EBD_7374

• Corporate Office : 45, 2nd Floor, Maharishi Dayanand Marg, Corner Market,
Malviya Nagar, New Delhi-110017
Tel. : 011-49842349 / 49842350

by
Preetima Bajpai
Dr. Anuj Kumar

Typeset by Disha DTP Team

DISHA PUBLICATION
All Rights Reserved

© Copyright Publisher
No part of this publication may be reproduced in any form without prior permission of the publisher. The publisher do
not take any legal responsibility for any errors or misrepresentations that might have crept in. We have tried and made
our best efforts to provide accurate up-to-date information in this book.

For further information about the books from DISHA,

Log on to www.dishapublication.com or email to info@dishapublication.com

(ii)
 Contents
S. No. Chapters Page No.
1. Some Basic Concepts of Chemistry 1-12
2. Structure of Atom 13-26
3. Classification of Elements and Periodicity in Properties 27-38
4. Chemical Bonding and Molecular Structure 39-54
5. States of Matter 55-68
6. Thermodynamics 69-82
7. Equilibrium 83-100
8. Redox Reactions 101-110
9. Hydrogen 111-122
10. The s-Block Elements 123-134
11. The p-Block Elements (Group 13 and 14) 135-146
12. Organic Chemistry – Some Basic Principles and Techniques 147-164
13. Hydrocarbons 165-182
14. Environmental Chemistry 183-194
15. The Solid State 195-208
16. Solutions 209-224
17. Electrochemistry 225-240
18. Chemical Kinetics 241-258
19. Surface Chemistry 259-272
20. General Principles and Processes of Isolation of Elements 273-284
21. The p-Block Elements (Group 15, 16, 17 and 18) 285-300
22. The d-and f-Block Elements 301-314
23. Coordination Compounds 315-330
24. Haloalkanes and Haloarenes 331-346
25. Alcohols, Phenols and Ethers 347-362
26. Aldehydes, Ketones & Carboxylic acids 363-380
27. Amines 381-396
28. Biomolecules 397-412
29. Polymers 413-422
30. Chemistry In Everyday Life 423-432

Hints & Solutions

S. No. Chapters Page No.
1. Some Basic Concepts of Chemistry 433-442
2. Structure of Atom 443-450
3. Classification of Elements and Periodicity in Properties 451-455
4. Chemical Bonding and Molecular Structure 456-469
5. States of Matter 470-477
(iii)
 EBD_7374
6. Thermodynamics 478-485
7. Equilibrium 486-499
8. Redox Reactions 500-504
9. Hydrogen 505-509
10. The s-Block Elements 510-514
11. The p-Block Elements (Group 13 and 14) 515-519
12. Organic Chemistry – Some Basic Principles and Techniques 520-528
13. Hydrocarbons 529-539
14. Environmental Chemistry 540-542
15. The Solid State 543-349
16. Solutions 550-560
17. Electrochemistry 561-571
18. Chemical Kinetics 572-582
19. Surface Chemistry 583-588
20. General Principles and Processes of Isolation of Elements 589-592
21. The p-Block Elements (Group 15, 16, 17 and 18) 593-601
22. The d-and f-Block Elements 602-608
23. Coordination Compounds 609-618
24. Haloalkanes and Haloarenes 619-628
25. Alcohols, Phenols and Ethers 629-640
26. Aldehydes, Ketones & Carboxylic acids 641-651
27. Amines 652-661
28. Biomolecules 662-669
29. Polymers 670-673
30. Chemistry In Everyday Life 674-676

MOCK TEST
Mock Test - 1 MT-1-4

Mock Test - 2 MT-5-7

Mock Test - 3 MT-8-10

Mock Test - 4 MT-11-13

Mock Test - 5 MT-14-16

Hints and Solutions Mock Test (1-5) MT-17-32

(iv)
 1
Chapter
SOME BASIC CONCEPTS OF
CHEMISTRY

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Mole concept,
AIIMS 2 stoichiometry and 3/5 6.9
JEE Main 2 Stoichiometric calculations
BITSAT 2
 EBD_7374
2 CHEMISTRY
SOME BASIC CONCEPTS OF CHEMISTRY 3
 EBD_7374
4 CHEMISTRY

Exercise 1 : Topic-wise MCQs

10. Given P = 0.0030m, Q = 2.40m, R = 3000m, Significant figures
Topic 1: Properties of Matter and their Measurement
in P, Q and R are respectively
1. A mixture of sand and iodine can be separated by (a) 2, 2, 1 (b) 2, 3, 4 (c) 4, 2, 1 (d) 4, 2, 3
(a) crystallisation (b) distillation 11. Arrange the numbers in increasing no. of significant figures.
(c) sublimation (d) fractionation 0.002600, 2.6000, 2.6, 0.260
2. Difference in density is the basis of (a) 2.6 < 0.260 < 0.002600 < 2.6000
(a) ultrafiltration (b) molecular sieving (b) 2.6000 < 2.6 < 0.002600 < 0.260
(c) molecular attraction (d) gravity separation (c) 0.260 < 2.6 < 0.002600 < 2.6000
3. Which has highest weight ? (d) 0.002600 < 0.260 < 2.6 < 2.6000
(a) 1 m3 of water (b) A normal adult man
(c) 10 litre of Hg (d) All have same weight Topic 2: Laws of Chemical Combinations
4. Which one of the following set of units represents the
smallest and largest amount of energy respectively? 12. Which of the following is the best example of law of
(a) J and erg (b) erg and cal conservation of mass?
(c) cal and eV (d) eV and L-atm (a) 12 g of carbon combines with 32 g of oxygen to form
44 g of CO2
5. Many countries use Fahrenheit scale for expressing temperature
of atmosphere. If temperature in any such country is (b) When 12 g of carbon is heated in a vacuum there is no
measured 41°F then what is its value in celcius scale and change in mass
would you expect hot or cold atmosphere in that country? (c) A sample of air increases in volume when heated at
(a) 15°C, cold (b) 25°C, normal constant pressure but its mass remains unaltered
(c) 5°C, cold (d) 41°C, hot (d) The weight of a piece of platinum is the same before
and after heating in air
6. A sample was weighted using two different balances. The
results were 13. In one experiment, 4g of H2 combine with 32g of O2 to form
36g of H2O. In another experiment, when 50g of H2 combine
(i) 3.929 g (ii) 4.0 g
with 400g of O2 then 450g of H2O is formed. Above two
How would the weight of the sample be reported? experiments follow
(a) 3.93 g (b) 3g (c) 3.9 g (d) 3.929 g (a) The law of conservation of mass
7. If the true value for an experimental result is 6.23 and the (b) The law of constant composition
results reported by three students X, Y and Z are :
(c) Both (a) and (b)
X : 6.18 and 6.28
(d) Neither (a) nor (b)
Y : 6.20 and 6.023
14. Irrespective of the source, pure sample, of water always yields
Z : 6.22 and 6.24 88.89% mass of oxygen and 11.11% mass of hydrogen. This is
Which of the following option is correct : explained by the law of
(a) X precise, Y accurate, Z precise and accurate. (a) conservation of mass (b) multiple proportions
(b) X precise and accurate, Y not precise, Z precise (c) constant composition (d) constant volume
(c) Both X & Z precise & accurate, Y not precise. 15. The percentage of copper and oxygen in samples of CuO
(d) Both X & Y neither precise nor accurate, Z both precise obtained by different methods were found to be the same.
and accurate. The illustrate the law of
8. In the final answer of the expression (a) constant proportions (b) conservation of mass
(c) multiple proportions (d) reciprocal proportions
(29.2 - 20.2) (1.79 ´105 )
16. Which one of the following pairs of compounds illustrate
1.37
the law of multiple proportions ?
the number of significant figures is : (a) H2O and Na2O (b) MgO and Na2O
(a) 1 (b) 2 (c) 3 (d) 4 (c) Na2O and BaO (d) SnCl2 and SnCl4
9. The number of significant figures for the three numbers 17. Two samples of lead oxide were separately reduced to
161 cm, 0.161 cm, 0.0161 cm are metallic lead by heating in a current of hydrogen. The weight
(a) 3,4 and 5 respectively (b) 3,4 and 4 respectively of lead from one oxide was half the weight of lead obtained
(c) 3,3 and 4 respectively (d) 3,3 and 3 respectively from the other oxide. The data illustrates
SOME BASIC CONCEPTS OF CHEMISTRY 5

(a) law of reciprocal proportions

Topic 3: Atomic and Molecular Masses
(b) law of constant proportions
(c) law of multiple proportions 25. Molecular mass is defined as the
(d) law of equivalent proportions (a) mass of one atom compared with the mass of one
molecule
18. In compound A, 1.00g of nitrogen unites with 0.57g of
oxygen. In compound B, 2.00g of nitrogen combines with (b) mass of one atom compared with the mass of one atom
2.24g of oxygen. In compound C, 3.00g of nitrogen combines of hydrogen
with 5.11g of oxygen. These results obey the following law (c) mass of one molecule of any substance compared with
(a) law of constant proportion the mass of one atom of C-12
(b) law of multiple proportion (d) None of the above
(c) law of reciprocal proportion 26. The average atomic mass of neon based on following data
(d) Dalton’s law of partial pressure is :
19. The molecular weight of O2 and SO2 are 32 and 64 Isotope Relative abundance
20Ne 0.9051
respectively. At 15°C and 150 mm Hg pressure, one litre of
21Ne 0.0027
O2 contains ‘N’ molecules. The number of molecules in two
22Ne 0.0922
litres of SO2 under the same conditions of temperature and
pressure will be : (a) 0.33 u (b) 20.187 u (c) 6.729 u (d) 18.058 u
(a) N/2 (b) 1 N (c) 2 N (d) 4 N 27. What is the average atomic mass of bromine from the
20. 10 dm3 of N2 gas and 10 dm3 of gas X at the same temperature following data : (abundance is in %)
contain the same number of molecules, the gas X is Isotope Mass Abundance
(a) CO2 (b) CO (c) H2 (d) NO 79Br 78.9183361 50.69
21. One mole of a gas occupies a volume of 22.4 L. This is 81Br 80.916289 49.31
derived from (a) 79.9 (b) 76.6 (c) 75.9 (d) 69.9
(a) Berzelius’ hypothesis (b) Gay-Lussac’s law 28. What is the mass of an atom of oxygen (in g)?
(c) Avogadro’s law (d) Dalton’s law (a) 2.656 × 10–23 (b) 1.567 × 10–22
(c) 2.0 × 10 –22 (d) 3.5 × 10–23
22. Equal volumes of two gases A and B are kept in a container
at the same temperature and pressure. Avogadro’s law is 29. If the mass of the one atom is found to be 2.324784×10–23g,
invalid if then this atom can be ?
(a) the gases are reactive (a) Oxygen (b) Carbon
(b) the gases are non-reactive (c) Fluorine (d) Nitrogen
(c) gas A has more number of molecules than gas B. 30. Match the columns
(d) None of these Column-I Column-II
23. Consider the following statements. (A) C6H5NH2 (p) 84
(i) Atoms of H, O, N and C have identical properties but (B) C6H6 (q) 100
different mass. (C) C6H12 (r) 93
(ii) Matter is divisible into atoms which are further indivisible. (D) CaCO3 (s) 78
(iii) The ratio of N: H in NH3 is 1 : 3 and N : O in nitric oxide (a) A – (p), B – (r), C – (q), D – (s)
is 2 : 1. (b) A – (r), B – (s), C – (p), D – (q)
(iv) Dalton’s atomic theory support law of conservation (c) A – (r), B – (p), C – (q), D – (s)
of mass.
(d) A – (r), B – (q), C – (s), D – (p)
Which of the following pairs of statements is true according
31. If we consider that 1/6, in place of 1/12, mass of carbon
to Dalton’s atomic theory ?
atom is taken to be the relative atomic mass unit, the mass
(a) (i) and (ii) (b) (ii) and (iii) of one mole of a substance will
(c) (ii) and (iv) (d) (i) and (iv) (a) decrease twice
24. Assertion : Equal moles of different substances contain (b) increase two fold
same number of constituent particles. (c) remain unchanged
Reason : Equal weights of different substances contain (d) be a function of the molecular mass of the substance
the same number of constituent particles.
(a) Assertion is correct, reason is correct; reason is a Topic 4: Mole Concepts and Molar Masses
correct explanation for assertion. 32. What is the mass of 1 molecule of CO.
(b) Assertion is correct, reason is correct; reason is not a (a) 2.325 × 10–23 (b) 4.65 × 10–23
correct explanation for assertion. (c) 3.732 × 10–23 (d) 2.895 × 10–23
(c) Assertion is correct, reason is incorrect. 33. Calculate the volume at STP occupied by 240 gm of SO2.
(d) Assertion is incorrect, reason is correct. (a) 64 (b) 84 (c) 59 (d) 73
 EBD_7374
6 CHEMISTRY

34. At S.T.P. the density of CCl4 vapours in g/L will be nearest 48. How many moles of Al2(SO4)3 would be in 50 g of the
to: substance ?
(a) 6.87 (b) 3.42 (c) 10.26 (d) 4.57 (a) 0.083 mole (b) 0.952 mole
35. The number of gram molecules of oxygen in 6.02 × 1024 (c) 0.481 mole (d) 0.140 mole
CO molecules is 49. The mass of 1 mole of electrons is
(a) 10 g molecules (b) 5 g molecules (a) 9.1 × 10–28g (b) 1.008 mg
(c) 1 g molecules (d) 0.5 g molelcules (c) 0.55 mg (d) 9.1 × 10–27 g
36. The number of oxygen atoms in 4.4 g of CO2 is 50. 10 g of hydrogen and 64 g of oxygen were filled in a steel
(a) 1.2 × 1023 (b) 6 × 1022 vessel and exploded. Amount of water produced in this
(c) 6 × 10 23 (d) 12 × 1023 reaction will be:
37. Which has maximum number of molecules? (a) 3 mol (b) 4 mol (c) 1 mol (d) 2 mol
(a) 7 g N2 (b) 2 g H2 (c) 16 g NO2 (d) 16 g O2 51. Which has the maximum number of molecules among the
38. Number of atoms in 558.5g Fe (at. wt. of Fe = 55.85 g mol–1) following ?
is (a) 44 g CO2 (b) 48 g O3
(a) twice that in 60 g carbon (c) 8 g H2 (d) 64 g SO2
(b) 6.023 × 1022 52. The weight of one molecule of a compound C 60H122 is
(c) half that in 8 g He
(a) 1.2 × 10–20 gram (b) 1.4 × 10–21 gram
(d) 558.5 × 6.023 × 1023
(c) 5.025 × 1023 gram (d) 6.023 × 1023 gram
39. The number of molecules in 16 g of methane is
53. Match the columns.
16 Column-I Column-II
(a) 3.0 × 1023 (b) ´ 10 23
6.02 (A) 88 g of CO2 (p) 0.25 mol
(B) 6.022 × 1023 molecules (q) 2 mol
16 of H2O
(c) 6.023 × 1023 (d) ´ 10 23
3.0 (C) 5.6 litres of O2 at STP (r) 1 mol
40. Amount of oxygen in 32.2 g Na2SO4.10 H2O is (D) 96 g of O2 (s) 6.022 × 1023 molecules
(a) 20.8 g (b) 2.24 g (c) 22.4 g (d) 2.08 g (E) 1 mol of any gas (t) 3 mol
41. The number of moles of oxygen in one litre of air containing (a) A – (q), B – (r), C – (p), D – (t), E – (s)
21% oxygen by volume, under standard conditions are (b) A – (r), B – (q), C – (p), D – (t), E – (s)
(a) 0.0093 mole (b) 0.21 mole (c) A – (q), B – (p), C – (r), D – (t), E – (s)
(c) 2.10 mole (d) 0.186 mole (d) A – (q), B – (r), C – (p), D – (s), E – (t)
42. The number of molecules in 8.96 litre of a gas at 0ºC and 1 54. Assertion : Volume of a gas is inversely proportional to the
atm. pressure is approximately number of moles of gas.
(a) 6.023 × 1023 (b) 12.04 × 1023 Reason : The ratio by volume of gaseous reactants and
(c) 18.06 × 1023 (d) 24.08 × 1022 products is in agreement with their mole ratio.
43. The mass of a molecule of water is (a) Assertion is correct, reason is correct; reason is a
(a) 3 × 10–25 kg (b) 3 × 10–26 kg correct explanation for assertion.
–26
(c) 1.5 × 10 kg (d) 2.5 × 10–26 kg (b) Assertion is correct, reason is correct; reason is not a
44. One mole of CO2 contains : correct explanation for assertion.
(a) 3 g atoms of CO2 (c) Assertion is correct, reason is incorrect.
(b) 18.1 × 1023 molecules of CO2 (d) Assertion is incorrect, reason is correct.
(c) 6.02 × 1023 atoms of O 55. The maximum number of molecules are present in
(d) 6.02 × 1023 atoms of C (a) 15 L of H2 gas at STP (b) 5 L of N2 gas at STP
45. Volume of a gas at NTP is 1.12 × 10–7cm3. The number of (c) 0.5 g of H2 gas (d) 10 g of O2 gas
molecules in it is : 56. How many moles of magnesium phosphate, Mg 3(PO4)2 will
(a) 3.01 × 1012 (b) 3.01 × 1024 contain 0.25 mole of oxygen atoms?
(c) 3.01 × 1023 (d) 3.01 × 1020 (a) 1.25 × 10–2 (b) 2.5 × 10–2
46. How many atoms are contained in one mole of sucrose (c) 0.02 (d) 3.125 × 10–2
(C12H22O11)? 57. Volume occupied by one molecule of water
(a) 20 × 6.02 × 1023 atoms/mol (density = 1 g cm–3) is :
(b) 45 × 6.02 × 1023 atoms/mol (a) 9.0 × 10–23 cm3 (b) 6.023 × 10– 23 cm3
–23 3 (d) 5.5 × 10– 23 cm3
(c) 5 × 6.02 × 1023 atoms/mol (c) 3.0 × 10 cm
(d) None of these 58. The number of atoms in 0.1 mol of a triatomic gas is :
47. O2, N2 are present in the ratio of 1 : 4 by weight. The ratio of (NA = 6.02 ×1023 mol–1)
number of molecules is : (a) 6.026 × 1022 (b) 1.806 × 1023
(c) 3.600 × 10 23 (d) 1.800 × 1022
(a) 7 : 32 (b) 1 : 4 (c) 2 : 1 (d) 4 : 1
SOME BASIC CONCEPTS OF CHEMISTRY 7

59. 1 c.c. N2O at NTP contains : 70. 12 gm of Mg (atomic mass 24) will react completely with
1.8 6.02 hydrochloric acid to give
(a) ´ 10 22 atoms (b) ´ 10 23 molecules (a) One mol of H2
224 22400
(b) 1/2 mol of H2
(c) 1.32 ´ 10 23 electrons (d) All of the above (c) 2/3 mol of O2
224 (d) both 1/2 mol of H2 and 1/2 mol of O2
60. How much time (in hours) would it take to distribute one 71. 20.0 kg of N2(g) and 3.0 kg of H2(g) are mixed to produce
Avogadro number of wheat grains if 10 20 grains are NH3(g). The amount of NH3(g) formed is
distributed each second ? (a) 17 kg (b) 34 kg (c) 20 kg (d) 3 kg
(a) 0.1673 (b) 1.673 (c) 16.73 (d) 167.3 72. 20.0 kg of H2(g) and 32 kg of O2(g) are reacted to produce
H2O(l). The amount of H2O (l) formed after completion of
Topic 5: Percentage Composition, Molecular and
reaction is
Empirical Formula (a) 62 kg (b) 38 kg (c) 42 kg (d) 72 kg
61. Which one of the following is the lightest? 73. What is the weight of oxygen required for the complete
(a) 0.2 mole of hydrogen gas combustion of 2.8 kg of ethylene ?
(a) 2.8 kg (b) 6.4 kg (c) 9.6 kg (d) 96 kg
(b) 6.023 × 1022 molecules of nitrogen
74. In the reaction
(c) 0.1 g of silver
(d) 0.1 mole of oxygen gas 4 NH3 ( g ) + 5O2 ( g ) ® 4 NO( g ) + 6H2 O(l )
62. The empirical formula of a compound is CH2. One mole of When 1 mole of ammonia and 1 mole of O2 are made to react
this compound has a mass of 42 grams. Its molecular formula is : to completion,
(a) 1.0 mole of H2O is produced
(a) C3H6 (b) C3H8 (c) CH2 (d) C2H2
(b) 1.0 mole of NO will be produced
63. An organic compound contains carbon, hydrogen and
(c) all the oxygen will be consumed
oxygen. Its elemental analysis gave C, 38.71% and H, 9.67%.
(d) all the ammonia will be consumed
The empirical formula of the compound would be :
(a) CH3O (b) CH2O (c) CHO (d) CH4O 75. What is the molarity of 0.2N Na 2 CO 3 solution?
64. In a compound C, H and N atoms are present in 9 : 1 : 3.5 by (a) 0.1 M (b) 0 M (c) 0.4 M (d) 0.2 M
weight. Molecular weight of compound is 108. Molecular 76. The molar solution of H 2SO 4 is equal to :
formula of compound is
(a) N/2 solution (b) N solution
(a) C2H6N2 (b) C3H4N (c) C6H8N2 (d) C9H12N3
(c) 2N solution (d) 3N solution
65. The empirical formula of an acid is CH2O2, the probable 77. Volume of water needed to mix with 10 mL 10N HNO3 to get
molecular formula of acid may be : 0.1 N HNO3 is :
(a) C3H6O4 (b) CH2O (c) CH2O2 (d) C2H4O2 (a) 1000 mL (b) 990 mL (c) 1010 mL (d) 10 mL
66. A gaseous hydrocarbon gives upon combustion 0.72 g of 78. One kilogram of a sea water sample contains 6 mg of
water and 3.08 g. of CO2. The empirical formula of the dissolved O2. The concentration of O2 in the sample in
hydrocarbon is : ppm is
(a) C2H4 (b) C3H4 (c) C6H5 (d) C7H8 (a) 0.6 (b) 6.0 (c) 60.0 (d) 16.0
67. Which of the following is the correct empirical and 79. A 5 molar solution of H2SO4 is diluted from 1 litre to a volume
molecular formulae of a compound, if the molecular mass of 10 litres, the normality of the solution will be :
of a compound is 80 and compound contains 60% of C, (a) 1N (b) 0.1N (c) 5N (d) 0.5N
5% of H and 35% of N ? 80. 6.02 × 1020 molecules of urea are present in 100 ml of its
(a) C2H2N ; C4H4N2 (b) C3H4N2 ; C6H8N4 solution. The concentration of urea solution is
(c) C2H4N2 ; C4H8N4 (d) C2H2N ; C2H2N (a) 0.02 M (b) 0.01 M (c) 0.001 M (d) 0.1 M
68. Which of the following is the correct empirical and molecular (Avogadro constant, NA = 6.02 × 1023 mol–1)
formulae of a compound, if the molecular mass of a compound 81. Two solutions of a substance (non electrolyte) are mixed in
is 93 and compound containing 77.43% of C, 7.53% of H the following manner. 480 ml of 1.5 M first solution + 520 ml
and 15.05% of N ? of 1.2 M second solution. What is the molarity of the final
(a) C3H3.5N1.5 and C6H7N (b) C6H7N and C6H7N mixture?
(c) C3H3N and C6H7N (d) C3H3N and C6H6N2 (a) 2.70 M (b) 1.344 M (c) 1.50 M (d) 1.20 M
82. Match the columns.
Topic 6: Stoichiometry and Stoichiometric Calculations Column-I Column-II
(Physical quantity) (Unit)
69. If 1.5 moles of oxygen combines with Al to form Al2O3, the (A) Molarity (p) mol
mass of Al in g [Atomic mass of Al = 27] used in the
(B) Mole fraction (q) Unitless
reaction is
(C) Mole (r) mol L–1
(a) 2.7 (b) 54 (c) 40.5 (d) 81 (D) Molality (s) mol kg–1
 EBD_7374
8 CHEMISTRY

(a) A – (r), B – (q), C – (s), D – (p) 87. Which of the following option represents correct limiting
(b) A – (r), B – (p), C – (q), D – (s) reagents in reactions (i), (ii) and (iii) respectively.
(c) A – (r), B – (q), C – (p), D – (s) (i) C + O2 ® CO2
(d) A – (q), B – (r), C – (p), D – (s) (26g) (20g)
83. Assuming fully decomposed, the volume of CO2 released at
STP on heating 9.85 g of BaCO3 (Atomic mass, Ba = 137) will (ii) N2 + 3H2 ® 2NH3
be (60g) (80g)
(a) 2.24 L (b) 4.96 L (c) 1.12 L (d) 0.84 L (iii) P4 + 3O2 ® P4O6
84. The mass of BaCO3 produced when excess CO2 is bubbled (100g) (200g)
through a solution of 0.205 mol Ba(OH)2 is : (a) C, N2, O2 (b) C, N2, P4
(a) 81 g (b) 40.5 g (c) 20.25 g (d) 162 g (c) O2, H2, P4 (d) O2, N2, P4
85. For the reaction Fe2O3 + 3CO2 ® 2Fe + 3CO2, the volume of 88. 10 mL of 2(M) NaOH solution is added to 200 mL of
carbon monoxide required to reduce one mole of ferric oxide 0.5 (M) of NaOH solution. What is the final concentration ?
is (a) 0.57 (M) (b) 5.7 (M) (c) 11.4 (M) (d) 1.14 (M)
(a) 67.2 dm3 (b) 11.2 dm3 (c) 22.4 dm3 (d) 44.8 dm3 89. If maximum fluoride ion presence was set to be 4 ppm
86. Fat is an important source of energy and water, this is number of moles of fluoride in 10 ml drinking water ?
important for the desert animals like camel which store fat (a) 2.10 × 10–3 (b) 2.10 × 10–2
in its hump and provide water and energy. How many (c) 3.10 × 10 –3 (d) 3.3 × 10–2
grams and moles of H2O are produced from the combustion 90. The increasing order of molarity with 25 gm each of
of fat C57H110O6 from 450 gram of fat stored in hump of NaOH, LiOH, Al(OH)3, KOH, B(OH)3 in same volume of
camel ? water?
163 (a) Al(OH)3 < B(OH)3 < KOH < NaOH < LiOH
C57 H110O6 + O2 ® 57CO 2 + 55H 2O
2 (b) LiOH < NaOH < KOH < B(OH)3 < Al(OH)3
(a) 500.56 , 27.80 (b) 450, 26.80 (c) LiOH < NaOH < B(OH)3 < KOH < Al(OH)3
(c) 580, 25.0 (d) 400, 26.6 (d) NaOH < LiOH < B(OH)3 < Al(OH)3 < KOH

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 3. What will be the molarity of a solution, which contains 5.85
g of NaCl(s) per 500 mL?
1. Two students performed the same experiment separately (a) 4 mol L–1 (b) 20 mol L–1
and each one of them recorded two readings of mass which (c) 0.2 mol L –1 (d) 2 mol L–1
are given below. Correct reading of mass is 3.0 g. On the 4. If 500 mL of a 5 M solution is diluted to 1500 mL, what will
basis of given data, mark the correct option out of the be the molarity of the solution obtained?
following statements. (a) 1.5 M (b ) 1.66 M (c) 0.017 M (d) 1.59 M
5. The number of atoms present in one mole of an element is
Students Readings equal to Avogadro number. Which of the following element
(i) (ii) contains the greatest number of atoms?
(a) 4 g He (b) 46 g Na
A 3.01 2.99 (c) 0.40 g Ca (d) 12 g He
B 3.05 2.95 6. If the concentration of glucose (C 6H12O6) in blood is
0.9 g L–1, what will be the molarity of glucose in blood?
(a) Results of both the students are neither accurate nor (a) 5 M (b) 50 M (c) 0.005 M (d) 0.5 M
precise. 7. What will be the molality of the solution containing 18.25 g
(b) Results of student A are both precise and accurate. of HCl gas in 500 g of water?
(c) Results of student B are neither precise nor accurate. (a) 0.1 m (b) 1 M (c) 0.5 m (d) 1 m
(d) Results of student B are both precise and accurate. 8. One mole of any substance contains 6.022 × 10 23
2. A measured temperature on Fahrenheit scale is 200°F. What atoms/molecules. Number of molecules of H2SO4 present
will this reading be on celsius scale? in 100 mL of 0.02 M H2SO4 solution is........
(a) 40 °C (b) 94 °C (d) 93.3 °C (d) 30 °C (a) 12.044 × 1020 molecules (b) 6.022 × 1023 molecules
(c) 1 × 1023 molecules (d) 12.044 × 1023 molecules
SOME BASIC CONCEPTS OF CHEMISTRY 9

9. What is the mass percent of carbon in carbon dioxide? Past Year MCQs
(a) 0.034% (b) 27.27% (c) 3.4% (d) 28.7% 16. When 22.4 litres of H2(g) is mixed with 11.2 litres of Cl2(g),
10. The empirical formula and molecular mass of a compound each at S.T.P., the moles of HCl(g) formed is equal to:-
are CH2O and 180 g respectively .What will be the molecular [AIPMT 2014, S]
formula of the compound? (a) 1 mol of HCl(g) (b) 2 mol of HCl(g)
(a) C9H18O9 (b) CH2O (c) 0.5 mol of HCl(g) (d) 1.5 mol of HCl(g)
(c) C6H12O6 (d) C2H4O2 17. 1.0 g of magnesium is burnt with 0.56 g O2 in a closed vessel.
11. If the density of a solution is 3.12 g mL–1, the mass of Which reactant is left in excess and how much ?
1.5 mL solution in significant figures is......
(At. wt. Mg = 24 ; O = 16) [AIPMT 2014, S]
(a) 4.7 g (b ) 4680 ×10–3 g
(a) Mg, 0.16 g (b) O2, 0.16 g
(c) 4.680 g (d) 46.80 g
(c) Mg, 0.44 g (d) O2, 0.28 g
12. Which of the following statements about a compound is
18. Which has the maximum number of molecules among the
incorrect?
(a) A molecule of a compound has atoms of different following ? [AIIMS 2014, S]
elements. (a) 44 g CO2 (b) 48 g O3
(b) A compound cannot be separated into its constituent (c) 8 g H2 (d) 64 g SO2
elements by physical methods of separation. 19. The ratio of masses of oxygen and nitrogen in a particular
(c) A compound retains the physical properties of its gaseous mixture is 1 : 4. The ratio of number of their molecule
constituent elements. is: [JEE M 2014, S]
(d) The ratio of atoms of different elements in a compound (a) 1 : 4 (b) 7 : 32 (c) 1 : 8 (d) 3 : 16
is fixed. 20. The formation of CO and CO2 illustrates the law of
13. Which of the following statements is correct about the [BITSAT 2014, C]
reaction given below? (a) reciprocal proportion (b) conservation of mass
(c) multiple proportion (d) constant composition
4Fe (s) + 3O2 (g) ¾¾
® 2Fe2O3 (g)
21. A mixture of gases contains H2 and O2 gases in the ratio of
(a) Total mass of iron and oxygen in reactants = total mass 1 : 4 (w/w). What is the molar ratio of the two gases in the
of iron and oxygen in product therefore it follows law mixture ? [AIPMT 2015, S]
of conservation of mass. (a) 4 : 1 (b) 16 : 1 (c) 2 : 1 (d) 1 : 4
(b) Total mass of reactants = total mass of product, 22. 20.0 g of a magnesium carbonate sample decomposes on
therefore, law of multiple proportions is followed. heating to give carbon dioxide and 8.0 g magnesium oxide.
(c) Amount of Fe2O3 can be increased by taking any one What will be the percentage purity of magnesium carbonate
of the reactants (iron or oxygen) in excess. in the sample ? [AIPMT 2015, S]
(d) Amount of Fe2O3 produced will decrease if the amount (a) 75 (b) 96 (c) 60 (d) 84
of any one of the reactants (iron or oxygen) is taken in 23. The number of water molecules is maximum in :
excess. [AIPMT 2015, S]
14. Which of the following reactions is not correct according (a) 18 molecules of water (b) 1.8 gram of water
to the law of conservation of mass? (c) 18 gram of water (d) 18 moles of water
(a) 2Mg (s) + O2 (g) ¾¾ ® 2MgO (s) 24. If Avogadro number NA, is changed from 6.022 × 1023 mol–1 to
(b) C3H8 (g) + O2 (g) ¾¾ ® CO2 (g) + H2O (g) 6.022 × 1020 mol–1 this would change : [AIPMT 2015, S]
(c) P4 (s) + 5O2 (g) ¾¾ ® P4O10 (s) (a) the definition of mass in units of grams
(d) CH4 (g) + 2O2 (g) ¾¾ ® CO2 (g) + 2H2O (g) (b) the mass of one mole of carbon
15. Which of the following statements indicates that law of (c) the ratio of chemical species to each other in a balanced
multiple proportion is being followed? equation.
(a) Sample of carbon dioxide taken from any source will (d) the ratio of elements to each other in a compound
always have carbon and oxygen in the ratio 1 : 2. 25. What is the mass of precipitate formed when 50 mL of 16.9%
(b) Carbon forms two oxides namely CO2 and CO, where solution of AgNO3 is mixed with 50 mL of 5.8% NaCl
masses of oxygen which combine with fixed mass of solution?
carbon are in the simple ratio 2 : 1. (Ag = 107.8, N = 14, O = 16, Na = 23, Cl = 35.5)
(c) When magnesium burns in oxygen, the amount of [AIPMT 2015, S]
magnesium taken for the reaction is equal to the (a) 28 g (b) 3.5 g (c) 7 g (d) 14 g
amount of magnesium in magnesium oxide formed. 26. Sulphur forms the chlorides S2Cl2 and SCl2. The equivalent
(d) At constant temperature and pressure 200 mL of mass of sulphur in SCl2 is [AIIMS 2015, S]
hydrogen will combine with 100 mL oxygen to produce (a) 8 g/mol (b) 16 g/mol
200 mL of water vapour. (c) 64.8 g/mol (d) 32 g/mol
 EBD_7374
10 CHEMISTRY

27. The molecular formula of a commercial resin used for Oxygen (61.4%) ; Carbon (22.9%), Hydrogen (10.0%) ; and
exchanging ions in water softening is C8H7SO3– Na + Nitrogen (2.6%). The weight which a 75 kg person would
(Mol. wt. 206. What would be the maximum uptake of Ca2 + gain if all 1H atoms are replaced by 2H atoms is
ions by the resin when expressed in mole per gram resin ?
[JEE M 2017, S]
[JEE M 2015, S]
(a) 15 kg (b) 37.5 kg (c) 7.5 kg (d) 10 kg
2 1 1 1 36. 1 gram of a carbonate (M2CO3) on treatment with excess
(a) (b) (c) (d)
309 412 103 206 HCl produces 0.01186 mole of CO2. The molar mass of
28. The prefix 1018 is [BITSAT 2015, S] M2CO3 in g mol–1 is : [JEE M 2017, S]
(a) giga (b) kilo (c) exa (d) nano (a) 1186 (b) 84.3 (c) 118.6 (d) 11.86
29. Arrange the following in the order of increasing mass (atomic 37. Find which of the following compound can have mass ratios
mass: O = 16, Cu = 63, N = 14) [AIIMS 2016, S] of C:H:O as 6:1:24 [BITSAT 2017, S]
I. one atom of oxygen (a) HO-(C=O)-OH (b) HO-(C=O)-H
II. one atom of nitrogen (c) H-(C=O)-H (d) H3CO-(C=O)-H
III. 1 × 10–10 mole of oxygen 38. If a 25.0 mL sample of sulfuric acid is titrated with 50.0 mL of
IV. 1 × 10–10 mole of copper 0.025 M sodium hydroxide to a phenolphthalein endpoint,
(a) II < I < III < IV (b) I < II < III < IV what is the molarity of the acid? [BITSAT 2017, A]
(c) III < II < IV < I (d) IV < II < III < I (a) 0.020 M (b) 0.100 M (c) 0.025 M (d) 0.050 M
30. At 300 K and 1 atm, 15 mL of a gaseous hydrocarbon requires 39. A mixture of 2.3 g formic acid and 4.5 g oxalic acid is treated
375 mL air containing 20% O2 by volume for complete with conc. H2SO4. The evolved gaseous mixture is passed
combustion. After combustion the gases occupy 330 mL. through KOH pellets. Weight (in g) of the remaining product
Assuming that the water formed is in liquid form and the at STP will be [NEET 2018, S]
volumes were measured at the same temperature and
(a) 1.4 (b) 3.0 (c) 4.4 (d) 2.8
pressure, the formula of the hydrocarbon is:
40. In which case is number of molecules of water maximum?
[JEE M 2016, S]
(a) C4H8 (b) C4H10 (c) C3H6 (d) C3H8 (a) 18 mL of water [NEET 2018, S]
31. 1.25 g of a sample of Na2CO3 and Na2SO4 is dissolved in (b) 0.18 g of water
250 ml solution. 25 ml of this solution neutralises 20 ml of (c) 10–3 mol of water
0.1N H2SO4.The % of Na2CO3 in this sample is (d) 0.00224 L of water vapours at 1 atm and 273 K
[BITSAT 2016, S]
41. A binary mixture of bivalent metals having mass 2 g,
(a) 84.8% (b) 8.48% (c) 15.2% (d) 42.4%
molecular mass of A and B are 15 and 30 respectively, is
32. The normality of 26% (wt/vol) solution of ammonia (density
dissolved in HCl, it evolve 2.24 L H2 at STP, what is the mass
= 0.855 ) is approximately : [BITSAT 2016, S]
of A present in mixture? [AIIMS 2018, S]
(a) 1.5 (b) 0.4 (c) 15.3 (d) 4
(a) 1 g (b) 1.5 g
33. Volume of water needed to mix with 10 mL 10N HNO3 to get
0.1 N HNO3 is : [AIIMS 2017, S] (c) 0.5 g (d) 0.75 g
(a) 1000 mL (b) 990 mL (c) 1010 mL (d) 10 mL 42. Assertion : In the titration of Na2CO3 with HCl using methyl
34. Assertion : Equal moles of different substances contain orange indicator, the volume required at the equivalence
same number of constituent particles. [AIIMS 2017, C] point is twice that of the acid required using phenolphthalein
Reason : Equal weights of different substances contain indicator. [AIIMS 2018, S]
the same number of constituent particles. Reason : Two moles of HCl are required for the complete
(a) Assertion is correct, reason is correct; reason is a neutralization of one mole of Na2CO3.
correct explanation for assertion. (a) Assertion is correct, reason is correct; reason is a
(b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion.
correct explanation for assertion. (b) Assertion is correct, reason is correct; reason is not a
(c) Assertion is correct, reason is incorrect. correct explanation for assertion.
(d) Assertion is incorrect, reason is correct. (c) Assertion is correct, reason is incorrect.
35. The most abundant elements by mass in the body of a (d) Assertion is incorrect, reason is correct.
healthy human adult are :
SOME BASIC CONCEPTS OF CHEMISTRY 11

43. The ratio of mass percent of C and H of an organic 3Pb ( NO 3 ) 2 ( aq ) + Al2 (SO 4 )3 ( aq ) ¾¾
® 3PbSO 4 (s )
compound (CXHYOZ) is 6 : 1. If one molecule of the above
compound (CXHYOZ) contains half as much oxygen as + 2Al ( NO 3 )3 ( aq )
required to burn one molecule of compound C XHY
(a) 6.25 × 10–2 M (b) 2.421 × 10–2 M
completely to CO2 and H2O. The empirical formula of
(c) 0.1875 M (d) None of these
compound CXHYOZ is : [JEE M 2018, S]
45. 100 ml O2 and H2 kept at same temperature and pressure.
(a) C3H6O3 (b) C2H4O (c) C3H4O2 (d) C2H4O3
What is true about their number of molecules
44. The 25 mL of a 0.15 M solution of lead nitrate, Pb(NO3)2
[BITSAT 2018, C]
reacts with all of the aluminium sulphate, Al2(SO4)3, present
in 20 mL of a solution. What is the molar concentration of (a) NO2 > NH2 (b) NO2 < NH2
the Al2(SO4)3? [BITSAT 2018, S] (c) NO2 = NH2 (d) NO2 + NH2 = 1 mole

Exercise 3 : Try If You Can

1. A certain public water supply contains 0.10 ppb (part per 6. A bottle of an aqueous H2O2 solution is labelled as '28 V'
billion) of chloroform (CHCl3). How many molecules of H2O2 and the density of the solution (in g/mL) is 1.25.
CHCl3 would be obtained in 0.478 mL drop of this water? Choose the correct option:
(a) 4 × 10–13 × NA (b) 10–3 × NA (a) Molality of H2O2 solution is 2
(c) 4 × 10–10 × NA (d) None of these (b) Molarity of H2O2 solution is 5
2. If NA is Avogadro’s number, then number of valence (c) Molality of H2O2 solution is 2.15
electrons in 4.2g of nitride ions (N3–) is (d) None of these
(a) 2.4 NA (b) 4.2 NA (c) 1.6 NA (d) 3.2 NA 7. 4 mole of a mixture of Mohr's salt and Fe2(SO4)3 requires
3. A 25.0 mm × 40.0 mm piece of gold foil is 0.25 mm thick. The 500 mL of 1 M K2Cr2O7 for complete oxidation in acidic
density of gold is 19.32 g/cm3. How many gold atoms are in medium. The mole % of the Mohr's salt in the mixture is:
the sheet? (Atomic weight : Au = 197.0) (a) 25 (b) 50 (c) 60 (d) 75
(a) 7.7 × 1023 (b) 1.5 × 1023 8. Liquid benzene (C6H6) burns in oxygen according to the
(c) 4.3 × 1021 (d) 1.47 × 1022 equation
4. The relation between molarity (M) and molality (m) is given 2 C 6 H 6 (l ) + 15 O 2 ( g ) ¾
¾® 12 CO 2 ( g ) + 6 H 2 O ( g )
by:
How many litres of O2 at STP are needed to complete the
(p = density of solution (g/mL), M1 = molecular mass of combustion of 39 g of liquid benzene?(Mol. wt. of O2 = 32,
solute) C6H6 = 78)
1000 M 1000 pM (a) 74 L (b) 11.2 L (c) 22.4 L (d) 84 L
(a) m= (b) m=
1000 p - M1 1000 p - MM1 9. A gaseous compound is composed of 85.7% by mass carbon
and 14.3% by mass hydrogen. Its density is 2.28 g/litre at
1000 MM 1000 M 300 K and 1.0 atm pressure. Determine the molecular formula
(c) m= (d) m=
1000 p - MM1 1000 p - MM1 of the compound.
(a) C2H2 (b) C2H4 (c) C4H8 (d) C4H10
5. The 25 mL of a 0.15 M solution of lead nitrate, Pb(NO3)2
reacts with all of the aluminium sulphate, Al2(SO4)3, present 10. Consider the reaction 2 A + B + 3C ® P + 2Q . Starting with
in 20 mL of a solution. What is the molar concentration of 3 mol of A, 2 mol of B and 6 mol of C, number of moles of the
the Al2(SO4)3?
products P and Q would respectively be:
3Pb ( NO 3 ) 2 ( aq ) + Al2 (SO 4 )3 ( aq ) ¾¾
® 3PbSO 4 (s ) (a) 2 and 4 (b) 4 and 2 (c) 3 and 1.5 (d) 1.5 and 3
11. Percent by mass of a solute (molar mass = 28 g) in its aqueous
+ 2Al ( NO 3 )3 ( aq ) solution is 28. Calculate the mole fraction (X) and molality
(a) 6.25 × 10–2 M (b) 2.421 × 10–2 M (m) of the solute in the solution.
(c) 0.1875 M (d) None of these (a) X = 0.2, m = 10 (b) X = 0.2, m = 125/9
(c) X = 0.8, m = 125/9 (d) X = 0.8, m = 10
 EBD_7374
12 CHEMISTRY

12. 320 mg of a sample of magnesium having a coating of its (a) 34.75 (b) 69.5
oxide required 20 mL of 0.1 M hydrochloric acid for the (c) 89.5 (d) None of these
complete neutralisation of the latter. The composition of
14. A sample of peanut oil weighing 2 g is added to 25 mL of
the sample is:
0.40 M KOH. After saponification is complete, 8.5 mL of
(a) 87.5% Mg and 12.5% MgO 0.28 M H2SO4 is needed to neutralize excess of KOH. The
(b) 12.5% Mg and 87.5% MgO saponification number of peanut oil is:
(c) 80% Mg and 20% MgO (a) 146.72 (b) 223.44
(d) 20% Mg and 80% MgO (c) 98.9 (d) None of these
13. 32 g of a sample of FeSO4.7H2O were dissolved in dilute 15. What quantity (in mL) of a 45% acid solution of a
sulphuric acid and water and its volume was made up to mono-protic strong acid must be mixed with a 20% solution
1litre. 25 mL of this solution required 20 mL of 0.02 M KMnO4 of the same acid to produce 800 mL of a 29.875% acid solution?
solution for complete oxidation. Calculate the mass % of (a) 320 (b) 325 (c) 316 (d) 330
FeSO4.7H2O in the sample.

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 10 (b) 19 (c) 28 (a) 37 (b) 46 (b) 55 (a) 64 (c) 73 (c) 82 (c)
2 (d) 11 (a) 20 (b) 29 (d) 38 (a) 47 (a) 56 (d) 65 (c) 74 (c) 83 (c)
3 (a) 12 (a) 21 (c) 30 (b) 39 (c) 48 (d) 57 (c) 66 (d) 75 (a) 84 (b)
4 (d) 13 (c) 22 (d) 31 (a) 40 (c) 49 (c) 58 (b) 67 (a) 76 (a) 85 (a)
5 (c) 14 (c) 23 (c) 32 (b) 41 (a) 50 (b) 59 (d) 68 (b) 77 (b) 86 (a)
6 (a) 15 (a) 24 (c) 33 (b) 42 (d) 51 (c) 60 (b) 69 (b) 78 (b) 87 (d)
7 (d) 16 (d) 25 (c) 34 (a) 43 (b) 52 (b) 61 (c) 70 (b) 79 (a) 88 (a)
8 (c) 17 (c) 26 (b) 35 (b) 44 (d) 53 (a) 62 (a) 71 (a) 80 (b) 89 (a)
9 (d) 18 (b) 27 (a) 36 (a) 45 (a) 54 (d) 63 (a) 72 (d) 81 (b) 90 (a)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 6 (c) 11 (a) 16 (a) 21 (a) 26 (b) 31 (a) 36 (b) 41 (a)
2 (c) 7 (d) 12 (c) 17 (a) 22 (d) 27 (b) 32 (c) 37 (a) 42 (b)
3 (c) 8 (a) 13 (a) 18 (c) 23 (d) 28 (c) 33 (b) 38 (c) 43 (c)
4 (b) 9 (b) 14 (b) 19 (b) 24 (b) 29 (a) 34 (c) 39 (d) 44 (a)
5 (d) 10 (c) 15 (b) 20 (c) 25 (c) 30 (d) 35 (c) 40 (a) 45 (c)
Exercise 3 : Try If You Can
1 (a) 3 (d) 5 (a) 7 (d) 9 (c) 11 (b) 13 (b) 15 (c)
2 (a) 4 (d) 6 (c) 8 (d) 10 (d) 12 (a) 14 (a)
 Chapter
2 STRUCTURE OF ATOM

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Bohr’s model for hydrogen
AIIMS 2 atom, Quantum mechanical 4/5 8.1
JEE Main 3 model, Schrodinger wave
BITSAT 2 equation, Shape of orbitals
 EBD_7374
14 CHEMISTRY
STRUCTURE OF ATOM 15
 EBD_7374
16 CHEMISTRY

Exercise 1 : Topic-wise MCQs

10. Neutron is discovered by
Topic 1: Sub-Atomic Particles
(a) Chadwick (b) Rutherford
1. Which of the scientist were able to prove that atom is no (c) Yukawa (d) Dalton
longer non-divisible? 11. What is the ratio of mass of an electron to the mass of a
(a) Dalton (b) Michael Faraday proton?
(c) Thomson (d) Chadwick (a) 1 : 2 (b) 1 : 1 (c) 1 : 1837 (d) 1 : 3
2. Which of the following is never true for cathode rays ? 12. The increasing order for the values of e/m (charge/mass) is
(a) They possess kinetic energy. (a) e, p, n, a (b) n, p, e, a (c) n, p, a, e (d) n, a, p, e
(b) They are electromagnetic waves. 13. In which of the following the amount of deviation from
(c) They produce heat. their path in the presence of electric and magnetic field will
(d) They produce mechanical pressure. be maximum?
3. While performing cathode ray experiments, it was observed (a) N2– (b) N3– (c) N– (d) N
that there was no passage of electric current under normal 14. The deflection of the particles from their path in presence
conditions. Which of the following can account for this of electric and magnetic field will be maximum in which of
observation ? the following.
(a) Dust particles are present in air (a) O (b) N (c) U (d) He
(b) Carbon dioxide is present in air 15. Which of the following pairs have identical values of e/m?
(c) Air is a poor conductor of electricity under normal (a) A proton and a neutron
conditions (b) A proton and deuterium
(d) None of the above (c) Deuterium and an a-particle
4. Which is not true with respect to cathode rays? (d) An electron and g-rays
(a) A stream of electrons Topic 2: Atomic Models
(b) Charged particles
(c) Move with speed same as that of light 16. Rutherford’s experiment on the scattering of a -particles
(d) Can be deflected by magnetic fields showed for the first time that the atom has :
5. What is the optimum conditions required to study the (a) electrons (b) protons (c) nucleus (d) neutrons'
conduction of electricity through gases. 17. When atoms are bombarded with alpha particles, only, a
(a) High pressure and low voltage few in million suffer deflection, others pass out undeflected.
(b) High pressure and high voltage This is because
(c) Low pressure and high voltage (a) the force of repulsion on the moving alpha particle is small
(d) Low pressure and low voltage (b) the force of attraction between alpha particle and
6. In discharge tube experiment stream of negatively charged oppositely charged electrons is very small
particles travel from (c) there is only one nucleus and large number of electrons
(a) anode to cathode (b) cathode to anode (d) the nucleus occupies much smaller volume compared
(c) Both (a) and (b) (d) Electrons does not travel to the volume of the atom
7. Millikan performed an experiment method to determine 18. Rutherford’s a-particle dispersion experiment concludes
which of the following? (a) all positive ions are deposited at small part
(a) Mass of the electron (b) Charge of the electron (b) all negative ions are deposited at small part
(c) e/m ratio of electron (d) Both (a) and (b) (c) proton moves around the electron
8. Which is correct statement about proton? (d) neutrons are charged particles.
(a) Proton is nucleus of deuterium 19. Which of the following scientists explained his model on
(b) Proton is a-particle the basis of centrifugal force ?
(c) Proton is ionized hydrogen molecule (a) Thomson (b) Dalton
(d) Proton is ionized hydrogen atom (c) Millikan (d) Rutherford
9. When beryllium is bombarded with alpha particles (Chadwick’s 20. Which of the following does not contain number of neutrons
40
equal to that of 18
experiment) extremely penetrating radiations, which cannot Ar ?
be deflected by electrical or magnetic field are given out. These (a) 19 41 (b) 43 (c) 40 (d) 42
K 21 Sc 21 Sc 20 Ca
are : 21. Number of protons, neutrons and electrons in the element
(a) A beam of protons 231
89 X is
(b) Alpha rays
(c) A beam of neutrons (a) 89, 89, 242 (b) 89, 142, 89
(d) A beam of neutrons and protons (c) 89, 71, 89 (d) 89, 231, 89
STRUCTURE OF ATOM 17

22. Which of the following pairs will have same chemical (c) Radiation ener gy is n ot emitted or absorbed
properties ? continuously but in the form of small packets called
14 and 15
quanta
(a) 6 C 7 N (b) O2– and F– (d) This magnitude of energy associated with a quantum
(c) 40 40 35 37 is proportional to the frequency.
18 Ar and 19 K (d) 17 Cl and 17 Cl
23. What is the difference between two species if one has 31. The value of Planck's constant is 6.63 × 10–34 Js. The velocity
atomic mass = 14 and atomic number = 7 whereas the of light is 3.0 × 108 m s–1. Which value is closest to the
other has atomic mass = 14 and atomic number = 6? wavelength in nanometers of a quantum of light with frequency
(a) Neutrons (b) Protons of 8 × 1015 s–1 ?
(c) Electrons (d) All of these (a) 3 × 107 (b) 2 × 10–25 (c) 5 × 10–18 (d) 4 × 101
24. From the data given below A, B, C and D respectively are, 32. In the photo-electron emission, the energy of the emitted
electron is
(A) 10 e–, atomic no. 11 (B) 10 e–, atomic no. 6
(C) 10 e–, atomic no. 10 (D) 10 e–, atomic no. 9 (a) greater than the incident photon
(a) Na+, C4–, Ne, F– (b) C4–, Ne, Na–, F– (b) same as than of the incident photon
– +
(c) F , Na , Ne, C 4– (d) F–, Na+, C4–, Ne (c) smaller than the incident photon
25. Match the columns. (d) proportional to the intensity of incident photon
Column-I Column-II 33. In photoelectric effect, at which frequency electron will be
ejected with certain kinetic energy (n 0 = threshold
1 2
(A) 1 H, 1 H and 13 H (p) Isobars frequency).
14 14
(a) n > n0 (b) n0 > n (c) n0 ³ n (d) n ³ n0
(B) 6C and 7N (q) Isotopes 34. Which of the following statements are not correct about
(C) Na+ and Mg2+ (r) Isoelectronic species electromagnetic radiation ?
(a) A – (p), B – (q), C – (r) (i) Electromagnetic waves require medium to travel.
(b) A – (q), B – (p), C – (r) (ii) Different electromagnetic radiations travel at same
(c) A – (r), B – (q), C – (p) speed in vaccum.
(d) A – (p), B – (r), C – (q) (iii) The oscillating electric and magnetic fields produced
26. Chlorine exists in two isotopic forms, C1-37 and C1-35 but by oscillating charged particles are perpendicular to
its atomic mass is 35.5. This indicates the ratio of C1-37 and each other, but not to the direction of propagation.
C1-35 is approximately (iv) The oscillating electric field and magnetic field are
(a) 1 : 2 (b) 1 : 1 (c) 1 : 3 (d) 3 : 1 perpendicular to each other, and also to the direction
27. The number of electrons, neutrons and protons in a species of propagation.
are equal to 10, 8 and 8 respectively. The proper symbol of (a) (i), (ii) and (iii) (b) (ii) and (iii)
the species is (c) (i) and (iii) (d) (i) and (iv)
(a) 16O 8 (b) 18O 8 (c) 18Ne 10 (d) 16O82– 35. Which of the following statement(s) is/are incorrect
28. Assertion : All isotopes of a given element show the same regarding photoelectric effect?
type of chemical behaviour. (i) The number of electrons ejected is proportional to the
Reason : The chemical properties of an atom are controlled intensity of light.
by the number of electrons in the atom. (ii) There is some time lag between the striking of light
(a) Assertion is correct, reason is correct; reason is a beam on the metal surface and the ejection of electrons.
correct explanation for assertion. (iii) The kinetic energy of ejected electrons depends upon
(b) Assertion is correct, reason is correct; reason is not a the brightness of light.
correct explanation for assertion (iv) The kinetic energy of the ejected electron is
(c) Assertion is correct, reason is incorrect proportional to the frequency of the incident radiation.
(d) Assertion is incorrect, reason is correct. (a) (i) and (ii) (b) (ii) and (iii)
(c) (ii) only (d) (ii) and (iv)
Topic 3: Developments Leading to the Bohr’s Model of Atom
36. Assertion : Black body is an ideal body that emits and
29. If the wavelength of the electromagnetic radiation is absorbs radiations of all frequencies.
increased to thrice the digital value, then what will be the Reason : The frequency of radiation emitted by a body goes
percent change in the value of frequency of the from a lower frequency to higher frequency with an increase
electromagnetic radiation. in temperature.
(a) Increases by 33% (b) Decreases by 33% (a) Assertion is correct, reason is correct; reason is a
(c) Increases by 66% (d) Decreases by 66%
correct explanation for assertion.
30. Which one of the following is not the characteristic of
Planck’s quantum theory of radiation ? (b) Assertion is correct, reason is correct; reason is not a
(a) The energy is not absorbed or emitted in whole number correct explanation for assertion
or multiple of quantum (c) Assertion is correct, reason is incorrect
(b) Radiation is associated with energy (d) Assertion is incorrect, reason is correct.
 EBD_7374
18 CHEMISTRY

37. What will be the difference between electromagnetic 45. The third line of the Balmer series, in the emission spectrum
radiation shown in A and B respectively ? of the hydrogen atom, is due to the transition from the
(a) fourth Bohr orbit to the first Bohr orbit
(b) fifth Bohr orbit to the second Bohr orbit
(A) (c) sixth Bohr orbit to the third Bohr orbit
(d) seventh Bohr orbit to the third Bohr orbit
46. Which one of the following pairs is not correctly matched ?
(a) Rutherford-Proton (b) J.J. Thomson-Electron
(c) J.H. Chadwick-Neutron (d) Bohr-Isotopes
(B) 47. If r is the radius of the first orbit, the radius of nth orbit of
H-atom is given by
(a) rn2 (b) rn (c) r/n (d) r2 n2
(i) Velocity (ii) Wavelength 48. The radius of hydrogen atom in the ground state is 0.53 Å.
(iii) Frequency (iv) Energy The radius of Li2+ ion (atomic number = 3) in a similar state is
(a) (ii) only (b) (ii) and (iv) (a) 0.17 Å (b) 0.265 Å (c) 0.53 Å (d) 1.06 Å
(c) (ii), (iii) and (iv) (d) (iv) only 49. The energy of an electron in the nth Bohr orbit of hydrogen
38. Arrange the electromagnetic radiations a, b, c, d and e in atom is
increasing order of energy. Frequencies of a, b and c are 13.6 13.6
1015, 1014 and 1017 respectively whereas wavelength of (a) – 4 eV (b) – 3 eV
n n
(d) and (e) are 350 nm and 100 nm respectively ?
(a) a, b, c, d, e (b) a, b, d, e, c 13.6 13.6
(c) – 2 eV (d) – eV
(c) a, d, b, e, c (d) b, d, a, e, c n n
39. A 600 W mercury lamp emits monochromatic radiation of 49. The energy of second Bohr orbit of the hydrogen atom
wavelength 331.3 nm. How many photons are emitted from is -328 kJ mol -1; hence the energy of fourth Bohr orbit
the lamp per second ? (h = 6.626 × 10–34 Js; velocity of light would be:
= 3 × 108 ms–1) (a) -41 kJ mol-1 (b) -82 kJ mol-1
(a) 1 × 1019 (b) 1 × 1020 (c) 1 × 1021 (d) 1 × 1023 (c) -164 kJ mol -1 (d) -1312 kJ mol-1
40. Calculate the velocity of ejected electron from the metal 50. The energy of an electron in second Bohr orbit of hydrogen
surface when light of frequency 2 × 1015 Hz fall on the atom is :
metal surface and the threshold frequency is 7 × 1014 Hz (a) –5.44 × 10–19 eV (b) –5.44 × 10–19 cal
for metal ? –19
(c) –5.44 × 10 kJ (d) –5.44 × 10–19 J
(a) 1.37 × 106 (b) 1.26 × 106
(c) 1.45 × 10 7 (d) 1.37 × 107 51. The ionisation potential of a hydrogen atom is –13.6 eV.
What will be the energy of the atom corresponding to n = 2.
Topic 4: Bohr’s Model for Hydrogen Atom (a) – 3.4 eV (b) – 6.8 eV (c) – 1.7 eV (d) –2.7 eV
41. In continous spectrum light of _(i)
___ wavelength is deviated 52. The line spectrum of He+ ion will resemble that of
the ___
ii (a) hydrogen atom (b) Li+ ion
(a) (i) = longest, least (b) (ii) = shortest, least (c) helium atom (d) lithium atom
(c) (i) = shortest, most (d) (i) = longest, most 53. What does negative sign in the electronic energy for
42. An electron from one Bohr stationary orbit can go to next hydrogen atom convey.
higher orbit (a) Energy of electron when n = ¥
(a) by emission of electromagnetic radiation
(b) The energy of electron in the atom is lower than the
(b) by absorption of any electromagnetic radiation
energy of a free electron in motion
(c) by absorption of electromagnetic radiation of particular
frequency (c) The energy of electron in the atom is lower than the
(d) without emission or absorption of electromagnetic energy of a free electron of rest
radiation (d) The energy of electron decreases as it moves away
43. For a Bohr atom angular momentum M of the electron is from nucleus
(n = 0, 1, 2, .....) : 54. In which of the following Bohr’s stationary state, the
electron will be at maximum distance from the nucleus ?
nh 2 2 2 nh2 nh
(a) (b) n h (c) (d) (a) IInd (b) Ist (c) Vth (d) IIIrd
4p 4p 4p 2p 55. The wavelength of the radiation emitted, when in a hydrogen
44. According to Bohr's theory, the angular momentum of an atom electron falls from infinity to stationary state 1, would
electron in 5th orbit is be (Rydberg constant = 1.097×107 m–1)
(a) 10 h / p (b) 2.5 h / p (c) 25 h / p (d) 1.0 h / p (a) 406 nm (b) 192 nm (c) 91 nm (d) 9.1×10–8 nm
STRUCTURE OF ATOM 19

56. The frequency of radiation emitted when the electron falls 66. For Balmer series in the spectrum of atomic hydrogen, the
from n = 4 to n = 1 in a hydrogen atom will be (Given :
ionization energy of H=2.18 ×10 –18J atom –1 and h æ 1 1 ö
= 6.625 × 10–34 J s ) wave number of each line is given by v = R H çç 2 – 2 ÷÷
è n1 n2 ø
(a) 1.54 × 1015 s–1 (b) 1.03 × 1015 s–1
where RH is a constant and n1 and n2 are integers. Which of
(c) 3.08 × 1015 s–1 (d) 2.00 × 1015 s–1
the following statement(s) is (are) correct?
57. Which of the following transitions of electrons in the
hydrogen atom will emit maximum energy ? (i) As wavelength decreases, the lines in the series
(a) n5 ® n4 (b) n4 ® n3 converge.
(c) n3 ® n2 (d) all will emit same energy (ii) The integer n1 is equal to 2.
58. According to the Bohr theory, which of the following (iii) The ionization energy of hydrogen can be calculated
transitions in the hydrogen atom will give rise to the least from the wave number of these lines.
energetic photon ? (iv) The line of longest wavelength corresponds to n2 = 3.
(a) n = 6 to n = 1 (b) n = 5 to n = 4 (a) (i), (ii) and (iii) (b) (ii), (iii) and (iv)
(c) n = 6 to n = 5 (d) n = 5 to n = 3 (c) (i), (i) and (iv) (d) (ii) and (iv)
59. The wavelength (in cm) of second line in the Lyman series
67. Assertion : The radius of the first orbit of hydrogen atom is
of hydrogen atomic spectrum is (Rydberg constant 0.529Å.
= R cm–1)
Reason : Radius of each circular orbit (rn) = 0.529Å (n2/Z),
æ 8R ö æ 9 ö æ 4 ö æ 3R ö where n = 1, 2, 3 and Z = atomic number.
(a) ç ÷ (b) ç ÷ (c) ç ÷ (d) ç ÷
è 9 ø è 8R ø è 3R ø è 4 ø (a) Assertion is correct, reason is correct; reason is a
60. The shortest wavelength in hydrogen spectrum of Lyman correct explanation for assertion.
series when RH = 109678 cm–1 is (b) Assertion is correct, reason is correct; reason is not a
(a) 1002.7 Å (b) 1215.67 Å correct explanation for assertion
(c) 1127.30 Å (d) 911.7 Å
(c) Assertion is correct, reason is incorrect
61. What is the expression of frequency (n) associated with
(d) Assertion is incorrect, reason is correct.
absorption spectra of the photon.
68. An electron, e1 is moving in the fifth stationary state, and
R æ 1 1 ö another electron e2 is moving in the fourth stationary state.
(a) n= H ç 2 - 2 ÷ ni > nf The radius of orbit of electron, e1 is five times the radius of
h çn ÷
è i nf ø orbit of electron, e2 calculate the ratio of velocity of electron
RH æ 1 1 ö e1 (v1) to the velocity of electron e2 (v2).
(b) n= ç 2 - 2 ÷ nf > ni (a) 5 : 1 (b) 4 : 1 (c) 1 : 5 (d) 1 : 4
h çn ÷
è i nf ø 69. The Li2+ ion is moving in the third stationary state, and its
linear momentum is 7.3 × 10–34 kgms–1. Angular momentum
RH æ 1 1 ö
(c) n=– ç 2 - 2 ÷ nf > ni is.
h çn ÷ (a) 1.158 × 10–45 kg m2s–1 (b) 11.58 × 10–48 kg m2s–1
è i nf ø
(d) All the above are correct (c) 11.58 × 10–47 kg m2s–1 (d) 12 × 10–45 kg m2s–1
62. Bohr model can explain : 70. The Bohr orbit radius for the hydrogen atom (n = 1) is
(a) the solar spectrum approximately 0.530 Å. The radius for the first excited state
(b) the spectrum of hydrogen molecule (n = 2) orbit is (in Å)
(c) spectrum of any atom or ion containing one electron (a) 0.13 (b) 1.06 (c) 4.77 (d) 2.12
only 71. According to Bohr’s theory the energy required for an
(d) the spectrum of hydrogen atom only
electron in the Li2+ ion to be emitted from n = 2 state is
63. Which of the following statements do not form a part of
(given that the ground state ionization energy of hydrogen
Bohr’s model of hydrogen atom ?
atom is 13.6 eV)
(a) Energy of the electrons in the orbits are quantized
(b) The electron in the orbit nearest the nucleus has the (a) 61.2 eV (b) 13.6 eV (c) 30.6 eV (d) 10.2 eV
lowest energy 72. Among species H, Li2+, He+, Be3+ and Al3+ Bohr’s model
(c) Electrons revolve in different orbits around the nucleus was able to explain the spectra of
(d) The position and velocity of the electrons in the orbit (a) All of these
cannot be determined simultaneously. (b) None of these
64. Bohr’s theory can be applied to which of the following ions. (c) all other species except Be3+
(a) Na+ (b) Be2+ (c) Li+ (d) Li2+ (d) all other species except Al3+
65. Bohr’s model is not able to account for which of the
following. Topic 5: Towards Quantum Mechanical Model of the Atom
(a) Stability of atom. 73. If electron, hydrogen, helium and neon nuclei are all moving
(b) Spectrum of neutral helium atom. with the velocity of light, then the wavelength associated
(c) Energy of free electron at rest.
with these particles are in the order
(d) Calculation of radii of the stationary states.
 EBD_7374
20 CHEMISTRY

(a) Electron > hydrogen > helium > neon (a) H < Be, B < Li < K. (b) H > Li > K > Be > B
(b) Electron > helium > hydrogen > neon (c) H > Li > Be > B > K (d) H < Li < Be < B < K
(c) Electron < hydrogen < helium < neon 84. The velocity of particle A is 0.1 ms–1 and that of particle B is
(d) Neon < hydrogen < helium < electron 0.05 ms–1. If the mass of particle B is five times that of particle
74. The de Broglie wavelength of a tennis ball of mass 60 g A, then the ratio of de-Broglie wavelengths associated with
moving with a velocity of 10 metres per second is the particles A and B is
approximately (a) 2 : 5 (b) 3 : 4 (c) 6 : 4 (d) 5 : 2
(a) 10–31 metres (b) 10–16 metres 85. Two fast moving particles X and Y are associated with
–25
(c) 10 metres (d) 10–33 metres de Broglie wavelengths 1 nm and 4 nm respectively. If mass
Planck’s constant, h = 6.63 × 10–34 Js of X in nine times the mass of Y, the ratio of kinetic energies
75. If the energy difference between the ground state of an of X and Y would be
atom and its excited state is 4.4 × 10–4 J, the wavelength of (a) 3 : 1 (b) 9 : 1 (c) 5 : 12 (d) 16 : 9
photon required to produce the transition : 86. Uncertainty in position of an electron (mass = 9.1 × 10–28 g)
(a) 2.26 × 10–12 m (b) 1.13 × 10–22 m moving with a velocity of 3 × 104 cm/s accurate upto 0.001%
(c) 4.52 × 10–16 m (d) 4.52 × 10–22 m will be (use h/4p) in uncertainty expression where
76. The mass of a photon with a wavelength equal to h = 6.626 ×10–27 erg-second).
1.54 × 10–8 cm is (a) 1.93 cm (b) 3.84 cm (c) 5.76 cm (d) 7.68 cm
(a) 0.8268 × 10–34 kg (b) 1.2876 × 10–33 kg 87. The measurement of the electron position is associated with
(c) 1.4285 × 10 kg –32 (d) 1.8884 × 10–32 kg an uncertainty in momentum, which is equal to
77. The values of Planck's constant is 6.63 × 10–34 Js. The 1×10–18 g cm s–1. The uncertainty in electron velocity is,
velocity of light is 3.0 × 108 m s–1. Which value is closest to (mass of an electron is 9 × 10– 28 g)
the wavelength in nanometres of a quantum of light with (a) 1 × 109 cm s–1 (b) 1 × 106 cm s–1
frequency of 8 × 1015 s–1? 5
(c) 1 × 10 cm s –1 (d) 1 × 1011 cm s–1
(a) 5 × 10–18 (b) 4 × 101 (c) 3 × 107 (d) 2 × 10–25 88. In an atom, an electron is moving with a speed of 600 m/s
78. The de Broglie wavelength of a car of mass 1000 kg and with an accuracy of 0.005%. Certainity with which the
velocity 36 km/hr is : position of the electron can be located is ( h = 6.6 × 10–34 kg
(a) 6.626 × l0–34 m (b) 6.626 × 10–38 m m2s–1, mass of electron, em = 9.1 × 10–31 kg)
(c) 6.626 × 10 m –31 (d) 6.626 × 10– 30 m (a) 5.10 × 10 –3 m (b) 1.92 × 10 –3 m
79. Heisenberg's uncertainity principle is applicable to (c) 3.84 × 10 m –3 (d) 1.52 × 10 –4 m
(a) atoms only (b) electron only
Topic 6: Quantum Mechanical Model of Atom
(c) nucleus only (d) any moving object
80. The position of both, an electron and a helium atom is 89. The orientation of an atomic orbital is governed by
known within 1.0 nm. Further the momentum of the (a) Spin quantum number
electron is known within 5.0 × 10–26 kg ms–1. The minimum (b) Magnetic quantum number
uncertainty in the measurement of the momentum of the (c) Principal quantum number
helium atom is (d) Azimuthal quantum number
(a) 50 kg ms–1 (b) 80 kg ms–1 90. For which one of the following sets of four quantum
–26
(c) 8.0 × 10 kg ms –1 (d) 5.0 × 10–26 kg ms–1 numbers, an electron will have the heighest energy?
81. The Heisenberg uncertainity principle will be most n l m s
significant for which of the following object ? (a) 3 2 1 1/2
(a) Object A of mass 9.11 × 10–30 kg
(b) 4 2 –1 1/2
(b) Object B of mass 9.11 × 10–28 g
(c) 4 1 0 –1/2
(c) Object C of mass 9.11 × 10–24 mg
(d) Object D of mass 9.11 × 10–28 kg (d) 5 0 0 –1/2
82. Assertion : The position of an electron can be determined 91. Which of the following sets of quantum numbers is correct
exactly with the help of an electron microscope. for an electron in 4f orbital ?
Reason : The product of uncertainty in the measurement of (a) n = 4, l = 3, m = + 1, s = + ½
its momentum and the uncertainty in the measurement of (b) n = 4, l = 4, m = – 4, s = – ½
the position cannot be less than a finite limit. (c) n = 4, l = 3, m = + 4, s = + ½
(a) Assertion is correct, reason is correct; reason is a (d) n = 3, l = 2, m = – 2, s = + ½
correct explanation for assertion. 92. What is the correct orbital designation of an electron with
(b) Assertion is correct, reason is correct; reason is not a the quantum number, n = 4, l = 3, m = – 2, s = 1/2 ?
correct explanation for assertion (a) 3s (b) 4 f (c) 5p (d) 6s
(c) Assertion is correct, reason is incorrect 93. Which of the following represents correct set of the four
(d) Assertion is incorrect, reason is correct. quantum numbers for an electron in a 4d subshell ?
83. Arrange the following elements in the order of ease of
(a) 4, 2, 1, 0 (b) 4, 2, 1, – 1/2
detection of wave properties, in the de Broglie experiment.
(c) 4, 3, 2, + 1/2 (d) 4, 3, – 2, – 1/2
H, Li, Be, B, K
STRUCTURE OF ATOM 21

94. The total number of electrons that can be accommodated in 102. If there are five radial nodes, then what can be the correct
all orbitals having principal quantum number 2 and azimuthal representation of the orbital for n = 8.
quantum number 1 is (a) 8 d (b) 8 s (c) 8 p (d) 8 f
(a) 2 (b) 4 (c) 6 (d) 8 103. What can be the representation of the orbital having 3
angular nodes and n = 5.
95. Which of the following is not permissible arrangement of
electrons in an atom? (a) 5 d (b) 5 f (c) 5 p (d) 5 s
104. The number of orbitals present in the fifth shell will be
(a) n = 5, l = 3, m = 0, s = + 1/2
(a) 25 (b) 10 (c) 50 (d) 20
(b) n = 3, l = 2, m = – 3, s = – 1/2 105. The electronic configuration of gadolinium (Atomic number
(c) n = 3, l = 2, m = – 2, s = – 1/2 64) is
(d) n = 4, l = 0, m = 0, s = – 1/2 (a) [Xe] 4f 8 5d 0 6s2 (b) [Xe] 4f 3 5d 5 6s2
96. Which of the following sets of quantum numbers represents (c) [Xe] 4f 6 5d 2 6s2 (d) [Xe] 4f 7 5d 1 6s2
the highest energy of an atom? 106. The number of d-electrons retained in Fe2+
(At. no. of Fe = 26) ion is
(a) n = 3, l = 0, m = 0, s = +1/2
(a) 4 (b) 5 (c) 6 (d) 3
(b) n = 3, l = 1, m = 1, s = +1/2 107. The electronic configuration of an element is 1s2, 2s2 2p6,
(c) n = 3, l = 2, m = 1, s = +1/2 3s2 3p6 3d 5, 4s1. This represents its
(d) n = 4, l = 0, m = 0, s = +1/2 (a) excited state (b) ground state
97. Which set of quantum numbers are not possible? (c) cationic form (d) anionic form
n l m s 108. In a given atom no two electrons can have the same values
for all the four quantum numbers. This is called
(a) 3 2 0 +1/2 (a) Hund’s Rule (b) Aufbau principle
(b) 2 2 1 +1/2 (c) Uncertainty principle (d) Pauli’s exclusion principle
(c) 1 0 0 –1/2 109. The electronic configuration of Cu (atomic number 29) is
(d) 3 2 –2 +1/2 (a) 1s 2 , 2 s 2 2 p 6 ,3s 2 3 p 6 , 4 s 2 3d 9
98. What will be the sum of all possible values of l and m for (b) 1s 2 ,2 s 2 2 p 6 ,3s 2 3 p 6 3d 10 , 4 s1
n=5?
(c) 1s2 ,2s2 2 p6 ,3 p 2 3 p 6 ,4s2 4 p6 ,5s2 5 p1
(a) 12 (b) 13 (c) 4 (d) 9
99. The following quantum numbers are possible for how many (d) 1s 2 , 2 s 2 2 p 6 ,3 p 2 3 p 6 , 4 s 2 4 p 6 3d 3
orbital(s) n = 3, l = 2, m = +2 ? 110. The orbital diagram in which the Aufbau principle is violated is :
2s 2p 2s 2p
(a) 1 (b) 3 (c) 2 (d) 4
100. The orbitals are called degenerate when (a) ­¯ ­¯ ­ (b) ­ ­¯ ­ ­
(a) they have the same wave functions
(b) they have the same wave functions but different (c) ­¯ ­ ­ ­ (d) ­¯ ­¯ ­ ­
energies 111. Maximum number of electrons in a subshell of an atom is
(c) they have different wave functions but same energy determined by the following:
(d) they have the same energy (a) 2 l + 1 (b) 4 l – 2 (c) 2 n2 (d) 4 l + 2
112. The correct order of increasing energy of atomic orbitals is
101. Which of the following graph correspond to one node
(a) 5 p < 4 f < 6 s < 5 d (b) 5 p < 6 s < 4 f < 5 d
(c) 5 p < 5 d < 4 f < 6 s (d) None of these
113. For which element, the valence electron will be present in
Y Y the highest energy orbital.
(a) (b) (a) 3Li (b) 16S (c) 20Ca (d) 21Sc
114. Which of the following electronic configuration of d-orbital
a0 will have highest affinity for gaining an electron?
a0
(a)

Y
Y (b)
(c) (d)
(c)
a0
a0
(d)
 EBD_7374
22 CHEMISTRY

115. Match the columns. 119. Match the columns.

Column-I Column-II Column-I Column-II

(A) Y 2 (p) Energy can be emitted z

or absorbed in packets
(B) de Broglie (q) Significant only for
motion of microscopic (A) dx2 – y2 (p)
objects.
(C) Heisenberg’s (r) The probability of y x
finding an electron at a
point within an atom
(D) Planck’s (s) Every object in motion z
has a wave character.
(a) A – (q), B – (s), C – (r), D – (p)
(b) A – (r), B – (p), C – (q), D – (s) (B) dxy (q)
(c) A – (r), B – (s), C – (q), D – (p)
(d) A – (s), B – (p), C – (r), D – (q) y x
116. Match the columns.
Column-I Column-II
(Quantum number) (Information provided) z

(A) Principal (p) orientation of the orbital

quantum number
(C) dyz (r)
(B) Azimuthal (q) energy and size of orbital
quantum number
x
(C) Magnetic (r) spin of electron y
quantum number
(D) Spin quantum (s) shape of the orbital z
number
(a) A – (q), B – (s), C – (p), D – (r)
(b) A – (s), B – (q), C – (p), D – (r) (D) dz2 (s)
(c) A – (q), B – (p), C – (s), D – (r)
(d) A – (q), B – (s), C – (r), D – (p) x
y
117. Which of the following sets of quantum numbers is correct?
(a) n = 5, l = 4, m = 0, s = + ½ (a) A – (p), B – (s), C – (r), D – (q)
(b) n = 3, l = 3, m = +3, s = + ½ (b) A – (s), B – (p), C – (r), D – (q)
(c) n = 6, l = 0, m = +1, s = – ½ (c) A – (s), B – (p), C – (q), D – (r)
(d) n = 4, l = 2, m = +2, s = 0 (d) A – (s), B – (r), C – (p), D – (q)

118. Which combinations of quantum numbers, n, l , m and s for 120. The five d-orbitals are designated as d xy , d yz , d xz , d
x2 - y2
the electron in an atom does not provide a permissible and d 2. Choose the correct statement
solution of the wave equation ? z
(a) The shapes of the first three orbitals are similar but
1 1 that of the fourth and fifth orbitals are different
(a) 3, 2,1, (b) 3,1,1, - (b) The shapes of all five d-orbitals are similar
2 2
(c) The shapes of the first four orbitals are similar but that
1 1 of the fifth orbital is different
(c) 3, 3,1, - (d) 3, 2, - 2,
2 2 (d) The shapes of all five d-orbitals are different
STRUCTURE OF ATOM 23

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 6. Which of the following properties of atom could be
explained correctly by Thomson model of atom?
1. Which of the following conclusions could not be derived (a) Overall neutrality of atom
from Rutherford's a-particle scattering experiment? (b) Spectra of hydrogen atom
(a) Most of the space in the atom is empty. (c) Position of electrons, protons and neutrons in atom
(b) The radius of the atom is about 10–10 m while that of (d) Stability of atom
nucleus is 10–15 m. 7. Two atoms are said to be isobars if
(c) Electrons move in a circular path of fixed energy called (a) they have same atomic number but different mass
orbits. number
(d) Electrons and the nucleus are held together by (b) they have same number of electrons but different
electrostatic forces of attraction. number of neutrons
2. Which of the following options does not represent ground (c) they have same number of neutrons but different
state electronic configuration of an atom? number of electrons
(a) 1s22s22p63s23p63d 84s2 (d) sum of the number of protons and neutrons is same
(b) 1s22s22p63s23p63d 94s2 but the number of protons is different
(c) 1s22s22p63s23p63d104s1 8. The number of radial nodes for 3p orbital is ......... .
(d) 1s22s22p63s23p63d 54s1 (a) 3 (b) 4 (c) 2 (d) 1
3. The probability density plots of 1s and 2s orbitals are given 9. Number of angular nodes for 4d orbital is ........... .
in figure. (a) 4 (b) 3 (c) 2 (d) 1
10. Which of the following is responsible to rule out the
existence of definite paths or trajectories of electrons?
1s (a) Pauli's exclusion principle
2s (b) Heisenberg's uncertainty principle
The density of dots in a region represents the probability (c) Hund's rule of maximum multiplicity
density of finding electrons in the region. (d) Aufbau principle
11. Total number of orbitals associated with third shell will
On the basis of above diagram which of the following
be ............... .
statements is incorrect?
(a) 2 (b) 4 (c) 9 (d) 3
(a) 1s and 2s orbitals are spherical in shape.
12. Orbital angular momentum depends on ............ .
(b) The probability of finding the electron is maximum near
(a) l (b) n and l (c) n and m (d) m and s
the nucleus.
13. Chlorine exists in two isotopic forms Cl-37 and Cl-35, but
(c) The probability of finding the electron at a given its atomic mass is 35.5. This indicates the ratio of Cl-37 and
distance is equal in all directions. Cl-35 is approximately
(d) The probability density of electrons for 2s orbital (a) 1 : 2 (b) 1 : 1 (c) 1 : 3 (d) 3 : 1
decreases uniformly as distance from the nucleus 14. The pair of ions having same electronic configuration
increases. is .............. .
4. Which of the following statement is not correct about the (a) Cr3+, Fe3+ (b) Fe3+, Mn2+
characteristics of cathode rays? (c) Fe , Co 3+ 3+ (d) Sc3+, Cr 3+
(a) They start from the cathode and move towards the 15. For the electrons of oxygen atom, which of the following
anode. statements is correct?
(b) They travel in straight line in the absence of an external (a) Zeff for an electron in a 2s orbital is the same as Zeff for
electrical or magnetic field. an electron in a 2p orbital.
(c) Characteristics of cathode rays do not depend upon (b) An electron in the 2s orbital has the same energy as an
the material of electrodes in cathode ray tube. electron in the 2p orbital.
(d) Characteristics of cathode rays depend upon the (c) Zeff for an electron in 1s orbital is the same as Zeff for an
nature of gas present in the cathode ray tube. electron in a 2s orbital.
5. Which of the following statements about the electron is (d) The two electrons present in the 2s orbital have spin
incorrect? quantum numbers ms but of opposite sign.
(a) It is a negatively charged particle. 16. If travelling at same speeds, which of the following matter
(b) The mass of electron is equal to the mass of neutron. waves have the shortest wavelength?
(c) It is a basic constituent of all the atoms. (a) Electron (b) Alpha particle (He2+)
(d) It is a constituent of cathode rays. (c) Neutron (d) Proton
 EBD_7374
24 CHEMISTRY

Past Year MCQs 26. A stream of electrons from a heated filaments was passed
two charged plates kept at a potential difference V esu. If
17. What is the maximum number of orbitals that can be identified
e and m are charge and mass of an electron, respectively,
with the following quantum numbers?
then the value of h/l (where l is wavelength associated
n = 3, l = 1, ml = 0 [AIPMT 2014, A] with electron wave) is given by: [JEE M 2016, S]
(a) 1 (b) 2 (c) 3 (d) 4
(a) meV (b) 2meV (c) meV (d) 2meV
18. Calculate the energy in joule corresponding to light of
wavelength 45 nm : 27. An e– has magnetic quantum number as –3, what is its
principal quantum number? [BITSAT 2016, A]
(Planck’s constant h = 6.63 × 10 –34 Js; speed of light
(a) 1 (b) 2 (c) 3 (d) 4
c = 3 × 108 ms–1) [AIPMT 2014, A]
28. The first emission line in the atomic spectrum of hydrogen
(a) 6.67 × 1015 (b) 6.67 × 1011
in the Balmer series appears at [BITSAT 2016, S]
(c) 4.42 × 10–15 (d) 4.42 × 10–18
19. In hydrogen atomic spectrum, a series limit is found at 9R 7R
(a) cm -1 (b) cm -1
12186.3 cm–1. Then it belong to [AIIMS 2014, C] 400 144
(a) Lyman series (b) Balmer series
3R 5R
(c) Paschen series (d) Brackett series (c) cm -1 (d) cm -1
20. The correct set of four quantum numbers for the valence 4 36
electrons of rubidium atom (Z = 37) is: [JEE M 2014, S] 29. Which one is the wrong statement ? [NEET 2017, C]
(a) The uncertainty principle is DE ´ Dt ³ h / 4p
1 1
(a) 5, 0, 0, + (b) 5,1, 0, + (b) Half filled and fully filled orbitals have greater stability
2 2
due to greater exchange energy, greater symmetry and
1 1 more balanced arrangement.
(c) 5,1,1, + (d) 5, 0,1, +
2 2 (c) The energy of 2s orbital is less than the energy of
21. For azimuthal quantum number l = 3, the maximum number 2p orbital in case of Hydrogen like atoms
of electrons will be [BITSAT 2014, C] h
(a) 2 (b) 6 (c) 0 (d) 14. (d) de-Broglies's wavelength is given by l = ,
mn
æ Z2 ö where m = mass of the particle, n = group velocity of
22. Based on equation E = – 2.178 × 10-18 J çç 2 ÷÷ , certain the particle
èn ø 30. In Bohr series of lines of hydrogen spectrum, the third line
conclusions are written. Which of them is not correct ? from the red end corresponds to which one of the following
[AIIMS 2015, C] inter-orbit jumps of the electron for Bohr orbits in an atom
(a) Larger the value of n, the larger is the orbit radius. of hydrogen [AIIMS 2017, S]
(b) Equation can be used to calculate the change in energy (a) 5 ® 2 (b) 4 ® 1 (c) 2 ® 5 (d) 3 ® 2
when the electron changes orbit.
31. The radius of the second Bohr orbit for hydrogen atom is :
(c) For n = 1, the electron has a more negative energy than
it does for n = 6 which mean that the electron is more (Plank's const. h = 6.6262 × 10–34 Js ; mass of
loosely bound in the smallest allowed orbit. electron = 9.1091 × 10–31 kg ; charge of electron
(d) The negative sign in equation simply means that the e = 1.60210 × 10–19 C ; permittivity of vaccum
energy or electron bound to the nucleus is lower than Î0 = 8.854185 × 10–12 kg–1 m–3 A2) [JEE M 2017, A]
it would be if the electrons were at the infinite distance
from the nucleus. (a) 1.65Å (b) 4.76Å (c) 0.529Å (d) 2.12Å
23. Which of the following is the energy of a possible excited 32. The number of radial nodes of 3s and 2p orbitals are
state of hydrogen ? [JEE M 2015, A] respectively
(a) –3.4 eV (b) +6.8 eV (c) +13.6 eV (d) –6.8 eV [BITSAT 2017, C]
24. Two electrons occupying the same orbital are distinguished (a) 2, 0 (b) 0, 2 (c) 1, 2 (d) 2, 2
by [NEET 2016, C] 33. The energy of an electron in second Bohr orbit of hydrogen
(a) Principal quantum number atom is : [BITSAT 2017, A]
(b) Magnetic quantum number (a) –5.44 × 10–19 eV (b) –5.44 × 10–19 cal
(c) Azimuthal quantum number (c) –5.44 × 10–19 kJ (d) –5.44 × 10–19 J
(d) Spin quantum number 34. The angular speed of the electron in n th orbit of Bohr
25. Which transition in the hydrogen atomic spectrum will have hydrogen atom is [NEET 2018, C]
the same wavelength as the transition, n = 4 to n = 2 of He+ (a) Directly proportional to n
spectrum? [AIIMS 2016, A] (b) Inversely proportional of n
(a) n = 4 to n = 3 (b) n = 3 to n = 2 (c) Inversely proportional to n 2
(c) n = 4 to n = 2 (d) n = 2 to n = 1 (d) Inversely proportional to n 3
STRUCTURE OF ATOM 25

35. What is maximum wavelength of line of Balmer series of (a) Assertion is correct, reason is correct; reason is a
hydrogen spectrum (R = 1.09 × 107 m–1) [AIIMS 2018, A] correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a
(a) 400 nm (b) 654 nm correct explanation for assertion.
(c) 486 nm (d) 434 nm (c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct.
36. Assertion : Threshold frequency is the maximum frequency
required for the ejection of electron from the metal surface. 37. If the Planck’s constant h = 6.6×10–34 Js, the de Broglie
wavelength of a particle having momentum of 3.3 × 10–24
Reason : Threshold frequency is characteristic to a metal. kg ms –1 will be [BITSAT 2018]
[AIIMS 2018, C] (a) 0.002 Å (b) 0.5Å (c) 2Å (d) 500Å

Exercise 3 : Try If You Can

1. Which of the following statement concerning probability
1 m h 1 h m
density ( y 2 ) and radial distribution function (4pr 2 y 2 ) for (a) (b) 10 (c) (d) 10
10 h m 10 m h
a s-orbital of H-like species is correct? 8. A hydrogen-like atom with atomic number Z is in the higher
(a) y 2 is minimum at nucleus but 4pr 2 y 2 is maximum excited state of quantum number n. This excited state atom
at nucleus. can make a transition to the 1st excited state by successively
(b) y 2 is maximum at nucleus but 4pr 2 y 2 is minimum emitting two photons of energies 10 eV and 17eV,
at nucleus. respectively. Alternatively the atom from the same excited
(c) Both y 2 and 4pr 2 y 2 are maximum at nucleus. state can make a transition to 2nd excited state by emitting
(d) Both y 2 and 4pr 2 y 2 are minimum at nucleus. two photons of energies 4.25 eV and 5.95 eV, respectively.
2. If the shortest wavelength of the spectral line of H-atom in Determine Z and n.
the Lyman series is X, then the longest wavelength of the (a) n = 6, Z = 3 (b) n = 3, Z = 6
(c) n = 2, Z = 4 (d) n = 9, Z = 9
line in Balmer series of Li 2+ is
9. In a multi-electron atom, which of the following orbitals
x 5x 4x described by the three quantum members will have the same
(a) 9x (b) (c) (d)
9 4 5 energy in the absence of magnetic and electric fields?
3. A hydrogen atom in the ground state is excited by (A) n = 1, l = 0, m = 0 (B) n = 2, l = 0, m = 0
monochromatic radiation of wavelength l Å. The resulting (C) n = 2, l = 1, m = 1 (D) n = 3, l = 2, m = 1
spectrum consists of maximum 15 different lines. What is (E) n = 3, l = 2, m = 0
the wavelength l? (RH = 109737 cm–1) (a) (D) and (E) (b) (C) and (D)
(a) 937.3 Å (b) 1025 Å (c) (B) and (C) (d) (A) and (B)
(c) 1236 Å (d) None of these 10. 1.5 L He gas is taken at 500K and 560 mm pressure in which
4. If radiation corresponding to second line of "Balmer series" 90% He are converted into He+ ions. Spectral line analysis
of Li2+ ion, knocked out electron from first excited state of shows that 85% ions exist in the 3rd level, 10% in the 2nd
H-atom, then kinetic energy of ejected electron would be: level and rest in the ground level. Calculate the total energy
(a) 2.55 eV (b) 4.25 eV (c) 11.25 eV (d) 19.55 eV evolved when all ions return back to ground state.
5. Li 3+ and a proton are accelerated by the same potential, (a) 106 kJ (b) 957.1 kJ (c) 212 kJ (d) 104.9 kJ
then de-Broglie wavelengths l Li and l p have the ratio 11. If an electron undergoes transition from n = 2 to n = 1 in Li2+
ion, the energy of photon radiated will be best given by
(assume m Li = 9 m p )
(a) hv (b) hv1 + hv2
(a) 1 : 3 3 (b) 1 : 1 (c) 1 : 2 (d) 1 : 4 (c) hv1 + hv2 + hv3 (d) all of these
6. –17
Assume that 2 × 10 J of light energy is needed by the 12. If l0 and l be the threshold wavelength and the wavelength
interior of the human eye to see an object. How many of incident light, the speed of photoelectrons ejected from
photons of yellow light with l = 595.2 nm are needed to the metal surface is :
generate this minimum energy?
2h 2hc
(a) 6 (b) 30 (c) 45 (d) 60 (a) ( l0 - l ) (b) (l0 - l )
7. If the de-Broglie wavelength of a particle of mass m is 100 m m
times its velocity, then its value in terms of its mass (m) and
Planck’s constant (h) is 2hc æ l0 - l ö 2h æ 1 1 ö
(c) ç ÷ (d) ç - ÷
m è ll0 ø m è l0 l ø
 EBD_7374
26 CHEMISTRY

13. The radii of maximum probability for 3s, 3p and 3d electrons

are in the order (a) 3.5 RH (b) 4 RH (c) 8 RH (d) 8 RH
9
(a) (rmax )3d > (rmax )3 p > (rmax )3s
15. If two particles are associated with same kinetic energy, then
(b) (rmax )3d > (rmax )3s > (rmax )3 p
the de Broglie’s wavelength (l) of these particles is
(c) ( rmax )3 s > ( rmax ) 3 p > ( rmax )3 d
(a) directly proportional to the velocity
(d) none of these
(b) inversely proportional to the velocity
14. The wave number of electromagnetic radiation emitted
during the transition in between two energy levels of Li2+ (c) independent of mass and velocity
ion whose principal quantum number sum is 4 and difference (d) can not be predicted
is 2, is

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 13 (b) 25 (b) 37 (c) 49 (b) 61 (b) 73 (a) 85 (d) 97 (b) 109 (b)
2 (b) 14 (d) 26 (c) 38 (d) 50 (d) 62 (c) 74 (d) 86 (a) 98 (b) 110 (b)
3 (c) 15 (c) 27 (d) 39 (c) 51 (a) 63 (d) 75 (d) 87 (a) 99 (a) 111 (d)
4 (c) 16 (c) 28 (a) 40 (a) 52 (a) 64 (d) 76 (c) 88 (b) 100 (d) 112 (b)
5 (c) 17 (d) 29 (d) 41 (c) 53 (c) 65 (b) 77 (b) 89 (b) 101 (b) 113 (d)
6 (b) 18 (a) 30 (a) 42 (d) 54 (c) 66 (c) 78 (b) 90 (b) 102 (a) 114 (d)
7 (b) 19 (d) 31 (d) 43 (b) 55 (c) 67 (a) 79 (d) 91 (a) 103 (b) 115 (c)
8 (d) 20 (c) 32 (c) 44 (b) 56 (c) 68 (d) 80 (d) 92 (b) 104 (a) 116 (a)
9 (c) 21 (b) 33 (a) 45 (d) 57 (c) 69 (b) 81 (b) 93 (b) 105 (d) 117 (a)
10 (a) 22 (d) 34 (c) 46 (a) 58 (c) 70 (d) 82 (d) 94 (c) 106 (c) 118 (c)
11 (c) 23 (d) 35 (b) 47 (a) 59 (a) 71 (c) 83 (c) 95 (b) 107 (b) 119 (b)
12 (d) 24 (a) 36 (b) 48 (c) 60 (d) 72 (d) 84 (d) 96 (c) 108 (d) 120 (c)
Exercise 2 : Exemplar & Past Year MCQs
1 (c) 5 (b) 9 (c) 13 (c) 17 (a) 21 (d) 25 (d) 29 (c) 33 (d) 37 (c)
2 (b) 6 (a) 10 (b) 14 (b) 18 (d) 22 (c) 26 (b) 30 (a) 34 (d)
3 (d) 7 (d) 11 (c) 15 (d) 19 (c) 23 (a) 27 (d) 31 (d) 35 (b)
4 (d) 8 (d) 12 (a) 16 (b) 20 (a) 24 (d) 28 (d) 32 (a) 36 (d)
Exercise 3 : Try If You Can
1 (b) 3 (a) 5 (a) 7 (b) 9 (a) 11 (a) 13 (c) 15 (a)
2 (d) 4 (d) 6 (d) 8 (a) 10 (b) 12 (c) 14 (c)
 3
Chapter
CLASSIFICATION OF
ELEMENTS AND PERIODICITY
IN PROPERTIES

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Variation in periodic properties,
AIIMS 2 acid base behaviour of oxides 3/5 6.7
JEE Main 2 and hydroxides.
BITSAT 3
 EBD_7374
28 CHEMISTRY
CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES 29
 EBD_7374
30 CHEMISTRY

Exercise 1 : Topic-wise MCQs

the order of increasing atomic weights.
Topic 1: Genesis of Periodic Classification
(a) Iodine (b) Antimony
1. Periodic classification of elements is used to examine the (c) Bromine (d) Molybdenum
(a) periodic trends in physical properties of elements 12. Which of the following is correct about Eka-Aluminium and
(b) periodic trends in chemical properties of elements Eka-Silicon ?
(c) Both (a) and (b) (a) Oxides of Eka-Aluminium is Al2O3 and Eka-Silicon is
(d) None of the above Si2O3
2. Cl, Br, I, if this is Dobereiner’s triad and the atomic masses of (b) Oxides of Eka-Aluminium is Ga2O3 and Eka-Silicon is
Cl and I are 35.5 and 127 respectively the atomic mass of Br is GeO2
(a) 162.5 (b) 91.5 (c) 81.25 (d) 45.625 (c) Melting point of Eka-Aluminium is lower than the
3. If the two members of a Dobereiner triad are phosphorus melting point of Eka-Silicon
and antimony, the third member of this triad is (d) Both (a) and (c)
(a) arsenic (b) sulphur (c) iodine (d) calcium
4. Lothar Meyer plotted the physical properties such as atomic Topic 2: Modern Periodic Law and the Present Form of
volume, melting point and ...X... against atomic weight. Here, the Periodic Table
X refers to 13. Which of the scientists given below discovered that
(a) mass (b) boiling point periodic table should be based on the atomic number ?
(c) surface tension (d) None of these (a) Mendeleev (b) Newlands
5. The most significant contribution towards the development (c) Moseley (d) Lothar Meyer
of periodic table was made by 14. How many elements are there in 6th period of periodic table?
(a) Mendeleev (b) Avogadro (a) 18 (b) 8 (c) 30 (d) 32
(c) Dalton (d) Cavendish 15. Modern periodic table is based on the atomic number of the
6. Mendeleev classified elements in elements. The experiment which proved the significance of
(a) increasing order of atomic groups the atomic number was
(b) eight periods and eight groups (a) Millikan’s oil drop experiment
(c) seven periods and nine groups (b) Mosley’s work on X-ray spectra
(d) eight periods and seven groups (c) Bragg’s work on X-ray diffraction
7. Select the correct chronological order for the discoveries (d) Discovery of X-rays by Rontgen
of the following scientists. 16. The symbol and IUPAC name for the element with atomic
Dobereiner, Newlands, Chancourtois, Mendeleev number 120, respectively are
(a) Chancourtois, Dobereiner, Newlands, Mendeleev (a) Ubn and unbinilium (b) Ubn and unbiunium
(b) Dobereiner, Chancourtois, Newlands, Mendeleev (c) Ubn and unnibium (d) Ubn and unnilium
(c) Dobereiner, Newlands, Chancourtois, Mendeleev 17. Element with which of the following atomic number was
(d) Chancourtois, Newlands, Dobereiner, Mendeleev named by American Society as Rutherfordium, while by
8. The molecular formula of chloride of Eka-Aluminium and Soviet Society it was named as Kurchatovium?
Eka-Silicon respectively are (a) 108 (b) 104 (c) 114 (d) 110
(a) GaCl3 and SiO4 (b) GaCl3 and AlCl3 18. What is the IUPAC name of the element with atomic number
(c) AlCl3 and SiCl4 (d) GaCl3 and GeCl4 114 ?
9. Who developed long form of the periodic table? (a) Unununnium (b) Unnilquadium
(a) Lothar Meyer (b) Neils Bohr (c) Ununquadium (d) Unnilennium.
(c) Mendeleev (d) Moseley 19. The long form of periodic table consists of
10. Which fact is not valid for Dobereiner's triads? (a) seven periods and eight groups
(a) The atomic weight of middle element is roughly average (b) seven periods and eighteen groups
of the other two elements (c) eight periods and eighteen groups
(b) The properties of middle element is roughly average of (d) eighteen periods and eight groups
the other two elements 20. Which of the following statement(s) about the modern
(c) The elements of triads belong to the same group of periodic table is/are incorrect ?
modern periodic table (i) The elements in the modern periodic table are arranged
(d) The elements of triads have same valency electrons. on the basis of their decreasing atomic number
11. In the Mendeleev’s periodic table, which of the following (ii) The elements in the modern periodic table are arranged
element instead of having lower atomic weight was placed on the basis of their increasing atomic masses
after the element of higher atomic weight thereby ignoring
CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES 31

(iii) Isotopes are placed in adjoining group(s) in the periodic 29. Match the columns.
table Column-I Column-II
(iv) The elements in the modern periodic table are arranged (A) Newland law (p) Atomic mass vs
on the basis of their increasing atomic number of octaves Atomic volume
(a) (i) only (b) (i), (ii) and (iii) (B) Mendeleev (q) Li, Na, K
(c) (i), (ii) and (iv) (d) (iv) only (C) Lother Meyer (r) One to seven groups sub-
21. Match Column-I (IUPAC nomenclature of element) with divided into group A and
Column-II (IUPAC official name). B
Column-I Column-II (D) Dobereiner's triad (s) Only 56 elements known
(A) Unnilhexium (p) Lawrencium (a) A–(s); B–(r); C–(p); D–(q)
(B) Unniltrium (q) Dubnium (b) A–(s); B–(r); C–(p); D – (q)
(C) Unnilunium (r) Seaborgium (c) A–(s); B–(r); C–(q); D – (p)
(D) Unnilpentium (s) Mendelevium (d) A–(s); B–(r); C–(p); D – (q)
(a) A – (s), B – (p), C – (r), D – (q) 30. The electronic configuration of four elements are given
(b) A – (r), B – (p), C – (s), D – (q) below. Which elements does not belong to the same family
(c) A – (r), B – (s), C – (p), D – (q) as others?
(d) A – (q), B – (r), C – (p), D – (s) (a) [Xe] 4f 145d101s2 (b) [Kr] 4d105s2
22. Assertion : Atomic number of the element ununbium is 112. 2
(c) [Ne] 3s 3p 5 (d) [Ar] 3d10 4s2
Reason : Name for digits 1 and 2 is un- and bi-respectively 31. The elements with atomic numbers 9, 17, 35, 53 and 85 belong to
in latin words. (a) alkali metals (b) alkaline earth metals
(a) Assertion is correct, reason is correct; reason is a (c) halogens (d) noble gases
correct explanation for assertion. 32. Which of the following pairs has both members from the
(b) Assertion is correct, reason is correct; reason is not a same period of the periodic table.
correct explanation for assertion. (a) Na – Ca (b) Na – Cl (c) Ca – Cl (d) Cl – Br
(c) Assertion is correct, reason is incorrect. 33. The elements which are characterized by the outer electronic
(d) Assertion is incorrect, reason is correct. configuration ns1 to ns2 np6 are collectively called
(a) Transition elements (b) Representative elements
Topic 3: Electronic Configurations of Elements,
(c) Lanthanides (d) Inner transition elements
the Periodic Table and Types of Elements: 34. f-Block elements are called inner transition elements because
s, p, d, f –Blocks (a) they have properties similar to those of transition
23. Elements of which group form anions most readily? elements
(a) Oxygen family (b) Nitrogen family (b) they exist in between transition elements
(c) Halogens (d) Alkali metals (c) the last electron enters into the f-orbital of the
24. Consider the following statements: penultimate shell
(i) The discovery of inert gases later on did not disturb (d) the last electron enters into any orbital of penultimate
Mendeleev's arrangement. shell
(ii) In the present periodic table, periodicity in the 35. An element, which belongs to third period and group 16 in
properties of elements is related to the periodicity in the periodic table has electronic configuration.
their electronic configurations. (a) 1s2, 2s2 2p6, 3s2 3p3 (b) 1s2, 2s2 2p6, 3s2 3p4
2 2 6 2
(c) 1s , 2s 2p , 3s 3p 5 (d) 1s2, 2s2 2p4
Which of these statement(s) is/are correct ?
(a) (i) only (b) (ii) only 36. Which of the following is non-metallic ?
(c) Both (i) and (ii) (d) Neither (i) nor (ii) (a) B (b) Be (c) Mg (d) Al
25. Element with electronic configuration 1s2 2s2 2p6 3s2 3p6 37. Which group of the periodic table contains coinage metal ?
3d10 4s2 4p6 4d10 5s2 5p3 belongs to the following group of (a) IIA (b) IB
the periodic table (c) IA (d) None of these
(a) 2nd (b) 5th (c) 3rd (d) 7th 38. The only non-metal which is liquid at ordinary temperature is
26. Element having atomic no. of 56 belongs to which of the (a) Hg (b) Br2
following block of periodic table? (c) NH3 (d) None of these
(a) p- block (b) d-block (c) f- block (d) s-block 39. Which is a metalloid?
27. In the modern periodic table one of the following does not (a) Pb (b) Sb (c) Bi (d) Zn
have appropriate position – 40. In the long form of the periodic table all the non-metals are
(a) transition elements (b) inert gases placed in
(c) inner transition elements (d) halogens (a) s-block (b) p-block (c) f-block (d) d-block
28. If the atomic number of an element is 33, it will be placed in 41. Arrange the following elements in the order of their
the periodic table in the increasing non-metallic character
(a) First group (b) Third group Li, O, C, Be, F
(c) Fifth group (d) Seventh group. (a) F < O < C < Be < Li (b) Li < Be < C < O< F
(c) F < O < C < Be < Li (d) F < O < Be < C < Li
 EBD_7374
32 CHEMISTRY

42. Which of the following statements are correct? (a) 33 (b) 34 (c) 36 (d) 49
(i) The second period (n = 2) starts with lithium and third 50. Which of the following elements show the given properties?
electron enters the 2s orbital. (i) All elements are metals.
(ii) Successive filling of 3s and 3p orbitals gives rise to (ii) Most of the elements form coloured ions, exhibit
the third period of 8 elements from sodium to argon. variable valence and paramagnetism.
(iii) The fourth period (n = 4) starts at potassium and the (iii) Oftently used as catalysts.
added electron fill up the first 4s and 4p orbitals than (a) Chalcogens
3d orbital is filled. (b) Transition elements
(iv) Fifth period begins with rubidium with the filling of 5s (c) Inner transition elements
orbital and ends at xenon with the filling up of the 5p (d) Representative elements
orbital. 51. Which of the given elements A, B, C, D and E with atomic
(a) (i) and (ii) (b) (i), (ii) and (iii) number 2, 3, 7, 10 and 30 respectively belong to the same
(c) (iii) and (iv) (d) (i), (ii) and (iv) period?
43. Consider the following statements: (a) A, B, C (b) B, C, D (c) A, D, E (d) B, D, E
(i) The elements silicon, germanium and arsenic are called 52. Match the columns.
metalloids. Column-I Column-II
(ii) Metalloids have properties quite different from those (Name of element) (Period of element)
of metals and non-metals. (A) Hydrogen (p) 3
Which of these statement(s) is/are correct ? (B) Sodium (q) 4
(a) (i) only (b) (ii) only (C) Calcium (r) 6
(c) Both (i) and (ii) (d) Neither (i) nor (ii) (D) Barium (s) 1
44. Consider the following statements: (E) Iodine (t) 5
(i) Metals will be found on the right side of the periodic (a) A – (p), B – (s), C – (q), D – (r), E – (t)
table. (b) A – (s), B – (p), C – (q), D – (r), E – (t)
(ii) The elements P, S and O belong to the same period. (c) A – (s), B – (q), C – (p), D – (r), E – (t)
Which of these statement(s) is/are correct ? (d) A – (s), B – (p), C – (q), D – (t), E – (r)
(a) (i) only (b) (ii) only 53. Element X forms a chloride with the formula XCl2, which is a
(c) Both (i) and (ii) (d) Neither (i) nor (ii)
solid with a high melting point. X would most likely be in the
45. Match the columns.
same group of the periodic table as –
Column-I Column-II
(a) Na (b) Mg (c) Al (d) Si
(A) ‘s’ block elements (p) Cr
54. An element X belongs to fourth period and fifteenth group
(B) ‘p’ block elements (q) Na
of the periodic table. Which one of the following is true
(C) ‘d’ block elements (r) Ce
regarding the outer electronic configuration of X ? It has
(D) ‘f’ block elements (s) Si
(a) Partially filled d-orbitals and completely filled s-orbitals
(a) A – (s), B – (q), C – (p), D – (r)
(b) Completely filled s-orbital and completely filled
(b) A – (q), B – (s), C – (r), D – (p)
p-orbitals
(c) A – (q), B – (p), C – (s), D – (r)
(c) Completely filled s-orbital and half-filled p-orbitals
(d) A – (q), B – (s), C – (p), D – (r)
(d) Half-filled d-robitals and completely filled s-orbitals
46. Assertion : Helium is placed in group 18 along with p-block
55. Match the columns.
elements.
Column-I Column-II
Reason : It shows properties similar to p-block elements.
(A) Element with largest size (p) Boron
(a) Assertion is correct, reason is correct; reason is a
in second period
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a (B) Element with smallest size (q) Fluorine
correct explanation for assertion. in group 13
(c) Assertion is correct, reason is incorrect. (C) Element with maximum (r) Bromine
(d) Assertion is incorrect, reason is correct. non-metallic character
47. Which of the following elements are found in pitch blende? (D) Element with smallest size (s) Lithium
(a) Actinium and protoactinium in fourth period
(b) Neptunium and plutonium (E) Element with most metallic (t) Lead
(c) Actinium only character in group 14
(d) Both (a) and (b) (a) A – (s), B – (p), C – (q), D – (t), E – (r)
48. Which of the following period contain most of the man- (b) A – (p), B – (s), C – (q), D – (r), E – (t)
made radioactive elements? (c) A – (s), B – (q), C – (p), D – (r), E – (t)
(a) Seventh (b) Fifth (d) A – (s), B – (p), C – (q), D – (r), E – (t)
(c) Sixth (d) Both (a) and (c) 56. Assertion : Second period consists of 8 elements.
49. The electronic configuration of an element is Reason : Number of elements in each period is four times
1s22s22p63s23p3. What is the atomic number of the element, the number of atomic orbitals available in the energy level
which is just below the above element in the periodic table? that is being filled.
CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES 33

(a) Assertion is correct, reason is correct; reason is a 68. Which of the following metals requires the radiation of
correct explanation for assertion. highest frequency to cause the emission of electrons ?
(b) Assertion is correct, reason is correct; reason is not a (a) Na (b) Mg (c) K (d) Ca
correct explanation for assertion. 69. Halogens and chalcogens family have highly ...P.. electron
(c) Assertion is correct, reason is incorrect. gain enthalpy. Here, P refers to
(d) Assertion is incorrect, reason is correct. (a) negative (b) positive (c) zero (d) infinity
57. An element has electronic configuration 1s2 2s2 2p6 3s2 3p4. 70. Which of the following represents the correct order of
increasing electron gain enthalpy with negative sign for the
(a) Period = 3rd, block = p, group = 16
elements O, S, F and Cl ?
(b) Period = 5th, block = s, group = 1 (a) Cl < F < O < S (b) O < S < F < Cl
(c) Period = 3rd, block = p, group = 10 (c) F < S < O < Cl (d) S < O < Cl < F
(d) Period = 4th, block = d, group = 12 71. The electron affinity for the inert gases is –
Topic 4: Periodic Trends in Properties of Elements (a) zero (b) high (c) negative (d) positive
72. The element with positive electron gain enthalpy is
58. Which is the correct order of ionic sizes (a) hydrogen (b) sodium
(At. no. : Ce = 58, Sn = 50, Yb = 70 and Lu = 71) ? (c) oxygen (d) neon
(a) Ce > Sn > Yb > Lu (b) Sn > Ce > Yb > Lu 73. Which of the following will have the least negative electron
(c) Lu > Yb > Sn > Ce (d) Sn > Yb > Ce > Lu gain enthalpy?
59. The order of increasing sizes of atomic radii among the (a) P (b) S (c) Cl (d) F
elements O, S, Se and As is : 74. Which is the correct order of electronegativity ?
(a) As < S < O < Se (b) Se < S < As < O (a) F > N < O > C (b) F > N > O > C
(c) O < S < As < Se (d) O < S < Se < As (c) F > N > O < C (d) F < N < O =C
60. In the ions P3–, S2– and Cl–, the increasing order of size is 75. The correct order of decreasing electronegativity values
(a) Cl–, S2–, P3– (b) P3–, S2–, Cl– among the elements I-beryllium, II-oxygen, III-nitrogen and
2– –
(c) S , Cl , P 3– (d) S2–, P3–, Cl– IV-magnesium is
61. Which of the following is correct ? (a) II > III > I > IV (b) III > IV > II > I
(a) Isoelectronic ions have same nuclear charge (c) I > II > III > IV (d) I > II > IV > III
(b) Isoelectronic ions have same neutrons 76. An element having electronic configuration 1s22s22p63s2
(c) Isoelectronic ions have same number of electrons 3p64s1 forms
(d) All are correct (a) Acidic oxide (b) Basic oxide
62. On going down a main sub-group in the periodic table (c) Amphoteric oxide (d) Neutral oxide
(example Li to Cs in IA or Be to Ra in IIA), the expected trend 77. Consider the following statements:
of changes in atomic radius is a (i) Atomic radii decreases across a row of the periodic
(a) continuous increase table when we move from left to right.
(b) continuous decrease (ii) Atomic radii increases down the column as we move
(c) periodic one, an increase followed by a decrease from top to bottom.
(d) decrease followed by increase (iii) Although the order of elements is based on atomic
63. Why the size of an anion is larger than the parent atom? numbers, vertical families share similar chemical
(a) Due to increased repulsion among the electrons. properties.
(b) Due to decrease in effective nuclear charge. Which of the statement(s) given above is/are correct?
(c) Due to increased in effective nuclear charge. (a) (i) and (ii) (b) (i) and (iii)
(d) Both (a) and (b) (c) (ii) and (iii) (d) (i), (ii) and (iii)
64. Which ionisation potential (IP) in the following equations 78. Which of the following sequence correctly represents the
involves the greatest amount of energy ? decreasing acidic nature of oxides?
(a) Na ® Na + + e - (b) K + ® K 2+ + e - (a) Li2O > BeO > B2O3 > CO2 > N2O3
(c) C 2 + ® C 3+ + e- (d) Ca + ® Ca 2 + + e - (b) N2O3 > CO2 > B2O3 > BeO > Li2O
65. Arrange S, P, As in order of increasing ionisation energy (c) CO2 > N2O3 > B2O3 > BeO > Li2O
(a) S < P < As (b) P < S < As (d) B2O3 > CO2 > N2O3 > Li2O > BeO
(c) As < S < P (d) As < P < S 79. Match Column-I with Column-II and select the correct
66. Of the given electronic configurations for the elements, answer by the given codes.
which electronic configuration indicates that there will be Columnn-I Column-II
abnormally high difference in the second and third ionization (Atoms) (Properties)
energy for the element? (A) He (p) Highly electronegative
(a) 1s2 2s2 2p6 3s2 (b) 1s2 2s2 2p6 3s1 (B) F (q) Most electropositive
(c) 1s2 2s2 2p6 3s2 3p1 (d) 1s2 2s2 2p6 3s2 3p2 (C) Rb (r) Strongest reducing agent
67. Alkali metals are powerful reducing agents because (D) Li (s) Highest ionisation energy
(a) these are metals (a) A – (s), B – (q), C – (r), D – (p)
(b) their ionic radii are large (b) A – (p), B – (s), C – (q), D – (r)
(c) these are monovalent (c) A – (s), B – (p), C – (r), D – (q)
(d) their ionisation potential is low (d) A – (s), B – (p), C – (q), D – (r)
 EBD_7374
34 CHEMISTRY

80. Which of the following statement(s) is/are incorrect? III 1681 3374 – 328
(i) Ionization enthalpy is expressed in units of kJmol–1. IV 1008 1846 – 295
(ii) Ionization enthalpy is always positive. V 2372 5251 + 48
(iii) Second ionization enthalpy will be higher than the third The most reactive metal and the least reactive non-metal of
ionization enthalpy. these are respectively
(a) Only (ii) (b) Only (iii) (a) I and V (b) V and II (c) II and V (d) IV and V
(c) (ii) and (iii) (d) None of these 87. Among the following transition elements, pick out the
81. Consider the following statements element/elements with highest second ionization energy.
(i) The radius of an anion is larger than that of the parent atom. (A) V (At. no = 23) (B) Cr (At. no = 24)
(ii) The ionization energy generally increases with (C) Mn (At. no = 25) (D) Cu (At. no = 29)
increasing atomic number in a period. (E) Zn (At. no = 30)
(iii) The electronegativity of elements increases on moving (a) (A) and (C) (b) (B) and (D)
down a group. (c) (B) and (E) (d) Only (D)
Which of the above statements is/are correct? 88. As we move across the second period from C to F ionisation
(a) (i) alone (b) (ii) alone enthalpy increases but the trend from C to F for ionisation
(c) (i) and (ii) (d) (ii) and (iii) enthalpy is C < O < N < F. This is because
82. Match the Column-I and Column-II and select the correct (a) atomic radii of O > atomic radii of N
answer by given codes. (b) electronic configuration of N is more stable than
Column-I Column-II electronic configuration of O
(Elements) (Properties) (c) atomic radii of N > atomic radii of O
(A) Li+ < Al3+ < Mg2+ < K+ (p) EA (Electron affinity) (d) None of these
(B) Li+ > Al3+ > Mg2+ > K+ (q) Ionic radii 89. If ionisation enthalpy of oxygen is lesser than nitrogen
(C) Cl > F > Br > I (r) EN (Electronegativity) because of two of the four 2p-electrons occupy same
(D) F > Cl > Br > I (s) Effective nuclear charge 2p-orbital than why such case is not possible with fluorine
(a) A – (q), B – (s), C – (r), D – (p) which contain greater no of paired electrons.
(b) A – (q), B – (s), C – (p), D – (r) (a) due to greater size of atomic orbitals
(c) A – (s), B – (q), C – (r), D – (p) (b) due to smaller size of orbitals
(d) A – (s), B – (q), C – (p), D – (r) (c) due to nuclear charge overpower electronic repulsions.
83. Covalent radii of atoms varies in range of 72 pm to 133 pm (d) None of these
from F to I while that of noble gases He to Xe varies from 90. Which of the following statements is wrong ?
120pm to 220pm. This is because in case of noble gases (a) van der Waal’s radius of iodine is more than its covalent
(a) covalent radius is very large radius
(b) van der Waal radius is considered (b) All isoelectronic ions belong to same period of the
(c) metallic radii is considered periodic table
(d) None of these (c) I.E.1 of N is higher than that of O while I.E.2 of O is
84. The van der Waal and covalent radii of fluorine atom higher than that of N
respectively from the following figure are. (d) The electron gain enthalpy of N is almost zero while
294 pm that of P is 74.3 kJ mol–1
91. Assertion : Atomic size increases along a period.
Reason : Effective nuclear charge increases as the atomic
number increases resulting in the increased attraction of
F F F F electrons to the nucleus.
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion.
144 pm 144 pm (b) Assertion is correct, reason is correct; reason is not a
(a) 219 pm, 72 pm (b) 75 pm, 72 pm correct explanation for assertion.
(c) 147 pm, 72 pm (d) 147 pm, 144 pm (c) Assertion is correct, reason is incorrect.
85. Arrange the following in increasing order of ionic radii? (d) Assertion is incorrect, reason is correct.
C4–,N3–,F–,O2– 92. Which one of the following statements is incorrect ?
(a) C4– < N3– < O2– < F– (b) N3– < C4– < O2– < F– (a) Greater the nuclear charge, greater is the electron
(c) F–< O2– < N3– < C4– (d) O2– < F– < N3– < C4– affinity
86. The first (DiH1) and second (DiH2) ionization enthalpies (b) Nitrogen has zero electron affinity
(c) Electron affinity decreases from fluorine to iodine in
(in kJ mol –1) and the electron gain enthalpy (D egH)
17th group
(in kJ mol–1) of the elements I, II, III, IV and V are given
(d) Chlorine has highest electron affinity
below
93. The elements with zero electron affinity are
Element D iH1 D iH2 DegH
(a) Boron and Carbon (b) Beryllium and Helium
I 520 7300 – 60
(c) Lithium and Sodium (d) Fluorine and Chlorine
II 419 3051 – 48
CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES 35

94. Which of the following property of element is directly (a) Al3+ > Mg 2+ > Na + > F- > O 2 -
related to electronegativity? (b) Na + > Mg 2+ > Al3+ > O2- > F-
(a) Atomic radius (b) Ionization enthalpy (c) Na + > F - > Mg 2 + > O 2 - > Al3+
(c) Non-metallic character (d) None of these (d) O2- > F- > Na + > Mg 2+ > Al3+
95. Which is not the correct order for the stated property. 98. Assertion : Smaller the size of an atom greater is the
(a) Ba > Sr > Mg ; atomic radius electronegativity.
(b) F > O > N ; first ionization enthalpy Reason : Electronegativity refers to the tendency of atom so
(c) Cl > F > I ; electron affinity share electrons with other atom.
(d) O > Se > Te ; electronegativity (a) Assertion is correct, reason is correct; reason is a
96. The compounds of the s-block elements, with the exception correct explanation for assertion.
of lithium and ...X... are predominantly ionic. Here, X refers to (b) Assertion is correct, reason is correct; reason is not a
(a) hydrogen (b) helium correct explanation for assertion.
(c) magnesium (d) beryllium (c) Assertion is correct, reason is incorrect.
97. The correct sequence which shows decreasing order of the (d) Assertion is incorrect, reason is correct.
ionic radii of the elements is

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (a) F > Cl > Br > I (b) F < Cl < Br < I
(c) F < Cl > Br > I (d) F < Cl < Br < I
1. Consider the isoelectronic species, Na+, Mg2+, F– and O2. 8. The period number in the long form of the periodic table is
The correct order of increasing length of their radiiis equal to
(a) F– < O2– < Mg2+ < Na+ (a) magnetic quantum number of any element of the period
(b) Mg2+ < Na+ < F– < O2– (b) atomic number of any element of the period
(c) O2– < F– < Na+ < Mg2+ (c) maximum principal quantum number of any element of
(d) O2– < F– < Mg2+ < Na+ the period
2. Which of the following is not an actinoid? (d) maximum azimuthal quantum number of any element
(a) Curium (Z = 96) (b) Californium (Z = 98) of the period
(c) Uranium (Z = 92) (d) Terbium (Z = 65) 9. The elements in which electrons are progessively filled in
3. The order of screening effect of electrons of s, p, d and f 4f-orbital are called
orbitals of a given shell of an atom on its outer shell (a) actinoids (b) transition elements
electrons is (c) lanthanoids (d) halogens
(a) s > p > d > f (b) f > d > p > s 10. Which of the following is the correct order of size of the
(c) p < d < s > f (d) f > p > s > d given species
4. The first ionisation enthalpies of Na, Mg, Al and Si are in (a) I > I– > I+ (b) I+ > I– > I
+
(c) I > I > I – (d) I– > I > I+
the order
11. The formation of oxide ion O2– (g), from oxygen atom
(a) Na < Mg > Al < Si (b) Na > Mg > Al > Si
requires first an exothermic and then an endothermic step
(c) Na < Mg < Al < Si (d) Na > Mg > Al < Si
as shown below
5. The electronic configuration of gadolinium (Atomic O (g) + e– ® O– (g); DH° = – 141 kJ mol–1
number 64) is O– (g) + e– ® O2– (g); DH° = + 780 kJ mol–1
(a) [Xe] 4f 3 5d5 6s2 (b) [Xe] 4f 7 5d2 6s1 Thus, process of formation of O 2– in gas phase is
7
(c) [Xe] 4f 5d 6s 1 2 (d) [Xe] 4f 8 5d6 6s2 unfavourable even though O2– is isoelectronic with neon.
6. The statement that is not correct for periodic classification It is due to the fact that
of elements is (a) oxygen is more electronegative
(a) the properties of elements are periodic function of (b) addition of electron in oxygen results in larger size of
their atomic numbers. the ion
(b) non-metallic elements are less in number than metallic (c) electron repulsion outweighs the stability gained by
elements. achieving noble gas configuration
(c) for transition elements, the 3d-orbitals are filled with (d) O– ion has comparatively smaller size than oxygen atom
electrons after 3p-orbitals and before 4s-orbitals. Comprehension given below is followed by some multiple choice
(d) the first ionisation enthalpies of elements generally questions. Each question has one correct option. Choose the
increase with increase in atomic number as we go along correct option.
a period.
7. Among halogens, the correct order of amount of energy In the modern periodic table, elements are arranged in order of
released in electron gain (electron gain enthalpy) is increasing atomic numbers which is related to the electronic
 EBD_7374
36 CHEMISTRY

configuration. Depending upon the type of orbitals receiving the 22. The species Ar, K+ and Ca2+ contain the same number of
last electron, the elements in the periodic table have been divided electrons. In which order do their radii increase ?
into four blocks, viz s, p, d and f. [AIPMT 2015, A]
The modern periodic table consists of 7 periods and 18 groups. Each (a) Ca 2+ < Ar < K + (b) Ca 2+ < K + < Ar
period begins with the filling of a new energy shell. In accordance (c) K + < Ar < Ca 2+ (d) Ar < K + < Ca 2+
with the Aufbau principle, the seven periods (1 to 7) have 2, 8, 8, 18, 23. The formation of the oxide ion O2–(g), from oxygen atom
18, 32 and 32 elements respectively. requires first an exothermic and then an endothermic step
The seventh period is still incomplete. To avoid the periodic as shown below :
table being too long, the two series of f-block elements, called O(g) + e– ® O–(g); = –141 kJ mol–1
lanthanoids and actinoids are placed at the bottom of the main O– (g) + e– ® O2– (g); = +780 kJ mol –1
body of the periodic table. Thus process of formation of O 2– in gas phase is
12. The element with atomic number 57 belongs to unfavourable even though O2– is isoelectronic with neon. It
(a) s-block (b) p-block is due to the fact that [AIPMT 2015 RS, S]
(c) d-block (d) f-block (a) Electron repulsion outweighs the stability gained by
13. The last element of the p-block in 6th period is represented achieving noble gas configuration
by the outermost electronic configuration. (b) O– ion has comparatively smaller size than oxygen atom
(a) 7s2 7p6 (b) 5f 14 6d10 7s2 7p0 (c) Oxygen is more electronegative
14
(c) 4f 5d 6s 6p 10 2 6 (d) 4f 14 5d10 6s2 6p4 (d) Addition of electron in oxygen results in larger size of
14. Which of the elements whose atomic numbers are given the ion.
below, cannot be accommodated in the present set up of 24. In which of the following arrangements, the order is NOT
the long form of the periodic table? according to the property indicated against it?
(a) 107 (b) 118 (c) 126 (d) 102 [AIIMS 2015, A]
15. The electronic configuration of the element which is just (a) Li < Na < K < Rb :
above the element with atomic number 43 in the same group Increasing metallic radius
is ............ (b) I < Br < F < Cl :
(a) 1s2 2s2 2p6 3s2 3p6 3d5 4s2 Increasing electron gain enthalpy
(b) 1s2 2s2 2p6 3s2 3p6 3d5 4s3 4p6 (with negative sign)
(c) 1s2 2s2 2p6 3s2 3p6 3d 6 4s2 (c) B < C < N < O
(d) 1s2 2s2 2p6 3s2 3p6 3d7 4s2 Increasing first ionization enthalpy
16. The elements with atomic numbers 35, 53 and 85 are (d) Al3+ < Mg2+ < Na+ < F–
all ................ . Increasing ionic size
25. Assertion : Both Be and Al can form complexes such as
(a) noble gases (b) halogens
BeF42– and AlF63– respectively, BeF63– is not formed.
(c) heavy metals (d) light metals
Reason : In case of Be, no vacant d-orbitals are present in
17. Electronic configuration of four elements A, B, C and D are
its outermost shell. [AIIMS 2015, S]
given below
(a) Assertion is correct, reason is correct; reason is a
A. 1s2 2s2 2p6 B. 1s2 2s2 2p4
2 2 6 1 correct explanation for assertion.
C. 1s 2s 2p 3s D. 1s2 2s2 2p5
Which of the following is the correct order of increasing (b) Assertion is correct, reason is correct; reason is not a
tendency to gain electron? correct explanation for assertion.
(a) A < C < B < D (b) A < B < C < D (c) Assertion is correct, reason is incorrect.
(c) D < B < C < A (d) D < A < B < C (d) Assertion is incorrect, reason is correct.
26. The ionic radii (in Å) of N3–, O2– and F– are respectively :
Past Year MCQs
[JEE M 2015, A]
18. Which of the following orders of ionic radii is correctly (a) 1.71, 1.40 and 1.36 (b) 1.71, 1.36 and 1.40
represented ? [AIPMT 2014, A] (c) 1.36, 1.40 and 1.71 (d) 1.36, 1.71 and 1.40
(a) H– > H+ > H (b) Na+ > F– > O2– 27. The element, with atomic number 118, will be
(c) F– > O2– > Na+ (d) Al3+> Mg2+> N3– [BITSAT 2015, S]
19. The element with atomic number 117 has not been
(a) alkali (b) noble gas
discovered yet. In which family would you place this element
(c) lanthanide (d) transition element
if discovered? [AIIMS 2014, S]
28. In which of the following options the order of arrangement
(a) Alkali metals (b) Alkaline earth metals
does not agree with the variation of property indicated
(c) Halogens (d) Noble gases
20. Which has smallest size ? [BITSAT 2014, A] against it ? [NEET 2016, S]
(a) Na+ (b) Mg2+ (c) Ne (d) O2– (a) Al3+ < Mg2+ < Na+ < F– (increasing ionic size)
21. The valency shell of element A contains 3 electrons while (b) B < C < N < O (increasing first ionisation enthalpy)
the valency shell of element B contains 6 electrons. If A (c) I < Br < Cl < F (increasing electron gain enthalpy)
combines with B, the probable formula of the compound (d) Li < Na < K < Rb (increasing metallic radius)
formed will be [BITSAT 2014, S] 29. The correct decreasing order of first ionisation enthalpies
(a) AB2 (b) A2B (c) A2B3 (d) A3B2 of five elements of the second period is [AIIMS 2016, S]
CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES 37

(a) Be > B > C > N > F (b) N > F > C > B > Be 35. Both lithium and magnesium display several similar
(c) F > N > C > Be > B (d) N > F > B > C > Be properties due to the diagonal relationship; however, the
30. Which of the following atoms has the highest first ionization one which is incorrect is : [JEE M 2017, S]
energy? [JEE M 2016, S] (a) Both form basic carbonates
(a) K (b) Sc (c) Rb (d) Na (b) Both form soluble bicarbonates
31. The decreasing order of the ionization potential of the (c) Both form nitrides
following elements is [BITSAT 2016, S] (d) Nitrates of both Li and Mg yield NO2 and O2 on heating
36. Which of the following order is wrong?
(a) Ne > Cl > P > S > Al > Mg
[BITSAT 2017, C]
(b) Ne > Cl > P > S > Mg > Al
(a) NH 3 < PH 3 < AsH 3 — Acidic
(c) Ne > Cl > S > P > Mg > Al
(b) Li < Be < B < C — IE1
(d) Ne > Cl > S > P > Al > Mg (c) Al 2 O3 < MgO < Na 2 O < K 2 O — Basic
32. The element Z = 114 has been discovered recently.
(d) Li + < Na + < K + < Cs + — Ionic radius
It will belong to which of the following family/group and
37. Assertion : Second ionization enthalpy will be higher than
electronic configuration ? [NEET 2017, A] the first ionization enthalpy.
(a) Carbon family, [Rn] 5f 14 6d10 7s2 7p2 Reason : Ionization enthalpy is a quantitative measure of the
(b) Oxygen family, [Rn] 5f 14 6d10 7s2 7p4 tendency of an element to lose electron. [AIIMS 2018, C]
(c) Nitrogen family, [Rn] 5f 14 6d10 7s2 7p6 (a) Assertion is correct, reason is correct; reason is a
(d) Halogen family, [Rn] 5f 14 6d10 7s2 7p5 correct explanation for assertion.
33. The law of triads is applicable to a group of (b) Assertion is correct, reason is correct; reason is not a
[AIIMS 2017, C] correct explanation for assertion.
(a) Cl, Br, I (b) C, N, O (c) Assertion is correct, reason is incorrect.
(c) Na, K, Rb (d) H, O, N (d) Assertion is incorrect, reason is correct.
34. The group having isoelectronic species is : 38. Amongst the elements with following electronic
[JEE M 2017, S] configurations, which one of them may have the highest
(a) O2– , F–, Na+, Mg2+ (b) O– , F–, Na, Mg+ ionization energy? [BITSAT 2018, C]
(c) O2– , F–, Na , Mg2+ (d) O– , F–, Na+ , Mg2+ (a) Ne [3s23p2] (b) Ar [3d104s24p3 ]
(c) Ne [3s23p1] (d) Ne [3s23p3]

Exercise 3 : Try If You Can

1. Which of the following transformation requires least
Y
energy?
W X Z
(a) F- (g) ¾¾
® F(g) + e - (b) P - (g) ¾¾
® P(g) + e -
Here W, Y and Z are left, up and right elements with respect
- - - - to the element 'X' and 'X' belongs to 16th group and 3rd
(c) S (g) ¾¾
® S(g) + e (d) Cl (g) ¾¾
® Cl(g) + e
period. Then according to given information the incorrect
2. Incorrect order of radius is : statement regarding given elements is:
(a) Sr2+ < Rb+ < Br– < Se2– (b) Nb5+ < Zr4+ < Y3+ (a) Maximum electronegativity : Y
(c) Co > Co2+ > Co3+ > Co4+ (d) Ba2+ < Cs+ < Se2– < As3– (b) Maximum catenation property : X
3. Sum of first three ionization energies of Al is 53.0 eV atom–1 (c) Maximum electron affinity : Z
and the sum of first two ionization energies of Na is (d) Y exhibits variable covalency
52.2 eV atom–1. Out of Al(III) and Na(II) 6. Aqueous solutions of two compounds M1 – O – H and
(a) Na (II) is more stable than Al (III) M2 – O – H are prepared in two different beakers. If, the
(b) Al (III) is more stable than Na (II) electronegativity of M1 = 3.4, M2 = 1.2, O = 3.5 and H= 2.1
(c) Both are equally stable then the nature of two solutions will be respectively :
(d) Both are equally unstable (a) acidic, basic (b) acidic, acidic
4. Consider the following changes (c) basic, acidic (d) basic, basic
A ® A + + e - : E1 and A + ® A 2 + + e - : E 2 7. The formation of O2– (g) starting from O (g) is endothermic
The energy required to pull out the two electrons are E1 and by 603 kJ mol–1. If electron affinity of O(g) is –141 kJ mol–1,
E2 respectively. The correct relationship between two the second electron affinity of oxygen would be
energies would be (a) 603 kJ mol–1 (b) –603 kJ mol–1
(a) E1 < E2 (b) E1 = E2 (c) –744 kJ mol–1 (d) +744 kJ mol–1
(c) E1 > E2 (d) E1 ³ E2 8. The electron affinity of chlorine is 3.7 eV. 1 gram of chlorine
5. Consider the following four elements, which are represented is completely converted to Cl – ion in a gaseous state.
according to long form of periodic table (1 eV = 23.06 kcal mol–1).
 EBD_7374
38 CHEMISTRY

Energy released in the process is 12. Which of the following is the correct order of lattice energy?
(a) 4.8 kcal (b) 7.2 kcal (c) 8.2 kcal (d) 2.4 kcal (a) MgO < LiF < KBr (b) KBr < LiF < MgO
9. Among Al2O3, SiO2, P2O3 and SO2 the correct order of acid (c) LiF < KBr < MgO (d) LiF= KBr < MgO
strength is
13. Ionization potential and electron affinity of fluorine are 17.42
(a) Al2O3 < SiO2< SO2 < P2O3
and 3.45 eV atom–1 respectively. Electronegativity of fluorine
(b) SiO2< SO2 < Al2O3 < P2O3
will be approximately
(c) SO2< P2O3 < SiO2 < Al2O3
(d) Al2O3 < SiO2< P2O3 < SO2 (a) 2.7 (b) 3.7 (c) 4.07 (d) 6.7
10. Among O, O+, O2+ and O2–, the species having most positive 14. Select the correct order for the property given in brackets:
and most negative value of DHeg are respectively. (a) F+ (g) < Cl+ (g) : (EA order)
(a) O+ and O (b) O2+ and O2– (b) F (g) < Cl (g) : (DHeg order)
(c) O and O2– (d) O2– and O2+
11. Ionization energies of atoms A and B are 400 and 300 k cal (c) O (g) > S (g) : (DHeg order)
mol–1 respectively. The electron affinities of these atoms (d) S2– (g) > Cl– (g) : (IE order)
are 80.0 and 85.0 k cal mol–1 respectively. Then which is the 15. The set of three elements having successive atomic numbers
correct statement regarding electronegativity c ? and having the ionization energies of 2372, 520 and 890 kJ
(a) c A < c B (b) c A > c B per mol is
(c) cA = cB (d) none of these (a) H, He, Li (b) He, Li, Be (c) Li, Be, B (d) B, C, N

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 11 (a) 21 (b) 31 (c) 41 (b) 51 (b) 61 (c) 71 (a) 81 (c) 91 (c)
2 (c) 12 (d) 22 (a) 32 (b) 42 (d) 52 (b) 62 (a) 72 (d) 82 (b) 92 (c)
3 (a) 13 (c) 23 (c) 33 (b) 43 (c) 53 (b) 63 (d) 73 (a) 83 (b) 93 (b)
4 (b) 14 (d) 24 (c) 34 (b) 44 (d) 54 (c) 64 (b) 74 (a) 84 (c) 94 (c)
5 (a) 15 (b) 25 (b) 35 (b) 45 (d) 55 (d) 65 (a) 75 (a) 85 (c) 95 (b)
6 (c) 16 (a) 26 (d) 36 (a) 46 (c) 56 (c) 66 (a) 76 (b) 86 (c) 96 (d)
7 (b) 17 (b) 27 (c) 37 (b) 47 (d) 57 (a) 67 (d) 77 (d) 87 (b) 97 (d)
8 (d) 18 (c) 28 (c) 38 (b) 48 (a) 58 (b) 68 (b) 78 (b) 88 (b) 98 (c)
9 (b) 19 (b) 29 (b) 39 (b) 49 (a) 59 (c) 69 (a) 79 (d) 89 (c)
10 (b) 20 (b) 30 (c) 40 (b) 50 (b) 60 (a) 70 (b) 80 (b) 90 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 5 (c) 9 (c) 13 (c) 17 (a) 21 (c) 25 (a) 29 (c) 33 (a) 37 (b)
2 (d) 6 (c) 10 (d) 14 (c) 18 (N) 22 (b) 26 (a) 30 (b) 34 (a) 38 (d)
3 (a) 7 (c) 11 (c) 15 (a) 19 (c) 23 (a) 27 (b) 31 (b) 35 (a)
4 (a) 8 (c) 12 (c) 16 (b) 20 (b) 24 (c) 28 (b) 32 (a) 36 (b)
Exercise 3 : Try If You Can
1 (b) 3 (b) 5 (d) 7 (d) 9 (d) 11 (b) 13 (c) 15 (b)
2 (d) 4 (a) 6 (a) 8 (d) 10 (d) 12 (b) 14 (b)
 Chapter
4 CHEMICAL BONDING AND
MOLECULAR STRUCTURE

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

8
7
6
AIPMT /NEET
5
Number of Questions

AIIMS
4
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 4 Molecular Orbital Theory,
AIIMS 5 Dipole Moment, VSEPR 4/5 8.7
JEE Main 3 Theory
BITSAT 3
 EBD_7374
40 CHEMISTRY
CHEMICAL BONDING AND MOLECULAR STRUCTURE 41
 EBD_7374
42 CHEMISTRY

Exercise 1 : Topic-wise MCQs

(a) – 0.75, 0.6 (b) – 0.75, 1.0
Topic 1: Kossel-Lewis Approach to Chemical Bonding
(c) – 0.75, 1.25 (d) – 3, 1.25
1. The evolution of various theories of valence and the 10. Assertion : The correct Lewis structure of O3 may be drawn
interpretation of the nature of chemical bonds have closely as
been related to the developments in the understanding of +
(a) structure of atom 1

:
(b) electronic configuration of elements O
(c) periodic table 2 –

: :
: :
O O: 3
(d) All of the above
2. Who provide explanation of valence based on intertness Reason : The formal charges on atom 1, 2 and 3 are + 1, 0
of noble gases ? and –1 respectively.
(a) Lewis (b) K&o&ssel-Lewis (a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion.
(c) Langmuir (d) Sidgwick & Powell
(b) Assertion is correct, reason is correct; reason is not a
3. Who introduced the term covalent bond ?
correct explanation for assertion.
(a) Lewis (b) Langmuir
(c) Assertion is correct, reason is incorrect.
(c) Nyholm and Gillespie (d) Heitler and London
(d) Assertion is incorrect, reason is correct.
4. The bond formed as a result of the electrostatic attraction
11. Which of the following molecule(s) obey the octet rule?
between the positive and negative ions is termed as ...
(i) [BF4]–, (ii) [AlCl4]–, (iii) SO2, (iv) CCl4
(a) Chemical bond (b) Electrovalent bond
(a) (i), (ii), (iii), (iv) (b) (ii), (iii), (iv)
(c) Co-ordinate bond (d) Covalent bond
(c) (i), (iii), (iv) (d) (i), (ii), (iii)
5. When a metal atom combines with non-metal atom, the
non-metal atom will 12. Which of the following is the electron deficient molecule?
(a) lose electrons and decrease in size (a) C2H6 (b) B2H6 (c) SiH4 (d) PH3
(b) lose electrons and increase in size 13. Which of the following compounds does not follow the
octet rule for electron distribution?
(c) gain electrons and decrease in size
(a) PCl5 (b) PCl3 (c) H2O (d) PH3
(d) gain electrons and increase in size
14. Assertion : Atoms can combine either by transfer of
6. Which of the following is/are not the condition(s) for
valence of electrons from one atom to another or by
Lewis dot structure?
sharing of valence electrons.
(i) Each bond is formed as a result of sharing of an
Reason : Sharing and transfer of valence electrons is
electron pair between the atoms.
done by atoms to have an octet in their valence shell.
(ii) From the two combining atoms only one atom
(a) Assertion is correct, reason is correct; reason is a
contribute electron(s) to the shared pair.
correct explanation for assertion.
(iii) The combining atoms attain the outer shell noble gas
(b) Assertion is correct, reason is correct; reason is not a
configurations as a result of the sharing of electrons.
correct explanation for assertion.
(a) (i) and (iii) (b) (ii) and (iii)
(c) Assertion is correct, reason is incorrect.
(c) (ii) only (d) (iii) only
(d) Assertion is incorrect, reason is correct.
7. Which of the following Lewis representation of the
15. A pair of compound which have odd electrons in the group
molecules NF3, O3 and HNO3 is correct ?
NO, CO, ClO2, N2O5, SO2 and O3 are
+
(a) NO and ClO2 (b) CO and SO2
: :
: — :
: :

: :
: — :
: :

:F – N – F: O O=N–O–H
(c) ClO2 and CO (d) SO2 and O3
: —

: :

O O:
:

:F: :O: 16. Assertion : Sulphur compounds like SF6 and H2SO4 have
I II III 12 valence electrons around S atom.
Choose the correct option(s). Reason : All sulphur compounds do not follow octet rule.
(a) Only I (b) Only II (c) Only III (d) I, II and III (a) Assertion is correct, reason is correct; reason is a
8. The lowest energy structure is the one with the .......... correct explanation for assertion.
formal charges on the atoms. (b) Assertion is correct, reason is correct; reason is not a
(a) smallest (b) highest (c) zero (d) negative correct explanation for assertion.
9. In PO43– ion, the formal charge on each oxygen atom and (c) Assertion is correct, reason is incorrect.
P — O bond order respectively are (d) Assertion is incorrect, reason is correct.
CHEMICAL BONDING AND MOLECULAR STRUCTURE 43

(a) Assertion is correct, reason is correct; reason is a

Topic 2: Ionic or Electrovalent Bond
correct explanation for assertion.
17. Complete the following statement by choosing the (b) Assertion is correct, reason is correct; reason is not a
appropriate option. correct explanation for assertion.
Ionic bonds will be formed more easily between elements (c) Assertion is correct, reason is incorrect.
with comparatively A and elements with (d) Assertion is incorrect, reason is correct.
comparatively high negative value of B . Topic 3: Bond Parameters
(a) A = low electronegativity
B = ionization enthalpy 26. Which of the following methods is used for measuring
(b) A = low ionization enthalpy bond length ?
B = electron gain enthalpy (a) X-ray diffraction
(c) A = high ionization enthalpy (b) Electron-diffraction
B = electron gain enthalpy (c) Spectroscopic techniques
(d) A = high electronegativity (d) All of these
B = ionization enthalpy 27. .......... is measured as the radius of an atom’s core which is in
18. In ionic solids how crystal structure get stabilized contact with the core of an adjacent atom in a bonded situation.
(a) By the energy released in the formation of crystal lattice. (a) van der Waal’s radius (b) Bond length
(b) By achieving octet of electrons around the ionic (c) Covalent radius (d) Ionic radius
species in gaseous state. 28. Which of the following statement is correct?
(c) By electron gain enthalpy and the ionization enthalpy. (a) Amount of energy required to break one mole of
(d) None of these bonds of a particular type between two atoms in a
19. Energy required to completely separate one mole of a gaseous state is called bond enthalpy.
solid ionic compound into gaseous constituent ions is (b) The unit of bond enthalpy is kJ mol–1.
called .......... . (c) Larger the bond dissociation enthalpy, stronger will
(a) Ionisation enthalpy be the bond in the molecule.
(b) Electron gain enthalpy (d) All of these
(c) Bond dissociation enthalpy 29. Which one of the following pairs of molecules will have
(d) Lattice enthalpy permanent dipole moments for both members ?
20. Which of the following combination will form an (a) NO2 and CO2 (b) NO2 and O3
electrovalent bond ? (c) SiF4 and CO2 (d) SiF4 and NO2
(a) P and Cl (b) NH3 and BF3 30. Which one of the following is not correct representation of
(c) H and Ca (d) H and S resonance ?
21. Among the following which compound will show the highest – .. + + .. –
A. :O::C::O:

: :
:

: :

:O::C::O: :O::C:O:
lattice energy ? I II
:
III
(a) KF (b) NaF (c) CsF (d) RbF – –
:

:
:O: :O: :O:
22. Which of the following pairs will form the most stable ionic
bond ?
(a) Na and Cl (b) Mg and F B. C C C
(c) Li and F (d) Na and F –
–
:O:– –:O: :O:– :O O:
: :
:O:
23. Match the columns I II III :
:

Column-I Column-II Choose the correct option.

