rise .

ELECTROCHEMISTRY 655
 Conducting wire
FIGURE 2 An electrochemical
cell consists of two electrodes. Each
electrode is in contact with an elec- Zinc electrode
trolyte: the electrode and the elec-
trolyte make up a half -cell . The two
electrodes are connected by a wire , Copper electrode
and a porous barrier separates the
two electrolytes.

Copper ( ll) sulfate

Electrolyte

Zinc sulfate
Electrolyte

Porous barrier

Anode Cathode

If, however , we separate the substance that is oxidized from the sub-
stance that is reduced , the electron transfer is accompanied by a trans-
fer of electrical energy instead of energy as heat . One means of
separating oxidation and reduction half -reactions is with a porous bur -
ner, or suit bridge. This barrier prevents the metal atoms of one half -
reaction from mixing with the ions of the other half -reaction . Ions in the
two solutions can move through the porous barrier, which keeps a
charge from building up on the electrodes. Electrons can be transferred
from one side to the other through an external connecting wire. Electric
current moves in a closed loop path , or circuit , so this movement of elec-
trons through the wire is balanced by the movement of ions in solution.
Altering the system in Figure 1 as just described would simply involve
separating the copper and zinc, as shown in Figure 2. The Zn strip is in an
aqueous solution of ZnS04. The Cu strip is in an aqueous solution of
CuS04. Both solutions conduct electricity, so, as you learned in
Chapter 12, they are classified as electrolytes. An electrode is u conductor
used to establish electrical contact with a nonmetullic port of a circuit , such
as an electrolyte. In Figure 2, the Zn and Cu strips are electrodes. A sin -
gle electrode immersed in a solution of its ions is u half-cell.

The Half - Cells

In the half -cell that contains the Zn electrode in aqueous ZnS04 solution ,
the half - reaction is Zn ( s ) > Zn 2+( aq ) + 2e . The Zn metal loses two
electrons to form Zn:+ ions in solution , and therefore oxidation is taking
place in this half -cell. The electrode where oxidation occurs is culled the
anode. In the half -cell that contains the Cu electrode in aqueous CuS04
solution , the half - reaction is Cir ' Uiq ) + 2e~ Cu (.v ). In this half -
:~
reaction , the Cu ions in solution gain electrons to become Cu solid: that
is, reduction is taking place. The electrode where reduction occurs is culled
the cathode.

656 CHAPTER 20
 Recall from Chapter W that these two half -reactions cannot occur
separately. Both oxidation and reduction must occur in an electro-
chemical reaction. The two half -cells taken together make an electro-
SCllNKS. wV RA
Omloptd «d untiuitd fey tfce
SotJKt iMCfcm Au<yutio«
chemical cell. In the Zn/Cu electrochemical cell, the electrons move IFor a variety of links related to this
from the Zn electrode through the wire and down the Cu electrode to I chapter, go to wvAv. scilinks org
. I
the Cu2+ ions at the electrode-solution interface. Hie Cu2" ions are
reduced to solid Cu. and the resulting Cu atoms attach themselves to
I Topic: Electrical Energy
I SciLinks code: HC60475
^
the surface of the Cu electrode. For this reaction, charge is carried
through the barrier by a combination of Zn2* ( aq ) ions moving from the
anode to the cathode and the SO3 ( aq ) ions moving from the cathode
~

to the anode.

The Complete Cell

An electrochemical cell may be represented by the following notation:
anode electrode | anode solution | | cathode solution | cathode electrode
The double line represents the salt bridge, or porous barrier between ,

the two half -cells. For the present cell, the cell notation is
Zn( s) | Zr\ 2+ { aq ) || Cuz* ( aq ) | Cu(.r ).
The electrochemical reaction can be found by adding the anode half -
reaction to the cathode half-reaction. This overall (or net ) reaction is
the following redox reaction:
Zn( s ) + Cu: ^( aq ) Zn2 +( aq ) + Cu(s)
Although the two half -reactions occur at the same time, they occur
at different places in the cell. Thus, for the reaction to proceed, electrons
must pass through the wire that connects the two half -cells.
An electrochemical cell that consists of the Zn and Cu reaction
described above is called the Daniell Cell , named for the English Electrodes Porous barrier
chemist John Frederick Daniell. The Daniell Cell can generate enough
.
electricity to light up the light bulb shown in Figure 3 In electrochemi- FIGURE 3 The light bulb is
cal cells, either a chemical reaction produces electrical energy or an powered by the reaction in 1his cell.
electric current produces a chemical change.

SECTION REVIEW 3. Write the half -reaction in which \~ ( aq ) changes to

.
1 Why is the use of a salt bridge or porous barrier l2 (s). Would this reaction occur at the anode or
necessary in an electrochemical cell? cathode?
2. Given the Cu2 *( ag) | Cu(s) and Mg2+( ag) Mg(s) Critical Thinking
half -reactions, where Cu2+(ag) | Cu(s) is the cath - 4. RELATING IDEAS Is the net chemical result of an
ode reaction, electrochemical cell a redox reaction? Explain your
a. write the overall reaction. answer.
b. write the cell notation.

ELECTROCHEMISTRY 657
 SECTION 2
Voltaic Cells
OBJECTIVES
>J Describe the operation of
voltaic cells, including dry V oltaic cells use spontaneous oxidation - reduction reactions to convert
cells, lead-acid batteries, and chemical energy into electrical energy. Voltaic cells are also called galvan -
fuel cells. ic cells. The most common application of voltaic cells is in batteries .
> Identify conditions that lead
s

to corrosion and ways to

prevent it. How Voltaic Cells Work
Figure 4 shows an example of a voltaic cell: the Zn | | Cu electrochemi -
sj Describe the relationship
cal cell discussed in the previous section.
between voltage and the
movement of electrons. Electrons given up at the anode pass along the external connecting
wire to the cathode. The movement of electrons through the wire must
be balanced by the movement of ions in the solution. Thus, in Figure 4,
^ Calculate cell voltage/poten - sulfate ions in the CuS04 solution can move through the barrier into
tials from a table of standard the ZnSQ4 solution.
electrode potentials.

Zinc atoms losing two Porous barrier

electrons to become ions
Zinc atom . Zinc ion,
Copper
*
Zn Zn2* L 3 4
e~
a •
$
1
* *
Copper ( ll) sulfate,
CuS04, solution
Water
molecule,
H 20 Sulfate
ion, SO
^
~

Zinc sulfate,
e"
ZnS04, solution
&
Anode Cathode T

FIGURE 4 In a voltaic cell, electrons #

spontaneously flow from anode to cathode. -
Copper "
ion, Cu2*
Copper
atom, Cu
The copper strip gains mass as copper ions
become copper atoms. The zinc strip loses Copper ( ll) ions gaining two
mass as the zinc atoms become zinc ions. electrons to become atoms

658 CHAPTER 20
 The dry cells pictured in Figure 5 tire common sources of electrical
energy. Like the wet cell previously described , dry cells are voltaic cells.
The three most common types of dry cells are the zinc-carbon battery,
the alkaline battery, and the mercury battery. They differ in the sub-
stances being oxidized and reduced .

Zinc- Carbon Dry Cells

Batteries such as those used in flashlights are zinc-carbon dry cells.
These cells consist of a zinc container, which serves as the anode, filled
with a moist paste of Mn (X graphite, and NH 4C1, as illustrated in
Figure 6a. When the external circuit is closed , zinc atoms are oxidized
at the negative electrode, or anode.
(I FIGURE 5 Many common batter -
2+
Zn (s) * Zn ( aq ) + 2e
~
ies are simple voltaic dry cells.

Electrons move across the circuit and reenter the cell through the carbon
rod. The carbon rod is the cathode or positive electrode. Here MnCL is
reduced in the presence of FLO according to the following half - reaction .
-4
2 Mn 0:(.v ) + H:0( / ) + 2e- > Mn:03(s ) + 20H ( aq )
SCllNKS. mi numUmri hr MM
HriMMil hmu tndwri AtmMtkM

For a variety of links related to this

Alkaline Batteries chapter, go to vvww.scilinks.org
The batteries found in a portable compact disc player or other small elec-
tronic device are frequently alkaline dry cells. These cells do not have a
Topic: Batteries
SciLinks code: HC60139
^
carbon rod cathode, as in the zinc-carbon cell . The absence of the carbon
rod allows them to be smaller. Figure 6b shows a model of an alkaline bat -
tery. This cell uses a paste of Zn metal and potassium hydroxide instead of
a solid metal anode. The half -reaction at the anode is as follows.

* Zn ( OH ):(.v ) + 2e
~
Zn (s ) + 20 H ( aq )

The reduction half -reaction , the reaction at the cathode, is exactly the
same as that for the zinc-carbon drv cell.

(a ) zinc dry cell ( b) alkaline dry cell FIGURE 6 ( a ) In a zinc dry cell,
zinc is oxidized to Zn:* at the anode,
Carbon rod Zn - KOH and manganese!IV ) is reduced to
(cathode) anode paste
manganese! Ill ) at the cathode.
/Wv
Brass current ( b ) KOH makes ihe electrolyte
| collector paste in this batten basic. Thus, it is
'

Spacer •V - v* called an alkaline drv cell .

’ I fen KOH
electrolyte
Zinc shell Spacer

p
*

( anode) !* -* >
t
MnO2*
cathode mix

Steel jacket

Moist electrolytic paste of

ZnCI 2, Mn02 and NH 4CI

ELECTROCHEMISTRY 659
 Zn in KOH (anode)
FIGURE 7 It is important that
mercury batteries be recycled and
not just discarded because mercury Steel jacket
is a poisonous substance.
Separator

HgO, carbon (cathode)

Mercury Batteries
The tiny batteries found in hearing aids, calculators, and camera flashes
CHEMISTRY are mercury batteries, as shown in Figure 7, The anode half - reaction is
identical to that found in the alkaline dry cell. However, the cathode, or
'STO*
Module 10 : Electrochemical Cells reduction, half -reaction is different. The cathode half -reaction is
described bv the following equation.
0
HgO(s) + H:0( / ) + 2e~ > Hg( / ) + 2QH~{ aq )

Fuel Cells
A fuel cell is a voltaic cell in which the reactants are being continuous-
ly supplied and the products are being continuously removed.
Therefore, unlike a battery, a fuel cell could, in principle, work forever,
For a variety of links related to this
chapter, go to www.scilinks.org changing chemical energy into electrical energy.
Topic: Fuel Cells
SciLinks code: HC60625
^ Fuel cells based on the reactions listed below and shown in Figure 8
are used in the United States space program.

Cathode: 02(g) + 2H:0( / ) + 4e "

> 40H ( aq )
’

Anode: 2H:(g) + 4011~ ( aq ) » 4e + 4H20( / )

~

Net reaction: 2H 2 + 02 ——» 2H->0

Fuel cells are very efficient and have very low emissions.

Excess H 2(g) + H 20(g) Excess O 2(g) + H 20(g)

FIGURE 8 The reactions in

this fuel cell take place at carbon
electrodes that contain metal
catalysts. The water formed is Porous graphite Electrolyte solution Porous graphite
removed as a gas. anode cathode

660 CHAPTER 20
 Corrosion and Its Prevention
SCllNKS. Developed
NjtkMul SdtMt
nuuitamrd by tbt
Tf d n Avmuboa
Corrosion is an electrochemical process that has a large economic **
impact . Approximately 20% of all the iron and steel produced is used
For a variety of links related to this 1
chapter, go to www.scilinks.org I
to repair or replace corroded structures. One of the metals most com -
monly affected by corrosion is iron. Rust , hydrated iron( lll) oxide,
Topic: Corrosion
SciLinks code: HC60360
^
forms by the following overall reaction.
4Fe(s) + 302(g) + H20( /) > 2Fe:03 vvH:0( s)
*
The amount of hydration of the iron oxide, reflected by the coefficient
.vin the equation above, varies, and affects the color of the rust formed.
The mechanism for the corrosion of iron contains the following elec -
trochemical reactions.
> Fe:~( w ) + 2 e
~
Anode: Fe(s) /
Cathode: O2 ( g ) + 2H:0( / ) + 4e~ ~
> 40H ( aq )
The anode and cathode reactions occur at different regions of the metal
surface. The electric circuit is completed bv electron flow through the
metal itself, which acts like the wire in an electrochemical cell. The
water on the surface of the metal serves as the salt bridge. Thus, for cor -
rosion to occur, water and oxygen must be present with the iron.
As shown in Figurec), when the iron is exposed to water and oxygen, the
iron metal at the anodic site is oxidized to Fe:+ ions. The electrons released
at this site travel along the metal ( like the wire of a cell) to the cathodic
region, where oxygen is reduced. The Fe: ions travel along the moisture
^

FIGURE 9 The cathodic reaction

toward the cathodic regions. At the cathode, the Fe:" ions are further oxi-

^-
happens where the 02 concentration
dized to Fc ^ ions and form rust, which is hydrated iron oxide. Fe^C AfTO. is high. The anodic reaction happens
2Fe2+( aq ) + ( 3 + A )H:0( / ) > Fe 203 - AH:0( s) + 6H V/ ) + 2e~ in a region where the 0: concentra -
tion is low, such as a pit in the metal.

Water molecule, H 20

Oxygen molecule, 02
Iron(ll) ion, Fe 2 *
Hydroxide ion, OH

Anodic site: Cathodic site:

» 2e + Fe2 ' (ag) 02(aq) + 2 H20( /) + 4e~
Fe(s)

Iron, Fe
* » 40H (aqr )
Paint

Water layer
f Ion conduction

•TaV<«] T«
|
•Ji

ELECTROCHEMISTRY 661
 The presence of salt or high acidity speed the corrosion process,
because the movement of electrons is facilitated by the extra ions present .
I low can corrosion be prevented ? One way, which makes use of elec-
trochemical properties of metals, is to coat steel with zinc in a process
called galvanizing. Zinc is more easily oxidized than iron; therefore, zinc
will react before the iron is oxidized . This is called cathodic protection ,
and the more easily oxidized metal used is called a sacrificial anode.
The Alaskan oil pipeline, shown in Figure 10, is an example of steel that
is cathodically protected . However, instead of coating, zinc is connected to
the pipe by a wire. The zinc will oxidize before the iron in the steel does.
As the zinc anode corrodes, it gives electrons to the cathode, the steel , and
as the zinc anode does so. it prevents the steel from corroding. As the zinc
dissolves, it needs to be replaced. As long as zinc metal that is able to cor-
rode is present , the steel will be protected from corrosion .

FIGURE 10 The Alaskan pipeline

is cathodically protected by a
Electrical Potential
parallel zinc cable.
In a voltaic cell , the oxidizing agent at the cathode pulls the electrons
through the wire away from the reducing agent at the anode. The " pull. "

or driving force on the electrons, is called the electric potential. Electric

potential , or voltage, is expressed in units of volts ( V ) , which is the
.
potential energy per unit charge Current is the movement of the elec-
trons and is expressed in units of amperes, or amps ( A ).
Electrical potential is analogous to gravitational potential. Just as w ater
flows from a position of higher gravitational potential to a position of lower
— ,r i K r n
-

gravitational potential, electrons How from higher electric potential to

Careers in Chemistry lower electrical potential.
-
Go to go.hrw.com for a full length
article on careers in chemical Electrode Potentials
engineering. Reconsider the voltaic cell shown in Figure 4. There are two electrodes.
JS Keyword: HC 6 ELEX Zn and Cu . These two metals each have different tendencies for accept -
^ ing electrons. This tendency for the half - reaction of either copper or zinc
to occur as a reduction half - reaction in an electrochemical cell can he
quantified as a reduction potential . There are two half -cells in Figure 4: a
strip of zinc placed in a solution of ZnS04 and a strip of copper placed in
a solution of CuS04. The difference in potential between an electrode and
its solution is known us electrode potential . When these two half-cells are
connected and the reaction begins, a difference in potential is observed
between the electrodes. Finis potential difference, or voltage, is propor -
tional to the energy required to move a certain electric charge between
the electrodes. A voltmeter connected across the Zn | | Cu voltaic cell
measures a potential difference of about 1.10 V when the solution con -
centrations of Ziv ~ and Cu 2" ions are each 1 M .
The potential difference measured across the complete voltaic cell is
easily measured and equals the sum of the electrode potentials for the
two half - reactions. But an individual electrode potential cannot be meas-

662 CHAPTER 20
ured directly. This is because there can be no transfer of electrons unless
both the anode and the cathode are connected to form a complete cir - H 20)
cuit . A relative value for the potential of a half -reaction can be deter -
mined by connecting it to a standard half -cell as a reference. This
standard half -cell , shown in Figure 11, is called a standard hydrogen
electrode, or SHE . It consists of a platinum electrode dipped into a
1.00 M acid solution surrounded by hydrogen gas at 1 atm pressure and Pt wire *
25 C. Other electrodes are ranked according to their ability to reduce H 2( g )
hydrogen under these conditions.
The anodic reaction for the standard hydrogen electrode is described
by the forward half -reaction in the following equilibrium equation. Pt black ,

H 2(g ) f
- l
12 H +( aq ) + 2e ~
electrode

The cathodic half - reaction is the reverse. An arbitrary potential of

( ).( )( ) V is assigned to both of these half - reactions. The potential of a half FIGURE 11 A hydrogen
cell under standard conditions measured relative to the standard hydro - electrode is the standard reference
electrode for measuring electrode
gen electrode is a standard electrode potential . E". Electrode potentials
potentials. The electrode surface in
are expressed as potentials for reduction. These reduction potentials contact with the solution is actually
provide a reliable indication of the tendency of a substance to be a layer of hydrogen adsorbed onto
reduced . Figure 12 shows how the SHE is used to find the electrode the surface of the platinum.
potentials of the zinc and copper half -cells. Half - reactions for some
common electrodes and their standard electrode potentials are listed in
Table 1 on the next page.
Effective oxidizing agents, such as Cu:+ and F:. have positive E° val -
ues. Half -reactions with negative reduction potentials prefer oxidation
over reduction . Negative E" values indicate that the metal or other elec-
trode is more willing to give up electrons than hydrogen. Effective
reducing agents, such as Li and Zn. have negative E" values.
When a half - reaction is written as an oxidation reaction , the sign of its
electrode potential is reversed , as shown for the oxidation and reduction
half - reactions for zinc.

Zn:+ + 2e ’
> Zn
• E° = -0.76 V
Zn > Zn 2 + + 2e~
°
E = +0.76 V

Zinc strip, Copper

Zn strip, Cu

i i FIGURE 12 Tlie electrode poten -

tials of zinc and copper half -cells are
measured by coupling them with a
standard hydrogen electrode.

ELECTROCHEMISTRY 663
 TABLE 1 Standard Reduction Potentials
Standard Standard
electrode electrode
potential, E ° potential, E °
Half -cell reaction (in volts) Half-cell reaction (in volts)
F2 + 2e 4 12F “
+2.87 Fe3* + 3e~ < Fe -0.04
MnO + SH + 5 e + ~
Mn2+ + 4H20 +1.49 Pb2* + 2e~ <- ± Pb -0.13
^
Auu + 3e Z t Au'
+1.42 Sn 2 + + 2e~ 1Sn -0.14
Cl 2 + 2e~ <r 2cr +1.36 Ni2* + 2e ~
t Ni - 0.23
Cr:0 + 14H+ + 6r f 22Cru + 7H:0
^ = +1.33 Co2+ + 2e ~
^t cCod - 0.28

Mn02 + 4H" + 2e~ t Mn2+ + 2H - 0 . +1.21 Cd2+ + 2T -0.40

Br 2 + 2e’2 2Br +1.07 Fe 2+ + 2e~ f t Fe -0.41
2
Hg * + 2e
^ ~
Hg +0.85 S + 2e ~
S2‘
-0.51
4

Ag* + c
~
Ag +0.80 Cr3* + 3e ~
Cr -0.74
Hg2* + 2 e~ 2Hg +0.80 Zn2* + 2e~ t Zn -0.76
Fe3* + <T f t Fe2* +0.77 Al3* + 3e~ f * A1 - 1.66
,_
M11O 4 + £ 4 =-> MnOj "
+0.56 Mg2+ + 2e ~
Mg -2.37
12 + 2e~ 21 +0.54 Na ^ + e~ 2 t Na -2.71
Cu2* + 2e * Cu +0.34 2 ^
Ca * + 2e < ~
Ca - 2.76
Cu2* + e~ <- Cu" +0.16 Ba2+ + 2e’ t Ba - 2.90
S + 2W ( aq ) + 2e~ < » H:S( £/ £/ ) +0.14 K* + e~ ?K -2.93
2 H*( aq ) + 2e~ f >H O.(X ) Lir + e < > Li -3.04
2

The potential difference across the zinc /hydrogen cell is -0.76 V. so

zinc is considered to have an electrode potential of -0.76. The negative
CHEMISTRY a I number indicates that electrons flow from the zinc electrode, where zinc
is oxidized, to the hydrogen electrode, where aqueous hydrogen ions
Module 10 : Electrochemical Cells are reduced.
A copper half-cell coupled with the standard hydrogen electrode gives
a potential difference measurement of +0.34 V. Iliis positive number
indicates that Cu 2 ( aq ) ions are more readily reduced than H ( aq ) ions.
y *

Standard electrode potentials can be used to predict if a redox reac -

tion will occur spontaneously. A spontaneous reaction will have a posi-
tive value for £ " r //, which is calculated using the following equation.
(

°cell = EU cathode - E°anotle

E

The half-reaction that has the more negative standard reduction potential
will be the anode. Oxidation occurs at the anode, so the anode half-cell
reaction will be the reverse of the reduction reaction found in Table 1 For .
this reason, the total potential of a cell is calculated by subtracting the stan -
dard reduction potential for the reaction at the anode { E°im xlt ) from the
(

standard reduction potential for the reaction at the cathode ( E°calhode ) .

664 CHAPTER 20
 SAMPLE PROBLEM A For more help, go to the Math Tutor at the end of this chapter.
Write the overall cell reaction, and calculate the cell potential for a voltaic cell consisting of the following half -
cells: an iron ( Fe ) electrode in a solution of Fe(N03)3 and a silver ( Ag) electrode in a solution of AgINOv

SOLUTION
1 ANALYZE ,h( w/ ) and a second half -cell consists of
Given: A half -cell consists of Fe( s ) with Fe ( NO;
Ag( s ) with AgNO$ ( aq ).
Unknown: Encell

2 PLAN 1. Look up En for each half- reaction ( written as reductions) in Table 1 .

*
Fz +( aq ) + 3e "

°
Fe(s) E = -0.04 V Ag* ( t/ q ) + e °
Ag(.y ) E = +0.80 V
2. Determine the cathode and anode.

Fe in Fe(N03)3 is the anode because it has a lower reduction potential than Ag. Ag in
Ag( NO ) is therefore the cathode
^ .
3 COMPUTE .
1 Determine the overall cell reaction. Multiply the Ag half - reaction by 3 so that the num -
ber of electrons lost in that half-reaction equals the number of electrons gained in the
oxidation of iron. Reverse the iron half -reaction to be an oxidation half -reaction.
3 A g^ ( u q ) + Fe( s) 3 Ag(s) + Fe^ ( aq )

^
,
2. Calculate the cell potential by E0 = Evcalho(itt - En irHidr Note that when a half-reaction is
(

multiplied by a constant, the En value is not multiplied by that constant but remains the same.

Enceii = E 0cathode - E°anode = +0.80 V - ( -0.04 V ) = +0.84 V

4 EVALUATE riie calculated value for E" cell is positive, which confirms that it is a voltaic cell, as the prob-
lem states.

PRACTICE Answers in Appendix E

.
1 For each pair of half -cells, determine the overall electrochemical
reaction that proceeds spontaneously and the E° value. Go to go.hrw.com for
more practice problems
a. G+O /Cr 3* and NrVNi
^
b. SHE and Fe:7Fe v *
that ask you to calculate
cell potential.
Keyword: HC 6 ELEX

SECTION REVIEW 4. Given the Mn02/Mn2' and Cr3+/Cr half -cells,

1. What is a voltaic cell ? determine the overall electrochemical reaction
that occurs spontaneously and the E value.
°
2. What is electrode potential, and how is it used to
calculate information about an electrochemical cell? Critical Thinking
.
3 Given the Na*/Na and K+/K half -cells, determine 5. EVALUATING IDEAS A sacrificial anode is allowed
the overall electrochemical reaction that proceeds to corrode. Why is use of a sacrificial anode con-
spontaneously and the E° value. sidered to be a way to prevent corrosion?

ELECTROCHEMISTRY 665
 Chemistry in Action
Fuel- Cell Cars
The car of the future is quiet, has low The use of fuels such as methanol
emissions, and requires less mainte - solves the storage and fuel infrastruc -
nance than cars of today do. These ture problem, because these fuels can
are the promises of fuel-cell cars. The be stored similar to the way gasoline
development of fuel-cell cars has is stored. Therefore, these fuels can be
been pushed by state and federal pro- sold at current gasoline stations.
grams, legislation, and funding. There One should also consider the emis -
are a number of issues that need to sions and energy use involved in
be resolved before the large-scale Eventually, fuel-cell cars such as this making and delivering the hydrogen
manufacture of fuel-cell cars becomes one may replace gasoline-powered cars. fuel in addition to the emissions from
feasible. These include the fuel- the hydrogen fuel cell. Producing
storage capacity of the car, and the The range of fuel-cell powered cars is hydrogen fuel itself could involve sub -
fueling infrastructure. limited by the amount of fuel that can stantial emissions. Even so, fuel -cell
The technology currently favored for be stored in the storage tank. Current cars are still more efficient and have
automobiles is the proton- exchange storage now limits the cars to around greater environmental benefits than
membrane (PEM) fuel cell. The system 100 miles before refueling. Researchers the internal-combustion cars of today.
works by combining hydrogen with in this area are looking into carbon- Currently, all major car companies
oxygen taken from the outside air. The adsorption systems, which are refriger- are developing and researching fuel -
movement of the electrons (produced ated and pressurized tanks that can cell cars. Most companies have pro -
by the redox reaction) along an exter - store large amounts of hydrogen. totype cars and some cars are in use
nal route generates electricity, which Hydrogen is very combustible, but safe by governmental institutions. Which
is used eventually to turn the car hydrogen tanks have been developed. type will ultimately succeed in the
wheels. The process is two to three So today, the experts do not have any mass market is yet unknown. Experts
times more efficient than that of the more concern about the safety of agree, though, that for zero - emission
internal -combustion engine, and the hydrogen storage then they do about cars, hydrogen is the only major fuel
only products are water and a moder - gasoline storage. option that has been identified to
ate amount of energy as heat. In most However, the landscape is not yet date.
cases, a traditional car battery is used dotted with hydrogen refueling sta -
to operate the car's electrical system. tions. Current experimental users Questions
In principle, fuel cells can run on such as governmental institutions 1. Fuel cells that use hydrogen as
any hydrogen -rich fuel. Several can- must have their own hydrogen refu- fuel produce water and moderate
didate fuels that can power fuel cells eling stations. Auto companies say amounts of energy in the form of
are being investigated: methanol, there needs to be a consumer infra- heat as the only emissions. What
ethanol, natural gas, gasoline, and structure for the hydrogen fuel -cell kinds of negative effects might
liquid or compressed hydrogen. If cars before consumers will buy. On cars that use hydrogen-rich fuels
the fuel is not hydrogen gas, the the other hand, possible developers have on the environment ?
engine needs to include a reformer of such hydrogen stations say that
2. In the PEB fuel cell, the hydrogen
that can convert the other fuel (such there needs to be a demand before
ions are produced at which elec -
as methanol) to hydrogen. the infrastructure can form.
trode: the anode or cathode ?

666 CHAPTER 20
Electrolytic Cells SECTION 3

OBJECTIVES
S ome oxidation - reduction reactions do not occur spontaneously but >J Describe the nature of elec-
can be driven by electrical energy. If electrical energy is required to pro - trolytic cells.
duce a redox reaction and bring about a chemical change in an electro -
chemical cell, it is an electrolytic cell. Most commercial uses of redox Describe the process of elec-
^
reactions make use of electrolytic cells. trolysis in the decomposition
of water and in production of
metals.

How Electrolytic Cells Work Explain the process of

^
electroplating.
A comparison of electrolytic and voltaic cells can be seen in Figure 13.
The voltaic cell shown in Figure 13 has a copper cathode and a zinc
anode. If a battery is connected so that the positive terminal contacts the ^ Describe the chemistry of a
copper electrode and the negative terminal contacts the zinc electrode, rechargeable cell.
the electrons move in the opposite direction . The battery forces the cell
to reverse its reaction: the zinc electrode becomes the cathode, and the
copper electrode becomes the anode. The half - reaction at the anode, in
which copper metal is oxidized , can be written as follows:
o
Cu > Cu 2 ' + 2e
The reduction half - reaction of zinc at the cathode is written as follows: FIGURE 13 The direction in
which the electrons move reverses
n if a voltaic cell is connected to a
Zir + + 2e~ » Zn
direct current source to become an
electrolytic cell .

Voltaic Cell Electrolytic Cell

Zinc strip Copper strip

I
Zinc sulfate,
ZnS04,
solution

Anode Cathode
Copper (ll) sulfate,
CuS04, solution

Cathode
I¥
Anode

ELECTROCHEMISTRY 667
 There are two important differences between the voltaic cell and the
electrolytic cell.
1 . The anode and cathode of an electrolytic cell are connected to a bat -
tery or other direct -current source, whereas a voltaic cell serves as a
source of electrical energy.
2 . Electrolytic cells are those in which electrical energy from an external
source causes nonspontaneous redox reactions to occur. Voltaic cells
are those in which spontaneous redox reactions produce electricity. In
an electrolytic cell , electrical energy is converted to chemical energy:
in a voltaic cell , chemical energy is converted to electrical energy.

Electroplating
Dtvttoptd iMiftUtatd by «1* An electrolytic process in w hich a metal ion is reduced and a solid metal is
Njtwul WHKI Tf«km AimMMfi
deposited on a surface is called electroplating. An electroplating cell con -
For a variety of links related to this
chapter, go to www.scilinks . org tains a solution of a salt of the plating metal , an object to be plated ( the
Topic: Electroplating
SciLinks code: HC60492
^ cathode ) , and a piece of the plating metal ( the anode ). A silver-
plating cell contains a solution of a soluble silver salt and a silver anode.
The cathode is the object to be plated . The silver anode is connected to
the positive electrode of a battery or to some other source of direct cur -
rent . The object to be plated is connected to the negative electrode.
A cell in which silver is being electroplated onto a bracelet can be
seen in Figure 14. Silver ions are reduced at the cathode according to
the following half -reaction and deposited as metallic silver when elec-
trons flow through the circuit .

Ag" + e > Ag

CHEMISTRY u $ Silver strip, Ag

Module 10: Electrochemical Cells

>
Ag ( CN 2
/ solution

FIGURE 14 The bracelet in this

cell is being coated with a thin layer
of silver. Silver ions are replaced in
the solution as the pure silver anode
Power source
dissolves. Cathode Anode

668 CHAPTER 20
Meanwhile, metallic silver is oxidized at the anode according to the fol -
lowing half -reaction .
i
~
Ag * Ag + e
*

In effect, silver is transferred from the anode to the cathode of the cell .

Rechargeable Cells
A rechargeable cell combines the oxidation -reduction chemistry of
both voltaic cells and electrolytic cells. When a rechargeable cell con -
verts chemical energy to electrical energy, it operates as a voltaic cell .
But when the cell is recharged , it operates as an electrolytic cell, con -
verting electrical energy to chemical energy.
The standard 12 V automobile battery, shown in Figure 15, is a set of
six rechargeable cells. The anode in each cell is lead submerged in a
solution of H:S04. The anode half-reaction is described below.
Pb(s) + SOj-( aq ) PbSO4(s) 4 2e~
At the cathode, Pb02 is reduced according to the following equation.
Pb02(s) + 4H >g ) + SO j-( aq ) + 2e ~
PbS04(s) 4 2 H 20( / )
The net oxidation - reduction reaction for the discharge cycle is:
Pb( s ) + Pb02(s ) 4- 2 H:S04( M/ ) •
> 2 PbS04(s ) 4 2 H 20( / )
A car 's battery produces the electric energy needed to start its engine.
Sulfuric acid , present as its ions, is consumed , and lead ( II ) sulfate accu -
mulates as a white powder on the electrodes. Once the car is running,
the half - reactions are reversed by a voltage produced by the alternator.
The Pb. PbO:, and H 2S04 are regenerated. A battery can be recharged
as long as all reactants necessary for the electrolytic reaction are pre -
sent , and all reactions are reversible.

©
Intercell connectors

©
A

Pb plates FIGURE 15 The rechargeable

Pb 02 plates cells of a car battery produce electric-
H 2 S04(aqr ) ity from reactions between lead ( lV)
Intercell dividers oxide, lead , and sulfuric acid .

ELECTROCHEMISTRY 669
 Electrolysis
Electroplating and recharging a battery are examples of electrolysis.
Electrolysis is the process of passing a current through a cell for which the
cell potential is negative and causing an oxidation - reduction reaction to
occur That is. electrical energy is used to force a nonspontaneous chemi-
cal reaction to occur. For this cell reaction to occur, the external voltage
must be greater than the potential that would be produced by the spon -
taneous reverse cell reaction.
Electrolysis is of great industrial importance. It is used to purify
many metals from the ores in which they are found chemically com-
bined in Earth 's crust.

Electrolysis of Water
The electrolysis of water, shown in Figure 16, leads to the cell reaction
in which water is broken down into its elements. I F and 02. Recall that
hydrogen gas and oxygen gas combine spontaneously to form water and
are used to power fuel cells, which produce electricity. Therefore, the
reverse process ( electrolysis of water ) is nonspontaneous and requires
electrical energy. The following half -reactions occur at the anode and
cathode.
Anode: 6 KFO( / ) 4e + 02 ( g ) + 4H3O ( aq )
Cathode: 4H:0( / ) + 4e > 21F(g) + 401\ ( aq )
~

FIGURE 16 Electrical energy

from the battery is used to break
.
down water Hydrogen forms at
the cathode ( left tube ), and oxygen
forms at the anode ( right tube ).

670 CHAPTER 20
Aluminum Production by Electrolysis
Aluminum is ihe most abundant metal in Earth's crust , ll is a relative -
ly reactive metal; therefore, in nature, it is found as its oxide in an ore
called bauxite. Aluminum is now very useful commercially, but it was
not until 1 X 86 that a process to obtain pure aluminum metal was dis -
covered. Charles M. Hall ( from the United States) and Paul Heroult
( from France ) simultaneously, but independently, determined a practi -
cal method for producing aluminum; it is an electrolytic process called
the Hall-Heroult process.
Bauxite ore contains not only aluminum oxide ( AI2Q;). but oxides of
iron, silicon, and titanium. Therefore, the aluminum oxide ( called alu- Chemistry in Action
mina ) must first be separated from the other compounds in the ore. The Sodium Production
pure hydrated alumina ( Al203 v / H20 ) is obtained by treating bauxite by Electrolysis
with sodium hydroxide, which dissolves the alumina but does not dis- Sodium is such a reactive metal that
solve the other compounds in the ore. Hie alumina solution is then sep - preparing it through a chemical process
arated from the remaining solid compounds and reprecipitated to can be dangerous. Today, sodium is pro-
obtain pure alumina. The purified alumina is dissolved in molten cryo- duced mainly by the electrolysis of
molten sodium chloride. The melting
lite. Na3 AlF6. at 970 C in an electrochemical cell, and the aluminum point of sodium chloride is about
ions are reduced to aluminum metal. The liquid aluminum is denser 800°C; but mixing it with solid calcium
than the molten cryolite and alumina: therefore, the molten aluminum chloride lowers the melting point to
metal settles to the bottom of the cell and is drained off periodically. around 600°C. This mixture is intro-
The electrolytic solution contains a large number of aluminum - duced into an electrolytic cell called the
Downs Cell to retrieve the sodium
containing ions, and the chemistry of the electrochemical reaction is not metal, and the lower melting point
completely understood. Scientists still debate the exact species that par - allows the cell to use less electrical
ticipate in the half-reactions; but the overall cell reaction is energy to run.
2 AI203( / ) + 3C(.v )
* 4 A l( / ) + 3C02(s ).
where carbon is the anode and steel is the cathode in the cell.
The aluminum metal produced in this process is 99.5% pure. The
Hall-Heroult process made the production of aluminum economically
feasible. However, this process is the largest single user of electrical
energy in the United States—nearly 5 % of the national total. Recycling
aluminum saves almost 95 % of the cost of production. Aluminum recy -
cling is one of the most economically worthwhile recycling programs
that has been developed.

SECTION REVIEW Critical Thinking

1. Describe an electrolytic cell. 5. APPLYING CONCEPTS Copper ore contains zinc
2. Explain the process of electroplating. metal, which is oxidized along with Cu during the
electrolytic purification process. However, the Zn2+
3. What is a rechargeable cell ? ions are not then reduced when the Cu2+ ions are
4. Give an example of how electrolytic cells are used reduced to Cu at the cathode to obtain purified
in industry. copper metal. Explain how Zn can be oxidized
with Cu, but their ions not be reduced together.

ELECTROCHEMISTRY 671
 CHAPTER HIGHLIGHTS
Introduction to Electrochemistry
! Vocabulary • Electrochemistry is the branch of chemistry that deals with
electrochemistry electricity- related applications of redox reactions.
electrode •The electrode immersed in an electrolyte solution is a half -cell.
half -cell •The anode is the electrode where oxidation takes place. ITe
anode cathode is the electrode where reduction occurs.
cathode •The cell consists of electrodes connected by a wire along which
the electron travels and a salt bridge ( or porous barrier )
through which ions transfer to balance the charge.
• An electrochemical cell is a system
•
of electrodes and elec-
trolytes in which either chemical reactions produce electrical
energy or electric current produces chemical change.

Voltaic Cells
I Vocabulary • A voltaic cell , sometimes called a galvanic cell , uses a sponta -
voltaic cell neous redox reaction to produce electrical energy. Examples of
reduction potential voltaic cells are batteries and fuel cells.
electrode potential • Fuel cells are voltaic cells in which the reactants are continu -
standard electrode potential ously supplied and the products are continuously removed .
•The potential difference must be measured across a complete
cell because no transfer of electrons can occur unless both the
anode and cathode are connected to form a complete circuit.
Thus, the standard electrode potential for a half -cell is meas-
ured against the standard hydrogen electrode ( SHE ) .
.
•Standard reduction potentials E1' , are stated as reduction half -
reactions. Effective oxidizing agents have positive E" values,
while effective reducing agents have negative E" values.
• A voltaic cell has an £% value that is positive.
(

•Corrosion occurs when iron is exposed to oxygen and water.

One of the best methods to prevent corrosion is by the use of
sacrificial anodes.

Electrolytic Cells
I Vocabulary • Electrolytic cells are cells in which electrical energy from an
electrolytic cell external source causes a nonspontaneous reaction to occur.
electroplating • An electrolytic cell has an £" // value that is negative.
(

electrolysis • Electrolysis has great economic impact. Applications of

electrolytic cells are electroplating of metallic surfaces,
rechargeable batteries, aluminum production, and purification
of metals.

672 CHAPTER 20
 CHAPTER REVIEW
For more practice, go to the Problem Bank in Appendix D
13. a. What information is provided by the stan -
Introduction to dard reduction potential of a given half-cell?
Electrochemistry b. What does the relative value of the reduction
potential of a given half-reaction indicate
SECTION 1 REVIEW
about its oxidation-reduction tendency ?
1. In the half -cell Zn2*( aq ) + 2e » Zn( s), what 14. When the cell Ba( s ) | Ba 2 +( aq ) ! | SnI Sn( .v )
is the electrode and is this half -reaction an is running, what observations can be made?
anodic reaction or a cathodic reaction?
2. What role does the porous barrier play ? PRACTICE PROBLEMS
3 . For each of the following pairs of half -cells,
15. For each of the following pairs of half -cells,
write the overall reaction and the cell notation. determine the overall electrochemical reaction
Assume the first half-cell given in each pair is
that proceeds spontaneously:
the cathodic half -cell.
a. AgVAg. Co:7Co
a. Na7Na NrVNi .
b. Au "7 Au, Zn:7Zn
'
.
h. F2/F S /H2S
c. Br2/Bi", Cr^/Cr
c. Hg2"/ Hg. K 7K
d. MnO /Mn2 *, Co27Co
4. Describe the components of an electrochemical ^
cell and how the electrical charge travels °
16. Determine the values of E for the cells in the
previous problem.
through these components.
17. Suppose chemists had chosen to make the I2 +
2c *
2 T half - cell the standard electrode and
Voltaic Cells had assigned it a potential of zero volts.
a. What would be the En value for the Br 2 +
> 2Br half-cell?
~
SECTION 2 REVIEW 2e
5 . Describe a voltaic cell, and give two examples b. What would be the E° value for the Alu +
of a voltaic cell. 3c > Al half-cell?
6. What is the essential advantage of a fuel cell c. How much change would be observed in the
over batteries in the generation of electrical En value for the reaction involving Br 2 + I if
energy? the I2 half -cell is the standard?
7 . Explain why corrosion is a voltaic cell. 18. If a strip of Ni were dipped into a solution of
8. Discuss the advantages and disadvantages of -
AgNO , what would be expected to occur ?
corrosion-prevention methods. Explain, using E" values and equations.
9. Which half reaction would more likely be an
oxidation reaction: one with a standard reduc -
tion potential of -0.42 V. or one with a standard
Electrolytic Cells
reduction potential of +0.42 V ? SECTION 3 REVIEW
10. Why are dry -cell batteries called dry cells , even
19. What reaction happens at the cathode in an
though their chemistry involves water ?
electrolysis process?
11. a. Explain what is meant by the potential
20. Explain why water cannot be used in the electro-
difference between the two electrodes in an
chemical cell during the production of aluminum.
electrochemical cell.
21. Calculate the voltage of a cell in which the
b. How is this potential difference measured?
overall reaction is the electrolysis of aqueous
What units are used?
cadmium chloride into its elements.
12. The standard hydrogen electrode is assigned an
22. According to electrochemical data, can Ni be
electrode potential of 0.00 V. Explain why this
plated onto a zinc metal object using a nickel
voltage is assigned.
nitrate solution? Explain.

ELECTROCHEMISTRY 673
 CHAPTER REVIEW

.
23 Distinguish between a voltaic cell and an 32. How do the redox reactions for each of the fol -
electrolytic cell in terms of the nature of the lowing types of batteries differ ?
reaction involved. a. zinc-carbon
24. a . What is electroplating? b. alkaline
b. Identify the anode and cathode in such c. mercury
a process. 33. a . Why are some standard reduction potentials
positive and some negative?
b. Compare the En value for a metal with the
MIXED REVIEW reactivity of that metal.
25. Predict whether each of the following reactions
will occur spontaneously as written by deter - CRITICAL THINKING
mining the E" value for potential reaction .
Write and balance the overall equation for each 34. Applying Models Explain how the oxidation -
reaction that does occur spontaneously. reduction chemistry of both the voltaic cell
a . Mg + Sn 2+ > and the electrolytic cell are combined in the
b. K + AF + > chemistry of rechargeable cells.
c. Li + Zn
'
» 35. Applying Ideas In lead -acid batteries, such as
d . Cu + Cl: -> your car battery, the degree of discharge of the
26. Why is it possible for alkaline batteries to be battery can be determined by measuring the
smaller than zinc-carbon dry cells? density of the battery fluid. Explain how this
27. Draw a diagram of a voltaic cell whose two is possible.
half - reactions consist of Ag in AgNO -* and Ni in
36. Applying Ideas In lead -acid batteries, the
NiS04. Identify the anode and cathode, and
indicate the directions in which the electrons battery cannot be recharged indefinitely.
and ions are moving. Explain why not .
28. Can a solution of SnfNOV) be stored in an 37. Interpreting Graphics A voltaic cell is
aluminum container ? Explain ^ , using En values. pictured below. Identify the species that is
29. A voltaic cell is made up of a cadmium oxidized if current is allowed to flow.
electrode in a solution of CdS04 and a zinc
Digital voltmeter
electrode in a solution of ZnS04. The two
half -cells are separated by a porous barrier.
a . Which is the cathode, and which is the
anode?
b. In which direction are the electrons flowing?
c. Write balanced equations for the two half -
reactions. and write a net equation for the
combined reaction .
/ Cr2072
-
MnC> 4 v Cr
30. Would the following pair of electrodes make a
good battery ? Explain. Mn 2* Pt Pt — 3 ^

Cd Cd:+ + 2 e
~
H" \H *

Fe Fe2+ + 2e~
31. a . What would happen if an aluminum spoon
were used to stir a solution of ZnfNCLJ:?
b. Could a strip of Zn be used to stir a solution
of ARNOOj? Explain , using Eil values.

674 CHAPTER 20
 CHAPTER REVIEW

42 . In our portable society, batteries have become a

USING THE HANDBOOK
necessary power supply. As consumers, we want
38 . Aluminum is described in Group 13 of the to purchase batteries that will last as long as
Elements Handbook as a self -protecting metal, possible. Advertisements tell us that some bat -
and can be used in preventing corrosion of iron teries last longer than others, but do they really ?
structures. Using electrochemical data, explain Design an investigation to answer the question.
how aluminum protects iron structures. Is there a difference in longevity between the
major brands of AA batteries? Add a cost -effec-
tiveness component to your design.
RESEARCH & WRITING 43. When someone who has a silver filling in a
tooth bites down on an aluminum gum wrapper,
39. Go to the library, and find out about the saliva acts as an electrolyte. The system is an
electroplating industry in the United States. electrochemical cell that produces a small jolt of
What are the top three metals used for plating, pain. Explain what occurs, using half-cell reac -
and how many metric tons of each are used for tions and £" values.
electroplating each year in the United States?
40. Investigate the types of batteries being
considered for electric cars. Write a report on
the advantages and disadvantages of these
types of batteries.
i Graphing Calculator Equilibrium
Constant for an Electrochemical Cell
Go to go.hrw.com for a graphing calculator
ALTERNATIVE ASSESSMENT exercise that asks you to calculate an equilib -
rium constant for an electrochemical cell.
41. Performance Take an inventory of the types of
batteries used in vour home. Find out the volt -
j

age supplied by each battery and what electro-

chemical reaction each uses. Suggest why that
^ Keyword: HC 6 ELEX

electrochemical reaction is used in each case.

ELECTROCHEMISTRY 675
 Math Tutor CALCULATING CELL POTENTIALS

You have learned that electrons are transferred in all oxidation- reduction reactions.
Electrons from a substance being oxidized are transferred to another substance being
reduced. A voltaic cell is a simple device that physically separates the oxidation reac -
tion from the reduction reaction, thus forcing electrons released during oxidation to
travel through a wire to reach the site of reduction. If a device, such as a light bulb or
motor, is placed in the circuit, the moving electrons can perform useful work.
The potential, or voltage, of a given voltaic cell depends on how strongly the oxida -
tion process tends to give up electrons in addition to how strongly the reduction
.
process tends to take them The greater these two combined tendencies, the higher
the potential of the cell. A potential has been measured for each half -reaction, as you
can see in Table 1 on p. 664 . In a voltaic cell, the process with the more - negative
reduction potential will proceed as the oxidation reaction at the anode of the cell. The
more positive reaction will proceed as reduction at the cathode. The following exam -
ple shows you how to determine the potentials of different kinds of voltaic cells.

Problem-Solving TIPS
• In a voltaic cell ,the process that has the more negative reduction potential will
proceed as the oxidation reaction at the anode of the cell.

SAMPLE
Calculate the potential of a voltaic cell in which Hg:+ ions are reduced to Hg metal while
Zn metal is oxidized to Zn 2 + ions.
Reduction takes place at the cathode, so the cathode half-reaction is
Hg2+(r/ </ ) + 2e —> Hg( / )
~

Oxidation takes place at the anode, so the anode half-reaction is

Zn( s ) — > Zn2+( aq ) + 2e
~

To use the equation for cell potential, rewrite the anode half -reaction as a reduction
.
reaction Zn2+( aq ) + 2e '

—
> Zn(.v ).
Use '
Fable I on page 664 to find the standard reduction potential for each half -reaction.
Then, calculate the cell potential .
Hg2+( aq ) + 2e~ —> Hg( / ) E lho( ie = +0.85 V
Zn 2+( aq ) + 2e ~ ^
—> Zn(s ) E’node = -0.76 V
(

£",// = Ka,Me - Eanode = V - (-0.76 V) = 1.61 V

PRACTICE PROBLEMS
.
1 Calculate the potential of a voltaic cell in which 2. Calculate the potential of a cell in which
aluminum metal is oxidized to Al + ions while the reaction is
Cu:" ions are reduced to CiC ions. Pb(s) + Br:( / ) Pb2* ( aq ) + 2Br ( aq ) t

676 CHAPTER 20
Answer the following items on a separate piece of paper. 5. Refer to the table of reduction potentials below.
MULTIPLE CHOICE
Which metal, Zn or Au, can reduce Sir 4 ions to
Sn metal when placed in an aqueous solution of
.
1 The electrode at which reduction occurs is Sn2+ ions?
A . always the anode. .
A Zn
B. always the cathode. B. Au
C . either the anode or the cathode . C. Both Zn and Au can reduce Sn:+ ions
D. always the half-cell. .
D Neither Zn or Au can reduce Sn 2 ions ^

2. Refer to the table of standard reduction poten - 6. When silver is electroplated onto another metal .
tials below. A voltaic cell contains a strip of zinc Ag" is
metal in a solution containing zinc ions in one A. oxidized at the anode.
half -cell. The second is a strip of tin metal in a B. reduced at the anode.
solution containing tin ions. When this cell
C. oxidized at the cathode.
operates,
D. reduced at the cathode.
A. Sn is oxidized and Zn:* is reduced.
B. Sn is reduced and Zn24 is oxidized. 7. Which metal would best provide cathodic protec-
C. Sn:4 is oxidized and Zn is reduced. tion from corrosion for an iron bridge?
D. Sn is reduced and Zn is oxidized.
* A . Au
B. Sn
3. When a rechargeable cell is being recharged,
C. Cu
the cell acts as a(n)
D. Mg
A. fuel cell. C. voltaic cell.
B. electrolytic cell. D. Leclanche cell. SHORT ANSWER

4. Refer to the table of standard reduction poten- 8. In the production of aluminum by the
tials below. The standard potential of the cell Hall-Heroult process, is the aluminum metal
Sn | Sn2* 11 Cru | Cr is -0.60 V. What is the stan - produced at the cathode or the anode?
dard reduction potential of the Cru/Cr 9. The reduction potential for nitric acid is ( ).% V
electrode? ( reduction half- reaction is NO5 + 4H4 + 3e~
A. +0.88 V C. -0.88 V NO + 2 H:0 ). If gold ( Au ) is placed in a beaker
B. +0.74 V D. -0.74 V of 1 M nitric acid, will the gold dissolve ?
EXTENDED RESPONSE
Half - cell reaction Standard reduction
10. Given a voltaic cell consisting of a gold electrode
°
potential, £ (in volts)
in a gold nitrate solution in one half-cell and a
Au3 ' + 2>e < t Au • +1.50 zinc electrode in a zinc nitrate solution in the
Cu2" + 2e + Cu
~
+(134 other half-cell, what occurs once the wire is
2 +
Fe + 2 e Fe -0.41 connected to both electrodes?
Sn2+ + 2c - * Sn -0.14 .
11 If pure water is placed in a beaker with wires
Zn2+ + 2c <r t Zn~
-0.76 connected to a cathode and anode and electrical
Mg 2 + 2e z
*
Mg -2.37 voltage is applied, will electrolysis of water
occur ? Explain your answer.

Remember that if you can elimi-

nate two of the four answer choices, your chances of
choosing the correct answer choice will double.

ELECTROCHEMISTRY 677
 EXPERIMENT 20

Voltaic Cells
OBJECTIVES BACKGROUND
• Construct a Cu- Zn voltaic cell . In voltaic cells, oxidation and reduction half -reactions
take place in separate half -cells, which can consist of
• Design and construct two other voltaic cells. a metal electrode immersed in a solution of its metal
• Measure the potential of the voltaic cells. ions. The electrical potential , or voltage, that devel -
• Evaluate cells by comparing the measured ops between the electrodes is a measure of the com -
cell voltages with the voltages calculated bined reducing strength of one reactant and
from standard reduction potentials. oxidizing strength of the other reactant .

MATERIALS SAFETY
0.5 M AI2( S04 )J, 75 mL
0.5 M CuS04, 75 mL
0.5 M ZnS04, 75 mL For review of safety, please see Safety in the
Aluminum strip, 1 cm x 8 cm Chemistry Laboratory in the front of your book .

Copper strip, 1 cm x 8 cm PREPARATION

Zinc strip, 1 cm x 8 cm 1 . Follow vour teacher ’s instructions to create the
Distilled water data table that you will use to record your data
for three voltaic cells.
100 mL graduated cylinder
2. Remove any oxide coating from strips of alu -
Emerv cloth minum. copper, and zinc by rubbing them with
150 mL beakers, 3 an emery cloth . Keep the metal strips dry until
Salt bridge you are ready to use them.

Voltmeter 3 . Label three 150 mL beakers “AI:( S04 ) 3,”

“ 011504;’ and “ ZnS04.”
Wires with alligator clips, 2

PROCEDURE
1. Pour 75 mL of 0.5 M ZnS04 into the ZnS04
beaker and 75 mL of 0.5 M CuS04 into the
CuS04 beaker.
2 . Place one end of the salt bridge into the CuS04
solution and the other end into the ZnS04
solution .
3 . Place a zinc strip into the zinc solution and a
copper strip into the copper solution .

678 CHAPTER 20
 EXPERIMENT 20

4. Using the alligator clips, connect one wire to one 3. Organizing Ideas: Use the E" values for the half -
end of the zinc strip and the second wire to the reactions to determine the E? for each cell.
copper strip. Take the free end of the wire
4. Resolving Discrepancies: Compare the actual
attached to the zinc strip and connect it to one
,

terminal on the voltmeter. Take the free end of cell voltages you measured with the standard
the wire attached to the copper strip, and con - cell voltages in item 3. Explain why you would
nect it to the other terminal on the voltmeter. expect a difference.
The needle on the voltmeter should move to the
right . If your voltmeters needle points to the CONCLUSIONS
left , reverse the way the wires are connected to 1. Inferring Conclusions: Based on the voltages
the terminals of the voltmeter . Immediately that you measured which cell produces the most
,
record the voltage reading in your data table, energy ?
and disconnect the circuit .
2. Applying Ideas: On the basis of your data , which
5. Record the concentration of the solutions and metal is the strongest reducing agent ? Which
sketch a diagram of your electrochemical cell. metal ion is the strongest oxidizing agent ?
6. Rinse the copper and zinc strips with a very
small amount of distilled water. Collect the rinse
3. Applying Ideas: Indicate the direction of elec -
tron How in each of your cell diagrams.
from the copper strip in the CuS04 beaker and
the rinse from the zinc strip in the ZnS04
beaker. Rinse each end of the salt bridge into EXTENSIONS
the corresponding beaker. 1. Predicting Outcomes: Describe how and why
the reactions would stop if the cells had been
7. Use the table of standard reduction potentials in
left connected .
the textbook to calculate the standard voltages
for the other cells you can build using copper, 2. Designing Experiments: Design a method that
zinc, or aluminum . Build these cells and measure could use several of the electrochemical cells
their potentials following steps 1 -6. you constructed to generate more voltage than
any individual cell provided . ( Hint: consider
CLEANUP AND DISPOSAL
what would happen if you linked an Al - Zn cell
and a Zn -Cu cell. If your teacher approves your
8. Clean all apparatus and your lab sta - plan , test your idea. )
tion . Wash your hands. Place the pieces
of metal in the containers designated by
your teacher. Each solution should be
poured in its own separate disposal container.
Do not mix the contents of the beakers.

ANALYSIS AND INTERPRETATION

1. Organizing Ideas: For each cell that you con -
structed . write the equations for the two half -cell
reactions. Obtain the standard half -cell poten -
tials for the half - reactions from Table 1, and
write these E0 values after the equations.
2. Organizing Ideas: For each cell you tested , com -
bine the two half -reactions to obtain
the equation for the net reaction .

ELECTROCHEMISTRY 679
Nuclear Chemistry
High temperature plasmas are being studied
as potential sources of fusion energy.
The Nucleus SECTION 1

OBJECTIVES
J Explain what a nuclide is, and
A tomic nuclei are made of protons and neutrons, which are collec - describe the different ways
tively called nucleons. In nuclear chemistry, an atom is referred to as a nuclides can be represented.
nuclide and is identified by the number of protons and neutrons in
its nucleus. Nuclides can be represented in two ways. When a symbol j Define and relate the terms
such as 2q£Ra is used, the superscript is the mass number and the sub - mass defect and nuclear
script is the atomic number. The same nuclide can also be written as binding energy.
radium-228, where the mass number is written following the element
name.
> j Explain the relationship
between number of nucleons
and stability of nuclei.
Mass Defect and Nuclear Stability
^ Explain why nuclear reactions
Because an atom is made of protons, neutrons, and electrons, you occur, and know how to
might expect the mass of an atom to be the same as the mass of an balance a nuclear equation.
equal number of isolated protons, neutrons, and electrons. However,
this is not the case. Let s consider a ;He atom as an example. The com -
'

bined mass of two protons, two neutrons, and two electrons is calcu-
lated below.

2 protons: ( 2 x 1.007 276 amu) = 2.014 552 amu

2 neutrons: ( 2 x 1.008 665 amu ) = 2.017 330 amu
2 electrons: ( 2 x 0.000 548 6 amu ) = 0.001 097 amu
total combined mass: 4.032 979 amu

However, the atomic mass of a life atom has been measured to be

4.002 602 amu. The measured mass. 4.002 602 amu, is 0.030 377 amu less
than the combined mass. 4.032 979 amu, calculated above. This differ -
ence between the muss of an atom and the sum of the masses of its pro -
tons, neutrons, and electrons is called the mass defect.

Nuclear Binding Energy

What causes the loss in mass? According to Albert Einstein's equation
/: = me2 , mass can be converted to energy, and energy to mass. The mass
defect is caused bv the conversion of mass to energy upon formation of
the nucleus. The mass units of the mass defect can be converted to
energy units by using Einstein 's equation. First, convert 0.030 377 amu
-
to kilograms to match the mass units for energy, kg nr /s2.
CHEMISTRY
^
Module 2 : Models of the Atom

1.6605 x IQ
'
2' kg
29
0.030 377 amu x = 5.0441 X lO
’
kg
1 amu

NUCLEAR CHEMISTRY 681

 FIGURE 1 This graph shows the Binding Energy per Nucleon
relationship between binding energy 10x10s
per nucleon and mass number. The c 56

binding energy per nucleon is a mea -

8 9x10s 2 He 26
^ 238 u

sure of the stability of a nucleus.

5^
8x 10s
7 x10s
. ^5 6x 10s
. 1
92 U

w E 5x 10
s
f Li
| x10s5.4
* 3x10ss
£.
T3
2x10
C 1 x 10s iH
CO
0
0 20 40 60 80 100 120 140 160 180 200 220 240
Mass number

The energy equivalent can now be calculated .

CROSS - DISCIPLINARY fi = me
Quarks E = ( 5.0441 x Hr29 kg )( 3.00 x 10s m /s)2
= 4.54 x 10 " 12 kgmr/s2 = 4.54 x 10 12 J
'

Many subatomic particles have been

identified. Leptons and quarks are the This is the nuclear binding energy , the energy released w hen a nucleus
elementary particles of matter. The elec -
is formed from nucleons . This energy can also be thought of as the
tron is a lepton. Protons and neutrons
are made of quarks. There are six types amount of energy required to break apart the nucleus. Therefore, the
of quarks that differ in mass and charge . nuclear binding energy is also a measure of the stability of a nucleus.
They are named up, down, strange,
.
charm, bottom, and top Protons consist Binding Energy per Nucleon
of two up quarks and one down quark, The binding energy per nucleon is used to compare the stability of dif -
and neutrons consist of two down ferent nuclides, as shown in Figure 1 . The binding energy per nucleon is
quarks and one up quark. Although indi-
the binding energy of the nucleus divided by the number of nucleons it
vidual quarks have not been isolated,
their existence explains the patterns of contains. Die higher the binding energy per nucleon , the more tightly
nuclear binding and decay. the nucleons are held together . Elements with intermediate atomic
masses have the greatest binding energies per nucleon and are there -
fore the most stable.

Nucleons and Nuclear Stability

Stable nuclides have certain characteristics. When the number of protons
in stable nuclei is plotted against the number of neutrons, as shown in
Figure 2. a belt -like graph is obtained. This stable nuclei cluster over a
range of neutron - proton ratios is referred to as the hand of stability.
Among atoms having low atomic numbers, the most stable nuclei are
those with a neutron - proton ratio of approximately 1:1 . For example.
iHe. a stable isotope of helium with two neutrons and two protons, has a
neutron -proton ratio of 1 :1. As the atomic number increases, the stable
neutron - proton ratio increases to about 1.5:1 . For example. 2 l*
s Pb. with
124 neutrons and 82 protons has a neutron - proton ratio of 1.51:1.
,

This trend can be explained by the relationship between the nuclear

force and the electrostatic forces between protons. Protons in a nucleus
repel all other protons through electrostatic repulsion , but the short

682 CHAPTER 21
 The Band of Stability FIGURE 2 The neutron - proton
ratios of stable nuclides cluster
130 together in a region known as the
band of stability. As the number of
120
protons increases, the ratio increases
from 1 :1 to about 1.5:1.
110

100

90

80
c
o
3
<D
70
C

O
60
<v
-E
Q

3 50

40

30

20

10

0
0 10 20 30 40 50 60 70 80 90 100

Number of protons

range of the nuclear force allows them to attract only protons very close
to them , as shown in Figure 3. As the number of protons in a nucleus
increases, the repulsive electrostatic force between protons increases
faster than the nuclear force. More neutrons are required to increase
the nuclear force and stabilize the nucleus. Beyond the atomic number
83. bismuth , the repulsive force of the protons is so great that no stable
nuclides exist .
Stable nuclei tend to have even numbers of nucleons. Of the stable
nuclides, more than half have even numbers of both protons and neutrons.
Only five nuclides have odd numbers of both . This indicates that stability
— —
of a nucleus is greatest when the nucleons like electrons are paired.
The most stable nuclides are those having 2, 8. 20. 28. 50. 82. or 126
protons, neutrons, or total nucleons. This extra stability at certain num - FIGURE 3 Proton A attracts pro -

— —
bers supports a theory that nucleons like electrons exist at certain
energy levels. According to the nuclear shell model , nucleons exist in
ton B through the nuclear force but
repels it through the electrostatic
force. Proton A mainly repels proton
different energy levels, or shells, in the nucleus. The numbers of nucleons C through the electrostatic force
—.
thut represent completed nuclear energy levels 2 8, 20, 28, 50, 82 , and because the nuclear force reaches
—
126 are called magic numbers. onlv a few nucleon diameters.

NUCLEAR CHEMISTRY 683

 Nuclear Reactions
Unstable nuclei undergo spontaneous changes that change their num -
ber of protons and neutrons. In this process, they give off large amounts
of energy and increase their stability. These changes are a type of
nuclear reaction . A nuclear reaction is a reaction that affects the nucleus
of an atom. In equations representing nuclear reactions, the total of the
atomic numbers and the total of the mass numbers must be equal on
both sides of the equation. An example is shown below.
4
^
jBe 4- He + o«
Notice that when the atomic number changes, the identity of the ele -
ment changes. A transmutation is a change in the identity of a nucleus as
a result of a change in the number of its protons.

SAMPLE PROBLEM A
> llte + _?
Identity the product that balances the following nuclear reaction: jPo

SOLUTION
^
1 . The total mass number and atomic number must be equal on both sides of the equation .
2i 2 p0 .
> He + ?
mass number: 212 - 4 = 208 atomic number: 84 - 2 = 82
.
2 Tire nuclide has a mass number of 208 and an atomic number of 82.
3. The balanced nuclear equation is 284PO * :He + 282pb
^ Pb.

PRACTICE Answers in Appendix E

Using < ) / / to represent a neutron and _ { e to represent an electron ,

[

complete the following nuclear equations: Go to go.hrw.com for

more practice problems
Es + iHc _
'^
1. 2 + ?
0» that ask you to
J_ 'isoNd complete nuclear
2.
^ Pm + equations.
Keyword: HC 6 NUCX

SECTION REVIEW b. 4 Be -t- p He — *J

_+ 0n
1. Define mass defect.
2. How is nuclear stability related to the neutron -
c. + _? _ •

”
» Ne
Critical Thinking
proton ratio ?
4. INTERPRETING GRAPHICS Examine Figure 2, and
3. Complete and balance the following nuclear is a stable isotope of lithium. Explain
equations:
predict if fLi
your answer.
a. Re 4- _? 4 17§Re 4- ] H
^
684 CHAPTER 2 1
Radioactive Decay SECTION 2

OBJECTIVES
* Define and relate the terms
n 18%, Henri Becquerel was studying the possible connection radioactive decay and nuclear
between light emission of some uranium compounds after exposure to radiation.
sunlight and X -ray emission . He wrapped a photographic plate in a
lightproof covering and placed a uranium compound on top of it . He Describe the different types
then placed them in sunlight . The photographic plate was exposed even of radioactive decay and their
though it was protected from visible light , suggesting exposure by effects on the nucleus.
X rays. When he tried to repeat his experiment , cloudy weather pre -
vented him from placing the experiment in sunlight . To his surprise, the
Define the term half-life, and
plate was still exposed. This meant that sunlight was not needed to
explain how it relates to the
produce the rays that exposed the plate. The rays were produced by
stability of a nucleus.
radioactive decay. Radioactive decay is the spontaneous disintegration
of a nucleus into a slightly lighter nucleus, accompanied by emission of
particles, electromagnetic radiation , or both. The radiation that exposed ^ Define and relate the terms
the plate was nuclear radiation, particles or electromagnetic radiation decay series, parent nuclide,
emitted from the nucleus during radioactive decay. and daughter nuclide.
Uranium is a radioactive nuclide, an unstable nucleus that undergoes
radioactive decay . Studies by Marie Curie and Pierre Curie found that + Explain how artificial
of the elements known in 18%. only uranium and thorium were radioactive nuclides are made,
radioactive. In 1898. the Curies discovered two new radioactive metal - and discuss their significance.
lic elements, polonium and radium. Since that time, many other radioac-
tive nuclides have been identified . In fact , all of the nuclides beyond
atomic number 83 are unstable and thus radioactive.

Types of Radioactive Decay SC

/lNKS. iXVA
Omtoped uu) HumUmcd fry Ikf
A nuclide 's type and rate of decay depend on the nucleon content and NJtKMUl Sumer Tt«)*n AIMXIJCIOB

energy level of the nucleus. Some common types of radioactive nuclide For a variety of links related to this
chapter, go to www scilinjcs.org
emissions are summarized in Table 1.
Topic: Radioactive Decay
SciLinks code: HC61254
^
TABLE 1 Radioactive Nuclide Emissions
Type Symbol Charge Mass ( amu)
Alpha particle 2»e 2+ 4.001 5062
Beta particle -iP 1- 0.000 5486
Positron JiP 1+ 0.000 5486
Gamma ray Y 0 0

NUCLEAR CHEMISTRY 685

 FIGURE 4 An alpha par -
ticle. identical to a helium
nucleus, is emitted during
the radioactive decay of
some very heavv nuclei .

210 Pn
84 PO

Alpha Emission
An alpha particle ( a ) is two protons and two neutrons bound together
and is emitted from the nucleus during some kinds of radioactive decay.
Alpha particles are helium nuclei and have a charge of 2+. They are
often represented with the symbol ; He. Alpha emission is restricted
almost entirely to very heavy nuclei . In these nuclei , both the number of
neutrons and the number of protons need to be reduced in order to
increase the stability of the nucleus. An example of alpha emission is the
decay of 2 Po into : Pb, shown in Figure 4. The atomic number
^ ^
decreases bv two. and the mass number decreases by four .

Beta Emission
* $Pb +
^ He

Nuclides above the band of stability are unstable because their neu -
tron / proton ratio is too large. To decrease the number of neutrons, a
-1I n neutron can be converted into a proton and an electron. The electron is
emitted from the nucleus as a beta particle. A beta particle ( p ) is an elec -
tron entitled from the nucleus during some kinds of radioactive decay.

I
6" 1P + -°\ P
]
An example of beta emission , shown in Figure 5, is the decay of j*C into
l
*N. Notice that the atomic number increases by one and the mass num -
ber Slavs the same.

14 p
* TN + V /?
_
Positron Emission
FIGURE 5 Beta emission causes
Nuclides below the band of stability are unstable because their neu -
the transmutation of !j{C into MN.
Beta emission is a type of radioac - tron / proton ratio is too small. To decrease the number of protons, a pro-
tive decav in which a neutron is con - ton can be converted into a neutron by emitting a positron . A positron is
verted to a proton with the emission a particle that has the same mass as an electron , but has a positive charge,
of a beta particle. and is emitted from the nucleu s during some kinds of radioactive decay.

686 CHAPTER 21
 iP * o" + +\ P
into Ar. Notice
An example of positron emission is the decay of
that the atomic number decreases by one but the mass number stavs
the same .
^
38 1/
19 ^ isAr +
Electron Capture
Another type of decay for nuclides that have a neutron/proton ratio
that is too small is electron capture. In electron capture, an inner orbital
electron is captured by the nucleus of its own atom. The inner orbital
electron combines with a proton, and a neutron is formed.

i
6
"
An example of electron capture is the radioactive decay of J Ag into "^
14Pd. Just as in positron emission, the atomic number decreases by one
^
bui the mass number stavs the same.

l
‘IrAg + J/e > !$Pd
Gamma Emission
Gamma rays iyi are high -energy electromagnetic waves emitted from a
nucleus as it changes from an excited state to a ground energy state. The
position of gamma rays in the electromagnetic spectrum is shown in
Figure 6. The emission of gamma rays is another piece of evidence
supporting the nuclear shell model. According to the nuclear shell
model, gamma rays are produced when nuclear particles undergo
transitions in nuclear-energy levels. This is similar to the emission of FIGURE 6 Gamma rays, like visi -
photons ( light or X rays) when an electron drops to a lower energy ble light, are a form of electromag-
level which was covered in Chapter 4. Gamma emission usually occurs
,
netic radiation, but they have
immediately following other types of decay, when other types of decay a much shorter wavelength and
leave the nucleus in an excited state. are much higher in energy than
visible light.

Ultraviolet Infrared TV and FM Long

rays heat waves radio waves radio waves
1

E AM
-C X rays Microwaves radio waves
CT> c 1
c
a;

A
1
105
” 10 ’Mo " 10 10' 102 101 10*
10
0)
>
10 10 1
<T3
£

Gamma rays Visible light waves

NUCLEAR CHEMISTRY 687

 FIGURE 7 The half - life of radi - Rate of Decay
um - 226 is 1599 years. Half of the 20
remaining radium -226 decays by the
end of each additional half - life. 18

16
CT>
E 14
VO
PVl
12
E
a
o 10

o
c
D
o
E
<

1599 3198 4797 6396

Time ( years )

SC
/lNKS . Developed
Njtiooil
nuHrtJirwd by tin
Scteine Tracker* AUWMNI
Half - Life
For a variety of links related to this
chapter, go to www.scilinKorg
No two radioactive isotopes decay at the same rate. Half life, - is the
time required for half the atoms of a radioactive nuclide to decay. Look
Topic: Half - Life
SciLinks code: HC60709
.
at the graph of the decay of radium -226 in Figure 7 Radium - 226 has a
half - life of 1599 years. Half of a given amount of radium -226 decays in
1599 years. In another 1599 years, half of the remaining radium - 226
decays. Tliis process continues until there is a negligible amount of
radium -226. Each radioactive nuclide has its own half -life. More-stable
nuclides decay slowly and have longer half -lives. Less-stable nuclides
decay very quickly and have shorter half - lives, sometimes just a fraction
of a second. Some representative radioactive nuclides, along with their
half - lives, are given in Table 2,

TABLE 2 Representative Radioactive Nuclides

and Their Half -Lives
Nuclide Half-life Nuclide Half -life
?i H 12.32 years 163.7 ps
I 4p 5715 •years 2 * SRO 3.0 min
*

11? 14.28 days 2

SfAt 1.6 s
40\r
igN 1.3 x 109 years $U 4.46 x 1 ()9 years
27C0 5.27 years 2 Pu
£ 2.41 x 104 years

688 CHAPTER 21
 SAMPLE PROBLEM B For more help, go to the Math Tutor at the end of the chapter

Phosphorus- 32 has a half- life of 14.3 days. How many milligrams of phosphorus- 32 remain after 57.2 days
if you start with 4.0 mg of the isotope?

SOLUTION
1 ANALYZE Given: original mass of phosphorus- 32 = 4.0 mg
half-life of phosphorus- 32 = 14.3 days
time elapsed = 57.2 days
Unknown: mass of phosphorus-32 remaining after 57.2 days

2 PLAN To determine the number of milligrams of phosphorus-32 remaining, we must first find the
number of half-lives that have passed in the time elapsed. Then the amount of phosphorus-
32 is determined by reducing the original amount by half for every half-life that has passed.
I half -life
number of half- lives = time elapsed ( days ) x
14.3 davs
amount of phosphorus- 32 remaining =
original amount of phosphorus-32 x ^i for each half-life
I half- life
3 COMPUTE number of half-lives = 57.2 davs x =4 halt -lives
14.3 days
|
4 EVALUATE
amount of phosphorus-32 remaining = 4.0 mg x
^ ^
^
x x x = 0.25 mg

A period of 57.2 days is four half- lives for phosphorus-32. At the end of one half-life.
2.0 mg of phosphorus-32 remains: l.O mg remains at the end of two half- lives: 0.50 mg
remains at the end of three half- lives: and 0.25 mg remains at the end of four half- lives.

PRACTICE Answers / n Appendix E

1 . The half-life of polonium- 210 is 138.4 days. How many milligrams

of polonium-210 remain after 415.2 days if you start with 2.0 mg
of the isotope?
2 . Assuming a half-life of 1599 years, how many years will be needed
for the decay of 77 of a given amount of radium- 226?
3 . The half-life of radon-222 is 3.824 days. After what time will
one- fourth of a given amount of radon remain?
4. The half-life of cobalt -60 is 5.27 years. How many milligrams of
cobalt-60 remain after 52.7 years if you start with 10.0 mg?
Go to go.hrw.com for
5 . A sample contains 4.0 mg of uranium-238. After 4.46 x 109 years, more practice problems
the sample will contain 2.0 mg of uranium- 238. What is the half - that ask you to calculate
life of uranium- 238? the half -life or amount
of sample remaining.
Keyword: HC 6 NUCX

NUCLEAR CHEMISTRY 689

 Decay Series
One nuclear reaction is not always enough to produce a stable nuclide.
A decay series is a scries of radioactive nuclides produced by succes -
sive radioactive decay until a stable nuclide is reached . The heaviest
nuclide of each decay series is called the parent nuclide. The nuclides
produced by the decay of the parent nuclides are called daughter
nuclides. All naturally occurring nuclides with atomic numbers
greater than 83 are radioactive and belong to one of three natural
decay series. The parent nuclides are uranium - 238, uranium - 235, and
thorium -232. The transmutations of the uranium - 238 decay series are
charted in Figure 8.
Locate the parent nuclide, uranium -238, on the chart . As the nucleus
of uranium -238 decays, it emits an alpha particle. The mass number of
the nuclide, and thus the vertical position on the graph , decreases by
FIGURE 8 This chart shows the four. The atomic number, and thus the horizontal position , decreases by
transmutations that occur as two. The daughter nuclide is an isotope of thorium .
decays to the final, stable nuclide.
:'sJ; Ph. Deca \ usually follows the
$Th +
solid arrows. The dotted arrows
represent alternative routes of decay.
^ He

Uranium-238 Decay Series

242

238
238 92 U
4.5X 109y

234
234
90Th
234
..
91 Pa
^
234
92 U
24.1 d 1.2 min 2.5X 105y

230
230 90 Th
7.5 X 104 y

226
.
i
ai
226 88 Ra
1599 y
.a
E 222
3
c 222 86 Rn
</> 3.8 d
to
£ 218 218
218 84 PO 85 At
3.0 min
^ 1.6 s

214

210
282 Pb JttBi
27

210 . _ 210 ^ 210

81 TI 82 Pb 83 Bl
^
210
wPo
mm 19.9 min 163.7 ns

84 PO
s
min
= seconds
= minutes
1.3 min ^22.6 y ^5.01 d ^138.4 d d = days
206 . "* 206 y = years
81 Tl
206 ^ 82 Pb
4.2 min stable
= alpha emission
= beta emission

204
79 80 81 82 83 84 85 86 87 88 89 90 91 92 93
Atomic number

690 CHAPTER 2 1
 The half -life of - Th. about 24 days, is indicated on the chart . It
^
decays by giving off beta particles. This increases its atomic number,
and thus its horizontal position , by one. The mass number, and thus its
vertical position, remains the same.

* 29|Pa + - IP
2;
iTh
»

The remaining atomic number and mass number changes shown on

—
r i v f b ll l
the decay chart are also explained in terms of the particles given off . In Historical Chemistry

^ ^
the final step. Po loses an alpha particle to form Pb. This is a stable,
nonradioactive isotope of lead . Notice that 2{ Pb contains 82 protons, a
£
magic number. It contains the extra -stable nuclear configuration of a
Go to go. hrw. com for a full - length
article on Glenn Seaborg.
Keyword: HC 6 NUCX
completed nuclear shell .

Artificial Transmutations
Artificial radioactive nuclides are radioactive nuclides not found natu -
rally on Earth . They are made bv artificial transmutations, bombard -
ment of nuclei with charged and uncharged particles. Because neutrons
have no charge, they can easily penetrate the nucleus of an atom . FIGURE 9 This is an aerial
However, positively charged alpha particles, protons, and other ions are view of the Fermi International
repelled by the nucleus. Because of this repulsion , great quantities of Accelerator Laboratory ( Fermilab ),
energy are required to bombard nuclei with these particles. The neces- in Illinois. The particle accelerators
sary energy may be supplied by accelerating these particles in the mag - are underground. The Tevatron ring,
the larger particle accelerator, has a
netic or electrical field of a particle accelerator. An example of an
circumference of 4 mi. The smaller
accelerator is shown in Figure 9. ring ( top left ) is a new accelerator,
the Main Injector.
 TABLE 3 Reactions for the First Preparation of Several Transuranium Elements
Atomic number Name Symbol Nuclear reaction
238 y + l „

— ^_
93 neptunium Np > 23
%u
2

> 238 pu +
238Np 0
94 plutonium Pu

',
^
^ »Am + -|/J
2 PU + 2
95 americium Am /l

96 curium Cm 2
$Pu + ;He » 2%Cm + In
2 Bk + 2 Q «
97 berkelium Bk 2qsAm + iHe $
98 californium Cf 2
&;Cm + iHe 298Cf + 0»
99 einsteinium Es A
2 U + 15 /
$ i » $ES + 7_V /3
2-

f Fm + 8 V/? _
100
101
fermium
mendelevium
Fm
Md
2

2
$U + 17Q/I
$ES + jHe •
^
» yofMd + o «
2 Cm + 12C
102 nobelium No % 102 NO + 40«
| '
^
Lr 2 Cf + B + 4o
103 lawrencium 103
”

Artificial Radioactive Nuclides

Radioactive isotopes of all the natural elements have
been produced by artificial transmutation . In addition ,
production of technetium and promethium by artificial
transmutation has filled gaps in the periodic table. Their
positions are shown in Figure 10.
Artificial transmutations are also used to produce the
transuranium elements. Transuranium elements are ele-
ments with more than 92 protons in their nuclei. All of these
FIGURE 10 Artificial transmutations filled the gaps elements are radioactive. The nuclear reactions for the
in the periodic table, shown in red . and extended the sy nthesis of several transuranium elements are shown in
.
¥

periodic table with the transuranium elements, shown Table 3 Currently, 17 artificially prepared transuranium
in blue. elements have been named . Six more have been reported ,
but not confirmed. The positions of the transuranium ele-
ments in the periodic table are shown in Figure 10.

SECTION REVIEW 3. What fraction of a given sample of a radioactive

nuclide remains after four half -lives ?
1. Define radioactive decay.
4. When does a decay series end ?
2. a. What are the different types of common radio-
active decay ? Critical Thinking
b. List the types of radioactive decay that convert 5. INTERPRETING CONCEPTS Distinguish between
one nuclide into another . natural and artificial radioactive nuclides.

692 CHAPTER 21
Nuclear Radiation SECTION 3

OBJECTIVES
^ Compare the penetrating
I n Becquerel’s experiment , nuclear radiation from the uranium com - ability and shielding
pound penetrated the lightproof covering and exposed the film . Differ - requirements of alpha
ent types of nuclear radiation have different penetrating abilities. Nuclear particles, beta particles,
radiation includes alpha particles, beta particles, and gamma rays. and gamma rays.
Alpha particles can travel only a few centimeters in air and have a
low penetrating ability due to their large mass and charge. They cannot Define the terms roentgen
penetrate skin . However, they can cause damage inside the body if a and rem, and distinguish
substance that emits alpha particles is ingested or inhaled . Beta parti - between them.
cles, which are emitted electrons, travel at speeds close to the speed of
light and have a penetrating ability about 100 times greater than that
Describe three devices used
of alpha particles. Beta particles can travel a few meters in air. Gamma in radiation detection.
rays have the greatest penetrating ability. The penetrating abilities and
shielding requirements of different types of nuclear radiation are
shown in Figure 11 . J Discuss applications of
radioactive nuclides.

Radiation Exposure
Nuclear radiation can transfer the energy from nuclear decay to the elec-
trons of atoms or molecules and cause ionization. The roentgen ( R ) is a
unit used to measure nuclear radiation exposure; it is equal to the amount
of gamma and X ray radiation that produces 2 x 1( ) > ion pairs when it pass-
(

es through I cm' of dry air. Ionization can damage living tissue. Radiation
damage to human tissue is measured in rems ( roentgen equivalent , man ).
A rein is a unit used to measure the dose of any type of ionizing radiation
-
that factors in the effect that the radiation has on human tissue. Long term
exposure to radiation can cause DNA mutations that result in cancer and

FIGURE 11 lhe different pene -

trating abilities of alpha particles,
beta particles, and gamma rays
require different levels of shielding.
Alpha particles can be shielded with
just a sheet of paper. Lead or glass is
often used to shield beta particles.
Gamma rays are the most penetrat -
ing and require shielding with thick
layers of lead or concrete, or both .

NUCLEAR CHEMISTRY 693

 other genetic defects. DMA can he mutated directly by interaction with
radiation or indirectly by interaction with previously ionized molecules.
Everyone is exposed to environmental background radiation . Average
exposure for people living in the United States is estimated to be about 0.1
rem per year. However, actual exposure varies.The maximum permissible
dose of radiation exposure for a person in the general population is 0.5
rem per year. Airline crews and people who live at high altitudes have
increased exposure levels because of increased cosmic ray levels at high
altitudes. Radon-222 trapped inside homes also causes increased exposure.
Because it is a gas, radon released from certain rocks can move up through
the soil into homes through holes in the foundation. Radon trapped in
homes increases the risk of lung cancer, especially among smokers.

Radiation Detection
Film badges, Geiger- Muller counters, and scintillation counters are three
devices commonly used to detect and measure nuclear radiation . A film
badge and a Geiger- Muller counter are shown in Figure 12. As previ -
ously mentioned , nuclear radiation exposes film just as visible light
does. This property is used in film badges. Film badges use exposure of
film lo measure the approximate radiation exposure of people working
with radiation . Geiger- Muller counters are instruments that detect radia-
tion by counting electric pulses carried by gas ionized by radiation.
Geiger- Muller counters are typically used to detect beta - particles.
X rays, and gamma radiation. Radiation can also be detected when it
transfers its energy to substances that scintillate, or absorb ionizing radi -
ation and emit visible light . Scintillation counters are instruments that
FIGURE 12 Film badges ( a ) and
Geiger- Muller counters ( b ) are both
concert scintillating light to an electric signal for detecting radiation.
used to delect nuclear radiation .

.
04 AT >0 I
*

(a ) ( b)

694 CHAPTER 2 1
 Applications of Nuclear Radiation
Many applications are based on the fact that the physical and chemical
properties of stable isotopes are essentially the same as those of radio-
active isotopes of the same element. A few uses of radioactive nuclides are
discussed below.
Radioactive Dating
Radioactive dating is the process by which the approximate age of an
object is determined based on the amount of certain radioactive nuclides
present. Such an estimate is based on the fact that radioactive sub-
stances decay with known half -lives. Age is estimated by measuring FIGURE 13 Radioactive
either the accumulation of a daughter nuclide or the disappearance of nuclides, such as technetium -99,
can he used to detect bone cancer.
the parent nuclide.
In this procedure, technetium -99
Carbon-14 is radioactive and has a half -life of approximately 5715 accumulates in areas of abnormal
years. It can be used to estimate the age of organic material up to about hone metabolism. Detection of the
50 000 years old . Nuclides with longer half -lives are used to estimate the nuclear radiation then shows the
age of older objects; methods using nuclides with long half - lives have location of hone cancer.
been used to date minerals and lunar rocks more than 4 billion years old .
Radioactive Nuclides in Medicine
In medicine, radioactive nuclides, such as the artificial radioactive
nuclide cobalt-60, are used to destroy certain types of cancer cells. Many
radioactive nuclides are also used as radioactive tracers, which are
radioactive atoms that are incorporated into substances so that movement
of the substances can be followed by radiation detectors. Detection of
radiation from radioactive tracers can be used to diagnose cancer and
other diseases. See Figure 13.

Radioactive Nuclides in Agriculture

In agriculture, radioactive tracers in fertilizers are used to determine the
Mr>
Dmteprt m4 mlwH fcy llw
WitiQMl Some Trachen AIMCUUM
effectiveness of the fertilizer. The amount of radioactive tracer
For a variety of links related to this
absorbed by a plant indicates the amount of fertilizer absorbed . Nuclear chapter, goto
radiation is also used to prolong the shelf life of food. For example, Topic: Radioisotopes
gamma rays from cobalt -60 can be used to kill bacteria and insects that Sci Links code: HC61260
spoil and infest food.
' •

Nuclear Waste
Nuclear Fission and Nuclear Fusion
In nuclear fission , the nucleus of a very heavy atom , such as uranium , is
split into two or more lighter nuclei. The products of the fission include
the nuclei as well as the nucleons formed from the fragments’ radio-
active decay. Fission is the primary process powering nuclear reactors,
which include those on nuclear- powered submarines and aircraft carri -
ers. Fusion is the opposite process of fission . In fusion , very high tem -
peratures and pressures are used to combine light atoms, such as
hydrogen , to make heavier atoms, such as helium . Fusion is the primary

NUCLEAR CHEMISTRY 695

 process that fuels our sun and the stars. Creating and maintaining a
fusion reaction is more complex and expensive than performing fission.
Both fission and fusion release enormous amounts of energy that can be
converted into energy as heat and electrical energy, and both produce
.
nuclear waste Fission produces more waste than fusion . As new process-
es are developed to use energy from fission and fusion , a more vexing
question arises: how to contain , store, and dispose of nuclear waste.
Containment of Nuclear Waste
Ever> radioactive substance has a half - life, which is the amount of time
needed for half of a given material to decay. Radioactive waste from med -
ical research, for example, usually has a half - life that is a few months or less.
Some of the waste that is produced in a nuclear reactor will take hundreds
of thousands of years to decay, and it needs to be contained so that living
organisms can be shielded from radioactivity. There are two main types of
containment: on -site storage and off -site disposal .
Storage of Nuclear Waste
The most common form of nuclear waste is spent fuel rods from nuclear
power plants. These fuel rods can be contained above the ground by plac-
ing them in water pools or in dry casks. Each nuclear reactor in the United
States has large pools of water where spent rods can be stored , and some
.
of the radioactive materials will decay When these pools are full , the rods
are moved to dry casks, which are usually made of concrete and steel . Both
storage pools and casks are meant for only temporary storage before the
waste is moved to permanent underground storage facilities.

Disposal of Nuclear Waste

Disposal of nuclear waste is done with the intention of never retrieving
the materials. Because of this, building disposal sites takes careful plan -
ning. Currently, there are 77 disposal sites around the United States. The
U. S. Department of Energy is developing a new site near Las Vegas.
Nevada , called Yucca Mountain, for the permanent disposal of much of
this waste. Nuclear waste could be transported there by truck and train
—
beginning in 2010. This plan is controversial some organizations oppose
the idea of the disposal site, and others have proposed alternate plans.

SECTION REVIEW 3. What device is used to measure the radiation

.
1 What is required to shield alpha particles? Why are exposure of people working with radiation?
these materials effective? 4. Explain why nuclear radiation can be used to
2. a. What is the average exposure of people living preserve food .
in the United States to environmental back - Critical Thinking
ground radiation?
5. INFERRING CONCLUSIONS Explain how nuclear
b. How does this relate to the maximum permis- waste is contained, stored, and disposed of, and
sible dose ? how each method affects the environment.

696 CHAPTER 2 I
Nuclear Fission SECTION 4

and Nuclear Fusion OBJECTIVES

Define nuclear fission, chain
reaction, and nuclear fusion,
and distinguish between them.

sj Explain how a fission reaction

Nuclear Fission is used to generate power.

Review Figure 1 , which shows that nuclei of intermediate mass are the
most stable. In nuclear fission, u very heavy nucleus splits into more- Discuss the possible benefits
and the current difficulty of
stable nuclei of intermediate mass. This process releases enormous
controlling fusion reactions.
amounts of energy. Nuclear fission can occur spontaneously or when
nuclei are bombarded by particles. When uranium-235 is bombarded
with slow neutrons, a uranium nucleus may capture one of the neutrons,
making it very unstable. The nucleus splits into medium-mass nuclei with
the emission of more neutrons. The mass of the products is less than the
mass of the reactants. The missing mass is converted to energy.

Nuclear Chain Reaction on

When fission of an atom bombarded by neutrons produces more
neutrons, a chain reaction can occur. A chain reaction is a reac -
tion in which the material that starts the reaction is also one
o f the products and can start another reaction. As shown
in Figure 14, two or three neutrons can be given off
when uranium-235 fission occurs. These neutrons
can cause the fission of other uranium-235
nuclei. Again neutrons are emitted, which

1
on

on on

1
6n

FIGURE 14 Fission induction of uranium-235

by bombardment with neutrons can lead to a chain
reaction when a critical mass of uranium-235 is present .

NUCLEAR CHEMISTRY 697

 can cause the fission of still other uranium-235 nuclei. Iliis chain reaction
SCllNKS ,
Dmtofrtf **d manHmed by ti*
Nationil kkeace T*« hm AtiMutm*
-
continues until all of the uranium 235 atoms have split or until the neu -
trons fail to strike uranium-235 nuclei. If the mass of the uranium -235
For a variety of links related to this sample is below a certain minimum , too many neutrons will escape with -
out striking other nuclei , and the chain reaction will stop. The minimum
Topic: Fission
a
-f )
amount of nuclide that provides the number of neutrons needed to sustain
SciLinks code: HC60580 a chain reaction is called the critical mass. Uncontrolled chain reactions
Topic: Fusion provide the explosive energy of atomic bombs. Nuclear reactors use con -
Sci Links code: HC60629 trolled - ftssion chain reactions to produce energy and radioactive nuclides.

Nuclear Power Plants

Nuclear power plants use energy as heat front nuclear reactors to produce
electrical energy. They have five main components: shielding, fuel , con -
trol rods, moderator, and coolant . The components, shown in Figure 15 ,
are surrounded by shielding. Shielding is radiation -absorbing material
that is used to decrease exposure to radiation , especially gamma rays,
front nuclear reactors . Uranium -235 is typically used as the fissile fuel to
FIGURE 15 In this model of
produce energy as heat , which is absorbed by the coolant. Control rods
a nuclear power plant , pressurized
water is heated by fission of uranium -
are neutron -absorbing rods that help control the reaction by liittiti / tg the
235 . Iliis water is circulated to a number of free neutrons. Because fission of uranium - 235 is more effi -
steam generator. The steam drives ciently induced by slow neutrons, a moderator is used to slow down the
a turbine to produce electricity. fast neutrons produced by fission . Nuclear power plants can provide
Cool water from a lake or river is competitively priced electricity without emitting greenhouse gases or
then used to condense the steam particulates. Concerns about nuclear power include storage and dispos-
into water. The warm water from the al of spent radioactive fuel , as well as public perception .
condenser may be cooled in cooling
towers before being reused or
returned to the lake or river. | Water heated by nuclear reactor
Containment Water converted to steam
structure
\ Water used to condense steam

Steam turbine- generator

V
Electric
current
Control
rod Steam
generator
Condenser
t
Pump
( uranium /
fuel rod)
j

Moderator
and coolant
— v
l

( liquid water
under high
pressure)
Pump
Cool
water
* Warm
water

698 CHAPTER 2 1
 FIGURE 16 Fusion of hydrogen nuclei into
more -stable helium nuclei provides the energy of
our sun and other stars.

+ -f Energy
Nuclear fusion

Net Reaction: 4 H nuclei 2 He nucleus + 2 Ji /i particles -F Energy

Nuclear Fusion
The high stability of nuclei with intermediate masses can also be used
to explain nuclear fusion . In nuclear fusion, low -mass nuclei combine to
form a heavier, more stable nucleus. Nuclear fusion releases even more
energy per gram of fuel than nuclear fission . In our sun and stars that
are similar to the sun . hydrogen nuclei combine at extremely high tem -
perature and pressure to form a helium nucleus with a loss of mass and
release of energy. The net reaction is illustrated in Figure 16.
If fusion reactions can be controlled , they could be used for energy
generation. Researchers are currently studying ways to contain the
reacting plasma that is required for fusion. A plasma is an extremely hot
mixture of positive nuclei and electrons. There is no known material
that can withstand the initial temperatures, about 10s K , required to
induce fusion. Scientists use strong magnetic fields to suspend the
charged plasma inside a container but away from the walls.
Additionally, a large amount of energy is needed to initiate fusion reac-
tions. For fusion to be a practical energy source, more energy needs to
be generated by the reaction than is put into the reaction.

SECTION REVIEW 3. List the five main components of a nuclear power

1. Distinguish between nuclear fission and nuclear plant.
fusion. Critical Thinking
.
2 Define chain reaction. 4. RELATING IDEAS Explain how fusion is one of our
sources of energy.

NUCLEAR CHEMISTRY 699

 ISTORICAL CHEMISTRY

An Unexpected Finding
Historical Perspective
The discovery of the artificial
transmutation of uranium in
1934 triggered great excitement
iCTI
in science. Chemists who were 4 • t*
|
|preoccupied with identifying
|
what they thought were the
final missing elements of the
periodic table suddenly had to
consider the existence of ele-
ments beyond atomic number
92. Physicists began to probe
the stability of the nucleus more
deeply. By 1939, nuclear investi-
gators in both fields had collab-
orated to provide a stunning A This apparatus from Otto Hahn's lab was used to produce fission reactions.
explanation for the mysterious
results of uranium 's forced transformation. to Fermi, " We did not know enough chemistry to separate
the products of uranium disintegration from one another.”
Neutrons in Italy
Curiosity in Berlin
In 1934, uranium had the most protons, 92, of any known
Fermi's experiments caught the attention of a physicist in
element. But that year, Italian physicist Enrico Fermi
Berlin, Lise Meitner. Knowing that she could not perform
believed he had synthesized elements that have higher
the difficult task of chemically separating radionuclides
atomic numbers. After bombarding a sample of uranium
either, Meitner persuaded a colleague, radiochemist Otto
with neutrons, Fermi and his co -workers recorded measure-
Hahn, to help her explain Fermi's results. Joined by expert
ments that seemed to indicate that some uranium nuclei
chemical analyst Fritz Strassman, Meitner's team began
had absorbed neutrons and then undergone beta decay:
investigating neutron-induced uranium decay at the end
238 U 1
+„ »|2 9u » of 1934.
From the onset, Meitner's team, as well as all other sci-
entists at the time, operated under two false assumptions.
His report noted further, subsequent beta decays, by which The first involved the makeup of the bombarded nuclei. In
he hypothesized the existence of a whole new series of every nuclear reaction that had been observed, the result -
" transuranic " elements, now called transuranes: ing nucleus had never differed from the original by more
238 U than a few protons or neutrons. Thus, scientists assumed
92 ti »
that the products of neutron bombardment were radioiso-
294?? + -10 > 2lf ??? + _?/? topes of elements that were at most a few places in the
Unfortunately, Fermi and his group of scientists could not
periodic table before or beyond the atoms being bombard-
ed (as Fermi had presumed in hypothesizing the
verify the existence of the transuranes because, according
transuranes).

c* e
CHAPTER 2 1
•/
r . // 1
' gL -
C4
-
C Vt- C£ 6-
 The second assumption concerned the periodicity of the
transuranes. Because the elements Ac, Th, Pa, and U chemi-
cally resembled the transition elements in the third row of
the periodic table, La, Hf, Ta, and W, scientists believed that
elements beyond U would correspondingly resemble those
following W. Thus, the transuranes were thought to be
homologues of Re, Os, Ir, Pt, and the other transition ele-
ments in the third row. This belief was generally unques-
tioned and seemed to be confirmed. In fact, by 1937 Hahn
was sure that the chemical evidence of transuranes con-
firmed their location in the periodic table.
Meitner 's Exile
By 1938, the political situation in Germany had become
dangerous for Meitner. Because she was of Jewish descent,
she was targeted by the Nazis and fled to Sweden to escape
persecution. Meanwhile in Berlin, Hahn and Strassman, who
were critical of the Nazis, had to be careful. A The politicsof World War II prevented Lise
Despite being censored by the Nazis, Meitner's team Meitner from receiving the Nobel Prize in
continued to communicate through letters. Meitner could physics for explaining nuclear fission.
not formulate a satisfying physical explanation for the
chemical results of Hahn and Strassman, and she insisted For the discovery of this unexpected phenomenon,
that her partners reexamine their findings. Because of her which Meitner named nuclear fission, the talented Hahn
colleagues' great respect for her talent and expertise, they was awarded the 1944 Nobel Prize in chemistry. Because
quickly performed control experiments to test their results. of wartime politics, however, Lise Meitner did not receive
A Shocking Discovery the corresponding award in physics. She was not properly
Prompted by Meitner, Hahn and Strassman realized they recognized until well after her death in 1968 for her role
had been looking in the wrong place to find the cause of in clarifying the process that she first explained and
their results. In analyzing a fraction of a solution assay named.
that they had previously ignored, they found the critical
evidence they had been seeking. Questions
The analysis indicated that barium appeared to be a 1. What type of element did Fermi expect to find when
result of neutron bombardment of uranium. Suspecting the uranium absorbed a neutron and then ejected a beta
spectacular truth but lacking confidence, Hahn wrote to particle?
Meitner for an explanation. After consultation with her 2. What were the products of uranium disintegrations?
nephew, Otto Frisch, Meitner proposed that the uranium
nuclei had been broken apart into elemental fragments,
one of which was barium, Ba. On January 3, 1939, she
wrote to Hahn to congratulate him on the ground-breaking
SCllNKS. ft
Bawfcpti Md MMMM4 by Ike
kjboful Sciewe kecken AuocutoM
result. For a variety of links related to this
Thus, the " transuranes " turned out to be merely radioiso- .-
chapter, go to v vvw sc jinks org
topes of known elements—atomic fragments of uranium Topic: Enrico Fermi
atoms that had burst apart when struck by neutrons. SciLinks code: HC60521
 CHAPTER HIGHLIGHTS
The Nucleus
I Vocabulary •The difference between the sum of the masses of the nucleons
nucleon nuclear shell model and electrons in an atom and the actual mass of an atom is the
nuclide magic numbers mass defect , or nuclear binding energy.
mass defect nuclear reaction • Nuclear stability tends to be greatest when nucleons are
nuclear binding transmutation paired , when there are magic numbers of nucleons, and when
energy there are certain neutron - proton ratios.
• Nuclear reactions, which are represented by nuclear equations,
can involve the transmutation of nuclides.

Radioactive Decay
I Vocabulary • Radioactive nuclides become more stable by radioactive decay.
radioactive decay half - life • Alpha , beta , positron , and gamma emission , and electron cap-
nuclear radiation decay series ture are types of radioactive decay. The type of decay is related
radioactive nuclide parent nuclide to the nucleon content and the energy level of the nucleus.
alpha particle daughter nuclide • -
The half life of a radioactive nuclide is the length of time that it
beta particle artificial takes for half of a given number of atoms of the nuclide to decay.
positron transmutation • Artificial transmutations are used to produce artificial radioac-
electron capture transuranium tive nuclides, which include the transuranium elements.
element
gamma ray

Nuclear Radiation
I Vocabulary • Alpha particles beta particles and gamma rays have different
, ,

roentgen penetrating abilities and shielding requirements.

rem • Film badges. Geiger- Miiller counters, and scintillation detectors
film badge are used to detect radiation .
Geiger- Miiller counter • Everyone is exposed to environmental background radiation.
scintillation counter • Radioactive nuclides have many uses, including radioactive
radioactive dating dating, disease detection , and therapy.
radioactive tracer • Nuclear waste must be contained , stored, and disposed of in
nuclear waste a way that minimizes harm to people or the environment .
Nuclear Fission and Nuclear Fusion
I Vocabulary • Nuclear fission and nuclear fusion are nuclear reactions in
nuclear fission shielding which the splitting and fusing of nuclei produce more stable
chain reaction control rod nuclei and release enormous amounts of energy.
critical mass moderator • Controlled fission reactions produce energy and radioactive
nuclear reactor nuclear fusion nuclides.
nuclear power plant • Fusion reactions produce the sun 's energy in the form of heat
and light . If fusion reactions could be controlled , they would pro-
duce more usable energy per gram of fuel than fission reactions.

702 CHAPTER 21
 CHAPTER REVIEW

.
11 Balance the following nuclear equations.
The Nucleus ( Hint: See Sample Problem A.)

SECTION 1 REVIEW
.
a |qK - > 2 + _?
ifca
1. a. How does mass defect relate to nuclear bind- b. 25oTh + JL
. C+ _? » > iB
ing energy?
b. How does binding energy per nucleon vary
C
“
d. jN
with mass number? '
12. Write the
+I

c. How does binding energy per nucleon affect

nuclear equation for the release of
an alpha particle by :WPo.
the stability of a nucleus?
2 . Describe three ways in which the number of 13. Write the nuclear equation for the release of
a beta particle by Pb.
protons and the number of neutrons in a nu -
cleus affect the stability of the nucleus. ^
PRACTICE PROBLEMS
Radioactive Decay
3. The mass of a jjjNe atom is 19.992 44 amu. SECTION 2 REVIEW
Calculate the atom s mass defect. 14. Where on the periodic table are most of the
4. The mass of a ;Li atom is 7.016 00 amu. natural radioactive nuclides located?
Calculate the atom s mass defect. 15. What changes in atomic number and mass
5. Calculate the nuclear binding energy of one number occur in each of the following types
lithium-6 atom. The measured atomic mass of of radioactive decay ?
lithium -6 is 6.015 amu. a. alpha emission
.
6 Calculate the binding energies of the following b. beta emission
two nuclei, and indicate which nucleus releases c. positron emission
more energy when formed. You will need infor - d. electron capture
mation from the periodic table and the text. 16. Which types of radioactive decay cause the
a. atomic mass 34.988011 amu . transmutation of a nuclide? ( Hint: Review the
b. atomic mass 22.989767 amu, jfNa definition of transmutation. )
17. Explain how beta emission, positron emission,
7. a. W hat is the binding energy per nucleon for
and electron capture affect the neutron -proton
each nucleus in the previous problem?
ratio.
b. Which nucleus is more stable ?
18. Write the nuclear reactions that show
.
8. The mass of ?Li is 7.016 00 amu Calculate the
particle conversion for the following types of
binding energy per nucleon for Li.
^
9 . Calculate the neutron-proton ratios for the fol-
lowing nuclides:
radioactive decay:
a. beta emission
b. positron emission
a. ljjC c. 2$Pb
c. electron capture
b. ;
-l H d. *5oSn 19. Compare electrons, beta particles, and positrons.
10. a. Locate the nuclides in problem 9 on the 20. a. What are gamma rays?
.
graph in Figure 2 Which ones lie within the b. How do scientists think gamma rays are
band of stability ? produced?
b. For the stable nuclides, determine whether 21. How does the half-life of a nuclide relate to the
their neutron-proton ratio lends toward 1:1 stability of the nuclide ?
or 1.5:1. 22. List the three parent nuclides of the natural
decay series.

NUCLEAR CHEMISTRY 703

 CHAPTER REVIEW

23. How are artificial radioactive isotopes Nuclear Fission

produced ?
24. Neutrons are more effective for bombarding and Nuclear Fusion
atomic nuclei than protons or alpha particles SECTION 4 REVIEW
are. Whv?
35. How is the fission of a uranium -235 nucleus
25. Why are all of the transuranium elements
induced ?
radioactive ? ( Hint : See Section 1. )
36. How does the fission of uranium-235 produce a
chain reaction ?
PRACTICE PROBLEMS 37. Describe the purposes of the five major compo-
26. The half - life of plutonium-239 is 24 110 years. Of nents of a nuclear power plant .
an original mass of lOO.g, how much plutonium - 38. Describe the reaction that produces the sun ’s
239 remains after 96 440 years? ( Hint: See energy.
Sample Problem B. ) 39. What is one problem that must be overcome
27. The half - life of thorium -227 is 18.72 days. How
•
before controlled fusion reactions that produce
many days are required for three- fourths of a energy are a reality?
given amount of thorium - 227 to decay ?
°
,
28. Exactly lh of a given amount of protactinium -
234 remains after 26.76 hours. What is the MIXED REVIEW
half -life of protactinium -234?
29. How many milligrams of a 15.0 mg sample of 40. Balance the following nuclear reactions:
radium -226 remain after 6396 years? The half - a. “ijfNp -t /J + JL
life of radium -226 is 1599 years. b. jBe + iHe
c. _
+ ? gP
Nuclear Radiation d. HKr + JL + 34n
SECTION 3 REVIEW
.
41 After 4797 years, how much of the original
0.250 g of radium-226 remains? The half -life of
30. Why can a radioactive material affect photo- radium -226 is 1599 years.
graphic film even though the film is well 42. The parent nuclide of the thorium decay series
wrapped in black paper? is - Th . The first four decays are as follows:
.
31 How does the penetrating ability of gamma rays ^
alpha emission , beta emission , beta emission ,
compare with that of alpha particles and beta and alpha emission . Write the nuclear equations
particles? for this series of emissions.
32 . How does nuclear radiation damage biological 43. The half -life of radium - 224 is 3.66 days. What
tissue ? was the original mass of radium -224 if 0.0500 g
33 Explain how film badges. Geiger- Muller counters,
. remains after 7.32 days?
and scintillation detectors are used to detect 44. Calculate the neutron-proton ratios for the
radiation and measure radiation exposure. following nuclides, and determine where they
34. How is the age of an object that contains a lie in relation to the band of stability.
radioactive nuclide estimated ? a. 2$U c. $Fe
b.
‘go d.
^
Nd
45. Calculate the binding energy per nucleon of
in joules. The atomic mass of a 2$> U
nucleus is 238.050 784 amu .

704 CHAPTER 2 1
 CHAPTER REVIEW

46. The energy released by the formation of a

RESEARCH & WRITING
nucleus of sJJFe is 7.89 x 10 11 J. Use Einstein s
'

equation , E = me 2, to determine how much 53. Investigate the history of the Manhattan Project .
mass is lost ( in kilograms ) in this process. 54. Research the 1986 nuclear reactor accident at
47. Calculate the binding energy for one mole Chernobyl . Ukraine. What factors combined to
of deuterium atoms. The measured mass of cause the accident ?
deuterium is 2.0140 amu.
55. Find out about the various fusion -energy
research projects that are being conducted in
the United States and other parts of the world .
CRITICAL THINKING
What obstacles in finding an economical
48. Why do we compare binding energy per nuclear method of producing energy must still be
particle of different nuclides instead of the total overcome?
binding energy per nucleus of different
nuclides?
49. Why is the constant rate of decay of radioactive ALTERNATIVE ASSESSMENT
nuclei so important in radioactive dating?
50. Which of the following nuclides of carbon is 56. Using the library, research the medical uses of
more likely to be stable? State reasons for your radioactive isotopes such as cobalt -60 and
answer. technetium -99. Evaluate the benefits and risks
of using radioisotopes in the diagnosis and
a. > C
' b. llC treatment of medical conditions. Report your
51 . Which of the following nuclides of iron is more findings to the class.
likelv to be stable ? State reasons for •vour
m* *

answer.
a . 56
26
pp b. 26 Fe
52. Use the data in the table shown to determine
the following:
a . the isotopes that would be best for dating
i Graphing Calculator
Half- Lives
Go to go.hrw.com for a graphing calculator
ancient rocks
exercise that asks you to determine the
b. the isotopes that could be used as tracers
amount of a radioactive isotope based on
State reasons for your answers.
its half - life.
Element Half- Life
potassium -40 1.28 x 109 y A" Keyword: HC 6 NUCX
potassium -42 12.36 h
y
uranium-238 4.468 x 10 y
uranium - 239 23.47 min

NUCLEAR CHEMISTRY 705

 Math Tutor CALCULATING WITH HALF- LIFE

The rate at which a sample of a radioactive nuclide decays is expressed in terms of

half - life. This quantity is the time required for half of the atoms of a sample of a given
nuclide to decay. For example, it takes 37.2 min for half of the nuclei of chlorine - 38 to
decay to argon- 38. After 37.2 min, 0.50 g of a 1.0 g sample of chlorine- 38 will remain
and there will be 0.50 g of argon- 38. After two half - lives ( 74.4 min), the fraction of
chlorine- 38 that remains will be \ of or 4'
n
After n half - lives, the fraction of a radioactive nuclide that remains is|
( | , or 2 ‘ n.
If you know the amount of nuclide that was present initially and the amount of nuclide
that remains, you can determine the number of half -lives that have passed.

Problem-Solving TIPS
• Familiarize yourself with the values of some common powers of two ( 2", n = 1.2,
3, 4.5. 6, etc ). This will allow you to determine the number of half - lives quickly.

SAMPLE 1 SAMPLE 2
The half- life of polonium- 218 is 3.04 min. A sam- The half- life of potassium- 40 is 1.3 x 109 years.
ple of polonium contains 0.00558 g of " JJPo. What A volcanic rock contains of the amount of
~

21 s
mass o f H4Po will remain after 18.24 min? potassium- 40 found in newly formed rocks. When
First, you must determine the number of half - was the rock formed ?
lives that have passed in 18.24 min. First, determine the number of half-lives that
time elapsed have passed.
number of half-lives =
1
| I x 11-— x
^^
half -life
fraction remaining = =
18.24 min 9
\*
i
= 6.00 half - lives
3.04 min Therefore, three half - lives have passed. The
Then, to determine the mass of polonium-218 time since the rock was formed is 3 half - lives x
remaining, apply the following relationship. 1.3 x 109 rifFr | 3.9 x 10%.
nalNife 1 =

mass remaining = starting mass x

fraction remaining

\
mass : JPo remaining = 0.00558 g x -
t
‘
0.00558 g x — = 8.72 x 11% g 2 Po
(i4
^
PRACTICE PROBLEMS
1. A sample of chromium contains 8.9 x 10“ g of ° 2. The half -life of lead-202 is 53 000 years. A sam -
the radioactive nuclide chromium-51, which has ple of lead contains only of the expected
a half -life of 28 days. What mass of chromium - amount of lead-202. How old is the lead sample?
51 will remain in the sample after 168 days?

706 CHAPTER 2 \
Answer the following items on a separate piece of paper. 7. Which of the following nuclides is radioactive ?
MULTIPLE CHOICE A. loCa
.
1 Complete the following nuclear equation : B. 2$Ra
Os + _ P C. I2C
'
n

.'
A $Os ^ \
D. 2$Ph

^.
B. Os ' 8. The half -life of thorium -234 is 24 days. If you
C.
D
> Re
have a 42.0 g sample of thorium - 24, how much
will remain after 72 days?
2. The mass of the nucleus is
.
A 42.0 g
B. 21.0 g
A. greater than the mass of the protons and .
C 10.5 g
neutrons that make up the nucleus. D . 5.25 g
B. equal to the mass of the protons and
9. It takes 5.2 min for a 4.0 g sample of
neutrons that make up the nucleus.
francium -210 to decay until only 1.0 g is left .
C. less than the mass of the protons and
neutrons that make up the nucleus.
What is the half -life of francium 210? -
A. 1.3 min
.
D converted to energy.
B. 2.6 min
3 . Which type of radiation has the most penetrat - .
C 5.2 min
ing ability? D . 7.8 min
.
A an alpha particle
SHORT ANSWER
B. a beta particle
C. a gamma rav 10. Write the nuclear equation that represents the
.
D a neutron process in which a neutron in the nucleus is
changed to a proton with the emission of a
4. Which two particles have the same mass but beta particle.
opposite charge?
A. a beta particle and a positron 11. Describe a positron , and write its nuclear symbol.
B. a neutron and a proton EXTENDED RESPONSE
C. a proton and an electron .
12 Explain the difference between nuclear fission
.
D an alpha particle and a proton and nuclear fusion , and explain the energy
5. Which of the following nuclear equations is cor - changes that accompany each process.
rectly balanced ? 13. What is meant by the term mass defect ?
A. j Ar + }\e
.
B %\ + 2 ^ *
In
He + H
fla
^ ?
C . : Es + iHe tmMd + 2l,n
D. iN + He ^ 120 + TH
6. Gamma rays
'
^ ing
Keeping a positive attitude dur -
any test will help you focus on the test and likely
A. have the same energy as beta particles do.
improve your score.
.
B are visible light .
.
C have no charge and no mass.
D. are not a form of electromagnetic radiation .

NUCLEAR CHEMISTRY 707

 EXPERIMENT 21

Simulation of Nuclear Decay

Using Pennies and Paper
OBJECTIVES BACKGROUND
• Infer that the rate of decay can he simulated Radioactive isotopes are unstable. All radioactive
by a random process. matter decays, or breaks down , in a predictable pat -
tern . Radioactive isotopes release radiation as they
• Compare the numbers of pennies that are
disintegrate into daughter isotopes.
showing heads with the number showing
tails. The rate of decay is a measure of how fast an iso-
tope changes into its daughter isotope. The rate of
• Create a string plot that represents nuclear radioactive decay is conveniently characterized by
decay. the isotope 's half - life, the period of time it takes one -
• Relate observations to the rate of nuclear half of the original material to decay. Half -lives vary
decay. V
from billions of vears to fractions of a second.
*

• Graph the data.

SAFETY
• Compare the results of the two simulation
procedures.

MATERIALS
For a review' of safety, please see Safety in the
• colored paper or cloth strips, approximately Chemistry Laboratory in the front of your book .
65 cm x 2.5 cm ( 2 strips )
• graph paper PREPARATION
• one sheet of stiff poster board , 70 cm x 60 cm 1 . For Part A , make a data table that has at least
10 row's in your lab notebook by using the for-
• pennies or other objects supplied by mat described by your teacher.
your teacher ( 100 )
• scissors, tape, meter stick , pencil , and string PROCEDURE
• shoe box with lid Part A: Simulating radioactive decay with pennies
1 . Place 100 pennies into the shoe box so that the
head sides are up. The pennies will represent
atoms. Record 100 in the “ Unchanged atoms"
column and 0 in the “ Changed atoms" column .
2 . With the lid on the box. shake the box up and
down 5 times. We will count each shaking period
as being equivalent to 10 s.
3 . Open the lid , and remove all of the pennies that
have the tails side up. These pennies represent
the changed atoms.

708 CHAPTER 2 1
 EXPERIMENT 21

4. Count the number of pennies remaining in the CLEANUP AND DISPOSAL

box. Record this number in the 10 s row of the 15. Return the pennies and box to your
“ Unchanged atoms' column . Count the number
*

teacher. Dispose of the poster board ,

of changed atoms ( the pennies that you strips, and string as instructed by your
removed from the box ), and record the number teacher. Clean up your lab station .
table in the 10 s row.
5 . Each lab partner should predict how many times ANALYSIS AND INTERPRETATION
steps 2^4 will need to be repeated until only one Part A
unchanged atom remains. Record the time that 1. Predicting Outcomes: How long did it take to
each lab partner predicted . Remember that each have only 1 penny ( 0 pennies ) left in the box?
shaking period is counted as 10 s, so four shak - How close was your prediction in step 5 ?
ing periods would be recorded as 40 s.
2. Analyzing Data: Make a graph of your data on a
6. Repeat steps 2-4 by counting and recording -
piece of graph paper. Label the x axis “ Time"
each time until only 1 ( or 0 ) penny with the -
and the v axis “ Unchanged atoms." Plot the
head side up remains. number of unchanged atoms versus time. Draw
a smooth curve through the data points.
Part B: Simulating decay with paper
7. Draw an v-axis and .v-axis on the poster board 3. Analyzing Results: Each trial was comparable to
so that they are about 5 cm from the left side -
a 10 s period of time. How long did it take for
and the bottom edge respectively. Label the half of your pennies to be removed from the
.v-axis as “Time" and the v-axis as “Amount of box ? What is the half - life of the process?
material."
4. Interpreting Graphics: Use your graph to deter -
8. Along the .v-axis, draw marks every 10 cm from mine the time it takes to have only 25 % of the
the y-axis line. Label the first mark “0" and the unchanged atoms remaining. In your experi-
next mark “1," and so on. Each mark represents ment . how many pennies remained in the box at
1 minute. that time ?
9. Place one of the colored strips vertically with its Part B
lower edge centered on the 0 mark of the .v -axis. 5. Analyzing Results: How many half lives have
Tape the strip in place. passed after 4 minutes?
10. Fold the other colored strip in half , and cut it in 6. Interpreting Graphics: Using the string plot ,
the middle. Place one - half of the strip so that it determine how many minutes it took until only
is centered on the next mark , and tape the strip 20 % of the original material remained .
in place.
11. Fold the remaining piece of the strip in half, and CONCLUSIONS
cut it exactly in the middle. 1. Inferring Conclusions: If you started with a
12. Place one of the pieces so that it is centered on paper strip that was twice as long, would the
the next mark , and tape the piece in place. half - life change ?

13. Repeat steps 11 and 12. and each time, tape the 2. Inferring Conclusions: Is there a relationship
first piece vertically at the next .v-axis mark . between the graph from Part A and the string
Continue until you have at least 8 strips taped plot from Part B?
along the .v-axis.
14. Use the string to join the tops of each strip of
paper to make a continuous curve.

NUCLEAR CHEMISTRY 709

 CHAPTER 22

Organic Chemistry
Nanotubes are hollow cylinders of pure carbon, thousands
of times thinner than a human hair, and are dozens
of times stronger than steel by weight.
Organic Compounds SECTION 1

OBJECTIVES
Explain how the structure and
A II organic compounds contain carbon . However, not all
atoms bonding of carbon lead to the
carbon-containing compounds are classified as organic. There are a few diversity and number of
exceptions, such as Na:C03. CO, and CO % that are considered inor - organic compounds.
ganic. Organic compounds, then, can be defined as covalently bonded
compounds containing carbon , excluding carbonates and oxides . Compare the use of molecular
Figure 1 shows a few familiar items that contain organic compounds. and structural formulas to
represent organic compounds.

Carbon Bonding and the Diversity Compare structural and geo -

metric isomers of organic
of Organic Compounds compounds.
The diversity of organic compounds results from the uniqueness of car -
bon ' s structure and bonding. Carbon's electronic structure allows it to
bind to itself to form chains and rings, to bind covalently to other ele -
ments. and to bind to itself and other elements in different arrangements.

FIGURE 1 Aspirin polyethylene

,

in plastic hags, citric acid in fruit , and

amino acids in animals are all exam -
ples of organic compounds.

ORGANIC CHEMISTRY 711

 Carbon - Carbon Bonding
Carbon atoms are unique in their ability to form long chains and rings
of covalently bonded atoms. This type of bonding is known as catena -
tion , the covalent bonding of an element to itself to form chains or rings.
In addition , carbon atoms in these structures can be linked by single,
double, or triple covalent bonds. Examples of molecules containing car -
bon -atom rings and chains are shown in Figure 2.

Carbon Bonding to Other Elements

Besides binding to other carbon atoms, carbon atoms bind readily to
elements with similar electronegativities. Organic compounds consist of
carbon and these other elements. Hydrocarbons are composed of only
carbon and hydrogen ; they are the simplest organic compounds. Other
organic compounds contain hydrocarbon backbones to which other ele-
ments. primarily O. N. S. and the halogens, are attached . Figure 3 shows
a molecule in which carbon atoms are bound to other elements.

Arrangement of Atoms
The bonding capabilities of carbon also allow for different arrange -
FIGURE 2 Compare ihe shape of ments of atoms. This means that some compounds may contain the
a fatty acid found in cream with that same atoms but have different properties because the atoms are
of fructose, found in fruit . In the arranged differently. For example, the molecular formula C:H 60 repre -
fatty acid , the carbon atoms are in sents both ethanol and dimethyl ether. Compounds that have the same
chains. In fructose, carbon atoms
molecular formula but different structures are called isomers.
form a ring.

Structural Formulas
Organic chemists use structural formulas to represent organic compounds.
A structural formula indicates the number and types of atoms present in a
molecule and also shows the bonding arrangement of the atoms. An exam -
ple of a structural formula for an isomer of C4 HH ) is the following.
H FI H
-I
H C C
I
C- H
I
H H-C- H H
I
H
Structural formulas are sometimes condensed to make them easier
to read. In one type of condensed structure, hydrogen single covalent
bonds are not shown . The hydrogen atoms are understood to bind to the
atom they are written beside. The following structural and condensed
structural formulas represent the same molecule.

H H H
FIGURE 3 In firefly lucifcrin. car- I
bon atoms bind to hydrogen , H -C C C- H CH 3- CH - CH 3
oxygen , nitrogen and sulfur.
is the same as ,
,
H H -C- H H CH
Lucifcrin is responsible for the light
emitted from the tail of a firefly.
H

712 CHAPTER 22
 FIGURE 4 The structure
H OH of ethanol can be represented in
H C — C- H
- . - -
different ways Ball and stick and
l space - filling models represent the
H H three - dimensional shape of the
molecule.
Ball- and-stick model Space- filling model

Remember that the structural formula does not accurately show the
three-dimensional shape of the molecule. Three-dimensional shape is
depicted with drawings or models, as shown for ethanol in Figure 4.

Isomers
You have learned that isomers are compounds that have the same mol -
ecular formula but different structural formulas. Isomers can be further
classified bv structure and geometry.

Structural Isomers — iTfldn

Structural isomers, also called “constitutional isomers.' are isomers in which Chemical Content
the atoms are bonded together in different orders. For example the atoms of
,
Go to go.hrw.com for another ver -
the molecular formula C4H 10 can be arranged in two different ways. sion of this content. See the chapters
“ Carbon and Hydrocarbons and "

11 H H “ Other Organic Compounds."

H H H H
I I I H- C - ( -C- H
H-C-C-C- C- H
I I I l
H H H H
H —
H C- H H
H
Keyword: HC 60 RGX

butane methylpropane
Notice that the formula for butane shows a continuous chain of four
carbon atoms. The chain may be bent or twisted , but it is continuous.
The formula of methylpropane shows a continuous chain of three car -
bon atoms, with the fourth carbon atom attached to the second carbon
atom of the chain .
Structural isomers can have different physical or chemical proper -
ties. For example, butane and methylpropane have different melting
points, boiling points, and densities, as shown in Table 1 .

TABLE 1 Physical Properties of the Structural

Isomers Butane and 2-Methylpropane
Melting point Boiling point Density at 20° C
(°C) ( ° C) (g / mL )
butane -138.4 -0.5 0.5788
-
2 methylpropane -159.4 -11.633 0.549

ORGANIC CHEMISTRY 713

 FIGURE 5 Males of the Iowa o
strain of the European corn borer ( CH:)qCH:OCCH;
respond most strongly to mixtures of
the female sex attractant pheromone
that are %% cis isomer. But males
c / s- 11-tetradecenyl acetate
of the New York strain respond most
strongly to mixtures containing 97 % O
irons isomer. ( CH:)9CH2OCCH 3

CH;CH: H
trans - 11-tetradecenyl acetate

Geometric Isomers
Geometric isomers are isomers in which ( he order of atom bond ini* is
the same but the arrangement of atoms in space is different . Consider
the molecule 1,2- dichloroethene, which contains a double bond. The
double bond prevents free rotation and holds groups to either side of
the molecule. This means there can be two different 1,2-dichloroethene
geometric isomers, as shown below.

Cl Cl H Cl
/ /
/
c=c \ /
C=C
\
H H Cl H
CIS trans

The geometric isomer with the two chlorine atoms on the same side
of the molecule is called cis. The isomer with the chlorine atoms on
opposite sides of the molecule is called trans. Figure 5 shows an exam -
ple of geometric isomers that occur in nature.

SECTION REVIEW 2. What are three characteristics of carbon that con -

1. Which of the following represent the same tribute to the diversity of organic compounds?
molecule? .
3 Define the term isomer, and distinguish between
structural and geometric isomers.
a. H H H H H
I I I I I 4. Which of the following types of molecular
H- C-C-C-C-C- H
I I I I I representations can be used to show differences
H H H H H between isomers? Explain why each can or cannot.
a. molecular formula
,
b. CH -CH2-CH:-CH3 b. structural formula
c. three-dimensional drawing or model
,
c. CH -CH2-CH:
CH- )
Critical Thinking
5. INTERPRETING CONCEPTS Can molecules that
CH3
have molecular formulas C 4H10 and C4H 00 be ,
d. C5Hl 2 isomers of one another ? Why or why not ?

714 CHAPTER 22
 1V IrU ISTORICAL CHEMISTRY
The Beginnings of Organic Chemistry
Today, " organic chemistry " refers to The remainder of the 19th century
the study of carbon compounds. saw the syntheses of many other
However, organic chemistry was organic compounds. In 1845, acetic
originally thought of as unique acid was prepared in several steps
among all chemical sciences, from charcoal. Many other organic
because it emphasized the study of molecules, such as dyes and glucose
compounds that came from living (blood sugar), were synthesized in
organisms. Chemists of the early the last half of the 19th century.
19th century viewed organic com - Gradually, as more natural products
pounds as fundamentally different were prepared in chemistry laborato-
from inorganic compounds, such as ries, the concept of vitalism was
rocks and minerals, because organic abandoned.
compounds seemed to come only Today, urea, acetic acid, and
from living things. But because living many other organic chemicals are
organisms are built from carbon- produced in huge quantities.
containing molecules, organic chem- Organic chemists can synthesize
istry later came to mean the study of complex drug molecules, such as
carbon compounds, including those penicillin and taxol, which were
that are manufactured artificially. once available only from natural
A Friedrich Wohler was the first to
Like modern researchers, early sources. Using methods of organic
synthesize an organic compound
chemists were interested in the work - synthesis, chemists can also prepare
from inorganic chemicals.
ings of the body. They tried to charac- completely new drugs, polymers,
terize the chemicals in blood, tissue, In 1828, the young German flavors, and dyes that are not pre-
and urine. Urea, the molecule that the chemist Friedrich Wohler announced sent in nature.
human body excretes to get rid of that he had been able to make urea
ammonia waste, was first isolated from inorganic chemicals. Wohler Questions
from urine in 1773. Although scientists had been attempting to prepare 1. What do people usually mean by
could successfully isolate urea and ammonium cyanate, NH4OCN, from the term organic when they use
other organic compounds, they did not inorganic compounds, such as silver it to describe food, such as fruits
—
know how to synthesize that is, cyanate and ammonium chloride. But and vegetables?
make from other, simpler chemicals— Wohler unintentionally synthesized
2. Think of three things that you
organic compounds. This tended to urea as a byproduct of the reactions
use in your everyday life and
confirm a commonly -held belief, called that he carried out ! Wohler made an
that an organic chemist might be
vitalism, that organic compounds exciting discovery— the first example
able to make.
could only be made inside living of organic synthesis—by using the
organisms with the help of a special same principles of qualitative analy -
life force known as the " vital force." sis used by chemists today.

ORGANIC CHEMISTRY 715

 SECTION 2
Hydrocarbons
OBJECTIVES
J Distinguish among the struc-
tures of alkanes, alkenes, H ydrocarbons arc compounds that contain only carbon and hydro-
alkynes, and aromatic gen. They make up the simplest class of organic compounds. All other
hydrocarbons. organic compounds can be viewed as hydrocarbons in which one or
more hydrogen atoms have been replaced by other atoms or groups of
Write structural formulas and atoms.
names for alkanes, alkenes, Hydrocarbons are grouped mainly by the type of bonding between
and alkynes. carbon atoms. Saturated hydrocarbons arc hydrocarbons in which each
carbon atom in the molecule forms four single covalent bonds with other
atoms.
Relate properties of different
types of hydrocarbons to their
structures.

Alkanes
Hydrocarbons that contain only single bonds are alkanes. In Fable 2, the
SCllNKS.] Dmtoptd nd
* * U»
NJKOMI SOMM TiKfcm AuoojttM
molecular formulas, structural formulas, and space- filling models are
given for alkanes with one to four carbon atoms. If you examine the
For a variety of links related to this molecular formulas for successive alkanes in Table 2, you will see a
chapter, go to y/ ww.seijin_ks orej clear pattern. Each member of the series differs from the preceding one
Topic: Alkanes ^ by one carbon atom and two hydrogen atoms. For example, propane .
Sci Links code: HC60045 .
C\ HS, differs from ethane C2H6,by one carbon atom and two hydrogen
—
atoms, a — CH2 group.

H H H II H
I I
H C-C- H
- H-C C C- H
I I
H H H II II
ethane propane

Compounds that differ in this fashion belong to a homologous series.

A homologous series is one in which adjacent members differ by a con-
stant unit. It is not necessary to remember the molecular formulas for
all members of a homologous series. Instead, a general molecular for -
mula can be used to determine the formulas. Look at the molecular for -
mulas for ethane and propane. C2H(J and C,HS. They both fit the
formula C„IL/H.2. For ethane, n = 2. so there are two carbon atoms and
( 2 x 2 ) + 2 = 6 hydrogen atoms. For propane, n = 3. so there are three
carbon atoms and ( 2 x 3 ) + 2 = S hydrogen atoms. Now consider a mol-
ecule for which we do not know the molecular formula. Suppose a
member of this series has 30 carbon atoms in its molecules. Then n = 30.
and there are ( 2 x 30) + 2 = 62 hydrogen atoms. The formula is CM )\I62.

716 CHAPTER 22
 TABLE 2 Alkanes with One to Four Carbon Atoms
Molecular formulas Structural formulas Space- filling models

&
H - C -H
CH4
H
methane

H H

Q
I I
H- C - C -H

*
C:Hh I I
H H
ethane

H H H
I I I
H-C-C-C-H
C3H8 I l 1
H H H

propane

H H H H
H-C- C- C -C -H
I I I I
H H H H
butane
C4 Hh,
H H H
I
H -C C C- H
I
H H- C- H H
H
methylpropane

Notice that for alkanes with three or fewer carbon atoms, only one
molecular structure is possible. However, in alkanes with more than
three carbon atoms, the chains can be straight or branched. Thus,
alkanes with four or more carbon atoms have structural isomers. There
are two possible structural isomers for alkanes with four carbon atoms,
butane and 2-methylpropane.
The number of structural isomers increases greatly as the number of
carbon atoms in alkanes increases. There are three isomeric C5 H 2 alkanes. ,
five isomeric Q,HU alkanes, and nine isomeric C7H16 alkanes There are .
nearly 37 million possible isomers of C:5 Hs> though most have never been
prepared or isolated.

ORGANIC CHEMISTRY 717

 Cycloalkanes
Cycloalkanes are alkanes in w hich the carbon atoms are arranged in a
ring, or cyclic, structure. The structural formulas for cycloalkanes are
often drawn in a simplified form. In these skeletal representations, such
as the one below on the right, it is understood that there is a carbon
atom at each corner and enough hydrogen atoms to complete the four
bonds to each carbon atom.

CH,\
CHI CH2 or
/
CTT-CH,
cyclopentane cyclopentane
The general structure for cycloalkanes, C„H:,; shows that they have
f

2 x n hydrogen atoms, two fewer hydrogen atoms than noncyclic alka -

nes. have. This is because cycloalkanes have no free ends
where a carbon atom is attached to three hydrogen atoms. Another
example, of a four-carbon alkane and cycloalkane, is shown below.
H H
H H H H
i l l I H-C-C-H
H-OC-C-OH I
I I I I H-C-C - H
H H H H
H H
butane cvclobutane
C4H 0, C4HK

TABLE 3 Carbon- Atom Systematic Names of Alkanes

Chain Prefixes
Historically, the names of many organic compounds were derived from
Number of the sources in which they were found. As more organic compounds
carbon atoms Prefix
were discovered, a systematic naming method became necessary. The
meth - systematic method used primarily in this book was developed by the
eth - International Union of Pure and Applied Chemistry. 11 PAC
3 prop-
UnbranchedChain Alkane Nomenclature
4 but -
To name an unbranched alkane, find the prefix in Table 3 that corre-
5 pent - sponds to the number of carbon atoms in the chain of the hydrocarbon.
6 hex - Then add the suffix -ane to the prefix. An example is shown below.
7 hept - 3 4 s 7

8 oet -
CH 3-CH 2- CH2-CH 2- CH:-CH -CH3

9 non - heptane
10 dec - The molecule has a chain seven carbon atoms long, so the prefix hept -
is added to the suffix - ane to form heptane.

718 CHAPTER 22
 TABLE 4 Some Straight -Chain Alkyl Groups
Alkane Name Alkyl group Name
CH4 methane -CH3 methyl
CH3-CH3 ethane -CH2-CH3 ethyl
CH3-CH2- CH3 propane -CH2-CH2-CH3 propyl
CH3-CH2 CH2-CH3
- butane -CH2-CH2-CH2- CH3 butyl
CH3-CH2-CH2-CH2-CH3 pentane - CH2-CH2-CH2-CH2-CH3 pentyl

Branched- Chain Alkane Nomenclature

The naming ol branched-chain alkanes also follows a systematic
method. The hydrocarbon branches of alkanes are alkyl groups Alkyl .
groups are groups of atoms that are formed when one hydrogen atom is
removed from an alkane molecule. Alkyl groups are named by replacing
the suffix -arte of the parent alkane with the suffix - \7. Some examples
are shown in Table 4. Alkyl group names are used when naming
branched-chain alkanes. We will only present the method for naming
simple branched-chain alkanes with only straight -chain alkyl groups.
Consider the following molecule.

CH 3 CH3
CH3 CH2 CH:- CH -CH- CH -CH:-CH 3
- -

CH-CH3
CH,
To name this molecule, locate the parent hydrocarbon. The parent
hydrocarbon is the longest continuous chain that contains the most
straight -chain branches. In this molecule, there are two chains that are
eight carbon atoms long. The parent hydrocarbon is the chain that con-
tains the most straight -chain branches. Do not be tricked by the way the
molecule is drawn. The longest chain may be shown bent.

C H i C H;
I
1
,
'

CM ; CH; CH; ( I I Cl I CH -CH2-CH

Cl I CH;
CII

NOT

C H; C H;
C II; C H. =£H - CU - -CH; CH;
-CH3
CH3

ORGANIC CHEMISTRY 719

 To name the parent hydrocarbon, add the suffix ane to the prefix
oct - ( for a carbon - atom chain with eight carbon atoms) to form octane.
Now identify and name the alkyl groups.

CH; CH ,
CH,-CHT- CHT -CH-CH-CH CH: CH;
CH - CI 1 ,
CH ,
The three -CH;groups are methyl groups. The -CH2-CH3 group is an
ethyl group. Arrange the names in alphabetical order in front of the
name of the parent hydrocarbon.

ethyl mcthyloctane

To show that there are three methyl groups present, attach the prefix
CAREERS in Chemistry tri - to the name methyl to form trimethyl.

Petroleum Engineer ethvl trimethvloctane

Petroleum engineers search for under -
ground reservoirs of oil or natural gas. Now we need to show the locations of the alkyl groups on the parent
They then work with other scientists hydrocarbon. Number the octane chain so that the alkyl groups have
and engineers to develop and oversee
drilling and production operations. the lowest numbers possible.
Petroleum engineers are also respon-
sible for developing technology and CH CH; ,
methods to increase the amount of oil CH;-CH2- CH:- CH -CH- CH - CH:-CH;
or gas obtained and to lower the cost
:CH- CH;
of drilling and production operations. In
addition to possessing a broad range of I CM ;
engineering expertise (chemical,
mechanical, or electrical) a petroleum NOT
engineer must also apply the basic sci-
ences of chemistry, geology, physics,
and mathematics. CH; CH;
>
CH;- CH2- CHi - CH - CH2- CH CH:- CH;
CH;
CH ,
Place the location numbers of each of the alkyl groups in front of its
name. Separate the numbers from the names of the alkyl groups with
hyphens. The ethyl group is on carbon 3.

-
3 ethvl trimethvloctane

Because there are three methyl groups, there will be three numbers,
separated by commas, in front of trimethyl.

*
r -
3 - ethvl- 2,4,5 trimethvloctane
w J

The full name is 3-ethvl - 2.4.5 - trimethyloctane.

The procedure for naming simple branched-chain alkanes can be sum -
marized as shown in the list on the next page.

720 CHAPTER 22
Alkane Nomenclature
1. Name the parent hydrocarbon. Find the longest continuous chain
of carbon atoms that have straight -chain branches. Add the suffix
-ane to the prefix corresponding to the number of carbon atoms in
the chain.
2. Add the names of the alkyl groups. Add the names of the alkyl
groups in front of the name of the parent hydrocarbon in alpha-
betical order. When there is more than one branch of the same
alkyl group present, attach the appropriate numerical prefix to the
name: di = 2, tri = 3,tetra = 4, and so on. Do so after the names have
been put in alphabetical order.
3. Number the carbon atoms in the parent hydrocarbon. If one or
more alkyl groups are present, number the carbon atoms in the
continuous chain to give the lowest numbers possible in the name.
If there are two equivalent lowest positions with two different
alkyl groups, give the lowest number to the alkyl group that comes
first in the name. ( This will be the alkyl group that is first in alpha-
betical order, before any prefixes are attached.)
4. Insert position numbers. Put the position numbers of each alkyl
group in front of the name of that alkyl group.
5 . Punctuate the name. Use hyphens to separate the position num -
bers from the names. If there is more than one number in front of
a name, use commas to separate the numbers.

SAMPLE PROBLEM A
Name the following simple branched-chain alkane:
CH3-CH-CH,-CH-CH-CH3
' I I
CH3 CH3 CH3

SOLUTION .
1 Identify and name the parent hydrocarbon.
CH , CM - Clh- CII
I
- CH - CH,
I
CH 3 CH3 CH3
Because the longest continuous chain contains six carbon atoms, the parent hydrocarbon
is hexane.

2. Identify and name the alkyl groups attached to the chain.

CH3-CH-CH2-CH-CH-CH3
CII , CH3 CH?
There is only one type of alkyl group, with one carbon atom. Alkyl groups with one car -
bon atom are methyl groups. Add the name methyl in front of the name of the continu-
ous chain. Add the prefix tri - to show that there are three methyl groups present.

trimethylhexane
• »

ORGANIC CHEMISTRY 721

 3. Number the carbon atoms in the continuous chain so that the alkyl groups have the
lowest numbers possible.

I
CH
— —
CH‘3-CH CH -> CH-CH-CH
, I l
CH CH , ,
,
4. The methyl groups are on the carbon atoms numbered 2, 3 , and 5. Put the numbers of
the positions of the alkyl groups, separated by commas, in front of the name of the alkyl
group. Separate the numbers from the name with a hyphen .
2.3.5- trimethvihexane

PRACTICE Answers in Appendix E

Name the following molecules:

,
1 . CH - CH -CH ,-CH ,
l
CH ,
2. CH ,
,
CH -CH 2-CH-CH-CH 2-CH , Go to go. hrw.com for
CH -
) more practice problems
that ask you to name
CH3 alkanes.
Keyword: HC 60RGX

Properties and Uses of Alkanes

-
Properties for some straight chain alkanes are listed in Table 5 The .
trends in these properties can be explained by examining the structure
of alkanes. Hie carbon -hydrogen bonds of alkanes are nonpolar. The
only forces of attraction between nonpolar molecules are weak inter -
molecular forces, or London dispersion forces. The strength of London
dispersion forces increases as the mass of a molecule increases.

TABLE 5 Properties of Straight -Chain Alkanes

Molecular State at room
formula IUPAC name Boiling point (°C) temperature
CH 4 methane -164 gas
C2 H 6 ethane -88.6
C3 H 8 propane -42.1
C4H O , butane -0.5
C5H 12 pentane 36.1 liquid
CgH|g octane 125.7
,
CH H 22 decane 174.1
CnH* heptadecane 301.8 solid
C „H
: 42 eicosane 343

722 CHAPTER 22
Physical States
The physical states at which some alkanes exist at room temperature and
atmospheric pressure are found in Table 5. Alkanes that have the lowest
molecular mass— those with one to four carbon atoms—are gases.
Natural gas is a fossil fuel composed primarily of alkanes containing one
to four carbon atoms. These alkanes are gases because they are very small
molecules. Therefore, they have weak London dispersion forces between
them and are not held together tightly. Larger alkanes are liquids.
Gasoline and kerosene consist mostly of liquid alkanes. Stronger London
dispersion forces hold these molecules close enough together to form liq-
uids. Alkanes that have a very high molecular mass are solids, corre-
sponding to a greater increase in London dispersion forces. Paraffin wax
contains solid alkanes. It can be used in candles, as shown in Figure 6.

Boiling Points FIGURE 6 Paraffin wax, used in

The boiling points of alkanes, also shown in Table 5, increase with mol - candles, contains solid alkanes.
ecular mass. As London dispersion forces increase, more energy is Molecules of paraffin wax contain
26 to 30 carbon atoms.
required to pull the molecules apart. This property is used in the sepa -
ration of petroleum, a major source of alkanes. Petroleum is a complex
mixture o f di fferent hydrocarbons that varies greatly in composition. The
hydrocarbon molecules in petroleum contain from 1 to more than 50
carbon atoms. This range allows the separation of petroleum into dif -
ferent portions that have different boiling point ranges, as shown in
Table 6. In fractional distillation, components of a mixture are separat -
ed on the basis of boiling point, by condensation of vapor in a fraction -
ating column. Figure 7 shows an example of refinery towers in which the
process takes place. During its fractional distillation, petroleum is heat -
ed to about 37(1C. Nearly all components of the petroleum are vapor -
ized at this temperature. As the vapors rise in the fractionating column, FIGURE 7 Fractional distillation
.
or tower, they are gradually cooled Alkanes that have higher boiling takes place in petroleum refinery
towers.
points have higher condensation temperatures and condense for collec -
tion lower in the tower. For example, lubricating oils, which have high -
.
er condensation temperatures than gasoline has are collected lower in
the fractionating tower.

TABLE 6 Petroleum Fractions

Size range of Boiling-point
Fraction molecules range (°C)
Gasoline c4-ci: up to 200
Kerosene c iorC 14 180-290
Middle distillate, such as heating Ci 2_C20 185-345
oil. gas-turbine fuel, diesel
Wide-cut gas oil. such as C20-C36 345-540
lubricating oil. waxes
Asphalt above residues
 Unsaturated Hydrocarbons
Hydrocarbons that do not contain the maximum amount of hydrogen
are referred to as unsaturated . Unsaturated hydrocarbons are hydrocar -
bons in which not all carbon atoms have four single covalent bonds. An
unsaturated hydrocarbon has one or more double bonds or triple
bonds. Carbon atoms can easily form double and triple bonds to other

SCllNKS. Otrfloprd
MM
KUMUiMd by
NJIMMUI SutiKt Iddm AiMtubM
carbon atoms, so multiple bonds between carbon atoms are common in
organic compounds.
For a variety of links related to this
chapter, go to www.sal1nks.pr3 I Alkenes
Topic: Alkenes
Sci Links code: HC60046
^ Alkenes are hydrocarbons that contain double covalent bonds. Some
examples of alkenes are given in Table 7. Notice that because alkenes
have a double bond, the simplest alkene. ethene. has two carbon atoms.
Carbon atoms linked by double bonds cannot bind as many atoms as
those that are linked by only single bonds. An alkene with one double
bond has two fewer hydrogen atoms than the corresponding alkane.

H H H H
I
H-C-C-C-H
I
H H H
I
I
l
I
H-C C-C-H
l -
H H H
I I

C\ Hx ,
C H6

Thus. the general formula for noncyclic alkenes with one double bond
is CflHjfl.
Because alkenes have a double bond, they can have geometric iso -
mers. as shown in the examples below.

H H H CH3
\ \ /
C=C c c\=

CH, CH3 CH , /
H
ri.v -2 -butene f /vi/ w -2 -butene

TABLE 7 Structures of Alkenes

ethene propene trans- 2-butene c/s- 2 *butene
H H H H H CH3 H H
C-C
Structural s / \ / \
C=C \ yC C \
= C=C
formula
H
/
H CH , H CH, /
H ,
CH
/ \
CH ,

Ball- and- stick

model
K J j
J

724 CHAPTER 22
Systematic Names of Alkenes
The rules for naming a simple alkene are similar to those for naming an Chemistry in Action
alkane. The parent hydrocarbon is the longest continuous chain of car - Carbon Allotropes
bon atoms that contains the double bond . Carbon occurs in several different
bonding patterns, called allotropes,
CH7- CH3
I “
. .
ni^ C - CH - CH - CH , NOT
< n• < if ni ca
which have very different properties.
Diamond is a colorless, crystalline solid
form of carbon, in which each atom is
pentene hexane tetrahedrally bonded to four others in a
network fashion. This three-dimensional
The carbon atoms in the chain are numbered so that the first carbon
bonding makes diamond the hardest
atom in the double bond has the lowest number. material known.
Graphite is a soft, black, crystalline
—
CH-> CH3
form of carbon that is a fair conductor
- 2\ 3
CH2 C-CH2-CH2-CH3
4

1 -pentene
s
of electricity. The carbon atoms in
graphite are bonded together in layers.
Within each layer, each atom is bonded
to three other carbon atoms. But
The position number and name of the alkyl group are placed in front of
because adjacent layers are held
the double-bond position number. This alkyl group has two carbon atoms, together only by very weak London dis-
an ethyl group. It is on the second carbon atom of the parent hydrocarbon. persion forces, graphite is very soft.
Diamond and graphite have been
2-ethyl- 1-pentene known for thousands of years. In the
If there is more than one double bond, the suffix is modified to indi - mid-1980s, a new solid allotropic form
of carbon known as a fullerene, or,
cate the number of double bonds: 2 = -adiene , 3 = -atriene, and so on. informally, " Buckyball," was discovered
CH 2=CH -CH:-CH =CH2 in the soot that forms when carbon-
containing materials are burned with
1.4-pentadiene limited oxygen. The structure of a
fullerene consists of a near-spherical
The procedure for naming alkenes can be summarized as follows. cage of carbon atoms. The most stable
fullerene is C60, the structure of which
resembles the design of a soccer ball.
Alkene Nomenclature
Use the rules for alkane nomenclature on page 721, with the
following exceptions.
1. Name the parent hydrocarbon. Locate the longest continuous
chain that contains the double bond ( s ). If there is only one double
bond, add the suffix -ene to the prefix corresponding to the num-
ber of carbon atoms in this chain. If there is more than one dou-
ble bond, modify the suffix to indicate the number of double
bonds. For example, 2 = -adiene, 3 = -atriene, and so on.
2. Add the names of the alkyl groups.
3. Number the carbon atoms in the parent hydrocarbon. Number the
carbon atoms in the chain so that the first carbon atom in the dou -
ble bond nearest the end of the chain has the lowest number If .
numbering from both ends gives equivalent positions for two dou-
ble bonds, then number from the end nearest the first alkyl group.
4. Insert position numbers. Place double - bond position numbers
immediately before the name of the parent hydrocarbon alkene.
Place alkyl group position numbers immediately before the name
of the corresponding alkvl group.
5. Punctuate the name.

ORGANIC CHEMISTRY 725

 SAMPLE PROBLEM B
Name the following alkene . ,
CM
CH:-CH-C=CH 2
CH2-CH3

SOLUTION 1. Identify and name the parent hydrocarbon.

CH3
CII e i i - c cic
i
CH2-CH3
The parent hydrocarbon has four carbon atoms and one double bond, so it is named
butene.

2. Identify and name the alkyl groups.

CH
,
CH - CH - C=CH 2
CH , CH,
The alkvl groups are ethyl and methyl.
Place their names in front of the name of the parent hydrocarbon in alphabetical order.
ethyl methyl butene
3. Number the carbon chain to give the double bond the lowest position.
CH3
4
,
CH -CH-C=CH:
^

CH2-CH3
Place the position number of the double bond in front of butene. Place the position num -
bers of the alkyl groups in front of each alkyl group. Separate the numbers from the
name with hyphens. The full name is 2 -ethyl- 3 -methyM -butene.

PRACTICE Answers in Appendix E

Name the following alkenes:

. -
1 CH -CH2 CH2-CH=CH-CH3

2. ,
CH
, C H CH
CH '
CH ,
3. CH,
,-CH-CH
CH =CH -CH2-CH3
4. CH , -V rcfl'l11
Go to go.hrw.com for
CH CH , more practice problems
,C
CH - -CH2 CH=C-CH , that ask you to name
alkenes.
Keyword: HC 60RGX

726 CHAPTER 22
 FIGURE 8 a farnesene is a -
solid alkene found in the natural
wax covering of apples.
Can you determine
IUPAC
' 1 ! Ill ' jM
l . i r-' i i l k e i K - V
.

CH ; CH CH, CH CH CH
\ S \ / \ \ / X / X
c CH, C CH, C CH ,
CH , CH , CH ,
nt - farnesene

Properties and Uses of Alkenes

Alkenes are nonpolar and show trends in properties similar to those of
alkanes in boiling points and physical states. For example, a-farnesene
has 15 carbon atoms and 4 double bonds, as shown in Figure S. This
large alkene is a solid at room temperature and atmospheric pressure. It
is found in the natural wax covering of apples. Ethene. the smallest
alkene. is a gas. Ethene is commonly called ethylene.
Ethene is the hydrocarbon commercially produced in the greatest
quantity in the United States. It is used in the synthesis of many plas-
tics and commercially important alcohols. Ethene is also an important
plant hormone. Induction of flowering and fruit ripening, as shown in
Figure 9, are effects of ethene hormone action that can be manipulated
by commercial growers.

Alkynes
Hydrocarbons with triple covalent bonds are alkynes. Like the double
bond of alkenes. the triple bond of alkynes requires that the simplest
alkvne has two carbon atoms.
H -C =C - H
ethvne
_
The general formula for the alkynes is C„ H 2„ 2. Alkynes have four
fewer hydrogen atoms than the corresponding alkanes and two fewer
hydrogen atoms than the corresponding alkenes. The simplest alkvne is
ethvne. more commonly known as acetylene.
H H H H
H -C-OH
I
H H H
c=c \
H
—
H C=C- H

C,Hft C:H 4 C\ H 2
FIGURE 9 Ethene is a plant hor -
mone that triggers fruit ripening. At
ordinary conditions, ethene is a gas.

ORGANIC CHEMISTRY 111

 Systematic Naming of Alkynes
Alkync nomenclature is almost the same as alkene nomenclature. The
-
only difference is that the ene suffix of the corresponding alkene is
-
replaced with vne. A complete list of rules follows.

Alkyne Nomenclature
Use the rules for alkane nomenclature on page 721, with the
following exceptions.
.
1. Name the parent hydrocarbon Locate the longest continuous
chain that contains the triple bond( s ). If there is only one triple
-
bond , add the suffix yne. If there is more than one triple bond ,
modify the suffix. For example, 2 = -adiyne, 3 = -atriyne, and so on .
Chemistry in Action 2. Add the names of the alkyl groups.
-
Go to go. hrw.com for a full length 3. Number the carbon atoms in the parent hydrocarbon Number the .
article on synthetic diamonds. carbon atoms in the chain so that the first carbon atom in the
'I' - Keyword: HC 60 RGX
triple bond nearest the end of the chain has the lowest number.
.
4. Insert position numbers Place the position numbers of the triple
bond immediately before the name of the parent hydrocarbon
alkyne. Place alkyl group position numbers immediately before
the name of the corresponding alkyl group.
5. Punctuate the name.
Two examples of correctly named alkynes are given below.

CH 3-CH 2-CH:-C> CH
-
CH = C CH-Cf -L
CH3
l - pentvne 3- methvl l - butvne
*

Properties and Uses of Alkynes

Alkynes are nonpolar and exhibit the same trends in boiling points and
physical state as other hydrocarbons. The smallest alkyne. ethyne, is a
gas. The combustion of ethyne when it is mixed with pure oxygen pro-
duces the intense heat of welding torches, as shown in Figure 10 The .
common name of ethyne is acetylene, and these welding torches are
commonly called oxyacetylene torches.

FIGURE 10 Ethyne is the fuel

used in oxyacetylene torches.
Oxyacetylene torches can reach
r>
\v MS
temperatures of over 3000 C.

n FT
V ,
:
j
-
wm

c? -
-'
i.
m m
’ *

mJ
s
A Lila

728 CHAPTER 22
Aromatic Hydrocarbons
Aromatic hydrocarbons are hydrocarbons that have six-membered car -
Air/
Developed nd mjtitt jnwd by the
*
MJIMMMI Science Tmints Anotutio
bon rings and delocalized electrons. Benzene is the primary aromatic *
For a variety of links related to this
hydrocarbon . The molecular formula of benzene is C6Hft. One possible chapter, go to ilinks.org «
structural formula is a six -carbon atom ring with three double bonds.
Topic: Aromatic Compounds
SciLinks code: HC60095

However, benzene does not behave chemicallv like an alkene. The

J
H H
entire molecule lies in the same plane, as shown in Figure II. Benzene
contains resonance hybrid bonds, and the structure of the benzene ring H —H
allows electrons to be spread through delocalized /^ -orbitals over the
whole ring. The structural and skeletal formulas below show benzene as H H
a resonance hybrid, representing the delocalization of electrons.
FIGURE 11 Electron orbitals in
benzene overlap to form continuous
p-orbitals that allow the delocalized
electrons to spread uniformly over
the entire ring.

Aromatic hydrocarbons can be thought of as derivatives of benzene.

The simplest have one benzene ring, as shown in the following example.

methylbenzene

SECTION REVIEW .
4 Give examples of a property or use of three
1. List the basic structural features that characterize hydrocarbons.
each of the following hydrocarbons: 5. Name the following compounds:
a. alkanes a. CHj- CH, CH3
b. alkenes CH3-CH CH-CH,-CH3
c. alkynes b. CH,=CH- CH=CH2
d. aromatic hydrocarbons ,
c. CH -OC-CH2-CH3
2. Draw all of the condensed structural formulas that
can represent C5 H12. Critical Thinking
3. Give the systematic name for each compound in 6. ANALYZING INFORMATION Write the structural
your answers to item 2. formulas for an alkane, an alkene, and an alkyne
that have five carbon atoms each. Why are these
three hydrocarbons not considered isomers ?

ORGANIC CHEMISTRY 729

 SECTION 3
Functional Groups
OBJECTIVES
>J Define " functional group "
and explain why functional A functional group is an atom or group of atoms that is responsible for
groups are important. the specific properties of an organic compound. A given functional
group undergoes the same types of chemical reactions in every mole -
sj Identify alcohols, alkyl halides, cule in which it is found. Therefore, compounds that contain the same
ethers, aldehydes, ketones, functional group can be classified together.
carboxylic acids, esters, and
amines based on the function-
al group present in each.
Classes of Organic Compounds
^ Explain the relationships A functional group gives an organic compound properties that are very
between the properties and
structures of compounds with different from those of the corresponding hydrocarbon. The compounds
various functional groups. in Table S have four carbon atoms, but they have very different physi-
cal properties due to their different functional groups. Some functional
groups and their characteristic general formulas are shown in Table 9.

TABLE 8 Comparing Classes of Organic Compounds

Name Structural Formula Melting Point (°C) Boiling Point (°C) Density (g /mol)
Butane H H H H -138.4 -0.5 0.5788
t i l l
H-C-C- C- C-H
I I I I
H H H H

1 - Butanol H H H H -89.5 117.2 0.8098

I I I
HO- C-C- C C H
I I I I
H H H H

Butanoic acid O H H H -4.5 163.5 0.9577

I I
HO- C - C-C-C-H
I I I
H H H

2- B utanone H O H H -86.3 79.6 0.8054

I I! I I
H C-C (' C H
I I I
H H H

Diethvi ether H H H H -116.2 34.5 0.7138

I I I I
H-C- C- O-C-C-H
i I I I
H H H H

730 CHAPTER 22
 TABLE 9 Classes of Organic Compounds SCllNKS Dtwtoped «nd BMiliiiwI by tW
Class Functional group General formula NJIIMUI Stinct TNckm AMOUMMI

For a variety of links related to this

alcohol -OH R-OH chapter, go to www.scilinks.org
alkyl halide -A" ( A' = F, C1. Br, I ) R- X Topic: Alcohols
ether - O- R O- R' SciLinks code: HC60038

aldehyde O O
-C- H R C- H
-
ketone O O
-C- R-C - R'
amine -N
I — R- N - R”
R'
carboxylic acid O O
C- OH fl- C-OH
ester O O
-C- O- R-C -O - R'
FIGURE 12 Glycerol contains
three hydroxyl croups. Ill is structure
allows it to form multiple hydrogen
bonds with water. Glycerol is added
Alcohols
as a moisturizer to skin products.
Alcohols are organic compounds that contain one or more hydroxyl
groups. The general formula for a class of organic compounds consists glycerol
of the functional group and the letter R. which stands for the rest of the
molecule. The general formula for alcohols is R - OH .
Hydrogen bonding in alcohols can also explain other properties and
uses of alcohols. Cold creams, lipsticks, body lotions, and similar prod -
ucts generally include 1 ,2.3- propanetriol , commonly called glycerol ,
to keep them moist . A model for glycerol
is shown in Figure 12. Multiple hydroxyl
groups allow glycerol to form many hydro-
gen bonds with water molecules.
Alcohols are sometimes used today as
alternative fuels and as octane enhancers
in fuel for automobiles. Ethanol is com -
bined with gasoline, for example, in a one-
to- nine ratio to produce gasohol. Some
experts have promoted the use of gasohol
as a fuel for automobiles because it burns
more cleanly and efficiently. However,
there are also disadvantages. The combus-
tion of ethanol produces only about 60 %
as much energy per gram as the combus-
tion of gasoline does. The presence of
ethanol also causes increased water
absorption in the fuel.

ORGANIC CHEMISTRY
 SC Alkyl Halides
/ lNKS. Mft
»r *
Dcvfloped tmd HUMJMIMI t
NjtiOAAl VowKf TrjcKen AuMUtea
Alkyl halides are organic compounds in which one or more halogen
atoms — fluorine, chlorine,bromine, or iodine—are substituted for one or
For a variety of links related to this
more hydrogen atoms in a hydrocarbon. Because - X is often used to
chapter, go to wwu scilmkyo[g I
Topic: Alkyl halides
SciLinks code: HC60047
^ represent any halogen, an alkyl halide may be represented by the gen-
eral formula R - X.
Alkyl halides are some of the most widely used organic chemicals A .
family of alkyl halides that has received widespread attention in recent
m
.
years is the chlorofluorocarbons or CFCs. CFCs are alkvl halides that
7 #

.
contain both chlorine and fluorine The formulas for two widely used J

CFCs. Freon- 11 and Freon- 12, are shown below.

Cl F
I
F- C-Cl Cl C- F
-
I
Cl Cl
trichlorofluoromethane dichlorodifluoromethane
(Freon-11 ) ( Freon- 12)
CFCs. which have been used as liquid refrigerants, contribute to the
destruction of ozone in the upper atmosphere. When released into the
atmosphere. CFCs can break down and release free chlorine atoms.
solar radiation
CC1:F2 Cl + CC1F,
The released chlorine atoms attack molecules of ozone. 03, found in
the upper atmosphere. The ozone is converted to diatomic oxygen.
Cl + o3
* CIO 4- o:
Chlorine atoms are eventually regenerated in various ways, including
the reaction of CIO with O.
CIO 4 o > Cl 4 CL
This makes it possible for a single chlorine atom to destroy thou-
sands of ozone molecules. Because CFCs are a major cause of ozone
FIGURE 13 The nonstick coating depletion, more than 100 nations signed an agreement in 1987 to reduce
on this pan is made of Teflon, the amount of CFCs produced.
an alkvl halide. .
Another alkyl halide is tetrafluoroethene C2F4. It is joined in long
chains to make a material with the trade name Teflon \ Because of the
.
unreactive carbon- fluorine bond Teflon is inactive and stable to about
325 C. It also has a low coefficient of friction, which means that other
.
objects slide smoothly over its surface These properties enable Teflon
to be used in heat -resistant machine parts that cannot be lubricated. It

.V r is also used in making utensils with ‘ nonstick surfaces, such as the fry -
"

SCllNKS. *
Dmloptd and mMNtJMMd toy (he
Matxxul Sonne TMrittn Anocuboa
ing pan in Figure 13 -
For a variety of links related to this Ethers
chapter, go to wwv. scilinks. org I Ethers are organic compounds in which two hydrocarbon groups are
Topic: Ethers
Sci Links code: HC60537
^ bonded to the same atom of oxygen. They can be represented bv the gen-
eral formula R-O- R '. In this formula, /? ' may be the same hydrocar-
bon group as R or a different one. Like alkanes, ethers are not very
reactive compounds, so they are commonly used as solvents.

732 CHAPTER 22
 irone

CH ,
k " vanillin

CH=CH

cinnamaldehyde

O
benzaldehyde
/
CH3
raspberry ketone

FIGURE 14 Many common odors

and flavors come from aldehydes
and ketones.
Aldehydes and Ketones
Aldehydes and ketones contain the carbonyl group, shown below.
O
-C-
The difference between aldehydes and ketones is the location of the
carbonyl group. Aldehydes are organic compounds in which the car -
SCllNKS .] ,
Dratopcd MKJ mjMiUiiwd by Ike
Nitio«ul SoeiKe Tuckers Auocutoa
bonyl group is attached to a carbon atom at the end o f a carbon -atom
For a variety of links related to this
chain. Ketones are organic compounds in which the carbonyl group is chapter, go to www.scilinks.org *
attached to carbon atoms within the chain. These differences can be seen Topic: Aldehydes/ketones
in their general formulas, shown below. SciLinks code: HC60039
O o
fl-C-H fl- C - Rf
aldchvde ketone
Aldehydes and ketones are often responsible for odors and flavors.
Figure 14 gives some examples.

Amines
Amines are organic compounds that can be considered to be derivatives
of ammonia, NH ?. Amines are common in nature. They often form dur -
ing the breakdown of proteins in animal cells.
The unshared electron pair on the nitrogen atom makes amines act Chemical Content
as weak bases in aqueous solutions, as shown below. Cio to go.hrw.com for more infor -
mation on functional groups.
H+
K -N- R" + H- O- H ? ± R- N- /r + OH * Keyword: HC 60 RGX
'1'
R’ R'

ORGANIC CHEMISTRY 733

 () OH O Carboxylic Acids
HO 0 CH2-C- CH 2 C-OH Carboxylic acids are organic compounds that contain the carboxyl func -
OO tional group. A member of this class of organic compounds can be rep -
resented by the general formula shown below.
citric acid OH
O
R -C OH -

Carboxylic acids, like inorganic acids, react to lose a hydrogen ion

and become a negatively charged ion in water.
O
H,0
o
R-C- OH > R- c- cr + ir
Carboxylic acids are much weaker than many inorganic acids, such
as hydrochloric, sulfuric, and nitric acids. Acetic acid, the weak acid
in vinegar, is a carboxylic acid.
A number of carboxylic acids occur naturally in plants and animals.
For example, citrus fruits, shown in Figure 15, contain citric acid.
Benzoic, propanoic, and sorbic acids are used as preservatives. All three
j acids kill microorganisms that cause foods to spoil.

FIGURE 15 Citric acid, found Esters

in citrus fruits, contains three Esters are organic compounds that have carboxylic acid groups in which
carboxylic acid groups shown in the hydrogen of the hydroxyl group has been replaced by an alkyl group.
red on the structural formula. Esters are considered derivatives of carboxylic acids because of their
structural similarity to carboxylic acids. The general formula for an ester
is given below.

O
R - C-O- R'

SECTION REVIEW o
g -
.
1 Give the general formula and class of organic CH3- C- O- CH2- CH ,
compounds for each of the following:
h. O
a. CH3-OH
CH3-C-CH3
b. CH3-O-CH , 2. Compare the boiling points of alcohols, ethers, and
c. Br -CH:— CHi-CH , alkanes, and explain one reason for the differences.
d. O 3. How are aldehydes and ketones alike ? How do
CH,-CH:-C-OH they differ ?
e. O 4. How do the strengths of organic acids compare
,
CH -C- H
with the strengths of most inorganic acids ?

f. CH,-CH,-NH2 Critical Thinking

5. APPLYING MODELS Identify the functional groups
in vanillin, shown in Figure 14.

734 CHAPTER 22
 SECTION 4
Organic Reactions
OBJECTIVES
Describe and distinguish
Substitution Reactions between the organic
reactions: substitution,
A substitution reaction is one in which one or more atoms replace another addition, condensation,
atom or group of atoms in a molecule. The reaction between an alkane,
and elimination.
such as methane, and a halogen, such as chlorine, to form an alkyl halide
is an example of a substitution reaction. Notice that in this reaction, a Relate some functional
chlorine atom replaces a hydrogen atom on the methane molecule. groups to some characteristic
reactions.
H II
ll-C II + Cl Cl > H-C Cl + 11 Cl
Identify the two main types of
II H polymers and the basic reac -
methane chlorine chloromethane hydrogen chloride tion mechanisms by which
they are made.
Additional compounds can be formed by replacing the other hydro-
gen atoms remaining in the methane molecule. The products are
dichloromethane, trichloromethane, and tetrachloromethane.Trichloro-
methane is also known as chloroform, and tetrachloromethane is also
known as carbon tetrachloride. CFCs are formed by further substitution
reactions between chloroalkanes and HF.

Cl Cl
shr ,
Cl- C Cl + H I Cl C F + II Cl
-

Cl Cl
Cl I
SbF,
-
Cl C - F + H F Cl - C- F + H Cl
* I
Cl Cl

Addition Reactions
An addition reaction is one in which two pans of a molecule are added
to an unsaturated molecule, increasing; the saturation of the molecule. A
common type of addition reaction is hydrogenation. In hydrogenation ,
hydrogen atoms arc added to an unsaturated molecule. Vegetable oils
are triesters of unsaturated fatty acids, long chains of carbon atoms that
have many double bonds. The following equation shows just one por -
tion of an oil molecule. When hydrogen gas is blown through an oil,
hydrogen atoms may add to the double bonds in the oil molecule.

ORGANIC CHEMISTRY 735

 FIGURE 16 The fatty acid shown
in the model for vegetable oil con -
tains a double bond. During hydro-
genation . which is used to produce
margarine and vegetable shortening,
addition of hydrogen atoms removes
double bonds from fat tv acids.

ii II II II II II n H H H H II H H
CHEMISTRY . I c-oc-c-oc- c + H:
catalyst I l
c-oc-c-c-c- c
l I

Module 7: Equilibrium
H H H H H II II H
Die molecule still consists of long chains of carbon atoms, but it con -
tains far fewer double bonds. The conversion of these double bonds to
single bonds changes the material from an oil, which is a liquid, into a fat ,
which is a solid. When you see the word hydrogenated on a food prod-
uct . you know that an oil has been converted to a fat by this process.
Examples of an oil and hydrogenated fats are shown in Figure 16.

Condensation Reactions
A condensation reaction is one in w hich two molecules or parts of the
.
same molecule combine A small molecule, such as water, is usually
removed during the reaction. An example is the reaction between two
amino acids, which contain both amine and carboxyl groups. One
hydrogen from the amine group of one amino acid combines with the
hydroxyl from the carboxyl group of the other amino acid to form a
molecule of water. When repeated many times, this reaction forms
a protein molecule.

H H O H H O H H O H H O
I I I II I I II I l II
H -N - C- C OH + H N-C-C- OH > H-N-C-C N-C-C- OH + ITO
I
R R' R R'
amino acid amino acid dipeptide water

736 CHAPTER 22
 FIGURE 17 Sucrose is dehydrated
when it reacts with concentrated sul -
furic acid . Elimination of water pro-
Elimination Reactions duces a compound that is mostly
carbon .
An elimination reaction is one in which a simple molecule, such us water
or ammonia, is formed from adjacent carbon atoms of a larger molecule.
A simple example of an elimination reaction is the heating of ethanol in
the presence of concentrated sulfuric acid . Under these conditions, a
hydrogen atom bonded to one carbon atom and a hydroxyl group bonded
to the second carbon atom are removed from the ethanol molecule. A
molecule of water is formed as a result .

H OH
H-C-C-H
I A I I
.
H - C - C- H + H - 0
H H H H
ethanol ethene water

Another example of an elimination reaction is the dehydration of

sucrose with concentrated sulfuric acid , shown in Figure I 7.

Polymers
Polymers are large molecules made of many small units joined to each
other through organic reactions. The small units are monomers. A poly -
SCllNKS. Developed utd iMMlMfd by the
Hetwal Some Teachm Auouattoo
mer can be made from identical or different monomers. A polymer For a variety of links related to this
made from two or more different monomers is a copolymer. chapter, go to www.s g
Polymers are all around us. The foods we eat and clothes we wear are Topic: Polymers
'h
made of polymers. Some of the most common natural polymers include SciLinks code: HC61182
starch , cellulose, and proteins. Some synthetic polymers may be familiar
to you as plastics and synthetic fibers.

ORGANIC CHEMISTRY 737

 — r£f t?r n
Addition Polymers
Chemistry in Action
Go to go. hrw.com for a full - length An addition polymer is a polymer formed by addition reactions between
article on high - barrier plastics.
>*' - Keyword: HC 60 RGX
monomers that contain a double bond . For example, molecules of ethene
can polymerize with each other to form polyethene, commonly called
polyethylene.
catalys
// CH:= CH:
ethene
^ {CH2-CH 2
^
polyethylene

The letter n shows that the addition reaction can be repeated multiple
times to form a polymer n monomers long. In fact , this reaction can be
repeated hundreds or thousands of times.

Forms of Polyethylene and Related Polymers

Various forms of polyethylene, shown in Figure 18, have different
molecular structures. High -density polyethylene ( HDPE ) is a linear
polymer. It has a high density because linear molecules can pack togeth -
er closely. One use of HDPE is in plastic containers such as milk and
juice bottles because HDPE tends to remain stiff and rigid .

FIGURE 18 Properties of the

different forms of polyethylene are
reflected in their uses. Linear mol -
ecules of polyethylene can pack
together very closely, as shown in the
-
model of high density polyethylene
( HDPE ). The branches of branched
polyethylene keep the molecules
from packing tightly as shown in the
low -density polyethylene ( LDPE )
-
structure. The cross links of cross-
linked polyethylene ( cPE ) make it
very strong.

HDPE

738 CHAPTER 22
 Condensation Polymers
A condensation polymer is a polymer formed by condensation reac -
tions. Monomers of condensation polymers must contain two function -
al groups. This allows each monomer to link with two other monomers
by condensation reactions. Condensation polymers are usually copoly -
mers with two monomers in an alternating order.

Polyamides and Polyesters

One example of a condensation polymer is shown below. A carboxylic
acid with two carboxyl groups, adipic acid, and an amine with two amine
groups, hexanediamine. react with each other to form water.
H H O O
l
nH -
N-CH,-CH
«
,-CH2-CH2- CH-,-CH,-N
W W 4b
II + /1 HO C-CH^->-CH,-CH,-CH,^-C-OH
» mm

hexanediamine adipic acid

/ H HO 0\
v N-CH2-CH:-CH2-CH2-CH2-CH2-N C-CH:-CH2-CH2-CH2-C + n 1120
nylon 66 water
4
The product is a polyamide and contains the adipic acid monomer
and the hexanediamine monomer. This copolymer is known as nylon 66
because each of the monomers contains six carbon atoms. Nylon 66 is
one of the most widely used of all synthetic polymers.
Polyesters are another common type of condensation polymer. They
are formed from dialcohols and dicarboxylic acids, which undergo a con-
densation reaction to form an ester group, linking the alcohol end of a
monomer to the acid end of a monomer. Polyesters have many uses, such
as in tires, in food packaging, and as fibers in permanent press fabrics.

SECTION REVIEW 6. Would it be possible to have an addition polymer

.
1 Can an addition reaction occur between chlorine synthesized from a monomer that has only single
bonds? Why or why not ?
and ethane? Why or why not ?
.
2 Does an addition reaction increase or decrease the Critical Thinking
saturation of a molecule? 7. APPLYING MODELS Polyvinyl chloride ( PVC) is a
.
3 The condensation reaction between two amino polymer that is widely used in pipes and flooring.
acids has a water molecule as one product. Which It is an addition polymer made from chloroethene,
functional groups are the sources of the atoms in commonly known as vinyl chloride.
the water molecule? a. Draw the structure of vinyl chloride. Then, look
.
4 Explain how elimination reactions could be up the structure or check it with your teacher.
considered the opposite of addition reactions. b. Write the reaction for the polymerization of
5. Why can a molecule that has only one functional vinyl chloride to form polyvinyl chloride (PVC).
group not undergo a condensation reaction to
form a polymer?

ORGANIC CHEMISTR Y 739

 CHAPTER HIGHLIGHTS
Organic Compounds
I Vocabulary •The ability of carbon to bond to other elements and to allow
organic compound different arrangements of atoms contributes to the diversity of
catenation carbon compounds.
hydrocarbon •Isomers are compounds that have the same molecular formula
isomer but different structures. In structural isomers, the atoms are
structural formula bonded together in different orders. In geometric isomers, the
structural isomer order of atom bonding is the same, but the atoms are oriented
geometric isomer differently in space.

Hydrocarbons
I Vocabulary •Alkanes are saturated hydrocarbons; they contain only single
saturated unsaturated bonds. Physical trends in alkanes correspond to trends in
hydrocarbon hydrocarbon alkane size and amount of branching.
alkane alkene •Organic compounds are named according to a systematic
cycloalkane alkyne method.
alkyl group aromatic
•Unsaturated hydrocarbons have one or more multiple carbon -
natural gas hydrocarbon
carbon bonds: these include alkenes. alkynes, and aromatic
petroleum benzene
hvdrocarbons.

Functional Groups
I Vocabulary •Functional groups are responsible for the properties of the
functional group organic compound that contains the functional group.
alcohol •Alcohols contain the hydroxyl functional group.
alkyl halide •Alkyl halides contain one or more halogen atoms.
ether •Two alkyl groups are joined to an oxygen atom in ethers.
aldehyde •Both aldehydes and ketones contain the carbonyl group.
ketone •Amines are derivatives of ammonia.
amine •Carboxylic acids contain carboxyl groups.
carboxylic acid •In esters, the hydrogen atom of a carboxylic acid group has
ester been replaced with an alkyl group.

Organic Reactions
I Vocabulary •In substitution reactions, an atom or group of atoms is replaced.
substitution reaction In addition reactions, an atom or group of atoms is added to a
addition reaction double or triple bond.
condensation reaction •In a condensation reaction, two molecules combine. In an elim -
elimination reaction ination reaction, a small molecule forms from a large molecule.
polymer •Polymers are large molecules made of many repeating units
monomer called monomers. A copolymer consists of two or more differ -
copolymer ent monomers.

740 CHAPTER 22
 CHAPTER REVIEW
b. alkene series
Organic Compounds c. alkyne series
SECTION 1 REVIEW 9. a. What is a homologous series?
1. a. What is catenation? b. By what method are straight-chain hydrocar -
b. How does catenation contribute to the diver - bons named?
c. Name the straight -chain alkane with the
sity of organic compounds?
2. a. What information about a compound is pro- molecular formula C1( )H22
10. What are cycloalkanes?
vided by a structural formula ?
b. How are structural formulas used in organic 11. a. What trend occurs in the boiling points
chemistry? of alkanes?
b. How would you explain this trend?
3. Can molecules with the molecular formulas
C4H10 and C4Hl0O be structural isomers of one c. How is the trend in alkane boiling points
another ? Whv or why not ? used in petroleum fractional distillation?
4. Can molecules with only single bonds ( and no 12. Give examples of ethene s commercial uses.
rings ) have geometric isomers? Why or why not ? 13. Give one use for ethyne.
14. What is the name of the parent hydrocarbon
of simple aromatic hydrocarbons?
Hydrocarbons
PRACTICE PROBLEMS
SECTION 2 REVIEW
15. Name the following molecules. ( Hint: See
5 . What are hydrocarbons, and what is their
Sample Problem A .)
importance?
a. CH 3-CH 2-CH 2- CH:-CH:-CH2-CH3
6. a. What do the terms saturated and unsaturated
mean when applied to hydrocarbons? b. CH3
b. What other meanings do these terms have in CH,-C- CH,- CH - CH - CH ;
'
1 I
chemistry? CH3 CH3
c. Classify alkenes. alkanes, alkynes. and aro -
matic hydrocarbons as either saturated or c. CH3 CH2-CH2-CH 2-CH3
unsaturated. CH3-C-CH2-CH2-CH-CH2-CH2-CH2-CH3
7. Classify each of the following as an alkane, CH3
alkene. alkvnc. or aromatic hydrocarbon.
a
.
16 Give the complete, uncondensed, structural for -
.
mula for each of the following alkanes ( Hint:
See Sample Problem A . )
a. decane
CH:- CH3 b. 3,3-dimethylpentane
17 . Give the condensed structural formula for
b. CH3- CH=CH:
2,2.4.4 - tetramethylpentane.
c. CH;
l
.
18 For each of the following, determine whether
CH=C-CH-CH:-CH3 the alkane is named correctly. If it is not. give
d. CH3- CH -CH 2- CH 2-CH:-CH:-CH3
the correct name .
a. 1 -melhylpropane
CH3 b. nonane
8. Give the general formula for the members c. 4-methylhexane
of the following: d. 4-ethvl-2-methvlhexane
a. alkane series

ORGANIC CHEMISTRY 741

 CHAPTER REVIEW

19. Name the following alkenes. ( Hint: See Sample 25. Aldehydes and ketones both contain the same
Problem B.) functional group. Why are they classified as sep -
a. CH2=CH- CH2 -CH 2-CH3 arate classes of organic compounds?
26. How are esters related to carboxylic acids?
b. CHV H
/ 27. What element do amines contain besides car -
C=C
CH,/ \
CH , bon and hydrogen?
28. Explain why an amine acts as a base.
c. CH 3 .
29 What classes of organic compounds contain
CH:=CH -C- CH , CH,
- oxygen?
CHi
CH , Organic Reactions
d. CH=C- CH,-CH,-CH =CH,
l
CH , SECTION 4 REVIEW
30. What type of chemical reaction would you
20. Name the following alkynes: expect to occur between 2-octene and hydrogen
a. CH=C-CH3 bromide. HBr ?
b. CH3-C=C-CH-CH3 .
31 How many molecules of chlorine. Cl2, can be

CH , added to a molecule of l-propene? a molecule

of 1-propyne?
,
c. CH - CH — C=C — CH — CH , 32. Compare substitution and addition reactions.
CH , CH , 33. In a chemical reaction, two small molecules are

,
d. CH=C CH -CH;- CH: C=CH
joined and a water molecule is produced. What
type of reaction took place?
34. What are two reactions by which polymers can
be formed ?
Functional Groups 35. What is the structural requirement for a mole-
cule to be a monomer in an addition polymer?
SECTION 3 REVIEW
36. Which of the following reactions is a substitu-
21. Write the general formula for each of the tion reaction ?
following:
-
a. CHi CHi + Cl . * »CI- CH2-CH2- CI
b. CH,-CH -CH -CH, + Cl
a. alcohol
4 4< M

.
b ether ->
c. alkyl halide
2
-
2
- -
2
Cl CHi CHi ChH CH
- , + HCI
22. Based on the boiling points of water and c. o
methanol, in which would you expect to observe CH;- OH + CH3-C-OH ->
a greater degree of hydrogen bonding? Explain o
your answer.
CH 3- OO-CH 3 + H 2O
23. a. Why is glycerol used in moisturizing skin
lotions? 37. Which of the following reactions is an addition
b. How does this relate to the chemical struc - reaction?
ture of glycerol ? a. CH3-CH:- CH=CH 2 + Br:
24. Write the general formula for each of the CH3- CH2 — CH- CTH- Br
following: Br
a. aldehyde d. ester
b. ketone e. amine
c. carboxylic acid

742 CHAPTER 22
 CHAPTER REVIEW

c. C)
heat
,
85% H P04
» .
CHj-CH -OH + CH 3-C-OH
o
-»

CH 3-CH 2-0-C-CH3 + ICO

CH 3-C-OH + CH -OH o
*
o CH 3-C-CH3 OH

CH -C- O-CH + H:0 ,

38. Which of the following reactions is a condensa - O
tion reaction ? CH = CH -C-CH + H:0 ,
a. Br
ether
41. Classify each of the following reactions as a
=
CH3C CH + HBr * CH 3-C =CH2
substitution reaction or an addition reaction:
Br
ZnCI,
cci4 -
a . CH3-CH 2 CH 2-CH 2-OH + HC'l heat
.
*
CH 3-CH 2-CH 2 -CH 2-Cl + H 2O
Br
e. CH 3- CH 2- OH + CH 3-CH 2-OH 4
.
H SO b. CH 2 = CH 2 + HBr 25°C
ether » CH 3-CH 2 Br -
^ CH -.=CH -C1
HgCt,
CH 3- CH 2-0-CH 2-CH 3 + H 2O c. CH = CH + HC1 -
39. Which of the following reactions is an elimina - d. \ CH3
tion reaction ?
a. CH 2 = CH -CH 2-CH 3 + Cl 2 *
^ + HBr
ether

C1-CH 2-CH- CH 2-CH 3

42. Identify each of the following reactions as an
Cl addition , substitution , elimination , or condensa -
b. OH tion reaction:
H ,0 *
a. O OH
CH3-CH- CH3 >
CH3-CH = CH 2 + H 2 O CH3-C OH + CH 3-CH-CH3 »
-

c. CH3CH + CB, lighl or

CH ,CHX1 + HC1 O CHJ ,
heat
)
II
CH 3-C-0-CH-CH 3 + H - 0
I
.
b. CH:=CH-CH 3 + Cl2 >
MIXED REVIEW C1-CH 2-CH-CH 3

40. Classify each of the following reactions as

an elimination reaction or a condensation reac-
light or
tion : heat
a. Br
CH3-C=CH 2 + NaNH2 »
CH3C=CH + NaBr + NH3
HrOMHF
h. OH 50 C
85 % H 3 PO4
CH 3-CH 2-CH-CH 3 heat
CH3-CH=CH-CH3 + H 2O

ORGANIC CHEMISTRY 743

 CHAPTER REVIEW

43. Give the molecular formula for each type of c. To what homologous series do each of these
hydrocarbon il it contains seven carbon atoms. compounds belong?
a . an alkane 51. The reaction of methane with oxygen produces
b. an alkene two different oxides of carbon . Review this
c. an alkyne material in the Elements Handbook , and answer
44. a . Alkyne nomenclature is very similar to the following:
the nomenclature of what other group of a . What condition determines whether the prod -
hydrocarbons? uct of the methane reaction is CO: or CO?
b. I low do these nomenclatures differ? b. If a home heating system is fueled by natural
.
45 a . What are delocalized electrons? gas. what difference does it make if the com -
b. What is their effect on the reactivity of aro- bustion produces C02 or CO ?
matic hydrocarbons? 52. Silicon is similar to carbon in forming long-
chain compounds. Review the material on sili -
con in the Elements Handbook and answer the
CRITICAL THINKING following.
a. How does a long-chain silicon compound dif -
46. Inferring Conclusions Why are organic com - fer in composition from a long-chain carbon
pounds with covalent bonds usually less stable compound ?
when heated than inorganic compounds with b. The simplest alkane is methane. Methyl
ionic bonds? groups are found in all alkanes. What is a
47. Inferring Relationships The element that common subunit of a silicate? What is the
appears in the greatest number of compounds geometry of that subunit ?
is hydrogen . The element found in the second .
53 Mercury in the environment poses a hazard to
greatest number of compounds is carbon. Why living things. Review the section on mercury
are there more hydrogen compounds than car- poisoning in the Elements Handbook .
bon compounds? a. Draw a structural formula for the organic
.
48 Relating Ideas As the number of carbon mercury compound described in that section.
atoms in an alkane molecule increases, does the b. What is the IUPAC name for this compound ?
percentage by mass of hydrogen increase,
decrease, or remain the same?
RESEARCH & WRITING
49. Applying Ideas l low does ethylene glycol pro-
tect radiator fluid in an automobile from both 54. Chemical and Engineering News publishes a list
freezing in the winter and boiling over in the once a year of the top 50 chemicals. Find out
summer? which chemicals on the current year’s list are
hydrocarbons, and report your findings to the
class.
USING THE HANDBOOK 55. C onsult reference materials at the library, and
read about products made from hydrocarbons.
50. The top I 0 chemicals produced in the United Keep a list of the number of petroleum - related
States are listed in Table 7 B of the Elements products you use in a single day.
Handbook . Review this material , and answer 56. The widespread use of synthetic polymers in
the following: modern society has led to a number of new-
a. Which of the top ten compounds are organic? environmental problems. Find out what some
b. Write structural formulas for the compounds of these problems are and what can be done
you listed in item ( a ) . to reduce them .

744 CHAPTER 22
 CHAPTER REVIEW

61. Keep a list of the food you consume in a single

ALTERNATIVE ASSESSMENT
day. Compare the content labels from those
57. Performance Models are often used to visual- foods, and then list the most commonly used
ize the three-dimensional shape of molecules. chemicals in them. With the aid of your teacher
Using gumdrops as atoms and toothpicks to and some reference books, try to classify the
bond them together, construct models of organic chemicals by their functional groups.
different hydrocarbons. Use large gumdrops for 62. As a class or small group, research the preserva -
carbon and smaller gumdrops for hydrogen. tives used in various foods. Examine their
58. Performance Using your gumdrop models, chemical structures. Determine a way to test for
demonstrate why alkenes can have geometric organic functional groups of possibly hazardous
isomers, while alkanes ( except cycloalkanes ) preservatives.
cannot .
59. Performance Devise a set of experiments to
study how well biodegradable plastics break
.
down If your teacher approves vour plan,
conduct an experiment to lest the procedure
on products labeled “biodegradable."
s Graphing Calculator
I 1ydrocarhon Formulas
.
Go to go.hm com for a graphing calculator
exercise that asks you to find the formula of
60. Performance Your teacher will make available
any straight -chain hydrocarbon, given the
unlabeled samples of benzoic acid, ethyl alco-
number of carbon atoms and the number of
hol. and hexanediamine. Develop an experi -
double bonds in the compound.
ment to identify each. If your teacher approves
your plan, identify the unknown substances. si - Keyword: HC 60 RGX

ORGANIC CHEMISTRY 745

 Math Tutor CALCULATING EMPIRICAL FORMULAS

An empirical formula shows the simplest whole- number ratio among the elements in a
compound. For example, the simplest ratio among the atoms in benzene, C6H6, can

^,
be expressed by the empirical formula CH (or C H ). Empirical formulas may be calcu-
lated from simple analytical data, as shown in the example below.

Problem-Solving TIPS
• Sometimes, you can deduce the mole ratios of the elements in a compound just
by examining the moles of each element. If not. divide the moles of each ele-
ment by the moles of the least abundant element in the compound.

SAMPLE
l ind the empirical formula of acetone, a common organic solvent , whose composition by
mass is 62.04% carbon, 10.41% hydrogen, and 27.55 % oxygen.
The easiest way to calculate an empirical formula from percentage composition is to con -
sider a 100.00 g sample of the compound. In this case, a 100.00 g sample would contain
62.04 g of carbon, 10.41 g of hydrogen, and 27.55 g of oxygen. Convert each mass to moles
so that you can compare the mole ratio of the three elements.
1 mol C
62.04 g C x = 5.166 mol C
12.01 gC
1 mol H
10.41 g H x = 10.33 mol H
1.008 g H
1 mol O
27.55 g O x = 1.722 mol O
16.00 gO
5.166 mol C 10.33 mol H 1.722 mol O
1.722 1.722 1.722
3.000 mol C : 5.999 mol H : 1.000 mol O
As you can see. the empirical formula of this compound is C H O.
^ ^
PRACTICE PROBLEMS
1. Urea was the first organic compound to be 4.17 % hydrogen, and 66.05% bromine, by
synthesized in the laboratory. Urea's composi - mass. What is the empirical formula of this
tion by mass is 20.00% carbon. 6.71 % hydro - compound?
gen. 46.65 % nitrogen, and 26.64% oxygen. 3. Hie composition bv mass of lactic acid is
What is the empirical formula of urea ? 40.00% carbon. 6.71 % hydrogen, and 53.28%
2. An organic compound sometimes used in the oxygen. What is the empirical formula of lac -
manufacture of perfumes is 29.78 % carbon . tic acid?

746 CHAPTER 22
Answer the following items on a separate piece of paper. 7. Examine the following structural formula:
MULTIPLE CHOICE II
1. Which of the following hydrocarbons must be H- C- H
an alkane ?
H H H
A . C?H?
B. ( 5 H 10 H- C- C ( OH
C. C7 Hi: II II H

^ ^
D * 14 30 H- C- H
2. A hydrocarbon with the formula CSHIS is called H
A . octene.
The correct name for this compound is
B. octyne.
A . 2.2- dimethylbutane.
C. octane.
B. 1.1. 1 - trimethvlpropane.
D. propane.
C. 2 - ethyl- 2- methylpropane.
3. During a condensation polymerization reaction , D. 3,3- dimethylbutane.
A. single bonds replace all double bonds that
8. Organic functional groups
are present in the monomer.
A . give characteristic properties to compounds
B. water is often produced.
that contain them.
C. alcohol groups are formed.
B. always contain oxygen.
D. an aldehyde group is changed to a ketone
C. always contain a double or triple bond.
group.
D. are present in every organic compound.
4. In naming an organic compound, we
SHORT ANSWER
A . should remember that naming the locations
of all functional groups is optional. 9. What feature must be present in a compound
B. do not consider the number of carbon atoms for it to undergo an addition reaction?
in the molecule as a factor. 10. Organic compounds of what class contain only
C. begin by identifying and naming the longest two elements?
hydrocarbon chain. EXTENDED RESPONSE
D. ignore side chains when we name the molecule.
11. Describe the difference between substitution
5. Which of the following compounds cannot have and addition reactions. Your answer should
different isomers? mention the degree of saturation of the organic
A. C7 Hlh compound.
B. CSH 10
12. Explain why some alkanes are gases, others
,
C. C HS are liquids, and still others are solids at room
D . ChHi:Oh temperature.
6. Compounds that differ only in the order in
which the atoms are bonded together are called
A . condensation polymers.
B. addition polymers.
C. structural isomers.
D. geometric isomers.
If you become short on time,
quickly scan the unanswered questions to see which
might be easiest to answer.

ORGANIC CHEMISTRY 747

 EXPERIMENT 22

Polymers and Toy Balls

OBJECTIVES BACKGROUND
• Synthesize two different polymers. What polymers make the best toy balls? Two pos-
sibilities are latex rubber and a polymer produced
• Prepare a small toy ball from each polymer. from ethanol and sodium silicate. Latex rubber is a
• Observe the similarities and differences polymer of covalently bonded atoms.
between the two types of balls. The polymer formed from ethanol , C2 H 5OH .
• Measure the density of each polymer. and a solution of sodium silicate. Na 2Si307, also has
covalent bonds. It is known as water glass because it
• Compare the bounce height of the two halls. dissolves in water.
In this experiment , you will synthesize rubber and
MATERIALS the ethanol silicate polymer and test their properties.
2 L beaker, or plastic bucket or tub
3 ml . 50 % ethanol solution
SAFETY

5 oz paper cups, 2
10 mL 5% acetic acid solution ( vinegar )
25 mL graduated cylinder For review of safety, please see Safety in the
Chemistry Laboratory in the front of your book .
10 mL graduated cylinder
10 mL liquid latex PREPARATION
12 mL sodium silicate solution 1 . Organizing Data: Create a data table in your lab
notebook in which the columns are labeled ‘Trial.”
distilled water
“ Height (cm ) " “ Mass (g)," and “ Diameter ( cm ) ”
gloves Create three rows ( Trials 1 , 2. and 3 ) in your table.
meterstick
paper towels PROCEDURE
wooden stick 1. Fill the 2 L beaker, bucket , or tub about half - full
with distilled water.
2 . Using a clean 25 mL graduated cylinder, meas-
ure 10 niL of liquid latex and pour it into one of
the paper cups.
3. Thoroughly clean the 25 mL graduated cylinder
with soap and water, and then rinse it with
distilled water.

748 CHAPTER 22
 EXPERIMENT 22

4. Measure 10 mL of distilled water. Pour it into 15. Drop each ball several times, and record your
the paper cup with the latex. observations.
5. Measure 10 mL of the 5 % acetic acid solution , and 16. Drop one ball from a height of l m . and measure
pour it into the paper cup with the latex and water. its bounce. Perform three trials for each ball .

6. Immediately stir the mixture with the wooden 17. Measure the diameter and mass of each ball .
stick .
CLEANUP AND DISPOSAL
7. As you continue stirring, a polymer lump will form
around the wooden stick. Pull the stick with the 18. Dispose of any extra solutions in the
containers indicated by your teacher .
polymer lump from the paper cup. and immerse
Clean up your lab area . Remember
the lump in the 2 L beaker, bucket , or tub.
to wash your hands thoroughly when your
8. While wearing gloves, gently pull the lump lab work is finished .
from the wooden stick . Be sure to keep the
lump immersed under the water. ANALYSIS AND INTERPRETATION
9. Keep the latex rubber underwater , and use your .
1 Analyzing Information: List at least three
gloved hands to mold the lump into a ball. Then , of your observations of the properties of the
squeeze the lump several times to remove any two balls.
unused chemicals. You may remove the latex rub- 2. Organizing Data: Calculate the average height
ber from the water as you roll it in your hands to of the bounce for each type of ball.
smooth the ball.
3. Organizing Data: Calculate the volume for each
10. Set aside the latex rubber ball to dry. While it ball. Even though the balls may not be perfectly
is drying, proceed to step 11. spherical , assume that they are. ( Hint: The
volume of a sphere is equal to 4A X K X r\
11. In a clean 25 mL graduated cylinder, measure
where r is the radius of the sphere, which is one-
12 mL of sodium silicate solution , and pour it
half of the diameter. ) Then , calculate the density
into the other paper cup.
of each ball , using your mass measurements.
12. In a clean 10 mL graduated cylinder, measure
3 mL of 50% ethanol. Pour the ethanol into CONCLUSIONS
the paper cup with the sodium silicate, and mix
1. Inferring Conclusions: Which polymer would
with the wooden stick until a solid substance
you recommend to a toy company for making
is formed .
new toy balls? Explain your reasoning.
13. While wearing gloves, remove the polymer that
2. Evaluating Viewpoints: What are some other
forms and place it in the palm of one hand .
possible practical applications for each of the
Gently press it with the palms of both hands until
polymers you made?
a ball that does not crumble is formed . This step
takes a little time and patience. The liquid that
comes out of the ball is a combination of EXTENSIONS
ethanol and water. Occasionally, moisten the 1. Predicting Outcomes: Explain w hy you would
ball by letting a small amount of water from a not be able to measure the volumes of the balls
faucet run over it . When the ball no longer by submerging them in water.
crumbles, you are ready to go to the next step.
14. Observe as many physical properties of the
balls as possible, and record your observations
in your lab notebook .

ORGANIC CHEMISTRY 749

 CHAPTER 23

Biological Chemistry
Chemical reactions occur in all living organisms.

J \ V?
4
>

For advanced project ideas

from Scientific American, V
visit go.hrw.com and type
in the keyword HC6SAH.
Honeybib Pollinating a Poppy
r
Carbohydrates SECTION 1

and Lipids OBJECTIVES

Describe the structural char -
acteristics of simple carbohy -
drates and complex
carbohydrates.
B iochemistry is the study of the chemicals and reactions that occur in
living things. Biochemical compounds are often large and complex organ-
ic molecules, but their chemistry is similar to that of the smaller organic
^ Explain the role of carbohy -
drates in living systems.
molecules you studied in Chapter 22. Now you will study many important
biochemical molecules and learn why they are needed to slay healthy.
w Describe the structural char -
Two of the most common types of molecules that you may know about
acteristics of lipid molecules.
are carbohydrates and lipids. These molecules are important parts of the
food that you eat and provide most of the energy that your body needs.
Identify the functions of lipids
in living cells.

Carbohydrates
Sugars, starches, and cellulose belong to the large group of biochemical
molecules called carbohydrates. Carbohydrates are molecules that are
composed of carbon , hydrogen , and oxygen atoms in a 1:2:1 ratio , and
provide nutrients to the cells of living things. They are produced by
plants through a process called photosynthesis. Cellulose provides struc -
ture and support for plants and starch stores energy in plants. Because
animals cannot make all of their own carbohydrates, they must get them FIGURE 1 Glucose and fructose
from food. Carbohydrates provide nearly all of the energy that is avail - .
both have 6 C 12 H. and 6 O atoms.
able in most plant - derived food. The arrangement of the C. H. and O
atoms determines the shape and
Monosaccharides properties of each sugar.
A monosaccharide is a simple sugar that is the basic subunit of a carbo - CH ’OH
hydrate. A single monosaccharide molecule contains three to seven car - A
bon atoms. Monosaccharide compounds are typically sweet - tasting,
H
C
/H °V Hc
white solids at room temperature. Because they have polar, hydroxyl I ?H
\
OHY vTOH
c
( — O H ) groups in their molecular structures, they are very soluble in
H OH
water. The most common monosaccharides are glucose ( also called dex-
glucose
trose ) and fructose. Although both of these monosaccharides have the
formula C6(H20 )6. their structural formulas differ. As Figure 1 shows, CH:OH o H
glucose in a water solution forms a ring made up of five carbon atoms
C H OH/ i
and one oxygen atom, and fructose in a water solution forms a ring CH 3OH
HO
made up of four carbon atoms and one oxygen atom. Notice that both
compounds have five - OH groups in their structures. OH H
fructose

BIOLOGICAL CHEMISTRY 751

 Glucose is ihe most abundant monosaccharide in nature. It is also the
most important monosaccharide nutritionally for animals because glu -
cose provides energy for cellular activities. The carbohydrates we eat
are broken down into glucose, which may be used immediately by cells
or stored in the liver as glycogen for later use. Glucose is also found in
some fruits, corn , and the sap of plants.
Fructose, also called fruit sugar, is found in most fruits and in honey.

ivm The sweetest naturally occurring sugar , fructose is sweeter than table
sugar. Because of its sweetness, fructose is sometimes used as a low -
calorie sweetener because less fructose is needed to produce the same
sweetness that table sugar does.

Disaccharides
LA Generally, when someone asks for “sugar, ' the person is asking for the

21
*

,
disaccharide sucrose. C H O A disaccharide is a sugar that consists
^
of two monosaccharide ^units that are joined together. Like monosaccha -
rides, disaccharides have polar hydroxy groups in their molecular struc-
FIGURE 2 Most of the sugar pro-
tures and therefore are water soluble. A molecule of sucrose forms
duced throughout the world comes
from sugar beets such as those when a glucose molecule bonds to a fructose molecule. Commercially
shown here, or from sugar cane. available sugar comes from sugar cane or sugar beets, such as those
shown in Figure 2. Another important disaccharide is lactose, or milk
sugar. Lactose is made up of a sugar called galactose and glucose.
Human milk is 7 to 8% lactose, but cow s milk is only 4 % to 5 % lactose.
Infant formula may be enriched with lactose to simulate human milk .

Carbohydrate Reactions
Carbohydrates undergo two important kinds of reactions: condensation
reactions and hydrolysis reactions. A condensation reaction is a reaction
in which two molecules or parts of the same molecule combine. Figure 3
shows a condensation reaction in which a molecule of glucose combines
with a molecule of fructose to yield a molecule of sucrose. Note that in
this reaction a molecule of water is also formed.
Disaccharides and longer-chain polysaccharides can be broken down
into smaller sugar units bv hvdrolvsis. Hydrolysis is a chemical reaction
between water and another substance to form two or more new sub -
stances. Sucrose will undergo a hydrolysis reaction with water, forming
glucose and fructose. This hydrolysis, or “ water-splitting, reaction occurs
**

in many common processes, such as in the making of jams and jellies.

FIGURE 3 The disaccharide
sucrose is formed by a condensation
reaction between glucose and
fructose.

-
CH OII
CH ,OH ,Q
H /, °\ H
c + ci \
( )
/ \
H
+- H H
f \?H
OHY VI
C OH HOK \!
11 OH OH
glucose fructose sucrose water

752 CHAPTER 23
 Cooking sucrose with high acid foods, such as berries and fruits,
SC
causes it to break down into a mixture of equal parts of glucose and
fructose. This new mixture provides the sweet taste in jams and jellies,
/ lNKS. OtTdopttf Md h rw
mtHwtil StKiKv Tutfctn AMKMM
which is sweeter than the starting sugar. When lactose is broken For a variety of links related to this
down , glucose and galactose are formed . Some people do not produce chapter, go to www.scillnks.Ofg
the enzyme needed to break down the milk sugar in dairy products. Topic: Carbohydrates
This condition is called lactose intolerance. People who have this may SciLinks code: HC 60213
feel ill when they drink milk or eat foods that have milk in them .

Polysaccharides
When many monosaccharides or disaccharides combine in a series of
condensation reactions, they form a polysaccharide. A polysaccharide is
a carbohydrate made up of long chains of simple sugars. Cellulose,
starch , and glycogen are polymers of glucose, or polysaccharides, that
contain many glucose monomer units.
As shown in Figure 4, the glucose molecules in cellulose chains are
arranged in such a way that hydrogen bonds link the hydroxy groups
of adjacent glucose molecules to form insoluble fibrous sheets. These
sheets of cellulose are the basic component of plant cell walls. More
than 50 % of the total organic matter in the world is cellulose. People
cannot digest cellulose, but when we eat fiber, which is cellulose, it
speeds the movement of food through the digestive tract .
Microorganisms that can digest cellulose are present in the digestive
tracts of some animals. Cows and other ruminants have a special stom -
ach chamber that holds the plants they eat for long periods of time,
during which these micro-organisms can break down the cellulose into
glucose.
Starch is the storage form of glucose in plants. Starch from foods
such as potatoes and cereal grains makes up about two- thirds of the
food eaten by people throughout the world . Starch in food is broken
down into glucose during digestion . Glucose is broken down further in FIGURE 4 Glucose is the mono-
metabolic reactions that will he discussed later in this chapter. saccharide subunit for glycogen cel - ,

lulose, and starch . Notice that these

three polymers differ in their
arrangement of glucose monomers.

glucose monomers
—
)

Cellulose chains
linked by —
OH C
hydrogen bonds 1
'
11 0
glucose
•t t

glycogen cellulose starch

BIOLOGICAL CHEMISTRY 753

 5< Lipids
7INKS Mft
Ofkriopeii Md nuInlMMd by (W
MMNMI Some TMckm AuotutkM
Lipids are another important class of nutrients in our diet. They are
For a variety of links related to this
chapter, go to .. v.\ scijinks. org found in dairy products, grains, meats, and oils. A lipid is a type of bio-
Topic: Lipids
IS
'
chemical that does not dissolve in water; has a high percentage of C and
SciLinks code: HC60881 II atoms, ami is soluble in nonpolar solvents. As a class, lipids are not
nearly as similar to each other as carbohydrates are. Long-chain fatly
acids, phospholipids, steroids, and cholesterol are lipids.