(A) HCl (p) Covalent compound with (a) Only A (b) Only B
directional bond (c) Both A and B (d) None of these
(B) CO2 (q) Ionic compound with 31. Which of the following structure represents structure of
non-directional bonds O3 more accurately?
(C) NaCl (r) Polar molecule
O O
(D) CCl4 (s) Non-polar molecule
12

14
pm
m

1p

8
8p

(a) A – (p, q, r), B – (q, r), C – (p, q), D – (r)

pm
1
m

12
14

(b) A – (q), B – (r), C – (p), D – (s) O O O O

(c) A – (p, r), B – (p, s), C – (q), D – (p, s)
(d) A – (q), B – (r), C – (p, q), D – (s) I II
24. Which of the following substances has the greatest ionic
character ? O
12

(a) Cl2O (b) NCl3 (c) PbCl2 (d) BaCl2

pm

8
pm
8

25. Assertion : The lesser the lattice enthalpy more stable is

12

the ionic compound. O O

Reason : The lattice enthalpy is greater, for ions of highest III
charge and smaller radii. (a) I (b) II (c) III (d) I and II
 EBD_7374
44 CHEMISTRY

32. Which of the following is/are misconception(s) associated 45. Hydrogen chloride molecule contains
with resonance ? (a) polar covalent bond (b) double bond
(i) The molecule exist for a certain fraction of time in one (c) co-ordinate bond (d) electrovalent bond
cannonical form and for other fractions of time in 46. Which one of the following molecules is expected to have
other cannonical forms. zero dipole moment?
(ii) The cannonical forms have no real existence. (a) H2O (b) CO2 (c) SO2 (d) CaF2
(iii) There is no such equilibrium between the cannonical 47. From the given figure the van der Waal radius and covalent
forms. radius of the hydrogen atom respectively are
(a) (i) only (b) (ii) and (iii) 62 pm
(c) (i) and (iii) (d) (iii) only
33. The molecule which has zero dipole moment is
(a) CH3Cl (b) NF3 (c) BF3 (d) ClO2
34. Resonance is due to 240 pm
(a) delocalization of sigma electrons
(b) delocalization of pi electrons (a) 151, 31 (b) 120, 31
(c) migration of protons (c) 31, 100 (d) 30, 120
(d) Both (a) and (b) 48. The correct order of dipole moments of HF, H 2S and H 2 O is
35. Arrange the following in increasing order of covalent
(a) HF < H 2S < H 2 O (b) HF < H 2S > H 2 O
character (i) NaCl, (ii) RbCl, (iii) MgCl2, (iv) AlCl3 ?
(a) (i), (ii), (iii), (iv) (b) (iv), (ii), (i), (iii) (c) HF > H 2 S > H 2 O (d) HF > H 2 O < H 2S
(c) (ii), (i), (iii), (iv) (d) (iii), (i), (ii), (iv) Topic 4: The Valence Shell Electron Pair Repulsion
36. Which of the following salt shows maximum covalent (VSEPR) Theory
character?
(a) AlCl3 (b) MgCl2 (c) CsCl (d) LaCl3 49. According to VSEPR theory the geometry of a covalent
37. The covalent bond length is the shortest in which one of molecules depends upon
the following bonds? (a) the number of bond pairs of electrons
(a) C — O (b) C — C (c) C º N (d) O — H (b) the number of lone pairs of electrons
38. The most polar bond is (c) the number of electron pairs present in the outer shell
(a) C – F (b) C – O (c) C – Br (d) C – S of the central atom
39. Which of the following possess dipole moment SF6(i), (d) All of the above
SO2(ii), H2S(iii) , SF4(iv) ? 50. The geometry of ClO3– ion according to Valence Shell
(a) (ii) and (iii) (b) (i) and (iii) Electron Pair Repulsion (VSEPR) theory will be
(c) (ii), (iii) and (iv) (d) (i) and (ii) (a) planar triangular (b) pyramidal
40. According to Fajan’s rule, covalent bond is favoured by (c) tetrahedral (d) square planar
(a) Large cation and small anion 51. In BrF3 molecule, the lone pairs occupy equatorial positions
(b) Large cation and large anion to minimize
(c) Small cation and large anion (a) lone pair - bond pair repulsion only
(d) Small cation and small anion (b) bond pair - bond pair repulsion only
41. Assertion : CH2Cl2 is non-polar and CCl4 is polar molecule. (c) lone pair - lone pair repulsion and lone pair - bond pair
Reason : Molecule with zero dipole moment is non-polar in repulsion
nature. (d) lone pair - lone pair repulsion only
(a) Assertion is correct, reason is correct; reason is a 52. Which of the following is the correct increasing order of
correct explanation for assertion. lone pair of electrons on the central atom?
(b) Assertion is correct, reason is correct; reason is not a (a) IF7 < IF5 < CIF3 < XeF2
correct explanation for assertion. (b) IF7 < XeF2 < CIF2 < IF5
(c) Assertion is correct, reason is incorrect. (c) IF7 < CIF3 < XeF2 < IF5
(d) Assertion is incorrect, reason is correct. (d) IF7 < XeF2 < IF5 < CIF3
42. Among the following, the molecule of high dipole moment 53. Match Column-I with Column-II and Column-III and choose
is the correct option from the given codes.
(a) CCl4 (b) NH3 (c) H2O (d) CHCl3 Column-I Column-II Column-III
43. The correct sequence of increasing covalent character Molecule (No. of lone (Shape of molecule)
is represented by pairs and
(a) LiCl < NaCl < BeCl2 (b) BeCl2 < LiCl < NaCl bond pairs)
(c) NaCl < LiCl < BeCl2 (d) BeCl2 < NaCl < LiCl (A) NH3 (i) 1, 2 (p) Bent
44. Polarisibility of halide ions increases in the order (B) SO2 (ii) 1, 4 (q) Trigonal pyramidal
(a) F –, I – , Br–, Cl– (b) Cl –, Br – , I–, F– (C) SF4 (iii) 2, 3 (r) T-shape
– –
(c) I , Br , Cl , F – – (d) F –, Cl – , Br–, l– (D) ClF3 (iv) 1, 3 (s) See-Saw
CHEMICAL BONDING AND MOLECULAR STRUCTURE 45

(a) A – (iv, q); B – (ii, p); C – (i, r); D – (iii, s) 64. Assertion : In NH3, N is sp3 hybridised, but angle is found
(b) A – (iv, q); B – (i, p); C – (ii, s); D – (iii, r) to be 107°.
(c) A – (i, p); B – (iii, s); C – (iv, r); D – (ii, q) Reason : The decrease in bond angle is due to repulsion
(d) A – (iv, p); B – (i, r); C – (iii, q); D – (ii, s) between the lone pair.
54. The number of lone pair and bond pair of electrons on the (a) Assertion is correct, reason is correct; reason is a
sulphur atom in sulphur dioxide molecule are respectively correct explanation for assertion.
(a) 1 and 3 (b) 4 and 1 (c) 3 and 1 (d) 1 and 4 (b) Assertion is correct, reason is correct; reason is not a
55. A molecule has two lone pairs and two bond pairs around correct explanation for assertion.
the central atom. The molecule shape is expected to be (c) Assertion is correct, reason is incorrect.
(a) V-shaped (b) triangular (d) Assertion is incorrect, reason is correct.
(c) linear (d) tetrahedral 65. Match the columns
56. Using VSEPR theory, predict the species which has square Column-I Column-II
pyramidal shape
(a) SnCl2 (b) CCl4 (c) SO3 (d) BrF5 (A) Trigonal planar (p) PCl5
57. Assertion : Lone pair-lone pair repulsive interactions are

:
greater than lone pair-bond pair and bond pair-bond pair
interactions.
120°
Reason : The space occupied by lone pair electrons is
more as compared to bond pair electrons. A
(a) Assertion is correct, reason is correct; reason is a :

:
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a (B) Tetrahedral (q) NH4+
correct explanation for assertion.

:
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct. 109.5°
58. Among the following molecules : SO2, SF4, ClF3, BrF5 and A
XeF4, which of the following shapes does not describe any
of the molecules mentioned? :

:
(a) Bent (b) Trigonal bipyramidal
(c) See-saw (d) T-shape
59. Which of the following structure is most stable ?
:

F .. F (C) Trigonal bipyramidal (r) SF6

F
..

..

Cl F F Cl Cl F
:
..

.. F F ..
F 90°
I II III : :
A
Choose the correct option. 120°
(a) Only I
:

(b) Only II
(c) Only III
(d) All three have same stability
:

60. A s-bonded molecule MX3 is T-shaped. The number of non- (D) Octahedral (s) BF3
bonding pairs of electron is
(a) 0
:

(b) 2 90°
(c) 1
:
:

(d) can be predicted only if atomic number of M is known. 90° A

61. Which of the following molecules has trigonal planar
:

geometry?
(a) BF3 (b) NH3 (c) PCl3 (d) IF3
:

62. Which of the following molecules is planar? (a) A – (p), B – (q), C – (r), D – (s)
(a) SF4 (b) XeF4 (c) NF3 (d) SiF4
(b) A – (s), B – (r), C – (q), D – (p)
63. The shape of stannous chloride molecule is
(a) see-saw (b) square planar (c) A – (s), B – (q), C – (p), D – (r)
(c) trigonal pyramidal (d) bent (d) A – (r), B – (p), C – (q), D – (s)
 EBD_7374
46 CHEMISTRY

76. Assertion : pi bonds are weaker than s bonds.

Topic 5: Valence Bond Theory
Reason : pi bonds are formed by the overlapping of p-p
66. Look at the following potential energy curve which of the orbitals along their axes.
following correctly represents the most stable state of (a) Assertion is correct, reason is correct; reason is a
hydrogen molecule. correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion.
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct.
A D 77. Which of the following represents zero overlap of atomic
O C orbitals.
Energy

(a) – + + z
pz
s

B Internuclear distance ¾® (b) + – + z

pz
(a) A (b) B (c) C (d) D s
67. Which of the following statements is false ?
(a) H2 molecule has one sigma bond +
(b) HCl molecule has one sigma bond
(c) Water molecule has two sigma bonds and two lone (c) + z
pairs – s
(d) Acetylene molecule has three pi bonds and three sigma
bonds pz
68. The number of sigma (s) and pi (p) bonds present in 1,3,5,7
octatetraene respectively are (d) All of these
(a) 14 and 3 (b) 17 and 4 (c) 16 and 5 (d) 15 and 4 78. The strength of bonds formed by s–s and p–p, s–p overlap
69. Allyl cyanide molecule contains in the order of
(a) 9 sigma bonds, 4 pi bonds and no lone pair (a) s–p > s–s > p–p (b) p–p > s–s > s–p
(b) 9 sigma bonds, 3 pi bonds and one lone pair (c) s–s > p–p > s–p (d) s–s > s–p > p–p
(c) 8 sigma bonds, 5 pi bonds and one lone pair Topic 6: Hybridisation
(d) 8 sigma bonds, 3 pi bonds and two lone pairs
79. As the s-character of hybridised orbital increases, the bond
70. The molecule not having p-bond is
angle
(a) Cl2 (b) O2 (c) N2 (d) CO2
(a) increase (b) decrease
71. In hexa-1, 3-diene-5-yne the number of C — C d, C — C p
(c) becomes zero (d) does not change
and C — H s bonds, respectively are
80. The nature of hybridisation in the ammonia molecule is
(a) 5, 4 and 6 (b) 6, 3 and 5
(a) sp2 (b) dp 2 (c) sp (d) sp3
(c) 5, 3 and 6 (d) 6, 4 and 5
81. The shape of sulphate ion is
72. The angle between the overlapping of one s-orbital and one
(a) square planar (b) triagonal
p-orbital is
(c) trigonal planar (d) tetrahedral
(a) 180° (b) 120° (c) 109°28' (d) 120° 60' 82. Which of the following will have sp3d 3 hybridisation?
73. The enolic form of a acetone contains (a) BrF5 (b) PCl5 (c) XeF6 (d) SF6
(a) 9 sigma bonds, 1 pi bond and 2 lone pairs 83. Which of the following molecule does not have a linear
(b) 8 sigma bonds, 2 pi bonds and 2 lone pairs arrangement of atoms ?
(c) 10 sigma bonds, 1 pi bond and 1 lone pair (a) H2S (b) C2H2 (c) BeH2 (d) CO2
(d) 9 sigma bonds, 2 pi bonds and 1 lone pair 84. In which one of the following molecules the central atom
74. Linear combination of two hybridized orbitals belonging to said to adopt sp2 hybridization?
two atoms and each having one electron leads to a (a) BeF2 (b) BF3 (c) C2H2 (d) NH3
(a) sigma bond 85. Considering the state of hybridization of carbon atoms, find
(b) double bond out the molecule among the following which is linear ?
(c) co-ordinate covalent bond (a) CH3– CH = CH–CH3
(d) pi bond. (b) CH3 – C º C – CH3
75. Which of the following statements is not correct ? (c) CH2 = CH – CH2 – C º CH
(a) Double bond is shorter than a single bond (d) CH3 – CH2 – CH2 – CH3
(b) Sigma bond is weaker than a p (pi) bond 86. Equilateral shape has
(c) Double bond is stronger than a single bond (a) sp hybridisation (b) sp2 hybridisation
(d) Covalent bond is stronger than hydrogen bond 3
(c) sp hybridisation (d) None of these
CHEMICAL BONDING AND MOLECULAR STRUCTURE 47

87. In which of the following species is the underlined carbon (c) Promotion of electron is not essential condition for
having sp3 - hybridisation ? hybridization.
(a) CH 3 – COOH (b) CH 3 CH 2 OH (d) Pure atomic orbitals are more effective in forming stable
bonds than hybrid orbitals.
(c) CH 3 COCH 3 (d) CH 2 = CH - CH 3
100. Match Column-I (molecule) with Column-II (type of
88. 3
A sp -hybrid orbital contains hybridisation) and choose the correct option from the
(a) 25% s-character (b) 75% s-character codes given below.
(c) 50% s-character (d) 25% p-character Column-I Column-II
89. Pick out the incorrect statement from the following
(Molecule) (Type of hybridisation)
(a) sp hybrid orbitals are equivalent and are at an angle
of 180° with each other (A) SF6 (p) sp3d
(b) sp 2 hybrid orbitals are equivalent and bond angle (B) PF5 (q) sp3
between any two of them is 120° (C) BCl3 (r) sp3d 2
(c) sp 3d 2 hybrid orbitals are equivalent and are oriented (D) C2H6 (s) sp2
towards corners of a regular octahedron (a) A – (r), B – (p), C – (s), D – (q)
(d) sp 3d 3 hybrid orbitals are not equivalent (b) A – (r), B – (p), C – (q), D – (s)
90. All carbon atoms are sp2 hybridised in (c) A – (p), B – (r), C – (q), D – (s)
(a) 1, 3-butadiene (b) CH2 = C = CH2 (d) A – (p), B – (r), C – (s), D – (q)
(c) cyclohexane (d) 2-butene
101. What is the correct mode of hybridisation of the central
91. Hybridization present in ClF3 is
atom in the following compounds?
(a) sp2 (b) sp3 (c) dsp 2 (d) sp3d
+
92. Hybridisation states of C in CH3 and CH4 are NO2– SF4 PF6–
(a) sp2 & sp3 (b) sp3 & sp2
2
(c) sp & sp 2 (d) sp3 & sp3 (a) sp sp2 sp 3
(b) sp 2 3
sp d sp 3d 2
93. In which of the following species, all the three types of
(c) sp 2 sp 3 d 2sp 3
hybrid carbons are present?
(a) CH2 = C = CH2 (b) CH3 – CH= CH – CH+2 (d) sp3 sp3 sp 3d 2
(c) CH3 – C º C – CH2 + (d) CH3 – CH= CH – CH–2 102. The type of hybridization in xenon atom and the number of
94. Hybridization and structure of I3– are lone pairs present on xenon atom in xenon hexafluoride
(a) sp2 and trigonal planar molecule are respectively
(b) sp3d 2 and linear (a) sp3d 3 , one (b) sp3d 3 , two
(c) sp3d and linear (c) sp3d 3 , two (d) sp3d 2 , zero
(d) sp3 and T-shape 103. If an organic compound contain 92.3% C and 7.7% H, than
95. What is the change in hybridization when AlCl3 changes number of sp3, sp2 and sp hybridized carbon atoms in all
to [Al2Cl6]3– ? possible structures of compound respectively are (molecular
(a) sp3d to sp3d 2 (b) sp3 to sp3d mass = 52 g/mol)
2
(c) sp to sp d 3 2 (d) None of these
(a) 1, 2, 5 (b) 0, 4, 4
96. In an octahedral structure, the pair of d orbitals involved in
d 2sp3 hybridization is (c) 0, 8, 4 (d) None of these
(a) d x2 - y 2 , d z 2 (b) d xz, d 2 2 Topic 7: Molecular Orbital Theory
x -y
(c) d d (d) d xy, d yz 104. Molecular orbital theory was given by
z 2 , xz
(a) Kossel (b) Mosley
97. The trigonal bipyramidal geometry is obtained from the
hybridisation (c) Mulliken (d) Werner
(a) dsp 3 or sp 3d (b) dsp 2 or sp 2d 105. With increasing bond order, stability of bond
2 3
(c) d sp or sp d 3 2 (d) None of these (a) Remain unaltered (b) Decreases
98. The types of hybridisation of the five carbon atoms from (c) Increases (d) None of these
left to right in the molecule 106. The given increasing order of energies of various
CH3 — CH == C == CH — CH3 are molecular orbitals is not true for which of the following
(a) sp3, sp2, sp2, sp2, sp3 (b) sp3, sp, sp2, sp2, sp3 molecule?
(c) sp3, sp2, sp, sp2, sp3 (d) sp3, sp2, sp2, sp, sp3 s1s < s*1s < s2s < s*2s < (p2px = p2py) < s2pz < (p*2px
99. Which one of the following is not correct in respect of = p*2py) < s*2pz
hybridization of orbitals? (a) B2 (b) C2 (c) N2 (d) O2
(a) The orbitals present in the valence shell only are
107. If Nx is the number of bonding orbitals of an atom and Ny is
hybridized.
the number of antibonding orbitals, then the molecule/atom
(b) The orbitals undergoing hybridization have almost
will be stable if
equal energy.
(a) Nx > Ny (b) Nx = Ny (c) Nx < Ny (d) Nx £ Ny
 EBD_7374
48 CHEMISTRY

108. Assertion : The bond order of helium is always zero. while in antibonding molecular orbital it is located
Reason : The number of electrons in bonding molecular between the nuclei of the bonded atoms.
orbital and antibonding molecular orbital is equal. (a) Assertion is correct, reason is correct; reason is a
(a) Assertion is correct, reason is correct; reason is a correct explanation for assertion.
correct explanation for assertion. (b) Assertion is correct, reason is correct; reason is not a
(b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion.
correct explanation for assertion. (c) Assertion is correct, reason is incorrect.
(c) Assertion is correct, reason is incorrect. (d) Assertion is incorrect, reason is correct.
(d) Assertion is incorrect, reason is correct. 116. Among the following species, identify the pair having same
109. In an anti-bonding molecular orbital, electron density is bond order CN–, O2– , NO+, CN+
minimum (a) CN– and O2– (b) O2– and NO+
(a) around one atom of the molecule –
(c) CN and NO + (d) CN– and CN+
(b) between the two nuclei of the molecule 117. The compound which cannot be formed is
(c) at the region away from the nuclei of the molecule (a) He (b) He + (c) He 2 (d) He + 2
(d) at no place
118. Bond order in benzene is
110. When two atomic orbitals combine, they form
(a) 1 (b) 2
(a) one molecular orbital (b) two molecular orbital
(c) 1.5 (d) None of these
(c) three molecular orbital (d) four molecular orbital
111. Paramagnetism is exhibited by molecules Topic 8: Bonding in Some Homonuclear Diatomic Molecules
(a) not attracted into a magnetic field
(b) containing only paired electrons 119. The bond order in N2+ is
(c) carrying a positive charge (a) 1.5 (b) 3.0 (c) 2.5 (d) 2.0
(d) containing unpaired electrons 120. Which molecule has the highest bond order?
112. Atomic orbital is monocentric while a molecular orbital is (a) N2 (b) Li2 (c) He2 (d) O2
polycentric. What is the meaning of above statements? 121. Which one of the following molecules is expected to exhibit
(a) Electron density in atomic orbital is given by the diamagnetic behaviour ?
electron distribution around a nucleus in an atom. (a) C2 (b) N2 (c) O2 (d) S2
While in molecular orbital it is given by the electron 122. The correct statement with regard to H+2 and H2– is
distribution around group of nuclei in a molecule. (a) both H2+ and H–2 are equally stable
(b) While an electron in an atomic orbital is influenced (b) both H2+ and H2– do not exist
by one nucleus, in a molecular orbital it is influenced (c) H2– is more stable than H+2
by two or more nuclei depending upon the number (d) H2+ is more stable than H2-
of atoms in the molecule. 123. Mark the incorrect statement in the following
(c) The electron in an atomic orbital is present in one (a) the bond order in the species O2, O2+ and O2– decreases
nucleus while in molecular orbital electrons are as O 2+ > O 2 > O -2
present on more than one nuclei depending upon the
(b) the bond energy in a diatomic molecule always
number of atoms in the molecule.
increases when an electron is lost
(d) All of these
(c) electrons in antibonding M.O. contribute to repulsion
113. The difference in energy between the molecular orbital
between two atoms.
formed and the combining atomic orbitals is called
(d) with increase in bond order, bond length decreases
(a) bond energy (b) activation energy
and bond strength increases.
(c) stabilization energy (d) destabilization energy
124. According to molecular orbital theory which of the following
114. Which of the following statements is/are not correct for
statement about the magnetic character and bond order is
combination of atomic orbitals?
(i) The combining atomic orbitals must have the same or correct regarding O +2
nearly the same energy. (a) Paramagnetic and Bond order < O2
(ii) Greater the extent of overlap, the greater will be the (b) Paramagnetic and Bond order > O2
electron density between the nuclei of a moleculer (c) Diamagnetic and Bond order < O2
orbital. (d) Diamagnetic and Bond order > O2
(iii) 2pz orbital of one atom can combine with either of 125. Arrange the following in increasing order of bond length
2px, 2py or 2pz orbital of other atom as these orbitals
have same energy. (i) N2 (ii) N +2 (iii) N 22+
(a) (i) and (ii) (b) (iii) only (a) (ii), (i) and (iii) (b) (ii), (iii) and (i)
(c) (i) only (d) (ii) and (iii) (c) (iii), (ii) and (i) (d) (i), (ii) and (iii)
115. Assertion : Bonding molecular orbital has greater stability
126. Which of the following molecule exist ?
than corresponding antibonding molecular orbital.
Reason : The electron density in a bonding molecular (a) He2 (b) Be2
orbital is located away from the space between the nuclei (c) Li2 (d) Both (a) and (b)
CHEMICAL BONDING AND MOLECULAR STRUCTURE 49

127. The molecule which has the highest bond order is (c) hydrogen bonding interactions
(a) C2 (b) N2 (c) B2 (d) O2 (d) dipole-dipole interactions
128. The ground state electronic configuration of valence shell 138. Methanol and ethanol are miscible in water due to
electrons in nitrogen molecule (N 2 ) is written as (a) covalent character
KK s2 s 2 , s * 2s 2 , p2 p 2x , p 2 p 2y s 2 p 2z . Bond order in (b) hydrogen bonding character
nitrogen molecule is (c) oxygen bonding character
(a) 0 (b) 1 (c) 2 (d) 3 (d) None of these
129. Which of the following is not correct with respect to bond 139. The hydrogen bond is shortest in
length of the species ? (a) S — H --- S (b) N — H --- O
(c) S — H --- O (d) F — H --- F
(a) C2 > C22 - (b) B+2 > B2
140. Hydrogen bonding is maximum in
(c) Li 2+
> Li 2 (d) O2 > O-2 (a) C2H5OH (b) CH3OCH3
130. Bond order normally gives idea of stability of a molecular (c) (CH3)2 C = O (d) CH3CHO
species. All the molecules viz. H2, Li2 and B2 have the same 141. Intramolecular hydrogen bond exists in
bond order yet they are not equally stable. Their stability (a) ortho nitrophenol (b) ethyl alcohol
order is (c) water (d) diethyl ether
(a) H2 > B2 > Li2 (b) Li2 > H2 > B2 142. The boiling point of p-nitrophenol is higher than that of
(c) Li2 > B2 > H2 (d) B2 > H2 > Li2 o-nitrophenol because
(a) NO2 group at p-position behave in a different way from
131. In O-2 , O2 and O -2 2 molecular species, the total number of
that at o-position.
antibonding electrons respectively are (b) intramolecular hydrogen bonding exists in
(a) 7, 6, 8 (b) 1, 0, 2 (c) 6, 6, 6 (d) 8, 6, 8 p-nitrophenol.
132. N2 and O2 are converted to monopositive cations N2+ and (c) there is intermolecular h ydrogen bonding in
O2+ respectively. Which is incorrect ? p-nitrophenol.
(a) In N2+ the N–N bond is weakened
(d) p-nitrophenol has a higher molecular weight than
(b) In O2+ the bond order increases
o-nitrophenol.
(c) In O2+ the paramagnetism decreases
143. Which one of the following is the correct order of interactions ?
(d) N2+ becomes diamagnetic
(a) Covalent < hydrogen bonding < vander Waals < dipole-
133. According to MO theory which of the following lists ranks
dipole.
the nitrogen species in terms of increasing bond order?
(b) vander Waals < hydrogen bonding < dipole < covalent.
(a) N 2– –
2 < N2 < N2 (b) N 2 < N 22– < N 2– (c) vander Waals < dipole-dipole < hydrogen bonding
(c) N 2– < N 2– (d) N 2– < N 2 < N 2– < covalent.
2 < N2 2
(d) Dipole-dipole < vander Waals < hydrogen bonding
Topic 9: Hydrogen Bonding < covalent.
OH
134. In which of the following state of compound the
144. The vapour pressure of is higher than
magnitude of H-bonding will be maximum and in which
case it will be minimum ? NO 2
OH
(a) Maximum = Solid, Minimum = Liquid
(b) Maximum = Liquid, Minimum = Gas due to
(c) Maximum = Solid, Minimum = Gas O 2N
(d) Maximum = Gas, Minimum = Solid (a) dipole moment (b) dipole-dipole interaction
135. Which of the following are correctly classified ? (c) H-bonding (d) lattice structure
Intermolecular Intramolecular 145. The reason for exceptionally high boiling point of water is
H-bonding H-bonding (a) its high specific heat
(a) HF H2O (b) its high dielectric constant
(b) CH3OH HF (c) low ionization of water molecule
(c) H2O o-nitrophenol (d) hydrogen bonding in the molecules of water
(d) HF p-nitrophenol 146. Assertion : Water is one of the best solvent.
136. The boiling points at atmospheric pressure of HF, H2S, NH3 Reason : H-bonding is present in water molecules.
can be arranged in the following order: (a) Assertion is correct, reason is correct; reason is a
(a) HF > NH3 > H2S (b) HF > H2S > NH3 correct explanation for assertion.
(c) HF < H2S < NH3 (d) HF < NH3 < H2S (b) Assertion is correct, reason is correct; reason is not a
137. The low density of ice compared to water is due to correct explanation for assertion.
(a) induced dipole-induced dipole interactions (c) Assertion is correct, reason is incorrect.
(b) dipole-induced dipole interactions (d) Assertion is incorrect, reason is correct.
 EBD_7374
50 CHEMISTRY

147. Acetic acid exists as dimer in benzene due to

O
(a) condensation reaction
(b) hydrogen bonding H C CHO CHO NO 2
(c) presence of carboxyl group OH
(d) presence of hydrogen atom at a-carbon
148. Hydrogen bonding is formed in compounds containing OH
hydrogen and OH OH
(a) highly electronegative atoms (A) (B) (C) (D)
(b) highly electropositive atoms
(c) metal atoms with d-orbitals occupied (a) A (b) B and D
(c) B, C and D (d) A and C
(d) metalloids 150. Maximum number of H-bonds that can be formed by a water
149. Which among the following can form intermolecular molecule is
H – bonding ? (a) 2 (b) 3 (c) 4 (d) 6

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 8. Number of p bonds and s bonds in the following structure
is
1. Isostructural species are those which have the same shape
and hybridisation. Among the given species identify the H H
isostructural pairs.
H H
(a) [NF3 and BF3] (b) [BF4- and NH +4 ]

(c) [BCl3 and BrCl3] (d) [NH3 and NO3- ] H H

2. Polarity in a molecule and hence the dipole moment depends
primarily on electronegativity of the constituent atoms and H H
shape of a molecule. Which of the following has the highest (a) 6, 19 (b) 4, 20 (c) 5, 19 (d) 5, 20
dipole moment? 9. Which molecule/ion out of the following does not contain
(a) CO2 (b) HI (c) H2O (d) SO2 unpaired electrons?
3. The types of hybrid orbitals of nitrogen in NO+2 , NO3- and (a) N +2 (b) O2 (c) O 22 - (d) B2
NH +4 respectively are expected to be 10. In which of the following molecule/ion all the bonds are
not equal?
(a) sp, sp3 and sp2 (b) sp, sp2 and sp3
2
(c) sp , sp and sp 3 (d) sp2, sp3 and sp (a) XeF4 (b)BF4- (c) C2H4 (d) SiF4
4. Hydrogen bonds are formed in many compounds e.g., H2O, 11. In which of the following substances will hydrogen bond
HF, NH3. The boiling point of such compounds depends to be strongest?
an extent on the strength of hydrogen bond and the number (a) HCl (b) H2O (c) HI (d) H2S
of hydrogen bonds. The correct decreasing order of the 12. If the electronic configuration of an element is
boiling points above compounds is 1s2 2s2 2p6 3s2 3p6 3d 2 4s2, the four electrons involved in
(a) HF > H2O > NH3 (b) H2O > HF > NH3 chemical bond formation will be
(c) NH3 > HF > H2O (d) NH3 > H2O > HF (a) 3p6 (b) 3p6, 4s2 (c) 3p6, 3d 2 (d) 3d 2, 4s2
5. In PO34- ion the formal charge on the oxygen atom of 13. Which of the following angle corresponds to sp 2
hybridisation?
P – O bond is (a) 90° (b) 120° (c) 180° (d) 109°
(a) + 1 (b) – 1 (c) – 0.75 (d) + 0.75 Direction (Q. no. 14-17) The electronic configurations of the
6. -
In NO 3 ion, the number of bond pairs and lone pairs of elements A, B and C are given below. Answer the questions from
14 to 17 on the basis of these configurations.
electrons on nitrogen atom are A 1s2 2s2 2p6
(a) 2, 2 (b) 3, 1 (c) 1, 3 (d) 4, 0 B 1s 2 2s2 2p6 3s2 3p3
7. Which of the following species has tetrahedral geometry? C 1s 2 2s2 2p 6 3s2 3p5
(a) BH -4 (b) NH -2 (c) CO32 - (d) H3 O+
CHEMICAL BONDING AND MOLECULAR STRUCTURE 51

14. Stable form of A may be represented by the formula (b) If both Assertion and Reason are correct, but Reason
(a) A (b) A 2 (c) A 3 (d) A 4 is not the correct explanation of Assertion.
15. Stable form of C may be represented by the formula (c) If Assertion is correct but Reason is incorrect.
(a) C (b) C2 (c) C3 (d) C4 (d) If both the Assertion and Reason are incorrect.
16. The molecular formula of the compound formed from B and 27. Assertion : Cuprous ion (Cu+) has unpaired electrons while
C will be cupric ion (Cu++) does not.
(a) BC (b) B2C (c) BC2 (d) BC3 Reason : Cuprous ion (Cu+) is colourless whereas cupric
17. The bond between B and C will be ion (Cu++) is blue in the aqueous solution.
(a) ionic (b) covalent [AIIMS 2014, C]
(c) hydrogen (d) coordinate (a) If both Assertion and Reason are correct and Reason
18. Which of the following order of energies of molecular is the correct explanation of Assertion.
orbitals of N2 is correct? (b) If both Assertion and Reason are correct, but Reason
(a) (p2py ) < (s2pz ) < (p*2px ) » (p*2py ) is not the correct explanation of Assertion.
(b) (p2py ) > (s2pz ) > (p*2px ) » (p*2py ) (c) If Assertion is correct but Reason is incorrect.
(c) (p2py ) < (s2pz) < (p*2px) » (p*2py ) (d) If both the Assertion and Reason are incorrect.
(d) (p2py ) > (s2pz) < (p*2px) » (p*2py ) 28. Which one of the following properties is not shown by NO?
19. Which of the following statement is not correct from the [JEE M 2014, A]
view point of molecular orbital theory? (a) It is diamagnetic in gaseous state
(a) Be2 is not a stable molecule. (b) It is neutral oxide
(c) It combines with oxygen to form nitrogen dioxide
(b) He2 is not stable but He +2 is expected to exist.
(d) It’s bond order is 2.5
(c) Bond strength of N 2 is maximum amongst the
29. For which of the following molecule significant m ¹ 0?
homonuclear diatomic molecules belonging to the
second period. [JEE M 2014, A]
(d) The order of energies of molecular orbitals in N2 Cl CN
molecule is
s2s < s*2s < s2pz < (p2px ; p2py) < (p*2px ; p*2py )
(i) (ii)
< s*2pz
20. Which of the following options represents the correct bond
order? Cl CN
(a) O -2 > O 2 > O 2+ (b) O -2 < O 2 < O2+ OH SH

(c) O -2 > O 2 < O 2+ (d) O -2 < O 2 > O 2+

21. The electronic configuration of the outer most shell of the (iii) (iv)
most electronegative element is
(a) 2s22p5 (b) 3s23p5 (c) 4s24p5 (d) 5s25p5 OH SH
22. Amongst the following elements whose electronic (a) Only (i) (b) (i) and (ii)
configuration are given below, the one having the highest (c) Only (iii) (d) (iii) and (iv)
ionisation enthalpy is 30. Which one of the following pairs is isostructural (i.e., having
(a) [Ne]3s23p1 (b) [Ne]3s23p3 the same shape and hybridization)? [BITSAT 2014, S]
2
(c) [Ne]3s 3p 2 (d) [Ar]3d104s24p3
(a) é BCl3 and BrCl3- ù (b) é NH3 and NO3- ù
Past Year MCQs ë û ë û
23. Be2+ is isoelectronic with which of the following ions?
[AIPMT 2014, A]
(c) [ NF3 and BF3 ] (d) é BF4- and NH +4 ù
ë û
(a) H+ (b) Li+ (c) Na+ (d) Mg2+ 31. The molecules BF3 and NF3 are both covalent compounds,
24. Which of the following molecules has the maximum dipole but BF3 is non polar whereas NF3 is polar. The reason for
moment ? [AIPMT 2014, A] this is [BITSAT 2014, C]
(a) CO2 (b) CH4 (c) NH3 (d) NF3 (a) atomic size of Boron is larger than nitrogen
25. Which one of the following species has plane triangular (b) Boron is metal while nitrogen is gas
shape ? [AIPMT 2014, A] (c) B – F bonds are non-polar while N – F bonds are polar
(a) N3– (b) NO3– (c) NO2– (d) CO2 (d) BF3 is planar but NF3 is pyramidal
26. Assertion : LiCl is predominantly a covalent compound. 32. The correct bond order in the following species is:
Reason : Electronegativity difference between Li and Cl is [AIPMT 2015, A]
too small. [AIIMS 2014, C] (a) O 22+ < O2– < O 2+ (b) O +2 < O 2– < O 22+
(a) If both Assertion and Reason are correct and Reason
is the correct explanation of Assertion. (c) O 2– < O 2+ < O 22+ (d) O 22+ < O 2+ < O 2–
 EBD_7374
52 CHEMISTRY

33. Which of the following pairs of ions are isoelectronic and greater than 90°
isostructural ? [AIPMT 2015, A] (b) The H–O–H bond angle in H2O is larger than the
H–C–H bond angle in CH4.
(a) ClO3– , CO32– (b) SO32– , NO3–
(c) The H–O–H bond angle in H2O is smaller than the
(c) ClO3– , SO32– (d) CO32– , SO32– H–N–H bond angle in NH3.
(d) The H–C–H bond angle in CH4 is larger than the
34. Which of the following options represents the correct bond
H–N–H bond angle in NH3.
order ? [AIPMT 2015, A]
42. Predict the correct order among the following :
(a) O 2– < O 2 < O 2+ (b) O –2 > O2 < O 2+ [NEET 2016, C]
(a) lone pair- lone pair > lone pair - bond pair > bond pair -
(c) O 2– < O2 > O 2+ (d) O –2 > O2 > O2+ bond pair
35. Maximum bond angle at nitrogen is present in which of the (b) lone pair - lone pair > bond pair - bond pair > lone pair
following? [AIPMT 2015, S] - bond pair
(b) NO +2 (c) bond pair - bond pair > lone pair - bond pair > lone pair
(a) NO 2– (c) NO3– (d) NO 2
- lone pair
36. Which of the following species contains equal number of (d) lone pair - bond pair > bond pair - bond pair > lone pair
s- and p-bonds : [AIPMT 2015, S] - lone pair
(a) XeO4 (b) (CN)2 43. XeO4 molecule is tetrahedral having : [AIIMS 2016, S]
(c) CH2(CN)2 (d) HCO3– (a) Two pp – dp bonds (b) One pp – dp bonds
(c) Four pp – dp bonds (d) Three pp – dp bonds
37. Decreasing order of stability of O2 , O- + 2-
2 ,O 2 and O2 is : 44. Among the following species, identify the pair having same
[AIPMT 2015, A] bond order CN–, O2– , NO+, CN+ [AIIMS 2016, A]
(a) CN– and O2– (b) O2– and NO+
(a) O+ - 2-
2 > O2 > O2 > O2 (c) CN– and NO+ (d) CN– and CN+
(b) O 22- > O- +
2 > O2 > O2
45. Assertion : Lone pair-lone pair repulsive interactions are
greater than lone pair-bond pair and bond pair-bond pair
(c) O2 > O+ 2- -
2 > O2 > O2
interactions.
Reason : The space occupied by lone pair electrons is more
(d) O- 2- +
2 > O2 > O2 > O2
as compared to bond pair electrons. [AIIMS 2016, C]
(a) If both Assertion and Reason are correct and Reason
38. In which of the following pairs, both the species are not
is the correct explanation of Assertion.
isostructural ? [AIPMT 2015, A]
(b) If both Assertion and Reason are correct, but Reason
(a) SiCl4 , PCl+
4 (b) diamond, silicon carbide is not the correct explanation of Assertion.
(c) NH3, PH3 (d) XeF4, XeO4 (c) If Assertion is correct but Reason is incorrect.
39. Match List I and List II and pick out correct matching codes (d) If both the Assertion and Reason are incorrect.
from the given choices : [AIIMS 2015, S] 46. The species in which the N atom is in a state of sp
List I List II hybridization is : [JEE M 2016, S]
Compound Structure (a) NO-3 (b) NO2 (c) NO+2 (d) NO-2
A. ClF3 1. Square planar
B: PCl5 2. Tetrahedral 47. In PO 34– , the formal charge on each oxygen atom and the P
C. IF5 3. Trigonal bipyramidal - O bond order respectively are [BITSAT 2016, A]
D. CCl4 4. Square pyramidal (a) –0.75, 0.6 (b) –0.75, 1.0
E. XeF4 5. T-shaped (c) –0.75, 1.25 (d) –3, 1.25
Codes 48. Which of the following pairs of species have the same bond
(a) A-5, B-4, C-3, D-2, E-1 order ? [NEET 2017, S]
(b) A-5, B-3, C-4, D-2, E-1 (a) O2, NO+ (b) CN–, CO (c) N 2 , O 2- (d) CO, NO
(c) A-5, B-3, C-4, D-1, E-2
49. Which of the following pairs of compounds is isoelectronic
(d) A-4, B-3, C-5, D-2, E-1 and isostructural ? [NEET 2017, A]
40. The P—P—P angle in P 4 molecule and
S—S—S angle in S8 molecule is (in degree) respectively (a) TeI2,XeF2 (b) IBr2- , XeF2
[BITSAT 2015, S] (c) IF3, XeF2 (d) BeCl2,XeF2
(a) 60°, 107° (b) 107°, 60° 50. The species, having bond angles of 120° is :-
(c) 40°, 60° (d) 60°, 40° [NEET 2017, S]
41. Consider the molecules CH4, NH3 and H2O. Which of the (a) ClF3 (b) NCl3 (c) BCl3 (d) PH3
given statements is false? [NEET 2016, C] 51. Which of the following substances has the least covalent
(a) The H–C–H bond angle in CH4, the H–N–H bond angle character ? [AIIMS 2017, C]
in NH3, and the H–O–H bond angle in H2O are all (a) Cl2O (b) NCl3 (c) PbCl2 (d) BaCl2
CHEMICAL BONDING AND MOLECULAR STRUCTURE 53

52. Which of the following species is not paramagnetic ? 60. Total number of lone pair of electrons in I3– ion is :
[JEE M 2017, S]
[JEE M 2018, A]
(a) NO (b) CO (c) O2 (d) B2
53. Which of these compounds are directional? (a) 3 (b) 6 (c) 9 (d) 12
[BITSAT 2017, S] 61. According to molecular orbital theory, which of the following
(a) NaCl (b) CO2 (c) BaO (d) CsCl2 will not be a viable molecule? [JEE M 2018, A]
54. Which of the following shows correct order of bond length?
[BITSAT 2017, A] (a) He22+ (b) He+2 (c) H2– (d) H 2–
2
(a) O2+ > O2 > O2– > O22– (b) O2+ < O2– > O2 < O22– 62. Which of the following compounds contain(s) no covalent
(c) O2+ > O2 < O2– > O22– (d) O2+ > O2 < O2– > O22– bond(s)? [JEE M 2018, S]
55. In the structure of ClF3, the number of lone pair of electrons
KCl, PH3, O2, B2H6, H2SO4
on central atom ‘Cl’ is [NEET 2018, S]
(a) One (b) Two (c) Three (d) Four (a) KCl, B2H6, PH3 (b) KCl, H2SO4
56. Consider the following species : [NEET 2018, A] (c) KCl (d) KCl, B2H6
CN+, CN–, NO and CN 63. Which of the following is the correct and increasing order
Which one of these will have the highest bond order? of lone pair of electrons on the central atom?
(a) NO (b) CN– (c) CN (d) CN+ [BITSAT 2018, S]
57. Which of the following pair of molecules does not have (a) IF7 < IF5 < CIF3 < XeF2 (b) IF7 < XeF2 < CIF2 < IF5
identicle structure? [AIIMS 2018, A]
(a) I3–, BeF2 (b) HClO, SO2 (c) IF7 < CIF3 < XeF2 < IF5 (d) IF7 < XeF2 < IF5 < CIF3
(c) BF3, ICl3 (d) BrF4–, XeF4 64. According to molecular orbital theory which of the following
58. Which contains atleast one e– in s2p bonding MO? statement about the magnetic character and bond order is
[AIIMS 2018, C] correct regarding O +2 [BITSAT 2018, S]
(a) O2 (b) B2 (c) C2 (d) Li2 (a) Paramagnetic and Bond order < O2
59. Assertion : Geometry of SF4 molecule can be termed as
distorted tetrahedron, a folded square or see saw. (b) Paramagnetic and Bond order > O2
Reason : Four fluorine atoms surround or form bond with (c) Diamagnetic and Bond order < O2
sulphur atom. [AIIMS 2018, S] (d) Diamagnetic and Bond order > O21

Exercise 3 : Try If You Can

1. Which of the following hydrocarbons has the lowest dipole 4. The AsF5 molecule is trigonal bipyramidal. The hybrid orbitals
moment ? used by the As atom for bonding are
H3C CH3 (a) d x2 - y2 , d z 2 , s, px , p y (b) d xy ,s, px , py , pz
(a) C (b) CH 3C º CCH 3 (c) s, px , py , pz , d 2 (d) d 2 2 , s, px , p y , pz
z x -y
H H 5. Which of the following species contains minimum number
(c) CH 3CH 2 C º CH (d) CH 2 = CH – C º CH of atoms in ‘XY’ plane?
2. –
Although CN ion and N2 molecule are isoelectronic, yet (a) XeF5– (b) SF6 (c) IF7 (d) All
N2 molecule is chemically inert because of 6. In which of the following species maximum atom can lie in
(a) presence of more number of electrons in bonding orbitals same plane?
(b) lone bond energy (a) XeF2O2 (b) PCl5 (c) AsH +4 (d) XeF4
(c) absence of bond polarity 7. Which of the following orbital combination can not form
(d) uneven electron distribution. p-bond ?
3. Read the following statements and choose the correct option. (a) px + px sideways overlapping
(b) d + p y sideways overlapping
(i) P—O bond length order in : PO3– 2– –
4 > HPO3 > H2PO2 x2 - y 2
(c) dxy + dxy sideways overlapping
q1 q2 (d) dyz + py sideways overlapping
(ii) q2 > q1 8. In which of the following combination hybridisation of
central atom (*) does not change?
* * –
(iii) Between C2H4 and C2H4, C—H is stronger in C2H2. (a) H 2O + C O2 (b) H3 BO3 + OH
*
(a) (i) (b) (i), (ii) & (iii) (c) (i) & (ii) (d) (ii) & (iii) (c) BF3 + N H3 (d) None of these
 EBD_7374
54 CHEMISTRY

9. In which of the following ionization processes the bond 12. The relative stabilities of CN, CN+ and CN– are in the order
energy has increased and also the magnetic behaviour has (a) CN > CN+ > CN– (b) CN– > CN > CN+
changed from paramagnetic to diamagnetic ? –
(c) CN > CN > CN+ (d) CN+ > CN > CN–
(a) NO ® NO + (b) N 2 ® N 2 + 13. Which of the following ions does not involve pp – dp
bonding?
(c) C2 ® C2 + (d) O2 ® O2 +
(a) SO 32 - (b) PO 34- (c) NO 3- (d) XeOF4
10. In forming (i) N 2 ® N +2
and (ii) O2 ® O2+ ; the electrons
14. Select the most stable cation
respectively are removed from :
(a) (p*2py or p*2px) and (p*2py or p*2px) (a) NH +4 (b) CH 5+ (c) H3 O + (d) FH +2
(b) (p 2py or p 2px) and (p2py or p2px) 15. Which of the following is most appropriate structure of
(c) (p2py or p2px) and (p*2py or p*2px) C3O2?
(d) (p*2py or p*2px) and (p2py or p2px) (a) O= C =O ® C =O
11. CrO2Cl2 has
(a) tetragonal structure (b) O ® O = C = C = C
(b) distorted tetrahedral structure (c) C = O ® C = C = O
(c) square pyramidal structure
(d) O = C = C = C = O
(d) octahedral structure

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (d) 16 (c) 31 (c) 46 (b) 61 (a) 76 (a) 91 (d) 106 (d) 121 (a, b) 136 (a)
2 (b) 17 (b) 32 (a) 47 (b) 62 (b) 77 (c) 92 (a) 107 (a) 122 (d) 137 (c)
3 (b) 18 (a) 33 (c) 48 (a) 63 (d) 78 (d) 93 (c) 108 (a) 123 (b) 138 (b)
4 (b) 19 (d) 34 (b) 49 (d) 64 (a) 79 (a) 94 (c) 109 (b) 124 (b) 139 (d)
5 (d) 20 (c) 35 (c) 50 (b) 65 (c) 80 (d) 95 (c) 110 (b) 125 (d) 140 (a)
6 (c) 21 (b) 36 (a) 51 (c) 66 (b) 81 (d) 96 (a) 111 (d) 126 (c) 141 (a)
7 (a) 22 (b) 37 (d) 52 (a) 67 (d) 82 (c) 97 (a) 112 (b) 127 (b) 142 (c)
8 (a) 23 (c) 38 (a) 53 (b) 68 (b) 83 (a) 98 (c) 113 (c) 128 (d) 143 (b)
9 (c) 24 (d) 39 (c) 54 (d) 69 (b) 84 (b) 99 (d) 114 (b) 129 (d) 144 (c)
10 (a) 25 (d) 40 (c) 55 (a) 70 (a) 85 (b) 100 (a) 115 (c) 130 (N) 145 (d)
11 (d) 26 (d) 41 (d) 56 (d) 71 (a) 86 (b) 101 (b) 116 (c) 131 (a) 146 (b)
12 (b) 27 (c) 42 (c) 57 (a) 72 (a) 87 (b) 102 (a) 117 (c) 132 (d) 147 (b)
13 (a) 28 (d) 43 (c) 58 (b) 73 (a) 88 (a) 103 (c) 118 (c) 133 (a) 148 (a)
14 (a) 29 (b) 44 (d) 59 (a) 74 (a) 89 (d) 104 (c) 119 (c) 134 (c) 149 (c)
15 (a) 30 (c) 45 (a) 60 (b) 75 (b) 90 (a) 105 (c) 120 (a) 135 (c) 150 (c)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 8 (c) 15 (b) 22 (b) 29 (d) 36 (a) 43 (c) 50 (c) 57 (c) 64 (b)
2 (c) 9 (c) 16 (d) 23 (b) 30 (d) 37 (a) 44 (c) 51 (d) 58 (a)
3 (b) 10 (c) 17 (b) 24 (c) 31 (d) 38 (d) 45 (a) 52 (b) 59 (b)
4 (b) 11 (b) 18 (a) 25 (b) 32 (c) 39 (b) 46 (c) 53 (b) 60 (c)
5 (c) 12 (d) 19 (d) 26 (c) 33 (c) 40 (a) 47 (c) 54 (b) 61 (d)
6 (d) 13 (b) 20 (b) 27 (d) 34 (a) 41 (b) 48 (b) 55 (b) 62 (c)
7 (a) 14 (a) 21 (a) 28 (a) 35 (b) 42 (a) 49 (b) 56 (b) 63 (a)
Exercise 3 : Try If You Can
1 (b) 3 (b) 5 (b) 7 (b) 9 (a) 11 (b) 13 (c) 15 (d)
2 (c) 4 (c) 6 (d) 8 (c) 10 (c) 12 (b) 14 (a)
 5
Chapter
STATES OF MATTER

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Kinetic theory of gases, Deviation
AIIMS 3 from ideal behaviour, critical 3/5 7.1
JEE Main 3 phenomenon and liquefaction of
BITSAT 2 gases
 EBD_7374
56 CHEMISTRY
STATES OF MATTER 57
 EBD_7374
58 CHEMISTRY

Exercise 1 : Topic-wise MCQs

(A) HCl (B) SF6 and (C) NaCl
Topic 1: Intermolecular Forces
(a) A, B, C (b) A, C, B (c) B, A, C (d) B, C, A
1. Which of the following is not a type of van der Waal's 9. Which of the following statements are correct regarding the
forces? characteristic of gases ?
(a) Dipole - dipole forces (i) Gases are highly compressible.
(b) Dipole - induced dipole forces (ii) Gases exert pressure equally in all directions.
(c) Ion - dipole forces (iii) Gases have much higher density than the solids and
(d) London forces liquids.
2. Who proposed the concept of dispersion force ? (iv) Gases mix evenly and completely in all proportion
(a) Heitler and London (b) van der Waal without any mechanical aid.
(c) Gay Lussac (d) Fritz London Choose the correct option.
3. Dipole-dipole interaction is stronger than the London forces (a) (i), (ii) and (iii) (b) (ii), (iii) and (iv)
but is weaker than ion-ion interaction because (c) (i), (ii) and (iv) (d) (i), (ii), (iii) and (iv)
(a) only partial charges are involved 10. Assertion : Gases expand and occupy all the space available
(b) only total charges are involved to them
(c) both (a) and (b) Reason : There is no force of attraction between the particles
(d) sometimes (a) and sometimes (b) of a gas at ordinary temperature and pressure.
4. Dipole-induced dipole interactions are present in which of (a) Assertion is correct, reason is correct; reason is a
the following pairs : correct explanation for assertion.
(a) Cl2 and CCl4 (b) HCl and He atoms (b) Assertion is correct, reason is correct; reason is not a
(c) SiF4 and He atoms (d) H2O and alcohol correct explanation for assertion
5. Which of the following exhibits the weakest intermolecular (c) Assertion is correct, reason is incorrect
forces ? (d) Assertion is incorrect, reason is correct.
(a) NH3 (b) HCl (c) He (d) H2O
6. Assertion : Three states of matter are the result of balance Topic 2: Intermolecular Forces Vs Thermal Interactions
between intermolecular forces and thermal energy of the
11. Which of the following statements regarding thermal energy
molecules.
is correct ?
Reason : Intermolecular forces tend to keep the molecules
(a) Thermal energy is the measure of average kinetic energy
together but thermal energy of molecules tends to keep them
of the particles of the matter and is thus responsible
apart.
for movement of particles.
(a) Assertion is correct, reason is correct; reason is a
(b) Intermolecular forces tend to keep the molecules
correct explanation for assertion.
together but thermal energy of the molecules tends to
(b) Assertion is correct, reason is correct; reason is not a
keep them apart.
correct explanation for assertion
(c) Three states of matter are the result of balance between
(c) Assertion is correct, reason is incorrect
intermolecular forces and the thermal energy of the
(d) Assertion is incorrect, reason is correct.
molecules.
7. Which of the following statements are correct ?
(d) All of the above
(i) Hydrogen bonding is a special case of dipole - dipole
12. Which of the following are arrangement in the correct order?
interaction.
I. Gas > Liquid > Solid (Thermal energy)
(ii) Energy of hydrogen bond varies between 10 to
II. Solid > Liquid > Gas (Intermolecular force)
100 kJ mol–1.
Select the correct option.
(iii) Hydrogen bonds are powerful force in determining the
(a) I only (b) II only
structure and properties of compounds like proteins,
(c) Both I and II (d) None of these
nucleic acids etc.
13. Which one of the following statements is not correct about
(iv) Strength of the hydrogen bond is determined by the
the three states of matter i.e., solid, liquid and gaseous ?
coulombic interaction between the lone-pair electrons
(a) Molecules of a solid possess least energy whereas
of the electronegative atom of one molecule and the
those of a gas possess highest energy.
hydrogen atom of other molecule.
(b) The density of solid is highest whereas that of gases is
(a) (i) and (ii) (b) (i), (ii) and (iii)
lowest
(c) (ii), (iii) and (iv) (d) All of these
(c) Gases like liquids possess definite volumes
8. Arrange the following in increasing order their
(d) Molecules of a solid possess vibratory motion
intermolecular interaction
STATES OF MATTER 59

21. Match the graphs between the following variables (Column-I)

Topic 3: The Gaseous State and Gas Laws
with their names (Column-II) :
14. The first reliable measurement on properties of gases was Column-I Column-II
made by ______________ (Graphs) (Names)
(a) Gay Lussac (b) Jacques charles (A) Pressure vs temperature (p) Isotherms
(c) Robert Boyle (d) Avogadro graph at constant
15. Which of following graph(s) represents Boyle's law molar volume.
(B) Pressure vs volume (q) Constant temperature
graph at constant curve
I. P II. P temperature
(C) Volume vs temperature (r) Isochores
V V graph at constant
pressure
(s) Isobars
III. P IV. P (a) A – (p), B – (r), C – (s)
(b) A – (r), B – (p), C – (s)
1/V 1/V (c) A – (r), B – (q), C – (p)
(a) Only I (b) II and IV (c) I and III (d) Only III (d) A – (s), B – (q), C – (r)
16. 600 c.c. of a gas at a pressure of 750 mm of Hg is compressed 22. Air at sea level is dense. This is a practical application of
to 500 c.c. Taking the temperature to remain constant, the (a) Boyle’s law (b) Charle’s law
increase in pressure, is (c) Kelvin’s law (d) Brown’s law
(a) 150 mm of Hg (b) 250 mm of Hg
23. 500 mL of air at 760 mm pressure were compressed to 200
(c) 350 mm of Hg (d) 450 mm of Hg mL. If the temperature remains constant, what will be the
17. Match the columns pressure after compression?
Column-I Column-II (a) 1800 mm (b) 1900 mm
(A) Boyle's law (p) V µ n at constant T
(c) 2000 mm (d) 1500 mm
and P
24. When a sample of gas is compressed at constant temperature
(B) Charle's law (q) Ptotal = P1+ P2+ P3+ ....
from 15 atm to 60 atm, its volume changes from 76 cm3 to
at constant T, V 20.5 cm3. Which of the following statements are possible
PV explanations of this behaviour?
(C) Dalton's law (r) < Constant
T (1) The gas behaves non-ideally
(D) Avogadro law (s) V µ T at constant n (2) The gas dimerises
and P (3) The gas is adsorbed into the vessel walls
1
(t) P µ at constant n (a) 1, 2 and 3 (b) 1 and 2 only
V (c) 2 and 3 only (d) 1 only
and T 25. Pressure in well inflated tyres of automobiles is almost
(a) A – (t), B – (s), C – (q), D – (p) constant, but on a h ot summer day this increases
(b) A – (s), B – (q), C – (p), D – (t) considerably and tyre may burst if pressure is not adjusted
(c) A – (r), B – (t), C – (q), D – (p) properly. During winters, on a cold morning one may find
(d) A – (t), B – (q), C – (s), D – (r) the pressure in the tyres of a vehicle decreased considerably.
18. The lowest hypothetical or imaginary temperature at which Which of the following law explain the above observations?
gases are supposed to occupy zero volume is called
_________ (a) Charle's Law (b) Avogadro Law
(c) Boyle's Law (d) Gay Lussac's Law
(a) Kelvin temperature (b) absolute zero
26. On a ship sailing in pacific ocean where temperature is 23.4°C,
(c) Charle's temperature (d) constant temperature
a balloon is filled with 2 L air. What will be the volume of the
19. 500 mL of nitrogen at 27°C is cooled to –5°C at the same balloon when the ship reaches Indian ocean, where
pressure. The new volume becomes temperature is 26.1°C ?
(a) 326.32 mL (b) 446.66 mL (a) 2.018 L (b) 2.8 L (c) 3.5 L (d) 1.5 L
(c) 546.32 mL (d) 771.56 mL
27. Which of the following volume (V) - temperature (T) plots
20. What is the value of X in °C for given volume vs temperature
represents the behaviour of one mole of an ideal gas at one
curve ?
P1 P < P < P < P atmospheric pressure ?
P2 1 2 3 4
V(L) V(L)
P3 (36.8 L (26.8 L
Volume P4 (22.4 L 373 K) (22.4 L 373 K)
(a) 273K) (b) 273K)

X Temperature (°C)
(a) 0° C (b) 273.15° C
(c) – 273.15° C (d) 300° C T(K) T(K)
 EBD_7374
60 CHEMISTRY

38. Pressure of a mixture of 4 g of O2 and 2 g of H2 confined in

V(L)
V(L) a bulb of 1 litre at 0°C is
(30.6 L
373 K) (22.4 L (a) 25.215 atm (b) 31.205 atm
273K)
(c) (22.4 L (d) (14.2 L (c) 45.215 atm (d) 15.210 atm
273K) 373 K) 39. If three unreactive gases having partial pressures PA, PB
T(K)
and PC and their moles are 1, 2 and 3 respectively then their
T(K)
total pressure will be
28. At constant temperature, for a given mass of an ideal gas
(a) The ratio of pressure and volume always remains (a) P = PA + PB + PC (b) P = PA + PB + PC
6
constant.
(b) Volume always remains constant. PA + PB + PC
(c) P= (d) None of these
(c) Pressure always remains constant. 3
(d) The product of pressure and volume always remains 40. Dalton’s law of partial pressure will not apply to which of
constant. the following mixture of gases
29. If 500 mL of gas A at 400 torr and 666.6 mL of B at 600 torr are (a) H2 and SO2 (b) H2 and Cl2
placed in a 3 litre flask, the pressure of the system will be (c) H2 and CO2 (d) CO2 and Cl2
(a) 200 torr (b) 100 torr (c) 550 torr (d) 366 torr 41. The pressure exerted by 6.0g of methane gas in a 0.03 m3
30. For 1 mol of an ideal gas at a constant temperature T, the vessel at 129°C is (Atomic masses : C = 12.01, H = 1.01 and
plot of (log P) against (log V) is a (P : Pressure, V : Volume) R = 8.314 JK–1 mol –1)
(a) Straight line parallel to x-axis. (a) 31684 Pa (b) 215216 Pa
(b) Straight line with a negative slope. (c) 13409 Pa (d) 41648 Pa
(c) Curve starting at origin. 42. A gaseous mixture was prepared by taking equal mole of CO
(d) Straight line passing through origin. and N 2. If the total pressure of the mixture was found
1 atmosphere, the partial pressure of the nitrogen (N2) in the
Topic 4: Ideal Gas Equation mixture is
31. At STP molar volume of an ideal gas or a combination of (a) 0.5 atm (b) 0.8 atm (c) 0.9 atm (d) 1 atm
ideal gases is ___________ 43. A bubble of air is underwater at temperature 15°C and the
(a) 22.71098 L mol–1 (b) 20.71098 L mol–1 pressure 1.5 bar. If the bubble rises to the surface where the
(c) 22.4139 L mol –1 (d) 24.78 L mol–1 temperature is 25°C and the pressure is 1.0 bar, what will
32. 4.4 g of a gas at STP occupies a volume of 2.24 L, the gas happen to the volume of the bubble ?
can be (a) Volume will become greater by a factor of 1.6.
(a) O2 (b) CO (c) NO2 (d) CO2 (b) Volume will become greater by a factor of 1.1.
33. An ideal gas is one which obeys the gas laws under (c ) Volume will become smaller by a factor of 0.70.
(a) a few selected experimental conditions (d) Volume will become greater by a factor of 2.5.
(b) all experimental conditions 44. A mixture contains 64 g of dioxygen and 60 g of neon at a
total pressure of 10 bar. The partial pressures in bar of
(c) low pressure alone
dioxygen and neon are respectively (atomic masses O = 16,
(d) high temperature alone
Ne = 20)
34. Select one correct statement. In the gas equation, PV = nRT
(a) 4 and 6 (b) 6 and 4 (c) 5 and 5 (d) 8 and 2
(a) n is the number of molecules of a gas 45. Value of universal gas constant (R) depends upon
(b) V denotes volume of one mole of the gas (a) Number of moles of gas
(c) n moles of the gas have a volume V (b) Volume of gas
(d) P is the pressure of the gas when only one mole of gas (c) Temperature of gas
is present. (d) None of these
35. The correct value of the gas constant ‘R’ is close to : 46. Two vessels of volumes 16.4 L and 5 L contain two ideal
(a) 0.082 litre-atmosphere K gases of molecular existence at the respective temperature
(b) 0.082 litre-atmosphere K–1 mol–1 of 27°C and 227°C and exert 1.5 and 4.1 atmospheres
(c) 0.082 litre – atmosphere–1 K mol–1 respectively. The ratio of the number of molecules of the
(d) 0.082 litre –1 atmosphere – 1 K mol former to that of the later is
36. If P, V, M, T and R are pressure, volume, molar mass, 1 1
(a) 2 (b) 1 (c) (d)
temperature and gas constant respectively, then for an ideal 2 3
gas, the density is given by 47. 56 g of nitrogen and 96 g of oxygen are mixed isothermally
and at a total pressure of 10 atm. The partial pressures of
RT P PM
(a) (b) (c) M (d) oxygen and nitrogen (in atm) are respectively
PM RT V RT (a) 4, 6 (b) 5, 5 (c) 2, 8 (d) 6, 4
37. At N.T.P the volume of a gas is found to be 273 ml. What will 48. If 10–4 dm3 of water is introduced into a 1.0 dm3 flask at 300 K,
be the volume of this gas at 600 mm of Hg and 273°C? how many moles of water are in the vapour phase when
(a) 391.8 mL (b) 380 mL (c) 691.6 mL (d) 750 mL equilibrium is established ?
STATES OF MATTER 61

(Given : Vapour pressure of H2O at 300 K is 3170 Pa; (a) 5.25 bar, 10 bar (b) 19.75 bar, 5.25 bar
R = 8.314 J K–1 mol–1) (c) 19.75 bar, 10 bar (d) 5.75 bar, 19.75 bar
(a) 5.56× 10–3 mol (b) 1.53 × 10–2 mol 57. 0.5 mole of each H2, SO2 and CH\4 are kept in a container. A
–2
(c) 4.46 × 10 mol (d) 1.27 × 10–3 mol hole was made in the container. After 3 h, the order of partial
49. Three different gases X, Y and Z of molecular masses 2, 16 pressures in the container will be
and 64 were enclosed in a vessel at constant temperature till pSO 2 > pCH 4 > pH 2 pH 2 > pSO 2 > pCH 4
(a) (b)
equilibrium is reached. Which of the following statement is
correct? (c) pH 2 > pCH 4 > pSO 2 (d) pSO 2 > pH 2 > pCH 4
(a) Gas Z will be at the top of the vessel
58. What is the ratio of pressure of the 2 g of hydrogen to
(b) Gas Y will be at the top of the vessel
that of 4 g of helium at temperature of 298 K, 20 mL
(c) Gas Z will be at the bottom and X will be at the top
volume? (consider the ideal behaviour)
(d) Gases will form homogenous mixture
(a) 1 : 2 (b) 2 : 1 (c) 1 : 1 (d) 2 : 2
50. Consider the case of hot air balloon, density of air at 20°
C is 1.2 kg/m3, if the air was heated to 99°C, density of air Topic 5: Kinetic Molecular Theory of Gases
becomes 0.94 kg/m3. What would be the volume (in m3) 59. According to the kinetic theory of gases, in an ideal gas,
at 20°C if the volume at 99°C is 2800 m3 and how much between two successive collisions a gas molecule travels
air (in kg) has been escaped at 99°C , if the air in inflated (a) in a wavy path
balloon was heated to 99°C (if the inflated volume of (b) in a straight line path
balloon was found to be 2800 m3) respectively are (c) with an accelerated velocity
(a) 2243, 728 (b) 3495.3, 596 (d) in a circular path
(c) 2687, 593 (d) 2956, 771 60. Gases consist of large number of identical particles (atoms
51. 16 g of oxygen and 3 g of hydrogen are mixed and kept at or molecules) that are so small and so far apart on the average
760 mm of Hg pressure and 0° C. The total volume occupied that the actual volume of the molecules is negligible in
by the mixture will be nearly comparison to the empty space between them.
(a) 22.4 litres (b) 33.6 litres Above given statement explain which property of gases ?
(c) 448 litres (d) 44800 mL (a) Gases occupy all the space available to them.
52. The density of neon will be highest at (b) Gases has fixed shape.
(a) S.T.P. (b) 0ºC, 2 atm (c) Compressibility of gases.
(c) 273ºC, 1 atm. (d) 273ºC, 2 atm. (d) None of these.
53. An evacuated glass vessel weights 50 g when empty, 61. Which of the following assumption of kinetic molecular
144.0 g when filled with a liquid of density 0.47 g mL–1 and theory states that gases do not have fixed shape ?
50.5 g when filled with an ideal gas at 760 mm Hg at 300 (a) Particles of a gas move in all possible directions in
K. The molar mass of the ideal gas is straight line.
(Given R = 0.0821 L atm K–1 mol–1) (b) Particles of a gas are always in constant and random motion.
(a) 61.575 (b) 130.98 (c) 123.75 (d) 47.87 (c) Total energy of molecules before and after the collision
54. When 2 gm of a gas A is introduced into an evaluated flask remains same.
kept at 25ºC, the pressure is found to be one atmosphere. If (d) None of these
3 gm of another gas B is then added to the same flask, the 62. Kinetic theory of gases proves
total pressure becomes 1.5 atm. Assuming ideal gas (a) only Boyle’s law (b) only Charles’ law
behaviour, calculate the ratio of the molecular weights (c) only Avogadro’s law (d) All of these
MA : MB. 63. Which one of the following is the wrong assumption of
(a) 1 : 3 (b) 1 : 1 (c) 2 : 1 (d) 3 : 1 kinetic theory of gases ?
55. Two vessels containing gases A and B are interconected as (a) Momentum and energy always remain conserved.
shown in the figure. The stopper is opened, the gases are (b) Pressure is the result of elastic collision of molecules
allowed to mix homogeneously. The partial pressures of A with the container’s wall.
and B in the mixture will be, respectively (c) Molecules are separated by great distances compared
Gas A Gas B to their sizes.
(d) All the molecules move in straight line between collision
12 L 8L and with same velocity.
8 atm 5 atm Topic 6: Behaviour of Real Gases : Deviation from Ideal Gas
Behaviour
(a) 8 and 5 atom (b) 9.6 and 4 atm 64. When is deviation more in the behaviour of a gas from the
(c) 4.8 and 2 atm (d) 6.4 and 4 atm ideal gas equation PV = nRT ?
56. A neon-dioxygen mixture contains 70.6 g O2 and 167.5 g (a) At high temperature and low pressure
neon. If pressure of the mixture of gases in the cylinder is 25 (b) At low temperature and high pressure
bar. What is the partial pressure of O2 and Ne in the mixture (c) At high temperature and high pressure
respectively ? (d) At low temperature and low pressure
 EBD_7374
62 CHEMISTRY

65. In van der Waal’s equation of state of the gas law, the (iii) Value of 'a' is measure of magnitude of intermolecular
constant ‘b’ is a measure of attractive forces within the gas and depends on
(a) volume occupied by the molecules temperature and pressure of gas.
(b) intermolecular attraction (iv) At high pressure volume occupied by the molecules
(c) intermolecular repulsions also becomes significant because instead of moving in
(d) intermolecular collisions per unit volume volume V, these are now restricted to volume (V-nb)
66. In van der Waal’s equation of state for a non-ideal gas, the (a) (i) and (iv) (b) (i), (ii) and (iii)
term that accounts for intermolecular forces is (c) (i), (iii) and (iv) (d) (i) and (iii)
æ a ö 73. In case of CO and CH4 curve goes to minima then
(a) (V – b) (b) RT (c) çP + 2 ÷ (d) (RT)–1 increases with increase in pressure but in case of H2
è V ø
and He the curve is linear because:
67. A gas described by van der Waal’s equation
(i) behaves similar to an ideal gas in the limit of large molar CO CH4
volume H2
(ii) behaves similar to an ideal gas in the limit of large
pressure He
(iii) is characterised by van der Waal's coefficients that are
dependent on the identity of the gas but are
independent of the temperature PV Ideal gas
(iv) has the pressure that is lower than the pressure exerted
by the same gas behaving ideally
(a) (i) and (ii) (b) (i) and (iii)
(c) (i), (ii) and (iii) (d) (ii) and (iv)
68. The units of constant ‘a’ in van der Waal’s equation is P
(a) dm6 atm mol–2 (b) dm3 atm mol–1 (a) Intermolecular interactions for H2 and He are very
(c) dm atm mol –1 (d) atm mol–1 low.
69. The van der Waal’s constant ‘a’ for four gases P, Q, R and S (b) Molecular size or atomic size for H2 and He is small.
are 4.17, 3.59, 6.71 and 3.8 atm L2 mol–2 respectively. (c) Both (a) and (b)
Therefore, the ascending order of their liquefaction is (d) Neither (a) nor (b)
(a) R < P < S < Q (b) Q < S < R < P Topic 7: Liquifaction of Gases
(c) Q < S < P < R (d) R < P < Q < S
70. From the given figure what can be said about the gases 74. The gas with the highest critical temperature is
does not deviate much from ideal gases at (a) H2 (b) He (c) N2 (d) CO2
75. An ideal gas can’t be liquefied because
Real (a) its critical temperature is always above 0°C
Ideal
(b) Its molecules are relatively smaller in size
(c) it solidifies before becoming a liquid
(d) forces between its molecules are negligible
Pressure

76. Above Boyle point, real gases show ______X _______ from
ideality and Z values are _______Y ________ than one.
(a) X = Negative deviation, Y = Less
(b) X = Negative deviation, Y = Greater
(c) X = Positive deviation, Y = Less
Volume
(a) Higher pressure and low volume. (d) X = Positive deviation, Y = Greater
(b) Low pressure and low volume. 77. Select the one that when used would be considered as best
(c) High pressure and high volume. condition for liquification of a gas.
(d) Low pressure and high volume. (a) Increasing the temperature.
71. The compressibility factor for a real gas at high pressure is : (b) Decreasing the pressure.
(c) Increasing the pressure and decreasing the temperature.
RT pb pb
(a) 1 + (b) 1 (c) 1 + (d) 1 – (d) Decreasing the pressure and increasing the temperature.
pb RT RT 78. Following table represents critical temperature of some
gases. Arrange these gases in their increasing order of
72. Which of the following statements are correct ? liquifaction.
(i) Real gases show deviations from ideal gas law because
molecules interact with each other. Gas H2 He N2 O2
(ii) Due to interaction of molecules the pressure exerted Tc / K 33.2 5.3 126 154.3
by the gas is given as :
an 2 (a) He < N2 < H2 < O2 (b) H2 < He < N2 < O2
p real = p ideal + 2 (c) He < H2 < N2 < O2 (d) O2 < N2 < H2 < He
V
STATES OF MATTER 63

79. Choose the correct statement based on the following 84. The kinetic energy of molecules in gaseous state is
isotherms of carbon dioxide at various temperature. (a) more than those in the liquid state
G (b) less than those in the liquid state
H (c) equal to those in the liquid state
50°C
(d) less than those in solid state
P3 85. A pin or a needle floats on the surface of water, the reason
D 31.1°C for this is
(a) surface tension (b) less weight
73 (c) upthrust of liquid (d) None of the above
Pressure

(Pc ) E 86. Which of the following phenomena is caused by surface

33.98°C
C 21.5°C (Tc ) tension ?
P2 B
F (a) Particles at the bottom of river remain separated but
they stick together when taken out.
P1
13.1°C
(b) A liquid rise in a thin capillary.
A (c) Small drops of mercury from spherical bead instead of
spreading on the surface.
V3 V2 Vc V1 (d) All of the above
Volume 87. A drop of oil is placed on the surface of water. Which of the
(i) We can move from point A to F vertically by increasing following statement is correct ?
the temperature. (a) It will remain on it as a sphere
(ii) We can reach the point G by compressing the gas at (b) It will spread as a thin layer
constant temperature. (c) It will be partly as spherical droplets and partly as thin
(iii) We can move down from G towards D by increasing film
the temperature. (d) It will float as a distorted drop on the water surface
(iv) As soon as we cross the point D on the critical isotherm 88. When the temperature increases, the viscosity of
we get liquid. (a) gases decreases and viscosity of liquids increases
(a) (i) and (ii) (b) (i), (ii) and (iii) (b) gases increases and viscosity of liquids decreases
(c) (i), (ii) and (iv) (d) (i), (ii), (iii) and (iv) (c) gases and liquids increases
Topic 8: Liquid State (d) gases and liquids decreases
89. The surface tension of which of the following liquid is
80. At 1 atm pressure boiling temperature is called _____X____. maximum?
If pressure is 1 bar then the boiling point is called (a) C2H5OH (b) CH3OH
_____Y _____ of the liquid. (c) H2O (d) C6H6
(a) X = Standard boiling point, Y = Normal boiling point 90. In which phenomena water changes into water vapour below
(b) X = Normal boiling point, Y = Standard boiling point its b.p. ?
(c) X = Critical boiling point, Y = Normal boiling point (a) Evaporation (b) Condensation
(d) X = Critical boiling point, Y = Standard boiling point (c) Boiling (d) No such phenomena exist
81. Assertion : The temperature at which vapour pressure of a 91. The liquid which has the highest rate of evaporation is
liquid is equal to the external pressure is called boiling (a) petrol (b) nail-polish remover
temperature. (c) water (d) alcohol
Reason : At high altitude atmospheric pressure is high.
92. The correct order of viscosity of the following liquids will
(a) Assertion is correct, reason is correct; reason is a
be
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a (a) Water < methyl alcohol < dimethyl ether < glycerol
correct explanation for assertion (b) methyl alcohol < glycerol < water < dimethyl ether
(c) Assertion is correct, reason is incorrect (c) dimethyl ether < methyl alcohol < water < glycerol
(d) Assertion is incorrect, reason is correct. (d) glycerol < dimethyl ether < water < methyl alcohol
82. Which of the following statement is incorrect ? 93. Assertion : Liquids tend to have maximum number of
(a) Standard boiling point of liquid is slightly lower than molecules at their surface.
the normal boiling point. Reason : Small liquid drops have spherical shape.
(b) 1 atm pressure is slightly less than 1 bar pressure (a) Assertion is correct, reason is correct; reason is a
(c) The normal boiling point of water is 100°C and its correct explanation for assertion.
standard boiling point is 99.6°C (b) Assertion is correct, reason is correct; reason is not a
(d) None of the above correct explanation for assertion
83. A liquid can exist only (c) Assertion is correct, reason is incorrect
(a) between triple point and critical temperature
(d) Assertion is incorrect, reason is correct.
(b) at any temperature above the melting point
(c) between melting point and critical temperature 94. Which among the following has lowest surface tension ?
(d) between boiling and melting temperature (a) Hexane (b) Water
(c) CH3OH (d) CH3CH2OH
 EBD_7374
64 CHEMISTRY

95. Water droplets was not able to maintain its spherical (i) Velocity with which honey is flowing is slower in A
shape in the presence of gravity but mercury does, why ? than B (q being same in both cases)
(a) Force of attraction between atoms of mercury is very (ii) Velocity increases with increase in temperature.
high than that of molecules in case of water. (a) (i) and (ii) (b) Only (i)
(b) Surface tension of mercury is very high. (c) Only (ii) (d) Neither (i) nor (ii)
(c) Both (a) and (b) 97. Choose the incorrect statement in the following.
(d) Neither (a) nor (b) (a) Surface tension is the force acting per unit length
96. Consider the case of honey flowing over a slope for this perpendicular to the line drawn on the surface of the
situation which of the following statement(s) is/are liquid
correct ? (b) Surface tension of a liquid increases with increase in
temperature
(c) The SI unit of surface tension is J m–2
(d) Viscosity is a measure of resistance for the flow of
liquid

q (A) q (B)

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (c) polarisability of interacting particles
(d) strength of permanent dipoles in the particles
1. A person living in shimla observed that cooking food 5. Dipole-dipole forces act between the molecules possessing
without using pressure cooker takes more time. The reason permanent dipole. Ends of dipoles possess 'partial charges'.
for this observation is that at high altitude The partial charge is
(a) pressure increases (b) temperature decreases (a) more than unit electronic charge
(c) pressure decreases (d) temperature increases (b) equal to unit electronic charge
2. Which of the following property of water can be used to (c) less than unit electronic charge
explain the spherical shape of rain droplets? (d) double the unit electronic charge
(a) Viscosity (b) Surface tension 6. The pressure of a 1 : 4 mixture of dihydrogen and dioxygen
(c) Critical phenomena (d) Pressure enclosed in a vessel is one atmosphere. What would be the
3. A plot of volume (V) versus temperature (T) for a gas at partial pressure of dioxygen?
constant pressure is a straight line passing through the (a) 0.8 × 105 atm (b) 0.008 Nm–2
origin. The plots at different values of pressure are shown 4
(c) 8 × 10 Nm –2 (d) 0.25 atm
in figure. Which of the following order of pressure is correct 7. As the temperature increases average kinetic energy of
for this gas? molecules increases. What would be the effect of increase of
temperature on pressure provided the volume is constant?
P1 (a) Increases (b) Decreases
P2
Volume (mL) ®

P3 (c) Remains same (d) Becomes half

P4 8. Gases possess characteristic critical temperature which
depends upon the magnitude of intermolecular forces
between the particles. Following are the critical
temperatures of some gases.
Gases H 2 He O 2 N2
Temperature (K) ® Critical temperature in Kelvin 33.2 5.3 154.3 126
From the above data what would be the order of liquefaction
(a) P1 > P2 > P3 > P4 (b) P1 = P2 = P3 = P4
of these gases? Start writing the order from the gas
(c) P1 < P2 < P3 < P4 (d) P1 < P2 = P3 < P4
liquefying first
4. The interaction energy of London force is inversely
(a) H2, He, O2, N2 (b) He, O2, H2, N2
proportional to sixth power of the distance between two
(c) N2, O2, He, H2 (d) O2, N2, H2, He
interacting particles but their magnitude depends upon
9. What is SI unit of viscosity coefficient (h)?
(a) charge of interacting particles
(a) Pascal (b) Nsm–2 (c) km–2s (d) Nm–2
(b) mass of interacting particles
STATES OF MATTER 65

10. Atmospheric pressures recorded in different cities are as (a) Repulsive forces between molecules of gas
follows (b) Attractive forces between molecules of gas
Cities Shimla Bengaluru Delhi Mumbai (c) Volume occupied by gas molecules
2
p in N/m 1.01 ´ 10 5
1.2 ´ 10 5
1.02 ´ 10 1.21 ´ 105 5 (d) All of these
Consider the above data and mark the place at which liquid 19. A gas such as carbon monoxide would be most likely to
will boil first. obey the ideal gas law at : [NEET 2015 RS, C]
(a) Shimla (b) Bengaluru (c) Delhi (d) Mumbai (a) high temperatures and low pressures.
11. Which curve in figure represents the curve of ideal gas? (b) low temperatures and high pressures.
F (c) high temperatures and low pressures.
E D (d) low temperatures and low pressures.
C A 20. Cyclopropane and oxygen at partial pressures 170 torr and
PV ®

B 570 torr respectively are mixed in a gas cylinder. What is the

ratio of the number of moles of cyclopropane to the number
of moles of oxygen (nC3H6/nO2)? [AIIMS 2015, S]
170 ´ 42 170 æ 170 570 ö
0 P® (a) = 0.39 (b) ç + ÷ » 0.19
(a) Only B (b) C and D (c) E and F (d) A and B 570 ´ 32 42 è 42 32 ø
12. Increase in kinetic energy can overcome intermolecular 170 170
forces of attraction. How will the viscosity of liquid be (c) = 0.23 (d) = 0.30
740 570
affected by the increase in temperature?
(a) Increase 21. The intermolecular interaction that is dependent on the inverse
(b) No effect cube of distance between the molecules is :[JEE M 2015, C]
(c) Decrease (a) London force (b) hydrogen bond
(d) No regular pattern will be followed (c) ion - ion interaction (d) ion - dipole interaction
13. How does the surface tension of a liquid vary with increase 22. One mole of a monoatomic real gas satisfies the equation
in temperature? P(V – b) = RT where b is a constant. The relationship of
(a) Remains same interatomic potential V(r) and interatomic distance r for the
(b) Decreases gas is given by [JEE M 2015, S]
(c) Increases
(d) No regular pattern is followed
Past Year MCQs
14. Equal masses of H2,O2 and methane have been taken in a
container of volume V at temperature 27°C in identical (a)
conditions. The ratio of the volumes of gases H2 : O2 :
methane would be : [NEET 2014, S]
(a) 8 : 16 : 1 (b) 16 : 8 : 1 (c) 16 : 1 : 2 (d) 8 : 1 : 2
15. A bottle of dry ammonia and a bottle of dry hydrogen
chloride connected through a long tube are opened
simultaneously at both ends the white ammonium chloride
(b)
ring first formed will be [AIIMS 2014, C]
(a) at the centre of the tube.
(b) near the hydrogen chloride bottle.
(c) near the ammonia bottle.
(d) throughout the length of the tube.
16. The gas with the highest critical temperature is
[AIIMS 2014, C]
(a) H2 (b) He (c) N2 (d) CO2 (c)
17. If Z is a compressibility factor, van der Waals equation at
low pressure can be written as: [JEE M 2014, S]
RT a
(a) Z =1 + (b) Z =1 -
Pb VRT
Pb Pb
(c) Z =1- (d) Z = 1 +
RT RT (d)
18. In Van der Waal’s equation the constant b is the measure of
[BITSAT 2014, C]
 EBD_7374
66 CHEMISTRY

23. Equal moles of hydrogen and oxygen gases are placed in a 29. Pure hydrogen sulphide is stored in a tank of 100 litre capacity
container with a pin-hole through which both can escape. at 20°C and 2 atm pressure. The mass of the gas will be
What fraction of the oxygen escapes in the time required for [AIIMS 2017, A]
one-half of the hydrogen to escape ? [NEET 2016, A] (a) 34 g (b) 340 g (c) 282.68 g (d) 28.24 g
(a) 1/8 (b) 1/4 (c) 3/8 (d) 1/2 30. Assertion : At critical temperature liquid passes into
24. When a sample of gas is compressed at constant temperature gaseous state imperceptibly and continuously.
from 15 atm to 60 atm, its volume changes from 76 cm3 to Reason : The density of liquid and gaseous phase is equal
20.5 cm3. Which of the following statements are possible to critical temperature. [AIIMS 2017, C]
exlanations of this behaviour? [AIIMS 2016, C] (a) If both Assertion and Reason are correct and Reason
(1) The gas behaves non-ideally is the correct explanation of Assertion.
(b) If both Assertion and Reason are correct, but Reason
(2) The gas dimerises
is not the correct explanation of Assertion.
(3) The gas is adsorbed into the vessel walls
(c) If Assertion is correct but Reason is incorrect.
(a) 1, 2 and 3 (b) 1 and 2 only (d) If both the Assertion and Reason are incorrect.
(c) 2 and 3 only (d) 1 only 31. Which of the following represents Gay Lussac's law ?
25. Assertion : Gases do not liquefy above their critical [BITSAT 2017, A]
temperature, even on applying high pressure. P
Reason : Above critical temperature, the molecular speed is I. = constant II. P1T2 = P2T1
T
high and intermolecular attractions cannot hold the
III. P1V1 = P2V2
molecules together because they escape because of high
speed. [AIIMS 2016, C] Choose the correct option.
(a) If both Assertion and Reason are correct and Reason (a) I, II and III (b) II and III
is the correct explanation of Assertion. (c) I and III (d) I and II
32. The correction factor ‘a’ to the ideal gas equation corresponds
(b) If both Assertion and Reason are correct, but Reason
to [NEET 2018, C]
is not the correct explanation of Assertion.
(1) Density of the gas molecules
(c) If Assertion is correct but Reason is incorrect.
(2) Volume of the gas molecules
(d) If both the Assertion and Reason are incorrect. (3) Forces of attraction between the gas molecules
26. Two closed bulbs of equal volume (V) containing an ideal (4) Electric field present between the gas molecules
gas initially at pressure Pi and temperature T 1 are 33. Given van der Waals constants for NH3, H2, O2 and CO2 are
connected through a narrow tube of negligible volume as respectively 4.17, 0.244, 1.36 and 3.59, which one of the
shown in the figure below. The temperature of one of the following gases is most easily liquefied? [NEET 2018, C]
bulbs is then raised to T2. The final pressure pf is : (a) NH3 (b) H2 (c) CO2 (d) O2
[JEE M 2016, A] 34. In vander waal equation at constant temperature of 300 K,
a = 1.4 atm L2 mol–2, V = 100 mL , n = 1 mole, what is pressure
T1 T1 T1 T2 of gas ? [AIIMS 2018, A]
(a) 42 atm (b) 210 atm (c) 500 atm (d) 106 atm
Pf,V Pf,V
35. Assertion : When ideal gas expand from P1 ,V1 ,T1 to
P2 ,V2 ,T2 in multiple steps, work done is high in case where
æ T ö æ T T ö which number of steps are high.
(a) 2 Pi ç 2 ÷ (b) 2 Pi ç 1 2 ÷
è T1 + T2 ø è T1 + T2 ø Reason : Work is path function. [AIIMS 2018, C]
(a) If both assertion and reason are true and reason is the
æ T T ö æ T1 ö correct explanation of assertion.
(c) Pi ç 1 2 ÷ (d) 2 Pi ç
è T1 + T2 ø è T1 + T2 ÷ø (b) If both assertion and reason are true but reason is not
the correct explanation of assertion.
27. The average kinetic energy of an ideal gas per molecule in (c) If assertion is true but reason is false.
SI unit at 25° C will be (d) If both assertion and reason are false.
[BITSAT 2016, A] 36. Assertion : Compressibility factor (Z) for non-ideal gases
-21
(a) 6.17 × 10 kJ (b) 6.17 × 10–21 J can be greater than 1.
(c) 6.17 × 10 J –20 (d) 7.16 × 10–20 J Reason : Non-ideal gases always exert higher pressure than
28. At what temperature, the rate of effusion of N2 would be expected. [AIIMS 2018, C]
1.625 times than that of SO2 at 50o C ? [BITSAT 2016, C] (a) If both assertion and reason are true and reason is the
(a) 110 K (b) 173 K (c) 373 K (d) 273 K correct explanation of assertion.
STATES OF MATTER 67

(b) If both assertion and reason are true but reason is not 37. It V is the volume of one molecule of gas under given
the correct explanation of assertion. conditions, the van der Waal’s constant b is [BITSAT 2018]
(c) If assertion is true but reason is false. 4V N0
(d) If both assertion and reason are false. (a) 4 V (b) (c) (d) 4VN0
N0 4V

Exercise 3 : Try If You Can

1. A container contains certain gas of mass ‘m’ of high (a) Pressure of the gas is minimum in (III) container
pressure. Some of the gas has been allowed to escape from (b) Pressure of the gas is equal in I and II container
the container and after some time the pressure of the gas (c) Pressure of the gas is maximum in (I)
becomes half and its absolute temperature 2/3 rd. The (d) The ratio of pressure in II and III container is 4 : 3
amount of the gas escaped is 6. I, II, and III are three isotherms, respectively, at T1, T2 and
(a) 2/3 m (b) 1/2 m (c) 1/4 m (d) 1/6 m T3. Temperature will be in order
2. A volume V of a gas at temperature T1 and a pressure p is
enclosed in a sphere. It is connected to another sphere of
volume V/2 by a tube and stopcock. The second sphere is
initially evacuated and the stopcock is closed. If the stopcock
P
is opened the temperature of the gas in the second sphere
becomes T2. The first sphere is maintained at a temperature
T1. What is the final pressure p1 within the apparatus ? I
2pT2 2pT2 II
(a) (b) T + 2T III
2T2 + T1 2 1
V3 V2 V1
pT2 2pT2
(c) (d) T + T (a) T1 = T2 = T3 (b) T1 < T2 < T3
2T2 + T1 1 2 (c) T1 > T2 > T3 (d) T1 > T2 = T3
3. Cyclopropane and oxygen at partial pressures 170 torr and 7. Starting out on a trip into the mountains, you inflate the
570 torr respectively are mixed in a gas cylinder. What is the tires on your automobile to a recommended pressure of
ratio of the number of moles of cyclopropane to the number 3.21 × 105 pa on a day when the temperature is – 5.0°C. You
of moles of oxygen (nC3H6/nO2)? drive to the beach, where the temperature is 28.0°C. Assume
170 ´ 42 that the volume of the tire has increased by 3%. What is
170 æ 170 570 ö
(a) = 0.39 (b) ç + ÷ » 0.19 the final pressure in the tyres?
570 ´ 32 42 è 42 32 ø (a) 350 Pa (b) 3500 Pa
170 170 (c) 3.5 × 105 Pa (d) None of these
(c) = 0.23 (d) = 0.30
740 570 8. At STP, a container has 1 mole of He, 2 mole Ne, 3 mole O 2
4. At 100°C and 1 atm, if the density of liquid water is 1.0 g cm–3 and 4 mole N2. without changing total pressure if 2 mole of
and that of water vapour is 0.0006 g cm–3, then the volume O2 is removed. The partial pressure of O2 will be decreased by:
occupied by water molecules in 1 litre of steam at that (a) 26% (b) 40% (c) 58.33% (d) 66.66%
temperature is 9. The van der Waal's equation for n = 1 mol may be expressed
(a) 6 cm3 (b) 60 cm3 (c) 0.6 cm3 (d) 0.06 cm3 æ RT ö 2 aV ab
as V 3 - ç b + ÷V + - =0
5. There are three closed containers in which equal amount of ç p ÷ø p p
è
the gas are filled. Where V is the molar volume of the gas. Which of the
following is correct?
(a) For a temperature less than Tc, V has three real roots
(b) For a temperature more than Tc, V has one real and two
10cm imaginary roots
R=10cm
(c) For a temperature equal to Tc all three roots of V are
real and identical
Sphere (d) All of these
10cm (hollow)
(cube) 10 cm 10. For real gases van der Waals equation is written as
(I) (II) (III)
æ an 2 ö
If all the containers are placed at the same temperatures, çè p + ÷ (V– nb) = nRT
V2 ø
then find the incorrect options – where ‘a’ and ‘b’ are van der Waals constants.
 EBD_7374
68 CHEMISTRY

Two sets of gases are : in the larger flask B2 exerts a pressure of 1 atm at 400 K
(I) O2, CO2, H2 and He when they are separated out by a close valve. The gases
(II) CH4, O2 and H2 are mixed by opening the stop cock and after the end of the
The gases given in set-I in increasing order of ‘b’ and gases reaction the flask are cooled to 250 K.
given in set-II in decreasing order of ‘a’, are arranged below.
Select the correct order from the following :
(a) (I) He < H2 < CO2 < O2 (II) CH4 > H2 > O2 AB (g) B2 (g)
(b) (I) O2 < He < H2 < CO2 (II) H2 > O2 > CH4
(c) (I) He < H2 < O2 < CO2 (II) CH4 > O2 > H2 8.21 L
(d) (I) H2 < O2 < He < CO2 (II) O2 > CH4 > H2 8.21 L
11. A mixture of Ne and Ar kept in a closed vessel at 250 K has The final pressure is :
a total K.E. = 3kJ. The total mass of Ne and Ar is 30 g. Find (a) 0.156 atm (b) 0.3125 atm
mass % of Ne in gaseous mixture at 250 K. (c) 0.625 atm (d) 3.2 atm
(a) 61.63 (b) 38.37 (c) 50% (d) 28.3 14. For a real gas (mol. mass = 60) if density at critical point is
12. Which gas shows real behaviour? 4 ´105
(a) 16 g O2 at 1 atm and 273 K occupies 11.2 L 0.80 g/cm3 and its Tc = K, then van der waals’
821
(b) 1 g H2 in 0.5 L flask exerts pressure of 24.63 atm at
300 K constant a (in atm L2 mol–2) is
(c) 1 mole NH3 at 300 K and 1 atm occupies volume 22.4 L (a) 0.3375 (b) 3.375 (c) 1.68 (d) 0.025
(d) 5.6 L of CO2 at 1 atm and 273 K is equal to 11 g 15. A spherical balloon of 21 cm diameter is to be filled up with
13. At room temperature following reaction goes to completion hydrogen at STP from a cylinder containing the gas at
2AB(g) + B2(g) ® 2AB2(g) 20 atm at 28 °C. If the cylinder can hold 2.82 L of water, the
AB2 is solid with negligible vapour pressure below 0°C. At number of balloons that can be filled up are
300 K, AB in the smaller flask exerts a pressure of 3 atm and (a) 5 (b) 7 (c) 9 (d) 10

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 11 (d) 21 (b) 31 (a) 41 (d) 51 (d) 61 (b) 71 (c) 81 (c) 91 (a)
2 (d) 12 (c) 22 (a) 32 (d) 42 (a) 52 (b) 62 (d) 72 (a) 82 (b) 92 (c)
3 (a) 13 (c) 23 (b) 33 (b) 43 (a) 53 (a) 63 (d) 73 (c) 83 (d) 93 (d)
4 (b) 14 (c) 24 (d) 34 (c) 44 (a) 54 (a) 64 (b) 74 (d) 84 (a) 94 (a)
5 (c) 15 (c) 25 (d) 35 (b) 45 (d) 55 (c) 65 (a) 75 (d) 85 (a) 95 (c)
6 (a) 16 (a) 26 (a) 36 (d) 46 (a) 56 (d) 66 (c) 76 (d) 86 (d) 96 (a)
7 (d) 17 (a) 27 (c) 37 (c) 47 (d) 57 (a) 67 (b) 77 (c) 87 (b) 97 (b)
8 (c) 18 (b) 28 (d) 38 (a) 48 (d) 58 (c) 68 (a) 78 (c) 88 (b)
9 (c) 19 (b) 29 (a) 39 (a) 49 (d) 59 (b) 69 (c) 79 (a) 89 (c)
10 (a) 20 (c) 30 (b) 40 (b) 50 (a) 60 (c) 70 (d) 80 (b) 90 (a)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (c) 5 (c) 9 (b) 13 (b) 17 (b) 21 (b) 25 (a) 29 (c) 33 (a) 37 (d)
2 (b) 6 (c) 10 (a) 14 (c) 18 (c) 22 (c) 26 (a) 30 (a) 34 (d)
3 (c) 7 (a) 11 (a) 15 (b) 19 (a) 23 (a) 27 (b) 31 (d) 35 (b)
4 (c) 8 (d) 12 (c) 16 (d) 20 (d) 24 (d) 28 (c) 32 (c) 36 (c)
Exercis e 3 : Try If You Can
1 (c) 3 (d) 5 (b) 7 (c) 9 (d) 11 (d) 13 (c) 15 (d)
2 (a) 4 (c) 6 (c) 8 (c) 10 (c) 12 (c) 14 (b)
 Chapter
6 THERMODYNAMICS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

8
7
6
AIPMT /NEET
5
Number of Questions

AIIMS
4
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 5 Criteria for spontaneity,
AIIMS 3 Entropy, Calculation of work 4/5 8.1
JEE Main 3 done, Gibbs free energy
BITSAT 2
 EBD_7374
70 CHEMISTRY
THERMODYNAMICS 71
 EBD_7374
72 CHEMISTRY

Exercise 1 : Topic-wise MCQs

9. Adiabatic expansions of an ideal gas is accompanied by
Topic 1: Thermodynamics
(a) decrease in DE
1. Which of the following statements is not true regarding the (b) increase in temperature
laws of thermodynamics ? (c) decrease in DS
(a) It deal with energy changes of macroscopic systems. (d) no change in any one of the above properties
(b) It deal with energy changes of microscopic systems.
10. Assertion : Absolute value of internal energy of a substance
(c) It does not depends on the rate at which these energy
cannot be determined.
transformations are carried out.
(d) It depends on initial and final states of a system Reason : It is impossible to determine exact values of
undergoing the change. constitutent energies of the substances.
2. Which of the following is closed system ? (a) Assertion is correct, reason is correct; reason is a
(a) Jet engine correct explanation for assertion.
(b) Tea placed in a steel kettle (b) Assertion is correct, reason is correct; reason is not a
(c) Pressure cooker correct explanation for assertion
(d) Rocket engine during propulsion (c) Assertion is correct, reason is incorrect
3. The state of a thermodynamic system is described by its (d) Assertion is incorrect, reason is correct.
measurable or macroscopic (bulk) properties. These are 11. Read the following statements carefully and choose the
(a) Pressure and volume correct option
(b) Pressure, volume, temperature and amount (i) Internal energy, U, of the system is a state function.
(c) Volume, temperature and amount (ii) –w shows, that work is done on the system.
(d) Pressure and temperature (iii) +w shows, that work is done by the system
4. Which of the following are not state functions ?
(a) (i) and (ii) are correct (b) (ii) and (iii) are correct
(I) q + w (II) q
(c) (i) and (iii) are correct (d) Only (i) is correct
(III) w (IV) H - TS
(a) (I) and (IV) (b) (II), (III) and (IV) 12. According to the first law of thermodynamics which of the
(c) (I), (II) and (III) (d) (II) and (III) following quantities represents change in a state function ?
5. Among the following the state function(s) is (are) (a) qrev (b) qrev – Wrev
(i) Internal energy (c) qrev/Wrev (d) qrev + Wrev
(ii) Irreversible expansion work 13. According to the first law of thermodynamics, DU = q + W.
(iii) Reversible expansion work In special cases the statement can be expressed in different
(iv) Molar enthalpy ways. Which of the following is not a correct expression ?
(a) (ii) and (iii) (b) (i), (ii) and (iii) (a) At constant temperature q = –W
(c) (i) and (iv) (d) (i) only (b) When no work is done DU = q
6. Enthalpy change (DH) of a system depends upon its (c) In gaseous system DU = q + PDV
(a) Initial state (d) When work is done by the system : DU = q + W
(b) Final state 14. Assertion : A process is called adiabatic if the system does
(c) Both on initial and final state not exchange heat with the surroundings.
(d) None of these
Reason : It does not involve increase or decrease in
7. Which of the following factors affect the internal energy of
temperature of the system.
the system ?
(a) Assertion is correct, reason is correct; reason is a
(a) Heat passes into or out of the system.
correct explanation for assertion.
(b) Work is done on or by the system.
(c) Matter enters or leaves the system. (b) Assertion is correct, reason is correct; reason is not a
(d) All of the above correct explanation for assertion
8. Assertion : T, P and V are state variables or state functions. (c) Assertion is correct, reason is incorrect
Reason : Their values depend on the state of the system (d) Assertion is incorrect, reason is correct.
and how it is reached.
Topic 2: Applications
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion. 15. Figure below is showing that one mole of an ideal gas is
(b) Assertion is correct, reason is correct; reason is not a fitted with a frictionless piston. Total volume of the gas is Vi
correct explanation for assertion and pressure of the gas inside is p. If external pressure is p ex
(c) Assertion is correct, reason is incorrect which is greater than p is applied, piston is moved inward
(d) Assertion is incorrect, reason is correct. till the pressure inside becomes equal to pex.
THERMODYNAMICS 73

21. If a reaction involves only solids and liquids which of the

Pex following is true ?
(a) DH < DE (b) DH = DE
Pressure, P

(c) DH > DE (d) DH = DE + RTDn

Area = PexDV 22. During isothermal expansion of an ideal gas, its
(a) internal energy increases
(b) enthalpy decreases
(c) enthalpy remains unaffected
Vf Vi Volume, V
(d) enthalpy reduces to zero.
Pex 23. Assume each reaction is carried out in an open container.
For which reaction will DH = DE ?
(a) C(s) + 2H2O (g) ® 2H2 (g) + CO2 (g)
(b) PCl5 (g) ® PCl3 (g) + Cl2 (g)
(c) 2CO (g) + O2 (g) ® 2CO2 (g)
Pex
(d) H2 (g) + Br 2 (g) ® 2 HBr (g)
1
24. For the reaction CO (g ) + O 2 (g ) ® CO 2 (g )
2
l Which one of the statement is correct at constant T and P ?
What does the shaded area represents in the figure ? (a) DH = DE
(a) Work done (b) Pressure change
(b) DH < DE
(c) Volume change (d) Temperature change
(c) DH > DE
16. When 1 mol of a gas is heated at constant volume,
temperature is raised from 298 to 308 K. If heat supplied to (d) DH is independent of physical state of the reactants
the gas is 500 J, then which statement is correct ? 25. Assertion : At constant temperature and pressure whatever
(a) q = w = 500 J, DU = 0 (b) q = DU = 500 J, w = 0 heat absorbed by the system is used in doing work.
(c) q = –w = 500 J, DU = 0 (d) DU = 0, q = w = –500 J Reason : Internal energy change is zero.
17. Which of the following statements/relationships is not (a) Assertion is correct, reason is correct; reason is a
correct in thermodynamic changes ? correct explanation for assertion.
(a) DU = 0 (isothermal reversible expansion of a gas) (b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion
V
(b) w = – nRT ln 2 (isothermal reversible expansion of (c) Assertion is correct, reason is incorrect
V1 (d) Assertion is incorrect, reason is correct.
an ideal gas) 26. Match the columns
V Column-I Column-II Vf
(c) w = nRT ln 2 (isothermal reversible expansion of an (A) Free expansion at (p) q = – w = nRT ln V
V1 i
DV = 0
ideal gas) (B) Isothermal irreversible (q) DU = wad
(d) For a system of constant volume heat involved directly change
changes to internal energy. (C) Isothermal reversible (r) DU = qv
18. An ideal gas expands in volume from 1×10–3 to 1 × 10–2 m3 at change
300 K against a constant pressure of 1×105 Nm–2. The work (D) For adiabatic change (s) q = – w = Pex (Vf – Vi)
done is (a) A – (s), B – (p), C – (r), D – (q)
(a) 270 kJ (b) – 900 kJ (c) – 900 J (d) 900 kJ (b) A – (r), B – (q), C – (p), D – (s)
19. The difference between DH and DU is usually significant (c) A – (r), B – (s), C – (p), D – (q)
for systems consisting of (d) A – (q), B – (r), C – (s), D – (p)
(a) only solids (b) only liquids 27. Match the columns
(c) both solids and liquids (d) only gases Column-I Column-II
20. Match the columns (A) pext = 0 (p) Free expansion of an
Column-I Column-II ideal gas
(A) Cm (p) Cv DT (B) q = pext (Vf – Vi) (q) Adiabatic change
(B) q (q) C/n (C) q = 2.303 nRT log (Vf / Vi) (r) Isothermal reversible
(C) DU (r) Cp DT change
(D) DH (s) C DT (D) DU = Wad (s) Isothermal irreversible
(a) A – (q), B – (s), C – (r), D – (p) change
(b) A – (q), B – (s), C – (p), D – (r) (a) A – (p), B – (s), C – (r), D – (q)
(c) A – (s), B – (q), C – (p), D – (r) (b) A – (p), B – (q), C – (r), D – (s)
(d) A – (q), B – (p), C – (r), D – (s) (c) A – (p), B – (r), C – (s), D – (q)
(d) A – (p), B – (r), C – (q), D – (s)
 EBD_7374
74 CHEMISTRY

28. Assertion : For an isothermal reversible process Q = –W i.e. 37. The internal energy change when a system goes from state A
work done by the system equals the heat absorbed by the system. to B is 40 kJ/mol. If the system goes from A to B by a reversible
Reason : Enthalpy change (DH) is zero for isothermal path and returns to state A by an irreversible path what would
process. be the net change in internal energy ?
(a) Assertion is correct, reason is correct; reason is a (a) > 40 kJ (b) < 40 kJ (c) Zero (d) 40 kJ
correct explanation for assertion. 38. Under isothermal condition for one mole of ideal gas what
(b) Assertion is correct, reason is correct; reason is not a is the ratio of work done under reversible to irreversible
correct explanation for assertion
process, initially held at 20 atm undergoes expansion from
(c) Assertion is correct, reason is incorrect
1L to 2L, at 298K, under external pressure of 10 atm?
(d) Assertion is incorrect, reason is correct.
29. For the reaction (a) 1.7 (b) 2.0 (c) 1.4 (d) 1.0
39. An ideal gas is allowed to expand both reversibly and
C3 H8 (g) + 5O2 (g) ® 3CO2 (g) + 4H 2 O(l) irreversibly in an isolated system. If T i is the initial
at constant temperature, DH – DE is temperature and Tf is the final temperature, which of the
(a) – RT (b) + RT (c) – 3 RT (d) + 3 RT following statements is correct?
30. Consider the reaction : N 2 + 3H 2 ® 2 NH 3 carried out at (a) (Tf)rev = (Tf)irrev
constant temperature and pressure. If DH and DU are the (b) Tf = Ti for both reversible and irreversible processes
enthalpy and internal energy changes for the reaction, which (c) (Tf)irrev > (Tf)rev
of the following expressions is true ? (d) Tf > Ti for reversible process but Tf = Ti for irreversible
(a) DH > DU (b) DH < DU process
(c) DH = DU (d) DH = 0 40. Assertion : The mass and volume of a substance are the
31. Among the following, the intensive properties are extensive properties and are proportional to each other.
(i) molar conductivity (ii) electromotive force Reason : The ratio of mass of a sample to its volume is an
(iii) resistance (iv) heat capacity intensive property.
(a) (ii) and (iii) (b) (i), (ii) and (iii) (a) Assertion is correct, reason is correct; reason is a
(c) (i) and (iv) (d) (i) only correct explanation for assertion.
32. Which is an extensive property of the system ? (b) Assertion is correct, reason is correct; reason is not a
(a) Volume (b) Viscosity correct explanation for assertion
(c) Temperature (d) Refractive index (c) Assertion is correct, reason is incorrect
33. Which of the following factors do not affect heat capacity? (d) Assertion is incorrect, reason is correct.
(a) Size of system (b) Composition of system 41. How many molecules of ATP, undergo hydrolysis to raise
(c) Nature of system (d) Temperature of the system the temperature of 180 kg of water which was originally at
34. If DH is the change in enthalpy and DE, the change in room temperature by 1°C ? C{P,m} water = 75.32 J/mol/K,
internal energy accompanying a gaseous reaction, then DH{P} for ATP hydrolysis= 7 kcal/mol
(a) DH is always greater than DE (a) 1.5 × 1025 (b) 2.00 × 1023
(c) 3.4 × 10 25 (d) 4.0 × 1024
(b) DH < D E only if the number of moles of the products
is greater than the number of moles of the reactants 42. What is the amount of heat (in Joules) absorbed by 18 g of
water initially at room temperature heated to 100°C ? If 10 g
(c) D H is always less than D E
of Cu is added to this water , than decrease in temperature
(d) D H < D E only if the number of moles of products is
(in Kelvin) of water was found to be? C (p,m) for water
less than the number of moles of the reactants
35. For an isothermal reversible expansion process, the value 75.32 J/mol K ; C (p,m) for Cu = 24.47 J/mol K.
of q can be calculated by the expression (a) 5649, 369 (b) 5544, 324
(c) 5278, 342 (d) 3425, 425
V2 V 43. Calorie is equivalent to :
(a) q = 2.303nRT log q = -2.303nRT log 2
V1 (b) V1 (a) 0.4184 Joule (b) 4.184 Joule
V1 (c) 41.84 Joule (d) 418.4 Joule
(c) q = -Pexp nRT log V (d) None of these
2 44. Equal volumes of two monoatomic gases, A and B, at same
36. Assertion : Internal energy is an extensive property. temperature and pressure are mixed. The ratio of specific
Reason : Internal energy depends upon the amount of the heats (Cp/Cv) of the mixture will be :
system.
(a) 0.83 (b) 1.50 (c) 3.3 (d) 1.67
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion. 45. The molar heat capacity of water at constant pressure is
(b) Assertion is correct, reason is correct; reason is not a 75 JK–1 mol–1. When 1kJ of heat is supplied to 100 g of
correct explanation for assertion water, which is free to expand, the increase in temperature
(c) Assertion is correct, reason is incorrect of water is
(d) Assertion is incorrect, reason is correct. (a) 6.6 K (b) 1.2 K (c) 2.4 K (d) 4.8 K
THERMODYNAMICS 75

46. Assertion : First law of thermodynamics is applicable to an Enthalpy for the reaction,
electric fan or a heater.
Reason : In an electric fan, the electrical energy is converted H H H H
| | | |
into mechanical work that moves the blades. In a heater,
C = C + H - H ¾¾
® H - C- C - H
electrical energy is converted into heat energy. | | | |
(a) Assertion is correct, reason is correct; reason is a H H H H
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a will be:
correct explanation for assertion (a) – 243.6 kJ mol–1 (b) –120.0 kJ mol–1
(c) 553.0 kJ mol –1 (d) 1523.6 kJ mol–1
(c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct. 53. The following two reactions are known :
Fe2O3(s) + 3CO (g) ¾¾ ® 2Fe(s) + 3CO2(g); DH = –26.8 kJ
Topic 3: Enthalpy Change, DrH of a Reacion – Reaction Enthalpy FeO(s) + CO(g) ¾¾ ® Fe(s) + CO2(g); DH = –16.5 kJ
47. Which of the following is not true regarding thermo-chemical The value of D H for the following reaction
equations? Fe2O3(s) + CO(g) ¾¾ ® 2FeO(s) + CO2(g) is;
(a) The coefficients in a balanced thermo-chemical (a) + 6.2 kJ (b) + 10.3 kJ (c) – 43.3 kJ (d) – 10.3 kJ
equation refer to the number of moles of reactants and 54. Assertion : When a solid melts, decrease in enthalpy is
products involved in the reaction observed.
(b) The coefficients in a balanced thermo-chemical Reason : Melting of a solid is endothermic.
equation refer to the number of molecules of reactants (a) Assertion is correct, reason is correct; reason is a
and products involved in the reaction correct explanation for assertion.
(c) The numerical value of Dr H refers to the number of (b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion
moles of substances specified by an equation.
(c) Assertion is correct, reason is incorrect
-
(d) Standard enthalpy change Dr Hd will have units as (d) Assertion is incorrect, reason is correct.
-1
kJ mol . 55. If enthalpies of formation of C 2 H 4 (g) , CO2(g) and
48. If enthalpies of formation of C 2 H 4 (g) , CO 2(g) and H 2 O(l) at 25°C and 1atm pressure are 52, – 394 and
H 2 O(l) at 25°C and 1atm pressure are 52, – 394 and –286 kJ/mol respectively, the change in enthalpy is equal to
– 286 kJ/mol respectively, the change in ethalpy is equal to (a) – 141.2 kJ/mol (b) – 1412 kJ/mol
(a) – 141.2 kJ/mol (b) – 1412 kJ/mol (c) + 14.2 kJ/mol (d) + 1412 kJ/mol
(c) + 14.2 kJ/mol (d) + 1412 kJ/mol 56. Hess’s law is used to calculate :
49. The enthalpy change for a reaction does not depend upon (a) enthalpy of reaction. (b) entropy of reaction
(a) use of different reactants for the same product (c) work done in reaction (d) All of the above
(b) the nature of intermediate reaction steps 57. Which of the following statement is incorrect ?
(c) the differences in initial or final temperatures of (a) The standard enthalpy of reaction is the enthalpy
involved substances change for a reaction when all the participating
(d) the physical states of reactants and products substances are in their standard states.
50. Assertion : The value of enthalpy of neutralization of weak (b) The standard state of a substance at a specified
acid and strong base is numerically less than 57.1 kJ. temperature is its pure form at 1 bar.
Reason : All the OH– ions furnished by 1 g equivalent of (c) The standard state of solid iron at 298 K is pure iron at
strong base are not completely neutralized. 1 bar
(a) Assertion is correct, reason is correct; reason is a (d) Standard conditions are denoted by adding the
correct explanation for assertion. - to the symbol DH e.g., -DH d-
superscript d
(b) Assertion is correct, reason is correct; reason is not a 58. What is the internal energy (kJ) change occurs when 36 g
correct explanation for assertion of H2O(l) converted to H2O(g)? DH°(vapourisation) =
(c) Assertion is correct, reason is incorrect 40.79kJ/mol
(d) Assertion is incorrect, reason is correct. (a) 75.38 (b) 80.98 (c) 70.98 (d) 45.89
51. Given that bond energies of H – H and Cl – Cl are 430 kJ mol– 1 59. Consider the reaction :
and 240 kJ mol–1 respectively and DHf for HCl is – 90 kJ mol– 1, 4NO2 (g) + O2 (g) ® 2N 2O5 (g),
bond enthalpy of HCl is
(a) 380 kJ mol–1 (b) 425 kJ mol–1 DrH = – 111 kJ.
(c) 245 kJ mol–1 (d) 290 kJ mol–1 If N2O5(s) is formed instead of N2O5(g) in the above reaction,
52. From the following bond energies: the DrH value will be :
H – H bond energy: 431.37 kJ mol–1 (given, DH of sublimation for N2O5 is –54 kJ mol–1)
C = C bond energy: 606.10 kJ mol–1 (a) + 54 kJ (b) + 219 kJ (c) – 219 J (d) – 165 kJ
C – C bond energy: 336.49 kJ mol–1 60. The standard enthalpy of formation (Df H° 298) for methane,
C – H bond energy: 410.50 kJ mol–1 CH4 is – 74.9 kJ mol–1. In order to calculate the average
 EBD_7374
76 CHEMISTRY

energy given out in the formation of a C – H bond from this (iii) CO2(g) + H2(g) = CO(g) + H2O(l)
it is necessary to know which one of the following? DH = – X3 kJ mol–1
(a) The dissociation energy of the hydrogen molecule, H2.
5
(b) The first four ionisation energies of carbon. (iv) C 2 H 2 (g) + O2 (g) = 2CO2(g) + H2O(l)’
(c) The dissociation energy of H2 and enthalpy and 2
sublimation of carbon (graphite). DH = + 4X4 kJ mol–1
(d) The first four ionisation energies of carbon and electron Enthalpy of formation of H2O (l) is
affinity of hydrogen. (a) + X3 kJ mol– 1 (b) – X4 kJ mol– 1
(c) + X1 kJ mol – 1 (d) – X2 kJ mol– 1
Topic 4: Enthalpies for Different Types of Reactions 67. Diborane is a potential rocket fuel which undergoes
61. Which of the following statements is true for the given combustion according to the equation
reaction? B2 H 6 (g) + 3O 2 (s) ¾¾
® B2 O 3 (s) + 3H 2O(g)
Na ( s ) ® Na ( g ) ; DHd- = 108.4 kJ mol –1 Calculate the enthalpy change for the combustion of
(a) The enthalpy of atomization is same as the enthalpy of diborane. Given
vaporisation 3
(i) 2B(s) + O 2 (g) ¾¾ ® B2 O3 (s); DH = –1273 kJ per mol
(b) The enthalpy of atomization is same as the enthalpy of 2
sublimation. 1
(c) The enthalpy of atomization is same as the bond (ii) H 2 (g) + O 2 (g) ¾¾ ® H 2O(l); DH = –286 kJ per mol
2
enthalpy
(d) The enthalpy of atomization is same as the enthalpy of
(iii) H 2 O(l) ¾¾ ® H 2 O(g); DH = 44 kJ per mol
solution (iv) 2B (s) + 3H2 (g) ¾¾ ® B2H6 (g); DH = 36 kJ per mol
62. Given that heat of neutralisation of strong acid and strong (a) + 2035 kJ per mol (b) – 2035 kJ per mol
base is – 57.1 kJ. The heat produced when 0.25 mole of HCl is (c) + 2167 kJ per mol (d) – 2167 kJ per mol
neutralised with 0.25 mole of NaOH in aqueous solution is : Topic 5: Spontaneity, Gibbs Energy Change and
(a) 14.275 kJ (b) 57.1 kJ (c) 22.5 kJ (d) 28.6 kJ
Equilibrium Constant
63. Match the columns
Column-I Column-II 68. Pick out the wrong statement
13 (a) The standard free energy of formation of all elements
(A) C4 H10 + O 2 ® (p) Enthalpy of atomisation is zero
2 (b) A process accompanied by decrease in entropy is
4CO2 + 5H 2O; DH = – w spontaneous under certain conditions
(B) CH4 ® C + 4H ; DH = x (q) Enthalpy of formation (c) The entropy of a perfectly crystalline substance at
(C) H2+ Br2 ® 2HBr ; DH = y (r) Enthalpy of combustion absolute zero is zero
(D) Na–(s) ® Na(g) ; DH = z (s) Enthalpy of sublimation (d) A process that leads to increase in free energy will be
(a) A – (s), B – (p), C – (q), D – (r) spontaneous
(b) A – (q), B – (r), C – (p), D – (s) 69. Identify the correct statement for change of Gibbs energy
(c) A – (r), B – (p), C – (q), D – (s) for a system (DGsystem) at constant temperature and pressure
(d) A – (p), B – (q), C – (s), D – (r) (a) If DGsystem = 0, the system has attained equilibrium
64. For complete combustion of ethanol, (b) If DGsystem = 0, the system is still moving in a particular
C2 H5OH ( l ) + 3O 2 ( g ) ¾¾
® 2CO2 ( g ) + 3H 2 O ( l ) , direction
the amount of heat produced as measured in bomb (c) If DGsystem < 0, the process is not spontaneous
calorimeter, is 1364.47 kJ mol–1 at 25ºC. Assuming ideality (d) If DGsystem > 0, the process is not spontaneous
the enthalpy of combustion, DcH, for the reaction will be: 70. Identify the correct statement regarding a spontaneous
process:
(R = 8.314 kJ mol–1)
(a) Lowering of energy in the process is the only criterion
(a) -1366.95 kJ mol-1 (b) -1361.95 kJ mol-1 for spontaneity.
(c) -1460.95 kJ mol-1 (d) -1350.50 kJ mol-1 (b) For a spontaneous process in an isolated system, the
65. Standard enthalpy of vapourisation Dvap H° for water at change in entropy is positive.
100°C is 40.66 kJ mol–1. The internal energy of vaporisation (c) Endothermic processes are never spontaneous.
of water at 100°C (in kJ mol–1) is : (d) Exothermic processes are always spontaneous.
(a) + 37.56 (b) – 43.76 (c) + 43.76 (d) + 40.66 71. A chemical reaction will be spontaneous if it is accompanied
(Assume water vapour to behave like an ideal gas). by a decrease of
66. Consider the following reactions: (a) entropy of the system.
(i) H +(aq) + OH–(aq) = H2O(l), (b) enthalpy of the system.
DH = – X1 kJ mol–1 (c) internal energy of the system.
1 (d) free energy of the system.
(ii) H2(g) + O2(g) = H2O(l), 72. In which of the following entropy decreases?
2
DH = – X2 kJ mol–1 (a) Crystallization of sucrose solution
THERMODYNAMICS 77

(b) Rusting of iron (c) Assertion is correct, reason is incorrect

(c) Melting of ice (d) Assertion is incorrect, reason is correct.
(d) Vaporization of camphor 80. A reaction is spontaneous at low temperature but non-
73. For the gas phase reaction, spontaneous at high temperature. Which of the following is
ˆˆ† PCl (g) + Cl (g)
PCl (g) ‡ˆˆ true for the reaction?
5 3 2
(a) DH > 0, DS > 0 (b) DH < 0, DS > 0
which of the following conditions are correct ? (c) DH > 0, DS = 0 (d) DH < 0, DS < 0
(a) DH = 0 and DS < 0 (b) DH > 0 and DS > 0 81. At the sublimation temperature, for the process
(c) DH < 0 and DS < 0 (d) DH > 0 and DS < 0 ˆˆ† CO2(g)
CO2(s) ‡ˆˆ
74. The factor of DG values is important in metallurgy. The DG (a) DH, DS and DG are all positive
values for the following reactions at 800ºC are given as : (b) DH > 0, DS > 0 and DG < 0
S2 (s) + 2O2 (g) ¾¾
® 2SO2 (g) ; DG = – 544 kJ (c) DH < 0, DS > 0 and DG < 0
(d) DH > 0, DS > 0 and DG = 0
® 2ZnS(s) ; DG = – 293 kJ
2Zn(s) + S2 (s) ¾¾
82. Choose the reaction with negative DS value.
2Zn(s) + O2 (g) ¾¾ ® 2ZnO(s) ; DG = – 480 kJ (a) 2NaHCO3(s) ® Na2CO3(s) + CO2(g) + H2O(g)
Then DG for the reaction : (b) Cl2(g) ® 2Cl(g)
2ZnS(s) + 3O 2 (g) ¾¾ ® 2ZnO(s) + 2SO 2 (g) (c) 2SO2(g) + O2(g) ® 2SO3(g)
will be : (d) 2KClO3(s) ® 2KCl(s) + 3O2(g)
(a) –357 kJ (b) –731 kJ 83. Match the columns
(c) –773 kJ (d) –229 kJ Column-I Column-II
75. Identify the correct statement regarding entropy. (A) DH = –ve ; DS = –ve (p) Reaction will be
DG = –ve non-spontaneous at
(a) At absolute zero temperature, entropy of a perfectly
high temperature
crystalline substance is taken to be zero. (B) DH = –ve ; DS = –ve (q) Reaction will be
(b) At absolute zero temperature, the entropy of a perfectly DG = +ve non-spontaneous at
crystalline substance is positive. low temperature
(c) Absolute entropy of a substance cannot be determined. (C) DH = +ve ; DS = +ve (r) Reaction will be
(d) At 0°C, the entropy of a perfectly crystalline substance DG = +ve spontaneous at low
is taken to be zero temperature
76. Match the columns (D) DH = +ve ; DS = +ve (s) Reaction will be
Column-I Column-II DG = –ve spontaneous at high
(A) Exothermic (p) DH = 0, DE = 0 temperature
(B) Spontaneous (q) DG = 0 (a) A – (q), B – (r), C – (p), D – (s)
(C) Cyclic process (r) DH is negative (b) A – (r), B – (p), C – (q), D – (s)
(D) Equilibrium (s) DG is negative (c) A – (r), B – (q), C – (s), D – (p)
(a) A – (q), B – (r), C – (p), D – (s) (d) A – (q), B – (s), C – (p), D – (r)
(b) A – (s), B – (p), C – (r), D – (q) 84. Assertion : An exothermic process which is non-
(c) A – (p), B – (q), C – (s), D – (r) spontaneous at high temperature may become spontaneous
(d) A – (r), B – (s), C – (p), D – (q) at a low temperature.
77. Unit of entropy is Reason : There occurs a decrease in entropy factor as the
temperature is decreased.
(a) JK–1 mol–1 (b) J mol–1
–1 –1 –1 (a) Assertion is correct, reason is correct; reason is a
(c) J K mol (d) JK mol–1 correct explanation for assertion.
78. Considering entropy (S) as a thermodynamic parameter, the (b) Assertion is correct, reason is correct; reason is not a
criterion for the spontaneity of any process is correct explanation for assertion
(a) DSsystem + DSsurroundings > 0 (c) Assertion is correct, reason is incorrect
(b) DSsystem - DSsurroundings > 0 (d) Assertion is incorrect, reason is correct.
85. What is the equilibrium constant if ATP hydrolysis by water
(c) DSsystem > 0 only produce standard free energy of –50 kJ/mol under normal
(d) DSsurroundings > 0 only body conditions ?
79. Assertion : Many endothermic reactions that are not (a) 2.66 × 108 (b) 5.81 × 108
(c) 1.18 × 10 7 (d) 1.98 × 108
spontaneous at room temperature become spontaneous at
high temperature. 86. A reaction with DH = 0, is found to be spontaneous. This is
due to
Reason : Entropy of the system increases with increase in
(a) DS is negative (b) DS is positive
temperature.
(c) TDS is positive (d) Both (b) and (c)
(a) Assertion is correct, reason is correct; reason is a 87. In an irreversible process taking place at constant T and P and
correct explanation for assertion. in which only pressure-volume work is being done, the change
(b) Assertion is correct, reason is correct; reason is not a in Gibbs free energy (dG) and change in entropy (dS), satisfy
correct explanation for assertion the criteria
 EBD_7374
78 CHEMISTRY

(a) (dS)V, E > 0, (dG)T, P < 0 (a) 1118 K (b) 1008 K (c) 1200 K (d) 845 K.
(b) (dS)V, E = 0, (dG)T, P = 0 89. For vaporization of water at 1 atmospheric pressure, the values
(c) (dS)V, E = 0, (dG)T, P > 0 of DH and DS are 40.63 kJmol–1 and 108.8 JK–1 mol–1,
(d) (dS)V, E < 0, (dG)T, P < 0 respectively. The temperature when Gibbs energy change
88. In conversion of lime-stone to lime, (DG) for this transformation will be zero, is:
CaCO3 (s) ® CaO(s) + CO 2 (g) the values of DH° and DS° (a) 293.4 K (b) 273.4 K (c) 393.4 K (d) 373.4 K.
90. A reaction occurs spontaneously if
are + 179.1 kJ mol-1 and 160.2 J/K respectively at 298 K and 1
(a) TDS < DH and both DH and DS are + ve
bar. Assuming that DH° and DS° do not change with (b) TDS > DH and DH is + ve and DS is - ve
temperature, temperature above which conversion of (c) TDS > DH and both DH and DS are + ve
limestone to lime will be spontaneous is (d) TDS = DH and both DH and DS are + ve

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 13
(d) C 4 H10 ( g ) +O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) ;
1. Thermodynamics is not concerned about 2
(a) energy changes involved in a chemical reaction D c H = +2658.0 kJ mol-1
(b) the extent to which a chemical reaction proceeds 6. DfU° of formation of CH4(g) at certain temperature is
(c) the rate at which a reaction proceeds –393 kJ mol–1. The value of DfH° is
(d) the feasibility of a chemical reaction (a) zero (b) < DfU°
2. Which of the following statement is correct? (c) > Df U° (d) equal to Df U°
(a) The presence of reacting species in a covered beaker 7. In an adiabatic process, no transfer of heat takes place
is an example of open system. between system and surroundings. Choose the correct
(b) There is an exchange of energy as well as matter between option for free expansion of an ideal gas under adiabatic
the system and the surroundings in a closed system. condition from the following.
(c) The presence of reactants in a closed vessel made up (a) q = 0, DT ¹ 0, W = 0 (b) q ¹ 0, DT = 0, W = 0
of copper is an example of a closed system. (c) q = 0, DT = 0, W = 0 (d) q = 0, DT < 0, W ¹ 0
(d) The presence of reactants in a thermos flask or any 8. The pressure-volume work for an ideal gas can be calculated
other closed insulated vessel is an example of a closed Vf
system. by using the expression W = - ò pex dV. The work can also
3. The state of a gas can be described by quoting the Vi
relationship between be calculated from the pV-plot by using the area under the
(a) pressure, volume, temperature curve within the specified limits. When an ideal gas is
(b) temperature, amount, pressure compressed (a) reversibly or (b) irreversibly from volume Vi
(c) amount, volume, temperature to Vf . Choose the correct option.
(d) pressure, volume, temperature, amount (a) W (reversible) = W (irreversible)
4. The volume of gas is reduced to half from its original volume. (b) W (reversible) < W (irreversible)
(c) W (reversible) > W (irreversible)
The specific heat will be
(d) W (reversible) = W (irreversible) + pex.DV
(a) reduce to half (b) be doubled
9. The entropy change can be calculated by using the
(c) remain constant (d) increase four times
q
5. During complete combustion of one mole of butane, expression DS = rev . When water freezes in a glass beaker,,
2658 kJ of heat is released. The thermochemical reaction for T
choose the correct statement amongst the following.
above change is (a) DS (system) decreases but DS (surroundings) remains
(a) 2C4 H10 ( g ) + 13O 2 ( g ) ® 8CO 2 ( g ) + 10H 2O ( l ) ; the same
D c H = -2658.0 kJ mol-1 (b) DS (system) increases but DS (surroundings) decreases
(c) DS (system) decreases but DS (surroundings) increases
13
(b) C 4 H10 ( g ) + O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) ; (d) DS (system) decreases but DS (surroundings) also
2 decreases
D c H = -1329.0 kJ mol-1 10. On the basis of theromochemical equations (1), (2) and (3),
13 find out which of the algebraic relationships given in options
(c) C 4 H10 ( g ) + O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) ;
2 (a) to (d) is correct
D c H = -2658.0 kJ mol-1 1. C (graphite) + O2 (g) ® CO2 (g); DrH = x kJ mol–1
THERMODYNAMICS 79

1 (b) Assertion is correct, reason is correct; reason is not a

2. C (graphite) + O (g) ® CO (g); DrH = y kJ mol–1 correct explanation for assertion.
2 2
1 (c) Assertion is correct, reason is incorrect.
3. CO (g) + O (g) ® CO2 (g); DrH = z kJ mol–1 (d) Assertion is incorrect, reason is correct.
2 2
(a) z = x + y (b) x = y – z 19. For complete combustion of ethanol,
(c) x = y + z (d) y = 2z – x C 2 H 5 OH(l) + 3O 2 (g) ¾¾ ® 2CO 2 (g) + 3H 2 O(l),
11. Consider the reactions given below. On the basis of these the amount of heat produced as measured in bomb
reactions find out which of the algebraic relationship given calorimeter, is 1364.47 kJ mol–1 at 25ºC. Assuming ideality
in options (a) to (d) is correct? the enthalpy of combustion, DcH, for the reaction will be:
1. C (graphite) + 4 H (g) ® CH4 (g); DrH = x kJ mol–1 (R = 8.314 kJ mol–1) [JEE M 2014, S]
2. C (graphite) + 2H2 (g) ® CH4 (g); DrH = y kJ mol–1 (a) – 1366.95 kJ mol–1 (b) – 1361.95 kJ mol–1
(a) x = y (b) x = 2y (c) x > y (d) x < y (c) – 1460.95 kJ mol–1 (d) – 1350.50 kJ mol–1
12. The enthalpies of elements in their standard states are taken 20. The heats of neutralisation of CH3COOH, HCOOH, HCN
as zero. The enthalpy of formation of a compound and H2S are – 13.2, – 13.4, – 2.9 and – 3.8 kcal per equivalent
(a) is always negative respectively. Arrange the acids in increasing order of acidic
(b) is always positive strength. [BITSAT 2014, C]
(c) may be positive or negative (a) HCOOH > CH3COOH > H2S > HCN
(d) is never negative (b) CH3COOH > HCOOH > H2S > HCN
13. Enthalpy of sublimation of a substance is equal to (c) H2S > HCOOH > CH3COOH > HCN
(a) enthalpy of fusion + enthalpy of vaporisation (d) HCOOH > H2S > CH3COOH > HCN
(b) enthalpy of fusion 21. If the enthalpy of vaporization of water is 186.5 kJmol–1, the
(c) enthalpy of vaporisation entropy if its vaporization will be : [BITSAT 2014, S]
(d) twice the enthalpy of vaporisation (a) 0.5 JK–1mol–1 (b) 1.0 JK–1mol–1
14. Which of the following is not correct? (c) 1.5 JK–1mol–1 (d) 2.0 JK–1mol–1
(a) DG is zero for a reversible reaction. 22. The heat of combustion of carbon to CO2 is – 393.5 kJ/mol.
(b) DG is positive for a spontaneous reaction. The heat released upon formation of 35.2 g of CO2 from
(c) DG is negative for a spontaneous reaction. carbon and oxygen gas is [AIPMT 2015, S]
(d) DG is positive for a non-spontaneous reaction. (a) –315 kJ (b) +315 kJ (c) –630 kJ (d) –3.15 kJ
Past Year MCQs 23. Following reaction occurrs in an automobile
2C8H18 (g) + 25O2 (g) ® 16CO2 (g) + 18H 2 O(g).
15. Which of the following statements is correct for the
spontaneous adsorption of a gas ? [AIPMT 2014, C] The sign of DH, DS and DG would be [AIIMS 2015, S]
(a) DS is negative and, therefore, DH should be highly (a) +, –, + (b) –, +, – (c) –, +, + (d) +, +, –
positive 24. The enthalpy changes for the following processes are listed
(b) DS is negative and therefore, DH should be highly below : [AIIMS 2015, S]
negative Cl2(g) ® 2Cl(g), 242.3 kJ mol–1
(c) DS is positive and, therefore, DH should be negative I2(g) ® 2I(g), 151.0 kJ mol–1
(d) DS is positive and, therefore, DH should also be highly ICl(g) ® I(g) + Cl(g), 211.3 kJ mol–1
positive I2(s) ® I2(g), 62.76 kJ mol–1
16. For the reaction : [AIPMT 2014, S] Given that the standard states for iodine and chlorine are
X2O4(l) ® 2XO2(g) I2(s) and Cl2(g), the standard enthalpy of formation for ICl(g) is:
DU = 2.1 k cal, DS = 20 cal K–1 at 300 K (a) +16.8 kJ mol–1 (b) +244.8 kJ mol–1
(c) –14.6 kJ mol –1 (d) –16.8 kJ mol–1
Hence DG is:-
(a) 2.7 k cal (b) – 2.7 k cal 25. A spontaneous reaction is impossible if
(c) 9.3 k cal (d) – 9.3 k cal [BITSAT 2015, C]
17. What is the enthalpy change for, (a) both DH and DS are negative
(b) both DH and DS are positive
2H 2 O2 (l) ® 2 H 2O(l) + O2 (g) if heat of (c) DH is negative and DS is positive
formation of H2O2 (l) and H2O (l) are –188 and (d) DH is positive and DS is negative
–286 kJ/mol respectively? [AIIMS 2014, S] 26. Which law of the thermodynamics helps in calculating the
(a) –196 kJ/mol (b) + 948 kJ/mol absolute entropies of various substances at different
(c) + 196 kJ/mol (d) –948 kJ/mol temperatures? [BITSAT 2015, C]
18. Assertion : For a reaction 2NH3(g) ® (a) First law (b) Second law
N2(g) + 3H2 (g); DH > DE. (c) Third law (d) Zeroth law
Reason : Enthalpy change is always greater than internal 27. The correct thermodynamic conditions for the spontaneous
energy change. [AIIMS 2014, C] reaction at all temperatures is [NEET 2016, C]
(a) Assertion is correct, reason is correct; reason is a (a) DH < 0 and DS = 0 (b) DH > 0 and DS < 0
correct explanation for assertion. (c) DH < 0 and DS > 0 (d) DH < 0 and DS < 0
 EBD_7374
80 CHEMISTRY

28. Choose the reaction in which DH is not equal to DU ? (a) 524.1 (b) 41.2 (c) – 262.5 (d) – 41.2
[AIIMS 2016, C] 37. DU is equal to [JEE M 2017, C]
(a) C(graphite) + O2(g) ® CO2(g) (a) Isochoric work (b) Isobaric work
(b) C2H4(g) + H2(g) ® C2H6(g) (c) Adiabatic work (d) Isothermal work
(c) 2C(graphite) + H2(g) ® C2H2(g) 38. For a given reaction, DH = 35.5 kJ mol –1 and
(d) H2(g) + I2(g) ® 2HI(g) DS = 83.6 JK–1 mol–1. The reaction is spontaneous at :
29. The standard enthalpies of combustion of C 6 H6(l), (Assume that DH and DS do not vary with tempearature)
C(graphite) and H2(g) are respectively – 3270 kJ mol–1, – 394 [BITSAT 2017, C]
kJ mol–1 and – 286 kJ mol–1. What is the standard enthalpy (a) T > 425 K (b) All temperatures
of formation of C6H6(l) in kJ mol–1 ? [AIIMS 2016, S] (c) T > 298 K (d) T < 425 K
(a) – 48 (b) + 48 (c) – 480 (d) + 480 1
39. For the reaction CO (g ) + O 2 (g ) ® CO 2 (g )
30. The heats of combustion of carbon and carbon monoxide 2
Which one of the statement is correct at constant T and P ?
are –393.5 and –283.5 kJ mol–1, respectively. The heat of
[BITSAT 2017, C]
formation (in kJ) of carbon monoxide per mole is :
(a) DH = DE (b) DH < DE
[JEE M 2016, S]
(c) DH > DE
(a) – 676.5 (b) – 110.5 (c) 110.5 (d) 676.5
31. Given (d) DH is independent of physical state of the reactants
Reaction Energy Change (in kJ) 40. The bond dissociation energies of X2, Y2 and XY are in
Li(s) ® Li(g) 161 the ratio of 1 : 0.5 : 1. DH for the formation of XY is –200 kJ
Li(g) ® Li+(g) 520 mol–1. The bond dissociation energy of X2 will be
1 [NEET 2018, S]
F (g) ® F(g) 77 (a) 200 kJ mol–1 (b) 100 kJ mol–1
2 2
F(g) + e– ® F–(g) (Electron gain enthalpy) (c) 400 kJ mol–1 (d) 800 kJ mol–1
Li+ (g) + F–(g) ® Li F(s) – 1047 41. Which of following factor always increases for spontane-
1 ous process? [AIIMS 2018, S]
Li(s) + F2(g) ® Li F(s) – 617
2 (a) DS (b) DH
DH
Based on data provided, the value of electron gain enthalpy (c) DH – TDS (d) DS –
of fluorine would be : [BITSAT 2016, S] T
42. 1 mole of an ideal gas expands isothermally and reversibly
(a) – 300 kJ mol–1 (b) – 350 kJ mol–1
from 2 lit to 4 lit and 3 moles of same gas expand from 2 lit to
(c) – 328 kJ mol–1 (d) – 228 kJ mol–1
32. For a particular reversible reaction at temperature T, DH and x lit and doing same work, what is ‘x’?
1 2
DS were found to be both +ve. If Te is the temperature at (8) 3
(a) (b) (4) 3 (c) 2 (d) 4 lit
equilibrium, the reaction would be spontaneous when
43. The combustion of benzene (l) gives CO2 (g) and H2O (l).
[BITSAT 2016, S]
Given that heat of combustion of benzene at constant
(a) Te > T (b) T > Te
volume is –3263.9 kJ mol–1 at 25°C; heat of combustion
(c) Te is 5 times T (d) T = Te
(in kJ mol–1) of benzene at constant pressure will be :
33. A gas is allowed to expand in a well insulated container
(R= 8.314 JK–1 mol–1) [JEE M 2018, S]
against a constant external pressure of 2.5atm from an initial
(a) 4152.6 (b) – 452.46
volume of 2.50 L to a final volume of 4.50L. The change in
(c) 3260 (d) – 3267.6
internal energy DU of the gas in joules will be:-
[NEET 2017, S] 44. Which of the following lines correctly show the temperature
(a) – 500 J (b) – 505 J (c) + 505 J (d) 1136.25 J dependence of equilibrium constant, K, for an exothermic
34. For a given reaction, DH = 35.5 kJ mol -1 and DS = 83.6 reaction? [JEE M 2018, S]
JK -1 mol -1. The reaction is spontaneous at : (Assume that ln K A
DH and DS do not vary with tempearature) [NEET 2017, S]
(a) T > 425 K (b) All temperatures B 1
(c) T > 298 K (d) T < 425 K (0, 0) T(K)
++
35. The molar heat capacity of water at constant pressure is 75 ++ C
++
JK–1 mol–1. When 1kJ of heat is supplied to 100 g of water, ++
D
which is free to expand, the increase in temperature of water
(a) A and B (b) B and C
is [AIIMS 2017, S]
(c) C and D (d) A and D
(a) 6.6 K (b) 1.2 K (c) 2.4 K (d) 4.8 K
45. For vaporization of water at 1 atmospheric pressure, the values
36. The D f H° for CO2(g) , CO(g) and H2O(g) are –393.5, of DH and DS are 40.63 kJmol–1 and 108.8 JK–1 mol–1,
–110.5 and –241.8 kJ/mol respectively, the standard enthalpy respectively. The temperature when Gibbs energy change
change (in kJ) for the reaction (DG) for this transformation will be zero, is:[BITSAT 2018]
CO2(g) + H2(g) ® CO(g) + H2O(g) is : [AIIMS 2017, C] (a) 293.4 K (b) 273.4 K (c) 393.4 K (d) 373.4 K.
THERMODYNAMICS 81

Exercise 3 : Try If You Can

1. Which of the following expressions is true for an ideal gas? 8. For the reaction taking place at certain temperature
æ dV ö æ dP ö ˆˆ† 2NH3 ( g ) + CO 2 ( g ) ,
NH 2 COONH 4 ( s ) ‡ˆˆ
(a) ç ÷ =0 (b) ç ÷ =0
è dT ø P è dT ø V if equilibrium pressure is 3X bar then DrG° would be
(a) – RT ln 9 – 3RT ln X (b) RT ln 4 – 3RT ln X
æ dU ö æ dU ö
(c) ç ÷ =0 (d) ç ÷ =0 (c) – 3RT ln X (d) None of these
è dV øT è dT øV 9. The heat of combustion of ethane gas is 368 kcal/mol.
æ 5 ö Assuming that 60% of the heat is useful, how many m3 of
2. 0.5 mole each of two ideal gases A ç Cv,m = R ÷ and ethane measured at STP must be burnt to supply enough
è 2 ø
heat to convert 50 kg of water at 10oC to steam at 100oC?
B (Cv,m = 3R) are taken in a container and expanded reversibly
(Specific heat of water is 1 cal/g, heat of vaporisation of
and adiabatically, during this process temperature of
H2O is 540 cal/g)
gaseous mixture decreased from 350 K to 250 K. Find DH
(a) 2.196 m3 (b) 1.196 m3 (c) 4.196 m3 (d) 3.196 m3
(in cal/mol) for the process:
10. The factor of DG values is important in metallurgy. The DG
(a) – 100 R (b) – 137.5 R
values for the following reactions at 800ºC are given as :
(c) – 375 R (d) None of these
3. A heating coil is immersed in a 100 g sample of H2O (l) at S2 (s) + 2O 2 (g) ¾¾
® 2SO2 (g) ; DG = – 544 kJ
1 atm and 100°C in a closed vessel. In this heating process,
® 2ZnS(s) ; DG = – 293 kJ
2Zn(s) + S2 (s) ¾¾
60% of the liquid is converted in to gaseous form at constant
pressure of 1 atm. Densities of liquid and gaseous water ® 2ZnO(s) ; DG = – 480 kJ
2Zn(s) + O 2 (g) ¾¾
under these conditions are 1000 kg/m3 and 0.60 kg/m3 Then DG for the reaction :
respectively. Magnitude of the work done for the process
2ZnS(s) + 3O 2 (g) ¾¾
® 2ZnO(s) + 2SO 2 (g)
is :
(a) 4997 J (b) 4970 J will be :
(c) 9994 J (d) None of these 11. If bond enthalpies of N º N, H –H and N –H bonds are x1,
4. Given that: x2 and x3 respectively, DH of for NH3 will be
(i) D f H° of N 2O is 82 kJ mol–1 (a) x1 + 3x2 – 6x3 (b) ½x1 + 3/2x2 – 3x3
(c) 3x3 – ½x1 – 3/2x2 (d) 6x3 – x1 – 3x2
(ii) Bond energies of N º N, N=N, O = O and N = O are 946,
12. If H is considered as the function of P and T, then which of
418, 498 and 607 kJ mol–1 respectively,
the following relations is /are correct?
The resonance energy of N2O is :
(a) – 88 kJ (b) – 66 kJ (c) –62 kJ (d) –44 kJ æ dH ö æ dH ö
(a) dH = ç ÷ dT + ç ÷ dP
5. Calculate enthalpy change for the change è dT øP è dP øT
8S(g) ¾® S8(g), given that
æ dH ö
® 2H(g) + 2S(g), DH = 239.0 k cal mol-1 ;
H 2S2 (g) ¾¾ (b) dH = Cp dT + ç ÷ dP
è dP øT
® 2H(g) + S(g), D H = 175.0 k cal mol -1
H 2S(g) ¾¾
(a) + 512.0 k cal (b) – 512.0 k cal æ dH ö
(c) 508.0 k cal (d) – 508.0 k cal
(c) ç ÷ = –V
è dP øT
6. Fixed mass of an ideal gas contained in a 24.63 L sealed
(d) all
rigid vessel at 1 atm is heated from – 73°C to 27°C. Calculate
13. If the ratio of molar heat capacities of a gas at constant
change in gibb's energy if entropy of gas is a function of
temperature as S = 2 + 10–2 T (J/K): (Use 1 atm L = 0.1 kJ) CP
pressure and constant volume i.e., = g , the respective
(a) 1231.5 J (b) 1281.5 J Cv
(c) 781.5 J (d) 0
values of CP and Cv are
7. The densities of graphite and diamond at 298 K are 2.25
and 3.31 g cm–3, respectively. If the standard free energy R gR gR R
(a) , (b) ,
difference (DGº) is equal to 1895 J mol–1, the pressure at g -1 g -1 g -1 g -1
which graphite will be transformed into diamond at 298 K is
(a) 9.92 × 105 Pa (b) 11.094 × 108 Pa g -1 g -1 g -1 g -1
(c) , (d) ,
(c) 10.952 × 107 Pa (d) 9.92 × 106 Pa gR R R gR
 EBD_7374
82 CHEMISTRY

14. Heat of neutralization of a strong acid HA and a weaker acid 15. The bond dissociation energies of CH 4 and C 2 H 6
HB with KOH are – 13.7 and – 12.7 k cal mol–1. When 1 mole respectively are 360 and 620 k cal mol–1. The C – C bond
of KOH was added to a mixture containing 1 mole each of energy would be
HA and HB, the heat change was – 13.5 kcal. In what ratio is (a) 260 k cal/mol (b) 180 k cal/mol
the base distributed between HA and HB. (c) 130 k cal/mol (d) 80 k cal/mol
(a) 3 : 1 (b) 1 : 3 (c) 4 : 1 (d) 1 : 4

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 10 (a) 19 (d) 28 (a) 37 (c) 46 (a) 55 (b) 64 (a) 73 (b) 82 (c)
2 (c) 11 (d) 20 (b) 29 (c) 38 (a) 47 (b) 56 (a) 65 (a) 74 (b) 83 (b)
3 (b) 12 (d) 21 (b) 30 (b) 39 (c) 48 (b) 57 (c) 66 (d) 75 (a) 84 (b)
4 (d) 13 (d) 22 (c) 31 (a) 40 (b) 49 (b) 58 (a) 67 (b) 76 (d) 85 (a)
5 (c) 14 (c) 23 (d) 32 (a) 41 (a) 50 (c) 59 (d) 68 (d) 77 (a) 86 (b)
6 (c) 15 (a) 24 (b) 33 (d) 42 (a) 51 (b) 60 (a) 69 (a) 78 (a) 87 (a)
7 (d) 16 (b) 25 (a) 34 (d) 43 (b) 52 (b) 61 (b) 70 (b) 79 (b) 88 (a)
8 (c) 17 (c) 26 (c) 35 (a) 44 (d) 53 (a) 62 (a) 71 (d) 80 (d) 89 (d)
9 (a) 18 (c) 27 (b) 36 (a) 45 (c) 54 (d) 63 (c) 72 (a) 81 (d) 90 (c)
Exercise 2 : Exemplar & Past Year MCQs
1 (c) 6 (b) 11 (c) 16 (b) 21 (a) 26 (c) 31 (c) 36 (b) 41 (d)
2 (c) 7 (c) 12 (c) 17 (a) 22 (a) 27 (c) 32 (b) 37 (c) 42 (b)
3 (d) 8 (b) 13 (a) 18 (c) 23 (b) 28 (b) 33 (b) 38 (a) 43 (d)
4 (c) 9 (c) 14 (b) 19 (a) 24 (a) 29 (b) 34 (a) 39 (b) 44 (a)
5 (c) 10 (c) 15 (b) 20 (a) 25 (d) 30 (b) 35 (c) 40 (d) 45 (d)
Exercise 3 : Try If You Can
1 (c) 3 (c) 5 (b) 7 (b) 9 (d) 11 (b) 13 (b) 15 (d)
2 (c) 4 (a) 6 (c) 8 (d) 10 (b) 12 (d) 14 (d)
 Chapter
7 EQUILIBRIUM

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

8
7
6
AIPMT /NEET
5
Number of Questions

AIIMS
4
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 7 Buffer solution,
AIIMS 6 salt hydrolysis and 3.5/5 8.5
JEE Main 5 solubility product
BITSAT 5
 EBD_7374
84 CHEMISTRY
EQUILIBRIUM 85
 EBD_7374
86 CHEMISTRY

Exercise 1 : Topic-wise MCQs

(b) It cannot be influenced by a catalyst
Topic 1: Equilibrium in Physical Processes, Equilibrium
(c) Number of moles of reactants and products is always
in Chemical Processes - Dynamic Equilibrium equal
1. Which of the following is not a general characteristic of (d) It can be attained only in a closed container
equilibria involving physical processes ? 7. If a system is at equilibrium, the rate of forward to the reverse
(a) Equilibrium is possible only in a closed system at a reaction is :
given temperature. (a) less (b) equal
(b) All measurable properties of the system remain (c) high (d) at equilibrium
constant. 8. Consider the following graph and mark the correct statement.
(c) All the physical processes stop at equilibrium.
(d) The opposing processes occur at the same rate and HI
there is dynamic but stable condition.
HI
2. Boiling point of the liquid depends on the atmospheric Conc.
pressure. It depends on the altitude of the place; at high H2+I2 H 2 + I2
altitude the boiling point…………..
(a) increases
(b) decreases Time Equal Time
(c) either decreases or increases
(d) remains same (a) Chemical equilibrium in the reaction, H 2 + I2 ƒ 2HI
3. A reaction is said to be in equilibrium when can be attained from either directions.
(a) the rate of transformation of reactant to products is (b) Equilibrium can be detained when H2 and I2 are mixed
equal to the rate of transformation of products to the in an open vessel.
reactants. (c) The concentrations of H2 and I2 keep decreasing while
(b) 50% of the reactants are converted to products. concentration of HI keeps increasing with time.
(c) the reaction is near completion and all the reactants are (d) We can find out equilibrium concentration of H2 and I2
converted to products. from the given graph.
(d) the volume of reactants is just equal to the volume of 9. Match the Column-I with Column-II and mark the appropriate
the products. choice.
4. If the synthesis of ammonia from Haber's process is carried Column-I Column-II
out with exactly the same starting conditions (of partial (A) Liquid ‡ˆˆˆˆ† Vapour (p) Saturated solution
pressure and temperature) but using D2 (deuterium) in place ˆˆ† Liquid
(B) Solid ‡ˆˆ (q) Boiling point
of H2. Then
(C) Solid ‡ˆˆˆˆ† Vapour (r) Sublimation point
(a) the equilibrium will be disturbed
ˆˆ†
(D) Solute (s) ‡ˆˆ Solute (s) Melting point
(b) the composition of reaction mixture will remain same at
equilibrium. (solution)
(c) Use of isotope in reaction will not produce ammonia. (a) A – (p) ; B – (r) ; C – (q) ; D – (s)
(d) At equilibrium rate of forward reaction will be greater (b) A – (q) ; B – (s) ; C – (r) ; D – (p)
than the rate of reverse reaction (c) A – (s) ; B – (q) ; C – (p) ; D – (r)
5. A small amount of acetone is taken in a watch glass and it is (d) A – (r) ; B – (s) ; C – (q) ; D – (p)
kept open in atmosphere. Which statement is correct for the 10. You must have seen that when a soda water bottle is opened,
given experiment? some of the carbon dioxide gas dissolved in it fizzes out
(a) The rate of condensation from vapour to liquid state is rapidly. There is equilibrium between the molecules in the
higher than the rate of evaporation. gaseous state and the molecules dissolved in the liquid
(b) The rate of condensation from vapour to liquid state is under pressure i.e.,
equal to the rate of evaporation. ˆˆ† CO (in solution)
CO2(gas) ‡ˆˆ 2
(c) The rate of condensation from vapour to liquid state is Which of the following statements is/are correct regarding
much less than the rate of evaporation. this?
(d) The rate of condensation from vapour to liquid state is (i) The phenomenon arises due to difference in solubility
equal or less than the rate of evaporation. of carbon dioxide at different pressures.
6. Which of the following is not true about a reversible (ii) This equilibrium is governed by Henry's law.
reaction? (iii) The amount of CO2 gas dissolved in liquid increases
(a) The reaction does not proceed to completion with decrease of temperature.
EQUILIBRIUM 87