Fatty Acids and Triglycerides

Fatty acids consist of a long, nonpolar hydrocarbon " tail" and a polar car-
boxylic acid functional group at the " head. Fatty acids are the simplest lipid
"

molecules. They have hydrophilic polar heads, hut their hydrocarbon chains
make them insoluble in water. Fatty acids can also be saturated or unsatu-
rated. Saturated fatty acids have no carbon -carbon double bonds, while
unsaturated fatty acids have one or more double bonds in the hydrocarbon
chain. The lipid shown below is oleic acid.

H H H H H H H H H H H H H H H
c — c-c —c-c-c-c-c-c=c —c —c-c-c-c-c —C-C-H
/
no I I H H H H H I I H H I I I I H H H H LI H

V
hydrophilic region hydrophobic region

Triglycerides are the major component of the fats and this in your diet .
They are formed by condensation reactions in which three fatty acid mol -
ecules bond to one glycerol ( a type of alcohol ) molecule. Fats, such as but -
ter and lard, come from animals, while oils come from plant sources, such
.
as coconuts, peanuts, corn, and olives, as shown in Figure 5 Because they
have a large amount of saturated fatty acids, fats are solids at room tem -
perature. Oils have more unsaturated fatty acids than fats, and are liquids.
FIGURE 5 Fats, such as lard and
Like other animals, humans make fat. which is stored in adipose tissue
butter, arc obtained from animals.
Oils are found in mans different until it is needed as an energy source. Fat has about twice as much energy
plants. per gram as carbohydrates or proteins do. Tlius, fat is an efficient form of
energy storage.
Fats have another important commercial value based on their ability
to react with sodium hydroxide, NaOH. commonly known as lye . When
a fat combines with NaOH . an acid - base reaction called saponification
occurs, and a salt and water form. This salt is made up of molecules that
have long carboxylic acid chains and is called soap. A molecule of soap
has a charged ionic head and a nonpolar hydrocarbon tail. This struc -
ture allows the ionic head of a soap molecule to dissolve in water and
the nonpolar tail to dissolve in nonpolar greases. This property gives the
soap its cleaning ability. The chemistry of this reaction is also used as a
way of classifying lipids. Lipids that react with a base to form soap are
called saponifiable lipids, which include fats, oils, and fatty acids.

754 CHAPTER 23
Other Important Lipids
Compound saponifiable lipids play an important role in biochemical
processes. These lipids are structurally similar to triglycerides in that at
SCllNKS. Dmtoped and luirtainrd by
NalKMJi SotiKf Trackers Auouatioa
least one fatty acid is bonded to the central glycerol or glycerol-like unit. For a variety of links related to this
.
These molecules may also have phosphate groups sugar units. or nitrogen - chapter, go to wvAV. scilinks . org
b
containing groups. Phospholipids, shown in Figure 6, are compound Topic: Function of the Cell
saponifiable lipids and are the main structural component of cell mem - Membrane
branes. Phospholipids are arranged in a bilayer; or double layer at the,
Sci Links code: HC60627
surface of the cell. As Figure 6 shows, the hydrophilic heads of the phos -
pholipids are on the outside surfaces of the bilayer. The heads are in
contact with water-containing solutions inside of the cell and surround-
ing the cell. The hydrophobic tails point toward the interior of the mem -
brane. away from water-containing solutions. The cell membrane forms
a boundary between the cell and its external environment . Only certain
.
substances may pass through the cell membrane This enables the cell to
maintain a stable internal environment .
Nonsaponiflable lipids are nonpolar compounds that do not form
soap. They include steroids, many vitamins, and bile acids. Cholesterol is
a steroid present in animal cell membranes and is a precursor of many
hormones.

I FIGURE 6

1 Polar -
Polar
head

- Nonpolar
- Non - -

polar
tails
- Polar
A phospholipid's " head " Phospholipids are arranged in a bilayer, with
is polar, and its two fatty the hydrophilic heads pointing outward and
" tails " are nonpolar. the hydrophobic tails pointing inward.

SECTION REVIEW Critical Thinking

1. Describe two functions of carbohydrates in living 4. ANALYZING RELATIONSHIPS Glucose is soluble in
systems. water. Why is cellulose, which is made up of glu-
2. Carbohydrates make up about 2 % of the mass of cose, insoluble in water ?
the human body, yet we need about 1 tsp of glu- 5. EVALUATING IDEAS Carbohydrates make up about
cose every 15 min to maintain energy for our cells. 90% of the mass of cotton. Why don't humans
Where does all of this glucose come from? include cotton in their diet ?
3. What is the difference between saponifiable and
nonsaponifiable lipids?

BIOLOGICAL CHEMISTRY 755

 SECTION 2
Amino Acids
OBJECTIVES
J Describe the basic structure of
and Proteins
amino acids and the forma -
tion of polypeptides.

^ Determine the significance of

A mino acid molecules are the basic building blocks of proteins.
amino acid side chains to the Although only 20 types of amino acids are found in human proteins,
three- dimensional structure of more than 700 types of amino acids occur in nature. The human body
a protein and the function of can synthesize only 11 of the 20 amino acids as needed. The other nine,
a protein. called the essential amino acids, have to be supplied bv the food that
we eat .
Describe the functions of pro-
teins in cells.

Amino Acids
v Identify the effects of enzymes
on biological molecules. Amino acids are organic molecules that contain two functional groups: a
—
basic NH2 amino group and an acidic COOH carboxylic acid group.
All of the 20 amino acids have the general structure shown in Figure 7.
The * * R " represents a side chain that is different for each amino acid.
FIGURE 7 Amino acids have the The R -groups of the amino acids present in a protein determine the
same basic structure. The R repre - protein's biological activity. The structures of four amino acids —cys-
sents a side chain. teine, valine, glutamic acid, and histidine —are shown below.

H R SH
s
.
CH3
\
N CH , cit

/ ITN — C — COOH H2N — C— COOH

II H II
II
or cysteine valine

R
II,N — C —COOH
II
VOH
CH,
CH ?
IFN— C — COOl I
H:N — C — COOII
II I
!1
glutamic acid
histidine

756 CHAPTER 23
Amino Acid Reactions
Two amino acids can react with each other in an acid-base reaction sim -
ilar to those discussed in Chapter 14. Hie basic amino group of one
amino acid reacts with the acidic carboxylic acid group of another
amino acid, forming a peptide, and a molecule of water is lost.This reac -
tion. shown below, is classified as a condensation reaction because the
two amino acid molecules join together, and water is formed. The bond
formed is called a peptide bond , and the product is a dipeptide because
it is made up of two amino acid units. Longer chains are called polypep -
tides , and chains of 50 or more amino acids are called proteins.

peptide bond

O
/ \
H O H H H H

dipeptide

Peptide bonds can be broken by enzymes called proteases. These

enzymes are found in cells and tissues where they aid in the digestion of
proteins from food, or where they degrade unneeded or damaged proteins.

Proteins
Proteins are found in all living cells and are the most complex and var -
ied class of biochemical molecules. A protein is an organic biological
polymer that is made up of polypeptide chains of 50 or more amino acids
and is an important building block of all cells. The name protein comes
from the Greek proteins, which means “of first importance.* This name
*

was chosen to show the importance of proteins in living things.

Proteins are the second most common molecules found in the human
body ( after water ) and make up about 10% to 20% of the mass of a cell.
Made up of specific sequences of amino acids, proteins have molecular
masses that range from 6000 to more than 0 million atomic mass units.
About 0000 different protein molecules are found in cells in the human
body. Nitrogen accounts for about 15 % of the mass of a protein mole -
cule. which makes the structure of a protein quite different from that of
a carbohydrate or lipid. Most proteins also contain sulfur, and some
contain phosphorus or other elements, such as iron. zinc, and copper.
The importance of proteins in living things comes from their many
different functions. Besides being the body 's main food source for nitro- Of wlopfd M4 MMtiuml fcy Ifcr
mtiwul Sonut lc«dwn AttouatlM
gen and sulfur, proteins have many important catalytic, structural, regu- For a variety of links related to this
lator } . and antibody defense functions. Some different kinds of proteins chapter go to wvvw.sciljnks.org
are keratin, which is the main component of hair and fingernails; Topic: Protein Synthesis
enzymes, which catalyze biochemical reactions; hemoglobin , which car - SciLinks code: HC61240
ries oxygen in the blood; insulin, which regulates glucose levels: and
antibodies, which protect the body from foreign substances.

BIOLOGICAL CHEMISTRY 757

 Arrangement of Amino Acids
in Peptides and Proteins
Each peptide, polypeptide, or protein is made lip of a special sequence of
amino acids. A simple set of three-letter abbreviations is used to represent
each amino acid in these kinds of molecules. For example, the dipeptide
from glycine, shown in Figure 8, and glutamic acid would be written as
GIv-Glu . The dipeptide Glu-Glv is an isomer of Gly-GIu. Both have the
same numbers of C, M . O, and N atoms but in a different order. For the
tripeptide Val-Asp-His. made up of valine, asparagine, and histidine, there
are five isomers. There are 120 possible isomers for a pentapeptide of five
different amino acids. Even though there are only 20 types of amino acids
in proteins found in the human body, an incredibly large number of
polypeptide and protein molecules are possible. Even for a small protein
made up of 100 amino acids, the number of possible combinations of the
,
20 amino acids is 20 m! Polypeptide and protein function depend not only
on the kinds and number of amino acids but also on their order. Later, you
will see that even the difference of only one amino acid in a polypeptide
or protein chain can cause a big change in a protein s activity in a cell .
FIGURE 8 A scanning electron
micrograph showing crystals of the Amino Acid Side - Chain Reactions
amino acid glycine , one of the build -
—
The properties of amino acids and ultimately polypeptides and pro-
ing blocks of proteins.
—
teins depend on the properties of the side chains present. For example,
the side chain of glutamic acid is acidic, and the side chain of histidine is
basic. The side chains of asparagine and several other amino acids are
polar. In addition, both glutamic acid and asparagine can form hydrogen
bonds, shown in Figure 9. Some amino acid side chains can form ionic or
covalent bonds with other side chains. Cysteine is a unique amino acid ,
because the -SH group in cysteine can form a covalent bond with anoth -
—
er cysteine side chain . Figure 9 shows that two cysteine units at different
FIGURE 9 Iliree kinds of interac-
tions between side chains on a —
points on a protein molecule can bond to form a disulfide bridge. Such
bonding can link two separate polypeptides or can cause one long protein
polypeptide molecule are shown
to bond onto itself to form a loop. In fact. curly hair is a result of the pres-
here. These interactions help deter -
mine the shape of a protein . ence of many disulfide bridges in hair protein.

Hydrophobic
environment
Disulfide bridge Hydrogen bonds
( covalent bond )
CH 3 H3C II
II H C-CH , —
H 3C C II I
N— H
C — S — S —C I! H c c — H H

— ——
I I
H II II
o c c c-
valine valme H 6 HI HI
cysteine cysteine asparagine glutamic acid

Polypeptide

758 CHAPTER 23
 Shape and Structure of Protein Molecules
The interaction of amino acid side chains determines the shape and
structure of proteins, which in turn are important to the proteins’ bio-
logical functions. In a polypeptide chain or protein, the sequence of the
amino acids is called the primary ( I ' ) structure.' The secondary ( 2 ) struc-
ture describes how the chain is coiled or otherwise arranged in space. For
example, the alpha ( or ) helix is a secondary structure that resembles a
coiled spring. Another type of secondary structure is the beta ( j i ) pleat -
ed sheet which has accordion- like folds. Both of these secondary struc -
,

tures form because hydrogen bonding occurs between a hydrogen atom

attached to the nitrogen atom in one peptide bond and the oxygen atom
of another peptide bond farther down the backbone of the protein.
In a protein the amino acid side chains project out in such a way that
,

they often interact with other side chains located at various positions
along the protein backbone. These interactions give the protein its char -
acteristic three - dimensional shape, which is called its tertiary (3 ) struc-
ture. The side -chain interactions can include hydrogen bonding, salt
bridges, and cysteine-cysteine disulfide bonds. Hydrophobic interac -
tions that occur between nonpolar side chains also contribute to a pro-
tein's tertiary structure. Because nonpolar side groups are repulsed by
the water found in cells and body fluids, these groups tend to be found
in the interior of the protein, where contact with water is minimal. Polar
and ionic side chains tend to be on the protein surface, where they are
in contact with water. In some proteins, different polypeptides, each of
which has its own 3 structure, come together. In the case of hemoglo-
bin. four different polypeptides make up the quaternary ( 4°) structure.
The four structural levels of proteins are shown in Figure 10.

FIGURE 10

’ ’
\ s
"

*
• . . - VSS
a ) Primary Structure

d) Quaternary
Structure

b) Secondary Structure

c) Tertiary Structure

BIOLOGICAL CHEMISTRY 759

 TABLE 1 Biological Functions of Proteins
Type of Protein Function Examples
Storage storage of amino Casein protein in milk supplies amino acids for baby mammals.
acids Egg white protein , or ovalbumin , is a source of amino acids for
developing embryos. Plants store proteins in seeds.
Transport transport of Proteins transport molecules across cell membranes.
substances Hemoglobin in blood transports oxygen .
Structural support Spiders produce silk fibers, which are proteins, to make webs.
Collagen and elastin give connective tissues strength and
flexibility. Keratin is found in hair , feathers, horns, hooves,
and nails.
Contractile movement Actin and myosin fibers cause movement in muscles. Contractile
fibers in cilia and flagella help propel single-celled organisms.
Enzymatic catalysis of chemical Enzymes break down large molecules in food within the
reactions digestive system .
Hormonal coordination of Pancreatic insulin helps regulate blood -sugar levels.
processes in an
organism
Receptor response of cell to Nerve cell membranes have chemical receptors that
chemical stimuli detect chemical signals released by other nerve cells.
Defensive protection against Antibodies attack pathogenic viruses and bacteria.
disease

Biological Functions of Proteins

From Table 1 , you can see that almost everything that occurs in a living
organism depends on one or more proteins. Scientists have discovered
that the specific function of a protein is related to the protein 's shape.
The shape of a protein can generally be described as fibrous or globu -
lar . Fibrous proteins are insoluble in water and are long. thin , and phys-
ically strong. Globular proteins are generally soluble in water and are
twisted and folded into a globe-like shape.
Fibrous proteins give strength and protection to structures in living
things. Keratin is a fibrous protein whose secondary structure is almost
entirely alpha helical in shape. The keratin in nails and hooves is much
stil ler than the keratin in fur or wool because of the large number of side-
chain interactions that occur between the nail and hoof proteins. Collagen ,
found in bone and tendons, is a triple helix of three intertwined alpha
helices, which gives these tissues their strength. Fibrin found in silk has a
beta - pleated sheet structure. Elastins in blood tissue, fibrins in blood clots,
and myosins found in muscle tissue are other kinds of fibrous proteins.
Globular proteins regulate body functions, catalyze reactions, and
transport substances. The regulatory hormone insulin is a small protein
of 51 amino acids in two polypeptide chains. Myoglobin transports oxy -
gen in the muscles, and hemoglobin transports oxygen in the blood .
Casein, found in milk and used for food , is also a globular protein. It
contains phosphorus, which is needed for bone growth.

760 CHAPTER 23
Amino Acid Substitution
A protein 's amino acid sequence determines its three -dimensional
structure, which in turn determines its function. Even a single substitu-
tion of one amino acid for another can change the shape and function
of a protein. For example, the genetic disease sickle cell anemia can hap -
pen when one amino acid—glutamic acid—is replaced bv a molecule of
valine. This change in only 1 of 146 amino acids in one of the two pro-
tein chains in the hemoglobin molecule causes a major change in the
shape of the molecule. This change in the shape of the hemoglobin mol-
ecule causes the red blood cells to sickle when oxygen levels are rela-
tively low ( as is the case in most body tissues). The sickled cells tend to
clog small blood vessels, which prevents the transport of enough oxygen
to tissue cells. As a result, people who have sickle cell anemia suffer from
.
shortness of breath Figure 11 shows the shape of normal red blood cells
and sickled cells. The sickle cell gene is more common in some groups of
people than it is in others. In areas where the disease malaria is common,
scientists have discovered that sickled cells are more resistant to malari -
.
al infection than other cells are So, people who have sickle cell anemia
are more resistant to malaria than other people are.

I FIGURE 11

H
V°
CH2
CH,
H2N— C—COOH
H
glutamic acid

(b) Hemoglobin consists of (c) Each of the chains is a poly -

( a) The round, flat shape of healthy red blood four polypeptide chains; the mer of 141 or 146 amino acid
cells shows they have normal hemoglobin area where the change in sickle units, such as the glutamic acid
molecules. cell hemoglobin occurs is monomer shown here.
shown in green.

,
’CvCH/
H CH

H,N — C—COOH
H
valine

(e) A genetic mutation causes (f ) The sickle shape of the cell

one glutamic acid to be comes from the different shape of
(d) Because of their shape, sickle cells clog replaced by valine in the the hemoglobin caused by the
small blood vessels. hemoglobin molecules, as substitution of valine for glutamic
shown in red. acid.

BIOLOGICAL CHEMISTRY 761

 ISTORICAL CHEMISTRY

Dr. Charles Drew and Blood Transfusions

Prior to the 1900 s, severe bleeding many as 50% of hemophiliacs in the
often resulted in death. But today United States could have been infect-
blood is stored at blood banks, where ed with HIV because of their frequent
people " deposit " blood so that they transfusions. Although current screen-
or others can " withdraw " it when ing procedures to detect HIV, hepatitis,
needed. Charles Drew was a pioneer and other diseases have almost com-
in the work of blood transfusions,
1 pletely removed the risk of transfusing
especially in the use of plasma and infected blood, some people choose to
the development of blood banks. bank their own blood before undergo-
ing surgery.
The Need for Blood
While in medical school, Drew real - Blood Substitutes
ized that many lives could be saved The AIDS epidemic has sped up
if blood could be stored for transfu- attempts to find an artificial blood
sions. Before 1937, most patients substitute. Perfluorocarbons ( PFCs),
needing blood received it directly Charles Drew was a pioneer in the which are made by replacing the
development of blood banks.
from a donor at the time it was hydrogen atoms of hydrocarbons
needed. In 1938, Drew and physician also found that plasma could be with fluorine atoms, are possible
John Scudder from Britain studied dehydrated and stored. substitutes. Oxygen binds to PFCs
the chemistry of blood to try to find During World War II, Drew was the 10 to 20 times more readily than it
a way to preserve blood. Drew rec - medical supervisor for the " Blood for binds to plasma or water, and prod -
ognized that extracting blood plas- Britain " program. He also coordinat- ucts using PFCs have a shelf life of
ma could help solve the problems of ed the American blood storage up to two years. Another substitute
storing blood. program by setting up collection is a hemoglobin -based oxygen carri -
There are two main components centers, standardizing blood bank er ( HBOC). HBOCs may be able to
of blood: blood cells and plasma. equipment, and establishing record- transport oxygen until a body is able
Red blood cells, white blood cells, keeping procedures and criteria to to replenish its red blood cells. If
and platelets make up 45% of the ensure the safety of blood products. these products are successful, they
volume of blood, while plasma When the United States entered the could provide a supply of blood sub-
makes up 55 % of blood. Plasma is war, the blood supply was ready, and stitutes that do not require typing
amber colored and is about 90% stored blood and plasma saved sev - and do not depend on donors.
water. It has more than 100 solutes, eral thousand lives.
including nutrients, antibodies, hor -
A Safer Blood Supply
Questions
mones, and proteins. Drew discov - 1. What was Dr. Drew's contribu-
With the emergence of HIV and AIDS
ered that plasma could be used as tion to medicine?
in the 1980s, the methods of blood
an emergency substitute for blood
transfusion needed to be modified. 2. Why are scientists searching for
without testing for blood type,
Some transfused blood was found to blood substitutes ?
because the ABO blood types are
be contaminated with HIV. Before
removed with the red blood cells. He
modifications were put into place, as

762 CHAPTER 23
 Proteins as Enzymes
An enzyme is a prowin that analyzes a biochemical reaction. Enzymes
make up the largest and most highly specialized class of proteins. All liv -
ing things have enzymes: as many as 30( H) enzymes can be found in a sin-
gle cell. Most enzymes are water-soluble, globular proteins. The amino
acid side chains and the three-dimensional shape of enzymes play a very
important role in the enzymatic activity. You will remember from
( hapter 17 that catalysts speed up a reaction but do not change as a result

of the reaction. An enzyme also does not change the amount of product
that is formed in a reaction; it only decreases the time it takes to form the
product. Enzymes catalyze both decomposition and synthesis reactions.
Enzymes are also very efficient. For example, the enzyme carbonic
anhydrase acts on carbonic acid to break it down into carbon dioxide
and water. A single molecule of carbonic anhydrase can break down
36 million carbonic acid molecules in I minute ! Carbon dioxide is car -
ried from all the parts of the body to the lungs as carbonic acid in the
blood. In the lungs, carbonic acid is broken down by carbonic anhydrase
into C02 and water vapor and then is removed from the lungs as a per -
son exhales .
Enzyme Specificity
In addition to being highly efficient, enzymes are very specific. Often, they
catalyze just a single reaction as carbonic anhydrase does. In another
example, the enzyme peroxidase is responsible only for the decomposition
of hydrogen peroxide to water and oxygen. Have you ever put hydrogen
peroxide on a minor cut? In the bottle, hydrogen peroxide is relatively sta-
ble. but as soon as it comes into contact with your wound, the peroxidase
enzyme in the blood catalyzes its decomposition. You see bubbling, which
is the result of the gaseous oxygen from the decomposing hydrogen per -
oxide. As you can see in Figure 12, enzymes act by binding to a specific
substrate molecule. For example, hydrogen peroxide is the substrate in the

FIGURE 12

( a) The enzyme reacts with the (b) The substrate - enzyme .

( c ) . . . proceed to the products
substrate in a fast, reversible complex can either revert to
reaction. the reactants o r . . .

BIOLOGICAL CHEMISTRY 763

 reaction just discussed . The shape of the
Activation Energy With and Without an Enzyme
enzyme is such that a molecule of
hydrogen peroxide can fit into the
-o Activation energy enzyme at a specific part of the enzyme
JD without an enzyme molecule, called the active site. The
a; o
c
LU
_
i/
Q
.
u

>
resulting compound is called the
Activation energy enzyme -substrate complex. In the
with an enzyme
enzyme-substrate complex, hydrogen -
>N o Reactants oxygen bonds break , and oxygen -
CD \OJA
<D 01
oxygen bonds form . Then, the enzyme
c
LU d) releases the products and is ready to
react with another substrate molecule.
^ Products
This model of enzyme action is called
Reaction progress the lock aml key model.

FIGURE 13 Enzymes decrease Enzymes and Reaction Rates

the activation energy of a chemical The presence of an enzyme in a chemical reaction can increase the rate
reaction. However, the energy
of a reaction by a factor of up to lO20. In Chapter 17. you saw that a reac-
change from reactants to products is
the same for both the catalyzed and
tion can occur when two atoms or molecules collide. But only collisions
the non -catalvzed reaction. that have enough energy to overcome the activation energy and have
the proper orientation change reactants into products. As you can see
from the graph in Figure 13, an enzyme that catalyzes a chemical reac-
tion causes an increase in the rate of the reaction by reducing the acti -
vation energy. The enzyme lowers the activation energy by forming the
enzyme-substrate complex , which makes breaking bonds in the reac-
tants and forming new bonds in the products easier. The net amount of
energy required for the reaction or released by the reaction is not
changed by the action of an enzyme.

Temperature and Enzyme Activity

FIGURE 14 Most enzymes have
maximum activity within a narrow
Proteins, including enzymes, are also affected by changes in tempera -
ture. The graph in Figure 14 shows the relatively narrow range of tem -
temperature range. Denaturation in
many occurs at temperatures above peratures within which enzymes typically have maximum activity.
50 ( and causes a decrease in activity. Enzymes in the human body work optimally at the normal body tem -
perature of 37 C ( 98.6° F ). At temperatures above 50°C to 60°C
Enzyme Inhibition enzymes typically show a decline in activity. High heat can denature, or
alter, the shape of a protein , which in turn alters the protein s function .
'

Denaturation is a change in a protein 's characteristic three -dimensional

shape due to changes of its secondary tertiary. and quaternary structure.
If you have ever cooked an egg. you have caused protein denaturation .
The white of an egg is a solution of the protein albumin . When the egg
is placed in a hot frying pan. a dramatic change takes place and the
semitransparent solution turns into a white solid . Because the primary
structure is retained in denaturation, the nutritional value of the egg
white is not affected . The process is not reversible, however, cooling a
fried egg does not reverse the denaturation . When food is cooked , the
20 40 60 80
-
three dimensional structure of the protein is altered , making the food
.
T C easier to digest .

764 CHAPTER 23
pH and Enzyme Activity
Enzymes also typically have maximum activity within a relatively nar -
row range of pH. The optimal pH for normal cell enzyme functions is
almost neutral, about 7.3 to 7.4. Changes in pH can cause changes in
protein structure and shape. For example, adding acid or base can inter -
fere with the side -chain interactions and thus change the shape of a pro-
tein. Most enzymes become inactivated, or no longer work, because of
denaturation when the pH changes. When milk sours ( because lactic
acid has formed ), it curdles, and curds of the protein casein form. Yogurt
is made by growing acid-producing bacteria in milk, which causes the
casein to denature, giving yogurt its consistency.
The digestion of dietary protein bv enzymes begins in the stomach.
When food is swallowed, the stomach lining produces HCI and pre-
enzymes, inactive forms of protein-digesting enzymes. These pre -
enzymes travel from the stomach lining into the stomach before they
become activated by the stomach's low pH of 1.5 to 2.0. This process is
important because it prevents the active form of the enzymes from
digesting the stomach lining. A layer of mucus protects the lining of the
stomach from the enzymes it contains. Once activated, the enzymes
catalyze the breakdown of the proteins in food into shorter polypep-
tide segments. Pepsin is a stomach enzyme found in adults. The partial -
ly digested protein in food travels into the small intestine, where the
pH is 7 to S. Under these conditions, the enzyme trypsin becomes
active. It catalyzes the hydrolysis of the polypeptide segments into
amino acids, which are absorbed through the intestinal wall and enter
the bloodstream. The body uses these newly acquired amino acids to FIGURE 15 The fish treated with
make other amino acids and new protein molecules. Figure 15 shows lime has turned white because the
how the protein in raw fish looks before and after it is soaked in acidic acidic lime juice denatures the pro-
lime juice. Because the acidic lime juice denatures protein in the fish, tein in raw fish.
the acid - treated fish looks very different .

SECTION REVIEW Critical Thinking

1. Which elements do amino acids and proteins have 5 . RELATING IDEAS Explain how the ball- like struc -
in common with carbohydrates and lipids? ture of globular proteins allows them to be water
2. What is the difference between an amino acid and soluble.
a protein ? 6. INFERRING CONCLUSIONS If an essential amino
3. Explain the difference between fibrous proteins acid is in short supply in the diet, it can become a
and globular proteins. limiting reactant in building any protein that con-
tains the amino acid. Explain why, under these
4. Why are only small amounts of enzymes found in conditions, the only way that the cell could make
the body ? that protein would be to degrade one of its pro-
teins that contain the limiting amino acid.

BIOLOGICAL CHEMISTRY 765

SECTION 3
Metabolism
OBJECTIVES
SJ Describe the role of ATP in
cells. M etaholism is the sum of nil the chemical processes that occur in an
organism. Complex molecules are broken down into smaller ones
Explain how energy is released through catabolism, and simple molecules are used to build bigger ones
by metabolic reactions. through a process called anabolism. A metabolic pathway is a series of
linked chemical reactions that occur within a cell and result in a specif -
ic product or products. The major metabolic pathways for most organ -
j Summarize the relationship isms are similar. So. one can study the basic metabolic pathways in
between anabolism and simple organisms to get information about the reactions in organisms
catabolism.
that are more complex, including humans.

ATP: Energy for the Cell

SCllNKS D vtiop«4
*
kV ft
uiii<ii««d ky Ike
Mtftoul $o«Kt tocken AIMCUMM Just as it takes energy to run a chemical factory, cells require energy to
For a variety of links related to this make the proteins, carbohydrates, lipids, and nucleic acids that are nec -
chapter, go to www.scilinks.org
essary for life. In addition, the body needs energy as heat to keep warm,
Topic : Exothermic and mechanical energy to move muscles and pump blood, and electrical
Endothermic Reactions
energy to move ions across cell membranes. The original source for
SciLinks code: HC60555
almost all of the energy needed by living systems is the sun. Autotrophs,
such as plants, algae, and photosynthetic bacteria, can use sunlight,
water , and CO:to make carbon-containing biomolecules, including car -
bohydrates. This process is called photosynthesis and occurs in the cells
of plants and algae, such as those shown in Figure 16, within structures
called cliloroplasts. Chloroplasts contain chlorophyll, an organic mole -
FIGURE 16 The cells of algae and
cule that absorbs solar energy. This energy is captured immediately in
green plants contain chlorophyll, the
two compounds, one of which is adenosine triphosphate ( ATP ). ATP
green pigment that absorbs light
energy from the sun. is a high -energy molecule that plant cells use to make carbohydrates.
The other compound, known as NAD PH . is also used in carbohydrate -
forming reactions.
Unlike plants, animals cannot use the sun s energy to convert C():
into food. Animals must get the energy that they need to sustain life by
consuming plants and other animals. Living things, including most
microorganisms, which depend on plants or other animals for food , are
called heterotrophs. Heterotrophs use the energy obtained in the
breakdown of complex molecules to drive chemical reactions in cells.
The carbohydrates, lipids, and amino acids that heterotrophs consume
undergo several energy - yielding reactions as they break down into sim-
pler molecules. Some of this energy is stored in the ATP molecules,
which cells use to drive a wide variety of metabolic reactions .
CHAPTER 23
 Light FIGURE 17 ATP is formed
energy by photosynthesis or catabo -
lism . Cell activities that
require energy are powered
by ATP hydrolysis. " P,"
represents a phosphate.
ATP hydrolysis
releases energy for
Photosynthesis Catabolism Biosynthesis
The ATP Cycle Osmotic work
Cell motility/muscle
contraction

Energy Activities
The cycle between ATP and ADP, adenosine diphosphate, is the prima -
ry energy exchange mechanism in the body. Figure 17 provides an
overview of the ATP cycle in cells. In this energy cycle. ATP is the mol-
ecule that serves to carry energy from energy-storing molecules, carbo-
hydrates. lipids, and proteins to specific energy -requiring processes in
cells. When ATP is hydrolyzed to ADP, energy is released to power the
cell 's activities. The molecular structures of ATP and ADP are closely
related, as shown in Figure IS.
The difference in the number of phosphate groups between ATP and
ADP molecules is the key to the energy exchange in metabolic reac -
tions. The chemical equation below shows the hydrolysis reaction bv
which ATP is converted into ADP and a phosphate group (represented
by the gold-colored ball in Figure 17 ). The free energy for this reaction
is -31 kJ, which is the amount of energy available to do work .

ATPUaq ) + H :0 ( / ) > ADP3 ( aq ) + H:PC> 4 ( aq ) AG = -31 kJ

"

FIGURE 1B The hydrolysis of

ATP produces ADP and releases
energy.

Adenosine triphosphate ( ATP ) Adenosine diphosphate ( A D P )

BIOLOGICAL CHEMISTRY 767

 FIGURE 19 Catabolic CELL MACROMOLECULES
ENERGY- YIELDING
pathways release free ener - NUTRIENTS Proteins
gy in the form of ATP and
Carbohydrates Polysaccharides
NADH. Anabolic pathways Fats Lipids
consume energy released Proteins Nucleic acids
by catabolic
pathways.
ATP
Catabolism Anabolism
(oxidative, CHEMICAL
(reductive,
exergonic) ENERGY
endergonic)

NADH

ENERGY- POOR END PRECURSOR MOLECULES

PRODUCTS Amino acids
H 20 Sugars
co2 Fatty acids
NH3 Nitrogenous bases

Catabolism
SC
/ lNKS.] Dmlopcd and nuMtimcd by HM
The energy that your body needs to maintain its temperature and drive
its biochemical reactions is provided through catabolic processes.
Nitio«ijl feitfKt TeariNn AMOtiJtiM

For a variety of links related to this

Figure 19 illustrates the relationship between the pathways of catabo-
chapter, go to . . j lism and anabolism. Catabolism is the part of metabolism in which com -
Topic: Food as Fuel
SciLinks code: HC60591
^ piex compounds break down into simpler ones and is accompanied by
the release of energy. First, enzymes break down the complex com -
pounds in food—carbohydrates, fats, and proteins—into simpler
. J molecules.
Carbohydrate digestion begins in the mouth, where the enzyme amy -
lase in saliva begins to break down polysaccharides. The food then pass-
es through the esophagus, then the stomach,and into the small intestine.
Here, additional enzymes are secreted to complete the hydrolysis of
carbohydrates to form glucose and other monosaccharides.
Digestion of fats occurs only in the small intestine. Protein digestion
begins in the stomach and is completed in the small intestine. During
the digestion of both fats and proteins, complex molecules hydrolyze
into simpler ones. Fats are broken down into fatty acids and glycerol.
Proteins are broken down into amino acids.
These products are absorbed across the wall of the small intestine
into the blood and are transported to cells. Once in the cells, each glu -
cose molecule is broken down through glycolysis into two molecules of
pyruvate, which enter the mitochondria and feed into a complex series
of reactions called the citric acid cycle, or Krebs cycle. Hie citric acid
cycle produces carbon dioxide and other molecules, such as NADII and
ATP. This NADH and ATP then move through another set of reactions
to produce more ATP and water.

768 CHAPTER 23
 The amount of energy released in catabolism depends TABLE 2 Approximate "Cost"
on the amount of ATP that is made as the products of of Daily Activities
digestion are oxidized. The catabolism of 1 glucose mole-
cule generally may produce up to a total of 36 ATP mol - Energy ATP
Activity required (ki) required (mol)
ecules. This accounts for about 40% of the energy
released by the complete oxidation of glucose. Most of Running 1120 56
the energy not converted to ATP is lost by the body as Swimming 840 42
energy in the form of heat . Table 2 shows how much ATP Bicycling 1400 70
is needed for some daily activities.
Walking 560 28

Anabolism
Cells use the simple molecules that result from the breakdown of food
to make larger, more complex molecules. Energy released during catab -
olism powers the synthesis of new molecules as well as the active trans -
port of ions and molecules across cell membranes. Anabolic processes
are the energy -consuming pathways by which cells produce the mole-
cules that they need for sustaining life and for growth and repair. The
conversion of small biomolecules into larger ones is called anabolism.
In an anabolic pathway, small precursor molecules are converted into
complex molecules, including lipids, polysaccharides, proteins, and
nucleic acids. Energy from ATP and NADH is necessary for these
biosynthesis reactions to occur. Figure 19 illustrates that catabolism and
anabolism occur simultaneously and that ATP and NADH serve as
chemical "links ” between the two processes.
One important anabolic pathway that is common to animals, plants,
.
fungi, and microorganisms is gluconeogenesis As the name implies, glu-
cose is synthesized in this pathway from non-carbohydrate substances,
including lactate, pyruvate, glycerol, and most of the amino acids. In
mammals, glucose from the blood is the fuel source for the brain and
nervous system as well as for the kidney medulla, red blood cells, and
embryonic tissues .

SECTION REVIEW 5. Why are diets that are severely restrictive in carbo-
1. List four ways in which the body uses energy. hydrate intake potentially dangerous to a person's
health?
2. What is the total energy (in kilojoules) stored in the
36 ATP molecules that are made from the metabo- Critical Thinking
lism of 1 molecule of glucose in skeletal tissue? 6. RELATING CONCEPTS When a molecule of glucose
3. The teeth break large pieces of food into smaller is oxidized, only about 40% of the energy is cap -
ones. However, this process is not considered part tured in ATP molecules, and the rest is lost as
of digestion. Explain why. energy in the form of heat. What do you think
4. How does the digestion of fat in a strip of ham dif- would happen if this energy remained in the body
fer from the digestion of starch in a piece of toast ? as heat ?

BIOLOGICAL CHEMISTRY 769

 SECTION 4
Nucleic Acids
OBJECTIVES
yj Describe the structure of the
nucleic acids DNA and RNA . N ucleic acids contain all of the genetic information of an organism.
They are the means by which a living organism stores and conveys
>j Explain the functions of DNA instructional information for all of its activities. They are also the means
and RNA in the cell. by which an organism can reproduce. The two nucleic acids found in
organisms are deoxyribonucleic acid ( D N A ) and ribonucleic acid
( R N A ).
^ Describe applications of mod-
ern gene technology.

Nucleic Acid Structure

A nucleic acid is an organic compound , either RNA or D N A , whose
molecules carry genetic information and is made up of one or two chains
of monomer units called nucleotides. However , unlike the monomer
units in polysaccharides and polypeptides, each nucleotide monomer
can be further hydrolyzed into three different molecules. A nucleotide
molecule is composed of a five-carbon sugar unit that is bonded to both
a phosphate group and a cyclic organic base containing nitrogen.
.
The sugar unit in DNA is deoxyribose and the sugar unit in RNA is
ribose. The diagram below shows the sugar- phosphate arrangement in
three nucleotides.
- phosphate-sugar- phosphate-sugar- phosphate-sugar-

base base base

FIGURE 20 There are five com - The five nitrogenous bases found in nucleic acids are shown in
mon nitrogenous bases. Thymine Figure 20. Adenine ( A ) , guanine ( G ) , and cytosine ( C ) are found in both
.
( T ), cytosine ( C ) and uracil ( U ) DNA and RNA . Thymine ( T ) is found only in DNA . and uracil ( U ) is
have a single six- member ring. found only in RNA .
Adenine ( A ) and guanine ( G ) have
a six - member ring connected to a
five - member ring.

adenine guanine cytosine thymine uracil

770 CHAPTER 23
 DNA: Deoxyribonucleic Acid
Every single instruction for all of the traits that you have inherited and all
of the life processes that occur in your cells is contained in your DNA . It SCllNKS. LV ft
Dntloptd and MMMDH fey DM
MATRONAL Some Iracfean Aivxiatkro
is no wonder then that DNA molecules are the largest molecules found
For a variety of links related to this
in cells. Living organisms vary widely in the size and number of DNA
molecules in their cells. Some bacterial cells contain only 1 DNA mole-
chapter, go to • links.org -
Topic: DNA
cule. while human cells contain 4b relatively large DNA molecules. Each SciLinks code: HC60418
human cell contains about 2 m of DNA. which is divided and packed into Topic: DNA Replication
the cell's 4b chromosomes. An average cell is only about b / / m in diame- Sci Links code: HC60420
ter and contains many organelles and structures. To fit in a cell, DNA
must undergo extensive twisting, coiling, folding, and wrapping.
The Swedish scientist Friedrich Miescher first extracted DNA from
cells in 1 X68. but its three-dimensional structure was not discovered
until 1953. Using the X -ray data of Maurice Wilkins and Rosalind
Franklin, James Watson of the United States and Francis Crick of
England proposed that DNA was a double helix. In this structure, which
has been confirmed by numerous methods, two strands of the sugar-
phosphate backbone are wound around each other, and the nitrogenous
bases point inward, as shown in Figure 21. rhe sequence of these
nitrogenous bases along the phosphate-sugar backbone in DNA forms
the code responsible for transferring genetic information. The three -
dimensional DNA molecule is similar to a twisted ladder. The sides of
the ladder are the sugar-phosphate backbone, and the rungs are base
pairs of A -T ( adenine-thymine) or G-C ( guanine - cytosine ) bases
extending between the two backbones. Hydrogen bonding between
these pairs of nitrogenous bases holds the rungs of the ladder together.

FIGURE 21 Hydrogen bonding between base pairs makes

the three- dimensional structure of DNA stable. Base pairing
occurs between adenine and thymine or guanine and cytosine,
keeping the distance between the strands constant .

Adenine

Guanine

y
V

Cytosine

BIOLOGICAL CHEMISTRY 771

 FIGURE 22 The double helix of
Nitrogenous Base Pairs
DNA can be seen by using scanning In the DNA double helix, base pairing
tunneling microscopy ( STM ). exists only between A I and between
—
C G. as you saw in Figure 21. The rea -
son is that the pairing between one
single - ringed base and one double -
ringed base provides the correct orien -
tation for the hydrogen bonds to form
between the two sides of the DNA lad -
der. One thymine and one adenine
form a link between the two strands of
a DNA molecule that is exactly the
yrTld 11
^ same size as the link formed by one
cytosine and one guanine.
Historical Chemistry
Go to go. hrw. com for full -length
The double - helix configuration of
article on the discovery of the struc- DNA . shown in Figure 22, can be seen
ture of DNA . by using a scanning tunneling microscope ( STM ). The discovery of the
relative quantities of the nitrogenous bases A . T, G , and C present in
Keyword: HC 6 BI0 X
DNA was the key to determining the three-dimensional molecular
structure. Analysis of DNA from different organisms reveals that the
amounts of A\ and T are the same and that the amounts of G and C are
the same for all members of the same species. In humans, DNA is
about 30% A , 30% Tt 20% G . and 20% G
The interaction between base pairs accounts for the ability of DNA to
replicate, as you will see in the next section. Just as combinations of the
26 letters of the alphabet form words that tell a story in a novel , combi -
FIGURE 23 DNA replicates .
nations of the four-letter alphabet of A T, G. and C form the genes that
when its double helix unwinds and define our heredity. Each gene is a section of DNA that contains a spe-
becomes single stranded . The single cific sequence of four bases ( A. G. T. and C ) and encodes instructions for
strands are used as a template for protein synthesis. As of 2004, researchers with the Human Genome
the formation of new complemen - Project had discovered that the human body contains about 20 000 to
tary strands.
25 ( KK ) genes.

DNA Replication
Original Like the two sides of a zipper, the two strands of the double helix of
DNA are not identical. Instead , the two strands are complements ol
each other. Thus, a base on one strand is paired through hydrogen bond -
ing to its complementary base on the other strand. For example, if one
strand sequence is AGCTC, the complementary strand sequence will be
TCGAG.
Each time a cell divides, an exact copy of the DNA of the parent cell
^^Complementarystrand
*
S| is reproduced for the daughter cells. The process by which an identical
' copy of the original DNA is formed is called DNA replication. As repli -
V cation begins, a portion of the two strands of the original DNA unzips,
m’ as shown in Figure 23. Each strand can then act as a template for the
V synthesis of a new, complementary strand . The result is two new DNA
New molecules, which have the same base pair sequence as the original dou -
helixes ble helix.

772 CHAPTER 23
 RNA: Ribonucleic Acid
RNA molecules are responsible for the synthesis of proteins, which in
turn control the operation and function of the cell . RNA differs from
DNA in lour basic ways: ( 1 ) the sugar unit in the backbone of RNA is
ribose rather than deoxyribose. ( 2 ) RNA contains the base uracil , U,
instead of thymine, which occurs in DNA . (3 ) RNA is a single-stranded
molecule rather than a double -stranded helix like DNA . and
( 4 ) RNA molecules typically consist of 75 to a few thousand nucleotide
units rather than the millions that exist in DNA. Even though RNA is
much smaller than DNA . RNA is still large enough to twist , coil. bend ,

and fold back onto itself. In fact , it is not uncommon for up to 50% of an
RNA molecule to have a double- helix structure. The reason is that the
base sequences along the helical regions of the RNA strand are comple -
mentary. which makes hydrogen bonding between bases possible.

Synthesis of RNA
RNA is synthesized in the nucleus of eukaryotic cells, where DNA
and protein molecules actually help synthesize specific RNA mole -
cules. RNA can also be seen by STM . as shown in Figure 24. As RNA
is synthesized , some information contained in the DNA is transferred
to the RNA molecules. Like the genetic information of DNA , the
genetic information of RNA is carried in its nucleotide sequence.
One type of RNA molecule is called messenger RNA ( mRNA )
because it carries the instructions for making proteins out into the
cytosol , where proteins are produced on ribosomes. A ribosome is a
cell organelle that is composed of RNA and protein. Ribosomes are the
main site of protein production in cells. The DNA template is also
used to make two other types of RNA molecules: ribosomal RNA
( rRNA ) and transfer RNA ( tRNA ) . Both of these types of RNA also
leave the nucleus and come together in the ribosome where they help FIGURE 24 Scanning tunneling
synthesize proteins. Ribosomal RNA becomes part of the structure of micrograph of RNA strands being
the ribosome , and tRNA is used to transfer amino acids into the ribo - transcribed in a cell .
some. Only mRNA carries the coded genetic
information that is translated into proteins.
DNA supplies all of the information necessary
for RNA to be used to make the proteins needed
by the body. The portion of DNA that holds the
specific genetic code for a single, specific mRNA
molecule is a gene. As you learned previously,
each gene is a section of the DNA chain that con -
tains a specific sequence of the bases A. G, T. and
C. A gene has the information necessary in this
sequence to direct RNA to produce several pro-
teins that have specific functions.

BIOLOGICAL CHEMISTRY 773

 RNA and Protein Synthesis
CAREERS in Chemistry RNA is made from DNA in a process that is similar to how DNA repli-
.
cates itself At a gene, aportion of DNA unwinds and RNA is assem -
Forensic Chemist bled using the same complementary base pairs as DNA except that
A forensic chemist applies scientific uracil replaces the thymine. When a signal to stop is received, the RNA
methodology to physical evidence. is released. As in DNA replication, the RNA sequence that forms has
Forensic chemists focus on analyzing the complementary base pairs of the DNA gene. The DNA sequence
evidence that has been collected at a
crime scene. They then report any con - below would form the complementary RNA sequence shown.
clusions that they can draw from the
analysis. Understanding evidence DNA strand: C C C C A C C C T A C G G T G
requires knowledge of biology, materi - RNA strand: G GG G U G G G A U G C C A C
als science, and genetics in addition to
chemistry. Because forensic chemists
A sequence of three bases in mRNA codes for a specific amino acid.
are often asked to testify in court, they
need to be comfortable speaking in Thus, the sequence CAG codes for glutamic acid, and GUC codes for
public and able to give clear and con- valine. There are 64 ( 4 \) unique combinations of three - base sequences
cise explanations to those who do not made from four bases. Because only 20 amino acids require codes, some
have a background in science. of the amino acids have more than one code. For example, leucine is
coded by six three-base sequences: UUA, UUG, CUU, CUC, CUA. and
CUG. The genetic code is universal, meaning that the same three-base
sequence always codes for the same amino acid regardless of whether
the organism is a bacterium or a human. The "stop ” signal in the gene is
also a three-base code: UAG, UAA. or UGA.

Technology and Genetic Engineering

The discover)' of DNA's function in life has provided new options for
the production of food, medical diagnosis and treatments, and increased
.
understanding of genetic disorders Scientists in the field of genetic
engineering study how manipulation of an organism's genetic material
can modify the proteins that are produced and the changes that result
in the organism. Although the selective breeding of plants and animals
has been practiced for hundreds of years, today genetic engineering
refers to recombinant DNA technology that is used for cloning and the
creation of new forms of life. Because the technique is so powerful, it is
controversial and must be used responsibly.

DNA Fingerprinting
One of the most visible uses of molecular technology is DNA finger -
printing. DNA is unique to an individual except for identical twins. This
technology is used in criminal investigations and victim identification.
Often there are only very small samples available,such as a single drop of
blood or one strand of hair. The technique of the polymerase chain reac-
tion ( PCR ) may be used to copy a DNA sample to supply sufficient DNA
FIGURE 25 A DNA autoradi-
ograph shows the pattern of DNA for identification. The processes of electrophoresis and autoradiography
fragments of an organism after they may be used to compare DNA from a sample with the DNA of a known
have been separated from each individual to confirm identification, as Figure 25 shows. DNA technology
other hv electrophoresis. can also be used to test paternity or to trace heredity.

774 CHAPTER 23
Cloning
One meaning of the word cloning is the process of making an exact copy
o f an organism. One example of a natural occurrence of cloning, the for -
mation of identical twins, is the result of a chance splitting of the embry -
onic cells very early in the growth of a zygote. Artificial cloning, using
stem cells from animals or meristem cells from plants, can produce iden -
tical replicas of the parent cells or. under specialized conditions, a com -
plete organism that is identical to the original organism. The orchid
shown in Figure 26 is a clone of its parent plant. Cloning of plants may
hold promise for increasing the yields of crops. Recently, scientists at
Pennsylvania State University cloned cocoa plants from cocoa flowers.
When cocoa trees are planted from seed, as many as 50% do not mature
with the desired characteristics. My planting young trees that are clones of
plants with desirable characteristics, farmers may be able to increase their
cocoa production.
FIGURE 26 Growers can produce
The first animal to be cloned, a sheep named Dolly, was born in 1996
many orchids by artificial cloning of
in Scotland. Dolly was euthanized in 2003 because of lung disease. She the meristem tissue of a single
had also been diagnosed with arthritis. Both diseases are normally orchid plant .
found in sheep older than Dolly was.

Recombinant DNA Technology

Recombinant DNA technology has been used to insert DNA from one
organism into another. One technique involves splicing a gene from one
organism's DNA into a molecule of DNA from another organism.
Escherichia coli. a bacterium found in animal intestinal tracts, are often
used by biologists as cellular factories for the production or manufac -
ture of DNA fragments cloned from other organisms. In some instances,
/:. coli can even be used to produce protein from DNA cloned from
other organisms.
One of the first applications of genetic engineering was the synthesis
of human insulin. Previously, most diabetics had to use either pig or cow
insulin. But insulin from animals is not exactly the same as human
insulin. Today, most insulin used is produced in bacteria and harvested.
Human growth hormone is also commercially produced by using
recombinant DNA technology.

SECTION REVIEW 4. Why is a very small trace of blood enough for DNA
.
1 What sugar is present in DNA ? What sugar is pre - fingerprinting?
sent in RNA ?
Critical Thinking
.
2 Explain why the two strands of the DNA double
5. INTERPRET AND APPLY Is it possible to specify
helix are said to be complementary instead of
identical. 20 amino acids by using only two base pairs
instead of three for coding?
3. Describe how DNA uses the genetic code to con-
trol the synthesis of proteins. 6. DRAWING CONCLUSIONS Why is the arrangement
of base pairs that is found in DNA ideal for holding
the double helix of DNA together ?

BIOLOGICAL CHEMISTRY 775

 CHAPTER HIGHLIGHTS
Carbohydrates and Lipids
I Vocabulary •Carbohydrates are nutrients that are produced by plants and
carbohydrate are made up of carbon, oxygen, and hydrogen.
monosaccharide •Monosaccharides are the simplest carbohydrates.
disaccharide Carbohydrates made of two monosaccharides are called disac -
condensation reaction charides, and carbohydrates made of more than two monosac -
hydrolysis charides are called polysaccharides .
polysaccharide •Carbohydrates undergo condensation reactions and hydrolysis
lipid reactions.
fatty acid •Lipids are a varied group of biochemical molecules that have a
saponification high percentage of C and H atoms.

Amino Acids and Proteins

I Vocabulary •Amino acid molecules are the basic building blocks of proteins.
amino acid •Proteins are biopolymers, each of which has a unique sequence
protein of the acid monomer molecules.
enzyme •The specific function of a protein is related to the shape of the
denaturation protein.
•Side-chain interactions between amino acids result in sec-
ondary. tertiary, and quaternary protein structures.

Metabolism
I Vocabulary •ATP is a high-energy storage compound that the body uses to
metabolism store and provide energy for life.
autotroph •The metabolic pathways involve both the conversion of ATP
adenosine triphosphate ( ATP) to ADP and the conversion of ADP to ATP.
heterotroph •Metabolic pathways are classified as two types: catabolism and
adenosine diphosphate ( ADP) anabolism.
catabolism •Catabolism includes reactions in which large molecules are
anabolism changed into simpler molecules. These reactions release energy.
•Anabolic processes are energy-consuming pathways by which
cells produce the molecules needed for growth and repair.

Nucleic Acids
I Vocabulary •Deoxyribonucleic acid ( DNA ) and ribonucleic acid ( RNA ) are
nucleic acid nucleic acids, the compounds by which living organisms can
DNA replication reproduce themselves.
cloning •Nucleic acids are polymers of monomer units called nucleotides .
•The two strands of the double helix of DNA are complemen-
tary to each other, not identical. These strands are held togeth-
er by hydrogen bonding of the base pairs.
•RNA is used as a template to produce proteins in the cell.

776 CHAPTER 23
 CHAPTER REVIEW

Carbohydrates and Lipids .

14 Explain the cause of the genetic disease sickle
cell anemia.
SECTION 1 REVIEW 15. Why is the water solubility of fibrous proteins
so different from that of globular proteins?
1. Describe the general chemical formula of
carbohydrates.
2. Name two examples from each of the following PRACTICE PROBLEMS
classes of carbohydrates: monosaccharides, dis - 16. Draw the structures of two dipeptides made up
accharides. and polysaccharides. of glycine and valine.
3. What different roles do the polysaccharides 17. I low many different tripeptides can be formed
starch and cellulose play in plant systems? from two molecules of glycine and one mole -
4. What word is used to describe fatty acids that cule of cysteine ? Write all of the structures by
contain at least one double bond? using the three-letter codes Gly and Cvs.
5 . Why are some triglycerides liquid, while others
are solid?
6. What reagents are used to make soaps? Metabolism
SECTION 3 REVIEW
PRACTICE PROBLEMS
18. What chemical gains the metabolic energy that
7. Draw the structural formula for glucose. is released as glucose is broken down in the
8. Using structural formulas, write the equation
body ?
showing the formation of maltose, which is the 19. What does ATP stand for ? What is the role of
disaccharide made of two glucose units. ATP in living things ?
9. Write the equation representing the formation 20. Describe the steps that occur in the digestion of
of a soap molecule from stearic acid . fats.
C17H3SCOOH, and sodium hydroxide. .
21 Review the following diagram of catabolism.

glucose
Amino Acids and Proteins glycogen proteins

SECTION 2 REVIEW
10. Describe the structure of an amino acid. Then,
fats glycerol -
+
* I
amino acids
fatty acids
explain how amino acids become linked togeth- pyruvate
er to form a protein.
11. Circle and identify the carboxylic acid acetate
groups and the amino groups in the following I
molecule:
r
ATP 1
O H O H production

NTT — CH — C — N — CM — C — N — CH — COOH
CH , CH — OH CH, According to the diagram, what could happen
in the cell when glucose and glycogen reserves
COOH CH , C — NIT
are nearly gone ?
O

12. Can two types of enzymes contain the same PRACTICE PROBLEMS
number and kinds of amino acids? Explain. 22. Draw the structure of ATP Circle the bond that
.
13 What happens when a protein is denatured ? breaks when A DP forms.

BIOLOGICAL CHEMISTRY 777

 CHAPTER REVIEW

33 . Is each of the following statements about pro-

Nucleic Acids teins and triglycerides true or false ?
SECTION 4 REVIEW a. Both contain the amide functional group.

23. What are the three components of a nucleotide? b. Both are a part of a major class of biochemi-
24. I low are the two polynucleotide chains of DNA cal molecules.
c. Both hydrolyze in order to enter the mela-
held together ? * v

25 . Describe in general terms the process of DNA bolic pathway in humans.

34. Circle the hydrophobic part in each of the fig-
replication.
26 . What are the main differences between DNA ures shown below.
and RNA ? a. H3C CH3
\ X
27 . Describe the similarities and differences C II
between the three kinds of RNA molecules. .
H N— C — COOH
28. What is a ribosome? What is the function of a Ii
ribosome in a cell ?

PRACTICE PROBLEMS
b- HO
\
c
/>
29. The following sequence of bases might be found H— C-H
on the gene that codes for oxytocin, the human H— C — H
pituitary hormone:
H —C— H
TACACAATGTAAGTTTTGACGGGGGAC-
CCTATC H—C — H
a. What is the sequence of bases on the com - H— C — H
plementary strand of DNA ? H— C — H
b. What is the sequence of bases that would
occur on a strand of mRNA that was tran -
— —
H C H

scribed from the oxytocin DNA sequence? H— C

H— C
H— C — H
MIXED REVIEW H-C-l l
30. Name the four main elements that make up H —C— H
compounds found in living organisms. H — C— H
31 . In each of the following groups, one of the
H — C- H
items does not belong in the group. Identify the
odd item in the group and explain why it is dif - H— C — H
ferent . Explain how the other items are related. H— C — H
a. glycogen, starch, fructose, and cellulose
H — C —H
b. amino acids, dipeptides, polypeptides, and
II
proteins
c. fats. oils, and fatty acids
d. cytosine, adenine, and guanine
32. What is the human body ’s storage form of each
of the following?
a. glucose
b. lipids
c. protein

778 CHAPTER 23
 CHAPTER REVIEW

.
35 Both celery and potato chips are composed of 41. Using Analogies Explain why the model of
molecules that are polymers of glucose. Explain enzyme action is called the “lock and key *’
why celery is a good snack for people on a diet model.
while potato chips are not.
.
36 Carbohydrates* fats, and proteins can provide
energy lor an organism. RESEARCH & WRITING
a. Which class of substances most rapidly pro -
vides energy? 42. Conduct library research about how Olestra
b. Which class can be used as a building materi- decreases fat and caloric content of potato
al in the human body ? chips. What are the advantages and disadvan-
c. Which is the most efficient as an energy stor - tages of Olestra in food products?
age system? .
43 Write a summary discussing what you have
.
37 Describe the basic structure of the cell learned about the four major classes of organic
membrane. What is the cell membranes compounds found in living things—carbohy -
main function? .
drates lipids, proteins, and nucleic acids. Include
a description of how these organic molecules
are used bv the bodv.
CRITICAL THINKING
.
38 Interpreting Concepts A diet that consists ALTERNATIVE ASSESSMENT
primarily of corn can result in a protein-
deficiency disease called kw ashiorkor . What .
44 Amylase, the enzyme present in the mouth, cat -
does this information indicate about the protein alyzes the digestion of starch. Hie pH of the
content of corn? mouth is almost neutral.
.
39 Inferring Relationships Explain how a similar a. Do you think that amylase is active in the
reaction forms three kinds of biological poly - stomach after you swallow the food? Why or
mers: polysaccharides, polypeptides, and nucleic why not?
acids. b. Design an experiment you could perform to
test your answer to item a. Note: A common
40. Evaluating Ideas Some diets recommend test for the presence of starch is the addition
severely restricting or eliminating the intake of of tincture of iodine, which will produce a
carbohydrates. Why is it not a good idea to elimi - blue color if starch is present.
nate all carbohvdrates from the diet ?

BIOLOGICAL CHEMISTRY 779

 Math Tutor INTERPRETATION OF THE GENETIC CODE

In protein synthesis, the DNA sequence of bases is transcribed onto messenger RNA
(mRNA). The mRNA base sequence is the complement of the DNA sequence except
that uracil takes the place of thymine as the complement of adenine.

Problem-Solving TIPS
• Find the first base of the mRNA triplet along the left side of the table.
• Follow that row to the right until you are beneath the second base of the triplet.
• Move up or down in the square that corresponds to the second base until you are
even, on the right side of the chart , with the third base of the triplet.

The Genetic Code ( mRNA )

First Second base Third

base U C A G base
vvv Phenylalanine ucu UAU
TVrosine
UGU
Cvsteine
U
l VC LC ( l AC UGC * C
U Serine
lieA l AA UGA —Stop A

—
It A
Leucine Stop
DUG UCG DAG : GG Tryptophan G
CUU ecu CAU CCH U
Histidine
< l < ccc ( At * CGC C
C Leucine Proline Arginine
CIA
Cl
AUU
( . CCA
CCC*
ACU
. CAA
.
( AC *

A AD
Glutamine
CGA
CGG
AGU
G
U
A

Asparagine Serine
At C Isoleucine ACC AAC AGC C
A Ilireonine
\l
AUG Start
GUI T
A
—
ADA
ACG
GCU
AAA
A AG
GAli
Lysine
AGA
AGC
GGU
. Arginine
A
G
U
Aspartic acid
GDC GCC G \< GGC | C
G Valine Alanine Glvcine
CiDA GCA GAA GGA A
Glutamic acid
GDG GCG GAG CiGG G

SAMPLE
What sequence of amino acids will be incorporated into protein as a result of the mRNA
sequence UU ACCCG A G A A G UCC?
Divide the sequence into groups of three to clearly see the separate codons.
UUACCCG AG A AGUCC = UUA l CCC I GAG I A AG I UCC
Now, use the table to determine the match between codons and amino acids.
UUA I CCC GAG I AAG I UCC
leucine proline glutamic acid lysine serine

PRACTICE PROBLEMS
.
1 What amino acid sequence will be added to a 2. What amino acid sequence will be added to a
protein as a result of the mRNA sequence protein as a result of the mRNA sequence
UUACACGACUAUAAUUGG? CUAACCGGGUGAGCUUCU?

780 CHAPTER 23
^ n 12 1

^{
8
7 5

Answer the following items on a separate piece of paper. .

7 Which of the following statements about fats is
true?
MULTIPLE CHOICE
A. Fats serve as a reserve supply of energy.
.
1 Which of the following statements about B. Fats are stored in the adipose tissue.
enzymes is true?
C. Fats act as insulators.
A . Enzymes can be biological catalysts.
D. All of the above
B. Enzymes increase the speed of a chemical
reaction. 8. When carbohydrates are unavailable or unable
to provide the energy needs of the body.
C. Enzymes are highly specific.
D. All of the above A . glucose is converted to glycogen.
B. proteins or fats are used for energy.
.
2 Which of the following statements about dena - C. amino acids form proteins.
turing is true?
D. All of the above
A . Denaturing occurs when a protein unfolds.
B. Denaturing occurs when a carbohydrate is 9. Which of the following statements is true ?
heated, A . RNA contains the base uracil rather than
.
C Denaturing does not affect the tertiary struc - thymine, which occurs in DNA .
ture of an enzyme. B. Both RNA and DNA are double-stranded
D . Denaturing increases the rate of a chemical helixes.
reaction. C. The rihose sugar unit is in the backbone
of DNA .
.
3 The process in which molecules in a cell break
D. None of the above
down to produce smaller molecules and energy
is called SHORT ANSWER
A . glycogenesis. 10. Draw a simple dipeptide, and label the function -
B. biosynthesis. al groups and peptide linkage.
C. catabolism.
D. metabolism.
.
11 Describe the shape of the DNA molecule, and
discuss how the DNA molecule is held in this
.
4 Which of the following is partially digested by shape.
saliva in the mouth? EXTENDED RESPONSE
A. glucose
B. starch .
12 The body has numerous energy reserves. What
are they, and where are they found in the body ?
C. fat
Which of these reserves provides the greatest
D. protein
source of quick energy ?
5. In the human body, the storage form of
A . glucose is maltose.
.
13 Explain how it is possible to denature a protein
without breaking the polypeptide chain.
B. triglycerides is protein.
C. carbohydrates is glycogen.
D. nucleic acids is amino acids.
.
6 The purpose of insulin is to
A . regulate glucose levels in the body.
B. catalyze the oxidation of fatty acids.
C. stimulate RNA production.
D. initiate DNA replication. If a question or an answer
choice contains an unfamiliar term, try to break the
word into parts to determine its meaning.

BIOLOGICAL CHEMISTRY 781

 SEE PRE- LAB
EXPERIMENT 23 EXTRACTION AND FILTRATION

Casein Glue
OBJECTIVES BACKGROUND
• Recognize the structure of a protein. Cow s milk contains averages of 4.4 % fat , 3.8% pro-
tein. and 4.9 % lactose. At the normal pH of milk ,
• Predict and observe the result of acidifying
6.3 to 6.6, the protein remains dispersed because it
milk .
has a net negative charge due to the dissociation of
• Prepare and test a casein glue. the carboxylic acid group, as shown in Figure A below.
• Deduce the charge distribution in proteins As the pH is lowered bv the addition of an acid , the
as determined by pH . protein acquires a net charge of zero, as shown in
Figure B. After the protein loses its negative charge, it
MATERIALS can no longer remain in solution , and it coagulates
into an insoluble mass. The precipitated protein is
KM ) inL graduated cylinder
known as casein and has a molecular mass between
250 ml . beaker 75 000 and 375 000 amu. The pH at which the net
250 inL Erlenmeyer flask charge on a protein becomes zero is called the iso-
electric pH . For casein , the isoelectric pH is 4.6.
funnel
glass stirring rod
hot plate —
H:N - protein | COO ‘
H ,N — protein - COO
FIGURE A FIGURE B
medicine dropper
baking soda, NaHCOj
In this experiment , you will coagulate the protein
nonfat milk in milk by adding acetic acid . Hie casein can then be
paper separated from the remaining solution by filtration .
paper towel This process is known as separating the curds from
the whey. The excess acid in the curds can be neutral -
thermometer ized by the addition of sodium hydrogen carbonate.
white vinegar NaHC03. The product of this reaction is casein glue.
Do not eat or drink any materials or products of this
wooden splints, 2
lab.

SAFETY

For review of safety, please see Safety in the

Chemistry Laboratory in the front of vour book .

782 CHAPTER 23
 EXPERIMENT 23

PREPARATION FIGURE C
Paper
Use a folded
1. Prepare your notebook for recording observa - towel
paper towel
tions at each step of the procedure. in the funnel
to separate
2. Predict the characteristics of the product that the curds. Curds
will be formed when the acetic acid is added
to the milk . Record your predictions in your
notebook .

PROCEDURE
1. Pour 125 mL of nonfat milk into a 250 mL beaker.
Add 20 mL of 4 % acetic acid ( white vinegar ). Whey

2. Place the mixture on a hot plate and heat it

to 60°C. Record your observations in your lab
notebook , and compare them with the predic -
tions you made in Preparation step 2.
3 . Filter the mixture through a folded piece of
paper towel into an Erlenmeyer flask , as shown 2. Evaluating Methods: In this experiment , what
in Figure C. happened to the lactose and fat portions of
4. Discard the filtrate, which contains the whey.
the milk ?
Scrape the curds from the paper towel back into
the 250 mL beaker. CONCLUSIONS
5. Add 1.2 g of NaHC03 to the beaker and stir. 1. Inferring Conclusions: Figure A shows that the
Slowly add drops of water, stirring intermittent - net charge on a protein is negative at pH values
ly. until the consistency of white glue is obtained . higher than its isoelectric pH because the car -
boxyl group is ionized . Figure B shows that at
6. Use your glue to fasten together two pieces of the isoelectric pH , the net charge is zero. Predict
paper. Also fasten together two wooden splints. the net charge on a protein at pH values lower
Allow the splints to dry overnight , and then test than the isoelectric point , and draw a diagram
the joint for strength . to represent the protein .

CLEANUP AND DISPOSAL

7. Clean all apparatus and your lab
EXTENSIONS
station . Return equipment to its proper 1. Relating Ideas: Figure B represents a protein
place. Dispose of chemicals and solu - as a dipolar ion. or zwitterion . The charges in
tions in the containers designated by your a zwitterion suggest that the carboxyl group
teacher. Do not pour any chemicals down the donates a hydrogen ion to the amine group. Is
drain or in the trash unless your teacher directs there any other way to represent the protein in
you to do so. Wash your hands thoroughly before Figure B so that it still has a net charge of zero?
you leave the lab and after all work is finished.
2. Designing Experiments: Design a strength -
testing device for the glue joint between the
ANALYSIS AND INTERPRETATION two wooden splints. If your teacher approves
1. Organizing Ideas: Write the net ionic equation your design , create the device and use it to
for the reaction between the excess acetic acid test the strength of the glue.
and the sodium hydrogen carbonate. Include the
physical states of the reactants and products.

BIOLOGICAL CHEMISTRY 783

 Elements Handbook
CROUP 1 ALKALI METALS 786 CROUPS 3-12 TRANSITION METALS 798
APPLICATIONTechnology APPLICATIONGeology
Sodium Vapor Lighting 788 Gemstones and Color 801
APPLICATION Health APPLICATION Technology
Electrolyte Balance in the Body 789 Alloys 802
APPLICATIONThe Environment
CROUP 2 ALKALINE EARTH METALS 792 Mercury Poisoning 805
APPLICATION Technology APPLICATION Health
Fireworks 794 Elements in the Body 806
APPLICATION Health Role of Iron 807
Calcium: An Essential
Mineral in the Diet 796 CROUP 13 BORON FAMILY 808
Magnesium: An Essential
Mineral in the Diet 796 Technology
APPLICATION
Aluminum 810
Aluminum Alloys 811

784 ELEMENTS HANDBOOK

GROUP 14 CARBON FAMILY 812 GROUP 15 NITROGEN FAMILY 828
APPLICATION Chemical Industry APPLICATION Biology
Carbon and the Reduction Plants and Nitrogen 830
of Iron Ore 814
APPLICATION Chemical Industry
Carbon Dioxide 815 Fertilizers 831
Carbon Monoxide 815
APPLICATION Biochemistry GROUP 16 OXYGEN FAMILY 832
Carbon Dioxide and Respiration 816
Macromolecules 819
APPLICATION Chemical Industry
Oxides 834
APPLICATION The Environment
Carbon Monoxide Poisoning 818 APPLICATION The Environment
Ozone 836
APPLICATION Chemical Industry
APPLICATION Chemical Industry
Silicon and Silicates 825 Sulfuric Acid 837
Silicones 825
APPLICATIONTechnology
GROUP 17 HALOGEN FAMILY 838
Semiconductors 826
APPLICATION The Environment
Chlorine in Water Treatment 840
Fluoride and Tooth Decay 841

ELEMENTS HANDBOOK 785

 GROUP 1
ALKALI METALS

3
CHARACTERISTICS Li
Lithium
• do not occur in nature as free elements 6.941

• are reactive metals and are obtained by reducing

|He|2s
' Atomic radius
the 1+ ions in their natural compounds ii increases
Na
• are stored under kerosene or other hydrocarbon Sodium
solvent because they react with water vapor or 22.989 770
Ionic radius
oxygen in air INeps1
increases
• consist of atoms with one electron in the K
19

outermost energy level Potassium

39.0983 Chemical reactivity
• form colorless ions in solution , each of which has [ Ar )4 s i increases
a 1+ charge
37
• form ionic compounds Rb
Rubidium Electronegativity
• form water-soluble bases 854678 decreases
• are strong reducing agents |Kr]5s
'
55
• consist of atoms that have low ionization energies Cs Ionization energy
• are good heat and electrical conductors Cesium
132.905 43 decreases
• are ductile , malleable, and soft enough to be cut [ Xe|6 s
with a knife 87

• have a silvery luster low density, and low melting

, Fr
Francium
point ( 223 )
[ Rn|7 s

Lithium was discovered in 1817. It is found Sodium derives its name from the word Potassium was first isolated in 1807 from
in most igneous rocks and is used in bat* soda. It was first isolated in 1807 from the the electrolysis of caustic potash, KOH .
teries as an anode because it has a very low electrolysis of caustic soda, NaOH. Sodium
reduction potential. Lithium is soft and is is soft enough to be cut with a knife. It is
stored in oil or kerosene to prevent it from shiny until it reacts with oxygen, which
reacting with the air. causes the surface to lose its luster.

786 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

COMMON REACTIONS
With Water to Form Bases and Hydrogen Gas
Example: 2Na(.v ) + 21 LO( / ) > 2NaOH ( tf </ ) + H2(g)
Li. K , Rh, and Cs also follow this pattern.

With Acids to Form Salts and Hydrogen Gas

Example: 2 N ’t\( s ) + 21 lCl ( aq ) » 2NaCl(«r/ ) + H2(g)
Li. K, Rh. and Cs also follow this pattern.

With Halogens to Form Salts

Example: 2N \
< ( s ) + F2( g) 2NaF(.v ) A small piece of potassium dropped into water will
Li, K. Rh, and Cs also follow this pattern in reacting react explosively, releasing H2 to form a strongly
basic hydroxide solution. The energy of the reac-
with F:, Cl2, Br:. and I2.
tion ignites the hydrogen gas that is produced.

With Oxygen to Form Oxides, Peroxides, or Superoxides

Lithium forms an oxide.
4Li(.v) + 02(g) > 2LLO( .v)
Sodium also forms a peroxide.
2Na(.y ) + 02(g) > Na202(s)
Alkali metals with higher molecular masses can also
form superoxides.
K (.y) + 02(g) > K02(5)
Rh and Cs also follow this pattern.
Sodium reacts vigorously with chlorine to produce
NaCI. Most salts of Group 1 metals are white
Alkali- Metal Oxides with Water to Form Bases crystalline compounds.
Oxides of Na, K . Rh, and Cs can be prepared indirectly.
These basic anhydrides form hydroxides in water.
Example: K :Q ( s ) + lLO( / )
* 2KOH( a q )
Li. Na. Rh. and Cs also follow' this pattern.

ANALYTICAL TEST

Alkali metals are easily detected by flame tests

because each metal imparts a characteristic
color to a flame.
When sodium and potassium are both
Lithium Sodium
present in a sample, the yellow color of
the sodium masks the violet color of the
potassium. The violet color can be seen
only w hen the combined sodium-potassium
flame is viewed through a cobalt -blue glass.
The glass blocks the yellow flame of sodium
and makes it possible to see the violet flame
i
of potassium.

Potassium Rubidium Cesium

ALKALI METALS 787

 ELEMENTS HANDBOOK

PROPERTIES OF THE CROUP 1 ELEMENTS

Li Na K Rb Cs Fr

Melting point (°C) 180.5 97.8 63.25 38.89 28.5 27

Boiling point (°C) 1342 882.9 760 691 668 677

Density (g/cm3) 0.534 0.971 0.862 1.53 1.87

Ionization energy ( kJ/mol ) 520 496 419 403 376
Atomic radius ( pm ) 152 186 227 248 265 270
Ionic radius ( pm ) 76 102 138 152 167 180

Common oxidation number in compounds +1 +1 +1 +1 +1

Crystal structure bcc * bcc bcc bcc bcc

Hardness ( Mohs ' scale ) 0.6 0.4 0.5 0.3 0.2

*bodv -centered cubic

APPLICATION Technology
Sodium Vapor Lighting The light intensity per watt for sodium vapor
The flame test for sodium shows two bright lines at lamps far exceeds that of fluorescent lamps, high-
589.0 and 589.6 nm, which is the yellow range of the pressure mercury vapor lamps, tungsten halogen
emission spectrum. Sodium can be vaporized at high lamps, and incandescent bulbs.
temperatures in a sealed tube and made to give off
light using two electrodes connected to a power
source. Sodium vapor lighting is often used along
highways and in parking lots because it provides
good illumination while using less energy than other
types of lighting.
Sodium vapor lighting comes in both low-pressure
and high-pressure bulbs. Low pressure lamps reach
-
an internal temperature of 270°C to vaporize the
sodium under a pressure of about 1 Pa. High-pressure
lamps contain mercury and xenon in addition to sodi-
um. These substances reach an internal temperature
of 1100°C under a pressure of about 1( X ) (MX ) Pa. The
high-pressure lamp provides a higher light intensity.
The design of both types of lamps must take into
account the high reactivity of sodium, which increases
at high temperatures. Because ordinary glass will
react with sodium at 250°C. a special sodium-resistant
glass is used for low-pressure lamps. High-pressure
lamps use an aluminum oxide material for the column
containing the sodium, mercury, and xenon. Both
types of lamps contain tungsten electrodes.

788 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

APPLICATION Health
Electrolyte Balance in the Body
The elements of Group 1 are important to a person’s TABLE 1 A Sodium- Potassium
diet and body maintenance because they form ionic Concentration in Body Fluids
compounds. These compounds are present in the Inside cells Outside cells or in plasma
body as solutions of the ions. All ions carry an elec- Cation ( 1111110I/L ) ( nimol/L )
tric charge, so they are electrolyte solutes. Two of Na 4 12 145
the most important electrolyte solutes found in the
body are K and Na * ions. Both ions facilitate the
' K+ 140 4
transmission of nerve impulses and control the
amount of water retained by cells. The sodium and potassium ion concentrations in
body fluids are shown in Table 1 A. Sodium ions are
found primarily in the fluid outside cells, while
potassium ions are largely found in the fluid inside
cells. Anions are present in the fluids to balance the
electrical charge of the Na 4 and 1C cations.
Abnormal electrolyte concentrations in blood
serum can indicate the presence of disease. The ion
concentrations that vary as a result of disease are
Na . K \ Cl , and HCO3. Sodium ion concentration is
* ”

a good indicator of the water balance between blood

and tissue cells. Unusual potassium ion levels can
indicate kidney or gastrointestinal problems.
Chloride ion is the anion that balances the positive
charge of the sodium ion in the fluid outside the cells.
It also diffuses into a cell to maintain normal elec -
During situations where the body is losing water rapidly through trolyte balance when hydrogen carbonate ions diffuse
intense sweating or diarrhea for a prolonged period ( more than 5 out of the cell into the blood. Table 1 B shows med-
hours ), a sports drink can hydrate the body and restore electrolyte ical conditions associated with electrolyte imbalances.
balance.

TABLE 1 B Electrolyte Imbalances

Causes of imbalance
Electrolyte Normal range ( mmol/L ) Excess DeficiencyV

Sodium, Na 4
135- 145 hypernatremia (increased hyponatremia (dehydration;
urine excretion; excess diabetes-related low blood
water loss ) pH; vomiting; diarrhea )
Potassium, K 3.5-5.0 hyperkalemia ( renal hypokalemia
failure; low blood pH) ( gastrointestinal conditions )
Hydrogen carbonate, 24-30 hypercapnia ( high blood hypocapnia ( low blood pH:
HCO3 pH; hypoventilation ) hyperventilation; dehydration )
C hloride, Cl 100-106 hyperchloremia hypochloremia
(anemia; heart conditions; ( acute infection; burns;
dehydration ) hypoventilation)

ALKALI METALS 789

 ELEMENTS HANDBOOK

Sodium- Potassium Pump normal operation of the nervous system . This

in the Cell Membrane unequal concentration of ions creates a voltage
The process of active transport allows a cell to across nerve cell membranes. When a nerve cell is
maintain its proper electrolyte balance. To keep stimulated , sodium ions diffuse into the cell from the
the ion concentrations at the proper levels shown surrounding fluid , raising voltage across the nerve
in Table IB, a sodium - potassium pump embedded cell membrane from -70 mV to nearly +60 mV.
in the cell membrane shuttles sodium ions out of Potassium ions then diffuse out of the cell into
the cell across the cell membrane. A model for the surrounding fluid , restoring the voltage across the
the action of the sodium - potassium pump is nerve cell membrane to -70 mV. This voltage fluctua -
shown below. tion initiates the transmission of a nerve impulse.
The amount of Na + inside the cell has increased
Nerve Impulses and Ion Concentration slightly, and the amount of K outside the cell has
'

The difference in Na and K concentrations inside

* 4

decreased. But the sodium - potassium pump will

and outside nerve cell membranes is essential for the restore these ions to their proper concentrations.

(a) Naf binds to the pump, which stimulates a

Concentration outside the cell
reaction that changes the shape of the pump.
Na = 145 mmol/L
K = 4 mmol/L

OUTSIDE
( d ) This reaction causes K * to be
expelled into the cell.

( b ) When the
INSIDE
Concentration inside the cell pump changes
Na * = 12 mmol/L shape, it expels
K ' = 140 mmol/L Naf outside of
the cell.

The sodium - potassium pump is a

protein embedded within the cell (c) The new shape of the protein allows it to bind
membrane that allows the passage of with K \ which stimulates another reaction to
Na + and K* into and out of the cell. Each change the protein's shape.
figure depicts the action of a single protein .

790 ELEMENTS HANDBOOK

16 L sivi 3w iivxiv

Answers 1 . e: 2. c: 3. b: 4. c; 5. c: 6. all of them: 7. d: 8. b. processed foods can

contain very high levels of sodium: 9. a. b, c: 10. Salt is not pure sodium.

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 GROUP 2
ALKALINE EARTH
METALS
4
CHARACTERISTICS Be
Beryllium
• do not occur naturally as free elements 9.012 182
[He] 2s 2
• occur most commonly as the carbonates, Atomic radius
phosphates, silicates, and sulfates 12 increases
Mg
• occur naturally as compounds that are either Magnesium
24.3050
insoluble or only slightly soluble in water
lNe!3$ 2
Ionic radius
• consist of atoms that contain two electrons in their 20 increases
outermost energy level
Ca
Calcium
• consist of atoms that tend to lose two electrons 40.078
per atom , forming ions with a 2+ charge [ Ar ]4s
Chemical reactivity
• are less reactive than alkali metals 38
increases
• form ionic compounds primarily Sr
Strontium
87.62
• react with water to form bases and hydrogen gas |Kr ]5s 2 Electronegativity
• are good heat and electrical conductors 56
decreases
• are ductile and malleable Ba
Barium
• have a silvery luster 137.327
[ Xel6s Ionization energy
• include the naturally radioactive element radium 88
decreases

Calcium carbonate is a major component of marble.

Beryllium is found in the

Ra
Radium
( 226)
[ Rn)7s 2 \
mineral compound beryl.
Beryl crystals include the
dark green emerald and
the blue - green aquama-
rine. The colors of these
gems come from other
metal impurities.

The mineral
dolomite,
CaC03' MgC03 , is a
natural source of
both calcium and
magnesium.

792 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

COMMON REACTIONS
With Water to Form Bases and Hydrogen Gas
Example: Mg(s) + 2H:0( / ) > Mg(OH ) 2( aq ) + H2(g)
Ca. Sr. and Ba also follow this pattern.

With Acids to Form Salts and Hydrogen Gas

Example: Mg(s) + 2HC1( a q ) MgCl2(<wy ) + H 2 ( g )
Be. Ca, Sr. and Ba also follow this pattern.

With Halogens to Form Salts

Example: Mg(.v ) + F\(g) > MgF2(s)
.
Ca, Sr and Ba also follow this pattern in reacting
with F:, Ck Br:, and F.
Calcium reacts with water to form hydrogen gas.
With Oxygen to Form Oxides or Peroxides
Magnesium forms an oxide.
() (g)
2 \lg( v ): •
> 2MgO(.v)
Be and Ca also follow this
pattern.

Strontium also forms a peroxide.

Sr(.v ) + 0:( g) » Sr02(s)
Ba also reacts in this wav.
With Hydrogen to Form Hydrides
Example: Mg( s) + FF(g) > MgH2(5)
Ca. Sr. and Ba also follow this pattern.

With Nitrogen to Form Nitrides

Example: 3Mg($) + N:( g)
Mg3N2(s)
Be and Ca also follow this
pattern.
Magnesium burns in air to form MgO Magnesium reacts with HCI to produce
and Mg3N2. .
/WgC/2(aq)

ANALYTICAL TEST
Flame tests can be used to identify three of the alka-
line earth elements. The colors of both calcium and
strontium can be masked by the presence of barium,
which produces a green flame.

Calcium Strontium Barium

ALKALINE EARTH METALS 793

 ELEMENTS HANDBOOK

PROPERTIES OF THE CROUP 2 ELEMENTS

Be Mg Ca Sr Ba Ka

Melting point ( C) 1278 ± 5 649 839 ± 2 769 725 7( H )

Boiling point ( C) 2467 1090 1484 1384 1640 1140

Density ( g/cnv' ) 1.85 1.74 1.54 2.6 3.5i 5

Ionization energy ( kJ/mol ) 900 738 590 550 503 509

Atomic radius ( pm ) 112 160 197 215 222 220

Ionic radius ( pm ) 45 72 1( H) 118 136 148

Common oxidation number +2 +2 +2 +2 +2 +2

in compounds
Crystal structure hep* hep fee * * fee bee bee
Hardness ( Mohs * scale ) 4.0 2.0 1.5 1.8 1.5

“ hexagonal close- packed -

** facc centered cubic

APPLICATION Technology
Fireworks
Fireworks are made from pyrotechnics chemical
substances that produce light and smoke when they
—
are ignited. Pyrotechnics are also used in flares,
smoke bombs, explosives, and matches. An aerial
fireworks device is a rocket made of a cylinder,
chemicals inside the cylinder, and fuses attached to
the cylinder. The illustration on the right shows how
the device works. The lift charge at the bottom of
the cylinder consists of a small amount of black gun -
powder. When the side fuse ignites the gunpowder, it
explodes like a small bomb. The gunpowder consists
of potassium nitrate, charcoal, and sulfur. When
these three chemicals react with one another, they
produce gases. In this case, the gases produced are
Time -delay - Red bursts
star
carbon monoxide, carbon dioxide, sulfur dioxide, fuses activate
and nitrogen monoxide. These hot gases expand the reactions Blue
very rapidly, providing the thrust that lifts the in the other star bursts
chambers
rocket into the sky.
Ignition fuse Flash and
About the time the shell reaches its maximum sound mixture
activates the
altitude and minimum speed, the time fuse
reaction in
ignites the chemicals contained in the cylinder. the bottom Black powder
propellant
The chemicals inside the cylinder determine chamber
the color of the burst . The cylinder of a multiple- hurst rocket contains separate reaction
chambers connected by fuses. A common fuse ignites the propel -
lant and the time- delay fuse in the first reaction chamber.

794 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

Chemical Composition and Color Flares

One of the characteristics of fireworks that we Flares operate on a chemical principle that is differ -
enjoy most is their variety of rich colors. These ent from that of fireworks. A typical flare consists
colors are created in much the same way as the of finely divided magnesium metal and an oxidizing
colors produced during a flame lest . In a fireworks agent. When the flare is ignited, the oxidizing agent
device, the chloride salt is heated to a high tempera - reacts with the magnesium metal to produce magne -
ture. causing the excited atoms to give off a burst sium oxide. This reaction releases so much energy
of light. The color of light produced depends on that it produces a glow like that of the filaments in
the metal used. The decomposition of barium a light bulb. The brilliant white light produced by
chloride. BaCI:. for example, produces a burst of the flare is caused bv billions of tiny particles of
green light , whereas strontium chloride. SrC'F. magnesium that glow when they react. If slightly
releases red light. larger particles of magnesium metal are used in the
People who design fireworks combine artistry flare, the system glows for a longer period of time
with a technical knowledge of chemical properties. because the particles' reaction with the oxidizing
They have found ways to combine different colors agent is slower.
within a single cylinder and to make parts of the A colored flare can be thought of as a combina -
cylinder explode at different times. Fireworks tion of a white flare and a chemical that produces
designers have a technical knowledge of projectile colored light when burned.
motion that is used to determine the height, direc - For example, a red flare
tion, and angle at which a fireworks device will can be made from magne -
explode to produce a fan. fountain, flower, stream, sium metal, an oxidizing
comet, spider, star, or other shape . agent, and a compound of
strontium. When the flare
Strontium and the Visible Spectrum is ignited, the oxidizing
When heated, some metallic elements and their com - agent and magnesium
pounds emit light at specific wavelengths that are metal react , heating the
characteristic of the element or compound. Visible magnesium to white-hot
light includes wavelengths between about 400 and temperatures. The energy
700 nanometers. The figure below shows the emis- from this reaction causes
sion spectrum for strontium. When heated, strontium the strontium compound A flare is made up of
gives off the maximum amount of visible light at to give off its characteris - billions of reacting
about 700 nanometers, which tic red color. magnesium particles.
falls in the red- light region of For safety reasons, some fireworks manufacturers
the visible spectrum. store their products in metal sheds separated by
sand banks. Also, people who work with fireworks
are advised to wear cotton clothing because cotton
is less likely than other fabrics to develop a static
charge, which can cause a spark and accidentally
The emission spec
trum for strontium
- ignite fireworks.
shows strong bands
in the red region of
the visible light
spectrum .

ALKALINE EARTH METALS 795

 ELEMENTS HANDBOOK

APPLICATION Health
Calcium: An Essential Mineral
in the Diet
Calcium is the most abundant mineral in the body.
It is the mineral that makes up a good portion of
the teeth and the bone mass of the body. A small
percentage of calcium in the body is used in the
reactions by which cells communicate and in the
regulation of certain body processes. Calcium is so
important to normal body functioning that if the
calcium level of the blood falls far below normal,
hormones signal the release of calcium from bone
and signal the gastrointestinal tract to absorb more
calcium during the digestion process. Dairy products are generally good sources of calcium.
A prolonged diet that is low in calcium is linked
to a disease characterized by a decrease in bone
mass, a condition called osteoporosis. Reduced Magnesium: An Essential Mineral
bone mass results in brittle bones that fracture easi - in the Diet
ly. Osteoporosis generally occurs later in life and is Though magnesium has several functions in the body,
more prevalent in females. However, because you one of the more important functions is its role in the
achieve peak bone mass during the late teens or absorption of calcium by cells. Magnesium, like so -
early twenties, it is critical that your diet meet the dium and potassium, is involved in the transmission
recommended requirements to increase your peak .
of nerve impulses Like calcium, magnesium is a
bone mass. The recommended dietary intake for component of bone.
calcium is 1000 mg per day. Maintaining that level A major source of magnesium in the diet is
in the diet along with regular exercise through adult - plants. Magnesium is the central atom in the green
hood are thought to reduce the rate of bone loss plant pigment chlorophyll. The structure of chloro-
later in life. Excess calcium in the diet ( consuming phyll in plants is somewhat similar to the structure
more than 2500 mg daily ) can interfere with the of heme— the oxygen-carrying molecule in animals.
absorption of other minerals. ( See page 816 for the heme structure.)

TABLE 2 A Good Sources of Calcium in the Diet

Food Serving size Calcium present ( mg )
Broccoli 6.3 oz 82
Cheddar cheese 1 oz 204
Cheese pizza, frozen pizza for one 375
Milk, low - fat 1 % 8 oz 300
Tofu, regular 4 oz 130
Vegetable pizza, frozen pizza for one 500
Yogurt, low- fat 8 oz 415
Yogurt , plain whole milk 8 oz 274

796 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

The recommended dietary intake of magnesium

is 400 mg per day. This is equivalent to just 4 oz of
bran cereal. Because magnesium levels are easily
maintained by a normal diet , it is unusual for
anyone to have a magnesium deficiency. Most
magnesium deficiencies are the result of factors
that decrease magnesium absorption . People with
gastrointestinal disorders, alcohol abusers, and the
critically ill are most likely to have these types of
absorption problems.
Excess magnesium in the diet is excreted by the
kidneys, so there are no cumulative toxic effects.

CEL
CH CH ,

CH , CH 2CH 3
N N
\ /
Spinach is a good source of magnesium. Magnesium is the central Mg
atom in the green plant pigment chlorophyll. The chlorophyll
/ \
CH , /= N N
structure is shown on the right. \ CH ,
o H
CH, CH CH CH
C CH 2 H
o CH 2 H C O
CH 3 %
CH3O o

TABLE 2 B Good Sources of Magnesium in the Diet

Food Serving size Magnesium present ( mg )
Barley, raw 1 cup 244
Beef broiled sirloin
, 4 oz 36
Cabbage , raw 1 med . head 134
Cashews, dry-roasted 1 oz 74
Chicken , roasted breast 4 oz 31
Lima beans, boiled 1 / 2 cup 63
Oatmeal 1 oz 39
Potato, baked 7.1 oz 115
Prunes , dried 4 oz 51
Rice bran 8 oz 648
Salmon canned
, 4 oz 39
Spinach , raw 10 oz 161

ALKALINE EARTH METALS 797

 CROUPS 3-12
TRANSITION METALS

CHARACTERISTICS
• consist of metals in Groups 3 through 12
• contain one or two electrons in their outermost
energy level
• are usually harder and more brittle than metals
in Groups 1 and 2
• have higher melting and boiling points than
metals in Groups 1 and 2
• are good heat and electrical conductors
• are malleable and ductile
• have a silvery luster except copper and gold
,

• include radioactive elements with numbers

•

— >

.
89 through 112
• include mercury the only liquid metal at room
*‘
temperature
,
A. *
• have chemical properties that differ from
each other
Iron ore is obtained from surface
• tend to have two or more common oxidation .
mines Hematite, Fe203, is the most common
states iron ore.
• often form colored compounds
• may form complex ions

Gold, silver, platinum, palladium, iridium, rhodium, ruthenium, and

osmium are sometimes referred to as the noble metals because
Copper ores are also obtained from surface they are not very reactive. These metals are found in coins, jewel-
mines. Copper ore is shown here. .
ry, and metal sculptures

798 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

COMMON REACTIONS
Because this region of the periodic table is so large,
you would expect great variety in the types of reac -
tion characteristics of transition metals. For exam -
ple. copper oxidizes in air to form the green patina
you see on the Statue of Liberty. Copper reacts with
concentrated HNO3 but not with dilute HNO3. Zinc,
on the other hand, reacts readily with dilute HC1.
Iron oxidizes in air to form rust, but chromium is
generally unreactive in air. Some common reactions
for transition elements are shown by the following.
Copper reacts with oxygen Copper reacts with concen-
in air. trated nitric acid.
May form two or more different ions
Example: Fe ( s ) > Fe 2 + ( aq ) + 2 e
Example: Fe(s) > Fc ' * ( aq ) + 3e
~

May react with oxygen to form oxides

Example: 4Cr(s) + 302(g) > 2Cr:03(.v )
Example: 2Cu(.v ) + 02(g) > 2CuO(.v )

May react with halogens to form halides

Example: Ni(.v ) + Cl 2 ( g) > NiCl2(.v )

May form complex ions

Zinc reacts with dilute Soluble iron(lll ) salts form insolu -
hydrochloric acid. ble Fe(OH )3 when they are reacted
See examples in the lower right . with a hydroxide base.

CU [ (CH 3) 2SO ] 2 CI2 -

Cu( NH 3) 4S04 H20

CO( NH 3) 4 C03 ] N03

[ CO(NH 3) 5 ( N02)] CI2 K 3[Fe(C204) 3 ]

Cr (N03)3 K 2Cr 20; K 2 Cr 04
Complex ions belong to a class of compounds
called coordination compounds. Coordination
Chromium has several common oxidation states, represented here by aqueous compounds show great variety in colors.
solutions of its compounds. The violet and green solutions contain chromium in the +3 Several transition-metal coordination com -
state, and the yellow and orange solutions contain chromium in the +6 oxidation state. pounds are shown.

TRANSITION METALS 799

 ELEMENTS HANDBOOK

ANALYTICAL TEST
Flame tests are not commonly used to identify tran-
sition metals. The presence of a certain transition-
metal ion in a solution is sometimes obvious from
the solution s color. Some transition-metal ions can
'

be more accurately identified using a procedure

called qualitative analysis. Qualitative analysis is the
identification of ions by their characteristic reactions.
The transition-metal ions most often identified
through qualitative analysis include copper, nickel,
zinc, chromium, iron cobalt, cadmium, manganese,
and tin. Most tests to identify the presence of an ion
in a mixture involve causing the ion to precipitate KMn04 CuS04

out of solution. Some of the more dramatic precipi- Some transition metal ions can be identified by
tation reactions for transition metals are shown. characteristic colors of their salt solutions.

s
%
'Wi

Copper ( formation of Cadmium ( formation Zinc ( formation of ZnS ) Chromium (formation

[CumjJfOH );) ofCdS ) ofPbCrOJ
1
I! I
.
bh

Iron ( formation of Manganese ( formation Nickel ( formation of a nickel

IFe(SCN )]2* ) ofMnOJ dimethylglyoxime complex )

800 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

PROPERTIES OF SOME TRANSITION METALS

Cr Fe Co Ni Cu Zn Ag Au Hg
Melting point (°C) 1857 ± 20 1535 1495 1455 1083 420 962 1064 -38.8

Boiling point (°C) 2672 2750 2870 2732 2567 907 2212 2808 ± 2 356.6
Density (g/cm ' ) 7.20 7.86 8.9 8.92 8.96 7.14 10.5 19.3 13.5
Ionization energy ( kJ/mol ) 653 762 760 737 746 906 731 890 1007
Atomic radius ( pm ) 128 126 125 124 128 134 144 144 151
Common oxidation numbers +2, +3, +6 +2, +3 +2, +3 +2 + 1 . +2 -t- 2 fl
•
+ 1, +3 +l, +2

APPLICATION Geology
Gemstones and Color a greenish color and is known as emerald. In another
A gemstone is a mineral that can be cut and pol- variation, if vanadium ions. V ' \ replace a few Al +
ished to make gems for an ornament or piece of ions in corundum, the result is a gemstone known as
jewelry. At one time, all gemstones were naturally alexandrite. This gemstone appears green in reflected
occurring minerals mined from Earth's crust. Today, natural light and red in transmitted or artificial light.
however, chemists can duplicate natural processes to Table 3 A lists transition metals that are respon-
produce artificial gemstones. Amethyst, emerald, sible for the colors of various gemstones. The table
jade, opal, ruby, sapphire, and topaz occur naturally provides only a general overview, however, as most
and can also be produced synthetically. naturally occurring gemstones occur in a range
The color of a gemstone is determined by the pres- of hues, depending on the exact composition of
ence of small amounts of one or more transition met - the stone.
als. For example, aluminum oxide, AFO3, often
occurs naturally as corundum —a clear, colorless min- Artificial Gemstones
eral. However if as few as 1 to 2% of the aluminum
, In 1902, the French chemist Auguste Verneuil found
ions, Al3 \ are replaced by chromium ions, Cr \ the a way to melt a mixture of aluminum oxide and
corundum lakes on a reddish color and is known as chromium salts and then cool the mixture very
ruby. If a small fraction of aluminum ions in corun- slowly to produce large crystals of reddish aluminum
dum are replaced by Fe3* and Ti3 \ the corundum has oxide — rubies.

Sapphire Peridot Garnet

TRANSITION METALS 801

 ELEMENTS HANDBOOK

TABLE 3A Transition Metals and Gemstone Colors

Gemstone Color Element

Amethyst purple iron

Aquamarine blue iron

Emerald green iron/ titanium

Garnet red iron

Peridot yellow-green iron

Ruby red chromium

Sapphire blue iron/ titanium
Spinel colorless to red to black varies

Turquoise blue copper

Verneuils method, although somewhat modified,

is still the one most widely used today for the manu-
facture of colored gemstones. When magnesium
oxide is substituted for aluminum oxide, a colorless
spinel-like product is formed. The addition of vari-
ous transition metals then adds a tint to the spinel
that results in the formation of synthetic emerald,
aquamarine, tourmaline, or other gemstones. Synthetic sapphire Synthetic ruby
Synthetic gems look very much like their natural
counterparts.

APPLICATION Technology
Alloys
An alloy is a mixture of a metal and one or more
other elements. In most cases, the second compo -
nent of the mixture is also a metal.
Alloys are desirable because mixtures of elements
usually have properties different from and often
superior to the properties of individual metals. For
example, many alloys that contain iron are harder,
stronger, and more resistant to oxidation than iron
itself.

Amalgams are alloys that contain mercury. They are soft

and pliable when first produced, but later become solid
and hard. Dental fillings were once made of an amalgam
of mercury and silver. Concerns about the possible
toxicity of mercury led to the development of other
.
filling materials

802 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

Cast Iron and Steel a banded product that is tough but not very hard.
The term steel applies to any alloy consisting of iron However, if the cast iron is cooled quickly, the com -
and less than 1.5 % carbon, and often other ele - ponents of the original mixture cannot separate
ments. When iron ore is treated with carbon in the from each other, forming a product that is both tough
form of coke to extract pure iron metal, some of the and hard.
carbon also reacts with the iron to produce a form of
iron carbide known as cementite. The reaction can
be represented by the following equation.

3Fe 4- C
* Fe3C
Cast iron is a mixture that consists of some pure iron,
known as ferrite, some cementite, and some carbon
atoms trapped within the crystalline structure of the
iron and cementite. The rate at which cast iron is
cooled changes the proportion of these three compo- Stainless steel, which is hard and resists corrosion, is made of iron
nents. If the cast iron is cooled slowly, the ferrite and and chromium ( 12-30% ). The properties of stainless steel make it
cementite tend to separate from each other, forming a suitable alloy for making cutlery and utensils.

TABLE 3 B Composition and Uses of Some Alloys

Name of alloy Composition Uses
Brass copper with up to 50% zinc, inexpensive jewelry: hose nozzles and couplings: piping:
some lead, and a small stamping dies
amount of tin

Bronze copper with up to 12 % tin coins and medals: heavy gears: tools: electrical hardware
Coin metal copper: 75 % United States coins
nickel: 25 %
Duralumin aluminum: 95 % aircraft, boats, railroad cars, and machinery because of its
copper: 4 % high strength and resistance to corrosion
magnesium: 0.5%
manganese: < 1 %
Nichrome nickel: 80-85 % heating elements in toasters, electric heaters, etc.
chromium: 15-20%
Phosphor bronze bronze with a small springs, electrical springs, boat propellers
amount of phosphorus
Solder lead: 50%. tin: 50% joining two metals to each other
or
tin: 98%, silver: 2 % joining copper pipes

Sterling silver silver: 92.5 % jewelry, art objects, flatware

copper: 7.5 %
Type metal lead: 75-95% used to make type for printing because it expands as it cools
antimony: 2- 18%
tin: trace

TRANSITION METALS 803

ELEMENTS HANDBOOK

•••••••
******
*******f******* •• •• #
#
901##
^ ••^•*•* ••
* * ••
• •
••••
•••
* * * * * * * •••••••
Interstitial crystal
A smaller atom or ion fits into a small space between particles
in the array.
Substitutional crystal
A larger atom or ion is substituted for a particle in the array.

Structures and Preparation of Alloys Techniques for making alloys depend on the
Alloys generally crystallize in one of two ways, metals used in the mixture. In some cases, the two
depending on relative sizes of atoms. If the atoms of metals can simply be melted together to form a mix -
one of the metals present are small enough to fit into ture. The composition of the mixture often varies
the spaces between the atoms of the second metal, within a range, evidence that the final product is
they form an alloy with an interstitial structure ( inter indeed a mixture and not a compound. In other
means “between, ' and stitial means “ to stand * ). If
* '
cases, one metal may be melted first and the second
atoms of the two metals are of similar size or if one dissolved in it . Brass is prepared in this way. If
is larger, the atoms of one metal can substitute for copper and zinc were heated together to a high tem -
the atoms of the second metal in its crystalline struc - perature, zinc ( bp 907°C) would evaporate before
ture. Such alloys are substitutional alloys. Models for copper ( mp 1084 C ) melted. Therefore, the copper
both types of crystals are shown above. is melted first, and the zinc is added to it.

: m

. 9
u *

.8

Brass has a high luster and resembles gold when cleaned and polished. A brass object Sterling silver is more widely used than pure
can be coated with a varnish to prevent reactions of the alloy with air and water. silver because it is stronger and more durable .
804 ELEMENTS HANDBOOK
 ELEMENTS HANDBOOK

APPLICATION The Environment

Mercury Poisoning Hatters often displayed the nerve and mental impair -
Mercury is the only metal that is liquid at room tem - ments associated with overexposure to mercury.
perature. It has a very high density compared with
most other common transition metals and has a very Methylmercury in Freshwater Ecosystems
large surface tension and high vapor pressure. Mercury Mercury. Hg, can be found in our environment and
and many of its compounds must be handled with in our food supply. Fortunately, the body has some
extreme care because they are highly toxic. Mercury protective mechanisms to deal with trace amounts
spills are especially hazardous because the droplets of mercury. However, levels of mercury and of
scatter easily and are often undetected during cleanup. methylmercury. ( CH 3 ) Hg \ are increasing in the
These droplets release toxic vapors into the air. environment due to mercury mining operations
Overexposure to mercury vapor or its compounds and runoff from the application of pesticides and
can occur by absorption through the skin , respiratory fungicides.
tract , or digestive tract . Mercury is a cumulative poi - Mercury is easily converted to methylmercury by
son. which means that its concentration in the body bacteria . Methylmercury is more readily absorbed by
increases as exposure increases. cells than mercury itself . As a result , methylmercury
Mercury that enters the body damages the kid - accumulates in the food chain as shown in the dia -
nevs. heart , and brain . The action of mercurv on the
j T * »
gram below. A serious incident of methylmercury poi -
brain affects the nervous system . Symptoms of mer - soning occurred in Japan in the 1950s. People living in
cury poisoning include numbness, tunnel vision , gar - Minamata. Japan , were exposed to high levels of
bled speech , bleeding and inflammation of the gums, methylmercury from eating shellfish.
muscle spasms, anemia and emotional disorders, such
, In the United States, there is concern about mer -
as depression , irritability, and personality changes. curv levels in fish from some freshwater lakes.
The saying “ mad as a hatter probably came about
*'
Though environmental regulations have reduced the
because of mercury poisoning. Mercury salts were level of lake pollutants, it takes time to see a reduc-
once routinely used to process the fell used in hats. tion in the concentration of an accumulated poison .

Sewage

Mercury enters
water ecosystem \
from lab chemicals . and each other
industrial waste,
runoff of fungicides

Bacteria convert Hg Plankton

and inorganic Hg eat bacteria Concentrations of methylmercury increase
compounds to (CH 3)Hg at higher levels of the food chain.

TRANSITION METALS 805

ELEMENTS HANDBOOK

APPLICATION Health
Abundance of Elements in the Body
Elements in the Body (by mass)
The lour most abundant elements in the
body (oxygen, carbon, hydrogen and nitro - ,

gen ) are the major components of organic

biomolecules, such as carbohydrates, pro -
teins. fats, and nucleic acids. Other Carbon
elements compose a dietary category of 18.5 %
compounds called minerals. Minerals are
considered the inorganic elements of the
Hydrogen
body. Minerals fall into two categories— 9.5 %
the major minerals and the trace min-
Oxygen
erals. or trace elements, as they are 65.0%
Phosphorus
sometimes called. Notice in the 1.0 %
periodic table below that most ele - Calcium 1.5 %
ments in the trace elements category
of minerals are transition metals. Other 1.3 %
Trace elements are minerals with Potassium
Sulfur
dietary daily requirements of UK) mg or Sodium
Nitrogen 3.2 %
less. They are found in foods derived from Chlorine
both plants and animals. Though these Magnesium
Trace elements
in
elements are present very small quanti -
ties. they perform a variety of essential
functions in the body, as shown in Table
3C on the next page.

Group 18
1 Elements in organic matter 2
H
Major minerals He
Group 1 Group 2 Group 13 Group 14 Group 15 Group 16 Group 17
3 4 5 6 7 8 9 10
Trace elements
Li Be B C N O F Ne
11 12 13 14 15 16 17 18

Na Mg Al Si P S Cl Ar
Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
87 88 89
Fr Ra Ac

806 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

TABLE 3 C
Role of Iron
Transition Metal Trace Elements
Most iron in the body is in hemoglobin. Fe3+ ;is the
Transition central ion in the heme molecule, which is a compo-
metal Function nent of the proteins hemoglobin and myoglobin.
Vanadium. function not fully determined, but Hemoglobin in red blood cells transports oxygen to
Cadmium linked to a reduced growth rate and cells and picks up carbon dioxide as waste. Myoglobin
impaired reproduction is a protein that stores oxygen to be used in muscle
contraction. Iron is also in the proteins of the elec-
Chromium needed for glucose transport to cells
tron transport system and the immune system.
Manganese used in the enzyme reactions that Mechanisms of the body control the rate of iron
synthesize cholesterol and metabo- absorption from food in the diet . When iron
lize carbohydrates reserves are low, chemical signals stimulate cells of
Iron central atom in the heme mol - the intestines to absorb more iron during digestion.
ecule—a component of hemoglobin, If the diet is low in iron, causing a deficiency, hemo -
which binds oxygen in the blood for globin production stops and a condition called iron-
transport to cells deficiency anemia results. The blood cells produced
Cobalt a component of vitamin B during this state are stunted and unable to deliver
^ adequate oxygen to cells. As a result, a person with
Nickel enzyme cofactor in the metabolism iron-deficiency anemia feels tired and weak and has
of fatty acids and amino acids
difficulty maintaining normal body temperature.
Copper a major component of an enzyme The recommended daily intake of iron is 15 mg. The
that functions to protect cells from recommended level doubles for pregnant women.
damage Iron supplements are for people who do not get
Zinc needed for tissue growth and repair enough iron in their daily diets. Table 3D lists some
and as an enzyme cofactor foods that are good sources of iron in the diet. Too
much iron can be toxic because the body stores iron
Molybdenum enzyme cofactor in the production
once it is absorbed. Abusing iron supplements can
of uric acid
cause severe liver and heart damage.

TABLE 3 D Sources of Iron in Foods

Food Serving size Iron present ( mg )

Beef roast ( lean cut ) 4 oz 3.55

Beef. T-bone steak ( lean cut ) 4 oz 3.40
Beef, ground ( hamburger ) 4 oz 2.78
Broccoli 0.3 oz 1.50

Chicken, breast 4 oz 1.35

Chicken, giblets 4 oz 7.30
Oatmeal, instant enriched 1 pkg 8.35
Pita bread, white enriched 6 1 /2 in. diameter 1.40
Pork roast 4 oz 1.15
Prunes 4 oz 2.00
Raisins 4 oz 1.88

TRANSITION METALS 807

 GROUP 13
BORON FAMILY

CHARACTERISTICS
B
Boron
• do not occur in nature as free elements 10.811
|Hel2$ty Atomic radius
• are scarce in nature (except aluminum, which is
the most abundant metallic element ) increases
13
• consist of atoms that have three electrons in their A1
Aluminum
outer energy level 26.981 538
|Nel3sV
• are metallic solids (except boron, which is a solid
metalloid) 31
Ionic radius
• are soft and have low melting points (except Ga increases
Gallium
boron, which is hard and has a high melting point )
,
69723
|Ar|3d 04sV
• are chemically reactive at moderate temperatures
(except boron ) 49
In
Indium
Boron is a covalent
,
114.818
[ Kr )4 d 05 sV
Ionization energy
decreases
solid. Other members

\
of the family are 81
metallic solids. T1
Thallium
204.3833 ,
|Xe|4 /145d 06 $ V

The warmth of a person's hand will melt gal -

lium. Gallium metal has the lowest melting Aluminum is the most abundant metal in Earth's
point (29.77°0 of any metal except mercury. crust. It exists in nature as an ore called bauxite.

808 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

COMMON REACTIONS
The reaction chemistry of boron differs greatly from
that of the other members of this family. Pure boron
t
is a covalent network solid whereas the other mem -
,
Mg
bers of the family are metallic crystals in pure form.
Boron resembles silicon more closely than it resembles
the other members of its family.
Al
Fe203
With Strong Bases to Form Hydrogen Gas and a Salt
Example: 2 Al ( s ) + 2NaOH ( </ </ ) + 2H20( / ) » A mixture of powdered alu -
2NaAIO2(0<7 ) + 3H2(g) minum and iron( lll ) oxide is
Ga also follows this pattern. called thermite. Al reacts with
Fe203 using Mg ribbon as a
fuse to provide activation
With Dilute Acids to Form Hydrogen Gas and a Salt energy. The energy produced
Example: 2 AI(.v ) + 6 HC\( at / ) ,
» 2AlCl- ( <if/ ) + 3H2(g) by the thermite reaction is suf -
ficient to produce molten iron
Ga, In. and Tl follow this pattern in reacting
as a product.
with dilute HF. HCI, HBr. and HI.

With Halogens to Form Halides

Example: 2 Al(.v ) + 3Cl2(g) » 2 AICl3( s )
B, Al, Ga, In. and Tl also follow this pattern in react -
ing with F2. Cl 2. Br 2. and I2 ( except BF3).

With Oxygen to Form Oxides

Example: 4A1($) + 302(g) > 2 AI203(s)
Ga, In. and Tl also follow this pattern.

ANALYTICAL TEST
Other than atomic absorption spec -
troscopy, there is no simple analytical
test for all the members of the boron
family.

The confirmatory test for the presence of

aluminum in qualitative analysis is the red color
formed by aluminum and the organic compound
aluminon, C22 H23N 309 . Aluminum forms a thin layer of Al 2Oy which protects
the metal from oxidation and makes it suitable for
outdoor use .

BORON FAMILY 809

ELEMENTS HANDBOOK

PROPERTIES OF THE CROUP 13 ELEMENTS

It AI Ciii 111 II

Melting point ( C ) 2300 660.37 29.77 156.61 303.5

Boiling point ( C ) 2550 2467 2403 2080 1457

Density ( g/cnT ) 2.34 2.702 5.904 7.31 11.85

Ionization energy (kJ /mol) 801 578 579 558 589

Atomic radius ( pm ) 85 143 135 167 170

Ionic radius ( pm ) 54 62 80 89

Common oxidation
+3 +3 4- 1, +3 + 1. +3 +K +3
number in compounds
Crystal structure monoclinic fee orthorhombic fee hep
Hardness ( Mohs* scale ) 9.3 2.75 1.5 1.2 1.2

APPLICATION Technology
Aluminum
Chemically, aluminum is much more active than cop -
-
per. and it belongs to the category ol self protecting
metals. These metals are oxidized when exposed to
oxygen in the air and form a hard, protective metal
oxide on the surface. The oxidation of aluminum is
shown by the following reaction .
4 Al(.v ) + 302( g ) > 2 A 12Q3(.V )

This oxide coating protects the underlying metal

from further reaction with oxygen or other sub-
stances. Self-protecting metals are valuable in them -
selves or when used to coat iron and steel to keep
them from corroding.
Aluminum is a very good conductor of electric
current . Many years ago. most high-voltage electric
power lines were made of copper. Although copper These high - voltage transmission lines are made of
is a better conductor of electricity than aluminum, aluminum supported with steel cables.
copper is heavier and more expensive. Today more
than 90% of high- voltage transmission lines are .
because the aluminum oxidized AU03 built up and
made of relatively pure aluminum. The aluminum increased electric resistance at points where wires
wire does not have to be self-supporting because connected to outlets, switches, and other metals. As
steel cable is incorporated to bear the weight of current Rowed through the extra resistance, enough
the wire in the long spans between towers. energy as heat was generated to cause a fire. Though
In the 1960s. aluminum electric wiring was used in some homes have been rewired, aluminum wiring is
many houses and other buildings. Over time, however. still prevalent in many homes.

810 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

Aluminum Alloys To heater Bypass

Water cools
Because aluminum has a low density and is inexpen-
sive, ii is used to construct aircraft, boats, sports From heater
equipment, and other lightweight, high-strength
objects. The pure metal is not strong, so it is mixed
with small quantities of other metals— usually man-
ganese. copper, magnesium, zinc, or silicon— to pro -
duce strong low -density alloys. Typically, 80% of a
modern aircraft frame consists of aluminum alloy.
Cross- flow
Aluminum and its alloys are good heat conduc - radiator
tors. An alloy of aluminum and manganese is used
to make cookware. High-quality pots and pans
made of stainless steel may have a plate of aluminum
Si
on the bottom to help conduct energy as heat quick - *
ly to the interior. .. v
ft

Automobile radiators made of aluminum

conduct energy as heat as hot coolant from the
.
am* BBSS
vrv ” . 5
'

iS
engine enters the bottom of the radiator. The
—
. - »
•jinvvr " •

coolant is deflected into several channels. These

In this aluminum car radiator,
many thin vanes of aluminum
imwwiwuuiww f
mmmmmuaummg -- t

channels are covered by thin vanes of aluminum, S“SK :

conduct energy as heat, transfer - ^
mwnwmmmmr
WUUUmW..
which conduct energy away from the coolant and .
ring it from the coolant to the air
'YUr

transfer it to the cooler air rushing past. By the lime Coolant is cycled from the hot engine
through the radiator and back to the engine.
the coolant reaches the lop of the radiator, its tem -
perature has dropped so that when it Hows back into
the engine it can absorb more energy as heat. To
keep the process efficient, the outside of a radiator
should be kept unobstructed and free of dirt
buildup.

TABLE 4 A Alloys of Aluminum and Their Uses

Principal alloying
elemcnt ( s )* Characteristics Application examples
Manganese moderately strong, easily worked cookware, roofing, storage tanks, lawn furniture
Copper strong, easily formed aircraft structural parts: large, thin structural
panels
Magnesium strong, resists corrosion, easy to weld parts for boats and ships, outdoor decorative
objects, tall poles
Zinc and magnesium very strong, resists corrosion aircraft structural parts, vehicle parts, anything
that needs high strength and low weight
Silicon expands little on heating and cooling aluminum castings
Magnesium and silicon resists corrosion, easily formed exposed parts of buildings, bridges
All these allovs have small amounts of other elements.

BORON FAMILY 811

 GROUP 14
CARBON FAMILY

CHARACTERISTICS C
Carbon
• include a nonmetal ( carbon), two metalloids 120107
(silicon and germanium ), and two metals |He]2 sV
( tin and lead)
Atomic radius
14 increases
• vary greatly in both physical and chemical Si
properties Silicon
28.0855
[ Ne]3s 23p2
• occur in nature in both combined and elemental Ionization energy
forms decreases
32
• consist of atoms that contain four electrons in the Ge
outermost energy level Germanium
,
72.64
|Arl3 d 04sV
• are relatively unreactive
• tend to form covalent compounds ( tin and lead 50

also form ionic compounds) Sn

Tin
,
118.710
(Kr|4</ 05sV

Lead has a low reactivity 82

and is resistant to
corrosion. It is very
Pb
Lead
soft, highly ductile,
and malleable.
Lead is toxic and,
,207.2
[Xe|4/ 45 / 106sV
(
f
like mercury, it is
a cumulative
poison .

Tin, which is shown on the right, is a self - protecting

metal like lead, but unlike lead it has a high luster. Tin
occurs in nature in cassiterite ore, which is shown above.

812 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

COMMON REACTIONS
With Oxygen to Form Oxides
Example: Sn (s ) + O2( g ) » SnO2(s)
Pb follows this pattern , as do C, Si , and Ge at high temperatures.

With Acids to Form Salts and Hydrogen Gas

Only the metallic elements of this group react slowly with aqueous acids.
Example: Sn (s) + 2HC1( aq ) > SnCI 2 ( aq ) + H 2 ( g )
Both Sn and Pb can also react to form tin ( IV ) and lead ( IV ) salts, respectively.

With Halogens to Form Halides

Example: Sn ( s ) + 2Cl2(g ) > SnCl 4 (.v )
Si. Ge, and Pb follow this pattern, reacting with F2, Cl 2. Br2. and I 2.

ANALYTICAL TEST
Ionic compounds of tin and lead can be identified in
aqueous solutions by adding a solution containing
sulfide ions. The formation of a yellow precipitate
indicates the presence of Sn 4 \ and the formation of
a black precipitate indicates the presence of Pb .

Sn4*{ aq ) + 2S2~( aq ) -> SnS:( .v )

Pb:‘ ( aq ) + S 2 ( aq )
~

* PbS( .v )

SnS2

PROPERTIES OF THE CROUP 14 ELEMENTS

c Si ( it* Sn Ph
Melting point ( C ) 3500/ 3652* 1410 937.4 231.88 327.502
Boiling point ( C ) 4827 2355 2S30 2260 1740
Density ( g/cnv ' ) 3.51 /2.25* 2.33 ± 0.01 5.323 7.28 11.343
Ionization energy ( kJ / mol ) 1086 787 762 709 716
Atomic radius ( pm ) 77 118 122 140 175
Ionic radius ( pm ) 260 ( C4- ion ) 118 ( Sn 2+ ion ) 119 ( Pb2 * ion )
Common oxidation +4, -4 +4 +2, ±4 +2, +4 +2. +4
number in compounds
Crystal structure cubic/hexagonal* cubic cubic tetragonal fee
Hardness ( Mohs ' scale ) 10/0.5* 6.5 6.0 1.5 1.5
* The data are for two allotropic forms: diamond / raphite
^
CARBON FAMILY 813
ELEMENTS HANDBOOK

APPLICATION Chemical Industry

Carbon and the Reduction of Iron Ore The calcium oxide then combines with silica, a
Some metals, especially iron, are separated from their silicon compound, to form calcium silicate slag.
ores through reduction reactions in a blast furnace. The relatively high carbon content of iron
The blast furnace gets its name from the fact that produced in a blast furnace makes the metal hard but
air or pure oxygen is blown into the furnace, where brittle. It also has other impurities, like sulfur and
it oxidizes carbon to form carbon monoxide, CO. phosphorus, that cause the recovered iron to be brit -
Carbon and its compounds are important reactants tle. The conversion of iron to steel is essentially a
in this process. purification process in which impurities are removed
What happens inside the blast furnace to recover by oxidation. This purification process is carried out
the iron from its ore ? The actual chemical changes in another kind of furnace at very high temperatures.
that occur are complex. A simplified explanation All steel contains 0.02 to 1.5 % carbon. In fact, steels
begins with the reaction of oxygen in hot air with are graded by their carbon content. Low -carbon
coke, a form of carbon. Some of the coke burns to steels typically contain 0.02 to 0.3 % carbon. Medium -
form carbon dioxide. carbon steels typically contain 0.03 to 0.7% carbon.
High-carbon steels contain 0.7 to 1.5 % carbon.
C( s ) + O2( g ) > CO20? )

As the concentration of oxygen is decreased, the Exhaust gases

( mostly H2 and CO)
carbon dioxide comes in contact with pieces of hot
coke and is reduced to carbon monoxide.

C02(g) + C( s ) > 2CO( s )

The carbon monoxide now acts as a reducing agent

to reduce the iron oxides in the ore to metallic iron.

Limestone,
Fe 203(.v ) + 3CO( ) > 2Fe ( / ) + 3C02(#)
* coke (a source
of carbon)
The reduction is thought to occur in steps as the and iron ore
temperature in the furnace increases. The following Compressed
are some of the possible steps. air or pure 02

I e 203 -> ,
FC Q4 > FeO > Fe

The white-hot liquid iron collects in the bottom of

the furnace and is removed every four or five hours.
The iron may be cast in molds or converted to steel Molten
in another process. iron

Limestone, present in the center of the furnace,

decomposes to form calcium oxide and carbon
dioxide.

CaCO3(5) CaO( .v ) + COjO?)

Molten iron flowing from the bottom of a blast furnace has
been reduced from its ore through a series of reactions at high
temperatures in different regions of the furnace.

814 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

Carbon Dioxide carbon dioxide are summarized in the diagram of

C arbon dioxide is a colorless gas with a faintly irri - the carbon cycle, which is pictured below.
tating odor and a slightly sour taste. The sour taste
is the result of the formation of carbonic acid when Carbon Monoxide
CO: dissolves in the water in saliva. It is a stable gas Carbon monoxide is a poisonous gas produced
that does not burn or support combustion. At tem - naturally by decaying plants, certain types of algae,
peratures lower than 31°C and at pressures higher volcanic eruptions, and the oxidation of methane in
than 72.c) atm. C02 condenses to the liquid form. the atmosphere.
-
A phase diagram for CO is found in the chapter
review section of Chapter 10. At normal atmospher -
Because CO is colorless, odorless, and tasteless,
it is difficult to detect. It is slightly less dense than
ic pressure, solid C() 2 ( dry ice ) sublimes at -78.5 C. air and slightly soluble in water. Its main chemical
The linear arrangement of carbon dioxide molecules uses are in the reduction of iron, described on page
makes them nonpolar. 814. and the production of organic compounds, such
CO: is produced by the burning of organic fuels as methanol.
and from respiration processes in most living things.
Most C02 released into the atmosphere is used by CO( g ) + 2H2( g) ,
> CH OH( / )
plants during photosynthesis. Recall that photosyn-
Carbon monoxide is also produced during the
thesis is the process bv which green plants and some
incomplete combustion of organic fuels. Incomplete
forms of algae and bacteria make food. During
combustion of methane occurs when the supply of
photosynthesis, CC) 2 reacts with ll2(), using the
oxygen is limited.
energy from sunlight. The relationships among the
various processes on Earth that convert carbon to 2CH4(g) + 3Q2(g) > 2CO(g) + 4H20(g)

C02 in atmosphere

Photosynthesis

Respiration

Diffusion

Respiration

Dissolved
organic matter
eu t Deep ocean

The processes that recycle C02 are

collectively called the carbon cycle.
CARBON FAMILY 815
ELEMENTS HANDBOOK

APPLICATION Biochemistry
Carbon Dioxide and Respiration Carbon dioxide produced during respiration
Many organisms, including humans, carry out cellular is a waste product that must be expelled from an
respiration. In this process, cells break down food organism. Various things happen when C02 enters
molecules and release the energy used to build those the blood. Seven percent dissolves in the plasma,
molecules during photosynthesis. Glucose, QH 1:06. is about 23 % binds loosely to hemoglobin,
a common substance broken down in respiration. The and the remaining 70% reacts reversibly
following chemical equation expresses this process. with water in plasma to form hydrogen carbonate,
HCO7 ions. To form HCO3 ions, C02 first combines
ChHl 2Oh + ^02 > 6C02 + 6H2Q + energy with H20 to form carbonic acid, H 2C02, in a
reversible reaction.
In humans and most other vertebrate animals, the

* H:CO,(«</ )
oxygen needed for this reaction is delivered to cells C02 ( aq ) + H:0( / )
by hemoglobin found in red blood cells. Oxygen
binds with hemoglobin as blood passes through cap - The dissolved carbonic acid ionizes to HCO3 ions
illaries in the lungs, as represented by the following
reaction.
and aqueous H ‘ ions in the form of H O ’.-
U 2CO )( aq ) + H2Q H3O ' { ( iq ) + HCO
Hb + O, » HbO: ^ tu / )

Hb represents the hemoglobin molecule, and Hb02 The combined equilibrium reaction follows.
represents oxyhemoglobin, which is hemoglobin
with bound oxygen. When the red blood cells pass C02 ( aq ) + 21I20( / ) * H3Cy ( aq ) + HCO }( aq )
through capillaries near cells that have depleted
their oxygen supply through respiration, the reaction When the blood reaches the lungs, the reaction
reverses and oxyhemoglobin gives up its oxygen. reverses and the blood releases C02. which is
then exhaled to the surroundings.
> Mb + 0*1

Oxygen
molecule

COOH

COOH

Heme Hemoglobin ( protein) Red blood cells

The oxygen carrier molecule, heme, is a component of the more- complex protein
hemoglobin. Note that each hemoglobin molecule has four heme subunits. Hemoglobin
is a component of red blood cells.

816 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

Exchange of C02 and 02 in the Lungs Acidosis and Alkalosis

Why does C02 leave the blood as it passes through In humans, blood is maintained between pH 7.3 and
the lungs capillaries, and why does 02 enter the 7.5. The pi I of blood is dependent on the concentra-
blood? The exchange is caused by the difference in tion of CO: in the blood. Look again at this equilib-
concentrations of C02 and 02 in the blood and in rium system.
the atmosphere. Oxygen is 21% of the atmosphere.
Although the amount of C02 varies from place to => H30*(IM/ ) + HCG3( r </ )
CO2 ( aq ) + 2H20( / ) 4 /

place, it averages about 0.033% of the atmosphere.

Thus. 02 is about 640 times more concentrated in Notice that the right side of the equation contains
the atmosphere than is CO:. the H3CT ion. which determines the pH of the
Substances tend to diffuse from regions of higher blood. If excess H3CT enters the blood from tissues,
concentration toward regions of lower concentration. the reverse reaction is favored. Excess H30+ com -
Thus, when blood reaches the capillaries of the lung. bines with HC03 10 produce more C02 and H 2Q. If
C) 2 from the air diffuses into the blood, where its the H3CT concentration begins to fall, the forward
pressure is only 40 mm Hg, while C02 diffuses out of reaction is favored, producing additional H3CT and
the blood, where its pressure is 45 mm Hg. and into HC03. To keep H30+ in balance, adequate amounts
the air. The diagram below summarizes the process. of both C02 and HCO3 must be present. If some -
thing occurs that changes these conditions, a person
can become very ill and can even die.
02 molecule C02 diffuses into Hyperventilation occurs when a person breathes
C02 molecule 1 the alveoli to too rapidly for an extended time. Too much C02 is
be exhaled
eliminated, causing the reverse reaction to be favored,
02 diffuses from and H30 and HCOJ are used up. As a result, the
*

the alveoli into person develops a condition known as alkalosis

the blood to be
carried to cells because the pH of the blood rises to an abnormal
through the alkaline level. The person begins to feel lightheaded
capillaries and faint, and, unless treatment is provided, he or she
may fall into a coma. Alkalosis is treated by having
.
the victim breathe air that is rich in CO- . One way to
accomplish this is to have the person breathe with a
bag held lightly over the nose and mouth. Alkalosis
Alveolus is also caused by fever, infection, intoxication, hys-
of the lung teria. and prolonged vomiting.
Capillary Flie reverse of alkalosis is a condition know n as
in the lung acidosis. This condition is often caused by a depletion
of HC03 ions from the blood, which can occur as a
result of kidney dysfunction. The kidney controls the
excretion of HC03 ions. If there are too few HC03
ions in solution, the forward reaction is favored and
H30+ ions accumulate, which lowers the bloods pH.
Acidosis can also result from the body ’s inability to
expel C02, which can occur during pneumonia,
emphysema, and other respiratory disorders. Perhaps
the single most common cause of acidosis is uncon -
The pressure of 02 in the blood entering the lung is much lower
than it is in the atmosphere. As a result, 02 diffuses into the blood. trolled diabetes, in which acids normally excreted in
The opposite situation exists for Q02, so it diffuses from the blood the urinarv svstem are instead retained bv the bodv.
into the air. Note that blood leaving the lung still contains a
significant concentration of C02.

CARBON FAMILY 817

 ELEMENTS HANDBOOK

APPLICATION The Environment

Carbon Monoxide Poisoning The level of danger posed by carbon monoxide
Standing on a street corner in any major city exposes depends on two factors: the concentration of the
a person to above-normal concentrations of carbon gas in the air and the amount of time that a person
monoxide from automobile exhaust. Carbon monox - is exposed to the gas. Table 5 A shows the effects of
ide also reacts with hemoglobin. The following reac - increasing levels of carbon monoxide in the blood-
tion takes place in the capillaries of the lung. stream. These effects vary considerably depending
on a person's activity level and metabolic rate.
1 lb + CO > HbCO
Unlike CO: or 0:. CO binds strongly to hemo-
globin. Carboxvhemoglobin. HbCO, is 200 times
.
more stable than oxyhemoglobin. Hb02 So as blood
circulates, more and more CO molecules bind to
hemoglobin, reducing the amount of 02 bond sites
available for transport. Eventually. CO occupies so
many hemoglobin binding sites that cells die from
lack of oxygen. Symptoms of carbon monoxide
poisoning include headache, mental confusion, dizzi-
ness, weakness, nausea, loss of muscular control, and
decreased heart rate and respiratory rate. The victim
loses consciousness and will die without treatment.
If the condition is caught in time, a victim of
carbon monoxide poisoning can be revived by breath-
ing pure oxygen. This treatment causes carboxy -
hemoglobin to be converted slowly to oxyhemoglo-
bin according to the following chemical equation.
O, + HbCO > CO + Hb02
Carbon monoxide detectors are now available to reduce the risk
Mild carbon monoxide poisoning usually does not
of poisoning from defective home heating systems. The Consumer
have long- term effects. In severe cases, cells are Products Safety Commission recommends that all homes have a CO
destroyed. Damage to brain cells is irreversible. .
detector with a UL label

TABLE 5 A Symptoms of CO Poisoning at Increasing Levels of CO Exposure and Concentration

Concentration of CO in air ( ppm ) * Hemoglobin molecules as HbCO Visible effects
100 for 1 hour or less 10 % or less no visible symptoms

500 for 1 hour or less 20% mild to throbbing headache, some

dizziness, impaired perception
5(H) for an extended period of time 30-50% headache, confusion, nausea, dizziness,
muscular weakness, fainting
1000 for 1 hour or less 50-80% coma, convulsions, respiratory failure,
death
ppm is parts per million

818 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

APPLICATION Biochemistry

Macromolecules Proteins
Large organic polymers are called macromolecules Proteins are macromolecules formed by condensation
( the prefix macro means “large" ). Macromolecules reactions between amino acid monomers. Proteins
play important roles in living systems. Most macro- contain carbon, oxygen, hydrogen, nitrogen, and
molecules essential to life belong to four main usually some sulfur.
classes, three of which we know as nutrients in food: All amino acids have a carboxyl group, —COOIL
1. Proteins Flair, tendons, ligaments, and silk are and an amino group. —NFL, attached to a central car -
made of protein. Other proteins act as hormones, bon atom, which is also attached to hydrogen. H. —
transport substances throughout the body, and Amino acids differ from one another al the fourth
fight infections. Enzymes are proteins that con- bond site of the central carbon, which is attached to
.
trol the body 's chemical reactions Proteins pro- a group of atoms ( called an R group ). R groups dif -
vide energy, yielding 17 kJ / g. fer from one amino acid to another, as shown in the
2 . Carbohydrates Sugars, starches, and cellulose structures for several amino acids below. I he proteins
are carbohydrates. Carbohydrates are sources of all organisms contain a set of 20 common amino
of energy, yielding 17 kJ / g. acids. The reaction that links amino acids is a con -
3. Lipids Fats. oils, waxes, and steroids are lipids, densation reaction, which is described in Chapter 22.
nonpolar substances that do not dissolve in water. Each protein has its own unique sequence of
Fats are sources of energy, yielding 38 kJ / g. amino acids. A complex organism has at least several
4 . Nucleic acids DNA and RNA are nucleic acids. thousand different proteins, each with a special
In most organisms, DNA is used to store heredi- structure and function. For instance, insulin, a hor -
tary information and RNA helps to assemble mone that helps the body regulate the level of
proteins. sugar in the blood, is made up of two linked chains.

Amino acids have the same general NIL //

o
structure. These examples show some ( C\
of the variations within this class of
compounds. II Oil
General structure

NH; o O NH: o O NH; o

C’H;-C-C
I \
oil
.
IIA C - CH -C-C
OH
HA 0 OH - CIH- C-C
OH
H H H
Alanine Asparagine Glutamine

NH: o
II CH, NH, o NH2 o
CH CH,, C
C C II C CH-.-C-C ClI , S CIO CH -C-C
, CH,
\
CH H OH II OH H OH
Isoleucine Leucine Methionine

,o NH,
NH
.-
CH - C — C
H OH
CH
NH2 O
CH-C- C
OH H
y
s
OH
.
- -
CH -C C
i
I
H
Lro
\
OH
Phenylalanine Threonine Tyrosine

CARBON FAMILY 819

ELEMENTS HANDBOOK

Hemoglobin is a complex protein

made of hundreds of amino acids.
Its 3- dimensional shape is called
a tertiary structure. Tertiary
structures break down
when a protein
is denatured.

The chains are held together by S —S bonds between

sulfur atoms in two cysteine amino acids. Insulin is
one of the smaller proteins, containing only 51 amino
acids. In contrast, hemoglobin, which carries oxygen
in the blood, is a large protein consisting of four long
chains with the complicated three -dimensional struc - Vitamin C. ChH806
tures shown above. Proteins can lose their shape with
Water-soluble
increases in temperature or changes in the chemical
composition of their environment. When they are
returned to normal surroundings, they may fold or
coil up again and re - form their original structure.
Changing even one amino acid can change a cn?
protein 's structure and function. For example, the Vitamin A. C:0HM)O
difference between normal hemoglobin and the Fat -soluble
hemoglobin that causes sickle cell anemia is just
one amino acid substituted for another. You can see why we need vitamins and minerals in
our diet — to enable our enzymes to work . You can
Enzymes also see why we need only small amounts of them.
You learned how enzymes alter reaction rates in Minerals and coenzymes are not destroyed in bio-
Chapter 17. Some enzymes cannot bind to their chemical reactions. Like enzymes, coenzymes and
substrates without the help of additional molecules. minerals can be used over and over again.
These may be minerals, such as calcium or iron ions, Temperature and pll have the most significant
or helper molecules called coenzymes that play effects on the rates of reactions catalyzed by enzymes.
accessory roles in enzyme-catalyzed reactions. Many Most enzymes work best in a solution of approxi -
vitamins are coenzymes or parts of coenzymes. mately neutral pH. Most body cells have a pi 1 of 7.4.
Vitamins are organic molecules that we cannot However, some enzymes function only in acidic or
manufacture and hence need to eat in small amounts. basic environments. For example, pepsin, the collective

820 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

H O H
\ #
C H-C-OH
H-C-OH c=o
HO-C- H HO-C-H
!
H-C-OH H-C-OH
I
H - C- OH H-C-OH
CH:OH CH2OH
- Glucose -Fructose

H O H O
\ S \ S
c c
I
The protein in fish is denatured by the low pH of lime juice. Notice H - C- OH CH2
that the flesh shown with the limes has turned white compared
with the flesh at normal pH. H-C- OH H -C- OH
H-C- OH H - C- OH
term for the digestive enzymes found in the human
CH2OH CH2OH
stomach, works best at a very acidic piI of about 1.5.
-
DRibose 2-Deoxy -D-ribose
Cells that line the stomach secrete hydrochloric acid
to produce this low pH environment. When food Monosaccharides chain representation
travels down the digestive tract , it carries these
enzymes out of the stomach into the intestine. In the Two monosaccharides may be joined together to
intestine, stomach enzymes stop working because form a disaccharide. Sucrose, shown below, is a di -
sodium bicarbonate in the intestine raises the pH saccharide. A disaccharide can be hydrolyzed to pro-
to about 8. Digestive enzymes in the intestine are duce the monosaccharides that formed it. By a
formed by the pancreas and work best at pH 8. series of condensation reactions, many monosac -
Most chemical reactions, including enzyme charides can be joined to form a polymer called a
reactions, speed up with increases in temperature. polysaccharide (commonly known as a complex
However, high temperatures (above about 60 C ) carbohydrate ).
destroy, or denature, protein by breaking up the
three-dimensional structure. For example, the protein
in an egg or a piece of meat denatures when the egg CH2OH
O
CH OH .
or meat is cooked. Proteins in the egg white become HO
opaque when denatured. Heating can preserve food OH
HOH
by denaturing the enzymes of organisms that cause
decay. In milk pasteurization, the milk is heated OH OH
to denature enzymes that would turn it sour. Lactose —made from glucose and galactose
Refrigeration and freezing also help preserve food
by slowing the enzyme reactions that cause decay. Cl HOH
j__ o HOH2C ^ O
HO H
Carbohydrates
Carbohydrates are sugars, starches, and related OH O HO
CTFOH
compounds. The monomers of carbohydrates are
OH OH
monosaccharides, or simple sugars, such as fructose
and glucose. A monosaccharide contains carbon, Sucrose —made from glucose and fructose
hydrogen, and oxygen in about a 1:2:1 ratio, which
is an empirical formula of CH2Q.

CARBON FAMILY 821

 ELEMENTS HANDBOOK

glucose monomers
c 11 ,011

-
II/ 1
Ai
i \?H
one Vi
C OH
\
II
c
Cellulose chains
linked by —
hydrogen bonds
•••,
H OH
glucose

••• ;

gl \ cogen cellulose starch

Glucose is the structural unit for glycogen, cellulose, and starch. Notice that these three
polymers differ in the arrangement of glucose monomers.

Three important polysaccharides made of glucose Lipids

monomers are glycogen, starch, and cellulose. Ani - Lipids are a varied group of organic compounds
mals store energy in glycogen. The liver and muscles that share one property: they are not very soluble in
remove glucose from the blood and condense it into water. Lipids contain a high proportion of C— 11
glycogen, which can later be hydrolyzed back into bonds, and they dissolve in nonpolar organic sol -
glucose and used to supply energy as needed. vents. such as ether, chloroform, and benzene.
Starch consists of two kinds of glucose polymers. Fatty acids are the simplest lipids. A fatty acid
It is hydrolyzed in plants to form glucose for energy consists of an unbranched chain of carbon anti
and for building material to produce more cells. hydrogen atoms with a carboxyl group at one end.
I he structural polysaccharide cellulose is probably Bonding within the carbon chain gives both saturat -
the most common organic compound on Earth. ed and unsaturated fatty acids, just as the simple
Glucose monomers link cellulose chains together at hydrocarbons ( see Chapter 22 ) can be saturated or
the hydroxyl groups to form cellulose fibers. Cotton unsaturated.
fibers consist almost entirely of cellulose. The bonds in a carboxyl group are polar, and
so the carboxyl end of a fatty acid attracts water

H H H H H H H H FI FI H H H H H O
I I I I I I I I I I I I I I I
H- ( C ( C - C- C - C ( c c c c c c c c
- - - - - - -
I I I I I I I I I I I I I I I
II H H H H H H H H H H H H H H OH
Palmitic acid — saturated

II H H H H H H H H H H H H H H O
I I I I I I I
I
H-C - C - C- C-C-C-C-C- C=C-C- C- C-C-C- C-C-C
I I I I I I I I I I I I I I I I I \
II 11 H H II H H II II II II II H II II II II OH
Oleic acid — monounsaturated

H H H H H II H H H H H H H ()
.

I I I I I I i I I
H C C C C C C C C C C C - C- C-C-C- C-C-(
- - - - - - = - - = -
I I I
H H H H H H H H H H HUH H H H H OH
Linoleic acid — polyunsaturated
These examples of common fatty acids show the differences in saturation level.

822 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

This phospholipid
molecule contains
two fatty - acid chains.

The fatty acids are oriented toward the

The lipid bilayer is the framework interior of the bilayer because they have
of the cell membrane. a low attraction for water.

Y *
rJ

_*
A
frEt a
i

This phospholipid
chain is part of
the lipid bilayer.

molecules. The carbon-hydrogen bonds of a lipid s and the fatty acid tails are nonpolar, as shown in the
hydrocarbon chain are nonpolar, however. The polar model above.
end will dissolve in water, and the other end will dis - Most fatty acids found in foods and soaps belong
solve in nonpolar organic compounds. T his behavior to a class of compounds called triglycerides. The fat
enables fatty acids to form membranes when they content shown on a nutrition label for packaged food
are dropped into water. It also gives soaps and deter - represents a mixture of the triglycerides in the food.
gents their cleaning power. Triglycerides have the general structure shown below.
Lipids are the main compounds in biological mem- Fatty acids are usually combined with other
branes. such as the cell membrane. Because lipids are molecules to form classes of biomolecules called
insoluble, the lipid bilayer of a cell membrane is glycolipids ( made from a carbohydrate and a lipid )
adapted to keep the contents of the cell inside sepa- or lipoproteins ( made from a lipid and a protein).
rated from the outer environment of the cell. These compounds are also parts of more -complex
The structural component of a cell membrane is a lipids found in the body.
phospholipid. The “ head" of the phospholipid is polar.

H () H O H
H-CfC„H2„ C > FI-C-tQH C- O- C- H
H
\
OH
II 11 ^
I
H O HO-C-H H O
I I
H CtC „H 2nfC + HO - C- H H - CHC H2 -)- C- O - C- H

H OH HO- C-H H
i
H H il O
O
H-CfC„H2 ,tC )
H-CfC„H:„tC-0-C- H
H OH H H
Saturated fatty acids + Glycerol Triglyceride
*
Triglycerides are made from three long - chain fatty acids bonded to a glycerol backbone .
CARBON FAMILY 823
 ELEMENTS HANDBOOK

Nucleic Acids Adenine 1

Nucleic acids are macromolecules that transmit NH,
ATP structure
genetic information. Deoxyribonucleic acid ( DNA ) C -N
is the material that contains the genetic information N C
that all organisms pass on to their offspring during C-H
H-C C /
reproduction. This information includes instructions N^ ^N
cr cr oi -
for making proteins as well as for making the other
nucleic acid, ribonucleic acid ( RNA ). Ribonucleic
acid ( RNA ) assists in protein synthesis bv helping to
i
II
o
i
O P O - P- O-P- O - CH
o
II II
o '
./ O

H/ Ribose
coordinate the process of protein assembly. 1 Triphosphate HV H
Nucleotides are the monomers of nucleic acids. OH OH
A nucleotide has three parts: one or more phos-
phate groups, a sugar containing five carbon atoms, nucleotide that supplies the energy for many meta -
and a ring-shaped nitrogen base, as shown below. bolic reactions.
RNA nucleotides contain the simple sugar ribose . The bases in nucleic acids attract each other in
DNA nucleotides contain deoxvribose (ribose pairs, a phenomenon known as base -pairing. DNA is
stripped of one oxygen atom ). Structures for both of made of four different nucleotides— those containing
these sugars are shown on page «S21. Cells contain the bases adenine ( A ), thymine (T), guanine (G), and
nucleotides with one, two, or three phosphate cytosine ( C ). The attraction between base pairs is
groups attached. Besides being the monomers of hydrogen bonding. Adenine forms hydrogen bonds
nucleic acids, several nucleotides play other roles. with thymine. Similarly, cytosine bonds to guanine.
For example, adenosine triphosphate ( ATP ) is the This base-pairing holds strands of DNA together.

o NH: o
H:N V H H,C C H H /
C
c c/
••
(
- C N C N C N
H- C II I
N c /N c c c c ''N-C C
' II II N ( ) n" ^O II
N Nil,
C=N
/ H II
II
| Adenine IThymine Cytosine I Guanine

Deoxyribose
Phosphate group

Hydrogen bonds
Uracil. RNA onlv

824 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

APPLICATION Chemical Industry

Silicon and Silicates It is now known that asbestos is a carcinogen .
Silicon is as important in the mineral world as car - When handled , asbestos releases dust particles that
bon is in living systems. Silicon dioxide and silicates are easily inhaled and can cause lung cancer.
make up about 87 % of Earth s crust. Silicates are a Asbestos materials found in older homes and build -
class of compounds containing silicon , oxygen , one ings should be removed by firms licensed by the
or more metals, and possibly hydrogen. Many miner - Environmental Protection Agency ( EPA ).
al compounds are silicates. Sand is probably the
most familiar silicate. Silicones
Glasses consist of 75 % silicate. Borosilicate glass Silicones are a class of organic silicon polymers
is the special heat - resistant glass used in making composed of silicon , carbon , oxygen , and hydrogen.
laboratory beakers and flasks. The addition of 5% The silicon chain is held together by bonding with
boron oxide to the glass increases the softening the oxygen atoms. Each silicon atom is also bonded
temperature of the glass. Because boron and silicon to different hydrocarbon groups to create a variety
atoms have roughly similar radii , these atoms can of silicone structures.
be substituted for one another to make boro- Silicones are widely used for their adhesive and
silicate glass. protective properties. They have good electric insulat -
Asbestos is the name given to a class of fibrous ing properties and are water-repellent. Some silicones
magnesium silicate minerals. Asbestos is very strong have the character of oils or greases, so they are used
and flexible , and it does not burn , so it was widely as lubricants. Silicones are also used in automobile
used as a heat-insulating material. and furniture polishes as protective agents.

Silicon has the

ability to form
long chain com -
pounds by bond- J
< r Silicones also
have a tetrahe-
dral structure
How does this
.
ing with oxygen. structure differ ..
The Si04 subunit from that of a
in this silicate is silicate?
tetrahedral.

Because of their protective properties, silicones are used in a

Silicates exist in a variety of mineral forms, including mica. number of consumer products, from cosmetics to caulkings.

CARBON FAMILY 825

 ELEMENTS HANDBOOK

APPLICATION Technology
Semiconductors and photovoltaic cells ( “ solar cells ). Though silicon
'

When electrons can move freely through a material, is the basis of most semiconductor devices in the
the material is a conductor. The electrons in metals computer industry, pure silicon has little use as a
are loosely held and require little additional energy semiconductor. Instead, small amounts of impurities
to move from one vacant orbital to the next. A set of are added to increase its conductive properties.
overlapping orbitals is called a conduction bund . Adding impurities to silicon is called doping, and the
Because electrons can easily jump to the conduction substances added are dopants. The dopant is usually
band, metals conduct electricity when only a very incorporated into just the surface layer of a silicon
small voltage is applied. chip. Typical dopants include the Group 15 elements
Semiconductors conduct a current if the voltage phosphorus and arsenic and the Group 13 elements
applied is large enough to excite the outer- level elec - boron, aluminum, gallium, and indium.
trons of their atoms into the higher energy levels. A silicon atom has four electrons in its outer
With semiconductors, more energy, and thus a higher energy level whereas Group 13 atoms have three
voltage, is required to cause conduction. By contrast, and Group 15 atoms have five. Adding boron to
nonmetals are insulators because they do not con- silicon creates a mix of atoms having four valence
duct at ordinary voltages, loo much energy is needed electrons and atoms having three valence electrons.
to raise their outer electrons into conduction bands. Boron atoms form only three bonds with silicon,
Semiconductor devices include transistors: diodes, whereas silicon forms four bonds with other silicon
including light -emitting diodes ( LEDs): some lasers: atoms. The unbonded spot between a silicon atom

Metals Semiconductors Insulators

Conduction band Conduction band

(empty) (empty)

Small energy
Conduction gap
QJ
bands Large energy gap —
C forbidden zone
LU

Filled band

Filled band

J Partially
filled band
Overlapping
bands

This model shows the difference in the levels of energy required to excite electrons into the
conduction band in metals, semiconductors, and insulators. The forbidden zone is too great
an energy gap in insulators for these elements to function as conductors. The energy gap for
semiconductors is small enough that it can be crossed under certain conditions.

826 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

1 Group 18

H Dopants
2

Group 1 Group 2 Group 13 Group 14 Group IS Group 16 Group 17

He
3 4
Semiconductor elements 5 6 7 8 9 10
Li Be Forms semiconductor compounds B C N O F Ne
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9 Group 10 Group 11 Group 12
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg TI Pb Bi Po At Rn
87 88 89
Fr Ra Ac

Semiconductor elements and dopants fall in the metalloid region of the periodic table.
Semiconductor compounds often contain metals.

and a boron atom is a hole that a free electron can Doping silicon with phosphorus or arsenic pro-
occupy. Because this hole “attracts" an electron, it is duces the opposite effect. When phosphorus is
viewed as if it were positively charged. Semiconduc - added to silicon, it forms four bonds to silicon atoms
tors that are doped with boron , aluminum, or gallium and has a nonbonding electron left over. This extra
are p -type semiconductors, the p standing for “posi - electron is free to move through the material when a
tive." P-type semiconductors conduct electricity voltage is applied, thus increasing its conductivity
better than pure silicon because they provide spaces compared with pure silicon. These extra electrons
that moving electrons can occupy as they flow have a negative charge. Therefore, the material is
through the material. an n -type semiconductor . Compare these two types
of semiconductors in the models below.

Positive hole Mobile electron

•• •• •• ••

•• 9 9 9 9 9 9
•• •• • 9
•• •• •• •• ••
9 9 9 9 I 9 9
9 9 9 9 9 9

Pure Si crystal p- type n- type

Each silicon atom in the pure crystal is surrounded by four pairs of electrons. The p - type
semiconductor model contains an atom of boron with a hole that an electron can occupy.
The n - type semiconductor model contains an atom of arsenic, which provides the extra
electron that can move through the crystal.

CARBON FAMILY 827

 GROUP 15
NITROGEN FAMILY

7
CHARACTERISTICS
N
Nitrogen
• consist of two nonmetals ( nitrogen and phospho- 14.0067
rus ) , two metalloids ( arsenic and antimony ), and |He|2sV Atomic radius
one metal ( bismuth ) increases
15
• Nitrogen is most commonly found as atmospheric P
N:: phosphorus as phosphate rock; and arsenic, Phosphorus
antimony, and bismuth as sulfides or oxides. 30.973 761
Ionic radius
( Ne]3sV
Antimony and bismuth are also found as free increases
elements. 33

• range from very abundant elements ( nitrogen and As

Arsenic
phosphorus ) to relatively rare elements ( arsenic, ,
74.921 60 Ionization energy
antimony, and bismuth ) [ Ar ]3£/ 04$ V
decreases
• consist of atoms that contain five electrons in their
outermost energy level
• tend to form covalent compounds, most common-
ly with oxidation numbers of +3 or +5
Sb
51

Antimony
121.760
|Kr ]4 d105sV
I
Electronegativity
decreases
• exist in two or more allotropic forms, except 83
nitrogen and bismuth Bi
Bismuth
• are solids at room temperature, except nitrogen 208.980 38
[XeW’V
^sV
Some matches con -
tain phosphorus
compounds in the
match head. Safety
matches contain
phosphorus in the
striking strip on
the matchbox.

Phosphorus
Phosphorus exists in three
allotropic forms. White
phosphorus must be kept r *
-n
underwater because it catches
on fire when exposed to air. £
You can see the contrast in physical properties among the ele - The red and black forms are
T
ments of this family. Arsenic, antimony, and bismuth are shown. stable in air.

828 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

COMMON REACTIONS
With Oxygen to Form Oxides With Metals to Form Binary Compounds
Example: P4(s) + 502(g ) — PPinC ) Example: 3Mg($) + N2(g) » Mg2N2(s)
. * '
As Sb. and Bi follow this reaction pattern, but as
monatomic elements. N reacts to form NO and N02.
It also reacts as N: to form N203 and N205.

ANALYTICAL TEST

There are no simple analytical tests for the presence

of nitrogen or phosphorus compounds in a sample.
Antimony produces a pale green color in a flame
test, and arsenic produces a light blue color. Arsenic,
antimony, and bismuth are recognized in qualitative
analyses bv their characteristic sulfide colors.

Formation of sulfides is the confirmatory qualitative analysis Arsenic flame test Antimony flame test
test for the presence of bismuth, antimony, and arsenic.

PROPERTIES OF THE CROUP 15 ELEMENTS

N p* As Sh Bi
Melting point (°C) -209.86 44.1 817 ( 28 atm) 630.5 271.3
Boiling point ( C ) -195.8 280 613 (sublimes) 1750 1560 ± 5
Density ( g/cnr ) 1.25 x 1(T3 1.82 5.727 6.684 9.80
Ionization energy ( kJ/mol ) 1402 1012 947 834 703

Atomic radius (pm) 75 110 120 140 150

Ionic radius ( pm ) 146 (N- ) 3-
212 ( P 3*) 76 ( Sb3+) 103 ( Bi 3+)
Common oxidation -3. +3, +5 -3, +3, +5 +3, +5 +3, +5 +3
number in compounds
Crystal structure! cubic ( as a solid ) cubic rhombohedral hep rhombohedral
Hardness ( Mohs * scale ) none ( gas ) 3.5 3.0 2.25
1
Data given apply to white phosphorus,
t C rystal structures are for the most common allotropes.

NITROGEN FAMILY 829

 ELEMENTS HANDBOOK

APPLICATION Biology
Plants and Nitrogen pheric N: to make NH3 is called nitrogen fixation.
All organisms, including plants, require certain ele - Several kinds of nitrogen- fixing bacteria live in the
ments to survive and grow. These elements include soil and in the root nodules of plants called legumes.
carbon, hydrogen, oxygen, nitrogen, phosphorus, Legumes obtain the nitrogen they need through a
potassium, sulfur, and several other elements needed .
symbiotic relationship with nitrogen- fixing bacteria
in small amounts. An organism needs nitrogen to Legumes include peas, beans, clover, alfalfa, and
synthesize structural proteins, enzymes, and the locust trees. The bacteria convert nitrogen into ammo-
nucleic acids DNA and RNA. .
nia, NH3 which is then absorbed by the host plants.
Carbon, hydrogen, and oxygen are available to Because wheat, rice. corn, and potatoes cannot
plants from carbon dioxide in the air and from water perform the same feat as legumes, these plants
in both the air and the soil. Nitrogen is necessary for depend on nitrogen- fixing bacteria in the soil. Soil
plants' survival. Although nitrogen gas. N->. makes up bacteria convert NH3 into nitrate ions, NOT the
78% of air. most plants cannot take nitrogen out of form of nitrogen that can be absorbed and used by
the air and incorporate it into their cells, because the plants. These plants also often need nitrogen fertil-
strong triple covalent bond in N: is not easily broken. izers to supplement the work of the bacteria. Besides
Plants need nitrogen in the form of a compound that supplying nitrogen, fertilizers are manufactured to
they can take in and use. The process of using atmos- contain phosphorus, potassium, and trace minerals.

Nitrogen - fixing bacteria,

Rhizobium, live in these
small nodules that grow
on the roots of soybeans .

Soybeans are legumes that live in a symbiotic

relationship with nitrogen - fixing bacteria.

830 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

APPLICATION Chemical Industry

Fertilizers the container. These numbers are the N - P-k formula
Fertilizers can supply nitrogen to plants in the form of the fertilizer and indicate the percentage of N, P.
of ammonium sulfate, ammonium nitrate, and urea, and k. respectively. A fertilizer graded as 6- 12-6, for
all of which are made from NH V Now you know example, contains 6% nitrogen. 12 % phosphorus,
why there is such a demand for ammonia. Though and 6% potassium by weight.
some soils contain sufficient concentrations of phos- Nitrogen stimulates overall plant growth.
phorus and potassium, most soils need additional Phosphorus promotes root growth and flowering.
nitrogen for adequate plant growth. Ammonia, Potassium regulates the structures in leaves that
ammonium nitrate, or urea can fill that need. allow C02 to enter the leaf and 0: and H20 to exit.
Most fertilizers contain all three major plant nutri - Fertilizers are available in N - P- k formulas best suit -
ents N. P. and k. and are called complete fertilizers . ed for their intended use. For example, plants that
A typical complete fertilizer might contain ammo- produce large amounts of carbohydrates ( sugars )
nium nitrate or sodium nitrate to provide nitrogen. need more potassium than most other types of
Calcium dihydrogen phosphate, Ca( H:P04)2, or the plants. Grain crops need higher concentrations of
anhydrous form of phosphoric acid P4O 10, can pro-. .
phosphorus Lawn fertilizers applied in the spring
vide phosphorus. Potassium chloride, KCI, or potas- are generally high in nitrogen to stimulate shoot
sium oxide. k:0. can provide potassium. growth in grasses. Lawn fertilizers applied in the fall
The proportion of each major nutrient in a fertil- of the year should have a higher phosphorus content
izer is indicated by a set of three numbers printed on to stimulate root growth during the winter.

TABLE 6 A Some Commercial Fertilizers and Uses

Fertilizer composition ( N- P- K ) Uses
1 - 2- 1 ratio earlv -spring application for trees and shrubs with flowers and fruit:
10-20-10 15-30 15 - general-purpose feedings of the following: cucumbers, peppers, tomatoes
3- 1- 2 ratio lawns and general-purpose feedings of the following: trees, shrubs,
12 - 4 -N 15 - 5- 10 21 - 7- 4 16- 4- 8 most berries, apple trees, grapes, vines, walnut trees, broccoli, cabbage,
20- 5- 10 carrots, onions
High nitrogen pecan trees, lawns, early feedings of corn
33-0-0 21 -0-0 40-4-4 30-6-6
balanced general purpose feeding of the following: broccoli, cabbage, melons,
13- 13- 13 potatoes
Special purpose: acid-loving azaleas, rhododendrons, camellias, gardenias
flowering shrubs
12- 10- 4
Special purpose roses
18-2446
Special purpose: flowering flowering plants and shrubs (annuals and perennials)
12-55-6
Special purpose: root growth starter fertilizer for transplants
5-20-10

NITROGEN FAMILY 831

 CROUP 16
OXYGEN FAMILY

CHARACTERISTICS
O
Oxygen
• occur naturally as free elements and in combined 15.9994
states (He)2sV Atomic radius
• consist of three nonmetals ( oxygen , sulfur, and increases
16
selenium ), one metalloid ( tellurium ), and one
metal ( polonium )
• consist of atoms that have six electrons in their
s
Sulfur
32.065
INe|3sV
1
Ionic radius
increases
outermost energy level
34
• tend to form covalent compounds with other Se
elements Selenium

• exist in several allotropic forms

70 qc
|Ar|3 </ 04sV
, Ionization energy
decreases
• tend to exist as diatomic and polyatomic molecules, 52
such as Oi, O3, S6, S8, and Se8 Te
Tellurium
• commonly exist in compounds with the -2 oxida - 127.60 Electronegativity
[ Kr|4 d 5$y decreases
tion state but often exhibit other oxidation states '°

\
84
Sulfur is found naturally in Po
underground deposits and Polonium
in the steam vents near
( 209)
[ Xel4 fu5d 06$y
,
volcanoes.

Two allotropic forms

of sulfur are
orthorhombic and
TS \ . monoclinic. Each has
. * *1 V •V
U a different crystal
i
/

%
1 • • - . I structure .
r .*
.. h.
\ AM '
-
-
3 / '
: '• A
> . v • V \

- -V /

/
Orthorhombic -/

9
Sulfur exists in combined forms in many minerals. Iron pyrite, FeS2,
black galena, PbS, and yellow orpiment, As Sj , are shown. Monoclinic
^
832 ELEMENTS HANDBOOK
 ELEMENTS HANDBOOK

COMMON REACTIONS
With Metals to Form Binary Compounds
Example: 8Mg(s) + SH( / ) » 8MgS(s)
02, Se , and Te follow this pattern in reacting with /\
Na . . Mg. and Al.
K, Ca
\ /
With Oxygen to Form Oxides
Example: Se( s ) + O 2 ( g ) > Se02(s)
.
S Te. and Po follow this pattern. S, Se, and Te can form
SQ3, Se03. and Te03.

With Halogens to Form Binary Compounds

Example : S8( l ) + 8C ( g )
12 > 8Sd2(/)
O, Se. Te. and Po follow this pattern in reacting with
F2. Cl2, Br 2, and I2

With Hydrogen to Form Binary Compounds

Sulfur exists as S8 molecules in which the
2Hi(g) + 02(g) 2H20( / )
* atoms are bonded in a ring, as shown by
the ball -and -stick and space - filling models.

ANALYTICAL TEST
There is no simple analytical test to identify all ele - splint test, in which a glowing splint bursts into flame
ments of this family. Selenium and tellurium can be when thrust into oxygen. Elemental sulfur is typically
identified by flame tests. A light blue flame is charac - identified by its physical characteristics, especially its
teristic of selenium, and a green flame is characteris- color and its properties when heated. It melts to form
tic of tellurium. Oxygen can be identified by the a viscous brown liquid and burns with a blue flame.

A glowing splint thrust into oxygen bursts Sulfur burns with a characteristically deep Molten sulfur returns to its orthorhombic
into a bright flame. blue flame. form upon cooling.

OXYGEN FAMILY 833

 ELEMENTS HANDBOOK

PROPERTIES OF THE CROUP 16 ELEMENTS

() S Se Te Po
Melting point ( C) -218.4 119.0 217 449.8 254
Boiling point ( C ) -182.962 444.674 685 989.9 962
1.429 x HI 3 1.96 4.82 6.24 9.4
Density ( g/cnv ) "

Ionization energy ( kJ / mol ) 1314 10( H ) 941 869 812

Atomic radius ( pm ) 73 103 119 142 168

Ionic radius ( pm ) 140 184 198 221

Common oxidation
number in compounds
-i —2. 4 + , 46
*
-2. 4-2. 44 , 4-6 -2 , 4-2. 44. +6 -2. +2, -M . +6

Crystal structure* orthorhombic, orthorhombic. hexagonal hexagonal cubic.

rhombohedral , monoclinic rhombohedral
cubic ( when solid )
Hardness ( Mohs' scale ) none ( gas ) 2.0 2.0 2.3
Most dements of this family can have more than one crystal structure.

APPLICATION Chem icaI Industry

Oxides If a hydroxide formed by a metal oxide is water -
Oxides of the reactive metals are ionic compounds. soluble , it dissolves to form a basic solution. An
I he oxide ion from any soluble oxide reacts immedi - oxide that reacts with water to form a basic solution
*

ately with water to form hydroxide ions as repre- is called a basic oxide or a basic anhydride. Table 7 A
sented by the following equation . on the next page lists oxides that form basic solu -
tions with water.
02~( aq ) 4- H20( / ) ~
> 20 H ( aq )
Molecular Oxides
The reactive metal oxides of Groups 1 and 2 react Nonmetals, located on the right side of the periodic
vigorously with water and release a large amount of table , form molecular oxides. For example, sulfur
energy as heat. The product of the reaction is a metal forms two gaseous oxides: sulfur dioxide. S02. and
hydroxide. The following equation is an example of sulfur trioxide , SOv In reactions typical of nonmetal
this reaction. oxides, each of the sulfur oxides reacts with water to
form an oxyacid .
Na ,0 ( .s ) + I F O( / ) > 2 NaOH ( aq ) An oxide that reacts with water to form an acid is
called an acidic oxide or an acid anhydride. As with
A basic oxide can be thought of as the dehydrated
the basic anhydrides, each acid anhydride can be
form of a hydroxide base. Oxides of the less reactive
thought of as the dehydrated form of the appro-
metals, such as magnesium , can be prepared by
priate oxyacid. For example , when sulfuric acid
using thermal decomposition to drive off the water.
decomposes, the loss of H:0 leaves the oxide S03,
which is an anhydride.
Mg( OH )i (s )
^ MgO(.v ) + H20(# )

I l 2SO A( aq ) heat
H 20(g ) + so3(s )
Hydroxides of the reactive metals of Group 1 are 4

too stable to decompose in this manner.

834 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

Amphoteric Oxides
Table 7 A lists some common oxides of main-group ,
MgO(s) + H:S04( // /. aq ) » MgS04( </ </ ) + H:Q( / )
-

elements. You can see that the active metal oxides

The reaction between a basic metal oxide, such
are basic and that the nonmetal oxides are acidic.
as MgO, and an acidic nonmetal oxide, such as C02,
Between these lies a group of oxides, the amphoteric
lends to produce an oxygen-containing salt. The dry
oxides. The bonding in amphoteric oxides is inter -
mediate between ionic and covalent bonding. As
oxides are mixed and heated without water. Salts
a result , oxides of this type show behavior inter-
such as metal carbonates, phosphates, and sulfates
can be made bv this synthesis reaction.
mediate between that of acidic oxides and basic
oxides, and react as both acids and bases. MgO( s ) + C02(g) ,
> MgCO ( j)
.
Aluminum oxide. A1203 is a typical amphoteric
. + P401 )(.v )
(SCaO ( v ) > 2Ca3( P04)2(s )
oxide. With hydrochloric acid, aluminum oxide acts (

as a base. The reaction produces a salt and water. CaO(s) + SO;(g) » CaS04(.v )
Al203(.v ) + 6HCI(w/ ) 2 AlCI3( tf </ ) + 3H20( / ) Reactions of Hydroxides with
Nonmetal Oxides
With aqueous sodium hydroxide, aluminum oxide
acts asan acid. The reaction forms a soluble ionic Nonmetal oxides tend to be acid anhydrides The .
compound and water. That compound contains reaction of a hydroxide base with a nonmetal oxide
aluminate ions. AI02. ( The A 1CK formula is used .
is an acid-base reaction The product is either a salt
or a salt and water, depending on the identities and
here rather than the more precise hydrated alumi -
nate formula, Al( OH ) 4. ) relative quantities of reactants. For example. 2 mol
of the hydroxide base sodium hydroxide and 1 mol
AI2Q 3(.v ) + 2NaOH(tf </ ) 2NaAI02( u</ ) + 1 TO( / ) of the nonmetal oxide carbon dioxide form sodium
carbonate, which is a salt, and water.
Reactions of Oxides
In the reaction between an acid and a metal oxide, C02(g) + 2NaOH( tf </ ) -» Na 2C03( rt </ ) + H:0( / )
the products are a salt and water —the same as the
However, if sodium hydroxide is limited, only sodium
products in a neutralization reaction. For example, hydrogen carbonate is produced.
when magnesium oxide reacts with dilute sulfuric
acid, magnesium sulfate and water are produced. CO:(g) + NaOH( aq ) > NaHCO
^)
TABLE 7 A Periodicity of Acidic and Basic Oxides of Main- Group Elements
Group Number
1 2 13 14 15 16 17

Li20 BeO B:0 , co2 N2Os

basic amphoteric acidic acidic acidic
Na20 MgO AI2O? Si02 PA » so, ci2o
basic basic amphoteric acidic acidic acidic acidic
K:0 CaO Ga203 Ge02 As4Oh SeO T
basic basic amphoteric amphoteric amphoteric acidic
Rb:Q SrO In203 Sn02 Sb406 TeO , i,o5
basic basic basic amphoteric amphoteric acidic acidic
Cs2( ) BaO TI2O , PbO: Bi203
basic basic basic amphoteric basic

OXYGEN FAMILY 835

 ELEMENTS HANDBOOK

APPLICATION The Environment

Ozone to reach Earths surface in large amounts, life would
Ozone. O v is an allotrope of oxygen that is important .
he impossible Even now, the normal amount of ultra-
for life on Earth. Like 02, 03 is a gas at room tem - violet light reaching Earth's surface is a major cause
perature. However, unlike 02, 03 is a poisonous of skin cancer and the damage to DNA molecules
bluish gas with an irritating odor at high concentra- that causes mutations. One life-form that is very sen-
w

tions. The triatomic ozone molecule is angular ( bent ) sitive to ultraviolet radiation is the phytoplankton in
with a bond angle of about 116.5°. The O—O bonds in the oceans. These organisms carry out photosynthesis
ozone are shorter and stronger than a single bond but , and are the first level of oceanic food webs.
longer and weaker than a double bond. The ozone
molecule is best represented by two resonance hybrid Ozone and Air Pollution
structures. Ozone in the lower atmosphere is a harmful pollu-
:o: Q: tant . Ozone is highly reactive and can oxidize or -
o: • .
ganic compounds The products ol these reactions
Q: :o:
are harmful substances that , when mixed with air.
water vapor, and dust, make up photochemical smog .
Ozone forms naturally in Earth 's atmosphere more
This mixture is the smog typically found in cities.
than 24 km above the Earth 's surface in a layer called
Typically, ozone is produced in a complex series
the stratosphere. There, O, molecules absorb energy
of reactions involving unburned hydrocarbons and
from ultraviolet light and split into free oxygen atoms.
nitrogen oxides given off from engines in the form
ultraviolet light of exhaust and from fuel-burning power plants.
o2( » 20
^) When fuel burns explosively in the cylinder of an
A free oxygen atom has an unpaired electron and is internal-combustion engine, some of the nitrogen in
highly reactive. A chemical species that has one or the cylinder also combines with oxygen to form NO,
a very reactive nitrogen oxide free radical.
more unpaired or unshared electrons is referred to as
a free radical . A free radical is a short - lived fragment
N2(£ ) + 02(g) 2NO
of a molecule. The oxygen free radical can react with
a molecule of 02 to produce an ozone molecule.
When the free radical reaches the air. it reacts with
oxygen to produce N02 radicals, which react with
o 02(g) > Q3(g) water in the air to produce HN03.

A molecule of 03 can then absorb ultraviolet light

2NO + 02(g) 2NO:
and split to produce 02 and a free oxygen atom.
3NO> + H-»0 /
( ) > 0 + 2HN03( <W/ )
N
ultras iolcl light
03(g) > 0-»( g ) + o
In sunlight, nitrogen dioxide decomposes to give
nitric oxide and an atom of oxygen. Note that the NO
The production and breakdown of ozone in the
produced is free to undergo the previous reaction
stratosphere are examples of photochemical pro -
once more.
cesses, in which light causes a chemical reaction.
In this way, 03 is constantly formed and destroyed NO,
sunlight
NO + O
in the stratosphere, and its concentration is deter -
mined by the balance among these reactions. The Just as it is in the stratosphere, a free oxygen atom
breakdown of ozone absorbs the suns intense ultra - in the lower atmosphere is highly reactive and reacts
violet light in the range of wavelengths between with a molecule of diatomic oxygen to form ozone.
200 nm and 320 nm. Light of these wavelengths dam -
ages and kills living cells, so if these wavelengths were O + 02( g ) » 03( £)

836 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

Sulfuric Acid Properties and Uses of Sulfuric Acid

Sulfuric acid is the so-called "king of chemicals " Concentrated sulfuric acid is a good oxidizing agent .
because it is produced in the largest volume in the During the oxidation process, sulfur is reduced from
United States. It is produced by the contact process. +6 to +4 or -2. The change in oxidation state for a
This process starts with the production of SO: by reaction depends on the concentration of the acid
burning sulfur or roasting iron pyrite. FeS2. The and on the nature of the reducing agent used in the
purified sulfur dioxide is mixed with air and passed reaction.
through hot iron pipes containing a catalyst . The Sulfuric acid is also an important dehydrating
contact between the catalyst, S02, and C) 2 produces agent. Gases that do not react with H 2 S04 can
sulfur trioxide, SO3, and gives the contact process its be dried by being bubbled through concentrated
name. SO3 is dissolved in concentrated H 2 S()4 to sulfuric acid. Organic compounds, like sucrose, are
produce pyrosulfuric acid. U 2 S 2Q7. dehydrated to leave carbon, as shown by the follow -
ing reaction.
SQ3( g) + H2S04(tfr/ ) » H2s20-}( aq )
Ci:H22On (.v ) + 11 H 2S04(M/ )
The pyrosulfuric acid is then diluted with water to 12C( s) + 11H2S04 H20( / )
produce sulfuric acid.
The decomposition of sucrose proceeds rapidly, as
H2S2O7(«? ) + H20( / ) » 2H 2SQ4(£M/ ) shown in Figure 17 on page 737.
About 60% of the sulfuric acid produced in this
country is used to make superphosphate, which is a
Other: detergents, mixture of phosphate compounds used in fertilizers.
drugs, dyes,
paint, paper,
explosives
15 %

TABLE 7 B Top Ten Chemicals

Raw material -~ Produced in the U.S.
for other
chemicals
\15% Physical
Rank Chemical state Formula
Fertilizer
l sulfuric acid / H2SO4
5%
Petroleum
9 nitrogen 8 N2
refining 5%
/ 3 oxygen 8
Metal 4 ethylene 8 C2H4
processing
5 calcium oxide 5 CaO
( lime )

6 ammonia 8 NH3
7 phosphoric acid / H;,P04
H 2 SO 4 8 sodium hydroxide 5 NaOH
Important uses of the U.S. supply of sulfuric acid
9 propylene 8 C3H „
10 chlorine 8 CU

OXYGEN FAMILY 837

 CROUP 17
HALOGEN FAMILY
I
9
CHARACTERISTICS
F
Fluorine
• are all nonmetals and occur in combined form 18.998 4032
in nature, mainly as metal halides |He]2sV Atomic radius
• are found in the rocks of Earth’s crust and 17
increases
dissolved in sea water Cl
Chlorine
• range from fluorine , the 13th most abundant ele- 35.453
ment , to astatine, which is one of the rarest (Ne)3sV Ionic radius
elements increases
35
• exist at room temperature as a gas ( F2 and Cl 2 ), a Br
Bromine
liquid ( Br:). and a solid ( I: and At ) 79.904
'° V
|Ar )3d 4$ Ionization energy
• consist of atoms that have seven electrons in their decreases
outermost energy level 53

• tend to gain one electron to form a halide, X "

ion , i
Iodine
but also share electrons and have positive ,
126.904 47
[ Kr|4 d 05sV Electronegativity
oxidation states decreases
• are reactive, with fluorine being the most reactive 85
of all nonmetals At
Astatine
( 210 )
[ Xe|4 / u5 rt$ V \

Halogens are the only family that contains elements representing all three states Iodine sublimes to produce a violet vapor that
of matter at room temperature. Chlorine is a yellowish green gas; bromine is a recrystallizes on the bottom of the evaporating dish
reddish brown liquid; and iodine is a purple- black solid. filled with ice.

838 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

COMMON REACTIONS*
With Metals to Form Halides
I Chlorine com -

1
Example: Mg(s) + CU ( g ) — MgCM.v ) bines readily with
iron wool, which
Example: Sn(s ) -f 2F2(g) SnF4(i)
ignites in chlorine
The halide formula depends on the oxidation state of the metal. gas to form FeCI3.

With Hydrogen to Form Hydrogen Halides

Example: H2(g) + F2(g) -4 2HF( g)
.
Cl2, Br 2 and F also follow this pattern .
With Nonmetals and Metalloids to Form Halides
Example: Si( s) + 2CI2 ( g) 4 SiCl4($)
Example: N2(g) + 3F2(g) 4 2NF3(g)
Example: P4(.v ) + 6Br 2( / ) 4 4 PBr 3(.v )
The formula of the halide depends on the oxidation state of the
metalloid or nonmetal.

With Other Halogens to Form Interhalogen Compounds

Example: Br 2( / ) + 3F2(g) > 2BrF3( / )
* Chemists assume that astatine undergoes similar reactions,
but few chemical tests have been made.

Hydrofluoric acid is used to etch patterns into glass. Shown here from left to right are precipitates of AgCI, AgBr, and Agl.

ANALYTICAL TEST
As with most elements, the presence of each of the Cl ( aq ) -f Ag+( aq ) —» AgCl(s)
halogens can he determined by atomic absorption Br ( aq ) + Ag* ( aq )
~
—» AgBr( 5 )
spectroscopy. Fluorides react with concentrated l ~( aq ) + Ag+( aq ) — 4 Agl( 5 )
sulfuric acid. I 12 S04. to release hydrogen fluoride
gas. Three of the halide ions can be identified in
solution bv their reactions with silver nitrate.

HALOGEN FAMILY 839

 ELEMENTS HANDBOOK

PROPERTIES OF THE CROUP 17 ELEMENTS

F Cl Br I At

Melting point ( C) -219.62 - 100.98 -7.2 113.5 302

Boiling point ( C) - 188.14 -34.6 58.78 184.35 337
3
Density (g/cm ') 1.69 x 10 -'
'
3.214 x 10 "
3.119 4.93 not known

Ionization energy (kJ/mol ) 1681 1251 1140 1008

Atomic radius ( pm ) 72 100 114 133 140

Ionic radius (pm) 133 181 196 220

Common oxidation -1 -1.4 1.4-3, 4-5. 4-7
*
— 1. + 1. +3, +5, +7 — 1. + 1. +3, f5, +7 -K +5
*

number in compounds
Crystal structure cubic orthorhombic orthorhombic orthorhombic not known

APPLICATION The Environment

Chlorine in Water Treatment When chlorine is added to water, the following reac -
For more than a century, communities have treated tion produces HC1 and hypochlorous acid. HOC1.
their water to prevent disease. A treatment process
widely used in the United States is chlorination. All Cl2( tg ) + H20( / ) 4 HCI( ^/ ) 4- HOCI( < / </ )
-
halogens kill bacteria and other microorganisms.
Chlorine, however, is the only halogen acceptable Hypochlorous acid is a weak acid that ionizes to give
for large-scale treatment of public water supplies. hydrogen ions and hypochlorite ions. OCT.

HOCl( < / </ ) 4- H:0( / ) 4 H3C)+( aq ) 4- OC|-( tf <7 )

CL PH
3.0 §8 2
1.5 § 7.8

1.0 7.6
I» 7.2
°0.3- I
5a SOW ASH

§ 6.8
S
*
Swimming pools are
routinely tested to be
sure the chlorine level
is safe.

Ca (CIO) 2

The "chlorine " used in swimming pools is really the compounds shown above and not chlorine at all.

840 ELEMENTS HANDBOOK

 ELEMENTS HANDBOOK

The OCI ions are strong oxidizing agents that can Aurora, Illinois, a city that was similar to Grand
destroy microorganisms . Rapids and Muskegon, except that it had a natural F~
In some water- treatment plants, calcium hypo - concentration of 1.2 ppm in the water supply. After
chlorite, Ca( CIO ) ?, a salt of hypochlorous acid, is 10 years, the rate of tooth decay in Grand Rapids had
added to water to provide OCI ions. Similar treat - dropped far below that in Muskegon and was about
ments are used in swimming pools. the same as it was in Aurora.
Nearly a hundred cities in the United States and Tooth enamel is made of a strong, rocklike materi-
thousands of communities in Europe use chlorine in al consisting mostly of calcium hydroxyphosphate,
the form of chlorine dioxide, CIO:, as their primary Cas( P04h( 0H ). also known as apatite. Apatite is
means of disinfecting water. The main drawback to an insoluble and very hard compound—ideal for
the use of CIO: is that it is unstable and cannot be tooth enamel. Sometimes, however, saliva becomes
stored. Instead, CIO ? must be prepared on location more acidic, particularly after a person eats a high -
by one of the following reactions involving sodium sugar meal. Acids ionize to produce hydronium ions,
chlorite, NaCIO?. which react with the hydroxide ion. OH -, in the
apatite to form water. The loss of OH - causes
IONaC10:( </ </ ) + 5H?S04(M/ ) > the apatite to dissolve.
8CIO?(g) + 5Na? S04( fl / ) + 2 \ \ C \ ( i u j ) + 4H:0( / )
* Ca5( PO4 h( OH)(.0 + H }0+ { aq )
2NaCIO:( < / </ ) + Cl,(g) » 2CI02(S) + 2NaCI( fl<y ) 5Ca2+( a<7 ) + 3POl ( aq ) + 2H:0( / )
'

The expense of using CIO? makes it less desirable Saliva supplies more OH ions, and new apatite is
"

than Cl: in water- treatment systems unless there formed, but slowly.
are other considerations. For example, the use of If fluoride ions are present in saliva, some fluor -
CIO is likely to result in purified water with less
? .
apatite Ca 5( PQ4 ) 3 F. also forms.
of the aftertaste and odor associated with water
5Ca2 ~ ( aq ) + 3P04 ( a q ) + F ( aq )
purified by Cl . ?
* Ca5( P04)3F(.v)
Fluoride and Tooth Decay Fluorapatite resists attack by acids, so the tooth
In the noticed that people living in
1940s, scientists enamel resists decay better than enamel containing
communities that have natural water supplies with no fluoride.
.
high concentrations of fluoride ions F , have signifi- When the beneficial effect of fluoride had been
cantly lower rates of dental caries ( tooth decay ) than established, public health authorities proposed that
most of the population. fluoride compounds be added to water supplies in
In June 1944. a study on the effects of water fluori - low- fluoride communities. Fluoridation started in
dation began in two Michigan cities, Muskegon and the 1950s. and bv 1965, nearly every medical and
Grand Rapids, where the natural level of fluoride in denial association in the United States had endorsed
drinking water was low ( about 0.05 ppm ). In Grand fluoridation of water supplies. In the past decade,
Rapids, sodium fluoride. NaF. was added to the drink - however, that trend slowed as opposition to
ing water to raise levels to 1.0 ppm. In Muskegon, no fluoridation grew.
fluoride was added. Also included in the study was

HALOGEN FAMILY 841

 Preparing for Chemistry Lab
Performing experiments in the chemistry laboratory provides you with the opportu -
nity to learn important lab techniques and observe interesting chemical reactions.
Taking the time to prepare for your lab activity will help ensure that you understand
the procedures you are to follow and that your experiment runs smoothly and safely.
You can prepare for each lab activity by reviewing the lab preparation tips below.

• Read the experiment thoroughly and familiarize yourself with what you will do at
,

each step in the procedure. If there is any part of the experiment that you do not
understand , ask your teacher before you start the experiment.

• Do any assigned pre-lab exercises. These will generally cover any calculations or
important observations that you will make.

• Prepare data tables ahead of time. If you have the data table ready before you
begin , you will be able to record your observations as they happen , in the appropri -
ate spaces.

• Review the materials list for the experiment . Make sure that you have all the items
you need to perform the experiment . If you are missing any items or if any items
are broken or unusable , let vour teacher know before you begin the lab.

• Review all safety guidelines and safety icons" at the beginning of each experiment.
Read “Safety in the Chemistry Laboratory in the front of your book for a com -
plete explanation of the safety rules that you should follow in the lab.

• Know where the emergency eyewash station , safety shower, and fire extinguisher

are located , and be sure you know how to use them . If you cannot locate the lab
safety equipment or you do not know how to use any equipment , ask your teacher
for help.

• Know the proper disposal procedures for the experiment. Your teacher will tell you
what to do with any substances that need to be disposed of.

842 LABORATORY PROGRAM

Pre - Laboratory Procedures
The Pre - Laboratory Procedures help you develop solid laboratory skills
before you do an actual experiment.

Extraction and Filtration 844

Gravimetric Analysis 846

Paper Chromatography 848

Volumetric Analysis 850

Calorimetry 852

LABORATORY PROGRAM 843

 PRE- LABORATORY PROCEDURE

Extraction and Filtration

Extraction, the separation of substances in a mixture by using a solvent, depends on solu-
bility. For example, sand can be separated from salt by adding water to the mixture. The salt
dissolves in the water, and the sand settles to the bottom of the container. The sand can be
recovered by decanting the water. The salt can then be recovered by evaporating the water.

Filtration separates substances based on differences in their physical states or in the size
of their particles. For example, a liquid can be separated from a solid by pouring the mix-
ture through a paper- lined funnel, or if the solid is denser than the liquid, the solid will set-
tle to the bottom of the container, which will leave the liquid on top. The liquid can then be
decanted, which will leave the solid.

SETTLING AND DECANTING GRAVITY FILTRATION

1. Fill an appropriate-sized beaker with the solid- 1. Prepare a piece of filter paper as shown in
liquid mixture provided by your teacher. Allow Figure B. Fold it in half and then in half again.
the beaker to sit until the bottom is covered Tear the corner of the filter paper, and open the
with solid particles and the liquid is clear. filter paper into a cone. Place it in the funnel.
2. Grasp the beaker with one hand. With the
other hand, pick up a stirring rod and hold
it along the lip of the beaker. Tilt the beaker
slightly so that
liquid begins
to pour out in
a slow, steady
stream, as
shown in
Figure A .

FIGURE A FIGURE B Folding the filter paper

Settling and decanting

844 -
PRE LABORATORY PROCEDURE
 2. Turn the water off . Attach the pressurized rub-
ber tubing to the horizontal arm of the T. ( You
do not want water to run through the tubing. )
3. Attach the free end of the rubber tubing to the
side arm of a filter flask . Check for a vacuum .
Turn on the water so that it rushes out of the
faucet ( refer to step 1 ). Place the palm of your
hand over the opening of the Erlenmeyer flask.
You should feel the vacuum pull your hand
inward. If you do not feel any pull or if the pull
is weak , increase the flow of water. If increasing
the flow of water fails to work , shut off the
water and make sure your tubing connections
are tight .
4. Insert the neck of a Buchner funnel into a
one-hole rubber stopper until the stopper is
FIGURE C Gravity filtration
about two- thirds to three-fourths up the neck
of the funnel . Place the funnel stem into the
Erlenmeyer flask so that the stopper rests in
2. Put the funnel , stem first , into a filtration flask , the mouth of the flask , as shown in Figure D.
or suspend it over a beaker by using an iron
ring, as shown in Figure C. 5. Obtain a piece of round filter paper. Place it
inside the Buchner funnel over the holes. Turn
3. Wet the filter paper with distilled water from on the water as in step 1. Hold the filter flask
a wash bottle. The paper should adhere to the with one hand , place the palm of your hand
sides of the funnel , and the torn corner should over the mouth of the funnel, and check for
prevent air pockets from forming between the a vacuum .
paper and the funnel.
4. Pour the mixture to be filtered down a stirring 6. Pour the mixture to be filtered into the funnel .
rod into the filter. The stirring rod directs the Use a wash bottle to rinse all of the mixture
mixture into the funnel and reduces splashing. from the beaker into the funnel.
5. Do not let the level of the mixture in the funnel
rise above the edge of the filter paper.
6. Use a wash bottle to rinse all of the mixture
from the beaker into the funnel .

VACUUM FILTRATION
1. Check the T attachment to the faucet. Turn on
the water. Water should run without overflowing
the sink or spitting while creating a vacuum . To
test for a vacuum , cover the opening of the hori -
zontal arm of the T with your thumb or index
finger. If you feel your thumb being pulled
inward , there is a vacuum . Note the number
of turns of the knob that are needed to produce
the flow of water that creates a vacuum . FIGURE D Vacuum filtration

EXTRACTION AND FILTRATION 845

 PRE- LABORATORY PROCEDURE

Gravimetric Analysis
Gravimetric analytical methods are based on accurate and precise mass measurements.
They are used to determine the amount or percentage of a compound or element in a sam-
ple material. For example, if we want to determine the percentage of iron in an ore or the
percentage of chloride ion in drinking water, gravimetric analysis would be used.

A gravimetric procedure generally involves reacting the sample to produce a reaction product
that can be used to calculate the mass of the element or compound in the original sample.
For example, to calculate the percentage of iron in a sample of iron ore, determine the mass
of the ore. The ore is then dissolved in hydrochloric acid to produce FeCI 3. The FeCl 3 pre-
cipitate is converted to a hydrated form of Fe 203 by adding water and ammonia to the sys-
tem. The mixture is then filtered to separate the hydrated Fe 203 from the mixture. The
hydrated Fe 203 is heated in a crucible to drive the water from the hydrate, producing anhy-
drous Fe 203 . The mass of the crucible and its contents is determined after successive heat-
ing steps to ensure that the product has reached constant mass and that all of the water
has been driven off. The mass of Fe 203 produced can be used to calculate the mass and per -
centage of iron in the original ore sample.

Gravimetric procedures require accurate and precise techniques and measurements to

obtain suitable results. Possible sources of error are the following:
1. The product (precipitate ) that is formed is contaminated.
2 . Some product is lost when transferring the product from a filter to a crucible.
3 . The empty crucible is not clean or is not at constant mass for the initial mass
measurement .
4. The system is not heated sufficiently to obtain an anhydrous product .

GENERAL SAFETY shower and eyewash station and the

Always wear safety goggles and a lab procedure for using them.
apron to protect your eyes and clothing. When using a Bunsen burner, confine long
If you get a chemical in your eyes, immedi- hair and loose clothing. Do not heat glass-
ately flush the chemical out at the eyewash ware that is broken, chipped, or cracked.
station while calling to your teacher. Use tongs or a hot mitt to handle heated
Know the location of the emergency lab glassware and other equipment; heated

846 PRELABORATORY PROCEDURE

 glassware does not always look hot.
If your clothing catches fire, WALK to
the emergency lab shower and use it to
put out the fire.
Never put broken glass or ceramics in a
regular waste container. Broken glass and
ceramics should be disposed of in a sepa-
rate container designated by your teacher.

SETTING UP THE EQUIPMENT

1. The general setup for heating a sample in a
crucible is shown in Figure A. Attach a metal
ring clamp to a ring stand, and lay a clay
triangle on the ring.

CLEANING THE CRUCIBLE

2. Wash and drv a metal or ceramic crucible
and lid. Cover the crucible with its lid, and use
a balance to obtain its mass. If the balance is
located far from your working station, use cru- FIGURE A
cible tongs to place the crucible and lid on a
piece of wire gauze. Carry the crucible to the
balance, using the wire gauze as a tray.

HEATING THE CRUCIBLE TO

OBTAIN A CONSTANT MASS
3. After recording the mass of the crucible and
lid, suspend the crucible over a Bunsen burner
by placing it on the clay triangle, as shown in
Figure B. Then, place the lid on the crucible so FIGURE B
that the entire contents are covered.
4. Light the Bunsen burner. Heat the crucible for
5 min with a gentle flame, and then adjust the
burner to produce a strong flame. Heat for
5 min more. Shut off the gas to the burner.
Allow the crucible and lid to cool. Using cru-
cible tongs, carry the crucible and lid to the bal-
ance, as shown in Figure C. Measure and record
the mass. If the mass differs from the mass FIGURE C
before heating, repeat the process until mass
data from heating trials are within 1% of each
other. This measurement assumes that the cru- Gravimetric methods are used in Experiment 7
cible has a constant mass. The crucible is now to synthesize magnesium oxide and in Experiment 9
ready to be used in a gravimetric analysis proce- to separate SrCO from a solution.
^
dure. Details will be found in the following
experiments.

GRAVIMETRIC ANALYSIS 847

 PRE- LABORATORY PROCEDURE

Paper Chromatography
Chromatography is a technique used to separate substances dissolved in a mixture. The
Latin roots of the word are chromato, which means " color/ and graphy, which means " to
1

write." Paper is one medium used to separate the components of a solution.

Paper is made of cellulose fibers that are pressed together. As a solution passes over the
fibers and through the pores, the paper acts as a filter and separates the mixture 's compo-
nents. Particles of the same component group together, producing a colored band .
Properties such as particle size, molecular mass, and charge of the different solute particles
in the mixture affect the distance the components will travel on the paper. The components
of the mixture that are the most soluble in the solvent and the least attracted to the paper
will travel the farthest . Their band of color will be closest to the edge of the paper.

GENERAL SAFETY you will get a broad, tailing trace with little
Always wear safety goggles and a lab or no detectable separation.
apron to protect your eyes and clothing. 4. Use the pencil to poke a small hole in the center
If you get a chemical in your eyes, immedi- of the spotted filter paper. Insert a wick through
ately flush the chemical out at the eyewash the hole. A wick can be made by rolling a tri-
station while calling to your teacher. Know angular piece of filter paper into a cylinder: start
the location of the emergency lah shower
and eyewash station and the procedure for Hole for wick
using them.

,
PROCEDURE
.
1 Use a lead pencil to sketch a circle about the size
1
of a quarter in the center of a piece of circular 6 2
filter paper that is 12 cm in diameter . 5 3
2. Write one numeral for each substance, including 4
any unknowns, around the inside of this circle.
In this experiment , six mixtures are to be sepa-
rated, so the circle is labeled ‘T* through “6, as
" \
shown in Figure A .
3. Use a micropipet to place a spot of each sub -
FIGURE A Filter paper used in paper chromatography is
stance to be separated next to a number. Make spotted with the mixtures to be separated . Each spot is labeled
one spot per number. If the spot is too large, with a numeral or a name that identifies the mixture to be separated.
A hole punched in the center of the paper will attach to a wick that
delivers the solvent to the paper.

848 PRE -LABORATORY PROCEDURE

1 Wick
Hole punched Filter paper
with pencil

2
4 — 1
3

v
3
Petri dish or lid with solvent

FIGURE C The wick is inserted through the hole of the spotted

filter paper. The filter paper with the wick is then placed on top of
a Petri dish or lid filled two-thirds full of water or another solvent.

Cut the triangle from filter paper. Roll the paper into
FIGURE B
a cylinder, starting at the narrow end. .
7 When the solvent is 1 cm from the outside edge
of the paper, remove the paper from the Petri
dish and allow the chromatogram to dry. Sample
atthe point of the triangle, and roll toward its
chromatograms are shown in Figures D and E.
base. See Figure B.
Most writing or drawing inks are mixtures of various
5. Fill a Petri dish or lid two- thirds full of solvent
components that give them specific properties.
( usually water or alcohol).
Therefore, paper chromatography can be used to
6. Set the bottom of the wick in the solvent so study the composition of an ink. Experiment 12
that the filter paper rests on the top of the investigates the composition of ball-point -pen ink.
Petri dish. See Figure C.

FIGURE D Each of the original spots has migrated along with the FIGURE E This chromatogram is unacceptable due to bleeding,
solvent toward the outer edge of the filter paper. For each substance or spread of the pigment front. Too much ink was used in the spot,
that was a mixture, you should see more than one distinct spot of or the ink was too soluble in the solvent.
color in its trace.

PAPER CHROMATOGRAPHY 849

 PRE- LABORATORY PROCEDURE

Volumetric Analysis
Volumetric analysis, the quantitative determination of the concentration of a solution, is
achieved by adding a substance of known concentration to a substance of unknown con-
centration until the reaction between them is complete. The most common application of
volumetric analysis is titration.

A buret is used in titrations. The solution with the known concentration is usually in the
buret . The solution with the unknown concentration is usually in the Erlenmeyer flask . A few
drops of a visual indicator are also added to the flask . The solution in the buret is then added
to the flask until the indicator changes color, which signals that the reaction between the two
solutions is complete. Then, the volumetric data obtained and the balanced chemical equa -
tion for the reaction are used to calculate the unknown concentration.

GENERAL SAFETY
Always wear safety goggles and a lab
A apron to protect your eyes and clothing.
If you get a chemical in your eyes, immedi-
ately flush the chemical out at the eyewash
station while calling to your teacher. Know
the location of the emergency lab shower
and eyewash station and the procedure for
using them.
The general setup for a titration is shown in Figure A .
The steps for setting up this technique follow.

ASSEMBLING THE APPARATUS

s\ 1. Attach a buret clamp to a ring stand.

2. Thoroughly wash and rinse a buret . If water

droplets cling to the walls of the buret , wash
Wr . it again and gently scrub the inside walls with
a buret brush.
c 3. Attach the buret to one side of the buret clamp .

4. Place an Erlenmeyer flask for waste solutions

FIGURE A under the buret tip , as shown in Figure A .

850 PRE -LABORATORY PROCEDURE

 II

? H
'
\
FIGURE B FIGURE C

OPERATING THE STOPCOCK READING THE BURET

1. The stopcock should be operated with the left 1. Drain the buret until the bottom of the meniscus
hand. This method gives better control but may is on the zero mark or within the calibrated
prove awkward at first for right- handed students. portion of the buret . If the solution level is not
The handle should be moved with the thumb at zero, record the exact reading. If you start
and first two fingers of the left hand , as shown from the zero mark , your final buret reading
in Figure B. will equal the amount of solution added .
Remember, burets can be read to the second
2 . Rotate the stopcock back and forth . It should
decimal place. Burets are designed to read the
move freely and easily. If it sticks or will not
volume of liquid delivered to the flask , so num -
move , ask your teacher for assistance. Turn the
bers increase as you read downward from the
stopcock to the closed position. Use a wash bot -
top. For example , the meniscus in Figure C is
tle to add 10 mL of distilled water to the buret .
at 30.84 mL, not 31.16 mL.
Rotate the stopcock to the open position . The
water should come out in a steadv stream . If 2 . Replace the waste beaker with an Erlenmeyer
no water comes out or if the stream of water flask containing a measured amount of the
is blocked , ask your teacher to check the solution of unknown concentration .
stopcock for clogs.
Experiment 15 is an example of a back - titration
applied to an acid - base reaction ; it can be performed
FILLING THE BURET on a larger scale if micropipets are replaced with
1 . To fill the buret , place a funnel in the top of burets.
the buret. Slowly and carefully pour the solution
of known concentration from a beaker into the
funnel . Open the stopcock , and allow' some
of the solution to drain into the waste beaker.
Then , add enough solution to the buret to raise
the level above the zero mark , but do not allow
the solution to overflow;

VOLUMETRIC ANALYSIS 851

 PRE - LABORATORY PROCEDURE

Calorimetry
Calorimetry, the measurement of the transfer of energy as heat, allows chemists to deter-
mine thermal constants, such as the specific heat of metals and the enthalpy of solution.

When two substances at different temperatures touch one another, energy as heat flows
from the warmer substance to the cooler substance until the two substances are at the
same temperature. The amount of energy transferred is measured in joules. (One joule
equals 4.184 calories.)

A device used to measure the transfer of energy as heat is a calorimeter. Calorimeters vary in
construction depending on the purpose and the accuracy of the energy measurement required.
No calorimeter is a perfect insulator; some energy is always lost to the surroundings as heat.
Therefore, every calorimeter must be calibrated to obtain its calorimeter constant.

GENERAL SAFETY
Always wear safety goggles and a lab Thermometer Stirrer

A apron to protect your eyes and clothing.

If you get a chemical in your eyes, immedi-
Hole for
thermometer
Hole for stirrer

ately flush the chemical out at the eyewash

station while calling to your teacher. Know
the location of the emergency lab shower
and eyewash station and the procedure for Calorimeter
using them.
Turn off hot plates and other heat sources
Calorimeter
when not in use. Do not touch a hot plate base
after it has just been turned off; it is
probably hotter than you think. Use
tongs when handling heated containers.
Never hold or touch containers with
Beaker
your hands while heating them.
The general setup for a calorimeter made from
plastic- foam cups is shown in Figure A. The steps
for constructing this setup follow.

FIGURE A Position the hole for the stirrer so that the

thermometer is in the center of the wire ring.