(iv) The amount of CO2 gas dissolved in liquid decreases 17. ˆˆ† C . The unit of equilibrium constant is :
In A + B ‡ˆˆ
with increase of temperature. (a) Litre mol–1 (b) Mol litre
(a) (i), (ii) and (iv) are correct (c) Mol litre–1 (d) No unit
(b) (i) , (iii) and (iv) 18. In which of the following equilibrium Kc and Kp are not equal?
(c) (i), (ii) and (iii) are correct (a) 2 NO(g) ƒ N 2 (g)+O 2 (g)
(d) only (iii) is correct
(b) SO 2 (g)+NO2 (g) ƒ SO3 (g)+NO(g)
Topic 2: Law of Chemical Equilibrium and Equilibrium
(c) H 2 (g)+I 2 (g) ƒ 2HI(g)
Constant, Homogenous Equilibria, Heterogenous Equilibria
(d) 2C(s)+O 2 (g) ƒ 2CO2(g)
11. The equilibrium constant for the reversible reaction
19. ˆˆ† 2CO(g) , the partial
For the reaction C(s) + CO 2 (g) ‡ˆˆ
N2 + 3H2 2NH3 is K and for reaction
pressures of CO2 and CO are 2.0 and 4.0 atm respectively at
1 3
N2 + H2 NH3, the equilibrium constant is K ' equilibrium. The Kp for the reaction is.
2 2
(a) 0.5 (b) 4.0 (c) 8.0 (d) 32.0
The K and K ' will be related as: 20. For a chemical reaction ;
(a) K × K ' = 1 (b) K = K ' A (g) + B (l) ƒ D (g) + E (g)
(c) K ' = K (d) K = K ' Hypothetically at what temperature, Kp = Kc
12. The rate constant for forward and backward reaction of (when, R = 0.08 l-atm/mol-K)
hydrolysis of ester are 1.1 ´ 10–2 and 1.5 ´ 10–3 per minute (a) T = 0 K (b) T = 1K
respectively. Equilibrium constant for the reaction (c) T = 12.5 K (d) T = 273 K
21. For the reaction C(s) + CO2(g) ® 2CO(g), Kp = 63 atm at
CH3COOC2 H 5 + H + CH 3COOH + C 2 H 5OH is
1000 K. If at equilibrium : PCO = 10 PCO , then the total
(a) 4.33 (b) 5.33 (c) 6.33 (d) 7.33 pressure of the gases at equilibrium is
2

13. A reaction is A + B C + D. Initially we start with (a) 6.3 atm (b) 6.93 atm (c) 0.63 atm (d) 0.693 atm
equal concentrations of A and B. At equilibrium we find 22. The Kp/Kc ratio will be highest in case of
that the moles of C is two times of A. What is the equilibrium 1
(a) CO (g) + O2 (g) ‡ˆˆ ˆˆ† CO2 (g)
constant of the reaction? 2
1 1 ˆˆ† 2HI (g)
(b) H2 (g) + I2 (g) ‡ˆˆ
(a) (b) (c) 4 (d) 2
4 2 ˆˆ†
(c) PCl5 (g) ‡ˆˆ PCl3(g) + Cl2 (g)
14. In the following equilibrium reaction (d) 7H2 (g) + 2NO2 (g) ‡ˆˆˆˆ† 2NH3 (g) + 4H2O(g)
2A ‡ˆˆˆ†ˆ B + C, 23. Steam reacts with iron at high temperature to give hydrogen
the equilibrium concentrations of A, B and C are 1 × 10–3 M, gas and Fe3O4 (s). The correct expression for the equilibrium
2 × 10–3 M and 3 × 10–3 M respectively at 300 K. The value constant is
of Kc for this equilibrium at the same temperature is
PH2 (PH 2 ) 4
1 1 (a) 2
(b)
(a) (b) 6 (c) (d) 36
6 36 PH2 O (PH 2O ) 4
2
15. Given the reaction between 2 gases represented by A2 and
B2 to give the compound AB(g). (PH 2 ) 4 [Fe 3 O 4 ] [Fe 3O 4 ]
(c) (d)
A2(g) + B2(g) ƒ 2 AB(g). 4
(PH 2 O ) [Fe] [Fe]
At equilibrium, the concentration
24. Equilibrium constant (K) for the reaction
of A2 = 3.0 × 10–3 M
Ni(s) + 4CO(g) ‡ˆˆ
ˆˆ†ˆ Ni(CO)4(g) can be written in terms of
of B2= 4.2 × 10–3 M
of AB = 2.8 × 10–3 M (1) Ni(s) + 2CO2 (g) + 2C(s) ‡ˆˆ
ˆˆ† ˆ Ni(CO)4(g);
lf the reaction takes place in a sealed vessel at 527 °C, then equilibrium constant = K1.
the value of Kc will be : (2) CO2(g) + C(s) ‡ˆˆ
ˆˆ† ˆ 2CO(g);
(a) 2.0 (b) 1.9 (c) 0.62 (d) 4.5 equilibrium constant = K2.
16. The thermal dissociation of calcium carbonate showing What is the relation between K, K2 and K2 ?
heterogeneous equilibrium is (a) K = (K1)/(K2)2 (b) K = (K1 . K2)
ˆˆ† CaO(s) + CO 2 (g)
CaCO3 (s) ‡ˆˆ (c) K = (K1) (K2)2 (d) K = K1/K2
For this reactions which of the following is/are true 25. Unit of equilibrium constant for the given reaction is
ˆˆ† Ni (CO) (g)
Ni(s) + 4CO(g) ‡ˆˆ
(i) K´c = [CO2(g)] 4
(ii) Kp = pCO (a) (mol/L) (b) (mol/L)3 (c) (mol/L)–4 (d) (mol/L)4
–3
2 26. Two moles of PCl5 were heated in a closed vessel of 2L. At
(iii) [CaCO3(s)] and [CaO(s)] are both constant
equilibrium 40% of PCl5 is dissociated into PCl3 and Cl2.
(iv) [CO2(g)] is constant
The value of equilibrium constant is
(a) (i), (ii) and (iv) (b) (i), (ii) and (iii)
(a) 0.53 (b) 0.267 (c) 2.63 (d) 5.3
(c) (ii) and (iv) (d) (i), (iii) and (iv)
 EBD_7374
88 CHEMISTRY

27. For the following three reactions a, b and c, equilibrium 1

(III) NO2 N 2 + O2
constants are given: 2
(i) CO(g) + H 2O(g) ƒ CO 2 (g) + H 2 (g); K1 The correct relation from the following is
(ii) CH4 (g) + H2O(g) ƒ CO(g) + 3H2 (g); K 2 1 1 1 1
(a) K1 = = (b) K1 = =
K 2 K3 K 2 ( K )2
(iii) CH4 (g) + 2H2O(g) ƒ CO2 (g) + 4H2 (g);K3 3
1
(a) K1 K 2 = K 3 (b) K 2 K3 = K1 (c) K1 = K 2 = K3 (d) K1 =
= K3
K2
(c) K3 = K1 K2 (d) K3 .K 32 = K12 34. Assertion : Kp can be less than, greater than or equal to Kc.
28. For the reversible reaction, Reason : Relation between Kp and Kc depends on the change
in number of moles of gaseous reactants and products (Dn).
N2(g) + 3H2(g) 2NH3(g) at 500°C, the value of Kp is
–5
(a) Assertion is correct, reason is correct; reason is a
1.44 × 10 when partial pressure is measured in atmospheres. correct explanation for assertion.
The corresponding value of Kc, with concentration in mol (b) Assertion is correct, reason is correct; reason is not a
litre–1, is correct explanation for assertion
1.44 ´10 -5 1.44 ´10 -5 (c) Assertion is correct, reason is incorrect
(a) (b)
(0.082 ´ 500)- 2 (8.314 ´ 773)- 2 (d) Assertion is incorrect, reason is correct.
1.44 ´10 -5 1.44 ´10 -5 Topic 3: Applications of Equilibrium Constants
(c) (d)
(0.082 ´ 773) 2
(0.082 ´ 773) -2 Relationship between Equilibrium Constant (K),
29. PCl5 is dissociating 50% at 250°C at a total pressure of Reaction Quotient (Q) and Gibbs Energy (G)
P atm. If equilibrium constant is Kp, then which of the Factors Affecting Equilibria
following relation is numerically correct ?
(a) Kp = 3P (b) P = 3Kp 35. In a reversible chemical reaction having two reactants in
equilibrium, if the concentration of the reactants are doubled
2KP 2P then the equilibrium constant will
(c) P = (d) Kp =
3 3 (a) Also be doubled (b) Be halved
30. The dissociation equilibrium of a gas AB2 can be represented (c) Become one-fourth (d) Remain the same
as : 36. If for the reaction
ˆˆ† 2AB(g) + B2 (g)
2AB2 (g) ‡ˆˆ N2 + 3H2 ‡ˆˆ ˆˆ† 2NH3, DH = –92.38 kJ/mol than what
The degree of dissociation is ‘x’ and is small compared to 1. happens if the temperature is increased?
The expression relating the degree of dissociation (x) with (a) Reaction proceed forward
equilibrium constant Kp and total pressure P is : (b) Reaction proceed backward
(a) (2Kp/P) (b) (2Kp/P) 1/3 (c) No effect on the formation of product
(d) None of these
(c) (2Kp/P)1/2 (d) (Kp/P) 37. If Kc is in the range of ………………… appreciable
31. For the decomposition of the compound, represented as concentrations of both reactants and products are present.
ˆˆ† 2NH 3 ( g ) + CO 2 ( g )
NH 2 COONH 4 ( s ) ‡ˆˆ (a) 10–4 to 104 (b) 10 – 3 to 103
the Kp = 2.9 × 10–5 atm3. (c) 103 to 10– 3 (d) 10 – 5 to 103
If the reaction is started with 1 mol of the compound, the 38. The reaction quotient (Q) for the reaction
total pressure at equilibrium would be : ˆˆ† 2NH 3 (g)
N 2 (g) + 3H 2 (g) ‡ˆˆ
(a) 1.94 × 10–2 atm (b) 5.82 × 10–2 atm
–2
(c) 7.66 × 10 atm (d) 38.8 × 10–2 atm [ NH 3 ]2
is given by Q = . The reaction will proceed from
32. The values of Kp1 and Kp2 for the reactions [ N 2 ] [ H 2 ]3
ˆˆ† Y + Z right to left if
X ‡ˆˆ ...(1) (a) Q = 0 (b) Q = Kc (c) Q < Kc (d) Q > Kc
ˆˆ† 2B
and A ‡ˆˆ ...(2) where Kc is the equilibrium constant
39. On doubling P and V with constant temperature the
are in the ratio of 9 : 1. If degree of dissociation of X and A be equilibrium constant will
equal, then total pressure at equilibrium (1) and (2) are in the (a) remain constant (b) become double
ratio : (c) become one-fourth (d) None of these
(a) 3 : 1 (b) 1 : 9 (c) 36 : 1 (d) 1 : 1 40. The reaction quotient Q is used to
33. K1, K2 and K3 are the equilibrium constants of the following (a) predict the extent of a reaction on the basis of its
reactions (I), (II) and (III) respectively: magnitude
(I) N2 + 2O2 2NO2 (b) predict the direction of the reaction
(c) calculate equilibrium concentrations
(II) 2NO2 N2 + 2O2 (d) calculate equilibrium constant
EQUILIBRIUM 89

41. The equilibrium which remains unaffected by pressure (c) low temperature and low pressure
change is (d) low temperature and high pressure
ˆˆ† 2NO(g)
(a) N 2 (g) + O2 (g) ‡ˆˆ 49. In a vessel N2, H2 and NH3 are at equilibrium. Some helium
ˆˆ† 2SO3 (g)
(b) 2SO2 (g) + O2 (g) ‡ˆˆ gas is introduced into the vessel so that total pressure
ˆˆ† 3O2 (g)
(c) 2O3 (g) ‡ˆˆ increases while temperature and volume remain constant.
According to Le Chatelier’s principle, the dissociation of NH3
ˆˆ† N 2 O4 (g)
(d) 2NO2 (g) ‡ˆˆ (a) increases (b) decreases
o
42. Usin g th e equation ( K = e-DG /RT ), the reaction (c) remains unchanged (d) equilibrium is disturbed
spontaneity can be interpreted in terms of the value of DG° 50. In a two-step exothermic reaction
is/are A2(g) + B2(g) 3C(g) D(g)
o
-D G /RT Step 1 Step 2
(a) If DG o > 0 , then – DG o /RT
T is positive, and e Steps 1 and 2 are favoured respectively by
> 1 making K > 1, which implies a spontaneous reaction (a) high pressure, high temperature and low pressure, low
or the reaction which proceeds in the forward direction temperature
to such an extent that the products are present (b) high pressure, low temperature and low pressure, high
predominantly. temperature
(b) If DG o > 0 , then – DG o /RT T is negative, and (c) low pressure, high temperature and high pressure, high
o
e -D G / RT < 1 making K < 1, which implies a non- temperature
spontaneous reaction or a reaction which proceeds in (d) low pressure, low temperature and high pressure, low
the forward direction to such a small degree that only a temperature
very minute quantity of product is formed. 51. Assertion : If a volume is kept constant and an inert gas
(c) Both (a) and (b) such as argon is added which does not take part in the
(d) None of the above reaction, the equilibrium remains undisturbed.
43. According to Le-chatelier’s principle, adding heat to a solid Reason : It is because the addition of an inert gas at constant
ˆˆ† liquid equilibrium will cause the volume does not change the partial pressure or the molar
‡ˆˆ
(a) temperature to increase concentrations of the substance involved in the reaction.
(b) temperature to decrease (a) Assertion is correct, reason is correct; reason is a
(c) amount of liquid to decrease correct explanation for assertion.
(d) amount of solid to decrease (b) Assertion is correct, reason is correct; reason is not a
44. The correct relationship between free energy change in a correct explanation for assertion
reaction and the corresponding equilibrium constant, Kc is (c) Assertion is correct, reason is incorrect
(a) DG = RT ln Kc (b) – DG = RT ln Kc (d) Assertion is incorrect, reason is correct.
(c) DG° = RT ln Kc (d) –DG° = RT ln Kc 52. The exothermic formation of ClF3 is represented by the
45. Which of the following reaction will be favoured at low equation :
pressure ? ˆˆ† 2ClF (g); DH = – 329 kJ
Cl2(g) + 3F2(g) ‡ˆˆ 3
ˆˆ† 2HI
(a) H 2 + I 2 ‡ˆˆ Which of the following will increase the quantity of ClF3 in
an equilibrium mixture of Cl2, F2 and ClF3?
(b) ˆˆ† 2NH3
N 2 + 3H 2 ‡ˆˆ (a) Adding F2
(c) ˆˆ† PCl3 + Cl 2
PCl5 ‡ˆˆ (b) Increasing the volume of the container
ˆˆ† 2NO
(d) N 2 + O 2 ‡ˆˆ (c) Removing Cl2
46. For the manufacture of ammonia by the reaction (d) Increasing the temperature
ˆˆ† 2NH3 + 2 kcal 53. Match the columns
N2 + 3H2 ‡ˆˆ
Column-I Column-II
the favourable conditions are (A) Qc < Kc, (p) Net reaction goes from
(a) Low temperature, low pressure and catalyst right to left.
(b) Low temperature, high pressure and catalyst (B) Qc > Kc, (q) Net reaction goes from
(c) High temperature, low pressure and catalyst left to right.
(d) High temperature, high pressure and catalyst (C) Qc = Kc, (r) No net reaction occurs.
47. Which one of the following information can be obtained on (a) A – (p), B – (q), C – (r)
the basis of Le Chatelier principle? (b) A – (r), B – (q), C – (p)
(a) Dissociation constant of a weak acid (c) A – (p), B – (r), C – (q)
(b) Entropy change in a reaction (d) A – (q), B – (p), C – (r)
(c) Equilibrium constant of a chemical reaction 54. Read the following statements and choose the correct option
(d) Shift in equilibrium position on changing value of a (i) The numerical value of the equilibrium constant for a
constraint reaction indicates the extent of the reaction.
48. Suitable conditions for melting of ice : (ii) An equilibrium constant give information about the
(a) high temperature and high pressure rate at which the equilibrium is reached.
(b) high temperature and low pressure
 EBD_7374
90 CHEMISTRY

(iii) If Kc > 103, products predominate over reactants, i.e., if (a) in the direction of stronger base and stronger acid
Kc is very large, the reaction proceeds nearly to (b) in the direction of formation of stronger base and
completion. weaker acid
(iv) If Kc < 10–3, reactants predominate over products, i.e., (c) in the direction of formation of weaker base and weaker
if Kc is very small, the reaction proceeds rarely. acid
(a) (i), (ii) and (iv) are correct (d) in the direction of formation of weaker base and
stronger acid
(b) (i) , (iii) and (iv)
64. Three reactions involving H2PO4– are given below:
(c) (i), (ii) and (iii) are correct
(i) H3PO4 + H2O® H3O+ + H2PO4–
(d) only (iii) is correct
(ii) H2PO4– + H2O ® HPO42– + H3O+
Topic 4: Acids, Bases and Salts Ionisation of Acids and Bases (iii) H2PO4– + OH– ® H3PO4 + O2–
55. A base, as defined by Bronsted theory, is a substance which In which of the above does H 2 PO-4 act as an acid ?
can (a) (ii) only (b) (i) and (ii)
(a) lose a pair of electrons (c) (iii) only (d) (i) only
(b) donate protons 65. The value of the ionic product of water
(c) gain a pair of electrons (a) depends on volume of water
(d) accept protons (b) depends on temperature
(c) changes by adding acid or alkali
56. Conjugate acid of NH -2 is : (d) always remains constant
(a) NH4+ (b) NH3 (c) NH2 (d) NH 66. Match the columns
57. Which of the following molecules acts as a Lewis acid ? Column-I Column-II
(a) (CH3)2 O (b) (CH3)3 P (A) Hydrochloric acid (p) Lemon and orange
(c) (CH3)3 N (d) (CH3)3 B (B) Acetic acid (q) Tamarind paste.
58. Among boron trifluoride, stannic chloride and stannous (C) Citric and ascorbic (r) Digestive juice
chloride, Lewis acid is represented by acids
(a) only stannic chloride (D) Tartaric acid (s) Constituent of vinegar
(b) boron trifluoride and stannic chloride (a) A – (q), B – (r), C – (p), D – (s)
(c) boron trifluoride and stannous chloride (b) A – (r), B – (s), C – (p), D – (q)
(d) only boron trifluoride (c) A – (s), B – (p), C – (q), D – (r)
59. Which one of the following molecular hydrides acts as a (d) A – (r), B – (p), C – (s), D – (q)
Lewis acid? 67. The pH of a 10–3 M HCl solution at 25°C if it is diluted 1000
(a) NH3 (b) H2O (c) B2H6 (d) CH4 times, will be –
60. Which one of the following is the correct statement ? (a) 3 (b) zero (c) 5.98 (d) 6.02
(a) HCO3– is the conjugate base of CO32–. 68. How many litres of water must be added to 1 litre of an
(b) NH2– is the conjugate acid of NH3. aqueous solution of HCl with a pH of 1 to create an aqueous
(c) H2SO4 is the conjugate acid of HSO4–. solution with pH of 2 ?
(a) 0.1 L (b) 0.9 L (c) 2.0 L (d) 9.0 L
(d) NH3 is the conjugate base of NH2–.
69. What is the approximate pH of a 1 × 10–3 M NaOH solution?
61. Match the columns
(a) 3 (b) 11 (c) 7 (d) 1 × 10–11
Column-I Column-II 70. Calculate the pOH of a solution at 25°C that contains
(A) HClO4 (p) Strong base 1× 10– 10 M of hydronium ions, i.e. H3O+.
(B) HNO2 (q) Strong acid (a) 4.000 (b) 9.0000 (c) 1.000 (d) 7.000
(C) NH2– (r) Weak base 71. The pH value of a 10 M solution of HCl is
(D) HSO4– (s) Weak acid (a) less than 0 (b) equal to 0
(a) A – (s), B – (q), C – (p), D – (r) (c) equal to 1 (d) equal to 2
(b) A – (q), B – (s), C – (p), D – (r) 72. What is the H+ ion concentration of a solution prepared by
(c) A – (r), B – (p), C – (q), D – (s) dissolving 4 g of NaOH (Atomic weight of Na = 23 amu) in
(d) A – (s), B – (q), C – (p), D – (r) 1000 ml?
62. Water is well known amphoprotic solvent. In which chemical (a) 10–10 M (b) 10–4 M (c) 10–1 M (d) 10–13 M
reaction water is behaving as a base? 73. In HS–, I–, RNH2 and NH3, order of proton accepting
(a) H 2SO 4 + H 2 O ¾¾ ® H 3O + + HSO 4 – tendency will be
(a) I– > NH3 > RNH2 > HS–
(b) ® H 3 O + + OH –
H 2 O + H 2 O ¾¾
(b) HS– > RNH2 > NH3 > I–
(c) H2O + NH2 – ¾¾
® NH3 + OH – (c) RNH2 > NH3 > HS– > I–
(d) H 2 O + NH 3 ¾¾ ® NH 4+ + OH – (d) NH3 > RNH2 > HS– > I–
63. An acid/ base dissociation equilibrium is dynamic involving 74. A weak acid, HA, has a Ka of 1.00 × 10–5. If 0.100 mole of this
a transfer of proton in forward and reverse directions. Now, with acid dissolved in one litre of water, the percentage of acid
passage of time in which direction equilibrium is favoured? dissociated at equilbrium is closest to
(a) 1.00% (b) 99.9% (c) 0.100% (d) 99.0%
EQUILIBRIUM 91

75. A monobasic weak acid solution has a molarity of 0.005 and (ii) At 298K [H+] = [OH–] = 10–7
pH of 5. What is the percentage ionization in this solution? (iii) Kw does not depends upon temperature
(a) 2.0 (b) 0.2 (c) 0.5 (d) 0.25 (iv) Molarity of pure water = 55.55 M
76. Calculate the pH of a solution obtained by diluting 1 mL of (a) (i), (ii) and (iii) (b) (i), (ii) and (iv)
0.10 M weak monoacidic base to 100 mL at constant (c) (i) and (iv) (d) (ii) and (iii)
temperature if Kb of the base is 1 × 10–5 ? 87. In qualitative analysis, in III group NH4Cl is added before
(a) 8 (b) 9 (c) 10 (d) 11 NH4OH because
77. Equimolar solutions of HF, HCOOH and HCN at 298 K have (a) to increase the concentration of NH4+ions
the values of Ka as 6.8 × 10–4 and 4.8 × 10–9 respectively. (b) to increase concentration of Cl– ions
What is the observed trend of dissociation constants in (c) to reduce the concentration of OH– ions
successive stages ? (d) to increase concentration of OH– ions
(a) HF > HCN > HCOOH (b) HF > HCOOH > HCN 88. The solubility of AgI in NaI solution is less than that in pure
(c) HCN > HF > HCOOH (d) HCOOH > HCN > HF water because :
78. At 25°C, the dissociation constant of a base, BOH, is (a) the temperature of the solution decreases
1.0 ´ 10 -12. The concentration of hydroxyl ions in (b) solubility product to AgI is less than that of NaI
0.01 M aqueous solution of the base would be (c) of common ion effect
(a) 1.0 ´ 10-5 mol L-1 (b) 1.0 ´ 10-6 mol L-1 (d) AgI forms complex with NaI
-6
(c) 2.0 ´ 10 mol L -1 (d) 1.0 ´ 10-7 mol L-1 89. Which of the following statements about pH and H+ ion
79. Which of the following pKa value represents the strongest concentration is incorrect?
acid ? (a) Addition of one drop of concentrated HCl in NH4OH
(a) 10–4 (b) 10–8 (c) 10–5 (d) 10–2 solution decreases pH of the solution.
80. Which equilibrium can be described as an acid-base reaction (b) A solution of the mixture of one equivalent of each of
using the Lewis acid-base definition but not using the CH3COOH and NaOH has a pH of 7
Bronsted-Lowry definition? (c) pH of pure neutral water is not zero
(a) 2NH3 + H2SO4 2NH4+ + SO42– (d) A cold and concentrated H2SO4 has lower H+ ion
concentration than a dilute solution of H2SO4
(b) NH3 + CH3COOH NH4+ + CH3COO–
90. H2S gas when passed through a solution of cations
(c) H2O + CH3COOH H3O+ + CH3COO– containing HCl precipitates the cations of second group
(d) [Cu(H2O)4]2– + 4 NH3 [Cu(NH3)4]2+ + 4H2O of qualitative analysis but not those belonging to the
fourth group. It is because
81. The dissociation constant of two acids HA1 and HA2 are
(a) presence of HCl decreases the sulphide ion
3.14 × 10– 4 and 1.96 × 10– 5 respectively. The relative strength
concentration.
of the acids will be approximately
(b) solubility product of group II sulphides is more than
(a) 1 : 4 (b) 4 : 1 (c) 1 : 16 (d) 16 : 1
that of group IV sulphides.
82. Given
K
(c) pr esen ce of HCl increases the sul phi de ion
a ® H O+ + F-
HF + H 2 O ¾¾¾ 3 concentration.
K
F- + H 2 O ¾¾¾ b ® HF + OH - (d) sulphides of group IV cations are unstable in HCl.
91. 100 mL of 0.04 N HCl aqueous solution is mixed with 100 mL
Which of the following reaction is correct
1 of 0.02 N NaOH solution. The pH of the resulting solution is:
(a) Kb = Kw (b) K b = (a) 1.0 (b) 1.7 (c) 2.0 (d) 2.3
Kw
Ka 92. At 100°C the Kw of water is 55 times its value at 25°C. What
(c) Ka × Kb = Kw (d) = Kw
Kb will be the pH of neutral solution? (log 55 = 1.74)
83. At 298K a 0.1 M CH3COOH solution is 1.34% ionized. The (a) 6.13 (b) 7.00 (c) 7.87 (d) 5.13
ionization constant Ka for acetic acid will be 93. Ionisation constant of CH3COOH is 1.7 × 10 –5 if
(a) 1.82 × 10– 5 (b) 18.2 × 10 –5 concentration of H+ ions is 3.4 × 10–4M, then find out initial
(c) 0.182 × 10 –5 (d) None of these concentration of CH3COOH molecules
84. Equal volumes of three acid solutions of pH 3, 4 and 5 are (a) 3.4 × 10–4 M (b) 3.4 × 10–3 M
mixed in a vessel. What will be the H+ ion concentration in (c) 6.8 × 10–3 M (d) 6.8 × 10–4 M
the mixture ? 94. Values of dissociation constant, Ka are given as follows :
(a) 1.11 × 10–4 M (b) 3.7 × 10–4 M Acid Ka
(c) 3.7 × 10 M– 3 (d) 1.11× 10–3 M HCN 6.2 × 10–10
85. The pKa of a weak acid, HA, is 4.80. The pKb of a weak base, HF 7.2 × 10–4
BOH, is 4.78. The pH of an aqueous solution of the HNO2 4.0 × 10–4
correspondng salt, BA, will be Correct order of increasing base strength of the base CN–,
(a) 9.58 (b) 4.79 (c) 7.01 (d) 9.22 F– and NO–2 will be :
_ _
86. Which of the following statements are correct ? (a) F- < CN - < NO2 (b) NO2 < CN - < F-
_ _
(i) Ionic product of water (Kw) = [H+] [OH–] = 10–14 M2 (c) F- < NO2 < CN - (d) NO2 < F- < CN -
 EBD_7374
92 CHEMISTRY

95. The dissociation constants for acetic acid and HCN at 25°C 105. At 25°C, the solubility product of Mg(OH)2 is 1.0 × 10–11.
are 1.5 × 10–5 and 4.5 × 10–10 respectively. The equilibrium At which pH, will Mg2+ ions start precipitating in the form
constant for the equilibrium of Mg(OH)2 from a solution of 0.001 M Mg2+ ions?
CN– + CH3COOH ƒ HCN + CH3COO– would be: (a) 9 (b) 10 (c) 11 (d) 8
(a) 3.3 × 10– 5 (b) 3.3 × 10– 4 106. When a buffer solution, sodium acetate and acetic acid is
(c) 3.3 × 10 4 (d) 3.3 × 105 diluted with water :
96. If degree of dissociation of pure water at 100°C is (a) Acetate ion concentration increases
1.8 × 10–8, then the dissociation constant of water will be (b) H+ ion concentration increases
(density of H2O = 1 g/cc) (c) OH– ion conc. increases
(a) 1 × 10–12 (b) 1 × 10–14 (d) H+ ion concentration remains unaltered
(c) 1.8 × 10–12 (d) 1.8 × 10–14 107. The product of ionic concentration in a saturated solution
97. Ionisation of weak acid can be calculated by the formula of an electrolyte at a given temperature is constant and is
known as
Ka 100 (a) Ionic product of the electrolyte
(a) 100 (b)
C 1 + 10(pKa - pH) (b) Solubility product
(c) Both (a) and (b) (d) None of these (c) Ionization constant
98. Which of the following statements are correct ? (d) Dissociation constant
(i) The extent of dissociation of an acid depends on the 108. pH of a saturated solution of Ba(OH)2 is 12. The value of
strength and polarity of the H –– A bond (where A is an solubility product (Ksp) of Ba(OH)2 is :
electronegative element.) (a) 3.3 × 10– 7 (b) 5.0 × 10–7
(c) 4.0 × 10 –6 (d) 5.0 × 10–6
(ii) As the strength of H–A bond increases, the energy
required to break the bond decreases. 109. What is the molar solubility of Fe(OH)3 if Ksp = 1.0 ×10–38 ?
(iii) As the electronegativity difference between the atoms (a) 3.16×10–10 (b) 1.386×10–10
H and A increases, acidity increases (c) 1.45×10 –9 (d) 1.12×10–11
(a) (i) and (ii) (b) (ii) and (iii) 110. If s and S are respectively solubility and solubility product
(c) (i) and (iii) (d) (i), (ii) and (iii) of a sparingly soluble binary electrolyte then :
1
Topic 5: Buffer Solutions (a) s = S (b) s = S2 (c) s = S1/ 2 (d) s = S
2
Solubility Equilibria of Sparingly Soluble Salts 111. Why only As3+ gets precipitated as As2S3 and not Zn2+ as
ZnS when H2S is passed through an acidic solution
99. The pKa of a weak acid (HA) is 4.5. The pOH of an aqueous
containing As3+ and Zn2+?
buffer solution of HA in which 50% of the acid is ionized is
(a) Solubility product of As2S3 is less than that of ZnS
(a) 7.0 (b) 4.5 (c) 2.5 (d) 9.5
(b) Enough As3+ are present in acidic medium
100. A buffer solution is prepared in which the concentration of
(c) Zinc salt does not ionise in acidic medium
NH3 is 0.30M and the concentration of NH4+ is 0.20 M. If the
(d) Solubility product changes in presence of an acid
equilibrium constant, Kb for NH3 equals 1.8 × 10–5, what is
112. Solid Ba(NO 3 ) 2 is gradually dissolved in a
the pH of this solution ? (log 2.7 = 0.433).
1.0 × 10–4 M Na2CO3 solution. At which concentration of
(a) 9.08 (b) 9.43 (c) 11.72 (d) 8.73
Ba2+, precipitate of BaCO3 begins to form ? (Ksp for BaCO3
101. What is [H+] in mol/L of a solution that is 0.20 M in
= 5.1 × 10–9)
CH3COONa and 0.10 M in CH3COOH ? Ka for CH3COOH
(a) 5.1 × 10–5 M (b) 7.1 × 10–8 M
= 1.8 × 10–5. –5
(c) 4.1 × 10 M (d) 8.1 × 1–7 M
(a) 3.5 × 10–4 10-4 (b) 1.1 × 10–5
–5 113. A buffer solution is prepared by mixing 10 ml of 1.0 M
(c) 1.8 × 10 (d) 9.0 × 10–6
CH3COOH and 20 ml of 0.5 M CH3COONa and then diluted
102. Which of the following pairs constitutes a buffer?
to 100 ml with distilled water. If pKa of CH3COOH is 4.76,
(a) NaOH and NaCl (b) HNO3 and NH4NO3
what is the pH of the buffer solution ?
(c) HCl and KCl (d) HNO2 and NaNO2
(a) 5.8 (b) 4.34 (c) 5.21 (d) 4.76
103. Buffer solutions have constant acidity and alkalinity because
114. Solubility product of silver bromide is 5.0 × 10–13. The
(a) these give unionised acid or base on reaction with
quantity of potassium bromide (molar mass taken as
added acid or alkali.
120 g mol–1) to be added to 1 litre of 0.05 M solution of
(b) acids and alkalies in these solutions are shielded from
silver nitrate to start the precipitation of AgBr is
attack by other ions.
(a) 1.2 × 10–10 g (b) 1.2 × 10–9 g
(c) they have large excess of H+ or OH– ions –5
(c) 6.2 × 10 g (d) 5.0 × 10–8 g
(d) they have fixed value of pH
115. Solubility product constant (Ksp) of salts of types MX, MX2
104. The Ksp for Cr(OH)3 is 1.6 × 10–30. The solubility of this
and M3X at temperature T are 4.0 × 10–8, 3.2 × 10–14 and
compound in water is :
2.7 × 10–15, respectively. Solubilities (mol dm–3) of the salts
(a) 4
1.6 ´ 10 -30 (b) 4
1.6 ´ 10 -30 / 27 at temperature 'T' are in the order –
(a) MX > MX2 > M3X (b) M3X > MX2 > MX
(c) 1.6 ´ 10-30/ 27 (d) 1.6 ´ 10 -30 (c) MX2 > M3X > MX (d) MX > M3X > MX2
EQUILIBRIUM 93

116. In qualitative analysis, the metals of Group I can be separated 117. A buffer solution is prepared by mixing 0.1 M ammonia and
from other ions by precipitating them as chloride salts. A 1.0 M ammonium chloride. At 298 K, the pKb of NH4OH is
solution initially contains Ag+ and Pb2+ at a concentration 5.0. The pH of the buffer is
of 0.10 M. Aqueous HCl is added to this solution until the (a) 10.0 (b) 9.0 (c) 6.0 (d) 8.0
Cl– concentration is 0.10 M. What will the concentrations of 118. What is the correct relationship between the pHs of
Ag+ and Pb2+ be at equilibrium? isomolar solutions of sodium oxide (pH1), sodium
(Ksp for AgCl = 1.8 × 10–10, Ksp for PbCl2 = 1.7 × 10–5) sulphide (pH2), sodium selenide (pH3) and sodium
(a) [Ag+] = 1.8 × 10–7 M ; [Pb2+] = 1.7 × 10–6 M telluride (pH4)?
(b) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–5 M (a) pH1 > pH2 > pH3 > pH4
(c) [Ag+] = 1.8 × 10–9 M ; [Pb2+] = 1.7 × 10–3 M (b) pH1 > pH2 » pH3 > pH4
(d) [Ag+] = 1.8 × 10–11 M ; [Pb2+] = 8.5 × 10–4 M (c) pH1 < pH2 < pH3 < pH4
(d) pH1 < pH2 < pH3 » pH4

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 6. When hydrochloric acid is added to cobalt solution at room
1. We know that the relationship between Kc and Kp is temperature, the following reaction takes place and thus
Kp = Kc (RT)Dn the reaction mixture becomes blue. On cooling the mixture
What would be the value of Dn for the reaction? it becomes pink. On the basis of this information mark the
ˆˆ† NH 3 (g ) + HI ( g ) correct answer.
NH 4 Cl ( s ) ‡ˆˆ 3+
ˆˆ†
éë Co ( H 2 O )6 ùû ( aq ) + 4Cl- ( aq ) ‡ˆˆ
(a) 1 (b) 0.5 (c) 1.5 (d) 2
2. For the reaction, H 2 ( g ) + I2 ( g ) ‡ˆˆ ˆˆ† 2HI (g ) , the Pink

standard free energy is DG° > 0. The equilibrium constant [CoCl4 ]2- ( aq ) + 6H 2O ( l )
Blue
(K) would be
(a) DH > 0 for the reaction
(a) K = 0 (b) K > 1 (c) K = 1 (d) K < 1
(b) DH < 0 for the reaction
3. Which of the following is not a general characteristic of
(c) DH = 0 for the reaction
equilibria involving physical processes?
(d) The sign of DH cannot be predicted on the basis of
(a) Equilibrium is possible only in a closed system at a
this information
given temperature.
7. The pH of neutral water at 25°C is 7.0. As the temperature
(b) All measurable properties of the system remain
increases, ionisation of water increases, however, the
constant.
concentration of H+ ions and OH– ions are equal. What will
(c) All the physical processes stop at equilibrium.
be the pH of pure water at 60°C?
(d) The opposing processes occur at the same rate and
(a) Equal to 7.0 (b) Greater than 7.0
there is dynamic but stable condition.
(c) Less than 7.0 (d) Equal to zero
4. PCl5, PCl3, and Cl2 are at equilibrium at 500 K in a closed 8. The ionisation constant of an acid, Ka is the measure of
container and their concentrations are 0.8 × 10–3 mol L–1, strength of an acid. The Ka values of acetic acid, hypochlorous
1.2 × 10–3 mol L–1 and 1.2 × 10–3 mol L–1 respectively. The acid and formic acid are 1.74 × 10–5, 3.0 × 10–8 and 1.8 × 10–4
value of Kc for the reaction respectively. Which of the following orders of pH of 0.1
ˆˆ† PCl3 ( g ) + Cl2 ( g ) will be
PCl5 ( g ) ‡ˆˆ mol dm–3 solutions of these acids is correct?
(a) 1.8 × 103 mol L–1 (b) 1.8 × 10–3 (a) Acetic acid > hypochlorous acid > formic acid
–3
(c) 1.8 × 10 mol L –1 (d) 0.55 × 104 (b) Hypochlorous acid > acetic acid > formic acid
5. Which of the following statements is incorrect? (c) Formic acid > hypochlorous acid > acetic acid
(a) In equilibrium mixture of ice and water kept in perfectly (d) Formic acid > acetic acid > hypochlorous acid
insulated flask, mass of ice and water does not change 9. K a1 , Ka 2 and K a 3 are the respective ionisation constants
with time for the following reactions.
(b) The intensity of red colour increases when oxalic acid ˆˆ† H + + HS-
H 2S ‡ˆˆ
is added to a solution containing iron (III) nitrate and
ˆˆ† H + + S 2 -
H S - ‡ˆˆ
potassium thiocyanate
ˆˆ† 2H + + S 2 -
H 2 S ‡ˆˆ
(c) On addition of catalyst the equilibrium constant value
is not affected The correct relationship between K a1 , Ka 2 and K a 3 is
(d) Equilibrium constant for a reaction with negative DH (a) K a3 = K a1 ´ K a 2 (b) K a3 = K a1 + K a 2
value decreases as the temperature increases. K a3 = K a1 - K a 2 K a3 = K a1 / K a 2
(c) (d)
 EBD_7374
94 CHEMISTRY

10. Acidity of BF3 can be explained on the basis of which of 19. In which of the following reactions, the equilibrium remains
the following concepts? unaffected on addition of small amount of argon at constant
(a) Arrhenius concept volume?
(b) Bronsted Lowry concept ˆˆ† 2HI ( g )
(a) H 2 ( g ) + I2 ‡ˆˆ
(c) Lewis concept
(d) Bronsted Lowry as well as Lewis concept (b) ˆˆ† PCl3 ( g ) + Cl2 ( g )
PCl5 ( g ) ‡ˆˆ
11. Which of the following will produce a buffer solution when (c) ˆˆ† 2NH 3 ( g )
N 2 ( g ) + 3H 2 ( g ) ‡ˆˆ
mixed in equal volumes?
(d) The equilibrium will remain unaffected in all the three
(a) 0.1 mol dm–3 NH4OH and 0.1 mol dm–3 HCl
cases
(b) 0.05 mol dm–3 NH4OH and 0.1 mol dm–3 HCl
(c) 0.1 mol dm–3 NH4OH and 0.05 mol dm–3 HCl Past Year MCQs
(d) 0.1 mol dm–3 CH3COONa and 0.1 mol dm–3 NaOH 20. For the reversible reaction, [AIPMT 2014, C]
12. In which of the following solvent silver chloride is most N2(g) + 3H2(g) 2NH3(g) + heat
soluble? The equilibrium shifts in forward direction
(a) 0.1 mol dm–3 AgNO3 solution (a) By increasing the concentration of NH3(g)
(b) 0.1 mol dm–3 HCl solution (b) By decreasing the pressure
(c) H2O (c) By decreasing concentration of N2(g) and H2(g)
(d) Aqueous ammonia (d) By increasing pressure and decreasing temperature.
13. What will be the value of pH of 0.01 mol dm–3 CH3COOH 21. For a given exothermic reaction, Kp and KP¢ are the equilibrium
(Ka = 1.74 × 410–5)? constants at temperatures T1 and T2, respectively. Assuming
(a) 3.4 (b) 3.6 (c) 3.9 (d) 3.0 that heat of reaction is constant in temperature range
14. Ka for CH3COOH is 1.8 × 10–5 and Kb for NH4OH is
between T1 and T2, it is readily observed that:
1.8 × 10–5.The pH of ammonium acetate will be
[AIPMT 2014, C]
(a) 7.005 (b) 4.75
(a) Kp > KP¢ (b) Kp < KP¢
(c) 7.0 (d) Between 6 and 7
15. Which of the following options will be correct for the stage 1
ˆˆ† B?
of half completion of the reaction A ‡ˆˆ (c) Kp = KP¢ (d) Kp =
K¢p
– –
(a) DG = 0 (b) DG > 0
– 22. Which of the following salts will give highest pH in water?
(c) DG < 0 (d) DGs = - RT ln K [AIPMT 2014, C]
16. On increasing the pressure, in which direction will the gas (a) KCl (b) NaCl
phase reaction proceed to re-establish equilibrium, is (c) Na2CO3 (d) CuSO4
predicted by applying the Le-Chatelier's principle. Consider 23. Using the Gibbs energy change, DG° = + 63.3kJ, for the
the reaction, following reaction, [AIPMT 2014, A]
N 2 (g) + 3H 2 ‡ˆˆˆˆ† 2NH3 ( g )
Ag2CO3 2Ag+ (aq) + CO32–(aq)
Which of the following is correct, if the total pressure at the Ksp of Ag2CO3(s) in water at 25°C is:-
which the equilibrium is established, is increased without (R = 8.314 J K–1 mol–1)
changing the temperature? (a) 3.2 × 10–26 (b) 8.0 × 10–12
(a) K will remain same –3
(c) 2.9 × 10 (d) 7.9 × 10–2
(b) K will decrease
24. Which of the following equilibria will shift to right side on
(c) K will increase
increasing the temperature? [AIIMS 2014, C]
(d) K will increase initially and decrease when pressure is
(a) CO (g) + H2O (g) ‡ˆˆˆˆ† CO (g) + H (g)
very high 2 2
17. What will be the correct order of vapour pressure of water, (b) 2SO2(g) + O2 (g) ‡ˆˆˆˆ† 2SO (g)
3
acetone and ether at 30°C? Given that among these 1
compounds, water has maximum boiling point and ether ˆˆ† H (g) +
(c) H2O (g) ‡ˆˆ O 2 (g)
2
2
has minimum boiling point?
ˆˆ† 2H O (g) + 2Cl (g)
(d) 4HCl (g) + O2 (g) ‡ˆˆ
(a) Water < ether < acetone 2 2
(b) Water < acetone < ether 1 ˆˆ†SO3 (g) , if
25. For the reaction SO2 (g) + O2 (g) ‡ˆˆ
(c) Ether < acetone <water 2
(d) Acetone < ether < water K P = K C ( RT ) where the symbols have usual meaning
x
18. At 500 K, equilibrium constant, Kc, for the following reaction then the value of x is (assuming ideality): [JEE M 2014, A]
is 5.
1 1
1 1
ˆˆ† HI ( g )
H 2 ( g ) + I 2 ( g ) ‡ˆˆ (a) –1 (b) - (c) (d) 1
2 2
2 2 26. For a given exothermic reaction, Kp and KP¢ are the equilibrium
What would be the equilibrium constant KC for the reaction ?
2HI(g) ƒ H2(g) + I2(g) constants at temperatures T1 and T2, respectively. Assuming
(a) 0.04 (b) 0.4 (c) 25 (d) 2.5 that heat of reaction is constant in temperature range
EQUILIBRIUM 95

between T1 and T2, it is readily observed that: (a) If both Assertion and Reason are correct and Reason
[BITSAT 2014, C] is the correct explanation of Assertion.
(a) Kp > KP¢ (b) Kp < KP¢ (b) If both Assertion and Reason are correct, but Reason
is not the correct explanation of Assertion.
1 (c) If Assertion is correct but Reason is incorrect.
(c) Kp = KP¢ (d) Kp =
K¢p (d) If both the Assertion and Reason are incorrect.
35. The following reaction is performed at 298 K.
27. If the value of an equilibrium constant for a particular reaction
2NO(g) + O2(g) 2NO2(g)
is 1.6 × 1012, then at equilibrium the system will contain :-
The standard free energy of formation of NO(g) is
[AIPMT 2015, C]
86.6 kJ/mol at 298 K. What is the standard free energy of
(a) mostly reactants
formation of NO2(g) at 298 K? (Kp = 1.6 × 1012)
(b) mostly products
[JEE M 2015, S]
(c) similar amounts of reactants and products
(d) all reactants ln (1.6 ´ 1012 )
28. If the equilibrium constant for (a) 86600 –
R (298)
N2(g) + O2(g) 2NO(g) is K,
(b) 0.5[2 × 86,600 – R(298) ln(1.6 × 1012)]
the equilibrium constant for [AIPMT 2015 RS, A]
(c) R(298) ln(1.6 × 1012) – 86600
1 1 (d) 86600 + R(298) ln(1.6 × l012)
N2(g) + O2(g) NO(g) will be:
2 2 36. The standard Gibbs energy change at 300 K for the reaction
1 ˆˆ† B + C is 2494.2 J. At a given time, the composition
2A ‡ˆˆ
1
(a) K2 (b) K (c) K (d) K2 1 1
2 of the reaction mixture is [A] = , [B] = 2 and [C] = . The
2 2
29. Which of the following statements is correct for a reversible reaction proceeds in the : [R = 8.314 J/K/mol, e1 = 2.718]
process in a state of equilibrium ? [AIPMT 2015, A] [JEE M 2015, C]
(a) DG = 2.30 RT log K (b) DGº = –2.30 RT log K (a) forward direction because Q < KC
(c) DGº = 2.30 RT log K (d) DG = –2.30 RT log K (b) reverse direction because Q < KC
30. What is the pH of the resulting solution when equal volumes (c) forward direction because Q > KC
of 0.1 M NaOH and 0.01 M HCl are mixed ? (d) reverse direction because Q > KC
[AIPMT 2015 RS, S] 37. Which of the following according to Le-Chatelier’s principle
(a) 12.65 (b) 2.0 (c) 7.0 (d) 1.04 is correct? [BITSAT 2015, C]
31. The Ksp of Ag2CrO4, AgCl, AgBr and AgI are respectively, (a) Increase in temperature favours the endothermic reaction
1.1 × 10–12, 1.8 × 10–10, 5.0 × 10–13, 8.3 × 10–17. Which one of (b) Increase in temperature favours the exothermic reaction
the following salts will precipitate last if AgNO3 solution is (c) Increase in pressure shifts the equilibrium in that side
added to the solution containing equal moles of NaCl, NaBr, in which number of gaseous moles increases
NaI and Na2CrO4? [AIPMT 2015, S] (d) All of the above are true
(a) AgCl (b) AgBr (c) Ag2CrO4 (d) AgI 38. What is the correct increasing order of Bronsted bases?
32. Which one of the following pairs of solution is not an acidic [BITSAT 2015, C]
buffer ? [AIPMT 2015 RS, C]
(a) HClO4 and NaClO4 (b) CH3COOHandCH3 COONa (a) ClO -4 < ClO3- < ClO-2 < ClO -
(c) H2CO3 and Na2CO3 (d) H3PO4 and Na3PO4
(b) ClO-4 > ClO3- > ClO -2 > ClO-
33. The reaction 2A(g) + B(g) ƒ 3C(g) + D(g) is began with
the concentrations of A and B both at an initial value of 1.00 (c) ClO3- < ClO4- < ClO2- < ClO -
M. When equilibrium is reached, the concentration of D is
measured and found to be 0.25 M. The value for the (d) ClO- > ClO3- > ClO 2- < ClO 4-
equilibrium constant for this reaction is given by the 39. Consider the following liquid - vapour equilibrium.
expression [AIIMS 2015, S] Liquid Vapour
(a) [(0.75)3 (0.25)] ¸ [(0.75)2 (0.25)] Which of the following relations is correct ?
(b) [(0.75)3 (0.25)] ¸ [(1.00)2 (1.00)] [NEET 2016, C]
(c) [(0.75)3 (0.25)] ¸ [(0.50)2 (0.75)]
(d) [(0.75)3 (0.25)] ¸ [(0.50)2 (0.25)]
dlnG DH v dlnP DH v
(a) 2
= (b) =
34. Assertion : Buffer system of carbonic acid and sodium dT RT 2 dT RT
bicarbonate is used for the precipitation of hydroxides of
dlnP -DH v dlnP -DH v
third group elements. [AIIMS 2015, C] (c) 2
= 2 (d) =
Reason : It maintains the pH to a constant value, about 7.4. dT T dT RT 2
 EBD_7374
96 CHEMISTRY

40. MY and NY3, two nearly insoluble salts, have the same Ksp [BITSAT 2016, A]
values of 6.2 × 10–13 at room temperature. Which statement
(a) Ls ® Ksp = S pq (pq) P + q
would be true in regard to MY and NY3 ? [NEET 2016, C]
(a) The molar solubilities of MY and NY3 in water are (b) Ls = S
p+q p q
.p q
identical.
(b) The molar solubility of MY in water is less than that of (c) Ls ® Ksp = Sp + q .p q q p
NY3
(d) Ls ® Ksp = Spq p p q q
(c) The salts MY and NY3 are more soluble in 0.5 M KY
than in pure water. 47. The percentage hydrolysis of 0.15 M solution of ammonium
(d) The addition of the salt of KY to solution of MY and acetate, Ka for CH3COOH is 1.8 × 10–5 and Kb for NH3 is
NY3 will have no effect on their solubilities. 1.8 × 10–5 [BITSAT 2016, S]
41. Consider the nitration of benzene using mixed conc. of (a) 0.556 (b) 4.72 (c) 9.38 (d) 5.56
H2SO4 and HNO3. If a large amount of KHSO4 is added to 48. In a closed system, A(s) 2B(g) + 3C(g), if partial pressure
the mixture, the rate of nitration will be [NEET 2016, C] of C is doubled, then partial pressure of B will be
(a) faster (b) slower [BITSAT 2016, S]
(c) unchanged (d) doubled (a) 2 2 times the original value
42. The solubility product (Ksp) of the following compounds
are given at 25°C. 1
(b) times the original value
Compound Ksp 2
AgCl 1.1 × 10–10 (c) 2 times the original value
AgI 1.0 × 10–16
1
PbCrO4 4.0 × 10–14 (d) times the original value
Ag2CO3 8.0 × 10–12 2 2
The most soluble and least soluble compounds are 49. The degree of dissociation of PCl 5(a) obeying the
respectively. [AIIMS 2016, A] equilibrium PCl5 PCl3 + Cl2 is related to the equilibrium
(a) AgCl and PbCrO4 pressure by [BITSAT 2016, S]
(b) AgI and Ag2CO3
(c) AgCl and Ag2CO3 1 1
(a) aµ (b) aµ
(d) Ag2CO3 and AgI 4 P
P
43. Assertion : Addition of silver ions to a mixture of aqueous
sodium chloride and sodium bromide solution will first 1
(c) aµ (d) a µ P
precipitate AgBr rather than AgCl. P2
Reason : Ksp of AgCl > Ksp of AgBr. [AIIMS 2016, C] 50. The equilibrium constant of the following are :
(a) If both Assertion and Reason are correct and Reason N2 + 3H2 ƒ 2NH3 ; K1 [NEET 2017, A]
is the correct explanation of Assertion. N2 + O2 ƒ 2NO ; K2
(b) If both Assertion and Reason are correct, but Reason
1
is not the correct explanation of Assertion. ˆˆ† H 2 O ; K
H 2 + O2 ‡ˆˆ
2 3
(c) If Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect. The equilibrium constant (K) of the reaction :
44. Two equilibria, AB ‡ˆˆˆˆˆ† +
ˆ A + B and
- 2NO + 3H2O, will be;
- ˆˆˆ † -
AB + B ‡ˆˆ ˆ AB2 are simultaneously maintained in a (a) K 2 K 33 / K1 (b) K2K3/K1
solution with equilibrium constants, K1 and K2 respectively.
The ratio of [A+] to [AB2–] in the solution is (c) K 32 K 3 / K1 (d) K1K 33 / K 2
[AIIMS 2016, C] 51. A 20 litre container at 400 K contains CO2(g) at pressure
(a) directly proportional to [B–] 0.4 atm and an excess of SrO (neglect the volume of solid
(b) inversely proportional to [B–] SrO). The volume of the container is now decreased by
(c) directly proportional to the square of [B–] moving the movable piston fitted in the container. The
(d) inversely proportional to the square of [B–] maximum volume of the container, when pressure of CO2
45. The equilibrium constant at 298 K for a r eaction attains its maximum value, will be :-
A+ B C + D is 100. If the initial concentration of all the (Given that : SrCO3 (s) SrO (s) + CO2(g), Kp = 1.6 atm)
four species were 1 M each, then equilibrium concentration [NEET 2017, A]
of D (in mol L–1) will be : [JEE M 2016, S] (a) 10 litre (b) 4 litre (c) 2 litre (d) 5 litre
(a) 1.818 (b) 1.182 (c) 0.182 (d) 0.818 52. Concentration of the Ag+ ions in a saturated solution of
46. For a sparingly soluble salt ApBq, the relationship of its Ag2C2O4 is 2.2 × 10–4 mol L–1. Solubility product of Ag2C2O4
solubility product Ls ® Ksp with its solubility (S) is is :- [NEET 2017, A]
EQUILIBRIUM 97

(a) 2.66 × 10–12 (b) 4.5 × 10–11 61. Assertion : If Qc (reaction quotient) < KC (equilibrium
(c) 5.3 × 10 –12 (d) 2.42 × 10–8 constant) reaction moves in direction of reactants.
53. Which of the following can form buffer solution? Reason : Reaction quotient is defined in the same way as
[NEET 2017, C] equilbrium constant at any stage of the reaction.
(a) aq.NH3 + NH4OH (b) KOH + HNO3 [AIIMS 2018, C]
(c) NaOH + HCl (d) KI + KOH (a) If both Assertion and Reason are correct and Reason
54. For the following reaction in gaseous phase is the correct explanation of Assertion.
1 (b) If both Assertion and Reason are correct, but Reason
CO(g) + O 2 (g) ® CO 2 (g), Kp / K c is
2 is not the correct explanation of Assertion.
[AIIMS 2017, A] (c) If Assertion is correct but Reason is incorrect.
(a) (RT)1/2 (b) (RT)–1/2 (c) (RT) (d) (RT)–1 (d) If both the Assertion and Reason are incorrect.
55. pKa of a weak acid (HA) and pKb of a weak base (BOH) are 62. Which of the following salts in the most basic in aqueous
3.2 and 3.4, respectively. The pH of their salt (AB) solution solution? [JEE M 2018, S]
is [JEE M 2017, A] (a) Al(CN)3 (b) CH3COOK
(a) 7.2 (b) 6.9 (c) 7.0 (d) 1.0 (c) FeCl3 (d) Pb(CH3COO)2
56. Which of the following can act as both Bronsted acid and 63. An aqueous solution contains 0.10 MH2S and 0.20 M HCl.
Bronsted base? [BITSAT 2017, C] If the equilibrium constants for the formation of HS– from
(a) Na2CO3 (b) OH– (c) HCO3– (d) NH3 H2S is 1.0 × 10–7 and that of S2– from HS– ions is 1.2 × 10–13
57. Which one of the following conditions will favour maximum then the concentration of S2– ions in aqueous solution is:
formation of the product in the reaction, [NEET 2018, C] [JEE M 2018, S]
ˆˆ† X 2 (g) D r H = –X kJ :
A 2 (g) + B2 (g) ‡ˆˆ (a) 5 × 10–8 (b) 3 × 10–20
(a) Low temperature and high pressure (c) 6 × 10–21 (d) 5 × 10–19
(b) Low temperature and low pressure 64. An aqueous solution contains an unknown concentration
(c) High temperature and low pressure of Ba2+. When 50 mL of a 1 M solution of Na 2SO4 is added,
(d) High temperature and high pressure BaSO4 just begins to precipitate. The final volume is 500 mL.
58. The solubility of BaSO4 in water is The solubility product of BaSO4 is 1 × 10–10. What is the
2.42 × 10–3 gL–1 at 298 K. The value of its solubility product original concentration of Ba2+ ? [JEE M 2018, A]
(Ksp) will be (a) 5 × 10–9 M (b) 2 × 10–9 M
(Given molar mass of BaSO4 = 233 g mol–1) (c) 1.1 × 10–9 M (d) 1.0 × 10–10 M
[NEET 2018, A] 65. For the reaction taking place at certain temperature
(a) 1.08 × 10–10 mol2L–2
(b) 1.08 × 10–12 mol2L–2 ˆˆ† 2NH 3 ( g ) + CO 2 ( g ) ,
NH 2 COONH 4 ( s ) ‡ˆˆ
(c) 1.08 × 10–8 mol2L–2 if equilibrium pressure is 3X bar then DrG° would be
(d) 1.08 × 10–14 mol2L–2 [BITSAT 2018, C]
59. Following solutions were prepared by mixing different (a) – RT ln 9 – 3RT ln X (b) RT ln 4 – 3RT ln X
volumes of NaOH and HCl of different concentrations : (c) – 3RT ln X (d) None of these
M M 66. The pH of 0.1 M solution of the following salts increases in
i. 60 mL HCl + 40 mL NaOH [NEET 2018, S] the order : [BITSAT 2018, C]
10 10
(a) NaCl < NH4Cl < NaCN < HCl
M M (b) HCl < NH4Cl < NaCl < NaCN
ii. 55 mL HCl + 45 mL NaOH
10 10 (c) NaCN < NH4Cl < NaCl < HCl
(d) HCl < NaCl < NaCN < NH4Cl
M M
iii. 75 mL HCl + 25 mL NaOH 67. When N2O5 is heated at certain temperature, it dissociates
5 5
ˆˆ† N 2 O3 ( g ) + O2 ( g ) ; Kc = 2.5. At the
as N 2 O5 ( g ) ‡ˆˆ
M M
iv. 100 mL HCl + 100 mL NaOH same time N2O3 also decomposes as :
10 10
pH of which one of them will be equal to 1? ˆˆ† N 2 O ( g ) + O 2 ( g ) . If initially 4.0 moles of
N 2 O3 ( g ) ‡ˆˆ
(a) (ii) (b) (i) (c) (iii) (d) (iv)
60. ˆˆ† 2C
A + 2B ‡ˆˆ K= ? N2O5 are taken in 1.0 litre flask and allowed to dissociate.
Concentration of O2 at equilibrium is 2.5 M. Equilibrium
2 moles of each A and B are present in 10 L solution. The
concentration of N2O5 is : [BITSAT 2018, S]
product C formed 1 mole. Calculate Kc [AIIMS 2018, A]
(a) 1.0 M (b) 1.5 M
(a) 1.5 (b) 6.67 (c) 0.15 (d) 2.3 (c) 2.166 M (d) 1.846 M
 EBD_7374
98 CHEMISTRY

Exercise 3 : Try If You Can

1. Consider the following equilibrium pressure in the flask rises to 0.84 atm? The equilibrium
constant for NH4HS decomposition at this temperature is
N 2 O4 ( g ) ƒ 2NO 2 ( g )
(a) 0.11 (b) 0.17 (c) 0.18 (d) 0.30
Then the select the correct graph, which shows the variation 5. A vessel of 250 litre was filled with 0.01 mole of Sb2S3 and
in concentrations of N2O4 against concentrations of N2O4: 0.01 mole of H2 to attain the equilibrium at 440°C as

ˆˆ† 2Sb ( s ) + 3H 2S ( g )
Sb 2 S3 ( s ) + 3H 2 ( g ) ‡ˆˆ
¾®
¾®

After equilibrium, the H2S formed was analysed by

[N O 2 ]
[NO2]

dissolved it in water and treating with excess of Pb2+ to

(a) (b) give 1.19 g of PbS as precipitate. What is the value of K c at
440°C?
[N2O4] ¾® [N2O4] ¾®
(a) 1 (b) 2 (c) 4 (d) 8
6. 8 mole of a gas AB3 are introduced into a 1.0 dm3 vessel.
It dissociates as 2AB3 (g) ƒ A 2 (g) + 3B2 (g)
¾®

¾®

At equilibrium, 2 mole of A2 is found to be present. The

equilibrium constant for the reaction is
[N O 2 ]

[N O 2 ]

(c) (d) (a) 2 mol2 L–2 (b) 3 mol2 L–2

(c) 27 mol2 L–2 (d) 36 mol2 L–2
[N2O4] ¾® [N2O4] ¾® 7. Based upon the following hypothetical equilibrium at 273 K
XCl2. 6H2O(s) XCl2. 2H2O(s) + 4 H2O(g) ;
2. Equilibrium constant for the reaction,
Kp = 8.1 × 10 atm 4
–11
CaCO3 (s) ƒ CaO (s) + CO2 (g), follows the equation
Y2HPO4. 12H2O(s) Y2HPO4. 7H2O(s) + 5H2O(g) ;
8400 –9
Kp = 3. 2 × 10 atm 5
ln Kp = 7 – , where T = absolute temperature. Find the
T Z2SO4. 10H2O(s) Z2SO4(s) + 10H2O(g) ;
equilibrium temperature if decomposition of CaCO3 –30
Kp = 1.0 × 10 atm 10
produces CO 2 gas having partial pressure equal to Which is the most effective dehydrating agent at 273 K
atmospheric pressure. (Aqueous tension at 273 K = 6.0 × 10–3 atm)
(a) 1200 °C (b) 927 K (c) 927 °C (d) None (a) X Cl2. 6H2O(s) (b) Y2 HPO4. 7H2O(s)
3. Phosphorus pentachloride dissociates as follows, in a closed (c) Z2SO4(s) (d) Z2SO4. 10H2O(s)
reaction vessel
8. For the equilibrium reaction
PCl5(g) PCl3(g) + Cl2(g)
2NOBr (g) 2NO (g) + Br2 (g)
If total pressure at equilibrium of the reaction mixture is P
and degree of dissociation of PCl5 is x, the partial pressure P
If PBr2 = , where P is total pressure at equilibrium. The
of PCl3 will be 9
æ x ö æ x ö Kp
(a) çè ÷P (b) çè ÷P ratio is equal to
x - 1ø 1- xø P
æ x ö æ 2x ö 1 1 1 1
(c) çè ÷P (d) çè ÷P (a) (b) (c) (d)
x + 1ø 1- xø 3 81 9 27
4. An amount of solid NH4HS is placed in a flask already
containing ammonia gas at a certain temperature and 9. ˆˆ† 2NH3 at
For a reversible gaseous reaction N2 + 3H 2 ‡ˆˆ
0.50 atm pressure. Ammonium hydrogen sulphide equilibrium, if some moles of H2 are replaced by same
decomposes to yield NH3 and H2S gases in the flask. When number of moles of T2 (T is tritium, isotope of H and assume
the decomposition reaction reaches equilibrium, the total isotopes do not have different chemical properties) without
affecting other parameter, then :
EQUILIBRIUM 99

(a) the sample of ammonia obtained after sometime will be 12. For the reaction N 2 O4 (g) ƒ 2NO2 (g) , the value of Kp is
radioactive.
(b) moles of N2 after the change will be different as 1.7 ×103 at 500 K and 1.7 × 104 at 600 K. Which of the
compared to moles of N2 present before the change following is/are correct?
(c) the value of KP or Kc will change (a) The proportions of NO2 in the equilibrium mixture is
(d) the average molecular mass of new equilibrium will be increased by decrease in pressure.
same as that of old equilibrium (b) The standard enthalpy change for the forward reaction
10. The preparation of SO3(g) by reaction in negative.
1
SO 2 ( g ) + O 2 ( g ) ƒ SO 3 ( g ) (c) Units of Kp are atm–1.
2
is an exothermic reaction. If the preparation follows the (d) At 500 K the degree of dissociation of N2O4 decreases
following temperature-pressure relationship for its % yield, by 50% by increasing the pressure by 100%.
then for temperatures T1, T2 and T3. The correct option is : 13. For the complexation reaction
Ag + (aq) + 2NH 3 (aq) [Ag(NH 3 ) 2+ ](aq) ,
50 the rates of forward and reverse reactions are given by :
40 T3 (rate)f = 1.0 × 106 L2 mol –2 s–1[Ag+][NH3]2
30 (rate)r = 2.0 × 10–2 s–1 [Ag(NH3)2]+
% yield

T2
20 The instability constant of the complex is :
10 T1 (a) 5.0 × 109 (b) 2.0 × 10–4
(c) 2.0 × 10 –4 (d) 2.0 × 10–8
1 2 3 4
14. A solution is saturated with respect to SrCO3 and SrF2. The
Pressure (atm)
[CO32–] was found to be 1.2 × 10–3 M. The concentration of
F– in the solution would be
(a) T3 > T2 > T1 (b) T1 > T2 > T3
(c) T1 = T2 = T3 Given Ksp of SrCO3 = 7.0 ´ 10–10 M2,
(d) Nothing could be predicted about temperature through Ksp of SrF2 = 7.9 ´ 10–10 M3,
given information (a) 1.3 × 10–3 M (b) 2.6 × 10–2 M
11. Calculate DrG for the reaction at 27°C (c) 3.7 × 10–2 M (d) 5.8 × 10–7 M
ˆˆ† 2Ag ( s ) + 2H + ( aq )
H 2 ( g ) + 2Ag + ( aq ) ‡ˆˆ 15. The 0.001M Solution of Mg (NO3)2 is adjusted to pH 9, Ksp
of Mg(OH)2 is 8.9 × 10–12. At this pH
+ -5
Given : PH 2 = 0.5 bar; éë Ag ùû = 10 M; (a) Mg(OH)2 will be precipitated
[H+] = 10–3 M; DrG° [Ag+(aq)] = 77.1 kJ/mol (b) Mg(OH)2 is not precipitated
(a) – 154.2 kJ/mol (b) – 178.9 kJ/mol (c) Mg(OH)3 will be precipitated
(c) – 129.5 kJ/mol (d) None of these (d) Mg(OH)3 is not precipitated
 EBD_7374
100 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 13 (c) 25 (a) 37 (b) 49 (c) 61 (b) 73 (c) 85 (c) 97 (c) 109 (b)
2 (b) 14 (b) 26 (b) 38 (d) 50 (d) 62 (a) 74 (a) 86 (c) 98 (c) 110 (c)
3 (a) 15 (c) 27 (c) 39 (a) 51 (a) 63 (c) 75 (b) 87 (c) 99 (d) 111 (a)
4 (b) 16 (b) 28 (d) 40 (b) 52 (a) 64 (a) 76 (c) 88 (c) 100 (b) 112 (a)
5 (c) 17 (a) 29 (b) 41 (a) 53 (d) 65 (b) 77 (b) 89 (b) 101 (d) 113 (d)
6 (c) 18 (d) 30 (b) 42 (c) 54 (b) 66 (b) 78 (d) 90 (a) 102 (d) 114 (b)
7 (b) 19 (c) 31 (b) 43 (d) 55 (d) 67 (c) 79 (b) 91 (c) 103 (a) 115 (d)
8 (a) 20 (c) 32 (c) 44 (d) 56 (b) 68 (d) 80 (d) 92 (a) 104 (b) 116 (c)
9 (b) 21 (b) 33 (b) 45 (c) 57 (d) 69 (b) 81 (b) 93 (c) 105 (b) 117 (a)
10 (a) 22 (c) 34 (a) 46 (b) 58 (c) 70 (a) 82 (c) 94 (c) 106 (d) 118 (a)
11 (c) 23 (b) 35 (d) 47 (d) 59 (c) 71 (a) 83 (a) 95 (c) 107 (b)
12 (d) 24 (a) 36 (b) 48 (a) 60 (c) 72 (d) 84 (b) 96 (d) 108 (b)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (d) 8 (d) 15 (a) 22 (c) 29 (b) 36 (d) 43 (a) 50 (a) 57 (a) 64 (c)
2 (d) 9 (a) 16 (a) 23 (b) 30 (a) 37 (a) 44 (d) 51 (d) 58 (a) 65 (d)
3 (c) 10 (c) 17 (b) 24 (c) 31 (c) 38 (a) 45 (a) 52 (c) 59 (c) 66 (b)
4 (b) 11 (c) 18 (a) 25 (b) 32 (a) 39 (d) 46 (b) 53 (a) 60 (d) 67 (d)
5 (b) 12 (d) 19 (d) 26 (a) 33 (c) 40 (b) 47 (a) 54 (b) 61 (b)
6 (a) 13 (a) 20 (d) 27 (b) 34 (d) 41 (b) 48 (d) 55 (b) 62 (b)
7 (c) 14 (c) 21 (a) 28 (a) 35 (b) 42 (d) 49 (b) 56 (c) 63 (b)
Exercis e 3 : Try If You Can
1 (b) 3 (c) 5 (a) 7 (c) 9 (a) 11 (c) 13 (d) 15 (b)
2 (c) 4 (a) 6 (c) 8 (b) 10 (b) 12 (a) 14 (c)
 8
Chapter
REDOX REACTIONS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Redox reactions and electrode
AIIMS 2 potential, balancing of redox 2/5 4.7
JEE Main 1 reactions
BITSAT 2
 EBD_7374
102 CHEMISTRY
REDOX REACTIONS 103
 EBD_7374
104 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Redox Reactions in Terms of Electron 8. Match the columns

Column-I Column-II
Transfer Reactions (A) 2Mg + O2 ¾® 2MgO (p) Removal of hydrogen
1. Given reaction, (B) Mg + Cl2 ¾® MgCl2 (q) Removal of
2K4[Fe(CN)6] (aq) + H2O2 (aq) ¾® electropositive element
2K3[Fe(CN)6](aq) + 2KOH(aq) (C) 2H2S + O2 ¾® (r) Addition of oxygen
The above given reaction is oxidation reaction due to 2S + 2H2O
(a) removal of a hydrogen from H2O2 (D) 2KI + H2O + O3 ¾® (s) Addition of
(b) addition of electropositive potassium to H2O2 2KOH + I2 + O2 electronegativeelement,
(c) removal of electropositive element potassium from chlorine
potassium ferrocyanide (K4[Fe(CN)6]) (a) A – (s), B – (q), C – (p), D – (r)
(d) All of the above are the correct reasons. (b) A – (r), B – (s), C – (p), D – (q)
(c) A – (s), B – (r), C – (q), D – (p)
2. In the reaction given below, identify the species undergoing
(d) A – (r), B – (p), C – (s), D – (q)
redox reaction
9. Assertion : In a reaction
2Na(s) + H2(g) ¾® 2NaH(s) Zn(s) + CuSO4 (aq) ¾® ZnSO4(aq) + Cu(s)
(a) Na is reduced and hydrogen is oxidised Zn is a reductant but itself get oxidized.
(b) Na is oxidised and hydrogen is reduced Reason : In a redox reaction, oxidant is reduced by accepting
(c) Na undergoes oxidation and hydrogen undergoes electrons and reductant is oxidized by losing electrons.
reduction (a) Assertion is correct, reason is correct; reason is a
(d) Both (b) and (c) correct explanation for assertion.
3. Which of the following is correct code for x and y in the (b) Assertion is correct, reason is correct; reason is not a
following reaction. correct explanation for assertion
x (c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct.
2Na(s) + S(s) ¾¾
® Na2S(s) 10. If rod of a metal (x) is put in a metal ion solution which is
blue in colour , solution turn colorless. The metal rod and
y solution respectively are?
(i) x = oxidation reaction, y = reduction reaction (a) Zinc and Cu(II) (b) Zinc and Ni(II)
(ii) x = gain of two electrons, y = loss of two electrons, (c) Aluminium and Cu(II) (d) Both (a) and (c)
(iii) x = reduction reaction, y = oxidation reaction 11. In which of the following reactions, there is no change in
(iv) x = loss of two electrons, y = gain of two electrons valency ?
(a) (i) and (ii) (b) (i) and (iv) (a) 4 KClO3 ¾ ¾® 3KClO4 + KCl
(c) (ii) and (iii) (d) (iii) and (iv) (b) SO2 + 2H2S ¾ ¾® 2H2O + 3S
4. Which of the following involves transfer of five electrons ? (c) BaO2 + H2SO4 ¾ ¾® BaSO4 + H2O2
CrO24 - ® Cr3+
(d) 3 BaO + O2 ¾ ¾® 2 BaO2.
(a) MnO-4 ® Mn 2 + (b)
(c) MnO42 - ® MnO 2 (d) Cr2 O27 - ® 2Cr 3+ Topic 2: Oxidation Number
5. One mole of N2H4 loses 10 moles of electrons to form a new 12. In which of the following compounds oxygen has highest
compound, y. Assuming that all nitrogen appear in the new oxidation state and in which it has lowest oxidation state?
compound, what is the oxidation state of nitrogen in y (There OF2, H2O2, KO2, O2F2
is no change in the oxidation state of hydrogen ) (a) Highest = KO2, lowest = H2O2
(a) –1 (b) –3 (c) +3 (d) +5 (b) Highest = OF2, lowest = K2O2
6. When a strip of metallic zinc is placed in an aqueous (c) Highest = OF2, lowest = KO2
solution of copper nitrate the blue colour of the solution (d) Highest = KO2, lowest = H2O2
disappear due to formation of 13. ‘Oxidation number of H in NaH, CaH2 and LiH, respectively
(a) Cu2+ (b) Zn 2+ (c) ZnS (d) CuS is
(a) +1, +1, –1 (b) –1, +1, + 1
7. The number of electrons involved in the reduction of one
(c) +1, + 1, + 1 (d) –1,–1, –1
nitrate ion to hydrazine is
14. The oxidation number of chromium in potassium dichromate is
(a) 8 (b) 5 (c) 3 (d) 7 (a) + 6 (b) – 5 (c) – 2 (d) + 2
REDOX REACTIONS 105

15. The oxidation number of sulphur in S 8, S 2F 2 , H2 S 34. Atomic number of an element is 22. The highest O.S.
respectively, are exhibited by it in its compounds is
(a) 0, +1 and –2 (b) +2, +1 and –2 (a) 1 (b) 2 (c) 3 (d) 4
(c) 0, +1 and +2 (d) –2, +1 and –2 35. Match Column-I (compound) with Column-II (oxidation
16. Oxidation number of cobalt in K[Co(CO)4] is state of underlined element) and choose the correct
(a) +1 (b) +3 (c) –1 (d) –3 option.
17. Oxidation number of nitrogen in (NH4)2SO4 is Column - I Column - II
(a) –1/3 (b) –1 (c) +1 (d) –3 (A) CuO (p) 4
18. Oxidation number of carbon in CH2Cl2 is (B) MnO2 (q) 3
(a) –4 (b) +4 (c) 0 (d) –2 (C) HAuCl4 (r) 2
19. In which of the following compounds, iron has lowest (D) Tl2O (s) 1
oxidation state? (a) A – (r), B – (p), C – (q), D – (s)
(a) K 3[Fe(CN ) 6 ] (b) A – (s), B – (r), C – (p), D – (q)
(b) K 4 [Fe(CN) 6 ] (c) A – (r), B – (s), C – (p), D – (q)
(c) FeSO 4 .( NH 4 ) 2 SO 4 .6H 2 O (d) A – (s), B – (q), C – (p), D – (r)
(d) Fe(CO)5 36. Assertion : HClO4 is a stronger acid than HClO3.
20. The oxidation state of osmium (Os) in OsO4 is Reason : Oxidation state of Cl in HClO4 is +VII and in HClO3
(a) + 7 (b) + 6 (c) + 4 (d) + 8 +V.
21. Which of the following transition metal has zero oxidation (a) Assertion is correct, reason is correct; reason is a
state ? correct explanation for assertion.
(a) [Fe(CO)5] (b) NH2.NH2 (b) Assertion is correct, reason is correct; reason is not a
(c) NOClO4 (d) CrO5 correct explanation for assertion
22. In which of the compounds does 'manganese' exhibit highest (c) Assertion is correct, reason is incorrect
oxidation number ? (d) Assertion is incorrect, reason is correct.
(a) MnO2 (b) Mn 3O4 37. Among NH3, HNO3, NaN3 and Mg3N2 the number of
(c) K2MnO4 (d) MnSO4 molecules having nitrogen in negative oxidation state is
23. Among the following, identify the species with an atom in (a) 1 (b) 2 (c) 3 (d) 4
+6 oxidation state 38. The correct decreasing order of oxidation number of oxygen
(a) MnO–4 (b) Cr ( CN ) 36 – in compounds BaF2, O3, KO2 and OF2 is
(a) BaO2 > KO2 > O3 > OF2
(c) NiF62 – (d) CrO 2 Cl 2 (b) OF2 > O3 > KO2 > BaO2
24. Which reaction involves neither oxidation nor reduction? (c) KO2 > OF2 > O3 > BaO2
(a) CrO 24 - ¾¾ ® Cr2 O 72- (b) Cr ¾¾ ® CrCl3 (d) BaO2 > O3 > OF2 > KO2
+ 2-
(c) Na ¾¾ ® Na (d) 2S2 O3 ¾¾ ® S4 O62 - 39. Oxidation numbers of P in PO3– 2–
4 , of S in SO 4 and that of
25. In which of the following compounds, the oxidation number Cr in Cr2O72– are respectively
of iodine is fractional ? (a) + 3, + 6 and + 5 (b) + 5, + 3 and + 6
(a) IF7 (b) I -3 (c) IF5 (d) IF3 (c) – 3, + 6 and + 6 (d) + 5, + 6 and + 6
26. The correct name for NO2 using stock notation is Topic 3: Types of Redox Reactions, Balancing of
(a) nitrogen dioxide (b) nitrogen (IV) oxide Redox Reactions
(c) nitrogen per oxide (d) All of these
27. The oxide, which cannot act as a reducing agent, is 40. Which of the following do not show disproportionation
(a) NO2 (b) SO2 (c) CO2 (d) ClO2 reaction?
28. The oxidation state of Fe in Fe3O4 is ClO–4, F2, Cl2, ClO2–, ClO2–, P4, S8, and ClO–
(a) + 3 (b) 8/3 (c) + 6 (d) + 2 (a) ClO2–, ClO4–, and ClO– (b) F2 only
29. In oxygen difluoride, the oxidation number of oxygen is (c) F2 and ClO4– (d) ClO4– only
(a) – 2 (b) – 1 (c) + 2 (d) +1, – 2 41. Which one of the following reactions involves
30. Oxygen has an oxidation state of +2 in the compound disproportionation?
(a) H 2O2 (b) CO2 (c) H 2 O (d) F2 O (a) 2H2SO4 + Cu ¾® CuSO4 + 2H2O + SO2
(b) As2O3 + 3H2S ¾® As2S3 + 3H2O
31. The average oxidation state of sulphur in Na2S4O6 is
(c) 2KOH + Cl2 ¾® KCl + KOCl + H2O
(a) +2.5 (b) +2 (c) +3.0 (d) +3.5
(d) Ca3P2 + 6H2O ¾® 3Ca(OH)2 + 2PH3
32. Which of the following species can function both as
42. The following species will not exhibit disproportionation
oxidizing as well as reducing agent ? reaction
(a) Cl – (b) ClO4– (c) ClO – (d) MnO4– (a) ClO– (b) ClO -2 (c) ClO3- (d) ClO -4
33. In the compounds KMnO 4and K 2Cr 2O 7 the highest 43. In the reaction
oxidation state is of the element
(a) potassium (b) manganese 3Br2 + 6CO32 - + 3H 2 O ¾¾ ® 5Br - + BrO3– + 6HCO3-
(c) chromium (d) oxygen (a) Bromine is oxidised and carbonate is reduced.
(b) Bromine is reduced and water is oxidised
 EBD_7374
106 CHEMISTRY

(c) Bromine is neither reduced nor oxidised 56. If aqueous solution of H2O2 is made acidic. For this which
(d) Bromine is both reduced and oxidised of the following statement(s) is/are correct ?
44. Which of the following elements does not show (i) This aqueous solution oxidizes I–
disproportionation tendency? (ii) This aqueous solution oxidizes F–
(a) Cl (b) Br (c) F (d) I (a) Both statements (i) and (ii) are correct.
45. Phosphorus, sulphur and chlorine undergo disproportion (b) Statement (i) is correct and (ii) is incorrect.
in the ...A... medium. (c) Statement (ii) is correct and (i) is incorrect.
Here, A refers to (d) Both statements (i) and (ii) are incorrect.
(a) acidic (b) alkaline 57. Match the columns
(c) neutral (d) Both (a) and (b) Column-I Column-II
+1 -2 0 0
D (A) V2O5(s) + 5 Ca(s) ¾® (p) Disproportionation
46. The reaction, 2H 2 O(l) ¾¾ ® 2H 2 (g) + O 2 (g) is an
2V(s) + 5 CaO(s) reaction
example of D
(a) addition reaction (b) decomposition reaction (B) CH4(g) + 2O2(g) ¾¾® (q) Decomposition
(c) displacement reaction (d) None of these CO2(g) + 2 H2O(l) reaction
47. How will you balance the total ionic charge of reactant (C) P4(s) + 3OH–(aq) + 3H2O(l)(r) Combination
and products if reaction is carried out in acidic solution? ® PH3(g) + 3H 2 PO –2 ( aq ) reaction
(a) By using H+ ions
D
(b) By using OH– ions (D) 2 KClO3(s) ¾¾® (s) Displacement
(c) Adding H2O molecules to the reactant or product 2KCl(s) + 3O2(g) reaction
(d) Multiplying by suitable coefficients. (a) A – (s), B – (q), C – (r), D – (p)
48. Consider the following reaction occuring in basic medium (b) A – (s), B – (r), C – (p), D – (q)
2MnO –4 (aq)+Br – (aq) ¾¾® 2MnO2 (s) + BrO3– (aq) (c) A – (r), B – (s), C – (q), D – (p)
How the above reaction can be balanced further? (d) A – (r), B – (s), C – (p), D – (q)
(a) By adding 2 OH– ions on right side 58. Assertion : The reaction :
(b) By adding one H2O molecule to left side D
CaCO3 (s) ¾¾® CaO(s) + CO 2 (g)
(c) By adding 2H+ ions on right side is an example of decomposition reaction
(d) Both (a) and (b) Reason : Above reaction is not a redox reaction.
49. For the reaction : NH 3 + OCl - ¾ ¾® N 2 H 4 + Cl - in basic (a) Assertion is correct, reason is correct; reason is a
medium, the coefficients of NH3, OCl– and N2H4 for the correct explanation for assertion.
balanced equation are respectively (b) Assertion is correct, reason is correct; reason is not a
(a) 2, 2, 2 (b) 2, 2, 1 (c) 2, 1, 1 (d) 4, 4, 2 correct explanation for assertion
50. C2H6 (g) + nO2(g) ® CO2(g) + H2O(l) (c) Assertion is correct, reason is incorrect
In this equation, the ratio of the coefficients of CO2 and (d) Assertion is incorrect, reason is correct.
H2O is 59. When Cl2 gas reacts with hot and concentrated sodium
(a) 1 : 1 (b) 2 : 3 (c) 3 : 2 (d) 1 : 3 hydroxide solution, the oxidation number of chlorine
changes from
51. 2MnO -4 + 5H 2 O 2 + 6H + ® 2 Z + 5O 2 + 8H 2 O. In this
(a) zero to +1 and zero to –5
reaction Z is (b) zero to –1 and zero to +5
(a) Mn 2+ (b) Mn 4+ (c) MnO2 (d) Mn (c) zero to –1 and zero to +3
52. In the redox reaction, (d) zero to +1 and zero to –3
xKMnO4 + NH3 ¾® yKNO3 + MnO2 + KOH + H2O 60. Which of the following act as reducing agents ?
(a) x = 4, y = 6 (b) x = 3, y = 8
(c) x = 8, y = 6 (d) x = 8, y = 3 (i) PO34- (ii) SO3 (iii) PO32 - (iv) NH3
53. What is ‘A’ in the following reaction (a) (i), (ii) and (iii) (b) Only (iii)
2Fe3+(aq) +Sn2+(aq) ® 2Fe2+(aq) + A (c) (i), (iii) and (iv) (d) (iii) and (iv)
(a) Sn3+ (aq) (b) Sn4+ (aq) 61. In the reaction shown below, oxidation state of the carbon
(c) Sn2+ (aq) (d) Sn in reactant and product are (i) and (ii) respectively? Is the
54. Given : given reaction a redox reaction?
X Na2HAsO3 + Y NaBrO3 + Z HCl ® NaBr Na2CO3(aq) + HCl (aq)
+ H3AsO4 + NaCl
® Na ( aq ) + Cl ( aq ) + H 2 O ( l ) + CO 2 ( g )
Å -
The values of X, Y and Z in the above redox reaction are ¾¾
respectively (a) (i) 6, (ii) 4, yes (b) (i) 6, (ii) 6, No
(a) 2, 1, 2 (b) 2, 1, 3 (c) 3, 1, 6 (d) 3, 1, 4 (c) (i) 4, (ii) 4, No (d) (i) 4, (ii) 4, yes
55. The values of x and y in the following redox reaction 62. What products are expected from the disproportionation
x Cl 2 + 6OH - ¾ ¾® ClO 3- + y Cl - + 3H 2O are reaction of hypochlorous acid?
(a) HCl and Cl2O (b) HCl and HClO3
(a) x = 5, y = 3 (b) x = 2, y = 4
(c) HClO3 and Cl2O (d) HClO2 and HClO4
(c) x = 3, y = 5 (d) x = 4, y = 2
REDOX REACTIONS 107

63. In the disproportionation reaction and reducing agent respectively –

3 HClO3 ¾® HClO4 + Cl2 + 2O2 + H2O, the equivalent mass (a) D2+/D and B2+/B (b) B2+/B and D2+/D
of the oxidizing agent is (molar mass of HClO3 = 84.45) 2+
(c) D /D and C /C 2+ (d) C2+/C and D2+/D
(a) 16.89 (b) 32.22 (c) 84.45 (d) 28.15 72. The standard reduction potentials at 298K for the following
64. Consider the following reaction : half reactions are given against each
xMnO 4– + yC 2 O 2– + Zn2+ (aq) + 2e ƒ Zn(s) ; –0.762 V
4 + zH ¾¾
®
z Cr3+ (aq) + 3e ƒ Cr (s); –0.740 V
xMn 2+ + 2yCO 2 + H 2 O 2H+ (aq) + 2e ƒ H2 (g) ; 0.00 V
2 Fe3+ (aq) + e ƒ Fe2+ (aq) ; 0.770 V
The value’s of x, y and z in the reaction are, respectively :
(a) 5, 2 and 16 (b) 2, 5 and 8 Which is the strongest reducing agent?
(a) Zn (s) (b) Cr (s) (c) H2(g) (d) Fe3+ (aq)
(c) 2, 5 and 16 (d) 5, 2 and 8
73. Electrode potential data are given below :
65. In the balanced chemical reaction
IO3- + aI - + bH + ¾¾® cH 2 O + dI 2 Fe +(aq
3 -
) +e ¾¾® Fe (+aq
2
); E° = +0.77 V
a, b, c and d respectively corresponds to Al3(+aq) + 3e - ¾ ¾® Al (s) ; E° = – 1.66 V
(a) 5, 6, 3, 3 (b) 5, 3, 6, 3 - -
Br2 (aq) + 2e ¾ ¾® 2Br (aq) ; E° = + 1.08V
(c) 3, 5, 3, 6 (d) 5, 6, 5, 5
66. If equal volume of reactants are used, than no. moles of Based on the data, the reducing power of Fe2+, Al and Br–
KMnO4 (moles per liter) used in acidic medium required to will increase in the order
completely oxidises the 0.5 M FeSO3? (a) Br– < Fe2+ < Al (b) Fe2+ < Al < Br –
–
(c) Al < Br < Fe 2+ (d) Al < Fe2+ < Br–
(a) 0.3 (b) 0.1 (c) 0.2 (d) 0.4
67. Acidic medium used in KMnO4 can be made from which of 74. The standard reduction potentials for Cu2+/Cu; Zn2+/Zn;
the following acids? Li +/Li; Ag +/Ag and H+/H2 are + 0.34 V, – 0.762 V,
(a) HCl (b) H2SO4 (c) HI (d) HBr – 3.05 V, + 0.80 V and 0.00 V respectively. Choose the
strongest reducing agent among the following
Topic 4: Redox Reactions and Electrode Process (a) Zn (b) H2 (c) Ag (d) Li
68. Given E– 75. Given :
(i) Mg2+/Mg(s), E– = –2.36 Eo 1 = 1.36 V, E o 3+ = - 0.74 V,
-
(ii) Ag+/Ag(s), E– = 0.80 2
Cl2 / Cl Cr / Cr

(iii) Al3+/Al(s), E– = –1.66

(iv) Cu2+/Cu(s), E– = 0.52 Eo = 1.33V, E o = 1.51V
Cr2O 72 - / Cr3+ MnO -4 / Mn 2 +
Out of the above given elements which is the strongest The correct order of reducing power of the species
oxidising agent and which is the weakest oxidising agent ? (Cr, Cr3+, Mn2+ and Cl–) will be
(a) (iv) is the strong whereas (ii) is the weakest oxidising (a) Mn2+ < Cl– < Cr3+ < Cr
agent (b) Mn2+ < Cl3+ < Cl– < Cr
(b) (ii) is the strongest whereas (i) is the weakest (c) Cr3+ < Cl– < Mn2+ < Cr
oxidising agent (d) Cr3+ < Cl– < Cr < Mn2+
(c) (i) is the strongest whereas (ii) is the weakest 76. E– Values of some redox couples are given below. On the
oxidising agent basis of these values choose the correct option.
(d) (ii) is the strongest whereas (iii) is the weakest E– values : Br 2/Br – = + 1.90; Ag+ /Ag(s) = + 0.80
oxidising agent Cu2+ /Cu(s) = + 0.34; I2(s) /I– = 0.54
69. Stronger is oxidising agent, more is (a) Cu will reduce Br – (b) Cu will reduce Ag
(a) standard reduction potential of that species (c) Cu will reduce I – (d) Cu will reduce Br2
(b) the tendency to get it self oxidised 77. Arrange the following in the order of their decreasing
(c) the tendency to lose electrons by that species electrode potentials : Mg, K, Ba and Ca
(d) standard oxidation potential of that species (a) K, Ca, Ba, Mg (b) Ba, Ca, K, Mg
70. Standard reduction potentials of the half reactions are (c) Ca, Mg, K, Ba (d) Mg, Ca, Ba, K
given below : 78. The standard electrode potentials of four elements A, B, C
F2(g) + 2e– ¾® 2F– (aq); E° = + 2.85 V and D are –3.05, –1.66, –0.40 and +0.80. The highest chemical
Cl2(g) + 2e– ¾® 2Cl–(aq); E° = + 1.36 V reactivity will be exhibited by
Br2(l) + 2e– ¾® 2Br–(aq); E° = + 1.06 V (a) A (b) B (c) C (d) D
I2(s) + 2e– ¾® 2I–(aq); E° = + 0.53 V 79. Which of the following statements are correct concerning
The strongest oxidising and reducing agents respectively redox properties?
are : (i) A metal M for which E° for the half life reaction
(a) F2 and I– (b) Br2 and Cl– ˆˆ† M is very negative will be a good
– Mn+ + ne– ‡ˆˆ
(c) Cl2 and Br (d) Cl2 and I2
71. Standard electrode potentials of redox couples reducing agent.
A2+/A, B2+/B, C/C2+ and D2+/D are 0.3V, – 0.5V, – 0.75V and (ii) The oxidizing power of the halogens decreases from
0.9V respectively. Which of these is best oxidising agent chlorine to iodine.
 EBD_7374
108 CHEMISTRY

(iii) The reducing power of hydrogen halides increases from (ii) A positive E– means that the redox couple is weaker
hydrogen chloride to hydrogen iodide reducing agent than the H+/H2.
(a) (i), (ii) and (iii) (b) (i) and (ii) Which of the following code is incorrect regarding above
(c) (i) only (d) (ii) and (iii) statements?
80. Which of the following statement(s) is/are correct ? (a) Only (i) (b) only (ii)
(i) A negative value of E– means that the redox couple is a (c) Both (i) and (ii) (d) Neither (i) nor (ii)
weaker reducing agent than the H+/H2 couple.

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (d) Bromine undergoes oxidation and iodine undergoes
reduction in these reactions
1. Which of the following is not an example of redox reaction?
(a) CuO + H 2 ¾¾ 6. The oxidation number of an element in a compound is
® Cu + H 2 O
evaluated on the basis of certain rules. Which of the
(b) Fe2 O3 + 3CO ¾¾ ® 2Fe + 3CO 2 following is incorrect in this respect?
(c) 2K + F2 ¾¾ ® 2KF (a) The oxidation number of hydrogen is always + 1
(d) BaCl 2 + H 2SO 4 ¾¾ ® BaSO 4 + 2HCl (b) The algebraic sum of all the oxidation numbers in a
Redox reactions are those reactions which involve change compound is zero
in oxidation number of the reactants. (c) An element in the free or the uncombined state bears
–
2. The more positive the value of E , the greater is the oxidation number zero
tendency of the species to get reduced. Using the standard
(d) In all its compounds, the oxidation number of fluorine
electrode potential of redox couples given below find out
is –1
which of the following is the strongest oxidising agent.
– 7. In which of the following compounds, an element exhibits
E values : Fe3+/Fe2+ = + 0.77V ; I2(s)/I – = + 0.54; two different oxidation states?
Cu2+/Cu = + 0.34; Ag+/Ag = 0.80 V
(a) NH2OH (b) NH4NO3 (c) N2H4 (d) N3H
(a) Fe3+ (b) I2(s) (c) Cu2+ (d) Ag+
–
8. Which of the following arrangements represent increasing
3. E values of some redox couples are given below. On the oxidation number of the central atom?
basis of these values choose the correct option.
–
(a) CrO2- , ClO3- , CrO24 - , MnO4-
E values: Br 2/Br – = + 1.09
Ag+/ Ag(s) = + 0.80 (b) ClO3- , CrO 42 - , MnO -4 , CrO -2
Cu2+/Cu(s) = + 0.34; I2 (s) / I– = + 0.54 (c) CrO2- , ClO3- , MnO4- , CrO42 -
(a) Cu will reduce Br – (b) Cu will reduce Ag
(d) CrO 24 - , MnO -4 , CrO 2- , ClO 3-
(c) Cu will reduce I – (d) Cu will reduce Br 2
4. Using the standard electrode potential, find out the pair 9. The largest oxidation number exhibited by an element
between which redox reaction is not feasible. depends on its outer electronic configuration. With which
– of the following outer electronic configurations the element
E values: Fe3+/ Fe2+ = + 0.77; I2/I– = + 0.54; will exhibit largest oxidation number ?
Cu2+ / Cu = +0.34; Ag+ / Ag = + 0.80 V
(a) Fe3+ and I– (b) Ag+ and Cu (a) 3d1 4s2 (b) 3d2 4s2 (c) 3d5 4s1 (d) 3d5 4s2
3+
(c) Fe and Cu (d) Ag and Fe3+ 10. Identify disproportionation reaction
Determine the E°cell of the four redox reactions. If the value (a) CH 4 + 2O 2 ¾¾ ® CO 2 + 2H 2 O
of E°cell of a reaction is negative, that reaction will not take (b) CH 4 + 4Cl 2 ¾¾
® CCl4 + 4HCl
place.
5. Thiosulphate reacts differently with iodine and bromine in (c) 2F2 + 2OH - ¾¾
® 2F - + OF2 + H 2 O
the reactions given below. (d) 2NO 2 + 2OH - ¾¾
® NO 2- + NO 3- + H 2 O
2S2 O32 - + I 2 ® S4 O62 - + 2I - 11. Which of the following elements does not show
disproportionation tendency?
S2 O32 - + 2Br 2 + 5H 2 O ® 2SO 24 - + 2Br - + 10H +
(a) Cl (b) Br (c) F (d) I
Which of the following statements justifies the above dual Past Year MCQs
behaviour of thiosulphate?
(a) Bromine is a stronger oxidant than iodine 12. Which of the following involves transfer of five
(b) Bromine is a weaker oxidant than iodine electrons ? [AIIMS 2014, C]
(c) Thiosulphate undergoes oxidation by bromine and (a) MnO -4 ® Mn 2+ (b) CrO 24- ® Cr 3+
reduction by iodine in these reactions (c) MnO42- ®MnO2 (d) Cr2O27- ® 2Cr3+
REDOX REACTIONS 109

13. Oxidation numbers of P in PO3– 2– (a) XeF4 + O2F2 ® XeF6 + O2

4 , of S in SO4 and that of
Cr in Cr2O27– are respectively [AIIMS 2015, S] (b) XeF2 + PF5 ® [XeF]+ PF6–
(a) + 3, + 6 and + 5 (b) + 5, + 3 and + 6 (c) XeF6 + H2O ® XeOF4 + 2HF
(c) – 3, + 6 and + 6 (d) + 5, + 6 and + 6 (d) XeF6 + 2H2O ® XeO2F2 + 4HF
14. Which of the following species can function both as 17. For the redox reaction [NEET 2018, S]
oxidizing as well as reducing agent ? [AIIMS 2016, C] MnO 4– + C 2 O 2– +
+ H ¾¾
® Mn 2+
+ CO 2 + H 2 O
4
(a) Cl – (b) ClO4 – (c) ClO – (d) MnO4– The correct coefficients of the reactants for the balanced
15. Consider the following reaction occuring in basic medium equation are
[AIIMS 2017, S] MnO4– Cr2O42– H+
2MnO 4– (aq) + Br – (aq) ¾ ¾
® 2MnO 2 (s) + BrO 3– (aq) (a) 16 5 2
(b) 2 5 16
How the above reaction can be balanced further?
(c) 5 16 2
(a) By adding 2 OH– ions on right side (d) 2 16 5
(b) By adding one H2O molecule to left side 18. The oxidation states of Cr in [Cr(H2O)6]Cl3, [Cr(C6H6)2], and
(c) By adding 2H+ ions on right side K2[Cr(CN)2(O)2(O)2(NH3)] respectively are :
(d) Both (a) and (b) [JEE M 2018, S]
16. Which of the following reactions is an example of a redox (a) +3, +4, and +6 (b) +3, +2, and +4
reaction? [JEE M 2017, C] (c) +3, 0, and +6 (d) +3, 0, and + 4

Exercise 3 : Try If You Can

1. Which of the following reactions do not involve oxidation 4. Which of the following reactions does not involve either
reduction? oxidation or reduction?
I. 2Cs + 2H 2 O ¾¾ ® 2CsOH + H 2
(a) VO 2+ ¾¾
® V2O3 ® Na +
(b) Na ¾¾
II. 2CuI 2 ¾¾
® 2Cul + I2
(c) CrO24 - ¾¾
® Cr2 O 72- (d) Zn 2+ ¾¾
® Zn
III. NH 4Br + KOH ¾¾
® KBr + NH3 + H 2O
5. To an acidic solution of an anion, a few drops of KMnO4
IV. ® K 4 [Fe ( CN )6 ]
4KCN + Fe ( CN )2 ¾¾ solution are added. Which of the following, if present, will
(a) I, II (b) I, III (c) I, III, IV (d) III, IV not decolourise the KMnO4 solution?
2. Which of the following represents redox reactions? (a) CO32– (b) NO -2 (c) S2– (d) Cl -
-
I. Cr2 O 7 2 - + 2OH ¾¾
® 2CrO 42 - + H 2 O 6. The oxidation number of phosphorus in Ba(H2PO2)2 is
Zn + CuSO 4 ¾¾
® ZnSO 4 + Cu (a) +3 (b) +2 (c) +1 (d) –1
II.
7. Zn gives H2 gas with H2SO4 and HCl but not with HNO3
- because
III. 2MnO -4 + 3Mn 2+ + 4OH ¾¾
® 5MnO2 + 2H 2O
(a) Zn acts as an oxidising agent when it reacts with HNO3
IV. 2Cu + ¾¾ ® Cu + Cu 2 + (b) HNO3 is weaker acid than H2SO4 and HCl
(a) I, II (b) I, III (c) III, IV (d) II, III, IV (c) In electrochemical series, Zn is above hydrogen
3. Which of the following is an intermolecular redox reaction? (d) NO3- is reduced in preference to hydronium ion
8. The oxidation state of nitrogen is correctly given for
-
(a) OH Compound Oxidation state
2OCH — CHO ¾¾¾
® HOCH 2 — CH 2OH
(a) é Co ( NH3 )5 Clù Cl2 0
Al( OC2 H5 )3
ë û
(b) 2C6 H5CHO ¾¾¾¾¾¾® C 6 H5COOH + (b) NH2OH –2
(c) (N2H5)2SO4 +2
C6 H5CH 2 OH (d) Mg3N2 –3
(c) ® 2Cr2 (SO 4 )3 +
4CrO 5 + 6H 2SO 4 ¾¾ 9. Which of the following statements is not correct?
(a) The oxidation number of S in (NH4)2S2O8 is +6.
6H 2O + 7O2 (b) The oxidation number of Os in OsO4 is +8.
(c) The oxidation number of S in H2SO5 is +8.
(d) As 2S3 + HNO3 ¾¾
® H 3 AsO 4 + H 2SO 4 + NO (d) The oxidation number of O in KO2 is –1/2.
 EBD_7374
110 CHEMISTRY

10. The oxidation states of sulphur in the anions SO32– , 14. Which of the following is not a disproportionation reaction?
S2O42–, and S2O62– follow the order.
Al( OEt )
(a) S2O42– < SO32– < S2O62– (b) SO32– < S2O42– < S2O62– (a) 2PhCHO ¾¾¾¾3¾ ® PhCOOCH 2 Ph
(c) S2O42– < S2O62– < SO32– (d) S2O62– < S2O62– < SO32–
–
2- H+ 3+ + oxidised product of X, (b) CHO – CH 2 OH COO
11. Cr2O7 + X ¾¾¾ ® Cr + H 2 O + OH ¾¾
® +
X in the above reaction cannot be COOH COO– COO –
(a) C2O42– (b) Fe2+ (c) SO42– (d) S2–
12. The equivalent mass of oxidising agent in the following (c) NaH + H 2O ¾¾
® NaOH + H 2
reaction is
(d) All of the above.
SO 2 + 2H 2S ¾¾ ® 3S + 2H 2 O
15. The standard reduction potentials at 298K for the following
(a) 32 (b) 64 (c) 16 (d) 8
13. Which of the following is not a disproportionation reaction? half reactions are given against each
D Zn2+ (aq) + 2e ¾® Zn(s) ; –0.762 V
I. NH4 NO3 ¾¾® N2O + H 2O
Cr3+ (aq) + 3e ¾® Cr (s); –0.740 V
D 2H+ (aq) + 2e ¾® H2 (g) ; 0.00 V
II. ® PH 3 + HPO 2-
P4 ¾¾
III. D Fe3+ (aq) + e ¾® Fe2+ (aq) ; 0.770 V
PCl5 ¾¾® PCl3 + Cl 2
Which is the strongest reducing agent?
IV. ® O 2 + 2e-
H 2 O 2 ¾¾ (a) Zn (s) (b) Cr (s)
(a) I, II (b) I, III, IV (c) II, IV (d) I, III (c) H2(g) (d) Fe3+ (aq)

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 9 (a) 17 (d) 25 (b) 33 (b) 41 (c) 49 (c) 57 (b) 65 (a) 73 (a)
2 (d) 10 (d) 18 (c) 26 (b) 34 (d) 42 (d) 50 (b) 58 (b) 66 (a) 74 (d)
3 (b) 11 (c) 19 (d) 27 (c) 35 (a) 43 (d) 51 (a) 59 (b) 67 (b) 75 (a)
4 (a) 12 (c) 20 (d) 28 (b) 36 (b) 44 (c) 52 (d) 60 (d) 68 (b) 76 (d)
5 (c) 13 (d) 21 (a) 29 (c) 37 (c) 45 (b) 53 (b) 61 (c) 69 (a) 77 (d)
6 (b) 14 (a) 22 (c) 30 (d) 38 (b) 46 (b) 54 (c) 62 (b) 70 (a) 78 (a)
7 (d) 15 (a) 23 (d) 31 (a) 39 (d) 47 (a) 55 (c) 63 (a) 71 (c) 79 (a)
8 (b) 16 (c) 24 (a) 32 (c) 40 (c) 48 (d) 56 (b) 64 (c) 72 (a) 80 (a)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (d) 3 (d) 5 (a) 7 (b) 9 (d) 11 (c) 13 (d) 15 (d) 17 (b)
2 (d) 4 (d) 6 (a) 8 (a) 10 (d) 12 (a) 14 (c) 16 (a) 18 (c)
Exercis e 3 : Try If You Can
1 (d) 3 (d) 5 (a) 7 (d) 9 (c) 11 (c) 13 (b) 15 (a)
2 (d) 4 (c) 6 (c) 8 (d) 10 (a) 12 (c) 14 (c)
 9
Chapter
HYDROGEN

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Hardness of water, structure
AIIMS 2 and properties of hydrogen 2/5 5.2
JEE Main 2 peroxide
BITSAT 2
 EBD_7374
112 CHEMISTRY
HYDROGEN 113
 EBD_7374
114 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Position of Hydrogen in the Periodic Topic 2: Preparation of Dihydrogen

Table and Dihydrogen 8. Which of the following reaction(s) represents commercial
1. Hydrogen can behave as a metal method for production of dihydrogen?
(a) at very high temperature 673 K
(i) CO(g) + H2O(g) ¾¾¾¾
catalyst
® CO (g) + H (g)
2 2
(b) at very low temperature
(c) at very high pressure electrolysis
(ii) 2H2O(l) ¾¾¾ ¾ ¾¾ ¾
traces of acid/base
® 2H2(g) + O2(g)
(d) at very low pressure
2. The property of hydrogen which distinguishes it from alkali (iii) Zn + 2H + ¾¾
® Zn2+ + H2
metals is 1270K
(iv) CH4(g) + H2O(g) ¾¾ ¾¾ ® CO(g) + 3H2(g)
(a) its electropositive character Ni

(b) its affinity for non metal (a) (i), (ii) and (iii) (b) (iii) only
(c) its reducing character (c) (i), (ii) and (iv) (d) (ii), (iii) and (iv)
(d) its non-metallic character 9. Which of the following is formed when zinc reacts with
sodium hydroxide?
3. Which of the following statements is correct ?
(a) Hydrogen gas (b) Sodium zincate
(a) Hydrogen has same IP as alkali metals.
(c) Zinc oxide (d) Both (a) and (b)
(b) Hydrogen has same electronegativity as halogens.
10. Which of the following statements is correct?
(c) It has oxidation number of –1 and +1. (a) Production of syn gas from coal is called coal gasification.
(d) It will not be liberated at anode.
673K
4. Number of neutrons in three isotopes of hydrogen, protium, (b) CO(g) + H2O(g) ¾¾¾¾
catalyst
® CO (g) + H (g) represents
2 2
deuterium and tritium respectively is
(a) 0, 1, 2 (b) 1, 1,1 (c) 2, 1, 0 (d) 2, 0, 1 water gas shift reaction.
5. Choose the incorrect statement (c) CO2 formed in water gas shift reaction is removed by
scrubbing with sodium zincate solution.
(a) Dihydrogen can release more energy than petrol.
(d) Both (a) and (b)
(b) The only pollutant in combustion of dihydrogen is
11. Which one of the following pairs of substances on reaction
carbon dioxide.
will not evolve H2 gas?
(c) Hydrogen economy is based on the principle of
(a) Iron and H2SO4 (aqueous)
transportation and storage of energy in the form of
(b) Iron and steam
liquid or gaseous dihydrogen.
(c) Copper and HCl (aqueous)
(d) Hydrogen economy has advantage that energy is
(d) Sodium and ethyl alcohol
transmitted in the form of dihydrogen and not as
12. Which of the following metal evolves hydrogen on reacting
electric power.
with cold dilute HNO3 ?
6. Which of the following fuel is used for runnning the
(a) Mg (b) Al (c) Fe (d) Cu
automobiles first time in the history of India during October
13. In Bosch’s process which gas is utilised for the production
2005?
of hydrogen gas ?
(a) D2O (b) H2O2 (c) D2 (d) H2 (a) Producer gas (b) Water gas
7. +
Assertion: H does not exist freely and is always associated (c) Coal gas (d) None of these
with other atoms or molecules. 14. Hydrogen is not obtained when zinc reacts with
Reason: Loss of the electron from hydrogen atom results (a) Cold water (b) dil. HCl
in nucleus (H+) of ~ 1.5 × 10–3 pm size. This is extremely (c) dil. H2SO4 (d) Hot NaOH (20%)
small as compared to normal atomic and ionic sizes of 50 15. Which one of the following pairs of substances will not
to 200 pm. produce hydrogen when reacted together?
(a) Assertion is correct, reason is correct; reason is a (a) Copper and conc. nitric acid
correct explanation for assertion. (b) Ethanol and metallic sodium
(b) Assertion is correct, reason is correct; reason is not a (c) Magnesium and steam
correct explanation for assertion (d) Phenol and metallic sodium
(c) Assertion is correct, reason is incorrect 16. Very pure hydrogen (99.9%) can be made by which of the
(d) Assertion is incorrect, reason is correct. following processes ?
HYDROGEN 115

(a) Reaction of methane with steam 25. Choose the correct option for following hydrides.
(b) Mixing natural hydrocarbons of high molecular weight B2H6, CH4, NH3 and HF
(c) Electrolysis of water (a) Electron deficient hydride = B2H6 and HF
(d) Reaction of salts like hydrides with water Electron precise hydride = CH4
Topic 3: Properties of Dihydrogen Electron rich hydride = NH3
(b) Electron deficient hydride = B2H6
17. Which of the following is formed on reaction of carbon Electron precise hydride = CH4
monoxide gas with dihydrogen in presence of cobalt as a Electron rich hydride = NH3 and HF
catalyst? (c) Electron deficient hydride = CH4
(a) Methanal (b) Methanol Electron precise hydride = B2H6
(c) Methane (d) Formic acid Electron rich hydride = NH3 and HF
18. Which of the following is not a use of dihydrogen ? (d) Electron deficient hydride = CH4 and HF
(a) It used in fuel cells for generating electrical energy. Electron precise = B2H6
(b) Atomic hydrogen and oxy-hydrogen torches are Electron rich hydride = NH3,
used for cutting and welding purposes. 26. Which hydride is an ionic hydride ?
(c) It used in the synthesis of hydroquinone and tartaric acid. (a) H2S (b) TiH1.73 (c) NH3 (d) NaH
(d) Both (b) and (c) 27. Metal hydride on treatment with water gives
19. Which of the following statement(s) is/are incorrect? (a) H2O2 (b) H2O (c) Acid (d) Hydrogen
(i) Dihydrogen reduces copper (II) oxide to copper 28. The polymeric hydride is
(ii) Reaction of dihydrogen with sodium gives sodium (a) CaH2 (b) NaH (c) BaH2 (d) MgH2
hydride. 29. Ionic hydrides reacts with water to give
(iii) Hydroformylation of olefins yields aldehydes which (a) acidic solutions (b) hydride ions
further undergo reduction to give alcohols. (c) basic solutions (d) electorns
(iv) Hydrogenation of vegetable oils using iron as 30. Which of the following is incorrect statement?
catalyst gives edible fats. (a) s-block elements, except Be and Mg, form ionic hydride
(a) (i), (ii) and (iii) (b) (i) and (iv) (b) BeH4, MgH2, CuH2, ZnH2, CaH2 and HgH2 are
(c) (iv) only (d) (iii) and (iv) intermediate hydride
20. Hydrogen will not reduce (c) p-block elements form covalent hydride
(a) heated cupric oxide (d) heated ferric oxide (d) d-and f-block elements form ionic hydride
(c) heated stannic oxide (d) heated aluminium oxide 31. LiAlH4 is used as :
21. Why is water gas (mixture of CO and H2) also called ‘syn
(a) An oxidizing agent (b) A reducing agent
gas’?
(c) A mordant (d) A water softener
(a) Because it is synthesised from sewage, saw – dust,
32. Water is :
scrap wood etc.
(b) Because it is synthesised from methane gas. (a) more polar than H2S
(c) Because it is used in the synthesis of methanol and (b) more or less identical in polarity with H2S
a number of hydrocarbons. (c) less polar than H2S
(d) None of these (d) None of these
33. The storage tanks used for H2 are made up of which metal
Topic 4: Hydrides
alloy(s)
22. Elements of which of the following group do not form (i) NaNi5 (ii) B2H6
hydrides? (iii) Ti–TiH2 (iv) Mg–MgH2
(a) Alkali metals (b) Halogens (a) (iii) and (iv) (b) (i) and (ii)
(c) Alkaline earth metals (d) Noble gases (c) (i), (iii) and (iv) (d) (ii), (iii) and (iv)
23. Which of the following statements is incorrect? 34. –
The hydride ion, H , is a stronger base than the hydroxide
(a) Ionic hydrides are stoichiometric compounds of ion, OH–. Which one of the following reactions will occur if
dihydrogen formed with most of s-block elements. sodium hydride (NaH) is dissolved in water?
(b) Ionic hydrides are crystalline, non-volatile and non- (a) H - (aq) + H 2 O(l) ® H 3O - (aq)
conducting in solid state.
(b) H - (aq) + H 2O(l) ® OH- (aq) + H 2 (g)
(c) Melts of ionic hydrides conduct electricity and
liberate dihydrogen gas at cathode. (c) H - (aq) + H 2 O(l) ® OH - (aq) + 2 H + (aq) + 2e -
(d) Both (a) and (c) (d) H - ( aq ) + H 2 O ( l) ® No reaction
24. Saline hydrides react explosively with water, such fires can Topic 5: Water
be extinguished by
35. The unusual properties of water in the condensed phase
(a) water (b) carbon dioxide
(liquid and solid states) are due to the
(c) sand (d) None of these
 EBD_7374
116 CHEMISTRY

(a) presence of hydrogen and covalent bonding between 46. Which one the following removes temporary hardness of
the water molecules water ?
(b) presence of covalent bonding between the water (a) Slaked lime (b) Plaster of Paris
molecules (c) Epsom (d) Hydrolith
(c) presence of extensive hydrogen bonding between water 47. Assertion : Hard water is not suitable for laundary.
molecules Reason : Soap containing sodium stearate reacts with hard
(d) presence of ionic bonding water to precipitate out as calcium or magnesium stearate.
36. The boiling point of water is exceptionally high because (a) Assertion is correct, reason is correct; reason is a
(a) there is covalent bond between H and O correct explanation for assertion.
(b) water molecule is linear (b) Assertion is correct, reason is correct; reason is not a
(c) water molecules associate due to hydrogen bonding correct explanation for assertion.
(d) water molecule is not linear (c) Assertion is correct, reason is incorrect.
37. Water possesses a high dielectric constant, therefore : (d) Assertion is incorrect, reason is correct.
(a) it always contains ions 48. Match the columns
Column-I Column-II
(b) it is a universal solvent
(A) Coordinated water (p) [Cu(H2O)4]4+SO2– 4. H2O
(c) can dissolve covalent compounds
(B) Interstitial water (q) C17H35COONa
(d) can conduct electricity
(C) Hydrogen-bonded (r) BaCl2.2H2O
38. At its melting point ice is lighter than water because
water (s) [Cr(H2O)6]3+ 3Cl–
(a) H2O molecules are more closely packed in solid state
(a) A – (r), B – (s), C – (q) (b) A – (q), B – (r), C – (s)
(b) ice crystals have hollow hexagonal arrangement of H2O
(c) A – (r), B – (q), C – (p) (d) A – (s), B – (r), C – (p)
molecules.
49. Match the Column-I with Column-II and mark the appropriate
(c) on melting of ice the H2O molecule shrinks in size
choice.
(d) ice froms mostly heavy water on first melting.
Column-I Column-II
39. The low density of ice compared to water is due to
(A) Syn gas (p) Na6P6O18
(a) hydrogen-bonding interactions
(B) Calgon (q) NaAlSiO4
(b) dipole-dipole interactions
(C) Permutit (r) CO + H2
(c) dipole-induced dipole interactions
(D) Producer gas (s) CO + N2
(d) induced dipole-induced dipole interactions
(a) (A) – (p), (B) – (q), (C) – (r), (D) – (s)
40. When two ice cubes are pressed over each other, they unite
(b) (A) – (r), (B) – (p), (C) – (q), (D) – (s)
to form one cube. Which of the following forces is
(c) (A) – (r), (B) – (q), (C) – (s), (D) – (p)
responsible to hold them together ?
(d) (A) – (r), (B) – (q), (C) – (p), (D) – (s)
(a) Van der Waals forces (b) Hydrogen bond formation
50. Assertion : Calgon is used for remvoing permanent hardness
(c) Covalent attraction (d) Ionic interaction
of water.
41. Which of the following metals reacts with H 2 O at room
Reason : Calgon forms precipitates with Ca2+ and Mg2+.
temp?
(a) Assertion is correct, reason is correct; reason is a
(a) Ag (b) Fe (c) Al (d) Na
correct explanation for assertion.
42. Which of the following groups of ions makes the water
(b) Assertion is correct, reason is correct; reason is not a
hard?
correct explanation for assertion.
(a) Sodium and bicarbonate(b) Magnesium and chloride
(c) Assertion is correct, reason is incorrect
(c) Potassium and sulphate (d) Ammonium and chloride
(d) Assertion is incorrect, reason is correct.
43. Calgon used as a water softener is
(a) Na 2 [Na 4 (PO3 ) 6 ] (b) Na 4 [ Na 2 (PO 3 ) 6 ] Topic 6: Hydrogen Peroxide (H2O2)
51. In lab H2O2 is prepared by
(c) Na 4 [Na 4 (PO 4 )5 ] (d) Na 4 [ Na 2 ( PO 4 ) 6 ]
(a) Cold H2SO4 + BaO2 (b) HCl + BaO2
44. Polyphosphates are used as water softening agents because (c) Conc. H2SO4 + Na2O2 (d) H2 + O2
they 52. HCl is added to following oxides. Which one would give
(a) form soluble complexes with anionic specise H2O2
(b) precipitate anionic species (a) MnO2 (b) PbO2 (c) BaO (d) None
(c) forms soluble complexes with cationic species 53. 30 volume hydrogen peroxide means
(d) precipitate cationic species (a) 30% of H 2 O 2 solution
45. Permanent hardness of water can be removed by adding
(b) 30 cm3 solution contains 1g of H 2 O 2
Calgon (NaPO3)n. This is an example of
(a) Adsorption (b) Exchange of ion (c) 1 cm3 of solution liberates 30 cm3 of O2 at STP
(c) Precipitation (d) None (d) 30 cm3 of solution contains 1 mole of H2O2
HYDROGEN 117

54. The volume strength of 1.5 N H2O2 solution is : (c) 2MnO4– + 3H2O2 ® 2MnO2 + 3O2 +2H2O+2OH¯
(a) 8.4 (b) 8.0 (c) 4.8 (d) 3.0 (d) I2 + H2O2 + 2OH¯ ® 2I¯ + 2H2O + O2
55. Commercial 10 volume H2O2 is a solution with a strength of 67. Which of the following is not true for hydrogen peroxide?
approximately (a) H2O2 decomposes slowly on exposure to light.
(a) 15% (b) 3% (c) 1% (d) 10% (b) It is kept away from dust because dust can induce
56. Which of the following is the true structure of H2O2 ? explosive decomposition of the compound.
(a) H – O – O – H (b) H (c) H2O2 is used as bleaching agent for textiles, paper
O O pulp etc.
H
H (d) It is used as a moderator in nuclear reactor.
+ H
(c) O – O– (d) O O. 68. The decomposition of H2O2 is accelerated by –
H H (a) glycerine (b) alcohol
57. In the hydrogen peroxide molecule : (c) phosphoric acid (d) Pt powder
(a) O – H bonds are polar but molecule is non-polar. 69. H2O2 is
(b) The four atoms are arranged in a non-linear and non- (a) Poor polar solvent than water
planar manner. (b) Better polar solvent than H2O
(c) All the four atoms are in same plane. (c) Both have equal polarity
(d) Two hydrogen atoms are connected to one of the oxygen. (d) Better polar solvent but its strong auto-oxidising ability
58. H2O2 is a limits its use as such
(a) Weak acid (b) Weak base 70. Which of the following is wrong about H2O2? It is used
(c) Neutral (d) None of these (a) As aerating agent in production of spong rubber
59. When H2O2 is oxidised the product is (b) As an antichlor
(a) OH– (b) O2 (c) O2– (d) HO2– (c) For restoring white colour of blackened lead painting
60. Which of the following is false about H2O2 (d) None of these
(a) Act as both oxidising and reducing agent 71. Which of the following statements are correct?
(b) Two OH bonds lies in the same plane (i) Hydrogen peroxide is industrially prepared by the
(c) Pale blue liquid auto-oxidation of 2-alkylanthraquinols.
(d) Can be oxidised by ozone (ii) One millilitre of 30% H2O2 means that solution will
61. In which of the following reactions, H2O2 acts as a reducing give 100 V of oxygen at STP.
agent (iii) Dihedral angle of H2O2 in gas phase is 90.2° and in
(a) PbO2(s) + H2O2 (aq) ® PbO(s) + H2O(l) + O2 (g) solid phase dihedral angle is 111.5°.
(b) Na2SO3 (aq) + H2O2(aq) ® Na2SO4(aq) + H2O(l) (a) (i), (ii) and (iii) (b) (i) and (iii)
(c) 2KI(aq) + H2O2 (aq) ® 2KOH (aq) + I2(s) (c) (ii) and (iii) (d) (i) and (ii)
(d) KNO2(aq) + H2O2 (aq) ® KNO3 (aq) + H2O(l) 72. Assertion : H2O2 is not stored in glass bottles.
62. H2O2 ® 2H+ + O2 + 2e– ; E° = – 0.68 V. This equation Reason : Alkali oxides present in glass catalyse the
represents which of the following behaviour of H2O2. decomposition of H2O2.
(a) Reducing (b) Oxidising (a) Assertion is correct, reason is correct; reason is a
(c) Acidic (d) Catalytic correct explanation for assertion.
63. The reaction (b) Assertion is correct, reason is correct; reason is not a
H 2S + H 2 O 2 ¾¾® S + 2H 2 O manifests correct explanation for assertion.
(a) Acidic nature of H2O2 (b) Alkaline nature of H2O2 (c) Assertion is correct, reason is incorrect.
(c) Oxidising action of H2O2(d) Reducing action of H2O2. (d) Assertion is incorrect, reason is correct.
64. Which of the following statements is incorrect ? 73. Identify x and y in following reaction:
(a) H2O2 can act as an oxidising agent
2HSO-4 (aq) ¾¾¾¾¾
electrolysis hydrolysis
(b) H2O2 can act as a reducing agent ® x ¾¾¾¾¾ ®
y + 2H+(aq) + H2O2(aq)
(c) H2O2 has acidic properties
(a) x = H2SO4 (aq), y = 2HSO-4 (aq)
(d) H2O2 has basic properties
65. Which one of the following undergoes reduction with (b) x = HO3SOOSO3H(aq), y = 2HSO -4 (aq)
hydrogen peroxide in an alkaline medium ? (c) x = HO3SOOSO3H (aq), y = H2SO4(aq)
(a) Mn 2+ (b) HOCl (c) PbS (d) I2 (d) x = H2SO4(aq) , y = HO3SOOSO3H(aq)
66. Which of the following does not represent reducing Topic 7: Heavy Water (D2O)
action of H2O2? 74. What is formed when calcium carbide reacts with heavy
(a) PbS(s) + 4H2O2(aq) ® PbSO4(s) + 4H2O(l) water?
(b) HOCl + H2O2 ® H3O + + Cl¯ + O2 (a) C2D2 (b) CaD2 (c) Ca2D2O (d) CD2
 EBD_7374
118 CHEMISTRY

75. D2O is used in 78. D2O is preferred to H2O, as a moderator, in nuclear reactors
(a) motor vehicles (b) nuclear reactor because
(c) medicine (d) insecticide (a) D2O slows down fast neutrons better
(b) D2O has high specific heat
76. Complete the following reaction.
(c) D2O is cheaper
Al4C3 + D2O ® x + y
(d) None of these
(a) x = C2D2 and y = Al(OD)3 79. Which of the following is not true?
(b) x = CD4 and y = Al(OD)3 (a) D2O freezes at lower temperature than H2O
(c) x = CO2 and y = Al2D3 (b) Reaction between H2 and Cl2 is much faster than D2
(d) x = CD4 and y = Al2D3 and Cl2
77. Which of the following is correct about heavy water ? (c) Ordinary water gets electrolysed more rapidly than D2O
(a) Water at 4°C having maximum density is known as (d) Bond dissociation energy of D2 is greater than H2
heavy water 80. Heavy water reacts respectively with CO2, SO3, P2O5 and
N2O5 to give the compounds :
(b) It is heavier than water (H2O)
(a) D2CO3, D2SO4, D3PO2, DNO2
(c) It is formed by the combination of heavier isotope of (b) D2CO3, D2SO4, D3PO4, DNO2
hydrogen with oxygen (c) D2CO3, D2SO3, D3PO4, DNO2
(d) None of these (d) D2CO3, D2SO4, D3PO4, DNO3

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 5. Radioactive elements emit a, b and g rays and are
characterised by their half-lives. The radioactive isotope
1. Hydrogen resembles halogens in many respects for which
of hydrogen is
several factors are responsible. Of the following factors
(a) protium (b) deuterium (c) tritium (d) hydronium
which one is most important in this respect?
6. Consider the reactions
(a) Its tendency to lose an electron to form a cation.
(i) H2O2 + 2HI ¾¾ ® I2 + 2H2O
(b) Its tendency to gain a single electron in its valence
shell to attain stable electronic configuration. (ii) HOCl + H2O2 ¾¾
® H3O + + Cl– + O2
(c) Its low negative electron gain enthalpy value. Which of the following statements is correct about H2O2 with
(d) Its small size. reference to these reactions ? Hydrogen peroxide is .....
2. Why does H+ ion always get associated with other atoms or (a) an oxidising agent in both (i) and (ii)
molecules? (b) an oxidising agent in (i) and reducing agent in (ii)
(a) Ionisation enthalpy of hydrogen resembles that of alkali (c) a reducing agent in (i) and oxidising agent in (ii)
metals. (d) a reducing agent in both (i) and (ii)
(b) Its reactivity is similar to halogens. 7. The oxide that gives H2O2 on treatment with dilute H2SO4 is
(c) It resembles both alkali metals and halogens. (a) PbO2 (b) BaO2.8H2O
(d) Loss of an electron from hydrogen atom results in a (c) MnO2 (d) TiO2
nucleus of very small size as compared to other atoms 8. Which of the following equations depict the oxidising nature
or ions. Due to small size it cannot exist free. of H2O2?
3. Metal hydrides are ionic, covalent or molecular in nature.
(a) 2MnO -2 + 6H + + 5H 2 O 2 ¾¾
® 2Mn 2+ + 8H 2 O + 5O 2
Among LiH, NaH, RbH, CsH, the correct order of increasing
ionic character is
(b) 2Fe3+ + 2H + + H 2 O 2 ¾¾
® 2Fe 2+ + 2H 2 O + O 2
(a) LiH > NaH > CsH > KH >RbH
(b) LiH < NaH < KH < RbH < CsH (c) 2I - + 2H + + H 2 O 2 ¾¾
® I 2 + 2H 2 O
(c) RbH > CsH > NaH > KH > LiH
(d) NaH > CsH > RbH > LiH > KH (d) KIO 4 + H 2 O 2 ¾¾
® KIO 3 + H 2 O + O 2
4. Which of the following hydrides is electron-precise hydride? 9. Which of the following equation depict reducing nature of
(a) B2H6 (b) NH3 (c) H2O (d) CH4 H2O2?
HYDROGEN 119

17. Elements of which of the following group(s) of periodic table

(a) 2[Fe(CN) 6 ]4 - + 2H + + H 2 O 2 ¾¾
®
do not form hydrides?
3- (a) Groups 7, 8, 9 (b) Group 13
2 [ Fe ( CN )6 ] + 2H 2 O (c) Groups 15, 16, 17 (d) Group 14
(b) I 2 + H 2 O 2 + 2OH - ¾¾
® 2I - + 2H 2 O + O 2 18. Only one element of ........ forms hydride.
(a) group 6 (b) group 7 (c) group 8 (d) group 9
(c) Mn 2 + + H 2O 2 ¾¾
® Mn 4+ + 2OH -
Past Year MCQs
(d) PbS + 4H 2 O 2 ¾¾
® PbSO 4 + 4H 2 O
10. Hydrogen peroxide is .......... . 19. (i) H2O2 + O3 ® H2O + 2O2
(a) an oxidising agent (ii) H2O2 + Ag2O ® 2Ag + H2O + O2
(b) a reducing agent Role of hydrogen peroxide in the above reactions is
(c) both an oxidising and a reducing agent respectively - [AIPMT 2014, C]
(d) neither oxidising nor reducing agent (a) Oxidizing in (i) and reducing in (ii)
11. Which of the following reactions increases production of (b) Reducing in (i) and oxidizing in (ii)
dihydrogen from synthesis gas? (c) Reducing in (i) and (ii)
(d) Oxidizing in (i) and (ii)
CH 4 ( g ) + H 2 O ( g ) ¾¾ ¾¾
® CO ( g ) + 3H 2 ( g )
1270 K
(a) Ni
20. Assertion : HOF bond angle in HFO is higher than HOCl
bond angle in HClO.
C ( s ) + H 2 O ( g ) ¾¾¾¾
® CO ( g ) + H 2 (g )
1270 K
(b) Reason : Oxygen is more electronegative than halogens.
[AIIMS 2014, S]
CO ( g ) + H 2 O ( g ) ¾¾¾¾
® CO 2 ( g ) + H 2 ( g )
673K (a) If both Assertion and Reason are correct and Reason
(c) Catalyst is the correct explanation of Assertion.
1270 K (b) If both Assertion and Reason are correct, but Reason
(d) C 2 H 6 + 2H 2 O ¾¾¾¾
® 2CO + 5H 2 is not the correct explanation of Assertion.
Ni
12. When sodium peroxide is treated with dilute sulphuric acid, (c) If Assertion is correct but Reason is incorrect.
we get ........ . (d) If both the Assertion and Reason are incorrect.
(a) sodium sulphate and water 21. In which of the following reactions H2O2 acts as a reducing
(b) sodium sulphate and oxygen agent? [JEE M 2014, C]
(c) sodium sulphate, hydrogen and oxygen (i) H 2 O 2 + 2H + + 2e - ® 2H 2 O
(d) sodium sulphate and hydrogen peroxide
13. Hydrogen peroxide is obtained by the electrolysis of .... . (ii) H 2 O 2 + 2e - ® O2 + 2H +
(a) water (b) sulphuric acid
(c) hydrochloric acid (d) fused sodium peroxide (iii) H 2 O 2 + 2e - ® 2OH -
14. Which of the following reactions is an example of use of
water gas in the synthesis of other compounds? (iv) H 2 O 2 + 2OH - - 2e - ® O2 + 2H 2 O
(a) (i), (iii) (b) (iii), (iv)
CH 4 ( g ) + H 2 O ( g ) ¾¾¾¾
® CO ( g ) + H 2 ( g )
1270 K
(a) Ni (b) (i), (ii) (d) (ii), (iv)
22. The alkali metals form salt-like hydrides by the direct
CO ( g ) + H 2 O ( g ) ¾¾¾¾
® CO 2 ( g ) + H 2 ( g )
673 K
(b) Catalyst synthesis at elevated temperature. The thermal stability of
these hydrides decreases in which of the following orders?
C n H 2n + 2 + nH 2 O ( g ) ¾¾¾¾
1270 K [AIIMS 2015, C]
(c) ® nCO + ( 2n + 1) H 2
Ni
(a) CsH > RbH > KH > NaH > LiH
(b) KH > NaH > LiH > CsH > RbH
CO ( g ) + 2H 2 ( g ) ¾¾¾¾
Cobalt
(d) ® CH3OH ( l)
Catalyst (c) NaH > LiH > KH > RbH > CsH
15. Which of the following ions will cause hardness in water (d) LiH > NaH > KH > RbH > CsH
sample? 23. Assertion : Hydrogen combines with other elements by
(a) Ca2+ (b) Na+ (c) Cl– (d) K+ losing, gaining or sharing of electrons. [AIIMS 2015, C]
16. Which of the following compounds is used for water Reason : Hydrogen forms electrovalent and covalent bonds
softening? with other elements.
(a) Ca3(PO4)2 (b) Na3PO4 (a) If both Assertion and Reason are correct and Reason
(c) Na6P6O18 (d) Na2HPO4 is the correct explanation of Assertion.
 EBD_7374
120 CHEMISTRY

(b) If both Assertion and Reason are correct, but Reason 29. When zeolite (hydrated sodium aluminium silicate) is treated
is not the correct explanation of Assertion. with hard water the sodium ions are exchanged with
(c) If Assertion is correct but Reason is incorrect. [AIIMS 2017, A]
(d) If both the Assertion and Reason are incorrect. (a) H+ ions (b) Ca2+ ions
24. From the following statements regarding H2O2, choose the
(c) SO 2–
4 ions (d) OH– ions
incorrect statement : [JEE M 2015, S]
(a) It has to be stored in plastic or wax lined glass bottles in dark 30. Identify the structure of water in the gaseous phase.
(b) It has to be kept away from dust [BITSAT 2017, C]
(c) It can act only as an oxidizing agent +
(d) It decomposes on exposure to light (a) H–O–H (b) H – O – H
25. Which one the following removes temporary hardness of H
water ? [BITSAT 2015, A] 2 d–

(a) Slaked lime (b) Plaster of Paris O 95

.7
(c) pm (d) None of these
d+ 104.5° d+
(c) Epsom (d) Hydrolith H H
26. Which of the following statements about hydrogen is 31. The label on a bottle of H2O2 solution reads as ‘10 volume’.
incorrect ? [NEET 2016, C] The concentration of H2O2 in percentage by volume is
(a) hydrogen has three isotopes of which tritium is the
[AIIMS 2018, S]
most common.
(a) 4.05% (b) 3.03% (c) 6.06% (d) 2.03%
(b) Hydrogen never acts as cation in ionic salts
32. Hydrogen peroxide oxidises [Fe(CN)6]4– to [Fe(CN)6]3– in
(c) Hydronium ion, H3O+ exists freely in solution
acidic medium but reduces [Fe(CN)6]3– to [Fe(CN)6]4– in
(d) Dihydrogen does not act as a reducing agent
alkaline medium. The other products formed are respectively:
27. Which of the following statements is incorrect?
[AIIMS 2016, C] (a) (H2O + O2) and H2O [JEE M 2018, S]
(a) Ionic hydrides are stoichiometric compounds of (b) (H2O + O2) and (H2O + OH–)
dihydrogen formed with most of s-block elements. (c) H2O and (H2O + O2)
(b) Ionic hydrides are crystalline, non-volatile and non- (d) H2O and (H2O + OH–)
conducting in solid state. 33. Consider the reactions
(c) Melts of ionic hydrides conduct electricity and liberate (A) H2O2 + 2HI ® I2 + 2H2O
dihydrogen gas at cathode. (B) HOCl + H2O2 ® H3O+ + Cl– + O2
(d) Both (a) and (c) Which of the following statements is correct about H2O2
28. Which one of the following statements about water is FALSE? with reference to these reactions? Hydrogen peroxide is
[JEE M 2016, C] ______ . [BITSAT 2018, C]
(a) There is extensive intramolecular hydrogen bonding (a) an oxidising agent in both (A) and (B)
in the condensed phase. (b) an oxidising agent in (A) and reducing agent in (B)
(b) Ice formed by heavy water sinks in normal water. (c) a reducing agent in (A) and oxidising agent in (B)
(c) Water is oxidized to oxygen during photosynthesis.
(d) a reducing agent in both (A) and (B)
(d) Water can act both as an acid and as a base.
HYDROGEN 121

Exercise 3 : Try If You Can

1. When 50% solution of H2SO4 is electrolysed by passing a (c) Calcium forms soluble compounds with stearate ions
current of high density at low temperature the main products present in soap.
of electrolysis are: (d) Both calcium and sodium form insoluble compounds
(a) oxygen and hydrogen
with stearate ions present in soap.
(b) H2 and peroxy disulphuric acid
(c) H2 and SO2 8. The hydride ion, H–, is a stronger base than the hydroxide
(d) O2 and peroxy disulphuric acid ion, OH–. Which one of the following reactions will occur if
2. Hydrogen can be fused to form helium at sodium hydride (NaH) is dissolved in water?
(a) high temperature and high pressure (a) H - (aq) + H 2 O(l) ® H 3O - (aq)
(b) high temperature and low pressure
(c) low temperature and high pressure (b) H - (aq) + H 2 O(l) ® OH - (aq) + H 2 (g)
(d) low temperature and low pressure
3. When a substance A reacts with water it produces a (c) H - (aq) + H 2 O(l) ® OH - (aq) + 2 H + (aq) + 2e –
combustible gas B and a solution of substance C in water. (d) H - (aq) + H 2 O(l) ® No reaction
When another substance D reacts with this solution of C, it
also produces the same gas B on warming but D can produce 9. 34 g of H2O2 is present in 1120 mL of solution. This solution
gas B on reaction with dilute sulphuric acid at room is called
temperature. A imparts a deep golden yellow colour to a (a) 10 vol solution (b) 20 vol solution
smokeless flame of Bunsen burner. A, B, C and D (c) 34 vol solution (d) 32 vol solution
respectively are
10. A 5.0 mL solution of H2O2 liberates 1.27 g of iodine from an
(a) Na , H2, NaOH, Zn
acidified KI solution. The percentage strength of H2O2 is
(b) K, H2, KOH, Al
(a) 11.2 (b) 5.6 (c) 1.7 (d) 3.4
(c) Ca, H2, Ca(OH)2, Sn
11. If 100 mL of acidified 2 N H2O2 is allowed to react with
(d) CaC2, C2H2, Ca(OH)2, Fe KMnO4 solution till there is a light tinge of purple colour.
4. When same amount of zinc is treated separately with excess The volume of oxygen produced at STP is
of sulphuric acid and excess of sodium hydroxide solution (a) 2.24 L (b) 1.12 L (c) 3.36 L (d) 4.48 L
the ratio of volumes of hydrogen evolved is
12. 100 mL of 0.01 M KMnO4 oxidises 100 mL H2O2 in acidic
(a) 1 : 1 (b) 1 : 2 (c) 2 : 1 (d) 9 : 4
medium. Volume of the same KMnO4 required in alkaline
5. Pick out the correct statement medium to oxidise 100 mL of the same H2O2 will be (MnO4–
(a) By decreasing the temperature pure para-hydrogen can changes to Mn2+ in acidic medium and to MnO2 in alkaline
be obtained medium)
(b) By increasing the temperature pure ortho-hydrogen
can be obtained 100 500 300
(a) mL (b) mL (c) mL (d) None
(c) By decreasing the temperature pure ortho-hydrogen 3 3 5
can be obtained
13. 10 mL of H2O2 solution (volume strength = x) requires 10 mL
(d) By increasing the temperature pure para-hydrogen can of N/0.56 MnO4– solution in acidic medium. Hence x is
be obtained
(a) 0.56 (b) 5.6 (c) 0.1 (d) 10
6. When a sample of hard water is passed through the layer
of sodium zeolite resulting which of the following ions will 14. The normality and volume strength of a solution made by
not be present in the resulting sample of water obtained? mixing 1.0 L each of 5.6 volume and 11.2 volume H2O2
(a) Mg2+ and Ca2+ (b) Ca2+ and Na+ solution are :
(c) Mg2+ and CO32 - (d) CO32 - and Cl– (a) 1 N, 5.6 vol (b) 1.5 N. 5.6 vol
7. Why do calcium ions make water hard but sodium ions do (c) 1.5 N, 8.4 vol (d) 1 N, 8.4 vol
not? 15. The purity of H2O2 in a given sample is 85%. Calculate the
(a) Calcium forms insoluble compounds with stearate ions weight of impure sample of H2O2 which requires 10 mL of
present in soap.
M/5 KMnO4 solution in titration in acidic medium
(b) Sodium forms insoluble compounds with stearate ions
present in soap. (a) 2 g (b) 0.2 g (c) 0.17 g (d) 0.15 g
 EBD_7374
122 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 9 (d) 17 (b) 25 (b) 33 (c) 41 (d) 49 (b) 57 (b) 65 (b, d) 73 (b)
2 (d) 10 (d) 18 (c) 26 (d) 34 (b) 42 (b) 50 (c) 58 (a) 66 (a) 74 (a)
3 (c) 11 (c) 19 (c) 27 (d) 35 (c) 43 (a) 51 (a) 59 (b) 67 (d) 75 (b)
4 (a) 12 (a) 20 (d) 28 (d) 36 (c) 44 (c) 52 (d) 60 (b) 68 (d) 76 (b)
5 (b) 13 (b) 21 (c) 29 (c) 37 (b) 45 (b) 53 (c) 61 (a) 69 (d) 77 (c)
6 (d) 14 (a) 22 (d) 30 (d) 38 (b) 46 (a) 54 (a) 62 (a) 70 (d) 78 (d)
7 (a) 15 (a) 23 (c) 31 (b) 39 (a) 47 (a) 55 (b) 63 (c) 71 (d) 79 (a)
8 (c) 16 (d) 24 (c) 32 (a) 40 (b) 48 (d) 56 (b) 64 (d) 72 (a) 80 (d)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (b) 5 (c) 9 (b) 13 (b) 17 (a) 21 (d) 25 (a) 29 (b) 33 (b)
2 (d) 6 (b) 10 (c) 14 (d) 18 (a) 22 (d) 26 (a, d) 30 (c)
3 (b) 7 (b) 11 (c) 15 (a) 19 (a) 23 (a) 27 (c) 31 (b)
4 (d) 8 (c) 12 (d) 16 (c) 20 (d) 24 (c) 28 (a) 32 (c)
Exercis e 3 : Try If You Can
1 (b) 3 (a) 5 (a) 7 (a) 9 (a) 11 (a) 13 (d) 15 (b)
2 (a) 4 (a) 6 (a) 8 (b) 10 (d) 12 (b) 14 (c)
 10 Chapter
THE s-BLOCK ELEMENTS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Variation in periodic properties,
AIIMS 3 preparation and properties of 3/5 6.9
JEE Main 3 alkali and alkaline earth metal
BITSAT 2
 EBD_7374
124 CHEMISTRY
THE s-BLOCK ELEMENTS 125
 EBD_7374
126 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Group 1 Elements: Alkali Metals (a) Nickel (b) Aluminium

(c) Silver (d) Lead
1. Which of the following alkali metal is highly radioactive? 15. Which of the following metal is used as a coolant in
(a) Rubidium (b) Caesium breeder nuclear reactors?
(c) Francium (d) Both (a) and (c) (a) Potassium (b) Sodium
2. Which of the following statements is not correct for alkali (c) Caesium (d) Rubidium
metals? 16. Select the correct statements
(a) Alkali metals are the most electropositive metals. (i) Cs+ is more highly hydrated that the other alkali metal ions
(b) Alkali metals exist in free state in nature. (ii) Among the alkali metals Li, Na, K and Rb, lithium has
(c) These metals have the largest size in a particular the highest melting point
period of the periodic table. (iii) Among the alkali metals only lithium forms a stable
(d) Both (b) and (c) nitride by direct combination with nitrogen
3. Ionization potential of Na would be numerically the same as (a) (i), (ii) and (iii) (b) (i) and (ii)
(a) electron affinity of Na+ (c) (i) and (iii) (d) (ii) and (iii)
(b) electronegativity of Na+ 17. Suppose an element is kept in air chamber, than air content
(c) electron affinity of He was evaluated after sometime , oxygen and nitrogen content
(d) ionization potential of Mg was found to be low comparitively. The given element will be
4. Which one of the following properties of alkali metals (a) Li (b) Rb (c) Na (d) K
increases in magnitude as the atomic number rises in the
Topic 2: General Characteristics of the Compounds of
group ?
(a) Ionic radius (b) Melting point the Alkali Metals
(c) Electronegativity (d) First ionization energy. 18. Which of the following is used as a source of oxygen in
5. Which of the following has density greater than water? space capsules, submarines and breathing masks ?
(a) Li (b) Na (c) K (d) Rb (a) Li 2O (b) Na 2O 2 (c) KO2 (d) K 2O2
6. The elements of group 1 provide a colour to the flame of
Bunsen burner due to 19. Which is the most basic of the following?
(a) low ionization potential (a) Na 2O (b) BaO (c) As2O3 (d) Al2O3
(b) low melting point 20. Which is most basic in character ?
(c) softness (a) CsOH (b) KOH (c) NaOH (d) LiOH
(d) presence of one electron in the outermost orbit 21. Which compound will show the highest lattice energy ?
7. The element which on burning in air gives peroxide is (a) RbF (b) CsF (c) NaF (d) KF
(a) lithium (b) sodium (c) rubidium (d) caesium 22. In crystals which one of the following ionic compounds
8. Which one of the alkali metals, forms only, the normal oxide, would you expect maximum distance between centres of
M2O on heating in air ? cations and anions?
(a) Rb (b) K (c) Li (d) Na (a) LiF (b) CsF (c) CsI (d) LiI
9. The ionic mobility of alkali metal ions in aqueous solution is 23. Among LiI, NaI, KI, the one which is more ionic and more
maximum for soluble in water is
(a) Li+ (b) Na+ (c) K+ (d) Rb+ (a) KI (b) NaI (c) LiI (d) None
10. Which of the following pairs of substances would give same 24. Which of the following statement(s) is/are correct regarding
gaseous product on reaction with water? Li2CO3 and Na2CO3 ?
(a) Na and Na2O2 (b) Ca and CaH2 (i) Sodium salt evolve CO2 at higher temperature.
(c) Ca and CaO (d) Ba and BaO2 (ii) Polarization of Na+ is lesser than that of Li+.
11. Which hydride is most stable (a) Both statements (i) and (ii) are correct
(a) NaH (b) KH (c) CsH (d) LiH (b) Both statements (i) and (ii) are incorrect
12. The most stable compound is (c) Statement (ii) is correct explanation for statement (i)
(a) LiF (b) LiCl (c) LiBr (d) LiI (d) Statement (i) is correct explanation for statement (ii)
13. Which of the following represents a correct sequence of 25. Which of the following statements is incorrect?
reducing power of the following elements? (a) Alkali metal hydroxide are hygroscopic
(a) Li > Cs > Rb (b) Rb > Cs > Li (b) Dissolution of alkali metal hydroxide is endothermic
(c) Cs > Li > Rb (d) Li > Rb > Cs (c) Aqueous solution of alkali metal hydroxides are
14. Which of the following metal is used along with lithium strongly basic
to make the alloy named ‘white metal’ ? (d) Alkali metal hydroxides form ionic crystals
THE s-BLOCK ELEMENTS 127