852 -
PRE LABORATORY PROCEDURE
CONSTRUCTING THE CALORIMETER
1 . Trim the lip of one plastic-foam cup, and use
that cup as the top of your calorimeter. The
other cup will be used as the base.
Heated distilled
2. Use the pointed end of a pencil to gently water
make a hole in the center of the calorimeter
top. The hole should be large enough to insert
a thermometer. Make a hole for the wire stirrer.
As you can see in Figure A , this hole should Calorimeter
be positioned so that the wire stirrer can be top with
raised and lowered without interfering with thermometer
and stirrer
the thermometer.
3. Place the calorimeter in a beaker to prevent it
from tipping over.
FIGURE C When transferring warm water from the beaker
to the calorimeter, hold the bottom of the calorimeter steady
so it does not tip over.
CALIBRATING A PLASTIC- FOAM
CUP CALORIMETER
1 . Measure 50 mL of distilled water in a graduated the stirrer gently up and down to mix the con -
tents thoroughly. Take care not to break the
cylinder. Pour it into the calorimeter. Measure
thermometer.
and record the temperature of the water in the
plastic-foam cup. 4. Watch the thermometer, and record the highest
2 . Pour another 50 mL of distilled water into a temperature attained ( usually after about 30 s ).
beaker. Set the beaker on a hot plate, and warm 5 . Empty the calorimeter.
the water to about 60°C, as shown in Figure B.
6. The derivation of the equation to find the
Measure and record the temperature of the water.
calorimeter constant starts with the following
3. Immediately pour the warm water into the cup, relationship.
as shown in Figure C. Cover the cup, and move Energy lost by the warm water = Energy gained by
the cool water + Energy gained by the calorimeter
(
1warm H20 —as
Qcool H20 Qcalorimeter
The energy lost heat by the warm water is
calculated by the following equation .
Qwarm H20 = masswarm H ^0 x 4.184 J /g*°C x A/
The energy gained as heat by the calorimeter
system equals the energy lost as heat by the
warm water. You can use the following equation
to calculate the calorimeter constant C ' for your
calorimeter.
Qcalorimeter Q warm H:0
,
( masscooi H O ) ( 4.184 J /g*°C ) ( A/COO H 2O ) +
2
( ’(&
rcool H,o)
FIGURE B Heat the distilled water to approximately 60°C.
Substitute the data from your calibration , and
solve for C \

CALORIMETRY 853
 APPENDIX A

TABLE A -1 SI MEASUREMENT
Metric Prefixes Length
Prefix Symbol Factor of Base Unit 1 kilometer ( km ) 1 000 m
g«ga G 1 000 (XX) 000 1 meter ( m ) = SI base unit of length
mega M 1 ( MX ) 000 1 centimeter ( cm ) = 0.01 m
kilo k 1 000 1 millimeter ( mm ) = 0.001 m
hecto h 100 1 micrometer ( Jim ) = O.( XM) 001 m
deka da 10 1 nanometer ( n m ) = 0.000 000 001 m
deci d 0.1 1 picometer ( pm ) = 0.000 ( MM ) 000 001 m
centi c 0.01
0.001
Area
milli ni

micro H 0.000 001 1 square kilometer ( km 2 ) = 100 hectares ( ha )

nano n 0.000 000 001 1 hectare ( ha ) = 10 000 square
0.000 ( MM ) ( MM ) ( Mil meters ( m 2)
pico P
1 square meter ( m 2 ) = 10 000 square
centimeters (cm 2)
Mass
1 square centimeter ( cm 2 ) = 100 square
1 kilogram ( kg ) = SI base unit of mass millimeters ( mm 2 )
1 gram ( g ) = 0.001 kg
1 milligram ( mg ) = O.( MM ) 001 kg Volume
1 microgram ( fig ) = 0.000 000 001 kg 1 liter ( L ) = common unit for
liquid volume ( not SI )
1 cubic meter ( m3) 1000 L
1 kiloliter ( kL ) 1000 L
1 milliliter ( ml. ) = 0.001 L
1 milliliter ( ml . ) = 1 cubic centimeter (cm 3)

TABLE A- 2 UNIT SYMBOLS

UI11 U atomic mass unit ( mass ) mol mole ( quantity )
atm atmosphere ( pressure , non -SI ) M molarity (concentration )
Bq becquerel ( nuclear activity ) N newton ( force )
°C degree Celsius ( temperature ) Pa pascal ( pressure )
.1 joule ( energy ) s second ( time )
K kelvin ( temperature , thermodynamic ) V volt ( electric potential difference )

854 APPENDIX A
 TABLE A- 3 SYMBOLS
Symbol Meaning Symbol Meaning
a = helium nucleus ( also *} He ) emission AH ° = standard enthalpy of reaction
from radioactive materials AH °j = standard molar enthalpy of
P = electron (also _" e ) emission from formation
radioactive materials Ka = ionization constant ( acid )
Y = high-energy photon emission from Kb = dissociation constant ( base )
radioactive materials
^K eg = equilibrium constant
A .
= change in a given quantity ( e.g. A //
sn = solubility -product constant
for change in enthalpy )
KE = kinetic energy
c = speed of light in vacuum
m mass
CP = specific heat capacity (at constant
= Avogadros number
I)
pressure )
density
"
n
A
number of moles
r pressure
Ea = activation energy
pH = measure of acidity ( —log[ H CV ] )
E° = standard electrode potential ^
R ideal gas law constant
°
E cell = standard potential of an electro-
chemical cell S = entropy
CM = Gibbs free energy
S ° = standard molar entropy
7 = temperature ( thermodynamic, in
&G ° = standard free energy of reaction kelvins)
AG ° / = standard molar free energy of
formation t = temperature ( ± degrees Celsius )
V volume
// = enthalpy
v = velocity

TABLE A- 4 PHYSICAL CONSTANTS

Quantity Symbol Value
Atomic mass unit amu 1.660 5389 X 10-27 kg
Avogadro’s number NA 6.022 142 X I023 /mol
Electron rest mass mc 9.109 3826 X lO--11 kg
5.4858 x 104 amu
Ideal gas law constant R 8.314 L • kPa /( mol K ).
0.0821 L • atm/(mol • K )
Molar volume of ideal gas at STP VM 22.414 10 L/mol
Neutron rest mass ni „ 1.674 9273 X 10 27 kg
~

l. 665 amu
( K )8

Normal boiling point of water Th 373.15 K = 1Q0.0°C

Normal freezing point of water II 273.15 K = 0.00°C
Planck 's constant /; 6.626 069 X 1(H4 J • s
Proton rest mass mp 1.6726217 X 10~27 kg
1.007 276 amu
Speed of light in a vacuum t 2.997 924 58 X 10« m /s
Temperature of triple point of water 273.16 K = 0.01°C

APPENDIX A 855
 TABLE A- 5 ENTHALPY OF COMBUSTION
Substance Formula State AHc Substance Formula State AHC
hydrogen H2 g -285.8 benzene C6H6 / -3267.6
graphite C s -393.5 toluene C7H8 / -3910.3
carbon monoxide CO g -283.0 naphthalene ,
C OH8 s -5156.3
methane CH4 g -890.8 anthracene Q 4H10 A* -7163.0
ethane C2H6 £ -1560.7 methanol CH3OH / -726.1
propane C3H8 g -2219.2 ethanol C2H5OH / -1366.8
butane C4H10 g -2877.6 ether (C2H5)20 / -2751.1
pentane C5H 12 g -3535.6 formaldehyde CH:0 g -570.7
hexane Cf,H14 / -4163.2 glucose Q,H12Q6 s -2803.0
heptane C7H „ / -4817.0 sucrose ,
C 2H220 „ S -5640.9
octane C8H18 / -5470.5 A / / . = enthalpy of combustion of the given
(

ethene ( ethylene ) C2H4 g -1411.2 substance. All values of AHc are expressed as
kJ/mol of substance oxidized to H20( /) and/ or
propene ( propylene ) C3 H(s g -2058.0
C02(g) at constant pressure and 25 C.
etliyne ( acetylene ) g -1301.1 s = solid. / = liquid, g = gas

TABLE A -6 THE ELEMENTS— SYMBOLS, ATOMIC NUMBERS, AND ATOMIC MASSES

Name of Atomic Atomic Name of Atomic Atomic
element Symbol number mass element Symbol number mass
actinium Ac 89 [ 227.0278 ] copper Cu 29 63.546
aluminum A1 13 26.981539 curium Cm 96 [ 247.0703 ]
americium Am 95 [ 243.0614 ] darmstadtium Ds no [ 271 ]
antimony Sb 51 121.757 duhnitim Db 105 [ 262.1141
argon Ar 18 39.948 dysprosium Dv 66 162.50
arsenic As 33 74.92159 einsteinium Es 99 [ 252.083 ]
astatine At 85 [ 209.9871 ] erbium Er 68 167.26
barium Ba 56 137.327 europium Eu 63 151.966
herkelium Bk 97 [ 247.0703 ] fermiiim Fm 100 [ 257.0951 ]
beryllium Be 4 9.012182 fluorine F 9 18.9984032
bismuth Bi 83 208.98037 francium Fr 87 [ 223.0197 ]
huhrium Bh 107 [ 262.12 ] gadolinium Cid 64 157.25
boron B 5 10.811 gallium Ga 31 69.723
bromine Br 35 79.904 germanium Cie 32 72.61
cadmium Cd 48 112.411 gold Au 79 196.96654
calcium Ca 20 40.078 hafnium HI 72 178.49
californium Cf 98 [ 251.0796 ] hussium Hs 108 [ 265 ]
carbon C 6 12.011 helium Hc 4.002602
cerium Ce 58 140.115 liolmiiim Ho 67 164.930
cesium Cs 55 132.90543 hydrogen H 1.00794
chlorine Cl 17 35.4527 indium In 49 114.818
chromium Cr 24 51.9961 iodine I 53 126.904
cobalt Co 27 58.93320 iridium Ir 77 192.22

856 APPENDIX A
 TABLE A - 6 CONTINUED
Name of Atomic Atomic Name of Atomic Atomic
element Symbol number mass element Symbol number mass
iron Fe 26 55.847 rhodium Rh 45 102.906
krypton Kr 36 83.80 rubidium Rb 37 85.4678
lunthunum La 57 138.9055 ruthenium Ru 44 101.07
Inwrencium Lr 103 [ 262.11 ] rutherfordium Rf 104 [ 261.11 ]
lend Pb 82 207.2 samarium Sni 62 150.36
lithium Li 3 6.941 scandium Sc 21 44.955910
lutctium Lu 71 174.967 seahorgium Sg 106 [ 263.118 ]
magnesium Mg 12 24.3050 selenium Se 34 78.96
manganese Mn 25 54.93805 silicon Si 14 28.0855
meitnerium Ml 109 [ 266 ] silver Ag 47 107.8682
mendelevium Md 101 [ 258.10 ] sodium Na 11 22.989768
mercury Hg 80 200.59 strontium Sr 38 87.62
molybdenum Mo 42 95.94 sulfur S 16 32.066
neodMiiium Nd 60 144.24 tantalum Ta 73 180.9479
neon Ne 10 20.1797 technetium Tc 43 [ 97.9072 ]
neptunium Np 93 [ 237.0482 ] tellurium Te 52 127.60
nickel Ni 28 58.6934 terbium Tb 65 158.92534
niobium Nb 41 92.90638 thallium T1 81 204.3833
nitrogen N 7 14.00674 thorium Th 90 232.0381
nohclium No 102 [ 259.1009 ] thulium Tm 69 168.93421
osmium Os 76 190.23 tin Sn 50 118.710
oxygen O 8 15.9994 titanium Ti 22 47.88
palladium Pd 46 106.42 tungsten W 74 183.84
phosphorus P 15 30.9738 uranium U 92 238.0289
platinum Pt 78 195.08 yunuditim V 23 50.9415
plutonium Pu 94 [ 244.0642 ] xenon Xe 54 131.29
polonium Po 84 [ 208.9824 ] ytterbium Yb 70 173.04
potassium K 19 39.0983 yttrium Y 39 88.90585
praseodymium Pr 59 140.908 zinc Zn 30 65.39
promethium Pm 61 [ 144.9127 ] zirconium Zr 40 91.224
protactinium Pa 91 231.03588 A value given in brackets denotes the mass number of
radium Ra 88 [226.0254 ] the most stable or most common isotope. The atomic
masses of most of these elements are believed to have
radon Rn 86 [ 222.0176 ]
an error no greater than ± 1 in the last digit given.
rhenium Re 75 186.207

APPENDIX A 857
 TABLE A- 7 COMMON IONS
Cation Symbol Anion Symbol
nliiininum Al3 + acetate CH3COO -
ammonium NH|+ bromide Br -
As- +
arsenic(III)
' carbonate C05
barium Ba2 + chlorate CIO;
3
calcium Ca 2 chloride Cl *

chromiiim ( H ) Cr2 + chlorite CIO;

chromiiim ( lll ) Cr3 + chromate CrO 2 -
cobalt ( ll ) Co2 f cyanide CN -
cobalt < III )
,
Co + dichromate Cr -,02 -
copper!I ) Cuf lluoride F"
copper!II ) Cu 2 * hexacyanoferrate!11 ) Fe( CN) j *
livdronium H3O 4
licxacyanof'crratc !III ) Fe( CN ) g
iron ( I I ) Fe2 + hydride H
iron!Ill ) Fe3 hydrogen carbonate HCO;
lead!II ) Pb2+ hydrogen sulfate HSO4
magnesium Mg2+ hydroxide OH
mercury!I) Hg22 + hypochlorite CIO
mercury!II ) Hg2+ iodide I
nickel!II ) Ni2 nitrate NO;
potassium K+ nitrite NO;
silver Ag+ oxide O2
sodium Na * perchlorate ClOj
strontium Sr2 > permanganate Mn04
tin < II ) Sn2 * peroxide or
tin! IV ) Sn4+ phosphate i>( ) ;
titanium!Ill ) Tiu sulfate SOj -

titanium!IV ) Ti4* sulfide S2 ~

/ me Zn2+ sulfite SO|-

858 APPENDIX A
 TABLE A -8 WATER - VAPOR PRESSURE
Temperature Pressure Pressure Temperature Pressure Pressure
(°C ) (mm Hg) (kPa) (°C) (mm Hg) ( kPa)
0.0 4.6 0.61 23.0 21.1 2.81
5.0 6.5 0.87 23.5 21.7 2.90
10.0 9.2 1.23 24.0 22.4 2.98
15.0 12.8 1.71 24.5 23.1 3.10
15.5 13.2 1.76 25.0 23.8 3.17
16.0 13.6 1.82 26.0 25.2 3.36
16.5 14.1 1.88 27.0 26.7 3.57
17.0 14.5 1.94 28.0 28.3 3.78
17.5 15.0 2.00 29.0 30.0 4.01
18.0 15.5 2.06 30.0 31.8 4.25
18.5 16.0 2.13 35.0 42.2 5.63
19.0 16.5 2.19 40.0 55.3 7.38
19.5 17.0 2.27 50.0 92.5 12.34
20.0 17.5 2.34 60.0 149.4 19.93
20.5 18.1 2.41 70.0 233.7 31.18
21.0 18.6 2.49 80.0 355.1 47.37
21.5 19.2 2.57 90.0 525.8 70.12
22.0 19.8 2.64 95.0 633.9 84.53
22.5 20.4 2.72 100.0 760.0 101.32

TABLE A - 9 DENSITIES OF GASES AT STP TABLE A- 10 DENSITY OF WATER

Gas Density ( g / L) Temperature (°C ) Density ( g / cm 3)
air, cln l.293 0 0.999 84
ammonia 0.771 i 0.999 94
carbon dioxide 1.997 3.98 ( maximum ) 0.999 973
carbon monoxide 1.250 4 0.999 97
chlorine 3.214 6 0.999 94
dinitrogen monoxide 1.977 8 0.999 85
etliyne ( acetylene ) 1.165 10 0.999 70
helium 0.1785 14 0.999 24
hydrogen 0.0899 16 0.998 94
hydrogen chloride 1.639 20 0.998 20
hydrogen sulfide 1.539 25 0.997 05
methane 0.7168 30 0.995 65
nitrogen 1.2506 40 0.992 22
nitrogen monoxide ( at 10°C ) 1.340 50 0.988 04
oxygen 1.429 60 0.983 20
sulfur dioxide 2.927 70 0.977 77
80 0.971 79
90 0.965 31
100 0.958 36

APPENDIX A 859
 TABLE A -11 SOLUBILITIES OF GASES IN WATER
Volume of gas ( in liters ) at STP that can be dissolved in l L of water at the temperature (°C) indicated.
Gas 0 °C 10° C 20 °C 60° C
air 0.029 IS 0.022 84 0.018 68 0.012 16
ummoma 1130 870 680 200
carbon dioxide 1.713 1.194 0.878 0.359
carbon monoxide 0.035 37 0.028 16 0.023 19 0.014 88
chlorine 3.148 2.299 1.023
hydrogen 0.021 48 0.019 55 0.018 19 0.016 00
hydrogen chloride 512 475 442 339
hydrogen sulfide 4.670 3.399 2.582 1.190
methane 0.055 63 0.041 77 0.033 08 0.019 54
nitrogen* 0.023 54 0.018 61 0.015 45 0.010 23
nitrogen monoxide 0.073 81 0.057 09 0.047 06 0.029 54
oxygen 0.048 89 0.038 02 0.031 02 0.019 46
sulfur dioxide 79.789 56.647 39.374
* Atmospheric nitrogen-98.815% N > 1.185 % inert gases

TABLE A -12 SOLUBILITY CHART

ZJ ZJ ZJ
ZJ
ZJ -c ~ ZJ ZJ rz
“C 7Z
*
-
“C

—
7Z ZJ ZJ ZJ ZJ ZJ
mm • a ZJ BL
TZ JJJ

—s
£ s
ZJ
?! u
•mm
• £
w
#

rz ZJ ZJ ZJ ZJ
•mm £
2 . =
/ /.

aluminum S S s ASS a A I S d
ammonium S s s s s s s s s s s s
barium S S P S S A S S S S A S a d
calcium S S P S S s s s s p P P s s
copper! II ) S S s s A S A A A S A
hydrogen S s s s s s s s l s s
iron ( ll ) S P S S A S S A A S A
iron! Ill ) S S S A A S S A P P d
lead ( ll ) S S A S SAP P S P A A P A
magnesium S S P S s s A s s A P A S d
manganese! II ) S S P S S A S S A P I S A
mercury! I ) P A A S a P A S A A P 1
mercury! II ) S S S S P A P S P A d I
potassium S S s s s s s s s s s s s s
silver P a A S a P I S P A P A
sodium S S s s s s s s S d s s s s
strontium S S P s S P S S S S A A P S
till! II ) d S S S A A S d A A S A
tin ( IV ) S S S S P d A S A
zinc S s P S S P A S S P A A S A
S = soluble in water. A = soluble in acids, insoluble in water. P = partially soluble in water, soluble in dilute acids.
I = insoluble in dilute acids and in water a slightly soluble in acids, insoluble in water, d = decomposes in water.
=

860 APPENDIX A
 TABLE A- 13 SOLUBILITY OF COMPOUNDS
Solubilities are given in grams of solute that can be dissolved in KM) g of water at the temperature (°C)
indicated.
Compound Formula 0°C 20°C 60°C 100°C
aliiiiiiiiiiin sulfate A12( S04 )3 31.2 36.4 59.2 89.0
ammonium chloride NH4 1C 29.4 37.2 55.3 77.3
ammonium nitrate NH4NO3 118 192 421 871
ammonium sulfate ( NH4 ) 2 S04 70.6 75.4 88 103
barium carbonate BaC03 * 0.00221 S°
* 0.0065
barium chloride dihydrate -
BaCl2 2H:Q 31.2 35.8 46.2 59.4
barium hydroxide Ba( OH)2 1.67 3.89 20.94 101.40800
barium nitrate Ba( NQ 3 )2 4.95 9.02 20.4 34.4
barium sulfate BaSQ 4 * 0.000 246-5“ —* 0.000 413
calcium carbonate CaCQ 3 * 0.0014250 * O.OOI 8750
calcium fluoride CaF2 0.001618° 0.001726" * *
calcium hydrogen carbonate Ca ( HC03 )2 16.15 16.60 17.50 18.40
calcium hydroxide
>
•
Ca ( Oli ) 2 0.189 0.173 0.121 0.076
calcium sulfate CaS04 * 0.20930" * 0.1619
copper ( ll ) chloride CuCh 68.6 73.0 96.5 120
copper ( II ) sulfate pentahydrate CuSQ4 • 5H20 23.1 32.0 61.8 114
leud ( II ) chloride PbCl 2 0.67 1.00 1.94 3.20
lead( II ) nitrate Pb( N03 ) 2 37.5 54.3 91.6 133
lithium chloride LiCI 69.2 83.5 98.4 128
lithium sulfate Li2S04 36.1 34.8 32.6 30.990°
magnesium hydroxide Mg(OH )2 * 0.0009 ls° ,
* 0.004
magnesium sulfate MgSQ 4 22.0 33.7 54.6 68.3
mercury (l) chloride Hg2CI2 * 0.0( H ) 2025" 0.001430 —*
mercury (II ) chloride HgCI2 3.63 6.57 16.3 61.3
potassium bromide KBr 53.6 65.3 85.5 104
potassium chlorate KCIO3 3.3 7.3 23.8 56.3
potassium chloride KC1 28.0 34.2 45.8 56.3
potassium chromate K 2CrQ4 56.3 63.7 70.1 74.5‘*r
potassium iodide KI 128 144 176 206
potassium nitrate KNO3 13.9 31.6 106 245
potassium permanganate KMnQ4 2.83 6.34 22.1 *
potassium sulfate K:SQ 4 7.4 11.1 18.2 24.1
silver acetate AgC2 H30, 0.73 1.05 1.93 2.59S( r ‘
silver chloride AgCl 0.000 089 lo° —* * 0.0021
silver nitrate AgNQ 3 122 216 440 733
sodium acetate NaC2 H302 36.2 46.4 139 170
sodium chlorate NaCI03 79.6 95.9 137 204
sodium chloride NaCl 35.7 35.9 37.1 39.2
sodium nitrate NaNQ 3 73.0 87.6 122 180
sucrose f i:H220 n 179.2 203.9 287.3 487.2
Dashes indicate that values are not available.

APPENDIX A 861
 TABLE A- 14 ENTHALPY OF FORMATION
Substance State A Hf Substance State A Hf
ammonia 8 - 45.9 lead!IV ) oxide s - 274.5
ammonium chloride 5 - 314.4 lead ( II ) nitrate s - 451.9
ammonium sulfate 5 - l 180.9 lead( ll ) sulfate s - 919.94
barium chloride .v -858.6 lithium chloride s - 408.6
barium nitrate .v - 768.2 lithium nitrate x - 483.1
barium sulfate .v - 1473.2 magnesium chloride .v - 641.5
benzene 8 4- 82.88 magnesium oxide .v -601.6
benzene / 4- 49.080 magnesium sulfate s - 1261.79
calcium carbonate 5 - 1207.6 manganese!IV ) oxide .v - 520.0
calcium chloride 5 - 795.4 munganese( ll ) sulfate .v - 1065.3
calcium hydroxide .v - 983.2 mercury!I) chloride 5 - 264.2
calcium nitrate 5 - 938.2 mercury!II ) chloride s - 230.0
calcium oxide s - 634.9 mercury!II) oxide ( red ) s - 90.8
calcium sulfate 5 - 1434.5 methane ft - 74.9
carbon !diamond ) s 4- 1.9 nitrogen dioxide 8 +33.2
carbon ( graphite ) v 0.00 nitrogen monoxide 8 + 90.29
carbon dioxide 8 “ 393.5 dinitrogen monoxide 8 + 82.1
carbon monoxide 8 110.5 dinitrogen tetroxide 8 + 9.2
copper!II ) nitrate 5 -302.9 oxygen ( 02 ) 8 0.00
copper!II ) oxide .v - 157.3 ozone ( O3) g + 142.7
copper!II ) sulfate 5 - 771.4 tetraphosphorus decoxide 5 -3009.9
ethane g - 83.8 potassium bromide 5 - 393.8
ethyne ( acetylene ) g + 228.2 potassium chloride s - 436.49
hydrogen ( H2 ) 8 0.00 potassium hydroxide 5 - 424.58
hydrogen bromide 8 - 36.29 potassium nitrate s — 494.6
hydrogen chloride 8 - 92.3 potassium sulfate s - 1437.8
hydrogen fluoride 8 - 273.3 silicon dioxide ( quartz ) .v - 910.7
hydrogen iodide g + 26.5 silver chloride 5 - 127.01 ± 0.5
hydrogen oxide ( water ) g - 241.8 silver nitrate 5 - 120.5
hydrogen oxide ( water ) / - 285.8 silver sulfide s - 32.59
hydrogen peroxide 8 - 136.3 sodium bromide A - 361.8
hydrogen peroxide / - 187.8 sodium chloride 5 - 385.9
hydrogen sulfide 8 - 20.6 sodium hydroxide s - 425.9
iodine ( I 2 ) s 0.00 sodium nitrate 5 - 467.9
iodine ( I2 ) 8 + 62.4 sodium sulfate / - 1387.1
iron!II ) chloride 5 - 399.4 sulfur dioxide 8 - 296.8
iron!II ) oxide s - 272.0 sulfur trioxide g - 395.7
iron!Ill ) oxide .v - 824.2 tin( IV ) chloride / - 511.3
iron!II ) sulfate .v - 928.4 zinc nitrate 5 - 483.7
iron!II ) sulfide .v - 100.0 zinc oxide s - 350.5
lead!II ) oxide .v - 217.3 zinc sulfate v - 980.14
, . ,
A / / is enthalpy of formation of the given substance from its elements All values of A / / are expressed as kJ/mol at
, .
25w( \ Negative values of A / / indicate exothermic reactions. \ = solid / - liquid, g = gas

862 APPENDIX A
 TABLE A-15 PROPERTIES OF COMMON ELEMENTS
Form / color Density Melting point Boiling point Common
Name at room temperature ( g/ cm 3 ) t (°C ) (°C ) oxidation states
aluminum silver metal 2.702 660.37 2467 3+
arsenic gray metalloid 5.72714 817 ( 28 atm ) 613 ( sublimes ) 3 — . 3 +, 5 +
barium bluish white metal 3.51 725 1640 2+
bromine red-brown liquid 3.119 - 7.2 58.78 1 —. 1 +, 3 +, 54- , 7 +
calcium silver metal 1.54 839 ± 2 1484 2+
carbon diamond 3.51 3500 (63.5 atm ) 3930 2 +, 4 +
graphite 2.25 3652 ( sublimes )
chlorine green-yellow gas 3.214* — 100.98 - 34.6 1 — , 1 +, 3 +. 5 +, 74-
chromium gray metal 7.2028 1857 ± 20 2672 .
2 +, 3 + 64-
cobalt gray metal 8.9 1495 2870 2 +. 3 +
copper red metal 8.92 1083.4 ± 0.2 2567 1 + 2+
t

tluorine yellow gas 1.69 - 219.62 - 188.14

germanium gray metalloid *
5.32325 937.4 2830 4+
gold yellow metal 19.31 1064.43 2808 ± 2 H-. 3 +
helium colorless gas 0.1785 * - 272.2 ( 26 atm) - 268.9 0
Imlrogen colorless gas 0.0899* - 259.14 - 252.8 1-, 1 +
iodine blue-black solid 4.93 113.5 184.35 1 — , 1 +, 3 4- , 5 ± , 7 4-
iron silver metal 7.86 1535 2750 24-, 34-
lead bluish white metal 11.343716 327.502 1740 2 +, 4 +
lithium silver metal 0.534 180.54 1342
magnesium silver metal 1.745 648.8 1107 2+
manganese grav - white metal 7.20 1244 ± 3 1962 2 +, 34-, 44-, 6+, 74-
mercury silver liquid metal 13.5462 - 38.87 356.58 l + , 2+
neon colorless gas 0.9002 * - 248.67 - 245.9 0
nickel silver metal 8.90 1455 2732 24- , 34-
nitrogen colorless gas 1.2506* - 209.86 - 195.8 3 — , 34-, 54-
oxygen colorless gas 1.429* - 218.4 - 182.962 2-
phosphorus yellow solid 1.82 44.1 280 3 -, 3+, 54-
platinum silver metal 21.45 1772 3827 ± 100 24-, 4 +
potassium silver metal 0.86 63.25 760 1+
silicon gray metalloid 2.33 ± 0.01 1410 2355 24- , 4 + Ml
silver white metal 10.5 961.93 2212 1+
sodium silver metal 0.97 97.8 882.9 1+
strontium silver metal 2.6 769 1384 2+
sulfur vellow solid 1.96 119.0 444.674 2-, 4 +, 6 +
tin white metal 7.28 231.88 2260 24-, 4+
titanium white metal 4.5 1660 ± 10 3287 24-, 34-, 4 +
uranium silver metal 19.05 ± 0.0225 1132.3 ± 0 . 8 3818 34-, 44- , 6 +
zinc blue - white metal 7.14 419.58 907 2+
t Densities obtained at 20°C unless otherwise noted ( superscript )
Density of fluorine given in g/L at 1 atm and 15°C
*
* Densities of gases given in g/L at STP

APPENDIX A 863
 APPENDIX B

Study Skills for Chemistry

Table of Contents

Succeeding in Your Chemistry Class 865

Making Concept Maps 868

Making Power Notes 871

Making Two-Column Notes 873

Using the K / W / L Strategy 874

Using Sequencing / Pattern Puzzles 875

Other Reading Strategies 876

Other Studying Strategies 877

Cooperative Learning Techniques 878

864 APPENDIX B
 APPENDIX B

Study Skills for Chemistry

Using the K / W / L strategy ( see page 874 ) can
Succeeding in Your help you relate new material to what you
Chemistry Class already know and what you need to learn .

Your success in this course will depend on your Taking Notes in Class
ability to apply some basic study skills to learn - • Be prepared to take notes during class. Have
ing the material. Studying chemistry can be diffi- your materials organized in a notebook .
cult , but you can make it easier using simple Separate sheets of paper can be easily lost .
strategies for dealing with the concepts and • Don't write down everything your teacher says.
problems. Becoming skilled in using these strate- Try to tell which parts of the lecture are impor -
gies will be your keys to success in this and many tant and which are not . Reading the text before
other courses. class will help in this. You will not be able to
write down everything, so you must try to write
Reading the Text
down only the important things.
• Read the assigned material before class so that • Recopying notes later is a waste of time and
the class lecture makes sense. Use a dictionary does not help you learn material for a test . Do
to help you build and interpret vocabulary.
Remember that , while reading, one of your
tasks is to figure out what information is
important .
Working together with others using Paired
Reading and Discussion strategies can help you
decide what is important and clarify the
material . ( For more discussion , see Other
Reading Strategies on page 876. )
• Select a cjuiet setting away from distractions
so that you can concentrate on what you are
reading.
• Have a pencil and paper nearby to jot down
notes and questions you may have. Be sure to
get these questions answered in class. Power
Notes ( see page 871 ) can help you organize the
notes you take and prepare you for class.
• Use the Objectives in the beginning of each
section as a list of w hat you need to know from
the section . Teachers generally make their tests
based on the text objectives or their own objec-
tives. Using the objectives to focus your read -
ing can make your learning more efficient .

APPENDIX B 865
 it right the first time. Organize your notes as an assigned problem to one of the Sample
you are writing them down so that you can Problems in the chapter, it shows that you
make sense of your notes when you review understand the material.
them without needing to recopy them. •The four steps: Analyze, Plan, Compute, and
Evaluate should he the steps you go through
Reviewing Class Notes
.
when working assigned problems These steps
will allow you to organize your thoughts and
• Review your notes as soon as possible after help you develop your problem-solving skills.
class. Write down any questions you may have • Never spend more than 15 minutes trying to
about the material covered that day. Be sure solve a problem. If you have not been able to
to get these questions answered during the come up with a plan for the solution after 15
next class. You can work with friends to use minutes, additional time spent will only cause
strategies such as Paired Summarizing and .
vou to become frustrated What do vou do?
.
L.I.N.K . (See page 878 )
• r

.
( jet help! See your teacher or a classmate Find
• Do not wait until the test to review. By then out what it is that Jvou do not understand.
you will have forgotten a good portion of the • Do not try to memorize the Sample Problems:
material. spend your time trying to understand how the
• Be selective about what you memorize. You solution develops. Memorizing a particular
cannot memorize everything in a chapter. First sample problem will not ensure that you
of all, it is too time consuming. Second, memo- understand it well enough to solve a similar
rizing and understanding are not the same problem.
thing. Memorizing topics as they appear in • Always look at your answer and ask yourself if
your notes or text does not guarantee that you it is reasonable and makes sense. Check to be
will be able to correctly answer questions that sure vou have the correct units and numbers of
require understanding of those topics. You significant figures.
should only memorize material that you under -
stand. Concept Maps and other Reading
Organizers, Sequencing/Pattern Puzzles, and
Prediction Guides can help you understand key
ideas and major concepts. ( See pages 868, 875.
and 877. )

Working Problems
In addition to understanding the concepts, the
ability to solve problems will be a key to your
success in chemistry. You will probably spend a
lot of time working problems in class and at
home. The ability to solve chemistry problems is
a skill, and like any skill, it requires practice.
• Always review the Sample Problems in the
chapter. The Sample Problems in the text pro-
vide road maps for solving certain types of
problems. Cover the solution while trying to
work the problem yourself.
• The problems in the Chapter Review are simi-
lar to the Sample Problems. If you can relate

866 APPENDIX B
Completing Homework 1. You are hearing the information , which is
Your teacher will probably assign questions and effective in helping you learn .
problems from the Section Reviews and Chapter .
2 If you cannot recite the ideas, it should be a
Reviews or assign Modern Chemistry Daily clue that you do not understand the material ,
I lomework . The purpose of these assignments is and you should begin rereading or reviewing
to review what you have covered in class and to the material again .
see if you can use the information to answer ques- • Studying with a friend provides a good oppor -
tions or solve problems. As in reviewing class tunity for recitation. If you can explain ideas to
notes, do your homework as soon after class as your study partner, you know the material.
possible while the topics are still fresh in your Taking an exam
mind . Do not wait until late at night , when you are
• Get plenty of rest before the exam so that you
more likely to be tired and to become frustrated .
can think clearly. If you have been awake all
night studying, you are less likely to succeed
Preparing for and Taking Exams than if you had gotten a full night of rest .
Reviewing for an exam • Start with the questions you know . If you get
stuck on a question , save it for later. As time
• Don't panic and don’t cram! It takes longer to
passes and you work through the exam , you
learn if you are under pressure. If you have fol -
may recall the information you need to answer
lowed the strategies listed here and reviewed
a difficult question or solve a difficult problem .
along the way, studying for the exam should be
less stressful .
Good luck !
• When looking over your notes and concept
maps, recite ideas out loud. There are two rea -
sons for reciting:

APPENDIX B 867
 because you work with only the key ideas and
Making Concept Maps how they fit together.
The concept map shown as Map A was made
Making concept maps can help you decide what from vocabulary terms in Chapter 1 . Vocabulary
material in a chapter is important and how to terms are generally labels for concepts, and con-
efficiently learn that material. A concept map cepts are generally nouns. In a concept map.
presents key ideas, meanings, and relationships linking words are used to form propositions that
for the concepts being studied. It can be thought connect concepts and give them meaning in con -
of as a visual road map of the chapter. Learning text. For example, on the map below, “ matter is
happens efficiently when you use concept maps described by physical properties' is a proposition.
*

Map A A
matter
r
is classified as is described by

A pure A A
chemical A physical
mixtures
substances r properties properties

which consist of is changed by

A A A
elements compounds
which describe
energy
w V W

which can be which causes

A t A
homogeneous heterogeneous
r w chemical physical
^ changes changes v
which can be
which are such as
described by

nonmetals T metalloids chemical change of

reactions state

where to/from

form

products

868 APPENDIX B
 Studies show that people are better able to 2. Select a main concept for the map.
remember materials presented visually. A con - We will use matter as the main concept for this
cept map is better than an outline because you map.
can see the relationships among many ideas. 3. Build the map by placing the concepts accord -
Because outlines are linear, there is no way of ing to their importance under the main con -
linking the ideas from various sections of the cept , matter.
outline. Read through the map to become famil - One way of arranging the concepts is shown in
iar with the information presented. Then look at Map B.
the map in relation to all of the text pages in
Chapter 1 ; which gives a better picture of the
—
important concepts the map or the full chapter?

To Make a Concept Map

1 . List all the important concepts.
We ll use some of the boldfaced and italicized
terms from Chapter 1 , Section 2.
matter mixture
compound pure substance
element
homogenous mixture
heterogeneous mixture
• From this list , group similar concepts together.
For example, one way to group these concepts
—
would be into two groups one that is related
to mixtures and one that is related to pure
substances.
mixture pure substance
heterogeneous mixture compound
homogeneous mixture element

Map B
matter

A pure A
mixtures
substances w T

A A homogeneous A heterogeneous
elements compounds
r v mixtures v mixtures V

APPENDIX B 869
 4. Add linking words to give meaning to the
arrangement of concepts. Practice
When adding the links, he sure that each .
1 Classify each of the following as either a
proposition makes sense. To distinguish con - concept or linking word( s ).
cepts from links, place your concepts in circles, a. classification
ovals, or rectangles, as shown in the maps.
Then make cross-links. Cross-links are made .
b is classified as
of propositions and lines connecting concepts .
c forms
across the map. Links that apply in only one
d. is described by
direction are indicated with an arrowhead.
Map C is a finished map covering the main .
e reaction
ideas listed in Step 1 . f. reacts with
Making maps might seem difficult at first ,
hut the process forces you to think about the
.
g metal
meanings and relationships among the con- h. defines
cepts. If you do not understand those relation -
ships, you can get help early on.
.
2 Write three propositions from the informa -
tion in Map A.
Practice mapping by making concept maps
about topics you know. For example, if you
know a lot about a particular sport, such as
basketball, or if you have a particular hobby,
such as playing a musical instrument, you can
use that topic to make a practice map. By per - 3. List two cross-links shown on Map C .
fecting your skills with information that you
know very well, you will begin to feel more
confident about making maps from the infor -
mation in a chapter.
Remember, the time you devote to map-
ping will pay off when it is time to review for
an exam.

Map C A
matter
W

is composed of
pure A
are made from mixtures
substances V r
which can be which can be

A A homogeneous A heterogeneous
elements form compounds
r r mixtures w mixtures v

870 APPENDIX B
 2. Using the text , select some Power 2 words to
Making Power Notes support your Power 1 word.
We ' ll use the terms nucleus and electrons;
Power notes help you organize the chemical con - which are two parts of an atom.
cepts you are studying by distinguishing main
ideas from details. Similar to outlines, power Power 1: Atom
notes are linear in form and provide you with a
Power 2: Nucleus
framework of important concepts. Power notes
are easier to use than outlines because their Power 2: Electrons
structure is simpler. Using the power notes num -
bering system you assign a / to each main idea 3. Select some Power 3 words to support your
and a 2, 3, or 4 to each detail . Power 2 words.
Power notes are an invaluable asset to the We ll use the terms positively charged and neg -
learning process, and they can be used frequently atively charged, two terms that describe the
.
throughout your chemistry course You can use Power 2 words.
power notes to organize ideas while reading your
text or to restructure your class notes for study - Power 1: Atom
ing purposes. Power 2: Nucleus
To learn to make power notes, practice first by
Power 3: Positively charged
using single- word concepts and a subject you are
Power 2: Electrons
especially interested in , such as animals, sports,
or movies. As you become comfortable with Power 3: Negatively charged
structuring power notes, integrate their use into
vour study of chemistry. For an easier transition ,
start with a few boldfaced or italicized terms.
Later you can strengthen your notes by expanding
these single-word concepts into more-detailed
phrases and sentences. Use the following general
format to help you structure your power notes.

Power 1: Main idea

Power 2: Detail or support for power 1
Power 3: Detail or support for power 2
Power 4: Detail or support for power 3

1. Pick a Power I word from the text.

The text you choose does not have to come
straight from your chemistry textbook. You may
be making power notes from your lecture notes
or from an outside source. We ll use the term
atom found in Chapter 3. Section 2 of your
textbook .

Power 1: Atom

APPENDIX B 871
4. Continue to add powers to support and detail
the main idea as necessary. Practice
There are no restrictions on how many power 1. Use a periodic table and the power notes
numbers you can use in your notes. If you structure below to organize the following
have a main idea that requires a lot of support , terms: alkaline -earth metals, nonmetals, cal -
add more powers to help you extend and orga - cium, sodium, halogens, metals, alkali met -
nize your ideas. Be sure that words having the .
als, chlorine, barium and iodine.
same power number have a similar relation - 1
ship to the power above. Power 1 terms do not
have to be related to each other. You can use 2
power notes to organize the material in an
3
entire section or chapter of your text . Doing
so will provide you with an invaluable study 2
guide for your classroom quizzes and tests.
3
Power 1: Atom
Power 2: Nucleus 3
Power 3: Positively charged
1
Power 3: Protons
Power 4: Positively charged 2
Power 3: Neutrons
3
Power 4: No charge
Power 2: Electrons 3
Power 3: Negatively charged

872 APPENDIX B
 alkaline-earth metals, the halogens, and the
Making Two- Column Notes noble gases.
2. Divide a blank sheet of paper into two
Two-column notes can be used to learn and columns and write the main ideas in the left -
review definitions of vocabulary terms, examples hand column. Summarize your ideas using
of multiple-step processes, or details of specific quick phrases that are easy for you to under -
concepts. The two-column-note strategy is sim- stand and remember. Decide how many details
ple: write the term, main idea, step-by-step you need for each main idea, and write that
process, or concept in the left -hand column, and number in parentheses under the main idea.
the definition, example, or detail on the right. 3. Write the detail notes in the right -hand col-
One strategy for using two-column notes is to umn. Be sure you list as many details as you
organize main ideas and their details. The main designated in the main -idea column. The table
ideas from your reading are written in the left - below shows some details that correspond to
hand column of your paper and can be written as the main ideas in Chapter 5, Section 2.
questions, key words, or a combination of both. The two-column method of review is perfect
Details describing these main ideas are then whether you use it to study for a short quiz or
written in the right -hand column of your paper. for a test on the material in an entire chapter.
.
1 Identify the main ideas. The main ideas for a Just cover the information in the right -hand col -
chapter are listed in the section objectives. umn with a sheet of paper, and after reciting
However, you decide which ideas to include in what you know, uncover the notes to check your
your notes. For example, the table below answers. Then ask yourself what else you know
shows some main ideas from the objectives in about that topic. Linking ideas in this way will
Chapter 5, Section 2. help you to gain a more complete picture of
•Describe the locations in the periodic table chemistry.
and the general properties of the alkali metals.

Main Idea Detail Notes

• Alkali metals •Group 1

( 4 details) •highly reactive
• ns 1 electron configuration
•soft, silvery
•Alkaline-earth metals •Group 2
(4 details ) •reactive
• ns2 electron configuration
•harder than alkali metals
• Halogens (3 details ) •Group 17
•reactive
•nonmetallic
•Noble gases (3 details) •Group 18
•low reactivity
•stable ns2np6 configuration

APPENDIX B 873
 4. Think about what you want to know about the
Using the K / W / L Strategy information in the objectives, and write these
ideas in the second column. Include informa -
The K / W / L strategy stands for “ what I Know — tion from both the section objectives and any
what I Want to know — what I Learned." You
other objectives your teacher has given you.
start by brainstorming about the subject matter
5. While reading the section or afterwards, use
before reading the assigned material. Relating the third column to write down the informa -
new ideas and concepts to those you have tion you learned. While reading, pay close
learned previously will help you better under - attention to any information about the topics
stand and apply the new knowledge you obtain .
you wrote in the “ What 1 Want to Know " col -
The section objectives throughout your textbook umn . If you do not find all of the answers you
are ideal for using the K / W / L strategy. are looking for, you may need to reread the
1. Read the section objectives. You may also
section or reference a second source . Be sure
want to scan headings, boldfaced terms, and
to ask your teacher if you still cannot find the
illustrations before reading. Here are two of
information after reading the section a second
the objectives from Chapter 1 . Section 2 to use
time.
as an example.
It is also important to review your brain-
• Explain the gas, liquid, and solid states in stormed ideas when you have completed read-
terms of particles.
ing the section . Compare your ideas in the first
• Distinguish between a mixture and a pure column with the information you wrote down
substance. in the third column. If you find that some of
2. Divide a sheet of paper into three columns,
your brainstormed ideas are incorrect , cross
and label the columns “What I Know," “ What
them out. It is extremely important to identify
I Want to Know," and “ What I Learned." and correct any misconceptions you had prior
3. Brainstorm about what you know about the
to reading before you begin studying for vour
information in the objectives, and write these
test .
ideas in the first column. Because this chart
is designed primarily to help you integrate
your own knowledge with new information, it
is not necessary to write complete sentences.

What I Know What I Want to Know What I Learned

• gas has no definite shape or •how gas, liquid , and solid states •molecules in solid and liquid
volume are related to particles states are close together, but are
•liquid has no definite shape but far apart in gas state
,
•how mixtures and pure sub-
has definite volume stances are different •molecules in solid state have
•solid has definite shape and fixed positions, but molecules in
volume liquid and gas states can flow

•mixture is combination of sub - •mixtures are combinations of

stances pure substances

•pure substance has only one •pure substances have fixed

component compositions and definite
properties

874 APPENDIX B
 3. Place the strips in their proper
Using Sequencing / Pattern sequence. Confirm the order of the process
Puzzles bv checking- vour text or your class notes.
J SX ml J

You can use pattern puzzles to help you

•List the given and unknown information.
remember sequential information. Pattern
puzzles are not just a tool for memorization.
•Look at the periodic table to determine the molar mass
'
They also promote a greater understanding of of the substance .
a variety of chemical processes, from the steps
•Write the correct conversion factor to convert moles to grams.
in solving a mass-mass stoichiometry problem to
the procedure for making a solution of specified • Multiply the amount of substance by the conversion factor.
molarity. •Solve the equation and check your answer.

1. Write clown the steps of a process in your own

words. For an example, we will use the
Pattern puzzles are especially helpful when
process for converting the amount of a sub-
you are studying for your chemistry tests. Before
stance in moles to mass in grams. ( See Sample
tests, use your puzzles to practice sequencing and
Problem B on page N4. ) On a sheet of note -
to review the steps of chemistry processes. You
book paper, write down one step per line, and
and a classmate can also take turns creating your
do not number the steps. Also, do not copy
own pattern puzzles of different chemical
the process straight from your textbook.
Writing the steps in your own words pro-
processes and putting each others puzzles in the
correct sequence. Studying with a classmate in
motes a more thorough understanding of the
this manner will help make studying fun and will
process. You may want to divide longer steps
enable you to help each other.
into two or three shorter steps.

•List the given and unknown information.

•Look at the periodic table to determine the molar mass
of the substance.

•Write the correct conversion factor to convert moles to grams.

•Multiply the amount of substance by the conversion factor.
•Solve the equation and check your answer.

2. Cut the sheet of paper into strips with only

one step per strip of paper. Shuffle the strips
of paper so that they are out of sequence.

•Look at the periodic table to determine the molar mass

of the substance.

• Solve the equation and check your answer.

•List the given and unknown information .

•Multiply the amount of substance by the conversion factor.
• Write the correct conversion factor to convert moles to grams.

APPENDIX B 875
 ic table on pages 140- 141 or on the inside back
Other Reading Strategies cover of your book so you can easily locate it
and use it for reference as you study different
Brainstorming aspects of chemistry and solve problems involv -
Brainstorming is a strategy that helps you recog- ing elements and compounds.
nize and evaluate the knowledge you already
have before you start reading. It works well indi -
vidually or in groups. When you brainstorm, you Interpreting Graphic Sources of
start with a central term or idea, then quickly list Information
all the words, phrases, and other ideas that you Charts, tables, photographs, diagrams, and other
think are related to it. illustrations are graphic, or visual, sources of
Because there are no “ right or “ wrong *
** *

information. The labels and captions, together

answers, you can use the list as a basis for classi - with the illustrations help you make connections
fying terms, developing a general explanation, or between the words and the ideas presented in
speculating about new relationships. For exam- the text .
ple, you might brainstorm a list of terms related
to the word element before you read Chapter 1.
Section 2. The list might include gold, metals,
Reading Response Logs
chemicals, silver, carbon, oxygen, and water. As
you read the textbook, you might decide that Keeping a reading response log helps you inter -
some of the terms you listed are not elements. pret what you read and gives you a chance to
Later, you might use that information to help you express your reactions and opinions about what
distinguish between elements and compounds. you have read. Draw a vertical line down the
center of a piece of paper. In the left -hand col -
umn. write down or make notes about passages
Building/ Interpreting Vocabulary you read to which you have reactions, thoughts,
Using a dictionary to look up the meanings of feelings, questions, or associations. In the right -
prefixes and suffixes as well as word origins and hand column, write what those reactions,
meanings helps you build your vocabulary and thoughts, feelings, questions, or associations are.
interpret what you read. If you know the mean- For example, von might keep a reading response
ing of prefixes like kilo- ( one thousand) and log when studying about Nuclear Energy in
mi Hi - ( one thousandth ), you have a good idea Chapter 21.
what kilograms, kilometers, milligrams, and mil-
limeters are and how they are different . ( See
page 35 for a list of SI Prefixes. )
Knowledge of prefixes, suffixes, and word ori -
gins can help you understand the meaning of
.
new words For example, if you know the suffix
-protic comes from the same word as proton, it
will help you understand what monoprotic and
polyprotic acids are ( see page 479 ).

Reading Hints
Reading hints help you identify and bookmark
important charts, tables, and illustrations for
easy reference. For example, you may want to
use a self-adhesive note to bookmark the period-

876 APPENDIX B
 relationship as you read Chapter 11, Section 2:
Other Studying Strategies At constant pressure, increase in temperature
( cause ) —> increase in gas volume ( effect ).
Comparing and Contrasting
Comparing and contrasting is a strategy that Making a Prediction Guide
helps you note similarities and differences A prediction guide is a list of statements about
between two or more objects or events. When which you express and try to justify your opin -
you determine similarities, you are comparing. ions based on your current knowledge. After
When you determine differences, you are con - reading the material, you re -evaluate your opin -
trasting. ion in light of what you learned. Using prediction
You can use comparing and contrasting to guides helps you evaluate your knowledge, iden -
help you classify objects or properties, differenti- tify assumptions you may have that could lead to
ate between similar concepts, and speculate mistaken conclusions, and form an idea of
about new relationships. For example, as you expected results.
read Chapter 1 you might begin to make a table 1. Read the statements your teacher writes on
in which you compare and contrast metals, non - the board. For example, look at the five
metals, and metalloids. As you continue to learn statements from Dalton 's theory listed on page
about these substances in Chapters 4 and 5, you 68 of your textbook.
can add to your table, giving you a better under - 2. Decide whether you think each statement is
standing of the similarities and differences true or false and discuss reasons why you think
among elements. so.
3. After reading the section, re- evaluate your
Identifying Cause and Effect opinion of each statement. Discuss why your
Identifying causes and effects as you read helps opinion changed or remained the same.
you understand the material and builds logical Find passages in the text that account for
reasoning skills. An effect is an event or the result the change of reinforcement of your
of some action. A cause is the reason the event or .
opinions For example, you might have
action occurred. Signal words, such as because, so, agreed with all five statements from Dalton's
since, therefore, as a result, and depends on, indi- theory before reading the text . Then, after
cate a cause-and-effect relationship. reading about atoms and subatomic particles,
You can use arrows to show cause and effect. you might have changed your opinion about
For example, you might write this cause-and-effect .
the first statement

/ \

APPENDIX B 877
 Summarizing/ Paired Summarizing
Cooperative Learning A summary is a brief statement of main ideas or
Techniques important concepts. Making a summary of what
you have read provides you with a way to review
Reading with a Partner what you have learned, see what information
Reading with a partner is a strategy that can help needs further clarification, and helps you make
you understand what you read and point out connections to previously studied material.
where more explanation is needed. Paired summarizing helps strengthen your
1. First read the text silently by yourself. Use
v r
ability to read, listen, and understand. It is espe-
self-adhesive notes to mark those parts of the cially useful when a section of text has several
text that you do not understand. For exam - subdivisions, each dealing with different concepts,
ple, you might have difficulty with some of the such as Chapter 2. Section 3 in your textbook .
material about quantum numbers in Section 2 1. First read the material silently by yourself.
w %> %

of Chapter 4. while another student under - 2. Then you and your partner take turns being
stands quantum numbers but has trouble with the “listener " and the “reteller." The reteller
electron configurations in Section 3. summarizes the material for the listener, who
2. Work with a partner to discuss the passages does not interrupt until the reteller has fin -
each of you marked. Take turns listening and ished. If necessary, the reteller may consult the
trying to clarify the difficult passages for each text, and the listener may ask for clarification .
other. Together, study the related tables and The listener then states any inaccuracies or
illustrations and explain to each other how omissions made by the reteller.
they relate to the text . 3. Work together to refine the summary. Make
3. For concepts that need further explanation, sure the summary states the important ideas in
work together to formulate i|uestions for class a clear and concise manner.
discussion or for your teacher to answer.
Discussing Ideas
Discussing ideas with a partner or in a group
Using L.I.N.K . before you read is a strategy that can help
The L.I.N. K . strategy stands for List. Inquire. vou broaden vour knowledge base and decide
Notes, Know. It is similar to the K / W /L strategy, what concepts to focus on as you are reading .
but you work as a class or in groups. Discussing ideas after you have read a section or
1. Brainstorm all the words, phrases, and ideas chapter can help you check your understanding,
associated with the term your teacher pro- clarify difficult concepts, and lead you to specu -
vides. Volunteers can keep track of contribu - late about new ideas.
tions on the board or on a separate sheet of
paper.
2. Your teacher will direct you in a class or group
discussion about the words and ideas
listed. Now is the time to inquire, or ask your
teacher and other students for clarification of
the listed ideas.
3. At the end of the discussion, make notes about
everything you can remember. Look over
your notes to see if you have left anything out.
4. See what you now know about the given con-
cept based on your own experience and the
discussion.

878 APPENDIX B
 APPENDIX C

Graphing Calculator
Technology
( harts, graphs, and data analysis arc essential ele- appropriate TI Connectivity computer- to -
ments of chemistry . To be successful in your study calculator cable and TI Connect software
of chemistry, you must know how to make and
a computer that has Internet access
interpret graphs and must understand the relation-
ships between different variables. The detailed instructions on how to download the
Your graphing calculator can be a powerful tool calculator programs can be found at go.hrw.com
for analyzing chemical data. In addition to using your ( keyword HC6 CALC ).
calculator to organize and graph data, you can pro-
gram your calculator to perform specialized functions.
In the text, you can use your graphing calcula -
Calculator-Based
tor to help solve the Chapter Review exercises. In Laboratories
addition, specific Graphing Calculator exercises Analyzing your data properly is as important as
referred to in the Chapter Reviews will help you using good experimental technique in the chemistry
explore the capabilities of your calculator while lab. Your results w ill be meaningless if you do not
enhancing your understanding of mathematical know how to interpret them. The Calculator-Based
relationships that are important in chemistry. The Laboratory 2 ( CBL 2 ) data-collection interface
CBL 2 and LabPro - probeware experiments will bv Texas Instruments and the Vernier LabPro '
J

enable you to become adept at analyzing experi - data-collection interface by Vernier Software &
mental data. Technology can simplify the process of obtaining
and analyzing experimental data.
The data-collection interface
Graphing Calculator Exercises mimics expensive electronic labo-
The go.hrw.com site provides downloadable pro - ratory equipment and allows you
grams for the TI-83 Plus and the TI-84 Plus graph - to collect real experimental data
ing calculator families. These programs include data that are stored directly onto your
sets to analyze. I ' sing these programs will improve
calculator. As a result, you will not
your ability to handle scientific data. have to record and graph vour
You will learn to use your calculator to graph data manually. Instead, your data
data. Then, you will interpret the graphs and w ill are automatically tabulated, and
extract the information required to answer the you can view real-time graphs.
questions in the exercises. You will gain experience Consequently, you have more
with simple linear relationships, such as the rela - Vw
time to interpret your experi -
tionship between energy and temperature, and com- mental results. The interface
plex relationships, such as the relationship between and probes allow you to col - fib
pH and titrant volume, w hich is represented by a lect experimental data, and
titration curve. with the DataMate App '

To solve the Graphing Calculator exercises in the ^ £'

t
the information coming from
Chapter Reviews and to download the programs, the probes is automatically 9
L
you will need recognized.
a graphing calculator ( Tl -83 Plus or TI-84 Plus )

APPENDIX C 879
 Additional information about these and other
applications for your calculator is available at
education.ti.com. These applications are standard
for some models of TI calculators and can be
obtained from Texas Instruments and downloaded
onto other models.

Troubleshooting
Calculator instructions in the Modern Chemistry
program are written for the 11-84 Plus. You may
use other graphing calculators, but some of the
programs and instructions may require minor
adjustments.
The CBL 2 set -up is shown above. In some
labs, you will use a temperature sensor, a pressure Calculator- based probeware experiments are
written for the CBL 2 rM and LabPro - interfaces.
sensor, a voltage sensor, and a colorimeter to collect
data. You will then analyze the data on your calcu- Older versions of the experiments for the origi-
nal CBL are available at go.hrw.com.
lator to obtain the results of your experiment. To
perform the calculator-based probeware experi - The DataMate App is not compatible with the
ments, you will need original CBLrM system. For more information
and user manuals for the CBL 2 rM and the
a graphing calculator ( IT -83 Plus or 11-84 Plus ) ,
CBL M systems, v isit cducation.ti.com/guides
the CBL 2
, NI
or LabPro® data collection interface
If you have problems loading programs or appli -
the appropriate Texas Instruments or Vernier cations onto your calculator, you may need to
probe for the experiment clear programs or other data from your calcula -
the probeware experiment tor 's memory .
The probeware experiments are available at Always make sure that you are downloading the
go.hrw.com ( keyword HC6 CBL ). For additional version of the software that is correct for your
information about the C BL 2 and LabPro hardware calculator and that you have the latest operating
or software, visit cducation.ti.com or system for your calculator and your CBL 2 .
www.vcmier.com If you need additional help, Texas Instruments
and Vernier Software & Technology can provide
Making the Most of your technical support. Contact TI at cducation.ti.com
or 1 -800 - II- CARLS and Vernier at
Calculator info@ vcrnnicr.com or 1-888-837-6437.
In addition to organizing and graphing scientific
data. Texas Instruments calculators have other
applications that are available for use in chemistry.
The Periodic Table App provides an electronic 90 ) Go To: go hrw.com
.
I/ nriv Keyword: HC6 CALC
version of the periodic table as well as information I .iom
about the elements.
This Web site contains links for
The Science Tool App provides various physical downloading programs and appli-
constants and allows you to convert between differ - cations that you will need for the
ent units and to determine the number of significant
1 Graphing Calculator exercises.

figures for calculations.

880 APPENDIX C
 APPENDIX D

Problem Bank
Conversions: Chap. 2, Sec. 2 .
8 I low many palisade cells from plant leaves would lit in
a volume of 1.0 cm3 of cells if the average volume of a
Converting Simple SI Units palisade cell is 0.0147 mm3 ?
.
1 State the following measured quantities in the units
indicated. Mixed Review
.
a 5.2 cm of magnesium ribbon in millimeters .
9 Convert each of the following quantities to the required
b. 0.049 kg of sulfur in grams unit.
.
c 1.60 mL of ethanol in microliters .
a 12.75 Mm to kilometers
d. 0.0025 g of vitamin A in micrograms h. 277 cm to meters
.
e 0.020 kg of tin in milligrams .
c 30 560 m: to hectares ( 1 ha - 10 000 m2 )
.
f 3 kL of saline solution in liters cl. 81.0 cm-' to square meters
2. State the following measured quantities in the units .
e 300 000 km to megameters
indicated. .
10 Convert each of the following quantities to the
.
a 150 mg of aspirin in grams required unit .
b. 2500 mL of hydrochloric add in liters .
a 0.62 km to meters
.
c 0.5 g of sodium in kilograms b. 3857 g to milligrams
.
d 55 L of carbon dioxide gas in kiloliters .
c 0.0036 mL to microliters
.
e 35 mm in centimeters .
d 0.342 metric tons to kg ( 1 metric ton = 1000 kg)
f. 8740 m in kilometers .
e 68.71 kL to liters
.
g 209 nm in millimeters 11. Convert each of the following quantities to the
h. 500 000 /ig in kilograms required unit .
3. The greatest distance between Earth and the .
a 856 mg to kilograms
sun during Earth 's revolution is 152 million .
b I 210 000 tg to kilograms
^
.
kilometers What is this distance in .
c 6598 fxL to cubic centimeters ( 1 mL = I cm 3 )
mega meters? cl. 80 600 nm to millimeters
4 . How many milliliters of water will it take .
e 10.74 cm 3 to liters
to fill a 2.00 L bottle that already contains .
12 Convert each of the following quantities to the
1.87 L of water? required unit.
5. A piece of copper wire is 150 cm long. How .
a 7.93 L to cubic centimeters
long is the wire in millimeters? How many b. 0.0059 km to centimeters
50 mm segments of wire can be cut from the length? .
c 4.19 L. to cubic decimeters
cl. 7.48 nv to square centimeters
6 . The ladle at an iron foundry can hold 8500 kg .
e 0.197 m3 to liters
of molten iron: 646 metric tons of iron arc
needed to make rails. How many ladlefuls .
13 An automobile uses 0.05 mL of oil for each kilometer
of iron will it take to make 646 metric tons it is driven. How much oil in liters is consumed if the
of iron? ( 1 metric ton = 1 ( MX ) kg ) automobile is driven 20 000 km?
14. How many microliters are there in a volume of
Converting Derived SI Units 370 mm - of cobra venom ?
.
7 State the following measured quantities in the units .
15 A baker uses 1.5 tsp of vanilla extract in each cake .
indicated. How much vanilla extract in liters should the baker
a. 310 ( HH ) cm - of concrete in cubic meters order to make 800 cakes? ( 1 tsp = 5 mL )
b. 6.5 m: of steel sheet in square centimeters
.
c 0.035 m3 of chlorine gas in cubic .
16 A person drinks eight glasses of water each day and.
centimeters each glass contains 300 mL. How many liters of water
.
d 0.49 cm- of copper in square millimeters will that person consume in a year ? What is the mass
.
e 1200 dm3 of acetic acid solution in of this volume of water in kilograms? ( Assume one
year has 365 days and the density of water is
cubic meters
.
f 87.5 mm - of actinium in cubic centimeters l.OOkg/L.)
.
g 250 000 cm* of polyethylene sheet in .
17 At the equator Earth rotates with a velocity of about
square meters 465 m/ s .
APPENDIX D 881
 .
a What is this velocity in kilometers per hour? 31. A heater gives oft energy as heat at a rate of 330
.
b What is this velocity in kilometers per day ? .
kJ /min What is the rate of energy output in kilocalo-
.
IS A chemistry teacher needs to determine what quantity ries per hour? ( 1 cal = 4.184 J )
of sodium hydroxide to order. If each student will use .
32 The instructions on a package of fertilizer tell sou to
130 g and there are 60 students, how many kilograms apply it at the rate of 62 g/m:. How much fertilizer in
of sodium hydroxide should the teacher order ? kilograms would vou need to apply to 1.0 ha? ( 1 ha =
.
19 The teacher in item IS also needs to order plastic tub- 10 0( H ) m 2)
ing. If each of the 60 students needs 750 mm of tubing, .
33 A water tank leaks water at the rate of 3.9 mL/h If.
what length of tubing in meters should the teacher the tank is not repaired, what volume of water in liters
order ? \sill it leak in a year ? Show your setup for solving this.

20. Convert the following to the required units, I lint: Use one conversion factor to convert hours to
.
a 550 fiL : h to milliliters per day days and another to convert days to years, and assume
.
li 9.00 metric tons /h to kilograms per minute that one year has 365 days.
.
c 3.72 L/h to cubic centimeters per minute .
34 A nurse plans to give flu injections of 50 /iL each from
(I. 6.12 km / h to meters per second .
a bottle containing 2.0 mL of vaccine I low many
21. Express the following in the units indicated, closes are in the bottle ?
.
a 2.97 kg/l as grams per cubic centimeter
h. 4128 g/ dm 2 as kilograms per square centimeter
.
c 5.27 g/cm 3 as kilograms per cubic decimeter Significant Figures: Chap. 2, Sec . 2
.
d 6.91 kg m ' as milligrams per cubic millimeter
.
35 Determine the number of significant figures in the ltd -
> > A gas has a density of 5.56 g/L.
* *
mm
lowing measurements,
.
a What volume in milliliters would 4.17 g of this gas
.
a 640 cm .f 20.900 cm
occupy ?
h. What would be the mass in kilograms of 1 m3 of
.
1» 200.0 mL .g O.(HH) 000 56 g/L

this gas?
..
c 0.52( H ) g .
.
h 0.04002 kg/m3
d 1.005 kg i 790 ( H )! cm2
23. I he average density of living matter on Earths land .
e 10 000 L .j 665.000 kg m /s:
#

areas is 0.10 g em 2. What mass of living matter in kilo- .

36 Perform the following calculations, and express the
grams would occupy an area of 0.125 ha ? result in the correct units and number of significant
.
24. A textbook measures 250. mm long 224 mm wide, and figures .
50.0 mm thick. It has a mass of 2.94 kg. .
a 47.0 m -4 2.2 s
.
a What is the volume of the book in cubic meters? .
h 140 cm x 35 cm
.
b What is the density of the book in grams per cubic
centimeter ?
.
. -
c 5.88 kg 200 m 3
cl 0.00 50 m2 X 0.042 m
.
c What is the area of one cover in square meters? c\ 300.3 L -s- 180. s
.
25 A glass dropper delivers liquid so that 25 drops equal .
f 33.00 cm 2 x 2.70 cm
LOO mL . .
g 35 000 kJ + 0.250 min
.
a What the volume of one drop in milliliters?
is 37. Perform the following calculations and express the
b. How many milliliters are in 37 drops ? results in the correct units and number of significant
. How many drops would be required to gel 0.68 L?
c figures.
.
26 I xpress each of the following in kilograms and grams, .
a 22.0 m + 5.28 m 4- 15.5 m
.
a 504 700 mg .
c 122 mg .
b 0.042 kg + 1,229 kg 4- 0.502 kg
1». 9 2( H) ooo Mg d. 7195 eg c. 170 cm • 3.5 cm2
'
28 cm '
. .
d 0.003 L 4 0.0048 L 4 0.100 L.
27 I xpress each of the following in liters and milliliters,
a 582 cm. ;
.
c 1.18 dm3
.
e 24.50 dL 4- 4.30 dL 4- 10.2 dL
.
I) 0.0025 m3 .
d 32 900 jd.
f. 32( H ) mg + 325 mg - 688 mg
g. 14 ( HH ) kg 4 8000 kg * 590 kg
.
28 Express each o! the following in grams per liter and
kilograms per cubic meter. Mixed Review
.
a 1 ,37 g/cm ' .
d 38 ( MM ) g/m ' 38. Determine the number ot significant figures in the fol -
.
b 0.692 kg/dm ' .
e 5.79 mg/mm3 lowing measurements.
.
c 5.2 kg/L .
f 1.1 /ig/niL ..
a 0.0120 m .
f 1000 kg
.
29 An industrial chemical reaction is run for 30.0 h and h 100.5 mL .
g 180. mm
produces 648.0 kg of product. What is the average rate
of product production in the stated units ?
..
c 101 g
d 350 cm 2 .
.
h 0.4936 L
i 0.020 7( H ) s
.
a grams per minute .
e 0.97 km
b. kilograms per day .
39 Round the following quantities to the specified num -
.
c milligrams per millisecond ber of significant figures.
.
30 What is the speed of a car in meters per second when .
a 5 487 129 m to three significant figures
it is moving at HH). km h ? .
h 0.013 479 265 ml to six significant figures

882 APPENDIX D
 c. 31 947.972 cm 2 to lour significant figures 48. A container measures 30.5 mm X 202 mm X 153 mm .
cl. 192.6739 m: to five significant figures When it is full of a liquid, it has a mass of 1.33 kg.
e. 786.9164 cm to two significant figures When it is empty, it has a mass of 0.30 kg. What is the
f. 3N9 277 6( H ) J to six significant figures density of the liquid in kilograms per liter ?
g. 225 834.762 cm- to seven significant figures 49. If 7.76 km of wire has a mass of 3.3 kg. what is the
40. Perform the following calculations, and express the mass of the wire in g/m? What length in meters would
answer in the correct units and number of significant have a mass of 1.0 g?
figures. 50. A container of plant food recommends an application
a. 651 cm x 75 cm rate of 52 kg/ha . If the container holds 10 kg of plant
h. 7.835 kg -r 2.5 1. food, how many square meters will it cover? ( I ha =
c. 14.75 L -s- 1.20 s 10 000 m2 )
d. 360 cm X 51 cm X 9.07 cm
51. A chemical process produces 974 550 k .I of energy as
e. 5.18 m x 0.77 m x 10.22 m
heat in 37.0 min . What is the rate in kilojoules per
.
f 34.95 g -r 11.169 cm-'
minute ? What is the rate in kilojoules per second?
41. Perform the following calculations, and express the 52. A water pipe fills a container that measures 189 cm x
answer in the correct units and number of significant 307 cm x 272 cm in 97 s.
figures. a. What is the volume of the container in cubic meters?
a. 7.945 J + 82.3 J - 0.02 J b. What is the rate of flow in the pipe in liters per
b. 0.0012 m - 0.000 45 m - 0.000 11 m
minute ?
.
c 500 g • 432 g + ? 8 - c. What is the rate of flow in cubic meters per hour ?
d. 312 kPa 4 04)035 kPa - 0.147 kPa
t*. 312 dL 31.2 JL 3.12 dL - 53. Perform the following calculations, and express the
f. 1701 kg + 50 kg + 43 kg results in the correct units and with the proper num-
ber of significant figures. Note , in problems with mul -
42. A rectangle measures 87.59 cm by 35.1 mm. Express tiple steps, it is better to perform the entire calculation
its area with the proper number of significant figures and then round to significant figures.
in the specified unit . a. ( 0.054 kg 4 1.33 kg ) X 5.4 m2
a. in cm 2 c. in m- b. 67.35 cm 2 4 ( 1.401 cm - 0.399 cm )
b. in mm2 c. 4.198 kg x ( 1019 m 2 - 40 m 2 ) 4 ( 54.2 s x 31.3 s )
43. A box measures 900. mm by 31.5 mm by 6.3 cm. State d. 3.14159 m x ( 4.17 m 4- 2.150 m )
its volume with the proper number of significant fig- e. 690 (MH) m 4 ( 5.022 h - 4.31 h )
ures in the specified unit . f. ( 6.23 cm 3.111 cm - 0.05 cm ) x 14.99 cm
a. in cm * c. in nun3
b. in m
;

44. A 125 mL sample of liquid has a mass of 0.16 kg.

Scientific Notation: Chap. 2, Sec . 3
What is the density of the liquid in the following mea- Converting Quantities to Scientific Notation
surements? 54. Express the following quantities in scientific notation.
a. kg/m * c. kg/dm3 a. 8 800 000 000 m
b. g/mL b. 0.0015 kg
45. Perform the following calculations, and express the .
c 0.000 000 000 06 kg/m3
results in the correct units and with the proper num - d. 8 002 ( M )( ) Hz
ber of significant figures. e. 0.009 003 A
a. 13.75 mm x 10.1 mm x 0.91 mm f. 70 000 000 000 000 000 km
b. 89.4 cm2 x 4.8 cm g. 6028 L
c. 14.9 m ' -r 3.0 m 2 h. 0.2105 g
d. 6.975 m X 30 m X 21.5 m i. 6( H ) 005 000 kJ /h
j. 33.8 m:
46. What is the volume of a region of space that measures
752 m X 319 m X 110 m ? Give your answer in the cor -
rect unit and with the proper number of significant
Calculating with Quantities
figures. in Scientific Notation
55. Carry out the following calculations. Express the results
47. Perform the following calculations, and express the in scientific notation and with the correct number of
results in the correct units and with the proper num - significant figures.
ber of significant figures. a. 4.74 x l ( )4 km 4 7.71 x 103 km 4 1.05 x 103 km
a. 7.382 g + 1.21 g 4 4.7923 g b. 2.75 x It) 4 m 4 8.03 x 10 ~5 m 4 2.122 x 10" 3 m
'

b. 51.3 mg 4- 83 mg - 34.2 mg c. 4.0 X nr 5 m3 4 6.85 x 10~6 m3 - 1.05 x 10 5 m3

~

c. 0.007 L - 0.0037 L 4- 0.012 L d. 3.15 x 102 mg 4 3.15 x 103 mg 4 3.15 X 104 mg

cl. 253.05 cm2 4 33.9 cm 2 + 28 cm2 . -
e 3.01 x 1022 atoms 4 1.19 x 1023 atoms 9.80 x
.
e 14.77 kg 4 0.086 kg - 0.391 ke I 0:i atoms
f. 319 mL 13.75 mL - 20. mL f. 6.85 x 101 nm 4 4.0229 x 10s nm - 8.38 x 10* nm

APPENDIX D 883
 .
56 Carry out the following computations, and express the .
64 Light travels at a speed of about 300 000 km/ s.
result in scientific notation. . Express this value in scientific notation
a ,
.
a 7.20 x 103 cm x 8.08 x 103 cm h. Convert this value to meters per hour,
.
I) 3.7 X 104 mm x 6.6 x 104 mm X 9.89 x 103 mm .
c What distance in centimeters does light travel in
.
c 8.27 • | ( » - m < 23 > 1
1
m X 3.00 X 10 4 m
" 1 /is?
.
d 4.44 x 10 » m x 5.55 x 1019 m x 7.69 x 10 12 kg
“ "

.
.
e 6.55 x Ufi dm X 7.89 x 109 dm x 4.01893 X 105 dm
65 There are 7.11 x 1024 molecules in 100.0 cm3 of a cer -
tain substance.
.
57 C arry out the following computations, and express the .
a What is the number of molecules in 1.09 cm3 of the
result in scientific notation.
.
a 2.290 x l()7 cm
.
4.33 x 103 s
h 1.788 x 10 5 L -5- 7.111 X 10" 3 m-
~ - substance?
b. What would be the number of molecules in 2.24 x
104 cm ' of the substance ?
.
c 5.515 x l l R r 6.04 x Ufi km .
c What number of molecules are in 9.01 x 10“ cm3
*
.
d 3.29 X 10 4 km + 1.48 X 10 - min
. 10
e 4.73 x 10 4 g 4- ( 2.08 x 10 3 km x 5.60 x
4 km )
of the substance?
66. The number of transistors on a particular integrated
circuit is 3 578 000. and the integrated circuit measures
9.5 mm x 8.2 mm.
Mixed Review .
a What is the area occupied by each transistor ?
.
58 Express the following quantities in scientific notation, h. Using your answer from ( a ), how many transistors
.
a 158000 km could be formed on a silicon sheet that measures
.
h 0.000 009 782 L 353 mm x 265 mm?
.
c 837 100 000 cm
;
.
67 A solution has 0.0501 g of a substance in 1.00 L.
d. 6 500 000 000 mm2
Express this concentration in grams per microliter.
.
e 0.005 93 g
.
f 0.000 (KM) 006 13 m 68. Cesium atoms are the largest of the naturally occur -
.
g 12 552 (MX) J .
ring elements They have a diameter of 5.30 x 10 10 m.
.
h 0.000 008 004 g/L C alculate the number of cesium atoms that would
i. 0.010 995 kg have to be lined up to give a row of cesium atoms
.
j 1050 000 000 Hz 2.54 cm ( 1 in. ) long .
59. Perform the following calculations, and express the .
69 The neutron has a volume of approximately 1.4 X
result in scientific notation with the correct number of 10 44 m3 and a mass of 1.675 x 10 24 g. Calculate the
significant figures. density of the neutron in g/m\ What is the mass of
.
a 2.48 X 102 kg + 9.17 x Ufi kg + 7.2 x 101 kg 1.0 cm3 of neutrons in kilograms?
.
b 4.07 X 10 “ 5 mg + 3.966 x II)'4 mg + 7.1 x
.
70 The pits in a compact disc are some of the smallest
10“: mg
.
c 1.39 x 104 m3 + 6.52 x 102 m3 - 4.8 X Ufi m3
-
things ever mass produced mechanically by humans.
These pits represent the Is and 0s of digital informa -
.
d 7.70 x 10 9 m - 3.95 x 10 * m + 1.88 x 10 "7 m
"

tion on a compact disc. These pits are only 1.6 X

.
c* 1.111 x Ufi J + 5.82 x 104 J + 3.01 x Ufi J
10 K m deep ( 1 /4 the wavelength of red laser light ).
.
f 9.81 x 1027 molecules + 3.18 X 1025 molecules - How many of these pits would have to be stacked on
2.09 x in26 molecules
top of each other to make a hole 0.305 m deep?
g. 1.36 x 10 cm 4 3.456 x 10 cm — 1.01 x 10 cm +
5.122 x 105 cm
* * .
71 22 400 mL of oxygen gas contains 6.022 x 1023 oxygen
.
60 Perform the following computations, and express the molecules at O 'C and standard atmospheric pressure.
result in scientific notation with the correct number of .
a How many oxygen molecules are in 0.100 mL of
gas?
significant figures.
. .
b How many oxygen molecules are in 1.00 L of gas?
a 1.54 X Ur 1 L + 2.36 X 10 4 s
.
h 3.890 X 104 mm X 4.71 X 10: nun2 .
c What is the average space in milliliters occupied by
.
c 9.571 x 103 kg 3.82 x 10 1 m2
* 1.97 x Ufi s
one oxygen molecule ?
.
d 8.33 X Ufi km
,
72. The mass ol the atmosphere is calculated to be
.
e 9.36 x 102 m x 3.82 x ufi m X 9.01 X 10 1 m “
.
5.136 x 10 H kg and there are 6 500 000 000 people

.
.
f 6.377 x 104 J 7.35 x 10 ~ 3 s
-
61 Your electric company charges you for the electric
living on Earth. Calculate the following values,
.
a The mass of atmosphere in kilograms per person,
. . h. The mass of atmosphere in metric tons per person,
energy you use measured in kilowatt - hours ( kWh )
One kWh is equivalent to 3 600 000 J. Express this .
c If the number of people increases to 9 500 000 000,
quantity in scientific notation . what is the mass in kilograms per person?
.
62 The pressure in the deepest part of the ocean is .
73 The mass of the sun is 1.989 x I 03 kg, and the mass
°
11 200 000 Pa. Express this pressure in scientific of Earth is 5.974 x 1024 kilograms. How many Earths
notation. would be needed to equal the mass of the sun ?
.
63 Convert 1.5 km to millimeters, and express the result 74. A new landfill has dimensions of 2.3 km X 1.4 km x
in scientific notation. 0.15 km.

884 APPENDIX D
 .
a Whal is I he volume in cubic kilometer?
Shape Dimensions
b. What is the volume in cubic meters?
c. II 250 000 000 objects averaging 0*060 m 3 each are .
a 2.27 g/cm 3 3.93 kg ?L cube ?m x ?m x?m
placed into the landfill each year how many years
, 1». 1.85 g/cm ; ?g ? cm 1 rectangle 33 mm X
will it take to fill the landfill? 21 mm x 7.2 mm
.
75 A dietary calorie ( C ) is exactly equal to 1000 cal. If .
c 3.21 g / L ? kg ? dm 3 sphere 3.30 m diameter
your daily intake of food gives you 24( H ) C. what is
cl. ? g/cm 3 497 g ? m' cylinder 7.5 cm diameter X
your intake in joules per day ? ( 1 cal = 4.184 J )
12 cm
.
e 0,92 g /cm 3 ? kg ? cm 3 rectangle 3.5 m X 1.2 m X
0.65 m
Four Steps for Solving
Quantitative Problems: Chap . 2, .
85 When a sample of a metal alloy that has a mass of
Sec . 3 9.65 g is placed into a graduated cylinder containing
water, the volume reading in the cylinder increases
76. Gasoline has a density of 0.73 g /cm 3. How many liters from 16.0 mL to 19.5 ml. What is the density of the
of gasoline would be required to increase the mass of alloy sample in grams per cubic centimeter ?
an automobile from 1271 kg to 1305 kg ? 86. Pure gold can be made into extremely thin sheets
77. A swimming pool measures 9.0 m long by 3.5 m wide called gold leaf . Suppose that 50. kg of gold is made
.
bv 1.75 m deep What mass of water in metric tons into gold leaf having an area of 3620 m:. The density
( 1 metric ton = 1000 kg) does the pool contain when of gold is 19.3 g/cm 3.
filled ? The densitv of the water in the pool is a. How thick in micrometers is the gold leaf ?
0.997 g/cm 3. b. A gold atom has a radius of 1.44 x 10 10 m . I low
78. A tightly packed box of crackers contains 250 g of many atoms thick is the gold leaf ?
crackers and measures 7.0 cm x 17.0 cm X 19.0 cm . 87. A chemical plant process requires that a cylindrical
What is the average density in kilograms per liter of reaction tank be filled with a certain liquid in 238 s.
the crackers in the package ? Assume that the unused The tank is 1.2 m in diameter and 4.6 m high . What
volume is negligible. flow rate in liters per minute is required to fill the
reaction tank in the specified time ?
88. I he radioactive decay of 2.8 g of plutonium -238
Mixed Review
generates 1.0 joule of energy as heat every second.
Solve these problems by using the Four Steps for Plutonium has a density of 19.86 g/cm 3. How many calo-
Solving Quantitative Problems. ries ( 1 cal 4.184 J ) of energy as heat will a rectangular
piece of plutonium that is 4.5 cm x 3.05 cm x 15 cm
79. The aluminum foil on a certain roll has a total area of generate per hour?
18.5 m 2 and a mass of 1275 g. Using a density of 2.7 g
per cubic centimeter for aluminum , determine the 89. The mass of Earth is 5.974 X 1024 kg. Assume that
thickness in millimeters of the aluminum foil. Earth is a sphere of diameter 1.28 x 104 km and calcu -
late the average density of Earth in g/cm 3.
80. If a liquid has a density of 1.17 g/ cm 3. how many liters
of the liquid have a mass of 3.75 kg? 90. What volume of magnesium in cubic centimeters
would have the same mass as 1.82 dm 3 of platinum?
81. A stack of 500 sheets of paper measuring 28 cm x 21 cm The density of magnesium is 1.74 g/cm '. and the den -
is 44.5 mm high and has a mass of 2090 g. What is the sity of platinum is 21.45 g/cm 3.
density of the paper in grams per cubic centimeter?
91. A roll of transparent tape has 66 m of tape on it . If an
82. A triangular-shaped piece of a metal has a mass of average of 5.0 cm of tape is needed each time the tape
6.58 g . The triangle is 0.560 mm thick and measures is used , how many uses can you get from a case of
36.4 mm on the base and 30.1 mm in height. What tape containing 24 rolls?
is the density of the metal in grams per cubic centi -
meter ? 92. An automobile can travel 38 km on 4.0 L. of gasoline.
If the automobile is driven 75 % of the days in a year
83. A packing crate measures 0.40 m X 0.40 m X 0.25 m . and the average distance traveled each day is 86 km .
You must fill the crate with boxes of cookies that each how many liters of gasoline will be consumed in one
measure 22.0 cm x 12.0 cm X 5.0 cm . How many year ( assume the year has 365 days )?
boxes of cookies can fit into the crate ?
93. A hose delivers water to a swimming pool that mea -
84. Calculate the unknown quantities in the following sures 9.0 m long by 3.5 m wide by 1.75 m deep. It
table. Use the following relationships for volumes of requires 97 h to fill the pool . At what rate in liters per
the various shapes. minute will the hose fill the pool ?
Volume of a cube = l x l x l
Volume of a rectangle = / X w x h 94. Automobile batteries are filled with a solution of sul -
Volume of a sphere = 4/37rr 3 furic acid , which has a density of 1.285 g/cm 3. The
Volume of a evlinder = TTT 1 X h solution used to fill the battery is 38 % ( by mass )

APPENDIX D 885
 sulfuric acid . How many grams of sulfuric acid arc pre - h. 0.005 20 mol of nitrogen gas. No
sent m 5( H ) mL of bauerv acid ? c. 1.05 mol of phosphorus trichloride , PCI3
d. 3.5 x 10 5 mol of vitamin C. ascorbic acid . C , HsO„
'
(

104. Calculate the number of formula units in the following

Mole Concept: Chap. 3, Sec. 3; amounts.
Chap. 7, Sec. 3 a. 1.25 mol of potassium bromide. KBr
b. 5.00 mol of magnesium chloride . MgCl 2
Problems Involving Atoms and Elements c. 0.025 mol of sodium carbonate Na2CC> 3
,

95. Calculate the number of moles in each of the following d . 0.82 X 10 6 mol of lead( II ) nitrate . Pb( NC> 3)2
'

masses. 105. Calculate the amount in moles of the following num -

a. 64.1 g of aluminum bers of molecules or formula units.
b. 28.1 g of silicon a. 3.34 x 1034 formula units of Cu( OH )2
c. 0.255 g of sulfur ,
b. 1.17 x I 0 h molecules of H 2S
d . 850.5 g of zinc c. 5.47 x 1021 formula units of nickel ( II ) sulfate .
96. Calculate the mass of each o! the following amounts . NiS04
a . 1 , 22 mol sodium d . 7.6b x I 01 " molecules of hydrogen peroxide , H 202
.
b 14.5 mol copper 106. Calculate the mass of each of the following quantities ,
c. 0.275 mol mercury a. 2.41 x l ( ):4 molecules of hydrogen . 1 C
d . 9.37 x 10 3 mo| magnesium
“

h. 5.00 x 1021 formula units of aluminum hydroxide ,

97. Calculate the amount in moles in each of the following AI ( OH )3
quantities. c. 8.25 X 1022 molecules of bromine pentafluoride ,
a. 3.01 X 1 ( ): * atoms of rubidium BrF5
b. 8.08 x 10:: atoms of krypton d. 1.20 x It)23 formula units of sodium oxalate .
c. 5 700 000 000 atoms of lead Na2C204
d . 2.997 x 10:' atoms of vanadium 107. Calculate the number of molecules or formula units in
98. Calculate the number of atoms in each of the follow - each of the following masses.
ing amounts. a. 22.9 g of sodium sulfide . Na2S
a. 1.004 mol bismuth b. 0.272 g of nickel ( II ) nitrate . Ni ( NC>3)2
b. 2.5 mol manganese c. 260 mg of acrylonitrile . CH 2 CHCN
c. 0.000 0002 mol helium
d . 32.6 mol strontium
Mixed Review
99. Calculate the number of atoms in each of the follow - 108. Calculate the number of moles in each of the following
ing masses. masses.
a. 54.0 g of aluminum a . 0.039 g of palladium
b. 69.45 g of lanthanum b. 8200 g of iron
c. 0.697 g of gallium c. 0.0073 kg of tantalum
d. 0.000 000 020 g beryllium d. 0.006 55 g of antimony
100. Calculate the mass of the following numbers of atoms, e. 5.64 kg of barium
a . 6.022 X 10:J atoms of tantalum 109. Calculate the mass in grams of each of the following
h. 3.01 X 10:1 atoms of cobalt amounts .
c. 1.506 x |( p4 atoms of argon a. 1.002 mol of chromium
d. 1.20 x 10- atoms of helium h. 550 mol of aluminum
c. 4.08 x 10 “8 mol of neon
Problems Involving Molecules, Formula d . 7 mol of titanium
Units, and Ions e. 0.0086 mol of xenon
101 . Calculate the number of moles in each of the following
*
I . 3.29 x 104 mol of lithium
masses. 110. Calculate the number of atoms in each of the follow -
a. 3.00 g of boron tribromide . BBr ing amounts.
b. 0.472 g of sodium fluoride . NaF
* a. 17.0 mol of germanium
c. 7.50 x 10- g of methanol , CH 3OH b. 0.6144 mol of copper
d . 50.0 g of calcium chlorate . Ca ( CIO 0: c. 3.02 mol of tin
102. Determine the mass of each of the following amounts. d . 2.0 x 106 mol of carbon
a. 1.366 mol of NH 3 e. 0.0019 mol of zirconium
b. 0.120 mol of glucose . CftHj 20$ .f 3.227 x 10 10 mol of potassium
c. 6.94 mol barium chloride . BaCF 111 . Calculate the number of moles in each of the follow -
cl . 0.005 mol of propane . C;, HS ing quantities.
103. Calculate the number of molecules in each of the fol - a. 6.022 x 10:4 atoms of cobalt
lowing amounts. b. 1.06 X 1023 atoms of tungsten
a. 4.99 mol of methane . CH 4 c. 3.008 X 10|g atoms of silver

886 APPENDIX D
 cl. 950 000 ( KM ) atoms of plutonium many moles are in a troy ounce of gold? How many
.
e 4.61 x lo 1 atoms of radon
.
moles are in a troy ounce of platinum? of silver ?
f 8 trillion atoms of cerium 120. A chemist needs 22.0 g of phenol, C H OH. for an
112. Calculate the number of atoms in each of the follow - experiment. Mow many moles of phenol
^ ^ is this
?
.
ing masses 121. A student needs 0.015 mol of iodine crystals, L. for an
a /u.0082 got gold experiment. What mass of iodine crystals should the
.
b 812 g of molybdenum student obtain ?
.
c 2.00 x ID2 mg of americium
122. 1'he weight of a diamond is given in carats. One carat
cl. 10.09 kg of neon
is equivalent to 200. mg. A pure diamond is made up
.
e 0.705 mg of bismuth
.
entirely of carbon atoms How many carbon atoms
.
f 37 /ig of uranium
make up a 1.00 carat diamond?
.
113 Calculate the mass of each of the following.
123. 8.00 g of calcium chloride, CaCL. is dissolved in
.
a 8.22 x 10- : atoms of rubidium
1.000 kg of water.
.
b 4.05 Avogadro's constants of manganese atoms
a. How many moles of CaCB are in solution? I low
.
c 9.96 x UP atoms of tellurium
many moles of water are present ?
cl. 0.000 025 Avogadro's constants of rhodium atoms
.
c 88 300 ( HH ) 000 000 atoms of radium
.
b Assume that the ionic compound. CaCh . separates
completely into Ca: and Cl ions when it dissolves
.
f 2.94 x 10 ' atoms of hafnium
' in water. How many moles of each ion are present
.
114 Calculate the number of moles in each of the follow - in the solution?
ing masses.
124. How many moles are in each of the following masses?
. .
a 45.0 g of acetic acid CH3COOH
.
a 453.6 i! < l .( HK ) pound ) of sucrose ( table suuar ).
.
b 7.04 g of lead(Il ) nitrate, PbfNOp
.
c 5000 kg of iron(III) oxide. Ci:H23On
b. I .( KH ) pound of table salt. NaC'l
. .
d 12.0 mg of ethylamine CTLNIH
125. When the ionic compound NH4C1 dissolves in water, it
. .
e 0.003 22 g ol stearic acid C 17H35COOH
breaks into one ammonium ion. NH4 ~ . and one chlo-
. .
f 50.0 kg of ammonium sulfate (NH SOj
. ^
115 Calculate the mass of each of the following amounts. ride ion. Cl . If you dissolved 10.7 g of NH4 CI in
water, how many moles of ions would be in solution?
. .
a 3.00 mol of selenium oxybromide SeOBn
126. What is the total amount in moles of atoms in a jar
.
b 488 mol of calcium carbonate. CaCO
.
c 0.0091 mol of retinoic acid. C20H28O2 * that contains 2.41 x 1024 atoms of chromium, 1.51 x
cl. 6.00 x 10“ s mol of nicotine, C|0H|4N: HP atoms of nickel, and 3.01 X KP atoms of copper?
. .
e 2.50 mol of strontium nitrate Sr( NCh) 2 .
127 The density of liquid water is 0.997 g/ mL at 25 C \
.
f 3.50 x 10 h mol of uranium hexafluoride. UFf, a. Calculate the mass ol 250.0 mL ( about a cupful ) of
116. Calculate the number of molecules or formula units in water.
each of the following amounts. .
b How manv *
moles of water are in 250.0 mL of
.
a 4.27 mol of tungsten!VI ) oxide, WO3 water? Hint: Use the result of ( a ).
.
b 0.003 00 mol of strontium nitrate. SrlNO b .
c Calculate the volume that would be occupied by
.
c 72.5 mol of toluene. ChH CH ,
^
^ 2.000 mol of water at 25 C.
cl. What mass of water is 2.000 mol of water ?
cl. 5.11 x 10 mol of a- tocopherol ( vitamin E ),
C: H5<)0:
^
.
128 An Avogadro's constant ( l mol ) of sugar molecules
.
e 1500 mol of hydrazine, N 2H4 .
has a mass of 342 g but an Avogadro's constant
.
f 0.989 mol of nitrobenzene CJLNCL ( l mol ) of water molecules has a mass of only IS g.
.
117 Calculate the number of molecules or formula units in Explain why there is such a difference between the
each of the following masses. mass of l mol of sugar and the mass of l mol of water.
.
a 285 g of iron( III ) phosphate, FeP04 .
129 Calculate the mass of aluminum that would have the
.
b 0.0084 g of C5H5N same number of atoms as 6.35 g of cadmium.
.
c 85 mg of 2-methvl- 1-propanol, ( Cl U CHCIUOI I 130. A chemist weighs a steel cylinder of compressed ox > -
.^
d. 4.6 x 10 4 g of mercury!II) acetate Hg(C2H3C>2)2 gen, O2, and finds that it has a mass of 1027.8 g. After
.
e 0.0067 g of lithium carbonate, IJ2CO3 some of the oxygen is used in an experiment, the
.
118 Calculate the mass of each of the following quantities . cylinder has a mass of 1023.2 g. How many moles of
.
a 8.39 x l(p molecules of fluorine, P2 oxygen gas are used in the experiment ?
.
b 6.82 x HP formula units of beryllium sulfate. .
131 Suppose that you could decompose 0.250 mol of Ag:S
BeS04 into its elements.
.
c 7.004 x 1 (P molecules of chloroform, CHCI3 .
a How many moles of silver would you have ? How
.
d 31 billion formula units of chromium!Ill ) formate. many moles of sulfur would you have?
Cr(CHO:)3 b. How many moles of Ag2S are there in 38.8 g of
. .
e 6.3 x 10ls molecules of nitric acid HN04 Ag2S? How many moles of silver and sulfur would
.
f 8.37 x l(p molecules of freon 114. C2CI2F.4 be produced from this amount of Ag^ S?
.
119 Precious metals are commonly measured in troy .
c Calculate the masses of silver and sulfur produced
ounces. A troy ounce is equivalent lo 31.1 g. How .
in ( b)

APPENDIX D 887
 Percentage Composition: Chap. 7, u. oxygen in 4.00 g of manganese dioxide, MnOi
h. aluminum in 50.0 metric tons of aluminum oxide,
Sec . 3
Al204
132. Determine the percentage composition of each of the c. silver in 325 g silver cyanide. AgCN
following compounds. d. gold in 0.780 g of gold( III ) selenide. Au^Se
e. selenium in 683 g sodium selenite . Na 2 Se 04
^
a. sodium oxalate. Na 2CN04
h. ethanol. C2H5OH f. chlorine in 5.0 x 104 e of 1.1-dichloropropane,
c. aluminum oxide, AUO3 CHCI2CH2CH3
<1. potassium sulfate. K 2S04 140. Calculate the percentage of water in each of the fol -
133. Suppose that a laboratory analysis of white powder lowing hydrates.
showed 42.59% Na . 12.02 % C, and 44.99 % oxygen. a. strontium chloride hexahvdrate . SrCl2 # 6H20
Would you report that the compound is sodium oxalate 1). zinc sulfate heptahydrate. ZnS04*7H20
or sodium carbonate ? ( Use 43.38 % Na , 11.33 % C. and c. calcium tluorophosphate dihvdrate. CaFPO I-UO
45.29% O for sodium carbonate , and 34.31 % Na. ^
d. beryllium nitrate trihydrate , Be ( NO 02 # 3 H 2O
17.93 % C. and 47.76 % O for sodium oxalate. ) 141. Calculate the percentage of the given element in each
134. Calculate the mass of the given element in each of the of the following hydrates. You must first determine
following compounds. the formulas of the hydrates.
a. bromine in 50.0 g potassium bromide. KBr a. nickel in nickel( Il ) acetate tetrahydrate
h. chromium in 1.00 kg sodium dichromate, Na 2Cr 207 b. chromium in sodium chromate tetrahydrate
e. nitrogen in 85.0 me of the amino acid lysine. c. cerium in cerium( IV ) sulfate tetrahydrate
CftH|4N202 142. Cinnabar is a mineral that is mined in order to pro -
cl. cobalt in 2.84 g cobalt ( ll ) acetate, Co( C;lU02 ) 2
duce mercury. Cinnabar is mercury( ll ) sulfide. HgS.
Hydrates What mass of mercury can be obtained from 50.0 kg
135. Calculate the percentage of water in each of the follow -
of cinnabar?
ing hydrates. 143. The minerals malachite, Cu2 ( OI I ) 2C04 . and chalcopy-
a. sodium carbonate decahydrate, Na 2CO 4 * l 0H 2 O rite, CuFeS2 , can be mined to obtain copper metal.
h. nickel ( II ) iodide hexahvdrate. NiI 2 »6H20 I low much copper could be obtained from l .00 X
c. ammonium hexacyanoferrate( Ill ) trihydrate 10 ' kg of each? Which of the two has the greater cop-
( commonlv called ammonium ferrievanide ), per content ?
( NH4 ):Fe(CN )6 *3H20
144. Calculate the percentage of the given element in each
cl. aluminum bromide hexahvdrate
of the following hydrates.
Mixed Review a. vanadium in vanadium oxysulfate dihvdrate .
136. Write formulas lor the following compounds and deter- -
V0S04 2H20
h. tin in potassium stannate trihydrate. K Sn 04* 3IT 0
mine the percentage composition of each.
a. nitric acid c. chlorine in calcium chlorate dihvdrate,
h. ammonia CaCICV 2H:0
c. mercury( ll ) sulfate 145. Heating copper sulfate pentahydrate will evaporate
d. anlimony( V ) fluoride the water from the crystals, leaving anhydrous copper
137. Calculate the percentage composition ol the following sulfate, a white powder. Anhydrous means “ without
compounds. water. " What mass of anhydrous C11SO4 would be pro -
a. lithium bromide. l iBr. duced by heating 500.0 g of CUS0J * 5 H 20?
b. anthracene. C|41 l | < > 146. Silver metal may be precipitated from a solution of sil -
c. ammonium nitrate, NI 14N( ) 4 ver nitrate by placing a copper strip into the solution.
cl. nitrous acid. HN02 What mass of AgNO would you dissolve in water in
e. silver sulfide. Ag2S order to get 1.00 g of^silver ?
I. iron! 11 ) thiocyanate, Fe( SCN ) 2
g. lithium acetate 147. A sample of Ag2 S has a mass of 62.4 g. What mass of
h. nickeK 11 ) formate each element could be obtained by decomposing this
sample ?
138. Calculate the percentage of the given element in each
of the following compounds. 148. A quantity of epsom salts, magnesium sulfate heptahy -
a. nitrogen in urea. NH2CONH2 drate. MgS04*7H20. is heated until all the water is
b. sulfur in sulfuryl chloride, SQ 2 C12 driven off. The sample loses 11.8 g in the process.
c. thallium in thallium! I I I ) oxide. TBO3 What was the mass of the original sample ?
cl. oxygen in potassium chlorate. KCIO3 149. The process of manufacturing sulfuric acid begins with
e. bromine in calcium bromide. CaBr2 the burning of sulfur. What mass of sulfur would have
f. tin in tint IV ) oxide. Sn02 to be burned in order to produce 1.00 ke of H1SO4 ?
139. Calculate the mass of the given element in each of the Assume that all of the sulfur ends up in the sulfuric
following quantities. acid.

888 APPENDIX D
 Empirical Formulas: Chap. 7, Sec. 4 b. a 0.470 g sample contains 0.144 g of manganese,
0.074 g of nitrogen, and 0.252 g of oxygen
.
150 Determine the empirical formula for compounds that .
c a 3.880 g sample contains 0.691 g of magnesium.
have the following analyses. 1.824 g of sulfur, and 1.365 g of oxygen
a. 28.4 % copper, 71.6% bromine .
cl. a 46,25 g sample contains 14.77 g of potassium
.
h 39.0% potassium. 12.0% carbon. 1.01 % hydrogen, 9.06 g of oxygen, and 22.42 g of tin

.
and 47.9 % oxygen
c 77.3 % silver, 7.4 % phosphorus. 15.3 % oxygen
.
156 Determine the empirical formula for compounds that
have the following analyses:
.
cl 0.57% hydrogen. 72.1% iodine. 27.3 % oxygen . ’
a 60.9 % As and 39.1 % S
151. Determine the simplest formula for compounds that .
b 76.89% Re and 23.12 % O
have the following analyses. The data may not be exact, .
c 5.04 % H, 35.00% N, and 59.96 % O
a. 36.2 % aluminum and 63.8% sulfur . .
d. 24.3 % Fe 33.9% Cr and 41.8% O
I). 93.5 % niobium and 6.50% oxygen .
e 54.03% C. 37.81 % N, and 8.16 % H
.
c 57.6 % strontium, 13.8 % phosphorus, and 28.6% . .
f 55.81 % C. 3.90% H 29.43% F. and 10.85 % N
oxygen .
157 Determine the molecular formulas for compounds
.
cl 28.5 % iron. 48.6% oxygen, and 22.9% sulfur having the following empirical formulas and molar
152. Determine the molecular formula of each of the fol - masses.
lowing unknown substances. a. C2 H4S: experimental molar mass 179
a. empirical formula CTD .
b C 7H4O; experimental molar mass 176
experimental molar mass 28 g/mol .
c CNHJOTJ experimental molar mass 119
.
b empirical formula B ?Hs .
cl Cd DO. experimental molar mass 254
experimental molar mass 54 g/mol .
158 Use the experimental molar mass to determine the
c. empirical formula OHCl molecular formula for compounds having the follow -
experimental molar mass 179 g/ mol ing analyses.
.
d empirical formula C(,HhO .
1» 41.39% carbon, 3.47 % hydrogen, and 55.14 % oxy -
experimental molar mass 290 g/mol gen: experimental molar mass 116.07
e. empirical formula C3H2O . .
b 54.53 % carbon 9.15 % hydrogen, and 36.32 % oxy -
experimental molar mass 216 g/mol gen: experimental molar mass 88
.
c 64.27 % carbon. 7.19% hydrogen, and 28.54 % oxy -
gen: experimental molar mass 168.19
Mixed Review .
159 A 0.400 g sample of a white powder contains 0.141 g
.
153 Determine the empirical formula for compounds that of potassium. 0.115 g of sulfur, and 0.144 g of oxygen .
have the following analyses. What is the empirical formula for the compound ?
.
a 66.0% barium and 34.0% chlorine
.
I) 80.38% bismuth. 18.46% oxygen, and 1.16% hydrogen 160. A 10.64 g sample of a lead compound is analyzed and
.
c 12.67 % aluminum. 19.73 % nitrogen, and 67.60% found to be made up of 9.65 g of lead and 0.99 g of
oxygen. Determine the empirical formula for this com -
oxygen
. .
d 35.64 % zinc, 26.18 % carbon 34.88% oxygen, and pound.
3.30% hydrogen .
161 A 2.65 g sample of a salmon-colored pow der contains
.
t* 2.8% hydrogen, 9.8% nitrogen, 20.5 % nickel, 0.70 g of chromium. 0.65 g of sulfur, and 1.30 g of oxy -
44.5 % oxygen, and 22.4 % sulfur .
gen. The molar mass is 392.2 What is the formula of
.
f 8.09% carbon. 0.34 % hydrogen, 10.78 % oxygen, the compound ?
and 80.78% bromine .
162 Ninhydrin is a compound that reacts with amino acids
154. Sometimes, instead of percentage composition, you .
and proteins to produce a dark -colored complex It is
.
will have the composition of a sample by mass Using used by forensic chemists and detectives to see finger -
the actual mass of the sample, determine the empiri - prints that might otherwise be invisible. Ninhydrin s
cal formula for compounds that have the following .
composition is 60.68% carbon 3.40% hydrogen, and
analyses. 35.92 % oxygen. What is the empirical formula for nin-
.
a a 0.858 g sample of an unknown substance is com
- hydrin?
posed of 0.537 g of copper and 0.321 g of fluorine .
163 Histamine is a substance that is released by cells in
b. a 13.07 g sample of an unknown substance is com- response to injury, infection, stings, and materials that
.
posed of 9.48 g of barium 1.66 g of carbon, and cause allergic responses, such as pollen. Histamine
1.93 g of nitrogen causes dilation of blood vessels and swelling due to
.
c a 0.025 g sample of an unknown substance is com - accumulation of fluid in the tissues. People sometimes
.
posed of 0.0091 g manganese 0.0106 g oxygen, and take histamine drugs to counteract the effects of
0.0053 g sulfur histamine. A sample of histamine having a mass of
.
155 Determine the empirical formula for compounds that .
385 mg is composed of 208 mg of carbon 31 mg of
have the following analyses . hydrogen, and 146 mg of nitrogen. The molar mass of
.
a a 0.0082 g sample contains 0.0015 g of nickel and .
histamine is 111 g/mol What is the molecular formula
0.( MI67 g of iodine for histamine ?

APPENDIX 0 889
164. You analyze two substances in the laboratory and dis- 172. Hydrogen is generated by passing hot steam over iron,
cover that each has the empirical formula ( I FO. You .
which oxidizes to form Fe 304 in the following equa -
can easily see that thc \ are different substances tion:
because one is a liquid with a sharp, biting odor and 3Fe( v ) + 4H20( g ) — 4H2( g) + Fe 304( .v )
the other is an odorless, crystalline solid. I low can you *
account for the fact that both have the same empirical
.
a If 625 g of Fe304 is produced in the reaction, how
many moles of hydrogen are produced at the
formula?
same time?
.
Ii How many moles of iron would be needed to gener -
ate 27 g of hydrogen?