26. Suppose metal react with the oxygen to form oxide, than (a) strongest reducing agent
aqueous solution of this oxide when added to a solution of HI, (b) poorest reducing agent
solution turn yellowish brown in colour. This compound is (c) strongest oxidising agent
(a) Na2O (b) Li2O (c) NaOH (d) Na2O2 (d) poorest oxidising agent
27. Which of the following salt of lithium is most soluble in 36. Assertion: Lithium salts are mostly hydrated.
organic solvent ? Reason : The hydration enthalpy of alkali metal ions
(a) LiF (b) LiCl (c) LiBr (d) LiI decreases with increase in ionic sizes.
(a) Assertion is correct, reason is correct; reason is a
Topic 3: Anomalous Properties of Lithium
correct explanation for assertion.
28. The products obtained on heating LiNO2 will be (b) Assertion is correct, reason is correct; reason is not a
(a) Li 2 O + NO2 + O2 (b) Li 3 N + O 2 correct explanation for assertion
(c) Assertion is correct, reason is incorrect
(c) Li 2O + NO + O 2 (d) LiNO3 + O2 (d) Assertion is incorrect, reason is correct.
29. Complete the following two reactions.
(i) 4LiNO3 ® x + O2 Topic 4: Some Important Compounds of Sodium
(ii) 2NaNO3 ® y + O2 37. In Solvay ammonia process, sodium bicarbonate is
(a) x = LiNO2, y = NaNO2 precipitated due to
(b) x = Li2O + NO2, y = Na2O + NO2 (a) presence of NH3
(c) x = Li2O + NO2, y = NaNO2 (b) reaction with CO2
(d) x = LiNO2, y = Na2O + NO2 (c) reaction with brine solution
30. Which of the following does not illustrate the anomalous (d) reaction with NaOH
properties of lithium? 38. Sodium carbonate is manufactured by Solvay process. The
(a) The melting point and boiling point of Li are comparatively products which can be recycled are
high (a) CO2 and NH3 (b) CO2 and NH4Cl
(b) Li is much softer than the other group I metals (c) NaCl and CaO (d) CaCl2 and CaO.
(c) Li forms a nitride Li3N unlike group I metals 39. How NH3 is recovered in Solvay process?
(d) The ion of Li and its compounds are more heavily (a) By reaction of NH4Cl and Ca(OH)2
hydrated than those of the rest of the group (b) By reaction of NH4HCO3 and NaCl
31. Why lithium react less vigorously with water than other (c) By reaction of (NH4)2CO3 with H2O
alkali metals? (d) By any of the above
(a) Lithium has most negative E– value 40. Why Solvay process cannot be extended to the manufacture
(b) Lithium has small size and very high hydration of potassium carbonate?
energy. (a) Ammonium hydrogen carbonate does not react with
(c) Lithium has least negative E– value potassium chloride.
(d) Both (a) and (b) (b) Potassium hydrogen carbonate is too soluble to be
32. Lithium is strongest reducing agent among alkali metals due precipitated by the addition of ammonium
to which of the following factor? hydrogencarbonate to a saturated solution of
(a) Ionization energy (b) Electron affinity potassium chloride.
(c) Hydration energy (d) Lattice energy (c) Ammonium carbonate is precipitated out instead of
33. Assertion : Lithium carbonate is not so stable to heat. potassium hydrogen carbonate on reaction of
Reason : Lithium being very small in size polarizes large ammonium hydrogen carbonate with potassium
CO32 - ion leading to the formation of more stable Li2O chloride
and CO2 (d) None of the above
(a) Assertion is correct, reason is correct; reason is a 41. Which of the following is/are present as impurity in crude
correct explanation for assertion. sodium chloride, obtained by crystallisation of brine
(b) Assertion is correct, reason is correct; reason is not a solution?
correct explanation for assertion (i) Sodium sulphate (ii) Calcium chloride
(c) Assertion is correct, reason is incorrect (iii) Magnesium chloride (iv) Potassium chloride
(d) Assertion is incorrect, reason is correct. (a) (i), (ii) and (iv) (b) (ii) and (iii)
34. The melting point of lithium (181°C) is just double the melting (c) (iii) and (iv) (d) (i), (ii) and (iii)
point of sodium (98°C) because 42. Which is manufactured by electrolysis of fused NaCl?
(a) down the group, the hydration energy decreases (a) NaOH (b) Na (c) NaClO (d) NaClO3
(b) down the group, the ionization energy decreases 43. Baking powder contains :
(c) down the group the cohesive energy decreases (a) NaHCO3, Ca(H2PO2)2 and starch
(d) None of these (b) NaHCO3, Ca(H2PO2)2
35. Li has the maximum value of ionisation potential among (c) NaHCO3, starch
alkali metals i.e. lithium has the minimum tendency to ionise (d) NaHCO3
to give LI+ ion. Thus, in aq. solution lithium is
 EBD_7374
128 CHEMISTRY

44. Match the columns. (a) A – (q), B – (s), C – (r), D – (p), E – (t)
Column-I Column-II (b) A – (s), B – (q), C – (r), D – (p), E – (t)
(Sodium compound) (Uses) (c) A – (t), B – (r), C – (s), D – (p), E – (q)
(A) Sodium carbonate (p) In fire extinguisher (d) A – (q), B – (p), C – (r), D – (p), E – (t)
(B) Sodium chloride (q) In manufacture of 55. Which one of the following does not react with water even
glass, soap, borax under red hot condition?
and caustic soda. (a) Na (b) Be (c) Ca (d) K
(C) Sodium hydroxide (r) In preparation of Na2O2, 56. Aqueous solution of group 2 is precipitated by adding
NaOH and Na2CO3 Na2CO3, then this precipitate is tested on flame, no light in
(D) Sodium hydrogen (s) In petroleum refining visible region is observed , this element can be
carbonate (a) Ba (b) Mg (c) Ca (d) Sr
(a) A – (q), B – (r), C – (s), D – (p) 57. Which of the following statement(s) is/are correct?
(b) A – (s), B – (q), C – (r), D – (p) (i) The atomic and ionic radii of alkaline earth metals are
(c) A – (p), B – (s), C – (r), D – (q) smaller than those of the corresponding alkali metals
(d) A – (s), B – (r), C – (p), D – (q) in the same periods.
45. The raw materials in Solvay Process are (ii) Second ionisation enthalpies of the alkaline earth
(a) Na2CO3, CaCO3 and NH3 metals are smaller than those of the corresponding
(b) Na2SO4, CaCO3 and NH3 alkali metals.
(c) NaCl, NH3 and CaCO3 (iii) Compounds of alkaline earth metals are more
(d) NaOH, CaO and NH3. extensively hydrated than those of alkali metals
(a) (i) and (ii) (b) (ii) and (iii)
Topic 5: Group 2 Elements: Alkaline Earth Metals
(c) (i) and (iii) (d) (i), (ii) and (iii)
46. The metal that produces red-violet colour in the non- 58. Assertion : Radium is most abundant s-block element.
luminous flame is Reason : s-block elements are non-radioactive in nature.
(a) Ba (b) Ag (c) Rb (d) Pb (a) Assertion is correct, reason is correct; reason is a
47. Which of the following atoms will have the smallest size ? correct explanation for assertion.
(a) Mg (b) Na (c) Be (d) Li (b) Assertion is correct, reason is correct; reason is not a
48. The first ionization energy of magnesium is lower than the correct explanation for assertion.
first ionization energy of (c) Assertion is correct, reason is incorrect.
(a) Lithium (b) Sodium (c) Calcium (d) Beryllium (d) Assertion is incorrect, reason is correct.
49. The most electropositive amongst the alkaline earth metals 59. Compared with the alkaline earth metals, the alkali metals
is exhibit
(a) beryllium (b) magnesium (a) smaller ionic radii (b) highest boiling points
(c) calcium (d) barium (c) greater hardness (d) lower ionization energies
50. Alkaline earth metals are not found free in nature because
of Topic 6: General Characteristics of Compounds of
(a) their thermal instability the Alkaline Earth Metals
(b) their low melting points 60. Which of the following relations is correct with respect to
(c) their high boiling points first (I) and second (II) ionization potentials of sodium and
(d) their greater chemical reactivity magnesium?
51. A firework gives out crimson coloured light. It contains a
(a) I Mg = II Na (b) I Mg < II Na
salt of
(a) Ca (b) Na (c) Sr (d) Ba (c) I Na > I Mg (d) II Na > IIMg
52. Out of the following elements which one do you expect to 61. The first ionization energies of alkaline earth metals are
be most reactive, chemically ? higher than those of alkali metals. This is because
(a) Mg (b) Ca (c) Sr (d) Ba (a) there is no change in the nuclear charge
(b) there is decrease in the nuclear charge of alkaline earth
53. The metals A and B form oxide but B also forms nitride when
metals
both burn in air. The A and B are (c) there is increase in the nuclear charge of alkaline earth
(a) Cs, K (b) Mg, Ca (c) Li, Na (d) K, Mg metals
54. Match the columns (d) none of these
Column-I Column-II 62. Arrange the following compounds in order of increasing
(Alkali metal) (Colour imparted to an solubility
oxidizing flame) (i) MgF2 (ii) CaF2, (iii) BaF2
(A) Cs (p) Yellow (a) (i) < (ii) < (iii) (b) (ii) < (i) < (iii)
(B) Rb (q) Blue (c) (ii) < (iii) < (ii) (d) (iii) < (ii) < (i)
(C) K (r) Violet 63. Which one of the following is the most soluble in water?
(D) Na (s) Red violet (a) Mg(OH)2 (b) Sr(OH)2
(E) Li (t) Crimson red (c) Ca(OH) 2 (d) Ba(OH) 2
THE s-BLOCK ELEMENTS 129

64. Which of the following alkaline earth metal hydroxides is 77. Which of the following statement is false ?
amphoteric in character (a) Strontium decomposes water readily than beryllium
(a) Be(OH)2 (b) Ca(OH)2 (c) Sr(OH)2 (d) Ba(OH)2 (b) Barium carbonate melts at a higher temperature than
65. Of the metals Be, Mg, Ca and Sr of group 2 A. In the periodic calcium carbonate
table the least ionic chloride would be formed by (c) Barium hydroxide is more soluble in water than
(a) Be (b) Mg (c) Ca (d) Sr magnesium hydroxide
66. The solubilities of carbonates decrease down the magnesium (d) Beryllium hydroxide is more basic than barium
group due to a decrease in hydroxide.
(a) hydration energies of cations
Topic 7: Anomalous Behaviour of Beryllium
(b) inter-ionic attraction
(c) entropy of solution formation 78. Beryllium shows diagonal relationship with aluminium.
(d) lattice energies of solids Which of the following similarity is incorrect ?
67. The correct order of increasing thermal stability of K2CO3, (a) Be forms beryllates and Al forms aluminates
MgCO3, CaCO3 and BeCO3 is (b) Be(OH)2 like Al(OH)3 is basic.
(a) BeCO3< MgCO3 < CaCO3 < K2CO3 (c) Be like Al is rendered passive by HNO 3 .
(b) MgCO3 < BeCO3 < CaCO3 < K2CO3 (d) Be2C like Al4C3 yields methane on hydrolysis.
(c) K2CO3 < MgCO3 < CaCO3 < BeCO3 79. Which of the following statement(s) is/are correct regarding
(d) BeCO3 < MgCO3 < K2CO3 < CaCO3 Al and Be ?
68. In which of the following the hydration energy is higher (i) Both of these react with alkali.
than the lattice energy? (ii) There is diagonal relationship among these elements.
(a) MgSO4 (b) RaSO4 (c) SrSO4 (d) BaSO4 (a) Both (i) and (ii) (b) Only (i)
69. Which of the following is/are not characteristic (c) Only (ii) (d) Neither (i) nor (ii)
property(ies) of alkaline earth metals ? 80. Assertion : Compounds of beryllium is largely covalent and
(i) All alkaline earth metal oxides are basic in nature and get hydrolysed easily.
forms sparingly soluble hydroxides with water. Reason : This is due to high value of ionisation potential
(ii) The hydrated chlorides, bromides and iodies of Ca, and small size of Be.
Sr and Ba on heating undergoes hydrolysis while (a) Assertion is correct, reason is correct; reason is a
corresponding hydrated halides of Be and Mg on correct explanation for assertion.
heating undergo dehydration. (b) Assertion is correct, reason is correct; reason is not a
(iii) Nitrates of alkaline earth metals decompose on correct explanation for assertion.
heating as below (c) Assertion is correct, reason is incorrect.
2M(NO3)2 ® 2MO + 4NO2 + O2 (d) Assertion is incorrect, reason is correct.
(a) (i) only (b) (ii) only Topic 8: Some Important Compounds of Calcium
(c) (i) and (iii) (d) (i) and (ii)
70. Which of the following on thermal decomposition yields a 81. The substance not likely to contain CaCO3 is
basic as well as acidic oxide ? (a) gypsum (b) sea shells
(a) NaNO3 (b) KClO3 (c) CaCO3 (d) NH4NO3 (c) dolomite (d) a marble statue
71. Which one of the following on hydrolysis, gives the 82. Plaster of Paris on making paste with little water sets to
corresponding metallic hydroxide, H2O2 and O2? hard mass due to formation of
(a) Li2O (b) Na2O2 (c) NaO2 (d) Na2O (a) CaSO4 (b) CaSO4.1/2H2O
72. Which of the following oxides of potassium is not known ? (c) CaSO4.H2O (d) CaSO4.2H2O
(a) K2O (b) K2O4 (c) KO3 (d) K2O3 83. The formula for calcium chlorite is
(a) Ca(ClO4)2 (b) Ca(ClO3)2
73. Property of the alkaline earth metals that increases with
(c) CaClO2 (d) Ca(ClO2)2
their atomic number is
84. Bone ash contains
(a) solubility of their hydroxides in water
(a) CaO (b) CaSO4
(b) solubility of their sulphates in water (c) Ca3 (PO4)2 (d) Ca(H2PO4)2
(c) ionization energy 85. Mortar is a mixture of
(d) electronegativity (a) CaCO3, sand and water
74. Magnesium burns in CO2 to form (b) slaked lime and water
(a) MgO + C (b) MgO + CO (c) slaked lime, sand and water
(c) MgCO3 (d) MgO. (d) CaCO3 and CaO
75. Which of the following will precipitate first when aqueous 86. Which gas is released when CaCO3 reacts with dilute HCl?
solution containing sulphate ions are added? (a) H2 (b) CO2 (c) O2 (d) Cl2
(a) Mg2+ (b) Ca2+ (c) Sr2+ (d) Ba2+ 87. Setting of cement is an
76. If the fluoride salts of group 2 metals are dissolved in (a) exothermic reaction
water,than which of the following will show high solubility? (b) endothermic reaction
(a) BaF2 (b) RbF2 (c) CaF2 (d) BeF2 (c) neither endothermic nor exothermic
(d) example of neutralisation reaction
 EBD_7374
130 CHEMISTRY

88. For a good quality cement what should be the ratio of (a) A – (p), B – (s), C – (q), D – (r)
following : (b) A – (s), B – (p), C – (r), D – (q)
I. Silica to alumina (c) A – (q), B – (r), C – (p), D – (s)
II. CaO to the total of oxides of SiO2, Al2O3 and Fe2O3 (d) A – (r), B – (q), C – (s), D – (p)
(a) I = 2.5 to 4 (b) I = Nearly 4 92. Bleaching powder is obtained by the interaction of chlorine
II = Greater than 2 II = Less than 2 with
(c) I = 2.5 (d) I = 2.5 to 4
(a) dil. solution of Ca(OH)2
II = Closer to 2 II = Closer to 2
(b) dry CaO
89. Which of the following statements are correct ?
(i) Copper - beryllium alloys are used in the preparation (c) conc. solution of Ca(OH)2
of high strength springs (d) dry slaked lime
(ii) Metallic beryllium is used for making window X-ray Topic 9: Biological Importance of s-Block Elements
tubes.
93. Which of the following are found in biological fluids Na+,
(iii) Magnesium powder is used in incendiary bombs and
singnals. Mg2+, Ca2+, K+, Sr2+, Li+ and Ba2+
(iv) Barium is used in treatment of cancer. (a) Mg2+, Ca2+, and Sr2+
(a) (i), (ii) and (iv) (b) (i) and (iii) (b) Na2 +and K+
(c) (i), (ii) and (iii) (d) (i), (ii), (iii) and (iv) (c) Na+, K+, Mg2+and Ca2+
90. Match the columns (d) Sr+, Li and Ba2+
Column-I Column-II 94. Calcitonin and parathyroid hormone regulate concentration
(A) Quick lime (p) Ca(OH)2 of which of the following element in plasma?
(B) Slaked lime (q) CaO (a) Calcium (b) Magnesium
(C) Bleaching powder (r) Ca(OCl)2 (c) Sodium (d) Potassium
(D) Plaster of Paris (s) CaSO4. H2O 95. Which of the following metal is found in green colouring
(a) A – (p), B – (q), C – (r), D – (s) pigment chlorophyll of plants?
(b) A – (s), B – (r), C – (q), D – (p) (a) Fe (b) Mg (c) Na (d) Al
(c) A – (q), B – (p), C – (r), D – (s)
96. Which of the following is the most abundant ion within
(d) A – (q), B – (p), C – (s), D – (r)
cell fluids?
91. Match the columns
(a) Sodium ions (b) Potassium ions
(A) Quick lime (p) Setting fractured bones
(B) Plaster of Paris (q) A constituent of chewing (c) Calcium ions (d) None of these
gum 97. The ions which participate in the transmission of nerve
(C) Slaked lime (r) Manufacture of bleaching signals
powder (a) Na+ (b) Be2+ (c) Cs+ (d) Ba2+
(D) Limestone (s) Manufacture of dyestuffs

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (a) MgCO3 (b) CaCO3 (c) SrCO3 (d) BaCO3
5. Which of the following carbonates given below is unstable
1. The alkali metals are low melting. Which of the following
in air and is kept in CO2 atmosphere to avoid decomposition?
alkali metal is expected to melt if the room temperature rises
to 30°C? (a) BeCO3 (b) MgCO3 (c) CaCO3 (d) BaCO3
(a) Na (b) K (c) Rb (d) Cs 6. Metals form basic hydroxides. Which of the following metal
2. Alkali metals react with water vigorously to form hydroxides hydroxide is the least basic?
and dihydrogen. Which of the following alkali metals reacts (a) Mg(OH)2 (b) Ca(OH)2
with water least vigorously? (c) Sr(OH)2 (d) Ba(OH)2
(a) Li (b) Na (c) K (d) Cs 7. Some of the Group 2 metal halides are covalent and soluble
3. The reducing power of a metal depends on various factors. in organic solvents. Among the following metal halides,
Suggest the factor which makes Li, the strongest reducing the one which is soluble in ethanol is
agent in aqueous solution. (a) BeCl2 (b) MgCl2 (c) CaCl2 (d) SrCl2
(a) Sublimation enthalpy (b) lonisation enthalpy 8. The order of decreasing ionisation enthalpy in alkali metals
(c) Hydration enthalpy (d) Electron–gain enthalpy
is
4. Metal carbonates decompose on heating to give metal oxide
(a) Na > Li > K > Rb (b) Rb < Na < K < Li
and carbon dioxide. Which of the metal carbonates is most
stable thermally? (c) Li > Na > K > Rb (d) K < Li < Na < Rb
THE s-BLOCK ELEMENTS 131

9. The solubility of metal halides depends on their nature, 21. Dehydration of hydrates of halides of calcium, barium and
lattice enthalpy and hydration enthalpy of the individual strontium i.e., CaCl2. 6H2O, BaCl2.2H2O, SrCl2.2H2O can be
ions. Amongst fluorides of alkali metals, the lowest achieved by heating. These become wet on keeping in air.
solubility of Li in water is due to Which of the following statements is correct about these
(a) ionic nature of lithium fluoride halides?
(b) high lattice enthalpy (a) Act as dehydrating agent
(c) high hydration enthalpy for lithium ion (b) Can absorb moisture from air
(d) low ionisation enthapy of lithium atom (c) Tendency to form hydrate decreases form calcium to
10. Amphoteric hydroxides react with both alkalies and acids. barium
Which of the following Group 2 metal hydroxides is soluble (d) All of the above
in sodium hydroxide?
Past Year MCQs
(a) Be(OH)2 (b) Mg(OH)2 (c) Ca(OH)2 (d) Ba(OH)2
11. In the synthesis of sodium carbonate, the recovery of 22. Which of the following is commercially known as oxone ?
ammonia is done by treating NH4Cl with Ca(OH)2. The [AIIMS 2014,C]
by – product obtained in this process is (a) Na2O2 + HCl (b) Na2O + HCl
(a) CaCl2 (b) NaCl (c) NaOH (d) NaHCO3 (c) Na2O2 + Na2 (d) none of these
12. When sodium is dissolved in liquid ammonia, a solution of 23. Assertion : K, Rb and Cs (all belonging to group 1) can also
deep blue colour is obtained. The colour of the solution is form superoxides.
due to Reason : The ionic radii of K, Rb and Cs show the following
(a) ammoniated electron (b) sodium ion trend Cs+ < Rb+ < K+. [AIIMS 2014,C]
(c) sodium amide (d) ammoniated sodium ion (a) Assertion is correct, reason is correct; reason is a
13. By adding gypsum to cement correct explanation for assertion.
(a) setting time of cement becomes less (b) Assertion is correct, reason is correct; reason is not a
(b) setting time of cement increases correct explanation for assertion
(c) colour of cement becomes light (c) Assertion is correct, reason is incorrect
(d) shining surface is obtained (d) Assertion is incorrect, reason is correct.
14. Dead burnt plaster is 24. Which one of the following alkaline earth metal sulphates
has its hydration enthalpy greater than its lattice enthalpy ?
1
(a) CaSO4 (b) CaSO4 . H 2 O [JEE M 2015, 2014,C]
2 (a) BaSO4 (b) SrSO4 (c) CaSO4 (d) BeSO4
(c) CaSO4.H2O (d) CaSO4.2H2O 25. Which of the following among alkali metal is most reactive ?
15. Suspension of slaked lime in water is known as [BITSAT 2014,C]
(a) lime water (a) Na (b) K (c) Rb (d) Cs
(b) quick lime 26. The function of "Sodium pump" is a biological process
(c) milk of lime operating in each and every cell of all animals. Which of the
(d) aqueous solution of slaked lime following biologically important ions is also a consituent of
16. Which of the following elements does not form hydride by this pump : [AIPMT 2015,S]
direct heating with dihydrogen? (a) Mg2+ (b) K+ (c) Fe2+ (d) Ca2+
(a) Be (b) Mg (c) Sr (d) Ba 27. Solubility of the alkaline earth's metal sulphates in water
17. The formula of soda ash is decreases in the sequence :- [AIPMT 2015,C]
(a) Na2CO3.10H2O (b) Na2CO3.2H2O (a) Ca > Sr > Ba > Mg (b) Sr > Ca > Mg > Ba
(c) Na2CO3.H2O (d) Na2CO3 (c) Ba > Mg > Sr > Ca (d) Mg > Ca > Sr > Ba
18. A substance which gives brick red flame and breaks down 28. On heating which of the following releases CO2 most easily?
on heating to give oxygen and a brown gas is [AIPMT 2015 RS,C]
(a) magnesium nitrate (b) calcium nitrate (a) K2CO3 (b) Na2CO3 (c) MgCO3 (d) CaCO3
(c) barium nitrate (d) strontium nitrate 29. Lithophone is : [BITSAT 2015,C]
19. Which of the following statements is true about Ca(OH)2? (a) ZnSO4 + PbS (b) BaSO4 + ZnS
(a) It is used in the preparation of bleaching powder. (c) PbO2 (d) ZnSO4
(b) It is a light blue solid. 30. Which of the following statements is false ?
(c) It does not possess disinfectant property. [NEET 2016,C]
(d) It is used in the manufacture of cement. (a) Mg2+ ions form a complex with ATP
20. A chemical ‘A’ is used for the preparation of washing soda (b) Ca2+ ions are important in blood clotting
to recover ammonia.When CO2 is bubbled through an (c) Ca2+ ions are not important in maintaining the regular
aqueous solution of ‘A’, the solution turns milky. It is used beating of the heart.
in white washing due to disinfectant nature. What is the (d) Mg2+ ions are important in the green parts of plants.
chemical formula of ‘A’? 31. Which of the following is not correct ? [AIIMS 2016,S]
(a) Ca(HCO3)2 (b) CaO
heat
(c) Ca(OH)2 (d) CaCO3 (a) 2Li 2 O ¾¾¾® Li 2 O 2 + 2Li
673K
 EBD_7374
132 CHEMISTRY

heat 36. Which of the following oxides is most acidic in nature?

(b) 2K 2O ¾¾¾® K 2 O 2 + 2K [NEET 2018, C]
673K
(a) MgO (b) BeO (c) CaO (d) BaO
heat
(c) 2Na 2 O ¾¾¾® Na 2O 2 + 2Na 37. Magnesium reacts with an element (X) to form an ionic
673K
compound. If the ground state electronic configuration of
heat
(d) 2Rb 2O ¾¾¾® Rb 2 O 2 + 2Rb (X) is 1s2 2s2 2p3, the simplest formula for this compound is
673K
[NEET 2018, C]
32. The main oxides formed on combustion of Li, Na and K in
(a) Mg2X3 (b) MgX2 (c) Mg3X2 (d) Mg2X
excess of air are, respectively: [JEE M 2016, S]
38. Among CaH2, BeH2, BaH2, the order of ionic character is
(a) Li2O2, Na2O2 and KO2 (b) Li2O, Na2O2 and KO2
[NEET 2018, C]
(c) Li2O, Na2O and KO2 (d) LiO2, Na2O2 and K2O
(a) BeH2 < CaH2 < BaH2 (b) CaH2 < BeH2 < BaH2
33. Assertion : Lithium carbonate is not so stable to heat.
(c) BaH2 < BeH2 < CaH2 (d) BeH2 < BaH2 < CaH2
Reason : Lithium being very small in size polarizes large
39. Following are colours shown by some alkaline earth
CO32 - ion leading to the formation of more stable Li2O metals in flame test. Which of the following are not
and CO2 [AIIMS 2017, C] correctly matched? [BITSAT 2018, A]
(a) Assertion is correct, reason is correct; reason is a Metal Colour
correct explanation for assertion. (i) Calcium Apple green
(b) Assertion is correct, reason is correct; reason is not a (ii) Strontium Crimson
correct explanation for assertion (iii) Barium Brick red
(c) Assertion is correct, reason is incorrect (a) (i) and (iii) (b) (i) only
(d) Assertion is incorrect, reason is correct. (c) (ii) only (d) (ii) and (iii)
34. Which of the following is not present in Portland cement? 40. Beryllium shows diagonal relationship with aluminium.
[BITSAT 2017, A] Which of the following similarity is incorrect ?
(a) Ca2SiO4 (b) Ca3SiO5 [BITSAT 2018, C]
(c) Ca3(PO4)2 (d) Ca3Al2O6 (a) Be forms beryllates and Al forms aluminates
35. Dead burn plaster is [BITSAT 2017, A] (b) Be(OH)2 like Al(OH)3 is basic.
(a) CaSO4.2H2O (b) MgSO4. 7H2O (c) Be like Al is rendered passive by HNO3.
(c) CaSO4.½ H2O (d) CaSO4 (d) Be2C like Al4C3 yields methane on hydrolysis.

Exercise 3 : Try If You Can

1. The alkali metals form salt-like hydrides by the direct (2) Stability of Na2O2 < K2O2 < Rb2O2 < Cs2O2 peroxides
synthesis at elevated temperature. The thermal stability of (3) Stability of LiHCO3 < NaHCO3 < KHCO3 < RbHCO3 <
these hydrides decreases in which of the following order?
CsHCO3
(a) NaH > LiH > KH > RbH > CsH
(b) LiH > NaH > KH > RbH > CsH (4) Melting point NaF < NaCl < NaBr < NaI
(c) CsH > RbH > KH > NaH > LiH (a) 1 and 4 (b) 1 and 3
(d) KH > NaH > LiH > CsH > RbH (c) 1 and 2 (d) 2 and 3
2. Incorrect statement is: 5. In the following sequence of reaction, identify the
(a) NaHCO3 and KHCO3 have same crystal structure compounds (A), (B) (C) and (D) :
(b) On heating LiNO3 decomposes into Li2O and NO2
(c) Among alkali metals, Li metal impart red colour to flame
Na 2 CO3 ¾¾¾
SO
( )
2 ® A ¾¾¾¾
2 3
® ( B) ¾¾¾
Na CO
® ( C) ¾¾¾¾
S
3
® ( D)
Heat
AgNO

Solution
(d) Li2SO4 does not form alum
(a) Na2SO3, NaHSO3, Na2S, Ag2S
3. The solubility of metal halides depends on their nature,
(b) NaHSO3, Na2SO3, Na2S2O3, Ag2S
lattice enthalpy and hydration enthalpy of the individual
ions. Amongst fluorides of alkali metals, the lowest (c) NaHSO3, Na2SO4, Na2S, Ag2O
solubility of LiF in water is due to: (d) Na2SO3, Na2SO4, Na2S2O3, Ag
(a) Ionic nature of lithium fluoride
ZnCl 2 + NaHCO3 ¾¾¾® ( A ) ¾¾¾
® ( B) + ( C) +
Heat Heat
6.
(b) High lattice enthalpy
(c) High hydration enthalpy of lithium ion
H 2O ( B ) + NaOH ® ( D )
(d) Low ionisation enthalpy of lithium atom
4. Which is not correctly matched Identify the compound (D) present in the solution.
(1) Basic strength Cs2O < Rb2O < K2O < Na2O < Li2O of (a) ZnCO3 (b) Zn(OH)2
oxides (c) ZnO (d) Na2ZnO2
THE s-BLOCK ELEMENTS 133

7. To an acidified dicrhomate solution, a pinch of Na2O2 is (c) Hydration energy of MgSO4 is higher in comparison
added and shaken. What is observed? to its lattice energy
(a) Blue colour on surface (d) Ionic potential (charge/radius ratio) of Mg2+ is very
(b) Green colour in the lower layer low
(c) On adding Na2O2 to an acidified dichromate solution 11. Which one of the following processes will produce hard
a blue colour is appears on surface. An unstable water ?
performic acid is formed which decompose after some (a) Saturation of water with MgCO3
time with evolution of oxygen and a green aqueous (b) Saturation of water with CaSO4
solution of chromic sulphate is formed in lower layer (c) Addition of Na2SO4 to water
evolution of oxygen (d) Saturation of water with CaCO3
(d) All of these 12. A solid compound ‘X’ on heating gives CO2 gas and a
8. The basic character of the alkaline earth metal hydroxides residue. The residue mixed with water forms ‘Y’. On passing
is as follows : an excess of CO2 through ‘Y’ in water, a clear solution ‘Z’, is
(a) Mg(OH)2 > Ba(OH)2 > Ca(OH)2 > Sr(OH)2 obtained. On boiling ‘Z’, compound ‘X’ is reformed. The
(b) Be(OH)2 > Sr(OH)2 > Ca(OH)2 > Mg(OH)2 compound ‘X’ is
(c) Sr(OH)2 > Ca(OH)2 > Ba(OH)2 > Mg(OH)2 (a) Ca(HCO3)2 (b) CaCO3
(d) Mg(OH)2 > Ba(OH)2 > Sr(OH)2 > Ca(OH)2 (c) Na2CO3 (d) K2CO3
9. Na2SO4 is soluble in water whereas BaSO4 is sparingly 13. All of the following substances react with water. The pair
soluble because that gives the same gaseous product is
(a) The lattice enthalpy of Na 2SO 4 is less than its (a) K and KO2 (b) Na and Na2O2
hydration enthalpy. (c) Ca and CaH2 (d) Ba and BaO2
(b) Sodium is monovalent ion whereas barium is a divialent 14. In curing cement plasters, water is sprinkled from time to
ion. time. This helps in
(c) The hydration enthalpy of sodium sulphate is less (a) developing interlocking needle-like crystals of hydrated
than its lattice enthalpy. silicates
(d) The lattice enthalpy of barium sulphate is less than (b) hydrating sand and gravel mixed with cement
its hydration enthalpy. (c) converting sand into silicic acid
10. Which one is the correct statement with reference to (d) keeping it cool
solubility of MgSO4 in water? more CO
15. KO2 + CO2 + H2O ¾¾ ¾ ¾¾ 2®
[X] + [Y]
(a) SO42– ion mainly contributes towards hydration energy Products [X] and [Y] are respectively :
(b) Sizes of Mg2+ and SO42– are similar (a) K2CO3, O2 (b) KHCO3, O2
(c) KOH, K2CO3 (d) KHCO3, H2O
 EBD_7374
134 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 11 (d) 21 (c) 31 (b) 41 (d) 51 (c) 61 (c) 71 (c) 81 (a) 91 (b)
2 (b) 12 (a) 22 (c) 32 (c) 42 (b) 52 (d) 62 (b) 72 (b) 82 (d) 92 (d)
3 (a) 13 (a) 23 (a) 33 (a) 43 (a) 53 (d) 63 (d) 73 (a) 83 (d) 93 (c)
4 (a) 14 (d) 24 (c) 34 (c) 44 (a) 54 (a) 64 (a) 74 (a) 84 (c) 94 (a)
5 (d) 15 (b) 25 (b) 35 (a) 45 (c) 55 (b) 65 (a) 75 (d) 85 (c) 95 (b)
6 (a) 16 (d) 26 (d) 36 (a) 46 (c) 56 (b) 66 (a) 76 (a) 86 (b) 96 (b)
7 (b) 17 (a) 27 (d) 37 (c) 47 (c) 57 (d) 67 (a) 77 (d) 87 (a) 97 (a)
8 (c) 18 (c) 28 (a) 38 (a) 48 (d) 58 (d) 68 (a) 78 (b) 88 (d)
9 (d) 19 (a) 29 (c) 39 (a) 49 (d) 59 (d) 69 (d) 79 (a) 89 (c)
10 (b) 20 (a) 30 (b) 40 (b) 50 (d) 60 (d) 70 (c) 80 (a) 90 (c)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (d) 5 (a) 9 (b) 13 (b) 17 (d) 21 (d) 25 (d) 29 (b) 33 (a) 37 (c)
2 (a) 6 (a) 10 (a) 14 (a) 18 (b) 22 (a) 26 (b) 30 (c) 34 (c) 38 (a)
3 (c) 7 (a) 11 (a) 15 (c) 19 (a) 23 (c) 27 (d) 31 (a) 35 (d) 39 (a)
4 (d) 8 (c) 12 (a) 16 (a) 20 (c) 24 (d) 28 (c) 32 (b) 36 (b) 40 (b)
Exercis e 3 : Try If You Can
1 (b) 3 (b) 5 (b) 7 (d) 9 (a) 11 (b) 13 (c) 15 (b)
2 (a) 4 (a) 6 (d) 8 (b) 10 (c) 12 (b) 14 (a)
 11 Chapter
THE p-BLOCK ELEMENTS
(GROUP 13 AND 14)

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 7 Compounds of boron, silicates,
AIIMS 6 structural difference in 3.5/5 6.5
JEE Main 5 allotropes of carbon
BITSAT 5
 EBD_7374
136 CHEMISTRY
THE p-BLOCK ELEMENTS (GROUP 13 AND 14) 137
 EBD_7374
138 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Group 13 Elements: The Boron Family 11. AlCl3 on hydrolysis gives
(a) Al2O3. H2O (b) Al(OH)3
1. Which of the following is most abundant in the earth crust ? (c) Al2O3 (d) AlCl3.6H2O
(a) Boron (b) Aluminium 12. Which metal is protected by a layer of its own oxide?
(c) Gallium (d) Thallium (a) Al (b) Ag (c) Au (d) Fe
2. The relationship between first, second and third ionisation 13. Which of the following does not react with aqueous
enthalpies of each group-13 element is NaOH ?
(a) DiH1 > DiH2 > DiH3 (b) DiH1 < DiH2 < DiH3 (a) B (b) Al (c) Ga (d) Tl
(c) DiH1 = DiH2 > DiH3 (d) DiH3 > DiH1 > DiH2 14. Which of the following hydroxide is acidic ?
3. Which of the following is/are true regarding gallium? (a) Al(OH)3 (b) Ca(OH)3
(i) It has unusually low melting point (303 K). (c) Tl(OH)3 (d) B(OH)3
(ii) It exist in liquid state during summer. 15. Which among the following oxides react with alkali?
(iii) It has a high boiling point (2676 K). B2O3, Al2O3 and Tl2O
The correct option is (a) B2O3 and Al2O3 (b) Al2O3 and Tl2O
(a) (i) and (ii) (b) (i) and (iii) (c) Only B2O3 (d) B2O3 and Tl2O
(c) (i), (ii) and (iii) (d) (ii) and (iii) 16. What is x in the following reaction?
4. The element which shows least metallic character is Al(s) + NaOH (aq) + H2O (l) ® x + H2(g)
(a) Indium (b) Boron (a) Na2[Al(OH)4]– (b) Na+[Al(OH)4]–
(c) Aluminium (d) Gallium (c) Na2[Al(OH)6] – (d) Na+ [Al(OH)6]–
5. Which of the following does not form M3+ ion? 17. Assertion : Atomic radius of gallium is higher than that
(a) Boron (b) Aluminium of aluminium
(c) Indium (d) Gallium Reason : The presence of additional d-electron offer poor
6. Thallium shows different oxidation states because screening effect for the outer electrons from increased
(a) it is transition element nuclear charge.
(b) of inert pair effect (a) Assertion is correct, reason is correct; reason is a
(c) of its amphoteric character correct explanation for assertion.
(d) of its higher reactivity (b) Assertion is correct, reason is correct; reason is not a
7. Which out of the following compounds does not exist? correct explanation for assertion
(a) BF3 (b) TlCl3 (c) Assertion is correct, reason is incorrect
(c) TlCl5 (d) Both (b) and (c) (d) Assertion is incorrect, reason is correct.
8. Aluminium vessels should not be washed with materials
containing washing soda because Topic 2: Important Trends and Anomalous Properties of Boron
(a) washing soda is expensive 18. The strongest Lewis acid is
(b) washing soda is easily decomposed (a) BF3 (b) BCl3 (c) BBr3 (d) BI3
(c) washing soda reacts with aluminium to form soluble 19. NH3 and BF3 form an adduct readily because they form
aluminate (a) a coordinate bond (b) a hydrogen bond
(d) washing soda reacts with aluminium to form insoluble (c) an ionic bond (d) a covalent bond
aluminium oxide 20. The factor responsible for weak acidic nature of B–F bonds
9. Amphoteric oxide among the following is in BF3 is
(a) B2O3 (b) Ga2O3 (c) In2O3 (d) Tl2O3 (a) large electronegativity of fluorine
10. Which of the following statement(s) is/are incorrect ? (b) three centred two electron bonds in BF3
(i) Trichlorides on hydrolysis in water form tetrahedral (c) pp - dp back bonding
[M(OH)4]– species. (d) pp - pp back bonding
(ii) Hybridisation state of metal in tetrahedral species is 21. What is the oxidation state and hybridisation of boron in
sp3. compound formed when BCl3 undergoes reaction with the
(iii) Aluminium chloride in acidified aqueous solution water?
forms [Al(OH)4]– ion. (a) 3, sp2d (b) 3, sp3 (c) 4, sp3 (d) 3, sp2d
(a) (i) and (ii) (b) (ii) only 22. Which of the following statement(s) is/are incorrect ?
(c) (iii) only (d) (i) and (iii) (i) Higher boranes are not flammable.
THE p-BLOCK ELEMENTS (GROUP 13 AND 14) 139

(ii) Boranes are hydrolysed by water to give orthoboric 32. Match the columns
acid. Column-I Column-II
(iii) Boranes undergoes cleavage reactions with Lewis (A) Borax-bead (p) Alum
bases to give borane adducts. (B) Inorganic benzene (q) Diborane
(a) (i) only (b) (ii) and (iii) (C) Antiseptic (r) Metaborate
(c) (iii) only (d) (i) and (ii) (D) Bridged hydrogens (s) Borazole
(a) A – (p), B – (r), C – (q), D – (s)
Topic 3: Some Important Compounds of Boron (b) A – (r), B – (s), C – (p), D – (q)
23. In borax bead test which compound is formed? (c) A – (s), B – (r), C – (p), D – (q)
(a) Ortho-borate (b) Meta-borate (d) A – (q), B – (r), C – (s), D – (p)
(c) Double oxide (d) Tetra-borate 33. Which one of the following is the correct statement?
(a) Boric acid is a protonic acid
24. Orthoboric acid
(b) Beryllium exhibits coordination number of six
(a) donate proton to form H2BO3–
(c) Chlorides of both beryllium and aluminium have bridged
(b) accept proton of form H4BO3+
structures in solid phase
(c) donate OH– to form H2BO2+ (d) B2H6.2NH3 is known as ‘inorganic benzene’
(d) accept OH– to form [B(OH)4]– 34. Which of the following statements about H3BO3 is not
25. H3BO3 on heating up to 373 K yields: correct?
(a) boric anhydride (b) orthoboric acid (a) It is a strong tribasic acid
(c) metaboric acid (d) tetraboric acid (b) It is prepared by acidifying an aqueous solution of borax
26. Boric acid is polymeric due to (c) It has a layer structure in which planar BO3 units are
(a) its acidic nature joined by hydrogen bonds
(b) the presence of hydrogen bonds (d) It does not act as proton donor but acts as a Lewis acid
(c) its monobasic nature by accepting a lone pair of electrons
(d) its geometry 35. Identify the statement that is not correct as far as structure
27. Match Column-I (Compound of boron) with Column-II of diborane is concerned
(Use) and choose the correct option. (a) There are two bridging hydrogen atoms and four
Column-I Column-II terminal hydrogen atoms in diborane
(b) Each boron atom forms four bonds in diborane
(A) Metal borides (p) Flux for soldering metals
(c) The hydrogen atoms are not in the same plane in
(B) Boron fibres (q) Bullet-proof vest
diborane
(C) Borax (r) As a mild antiseptic
(d) All, B – H bonds in diborane are similar
(D) Boric acid (s) As control rods in 36. Which of the following structure is similar to graphite?
nuclear industry (a) B (b) B4C (c) B2H6 (d) BN
(a) A – (q), B – (s), C – (r), D – (p) 37. Orthoboric acid when heated to red hot gives
(b) A – (q), B – (s), C – (p), D – (r) (a) metaboric acid (b) pyroboric acid
(c) A – (s), B – (q), C – (r), D – (p) (c) boron and water (d) boric anhydride
(d) A – (s), B – (q), C – (p), D – (r) 38. Inorganic benzene is
28. In reaction (a) B3H3N3 (b) BH3NH3 (c) B3H6N3 (d) H3B3N6
BF3 + 3LiBH4 ® 3LiF + X ; X is 39. The structure of diborane (B2H6) contains
(a) B4H10 (b) B2H6 (c) BH3 (d) B3H8 (a) four 2c-2e– bonds and four 3c-2e– bonds
(b) two 2c-2e– bonds and two 3c-3e– bonds
29. In diborane
(c) two 2c-2e– bonds and four 3c-2e– bonds
(a) 4–bridged hydrogens and two terminal hydrogens are (d) four 2c-2e– bonds and two 3c-2e– bonds
present 40. Reaction of diborane with ammonia gives initially
(b) 2– bridged hydrogens and four terminal hydrogens (a) B2H6 .NH3 (b) Borazole
are present (c) B2H6 .3NH3 (d) [BH2(NH3)2]+[BH4]–
(c) 3–bridged and three terminal hydrogens are present 41. Select the correct statements for diborane :
(d) None of these (i) Boron is approximately sp3 hybridized
30. Diborane upon hydrolysis gives (ii) B – H – B angle is 180°
(a) boric anhydride (b) metaboric acid (iii) There are two terminal B – H bonds for each boron
(c) orthoboric acid (d) boron oxide atom
(iv) There are only 12 bonding electrons
31. The bonds present in borazole or inorganic benzene are
(a) (i), (ii) and (iv) (b) (i), (ii) and (iii)
(a) 9 s, 6p (b) 12 s, 3p (c) 6 s, 9p (d) 15 s only (c) (ii), (iii) and (iv) (d) (i), (iii) and (iv)
 EBD_7374
140 CHEMISTRY

42. Identify (i) to (v) in reactions (1) and (2) on the basis of (c) Assertion is correct, reason is incorrect
your identification choose the correct code for matching (d) Assertion is incorrect, reason is correct.
Column-I with Column-II.
D D Topic 5: Group 14 Elements : The Carbon Family
1. Na2B4O7.10H2O ¾¾
® (i) ¾¾
® (ii) + (iii)
50. Mark the oxide which is amphoteric in character
2. Na2B4O7.7H2O ¾¾ ® (iv) + (v)
(a) CO2 (b) SiO 2 (c) SnO2 (d) CaO
Column-I Column-II
(A) (i) (p) H3BO3 51. The inert pair effect is most prominent in
(B) (ii) (q) B2O3 (a) C (b) Pb (c) Ge (d) Si
(C) (iii) (r) NaBO2 52. The most stable +2 oxidation state is exhibited by
(D) (iv) (s) NaOH (a) Fe (b) Sn (c) Pb (d) Si
(E) (v) (t) Na2B4O7 53. The oxide of lead used in lead accumulators is
(a) A – (t), B – (s), C – (p), D – (q), E – (r) (a) PbO (b) Pb 2 O3 (c) Pb3O 4 (d) PbO 2
(b) A – (r), B – (q), C – (s), D – (p), E – (t) 54. Least thermally stable is
(c) A – (t), B – (r), C – (q), D – (p), E – (s) (a) CCl4 (b) SiCl4 (c) GeCl4 (d) GeBr4
(d) A – (t), B – (r), C – (s), D – (q), E – (p) 55. Which of the following halides is the most stable?
43. What is the colour obtained when borax is heated in a (a) CF4 (b) CI4 (c) CBr4 (d) CCl4
Bunsen burner flame with CoO? 56. Unlike the other elements of its group carbon and silicon
(a) Blue (b) Black (c) Green (d) Violet does not form MX2 type molecules because
44. The hybridisation of boron atom in orthoboric acid is (a) energetically this is not possible
(a) sp (b) sp2 (c) sp3 (d) sp3 d (b) carbon undergoes catenation
45. Which of the following reaction shows production of (c) it is non-metallic
diborane on industrial scale ? (d) carbon does not contain d-orbital
(a) 4BF3 + 3LiAlH4 ¾¾
® 2B2H6 + 3LiF + 3AlF3 57. Which of the following is/are not correctly matched ?
(i) GeO2 – Acidic (ii) PbO2– Amphoteric
(b) 2NaBH4 + I2 ¾¾
® B2H6 + 2NaI + H2 (iii) CO – Neutral (iv) SiO2 – Amphoteric
450K (a) (i) and (iv) (b) (iv) only
(c) 2BF3 + 6NaH ¾¾¾® B2H6 + 6NaF
(d) Both (b) and (c) (c) (ii) only (d) (iii) only
46. The product/s formed when diborane is hydrolysed is/are 58. The stability of dihalides of Si, Ge, Sn and Pb increases
(a) B2O3 and H3BO3 (b) B2O3 only steadily in the sequence
(c) H3BO3 and H2 (d) H3BO3 only (a) PbX 2 << SnX 2 << GeX 2 << SiX 2
(b) GeX2 << SiX2 << SnX2 << PbX2
Topic 4: Uses of Boron and Aluminium and Their Compounds (c) SiX2 << GeX2 << PbX2 << SnX2
(d) SiX2 << GeX2 << SnX2 << PbX2.
47. Which of the following properties of aluminium makes it 59. The reducing power of divalent species decreases in the
useful for food packaging ? order
(a) Good electrical conductivity (a) Ge > Sn > Pb (b) Sn > Ge > Pb
(b) Good thermal conductivity (c) Pb > Sn > Ge (d) None of these
(c) Low density 60. The elements commonly used for making transistors are
(d) Non toxicity (a) C and Si (b) Ga and In
48. BF3 is used as a catalyst in several industrial processes (c) P and As (d) Si and Ge
due to its 61. The element which is exclusively applied as semi-conductor
(a) strong reducing nature (a) Au (b) Ge (c) Pt (d) Si
(b) weak reducing action 62. Which of the following is not correct?
(c) strong Lewis acid nature (a) Ge(OH)2 is amphoteric
(d) weak Lewis acid character (b) GeCl2 is more stable than GeCl4
49. Assertion : The use of aluminium and its compounds for (c) GeO2 is weakly acidic
domestic purposes is now reduced considerably. (d) GeCl4 in HCl forms [ GeCl2]2– ion
Reason : The highly toxic nature of aluminium is the 63. The main reason that SiCl4 is easily hydrolysed as compared
responsible factor. to CCl4 is that
(a) Assertion is correct, reason is correct; reason is a (a) Si-Si bond is weaker
correct explanation for assertion. (b) SiCl4 can form hydrogen bonds
(b) Assertion is correct, reason is correct; reason is not a (c) SiCl4 is covalent
correct explanation for assertion (d) Si can extend its coordination number beyond four
THE p-BLOCK ELEMENTS (GROUP 13 AND 14) 141

64. Which halide is least stable and has doubtful existence Topic 6: Important Trends and Anomalous Behaviour of Carbon
(a) CI4 (b) GeI4 (c) SnI4 (d) PbI4
65. PbF4, PbCl4 exist but PbBr 4 and PbI4 do not exist because of 74. Carbon and silicon belong to group 14. The maximum
coordination number of carbon in commonly occurring
(a) large size of Br– and I–
compounds is 4, whereas that of silicon is 6. This is due to
(b) strong oxidising character of Pb4+
(a) large size of silicon
(c) strong reducing character of Pb4+
(b) more electropositive nature of silicon
(d) low electronegativity of Br – and I–. (c) availability of d-orbitals in silicon
66. Lead pipes are readily corroded by (d) Both (a) and (b)
(a) H2SO4 (b) HCl 75. The catenation tendency of C,Si and Ge is in the order
(c) CH3COOH (d) pure water Ge < Si < C.The bond energies (in kJ mol–1) of C-C,Si-Si and
67. Lead pipes are not suitable for drinking water because Ge-Ge bonds, respectively are
(a) lead forms basic lead carbonate (a) 167, 180, 348 (b) 180, 167, 348
(b) lead reacts with water containing air to form Pb(OH)2 (c) 348, 167, 180 (d) 348, 180, 167
(c) a layer of lead dioxide is deposited over pipes 76. The element that does not show catenation among the
(d) lead reacts with air to form litharge following p-block elements is
68. Which of the following species exists (A) [SiF 6] 2– , (a) carbon (b) silicon
(B) [GeCl6]2– and (C) [CCl6]2– ? (c) germanium (d) lead
(a) (A) and (B) (b) (B) and (C)
Topic 7: Allotropes of Carbon
(c) Only (C) (d) (A) and (C)
69. Ge(II)compounds are powerful reducing agents 77. Buckminster fullerene is
whereas Pb(IV)compounds are strong oxidants .It is because (a) pure graphite (b) C-60
(a) Pb is more electropositive than Ge (c) diamond (d) C-90
(b) ionization potential of lead is less than that of Ge 78. The hybridisation state of carbon in fullerene is
(c) ionic radii of Pb2+ and Pb4+ are larger than those of (a) sp (b) sp2 (c) sp3 (d) sp3d
Ge2+ and Ge4+ 79. In graphite, electrons are
(d) of more pronounced inert pair effect in lead than (a) localised on every third C-atom
in Ge (b) present in anti-bonding orbital
70. A group 14 element is oxidised to form corresponding oxide (c) localised on each C-atom
which is gaseous in nature, when dissolved in water pH of (d) spread out between the structure
80. The percentage of s-character of the hybrid orbitals of carbon
the water decreases further addition of group 2 hydroxides
in graphite and diamond are respectively
leads to precipitation. This oxide can be
(a) 33, 25 (b) 50, 50 (c) 67, 25 (d) 33, 67
(a) GeO2 (b) CO (c) CO2 (d) SnO2
81. Match columns
71. Which among the following can act as reducing agent
Column-I Column-II
(A)SnCl2, (B)CO and (C)PbCl2 ? (A) Graphite fibres (p) Abrasive for sharpening
(a) (A) and (B) (b) (B) and (C) hard tools
(c) (C) and (A) (d) Only (B) (B) Carbon black (q) Formation of light
72. Lead is not affected by dil. HCl in cold because weight composites.
(a) Pb is less electronegative than H (C) Charcoal (r) Used in water filters to
(b) PbO film is formed which resists chemical attack by remove organic
acid contaminators
(c) PbCl2 protective coating gets formed on Pb surface (D) Diamond (s) As filler in automobile
(d) PbO2 film is always present on Pb surface, which resist tyres
chemical attack (a) A – (s), B – (q), C – (r), D – (p)
73. Assertion : PbI4 of lead does not exist. (b) A – (q), B – (s), C – (r), D – (p)
Reason : Pb–I bond initially formed during the reaction (c) A – (q), B – (r), C – (s), D – (p)
does not release enough energy to unpair 6s2 electrons. (d) A – (p), B – (r), C – (s), D – (q)
(a) Assertion is correct, reason is correct; reason is a 82. Graphite is a soft solid lubricant extremely difficult to melt.
correct explanation for assertion. The reason for this anomalous behaviour is that graphite
(a) is an allotropic form of diamond
(b) Assertion is correct, reason is correct; reason is not a
(b) has molecules of variable molecular masses like polymers
correct explanation for assertion
(c) has carbon atoms arranged in large plates of rings of
(c) Assertion is correct, reason is incorrect
strongly bound carbon atoms with weak inter plate bonds
(d) Assertion is incorrect, reason is correct.
(d) is a non-crystalline substance
 EBD_7374
142 CHEMISTRY

83. What is the hybridisations of carbon atoms present in 93. CO2 is used for extinguishing fire because
diamond, graphite and fullerene respectively ? (a) it has a relatively high critical temperature
(a) sp3, sp2 and sp2 (b) sp2, sp3 and sp2 (b) in solid state, it is called dry ice
2 2
(c) sp , sp and sp 3 (d) sp3, sp3 and sp2 (c) it is neither combustible nor a supporter of combustion
84. Which one of the following allotropic forms of carbon is (d) it is a colourless gas
isomorphous with crystalline silicon? 94. The correct statement with respect to CO is
(a) Graphite (b) Coal (c) Coke (d) Diamond (a) it combines with H2O to give carbonic acid
85. Assertion : Graphite is thermodynamically most stable (b) it reacts with haemoglobin in RBC
allotrope of carbon. (c) it is powerful oxidising agent
Reason : D f H d- of graphite is taken as zero. (d) it is used to prepare aerated drinks
(a) Assertion is correct, reason is correct; reason is a 95. Which of the following statement(s) is / are incorrect for
correct explanation for assertion. CO2?
(b) Assertion is correct, reason is correct; reason is not a (i) In laboratory CO2 is prepared by the action of dilute
correct explanation for assertion HCl on calcium carbonate
(c) Assertion is correct, reason is incorrect (ii) Carbon dioxide is a poisonous gas
(d) Assertion is incorrect, reason is correct. (iii) Increase in carbon dioxide content in atmosphere
lead to increase in green house effect.
Topic 8: Some Important Compounds of Carbon and Silicon (iv) CO2 as dry ice is used as a refrigerant for ice cream
and frozen food.
86. Crystalline form of silica is called
(a) (i) and (ii) (b) Only (ii)
(a) crystalline silicon (b) quartz
(c) (i), (ii) and (iii) (d) (ii) and (iii)
(c) rock (d) talc
96. Which of the following is used in surgical and cosmetic
87. Glass reacts with HF to produce
plants?
(a) SiF4 (b) H2SiF6 (c) H2SiO3 (d) Na3AlF6
(a) Silicones (b) Silicates
88. Producer gas is the mixture of (c) Silica (d) None of these
(a) CO + N2 (b) CO + H2 97. Which type of zeolite is used to convert alcohols directly
(c) CO + water vapours (d) N2 + CH4 into gasoline ?
89. In silica (SiO2), each silicon atom is bonded to (a) ZSM – 3 (b) ZSM – 5
(a) two oxygen atoms (c) ZSM – 2 (d) All of these
(b) four oxygen atoms 98. Which one of the following statements about the zeolites is
(c) one silicon and two oxygen atoms false ?
(d) one silicon and three oxygen atoms (a) They are used as cation exchangers
90. R3SiCl on hydrolysis forms (b) They have open structure which enables them to take
(a) R3SiOH (b) R3Si – O – SiR3 up small molecules
(c) R2Si = O (d) None of these (c) Zeolites are aluminosilicates having three dimensional
91. Which of the following statements is false? network
(a) Water gas is a mixture of hydrogen and carbon monoxide (d) None of the above
(b) Producer gas is a mixture of CO and nitrogen 99. Coal gas is a mixture of
(c) Water gas is a mixture of water vapour and hydrogen (a) H2O and CO (b) H2, CO, N2 and CH4
(d) Natural gas consists of methane, ethane and gaseous (c) H2 and CO (d) CH4 and CO
hydrocarbons. 100. _____ helps to maintain pH of blood between 7.26 to 7.42
92. Which gas is essential constituent of almost all fuel gases? (a) CO2 (b) H2CO3
(a) CO2 (b) N2 (c) CO (d) H2O
(c) CO32 - (d) H2CO3/HCO3–
THE p-BLOCK ELEMENTS (GROUP 13 AND 14) 143

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs benzene. The compound X can be prepared by treating

BF3 with lithium aluminium hydride. The compounds X and
1. The elements which exists in liquid state for a wide range of
Y are represented by the formulas.
temperature and can be used for measuring high temperature is
(a) B2H6, B3N3H6 (b) B2O3, B3N3H6
(a) B (b) Al (c) Ga (d) In
(c) BF3, B3N3H6 (d) B3N3H6, B2H6
2. Which of the following is a Lewis acid?
12. Quartz is extensively used as a piezoelectric material, it
(a) AlCl3 (b) MgCl2 (c) CaCl2 (d) BaCl2
contains .............. .
3. The geometry of a complex species can be understood from
(a) Pb (b) Si (c) Ti (d) Sn
the knowledge of type of hybridisation of orbitals of central
13. The most commonly used reducing agent is
atom. The hybridisation of orbitals of central atom in
(a) AlCl3 (b) PbCl2 (c) SnCl4 (d) SnCl2
[B(OH4)]– and the geometry of the complex are respectively.
14. Dry ice is
(a) sp3, tetrahedral (b) sp3, square planar
(a) solid NH3 (b) solid SO2
(c) sp3d2, octahedral (d) dsp2, square planar
(c) solid CO2 (d) solid N2
4. Which of the following oxides is acidic in nature?
15. Cement, the important building material is a mixture of oxides
(a) B2O3 (b) Al2O3 (c) Ga2O3 (d) In2O3
of several elements. Besides calcium, iron and sulphur,
5. The exhibition of highest coordination number depends
oxides of elements of which of the group (s) are present in
on the availability of vacant orbitals in the central atom.
the mixture?
Which of the following elements is not likely to act as central
(a) Group 2 (b) Groups 2, 13 and 14
atom in MF63- ?
(c) Group 2 and 13 (d) Groups 2 and 14
(a) B (b) Al (c) Ga (d) In
6. Boric acid is an acid because its molecule Past Year MCQs
(a) contains replaceable H+ ion 16. Carborundum is obtained when silica is heated at high
(b) gives up a proton temperature with [AIIMS 2014, S]
(c) accepts OH– from water releasing proton
(a) carbon (b) carbon monoxide
(d) combines with proton from water molecule
(c) carbon dioxide (d) calcium carbonate
7. Catenation i.e., linking of similar atoms depends on size
17. Assertion : Pb4+ compounds are stronger oxidizing agents
and electronic configuration of atoms. The tendency of
than Sn4+ compounds.
catenation in group 14 elements follows the order
Reason : The higher oxidation states for the group 14
(a) C > Si > Ge > Sn (b) C > > Si > Ge » Sn
elements are more stable for the heavier members of the
(c) Si > C > Sn > Ge (d) Ge > Sn > Si > C
group due to ‘inert pair effect’. [AIIMS 2014, C]
8. Silicon has a strong tendency to form polymers like
(a) If both Assertion and Reason are correct and Reason
silicones. The chain length of silicone polymer can be
is the correct explanation of Assertion.
controlled by adding.
(b) If both Assertion and Reason are correct, but Reason
(a) MeSiCl3 (b) Me2SiCl2
is not the correct explanation of Assertion.
(c) Me3SiCl (d) Me4Si
(c) If Assertion is correct but Reason is incorrect.
9. Ionisation enthalpy (DiH kJ mol–1) for the elements of group (d) If both the Assertion and Reason are incorrect.
13 follows the order 18. The stability of +1 oxidation state among Al, Ga, In and Tl
(a) B > Al > Ga > In > Tl (b) B < Al < Ga < In < Tl increases in the sequence : [AIPMT 2015 RS, A]
(c) B < Al > Ga < In > Tl (d) B > Al < Ga > In < Tl (a) Ga < In < Al < Tl (b) Al < Ga < In < Tl
10. In the structure of diborane, (c) Tl < In < Ga < Al (d) In < Tl < Ga < Al
(a) All hydrogen atoms lie in one plane and boron atoms 19. Which of the following oxides is strongly basic?
lie in a plane perpendicular to this plane [AIIMS 2015, A]
(b) 2 boron atoms and 4 terminal hydrogen atoms lie in (a) B2O3 (b) Al2O3 (c) Ga2O3 (d) Tl2O3
the same plane and 2 bridging hydrogen atoms lie in 20. Chemically borax is [AIIMS 2015, S]
the perpendicular plane (a) Sodium metaborate
(c) 4 bridging hydrogen atoms and boron atoms lie in one (b) Sodium orthoborate
plane and two terminal hydrogen atoms lie in a plane (c) Sodium tetraborate
perpendicular to this plane (d) Sodium tetraborate decahydrate
(d) All the atoms are in the same plane 21. Which of the following is the most basic oxide?
11. A compound X, of boron reacts with NH3 on heating to [BITSAT 2015, A]
give another compound Y which is called inorganic (a) Sb2O3 (b) Bi2O3 (c) SeO2 (d) Al2O3
 EBD_7374
144 CHEMISTRY

22. Ordinary glass is : [BITSAT 2015, A] 29. Which one of the following elements is unable to form
(a) Sodium silicate MF63– ion? [NEET 2018, S]
(b) Calcium silicate
(c) Sodium and calcium silicate (a) Ga (b) Al (c) In (d) B
(d) Mixed salt of Na and Ca 30. In Alum : K2SO4.Al2(SO4)324H2O
23. The liquefied metal which expands on solidification is :
Which metal can replace Al? [AIIMS 2018, S]
[AIIMS 2016, S]
(a) Ga (b) Al (c) Zn (d) In (a) Cr (b) Mn (c) In (d) Sc
24. A neutral molecule XF3 has a zero dipole moment. The 31. Assertion : Both Be and Al can form complexes such as
element X is most likely [AIIMS 2016, S] BeF42– and AlF63– respectively. BeF63– is not formed.
(a) chlorine (b) boron (c) nitrogen (d) carbon Reason : In case of Be, no vacant d-orbitals are resent in its
25. Which of the following forms the base of talcum powder?
outermost shell. [AIIMS 2018, C]
(a) Zinc stearate [BITSAT 2016, A]
(b) Sodium aluminium silicate (a) If both Assertion and Reason are correct and Reason
(c) Magnesium hydrosilicate is the correct explanation of Assertion.
(d) Chalk (b) If both Assertion and Reason are correct, but Reason
26. It is because of inability of ns2 electrons of the valence shell is not the correct explanation of Assertion.
to participate in bonding that: [NEET 2017, A] (c) If Assertion is correct but Reason is incorrect.
(a) Sn2+ is oxidising while Pb4+ is reducing
(d) If both the Assertion and Reason are incorrect.
(b) Sn2+ and Pb2+ are both oxidising and reducing
(c) Sn4+ is reducing while Pb4+ is oxidising 32. Which of the following are Lewis acids? [JEE M 2018, A]
(d) Sn2+ is reducing while Pb4+ is oxidising (a) PH3 and BCl3 (b) AlCl3 and SiCl4
27. Assertion : Atomic radius of gallium is higher than that of (c) PH3 and SiCl4 (d) BCl3 and AlCl3
aluminium
33. When metal ‘M’ is treated with NaOH, a white gelatinous
Reason : The presence of additional d-electron offer poor
precipitate ‘X’ is obtained, which is soluble in excess of
screening effect for the outer electrons from increased
nuclear charge. [AIIMS 2017, A] NaOH. Compound ‘X’ when heated strongly gives an oxide
(a) If both Assertion and Reason are correct and Reason which is used in chromatography as an adsorbent. The metal
is the correct explanation of Assertion. ‘M’ is : [JEE M 2018, A]
(b) If both Assertion and Reason are correct, but Reason (a) Zn (b) Ca (c) Al (d) Fe
is not the correct explanation of Assertion. 34. An element X occurs in short period having configuration
(c) If Assertion is correct but Reason is incorrect. ns2 np1. The formula and nature of its oxide is
(d) If both the Assertion and Reason are incorrect.
[BITSAT 2018, S]
28. The correct order of atomic radii in group 13 elements is
[NEET 2018, A] (a) XO3, basic (b) XO3, acidic
(a) B < Al < In < Ga < Tl (b) B < Al < Ga < In < Tl (c) X2O3, amphoteric (d) X2O3, basic
(c) B < Ga < Al < In < Tl (d) B < Ga < Al < Tl < In

Exercise 3 : Try If You Can

1. Aqueous solution of borax acts as a buffer because 3. Borax is converted into crystalline boron by the following
(a) It contains tribasic acid and strong base. steps:
(b) It contains weak acid and its salt with strong base. X D Y
(c) It contains number of neutral water molecules. Borax ¾¾® H3BO3 ¾¾® B2O3 ¾¾® B
D
(d) None of the above. X and Y are respectively:
2. Anhydrous aluminium chloride (Al 2Cl 6) is covalent (a) HCl, Mg (b) HCl, C (c) C, Al (d) HCl, Al
compound and soluble in water giving:
4. The dissolution of Al(OH)3 by a solution of NaOH results
(a) Al3+ and Cl– ions
in the formation of:
(b) [Al(H2O)6]3+ and Cl– ions
(c) [AlCl2 (H2O)4]+ and [AlCl4 (H2O)2]– ions (a) [Al(H2O)4 (OH2)]+ (b) [Al(H2O)3 (OH)3]
(d) none of the above (c) [Al[H2O)2 (OH4)]– (d) [Al(H2O)6 (OH3)]
THE p-BLOCK ELEMENTS (GROUP 13 AND 14) 145

5. The straight chain polymer is formed by : 11. In the following reactions, the Pb compounds A and B are
(a) Hydrolysis of CH3SiCl 3 followed by condensation
respectively.
polymerisation.
(b) Hydrolysis of (CH 3 ) 4 Si followed by addition
polymerisation. HNO3
A
(c) Hydrolysis of (CH3)2SiCl2 followed by condensation
polymerisation. Pb3O4
(d) Hydrolysis of (CH3)3SiCl followed by condensation
polymerisation. B
HNO 3 + H 2O 2
6. Which of the following reaction does not take place?
(a) 2HgCl2 + Sn 2+ ® Hg 2Cl2 + Sn 4+ + 2Cl-
(a) Pb(NO3)2 + PbO2 and Pb(NO3)2
(b) 2Fe3+ + Sn 2 + ® Sn 4+ + 2Fe2 +
(b) Pb(NO3)2 and Pb(NO3)2
(c) 2Fe 2+ + Sn 2 + ® 2Fe3+ + Sn
(c) PbO2 and Pb(NO3)2
(d) Hg 2Cl 2 + Sn 2 + ® 2Hg + Sn 4+ + 2Cl-
(d) Pb(NO3)2 and PbO2 + Pb(NO3)2
7. (Si2O5 )2n–
n
anion is obtained when: 12. The water repelling characteristic of silicones is due to
(a) no oxygen of a SiO44- tetrahedron is shared with (a) the presence of alkyl group pointed towards surface
another SiO44- tetrahedron (b) strong Si–O–Si-bonds
(c) low surface area
(b) one oxygen of a SiO44- tetrahedron is shared with
(d) high van der Waal’s forces
another SiO44- tetrahedron 13. Diborane can be prepared by which of the following
4- methods?
(c) two oxygen of a SiO4 tetrahedron are shared with
(a) heating
4-
another SiO4 tetrahedron Mg 3 B2 + H 3 PO 4 ¾¾¾¾
®

(d) three oxygen of a SiO44- tetrahedron are shared with (b) BX 3 + LiAlH 4 ¾¾¾¾¾
ether
®
X = F, Cl, Br
another SiO44- tetrahedron 180 °C
8. The gas evolved on heating CaF2 and SiO2 with concentrated
(c) BF3 (g) + NaH ¾¾¾¾
®
H2SO4, on hydrolysis gives a white gelatinous precipitate. in diglyme
The precipitate is: (d) NaBH 4 + I 2 ¾¾ ¾ ¾ ¾ ®
solution
(a) hydrofluorosilicic acid (b) silica gel
(c) silicic acid (d) calcium fluorosilicate 14. Organosilicon compound can be prepared by which of the
9. On addition of excess of sodium hydroxide solution to following methods?
stannous chloride solution, we obtain :
(a) Mg 2Si + H 2SO 4 ®
(a) Sn(OH)2 (b) SnO2 .H2O
(c) Na2SnO2 (d) None of these (b) SiCl4 + Li(AlH4 ) ®
10. On controlled hydrolysis and condensation, R3SiCl yields (c) CH3SiCl3 + CH3MgCl ®
(a) R3Si – O – SiR3 (b) -(R3Si – O – SiR3)- n
Cu catalyst
R R (d) Si + CH3 Cl ¾¾¾¾¾
280 - 300°C
®
| |
– Si – O – Si – 15. Which of the following carbides consists of C34 - type of
| | anionic part?
(c) R3SiOH (d) O O
| | (a) Al4C3 (b) CaC2 (c) B4C (d) Mg2C3
– Si – O – Si –
| |
R R
 EBD_7374
146 CHEMISTRY

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 11 (b) 21 (b) 31 (b) 41 (d) 51 (b) 61 (b) 71 (a) 81 (b) 91 (a)
2 (b) 12 (a) 22 (a) 32 (b) 42 (c) 52 (c) 62 (b) 72 (c) 82 (c) 92 (c)
3 (c) 13 (a) 23 (b) 33 (c) 43 (a) 53 (d) 63 (d) 73 (a) 83 (a) 93 (c)
4 (b) 14 (d) 24 (d) 34 (a) 44 (b) 54 (d) 64 (d) 74 (c) 84 (d) 94 (b)
5 (a) 15 (a) 25 (c) 35 (d) 45 (c) 55 (a) 65 (b) 75 (d) 85 (a) 95 (b)
6 (b) 16 (b) 26 (b) 36 (d) 46 (c) 56 (a) 66 (c) 76 (d) 86 (b) 96 (a)
7 (c) 17 (c) 27 (d) 37 (b) 47 (c) 57 (b) 67 (b) 77 (b) 87 (b) 97 (b)
8 (c) 18 (d) 28 (b) 38 (c) 48 (d) 58 (d) 68 (a) 78 (b) 88 (a) 98 (d)
9 (b) 19 (a) 29 (b) 39 (d) 49 (a) 59 (a) 69 (d) 79 (d) 89 (b) 99 (b)
10 (c) 20 (d) 30 (c) 40 (d) 50 (c) 60 (d) 70 (c) 80 (a) 90 (b) 100 (d)
Exercise 2 : Exemplar & Past Year MCQs
1 (c) 5 (a) 9 (d) 13 (d) 17 (c) 21 (b) 25 (c) 29 (d) 33 (c)
2 (a) 6 (c) 10 (b) 14 (c) 18 (b) 22 (c) 26 (d) 30 (a) 34 (c)
3 (a) 7 (b) 11 (a) 15 (b) 19 (d) 23 (a) 27 (c) 31 (a)
4 (a) 8 (c) 12 (b) 16 (a) 20 (d) 24 (b) 28 (c) 32 (d)
Exercise 3 : Try If You Can
1 (b) 3 (d) 5 (c) 7 (d) 9 (c) 11 (d) 13 (a, b, c, d) 15 (d)
2 (c) 4 (c) 6 (c) 8 (d) 10 (a) 12 (a) 14 (c, d)
 12 Chapter
ORGANIC CHEMISTRY–SOME
BASIC PRINCIPLES & TECHNIQUES

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 3 Reaction Mechanism,
AIIMS 3 IUPAC Nomenclature, 4/5 8.2
JEE Main 3 Isomerism
BITSAT 2
 EBD_7374
148 CHEMISTRY
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 149
 EBD_7374
150 CHEMISTRY

Exercise 1 : Topic-wise MCQs

(a) A – (r), B – (p), C – (s), D – (q)

Topic 1: Tetravalence of Carbon: Shapes of Organic Compounds
(b) A – (s), B – (p), C – (q), D – (r)
1. Which of the following statement(s) is/are correct ? (c) A – (p), B – (r), C – (s), D – (q)
(i) A carbon atom having an sp hybrid orbital is less (d) A – (r), B – (p), C – (q), D – (s)
electronegative than carbon atoms possessing sp2 or 7. Which of the following compounds contains 1°, 2°, 3° as
sp3 hybridised orbitals. well as 4° carbon atoms ?
(ii) p-bonds provide the most reactive centres in the (a) Neopentane (b) 2-methyl pentane
molecules containing multiple bonds (c) 2,3-dimethyl butane (d) 2,2,3-trimethyl pentane
(iii) The number of s and p bonds in compound 8. The compound which has one isopropyl group is
CH2= C= CHCH3 are 7 and 2 respectively. (a) 2, 2, 3, 3 - Tetramethylpentane
(a) (i) and (iii) (b) (ii) and (iii) (b) 2, 2 - Dimethylpentane
(c) (ii) only (d) (i) only (c) 2, 2, 3- Trimethylpentane
2. The state of hybridization of C2, C3, C5 and C6 of the (d) 2- Methypentane
hydrocarbon, 9. Assertion : The general formula for a dihydric alcohol is
CH3 CH3
| | CnH2n(OH)2
CH3 C CH = CH CH C º CH Reason : Ethylene glycol is a dihydric alcohol.
7 6| 5 4 3 2 1 (a) Assertion is correct, reason is correct; reason is a
CH3 correct explanation for assertion.
is in the following sequence (b) Assertion is correct, reason is correct; reason is not a
(a) sp3, sp2, sp2 and sp (b) sp, sp2, sp2 and sp3 correct explanation for assertion
2 3 2 (c) Assertion is correct, reason is incorrect
(c) sp, sp , sp and sp (d) sp, sp3, sp2 and sp3
(d) Assertion is incorrect, reason is correct.
x
3. The compound in which C uses its sp3 - hybrid orbitals for Topic 3: Nomenclature of Organic Compounds
bond formation is
X X 10. Which of the following compounds has wrong IUPAC
(a) HCOOH (b) (H 2 N)2CO name?
X X (a) CH3–CH2–CH2 –COO–CH2CH3 ® ethyl butanoate
(c) (CH3 )3COH (d) CH 3 C HO
(b) CH3 - CH - CH 2 - CHO ® 3-methyl-butanal
Topic 2: Structural Representation of Organic Compounds |
4. 2- Pentene contains CH3
(a) 15 s- and one p- bond (b) 14 s-and one p- bond (c) CH3 - CH - CH - CH ® 2-methyl-3-butanol
3
(c) 15 s- and two p- bonds (d) 14 s- and two p- bonds | |
5. The correct decreasing order of priority of functional OH CH 3
groups is O
(a) – SO3H , – OH, – COCl, C = C ||
(d) CH3 - CH - C - CH 2 - CH3 ® 2-methyl-3-pentanone
(b) – COOH, – SO3H, – COOR, – OH |
(c) – C º C, – NH2, – OH, C = O CH3
(d) – CN, – CONH2, C = O, – OH 11. IUPAC name of following compound is :
6. Match the columns H
Column-I Column-II
CH3 - C - CH2 - CH3
(A) Non–benzenoid compound (p)
O
(B) Alicyclic compound (q) (a) 2 - cyclohexylbutane (b) 2 - phenylbutane
(c) 3 - cyclohexylbutane (d) 3 - phenylbutane
(C) Benzenoid compound (r)
12. What is the IUPAC name of the following compound ?
S
(D) Heterocyclic aromatic NH 2

compound (s)
(a) 2-methyl-4-hexanamine (b) 5-methyl-3-hexanamine
O (c) 2-methyl-4-amino hexane (d) 5-methyl-3-amino hexane
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 151

13. Which one of the following is ethyl-4-(dimethyl amino) 20. The IUPAC name for
butanoate ? Cl
NO2

(a) (MeNH) 2 OEt

CH3
(a) 1-Chloro-2-nitro-4-methyl benzene
(b)
OEt (b) 1-Chloro-4-methyl-2-nitrobenzene
NH 2 (c) 2-Chloro-1-nitro-5-methyl benzene
(d) m-Nitro-p-chlorotoluene
21. What is the IUPAC name of the following compound ?
(c) H2N COOH
OEt
Br

(d) Me 2 N
OEt
14. Identify the correct IUPAC name of the compound given
below CH 2 CH 3
(a) 6 – bromo – 4 – ethylbenzene carboxylic acid
(b) 2 – bromo – 4 – ethylbenzene carboxylic acid
(c) Ortho – bromo – paraethyl benzoic acid
H (d) 4 – bromo – 3 – ethyl benzoic acid
22. Match Column-I (organic compound) with Column-II
(common name of the compound) and choose the correct
option.
(a) 4 – benzyl – 5 – methyl hexanal Column-I Column-II
(b) 2 – methyl – 3 – phenyl hexanal (Organic compound) (Common name of
(c) 5 – isopropyl – 5 – phenyl butanal compound)
(d) 5 – methyl – 4 – phenyl hexanal (A) C6H5OCH3 (p) Neopentane
15. IUPAC name of (CH3)3 CCl is (B) H3CCH2CH2 OH (q) Anisole
(a) 1-butyl chloride (C) (H3C)4C (r) Acetophenone
(b) 3-chloro butane (D) C6H5COCH3 (s) n–Propyl alcohol.
(c) 2-chloro-2-methylpropane (a) A – (r), B – (s), C – (p), D – (q)
(d) 2-butyl chloride (b) A – (r), B – (p), C – (s), D – (q)
16. IUPAC name of the following compound (c) A – (q), B – (s), C – (p), D – (r)
(d) A – (q), B – (s), C – (r), D – (p)
O 23. Assertion : IUPAC name of the following organic
CH3 compound is 3, 4, 7 – trimethyloctane
C N
CH3 CH3 - CH - CH 2 - CH 2 - CH - CH - CH 2 - CH3
(a) N, N-dimethylcyclopropane carboxamide | | |
(b) N-methylcyclopropanamide' CH3 CH3 CH3
(c) cyclopropionamide Reason : The numbering is done in such a way that the
(d) None of these branched carbon atoms get the lowest possible numbers.
17. Which of the following is a 3-methylbutyl group? (a) Assertion is correct, reason is correct; reason is a
(a) CH3CH2CH2CH2CH2– correct explanation for assertion.
(b) (CH3CH2)2CH– (b) Assertion is correct, reason is correct; reason is not a
(c) (CH3)3CCH2– correct explanation for assertion
(d) (CH3)2CHCH2CH2– (c) Assertion is correct, reason is incorrect
18. The IUPAC name of the compound (d) Assertion is incorrect, reason is correct.
CH3 — CH(CH3) — CO – CH3, is 24. The IUPAC name of the following compound is
(a) 3-methyl 2-butanone N
(b) 2-methyl 3-butanone
(c) isopropyl methyl ketone H O
(d) methyl isopropyl ketone (a) N – phenyl ethanamide
19. The IUPAC name of neopentane is (b) N – phenyl ethanone
(a) 2, 2-dimethylpropane (b) 2-methylpropane (c) N – phenyl methanamide
(c) 2, 2-dimethylbutane (d) 2-methylbutane (d) None of these
 EBD_7374
152 CHEMISTRY

OH 35. The compounds CH3CH == CHCH3 and

CH3CH2CH == CH2
25. IUPAC name of is : (a) are tautomers
(b) are position isomers
OH (c) contain same number of sp3– sp3, sp3– sp2 and sp2– sp2
(a) But – 2 ene – 2, 3– diol carbon-carbon bonds
(b) Pent – 2 –ene – 2, 3 – diol (d) exist together in dynamic equilibrium
(c) 2 – methylbut – 2 – ene – 2, 3 – diol 36. Match the columns
(d) Hex – 2 – ene – 2, 3 – diol Column-I Column-II
O (A) CH3COOH & (p) Functional isomers
HCOOCH3
CH2– C – OH (B) 1 butene & (q) Metamers 2-butene
OH (C) diethyl ether & (r) Position isomers
26. The IUPAC name of compound C is:
COOH methyl propyl ether
(D) dimethyl ether (s) Chain isomers and
CH2– COOH
and ethanol ethanol
(a) 1, 2, 3 - tricarboxy - 2, 1 - propane
(a) A – (p), B – (r), C – (q), D – (p)
(b) 3 - carboxy - 3 hydroxy - 1 , 5 - pentanedioic acid (b) A – (q), B – (r), C – (s), D – (p)
(c) 3 - hydroxy - 3 - carboxy - 1, 5 - pentanedioic acid (c) A – (q), B – (s), C – (p), D – (r)
(d) 2 - hydroxy propane -1, 2, 3 - tricarboxylic acid. (d) A – (q), B – (p), C – (s), D – (r)
Topic 4: Isomerism 37. Assertion : Chain isomerism is observed in compounds
containining four or more than four carbon atoms
27. Which organic structure among the following is not an
Reason : Only alkanes show chain isomerism
isomer of the compound
(a) Assertion is correct, reason is correct; reason is a
CH3–CO–CH2CH2CH2CH3 ?
correct explanation for assertion.
(a) CH3CH2OCH =CHCH2CH3
(b) Assertion is correct, reason is correct; reason is not a
(b) CH3CH = CHCH2CH2CHO correct explanation for assertion
(c) (CH3)2CH–CO–CH2CH3 (c) Assertion is correct, reason is incorrect
(d) CH3CH2COCH2CH2CH3 (d) Assertion is incorrect, reason is correct.
28. Which of the following compounds is isomeric with 2, 2, 4, 38. The number of possible open chain (acyclic) isomeric
4- tetramethylhexane? compounds for molecular formula C5H10 would be
(a) 3-ethyl -2, 2- dimethylpentane (a) 8 (b) 7 (c) 6 (d) 5
(b) 4-isopropylheptane 39. Which of the following compounds will show metamerism?
(c) 4-ethyl-3-methyl-4-n-propyloctane (a) CH3 – CO – C2H5 (b) C2H5 – S – C2H5
(d) 4, 4-diethyl-3-methylheptane (c) CH3 – O – CH3 (d) CH3 – O – C2H5
29. Which are isomers ? 40. The compound C4H10O can show
(a) ethyl alcohol and dimethyl ether (a) metamerism (b) functional isomerism
(b) acetone and acetaldehyde (c) position isomerism (d) All of these
(c) propionic acid and propanone 41. Which pair of isomerism is not possible together?
(d) methyl alcohol and dimethyl ether (a) Ring-chain and functional
30. Methoxyethane and propanol are the examples of isomerism (b) Geometrical and optical
of the type (c) Metamerism and functional
(a) structural (b) position (d) Metamerism and chain
(c) functional (d) tautomerism
31. Isomers of propionic acid are Topic 5: Fundamental Concepts in Organic Reaction Mechanism
(a) HCOOC2H5 and CH3COOCH3 42. Which of the following statements is not correct ?
(b) HCOOC2H5 and C3H7COOH (a) Carbocation posses sextet of electrons.
(c) CH3COOCH3 and C3H7OH (b) The order of carbocation stability is :
(d) C3H7OH and CH3COCH3 + + +
32. C6H5C º N and C6H5N ® < C are which type of isomers? CH3 > (CH3 )2 CH > (CH3 )3 C
(a) Position (b) Functional (c) Carbocations have trigonal planar shape
(c) Tautomerism (d) Linkage (d) Carbocations are formed by heterolytic cleavage
33. A functional isomer of 1-butyne is 43. Which of the following ions is most stable ?
(a) 2-butyne (b) 1-butene + +
(c) 2-butene (d) 1, 3-butadiene (a) CH - C - CH (b) CH 3 CH 2 CH 2
3 3
34. In which of the following, functional group isomerism is not |
possible? CH 3
(a) Alcohols (b) Aldehydes +
(c) CH 3CHCH 2 CH 3 (d) None of these
(c) Alkyl halides (d) Cyanides
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 153

44. The order of stability of the following carbocations : (a) sp3-hybridised (b) sp2-hybridised
(c) sp-hybridised (d) sp2d-hybridised
Å
CH 2 52. In which of the following homolytic bond fission takes place ?
(a) Alkaline hydrolysis of ethyl chloride
Å Å (b) Addition of HBr to double bond
CH 2 = CH - C H 2 ; CH3 - CH 2 - CH 2 ; is : (c) Photochlorination of methane
I II (d) Nitration of benzene
III 53. The increasing order of stability of the following free radicals
(a) III > II > I (b) II > III > I is
(c) I > II > III (d) III > I > II • • • •
45. Select the most stable carbocation amongst the following (a) (C6H5)2 C H < (C6H5)3 C < (CH3)3 C < (CH3)2 C H
• • • •
+ (b) (CH3)2 C H < (CH3)3 C < (C6H5)2 C H < (C6H5)3C
(a) • • • •
(c) (CH3)3 C < (CH3)2 C H < (C6H5)2 C H < (C6H5)3 C
• • • •
(b) (d) (C6H5)3C < (C6H5)2 C H < (CH3)3 C < (CH3)2 C H
+
54. Which of the following orders regarding relative stability of
free radicals is correct?
(a) 3° < 2° < 1° (b) 3° > 2° > 1°
(c) +
(c) 1° < 2° > 3° (d) 3° > 2° < 1°
55. The most stable free radical among the following is
· ·
(a) C6 H5 CH 2CH 2 (b) C6 H 5 CHCH 3
(d) + · ·
(c) CH 3CH 2 (d) CH 3 CHCH 3
46. What is the correct order of decreasing stability of the 56. The least stable free radical is
following cations?
(a) CH3 CH& (b) CH3CH2 CH &
2 2
Å
(c) (CH3)2 CH& &
(d) CH 3
I. CH3 — CH— CH3
57. Which of the following is strongest nucleophile
Å (a) Br– (b) : OH–
II. CH3 — CH— OCH 3 (c) : CN
-
(d) C2 H 5O :
Å 58. Which of the following represents a set of nucleophiles?
III. CH3 — CH— CH 2 — OCH3 (a) BF3, H2O, NH2– (b) AlCl3, BF3, NH3
(a) II > I > III (b) II > III > I (c) CN–, RCH2–, ROH (d) All of these
(c) III > I > II (d) I > II > III 59. Which of the following species does not act as a
47. The most stable carbocation among the following is nucleophile?
(a) ROH (b) ROR (c) PCl3 (d) BF3
+ +
(a) C6 H5 CHC6 H5 (b) C6 H5CH 2 60. Which of the following pairs represent electrophiles?
(a) AlCl3, H2O (b) SO3, NO2+
+ + (c) BF3, H2O (d) NH3, SO3
(c) CH3 CH 2 (d) C6 H5CH 2CH 2
61. Which out of A, B, C and D is/are not correctly
48. The organic reactions which proceed through heterolytic categorised.
bond cleavage called ________
(a) ionic (b) polar Nucleophile Electrophile
(c) nonpolar (d) Both (a) and (b) A. HS- Cl+
49. The shape of methyl carbanion is similar to that of –
B. BF3 (CH3 )3N
(a) BF3 (b) NH3
(c) methyl free radical (d) methyl carbocation +
C. H 2 N - -C = O
50. Arrange the carbanions,
(CH3 )3 C , C Cl3 , (CH3 ) 2 CH , C6 H5 CH 2 D. R 3C - X C2 H 5 O -
in order of their decreasing stability : (X = H alogen)
(a) (CH3 )2 C H > C Cl3 > C6 H5 C H 2 > (CH3 )3 C (a) B, C and D (b) C and D
(c) C only (d) B and D
(b) C Cl3 > C6 H5 CH 2 > (CH3 )2 CH > (CH3 )3 C 62. Arrangement of (CH3)3 – C –, (CH3)2 – CH –, CH3 – CH2 –
when attached to benzyl or an unsaturated group in
(c) (CH3 )3 C > (CH3 )2 CH > C6 H5 CH 2 > CCl3
increasing order of inductive effect is
(d) C6 H5 CH 2 > CCl3 > (CH3 )3 C > (CH3 )2 CH (a) (CH3)3 –C – < (CH3)2 – CH – < CH3 – CH2–
51. Homolytic fission of C–C bond in ethane gives an (b) CH3 –CH2– < (CH3)2– CH – < (CH3)3 –C –
intermediate in which carbon is (c) (CH3)2 – CH– < (CH3)3 –C – < CH3—CH2–
(d) (CH3)3 – C– < CH3 –CH2 – < (CH3)2 –CH –
 EBD_7374
154 CHEMISTRY

63. Polarization of electrons in acrolein may be written as 71. Hyperconjugation is most useful for stabilizing which of
d- d+ d- d+ the following carbocations ?
(a) CH 2 = CH - CH = O (b) CH 2 = CH - CH = O
d+
(a) neo-Pentyl (b) tert-Butyl
d- d- d-
(c) CH 2 = CH - CH = O (d) CH 2 = CH - CH = O (c) iso-Propyl (d) Ethyl
64. Point out the incorrect statement about resonance? 72. Which of the following is an example of elimination reaction?
(a) Resonance structures should have equal energy (a) Chlorination of methane
(b) In resonating structures, the constituent atoms must (b) Dehydration of ethanol
be in the same position (c) Nitration of benzene
(c) In resonating structures, there should not be same (d) Hydroxylation of ethylene
number of electron pairs 73. CH3 – Br + NH3 ® CH 3 – NH 2 + HBr
(d) Resonating structures should differ only in the location The above reaction is classified as
of electrons around the constituent atoms (a) substitution (b) addition
65. In which of the following, resonance will be possible? (c) elimination (d) rearrangement
(a) CH3 - CH 2 - CH 2 - CHO 74. Which of the following is/are correct for inductive effect ?
(b) CH 2 = CH - CH = O (i) In inductive effect polarisation of sigma bond is
(c) CH 3COCH 3 caused by the adjacent s bond.
(d) CH 2 = CH - CH 2 - CH = CH 2 (ii) Halogens, – NO2 , – CN, and – CH3 are electron
66. Assertion : Aniline is better nucleophile than anilium ion. withdrawing groups.
Reason : Anilium ion has +ve charge. (iii) –CH2CH3and –OC6H5 are electron donating groups.
(a) Assertion is correct, reason is correct; reason is a (a) (i) only (b) (ii) only
correct explanation for assertion. (c) (i) and (iii) (d) (i), (ii) and (iii)
(b) Assertion is correct, reason is correct; reason is not a 75. Which of the following statements regarding the resonance
correct explanation for assertion energy of benzene is correct?
(c) Assertion is correct, reason is incorrect (a) Resonance energy is the energy required to break the
(d) Assertion is incorrect, reason is correct. C–H bond in benzene
67. Which of the following is not correctly matched ? (b) Resonance energy is the energy required to break the
Group showing + R effect Group showing – R effect C–C bond in benzene
(a) – NHCOR – COOH (c) Resonance energy is a measure of stability of benzene
(d) Resonance energy is the energy required to convert
(b) C=O – OH
(c) – OR – CHO
(d) – OCOR – NO2
68. Assertion : Energy of resonance hybrid is equal to the
average of energies of all canonical forms. 76. Assertion : Different number of electron pairs are present in
Reason : Resonance hybrid cannot be presented by a single resonance structures.
structure. Reason : Resonance structures differ in the location of
(a) Assertion is correct, reason is correct; reason is a electrons around the constituent atoms.
correct explanation for assertion. (a) Assertion is correct, reason is correct; reason is a
(b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion.
correct explanation for assertion (b) Assertion is correct, reason is correct; reason is not a
(c) Assertion is correct, reason is incorrect correct explanation for assertion
(d) Assertion is incorrect, reason is correct. (c) Assertion is correct, reason is incorrect
69. The kind of delocalization involving sigma bond orbitals is (d) Assertion is incorrect, reason is correct.
called 77. The polarity is produced in the molecule by the interaction
(a) inductive effect (b) hyperconjugation effect of two p – bonds or between a p – bond and lone pair of
(c) electromeric effect (d) mesomeric effect electrons present on an adjacent atom.
70. Choose the correct order of stability of carbocation using The above statement is true for which of the following ?
concept of hyperconjugation. (a) Inductive effect (b) Electromeric effect
(c) Resonance effect (d) Hyperconjugation
CH3 CH3 78. Which of the following represents the correct order of
|Å |Å Å Å stability of the given carbocations ?
CH3 - C CH3 - C CH3 CH 2 CH 3 + |+ + + |+ +
| | (a) F3C > F3C - C > CH3 (b) H3C > F3C - C > F3C
CH3 H | |
I II III IV |+
|+ + + + +
(a) I < II < III < IV (b) IV < III < II < I (c) F3C - C > F3C > H3C (d) F3C - C > H3C > F3C
| |
(c) III < IV < II < I (d) None of these
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 155

79. The most stable carbanion among the following is

Topic 6: Methods of Purification of Organic Compounds
CH – CH –
2 2 CH – 2 85. The best method for the separation of naphthalene and
benzoic acid from their mixture is:
(a) (b) (a) distillation (b) sublimation
(c) chromatography (d) crystallisation
86. In steam distillation the vapour pressure of volatile organic
CH2– CH2– compound is
(a) equal to atmospheric pressure
(b) double the atmospheric pressure
(c) (d) (c) less than atmospheric pressure
(d) more than atmospheric pressure
87. Fractional distillation is used when
OCH3 NO2 (a) there is a large difference in the boiling point of liquids
(b) there is a small difference in the boiling points of
80. Which one of the following is a free-radical substitution
liquids
reaction?
(c) boiling points of liquids are same
(a) CH 3CHO + HCN ¾
¾® CH 3CH ( OH ) CN (d) liquids form a constant boiling mixture
88. Purification of petroleum is carried out by
CH3 CH2Cl (a) fractional distillation (b) steam distillation
(b) +Cl2
Boiling
(c) vacuum distillation (d) simple distillation
89. Distillation under reduced pressure is employed for
CH3 (a) C6H6
Anh. AlCl3
(c) +CH3Cl (b) petrol
(c) CH2OHCHOHCH2OH
(d) organic compounds used in medicine
CH2Cl CH2NO2
90. Glycerol can be separated from spent lye in soap industry
(d) + AgNO2
by which of the following method ?
(a) Steam distillation
81. Rate of the reaction
(b) Fractional distillation
O O – (c) Distillation under reduced pressure
R – C + Nu R – C + Z is fastest when Z is (d) Differential extraction
Z Nu
91. The latest technique for the purification of organic
-
(a) OC2 H5 (b) NH 2 (c) Cl– (d) OCOCH3 compounds is
82. For (i) I–, (ii) Cl– , (iii) Br – , the increasing order of (a) chromatography (b) fractional distillation
nucleophilicity would be (c) crystallization (d) vacuum distillation
(a) Cl– < Br– < I– (b) I– < Cl– < Br– 92. Which of the following is used as an adsorbent in
– –
(c) Br < Cl < I – (d) I– < Br– < Cl– adsorption chromatography ?
83. Which of the following is least reactive in a nucleophilic (a) Silica gel (b) Alumina
substitution reaction. (c) Zeolite (d) Both (a) and (b)
(a) (CH 3 )3 C - Cl (b) CH 2 = CHCl 93. Which of the following acts as the stationary phase in
paper chromatography ?
(c) CH 3CH 2Cl (d) CH 2 = CHCH 2 Cl (a) Water (b) Alumina
84. Which of the following does not represent formation of (c) Silica gel (d) None of these
reactive intermediate correctly ? 94. The most satisfactory method to separate mixture of sugars
+ is
-
(i) CH3 - CN ® C H3 + CN (a) fractional crystallisation
(b) sublimation
- + (c) chromatography
(ii) CH 3 - Cu ® CH3 + Cu
(d) benedict reagent
+ 95. Chromatography is a valuable method for the separation,
(iii) CH 3 - Br ® CH3 + Br - isolation, purification and identification of the constituents
of a mixture and it is based on general principle of
+
(iv) CH 3 - Cl ® CH3 + Cl- (a) phase rule (b) phase distribution
(a) (ii) only (b) (ii) and (iii) (c) interphase separation (d) phase operation
(c) (ii) and (iv) (d) (iii) and (iv) 96. In paper chromatography
(a) moving phase is liquid and stationary phase in solid
(b) moving phase is liquid and stationary phase is liquid
 EBD_7374
156 CHEMISTRY

(c) moving phase is solid and stationary phase is solid 104. Match the columns
(d) moving phase is solid and stationary phase is liquid Column - I Column - II
97. Which of the following statements are correct for (Elements) (Colour of precipitate
fractional distillation ? formed in Lassaigne’s test)
(i) Fractional distillation method is used if the two (A) Nitrogen (p) Yellow
liquids have sufficiently large difference in their (B) Sulphur (q) Prussian blue
boiling points. (C) Chlorine (r) Voilet
(ii) A fractionating column provides many surfaces for (D) Phosphorus (s) White
heat exchange between the ascending vapours and (a) A – (q), B – (r), C – (p), D – (s)
the descending condensed liquid. (b) A – (r), B – (q), C – (p), D – (s)
(iii) Each successive condensation and vaporisation unit (c) A – (q), B – (r), C – (s), D – (p)
in the fractionating column is called a theoretical plate. (d) A – (r), B – (q), C – (s), D – (p)
(iv) Fractional distillation method is used to separate 105. In Lassaigne’s test, the organic compound is fused with a
different fractions of crude oil in petroleum industry. piece of sodium metal in order to
(a) (i), (ii) and (iv) (b) (ii), (iii) and (iv) (a) increase the ionisation of the compound
(c) (i), (ii) and (iii) (d) (i), (ii), (iii) and (iv) (b) decrease the melting point of the compound
98. Assertion : Simple distillation can help in separating a (c) increase the reactivity of the compound
mixture of propan-1-ol (boiling point 97°C) and propanone
(d) convert the covalent compound into a mixture of ionic
(boiling point 56°C).
compounds
Reason : Liquids with a difference of more thatn 20°C in
106. The Lassaigne’s extract is boiled with dil. HNO3 before
their boiling points can be separated by simple distillation.
testing for halogens because
(a) Assertion is correct, reason is correct; reason is a
(a) silver halides are soluble in HNO3
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a (b) Na2S and NaCN are decomposed by HNO3
correct explanation for assertion (c) Ag2S is soluble in HNO3
(c) Assertion is correct, reason is incorrect (d) AgCN is soluble is HNO3
(d) Assertion is incorrect, reason is correct. 107. In quantitative analysis of carbon and hydrogen, the
99. Assertion : Components of a mixture of red and blue inks mass of water produced is determined by passing the
can be separated by distributing the components between mixture through a weighed U – tube containing ___X___
stationary and mobile phases in paper chromatography. and carbon dioxide is absorbed in concentrated solution
Reason : The coloured components of inks migrate at of ___Y___
different rates because paper selectively retains different (a) X = CaCl2 , Y = NaOH
components according to the difference in their partition (b) X = Ca(OH)2 , Y = CuSO4
between the two phases. (c) X = CuSO4 , Y = Ca(OH)2
(a) Assertion is correct, reason is correct; reason is a (d) X = CaCl2 , Y = KOH
correct explanation for assertion. 108. Kjeldahl method is not applicable to which of the
(b) Assertion is correct, reason is correct; reason is not a following ?
correct explanation for assertion (a) Nitro compounds (b) Azo compounds
(c) Assertion is correct, reason is incorrect (c) Pyridine (d) All of these.
(d) Assertion is incorrect, reason is correct. 109. Duma's method involves the determination of nitrogen
100. The most suitable method for separtion of a 1 : 1 mixture of ortho content in the organic compound in form of
and para nitrophenols is (a) NH3 (b) N2
(a) Sublimation (b) Chromatography (c) NaCN (d) (NH4)2SO4
(c) Crystallization (d) Steam distillation 110. In Kjeldahl’s method nitrogen present is estimated as
Topic 7: Qualitative and Quantitative Analysis of (a) N2 (b) NH3
(c) NO2 (d) None of these
Organic Compounds
111. In Kjeldahl's method of estimation of nitrogen, K2SO4 acts
101. In sodium fusion test of organic compounds, the nitrogen as
of the organic compound is converted into (a) oxidising agent (b) catalytic agent
(a) sodamide (b) sodium cyanide (c) hydrolysing agent (d) boiling point elevator
(c) sodium nitrite (d) sodium nitrate 112. 0.5g of an organic compound containing nitrogen on
102. Which of the following compounds does not show Kjeldahlising required 29 mL of N/5 H2SO4 for complete
Lassaigne’s test for nitrogen ? neutralization of ammonia. The percentage of nitrogen in
(a) Urea (b) Hydrazine the compound is
(c) Phenylhydrazine (d) Azobenzene (a) 34.3 (b) 16.2 (c) 21.6 (d) 14.8
103. The compound formed in the positive test for nitrogen with 113. The percentage of sulphur in an organic compound whose
the Lassaigne solution of an organic compound is 0.32 g produces 0.233 g of BaSO4 [At. wt. Ba = 137, S = 32]
(a) Fe4[Fe(CN)6]3 (b) Na3[Fe(CN)6] is
(c) Fe(CN)3 (d) Na4[Fe(CN)5NOS] (a) 1.0 (b) 10.0 (c) 23.5 (d) 32.1
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 157

114. 2.79 g of an organic compound when heated in Carius tube (ii) A spiral of silver is introduced if the organic compound
with conc. HNO 3 ; H 3PO 4 formed converted into contains halogens.
(iii) The copper oxide in the combustion tube is replaced
MgNH 4 .PO 4 ppt. The ppt. on heating gave 1.332 g of
by lead chromate if the organic compound contains
Mg 2 P2O 7 . The percentage of P in the compound is sulphur.
(a) 23.33% (b) 13.33% (c) 33.33% (d) 26.66% (a) (i) and (ii) are correct (b) (i) and (iii) are correct
115. A compound contains 38.8% C, 16% H and 45.2% N. The (c) (ii) and (iii) are correct (d) All are correct
formula of compound would be :
118. Assertion : Sulphur present in an organic compound can
(a) CH 3 NH 2 (b) CH 3CN be estimated quantitatively by Carius method.
(c) C 2 H 5CN (d) C H2(NH2)2 Reason : Sulphur is separated easily from other atoms in the
116. In Kjeldahl’s method for the estimation of N2, potassium molecule and gets precipitated as light yellow solid.
sulphate and copper sulphate are used. On the basis of (a) Assertion is correct, reason is correct; reason is a
their functions which of the following statement(s) is/are correct explanation for assertion.
correct? (b) Assertion is correct, reason is correct; reason is not a
(i) Potassium sulphate raises the bpt. and ensures correct explanation for assertion
complete reaction. (c) Assertion is correct, reason is incorrect
(ii) Copper sulphate acts as catalyst.
(iii) Potassium sulphate acts as catalyst and copper (d) Assertion is incorrect, reason is correct.
sulphate raises the bpt. 119. The molecular mass of an organic compound which contains
(a) Only (iii) is correct (b) (i) and (ii) are correct only one nitrogen atom can be
(c) Only (ii) is correct (d) None is correct (a) 152 (b) 146 (c) 76 (d) 73
117. In the estimation of carbon and hydrogen by combustion 120. 0.25 g of an organic compound on Kjeldahl's analysis gave
method which of the following is/are correct ? enough ammonia to just neutralize 10cm3 of 0.5 M H2SO4.
(i) A spiral of copper is introduced at the right extreme of The percentage of nitrogen in the compound is
combustion tube if the organic compound contains
nitrogen. (a) 28 (b) 56 (c) 14 (d) 112

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (c) 2-chloro-1-nitro-5-methylbenzene
1. Which of the following is the correct IUPAC name? (d) m-nitro-p-chlorotoluene
(a) 3-ethyl-4, 4-dimethylheptane 4. Electronegativity of carbon atoms depends upon their state
(b) 4, 4-dimethyl-3-ethylheptane of hybridisation. In which of the following compounds, the
(c) 5-ethyl-4, 4-dimethylheptane carbon marked with asterisk is most electronegative?
(d) 4, 4-bis(methyl)-3-ethylheptane (a) CH3 – CH2 – *CH2 – CH3
(b) CH3 – *CH = CH – CH3
O O
|| || (c) CH3 – CH2 – C º *CH
2. The IUPAC name for CH3 - C - CH 2 - CH 2 - C - OH is (d) CH3 – CH2 – CH = *CH2
5. In which of the following functional groups, isomerism is
(a) 1-hydroxypentane-1, 4-dione
not possible?
(b) 1, 4-dioxopentanol
(a) Alcohols (b) Aldehydes
(c) 1-carboxybutan-3-one
(c) Alkyl halides (d) Cyanides
(d) 4-oxopentanoic acid
6. The fragrance of flowers is due to the presence of some
3. The IUPAC name for
Cl steam volatile organic compounds called essential oils.
These are generally insoluble in water at room temperature
NO2 but are miscible with water vapour in vapour phase. A
suitable method for the extraction of these oils from the
flowers is
(a) distillation
CH3 (b) crystallisation
(a) 1-chloro-2-nitro-4-methylbenzene (c) distillation under reduced pressure
(b) 1-chloro-4-methyl-2-nitrobenzene (d) steam distillation
 EBD_7374
158 CHEMISTRY

7. During hearing of a court case, the judge suspected that 15. The addition of HCl to an alkene proceeds in two steps.
some changes in the documents had been carried out. He The first step is the attack of H+ ion to C —
— C portion
asked the forensic department to check the ink used at two
different places. According to you which technique can which can be shown as
give the best results?
(a) Column chromatography (a) +
C—
H —C
(b) Solvent extraction
(c) Distillation
(d) Thin layer chromatography (b) H + —C
C—
8. The principle involved in paper chromatography is
(a) adsorption (b) partition (c) + —C
H C—
(c) solubility (d) volatility
9. What is the correct order of decreasing stability of the (d) All of these are possible
following cations?
Past Year MCQs
Å Å
I. CH3 - C H - CH3 II. CH3 - C H - OCH3 16. Which of the following compounds will un dergo
Å racemisation when solution of KOH hydrolyses?
III. CH3 - C H - CH 2 - OCH3 [AIPMT 2014, S]
(a) II > I > III (b) II > III > I CH2Cl
(c) III > I > II (d) I > II > III
10. Correct IUPAC name for H3C – CH – CH – CH3 is ......... . (i) (ii) CH3CH2CH2Cl
| |
C2H5 C2H5 CH3
(a) 2-ethyl-3-methylpentane CH3
(b) 3, 4-dimethylhexane | C
(c) 2-sec-butylbutane (iii) H3C - C H - CH2Cl (iv) H Cl
C2H3
(d) 2, 3-dimethylbutane
11. In which of the following compounds the carbon marked (a) (i) and (ii) (b) (ii) and (iv)
with asterisk is expected to have greatest positive charge? (c) (iii) and (iv) (d) (iv)
(a) *CH3 — CH2 — Cl (b) *CH3 — CH2 — Mg+Cl–
(c) *CH3 — CH2 — Br (d) *CH3 — CH2 — CH3 17. The molecular formula of diphenyl methane,
12. Ionic species are stabilised by the dispersal of charge. CH2 , is C13H12.
Which of the following carboxylate ion is the most stable?
O O How many structural isomers are possible when one of the
|| || hydrogens is replaced by a chlorine atom?
(a) CH3 - C - O - (b) Cl - CH 2 - C - O - [AIIMS 2014, S]
O O (a) 6 (b) 4 (c) 8 (d) 7
||
-
F || 18. The compound CHCl == CHCHOHCOOH with molecular
(c) F - CH 2 - C - O (d) CH - C - O-
formula C4H5O3Cl can exhibit [AIIMS 2014, C]
F
13. Electrophilic addition reactions proceed in two steps. The (a) geometric, optical position and functional isomerism
first step involves the addition of an electrophile. Name the (b) geometric, optical and functional isomerism only
type of intermediate formed in the first step of the following
(c) position and functional isomerism only
addition reaction. H3C – HC = CH2 + H+ ----® ?
(a) 2° carbanion (b) 1° carbocation (d) geometric and optical isomerism only
(c) 2° carbocation (d) 1° carbanion 19. Assertion : In the third group of qualitative analysis, NH4Cl
14. Covalent bond can undergo fission in two different ways. is added to NH4OH medium.
The correct representation involving a heterolytic fission Reason : This is to convert the ions of group into their
of CH3 – Br is respective chlorides. [AIIMS 2014, C]
(a) Å (a) If both Assertion and Reason are correct and Reason
CH 3 - Br ¾¾
® CH 3 + Br
is the correct explanation of Assertion.
r
® CH 3 + Br s
(b) CH 3 - Br ¾¾ (b) If both Assertion and Reason are correct, but Reason
r is not the correct explanation of Assertion.
(c) CH - Br ¾¾
3 ® CH 3 + Br s
(c) If Assertion is correct but Reason is incorrect.
(d) CH - Br ¾¾ r s (d) If both the Assertion and Reason are incorrect.
3 ® CH 3 + Br
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 159

20. For which of the following molecule significant m ¹ 0? Which of the given compounds can exhibit tautomerism?
[AIPMT 2015, A]
[JEE M 2014, C]
(a) I and III (b) II and III
Cl CN (c) I, II and III (d) I and II
25. Which of the following statements is not correct for a
nucleophile? [AIPMT 2015 RS, C]
(i) (ii) (a) Nucleophile is a Lewis acid
(b) Ammonia is a nucleophile
Cl CN (c) Nucleophiles attack on less e– density sites
(d) Nucleophiles are not electron seeking.
OH SH 26. Consider the following compounds [AIPMT 2015, S]
CH3 Ph
(iii) (iv) CH3—C—CH— Ph—C—PH
CH3
OH SH CH3
(I) (II) (III)
(a) Only (i) (b) (i) and (ii)
(c) Only (iii) (d) (iii) and (iv) Hyperconjugation occurs in :
(a) II only (b) III only (c) I and III (d) I only
21. Arrangement of (CH3)3 C –, (CH3)2 CH –, CH3 CH2 – when
27. Which of the following is the most correct electron
attached to benzyl or an unsaturated group in increasing
displacement for a nucleophilic reaction to take place?
order of inductive effect is [BITSAT 2014, C]
[AIPMT 2015, S]
(a) (CH3)3C – < (CH3)2 CH – < CH3 CH2–
(b) CH3CH2– < (CH3)2CH – < (CH3)3C – H H2
(a) H3C—C = C – C – Cl
(c) (CH3)2CH – <(CH3)3C – < CH3CH2– H
(d) (CH3)3C – < CH3CH2 – < (CH3)2CH – H H2
(b) H 3C—C = C – C – Cl
22. Which of the following compounds has wrong IUPAC H
name? [BITSAT 2014, S] H H2
(a) CH3 – CH2 – CH2 – COO – CH2CH3 (c) H 3C—C = C – C – Cl
H
® ethyl butanoate H H2
(b) CH3 – CH – CH2 – CHO ® 3-methyl-butanal (d) H 3C—C = C – C – Cl
| H
CH3 28. Tautomerism is exhibited by – [AIIMS 2015, S]

(c) CH3 - CH - CH - CH3 ® 2-methyl-3-butanol

| | (1) CH = CH – OH
OH CH3

O (2) O O
||
(d) CH3 - CH - C - CH 2 - CH3
| ® 2-methyl-3-pentanone
CH3 (3) O

23. Two possible stereo-structures of CH3CHOHCOOH, which O

are optically active, are called. [AIPMT 2015 RS, C]
(a) Diastereomers (b) Atropisomers (4) O
(c) Enantiomers (d) Mesomers
24. Given
O
CH3 CH3 CH3 (a) (1), (3) and (4) (b) (2), (3), and (4)
(c) All of these (d) None of these
CH3 CH3 29. Name of the compound given below is
CH3
O O O
(I) (II) (III)
 EBD_7374
160 CHEMISTRY

(a) 3- methyl -4- ethyloctane [AIIMS 2013, 2015, S] 36. In Lassaigne's test for the detection of halogens, the sodium
(b) 2, 3- diethylheptane fusion extract is first boiled with concentrated nitric acid.
(c) 5- ethyl - 6- methyloctane This is [AIIMS 2016, S]
(d) 4- ethyl- 3- methyloctane (a) to remove silver halides
30. Which of the following compounds will exhibit geometrical (b) to decompose Na2S and NaCN, if present
isomerism ? [JEE MAIN 2015, S] (c) to dissolve Ag2S
(a) 2 - Phenyl -1 - butene (d) to dissolve AgCN, if formed
(b) 1, 1 - Diphenyl - 1 - propene 37. Consider the following bromides :
(c) 1 - Phenyl - 2 - butene Me Me
(d) 3 - Phenyl -1 - butene Me Br Me
31. Which of the following molecules is least resonance
Br Br
stabilized? [JEE M 2015, S] (A) (B)
The correct order of SN1 reactivity is
(a) (b) [AIIMS 2016, S]
O (a) B > C > A (b) B > A > C
(c) C > B > A (d) A > B > C
38. Which of the following has two stereoisomers?
[BITSAT 2016, A]
(c) (d) CH =CH2 CH=CH2
N O | | CH =CH2
CH3 - N +- H CH3 - N+- H
|
32. The anthracene is purified by [BITSAT 2015, S] | | H 3C - N
..-H
(a) crystallisation (b) filtration CH2CH3 CH3
(III)
(c) distillation (d) sublimation (I) (II)
33. Which of the following biphenyls is optically active ? (a) None of these (b) Only I
[NEET 2016, A] (c) Only III (d) I and III
Br Br 39. Which of the following compounds has all the four types
O2N (1°, 2°, 3° and 4°) of carbon atoms?
[BITSAT 2016, S]
(a) (b)
(a) 2, 3, 4-Trimethylpentane
(b) neo-Pentane
I I I
(c) 2, 2, 4-Trimethylpentane
I CH3 (d) None of the three
40. The IUPAC name of the compound is : [NEET 2017, S]
(c) (d)
O O
I CH3 H C
34. The correct statement regarding the comparison of
staggered and eclipsed conformation of ethane, is
[NEET 2016, C] (a) 5-formylhex-2-en-3-one
(a) The staggered conformation of ethane is less stable (b) 5-methyl-4-oxohex-2-en-5-al
than eclipsed conformation, because staggered (c) 3-keto-2-methylhex-5-enal
conformation has torsional strain (d) 3-keto-2-methylhex-4-enal
(b) The eclipsed conformation of ethane is more stable 41. The correct statement regarding electrophile is:-
than staggered conformation, because eclipsed [NEET 2017, C]
conformation has no torsional strain (a) Electrophile is a negatively charged species and can
(c) The eclipsed conformation of ethane is more stable form a bond by accepting a pair of electrons from
than staggered conformation even though the eclipsed another electrophile
conformation has torsional strain (b) Electrophiles are generally neutral species and can form
(d) The staggered conformation of ethane is more stable a bond by accepting a pair of electrons from a
than eclipsed conformation, because staggered nucleophile
conformation has no torsional strain. (c) Electrophile can be either neutral or positively charged
35. The pair of electron in the given carbanion, CH3C º C- , is species and can form a bond by accepting a pair of
electrons from a nucleophile
present in which of the following orbitals ?
(d) Electrophile is a negatively charged species and can
[NEET 2016, C] form a bond by accepting a pair of electrons from a
(a) 2p (b) sp3 (c) sp2 (d) sp nucleophile
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 161

42. Assertion : NF3 is a weaker ligand than N(CH3)3. (b) 3-Hydroxy cyclohex-5-en-1-one
[AIIMS 2017, C] (c) 8-Hydroxy cyclohex-3-en-1-one
Reason : NF3 ionizes to give F– ions in aqueous solution. (d) 7-Hydroxy cyclohex-5-en-1-one
(a) If both Assertion and Reason are correct and Reason 50. The correct order of nucleophilicity of the following spe-
is the correct explanation of Assertion. cies is [AIIMS 2018, C]
(b) If both Assertion and Reason are correct, but Reason (i) OH – (ii) HS–
is not the correct explanation of Assertion. – –
(iii) Ph – O (iv) C2H5 – O
(c) If Assertion is correct but Reason is incorrect.
(a) i > ii > iii > iv (b) ii > iv > i > iii
(d) If both the Assertion and Reason are incorrect.
43. The strongest ortho - para and strongest meta - directing (c) ii > iii > i > iv (d) iii > iv > i > ii
groups respectively are [AIIMS 2017, S] 51. For geometrical isomers of 3-hexene : [AIIMS 2018, S]
(a) –NO2 and –NH2 H C 2H 5 H H
(b) –CONH2 and –NH2 C=C & C=C
C 2H 5 H C 2H 5 C 2H 5
(c) –NH2 and –CONH2
(d) –NH2 and –NO2 (a) M.P. is high and dipole moment high for trans
44. The increasing order of the reactivity of the following halides (b) M.P. is law and dipole moment low for trans
for the SN1 reaction is [JEE M 2017, S] (c) M.P. is high and dipole moment low for trans
(d) M.P. is low and dipole moment high for trans
CH3CHCH2CH3 CH3CH 2CH2Cl
| 52. Assertion : 2, 4-Dimethyl hex-2-ene has 4 stereoisomers.
Cl (II)
Reason : It shows geometrical isomerism.[AIIMS 2018, C]
(I)
(a) If both assertion and reason are true and reason is the
p-H3CO–C6H4–CH2Cl correct explanation of assertion.
(III)
(b) If both assertion and reason are true but reason is not
(a) (III) < (II) < (I) (b) (II) < (I) < (III)
the correct explanation of assertion.
(c) (I) < (III) < (II) (d) (II) < (III) < (I)
45. Which of the following does not contain Plane of symmetry? (c) If assertion is true but reason is false.
[BITSAT 2017, S] (d) If both assertion and reason are false.
(a) trans-1,3 dichloro cyclohexane 53. The increasing order of basicity of the following compounds
(b) trans-1,2 dichloro cyclohexane is [JEE M 2018, A]
(c) cis-1,2 dichloro cyclohexane (i) (ii)
(d) trans-1,3 cyclopentane
46. A compound of molecular formula of C7H16 shows optical
isomerism, compound will be [BITSAT 2017, A] (iii) (iv)
(a) 2, 3-Dimethylpentane (b) 2,2-Dimethylbutane
(a) (i) < (ii) < (iii) < (iv) (b) (ii) < (i) < (iii) < (iv)
(c) 3-Methylhexane (d) None of the above
(c) (ii) < (i) < (iv) < (iii) (d) (iv) < (ii) < (i) < (iii)
47. Which of the following molecules represents the order of
54. Which of the following is strongest nucleophile
hybridisation sp2, sp2, sp, sp from left to right atoms?
[BITSAT 2018, C]
[NEET 2018, A]
(a) HC º C – C º CH (a) Br– (b) : OH– (c) : CN - (d) C2 H 5O :
(b) CH2 = CH – C º CH 55. The IUPAC name of the compound is [BITSAT 2018, S]
(c) CH3 – CH = CH – CH3
(d) CH2 = CH – CH = CH2
48. Which of the following is correct with respect to – I effect
HO
of the substituents? (R = alkyl) [NEET 2018, C]
(a) – NH2 < – OR < – F (b) – NR2 < – OR < – F (a) 3, 3-dimethyl - 1- cyclohexanol
(c) – NR2 > – OR > – F (d) – NH2 > – OR > – F (b) 1, 1-dimethyl-3-hydroxy cyclohexane
(c) 3, 3-dimethyl-1-hydroxy cyclohexane
OH (d) 1, 1-dimethyl-3-cyclohexanol
56. Which of the following will have a meso-isomer also?
49. [AIIMS 2018, S] (a) 2, 3- Dichloropentane [BITSAT 2018, C]
(b) 2, 3-Dichlorobutane
O (c) 2-Chlorobutane
The IUPAC name for the given structure is (d) 2-Hydroxypropanoic acid
(a) 5-Hydroxy cyclohex-3-en-1-one
 EBD_7374
162 CHEMISTRY

Exercise 3 : Try If You Can

OH
1. The IUPAC name of 5.
O

(1) (2)
(a) 2, 6-Dimethylhepta-2, 5-dienoic acid
(b) 3, 7-Dimethylhepta-2, 5-dienoic acid
(c) 1-Hydroxy-2, 6-dimethylhepta-2, 5-dienone
(d) none of these
2. How many number of compounds, which have same (3) (4)
IUPAC name? Choose the statement that best describes given compounds.
OH OH (a) 1, 3, 4 represent same compound
(b) 1 and 3 are isomer of 2 and 4
OH (c) 1, 4 are isomer of 2 and 3
(d) All the structure represent the same compound
OH 6. The structure :
CH 3 H
OH
C=C H
OH CH 3 C shows
COOH
CH 3
OH OH
(a) tautomerism
(a) 0 (b) 1 (c) 2 (d) 3
(b) geometrical isomerism
3. Total number of a-hydrogen in given compound is: (c) optical isomerism
(d) geometrical and optical isomerism
7. Most stable carbocation among the following is:
CH3 +
(a) + (b)

+ +
(c) CH2 (d) CH3
(a) 4 (b) 5 (c) 6 (d) 7
+
4. Identify which of the strucutre below are meso structures? O
O O +
O O 8.
(1) (2) +
O O (I) (II) (III)
The most stable canonical structure among the given
O structure is :
O (a) I (b) II
O O
O O (c) III (d) all are equally stable
(3) (4)
9. Which of the following is the strongest base?
O O NH2 NMe2
O
(a) (b)
(5) O O
NH2 NMe2
(a) 1 and 3 (b) 1, 3 and 5 Me Me Me3C CMe3
(c) (d)
(c) 1, 3 and 4 (d) 2 and 5
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 163

10. Select the appropriate relation with respect to acidity of X, 14. Which of the following structure represent meso-
Y, Z for the given compound, with increasing order. compounds?
+ + H OH
H3N NH3 OH
Z X (i)
H
COOH
Y CH 3
(a) Z > X > Y (b) Y > Z > X (ii)
H
(c) Z < X > Y (d) X > Y > Z
11. The correct arrangement for leaving tendency among the OH
following groups is
(iii)
–
F- NH -2 H2O H3C SO2O F3CSO 2 O -
I II III V
CH 3 CH 3
IV
(a) III > I > II > IV > V (b) V > IV > III > I > II
(c) I > III > II > IV > V (d) V > IV > I > III > II Br H
12. 2, 4, 6- Trinitroiodobenzene has three C–N bonds | CH 3
C
I (iv) |
O2N a b NO2 C
labelled as a, b and c. The correct bond H 3C Br H

c (a) (i) and (ii) (b) (iii) and (iv)

NO2 (c) (i) , (ii) and (iii) (d) All the four
15. An organic compound X of the formula C 4 H8 Cl 2 on
length of the three bonds is
treatment with aqueous sodium hydroxide gives another
(a) a = b = c (b) a > b > c
compound Y which forms an oxime and undergoes haloform
(c) a = b > c (d) a = b < c
reaction, but does nto reduce Tollens’ reagent. The
O NHCH3 compound X should be
(a) Me2 CHCHCl 2
13. IUPAC name Cl is
(b) CH3CH 2CH 2 CHCl2
O
(c) CH3 CH 2 CCl 2 CH 3
(a) 4- Acetamido-6-chloropexen-3-one
(b) 4-Chloromethyl-1-methylamono-1-oxohent-4-en-3one Cl Cl
(c) N-Methyl-2-(2'-chloroethyl)-3-keto-4-pentenamide | |
(d) CH3 CH CHCH3
(d) 4-Chloroethyl-3-keto-5-methylamidopentene
 EBD_7374
164 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 13 (d) 25 (b) 37 (c) 49 (b) 61 (d) 73 (a) 85 (b) 97 (b) 109 (b)
2 (d) 14 (d) 26 (d) 38 (c) 50 (b) 62 (b) 74 (c) 86 (d) 98 (a) 110 (b)
3 (c) 15 (c) 27 (b) 39 (b) 51 (b) 63 (d) 75 (c) 87 (b) 99 (a) 111 (d)
4 (b) 16 (a) 28 (b) 40 (d) 52 (c) 64 (c) 76 (d) 88 (a) 100 (d) 112 (b)
5 (b) 17 (d) 29 (a) 41 (c) 53 (b) 65 (b) 77 (c) 89 (c) 101 (b) 113 (b)
6 (b) 18 (a) 30 (c) 42 (b) 54 (b) 66 (a) 78 (b) 90 (c) 102 (b) 114 (b)
7 (d) 19 (a) 31 (a) 43 (a) 55 (b) 67 (b) 79 (d) 91 (a) 103 (a) 115 (a)
8 (d) 20 (b) 32 (b) 44 (d) 56 (d) 68 (d) 80 (b) 92 (d) 104 (c) 116 (b)
9 (b) 21 (b) 33 (d) 45 (b) 57 (c) 69 (b) 81 (c) 93 (a) 105 (d) 117 (d)
10 (c) 22 (c) 34 (c) 46 (a) 58 (c) 70 (b) 82 (a) 94 (c) 106 (b) 118 (c)
11 (b) 23 (d) 35 (b) 47 (a) 59 (d) 71 (b) 83 (b) 95 (b) 107 (d) 119 (d)
12 (b) 24 (a) 36 (a) 48 (d) 60 (b) 72 (b) 84 (d) 96 (b) 108 (d) 120 (b)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (a) 7 (d) 13 (c) 19 (c) 25 (a) 31 (d) 37 (a) 43 (d) 49 (a) 55 (a)
2 (d) 8 (b) 14 (b) 20 (d) 26 (b) 32 (d) 38 (b) 44 (b) 50 (b) 56 (b)
3 (b) 9 (a) 15 (b) 21 (b) 27 (b) 33 (b) 39 (c) 45 (c) 51 (c)
4 (c) 10 (b) 16 (d) 22 (c) 28 (a) 34 (d) 40 (d) 46 (a) 52 (d)
5 (c) 11 (a) 17 (b) 23 (c) 29 (d) 35 (d) 41 (c) 47 (b) 53 (c)
6 (d) 12 (d) 18 (a) 24 (c) 30 (c) 36 (b) 42 (c) 48 (a) 54 (c)
Exercis e 3 : Try If You Can
1 (a) 3 (c) 5 (a) 7 (a) 9 (d) 11 (b) 13 (c) 15 (c)
2 (a) 4 (a) 6 (c) 8 (c) 10 (b) 12 (c) 14 (b)
 13 Chapter
HYDROCARBONS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

8
7
6
AIPMT /NEET
5
Number of Questions

AIIMS
4
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 4 Substitution reaction in alkanes,
AIIMS 5 conformation of ethane, addition 4/5 8.4
reaction in alkenes, ozonolysis,
JEE Main 4 Friedel craft reaction, electrophilic
BITSAT 3 substitution reaction
 EBD_7374
166 CHEMISTRY
HYDROCARBONS 167
 EBD_7374
168 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Alkanes 12. Liquid hydrocarbons can be converted to a mixture of

gaseous hydrocarbons by :
1. The number of chain isomers possible for the hydrocarbon
(a) oxidation
C5H12 is
(b) cracking
(a) 1 (b) 2 (c) 3 (d) 4 (c) distillation under reduced pressure
2. Name of the given compound - (d) hydrolysis
CH3 13. n-Hexane isomerises in presence of anhydrous aluminium
CH3 chloride and hydrogen chloride gas to give
(a) 2-Methyl pentane (b) 3-Methyl pentane
CH3 (c) Both (a) and (b) (d) Neither (a) nor (b)
14. How many conformations are possible for ethane ?
CH3 (a) 2 (b) 3 (c) infinite (d) one
(a) 2, 3-diethyl heptane (b) 5-ethyl-6-methyl octane 15. Spatial arrangements of atoms which can be converted into
(c) 4-ethyl-3-methyl octane (d) 3-methyl-4-ethyl octane one another by rotation around a C–C single bond are called
3. Which of the following statements is false for isopentane/ (a) Stereoisomers (b) Tautomers
(a) It has three CH3 groups (c) Optical isomers (d) Conformers
(b) It has one CH2 group 16. Which of the following statements are correct regarding
(c) It has one CH group structure of methane ?
(d) It has a carbon which is not bonded to hydrogen (i) Methane has tetrahedral structure.
4. Molecular formula of which of the following alkane can exist (ii) The bond angle between all H – C – H bonds is 109.5°.
in more than one structure ? (iii) The carbon atom is sp2 hybridized.
(a) CH4 (b) C2H6 (c) C3H8 (d) C4H10 (iv) C – C and C – H bond lengths are 154 pm and 112 pm
respectively.
5. The reaction,
(a) (i), (ii) and (iii) (b) (i), (iii) and (iv)
CH 3 - Br + 2Na + Br – CH 3 ® the product, is called (c) (i), (ii) and (iv)(d) (i), (ii), (iii) and (iv)
(a) Wurtz reaction (b) Perkin’s reaction 17. In the preparation of alkanes from hydrogenation of alkenes
(c) Aldol condensation (d) Levit reaction and alkynes, finely divided catalysts are used which of the
6. Pure methane can be produced by following statement(s) is/are correct regarding these
(a) Wurtz reaction catalysts
(b) Kolbe’s electrolytic method (i) Platinum and palladium catalyse the reaction at room
(c) Soda-lime decarboxylation temperature.
(d) Reduction with H2 (ii) Nickel catalyses the reaction at relatively higher
7. Sodium salts of carboxylic acids on heating with soda lime temperature and pressure.
give alkanes containing _______ than the carboxylic acid. (iii) Platinum and palladium catalyse the reaction at higher
(a) one carbon more (b) one carbon less temperature.
(c) two carbon less (d) Either (a) or (b) (a) (i) and (iii) (b) (i) and (ii)
8. In the free radical chlorination of methane, the chain initiating (c) (ii) and (iii) (d) (i) only
step involves the formation of 18. Which of the following statements are correct ?
(a) chlorine free radical (b) hydrogen chloride (i) The rate of reactivity of alkanes with halogens is
(c) methyl radical (d) chloromethyl radical. F2 > Cl2 > Br2 > I2.
9. Which one of the following gives only one monochloro (ii) Rate of replacement of hydrogens of alkanes is
derivative? 3° > 2º > 1°
(a) n-Hexane (b) 2-MMethylpentane (iii) Fluorination of alkanes is a very slow process.
(c) 2, 3-Dimethylpentane (d) neo-Pentane (iv) Iodination of alkanes is too violent to be controlled.
10. Photochemical halogenation of alkane is an example of (a) (i), (ii) and (iii) (b) (i) and (ii)
(a) electrophilic substitution (c) (ii) and (iii) (d) (i) and (iv)
(b) electrophilic addition 19. Which of the following statements are correct ?
(c) nucleophilic substitution (i) Decomposition reaction of higher alkanes into smaller
(d) free radical substitution fragments by the application of heat is called pyrolysis.
11. Complete combustion of CH4 gives : (ii) Pyrolysis and cracking are different processes.
(a) CO2 + H2O (b) CO2 + H2 (iii) Dodecane on pyrolysis gives a mixture of heptane and
(c) COCl2 (d) CO + CO2 + H2O pentene.
HYDROCARBONS 169

(iv) Pyrolysis follows free radical mechanism. (a) Assertion is correct, reason is correct; reason is a
(a) (i), (ii) and (iii) (b) (i), (ii) and (iv) correct explanation for assertion.
(c) (i), (iii) and (iv) (d) (ii) and (iv) (b) Assertion is correct, reason is correct; reason is not a
20. Which of the following statement(s) is/are correct ? correct explanation for assertion
(i) Alkanes can have infinite number of conformations by (c) Assertion is correct, reason is incorrect
rotation around a C – C single bonds. (d) Assertion is incorrect, reason is correct.
(ii) Rotation around C – C single bond is completely free. 26. A hydrocarbon A on chlorination gives B which on heating
(iii) Rotation is hindered by a small energy barrier of with alcoholic potassium hydroxide changes into another
1-20 kJ mol–1 due to torsional strain. hydrocarbon C. The latter decolourises Baeyer's reagent
(a) (i) and (ii) (b) (i) and (iii) and on ozonolysis forms formaldehyde only. A is
(c) (ii) and (iii) (d) Only (iii) (a) Ethane (b) Butane
21. Which of the following statements are correct ? (c) Methane (d) Ethene
(i) Stability of conformation is affected due to torsional 27. Which of the following compounds can yield only one
strain. monochlorinated product upon free radical chlorination?
(ii) Magnitude of torsional strain depends upon the angle (a) Propane (b) 2, 2-Dimethylpropane
of rotation about C – C bond. (c) 2-Methylpropane (d) n-Butane
(iii) Eclipsed form has least torsional strain.
Topic 2: Alkenes
(iv) Staggered form has maximum torsional strain.
(a) (i) and (iii) (b) (i) and (ii) 28. The restricted rotation about carbon-carbon double bond
(c) (iii) and (iv) (d) (i) and (iv) in 2- butene is due to
22. Match the columns (a) overlap of one s- and one sp2-hybridized orbitals
Column-I Column-II (b) overlap of two sp2-hybridized orbitals
(A) CH2 = CH2 ® CH3 – CH3 (p) H2, Zn, H+ (c) overlap of one p-and one sp2-hybridized orbitals
(B) CH3Cl ® CH4 (q) NaOH, CaO (d) sideways overlap of two p-orbitals
(C) CH3Br ® CH3CH3 (r) H2, Pt/Pd 29. IUPAC name of the following compound will be
(D) CH3COONa ® CH4 (s) Na, dry ether CH3 - CH = C - CH 2 - CH3
(a) A – (r), B – (p), C – (s), D – (q) |
(b) A – (p), B – (s), C – (r), D – (q) CH 2 - CH 2 - CH3
(c) A – (s), B – (q), C – (p), D – (r) (a) 3–Ethyl–2–hexene (b) 3–Propyl–2–hexene
(d) A – (q), B – (p), C – (s), D – (r) (c) 3–Propyl–3–hexene (d) 4–Ethyl–4–hexene
23. Match the columns 30. The name of ClCH 2 - C = C - CH 2 Cl according to
Column-I Column-II | |
Br Br
Cu/523K/100 atm
(A) CH4 + O2¾¾¾¾¾¾¾ (p) HCHO
® IUPAC nomenclature system is
Mo O (a) 2, 3- dibromo -1, 4- dichlorobutene-2
(B) CH4 + O2 ¾¾¾¾
2 3®
D
(q) (CH3)3COH
(b) 1, 4- dichloro-2, 3- dibromobutene-2
(CH COO) Mn (c) Dichlorodibromobutene
(C) C2H6 + O2 ¾¾¾¾¾¾¾
3
D
2 ® (r) CH3OH
(d) Dichlorodibromobutane
KMnO 31. Which one of the following exhibits geometrical isomerism?
(D) (CH3)3CH ¾¾ ¾ ¾® 4
oxidation
(s) CH3COOH
(a) 1, 2-dibromopropene (b) 2, 3-dimethylbut-2-ene
(a) A – (s), B – (p), C – (r), D – (s)
(c) 2, 3-dibromobut-2-ene (d) Both (a) and (c)
(b) A – (q), B – (p), C – (s), D – (r)
32. The compounds CH3CH == CHCH3 and
(c) A – (r), B – (p), C – (s), D – (q)
CH3CH2CH == CH2
(d) A – (p), B – (q), C – (r), D – (s)
(a) are tautomers
24. Assertion : CH4 does not react with Cl2 in dark.
(b) are position isomers
Reason : Chlorination of CH4 takes place in sunlight.
(a) Assertion is correct, reason is correct; reason is a (c) contain same number of sp3 – sp3, sp3 – sp2 and sp2
correct explanation for assertion. – sp2 carbon-carbon bonds
(b) Assertion is correct, reason is correct; reason is not a (d) exist together in dynamic equilibrium
correct explanation for assertion 33. Consider the following statements : A hydrocarbon of
(c) Assertion is correct, reason is incorrect molecular formula C5H10 is a
(d) Assertion is incorrect, reason is correct. I. monosubstituted alkene
25. Assertion : Iodination of alkanes is reversible. II. disubstituted alkene
Reason : Iodination is carried out in presence of iodic acid. III. trisubstituted alkene
 EBD_7374
170 CHEMISTRY

Which of the following statement(s) is(are) correct?