Stoichiometry: Chap. 9, Sec. 1-2

.
173 Calculate the mass of silver bromide produced from
22.5 g of silver nitrate in the following reaction:
.
165 How mans moles of sodium will react with water to 2 AgN03( <w/ ) + MgBri( tf </ ) » — -
2 AgBr (.v ) Mg( NO;):( < / < / )
produce 4.0 mol of hydrogen in the following reac -
tion ? .
174 What mass of acetylene. CMC. will be produced from
2Na ( .v ) 2H:0( / ) -4 2NaOH( aq ) -f H:( g ) the reaction of 90, g of calcium carbide. ( aC\ with
water in the following reaction?
.
166 How main moles of lithium chloride will be formed
CaC':( .v ) + 2H:0( / ) -> C2H2( g) + Ca( OH ) 2( j?)
by the reaction of chlorine with 0.046 mol of lithium
bromide in the following reaction ? .
175 Chlorine gas can be produced in the laboratory by
2 LiBr ( m/ ) + CF( g) —> 2LiCl(r/ t/ ) 4- Br2( / ) adding concentrated hydrochloric acid to
nianganese ( IV ) oxide in the following
.
167 Aluminum will react with sulfuric acid in the following reaction:
reaction.
2 AI( s ) + 3H:S04( / ) -> AI2( SOM a q ) + 3H2( g) <
Mn02 5 ) 4- 4HCl( fl</ ) ->
MnCF(tf </ ) 4- 2HiO( / ) + Cli( g)
.
a How many moles of H2S04 will react w ith 18 mol .
a Calculate the mass of Mn02 needed to produce

.
A I? 25.0 g of CF .
b How many moles of each product will be produced? .
b What mass of MnCF is produced when 0.091 g of
168 . Propane burns in excess oxygen according to the fol - CF is generated?
lowing reaction.
-
Cdts 502 -4 3C02 41 HO
a. I low many moles each of C02 and IFO are formed
Mixed Review
from 3.85 mol of propane? .
176 I low many moles of ammonium sulfate can be made
.
h If 0.647 mol of oxygen are used in the burning of from the reaction of 30.0 mol of NIF with IFS04 accord-
ing to the following equation:
propane, how many moles each of C02 and HO
are produced? Ilow many moles of CO Is are con- 2NH , 4- H:SQ 4 -4 ( NH4 )2S04
sumed? .
177 In a very violent reaction called a thermite reaction,
169 . Phosphorus burns in air to produce a phosphorus aluminum metal reacts with iron( IIl) oxide to form
iron metal and aluminum oxide according to the fol -
oxide in the following reaction:
4P( .s ) 4- 502( g) - P4Oio( x )
lowing equation:
* 2Fe 4- AFO3
.
a What mass of phosphorus will be needed to pro-
Fe203 4- 2 A 1
,
duce 3.25 mol of P40 y? .
a What mass of Al w ill react with 150 g of Fe 203 ?
.
.
h Ii 0.489 mol of phosphorus burns, what mass of b If 0.905 mol AFO3 is produced in the reaction, what
mass of Fe is produced?
oxygen is used? What mass ot P 4 Ojn is produced?
170 . Hydrogen peroxide breaks down, releasing oxygen, in
.
c How many moles of Fe->03 will react with 99.0 c of
A I?
the following reaction.
2H:0:( aq ) -> 2 H:0( / ) 4- 0:( g )
. .
178 The reaction N2( g) 4- 3H2( g) -4 2NIF( e ) is used to
produce ammonia commercially. If 1.40 g of N2 are
.
a What mass of oxygen is produced when 1.840 mol used in the reaction, how many grams of I F will be
of H202 decompose? needed?
.
h What mass of water is produced when 5.0 mol 02 is
.
179 What mass of sulfuric acid. IF$04 , is required to react
produced by this reaction ?
with 1.27 g of potassium hydroxide, KOH ? The prod-
171 . Sodium carbonate reacts with nitric acid according to ucts of this reaction are potassium sulfate and water.
the following equation:
180. Ammonium hydrogen phosphate. ( NH4)2HP04. a
-
Na:COd v ) 2HN03 -> 2NaN03 + C02 4- H:0 common fertilizer: is made from reacting phosphoric
.
a How many moles of Na2C03 are required to pro- acid, H 3P04. w i t h ammonia.
duce 100.0 g of NaNOy? .
a Write the equation for this reaction.
h. If 7.50 g of Na2C03 reacts, how many moles of CCF .
b If 10.00 g of ammonia react , how many moles o!
are produced? fertilizer w ill be produced?

890 APPENDIX D
 c. What mass of ammonia will react with 2800 kg of water with few trace pollutants. If 95.0 g of IHO are
H 3 PO4 ? produced during the combustion of ethanol, how
181. I he following reaction shows the synthesis of zinc cit - many grams of ethanol were present at the beginning
rate. a ingredient in toothpaste, from zinc carbonate of the reaction ?
and citric acid: 189. Sulfur dioxide is one of the major contributors to acid
3ZnCO,( r ) 4 2ChHK07( fl < / ) -> rain. Sulfur dioxide can react with oxygen and water in
,<
Zn C*H5O7)2(<*0 ) + 3H20( / ) 3C02(#)
a. I low many moles of ZnCCh and C6 Hs07 are
required to produce 30.0 mol of Zn ( C \, H 5O7 ):?
- the atmosphere to form sulfuric acid , as shown in the
following equation:
2 H:Q ( / ) 4 0:( g ) 4 2SO:( g ) 2 H 2S04( </ </ )
*
b. What quantities, in kilograms, of H 20 and < 0: are If 50. 1 g of sulfur dioxide from pollutants reacts with
(
produced by the reaction of 500. mol of citric acid ? .
water and oxygen found in the air how many grams of
182. Methyl butanoate, an oily substance with a strong sulfuric acid can be produced ? How many grams of
fruity fragrance can be made by reacting butanoic acid oxygen are used in the process?
with methanol according to the following equation: 190. When heated , sodium bicarbonate. NaHC03. decom -
( MI 7COOH + CH OH -> C;H , 7COOCHI 4- H:0 poses into sodium carbonate. Na 2C04 . water, and car -
.
a What mass of methyl butanoate is produced from bon dioxide. If 5.00 g of NaHC03 decomposes, what is
the mass of the carbon dioxide produced ?
the reaction of 52.5 g of butanoic acid ?
b. In order to purify methyl butanoate. water must be .
191. A reaction between hydrazine N 2 H 4 . and dinitrogen
removed. What mass of water is produced from the tetroxide. N:04 . has been used to launch rockets into
reaction of 5800. g of methanol ? space. The reaction produces nitrogen gas and water
183. Ammonium nitrate decomposes to yield nitrogen gas. vapor.
water, and oxygen gas in the following reaction: .
a Write a balanced chemical equation for this reaction ,
h. What is the mole ratio of N:04 to N 2?
2 NH 4 N03 -> 2 N: 4 02 4 4H20
.
a How many moles of nitrogen gas are produced
.
e How many moles of N: will be produced if
20 000 mol of N > H 4 are used by a rocket ?
when 36.0 g of NH 4 NO3 reacts? d. I low many grams of I HO are made when 450. kg of
.
h II 7.35 mol of ITO are produced in this reaction, N 204 are consumed ?
what mass of NH 4 N 03 reacted ?
184. Lead ( II ) nitrate reacts with potassium iodide to pro-
.
192 Joseph Priestley is credited with the discovery of oxy -
gen . He produced 02 by heating mercury ( II ) oxide.
duce lead ( II ) iodide and potassium nitrate. If 1.23 mg
HgO, to decompose it into its elements. How many
of lead nitrate are consumed , w hat is the mass of the
moles of oxygen could Priestley have produced if he
potassium nitrate produced ?
185. A car battery produces electrical energy with the fol -
.
had decomposed 517.S4 g of mercury oxide?
lowing chemical reaction: 193. Iron ( III ) chloride. FeCI 3. can be made by the reaction
Pb( .v ) 4 Pb02( s ) 4 2 HiSO4 ( < w/ ) >—
2 PbSO40 ) f 2 II > ( ) ( / )
of iron with chlorine gas. How much iron , in grams,
will be needed to completely react with 58.0 g of CL ?
194. Sodium sulfide and cadmium nitrate undergo a
If the battery loses 0.34 kg of lead in this reaction ,
double-displacement reaction as shown by the follow -
how many moles of lead ( U ) sulfate are produced ?
ing equation:
186. In a space shuttle , the 0O2 that the crew exhales is ,
removed from the air by a reaction within canisters of
Na:S 4 Cd ( N 03)2 -4 2 NaNO 4 CdS
lithium hydroxide . On average, each astronaut exhales What is the mass, in milligrams of cadmium sulfide
,

about 20.0 mid of CO ? daily. What mass of water will that can be made from 5.00 mg of sodium sulfide?
be produced when this amount reacts with LiOH ? The 195. Potassium permanganate and glycerin react explo-
other product of the reaction is Li 2C03. sively according to the following equation:
187. Water is sometimes removed from the products of a 14 k \ lnt > 4 4 4 CTU ( OH ) , ->
reaction b \ placing them in a closed container with
excess P4Oj0. Water is absorbed by the following reac-
-
7 K 2C03 7 Mn:Q 4 ^ 5CQ2 4 16 ITO
a. How many moles of carbon dioxide can be pro-
tion: duced from 4.44 mol of KMn 04?
,
P40 „ 4 6H20 4H 3P04 .
h If 5.21 g of H ;C ) are produced , how many moles of
11. What mass of water can be absorbed bv LOO x .
glycerin , CTMOHh were used ?
,
102 g of P40 o ? .
c If 3.39 mol of potassium carbonate are made , how
h. If the P4O|0 in the container absorbs 0.614 mol of many grams of manganese( IU ) oxide are also
water, what mass of 1TPQ4 is produced ? made?
.
c If the mass of the container of P4 Ojo increases from .
cl How many grams of glycerin w ill be needed to react
56.64 g to 63.70 g. how many moles of water are with 50.0 g of KMn04? How mans grams of C02
absorbed ? will be produced in the same reaction ?
188. Ethanol. CTHOH . is considered a clean fuel because 196. Calcium carbonate found in limestone and marble
it burns in oxygen to produce carbon dioxide and reacts with hydrochloric acid to form calcium chloride.

APPENDIX D 891
 carbon dioxide , and water according to the following If 1.72 mol of ZnS is heated in the presence of
equation: 3.04 mol of O2 , which reactant will be used up?
CaC03( j) 4 2HC\ ( aq ) ->
- Balance the equation first .
CaCI2( rif/ ) 4- C02 ( g ) 4- H20( / ) 203. Use the following equation lor the oxidation of alu-
‘

a. What mass of HCI will be needed to produce 5.00 x minum in the following problems:
10- kg of CaCl2? 4 A 1 + 302 2AI203
h. What mass of C02 could be produced from the a. Which reactant is limiting if 0.32 mol Al and
reaction of 750 g of CaC03? 0.26 mol 02 are available ?
197. The fuel used to power the booster rockets on the I). How many moles of AI 7 O3 are formed from the
space shuttle is a mixture of aluminum metal and reaction of 6.38 x 10 ' mol of 02 and 0.15 x
ammonium perchlorate. The following balanced equa- 10 ' mol of AI?
tion represents the reaction of these two ingredients: c. If 3.17 g of Al and 2.55 g of 02 are available, which
reactant is limiting?
3 A 1( A ) 4- 3NH4CI04( 5) ->
Al203( 5 ) + AICl3( g) 4- 3NO( g) 4- 6H20( g) 204. In the production of copper from ore containing cop-
a. If 1.50 x 10s g of Al react , what mass of NH4CIO4,
per ( ll ) sulfide, the ore is first roasted to change it to
the oxide according to the following equation:
in grams, is required?
b. If aluminum reacts with 620 kg of NH4 CIO4 , what 2CuS + 302 2CuO 2SO:
mass of nitrogen monoxide is produced? a. If 100 g of CuS and 56 g of 02 are available, which
198. Phosphoric acid is typically produced by the action of reactant is limiting?
sulfuric acid on rock that has a high content of calcium b. What mass of CuO can be formed from the reaction
phosphate according to the following equation: of 18.7 g of CuS and 12.0 g of 02?
3H 2 S04 4- Ca3( P04)2 4- 6H20 205. A reaction such as the one shown here is often used to
-
3[CaS04 2H20 ] 4- 2H3PO4 demonstrate a single- displacement reaction:
a. If 2.50 x 1 T kg of H2S04 react , how many moles of
( 3CuS04(tfr/ ) + 2Fe ( .v ) —> 3 Cu(.v ) + Fe2( S04)3( aq )
H3PO4 can be made? If you place 0.092 mol of iron filings in a solution con -
b. What mass of calcium sulfate dihydrate is produced taining 0.158 mol of CuSOj. what is the limiting re-
by the reaction of 400. kg of calcium phosphate? actant ? How many moles of Cu will be formed ?
c. If the rock being used contains 78.8% Ca3( P04 )2.
206. In the reaction BaCOi + 2HN03 —> Ba ( N03)2 +
how many metric tons of H3PO 4 can be produced
C02 + H20, what mass of Ba(N03)2 can be formed
from 68 metric tons of rock ?
by combining 55 g BaCOj and 26 g HNO3?
199. Rusting of iron occurs in the presence of moisture
207. Bromine replaces iodine in magnesium iodide by the
according to the following equation:
following process:
4 Fe( .v ) 4 3C>2( g)
-
2Fe203(.v )
Mgl2 4- Br 2 —> MgBr2 4- I 2
Suppose that 3.19% of a heap of steel scrap with a
mass of 1650 kg rusts in a year. What mass will the a. Which is the excess reactant when 560 g of Mgl2
heap have after one year of rusting? and 360 g of Br2 react , and what mass remains?
b. What mass of I 2 is formed in the same process?
208. Nickel replaces silver from silver nitrate in solution
Limiting Reactants: Chap. 9, Sec . 3 according to the following equation:
200. Aluminum oxidi/es according to the following equation: 2 AgN03 4- Ni —> 2 Ag 4- Ni( N03)2
4 A 1 4- 301 2 A120 , a. If you have 22.0 g of Ni and 1 12 g of AgN03 which f

reactant is in excess?
Powdered Al 0.048 mol is placed into a container
( )
I). What mass of nickel( II ) nitrate would be produced
containing 0.030 mol 02 . What is the limiting given the quantities above?
reactant ?
209. Carbon disulfide, CS2 , is an important industrial sub-
201. A process by which zirconium metal can be produced
stance. Its fumes can burn explosively in air to form
from the mineral zirconium! IV ) orthosilicate . ZrSiC)4 .
sulfur dioxide and carbon dioxide:
starts bv reacting it with chlorine gas to form zirconi-
um! IV ) chloride: CS2( g) + 02( K ) -> S02( g) + C02(g)
ZrSi04 4- 2CI2 - ZrCI4 4- Si02 4- C)2 If 1.60 mol of C’S2 burns with 5.60 mol of 02 . how
* many moles of the excess reactant will still be present
What mass of ZrCI4 can be produced if 862 g of
when the reaction is over?
ZrSi04 and 950. g of Cl2 are available ? You must first
determine the limiting reactant. 210. Although poisonous, mercury compounds were once
used to kill bacteria in wounds and on the skin. One was
Mixed Review called “ammoniated mercury and is made from mer-
"

202. I Icating zinc sulfide in the presence of oxygen yields cury( ll ) chloride according to the following equation:
the following: HgCI2( < / r/ ) 4- 2NH3( </</ ) —»
ZnS 4- .
0- -> ZnO 4- SO - . Hg( NH2 )CI (.v ) + NH4CI( aq )

892 APPENDIX D
 a. What mass of Hg( NH2 )Cl could he produced from a. Given 27.5 g of TbF,and 6.96 g of Ca. how many
0.91 g of HgCl2 assuming plenty of ammonia is grams of terbium could be produced?
available? b. How many grams of the excess reactant is left over?
.
b What mass of Hg(NH2 )Cl could be produced from
,
0.91 g of HgCI2 and 0.15 g of NH in solution ?
.
211 Aluminum chips arc sometimes added to sodium
hydroxide-based drain cleaners because they react to Percentage Yield: Chap. 9, Sec . 3
generate hydrogen gas which bubbles and helps loosen
material in the drain. The equation follows: 218. Calculate the percentage yield in each of the following
Al( .v ) + NaOH( aq ) + H:0( / ) NaAlO2( aq ) + H2( ) cases .
.
a Balance the equation . * .
a theoretical yield is 50.0 a of product; actual yield is
41.9 g
b. How many moles of Hi can be generated from .
b theoretical y ield is 290 ke of product: actual y ield is
0.57 mol Al and 0.37 mol NaOII in excess water ? 270 kg
.
c Which reactant should be limiting in order for the .
c theoretical yield is 6.05 x 104 kg of product; actual
mixture to be most effective as a drain cleaner ? yield is 4.18 X 104 kg
Explain your choice. .
d theoretical yield is 0.00192 g of product: actual yield
.
212 Copper is changed to copper ( II ) ions bv nitric acid is 0.00089 g
according to the following equation; .
219 In the commercial production of the element arsenic,
4HN03 + Cu -> CU(N03 ): + 2NO: 4- 2H:0 arsenic( III ) oxide is healed with carbon, which
. ,
a How many moles each of UNO and Cu must react
reduces the oxide to the metal according to the follow-

—
ing equation:
.
in order to produce 0.0845 mol of NOV?
,
b If 5.94 g of Cu and 23.23 g of HNO are combined,
which reactant is in excess?
2 As:03 + 3C
.
3C02 4 As
-
a. If S.87 g of As203 is used in the reaction and 5.33 g
of As is produced, what is the percentage yield?
.
213 One industrial process for producing nitric acid begins
h. If 67 g of carbon is used up in a different reaction
with the following reaction:
,
4NH + 502 -4 4NO 6H O
and 425 g of As is produced, calculate the percent -
age yield of this reaction .
. ,
a If 2.90 mol NH and 3.75 mol 02 are available, how Mixed Review
many moles of each product are formed?
.
b Which reactant is limiting if 4.20 x I 04 g of NH; 220. Ethyl acetate is a syvcet -snielling solvent used in var -
nishes and fingernail-polish remover. It is produced
and 1.31 x 10s g of 02 are available ?
.
c What mass of NO is formed in the reaction of industrially by heating acetic acid and ethanol together
,
869 kg of NH and 2480 kg 02? in the presence of sulfuric acid, which is added to speed
up the reaction. The ethyl acetate is distilled off as it is
. . .
214 Acetaldehyde CH3CHO is manufactured by the reac -
tion of ethanol with copper(II) oxide according to the
formed. The equation for the process is as follows:
acetic at id ethanol
following equation: H' SOx
CH3COOH + CH3CH 2OH
CH3CH 2OH 4- CuO -> CH3CHO + II20 + Cu
What mass of acetaldehyde can be produced by the
ethyl acetate
CH3COOCH2CH 4- H2O ,
reaction between 620 g of ethanol and 1020 g of CuO? Determine the percentage yield in the following cases .
What mass of w hich reactant will be left over ? .
a 68.3 g ol ethyl acetate should be produced but only

.
215 Hydrogen bromide can be produced by a reaction 43.9 g is recovered.
.
b 0.0419 mol of ethyl acetate is produced but

SO .
among bromine, sulfur dioxide, and water as follows:
Br 2 4- H20 -> 2HBr 4- H 2 S04
If 250 g of S02 and 650 g of Br2 react in the presence
.
0.0722 mol is expected ( Hint: Percentage yield can
also be calculated by dividing the actual yield in
moles by the theoretical yield in moles. )
of excess water, w hat mass of HBr will be formed? .
c 4.29 mol of ethanol is reacted with excess acetic
acid, but only 2.98 mol of ethyl acetate is produced.
.
216 Sulfur dioxide can be produced in the laboratory by
.
cl A mixture of 0.58 mol ethanol and 0.82 mol acetic
the reaction of hydrochloric acid and a sulfite salt such
acid is reacted and 0.46 mol ethyl acetate is pro -
as sodium sulfite:
duced. ( Hint : What is the limiting reactant ? )
Na2S03 4- 2HCI -> 2NaCI 4- S02 4- H 20
221. Assume the following hypothetical reaction takes
What mass of S02 can be made from 25.0 g of \ a 2SO, place:

.
and 22.0 g of HC1?
217 The rare -earth metal terbium is produced from ter -
2 A 4- 7B 4C 3D -
C alculate the percentage yield in each of the following
bium ( III ) fluoride and calcium metal by the following cases.
single-displacement reaction: .
u The reaction of 0.0251 mol of A produces
,
2TbF - 4- 3Ca 3CaF: + 2Tb 0.0349 mol of C.

APPENDIX D 893
 .
h The reaction of 1.19 mol of A produces 1.41 mol of I ). . .
226 In the past , hydrogen chloride HCI. was made using
.
c The reaction of ISM mol of B produces 39 mol of D. -
the salt cake method as shown in the following equa -
d. The reaction ot 35( H ) mol of B produces 17( H ) mol tion :
of C 2 NaCl (s) + H:SOA( uq ) -> Na 2S04(.s ) 4- 2 HCI ( g )
222. Elemental phosphorus can be produced by heating If 30.0 g of NaCl and 0.250 mol of H 2S04 are avail -
calcium phosphate from rocks with silica sand ( Si02 ) able. and 14.6 g of HCI is made, what is the percent -
and carbon in the form of coke. The following reac- age yield ?
tion takes place:
3CaSi 03 4 2 P 4 5CO
227. Cyanide compounds such as sodium cyanide. NaCN .
Ca 3( P04 )2 + 3Si 02 + 5C are especially useful in gold refining because they will
a. If 57 mol of Ca 4( P04 )2 is used and 101 mol of react with gold to form a stable compound that can
CaSiOj is obtained , what is the percentage yield ? then be separated and broken down to retrieve the
h. Determine the percentage yield obtained if gold . Ore containing only small quantities of gold can
1280 mol of carbon is consumed and 622 mol of be used in this form of "chemical mining.’ The equa - *

CaSiO; is produced. tion for the reaction follows:

.
c The engineer in charge of this process expects a 4 Au + 8NaCN 4 2 HT ) + ( ),
yield of 81.5 %. If 1.4 X 10s mol of Ca 3( P04 ): is 4 NaAu ( CN ): + 4 NaOH
used , how many moles of phosphorus w ill be pro-
duced ?
.
a What percentage yield is obtained if 410 g of gold
produces 540 g of NaAu ( CN ) 2?
.
223 Tungsten ( W ) can be produced from its oxide by h. Assuming a 79.6 % yield in the conversion of gold
reacting the oxide with hydrogen at a high tempera -
lure according to the following equation :
.
to NaAu ( CN )2 w hat mass of gold would produce
1.00 kg of NaAu ( CN )2?
WO} 4- 3H; W 4 31 IT ) .
c Given the conditions in ( b ). what mass of gold ore
.
a What is the percentage yield if 56.9 g of WO3 yields that is ( ).( H ) 1 % gold would be needed to produce
1.00 kg of NaAu ( CN ):?
41.4 g of tungsten ?
1 ». How many moles of tungsten will be produced from 228. Diiodine pentoxide is useful in devices such as respira -
3.72 g of WO3 if the yield is 92.0% ? tors because it reacts with the dangerous gas carbon
.
c A chemist carries out this reaction and obtains monoxide, CO, to produce relatively harmless C02
11.4 g of tungsten . If the percentage yield is 89.4 %. according to the following equation:
what mass of WO3 was used ? I 205 + 5CO -> I 2 + 5C02
224. C arbon tetrachloride. CCI 4 . is a solvent that was once .
a In testing a respirator, 2.00 g of carbon monoxide gas
used in large quantities in dry cleaning. Because it is a
dense liquid that does not burn, it was also used in fire
is passed through diiodine pentoxide. Upon analyz -
ing the results, it is found that 3.17 g of I 2 was pro-
extinguishers. Unfortunately, its use was discontinued duced. Calculate the percentage yield of the reaction.
because it was found to be a carcinogen. It was manu - I >. Assuming that the yield in ( a ) resulted because
factured by the following reaction: some of the CO did not react , calculate the mass of
CS2 4 302 -4 CCI4 4 S;CI: CO that passed through.
The reaction was economical because the byproduct .
229 Sodium hypochlorite. NaClO. the main ingredient in
disulfur dichloride. S202. could be used by industry household bleach , is produced by bubbling chlorine
in the manufacture of rubber products and other gas through a strong lye ( sodium hydroxide, NaOl I )
materials. solution . The following equation shows the reaction
.
a What is the percentage yield of CCI4 if 719 kg is that occurs:
produced from the reaction of 410. kg of CS2? 2 NaOH ( a t / ) 4- Cl 2( g ) ->
I ). If 67.5 g of Cl 2 are used in the reaction and 39.5 g of NaClO / */ ) 4 NaClO( a t/ ) 4 HT ) ( / )
S2CI 2 is produced , w hat is the percentage yield ?
.
c If the percentage yield of the industrial process is a. What is the percentage yield of the reaction if
83.3% . how many kilograms of CS2 should be react - 1.2 kg of Cl 2 reacts to form 0.90 kg of NaClO?
ed to obtain 5.(JO x 1 ( H ke of CCI 4? How many kilo- h. If a plant operator wants to make 25 metric tons of
grams of S2CI 2 will be produced , assuming the same NaClO per day at a yield of 91.8% , how many met -
yield for that product ? ric tons of chlorine gas must be on hand each day?
225. Nitrogen dioxide. N 02. can be converted to dinitro-
.
c What mass of NaCl is formed per mole of chlorine
gas at a yield of 81.8 % ?
gen pentoxide. N > ( )^. b \ reacting it with ozone, O3. cl. At w hat rate in kg per hour must NaOH be replen -
rhe reaction of NO: takes place according to the fol - ished if the reaction produces 370 kg/ h of NaClO at
lowing equation: a yield of 79.5 % ? Assume that all of the NaOH
2 N 02( g) 4 03( g ) -> NT)*( .v or g ) 4 02( g) reacts to produce this yield.
a. C alculate the percentage yield for a reaction in w hich 230. Magnesium burns in oxygen to form magnesium
0.38 g of N02 reacts and 0.36 g of NT )* is recovered, oxide . However, when magnesium burns in air, which
h. What mass of NT )* will result from the reaction of is only about one- fifth oxygen, side reactions form
6.0 mol of NO» if there is a 61.1 % yield in the reaction ? other products, such as magnesium nitride, MgjNN.

894 APPENDIX D
 .
a Write a balanced equation for the burning ot mag- oxide reacts with the water to form a base that can
nesium in oxygen. neutralize the acid as shown in the following reaction:
b. If enough magnesium burns in air to produce 2.04 g CaO( s ) 4- ICO( / ) - Ca( OH)2( s)
of magnesium oxide but only 1.79 g is obtained,
If 2.67 x 1 ( ): mol of base are needed to neutralize the
what is the percentage yield?
.
c Magnesium will react with pure nitrogen to form
acid in a lake, and the above reaction has a percentage
.
yield of 54.3 % what is the mass, in kilograms, of lime
the nitride. Mg3N2 . Write a balanced equation for
that must be added to the lake?
this reaction.
cl. If 0.097 mol of Mg react with nitrogen and
0.027 mol of Mg3N2 is produced, what is the
percentage yield of the reaction? Gas Laws: Chap. 11, Sec. 2
.
231 Some alcohols can be converted to organic acids bv Boyle 's Law
using sodium dichromate and sulfuric acid. The fol - In each of the following problems, assume that the
lowing equation shows the reaction of 1 -propanol to
propanoic acid: temperature ami molar quantity of gas do not
change.
3CTCCLCCFCOH 4 2Na 07 + 8LCS04 ->
^
3CH 3CH 2COOH + 2CT2(S04)3 + 2Na2S04 + 11H:0 237. Calculate the unknown quantity in each of the follow -
.
a If 0.89 g of l -propanol reacts and 0.88 g of propanoic ing measurements of gases.
acid is produced, what is the percentage yield?
h. A chemist uses this reaction to obtain 1.50 mol of
propanoic acid. The reaction consumes 136 g of
propanol. Calculate the percentage yield, .
a 3.0 aim 25 mL 6.( 1 atm ? mL
.
c Some 1 -propanol of uncertain purity is used in the h. 99.97 kPa 550. mL ? kPa 275 mL
reaction. If 116 g of Na2Cr 207 are consumed in the
reaction and 28.1 g of propanoic acid are produced, .
c 0.89 atm ?L 3.56 atm 20.0 L
what is the percentage yield? .
d ? kPa 800. mL 500. kPa 160. mL
.
232 Acrylonitrile. C;H3N( g ). is an important ingredient in .
e 0.040 atm ?L 250 atm 1.0 X 10 -L
the production of various fibers and plastics .
Acrylonitrile is produced from the following reaction:
CdMg ) + NH3( g) + 02( g) .
C3H3N( g) + H20( g)
.
238 A sample of neon gas occupies a volume of 2.8 l. at
1.8 atm. What will its volume be at 1.2 atm ?
If 850. g of C3Hft is mixed with 300. g of NH3 and .
239 To what pressure would you have to compress 48.0 L
.
unlimited 02 to produce 850. g of acrylonitrile, w hat of oxygen gas at 99.3 kPa in order to reduce its vol -
is the percentage yield? You must first balance the ume to 16.0 L ?
equation.
.
240 A chemist collects 59.0 mL of sulfur dioxide gas on a
. . .
233 Methanol CH3OH is frequently used in race cars as day when the atmospheric pressure is 0.989 atm On .
fuel. It is produced as the sole product of the combina - the next day, the pressure has changed to 0.967 atm.
tion of carbon monoxide gas and hydrogen gas. What will the volume of the S02 gas be on the second
.
a If 430. kg of hydrogen react , what mass of methanol day ?
could be produced ?
h. If 3.12 X 103 kg of methanol are actually produced, .
241 2.2 L of hydrogen at 6.5 atm pressure is used to fill a
what is the percentage yield? balloon at a final pressure of 1.15 atm. What is its final
volume ?
, .
234. The compound. C<1H (>N2 is one of the starting materi -
.
als in the production of nylon It can be prepared from Charles's Law
the following reaction involving adipic acid, Q,L1|O04 :
In each of the following problems, assume that the
<
CVI10O4 / ) + 2NH3(S ) 4 4H2( g) ->
C6HU,N,( / ) + 4H 20 pressure and molar quantity of gas do not change.

What is the percentage yield if 750. g of adipic acid

.
242 Calculate the unknown quantity in each of the follow -
ing measurements of gases:
results in the production of 578 g of ChH|f,N2 ?
.
235 Plants convert carbon dioxide to oxygen during photo-
synthesis according to the follow ing equation: i V2
CO 2 4 ICO -> CftH 206 4- 02
* , .
a 40.0 mL 280. K ? mL 350. k
Balance this equation, and calculate how much oxygen .
I) 0.606 L 300. k 0.404 L ?k
would be produced if 1.37 x 104 g of carbon dioxide
reacts with a percentage yield of 63.4% . .
c ? mL 292 k 250. mL 365 k
.
d 100. mL ?k 125 ml 305 k
. .
236 Lime CaO. is frequently added to streams and lakes
e. 0.0024 L 22 C ?L 14 C
which have been polluted by acid rain. The calcium

APPENDIX 0 895
243. A balloon full of air has a volume of 2.75 L at a tem - has displaced a volume of 15 mL of water is 207.33 kPa .
perature of 18 C. What is the balloon’s volume at What is the pressure of the I LS gas collected?
45° C?
In each of the following problems , assume that the
244. A sample of argon has a volume of 0.43 mL at 24 C.
At what temperature in degrees Celsius will it have a molar quantity of gas does not change.
volume of 0.57 mL? 251 . Some hydrogen is collected over water at 10 C and
105.5 kPa pressure . The total volume of the sample
Gay - Lussac 's Law was 1.93 L . Calculate the volume of the hydrogen cor-
In each of the billowing problems, assume that the rected to STP.
volume and molar quantity of gas do not change. 252. One student carries out a reaction that gives off
methane gas and obtains a total volume by water dis-
245. Calculate the unknown quantity in each of the follow - placement of 338 mL at a temperature of 19 C and a
ing measurements of gases. pressure of 0.9566 atm . Another student does the
identical experiment on another day at a temperature
of 26 C and a pressure of 0.989 atm . Which student
.
a 1.50 atm 273 K ? atm 410 K
collected more CH4?
1». 0.208 atm 3( H ). K 0.156 atm ?K Mixed Review
.
c ? kPa 52 C 99.7 kPa 77°C hi each of the following problems, assume ( hat the
d. 5.20 atm •> £ *
4.16 atm - 13° C* molar quantity of gas does not change.
.
e 8.33 x K ) - 4 - 84 C 3.92 x 10 3 ? °C 253. Calculate the unknown quantity in each of the follow-
atm atm ing measurements of gases.

246. A cylinder of compressed gas has a pressure of 4.882

atm on one day. The next da \ , the same cylinder of gas
a. 127.3 kPa 796 cm ' ? kPa 965 cm 3
has a pressure of 4.690 atm . and its temperature is
8 C. What was the temperature on the previous day in .
b 7.1 x 102 atm ? mL 9.6 x 10 1 atm 3.7 x I 03 mL
C? c. ? kPa 1.77 L 30.79 k Pa 2.44 L
247. A mylar balloon is filled with helium gas to a pressure d. 114 kPa 2.93 dm 3 4.93 X 104 kPa ? dm 3
of 107 kPa when the temperature is 22 C\ If the tem -
perature changes to 45 C. what will be the pressure of c. 1.00 atm 120. ml. ? atm 97.0 ml .
the helium in the balloon? f. 0.77 atm 3.6 m 3 1.90 atm ? m3

The Combined Gas Law

254. A gas cylinder contains 0.722 m3 of hydrogen gas at a
hi each of the following problems, it is assumed pressure of 10.6 atm . If the gas is used to fill a balloon
that the molar quantity of gas does not change. at a pressure of 0.96 atm . what is the volume in m3 of
248. Calculate the unknown quantity in each of the follow - the filled balloon?
ing measurements of gases . 255. A weather balloon has a maximum volume of 7.50 X
103 L . The balloon contains 195 L of helium gas at a
pressure of 0.993 atm . What will be the pressure when
a. 99.3 225 ml . 15 C 102.8 ? 111 L 24 C the balloon is at maximum volume?
k Pa kPa
256. A rubber ball contains 5.70 x 10 1 dm3 of gas at a
b. 0.959 3.50 L 45 C ? atm 3.70 L. 37 C pressure of 1.05 atm . What volume will the gas occupy
atm at 7.47 atm?
.
c 0.0036 62 mL 373 k 0.0029 64 mL ?k 257. Calculate the unknown quantity in each of the follow -
atm atm ing measurements of gases .
d . 100. 43.2 mL 19 C 101.3 ? mL 0& C
kPa kPa

a. 26.5 mL ?k 32.9 mL 290. k

249. A student collects 450.111 L of HCl ( tf ) hydrogen chloride b. ? dm 3 100. C 0.83 dm 3 29 (
gas at a pressure ol 100. kPa and a temperature of 17°C. .
c 7.44 X 104 mm 3 870. C 2.59 x 10- mm 3 ? °C
What is the volume of the HCI at 0 C and 101.3 kPa?
d. 5.63 X 10 2 L 132 k ?L 190. k
Dalton 's Law of Partial Pressures .
e ? cm3 243 k 819 cm3 409 k
250. A chemist collects a sample of I LS ( g ) over water at a - 246 C
f. 679 m 3 J ( ? nT
temperature of 27 C. The total pressure of the gas that

896 APPENDIX D
 .
258 A bubble of carbon dioxide gas in some unbaked .
266 Hydrogen gas is collected by water displacement .
bread dough has a volume of 1.15 cm3 at a tempera - Total volume collected is 0.461 L at a temperature of
ture of 22 C. What volume will the bubble have when 17 C and a pressure of 0.989 atm. What is the pressure
the bread is baked and the bubble reaches a tempera - of dry hydrogen gas collected?
ture of 99°C? .
267 One container with a volume of 1.00 L contains argon
.
259 A perfectly elastic balloon contains 6.75 dm3 of air at at a pressure of 1.77 atm, and a second container
a temperature of 40. C. What is the temperature if the of 1.50 L volume contains argon at a pressure of
balloon has a volume of 5.03 dm 3? 0.487 atm. They are then connected to each other so
that the pressure can become equal in both containers.
.
260 Calculate the unknown quantity in each of the follow - What is the equalized pressure? Hint: Each sample of
ing measurements of gases. gas now occupies the total space. Dalton 's law of par -
tial pressures applies here.
.
268 Oxygen gas is collected over water at a temperature of
a. 0.777 atm ?C 5.6 atm I 92°C .
10. C and a pressure of 1.02 atm The volume of gas
plus water vapor collected is 293 ml,. What volume of
b. 152 k Pa 302 K ? kPa It K oxygen at STP was collected?
.
c ? atm - 76T 3.97 atm 27 C .
269 A 500 mL bottle is partially filled with water so that the
.
<1 395 atm 46 C 706 atm ?*C total volume of gases ( water vapor and air ) remaining
. ? atm in the bottle is 325 cm3, measured at 20.°C and 101.3
t* -37°C 350. atm 2050 C
kPa. The bottle is sealed and taken to a mountamtop
f. 0.39 aim 263 K 0.058 atm ?K where the pressure is 76.24 kPa and the temperature is
IO C. If the bottle is upside down and the seal leaks,
how much water will leak out ? The key to this problem
.
261 A 2 L bottle containing only air is sealed at a tempera - is to determine the pressure in the 325 cm 3 space when
ture of 22°C and a pressure of 0.982 atm . The bottle is
the bottle is at the top of the mountain.
placed in a freezer and allowed to cool to 3 C. What
is the pressure in the bottle? .
270 An air thermometer can be constructed by using a
glass bubble attached to a piece of small-diameter
.
262 The pressure in a car lire is 2.50 atm at a temperature glass tubing. The tubing contains a small amount of
of 33 C . What would the pressure be if the tire were colored water that rises when the temperature in-
allowed to cool to 0 "C? Assume that the tire does not creases and the trapped air expands. You want a
change volume. 0.20 cm3 change in volume to equal a 1 C change in
.
263 A container filled with helium gas has a pressure of .
temperature What total volume of air at 20. C
127.5 kPa at a temperature of 290. K . What is the tem - should be trapped in the apparatus below the liquid?
perature when the pressure is 3.51 kPa? .
271 A sample of nitrogen gas is collected over water, yield -
.
264 Calculate the unknown quantity in each of the follow - ing a total volume of 62.25 ml at a temperature of
,

ing measurements of gases. 22 C and a total pressure of 97.7 kPa. At what pres-
sure will the nitrogen alone occupy a volume of
50.00 mL at the same temperature?
.
272 The theoretical yield of a reaction that gives off nitro-
.
a 1.03 1.65 L 19 C 0.920 atm ?I 46 C gen trifluoride gas is 844 mL at STP. What total vol -
atm ume of NFj plus water vapor will be collected over
water at 25 C and a total pressure of 1.017 atm?
.
h 107.0 3.79 dm3 73 C ? kPa 7.58 dm3 217 C
kPa .
273 A weather balloon is inflated with 2.94 kL of helium
.
c 0.029 249 ml. ?K 0.0)8 aim 197 ml. 293 k
at a location where the pressure is 1.06 atm and the
temperature is 32 C. What will be the volume of the
aim
balloon at an altitude where the pressure is 0.092 atm
.
cl 113 ? mm -
12 C 149 kPa 3.18 X - 18°C and the temperature is - 35 C?
k Pa 103 mm3
. .
274 The safety limit for a certain can of aerosol spray is
e 1.15
atm
0.93 m 3 - 22 C* 1 , 01 aim 0.85 m3 ?°C .
95 C If the pressure of the gas in the can is 2.96 atm
when it is 17 C. what will the pressure be at the safety
f. ? atm 156 cm3 195 K 2.25 aim 468 cm 3 585 K limit ?
275. A chemistry student collects a sample of ammonia gas
at a temperature of 39 C. Later, the student measures
265. A scientist has a sample of gas that was collected
several days earlier. The sample has a volume of .
the volume of the ammonia as 108 mL but its temper -
ature is now 21°C. What was the volume of the ammo-
392 cm3 at a pressure of 0.987 atm and a temperature
of 21 ( \ On ihe day the gas was collected, ihe temper - nia when it was collected ?
ature was 13 C and the pressure was 0.992 atm. What .
276 A quantity of ( XT gas occupies a volume of 624 1 at a
volume did the gas have on the day it was collected? pressure of 1.40 atm. If this CCT is pumped into a gas

APPENDIX D 897
 cylinder that has a volume of 80.0 L, what pressure .
284 Use the ideal-gas-law equation to calculate the
will the CO'* exert on the cylinder ? unknown quantity in each of the following sets of
measurements .
The Ideal Gas Law: Chap. 11, Sec. 3
a. 0.955 atm 3.77 L 8.23 g ? g/mol 25 C
.
277 Use the ideal-gas-law equation to calculate the .
b 105.0 kPa 50.0 mL ?g 48.02 g/mol 0 C
unknown quantity in each of the following sets of
measurements. You will need to convert Celsius tem - .
c 0.782 atm ?L 3.20 X 10 - g 2.02 g/ mol
* -5 C
peratures to Kelvin temperatures and volume units to d. ? atm 2,00 L 7.19 g 159.8 g/mol 185 C
liters. .
e 107.2 kPa 26.1 mL 0.414 g ? g/mol 45 C

.
285 Determine the volume of one mole of an ideal gas at
25 C and 0.915 kPa.
.
a 1.09 atm ? 1. 0.0881 302 K
mol .
286 Calculate the unknown quantity in each of the follow -
.
b 94,9 kPa 0.0350 I ? mol 55°C ing sets of measurements.

.
c ? kPa 15.7 L. 0.815 - 2o.r Molar Mass Density t
mol
.
d 0.5( H ) atm 629 mL 0.0337 ?K
a. 1.12 atm ? g/mol 2.40 g/ L. VC
mol .
b 7.50 atm 30.07 g mol ? g/ L 20. C
.
e 0.950 atm ? I. 0.0818 19°C c. 97.4 kPa 104.09 g/mol 4.37 g/ L ? C
mol
d. ? atm 77.95 g/mol 6.27 g/ L 66 C
.
f 107 k Pa 39.0 ml ? mol 27 JC
287. What pressure in atmospheres will 1.36 kg of NT ) gas
exert when it is compressed in a 25.0 L cylinder and is
278. A student collects 425 mL of oxygen at a temperature stored in an outdoor shed where the temperature can
of 24 C and a pressure of 0.899 atm. I low many moles reach 59 C during the summer?
of oxygen did the student collect ?
.
288 Aluminum chloride sublimes at high temperatures.
What density will the vapor have at 225 C and
Applications of the Ideal Gas Law
0.939 atm pressure ?
.
279 A sample of an unknown gas has a mass of 0.116 g. It
occupies a volume of 25.0 mL at a temperature of .
289 An unknown gas has a density of 0.0262 g/mL at a
127 C and has a pressure of 155.3 kPa Calculate the . pressure of 0.918 atm and a temperature of 10. C.
molar mass of the gas. What is the molar mass of the gas?
.
280 Determine the mass of COi gas that has a volume of .
290 A large balloon contains 11.7 g of helium. What vol -
7.10 1. at a pressure of 1.11 atm and a temperature of ume will the helium occupy at an altitude of 10 ( HH ) m .
.
31 C I lint : Solve the equation for / / /. and calculate the where the atmospheric pressure is 0.262 atm and the
molar mass using the chemical formula and the periodic temperature is - 50. C?
table. .
291 A student collects ethane by water displacement at
281. What is the density 9 silicon tctralluoride gas at 72 C a temperature of 15 C ( vapor pressure of water is
and a pressure of 144.5 kPa? ‘ 1.5988 kPa ) and a total pressure of KKLO kPa. The vol -
.
282 At what temperature will nitrogen gas have a density ume of the collection bottle is 245 mL. How many
of 1.13 g/L at a pressure of 1.09 atm? moles of ethane are in the bottle ?
.
292 A reaction yields 3.75 L of nitrogen monoxide. 1 he
Mixed Review volume is measured at 19 C and at a pressure of
. -
283 I Jse the ideal gas- law equation to calculate the 1.10 atm. What mass of NO was produced bv the reac -
unknown quantity in each of the following sets <9 mea - '
tion ?
surements. .
293 A reaction has a theoretical yield of 8.83 g of ammo-
nia. The reaction gives off 10.24 L of ammonia mea -
sured at 52 C and 105.3 kPa. What was the percent
yield of the reaction?
.
a 0.0477 atm 15 2( H ) L ? mol - 15 C .
294 An unknown gas has a density of 0.405 g/ L at a pres-
b. ? k Pa (XI 19 mL .
O ( HH ) 350 mol 0C sure of 0.889 atm and a temperature of 7 C Calculate .
.
c 500.0 kl’a 250. ml 0.120 mol ? C its molar mass.

.
cl 19.5 atm •t 4.7 X HH mol 3( H ) . r .
295 A paper label has been lost from an old tank ol com -
pressed gas. To help identify the unknown gas. you

898 APPENDIX D
 mustcalculate its molar mass. It is known that the 307. A sample of ethanol burns in 02 to form C02 and
tank has a capacity of 90.0 L and weighs 39.2 kg when IUO according to the following equation:
empty. You find its current mass to be 50.5 kg. The
C2H5OH + 30: -> 2C03 4 3H20
gauge shows a pressure of 1780 kPa when the temper -
ature is lcS C. What is the molar mass of the gas in the If the combustion uses 55.8 ml. of oxygen measured at
cylinder ? 2.26 atm and 40. C\ what volume of C02 is produced
when measured at STP?
296. What is the pressure inside a tank that has a volume
of 1.20 X HP L and contains 12.0 kg of MCI gas at a 308. Dinitrogen pentoxide decomposes into nitrogen diox -
temperature of 18°C? ide and oxygen. If 5.00 L of N 2Os reacts at STP, what
volume of N02 is produced when measured at 64.5 C
297. What pressure in kPa is exerted at a temperature of
and 1.76 atm?
20. C by compressed neon eas that has a density of
2.70 g/L? 309. Complete the table below using the following equa -
tion. which represents a reaction that produces alu-
298. A tank with a volume of 658 ml. contains 1.50 g of
minum chloride:
neon gas. The maximum safe pressure that the tank
can withstand is 4.50 x 102 kPa . At what temperature 2 AI( x ) 4- 3CI2( £ ) -> 2 A 1C13( S)
will the tank have that pressure?
299. The atmospheric pressure on Mars is about 6.75 milli-
Mass Volume Mass
bars ( 1 bar = 100 kPa = 0.9869 atm ) , and the night -
time temperature can be about — 75°C on the same Al Cl2 Conditions AlCl ,
day that the daytime temperature goes up to - S C. a. excess ?L SIP 7.15 g
What volume would a bag containing 1.00 g of H2 gas b. 19.4 g ?L SIP NA
have at both the daytime and nighttime temperatures?
300. What is the pressure in kPa of 3.95 mol of Cl2 gas if it
.
c 1.559 ?L 20. C and NA
kg 0.945 atm
is compressed in a cylinder with a volume of 850. mL
at a temperature of 15°C? d. excess 920. 1. SIP '
• g
301. What volume in mL will 0.00660 mol of hydrogen gas e. ? g 1.049 ml . 37‘ C and NA
occupy at a pressure of 0.907 atm and a temperature 5.00 atm
of 9 C? r. 500.00 ? nP 15 Cand NA
302. What volume will 8.47 kg of sulfur dioxide gas occupy kg 83.0 kPa
at a pressure of 89.4 kPa and a temperature of 40. C?
303. A cylinder contains 908 g of compressed helium . It is
to be used to inflate a balloon to a final pressure of
Mixed Review
128.3 kPa at a temperature of 2 C. What will the vol - 310. The industrial production of ammonia proceeds accord -
ume of the balloon be under these conditions? ing to the following equation:
304. The density of dry air at 27°C and 100.0 kPa is N:( g ) 3H2( g ) -> 2NH3($)
1.162 g/L. Use this information to calculate the molar a. What volume of nitrogen at STP is needed to react
mass of air (calculate as if air were a pure substance ). with 57.0 mL of hydrogen measured at STP?
b. What volume of NH3 at STP can be produced from
the complete reaction of 6.39 x 104 L of hydrogen?
Stoichiometry of Gases: Chap. 11, c. If 20.0 mol of nitrogen is available, what volume of
Sec. 3 NH3 at STP can be produced?
d. What volume of ll 2 at STP will be needed to pro-
.
305 In one method of manufacturing nitric acid, ammonia duce 8( H ). L of ammonia, measured at 55°C and
is oxidized to nitrogen monoxide and water: 0.9( H ) atm?
,
4NH ( g ) 4 5 0 2 ( g ) -> 4NO( g ) 4 6H20( / ) 311. Propane burns according to the following equation:
What volume of oxvgcn will be used in a reaction of C3H8( g) 4 502( g) > 3C02( .g ) 4 4 H:0( g)
-

28( H ) I . of NH3 ? What volume of NO will be pro- a. What volume of water vapor measured at 250. C
duced ? All volumes are measured under the same and 1 .( H ) atm is produced when 3.0 I. of propane at
conditions. STP is burned?
306. Fluorine gas reacts violently with water to produce b. What volume of oxygen at 20.°C and 102.6 kPa is
hydrogen fluoride and ozone according to the follow - used if 640. 1. of CQ 2 is produced? The C02 is also
ing equation: measured at 20. C and 102.6 kPa.
c. If 465 mL of oxygen at S I P is used in the reaction,
3F\( g ) 4 3H2Q( / ) 6HF( g ) 4 03(g) what volume of C02 , measured at 37 C and
What volumes of 03 and HF gas would be produced 0.973 atm, is produced?
bv the complete reaction of 3.(4 ) X 104 ml of fluorine
. d. When 2.50 L of C3H8 at STP burns, what total vol-
gas? All gases are measured under the same condi- ume of gaseous products is formed? The volume of
tions. the products is measured at 175 C and 1.14 atm.

APPENDIX D 899
 .
312 Carbon monoxide will burn in air to produce CO2 between calcium phosphide and water according to
according to the following equation: the following equation :
2C O ( g ) + O 2( g ) -» 2C02( s )
What volume of oxygen at STP will be needed to react
—
Ca3P2( s) 4 6 H 20( / ) >
3Ca ( OH )2(s and u q ) 4- 2PH 3( g)
with 3500. L. of CO measured at 20.°C and a pressure What volume of phosphine, measured at 18 C and
of 0.953 atm ? 102.4 kPa. is produced bv the reaction of 8.46 g of
.
313 Silicon letrafluoride gas can be produced by the action Ca3P2?
of HF on silica according to the following equation: 320. In one method of producing aluminum chloride. MCI
SiO:( i ) + 4 HF( g ) -> SiF4( g ) 4 2 H20( / ) gas is passed over aluminum and the following reac-
tion lakes place:
LOO I. of I IF gas under pressure at 3.48 atm and a
temperature of 25 UC reacts completely with Si 02 to 2AI (s ) 4- 6HCl( g) -* 2 AlCl3( g ) 4- 3H 2( g )
.
form SiF 4 . What volume of SiF4 measured at 15°C
' What mass of AI should be on hand in order to pro-
and 0.940 atm. is produced by this reaction ? duce 6.0 X 103 kg of AICI 3? What volume of com -
314. One method used in the eighteenth century to gener - pressed HC1 at 4.71 atm and a temperature of 43°C
ate hydrogen was to pass steam through red - hot steel
should be on hand at the same time?
tubes. The following reaction takes place: .
321 Urea , ( NH2 )2CO, is an important fertilizer that is
3 Fc ( .v ) + 4 H 20( g) Fe304( 5) 4- 4H 2( g) manufactured by the following reaction:
.
a What volume of hydrogen at STP can be produced 2 NHj( g ) + C02(g ) - ( NH 2 )2CO( 5) 4 H20( g)
by the reaction of 6.28 g of iron ? What volume of NH 3 at SI P will be needed to pro-
.
h What mass of iron will react with 500. L of steam at duce 8.50 X 104 kg of urea if there is an 89.5 % yield in
250. C and 1.00 atm pressure ? the process?
.
c If 285 g of Fe 304 are formed , what volume of 322. An obsolete method of generating oxygen in the labo -
.
hydrogen , measured at 20. C and 1.06 atm is pro- ratory involves the decomposition of barium peroxide
duced ? by the following equation:
315. Sodium reacts vigorously with water to produce
hydrogen and sodium hydroxide according to the fol - —
2 Ba02(s) » 2BaO( s) 4- 02( g )
What mass of Ba 02 reacted if 265 mL of 02 is collect -
lowing equation:
ed by water displacement at 0.975 atm and 10.°C?
2 Na ( v ) 4- 2 H 20( / ) -> 2 NaOH ( aq ) 4- U 2( g )
323. It is possible to generate chlorine gas by dripping con -
If 0.027 g of sodium reacts with excess water, what vol - centrated HC1 solution onto solid potassium perman -
ume of hydrogen at STP is formed ? ganate according to the following equation:
.
316 Diethyl ether burns in air according to the following 2KMn04( £w / ) + 16 HCl ( fl<7 )
equation: 2 KCI ( a q ) 4- 2 MnCI2( </<7 ) + 8H 20( / ) + 5C12 ( g )
C4 H10O( / ) 4- 6Q:( g ) -4 4C02( ) 4- 5H 20( / ) If excess MCI is dripped onto 15.0 g of KMn 04 , what
*
If 7.15 L of C02 is produced at a temperature of volume of Cl 2 will be produced ? The Cl 2 is measured
125 C and a pressure of 1.02 atm , what volume of oxy - at 15°C and 0.959 atm .
gen . measured at STP, was consumed and what mass 324. Ammonia can be oxidized in the presence * >1 a plat - '

of diethyl ether was burned ? inum catalyst according to the following equation:
317. When nitroglycerin detonates, it produces large vol - 4 NI l 3( g ) 4- 50:( g ) -4 4 NO ( g ) 4 6H20( / )
umes of hot gases almost instantly according to the The NO that is produced reacts almost immediately
following equation: with additional oxygen according to the following
,
4C3 H5N 3OI ( / ) -> equation :
6 N:( g ) + 12CQ2( g ) 4 10H2O( g ) 4 02( g )
2 NO( g ) 4 O2( 8 ) -> 2 N02( g )
a. When 0.100 mol of nitroglycerin explodes, what If 35.0 kL of oxygen at STP react in the first reaction ,
volume of each gas measured at STP is produced ? what volume of NH 3 at STP reacts with it ? What vol -
h. What total volume of gases is produced at 300.°C ume of N02 at STP will be formed in the second reac-
and LOO atm w hen 10.0 g of nitroglycerin explodes? tion , assuming there is excess oxygen that was not
318. Dinitrogen monoxide can be prepared by heating used up in the first reaction ?
ammonium nitrate, which decomposes according to 325. Oxygen can be generated in the laboratory by heating
the following equation: potassium chlorate. The reaction is represented by the
NH4 N03(S ) -4 NiO( g) 4 2 H2O(0 following equation:
What mass of ammonium nitrate should be decom - 2 KCI 03( J ) -4 2 KCI ( A ) 4 302( g )
posed in order to produce 250. mL of NT ), measured What mass of KCI03 must be used in order to gener -
at STP? ate 5.00 I . of 02. measured at STP?
.
319 Phosphine. PH * , is the phosphorus analogue to 326. One of the reactions in the Solvay process is used to
ammonia. NH 3 . It can be produced by the reaction make sodium hydrogen carbonate. It occurs when car-

900 APPENDIX D
 bon dioxide and ammonia are passed through concen - 334. What is the molarity of a solution that contains
trated salt brine. The following equation represents 390.0 g of acetic acid. CH3COOH , dissolved in
the reaction: enough acetone to make 1000.0 mL of solution ?
- -
NaCl ( aq ) + H » 0( / ) + CO? ( g ) + NH 3( g ) » 335. What mass of glucose. C6 H 12Oh , would be required to
NaHC03( s) + NH 4 CI ( <w/ ) prepare 5.000 X 103 L of a 0.215 M solution ?
.a What volume of NH3 at 25°C and 1.00 atm pressure .
336 What mass of magnesium bromide would be required
will be required if 38 ( XX ) L of CO? , measured to prepare 720. mL of a 0.0939 M aqueous solution ?
under the same conditions, react to form NaHCOy? 337. What mass of ammonium chloride is dissolved in
.
b What mass of NaHCOy can be formed when the
300. mL of a 0.875 M solution ?
gases in ( a ) react with NaCl ?
.
c If this reaction forms 46.0 kg of NaHCOy , what vol - Molality
ume of NH3. measured at STB reacted ? 338. Determine the molality of a solution of 560 g of ace -
cl. What volume of CO ? , compressed in a tank at tone, CH3COCH 3 t in 620 g of water.
5.50 atm and a temperature of 42 °C. will be needed
to produce 100.00 kg of NaHC03? .
339 What is the molality of a solution of 12.9 g of fructose,
. 0, Hj ?Oft , in 31.0 g of water ?
327 The combustion of butane is represented in the fol - 340. How many moles of 2 - butanol , CH3CHOHCH 2 CH 3 ,
lowing equation:
2C4 H 10( g) + 130?( g) 8CO? ( g ) 4 10 H 2O( / )
must be dissolved in 125 g of ethanol in order to pro
duce a 12.0 m 2 - butanol solution ? What mass of
-
a. If 4.74 g of butane react with excess oxygen , what 2 - butanol is this?
volume of CO:, measured at 150.°C and 1.14 atm .
will be formed ? Mixed Review
.
b What volume of oxygen , measured at 0.980 atm and 341. Complete the table below by determining the missing
75°C. will be consumed by the complete combus - quantity in each example. All solutions are aqueous.
tion of 0.500 g of butane ? Any quantity that is not applicable to a given solution is
.
c A butane - fueled torch has a mass of 876.2 g. After marked NA .
burning for some time, the torch has a mass of
859.3 g. What volume of C02 . at STP. was formed
while the torch burned ? Mass Quart lily Quantify
d. What mass of H 20 is produced when butane burns
of Solute of Solution of Sol yent
and produces 3720 L of CO ? , measured at 35°C and
0.993 atm pressure? Solution Made Used Made Used
a. 12.0% KMnQ4 ? g KMn04 500.0 g ? g H 2Q
.
b 0.60 M BaCI ? ? gBaCI2 1.750 L NA
Concentration of Solutions: .
c 6,20 m glycerol, ? g glycerol NA 800.0 g
HOCH2CHOHCH2OH H?Q
Chap. 12, Sec. 3
d. ? M K:Cr:07 12.27 g 650. mL NA
Percentage Concentration K 2Cr 207
328. What is the percentage concentration of 75.0 g of .
c* ? m CaCI? 288 g CaCl2 NA 2.04 kg
ethanol dissolved in 500.0 g of water? H ?0
.
329 A chemist dissolves 3.50 g of potassium iodate and .
f 0.160 M NaCl ? g NaCl 25.0 mL NA
6.23 g of potassium hydroxide in 805.05 g of water.
What is the percentage concentration of each solute in g. 2.00 m glucose, ? g glucose ? g solution 1.50 kg
the solution ? QTI 12 d„ H2O
.
330 A student wants to make a 5.00% solution of rubi -
dium chloride using 0.377 g of the substance. What
mass of water will be needed to make the solution ? .
342 How many moles of H 2S04 are in 2.50 L of a 4.25 M
.
331 What mass of lithium nitrate would have to be dis- aqueous solution?
solved in 30.0 g of water in order to make an 18.0% 343. Determine the molal concentration of 71.5 g of lin -
solution ? . .
oleic acid C|gH3202 in 525 g of hexane. C*H|4 .
344. You have a solution that is 16.2 % sodium thiosulfate.
Molarity Na 2S203. bv mass.
.
332 Determine the molarity of a solution prepared by dis- a. What mass of sodium thiosulfate is in 80.0 g of solu -
solving 141.6 g of citric acid. CdLOlCOOl 1 )3 , in water tion ?
and then diluting the resulting solution to 35( X).0 mL . I >. How many moles of sodium thiosulfate are in 80.0 g
.
333 What is the molarity of a salt solution made by dis- of solution ?
solving 280.0 mg of NaCl in 2.00 mL of water? .
c If 80.0 g of the sodium thiosulfate solution is diluted
Assume the final volume is the same as the volume of to 250.0 mL with water, what is the molarity of the
the water. resulting solution ?

APPENDIX D 901
345. What mass of anhydrous cobalt ( II ) chloride would be 360. Many substances are hydrates. Whenever you make a
needed in order to make 650.00 mL of a 4.00 M solution , it is important to know whether or not the
cobalt ( II ) chloride solution ? solute you are using is a hydrate and. if it is a hydrate,
.
346 A student wants to make a 0.150 M aqueous solution how many molecules of water are present per formula
unit of the substance. This water must be taken into
of silver nitrate. AgNCh. and has a bottle containing
11.27 g of silver nitrate. What should be the final vol - account when weighing out the solute. Something else
ume of the solution ? to remember w hen making aqueous solutions from
hydrates is that once the hydrate is dissolved , the
347. What mass of urea . NH 2 CONH:. must be dissolved in
water of hydration is considered to be part of the sol -
2250 g of water in order to prepare a 1.50 m solution ?
vent . A common hydrate used in the chemistry labora -
348. What mass of barium nitrate is dissolved in 21.29 mL tory is copper sulfate pentahydrate, CuS04 *51 L0.
of a 3.38 M solution ? Describe how you would make each of the following
349. Describe what you would do to prepare 100.0 g of a solutions using CuS04* 5 I LO. Specify masses and vol -
3.5 % solution of ammonium sulfate in water. umes as needed .
.
350 What mass of anhydrous calcium chloride should be .
a 100. g of a 6.00% solution of CuS04
dissolved in 590.0 g of water in order to produce a b. LOO L of a O.S( M ) M solution of CuS04
0.S2 m solution ? .
c a 3.5 ni solution of CuS04 in 1.0 kg of water
351. I low many moles ot ammonia are in 0.250 L of a 361 . What mass of calcium chloride hexahydrate is required
5.00 M aqueous ammonia solution ? If this solution in order to make 700.0 mL of a 2.50 M solution ?
were diluted to 1.000 I .. what would be the molaritv of
the resulting solution ?
362 . What mass of the amino acid arginine. C,, H |4 N 4 CL .
would be required to make 1.250 L of a 0.( X )205 M solu -
352. What is the molar mass of a solute if 62.0 g of the tion ?
solute in 125 g of water produce a 5.3 m solution ? 363 . How much water would you have to add to 2.402 kg of
353. A saline solution is 0.9% NaCl. What masses of NaCI nickel ( ll ) sulfate hexahydrate in order to prepare a
and water would be required to prepare 50. L of this 25.00 % solution?
saline solution ? Assume that the density of water is
1.000 g / mL and that the NaCI does not add to the vol -
364 . What mass of potassium aluminum sulfate dodecahy -
drale, KA 1 ( S04 L 121 LO. would be needed to prepare
#

ume of the solution .

35.00 g of a 15.00 % KAI ( S04 ) 2 solution ? What mass
354. A student weighs an empty beaker on a balance and of water would be added to make this solution?
finds its mass to be 68.60 g. The student weighs the
beaker again after adding water and finds the new
mass to be 115.12 g. A mass of 4.08 g of glucose is
then dissolved in the water. What is the percentage
Dilutions: Chap . 12, Sec . 3
concentration of glucose in the solution ? 365. C omplete the table below by calculating the missing
355. The density of ethyl acetate at 20 C is 0.902 g/ mL. value in each row'.
What volume of ethyl acetate at 20 C would be
required to prepare a 2.0 % solution of cellulose Molarity Volume Molarity Volume
nitrate using 25 g of cellulose nitrate ? of Slock o f Stock of Dilute of Dilute
.
356 Aqueous cadmium chloride reacts with sodium sulfide Solution Solution Solution Solution
to produce bright -yellow cadmium sulfide. Write the
balanced equation for this reaction and answer the fol -
a. 0.5( H ) M 20.00 ml . ? M KBr KK ).(H ) mL
KBr
lowing questions.
a. I low many moles of CdCL are in 50.00 mL of a 1». LOOM ? mL 0.075 M 500.00 ml
3.91 M solution ? LiOH LiOH
1». If the solution in ( a ) reacted with excess sodium sul - .
c ? M ill 5.00 ml. 0.0493 M 1 ( H ) .( H ) mL
fide. how many moles of CdS would be formed ? HI
c. What mass of CdS would be formed?
.
d 12.0 M 0.250 l. 1.8 M HCl ?L
357. What mass of H 2S04 is contained in 60.00 mL of a HCl
5.85 M solution of sulfuric acid ?
358. A truck carrying 22.5 kL of 6.83 M aqueous hydro-
.
e 7.44 M ? mL 0.093 M 4.00 L
NIL, Nil ;
chloric acid used to clean brick and masonry has over-
turned . The authorities plan to neutralize the acid with
sodium carbonate. How many moles of HCl will have 366. What volume of w ater w ould be added to 16.5 mL of a
to be neutralized ? 0.0813 M solution of sodium borate in order to get a
0.02( X ) M solution ?
.
359 A chemist wants to produce 12.00 g of barium sulfate
bv reacting a 0.600 M BaCL solution with excess Mixed Review
lhS( ) 4 . as shown in the reaction below. What volume
367. What is the molarity of a solution of ammonium chlo-
of the BaCL solution should be used ? ride prepared by diluting 50.00 mL of a 3.79 M NH 4 ( I
BaCL H:SQ4 BaSQ4 + 2HCI solution to 2.00 L?

902 APPENDIX D
368. A student takes a sample of KOH solution and dilutes of a 1.22 M solution of acetic acid. You decide to use a
it with 100.00 ml of water. The student determines
, 6.45 M acetic acid solution that you have on hand.
that the diluted solution is 0.046 M KOI I . hut has for
gotten to record the volume of the original sample.
- What procedure should the technicians use in order to
get the solution they need ?
Ihe concentration of the original solution is 2.09 M . 377. A chemical test has determined the concentration of a
What was the volume of the original sample? solution of an unknown substance to be 2.41 M . A
.
369 A chemist wants to prepare a stock solution of H 2SO4 100.0 mL volume of the solution is evaporated to dry -
so that samples of 20.00 mL will produce a solution ness, leaving 9.56 g of crystals of the unknown solute.
with a concentration of 0.50 M when added to Calculate the molar mass of the unknown substance.
100.0 ml. of water. 378. Tincture of iodine can be prepared by dissolving 34 g
.
a What should the molarity of the stock solution be? of L and 25 g of KI in 25 ml. of distilled water and
h. If the chemist wants to prepare 5.00 L of the stock diluting the solution to 500. mL with ethanol . What is
solution from concentrated H2SO4 . which is 18.0 M . the molarity of L in the solution ?
what volume of concentrated acid should he used ?
379. Phosphoric acid is commonly supplied as an 85 % solu -
c. The density of 18.0 VI ICSO4 is 1.84 g/ mL. What
tion . What mass of this solution would be required to
mass of concentrated ILSO4 should he used to make
the stock solution in ( h ) ?
prepare 600.0 mL of a 2.80 M phosphoric acid solu -
tion ?
370. To what volume should 1.19 mL of an 8.00 M acetic
acid solution he diluted in order to obtain a final solu - 380. Commercially available concentrated sulfuric acid is
18.0 M LLSO 4 . What volume of concentrated H 3SO4
tion that is 1.50 M ?
would you use in order to make 3.00 L of a 4.0 M
371. What volume of a 5.75 M formic acid solution should be stock solution ?
used to prepare 2.00 L of a l .( X ) M formic acid solution?
381. Describe how to prepare LOO 1. of a 0.495 M solution
372. A 25.00 mL sample of ammonium nitrate solution pro - of urea , Nl LCONI L , starting with a 3.07 M stock
duces a 0.186 M solution when diluted with 50.00 mL solution.
of water. What is the molarity of the stock solution ?
382. Honey is a solution consisting almost entirely of a
373. Given a solution of known percentage concentration mixture of the hexose sugars fructose and glucose:
by mass, a laboratory worker can often measure out a both sugars have the formula C H O*, but they differ
calculated mass of the solution in order to obtain a in molecular structure.
^ ^
certain mass of solute. Sometimes, though , it is a. A sample of honey is found to be 76.2 % C H O
impractical to use the mass of a solution , especialh by mass. What is the molality of the hexose^ sugars
^ ^
with fuming solutions, such as concentrated IIC1 and in honey ? Consider the sugars to be equivalent ,
concentrated IINO 3 . Measuring these solutions by h. The density of the honey sample is 1.42 g/ mL. What
volume is much more practical . In order to determine mass of hexose sugars are in LOO 1. of honey? What
the volume that should be measured , a worker would is the molarity of the mixed hexose sugars in
need to know the density of the solution. This infor - honey?
mation usually appears on the label of the solution
bottle. 383. Industrial chemicals used in manufacturing are almost
never pure, and the content of the material may vary
a. Concentrated hydrochloric acid is 36 % HCI by
mass and has a density of 1.18 g/ mL. What is the from one batch to the next . For these reasons, a sam -
volume of 1.0 kg of this HCI solution ? What vol - ple is taken from each shipment and sent to a labora -
tory. where its makeup is determined . This procedure
ume contains 1.0 g of HCI ? What volume contains
is called assaying. Once the content of a material is
1.0 mol of HC I ?
h. I he density of concentrated nitric acid is 1.42 g/ mL,
known , engineers adjust the manufacturing process to
and its concentration is 71 % HNO3 by mass What . account lor the degree of purity of the starting
chemicals.
volume of concentrated HNO3 would be needed to
prepare 10.0 L of a 2.00 M solution of IINO3 ? Suppose you have just received a shipment of sodi -
.
c What volume of concentrated HCI solution would
um carbonate, Na -T'O * . You weigh out 50.00 g of the
be needed to prepare 4.50 L of 3.0 M HCI ? See ( a ) material , dissolve it in water, and dilute the solution to
for data. 1.000 L. You remove 10.00 mL from the solution and
dilute it to 50.00 mL. Bv measuring the amount of a
374. A 3.8 M solution of FeSQ4 solution is diluted to eight .
second substance that reacts with Na CO you deter-
limes its original volume . What is the molarity of the mine that the concentration of sodium
*
^ carbonate in
diluted solution ? the diluted solution is 0.0890 VI . Calculate the percent -
375. A chemist prepares 480. mL of a 2.50 M solution of age of Na CO * in the original batch of material . I he
K 2Cr207 in water. A week later, the chemist wants to molar mass ^ of Na CO is 105.99 g. ( Hint: Determine
use the solution , but the stopper has been left off the the number of moles ^ in* the original solution and con -
flask and 39 mL of water has evaporated. What is the vert to mass of Na CO . )
new molarity of the solution? . ^ ^
384 A student wants to prepare 0.600 L of a stock solution
.
376 You must w rite out procedures for a group of lab tech - of copper( II ) chloride so that 20.0 mL of the stock
nicians. One test they will perform requires 25.00 mL solution diluted by adding 130.0 ml . of water will yield

APPENDIX D 903
 a 0.250 M solution. What mass of CuCU should be .
397 Calculate the molar mass of a nonelectrolyte that low -
used to make the stock solution? ers the freezing point of 25.00 g of water to - 3.9 C
.
385 You have a bottle containing a 2.15 M BaCty solution. when 4.27 g of the substance is dissolved in the water .
You must tell other students how to dilute this solu- .
398 What is the freezing point of a solution of 1.17 g of
tion to get various volumes of a 0.65 M BaCL solution. . ,
1-naphthol CK HKO. dissolved in 2.00 mL of benzene
By what factor w ill you tell them to dilute the stock at20 C? The density of benzene at 2D ( IS 0.876
solution? In other words, when a student removes any g/mL. fcf for benzene is - 5.12 C // / / . and benzene's
.
volume I', of the stock solution, how many times V of normal freezing point is 5.53 C.
water should be added to dilute to 0.65 M? 399. The boiling point of a solution containing 10.44 g of an
386. You have a bottle containing an 18.2 % solution of unknown nonelectrolyte in 50.00 g of acetic acid is
strontium nitrate ( density = 1.02 g/mL ). 159.2 C. What is the molar mass of the solute ?
a. What mass of strontium nitrate is dissolved in .
400 A 0.0355 g sample of an unknown molecular com -
80,0 mL of this solution ? pound is dissolved in l.(XX) g of liquid camphor at
.
1» How many moles of strontium nitrate are dissolved 200.0 C. Upon cooling, the camphor freezes at
in 80.0 mL of the solution ? 157.7 C. Calculate the molar mass of the unknown
.
c If 80.0 mL of this solution is diluted with 420.0 mL compound.
of water, what is the molaritv of the solution?
401. Determine the boiling point of a solution of 22.5 g of
f ructose. C H O . in 294 g of phenol
^ ^ * .
.
402 Ethylene glycol. HOCI DCIUOH. is effective as an
antifreeze, but it also raises the boiling temperature of
automobile coolant, which helps prevent loss of
Colligative Properties: Chap. 13, coolant when the weather is hot .
Sec. 2 .
a What is the freezing point of a 50.0% solution of
ethylene glycol in water?
.
387 Determine the freezing point of a solution of h. What is the boiling point of the same 50.0% solution?

water.
.
60.0 g of glucose, Cf HjiOft, dissolved in 80.0 g of .
403 The value of Af for cyclohexane is - 20.0 ( Im , and its
'

normal freezing point is 6.6 C. A mass of 1.604 g of a

.
388 What is the freezing point of a solution of 645 g of waxy solid dissolved in 10.000 g of cyclohexane results
urea. I-LNCONH? . dissolved in 980. g of water? in a freezing point of - 4.4 C. Calculate the molar
.
389 What is the expected boiling point of a brine solution mass of the solid.
containing 30.00 g of KBr dissolved in 100.00 g of .
404 What is the expected freezing point of an aqueous
water ? .
solution of 2.62 kg of nitric acid HNO3 . in a solution
.
390 What is the expected boiling point of a CaCL solution with a total mass of 5.91 kg? Assume that the nitric
acid is completely ionized .
containing 385 g of CaCL dissolved in 1.230 x 10 ' g of
water ? .
405 An unknown organic compound is mixed with
391. A solution of 0.827 g of an unknown non -electrolyte 0.5190 g of naphthalene crystals to give a mixture hav -
compound in 2.500 g of water has a freezing point of ing a total mass of 0.5959 g. The mixture is heated
10.18 C. Calculate the molar mass of the compound. until the naphthalene melts and the unknown sub-
.
392 A 0.171 g sample of an unknown organic com -
.
stance dissolves Upon cooling, the solution freezes at
a temperature of 74.8 C. What is the molar mass of
pound is dissolved in ether. The solution has a the unknown compound?
total mass of 2.470 g. The boiling point of the
solution is found to be 36.43 C \ What is the .
406 What is the boiling point of a solution of 8.69 g of the
molar mass of the organic compound? .
electrolyte sodium acetate NaCHjCOO, dissolved in
15.00 g of water?

Mixed Review
.
407 What is the expected freezing point of a solution of
110.5 g of II2 SO4 in 225 g of water ? Assume sulfuric
In each of the following problems, assume that the acid completely dissociates in water.
solute is a nonelectrolyte unless otherwise stated 408. A compound called pyrene has the empirical formula
.
393 Calculate the freezing point and boiling point of a solu-
.
CKI IS . When 4.04 g of pyrene is dissolved in 10 ( K) g of
benzene, the boiling point of the solution is 85.1 C.
tion of 383 g of glucose dissolved in 400. g of water.
Calculate the molar mass of pyrene and determine its
.
394 Determine the boiling point of a solution of 72.4 g ol molecular formula. The molal boiling-point constant
glycerol dissolved in 122.5 g of water. for benzene is 2.53 C / m. Its normal boiling point is
395. What is the boiling point of a solution of 30.20 g of 80.1°C.
.
ethylene glycol 1 IOC 1HC1 LOI I. in 88.40 g of phenol? . .
409 What mass of CaCh when dissolved in 100.00 g of
. .
396 What mass of ethanol. CIL C ILOH. should be dis-
solved m 450. g of water to obtain a freezing point of
water, gives an expected freezing point of - 5.0 'C;
CaCty is ionic ? What mass of glucose would give the
4.5 C? same result ?

904 APPENDIX D
 .
410 A compound has the empirical formula CH:0. When .
423 What are the pOH values of solutions with the follow -
0.0866 g is dissolved in 1.000 g of ether, the solutions ing hydronium ion concentrations?
boiling point is 36.5°C. Determine the molecular for - .
a 2.51 x 10- 13 vi
mula of this substance. .
b 4.3 X 10 3 M
“

.
411 What is the freezing point of a 2«S.6% ( bv mass) aque - .
c 9.1 x 10“6 M
ous solution of HCI? Assume the HCI is 100% ion- .
d 0.070 M
ized. .
424 A solution is prepared by dissolving 3.50 g of sodium
.
412 What mass of ethylene glycol. HOC!LCILOH. must hydroxide in water and adding water until the total
volume of the solution is 2.50 L. What are the OH "
be dissolved in 4.510 kg of water to result in a freezing
and H ;Q + concentrations?
point of 18.0 ' C? What is the boiling point of the
same solution? .
425 if 1.00 L of a potassium hydroxide solution with a pH
.
413 A water solution containing 2.00 g of an unknown of 12.90 is diluted to 2.00 L. what is the pi 1 of the
molecular substance dissolved in 10.00 g of water has a resulting solution?
freezing point of - 4.1) C.
.
a Calculate the molality of the solution.
.
b When 2.00 g of the substance is dissolved in acetone Mixed Review
instead of in water, the boiling point of the solution 426. Calculate the H3O " and OH concentrations in the
is 58.9 C. The normal boiling point of acetone is
'

.
following solutions Each is either a strong acid or a
.
56.00 C and its Kf , is 1.71 dm. Calculate the molal- .
strong base
ity of the solution from this data. .
a 0.05 M sodium hydroxide
.
414 A chemist wants to prepare a solution with a freezing .
h 0.0025 M sulfuric acid
point of - 22.0 C and has 100.00 g of glycerol on .
c 0.013 M lithium hydroxide
hand. What mass of water should the chemist mix with .
cl 0.150 M nitric acid
the glycerol? .
e 0.0200 M calcium hydroxide
.
415 An unknown carbohydrate compound has the empiri- .
f 0.390 M perchloric acid
cal formula CUT). A solution consisting of 0.515 g of .
427 What is the pH of each solution in item 426?
the carbohydrate dissolved in 1.717 g of acetic acid 428. Calculate [ H3O ’
] and [ OH ] in a 0.160 M solution of
“

freezes at 8.8 C. What is the molar mass of the carbo- potassium hydroxide. Assume that the solute is 100%
hydrate ? What is its molecular formula ? dissociated at this concentration.
.
416 An unknown organic compound has the empirical for - .
429 The pH of an aqueous solution of NaOH is 12.9. What
mula C' d l O. A solution of 3.775 g of the unknown is the molarity of the solution?
compound dissolved in 12.00 g of water is cooled until
430. What is the pH of a 0.001 25 M HBr solution? If
it freezes at a temperature of - 4.72 C. Determine the
175 mL of this solution is diluted to a total volume of
molar mass and the molecular formula of the com-
3.00 L, what is the pll of the diluted solution?
pound.
.
431 What is the pll of a 0.0001 VI solution of NaOH?
What is the pH of a 0.0005 M solution of NaOH?
pH: Chap. 15, Sec. 1 432. A solution is prepared using 15.0 mL of 1.0 M HCI
and 20.0 mL of 0.50 M HNO3 . The final volume of the
.
417 The hydroxide ion concentration of an aqueous solu - solution is 1.25 L. Answer the following questions:
tion is 6.4 x in 5 M. What is the hydronium ion con- a. What are the [ HjO * ] and [ OH | in the final solu-
centration? tion?
b. What is the pl l of the final solution ?
.
418 Calculate the ICO ‘ and OH concentrations in a
7.50 x 10 4 VI solution of HNO3 , a strong acid . 433. A container is labeled 500.0 mL of 0.( X ) 1 57 M nitric
acid solution. A chemist finds that the container was
.
419 Determine the pH of a 0.001 18 M solution of HBr.
not sealed and that some evaporation has taken place.
.
420. a What is the pH of a solution that has a hydronium The volume of solution is now 447.0 mL.
ion concentration of 1.0 M? a. What was the original pH of the solution?
.
b What is the pH of a 2.0 M solution of HCI. assum - b. What is the pH of the solution now?
ing the acid remains 100% ionized?
. .
c What is the theoretical pH of a 10 M solution of
.
434 Calculate the hydroxide ion concentration in an aque-
ous solution that has a 0.000 35 M hydronium ion con -
HCI?
centration.
.
421 What is the pH of a solution with the following
435. A solution of sodium hydroxide has a pH of 12.14. If
hydroxide ion concentrations?
'
.
a 1 X 1() S M
50.00 mL of the solution is diluted to 2.000 L with
.
b 5 X 10 ~H M
water, what is the pH of the diluted solution ?
.
c 2.90 X 10 “ 11 M 436. An acetic acid solution has a pH of 4.0. What are the
.
422 What are the pOH and hydroxide ion concentration of [ H O * | and [ OH ) in this solution?
^ _
437. What is the pH of a O.( KX ) 460 M solution of Ca ( OI ! ) >?
a solution with a pH of 8.92?

APPENDIX D 905
 .
438 A solution of strontium hydroxide with a pi I of 11.4 is Titrations: Chap. 15, Sec. 2
to he prepared. What mass of strontium hydroxide
would he required to make 1.00 L of this solution? In each of the following problems , the acids and
. .
439 A solution of ML has a pH of 11.00 What are the bases react in a mote ratio o f 1 mol base : / mol
concentrations of hvdronium and hydroxide ions in acid.
this solution?
.
440 Acetic acid does not completely ionize in solution. .
451 A student titrates a 20.00 mL sample of a solution ol
Percent ionization of a substance dissolved in water is HBr with unknown molarity. The titration requires
equal to the moles of ions produced as a percentage of 20.05 mL of a 0.1819 \ \ solution of NaOl 1. What is the
the moles of ions that would be produced if the sub- molarity of the HBr solution?
.
stance were completely ioni /ed Calculate the percent .
452 Vinegar can be assayed to determine its acetic
ionization of acetic acid in the following solutions. acid content . Determine the molarity of acetic
.
a 1.0 M acetic acid solution with a pH of 2.40 acid in a 15.00 mL sample of vinegar that requires
.
b 0.10 M acetic acid solution with a pH of 2.90 22.70 mL of a 0.550 M solution of NaOH to reach
.
c 0.010 M acetic acid solution with a pH of 3.40 the equivalence point.
.
441 alculate the pH of a solution that contains 5.00 g of
( .
453 A 20.00 mL sample of a solution of Sr ( OtI L is titrated
11NO; in 2.0t > L of solution. to the equivalence point with 43.03 mL of 0.1159 M
.
442 A solution of MCI has a pH of 1.50. Determine the pH HCI. What is the molarity of the Sr ( C ) H ); solution?
of the solutions made in each of the following ways. .
454 A 35.00 mL sample of ammonia solution is titrated to
.
a 1.00 mL of the solution is diluted to 1000 mL with . the equivalence point with 54.95 mL of a 0.400 M sul -
water. furic acid solution. What is the molarity of the ammo-
b. 25.00 mL diluted to 200. mL with distilled water.
is nia solution ?
c. 18.83 ml of the solution is diluted to 4.000 L with dis-
tilled water. In the problems below , assume that impurities are
.
(I 1.50 L is diluted to 20.0 kL with distilled water. not acidic or basic and that they do not react in an

.
443 An aqueous solution contains 10 000 times more acid - base titration.
hvdronium ions than hydroxide ions. What is the con - .
455 A supply of glacial acetic acid has absorbed water
centration of each ion ? from the air. It must be assayed to determine the actu -
.
444 A potassium hydroxide solution has a pH of 12.90 . al percentage of acetic acid. 2.000 g of the acid is di -
Enough acid is added to react with half of the OH luted to KK ).( K ) mL. and 20.00 mL is titrated with a
ions present. What is the pi I of the resulting solution? solution of sodium hydroxide. The base solution has a
Assume that the products of the neutralization have concentration of 0.218 M. and 28.25 mL is used in the
no effect on pH and that the amount of additional .
titration Calculate the percentage of acetic acid in the
produced is negligible.
water .
original sample Write the titration equation to gel the
445. A hydrochloric acid solution has a pH of 1.7( 1. What is mole ratio.
the 111 ,0 | in this solution? Considering that IiCI is a 456. A shipment of crude sodium carbonate must be
strong acid, what is the 1 ICI concentration of the solu - assayed for its NaKD; content. You receive a small
tion ? jar containing a sample from the shipment and weigh
446. What is the molarity of a solution of the strong base out 9.709 g into a flask , where it is dissolved in water
Ca( OHb in a solution that has a pH of 10.80? and diluted to 1.0000 I. with distilled water. A
10.00 mL sample is taken from the flask and titrated
447. You have a LOO M solution of the strong acid. HCI.
to the equivalence point with 16.90 ml. of a 0.1022 M
What is the pH of this solution? You need a solution
HCI solution. Determine the percentage of NaK'O in
of pi I 4.00. To what volume would you dilute 1.00 L of
the sample. Write the titration equation to get the *
the HCI solution to get this pH? To what volume
would you dilute 1.00 L of the pH 4.00 solution to gel
mole ratio .
a solution id pH 6.00? To what volume would you
dilute 1.00 L of the pH 4.00 solution to get a solution Mixed Review
of pH 8.00?
.
457 A 50.00 mL sample of a potassium hydroxide is titrated
. .
448 A solution of chloric acid IK K );,, a strong acid, has a with a 0.8186 M HCI solution. The titration requires
pH of 1.28. How many moles of NaOH would be 27.87 mL of the HCI solution to reach the equivalence
required to react completely with the HCIO, in 1.00 l. .
point What is the molarity of the K. OH solution?
of the solution? What mass of NaOH is required? .
458 A 15.00 mL sample of acetic acid is titrated with
.
449 A solution of the weak base N11;has a pH of 11.90. 34.13 mL of 0.9940 M NaOH. Determine the molarity
I low many moles of 1 ICI would have to be added to of the acetic acid.
1.00 L of the ammonia to react with all of the OH 459. A 12.00 mL sample of an ammonia solution is titrated
ions present at pH 11.90? .
with 1.499 M UNO; solution A total of 19.48 mL of
.
450 I he piI of a citric acid solution is 3.15. What are the acid is required to reach the equivalence point. What
[ HyO * ] and [ OH ] in this solution? is the molarity of the ammonia solution ?

906 APPENDIX D
 .
460 A certain acid and base react in a 1 : 1 ratio, .
471 An ammonia solution of unknown concentration is
a. If the acid and base solutions are of equal concen - .
titrated with a solution of hydrochloric acid The HCI
tration. what volume of acid will titrate a 20.00 mL solution is 1.25 M. and 5.19 mL are required to titrate
sample of the base ? 12.61 mL of the ammonia solution. What is the molar -
.
h If the acid is twice as concentrated as the base, what ity of the ammonia solution?
volume of acid will be required to titrate 20.00 mL
of the base?
.
472 What volume of 2.811 M oxalic acid solution is needed
to react to the equivalence point with a 5.090 g sample
.
c How much acid will be required if the base is four
of material that is 92.10% NaOH? Oxalic acid is a
times as concentrated as the acid, and 20.00 mL of
diprotic acid.
base is used?
.
461 A 10.00 ml sample of a solution of hydrofluoric acid. .
473 Standard solutions of accurately known concentration
I IF, is diluted to 500.00 mL. A 20.00 mL sample of the are available in most laboratories. These solutions are
diluted solution requires 13.51 mL ol a 0.15( H) M used to titrate other solutions to determine their con -
NaOH solution to be titrated to the equivalence point. centrations. Once the concentration of the other solu-
What is the molarity of the original IIF solution? tions are accurately know n, they may be used to
.
462 A solution ol oxalic acid, a diprolie acid, is used to
titrate solutions of unknowns .
The molarity of a solution of IICI is determined by
titrate a 16.22 mL sample of a 0.5030 M KOII solu- titrating the solution with an accurately known solu-
tion. If the titration requires 18.41 mL of the oxalic-
acid solution, what is its molarity?
.
tion of Ba( OI IF which has a molar concentration of
.
0.1529 M A volume of 43.09 mL of the BatOl 1 ) -» solu-
.
463 A ILSO4 solution of unknown molarity is titrated with tion titrates 26.06 mL of the acid solution. The acid
a 1.209 M NaOH solution. The titration requires solution is in turn used to titrate 15.00 mL of a solu -
42.27 mL of the NaOH solution to reach the equiva - tion of rubidium hydroxide. The titration requires
lent point with 25.00 mL of the IKSO4 solution. What 27.05 mL of the acid.
is the molarity of the acid solution? a. What is the molarity of the HCI solution?
. .
464 Potassium hydrogen phthalatc KHQH4O4 is a solid. b. What is the molarity of the RbOl 1 solution?
acidic substance that reacts in a 1 : 1 mole ratio with
bases that have one hydroxide ion. Suppose that
.
474 A truck containing 28( H ) kg of a 6.0 M hydrochloric
acid has been in an accident and is in danger of
0.7025 g of potassium hydrogen phthalatc is titrated to spilling its load. What mass of Ca( OH ): should be sent
the equivalence point by 20.18 mL of a KOH solution. to the scene in order to neutralize all of the acid in
What is the molarity of the KOH solution? case the tank bursts? The density of the 6.0 M HCI
.
465 A solution of citric acid, a triprotic acid, is titrated solution is 1.10 g/mL.
with a sodium hydroxide solution. A 20.00 mL sample .
475 A I.( H ) ml . sample of a fairly concentrated nitric acid
of the citric acid solution requires 17.03 mL of a
solution is diluted to 2( H ).( M) mL. A 10.00 mL sample ol
2.025 M solution of NaOH to reach the equivalence
the diluted solution requires 23.94 mL of a 0.0177 N1
point. What is the molarity of the acid solution?
solution of Ba( OH ): to be titrated to the equivalence
.
466 A flask contains 41.04 mL of a solution of potassium point . Determine the molarity of the original nitric -
.
hydroxide The solution is titrated and reaches an
acid solution.
equivalence point when 21.65 mL of a 0.6515 M solu-
tion of HNO3 is added. Calculate the molarity of the .
476 What volume of 4.494 M FLSO4 solution would be
base solution . required to react to the equivalence point with
7.2280 g of LiOH ( .v ) ?
.
467 A bottle is labeled 2.00 M FLSO 4 . You decide to
titrate a 20.00 mL sample with a 1.85 M NaOH solu-
tion. What volume of NaOH solution would you
expect to use if the label is correct ?
.
468 What volume of a 0.5200 M solution of ILSO4 would
Thermochemistry: Chap. 16, Sec. 1
be needed to titrate 1 ( K ).( H ) mL of a 0.1225 M solution
ofSr( OH )2?
.
469 A sample of a crude grade of KOH is sent to the lab
.
477 Calculate the reaction enthalpy for the following
to be tested for KOH content . A 4.005 g sample is
dissolved and diluted to 200.00 mL with water A .
reaction:
.
5COi(g) + SiiNjf .v ) —» 3SiO(.s ) + 2N O( g) + 5CO(.g)
25.00 mL sample of the solution is titrated with a
0.4388 M HCI solution and requires 19.93 mL to reach
the equivalence point. How many moles of KOI I were
.,
lise the following equations and data:
( I ) CO( g ) + SiO (s)

(2)
SiO( ,g) + CO,( g)
SCCMg ) + Si N4( s ) ->
in the 4.005 g sample ? What mass of KOH is this?
What is the percent of KOH in the crude material ? 3Si02(.v ) + 2N:0( g ) + 8CO( g )
.
470 What mass of magnesium hydroxide would be Attraction 1 = + 520.9 kJ
required for the magnesium hydroxide to react to
the equivalence point with 558 mL of 3.18 VI Attreaction 2 = + 461.05 kJ
hydrochloric acid?

APPENDIX D 907
 Combustion of butanol:
Determine All for each of the following three reac-
tants. ,
C4HI OH( / ) + 602(g) -> 4C02( g) + 5 HiO( / )
A / / = - 2675.9 kJ/mol
478. The following reaction is used to make CaO from (

limestone: Combustion ol butanoic acid:

CaCOj( $ ) - CaO(.v ) 4- C02( g) C3H7COOH( /) 4 502( g) -> 4C02( g ) 4 4H20( / )
*
.
479 The following reaction represents the oxidation of A / /, = - 2183.6 kJ/mol
FeO to Fe2Oj: 488. Determine the free energy change for the reduction of
2FeO( .v ) 4- 02( g) —> Fe203( v ) . CuO with hydrogen. Products and reactants are at 25 C.
.
480 Fhe following reaction of ammonia and hydrogen flu - CUO(J) + H2(g) -4 Cu(.v ) -f- H20( /)
oride produces ammonium fluoride: A / / = - 128.5 kJ/mol
NH3(g) + HF( g) -4 NH4F(s) A A = - 70.1 J /mol * K
. .
481 Calculate the free energy change AG, for the combus- .
489 Calculate the enthalpy change at 25 C for the reaction
tion of hydrogen sulfide according to the following .
of sodium iodide and chlorine Use only the data given.
chemical equation. Assume reactants and products are Nal ( .v) + Cl2(gJ > NaCI(.v) 4 I2( /;
—
at 25 X: A.V = - 79.9 J/mol*K
<
H2S(g ) 4 02 g) -» H20( /) S02(g) - AG = 98.0 kJ/mol —
A //readion = -562.1 kJ/mol
“ .
490 The element bromine can be produced by the reaction
A rcacuon = 0,09278 kJ /mol*K of hydrogen bromide and manganese(IV ) oxide:
.
^
482 Calculate the free energv change for the decomposi- 4HBr (g) 4- MnOi(.v ) -4 MnBr2(s) 2H20( /) 4- Br 2( /) 4

tion of sodium chlorate. Assume reactants and prod- A / / for the reaction is 291.3 kJ/mol at 25 C. Use this
value and the following values of A / / ' to calculate
1
ucts are at 25 C:
NaCIOjG ) — NaCI( .v ) 4- 02( g) A / / ? of MnBr2(s ).
J
“ 19.1 kJ /Illol A = - 36.29 kJ /mol
^^
rcaclion

A.Vreaction = '0.1768 kJ / mol * K A H / MnO. = - 520.0 kJ/mol

{)

.
483 Calculate the free energy change for the combustion A// ‘‘ t ( >
= - 285.8 kJ/mol
.
of I mol of ethane Assume reactants and products arc
'
A / /!Mir, = 0.00 kJ / mol
. , ! 25 C:
C:FUg) 4 02(g) -4 2C02(g) 3H >Q( /)
.
491 Calculate the change in entropy, A.V. at 25 C for the
reaction of calcium carbide w ith water to produce
- ~ 1561 kJ /mol
^^
rcacuon
AArcnclIon = - 0.4084 kJ/mol K
Mixed Review
- acetylene gas:
CaC:(.v ) 4 2H ?0( /) -» C2H2( g) + Ca( OH)2( v )
AG = - 147.7 kJ /mol
.
484. Calculate AII for the reaction of fluorine with water: A / / = - 125.6 kJ/mol
F2(g) 4 H20( /) -> 2HF( g) 4 02(g) .
492 Calculate the free energy change for the explosive
.
485 Calculate AII for the reaction ol calcium oxide and
decomposition of ammonium nitrate at 25 C Note .
that IDO is a gas in this reaction:
sulfur trioxide:
,
NH4NO (.v ) -4 N:0( g) 4 2H:0(g)
CaO( .v ) SOi(g) -4 CaS04 ( .v )
t \ e Ilie follow ing equations and data:
H:0< / ) 4 SOTO -> H2 S04( /)
.
A.V = 446.4 J/mol K -
493 In locations where natural gas, which is mostly
methane, is not available, many people burn propane,
A// - 132.5 kJ/mol which is delivered by truck and stored in a tank under
H2S04( / ) 4 Ca( \ ) -4 CaS04(.v ) H2(g) pressure.
Ml = -602.5 kJ/mol .
a Write the chemical equations for the complete com -

Ca(.v ) 4- 02( g ) -> CaO( .v )

bustion of I mol of methane Cll4 and I mol of . .
propane. C' d Is-
A// = 634.9 kJ/mol b. Calculate the enthalpy change for each reaction to
H:(g) 4 Q2(g) -4 H20( /) determine the amount of energv as heat evolved by
burning 1 mol of each fuel.
.
-
Ml = 285.8 kJ /mol
486 Calculate Ml for the reaction of sodium oxide with
.
c Using the molar enthalpies ol combustion you calcu-
lated. determine the energy output per kilogram
sulfur dioxide: ol each fuel. Which fuel yields more energy per
Na20( .v ) 4 S02( g ) -4 Na2 S03( .v ) unit mass?
.
487 I se enthalpies of combustion to calculate A / / for the .
494 The hydration of acetylene to form acetaldehyde is
oxidation of 1 - butanol to make butanoic acid: shown in the following equation:
C4FUOH< / ) 4 Q2( g ) -4 Cdl7COOII( / ) 4 H20( /) C2ll2(g) 4 H2Q( / ) -> CH3CHO( /)

908 APPENDIX D
 Use enthalpies of combustion for C2H2 and CH3CHO For problems 49S-499
to compute the enthalpy of the above reaction.
. A //1J? A
CiH2( g) 202(g) 2 ( ( );( ' ) H20(/
* ^ <
> Substance ( kj / mol ) Substance
1
( kj / mol )
A / / - - 1299.6 kJ/mol
CH3CHO( / ) 4 202 ( g ) -> 2C02(g) + 2H20( /) N\h( g ) - 45.9 HF(g) - 273.3
A / / = - 1166.9 kJ/mol NHjCIf.v ) - 314.4 H2Q(g) -241.82
495. Calculate the enthalpy for the combustion of decane. NH4F(.V ) - 125 H:Q( / ) - 285.8
A / / '/ for liquid decane is - 300.9 kJ/mol . NH4NO (s ) , -365.56 H:0:( / ) - 187.8
C|0H22( /) + 1S02(g) -4 10CO2(g) 4 11H20( / )
Br2( /) 0.00 H2S04( /) - 813.989
.
496 Find the enthalpy of the reaction of magnesium oxide
CaCQ 3(5 ) - 1207.6 FeO( j) - 825.5
with hydrogen chloride:
CaO(.v ) - 634.9 Fe203( j) - 1118.4
MgO(s) 4 2HCI( g) -> MgCl2(5) + H20( /)
- 74.9
Use the following equations and data . Cl U ( g ) MnQ2( 5 ) - 520.0

Mg(.v ) 4 2HCI(g) MgCI2(.v ) 4 H2(g) C 3HH( g ) - 104.7 N20( g ) 482.1

A / / = - 456.9 kJ /mol C O2 ( g ) - 393.5 C>:( g ) 0.00
Mg(5 ) 4 Q2(g) MgO( .v ) F2( g ) 0.00 Na:()( s ) - 414.2
A / / ~ - 601.6 kJ mol H2(g) 0.00 Na:SOdv ) -not
H20( /J -> U 2( g ) + 02(g) HBr i g ) - 36.29 SO:( c0 - 296.8
A / / = 4 285.8 kJ /mol HCI(g) - 92.3 SO3(g) -395.7
.
497 What is the free energy change for the following reac -
tion at 25 C?
2NaOH(.v ) + 2Na( ) —
* A /2/ ?Na20=(j)-4425.9 \ \ 2( g )
At equilibrium, the concentration of A is 2.24 x
A.S = 10.6 J / mol K #
kJ / mol
/ N»OH 10 2 M and the concentrations of both C and D are
498. The following equation represents the reaction 6.41 X 10 - - M.
between gaseous HCI and gaseous ammonia to form .
b A 4 B +* C 4 D
'
solid ammonium chloride: At equilibrium, the concentrations of both A and B
NH3(fl) 4 HCI(g) NH4CI( X ) are 3.23 x 10 5 M and the concentrations of both C
“

Calculate the entropy change in J /mol*K for the reac - and D are 1.27 X 10“2 M.
tion of hydrogen chloride and ammonia at 25 C using .
c A 4 B < j2C
the following data and the table following item 500. A t equilibrium, the concentrations of both A and B
are 7.02 X It ) - - M and the concentration of C is
AG = - 91.2 kJ /mol
2.16 X 10- 2 M.
'
.
499 The production of steel from iron involves the removal
.
of many impurities in the iron ore. The following equa -
tions show some of the purifying reactions. Calculate
d 2A
^
2C 4 D
At equilibrium, the concentration of A is 6.59 x
the enthalpy for each reaction. Use the table I0" 4 M. The concentration of C is 4.06 X 10 M, '
following item 500 and the data given below, and the concentration of D is 2.03 X 10 - M.
. '
.
a 3C(.v ) 4 Fe 2Odx ) -> 3CO(g) 4 2Fe(.v ) e A 4 B 4C 4 D + E
^
A / / ?f t < »,v i - 110.53 kJ/mol At equilibrium, the concentrations of both A and B
.
b 3 Mn (.s ) 4 Fe *»03( v ) . 3 MnO(.v ) 4 2Fe(.v ) are 3.73 x 10 4 M and the concentrations of C D . .
A /C , , 384.9 kJ/mol and E are 9.35 • 10 1 M .
f. 2 A + B 2C
. .
c 12 P(s ) 4 l0Fe:O3(.v ) -> 3P4Oln( v ) + 20Fe( s )
At equilibrium, the concentration of A is
A / /? - 3009.9 kJ /mol
. .• 5.50 X 10“ M. the concentration of B is 2.25 x 10 -
'.
/ Wo
d 3Si( v ) 4 2Fe203(s) -» 3SiO ->(.v ) 4 4Fe(.v ) '
and the concentration of C is 1.02 x 10 : M .
A / / f? = -910.9 kJ /mol
.
e 3S( s ) 4 2Fe203(s) —> 3 SQ2(g) 4Fe(.v )
.
501 Calculate the concentration of product D in the fol-
lowing hypothetical reaction:
2 A ( g ) «2 2C( g ) 4 D i g )
At equilibrium, the concentration of A is
Equilibrium: Chap. 18, Sec. 1 1.88 x 10 1 M, the concentration of C is 6.56 VI,
and the equilibrium constant is 2.403 X II)2.
.
500 Calculate the equilibrium constants for the following
502. At a temperature of 700 K. the equilibrium constant is
hypothetical reactions. Assume that all components of
the reactions are gaseous, '
3.164 x 10- for the following reaction system for the
hydrogenation of ethene. C2H4 , to ethane, C2Hft:
.
a A —» C 4 D
CIH4( J? ) + H;(g) £? C2Hh( g)

APPENDIX D 909
 What will be the equilibrium concentration of .
a The equilibrium constant for this reaction at 5( H ) K
ethene if the concentration of Il2 is 0.0619 M and .
is 1.671 x I04 What concentration of NO: is pres-
the concentration of C21lh is 1.055 M? ent at equilibrium if [ NO| 6.2( H ) X 10 : M and
«.
[ 0:1 = 305 x |() - 3 M?
Mixed Review I>. At 1000 K . the equilibrium constant, K . for the
.
503 I sing the reaction A
' .
+ 2B C + 21) determine the same reaction is 1.315 x 10 What will be the con -
equilibrium constant if the following equilibrium con- centration of NO: at 1000 K given the same concen-
centrations are found. All components are gases. trations of NO and 02 as were in ( a ) ?
|A ) = 0.0567 M .
510 Consider the following hypothetical reaction, for
[ R ] = 0.1171 M which K = l at 300 K :

-
[ C ] O.( KH) 3378 M
| F>| = 0.000 6756 M .
a If the
AO? ) + B( s ) 2 2C( g )
reaction begins with equal concentrations of
.
504 In the reaction 2 A 2C 4 2 D. determine the equilib- A and B and a zero concentration of C. what can
rium constant when the following equilibrium concen - you say about the relative concentrations of the
trations are found. All components are gases . components at equilibrium ?
I>. Additional C is introduced at equilibrium, and the
|A ] = 0.1077 M
temperature remains constant. When equilibrium is
[ Cl 0.000 4104 M restored, how will the concentrations of all compo-
[ D] = 0.000 4104 M nents have changed ? How will K have changed?
.
505 Calculate the equilibrium constant for the following
.
reaction Note the phases of the components.
511. The equilibrium constant for the following reaction of
hydrogen gas and bromine gas at 25 C is 5.628 x l ( ) s:
,
2 A ( .g ) + B ( s ) Z C( g ) D( g ) H 2(g) + Br2( g ) £? 2HBr( g )
I he equilibrium concentrations of the components are
’
.
a Write the equilibrium expression for this reaction,
|A 1 = 0.0922 VI h. Assume that equimolar amounts of H2 and Br:
|C| = 4.11 X It ) 4 M .
were present at the beginning Calculate the equi -
librium concentration of H2 if the concentration of
[ D| = S.22 x 10 4 M
HBr is 0.500 VI.
506. The equilibrium constant of the following reaction for .
c If equal amounts of II2 and Br: react, which reac -
the decomposition of phosgene at 25 C is tion component will be present in the greatest con-
4.2S2 x 10 centration at equilibrium ? Explain your reasoning.