Br
(a) I, II and III (b) I and II |
(c) II and III (d) I and III (b) CH3 - C- CH 2 - CH3
34. Geometrical isomerism is not shown by |
CH3
CH3
| (c) CH3 - CH- CH - CH 3
(a) CH3CH 2C= C CH 2CH 3 | |
| Br CH3
CH3
(d) CH 3 - CH - CH - CH 3
| |
(b) C 2 H 5 - C = C - CH 2 I
| | CH 3 Br
H H 43. Butene-1 may be converted to butane by reaction with
(c) CH 2 = C(Cl)CH3 (a) Sn – HCl (b) Zn – Hg
(c) Pd/H2 (d) Zn – HCl
(d) CH 3 - CH = CH - CH = CH 2 44. Alkenes usually show which type of reactions?
35. By which reaction ethene is obtained from ethyne? (a) addition (b) substitution
(a) oxidation (b) polymerisation (c) elimination (d) superposition
(c) hydrogenation (d) dehydrogenation 45. A reagent used to test unsaturation in alkene is -
36. The major product formed when 2-bromobutane is treated (a) ammonical Cu2Cl2 (b) ammonical AgNO3
with alcoholic KOH is (c) solution of Br2 in CCl4 (d) conc. H2SO4
(a) 2-Butanol (b) 1-Butene 46. In the given reaction
(c) 1-Butanol (d) trans-2-butene X
CH 3CH 2 CH = CHCH 3 ¾¾®
37. Ethyl alcohol is heated with conc. H 2SO4 . The product
CH3CH 2COOH +CH3COOH
formed is :
The X is
(a) H3C - C - OC2 H5 (b) C2 H 6
(a) C2 H5ONa (b) Conc. HCl +Anhy.ZnCl2
||
O (c) Anh. AlCl3 (d) KMnO4/OH–
47. The negative part of an addendum adds on to the carbon
(c) C2 H 4 (d) C2 H 2 atom joined to the least number of hydrogen atoms. This
38. When hydrochloric acid gas is treated with propene in statement is called
presence of benzoyl peroxide, it gives (a) Thiele’s theory (b) Peroxide effect
(a) 2-Chloropropane (b) Allyl chloride (c) Markownikoff’s rule (d) Baeyer’s strain theory
(c) No reaction (d) n-Propyl chloride. 48. In the following sequence of reactions, the alkene affords
39. "The addition of unsymmetrical reagents to unsymmetrical the compound ‘B’
alkenes occurs in such a way that the negative part of the O H O
CH 3 - CH = CH - CH 3 ¾¾3¾
® A ¾¾¾
2 ® B.
addendum goes to that carbon atom of the double bond Zn
which carries lesser number of hydrogen atoms" is called The compound B is
by : (a) CH3CH2CHO (b) CH3COCH3
(a) Saytzeff rule (b) Markownikoff's rule (c) CH3CH2COCH3 (d) CH3CHO
(c) Kharasch effect (d) Anti-Saytzeff rule 49. One mole of a symmetrical alkene on ozonolysis gives two
40. When one mole of an alkene on ozonolysis produces 2 moles moles of an aldehyde having a molecular mass of 44 u. The
of propanone, the alkene is alkene is
(a) 3-methyl-1-butene (b) 2, 3-dimethyl-1-butene (a) propene (b) 1-butene
(c) 2, 3-dimethyl-2-pentene (d) 2, 3-dimethyl-2-butene (c) 2-butene (d) ethene
41. Reaction of HBr with propene in the presence of peroxide 50. The alkene that will give the same product with HBr in the
gives absence as well as in the presence of peroxide is
(a) isopropyl bromide (b) 3-bromo propane (a) 2-butene (b) 1-butene
(c) allyl bromide (d) n-propyl bromide (c) propene (d) 1-hexene

42. H 3 C - CH - CH = CH 2 + HBr ® A 51. Ethylene reacts with alkaline KMnO4 to form

|
(a) Oxalic acid (b) HCHO
CH 3 (c) Ethyl alcohol (d) Glycol
A(predominantly) is : 52. The reaction of HI with CH3 – CH = CH2 at 400°C yields :
(a) CH 3 - CH - CH 2 - CH 2 Br (a) CH2 I – CH = CH2 (b) CH3 – CHI – CH3
|
(c) CH3 – CH2 – CH2 I (d) CH2I – CH2 – CH2I
CH 3
HYDROCARBONS 171

53. Ethene when treated with Br2 in the presence of CCl4 which (b) Assertion is correct, reason is correct; reason is not a
compound is formed? correct explanation for assertion
(a) 1, 2-dibromoethane (b) 1-bromo-2-chloroethane (c) Assertion is correct, reason is incorrect
(c) Both (a) and (b) (d) 1, 1, 1-tribromoethane (d) Assertion is incorrect, reason is correct.
54. The test for unsaturation is confirmed by the decolourisation 61. The nodal plane in the p-bond of ethene is located in
of which of the following (a) the molecular plane
(a) Iodine water (b) CuSO4 solution (b) a plane parallel to the molecular plane
(c) Bromine water (d) All of these (c) a plane perpendicular to the molecular plane which bisects
55. Isopropyl alcohol is obtained by reacting which of the the carbon - carbon s -bond at right angle
following alkenes with conc. H2SO4 and H2O (d) a plane perpendicular to the molecular plane which
(a) Ethylene (b) Propylene contains the carbon - carbon s -bond.
(c) 2-methyl propene (d) Isoprene 62. The IUPAC name of the compound having the formula
56. Which of the following statements are correct ? (CH3)3CCH = CH2 is –
(i) The general formula of alkenes is CnH2n. (a) 3, 3, 3-trimethyl-1-propane
(ii) Alkenes are also known as paraffins. (b) 1, 1, 1-trimethyl-1-butene
(iii) Bond length of C–C double bond in alkene is shorter (c) 3, 3-dimethyl-1-butene
than C–C single bond in alkane. (d) 1, 1-dimethyl-1, 3-butene
(iv) Carbon–Carbon double bond in alkene consists of two 63. Correct order of stability is :
sigma bonds. (a) cis -2- butene > 1-butene > trans -2-butene
(v) Alkenes are easily attacked by electrophilic reagent. (b) trans-2-butene > cis-2-butene > 1-butene
(a) (i) and (iv) (b) (i), (iii) and (v) (c) 1-butene > cis-2-butene > trans-2- butene
(c) (i) and (iii) (d) (i), (ii), (iv) and (v) (d) cis-2-butene > trans-2-butene > 1-butene
57. Which of the following statements are correct ? 64. Which of the following is correct set of physical properties
(i) Cis form of alkene is polar whereas trans form is of the geometrical isomers?
non-polar CH3 CH3
(ii) Cis form of alkene is non-polar whereas trans form is
polar.
(iii) In case of solid alkenes the trans isomer has higher
melting point than the cis isomer. Dipole moment B.P. M.P. Stability
(iv) Cis and trans both form have same properties. (a) I > II I > II II > I I > II
(a) (i) and (iii) (b) (ii) and (iii) (b) II > I II > I II > I II > I
(c) (i), (iii) and (iv) (d) (i) and (iv) (c) I > II I > II I > II I > II
58. Match the columns (d) II > I II > I I > II I > II
Column-I Column-II 65. But-2-ene exhibits cis,trans-isomerism due to
(A) CH º CH + H2 ¾¾ ® CH 2 = CH 2 (p) Zn (a) rotation around C3 – C4 sigma bond
(B) CH 3CH 2 Br ¾¾
® CH2 = CH2 (q) Conc. H2SO4 (b) restricted rotation around C = C bond
(c) rotation around C1 – C2 bond
(C) CH 2 BrCH 2 Br ¾¾ ® CH2 = CH2 (r) Pd/C (d) rotation around C2 – C3 double bond
(D) CH3CH2OH ¾¾ ® CH2 = CH2 (s) Alc. KOH 66. When 3, 3-dimethyl 2-butanol is heated with H2SO4, the
(a) A – (r), B – (s), C – (p), D – (q) major product obtained is
(b) A – (s), B – (r), C – (q), D – (p) (a) 2,3-dimethyl 2-butene
(c) A – (q), B – (p), C – (s), D – (r) (b) 3, 3-dimethyl 1- butene
(d) A – (r), B – (s), C – (q), D – (p) (c) 2, 3-dimethyl 1- butene
59. Assertion : 1-Butene on reaction with HBr in the presence (d) cis & trans isomers of 2, 3-dimethyl 2-butene
of a peroxide produces 1-bromobutane. 67. Reaction of hydrogen bromide with propene in the absence
Reason : It involves the free radical mechanism. of peroxide is a/an
(a) Assertion is correct, reason is correct; reason is a (a) free radical addition
correct explanation for assertion. (b) nucleophilic addition
(b) Assertion is correct, reason is correct; reason is not a (c) electrophilic substitution
correct explanation for assertion (d) electrophilic addition
(c) Assertion is correct, reason is incorrect 68. CH2 = CHCl reacts with HCl to form
(d) Assertion is incorrect, reason is correct. (a) CH2Cl – CH2Cl (b) CH3 – CHCl2
60. Assertion : All the hydrogen atoms in CH2 = C = CH2 lie in (c) CH2 = CHCl.HCl (d) None of these
one plane. 69. The only alcohol that can be prepared by the indirect
Reason : Carbon atoms are sp2 and sp hybridized. hydration of alkene is
(a) Assertion is correct, reason is correct; reason is a (a) Ethyl alcohol (b) Propyl alcohol
correct explanation for assertion. (c) Isobutyl alcohol (d) Methyl alcohol
 EBD_7374
172 CHEMISTRY

70. In the presence of peroxide, hydrogen chloride and hydrogen (a) CH 3CH 2 CH 2 C º CCH 2CH 2 CH3
iodide do not give anti-Markownikov’s addition to alkenes
because (b) CH 3CH 2C º CH
(a) Both are highly ionic (c) CH 3CH = CHCH3
(b) One is oxidising and the other is reducing
(c) One of the steps is endothermic in both the cases (d) CH 3CH 2C º CCH 2CH3
(d) All the steps are exothermic in both the cases 81. Which of these will not react with acetylene?
71. Which of the following statements is incorrect regarding (a) NaOH (b) Ammonical AgNO3
dehydrohalogenation of alkenes ? (c) Na (d) HCl.
(a) During the reaction hydrogen atom is eliminated from 82. When acetylene is passed over heated iron tube, the product
the b - carbon atom. obtained is –
(b) Rate of reaction for same alkyl group; (a) C2H2 (b) C4H4 (c) C6H6 (d) C8H8
Iodine > Bromine > Chlorine 83. But–2–yne on chlorination gives
(c) Rate of reaction; (CH3)3C – > (CH3)2CH – > CH3CH2 – (a) 1 –chlorobutane
(d) Only nature of halogen atom determines rate of the (b) 1, 2 –dichlorobutane
reaction. (c) 1, 1, 2, 2 –tetrachlorobutane
(d) 2, 2, 3, 3 –tetrachlorobutane
Topic 3: Alkynes
84. When propyne reacts with aqueous H2SO4 in the presence
72. The IUPAC name of the compound of HgSO4, the major product is
CH3CH = CHC º CH is (a) Propanal
(a) Pent-l-yn-3-ene (b) Pent-4-yn-2-ene (b) Propyl hydrogen sulphate
(c) Pent-3-en-1-yne (d) Pent-2-en-4-yne (c) Acetone
73. Number of alkynes for formula C5H8 is – (d) Propanol
(a) 2 (b) 3 (c) 4 (d) 5 85. Propyne on polymerisation gives
(a) Mesitylene (b) Benzene
Reagent
74. R - CH 2 - CCl 2 - R ¾¾¾¾® R - C º C - R (c) Ethyl benzene (d) Propyl benzene
The reagent is 86. What happens when a mixture of acetylene and hydrogen
(a) Na (b) HCl in H2O is passed over heated Lindlar’s catalyst ?
(c) KOH in C2H5OH (d) Zn in alcohol. (a) Ethane and water are formed
75. Calcium carbide when treated with water gives : (b) Ethylene is formed
(a) ethylene (b) methane (c) Acetylene and ethane are formed
(c) acetylene (d) ethane (d) None of these
76. Which one of the following has the minimum boiling 87. Which of the following reaction is shown by alkynes ?
point ? (a) Addition (b) Substitution
(a) 1-Butene (b) 1-Butyne (c) Polymerization (d) All of these
(c) n- Butane (d) Isobutane 88. Which of the following reactions will yield 2,
77. Ammonical silver nitrate forms a white precipitate easily 2-dibromopropane ?
with (a) HC º CH + 2HBr ®
(a) CH3C º CH (b) CH3C º CCH3 (b) CH3C º CH + 2HBr ®
(c) CH3CH = CH 2 (d) CH2 = CH2 (c) CH3CH = CH 2 + HBr ®
78. When acetylene is passed through dil. H2SO4 in presence (d) CH3CH = CHBr + HBr ®
of HgSO4, the compound formed is
(a) ether (b) acetaldehyde 89. In the given reactions
A
(c) acetic acid (d) ketone CH 3C º CH ¾¾® CH 3CBr2 CHBr2
79. Which of the following will be the final product when C 2H2 B
reacts with HCl CH 3C º CH ¾¾
® CH 3CBr2 CH 3
Hg 2 + H +
CH 2 CH3 CH3C º CH ¾¾¾¾¾
®C
333 K
(a) P (b) |
CHCl CHCl 2 Hg 2+ H +
HC º CH ¾¾¾¾¾
®D
333 K
CHCl A, B, C and D are respectively
(c) P (d) None of these (a) HBr, Br2, CH3COCH3, CH3CHO
CHCl
(b) Br2, HBr, CH3COCH3, CH3CHO
80. The hydrocarbon which can react with sodium in liquid (c) HBr, HBr, CH3COCH3, CH3CHO
ammonia is (d) Br2, HBr, CH3CH2CHO, CH3CHO
 HYDROCARBONS 173

90. Which of the following polymer can be used as electrodes Topic 4: Aromatic Hydrocarbons
in batteries ?
98. Aromatic compounds burn with sooty flame because
(a) Polypropene (b) Polyacetylene
(a) they have a ring structure of carbon atoms
(c) Polyethene (d) Polyisoprene
(b) they have a relatively high percentage of hydrogen
91. Which of the following statements are correct ?
(c) they have a relatively high percentage of carbon
(i) Alkynes on reduction with palladised charcoal form
(d) they resist reaction with oxygen of air
cis alkenes.
99. The conditions for aromaticity is :
(ii) Alkynes on reduction with palladised charcoal form
(a) molecule must have cyclic clouds of delocalised p
trans alkenes.
electrons
(iii) Alkynes on reduction with sodium in liquid ammonia
(b) molecule must contain (4n + 2) p electrons
form trans alkenes.
(c) Both (a) and (b)
(iv) Propyne on reduction with palladised charcoal form a
(d) None of the above
mixture of cis and trans propene.
100. Select the true statement about benzene amongst the
(a) (i) and (iv) (b) (i) and (iii)
following
(c) (ii) and (iv) (d) (i), (iii) and (iv)
(a) Because of unsaturation benzene easily undergoes
92. How many structural isomers are possible for the alkyne
addition
C6H10 ?
(b) There are two types of C – C bonds in benzene molecule
(a) 7 (b) 6 (c) 8 (d) 5
(c) There is cyclic delocalisation of pi-electrons in benzene
93. Which of the following will have least hindered rotation
(d) Monosubstitution of benzene gives three isomeric
around carbon - carbon bond ?
products.
(a) Ethane (b) Ethylene
101. Benzene can be directly obtained from
(c) Acetylene (d) Hexachloroethane
(a) Acetylene (b) Phenol
94. Acetylenic hydrogens are acidic because
(c) Chlorobenzene (d) All the above
(a) Sigma electron density of C – H bond in acetylene is
nearer to carbon, which has 50% s-character COONa
(b) Acetylene has only one hydrogen on each carbon
(c) Acetylene contains least number of hydrogens among 102. NaOH + CaO
A
the possible hydrocarbons having two carbons
(d) Acetylene belongs to the class of alkynes with
molecular formula, CnH2n – 2. The product A is
95. The correct increasing order of acidity of the following (a) Benzene (b) Benzaldehyde
alkynes (c) Toluene (d) Benzoic acid
103. In a reaction of C6H5Y, the major product (> 60%) is
(1) CH3 - C º C - CH3
m-isomer, so the group Y is
(2) CH3 - C º CH (a) –COOH (b) –NH2
(3) CH º CH (c) –OH (d) –Cl
(a) 1 < 2 < 3 (b) 2 < 3 < 1 HNO Br
(c) 3 < 2 < 1 (d) 1 < 3 < 2 104. ¾¾¾¾ 3 ® A ¾¾¾®2 B. The compound B is
H SO 2 FeBr
4 2
96. Identify the alkyne in the following sequence of reactions.
H Ozonolysis Wacker NO2 NO2
Alkyne ¾¾¾¾¾¾¾
2 ® A ¾¾¾¾¾
® B ¬¾¾¾¾
Lindlar's catalyst only Process Br
(a) (b)
(a) H3C - C º C - CH3
Br
(b) H3C - CH 2 - C º CH NO2
NO2
=
(c) H 2C CH - C º CH
(d) HC º C - CH 2 - C º CH (c) (d)
97. Which of the following represents the correct order of acidic Br Br
Br
strength ?
105. Chlorobenzene is o, p-directing in electrophilic substitution
(i) HC º CH > H 2C = CH 2 > CH3 - CH3
reaction. The directing influence is explained by
(ii) HC º CH > CH3 - CH3 > H 2C = CH 2 (a) + M of Ph (b) +I of Cl
(iii) CH3C º CH > HC º CH > CH3 - C º C - CH3 (c) + M of Cl (d) + I of Ph
(iv) HC º CH > CH3 - C º CH > CH3 - C º C - CH3 106. Catalytic hydrogenation of benzene gives
(a) (i) and (iii) (b) (ii) and (iv) (a) xylene (b) cyclohexane
(c) (i) and (iv) (d) (i) and (iv) (c) benzoic acid (d) toluene
 EBD_7374
174 CHEMISTRY

107. The strongest ortho - para and strongest meta - directing (iv) They are also produced in human body due to various
groups respectively are biochemical reactions.
(a) –NO2 and –NH2 (b) –CONH2 and –NH2 (a) (i), (ii) and (iv) (b) (i), (iii) and (iv)
(c) –NH2 and –CONH2 (d) –NH2 and –NO2 (c) (ii), (iii) and (iv) (d) (i), (ii) and (iii)
108. For the formation of toluene by Friedal Craft reaction, 118. Match the following reactants in Column I with the
reactants used in presence of anhydrous AlCl 3 are corresponding reaction products in Column II and choose
(a) C2H2 and CCl4 (b) CH4 and CaCN2 the correct option from the codes given below.
(c) C6H6 and CH3Cl (d) C2H5 OH and Zn Column - I Column - II
109. Benzene can be obtained in the reaction AlCl3
(A) Benzene + Cl2 ¾¾¾® (p) Benzoic acid
(a) Ethene + 1, 3-butadiene
(b) Trimerisation of ethyne (B) Benzene + CH3Cl (q) Methyl phenyl
(c) Reduction of PhCHO AlCl3
¾¾¾® ketone
(d) All of these
(C) Benzene + CH3COCl (r) Toluene
BHC, anhydrous
110. C6 H6 + CH3Cl ¾¾¾¾¾¾¾ ® C6 H5CH3 + HCl AlCl
AlCl 3 ¾¾¾®
3
is an example of
KMnO4 / NaOH
(a) Friedel - Craft’s reaction (D) Toluene ¾¾¾¾¾¾ ¾
® (s) Chlorobenzene
(b) Kolbe’s synthesis (a) A – (s), B – (r), C – (q), D – (p)
(c) Wurtz reaction (b) A – (s), B – (r), C – (p), D – (q)
(d) Grignard reaction (c) A – (r), B – (s), C – (p), D – (q)
111. Benzene reacts with CH3COCl + AlCl3 to give (d) A – (r), B – (s), C – (q), D – (p)
(a) chlorobenzene (b) toluene 119. Match the columns
(c) benzyl chloride (d) acetophenone Column - I Column - II
112. Benzene on reaction with ozone forms __________. (A) Alkyl halide + Alkyl halide (p) Sulphonation
(a) 2 molecules of aldehyde and 1 molecule of ketone in presence of dry ether
(b) 2 molecules of ketone and 1 molecule of aldehyde (B) Arene + Acid halide (q) Wurtz reaction
(c) triozonide in presence of AlCl3
(d) hexaozonide (C) Arene + Fuming sulphuric (r) Catalytic
113. AlCl3 acts as ________ in Friedel-Crafts reaction in presence of AlCl3 hydrogenation
(a) nucleophile (b) electrophile (D) Arene + Hydrogen (s) Friedel-Crafts
(c) free radical (d) intermediate in presence of Ni reaction
114. The electrophilic substitution reactions of benzene takes (a) A - (p), B - (r), C - (q); D - (s)
place via (b) A - (s), B - (q), C - (r); D - (p)
(i) generation of electrophile (c) A - (r), B - (p), C - (s); D - (q)
(ii) generation of nucleophile (d) A - (q), B - (s), C - (p); D - (r)
(iii) formation of carbocation intermediate 120. Match the columns
(iv) removal of proton from the carbocation intermediate Column - I Column - II
(a) (i), (iii) and (iv) (b) (ii), (iii) and (iv) (A) Aromatic (p) Planar
(c) (i) and (iv) (d) (ii) and (iv) (B) Antiaromatic (q) Non-planar
115. During the nitration of benzene. In the process of generation (C) Huckel rule (r) 4 np localised
of nitronium ion sulphuric acid behaves as a/an ______ electrons
and nitric acid behave as a/an _________. (D) Cyclo-octatetraene (s) (4 n + 2)p delocalised
(a) base, acid (b) acid, base electrons
(c) strong acid, weak acid (d) weak acid, strong acid (a) A - (p, s), B - (p, r), C - (s), D - (q, r)
116. Benzene is highly unsaturated but it does not undergo (b) A - (p, r), B - (p, s), C - (s), D - (q, r)
addition reaction because (c) A - (p, s), B - (s), C - (p, r), D - (q, r)
(a) p-electrons of benzene are delocalised. (d) A - (q, r), B - (p, r), C - (s), D - (p, s)
(b) cyclic structures do not show addition reaction 121. Assertion : Tropylium cation is aromatic in nature
(c) benzene is a non-reactive compound
(d) All of the above
117. Which of the following statements are correct ?
(i) Polynuclear hydrocarbons contain two or more benzene Reason : The only property that determines its aromatic
rings fused together. behaviour is its planar structure.
(ii) Polynuclear hydrocarbons have carcinogenic property. (a) Assertion is correct, reason is correct; reason is a
(iii) Polynuclear hydrocarbons are formed on incomplete correct explanation for assertion.
combustion of organic materials like tobacco, coal and (b) Assertion is correct, reason is correct; reason is not a
petroleum. correct explanation for assertion
HYDROCARBONS 175

(c) Assertion is correct, reason is incorrect (b) 7 p-orbitals and 7 unpaired electrons
(d) Assertion is incorrect, reason is correct. (c) 6 p-orbitals and 7 unpaired electrons
122. Which one of these is not compatible with arenes? (d) 6 p-orbitals and 6 unpaired electrons
(a) Greater stability 127. (i) Chlorobenzene and (ii) benzene hexachloride are
obtained from benzene by the reaction of chlorine, in the
(b) Delocalisation of p-electrons
pesence of
(c) Electrophilic additions
(a) (i) Direct sunlight and (ii) anhydrous AlCl3
(d) Resonance (b) (i) Sodium hydroxide and (ii) sulphuric acid
123. The carbon-carbon bond length in benzene is (c) (i) Ultraviolet light and (ii) anhydrous FeCl3
(a) Same as in C2H4 (d) (i) Anhydrous AlCl3 and (ii) direct sunlight
(b) In between C2H6 and C2H2 128. A group which deactivates the benzene ring towards
(c) In between C2H4 and C2H2 electrophilic substitution but which directs the incoming
(d) In between C2H6 and C2H4 group principally to the o-and p-positions is
124. Point out the wrong statement in relation to the structure of (a) –NH2 (b) –Cl (c) –NO2 (d) –C2H5
benzene 129. Benzene can be obtained by heating either benzoic acid
with X or phenol with Y. X and Y are respectively.
(a) It forms only one monosubstitution product
(a) Zinc dust and soda lime
(b) The C - C bond distance in benzene is uniformly 1.397Å (b) Soda lime and zinc dust
(c) It is a resonance hybrid of a number of canonical forms (c) Zinc dust and sodium hydroxide
(d) It has three delocalised p-molecular orbitals (d) Soda lime and copper
125. The ratio of s to p bonds in benzene is : 130. Which of the following chemical system is non aromatic?
(a) 2 (b) 3 (c) 4 (d) 8
(a) (b)
.
126. The radical, CH2 is aromatic because it has :

(a) 7 p-orbitals and 6 unpaired electrons (c) (d)

S

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (c) 3-ethyl-5-isopropyloctane
(d) 3-isopropyl-6-ethyloctane
1. Arrange the following in decreasing order of their boiling 5. The addition of HBr to 1-butene gives a mixture of products
points. A, B and C.
1. n–butane 2. 2-methylbutane
3. n–pentane 4. 2, 2-dimethylpropane Br C2H5
(a) 1 > 2 > 3 > 4 (b) 2 > 3 > 4 > 1
(c) 4 > 3 > 2 > 1 (d) 3 > 2 > 4 > 1 C C
(A) H5C2 CH3 (B) H CH3
2. Arrange the halogens F2, Cl2, Br 2, I2, in order of their
increasing reactivity with alkanes. H Br
(a) I2 < Br2 < Cl2 < F2 (b) Br2 < Cl2 < F2 < I2 (C) CH3 - CH 2 - CH 2 - CH 2 - Br
(c) F2 < Cl2 < Br2 < I2 (d) Br2 < I2 < Cl2 < F2
The mixture consists of
3. The increasing order of reduction of alkyl halides with zinc
(a) A and B as major and C as minor products
and dilute HCl is
(b) B as major, A and C as minor products
(a) R – Cl < R – I < R – Br (b) R — Cl < R – Br < R – I
(c) B as minor, A and C as major products
(c) R – I < R – Br < R – Cl (d) R – Br < R – I < R – Cl
(d) A and B as minor and C as major products
4. The correct IUPAC name of the following alkane is
6. Which of the following will not show geometrical isomerism?
H3 C - CH2 - CH - CH2 - CH2 - CH - CH2 - CH3 F H F F
| | (a) C=C (b) C=C
CH CH 2 Cl D Cl Cl
|
CH3 H3C C2H5 CH3 CH3
CH3 CH3
(c) C=C (d) C=C
(a) 3, 6-diethyl-2-methyloctane H5C2 CH3 C2H5
CH3
(b) 5-isopropyl-3-ethyloctane
 EBD_7374
176 CHEMISTRY

7. Arrange the following hydrogen halides in order of their 14. Assertion : Tropylium cation is aromatic in nature
decreasing reactivity with propene.
(a) HCl > HBr > HI (b) HBr > HI > HCl
(c) HI > HBr > HCl (d) HCl > HI > HBr
8. Arrange the following carbanions in order of their decreasing Reason : The only property that determines its aromatic
stability. behaviour is its planar structure. [AIIMS 2014, 2016, C]
A. H3C — C º C – B. H — C º C – (a) If both Assertion and Reason are correct and Reason
C. H3C — CH 2 is the correct explanation of Assertion.
(b) If both Assertion and Reason are correct, but Reason
(a) A > B > C (b) B > A > C
is not the correct explanation of Assertion.
(c) C > B > A (d) C > A > B
(c) If Assertion is correct but Reason is incorrect.
9. Arrange the following alkyl halides in decreasing order of
(d) If both the Assertion and Reason are incorrect.
the rate of b – elimination reaction with alcoholic KOH.
15. The major organic compound formed by the raction of
H 1, 1, 1-trichloroethane with silver powder is:
| [JEE M 2014, S]
A. CH3 - C - CH 2 Br (a) Acetylene (b) Ethene
|
(c) 2 - Butyne (d) 2 - Butene
CH3
16. An organic compound A (C4H9Cl) on reaction with Na/
B. CH3 — CH2 — Br diethyl ether gives a hydrocarbon which on
C. CH3 — CH2 — CH2 — Br monochlorination gives only one chloro derivative, then A
(a) A > B > C (b) C > B > A is [BITSAT 2014, C]
(c) B > C > A (d) A > C > B (a) tert-butyl chloride (b) sec-butyl chloride
10. Which of the following reactions of methane is incomplete (c) isobutyl chloride (d) n-butyl chloride
combustion? 17. 2,3-Dimethyl-2-butene can be prepared by heating which of
Cu / 523 K /100 atm the following compounds with a strong acid ?
(a) 2CH 4 + O 2 ¾¾¾¾¾¾¾¾
® 2CH 3OH [AIPMT 2015 RS, S]
Mo O
(b) CH 4 + O 2 ¾¾¾¾
2 3 ® HCHO + H O
2 (a) (CH3)2 CH – CH – CH = CH2
|
CH3
(c) ® C ( s ) + 2H 2 O ( l )
CH 4 + O 2 ¾¾
(b) (CH3)3 C – CH = CH2
(d) ® CO 2 ( g ) + 2H 2 O ( l )
CH 4 + 2O 2 ¾¾ (c) (CH3)2C = CH – CH2 – CH3
Past Year MCQs (d) (CH3)2CH – CH2 – CH = CH2
11. Which of the following organic compounds has same 18. In the reaction with HCl, an alkene reacts in accordance
hybridization as its combustion product (CO2)? with the Markovnikoff's rule, to give a product 1-chloro-1-
[AIPMT 2014, S] methylcyclohexane. The possible alkene is :
(a) Ethane (b) Ethyne [AIPMT 2015 RS, A]
(c) Ethene (d) Ethanol CH2 CH3
12. Predict the nature of P in the following reaction
NaNH / inert solvent
2 ¾ ¾ ¾¾® P (a) (b)
CH 3 C º CCH 3 ¾¾ ¾ ¾
heat

(a) CH2 = CHCH = CH2 [AIIMS 2014, C]

(b) CH2= C = CH – CH3 CH3
(c) CH3CH2C º CH
(c) (a) and (b) (d)
(d) No reaction
13. Assertion : Trans-2-butene on reaction with Br2 gives meso-
2, 3-dibromobutane. [AIIMS 2009, 2014, C] 19. A single compound of the structure : [AIPMT 2015, A]
Reason : The reaction involves syn-addition of bromine. CH3 CH3
(a) If both Assertion and Reason are correct and Reason OHC C C
is the correct explanation of Assertion. C H C O
(b) If both Assertion and Reason are correct, but Reason H2 H2
is not the correct explanation of Assertion. is obtainable from ozonolysis of which of the following cyclic
(c) If Assertion is correct but Reason is incorrect. compounds ?
(d) If both the Assertion and Reason are incorrect.
HYDROCARBONS 177

(a) Bromine in carbon tetrachloride

H3C H3C CH3 (b) Bromine in acetic acid
(a) (b) (c) Alk KMnO4
H3C
(d) Ammonical silver nitrate.
25. Assertion : 1-Butene on reaction with HBr in the presence of a
CH3 peroxide produces 1-bromobutane. [AIIMS 2015, C]
H3C Reason : It involves the formation of a primary radical.
(c) (d) CH3 (a) If both Assertion and Reason are correct and Reason
CH3 is the correct explanation of Assertion.
(b) If both Assertion and Reason are correct, but Reason
20. The total number of p-bond electrons in the following is not the correct explanation of Assertion.
structure is : [AIPMT 2015, S] (c) If Assertion is correct but Reason is incorrect.
H H H (d) If both the Assertion and Reason are incorrect.
H3C 26. Which compound would give 5 - keto - 2 - methylhexanal
CH3 upon ozonolysis ? [JEE M 2015, A]
H3C CH3
CH3
H2C H CH3
(a) (b) H3C
(a) 8 (b) 12 (c) 16 (d) 4
21. Given: CH3
CH3
H3C CH3 H3C CH2 H2C CH2 CH3

(c) CH3 (d)

CH3
CH3 CH3 CH2 27. In the reaction
(I) (II) (III) (i) NaNH 2 / liq.NH3 (i) NaNH 2 / liq.NH 3
H - C º CH X Y
(ii) CH3CH 2 Br (ii) CH 3 CH 2 Br
The enthalpy of the hydrogenation of these compounds
will be in the order as : [AIPMT 2015, C] X and Y are [NEET 2016, S]
(a) III > II > I (b) II > III > I (a) X = 1-Butyne ; Y = 3-Hexyne
(c) II > I > III (d) I > II > III (b) X = 2-Butyne ; Y = 3-Hexyne
22. The oxidation of benzene by V2O5 in presence of air (c) X = 2-Butyne ; Y = 2-Hexyne
produces : [AIPMT 2015 RS, C] (d) X = 1-Butyne ; Y = 2-Hexyne
(a) benzoic anhydride (b) maleic anhydride 28. The alkene that will give the same product with HBr in the
(c) benzoic acid (d) benzaldehyde absence as well as in the presence of peroxide is
23. The reaction of C6H5CH = CHCH3 with HBr produces: [AIIMS 2016, S]
[AIPMT 2015, A] (a) 2-butene (b) 1-butene
(a) C6 H5CH 2CHCH3 (b) C6 H5CH 2CH 2CH 2Br (c) propene (d) 1-hexene
| 29. Assertion : Energy of resonance hybrid is equal to the
Br average of energies of all canonical forms.
CH=CHCH3
Reason : Resonance hybrid cannot be presented by a single
structure. [AIIMS 2016, C]
(c) (d) C 6 H 5 C HCH 2 CH3 (a) If both Assertion and Reason are correct and Reason
| is the correct explanation of Assertion.
Br
(b) If both Assertion and Reason are correct, but Reason
Br is not the correct explanation of Assertion.
24. Which is the most suitable reagent among the following to (c) If Assertion is correct but Reason is incorrect.
distinguish compound (3) from rest of the compounds ? (d) If both the Assertion and Reason are incorrect.
[AIIMS 2015, S] 30. The reaction of propene with HOCl (Cl 2 + H2O) proceeds
1. CH3– C º C – CH3 through the intermediate: [JEE M 2016, C]
2. CH 3 - CH 2 - CH 2 - CH 3 (a) CH 3 – CH ( OH ) - CH 2+
3. CH 3 - CH 2C º CH (b) CH 3 – CHCl - CH 2+
4. CH 3 - CH = CH 2.
(c) CH 3 – CH + - CH 2 – OH
(d) CH 3 – CH + - CH 2 – Cl
 EBD_7374
178 CHEMISTRY

31. The product of the reaction given below is: (a) A : H3C – C = CH2 B : H3C – C = CH2
| |
1. NBS/hv OH SO4
2. H 2O/K 2CO 3
X
[JEE M 2016, S] (b) A : H3C - C - CH3 B : H3C – C º CH
||
O
O CO2H
(c) A : H3C – C = CH2 B : H3C – C – CH3
| ||
(a) (b) OH O
(d) A : H3C – C = CH2 B : H3C - C - CH3
| ||
OH O
SO4
(c) (d) 37. The end product (C) in the following sequence of reactions is
[AIIMS 2017, A]
32. Give the possible structure of X in the following reaction : 1% HgSO
HC º CH ¾¾ ¾ ¾¾
4 ® A ¾¾ ¾
3 ¾
¾® B ¾¾®
CH MgX
¾ (C )
[O]
[BITSAT 2016, A] 20% H 2SO 4 H 2O
D O (a) acetic acid (b) isopropyl alcohol
C6H6 + D2SO4 ¾¾¾
2 ®
X
(c) acetone (d) ethanol
SO3D SO3D
38. In the given reaction
D X
(a) (b) CH3CH 2 CH = CHCH3 ¾¾®
CH3CH 2COOH +CH3COOH
The X is [AIIMS 2017, A]
D
SO3H (a) C2 H5ONa
D D
(b) Conc. HCl +Anhy.ZnCl2
D
(c) (d) (c) Anh. AlCl3
D D (d) KMnO4/OH–
D 39. Assertion : Benzene exhibit two different bond lengths, due
to C – C single and C = C double bonds. [AIIMS 2017, C]
H /Pt D /Pt
33. CH3C º CCH3 ¾¾¾¾ 2 ® A ¾¾¾¾ 2 ® B Reason : Actual structure of benzene is a hybrid of
The compounds A and B, respectively are following two structures.
[BITSAT 2016, A]
(a) cis-but-2ene and rac-2, 3-dideuterobutane ¬¾®
(b) trans-but-2ene and rac-2, 3-dideuterobutane
(c) cis-but-2ene and meso-2, 3-dideuterobutane 40. 3-Methyl-pent-2-ene on reaction with HBr in presence of
(d) trans-but-2ene and meso-2, 3-dideuterobutane peroxide forms an addition product. The number of possible
34. With respect to the conformers of ethane, which of the stereoisomers for the product is : [JEE M 2017, C]
following statements is true ? [NEET 2017, C]
(a) Six (b) Zero (c) Two (d) Four
(a) Bond angle changes but bond length remains same
(b) Both bond angle and bond length change 41. In the following structures, which two forms are staggered
(c) Both bond angles and bond length remains same conformations of ethane ? [BITSAT 2017, C]
(d) Bond angle remains same but bond length changes H
35. Which one is the correct order of acidity ? [NEET 2017, C] H H H
(a) CH º CH > CH3 – C º CH > CH2 = CH2 > CH3 – CH3 H
(b) CH º CH > CH2 = CH2 > CH3 – C º CH > CH3 – CH3 H
(c) CH3 – CH3 > CH2 = CH2 > CH3 – C º CH> CH º CH H H
H
(d) CH2 = CH2 > CH3 – CH = CH2 > CH3 – C º CH > CH º CH H
36. Predict the correct intermediate and product in the following H
reaction : [NEET 2017, S] H
H O, H SO (1) (2)
H3C - C º CH ¾¾¾¾¾¾
2 2 4 ® Intermediate ® product
HgSO 4 (A) (B)
HYDROCARBONS 179

H 45. What is impact on benzene in magnetic field?

H [AIIMS 2018, C]
H (a) Strongly attract (b) Weakly attract
H (c) Strongly repel (d) Weakly repel
H
H H 46. The trans-alkenes are formed by the reduction of alkynes
H H H H
H with: [JEE M 2018, C]
(3) (4) (a) H2-Pd/C, BaSO4 (b) NaBH4
(a) 1 and 4 (b) 2 and 3 (c) 1 and 2 (d) 1 and 3 (c) Na/liq. NH3 (d) Sn - HCl
42. Hydrocarbon (A) reacts with bromine by substitution to 47. In a set of reactions, ethylbenzene yielded a product D.
form an alkyl bromide which by Wurtz reaction is converted CH2CH 3 KMnO Br2 C 2H 5OH
to gaseous hydrocarbon containing less than four carbon ¾¾¾® 4
B ¾¾® C ¾¾¾®H+
D
KOH FeCl
atoms. (A) is [NEET 2018, S] 3

(a) CH º CH (b) CH2 = CH2 [BITSAT 2018, A]

(c) CH4 (d) CH3 – CH3
43. The compound C7H8 undergoes the following reactions: CH2 – CH – COOC 2H5
(a)
3Cl / D Br /Fe Zn /HCl Br
C7 H8 ¾¾¾¾
2 ® A ¾¾¾¾
2 ® B ¾¾¾¾® C
The product 'C' is [NEET 2018, S] Br
(a) m-bromotoluene
(b) o-bromotoluene (b)
(c) p-bromotoluene Br
(d) 3-bromo-2,4,6-trichlorotoluene
CH2 COOC2H5
44. In the reaction, Ph – CH2 – CH2 – C º C – CH3
Na/NH Cl2 /hv COOH
¾¾¾¾ 3® A
¾¾¾¾ ® B, B is [AIIMS 2018, A]
(a) Ph – CH(Cl) – CH2 CH3
C=C (c)
H H OCH2CH3
(b) Ph – CH(Cl) – CH2 H
C=C COOC2H5
H CH3
(c) Ph – CH2 – CH(Cl) – CH = CH – CH3 (d)
(d) None of these Br

Exercise 3 : Try If You Can

1. Arrange in the correct order of stability (decreasing order) (a) (I) > (II) > (III) > (IV) (b) (IV) > (III) > (II) » (I)
for the following molecules : (c) (I) > (II) » (III) > (IV) (d) (III) > (I) » (II) > (IV)
Me CH3 Ha
2.
Hb
H
H + Br• ®
(I) (II) H Me d
H OH
Me H
Me CH2 ¾ H c

H Br• will abstract which of the hydrogen most readily?

(a) a (b) b (c) c (d) d
H Me 3. An organic compound C4H6 on ozonolysis give HCHO, CO2,
H CH3CHO. Compound will be:
(III) (IV) H
(a) H2C CH — CH CH2
Me Me
Me (b) CH3— CH C CH2
 EBD_7374
180 CHEMISTRY

(c) CH3— C C — CH3 8. Products of the following reaction:

(d) (1) O
CH3CºCCH2CH3 ¾¾¾¾¾¾ 3
(2) oxidation
® ...... are:
CH3 CH3
C CH2 (a) CH3COOH + CO2
4. C CH2
CH3 CH3O (b) CH3COOH + HOOC ×CH2CH3
(A) (B) (c) CH3CHO + CH3CH2CHO
(d) CH3COOH + CH3COCH3
CH3
C CH2 9. Callene, C7H6, is expected to be a fairly polar aromatic
CH3OCH2 molecule. Which of the following resonance forms
contributes to the greatest extent towards the real structure
(C) (resonance hybrid) of the molecule?
Arrange the above in the decreasing order of reactivity
towards HBr:
(a) A > B > C (b) B > A > C + :–

(c) B > C > A (d) A > C > B (a) (b)

CH3
|
5. Isoprene, CH 2 = C - CH = CH 2 is treated with HCl, the
products formed will be a mixture of + –1

CH3 CH3
| | (c) (d)
(i) CH 3 - C - CH = CH 2 (ii) CH 2 = C - C = CH3 +
| |
Cl Cl
(P)
, hv
CH3 CH3 Cl 2
| |
(iii) CH 3 - C = CH - CH 2Cl (iv) ClCH 2 - C = CH - CH3 10. Cl
2 /A
lC
(a) (i) and (iii) (b) (ii) and (iii) l3

(c) (ii) and (iv) (d) All the four. (Q)

6. In the presence of platinum catalyst, hydrocarbon A adds Identify major product of both reactions P and Q respectively.
hydrogen to form n-hexane. When hydrogen bromide is
added to A instead of hydrogen, only a single bromo CH2 Cl
compound is formed. Which of the following is A?
Cl
(a) CH 3 — CH 2 — CH = CH — CH 2 — CH 3 (a)
(b) CH 3 — CH 2 — CH 2 — CH = CH — CH 3
(c) CH 3 — CH = CH — CH 2 — CH 2 — CH 3

(d) CH 2 = CH — CH 2 — CH 2 — CH 2 — CH 3

7. Me H Me (b)
Cl
H Cl

Me H
Cl
Hydrogenation of the above compound in the presence of (c)
poisoned palladium catalyst gives
(a) an optically active compound Cl
(b) an optically inactive compound
(c) a racemic mixture
(d) a diastereomeric mixture
HYDROCARBONS 181

H SO
13. HC º C - COOH ¾¾2 ¾¾
4® X
. The compound X is
Cl HgSO 4
(d)
(a) OHC.CH 2 .COOH (b) HOCH = CHCOOH
Cl Cl (c) both (a) and (b) (d) CH 2 = C(OH )COOH
11. Which of the following compounds are antiaromatic 14. Which of the following order is true regarding electrophilic
aromatic substitution of the three given compounds?

CH 3 CH 3 CH 3
O
– +
(I) (II) (III) (IV) (V) (VI)
CH 3
(a) (I) and (V) (b) (II) and (V)
CH 3
(c) (I) and (IV) (d) (III) and (VI) I II III

(a) II = III > I (b) II = III = I

(c) II >>> III > I (d) II >>> III = I
12. + HBr Z, Z is
15. A hydrocarbon with molecular formula C8H18 gives only
OH one monochloro derivative, on chlorination. The
compound is
Br (a) n-octane
Br
(b) iso-octane
(c) 2,2,4-trimethylpentane
(a) (b)
(d) 2,2,3,3-tetramethylbutane
OH OH

Br

(c) (d)

Br Br
 EBD_7374
182 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 14 (c) 27 (b) 40 (d) 53 (a) 66 (a) 79 (b) 92 (a) 105 (c) 118 (a)
2 (c) 15 (d) 28 (d) 41 (d) 54 (c) 67 (d) 80 (b) 93 (a) 106 (b) 119 (d)
3 (d) 16 (c) 29 (a) 42 (b) 55 (b) 68 (b) 81 (a) 94 (a) 107 (d) 120 (a)
4 (d) 17 (b) 30 (a) 43 (c) 56 (b) 69 (a) 82 (c) 95 (a) 108 (c) 121 (c)
5 (a) 18 (b) 31 (d) 44 (a) 57 (a) 70 (c) 83 (d) 96 (a) 109 (b) 122 (c)
6 (c) 19 (c) 32 (b) 45 (c) 58 (a) 71 (d) 84 (c) 97 (c) 110 (a) 123 (d)
7 (b) 20 (b) 33 (a) 46 (d) 59 (a) 72 (c) 85 (a) 98 (c) 111 (d) 124 (d)
8 (a) 21 (b) 34 (c) 47 (c) 60 (d) 73 (b) 86 (b) 99 (c) 112 (c) 125 (c)
9 (d) 22 (a) 35 (c) 48 (d) 61 (a) 74 (c) 87 (d) 100 (c) 113 (b) 126 (d)
10 (d) 23 (c) 36 (d) 49 (c) 62 (c) 75 (c) 88 (b) 101 (d) 114 (a) 127 (a)
11 (a) 24 (b) 37 (c) 50 (a) 63 (b) 76 (d) 89 (b) 102 (a) 115 (b) 128 (b)
12 (b) 25 (b) 38 (a) 51 (d) 64 (c) 77 (a) 90 (b) 103 (a) 116 (a) 129 (b)
13 (c) 26 (a) 39 (b) 52 (b) 65 (b) 78 (b) 91 (b) 104 (a) 117 (d) 130 (a)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (d) 6 (d) 11 (b) 16 (a) 21 (a) 26 (d) 31 (d) 36 (c) 41 (c) 46 (c)
2 (a) 7 (c) 12 (c) 17 (b) 22 (b) 27 (a) 32 (d) 37 (c) 42 (c) 47 (d)
3 (b) 8 (b) 13 (c) 18 (c) 23 (d) 28 (a) 33 (c) 38 (d) 43 (a)
4 (a) 9 (d) 14 (c) 19 (d) 24 (d) 29 (d) 34 (c) 39 (c) 44 (b)
5 (a) 10 (c) 15 (c) 20 (a) 25 (c) 30 (d) 35 (a) 40 (d) 45 (d)
Exercis e 3 : Try If You Can
1 (c) 3 (b) 5 (d) 7 (b) 9 (d) 11 (d) 13 (c) 15 (d)
2 (a) 4 (b) 6 (a) 8 (b) 10 (c) 12 (b) 14 (d)
 14 Chapter
ENVIRONMENTAL
CHEMISTRY

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Ozone layer deplection,
AIIMS 3 air and water pollution 2/5 4.8
JEE Main 2
BITSAT 2
 EBD_7374
184 CHEMISTRY
ENVIRONMENTAL CHEMISTRY 185
 EBD_7374
186 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Environmental and Atmospheric Pollution (c) don't have wavelength specific character.
(d) show wavelength specific behaviour near the earth
1. The type of pollution caused by spraying of DDT is while far from earth these have wavelength
(a) air and soil (b) air and water independent behaviour.
(c) air (d) air, water and soil 11. The greenhouse effect is because of the
2. What is DDT among the following ? (a) presence of gases, which in general are strong infrared
(a) Greenhouse gas absorbers, in the atmosphere
(b) A fertilizer (b) presence of CO2 only in the atmosphere
(c) Biodegradable pollutant (c) pressure of O3 and CH4 in the atmosphere
(d) Non-biodegradable pollutant (d) N2O and chlorofluorohydrocarbons in the atmosphere
3. The region containing water vapour is 12. The greenhouse gas is
(a) thermosphere (b) stratosphere (a) CO2 (b) SO2
(c) troposphere (d) mesosphere (c) N2 (d) H2S
4. High concentration of which of the following in atmosphere 13. Which of the following strategy is not a correct approach
leads to stiffness of flower buds which eventually fall off to reduce global warming ?
from plants? (a) Reducing the green house gas emission by limiting
(a) NO2 (b) SO2 the use of fossil fuels
(c) CFC (d) Smog (b) Increase the vegetation cover particularly the forest
5. The substance which is not regarded as a pollutant? for photosynthetic utilization of CO2
(a) NO2 (b) CO2 (c) Minimizing the use of nitrogen fertilizers in agriculture
(c) O3 (d) Hydrocarbons for reducing N2O emission
6. Which of the following is/are the hazardous pollutant(s) (d) Increasing the use of air conditioners, refrigeration
present in automobile exhaust gases? unit and production of plastic foams and propellants
(i) N2 (ii) CO in aerosal spray cans
(iii) CH4 (iv) Oxides of nitrogen 14. The substance having the largest concentration in acid
(a) (ii) and (iii) (b) (i) and (ii) rain is
(c) (ii) and (iv) (d) (i) and (iii) (a) H2CO3 (b) HNO3
7. The gas emitted by supersonic jet planes that slowly (c) HCl (d) H2SO4
depletes the concentration of ozone layer is 15. Which of the following statements is incorrect ?
(a) CO (b) NO (a) Smoke particulates consist of solid or mixture of solid
(c) SO2 (d) O2 and liquid particles formed during combustion of
8. Carbon monoxide (CO) is harmful to man because organic matter.
(a) it forms carbolic acid (b) Herbicides and insecticides that miss their target and
(b) it generates excess CO2 travel through air form mists.
(c) it is carcinogenic (c) Organic solvents, metals and metallic oxides form
(d) it competes with O2 for haemoglobin fume particles
9. Increase in global temperature increases the incidence of (d) None of these
which of the following infectious disease(s) 16. Which of the following green house gas is released in paddy
(i) Sleeping sickness (ii) Yellow fever field ?
(iii) Malaria (iv) Dengue I. CFCs II. CH4
(a) (ii) only (b) (i) and (ii) III. SO2
(c) (iii) and (iv) (d) (i), (ii), (iii) and (iv) (a) Only I (b) Only II
10. Green house gases (c) Only III (d) I and II
(a) allow shorter wavelength to enter earth's atmosphere 17. The main element of smog is
while doesn't allow longer wavelength to leave the (a) O3 and PAN (b) O3
earth's atmosphere. (c) PAN (d) PPN and PBN
(b) allow longer wavelength to enter earth atmosphere 18. Classical smog occurs in places of
while doesn't allow shorter wavelength to leave the (a) excess SO2 (b) low temperature
surface (c) high temperature (d) excess NH3
ENVIRONMENTAL CHEMISTRY 187

19. The smog is essentially caused by the presence of (c) Ozone absorbs infrared radiation.
(a) oxides of sulphur and nitrogen (d) Oxides of nitrogen in the atmosphere can cause the
(b) O2 and N2 depletion of ozone layer.
(c) O2 and O3 29. Which of the following chemical, harmful to ozone, is
(d) O3 and N2 released by chlorofluoro carbon?
20. Photochemical smog formed in congested metropolitan cities (a) Sulphur dioxide (b) Fluorine
mainly consists of (c) Chlorine (d) Nitrogen dioxide
(a) ozone, peroxyacetyl nitrate and NOx 30. In Antarctica ozone depletion is due to the formation of
(b) smoke, peroxyacetyl nitrate and SO2 following compound
(c) hydrocarbons, SO2 and CO2 (a) acrolein (b) peroxyacetyl nitrate
(d) hydrocarbons, ozone and SOx (c) SO2 and SO3 (d) chlorine nitrate
21. In almost all Indian metropolitan cities like Delhi, the major 31. Ozone is an important constituent of stratosphere because it
atmospheric pollutant(s) is/are (a) Destroys bacteria which are harmful to human life
(a) suspended particulate matter (SPM) (b) Prevents the formation of smog over large cities
(b) oxides of sulphur (c) Removes poisonous gases of the atmosphere by
(c) carbon dioxide and carbon monoxide reacting with them
(d) oxides of nitrogen (d) Absorbs ultraviolet radiation which is harmful to
22. The non-viable particulate among the following is human life
(a) dust (b) bacteria 32. The gas(es) not responsible for ozone depletion :
(c) moulds (d) fungi (a) NO and freons (b) SO2
23. The pollutants which came directly in the air from sources (c) CO2 (d) Both (b) and (c)
are called primary pollutants. Primary pollutants are 33. Which of the following statement(s) is / are correct ?
sometimes converted into secondary pollutants. Which of (i) Sulphuric acid, nitric acid as well as ammonium salts
the following belongs to secondary air pollutants? are components of acid rain.
(a) CO (b) Hydrocarbon (ii) Formation of acid rain can be reduced by using less
(c) Peroxyacetyl nitrate (d) NO sulphur content fossil fuels for power plants and
24. Which of the following statements about photochemical industries.
smog is wrong? (iii) Catalytic converters must be used in cars to reduce
(a) It has high concentration of oxidising agents the harmful effect of exhaust.
(b) It has low concentration of oxidising agent (iv) Main component of catalytic converter is ceramic
(c) It can be controlled by controlling the release of NO2, honey comb coated with metals like – Au, Ag, Pt etc.
hydrocarbons ozone, etc. (a) (i), (ii) and (iii) (b) (ii) and (iii)
(d) Plantation of some plants like pinus helps in controlling (c) (ii), (iii) and (iv) (d) (i), (ii), (iii) and (iv)
photochemical smog. 34. Which of the following statement(s) is/are correct ?
25. The biggest particulate matter is (i) Classical smog is a mixture of smoke, fog and sulphur
(a) HNO3 droplets (b) Soot dioxide.
(c) H2SO4 droplets (d) Fly ash (ii) Classical smog is also called oxidising smog
26. The aromatic compounds present as particulates are (iii) Hydrocarbons, NO2 and PAN are components of
(a) polycyclic aromatic hydrocarbons photochemical smog.
(b) benzene (a) (i) and (iii) (b) (i) and (ii)
(c) toluene (c) (iii) only (d) (i), (ii) and (iii)
(d) nitrobenzene 35. Match the columns
27. Which of the following can control the photochemical Column I Column II
smog ? (A) Acid rain (p) CHCl2 – CHF2
(A) Use of catalytic converters in automobiles. (B) Photochemical smog (q) CO
(B) Plantation of trees like pinus, pyrus, vitis etc. (C) Combination with (r) CO2
(C) Using less sulphur containing fossil fuels. haemoglobin
(a) A and C (b) B (D) Depletion of ozone (s) SO2
(c) A and B (d) A, B and C layer (t) Unsaturated
28. Identify the incorrect statement from the following : hydrocarbons
(a) Ozone absorbs the intense ultraviolet radiation of the (a) A – (r, s), B – (t, s), C – (q), D – (p)
sun. (b) A – (r), B – (s), C – (q), D – (p)
(b) Depletion of ozone layer is because of its chemical (c) A – (t,s), B – (s), C – (q), D – (r)
reactions with chlorofluoro alkanes. (d) A – (r), B – (t), C – (q), D – (p)
 EBD_7374
188 CHEMISTRY

36. Match the columns 43. In which of the following regions hydrogen and helium are
Column-I Column-II found ?
(A) Oxides of sulphur (p) Global warming (a) Stratosphere (b) Mesosphere
(B) Nitrogen dioxide (q) Damage to kidney (c) Exosphere (d) Troposphere
(C) Carbon dioxide (r) ‘Blue baby’ syndrome 44. Assertion : Uncatalysed oxidation of sulphur dioxide is a
(D) Nitrate in drinking (s) Respiratory diseases slow process.
water Reason : Particulate matter in polluted air catalyses the
oxidation of sulphur dioxide.
(E) Lead (t) Red haze in traffic and
(a) Assertion is correct, reason is correct; reason is a
congested areas
correct explanation for assertion.
(a) A – (t), B – (p), C – (r), D – (s), E – (q) (b) Assertion is correct, reason is correct; reason is not a
(b) A – (s), B – (t), C – (p), D – (r), E – (q) correct explanation for assertion
(c) A – (s), B – (q), C – (p), D – (t), E – (r) (c) Assertion is correct, reason is incorrect
(d) A – (q), B – (s), C – (t), D – (r), E – (p) (d) Assertion is incorrect, reason is correct.
37. SO2 is one of the air pollutants. SO2 45. Which of the following is the major cause of global
(a) is a lung irritant warming?
(b) dissolves in water to form acid rain (a) re-radiation of U.V. rays by CO2 and H2O
(c) both (a) and (b) (b) re-radiation of I.R. rays by CO2 and H2O
(d) none of the above (c) re-radiation of I.R. rays by O2 and N2
38. Formation of London smog takes place in (d) re-radiation of U.V. rays by O2 and N2
(a) winter during day time 46. Assertion : Dinitrogen and dioxygen do not react with
(b) summer during day time each other at a normal temperature.
(c) summer during morning time Reason : At high altitudes dinitrogen combines with
(d) winter during morning time dioxygen to form oxides of nitrogen
39. Which of the following statements about polar stratosphere (a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion.
clouds (PSCs) is not correct?
(b) Assertion is correct, reason is correct; reason is not a
(a) PSCs do not react with chlorine nitrate and HCl
correct explanation for assertion
(b) Type I clouds are formed at about –77ºC and contain (c) Assertion is correct, reason is incorrect
solid HNO3 . 3H2O (d) Assertion is incorrect, reason is correct.
(c) Type II clouds are formed at about –85ºC and contain 47. The false statement among the followings :
some ice (a) The average residence time of NO is one month
(d) A tight whirlpool of wind called Polar Vortex is formed (b) Limestone acts as a sink for SOx
which surrounds Antarctica (c) SOx can be removed from flue gases by passing
40. Assertion : Photochemical smog is oxidising in nature. through a solution of citrate ions
Reason : Photochemical smog contains NO2 and O3, which (d) Ammonia acts as a sink for NOx
are formed during the sequence of reactions. 48. Assertion : Green house effect was observed in houses
(a) Assertion is correct, reason is correct; reason is a used to grow plants and these are made of green glass.
correct explanation for assertion. Reason : Green house name has been given because glass
(b) Assertion is correct, reason is correct; reason is not a houses are made of green glass.
correct explanation for assertion (a) Assertion is correct, reason is correct; reason is a
(c) Assertion is correct, reason is incorrect correct explanation for assertion.
(d) Assertion is incorrect, reason is correct. (b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion
41. The gas responsible for ozone depletion :
(c) Assertion is correct, reason is incorrect
(a) NO and freons (b) SO2
(d) Assertion is incorrect, reason is correct.
(c) CO2 (d) CO 49. Which of the following is/are formed when ozone reacts
42. Assertion : Ozone is destroyed by solar radiation in upper with the unburnt hydrocarbons in polluted air?
stratosphere. (i) Formaldehyde (ii) Acrolein
Reason : Thinning of the ozone layer allows excessive UV (iii) Peroxyacetyl nitrate (iv) Formic acid
radiations to reach the surface of earth. (a) (i) and (iv) (b) (ii) only
(a) Assertion is correct, reason is correct; reason is a (c) (iii) only (d) (i), (ii) and (iii)
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a Topic 2. Water Pollution
correct explanation for assertion 50. Minamata disease of Japan is due to pollution of
(c) Assertion is correct, reason is incorrect (a) Aresenic (b) Lead
(d) Assertion is incorrect, reason is correct. (c) Cynide (d) Mercury
ENVIRONMENTAL CHEMISTRY 189

51. The high amount of E. coli in water is the indicator of (c) Clean water would have a BOD value of less than 5
(a) hardness of water ppm.
(b) industrial pollution (d) Oxides of sulphur, nitrogen and carbon are the most
(c) sewage pollution widespread air pollutant.
(d) presence of chlorine in water 62. Limit of BOD prescribed by Central pollution Control Board
52. A lake with an inflow of domestic sewage rich in organic for the discharge of industrial and municipal waste waters
waste may result in into natural surface waters, is
(a) drying of the lake very soon due to algal bloom (a) < 100 ppm (b) < 30 ppm
(b) an increase production of fish due to lot of nutrients (c) < 3.0 ppm (d) < 10 ppm
(c) death of fish due to lack of oxygen
63. Phosphate fertilizers when added to water leads to
(d) increased population of aquatic food web organisms
(a) increased growth of decomposers
53. Which of the following does not occur when the sewage is
(b) reduced algal growth
discharged into water ?
(c) increased algal growth
(a) Increase in O2
(b) Cyanophycean blooms occur (d) nutrient enrichment (eutrophication)
(c) Depletion of O2 layers 64. BOD of pond is connected with
(d) Eutrophication (a) microbes & organic matter
54. Which of the following metal is a water pollutant and causes (b) organic matter
sterility in human being (c) microbes
(a) As (b) Mn (d) none of these
(c) Mg (d) Hg 65. The maximum prescribed concentration of cadmium in
55. Assertion : Eutrophication shows increase in productivity drinking water in ppm is
in water. (a) 0.05 (b) 3
Reason : With increasing eutrophication, the diversity of (c) 2 (d) 0.005
the phytoplankton increases. 66. Eutrophication causes reduction in
(a) Assertion is correct, reason is correct; reason is a (a) dissolved oxygen (b) nutrients
correct explanation for assertion. (c) dissolved salts (d) All of the above
(b) Assertion is correct, reason is correct; reason is not a 67. Which of the following statements are not correct?
correct explanation for assertion (i) F– ion concentration above 2 ppm causes brown
(c) Assertion is correct, reason is incorrect mottling in teeth.
(d) Assertion is incorrect, reason is correct. (ii) Excessive F– (over 10 ppm) causes harmful effect to
56. Sewage water is purified by bones and teeth.
(a) aquatic plants (b) microoganisms (iii) Excessive lead in drinking water causes disease
(c) light (d) fishes methemoglobinemia
57. Water is often treated with chlorine to (iv) Deficiency of sulphate in drinking water causes
(a) remove hardness
laxative effect.
(b) increase oxygen content
(c) kill germs (a) (ii) and (iv) (b) (ii) and (iii)
(d) remove suspended particles (c) (ii), (iii) and (iv) (d) (iii) and (iv)
58. Which causes death of fish in water bodies polluted by 68. Assertion : If BOD level of water in a reservoir is less than
sewage? 5 ppm it is highly polluted.
(a) Foul smell (b) Pathogens Reason : High biological oxygen demand means low activity
(c) Herbicides (d) Decrease in D.O. of bacteria in water.
59. B.O.D. test or biochemical oxygen demand test is made for (a) Assertion is correct, reason is correct; reason is a
measuring correct explanation for assertion.
(a) air pollution (b) water pollution (b) Assertion is correct, reason is correct; reason is not a
(c) noise pollution (d) soil pollution
correct explanation for assertion
60. Brewery and sugar factory waste alters the quality of a water
body by increasing (c) Assertion is correct, reason is incorrect
(a) temperature (b) turbidity (d) Assertion is incorrect, reason is correct.
(c) pH (d) COD and BOD 69. Sewage mostly constitutes
61. Which one of the following statement is not true ? (a) Non-biodegradable pollutants
(a) pH of drinking water should be between 5.5 – 9.5. (b) Biodegradable pollutants
(b) Concentration of DO below 6 ppm is good for the (c) Effluents
growth of fish. (d) Air pollutants
 EBD_7374
190 CHEMISTRY

70. Assertion : The F – ions make the enamel on teeth much 80. Match the columns
harder. Column - I Column - II
Reason : F– ions converts hydroxyapatite (A) Concentration of (p) 6 ppm
[3(Ca(PO4)2 Ca(OH)2] into fluorapatite [3(Ca3(PO4)2. CaF2]. dissolved oxygen in
(a) Assertion is correct, reason is correct; reason is a cold water
correct explanation for assertion. (B) Concentration of (q) 17 ppm
(b) Assertion is correct, reason is correct; reason is not a dissolved oxygen
correct explanation for assertion below which growth
(c) Assertion is correct, reason is incorrect of fish gets inhibited
(d) Assertion is incorrect, reason is correct. (C) BOD value of clean (r) 5 ppm
71. A dental disease characterised by mottling of teeth is due to water
presence of a certain chemical element in drinking water. (D) BOD value of (s) 10 ppm
Which is that element? polluted water.
(a) Boron (b) Chlorine (a) A – (s), B – (s), C – (q), D – (p)
(c) Fluorine (d) Mercury (b) A – (p), B – (q), C – (r), D – (s)
72. Frequent occurrence of water blooms in a lake indicates (c) A – (s), B – (p), C – (r), D – (q)
(a) nutrient deficiency (d) A – (p), B – (s), C – (q), D – (r)
(b) oxygen deficiency 81. Negative soil pollution is
(c) excessive nutrient availability (a) reduction in soil productivity due to erosion and over
(d) absence of herbivores in the lake use
73. Lichens do not like to grow in cities (b) reduction in soil productivity due to addition of
(a) because of absence of the right type of algae and fungi pesticides and industrial wastes
(b) because of lack of moisture (c) converting fertile land into barren land by dumping
(c) because of SO2 pollution ash, sludge and garbage
(d) because natural habitat is missing (d) None of the above
74. Which is known as ‘Third poison of environment’ and also 82. Assertion : Excessive use of chlorinated synthetic
creates ‘Blue baby syndrome’ pesticides causes soil and water pollution.
(a) Nitrate present in water Reason : Such pesticides are non-biodegradables.
(b) Phosphate and detergents found in water (a) Assertion is correct, reason is correct; reason is a
(c) Cyanide correct explanation for assertion.
(d) Pesticides (b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion
Topic 3. Soil Pollution
(c) Assertion is correct, reason is incorrect
75. Chief source of soil and water pollution is (d) Assertion is incorrect, reason is correct.
(a) mining (b) agro industry 83. Thermal pollution affects mainly
(c) thermal power plant (d) All of the above (a) vegetation (b) aquatic creature
76. The quantity of DDT in food chain (c) rocks (d) air
(a) decreases (b) remains same 84. Which one of the following statements is correct ?
(c) increases (d) changes
(a) Extensive use of chemical fertilizers may lead to
77. The effect of polluted water on soil is, that
eutrophication of nearby water bodies
(a) it decreases fertility
(b) Both Azotobacter and Rhizobium fix atmospheric
(b) it contaminates ground water
nitrogen in root nodules of plants
(c) it renders soil acidic or basic
(d) all of the above (c) Cyanobacteria such as Anabaena and Nostoc are
78. Soil is polluted by important mobilizers of phosphates and potassium for
I. pesticides plant nutrition in soil
II. synthetic fertilizers (d) At present it is not possible to grow maize without
III. green manure chemical fertilizers
Choose the correct option. 85. Match the columns
(a) I and III (b) I and II Column I Column II
(c) II and III (d) I, II and III (A) Phosphate fertilisers (p) BOD level of water
79. Which of the following trophic level has least concentration in water increases
of toxins deposition ? (B) Methane in air (q) Acid rain
(a) Aquatic plant (b) Small fish (C) Synthetic detergents (r) Global warming
(c) Human being (d) Largest fish in water
ENVIRONMENTAL CHEMISTRY 191

(D) Nitrogen oxides in air (s) Eutrophication (iii) Technology has now been developed to produce
(a) A – (p,s), B – (r), C – (p), D – (q) electricity from the garbage.
(b) A – (p), B – (s), C – (r), D – (q) (a) (ii) only (b) (ii) and (iii)
(c) A – (s), B – (r), C – (q), D – (p) (c) (iii) only (d) All of these
(d) A – (p), B – (q), C – (s), D – (r) 88. Green chemistry means such reactions which :
Topic 4. Industrial waste, strategies to control (a) produce colour during reactions
(b) reduce the use and production of hazardous chemicals
Environmental pollution, Green chemistry
(c) are related to the depletion of ozone layer
86. “Reducing potentially hazardous waste through smarter (d) study the reactions in plants
production”. 89. Use of which of the following solvent in dry cleaning will
This represents a great step forward for result in less harm to ground water?
(a) green revolution (b) green chemistry (a) Cl2C = CCl2 (b) Liquid CO2
(c) industrial revolution (d) green biotechnology (c) H2O2 (d) None of these
87. Which of the following statement(s) is/are true about 90. Synthesis of ethanal commercially from which of the
waste recycling? following reagent is the part of green chemistry?
(i) Clothes can be made from recycled plastic waste. (a) CH3 CH2OH (b) CH2 = CH2
(ii) Fuel that has high octane rating and contains no lead (c) HC º CH (d) All of these
can be obtained from plastic waste.

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 6. Sewage containing organic waste should not be disposed
in water bodies because it causes major water pollution.
1. Which of the following gases in not a green house gas? Fishes in such a polluted water die because of
(a) CO (b) O3 (a) large number of mosquitoes
(c) CH4 (d) H2O vapour (b) increase in the amount of dissolved oxygen
2. Photochemical smog occurs in warm, dry and sunny climate. (c) decrease in the amount of dissolved oxygen in water
One of the following is not amongst the components of (d) clogging of gills by mud
photochemical smog, identify it. 7. Which of the following statements about photochemical
(a) NO2 smog is wrong?
(b) O3 (a) It has high concentration of oxidising agents
(c) SO2 (b) It has low concentration of oxidising agent
(d) Unsaturated hydrocarbon (c) It can be controlled by controlling the release of NO 2,
3. Which of the following statements is not true about classical hydrocarbons, ozone etc
smog? (d) Plantation of some plants like pinus helps in controlling
(a) Its main components are produced by the action of photochemical smog
sunlight on emissions of automobiles and factories 8. The gaseous envelope around the earth is known as
(b) Produced in cold and humid climate atmosphere. The lowest layer of this is extended upto 10 km
(c) It contains compounds of reducing nature from sea level, this layer is
(d) It contains smoke, fog and sulphur dioxide (a) stratosphere (b) troposphere
4. Biochemical Oxygen Demand, (BOD) is a measure of organic (c) mesosphere (d) hydrosphere
material present in water. BOD value less than 5 ppm 9. Dinitrogen and dioxygen are main constituents of air but
indicates a water sample to be these do not react with each other to form oxides of nitrogen
(a) rich in dissolved oxygen because ............... .
(b) poor in dissolved oxygen (a) the reaction is endothermic and requires very high
(c) highly polluted temperature
(d) not suitable for aquatic life (b) the reaction can be initiated only in presence of a
5. Which of the following statement(s) is/are wrong? catalyst
(a) Ozone is not responsible for green house effect (c) oxides of nitrogen are unstable
(b) Ozone can oxidise sulphur dioxide present in the (d) N2 and O2 are unreactive
atmosphere to sulphur trioxide 10. The pollutants which come directly in the air from sources
(c) Ozone hole is thinning of ozone layer present in stratosphere are called primary pollutants. Primary pollutants are
(d) Ozone is produced in upper stratosphere by the action sometimes converted into secondary pollutants. Which of
of UV rays on oxygen the following belongs to secondary air pollutants?
 EBD_7374
192 CHEMISTRY

(a) CO (b) Hydrocarbon 18. Assertion: Nitrogen and oxygen are the main components
(c) Peroxyacetyl nitrate (d) NO in the atmosphere but these do not react to form oxides of
11. Which of the following statements is correct? nitrogen. [JEE M 2015, S]
(a) Ozone hole is a hole formed in stratosphere from which Reason: The reaction between nitrogen and oxygen requires
ozone oozes out high temperature.
(b) Ozone hole is a hole formed in troposphere from which (a) The assertion is incorrect, but the reason is correct
ozone oozes out (b) Both the assertion and reason are incorrect
(c) Ozone hole is thinning of ozone layer of stratosphere (c) Both assertion and reason are correct, and the reason
at some places is the correct explanation for the assertion
(d) Ozone hole means vanishing of ozone layer around (d) Both assertion and reason are correct, but the reason
the earth completely is not the correct explanation for the assertion
12. Which of the following practices will not come under green 19. The disease caused the high concentration of hydrocarbon
chemistry? pollutants in atmosphere is/are [BITSAT 2015, S]
(a) If possible, making use of soap made of vegetable oils
(a) silicosis (b) TB (c) cancer (d) asthma
instead of using synthetic detergents.
20. Which of the following pollutants is main product of
(b) Using H2O2 for bleaching purpose instead of using
automobiles exhaust? [BITSAT 2015, S]
chlorine based bleaching agents
(c) Using bicycles for travelling small distances instead (a) C O (b) CO2
of using petrol/ diesel based vehicles (c) NO (d) Hydrocarbons
(d) Using plastic cans for neatly storing substances 21. The irritant red haze in the traffic and congested places is
due to presence of which of the following ?
Past Year MCQs [AIIMS 2016, S]
13. Which of the following is not a common component of (i) Oxides of sulphur
Photochemical Smog? [AIPMT 2014, S] (ii) Oxides of nitrogen
(a) Ozone (b) Acrolein (iii) Carbon dioxide
(c) Peroxyacetyl nitrate (d) Chlorofluorocarbons (iv) Mists, smoke and dust
14. The secondary precursors of photochemical smog are (v) Smog
(a) SO2 and NO2 [AIIMS 2014, S] (a) (i), (iv) and (v) (b) (iii) only
(b) SO2 and hydrocarbons (c) (ii) only (d) (ii) and (v)
(c) NO2 and hydrocarbons
22. The concentration of fluoride, lead, nitrate and iron in a
(d) O3 and PAN
water sample from an underground lake was found to be
15. When rain is accompanied by a thunderstorm, the collected
1000 ppb, 40 ppb, 100 ppm and 0.2 ppm, respectively. This
rain water will have a pH value [BITSAT 2014, S]
water is unsuitable for drinking due to high concentration
(a) Slightly lower than that of rain water without
of : [JEE M 2016, S]
thunderstorm
(a) Nitrate (b) Iron (c) Fluoride (d) Lead
(b) Slightly higher than that when the thunderstorm is
not there 23. Which of the following is a sink for CO ? [NEET 2017, C]
(c) Uninfluenced by occurrence of thunderstorm (a) Microorganism present in the soil
(d) Which depends upon the amount of dust in air (b) Oceans
16. Identify the wrong statement in the following: (c) Plants
[BITSAT 2014, S] (d) Haemoglobin
(a) Chlorofluorocarbons are responsible for ozone layer 24. A water sample has ppm level concentration of following
depletion anions
(b) Greenhouse effect is responsible for global warming F– = 10; SO42– = 100; NO3– = 50
(c) Acid rain is mostly because of oxides of nitrogen and the anion/anions that make/makes the water sample
sulphur unsuitable for drinking is/are : [JEE M 2017, S]
(d) Ozone layer does not permit infrared radiation from the (a) only NO3– (b) both SO42– and NO3–
sun to reach the earth (c) only F– (d) only SO42–
17. Assertion : Suspended particulate matter (SPM) is an 25. Which of the following is not involved in the formation of
important pollutant released by diesel vehicles. photochemical smog? [BITSAT 2017, 2005, S]
Reason : Catalytic converters greatly reduce pollution (a) Hydrocarbon (b) NO
caused by automobiles. [AIIMS 2015, S]
(c) SO2 (d) O3
(a) If Assertion is correct but Reason is incorrect.
26. Which oxide of nitrogen is not a common pollutant
(b) If both the Assertion and Reason are incorrect.
introduced into the atmosphere both due to natural and
(c) If both Assertion and Reason are correct and Reason
human activity? [NEET 2018, S]
is the correct explanation of Assertion.
(a) N2O5 (b) NO2 (c) NO (d) N2O
(d) If both Assertion and Reason are correct, but Reason
is not the correct explanation of Assertion.
ENVIRONMENTAL CHEMISTRY 193

27. The recommended concentration of fluoride ion in drinking 28. Identify the incorrect statement from the following :
water is up to 1ppm as fluoride ion is required to make teeth [BITSAT 2018, S]
enamel harder by converting [3Ca3(PO4)2. Ca(OH)2] to : (a) Ozone absorbs the intense ultraviolet radiation of the
[JEE M 2018, S] sun.
(a) [CaF2] (b) Depletion of ozone layer is because of its chemical
reactions with chlorofluoro alkanes.
(b) [3(CaF2).Ca(OH)2] (c) Ozone absorbs infrared radiation.
(c) [3Ca3(PO4)2.CaF2] (d) Oxides of nitrogen in the atmosphere can cause the
(d) [3{(Ca(OH)2}.CaF2] depletion of ozone layer.

Exercise 3 : Try If You Can

1. Recent reports of acid rains industrial cities are due to the 7. Minamata disease is a pollution related disease results from
effect of atmospheric pollution by: (a) oil spills into sea
(a) Excessive release of NO2 and SO2 by burning of fossil (b) accumulation of arsenic into atmosphere
fuels (c) release of industrial waste mercury into bodies water
(b) Excessive release of CO2 by burning of fuel like wood (d) release human organic waste into drinking water
and charcoal, cutting of forests and increased animal 8. Which of the following is/are formed when ozone reacts
population with the unburnt hydrocarbons in polluted air ?
(c) Excessive release of NH3 by industrial plants and coal (i) Formaldehyde (ii) Acrolein
gas (iii) Peroxyacetyl nitrate (iv) Formic acid
(d) Excessive release of CO in atmosphere by incomplete (a) (i) and (iv) (b) (ii) only
combustion of coke, charcoal and other carbonaceous (c) (iii) only (d) (i), (ii) and (iii)
fuels in paucity of oxygen 9. Addition of phosphate fertilisers to water bodies causes:
2. Which one of the following substances used in dry cleaning (a) increase in amount of dissolved oxygen in water
is a better strategy to control environmental pollution ? (b) deposition of calcium phosphate
(c) increase in fish population
(a) Sulphur dioxide (b) Carbon dioxide
(d) enhanced growth of algae
(c) Nitrogen dioxide (d) Tetrachloroethylene
10. Water sample is reported to be highly polluted if BOD
3. Green house gases can be arranged in ‘Global Warming
(Biological Oxygen Demand) value of sample becomes
Potential’ sequence as
(a) more than 17 ppm (b) equal to 10 ppm
(a) N2O > CFC > CH4 > CO2 (c) equal to 5 ppm (d) less than 5 ppm
(b) CFC > N2O > CH4 > CO2 11. What is the concentration of dissolved oxygen in cold
(c) CFC > CO2 > N2O > CH4 water ?
(d) CO2 > CFC > N2O > CH4 (a) 5 ppm (b) 10 ppm
4. In almost all Indian metropolitan cities like Delhi, the major (c) 200, 000 ppm (d) 100 ppm
atmospheric pollutant(s) is/are 12. BOD of pond is connected with
(a) suspended particulate matter (SPM) (a) Microbes & organic matter (b) Organic matter
(b) oxides of sulphur (c) Microbes (d) None of these
(c) carbon dioxide and carbon monoxide 13. Soil is polluted by
(d) oxides of nitrogen I. pesticides
5. In coming years, skin related disorders will be more common II. synthetic fertilizers
due to III. green manure
(a) pollutants in air (b) use of detergents Choose the correct option.
(c) water pollution (d) depletion of ozone layer (a) I and III (b) I and II
6. Which of the following statement is wrong? (c) II and III (d) I, II and III
(a) Polar stratospheric clouds (PSCs) are clouds formed 14. Which of the following trophic level has least concentration
over Antarctica of toxins deposition ?
(a) Aquatic plant (b) Small fish
(b) Acid rain dissolves heavy metals such as Cu, Pb, Hg
(c) Human being (d) Largest fish
and Al from soil, rocks and sediments.
(c) H2SO4 is major contributor to acid rain, HNO3 ranks 15. Most hazardous metal pollutant of automobile exhaust is
second and HCl third in this respect (a) Mercury (b) Tin
(d) Fishes grow as well in warm as in cold water (c) Cadmium (d) Lead
 EBD_7374
194 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (d) 10 (a) 19 (a) 28 (c) 37 (c) 46 (b) 55 (b) 64 (a) 73 (c) 82 (a)
2 (d) 11 (a) 20 (a) 29 (c) 38 (d) 47 (a) 56 (b) 65 (d) 74 (a) 83 (b)
3 (c) 12 (a) 21 (a) 30 (a) 39 (a) 48 (c) 57 (c) 66 (a) 75 (d) 84 (a)
4 (b) 13 (d) 22 (a) 31 (d) 40 (a) 49 (d) 58 (d) 67 (d) 76 (c) 85 (a)
5 (b) 14 (d) 23 (c) 32 (d) 41 (a) 50 (d) 59 (b) 68 (c) 77 (d) 86 (b)
6 (c) 15 (d) 24 (b) 33 (d) 42 (d) 51 (c) 60 (d) 69 (b) 78 (b) 87 (d)
7 (b) 16 (b) 25 (d) 34 (a) 43 (c) 52 (c) 61 (b) 70 (a) 79 (a) 88 (b)
8 (d) 17 (a) 26 (a) 35 (a) 44 (a) 53 (a) 62 (b) 71 (c) 80 (c) 89 (b)
9 (d) 18 (b) 27 (c) 36 (b) 45 (b) 54 (b) 63 (d) 72 (b) 81 (a) 90 (b)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (a) 4 (a) 7 (b) 10 (c) 13 (d) 16 (d) 19 (c) 22 (a) 25 (c) 28 (c)
2 (c) 5 (a) 8 (b) 11 (c) 14 (d) 17 (b) 20 (c) 23 (a) 26 (a)
3 (a) 6 (c) 9 (a) 12 (d) 15 (a) 18 (a) 21 (c) 24 (c) 27 (c)
Exercis e 3 : Try If You Can
1 (a) 3 (b) 5 (d) 7 (c) 9 (d) 11 (b) 13 (b) 15 (d)
2 (d) 4 (a) 6 (d) 8 (d) 10 (a) 12 (a) 14 (a)
 15 Chapter
THE SOLID STATE

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Packing imperfections,
AIIMS 3 defects in solids, unit cells. 4/5 8.2
JEE Main 2
BITSAT 2
 EBD_7374
196 CHEMISTRY
THE SOLID STATE 197
 EBD_7374
198 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Amorphous and Crystalline Solids 8. Assertion: Glass panes fixed to windows or panes of old
buildings are found to be slightly thicker at the bottom.
1. “Crystalline solids are anisotropic in nature. What is the Reason: Amorphous solids have a tendency to flow.
meaning of anisotropic in the given statement? (a) Assertion is correct, reason is correct; reason is a
(a) A regular pattern of arrangement of particles which correct explanation for assertion.
repeats itself periodically over the entire crystal. (b) Assertion is correct, reason is correct; reason is not a
(b) Different values of some of physical properties are correct explanation for assertion
shown when measured along different directions in (c) Assertion is correct, reason is incorrect
the same crystals. (d) Assertion is incorrect, reason is correct.
(c) An irregular arrangement of particles over the entire
crystal. Topic 2: Classification of Crystalline Solids
(d) Same values of some of physical properties are shown 9. Which of the following exists as covalent crystals in the
when measured along different directions in the same solid state?
crystals. (a) Iodine (b) Silicon
2. A crystalline solid (c) Sulphur (d) Phosphorus
(a) changes abruptly from solid to liquid when heated 10. The major binding force of diamond, silicon and quartz is
(b) has no definite melting point (a) electrostatic force (b) electrical attraction
(c) undergoes deformation of its geometry easily (c) covalent bond force (d) non-covalent bond force
(d) has an irregular 3-dimensional arrangements 11. In graphite electrons are :
3. Which of the following statements about amorphous solids (a) localised on each carbon atom
is incorrect ? (b) spread out between the sheets
(c) localised on every third carbon atom
(a) They melt over a range of temperature
(d) present in antibonding orbital.
(b) They are anisotropic
12. Which one of the following forms a molecular solid when
(c) There is no orderly arrangement of particles
solidified?
(d) They are rigid and incompressible (a) Silicon carbide (b) Calcium fluoride
4. Which of the following is not a crystalline solid? (c) Rock salt (d) Methane
(a) KCl (b) CsCl 13. Match the columns
(c) Glass (d) Rhombic S Column-I Column-II
5. Which of the following amorphous solid is used as (Type of solid) (Example of solid)
photovoltaic material for conversion of sunlight into (A) Molecular solid (p) Ag
electricity? (B) Ionic solid (q) SiC
(a) Quartz glass (b) Quartz (C) Metallic solid (r) CCl4
(c) Silicon (d) Both (a) and (b) (D) Covalent solid (s) MgO
6. Which of the following statement(s) is/are correct? (a) A – (s), B – (r), C – (p), D – (q)
(i) Crystalline solids have definite characteristic (b) A – (q), B – (s), C – (p), D – (r)
geometrical shape. (c) A – (r), B – (q), C – (p), D – (s)
(ii) Crystalline solids have long range order. (d) A – (r), B – (s), C – (p), D – (q)
(iii) Sodium chloride and quartz glass are examples of 14. Which of the following type of solid has high melting point
crystalline solids. and do not conduct electricity but its aqueous solution
(iv) Crystalline solids are isotropic in nature. and melt conduct electricity ?
(a) (i), (ii) and (iii) (b) (i), (ii) and (iv) (a) Covalent (b) Ionic
(c) (i) and (ii) (d) (i) only (c) Molecular (d) Metallic
7. Which of the following is true about the value of refractive
Topic 3: Crystal Lattice and Unit Cells
index of quartz glass ?
(a) Same in all directions 15. Potassium crystallizes with a
(b) Different in different directions (a) body-centred cubic lattice
(b) face-centred cubic lattice
(c) Cannot be measured
(c) simple cubic lattice
(d) Always zero
(d) orthorhombic lattice
THE SOLID STATE 199

16. Tetragonal crystal system has the following unit cell (b) A4B3
dimensions (c) A3B
(a) a = b = c, a = b = g = 90° (d) Composition can’t be specified
24. In a cubic lattice A atom occupy all the corners. If B atom
(b) a = b ¹ c, a = b = g = 90° occupy one of the opposite face, and atom C occupy the
(c) a ¹ b ¹ c, a = b = g = 90° remaining faces. The simplest formulae of the compound is
(a) ABC3 (b) ABC2 (c) ABC (d) AB2C
(d) a = b ¹ c, a = b = 90° g = 120° 25. A compound is formed by elements A and B. The crystalline
17. Match the columns cubic structure has the A atoms at the corners of the cube
Column-I Column-II and B atoms at the body centre. The simplest formula of the
(Crystal system) (Compounds) compound is
(A) Rhombohedral (p) KNO3 (a) AB (b) A6B (c) AB6 (d) A8B4
(B) Orthorhombic (q) Zinc blende 26. When molten zinc is converted into solid state, it acquires
(C) Cubic (r) CdS hcp structure. The number of nearest neighbours of Zn will
(D) Hexagonal (s) Calcite be
(a) A – (p), B – (q), C – (s), D – (r) (a) 6 (b) 12 (c) 8 (d) 4
(b) A – (r), B – (p), C – (q), D – (s) 27. Which of the following metal(s) show(s) hexagonal close
(c) A – (s), B – (p), C – (q), D – (r) packed structure (hcp) and which show face centred cubic
(d) A – (q), B – (r), C – (s), D – (p) (fcc) structure?
hcp fcc hcp fcc
Topic 4: Number of Atoms in Unit Cell
(a) Ag, Zn Mg, Cu (b) Mg, Zn Ag, Cu
18. An element occuring in the bcc structure has 12.08 × 1023 unit (c) Cu, Fe Al, Sn (d) Na, Li Zn, Cu
cells. The total number of atoms of the element in these cells 28. The number of octahedral voids present in a lattice is A .
will be The number of closed packed particles, the number of
(a) 24.16 × 1023 (b) 36.18 × 1023 tetrahedral voids generated is B the number of closed
(c) 6.04 × 1023 (d) 12.08 × 1023 packed particles
19. Which of the following statements(s) is/are incorrect? (a) A- equal, B- half (b) A- twice, B- equal
(i) Only 1/8th portion of an atom located at corner of a (c) A- twice , B- half (d) A- equal, B- twice
cubic unit cell is its neighbouring unit cell. 29. The Ca2+ and F– are located in CaF2 crystal, respectively at
(ii) Total number of atoms per unit cell for a face centered face centred cubic lattice points and in
cubic unit cell is 3 . (a) tetrahedral voids (b) half of tetrahedral voids
(iii) Atom located at the body center is shared between (c) octahedral voids (d) half of octahedral voids
two adjacent unit cells. 30. If Germanium crystallises in the same way as diamond, then
(a) (iii) only (b) (ii) only which of the following statement is not correct?
(c) (i) and (ii) (d) (ii) and (iii) (a) Every atom in the structure is tetrahedrally bonded to
20. The number of carbon atoms per unit cell of diamond unit 4 atoms.
cell is : (b) Unit cell consists of 8 Ge atoms and co-ordination
(a) 8 (b) 6 (c) 1 (d) 4 number is 4.
21. Na and Mg crystallize in bcc and fcc type crystals (c) All the octahedral voids are occupied.
respectively, then the number of atoms of Na and Mg present (d) All the octahedral voids and 50% tetrahedral voids
in the unit cell of their respective crystal is remain unoccupied.
(a) 4 and 2 (b) 9 and 14 (c) 14 and 9 (d) 2 and 4 31. The arrangement ABC ABC .......... is referred to as
Topic 5: Close-Packed Structure (a) Octahedral close packing
22. A solid has a structure in which ‘W’ atoms are located at the (b) Hexagonal close packing
corners of a cubic lattice ‘O’ atoms at the centre of edges (c) Tetrahedral close packing
and Na atoms at the centre of the cube. The formula for the (d) Cubic close packing
compound is 32. Match Column-I (Type of close packed structure) with
(a) Na2WO3 (b) Na2WO2 (c) NaWO2 (d) NaWO3 Column-II (Coordination number) and choose the correct
23. A substance AxBy crystallizes in a face centred cubic (fcc) option.
Column-I Column-II
lattice in which atoms ‘A’ occupy each corner of the cube
(A) One dimensional close (p) 12
and atoms ‘B’ occupy the centres of each face of the cube.
packed arrangement.
Identify the correct composition of the substance AxBy
(a) AB3 (B) Square close packing in (q) 6
two dimensions.
 EBD_7374
200 CHEMISTRY

(C) Two dimensional (r) 2 (a) 74% (b) 26%

hexagonal close packing. (c) 50% (d) none of these.
(D) Cubic close packed (s) 4 39. AB; crystallizes in a body centred cubic lattice with edge
arrangement. length ‘a’ equal to 387 pm. The distance between two
(a) A – (r), B – (s), C – (q), D – (p) oppositely charged ions in the lattice is :
(b) A – (r), B – (s), C – (p), D – (q) (a) 335 pm (b) 250 pm (c) 200 pm (d) 300 pm
(c) A – (s), B – (r), C – (q), D – (p) 40. Assertion : The packing efficiency is maximum for the fcc
(d) A – (s), B – (q), C – (p), D – (r) structure.
33. In the cubic close packing, the unit cell has ______. Reason : The cordination number is 12 in fcc structures.
(a) 4 tetrahedral voids each of which is shared by four (a) Assertion is correct, reason is correct; reason is a
adjacent unit cells. correct explanation for assertion.
(b) 4 tetrahedral voids within the unit cell. (b) Assertion is correct, reason is correct; reason is not a
(c) 8 tetrahedral voids each of the which is shared by four correct explanation for assertion
adjacent unit cells. (c) Assertion is correct, reason is incorrect
(d) 8 tetrahedral voids within the unit cells. (d) Assertion is incorrect, reason is correct.
34. Assertion : In crystal lattice, the size of the tetrahedral hole 41. Packing efficiency by arrangement of atoms in two
is larger than an octahedral hole. dimensional hexagonal close packing is
Reason : The cations occupy less space than anions in (a) 60.43 (b) 65.78 (c) 59.78 (d) 68.76
crystal packing.
Topic 7: Calculation Involving Unit Cell Dimensions
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion. 42. CsBr crystallises in a body centered cubic lattice. The unit
(b) Assertion is correct, reason is correct; reason is not a cell length is 436.6 pm. Given that the atomic mass of Cs =
correct explanation for assertion 133 and that of Br = 80 amu and Avogadro number being
(c) Assertion is correct, reason is incorrect 6.02 × 1023 mol–1, the density of CsBr is
(d) Assertion is incorrect, reason is correct. (a) 0.425 g/cm3 (b) 8.5 g/cm3
35. Match the columns (c) 4.25 g/cm 3 (d) 82.5 g/cm3
Column-I Column-II 43. Pottasium has a bcc structure with nearest neighbour
(A) Square close packing (p) Triangular voids distance 4.52 Å. Its atomic weight is 39. Its density (in kg m–3)
in two dimensions will be
(B) Hexagonal close (q) Pattern of spheres is (a) 454 (b) 804 (c) 852 (d) 910
packing in two repeated every fourth 44. The cubic unit cell of a metal (molar mass = 63.55g mol–1)
dimensions layer has an edge length of 362 pm. Its density is 8.92g cm–3.
(C) Hexagonal close (q) Coordination number 4 The type of unit cell is
packing in three dimensions (a) primitive (b) face centered
(D) Cubic close packing (s) Pattern of sphere is (c) body centered (d) end centered
in three dimensions repeated alternate layers 45. Iron crystallizes in a b.c.c. system with a lattice parameter of
(a) A – (r), B – (p), C – (s), D – (q) 2.861 Å. Calculate the density of iron in the b.c.c. system
(b) A – (p), B – (s), C – (q), D – (r) (Atomic weight of Fe = 56, NA = 6.02 × 1023 mol–1)
(c) A – (s), B – (p), C – (q), D – (s) (a) 7.92 g ml–1 (b) 8.96 g ml–1
(c) 2.78 g ml –1 (d) 6.72 g ml–1
(d) A – (r), B – (p), C – (s), D – (q)
46. An element (atomic mass = 100 g / mol) having bcc structure
Topic 6: Packing Efficiency has unit cell edge 400 pm. Then, density of the element is
36. The fraction of total volume occupied by the atoms present (a) 10.376 g/cm3 (b) 5.188 g/cm3
in a simple cube is (c) 7.289 g/cm 3 (d) 2.144 g/cm36
p p p p 47. A metal crystallizes in 2 cubic phases fcc and bcc whose
(a) (b) (c) (d) unit cell lengths are 3.5 Å and 3.0Å respectively. The ratio
3 2 4 2 4 6
of their densities is
37. Percentages of free space in cubic close packed structure
(a) 0.72 (b) 2.04 (c) 1.46 (d) 3.12
and in body centered packed structure are respectively
48. If ‘a’ stands for the edge length of the cubic systems : simple
(a) 30% and 26% (b) 26% and 32%
cubic, body centred cubic and face centred cubic, then the
(c) 32% and 48% (d) 48% and 26%
ratio of radii of the spheres in these systems will be
38. A metallic crystal crystallizes into a lattice containing a
respectively,
sequence of layers AB AB AB......Any packing of spheres
leaves out voids in the lattice. What percentage of volume 1 3 1 1 1
of this lattice is empty space? (a) a: a: a (b) a : 3a : a
2 4 2 2 2 2
THE SOLID STATE 201

(c) Interstitial (d) F – centre

1 3 3 59. Frenkel and Schottky defects are :
(c) a: a: a (d) 1a : 3a : 2a
2 2 2 (a) nucleus defects (b) non-crystal defects
49. Edge length of unit cell is 3.608 × 10–8 cm, which crystallizes (c) crystal defects (d) nuclear defects
in fcc and is determined to have a density of 8.92 g/cm 3. 60. In stoichiometric defects, the types of compound exhibit
The mass of four atoms is Frenkel defects have/has
(a) 4.18 × 10–22 (b) 1.67 × 10–21 (a) Low co-ordination nos.
(c) 2.09 × 10 –22 (d) 8.37 × 10–22 (b) High co-ordination
50. The edge length of unit cell of a metal having molecular (c) Small difference in the size of cations and anions
weight 75 g/mol is 5Å which crystallizes in cubic lattice. If (d) None of these
the density is 2g/cc then find the radius of metal atom. 61. The crystal with metal deficiency defect is
(NA = 6 × 1023). Give the answer in pm. (a) NaCl (b) FeO (c) KCl (d) ZnO
(a) 217 pm (b) 210 pm (c) 220 pm (d) 205 pm 62. Which of the following has Frenkel defects?
51. The number of atoms in 100 g of an fcc crystal with density, (a) Sodium chloride (b) Graphite
d = 10 g/cm3 and cell edge equal to 100 pm, is equal to (c) Silver bromide (d) Diamond
(a) 1 × 1025 (b) 2 × 1025 (c) 3 × 1025 (d) 4 × 1025 63. Crystal defect indicated in the diagram below is
52. A metallic element exists as cubic lattice. Each edge of the Na + Cl - Na + Cl - Na + Cl -
unit cell is 2.88 Å. The density of the metal is 7.20 g cm–3. Cl– c Cl– Na+ c Na+
How many unit cell will be present in 100 g of the metal? Na+Cl– c Cl– Na+ Cl–
(a) 6.85 × 102 (b) 5.82 × 1023 Cl– Na+ Cl–Na+ c Na+
(c) 4.37 × 105 (d) 2.12 × 106 (a) Interstitial defect
53. A metal has a fcc lattice. The edge length of the unit cell is (b) Schottky defect
404 pm. The density of the metal is 2.72 g cm–3. The molar (c) Frenkel defect
mass of the metal is : (d) Frenkel and Schottky defects
(NA Avogadro’s constant = 6.02 × 1023 mol–1) 64. In a solid lattice the cation has left a lattice site and is located
(a) 30 g mol–1 (b) 27 g mol–1 at an interstitial position, the lattice defect is :
(c) 20 g mol –1 (d) 40 g mol–1 (a) Interstitial defect (b) Valency defect
Topic 8: Imperfections in Solids (c) Frenkel defect (d) Schottky defect
65. Doping of AgCl crystals with CdCl2 results in
54. Which of the following statements is not correct ?
(a) Frenkel defect
(a) Vacancy defect results in decrease in density of
substance. (b) Schottky defect
(b) Vacancy defect can develop when a substance is (c) Substitutional cation vacancy
heated. (d) Formation of F - centres
(c) Interstitial defect increases the density of the 66. Which of the following defects is also known as dislocation
defect ?
substance.
(a) Frenkel defect
(d) Ionic solids show interstitial defects only.
(b) Schottky defect
55. When electrons are trapped into the crystal in anion vacancy,
(c) Non – stoichiometric defect
the defect is known as :
(d) Simple interstitial defect
(a) Schottky defect (b) Frenkel defect
67. Which of the following statements is /are correct?
(c) Stoichiometric defect (d) F-centre
(i) LiCl crystals are pink due to metal excess defect due
56. Schottky defect in crystals is observed when
to presence of extra L+i ion at interstitial sites.
(a) an ion leaves its normal site and occupies an interstitial
site (ii) Zinc oxide on heating turns yellow because its anionic
(b) unequal number of cations and anions are missing from sites are occupied by unpaired electrons.
the lattice (iii) In FeO crystals some Fe2+ are missing and the loss of
(c) density of the crystal increases positive charge is made up by the presence of required
number of Fe3+ ions.
(d) equal number of cations and anions are missing from
(a) (i) and (ii) (b) (i), (ii) and (iii)
the lattice
(c) (ii) and (iii) (d) (iii) only
57. The appearance of colour in solid alkali metal halides is
68. Match the columns
generally due to
Column-I Column-II
(a) Schottky defect (b) Frenkel defect
(A) Impurity defect (p) NaCl with anionic sites
(c) Interstitial positions (d) F-centre
F-centres
58. Which defect causes decrease in the density of crystal
(B) Metal excess defect (q) FeO with Fe3+
(a) Frenkel (b) Schottky
 EBD_7374
202 CHEMISTRY

(C) Metal deficiency (r) NaCl with Sr2+ and some (a) Diamagnetic (b) Ferromagnetic
defect cationic sites vacant (c) Ferrimagnetic (d) Antiferromagnetic
(a) A – (r), B – (p), C – (q) 79. Which of the following structure represents
(b) A – (p), B – (q), C – (r) ferrimagnetism?
(c) A – (r), B – (q), C – (p)
(a) ­¯­¯­¯ (b) ­­­­­
(d) A – (q), B – (p), C – (r)
69. A group 1 hydride crystal when heated in presence of its (c) ¯¯¯¯¯ (d) ­ ­ ¯ ­ ­ ¯
constituent metal vapour shows pink color. This metal can 80. White crystal of zinc oxide is heated
be (i) Metal excess defect is created.
(a) Na (b) K (c) Rb (d) Li (ii) Crystal become p-type semiconductor
70. Assertion : In any ionic solid (MX) with Schottky defects, (iii) Crystal become yellow in color.
the number of positive and negative ions are same. (iv) Free electron are created.
Reason : Equal number of cation and anion vacancies are (a) All statement(s) are correct.
present. (b) (i), (ii) and (iv)
(a) Assertion is correct, reason is correct; reason is a (c) (i), (ii) and (iii)
correct explanation for assertion.
(d) (ii) and (iv)
(b) Assertion is correct, reason is correct; reason is not a
81. Consider the Oxygen and chromium dioxide, both are placed
correct explanation for assertion
in magnetic field:
(c) Assertion is correct, reason is incorrect
(i) Oxygen is attracted strongly in a magnetic field.
(d) Assertion is incorrect, reason is correct.
(ii) Magnetic field persist in chromium dioxide while in
Topic 9: Electrical Properties and Magnetic Properties Oxygen not.
71. What is the energy gap between valence band and (a) Both Statements are correct.
conduction band in crystal of insulators ? (b) Statements (i) is correct only.
(a) Both the bands are overlapped with each other (c) Statements (ii) is correct only.
(b) Very small (d) Both Statements are incorrect.
(c) Infinite 82. Match the columns
(d) Very large Column-I Column-II
72. Doping of silicon (Si) with boron (B) leads to : (A) Mg in solid state (p) p-Type semiconductor
(a) n-type semiconductor (b) p-type semiconductor (B) MgCl2 in molten state (q) n-Type semiconductor
(c) metal (d) insulator
(C) Silicon with (r) Electrolytic conductors
73. To get a n- type semiconductor, the impurity to be added to
phosphorus
silicon should have which of the following number of
(D) Germanium with boron (s) Electronic conductors
valence electrons
(a) 1 (b) 2 (c) 3 (d) 5 (a) A – (q), B – (p), C – (r), D – (s)
74. The addition of arsenic to germanium makes the latter a (b) A – (p), B – (q), C – (s), D – (r)
(a) metallic conductor (b) intrinsic semiconductor (c) A – (s), B – (r), C – (q), D – (p)
(c) mixed conductor (d) extrinsic semiconductor (d) A – (r), B – (s), C – (p), D – (q)
75. Which of the folliowing metal oxides is anti-ferromagnetic 83. Assertion : Electrical conductivity of semiconductors
in nature? increases with increasing temperature.
(a) MnO2 (b) TiO2 (c) VO2 (d) CrO2 Reason : With increase in temperature, large number of
electrons from the valence band can jump to the conduction
76. Which of the following compound is like metallic copper in
band.
its conductivity and appearance?
(a) Assertion is correct, reason is correct; reason is a
(a) VO3 (b) TiO3 (c) ReO3 (d) CrO2
correct explanation for assertion.
77. Magnetic moment of electron is due to which of the
(b) Assertion is correct, reason is correct; reason is not a
following reason?
correct explanation for assertion
(a) Due to its orbital motion around the nucleus.
(c) Assertion is correct, reason is incorrect
(b) Due to its spin around its own axis.
(d) Assertion is incorrect, reason is correct.
(c) Due to negative charge on electron.
84. Which of the following is ferroelectric compound?
(d) Both (a) and (b). (a) BaTlO3 (b) K4[Fe(CN)6]
78. Which of the following type of substances can be (c) Pb2O3 (d) None of these
permanently magnetised?
THE SOLID STATE 203

85. Which one of the following statements is correct? 87. Match the columns
(a) NaCl is a paramagnetic salt Column-I Column-II
(Compound) (Magnetic Property)
(b) CuSO4 is a diamagnetic salt
(A) NaCl (p) Ferrimagnetic
(c) MnO is an example of ferromagnetic substance (B) MnO (q) Paramagnetic
(d) Ferrimagnetic substance like ZnFe 2O 4 becomes (C) CrCl3 (r) Ferromagnetic
paramagentic on heating (D) CrO2 (s) Diamagnetic
86. A solid with high electrical and thermal conductivity is (E) MgFe2O4 (t) Antiferromagnetic
(a) Si (b) Li (a) A – (p), B – (r), C – (q), D – (t), E – (s)
(b) A – (t), B – (q), C – (r), D – (p), E – (s)
(c) NaCl (d) Ice
(c) A – (r), B – (t), C – (q), D – (p), E – (s)
(d) A – (s), B – (t), C – (q), D – (r), E – (p)

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 6. Which of the following statement is not true about
amorphous solids?
1. Which of the following conditions favours the existence of
a substance in the solid state? (a) On heating they may become crystalline at certain
temperature
(a) High temperature (b) Low temperature
(b) They may become crystalline on keeping for long time
(c) High thermal energy (d) Weak cohesive forces
(c) Amorphous solids can be moulded by heating
2. Which of the following is not a characteristic of a crystalline
solid? (d) They are anisotropic in nature
(a) Definite and characteristic heat of fusion 7. The sharp melting point of crystalline solids is due to
(b) Isotropic nature (a) a regular arrangement of constituent particles
observed over a short distance in the crystal lattice
(c) A regular periodically repeated pattern of arrangement
of constituent particles in the entire crystal (b) a regular arrangement of constituent particles
observed over a long distance in the crystal lattice
(d) A true solid
(c) same arrangement of constituent particles in different
3. Which of the following is an amorphous solid? directions
(a) Graphite (C) (b) Quartz glass (SiO2) (d) different arrangement of constituent particles in
(c) Chrome alum (d) Silicon carbide (SiC) different directions.
4. Which of the following arrangements shows schematic 8. Iodine molecules are held in the crystals lattice by......... .
alignment of magnetic moments of antiferromagnetic (a) London forces
substances?
(b) dipole – dipole interactions
(a) (c) covalent bonds
(d) coulombic forces
(b) 9. Which of the following is a network solid?
(a) SO2 (solid) (b) I2
(c)
(c) Diamond (d) H2O (ice)
(d) 10. Which of the following solids is not an electrical conductor?
1. Mg(s) 2. TiO (s)
5. Which of the following is true about the value of refractive
index of quartz glass? 3. I2(s) 4. H2O(s)
(a) Same in all directions (a) Only 1 (b) Only 2
(b) Different in different directions (c) 3 and 4 (d) 2, 3 and 4
(c) Cannot be measured 11. Which of the following is not the characteristic of ionic
solids?
(d) Always zero
(a) Very low value of electrical conductivity in the molten
state
 EBD_7374
204 CHEMISTRY

(b) Brittle nature 23. In which of the following pair, most efficient packing is
(c) Very strong forces of interactions present?
(d) Anisotropic nature (a) hcp and bcc (b) hcp and ccp
12. Graphite is a good conductor of electricity due to the (c) bcc and ccp (d) bcc and simple cubic cell
presence of ........ . 24. The percentage of empty space in a body centred cubic
(a) lone pair of electrons (b) free valence electrons arrangement is ............ .
(c) cations (d) anions (a) 74 (b) 68 (c) 32 (d) 26
13. Which of the following oxides behaves as conductor or 25. Which of the following statement is not true about the
insulator depending upon temperature? hexagonal close packing?
(a) TiO (b) SiO2 (c) TiO3 (d) MgO (a) The coordination number is 12
14. Which of the following oxides shows electrical properties (b) It has 74% packing efficiency
like metals? (c) Tetrahedral voids of the second layer are covered by
(a) SiO2 (b) MgO (c) SO2(s) (d) CrO2 the spheres of the third layer
15. The lattice site in a pure crystal cannot be occupied by ..... (d) In this is arrangement spheres of the fourth layer are
(a) molecule (b) ion exactly aligned with those of the first layer
(c) electron (d) atom 26. In which of the following structures coordination number
for cations and anions in the packed structure will be same?
16. Graphite cannot be classified as ....... .
(a) Cl– ions form fcc lattice and Na+ ions occupy all
(a) conducting solid (b) network solid
octahedral voids of the unit cell
(c) covalent solid (d) ionic solid
(b) Ca2+ ions form fcc lattice and F– ions occupy all the
17. Cations are present in the interstitial sites in ...... . eight tetrahedral voids of the unit cell
(a) Frenkel defect (b) Schottky defect (c) O2– ions form fcc lattice and Na+ ions occupy all the
(c) vacancy defect (d) metal deficiency defect eight tetrahedral voids of the unit cell
18. Schottky defect is observed in crystals when ....... . (d) S2– ions form fcc lattice and Zn 2+ ions go into alternate
(a) some cations move from their lattice site to interstitial tetrahedral voids of the unit cell
sites 27. What is the coordination number in a square close packed
(b) equal number of cations and anions are missing from structure in two dimensions?
the lattice (a) 2 (b ) 3 (c) 4 (d) 6
(c) some lattice sites are occupied by electrons 28. Which kind of defects are introduced by doping?
(d) some impurity is present in the lattice (a) Dislocation defect (b) Schottky defect
19. Which of the following is true about the charge acquired (c) Frenkel defect (d) Electronic defect
by p – type semiconductors? 29. Silicon doped with electron rich impurity forms..... .
(a) Positive (a) p – type semiconductor
(b) Neutral (b) n – type semiconductor
(c) Negative (c) intrinsic semiconductor
(d) Depends on concentrations of p impurity (d) insulator
20. To get a n-type semiconductor from silicon, it should be
30. Which of the following statements is not true?
doped with a substance with valency ............ .
(a) Paramagnetic substances are weakly attracted by
(a) 2 (b) 1 (c) 3 (d) 5
magnetic field.
21. The total number of tetrahedral voids in the face-centred
(b) Ferromagnetic substances cannot be magnetised
unit cell is ......... .
permanently.
(a) 6 (b) 8 (c) 10 (d) 12
(c) The domains in antiferromagnetic substances are
22. Which of the following points defects are shown by AgBr(s) oppositely oriented with respect to each other.
crystals?
(d) Pairing of electrons cancels their magnetic moment in
1. Schottky defect 2. Frenkel defect the diamagnetic substances.
3. Metal excess defect 4. Metal deficiency defect 31. Which of the following is not true about the ionic solids?
(a) 1 and 2 (b) 3 and 4 (a) Bigger ions form the close packed structure
(c) 1 and 3 (d) 2 and 4 (b) Smaller ions occupy either the tetrahedral or the
octahedral voids depending upon their size
THE SOLID STATE 205

(c) Occupation of all the voids is not necessary 2 4

(a) a (b) a (c) 3 a (d)
3
a
(d) The fraction of octahedral or tetrahedral voids occupied 3 3 4 2
depends upon the radii of the ions occupying the voids –
39. If AgI crystallises in zinc blende structure with I ions at
32. A ferromagnetic substance becomes a permanent magnet lattice points. What fraction of tetrahedral voids is occupied
when it is placed in a magnetic field because........ . by Ag+ ions? [AIIMS 2014, A]
(a) all the domains get oriented in the direction of magnetic field (a) 25% (b) 50% (c) 100% (d) 75%
(b) all the domains get oriented in the direction opposite 40. Assertion : On heating ferromagnetic or ferrimagnetic
to the direction of magnetic field substances, they become paramagnetic.
(c) domains get oriented randomly Reason : The electrons change their spin on heating.
(d) domains are not affected by magnetic field [AIIMS 2014, C]
33. The correct order of the packing efficiency in different types (a) If both Assertion and Reason are correct and Reason
of unit cells is ...... . is the correct explanation of Assertion.
(a) fcc < bcc < simple cubic (b) If both Assertion and Reason are correct, but Reason
is not the correct explanation of Assertion.
(b) fcc > bcc > simple cubic
(c) If Assertion is correct but Reason is incorrect.
(c) fcc < bcc > simple cubic
(d) If both the Assertion and Reason are incorrect.
(d) bcc < fcc > simple cubic 41. CsCl crystallises in body centred cubic lattice. If ‘a’ is its
34. Which of the following defects is also known as dislocation edge length then which of the following expressions is
defect? correct? [JEE M 2014, S]
(a) Frenkel defect 3a
(a) r +r = 3a (b) r +r =
(b) Schottky defect Cs + Cl- Cs + Cl- 2
(c) Non – stoichiometric defect
3
(d) Simple interstitial defect (c) r +r =
a (d) rCs+ + rCl- = 3a
Cs+ Cl-2
35. In the cubic close packing, the unit cell has ....... .
42. The correct statement for the molecule, CsI3 is:
(a) 4 tetrahedral voids each of which is shared by four
adjacent unit cells [JEE M 2014, S]
(b) 4 tetrahedral voids within the unit cell (a) It is a covalent molecule.

(c) 8 tetrahedral voids each of which is shared by four (b) It contains Cs+ and I3- ions.
adjacent unit cells
(c) It contains Cs3+ and I– ions.
(d) 8 tetrahedral voids within the unit cells
(d) It contains Cs+, I– and lattice I2 molecule.
36. The edge lengths of the unit cells in terms of the radius of 43. A given metal crystallizes out with a cubic structure having
spheres constituting fcc, bcc and simple cubic unit cells edge length of 361 pm. If there are four metal atoms in one
are respectively ...... . unit cell, what is the radius of one atom? [AIPMT 2015, S]
4r 4r (a) 127 pm (b) 80 pm (c) 108 pm (d) 40 pm
(a) 2 2r, , 2r (b) , 2 2r, 2r
3 3 44. The vacant space in bcc lattice cell is : [AIPMT 2015, S]
4r 4r (a) 26 % (b) 48 % (c) 23 % (d) 32 %
(c) 2r, 2 2r, (d) 2r, , 2 2r
3 3 45. Which set of following characteristics for ZnS crystal is
37. Which of the following represents correct order of correct? [AIIMS 2015, A]
conductivity in solids? (a) Coordination number (4 : 4); ccp; Zn2+ ion in the
(a) kmetals >> kinsulators < ksemiconductors alternate tetrahedral voids
(b) kmetals << kinsulators < ksemiconductors (b) Coordination number (6 : 6); hcp; Zn 2+ ion in all
tetrahedral voids.
(c) kmetals. > ksemmiconductors > kinsulators = zero
(c) Coordination number (6 : 4); hcp; Zn 2+ ion in all
(d) kmetals < ksemiconductors > kinsulators ¹ zero octahedral voids
Past Year MCQs (d) Coordination number (4 : 4); ccp; Zn 2+ ion in all
tetrahedral voids.
38. If a is the length of the side of a cube, the distance between
46. Assertion : In close packing of spheres, a tetrahedral void
the body centered atom and one corner atom in the cube is surrounded by four spheres whereas an octahedral void
will be : [AIPMT 2014, S] is surrounded by six spheres.
 EBD_7374
206 CHEMISTRY

Reason : A tetrahedral void has a tetrahedral shape whereas 53. Sodium metal crystallizes in a body centred cubic lattice
an octahedral void has an octahedral shape. with a unit cell edge of 4.29Å. The radius of sodium atom is
[AIIMS 2015, A] approximately : [AIIMS 2017, S]
(a) If both Assertion and Reason are correct and Reason (a) 5.72Å (b) 0.93Å (c) 1.86Å (d) 3.22Å
is the correct explanation of Assertion. 54. A metal crystallises in a face centred cubic structure. If the
(b) If both Assertion and Reason are correct, but Reason edge length of its unit cell is 'a', the closest approach between
is not the correct explanation of Assertion. two atoms in metallic crystal will be : [JEE M 2017, S]
(c) If Assertion is correct but Reason is incorrect.
a
(d) If both the Assertion and Reason are incorrect. (a) 2a (b) 2 2 a (c) 2a (d)
2
47. Sodium metal crystallizes in a body centred cubic lattice
with a unit cell edge of 4.29Å. The radius of sodium atom is 55. The number of atoms per unit cell of bcc structure is
approximately : [JEE M 2015, S] [BITSAT 2017, A]
(a) 1 (b) 2 (c) 4 (d) 6
(a) 5.72Å (b) 0.93Å (c) 1.86Å (d) 3.22Å
56. Iron exhibits bcc structure at room temperature. Above
48. Graphite is a [BITSAT 2015, C] 900°C, it transforms to fcc structure. The ratio of density of
(a) molecular solid (b) covalent solid iron at room temperature to that at 900°C (assuming molar
(c) ionic solid (d) metallic solid mass and atomic radii of iron remains constant with
temperature) is [NEET 2018, A]
49. Molecules/ions and their magnetic properties are given
below. [AIIMS 2016, C] 3 4 3
Molecule/ion Magnetic property (a) (b)
2 3 2
(i) C6H6 (1) Antiferromagnetic
1 3 3
(ii) CrO2 (2) Ferrimagnetic (c) (d)
2 4 2
(iii) MnO (3) Ferromagnetic
57. Assertion : Schottky defect is produced in solids when
(iv) Fe3O4 (4) Paramagnetic
equal number of cations and anions are lost from lattice
(v) Fe3+ (5) Diamagnetic sites. This defect is observed in ionic crystals formed by
The correctly matched pairs in the above is cations and anions of nearly equal size.
(a) i-5, ii-3, iii-2, iv-1, v-4 (b) i-3, ii-5, iii-1, iv-4, v-2 Reason : We observe Schottky defect in crystals of KCl,
(c) i-5, ii-3, iii-1, iv-2, v-4 (d) i-5, ii-3, iii-1, iv-4, v-2 NaCl. [AIIMS 2018, C]
(a) If both Assertion and Reason are correct and Reason
50. Which one of the following statements about packing in
is the correct explanation of Assertion.
solids is incorrect ? [AIIMS 2016, S]
(b) If both Assertion and Reason are correct, but Reason
(a) Coordination number in bcc mode of packing is 8. is not the correct explanation of Assertion.
(b) Coordination number in hcp mode of packing is 12. (c) If Assertion is correct but Reason is incorrect.
(c) Void space in hcp mode of packing is 32%. (d) If both the Assertion and Reason are incorrect.
(d) Void space is ccp mode of packing is 26%. 58. The anions (A) form hexagonal closest packing and the
cations (C) occupy only 2/3 of octahedral holes. The
51. Al (at. wt 27) crystallizes in the cubic system with a cell edge
simplest formula of the ionic compound is :
of 4.05 Å . Its density is 2.7 g per cm3. Determine the unit
[AIIMS 2018, A]
cell type calculate the radius of the Al atom
(a) CA (b) C3A 2
[BITSAT 2016, A] (c) C4A 3 (d) C2A 3
(a) fcc, 2.432 Å (b) bcc, 2.432 Å 59. Which type of ‘defect’ has the presence of cations in the
(c) bcc, 1.432 Å (d) fcc, 1.432 Å interstitial sites? [JEE M 2018, C]
(a) Schottky defect (b) Vacancy defect
52. The non stoichiometric compound Fe 0.94O is formed when
(c) Frenkel defect (d) Metal deficiency defect
60. Each edge of a cubic unit cell is 400 pm long. If atomic mass
x % of Fe 2 + ions are replaced by as many 2 Fe 3 + ions, x is
3 of the element is 120 and its density is 6.25 g/cm3, the crystal
lattice is : (use NA = 6 × 1023) [BITSAT 2018, A]
[BITSAT 2016, S] (a) primitive (b) body centered
(a) 18 (b) 12 (c) 15 (d) 6 (c) face centered (d) end centered
THE SOLID STATE 207

Exercise 3 : Try If You Can

1. For two ionic solids CaO and KI, identify the wrong
statement amongst the following : 16 3 13 3 4 3 13 3
pr- + pr+ pr- + pr+
(c) 3 3 (d) 3 3
(a) The lattice energy of CaO is much large than that of KI
8(r+ + r- )3 8(r+ + r- )3
(b) KI is more soluble in water
(c) KI has higher melting point 7. The g-form of iron has fcc structure (edge length 386 pm)
(d) CaO has higher melting point and b-form has bcc structure (edge length 290 pm). The
ratio of density in g-form and b-form is
2. An alloy of copper, silver and gold is found to have copper
(a) 0.9788 (b) 1.02 (c) 1.57 (d) 0.6344
constituting the ccp lattice. If silver atoms accupy the edge
centres and gold is present at body centre, the alloy will 8. What is the density of Na2O having antiflurite-type crystal
structure, if the edge length of cube is 100 pm and what is
have the formula:
the effect on density by 0.05% Frenkel defect?
(a) Cu4Ag2Au (b) Cu4Ag4Au
(a) 823.5 g cm–3, density decreases
(c) Cu4Ag3Au (d) CuAgAu (b) 414.16 g cm–3, density decreases
3. The packing efficiency of the two-dimensional square unit (c) 823.5 g cm–3, density remains same
cell shown below is : (d) 414.16 g cm–3, density remains same
9. By X-ray diffraction it is found that nickel (at mass = 59 g
mol–1), crystallizes with ccp. The edge length of the unit
cell is 3.5 Å. If density of Ni crystal is 9.0 g/cm3 , then value
of Avogadro's number from the data is :
(a) 6.05 × 1023 (b) 6.11 × 1023
(c) 6.02 × 10 23 (d) 6.023 × 1023
L 10. MgO crystallizes in a cubic type crystal system. The ionic
radii for Mg2+ and O2– are 0.066 and 0.140 nm respectively.
(a) 39.27% (b) 68.02% (c) 74.05% (d) 78.54% One can conclude that the Mg2+ ions occupy:
4. First three nearest neighbour distances for primitive cubic (a) a cubic hole in a simple cubic structure
lattice are respectively (edge length of unit cell = a): (b) every tetrahedral hole in a close packed structure
(a) a, 2a , 3a (b) 3a , 2a , a (c) an octahedral hole in a cubic close packed structure
(d) every other tetrahedral hole in a close packed structure
(c) a 2a , 2a (d) a 3a , 2a 11. Coordination number of “C” in Be2C3 whose structure is
5. A body centered cubic lattice is made up of hollow spheres correlated with that of CaF2, is:
of B. Spheres of solid A are present in hollow spheres of B. (a) 2 (b) 4 (c) 6 (d) 8
Radius of A is half of radius of B. What is the ratio of total 12. An fcc lattice has a lattice parameter a = 400 pm. Calculate
volume of spheres of B unoccupied by A in a unit cell and the molar volume of the lattice including all the empty space.
volume of unit cell? (a) 10.8 mL (b) 96 mL (c) 8.6 mL (d) 9.6 mL
13. A metal crystallizes in bcc lattice. The percent fraction of
7 3p 7 3 edge length not covered by atom is
(a) (b)
64 128 (a) 10.4% (b) 13.4% (c) 12.4% (d) 11.4%
14. Which of the following has maximum value of cation/anion
7.p ratio?
(c) (d) None of these
24 (a) KCl (b) NaCl (c) CaF2 (d) MgCl2
6. Which of the following expression is correct for packing 15. A substance AxBy crystallizes in a face centred cubic (fcc)
fraction of NaCl if the ions along with one face are diagonally lattice in which atoms ‘A’ occupy each corner of the cube and
atoms ‘B’ occupy the centres of each face of the cube. Identify
removed?
the correct composition of the substance AxBy
13 3 16 3 13 3 4 3 (a) AB3
pr- + pr+ pr- + pr+ (b) A4B3
(a) 3 3 (b) 3 3
8(r+ + r- )3 8(r+ + r- )3 (c) A3B
(d) Composition can’t be specified
 EBD_7374
208 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 10 (c) 19 (d) 28 (d) 37 (b) 46 (b) 55 (d) 64 (c) 73 (d) 82 (c)
2 (a) 11 (b) 20 (a) 29 (a) 38 (b) 47 (c) 56 (d) 65 (c) 74 (d) 83 (a)
3 (b) 12 (d) 21 (d) 30 (c) 39 (a) 48 (a) 57 (d) 66 (a) 75 (a) 84 (a)
4 (c) 13 (d) 22 (d) 31 (d) 40 (b) 49 (a) 58 (b) 67 (d) 76 (c) 85 (d)
5 (c) 14 (b) 23 (a) 32 (a) 41 (a) 50 (a) 59 (c) 68 (a) 77 (d) 86 (b)
6 (c) 15 (a) 24 (b) 33 (d) 42 (b) 51 (d) 60 (a) 69 (d) 78 (b) 87 (d)
7 (a) 16 (b) 25 (a) 34 (d) 43 (d) 52 (b) 61 (b) 70 (a) 79 (d)
8 (a) 17 (c) 26 (b) 35 (a) 44 (b) 53 (b) 62 (c) 71 (d) 80 (b)
9 (b) 18 (a) 27 (b) 36 (d) 45 (a) 54 (d) 63 (b) 72 (b) 81 (c)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (b) 7 (b) 13 (c) 19 (b) 25 (d) 31 (d) 37 (a) 43 (a) 49 (c) 55 (b)
2 (b) 8 (a) 14 (d) 20 (d) 26 (a) 32 (a) 38 (d) 44 (d) 50 (c) 56 (d)
3 (b) 9 (c) 15 (c) 21 (b) 27 (c) 33 (b) 39 (b) 45 (a) 51 (d) 57 (b)
4 (d) 10 (c) 16 (d) 22 (a) 28 (d) 34 (a) 40 (a) 46 (c) 52 (a) 58 (d)
5 (a) 11 (a) 17 (a) 23 (b) 29 (b) 35 (d) 41 (c) 47 (c) 53 (c) 59 (c)
6 (d) 12 (b) 18 (b) 24 (c) 30 (b) 36 (a) 42 (b) 48 (b) 54 (d) 60 (b)
Exercis e 3 : Try If You Can
1 (c) 3 (d) 5 (d) 7 (a) 9 (b) 11 (d) 13 (b) 15 (a)
2 (c) 4 (a) 6 (a) 8 (d) 10 (c) 12 (d) 14 (c)
 16 Chapter
SOLUTIONS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Raoult’s Law.
AIIMS 3 Colligative Properties 4 8.2
JEE Main 2
BITSAT 2
 EBD_7374
210 CHEMISTRY
SOLUTIONS 211
 EBD_7374
212 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Types of Solutions and Expressing (a) 0.75 litre of 10 N HCl and 0.25 litre of 4 N HCl
Concentration of Solutions (b) 0.50 litre of 4 N HCl and 0.50 litre of 10 N HCl
(c) 0.67 litre of 4 N HCl and 0.33 litre of 10 N HCl
1. The term homogenous mixtures signifies that
(d) 0.80 litre of 4 N HCl and 0.20 litre of 10 N HCl
(a) its composition is uniform throughout the mixture.
15. Molarity of H2SO4 is 18 M. Its density is 1.8 g/ml. Hence
(b) its properties are uniform throughout the mixture.
molality is
(c) both composition and properties are uniform
(a) 36 (b) 200 (c) 500 (d) 18
throughout the mixture.
16. 200 ml of water is added to 500 ml of 0.2 M solution. What is
(d) neither composition nor properties are uniform
the molarity of this diluted solution ?
throughout the mixture.
(a) 0.5010 M(b) 0.2897 M(c) 0.7093 M(d) 0.1428 M
2. Molarity of liquid HCl will be, if density of solution is
17. How many grams of concentrated nitric acid solution should
1.17 g/cc
be used to prepare 250 mL of 2.0M HNO3 ? The concentrated
(a) 36.5 (b) 32.05 (c) 18.25 (d) 42.10
acid is 70% HNO3
3. 1 M, 2.5 litre NaOH solution is mixed with another 0.5 M,
(a) 90.0 g conc. HNO3 (b) 70.0 g conc. HNO3
3 litre NaOH solution. Then find out the molarity of resultant
(c) 54.0 g conc. HNO3 (d) 45.0 g conc. HNO3
solution
18. For preparing 0.1 N solution of a compound from its impure
(a) 0.80 M (b) 1.0 M (c) 0.73 M (d) 0.50 M
sample of which the percentage purity is known, the weight
4. An X molal solution of a compound in benzene has mole
of the substance required will be
fraction of solute equal to 0.2. The value of X is
(a) Less than the theoretical weight
(a) 14 (b) 3.2 (c) 1.4 (d) 2
(b) More than the theoretical weight
5. The molarity of pure water is
(c) Same as the theoretical weight
(a) 50 M (b) 18 M (c) 55.6 M (d) 100 M
(d) None of these
6. An aqueous solution of glucose is 10% in strength. The
volume in which 1 g mole of it is dissolved, will be N N N
19. If 50 mL H2SO4, 30 mL HNO3, 10 mL HCl is mixed
(a) 9 litre (b) 1.8 litre (c) 8 litre (d) 0.9 litre 10 3 2
and solution is made to 1L. Then normality of resultant
7. 10 g of NaCl is dissolved in 10 6 g of the solution. Its solution is
concentration is N N N
(a) 100 ppm (b) 0.1 ppm (c) 1 ppm (d) 10 ppm (a) (b) (c) (d) N
20 40 50
8. 2.5 litres of NaCl solution contain 5 moles of the solute. 20. A solution is prepared by dissolving 10 g NaOH in 1250 mL
What is the molarity? of a solvent of density 0.8 mL/g. The molality of the solution
(a) 5 molar (b) 2 molar in mol kg–1 is
(c) 2.5 molar (d) 12.5 molar (a) 0.25 (b) 0.2 (c) 0.008 (d) 0.0064
9. The mole fraction of the solute in one molal aqueous 21. For mixture containing “four” components which of the
solution? following is correct in term of mole fraction?
(a) 0.009 (b) 0.018 (c) 0.027 (d) 0.036 (a) x1+ x2+ x3+ x4 ¹ 1
10. 5 mL of N HCl, 20 mL of N/2 H2SO4 and 30 mL of N/3 HNO3 n3
(b) = x3
are mixed together and volume made to one litre. The n1 + n 2 + n 3
normality of the resulting solution is
n1 n
N N N N (c) x1 = = 1
(a) (b) (c) (d) n1 + n 2 + n 3 + n 4 Sn
5 10 20 40 (d) n1 + n2 + n3 + n4 = 1
11. 25mL of a solution of barium hydroxide on titration with a
22. Study the given statements and choose the correct option.
0.1 molar solution of hydrochloric acid gave a titre value of
(i) 3.62 mass percentage of sodium hypochlorite in water
35 mL. The molarity of barium hydroxide solution was
is used as commercial bleaching solution.
(a) 0.07 (b) 0.14 (c) 0.28 (d) 0.35
(ii) 35% volume percentage of ethylene glycol is used as
12. Mole fraction of the solute in a 1.00 molal aqueous solution
an antifreeze (as coolent in car engines).
is
(iii) Concentration of dissolved oxygen in a litre of sea
(a) 0.1770 (b) 0.0177 (c) 0.0344 (d) 1.7700
water is 5.8 ppm.
13. What is the normality of a 1 M solution of H3PO4 ?
(a) Statements (i) and (ii) are correct
(a) 0.5 N (b) 1.0 N (c) 2.0 N (d) 3.0 N
(b) Statements (i) and (iii) are correct
14. The volume of 4 N HCl and 10 N HCl required to make 1 litre
(c) Statements (ii) and (iii) are correct
of 6 N HCl are
(d) Statements (i),(ii) and (iii) are correct
SOLUTIONS 213

23. Match the columns 31. The solubility of a solid in a liquid is significantly affected
Column -I Column-II by temperature changes.
(A) Mass percentage (p) Medicine and pharmacy ˆˆ† Solution.
Solute + Solvent ‡ˆˆ
(B) Mass by volume (q) Concentration of The system being in a dynamic equilibrium must follow
pollutants in water Le-chatelier’s principle. Considering the Le-chatelier’s
(C) ppm (r) Industrial chemical principle which of the following is correct?
application (a) DHsol > 0; solubility ­ ; temperature ¯
(D) Volume percentage (s) Liquid solutions
(a) A – (q), B – (p), C – (s), D – (r) (b) DHsol < 0; solubility ¯ ; temperature ­
(b) A – (s), B – (r), C – (p), D – (q) (c) DHsol > 0; solubility ¯ ; temperature ­
(c) A – (r), B – (q), C – (s), D – (p) (d) DHsol < 0; solubility ­ ; temperature ­
(d) A – (r), B – (p), C – (q), D – (s)
24. Assertion : Molarity of a solution in liquid state changes 32. W1
with temperature. Piston W1 W2 W3
Reason : The volume of a solution changes with change in
temperature.
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a (a) (b)
correct explanation for assertion On the basis of the figure given above which of the following
(c) Assertion is correct, reason is incorrect is not true?
(d) Assertion is incorrect, reason is correct. (a) In figure (a) assuming the state of dynamic equilibrium
25. The normality of orthophosphoric acid having purity of 70 %
rate of gaseous particles entering and leaving the
by weight and specific gravity 1.54 is
(a) 11 N (b) 22 N (c) 33 N (d) 44 N solution phase is same.
26. Which of the following statements, regarding the mole (b) In figure (b) on compressing the gas number of
fraction (x) of a component in solution, is incorrect? gaseous particles per unit volume over the solution
increases.
(a) 0 £ x £ 1 (b) x £ 1
(c) x is always non-negative (d) None of these (c) Rate at which gaseous particles are striking the solution
to enter it, decreases.
Topic 2: Solubility (d) Rate at which gaseous particles are striking the solution
27. Which of the following factor do not affect solubility of to enter it, increases.
solid solute in liquid ? 33. The statement “If 0.003 moles of a gas are dissolved in 900 g
(a) Temperature (b) Pressure of water under a pressure of 1 atmosphere, 0.006 moles will
(c) Nature of solute (d) All of these be dissolved under a pressure of 2 atmospheres”, illustrates
28. At the state of dynamic equilibrium, for (a) Dalton’s law of partial pressure
solute + solvent solution. (b) Graham’s law
(a) Rate of dissolution = Rate of unsaturation. (c) Raoult’s law
(b) Rate of dissolution = Rate of unsaturation. (d) Henry’s law
(c) Rate of dissolution = Rate of saturation 34. According to Henry’s law, the amount of gas that will
(d) Rate of crystallization = Rate of saturation. dissolve in blood plasma or any other liquid is determined
29. Which of the following statements is incorrect? by which of these factor?
(a) A solution in which no more solute can be dissolved (a) Solubility of the gas in the liquid.
at the same temperature and pressure is called a (b) The total pressure of the gas mixture .
saturated solution. (c) pH of the liquid.
(b) An unsaturated solution is one in which more solute (d) The osmotic pressure of the gas mixture.
can be dissolved at the same temperature. 35. Henry’s law constant of oxygen is 1.4 × 10–3 mol. lit–1. atm–1 at
(c) The solution which is in dynamic equilibrium with 298 K. How much of oxygen is dissolved in 100 ml at 298 K
undissolved solute is the saturated solution. when the partial pressure of oxygen is 0.5 atm?
(d) The minimum amount of solute dissolved in a given (a) 1.4 g (b) 3.2 g (c) 22.4 mg (d) 2.24 mg
amount of solvent is its solubility. 36. At equillibrium the rate of dissolution of a solid solute in a
30. On dissolving sugar in water at room temperature solution volatile liquid solvent is ______.
feels cool to touch. Under which of the following cases (a) less than the rate of crystallisation.
dissolution of sugar will be most rapid ? (b) greater than the rate of crystallisation.
(a) Sugar crystals in cold water. (c) equal to the rate of crystallisation.
(b) Sugar crystals in hot water. (d) zero
(c) Powdered sugar in cold water. 37. A beaker contains a solution of substance ‘A’. Precipitation
(d) Powdered sugar in hot water. of substance ‘A’ takes place when small amount of ‘A’ is
added to the solution. The solution is ______.
 EBD_7374
214 CHEMISTRY

(a) saturated (b) supersaturated (c) at high altitudes the partial pressure of oxygen is equal
(c) unsaturated (d) concentrated to at the ground level.
38. Maximum amount of a solid solute that can be dissolved in (d) None of these.
a specified amount of a given liquid solvent does not depend 46. Read the following statements carefully and choose the
upon __________. correct option.
(a) Temperature (b) Nature of solute (i) Different gases have different KH values at the same
(c) Pressure (d) Nature of solvent temperature.
39. Low concentration of oxygen in the blood and tissues of (ii) Higher the value of KH at a given temperature, lower is
people living at high altitude is due to _________. the solubility of the nature of gas in the liquid.
(a) low temperature (iii) KH is a function of the nature of the gas.
(b) low atmospheric pressure (iv) Solubility of gases increases with increase of
(c) high atmospheric pressure temperature.
(d) both low temperature and high atmospheric pressure (a) (i), (ii) and (iv) are correct.
40. Value of Henry's constant KH _______. (b) (ii) and (iv) are correct.
(a) increases with increase in temperature. (c) (i), (ii) and (iii) are correct.
(b) decreases with increase in temperature. (d) (i) and (iv) are correct.
(c) remains constant. 47. Which one of the following gases has the lowest value of
(d) first increases then decreases. Henry’s law constant?
41. The value of Henry's constant KH is _______. (a) N2 (b) He (c) H2 (d) CO2
(a) greater for gases with higher solubility. 48. Equal masses of methane and oxygen are mixed in an empty
(b) greater for gases with lower solubility. container at 25°C. The fraction of the total pressure exerted
(c) constant for all gases. by oxygen is
(d) not related to the solubility of gases.
42. Which of the following graph is a correct representation of (a) 1/2 (b) 2/3 (c) 1 ´ 273 (d) 1/3
3 298
Henry’s law? 49. When a gas is bubbled through water at 298 K, a very dilute
(a) (b) solution of the gas is obtained. Henry’s law constant for the
Partial pressure of gas
Partial pressure of gas

gas at 298 K is 100 kbar. If the gas exerts a partial pressure of

1 bar, the number of millimoles of the gas dissolved in one
litre of water is
(a) 0.555 (b) 5.55 (c) 0.0555 (d) 55.5
50. What is the ratio of no. of moles of nitrogen to that of
oxygen in a container of 5 litre at atmospheric pressure?
Mole fraction of gas Mole fraction of gas (a) 1 : 1.71 (b) 1 : 2 (c) 2 : 1 (d) 1 : 24
in solution in solution
Topic 3: Vapour Presure of Liquid Solutions
(c) (d) 51. Iodine and sulphur dissolve in
Partial pressure of gas
Partial pressure of gas

(a) water (b) benzene

(c) carbon disulphide (d) ethanol
52. The decrease in the vapour pressure of solvent depends
on the
(a) quantity of non-volatile solute present in the solution
Mole fraction of gas Mole fraction of gas (b) nature of non-volatile solute present in the solution
in solution in solution (c) molar mass of non-volatile solute present in the
43. Which is an application of Henry’s law? solution
(a) Spray paint (b) Bottled water (d) physical state of non-volatile solute present in the
(c) Filling up atire (d) Soft drinks (soda) solution
44. Scuba divers may experience a condition called ______. 53. A plot of p1 or p2 vs the mole fractions x1 and x2 is given as.
To avoids this, the tanks used by scuba divers are filled
with air diluted with _____ . III p2°
p2
(a) Migrains, Hydrogen (b) Cramps, Nitrogen = p1 +
p Total
(c) Nausea, Oxygen (d) Bends, Helium II
Vapour pressure

45. People living at high attitudes often reported with a problem p° p2

1
of feeling weak and inability to think clearly. The reason for
this is. p
1
(a) at high altitudes the partial pressure of oxygen is less I
than at the ground level.
(b) at high altitudes the partial pressure of oxygen is more x1 = 1 Mole fraction x1 = 0
x2 = 0 x2 x2 = 1
than at the ground level.
SOLUTIONS 215

In this figure, lines I and II pass through the point for which. 62. Consider a and b are two components of a liquid mixture,
(a) x1 ¹ 1; x2 = 1 (b) x1 = x2 ¹ 1 their corresponding vapour pressure (mmHg) are
(c) x1 = 1; x2 ¹ 1 (d) x1 = x2 = 1 respectively 450 and 700 in pure states and total pressure
54. The vapour pressure of two liquids ‘P’ and ‘Q’ are 80 and given is 600. Then corresponding composition in liquid
60 torr, respectively. The total vapour pressure of solution phase will be
obtained by mixing 3 mole of P and 2 mole of Q would be (a) 0.4, 0.6 (b) 0.5, 0.5 (a) 0.6, 0.4 (d) 0.3, 0.7
(a) 72 torr (b) 140 torr (c) 68 torr (d) 20 torr 63. Which will form maximum boiling point azeotrope
55. 18 g of glucose (C6H12O6) is added to 178.2 g of water. The (a) HNO3 + H2O solution
vapour pressure of water for this aqueous solution is (b) C2H5OH + H2O solution
(a) 76.00 torr (b) 752.40 torr (c) C6H6 + C6H5CH3 solution
(c) 759.00 torr (d) 7.60 torr (d) None of these
56. PA and PB are the vapour pressure of pure liquid components,
Topic 4: Ideal and Non-Ideal Solution
A and B, respectively of an ideal binary solution. If XA
represents the mole fraction of component A, the total 64. A solution containing components A and B follows Raoult's
pressure of the solution will be. law when
(a) PA + XA (PB – PA) (b) PA + XA (PA– PB) (a) A – B attraction force is greater than A – A and B – B
(c) PB + XA (PB – PA) (d) PB + XA (PA – PB) (b) A – B attraction force is less than A – A and B – B
57. An 1% solution of KCl (I), NaCl (II), BaCl2 (III) and urea (IV) (c) A – B attraction force remains same as A–A and B –B
have their osmotic pressure at the same temperature in the (d) volume of solution is different from sum of volume of
ascending order (molar masses of NaCl, KCl, solute and solvent
BaCl2 and urea are respectively 58.5, 74.5, 208.4 and 65. Which one of the following is not correct for an ideal
60 g mole–1). Assume 100% ionization of the electrolytes at solution?
this temperature (a) It must obey Raoult’s law
(a) I < III < II < IV (b) III < I < II < IV (b) DH = 0
(c) I < II < III < IV (d) III < IV < I < II (c) DH = DV ¹ 0
58. A mixture of ethyl alcohol and propyl alcohol has a vapour (d) All are correct
pressure of 290 mm Hg at 300 K. The vapour pressure of 66. All form ideal solution except
propyl alcohol is 200 mm Hg. If the mole fraction of ethyl (a) C6H6 and C6H5CH3 (b) C2H6 and C2H5I
alcohol is 0.6, its vapour pressure (in mm Hg) at the same (c) C6H5Cl and C6H5Br (d) C2H5 I and C2H5OH.
temperature will be 67. Which one of the following is non-ideal solution
(a) 360 (b) 350 (c) 300 (d) 700 (a) Benzene + toluene
59. Two liquids X and Y form an ideal solution. At 300 K, vapour (b) n-hexane + n-heptane
pressure of the solution containing 1 mol of X and 3 mol of (c) Ethyl bromide + ethyl iodide
Y is 550 mm Hg. At the same temperature, if 1 mol of Y is (d) CCl4 + CHCl3
further added to this solution, vapour pressure of the 68. Mixtures of ethanol and acetone show positive deviation.
solution increases by 10 mm Hg. Vapour pressure ( in mm Hg) The reason is
of X and Y in their pure states will be, respectively (a) In pure ethanol, molecules are hydrogen bonded.
(a) 300 and 400 (b) 400 and 600 (b) In pure acetone, molecules are hydrogen bonded
(c) 500 and 600 (d) 200 and 300 (c) In both molecules are hydrogen bonded
60. The vapour pressure of pure benzene and toluene at a (d) None of these
particular temperature are 100 mm and 50 mm respectively. 69. A mixture of components A and B will show –ve deviation
Then the mole fraction of benzene in vapour phase in contact when
with equimolar solution of benzene and toluene is (a) DVmix > 0
(a) 0.67 (b) 0.75 (c) 0.33 (d) 0.50
(b) DHmix < 0
61. Read the following statements carefully and choose the
(c) A – B interaction is weaker than A – A and B – B
correct option
interactions
(i) The vapour pressure of a liquid decreases with increase
(d) A–B interaction is stronger than A–A and B–B
of temperature.
interactions.
(ii) The liquid boils at the temperature at which its vapour
pressure is equal to the atmospheric pressure. 70. Which of the following liquid pairs shows a positive
(iii) Vapour pressure of the solvent decreases in the deviation from Raoult’s law ?
presence of non-volatile solute. (a) Water - Nitric acid
(iv) Vapour pressure of the pure solvent and solution is a (b) Benzene - Methanol
function of temperature. (c) Water - Hydrochloric acid
(a) (i), (ii) and (iv) are correct (d) Acetone - Chloroform
(b) (i), (iii), and (iv) are correct 71. Negative deviation from Raoult’s law is observed in which
(c) (ii), (iii), and (iv) are correct one of the following binary liquid mixtures?
(d) (i), (ii) and (iii) are correct (a) Ethanol and acetone
(b) Benzene and toluene
 EBD_7374
216 CHEMISTRY

(c) Acetone and chloroform 78. At 300 K the vapour pressure of an ideal solution containing
(d) Chloroethane and bromoethane 1 mole of liquid A and 2 moles of liquid B is 500 mm of Hg.
72. A binary liquid solution is prepared by mixing n-heptane The vapour pressure of the solution increases by 25 mm of
and ethanol. Which one of the following statements is Hg, if one more mole of B is added to the above ideal solution
correct regarding the behaviour of the solution? at 300 K. Then the vapour pressure of A in its pure state is
(a) The solution is non-ideal, showing negative deviation (a) 300 mm of Hg (b) 400 mm of Hg
from Raoult’s Law. (c) 500 mm of Hg (d) 600 mm of Hg
(b) The solution is non-ideal, showing positive deviation Topic 5: Colligative properties and Determination of Molar Mass
from Raoult’s Law.
79. The relative lowering of the vapour pressure is equal to the
(c) n-heptane shows positive deviation while ethanol
ratio between the number of
shows negative deviation from Raoult’s Law.
(a) solute molecules to the solvent molecules
(d) The solution formed is an ideal solution.
(b) solute molecules to the total molecules in the solution
73. The azeotropic mixture of water (b.p.100°C) and HCl
(c) solvent molecules to the total molecules in the solution
(b.p.85°C) boils at 108.5°C. When this mixture is distilled it
(d) solvent molecules to the total number of ions of the
is possible to obtain
solute.
(a) pure HCl
80. Vapour pressure of benzene at 30°C is 121.8 mm Hg. When
(b) pure water 15 g of a non volatile solute is dissolved in 250 g of benzene
(c) pure water as well as pure HCl its vapour pressure decreased to 120.2 mm Hg. The molecular
(d) neither HCl nor H2O in their pure states weight of the solute (Mo. wt. of solvent = 78)
74. The system that forms maximum boiling azeotrope is (a) 356.2 (b) 456.8 (c) 530.1 (d) 656.7
(a) carbondisulphide – acetone 81. The value of P° for benzene is 640 mm of Hg. The vapour
(b) benzene – toluene pressure of solution containing 2.5gm substance in 39gm.
(c) acetone – chloroform benzene is 600mm of Hg the molecular mass of X is
(d) n-hexane – n-heptane (a) 65.25 (b) 130 (c) 40 (d) 80
75. Which one of the following binary mixtures forms an 82. The vapour pressure at a given temperature of an ideal
azeotrope with minimum boiling point type? solution containing 0.2 mol of a non-volatile solute and 0.8
(a) acetone-ethanol (b) H2O-HNO3 mol of solvent is 60 mm of Hg. The vapour pressure of the
(c) benzene-toluene (d) n-hexane-n-heptane pure solvent at the same temperature is
76. On the basis of information given below mark the correct (a) 150 mm of Hg (b) 60 mm of Hg
option. (c) 75 mm of Hg (d) 120 mm of Hg
(i) In bromoethane and chloroethane mixture 83. 12 g of a nonvolatile solute dissolved in 108 g of water
intermolecular interactions of A-A and B-B type are produces the relative lowering of vapour pressure of 0.1.
nearly same as A-B type interactions. The molecular mass of the solute is
(ii) In ethanol and acetone mixture A-A or B-B type (a) 80 (b) 60 (c) 20 (d) 40
intermolecular interactions are stronger than A-B type 84. The amount of solute (molar mass 60 g.mol–1) that must be
interactions. added to 180 g of water so that the vapour pressure of water
(iii) In chloroform and acetone mixture A-A or B-B type is lowered by 10% is
intermolecular interactions are weaker than A-B type (a) 30 g (b) 60 g (c) 120 g (d) 12 g
interactions. 85. The vapour pressure of water at 20°C is 17.5 mm Hg. If 18 g
(a) Solution (ii) and (iii) will follow Raoult's law. of glucose (C6H12O6) is added to 178.2 g of water at 20°C,
(b) Solution (i) will follow Raoult's law. the vapour pressure of the resulting solution will be
(c) Solution (ii) will show negative deviation from Raoult's (a) 17.325 mm Hg (b) 15.750 mm Hg
law. (c) 16.500 mm Hg (d) 17.500 mm Hg
(d) Solution (iii) will show positive deviation from Raoult's 86. Which one of the following is a colligative property ?
law. (a) Boiling point (b) Vapour pressure
77. Assertion : Azeotropic mixtures are formed only by (c) Osmotic pressure (d) Freezing point
non-ideal solutions and they may have boiling points either 87. Which one of the following aqueous solutions will exihibit
greater than both the components or less than both the highest boiling point ?
components. (a) 0.015 M urea (b) 0.01 M KNO3
Reason : The composition of the vapour phase is same as (c) 0.01 M Na2SO4 (d) 0.015 M glucose
that of the liquid phase of an azeotropic mixture. 88. The rise in the boiling point of a solution containing 1.8 g of
(a) Assertion is correct, reason is correct; reason is a glucose in 100 g of solvent is 0.1°C. The molal elevation
correct explanation for assertion. constant of the liquid is
(b) Assertion is correct, reason is correct; reason is not a (a) 0.01 K/m (b) 0.1 K/m (c) 1 K/m (d) 10 K/m
correct explanation for assertion 89. For an electrolyte, elevation of B.P. is directly proportional to
(c) Assertion is correct, reason is incorrect (a) molarity (b) molality
(d) Assertion is incorrect, reason is correct. (c) mole fraction (d) All of these
SOLUTIONS 217

90. Which of the following aqueous solution has minimum of the unknown solute?
freezing point ? (a) 60 (b) 80 (c) 72 (d) 63
(a) 0.01 m NaCl (b) 0.005 m C2H5OH 102. If 0.1 M solution of glucose and 0.1 M solution of urea are
(c) 0.005 m MgI2 (d) 0.005 m MgSO4. placed on two sides of the semipermeable membrane to equal
91. 1.00 g of a non-electrolyte solute (molar mass 250 g mol–1) heights, then it will be correct to say that
was dissolved in 51.2 g of benzene. If the freezing point (a) there will be no net movement across the membrane
depression constant, Kf of benzene is 5.12 K kg mol–1, the (b) glucose will flow towards urea solution
freezing point of benzene will be lowered by (c) urea will flow towards glucose solution
(a) 0.3 K (b) 0.5 K (c) 0.4 K (d) 0.2 (d) water will flow from urea solution to glucose
92. In a 0.2 molal aqueous solution of a weak acid HX the degree 103. Which observation(s) reflect(s) colligative properties?
of ionization is 0.3. Taking kf for water as 1.85, the freezing (i) A 0.5 m NaBr solution has a higher vapour pressure
point of the solution will be nearest to than a 0.5 m BaCl2 solution at the same temperature
(a) – 0.360ºC (b) – 0.260ºC (ii) Pure water freezes at the higher temperature than pure
(c) + 0.481ºC (d) – 0.481ºC methanol
93. The molecular weight of benzoic acid in benzene as (iii) a 0.1 m NaOH solution freezes at a lower temperature
determined by depression in freezing point method than pure water
corresponds to Choose the correct answer from the codes given below
(a) ionization of benzoic acid. (a) (i), (ii) and (iii) (b) (i) and (ii)
(b) dimerization of benzoic acid. (c) (ii) and (iii) (d) (i) and (iii)
(c) trimerization of benzoic acid. 104. Assertion : When NaCl is added to water a depression in
(d) solvation of benzoic acid. freezing point is observed.
94. A 0.5 molal solution of ethylene glycol in water is used as Reason : The lowering of vapour pressure of a solution
coolant in a car. If the freezing point constant of water be causes depression in the freezing point.
1.86°C per mole, the mixture shall freeze at (a) Assertion is correct, reason is correct; reason is a
(a) 0.93°C (b) –0.93°C (c) 1.86°C (d) –1.86°C correct explanation for assertion.
95. The freezing point of 1% solution of lead nitrate in water will (b) Assertion is correct, reason is correct; reason is not a
be correct explanation for assertion
(a) 2°C (b) 1°C (c) 0°C (d) below 0°C (c) Assertion is correct, reason is incorrect
96. A solution of sucrose (molar mass = 342 g mol –1) has been (d) Assertion is incorrect, reason is correct.
prepared by dissolving 68.5 g of sucrose in 1000 g of water. 105. Assertion : When a solution is separated from the pure
The freezing point of the solution obtained will be solvent by a semi- permeable membrane, the solvent
(Kf for water = 1.86 K kg mol –1). molecules pass through it from pure solvent side to the
(a) – 0.372°C (b) – 0.520°C solution side
Reason : Diffusion of solvent occurs from a region of high
(d) + 0.372°C (d) – 0.570°C
concentration solution to a region of low concentration
97. Blood cells retain their normal shape in solution which are
solution.
(a) hypotonic to blood (b) isotonic to blood
(a) Assertion is correct, reason is correct; reason is a
(c) hypertonic to blood (d) equinormal to blood. correct explanation for assertion.
98. Isotonic solutions have same (b) Assertion is correct, reason is correct; reason is not a
(a) molar concentration (b) molality correct explanation for assertion
(c) normality (d) None of these (c) Assertion is correct, reason is incorrect
99. Which of the following pairs of solution are isotonic at the (d) Assertion is incorrect, reason is correct.
same temperature ? 106. Someone has added a non electrolyte solid to the pure
(a) 0.1 M Ca(NO3)2 and 0.1 M Na2SO4 liquid but forgot that among which of the two beakers he
(b) 0.1 M NaCl and 0.1 M Na2SO4 has added that solid. This problem can be solved by
(c) 0.1 M urea and 0.1 M MgCl2 checking
(d) 0.2 M urea and 0.1 M NaCl (a) relative lower in vapour pressure
100. Osmotic pressure of 0.4% urea solution is 1.64 atm and that (b) elevation in boiling point
of 3.42% cane sugar is 2.46 atm. When the above two (c) depression in Freezing point
solutions are mixed, the osmotic pressure of the resulting (d) all above
solution is : 107. Vapour pressure of benzene at 30°C is 121.8 mm. When 15g
(a) 0.82 atm (b) 2.46 atm (c) 1.64 atm (d) 4.10 atm of a non-volatile solute is dissolved in 250 g of benzene, its
101. At 25°C, at 5 % aqueous solution of glucose (molecular vapour pressure is decreased to 120.2 mm. The molecular
weight = 180 g mol–1) is isotonic with a 2% aqueous solution weight of the solute is
containing an unknown solute. What is the molecular weight (a) 35.67 g (b) 356.7 g (c) 432.8 g (d) 502.7 g
 EBD_7374
218 CHEMISTRY

108. For a dilute solution containing 2.5 g of a non-volatile non- 114. Van’t Hoff factor is given by the expression ________.
electrolyte solute in 100 g of water, the elevation in boiling
point at 1 atm pressure is 2°C. Assuming concentration of Normal molar mass
(a) i=
solute is much lower than the concentration of solvent, the Abnormal molar mass
vapour pressure (mm of Hg) of the solution is
(take Kb = 0.76 K kg mol–1) Abnormal molar mass
(b) i =
(a) 724 (b) 740 (c) 736 (d) 718 Normal molar mass
109. The difference between the boiling point and freezing point
of an aqueous solution containing sucrose (molecular wt = Observed colligative property
(c) i=
342 g mole–1) in 100 g of water is 105°C. If K f and Calculated colligative property
Kb of water are 1.86 and 0.51 K kg mol–1 respectively, the (d) Both (a) and (c)
weight of sucrose in the solution is about 115. If a is the degree of dissociation of Na 2SO4, the Vant Hoff’s
(a) 34.2 g (b) 342 g (c) 7.2 g (d) 72 g factor (i ) used for calculating the molecular mass is
110. If the elevation in boiling point of a solution of non-volatile, (a) 1 + a (b) 1 – a
non-electrolytic and non-associating solute in a solvent
(c) 1 + 2a (d) 1 – 2a
(Kb = x K kg mol–1) is y K, then the depression in freezing
point of solution of same concentration would be (Kf of the 116. The freezing point of equimolal aqueous solutions will be
solvent = z K kg mol–1) highest for
(a) C6H5NH3+Cl– (aniline hydrochloride)
2xz yz xz yz
(a) (b) (c) (d) (b) Ca(NO3)2
y x y 2x
111. 1 g of a non-volatile, non-electrolyte solute of molar mass (c) La(NO3)3
250 g/mol was dissolved in 51.2 g of benzene. If the (d) C6H12O6 (glucose)
freezing point depression constant Kf of benzene is 5.12
117. At 25°C, the highest osmotic pressure is exhibited by 0.1 M
kg K mol–1. The freezing point of benzene is lowered by
solution of
(a) 0.3 K (b) 0.5 K (c) 0.2 K (d) 0.4 K
(a) CaCl2 (b) KCl (c) glucose (d) urea
Topic 6: Abnormal Molar Mass 118. Which one of the following salts will have the same value of
van’t Hoff factor (i) as that of K4[Fe(CN)6].
112. The van’t Hoff factor i for a compound which undergoes
dissociation in one solvent and association in other solvent (a) Al2(SO4)3 (b) NaCl
is respectively (c) Al(NO3)3 (d) Na2SO4.
(a) less than one and greater than one. 119. The elevation in boiling point of a solution of 13.44 g of
(b) less than one and less than one. CuCl2 in 1 kg of water using the following information will
(c) greater than one and less than one. be (Molecular weight of CuCl2= 134.4 g and Kb= 0.52 K
kg mol-1)
(d) greater than one and greater than one.
(a) 0.16 (b) 0.05 (c) 0.1 (d) 0.2
113. If the various terms in the given below expressions have
usual meanings, the van’t Hoff factor (i) cannot be calculated 120. Freezing point of an aqueous solution is – 0.186°C. If
by which one of the following expressions the values of Kb and Kf of water are respectively 0.52 K kg
mol–1 and 1.86 K kg mol–1, then the elevation of boiling
(a) pV = inRT point of the solution in K is
(b) DT f = iK f .m (a) 0.52 (b) 1.04 (c) 1.34 (d) 0.052
(c) DTb = iK b .m
°
Psolvent - Psolution æ n ö
(d) = iç ÷
°
Psolvent èN+nø
SOLUTIONS 219

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 10. The unit of ebullioscopic constant is
(a) K kg mol–1 or K (molality)–1
1. Which of the following units is useful in relating
(b) mol kg K–1 or K–1 (molality)
concentration of solution with its vapour pressure?
(a) Mole fraction (b) Parts per milion (c) kg mol–1 K–1or K–1 (molality)–1
(c) Mass percentage (d) Molality (d) K mol kg–1or K (molality)
2. On dissolving sugar in water at room temperature solution 11. In comparison to a 0.01 M solution of glucose, the depression
feels cool to touch. Under which of the following cases in freezing point of a 0.01 M MgCl2 solution is ....... .
dissolution of sugar will be most rapid? (a) the same (b) about twice
(a) Sugar crystals in cold water (c) about three time (d) about six times
(b) Sugar crystals in hot water 12. An unripe mango placed in a concentrated salt solution to
(c) Powdered sugar in cold water prepare pickle shrivels because .......... .
(d) Powdered sugar in hot water (a) it gains water due to osmosis
3. At equilibrium the rate of dissolution of a solid solute in a (b) it loses water due to reverse osmosis
volatile liquid solvent is ....... (c) it gains water due to reverse osmosis
(a) less than the rate of crystallisation (d) it loses water due to osmosis
(b) greater than the rate of crystallisation 13. At a given temperature, osmotic presure of a concentrated
(c) equal to the rate of crystallisation solution of a substance ............ .
(d) zero (a) is higher than that of a dilute solution
4. A beaker contains a solution of substance 'A'. Precipitation (b) is lower than that of a dilute solution
of substance 'A' takes place when small amount of 'A' is (c) it gains water due to reverse osmosis
added to the solution. The solution is ........ . (d) it loses water due to osmosis
(a) saturated (b) supersaturated 14. Which of the following statements is false?
(c) unsaturated (d) concentrated (a) Two different solutions of sucrose of same molality
5. Maximum amount of a solid solute that can be dissolved in prepared in diffferent solvents will have the same
a specified amount of a given liquid solvent does not depression in freezing point.
depends upon ......... . (b) The osmotic pressure of a solution is given by the
(a) temperature (b) nature of solute equation p = CRT (where, C is the molarity of the
(c) pressure (d) nature of solvent solution)
6. Low concentration of oxygen in the blood and tissues of
(c) Decreasing order of osmotic pressure for 0.01 M
people living at high altitude is due to ............ .
aqueous solutions of barium chloride, potassium
(a) low temperature
chloride, acetic acid and sucrose is
(b) low atmospheric pressure
BaCl2 > KCl > CH3COOH > sucrose
(c) high atmospheric pressure
(d) According to Raoult's law, the vapour pressure exerted
(d) both low temperature and high atmospheric pressure
by a volatile component of a solution is directly
7. Considering the formation, breaking and strength of
proportional to its mole fraction in the solution
hydrogen bond, predict which of the following mixtures
will show a positive deviation from Raoult's law? 15. The value of van't Hoff factors for KCl, NaCl and K2SO4
(a) Methanol and acetone respectively are ............ .
(b) Chloroform and acetone (a) 2, 2 and 2 (b) 2, 2 and 3
(c) Nitric acid and water (c) 1, 1 and 2 (d) 1, 1 and 1
(d) Phenol and aniline 16. Which of the following statement is false?
8. Colligative properties depend on ............ . (a) Units of atmospheric pressure and osmotic pressure
(a) the nature of the solute particles dissolved in solution are same
(b) the number of solute particles in solution (b) In reverse osmosis, solvent molecules move through a
(c) the physical properties of the solution particles semipermeable membrane from a region of lower
dissolved in solution concentration of solute to a region of higher
(d) the nature of solvent particles concentration
9. Which of the following aqueous solutions should have (c) The value of molal depression constant depends on
the highest boiling point? nature of solvent
(a) 1.0 M NaOH (b) 1.0 M Na2SO4 (d) Relative lowering of vapour pressure, is a dimensionless
(c) 1.0 M NH4NO3 (d) 1.0 M KNO3 quantity
 EBD_7374
220 CHEMISTRY

17. Value of Henry's constant KH ............. . and same capacity as shown in figure.
(a) increases with increase in temperature
(b) decreases with increase in temperature
(c) remains constant A B
(d) first increases then decreases
18. The value of Henry's constant, KH is ............. . NaCl solution
Water
(a) greater for gases with higher solubility
(b) greater for gases with lower solubility At a given temperature, which of the following statement is
(c) constant for all gases correct about the vapour pressure of pure water and that of
(d) not related to the solubility of gases NaCl solution?
19. Consider the figure and mark the correct option. (a) Vapour pressure in container (A) is more than that in
container (B)
Piston (A) Piston (B) (b) Vapour pressure in container (A) is less than that in
container (B)
SPM
(c) Vapour pressure is equal in both the containers
(d) Vapour pressure in container (B) is twice the vapour
Concentrated
pressure in container (A)
Fresh water sodium chloride 23. If two liquids A and B form minimum boiling azeotrope at
(A) solution in some specific composition then
water (B) (a) A — B interactions are stronger than those between
A — A or B — B
(a) Water will move form side (A) to side (B) if a pressure (b) vapour pressure of solution increases because more
lower than osmotic pressure is applied on piston (B) number of molecules of liquids A and B can escape
(b) Water will move from side (B) to side (A) if a pressure from the solution
greater than osmotic pressure is applied on piston (B) (c) vapour pressure of solution decreases because less
(c) Water will move from side (B) to side (A) if a pressure number of molecules of only one of the liquids escape
equal to osmotic pressure is applied on piston (B) from the solution
(d) Water will move from side (A) to side (B) if pressure (d) A — B interactions are weaker than those between
equal to osmotic pressure is applied on piston (A) A — A or B — B
20. We have three, aqueous solutions of NaCl labelled as 'A', 24. 4 L of 0.02 M aqueous solution of NaCl was diluted by
'B' and 'C' with concentrations 0.1 M,0.01M and 0.001 M, adding 1 L of water. The molality of the resultant solution
respectively. The value of van't Hoff factor for these is .................
solutions will be in the order ........... . (a) 0.004 (b) 0.008 (c) 0.012 (d) 0.016
(a) iA < iB < iC (b) iA > iB > iC 25. On the basis of information given below mark the correct
(c) iA = iB = iC (d) iA < iB > iC option.
21. On the basis of information given below mark the correct Information On adding acetone to methanol some of the
option. hydrogen bonds between methanol molecules break.
Information (a) At specific composition methanol-acetone mixture will
(i) In bromoethane and chloroethane mixture form minimum boiling azeotrope and will show positive
intermolecular interactions of A — A and B — B type deviation from Raoult's law
are nearly same as A — B type interactions. (b) At specific composition methanol-acetone mixture will
(ii) In ethanol and acetone mixture A — A or B — B type form maximum boiling azeotrope and will show positive
intermolecular interactions are stronger than A — B deviation from Raoult's law
type interactions. (c) At specific composition methanol-acetone mixture will
(iii) In chloroform and acetone mixture A — A or B — B form maximum boiling azeotrope and will show negative
type intermolecular interactions are weaker than deviation from Raoult's law
A — B type interactions. (d) At specific composition methanol-acetone mixture will
(a) Solution (ii) and (iii) will follow Raoult's law form minimum boiling azeotrope and will show negative
(b) Solution (i) will follow Raoult's law deviation from Raoult's law
(c) Solution (ii) will show negative deviation from Raoult's 26. KH value for Ar (g), CO2 (g), HCHO (g) and CH4 (g) are
law 40.39, 1.67, 1.83 × 10–5 and 0.413 respectively.
(d) Solution (iii) will show positive deviation from Raoult's Arrange these gases in the order of their increasing
law solubility.
22. Two beakers of capacity 500 mL were taken. One of these (a) HCHO < CH4 < CO2 < Ar
beakers labelled as "A" was filled with 400 mL water (b) HCHO < CO2 < CH4 < Ar
whereas the beaker labelled "B" was filled with 400 mL of (c) Ar < CO2 < CH4 < HCHO
2M solution of NaCl. At the same temperature both the (d) Ar < CH4 < CO2 < HCHO
beakers were placed in closed containers of same material
SOLUTIONS 221

Past Year MCQs mole fraction of the solute in the solution is 0.2. What should
be the mole fraction of the solvent if the decrease in the
27. Of the following 0.10m aqueous solutions, which one will vapour pressure is to be 20 mm of Hg ? [AIIMS 2015, S]
exhibit the largest freezing point depression? (a) 0.8 (b) 0.6 (c) 0.4 (d) 0.2
[AIPMT 2014, A] 37. A solution of urea (mol. mass 56 g mol-1) boils at 100.18°C
(a) KCl (b) C6H12O6 at the atmospheric pressure. If Kf and Kb for water are 1.86
(c) Al2(SO4)3 (d) K2SO4 and 0.512 K kg mol-1 respectively, the above solution will
28. Which of the following 0.10 m aqueous solutions will have freeze at [AIIMS 2015, S]
the lowest freezing point ? [AIIMS 2014, A] (a) 0.654°C (b) - 0.654°C
(a) Al2(SO4)3 (b) C6H12O6 (c) 6.54°C (d) - 6.54°C
(c) KCl (d) C12H22O11 38. 3 g of activated charcoal was added to 50 mL of acetic acid
29. A solution containing 10g per dm3 of urea (molecular mass solution (0.06N) in a flask. After an hour it was filtered and
= 60 gmol–1) is isotonic with a 5% solution of a non volatile the strength of the filtrate was found to be 0.042 N. The
solute. The molecular mass of this non volatile solute is amount of acetic acid adsorbed (per gram of charcoal) is :
[AIIMS 2014, A] [JEE M 2015, S]
(a) 300 g mol–1 (b) 350 g mol–1 (a) 42 mg (b) 54 mg (c) 18 mg (d) 36 mg
(c) 200 g mol–1 (b) 250 g mol–1 39. The vapour pressure of acetone at 20°C is 185 torr. When
30. Consider separate solutions of 0.500 M C2H5OH(aq), 1.2 g of a non-volatile substance was dissolved in 100 g of
0.100 M Mg3(PO4)2 (aq), 0.250 M KBr(aq) and 0.125 M acetone at 20°C, its vapour pressure was 183 torr. The molar
Na3PO4(aq) at 25°C. Which statement is true about these mass (g mol–1) of the substance is : [JEE M 2015, S]
solutions, assuming all salts to be strong electrolytes? (a) 128 (b) 488 (c) 32 (d) 64
[JEE M 2014, A] 40. Which of the following statement about the composition of
(a) They all have the same osmotic pressure. the vapour over an ideal 1 : 1 molar mixture of benzene and
(b) 0.100 M Mg3(PO4)2(aq) has the highest osmotic toluene is correct? Assume that the temperature is constant
pressure. at 25°C. (Given : Vapour Pressure Data at 25°C, benzene =
(c) 0.125 M Na3PO4(aq) has the highest osmotic pressure. 12.8 kPa, toluene = 3.85 kPa) [NEET 2016, S]
(d) 0.500 M C2H5OH(aq) has the highest osmotic pressure. (a) The vapour will contain a higher percentage of benzene
31. Identify the correct order of solubilty of Na 2S. CuS and (b) The vapour will contain a higher percentage of toluene
ZnS in aqueous medium [BITSAT 2014, A] (c) The vapour will contain equal amounts of benezene
(a) CuS > ZnS > Na2S (b) ZnS > Na2S > CuS and toluene
(c) Na2S > CuS > ZnS (d) Na2S > ZnS > CuS (d) Not enough information is given to make a predication
32. Which one of the following electrolytes has the same value 41. At 100°C the vapour pressure of a solution of 6.5g of a
of van't Hoff factor (i) as that of the Al2(SO4)3 (if all are 100% solute in 100 g water is 732 mm. If Kb = 0.52, the boiling point
ionised) ? [AIPMT 2015, A] of this solution will be [NEET 2016, S]
(a) K3[Fe(CN)6] (b) Al(NO3)3 (a) 101°C (b) 100°C (c) 102°C (d) 103°C
(c) K4[Fe(CN)6] (d) K2SO4 42. A solution containing 1.8 g of a compound (empirical formula
33. The boiling point of 0.2 mol kg–1 solution of X in water is CH2O) in 40 g of water is observed to freeze at –0.465° C.
greater than equimolal solution of Y in water. Which one of The molecular formula of the compound is
the following statements is true in this case ? (Kf of water = 1.86 kg K mol–1) [AIIMS 2016, S]
[AIPMT 2015, A] (a) C2H4O2 (b) C3H6O3
(a) Molecular mass of X is greater than the molecular mass (c) C4H8O4 (d) C6H12O6
of Y. 43. Assertion : If a liquid solute more volatile than the solvent
(b) Molecular mass of X is less than the molecular mass of is added to the solvent, the vapour pressure of the solution
Y. may increase i.e., ps > po.
(c) Y is undergoing dissociation in water while X Reason : In the presence of a more volatile liquid solute,
undergoes no change. only the solute will form the vapours and solvent will not.
(d) X is undergoing dissociation in water. [AIIMS 2016, C]
34. Which one is not equal to zero for an ideal solution: (a) If both Assertion and Reason are correct and Reason
[AIPMT 2015, C] is the correct explanation of Assertion.
(a) DSmix (b) If both Assertion and Reason are correct, but Reason
(b) DVmix is not the correct explanation of Assertion.
(c) DP = Pobserved – PRaoult (c) If Assertion is correct but Reason is incorrect.
(d) DHmix (d) If both the Assertion and Reason are incorrect.
35. What is the mole fraction of the solute in a 1.00 m aqueous 44. 18 g glucose (C6H12O6) is added to 178.2 g water. The vapour
solution ? [AIPMT 2015, A] pressure of water (in torr) for this aqueous solution is:
(a) 0.177 (b) 1.770 (c) 0.0354 (d) 0.0177 [JEE M 2016, S]
36. The vapour pressure of a solvent decreases by 10 mm of Hg (a) 752.4 (b) 759.0 (c) 7.6 (d) 76.0
when a non-volatile solute was added to the solvent. The
 EBD_7374
222 CHEMISTRY

45. If molality of the dilute solutions is doubled, the value of 49. The freezing point of benzene decreases by 0.45°C when
molal depression constant (Kf ) will be:- [NEET 2017, S] 0.2g of acetic acid is added to 20 g of benzene. If acetic acid
(a) halved (b) tripled associates to form a dimer in benzene, percentage
(c) unchanged (d) doubled association of acetic acid in benzene will be
46. Which of the following is dependent on temperature? (Kf for benzene = 5.12 K kg mol–1) [JEE M 2017, S]
[NEET 2017, C] (a) 64.6% (b) 80.4% (c) 74.6% (d) 94.6%
(a) Molarity (b) Mole fraction 50. Raoult’s law becomes a special case of Henry’s law when
(c) Weight percentage (d) Molality [BITSAT 2017, C]
47. Which observation(s) reflect(s) colligative properties? (a) K H < p ° (b) K H = p1°
1
[NEET 2017, A] (c) K H ; p ° (d) K H ³ p °
(i) A 0.5 m NaBr solution has a higher vapour pressure 1 1
than a 0.5 m BaCl2 solution at the same temperature 51. 1 gm of polymer having molar mass 1,60,000 gm dissolves in
(ii) Pure water freezes at the higher temperature than pure 800 ml water, so calculate osmotic pressure on pascal at 27°
methanol C. [AIIMS 2018, C]
(iii) a 0.1 m NaOH solution freezes at a lower temperature (a) 0.78 (b) 0.90 (c) 0.50 (d) 1.94
than pure water
52. For 1 molal aqueous solution of the following compounds,
Choose the correct answer from the codes given below
which one will show the highest freezing point?
(a) (i), (ii) and (iii) (b) (i) and (ii)
(c) (ii) and (iii) (d) (i) and (iii) [JEE M 2018, A, C]
48. Assertion : If one component of a solution obeys Raoult’s (a) [Co(H2O)6]Cl3 (b) [Co(H2O)5Cl]Cl2.H2O
law over a certain range of composition, the other component (c) [Co(H2O)4Cl2]Cl. 2H2O (d) [Co(H2O)3Cl3].3H2O
will not obey Henry’s law in that range. 53. Chloroform, CHCl3, boils at 61.7 °C. If the Kb for chloroform
[AIIMS 2011, 2013, 2017, C] is 3.63°C/molal, what is the boiling point of a solution of
Reason : Raoult’s law is a special case of Henry’s law. 15.0 kg of CHCl3 and 0.616 kg of acenaphthalene, C12H10?
(a) If both Assertion and Reason are correct and Reason [BITSAT 2018, C]
is the correct explanation of Assertion. (a) 61.9 (b) 62.0 (c) 52.2 (d) 62.67
(b) If both Assertion and Reason are correct, but Reason 54. pH of a 0.1 M monobasic acid is found to be 2. Hence, its
is not the correct explanation of Assertion. osmotic pressure at a given temperature T K is
(c) If Assertion is correct but Reason is incorrect.
[BITSAT 2018, C]
(d) If both the Assertion and Reason are incorrect.
(a) 0.1 RT (b) 0.11 RT (c) 1.1 RT (d) 0.01 RT

Exercise 3 : Try If You Can

1. Formation of a solution from two components can be the solution at the same temperature is :
considered as
(i) Pure solvent ® separated solvent molecules, DH1 1 2 4 1
(a) (b) (c) (d)
(ii) Pure solute ® separated solute molecules, DH2 5 3 5 4
(iii) Separated solvent & solute molecules ® solution, 4. Liquids A and B form an ideal solution and the former has
DH3 stronger intermolecular forces. If XA and X'A are the mole
Solution so formed will be ideal if fractions of A in the solution and vapour in equilibrium,
(a) ΧHsoln < ΧH3 ,ΧH1 ,ΧH 2 then
(b) ΧHsoln < ΧH1 ∗ ΧH 2 ∗ ΧH3 X 'A X 'A
(c) ΧHsoln < ΧH1 ∗ ΧH 2 ,ΧH3 (a) =1 (b) >1
XA XA
(d) ΧHsoln < ΧH1 ,ΧH 2 ,ΧH3
2. The solubility of a specific non-volatile salt is 4 g in 100 g X 'A
(c) <1 (d) X A' +X A =1
of water at 25°C. If 2.0 g. 4.0 g and 6.0 g of the salt added XA
to100 g of water at 25°C, in system X, Y and Z. The vapour 5. Equal mass of a solute are dissolved in equal mass of two
pressure would be in the order: solvents A and B and formed very dilute solution. The
(a) X < Y < Z (b) X > Y > Z relative lowering of vapour pressure for the solution B has
(c) Z > X = Y (d) X > Y = Z twice the relative lowering of vapour pressure for the
3. Two liquids A and B have vapour pressure in the ratio solution A. If MA and MB are the molecular mass of solvents
A and B respectively, then:
PA° : PB° = 1 : 3 at a certain temperature. Assume A and B
(a) MA = MB (b) MB = 2 × MA
form an ideal solution and the ratio of mole fractions of A to (c) MA = 4MB (d) MA = 2MB
B in the vapour phase is 4 : 3, then the mole fraction of B in
SOLUTIONS 223

6. The correct relationship between the boiling points of very 11. Two moles of a liquid A ( pºA = 100 torr) and 3 moles of
dilute solutions of AlCl3 (T1) and CaCl2 (T2), having the
same molar concentration is liquid B ( pºB = 150 torr) form a solution having vapour
(a) T1 = T2 (b) T1 > T2 (c) T2 > T1 (d) T2 ³ T1 pressure of 120 torr. Based upon this observation one can
7. If M normal is the normal molecular mass and a is the degree conclude :
of ionization of K3[Fe(CN)6], then the abnormal molecular (a) Interactions between like molecules > those between
mass of the complex in the solution will be: unlike molecules
(a) M normal (1 + 2a)–1 (b) M normal (1 + 3a)–1 (b) Interaction between like molecules < those between
(c) M normal (1 + a) –1 (d) equal to Mnormal unlike molecules
8. X3Y2(i = 5) when reacted with A2B3(i = 5) in aqueous solution (c) Interaction between like molecules = those between
gives brown colour. These are separated by a semipermeable unlike molecules
membrane AB as shown. Due to osmosis there is: (d) DSmixing = 0
12. CNS– ions give red colour with Fe3+ ions in aqueous
0.5 M 0.01 M solution as :
+ -
X3Y2 A 2B 3 Fe 3(aq ) + 3CNS ( aq ) ® Fe( CNS) 3 ( aq )
red
If 0.1M KCNS solution is separated from 0.1M FeCl3
Side X Side Y solution by means of semipermeable membrane, red colour
will appear on:
(a) FeCl3 solution side (b) KCNS solution side
SPM
(c) both sides (d) neither side
(a) brown colour formation in side X 13. 0.010M solution an acid HA freezes at –0.0205ºC. If Kf for
(b) brown colour formation in side Y water is 1.860 K kg mol–1, the ionization constant of the
(c) formation in both of the sides X and Y conjugate base of the acid will be (assume 0.010
(d) no brown colour formation M = 0.010 m)
9. 5 g of Na2SO4 was dissolved in x g of H2O. The change in (a) 1.1 × 10–4 (b) 1.1 × 10–3
freezing point was found to be 3.82°C. If Na2SO4 is 81.5% (c) 9.0 × 10–11 (d) 9.0 × 10–12
ionised, the value of x 14. When the super cooled liquid starts freezing, the
(Kf for water = 1.86°C kg mol–1) is approximately : temperature
(molar mass of S = 32 g mol–1 and that of Na = 23 g mol–1) (a) falls to freezing point
(a) 15 g (b) 25 g (c) 45 g (d) 65 g (b) rises to freezing point
10. p1, p2, p3 and p4 atm are the osmotic pressures of 5% (mass/ (c) fluctuates
volume) solutions of urea, fructose, sucrose and KCl (d) remains constant
respectively at certain temperature. The correct order of their 15. Which of the following terms has units of temperature?
magnitudes is : mK f
I: Kf II : mK f III : iK f IV :
(a) p1 > p 4 > p 2 > p3 (b) p1 < p 4 < p 2 < p3 i
(c) p 4 > p1 > p 2 > p3 (d) p 4 > p1 > p3 > p 2 (a) I, II (b) I, III
(c) II, III (d) II, IV
 EBD_7374
224 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 13 (d) 25 (c) 37 (b) 49 (a) 61 (c) 73 (d) 85 (a) 97 (b) 109 (d)
2 (b) 14 (c) 26 (a) 38 (c) 50 (a) 62 (a) 74 (c) 86 (c) 98 (a) 110 (b)
3 (c) 15 (c) 27 (b) 39 (b) 51 (c) 63 (a) 75 (a) 87 (c) 99 (a) 111 (d)
4 (b) 16 (d) 28 (b) 40 (a) 52 (a) 64 (c) 76 (b) 88 (c) 100 (d) 112 (c)
5 (c) 17 (d) 29 (d) 41 (b) 53 (d) 65 (c) 77 (b) 89 (b) 101 (c) 113 (a)
6 (b) 18 (b) 30 (d) 42 (c) 54 (a) 66 (d) 78 (a) 90 (a) 102 (a) 114 (d)
7 (d) 19 (c) 31 (b) 43 (d) 55 (b) 67 (d) 79 (b) 91 (c) 103 (d) 115 (c)
8 (b) 20 (a) 32 (c) 44 (d) 56 (d) 68 (a) 80 (a) 92 (d) 104 (a) 116 (d)
9 (b) 21 (c) 33 (d) 45 (a) 57 (d) 69 (d) 81 (d) 93 (b) 105 (d) 117 (a)
10 (d) 22 (d) 34 (a) 46 (c) 58 (b) 70 (b) 82 (c) 94 (b) 106 (b) 118 (a)
11 (a) 23 (d) 35 (d) 47 (d) 59 (b) 71 (a) 83 (c) 95 (d) 107 (b) 119 (a)
12 (b) 24 (a) 36 (c) 48 (d) 60 (a) 72 (b) 84 (b) 96 (a) 108 (a) 120 (d)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (a) 7 (a) 13 (a) 19 (b) 25 (a) 31 (d) 37 (b) 43 (c) 49 (a)
2 (d) 8 (b) 14 (a) 20 (c) 26 (c) 32 (c) 38 (c) 44 (a) 50 (d)
3 (c) 9 (b) 15 (b) 21 (b) 27 (c) 33 (d) 39 (d) 45 (c) 51 (d)
4 (b) 10 (a) 16 (b) 22 (a) 28 (a) 34 (a) 40 (a) 46 (a) 52 (d)
5 (c) 11 (c) 17 (a) 23 (a) 29 (a) 35 (d) 41 (a) 47 (d) 53 (d)
6 (b) 12 (d) 18 (b) 24 (d) 30 (a) 36 (b) 42 (d) 48 (b) 54 (b)
Exercis e 3 : Try If You Can
1 (b) 3 (a) 5 (b) 7 (b) 9 (c) 11 (b) 13 (c) 15 (d)
2 (d) 4 (c) 6 (b) 8 (d) 10 (c) 12 (d) 14 (b)
 17 Chapter
ELECTROCHEMISTRY

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 3 Nernst equation, Relation
AIIMS 3 between equilibrium constant 4/5 7.5
JEE Main 2 & Gibbs energy, Electrolytic
BITSAT 3 Conduction.
 EBD_7374
226 CHEMISTRY
ELECTROCHEMISTRY 227
 EBD_7374
228 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Electrochemical Cells and Galvanic Cells (iii) Cu is cathode

(iv) Ag is anode
1. Which of the following statements about galvanic cell is (a) (ii), (iii) and (iv) (b) (ii), (iii) and (iv)
incorrect (c) (iii) and (iv) (d) (i) and (ii)
(a) anode is positive 9. The reference electrode is made by using
(b) oxidation occurs at the electrode with lower reduction (a) ZnCl2 (b) CuSO4
potential (c) HgCl2 (d) Hg2Cl2
(c) cathode is positive 10. Standard electrode potential for Sn4+ / Sn2+ couple is + 0.15 V
(d) reduction occurs at cathode and that for the Cr3+ / Cr couple is – 0.74 V. These two couples
2. Reaction that takes place at graphite anode in dry cell is in their standard state are connected to make a cell. The cell
(a) Zn 2+ + 2e- ¾¾ ® Zn(s) potential will be
(a) + 1.19 V (b) + 0.89 V
(b) Zn(s) ¾¾ ® Zn 2+ + 2e -
(c) + 0.18 V (d) + 1.83 V
(c) Mn 2 + + 2e- ¾¾ ® Mn(s) 11. A button cell used in watches functions as following
(d) Mn(s) ¾¾ ® Mn + + e - + 1.5V Zn(s) + Ag2O(s) + H2O(l)
3. In which of the following conditions salt bridge is not
2Ag(s) + Zn2+(aq) + 2OH–(aq)
required in a galvanic cell? If half cell potentials are :
(a) When galvanic cell is used in geyser. Zn2+(aq) + 2e– ® Zn(s); Eo = – 0.76 V
(b) When distance between oxidation half cell and Ag2O(s) + H2O (l) + 2e– ® 2Ag(s) + 2OH–(aq); Eo = 0.34 V
reduction half cell is negligible. The Eocell will be :
(c) Electrolytic solutions used in both the half cells are of (a) 0.42 V (b) 0.84 V
same concentration.
(c) 1.34 V (d) 1.10 V
(d) When both the electrodes are dipped in the same 12. Which of the following statements regarding given cell
electrolytic solution. representation is/are correct?
4. Which device converts chemical energy of a spontaneous Cd(s)|Cd2+(aq)||Ag+(aq)|Ag(s)
redox reaction into electrical energy? (i) In the given cell Cd electrode act as an anode whereas
(a) Galvanic cell (b) Electrolytic cell Ag electrode acts as a cathode.
(c) Daniell cell (d) Both (a) and (c)
(ii) In the given cell Cd electrode acts as a cathode whereas
5. Zn (s ) | Zn 2 + ( aq) | | Cu 2+ ( aq) |Cu( s) is Ag electrode acts as a anode.
(anode) (cathode) (iii) Ecell = E -E
Ag + /Ag Cd 2+ /Cd
(a) Weston cell (b) Daniel cell
(c) Calomel cell (d) Faraday cell (a) (i) and (ii) (b) Only (ii)
6. The tendency of an electrode to lose electrons is known as (c) Only (i) (d) (i) and (iii)
(a) electrode potential (b) reduction potential 13. If salt bridge is removed from two half-cells the voltage
(c) oxidation potential (d) e.m.f. (a) drops to zero (b) does not change
7. The chemical reaction, (c) increases gradually (d) increases rapidly
14. In the electrolytic cell, flow of electrons is from
2AgCl(s) + H 2 (g) ¾¾
® 2HCl(aq) + 2Ag(s) (a) cathode to anode in solution
taking place in a galvanic cell is represented by the notation (b) cathode to anode through external supply
(a) Pt(s) | H 2 (g),1 bar |1M KCl(aq) | AgCl(s) | Ag(s) (c) cathode to anode through internal supply
(d) anode to cathode through internal supply
(b) Pt(s) | H 2 (g),1 bar |1M HCl(aq) |1MAg + (aq) | Ag(s)
(c) Pt(s) | H 2 (g),1 bar |1M HCl(aq) | AgCl(s) | Ag(s) Topic 2: Nernst Equation

(d) Pt(s) | H 2 (g),1 bar |1M HCl(aq) | Ag(s) | AgCl(s) 15. For the given Nernst equation
é 2+ ù
8. For cell representation: RT ë Mg û
Cu(s)|Cu2+(aq)||Ag+(aq)|Ag(s) E cell = E°cell - ln
2F é + ù 2
Which of the following is correct? Ag
ë û
(i) Cu is reducing agent. Which of the following representation is correct?
(ii) Overall cell reaction is (a) Ag+|Ag||Mg2+|Mg (b) Mg2+|Mg||Ag|Ag+
Cu ( s ) + 2Ag + ( aq ) ¾¾
® Cu 2+ ( aq ) + 2Ag (s ) 2+
(c) Mg|Mg ||Ag |Ag + (d) Mg|Mg2+||Ag|Ag+
ELECTROCHEMISTRY 229

16. Without losing its concentration ZnCl2 solution cannot be 26. The e.m.f. of a Daniell cell at 298 K is E1.
kept in contact with ZnSO4 CuSO4
(a) Au (b) Al (c) Pb (d) Ag Zn Cu
17. Standard electrode potential of three metals X, Y and Z are (0.01 M) (1.0 M)
– 1.2 V, + 0.5 V and – 3.0 V, respectively. The reducing power When the concentration of ZnSO4 is 1.0 M and that of CuSO4
of these metals will be : is 0.01 M, the e.m.f. changed to E2. What is the relationship
(a) Y > Z > X (b) X > Y > Z between E1 and E2?
(c) Z > X > Y (d) X > Y > Z (a) E 2 = 0 ¹ E1 (b) E1 > E 2
18. Standard reduction potentials of the half reactions are given (c) E1 < E 2 (d) E1 = E 2
below :
27. The electrode potential E of a zinc electrode at
F2(g) + 2e– ® 2F– (aq); E° = + 2.85 V (Zn 2+ Zn)
Cl2(g) + 2e– ® 2Cl–(aq); E° = + 1.36 V 25°C with an aqueous solution of 0.1 M ZnSO 4 is
Br2(l) + 2e– ® 2Br–(aq); E° = + 1.06 V
I2(s) + 2e– ® 2I–(aq); E° = + 0.53 V 2.303RT
[ E° 2+ = – 0.76 V. Assume = 0.06 at 298 K].
The strongest oxidising and reducing agents respectively (Zn Zn) F
are (a) + 0.73 (b) – 0.79 (c) – 0.82 (d) – 0.70
(a) F2 and I– (b) Br2 and Cl– 28. In the cell reaction
(c) Cl2 and Br – (d) Cl2 and I2 Cu(s) + 2Ag + (aq) ¾¾ ® Cu 2+ (aq) + 2Ag(s) ,
19. The oxidation potentials of A and B are +2.37 and +1.66 V
respectively. In chemical reactions Eocell = 0.46 V. By doubling the concentration of Cu 2+, Eocell
(a) A will be replaced by B will become
(b) A will replace B (a) doubled
(c) A will not replace B (b) halved
(d) A and B will not replace each other (c) increases but less than double
20. A smuggler could not carry gold by depositing iron on the (d) decreases by a small fraction
gold surface since 29. What is the standard cell potential E° for an electrochemical
(a) gold is denser cell in which the following reaction takes place
(b) iron rusts spontaneously ?
(c) gold has higher reduction potential than iron Cl2 (g) + 2Br - ® Br2 (aq) + 2Cl - DG° = -50.6 kJ
(d) gold has lower reduction potential than iron
(a) 1.2 V (b) 0.53 V (c) 0.26 V (d) –0.53 V
21. The standard e.m.f. of a galvanic cell involving cell reaction
30. Which of the following is/are correct statement(s) for the
with n = 2 is found to be 0.295 V at 25°C. The equilibrium
addition of Li, K, Rb to the aqueous solution of Na +.
constant of the reaction would be
(Given F = 96500 C mol–1; R = 8.314JK–1mol–1) (i) The correct order of metals in which they reduce the
(a) 2.0 × 1011 (b) 4.0 × 1012 Na+ ion is Rb < K < Li.
(c) 1.0 × 102 (d) 1.0 × 1010 (ii) Reduction of metal ions would not take place.
22. The value of electrode potential (10–4 M) H+ | H2(1 atm) | Pt (a) Statement (i) and (ii) are correct.
at 298 K would be (b) Statement (i) is correct only.
(a) – 0.236 V (b) + 0.404 V (c) Statement (ii) is correct only.
(c) + 0.236 V (d) – 0.476 V (d) Neither (i) nor (ii) is correct.
23. According to Nernst equation, which is not correct if 31. Standard potentials (Eº) for some half-reactions are given
Q = Kc : below :
RT
(a) Ecell = 0 (b) ln Q = E ocell (i) Sn 4 + + 2e - ® Sn 2 + ; E º = +0.15 V
nF
nFEocell (ii) 2 Hg 2+ + 2e - ® Hg 2 2+ ; E º = +0.92 V
(c) K c = (d) o
e RT E cell = E cell
24. The standard emf of a cell, involving one electron change is (iii) PbO2 + 4H + + 2e- ® Pb 2 + + 2H 2O ; E º = +1.45 V
found to be 0.591 V at 25°C. The equilibrium constant of the Based on the above, which one of the following statements
reaction is (F = 96500 C mol–1) is correct ?
(a) 1.0 × 101 (b) 1.0 × 105 (a) Sn4+ is a stronger oxidising agent than Pb4+
(c) 1.0 × 10 10 (d) 1.0 ×1030 (b) Sn2+ is a stronger reducing agent than Hg22+
25. For the galvanic cell (c) Hg2+ is a stronger oxidising agent than Pb4+
Zn | Zn2+ (0.1M) || Cu2+ (1.0M)|Cu the cell potential increase if: (d) Pb2+ is a stronger reducing agent than Sn 2+
(a) [Zn2+] is increased 32. The correct order of E ° 2 + values with negative sign
M /M
(b) [Cu2+] is increased
for the four successive elements Cr, Mn, Fe and Co is
(c) [Cu2+] is decreased
(a) Mn > Cr > Fe > Co (b) Cr < Fe > Mn > Co
(d) surface area of anode is increased
(c) Fe > Mn > Cr > Co (d) Cr > Mn > Fe > Co
 EBD_7374
230 CHEMISTRY

33. Consider the following four electrodes: (a) 9.65 × 104 (b) antilog (24.08)
P = Cu2+ (0.0001 M)/Cu(s) (c) 37.3 (d) 1037.3.
Q = Cu2+ (0.1 M)/Cu(s) 41. What is the potential of half-cell consisting of
R = Cu2+ (0.01 M)/Cu(s) zinc electrode in 0.01 M ZnSO 4 solution at 25°C
S = Cu2+ (0.001 M)/Cu(s)
If the standard reduction potential of Cu2+/Cu is +0.34 V,
(E o
ox = 0.763 V )
the reduction potentials in volts of the above electrodes (a) 0.8221 V (b) 8.221 V (c) 0.5282 V (d) 9.282 V
follow the order. 42. The oxidation potential of 0.05 M H2SO4 is
(a) P > S > R > Q (b) S > R > Q > P (a) –2 × 0.0591 (b) –0.01 × 0.0591
(c) R > S > Q > P (d) Q > R > S > P (c) –2.321 × 0.0591 (d) +1 × 0.0591
34. At 298K the standard free energy of formation of H2O (l) is 43. For a relation
–237.20 kJ/mole while that of its ionisation into H+ ion D r G = - nFE cell
and hydroxyl ions is 80 kJ/mole, then the emf of the following E cell = E °cell in which of the following condition?
cell at 298 K will be (a) Concentration of any one of the reacting species
[Take Faraday constant F = 96500C] should be unity
H2 (g , 1 bar) | H+ (1M) | | OH– (1M) | O2(g, 1 bar) (b) Concentration of all the product species should be
(a) 0.40V (b) 0.81V unity.
(c) 1.23 V (d) – 0.40 V (c) Concentration of all the reacting species should be
35. If the following half cells have E° values as unity.
A3+ + e– ––––® A2+, E° = y2V (d) Concentration of all reacting and product species
should be unity.
A2+ + 2e– ––––® A, E° = –y1V
The E° of the half cell A3+ + 3e ––––® A will be Topic 3: Conductance of Electrolytic Solutions
2 y1 - y2 y2 - 2 y1 44. If 0.01 M solution of an electrolyte has a resistance of 40
(a) (b) ohms in a cell having a cell constant of 0.4 cm–1, then its
3 3
(c) 2y1 – 3y2 (d) y2 – 2y1 molar conductance in ohm–1 cm2 mol–1 is
(a) 102 (b) 104 (c) 10 (d) 103
36. Cu + (aq ) is unstable in solution and undergoes 45. Specific conductance of a 0.1 N KCl solution at 23ºC is
simultaneous oxidation and reduction according to the 0.012 ohm–1 cm–1. Resistance of cell containing the solution
reaction : at same temperature was found to be 55 ohm. The cell
constant is
2Cu +(aq) Cu 2+ (aq) + Cu( s )
(a) 0.0616 cm–1 (b) 0.66 cm–1
Choose correct Eº for given reaction if Eº Cu2+/Cu = 0.34 V –1
(c) 6.60 cm (d) 660 cm–1
and Eº Cu2+/Cu+ = 0.15 V
46. The unit of equivalent conductivity is
(a) –0.38 V (b) +0.49 V (c) +0.38 V (d) –0.19 V
(a) ohm cm
37. In a cell that utilises the reaction
(b) ohm–1 cm2 (g equivalent)–1
Zn( s) + 2H + (aq) ® Zn 2+ (aq) + H 2 ( g ) addition of H2SO4 (c) ohm cm2 (g equivalent)
to cathode compartment, will (d) S cm–2
(a) increase the E and shift equilibrium to the right 47. The resistance of 0.01 N solution of an electrolyte was found
(b) lower the E and shift equilibrium to the right to be 220 ohm at 298 K using a conductivity cell with a cell
(c) lower the E and shift equlibrium to the left constant of 0.88cm–1. The value of equivalent conductance
(d) increase the E and shift equilibrium to the left of solution is –
38. For a cell reaction involving two electron change, the (a) 400 mho cm2 g eq–1 (b) 295 mho cm2 g eq–1
(c) 419 mho cm g eq 2 –1 (d) 425 mho cm2 g eq–1
standard EMF of the cell is 0.295 V at 2°C. The equilibrium
constant of the reaction at 25°C will be: 48. Specific conductance of 0.1 M HNO3 is 6.3×10–2 ohm–1 cm–1.
(a) 29.5 × 10–2 (b) 10 The molar conductance of the solution is
(c) 1 × 1010 (d) 2.95 × 10–10 (a) 100 ohm–1 cm2 (b) 515 ohm–1 cm2
(c) 630 ohm cm –1 2 (d) 6300 ohm–1 cm2
39. Standard cell voltage for the cell Pb | Pb2+ || Sn2+ | Sn is
– 0.01 V. If the cell is to exhibit Ecell = 0, the value of 49. The unit of specific conductivity is
[Sn 2+] / [Pb2+] should be antilog of – (a) ohm cm–1 (b) ohm cm–2
(c) ohm cm–1 (d) ohm–1 cm–1
(a) + 0.3 (b) 0.5
(c) 1.5 (d) – 0.5 50. Which of the following solutions of KCl will have the highest
value of specific conductance?
40. The cell, Zn | Zn 2 + (1 M) || Cu 2+ (1 M) | Cu ( E °cell = 1.10 V) (a) 1.0 N (b) 0.1 N
was allowed to be completely discharged at 298 K. The (c) 1.0 ×10–2N (d) 1.0 ×10–3N
æ [Zn 2+ ] ö 51. Which of the following pair(s) is/are incorrectly matched?
relative concentration of Zn2+ to Cu2+ çç 2+ ÷
÷ is (i) R (resistance) – ohm (W)
è [Cu ] ø (ii) r (resistivity) – ohm metre (Wm)
ELECTROCHEMISTRY 231

(iii) G (conductance) – seimens or ohm (S) (b) infinite dilution each ion makes definite contribution
(iv) k (conductivity) – seimens metre–1 (Sm–1) to equivalent conductance of an electrolyte depending
(a) (i), (ii) and (iii) (b) (ii) and (iii) on the nature of the other ion of the electrolyte.
(c) (i), (ii) and (iv) (d) (iii) only (c) infinite dilution, each ion makes definite contribution
52. On which of the following magnitude of conductivity does to conductance of an electrolyte whatever be the nature
not depends? of the other ion of the electrolyte.
(a) Nature of material (b) Temperature (d) infinite dilution, each ion makes definite contribution
(c) Pressure (d) Mass of the material to equivalent conductance of an electrolyte, whatever
53. Which of the following expression correctly represents be the nature of the other ion of the electrolyte.
molar conductivity? 57. Which of the following expressions correctly represents
K KA the equivalent conductance at infinite dilution of Al2(SO4)3,
(a) Ùm = (b) Ù m = Given that L °Al3+ and L°SO2- are the equivalent
C l 4
(c) Ùm = KV (d) All of these conductances at infinite dilution of the respective ions?
1 ° 1
54. Which of the following represents variation of molar (a) L 3+ + L° 2- (b) 2L°Al3+ + 3LSO ° 2-
conductance of electrolyte with (concentration) ½ 3 Al 2 SO4 4
respectively for weak and strong electrolyte ? æ ° 2- ö ´ 6
(c) L°Al3+ + LSO° 2-
(d) èL°Al3+ + LSO
(i) (ii) 4 4 ø
m/(S cm mol )
m/(S cm mol )
–1

–1

58. Molar conductivities ( L° m ) at infinite dilution of NaCl, HCl

and CH3COONa are 126.4, 425.9 and 91.0 S cm2 mol–1
2

respectively. L°m for CH3COOH will be

(a) 425.5 S cm2 mol–1 (b) 180.5 S cm2 mol–1
2
(c) 290.8 S cm mol –1 (d) 390.5 S cm2 mol–1
1 1
c / (mol L) 2 59. At 25°C, the molar conductance at infinite dilution for the
c / (mol L) 2
strong electrolytes NaOH, NaCl and BaCl2 are 248 × 10–4,
(iii) (iv) 126 × 10 –4 and 280 × 10 –4 Sm 2mol –1 respectively.
m/(S cm mol )
–1

m/(S cm mol )
–1

L 0m Ba(OH)2 in S m2 mol –1 is
2

(a) 52.4 × 10–4 (b) 524 × 10–4

2

(c) 402 × 10 –4 (d) 262 × 10–4

60. At 25°C molar conductance of 0.1 molar aqueous solution
1 of ammonium hydroxide is 9.54 ohm-1 cm2mol-1 and at infinite
1
c / (mol L) 2
c / (mol L) 2
dilution its molar conductance is 238 ohm-1 cm2 mol-1. The
degree or ionisation of ammonium hydroxide at the same
(v)
m/(S cm mol )

concentration and temperature is:

–1

(a) 20.800% (b) 4.008% (c) 40.800% (d) 2.080%

61. The electrical properties and their r espective
2

SI units are given below. Identify the wrongly matched pair.

Electrical property SI unit
1
(a) Specific conductance S m–1
c / (mol L) 2 (b) Conductance S
(c) Equivalent conductance S m2 geq–1
Weak acid Strong acid
(a) (iv) (v) (d) Cell constant m
(b) (ii) (iv) 62. The ion of least limiting molar conductivity among the
(c) (i) (ii) following is
(d) (iii) (ii)
(a) SO 24 - (b) H+ (c) Ca 2+ (d) CH3 COO -
Electrolyte: KCl KNO 3 HCl NaOAc NaCl
55. 63. Molar ionic conductivities of a two-bivalent electrolytes
¥ 2 –1
L (S cm mol ) : 149.9 145 426.2 91 126.5 x2+ and y2– are 57 and 73 respectively. The molar conductivity
¥ of the solution formed by them will be
Calculate L HOAc using appropriate molar conductances
(a) 130 S cm2 mol–1 (b) 65 S cm2 mol–1
of the electrolytes listed above at infinite dilution in H 2 O (c) 260 S cm2 mol–1 (d) 187 S cm2 mol–1
at 25°C 64. Assertion : The resistivity for a substance is its resistance
(a) 217.5 (b) 390.7 (c) 552.7 (d) 517.2 when it is one meter long and its area of cross section is one
56. Kohlrausch’s law states that at square meter.
(a) finite dilution, each ion makes definite contribution to Reason : The SI units of resistivity is ohm metre (Wm).
equivalent conductance of an electrolyte, whatever be (a) If both assertion and reason are true and reason is the
the nature of the other ion of the electrolyte. correct explanation of assertion.
 EBD_7374
232 CHEMISTRY

(b) If both assertion and reason are true but reason is not 72. The conductivity of electrolytic solutions depends upon
the correct explanation of assertion. which of the following?
(c) If assertion is true but reason is false. (i) Size of ions produced
(d) If both assertion and reason are false. (ii) Viscosity of the solvent
65. Assertion : On increasing dilution, the specific conductance (iii) Concentration of electrolyte
keep on increasing. (iv) Solvation of ions produced
Reason : On increasing dilution, degree of ionisation of (a) (i) and (iii) (b) (i), (ii) and (iii)
weak electrolyte increases and molality of ions also (c) (i), (iii) and (iv) (d) All of these
increases.
Topic 4: Electrolytic Cells and Electrolysis
(a) If both assertion and reason are true and reason is the
correct explanation of assertion. 73. On electrolysis of dilute sulphuric acid using platinum
(b) If both assertion and reason are true but reason is not electrodes, the product obtained at the anode will be
the correct explanation of assertion. (a) hydrogen (b) oxygen
(c) If assertion is true but reason is false. (c) hydrogen sulphide (d) Sulphur dioxide
(d) If both assertion and reason are false. 74. If 0.5 amp current is passed through acidified silver nitrate
solution for 100 minutes. The mass of silver deposited on
66. A 0.5 M NaOH solution offers a resistance of 31.6 ohm in a
conductivity cell at room temperature. What shall be the cathode, is (eq.wt.of silver nitrate = 108)
approximate molar conductance of this NaOH solution if (a) 2.3523 g (b) 3.3575 g (c) 5.3578 g (d) 6.3575 g
75. Aluminium oxide may be electrolysed at 1000°C to furnish
cell constant of the cell is 0.367 cm–1.
(a) 234 S cm2 mole–1 (b) 23.2 S cm2 mole–1 aluminium metal (At. Mass = 27 amu; 1 Faraday = 96,500
2 –1 Coulombs). The cathode reaction is – Al3+ + 3e– ® Al
(c) 4645 S cm mole (d) 5464 S cm2 mole–1
To prepare 5.12 kg of aluminium metal by this method we
67. The equivalent conductances of two strong electrolytes at
require electricity of
infinite dilution in H2O (where ions move freely through a
(a) 5.49 × 101 C (b) 5.49 × 104 C
solution) at 25°C are given below :
(c) 1.83 × 107 C (d) 5.49 × 107 C
Lo CH3COONa = 91.0 S cm 2 / equiv. 76. Which of the following is the use of electrolysis?
o 2 (a) Electrorefining (b) Electroplating
L HCl = 426.2 S cm / equiv.
What additional information/ quantity one needs to calcu- (c) Both (a) & (b) (d) None of these
77. An electrolytic cell contains a solution of Ag2SO4 and has
late Lo of an aqueous solution of acetic acid?
platinum electrodes. A current is passed until 1.6 gm of O2
(a) L o of chloroacetic acid (ClCH2COOH) has been liberated at anode. The amount of silver deposited
(b) L o of NaCl at cathode would be
(c) L o of CH3COOK (a) 107.88 gm (b) 1.6 gm (c) 0.8 gm (d) 21.60 gm
(d) the limiting equivalent coductance of H + (l° + ) . 78. When 9650 coulombs of electricity is passed through a
H
68. Resistance of 0.2 M solution of an electrolyte is 50 W. The solution of copper sulphate, the amount of copper deposited
specific conductance of the solution is 1.3 S m–1. If is (given at. wt. of Cu = 63.6)
resistance of the 0.4 M solution of the same electrolyte is (a) 0318g (b) 3.18 g (c) 31.8g (d) 63.6g
260 W, its molar conductivity is : 79. Find the charge in coulombs required to convert 0.2 mole
(a) 6.25 × 10–4 S m2 mol–1 (b) 625 × 10–4 S m2 mol–1 VO3–2 into VO4–3 –
(c) 62.5 S m2 mol–1 (d) 6250 S m2 mol–1 (a) 1.93 × 104 (b) 9.65 × 104
69. The limiting molar conductivities of HCl, CH3COONa and (c) 1.93 × 10 5 (d) 9.65 × 105
NaCl are respectively 425, 90 and 125 mho cm2 mol–1 at 80. A silver cup is plated with silver by passing 965 coulombs
25°C. The molar conductivity of 0.1 M CH3COOH solutions of electricity. The amount of Ag deposited is :
is 7.8 mho cm2 mol–1 at the same temperature. The degree of (a) 107.89 g (b) 9.89 g (c) 1.0002 g (d) 1.08 g
dissociation of 0.1 M acetic acid solution at the same 81. The number of coulombs required to reduce 12.3 g of
temperature is nitrobenzene to aniline is :
(a) 0.10 (b) 0.02 (c) 0.15 (d) 0.03 (a) 115800 C (b) 5790 C (c) 28950 C (d) 57900 C
70. A weak electrolyte having the limiting equivalent 82. The amount of electricity that can deposit 108 g of Ag from
conductance of 400 S cm2. equivalent–1 at 298 K is 2% AgNO3 solution is:
ionized in its 0.1 N solution. The resistance of this solution (a) 1 F (b) 2 A (c) 1 C (d) 1 A
(in ohms) in an electrolytic cell of cell constant 0.4 cm–1 at 83. To deposit one equivalent weight of silver at cathode, the
this temperature is charge required will be
(a) 200 (b) 300 (c) 400 (d) 500 (a) 9.65 × 104 C (b) 9.65 × 103 C
71. Arrange the following in increasing order of their (c) 9.65 × 10 C 5 (d) 9.65 × 107 C
conductivity Na+ (A), K+ (B), Ca2+ (C), Mg2+(D) 84. The volume of oxygen gas liberated at NTP by passing a
(a) A, B, C, D (b) B, A, C, D current of 9650 coulombs through acidified water is
(c) C, A, D, B (d) A, B, D, C (a) 1.12 litre (b) 2.24 litre (c) 11.2 litre (d) 22.4 litre
ELECTROCHEMISTRY 233

85. Three faradays electricity was passed through an aqueous (i) NaCl (ii) KCl
solution of iron (II) bromide. The weight of iron metal (iii) RbCl (iv) KBr
(at. wt = 65) deposited at the cathode (in gm) is (a) (i), (ii) and (iii) (b) (ii), (ii) and (iv)
(a) 56 (b) 84 (c) 112 (d) 168 (c) (i), (ii) and (iv) (d) (i), (iii) and (iv)
86. On passing C ampere of electricity through a electrolyte 97. Which of the following statements is incorrect?
solution for t second. m gram metal deposits on cathode. (a) Both electronic and electrolytic conductance depends
The equivalent weight E of the metal is on the nature of conducting material.
(b) Both electronic and electrolytic conductance varies
C ´t C´m
(a) E= (b) E= similarly with temperature.
m ´ 96500 t ´ 96500 (c) Electronic conductance is independent but electrolytic
96500 ´ m C ´ t ´ 96500 conductance depends on the amount of the
(c) E= (d) E = conducting substance.
C ´t m
87. The number of electrons passing per second through a (d) All the above statements are incorrect.
cross-section of copper wire carrying 10–6 amperes of current 98. Which of the following statements is incorrect?
per second is found to be (a) Electrodes made up of gold participates in the chemical
(a) 1.6 × 10–19 (b) 6 × 10–35 reaction.
(c) 6 × 10–16 (d) 6 × 1012 (b) Electrolytic products of NaCl are Na and Cl2 whereas
88. Faraday’s laws of electrolysis will fail when of aqueous NaCl are NaOH, Cl2 and H2.
(a) temperature is increased (c) During electrolysis at cathode, reaction with higher
(b) inert electrodes are used value of E Å is preferred.
(c) a mixture of electrolytes is used (d) All of the above statements are incorrect.
(d) None of these cases 99. When electric current is passed through acidified water,
89. The electric charge for electrode decomposition of one gram 112 ml of hydrogen gas at STP collected at the cathode in
equivalent of a substance is 965 seconds. The current passed in amperes is
(a) one ampere per second (a) 1.0 (b) 0.5 (c) 0.1 (d) 2.0
(b) 96500 coulombs per second 100. On passing current through two cells, connected in series
(c) one ampere for one hour containing solution of AgNO3 and CuSO4, 0.18 g of Ag is
(d) charge on one mole of electrons deposited. The amount of the Cu deposited is:
90. In electrolysis of dilute H2SO4 using platinum electrodes (a) 0.529 g (b) 10.623 g (c) 0.0529 g (d) 1.2708 g
(a) H2 is evolved at cathode 101. In the electrolysis of water, one faraday of electrical energy
(b) NH2 is produced at anode would liberate
(c) Cl2 is obtained at cathode (a) one mole of oxygen (b) one gram atom of oxygen
(d) O2 is produced (c) 8 g oxygen (d) 22.4 lit. of oxygen
91. In electrolysis of NaCl when Pt electrode is taken then H2 is 102. Electrolysis of dilute aqueous NaCl solution was carried
liberated at cathode while with Hg cathode it forms sodium out by passing 10 milli ampere current. The time required to
amalgam. This is because liberate 0.01 mol of H2 gas at the cathode is
(a) Hg is more inert than Pt (1 Faraday = 96500 C mol–1)
(b) more voltage is required to reduce H+ at Hg than at Pt (a) 9.65 × 104 sec (b) 19.3 × 104 sec
(c) 28.95 × 10 sec4 (d) 38.6 × 104 sec
(c) Na is dissolved in Hg while it does not dissolve in Pt
(d) conc. of H+ ions is larger when Pt electrode is taken 103. What is the amount of chlorine evolved when 2 amperes of
92. Electrolysis of fused NaCl will give current is passed for 30 minutes in an aqueous solution of
(a) Na (b) NaOH NaCl ?
(c) NaClO (d) None of these (a) 66 g (b) 1.32 g (c) 33 g (d) 99 g
93. How many moles of Pt may be deposited on the cathode 104. On passing a current of 1.0 ampere for 16 min and 5 sec through
when 0.80 F of electricity is passed through a 1.0 M one litre solution of CuCl2, all copper of the solution was
solution of Pt4+? deposited at cathode. The strength of CuCl2 solution was
(a) 1.0 mol (b) 0.20 mol (c) 0.40 mol (d) 0.80 mol (Molar mass of Cu= 63.5; Faraday constant = 96,500 Cmol–1)
94. A current strength of 9.65 amperes is passed through excess (a) 0.01 N (b) 0.01 M (c) 0.02 M (d) 0.2 N
fused AlCl3 for 5 hours. How many litres of chlorine will be 105. 0.2964 g of copper was deposited on passage of a current of
liberated at STP? (F = 96500 C) 0.5 amp for 30 mins through a solution of copper sulphate.
(a) 2.016 (b) 1.008 (c) 11.2 (d) 20.16 Calculate the oxidation state of Cu (At. mass 63.56).
95. A solution of copper sulphate (CuSO4) is electrolysed for (a) +1 (b) +2 (c) +3 (d) +4
10 minutes with a current of 1.5 amperes. The mass of copper 106. One Faraday of electricity is passed through molten Al2O3,
deposited at the cathode (at. mass of Cu = 63u) is aqueous solution of CuSO4 and molten NaCl taken in three
(a) 0.3892g (b) 0.2938g (c) 0.2398g (d) 0.3928g different electrolytic cells connected in series. The mole ratio
96. Electrolysis of a salt solution was carried out, after some of Al, Cu and Na deposited at the respective cathode is
time solution turned yellow than salt can be (a) 2 : 3 : 6 (b) 6 : 2 : 3 (c) 6 : 3 : 2 (d) 1 : 2 : 3
 EBD_7374
234 CHEMISTRY

107. How much charge is required, when 1 mole of Cr2O72 - 117. Several blocks of magnesium are fixed to the bottom of a ship
to
reduce to form 1 mole of Cr 3+ ?
(a) make the ship lighter
(a) 6F (b) 3F (c) 1F (d) 2F (b) prevent action of water and salt
Topic 5: Batteries, Fuel Cells and Corrosion (c) prevent puncturing by under-sea rocks
108. During the charging of lead storage battery, the reaction at (d) keep away the sharks
anode is represented by 118. Which of the following batteries cannot be reused?
(a) Lead storage battery (b) Ni-Cd cell
(a) Pb2+ + SO24- ¾¾
® PbSO 4 (c) Mercury cell (d) Both (b) and (c)
(b) ® PbO2 + SO42 - + 4H + + 2e -
PbSO 4 + 2H 2 O ¾¾ 119. Which of the following is a merit of Ni–Cd cell over lead
storage battery?
(c) ® Pb 2+ + 2e -
Pb ¾¾ (a) Ni–Cd cell can be re-used.
(b) Ni–Cd cell is comparatively economical to manufacture
(d) Pb2 + + 2e- ¾¾ ® Pb (c) Ni–Cd cell has comparatively longer life
109. Which colourless gas evolves, when NH4Cl reacts with zinc (d) All the above are the merits of Ni–Cd cell over lead
in a dry cell battery storage battery.
(a) NH4 (b) N2 (c) H2 (d) Cl2 120. Which of the following statements regarding fuel cell is
110. In a hydrogen-oxygen fuel cell, combustion of hydrogen incorrect?
occurs to (a) These cells are eco-friendly.
(a) produce high purity water (b) These cells convert energy of combustion of fuels like
(b) create potential difference between two electrodes H2, CH4, CH3OH etc., directly into electrical energy.
(c) H2 – O2 fuel cell is used in Apollo space programme.
(c) generate heat
(d) Fuel cells produce electricity with an efficiency of about
(d) remove adsorbed oxygen from elctrode surfaces 100%.
111. Among the following cells: 121. Which of the following statement(s) is/ are incorrect for
Leclanche cell (i) corrosion of iron?
Nickel-Cadmium cell (ii) (i) Reaction occurring at anode is
Lead storage battery (iii) O 2 (g) + 4H + (aq) + 4e - ¾¾ ® 2H 2 O (l)
Mercury cell (iv) (ii) Reaction occurring at cathode is
primary cells are ® 2Fe 2 + + 4e -
2Fe (s) ¾¾
(a) (i) and (ii) (b) (i) and (iii) (iii) Rust is Fe2O3.xH2O
(c) (ii) and (iii) (d) (i) and (iv) (iv) H+ involved in corrosion reaction is provided from
112. The electrolyte used in Leclanche cell is H2CO3 which is formed due to dissolution of carbon
(a) paste of KOH and ZnO dioxide from air in to water.
(b) 38% solution of H2SO4 (a) (iv) only (b) (i) only
(c) moist paste of NH4Cl and ZnCl2 (c) (i) and (ii) (d) (i), (ii) and (iv)
122. When a lead storage battery is discharged
(d) moist sodium hydroxide
(a) SO2 is evolved
113. Which one of the following cells can convert chemical (b) Lead sulphate is consumed
energy of H2 and O2 directly into electrical energy? (c) Lead is formed
(a) Mercury cell (b) Daniell cell (d) Sulphuric acid is consumed
(c) Fuel cell (d) Lead storage cell 123. The most durable metal plating on iron to protect against
114. Hydrogen-Oxygen fuel cells are used in space craft to supply corrosion is
(a) power for heat and light (a) nickel plating (b) copper plating
(b) power for pressure (c) tin plating (d) zinc plating
124. Which of the following statements is incorrect regarding
(c) oxygen
dry (Leclanche) cell?
(d) water (a) Cathode used in the cell is coated by powdered
115. Prevention of corrosion of iron by zinc coating is called manganese dioxide and carbon.
(a) electrolysis (b) photoelectrolysis (b) Most common application of this cell is in our
(c) cathodic protection (d) galvanization transistors and clocks.
116. The best way to prevent rusting of iron is (c) At cathode, Mn is oxidised from + 3 to + 4.
(a) making it cathode (b) putting in saline water (d) At anode Zn is oxidised from 0 to + 2.
(c) Both of these (d) None of these
ELECTROCHEMISTRY 235

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (d) Ecell is an extensive property while DrG of cell reaction
is an intensive property.
1. Which cell measure standard electrode potential of copper
4. The difference between the electrode potentials of two
electrode?
electrodes when no current is drawn through the cell is
(a) Pt ( s ) |H 2 ( g, 0.1 bar )| |H + ( aq, 1 M )| |Cu 2+ ( aq, 1 M )| Cu called......
(a) cell potential (b) cell emf
(b) Pt ( s ) |H 2 ( g,1 bar )| |H + ( aq, 1 M )| |Cu 2+ ( aq, 2 M )| Cu (c) potential difference (d) cell voltage
5. Which of the following statement is not correct about an
(c) Pt ( s) |H2 ( g,1 bar )| |H+ ( aq,1 M)| |Cu 2+ ( aq, 1 M )| Cu inert electrode in a cell?
(a) It does not participate in the cell reaction
(d) Pt ( s) |H2 ( g,0.1bar) | |H+ ( aq, 0.1M)| |Cu 2+ ( aq,1 M)| Cu (b) It provides surface either for oxidation or for reduction
2. Electrode potential for Mg electrode varies according to the reaction
equation (c) It provides surface for conduction of electrons
(d) It provides surface for redox reaction
E = E°Mg2+ / Mg - 0.059 log 1 . 6. An electrochemical cell can behave like an electrolytic cell
Mg 2 + / Mg
2 [Mg 2+ ] when ......
(a) Ecell = 0 (b) Ecell > Eext
The graph of E vs log [Mg2+] is (c) Eext > Ecell (d) Ecell = Eext
Mg 2 + / Mg
7. Which of the statements about solutions of electrolytes is
not correct?
(a) Conductivity of solution depends upon size of ions
®

(a) E
Mg 2+ / Mg (b) Conductivity depends upon viscosity of solution
(c) Conductivity does not depend upon solvation of ions
present in solution
log [Mg2+] ® (d) Conductivity of solution increases with temperature
8. Using the data given below find out the strongest reducing
agent.
®

(b) E
Mg 2+ / Mg E° 3+ = 1.33 V; E° = 1.36 V
Cr2O2–
7 /Cr Cl2 /C –

E° = 1.51 V; E° = – 0.74 V
MnO4– /Mn 2 + Cr 3+ /Cr
2+
log [Mg ] ® (a) Cl– (b) Cr (c) Cr3+ (d) Mn2+
9. Use the data given in Q. 8 and find out which of the following
is the strongest oxidising agent?
®

(c) E
Mg 2+ / Mg (a) Cl– (b) Mn2+ MnO4- (d) Cr3+
(c)
10. Using the data given in Q. 8 find out in which option the
order of reducing power is correct.
log [Mg2+] ®
(a) Cr 3+ < Cl - > Mn 2 + < Cr
(b) Mn 2 + < Cl - > Cr 3+ < Cr
®

(d) E (c) Cr3+ < Cl - < Cr2O72 - < Mn 2 +

Mg 2+ / Mg
(d) Mn 2 + < Cr 3+ < Cl - < Cr
11. Use the data given in Q.8 and find out the most stable ion
log [Mg2+] ® in its reduced form.
3. Which of the following statement is correct? (a) Cl– (b) Cr3+ (c) Cr (d) Mn2+
(a) Ecell and D rG of cell reaction both are extensive 12. Use the data of Q. 8 and find out the most stable oxidised
properties. species.
(b) E cell and D rG of cell reaction both are intensive
(a) Cr3+ (b) MnO4- (c) Cr2 O72 - (d) Mn2+
properties.
(c) Ecell is an intensive property while DrG of cell reaction 13. The quantity of charge required to obtain one mole of
is an extensive property. aluminium from Al2O3 is ....... .
(a) 1 F (b) 6 F (c) 3 F (d) 2 F
 EBD_7374
236 CHEMISTRY

14. The cell constant of a conductivity cell ........ . (c) Assertion is correct, reason is incorrect
(a) changes with change of electrolyte (d) Assertion is incorrect, reason is correct.
(b) changes with change of concentration of electrolyte 22. Assertion : During electrolysis of CuSO4(aq) using copper
(c) changes with temperature of electrolyte electrodes, copper is dissolved at anode and deposited at
(d) remains constant for a cell cathode.
15. While charging the lead storage battery ......... . Reason : Oxidation takes place at anode and reduction at
(a) PbSO4 anode is reduced to Pb cathode. [AIIMS 2014, C]
(b) PbSO4 cathode is reduced to Pb (a) Assertion is correct, reason is correct; reason is a
(c) PbSO4 cathode is oxidised to Pb correct explanation for assertion.
(d) PbSO4 anode is oxidised to PbO2 (b) Assertion is correct, reason is correct; reason is not a
°
correct explanation for assertion
16. L m( NH4OH ) is equal to ....... . (c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct.
(a) L °m( NH + L °( NH - L °m( HCI )
4OH ) 4Cl) 23. Resistance of 0.2 M solution of an electrolyte is 50 W.
(b) L°m( NH ° °
Cl) + L m( NaOH ) - L m( NCI )
The specific conductance of the solution is 1.4 S m–1.
4
The resistance of 0.5 M solution of the same electrolyte is
(c) L °m( NH + L °m( NaCl) - L °m ( NaOH ) 280 W. The molar conductivity of 0.5 M solution of the
4Cl )
° ° ° electrolyte in S m2 mol–1 is: [JEE M 2014, A]
(d) L m( NaOH ) + L m( NaCl) - L m( NH 4Cl)
(a) 5 × 10–4 (b) 5 × 10–3 (c) 5 × 103 (d) 5 × 102
17. In the electrolysis of aqueous sodium chloride solution which 24. The equivalent conductance of NaCl at concentration C
of the half cell reaction will occur at anode? and at infinite dilution are lC and l¥, respectively. The correct
(a) Na + ( aq ) + e - ¾¾ °
® Na (s ) ; E cell = - 2.71V relationship between lC and l¥ is given as:
(b) 2H 2 O ( l ) ® O2 ( g ) + 4H + ( aq ) + 4e - ; E°cell = 1.23V (Where the constant B is positive) [JEE M 2014, S]
1 (a) l C = l ¥ + ( B) C (b) l C = l ¥ - ( B) C
(c) H ( aq ) + e ¾¾ ® H 2 (g ) ; E°cell = 0.00 V
+ -
2
1 (c) l C = l ¥ - ( B) C (d) l C = l ¥ + ( B) C
(d) Cl ( aq ) ¾¾ ® Cl2 ( g ) + e - ; E cell = 1.36 V
– °
2 25. Given below are the half-cell reactions: [JEE M 2014, A]
Past Year MCQs 2+ - 0
Mn + 2e ® Mn ; E = -1.18 V
18. When 0.1 mole MnO42– is oxidised the quantity of electricity
required to completely oxidise MnO42– to MnO4– is:
(
2 Mn 3+
)
+ e - ® Mn 2+ ; E 0 = +1.51V

[AIPMT 2014, A] The E0 for 3Mn ® Mn + 2Mn 3+ will be:

2+

(a) 96500 C (b) 2 × 96500 C (a) –2.69 V; the reaction will not occur
(b) –2.69 V; the reaction will occur
(c) 9650 C (d) 96.50 C
(c) –0.33 V; the reaction will not occur
19. The weight of silver (at wt. = 108) displaced by a quantity of
(d) –0.33 V; the reaction will occur
electricity which displaces 5600 mL of O2 at STP will be :-
26. The metal that cannot be obtained by electrolysis of an
[AIPMT 2014, A]
aqueous solution of its salts is: [JEE M 2014, C]
(a) 5.4 g (b) 10.8 g (c) 54.9 g (d) 108.0 g
(a) Ag (b) Ca (c) Cu (d) Cr
20. A 1.0 M with respect to each of the metal halides AX 3 , 27. In the cell reaction
BX 2 , CX 3 and DX 2 is electrolysed using platinum Cu(s) + 2Ag + (aq) ¾¾ ® Cu 2 + (aq) + 2Ag(s) ,
electrodes. If E0cell = 0.46 V. By doubling the concentration of Cu2+, E0cell
E oA 3+ / A = 1.50 V, E oB2+ / B = 0.3 V, is [BISAT 2014, S]
o
E oC3+ / C = -0.74 V, E D 2+ / D = -2.37 V. (a) doubled (b) halved
The correct sequence in which the various metals are (c) increases but less than double
deposited at the cathode is [AIIMS 2014, A] (d) decreases by a small fraction
(a) A, B, C, D (d) A, B, C 28. Cuaq+ is unstable in solution and undergoes simultaneous
(c) D, C, B, A (b) C, B, A oxidation and reduction according to the reaction :
21. Assertion : On increasing dilution, the specific conductance [BISAT 2014, A]
ˆˆ† Cu 2+ (aq) + Cu(s)
2Cu + (aq) ‡ˆˆ
keep on increasing.
Reason : On increasing dilution, degree of ionisation of choose correct Eº for above reaction if
weak electrolyte increases and molality of ions also Eº Cu2+/Cu = 0.34 V and Eº Cu2+/Cu+ = 0.15 V
increases. [AIIMS 2014, C] (a) –0.38 V (b) +0.49 V (c) +0.38 V (d) –0.19 V
(a) Assertion is correct, reason is correct; reason is a 29. Aqueous solution of which of the following compounds is
correct explanation for assertion. the best conductor of electric current? [AIPMT 2015 RS, C]
(b) Assertion is correct, reason is correct; reason is not a (a) Acetic acid, C2H4O2 (b) Hydrochloric acid, HCl
correct explanation for assertion (c) Ammonia, NH3 (d) Fructose, C6H12O6
ELECTROCHEMISTRY 237

30. A device that converts energy of combustion of fuels like 39. The equilibrium constant for the disproportionation reaction
hydrogen and methane, directly into electrical energy is [BITSAT 2016, A]
known as : [AIPMT 2015, C] 2Cu + (aq) ¾¾
® Cu(s) + Cu 2 + (aq)
(a) Electrolytic cell (b) Dynamo
at 25°C
(c) Ni-Cd cell (d) Fuel Cell
31. A hydrogen electrode is immersed in a solution with pH = 0 (E ° = 0.52 V, E° = 0.16 V) is
Cu + /Cu Cu 2 + /Cu
(HCl). By how much will the potential (reduction) change if
(a) 6 × 104 (d) 6 × 106 (c) 1.2 × 106 (d) 1.2 × 10–6
an equivalent amount of NaOH is added to the solution.
40. The EMF of the cell Tl/Tl+ (0.001M) || Cu2+ (0.01M) /Cu is
(Take pH2 = 1 atm), T = 298 K. [AIIMS 2015, S] 0.83. The cell EMF can be increased by [BITSAT 2016, C]
(a) increase by 0.41 V (b) increase by 59 mV (a) Increasing the concentration of Tl+ ions.
(c) decrease by 0.41 V (d) decrease by 59 mV (b) Increasing the concentration of Cu2+ ions.
(c) Increasing the concentration of Tl + and Cu2+ ions.
32. Two Faraday of electricity is passed through a solution of
(d) None of these
CuSO4. The mass of copper deposited at the cathode is
41. Ionic mobility of which of the following alkali metal ions is
(at. mass of Cu = 63.5 amu) [JEE M 2015, A]
lowest when aqueous solution of their salts are put under
(a) 2g (b) 127 g (c) 0 g (d) 63.5 g
an electric field ? [NEET 2017, C]
33. The efficiency of fuel cell is given by the expression, h is (a) K (b) Rb (c) Li (d) Na
[BITSAT 2015, A] 42. In the electrochemical cell :- [NEET 2017, A]
nFE cell nFE cell Zn | ZnSO4 (0.01M) | | CuSO4 (1.0 M) | Cu, the emf of this
(a) h = - ´ 100 (b) h = - ´ 100
DH DS Daniel cell is E1. When the concentration of ZnSO4 is
nFE cell changed to 1.0M and that of CuSO4 changed to 0.01M, the
(c) h = - ´ 100 (d) None of the above emf changes to E2. From the followings, which one is the
DA
34. The mass of the substance deposited when one Faraday of RT
charge is passed through its solution is equal to relationship between E1 and E4? (Given, = 0.059)
F
[BITSAT 2015, C] (a) E1 < E2 (b) E1 > E2
(a) relative equivalent weight (c) E2 = 0 ¹ E1 (d) E1 = E2
(b) gram equivalent weight 43. On the basis of the following E° values, the strongest
(c) specific equivalent weight oxidizing agent is : [AIIMS 2017, A]
(d) None of the above [Fe(CN)6]4– ®[Fe(CN)6]3– + e– ; E° = – 0.35 V
35. The pressure of H2 required to make the potential of H2- Fe2+ ® Fe3+ + e–; E° = – 0.77 V
electrode zero in pure water at 298 K is : [NEET 2016, A] (a) [Fe(CN)6]4– (b) Fe2+
(a) 10–14 atm (b) 10–12 atm (c) Fe3+ (d) [Fe(CN)6]3–
–10
(c) 10 atm (d) 10–4 atm 44. Consider the following cell reaction: [AIIMS 2017, A]
36. Given that the standard reduction potentials for M+/M and 2Fe(s) + O 2 (g) + 4H + (aq) ®
N+/N electrodes at 298 K are 0.52 V and 0.25 V respectively. 2Fe 2+ (aq) + 2H 2 O(l) ; E ° = 1.67V
2+ –3
At [Fe ] = 10 M, p(O2) = 0.1 atm and pH = 3, the cell
Which of the following is correct in respect of the following
electrochemical cell ? [AIIMS 2016, S] potential at 25ºC is
M/M+ | | N+/N (a) 1.47 V (b) 1.77 V (c) 1.87 V (d) 1.57 V
(a) The overall cell reaction is a spontaneous reaction. 45. Given [JEE M 2017, A]
(b) The standard EMF of the cell is – 0.27 V.
Eo = 1.36V, E o = –0.74V,
(c) The standard EMF of the cell is 0.77 V. Cl2 /Cl – Cr 3+ /Cr
(d) The standard EMF of the cell is – 0.77 V.
37. Galvanization is applying a coating of: [JEE M 2016, C] Eo = 1.33V,Eo = 1.51V.
Cr2O72- / Cr3+ MnO4– / Mn2+
(a) Cu (b) Zn (c) Pb (d) Cr
38. Electrolysis is carried out in three cells [BITSAT 2016, C] Among the following, the strongest reducing agent is
(A) 1.0 M CuSO4 Pt electrode (a) Cr (b) Mn 2+ (c) Cr3+ (d) Cl–
(B) 1.0 M CuSO4 copper electrodes 46. Assertion : Zinc can be used while copper cannot be used
(C) 1.0 M KCl Pt electrodes in the recovery of Ag from the complex [Ag(CN)2]–.
If volume of electrolytic solution is maintained constant in Reason : Zinc is a powerful reducing agent than copper.
each of the cell, which is correct set of pH changes in (A), [BITSAT 2017, C]
(B) and (C) cell respectively ? (a) Assertion is correct, reason is correct; reason is a
(a) decrease in all the three correct explanation for assertion.
(b) increase in all the three (b) Assertion is correct, reason is correct; reason is not a
(c) decrease, constant, increase correct explanation for assertion
(d) increase, constant, increase (c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct.
 EBD_7374
238 CHEMISTRY

47. Stronger is oxidising agent, more is [BITSAT 2017, C] 52. 0.1 mole, per litre solution is present in a conductivity cell
(a) standard reduction potential of that species where electrode of 100 cm2 area are placed at 1 cm apart and
(b) the tendency to get it self oxidised resistance observed is 5 × 103 Ohm, what is molar conduc-
(c) the tendency to lose electrons by that species tivity of solution? [AIIMS 2018, S]
(d) standard oxidation potential of that species
(a) 5 × 102 S cm2 mole–1 (b) 2 × 104 S cm2 mole–1
48. Which of the following relation represents correct relation
(c) 200 S cm2 mole–1 (d) 0.02 S cm2 mole–1
between standard electrode potential and equilibrium
constant? [BITSAT 2017, S] 53. Assertion : Reverse current flows in charging of lead stor-
age battry. [AIIMS 2018, C]
nFE °
nFE° Reason : During charging PbSO4 convert into Pb and PbO2
I. log K = II. K = e RT (a) If both assertion and reason are true and reason is the
2.303 RT
-nFE° correct explanation of assertion.
nFE°
III. log K = IV.. log K = 0.4342 (b) If both assertion and reason are true but reason is not
2.303 RT RT the correct explanation of assertion.
Choose the correct statement(s). (c) If assertion is true but reason is false.
(a) I, II and III are correct (b) II and III are correct (d) If both assertion and reason are false.
(c) I, II and IV are correct (d) I and IV are correct 54. For hydrogen-oxygen fuel cell, the cell reaction is
49. E° for the cell, ® 2H 2 O( l)
2H 2 ( g ) + O 2 ( g ) ¾¾
Zn | Zn 2+ (aq) | | Cu 2+ (aq)| Cu is 1.10 V at 25°C. The If DG °f (H 2O) = – 237.2 kJ mol–1, then emf of this cell is
equilibrium constant for the cell reaction [BITSAT 2017, A] [AIIMS 2018, A]
Zn + Cu 2+ (aq) ‡ˆˆ ˆˆ† Cu + Zn 2+ (aq) (a) + 2.46 V (b) – 2.46 V (c) + 1.23 V (d) – 1.23 V
55. How long (approximate) should water be electrolysed by
is of the order of
(a) 10–37 (b) 1037 (c) 10–17 (d) 1017 passing through 100 amperes current so that the oxygen
50. Specific conductance of 0.1 M HA is released can completely burn 27.66 g of diborane?
3.75 × 10–4 ohm–1 cm–1. If (Atomic weight of B = 10.8 u) [JEE M 2018, A]
(a) 6.4 hours (b) 0.8 hours(c) 3.2 hours(d) 1.6 hours
l¥ ( HA ) = 250 ohm -1 cm 2 mol -1 , the dissociation 56. On passing a current of 1.0 ampere for 16 min and 5 sec through
constant Ka of HA is : [BITSAT 2017, A] one litre solution of CuCl2, all copper of the solution was
(a) 1.0 × 10–5 (b) 2.25 × 10–4 deposited at cathode. The strength of CuCl2 solution was
(c) 2.25 × 10–5 (d) 2.25 × 10–13 (Molar mass of Cu= 63.5; Faraday constant = 96,500 Cmol–1)
51. Consider the change in oxidation state of bromine [BITSAT 2018, S]
corresponding to different emf values as shown in the (a) 0.01 N (b) 0.01 M (c) 0.02 M (d) 0.2 N
diagram below : [NEET 2018, S] 57. A 100.0 mL dillute solution of Ag+ is electrolysed for
– 1.82 V – 1.5 V 15.0 minutes with a current of 1.25 mA and the silver is
BrO4 ¾¾¾® BrO3 ¾¾¾® HBrO
removed completely. What was the initial [Ag+]?
¾¾

Br –¬¾¾¾ Br2 ¬¾¾¾ [BITSAT 2018, S]

1.0652 V 1.595 V (a) 2.32 × 10–1 (b) 2.32 × 10–4
Then the species undergoing disproportion-ation is
(c) 2.32 × 10–3 (d) 1.16 × 10–4
(a) BrO3– (b) BrO 4– (c) HBrO (d) Br2

Exercise 3 : Try If You Can

1. The e.m.f. of the cell Zn | Zn2+ (0.01M) | | Fe2+ (0.001M) | Fe at 3. A solution containing one mole per litre of each Cu(NO3)2,
298 K is 0.2905 then the value of equilibrium for the cell AgNO3, Hg2(NO3)2 and Mg(NO3)2, is being electrolysed
reaction is by using inert electrodes. The values of standard electrode
0.32 0.32 0.26 0.32 potentials in volts (reduction potentials) are Ag+ / Ag
(a) (b) (c) (d) = +0.80, Hg2+ 2+ 2+
e 0.0295 10 0.0295 10 0.0295 10 0.0591 2 / 2Hg = +0.79, Cu / Cu= +0.34, and Mg / Mg
2. In electrolysis of NaCl when Pt electrode is taken, then H2 is = –2.37 with increasing voltage, the sequence of deposition
liberated at cathode while with Hg cathode it forms sodium of metals on the cathode will be
amalgam. This is because (a) Ag, Hg, Cu, Mg (b) Mg, Cu, Hg, Ag
(a) Hg is more inert than Pt (c) Ag, Hg, Cu (d) Cu, Hg, Ag
(b) more voltage is required to reduce H+ at Hg than at Pt 4. From the following half - cell reactions and their standard
(c) Na is dissolved in Hg while it does not dissolve in Pt potentials, what is the smallest possible standard e.m.f. for
(d) conc. of H+ ions is larger when Pt electrode is taken spontaneous reactions?
ELECTROCHEMISTRY 239

PO 34- ( aq ) + 2H 2 O(l) + 2e - ¾¾
® HPO32 + 3OH - ( aq ) ; 10. Given the ionic equivalent conductivities for the following
ions:
E° = – 1.05 V
l°eq K+ = 73.5 cm2 ohm– 1 eq– 1
PbO2 (s) + H2O (l) + 2e– ¾¾
® PbO (s) + 2OH– (aq); l°eq Al3+ = 149 cm2 ohm– 1 eq– 1
E° = +0.28 V l°eq SO42– = 85.8 cm2 ohm– 1 eq– 1
IO 3- (aq ) + 2H 2 O(l) + 4e - ¾¾ ® IO - (aq ) + 4OH - (aq ) ; The L°eq for potash alum (K2 SO4. Al2(SO4)3. 24H2O) is
E° = + 0.56 V (a) 215.92 (b) 348.3 (c) 368.2 (d) 108.52
(a) + 0.00 V (b) + 0.74 V (c) + 0.56 V (d) + 0.28 V –
COO
5. Co | Co2+ (C2) || Co2+ (C1) | Co; for this cell, DG is negative if: 11. Given the ionic conductance of | , K+, and Na+ are 74,
–
(a) C2 > C1 (b) C1 > C2 COO
(c) C1 = C2 (d) unpredictable 2 – 1 – 1
50, and 73 cm ohm eq , respectively. The equivalent
6. Consider the following standard electrode potentials and COONa
calculate the equilibrium constant at 25° C for the indicated conductance at infinite dilution of the salt | is
disproportion nation reaction : COOK
(a) 197 cm2 ohm– 1 eq– 1 (b) 172 cm2 ohm– 1 eq– 1
® Mn(s) + 2Mn 3+ ( aq )
3Mn 2+ (aq) ¾¾ (c) 135.5 cm ohm eq2 – 1 – 1 (d) 160.5 cm2 ohm– 1 eq– 1
12. During conductometric titration of 0.1 M HCl with 1.0 M
Mn 3+ (aq) + e - ¾¾
® Mn 2+ (aq); E° = 1.51 V KOH, which is the correct observation.
Mn 2+ (aq) + 2e- ¾¾
® Mn(s); E° = -1.185 V (a) Resistance of the solution decreases upto equivalence
point and then increases
(a) 1.2 ´ 10–43 (b) 2.4 ´ 10–73 (b) Resistance increases upto equivalence point and then
(c) 6.3 ´ 10 –92 (d) 1.5 ´ 10–62 decreases
(c) Conductance increases upto equivalence point and
7. The temperature coefficient of a cell whose operation is then decreases
based on the reaction (d) Conductance decreases upto equivalence point and
Pb(s) + HgCl2 (aq) ¾¾
® PbCl2 (aq) + Hg (l) is : then becomes almost constant.
13. For the galvanic cell :
æ dE ö -4 -1
çè ÷ø = 1.5 ´ 10 VK at 298 K Al( s ) | Al3+ ( aq )(0.1M ) || Ag + ( aq )(0.1M ) | Ag( s) ,
dT p
which of the following is/are correct ?
The change in entropy (in J/K mol) during the operation (a) Reaction quotient Q = 1.0 × 10–2
is :
(b) log10Q = 3
(a) 8627 (b) 57.9 (c) 28.95 (d) 14.475
8. Given the following cell at 25° C (c) Q = 1.0 × 103
(d) Q = 1.0 × 102
H 2 CH3COOH NaOH H 2
Pt (1 atm) Pt. What will 14. If E1° is standard electrode potential for Fe/Fe2+ and E°2 is
(10 – 3 M) (10 – 3M) (1 atm)
be the potential of the cell? Given pKa of CH3COOH = 4.74 for Fe2+/Fe3+ and E °3 for Fe/Fe3+. A relation between E1° .
(a) – 0.42 V (b) 0.42 V (c) – 0.19 V (d) 0.19 V
E°2 and E °3 is:
9. The specific conductance of a saturated solution of silver
bromide is k S cm–1. The limiting ionic conductivity of Ag+ (a) 3E°3 = 2E1° + E °2 (b) E°3 = 2E1° + 3E °2
and Br– ions are x and y, respectively. The solubility of (c) E°3 = E1° + E °2 (d) E°3 = 3E1° - E °2
silver bromide in g L–1 is : (molar mass of AgBr = 188) 15. The equilibrium constant for the reaction is :
k ´ 1000 k
´ 188 In 2 + + Cu 2+ ¾¾
® In 3+ + Cu + at 298 K
(a) (b)
x-y x+y ° °
Given, E Cu 2+ / Cu + = 0.15 V, E In 3+ / In +
k ´ 1000 ´ 188 x + y 1000 = -0.42 V, E° 2+ + = -0.40 V
(c) (d) ´ In / In
x+y k 188 (a) 105 (b) 103 (c) 1010 (d) 106
 EBD_7374
240 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (a) 14 (d) 27 (b) 40 (d) 53 (d) 66 (b) 79 (a) 92 (a) 105 (b) 118 (c)
2 (b) 15 (c) 28 (d) 41 (a) 54 (c) 67 (b) 80 (d) 93 (b) 106 (a) 119 (c)
3 (d) 16 (b) 29 (c) 42 (d) 55 (b) 68 (a) 81 (d) 94 (d) 107 (b) 120 (d)
4 (d) 17 (c) 30 (c) 43 (c) 56 (d) 69 (b) 82 (a) 95 (b) 108 (b) 121 (c)
5 (b) 18 (a) 31 (b) 44 (d) 57 (c) 70 (d) 83 (a) 96 (a) 109 (c) 122 (d)
6 (c) 19 (b) 32 (a) 45 (b) 58 (d) 71 (d) 84 (b) 97 (b) 110 (b) 123 (d)
7 (b) 20 (c) 33 (d) 46 (b) 59 (b) 72 (d) 85 (b) 98 (a) 111 (d) 124 (c)
8 (d) 21 (d) 34 (a) 47 (a) 60 (b) 73 (b) 86 (c) 99 (a) 112 (c)
9 (d) 22 (a) 35 (b) 48 (c) 61 (d) 74 (b) 87 (d) 100 (c) 113 (c)
10 (b) 23 (d) 36 (c) 49 (d) 62 (d) 75 (d) 88 (d) 101 (c) 114 (b)
11 (d) 24 (c) 37 (a) 50 (a) 63 (a) 76 (c) 89 (d) 102 (b) 115 (d)
12 (d) 25 (b) 38 (c) 51 (c) 64 (b) 77 (d) 90 (a) 103 (b) 116 (a)
13 (a) 26 (b) 39 (a) 52 (d) 65 (d) 78 (b) 91 (b) 104 (a) 117 (b)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (c) 7 (c) 13 (c) 19 (d) 25 (a) 31 (c) 37 (b) 43 (c) 49 (b) 55 (c)
2 (a) 8 (b) 14 (d) 20 (b) 26 (b) 32 (d) 38 (c) 44 (d) 50 (c) 56 (a)
3 (c) 9 (c) 15 (a) 21 (d) 27 (d) 33 (a) 39 (c) 45 (a) 51 (c) 57 (d)
4 (b) 10 (b) 16 (b) 22 (a) 28 (c) 34 (b) 40 (b) 46 (a) 52 (d)
5 (d) 11 (d) 17 (d) 23 (a) 29 (b) 35 (a) 41 (c) 47 (a) 53 (a)
6 (c) 12 (d) 18 (c) 24 (c) 30 (d) 36 (b) 42 (b) 48 (c) 54 (c)
Exercis e 3 : Try If You Can
1 (b) 3 (c) 5 (b) 7 (c) 9 (c) 11 (c) 13 (d) 15 (c)
2 (b) 4 (d) 6 (c) 8 (a) 10 (a) 12 (b) 14 (a)
 18 Chapter
CHEMICAL KINETICS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 3 First order reaction kinetics,
AIIMS 2 Arrhenius equation, order 4/5 7.8
JEE Main 2 and molecularity.
BITSAT 2
 EBD_7374
242 CHEMISTRY
CHEMICAL KINETICS 243
 EBD_7374
244 CHEMISTRY

Exercise 1 : Topic-wise MCQs

10. Study the following graphs and choose the correct option
Topic 1: Rate of a Chemical Reaction
[R] 0
1. The rate law for the single- step reaction 2A + B ¾¾ ® 2C, (P)
is given by:

Concentration
Concentration
(a) rate = k [A].[B] c1 A c2 C
(b) rate = k [A]2.[B] c2 D[P]
B
(c) rate = k [2A].[B] c1
Dt D
(d) rate = k [A]2.[B]o
2. The rate of a chemical reaction tells us about, t4 t 2 t t4 t2 t
Time Time
(a) the reactants taking part in reaction (a) (b)
(b) the products formed in the reaction (i) in fig. a, A represents average rate and B represents
(c) how slow or fast the reaction is taking place instantaneous rate
(d) None of the above (ii) in fig. b, D represents average rate and C represents
3. Consider the reaction instantaneous rate
N2 (g) + 3H2 (g) ® 2 NH3 (g) (iii) fig. a, A represents instantaneous rate and B represents
d[ NH 3 ] d[H 2 ] average rate
The equality relationship between and - (iv) fig. b, C represents average rate and D represents
dt dt
is instantaneous rate
(a) (i) and (ii) are correct (b) (ii) and (iv) are correct
d[NH 3 ] 2 d[H 2 ] d[ NH 3 ] 3 d[H 2 ] (c) (i) and (iv) are correct (d) (ii) and (iii) are correct
(a) + =- (b) + =-
dt 3 dt dt 2 dt 11. In the following reaction, how is the rate of appearance of
d[ NH 3 ] d[H 2 ] d[ NH 3 ] 1 d[ H 2 ] underlined product related to the rate of disappearance of
(c) =- (d) =- the underlined reactant ?
dt dt dt 3 dt
4. The rate of reaction BrO 3- (aq) + 5Br - (aq) + 6H + ¾¾
® 3Br 2 (l) + 3H 2 O(l)
(a) increases as the reaction proceeds d[Br2 ] d[Br - ] d[Br2 ] 3 d[Br - ]
(b) decreases as the reaction proceeds (a) =- (b) =+
dt dt dt 5 dt
(c) remains the same as the reaction proceeds
(d) may decrease or increase as the reaction proceeds d[Br2 ] 3 d[Br - ] d[Br2 ] 5 d[Br - ]
(c) =- (d) =-
5. The unit of rate of reaction is dt 5 dt dt 3 dt
(a) mol/dm3 (b) mol/pound 12. The rate of the reaction 2N2O5 ® 4NO2 + O2 can be written
(c) mol/dm3 sec (d) mol/cm3 in three ways :
6. In the rate equation, when the conc. of reactants is unity -d[N 2O5 ] d[NO2 ]
then rate is equal to = k[N 2 O5 ] ; = k ¢ [N 2 O5 ]
dt dt
(a) specific rate constant
(b) average rate constant d[O2 ]
= k ¢¢ [N 2O5 ]
(c) instantaneous rate constant dt
(d) None of above The relationship between k and k' and between k and k¢¢ are:
7. The rate of reaction between two specific time intervals is (a) k¢ = 2k ; k¢ = k (b) k¢ = 2k ; k¢¢ = k / 2
called (c) k¢ = 2k ; k¢¢ = 2k (d) k¢ = k ; k¢¢ = k
(a) instantaneous rate (b) average rate 13. The reaction of hydrogen and iodine monochloride is given
(c) specific rate (d) ordinary rate as:
8. At the beginning the decrease in the conc. of reactants is H 2 (g) + 2ICl(g) ¾¾
® 2HCl(g) + I 2 (g)
(a) slow (b) moderate The reaction is of first order with respect to H2(g) and ICl(g),
(c) rapid (d) None of above following mechanisms were proposed.
9. The average rate and instantaneous rate of a reaction are Mechanism A:
equal
H 2 (g) + 2ICl(g) ¾¾
® 2HCl(g) + I 2 (g)
(a) at the start
(b) at the end Mechanism B:
(c) in the middle H 2 (g) + ICl(g) ¾¾
® HI(g);slow
(d) when two rate have time interval equal to zero HI(g) + ICl(g) ¾¾
® HCl(g) + I 2 (g);fast
CHEMICAL KINETICS 245

Which of the above mechanism(s) can be consistent with 21. For the following homogeneous reaction,
the given information about the reaction? k
(a) A and B both (b) Neither A nor B A + B ¾¾ ®C
(c) A only (d) B only the unit of rate constant is
(a) sec –1 (b) sec–1 mol L–1
Topic 2: Factors Influencing Rate of a Reactions –1
(c) sec mol L –1 (d) sec–1 mol–2 L2
14. Assertion: The rate of the reaction is the rate of change of 22. Velocity constant k of a reaction is affected by
concentration of a reactant or a product. (a) change in the concentration of the reactant
Reason: Rate of reaction remains constant during the course (b) change of temperature
of reaction. (c) change in the concentration of the product
(a) Assertion is correct, reason is correct; reason is a (d) None of the above
correct explanation for assertion. 23. The rate constant for the reaction 2 N 2 O 5 ¾ ¾® 4 NO 2 + O 2
(b) Assertion is correct, reason is correct; reason is not a is 3.10 × 10 sec . If the rate is 2.4 × 10 mol litre–1 sec–1
–5 –1 –5

correct explanation for assertion. then the concentration of N 2 O 5 (in mol litre–1) is :
(c) Assertion is correct, reason is incorrect.
(a) 0.04 (b) 0.8 (c) 0.07 (d) 1.4
(d) Assertion is incorrect, reason is correct.
24. The rate law for a reaction between the substances A and B
15. For the following reaction: NO2(g) + CO(g) ® NO(g) +
is given by Rate = k [A]n [B]m
CO2(g), the rate law is: Rate = k [NO2]2. If 0.1 mole of gaseous
On doubling the concentration of A and halving the
carbon monoxide is added at constant temperature to the
concentration of B, the ratio of the new rate to the earlier
reaction mixture which of the following statements is true?
rate of the reaction will be as
(a) Both k and the reaction rate remain the same 1
(b) Both k and the reaction rate increase (a) (m + n) (b) (n – m) (c) 2(n – m) (d) (m + n )
2
(c) Both k and the reaction rate decrease
(d) Only k increases, the reaction rate remain the same 25. In the reaction 2A + B ® A 2 B, if the concentration of A is
16. Which one of the following statements for the order of a doubled and that of B is halved, then the rate of the reaction will:
reaction is incorrect ? (a) increase 2 times (b) increase 4 times
(a) Order can be determined only experimentally. (c) decrease 2 times (d) remain the same
(b) Order is not influenced by stoichiometric coefficient of 26. The order of a reaction, with respect to one of the reacting
the reactants. component Y, is zero. It implies that:
(c) Order of reaction is sum of power to the concentration (a) the reaction is going on at a constant rate
terms of reactants to express the rate of reaction. (b) the rate of reaction does not vary with temperature
(d) Order of reaction is always whole number. (c) the reaction rate is independent of the concentration
17. The rate of the reaction 2NO + Cl2 ¾¾ of Y
® 2NOCl is given
(d) the rate of formation of the activated complex is zero
by the rate equation rate = k [NO]2 [Cl2] 27. The unit of rate constant for a zero order reaction is
The value of the rate constant can be increased by: (a) mol L–1 s–1 (b) L mol–1 s–1
(a) increasing the concentration of NO. (c) L2 mol–2 s–1 (d) s –1
(b) increasing the temperature. 28. Which one of the following reactions is a true first order
(c) increasing the concentration of the Cl 2 reaction?
(d) doing all of the above (a) Alkaline hydrolysis of ethyl acetate
18. Units of rate constant of first and zero order reactions in (b) Acid catalyst hydrolysis of ethyl acetate
terms of molarity M unit are respectively (c) Decomposition of N2O
(a) sec–1, Msec–1 (b) sec–1, M (d) Decomposition of gaseous ammonia on a hot platinum
–1
(c) Msec , sec –1 (d) M, sec–1. surface
19. A reaction involving two different reactants can never 29. What is order with respect to A, B, C, respectively
be [A] [B] [C] rate (M/sec.)
(a) bimolecular reaction (b) second order reaction 0.2 0.1 0.02 8.08 × 10–3
(c) first order reaction (d) unimolecular reaction 0.1 0.2 0.02 2.01 × 10–3
20. 3A ® B + C , it would be a zero order reaction when 0.1 1.8 0.18 6.03 × 10–3
(a) the rate of reaction is proportional to square of 0.2 0.1 0.08 6.464 × 10–2
concentration of A (a) –1, 1, 3/2 (b) –1, 1, 1/2 (c) 1, 3/2, –1 (d) 1, –1, 3/2
(b) the rate of reaction remains same at any concentration 30. The order of a reaction with rate equal to k[A]3/2 [B]–1/2 is :
of A 1 3
(a) 1 (b) - (c) - (d) 2
(c) the rate remains unchanged at any concentration of B 2 2
and C 31. For the reaction,
(d) the rate of reaction doubles if concentration of B is H+
increased to double CH3COCH3 + I2 ¾¾¾
® products
 EBD_7374
246 CHEMISTRY

The rate is governed by expression (i) Rate of reaction = Rate constant

dx (ii) Rate of reaction depends on concentration of ammonia.
= k[acetone][H + ] (iii) Rate of decomposition of ammonia will remain constant
dt
The order w.r.t. I2 is: until ammonia disappears completely.
(a) 1 (b) 0 (c) 3 (d) 2 (iv) Further increase in pressure will change the rate of
32. The rate constant of a reaction is 3.00 × 103 L mol–1 sec–1. reaction.
The order of this reaction will be: (a) (i), (iii) and (iv) (b) (i), (ii) and (iii)
(a) 0 (b) 1 (c) 2 (d) 3 (c) (ii) and (iv) (d) (i), (ii) and (iv)
33. During the kinetic study of the reaction, 2A + B ® C + D, 38. The hypothetical reaction A 2 + B 2 ¾ ¾® 2 AB ; follows
Fast
following results were obtained: the following mechanism A 2 ¾¾¾® A + A ,
Slow
–1 –1 A + B 2 ¾ ¾¾® AB + B , A + B ¾Fast ¾® AB .
¾
[A](mol L ) [B](mol L ) Initial rate of formation of
Run –1 –1 The order of the overall reaction is
D (mol L min )
–3
(a) 0 (b) 1 (c) 2 (d) 3/2
I 0.1 0.1 6.0 × 10 39. The initial rates of reaction
–2
II 0.3 0.2 7.2 × 10 3A + 2B + C ¾¾ ® Products, at different initial
–1
III 0.3 0.4 2.88 × 10 concentrations are given below:
IV 0.4 0.1 2.40 × 10
–2 Initial rate, [A]0, M [B]0, M [C]0, M
Ms–1
Based on the above data which one of the following is
5.0 × 10–3 0.010 0.005 0.010
correct?
5.0 × 10–3 0.010 0.005 0.015
(a) rate = k [A]2 [B] (b) rate = k[A] [B] 1.0 × 10–2 0.010 0.010 0.010
(c) rate = k [A]2 [B]2 (d) rate = k [A] [B]2 1.25 × 10–3 0.005 0.005 0.010
The order with respect to the reactants, A, B and C are
34. The chemical reaction 2O 3 ¾ ¾® 3O 2 proceeds as follows: respectively
Fast
O 3 ¾¾ ¾® O 2 + O ; O + O 3 ¾Slow
¾¾® 2O 2 the rate law (a) 3, 2, 0 (b) 3, 2, 1 (c) 2, 2, 0 (d) 2, 1, 0
expression should be
(a) r = k[O3]2 (b) r = k [O3]2[O2]–1 Topic 3: Integrated Rate Equations
3
(c) r = k [O3][O2] 2 (d) r = [O3][O2]2 40. Assertion: The rate of reaction is always negative.
35. Nitrogen monoxide, NO, reacts with hydrogen, H2, according Reason: Minus sign used in expressing the rate shows that
to the following equation: concentration of reactant is decreasing.
2NO(g) + 2H2(g) ® N2(g) + 2H2O(g) (a) Assertion is correct, reason is correct; reason is a
If the mechanism for this reaction were, correct explanation for assertion.
2NO(g) + H2(g) ® N2(g) + H2O2(g) ; slow (b) Assertion is correct, reason is correct; reason is not a
H2O2(g) + H2(g) ® 2H2O(g) ; fast correct explanation for assertion.
Which of the following rate laws would we expect to obtain (c) Assertion is correct, reason is incorrect.
experimentally? (d) Assertion is incorrect, reason is correct.
(a) Rate = k[H2O2][H2] (b) Rate = k[NO]2[H2] 41. The plot that represents the zero order reaction is :
2
(c) Rate = k[NO] [H2] 2 (d) Rate = k[NO][H2]
36. Which of the following statement(s) is/are correct? [R] [R]
(i) Rate of reaction decreases with passage of time as the (a) (b)
concentration of reactants decrease. t t
¾®

(ii) For a reaction

pP + qQ ¾¾ ® rR + sS [R]
(c) (d) ln[R]
Rate = k[P]x [Q]y where x = p and y = q t t ¾®
(iii) Rate law is the expression in which reaction rate is 42. The plot of concentration of the reactant vs time for a
given in terms of molar concentration of reactants with reaction is a straight line with a negative slope. The reaction
each term raised to some power, which may or may not follows a rate equation
be same as the stichiometric coefficient of the reacting (a) zero order (b) first order
species in a balanced chemical equation. (c) second order (d) third order
(a) (i) and (iii) (b) (i) and (ii) 43. The half-life of a reaction is inversely proportional to the
(c) (ii) and (iii) (d) (i) only square of the initial concentration of the reactant. Then the
37. At high pressure the following reaction is of zero order. order of the reaction is
(a) 0 (b) 1 (c) 2 (d) 3
2NH3 ( g ) ¾¾¾¾¾¾¾
® N 2 ( g ) + 3H 2 ( g )
1130 K
44. The rate equation for a reaction,
Platinum catalyst
N2O ¾® N2 + 1/2O2
Which of the following statements are correct for above is Rate = k[N2O]0 = k. If the initial concentration of the
reaction? reactant is a mol Lit–1, the half-life period of the reaction is
CHEMICAL KINETICS 247

a a k 56. The rate law for the reaction 2X + Y ® Z is Rate = k[X][Y].

(a) t1 = (b) - t 1 = ka (c) t 1 = (d) t 1 = The correct statement with regard to this relation is
2 k k a
2 2 2 2 (a) the rate of the reaction is independent of [X] and [Y]
45. Half life of a first order reaction is 4 s and the initial (b) for this reaction t1/2 is independent of initial
concentration of the reactant is 0.12 M. The concentration concentrations of reactant
of the reactant left after 16 s is (c) the rate of formation of Z is twice the rate of
(a) 0.0075 M(b) 0.06 M (c) 0.03 M (d) 0.015 M disappearance of X
46. The reaction A ¾® B follows first order kinetics. The time (d) the rate of disappearance of X is equal to rate of
disappearance of Y
taken for 0.8 mole of A to produce 0.6 mole of B is 1 hour.
57. Consider a reaction aG + bH ® Products. When
What is the time taken for conversion of 0.9 mole of A to
concentration of both the reactants G and H is doubled, the
produce 0.675 mole of B?
rate increases by eight times. However, when concentration
(a) 2 hours (b) 1 hour (c) 0.5 hour (d) 0.25 hour
of G is doubled keeping the concentration of H fixed, the
47. The rate of a first order reaction is 1.5 × 10–2 mol L–1 min–1 at
rate is doubled. The overall order of the reaction is
0.5 M concentration of the reactant. The half life of the reaction is
(a) 0 (b) 1 (c) 2 (d) 3
(a) 0.383 min(b) 23.1 min (c) 8.73 min (d) 7.53 min
58. Diazonium salt decomposes as
48. The rate constant for a first order reaction whose half-life, is
480 seconds is : C6 H 5 N +2 Cl - ® C6 H5Cl + N 2
(a) 2.88 × 10–3 sec–1 (b) 2.72 × 10–3 sec–1 At 0°C, the evolution of N2 becomes two times faster when
(c) 1.44 × 10 –3 sec–1 (d) 1.44 sec–1 the initial concentration of the salt is doubled. Therefore, it
49. The rate constant of a first order reaction is 6.9 ´10-3 s -1 . is
How much time will it take to reduce the initial concentration (a) a first order reaction
to its 1/8th value? (b) a second order reaction
(a) 100 s (b) 200 s (c) 300 s (d) 400 s (c) independent of the initial concentration of the salt
50. A reaction proceeds by first order, 75% of this reaction (d) a zero order reaction
was completed in 32 min. The time required for 50% 59. The following data pertains to reaction between A and B :
completion is S. [A] mol L–1 [B] mol L–1 Rate (mol L–1 time–1)
(a) 8 min (b) 16 min (c) 20 min (d) 24 min No.
51. Point out the wrong statement: 1 1.0 × 10–2 2.0 × 10–2 2.0 × 10–4
2 2.0 × 10 –2 2.0 × 10–2 4.0 × 10–4
For a first order reaction
3 2.0 × 10 –2 4.0 × 10–2 8.0 × 10–4
(a) time for half-change (t1/2) is independent of initial
concentration Which of the following inference(s) can be drawn from the
(b) change in the concentration unit does not change the above data ?
rate constant (k) (i) Rate constant of the reaction is 1.0 × 10–4.
(c) time for half-change × rate constant = 0.693 (ii) Rate law of the reaction is : rate = k[A][B]
(d) the unit of k is mol–1 min–1 (iii) Rate of reaction increases four times on doubling the
52. t 1 can be taken as the time taken for the concentration of a concentration of both the reactants.
Select the correct answer using the codes given below :
4
3 (a) (i), (ii) and (iii) (b) (i) and (ii)
reactant to drop to of its initial value. If the rate constant
4 t (c) (ii) and (iii) (d) (iii) only
for a first order reaction is k, the 1 can be written as 60. The decomposition of ammonia on tungsten surface at 500 K
4
(a) 0.75/k (b) 0.69/k (c) 0.29/k (d) 0.10/k follows zero order kinetics. The half-life period of this
53. Consider the reaction, 2A + B ® products. When reaction is 45 minutes when the initial pressure is 4 bar. The
concentration of B alone was doubled, the half-life did not half-life period (minutes) of the reaction when the initial
change. When the concentration of A alone was doubled, pressure is 16 bar at the same temperature is
the rate increased by two times. The unit of rate constant (a) 120 (b) 60 (c) 240 (d) 180
for this reaction is 61. A substance 'A' decomposes by a first order reaction starting
(a) s –1 (b) L mol–1 s–1 initially with [A] = 2.00 M and after 200 min, [A] becomes
(c) no unit (d) mol L–1 s–1. 0.15 M. For this reaction t1/2 is
54. For a first order reaction, a plot of log (a – x) against time is (a) 53.72 min (b) 50.49 min
a straight line with a negative slope equal to (c) 48.45 min (d) 46.45 min
62. If half-life of a substance is 5 yrs, then the total amount of
-k 2.303 Ea
(a) (b) – 2.303 k (c) (d) - 2.303 R substance left after 15 years, when initial amount is 64 grams
2.303 k is
55. In a reaction A ® Products, when start is made from (a) 16 grams (b) 2 grams (c) 32 grams (d) 8 grams.
8.0 × 10–2 M of A, half-life is found to be 120 minute. For the 63. In a 1st order reaction, reactant concentration C varies with
initial concentration 4.0 × 10–2 M, the half-life of the reaction time t as :
becomes 240 minute. The order of the reaction is : 1
(a) zero (b) one (c) two (d) 0.5 (a) increases linearly with t
C
 EBD_7374
248 CHEMISTRY

(b) log C decreases linearly with t (b) Assertion is correct, reason is correct; reason is not a
1 correct explanation for assertion.
(c) C decreases with
t (c) Assertion is correct, reason is incorrect.
1 (d) Assertion is incorrect, reason is correct.
(d) log C decreases with
t
64. For the first order reaction Topic 5: Temperature Dependence of the Rate of a Reaction
C 2 H 4 O(g) ® CH 4 (g) + CO(g) , the initial pressure of 70. In the Haber process for the manufacture of ammonia the
C2H4O(g) is 80 torr and total pressure at the end of 20 minutes following catalyst is used
is 120 torr. The time needed for 75% decomposition of C2H4O (a) Platinized asbestos
would be : (b) Iron with molybdenum as promoter
(a) 20 minutes (b) 40 minutes (c) Copper oxide
(c) 80 minutes (d) 120 minutes (d) Alumina
65. The integrated rate equations can be determined for 71. What is the activation energy for a reaction if its rate doubles
(a) zero order reactions (b) first order reactions when the temperature is raised from 20°C to 35°C?
(c) second order reactions (d) Both (a) and (b) (R = 8.314 J mol–1 K–1)
(a) 269 kJ mol–1 (b) 34.7 kJ mol–1
(c) 15.1 kJ mol –1 (d) 342 kJ mol–1
Topic 4: Pseudo First Order Reaction
72. A reaction having equal energies of activation for forward
66. Assertion: The order of a reaction may be negative. and reverse reaction has :
Reason: In some cases, the rate of reaction decreases as the (a) DG = 0 (b) DH = 0
concentration of the reactant increases. (c) DH = DG = DS = 0 (d) DS = 0
(a) Assertion is correct, reason is correct; reason is a
73. In an exothermic reaction if DH is the enthalpy then activation
correct explanation for assertion.
energy is
(b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion. (a) more than DH (b) less than DH
(c) Assertion is correct, reason is incorrect. (c) equal to DH (d) none of the above
(d) Assertion is incorrect, reason is correct. 1
74. In the Arrhenius plot of ln k vs , a linear plot is obtained
67. Which of the following statement(s) is/are correct ? T
(i) For a zero order reaction concentration [R] vs time (t) with a slope of –2 × 104 K. The energy of activation of the
gives a straight line plot reaction (in kJ mole–1) is (R value is 8.3 J K–1 mol–1)
[R]0
(ii) For a first order reaction log does not vary linearly (a) 83 (b) 166 (c) 249 (d) 332
with time. [R] 75. Plots showing the variation of the rate constant (k) with
(iii) Inversion of cane sugar is a pseudo first order reaction. temperature (T) are given below. The plot that follows
(a) (i) and (iii) (b) (i) only Arrhenius equation is
(c) (ii) and (iii) (d) (iii) only
68. The bromination of acetone that occurs in acid solution is
represented by this equation.
CH3COCH3 (aq) + Br2 (aq) ® CH3COCH2Br (aq) + H+ (aq) (a) (b)
+ Br– (aq)
These kinetic data were obtained for given reaction
concentrations.
Initial Initial rate, (c) (d)
Concentrations, M disappearance
of Br2, Ms–1 76. If the activation energy for the forward reaction is 150 kJ mol–1
[CH3 COCH3] [Br2] [H+] and that of the reverse reaction is 260 kJ mol–1, what is the
0.30 0.05 0.05 5.7×10–5 enthalpy change for the reaction ?
0.30 0.10 0.05 5.7 × 10–5 (a) 410 kJ mol–1 (b) –110 kJ mol–1
0.30 0.10 0.10 1.2 × 10–4 (c) 110 kJ mol–1 (d) – 410 kJ mol–1
0.40 0.05 0.20 3.1 × 10–4
77. In respect of the equation k = Ae - Ea / RT in chemical
Based on given data, the rate equations is:
kinetics, which one of the following statements is correct ?
(a) Rate = k[CH3COCH3][H+]
(b) Rate = k [CH3COCH3][Br2] (a) A is adsorption factor (b) Ea is energy of activation
(c) Rate = k [CH3COCH3] [Br2] [H+]2 (c) R is Rydberg’s constant (d) k is equilibrium constant
(d) Rate = k [CH3COCH3][Br2] [H+] 78. The activation energy for a reaction is 9.0 kcal/mol. The
69. Assertion: Hydrolysis of cane sugar is a first order reaction. increase in the rate constant when its temperature is
Reason: Water is present in large excesss during hydrolysis. increased from 298 K to 308 K is
(a) Assertion is correct, reason is correct; reason is a (a) 63% (b) 50% (c) 100% (d) 10%
correct explanation for assertion.
CHEMICAL KINETICS 249

79. In a reversible reaction the energy of activation of the (iii) A plot of log P versus 1/T is linear at constant volume
forward reaction is 50 kcal. The energy of activation for the (iv) A plot of P versus 1/V is linear at constant temperature
reverse reaction will be (a) (i) only (b) (ii) only
(a) < 50 kcal (c) (i) and (iv) (d) (i), (ii) and (iv)
(b) either greater than or less than 50 kcal 88. Match the columns.
(c) 50 kcal Column-I Column-II
(d) > 50 kcal (A) Catalyst alters the rate (p) cannot be fraction or zero
80. Which of the following statements best describes how a of reaction
catalyst works? (B) Molecularity (q) proper orientation is not
(a) A catalyst changes the potential energies of the there always.
reactants and products. (C) Second half life of first (r) by lowering the activation
(b) A catalyst decreases the temperature of the reaction order reaction energy
which leads to a faster rate. (D) Energetically favourable (s) is same as the first
(c) A catalyst lowers the activation energy for the reaction reactions are sometimes
by providing a different reaction mechanism. slow
(d) A catalyst destroys some of the reactants, which lowers (a) A – (q), B – (r), C – (s), D – (p)
the concentration of the reactants. (b) A – (r), B – (s), C – (p), D – (q)
81. A chemical reaction was carried out at 300 K and 280 K. The (c) A – (r), B – (p), C – (s), D – (q)
rate constants were found to be k1 and k2 respectively. then (d) A – (p), B – (r), C – (s), D – (q)
(a) k1 = 4k1 (b) k2 = 2k1 89. In a zero-order reaction for every 10° rise of temperature, the
(c) k2 = 0.25 k1 (d) k2 = 0.5 k1 rate is doubled. If the temperature is increased from 10°C to
82. For a first order reaction, the plot of log K against 1/T is a 100°C, the rate of the reaction will become :
straight line. The slope of the line is equal to (a) 256 times(b) 512 times (c) 64 times (d) 128 times
E 2.303 Ea -E a 90. For a first order reaction A®P, the temperature (T) dependent
(a) - a (b) - E R (c) - (d)
2.303 R
rate constant (k) was found to follow the equation
R a 2 . 303
83. Activation energy of the reaction is 1
log k = – (2000) + 6.0 . The pre-exponential factor A and
(a) the energy released during the reaction T
(b) the energy evolved when activated complex is formed the activation energy Ea, respectively, are
(c) minimum amount of energy needed to overcome the (a) 1.0 × 106 s–1 and 9.2 kJ mol–1
potential barrier (b) 6.0 s–1 and 16.6 kJ mol –1
(d) the energy needed to form one mole of the product (c) 1.0 × 106 s–1 and 16.6 kJ mol–1
84. In a reaction, the threshold energy is equal to (d) 1.0 × 106 s–1 and 38.3 kJ mol–1
(a) activation energy + normal energy of reactants 91. The activation energies of two reactions are E 1 and
(b) activation energy – normal energy of reactants E2 (E1 > E2). If the temperature of the system is increased
(c) normal energy of reactants – activation energy from T1 to T2, the rate constant of the reactions changes
(d) average kinetic energy of molecules of reactants from k1 to k1' in the first reaction and k2 to k2' in the second
85. For the exothermic reaction A + B ® C + D, DH is the heat reaction. Predict which of the following expression is correct?
of reaction and Ea is the energy of activation. The energy of k1' k '2 k1' k 2'
activation for the formation of A + B will be (a) = (b) >
k1 k 2 k1 k 2
(a) Ea (b) DH (c) Ea + DH (d) DH – Ea
86. Consider the following statements: k1' k '2 k1' k '2
(i) Increase in concentration of reactant increases the (c) < (d) = =1
k1 k 2 k1 k 2
rate of a zero order reaction.
(ii) Rate constant k is equal to collision frequency A if 92. A graph plotted between log k vs 1/T for calculating
Ea = 0. activation energy is shown by
(iii) Rate constant k is equal to collision frequency A if
Ea = ¥.
(iv) ln k vs T is a straight line. (a) log k (b) log k
(v) ln k vs 1/T is a straight line.
Correct statements are 1/T 1/T
(a) (i) and (iv) (b) (ii) and (v)
(c) (iii) and (iv) (d) (ii) and (iii)
87. The following statement(s) is (are) correct :
(i) A plot of log Kp versus 1/T is linear (c) log k (d) log k
(ii) A plot of log [X] versus time is linear for a first order
reaction, X ® P 1/T 1/T
 EBD_7374
250 CHEMISTRY

93. The rate constant, the activation energy and the arrhenius (b) The mechanism of a reaction will change when a
parameter of a chemical reaction at 25°C are 3.0 × 10–4s–1, catalyst is added.
104.4 kJ mol–1 and 6.0 × 1014 s–1 respectively. The value of (c) A catalyst provides a different activation energy for a
the rate constant as T ® ¥ is reaction.
(a) 2.0 × 1018 s–1 (b) 6.0 × 1014 s–1 (d) A catalyst changes the speed of a reaction, but not the
(c) Infinity (d) 3.6 × 1030 s–1 equilibrium constant.
94. The activation energy for a hypothetical 101. Collision theory is applicable to
reaction, A ® Product, is 12.49 kcal/mol. If temperature is (a) first order reactions (b) zero order reactions
raised from 295 K to 305 K, the rate of reaction increased by (c) bimolecular reactions (d) intra-molecular reactions
(a) 60% (b) 100% (c) 50% (d) 20% 102. According to the collision theory of reaction rates, the rate
95. A reactant (A) froms two products : of reaction increases with temperature due to
k (a) greater number of collision
A ¾¾
1 ® B,
Activation Energy Ea (b) higher velocity of reacting molecules
1
k2 (c) greater number of molecules having the activation energy
A ¾¾® C, Activation Energy Ea
2 (d) decrease in the activation energy
If Ea = 2 Ea , then k1 and k2 are related as : 103. In most cases, for a rise of 10 K temperature the rate constant
2 1
E a /RT Ea /RT is doubled to tripled. This is due to the reason that
(a) k2 = k1e 1 (b) k2 =k1e 2
(a) collision frequency increases by a factor of 2 to 3.
E /RT E /RT (b) fraction of molecules possessing threshold energy
(c) k2 = Ak1e a1 (d) k1 = 2k 2e a2
increases by a factor of 2 to 3
96. During decomposition of an activated complex. (c) activation energy is lowered by a factor of 2 to 3.
(i) energy is always released (d) none of these
(ii) energy is always absorbed 104. According to which theory activation energy and proper
(iii) energy does not change orientation of the molecules together determine the criteria
(iv) reactants may be formed for an effective collision ?
(a) (i), (ii) and (iii) (b) (i) and (iv) (a) Arrhenius theory
(c) (ii) and (iii) (d) (ii), (iii) and (iv) (b) Activated complex theory
97. Which of the following statements is incorrect ? (c) Collision theory
(a) Energy is always released when activated complex (d) Both (a) and (c)
decomposes to form products. 105. According to collision theory, not all collisions between
(b) Peak of the energy distribution curve corresponds to molecules lead to reaction. Which of the following
the most probable potential energy. statements provide reasons for the same ?
(c) Peak of the energy distribution curve corresponds to (i) The total energy of the two colliding molecules is less
the most probable kinectic energy. than some minimum amount of energy.
(d) When the temperature is raised maximum of energy (ii) Molecules cannot react with each other unless a
distribution curve moves to higher energy value and catalyst is present.
broadens out. (iii) Molecules that are improperly oriented during collision
98. Assertion: For each ten degree rise of temperature the will not react.
specific rate constant is nearly doubled. (iv) Molecules in different states of matter cannot react
Reason: Energy-wise distribution of molecules in a gas is with each other.
an experimental function of temperature. (a) (i) and (ii) (b) (i) and (iii)
(a) Assertion is correct, reason is correct; reason is a (c) (ii) and (iii) (d) (i) and (iv)
correct explanation for assertion.
106. Match the columns
(b) Assertion is correct, reason is correct; reason is not a
Column - I Column - II
correct explanation for assertion.
(A) Number of collisions per (p) Effective
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct. second per unit volume collisions.
of the reaction mixture.
Topic 6: Collision Theory of Chemical Reactions (B) Fraction of molecules (q) Collision
with energies equal to frequency
99. In terms of the ‘Collision Theory of Chemical Kinetics’, the or greater than Ea
rate of a chemical reaction is proportional to
(a) the change in free energy per second
(C) Molecules for which (r) e - Ea /RT
(b) the change in temperature per second Rate = Z ABe -Ea /RT
(c) the number of collisions per second
(d) the number of products molecules shows significant deviations
100. According to collision theory, which of the following is NOT (D) Collision in which molecules (s) Complex
a true statement concerning a catalyst? collide with sufficient K.E. molecules
(a) A catalyst changes the temperature of reaction. and proper orientation.
CHEMICAL KINETICS 251

(a) A – (q), B – (r), C – (s), D – (p) Column-I Column-II

(b) A – (r), B – (q), C – (s), D – (p) (A) X – A (p) Enthalpy of reaction
(c) A – (q), B – (s), C – (r), D – (p) (B) X – B (q) Energy of transition state
(d) A – (q), B – (r), C – (p), D – (s) (C) A – B (r) Activation energy of
107. The reason for almost doubling the rate of reaction on forward reaction
increasing the temperature of the reaction system by 10°C (D) X (s) Activation energy of
is backward reaction
(a) the value of threshold energy increases (a) A – (s), B – (r), C – (q), D – (p)
(b) collision frequency increases (b) A – (q), B – (r), C – (p), D – (s)
(c) the fraction of the molecule having energy equal to (c) A – (r), B – (s), C – (p), D – (q)
threshold energy or more increases (d) A – (s), B – (r), C – (p), D – (q)
(d) activation energy decreases 109. Collision theory is used to explain how chemical species
108. Consider the energy diagram of a reaction : B ® A, on the undergo a reaction. Using this theory and the kinetic
basis of given diagram select the correct code for matching molecular model, which of the following does NOT influence
Column-I and Column-II. the rate of a chemcial reaction?
(a) The temperature of the system
X (b) The geometry or orientation of the collision
(c) The velocity of the reactants at the point of collision
(d) All of the above influence the rate
Energy

110. Which of the following has been used to explain the subject
B
of chemical kinetics
A (a) Collision theory of bimolecular reactions
(b) The activated complex theory
(c) Arrhenius equation
Progress of reaction (d) All of these

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (a) Activation energy of forward reaction is E 1 + E2 and
product is less stable than reactant
1. The role of a catalyst is to change ........... .
(b) Activation energy of forward reaction is E 1 + E2 and
(a) Gibbs energy of reaction
product is more stable than reactant
(b) enthalpy of reaction
(c) Activation energy of both forward and backward
(c) activation energy of reaction
reaction is E1 +E2 and reactant is more stable than product
(d) equilibrium constant
(d) Activation energy of backward reaction is E1 and
2. In the presence of a catalyst, the heat evolved or absorbed
product is more stable than reactant
during the reaction ........ .
5. Consider a first order gas phase decomposition reaction
(a) increases (b) decreases
given below
(c) remains unchanged (d) may increase or decrease
A(g) ® B(g) + C(g)
3. Activation energy of a chemical reaction can be determined
The initial pressure of the system before decomposition of
by ...... .
A was pi. After lapse of time 't' total pressure of the system
(a) determining the rate constant at standard temperature
increased by x units and became 'pt'. The rate constant k for
(b) determining the rate constant at two temperatures
the reaction is given as ........... .
(c) determining probability of collision
(d) using catalyst 2.303 p 2.303 pi
(a) k= log i (b) k = log
4. Consider figure and mark the correct option. t pi - x t 2pi - pt
Activated complex 2.303 pi 2.303 p
(c) k= log (d) k = log i
t 2pi + p t t pi + x
E1
6. According to Arrhenius equation rate constant k is equal to
Energy

Products
A e - E a / RT
/RTT. Which of the following options represents the
E2

1
Reactants graph of ln k vs ?
T
Reaction coordinate
 EBD_7374
252 CHEMISTRY

(a) 8. Consider the Arrhenius equation given below and mark the
correct option. Ea
-
k = Ae RT
ln k (a) Rate constant increases exponentially with increasing
activation energy and decreasing temperature
(b) Rate constant decreases exponentially with increasing
1/T activation energy and decreasing temperature
(b) (c) Rate constant increases exponentially with decreasing
activation energy and decreasing temperature
(d) Rate constant increases exponentially with decreasing
ln k activation energy and increasing temperature
9. Which of the following statements is not correct about order
of a reaction?
1/T (a) The order of a reaction can be a fractional number
(c)
(b) Order of a reaction is experimentally determined
quantity
(c) The order of a reaction is always equal to the sum of
ln k the stoichiometric coefficients of reactants in the
balanced chemical equation for a reaction
(d) The order of a reaction is the sum of the powers of
1/T molar concentration of the reactants in the rate law
(d) expression
10. Consider the graph given in figure. Which of the following
options does not show instantaneous rate of reaction at
ln k
40th second?

1/T V5
7. A graph of volume of hydrogen released vs time for the V4
reaction between zinc and dil. HCl is given in figure. On the
basis of this mark the correct option.
V3

V5
V4 V2
V1

V3

O
20 30 40 50
V2
V1 V5 - V2 V4 - V2
(a) (b)
50 - 30 50 - 30

O V3 - V2 V3 - V1
20 30 40 50 (c) (d)
40 - 30 40 - 20
V3 - V2 11. Which of the following statements is correct?
(a) Average rate upto 40s is
40 (a) The rate of a reaction decreases with passage of time
V3 - V2 as the concentration of reactants decreases.
(b) Average rate upto 40s is (b) The rate of a reaction is same at any time during the
40 - 30
reaction.
V3
(c) Average rate upto 40s is (c) The rate of a reaction is independent of temperature
40 change.
V3 - V1 (d) The rate of a reaction decreases with increase in
(d) Average rate upto 40s is
40 - 20 concentration of reactant(s).
CHEMICAL KINETICS 253

12. Which of the following expressions is correct for the rate of (c) Collision of atoms or molecules possessing sufficient
reaction given below? threshold energy results into the product formation
5Br - ( aq ) + BrO 3- ( aq ) + 6H + (aq ) ® 3Br2 (aq ) + 3H 2 O ( l ) (d) Molecules should collide with sufficient threshold
energy and proper orientation for the collision to be
D [ Br - ] D [H+ ] D [ Br - ] 6 D [ H + ] effective
(a) =5 (b) = 16. A first order reaction is 50% completed in 1.26 × 1014 s. How
Dt Dt Dt 5 Dt
much time would it take for 100% completion?
D [ Br - ] 5 D [ H + ] D [ Br - ] D [ H+ ] (a) 1.26 × 1015 s (b) 2.52 × 1014 s
(c) = (d) =6 (c) 2.52 × 10 s 28 (d) Infinite
Dt 6 Dt Dt Dt 17. Compounds 'A' and 'B' react according to the following
13. Which of the following graphs represents exothermic chemical equation.
reaction? A(g) + 2B(g) ¾® 2C(g)
Activated complex Concentration of either 'A' or 'B' were changed keeping the
concentrations of one of the reactants constant and rates
were measured as a function of initial concentration.
Following results were obtained. Choose the correct option
Energy

for the rate equations for this reaction.

(I)
Reactants Experiment Initial Initial Initial
Products concentration concentration concentration of
–1 –1 –1 –1
of [A]/mol L of [B]/mol L [C]/mol L s
Reaction coordinate
1. 0.30 0.30 0.10
Activated complex 2. 0.30 0.60 0.40
3. 0.60 0.30 0.20

(a) Rate = k [A]2[B] (b) Rate = k [A] [B]2

(c) Rate = k [A] [B] (d) Rate = k [A]2[B]0
Energy

(II) 18. Which of the following statement is not correct for the
Products catalyst?
(a) It catalyses the forward and backward reactions to the
Reactants
same extent
Reaction coordinate (b) It alters DG of the reaction
Activated complex (c) It is a substance that does not changes the equilibrium
constant of a reaction
(d) It provides an alternate mechanism by reducing
activation energy between reactants and products.
19. The value of rate constant of a pseudo first order
Energy

(III)
reaction.............
Reactants Products (a) depends on the concentration of reactants present in
small amount
(b) depends on the concentration of reactants present in
Reaction coordinate excess
(a) Only (I) (b) Only (II) (c) is independent of the concentration of reactants
(c) Only (III) (d) Both (I) and (II) (d) depends only on temperature
14. Rate law for the reaction A + 2B ¾® C is found to be 20. Consider the reaction A ® B. The concentration of both the
Rate = k[A] [B] reactants and the products varies exponentially with time.
Concentration of reactant 'B' is doubled, keeping the Which of the following figures correctly describes the change
concentration of 'A' constant, the value of rate constant in concentration of reactants and products with time?
will be ...... .
[B]
(a) the same (b) doubled
(c) quadrupled (d) halved
15. Which of the following statements is incorrect about the
Concentration

collision theory of chemical reaction?

(a) It considers reacting molecules or atoms to be hard (a)
spheres and ignores their structural features [A]
(b) Number of effective collisions determines the rate of
Time
reaction
 EBD_7374
254 CHEMISTRY

[B] (a) 8 mm min–1 (b) 2 mm min–1

(c) 16 mm min–1 (d) 4 mm min–1
24. The decomposition of A follows two parallel first order
reactions [BITSAT 2014, S]
Concentration

(b) k1 = 1.26 ´ 10 -4 sec -1

[A] B
A k 2 = 3.8 ´ 10- 5 sec - 1
Time C

[B] The percentage distribution of B and C are

(a) 90 % B and 10 % C (b) 80 % B and 20 % C
(c) 60 % B abd 40 % C (d) 76.83% B and 23.17 % C
Concentration

25. The rate constant of the reaction A ® B is 0.6 × 10–3 mole per
(c) second. If the concentration of A is 5 M then concentration
[A] of B after 20 minutes is : [AIPMT 2015 RS, S]
(a) 1.08 M (b) 3.60 M (c) 0.36 M (d) 0.72 M
Time
26. When initial concentration of a reactant is doubled in a
reaction, its half-life period is not affected. The order of the
[A] reaction is : [AIPMT 2015, A]
(a) First
Concentration

(b) Second
(d) (c) More than zero but less than first
[B]
(d) Zero
Time 27. The activation energy of a reaction can be determined from the
Past Year MCQs slope of which of the following graphs ? [AIPMT 2015, C]
21. Half-lives of a first order and a zero order reaction are same. ln K l
(a) vs.T (b) ln K vs.
Then the ratio of the initial rates of first order reaction to T T
that of the zero order reaction is [AIIMS 2014, S] T l
(c) vs. (d) ln K vs . T
1 2 ln K T
(a) (b) 2 × 0.693 (c) 0.693 (d)
0.693 0.693 28. Select the rate law that corresponds to the data shown for
22. For the non - stoichimetre reaction 2A + B ® C + D, the the following reaction A + B ¾ ¾® C
following kinetic data were obtained in three separate [AIIMS 2015, S]
experiments, all at 298 K. [JEE M 2014, S] Expt. No. (A) (B) Initial Rate
1 0.012 0.035 0.10
Initial Initial Initial rate of 2 0.024 0.070 0.80
Concentration Concentration formation of C 3 0.024 0.035 0.10
–1 –1
(A ) (B ) (mol L s ) 4 0.012 0.070 0.80
–3 (a) Rate = k[B] 3 (b) Rate = k [B]4
0.1 M 0.1 M 1.2 × 10
0.1 M 0.2 M 1.2 × 10
–3 (c) Rate = k [A] [B]3 (d) Rate = k [A]2 [B]2
0.2 M 0.1 M –3 29. Assertion : If the activation energy of a reaction is zero,
2.4 × 10
temperature will have no effect on the rate constant.
The rate law for the formation of C is: [AIIMS 2015, C]
dc dc Reason : Lower the activation energy, faster is the reaction.
= k [ A][ B ] = k [ A] [ B ]
2
(a) (b) (a) If both Assertion and Reason are correct and the Reason
dt dt
is a correct explanation of the Assertion.
dc dc
= k [ A][ B ] = k [ A]
2
(c) (d) (b) If both Assertion and Reason are correct but Reason is
dt dt not a correct explanation of the Assertion.
1 (c) If the Assertion is correct but Reason is incorrect.
23. A gaseous reaction X 2 (g) ¾
¾® Y + Z (g)
2 (d) If both the Assertion and Reason are incorrect.
There is increase in pressure from 100 mm to 120 mm in 5 (e) If the Assertion is incorrect but the Reason is correct.
minutes. The rate of disappearance of X2 is
[BITSAT 2014, S]
CHEMICAL KINETICS 255

30. Higher order (>3) reactions are rare due to : [JEE M 2015, C] 39. Consider the reaction :
(a) shifting of equilibrium towards reactants due to elastic + -
collisions Cl 2 (aq) + H 2S(aq) ® S(s) + 2H (aq) + 2Cl (aq)
(b) loss of active species on collision The rate equation for this reaction is
(c) low probability of simultaneous collision of all the rate = k[Cl2 ][H 2S]
reacting species
(d) increase in entropy and activation energy as more Which of these mechanisms is/are consistent with this rate
molecules are involved equation? [BITSAT 2016, S]
31. In a first order reaction with time the concentration of the A. Cl 2 + H 2S ® H + + Cl - + Cl+ + HS- (slow)
reactant decreases [BITSAT 2015, C]
(a) linearly (b) exponentially Cl + + HS- ® H + + Cl- + S (fast)
(c) no change (d) None of these + -
B. H 2S ƒ H + HS (fast equilibrium)
32. The unit of rate constant for reactions of second order is
[BITSAT 2015, C] Cl 2 + HS- ® 2Cl - + H + + S (Slow)
(a) L mol–1s–1 (b) L–1 mol s–1 (a) B only (b) Both A and B
(c) L mol s–1 (d) s –1 (c) Neither A nor B (d) A only
33. The rate of a first-order reaction is 0.04 mol L–1s–1 at 10 seconds
40. Mechanism of a hypothetical reaction [NEET 2017, S]
and 0.03 mol L–1s–1 at 20 seconds after initiation of the reaction.
The half-life period of the reaction is [NEET 2016, S] X2 + Y2 ® 2XY is given below :
(a) 24.1 s (b) 34.1 s (c) 44.1 s (d) 54.1 s (i) X2 ® X + X(fast)
34. The addition of a catalyst during a chemical reaction alters (ii) X + Y2 ƒ XY + Y (slow)
which of the following quantities? [NEET 2016, C] (iii) X + Y ® XY (fast)
(a) Entropy (b) Internal energy The overall order of the reaction will be :
(c) Enthalpy (d) Activation energy
35. Collision theory is used to explain how chemical species (a) 2 (b) 0 (c) 1.5 (d) 1
undergo a reaction. Using this theory and the kinetic 41. A first order reaction has a specific reaction rate of
molecular model, which of the following does NOT influence 10–2 sec–1. How much time will it take for 20g of the reactant
the rate of a chemical reaction? [AIIMS 2016, C] to reduce to 5 g ? [NEET 2017, S]
(a) The temperature of the system (a) 138.6 sec (b) 346.5 sec (c) 693.0 sec (d) 238.6 sec
(b) The geometry or orientation of the collision 42. Which of the following relation represents correct relation
(c) The velocity of the reactants at the point of collision between standard electrode potential and equilibrium
(d) All of the above influence the rate constant? [AIIMS 2017, C]
36. For the following reaction: NO2(g) + CO(g) ® NO(g) +
nFE°
CO2(g), the rate law is: Rate = k [NO2]2. If 0.1 mole of gaseous I. log K =
carbon monoxide is added at constant temperature to the 2.303 RT
reaction mixture which of the following statements is true? nFE °
[AIIMS 2016, C] II. K = e RT
(a) Both k and the reaction rate remain the same nFE°
(b) Both k and the reaction rate increase III. log K =
2.303 RT
(c) Both k and the reaction rate decrease nFE °
(d) Only k increases, the reaction rate remain the same IV. log K = 0.4342
37. Decomposition of H2O2 follows a first order reaction. In RT
Choose the correct statement(s).
fifty minutes the concentration of H2O2 decreases from 0.5
to 0.125 M in one such decomposition. When the (a) I, II and III are correct (b) II and III are correct
concentration of H2O2 reaches 0.05 M, the rate of formation (c) I, II and IV are correct (d) I and IV are correct
of O2 will be: [JEE M 2016, S] 43. Assertion : The kinetics of the reaction –
(a) 2.66 L min–1 at STP (b) 1.34 × 10–2 mol min–1
(c) 6.96 × 10–2 mol min–1 (d) 6.93 × 10–4 mol min–1 mA + nB + pC ¾¾
® m ' X + n 'Y + p ' Z
38. In the reaction, dX
P + Q ¾¾® ? R + S obey the rate expression as = k[ A]m [ B ]n .
The time taken for 75% reaction of P is twice the time taken dt
for 50% reaction of P. The concentration of Q varies with Reason : The rate of the reaction does not depend upon the
reaction time as shown in the figure. The overall order of the concentration of C. [AIIMS 2011, 17, C]
reaction is [BITSAT 2016, S] (a) If both Assertion and Reason are correct and the Reason
is a correct explanation of the Assertion.
[Q]0 (b) If both Assertion and Reason are correct but Reason is
not a correct explanation of the Assertion.
[Q] (c) If the Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Time
(e) If the Assertion is incorrect but the Reason is correct.
(a) 2 (b) 3 (c) 0 (d) 1
 EBD_7374
256 CHEMISTRY

44. Two reactions R1 and R2 have identical pre-exponential 49. Rate of two reactions whose rate constants are k1 and k2
factors. Activation energy of R1 exceeds that of R2 by are equal at 300 K such that : [AIIMS 2018, C]
10 kJ mol–1. If k1 and k2 are rate constants for reactions R1 Ea2 – Ea1 = 2RT,
and R2 respectively at 300 K, then ln(k2/k1) is equal to : A
(R = 8.314 J mol–1K–1) [JEE M 2017, S] So calculate l n 2
A1
(a) 8 (b) 12 (c) 6 (d) 4 (a) l n 4 (b) 2 (c) log 2 (d) 2- l n 2
45. The rate of reaction between two reactants A and B 50. At 518°C, the rate of decomposition of a sample of gaseous
decreases by a factor of 4 if the concentration of reactant acetaldehyde, initially at a pressure of 363 Torr, was 1.00
B is doubled. The order of this reaction with respect to Torr s–1 when 5% had reacted and 0.5 Torr s–1 when 33%
reactant B is: [BITSAT 2017, S] had reacted. The order of the reaction is : [JEE M 2018, S]
(a) 2 (b) -2 (c) 1 (d) -1 (a) 2 (b) 3 (c) 1 (d) 0
46. For the reaction H2(g) + Br2 (g) ® 2HBr (g), the experimental 51. The accompanying figure depicts a change in concentra-
data suggest, rate = k[H2][Br2]1/2. The molecularity and order tion of species A and B for the reaction A ® B, as a function
of the reaction are respectively [BITSAT 2017, S] of time. The point of inter section of the two curves repre-
3 3 3 1 sents [BITSAT 2018, C]
(a) 2, (b) , (c) 1, 1 (d) 1,
2 2 2 2 [B]
47. The correct difference between first and second order
reactions is that [NEET 2018, C]

conc
(a) The rate of a first-order reaction does not depend on [A]
reactant concentrations, the rate of a second-order
Times
reaction does depend on reactant concentrations
(b) The half-life of a first-order reaction does not depend (a) t 1/2 (b) t 3/4
on [A]0, the half-life of a second-order reaction does (c) t 2/3
depend on [A]0 (d) Data insufficient to predict
(c) The rate of a first-order reaction does depend on 52. The rate constant of a reaction is 1.5 × 10– 3 at 25°C and
reactant concentrations, the rate of a second-order 2.1 × 10– 2 at 60°C. The activation energy is
reaction does not depend on reactant concentrations [BITSAT 2018, S]
(d) A first-order reaction can be catalyzed, a second-order
reaction cannot be catalyzed 35 2.1 ´ 10 – 2 298 ´ 333 21
(a) R log e (b) R loge
48. If a first order reaction is 80% complete in 60 minutes. Find 333 1.5 ´ 10 – 2 35 1.5
the t 1 of reaction? [AIIMS 2018, S]
298 ´ 333 298 ´ 333 2.1
2 (c) R loge 2.1 (d) R loge
35 35 1.5
(a) 30 min (b) 42 min (c) 25.85 min (d) 14.28 min

Exercise 3 : Try If You Can

1. The instantaneous rate of disappearance of MnO4– ion in rate constant is 4.5 × 10– 2. In an experiment, the initial titre
the following reaction is 4.56 × 10–3 Ms–1 value was 25 mL. The titre value will be 5 mL after a lapse of
2MnO4– + 10I– + 16H+ ® 2Mn2+ + 5I2 + 8H2O log e 5
(a) 4.5 × 10– 2 × 5 min (b) min
The rate of appearance I2 is : 4.5×10 – 2
(a) 4.56 × 10–4 Ms–1 (b) 1.14 × 10–2 Ms–1 log e 5/4
(c) 1.14 × 10–3 Ms–1 (d) 5.7 × 10–3 Ms–1 (c) min (d) None of these
4.5×10 – 2
2. The decomposition of H2O2 can be followed by titration
3. Decomposition of NH4NO2 (aq) into N2 (g) and 2H2O(l) is
with KMnO4 and is found to be a first order reaction. The
first order reaction. Which of the following graph is correct?
CHEMICAL KINETICS 257

[NH4NO2 ]

[NH4NO2 ]
P.E. P.E.
X
A+B X
(a) (b) (c) (d) A+B
AB
AB

time time R.C. R.C.