.
COCI:( K )
^ CO( g ) T Cl2 ( g )
a What is the concentration of COC'l2 when the con -
.
512 The following reaction reaches an equilibrium stale:
N:F40? ) 2NF?( g )
centrations of both CO and Cl2 are 5.90 x K ) 3 \ j 9
h. When the equilibrium concentration of COCR is At equilibrium at 25 C the concentration of NTj is
0.003 70 VI. w hat are the concentrations of CO and found to be 0.9989 M and the concentration of NT: s
OR? Assume the concentrations are equal. 1.131 X 10 5 M. Calculate the equilibrium constant of '
507. C’onsider the following hypothetical reaction. the reaction .
A ( g ) 4- B (.v ) .
513 The equilibrium between dinitrogen tetroxide and nitro -
a. UK
^ C( g ) + D( s )
I for this reaction at 500 K , what can you
gen dioxide is represented by the following equation:
say about the concentrations of A anti C at N:04( g ) 2N02(s )
equilibrium? A student places a mixture of the two gases into a
.
b If raising the temperature of the reaction results in closed gas tube and allows the reaction to reach equi -
an equilibrium with a higher concentration of C librium at 25 C. At equilibrium, the concentration ol
than A. how will the value of K change ? N204 is found to be 5.95 X 10 1 VI and the concentra -
508. I'he following reaction occurs when steam is passed tion of NO ? s found to be 5.24 X 10 : M. What is the
over hot carbon. The mixture of gases it generates is *
equilibrium constant of the reaction?
called water gas and is useful as an industrial fuel and
as a source of hydrogen for the production of ammonia.
.
514 Consider the following equilibrium system:

=
C(.Y ) 4 H:0(g) < > CO( g ) + H2( g )
I he equilibrium constant for this reaction is
' .
NaCN(.v )
a Write a
4
^ HCN g) NaCI
HCI(g )
complete expression equilibrium
for the
( 4 ( s)

constant of this system.

4.251 X 10 - at 8( H ) k. If the equilibrium concentra -
b. The equilibrium constant for this reaction is 2.405 X
tion of Il:0( g ) is 0.1990 VI. what concentrations of
10*\ What is the concentration of HC1 remaining
CO and H: would you expect to find?
when the concentration of HCN is 0.8959 M ?
509. When nitrogen monoxide gas comes in contact with
air. it oxidi/ es to the brown gas nitrogen dioxide .
515 The following reaction is used in the industrial pro -
according to the following equation: duction of hydrogen gas:
2NO(g) 4 02 ( g ) £ 2N02(K) CH4(g) 4 H20( g) £? CO(g) 4 3H:( g )

910 APPENDIX D
 The equilibrium constant of this reaction at 298 K Mixed Review
( 25 C ) is 3.896 x 10 but at 1100 K the constant is
3.112 x 102 . .
523 IIvdrazoic acid, HN3 , is a weak acid. The [H3O 4 ) of a
.
a What do these equilibrium constants tell you about
0.102 M solution of hvdrazoic acid is 1.39 x 10" 3 M.
Determine the pH of this solution, and calculate K l at
the progress of the reaction at the two tempera - (

25 C for HN3 .
tures?
.
I) Suppose the reaction mixture is sampled at .
524 Bromoacetic acid, BrCH2COOH. is a moderately
1100 K and found to contain 1.56 M of hydrogen . weak acid. A 0.2( H ) M solution of bromoacetic acid has
3.70 x 10- 2 M of methane, and 8.27 x 10 > M of a IHO ~ concentration of 0.0192 M. Determine the pH
gaseous H20. What concentration of carbon of this solution and the Ku of bromoacetic acid at
monoxide would you expect to find? 25°C .
.
516 Dinitrogen tetroxide, N204 . is soluble in cyclohexane, . .
525 A base B, dissociates in water according to the fol -
a common nonpolar solvent . While in solution. N204 lowing equation:
B + H:0 BH * 4- OH -
can break down into NO2 according to the following
equation: ^
C’omplete the following table for base solutions with
N204( cycl( >hexaiie ) N02(m7o/ie.Vf/m* ) the characteristics given .
At 20 ( '.the following concentrations were observed
for this equilibrium reaction: Initial im at
|N 204| = 2.55 X 10- 3 M // / Equilibrium IOH ~ ] Kh // /|0+ / /> //
[ N02| = 10.4 x 10 - 3 \\ .
a 0.4(H )
* M NA 2.70 X ?M
What is the value of the equilibrium constant for this 10 4 M "

reaction? Note: the chemical equation must be bal - .

b 0.005 50 M ? M 8.45 x ? NA
anced first . 10 4 M
.
517 The reaction given in item 516 also occurs when the .
c 0.0350 M ?M ?M ?M 11.29
dinitrogen tetroxide and nitrogen dioxide are dis- .
cl ? M 0.006 28 M .
O (XX ) NA
solved in carbon tetrachloride. CC14. another nonpolar 92 M
solvent.

^ :
N:04( CC /4 ) NO ( CC/ 4 )
.
526 The solubility of benzoic acid, C H COOH, in water
^
at 25 C is 2.9 g/L The pH of this^ saturated solution is
The following experimental data were obtained at
20 C:
.
2.92. Determine Ka at 25°C for benzoic acid. ( Hint:
|N204) = 2.67 x 10 -3 M first calculate the initial concentration of benzoic
[ NO,] = 10.2 x 10 3 M
“
acid ) .
Calculate the value of the equilibrium constant for this .
527 A 0.006 50 M solution of ethanolamine,
reaction occurring in carbon tetrachloride. H 2NCH2CH 2OH, has a pH of 10.64 at 25°C. Calculate
the K [ of ethanolamine. What concentration of undis-
}

sociated ethanolamine remains at equilibrium?

Equilibrium of Acids and Bases Ka 528. The weak acid hydrogen selenide H2Se has two . .
hydrogen atoms that can form hydronium ions. The
and Kb: Chap. 18, Sec. 3 second ionization is so small that the concentration of
the resulting H3O 4 is insignificant . If the [ II3O 4 ] of a
518. At 25 C. a 0.025 M solution of formic acid. HCOOH.
is found to have a hydronium ion concentration of
0.060 M solution of Il2 Se is 2.72 x 10 ‘ M at 25°C .
what is the K „ of the first ionization?
2.03 X 10 * M. Calculate the ionization constant of
formic acid. . .
529 Pyridine C5H5N, is a verv weak base. Its Kh at 25°C is
1.78 X 10 - 9 Calculate the [ OH ~ j and pH of a 0.140 M
519. The pH of a 0.4(H) M solution of iodic acid HIO3 , is . solution. Assume that the concentration of pyridine at
0.726 at 25 C. What is the K l at this temperature ?
(
equilibrium is equal to its initial concentration because
.
520 The pH of a 0.150 M solution of hvpochlorous acid, so little pyridine is dissociated.
HCIO. is found to be 4.55 at 25 C. Calculate the Ka .
530 A solution of a monoprotic acid. HA at equilibrium is .
for HCIO at this temperature. found to have a 0.0208 M concentration of nonionized
.
521 The compound propylamine, Cl HCIHOHNIH. is a acid. The pH of the acid solution is 2.17. Calculate the
weak base. At equilibrium, a 0.039 M solution of pro- initial acid concentration and K l for this acid.{

pylamine has an OH concentration of 3.74 x 10 1 M. .

531 Pyruvic acid, CH 3COCOOH. is an important interme -
Calculate the pH of this solution and Kfy for propyl- diate in the metabolism of carbohydrates in the cells
amine. of the body. A solution made by dissolving 438 mg of
.
522 The K l of nitrous acid is 4.6 X 10 4 at 25 C. Calculate
“
pyruvic acid in 10.00 mL of water is found to have a
.
(

the [ I HO ’ ) of a 0.0450 M nitrous acid solution pH of 1.34 at 25 C. Calculate Ka for pyruvic acid.

APPENDIX D 911
532. The [ H 3O'| of a solution of acetoacetic acid . .
540. Trimethvlamine ( CH 3 X3N. dissociates in water the
Cl I 3COCI\2COO\ I . is 4.38 x 10 “ 3 M at 25°C. The
concentration of nonionized acid is 0.0731 M at
—
same way that NH 3 does by accepting a proton from
a water molecule. The [ OH ] of a 0.0750 M solution
‘

equilibrium. Calculate Ka for acetoacetic acid at 25 C. of trimethvlamine at 25 C is 2.32 x 10 3 M. Calculate

*

-
533. The Ku of 2 chloropropanoic acid , CH3CHCICOOH , the pH of this solution and the A'. /, of trimethvlamine.
is 1.48 x 1 ( ) 3. Calculate the [ H 3O * ] and the pH of a 541. Dimethylamine. (CH JNH, is a weak base similar to
0.116 M solution of 2-chloropropionic acid . Let x =
,
^
the trimethvlamine in item 540. A 5.00 x 10 3 M solu -
tion of dimethylamine has a pH of 11.20 at 25°C.
”

[ H 0 + J. The degree of ionization of the acid is too

large to ignore. If your set up is correct , you will have Calculate the A'/, of dimethylamine. Compare this A /,
a quadratic equation to solve. with the A'/, for trimethvlamine that you calculated in
534. Sulfuric acid ionizes in two steps in water solution . For item 540. Which substance is the stronger base?
the first ionization shown in the following equation, 542. Hydrazine dissociates in water solution according to
the K l is so large that in moderately dilute solution
(
the following equations:
the ionization can he considered 100 %. -
H 2 NNH 2 4 H 20( / ) H2 NNH 3 (« </ ) 4- OH ( aq )
H 2S04 4- HzO -> l LO + 4- HS04 “
H:NNH{ ( <?</ ) + H:O( 0 ^ HjNNH ( aq ) + OH ( a t/ )
The second ionization is fairlv strong, and Ka = The A /, of this second dissociation is 8.9 x 10 ~ lft, so it
'

1.3 X l () - 2; contributes almost no hydroxide ions in solution and

HS04 4- H:O H 3cr +sof can be ignored here.
^
Calculate the total [ H30 ] and pH of a 0.0788 M
+ a. The pH of a 0.120 M solution of hydrazine at 25 C
is 10.50. Calculate for the first ionization of
H 2 S04 solution . Hint: If the first ionization is 100 % ,
what will [ HSO4 | and [ H 3O * ) be? Remember to hydrazine. Assume that the original concentration
account for the already existing concentration of of H 2 NNH 2 does not change,

.
—
ICO in the second ionization . Let .v [ SO;] |.
*

535 The hydronium ion concentration of a 0.100 M solu -

h. Make the same assumption as you did in ( a ) and
calculate the [ OH ) of a 0.020 VI solution ,

c. Calculate the pH of the solution in ( b ).

tion of cyanic acid . HOCN . is found to be 5.74 x
10 3 M at 25 C. Calculate the ionization constant of
cyanic acid. What is the pH of this solution?
Equilibrium of Salts, Ksp : Chap. 18,
536. A solution of hydrogen cyanide, HCN . has a 0.025 M Sec. 4
concentration. The cyanide ion concentration is found
to be 3.16 X 10 h M .*

.
543 Silver bromate, AgBr03, is slightly soluble in water. A
a. What is the hydronium ion concentration of this saturated solution is found to contain 0,276 g AgBrCh
solution ? dissolved in 150.0 mL of water. Calculate Kip for silver
b. What is the pH of this solution? bromate.
.
c What is the concentration of nonionized HCN in 544. 2.50 L of a saturated solution of calcium fluoride
the solution ? He sure to use the correct number of leaves a residue of 0.0427 g of CaF: when evaporated
significant figures. to dryness. Calculate the Ksp of CaF2 .
cl. Calculate the ionization constant of HCN .
.
e How would you characterize the strength of HCN .
545 The Kxp of calcium sulfate, CaS04, is 9.1 x 10 6. What
as an acid ? is the molar concentration of CaS04 in a saturated
f. Determine the [ H 30 + ] for a 0.085 M solution of solution?
HCN. 546. A salt has the formula X2 Y. and its Kxp is 4.25 X 10 . 7

.
537. A 1.20 M solution of dichloroacetic acid CCLHCOOH. .
a What is the molarity of a saturated solution of the

at 25 C has a hydronium ion concentration of 0.182 M . salt?

a. What is the pH of this solution ? b. What is the molarity of a solution of AZ if its Ksp is
.
b What is the A „ of dichloroacetic acid at 25 C? the same value ?
.
c What is the concentration of nonionized
In each of the following problems, include the cal -
dichloroacetic acid in this solution ?
cl . What can you say about the strength of culated ion product with your answer.
d i c h I oroace t ic ac i d ? .
547 Will a precipitate of Ca ( OI IL form when 320. mL of a
538. Phenol, C*, HsOH . is a very weak acid . The pH of a 0.046 M solution of NaOH mixes w ith 400. mL of a
0.215 M solution of phenol at 25 C is found to be 5.61. 0.085 M CaCI 2 solution ? Ksp of Ca ( OH ) 2 is 5.5 X 10 \
(

Calculate the A / for phenol.

( .
548 20.00 mL of a 0.077 M solution of silver nitrate.
539. A solution of the simplest amino acid , glycine AgNO . is mixed w i t h 30.00 mL of a 0.043 M solution
( N I I 2CH 2COOH ), is prepared by dissolving 3.75 g in
*
of sodium acetate. NaC 2 IL,02 . Does a precipitate
250.0 mL. of water at 25 C. The pl I of this solution is form? The Ksp of AgC2 H302 is 2.5 x 10 ~ \
found to be 0.890. .
549 If you mix 100. mL of 0.036 M Pb( C2 t L,C) 2 ) 2 with
a. Calculate the molarity of the glycine solution , 50. mL of 0.074 M NaCl. will a precipitate of PbCL
h. Calculate the A „ for glycine.
'
form ? The Ksp of PbCl2 is 1.9 x Hr 4 .
912 APPENDIX D
 .
550 If 20.00 mL of a 0.0090 M solution of ( NH 4 )2S is of a 0.0035 M solution of MgBr2 is mixed with ISO. mL.
mixed with 120.00 mL of a 0.0082 M solution of of a 0.0024 M Pb( C2 H ?02): solution at 25°C.
AI ( N 03) 3, does a precipitate form ? The K % p of A 12S3 a. What is the ion product of Br and Pb2 * in the
is 2.00 X 10“ 7. mixed solution ?
b. Does a precipitate form ?
Mixed Review 563. The Ksp of Mg ( OH ) 2 at 25°C is 1.5 X 10 » » .
551. The molar concentration of a saturated calcium chro- a. Write the equilibrium equation for the dissociation
mate , CaCr( )4 . solution is 0.010 M at 25 C\ What is the of Mg( OH >2 .
Kip of calcium chromate? b. What volume of water would be required to dis-
.
552 A 10.00 mL sample of a saturated lead selenate solu - solve 0.10 g of Mg( OH )2 ?
c. Considering that magnesium hydroxide is essen -
tion is found to contain 0.00136 g of dissolved PbSc 04
at 25 C. Determine the Ksp of lead selenate. tially insoluble, why is it possible to titrate a suspen -
sion of Mg( OH ) 2 to an equivalence point with a
553. A 22.50 mL sample of a saturated copper( I ) thio- strong acid such as HCI ?
cyanate , CuSCN, solution at 25°C is found to have a
564. Lithium carbonate is somewhat soluble in water; its
4.0 x 10 6 M concentration.
.
a Determine the Ksp of CuSCN .
Ksp at 25 C is 2.51 • 10 2 .
a. What is the molar concentration of a saturated
.
b What mass of CuSCN would be dissolved in
Li 2C03 solution ?
1.0 x 103 L of solution ?
b. What mass of Li 2C03 would you dissolve in order
.
554 A saturated solution of silver dichromate. Ag2Cr207 , to make 3440 mL of saturated solution ?
has a concentration of 3.684 x 10 3 M . Calculate the .
565 A 50.00 mL sample of a saturated solution of barium
Ksp of silver dichromate. hydroxide, Ba ( OH )2 , is titrated to the equivalence
.
555 The Ksp of barium sulfite. BaS03, at 25 C is point by 31.61 ml. of a 0.3417 M solution of HCI.
-
8.0 x 10 7 . Determine the Ksp of Ba (OH )2 .
.
a What is the molar concentration of a saturated solu - 566. Calculate the Ksp for salts represented by OR that dis-
tion of BaS03 ? sociate into two ions, Q f and R . in each of the fol -
b. What mass of BaSO would dissolve in 500. mL of lowing solutions:
^
water? .
a saturated solution of QR is 1.0 M
556. The Ksp of lead ( II ) chloride at 25"C is 1.9 X 10- 4. b. saturated solution of OR is 0.50 M
What is the molar concentration of a saturated solu - c. saturated solution of QR is 0.1 M
tion at 25°C? d. saturated solution of OR is 0.001 M
.
557 The Kxp of barium carbonate at 25°C is 1.2 x 10 x. 567. Suppose that salts OR . X 2 Y. KL2 , A3Z, and D 2 E 3
form saturated solutions that arc 0.02 M in concentra -
a. What is the molar concentration of a saturated solu -
tion of BaC03 at 25°C? tion . Calculate Ksp for each of these salts.
b. What volume of water would be needed to dissolve 568. The /Cv / > at 25 C of silver bromide is 5.0 x 10 What
0.10 g of barium carbonate? is the molar concentration of a saturated AgBr solu -
tion ? What mass of silver bromide would dissolve in
558. The Ksp of SrS04 is 3.2 x 10 7 at 25°C. 10.0 I. of saturated solution at 25°C?
a. What is the molar concentration of a saturated
SrS04 solution ? 569. The Ksp at 25°C for calcium hydroxide is 5.5 X 10 6.
b. If 20.0 L of a saturated solution of SrS04 were a. C alculate the molarity of a saturated Ca ( OH ) 2 solu -
evaporated to dryness, what mass of SrSQ4 would tion .
b. W hat is the Ol I concentration of this solution ?
remain ?
c. What is the pH of the saturated solution?
.
559 The Ksp of strontium sulfite, SrS03 , is 4.0 X 10 s at 570 The Ksp of magnesium carbonate is 3.5 X 10 s at
.
25 C. If 1.0000 g of SrS03 is stirred in 5.0 L of water 25 C. What mass of MgC03 would dissolve in 4.00 L
until the solution is saturated and then filtered , what of water at 25°C?
mass of SrSG3 would remain ?
560. I he Ksp of manganese( ll ) arsenate is 1.9 x 10 11 at
25 C. What is the molar concentration of Mn ^ ( As04 )2
m a saturated solution? Note that five ions are pro-
Redox Equations: Chap 19, Sec. 2 .
duced from the dissociation of Mn3( As04)2 . Reactions in Acidic Solution
.
561 Suppose that 30.0 mL of a 0.0050 M solution of Balance the following redox equations. Assume
Sr ( NOi )2 is mixed with 20.0 ml. of a 0.010 M solution that all reactions take place in an acid environment
of K 2S04 at 25 C. t he Ksp of SrS04 is 3.2 X 10 7. where Hf and IhO are readily available.
a. What is the ion product of the ions that can poten -
tially form a precipitate? 571. Fe 4- SnCl 4 FeCh T SnCI 2
.
b Does a precipitate form ? 572. H 203 + FeS04 4- H2S04 Fe 2( S04)3 4- H 20
562. Lead ( II ) bromide. PbBr 2 , is slightly soluble in water. 573. CuS 4 HN 03 -> CU ( N 03)2 4 NO 4 S 4- H20
I is Ksp is 6.3 x 10 <y at 25 C. Suppose that 120. mL 574. K 2Cr207 + HI -> Crl 3 4- KI 4- 12 -4 H 2Q

APPENDIX D 913
Reactions in Basic Solution 598. The following reaction occurs when gold is dissolved
in aqua regia. Balance the equation.
Balance the follow ing redox equations. Assume
Au 4 HC I 4- HNO3 -> HAUCI4 4 NO 4- H:0
that all reactions take place in a basic environment
where OH and II ->0 are readily available.
575. CO; + NH2OH -4 CO 4 N: HiO
576. Bi( OH)3 4- K 2SnO;-> Bi 4- K 2Sn03 Electrochemistry: Chap. 20, Sec. 2
( Both of the potassium-tin-oxygen compounds dissoci - Use the reduction potentials in the table on page
ate into potassium ions and tin-oxygen ions. ) 915 to determine whether the follow ing reactions

Mixed Review
are spontaneous as w ritten. Report the /:{ .// for the
reactions.
'
Balance each of ( he following redox equations. 599. Cu24 4- Fe -> Fe 2 f 4- Cu
Unless stated otherwise, assume that the reaction 600. Pb2 f 4- Fe 24 Fe3 + 4- Pb
occurs in acidic solution. :
601. Mn 4- 41 TO 4- Sn 2 + -4 Mn
+
04 4- SIC 4- Sn
577. Mg N: -> Mg3N2 602. MnOj 4- Cl2 -> Mn04 4- 2CI
"
4- “

578. SO; 4- Br2 4 H2S04

H:Q -4 HBr 4- 603. I lgj+ 4 2MnO| -> 21ig 4- 2Mn04
579. ITS Cl2 —> S 4- HCI
4 604. 2Li 4 Pb -> 2Li 4- Pb2
580. PbO, 4 HBr -
PbBr2 4- Br2 4 H:G - 605. Br: 4- 20 -4 2Br 4- CU
“

581. S 4 HN03 -> NO: 4- H:S04 -f H20

*
606. S 4- 21 -4 S2 4 U

582. Nnl03 4- N:ll4 4- HCI -> N2 4- NaICl2 4- ITO ( N2H4 If a cell is constructed in w hich the following pairs
is hydrazine: do not separate it into ions. )
of reactions are possible, what would be the cath -
583. MnO: 4 H202 4 HCI -4 MnCI2 4- O; 4 H:0 ode reaction , the anode reaction, and the overall
584. ASH3 4 NaCI03 -» H3 As04 4 NaCI ( AsH3 is arsine , cell voltage?
the arsenic analogue of ammonia. NH3.)
607. Ca 2 + 4 2e 4 > Ca ’
=
585. k 2 Cr:07 4 H 2C204 4 HCI -> CrCI3 4- CO; 4 KC1 + Fe34 4 3e ~
HiO ( H ?C204 is oxalic acid: it can be treated as
608. Ag+ 4 f f? Ag
^ Fe
2IC 4 c2
oJ-.) S 4 2H 4 + 2e +5 HiS “

586. Hg(N03)2 heal HgO 4 NO; O; ( The reaction is not

in solution. ) 609. Fe34 4 r < > Fe 2 * =
Sn:+ 4 2e Sn
587. HAUCI4 4 N 2H 4 -4 Au 4 N2 4 HCI ( HAuCI4 can be
610. Cu2 + 2e -
considered as H + 4 AUC14 . )
Au3+
4
^ Cu
588. Sb 2( S04 )3 4 KMn04 4 H20 -4
H3Sb04 4 K;S()4 4 MnS04 4 H 2SC)4
4 3c
^ Au

Mixed Review
589. Mn( N03)2 4 NaBi03 4 HN03 ->
Bi(N03)2 4 HMn04 4 NaN03 4 H20 Use reduction potentials to determine w hether the
reactions in the following / 0 problems are sponta -
590. H3 AS04 Zn HCI -4 AsH 3 4 ZnCl2 4 ITO
4 4
neous.
591. KCIOj 4 HCI -> Cl; 4 H;0 4 KCI
611. Ba 4 Sn 24 -4 Ba2 * 4 Sn
592. The same reactants as in item 591 can combine in the
following way when more KCI03 is present . Balance 612. Ni 4 Hg24 -> Ni2 < 4 Hg
the equation. 613. 2Cr3 + 4 7 1120 4 bFe34 -> Cr20| 4 14IT 4 6Fe2 *
KCIO3 4 HCI -4 CT 4 CIO; 4 ITO 4 KCI 614. Hi 4 Sn -> 2CI 4 Sn24
593. MnCl3 4 ITO -4 MnCl; 4 MnO; 4 HCI 615. Al 4 3 Ag 4 -4 Al34 4 3Ag
594. NaOH 4 H20 4 Al -4 NaAI( OH) 4 4 H: in basic 616. Hg;* 4 S2 - -4 2 Hg 4 s
solution 617. Ba 4 2 Ag 4 -4 Ba 24 4 2 Ag
595. Br2 4 Ca( OH ) 2 -> CaBr 2 4 Ca( Br03 ) 2 4 ITO in 618. 21 4 Ca 2 * -4 Ca
basic solution
12 4
619. Zn 4 2M11O , -> Zn24 4 2MnO ~

596. N 20 4 NaCIO 4 NaOH -4 NaCI 4 NaNO; 4 H20 in

620. 2C r *
’ •
4 3 Mg24 4 7H;0 -4 Cr 202 4 14 H 4 4 3 Mg
basic solution
597. Balance the following reaction, which can be used to
prepare bromine in the laboratory:
HBr 4 MnO; -4 MnBr 2 4 ITO 4 Br:

914 APPENDIX D
 624. MnOj 4 8H + 4 5e Mn 2 + 4 4H 20
In the follow ing problems, yo / f Are* g / mi a pair of
reduction hal f- reactions. If a cell were constructed S + 2H + 4 2e ~ <— IBS ^
in which the pairs of half reactions were possible, - .
625 Ca 2 + 4 2e ~
w hat would be the balanced equation for the Li * + e ~
Ca
^
overall cell reaction that would occur? Write the
half - reactions that occur at the cathode and anode\
626. Br ? 4 2e ~
^
Li
2 Br
Mn 04 4 8H + 4 5e Vln 2 + 4 4H20
and calculate the cell voltage.
627. Sn 2 + 4-
2c Sn
621. Cl: + 2e if* 20 ~

Fe3> 4 e‘ Fe2 +
Ni 2* 4 2e ~ —» Ni
622. Fe3 + + 3e Fe
628. Zn 2 + 4 2c
^
Zn
~
Cr 2Oj 4- 14H + 4 6e 2Cr3+ + 7 H 20
Hg2 + 4 2c < Hg
623. MnO 4 , MnO
’

— '
"
629. Ba 2 + 4 2c ++ Ra
*

^
3 +
Al 4 3e ” AI Ca 2 + 4 2e ~ & Ca
r
630. I lg2 + 2c ~ c? 2 Hg
Cd2 + + 2r
^ Cd

For problems 599-606

Standard Standard
Electrode Electrode
Potential, Potential,
Reduction E° Reduction
Half - reaction ( in volts ) Half - reaction ( in volts )
—>
Mn:+ 4 4 H O .
MnO 4 4 8H * 4 5c ~
41.50 Fe3* 4 5c +* Fe -0.04

Au3* 4
Cl: 4 2c
3c <
—2CIAu
- • 4 1.50
4 1.36
Pb2
Sn 24
4 2e
4 2c
Ph
Sn
-0.13
-0.14
Cr20} 1411
4 + 4 6c
2Cru 4 71 BO Ni 2 * -0.26
Mn 02 4 411 * 4 2c
4 1.23 4 2c
^ Ni
Mn 24 4 2H ?0 4 1.22 Cd 2 *4 2c Cd - 0.40
-0.45
Br2 4 2c
Hg24 V 2c
2 Br 4 1.07 Fe 24 + 2e Fe
^
Hg 40.85 S 4 2c S2
^ - 0.48

-0.76
Ag * 4 c
fig; 4 4 2c -
^
2 Hg
Ag 40.80
40.80
Zn 2 ‘ 4
Al 34 4 3e
2c
? A\
Zn
1.66
Fe34 4 e
Mn 04 4 e
* 2*
Fe
MnO'
— 40.77
40.56
Mg2 * 4
Na 4 e *2 Na
4
2e
^ Mg - 2.37
- 2.71
Ca 2 + 4 2c - - 2.87
U 4 2c
Cu 2* 4 2c Cu
40.54
40.34 Ba 2 * 4 2c
Ca
Ba
^ - 2.91
S 4 2 H +( aq ) 4 2c
1 LS ( ll ( / ) 40.14 K* 4 e - K 2.93
2c- z* Li -3.04
2 H +( aq ) 4
^ H2 0.( K ) Li * 4 e

APPENDIX D 915
 APPENDIX E

Selected Answers
Matter and Change Practice Problems E Practice Problems C

Math Tutor Practice .

1 2.156 g .
1 0.125 mol Ca
.
2 85.6 cm 2. 1.83 l <r 7 mol Au
X
..
1 a 5 significant figures
.
3 I.( H ) |jm2 .
3 8.18 x 10~3
b. 4 significant figures
4. 440 g
. .
2 a 4.21 g/cm Practice Problems D
b. 16.5 g Practice Problems F
.
1 2.49 x 10"12 mol Pb
1. 9.69 mL .
2 4.2 x 10 21 mol Sn
'

Measurements 2. 1.67 g/cm ' .

3 1.66 x 1024 atoms A 1
and Calculations 3. 5.12 x 1011 mm
4. 5.2 x 103 s Practice Problems E
Practice Problems A
Math Tutor Practice
.
1 7.3 x I0 7 g Ni
~

.
1 2.75 g/cm '
.
2 7.51 x 1022 atoms S
.
2 1.14 g ..
1 a 7.45 x nr 5 g .
3 66 g Au
.
3 5.60 mL .
b 5.984102 x \ 0h nm
. .
2 a -9.11 x 103 Math Tutor Practice
Practice Problems B I . 8.25 x lO 2
)
'
. .
1 a 2.25 g
.
1 1645 cm. 0.01645 km b. 59 300 L
.
2 0.000 014 g
Atoms: The Building
..
2 a 7.2 x I01 // g

Blocks of Matter
.
h 3.98 x 103 km
Practice Problems C
1 . -17% Practice Problems A
.
2 2.7 %
Arrangement of
.
1. 35 protons 35 electrons, Electrons in Atoms
Practice Problems D
2
,C
45 neutrons
3
Practice Problems A
..
1 a 5 .
3 phosphorus-30 _ U_ J T T
b. 6
. .
1 7 7,
Is 2s *
c 4 . Practice Problems B .
2 9. 2
(1. I .
1 126 gFc
e 5 . .
2 14.7 gK
Practice Problems B
.6
f 3. 0.310 gNa .
1 a. !.V22V 22//\3A 23/763 w4s 24pHd 10
2. a 7000 cm. .
4 957 g Ni
^
5.V 25/A |Kr ]4<7105.v 25/r\ 46
b. 7000. cm b. 27. 26, 1
.
c 7000.00 cm . ,
2 a. [ Kr ]4r / <l5.v 25/J2, 2
b. 10. germanium

916 APPENDIX £
 .
3 a. l.v 22s 22pft3s23p63rf 54.v 2 Practice Problems D Practice Problems C
I ). manganese
.
1. a p block , second period . 1. a. All are in the p block . E. J .
4. a. 9. U 22s22/763s 23p6 Group 17, halogens, fluorine, and M are in the same period ,
I). argon nonmetal , high reactivity and E, G . and t. are in the same
. .
b ( J block , fourth period group.
Practice Problems C Group 11 , transition elements, .
b E should have the highest
copper, inetal . low reactivity electron affinity: E , G , and L
1. a. 1.v:2\:2/ 3 Y 23//'.V 114.s 4//
^ are most likely to form 1- ions;
1

4r/ lu5s25/766s2, [ Xe )6s 2 Practice Problems E E should have the highest elec-
. .
h Be, Mg Ca , Sr tronegativity.
1. Li; F .
2. a. [ Xe ]4 5dui6 sl
fu c The ionic radius would be
h. Au. Cs, Pt 2. All of the elements are in larger.
Group 2. Of the four, barium
has the highest atomic number
.
d E. G, and L
Math Tutor Practice and is farthest down the group. Math Tutor Practice
Therefore, barium has the
1. 85.47 a mu
2. 28.1 amu
largest atomic radius because
atomic radii increase down a
.
1. a \ s 22s22 phy pl
^
h. l .rlv22 p6
group.
3. All of the elements are in .,
c 1 sr 2.v 22//'3.v23/A3< / 1{ ]4 s 24 ph
The Periodic Law Period 3. Of the four, silicon has 4c/ < )5.v25/r
the largest atomic number and d . I522v22p63.r3p6451
Practice Problems A therefore is the farthest to the .
2 . [Ne )3j*3/r
a
right on the periodic table . b . [ Kr ] Ss }
1. Group 1 , fifth period , .s block Therefore, silicon has the small -
est atomic radius because atom - c. |Kr|4Jl 05.v2.V
2. a. ns2 ,
d. |Ar )3d 04jsr4/? 3
.
b 1 .v22s~ 2/;63.r 3ph4.v2
ic radii decrease from left to
right across a period .
c. Ca, [ Ar|4s2
Practice Problems F Chemical Bonding
Practice Problems B
. .
1 a Q is in the p block . R is in
Practice Problems A
1. fourth period , d block . Group the v block . T is in the p block ,
10 and X is in the p block .
,
2. 4r/ u5.v2 .
b O and R , and X and T are in
See table below.
the same period. Q and T are in Practice Problems C
Practice Problems C the same group.

.
1 a. 3.V23/T
.
c O would have the highest .
I H ’• N • H or*
H- N- H
ionization energy, and R would
l >. chlorine, nonmetal have the lowest .
H II
. .
2 a fourth period. /? block . d. R 2. H • S : H or H - S- H
Group 15
.
b arsenic, metalloid
.
e R

Bonding
between Electronegativity Bond -
More negative
chlorine and difference type atom

calcium 3.0 - 1.0 = 2.0 ionic chlorine

oxygen 3.5 - 3.0 = 0.5 polar-covalent oxygen
bromine 3.0 - 2.8 = 0.2 nonpolar- chlorine
covalent

APPENDIX E 917
 H 2. a. silver chloride Practice Problem F
H I ). zinc oxide
-
3. H Si H or H Si - H
: : .
a 98.09 amu
H
.
c calcium bromide b. 164.10 amu
H .
d strontium fluoride .
c 94.97 amu
.
e barium oxide cl. 95.21 amu
4. : F =: P = F or : F- P - F = .
f calcium chloride
F : F:
Practice Problems C
Practice Problems B
Practice Problems D . .
1 a 2 mol Al. 3 mol S
1. a. CuBr,. eopper ( II ) bromide b. I mol Na. 1 mol N , 3 mol O
. 0=00
l h. FcO. iron ( II ) oxide c. I mol Ha . 2 mol O. 2 mol 11
2. H -ON : . .
c PbCl, Iead ( 11 ) chloride .
2. a 150.17 g/ mol
cl. HgS. mercury ( ll ) sulfide .
b 85.00 g/ mol
Practice Problems E .
e SnF2, tin ( II ) fluoride .
c 171.35 g/ mol
I . a. linear
. .
f Fe,03 iron ( III ) oxide
2. a. copper ( II ) oxide Practice Problems I
.
b tetrahedral
h. cobalt ( III ) fluoride
c. tetrahedral .
1. a 0.0499 mol
.
c tin ( IV ) iodide
I ). 61 mol
Practice Problems F cl. iron ( ll ) sulfide
2. a. 1.53 x 1023 molecules
.
1 a. bent or angular Practice Problems C .
h 2.20 x 10* molecules
.
h trigonal pyramidal - .
3 1170 g
.
1 a. Nal .
e CuS04
Math Tutor Practice b. CaCI: f. Na2C03 Practice Problems K
.
c K:S g. Ca ( N 02 )2
1. a. 74.51 % Pb. 25.49% Cl
1. a. * Si * d. LiN 03 h. KCI 04
l >. 52.55 % Ha. 10.72 % N ,
h. Sr * .
2. a silver oxide 36.73% O

2. a. H
b. calcium hydroxide
c. potassium chlorate
2. 43.85 % H O.
3. 96.0 g O; 6.00 mol O
H - S: d. ammonium hydroxide
e. iron ( III ) chromate Practice Problems M
.
b •O :
I, potassium hypochlorite
'

1. FeS
H * C *6* H
*

2. K ,Cr,07
Practice Problems D
.
3 CaHr2
1. a. sulfur trioxide
Chemical Formulas .
b iodine trichloride Practice Problems N
and Chemical c. phosphorus pentabromide
Compounds 1. C6H6
.
2 a. Cl 4 2. 11 ,0,
Practice Problems A b. PCI3

.
1 a. KI
.
c N 203 Math Tutor Practice
.
b MgCI 2 Practice Problem E 1. 43.38% Na. 11.33% C .
45.29 % O
c. Na 2S
a. +1, -1 f. + 1 , -1 2. 61.13 % I
.
d AI2S3 b. +4, -1 g. +5, -2
e. AIN
.
c +3. -1 h. + 1 . +5, -2
d. +4. -2 i. +5. -2
.
e + 1 , +5, -2 .
j. +2 - 1

918 APPENDIX E
 Practice Problems E Practice Problems E
Chemical Equations
and Reactions 1. a. 2 Na (.v ) + CM # ) 1. a. 60.0 g NH 4 NO3

Practice Problems B
2 NaCi(.v ) .
b 27.0 g FLO
h. ( u ( .v ) + 2 AgNO ^( r/</ ) > 2. 339 g Ag
Cu ( N 03)2( tf </ ) + 2 Ag ( .v )
1 . a. calcium + sulfur
sulfide: 8Ca (s ) 4 S8(,v ) •
—
* calcium
-. ,
c. Fe 0 (s ) + 3CO( # )
.
3 2.6 kg A1

KCaS ( .v ) 2 Fe ( x ) 4 3CO:( # ) Practice Problems F

b. hydrogen + fluorine
hydrogen fluoride: I Mg ) + Practice Problems F .
1. a FLO:
F2( K ) * 2 HF(£) 1. a.no
.
h 0.500 mol N 2 H 4
.
c aluminum 4- /inc chloride .
1» no .
c 0.250 mol N 2. 1.00 mol FLO
> zinc 4 aluminum chloride;
2 A 1 ( .v ) 4 3ZnCU ( fl</ ) c. yes; Cd ( .v ) 4 21 IBr ( </ </ )
Practice Problems G
3Zn ( \ ) 4 2 AICI 3( M/ ) CdBr 2( < / r/ ) 4 I L ( ,g )
.
2 a. Liquid carbon disulfide cl. yes: Mg( .v ) 4 21 LO( g ) > 1. a. Zn
reacts with oxygen gas to pro- Mg( OH );»( </</ ) + H 2( # ) I*. 0.75 mol Ss remains
duce carbon dioxide gas and .
2 Pb .
c 2.00 mol ZnS
sulfur dioxide gas. 3. Mn 2. a. carbon
b. Aqueous solutions of sodium
chloride and silver nitrate react I ). 2.40 mol FL and 2.40 mol CO
Math Tutor Practice
to produce aqueous sodium .
c 4.85 g FL and 67.2 g CO
nitrate and a precipitate of 1. C3Hh 4 502 3C024 4 IL0
silver chloride. .
2 a. 2 KI ( n q ) 4 CL ( # ) Practice Problems H
3. N . H 4 < / ) + ( M ,g ) N 2( £ ) 4 2 K C\ { i u/ ) 4 L (.v )
2 FLO( / ) 1. 79.7 %
h. 2 AI ( .v ) 4 3H 2S04( flc/ )
AI 2( SO4 h( a q ) 4 3FL( # ) 2. 3.70 gCu
Practice Problems C
Math Tutor Practice
1. a. Word : magnesium 4
hydrochloric acid magne - Stoichiometry 1. 24.48 mol S03
sium chloride 4 hydrogen
Formula: Mg 4 11Cl > Practice Problems A
.
2 30.75 g 02
MgCL + IL
Balanced: Mg 4 2 HCI *
1. 4 mol NH 3
MgCL 4 FL 2. 10. mol KC103 States of Matter
h. Word: nitric acid 4 magne -
sium hydroxide -» magnesium Practice Problems C Practice Problems A
nitrate 4 water 1. 169 kJ
Formula: UNO3( uc/ ) 4 1. 80.6 g MgO
Mg( OH )2(.v ) > 2. 300 g CftH1206 2. 2.19 x 1( P g
Mg ( N 03)2( c/c/ ) 4 H 20( / )
Balanced: 2 HN 03( c/ c/ ) 4 Practice Problems D Math Tutor Practice
Mg ( OHMv ) >
Mg( N03)2( c / c/ ) 4 2 FLO( / ) 1. 7.81 mol HgO 1. 11.65 kJ / mol
2. ( ;»( N ) * 2 1 L( )( / ) -
2. 7.81 mol Fig 2. 74.7 kJ
Ca ( OFI ) 2( c/cy ) 4 IL ( .g )

APPENDIX E 919
 IU)
Gases
Practice Problems J .
c Ba(N03)2(.v ) ->

.
1 CO? will effuse about 0.9 times Ba+( aq ) + 2N03 ( < /r/ ); 0.5 mol
Practice Problems A as fast as HC1 Ba 2+, 1 mol N03, 1.5 mol ions

.
1 177 kPa, 1330 mm Hg
.
2 160 g/mol
Practice Problems B
.
2 7.37 x \ ( f Pa
.
3 about 235 m/ s
.
1 Yes;
Practice Problems B Math Tutor Practice Ba2+(<?r/ ) + SO ] ( aq )
~
>
BaSO 4(.v )
.
I 700.0 torr 1. r = -t\rfT
2
.
2 No

Practice Problems C 2. 094 mL

1
.
3 Yes: NV and Cl ; Ba2+(<w/ ) +
"

SO ] ~( aq ) > BaSQ 4(.v )

.
1 l ( HH ) ml . He . :
4 Ni: { aq ) + S ( aq ) >
NiS(.v )
Practice Problems D
Solutions
Practice Problems C and D
1. 941 mL
Practice Problems A-C
.
2 9I°C .
.
1 -0.426 C
1 0.282 M K 1
. .
2 0.175 //?
Practice Problems E
2 0.0750 mol
.
.
3 -118.1°C
3 0.834 L
. .
4 a -9.0°C
.
1 1.30 atm
b. 4.8 m
2. 1.29 atm
Practice Problems D
.
3 219 C 1. 22.0 m acetone Practice Problems E
.
2 3.13 g CH3OH
.
1 0.15°C
Practice Problems F
Math Tutor Practice 2. 102.7°C
.
1 26.3 mL
3. 2.0 m
2. 3.94 x 105 Pa: or 394 kPa .
1 0.7( H ) M Na2S04 4. a. 0.75°C

Practice Problems G
.
2 0.4758 M Cd(NQ3) 2 b. 1.5 m

1. 159 LN2 Practice Problems F

.
2 0.629 mol II? Ions in Aqueous
Solutions and .
1 -7.4°C

Practice Problems H Colligative Properties 2. 2.6°C

3. 0.054 m NaCI
.
1 9.10 L H2 Practice Problems A
.
2 0.313 L 02
.
1 a. NH4CI( s)
IU)
» NHJ\ Uiq ) +
Math Tutor Practice
3. 236 L NO CL ( aq ); 1 1. -4.77°C
mol MH 4 . .
Practice Problems I 1 mol CL 2 mol ions. ILO
2 106.3 C

1. 2.01 atm .
1» Na:S(.v ) 2Na* ( aq )_ +
*.
S2 ( tK / ): 2 mol Na^ I mol S: .
.
2 3.98 atm
3 mol ions

920 APPENDIX E
 Practice Problems B
Acids and Bases Reaction Energy
. .
1 a pH = 3.0
Math Tutor Practice b. pH = 5.00
Practice Problems A
.
1 Formula equation: CuS04( <i</ ) + .
c pH = 10.0 .
1 0.14 J/(g*K )
Na2S( aq )
CuS(s)
Na2 SO A( aq ) + .
d pH = 12.00 .
2 329 K

Full ionic equation: C\r +( aq ) + Practice Problems C Practice Problems B

SO ] { (!( ] ) + 2Na* ( a</ ) + S2~( aq )
\
2Na+( aq ) + SO ~( aq ) +
CuS(.v )
.
1 pH = 3.17 1. -890.8 kJ
Net ionic equation: CU2*(<I <7 ) +
.
2 pH = 1.60 .
2 2 kJ
s2 </ )
> C 'uS(.v ) .
3 pH = 5.60
. Practice Problems C
.
2 Full ionic equation: Cd^ ( a q ) + 4 pH = 12.60
2C\~( aq ) + 2Na*( <f <?) + 1. -125.4 kJ
CO\~( aq ) 2Na*( a<7 ) + Practice Problems E
2CI~( aq ) + CdC03(s) .
2 +66.4 kJ
Net ionic equation: Cd2* ( aq ) + L IH30+1 = 1 x 10 5 M '

.
3 -296.1 kJ
l
CO ~( aq ) CdC03(s) 2. [ H,0+1 = 1 x 10- 12 M
3. H,0+] = 3.2 x 10-
-
M: 2
13
Practice Problems D
OH ] = 3.2 x 10 M '

Acid- Base Titration , .

1 above 333 K
4. |H 0*| = 2.1 x 10-4 M
and pH Math Tutor Practice
Practice Problems F
Practice Problems A 1. AH = -396.0 kJ
. , "
1. | H,0~ | = 1 x UH M:
1 0.157 M CH COOH
.
2 0.0128 M H:S04
.
2 Alt ' = -441.8 kJ
[ OH- ] = 1 x 10- ln M
2. II ;0 ‘ | = 1.0 X 10 1 M:
'

Math Tutor Practice

OH ] = 1.0 X 10- 11 M Reaction Kinetics
3. H-»0+] = 3.3 x 10- 13 M: .
1 pH = 3.07
Practice Problems A
OH ] = 3.0 x 10- 2 M .
2 8.9 x 10-5 M OH
. ,
4 H O+] = 5.0 x 10 1 M;
' ..
1 a See figure below
OH- ] = 2.0 x 10-4 M
= kJ/mol
iiErVyt,ru = +150 kJ/mol
Ea = 100 kJ /mol
£/ = 250 kJ/mol

100
11

O
E 0-
Reactants
>
01 - AE
0)
c
LU

-150
Products

Forward Reverse

APPENDIX E 921
 .
b exothermic; The energy ot
Chemical Equilibrium Electrochemistry
the reactants is greater than
the energy of the products.
Practice Problems A Practice Problems A
. .
2 a
. .
—° 125
100
1 0.286
.
2 4.9 x If ) '
1. a Cr,0? + 14H+ + 3Ni -
2Crv + 3Ni2+ + 7H O:
F? = 1.33 - (-0.23) = 1.56 V
.
^
t
75
50
? 25
Ea
Products
.
3 4.36

Practice Problems B
.
b 2Fe v + H, 2Fe24 + 2 H *:
E = 0.77 - 03 = 0.77 V
" )
o> AE
c 0
LLI Reactants .
1 1.9 x K)-4 Math Tutor Practice
Forward Reverse 2. 1.6 r
x l( 5
1. 1.82 V
h. A /. tonuinl = 39 kJ /niol
Practice Problems C
. "
2 K = 1.20 V
A /;rnrrvr = -39 kJ/mol
.
c endothermic; The energy of .
1 8.9 x nr 14 niol/L
the products is greater that the
energy of the products .
2 5.7 x 10 4 mol/L Nuclear Chemistry
.
3 a.
_ 154
E;
Practice Problems D
.
Practice Problems A
. ,ili
1 : ]Es + Hc - I
?E 136 Products
1 AgBr precipitates.
.
2 PbCI2 does not precipitate. 2. 46iPm + ?,e ^ * yj + im Md
(

>
‘ffiNd
> . A£
Practice Problems B
CJ> Math Tutor Practice
ai
c
LLi Reactants |AB:] .
1 0.25 mg
..
1 a A. =
.
2 6396 years
Forward Reverse I A ][ B ]“
|D2][E2] 2 .
3 7.648 days
.
h E „ ( reverse ) = 18 kJ /mol .
b K= .
4 0.00977 mg
IDE,]2
Practice Problems B .
2 k. = 2.6 x 10
y
' . g
5 4.46 x 10 years

.
1 rale = k \ A\ 2 Math Tutor Practice
.
2 27 Oxidation- Reduction .
1 1.4 x 10 6
g chromium-51
Reactions 2. 8 half -lives or 420 000 years
Practice Problems E ( expressed with 2 significant
Practice Problems A
.
1 R = A [ L ]|M ]2 figures )
.
2 R = A'[NO,]: .
1 Cu 4- 2H,S04 -
‘
4 CuSQ 4 + SO:
+ 2 H,C)
Math Tutor Practice .
2 8HNO3 + 6KI - » 6KNO3 + 31, Organic Chemistry
+ 2NO + 4 H,Q
1. R = A [ 0,||NO ], Practice Problems A
2. R = A [ H,|; Students should Math Tutor Practice .
1 methylbutane
observe that changing the con -
centration of C:H, has no effect .
1 2MnO, + NaCIO + 2NaOH , .
2 3-ethvl-4-methvlhexane
on the rate. The rate depends -> 2NaMn
04 + NaCI + 11,0
on only the concentration of .
2 N20 + 2KC10 + 2KOH
hydrogen. 2 KCI + 2 KNO, + H,0

922 APPENDIX E
Practice Problems B
Biological Chemistry
. -
1 2 hexene
2. 2 -methyl-2-butene or
Math Tutor Practice
methyl-2 -butene .
1 leucine-histidine-aspartic
.
3 2 -methyl-3-hexene acid-tyrosine-asparagine-
.
4 2,5 -dimethvl-2,5-heptadiene tryptophan
.
2 leucine-threonine-glycine; The
Math Tutor Practice codon UGA is a stop codon, so
no more amino acids will be
.
1 CH 4N:O added.
.
2 C3HsBr
.
3 CH20

APPENDIX E 923
 GLOSSARY

aldehyde an organic compound that angular momentum quantum number

A contains the carbonyl group. the quantum number that indicates
absolute zero the temperature at — CHO ( 733 ) the shape of an orbital ( 107 )
which all molecular motion stops alkali metal one of the elements of anion an ion that has a negative
( 0 K on the Kelvin scale or Group 1 of the periodic table ( lithi- charge ( 159 )
-273.I 6°C on the Celsius scale ) ( 371 ) um. sodium, potassium, rubidium, anode the electrode on whose surface
cesium, and francium ) ( 142 ) oxidation takes place; anions
accuracy a description of how close a
measurement is to the true value of alkaline- earth metal one of the ele- migrate toward the anode, and elec-
ments of Group 2 of the periodic trons leave the system from the
the quantity measured ( 44 )
table (beryllium, magnesium, calci - anode ( 656 )
acid-base indicator a substance that
um. strontium, barium, and radium ) aromatic hydrocarbon a member of
changes in color depending on the
( 142 ) the class of hydrocarbons ( of which
pl I of the solution that the sub-
stance is in ( 511 ) alkane a hydrocarbon characterized benzene is the first member ) that
by a straight or branched carbon consists of assemblages of cyclic
acid ionization constant the term K
chain that contains only single conjugated carbon atoms and that is
(605)
bonds ( 716 ) characterized by large resonance
actinide any of the elements of the energies ( 729 )
alkenc a hydrocarbon that contains
actinide series, which have atomic Arrhenius acid a substance that
one or more double bonds ( 724 )
numbers troni 89 ( actinium. Ac )
alkyl group a group ol atoms that increases the concentration ol
through 103 ( lawrencium. Lr ) ( 136 )
forms when one hydrogen atom is hvdronium ions in aqueous solution
activated complex a molecule in an ( 473 )
removed from an alkane molecule
unstable state intermediate to the
(719) Arrhenius base a substance that
reactants and the products in the
alkyl halide a compound formed from increases the concentration of
chemical reaction ( 565 )
an alkyl group and a halogen ( fluo- hvdroxide ions in aqueous solution
activation energy the minimum
amount of energy required to start a
.
rine chlorine, bromine, or iodine ) ( 473 )

chemical reaction ( 564 )

( 732 ) -
artificial transmutation the transfor
alkyne a hydrocarbon that contains mation of atoms of one element
activity series a series of elements into atoms of another element as
one or more triple bonds ( 727 )
that have similar properties and that a result of a nuclear reaction, such
are arranged in descending order ol alpha particle a positively charged
as bombardment with neutrons
chemical activity; examples of activi - atom that is released in the disinte -
( 691 )
ty series include metals and halo - gration of radioactive elements and
that consists of two protons and two atmosphere of pressure the pressure
gens ( 285 )
neutrons ( 686) of Earth s atmosphere at sea level:
actual yield the measured amount of exactly equivalent to 760 mm I Ig
a product of a reaction ( 317 ) amine an organic compound that can
( 364 )
be considered to be a derivative of
addition reaction a reaction in which atom the smallest unit of an element
ammonia (733)
an atom or molecule is added to an that maintains the chemical proper -
unsaturated molecule ( 735 ) amino acid any one of 20 different
ties of that element ( 6. 72 )
organic molecules that contain a
adensosine diphosphate ( AI ) P ) an atomic mass unit a unit of mass that
carboxyl and an amino group and
organic molecule that is involved in describes the mass of an atom or
that combine to form proteins ( 756)
energy metabolism: composed of a molecule: it is exactly 1 / 12 of the
nitrogenous base, a sugar, and two amorphous solid a solid in which the
mass of a carbon atom with mass
phosphate groups ( 766 ) particles are not arranged with peri -
number 12 (abbreviation, amu )
odicity or order ( 338 )
adenosine triphosphate ( ATP ) an ( SO)
organic molecule that acts as the amphoteric describes a substance,
such as water, that has the proper - atomic number the number of pro-
main energy source for cell processes: tons in the nucleus of an atom: the
composed of a nitrogenous base, a ties ol an acid and the properties ol
a base ( 485 )
atomic number is the same for all
sugar, and three phosphate groups atoms of an element ( 77 )
( 766 ) anabolism the metabolic synthesis of
proteins, fats, and other large bio- atomic radius one-half of the distance
alcohol ail organic compound that con- between the center of identical
tains one or more hydroxyl groups molecules from smaller molecules:
requires energy' in the form of ATI * atoms that are not bonded together
attached to carbon atoms ( 731 ) ( 150 )
( 769 )

924 GLOSSARY
Aulbau principle the principle that bond energy the energy required to cation an ion that has a positive
states that the structure of each suc- break the bonds in 1 mol of a chem - charge ( 159 )
cessive element is obtained by adding ical compound ( 181 ) chain reaction a continuous series of
one proton to the nucleus of the atom Boyle's law the law that states that for nuclear fission reactions ( 697 )
and one electron to the lowest-energy a fixed amount of gas at a constant change of state the change of a sub-
orbital that is available ( I I I ) temperature, the volume of the stance from one physical state to
autotroph an organism that produces gas increases as the pressure of another (8 )
its own nutrients from inorganic the gas decreases and the volume CharlesA law the law that states that
substances or from the environment of the gas decreases as the pressure for a fixed amount of gas at a con -
instead of consuming other organ - of the gas increases ( 370 ) stant pressure , the volume of the gas
isms ( 766 ) -
Bronsted Lowry acid a substance that increases as the temperature of the
average atomic mass the weighted donates a proton to another sub- gas increases and the volume of the
average of the masses of all natural - stance ( 478 ) gas decreases as the temperature of
ly occurring isotopes of an element
(81 )
-
Bronsted Lowry acid -base reaction the gas decreases ( 372 )
the transfer of protons from one chemical any substance that has a
Avogadro's law the law that states reactant ( the acid ) to another ( the defined composition ( 4 )
that equal volumes of gases at the base ) ( 479 ) chemical bond the attractive force
same temperature and pressure con - Bronsted - Lowry base a substance that that holds atoms or ions together
tain equal numbers of molecules accepts a proton ( 479 ) ( 175 )
( 379)
buffered solution a solution that can chemical change a change that occurs
Avogadro's number 6.02 x 10 '. the
'
resist changes in pH when an acid or when one or more substances
number of atoms or molecules in a base is added to it ; a buffer ( 606 ) change into entirely new substances
I mol ( 83 ) with different properties ( 9 )
chemical equation a representation of

B C a chemical reaction that uses symbols

to show the relationship between the
calorimeter a device used to measure reactants and the products ( 261 )
barometer an instrument that mea - the energy as heat absorbed or
sures atmospheric pressure ( 363 )
chemical equilibrium a state of bal -
released in a chemical or physical ance in w hich the rate of a forward
benzene the simplest aromatic hydro- change ( 531 ) reaction equals the rate of the
carbon ( 729 ) capillary action the attraction of the reverse reaction and the concentra -
beta particle a charged electron emit - surface of a liquid to the surface of a tions of products and reactants
ted during certain types of radioac- solid , which causes the liquid to rise remain unchanged ( 590 )
tive decay, such as beta decay ( 686 ) or fall ( 335 ) chemical equilibrium expression the
binary acid an acid that does not con - carbohydrate any organic compound equation for the equilibrium con -
tain oxygen , such as hydrofluoric that is made of carbon, hydrogen , stant . Krq ( 592 )
acid ( 468) and oxygen and that provides nutri - chemical formula a combination of
binary compound a compound com - ents to the cells of living things ( 751 ) chemical symbols and numbers to
posed of two different elements carboxylic acid an organic acid that represent a substance ( 178 )
( 222 ) contains the carboxyl functional chemical kinetics the area of chem -
boiling the conversion of a liquid to a group ( 734 ) istry that is the study of reaction
vapor within the liquid as well as at catabolism the chemical decomposi - rates and reaction mechanisms ( 568 )
the surface of the liquid at a specific tion of complex biological sub- chemical property a property of mat -
temperature and pressure: occurs stances. such as carbohydrates,
ter that describes a substance’s abili-
when the vapor pressure of the liq - proteins, and glycogen , accompa - ty to participate in chemical
uid equals the atmospheric pressure nied by the release of energy ( 768 ) reactions ( 8 )
( 544 )
catalysis the acceleration of a chemi - chemical reaction the process bv
boiling point the temperature and cal reaction by a catalyst ( 570 ) which one or more substances
pressure at which a liquid and a gas catalyst a substance that changes the change to produce one or more dif -
arc in equilibrium ( 344 ) rate of a chemical reaction without ferent substances ( 9 )
boiling - point elevation the difference being consumed or changed signifi - chemistry the scientific study of the
between the boiling point of a liquid cantly ( 570 ) composition, structure, and proper -
in pure stale and the boiling point of catenation the binding of an element ties of matter and the changes that
the liquid in solution; the increase to itself to form chains or rings ( 712 ) matter undergoes ( 3)
depends on the amount of solute cathode the electrode on whose sur-
particles present ( 450 ) face reduction takes place ( 656 )

GLOSSARY 925
 clone an organism that iv produced by conjugate base a base that forms decay series a series of radioactive
asexual reproduction and that is w hen an acid loses a proton ( 483 ) nuclides produced by successive
genetically identical to its parent ; to continuous spectrum the uninterrupt - radioactive decay until a stable
make a genetic duplicate ( 775 ) ed broad band of all colors ( wave- nuclide is reached ( 690 )
coefficient a small whole number that lengths ) emitted by incandescent decomposition reaction a reaction in
appears as a factor in front of a for - solids ( 100 ) which a single compound breaks
mula in a chemical equation ( 263 ) control rod a neutron -absorbing rod dow n to form two or more simpler
colligative property a property that is that helps control a nuclear reaction substances ( 279 )
determined by the number of parti - by limiting the number of free neu - denature to change irreversibly the
cles present in a system but that is
independent of the properties of the
trons ( 698 )
conversion factor a ratio that is
—
structure or shape and thus the
solubility and other properties of a
particles themselves ( 446 ) derived from the equality of two dif - protein by heating, shaking , or treat -
collision theory the theory that states ferent units and that can be used to ing the protein with acid , alkali , or
that the number of new compounds convert from one unit to the other other species ( 764 )
formed in a chemical reaction is ( 40 ) density the ratio of the mass of a sub-
equal to the number of molecules copolymer a polymer made from two stance to the volume of the sub-
that collide, multiplied by a factor different monomers ( 737 ) stance: often expressed as grams per
that corrects for low -energy colli - cubic centimeter for solids and liq -
covalent bond a bond formed w hen
sions ( 562 ) uids and as grams per liter for eases
atoms share one or more pairs of
colloid a mixture consisting of tiny electrons ( 175 ) (38)
particles that are intermediate in deposition the change of state from a
critical mass the minimum mass of a
size between those in solutions and gas directly to a solid ( 346 )
fissionable isotope that provides the
those in suspensions and that are number of neutrons needed to sus- derived unit a unit of measure that is
suspended in a liquid , solid , or gas a combination of other measure-
tain a chain reaction ( 698 )
( 403) ments ( 36 )
critical point the temperature and
combined gas law the relationship diffusion the movement of particles
pressure at which the gas and liquid
between the pressure, volume, and from regions of higher density to
states of a substance become identi-
temperature of a fixed amount of cal and form one phase ( 347 ) regions of lower density ( 331 )
gas ( 374 )
critical pressure the lowest pressure at dimensional analysis a mathematical
combustion reaction the oxidation which a substance can exist as a liq - technique for studying dimensions
reaction of an element or com - of physical quantities ( 40 )
uid at the critical temperature ( 348 )
pound , in which energy as heat is
critical temperature the temperature dipole a molecule or a part of a mole -
released ( 283 )
above which a substance cannot cule that contains both positively
common - ion effect the phenomenon and negatively charged regions
exist in the liquid state ( 347 )
in which the addition of an ion com - ( 204 )
mon to two solutes brings about crystal a solid whose atoms, ions , or
molecules are arranged in a definite diprotic acid an acid that has two
precipitation or reduces ionization
( 603 ) pattern ( 338 ) ionizable hydrogen atoms in
crystal structure the arrangement of each molecule, such as sulfuric acid
composition stoichiometry calcula - ( 480 )
tions involving the mass relation - atoms, ions, or molecules in a regu -
lar way to form a crystal ( 339 ) direct proportion the relationship
ships of elements in compounds
( 299 ) crystalline solid a solid that consists ol between two variables whose ratio is
crystals ( 338 ) a constant value ( 55 )
compound a substance made up of
disaccharide a sugar formed from two
atoms of two or more different ele - cycloalkane a saturated carbon chain
monosaccharides ( 752 )
ments joined by chemical bonds ( 7 ) that forms a loop or a ring ( 718 )
disproportionation the process by
concentration the amount of a partic-
ular substance in a given quantity of
which a substance is transformed
into two or more dissimilar sub-
a mixture, solution , or ore ( 41.8 ) D stances. usually by simultaneous oxi -
condensation the change ol state from dation and reduction ( 645 )
a gas to a liquid ( 342 ) Daltons law of partial pressures the
law that states that the total pres- dissociation the separating of a mole -
condensation reaction a chemical cule into simpler molecules, atoms,
sure of a mixture of gases is equal to
reaction in which two or more mole - radicals, or ions ( 435 )
the sum of the partial pressures of
cules combine to produce water or
the component gases ( 365 ) DNA replication the process of mak -
another simple molecule ( 736. 752 )
daughter nuclide a nuclide produced ing a copy of DNA ( 772 )
conjugate acid an acid that forms
by the radioactive decay of another
when a base gains a proton ( 483)
nuclide ( 690 )

926 GLOSSARY
double -displacement reaction a reac- electron capture the process in which enzyme a type of protein that speeds
tion in which a gas, a solid precipi - an inner orbital electron is captured up metabolic reactions in plants and
tate. or a molecular compound by the nucleus of the atom that con - animals without being permanently
forms from the apparent exchange tains the electron ( 687 ) changed or destroyed ( 763 )
of atoms or ions between two com - electron configuration the arrange - equilibrium in chemistry, the state in
pounds ( 282 ) ment of electrons in an atom which a chemical reaction and the
ductility the ability of a substance to ( 111 ) reverse chemical reaction occur at
be hammered thin or drawn out into electron -dot notation an electron - the same rate such that the concen -
a wire ( 1 % ) configuration notation in which only trations of reactants and products
the valence electrons of an atom of do not change ( 342 )
the a particular element are shown , equilibrium constant a number that
E indicated by dots placed around the
element 's symbol ( IS4 )
relates the concentrations of starting
materials and products of a
effervescence a bubbling of a liquid electronegativity a measure of the reversible chemical reaction to one
caused by the rapid escape of a gas ability of an atom in a chemical another at a given temperature
rather than by boiling ( 413 ) compound to attract electrons ( 592 )
effusion the passage of a gas under ( ltd ) equilibrium vapor pressure the vapor
pressure through a tinv opening electroplating the electrolytic process pressure of a system at equilibrium
(332) of plating or coating an object with ( 343 )
elastic collision a collision between a metal ( 668 ) equivalence point the point at which
ideally elastic bodies in which the element a substance that cannot be the two solutions used in a titration
final and initial kinetic energies are separated or broken down into sim - are present in chemically equivalent
the same ( 329) pler substances bv chemical means: amounts ( 516 )
electrochemistry the branch of chem - all atoms of an element have the ester an organic compound formed by
istry that is the study of the relation
ship between electric forces and
- same atomic number ( 6 ) combining an organic acid with an
alcohol such that water is eliminated
elimination reaction a reaction in
chemical reactions ( 655 ) which a simple molecule, such as ( 734 )
electrode a conductor used to estab- water or ammonia , is removed and a ether an organic compound in which
lish electrical contact with a nun - new compound is produced (737 ) two carbon atoms bond to the same
metallic part of a circuit , such as an empirical formula a chemical formula oxygen atom ( 732 )
electrolyte ( 656 ) that shows the composition of a evaporation the change of a substance
electrode potential the difference in compound in terms of the relative from a liquid to a gas ( 335 )
potential between an electrode and numbers and kinds of atoms in the excess reactant the substance that is
its solution ( 662 ) simplest ratio ( 245 ) not used up completely in a reaction
electrolysis the process in which an end point the point in a titration at ( 312 )
electric current is used to produce a which a marked color change takes excited state a state in which an atom
chemical reaction , such as the place ( 516 ) has more energy than it does at its
decomposition of water ( 279.670 ) enthalpy change the amount of ener - ground state ( 100 )
electrolyte a substance that dissolves gy released or absorbed as heat by a extensive property a property that
in water to give a solution that con
ducts an electric current ( 405 )
- system during a process at constant
pressure ( 534 )
depends on the extent or size of a
system ( 7 )
electrolytic cell an electrochemical enthalpy of combustion the energy
device in which electrolysis takes released as heal by the complete
place when an electric current is in
the device ( 667 )
combustion of a specific amount of
a substance at constant pressure or
F
electromagnetic radiation the radia - constant volume ( 539 ) family a vertical column of the peri -
tion associated with an electric and enthalpy of reaction the amount of odic table ( 17 )
magnetic field: it varies periodically energy released or absorbed as heal fatly acid an organic acid that is con -
and travels at the speed of light ( 97 ) during a chemical reaction ( 534 ) tained in lipids, such as fats or oils
electromagnetic spectrum all of the enthalpy of solution the amount of ( 754 )
frequencies or wavelengths of elec- energy released or absorbed as heat film badge a device that measures the
tromagnetic radiation ( 97 ) when a specific amount of solute approximate amount of radiation
electron affinity the energy needed to dissolves in a solvent ( 416 ) received in a given period of time by
remove an electron from a negative entropy a measure of the randomness people who work with radiation
ion to form a neutral atom or mole- or disorder of a system ( 547 ) ( 694 )
cule ( 157 )

GLOSSARY 927
 fluid a nonsolid slate of matter in gas a form of matter that does not Heisenberg uncertainty principle the
which the atoms or molecules are have a definite volume or shape (8 ) principle that stales that determin -
free to move past each other, as in a Gay - Lussac law the law that states ing both the position and velocity of
gas or liquid ( 333) ^
that the volume occupied by a gas at an electron or any other particle
formula equation a representation of a constant pressure is directly pro- simultaneously is impossible ( 105 )
the reactants and products of a portional to the absolute tempera - Henry's law the law that states that at
chemical reaction by their symbols ture (373) constant temperature, the solubility
or formulas ( 264 ) Gay - Lussacs law of combining vol - of a gas in a liquid is directly pro-
formula mass the sum of the average umes of gases the law that states portional to the partial pressure of
atomic masses of all atoms repre - that the volumes of gases involved the gas on the surface of the liquid
sented in the formula of any mole- in a chemical change can be repre - (413)
cule. formula unit , or ion ( 237 ) sented by a ratio of small whole Hess's law the overall enthalpy
formula unit the collection of atoms numbers ( 378 ) change in a reaction is equal to the
corresponding to an ionic com - -
Geiger Miillcr counter an instrument sum of the enthalpy changes for the
pound 's formula such that the molar that detects and measures the inten - individual steps in the process ( 539 )
mass of the compound is the same sity of radiation by counting the heterogeneous composed of dissimi -
as the mass of 1 mol of formula number of electric pulses that pass lar components ( 12 )
units ( 190) between the anode and the cathode heterogeneous catalyst a catalyst that
free energy the energy in a system in a tube filled with gas ( 694 ) is in a different phase from the
that is available for work : a system ’s geometric isomer a compound that phase of the reactants (570 )
capacity to do useful work (548 ) exists in two or more geometrically heterogeneous reaction a reaction in
free-energv change the difference different configurations ( 714 ) which the reactants are in two dif -
between the change in enthalpy. A / / , Graham's law of effusion the law that ferent phases ( 568 )
and the product of the Kelvin tem - states that the rale of effusion of a heterotroph an organism that obtains
perature and the entropy change , gas is inversely proportional to the organic food molecules bv eating
which is defined as 7AS, at a con - square root of the gas's density other organisms or their byproducts
stant pressure and temperature ( 548 ) ( 387 ) and that cannot synthesize organic
freezing the change of stale in which ground state the lowest energy state compounds from inorganic materials
a liquid becomes a solid as energy as of a quantized system ( 1 ( H ) ) ( 766 )
heat is removed (336 ) group a vertical column of elements in homogeneous describes something
freezing point the temperature at the periodic table: elements in a that has a uniform structure or com -
which a solid and liquid arc in equi - group share chemical properties ( 17 ) position throughout ( 12 )
librium at 1 atm pressure: the tem - homogeneous catalyst a catalyst that
perature at which a liquid substance is in the same phase as the reactants
freezes ( 345 )
freezing- point depression the differ -
H arc ( 570 )
homogeneous reaction a reaction in
ence between the freezing points of half-cell a single electrode immersed which all of the reactants and prod -
a pure solvent and a solution , which in a solution of its ions ( 656 ) ucts are in the same phase ( 562 )
is directly proportional to the half - life the time required for half of Huiid's rule the rule that states that
amount of solute present ( 44S ) a sample of a radioactive substance for an atom in the ground stale, the
frequency the number of cycles or to disintegrate by radioactive decay number of unpaired electrons is the
v ibrations per unit of lime; also the or by natural processes ( 688 ) maximum possible and these
number of waves produced in a half - reaction the part of a reaction unpaired electrons have the same
given amount of time ( 98) that involves only oxidation or spin ( 112 )
functional group the portion of a mol - reduction ( 633 ) hybrid orbitals orbitals that have the
ecule that is active in a chemical halogen one of the elements of Group properties to explain the geometry
reaction and that determines the 17 ( fluorine, chlorine, bromine , of chemical bonds between atoms
properties of many organic com - iodine, and astatine ); halogens com - ( 202 )
pounds ( 730 ) bine with most metals to form salts hybridization the mixing of two or
( 147 ) more atomic orbitals of the same
heat the energy transferred between atom to produce new orbitals;
G objects that are at different temper- hybridization represents the mixing
atures; energy is always transferred of higher- and lower-energy orbitals
-
gamma ray the high energy photon -
from higher temperature objects to to form orbitals of intermediate
emitted by a nucleus during fission
and radioactive decay ( 687 )
-
lower temperature objects until energy ( 201 )
thermal equilibrium is reached ( 532 )

928 GLOSSARY
hydration the strong affinity of water inverse proportion the relationship
molecules for particles of dissolved between two variables whose prod- L
or suspended substances that causes uct is constant ( 56)
lanthanide a member of the rare -
electrolytic dissociation ( 411 ) ion an atom, radical, or molecule that earth series of elements, whose
hydrocarbon an organic compound has gained or lost one or more elec- atomic numbers range from 58 ( ceri -
composed only of carbon and trons and has a negative or positive um ) to 71 ( lutetium) ( 136 )
hydrogen ( 712 ) charge ( 153 ) lattice energy the energy associated
hydrogen bond the intermolecular ionic bond a force that attracts elec - with constructing a crystal lattice
force occurring when a hydrogen trons from one atom to another, relative to the energy of all con -
atom that is bonded to a highly elec- which transforms a neutral atom stituent atoms separated by infinite
tronegative atom of one molecule is into an ion ( 175 ) distances ( 192 )
attracted to two unshared electrons ionic compound a compound com - law of conservation of mass the law
of another molecule ( 206 ) posed of ions bound together by that states that mass cannot be cre-
hydrolysis a chemical reaction electrostatic attraction ( 190 ) ated or destroyed in ordinary chemi -
between water and another sub- ioni/ ation the process of adding cal and physical changes ( 68)
stance to form two or more new or removing electrons from an law of definite proportions the law
substances; a reaction between atom or molecule, which gives the that states that a chemical com-
water and a salt to create an acid or atom or molecule a net charge pound always contains the same ele -
a base ( 60S, 752) ( 153.441 )
ments in exactly the same
hydronium ion an ion consisting of a ionization energy the energy required proportions by weight or mass ( 68 )
proton combined with a molecule < 4 to remove an electron from an atom law of multiple proportions the law
water: ( 441 ) or ion ( abbreviation. IE ) ( 153 ) that states that when two elements
hypothesis an explanation that is isomer one of two or more com - combine to form two or more com -
based on prior scientific research or pounds that have the same chemical pounds, the mass of one element
observations and that can be tested composition but different structures that combines with a given mass of
(30) ( 712 ) the other is in the ratio of small
isotope an atom that has the same whole numbers ( 68 )
number of protons ( or the same .
Lewis acid an atom. ion or molecule
atomic number ) as other atoms ol that accepts a pair of electrons ( 481 )
the same element do but that has a Lewis acid-base reaction the forma -
ideal gas an imaginary gas whose par - different number of neutrons ( and tion of one or more covalent bonds
ticles are infinitely small and do not thus a different atomic mass) between an electron-pair donor and
interact with each other ( 329 ) ( 78 ) an electron -pair acceptor ( 482 )
ideal gas constant the proportionality
constant that appears in the equa - . .
Lewis base an atom ion or molecule
that donates a pair of electrons ( 482 )
tion of stale for 1 mol of an ideal
gas: R - 0.082 057 84 L • at m/ mol •
J Lewis structure a structural formula
in which electrons are represented
K (384) joule the unit used to express energy:
by dots; dot pairs or dashes between
ideal gas law the law that states the equivalent to the amount of work two atomic symbols represent pairs
mathematical relationship of pres- done by a force of I N acting
in covalent bonds ( 185 )
.
sure ( / 0 volume ( V7 ). temperature through a distance of I m in the
.
( /'). the gas constant ( R ) and the direction of the force ( abbreviation, limiting reactant the substance that
controls the quantity of product that
number of moles of a gas ( / / ): P V = J) (531)
HR / ( 383 ) can form in a chemical reaction
( 312 )
immiscible describes two or more liq-
uids that do not mix with each other
( 412 )
K line-emission spectrum a diagram or
graph that indicates the degree to
ketone an organic compound in which which a substance emits radiant
intensive property a property that
a carbonyl group is attached to two energy with respect to wavelength
does not depend on the amount of ( 100)
'

matter present, such as pressure, alkyl groups: obtained by the oxida -

temperature, or density ( 7 ) tion of secondary alcohols ( 733 ) lipid a type of biochemical that docs
kinetic-molecular theory a theory that not dissolve in water, including fats
intermediate a substance that forms
explains that the behavior of physi - and steroids: lipids store energy and
in a middle stage of a chemical reac -
cal systems depends on the com- make up cell membranes ( 754 )
tion and is considered a stepping
stone between the parent substance bined actions of the molecules liquid the state of matter that has a
and the final product ( 562 ) constituting the system ( 329 ) definite volume but not a definite
shape ( 8 )

GLOSSARY 929
 London dispersion force Ihe inlermol - metalloid an element that has proper - mole ratio a conversion factor that
ecular attraction resuhing from the ties of both metals and nonmetals; relates the amounts in moles of any
uneven distribution of electrons and sometimes referred to as a semicon - two substances involved in a chemi -
the creation of temporary dipoles ductor ( 19) cal reaction ( 300 )
( 207 ) millimeters of mercury a unit of pres- molecular compound a chemical com -
sure ( 364 ) pound whose simplest units are mol-
miscible describes two or more liquids ecules ( 178 )
that can dissolve into each other in molecular formula a chemical formula
various proportions ( 412 ) that shows the number and kinds of
.
magic numbers the numbers ( 2 8. 20.
mixture a combination of two or atoms m a molecule, but not the
28 50, 82, and 126) ih .ii represent more substances that are not chemi - arrangement of the atoms ( 178 )
the number of particles in an extra
cally combined ( I I ) molecule the smallest unit of a sub-
stable atomic nucleus that has com-
model a pattern, plan, representation, stance that keeps all of the physical
pleted shells of protons and neu -
or description designed to show the and chemical properties of that sub-
trons ( 683 )
structure or workings of an object, stance; it can consist of one atom or
magnetic quantum number the quan- two or more atoms bonded together
system, or concept ( 31 )
tum number that corresponds to the ( 178 )
alignment of the angular momentum moderator a material that slows the
velocity of neutrons so that they monatomic ion an ion formed from a
component with a magnetic field
may be absorbed by the nuclei (698 ) single atom ( 220 )
( 108 )
molal boiling- point constant a quanti - monomer a simple molecule that can
main- group element an element in
ty calculated to represent the boil- combine with other like or unlike
-
the v-block or /7 -block of the period
ing-point elevation of a 1 - molal molecules to make a polymer ( 737 )
ic table ( 146 )
solution of a nonvolatile, nonelec - monoprotic acid an acid that can
malleability the ability of a substance
to be hammered or beaten into a
tronic solution ( 450 ) donate only one proton to a base
molal freezing-point constant a quan- ( 479 )
sheet ( 196 )
tity calculated to represent the monosaccharide a simple sugar that is
mass a measure of the amount of
matter in an object ( 6 ) -
freezing point depression of a
1 - molal solution of a nonvolatile ,
the basic subunit of a carbohydrate
(751)
mass defect the difference between nonelectrolyte solute ( 448 ) multiple bond a bond in which the
the mass of an atom and the sum
molality the concentration of a solu- atoms share more than one pair of
of the masses of the atom 's
tion expressed in moles of solute per electrons, such as a double bond or
protons, neutrons, and electrons
kilogram of solvent ( 422 ) a triple bond ( 187 )
( 681 )
molar enthalpy of formation the
mass number the sum of the numbers
amount of energy as heat resulting
of protons and neutrons that make
up the nucleus of an atom ( 78 )
from the formation of I mol of a
substance at constant pressure ( 537 )
N
matter anything that has mass and natural gas a mixture of gaseous
molar enthalpy of fusion the amount
takes up space ( 6 ) of energy as heat required to change hydrocarbons located under the sur -
melting the change of state in which a I mol of a substance from solid to face of Earth, often near petroleum
solid becomes a liquid by adding liquid at constant temperature and deposits; used as a fuel ( 723 )
enerev' as heat or changing pressure pressure ( 346 ) net ionic equation an equation that
( 338 )
molar enthalpy of vaporization the includes only those compounds and
melting point the temperature and amount of energy as heat required to ions that undergo a chemical change
pressure at which a solid becomes a evaporate I mol of a liquid at con- in a reaction in an aqueous solution
liquid ( 338 ) stant pressure and temperature ( 345) ( 439 )
metabolism the sum of all chemical molar mass the mass in grams of 1 mol neutralization the reaction of the ions
processes that occur in an organism of a substance ( 83 ) that characterize acids ( hydronium
( 766 ) ions ) and the ions that characterize
molarity a concentration unit of a
metal an element that is shiny and solution expressed as moles of bases ( hydroxide ions ) to form
that conducts heat and electricity solute dissolved per liter of solution water molecules and a salt ( 489 )
well ( 18 ) ( 418 ) newton the SI unit for force; the force
metallic bond a bond formed by the mole the SI base unit used to measure that will increase the speed of a 1 kg
attraction between positively the amount of a substance whose mass by 1 m/s each second that the
charged metal ions and the electrons number of particles is the same as force is applied ( abbreviation, N )
around them ( 195 ) ( 362 )
the number of atoms of carbon in
-
exactly 12 g of carbon 12 ( 83 )

930 GLOSSARY
noble gas one of the elements of nucleic acid an organic compound , oxidizing agent the substance that
Group 18 of the periodic table ( heli - either RNA or DNA. whose mole- gains electrons in an oxidation -
um. neon , argon , krypton , xenon , cules are made up of one or two reduction reaction and that is
and radon ); noble gases are unreac- chains of nucleotides and carry reduced ( 642 )
tive ( 117 ) genetic information ( 77( 1 ) oxyacid an acid that is a compound of
noble -gas configuration nucleon a proton or neutron ( 681 ) hydrogen , oxygen , and a third ele-
an outer main energy level fully nuclide an atom that is identified by ment . usually a nonmetal (469)
occupied , in most cases, by eight the number of protons and neutrons oxyanion a polyatomic ion that con -
electrons (118 ) in its nucleus ( 79, 681 ) tains oxygen ( 225 )
nomenclature a naming system ( 222 )
nonelectrolyte a liquid or solid sub -
stance or mixture that does not
allow an electric current ( 406 )
0 P
nonmetal an element that conducts orbital a region in an atom where parent nuclide a radionuclide that
heat and electricity poorly and that there is a high probability of finding yields a specific daughter nuclide as
docs not form positive ions in an electrons ( 106 ) a later member of a radioactive
electrolytic solution ( 19 ) order in chemistry, a classification ol series ( 690 )
nonpolar covalent bond a covalent chemical reactions that depends on partial pressure the pressure of each
bond in which the bonding electrons the number of molecules that gas in a mixture ( 365 )
are equally attracted to both bonded appear to enter into the reaction pascal the SI unit of pressure: equal
atoms ( 176 ) ( 572 ) to the force of I N exerted over an
nonvolatile substance a substance that organic compound a covalently bond -
ed compound that contains carbon , ( 364 )
.
area of 1 nr ( abbreviation Pa )
has little tendency to become a gas
under existing conditions ( 446 ) excluding carbonates and oxides Pauli exclusion principle the principle
'
( ll )
that states that two particles of a
nuclear binding energy the energy
released when a nucleus is formed osmosis the diffusion of water or certain class cannot be in exactly the
from nucleons ( 682 ) another solvent from a more dilute same energy state ( 112 )
nuclear fission the splitting of the solution (of a solute ) to a more con - percentage composition the percent -
nucleus of a large atom into two or centrated solution ( of the solute ) age by mass of each element in a
more fragments: releases additional through a membrane that is perme- compound ( 243)
able to the solvent ( 452 )
neutrons and energy ( 697) percentage error a figure that is calcu -
nuclear forces the interaction that osmotic pressure the external pres- lated by subtracting the accepted
binds protons and neutrons, protons sure that must be applied to stop value from the experimental value,
and protons, and neutrons and neu - osmosis ( 452 ) dividing the difference by the
trons together in a nucleus ( 76 ) oxidation a reaction that removes one accepted value, and then multiply -
nuclear fusion the combination of the or more electrons from a substance ing by 100 ( 45 )
nuclei of small atoms to form a larg - such that the substance s valence or percentage yield the ratio of the actu -
er nucleus: releases energy ( 699 ) oxidation stale increases ( 632 ) al yield to the theoretical yield , mul -
nuclear power plant a facility that oxidation number the number ol elec- tiplied by 100 ( 317 )
trons that must be added to or period in chemistry, a horizontal row
uses heat from nuclear reactors to
removed from an atom in a com - of elements in the periodic table
produce electrical energy ( 698 )
bined state to convert the atom into ( 17 )
nuclear radiation the particles that the elemental form ( 232 )
are released from the nucleus during periodic law the law that stales that
radioactive decay, such as neutrons , oxidation state the condition of an the repeating chemical and physical
electrons, and photons ( 685 ) atom expressed by the number of properties of elements change peri -
electrons that the atom needs to odically with the atomic numbers of
nuclear reaction a reaction that
reach us elemental form ( 232 ) the elements ( 135 )
affects the nucleus of an atom ( 684 )
oxidation - reduction reaction any periodic table an arrangement of the
nuclear reactor a device that uses chemical change in which one
controlled nuclear reactions to pro- elements in order of their atomic
species is oxidized ( loses electrons ) numbers such that elements with
duce energy or nuclides ( 698 ) and another species is reduced similar properties fall in the same
nuclear shell model a model which ( gains electrons ): also called redox column , or group ( 135 )
represents nucleons as existing in reaction ( 633 )
different energy levels, or shells, in petroleum a liquid mixture of com -
oxidized describes an element that plex hydrocarbon compounds: used
the nucleus ( 683 ) has lost electrons and that has widely as a fuel source ( 723 )
nuclear waste waste that contains increased its oxidation number ( 632 )
radioisotopes ( 696 )

GLOSSARY 931
 pll a value lhal is used to express the polymer a large molecule that is
acidity or alkalinity ( basicity ) of a formed by more than five R
system; each whole number on the monomers, or small units ( 737 )
radioactive dating the process by
scale indicates a tenfold change in polyprotic acid an acid that can which the approximate age of an
acidity; a pH of 7 is neutral, a pH of donate more than tine proton per object is determined based on the
less than 7 is acidic, and a pH of molecule ( 479 ) amount of certain radioactive
greater than 7 is basic ( 503 )
polysaccharide one of the carbohy- nuclides present ( 695 )
pll meter a device used to determine drates made up of long chains of sim- radioactive decay the disintegration
the pH ol a solution by measuring ple sugars: polysaccharides include of an unstable atomic nucleus into
the voltage between the two elec - starch, cellulose, and glycogen ( 753 ) one or more different nuclides,
trodes that arc placed in the solu -
positron a particle that has the same accompanied by the emission of
tion ( 512 )
mass and spin as an electron but radiation, the nuclear capture or
phase m chemistry, one ol the four that has a positive charge ( 6X6 ) ejection of electrons, or fission ( 685)
states or conditions in which a sub -
precipitate a solid that is produced as radioactive nuclide a nuclide that con -
stance can exist : solid, liquid, gas. or
a result of a chemical reaction in tains isotopes that decay and that
plasma: a part of matter that is uni -
solution ( 262 ) emit radiation ( 685 )
form ( 542 )
precision the exactness of a measure - radioactive tracer a radioactive mate -
phase diagram a graph of the rela-
ment ( 44 ) rial that is added to a substance so
tionship between the physical state
of a substance and the temperature pressure the amount of force exerted that its distribution can be detected
per unit area of a surface (361 ) later ( 695)
and pressure of the substance ( 347 )
primary standard a highly purified rale law the expression that shows
photoelectric effect the emission of
solid compound used to check the how the rate of formation of prod-
electrons from a material when light
concentration of a known solution uct depends on the concentration of
of certain frequencies shines on the
in a titration ( 517 ) all species other than the solvent
surface of the material ( 99)
principal quantum number the quan - that take part in a reaction ( 572 )
photon a unit or quantum of light: a
tum number that indicates the ener - rate - determining step in a multistep
particle of electromagnetic radiation
that has zero rest mass and carries a gy and orbital of an electron in an chemical reaction, the step that has
atom ( 107 ) the lowest velocity, which deter -
quantum of energy ( KM ) )
product a substance that forms in a mines the rate of the overall reac-
physical change a change of matter tion ( 576 )
from one form to another without a chemical reaction ( 9)
protein an organic compound that is reactant a substance or molecule that
change in chemical properties ( 7 )
made of one or more chains of participates in a chemical reaction ( 9 )
physical property a characteristic of a
amino acids and that is a principal reaction mechanism the way in which
substance that does not involve a
component of all cells ( 757 ) a chemical reaction takes place:
chemical change, such as density,
color, or hardness ( 7 ) pure substance a sample of matter, expressed in a series of chemical
either a single element or a single equations ( 561 )
plasma in physical science, a state of
matter that starts as a gas and then compound, that has definite chemi- reaction rate the rate at which a
cal and physical properties ( 13 ) chemical reaction takes place: mea -
becomes ionized: it consists of free -
moving ions and electrons, it takes sured by the rale of formation of the
on an electric charge, and its prop- product or the rate of disappearance
erties differ from those of a solid,
liquid, or gas ( 8 )
Q of the reactants ( 568 )
reaction stoichiometry calculations
quantity something that has magni- involving the mass relationships
pOH tile negative of the common log-
arithm of the hydroxide ion concen - tude. size, or amount ( 33 ) between reactants and products in a
tration of a solution ( 503) quantum the basic unit of electromag- chemical reaction ( 299 )
netic energy; it characterizes the real gas a gas that does not behave
polar describes a molecule in which
the positive and negative charges wave properties of electrons ( 99 ) completely like a hypothetical ideal
are separated ( 176 ) quantum number a number that spec- gas because of the interactions
ifies certain properties of electrons between the gas molecules ( 332 )
polar covalent bond a covalent bond
( 107) redox reaction [ see oxidation -
in which a pair of electrons shared
bv two atoms is held more closely quantum theory the study of the reduction reaction ] ( 633 )
by one atom ( 176 ) structure and behavior of the atom reduced describes a substance that
polyatomic ion an ion made of two or and of subatomic particles from the has gained electrons, lost an oxygen
view that all energy conics in liny, atom, or gained a hvdrogcn atom
more atoms ( 194 )
indivisible bundles ( 105 ) ( 633)

932 GLOSSARY
reducing agent a substance that has scientific notation a method of solution equilibrium the physical state
the potential to reduce another sub- expressing a quantity as a number in which the opposing processes of
stance ( 642 ) multiplied bv 10 to the appropriate dissolution and crystallization of a
reduction a chemical change in which power ( 50 ) solute occur at equal rates
electrons are gained, either by the scintillation counter an instrument (408)
removal of oxygen , the addition of that converts scintillating light into solvated describes a solute molecule
hydrogen , or the addition of elec- an electrical signal for detecting that is surrounded by solvent mole-
trons ( 633) and measuring radiation ( 694 ) cules ( 415 )
reduction potential the decrease in -
self ionization of water a process in solvent in a solution, the substance in
voltage that takes place when a pos - which two water molecules produce which the solute dissolves ( 402 )
itive ion becomes less positive or a hvdronium ion and a hydroxide specific heat the quantity of heat
neutral or when a neutral atom ion by transfer of a proton (499 ) required to raise a unit mass of
becomes negative ion ( 662 ) semipermcablc membrane a mem - homogeneous material 1 K or 1 °C in
rein the quantity of ionizing radiation brane that permits the passage of a specified way given constant pres-
that does as much damage to human only certain molecules ( 452 ) sure and volume ( 532)
tissue as I roentgen of high -voltage shielding a radiation -absorbing mater - spectator ions ions that are present in
X rays does ( 693 ) ial that is used to decrease radiation a solution in w hich a reaction is tak -
resonance the bonding in molecules leakage from nuclear reactors ( 698 ) ing place but that do not participate
or ions that cannot be correctly rep- SI Le Systeme International d ' Unites, in the reaction ( 439 )
resented by a single Lewis structure or the International System of t Hits, spin quantum number the quantum
( 189 ) which is the measurement system number that describes the intrinsic
reversible reaction a chemical reac- that is accepted worldwide ( 33 ) angular momentum ol a particle
tion in which the products re - form significant figure a prescribed decimal ( 110 )
the original reactants ( 266. 589) place that determines the amount of standard electrode potential the
roentgen a unit of radiation dose of X rounding off to be done based on the potential developed by a metal or
rays or gamma rays that is equal to precision of the measurement ( 46 ) other material immersed in an elec-
the amount of radiation that will single bond a covalent bond in which trolyte solution relative to the
produce 2.58 x 1 ( H of ions per kilo- two atoms share one pair of elec- potential of the hydrogen electrode,
gram ol air at atmospheric pressure trons ( 185 ) which is set at zero ( 663 )
(693) single -displacement reaction a reac- standard solution a solution of known
tion in which one element or radical concentration , expressed in terms of
takes the place of another element the amount of solute in a given
S or radical in a compound ( 281 ) amount of solvent or solution
(517)
solid the state of matter in which the
salt an ionic compound that forms volume and shape of a substance are standard temperature and pressure
when a metal atom or a positive fixed ( 8 ) lor a gas. the temperature ol 0°C
radical replaces the hydrogen of an and the pressure 1.00 atm ( 364 )
acid ( 231.489) solubility the ability of one substance
to dissolve in another at a given strong acid an acid that ionizes com -
saponification a chemical reaction in temperature and pressure; pletely in a solvent ( 474 )
which esters ol fatty acids react with expressed in terms of the amount of strong electrolyte a compound that
a strong base to produce glycerol solute that will dissolve in a given completely or largely dissociates in
and a fatty acid salt : the process that amount of solvent to produce a sat - an aqueous solution , such as soluble
is used to make soap ( 754 ) urated solution ( 410 ) mineral salts ( 442 )
saturated hydrocarbon an organic solubility product constant the equi - structural formula a formula that indi -
compound formed only by carbon librium constant for a solid that is in cates the location of the atoms,
and hvdrogen
’
linked bv single bonds equilibrium with the solid s dis- groups, or ions relative to one
( 716 )
solved ions ( 613 ) another in a molecule and that indi -
saturated solution a solution that can - soluble capable of dissolving in a par - cates the number and location of
not dissolve any more solute under chemical bonds ( 185. 712 )
ticular solvent ( 401 )
the given conditions ( 409) structural isomers two or more com -
solute in a solution , the substance that
scientific method a series of steps fol - dissolves in the solvent ( 402 ) pounds that have the same number
lowed to solve problems, including and kinds of atoms and the same
collecting data , formulating a solution a homogeneous mixture ol
molecular weight but that differ in
two or more substances uniformly
hypothesis, testing the hypothesis, the order in which the atoms are
and staling conclusions ( 29 ) dispersed throughout a single phase
( 402 ) attached to one another ( 713 )

GLOSSARY 933
 sublimation the process in which a thermochemistry the branch of chem -
solid changes direct!) into a gas ( the istry that is the study of the energy V
term is sometimes also used tor the changes that accompany chemical
valence electron an electron that is
reverse process ) ( 346 ) reactions and changes of state ( 531 )
found in the outermost shell of an
substitution reaction a reaction in titration a method to determine the atom and that determines the atom s
which one or more atoms replace concentration of a substance in solu - chemical properties ( 160 )
another atom or group of atoms in a tion by adding a solution of known
vaporization the process by which a
molecule ( 735 ) volume and concentration until the
liquid or solid changes to a gas ( 335 )
supercooled liquid a liquid that is reaction is completed , which is usu -
ally indicated bv a change in color volatile liquid a liquid that evaporates
cooled below its normal freezing readily or at a low temperature
point without solidifying ( 33S ) ( 515) '
( 343 )
supersaturated solution a solution transition element one of the metals
that can use the inner shell before voltaic cell a primary cell that consists
that holds more dissolved solute
of two electrodes made of different
than is required to reach equilibri - using the outer shell to bond ( 144 )
metals immersed in an electrolyte;
um at a given temperature ( 404 ) transition interval the range in con -
used to generate voltage ( 658 )
surface tension the force that acts on centration over which a variation in
the surface of a liquid and that tends a chemical indicator can be volume a measure of the size of a
to minimize the area of the surface observed ( 512 ) body or region in three -dimensional
( 335 )
space ( 37 )
transmutation the transformation of
VSEPR theory a theory that predicts
suspension a mixture in which parti - atoms of one element into atoms of
cles of a material are more or less a different element as a result of a some molecular shapes based on the
nuclear reaction (6S4 ) idea that pairs of valence electrons
evenly dispersed throughout a liquid
or gas ( 403 ) surrounding an atom repel each
transuranium element a synthetic
other ( 197 )
synthesis reaction a reaction in which element whose an atomic number is
two or more substances combine to greater than that of uranium ( atom -
form a new compound ( 276 ) ic number 92 ) ( 692 )
system a set ol particles or interacting triple point the temperature and pres- W
components considered to be a dis - sure conditions at which the solid ,
wavelength the distance from any
tinct physical entity for the purpose liquid , and gaseous phases of a sub-
point on a wave to an identical point
of study ( 29 ) stance coexist at equilibrium ( 347 )
on the next yvave ( 97 )
triprotie acid an acid that has three
weak acid an acid that releases lew'
ioni / able protons per molecule , such
hydrogen ions in aqueous solution
T as phosphoric acid ( 480 )
( 474 )
weak electrolyte a compound that dis-
temperature a measure of hoyv hot
sociates only t « » a small extent in
( or cold ) something is; specifically, a
measure of the average kinetic ener -
U aqueous solution ( 443 )
gy of the particles in an object ( 531 ) unit cell the smallest portion of a weight a measure of the gravitational
theoretical yield the maximum crystal lattice that shows the three - force exerted on an object; its value
can change w ith the location of the
amount of product that can be pro - dimensional pattern o! the entire
duced from a given amount of reac- lattice ( 339 ) object in the universe ( 35 )
tant ( 317 ) unsaturated hydrocarbon a hydrocar - word equation an equation in which
theory an explanation for some phe- bon that has available valence the reactants and products in a
nomenon that is based on observa - bonds, usually from double or triple chemical reaction are represented
tion , experimentation , and bonds with carbon ( 724 ) by yvords ( 263 )
reasoning ( 31 ) unsaturated solution a solution that
thermochemical equation an equation contains less solute than a saturated
that includes the quantity of energy solution does and that is able to dis -
as heat released or absorbed during solve additional solute ( 409 )
the reaction as written ( 535 )