10. For the equilibrium, A(g) ƒ B(g), DH is –40 kJ/mol. If the
ratio of the activation energies of the forward (E f) and
[NH4NO2 ]

[NH4NO2 ]
2
(c) (d) reverse (Eb) reactions is then :
3
(a) Ef = 80 kJ/mol; Eb = 120 kJ/mol
time time
(b) Ef = 60 kJ/mol; Eb = 100 kJ/mol
(c) Ef = 30 kJ/mol; Eb = 70 kJ/mol
k = 0.6 M min -1
4. For a reaction A ¾¾ ¾¾¾¾® 2B starting with 1 M (d) Ef = 70 kJ/mol; Eb = 30 kJ/mol
of 'A' only, concentration of B (in M) after 100 sec. and 11. A graph plotted between logk Vs 1/T for calculating
200 sec. is respectively? activation energy is shown by
(a) 2 and 4 (b) 1 and 2
(c) 2 and 3 (d) none of these log k
log k
5. For a particular reaction with initial conc. of the reactants (a) (b)
as a1 and a2, the half-life period are t1 and t2 respectively.
The order of the reaction (n) is given by :
1/T 1/T
log ( t 2 / t1 ) log ( t1 / t 2 )
(a) n =1+ (b) n =
log ( a 2 / a1 ) log ( a 2 / a1 )
log k
log k
log ( t1 / t 2 ) log ( t 2 /t1 ) (c) (d)
(c) n =1+ (d) n = 1 -
log ( a 2 / a1 ) log ( a 2 /a1 )
1/T
6. A first order reaction is half completed in 45 minutes. How 1/T
long does it need 99.9% of the reaction to be completed 12. Activation energy and pre-exponential factor of a chemical
(a) 5 hours (b) 7.5 hours (c) 10 hours (d) 20 hours reaction are 2 × 102 kJ mol–1 and 3.0 × 1015 s–1 respectively.
7. Cyclopropane rearranges to form propene If the rate constant of the reaction at 298 is 5.0 × 10 –1, its
value when T® ¥ is :
¾¾
® CH3 - CH = CH 2 (a) 2.0 × 105 s–1 (b) 1.5 × 1011 s–1
This follows first order kinetics. The rate constant is (c) 3.0 × 1015 s–1 (d) 2 × 102 s–1
2.714 × 10 –3 sec –1. The initial concentration of cyclopropane 13. For the reaction:
is 0.29 M. What will be the concentration of cyclopropane [Cr(H2O)6]3+ + [SCN –] ® [Cr(H2O)5NCS]2+ + H2O
after 100 sec
The rate law is: r = k[Cr(H2O)6]3+ + [SCN –].
(a) 0.035 M (b) 0.22 M (c) 0.145 M (d) 0.0018 M
The value of k is 2.0 × 10– 6 L mol– 1 s– 1 at 14°C and
8. The rate constants k1 and k2 for two different reactions are
1016 . e–2000/T and 1015 . e–1000/T, respectively. The temperature 2.2 × 10– 5 L mol– 1 s– 1 at 30°C. What is the value of Ea?
at which k1 = k2 is : (a) 26 kcal mol– 1 (b) 2.6 kcal mol– 1
(c) 2600 kcal mol– 1 (d) 260 kcal mol– 1
2000 1000
(a) 1000 K (b) K (c) 2000 K K (d) 14. Gaseous cyclobutane isomerizes to butadiene following first
2.303 2.303 order process which has half-life of 150.5 minutes at certain
9. For an exothermic chemical process occurring in two steps temperature. How long will take for the process to occur to
as follows the extent of 40% at the same temperature ?
(i) A + B ® X (slow) (ii) X ® AB (fast) (a) 103 minutes (b) 121 minutes
The progress of reaction can be best described by :
(c) 111 minutes (d) None of these
15. In the first order reaction 2 N 2 O 5 ¾
¾® 4 NO 2 + O 2 , if a
X
mol L-1 is the initial concentration of N 2 O5 , the
P.E. A+B P.E.
concentration of NO2 at time t will be
(a) AB (b)
A+B AB (a) a e -kt (b) a (1 - e - kt )
(reaction coordinate)
(d) 2a (1 - e - kt )
R.C.
R.C. (c) 2a ( e - kt -1)
 EBD_7374
258 CHEMISTRY

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 12 (b) 23 (b) 34 (b) 45 (a) 56 (N) 67 (a) 78 (a) 89 (b) 100 (a)
2 (c) 13 (d) 24 (c) 35 (c) 46 (b) 57 (d) 68 (a) 79 (b) 90 (d) 101 (c)
3 (a) 14 (c) 25 (a) 36 (a) 47 (b) 58 (a) 69 (a) 80 (c) 91 (b) 102 (a)
4 (d) 15 (a) 26 (c) 37 (a) 48 (c) 59 (c) 70 (b) 81 (c) 92 (b) 103 (b)
5 (c) 16 (d) 27 (a) 38 (d) 49 (c) 60 (d) 71 (b) 82 (d) 93 (b) 104 (c)
6 (a) 17 (b) 28 (c) 39 (d) 50 (b) 61 (a) 72 (b) 83 (c) 94 (b) 105 (b)
7 (b) 18 (a) 29 (d) 40 (c) 51 (d) 62 (d) 73 (d) 84 (a) 95 (c) 106 (a)
8 (c) 19 (d) 30 (a) 41 (c) 52 (c) 63 (b) 74 (b) 85 (c) 96 (b) 107 (b)
9 (d) 20 (b) 31 (b) 42 (a) 53 (b) 64 (b) 75 (a) 86 (b) 97 (b) 108 (d)
10 (a) 21 (c) 32 (c) 43 (d) 54 (a) 65 (d) 76 (b) 87 (d) 98 (a) 109 (d)
11 (c) 22 (b) 33 (d) 44 (a) 55 (c) 66 (a) 77 (b) 88 (c) 99 (c) 110 (d)
Exercise 2 : Exemplar & Past Year MCQs
1 (c) 7 (c) 13 (a) 19 (b) 25 (d) 31 (b) 37 (d) 43 (a) 49 (b)
2 (c) 8 (d) 14 (b) 20 (b) 26 (a) 32 (a) 38 (d) 44 (d) 50 (a)
3 (b) 9 (c) 15 (c) 21 (b) 27 (b) 33 (a) 39 (d) 45 (b) 51 (a)
4 (a) 10 (b) 16 (d) 22 (d) 28 (a) 34 (d) 40 (c) 46 (a) 52 (b)
5 (b) 11 (a) 17 (b) 23 (a) 29 (b) 35 (d) 41 (a) 47 (b)
6 (a) 12 (c) 18 (b) 24 (d) 30 (c) 36 (a) 42 (c) 48 (c)
Exercise 3 : Try If You Can
1 (b) 3 (d) 5 (c) 7 (b) 9 (c) 11 (b) 13 (d) 15 (d)
2 (b) 4 (d) 6 (b) 8 (d) 10 (a) 12 (c) 14 (c)
 19 Chapter
SURFACE CHEMISTRY

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Properties of colloids, Theory
AIIMS 2 of catalysis, Theory of 3/5 6.4
JEE Main 2 Adsorption.
BITSAT 2
 EBD_7374
260 CHEMISTRY
SURFACE CHEMISTRY 261
 EBD_7374
262 CHEMISTRY

Exercise 1 : Topic-wise MCQs

12. In Freundlich adsorption isotherm, the value of 1/n is :
Topic 1: Adsorption
(a) between 0 and 1 in all cases
1. Which is not correct regarding the physical adsorption of a (b) between 2 and 4 in all cases
gas on surface of solid? (c) 1 in case of physical adsorption
(a) On increasing temperature, adsorption increases (d) 1 in case of chemisorption
continuously 13. Which is adsorbed in maximum amount by activated charcoal?
(b) Enthalpy and entropy changes are negative (a) N2 (b) CO2 (c) Cl2 (d) O2
(c) Adsorption is more for some specific substance 14. Freundlich equation for adsorption of gases (in amount of x g)
(d) Reversible on a solid (in amount of m g) at constant temperature can be
2. How many layers are adsorbed in chemical adsorption? expressed as
(a) One (b) Two (c) Many (d) Zero
x 1 x 1
3. Adsorption due to strong chemical forces is called (a) log = log P + log K(b) log = log K + log P
(a) Chemisorption (b) Physisorption m n m n
(c) Reversible adsorption (d) Both (b) and (c) x x 1
(c) µ Pn (d) = log P + log K
4. In physical adsorption, gas molecules are bound on the m m n
solid surface by 15. Which is not correct regarding the adsorption of a gas on
(a) chemical forces (b) electrostatic forces surface of solid?
(c) gravitational forces (d) van der Waal’s forces (a) On increasing temperature, adsorption increases
5. Which of the following statements is not correct ? continuously
(a) Physical adsorption is due to van der Waal’s forces (b) Enthalpy and entropy changes are –ve
(b) Chemical adsorption first decreases with increase in (c) Adsorption is more for some specific substance
temperature. (d) This Phenomenon is reversible
(c) Physical adsorption is reversible 16. Which of the following is related to adsorption?
(d) Adsorption energy for a chemical adsorption is (i) DH = – ve (ii) DS = – ve
generally greater than that of physical adsorption. (iii) –TDS = – ve (iv) DG = – ve
6. Adsorption of gases on solid surface is exothermic reaction (a) (i), (ii) and (iv) (b) (ii) and (iii)
because (c) (iii) only (d) (i), (iii) and (iv)
(a) free energy increases (b) enthalpy is positive 17. Which of the following phenomenon occurs when the
(c) entropy increases (d) enthalpy is negative precipitate of Mg(OH)2 attains blue colour in presence of
7. The gas which is least adsorbed on charcoal (under identical magneson reagent?
conditions) is (i) Absorption of solvent
(a) HCl (b) O2 (c) CO2 (d) NH3 (ii) Adsorption of coloured substance
8. Adsorption is accompanied by (iii) Absorption and adsorption both of solvent
(a) decrease in enthalpy and increase in entropy (iv) Adsorption of solvent
(b) increase in enthalpy and increase in entropy (a) (i) and (ii) (b) (ii) only
(c) decrease in enthalpy and decrease in entropy (c) (ii) and (iv) (d) (iii) only
(d) increase in enthalpy and decrease in entropy
x
9. Choose the incorrect statement in respect of physisorption? 18. Assertion : The relation = k.p1/n is known as Freundlich
(a) It is not specific in nature m
(b) It arises because of van der Waal’s force adsorption isotherm, where ‘x’ is the mass of gas adsorbed
(c) It is reversible in nature by ‘m’ grams of adsorbate, ‘p’z is the equilibrium pressure,
(d) Enthalpy of adsorption is in the range 80-240 kJ mol–1 k and n are constants for given system and temperature.
10. For adsorption of a gas on a solid, the plot of log x/m vs 1
Reason : When several substances have same value of ,
log P is linear with slope equal to (‘n’ being whole number) n
1 the lines by which their adsorption isotherms can be
(a) k (b) log k (c) n (d)
n represented will meet at a point.
11. If x is amount of adsorbate and m is amount of adsorbent, which (a) If both Assertion and Reason are correct and Reason
of the following relations is not related to adsorption process ? is the correct explanation of Assertion.
(a) x / m = f (p) at constant T. (b) If both Assertion and Reason are correct, but Reason
(b) x / m = f (T) at constant p. is not the correct explanation of Assertion.
(c) p = f (T) at constant (x / m). (c) If Assertion is correct but Reason is incorrect.
x (d) If both the Assertion and Reason are incorrect.
(d) =p×T
m
SURFACE CHEMISTRY 263

19. Which of the following statements is incorrect regarding 26. Catalytic poisons act by :
physisorptions? (a) making the products chemically inactive.
(a) More easily liquefiable gases are adsorbed readily. (b) increasing the rate of the backward reaction.
(b) Under high pressure it results into multimolecular layer (c) chemical combination with any one of the reactants.
on adsorbent surface. (d) preferential adsorption on the catalyst surface.
(c) Enthalpy of adsorption ( DH adsorption) is low and 27. A catalyst :
positive. (a) lowers the activation energy
(d) It occurs because of van der Waal’s forces. (b) changes the rate constant
20. Which is correct about physical adsorption? (c) changes the product
(a) High temperature and high pressure favour adsorption
(d) itself destroyed in the reaction
(b) High temperature and low pressure favour adsorption
28. Active charcoal is a good catalyst because it
(c) Low temperature and high pressure favour adsorption
(a) is made up of carbon atoms.
(d) Low temperature and low pressure favour adsorption
(b) is very reactive.
21. Methylene blue, from its aqueous solution, is adsorbed on
activated charcoal at 25°C. For this process, which of the (c) has more adsorption power.
following statement is correct ? (d) has inert nature toward reagents.
(a) The adsorption requires activation at 25°C 29. Which of the following kind of catalysis can be explained
(b) The adsorption is accompanied by a decrease in by the adsorption theory ?
enthalpy (a) Homogeneous catalysis
(c) The adsorption increases with increase of temperature (b) Acid - base catalysis
(d) The adsorption is irreversible (c) Heterogeneous catalysis
22. In the adsorption of a gas on solid, Freundlich isotherm is (d) Enzyme catalysis
obeyed. The slope of the plot is zero. Then the extent of 30. Catalyst increases the rate of reaction by
adsorption is (a) decreasing threshold energy
(a) directly proportional to the pressure of the gas (b) decreasing activation energy
(b) inversely proportional to the pressure of the gas (c) increasing activation energy
(c) directly proportional to the square root of the pressure (d) decreasing equilibrium constant
of the gas 31. A catalyst can affect reversible reaction by
(d) independent of the pressure of the gas (a) changing equilibrium constant
23. Assertion : The enthalpy of physisorption is greater than (b) slowing forward reaction
chemisorption. (c) attaining equilibria in both directions
Reason : Molecules of adsorbate and adsorbent are held (d) None of these
by van der Waal’s forces in physisorption and by chemical 32. Which one of the following is an example of homogeneous
bonds in chemisorption. catalysis?
(a) If both Assertion and Reason are correct and Reason (a) Haber’s process of synthesis of ammonia
is the correct explanation of Assertion. (b) Catalytic conversion of SO2 to SO3 in contact process
(b) If both Assertion and Reason are correct, but Reason (c) Catalytic hydrogenation of oils
is not the correct explanation of Assertion. (d) Acid hydrolysis of methyl acetate.
(c) If Assertion is correct but Reason is incorrect. 33. Identify the correct statement regarding enzymes
(d) If both the Assertion and Reason are incorrect. (a) Enzymes are specific biological catalysts that cannot
24. Which of the following statements regarding difference be poisoned.
between adsorption and absorption is incorrect? (b) Enzymes are normally heterogeneous catalysts that
(a) Adsorption is a surface whereas absorption is a bulk are very specific in their action.
phenomena. (c) Enzymes are specific biological catalysts that can
(b) Water vapours are absorbed by anhydrous CaCl2 but normally function at very high temperatures
adsorbed by silica gel. (T » 1000K).
(c) Adsorption and absorption take place individually. (d) Enzymes are specific biological catalysts that possess
They can not occur simultaneously. well-defined active sites.
(d) All of the above statements are correct. 34. The action of enzymes in living system is to :
Topic 2: Catalysis (a) supply energy to tissues
(b) enhance immunity
25. The role of a catalyst in a reversible reaction is to
(c) circulate oxygen
(a) increase the rate of forward reaction (d) enhance the rate of biochemical reactions.
(b) decrease the rate of backward reaction 35. Hydrolysis of urea is an example of
(c) alter the equilibrium constant of the reaction (a) homogenous catalysis (b) heterogenous catalysis
(d) allow the equilibrium to be achieved quickly (c) biochemical catalysis (d) zeolite catalysis
 EBD_7374
264 CHEMISTRY

36. The efficiency of an enzyme in catalysing a reaction is due 42. Which of the following statements about a catalyst is true ?
to its capacity (a) A catalyst accelerates the reaction by bringing down
(a) to form a strong enzyme-substrate complex the free energy of activation
(b) to decrease the bond energies of substrate molecule (b) A catalyst also takes part in the reaction mechanism
(c) to change the shape of the substrate molecule (c) A catalyst makes the reaction more feasible by making
(d) to lower the activation energy of the reaction the DGº more negative
37. What is the role of molybdenum in Haber’s process for (d) A catalyst makes the equilibrium constant of the
manufacture of ammonia? reaction more favourable for the forward reaction
43. Which one of the following, statements is incorrect about
(a) As catalytic poison (b) As a catalytic promoter
enzyme catalysis?
(c) As a catalyst (d) As a reactant
(a) Enzymes are mostly protenious in nature.
38. Which of the following step(s) is/are not involved in the (b) Enzyme action is specific.
mechanism of adsorption theory of heterogeneous (c) Enzymes are denaturated by ultraviolet rays and at high
catalyst? temperature.
(i) Diffusion of reactants to the surface of the catalyst. (d) Enzymes are least reactive at optimum temperature.
(ii) Sorption of reactant molecules on the surface of the
catalyst. Topic 3: Colloids and Classification of Colloids
(iii) Occurrence of chemical reaction on the catalyst’s
surface through formation of an intermediate. 44. Milk is a colloid in which a
(iv) Desorption of reaction products from the catalyst’s (a) liquid is dispersed in a liquid
surface. (b) solid is dispersed in a liquid
(v) Diffusion of reaction products away from the catalyst’s (c) gas is dispersed in a liquid
surface. (d) sugar is dispersed in a liquid
(a) (i) only (b) (ii) and (iv) 45. The size of colloidal particles is between
(c) (ii) only (d) (i), (ii) and (v) (a) 10–7 – 10–9 cm (b) 10–9 – 10–11 cm
–5
(c) 10 – 10 cm –7 (d) 10–2 – 10–3 cm
39. Which of the following statement(s) is/are correct about
solid catalyst? 46. An example of dispersion of a liquid in a gas is :
(i) Same reactants may give different product by using (a) milk (b) vegetable oil
different catalysts. (c) foam (d) mist
47. Alloy is an example of
(ii) Catalyst is required in large quantities to catalyse
(a) gel (b) solidified emulsion
reactions.
(c) solid solution (d) sol
(iii) Catalyst does not change DH of reaction.
48. If dispersed phase is a liquid and the dispersion medium is a
(iv) Catalytic activity of a solid catalyst does not depend
solid, the colloid is known as
upon the strength of chemisorption. (a) a sol (b) a gel
(a) (i) and (iii) (b) (i) only (c) an emulsion (d) a foam
(c) (ii), (iii) and (iv) (d) (iii) and (iv) 49. Hair cream is an example of
40. Which of the following statement(s) is/are correct? (a) gel (b) sol (c) aerosol (d) foam
(i) Zeolites are good shape selective catalysts because 50. Which one of the following is correctly matched?
of their honeycomb-like structures. (a) Emulsion-smoke (b) Gel-butter
(ii) All zeolites are naturally occurring substance. (c) Aerosol-hair cream (d) Sol-whipped cream
(iii) An important zeolite catalyst used in the petroleum 51. Which one of the following in not a colloidal solution?
industry in ZSM-5. (a) Smoke (b) Ink (c) Blood (d) Air
(a) (i) only (b) (ii) only 52. Small liquid droplets dispersed in another liquid is called
(c) (i) and (iii) (d) (ii) and (iii) (a) gel (b) suspension
41. Match the columns (c) emulsion (d) true solution
Column-I Column-II 53. When dispersed phase is liquid and dispersion medium is
(Biochemical reactions) (Enzymes) gas then the colloidal system is called
(A) C6H12O6(aq) ¾¾® (p) Zymase (a) Smoke (b) Clouds (c) Jellies (d) Emulsions
2C2H5OH(aq) + 2CO2(g) 54. How non-polar and polar part in micelle are arranged ?
(B) NH2CONH2(aq) + H2O(l) ¾¾® (q) Pepsin (a) Polar at outer surface and non-polar at inner surface
2NH3(g) + CO2(g) (b) Polar at inner surface and non-polar at outer surface
(C) Proteins ¾¾® Peptides (r) Urease (c) Both polar and non-polar at inner surface
(D) C12H22O11(aq) + H2O(l) ¾¾® (s) Invertase (d) Distributed all over the surface
C6H12O6(aq) + C6H12O6(aq) 55. Surface tension of lyophilic sols is
(a) A – (p), B – (r), C – (q), D – (s) (a) lower than that of H2O
(b) A – (p), B – (q), C – (r), D – (s) (b) more than that of H2O
(c) A – (r), B – (p), C – (q), D – (s) (c) equal to that of H2O
(d) A – (p), B – (r), C – (s), D – (q) (d) either less or more than H2O depending upon the nature
of disperse phase
SURFACE CHEMISTRY 265

56. Which of the following is a lyophilic colloid ? (a) Ba+2 > Na+ > Al+3 (b) Al+3 > Na+ > Ba+2
(a) Milk (b) Gum (c) Fog (d) Blood +3
(c) Al > Ba > Na+2 + (d) Ba+2 > Al+3 > Na+
57. Lyophobic colloids are : 72. Tyndall effect is shown by
(a) gun proteins (b) protective colloids (a) sol (b) solution
(c) irreversible colloids (d) reversible colloids (c) plasma (d) precipitate
58. Which one is an example of multimolecular colloid system 73. The cause of Brownian movement is
(a) Soap dispersed in water (a) heat changes in liquid state
(b) Protein dispersed in water (b) convectional currents
(c) Gold dispersed in water (c) the impact of molecules of the dispersion medium on
(d) Gum dispersed in water the colloidal particles.
59. Example of intrinsic colloid is (d) attractive forces between the colloidal particles and
(a) glue (b) sulphur (c) Fe (d) As 2 S 3 molecules of dispersion medium.
60. Associated colloid among the following is 74. Which of the following acts as protective colloid?
(a) enzymes (b) proteins (a) Silica gel (b) Gelatin
(c) cellulose (d) sodium stearate (c) Sodium acetate (d) None of these
61. The formation of micelles takes place only above 75. Which of the following is not a property of colloidal
(a) inversion temperature (b) Boyle temperature solution?
(c) critical temperature (d) Kraft temperature (a) Heterogenity (b) Particle size > 100 nm
(c) Tyndall effect (d) Brownian movement
62. Which of the following is used for neutralising charge on
76. The charge on colloidal particles is due to
colloidal solution?
(a) presence of electrolyte
(a) Electrons (b) Electrolytes
(b) very small size of particles
(c) Positively charged ions (d) Compounds
(c) adsorption of ions from the solution
63. Pure water can be obtained from sea water by (d) None of these
(a) Centrifugation (b) Plasmolysis 77. In which of the following Tyndall effect is not observed ?
(c) Reverse osmosis (d) Sedimentation (a) Suspensions (b) Emulsions
64. Blood may be purified by (c) Sugar solution (d) Gold sol
(a) Dialysis (b) Electro-osmosis 78. Which of the following method is used for coagulation of
(c) Coagulation (d) Filtration the sol?
65. During dialysis (a) By mixing two oppositely charged sols.
(a) only solvent molecules can diffuse (b) By electrophoresis.
(b) solvent molecules, ions and colloidal particles can diffuse (c) By addition of electrolytes.
(c) all kinds of particles can diffuse through the semi- (d) All of the above.
permeable membrane 79. Which of the following is not the condition for Tyndall
(d) solvent molecules and ions can diffuse effect?
66. The electrolytic impurities of a sol can most easily be (a) The refractive indices of dispersed phase and
separated by dispersion medium should differ greatly in magnitude.
(a) dialysis (b) electrosmosis (b) The diameter of the dispersed particles is not much
(c) electrophoresis (d) electrodialysis smaller than the wavelength of light used.
67. The separation of colloidal particles from particles of (c) Tyndall effect is observed only when viewed from the
molecular dimensions is known as direction of the passage of light.
(a) sedimentation (b) dispersion (d) All of these are required conditions for Tyndall effect.
(c) pyrolysis (d) dialysis 80. Match the columns
68. The movement of colloidal particles towards their respective Column-I Column-II
electrodes in the presence of an electric field is known as : (A) As2S3 sol (p) Bredig’s Arc method
(a) electrolysis (b) brownian movement (B) Fe(OH)3 sol (q) Double decomposition
(c) electrodialysis (d) electrophoresis (C) Colloidal sols of metals (r) Peptization
69. Colloidal gold is prepared by like Au, Ag, Pt, etc.
(a) Mechanical dispersion (b) Peptisation (D) Conversion of freshly (s) Hydrolysis
(c) Bredig’s Arc method (d) Hydrolysis prepared precipitate
70. Peptization involves into a colloidal sol
(a) precipitation of colloidal particles (a) A – (q), B – (s), C – (r), D – (p)
(b) disintegration of colloidal aggregates (b) A – (q), B – (p), C – (s), D – (r)
(c) evaporation of dispersion medium (c) A – (s), B – (q), C – (p), D – (r)
(d) impact of molecules of the dispersion medium on the (d) A – (q), B – (s), C – (p), D – (r)
colloidal particles 81. The dispersed phase and dispersion medium in soap lather
71. Hardy-Schulze rule explains the effect of electrolytes on the are respectively
coagulation of colloidal solution. According to this rule, (a) gas and liquid (b) liquid and gas
coagulation power of cations follow the order (c) solid and gas (d) solid and liquid
 EBD_7374
266 CHEMISTRY

82. Which of the following is not a colloid ? (b) Hardy Schulze rule is related with coagulation
(a) Chlorophyll (b) Smoke (c) Brownian movement and Tyndall effect are shown by
(c) Ruby glass (d) Milk colloidal system
83. Which of the following forms a colloidal solution in water ? (d) Gold number is a measure of the protective power of
(a) NaCl (b) Glucose lyophilic colloid
(c) Starch (d) Barium nitrate 94. Match the columns
84. Which of the following forms cationic micelles above certain Column-I Column-II
concentration? (A) Butter (p) dispersion of liquid in liquid
(a) Sodium dodecyl sulphate (B) Pumice stone (q) dispersion of solid in liquid
(b) Sodium acetate (C) Milk (r) dispersion of gas in solid
(c) Urea (D) Paints (s) dispersion of liquid in solid
(d) Cetyl trimethyl ammonium bromide (a) A – (r), B – (s), C – (p), D – (q)
85. Which of the following does not contain a hydrophobic (b) A – (s), B – (r), C – (p), D – (q)
structure? (c) A – (q), B – (r), C – (p), D – (s)
(a) Linseed oil (b) Lanolin (d) A – (s), B – (r), C – (q), D – (p)
(c) Glycogen (d) Rubber 95. The disperse phase in colloidal iron (III) hydroxide and
86. Match the columns colloidal gold is positively and negatively charged,
Column-I Column-II respectively. Which of the following statements is NOT correct?
(A) Protective colloid (p) FeCl3 + NaOH (a) Coagulation in both sols can be brought about by
(B) Liquid - liquid colloid (q) Lyophilic colloids electrophoresis
(C) Positively charged colloid (r) Emulsion (b) Mixing the sols has no effect
(D) Negatively charged colloid (s) FeCl3 + hot water (c) Sodium sulphate solution causes coagulation in both
(a) A – (q), B – (r), C – (p), D – (s) sols
(b) A – (p), B – (r), C – (s), D – (q) (d) Magnesium chloride solution coagulates, the gold sol
(c) A – (q), B – (r), C – (s), D – (p) more readily than the iron (III) hydroxide sol.
(d) A – (r), B – (q), C – (s), D – (p) 96. Assertion: An ordinary filter paper impregnated with
87. Which one of the following is an examplefor multimolecular collodion solution stops the flow of colloidal particles.
colloid? Reason: Pore size of the filter paper becomes more than the
(a) Aqueous starch sol size of colloidal particle.
(b) Aqueous enzyme sol (a) If both Assertion and Reason are correct and Reason
(c) Alcoholic polystyrene sol is the correct explanation of Assertion.
(d) Aqueous sol of sodium laurylsulphate (b) If both Assertion and Reason are correct, but Reason
88. Bredig arc method cannot be used to prepare colloidal solution is not the correct explanation of Assertion.
of which of the following (c) If Assertion is correct but Reason is incorrect.
(a) Pt (b) Fe (c) Ag (d) Au (d) If both the Assertion and Reason are incorrect.
89. Colloidal solutions are not purified by 97. In Brownian movement or motion, the paths of the particles
(a) Dialysis (b) Electrodialysis are
(c) Ultrafiltration (d) Electrophoresis (a) Linear (b) Zig-zag (c) Uncertain (d) Curved
90. Which of the following ions can cause coagulation of 98. Which of the following statements is incorrect?
proteins ?
(a) Colloidal gold is used for intramuscular injection.
(a) Ag+ (b) Na+ (c) Mg2+ (d) Ca2+
(b) Colloidal solution of latex is used in preparation of
91. Assertion: Detergents with low CMC are more economical
rubber.
to use.
(c) Photographic films are prepared by coating an
Reason: Cleansing action of detergents involves the
emulsion of AgBr in gelatin over glass plate.
formation of micelles. These are formed when the
concentration of detergents becomes equal to CMC. (d) Tannin used in leather industry contains positively
(a) If both Assertion and Reason are correct and Reason charged colloidal particles.
is the correct explanation of Assertion. 99. How many of the following are negatively charged sols?
(b) If both Assertion and Reason are correct, but Reason Eosin dye, sol of charcoal, haemoglobin, Al2 O3.xH2O,
is not the correct explanation of Assertion. As2S3, TiO2.sol, copper sol
(c) If Assertion is correct but Reason is incorrect. (a) 3 (b) 4 (c) 6 (d) All of these
(d) If both the Assertion and Reason are incorrect. 100. Match the columns
92. Which of the following will be most effective in the Column-I Column-II
coagulation of Al(OH)3 sol ? (A) Argyrol (p) Kalazar
(a) KCN (b) BaCl2 (B) Antimony (q) Intramuscular injection
(c) NaCl (d) Mg3(PO4)2 (C) Colloidal gold (r) Stomach disorders
93. Point out the false statement : (D) Milk of magnesia (s) Eye lotion
(a) The colloidal solution of a liquid in liquid is called gel
SURFACE CHEMISTRY 267

(a) A – (r), B – (p), C – (s), D – (q) 104. Emulsions can be broken into constituent liquid by ______.
(b) A – (r), B – (p), C – (q), D – (s) (a) heating (b) freezing
(c) A – (s), B – (q), C – (p), D – (s) (c) centrifuging (d) All of these
(d) A – (s), B – (p), C – (q), D – (r) 105. Match the columns
101. Assertion : The value of colligative properties are of small Column-I Column-II
order for colloids as compared to true solution. (A) Oil in water emulsion (p) Clouds
Reason : Number of particles in colloidal solution is (B) Aerosols containing (q) Vanishing cream
comparatively smaller than true solutions. small droplets of water
(a) If both Assertion and Reason are correct and Reason suspended in air
is the correct explanation of Assertion. (C) When river water meets (r) Smoke
(b) If both Assertion and Reason are correct, but Reason the sea water
is not the correct explanation of Assertion. (D) Colloidal solution of (s) Formation of delta
(c) If Assertion is correct but Reason is incorrect. carbon, arsenic
(d) If both the Assertion and Reason are incorrect. compounds, dust etc.
in air
Topic 4: Emulsion and Colloids Around Us (a) A – (q), B – (p), C – (s), D – (r)
102. Which of the following is not true about the emulsion? (b) A – (p), B – (q), C – (s), D – (r)
(a) Emulsion can be broken into constituent liquids by (c) A – (q), B – (s), C – (p), D – (r)
heat, freezing (d) A – (q), B – (p), C – (r), D – (s)
(b) Emulsion of oil in water is generally unstable 106. How does a delta form at the meeting place of sea and river
(c) Emulsion do not show the Tyndall effect water?
(d) They show brownian motion (a) The electrolyte present in sea water coagulate the clay
103. Which of the following is not emulsifying agent for W/O (b) the electrolyte present in sea water has no role
emulsion? (c) the electrolyte present in river water coagulate the clay
(a) Lampblack (d) Both (a) and (c) are correct
(b) Long chain alcohol 107. .......... is a silver sol used as an eye lotion. Fill in the blank
(c) Proteins with an appropriate answer.
(d) Heavy metal salts of fatty acids (a) Amytol (b) Argyrol
(c) Ciprofloxacin (d) Both (a) and (b)

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (c) decrease in surface area of adsorbent
(d) decrease in strength of van der Waal's forces
1. Which of the following process does not occur at the 6. Extent of adsorption of adsorbate from solution phase
interface of phases? increases with ............... .
(a) Crystallisation (a) increase in amount of adsorbate in solution
(b) Heterogeneous catalysis (b) decrease in surface area of adsorbate
(c) Homogeneous catalysis (c) increase in temperature of solution
(d) Corrosion (d) decrease in amount of adsorbate in solution
2. At the equilibrium position in the process of 7. Which one of the following is not applicable to the
adsorption ................. . phenomenon of adsorption?
(a) DH > 0 (b) DH = TDS (a) DH > 0 (b) DG < 0 (c) DS < 0 (d) DH < 0
(c) DH > TDS (d) DH < TDS 8. Which of the following is not a favourable condition for
3. Which of the following interface cannot be obtained? physical adsorption?
(a) Liquid-liquid (b) Solid-liquid (a) High pressure
(c) Liquid-gas (d) Gas-gas (b) Negative DH
4. The term 'sorption' stands for ................ . (c) Higher critical temperature of adsorbate
(a) absorption (d) High temperature
(b) adsorption 9. Physical adsorption of a gaseous species may change to
(c) Both absorption and adsorption chemical adsorption with ............. .
(d) desorption (a) decrease in temperature
5. Extent of physisorption of a gas increases with ............. . (b) increase in temperature
(a) increase in temperature (c) increase in surface area of adsorbent
(b) decrease in temperature (d) decrease in surface area of adsorbent
 EBD_7374
268 CHEMISTRY

10. In physisorption adsorbent does not show specificity for 19. A colloidal system having a solid substance as a dispersed
any particular gas because ............. . phase and a liquid as a dispersion medium is classified
(a) involved van der Waal's forces are universal as .............. .
(b) gases involved behave like ideal gases (a) solid sol (b) gel (c) emulsion (d) sol
(c) enthalpy of adsorption is low 20. The values of colligative properties of colloidal solution are
(d) it is a reversible process of small order in comparison to those shown by true
11. Which of the following is an example of absorption? solutions of same concentration because of colloidal
particles ............
(a) Water on silica gel
(a) exhibit enormous surface area
(b) Water on calcium chloride (b) remain suspended in the dispersion medium
(c) Hydrogen on finely divided nickel (c) form lyophilic colloids
(d) Oxygen on metal surface (d) are comparatively less in number
12. On the basis of data given below predict which of the 21. Arrange the following diagrams in correct sequence of steps
following gases shows least adsorption on a definite amount involved in the mechanism of catalysis, in accordance with
of charcoal? modern adsorption theory.
A
Gas CO 2 SO 2 CH 4 H2 | | |
— O —O —O —
Critical temp./K 304 630 190 33 | | |
(I) —O—O—O—
(a) CO2 (b) SO2 (c) CH4 (d) H2 | | |
13. In which of the following reactions heterogeneous catalysis B
is involved? | | |
A — O —O —O —
NO( g )
(i) 2SO2 ( g ) + O 2 ( g ) ¾¾¾¾ ® 2SO3 ( g ) (II) B — O — O — O —
| | |

Pt ( s ) | | |
(ii) 2SO2 ( g ) ¾¾¾® 2SO3 ( g )
| | |
Fe(s ) A — O —O —O —
(iii) N 2 ( g ) + 3 H 2 ( g ) ¾¾¾® 2NH3 ( g ) | | |
(III) B — O—O—O—
HCl( l )
® CH3COOH ( aq )
(iv) CH3COOCH3 ( l) + H 2O ( l ) ¾¾¾¾ | | |

+ CH 3OH ( aq ) A
| | | |
(a) (ii), (iii) (b) (ii), (iii) and (iv) — O — O —O —
B
(c) (i), (ii) and (iii) (d) (iv) (IV) | | |
14. At high concentration of soap in water, soap behaves as — O—O—O—
...... | | |
(a) molecular colloid (b) associated colloid | | |
(c) macromolecular colloid (d) lyophilic colloid A — O —O —O —
15. Which of the following will show Tyndall effect? | + | | |
(V) B — O — O — O —
(a) Aqueous solution of soap below critical micelle | | |
concentration (a) I ® II ® III ® IV ® V (b) I ® III ® II ® IV ® V
(b) Aqueous solution of soap above critical micelle (c) I ® III ® II ® V ® IV (d) I ® II ® III ® V ® IV
concentration 22. Which of the following process is responsible for the
(c) Aqueous solution of sodium chloride formation of delta at a place where rivers meet the sea?
(d) Aqueos solution of sugar (a) Emulsification (b) Colloid formation
16. Method by which lyophobic sol can be protected (c) Coagulation (d) Peptisation
(a) by addition of oppositely charged sol 23. Which of the following curves is in according with
(b) by addition of an electrolyte Freundlich adsorption isotherm?
(c) by addition of lyophilic sol
(d) by boiling
®

17. Freshly prepared precipitate sometimes gets converted to

log x/m

log x/m

collodial solution by ................... . (a) (b)

(a) coagulation (b) electrolysis log p ® log p ®
(c) diffusion (d) peptisation
18. Which of the following electrolytes will have maximum
®

coagulating value for Ag/Ag+ sol?

log x/m

log x/m

(a) Na2S (b) Na3PO4 (c) Na2SO4 (d) NaCl (c) (d)
log p ® log p ®
SURFACE CHEMISTRY 269

24. Which of the following process is not responsible for the 29. The isoelectric-point of a colloidially dispersed material is
presence of electric charge on the sol particles? the pH value at which [BITSAT 2014, C]
(a) Electron capture by sol particles (a) the dispersed phase migrate in an electric field
(b) Adsorption of ionic species from solution (b) the dispersed phase does not migrate in an electric
(c) Formation of Helmholtz electrical double layer field
(d) Absorption of ionic species from solution (c) the dispersed phase has pH equal to 7
25. Which of the following phenomenon is applicable to the (d) the dispersed phase has pH equal to zero
process shown in the figure? 30. Gold numbers of protective colloids A, B, C and D are 0.50,
0.01, 0.10 and 0.005, respectively. The correct order of their
protective powers is [AIIMS 2015, A]
(a) D < A < C < B (b) C < B < D < A
(c) A < C < B < D (d) B < D < A < C
31. Which of the following ionic substances will be most
effective in precipitating the sulphur sol?
Solution of raw sugar [BITSAT 2015, A]
yellowish brown (a) KCl (b) BaCl2
(c) Fe2(SO4)3 (d) Na3PO4
32. Which one of the following characteristics is associated
with adsorption? [NEET 2016, C]
(a) DG is negative but DH and DS are positive
Column of
animal (b) DG, DH and DS all are negative
charcoal (c) DG and DH are negative but DS is positive
(d) DG and DS are negative but DH is positive
33. Fog is colloidal solution of [NEET 2016, C]
(a) Liquid in gas (b) Gas in liquid
Colourless
solution of (c) Solid in gas (d) Gas in gas
sugar 34. The disease kala azar is caused by [AIIMS 2016, C]
(a) colloidal antimony
(b) milk of magnesia
(c) argyrols
(a) Absorption (b) Adsorption (d) colloidal gold
(c) Coagulation (d) Emulsification 35. For a linear plot of log (x/m) versus log p in a Freundlich
adsorption isotherm, which of the following statements is
Past Year MCQs
correct? (k and n are constants) [JEE M 2016, S]
26. Which of the following statements is correct for the (a) Only 1/n appears as the slope.
spontaneous adsorption of a gas? [AIPMT 2014, C] (b) log (1/n) appears as the intercept.
(a) DS is negative and, therefore, DH should be highly (c) Both k and 1/n appear in the slope term.
positive (d) 1/n appears as the intercept.
(b) DS is negative and therefore, DH should be highly 36. Which one of the following statements is not correct?
negative [NEET 2017, C]
(c) DS is positive and, therefore, DH should be negative (a) The value of equilibrium constant is changed in the
(d) DS is positive and, therefore, DH should also be highly presence of a catalyst in the reaction at equilibrium
positive (b) Enzymes catalyse mainly bio-chemical reactions
(c) Coenzymes increase the catalytic activity of enzyme
27. Which property of colloids is not dependent on the charge
(d) Catalyst does not initiate any reaction
on colloidal particles? [AIPMT 2014, 2015, C]
37. Which one of the following impurities present in colloidal
(a) Coagulation (b) Electrophoresis solution cannot be removed by electrodialysis?
(c) Electro - osmosis (d) Tyndall effect [AIIMS 2017, C]
28. Under the influence of an electric field, the particles in a sol (a) Sodium chloride
migrate towards cathode. The coagulation of the same sol is (b) Potassium sulphate
studied using NaCl, Na2SO4 and Na3PO4 solutions. Their (c) Urea
coagulating values will be in the order [AIIMS 2014, A] (d) Calcium chloride
(a) NaCl > Na2SO4 > Na3PO4 38. Assertion : The enthalpy of physisorption is greater than
chemisorption. [AIIMS 2016, 17, C]
(b) Na2SO4 > Na3PO4 > NaCl
Reason : Molecules of adsorbate and adsorbent are held by
(c) Na3PO4 > Na2SO4 > NaCl van der Waal’s forces in physisorption and by chemical
(d) Na2SO4 > NaCl > Na3PO4 bonds in chemisorption.
 EBD_7374
270 CHEMISTRY

(a) If both Assertion and Reason are correct and Reason 42. Assertion : On passing electric current in colloidal solution
is the correct explanation of Assertion. they do not move towards anode or cathode.
(b) If both Assertion and Reason are correct, but Reason Reason : They do not contain any charge.[AIIMS 2018, C]
is not the correct explanation of Assertion. (a) If both assertion and reason are true and reason is the
(c) If Assertion is correct but Reason is incorrect. correct explanation of assertion.
(d) If both the Assertion and Reason are incorrect. (b) If both assertion and reason are true but reason is not
39. The Tyndall effect is observed only when following the correct explanation of assertion.
conditions are satisfied : [JEE M 2017, S]
(c) If assertion is true but reason is false.
(1) The diameter of the dispersed particles is much smaller
than the wavelength of the light used. (d) If both assertion and reason are false.
(2) The diameter of the dispersed particle is not much 43. Freundlich equation for adsorption of gases (in amount of x g)
smaller than the wavelength of the light used. on a solid (in amount of m g) at constant temperature can be
(3) The refractive indices of the dispersed phase and expressed as [BITSAT 2018, A]
dispersion medium are almost similar in magnitude. x 1 x 1
(4) The refractive indices of the dispersed phase and (a) log = log p + log K (b) log = log K + log p
m n m n
dispersion medium differ greatly in magnitude.
(a) (1) and (4) (b) (2) and (4) x x 1
(c) µ pn (d) = log p + log K
(c) (1) and (3) (d) (2) and (3) m m n
40. On which of the following properties does the coagulating 44. Which of the following feature of catalysts is described in
power of an ion depend? [NEET 2018, C] reactions given below? [BITSAT 2018, A]
(a) The magnitude of the charge on the ion alone
Cu / ZnO-Cr O
(b) Size of the ion alone (i) CO ( g ) + 2H2 ( g ) ¾¾¾¾¾¾¾ 3 ( )
2 3 ® CH OH g

(c) The sign of charge on the ion alone

CO ( g ) + H 2 ( g ) ¾¾® HCHO ( g )
Cu
(d) Both magnitude and sign of the charge on the ion (ii)
41. Removal of charge from colloids causes [AIIMS 2018, C]
(iii) CO ( g ) + 3H2 ( g ) ¾¾
Ni
® CH4 ( g ) + H2O ( g )
(a) Peptization (b) Coagulation
(a) Activity (b) Selectivity
(c) Dialysis (d) Breding arc method
(c) Catalytic promoter (d) Catalytic poison

Exercise 3 : Try If You Can

1. Which of the following adsorption isotherms represents (a) DH < 0, DS > 0, DG > 0 (b) DH < 0, DS < 0, DG < 0
the absorption of a gas by a solid involving multilayers of (c) DH > 0, DS > 0, DG < 0 (d) DH > 0, DS < 0, DG > 0
formation? (Ps = saturation pressure)
4. For the graph below, select correct order of temperature?
Ps T1
Ps Ps
Extent of T2
x x
(a) (b) adsorption
m m (x/m) T3
P P
Pressure (P)
Ps Ps (a) T1 > T2 > T3 (b) T2 > T3 > T1
(c) T3 > T2 > T1 (d) T1 = T2 = T3
x x
(c) (d) 5. 100 mL of 0.6 M acetic acid is shaken with 2 g activated
m m carbon. The final concentration of the solution after
P P adsorption is 0.5 M. What is the amount of acetic acid
2. 3.6 gram of oxygen is adsorbed on 1.2 g of metal powder. adsorbed per gram of carbon?
What volume of oxygen adsorbed per gram of the adsorbent (a) 0.6 g (b) 0.3 g (c) 1.2 g (d) None of these
at 1 atm and 273 K? 6. In an experiment, 200 mL of 0.5 M oxalic acid is shaken with
(a) 0.19Lg–1 (b) 1 Lg–1 10 g of activated charcoal and filtered. The concentration of
the filtrate is reduced to 0.4 M. The amount of adsorption
(c) 2.1 L g–1 (d) None of these
æ xö
3. Which of the following is true in respect of chemical çè ÷ø is
m
adsorption? (a) 0.9 (b) 1.8 (c) 0.18 (d) 0.09
SURFACE CHEMISTRY 271

7. On adding AgNO3 solution into KI solution, a negatively 12. Coagulation value of the electrolytes AlCl3 and NaCl for
charged colloidal sol is obtained when they are in : As2S3 sol are 0.093 and 52 respectively. How many times
(a) 50 mL of 0.1 M AgNO3 + 50 mL of 0.1 M KI AlCl3 has greater coagulating power than NaCl ?
(b) 50 mL of 0.1 M AgNO3 + 50 mL of 0.2 M KI (a) 930 (b) 520
(c) 50 mL of 0.2 M AgNO3 + 50 mL of 0.1 M KI (c) 560 (d) None of these
(d) none of these 13. The density of gold is 19 g/cm3. If 1.9 ´ 10 -4 g of gold is
8. A sol is prepared by addition of excess of AgNO3 solution dispersed in one litre of water to give a sol having spherical
in KI solution. The charge likely to develop on colloidal gold particles of radius 10 nm, then the number of gold
particle is: particles per mm3 of the sol will be :
(a) Positive (b) Negative
(a) 1.9 ´1012 (b) 6.3 ´ 1014
(c) No change (d) Both charges
9. The gold numbers of protective colloids A, B, C and D are (c) 6.3 ´1010 (d) 2.4 ´ 10 6
0.04, 0.004, 10 and 40 respectively. The protective powers 14. A lot of scum formation was observed during washing with
of A, B, C and D are in the order : hard water. The washing powder could be
(a) A > B > C > D (b ) B > A > C > D (a) C17 H 33COONa
(c) D > C > A > B (d) D > C > B > A
O
10. The disperse phase in colloidal iron (III) hydroxide and ||
colloidal gold is positively and negatively charged, (b) CH 3 (CH 2 )11 O S - O - Na +
||
respectively. Which of the following statements is NOT
O
correct?
(a) Coagulation in both sols can be brought about by O
electrophoresis ||
(c) CH 3 (CH 2 )11 - - S - O - Na +
(b) Mixing the sols has no effect ||
(c) Sodium sulphate solution causes coagulation in both O
sols (d) none of these
(d) Magnesium chloride solution coagulates, the gold sol 15. Flocculation value of BaCl2 is much less than that of KCl for
more readily than the iron (III) hydroxide sol sol A and flocculation value of Na2SO4 is much less than
11. A colloidal solution is subjected to an electric field. The that of NaBr for sol B. The correct statement among the
particles move towards anode. The coagulation of same sol following is :
is studied using NaCl, BaCl2 and AlCl3 solutions. The order (a) Both the sols A and B are negatively charged.
of their coagulation power should be – (b) Sol A is positively charged arid Sol B is negatively
(a) NaCl > BaCl2 > AlCl3 (b) BaCl2 > AlCl3 > NaCl charged.
(c) AlCl3 > BaCl2 > NaCl (d) BaCl2 > NaCl > AlCl3 (c) Both the sols A and B are positively charged.
(d) Sol A is negatively charged and sol B is positively
charged.
 EBD_7374
272 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (a) 12 (a) 23 (d) 34 (d) 45 (c) 56 (b) 67 (d) 78 (d) 89 (d) 100 (d)
2 (a) 13 (b) 24 (c) 35 (c) 46 (d) 57 (c) 68 (d) 79 (c) 90 (a) 101 (a)
3 (a) 14 (b) 25 (d) 36 (d) 47 (c) 58 (c) 69 (c) 80 (d) 91 (a) 102 (c)
4 (d) 15 (a) 26 (d) 37 (b) 48 (b) 59 (a) 70 (b) 81 (a) 92 (d) 103 (c)
5 (b) 16 (a) 27 (a) 38 (c) 49 (d) 60 (d) 71 (c) 82 (a) 93 (a) 104 (d)
6 (d) 17 (c) 28 (c) 39 (a) 50 (b) 61 (d) 72 (a) 83 (c) 94 (b) 105 (a)
7 (b) 18 (c) 29 (c) 40 (c) 51 (d) 62 (b) 73 (c) 84 (d) 95 (b) 106 (a)
8 (c) 19 (c) 30 (b) 41 (a) 52 (c) 63 (c) 74 (b) 85 (d) 96 (c) 107 (a)
9 (d) 20 (c) 31 (c) 42 (a) 53 (b) 64 (a) 75 (b) 86 (c) 97 (b)
10 (d) 21 (b) 32 (d) 43 (d) 54 (a) 65 (d) 76 (c) 87 (a) 98 (d)
11 (d) 22 (d) 33 (d) 44 (a) 55 (a) 66 (d) 77 (c) 88 (b) 99 (b)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (c) 6 (a) 11 (b) 16 (c) 21 (b) 26 (b) 31 (c) 36 (a) 41 (b)
2 (b) 7 (a) 12 (d) 17 (d) 22 (c) 27 (d) 32 (b) 37 (c) 42 (d)
3 (d) 8 (d) 13 (a) 18 (b) 23 (c) 28 (a) 33 (a) 38 (d) 43 (b)
4 (c) 9 (b) 14 (b) 19 (d) 24 (d) 29 (b) 34 (a) 39 (b) 44 (b)
5 (b) 10 (a) 15 (b) 20 (b) 25 (b) 30 (c) 35 (a) 40 (d)
Exercis e 3 : Try If You Can
1 (a) 3 (b) 5 (b) 7 (b) 9 (b) 11 (c) 13 (d) 15 (b)
2 (c) 4 (a) 6 (c) 8 (a) 10 (b) 12 (c) 14 (a)
 20 Chapter
GENERAL PRINCIPLES AND
PROCESSES OF ISOLATION
OF ELEMENTS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Thermodynamic principles of
AIIMS 3 metallurgy, refining of metals 3/5 6.9
JEE Main 2
BITSAT 2
 EBD_7374
274 CHEMISTRY
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 275
 EBD_7374
276 CHEMISTRY

Exercise 1 : Topic-wise MCQs

18. Leaching is a process of
Topic 1: Occurrence of Metals and Concentration of Ores
(a) reduction (b) concentration
1. Which one of the following is an ore of silver ? (c) refining (d) oxidation
(a) Argentite(b) Stibnite (c) Haematite(d) Bauxite 19. Which of the following metal is leached by cyanide process ?
2. Cinnabar is an ore of (a) Ag (b) Na (c) Al (d) Cu
(a) Hg (b) Cu (c) Pb (d) Zn 20. Which one of the following ores is not concentrated by
3. An example of an oxide ore is froth floatation process?
(a) Bauxite (b) Malachite (a) Copper pyrites (b) Pyrargyrite
(c) Zinc blende (d) Feldspar (c) Pyrolusite (d) Zinc blende
4. The natural materials from which an element can be extracted 21. In froth flotation process many chemicals (frother , collector,
economically are called activator, and depressant) are used. Which of the following
(a) ores (b) minerals is a frother ?
(c) gangue (d) None of these (a) CuSO4 (b) NaCN+ alkali
5. The most abundant metal on the surface of the earth is (c) Pine oil (d) Potassium xanthate
(a) Fe (b) Al (c) Ca (d) Na 22. Froth flotation process is based on
6. Which of the following is an ore of tin ? (a) wetting properties of ore particle
(a) Carborundum (b) Epsomite (b) specific gravity of ore particles
(c) Cassiterite (d) Spodumene (c) magnetic properties of ore particles
7. Which of the following is chalcopyrite? (d) electrical properties of ore particles
(a) CuFeS2 (b) FeS2 23. Hydro-metallurgical process of extraction of metals is based on
(c) KMgCl3.6H2O (d) Al2O3.2H2O (a) complex formation (b) hydrolysis
8. Haematite is the ore of (c) dehydration (d) dehydrogenation
(a) Pb (b) Cu (c) Fe (d) Au 24. Assertion : Levigation is used for the separation of oxide
9. Composition of azurite mineral is ores from impurities.
(a) CuCO3CuO (b) Cu(HCO3)2. Cu(OH)2 Reason : Ore particles are removed by washing in a current
(c) 2CuCO3.Cu(OH)2 (d) CuCO3. 2Cu(OH)2 of water.
10. Which one of the following is a mineral of iron ? (a) Assertion is correct, reason is correct; reason is a
(a) Malachite (b) Cassiterite correct explanation for assertion.
(c) Pyrolusite (d) Magnetite (b) Assertion is correct, reason is correct; reason is not a
11. Which one of the following is not a sulphide ore?
correct explanation for assertion
(a) Magnetite (b) Iron pyrites
(c) Assertion is correct, reason is incorrect
(c) Copper glance (d) Sphalerite
(d) Assertion is incorrect, reason is correct.
12. The most abundant element in the earth’s crust (by weight) is
25. Assertion : Leaching is a process of reduction.
(a) Si (b) Al (c) O (d) Fe
Reason : Leaching involves treatment of the ore with a
13. Which of the following pair is incorrectly matched ?
suitable reagent so as to make it soluble while impurities
(a) Magnetite – Fe3O4 (b) Copper glance – Cu2S
remains insoluble.
(c) Calamine – ZnCO3 (d) Zincite – ZnS
(a) Assertion is correct, reason is correct; reason is a
14. Which one of the following ores is best concentrated by
correct explanation for assertion.
froth-flotation method ?
(b) Assertion is correct, reason is correct; reason is not a
(a) Galena (b) Cassiterite
correct explanation for assertion
(c) Magnetite (d) Malachite
(c) Assertion is correct, reason is incorrect
15. Cassiterite is concentrated by
(d) Assertion is incorrect, reason is correct.
(a) levigation (b) electromagnetic separation
26. Copper can be extracted from
(c) floatation (d) liquefaction
16. While extracting an element from its ore, the ore is grounded (a) Kupfernical (b) Dolomite
and leached with dil. potassium cyanide solution to form the (c) Malachite (d) Galena
soluble product potassium argento cyanide. The element is 27. Which of the following metal is correctly matched with its
(a) Lead (b) Chromium ore?
(c) Manganese (d) Silver Metal Ore
17. The method of concentrating the ore which makes use of (a) Zinc Calamine
the difference in density between ore and impurities is called (b) Silver Ilmenite
(a) levigation (b) leaching (c) Magnesium Cassiterite
(c) magnetic separation (d) liquifaction (d) Tin Azurite
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 277

28. Which ore contains both iron and copper? 41. 2CuFeS2 + O 2 ¾¾ ® Cu 2 S + 2FeS + SO 2
(a) Cuprite (b) Chalcocite Which process of metallurgy of copper is represented by
(c) Chalcopyrite (d) Malachite above equation?
29. Which one of the following does not occur as sulphide ore? (a) Concentration (b) Roasting
(a) Zn (b) Cr (c) Ag (d) Fe (c) Reduction (d) Purification
30. Pyrolusite is a/an
(a) oxide ore (b) sulphide ore Topic 3: Thermodynamic Principles of Metallurgy
(c) carbide ore (d) Not an ore 42. According to Ellingham diagram, the oxidation reaction of
31. Sulphide ores of metals are usually concentrated by froth carbon to carbon monoxide may be used to reduce which
flotation process. Which one of the following sulphide ores one of the following oxides at the lowest temperature ?
offer an exception and is concentrated by chemical leaching? (a) Al2O3 (b) Cu2O (c) MgO (d) ZnO
(a) Galena (b) Copper pyrite 43. Which of the following condition favours the reduction of
(c) Sphalerite (d) Argentite a metal oxide to metal?
(a) DH = +ve, TDS = + ve at low temperature
Topic 2: Extraction of Crude Metal from Concentrated Ore (b) DH = +ve, TDS = – ve at any temperature
32. Main function of roasting is (c) DH = –ve, TDS = – ve at high temperature
(a) to remove volatile substances (d) DH = –ve, TDS = + ve at any temperature
(b) oxidation 44. Ellingham diagram normally consists of plots of
(c) reduction (a) DSº vs T (b) D fGº vs DSº
(d) slag formation (c) DGº vs T (d) DHº vs DT
33. Roasting is generally done in case of the 45. DG° vs T plot in the Ellingham’s diagram slopes downward
(a) oxide ores (b) silicate ores for the reaction
(c) sulphide ores (d) carbonate ores 1 1
(a) Mg + O2 ® MgO (b) 2Ag + O 2 ® Ag 2O
34. Function of the flux added during smelting is 2 2
(a) to make ore porous (b) to remove gangue 1 1
(c) to precipitate slag (d) to make reduction easier (c) C + O2 ® CO (d) CO + O 2 ® CO 2
2 2
35. Process followed before reduction of carbonate ore is 46. In the blast furnace iron oxide is reduced by
(a) calcination (b) roasting (a) silica (b) CO
(c) liquation (d) polling (c) carbon (d) limestone
36. Calcination is the process in which : 47. Furnaces are lined with calcium oxide because
(a) ore is heated above its melting point to expel H2O or (a) it gives off oxygen on heating
CO2 or SO2 (b) it gives strong light on heating
(b) ore is heated below its melting point to expel volatile (c) it is refractory and basic
impurities (d) it is not affected by acids
(c) ore is heated above its melting point to remove S, As 48. The following reactions take place in the blast furnace in
and Sb as SO2 ,As2O3 and Sb2O3 respectively the preparation of impure iron. Identify the reaction
(d) ore is heated below its melting point to expel H2O or pertaining to the formation of the slag.
CO2 (a) Fe2O3(s) + 3 CO(g) ®2 Fe (l) + 3 CO2 (g)
37. When a metal is to be extracted from its ore and the gangue (b) CaCO3 (s) ® CaO (s) + CO2 (g)
associated with the ore is silica, then (c) CaO (s) + SiO2(s) ® CaSiO3(s)
(a) an acidic flux is needed (d) 2C(s) + O2 (g) ®2 CO(g)
(b) a basic flux is needed 49. Refractory materials are generally used in furnaces because
(c) both acidic and basic fluxes are needed (a) they possess great structural strength
(d) Neither of them is needed (b) they can withstand high temperature
38. Which of the following fluxes is used to remove acidic (c) they are chemically inert
impurities in metallurgical process? (d) they do not require replacement
(a) Silica (b) Lime stone 50. Extraction of zinc from zinc blende is achieved by
(c) Sodium chloride (d) Sodium carbonate (a) electrolytic reduction
39. Which of the following reactions is an example for calcination (b) roasting followed by reduction with carbon
process ? (c) roasting followed by reduction with another metal
(a) 2Ag + 2HCl + (O ) ® 2AgCl + H 2 O (d) roasting followed by self-reduction
(b) 2Zn + O 2 ® 2 ZnO 51. In the extraction of Cu, the metal is formed in the bessemer
(c) 2ZnS + 3O 2 ® 2ZnO + 2SO 2 converter due to the reaction :
(d) MgCO3 ® MgO + CO 2 (a) Cu2S + 2Cu2O ¾¾ ® 6Cu + SO2
(b) Cu2S ¾¾ ® 2Cu + S
40. After partial roasting the sulphide of copper is reduced by
(a) cyanide process (b) electrolysis (c) Fe + Cu2O ¾¾ ® 2Cu + FeO
(c) reduction with carbon (d) self reduction (d) 2Cu2O ¾¾ ® 4Cu + O2
 EBD_7374
278 CHEMISTRY

52. Aluminothermic process is used for the extraction of metals, 60. Assertion : Copper obtained after bessemerization is known
whose oxides are as blister copper.
(a) fusible Reason : Blisters are produced on the surface of the metal
(b) not easily reduced by carbon due to escaping of dissolved SO2.
(c) not easily reduced by hydrogen (a) Assertion is correct, reason is correct; reason is a
(d) strongly basic correct explanation for assertion.
53. Blister copper is (b) Assertion is correct, reason is correct; reason is not a
(a) Impure Cu (b) Cu alloy correct explanation for assertion
(c) Pure Cu (d) Cu having 1% impurity (c) Assertion is correct, reason is incorrect
54. The furnace used to prepare commercial iron is lined with (d) Assertion is incorrect, reason is correct.
which of the following ? 61. Carbon and CO gas are used to reduce which of the following
(a) Haematite (b) Magnetite pairs of metal oxides for extraction of metals ?
(c) Ironpyrites (d) Both (a) and (b) (a) FeO, SnO (b) SnO, ZnO
55. Which form of the iron contains 4% carbon ? (c) BaO, Na2O2 (d) FeO, ZnO
(a) Cast iron (b) Pig iron 62. Consider the following reactions at 1000°C
(c) Wrought iron (d) Both (a) and (b) 1
A. Zn(s) + O (g) ® ZnO(s); DG° = -360kJ mol-1
56. Which of the following reaction takes place in blast furnace 2
2
during extraction of copper ? 1
(a) 2Cu 2S + 3O 2 ¾¾ ® 2Cu 2O + 2SO 2 B. C(gr) + O 2 (g) ® CO(g); DG° = -460 kJ mol –1
2
(b) 2FeS + 3O 2 ¾¾ ® 2FeO + 2SO 2 Choose the correct statement at 1000°C
(c) 2Cu 2O + Cu 2S ¾¾ ® 6Cu + SO 2 (a) zinc can be oxidised by carbon monoxide.
(d) All of these (b) zinc oxide can be reduced by graphite
57. Which of the following statements related to Ellingham (c) carbon monoxide can be reduced by zinc.
diagrams are correct ? (d) both statements (a) and (b) are true
(i) It provides a sound basis for the choice of reducing 63. Which of the following statements, about the advantage of
agent in the reduction of oxides. roasting of sulphide ore before reduction is not true?
(ii) Each Ellingham plot is represented by a straight line (a) The DG of of the sulphide is greater than those for CS2
untill unless there is some change in phase i.e. solid ® and H2S.
liquid, liquid ® gas and gas ® liquid occurs.
(b) The DGof is negative for roasting of sulphide ore to
(iii) Diagrams similar to Ellingham can be constructed for
oxide.
sulphides and halides which clearly indicates why
(c) Roasting of the sulphide to the oxide is thermo-
reduction of MxS is difficult in comparison to MxO.
dynamically feasible.
(iv) Ellingham diagrams predicts the tendency of reduction
(d) Carbon and hydrogen are suitable reducing agents for
with a reducing agent and kinetics of the reduction process.
reduction of metal sulphides.
(a) (i), (ii) and (iii) (b) (i) and (iii)
64. Which of the following statement is not correct about
(c) (i), (ii) and (iv) (d) (ii) and (iv)
Ellingham diagram?
58. Which of the following statement(s) is/are correct ?
(a) DG increases with an increase in temperature
(i) Cast iron is used in the manufacture of railway sleepers
(b) It consists of plots of DfGº vs T for formation of oxides
(ii) Wrought iron is used in the manufacture of anchors,
(c) a coupling reaction can be well expressed by this
bolts, chains etc.
diagram
(iii) Nickel steel is used in making pendulums.
(d) It express the kinetics of the reduction process
(a) Only (i) (b) (i) and (ii)
65. A coupled reaction takes place as follow–
(c) (i), (ii) and (iii) (d) Only (iii)
59. Match the columns A + B ––® C + D DGº = + x kj
Column - I Column - II D + E ––® F DGº = – y kj
(A) Fe 2 O3 .xH 2O(s) ¾¾® D (p) Slag formation for the spontaneity of reaction A + B + E –––® C + F,
which of the following is correct?
Fe 2O3 (s) + xH 2O(g) (a) 2x = y (b) x < y
(B) FeO + SiO2 ¾¾ ® FeSiO3 (q) Reduction of
iron oxide (c) x > y (d) x = (y) × TDS
(C) Discharge gas produced (r) Calcination 66. The value of Df Gº for formation of Cr2O3 is – 540 kJmol–1 and
during this process is utilised that of Al2O3 is – 827 kJ mol–1 What is the value of DrG° for
in manufacture of H2SO4. the reaction?
(D) Fe2 O3 + 3C ¾¾ ® 2Fe + 3CO (s) Roasting 4 2 2
Al(s) + Cr2 O 3 (s) ® Al 2 O 3 (s) + 4 Cr(s).
(a) A– (r), B – (p), C – (s), D – (q) 3 3 3 3
(b) A– (p), B – (r), C – (s), D – (q) (a) – 574 kJ mol –1 (b) –287 kJ mol –1
(c) A– (r), B – (s), C – (p), D – (q) (c) + 574 kJ mol–1 (d) +287 kJ mol–1
(d) A– (r), B – (p), C – (q), D – (s)
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 279

67. Before introducing FeO in blast furnace , it is converted to 75. Assertion : Zinc can be used while copper cannot be used
Fe2O3 by roasting so that in the recovery of Ag from the complex [Ag(CN)2]–.
(a) it may not be removed as slag with silica Reason : Zinc is a powerful reducing agent than copper.
(b) it may not evaporate in the furnace (a) Assertion is correct, reason is correct; reason is a
(c) presence of it may increase the m.pt. of charge correct explanation for assertion.
(d) None of these. (b) Assertion is correct, reason is correct; reason is not a
68. The temperature in °C at which Fe2O3 is finally reduced to correct explanation for assertion
Fe in the blast furnace is (c) Assertion is correct, reason is incorrect
(a) 993 (b) 797 (c) 897 (d) 1597 (d) Assertion is incorrect, reason is correct.
69. Which of the following statements regarding metallurgy of 76. In the cyanide extraction process of silver from argentite
iron is incorrect ? ore, the oxidising and reducing agents used are
(a) Reaction Fe3O 4 + 4CO ¾¾ ® 3Fe + 4CO 2 belongs to (a) O2 and CO respectively
lower temperature range (500 – 800K) of the blast furnace. (b) O2 and Zn dust respectively
(c) HNO3 and Zn dust respectively
(b) Reaction FeO + CO ¾¾ ® Fe + CO 2 belongs to higher
(d) HNO3 and CO respectively
temperature range (900 – 1500K) of the blast furnace.
77. Extraction of which of the following is based on oxidation ?
(c) The iron obtained from blast furnace is cast iron with
(a) Highly reactive metals
3% carbon.
(b) Moderately reactive metals
(d) For reduction of iron oxide to occur DG of the couple of
(c) Non-metals
following reactions should be negative
1 (d) Both (a) and (c)
FeO(s) ¾¾ ® Fe(s) + O 2 (g) 78. In Hall-Heroult process how much carbon anode is burnt
2
1 away to produce each 1kg of aluminium ?
C(s) + O2 (g) ¾¾ ® CO(g)
2 (a) 0.3 kg (b) 0.5 kg (c) 1 kg (d) 0.1 kg
Topic 4: Electrochemical Principles of Metallurgy
Topic 5: Refining, uses of Aluminium, Copper, Zinc and Iron
and Oxidation Reduction
70. Electrometallurgical process is used to extract 79. The process of zone refining is used in the purification of
(a) Fe (b) Pb (c) Na (d) Ag (a) Si (b) Al (c) Ag (d) Cu
71. The electrolytic method of reduction is employed for the 80. Van Arkel method of purification of metals involves
preparation of metals that converting the metal to a
(a) are weakly electropositive (a) volatile stable compound
(b) are moderately electropositive (b) volatile unstable compound
(c) are strongly electropositive (c) non volatile stable compound
(d) form oxides (d) None of the above
72. Aluminium is extracted from alumina (Al2O3 ) by electrolysis 81. The method not used in metallurgy to refine the impure
of a molten mixture of metal is
(a) Al2O3 + HF + NaAlF4 (b) Al2O3 + CaF2 + NaAlF4 (a) Mond’s process (b) Van–Arkel process
(c) Al2O3 + Na3AlF6 + CaF2 (d) Al2O3 + KF + Na3AlF6
(c) Amalgamation process (d) Liquation
73. In the extraction of aluminium by Hall-Heroult process,
82. Which of the following pairs of metals is purified by van
purified Al2O3 is mixed with CaF2 to
Arkel method ?
(i) lower the melting point of Al2O3.
(a) Ga and In (b) Zr and Ti
(ii) increase the conductivity of molten mixture.
(iii) reduce Al3+ into Al(s). (c) Ag and Au (d) Ni and Fe
(iv) acts as catalyst. 83. Method used for obtaining highly pure silicon which is used
(a) (i) and (ii) (b) (i), (ii) and (iii) as a semiconductor material, is
(c) (iii) and (iv) (d) (ii), (iii) and (iv) (a) oxidation (b) electrochemical
74. Match the columns. (c) crystallization (d) zone refining
Column-I Column-II 84. What is anode mud?
(A) Blisterred Cu (p) Aluminium (a) Fan of anode
(B) Blast furnace (q) 2Cu2O + Cu2S ® 6Cu + SO2 (b) Metal of anode
(C) Reverberatory (r) Iron (c) Impurities collected at anode in electrolysis during
furnace purification of metals
(D) Hall-Heroult (s) FeO + SiO2 ® FeSiO3 (d) All of these
process (t) 2Cu2S + 3O2 ® 2Cu2O + 2SO2 85. Which of the following metal is used in the manufacture of
(a) A – (q), B – (r), C – (s), D – (p) dye-stuffs and paints ?
(b) A – (p), B – (q), C – (r), D – (t) (a) Copper (b) Zinc
(c) A – (t), B – (s), C – (r), D – (q)
(c) Aluminium (d) Magnesium
(d) A – (s), B – (t), C – (r), D – (q)
 EBD_7374
280 CHEMISTRY

86. Match the columns. (c) Antimony, tellurium, silver and gold are some of the
Column-I Column-II metals deposits as anode mud during this process
(A) Coloured bands (p) Zone refining (d) Zinc can be also refined by electrolytic refining method.
(B) Impure metal to volatile (q) Fractional 93. Which of the following is incorrectly matched ?
complex distillation Metal Uses
(C) Purification of Ge and Si (r) Mond Process (a) Wrought iron Casting stoves, gutter
(D) Purification of mercury (s) Chromatography pipes, toys etc.
(t) Liquation (b) Copper Coinage alloy
(a) A – (p), B – (q), C – (s), D – (t) (c) Aluminium Extraction of chromium and
(b) A – (s), B – (r), C – (p), D – (q) manganese
(c) A – (r), B – (s), C – (p), D – (q) (d) Nickel steel Measuring tapes
(d) A – (t), B – (s), C – (r), D – (q) 94. Match the columns
87. In electro-refining of metal the impure metal is used to make Column-I Column-II
the anode and a strip of pure metal as the cathode, during (A) Distillation (p) Zr
the electrolysis of an aqueous solution of a complex metal (B) Electrolytic refining (q) Ga
salt. This method cannot be used for refining of (C) Liquation (r) Cu
(D) Zone refining (s) Hg
(a) Silver (b) Copper
(E) Vapour phase refining (t) Sn
(c) Aluminium (d) Sodium (a) A – (r), B – (s), C – (t), D – (q), E – (p)
88. During the process of electrolytic refining of copper, some (b) A – (s), B – (r), C – (t), D – (q), E – (p)
metals present as impurity settle as ‘anode mud’. These are (c) A – (s), B – (t), C – (r), D – (q), E – (p)
(a) Fe and Ni (b) Ag and Au (d) A – (s), B – (r), C – (p), D – (q), E – (t)
(c) Pb and Zn (d) Sn and Ag 95. Assertion : Lead, tin and bismuth are purified by liquation
89. If the impurities in a metal has a greater affinity for oxygen method.
and is more easily oxidised than the metal, then the Reason : Lead, tin and bismuth have low m.p. as compared
purification of metal may be carried out by to impurities.
(a) distillation (b) zone refining (a) Assertion is correct, reason is correct; reason is a
(c) electrolytic refining (d) cupellation correct explanation for assertion.
90. Match the columns (b) Assertion is correct, reason is correct; reason is not a
Column-I Column-II correct explanation for assertion
(A) Cyanide process (p) Ultrapure Ge (c) Assertion is correct, reason is incorrect
(B) Floatation process (q) Pine oil (d) Assertion is incorrect, reason is correct.
(C) Electrolytic reduction (r) Extraction of Al 96. Match the columns
(D) Zone refining (s) Extraction of Au Column-I Column-II
(a) A – (r), B – (p), C – (s), D – (q) (A) This metal is used in (p) Zinc
(b) A – (s), B – (q), C – (r), D – (p) extraction of chromium
(c) A – (r), B – (q), C – (s), D – (p) and manganese.
(d) A – (s), B – (p), C – (r), D – (q) (B) Common metal in brass (q) Aluminium
91. Germanium of very high purity is obtained by and bronze.
(a) liquation (b) vapour phase refining (C) Common metal in brass (r) Copper
(c) distillation (d) zone refining and german silver.
92. Which of the following statements regarding electrolytic (D) Substance used in making (s) Stainless steel
refining of copper is incorrect ? cycles, automobiles,
(a) In this process anode is made up of impure copper and utensils, etc.
pure copper strips are taken as cathode. (a) A – (q), B – (r), C – (p), D – (s)
(b) Acidic or basic solution of copper sulphate is used as (b) A – (r), B – (q), C – (p), D – (s)
electrolyte (c) A – (q), B – (p), C – (r), D – (s)
(d) A – (q), B – (r), C – (s), D – (p)

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 2. When copper ore is mixed with silica in a reverberatory
furnace copper matte is produced. The copper matte contains
1. In the extraction of chlorine by electrolysis of brine ...........
(a) sulphides of copper (II) and iron (II)
(a) oxidation of Cl– ion to chlorine gas occurs
(b) sulphides of copper (II) and iron (III)
(b) reduction of Cl– ion to chlorine gas occurs
(c) sulphides of copper (I) and iron (II)
(c) for overall reaction D G s has negative value
(d) sulphides of copper (I) and iron (III)
(d) a displacement reaction takes place
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 281

3. Which of the following reactions is an example of auto- Direction (Q. No. 11-13) Answer the questions on the basis of

. .
reduction? figure.
(a) Fe3 O 4 + 4CO ¾¾ ® 3Fe + 4CO 2 –200 eO

–300 .
2F
D.

D G°/kJ mol of O2 ®
®
(b) Cu 2 O + C ¾¾ ® 2Cu + CO O 2

(c) Cu 2+ ( aq ) + Fe (s ) ¾¾
® Cu (s ) + Fe 2 + ( aq ) . ...
A E e+
2 F C + O2 ® CO2
–400
.

–1
B
–500 .
2C
1 1 O2 +
(d) Cu 2 O + Cu 2S ¾¾ ® 3Cu + SO 2 + O
®
2 2 2 CO 2C
O2 2
2C
4. A number of elements are available in earth's crust but most –600 ® O

abundant elements are ................

(a) Al and Fe (b) Al and Cu –700
0 400 800 1200 1600 2000
(c) Fe and Cu (d) Cu and Ag
5. Zone refining is based on the principle that .................. Temperature (°C) ®
(a) impurities of low boiling metals can be separated by 11. Choose the correct option of temperature at which carbon
distillation. reduces FeO to ion and produces CO.
(b) impurities are more soluble in molten metal than in solid (a) Below temperature at point A
metal. (b) Approximately at the temperature corresponding to
(c) different components of a mixture are differently point A
adsorbed on an adsorbent. (c) Above temperature at point A but below temperature
(d) vapours of volatile compound can be decomposed in at point D
pure metal. (d) Above temperature at point A
6. In the extraction of copper from its sulphide ore, the metal is 12. Below point 'A' FeO can .....................
formed by the reduction of Cu2O with (a) be reduced by carbon monoxide only.
(a) FeS (b) CO (b) be reduced by both carbon monoxide and carbon.
(c) Cu2S (d) SO2 (c) be reduced by carbon only.
7. Brine is electrolysed by using inert electrodes. The reaction (d) not be reduced by both carbon and carbon monoxide.
at anode is ................. 13. For the reduction of FeO at the temperature corresponding
to point D, which of the following statements is correct?
1
(a) Cl - ( aq ) ¾¾
® Cl2 ( g ) + e - ; E ºcell = 1.36 V (a) DG value for the overall reduction reaction with carbon
2 monoxide is zero.
(b) DG value for the overall reduction reaction with a
(b) 2H 2 O ( l ) ¾¾
® O 2 ( g ) + 4H + + 4e - ; E ºcell = 1.23 V mixture of 1 mol carbon and 1 mol oxygen is positive.
(c) DG value for the overall reduction reaction with a
(c) Na + ( aq ) + e - ¾¾
® Na (s ) ; E ºcell = 2.71 V mixture of 2 mol carbon and 1 mol oxygen will be
positive.
1
(d) H + ( aq ) + e - ¾¾
® H 2 ( g ) ; E ºcell = 0.00 V (d) DG value for the overall reduction reaction with carbon
2 monoxide is negative.
8. In the metallurgy of aluminium ..............
Past Year MCQs
(a) Al3+ is oxidised to Al (s).
(b) graphite anode is oxidised to carbon monoxide and 14. The metal that cannot be obtained by electrolysis of an
carbon dioxide. aqueous solution of its salts is: [AIPMT 2014, C]
(c) oxidation state of oxygen changes in the reaction at (a) Ag (b) Ca (c) Cu (d) Cr
anode. 15. "Metals are usually not found as nitrates in their ores".
(d) oxidation state of oxygen changes in the overall Out of the following two ((i) and (ii)) reasons which is/are
reaction involved in the process. true for the above observation ? [AIPMT 2015, C]
9. Electrolytic refining is used to purify which of the following (i) Metal nitrates are highly unstable.
metals? (ii) Metal nitrates are highly soluble in water.
(a) Cu and Zn (b) Ge and Si (a) (i) and (ii) are false
(c) Zr and Ti (d) Zn and Hg (b) (i) is false but (ii) is true
10. Extraction of gold and silver involves leaching the metal (c) (i) is true but (ii) is false
with CN – ion. The metal is recovered by .......... (d) (i) and (ii) are true
(a) displacement of metal by some other metal from the 16. In the extraction of copper from its sulphide ore, the metal
complex ion. finally obtained by the reduction of cuprous oxide with :
(b) roasting of metal complex. [AIPMT 2015 RS, C]
(c) calcination followed by roasting. (a) iron (II) sulphide (b) carbon monoxide
(d) thermal decomposition of metal complex. (c) copper (I) sulphide (d) sulphur dioxide
 EBD_7374
282 CHEMISTRY

17. In the context of the Hall - Heroult process for the extraction 24. The main reactions occurring in blast furnace during
of Al, which of the following statements is false ? extraction of iron from haematite are________.
[AIPMT 2015, C] (i) Fe2O3 + 3CO —® 2Fe + 3CO2
3+
(a) Al is reduced at the cathode to form Al (ii) FeO + SiO2 —® FeSiO3
(b) Na3AlF6 serves as the electrolyte (iii) Fe2O3 + 3C —® 2Fe + 3CO
(c) CO and CO2 are produced in this process (iv) CaO + SiO2 —® CaSiO3 [AIIMS 2016, A]
(d) Al2O3 is mixed with CaF2 which lowers the melting point (a) (i) and (iii) (b) (ii) and (iv)
of the mixture and brings conductivity (c) (i) and (iv) (d) (i), (ii) and (iii)
18. Sulfide ores are common for the metals [AIIMS 2015, C] 25. Extraction of gold and silver involves leaching with CN–
(a) Ag, Cu and Pb (c) Ag, Cu and Sn ion. Silver is later recovered by [NEET 2017, C]
(b) Ag, Mg and Pb (d) Al, Cu and Pb (a) distillation (b) zone refining
19. Match List I with List II and select the correct answer using (c) displacement with Zn (d) liquation
the codes given below the list [AIIMS 2015, C] 26. 2CuFeS2 + O 2 ¾¾ ® Cu 2 S + 2FeS + SO 2
List I List II Which process of metallurgy of copper is represented by
1. Ti A. Bauxite above equation? [AIIMS 2017, C]
2. Si B. Cerussite (a) Concentration (b) Roasting
3. Al C. van-Arkel method (c) Reduction (d) Purification
4. Pb D. Zone refining 27. Assertion : Coke and flux are used in smelting.
(a) 1–B, 2–A, 3–C, 4–D (b) 1–B, 2–C, 3–A, 4–B [AIIMS 2017, C]
(c) 1–C, 2–A, 3–B, 4–D (d) 1–C, 2–D, 3–A, 4–B Reason : The phenomenon in which ore is mixed with
20. Match the catalysts to the correct processes : suitable flux and coke is heated to fusion is known as
Catalyst Process [JEE M 2015, A] smelting.
(A) TiCl4 (i) Wacker process (a) If both Assertion and Reason are correct and Reason
(B) PdCl2 (ii) Ziegler - Natta polymerization is the correct explanation of Assertion.
(C) CuCl2 (iii) Contact process (b) If both Assertion and Reason are correct, but Reason
(D) V2O5 (iv) Deacon's process is not the correct explanation of Assertion.
(a) (A) - (ii), (B) - (iii), (C) - (iv), (D) - (i) (c) If Assertion is correct but Reason is incorrect.
(b) (A) - (iii), (B) - (i), (C) - (ii), (D) - (iv) (d) If both the Assertion and Reason are incorrect.
(c) (A) - (iii), (B) - (ii), (C) - (iv), (D) - (i) 28. Assertion : Galvanised iron does not rust. [AIIMS 2017, C]
(d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii) Reason : Zinc has a more negative electrode potential than
21. Semiconductor materials like Si and Ge are usually purified iron.
by [BITSAT 2015, C] (a) If both Assertion and Reason are correct and Reason
(a) distillation (b) zone refining is the correct explanation of Assertion.
(c) liquation (d) electrolytic refining (b) If both Assertion and Reason are correct, but Reason
22. Match items of Column I with the items of Column II and is not the correct explanation of Assertion.
assign the correct code : [NEET 2016, A] (c) If Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
Column-I Column-II
29. Electrometallurgical process is used to extract
(A) Cyanide process (i) Ultrapure Ge
[BITSAT 2017, C]
(B) Froth floatation process (ii) Dressing of ZnS
(a) Fe (b) Pb (c) Na (d) Ag
(C) Electrolytic reduction (iii) Extraction of Al
30. Considering Ellingham diagram, which of the following
(D) Zone refining (iv) Extraction of Au metals can be used to reduce alumina? [NEET 2018, C]
(v) Purification of Ni (a) Fe (b) Zn (c) Cu (d) Mg
Code : 31. Assertion : During calcination, the ore is heated well below
(A) (B) (C) (D) its melting point in the limited supply of air.
(a) (iv) (ii) (iii) (i) Reason : The process of calcination is carried out for
(b) (ii) (iii) (i) (v) sulphide ores. [AIIMS 2018, C]
(a) If both Assertion and Reason are correct and Reason
(c) (i) (ii) (iii) (iv)
is the correct explanation of Assertion.
(d) (iii) (iv) (v) (i)
(b) If both Assertion and Reason are correct, but Reason
23. Which one of the following ores is best concentrated by
is not the correct explanation of Assertion.
froth floatation method? [NEET 2016, C]
(c) If Assertion is correct but Reason is incorrect.
(a) Galena (b) Malachite
(d) If both the Assertion and Reason are incorrect.
(c) Magnetite (d) Siderite
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 283

Exercise 3 : Try If You Can

1. Consider the following reactions : (c) no reducing agent is found suitable for reducing a
D sulphide ore
2XS + 3O 2 ¾¾® 2XO + 2SO 2
(d) a sulphide ore cannot be reduced at all
D
2XO + XS ¾¾® 3' X '+ SO 2 8. Aluminium is prepared in large quantities by
Then 'X' can not be: (a) heating cryolite in a limited quantity of air
(a) Hg (b) Pb (c) Zn (d) Cu (b) reducing aluminium oxide with coke
2. XCl2 ( excess ) + YCl 2 ¾¾
® XCl 4 + Y ¯ ; (c) reducing aluminium oxide with sodium
D 1 (d) electrolysing aluminium oxide dissolved in fused
YO ¾¾¾¾ ® O 2 + Y, Ore of Y would be: electrolyte
> 400° 2
(a) Siderite (b) Cinnabar 9. Complexes formed in the following methods are
(c) Malachite (d) Hornsilver I. Mond's process for purification of nickel.
3. Which of the following combination represents the correct II. Removal of lead poisoning from the body.
matching of metals with the most commonly employed ores III. Cyanide process for extraction of silver.
for their extraction? IV. Froth flotation process for separation of ZnS from
Fe Zn Cu Al galena ore by using depressant.
(a) Haematite Sphalerite Copper Bauxite I II III IV
pyrites (a) Ni(CO)4 [Pb(EDTA]2– [Ag(CN)2]– [Zn(CN)2]
(b) Iron pyrites Zincite Cuprite Clay (b) Ni(CO)4 [Pb(EDTA]2– [Ag(CN)4]– [Zn(CN)4]2–
(c) Siderite Calamine Malachite Alumminium (c) Ni(CO)6 [Pb(EDTA)]4– [Ag(CN)2]– [Zn(CN)6]4–
phosphate (d) Ni(CO)4 [Pb(EDTA)]2– [Ag(CN)4]3– [Zn(CN)4]2–
(d) Chalcocite Magnetite Copper Bauxite 10. Four metals and their methods of refinement are given
glance i. Ni, Cu, Zr, Ga
4. All ores are minerals, while all minerals are not ores because ii. Electrolysis, Van Arkel process, zone refining, Mond's
(a) the metal can’t be extracted economically from all the process
minerals Choose the right method for each :
(b) minerals are complex compounds
(a) Ni: Electrolysis; Cu: Van Arkel process; Zr: Zone
(c) the minerals are obtained from mines refining; Ga: Mond's process.
(d) All of these are correct
(b) Ni: Mond's process; Cu: Electrolysis; Zr: Van Arkel
5. Consider the following reactions at 1000°C.
process; Ga: Zone refining
D
(I) Zn ( s ) + 1/ 2 O 2 ( g ) ¾¾® ZnO ( g ) ; (c) Ni: Mond's process; Cu: Van Arkel process; Zr: Zone
DG° = –360 kJ mol–1 refining; Ga: Electrolysis.
D (d) Ni: Electrolysis; Cu: Zone refining; Zr: Van Arkel
(II) C ( s ) + 1/ 2O2 (g ) ¾¾® CO ( g ) ;
process; Ga: Mond's process
DG° = –460 kJ mol–1
11. The method of zone refining of metals is based on the
and choose the correct statement at 1000°C.
principle of
(a) ZnO is more stable than CO
(b) ZnO can be reduced to Zn by C (a) Greater solubility of the impurity in the molten state
than in the solid
(c) ZnO and CO are formed at equal rate
(d) ZnO can not be reduced to Zn by C (b) Greater mobility of the pure metal than that of the
impurity
6. D¦G– vs T plot in the Ellingham diagram slopes downward
for the reaction (c) Higher melting point of the impurity than that of the
pure metal
1 1
(a) Mg + O2 ® MgO (b) 2Ag + O 2 ® Ag 2O (d) Greater noble character of the solid metal than that of
2 2 the impurity
1 1
(c) C + O2 ® CO (d) CO + O 2 ® CO 2 12. Select the property which forms the basis of
2 2 hydrometallurgical process that is used for extraction of
7. A sulphide ore is generally roasted to the oxide before gold.
reduction, because
(a) Gold is electropositive metal
(a) the enthalpy of formation of CO2 is more than that of
(b) Gold is less reactive metal
CS2
(b) a metal sulphide is generally more stable than the metal (c) Gold forms complexes that are water soluble
oxide (d) Gold forms salts, which are water soluble
 EBD_7374
284 CHEMISTRY

13. When CuSO4 is electrolysed using platinum electrodes, 15. Which of the following statements is correct ?
(a) copper is liberated at cathode, sulphur at anode (a) Gangues are carefully chosen to combine with the slag
(b) copper is liberated at cathode, oxygen at anode present in the ore to produce easily fusible flux to carry
(c) sulphur is liberated at cathode, oxygen at anode away the impurities
(d) oxygen is liberated at cathode, copper at anode (b) Slags are carefully chosen to combine with the flux
14. In electro-refining of metal, the impure metal is used to present in the ore to produce easily fusible gangue to
make the anode and a strip of pure metal as the cathode, carry away the impurities
during the electrolysis of an aqueous solution of a complex (c) Gangues are carefully chosen to combine with the flux
metal salt. This method cannot be used for refining of present in the ore to produce easily fusible slag to
(a) Silver (b) Copper carry away the impurities
(c) Aluminium (d) Sodium (d) Fluxes are carefully chosen to combine with the gangue
present in the ore to produce easily fusible slag to
carry away the impurities

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (a) 11 (a) 21 (c) 31 (d) 41 (b) 51 (d) 61 (d) 71 (c) 81 (c) 91 (d)
2 (a) 12 (c) 22 (a) 32 (a) 42 (b) 52 (b) 62 (b) 72 (c) 82 (b) 92 (b)
3 (a) 13 (c) 23 (a) 33 (c) 43 (d) 53 (d) 63 (d) 73 (a) 83 (d) 93 (a)
4 (a) 14 (c) 24 (c) 34 (b) 44 (c) 54 (a) 64 (d) 74 (a) 84 (c) 94 (b)
5 (b) 15 (b) 25 (d) 35 (a) 45 (c) 55 (b) 65 (d) 75 (a) 85 (b) 95 (a)
6 (c) 16 (d) 26 (c) 36 (d) 46 (b) 56 (d) 66 (b) 76 (b) 86 (b) 96 (a)
7 (a) 17 (a) 27 (a) 37 (b) 47 (c) 57 (b) 67 (a) 77 (c) 87 (d)
8 (c) 18 (b) 28 (c) 38 (b) 48 (c) 58 (c) 68 (a) 78 (b) 88 (b)
9 (c) 19 (a) 29 (b) 39 (d) 49 (b) 59 (a) 69 (c) 79 (a) 89 (d)
10 (d) 20 (c) 30 (a) 40 (d) 50 (b) 60 (a) 70 (c) 80 (a) 90 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (a) 5 (b) 8 (b) 11 (d) 14 (b) 17 (b) 20 (b) 23 (c) 26 (b) 29 (d)
2 (c) 6 (c) 9 (a) 12 (a) 15 (b) 18 (a) 21 (c) 24 (c) 27 (a) 30 (d)
3 (d) 7 (a) 10 (a) 13 (a) 16 (a) 19 (d) 22 (a) 25 (b) 28 (c) 31 (c)
4 (a)
Exercise 3 : Try If You Can
1 (c) 3 (a) 5 (b) 7 (a) 9 (b) 11 (a) 13 (b) 15 (d)
2 (b) 4 (a) 6 (c) 8 (d) 10 (b) 12 (c) 14 (d)
 21 Chapter
THE p-BLOCK ELEMENTS
(GROUP 15, 16, 17 AND 18)

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Structure of oxoacids of
AIIMS 3 phosphorous, Sulphur and 3.8/5 9
JEE Main 2 Halogen Interhalogen
BITSAT 2 compounds
 EBD_7374
286 CHEMISTRY
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 287
 EBD_7374
288 CHEMISTRY

Exercise 1 : Topic-wise MCQs

(a) Non metallic character (b) Inert pair effect
Topic 1: Group 15 Elements
(c) High electronegativity (d) Large ionization energy
1. Ionic radii (in Å) of As3+, Sb3+ and Bi3+ follow the order 13. Pure nitrogen is prepared in the laboratory by heating a mixture
(a) As3+ > Sb3+ > Bi3+ (b) Sb3+ > Bi3+ >As3+ of
3+
(c) Bi > As > Sb3+ 3+ (d) Bi3+ > Sb3+ > As3+ (a) NH4OH + NaCl (b) NH4NO3 + NaCl
2. Which of the following statements is not correct for (c) NH4Cl + NaOH (d) NH4Cl + NaNO2.
nitrogen? 14. Most acidic oxide among the following is –
(a) Its electronegativity is very high
(a) N2O5 (b) P2O5 (c) N2O4 (d) As2O 3
(b) d-orbitals are available for bonding
15. Which of the following species has the highest dipole moment?
(c) It is a typical non-metal
(d) Its molecular size is small (a) NH3 (b) PH3 (c) AsH3 (d) SbH3
3. Collectively the elements of group 15 are called – 16. The correct decreasing order of basic strength is:
(a) pnicogens (b) pnicopens (a) AsH3 > SbH3 > PH3 > NH3
(c) nicopen (d) None of these (b) SbH 3 > AsH 3 > PH 3 > NH 3
4. Which one of the following elements is most metallic ?
(c) NH 3 > PH 3 > AsH 3 > SbH 3
(a) P (b) As (c) Sb (d) Bi
5. Which of the following group 15 element forms metallic (d) PH 3 > AsH 3 > SbH 3 > NH 3
bonds in elemental state ? 17. Liquid ammonia bottles are opened after cooling them in ice
(a) As (b) P (c) Sb (d) Bi for sometime. It is because liquid NH3
6. The three important oxidation states of phosphorus are (a) Brings tears to the eyes
(a) –3, +3 and +5 (b) –3, +3 and –5
(b) Has a high vapour pressure
(c) –3, +3 and +2 (d) –3, +3 and +4
7. Nitrogen is relatively inactive element because (c) Is a corrosive liquid
(a) its atom has a stable electronic configuration (d) Is a mild explosive
(b) it has low atomic radius 18. Ammonia is generally manufactured for fertilizers by the
(c) its electronegativity is fairly high reaction
(d) dissociation energy of its molecule is fairly high (a) 2NH 4Cl + Ca(OH) 2 ® CaCl 2 + 2H 2O + 2NH3
8. Which of the following has the highest pp – pp bonding
tendency ? (b) By passing an electric discharge in a mixture of N2 and
(a) N (b) P (c) As (d) Sb H2
9. Pick out the wrong statement. (c) By passing a mixture of N2 and H2 under high pressure
(a) Nitrogen has the ability to form pp-pp bonds with itself. and moderate temperature over a catalyst
(b) Bismuth forms metallic bonds in elemental state. (d) None of these
(c) Catenation tendency is higher in nitrogen when 19. Nitrogen dioxide cannot be obtained by heating :
compared with other elements of the same group. (a) KNO3 (b) Pb(NO3)2
(d) Nitrogen has higher first ionisation enthalpy when (c) Cu(NO3)2 (d) AgNO3
compared with other elements of the same group. 20. Which of the following oxides is neutral ?
10. Nitrogen forms N2, but phosphorus is converted into P4 (a) N2O3 (b) N2O4 (c) N2O5 (d) N2O
from P, the reason is 21. Which of the following oxides of nitrogen is a coloured
(a) Triple bond is present between phosphorus atom gas?
(b) pp – pp bonding is strong (a) N2O (b) NO (c) N2O5 (d) NO2
(c) pp – pp bonding is weak 22. In which one of the following oxides of nitrogen, one
(d) Multiple bond is formed easily nitrogen atom is not directly linked to oxygen?
11. What causes nitrogen to be chemically inert ? (a) NO (b) N2O4 (c) N2O (d) N2O3
(a) Multiple bond formation in the molecule 23. Which of the following oxides of nitrogen reacts with FeSO4
(b) Absence of bond polarity to form a dark brown compound
(c) Short internuclear distance (a) N2O (b) NO (c) NO2 (d) N2O3
(d) High bond energy 24. Which oxide of nitrogen is obtained on heating ammonium
12. Among the 15th group elements, as we move from nitrogen nitrate at 250ºC ?
to bismuth, the pentavalency becomes less pronounced and (a) Nitric oxide (b) Nitrous oxide
trivalency becomes more pronounced due to
(c) Nitrogen dioxide (d) Dinitrogen tetraoxide
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 289

25. Which of the following can be used as an anaesthesia ? 37. Phosphine is not evolved when
(a) N2O (b) NO (c) NCl3 (d) NO2 (a) white phosphorus is boiled with a strong solution of
26. A deep brown gas is formed by mixing two colourless gases Ba(OH)2
which are (b) phosphorus acid is heated
(a) NO2 and O2 (b) N2O and NO (c) calcium hypophosphite is heated
(c) NO and O2 (d) NH3 and HCl (d) metaphosphoric acid is heated.
27. The catalyst used in the manufacture of HNO 3 by 38. Pure phosphine is not combustible while impure phosphine
is combustible, this combustibility is due to presence of
Ostwald’s process is :
(a) platinum gauze (b) vanadium pentoxide (a) P2 H 4 (b) N2 (c) PH 5 (d) P2 O5
(c) finely divided nickel (d) platinum black . 39. When orthophosphoric acid is heated to 600°C, the product
28. Concentrated nitric acid, upon long standing, turns yellow formed is
brown due to the formation of (a) PH3 (b) P2O5 (c) H3PO3 (d) HPO3
(a) NO (b) NO2 (c) N2O (d) N2O4 40. P2O5 is heated with water to give
29. Which of the following trihalide is unstable? (a) hypophosphorous acid(b) phosphorous acid
(a) NF3` (b) AsCl3 (c) SbBr3 (d) NCl3 (c) hypophosphoric acid (d) orthophosphoric acid
30. Which of the following is the strongest reducing agent ? 41. Basicity of orthophosphoric acid is
(a) NH3 (b) PH3 (c) BiH3 (d) SbH3 (a) 2 (b) 3 (c) 4 (d) 5
31. The nitrogen oxides that contain(s) N–N bond(s) is /are 42. PCl3 reacts with water to form
(i) N2O (ii) N2O3 (iii) N2O4 (iv) N2O5 (a) PH3 (b) H3PO4 and HCl
(a) (i) , (ii) (b) (ii) , (iii) , (iv) (c) POCl3 (d) H3PO4
(c) (iii) , (iv) (d) (i), (ii) and (iii) 43. The number of hydrogen atom(s) attached to phosphorus
32. Zinc on reaction with dilute HNO3 gives x and zinc on atom in hypophosphorous acid is
reaction with concentrated HNO3 gives y. Identify x and y. (a) three (b) one (c) two (d) zero
(a) x = NO2 , y = N2O (b) x = N2O , y = NO 44. The number of P – O – P bonds in cyclic metaphosphoric
(c) x = NO , y = NO2 (d) x = N2O , y = NO2 acid is
33. Which of the following is incorrect for white and red (a) zero (b) two (c) three (d) four
phosphorus ?
(a) They are both soluble in CS2 45. Oxidation states of P in H4 P2O5 , H4 P2O6 , and H4 P2O7 ,
(b) They can be oxidised by heating in air are respectively:
(c) They consist of the same kind of atoms (a) + 3, + 5, + 4 (b) + 5, + 3, + 4
(d) They can be converted into one another (c) + 5, + 4, + 3 (d) + 3, + 4, + 5
34. Which property of white phosphorus is common to 46. How many bridging oxygen atoms are present in P4O10?
red phosphorous ? (a) 5 (b) 6 (c) 4 (d) 2
(a) It burns when heated in air. 47. Which of the following statements is not valid for oxoacids
(b) It reacts with hot caustic soda solution to give of phosphorus?
phosphine. (a) Orthophosphoric acid is used in the manufacture of
(c) It shows chemiluminescence. triple superphosphate.
(d) It is soluble in carbon disulphide. (b) Hypophosphorous acid is a diprotic acid.
35. Which of the following statements regarding allotropic (c) All oxoacids contain tetrahedral four coordinated
forms of phosphorus is incorrect? phosphorus.
(a) White phosphorus is more reactive than red and black (d) All oxoacids contain atleast one P = O and one P — OH
due to high angular strain. group.
(b) Red phosphorus on heating catches fire and give 48. What is hybridization of P in PCl5 ?
dense red fumes of P4O10. (a) sp3 (b) sp3d 2 (c) sp3d (d) sp2
(c) Red phosphorus is polymeric in nature consisting of 49. Which of the following is a cyclic phosphate ?
chains of P4 tetrahedral. (a) H3P3O10 (b) H6P4O13
(d) Black phosphorus has two forms a-black and b-black (c) H5P5O15 (d) H7P5O16
phosphorus 50. P—O—P bond is present in
36. One mole of calcium phosphide on reaction with excess (a) H4P2O6 (b) H4P2O5
water gives (c) Both (a) and (b) (d) Neither (a) nor (b)
(a) one mole of phosphine 51. Among the oxyacids of phosphorus, the dibasic acid is
(b) two moles of phosphoric acid (a) H4P2O7 (b) H3PO2 (c) HPO3 (d) H3PO3
(c) two moles of phosphine 52. The basicity of pyrophosphorus acid is
(d) one mole of phosphorus pentoxide
(a) 2 (b) 4 (c) 1 (d) 5
 EBD_7374
290 CHEMISTRY

53. The oxidation state of phosphorus in cyclotrimeta- 60. Blue solid which is obtained on reacting equimolar amounts
phosphoric acid is of two gases at 245K is?
(a) +3 (b) +5 (c) –3 (d) +2 (a) N2O (b) N2O3 (c) N2O4 (d) N2O5
54. Which acid has P – P linkage ? 61. Concentrated nitric acid, upon long standing, turns yellow
(a) Hypophosphoric acid (b) Pyrophosphoric acid brown due to the formation of
(c) Metaphosphoric acid (d) Orthophosphoric acid (a) NO (b) NO2 (c) N2O (d) N2O4
55. Which of the following statements are correct? 62. In the reaction
(i) All the three N—O bond lengths in HNO3 are equal. 4HNO 3 + P4 O10 ® 4HPO 3 + X , the product X is
(ii) All P—Cl bond lengths in PCl5 molecule in gaseous
state are equal. (a) N2O5 (b) N2O3 (c) NO2 (d) H2O
(iii) P4 molecule in white phohsphorus have angular strain 63. Match the columns.
therefore white phosphorus is very reactive. Column-I Column-II
(iv) PCl5 is ionic in solid state in which cation is tetrahedral (Oxyacid) (Materials for
and anion is octahedral. preparation)
(a) (i) and (iv) (b) (iii) and (iv) (A) H3PO2 (p) Red P + alkali
(c) (ii) and (iii) (d) (ii) only
56. Match the columns
Column-I Column-II (B) H3PO3 (q) P4O10 + H2O
(C) H3PO4 (r) P2O3 + H2O
673K
(A) 2Pb(NO3)2 ¾¾¾® (p) High pressure favours (D) H4P2O6 (s) White P + alkali
4NO2 + 2PbO + O2 the formation of (a) (A) – (s), (B) – (r), (C) – (q), (D) – (p)
product (b) (A) – (p), (B) – (r), (C) – (q), (D) – (s)
(B) N2(g) + O2(g) ƒ (q) Product formed is acidic (c) (A) – (s), (B) – (r), (C) – (p), (D) – (q)
2NO(g) brown gas (d) (A) – (q), (B) – (r), (C) – (p), (D) – (s)
(C) NH4NO3 ¾¾ D (r) This reaction occurs at 64. The structural formula of hypophosphorous acid is
®
N2O + 2H2O a high temperature O O
about 2000 K
P P
(D) N2(g) + 3H2(g) ƒ (s) Product formed is a (a) H (b) H
OH OH
2NH3(g) neutral colourless gas H OH
(a) A – (r, s), B – (q), C – (s), D – (p)
(b) A – (q), B – (r,s), C – (s), D – (p) O O
(c) A – (q), B – (s), C – (r, s), D – (p) P P
(d) A – (q), B – (r, s), C – (p), D – (s) (c) HO (d) H
OH OOH
57. Assertion : Dinitrogen is inert at room temperature. OH OH
Reason : Dinitrogen directly combines with lithium to form 65. Ammonia on catalytic oxidation gives an oxide from which
ionic nitrides. nitric acid is obtained. The oxide is :
(a) Assertion is correct, reason is correct; reason is a (a) N 2 O3 (b) NO (c) NO 2 (d) N 2 O5
correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a 66. In which of the following equations the product formed
correct explanation for assertion has similar oxidation state for nitrogen?
(c) Assertion is correct, reason is incorrect (i) D
NH4NO3 ¾¾ ® N2O + 2H2O
(d) Assertion is incorrect, reason is correct.
58. In nitrogen family, the H-M-H bond angle in the hydrides 673K
(ii) 2Pb(NO3)2 ¾¾¾® 4NO2 + 2PbO + O2
gradually becomes closer to 90º on going from N to Sb. This
shows that gradually (iii) 4HNO3 + P4O10 ¾¾
® 4HPO3 + 2N2O5
(a) The basic strength of the hydrides increases Cool
(b) Almost pure p-orbitals are used for M-H bonding ˆˆˆˆ† N O
(iv) 2NO2 ‡ˆˆˆˆ 2 4
(c) The bond energies of M-H bonds increase Heat
(d) The bond pairs of electrons become nearer to the central (a) (i) and (iii) (b) (ii) and (iv)
atom (c) (i) and (v) (d) (iii) and (iv)
59. The deep blue colour produced on adding excess of 67. What is Z in following reaction
ammonia to copper sulphate is due to presence of CuSO4 + Z ® Cu3P2 +H2SO4
HgCl2 + Z ® Hg3P2 +HCl
(a) Cu 2 + (b) Cu ( NH 3 ) 24 +
(a) White phosphorus (b) Red phosphorus
(c) Cu ( NH 3 ) 26 + (d) Cu( NH3 ) 22 + (c) Phosphine (d) Orthophosphoric acid
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 291

68. Match the columns 81. Atomicity of sulphur in rhombic sulphur is

Column - I Column - II (a) 1 (b) 2 (c) 8 (d) 6
(A) Used in manufacture (p) Ammonia 82. Which of the following form of the sulphur shows
of calcium cyanamide paramagnetic behaviour ?
(B) Used in manufacture (q) Nitric acid (a) S8 (b) S6 (c) S2 (d) All of these
of nitric acid 83. What is X in the following reaction ?
(C) Used in pickling of (r) Dinitrogen X
2SO2(g) + O2(g) ¾¾® 2SO3(g)
stainless steel (a) V2O5 (b) CuO (c) CuCl2 (d) MnO2
(a) A – (r), B – (p), C – (q) (b) A – (p), B – (r), C – (q) 84. Which of the following oxo acid of sulphur has O–O bond ?
(c) A – (r), B – (q), C – (p) (d) A – (q), B – (p), C – (r) (a) H2S2O7 (b) H2S2O8 (c) H2S2O6 (d) H2S2O5
69. Assertion : When a metal is treated with conc. HNO3 it 85. Carbohydrates on reaction with conc. H2SO4 becomes
generally yields a nitrate, NO2 and H2O. charred due to
Reason : Conc. HNO3 reacts with metal and first produces a (a) hydrolysis (b) dehydration
metal nitrate and nascent hydrogen. The nascent hydrogen (c) hydration (d) oxidation
then further reduces HNO3 to NO2. 86. Which of the following is the key step in the manufacture of
(a) Assertion is correct, reason is correct; reason is a sulphuric acid ?
correct explanation for assertion. (a) Burning of sulphur or sulphide ores in air to generate
(b) Assertion is correct, reason is correct; reason is not a SO2
correct explanation for assertion (b) Conversion of SO2 to SO3 by the reaction with oxygen
(c) Assertion is correct, reason is incorrect in presence of catalyst.
(d) Assertion is incorrect, reason is correct. (c) Absorption of SO3 in H2SO4 to give oleum.
(d) Both (b) and (c)
Topic 2: Group 16 Elements 87. Hybridization of S in SO3 is
(a) sp2 (b) sp3 (c) sp2d (d) sp3d 2
70. Which of the following hydrides has the lowest boiling 88. The acid which has a peroxy linkage is
point? (a) Sulphurous acid (b) Pyrosulphuric acid
(a) H2O (b) H2S (c) H2Se (d) H2Te (c) Dithionic acid (d) Caro’s acid
71. Which of the following hydrides is most acidic ? 89. S – S bond is not present in
(a) H2Te (b) H2Se (c) H2O (d) H2S
(a) S 2 O 24 - (b) S2 O 52 - (c) S2 O 32 - (d) S2 O 27 -
72. Which of the following hydrides shows the highest boiling
point ? 90. On addition of conc. H2SO4 to a chloride salt, colourless
(a) H2O (b) H2S (c) H2Se (d) H2Te fumes are evolved but in case of iodide salt, violet fumes
come out. This is because
73. Which is the best oxidising agent among the following ?
(a) H2SO4reduces HI to I2
(a) S (b) O (c) Se (d) Te
(b) HI is of violet colour
74. Which of the following oxide is amphoteric ? (c) HI gets oxidised to I2
(a) SnO2 (b) CaO (c) SiO2 (d) CO2 (d) HI changes to HIO3
75. Which of the following is not correctly matched ? 91. Caro’s acid is
(a) SF4 – gas (b) SeF4 – liquid (a) H2SO3 (b) H3S2O5 (c) H2SO5 (d) H2S2O8
(c) TeF4 – solid (d) SF6 – solid 92. Sulphuric acid reacts with PCl5 to give
76. The compound which gives off oxygen on moderate heating
(a) thionyl chloride (b) sulphur monochloride
is :
(c) sulphuryl chloride (d) sulphur tetrachloride
(a) cupric oxide (b) mercuric oxide
93. The correct statement(s) about O3 is(are)
(c) zinc oxide (d) aluminium oxide
(i) O—O bond lengths are equal
77. Which of the following is not oxidized by O3 ?
(ii) Thermal decomposition of O3 is endothermic
(a) KI (b) FeSO4 (c) KMnO4 (d) K2MnO4
(iii) O3 is diamagnetic in nature
78. Oxygen gas can be prepared from solid KMnO4 by : (iv) O3 has a bent structure
(a) treating the solid with H 2 gas (a) (i) and (iii) (b) (ii) and (iii)
(c) (i), (ii) and (iv) (d) (i) and (iv)
(b) strongly heating the solid 94. Assertion : Bond angle of H2S is smaller than H2O.
(c) dissolving the solid in dil. H 2SO 4 Reason : Electronegativity of the central atom increases,
(d) dissolving solid in dil. HCl bond angle decreases.
79. Which of the following on thermal decomposition gives (a) Assertion is correct, reason is correct; reason is a
oxygen gas ? correct explanation for assertion.
(a) Ag2O (b) Pb3O4 (c) PbO2 (d) All of these (b) Assertion is correct, reason is correct; reason is not a
80. Which of the following is an acidic oxide? correct explanation for assertion
(a) Mn 2O7 (b) Na2O (a) N2O (b) BaO (c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct.
 EBD_7374
292 CHEMISTRY

95. It is possible to obtain oxygen from air by fractional 106. Which of the following halogen does not exhibit positive
distillation because oxidation state in its compounds?
(a) oxygen is in a different group of the periodic table from (a) Cl (b) Br (c) I (d) F
nitrogen 107. Which of the following is the best description for the
(b) oxygen is more reactive than nitrogen behaviour of bromine in the reaction given below ?
(c) oxygen has higher b.p. than nitrogen
(d) oxygen has a lower density than nitrogen. H 2 O + Br2 ® HOBr + HBr
96. Electronegativity of oxygen is more than sulphur yet H2S is (a) Proton acceptor only
acidic while water is neutral. This is because (b) Both oxidized and reduced
(a) water is highly associated compound (c) Oxidized only
(b) molecular mass of H2S is more than H2O (d) Reduced only
(c) H2S is gas while H2O is a liquid 108. Among the following which is the strongest oxidising agent?
(d) H–S bond is weaker than H–O bond (a) Br2 (b) I2 (c) Cl2 (d) F2
97. Assertion : Both rhombic and monoclinic sulphur exist as
109. The correct order of heat of formation of halogen acids is
S8 but oxygen exists as O2.
Reason : Oxfygen forms pp – pp multiple bond due to small (a) HI > HBr > HCl > HF (b) HF > HCl > HBr > HI
size and small bond length but pp – pp bonding is not possible (c) HCl > HF > HBr > HI (d) HCl > HBr > HF > HI
in sulphur. 110. Which of the following is most volatile ?
(a) Assertion is correct, reason is correct; reason is a (a) HI (b) HBr (c) HCl (d) HF
correct explanation for assertion. 111. At room temperature, HCl is a gas while HF is a low boiling
(b) Assertion is correct, reason is correct; reason is not a liquid. This is because
correct explanation for assertion (a) H- F bond is covalent (b) H- F bond is ionic
(c) Assertion is correct, reason is incorrect (c) HF has metallic bond (d) HF has hydrogen bond
(d) Assertion is incorrect, reason is correct. 112. The bleaching action of chlorine is due to
(a) reduction (b) hydrogenation
Topic 3: Group 17 Elements (c) chlorination (d) oxidation
98. Among F, Cl, Br and I the lowest ionization potential will be 113. Cl2 reacts with hot and conc. NaOH to give –
of (a) NaClO (b) NaClO3 (c) NaClO2 (d) NaClO4
(a) fluorine (b) chlorine (c) bromine (d) iodine 114. When chlorine reacts with cold and dilute solution of sodium
99. The electronegativity follows the order hydroxide, the products obtained are
(a) F > O > Cl > Br (b) F > Cl > Br > O (a) Cl– + ClO– (b) Cl– + ClO -2
(c) O > F > Cl > Br (d) Cl > F > O > Br
100. Electron gain enthalpy with negative sign of fluorine is less (c) Cl– + ClO3- (d) Cl– + ClO -4
than that of chlorine due to : 115. Which of the following is used in the preparation of chlorine?
(a) High ionization enthalpy of fluorine (a) Only MnO2
(b) Smaller size of chlorine atom (b) Only KMnO4
(c) Smaller size of fluorine atom (c) Both MnO2 and KMnO4
(d) Bigger size of 2p orbital of fluorine (d) Either MnO2 or KMnO4
101. Which one of the following order is correct for the bond 116. The reaction of KMnO4 and HCl results in
energies of halogen molecules ? (a) oxidation of Mn in KMnO4 and production of Cl2
(a) I2 > Cl2 > Br2 (b) Br2 > Cl2 > I2 (b) reduction of Mn in KMnO4 and production of H2
(c) I2 > Br2 > Cl2 (d) Cl2 > Br2 > I2 (c) oxidation of Mn in KMnO4 and production of H2
102. The correct order of reactivity of halogens with alkalies is (d) reduction of Mn in KMnO4 and production of Cl2
(a) F > Cl > Br > I (b) F < Cl > Br < I 117. Bleaching powder on standing forms mixture of :
(c) F < Cl < Br < I (d) F < Cl < Br > I (a) CaO + Cl 2 (b) CaO + CaCl 2
103. The correct order of increasing oxidising power is
(c) HOCl + Cl 2 (d) CaCl 2 + Ca (ClO3 ) 2
(a) F2 > Br2 > Cl2 > I2 (b) F2 < Cl2 < Br2 < I2
(c) Cl2> Br2 > F2 > I2 (d) I2 < Br2 < Cl2 < F2 118. Hydrochloric acid at 25ºC is
104. Fluorine is a stronger oxidising agent than chlorine in (a) ionic and liquid (b) covalent and liquid
aqueous solution. This is attributed to many factors except (c) ionic and gas (d) None of these
(a) heat of dissociation (b) ionisation potential 119. Gaseous HCl is a poor conductor of electricity while its
(c) heat of hydration (d) electron affinity aqueous solution is a good conductor this is because
105. Fluorine exhibits an oxidation state of only –1 because (a) H 2 O is a good conductor of electricity
(a) it can readily accept an electron (b) a gas cannot conduct electricity but a liquid can
(b) it is very strongly electronegative (c) HCl gas does not obey Ohm’s law, whereas the solution
(c) it is a non-metal does
(d) it belongs to halogen family (d) HCl ionises in aqueous solution
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 293

120. Which one is most stable to heat – 128. The correct order of the thermal stability of hydrogen halides
(a) HClO (b) HClO2 (c) HClO3 (d) HClO4 (H–X) is
121. Interhalogen compounds are more reactive than the (a) HI > HCl < HF > HBr (b) HCl< HF > HBr < HI
individual halogen because (c) HF > HCl > HBr > HI (d) HI < HBr > HCl < HF
(a) two halogens are present in place of one 129. In the case of alkali metals, the covalent character decreases
(b) they are more ionic in the order:
(c) their bond energy is less than the bond energy of the (a) MF > MCl > MBr > MI (b) MF > MCl > MI > MBr
halogen molecule (c) MI > MBr > MCl > MF (d) MCl > MI > MBr > MF
(d) they carry more energy 130. Which of the following order is/are incorrect regarding the
122. Which of the following is not the characteristic of
property indicated against it?
interhalogen compounds ?
(i) HF > HI > HBr > HCl : Thermal stability
(a) They are more reactive than halogens
(ii) Cl2O7 > Cl2O6 > ClO2 > Cl2O : Acidic character
(b) They are quite unstable but none of them is explosive
(c) They are covalent in nature (iii) SbCl3 > SbCl5 : Covalent character
(d) They have low boiling points and are highly volatile. (iv) MCl > MBr : Ionic character
123. In which of the following reactions chlorine is both reduced (a) (iii) only (b) (ii) only
and oxidized? (c) (i) and (iii) (d) (ii) and (iv)
(a) 2KMnO4 + 16HCl¾¾ ® 2KCl + 2MnCl2 + 8H2O + 5Cl2 131. What is X and Y in the given reactions ?
2X2 (g) + 2H2O (l) ® 4H+ (aq) + 4X– (aq) + O2 (g)
(b) 6NaOH + 3Cl2 ¾¾ ® 5NaCl + NaClO3 + 3H2O
Y2 (g) + H2O (l) ® HY(aq) + HOY(aq)
(c) NH3 + 3Cl2 ¾¾ ® NCl3 + 3HCl (a) X = Cl , Y = F (b) X = Cl , Y = Br
(d) I2 + 6H2O + 5Cl2 ¾¾ ® 2HIO3 + 10HCl (c) X = F , Y = Cl (d) X = I , Y = F
124. Which of the following is observed when Cl2 reacts with 132. Which of the following is correct about the reaction?
hot and concentrated NaOH?
heat
(a) NaCl , NaOCl (b) NaCl , NaClO2 3NaClO ¾¾¾ ® NaClO3 + 2NaCl
(c) NaCl , NaClO3 (d) NaOCl , NaClO3 (a) It is disproportionation reaction
125. Which of the following statements regarding properties of (b) Oxidation number of Cl decreases as well as increases
halogens are correct? in this reaction
(i) Due to small size electron gain enthalpy of fluorine is (c) This reaction is used for the manufacture of halates
less than that of chlorine. (d) All of these
(ii) Iodine has same physical state but different colour as
compare to other members of the group. 133. Which pair gives Cl 2 at room temperature :
(iii) Fluorine shows no positive oxidation state. (a) NaCl + Conc. H 2SO 4 (b) Conc. HCl + KMnO4
(iv) In X2(g) + H2O(l) ¾¾ ® HX(aq) + HOX(aq)
(where X2 = Cl or Br) (c) NaCl + Conc. HNO 3 (d) NaCl + MnO2
(a) (i), (ii) and (iv) (b) (i), (iii) and (iv)
(c) (ii), (iii) and (iv) (d) (iii) and (iv) Topic 4: Group 18 Elements
126. Which of the following statements are correct?
134. Which of the following noble gases do not have an octet of
(i) Among halogens, radius ratio between iodine and
electrons in its outermost shell?
fluorine is maximum.
(a) Neon (b) Radon (c) Argon (d) Helium
(ii) Leaving F—F bond, all halogens have weaker X—X
135. In the following four elements, the ionisation potential of
bond than X—X¢ bond in interhalogens.
which one is the highest ?
(iii) Among interhalogen compounds maximum number of
(a) Oxygen (b) Argon (c) Barium (d) Cesium
atoms are present in iodine fluoride.
(iv) Interhalogen compounds are more reactive than 136. Gradual addition of electronic shells in the noble gases
halogen compounds. causes a decrease in their
(a) (i) and (ii) (b) (i), (ii) and (iii) (a) ionisation energy (b) atomic radius
(c) (ii) and (iii) (d) (i), (iii) and (iv) (c) boiling point (d) density
127. Which one of the following arrangements does not give 137. Which of the following noble gas is least polarisable?
the correct picture of the trends indicated against it ? (a) He (b) Xe (c) Ar (d) Ne
(i) F2 > Cl2 > Br2 > I2 : Oxidizing power 138. In which of the following groups, when He is placed, its all
(ii) F2 > Cl2 > Br2 > I2 : Electron gain enthalpy the properties are satisfied
(iii) F2 > Cl2 > Br2 > I2 : Bond dissociation energy (a) with alkali metals (b) with halogens
(iv) F2 > Cl2 > Br2 > I2 : Electronegativity. (c) with inert gases (d) None of these
(a) (ii) and (iv) (b) (i) and (iii) 139. The most abundant inert gas in the atmosphere is
(c) (ii) and (iii) (d) (ii), (iii) and (iv) (a) He (b) Ne (c) Ar (d) Kr
 EBD_7374
294 CHEMISTRY

140. The lowest boiling point of helium is due to its 158. XeF6 on complete hydrolysis gives
(a) inertness (a) Xe (b) XeO2 (c) XeO3 (d) XeO4
(b) gaseous nature 159. Shape of XeOF4 is
(c) high polarisability (a) octahedral (b) square pyramidal
(d) weak van der Waal’s forces between atoms (c) pyramidal (d) T-shaped
141. Which of the noble gas has highest polarisability? 160. Which is a planar molecule ?
(a) He (b) Ar (c) Kr (d) Xe (a) XeO4 (b) XeF4 (c) XeOF4 (d) XeO2F2
142. The noble gas which was discovered first in the sun and 161. Which of the following has sp3 hybridization ?
then on the earth (a) XeO3 (b) BCl3 (c) XeF4 (d) BBr3
(a) argon (b) xenon (c) neon (d) helium 162. Number of lon e pairs of electrons on Xe atoms
143. Which of the following noble gases has the highest positive XeF2, XeF4 and XeF6 molecules are respectively
electron gain enthalpy value? (a) 3, 2 and 1 (b) 4, 3 and 2
(a) Helium (b) Krypton (c) Argon (d) Neon (c) 2, 3 and 1 (d) 3, 2 and 0
144. Which inert gas show abnormal behaviour on liquefaction 163. Which statement about noble gases is not correct?
(a) Xe (b) He (c) Ar (d) Kr (a) Xe forms XeF6
145. Which has trigonal bipyramidal shape ? (b) Ar is used in electric bulbs
(a) XeOF4 (b) XeO3 (c) XeO3F2 (d) XeOF2 (c) Kr is obtained during radioactive disintegration
146. The correct order of solubility in water for He, Ne, Ar, Kr, (d) He has the lowest b.pt among all the noble gases
Xe is 164. Trigonal bipyramidal geometry is shown by :
(a) He > Ne > Ar > Kr > Xe (a) XeO3F2 (b) XeO3F2
(b) Ne > Ar > Kr > He > Xe (c) FXeOSO2F (d) [XeF8]2–
(c) Xe > Kr > Ar > Ne > He 165. The ease of liquefaction of noble gases increases in the
(d) Ar > Ne > He > Kr > Xe order
147. Which one of the following elements is most reactive ? (a) He < Ne < Ar < Kr < Xe
(a) He (b) Ne (c) Ar (d) Xe (b) Xe < Kr < Ne < Ar < He
148. Noble gases are group of elements which exhibit very (c) Kr < Xe < He < Ne < Ar
(a) high chemical activity (d) Ar < Kr < Xe < Ne < He
(b) low chemical activity 166. Argon is used
(c) minimum electronegativity (a) in filling airships
(d) much paramagnetic properties (b) to obtain low temperature
149. In XeF2, XeF4, XeF6 the number of lone pairs on Xe are (c) in high temperature welding
respectively (d) in radiotherapy for treatment of cancer
(a) 2, 3, 1 (b) 1, 2, 3 (c) 4, 1, 2 (d) 3, 2, 1. 167. Noble gases are used in discharge tubes to gives different
150. Total number of lone pair of electrons in XeOF4 is colours. Reddish orange glow is due to
(a) 0 (b) 1 (c) 2 (d) 3 (a) Ar (b) Ne (c) Xe (d) Kr
151. End-product of the hydrolysis of XeF6 is 168. Which one of the following statements regarding helium is
(a) XeF4O (b) XeF2O2 (c) XeO3 (d) XeO3– incorrect ?
152. Which one of the following reactions of xenon compounds (a) It is used to pr oduce an d sustain powerful
is not feasible? superconducting magnets.
(a) 3XeF4 + 6H 2 O ¾¾ ® 2Xe + XeO 3 +12HF +1.5O 2 (b) It is used as a cryogenic agent for carrying out
experiments at low temperatures.
(b) 2XeF2 + 2H 2 O ¾¾ ® 2Xe + 4HF + O 2 (c) It is used to fill gas balloons instead of hydrogen
(c) XeF6 + RbF ¾¾ ® Rb[XeF7 ] because it is lighter and non-inflammable.
(d) XeO3 + 6HF ¾¾ ® XeF6 + 3H 2 O (d) It is used in gas-cooled nuclear reactors.
153. Which of the following has maximum number of lone pairs 169. The coloured discharge tubes for advertisement mainly
associated with Xe ? contain
(a) XeF4 (b) XeF6 (c) XeF2 (d) XeO3 (a) xenon (b) helium (c) neon (d) argon
154. The shape of XeO2F2 molecule is 170. Sea divers go deep in the sea water with a mixture of which
(a) trigonal bipyramidal (b) square planar of the following gases
(c) tetrahedral (d) see-saw (a) O2 and He (b) O2 and Ar
155. XeF4 on partial hydrolysis produces (c) O2 and CO2 (d) CO2 and Ar
(a) XeF4 (b) XeOF2 (c) XeOF4 (d) XeO3 171. Which of the following is the life saving mixture for an
156. Which element out of He, Ar, Kr and Xe forms least number asthma patient ?
of compounds ? (a) Mixture of helium and oxygen
(a) He (b) Ar (c) Kr (d) Xe (b) Mixture of neon and oxygen
157. The element which has not yet been reacted with F2 is (c) Mixture of xenon and nitrogen
(a) Ar (b) Xe (c) Kr (d) Rn (d) Mixture of argon and oxygen
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 295

172. Which of the following statements are true? (a) Ar (b) Ne (c) Rn (d) He
(i) Only type of interactions between particles of noble 176. Match the columns
gases are due to weak dispersion forces. Column - I Column - II
(ii) Ionisation enthalpy of molecular oxygen is very close (A) XeF4 (p) Contains similar types
to that of xenon. of bonds
(iii) Hydrolysis of XeF6 is redox reaction. (B) XeOF4 (q) Contains maximum lone
(iv) Xenon fluorides are not reactive. pair
(a) (i) and (iii) (b) (i) and (ii) (C) XeF2 (r) Square pyramidal
(c) (ii) and (iii) (d) (iii) and (iv) geometry
173. Which of the following element has the property of diffusing (D) XeO3 (s) Contains one lone pair
through most commonly used laboratory materials such as (a) A – (p), B – (r, s), C – (p, q), D – (p, s)
rubber, glass or plastics. (b) A – (r, s), B – (p), C – (r, s), D – (p, s)
(a) Xe (b) Rn (c) He (d) Ar
(c) A – (p), B – (p, q), C – (r, s), D – (p, s)
174. Which of the following statements are correct?
(d) A – (p), B – (r, s), C – (p, s), D – (p, q)
(i) Natural abundance of noble gases is ~ 1% by volume
of which Ar is the major constituent. 177. What are the products formed in the reaction of xenon
hexafluoride with silicon dioxide ?
(ii) Noble gases have high positive values of electron gain
enthalpy. (a) XeSiO4 + HF (b) XeF2 + SiF4
(iii) Preparation of XeF2 requires F2 in excess amount. (c) XeOF4 + SiF4 (d) XeO3 + SiF2
(iv) Complete hydrolysis of all three XeF2, XeF4 and XeF6 178. XeO4 molecule is tetrahedral having :
gives Xe as one of product. (a) Two pp – dp bonds (b) One pp – dp bonds
(a) (i) and (iii) (b) (ii) and (iv)
(c) Four pp – dp bonds (d) Three pp – dp bonds
(c) (i) and (ii) (d) (ii) and (iii)
175. Which of the following is used to produce and sustain
powerful superconducting magnets to form an essential part
of NMR spectrometer ?

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (a) Carbon (b) Nitrogen
(c) Phosphorus (d) Boron
1. On addition of conc. H2SO4 to a chloride salt, colourless 5. Which of the following pairs of ions are isoelectronic and
fumes are evolved but in case of iodide salt, violet fumes isostructural?
come out. This is because
(a) H2SO4 reduces HI to I2 (b) HI is of violet colour (a) CO32 - , NO3- (b) ClO3- , CO32-
(c) HI gets oxidised to I2 (d) HI changes to HIO3
2. In qualitative analysis when H2S is passed through an (c) SO32- , NO3- (d) ClO3- , SO32 -
aqueous solution of salt acidified with dil. HCl, a black 6. Affinity for hydrogen decreases in the group from fluorine
precipitate is obtained. On boiling the precipitate with to iodine. Which of the halogen acids should have highest
dil. HNO3, it forms a solution of blue colour. Addition of bond dissociation enthalpy?
excess of aqueous solution of ammonia to this solution (a) HF (b) HCl (c) HBr (d) HI
gives ............ . 7. Bond dissociation enthalpy of E — H (E = element) bonds is
(a) deep blue precipitate of Cu(OH)2 given below. Which of the following compounds will acts
(b) deep blue solution of [Cu(NH3)4]2+ as strongest reducing agent?
(c) deep blue solution of Cu(NO3)2 Compound NH 3 PH 3 AsH 3 SbH 3
(d) deep blue solution of Cu(OH)2. Cu(NO3)2
-1
3. In a cyclotrimetaphosphoric acid molecule, how many single D diss ( E — H ) / kJ mol 389 322 297 255
and double bonds are present? (a) NH3 (b) PH3
(a) 3 double bonds; 9 single bonds (c) AsH3 (d) SbH3
(b) 6 double bonds; 6 single bonds 8. On heating with concentrated NaOH solution in an inert
(c) 3 double bonds; 12 single bonds atmosphere of CO2, white phosphorus gives a gas. Which
(d) Zero double bond; 12 single bonds of the following statement is incorrect about the gas?
4. Which of the following elements can be involved in (a) It is highly poisonous and has smell like rotten fish
pp – dp bonding? (b) It's solution in water decomposes in the presence of light
 EBD_7374
296 CHEMISTRY

(c) It is more basic than NH3 22. A black compound of manganese reacts with a halogen acid
(d) It is less basic than NH3 to give greenish yellow gas. When excess of this gas reacts
9. Which of the following acids forms three series of salts? with NH3 an unstable trihalide is formed. In this process the
(a) H3PO2 (b) H3BO3 oxidation state of nitrogen changes from ........... .
(c) H3PO4 (d) H3PO3 (a) – 3 to + 3 (b) – 3 to 0
10. Strong reducing behaviour of H3PO2 is due to (c) – 3 to + 5 (d) 0 to – 3
(a) low oxidation state of phosphorus 23. In the preparation of compounds of Xe, Bartlett had taken
-
(b) presence of two — OH groups and one P — H bond O+2 Pt F6 as a base compound. This is because
(c) presence of one — OH group and two P — H bonds (a) both O2 and Xe have same size.
(d) high electron gain enthalpy of phosphorus (b) both O2 and Xe have same electron gain enthalpy.
11. On heating lead nitrate forms oxides of nitrogen and lead. (c) both O2 and Xe have almost same ionisation enthalpy.
The oxides formed are ................. . (d) both Xe and O2 are gases.
(a) N2O, PbO (b) NO2, PbO 24. In solid state PCl5 is a ................. .
(c) NO, PbO (d) NO, PbO2 (a) covalent solid
12. Which of the following elements does not show allotropy? (b) octahedral structure
(a) Nitrogen (b) Bismuth (c) ionic solid with [PCl 6]+ octahedral and [PCl 4] –
(c) Antimony (d) Arsenic tetrahedral
13. Maximum covalency of nitrogen is ................... . (d) ionic solid with [PCl 4]+ tetrahedral and [PCl 6] –
(a) 3 (b) 5 (c) 4 (d) 6 octahedral
14. Which of the following statements is wrong? 25. Reduction potentials of some ions are given below. Arrange
(a) Single N — N bond is stronger than the single P — P them in decreasing order of oxidising power.
bond.
(b) PH3 can act as a ligand in the formation of coordination - - -
Ion ClO4 IO4 BrO4
compounds with transition elements.
Reduction potential
(c) NO2 is paramagnetic in nature. E° = 1.19V E° = 1.65V E° = 1.74V
(d) Covalency of nitrogen in N2O3 is four. E° / V
15. A brown ring is formed in the ring test for NO3- ion. It is due
to the formation of (a) ClO -4 > IO 4- < BrO 4-(b) IO 4- > BrO -4 < ClO 4-
(a) [Fe (H2O)5 (NO)]2+ (b) FeSO4 . NO2 (c) BrO 4- > IO-4 < ClO4- (d) BrO4- > ClO 4- < IO4-
(c) [Fe (H2O)4 (NO)2]2+ (d) FeSO4 . HNO3 26. Which of the following is isoelectronic pair?
16. Elements of group- 15 form compounds in +5 oxidation state.
(a) ICl2, ClO2 (b) BrO -2 , BrF2+
However, bismuth forms only one well characterised
compound in +5 oxidation state. The compound is (c) ClO2, BrF (d) CN–, O3
(a) Bi2O5 (b) BiF5 (c) BiCl5 (d) Bi2S5 Past Year MCQs
17. On heating ammonium dichromate and barium azide
separately we get 27. Acidity of diprotic acids in aqueous solutions increases in
(a) N2 in both the cases the order : [AIPMT 2014, C]
(b) N2 with ammonium dichromate and NO with barium (a) H2S < H2Se < H2Te (b) H2Se < H2S < H2Te
azide (c) H2Te < H2S < H2Se (d) H2Se < H2Te < H2S
(c) N2O with ammonium dichromate and N2 with barium 28. When Br2 is treated with aqueous solutions of
azide
NaF, NaCl and NaI separately [AIIMS 2014, S]
(d) N2O with ammonium dichromate and NO2 with barium
azide (a) F2, Cl2 and I2 are liberated
18. In the preparation of HNO3 , we get NO gas by catalytic (b) only F2 and Cl2 are liberated
oxidation of ammonia. The moles of NO produced by the (c) only I2 is liberated
oxidation of two moles of NH3 will be ................. . (d) only Cl2 is liberated
(a) 2 (b) 3 (c) 4 (d) 6
29. Among the following oxoacids, the correct decreasing order
19. The oxidation state of central atom in the anion of compound
of acid strength is: [JEE M 2014, C]
NaH2PO2 will be ................. .
(a) + 3 (b) + 5 (c) + 1 (d) – 3 (a) HOCl > HClO2 > HClO3 > HClO4
20. Which of the following is not tetrahedral in shape? (b) HClO4 > HOCl > HClO 2 > HClO3
(a) NH+4 (b) SiCl4
(c) SF4 (d) SO42– (c) HClO4 > HClO3 > HClO2 > HOCl
21. Hot conc. H2SO4 acts as moderately strong oxidising agent. (d) HClO2 > HClO 4 > HClO3 > HOCl
It oxidises both metals and non-metals. Which of the 30. Starch can be used as an indicator for the detection of traces
following element is oxidised by conc. H2SO4 into two of [BITSAT 2014, A]
gaseous products? (a) glucose in aqueous solution
(a) Cu (b) S (c) C (d) Zn (b) proteins in blood
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 297

(c) iodine in aqueous solution 40. Which among the following is the most reactive ?
(d) urea in blood [JEEM 2015, C]
31. Which of the following halogens exhibit only one oxidation (a) I2 (b) IC1 (c) Cl2 (d) Br2
state in its compounds ? [BITSAT 2014, C] 41. Assertion: Nitrogen and oxygen are the main components
(a) Bromine (b) Chlorine in the atmosphere but these do not react to form oxides of
(c) Fluorine (d) Iodine nitrogen.
32. Strong reducing behaviour of H3PO2 is due to Reason: The reaction between nitrogen and oxygen requires
[AIPMT 2015 RS, C] high temperature. [JEEM 2015, C]
(a) presence of one –OH group and two P–H bonds (a) The assertion is incorrect, but the reason is correct
(b) high electron gain enthalpy of phosphorus (b) Both the assertion and reason are incorrect
(c) high oxidation state of phosphorus (c) Both assertion and reason are correct, and the reason
(d) presence of two –OH groups and one P–H bond. is the correct explanation for the assertion
33. Nitrogen dioxide and sulphur dioxide have some properties (d) Both assertion and reason are correct, but the reason
in common. Which property is shown by one of these is not the correct explanation for the assertion
compounds, but not by the other? [AIPMT 2015, C] 42. Which one has the highest boiling point ? [JEE M 2015, C]
(a) is a reducing agent (a) Kr (b) Xe (c) He (d) Ne
(b) is soluble in water 43. Which of the following fluorides of xenon is impossible?
(c) is used as a food-preservative [BITSAT 2015, C]
(d) forms 'acid-rain' (a) XeF2 (b) XeF3 (c) XeF4 (d) XeF6
34. Which of the statements given below is incorrect?
44. Which of the following is a strong base?[BITSAT 2015, C]
[AIPMT 2015 RS, C]
(a) PH3 (b) AsH3 (c) NH3 (d) SbH3
(a) Cl2O7 is an anhydride of perchloric acid
45. Which is the correct statement for the given acids?
(b) O3 molecule is bent
[NEET 2016, C]
(c) ONF is isoelectronic with O2N–.
(d) OF2 is an oxide of fluorine (a) Phosphinic acid is a diprotic acid while phosphonic
35. The variation of the boiling point of the hydrogen halides is acid is a monoprotic acid
in the order HF > HI > HBr > HCl. [AIPMT 2015 RS, C] (b) Phosphinic acid is a monoprotic acid while phosphonic
What explains the higher boiling point of hydrogen fluoride? acid is a diprotic acid
(a) The electronegativity of fluorine is much higher than (c) Both are triprotic acids
for other elements in the group. (d) Both are diprotic acids
(b) There is strong hydrogen bonding between HF 46. The product obtained as a result of a reaction of nitrogen
molecules with CaC2 is [NEET 2016, C]
(c) The bond energy of HF molecules is greater than in (a) Ca(CN)2 (b) CaCN (c) CaCN3 (d) Ca2CN
other hydrogen halides. 47. Which one of the following orders is correct for the bond
(d) The effect of nuclear shielding is much reduced in dissociation enthalpy of halogen molecules?[NEET 2016, C]
fluorine which polarises the HF molecule. (a) I2 > Br2 > Cl2 > F2 (b) Cl2 > Br2 > F2 > I2
36. Which one of the following statements regarding helium is (c) Br2 > I2 > F2 > Cl2 (d) F2 > Cl2 > Br2 > I2
incorrect ? [AIIMS 2015, A] 48. Match the compounds given in column I with the
(a) It is used to pr oduce an d sustain powerful hybridisation and shape given in column II and mark the
superconducting magnets. correct option. [NEET 2016, C]
(b) It is used as a cryogenic agent for carrying out Column-I Column-II
experiments at low temperatures. 1. XeF6 (i) Distorted octahedral
(c) It is used to fill gas balloons instead of hydrogen 2. XeO3 (ii) Square planar
because it is lighter and non-inflammable. 3. XeOF4 (iii) Pyramidal
(d) It is used in gas-cooled nuclear reactors. 4. XeF4 (iv) Square pyramidal
37. Assertion : Silicones are hydrophobic in nature. Code :
[AIIMS 2015, C] 1 2 3 4
Reason : Si – O – Si linkages are moisture sensitive. (a) (i) (iii) (iv) (ii)
38. Regarding F– and Cl– which of the following statements is/ (b) (i) (ii) (iv) (iii)
are correct? [AIIMS 2015, C] (c) (iv) (iii) (i) (ii)
(i) Cl– can give up an electron more easily than F– (d) (iv) (i) (ii) (iii)
(ii) Cl– is a better reducing agent than F– 49. Assertion : SF6 cannot be hydrolysed but SF4 can be.
(iii) Cl– is smaller in size than F– Reason : Six F atoms in SF6 prevent the attack of H2O on
(iv) F– can be oxidized more readily than Cl– sulphur atom of SF6. [AIIMS 2016, C]
(a) (i) and (ii) (b) (i), (ii) and (iv) (a) If both assertion and reason are true and reason is the
(c) (iii) and (iv) (d) Only (i)
correct explanation of assertion.
39. The ionic radii (in Å) of N3–, O2– and F– are respectively :
(b) If both assertion and reason are true but reason is not
[JEEM 2015, C]
(a) 1.71, 1.40 and 1.36 (b) 1.71, 1.36 and 1.40 the correct explanation of assertion.
(c) 1.36, 1.40 and 1.71 (d) 1.36, 1.71 and 1.40 (c) If assertion is true but reason is false.
(d) If both assertion and reason are false.
 EBD_7374
298 CHEMISTRY

50. What is X and Y in the given reactions ? [AIIMS 2016, S] 60. Which of these doesn’t exist? [BITSAT 2017, C]
2X2 (g) + 2H2O (l) ® 4H+ (aq) + 4X– (aq) + O2 (g) (a) PH3 (b) PH5 (c) LuH3 (d) PF5
Y2 (g) + H2O (l) ® HY(aq) + HOY(aq) 61. Which of the following shows nitrogen with its increasing
(a) X = Cl , Y = F (b) X = Cl , Y = Br
order of oxidation number? [BITSAT 2017, C]
(c) X = F , Y = Cl (d) X = I , Y = F
51. The pair in which phosphorous atoms have a formal (a) NO < N2O < NO2 < NO3– < NH4+
oxidation state of + 3 is : [JEE M 2016, C] (b) NH4+ < N2O < NO2 < NO3– < NO
(a) Orthophosphorous and hypophosphoric acids
(b) Pyrophosphorous and pyrophosphoric acids (c) NH4+ < N2O < NO < NO2 < NO3–
(c) Orthophosphorous and pyrophosphorous acids (d) NH4+ < NO < N2O < NO2 < NO3–
(d) Pyrophosphorous and hypophosphoric acids
62. The correct order of N-compounds in its decreasing order
52. The by product of solvay-ammonia process is
[BITSAT 2016, A] of oxidation states is [NEET 2018, C]
(a) CO2 (b) NH3 (c) CaCl2 (d) CaCO3 (1) HNO3, NO, N2, NH4Cl
53. Laughing gas is [BITSAT 2016, A] (2) HNO3, NO, NH4Cl, N2
(a) nitrogen pentoxide(b) nitrous oxide (3) NH4Cl, N2, NO, HNO3
(c) nitrogen trioxide (d) nitric oxide (4) HNO3, NH4Cl, NO, N2
54. In which pair of ions both th e species contain 63. Which of the following statements is not true for halogens?
S – S bond? [NEET 2017, S]
[NEET 2018, C]
(a) S4 O62- ,S2 O32 - (b) S2 O72- ,S2 O82 - (1) All form monobasic oxyacids
(2) All are oxidizing agents
(c) S4 O62- ,S2 O72 - (d) S2 O72- ,S2 O32 -
(3) Chlorine has the highest electron-gain enthalpy
55. Match the interhalogen compounds of column-I with the (4) All but fluorine shows positive oxidation states
geometry in column II and assign the correct code.
[NEET 2017, C] 64. Which gas is used as cooling tube of MRI tube?
Column-I Column-II [AIIMS 2018, A]
1. XX' (i) T-shape (a) He (b) Ar (c) CO2 (d) N2
2. XX'3 (ii) Pentagonal bipyramidal 65. Assertion : Pb3O4 react with HNO3 and from PbO2
3. XX'5 (iii) Linear
Reason : Lead is stable in +4 oxidation state.
4. XX'7 (iv) Square pyramidal
(v) Tetrahedral [AIIMS 2018, C]
Code : (a) If both assertion and reason are true and reason is the
1 2 3 4 correct explanation of assertion.
(a) (iii) (i) (iv) (ii) (b) If both assertion and reason are true but reason is not
(b) (v) (iv) (iii) (ii) the correct explanation of assertion.
(c) (iv) (iii) (ii) (i) (c) If assertion is true but reason is false.
(d) (iii) (iv) (i) (ii) (d) If both assertion and reason are false.
56. Which of the following fluorides does not exist? 66. Which of the following has correct increasing order of
[AIIMS 2017, C] hydrolysis ? [AIIMS 2018, C]
(a) NF5 (b) PF5
(c) AsF 5 (d) SbF5 (a) CCl4 < MgCl2 < AlCl3 < SiCl4 < PCl5
57. Which of the following are peroxoacids of sulphur? (b) PCl5 < MgCl2 < AlCl3 < SiCl4 < CCl4
[AIIMS 2017, S] (c) PCl5 < SiCl2 < MgCl2 < AlCl3 < CCl4
(a) H2SO5 and H2S2O8 (d) none of these
(b) H2SO5 and H2S2O7
(c) H2S2O7 and H2S2O8 67. The compound that does not produce nitrogen gas by the
(d) H2S2O6 and H2S2O7 thermal decomposition is : [JEE M 2018, A]
58. Assertion : HClO4 is a stronger acid than HClO3. (a) Ba(N3)2 (b) (NH4)2Cr2O7
[AIIMS 2017, C] (c) NH4NO2 (d) (NH4)2SO4
Reason : Oxidation state of Cl in HClO4 is +VII and in HClO3 +V. 68. Which of the following is not a member of chalcogens?
(a) If both assertion and reason are true and reason is the [BITSAT 2018, C]
correct explanation of assertion.
(a) O (b) S (c) Se (d) Po
(b) If both assertion and reason are true but reason is not
69. Pick out the wrong statement. [BITSAT 2018, C]
the correct explanation of assertion.
(c) If assertion is true but reason is false. (a) Nitrogen has the ability to form pp-pp bonds with itself.
(d) If both assertion and reason are false. (b) Bismuth forms metallic bonds in elemental state.
59. The products obtained when chlorine gas reacts with cold (c) Catenation tendency is higher in nitrogen when
and dilute aqueous NaOH are : [JEE M 2017, S] compared with other elements of the same group.
(a) ClO– and ClO3– (b) ClO2– and ClO3– (d) Nitrogen has higher first ionisation enthalpy when
(c) Cl– and ClO– (d) Cl– and ClO2– compared with other elements of the same group.
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 299

Exercise 3 : Try If You Can

1. NH 4 ClO4 + HNO 3 (dil.) ¾¾
® HClO 4 + [X] 9. A certain compound (X) when treated with copper sulphate,
[X] ¾¾
D
® Y(g)
solution yields a brown precipitate. On adding hypo
solution the precipitate turns white. The compound is
[X] and [Y] are respectively –
(a) K2CrO3 (b) KI (c) KBr (d) K3PO4
(a) NH4NO3 & N2O (b) NH4NO2 & N2
(c) HNO4 & O2 (d) None of these 10. MF + XeF4 ¾¾ (
® ' A ' M + = Alkali metal cation )
2. When SO2 gas is passed through an acidified solution of The state of hybridisation of the central atom in 'A' and
K2Cr2O7 shape of the species are:
(a) the solution becomes blue (a) sp3d, TBP
(b) the solution becomes colourless (b) sp3d3, distorted octahedral
(c) SO2 is reduced (c) sp3d3, pentagonal planar
(d) green Cr2(SO4)3 is formed (d) No compound formed at all
3. A metal ‘M’ reacts with nitrogen gas to give ‘M3N’. ‘M3N’ 11. In the solid state, SO3 may have structure
on heating at high temperature gives back ‘M’ and on O O
reaction with water produces a gas ‘B’. Gas ‘B’ reacts with S
aqueous solution of CuSO4 to form a deep blue compound.
‘M’ and ‘B’ respectively are : O O
(a) O O
(a) Li and NH3 (b) Ba and N2 S S
(c) Na and NH3 (d) Al and N2 O O O
4. Ordinary strong solution of HCl, HNO3 and H2SO4 contains
roughly O O O
(a) 1/5, 2/3 and 3/3 fractions of pure acid and water S S S
(b)
respectively
O O O O O O
(b) 2/3, 1/5 and 3/3 fractions of pure acid and water
respectively (c) a & b both
(c) 2/3, 3/3 and 1/5 fractions of pure acid and water (d) None of these
respectively 12. A certain salt (X) gives the following tests :
(d) None (i) Its aqueous solution is alkaline to litmus.
5. When an inorganic compound reacts with SO2 in aqueous
(ii) On strongly heating it swells to give a glassy bead
medium produces (A). (A) on reaction with Na2CO3 gives
the compound (B) which with sulphur give a substance (C) (iii) When concentrated sulphuric acid is added to a hot
used in photography. The compound (C) is concentrated solution of (X), crystals of H3BO3
(a) Na2S2O3 (b) Na2SO4 (c) Na2S (d) Na2S2O7 separate out. Identify the colour of these crystals.
6. The correct order of S—S bond length in following (a) White (b) Blue (c) Brown (d) Violet
oxyanions is: 13. All the three atoms of ozone are used up when it reacts
(I) S2 O24- (II) S2 O52- (III) S2 O62- with
(a) I > II > III (b) I > III > II (a) H2O2 (b) PbS (c) KI (d) SO2
(c) III > II > I (d) III > I > II 14. P2H4 can be removed from phosphine containing traces of
7. A yellow metallic powder when burnt in a stream of fluorine it :
produced a colourless, thermally stable and chemically inert (a) by passing impure PH3 gas through a freezing mixture
gas ‘X’. A gas ‘Y’, which is colourless and consists of the (b) by passing the impure PH3 gas through HI and then its
same elements as are present in gas ‘X’, is obtained by treatment with KOH (aq)
heating together sulphur dichloride and sodium fluoride.
(c) by both (a) and (b)
Gases ‘X’ and ‘Y’ respectively are
(a) SF4 and SF6 (b) SF4 and S2F2 (d) by none of these
(c) SF6 and SF4 (d) None of these 15. Amatol that is used as an explosive has the composition
8. A greenish yellow gas reacts with an alkali metal hydroxide (a) 80% of NH4NO3 + 20% TNT
to form a halate which can be used in fireworks and safety (b) 20% of NH4NO3 + 80% TNT
matches. The gas and the halate are
(c) 30% of NH4NO2 + 20% TNT
(a) Br2, KBrO3 (b) Cl2, KClO3
(c) I2, NaIO3 (d) I2, KIO3 (d) 20% of NH4NO2 +80% TNT
 EBD_7374
300 CHEMISTRY

ANSW ER KEYS
Exercise 1 : Topic-wise MCQs
1 (d) 19 (a) 37 (d) 55 (b) 73 (b) 91 (c) 109 (b) 127 (c) 145 (b) 163 (c)
2 (b) 20 (d) 38 (a) 56 (b) 74 (a) 92 (c) 110 (c) 128 (c) 146 (c) 164 (b)
3 (a) 21 (d) 39 (d) 57 (c) 75 (d) 93 (c) 111 (d) 129 (c) 147 (d) 165 (a)
4 (d) 22 (c) 40 (d) 58 (b) 76 (b) 94 (c) 112 (d) 130 (a) 148 (b) 166 (c)
5 (d) 23 (b) 41 (b) 59 (b) 77 (c) 95 (c) 113 (b) 131 (c) 149 (d) 167 (b)
6 (a) 24 (b) 42 (b) 60 (b) 78 (b) 96 (d) 114 (a) 132 (d) 150 (b) 168 (c)
7 (d) 25 (a) 43 (c) 61 (b) 79 (d) 97 (a) 115 (d) 133 (b) 151 (c) 169 (c)
8 (a) 26 (c) 44 (c) 62 (a) 80 (a) 98 (d) 116 (d) 134 (d) 152 (d) 170 (a)
9 (c) 27 (a) 45 (d) 63 (a) 81 (c) 99 (a) 117 (d) 135 (b) 153 (c) 171 (a)
10 (c) 28 (b) 46 (b) 64 (a) 82 (c) 100 (c) 118 (d) 136 (a) 154 (d) 172 (b)
11 (d) 29 (d) 47 (b) 65 (c) 83 (a) 101 (d) 119 (d) 137 (a) 155 (b) 173 (c)
12 (b) 30 (c) 48 (c) 66 (b) 84 (b) 102 (a) 120 (d) 138 (c) 156 (a) 174 (c)
13 (d) 31 (d) 49 (c) 67 (c) 85 (b) 103 (d) 121 (c) 139 (c) 157 (a) 175 (d)
14 (a) 32 (d) 50 (b) 68 (a) 86 (b) 104 (b) 122 (d) 140 (d) 158 (c) 176 (a)
15 (a) 33 (a) 51 (d) 69 (a) 87 (a) 105 (b) 123 (b) 141 (d) 159 (b) 177 (c)
16 (c) 34 (a) 52 (a) 70 (b) 88 (d) 106 (d) 124 (c) 142 (d) 160 (b) 178 (c)
17 (b) 35 (b) 53 (b) 71 (a) 89 (d) 107 (b) 125 (b) 143 (d) 161 (a)
18 (c) 36 (c) 54 (a) 72 (a) 90 (c) 108 (d) 126 (d) 144 (b) 162 (a)
Exercis e 2 : Exemplar & Pas t Year MCQs
1 (c) 8 (c) 15 (a) 22 (a) 29 (c) 36 (c) 43 (b) 50 (c) 57 (a) 64 (a)
2 (b) 9 (c) 16 (b) 23 (c) 30 (c) 37 (b) 44 (c) 51 (c) 58 (b) 65 (c)
3 (c) 10 (c) 17 (a) 24 (d) 31 (c) 38 (d) 45 (b) 52 (c) 59 (c) 66 (a)
4 (c) 11 (b) 18 (a) 25 (c) 32 (a) 39 (a) 46 (a) 53 (b) 60 (b) 67 (d)
5 (a) 12 (a) 19 (c) 26 (b) 33 (c) 40 (b) 47 (b) 54 (a) 61 (c) 68 (d)
6 (a) 13 (c) 20 (c) 27 (a) 34 (d) 41 (c) 48 (a) 55 (a) 62 (a) 69 (c)
7 (d) 14 (a) 21 (c) 28 (c) 35 (b) 42 (b) 49 (a) 56 (a) 63 (d)
Exercis e 3 : Try If You Can
1 (a) 3 (a) 5 (a) 7 (c) 9 (b) 11 (a) 13 (d) 15 (a)
2 (d) 4 (a) 6 (a) 8 (b) 10 (c) 12 (a) 14 (c)
 22 Chapter
THE d-AND f–BLOCK
ELEMENTS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

8
7
6
AIPMT /NEET
5
Number of Questions

AIIMS
4
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Properties of transition
AIIMS 3 elements, Lanthanoid 3.8/5 7.8
JEE Main 2 contraction
BITSAT 2
 EBD_7374
302 CHEMISTRY
THE d-AND f–BLOCK ELEMENTS 303
 EBD_7374
304 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: General Properties and Electronic 14. In first transition series, the melting point of Mn is low
because
Configuration of d–Block Elements (a) due to d10 configuration, metallic bonds are strong
1. The transition elements have a general electronic configu- (b) due to d7 configuration, metallic bonds are weak
ration (c) due to d5 configuration, metallic bonds are weak
(d) None of these
(a) ns 2, np 6, nd 1 -10
15. The common oxidation states of Ti are
(b) ( n - 1) d 1-10, ns 0 - 2, np 0 - 6 (a) + 2 and + 3 (b) + 3 and + 4
(c) (n - 1) d 1-10, ns1- 2 (c) – 3 and – 4 (d) + 2, + 3 and + 4
16. Maximum oxidation state is shown by
(d) n d 1-10, ns1- 2 (a) Os (b) Mn (c) Co (d) Cr
2. Number of unpaired electrons in Ni2+(Z=28) is 17. Which of the following pairs has the same size?
(a) 4 (b) 2 (c) 6 (d) 8 (a) Fe2+, Ni2+ (b) Zr4+, Ti4+
3. Which of the following element is not a member of transition (c) Zr 4+, Hf 4+ (d) Zn 2+, Hf 4+
elements ? 18. For the four successive transition elements (Cr, Mn, Fe and
(a) Zn (b) Pt (c) Ce (d) Mo Co), the stability of +2 oxidation state will be there in which
4. The number of unpaired electrons in gaseous species of of the following order?
Mn3+, Cr 3+ and V3+ respectively are. (a) Mn > Fe > Cr > Co (b) Fe > Mn > Co > Cr
(a) 4, 3 and 2 (b) 3, 3 and 2 (c) Co > Mn > Fe > Cr (d) Cr > Mn > Co > Fe
(c) 4, 3 and 2 (d) 3, 3 and 3 19. Iron exhibits +2 and + 3 oxidation states. Which of the
5. The first element in the 3d-transition series is following statements about iron is incorrect ?
(a) Sc (b) Ti (c) V (d) Ca (a) Ferrous oxide is more basic in nature than the ferric oxide.
6. Which of the following has more unpaired d-electrons? (b) Ferrous compounds are relatively more ionic than the
(a) Zn+ (b) Fe2+ (c) Ni+ (d) Cu+ corresponding ferric compounds.
7. Correct electronic configuration of Cr (Z = 24) is (c) Ferrous compounds are less volatile than the
(a) 1s2 2s2 2p6 3s2 3p6 3d 7 4s1 corresponding ferric compounds.
(b) 1s2 2s2 2p6 3s2 3p6 3d 5 4s1 (d) Ferrous compounds are more easily hydrolysed than
(c) 1s2 2s2 2p6 3s2 3p6 3d 7 4s2 the corresponding ferric compounds.
(d) 1s2 2s2 2p6 3s2 3p6 3d 6 4s2 20. Of the following outer electronic configurations of atoms, the
8. Which one of the following ions has electronic configuration highest oxidation state is achieved by which one of them?
[Ar] 3d 6 ? (a) (n – 1)d 3 ns2 (b) (n – 1)d 5 ns1
8
(c) (n – 1)d ns 2 (d) (n – 1)d 5 ns2
(a) Ni3+ (b) Mn 3+ (c) Fe3+ (d) Co3+
(At. Nos. Mn = 25, Fe = 26, Co = 27, Ni = 28) 21. For d block elements the first ionization potential is of the
9. (n–1) d10 ns2 is the general electronic configuration of order
(a) Fe, Co, Ni (b) Cu, Ag, Au (a) Zn > Fe > Cu > Cr (b) Sc = Ti < V = Cr
(c) Zn, Cd, Hg (d) Se, Y, La (c) Zn < Cu < Ni < Co (d) V > Cr > Mn > Fe
10. Which one of the following is an example of non-typical 22. Which of the following does not represent the correct order
transition elements ? of the properties indicated ?
(a) Li, K, Na (b) Be, Al, Pb (a) Ni2+ > Cr2+ > Fe2+ > Mn2+ (size)
(c) Zn, Cd, Hg (d) Ba, Ga, Sr. (b) Sc > Ti > Cr > Mn (size)
11. Which of the following has the maximum number of unpaired (c) Mn2+ > Ni2+ < Co2+ <Fe2+ (unpaired electron)
electrons? (d) Fe2+ > Co2+ > Ni2+ > Cu2+ (unpaired electron)
23. Zinc and mercury do not show variable valency like d-block
(a) Ti2+ (b) Fe2+ (c) Cr+ (d) Cu+
7+ elements because
12. The no. of unpaired electrons in Mn ions
(a) they are soft
(At. no. of Mn = 25) is
(b) their d-shells are complete
(a) 0 (b) 1 (c) 2 (d) 3
(c) they have only two electrons in the outermost subshell
13. Which of the following species is/are paramagnetic?
(d) their d-shells are incomplete
Fe2+, Zn0, Hg2+, Ti4+
24. Which of the following transition element shows the
(a) Fe2+ only (b) Zn 0 and Ti4+
highest oxidation state ?
(c) Fe2+ and Hg2+ (d) Zn 0 and Hg2+ (a) Mn (b) Fe (c) V (d) Cr
THE d-AND f–BLOCK ELEMENTS 305