934 GLOSSARY
 INDEX

Page references followed b \ hvdronium and hydroxide industrial production of. 671 net ionic equations, 439 -440
/ refer to figures. Page refer - .
ions in 501-502 oxides, 835.835/ osmotic pressure. 452-453 .
ences followed by / refer to industrial. 470-471 properties. 18/, 808- 809, 452/
tables. ionization constants. 808/ 809/ 810/ precipitation reactions.
605-606. 606/, 628- 629 in water purification . 437- 440. 437 /. 438/
Lewis, 481-482.482/ 273 -274 standard solutions 517 .
monoprotic and polvprotic. amalgams. 402/, 802 /’
A 479- 481, 480/ amines, 731 /, 733
strong and weak elec-
trolytes, 442- 443, 442 /
absolute zero. 371 neutralization reactions 468 . . amino acids v a pur- pressure lowering,
absorption. 102. 102 / 472. 487-489, 488/ . chemical structures of 756 . . 446 - 447. 446/ 447/
accuracy, 44- 46. 44 / 517-521 .
756/ 819.819/ area, units of. 854 /
acetic acid nomenclature, 230 231.230/, in the genetic code 780 . argon. 114 - 115, 117 /, 118
as buffer. 606- 607 468- 469. 468/. 469/ in peptides and proteins, .
Aristotle 43. 67
common- ion effect in. .
organic 474- 475 757-758.758/ aromatic hydrocarbons, 729
603- 604, 604/
hydrolysis of ions in. 610/
properties 468 .
strength of. 474 - 475. 474 /.
synthesis of, 774
ammonia
Arrhenius, Svante 473
Arrhenius acids and bases,
611 484- 485.485 /. 501 /, 509 in amines. 733 .
473 -476 473/ 474 / 475 / . .
ionization constant. .
actinides 136. 148. 157/ as base, 475. 475 / 482 . 476/ 482 /
605— 607, 606/ activated complexes, 565-567. oxidation of, 309 arsenic, 118/, 139.229,
properties. 471 565/ .
polarity of 205, 205/ .
828 - 829 829/
strength of. 474 - 475. 475/ activation energy. 465/ 564 production of, 597. 598 600 artificial transmutations.
484 567. 564/ 565/ 764. 764 / structure of, 199, 199/ 202 691- 692, 691/ 692/ 692/
acetone, 746 active sites, 763 ammonium ions, 194, 194 /, asbestos, 825
acetylene. 727 activity series, 285 287. 286/ 610- 612.611/ atmospheres ( units ) . 364- 365 ,
acid-base indicators actual yield 317. amorphous solids. 338. 341 364 /
. .
colors of 500/ 512/ 513/ addition polymers 738. 738 /. amphoteric compounds, atmospheric pressure,
equivalence point and, addition reactions, 735 736 485 - 487. 486/ 487/ .
362-363 362/ 363/ 365
516-517, 516/ 517/ .
adenine 770. 770/ 824/ amphoteric oxides, 835 atomic masses. 81-82, 82 /, 128.
function of. 511-512.511/ adenosine diphosphate ( ADP ), anabolism. 769 133, 856/-857/
lab procedure. 496 - 497 767. 767/ angular momentum quantum atomic mass units ( amu ). 76/ .
pH paper. 468. 468 /; 471, adenosine triphosphate ( ATP ). number. 107 108. 108/ 80. 855/
512.515/ 766- 769. 767/. 769/. 824/
'
anhydrides, 834 atomic number, 77, 856/ 857 /
.
in titrations 515-521. 515 /, AIDS/HIV infection, 762 anions atomic radii, 150-152 150/ .
516/ 517/ 518/-519/ air hags, 380 hydrolysis ol. 60N- 609 608 / . 151/ 152/ 163
acid ionization constants . air pollution. 836 ionic radii, 159 160, 159/ atoms, 66 -87
605-606, 606/. 628- 629 alcohols, 731. 731/ 731 / nomenclature. 220 221 - . in ancient science 43. 67 .
acidosis. 817 aldehydes, 731 /. 733. 733/ 221/ 221 / atomic number 77. .
acid rain, 279. 489. 489/ 510 .
alkali metals 142 . 142/ oxyanions. 225 -227. 226/, 856/ - 857 /
acids, 466- 489. See also pll 786- 791. 786 /; 788/ 230 .
atomic theory 67-69. 69 /
amphoteric compounds. alkaline batteries, 659. 659 / anodes, 72/ 656. 656/ average atomic masses.
485-487, 486 /; 487/ alkaline-earth metals. 142 . .
antibodies, 756 760/ 81- 82.82/
Arrhenius, 473- 474.473/ 142/ 792-797, 792/ 794 / aqueous solutions, 434 456 Bohr model. 102- 103 102/ .
.
474/ 482 /
Brunsled-Lowry. 478- 481.
alkanes. 716 724, 717/, 718
719/, 722/. 723 /
*. attraction between dis-
sociated ions 456 .
103 /
.
definition 6. 6/ 72
480/ 482/ alkenes, 724 - 727, 724 /. 727 / -
boiling point elevation . isotopes. 77- 80. 78/ 78 /, 79 /
conjugate. 483 485. 485/ . alkyl groups, 719- 722. 719/ 450-451 mass numbers. 78 78/ .
-
608 609 alkyl halides. 731 /. 732. 735 calculating hvdronium and orbitals, 106 - 110. 107/ 108/
decomposition of. 280 alkynes, 727 - 728. 728/ hydroxide ion concentra- .
108/ 109/ 110/
displacement reactions in . allotropcs. 725 tion of, 501 502 plum pudding model. 73
281 alloys, 402-403. 402 /. 403/, dissociation in. 435-439. quantum model. 104- 110,
experimental determination 802- 804.803/. 804/. 811, 811/ 435/ 438/ .
107/ 108/ 108/ 109/ 1 10/
of. 496- 497 alpha particles, 74. 75/, 685 /. electrolysis. 444- 445. 444/ relative atomic masses .
household. 472 686. 686 / . 690/. 693. 693/ freezing-point depression, -
80 81
hydrolysis of salts. 608-612. aluminum .
448-450 448/. 454-456 . sizes of. 76
608/ 610/ 611/ alloys, 811. 811 / 455/
electron configuration. 117 / .
ionization 441.441 /

INDEX 935
 atoms ( continued ) .
batteries 659 -660, 659/ 660/ , bond length, 181 182 /, 187/ . electron configuration. 116/.
structure of, 72-76 74/, 75/ . 669, 669/ bond strength, 196 .
148 202. 202f
76/, nor .
Becquerel Henri 685. 693 . boron, 113, 116, 116/ , 183 . forms of. 542
subatomic particles 682 . benzene, 729. 729/ - .
808 809 808/ 810/ in iron ore reduction 814. .
ATP ( adenosine triphosphate ). beryllium, 116. 116/. 792-793 . boron family elements . 814/
766-769. 767/ 769/, 824/ 792/ 794/ 808 - 811.808/ 810/, 811 / .
isotopes 82/, 695
.
Aufbau principle 111. 116.116/ Berzelius, Jons Jacob, 444 boron trifluoride, 198. 198 /; oxidation numbers. 235 /
.
automobiles, 380 579, 666. beta particles, 685/, 686. 686/ 203 properties, 812-813 813 / .
.
669, 669/ 731.811 811/ . 693. 693/ .
Bosch Karl, 597 carbonated beverages 413. .
average atomic masses, 81-82, binary acids, 230-231. 230/, .
Boyle Robert, 369. 376-377, 413/
.
82/ 128 468 - 469. 468 /. See also acids 396 carbon- 14 dating, 695. See also
AvogadroA
S8Q/
law, 379 380, 379/ binary compounds, 222. 279
binary molecular compounds,
' . .
Boyle s law 369-370 369/ 370/
bromine, 118/, 146, 161/, 162 .
radioactive dating
carbon dioxide
.
Avogadro's number S3. 86. 855/ .
227 - 229 228/, 229/ . - .
235 / 838 839 838/ 839/ .
in the carbon cycle 815, 815/
binding energy per nucleon, 840/ dr \ iu . 358 359
.
682 682/ bronithvmol blue, 513/, 516 molecular geometry' of. 201
B biochemistry, 750-775, 819-824 -
Bronsted Lowry acids and nonpolarity of, 205/
amino acids, 756, 756/ bases, 478-481, 480/ 482 / phase diagram. 358f
balancing equations 757-758, 819.819/ Brounian motion 404 . properties, 815
formula equations 264-265. . carbohydrates, 751-753 . Buckyhalls, 725 .
in respiration 816-817, 817 /
267 752/ 753/ 766. 821-822 buffers,606- 607, 606/ 609 carbon family of elements .
.
by inspection 270-274. 294 DNA, 771-772.771/ 772/ .
butane, 713 713 /, 717/ 812- 827. See also under
redox equations. 637-641 . genetic engineering, names of individual
>50 774 7717741/ elements
using models, 284 lipids. 754-755 754 /; 755/. c carbon monoxide, 275. 815 .
-
ball and- stick models . 822-823 818.818/
197- 198. 197/ 198/ 713/ metabolism, 766 769. 767/ - .
caffeine 484 carbonyl groups, 733
Balmer spectral series, 103, 768/ 769/ calcium carboxy l groups, 734, 734 /
103 / nucleic acid structure. 770. dietary. 796, 796/ carboxy lic acids, 731 /, 734, 734/
band of stability, 682- 683. 683 / 770/ electron configuration, 118. careers in chemistry
barium, 121.618-620, proteins, 757-765 118/ analytical chemist, 516
792-793. 792/ 794/ RNA, 773 -774.773/ properties, 792-793 792/ . chemical technician. 300
. .
barometers 363 363/ 376 hioluminescence, 102 794/ computational chemist 204 .
base dissociation constants, 610 blocks, of elements. 138-139. .
reactivity 142, 142/ 793, 793/ environmental chemist, 408
base-pairing, 771-772. 771/ 824 139/ calorimeters, 531, 539, 539f, forensic chemist, 774
.
bases 471 489. See also pH blood. See alstt hemoglobin - .
852 853 852/ materials scientist. 145
amphoteric compounds. artificial. 417. 417/ 762 . - .
calorimetry 558 559 852- 853. petroleum engineer, 720
485 - 487 buffers in, 609 852/ 853/ pharmacist . 222
.
Arrhenius 473, 475 - 476 . carbon dioxide in. 816- 817. Cannizzaro, Stanislao, 133 casein, 760, 760/, 782-783
475/, 482/ 817/ capillary action, 335, 335/ catabolism, 768-769. 768/ 769/
Bionsled- Lowry 478 481. . -
sickle cell anemia, 761. 761/ carbohydrates catalysis, 570 571/ .
480/ 482 / transfusions 762 . chemical structure, 821-822, catalysts
calculating hydronium and Bohr, Niels, 101/ 102-103, 821/ 822/ catalytic converters, 579
hydroxide ion concentra - 102/ 103/ condensation reactions, in chemical equations, 26h
tion in. 501-502 boiling, 336, 344 -345, 344 /; 345 / .
752-753 752f 753f enzymes as. 763 -764, 763
conjugate, 483- 485, 485 / . -
boiling point elevation, digestion of 768 . heterogeneous vs. homo- ^
608 609 450- 451, 462 disaccharides 752, 752/ 821,. geneous, 570
dissociation constants. 610 boiling points If . $21/ reaction rate and, 570. 570/
experimental determination bonding types and, 203. 204 / monosaccharides, 751-752. 571/
of. 496- 497 of crystalline solids. 340/ 752/ 821.821/ catalytic converters, 579
household. 472 determining, 462 polysaccharides, 753. 753/ . .
catenation 712 712/
hydrolysis of salts, 608 - 612. of liquids. 344-345. 344/ 345/ carbon cathode rays, 72-73. 72/ 73 /
608/ 610/ 611 / of organic compounds. 722/ . aIlot ropes, 725 cathodes, 72/ 656. 656/
.
Lewis 481 - 482. 482/
neutralization reactions.
723. 723 / 730/ .
ot water, 344. 344/ 35 L 855/
in aromatic hydrocarbons, cathodic protection, 662. 662 /
729.729/ cations
487 - 489, 488/ bond angles, 199 - 201. 199/ Buckyhalls, 725 hydrolysis of, 609-610
properties, 471 472 200/, 350 carbon cycle, 815, 815/ . . .
ionic radii 159- 160 159/ 164
strength of, 475 476, 475 / . bond energy, 181. 182 / 187/ . covalent bonding in. nomenclature, 220 221 / . .
476f 484 -485, 485/ .
bonding See chemical bonding 186 - 188 187 / . 224 -225. 224f

936 INDEX
cellulose, 753, 753/ 822/
Celsius temperature scale 531
. .
base dissociation constants.
610
activated complexes.
565-567.565/
oxyacids of , 486/ 487
. -
properties. 383/ 838 839,
centrifuges 12. 12/ buffers. 606-607, 606/ .
activation energy 564-567 . 839/ 840/
. .
cesium 82/ , 121 177, 786 787 - . calcium -carbonate system . .
564/ 565/ 570. 764. 764 / '
size of . 150/
.
786/ 787/ 788/ 6( H )
common - ion effect .
activity series. 285 -287. 286/
addition. 735-736. 736/
water treatment by, 840-841 ,
chain reactions 697 698. 697 / - 840/
changes of state, 342-348 -
603 604, 604/ amino acid. 756 chlorofluorocarhons ( CFC s ) .
.
boiling 336. 344 -345 344 f, . determining equilibrium collision theory, 562-563. 732.735
345/ constants, 592. 626 563/ 569 .
chlorophy ll 766. 797/
chemical. 8 11.9/ - equilibrium expression. combustion , 283. 283/ cholesterol. 755
equilibrium and. 342-343. 591 595, 591£ 593 538-539, 539/ 856/ chromatography, 848 - 849,
342 /. 343/
*
factors in. 598-601, 599/ 601/ combustion synthesis 288. . 848/ 849/
freezing. 336. 342/. 345-346. hydrogen - iodine system . 288/ chromium, 118/. 119. 632, 632/
351 -
592 594. 593/ condensation . 736. 752-753. 798-81X). 799/ 800/ 801 /
.
melting. 338. 342/ 346-347 . ionization constant of water. 752/ 756 cis isomers 714. 724/ 724 /
phase diagrams. 347-348, 500-501. 500/, 600. 607 -
decomposition. 279 280. 280/ citric acid cy cle. 768
347/ 348/ precipitation calculations, definition, 261 .
cloning, 775 775/
( harks. Jacques, 371 618-620 double-displacement. . .
cohalt , 118/ 119 798-800.
C harles's law, 371 372, 371/ - reactions that go to comple - 282-283. 282/ 438 439. - .
799/ 800/, 801 / 807 /
372 f 396 tion . 601-603, 602/ 438/ 440 coefficients, equation, 263 .
chemical bonding, 174 -207 reversible reactions and . .
driving force of 546-550, 265, 268-269.537
carbon . 711-712, 711/ 712 / 589-591 548/ 549/ collagen , 760. 760/
.
covalent 178-189 . -
salt hydrolysis 608 612. elimination . 737. 737 / colligative properties, 446 456 -
definition. 175 608/ 610/ 611/ endothermic. 535-537, 537/ boiling- point elevation .
electronegativity and . solubility products. 613-620. 546. 549/ 450-451, 462
176 -177. 176/ 177 / 615/ enthalpy of. 534-542 536 /. . -
electrolytes and . 453 456.
enthalpy of vaporization.
196. 196/, 345.345/ 351
chemical equilibrium expres
sion, 592. 626
- 537/ 543/
exothermic, 415- 416.
453/ 455/
freezing- point depression .
inter molecular forces.
'
chemical formulas, 178 535 -536. 536/ 549/. 564 448-450, 44 S t . 4 s 4 -456,
203-207. 204/ 205/ 206/ . calculation of . 245-249 half - reactions, 633 635 - 455/, 462
207/ for covalent - network com - indications of . 261-262 of nonvolatile substances,
ionic. 190-194 pounds. 230 limiting vs. excess reactants. .
446-447 446/ 447/
metallic. 195-196. 195/ 190/. empirical. 245 -247. 312-316, 312/ osmotic pressure. 452-453 .
204/ 258 -259. 746 mechanisms of . 561-562, 561/ 452/
observable properties. formula masses. 237-238 neutralization, 468. 472, vapor- pressure lowering.
216-217 for ionic compounds. 222 487- 489. 488/ 517 521 - 446- 447. 446/ 447/
types of. 175-177. 176 /; molar masses, 83, 83/ .
nuclear 684, 697-698. 697/ collision theory, 562-563. 563/
177/ 216-217 238-242. 240/ percentage yield. 317-318 569
VSEPR theory. 197-201, lor molecular compounds. precipitation , 437- 439. 438/ colloids, 403- 405. 404/ 404 /
198/ 199/ 200/ 227-229. 228/. 229/ rate laws, 571-578. 584 combined gas law, 374 -375 396 .
chemical changes, 9 -10 for monatomic ions. reactions that go to comple - combustion reactions, 283,
chemical equations 262- 274 . 220-221.221 / tion . 601-603. 602/ 283/, 538 539, 539/ 856/
.
balancing 264 -267. oxidation numbers. 232-235. reversible. 266-267. 270. combustion synthesis, 288. 288/
270-274, 284 , 294. 235/ 589-590 common - ion effect. 603-604,
637-641.650 for polyatomic ions. single-displacement , 604/
coefficients in . 263. 265. 225-227, 226/ 281-282.281/ 285 composition stoichiometry, 299
268-269 -
significance of. 219 220 substitution . 735 compounds
elements in elemental state. . -
structural 712 713. 713/ synthesis. 270 -279, 277 f, 288 amphoteric, 485- 487. 486/,
262-263 chemical kinetics, 568. See also chemicals, definition of , 4 487/
net ionic equation . 439- 440 kinetics of reactions chemistry, science of, 3-5. binary. 222-223. 279
requirements of. 262-263 chemical properties, 8 - 10 See also history of definition , 7
significance of, 268 270, 269/ - chemical purity , 14. 14/ 14 / chemistry enthalpy of formation .
symbols in . 265-267. 266/ chemical reactions, 260-288. chlorine - -
537 538, 542 544. 543/
thermochemical. 535 See also chemical equations; chemical bonding. 177, \ 11{ . -
ionic 190 194.191/ 192/
word, 263-264, 268 chemical equilibrium ; kinet - .
183 183/ . -
193/ 220 227
chemical equilibrium 588-620 . -
ics of reactions; oxidation electron configuration. 117/ -
molecular. 178 179. 193 .
acid ionization constants. reduction reactions -
isotopes. 79 80 227-229. 441
605 -606. 606/. 628-629 acid - base, 483-489. 485/, oxidation numbers. 235/, .
nomenclature 220-225
486/ 487/ 488 /' 634-635 organic, 711

INDEX 937
 compounds ( continued ) .
corrosion, 545 661-662, 661 /, data collection, 29-30 I)NA ( deoxyribonucleic acid) .
oxidation numbers 232-235, . 662/ daughter nuclides, 690 771-772. 771/, 772 / '

235/, 634 -635 cosmic rays, 694 Daw, Humphry, 444 DMA fingerprinting, 774. 774 /
percentage composition. covalent bonding, 178 189 -
-
// block elements, 144 - 146, DNA replication, 772. 772/
242-244, 256 . .
compared to ionic 193 144/ 163 - 164 .
doping 826- 827
polyatomic ions in. 225 -226. 193/ .
de llroglie Louis, 104 .
Dorn, Ernst 115, 136
2261
solubility of. 861/
electron-dot notation.
184 - 186, 184 /
.
Debye Peter, 456
decanting procedure, 844
.
double bonds 186 188 187 /; - .
376
.
compressibility 331.334. 338. electronegativity and.
175-177, 176/ 177/ .
decay series, 690- 691 690/
decomposition reactions,
.
187/, 724 -725
double- displacement reactions,
282-283. 282/ 438-439,
concentration, 418 - 424 .
hybridization 201-203. 202 /; 279-280, 280f 438/ 440
chemical equilibrium and. 203 / decompression sickness, 368 Downs Cells 671 .
.
599 -600 599/
molality, 422- 424. 422 /; 454
intermolecular forces, 203- delocalized electrons, 195. 140. .
Drew Charles 762 .
207. 204 /. 205 /, 206/; 207/ 729. 729/ dry cells, 659- 660, 659/ 660 /
molarity. 418- 421.419 / 430, . Lewis structures 184 - 188, . Democritus, 43. 67 . -
dry ice 358 359, 500/
4W. 517-52I 5I8/-SIW . 214 denaturation, 764 -765 764 / . . ductility, 18. 196
.
notation 499 nomenclature. 227-229. 821
reaction rates and, 569 - 570 . .
228/ 229/ density
569/ 570/; 584 .
octet rule 182-183. 183/ calculation of 39 . E
titration and 517-521. . polyatomic ions, 194 . of familiar materials 38/ 39 . .
.
518/-519/ 528-529 199 -21Ml. 230. 230 / 294 . .
of gases 38. 331.398-399, effervescence, 413.413/
condensation, 342. 342 / redox reactions and . 859/ illusion. 332, 386-388. 386/
condensation polymers, 739 634-635 .
of liquids 334. 334/ .
Einstein Albert, 99 - 1 ( H ).
condensation reactions 736. . resonance structures 189 . of organic compounds, 730/ 681- 682
752- 753. 752 /. 756 VSEPR theory 197-201. . .
of solids 338 Einsteins equation, 681 - 682
conduction bands, 826. 826 / 198 /; 199/ 2( H )/ units of. 36/. 38 39, 38/ - elastic collisions, 329
conductivity, electrical,1. 18. covalent molecular crystals .
of water 351.859/ .
elast ins 760. 760/
628 - 629 .
340/ 341 deposition, 342 /, 346 .
electrical potential 662- 665,
conjugate acids and bases . -
covalent network bonding, derived units, 36-39, 36/, 38/ 663/ 664/, 676
.
483 - 485 485 / 608-609 . 189. 230.340. 341 / deuterium, 78, 78/ 79/ .
electric charge 73. 75
conservation of mass, 68- 69 . covalent network crystals, 340. diamonds, 542. 725 electric circuits, 656
.
69 /; 94 - 95 303 340/, 341/ diatomic molecules, 178. .
electric current 34 /. 405 - 406.
contact theory, 444
continuous spectrum, KM )
.
Crick Francis, 771
critical mass, 698
.
197-198 197/ 263/. 380
.
diffraction 104. 105 /
. . .
406/ 468 472
electrochemical cells, 655 657.
control rods, 698, 698 / .
critical point 347, 347 / diffusion 655/, 656/ 657/
conversion factors critical temperature, 347, 347 / .
of gases. 331 331 /; 336/ electrochemistry; 654- 671
.
molar mass 240 -242. 240/; Crookes, William, 596 .
386-388 386/ corrosion, 661-662.661/ 662/
301 crystalline solids, 338 of liquids. 334. 334/ definition. 655
.
mole ratios 245 -247 . binding forces in. 339 341. - .
of solids 339 electrical potentials .
3( M)-301.304-310.324 .
340/ 341/ . .
digestion 765 768-769 768/ . 662- 665. 663/ 664 /, 676
SI units, 40- 42 50 92 . . breakage and, 32.32/, 193. dimensional analysis, 40- 41 electrochemical cells.
using, 40- 42. 50. 92 193/ dipeptides, 756 .
655 -657 655/ 656/ 657/
copoly mers, 737. 739 .
hydrates 411, 411/ dipoles, 204 -206, 205/ 206 / . .
electrolysis 279, 670-671.
copper ionic bonding in, 191 - 192, .
diprotie acids 480. 480 / 670/
in the body, 807/ I9i /; 192/ directly proportional quan- .
electrolytic cells 667- 671,
in electrochemical cells . substitutions in, 804. 804/ tities. S 56, 55/ 551 667 /; 668/ 669f 670/
655 - 660. 655f 656/ 657/. . - .
types of 339 341 339/ 340/ . .
disaccharides 752 752/ 821. . rechargeable cells, 669, 669/
658f Curie, Marie and Pierre, 685 821/ voltaic cells. 658- 666 658 /; .
electron configuration. 118/ . cycloalkanes, 718 dispersed phase, 403 659/ 660/, 661/
119 cysteine, 756/; 758, 758/ displacement reactions, electrode potentials 662- 665, .
ionization energy , 164 cy tosine, 770. 770/ 824 / . .
281-283 281/ 282/ .
663/ 664/. 676
. .
isotopes 82 82 / disproportionation, 644-645 . electrodes, 656. 656/ 663. 663/
oxidation and reduction of. 645/ .
electroly sis, 279 444 445.
643. 643/ -
in photochromic lenses. 634
D dissociation, 435 439. 435/
438/
444/ 445/ 670-671, 670/
electrolytes, 405 - 406, 406 /
.
properties 18 /; 19, 798-800, Dalton's atomic theory; 68 69 dissolution, 407 408 407 /; . balance of. 789. 789/
799/ 800/ 801 / Dalton's law of partial pres - 547 548. 548 / . See ,ih < > colligative properties and.
reactivity, 799. 799 / sures, 365 -368. 366/ solubility .
453-456 453/ 455/
in tap water. 477 Daniell Cells, 656/ 657. 657/ disulfide bridges 758 758/ . .

938 INDEX
 in electrochemical cells. 656, in metallic bonding. electron affinity, 157 159.- .
equations See chemical
656/ 195 -196. 195/ 157/. 158/ equations
strong vs. weak , 442- 443. .
orbitals 106-110. 107/ 108/ electron configuration and . equilibrium. See chemical
442 f 108 / . 100 / . | 1 ) 1/ 111 -112, 111/ equilibrium
electrolytic cells, 667- 671. photoelectric effect , 99-100. -
of electrons, 100 103, 101/ equilibrium, in state changes,
667/ 668/ 669 /; 670/ 99 f 102/ 103/ 342-343
electromagnetic radiation . properties. 76/ enthalpy of combustion. equilibrium constants 592. .
-
97 100, 687.687/ See also unshared pairs. 185, 538-539, 539/ 856/
enthalpy of formation.
Sec also chemical
light 199-200. 199/ 2( H ) / equilibrium
electromagnetic spectrum . .
valence 160, 160/ -
537 538. 542-544, 543/ acid ionization. 605- 606.
97- 99. 98/ -
as waves. 104 106.105/ 107/ enthalpy of reaction , 606/, 628-629
.
electron affinity 157 159. 157 /; electroplating, 668-669, 668/ 534-537. 536/ 537/ base dissociation . 610
158/' elements, 16-20. See also enthalpy of solution. determining 626 .
electron capture, 687 families 415-416.415/ 41 h / ionization constant of water,
electron configurations . activity series, 285-287. 286/ entropy. 546-548, 547 /! 548/ 500-501, 500/, 600, 607
111 - 122 alkali metals. 142. 142/ 549/ measuring. 628-629
atomic radii and. 150-152. 786-791.786/ 788/ free. 548-550.549/ solubility products. 613- 620.
.
150/ 151 / 152/ 163 in ancient science. 43 in hydrogen bonding. 179. 615/
of //- block elements. artificial transmutations, 179 f equilibrium vapor pressure .
144 - 146, 144/ 691-692. 692/ 692/ .
ionization 153-156. 153/ . 343.343/
electron -dot notation . atomic masses. 81-82. 82 /. 154 /; 155/. 164 equivalence point , 516-517.
184 -186. 184/ 128. 133, 856/-857/ kinetic. 329-330, 386 516/ 517/
notation of. 112-113 atomic numbers, 77. 81-82. lattice. 192. 193/ error, 45-46
period number and , 1 lb- 82 /, 856/-857/ nuclear binding, 681-682. .
esters 731 /. 734
121. 116/. 117 /. 118/. 120/ in the body. 806-807, 806/ 682/ .
ethane 716. 717/
of v-block elements, 142. 142 / 807 / of photons. 100-101 .
ethanol 344/ 412.713/, 731
'

summary of , 111-112. 111/ definition. 6 quantum . 99 .

ethene 727, 727/
112/ 138-139 147/. 170 . Elements Handbook. specific heat , 532-534, 533/ ethers, 731 /. 732
valence electrons. 160. 160/ 786-841 units of , 531 ethyne 727.
writing, 170 enthalpy of formation. 538 enthalpy evaporation. 335-336.336/
-
electron dot notation . molar mass. 83. 83/ activation energy and . 342-343.343/
184 -186. 184/ 190- 191 238 242 . 240 f 564 -567, 564/ 565/ excess reactants, 312. 312/
electronegativity periodic table of . 140/- 141 / calculating, 539-542. 556 excited state. 100
acid strength and. 487 sy mbols for. 16. 16/. of combustion. 538-539. exothermic reactions
chemical bonding and . 856/-857/ 539/ 856/ activation energy in , 564.
.
176-177 176 /; 177/ transmutation of , 684. of formation. 537-538, 564/
-
dipole dipole forces . 691-692. 692/ 692 / 542-544, 543/ 902 / enthalpies of solution and .
204 -206, 205/ 206 /- transuranic. 692. 692/ 692 /. in free energy, 549 -550. 549/ 415- 416.416/, 549/
period trends, 161 - 164. 161/
162/
—
7( H ) 701
types of . 18-20, 18/ 19/
of fusion , 346. 356
Hess's law. 539-542 556. .
thermochemical equations
for. 535-536. 536/
electrons, 96 -122 elimination reactions, 737, 737 / 558-559 expansion of gases, 330
in Bohr model. 102-103 . .
emission 102. 102/ 130-131 of reaction. 534-537 536/ . explosives, 572. 597
102/ 103/ Kmpedokles, 43 537 / ; 543/ 546 exponents, 50-52
charge of . 73 empirical formulas, 245 247 , - in reversed equations 540 . extensive properties, 7
in covalent bonds. 179. 179 /, 258-259, 746 of solution. 415- 416. 415/ extraction procedure, 844-845
*

181- 182 , 181/ 182/ emulsions, 403, 404 / 416 /

delocalized. 195. 340, 729 . endothermic reactions, of vaporization , 196. 196/,
729/ 535-537. 537/ 546. 549/. 564 / 345. 345/ 351
F
*

-
discovery of . 72 73. 72/ 73/ end point. 516. 516/ enthalpy changes, 534
in electrochemical cells. energy , 530-550 .
entropy* , 546 -550 541 f, 548/ families, 808 837 -
- .
655 660 655 f 656/ 657/ activation, 564-567.564/ 549/
.
alkali metals. 142 . 142 / .
658/ 565/ 570. 764. 764/ enzymes 763-765 786-791.786/ 788/
Heisenberg uncertainty ATP. 766-769, 767/ 769/. .
coenzymes 820.820/ -
alkaline earth metals. 142.
.
principle 105 824/ pH and. 765. 820-821 142/ 792-797, 792/ 794/
in Lewis acids and bases. boiling and . 344 -345. 345 f as proteins, 756 -
boron , 808 811.808/ 810/,
481-482. 482/ bond . 181-182. 182/ 187/ . specificity of , 763-764. 763/ 811 /
-
line emission spectrum, catalysts and, 570.571/ temperature and . 764. 764/ carbon. 812-827
-
100 101. UK )/ 101/ . changes of state and . 10-11 , -
enzyme suhtrate complexes, halogens. 838-841, 840/
mass of , 73. 76/ 855/ . 344-352.345/ 763-764. 763/ nitrogen , 828 831.829/ 831 /- .

INDEX 939
 families [ continued ) -
freezing point depression . pressure, 361-367, 361/ - . .
half life 688 - 689 688/ 688 / .
.
oxygen 832-837. 834 / 835 / .
.
448- 450, 448/, 454-456 . 362/ 363/ 364/ .
706 708-709
transition metals, 144 - 146 4551. 462 properties 8 . half-reaction method of bal-
798-807 801/ . freezing points, 345 - 347. 462. solubility in water 860/ . ancing equations 637-641. .
Faraday, Michael, 444 445, 855/ stoichiometry of reactions. 650
445 f
.
freons, 732 381-382 half- reactions 633-635.
fats See lipids frequency, 98 -99 98/ . .
gasohol 731 Ilull- 1k rmill process 671 .
fatty acids, 754. 822 - 823 822/ . .
fructose 751-753 752/ 753/ . .
gasoline 412. 723 / halogens, 838- 841
-
/ block elements, 136. 821f gauge pressure, 398-399 activity series, 285-286 286/ .
148- 149, 163 - 164 .
fuel cells, 660 660/ 666 -
Gay Lussac, Joseph 373 . .
in alkyl halides 731 /, 732 .
Fermi, Enrico, 700 fullerene, 725 -
Gay Lussac's law, 373-374. 732/ 735
fertilizer production, 596 597. functional groups, 730-734 . 373/ 396 .
properties 147, 147/
831.831/ 730/, 731/ Gay - Lussac's law of combining -
838 839, 838/ 839/ 840/
fibrous proteins, 760 760/ .
.
fusion, 695-696 699 699 /. . volumes of gases, 378 .
reactions 278. 281-282
-
fifth period elements 119. 120/ .
Geiger Hans, 74. 74/ heat, 261.261/ 531-534. 532/
film badges 694. 694 / .
nitration, 12, 12/ 844 - 845.
-
Geiger Miiller counters, 694, 533/

844 /; 845/
G 694/
genes, 773
Heisenberg uncertainty princi-
ple, 105
.
fireworks 794-795, 794f . . -
gallium 118/ 808 809. 808f . genetic code 772. 780. .
helium 79/, 115, 136, 143
fission, 697- 698. 697/ 698f . 810/ genetic engineering, 774 775. hemoglobin
700 701 .
galvanic cells See voltaic cells 774/ in carbon monoxide poison-
flame tests, 130- 131, 787, .
galvanizing 662 geometric isomers, 714 714 / . *

ing. 275.818 818/ .

787/ , 793.793/ 829. 829/ ,
'
. gamma ray s, 685 /, 687. 687f . glacial acetic acid, 471 heme molecule in. 816, 816 /
833.833/ 693, 693 / glass, 32, 338. 825 iron in. 807. 807/
flavorings, 733/ gas constant, 384-385 384/ . . globular proteins, 760, 760/ in sickle cell anemia, 761.
.
fluids 330-331, 333 855 / gluconeogenesis, 769 761/
fluoridation, 283 841 . gases, 360-388 .
glucose, 751-753 752/, 753/ structure of, 759. 820 820/ .
fluorine Avogadro's law, 379-380. 816. 821f HenryV* law, 368. 413 - 415.
covalent bonding 183. 183 / . 379/ 380/ .
glutamic acid 756/ 758 758/ . 413/ 414/
electron configuration 116/ . .
Boyle s law 369-370. 369/ . 761/ hertz, 98
electronegativity 161, 161 / . 370/ 396 glycerol, 731, 731 / Hess's law, 539-542, 556.
.
properties 383/ 838-839 . Charles's law, 371 372 371 /; - . .
gly cogen 753. 753/ 822 / 558-559
839/ 840/ 372/ 396 gly colipids, 755 heterogeneous catalysts, 570 .
reactions, 278, 281-282 from chemical reactions, gold, 18/ 66 /; 402-403 403/ . 579
tooth decay and 281, 841 . 262. 262/ 282-283 602 . 798. 801 / heterogeneous mixtures, 11 / .
forces combined gas law 374-375, . Graham's law of eflusion . 12.401/
intermolecular 203-207 . . 396 386 -388, 386/ heterogeneous reactions,
204 /, 205/ 206 f , 207 / .
density of. 38 331.398-399 . gram/mole conversions, 84 568-569
nuclear. 76. 682-684. 683 / . 859/ graphite, 542. 725 hctcrotrophs, 766
68
pressure and, 361-362, 361f,
deviations from ideal behav -
ior. 332.332f
graphs, 30/ 55/ 57/
gravimetric analysis, 326-327,
-
highest occupied energy level
116
.
362/ Gay - Lussac’s law 373 -374. . 846 - 847 history of chemistry
units of, 362 373/ 396 graiity filtration, 844-845, . -
air pressure 376 377, 376/
forensic chemists, 774 Gay - Lussac 's law of combin - 844/ 845/ ancient Greek science . 43
formula equations, 264. See ing volumes of gases. 378 greenhouse gases, 579 .
combustion 302-303, 303/
also chemical equations
. .
Graham’s law of effusion, ground state, 100, 103, 103/ electrolysis .
444 - 445. 444 /,
formula masses 237-239 386-388 386f. -
ground state electron configu - 445/
’

248-249 Henry 's law. 368. 413 - 415, ration, 1 11 nitrogen fertilizer produc-
formula units, 190 413/ 414/ .
groups 17. See also families tion. 596-597
fossil fuels, 723 723 / . ideal gas law. 383, 383/ .
guanine 770. 770/ 824/ nuclear fission. 700-701
-
fourth period elements . kinetic-molecular theory of . organic chemistry. 715. 715 /
118 -119. 118/ 329 -332.330/ 331/ 332f periodic table, 114 - 115 .
fractional distillation 723. 723/ . measuring properties of.
H 115/ 133-135, 134/
Franklin, Rosalind 771 . 398-399 172- 173
free energy, 548-550, 549 / molar volumes, 380-381 Haber, Fritz, 597 homogeneous catalysts 570 .
free radicals 836 . noble. 20, 20/ 135 - 136, Halier process, 597, 598-600 homogeneous mixtures 11/ .
freezing, 336. 342/, 345 -346.351 135/ 332 .
Hahn, Otto 700-701, 700/ 12. 401/ See also solutions
partial pressures 365-368, . half-cells, 656-657, 656/ homogeneous reactions, 562
366/ 599 .
662- 665 663 f, 664 / homologous series, 716

940 INDEX
Hooke, Robert, 376 hy drolysis, 608-612. 608/ dissociation. 411.411/
hormones, 760/
Hiickcl, ({rich 456 .
610/ 611/ 752-753.753/
767, 767/
. -
435 439, 435/, 437/ 438/
.
formation of 190-194 191 f, .
K
Kelvin temperature scale
11liman Genome Project, 772 hydronium ions 192 ; 193 193
/ / /
hiimun growth hormone, 775 in acid solutions. 473 - 474. nomenclature 222-223, . 371-372, 531
.
lltind’s rule 112. 112/ 473/, 474/, 485 225 -226 ketones, 731 /, 733, 733/
.
hybridization , 201-203, 202 /, calculating concentration of . salts as 231. kinetic energy 329-330 386 .
*
kinetic - molecular theory
203/ 501-502 ionic radii, 159 - 160. 159/ .
hybrid orbitals 202. 202/ . ionization and 441 . 164
Boyle s law. 369. 369/
Dalton s law 366. 366/ .
hydrates, 243-244. 411.411/ pH scale and 503 -504 503/. . ionization
.
hydration, 411. 411/ 441 hydroxide ions, 501 Of aqueous solutions 441. . of gases 329-332, 330/
331/ 332 /
hydrocarbons, 716 -729 hydroxides, 280. 476. 476 /
"

441 /
alkanes, 716-724. 717/. 7 IS/, hydroxyl groups 487 731 . . . chemical equilibrium and. .
of liquids 333-336, 334/,
.
719/ 724/ 731 / 603 335/ 336/
.
alkenes, 724-727 724 / 727/ .
.
. hyphen notation, 79 .
energy 153 - 156, 153/, 154 /.
of solids 337-341. 337/
.
alkynes 727-728 728/
aromatic, 729, 729 /
hypotheses ( singular, hypoth
.
esis ) 30-31, 31/
- 155 /, 164
sell - ionization of water .
338/ 339/ 340/, 341/
kinetics of reactions, 560-579
enzymes and, 764. 764 /’
cycloalkanes, 718 - .
499 500 499/ 500/. . observing, 586-587
functional croups 730 734. . - 599 -600
rate-determining steps .
730/. 731 / ionization constants, 500-501,
isomers, 713 -714 576-577
nomenclature, 718-722. ibuprofen, 241-242
5006 600.605 607.606/
— rate- influencing factors .
.
718/ 719/ 725. 72S . ice, 342 /, 346-347
ionization energy ( IE ). 153
156, 153/ 154/ 155/ 164 . 568-570. 569/ 570/ 571/ .
saturated. 716 ideal conditions, 304 .
ions 153
578
structural formulas 712-713 . ideal gas constant 384-385. . .
hydronium 441, 473- 474. rate laws, 571-578, 584
reaction process, 561 567.
unsaturated, 724 -729, 724 / 384/, 855/ .
473/ 474 / 485. 485 /
hydrochloric acid, 441, 441/ ideal gases, 329-332 330 f . ionization and. 441. 441/
563/ 564/ 565 /
.
471, 480/, 4S4. 488-489, 331/ 332/ 383. 383 / .
monatomic 220-221.221 /
specific rate constant
488/ ideal gas law 383 383/ . . names of common. 858/
573-575
Krebs cycle, 768
hydrogen immiscibility, 412. 412 / polyatomic. 194. 199 -200.
Bohr mode! of. 102-103, .
indicators See acid-base .
230 230/ 294
.
krypton 115, 118/ 136 .
102/ 103/ indicators iron

electron configuration. induced dipoles, 205 206, alloys, 802-803.803 /

142-143
in fuel-cell cars 666 .
206/
.
inks 432-433
blast furnace reduction. 814.
814/
L
.
fusion of 699. 699/ -
inner shell electrons, 116 in blueprint paper, 296 -297 -
lactose, 752 753, 821 /
hydronium ions 441.473 - . . in the body. 807 807/ . . .
lanthanides 136 148 - 149 157/ .
.
474 473/ 474 / 485. 485/ .
insoluble substances 613
.
insulin 756. 760. 760/, 775. corrosion of. 661 662 661/ - . .
lattice energy 192. 193/
.
isotopes 77- 78 78/ 78/ 79/ . . . 819 820 - 662/ .
Lavoisier Antoine, 303 303 / .
82 / intensive properties 7 . electron configuration. 1 IS/.
law of conservation of mass,
68 - 69. 69/ 94 -95, 303
line-emission spectrum . interference, 104. 105 / I ( Mi . 119-120
.
.
100- 101 100/ 101 / intermediates, 562 ionization energy 164 . law of definite proportions
reactions with 468. 592 594 . - intermolccular forces 203 -207. . nomenclature. 224
68- 69. 69 /
.
.
solid 338 .
204/ 205/ 206/ 207 / oxidation of, 277, 277 /, law of multiple proportions
hydrogenation , 735 -736, interstitial crystals, 804 , 804 / .
314-315 652-653
68
*
736/ inversely proportional quan- .
properties 798 -8( H ) 799/ . law of partial pressures,
365 -368, 366/
hydrogen bonding .
tities, 56 56/, 57/ 800/ 801 /
bond length and energy. . .
iodine 120/ 235/ 592 594 . - . isoelectric point 782 . lead
in ear batteries. 669 669/ .
181-182, 181/ 182/ .
593/ 838 - 839, 838/ 839/ isomers, 712. 713 714. 713/
* - nomenclature, 224. 224 /
covalent bonding in. 176. 840/ 714/
. . poisoning. 477
177 /; 179 / ionic bonding 190 - 194 isotopes 77- 80. 78/ 78/ 79/, . properties. 812- 813. 812/
dipole -dipole forces in. 206. boiling points and. 204/ 82/
813/
206/ Covalent bonding compared IL PAC nomenclature, 718
in DNA, 771. 771/ 824/
in water, 349-350 349/. 350/ .
. .
with 193 193 /
electronegativity and.
LeChatelier, Henri Louis, 598
LeChateliers principle 598 . .
hydrogen peroxide, 644 - 645, 175 -177. 176/
603-604
763 ionic compounds
J .
length, 34/ 35 -36 36/ 854 / .
crystals, 340, 340/ leptons, 682
joules, 531.852
.
Lewis, G NH 481

INDEX 941
 Lewis acid base reaction.
- classification . 11 - 14 . 11 /. decomposition reactions.
482 12/ 13/ 279 -280, 280/
Lewis acids and bases, definition . 6 displacement reactions.
macromolecules, 819. See also kinetic-molecular theory of . 281-282
481 - 482. 482 /
Lewis structures, 184 188,
biochemistry
magic numbers, 683
329-332. 330/ 331/ 332 /
*

metallic bonding, 195- 1 % .

214 particle theory of , 67 195/ 1 %/
magnesium
light physical properties and as oxidizing and reducing
in chlorophyll, 797, 797/
from chemical reactions. changes. 7-8. 9/ agents. 642- 643, 643/
dietary. 796 -797. 797/ measurements, 28 -57 properties, 7, 18-19. 18 /',
261.261/
electron configuration , 117/ 195-196. 196/
diffraction and interference. accurac ) and precision in,
properties. 792-793, 792/
104. 105/ 106 44 - 46.44/ reaction with acids, 468
794 /
as particles. 99 - 100 direct proportions, 55 -56. self - protecting, 810
reactivity. 277 /! 793, 793/ synthesis reactions, 276-279,
photoelectric cl feel, 99-100, 55/ 55/
magnesium oxide, 258-259
99 / '
magnetic quantum number,
inverse proportions 56, 56/. . ’
277/
speed of . 855/ 57/ transition. 144-146, 798-807
.
as waves 97-99. 98/ -
108 109
scientific method , 29 -31 . methane, 198. 198/ 202. 202 /.
. .
lime 278 510
.
magnetite 314 -315
30/ 31/ 717 /
limiting reactants, 312 316
main -group elements,
scientific notation . 50-52. 62 .
methyl orange 513/. 516
-
line emission spectrum . 146 - 148, 147 /
significant figures. 24. .
metric units 854/
100 - 101 , 100/ 101 /
M A 1.1 )1 mass spectrometry,
46-50. 47/, 48/. 505 .
Mieschcr Friedrich, 771
lipids
236
malleability, 18, 196
SI unils, 33-42 Millikan. Robert A. 73 .
digestion of 768 . .
iMalllius Thomas, 5%
of water in popcorn. 64 -65 millimeters of mercury,
.
fatly acids 754 . 822-823 . . . . -
Meitner, Lise 700 701, 701/ 364 -365. 364/
822 /
manganese 118/, 119
652-653. 800.800/ 807/
melting, 338. 342/ 346-347. miscibility. 412. 412 /
hydrogenation, 735-736,
manometers 363.363/ . .
melting points 338. 340/. .
mixtures 11-12. 11/
736 / 730/ colloids. 403-405. 404 /! 404 /
margarine, 736. 736/
phospholipids. 755. 755/, Mendeleev, Dmitri, 1 14. separation procedure, 26 -27
823. 823/
.
Marsden Truest 74 . 74/ . 133-135, 134/ 172-173 solutions, 401 *403, 401/
.
structure of 822-823. 822/.
mass, 6
atomic, 81-82. 82/, 128 133 . . .
meniscus 335. 851 / 402/ 402 /. 403/
823 / mercaptans, 636 suspensions. 403
liquids
856/ -857/
conservation of 68 -69. 69/ .
mercury .
models 31
.
boiling 344 345. 344 /! amalgams. 802/ ball -and -stick . 197-198,
94 - 95. 303
345/ poisoning. 805. 805/ 197/ 198/ 199/ 205/ 713 /
equilibrium vapor pressure.
conversion to moles . properties. 10/ 144/ 798. Bohr, 102-103. 102/ 103 /
308 -310 constructing. 71
343. 343/ 801 /
critical . 698
freezing. 336. 342 /. 345-346 . of electrons 73. 76/ 855/ . . reversible reactions. lock and key. 764
351 589-590. 589/ nuclear shell. 683. 687
miscibility of. 412. 412 /
.
formula 237-238, 248-249 mercury batteries, 660, 660 / space-filling, 713/
molar, 39. 83. 83/ 238-240,
properties. 8. 333 336, 334/ - 240/! 248-249
messenger RNA ( mRNA ). .
moderators 698. 698/
335/ 336 f 773. 780 molnl boiling - point constants .
supercooled. 338
molecular. 237-238 248 249
of neutrons, 76/
. - metabolic pathways, 766 448/. 450-451
volatile. 343
numbers ol atoms and.
metabolism, 766-769. 767 /. -
molal freezing point constants,
448. 448/
liters, 37. 37/ 768/ 769/
.
lithium 116. I 16/ , 155 156.
82 -84
percentage composition . metallic bonding 195 196.. molality, 422 424. 422/. 454
.
155/ 786 -787. 786 /! 787/
242 244.256
195/ 196/ 204/ . molar enthalpy of formation,
788/
of protons, 75. 76 /. 855/
metallic crystals, 340-341 340/ . 537-538
litmus paper, 516
relative atomic, 80-81
.
metalloids 19 20 146- 147. molar enthalpy of fusion. 346.
lock ami key model, 764
. - . .
metals See also transition 356
.
logarithms 505 509 526 . units of 34 35, 34 / 854/
mass defect, 681
metals molar enthalpy of vaporization .
London dispersion forces 207. . mass number, 78. 78/
activity’ series. 285 -287, 286/ 345.345/ 351
.
207/ 722-723
mass spectrometry, 236. 236 /
alkali. 142. 142/ 786 -791. molarity, 418- 421 , 419/ 430.
lone pairs, 185. 199 -201.200/, 786/ 788/ 517-521 , 5 I 8/-5 I 9/
299/
materials scientists 145 . -
alkaline earth . 142. 142/ molar masses, 83. 83/,
luster 18. .
matter 2 - 20. See also states of
792-797.792/ 794/ 238-242. 240/. 248-249.
.
lye 754
matter
building blocks of. 6-7
alloys. 402-403. 402 /. 403/ 301.306-310.306/
Lwiian spectral series, 103.
chemical properties and
802-804. 803/ 804 f . - .
molar volumes, 380 381 855/
103/ as catalysts, 275, 579 molecular compounds, 178.
changes. 8 10 10/ - . corrosion. 545. 661-662. See also covalent bonding
classical ideas about , 43 661/ 662 / ionization of. 441.441 /

942 INDEX
 nomenclature. 227-229. nitrogen for electron configuration.
228/, 229/
.
properties 193. 193/
covalent bonds in. 187. 187/.
187/
112- 113.117. 117/
electron -dot, 184- 1.86, 184 /, '
0
molecular formulas, 178. 245. .
fertilizers. 596-597 831.831 / 190- 191 - .
octet rule , 182 183 183/
oleic acid , 754. 822/
248-249 .
fixation . 184. 596. 830 830/ for isotopes. 79, 79/
orbitals. 107-110. .See also
molecular geometry. 197 - 207 nomenclature, 229.229/ lor nuclides. 691
hybridization, 201-203.202/, oxidation reactions, 235/. for proportionality, 572 electron configurations
in covalent bonding,
203/ 541-542.594-595. lor reversible reactions . 181-182. 181/
intermolecular forces 203- . 600-601.601/ 590
hybridization . 201-203, 202/,
207. 204/, 205/ 206/ 207/ properties, 828-829. 829/ nuclear binding energy. ’

VSEPR theory, 197-201. nitrogen -containing bases. 770. 681-682. 682/ 203/
198/ 199/ 200/ 770/ 772, 780 nuclear chemistry, 680-701 models, 106. 107/
notation , 112-113
molecular masses, 237-238. nitrogen family elements. applications 695 . order of filling, 116/
248-249
molecules, 7. 178
-
828 831, 829/, 831/ artificial transmutations.
691-692.691/ 692/ 692/ quantum numbers and .
nitrogen narcosis, 368
107-110, 108/ 108/, 109/
mole ratios. 245 -247. 300-301. nitrous oxide , 579 band of stability. 682-683,
304 -310, 305/ 324 110/
noble gases, 20, 20 f 683/
order of reaction, 572-573
moles, S3 84.304 -310 .
discovery of. 114 -115 115/ chain reactions. 697-698.
monatomic ions, 220-221 . .
as ideal gases 332 697/
organic acids, 474 - 475, 734,
221 / in the periodic table. .
decay series 690-691 . 690/
734/
organic chemistry, 710-739
monomers, 737-739
monoprotic acids, 479
135-136, 135/
noble gas notation , 117. 117 / 700-701
-
fission , 695 698, 697/ 698/
alcohols. 731 , 731/ 731 /
monosaccharides, 751 -752. aldehydes, 731 /. 733. 733/
nomenclature. See also fusion , 695-696, 699, 699/
alkanes, 716-723, 717/, 718/.
752/ 821.821/ notation - - .
half life , 688 689 688/ 688/,
.
719/, 722 / 723/
Moseley. Henry. 135 for acids. 230-231, 230/, -
706. 708 709
multiple bonds. 180-188. 187/ 468- 469. 468/. 469/ mass defect , 681 alkenes, 724 -727, 724/, 727/
for covalent - network com -
alkyl halides, 731 /. 732, 732/
187/ nuclear binding energy,
735
muriatic acid . See hydrochloric pounds, 230 -
681 682, 682/
alkynes, 727-728, 728/
acid for ionic compounds. nuclear radiation, 685.
amines. 731 /, 733
222-223 693-696, 693/ 694/ 695/
carbon bonding, 711-712,
for molecular compounds. nuclear waste, 695-696
711/ 712/
N 227-229. 228/, 229/
lor monatomic ions,
radiation detection, 694. 694/
simulation of decay, carboxylic acids. 731 /, 734.
734/
NAI ) PH , 766 220-221.221 / 708-709
esters. 731 /, 734
names. See nomenclature for organic compounds. types of decay. 685-687.
uauotuhes, 710/ .
718-722, 718/. 719/ 725. 685/, 686/ 687/ .
ethers 731 /. 732
National Institute of Standards 728 nuclear forces, 76, 682-684, functional groups, 730-734,
730/, 731 /
and Technology ( NIST ) . 33 oxidation numbers and. 683/ 684/
natural gas. 723 234 -235, 235/, 642/ nuclear power plants, 698. history of, 715, 715/
hydrocarbons, 712. 712/,
Nernst , Walther, 597 for oxyanions, 225 -226. 698/
net ionic equations, 439 440. 226/, 469/ nuclear reactions, 684 . -
716 729
isomers, 712-714. 713/, 714/
603 for salts. 231 697-698. 697/
neutralization reactions, .
Stock system 221.224 - 225. nuclear reactors, 698 ketones, 73U 733.733/
487 - 489. 488/ 235 nuclear shell model , 683, 087 organic reactions, 735-739.
hydrolysis and . 610/, nonelectroly tes, 406. 406/ 447 nuclear sy mbol , 79 736/ 737/ 738/
611-612.611/ nonmetals, 19. 19/ 146 nucleic acids, 770 -775 polymers, 737-739. 738/
salts from , 468. 472 nonpolar-covalent bonds, DNA , 771 -772. 771/ 772/ 748-749
. - .
in titrations 515 521 515/
518/-519/
176 - 177. 176/ 177/ 204/ genetic engineering . structural formulas,
-
712 713, 713/
-
528 529 nonvolatile substances, 774 -775 . 774f
unsaturated hydrocarbons,
neutrons. 72. 76/ 855/. 446- 447. 446/ 447/ RNA , 773-774, 773/
724-729. 724/
newtons. 362 normal boiling point , 344. .
structure of. 770 770/ 824.
- .
organic reactions, 735 739
nickel 344/ 347/ 824/
in the body. 807/ normal freezing point, 345, 347 / nucleons, 681-682. 682/ 736/ 737/ 738/
osmotic pressure , 452- 453. 452 /
electron configuration. 118/. notation . See also -
nucleus, atomic. 72 76. 75/
oxidation, 632
119, 144 nomenclature 76/, 682-684. 683/ 684/
oxidation numbers, 232-235,
properties. 798-800, 800/1 for aqueous solutions. 435. nuclides, 79. 681.685. 691 692.-
SOI / 499. 592 692 / . .
235/ 631-632 631 /,
nitric acid , 309. 470 471 . for cycloalkanes. 718 nylon, 739 -
634 635
470/ for electrochemical cells. 657

INDEX 943
 -
oxidation reduction reactions. particles - -
of J and / block elements, radioactive decay, 689
630-645 .
alpha , 74. 75/ 685/ 686 693. . . -
163 164 photochemical processes 836 .
balancing equations for. 693/ electron affinity, 157-159. photochemical smog, 836
637-641.644. 650 .
beta , 685/ 686, 686/ 157f, 158/ photochromic lenses, 634
in blast furnaces. 814. 814 / colloids, 403- 405. 404/ 404/ elect ronegativitv, 161-164» photoelectric effect, 99-100, 99 /
covalent bonds and , positrons. 685/ 686-687 . 161 /, 162/ .
photons 1 ( H )-101
634-635 solvated , 415 415/ . .
ionic radii. 159-160 159/, 164 .
photosy nthesis 306-307 751 , .
disproportionation. subatomic 72 , 682 . .
ionization energy 153-156, 766, 766/
644 -645, 645/ .
pascals 364 365. 364/- 153/, 154/ 155/ 164 . pH paper, 8/; 468. 468/ 471 ,
in electrochemical cells. Paschen spectral series, 103, valence electrons, 160, 160/ 512.515/
655-657 103/ periods, of elements, 17. physical changes, 7-8 9 / .
-
half reactions 633 634 . - Pauli exclusion principle 112. . 138-139, 138/ physical chemistry, 4 , 70. 445
nomenclature. 642 / 112/ permanganate ions 652-653 . phy sical chemists, 70
oxidation number rules. 631 / .
Pauling Linus, 161 . 161 / peroxide ions, 644-645 physical constants, 855/
oxidation states. 232- 235. -
/ / block elements, 146 148, - .
petroleum 723. 723/ physical properties, 7- 8. 9 /
. -
235/ 631 632, 631 / 147 / petroleum engineers, 720 pickling 471 .
oxidizing and reducing pepsin, 765 pH, 498-521 picomctcrs ( pm ). 76
agents. 642 - 645. 642 /. 643/ peptide bonds, 756 acid and hast* strength and . .
Planck Max, 99
in photochromic lenses, 634 percentage composition . 509, 509/ Planck 's constant , 99. 855/
titration exercise on , 242-244. 256 buffered solutions, 606 - 607 . plasma ( blood ) 762 .
652 653 - percentage error, 45 606/ plasma ( state of matter ). 8. 680/
oxidation states, 232-235, 235/. percentage yield 317 318 . - calculations involving, platinum 144 .
631 632, 631/ perchloric acid, 484 505-509, 509/. 526 Plunkett, Roy, 4
.
oxides, 278-279 834 -835, 835/ periluorocarhons 417 417/ . . of common materials, 504/ pOH, 503
oxidizing agents, 642-645. 762 definition . 503 polar bonds, 176-177. 176/
642/, 643/ periodic law, 132-135, 134/ enzyme activity and. 765 177/ 204/
oxyucetylene torches, 728. 728/
oxy acids, 230-231. 230/, 469.
St'’t also periodic table of
the elements
hydrolysis of salts and .
608-612.608/ 610/ 611/
-
polar covalent bonds, 176-177.
176/ 177/ 204/
469/. 486/. 487 periodic table of atomic radii . indicators. 511-512 ($ee also polarity
oxy anions, 225 -227, 226/. 230, 151/ acid - base indicators ) acid strength and , 474
4691 periodic table or electron liming of streams. 510. 510/ in crystals, 340-341 , 340/
oxygen affinities 157/ . of neutral, acidic, and basic dipole-dipole forces,
discovery of . 303 periodic table of electronega - solutions. 500. 504 / 204 -206. 205/ 206/
electron configuration 116/ . . tivities, 161/ -
pH scale. 503 504.503/ 504/ dissolution and . 411- 412.
117 periodic table of ionization proteins and . 765. 782-783 412/
isotopes 82 / . energies, 153/ of rain water, 514 of hydroxyl groups. 487
molar mass 240 -241 . periodic table of the elements, self - ionization of water and , ideal gas behavior and , 332
ozone. 189. 579. 732. 836
. .
140/-141/ -
499 500. 499/ 5( H )/. London dispersion forces
- .
properties 10/ 832 833 artificial nuclides in . 692, 599-600 and . 207, 207/
834/ 692/ 692 / . of tap water. 477 in phospholipids, 755. 755/
reactions with 276 - 277 .
. designing, 137. 172-173 titration . 515-521, 516 f 823.823/
277/ 283, 283/ 302-303 electron configuration and. 9 / 518/ 519 / . 528 529 polar bonds. 176 - 177. 176/
resonance structures in . 189 116-122. 116/. 117 /, 118/. phase diagrams, 347 348, 347 /- . 177/ 204/
ozone, l «9. 579. 732. 836 120/ 348/ 358/ polonium, 685, 706. 832 834 / .
groups in . 135-136, 135/, phases, 342. 342/ polyamides, 739
136/ 143 (see also families ) .
phcnolphthalcin 513/, 516. 516/ polyatomic ions, 194. 199 - 200.
P history of . 133-135. 134/
new elements in . 114 -115
.
pi I indicators See acid base
indicators
- 230. 230/ 294
polyesters, 739
paper chromatography organization of , 16-17, 17/ pll meters, 512. 512/ polyethylene, 738, 738/
capillary action in, 335 335 / . periodicity in . 136. 136/ phospholipids, 755, 755/ 823 . poly merase chain reaction
in mixture separation. 12 . periods and blocks of. 823/ ( Pt R ) , 774
12/ 138-139, 139/ 142-149. .
phosphoric acid 469/ 469/ . polymer products 145, .
procedure, 432- 433. 144/, 163 - 164 471.480-481 748-749
-
848 849, 848/ 849/ periodic trends phosphorus .
polymers 737-739. 738/
parent nuclides 690 . acidic and basic oxides, 835, electron configuration, 117/ 748-749
partial pressures 365 368, . 835/ fertilizers. 831, 831 / poly peptides 756 .
.
366/ 599 atomic radii. 150-152 150/ . oxidation numbers, 235/ .
poly protie acids 479 481.48( 1/
particle accelerators. 691 , 691/ 151/ 152/ 163 properties, 19.828-829, polysaccharides, 753, 753/
828/ 829/ porous harriers. 656 657. 656 /

944 INDEX
positrons. 685 / 686 - 687 . primary structure, 759 radiation exposure, 693 694. rounding numbers, 48 48/ .
potassium principal quantum number, 694 / rubber, 748 -749
in electrolyte balance. .
107 107 / radioactive dating, 695 .
rubidium. 120/ 122. 786-787 .
789-790 789/ 790/ . . products, 9. 261 .
radioactive decay 685 692 786/ 787/ 788/
electron configuration. I IS. .
propane, 382 7 ] 6. 717 / decay series, 690-691, 690/ Rutherford. Ernest , 74. 75 /
I IS/ properties, chemical and half - life, 688- 689, 688/ 688/.
.
fertilizers 831, 831/ physical, 7-10. 9 / 706. 708-709
properties, 786-787 786/; . proportionality, 55 -57. 55/ simulation of. 708-709
S
.
787/ 788/ 55/, 56/, 57/ 572 types of. 685 687, 685 /,
-

reactivity of. 142/ proteins, 757-765 686/ 687/' sacrificial anodes, 662
potential difference, ( >62- 664. amino acids in, 757. 761. 761 / .
radioactive tracers, 695 695/ salt bridges, 656-657, 656/
676 biological functions, 760. 760/ radioactive wastes, 695 696 salts, 489
potential energy, 179, 179/ denaturalion 764. 764 / . radium, 685. 688. 688 /; .
as electrolytes 405 - 406. 406 /
pounds per square inch ( psi ) . digestion of. 765, 768 792- 793 , 792/ 794 / on freezing roads, 456 /
364 / as enzymes 550.760/ . . radon, 115. 136. 694 hydrates. 243 -244.411 411/ .
precipitates
from chemical reactions,
763 -765, 763/ 764 /
.
pH and 765, 782 -783.821
Ramsay, William. 114 - 115.
115/ 135- 136
hydrolysis of, 608 612, 608/
610/ 611/
-
262, 262/ 602 602/ . as polypeptides 756 . rate- determining steps . from neutralization reac -
from double-displacement shape and structure. 759, 759/ 576-577 .
tions. 468 472. 488 - 489,
.
reactions 282. 282/ side chain reactions 758.
- . rate laws lor reactions, 488/
438- 440. 438/ 758/ 571-578, 584 nomenclature 231 .
precipitation calculations . . . -
synthesis 736 773 774. 780 Rayleigh. Lord ( John William solubility product constants.
618-620 prutiiim. 78. 78/ 79/ Strutt >. 114. 114 /. 135 -
613 620, 615/, 620
precipitation reactions . proton-exchange membrane reactants, 9 , 261.312-316, sample problems approach,
437-439 437 / 438/. . ( PEM fuel cells ). 666 312/ 52-54
precision. 44 - 46. 44 / protons, 72 reaction mechanisms, 561-562. saponification, 754
preen/.y roes, 76 > atomic number and 77 . Sitf saturated hydrocarbons, 716.
prefixes nuclear binding energy and . reaction rates, 568. 591.591/ See also alkanes
acids, 231 682-683, 683/ See also kinetics of saturated solutions. 409. 409 /
carbon-atom chain 718/
molecular ctimpounds,
. .
properties 75 76/ 855/ . .
p-ty pe semiconductors, 827.
reactions
reaction stoichiometry,
scanning electron microscope
( SEM ). 3-4. 3/
227-229. 228 / 229/ . 827 /
'

299-301. See also scanning tunneling microscope

oxyanions. 226 pore substances, 11/, 13 - 14 , stoichiometry ( STM), 3/ 70 772/ 773/ .
Stock system and, 235 13/ 14/ 14 / reaction waves, 288, 288/ Schrndingcr wave equation,
. .
units 34 35/. 854/ purine bases, 770 real gases. 332. 332 / .
105-106 107/
pressure, 361, 361/ purity of reagents, 14. 14/ 14 / rechargeable cells, 669, 669 / scientific method, 29-31.31/
.
atmospheric 362-363, 362f ,
363/ 365
pyrimidine bases. n 70 recombinant DNA technology
775
. scientific notation, 50-52. 62
scintillation counters, 694
Boyle’s law, 369 -370.369/ .
redox reactions 633- 635.644. scuba dicing, 368
370f
combined gas law, 374 -375 Q See also oxidation-reduction
reactions
secondary structure, 759
second ionization energy,
critical, 347/ 348 qualitative analysis, 800, 800/ reducing agents, 642 645 . 642/, - .
155 156 155/
effect on chemical equilib- qualitative information, 29 />43/ second-period elements,
rium . 598 599 quantitative information, 29 reduction, 633. See also .
116-117 116/
.
force and 361-362.361/ quantity. 33 oxidation-reduction self-ionization of water,
362/ quantum, 99 reactions 499-500. 499/ 500/, 599
-
Gay Lussacs law 373 -374. . quantum numbers, 107 - 110. reduction potential. 662 self-oxidation, 645
373/ 107 /; 108/ 108/. 109/ I 10/ . relative atomic masses. 80- 81 self-reduction, 645
measuring. 363, 363/ See also electron reins, 693 semiconductors, 340 341 .
398-399 configurations resonance structures. 189, 729. .
826- 827 826/ 827/
.
osmotic 452- 453. 452/ quantum theory, 100-101. 105 729/ *
semipermeable membranes,
partial. 365 -368. 366/ 599 quarks, 682 respiration. 816 - 817. 816/ 817 / 452 453.452 /
solubility and. 413 quaternary structure, 759 reverse osmosis. 453 shielding. 698
.
units of 37, 364-365 364/ . reversible reactions, 266-267. significant figures, 24. 46-50,
vapor. 343 344. 343/ 344/
- 270. 589-590 . .
47/ 48/ 505
366. 446- 447
R rihosomul RNA ( rRNA ). 773 .
silicon, 117/ 230, 812-813 .
water- vapor 859/ . RNA ( ribonucleic acid ), 812/ 813/
Priestley, Joseph, 279. 302 .
radiation, 685 693 - 696 693/ . 773 -774 , 773f silver
primary standards, 517 694/ 695/ roentgens, 693 .
alloys 803/ 804 /.

INDEX 945
 silver { continued ) solutes standard molar volume of a sugars, 406, 406/, 751-753. 752/
electron configuration. 120/ .
dissolution rate 407- 408. gas . 380 381 sulfur
in photochromic lenses. 634 407/ standard solutions, 517 chemical bonding. 177
properties. 798. 799/ 801 / electrolytes, 405- 406. 406/. standard temperature and crystalline forms. 832f
solubility. 613- 614 442- 443 pressure (STP), 364 electron configuration. 117/
single- displacement reactions. solubility. 408 410. 408 /, .
starch 753. 753/ 822. 822/ oxidation numbers, 235, 235 /
-
281 282, 281 /. 285 409/ 410/ .
states of matter 328-352 properties. 832- 833. 832/
SI units, 33 42. 854 / solute- solvent interactions, changes of stale 342-348. . 833/ 834 /
base units. 34 36. 34 / 410- 415.411/ 412/ 413 / 342 /. 344 /; 345/ 347/ 348 / .
sulfuric acid 470
conversion factors. 40- 42. 414/ gas properties, 329- 332 . in acid rain. 489, 489/
50. 92 ty pes of, 402, 402 / 330 /; 331/ 332 / '
in .
car batteries, 669 669/
derived units, 36-39.36/. 38/ .
solution equilibrium 408- 409. liquid properties. 333-336. as diprotic acid, 480.480/
prefixes in. 34. 35 / 408 / 334 /; 335/ 336/ nomenclature, 469/
sodium .
solutions 400- 424 . See also solid properties. 337-341. production and uses of, 470.
in electrolyte balance. 789, aqueous solutions 337 /; 338/ 339/ 340/, 341 / 837, 837/ 837 /
7891 buffered. 606- 607. 606/ .
steel 803. 803/ 814 structure of. 469 /
electron configuration. 117. components of. 402, 402/ steroids, 755 superconductors, 18
I 17 / dissolution rate. 407- 408. .
Stock system 221.224 -225. supercooled liquids, 338
industrial production of. 671 407/ 235. 235 / supersaturated solutions, 409
oxidation stale, 632, 632/ enthalpies of. 415 - 416, 415/ .
stoichiometry 298-318 surface area, 407. 407/
properties. 786-787, 786/ 416 / composition vs. reaction. 299 568- 569
787/; 788/ entropy in. 547-548. 548 / gas, 581 182 .
surface melting 346
sodium chloride in Henry’s law. 368. gravimetric analysis and. surface tension, 335. 335 /
crystal structure, 191- 192. 413- 415, 413/ 414/ 326-327 surfactants, 417
191/ 192/ 338/ liquid- liquid miscibility. 412. limiting reactants. 312-316 .
suspensions 403. 404 / . 405
dissociation of. 435- 436, 412 / mass- mass calculations, symbols, unit 854 /
435/ 608 / molality. 422-424. 422/ 310-311 symbols
*
used in equations .
as electrolyte. 405 - 406. 406 / molarity. 418-421.419/ 430 mass- mole conversions. 265 - 267. 266 /. 855 /
ionic bonding in. 190- 191. nonelectrolytes in. 405- 406, 306-310 synthesis
*
reactions, 276-279.
190/ 191 / 406/ molar mass and. 301 277/ 288
lattice energy. 192. 193 / observing, 405 mole conversions. 304 -306
sodium hydroxide, 488 - 489. pressure and, 413 mole ratios and. 300-301.324
488/ 754
sodium-potassium pump. 790.
properties. 401/ 404 /
saturated vs. unsaturated,
percentage yield. 317-318
Strassman, f rit /, 700-701
T
790 / 409. 409/ strong acids, 474 - 475 . 474 /. temperature
solids, S. 337-341. 338/ 339/ solubility. 408 - 410. 408/ .
484 - 485, 485 / 501 / 509 . absolute zero, 371
340/. 341 / 409/ 410/ .
strong bases 475- 476. 475 /. Charles’s law, 371-372.371 /;
sols, 404 / . See also colloids solute - solvent interactions, 476 /; 484- 485, 485 / 372/
solubility, 408- 410 410- 415, 411/ 412/ 413/ strong electrolytes, 442 . 442 / combined gas law. 374-375
calculating. 617- 620
definition , 616
414 /
standard. 517
.
strontium 120/. 792- 793.792/
794 /. 795. 795/
critical. 347. 347 /
dissolution rate and, 408
dissociation. 435- 439. 435/ supersaturated . 409 structural formulas 185 . effect on chemical equilib-
.
437/ 437f, 438/ types of. 402- 403. 402 / .
structural isomers 713. 713 / rium. 600-601.601/
of gases in water. 860/ solvated particles, 415. 415 / subatomic particles, 72. 682 enzyme activitv and. 764 .
precipitation calculations. solvents, 402. 402/ 411 sublimation, 342 /. 346-347 764/
618-620 specific heat, 532-534, 533/ substitution reactions, 735 of gases, 33< I
precipitation reactions. .
specific rate constant 573 s 7 S substrate molecules, 763-764 . Gay- Lussac’s law, 373-374,
437- 439. 437 /. 438/ .
spectator ions 439. 489. 494 763/ 373f
pressure and, 413 .
speed 37 / sucrose, 752-753 heat and, 531-532, 532/
saturation. 409 . 409 / speed of light, 855 / chemical reactions. 737. reaction rale and. 569
solubility charts. 860/. 861 / spin quantum number 110. . 737/ 752-753. 752/ 753f scales. 371-372.531
solubility products. 613 - 616. 112 chemical structure. 178/ SI units of. 34 /
< > 15 / stainless steel, 803. 803/ 752/ 821/ solubility and. 410/, 414 —
temperature and. 410/. standard electrode potential, vapor pressure and. 447. 447 / 415, 414/
414- 415.414/ 663 - 664 . 663/ 664 / suffixes tensile strength, 18
solubility product constants, standard hydrogen electrode hydrocarbons, 720. 725. 728 tertiary structure. 759
614- 620.615/ ( SHE ). 663. 663/ molecular compounds. 228 Thales of Miletus, 43
soluble substances 401. oxvanions, 226-227 theoretical yield, 317

946 INDEX
 .
I henries 31, 31 / mercury poisoning 805. 805 /. .
corrosion in 661-662 661/. . water purification , 273 274.
.
Ihcrmile reaction 560/ 809/ -
properties. 144 146. 144/ 662/ 453
thermochemical equations, 798-800. 799/ 8( H)/ 801 / electrode potentials, water testing, 464 465
535 transmutation, 684 . 691-692. 662- 665. 663/ 664/, 676 water treatment, 840 841.840/
thermochemistry, 531-55( ) 691/ 692/ 692 / electrolytic cells compared Watson, James, 771
calorimeters, 531.539. 539/ transuranic elements, 092. with. 667-668, 667/ wavelength, 97-99 98 / .
-
558 559
definition . 531
692/ 692 /. 700-701 examples of . 659 660, 659 /, waves
triglycerides, 754. 823. 823/ 660/ diffraction and interference.
enthalpy of combustion. .
triple bonds 187. 187/ 187/ . operation of . 658, 658 / 104. 105/ 106
538-539, 539/, 856/ 727-728 volume electrons as, 104, 105/
enthalpy of formation. triple point, 347, 347/, 855/ Boyle s law , 369-370, 369/ light as. 97-99 98/ .
.
537-538 542-544, 543/ triprotic acids, 480 370/ Schrodinger wave equation .
enthalpy of reaction ,
534-537, 536 /, 537/
tritium , 78 -79, 78/ 79/
trypsin, 765
Charless law, 371-372.371/
372/
-..
105 106 107/
weak acids 474 - 475. 474 /,
entropy. 546 -548. 547/ 548/ tungsten, I 19. 144/ combined gas law. 374 -375 605- 606 606/.
free energy, 548 558* 549/ Tyndall effect, 404 . 404 f molar. 380-381 weak bases, 475- 476 475/ . .
heal and temperature. units of , 36/. 37, 37/ 854 / 476/
531-532, 532/ .
volumetric analysis 850-851 . weak electrolytes, 442 /. 443
Hesss law. 539 -542. 556.
558-559
u 850/ 851/
VSEPK theory * 197-201, 198/
weight , 35
weighted averages, 81 82, 128 -
specific heat. 532-534, 533/ uncertainty principle, 105 199/ 2( H )/ Wilkins, Maurice, 771
stability and. 538 unit cells, 339 Wohler, Friedrich , 715 . 715/
third ionization energy, 155. units. See SI units word equations, 263 264 268 - .
155/
-
third period elements,
unsaturated hydrocarbons,
724 -729. 724/
W
117-118. 117 / unsaturated solutions 409. . .
water 349-351
X
Thomson, Joseph John 73 . 409/ a s amphoteric substance.
thymine, 77( 1. 770/. 824 /
.
uracil, 770. 770/ 773. 824 / 485- 486 -
X ray diffraction patterns, 4
time, units of 34 / uranium .
boiling point 344. 344/ 351 ,
titanium, 118/. 119 .
chain reaction 697-698, 697/ 855/
decay series. 690-691. 690/
titration, 515 > 21
acid -base. 515 -517.516/, 51 If discovery of . 7( )0
as Bronsted - Lowrv acid. 478
changes of state in 8 9 f .. Y
balancing equations for. isotopes, 79. 82/ .
density 351 , 859/ Yucca Mountain nuclear waste
639-641 oxidation numbers. 233-234 dipole interactions 205-206. . site 696.
end point . 516 206/
equivalence point. 516 from double-displacement
lab exercises, 528-529,
652- 653
V .
reactions 283
.
electrolysis of 670.670/
z
procedures, 517 - 521.518/ vacuum filtration, 845 845 / . freezing point 855/ . zinc
519/, NS < » 851, 850/ 851/ vacuums, 376 -377 hydrogen bonding in , 206. in the body 807/ .
-
redox, 639 641 , 652-653 valence electrons, 160, 160/ 21 H in cathodic protection 662. .
Torricelli, Evangelista, 363. vaporization, 1 %, 335 336. .
ice. 342/. 346-347 349-350, 662/
363/ 376. 376/ 336/ 342 /. 345. 345/ 350/ in dry cells. 659. 659/
torr, 364. 364/ > apor pressure .
343 344 . 343 /, ionization constant. in electrochemical cells,
trace elements, 806 807. 806/ 344/ 366 500-501.500/, 6( H ). 607 655-660, 655/ 656 /; 657/
807 /. See also transition -
vapor pressure lowering, molecular geometry, 199. 658 f
metals .
446 - 447 446/ 447 / ’ 199 /; 202.202 f electron configuration. 118/ .
t r a n s f e r R N A ItRNA ), 773 variables, 30 phase diagram . *47 -348 . 119
trims isomers, 714 , 724 / i 724 /
transition intervals, 512. 513/
Verneuil , Auguste, 801 802 347/ 351 .
properties 798-800, 799/
visible spectrum, 98 / as pure substance. 13. 13 / 800/ 801 /
transition metals, 144 - 146,
798-807
vitamins, 755. 820, 820 / -
self ionization. 499-500.
499/ 5( H ) /, 599-600
as reducing agent. 643. 643/.
volatile liquids, 343 643/
.
alloys 802-804. 803/, 804/
in the body, 806 -807. 806/;
Volta, Alessandro, 444
voltage ( potential difference ),
structure of . 349-350, 349 /
lap. 477
-
zinc carbon dry cells, 659. 659/

807/ - .
662 664 676 triple point , 347, 347 /. 855/
gemstones. 801 802.801 /; voltaic cells, 658-666 water-vapor pressure. 859/
802 /

INDEX 947
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Amnld. Inc.: x ( lie), Richard B. Swint, M D 1 he
(I)left , ( r ) right , ( hkgd ) background .
Photo Researchers Inc. Table of Contents: r ( hi ). .
Texas Collection Baylor Unversity. NVaco Texas;.
. 1
F d Bock CORBIS: vi ( tl >. Sinclair Stammers/ .
\ ( blc ) 0 Sandra l\ any /FoodPlx/( icily Images: \
All photos, unles * otherwise noted , by Sam Photo
Diidgcnn/ IIRW. Coven W P Wergm F. F. Lrbe:
Researchers, Inc.; vi ( cl ). tij> National . .
( bl ) <• Paul Chesley/Geltv Images; \ i ( tie ) Greg
Institute Edmonds/Farth Images: \i ( blc ). '0 SuperSlock
of Standards A: technology / Photo
culator icon: Andy Christiansen 11 RVN Historical MI ( tl )
.
Electron Microscope lTnit; ARS -I ‘SIM CBL cal- Researchers. Inc : vi ( bl ). Lurehos Phototake;
1
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PictureQuest: \ i ( hi ) Jet Propulsion Laboratory
. * Silvestre Machudo/SupcrStock: vii (cl),
Chemistry feature icons: ( bkgd ). Charles D. > NOAO/Photo Researchers. lnc* vii ( bl ) , Alfred
.
NASA: xii ( tl ) EFDA JLTPhoto Researchers
4 .
Inc.: xii ( cl ) Photo Courtesy Chakrapani et al.; xi
.
1

Winters. Cross- Disciplinary Connection feature Pasieka

.
( bl ) Dr. Jeremy Burgess Photo Researchers. Inc.
/Sciencc Photo Library Photo Researchers,
icons: ( I ), Digital Art /CORBIS; ( c ). PhotoDvsc Inc. \ iii ( tl )
1 1

Dr. Dennis Kunkel/ Visuals

: / .
. Phil Degginger Bruce Coleman Inc.; . .
xiii ( bl ) J & I Weber/Peter Arnold. Inc Chapter I
get t vintages: ( r ).
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viii (bl ). Richard Megna/Fundamental Photographs.
Unlimited. Careers in Chemistry feature icons: ( 1 ). viii ( cl ), Robert Burch Bruce Coleman, Inc.; ix
2 ( c ), Sinclair Stammers Photo Researchers Inc. .
• kalu/ ny - 1 hatcher Getty Images ( c ).
. .
3 (br ) Volkcr Steger / Peter Arnold, Inc : 5 ( tr >
IAVA ill ). Andy Goldsworthy. Courtesy of the artist and
* Jon Pcingcish CORBIS: 13 ( bl ). Tom Pantages
Stephen Welstead/( ORBIS; ( r ). • Roger lulls Cialcric Lelong. New York.: ix ( cl ). Pictor .
Photography: Is ( c ) James Lyle Texas AA: M
Gem Images Chemistry in Vrtiou feature : icons
. . .
International ImageSlate / Alamy : ix ( bl ) ' Stephen l'mversit \: IK ( bc) Bruce Iverson; 20 ( t ) C. Bradley
ill. ' 0 Maximilian Stock Ltd Photo Researchers.
.
Inc ; ( c ). Lawrence Berkeley Laboratory Science
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Simpson Gellv Images; \ ( tl ) J A: I Wehei Peter Simmons Bruce Coleman Inc Chapter 2: 2S ( e ).

948 CREDITS
 National Institute of Standards A Technology / Wildlife; > \ I ( bl. hr ). Jerry Mason Science Photo
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Photo Researchers. Inc. Chapter 3: 66 ( c ). l ibrary/Pholo Researchers. Inc.: 5 I 2 ( hi ). Photo .
Jr. Bruce Coleman Inc.: 795 ( be ). PhotoTake: 796
• Eurchos/ Phototake : 68 ( ll ). Grant Heilman Researchers. Inc.. 513 ( all ) , Peter Van Slcen/IIRW ( tr ). Chris Rogers/ Rainbow : 797 Ml ). Dr. E. R
Photography. Inc.: 7o ( cr ). IBM Corporation/ Photo: 516 ( bl . br ). Richard Megna/Fundamental Deggtngcr/Color- Pic, Inc.; 798 ( br ). t Brent
'
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Research Division. Alinaden Research Center; S 3

'
Photographs Chapter 16: 530 ( c ). « Paul Cheslcy / C avedo / SuperStock ; 79S ( tr ). <0 Thomas Del
'

i ir. cr . hr ). Dennis Fagan IIRW. Chapter 4: 96 ( c ) . Gettv Images Chapter 17: 562 ( tl ), Larry Brase /Geltv Images; 798 ( cr ) . Larry Stepanowicz:
1
Silvestrc Machado / SupcrStock : 100 ( cl ). Stepanowicz: 573 ( br ). * Robert Harding World 798 ( be ). Ken Lucas/VisUuls Unlimited; 798 ( bl ).
• SuperStuck ; 105 ( tl ). Polytechnic Institute of linagcry/ Alamy Photos; 579 ( hi ), Dorling Kindersley £ > Bettmann CORBIS: 799 ( tl ). David R . Frazier
Brooklyn; 105 Or ) . Atlas ot optical phenomena by Limited courtesy of the Science Museum. I ondon/ Photolibrary; 79*4 ( cr ). L. S. Stepummicz/ Visunls
Michel Cagnel. Maurice Francon & Jean Claude Corbis Chapter 18: 588 tc ) . Greg Edmonds/ Earth Unlimited HOI ( all ) Lorn Pantages Photi >graphy;
Phrierr. Published by SpringerVerlag in 1962. Images; 593 ( all ). Di. E. R Degginger Color- Pic. 802 ( tr. tl ). 1 arry Stepanowicz; 802 ( br ) . Tom
1
Springer - Verlag; 114 ( bl ). Reprinted with per - Inc.; 597 ( ti ). Steve Mc( 'ulcheon/Visuals Unlimited; Pantages Photography; 803 ( tr ). « > Dan McCoy /
mission from Nature ( No. 1196. Vol. 46). 60S ( all ). Dennis Eagan / HRW; MS ( all ). John King 1
Rainbow ; 804 ( hi ), o 1Tank Morgan Rainbow; 804
’

C opyright 1 X92 Muetmllinu Magazines l imited; HRW ( huptcr 19: 630 ( c ) SuperStock (br ), Dan Rubin /I he Stock Shop/ Mcdichromc;
115 Ol ). Hlliott A Fry. photographers, courtesy PictureOuest : 633 ( tr ). Richard Megna 808 ( hr ). Visuals Unlimited; 808 ( be ). Arthur
AIP Emilio .Scgre Visual Archives, WE Meggers Fundamental Photographs; 636 ( c ). Renee Lynn Hill/ Visuals Unlimited: 809 ( hr ). Tom Pantages
Gallery ol Nobel Laureates; 130 ( e ). Photo lake . Photo Researchers. Inc.; 645 ( be ). Richard 1. Photography: 810 ( cr ) . ( ' CoC'o McCoy/ Rainbow:
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Inc.r 133 ( br ) . • SuperStock: 142 ( bl ). Dr. E. R . Eisner and Daniel Aneshansley. Cornell University. J & L Weber / Peter Arnold , Inc.; 81 X ( cr ) . Tom
Degginger / Coloi Pic, Inc.; 142 ( br ). Breek P .
( huptcr 20: 654 ( e ) Jet Propulsion Laboratory Pantages Photography: 820 ( tc ). Ir \ ing Gcis/
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Alfred Pasieka / Pcter Arnold. Inc .: 145 ( cr ). 666 ( c ). Getly / NewsCom. Chapter 21: 680 ( c ) .
'
* ’ Myron Jay Dorf /CORBIS; 829 ( c. cr ) . Dr. E R .
.

N ASA . 147 ( bl , el ). Dr . I R Degginger /Color-Pic. EFDA - JL I Photo Researchers. Inc. : 693 ( b ), Degginger /Color- Pic. Inc.; 830 ( br ) O George .
Inc. ( huptcr 6: 174 (c ) . Alfred Pasicka/Sciencc Fcrmilab National Accelerator Laboratory; 695 Glod/SuperStock: 830 ( bl ). • ) Petci Beck /COR -
Photo I ibrary/ Pholo Researchers. Inc.; 190 ( bl ) . Mi ) . 1991 peter Bcmdt, M.D RA \ 11 Rights BlS: 832 ( cl ). Heather Angel Natural Visions; 832
Bruce Iverson: I 1/ ' 01) Photri: 206 ( be ). Photri.
' Reserved: 699 M ) > Roger Ressmeycr ( < )RBIS; .
(cr br ). Dr. E. R . Degginger/Color- Pic Inc.; 839 .
Chapter 7: 2 IX ( c ) . Phil Degginger / Bruce 700 ( be ) , AIP Emilio Scgre Visual Archives; 701 ( bl ). Tom Tracy /The Stock Shop/ Mcdichromc .
.
Coleman, Ine. C hapter K: 260 ( e ) Robert Burch/ Mr ), AIP Emilio Scgre Visual \ rehives; 708 ( cl ) . Reference: 842 - 84 4 ( bkgd ). Yoav I e \ y Photolake:
Bruce Coleman. Inc.; 272 ( tr ) . I S Stepanowicz/ Peter Van Steen HRW Chapter 22: 7 |0 ( c ), Photo 843 ( t ). Photri: 864 ( c ). Stephen Simpson Getty
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Visuals l nlimited; 2XS ( all ). Institute of Structural Courtesy ( hakrapum ct ol.; 712 ( bl ). Gregory K Images: 866 ( br ). Science Photo Library/ Photo
Miicrokmelics and Materials Science ( ISMAN ); Scoti /Phoio Researchers, Inc.: 714 ( tc ). Runk / Researchers. Inc . . 867 ( c ). Photo Researchers. Inc.;
296 ( bl ) , Loin Pantages Photography. Chapter 9: Schoenberger/frrant Heilman Photography. Inc /. 869 (cr ), Bruce Iverson; 871 ( br ). " Ed Bock /COR -
298 ( e ). Riehard Megna Fundamental Photoglyphs. 715 ( c ). C> Science Photo Library / Photo BIS; 875 ( br ). Phil Degginger/ Bruce C oleman. Ine.:
>02 ( tr ) .
1
Stefano Bianchelti/CORBIS. Chapter Researchers. Inc.; 723 ( tr ). < 1 David Spindel/ S7S ( c ). J A I Weber/ Peter Arnold. Inc.
HI: 32 X ( c ). Andy Goldsworthy. Courtesy of the SuperStock ; 723 ( br ). c Keith Wood/Gettv
.
artist and Galcric Lclong New At >rk .: 334 ol ). Images: 728 ( bn. C> Kevin Anderson Getty
Photos by Charles I ). Winters: xi ( til, xiii ( be ) 3 .
. . .
(bl) 7 ( hi ), 8 ( bl ), 10 ( t ) 12 ( tl. tc) 13 ( br ). 14 ( all ),
Dennis Fagan I IRW . 335 ( er ), Harold A Esther
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images; 734 ( tl ) . Seth Joel/ Science Photo
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IS ( bl. br ) 19 ( all ) 26 ( bl ) 38 ( tl ) 73 ( tr ) 94 ( bl ) . .
I dgertott Foundation 2l 6. Courtesy ol Palm
. *
Press . Inc.; 336 (cl ) Dr. I R . Degginger/Color
I ibrarv /Photo Researchers, Inc.; 748 ( be), l Maries
( Arcil/ Visuals Unlimited: 748 ( bl ). Irim Pix Peter . . .
142 (tl. cl) 144 ( be br ) 147 ( cr, br ) 224 ( h ). 231
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( t ), 239 ( tr ). 258 ( bl ) 261 ( hr ) 262 ( all ) 270 ( el)
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Pie. Inc.; 337 ( br ). Photonica; 33S ( cl ). Photo lake; Arnold. Inc. Chapter 23: 750 ( c ). Dr. Jeremy
3.49 Or . cl ) . PhotoTake: 339 (c. cr. br. tl . tc >. Breck Burgess/ Photo Researchers. Inc.; 752 ( cl ) ,
. .
277 ( all ) 280 Me ) 281 ( br ) 316 ( br ) 334 ( bl be. .
<* Richard Hamilton Smith/CORBIS: 754 ( bl ).
hr ), 335 ( bl, be ). 337 ( be ), 358 ( bl ) 366 ( tc ) 371 . .
P Kent / Animals Animals/ Furth Scenes; 341 ( tr ).
Stephanie Lriedman HRW 757 ( tr ). Dr Jeremy . . .
( all ) 401 ( cl) 4t ( all ) 413 ( all ) , 437 ( t ), 438 ( b ) .
Dr E R Degginger / C olor-Pic. Inc. Chapter 11:
360 ( e ). Pictor International/ IrnageStalc/ ALimy; Burgess Photo Researchers, Inc.; 761 ( bl ) . • 1 1 iopal . . . . .
444 ( b c) 467 (bl ) 470 ( bl br ) 471 ( br ) 472 ( br ) . .
361 ( all ). Dennis Fagan/IIRW; 362 ( b ). NASA / '
Murti /Phototakc; 761 ( cl ) . 1 Microworks/
. .
476 ( tc ) 477 ( br ) 480 ( all ), 486 ( tc ) 488 ( b ). 490 .
SI PA Press; 36X ( bl ). ' < Royalty Free /CORBIS; Phototake: 762 ( bl ). National Portrait Gallcrv. . .
( bl ), 497 ( ll ) 512 ( cl. cr tr. tc, tl ), 528 ( bl ). 532 Mill ),
. . .
547 ( all ) 560 (c) 561 ( hr ) 569 ( all ) 570 (cl ) 587 . .
376 ( bl ). » > Bettmann/ C ( )RBIS ; 477 0 ). " James Smithsonian Institution / Art Resource . NY; 765
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Schwahel/ Panoramic Images: 377 ( c ). « ' Leo I .. .

(cr ) \ ndy Chrisliansen/HRW: /66 ( bl) Barry .
( hih 589 ( br ) 602 ( be ) 604 (clL 606 ( tl cl ) 628 ( bl .
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I arsoniPanoramic Images: 398 ( be ), age foto-
stock Kick ( iomez. Chapter 12: 4( Ni ( c ) . \ Stephen
Runk /S I'AN/Grant Heilman Photography. Inc.;
772 Me ). W Schonetl GSI Biophysik Darmstadt . . . . . . .
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Simpson/fieliy Images; 401 ( bl ) , Courtesy Dr . C*. Germany; 773 ( br ). « Kiseleva and Donald
. . . . .
W Dill , Texas AAM University - Corpus ( hrisii
Bell 1 ibrary: 403 ( tl ). • Neal Mishler/Cietts
I awceO / Visuals Unlimited; 774 ( bl ) , David
Parkcr / Photo Researchers. Inc.; 775 ( tr ). ( Maries . . * . . . . . .. .
( tl tr ) 793 ( tr cl cr ) 795 ( cr ) 79 ) ( bl br tr cl bl )
800 ( all), 808 (cl, bl ), 809 ( tr bl), 812 (cr cl br ) 813
(cr ), 821 Ml ), 825 ( all ), 828 ( bl, br ), 829 ( cl ), 832
Images; 404 ( cl ) , Richard Haynes HRW; 408 ( bl ).
Peter Van Steen I IRW Photo. Chapter 13: 434 ( c ),
Marden Filch Elements llandhouk: 784 785
( bkgd ) , Yoav Le \ y/ Photolake; 784 ( bl. be ), Tom . . .
( bl ), 833 ( all ) 838 ( all ). 839 Mr br ) 844 ( be ) 845 .
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( all ) 847 ( all ) 850 ( bl ) 851 ( all ) 872 ( tl ) 876 ( bl ) . .
Kent / Animal Animals * Earth Scenes; 787 ( cl. cr.
877 ( b )
'O Million Archived icily Images; 456 ( tl ) , *
Lawrence Stepanowicz Bruce C oleman. Inc. IK ). Lester Bergman/The Bergman Collection: Photos by Sergio Ported: xix ( tl ). \ \ ( ll ) 9 ( t ) 12 .
Chapter 14: 466 ( c ). Richard B Swint. M l ) I he 787 ( hi, br ). Dr. E. R , Degginger /Color-Pic, Inc.; Mr ), 29 (b ). 46 ( tl ). 61 ( br ), 265 ( bl ), ?7 X ( bl ) 282 .
Texas Collection. Baylor Unversity. Waco, Texas: 788 ( all ). Phi- Lo Photo; 789 ( cl ), John Langford/ ( bl ) 283 ( bl br ). 4.27 Mr ). 330 ( 0 ) 437 ( bl ). 479 Mr .
4 6 7 ( hr ). Peter Van Steen IIKW Photo; 4 7 9 ( tc ). I IRW': 791 ( bl ). PhotoTake: 792 ( bl ) . Dr. E . R . . . . . .
cr. br ). 403 ( Ir ) 419 ( I cl cr r, bl be, br ), 422 ( I b 432
Photo Researchers. Inc. ; 4 X9 ( cr ). <* Thomas
' Degginger /Color- Pic. Inc .* 792 ( be ) , Carl I rank / . .
( be ) 515 ( be ) 518 ( tr, cl. c, cr, bl, IK. br >, 519 ( tc. tr .
NiUen Photo Researchers. Inc. Chapter 15: 4*48 Photo Researchers. Inc.. 79? ( hr ). ( Jury Retherlord/ .. . .
cl. c cr bl. be br ) 601 ( tl. tc. tr. tr ). 694 ( bl br. IK ) . .
(c) 1
Sandra Ivanv /FoodPix/Getty Images; 500 Photo Researchers. Inc.; 792 ( cl ). Breck P. .. . . .
711 ( bl c IK br ) 727 ( br ) 786 ( IK . br ), 787 ( tc)
( hi. hr ). Riehard Megna /l undamental Photographs; Kent / Animals Animals/ Earih Scenes; 793 ( bl. IK ).
5 | o ( c ) , Massachusetts Division of Fisheries A PhotoTake: 793 ( br ). Larry Stepanowicz: 794 ( cr ).

CREDITS 949
 Periodic Table of the Elements
1

i
H
Hydrogen
1.007 94
'
15
Atomic number 6
Group 1
3
Group 2
4
Symbol
c
2 Li Be Name Carbon
Lithium Beryllium
6.941
Average atomic mass -
12.0107
9.012 182
[Heps
' Electron configuration [He]2s22p 2
11 12

3
Na Mg
Sodium Magnesium
T3
22.989 770 24.3050
O
aJ
[Ne|3s ' Group 3 Group 4 Group 5 Group 6 Group 7 Group 8 Group 9
CL
19 20 21 22 23 24 25 26 27

4 K Ca Sc Ti V Cr Mn Fe Co
Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt
39.0983 40.078 44.955 910 47.867 50.9415 51.9961 54.938 049 55.845 58.933 200
Mb ' [Mi/ Us 2
JArj3dJ4s 2 [Arli/V 2 2

37 38 39 40 41 42 43 44 45

5
Rb Sr Y Zr Nb Mo Tc Ru Rh
Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium
85.4678 87.62 88.905 85 91.224 92.906 38 95.94 (98) 101.07 102.905 50
|Kr|5s ' [Krj5 s 2 IKrHrf 'Sj1 [Krj4/ 2SsJ [Kf}4</ V [KrHdSsI [Kr ]4 (f5s ' «V
[Kr| [Kij4rfV

55 56 57 72 73 74 75 76 77

6 Cs Ba La Hf Ta W Re Os Ir
Cesium Barium Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Indium
132.905 43
m* '
137.327 138.9055
[XeJSd Ss 2
178.49
,
180.9479 183.84 186.207 190.23 192.217
' [XeHf 4 / 2
’* * 2
[Xei4 f 45</ V (Xe}4 f W
’ '
[XeHf Vfc 2
'
(Xe)4 / Vfe 2
" '
M4/ V 6sJ
87 88 89 104 105 106 107 108 109

7 Fr Ra Ac Rf Db Sg Bh Hs Mt
Francium Radium Actinium Rutheriordwm Dubmum Seaborgium Bohnum Hassium Meitnenum
(223) (226] (227) (261)
,
( 262) (266)
,
(264) (277)
,
(268)
[tops ' '
|to)6d 7s2 '
[Rnj5 f V27s2 [Rnl5 / 4fc/ J7s2
'
[Rnl5f Ws1 [Rn}5 / 46i/ 7s 2
* '
(to|5f W [RnJ5 / 4&/ 77j2

• The systematic names and symbols

for elements greater than 110 will
be used until the approval of trivial
names by IUPAC.
58 59 60 61 62
P internet connect i Ce Pr Nd Pm Sm
Cerium Praseodymium Neodymium Promethium Samarium
Topic: Periodic Table 140.116 140.907 65 144.24 (145) 150.36
Go To: go.hrw.com
Keyword: HOLT PERIODIC
' '
[Xej4 / 5d 6s 2 Jfc 2 [XeHfV WfHs1 ww
90 91 92 93 94
Visit the HRW Web site for updates
on the periodic table. Th Pa U Np A Pu
Thorium Protactinium Uranium Neptunium Plutonium
232.0381 231.035 88
[RntyWls 2
238.028 91
,
[Rn|5 / J6c/ 7s2
(237)
(Rn)5 fV7s2
(244)
(Rn]5f 7s*
 Hydrogen
Semiconductors
(also known as metalloids ) Group 18
2
Metals
Alkali metals
He
Helium
Alkaline- earth metals 4.002 602
*Transition metals Group 13 Group 14 Group 15 Group 16 Group 17 \Sl

* Other metals 5 6 7 8 9 10
Nonmetals B c N o Ne
Halogens Boron Carbon Nitrogen Oxygen Fluorine Neoo
10811 12.0107 14.0067 15.9994 18.998*4032 20.1797
M Noble gases |He)2sV [HeEV (Hej2iV [HefisV
m Other nonmetals
13 14 15 16 17 18
A1 Si P S Cl Ar
Aluminum Silicon Phosphorus Sulfur Chlorine Argon
26.981 538 28.0855 30.973 761 32.065 35.453 39.948
Group 10 Group 11 Group 12 [NeJJsV msv (NeJJsty 5 [Nejlsy

28 29 30 31 32 33 34 35 36
Ni Cu Zn Ga Ge As Se Br Kr
Nickel Copper Zmc Gallium Germanium Arsenic Selenium Bromine Krypton
58.6934 63546 65.409 69.723 72.64 74.921 60 78.96 79.904 83.798
,
(Afl3 *4sJ
^ (Afftrf 'V |Arp</ 'V IWW www (Arts</ #4s2y (ArprflsV [4rl

46 47 48 49 50 51 52 53 54
Pd Ag Cd In Sn Sb r
Te I Xe
Palladium Silver Cadmium Indium Bn Antimony Tellurium Iodine Xenon
106.42 107.8682 112.411 114.818 118.710 121.760 127.60 126.904 47 131.293
,
(Kx)4d’V WV (Kr|4dV [Kr}4</ 5sy
" ^y
[Krl (Krj4dlo5sJ50 [Kr|4d * 5s 25P4
° (KrjW y
^ iw/ B5sy
78 79 80 81 82 83 84 85 86
Pt Au Hg T1 Pb Bi Po At Rn
Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon
195.078
[XeHfW _ 196.966 55
(XeHTW
20059 204.3833
Wf 'V' teW p
207.2 208.980 38
[XeH/'VW
(209)
iwvw I P i m r v w
(210) (222)

110 111 112 113 114 115

Ds Uuu* Uub* Uut* Uuq* Uup*
Darmstadtium Ununumum Ununbium Ununtrium Ununquadium Ununpentium
(281) (272) (285) (284) (289) (288)
,
(Rn)5/ 46d*7sy (Rn)STV W
fnfl'Ws' [RnlST&W |Rn)5/i4fcW
'
A team at Lawrence Berkeley National Laboratories reported the discovery of elements 116 and 118 in June 1999.
The same team retracted the discovery in July 2001. The discovery of elements 113, 114, and 115 has been reported but not confirmed.

63 64 65 66 67 68 69 70 71
Eu Gd Tb Dy Ho Er Tm Yb Lu
Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium
151.964 157.25 158.925 34 162.500 164.930 32 167.259 168.934 21 173.04 174.967
(Xe}4W (XeJtfVfc 3 pqtflfc3 JX*J4W (XeHTW (Xe}4W (XejW [XeH/ V’ PWrVtf
95 96 97 98 99 100 101 102 103
Am Cm Bk Cf Es Fm Md No Lr
Americium Cunum Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrenoum
(243) (247) (247) (251) (252) (257) (258) (259) ( 262 )
NSW [Rnl VTs2
^ IRn|5/^7sa NS("71 i
[RnfSW MW [Rnltf’V WSW [RnjS / 46J 7 s ‘

The atomic masses listed in this table reflect the precision of current measurements. (Values listed in
parentheses are the mass numbers of those radioactive elements' most stable or most common isotopes.)
 MODERN

CHEMISTRY
1 Matter and Change 12 Solutions
2 Measurements and 13 Ions in Aqueous Solutions
Calculations and Colligative Properties
3 Atoms: The Building Blocks 14 Acids and Bases
of Matter
15 Acid- Base Titration and pH
4 Arrangement of Electrons
in Atoms 16 Reaction Energy <•

5 The Periodic Law 17 Reaction Kinetics

6 Chemical Bonding 18 Chemical Equilibrium

-> /
19 Oxidation- Reduction
ki

/
7 Chemical Formulas and
Chemical Compounds Reactions
X
8 Chemical Equations and 20 Electrochemistry /

Reactions 21 Nuclear Chemistry

9 Stoichiometry 22 Organic Chemistry /
r
10 States of Matter 23 Biological Chemistry
11 Cases

ISBN - 3 - D73 SMb - 7

90000

HOLT, RINEHART AND WINSTON

m A Harcourt Education Company 9 780030 73 5 4 6 2