25. Which one of the following transition elements does not Sc = 21, Fe = 26, Ti = 22, Mn = 25)
exhibit variable oxidation state? (a) Sc3+ (b) Fe2+ (c) Ti 3+ (d) Mn 2+
(a) Ni (b) Cu (c) Fe (d) Sc 36. Transition elements form coloured ions due to
26. Metallic radii of some transition elements are given below. (a) d-d transition (b) fully filled d-orbitals
Which of these elements will have highest density ? (c) smaller atomic radii (d) availability of s-electrons
Element : Fe Co Ni Cu 37. The catalytic activity of transition metals and their
Metallic radii/pm: 126 125 125 128 compounds is mainly due to
(a) Fe (b) Ni (c) Co (d) Cu (a) their magnetic behaviour
27. Which of the following statements is incorrect? (b) their unfilled d-orbitals
(a) Zn,Cd and Hg due to presence of completely filled (c) their ability to adopt variable oxidation state
d-orbitals [(n–1)d10ns2] are not studied along with (d) their chemical reactivity
other transition metals. 38. Which group contains coloured ions out of
(b) Zn, Cd and Hg have low m.p and are comparitively
(i) Cu 2+ (ii) Ti 4+ (iii) Co 2+ (iv) Fe 2 +
softer than other transition metals.
(c) Metallic bond made by elements with d 5 configuration (a) (i), (ii), (iii), (iv) (b) (i), (iii), (iv)
is stronger as compared to metalic bond made by (c) (ii), (iii) (d) (i), (ii)
elements with d 3 configuration. 39. If a non metal is added to the interstital sites of a metal, then
(d) Metals of 5d series forms strong metallic bonds as the metal becomes
compared with metals of 3d series. (a) softer (b) less tensile
28. Which of the following is incorrect? (c) less malleable (d) more ductile
(a) Mn shows oxidation state of +7 in MnF7 40. Which of the following ion(s) is/are oxidising in nature?
(b) Fe and Co shows +3 oxidation state in FeX3 and CoF3.
(c) V shows oxidation state of + 5 in VF5.
(i) (°
V2+ EM 2+ / M = -1.18 )
(d) Cu does not shows +2 oxidation state with I–.
29. Which one of the following ions is the most stable in (ii) Mn3+ E° ( M3 + / M 2 +
= +1.57 )
aqueous solution?
(a) V3+ (b) Ti3+ (c) Mn 3+ (d) Cr3+ (iii) Cr 2+ E° ( M2+ / M
= -0.91 )
(At. no. Ti = 22, V = 23, Cr = 24, Mn = 25)
30. Which one of the following does not correctly represent (a) (i) and (iii) (b) only (ii)
the correct order of the property indicated against it? (c) (ii) and (iii) (d) only (iii)
(a) Ti < V < Cr < Mn : increasing number of oxidation 41. Which of the following transition metal ion is colourless in
states aqueous solution?
(a) Ti4+ (b) Zn 2+
(b) Ti3+ < V3+ < Cr3+ < Mn3+ : increasing magnetic moment 4+
(c) V (d) Both (a) and (b)
(c) Ti < V < Cr < Mn : increasing melting points
(d) Ti < V < Mn < Cr : increasing 2nd ionization enthalpy 42. Match the columns
31. Which of the following ions has the maximum magnetic Column-I Column-II
moment? (Ion) (Mcalculated)
(a) Mn 2+ (b) Fe2+ (c) Ti3+ (d) Cr2+. (A) Ti2+ (p) 2.84
(B) Zn2+ (q) 5.92
32. Four successive members of the first row transition elements
(C) Mn 2+ (r) 0
are listed below with atomic numbers. Which one of them is
(D) Sc3+ (s) 4.90
expected to have the highest E° value ? (a) A – (s), B – (p), C – (q), D – (r).
M3+ / M 2+ (b) A – (r), B – (p), C – (q), D – (s).
(a) Cr(Z = 24) (b) Mn(Z = 25) (c) A – (p), B – (r), C – (q), D – (s).
(c) Fe(Z = 26) (d) Co(Z = 27) (d) A – (p), B – (s), C – (q), D – (r).
33. A compound of a metal ion M x + ( Z = 24 ) has a spin 43. Which of the following transition metal acts as a catalysis
in the reaction between iodide and persulphate ion?
only magnetic moment of 15 Bohr Magnetons. The (a) Fe2+ (b) Fe3+
number of unpaired electrons in the compound are (c) Ni2+ (d) Both (a) and (c)
(a) 2 (b) 4 (c) 5 (d) 3 44. A series-1 metal ion , M(II) aqueous solution react with the
34. Transition elements show magnetic moment due to spin KI to form iodine and a precipitate is formed, this M(II) can
and orbital motion of electrons. Which of the following be:
metallic ions have almost same spin only magnetic moment ? (a) Zn2+ (b) Mn 2+ (c) Cu2+ (d) Ni2+
(i) Co2+ (ii) Cr2+ (iii) Mn 2+ (iv) Cr3+ 45. Which of the following ions will exhibit colour in aqueous
(a) (i) and (iii) (b) (i) and (iv) solutions?
(c) (ii) and (iii) (d) (ii) and (iv)
(a) La 3+ (Z = 57) (b) Ti3+ (Z = 22)
35. The aqueous solution containing which one of the
following ions will be colourless? (Atomic number: (c) Lu 3+ (Z = 71) (d) Sc3+ (Z = 21)
 EBD_7374
306 CHEMISTRY

46. Mark the correct statement(s). (a) VO2 + ; VO2+ < TiO 2 + < CrO 24-
(i) Manganese exhibits +7 oxidation state +
(ii) Zinc forms coloured ions (b) VO 2+ ; TiO 2 < VO + 2-
2 < CrO 4
(iii) [CoF6]3– is diamagnetic (c) CrO 24 - < TiO 2 + < VO+2 < VO2 +
(iv) Sc forms +4 oxidation state
(v) Zn exhibits only +2 oxidation state (d) TiO 2 + < VO 2+ ; VO +2 < CrO 42-
(a) (i) and (ii) (b) (i) and (v) 55. In the form of dichromate, Cr (VI) is a strong oxidising agent
(c) (ii) and (iv) (d) (iii) and (iv) in acidic medium but Mo (VI) in MoO3 and W (VI) in WO3
47. Which of the following statements are correct ? are not because ____________ .
(i) The maximum oxidation state of Mn with the oxygen is (i) Cr (VI) is more stable than Mo(VI) and W (VI).
+VII while with fluorine is +IV. (ii) Mo (VI) and W(VI) are more stable than Cr(VI).
(ii) Fluorine is more oxidizing in nature than oxygen. (iii) Higher oxidation states of heavier members of group-6
(iii) Fluorine exhibit an oxidation state of –1. of transition series are more stable.
(iv) Seven fluorine cannot be accommodated around Mn. (iv) Lower oxidation states of heavier members of group-6
(a) (i), (ii) and (iii) (b) (ii), (iii) and (iv) of transition series are more stable.
(c) (i) and (iv) (d) (i), (ii), (iii) and (iv) (a) (i) and (ii) (b) (ii) and (iii)
48. Among the following series of transition metal ions, the one (c) (i) and (iv) (d) (ii) and (iv)
where all metal ions have 3d2 electronic configuration is 56. K2Cr2O7 on heating with aqueous NaOH gives
(At. nos. Ti = 22; V = 23; Cr = 24; Mn = 25) (a) CrO 24- (b) Cr(OH)3 (c) Cr2O 72- (d) Cr(OH)2
(a) Ti 3+ , V 2+ , Cr 3+ , Mn 4+ (b) Ti + , V 4+ , Cr 6+ , Mn 7+ 57. CrO3 dissolves in aqueous NaOH to give
(a) Cr2O72– (b) CrO42– (c) Cr(OH)3 (d) Cr(OH)2
(c) Ti 4+ , V 3+ , Cr 2+ , Mn 3+ (d) Ti 2+ , V 3+ , Cr 4+ , Mn 5+ 58. The oxidation state of chromium in the final product formed
49. Which one of the following transition metal ions shows by the reaction between KI and acidified potassium
magnetic moment of 5.92 BM? dichromate solution is
(a) Mn 2+ (b) Ti3+ (c) Cr3+ (d) Cu2+ (a) + 3 (b) + 2 (c) + 6 (d) + 4
50. In which of the following pairs both the ions are coloured in 59. The bonds present in the structure of dichromate ion are
aqueous solutions ? (a) four equivalent Cr – O bonds only
(a) Sc3+, Ti3+ (b) Sc3+, Co2+ (b) six equivalent Cr – O bonds and one O – O bond
2+
(c) Ni , Cu + (d) Ni2+, Ti3+ (c) six equivalent Cr – O bonds and one Cr – Cr bond
(At. no. : Sc = 21, Ti = 22, Ni = 28, Cu = 29, Co = 27) (d) six equivalent Cr – O bonds and one Cr – O – Cr bond
51. For the ions Zn 2+, Ni2+ and Cr3+ which among the following 60. Potassium dichromate when heated with concentrated
statements is correct? sulphuric acid and a soluble chloride, gives brown-red
(atomic number of Zn = 30, Ni = 28 and Cr = 24) vapours of
(a) All these are colourless (a) CrO3 (b) CrCl3 (c) CrO2Cl2 (d) Cr2O3
(b) All these are coloured 61. The acidic, basic or amphoteric nature of Mn 2O7, V2O5 and
(c) Only Ni2+ is coloured and Zn2+ and Cr3+ are colourless CrO are respectively
(d) Only Zn 2+ is colourless and Ni2+ and Cr3+ are coloured (a) acidic, acidic and basic
52. Cuprous ion is colourless while cupric ion is coloured (b) basic, amphoteric and acidic
because (c) acidic, amphoteric and basic
(a) both have half filled p-and d-orbitals (d) acidic, basic and amphoteric
(b) cuprous ion has incomplete d-orbital and cupric ion 62. Which of the following oxides of Cr is amphoteric
has a complete d-orbital (a) Cr O2 (b) Cr2O3 (c) CrO5 (d) CrO3
(c) both have unpaired electrons in the d-orbitals 63. In neutral or faintly alkaline medium, thiosulphate is
(d) cuprous ion has complete d-orbital and cupric ion has quantitatively oxidized by KMnO4 to
an imcomplete d-orbital. (a) SO32– (b) SO42– (c) SO2 (d) SO52–
53. The colour of the following ions V2+, V3+, V4+, Fe2+, Fe3+ are 64. KMnO4 can be prepared from K2MnO4 as per the reaction:
respectively 2MnO24 - + MnO2 + 4OH -
3MnO 24 - + 2H 2 O
(a) green, violet, blue, green, yellow
The reaction can go to completion by removing OH– ions
(b) yellow, green, violet, green, blue
by adding.
(c) violet, green, yellow, green, blue
(a) KOH (b) CO2 (c) SO2 (d) HCl
(d) yellow, green, blue, green, violet
65. In the laboratory, manganese (II) salt is oxidised to
Topic 2: Some Important Compounds of Transition Elements permanganate ion in aqueous solution by
(a) hydrogen peroxide (b) conc. nitric acid
54. Choose the correct increasing order of the oxidation state (c) peroxy disulphate (d) dichromate
of the central metal atom in the following oxoanions. 66. The starting material for the manufacture of KMnO4 is
(a) pyrolusite (b) manganite
VO+2 , VO2 + , TiO 2 + , CrO 24-
(c) magnatite (d) haematite
THE d-AND f–BLOCK ELEMENTS 307

67. If KMnO4 is reduced by oxalic acid in an acidic medium then (a) (i) and (iii) (b) (i) and (iv)
oxidation number of Mn changes from (c) (iv) only (d) (ii) and (iv)
(a) 4 to 2 (b) 6 to 4 (c) +7 to +2 (d) 7 to 4 75. Arrange the following increasing order of acidic character?
68. Match the columns Mn2O7(A), Mn2O3(B), MnO(C)?
Column-I Column -II (a) C, A, B (b) A, C, B (c) B, A, C (d) C, B, A
(A) Metal of the 3d-series (p) Manganese 76. Solution of oxalate is colourless. It is made acidic by adding
which does not form excess of H+, then titrated with KMnO4. Now at a moment
MO type oxide. if someone has added large amount of KMnO4, in it then
(B) Metal of the 3d-series (q) Vanadium no. of possible products are
which forms most (a) CO2, Mn2+, H2O (b) CO2, MnO2, H2O
covalent oxide. (c) MnO2, H2O, CO2 (d) CO2, MnO2, H2O, Mn2+
(C) Metal of the 3d-series (r) Scandium 77. Dichromate [Cr(VI) ] is a strong oxidizing agent whereas
which forms the Mo(VI) and W(VI) are found to be not. This is due to
amphoteric oxide. (a) Lanthanoid contraction
(a) A – (p), B – (r), C – (q) (b) A – (r), B – (p), C – (q) (b) Down the group metallic character increases
(c) A – (r), B – (q), C – (p) (d) A – (q), B – (p), C – (r) (c) Down the group metallic character decreases
69. Match the columns (d) Both (a) and (b)
Column-I Column-II 78. Which of the following conversions can be carried out by
(A) Compound formed when (p) acidified both acidified K2Cr2O4 and acidified KMnO4?
yellow CrO24 - is acidified. (i) Fe2+ ® Fe3+ + e– (ii) I– ®
MnO-4
(iii) I ® I2
– (iv) H2S ® S
(B) reagent oxidises Fe2+ to Fe3+ (q) Cr2 O72- (a) (i) and (iii) (b) (ii) and (iv)
(C) Compound produced when (r)
K2MnO4 (c) (i), (iii) and (iv) (d) (i), (ii) and (iii)
MnO2 is fused with KNO3
(D) Compound having dark (s) KMnO4 Topic 3: The Lanthanoids and Actinoids
purple crystals isostructural 79. The lanthanoide contraction is responsible for the fact that
with KClO4 (a) Zr and Y have about the same radius
(a) A – (q),B – (p), C – (r), D – (s) (b) Zr and Nb have similar oxidation state
(a) A – (p),B – (q), C – (r), D – (s) (c) Zr and Hf have about the same radius
(a) A – (q),B – (r), C – (p), D – (s) (d) Zr and Zn have the same oxidation state
(a) A – (q),B – (p), C – (s), D – (r) (Atomic numbers : Zr = 40, Y = 39, Nb = 41, Hf = 72, Zn = 30)
70. Acidified K2Cr2O7 solution turns green when Na2SO3 is 80. Which of the following factors may be regarded as the main
added to it. This is due to the formation of : cause of lanthanoide contraction?
(a) Cr2(SO4)3 (b) CrO42– (a) Greater shielding of 5d electrons by 4f electrons
(c) Cr2(SO3)3 (d) CrSO4 (b) Poorer shielding of 5d electrons by 4f electrons
71. Which of the statements is not true? (c) Effective shielding of one of 4f electrons by another in
(a) On passing H2S through acidified K2Cr2O7 solution, a the subshell
milky colour is observed. (d) Poor shielding of one of 4f electron by another in the subshell
(b) Na2Cr2O7 is preferred over K2Cr2O7 in volumetric 81. Lanthanoid which has the smallest size in +3 state is
analysis. (a) Tb (b) Er (c) Ce (d) Lu
(c) K2Cr2O7 solution in acidic medium is orange. 82. Lanthanum is grouped with f-block elements because
(d) K2Cr2O7 solution becomes yellow on increasing the (a) it has partially filled f-orbitals
pH beyond 7. (b) it is just before Ce in the periodic table
72. Which one of the following is an amphoteric oxide ? (c) it has both partially filled f and d-orbitals
(i) Mn 2O7 (ii) CrO (iii) V2O4 (iv) Cr2O3 (d) properties of lanthanum are very similar to the elements
(a) (i) and (ii) (b) (ii), (iii) and (iv) of f-block
(c) (iii) and (iv) (d) (ii) and (iv) 83. A reduction in atomic size with increase in atomic number is
73. Identify the product and its colour when MnO2 is fused a characteristic of elements of
with solid KOH in the presence of O2. (a) high atomic masses (b) d-block
(a) KMnO4, purple (b) K2MnO4, dark green (c) f-block (d) radioactive series
(c) MnO, colourless (d) Mn2O3, brown 84. Which of the following oxidation states is the most common
74. Which of the following oxidising reaction of KMnO4 occurs among the lanthanoids?
in acidic medium? (a) 3 (b) 4 (c) 2 (d) 5
(i) Fe2+ (green) is converted to Fe3+ (yellow). 85. Identify the incorrect statement among the following:
(ii) Iodide is converted to iodate. (a) 4f and 5f orbitals are equally shielded.
(iii) Thiosulphate oxidised to sulphate. (b) d-Block elements show irregular and erratic chemical
(iv) Nitrite is oxidised to nitrate. properties among themselves.
 EBD_7374
308 CHEMISTRY

(c) La and Lu have partially filled d-orbitals and no other (c) A – (s), B – (r), C – (q), D – (p)
partially filled orbitals. (d) A – (r), B – (s), C – (q), D – (p)
(d) The chemistry of various lanthanoids is very similar. 94. The +3 ion of which one of the following has half filled 4f
86. In context of the lanthanoids, which of the following subshell?
statements is not correct? (a) La (b) Lu (c) Gd (d) Ac
(a) There is a gradual decrease in the radii of the members 95. Although + 3 is the characteristic oxidation state for
with increasing atomic number in the series. lanthanoids but cerium also shows + 4 oxidation state
(b) All the members exhibit +3 oxidation state. because _________ .
(c) Because of similar properties the separation of (i) it has variable ionisation enthalpy
lanthanoids is not easy. (ii) it has a tendency to attain noble gas configuration
(d) Availability of 4f electrons results in the formation of (iii) it has a tendency to attain f 0 configuration
compounds in +4 state for all the members of the series. (iv) it resembles Pb4+
87. The correct order of ionic radii of Y3+, La3+, Eu3+ and Lu3+ is (a) (ii) and (iii) (b) (i) and (iv)
(a) La 3+ < Eu 3+ < Lu 3+ < Y 3+ (c) (ii) and (iv) (d) (i), (ii) and (iii)
(b) Y 3+ < La 3+ < Eu 3+ < Lu 3+ 96. Which of the following is the use of mischmetall ?
(c) Y 3+ < Lu 3+ < Eu 3+ < La 3+ (a) In bullets
(d) Lu 3+ < Eu 3+ < La 3+ < Y 3+ (b) In lighter flint
(Atomic nos. Y =39, La = 57, Eu = 63, Lu = 71) (c) As catalyst in petroleum cracking
88. Which of the following lanthanoid ions is diamagnetic ? (d) Both (a) and (b)
(At nos. Ce = 58, Sm = 62, Eu = 63, Yb = 70) 97. The approximate percentage of iron in mischmetal is
(a) Sm2+ (b) Eu2+ (c) Yb2+ (d) Ce2+ (a) 10 (b) 20 (c) 50 (d) 5
89. Which of the following exhibit only + 3 oxidation state ?
(a) U (b) Th (c) Ac (d) Pa Topic 4: Some Application of d–Block and f–Block Elements
90. Larger number of oxidation states are exhibited by the 98. Gun metal is an alloy of
actinoids than those by the lanthanoids, the main reason being (a) Cu and Al (b) Cu and Sn
(a) 4f orbitals more diffused than the 5f orbitals (c) Cu, Zn and Sn (d) Cu, Zn and Ni
(b) lesser energy difference between 5f and 6d than 99. Brass is an alloy of
between 4f and 5d orbitals (a) Zn and Sn (b) Zn and Cu
(c) more energy difference between 5f and 6d than between (c) Cu, Zn and Sn (d) Cu and Sn
4f and 5d orbitals 100. Which one of the following is coinage metal ?
(d) more reactive nature of the actionids than the (a) Zn (b) Cu (c) Sn (d) Pb.
lanthanoids 101. Bronze is an alloy of
91. The increasing order of the shielding of electrons by the (a) Pb + Sn + Zn (b) Cu + Sn
orbitals ns,np,nd,nf is (c) Pb + Zn (d) Cu + Zn
(a) ns,np,nd,nf (b) np,ns,nd,nf 102. An alloy of transition metal containing a non transition metal
(c) nd,nf,np,ns (d) nf,nd.np,ns as a constituent is
92. Consider the following statements (a) invar (b) bronze
(i) La(OH)3 is the least basic among hydroxides of (c) chrome steel (d) stainless steel
lanthanides. 103. Which of the following is not correctly matched?
(ii) Zr4+ and Hf4+ posses almost the same ionic radii. Compound of Use
(iii) Ce4+ can as an oxidizing agent. transition metal
Which of the above is/are true ? (a) TiO Pigment industry
(a) (i) and (iii) (b) (ii) and (iii) (b) MnO2 Dry battery cell
(c) (ii) only (d) (i) and (ii) (c) V2O5 Manufacture of H2SO4
93. Match the columns (d) PdCl2 Manufacture of polyethylene
Column-I Column-II 104. Which of the following statements are correct?
(A) Lanthanide hard as steel. (p) Lu (i) Interstitial compounds contain non-metal atoms
(B) Lanthanide with maximum (q) Tb trapped inside the metal crystal whereas alloys are
paramagnetic character in homogeneous blend of metals.
Ln4+ state. (ii) Steel and bronze are alloys of transition and non-
(C) Lanthanide with maximum (r) Sm transition metals.
value of E° for reaction (iii) Some boride containing interstitial compounds are very
Ln3+(aq)+3e– ® Ln(s). hard comparable to that of diamond.
(D) Lanthanide whose Ln 3+ ion is (s) Eu (iv) Interstitial compounds are chemically more reactive
diamagnetic in nature than parent metal.
(a) A – (r), B – (s), C – (p), D – (q) (a) (i) and (iii) (b) (ii) and (iv)
(b) A – (r), B – (q), C – (s), D – (p) (c) (ii) and (iii) (d) (i), (ii) and (iii)
THE d-AND f–BLOCK ELEMENTS 309

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 11. KMnO4 acts as an oxidising agent in acidic medium. The
number of moles of KMnO4 that will be needed to react
1. Electronic configuration of a transition element X in +3
with one mole of sulphide ions in acidic solution is
oxidation state is [Ar]3d5. What is its atomic number?
(a) 2 5 (b) 2 6 (c) 2 7 (d) 2 4 2 3 4 1
(a) (b) (c) (d)
2. The electronic configuration of Cu(II) is 3d9 whereas that 5 5 5 5
of Cu(I) is 3d10. Which of the following is correct. 12. Which of the following oxides are amphoteric?
(a) Cu(II) is more stable Mn2O7, CrO3, Cr2O3, CrO, V2O5, V2O4
(b) Cu(II) is less stable (a) V2O5, Cr2O3 (b) Mn2O7, CrO3
(c) Cu(I) and Cu(II) are equally stable (c) CrO, V2O5 (d) V2O5, V2O4
(d) Stability of Cu(I) and Cu(II) depends on nature of 13. Gadolinium belongs to 4f series. Its atomic number is 64.
copper salts Which of the following is the correct electronic
3. Metallic radii of some transition elements are given below. configuration of gadolinium?
Which of these elements will have highest density? (a) [Xe]4f 7 5d16s2 (b) [Xe]4f 6 5d26s2
(c) [Xe]4f 6d 8 2 (d) [Xe]4f 9 5s1
Element Fe Co Ni Cu 14. Interstitial compounds are formed when small atoms are
Metallic radii/pm 126 125 125 128 trapped inside the crystal lattice of metals. Which of the
(a) Fe (b) Ni (c) Co (d) Cu following is not the characteristic property of interstitial
4. Generally, transition elements form coloured salts due to compounds?
the presence of unpaired electrons. Which of the following (a) They have high melting points in comparison to pure
compounds will be coloured in solid state? metals
(a) Ag2SO4 (b) CuF2 (c) ZnF2 (d) Cu2Cl2 (b) They are very hard
5. On addition of small amount of KMnO4 to concentrated (c) They retain metallic conductivity
H2SO4, a green oily compound is obtained which is highly (d) They are chemically very reactive
explosive in nature. Identify the compound from the 15. The magnetic moment is associated with its spin angular
following. momentum and orbital angular momentum. Spin only
(a) Mn 2O7 (b) MnO2 (c) MnSO4 (d) Mn 2O3 magnetic moment value of Cr3+ ion is
6. The magnetic nature of elements depends on the presence
(a) 2.87 BM (b) 3.87 BM (c) 3.47 BM (d) 3.57 BM
of unpaired electrons. Identify the configuration of
16. KMnO4 acts as an oxidising agent in alkaline medium. When
transition element, which shows highest magnetic moment.
(a) 3d7 (b) 3d5 (c) 3d8 (d) 3d2 alkaline KMnO4 is treated with KI, iodide ion is oxidised
7. Which of the following oxidation state is common for all to ................. .
lanthanoids? (a) I2 (b) IO– (c) IO3- (d) IO-4
(a) + 2 (b) + 3 (c) + 4 (d) + 5
8. Which of the following reactions are disproportionation 17. Which of the following statements is not correct?
reactions? (a) Copper liberates hydrogen from acids
(i) Cu+ ® Cu2+ + Cu (b) In its higher oxidation states, manganese forms stable
(ii) 3MnO -4 + 4H + ® 2MnO 4- + MnO 2 + 2H 2 O compounds with oxygen and fluorine
(iii) 2KMnO4 ® K2MnO4 + MnO2 + O2 (c) Mn3+ and Co3+ are oxidising agents in aqueous solution
(iv) 2MnO 4- + 3Mn 2+ + 2H 2O ® 5MnO 2 + 4H + (d) Ti2+ and Cr2+ are reducing agents in aqueous solution
(a) (i) (b) (i), (ii) and (iii) 18. When acidified K2Cr2O7 solution is added to Sn2+ salt then
(c) (ii), (iii) and (iv) (d) (i) and (iv) Sn2+ changes to
9. When KMnO4 solution is added to oxalic acid solution, (a) Sn (b) Sn3+ (c) Sn4+ (d) Sn+
the decolourisation is slow in the beginning but becomes 19. Highest oxidation state of manganese in fluoride is
instantaneous after some time because +4 (MnF4) but highest oxidation state in oxides is +7
(a) CO2 is formed as the product (Mn2O7) because
(b) reaction is exothermic (a) fluorine is more electronegative than oxygen
(c) MnO -4 catalyses the reaction (b) fluorine does not possess d-orbitals
(d) Mn2+ acts as autocatalyst (c) fluorine stabilises lower oxidation state
10. There are 14 elements in actinoid series. Which of the (d) in covalent compounds, fluorine can form single bond
following elements does not belong to this series? only while oxygen forms double bond
(a) U (b) Np (c) Tm (d) Fm
 EBD_7374
310 CHEMISTRY

20. Although zirconium belongs to 4d transition series and 28. Which form coloured salts : [BITSAT 2014, C]
hafnium to 5d transition series even then they show similar (a) Non-metals (b) Metals
physical and chemical properties because ................ . (c) p-block elements (d) Transitional elements
(a) both belong to d-block 29. K4[Fe(CN)6] is used in detecting.
(b) both have same number of electrons [BITSAT 2014, A]
(c) both have similar atomic radius (a) Fe3+ ion (b) Cu+ ion (c) Cu3+ ion (d) Fe2+ ion
(d) both belong to the same group of the periodic table 30. Magnetic moment 2.84 B.M. is given by :-
21. Why is HCl not used to make the medium acidic in oxidation (At. nos, Ni = 28, Ti = 22, Cr = 24, Co = 27)
reactions of KMnO4 in acidic medium? [AIPMT 2015, C]
(a) Ti3+ (b) Cr2+ (c) Co2+ (d) Ni2+
(a) Both HCl and KMnO4 act as oxidising agents 2+
31. The number of d-electrons in Fe (Z = 26) is not equal to
(b) KMnO4 oxidises HCl into Cl2 which is also an oxidising
the number of electrons in which one of the following?
agent
[AIPMT 2015, S]
(c) KMnO4 is a weaker oxidising agent than HCl (a) p-electrons in Cl (Z = 17)
(d) KMnO4 acts as a reducing agent in the presence of HCl (b) d-electrons in Fe (Z = 26)
Past Year MCQs (c) p-electrons in Ne (Z = 10)
(d) s-electrons in Mg (Z = 12)
22. Reason of lanthanoid contraction is:- [AIPMT 2014, C]
32. The angular momentum of electron in 'd ' orbital is equal
(a) Negligible screening effect of ‘f ’ orbitals
to : [AIPMT 2015, C]
(b) Increasing nuclear charge
(c) Decreasing nuclear charge (a) 2h (b) 2 3 h (c) 0h (d) 6h
(d) Decreasing screening effect 33. Which is the correct order of increasing energy of the listed
23. The pair of compounds that can exist together is: orbitals in the atom of titanium? [AIPMT 2015 RS, C]
[AIPMT 2014, A]
(a) 3s 4s 3p 3d (b) 4s 3s 3p 3d
(a) FeCl3, SnCl2 (b) HgCl2, SnCl2
(c) 3s 3p 3d 4s (d) 3s 3p 4s 3d
(c) FeCl2, SnCl2 (d) FeCl3, KI
34. Which of the following processes does not involve oxidation
24. In acidic medium, H2O2 changes Cr2O7–2 to CrO5 which has of iron ? [AIPMT 2015, S]
two (–O–O) bonds. Oxidation state of Cr in CrO5 is:- (a) Decolourization of blue CuSO4 solution by iron
[AIPMT 2014, S] (b) Formation of Fe(CO)5 from Fe
(a) + 5 (b) + 3 (c) + 6 (d) – 10 (c) Liberation of H2 from steam by iron at high temperature
25. The reaction of aqueous KMnO4 with H2O2 in acidic (d) Rusting of iron sheets
conditions gives: [AIPMT 2014, S] 35. Assuming complete ionization, same moles of which of the
(a) Mn4+ and O2 (b) Mn2+ and O2 following compounds will require the least amount of
(c) Mn2+ and O3 (d) Mn4+ and MnO2 acidified KMnO4 for complete oxidation
26. Which series of reactions correctly represents chemical [AIPMT 2015 RS, S]
reactions related to iron and its compound? (a) FeSO4 (b) FeSO3 (c) FeC2O4 (d) Fe(NO2)2
[JEE M 2014, S] 36. Because of lanthanoid contraction, which of the following
dil . H 2SO 4
(a) Fe ¾¾¾¾¾ H 2SO 4 , O 2 pairs of elements have nearly same atomic radii ? (Numbers
® FeSO 4 ¾¾¾¾¾®
in the parenthesis are atomic numbers). [AIPMT 2015, C]
Fe 2 (SO4 )3 ¾¾¾
heat
® Fe (a) Zr (40) and Nb (41) (b) Zr (40) and Hf (72)
(b) O , heat dil. H SO (c) Zr (40) and Ta (73) (d) Ti (22) and Zr (40)
Fe ¾¾¾¾
2 ® FeO ¾¾¾¾¾
2 4®
heat 37. Gadolinium belongs to 4f series. It's atomic number is 64.
FeSO 4 ¾¾¾ ® Fe
Which of the following is the correct electronic configuration
(c) Cl , heat heat , air Zn
Fe ¾¾¾¾®
2 FeCl3 ¾¾¾¾® FeCl 2 ¾¾® Fe of gadolinium ? [AIPMT 2015 RS, C]
O2 , heat
(d) Fe¾¾¾¾ CO , 600°C
® Fe3O¾¾¾¾¾ ® (a) [Xe]4f 86d 2 (b) [Xe]4f 95s1
4
CO , 700°C (c) [Xe] 4f 75d16s2 (d) [Xe] 4f 65d26s2
FeO ¾¾¾¾¾
® Fe
38. Identify the incorrect statement among the following :
27. The equation which is balanced and represents the correct
product(s) is: [JEE M 2014, S] [AIIMS 2015, C]
(a) Lanthanoid contraction is the accumulation of
(a) Li 2 O + 2KCl ¾¾ ® 2LiCl + K 2 O successive shrinkages.
+
(b) é CoCl ( NH3 ) ù + 5H + ¾¾
® Co 2 + + 5NH +4 + Cl - (b) As a result of lanthanoid contraction, the properties of
ë 5û
2+ 4d series of the transition elements have no similarities
4-
(c) é Mg ( H 2 O ) ù + ( EDTA ) with the 5d series of elements.
ë 6û
2+ (c) Shielding power of 4f electrons is quite weak.
® ëé Mg ( EDTA )ûù + 6H 2 O
excess NaOH
¾¾¾¾¾¾ (d) There is a decrease in the radii of the atoms or ions as
(d) CuSO 4 + 4KCN ¾¾ ® K 2 éCu ( CN ) ù + K 2SO4 one proceeds from La to Lu.
ë 4û
THE d-AND f–BLOCK ELEMENTS 311

39. Assertion : Transition metals are good catalysts. Which of the above is/are true ?
Reason : V2O5 or Pt is used in the preparation of H2SO4 by (a) (I) and (III) (b) (II) and (III)
contact process. [AIIMS 2015, A] (c) (II) only (d) (I) and (II)
(a) Assertion is correct, reason is correct; reason is a 48. Assertion : Magnetic moment values of actinides are lesser
correct explanation for assertion. than the theoretically predicted values.
(b) Assertion is correct, reason is correct; reason is not a Reason : Actinide elements are strongly paramagnetic.
correct explanation for assertion [AIIMS 2013, 2016, C]
(c) Assertion is correct, reason is incorrect (a) Assertion is correct, reason is correct; reason is a
(d) Assertion is incorrect, reason is correct. correct explanation for assertion.
40. Match the catalysts to the correct processes : (b) Assertion is correct, reason is correct; reason is not a
[JEE M 2015, A] correct explanation for assertion
Catalyst Process
(c) Assertion is correct, reason is incorrect
(A) TiCl4 (i) Wacker process
(d) Assertion is incorrect, reason is correct.
(B) PdCl2 (ii) Ziegler - Natta
49. The reaction of zinc with dilute and concentrated nitric
polymerization
acid, respectively, produces: [JEE M 2016, S]
(C) CuCl2 (iii) Contact process
(D) V2O5 (iv) Deacon's process (a) NO and N2O (b) NO2 and N2O
(a) (A) - (ii), (B) - (iii), (C) - (iv), (D) - (i) (c) N2O and NO2 (d) NO2 and NO
(b) (A) - (iii), (B) - (i), (C) - (ii), (D) - (iv) 50. Which of the following compounds is metallic and
(c) (A) - (iii), (B) - (ii), (C) - (iv), (D) - (i) ferromagnetic? [JEE M 2016, C]
(d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii) (a) VO2 (b) MnO2 (c) TiO2 (d) CrO2
41. The color of KMnO4 is due to : [JEE M 2015, C] 51. Which of the following arrangements does not represent
(a) L ® M charge transfer transition the correct order of the property stated against it ?
(b) s - s* transition [BITSAT 2016, C]
(c) M ® L charge transfer transition (a) V2+ < Cr 2+ < Mn2+ < Fe2+ :paramagnetic behaviour
(d) d – d transition (b) i2+ < Co2+ < Fe2+ < Mn2+ : ionic size
42. Which one of given elements shows maximum number of (c) Co3+ < Fe3+ < Cr3+ < Sc3+ :
different oxidation states in its compounds? stability in aqueous solution
[BITSAT 2015, C] (d) Sc < Ti < Cr < Mn : number of oxidation states
(a) Am (b) Fm (c) La (d) Gd 52. Knowing that the chemistry of lanthanoids(Ln) is dominated
43. The number of elements present in the d-block of the by its + 3 oxidation state, which of the following statements
periodic table is [BITSAT 2015, CS] is incorrect? [BITSAT 2016, C]
(a) 40 (b) 41 (c) 45 (d) 46 (a) The ionic size of Ln (III) decrease in general with
44. Which one of the following statements is correct when SO2 increasing atomic number
is passed through acidified K2Cr2O7 solution ? (b) Ln (III) compounds are generally colourless.
[NEET 2016, S]
(c) Ln (III) hydroxide are mainly basic in character.
(a) The solution turns blue
(d) Because of the large size of the Ln (III) ions the bonding
(b) The solution is decolourized
in its compounds is predominantly ionic in character.
(c) SO2 is reduced
53. Name the gas that can readily decolourise acidified KMnO4
(d) Green Cr2(SO4)3 is formed
solution : [NEET 2017, S]
45. When copper is heated with conc. HNO3 it produces
[NEET 2016, S] (a) SO2 (b) NO2 (c) P2O5 (d) CO2
(a) Cu(NO3)2 and NO2 (b) Cu (NO3)2 and NO 54. The reason for greater range of oxidation states in actinoids
(c) Cu(NO3)2, NO and NO2(d) Cu(NO3)2 and N2O is attributed to :- [NEET 2017, C]
46. The electronic configurations of Eu(Atomic No. 63), (a) actinoid contraction
Gd(Atomic No. 64) and Tb (Atomic No. 65) are (b) 5f, 6d and 7s levels having comparable energies
[NEET 2016, C] (c) 4f and 5d levels being close in energies
(a) [Xe]4f 6s , [Xe]4f 6s and [Xe]4f 5d 16s2
7 2 8 2 8 (d) the redioactive nature of actinoids
55. Assertion : Transition metals show variable valency.
(b) [Xe]4f 75d16s2, [Xe]4f 7 5d1 6s2 and [Xe]4f 96s2
Reason : Transition metals have a large energy difference
(c) [Xe]4f 65d16s2, [Xe]4f 75d16s2 and [Xe]4f 85d16s2
between the ns2 and (n – 1)d electrons. [AIIMS 2017, C]
(d) [Xe]4f 76s2, [Xe]4f 75d16s2 and [Xe]4f 96s2
(a) Assertion is correct, reason is correct; reason is a
47. Consider the following statements [AIIMS 2016, C] correct explanation for assertion.
(I) La(OH) 3 is the least basic among hydroxides of (b) Assertion is correct, reason is correct; reason is not a
lanthanides. correct explanation for assertion
(II) Zr4+ and Hf4+ posses almost the same ionic radii. (c) Assertion is correct, reason is incorrect
(III) Ce4+ can as an oxidizing agent. (d) Assertion is incorrect, reason is correct.
 EBD_7374
312 CHEMISTRY

56. In the following reactions, ZnO is respectively acting as 60. A gas metal in bivalent state has approximately 23e–, what is
a/an: [JEE M 2017, C] spin magnetic moment in elemental state? [AIIMS 2018, S]
(A) ZnO + Na2O ® Na2ZnO2
(a) 2.87 (b) 5.5 (c) 5.9 (d) 4.9
(B) ZnO + CO2 ® ZnCO3
(a) base and acid (b) base and base 61. In acidic medium which of the following does not change its
(c) acid and acid (d) acid and base colour? [AIIMS 2018, S]
57. Cadmium is used in nuclear reactors for? –
(a) MnO4 (b) MnO4 2– (c) CrO 2–
4 (d) FeO42–
[BITSAT 2017, A] 62. AgNO3 does not decompose in/on: [AIIMS 2018, C]
(a) absorbing neutrons (b) cooling
(a) U.V. radiation (b) Skin (human)
(c) release neutrons (d) increase energy
58. Which one of the following ions exhibits d-d transition and (c) Water at 25°C (d) Glucose
paramagnetism as well? [NEET 2018, S] 63. On passing H2S gas in the following test tubes precipita-
– tion occurs. Find the correct match? [AIIMS 2018, S]
(a) CrO2– 4 (b) Cr2 O72– (c) MnO 2– 4 (d) MnO4
59. Match the metal ions given in Column I with the spin
magnetic moments of the ions given in Column II and assign
the correct code : [NEET 2018, S]
Column I Column II
a. Co3+ i. 8 BM
b. Cr3+ ii. 35 BM
c. Fe3+ iii. 3 BM
d. Ni2+ iv. 24 BM Yellow Black Orange Brown
v. 15 BM Cu, Sb, Zn, Pb, Sn, Ni
a b c d (a) Cd – Black (b) Sb – Orange
(a) iv v ii i (c) Ni – Yellow (d) Zn – Brown
(b) i ii iii iv 64. Which of the following exhibits minimum number of
(c) iii v i ii oxidation states ? [AIIMS 2018, C]
(d) iv i ii iii (a) Mn (b) Np (c) Th (d) Cr

Exercise 3 : Try If You Can

1. Out of TiF62– , CoF63– , Cu2Cl2 and NiCl 2–
4 (Z of Ti = 22, Co (c) Transition elements have high enthalpies of atomization
= 27, Cu = 29, Ni = 28), the colourless species are: and in 3d series increase regularly from Sc to Cu.
(d) On going down a group from 3d to 6d series the stability
(a) Cu2Cl2 and NiCl 2–
4 (b) TiF62– ,and Cu2Cl2 of higher oxidation state increases with increasing
atomic number.
(c) CoF63– ,and NiCl2–
4 (d) TiF62– ,and CoF63– , 4. When (NH4)2Cr2O7 is heated, the gas evolved is
2. The basic character of the transition metal monoxides (a) N2 (b) NO2 (c) O2 (d) Na2O
follows the order 5. A metal M and its compound can give the following
(Atomic Nos.,Ti = 22, V = 23, Cr = 24, Fe = 26) observable changes in a consequence of reactions
(a) TiO > VO > CrO > FeO (b) VO > CrO > TiO > FeO
é ù aqueous é White ù
® êColourless
(c) CrO > VO > FeO > TiO (d) TiO > FeO > VO > CrO dilute
M ¾¾¾¾ solutions ú ¾¾¾¾ ®ê ú
3. Which of the following statement is incorrect ? HNO3 ë û NaOH ë precipitate û
(a) Across a period from Sc to Cu the densities increase é White ù H 2S éColourless ù excess
with increasing atomic number. ê precipitate ú ¬¾¾
¾ ê solutions ú ¬¾¾¾¾¾
NaOH ( aq.)
ë û ë û
(b) The melting point of transition elements rise to a
maximum from Sc to Cr and then decreases from Fe to (a) Mg (b) Pb (c) Zn (d) Sn
Zn.
THE d-AND f–BLOCK ELEMENTS 313

6. heat ( )
( X ) + K 2CO3 + Air ¾¾¾ 11. A blue colouration is not obtained when
® Y
(a) ammonium hydroxide dissolves in copper sulphate
( Y ) + Cl2 ¾¾® ( Z ) Pink
Which of the following is correct? (b) copper sulphate solution reacts with K 4 [Fe(CN) 6 ]
(a) X = black, MnO2, Y = Blue, K2CrO4, Z = KMnO4 (c) ferric chloride reacts with sod. ferrocyanide
(b) X = green, Cr2O3, Y = Yellow, K2CrO4, Z = K2Cr2O7 (d) anhydrous CuSO4 is dissolved in water
(c) X = black, MnO2, Y = green, K2MnO4, Z = KMnO4 12. In nitroprusside ion the iron and NO exist as FeII and NO+
(d) X = black, Bi2O3, Y = colourless KBiO2, Z = KBiO3 rather than FeIII and NO. These forms can be differentiated
by
H S­ Excess
CuSO4 (aq.) ¾¾¾® M ¯ ¾¾¾¾ ®N+O
2 (a) estimating the concentration of iron
7. of KCN
(b) measuring the concentration of CN
Then final products N and O are respectively.
(c) measuring the solid state magnetic moment
(a) [Cu(CN)4 ]3- , (CN) 2 (b) CuCN, (CN)2 (d) thermally decomposing the compound.
º
13. Given E º = 1.52 V and E 3+ = 1.36V . Point
(c) [Cu(CN)4 ]2- , (CN) 2 (d) Cu (CN)2, K2S Au 3+ / Au Au / Au +
out the correct statement of the following
8. In the extraction of silver from argentite ore the ore
is treated with dilute solution of NaCN in water in the
presence of Y, whereby the following reaction takes place (a) Au3+ disproportionates into Au4+ and Au2+ in aqueous
solution
Ag 2 X + 4NaCN + 2Y ® 2Na éëAg (CN )2 ùû + Na 2XO 4 (b) Au3+ disproportionates into Au4+ and Au+ in aqueous
solution
X and Y in this reaction are represented by (c) Au+ disproportionates into Au3+ and Au in aqueous
(a) Cl and S (b) S and O2 (c) O and O2 (d) O and S solution
9. The dichromate ion is in equilibrium with chromate ion in (d) Au+ disproportionates into Au2+ and Au in aqueous
aqueous solution as : solution
14. A metal gives two chlorides ‘X’ and ‘Y’. The chloride ‘X’
2-
Cr2O 7(aq) + H2O 2CrO24-(aq) + 2H (+aq) gives a black precipitate with NH4OH. The chloride ‘Y’ gives
a white precipitate with NH4OH. ‘Y’ gives red precipitate
The oxoanion has with KI which is soluble in excess of KI. The formula of
(a) same oxidizing property in acidic and alkaline solutions chlorides ‘X’ and ‘Y’ respectively are
(b) better oxidizing property in acidic solution (a) Hg2Cl2 and HgCl2 (b) HgCl2 and ZnCl2
(c) ZnCl2 and Hg2Cl2 (d) None of these
(c) better oxidizing property in alkaline solution
15. First four ionization energies of Ni and Pt are given below:
(d) no oxidizing property in acidic or alkaline solution (IE1 + IE2) (IE3 + IE4)
10. Cerium (Z = 58) is an important member of the lanthanoids. Ni 2.49 ×103 kJ mol–1 8.8 × 103 kJ mol–1
Which of the following statements about cerium is Pt 2.66 × 103 kJ mol–1 6.7 × 103kJ mol–1
incorrect? From the data it can be concluded that
(a) The +4 oxidation state of cerium is not known in (a) Ni(II) compounds are thermodynamically more stable
solutions than Pt(II) compounds
(b) The +3 oxidation state of cerium is more stable than the (b) Pt(IV) compounds are thermodynamically more stable
+4 oxidation state than Ni(II) compounds.
(c) both correct
(c) The common oxidation states of cerium are +3 and +4 (d) none of these is correct
(d) Cerium (IV) acts as an oxidizing agent
 EBD_7374
314 CHEMISTRY

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 12 (a) 23 (b) 34 (b) 45 (b) 56 (a) 67 (c) 78 (c) 89 (c) 100 (b)
2 (b) 13 (a) 24 (a) 35 (a) 46 (b) 57 (b) 68 (b) 79 (c) 90 (b) 101 (b)
3 (c) 14 (c) 25 (d) 36 (a) 47 (d) 58 (a) 69 (a) 80 (b) 91 (d) 102 (b)
4 (c) 15 (d) 26 (d) 37 (c) 48 (d) 59 (d) 70 (a) 81 (d) 92 (b) 103 (d)
5 (a) 16 (a) 27 (a) 38 (b) 49 (a) 60 (c) 71 (b) 82 (d) 93 (d) 104 (a)
6 (b) 17 (c) 28 (a) 39 (c) 50 (d) 61 (c) 72 (c) 83 (c) 94 (c)
7 (b) 18 (a) 29 (d) 40 (b) 51 (d) 62 (a) 73 (b) 84 (a) 95 (a)
8 (d) 19 (d) 30 (c) 41 (d) 52 (d) 63 (b) 74 (b) 85 (a) 96 (d)
9 (c) 20 (d) 31 (a) 42 (c) 53 (d) 64 (b) 75 (d) 86 (d) 97 (d)
10 (c) 21 (a) 32 (d) 43 (b) 54 (b) 65 (c) 76 (d) 87 (c) 98 (c)
11 (c) 22 (a) 33 (d) 44 (c) 55 (b) 66 (a) 77 (b) 88 (c) 99 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 8 (a) 15 (b) 22 (a) 29 (a) 36 (b) 43 (a) 50 (d) 57 (a) 64 (c)
2 (a) 9 (d) 16 (c) 23 (c) 30 (d) 37 (c) 44 (d) 51 (a) 58 (c)
3 (d) 10 (c) 17 (a) 24 (c) 31 (a) 38 (b) 45 (a) 52 (b) 59 (a)
4 (b) 11 (a) 18 (c) 25 (b) 32 (d) 39 (b) 46 (d) 53 (a) 60 (c)
5 (a) 12 (a) 19 (d) 26 (d) 33 (d) 40 (d) 47 (b) 54 (b) 61 (a)
6 (b) 13 (a) 20 (c) 27 (b) 34 (b) 41 (a) 48 (b) 55 (c) 62 (c)
7 (b) 14 (d) 21 (b) 28 (d) 35 (a) 42 (a) 49 (c) 56 (d) 63 (b)
Exercise 3 : Try If You Can
1 (b) 3 (c) 5 (c) 7 (a) 9 (b) 11 (b) 13 (c) 15 (c)
2 (a) 4 (a) 6 (c) 8 (b) 10 (a) 12 (c) 14 (a)
 23 Chapter
COORDINATION COMPOUNDS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

8
7
6
AIPMT /NEET
5
Number of Questions

AIIMS
4
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 3 Isomerism and bonding in
AIIMS 3 coordination compounds, CFT 4.2/5 9
JEE Main 2
BITSAT 3
 EBD_7374
316 CHEMISTRY
COORDINATION COMPOUNDS 317
 EBD_7374
318 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Werner’s Theory of Coordination Compounds 8. Ligand in a complex salt are

Definitions of Some Important Terms Pertaining to (a) anions linked by coordinate bonds to a central metal
atom or ion
Coordination Compounds
(b) cations linked by coordinate bonds to a central metal
1. Which of the following postulates of Werner’s theory is or ion
incorrect? (c) molecules linked by coordinate bonds to a central
(a) Primary valencies are satisfied by negative ions. metal or ion
(b) Secondary valencies are satisfied by neutral molecules (d) ions or molecules linked by coordinate bonds to a
or negative ions. central atom or ion
(c) Secondary valence is equal to the coordination number 9. Which of the following does not form a chelate ?
and it depends upon the nature of ligand attached to (a) EDTA (b) Oxalate
metal. (c) Pyridine (d) Ethylenediamine
(d) The ions/ groups bound by the secondary linkages to 10. A bidenate ligand always
the metal have charecteristic spatial arrangements. (a) has bonds formed to two metals ions
2. One mole of the complex compound Co(NH3)5Cl3, gives 3 (b) has a charge of +2 or – 2
moles of ions on dissolution in water. One mole of the same (c) forms complex ions with a charge of +2 or –2
complex reacts with two moles of AgNO3 solution to yield (d) has two donor atoms forming simultaneously two
two moles of AgCl (s). The formula of the complex is sigma (s) bonds.
(a) [Co(NH3)3Cl3]. 2 NH3 11. An ambident ligand is one which
(b) [Co(NH3)4Cl2] Cl . NH3 (a) is linked to the metal atom through two donor atoms
(c) [Co(NH3)4Cl] Cl2. NH3 (b) has two donor atoms, but only one of them has the
(d) [Co(NH3)5Cl] Cl2 capacity to form a coordinate bond [or a sigma (s)
3. The number of ions formed on dissolving one molecule of bond]
FeSO4(NH4)2SO4.6H2O in water is: (c) has two donor atoms, but either of two can form a
(a) 4 (b) 5 (c) 3 (d) 6 coordinate bond
4. The coordination number of a central metal atom in a complex (d) forms chelate rings.
is determined by 12. NH2-NH2 serves as
(a) the number of ligands around a metal ion bonded by (a) Monodentate ligand (b) Chelating ligand
sigma and pi-bonds both (c) Bridging ligand (d) Both (a) and (c)
(b) the number of ligands around a metal ion bonded by 13. Which one of the following is NOT a ligand ?
pi-bonds (a) PH3 (b) NO+ (c) Na+ (d) F–
(c) the number of ligands around a metal ion bonded by 14. Choose the correct statement.
sigma bonds (a) Coordination number has nothing to do with the
(d) the number of only anionic ligands bonded to the metal number of groups or molecules attached to the central
ion. atom
5. The oxidation state of Cr in [Cr(NH3)4Cl2]+ is (b) Coordination number is the number of coordinating
(a) 0 (b) + 1 (c) + 2 (d) + 3 sites of all the ligands connected to the central atom
6. 4–
[EDTA] is a : or the number of coordinate bonds formed by the metal
(a) monodentate ligand (b) bidentate ligand atom with ligands
(c) quadridentate ligand (d) hexadentate ligand (c) Werner’s coordination theory postulates only one type
7. Some salts although containing two different metallic of valency
elements give test for only one of them in solution. Such (d) All the above are correct
salts are 15. O2 is a
(a) complex (b) double salts (a) Monodentate ligand (b) Bidenate ligand
(c) normal salts (d) None of these (c) Tridentate ligand (d) Hexadenate ligand
COORDINATION COMPOUNDS 319

16. Which of the following complexes are heteroleptic ? 22. Suppose someone made aqueous solution of NiCl2 and
(i) [Cr(NH3)6]3+ (ii) [Fe(NH3)4Cl2]+ recrystallized its aqueous solution in excess of water and
(iii) [Mn(CN)6]4– (iv) [Co(NH3)4Cl2] if two moles of precipitate AgCl was formed on treatment
(a) (i), (iv) (b) (ii) and (iv) with AgNO3, what is the most probable structure of the
(c) (i) and (ii) (d) (i) and (iv) compound ?
17. Identify the correct statements for the behaviour of (a) [Ni(Cl)2(H2O)4] (b) [Ni (H2O)6]Cl2
ethane- 1, 2-diamine as a ligand. (c) [Ni(H2O)5Cl] (d) [Ni (H2O)4Cl2].2H2O
(i) It is a neutral ligand.
Topic 2: Nomenclature of Coordination Compounds
(ii) It is a didentate ligand.
(iii) It is a chelating ligand. Isomerism in Coordination Compounds
(iv) It is a unidentate ligand.
23. K 3[Al(C 2O 4 )3 ] is called
(a) (i), (ii) and (iii) (b) (ii) and (iii)
(c) (iii) and (iv) (d) (i), (iii) and (iv) (a) Potassium aluminooxalate
18. Match the columns. (b) Potassium trioxalatoaluminate (III)
(c) Potassium aluminium (III) oxalate
Column-I Column-II
(d) Potassium trioxalatoaluminate (VI)
(Ligand) (Type of ligand)
24. The hypothetical complex chlorodiaquatriamminecobalt (III)
(A) Triphenylphosphine (p) Unidenate chloride can be represented as
(B) BF3 (q) Didentate (a) [CoCl(NH3)3(H2O)2]Cl2
(C) Ethylenediamine (r) Not a ligand (b) [Co(NH3)3(H2O)Cl3]
(D) Ethylenediaminetetracetateion (s) Hexadenate (c) [Co(NH2)3(H2O)2 Cl]
(a) A – (p), B – (r), C – (q), D – (s) (d) [Co(NH3)3(H2O)3]Cl3
(b) A – (p), B – (q), C – (r), D – (s) 25. The IUPAC name of the coordination compound
K3[Fe(CN)6] is
(c) A – (p), B – (r), C – (q), D – (s)
(a) Tripotassium hexacyanoiron (II)
(d) A – (p), B – (q), C – (s), D – (p) (b) Potassium hexacyanoiron (II)
19. Assertion : NF3 is a weaker ligand than N(CH3)3. (c) Potassium hexacyanoferrate (III)
Reason : NF3 ionizes to give F– ions in aqueous solution. (d) Potassium hexacyanoferrate (II)
(a) Assertion is correct, reason is correct; reason is a 26. The IUPAC name for the complex [Co(ONO)(NH3)5]Cl2 is
correct explanation for assertion. (a) pentaamminenitrito-N-cobalt(II) chloride
(b) Assertion is correct, reason is correct; reason is not a (b) pentaamminenitrito-N-cobalt(III) chloride
correct explanation for assertion (c) nitrito-N-pentaamminecobalt(III) chloride
(c) Assertion is correct, reason is incorrect (d) nitrito-N-pentaamminecobalt(II) chloride
(d) Assertion is incorrect, reason is correct. 27. Chemical formula for iron (III) hexacyanoferrate (II) is
20. A co-ordination complex compound of cobalt has the (a) Fe[Fe(CN)6] (b) Fe3[Fe(CN)6]
molecular formula containing five ammonia molecules, one (c) Fe3[Fe(CN)6]4 (d) Fe4[Fe(CN)6]3
nitro group and two chlorine atoms for one cobalt atom. 28. IUPAC name of Na 3[Co(ONO) 6 ] is
One mole of this compound produces three mole ions in an
(a) Sodium cobaltinitrite
aqueous solution. On reacting this solution with excess of
(b) Sodium hexanitrito cobaltate (III)
AgNO3 solution, we get two moles of AgCl precipitate. The (c) Sodium hexanitrocobalt (III)
ionic formula for this complex would be (d) Sodium hexanitritocobaltate (II)
(a) [Co(NH3)4 (NO2) Cl] [(NH3) Cl] 29. The number of geometrical isomers for [Pt(NH3)2Cl2] is
(b) [Co (NH3)5 Cl] [Cl (NO2)] (a) 2 (b) 1 (c) 3 (d) 4
(c) [Co (NH3)5 (NO2)] Cl2 30. Which of the following will give maximum number of isomers?
(d) [Co (NH3)5] [(NO2)2Cl2] (a) [Ni(C2O4) (en)2]2– (b) [Ni(en) (NH3)4]2+
(c) [Cr(SCN)2 (NH3)4]+ (d) [Co(NH3)4 Cl2]
21. What is the secondary valence of following compounds
31. Which one of the following octahedral complexes will not
PtCl2.2NH3, CoCl3.4NH3 and NiCl2.6H2O show geometric isomerism? (A and B are monodentate
if moles of AgCl precipitated per mole of the given ligands)
compounds with excess AgNO3 respectively are: 0, 1 and 2 (a) [MA5B] (b) [MA2B4]
(a) 6, 4, 4 (b) 4, 6, 6 (c) 4, 4, 6 (d) 2, 4, 6 (c) [MA3B3] (d) [MA4B2]
 EBD_7374
320 CHEMISTRY

32. The type of isomerism present in Pentaminenitrochromium 45. For the square planar complex [M (a) (b) (c) (d)] (where M
(III) chloride is = central metal and a, b, c and d are monodentate ligands),
(a) optical (b) linkage the number of possible geometrical isomers are
(c) ionisation (d) polymerisation. (a) 1 (b) 2 (c) 3 (d) 4
33. Which of the following compounds shows optical 46. Which of the following will exhibit optical isomerism ?
isomerism? (a) [Cr(en) (H2O)4]3+
(a) [Co(CN)6]3– (b) [Cr(C2O4)3]3– (b) [Cr(en)3]3+
(c) [ZnCl4] 2– (d) [Cu(NH3)4]2+ (c) trans-[Cr(en)(Cl2)(NH3)2]+
34. Which of the following ions can exhibit optical isomerism– (d) [Cr(NH3)6]3+
(a) [Co(NH3)4Cl2]+ (b) [Co(NH3)2Cl4]– 47. Which of the following will give maximum number of
(c) Cis-[Co(en)2Cl2]+ (d) trans-[Co(en)2Cl2]+ isomers?
35. Which would exhibit co-ordination isomerism (a) [Co(NH3)4Cl2] (b) [Ni(en)(NH3)4]2+
(a) [Cr(NH3)6][Co(CN)6] (b) [Co(en)2Cl2] (c) [Ni(C2O4)(en)2] (d) [Cr(SCN)2(NH3)4]2+
(c) [Cr(NH3)6]Cl3 (d) [Cr(en)2Cl2]+ 48. The compounds [PtCl2(NH3)4]Br2 and [PtBr2(NH3)4]Cl 2
constitutes a pair of
36. Which of the following does not show optical isomerism?
(a) coordination isomers (b) linkage isomers
(a) [Co(NH3)3Cl3]0 (b) [Co (en) Cl2 (NH3)2]+
3+ (c) ionization isomers (d) optical isomers
(c) [Co (en)3] (d) [Co (en)2Cl2]+
49. Which one of the following will not show geometrical
(en = ethylenediamine)
isomerism ?
37. The complexes [Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6]
(a) [Cr(NH3)4Cl2]Cl (b) [Co(en)2Cl2]Cl
[Co(CN)6] are the examples of which type of isomerism?
(c) [Co(NH3)5NO2]Cl2 (d) [Pt(NH3)2Cl2 ]
(a) Linkage isomerism
50. A similarity between optical and geometrical isomerism is
(b) Ionization isomerism
that
(c) Coordination isomerism
(a) each gives equal number of isomers for a given
(d) Geometrical isomerism
compound
38. The complex, [Pt(py)(NH3)BrCl] will have how many
(b) if in a compound one is present then so is the other
geometrical isomers ?
(c) both are included in stereoisomerism
(a) 3 (b) 4 (c) 0 (d) 2
(d) they have no similarity
39. Which of the following has a square planar geometry?
51. Which of the following type of isomerism is shown by given
(a) [PtCl4]2– (b) [CoCl4]2–
complex compound?
(c) [FeCl4]2– (d) [NiCl4]2–
NH3
(At. nos.: Fe = 26, Co = 27, Ni = 28, Pt = 78) H3N NO2
40. Which one of the following has an optical isomer? Co
(a) [Zn(en) (NH3)2]2+ (b) [Co(en)3]3+
O2N NO2
(c) [Co(H2O)4(en)]3+ (d) [Zn(en)2]2+ NH3
(en = ethylenediamine)
(a) Facial (b) Meridional
41. The ionisation isomer of [Cr(H2O)4Cl(NO2)]Cl is
(c) Cis (d) Both b and c
(a) [Cr(H2O)4(O2N)]Cl2
52. Match the complex species given in Column-I with the
(b) [Cr(H2O)4Cl2](NO2)
isomerism exhibited in Column-II and assign the correct
(c) [Cr(H2O)4Cl(ONO)]Cl
code:
(d) [Cr(H2O)4Cl2(NO2)].H2O
Column-I Column-II
42. Isomerism exhibited by [Cr(NH3)2(H2O)2Cl2]+ are –
(Complex species) (Isomerism)
(a) ionization, optical (b) hydrate, optical
(c) geometrical, optical (d) coordinate, geometrical (A) [Co[NH3)4Cl2]+ (p) optical
43. Which of the following complex will show geometrical as (B) cis-[Co(en)2Cl2]+ (q) ionisation
well as optical isomerism (en=ethylenediammine) (C) [Co(NH3)5(NO2)]Cl2 (r) coordination
(a) Pt(NH3)2Cl2 (b) [Pt(NH3)Cl4] (D) [Co(NH3)6][Cr(CN)6] (s) geometrical
(c) [Pt(en)3] 4+ (d) [Pt(en)2Cl2] (a) A – (s), B – (p), C – (q), D – (r)
44. The number of geometrical isomers from [Co(NH3)3(NO2)3] (b) A – (p), B – (r), C – (q), D – (s)
is (c) A – (q), B – (s), C – (p), D – (r)
(a) 2 (b) 3 (c) 4 (d) 0
(d) A – (p), B – (r), C – (s), D – (q)
COORDINATION COMPOUNDS 321

53. The formula for the complex, dichlorobis (urea) copper (II) (i) non-superimposable on its mirror images
is (ii) optically inactive
(a) [Cu{O = C (NH2)2}] Cl2 (iii) rotate plane polarised light
(b) [Cu{O = C (NH2)2}Cl]Cl (iv) planar
(c) [CuCl2 {O = C(NH2)2}2] (a) (i) and (ii) (b) (i) and (iv)
(d) [CuCl2] [{O = C (NH2)2}]2 (c) (i), (ii) and (iii) (d) (ii) only
54. Which of the following will give a pair of enantiomorphs?
(a) [Cr(NH3)6][Co(CN)6] (b) [Co(en)2Cl2]Cl Topic 3: Bonding in Coordination Compounds
(c) [Pt(NH3)4] [PtCl6] (d) [Co(NH3)4Cl2]NO2 61. The geometry of Ni(CO)4 and Ni(PPh3)2Cl2 are
(en =NH2CH2CH2NH2) (a) both square planar
55. [Co(NH3)4 (NO2)2] Cl exhibits (b) tetrahedral and square planar
(a) linkage isomerism, ionization isomerism and (c) both tetrahedral
geometrical isomerism (d) None of these
(b) ionization isomerism, geometrical isomerism and optical 62. Which of the following facts about the complex
isomerism [Cr(NH3)6]Cl3 is wrong?
(c) linkage isomerism, geometrical isomerism and optical (a) The complex involves d 2sp3 hybridisation and is
isomerism octahedral in shape.
(d) linkage isomerism, ionization isomerism and optical (b) The complex is paramagnetic.
isomerism (c) The complex is an outer orbital complex
56. Among the following coordination compounds/ions (d) The complex gives white precipitate with silver nitrate
(i) [Fe(CN)6]3– (ii) [Pt(NH3)2Cl2] solution.
(iii) [Co(NH3)6]3+ (iv) [Cr(H2O)6]Cl3 63. Which of the following statements is correct ?
Which species exhibit geometrical isomerism? (Atomic number of Ni = 28)
(a) (ii) only (b) (i) and (ii) (a) Ni(CO)4 is diamagnetic and [NiCl4]2– and [Ni(CN)4]2–
are paramagnetic
(c) (ii) and (iv) (d) (i) and (iii)
(b) Ni(CO)4and [Ni(CN)4]2– are diamagnetic and [NiCl4]2–
57. Identify the optically active compounds from the following :
is paramagnetic
(i) [Co(en)3 ]3+ (ii) trans - [Co(en) 2 Cl 2 ]+ (c) Ni(CO)4and [NiCl4]2–are diamagnetic and [Ni(CN)4]2–
is paramagnetic
(iii) cis - [Co(en) 2Cl 2 ]+ (iv) [Cr(NH3 )5 Cl]
(d) [NiCl4]2– and [Ni(CN)4]2– are diamagnetic and Ni(CO)4
(a) (i) and (iii) (b) (ii) and (iii) is paramagnetic
(c) (iii) and (iv) (d) (i), (iii) and (iv) 64. Which one of the following will show paramagnetism
58. For which value of the x, and y, the following square corresponding to 2 unpaired electrons?
planar compound shows geometrical isomers [Pt (Cl)x (Atomic numbers : Ni = 28, Fe = 26)
(Br)y]2– (a) [FeF6]3– (b) [NiCl4]2–
(a) 1, 3 (b) 3, 1 (c) 2, 2 (d) 1, 1 (c) [Fe(CN)6] 3– (d) [Ni(CN)4]2–
59. The terahedral complex [M(A)(B)(X)(Y)], where A,B,X and 65. Atomic number of Cr and Fe are respectively 25 and 26,
Y are different ligands and M is a metal ion is which of the following is paramagnetic?
(a) optically inactive (a) [Cr(CO)6] (b) [Fe(CO)5]
(b) rotate plane polarized light (c) [Fe(CN)6]4– (d) [Cr(NH3)6]3+
(c) incomplete information 66. CN– is a strong field ligand. This is due to the fact that
(a) it carries negative charge
(d) can’t be said
(b) it is a pseudohalide
60. The complex given is
3+ (c) it can accept electrons from metal species
en (d) it forms high spin complexes with metal species
67. Which one of the following cyano complexes would exhibit
the lowest value of paramagnetic behaviour ?
Co (a) [Co(CN)6]3+ (b) [Fe(CN)6]3–
(c) Mn(CN)6] 3– (d) [Cr(CN)6]3–
en (At. Nos : Cr = 24, Mn = 25, Fe = 26, Co = 27)
en
 EBD_7374
322 CHEMISTRY

68. [Sc(H2O)6]3+ ion is : 77. Which of the following is the limitation of valence bond
(a) colourless and diamagnetic theory?
(b) coloured and octahedral (a) It does not distinguish between weak and strong
(c) colourless and paramagnetic ligands.
(d) coloured and paramagnetic (b) It does not give quantitative interpretation of magnetic
69. The compound which is not coloured is data.
(a) K4[Fe(CN)6] (b) K3[Fe(CN)6] (c) It does not explain the colour exhibited by coordination
(c) Na2[CdCl4] (d) Na2[CuCl4] compounds
70. Which of the following complexes exhibits the highest (d) All of these
paramagnetic behaviour ? 78. Which complex of Co2+ will have the weakest crystal field
(a) [V(gly)2(OH)2(NH3)2]+ (b) [Fe(en)(bpy)(NH3)2]2+ splitting –
(c) [Co(ox)2(OH)2]2– (d) [Ti(NH3)6]3+ (a) [CoCl6]4– (b) [Co(CN)6]4–
where gly = glycine, en = ethylenediamine and bpy = (c) [Co(NH3)6] 2+ (d) [Co(en)3]2+
bipyridyl moities)
79. In which of the following complexes of the Co (at. no. 27),
(At.nosTi = 22, V = 23, Fe = 26, Co = 27)
will the magnitude of Do be the highest?
71. Which of the following complex ion is not expected to absorb
(a) [Co(CN)6]3– (b) [Co(C2O4)3]3–
visible light ? 3+
(c) [Co(H2O)6] (d) [Co(NH3)6]3+
(a) [Ni(CN)4]2– (b) [Cr(NH3)6]3+
2+ 80. Among the ligands NH3, en, CN– and CO the correct order
(c) [Fe(H2O)6] (d) [Ni(H2O)6]2+
of their increasing field strength, is :
72. Which one of the following is an outer orbital complex and
(a) NH3 < en < CN – < CO
exhibits paramagnetic behaviour ?
(b) CN – < NH3 < NH3 < en
(a) [Ni(NH3)6]2+ (b) [Zn(NH3)6)]2+
(c) [Cr(NH3)6] 3+ (d) [Co(NH3)6]3+ (c) en < CN – < NH3 < CO
73. Which of the following options are correct for [Fe(CN)6]3– (d) CO < NH3 < en < CN –
complex ? 81. Which of the following statements related to crystal field
(i) Possess d2sp3 hybridisation splitting in octahedral coordination entities is incorrect?
(ii) Possess sp3d2 hybridisation (a) The d 2 2 and dz 2 orbitals has more energy as
x –y
(iii) It is paramagnetic compared to dxy, dyz and dxz orbitals.
(iv) It is diamagnetic (b) Crystal field spitting energy (Do) depends directly on
(a) (i) and (iii) (b) (ii) and (iii) the charge of the metal ion and on the field produced
(c) (i) and (iv) (d) (ii) and (iv) by the ligand.
74. Which of the following statements is incorrect? (c) In the presence of Br– as a ligand the distribution of
(a) [MnCl6]3– is more paramagnetic than [Mn(CN)6]3– electrons for d4 configuration will be t 32 g , eg1,
(b) Both [Co(C2O4)3]3– and [CoF6]3– are paramagnetie. (d) In the presence of CN– as a ligand Do < P.
(c) [Fe(CN)6]3– forms inner orbital complex whereas 82. For which of the following ligands magnitude of the crystal
[FeF6]3– forms outer orbital complex.
field splitting (Do) will be greater than pairing energy (P)?
(d) Both (a) and (b).
(a) Cl– (b) SCN– (c) CO (d) S2–
75. The correct statement with respect to the complexes Ni(CO)4
83. Which of the following is the limitation of crystal field
and [Ni(CN)4]2– is
theory?
(a) nickel is in the same oxidation state in both
(i) Ligands are assumed as point charges.
(b) both have tetrahedral geometry
(ii) It does not accounts for the covalent character of
(c) both have square planar geometry
bonding between the ligand and the central atom.
(d) have tetrahedral and square planar geometry (iii) It does not explain how colour of coordination
respectively
compounds depends on ligand attached to central
76. Which of the following are inner orbital complex (i.e., metal atom/ion.
involving d2sp3 hybridisation) and is paramagnetic in (a) (i) and (ii) (b) (ii) and (iii)
nature?
(c) (ii) only (d) (i), (ii) and (iii)
(a) [Mn(CN)6]3– , [Fe(CN)6]3–, [Co(C2O4)3]3–
84. If magnetic moment of [MnBr4]2– is 5.9 BM. Predict the
(b) [MnCl6]3–, [FeF6]3–, [CoF6]3–
number of electrons?
(c) [Mn(CN)6]3–, [Fe(CN)6]3–
(a) 2 (b) 3 (c) 6 (d) 5
(d) [MnCl6]3– , [Fe(CN)6]3–, [Co(C2O4)3]3–
COORDINATION COMPOUNDS 323

85. Which of the following does not have a metal- carbon bond? 92. Match the columns.
(a) Al(OC2H5)3 (b) C2H5MgBr Column-I Column-II
(c) K[Pt(C2H4)Cl3] (d) Ni(CO)4 (Complexes) (Absorbed Light)
86. In Fe(CO)5, the Fe – C bond possesses (A) [Ni(H2O)4(en)]2+(aq) (p) Yellow Orange
(a) ionic character (b) s-character only (B) [Ni(H2O)4(en)2]2+(aq) (q) Blue–Green
(c) p-character (d) both s and p characters 2+
(C) [Ni(en)3] (aq) (r) Red
87. The unpaired electrons in Ni(CO)4 are (a) A – (r), B – (q), C – (p)
(a) zero (b) one (c) three (d) four (b) A – (p), B – (r), C – (q)
88. The correct structure of Fe(CO)5 is (Z=26 for Fe) (c) A – (q), B – (r), C – (p)
(a) octahedral (b) tetrahedral
(d) A – (r), B – (p), C – (q)
(c) square pyramidal (d) trigonal bipyramidal
93. Assertion : [Ti(H2O)6]3+ is coloured while [Sc(H2O)6]3+ is
89. Which of the following statements are correct? colourless.
(i) Square planar complexes of MABXL type show three Reason : d-d transition is not possible in [Sc(H2O)6]3+.
isomers-two cis and one trans.
(a) Assertion is correct, reason is correct; reason is a
(ii) Complexes of Ma3B3 type show three isomers-two cis correct explanation for assertion.
and one trans. (b) Assertion is correct, reason is correct; reason is not a
(iii) Optical isomerism is common in octahedral complexes correct explanation for assertion
involving bidentate ligands. (c) Assertion is correct, reason is incorrect
(iv) [Co(NH3)4Cl (NO2)]Cl show linkage isomerism. (d) Assertion is incorrect, reason is correct.
(v) Hydrate isomerism is another name of solvate 94. Which one of the following complexes is an outer orbital
isomerism. complex ?
(a) (i), (ii) and (iii) (b) (i), (iii) and (iv) (a) [Co(NH3)6]3+ (b) [Mn(CN)6]4–
(c) (ii), (iii) and (v) (d) (iii), (iv) and (v) (c) [Fe(CN)6]4– (d) [Ni(NH3)6]2+
90. Which of the following statements are correct? (Atomic nos. : Mn = 25; Fe = 26; Co = 27, Ni = 28)
(i) When light of wavelength 600nm is absorbed by 95. The d-electron configurations of Cr 2+, Mn2+, Fe2+ and Co2+
complex [Ti(H2O)6]3+ its configuration changes from are d 4, d 5, d 6 and d 7, respectively. Which one of the
following will exhibit minimum paramagnetic behaviour?
t12g e0g ¾¾
® t 02g e1g and it appears violet in colour.. (a) [Mn(H2O)6]2+ (b) [Fe(H2O)6]2+
(ii) Anhydrous CuSO4 is white but CuSO4 .5H2O is blue in (c) [Co(H2O)6]2+ (d) [Cr(H2O)6]2+
colour as presence of H2O as a ligand causes crystal (At, nos. Cr = 24, Mn = 25, Fe = 26, Co = 27)
field spitting. 96. Both [Ni(CO)4] and [Ni(CN)4]2– are diamagnetic. The
(iii) Ruby is aluminum oxide containing 0.5 – 1% Cr 3+ hybridisations of nickel in these complexes, respectively,
ions with d3 configuration. are
(iv) Crystal field theory predict correctly that anionic (a) sp3, sp3 (b) sp3, dsp2
ligands should exert the greater splitting effect. (c) dsp2, sp3 (d) dsp2, sp2
(a) (i), (ii) and (iii) (b) (ii) and (iii) 97. The value of the ‘spin only’ magnetic moment for one of the
(c) (i), and (ii) (d) (ii), (iii) and (iv) following configurations is 2.84 BM. The correct one is
(a) d 5 (in strong ligand field)
91. Which of the following statement(s) is/are incorrect?
(b) d 3 (in weak as well as in strong fields)
(i) In metal carbonyls M–C s bond is formed by the
donation of lone pair of electrons on the carbonyl (c) d 4 (in weak ligand fields)
carbon into a vacant orbital of metal. (d) d 4 (in strong ligand fields)
(ii) M—C p bond is formed by the donation of a pair of 98. According to valence bond theory which of the following
statement is correct about the complexes Ni(CO)4 and
electrons from a filled d orbital of metal into the vacant
[Ni(CN)4]2– if both are diamagnetic in nature
antibonding p* orbital of CO.
(a) both are tetrahedral
(iii) Bonding in metal carbonyls is called synergic bonding.
(b) both are square planar
(a) (i) and (ii) (b) (iii) only
(c) one is square planar and other is tetrahedral
(c) (ii) only (d) None of these
(d) one is tetrahedral and other is square planar
 EBD_7374
324 CHEMISTRY

99. Correct statements about the following complexes [MnCl6]3– (B) Extraction of silver. (q) [Ni(CO)4]
and [Mn(CN)6]3– respectively are. (C) Hydrogenation of (r) Na2EDTA
(a) Magnetic moment is 4.8 and 2.8 alkenes.
(b) inner sphere and outer sphere complexes. (D) Photography (s) [(Ph3P)3RhCl]
(c) sp3d 2 and d 2 sp3 complexes. (E) Purification of (t) [Ag(S2O3)2]3–
(d) Both (a) and (c). Nickel.
100. Which of the following complex ions is expected to absorb (a) A – (r) , B – (p), C – (s), D – (t), E– (q)
visible light? (b) A – (p) , B – (r), C – (s), D – (t), E– (q)
(a) [Ti (en)2(NH3)2]4 + (b) [Cr (NH3)6]3 + (c) A – (r) , B – (s), C – (p), D – (t), E– (q)
(c) [Zn (NH3)6] 2 + (d) [Sc (H2O)3 (NH3)3]3+ (d) A – (r) , B – (p), C – (s), D – (q), E– (t)
(At. no. Zn = 30, Sc = 21, Ti = 22, Cr = 24) 108. Match the columns.
101. Low spin complex of d 6 -cation in an octahedral field will Column-I Column-II
have the following energy : (Coordination compound) (Central metal atom)
-12 -12 (A) Chlorophyll (p) Rhodium
(a) D0 + P (b) D 0 + 3P
5 5 (B) Blood pigment (q) Cobalt
(C) Wilkinson catalyst (r) Calcium
-2 -2 (D) Vitamin B12 (s) Iron
(c) D 0 + 2P (d) D0 + P
5 5
(t) Magnesium
(D0= Crystal Field Splitting Energy in an octahedral field, (a) A – (t), B – (s), C – (p), D – (q)
P = Electron pairing energy) (b) A – (s), B – (q), C – (p), D – (r)
102. Which of the following carbonyls will have the strongest (c) A – (p), B – (q), C – (r), D – (s)
C – O bond ?
(d) A – (r), B – (t), C – (p), D – (q)
(a) [Mn (CO)6]+ (b) [Cr (CO)6]
109. C63H88CoN14O14P is the formulae of the Cyanocobalamine,
(c) [V (CO)6] – (d) [Fe (CO)5] (vitamin B12) it contain CN– and CN– is very poisonous,
103. For [Co2(CO)8], what is the total number of metal – carbon than why this compound does not prove to be fatal for
bonds and number of metal–metal bonds. us? (it inhibit the electron transport chain ?
(a) 10 ,1 (b) 8, 2 (c) 8, 1 (d) 10, 0 (a) CN– forms covalent bond
(b) CN– is coordinating to the cobalt as the ligand
Topic 4: Stability of Coordination Compounds,
Importance and Application of Coordination Compounds (c) CN– hydrolysis immediately
(d) All of these
ˆˆ† ML4
104. For the reaction of the type M + 4L ‡ˆˆ 110. Consider the following reactions.
(a) larger the stability constant, lower the proportion of [XY]
ML4 that exists in solution X + Y ƒ XY K1=
[X][Y]
(b) larger the stability constant, higher the proportion of
ML4 that exists in solution [XY2 ]
(c) smaller the stability constant, higher the proportion of XY + Y ƒ XY2 K2 =
[XY][Y]
ML4 that exists in solution
(d) None of the above [ XY3 ]
XY2 + Y ƒ XY3 K3 = XY Y
105. Which one of the following coordination compounds is [ 2 ][ ]
used to inhibit the growth of tumours?
On the basis of reactions above which of the following is
(a) Trans-platin (b) EDTA complex of calcium
incorrect?
(c) [(Ph3P)3RhCl] (d) Cis-platin
(a) Overall stability constant = K1K2K3
106. Calculate the value of log K3 when log values of K2, K1, K4
and b4 respectively are 4.0, 3.20, 4.0 and 11.9 ? [XY3 ]
(a) 2.0 (b) 2.7 (c) 3.0 (d) 2.5 (b) K1K2K3 =
[X][Y]3
107. Match the columns. 1
Column-I Column-I (c) Dissociation constant = Formation constant .
(A) Estimation of (p) [Ag(CN)2]– (d) All of the above are correct.
water hardness.
COORDINATION COMPOUNDS 325

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 9. Due to the presence of ambidentate ligands coordination
compounds show isomerism. Palladium complexes of the
1. Which of the following complexes formed by Cu2+ ions is
type [Pd(C6H5)2 (SCN)2] and [Pd(C6H5)2 (NCS)2] are
most stable?
(a) linkage isomers (b) coordination isomers
(a) Cu2+ + 4NH3 ® [Cu(NH3)4]2+, log K = 11.6 (c) ionisation isomers (d) geometrical isomers
(b) Cu2+ + 4CN– ® [Cu(CN)4]2–, log K = 27.3 10. The compounds [Co(SO4) (NH3)5] Br and [Co(SO4) (NH3)5]
(c) Cu2+ + 2en ® [Cu(en)2]2+, lok K = 15.4 Cl represent
(d) Cu2+ + 4H2O ® [Cu(H2O)4]2+, log K = 8.9 (a) linkage isomerism (b) ionisation isomerism
2. The colour of the coordination compounds depends on the (c) coordination isomerism (d) no isomerism
crystal field splitting. What will be the correct order of 11. A chelating agent has two or more than two donor atoms to
bind to a single metal ion. Which of the following is not a
absorption of wavelength of light in the visible region, for
chelating agent?
the complexes, [Co(NH3)6]3+, [Co(CN)6]3–, [Co(H2O)6]3+.
(a) Thiosulphato (b) Oxalato
(a) [Co(CN)6]3– > [Co(NH3)6]3+ > [Co(H2O)6]3+
(c) Glycinato (d) Ethane-1, 2-diamine
(b) [Co(NH3)6]3+ > [Co(H2O)6]3+ > [Co(CN)6]3– 12. Which of the following species is not expected to be a ligand?
(c) [Co(H2O)6]3+ > [Co(NH3)6]3+ > [Co(CN)6]3–
(a) NO (b) NH +4
(d) [Co(CN)6]3– > [Co(NH3)6]3+ < [Co(H2O)6]3+
3. When 0.1 mol CoCl3 (NH3)5 is treated with excess of AgNO3, (c) NH2CH2CH2NH2 (d) CO
0.2 mol of AgCl are obtained. The conductivity of solution 13. What kind of isomerism exists between [Cr(H2O)6] Cl 3
will correspond to (violet) and [Cr (H2O)5Cl] Cl2 . H2O (greyish-green)?
(a) 1 : 3 electrolyte (b) 1 : 2 electrolyte (a) Linkage isomerism
(b) Solvate isomerism
(c) 1 : 1 electrolyte (d) 3 : 1 electrolyte
(c) Ionisation isomerism
4. When 1 mole of CrCl3 . 6H2O is treated with excess of AgNO3,
(d) Coordination isomerism
3 moles of AgCl are obtained. The formula of the complex is
14. IUPAC name of [Pt(NH3)2Cl(NO2)] is
(a) [CrCl3(H2O)3] . 3H2O (b) [CrCl2(H2O)4]Cl . 2H2O
(a) Platinum diamminechloronitrite
(c) [CrCl(H2O)5]Cl2 . H2O (d) [Cr(H2O)6]Cl3 (b) Chloronitrito-N-ammineplatinum (II)
5. The correct IUPAC name of [Pt (NH3)2Cl2] is (c) Diamminechloridonitrito-N-platinum (II)
(a) Diamminedichloridoplatinum (II) (d) Diamminechloronitrito-N-plantinate (II)
(b) Diamminedichloridoplatinum (IV)
Past Year MCQs
(c) Diamminedichloridoplatinum (0)
(d) Dichloridodiammineplatinum (IV) 15. Among the following complexes the one which shows zero
6. The stabilisation of coordination compounds due to crystal field stabilization energy (CFSE): [AIPMT 2014, A]
chelation is called the chelating effect. Which of the (a) [Mn(H2O)6]3+ (b) [Fe(H2O)6]3+
following is the most stable complex species? (c) [Co(H2O)6]2+ (d) [Co(H2O)6]3+
(a) [Fe(CO)5] (b) [Fe(CN)6]3–
16. Which of the following complexes is used as an anti-cancer
(c) [Fe(C2O4)3]3– (d) [Fe(H2O)6]3+
agent: [AIPMT 2014, A]
7. Indicate the complex ion which shows geometrical isomerism.
(a) mer-[Co(NH3)3Cl3] (b) cis-[PtCl2(NH3)2]
(a) [Cr(H2O)4Cl2]+ (b) [Pt(NH3)3Cl]3–
(c) [Co(NH3)6]3– (d) [Co(CN)5(NC)]3– (c) cis-K2[PtCl2Br2] (d) Na2CoCl4
8. The CFSE for octahedral [CoCl6]4– is 18,000 cm–1. The CFSE 17. The coordination number and the oxidation state of the
for tetrahedral [CoCl4]2– will be element ‘E’ in the complex [E(en)2(C2O4)]NO2 (where (en) is
(a) 18,000 cm–1 (b) 16,000 cm–1 ethylene diamine) are, respectively, [AIIMS 2014, A]
(c0 8,000 cm–1 (d) 20,000 cm–1 (a) 6 and 2 (b) 4 and 2 (c) 4 and 3 (d) 6 and 3
 EBD_7374
326 CHEMISTRY

18. In the isoelectronic series of metal carbonyl, the CO bond 24. Cobalt (III) chloride forms several octahedral complexes with
strength is expected to increase in the order: ammonia. Which of the following will not give test of chloride
[AIIMS 2014, A] ions with silver nitrate at 25ºC ? [AIPMT 2015, A]
(a) [Mn(CO) 6 ] + < [Cr(CO)6 ] < [V (CO) 6 ] - (a) CoCl3·4NH3 (b) CoCl3·5NH3
(d) [V (CO)6 ] - < [Cr(CO)6 ] < [Mn(CO)6 ] + (c) CoCl3·6NH3 (d) CoCl3·3NH3
(c) [V (CO)6 ] - < [Mn(CO) 6 ] + < [Cr(CO) 6 ]
25. The sum of coordination number and oxidation number of
(d) [Cr(CO)6 ] < [Mn(CO)6 ] + < [V (CO) 6 ] -
the metal M in the complex [M(en)2(C2O4)]Cl (where en is
19. Which of the following is paramagnetic? [AIIMS 2014, S]
ethylenediamine) is: [AIPMT 2015 RS, S]
(a) [Fe (CN )6 ]4- (b) [Ni (CO )4 ]
(a) 9 (b) 6 (c) 7 (d) 8
(d) [CoF6 ]
3-
(c) [Ni (CO )4 ] 2-
26. The name of complex ion, [Fe(CN)6]3– is :
20. Assertion : Ethylenediaminetetraacetate ion forms an
octahedral complex with the metal ion. (a) Hexacyanoiron (III) ion [AIPMT 2015 RS, S]
Reason : It has six donor atoms which coordinate (b) Hexacyanitoferrate (III) ion
simultaneously to the metal ion. (c) Tricyanoferrate (III) ion
[AIIMS 2014, C] (d) Hexacyanidoferrate (III) ion
(a) If both Assertion and Reason are correct and Reason
27. Number of possible isomers for the complex [Co(en)2Cl2]Cl
is the correct explanation of Assertion.
will be (en = ethylenediamine) [AIPMT 2015 RS, S]
(b) If both Assertion and Reason are correct, but Reason
is not the correct explanation of Assertion. (a) 2 (b) 1 (c) 3 (d) 4
(c) If Assertion is correct but Reason is incorrect. 28. Which of these statements about [Co(CN)6]3– is true ?
(d) If both the Assertion and Reason are incorrect. [AIPMT 2015, C]
21. The octahedral complex of a metal ion M3+ with four (a) [Co(CN)6]3– has four unpaired electrons and will be in
monodentate ligands L1, L2, L3 and L4 absorb wavelengths a low-spin configuration.
in the region of red, green, yellow and blue, respectively.
(b) [Co(CN)6]3– has four unpaired electrons and will be in
The increasing order of ligand strength of the four ligands
a high spin configuration.
is: [JEE M 2014, A]
(c) [Co(CN)6]3– has no unpaired electrons and will be in a
(a) L 4 <L3 <L 2 <L1 (b) L1 <L3 <L 2 <L 4 high-spin configuration.
(d) [Co(CN)6]3– has no unpaired electrons and will be in a
(c) L3 <L 2 <L 4 <L1 (d) L1 <L 2 <L 4 <L3
low-spin configuration.
22. The equation which is balanced and represents the correct 29. Coordination compounds have great importance in biological
product(s) is: [JEE M 2014, S] systems. In this context which of the following statements
(a) Li 2O + 2KCl ® 2LiCl + K 2 O is incorrect ? [AIIMS 2015, C]
(a) Cyanocobalamin is B12 and contains cobalt
+
(b) é CoCl ( NH3 ) ù + 5H + ® Co 2+ + 5NH +4 + Cl - (b) Haemoglobin is the red pigment of blood and contains
ë 5û
iron
2+ 4- (c) Chlorophylls are green pigments in plants and contain
(c) é Mg ( H 2 O ) ù + ( EDTA )
excess NaOH
¾¾¾¾¾¾
®
ë 6û calcium
2+ (d) Carboxypeptidase - A is an exzyme and contains zinc.
éë Mg ( EDTA )ùû + 6H 2 O
30. Consider the following complex [Co(NH3)5CO3]ClO4. The
coordination number, oxidation number, number of d-
(d) CuSO 4 + 4KCN ® K 2 éëCu ( CN )4 ùû + K 2SO 4 electrons and number of unpaired d-electrons on the metal
are respectively [AIIMS 2015, S]
23. The correct order of magnetic moments (spin only values in
B.M.) among is [BITSAT 2014, A] (a) 6, 3, 6, 0 (b) 7, 2, 7, 1 (c) 7, 1, 6, 4 (d) 6, 2, 7, 3
(a) [Fe (CN) 6 ]4- > [MnCl 4 ]2- > [CoCl 4 ] 2- 31. Which of the following compounds is not colored yellow ?
(b) [MnCl 4 ]2- > [Fe (CN ) 6 ]4- > [CoCl 4 ] 2- [JEE M 2015, A]
(c) [MnCl 4 ]2- > [CoCl 4 ]2- > [ Fe (CN) 6 ] 4- (a) (NH4)3[As(Mo3O10)4] (b) BaCrO4
(d) [Fe(CN) 6 ]4- > [CoCl 4 ]2- > [ MnCl 4 ] 2-
(c) Zn2[Fe(CN)6] (d) K3[Co(NO2)6]
(Atomic nos. : Mn = 25, Fe = 26, Co = 27)
COORDINATION COMPOUNDS 327

32. The number of geometric isomers that can exist for square (a) [Mn(H2O)6]2+ and [Cr(H2O)6]2+
planar complex [Pt(Cl)(py)(NH3)(NH2OH)]+ is (py = pyridine). (b) [CoCl4]2– and [Fe(H2O)6]2+
[JEE M 2015, S] (c) [Cr(H2O)6]2+ and [CoCl4]2–
(a) 4 (b) 6 (c) 2 (d) 3 (d) [Cr(H2O)6]2+ and [Fe(H2O)6]2+
33. The color of KMnO4 is due to : [JEE M 2015, C] 43. The hypothetical complex chloro-diaquatriamminecobalt (III)
(a) L ® M charge transfer transition chloride can be represented as [BITSAT 2016, A]
(a) [CoCl(NH3)3(H2O)2 ]Cl2
(b) s - s* transition
(b) [Co(NH3)3(H2O)Cl3]
(c) M ® L charge transfer transition
(c) [Co(NH3)3(H2O)2Cl]
(d) d – d transition
(d) [Co(NH3)3(H2O)3]Cl3
34. The color of CoCl3.5NH3.H2O is [BITSAT 2015, A]
(a) red (b) orange 44. Which of the following is paramagnetic ?
(c) orange - yellow (d) pink [BITSAT 2016, C]
35. Some salts containing two different metallic elements give (a) [Fe(CN)6]4– (b) [Ni(CO)4]
test for only one of them in solution, such salts are (c) [Ni(CN)4]2– (d) [CoF6]3–
[BITSAT 2015, C]
45. HgCl2 and I2 both when dissolved in water containing I
(a) double salts (b) normal salts
ions the pair of species formed is : [NEET 2017, S]
(c) complex salts (d) None of these
36. Which of the following represents hexadentate ligand? (a) HgI2, I– (b) HgI24 - , I3-
[BITSAT 2015, 2009, C] (c) Hg2I2, I– (d) HgI2 , I3-
(a) EDTA (b) DMG
(c) Ethylenediamine (d) None of the above 46. The correct order of the stoichiometries of AgCl formed
37. The common name of K[PtCl3(h2.C2H4)] is when AgNO3 in excess is treated with the complexes :
[BITSAT 2015, S] CoCl3.6NH3, CoCl3.5NH3, CoCl3.4NH3 respectively is :-
(a) potassium salt (b) Zeise’s salt [NEET 2017, A]
(c) complex salt (d) None of these (a) 3 AgCl, 1 AgCl, 2 AgCl (b) 3 AgCl, 2 AgCl, 1 AgCl
38. Which of the following has longest C–O bond length? (Free (c) 2 AgCl, 3 AgCl, 1 AgCl (d) 1 AgCl, 3 AgCl, 2 AgCl
C–O bond length in CO is 1.128Å) [NEET 2016, S] 47. Correct increasing order for the wavelengths of absorption
(a) Ni(CO)4 (b) [Co(CO)4]– in the visible region the complexes of Co3+ is :
[NEET 2017, S]
(c) [Fe(CO)4]2– (d) [Mn(CO)6]+
(a) [Co(H2O)6]3+, [Co(en)3]3+, [Co(NH3)6]3+
39. The deep blue colour produced on adding excess of (b) [Co(H2O)6]3+, [Co(NH3)6]3+, [Co(en)3]3+
ammonia to copper sulphate is due to presence of (c) [Co(NH3)6]3+, [Co(en)3]3+, [Co(H2O)6]3+
[AIIMS 2016, A] (d) [Co(en)3]3+, [Co(NH3)6]3+, [Co(H2O)6]3+
(a) Cu 2 + (b) [ Cu(NH3 )4 ]2+ 48. Pick out the correct statement with respect to [Mn(CN)6]3–
(c) [Cu(NH 3 ) 6 ]
2+
(d) [Cu(NH3 )2 ]2 + [NEET 2017, S]
40. 0.02 mole of [Co(NH 3 ) 5Br]Cl 2 and 0.02 mole of (a) It is sp3d2 hybridised and tetrahedral
[Co(NH3)5Cl]SO4 are present in 200 cc of a solution X. The (b) It is d2sp3 hybridised and octahedral
number of moles of the precipitates Y and Z that are formed (c) It is dsp2 hybridised and square planar
when the solution X is treated with excess silver nitrate and (d) It is sp3d2 hybridised and octahedral
excess barium chloride are respectively 49. An example of a sigma bonded organometallic compound is :
[AIIMS 2016, A] [NEET 2017, A]
(a) Grignard's reagent (b) Ferrocene
(a) 0.02, 0.02 (b) 0.01, 0.02 (c) 0.02, 0.04 (d) 0.04, 0.02
(c) Cobaltocene (d) Ruthenocene
41. Which one of the following complexes shows optical
50. Which of the following coordination compounds would
isomerism? [JEE M 2016, S]
exhibit optical isomerism? [AIIMS 2017, A]
(a) trans-[Co(en)2Cl2]Cl (b) [Co(NH3)4Cl2]Cl (a) pentamminenitrocobalt (III) iodide
(c) [Co(NH3)3Cl3] (d) cis-[Co(en)2Cl2]Cl (b) diamminedichloroplatinum (II)
42. The pair having the same magnetic moment is: (c) trans-dicyanobis (ethylenediamine) chromium (III)
[At. No.: Cr = 24, Mn = 25, Fe = 26, Co = 27] chloride
(d) tris-(ethylendiamine) cobalt (III) bromide
[JEE M 2016, S]
 EBD_7374
328 CHEMISTRY
+2 +3
51. Assertion : [Fe(CN)6]3– is weakly paramagnetic while 59. Assertion : éë Cr ( H 2 O )6 ùû éëCr ( H 2O )6 ùû while convert-
[Fe(CN)6]4– is diamagnetic. ing, colour continuously changes.
Reason : [Fe(CN)6]3– has +3 oxidation state while [Fe(CN)6]4– Reason : CFSE increase during change. [AIIMS 2018, A]
has +2 oxidation state. [AIIMS 2017, C] (a) If both assertion and reason are true and reason is the
(a) If both Assertion and Reason are correct and Reason correct explanation of assertion.
is the correct explanation of Assertion. (b) If both assertion and reason are true but reason is not
(b) If both Assertion and Reason are correct, but Reason the correct explanation of assertion.
is not the correct explanation of Assertion. (c) If assertion is true but reason is false.
(c) If Assertion is correct but Reason is incorrect.
(d) If both assertion and reason are false.
(d) If both the Assertion and Reason are incorrect.
60. Consider the following reaction and statements:
52. On treatment of 100 mL of 0.1 M solution of CoCl 3 . 6H2O
[Co(NH3)4Br2]+ + Br– ® [Co(NH3)3Br3] + NH3
with excess AgNO3; 1.2 × 1022 ions are precipitated. The
[JEE M 2018, C]
complex is : [JEE M 2017, S]
(I) Two isomers are produced if the reactant complex ion
(a) [Co(H2O)4 Cl2]Cl.2H2O (b) [Co(H2O)3Cl3].3H2O
is a cis-isomer.
(c) [Co(H2O)6]Cl3 (d) [Co(H2O)5Cl]Cl2.H2O
(II) Two isomers are produced if the reactant complex ion
53. Which of the following complex shows sp3d2 hybridization?
is a trans -isomer.
[BITSAT 2017, S]
(III) Only one isomer is produced if the reactant complex
(a) [Cr(NO2)6]3- (b) [Fe(CN)6]4– ion is a trans -isomer.
(c) [CoF6]3- (d) [Ni(CO)4] (IV) Only one isomer is produced if the reactant complex
54. Which of the following complexes has square planar ion is a cis-isomer.
structure? [BITSAT 2017, A] The correct statements are:
(a) Ni(CO) 4 (b) [ Ni(CN) 4 ]2 - (a) (I) and (II) (b) (I) and (III)
(c) [ Ni(Cl) 4 ]2 - (d) [ Zn(NH3 )4 ]2 + (c) (III) and (IV) (d) (II) and (IV)
55. Iron carbonyl, Fe(CO)5 is [NEET 2018, C] 61. Which of the following element do not form complex with
(a) Tetranuclear (b) Mononuclear EDTA? [BITSAT 2018, C]
(c) Dinuclear (d) Trinuclear (a) Ca (b) Mg (c) Be (d) Sr
56. The type of isomerism shown by the complex [CoCl2(en)2] 62. Which one of the following cyano complexes would exhibit
is [NEET 2018, C] the lowest value of paramagnetic behaviour ?
(a) Geometrical isomerism
[BITSAT 2018, C]
(b) Coordination isomerism
(c) Linkage isomerism (a) [Co(CN) 6 ]3 - (b) [Fe(CN) 6 ]3 -
(d) Ionization isomerism (c) [Mn (CN) 6 ]3 - (d) [Cr (CN) 6 ]3 -
57. The geometry and magnetic behaviour of the complex (At. Nos : Cr = 24, Mn = 25, Fe = 26, Co = 27)
[Ni(CO)4] are [NEET 2018, C] 63. When an aqueous solution of copper (II) sulphate is
(a) Square planar geometry and diamagnetic saturated with ammonia, the blue compound crystallises
(b) Tetrahedral geometry and diamagnetic on evaporation. The formula of this blue compound is:
(c) Tetrahedral geometry and paramagnetic [BITSAT 2018, A]
(d) Square planar geometry and paramagnetic (a) [Cu(NH3)4]SO4. H2O (square planar)
58. Cr3+ in aquous medium forms 5 green coloured complex with
(b) [Cu(NH3)4]SO4 (Tetrahedral)
NH3 ligand. How many ligands are associated with it ?
[AIIMS 2018, S] (c) [Cu(NH3)6]SO4 (Octahedral)
(a) 3 (b) 4 (c) 5 (d) 6 (d) [Cu(SO4) (NH3)5] (Octahedral)
COORDINATION COMPOUNDS 329

Exercise 3 : Try If You Can

1. Incorrect matching for given complex compound/ion and A gives a white precipitate with AgNO3 solution and the
its characteristics: solution of B gives white precipitate with BaCl2 solution.
(a) [CrBrCl(en)2 ] Br Ionization and optical The type of isomerism exhibited by the complex is:
isomerism (a) Linkage isomerism (b) Ionisation isomerism
(c) Coordinate isomerism (d) Geometrical isomerism
(b) [CoBr3 ( H 2 O )3 ] Fac-mer and hydrate 6. Which of the following is correctly matched?
isomerism Column - I Column - II Column - III

(c) [PtCl 2 ( NH3 )4 ] Linkage isomerism and (a) [Cr(CO)6 ] Paramagnetic Octahedral, sp 3d 2

[Co(SCN)4 ] paramagnetic character (b) [ Fe(CO)5 ] Paramagnetic Trigonal bipyramidal, sp3d

(d) [Co(ox)3 ]3- Inner orbital complex and

(c) [ Co(CO)4 ] Paramagnetic Square planar, dsp 2

optical isomerism (d) [ Ni(CO)4 ]Diamagnetic Square planar, dsp 2

2. For complex ion/compound formation reactions 7. Which of the following order of stability of complex ion is
Incorrect?
(I) Co3+ (aq.) + EDTA 4 - ¾¾
®P 3- 3+
(a) [Fe(C 2 O 4 )3 ] < [Fe(H 2 O) 6 ]
(II) Ni 2 + (aq.) + dmg (excess) ¾¾¾¾
4 ®Q
NH OH (b) [ Fe(edta)]- > [ Fe(en)3 ]3+
+
(c) [ Ni(en)2 ]2+ > [ Ni(DMG)2 ]
(III) Zn 2 (aq.) + gly(excess) ¾¾
®R (d) [ Fe(CN)6 ]3- > [ Fe(CN)6 ]4-
4+ 8. Which of the following complex ions has electrons that
(IV) Pt (aq.) + en(excess) ¾¾
®S
are symmetrically filled in both t2g and eg orbitals ?
which of the following complex ion/compound does not (a) [FeF3]3– (b) [Mn(CN)6]4–
exhibit optical activity? (c) [CoF6]3– (d) [CO(NH3)6]2+
(a) P (b) Q (c) R (d) S
9. Which of the characteristic is not common between
2+
3. [ Ni(NH3 )6 ] + en ¾¾
® X + 2NH3 [Cu(en)2)2+ and [Ni(dmg)2] ?
(a) Geometry of complexes
[ Ni(NH3 )6 ] + 2en ¾¾® Y + 4NH3 (b) Hybridization of central metal cation
(c) Magnetic behaviour
[ Ni(NH3 )6 ] + 3en ¾¾® Z + 6NH3 (d) Number of stereoisomers
Which of them show optical as well as geometrical 10. Among the following complexes (K-P)
isomerism?
K3[Fe(CN)6] (K), [Co(NH3)6]Cl3 (L), Na3[Co(oxalate)3] (M),
(a) X (b) Y
[Ni(H2O)6]Cl2 (N), K2[Pt(CN)4] (O) and [Zn(H2O)6](NO3)2 (P)
(c) Z (d) All of these
the diamagnetic complexes are
4. [Cr(H2O)6]Cl3 (atomic number of Cr = 24) has a magnetic
(a) K, L, M, N (b) K, M, O, P
moment of 3.83 BM. The correct distribution of 3d-elections
in the chromium present in the complex is (c) L, M, O, P (d) L, M, N, O
1 1 1 11. [NiCl2 {P(C2H5)2(C6H5)}2] exhibits temperature dependent
(a) 3d1xy , 3d1yz ,3d1zx (b) 3d xy ,3d yz ,3d z 2 magnetic behaviour (paramagnetic/diamagnetic). The
coordination geometries of Ni2+ in the paramagnetic and
(c) 3d1 ,3d1 2 ,3d1zx diamagnetic states are respectively
(x 2 - y 2 ) z
(a) tetrahedral and tetrahedral
1 1 1
(d) 3d xy , 3d (x 2 - y2 ) ,3d xz (b) square planar and square planar
5. An octahedral complex with molecular composition (c) tetrahedral and square planar
M.5 NH3.Cl.SO4 has two isomers, A and B. The solution of (d) square planar and tetrahedral
 EBD_7374
330 CHEMISTRY

12. The magnetic moment of a certain complex (A) of Co was Choose the correct code:
found to be 4.89 BM and the EAN as 36. Co also forms (a) I only (b) II and III (c) I and IV (d) IV only
complex (B) with magnetic moment 3.87 BM and EAN as
14. Among the following pairs of complexes, in which case the
37, and complex (C) with EAN as 36 but diamagnetic. Which
D0 value is higher for the first one?
of the following statements is true regarding the above
observation? (a) [Co(NH3 )6 ]3+ and [Co(CN) 6 ]3-
(a) The oxidation states of Co in (A), (B) and (C) are +3, (b) [Co(F6 )]3– and [Co(NH3 )6 ]3+
+2 and +3, respectively.
(b) Complexes (A) and (B) have sp3d2 hybridisation state (c) [Co(H 2O)6 ]2+ and [Co(H 2 O)6 ]3+
while (C) has dsp3 hybridisation state. (d) [ Rh(H 2O)6 ]3+ and [Co(H 2O)6 ]3+
(c) The spin multiplicities of Co in (A), (B) and (C) are 3, 2 15. An aqueous solution of titanium chloride, when subjected
and 1, respectively.
to magnetic measurement, measured zero magnetic moment.
(d) The oxidation states of Co in (A), (B) and (C) are +6,
Assuming the octahedral complex in aqueous solution, the
+8 and +1, respectively.
formulae of the complex is:
13. Which of the following complex compound(s) is/are
paramagnetic and low spin? (a) [Ti(H2O)6 ] Cl2 (b) [Ti(H2 O)6 ] Cl4
(I) K 3 éë Fe ( CN 6 ) ùû (II) [ Ni(CO)4 ]
0

3+ 4–
(c) [TiCl3 (H 2O)3 ] (d) [TiCl2 (H2 O)4 ]
(III) [Cr(NH3 )6 ] (IV) [ Mn(CN)6 ]

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (c) 12 (c) 23 (b) 34 (c) 45 (c) 56 (a) 67 (a) 78 (a) 89 (b) 100 (b)
2 (d) 13 (c) 24 (a) 35 (a) 46 (b) 57 (a) 68 (a) 79 (a) 90 (b) 101 (b)
3 (b) 14 (b) 25 (c) 36 (a) 47 (d) 58 (b) 69 (c) 80 (a) 91 (d) 102 (a)
4 (c) 15 (b) 26 (b) 37 (c) 48 (c) 59 (b) 70 (c) 81 (d) 92 (d) 103 (a)
5 (d) 16 (b) 27 (d) 38 (a) 49 (c) 60 (c) 71 (a) 82 (c) 93 (a) 104 (b)
6 (d) 17 (a) 28 (d) 39 (a) 50 (c) 61 (c) 72 (a) 83 (a) 94 (d) 105 (d)
7 (a) 18 (c) 29 (a) 40 (b) 51 (b) 62 (c) 73 (a) 84 (d) 95 (c) 106 (b)
8 (d) 19 (c) 30 (c) 41 (b) 52 (d) 63 (b) 74 (b) 85 (a) 96 (b) 107 (a)
9 (c) 20 (c) 31 (a) 42 (c) 53 (c) 64 (b) 75 (d) 86 (d) 97 (d) 108 (a)
10 (d) 21 (b) 32 (b) 43 (d) 54 (b) 65 (d) 76 (c) 87 (a) 98 (d) 109 (b)
11 (c) 22 (b) 33 (b) 44 (a) 55 (a) 66 (b) 77 (d) 88 (d) 99 (d) 110 (a)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 8 (c) 15 (b) 22 (b) 29 (c) 36 (a) 43 (a) 50 (d) 57 (b)
2 (c) 9 (a) 16 (b) 23 (c) 30 (a) 37 (b) 44 (d) 51 (b) 58 (d)
3 (b) 10 (d) 17 (d) 24 (d) 31 (c) 38 (c) 45 (b) 52 (d) 59 (a)
4 (d) 11 (a) 18 (b) 25 (a) 32 (d) 39 (b) 46 (b) 53 (c) 60 (b)
5 (a) 12 (b) 19 (d) 26 (d) 33 (a) 40 (d) 47 (d) 54 (b) 61 (c)
6 (c) 13 (b) 20 (a) 27 (c) 34 (d) 41 (d) 48 (b) 55 (b) 62 (a)
7 (a) 14 (c) 21 (b) 28 (d) 35 (c) 42 (d) 49 (a) 56 (a) 63 (a)
Exercise 3 : Try If You Can
1 (b) 3 (b) 5 (b) 7 (c) 9 (c) 11 (c) 13 (c) 15 (b)
2 (b) 4 (a) 6 (c) 8 (a) 10 (c) 12 (a) 14 (d)
 24 Chapter
HALOALKENES AND
HALOARENES

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Nucleophilic substitution
reaction, chemical properties of
AIIMS 3 4.2/5 9
haloalkanes and haloarenes,
JEE Main 2 preparations and properties of
BITSAT 2 polyhalogen compounds
 EBD_7374
332 CHEMISTRY
HALOALKANES AND HALOARENES 333
 EBD_7374
334 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1. Classification and Nomenclature 6. Which one of the following is not an allylic halide?
(a) 4-Bromopent-2-ene
1. When two halogen atoms are attached to same carbon atom (b) 3-Bromo-2-methylbut-1-ene
then it is : (c) 1-Bromobut-2-ene
(a) vic-dihalide (b) gem-dihalide (d) 4-Bromobut-1-ene
7. IUPAC name of (CH3)3CCl is
(c) a, w-halide (d) a, b-halide
(a) 3-Chlorobutane
2. Read the following statements and choose the correct (b) 2-Chloro-2-methylpropane
option. (c) t-butyl chloride
(i) The general formula of alkyl halides is CnH2n+1 X (d) n-butyl chloride
(ii) The general formula of aryl halides is Cn Hn–1 X 8. IUPAC name of
(iii) In alkyl halides halogen atom(s) is attached to sp2 CH3CH2C(Br) = CH – Cl is
(a) 2-bromo-1-chlorobutene
hybridised carbon atom
(b) 1-chloro-2-bromobutene
(iv) In aryl halides halogen atom(s) is attached to sp2 (c) 3-chloro-2-bromobutene
hybridised carbon atom. (d) None of the above
(a) (i), (ii) and (iii) are correct 9. Which of the following halide is 2° ?
(b) (i), (ii) and (iv) are correct (a) Isopropyl chloride (b) Isobutyl chloride
(c) (ii), (iii) and (iv) are correct (c) n-Propyl chloride (d) n-Butyl chloride
10. Phosgene is a common name for
(d) (i), (ii), (iii) and (iv) are correct
(a) phosphoryl chloride
3. Match the columns (b) thionyl chloride
Column - I Column - II (c) carbon dioxide and phosphine
(A) CH2 = CH – CH2Cl (p) gem-Dichloride (d) carbonyl chloride
(B) CH2 = CHX (q) Vinylic halide
Topic 2. Methods of Preparation
(C) CH3CHCl2 (r) vic-Dichloride
11. Halogenation of alkanes is
(D) CH2Cl CH2Cl (s) Allylic halide (a) a reductive process (b) an oxidative process
(a) A – (r), B – (q), C – (p), D – (s) (c) an isothermal process (d) an endothermal process
(b) A – (q), B – (p), C – (s), D – (r) 12. Ethylene dichloride can be prepared by adding HCl to
(c) A – (s), B – (q), C – (p), D – (r) (a) ethane (b) ethylene
(c) acetylene (d) ethylene glycol
(d) A – (r), B – (p), C – (s), D – (q)
13. The best method for the conversion of an alcohol into an
4. The IUPAC name of the compound shown below is alkyl chloride is by treating the alcohol with
Cl (a) PCl5
(b) dry HCl in the presence of anhydrous ZnCl2
(c) SOCl2 in presence of pyridine
(d) none of these
14. In the preparation of chlorobenzene from aniline, the most
Br suitable reagent is
(a) chlorine in the presence of ultraviolet light
(a) 2-bromo-6-chlorocyclohex-1-ene (b) chlorine in the presence of AlCl3
(b) 6-bromo-2-chlorocyclohexene (c) nitrous acid followed by heating with Cu2Cl2
(c) 3-bromo-1-chlorocyclohexene (d) hCl and Cu2Cl2
(d) 1-bromo-3-chlorocyclohexene 15. Conant Finkelstein reaction for the preparation of alkyl iodide
5. A compound is formed by substitution of two chlorine for is based upon the fact that
two hydrogens in propane. The number of possible isomeric (a) sodium iodide is soluble in methanol, while sodium
compounds is chloride is insoluble in methanol
(b) sodium iodide is soluble in methanol, while NaCl and
(a) 4 (b) 3 (c) 5 (d) 2
NaBr are insoluble in methanol
HALOALKANES AND HALOARENES 335

(c) sodium iodide is insoluble in methanol, while NaCl and 21. Fluorobenzene (C6H5F) can be synthesized in the laboratory
NaBr are soluble (a) by direct fluorination of benzene with F2 gas
(d) the three halogens differ considerably in their (b) by reacting bromobenzene with NaF solution
electronegativity
(c) by heating phenol with HF and KF
CS
16. Silver acetate + Br2 ¾¾¾ 2 ®. The main product of this
(d) from aniline by diazotisation followed by heating the
reaction is diazonium salt with HBF4
(a) CH3 - Br (b) CH3COH
(c) CH 3COOH (d) None of these Topic 3. Physical and Chemical Properties
17. Aryl halides can not be prepared by the reaction of aryl 22. The decreasing order of boiling points of alkyl halides is
alcohols with PCl3, PCl5 or SOCl2 because (a) RF > RCl > RBr > RI (b) RBr > RCl > RI > RF
(a) phenols are highly stable compounds. (c) RI > RBr > RCl > RF (d) RCl > RF > RI > RBr
(b) carbon-oxygen bond in phenols has a partial double 23. Which of the following is liquid at room temperature (b.p. is
bond character. shown against it) ?
(c) carbon-oxygen bond is highly polar (a) CH3I 42ºC
(d) all of these (b) CH3Br 3ºC
18. Following statements are given regarding the preparation (c) C2H5Cl 12ºC
of aryl halides from toluene. Read the following statements (d) CH3F –78ºC
and choose the correct options.
24. Which of the following possesses highest melting point?
(i) Aryl chlorides and bromides can be easily prepared (a) Chlorobenzene (b) m-dichlorobenzene
by this method.
(c) o-dichlorobenzene (d) p-dichlorobenzene
(ii) The ortho and para isomers formed in the reaction can 25. Read the following statements and choose the correct
not be separated easily due to small difference in their answer
melting point.
(i) The boiling points of isomeric haloalkanes decrease
(iii) Reactions with iodine are reversible in nature and with increase in branching.
require the presence of an oxidising agent.
(ii) Among isomeric dihalobenzenes the para-isomers
(iv) Fluoro compounds are not prepared by this method have higher melting point than their ortho and meta-
due to low reactivity of fluorine. isomers.
(a) (i) and (iii) are correct (iii) The isomeric dihalobenzenes have large difference in
(b) (ii) and (iv) are correct their boiling and melting points
(c) (i), (ii), and (iii) are correct (iv) The isomeric dihalobenzenes have nearly same boiling
(d) All statements are correct point.
19. Match the columns (a) (i), (ii) and (iii) are correct
Column - I Column - II (b) (i) and (iii) are correct
2Cl / UV light (c) (ii) and (iv) are correct
(A) C2H6¾¾¾¾¾¾ ® (p) Finkelstein reaction
(d) (i), (ii) and (iv) are correct
C2H5Cl
26. Which of the following will have the maximum dipole
(B) C6H5NH2 (q) Free radical moment?
NaNO + HCl/Cu Cl (a) CH3F (b) CH3Cl (c) CH3Br (d) CH3I
¾¾¾¾¾¾¾¾2 2 2
® substitution
273- 278K
C6H5Cl 27. Which one is most reactive towards SN 1 reaction ?
(C) CH3Cl + NaI ¾¾ ® (r) Swarts reaction (a) C6H5CH(C6H5)Br (b) C6H5CH(CH3)Br
CH3I + NaCl (c) C6H5C(CH3)(C6H5)Br (d) C6H5CH2Br
(D) CH3 – Br + AgF ¾¾ ® (s) Sandmeyer’s reaction 28. A Grignard reagent may be made by reacting magnesium
CH3F + AgBr with
(a) A – (q), B – (s), C – (p), D – (r) (a) Methyl amine (b) Diethyl ether
(b) A – (q), B – (r), C – (p), D – (s) (c) Ethyl iodide (d) Ethyl alcohol
29. Most reactive halide towards SN1 reaction is
(c) A – (r), B – (p), C – (s), D – (q)
(a) n-Butyl chloride (b) sec-Butyl chloride
(d) A – (s), B – (r), C – (p), D – (q)
(c) tert-Butyl chloride (d) Allyl chloride
20. Hydrocarbon (CH3)3CH undergoes reaction with Br2 and 30. In SN1 reaction, the recemization takes place. It is due to
Cl2 in the presence of sunlight, if the reaction with Cl is (a) inversion of configuration
highly reactive and that with Br is highly selective so (b) retention of configuration
no.of possible products respectively is (are) (c) conversion of configuration
(a) 2, 2 (b) 2, 1 (c) 1, 2 (d) 1, 1 (d) Both (a) and (b)
 EBD_7374
336 CHEMISTRY

31. The order of reactivities of the following alkyl halides for a (a) Frankland’s reaction (b) Sandmeyer’s reaction
SN2 reaction is (c) Wurtz reaction (d) Kolbe’s reaction
(a) RF > RCl > RBr > RI (b) RF > RBr > RCl > RI 45. When 2-Bromobutane reacts with alcoholic KOH, the
(c) RCl > RBr > RF > RI (d) RI > RBr > RCl > RF reaction is called
32. Which among MeX, RCH2X, R2CHX and R3CX is most (a) halogenation (b) chlorination
reactive towards SN2 reaction? (c) hydrogenation (d) dehydrohalogenation
(a) MeX (b) RCH2X (c) R2CHX (d) R3CX 46. An alkyl halide by formation of its Grignard reagent and
33. Isopropyl chloride undergoes hydrolysis by heating with water yields propane. What is the original alkyl
(a) SN1 mechanism
halide ?
(b) SN2 mechanism
(c) SN1 and SN2 mechanisms (a) Methyl iodide (b) Ethyl iodide
(d) Neither SN1 nor SN2 mechanism (c) Ethyl bromide (d) Propyl bromide
34. Tertiary alkyl halides are practically inert to substitution by 47. An organic compound A (C 4H9Cl) on reaction with
SN2 mechanism because of Na/diethyl ether gives a hydrocarbon which on
(a) steric hindrance (b) inductive effect monochlorination gives only one chloro derivative, then A
(c) instability (d) insolubility is
35. Which of the following is an optically active compound ? (a) tert-butyl chloride (b) sec-butyl chloride
(a) 1-Butanol (b) 1-Propanol (c) isobutyl chloride (d) n-butyl chloride
(c) 2-Chlorobutane (d) 4-Hydroxyheptane 48. Reactivity order of halides for dehydrohalogenation is
36. An important chemical method to resolve a racemic mixture (a) R – F > R – Cl > R – Br > R –I
makes use of the formation of (b) R –I > R – Br > R – Cl > R – F
(a) a meso compound (b) enantiomers (c) R –I > R – Cl > R – Br > R – F
(c) diastereomers (d) racemates (d) R – F > R –I > R – Br > R – Cl
49. Which of following can be used as solvent for Grignard
37. The process of separation of a racemic modification into
reagent ?
d-and l -enantiomers is called (a) H2O (b) C2H5OH
(a) Resolution (b) Dehydration (c) CH3OH (d) C2H5OC2H5
(c) Revolution (d) Dehydrohalogenation 50. Chlorobenzene reacts with Mg in dry ether to give a
38. Which of the following will have a mesoisomer also? compound (A) which further reacts with ethanol to yield
(a) 2, 3- Dichloropentane (a) Phenol (b) Benzene
(b) 2, 3-Dichlorobutane (c) Ethylbenzene (d) Phenyl ether
(c) 2-Chlorobutane 51. Benzene reacts with n-propyl chloride in the presence of
(d) 2-Hydroxypropanoic acid anhydrous AlCl3 to give
39. Which of the following compounds is optically active ? (a) 3 – Propyl – 1 – chlorobenzene
(a) CH3CHClCOOH (b) CH3CH2CH2CH3 (b) n-Propylbenzene
(c) (CH3)2CHOH (d) (CH3)3CCl (c) No reaction
40. Racemic compound has (d) Isopropylbenzene
(a) equimolar mixture of enantiomers 52. C – Cl bond of chlorobenzene in comparison to C – Cl bond
(b) 1 : 1 mixture of enantiomer and diastereomer in methyl chloride is
(c) 1 : 1 mixture of diastereomers (a) Longer and weaker (b) Shorter and weaker
(d) 1 : 2 mixture of enantiomers (c) Shorter and stronger (d) Longer and stronger
41. An organic molecule necessarily shows optical activity if it 53. Which of the following is not used in Friedel-Craft’s
(a) contains asymmetric carbon atoms reaction?
(b) is non-polar (a) N–Phenyl acetanilide (b) Bromobenzene
(c) is non-superimposable on its mirror image (c) Benzene (d) Chlorobenzene
(d) is superimposable on its mirror image 54. Which one of the following is most reactive towards
42. Mg reacts with RBr best in nucleophilic substitution reaction?
(a) C2H5OC2H5 (b) C6H5OCH3 (a) CH 2 = CH - Cl (b) C6 H 5Cl
(c) C6H5N(CH3)2 (d) Equally in all the three
(c) CH 3CH = CH - Cl (d) ClCH 2 - CH = CH 2
43. 2-Bromopentane is heated with potassium ethoxide in
ethanol. The major product obtained is 55. Haloarenes are ortho and para directing due to
(a) 2-ethoxypentane (b) pentene-1 (a) Resonance in aryl halide
(c) trans-2-pentene (d) cis-pentene-2 (b) – I effect of halogen atom
44. An alkyl halide reacts with metallic sodium in dry ether. The (c) + I effect of halogen atom
reaction is known as : (d) Both (a) and (b)
HALOALKANES AND HALOARENES 337

56. Chloropicrin is obtained by the reaction of 61. CH 3 - CH 2 - C H - CH 3 obtained by chlorination of

(a) steam on carbon tetrachloride |
(b) nitric acid on chlorobenzene Cl
(c) chlorine on picric acid n-butane, will be
(d) nitric acid on chloroform (a) l-form (b) d-form
57. Which of these can be used as moth repellant (c) Meso form (d) Racemic mixture
(a) Benzene hexachloride (b) Benzal chloride 62. The number of possible enantiomeric pairs that can be
(c) Hexachloroethane (d) Tetrachloroethane produced during monochlorination of 2-methylbutane is
58. Read the following statements and choose the correct code (a) 2 (b) 3 (c) 4 (d) 1
(i) SN2 reactions follows a second order kinetics whereas 63. The number of structural and configurational isomers of a
SN1 reactions follows the first order kinetics bromo compound, C5H9Br, formed by the addition of HBr to
(ii) SN1 reactions follows the second order kinetics 2-pentyne respectively are
whereas SN2 follows the first order kinetics (a) 1 and 2 (b) 2 and 4 (c) 4 and 2 (d) 2 and 1
(iii) SN2 reactions take place in a single step whereas 64. Consider the following bromides :
SN1 reactions take place in two steps
(iv) Tertiary alkyl halides are least reactive towards SN2 Me Me
Me Br Me
reactions but we observe high reactivity towards SN1
reaction. Br Br
(a) (ii) and (iv) are correct (A) (B)
(b) (i) and (iii) are correct The correct order of SN1 reactivity is
(c) (i), (ii) and are correct (a) B > C > A (b) B > A > C
(d) (ii), (iii) and (iv) are correct (c) C > B > A (d) A > B > C
59. Read the following statements and choose the correct 65. Consider the reactions :
option.
(i) C H OH
(i) SN1 reactions are carried out through formation of (CH 3 ) 2 CH - CH 2 Br ¾¾2 ¾¾¾
5 ®
carbocation as an intermediate. (CH 3 )2 CH - CH 2OC 2H 5 + HBr
(ii) SN1 reactions are two step reactions in which step 1 is C H O-
(ii) 2 5
(CH 3 ) 2 CH - CH 2 Br ¾¾¾¾¾®
fast and irreversible.
(iii) Step 1 involves breaking of C–Br bond which obtain (CH 3 )2 CH - CH 2OC 2 H 5 + Br -
energy through solvation of halide. The mechanisms of reactions (i) and (ii) are respectively :
(iv) SN1 reactions are two step reactions in which step 2 is (a) SN1 and SN2 (b) SN1 and SN1
slow and reversible. (c) SN2 and SN2 (d) SN2 and SN1
(v) Allylic and benzylic halides show high reactivity 66. The organic chloro compound, which shows complete
toward SN1 reactions. stereochemical inversion during a SN2 reaction, is
(a) (i), (iii) and (v) are correct (a) (C2H5)2CHCl (b) (CH3)3CCl
(b) (ii), (iii) and (v) are correct (c) (CH3)2 CHCl (d) CH3Cl
(c) (i), (iii) and (iv) are correct
67. The correct order of reactivity of the halides, ethyl
(d) (i), (ii) and (iv) are correct
chloride (I) iso-propyl chloride (II) and benzyl chloride
60. Which of the statement(s) is/are true, regarding following (III) in SN1 reaction is
reaction? (a) I > II > III (b) III > II > I
R (c) II > I > III (d) I > III > II
R
Nu – – 68. The replacement of chlorine of chlorobenzene to give phenol
R' CBr R' CNu + Br
requires drastic conditions, but the chlorine of 2,
R'' R''
4-dinitrochlorobenzene is readily replaced since,
(i) The reaction involves the formation of transition state. (a) nitro groups make the aromatic ring electron rich at
(ii) Higher the nucleophilic character of the nucleophile, ortho/para positions
faster will be the reaction. (b) nitro groups withdraw electrons from the meta position
of the aromatic ring
(iii) The product is always optically inactive.
(c) nitro groups donate electrons at meta position
(a) (ii) only (b) (ii) and (iii)
(d) nitro groups withdraw electrons from ortho/para
(c) (i), (ii) and (iii) (d) Neither (i), (ii) nor (iii) positions of the aromatic ring
 EBD_7374
338 CHEMISTRY

Topic 4. Polyhalogen Compounds 79. If chloroform is left open in air in the presence of sunlight, it
gives
69. CFxCly [where x + y = 4]. These compounds are not used (a) carbon tetrachloride (b) carbonyl chloride
because
(c) mustard gas (d) lewisite
(a) these are fluorocarbons
(b) these are difficult to synthesise 80. Full name of DDT is
(c) they deplete ozone layer (a) 1, 1, 1-trichloro-2, 2-bis(p-chlorophenyl) ethane
(d) None of the these (b) 1, 1-dichloro-2, 2-diphenyl trimethylethane
70. Which of the following is used in fire extinguishers (c) 1, 1-dichloro-2, 2-diphenyl trichloroethane
(a) CH4 (b) CHCl3 (c) CH2Cl2 (d) CCl4
(d) None of these
71. Match the columns.
81. Assertion : Exposure of ultraviolet rays to human causes
Column - I Column - II
(Haloalkane/arene) (Applications) the skin cancer, disorder and disrupt the immune system.
(A) Iodoform (p) CF4 Reason : Carbon tetrachloride is released into air it rises to
(B) BHC (q) Antiseptic atmosphere and deplets the ozone layer.
(C) Freon - 14 (r) Moth repellant (a) Assertion is correct, reason is correct; reason is a
(D) Halothanes (s) Inhalative anesthetic correct explanation for assertion.
(E) p-Dichlorobenzene (t) Termite pesticide (b) Assertion is correct, reason is correct; reason is not a
(a) A – (q), B – (s), C – (t), D – (r), E – (p) correct explanation for assertion
(b) A – (q), B – (t), C – (p), D – (s), E – (r) (c) Assertion is correct, reason is incorrect
(c) A – (r), B – (s), C – (q), D – (p), E – (t) (d) Assertion is incorrect, reason is correct.
(d) A – (p), B – (r), C – (t), D – (q), E – (s) 82. Chronic chloroform exposure may cause damage to liver
72. Solvent which is used in the synthesis of chlorofluorocarbons and kidney, due to the formation of
(a) iodoform (b) chloroform (a) phosgene (b) methylene chloride
(c) carbon tetrachloride (d) methylene chloride (c) methyl chloride (d) carbon tetrachloride
73. Uses of dichloromethane is 83. Which one of the following has antiseptic property?
(a) paint remover (a) Dichloromethane (b) Trifluoromethane
(b) solvent in drugs manufacturing (c) Triiodomethane (d) Tetrachloromethane
(c) metal cleansing and finishing solvent 84. Chloroform cannot be prepared from which of the following?
(d) All of the above (a) CH3OH (b) C2H5OH (c) CH3CHO(d) (CH3)2CO
74. Haloforms are trihalogen derivatives of 85. Exposure of CCl4 causes
(a) Ethane (b) Methane (c) Propane (d) Benzene (a) Liver cancer in human
75. AgNO3 does not give precipitate with CHCl3 because (b) Damage to nerve cells
(a) CHCl3 does not ionise in water (c) Coma, unconsciousness
(b) CHCl3 does not react with AgNO3 (d) All of these
(c) CHCl3 is chemically inert 86. Natural ozone layer is unbalanced due to
(d) None of these (a) cloudiness of poisonous gases
76. Cl (b) presence of rain in the atmosphere
C–CCl3
(c) initiation of radical chain by freon
(d) All of the above
Cl H 87. Assertion : CCl4 is not a fire extinguisher.
Reason : CCl4 is insoluble in water.
The above structural formula refers to
(a) BHC (b) DNA (c) DDT (d) RNA (a) Assertion is correct, reason is correct; reason is a
77. Match the columns correct explanation for assertion.
Column - I Column - II (b) Assertion is correct, reason is correct; reason is not a
(A) Chloroform (p) Antiseptic correct explanation for assertion
(B) Iodoform (q) Insecticide (c) Assertion is correct, reason is incorrect
(C) Trichloromethane (r) Anesthetic (d) Assertion is incorrect, reason is correct.
(D) DDT (s) Propellant 88. Match the columns
(a) A – (s), B – (p), C – (r), D – (q) Column-I Column-II
(b) A – (r), B – (p), C – (s), D – (q) (A) Chloramphenicol (p) Goiter
(c) A – (q), B – (s), C – (p), D – (q) (B) Thyroxine (q) Surgery
(d) A – (r), B – (s), C – (p), D – (q) (C) Chloroquine (r) Typhoid
78. Which of the following are the harmful effects of methylene (D) Halothane (s) Malaria
chloride? (a) A – (q), B – (p), C – (s), D – (r)
(a) Impaired hearing and vision
(b) A – (r), B – (p), C – (s), D – (q)
(b) Dizziness, nausea and tingling
(c) A – (s), B – (r), C – (q), D – (p)
(c) Skin burning
(d) A – (p), B – (s), C – (q), D – (r)
(d) All of these
HALOALKANES AND HALOARENES 339

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (c) free radical addition reaction

(d) nucleophilic substitution reaction
1. The order of reactivity of following alcohols with halogen 5. Which of the following is halogen exchange reactions?
acids is .............. . (a) RX + NaI ® RI + NaX
(A) CH3CH 2 — CH 2 — OH (b) C C + HX C C

||

|
| |
(B) CH3CH 2 - CH - OH H X
|
CH3 (c) ZnCl
R — OH + HX ¾¾¾¾
2®R — X + H O
2
CH3 CH3 CH3
| Fe
+ X 2 ¾¾¾ ®
(C) CH3CH2 – CH – OH (d) dark
| X
CH3
CH3
(a) (A) > (B) > (C) (b) (C) > (B) > (A) +
(c) (B) > (A) > (C) (d) (A) > (C) > (B)
2. Which of the following alcohols will yield the X
corresponding alkyl chloride on reaction with concentrated 6. Which reagent will you use for the following reaction?
HCl at room temperature? CH3CH2CH2CH3 ® CH3CH2CH2CH2Cl
+ CH3CH2CHClCH3
(a) CH3CH 2 — CH 2 — OH
(a) Cl2 /UV light
(b) CH3CH 2 - CH - OH (b) NaCl + H2SO4
| (c) Cl2 gas in dark
CH3 (d) Cl2 gas in the presence of iron in dark
(c) CH3CH2 – CH—CH2OH 7. Arrange the following compounds in the increasing order
| of their densities.
CH3
Cl
CH3
|
(i) (ii)
(d) CH3CH2 – C – OH
|
CH3
3. Identify the compound Y in the following reaction. Cl Br
+
NH3 N 2 Cl (iii) (iv)
Na NO 2 + HCl
¾¾¾¾¾¾ ® ¾¾¾¾
Cu Cl
2 2 ®Y + N
273- 278 K 2 Cl Cl
Cl (a) (i) < (ii) < (iii) < (iv) (b) (i) < (iii) < (iv) < (ii)
(a) (c) (iv) < (iii) < (ii) < (i) (d) (ii) < (iv) < (iii) < (i)
(b)
8. Arrange the following compounds in increasing order of
their boiling points.
Cl
Cl CH3
(i) CH — CH2Br (ii) CH3CH2CH2CH2Br
CH3
(c) (d)
CH3
Cl |
Cl
4. Toluene reacts with a halogen in the presence of iron (III) (iii) H3C — C| — CH3
chloride giving ortho and para halo compounds. The
Br
reaction is
(a) electrophilic elimination reaction (a) (ii) < (i) < (iii) (b) (i) < (ii) < (iii)
(b) electrophilic substitution reaction (c) (iii) < (i) < (ii) (d) (iii) < (ii) < (i)
 EBD_7374
340 CHEMISTRY

9. In which of the following molecules carbon atom marked CH2 — CH — CH3

(c)
with asterisk ( * ) is asymmetric?
H D Cl

(i) C* (ii) C*
I Cl I Cl
Br Br
(d) Cl
H H
CH — CH2 — CH3
(iii) C* (iv) H C*
HO CH3 CH3
C2H5 C2H 5
(a) (i), (ii), (iii) and (iv) (b) (i), (ii) and (iii)
(c) (ii), (iii) and (iv) (d) (i), (iii) and (iv)
10. Which of the following structures is enantiomeric with the 16. A primary alkyl halide would prefer to undergo .................
molecule (A) given below? (a) SN1 reaction (b) SN2 reaction
(c) a-elimination (d) racemisation
H
CH3 17. Which of the following alkyl halides will undergo SN1
C reaction most readily?
Br (a) (CH3 )3 C — F (b) (CH3 )3 C — Cl
HC 5 2
(c) (CH3 )3 C — Br (d) (CH3 )3 C — I
(A)
18. Which is the correct IUPAC name for
H CH3
H CH3 — CH — CH 2 — Br ?
C2H5 C |
(a) C (b) . C2H5
Br
H3C Br C2H5
(a) 1-bromo-2-ethylpropane
H Br (b) 1-bromo-2-ethyl-2-mehylethane
Br H
C (c) 1-bromo-2-methylbutane
(c) (d) C
H3C C2H5 (d) 2-methyl-1-bromobutane
H5C2 CH3
19. What should be the correct IUPAC name for
11. Which of the following is an example of vic-dihalide? diethylbromomethane?
(a) Dichloromethane (b) 1, 2-dichloroethane (a) 1-bromo-1, 1-diethylmethane
(c) Ethylidene chloride (d) Allyl chloride (b) 3-bromopentane
12. The position of Br in the compound CH3CH = CHC(Br) (c) 1-bromo-1-ethylpropane
(CH3)2 can be classified as .............. . (d) 1-bromopentane
(a) allyl (b) aryl (c) vinyl (d) secondary 20. The reaction of toluene with chlorine in the presence of
13. Chlorobenzene is formed by reaction of chlorine with iron and in the absence of light yields ............ .
benzene in the presence of AlCl3. Which of the following
CH2Cl CH3
species attacks the benzene ring in this reaction?
(a) Cl– (b) Cl+ (c) AlCl3 (d) [AlCl4]– Cl
14. Ethylidene chloride is a/an ................ . (a) (b)
(a) vic-dihalide (b) gem-dihalide
(c) allylic halide (d) vinylic halide
15. What is 'A' in the following reaction? (c) H 3C Cl (d) Mixture of (b) and (c)
CH2 — CH — CH2 + HCl A 21. Chloromethane on treatment with excess of ammonia yields
mainly
æ CH3ö
(a) N, N-dimethylmethanamine çCH3 —N ÷
è CH3ø
(a) CH2 — CH — CH2
(b) N - methylmethanamine (CH3 — NH — CH3)
Cl (c) methanamine (CH3NH2)
(d) mixture containing all these in equal proportion
22. Molecules whose mirror image is non – superimposable
over them are known as chiral. Which of the following
(b) CH2 — CH2 — CH2 — Cl
molecules is chiral in nature?
(a) 2 - bromobutane (b) 1 - bromobutane
(c) 2 - bromopropane (d) 2 -bromopropan - 2 - ol
HALOALKANES AND HALOARENES 341

23. Reaction of C6H5CH2Br with aqueous sodium hydroxide

follows .......... . Cl Cl Cl
(a) SN1 mechanism CH3
(b) SN2 mechanism 29. (i) (ii) (iii)
(c) Any of the above two depending upon the temperature
of reaction
CH3 CH3
(d) Saytzeff rule
24. Which of the carbon atoms presents in the molecule given
(a) (iii) < (ii) < (i) (b) (ii) < (i) < (iii)
below are asymmetric?
(c) (iii) < (ii) < (i) (d) (i) < (iii) < (ii)
OH H O 30. Which is the correct increasing order of boiling points of
HO | | | ||
1 2 4 the following compounds?
|| C — C — C — C |
3

| | H 1 - iodobutane, 1 - bromobutane, 1 - chlorobutane, Butane

O H OH (a) Butane < 1-chlorobutane < 1- bromobutane <
(a) 1, 2, 3, 4 (b) 2, 3 (c) 1, 4 (d) 1, 2, 3 1 - iodobutabe
25. Which of the following compounds will give racemic mixture (b) 1 - iodobutane < 1 - bromobutane < 1 - chloroubutane
on nucleophilic substitution by OH – ion? < Butane
Br (c) Butane < 1 - iodobutane < 1 - bromobutane <
| 1 - chlorobutane
(i) CH3 — CH — Br (ii) CH3 — CH — CH3
| | (d) Butane < 1 - chlorobutane < 1 - iodobutane <
C2H5 C2H5 1 - bromobutane
31. Which is the correct increasing order of boiling points of
(iii) CH 3 — CH — CH3Br the following compounds?
| 1 - bromoethane, 1 - bromopropane,1 - bromobutane,
C2H5 Bromobenzene
(a) (i) (b) (i), (ii) and (iii) (a) Bromobenzene < 1 - bromobutane < 1 - bromopropane
(c) (ii) and (iii) (d) (i) and (iii) < 1- bromoethane
Direction (Q. No. 26 to 29) : In the questions 26 to 29 arrange the (b) Bromobenzene < 1 - bromobutane < 1 - bromopropane
compounds in increasing order of rate of reaction towards < 1- bromobutane
nucleophilic substitution. (c) 1 - bromopropane < 1 - bromorpropane < 1 - bromoethane
< Bromobenzene
Cl Cl Cl (d) 1 - bromoethane < 1 - bromopropane < 1 - bromobutane
NO2 < Bromobenzene
26. (i) (ii) (iii) Past Year MCQs
NO2 32. What products are formed when the following compounds
(a) (i) < (ii) < (iii) (b) (iii) < (ii) < (i) is treated with Br2 in the presence of FeBr3?
(c) (i) < (iii) < (ii) (d) (iii) < (i) < (ii) [AIPMT 2014, A]
Cl CH3
Cl Cl
CH3
27. (i) (ii) (iii)
CH3 CH3
(a) (i) < (ii) < (iii) (b) (i) < (iii) < (ii)
(c) (iii) < (ii) < (i) (d) (ii) < (iii) < (i) CH3 CH3
Br
Cl Cl Cl (a) and
O2N NO2 CH3 CH3
28. (i) (ii) (iii) Br

NO2 NO2 CH3 CH3

Br Br
(a) (iii) < (ii) < (i) (b) (ii) < (iii) < (i) (b) and
(c) (i) < (iii) < (ii) (d) (i) < (ii) < (iii)
CH3 CH3
 EBD_7374
342 CHEMISTRY

37. In an SN1 reaction on chiral centres there is :

CH3 CH3
[AIPMT 2015 RS, A]
Br (a) 100 % racemization
(c) and (b) inversion more than retention leading to partial
CH3 CH3 racemization
(c) 100 % retention
Br (d) 100 % inversion
38. The solution of a chemical compound reacts with AgNO3
CH3 CH3 solution to form a white preciptate of Y which dissolves in
NH4OH to give a complex Z. When Z is treated with dilute
(d) HNO3, Y reappears. The chemical compound X can be:
and [AIIMS 2015, S]
CH3 Br CH3 (a) NaCl (b) CH3Cl (c) NaBr (d) NaI
Br 39. Assertion : CHCl3 is stored in dark bottles.
Reason : CHCl3 is oxidised in dark. [AIIMS 2015, C]
33. Identify Z in (a) Assertion is correct, reason is correct; reason is a
Aq. NaOH correct explanation for assertion.
CH 3CH 2 CH 2 Br ¾¾ ¾ ¾¾® X
(b) Assertion is correct, reason is correct; reason is not a
Al O Cl / H O correct explanation for assertion
¾¾2¾ ¾3 ® Y ¾¾2¾¾ 2¾® Z
(c) Assertion is correct, reason is incorrect
[AIIMS 2014, A] (d) Assertion is incorrect, reason is correct.
(a) Mixture of CH3CHClCH2Cl and CH3CHOHCH2Cl 40. The synthesis of alkyl fluorides is best accomplished by :
(b) CH3CHOHCH2Cl [JEE M 2015, C]
(c) CH3CHClCH2OH (a) Finkelstein reaction
(d) CH3CHClCH2Cl (b) Swarts reaction
(c) Free radical fluorination
34. In SN2 reactions, the correct order of reactivity for the
(d) Sandmeyer's reaction
following compounds: [JEE M 2014, S] 41. The boiling point of alkyl halide are higher than those of
CH3Cl , CH3CH 2 Cl , (CH3 )2 CHCl and ( CH3 )3 CCl is: corresponding alkanes because of [BITSAT 2015, A]
(a) dipole-dipole interaction
(a) CH3 Cl > ( CH3 )2 CHCl (b) dipole-induced dipole interaction
(c) H-bonding
> CH3 CH 2Cl > ( CH3 )3 CCl (d) None of the above
42. For the following reactions : [NEET 2016, A]
(b) CH3Cl > CH 3CH 2 Cl (1) CH3CH2CH2Br + KOH ®
> ( CH3 )2 CHCl > ( CH 3 )3 CCl CH3CH = CH2+ KBr + H2O
(2) H3C CH3 H3C CH3
(c) CH3CH 2 Cl > CH3Cl + KOH + KBr
> ( CH3 )2 CHCl > ( CH 3 )3 CCl Br OH
Br
(d) ( CH3 )2 CHCl > CH3CH 2Cl (3)
+ Br2
Br
> CH3 Cl > ( CH3 )3 CCl
Which of the following statements is correct ?
35. The number of double bonds in gammexane is : (a) (1) and (2) are elimination reaction and (3) is addition
[BITSAT 2014, C] reaction
(a) 0 (b) 1 (c) 2 (d) 3 (b) (1) is elimination, (2) is substitution and (3) is addition
36. In which of the following compounds, the C - Cl bond reaction
ionisation shall give most stable carbonium ion? (c) (1) is elimination, (2) and (3) are substitution reactions
[AIPMT 2015, C] (d) (1) is substitution, (2) and (3) are addition reaction
43. Assertion : Alkylbenzene is not prepared by Friedel-Crafts
H alkylation of benzene.
CH — Cl Reason : Alkyl halides are less reactive than acyl halides.
H3C [AIIMS 2011, 2012, 2013, 2016, C]
C — Cl (a) Assertion is correct, reason is correct; reason is a
(a) H3C (b)
CH3 correct explanation for assertion.
(b) Assertion is correct, reason is correct; reason is not a
H H 3C H correct explanation for assertion
(c) C — Cl (d) C — Cl
O 2NH2C H H 3C (c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct.
HALOALKANES AND HALOARENES 343

44. 2-Chloro-2-methylpentane on reaction with sodium 49. The major product of the following reaction is :
methoxide in methanol yields: [JEE M 2016, A] [JEE M 2018, A]
CH3

(i) C2H5CH2C OCH3 (ii) C2H5CH2C = CH2

CH3 CH3

(iii) C2H5CH = C – CH3

(a) (b)
CH3
(a) (iii) only (b) (i) and (ii)
(c) All of these (d) (i) and (iii) (c) (d)
45. An aromatic compound has molecular formula C7H7Br. Give
the possible isomers and the appropriate method to
distinguish them. [BITSAT 2016, A] Cl
(a) 3 isomers; by heating with AgNO3 solution
(b) 4 isomers; by treating with AgNO3 solution 2 Br
(c) 4 isomers; by oxidation 50. ¾¾¾® Major product [AIIMS 2018, A]
FeBr3
(d) 5 isomers; by oxidation CH3
46. The synthesis of alkyl fluorides is best accomplished by:
[AIIMS 2017, C] Cl Cl
(a) Finkelstein reaction
Br
(b) Swarts reaction
(a) (b)
(c) Free radical fluorination
(d) Sandmeyer's reaction CH3 CH3
47. Assertion : SN2 reaction of an optically active aryl halide Br
with an aqueous solution of KOH always gives an alcohol Cl Cl
with opposite sign of rotation. Br
Reason : SN2 reactions always proceed with retention of
(c) (d)
configuration. [AIIMS 2013, 2017]
CH3 CH2 – Br
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion. 51. Reactivety order for SN 1 [AIIMS 2018, C]
(b) Assertion is correct, reason is correct; reason is not a
(i) CH3 – CH – CH2 – CH3
correct explanation for assertion |
(c) Assertion is correct, reason is incorrect Cl
(d) Assertion is incorrect, reason is correct. (ii) Ph – CH2 – CH – CH3
48. The major product obtained in the following reaction is : |
[JEE M 2017, A] Cl
Br Cl
|
H (iii) CH3 – C – CH2 – CH3
C6H5 t-BuOK |
D OCH3
C6H5
(a) (±)C6H5CH(OtBu)CH2C6H5 (iv) C H3 – C H2 – C H2 – Cl
(b) C6H5CH = CHC6H5 (a) i > ii > iii > iv (b) ii > i > iii > iv
(c) (+)C6H5CH(OtBu)CH2C6H5 (c) iii > ii > i > iv (d) iv > iii > ii > i
(d) (–)C6H5CH(OtBu)CH2C6H5
 EBD_7374
344 CHEMISTRY

Exercise 3 : Try If You Can

1. Which compound undergoes nucleophilic substitution with

(a) (b) Br
NaCN at the fastest rate? Br

Br Br
(a) Br (b) MgBr

Br (c) (d)
(c) Br (d)
2. Consider the following anions. 5. Under certain conditions an alkyl halide reacts with base to
O O give an alkene and HCl [Elimination Reaction] for example
R – CH2 – CH2 – Cl ® R – CH = CH2 + HCl
CF3 S O– C6H5 S O–
The extent of these reactions depends on the structure of
O O alkyl halides (e.g. primary, secondary or tertiary). The relative
(I) (II) extent to which such reactions take place is in the order
–
O O (of haloalkanes) :
(a) Primary < secondary < Tertiary
CH3 C O– (b) Primary > Secondary > Tertiary
(III) (IV)
(c) Primary > Secondary < Tertiary
When attached to sp3-hydridized carbon, their leaving group (d) Primary < Secondary > Tertiary
ability in nucleophilic substitution reaction decreases in the
peroxide
order: 6. CH 2 CH 2 + HBr ¾¾ ¾¾® A,
(a) I > II > III > IV (b) I > II > IV > III then A is
(c) IV > I > II > III (d) IV > III > II > I
3. Among the given halides, which one will give same product (a) CH 3 CH 2 Br
in both SN1 and SN2 reactions.
Br
CH3
(b) CH 3 CH 3
(I) CH3 CH CH2 CH CH3 Br Br
Br Br Br
CH3 Cl
(c) CH 3 CH 3
(II) (III)
Cl
(IV) CH3 CH Br (d) Br CH 2 CH 2 Br

Et 7. Identify correct reactivity order for SN1 reaction

(a) (III) only (b) (I) and (II) Cl Cl Cl
(c) (III) and (IV) (d) (I), (III) and (IV)
4. In the following reaction, compound (B) is

(i) (ii) Me Me (iii)

Dry D
Br + Mg ¾¾¾® A ¾¾ ®B
(1 eq.) ether

Br (a) i > ii > iii (b) ii > iii > i

(c) i > iii > ii (d) iii > i > ii
HALOALKANES AND HALOARENES 345

8. Formation of two isomeric cyanides in the following reaction. 12. Compound(s) that on hydrogenation produce(s) optically
CH3CH = CHCH2Cl + KCN(alc.) is due to active compound(s) is (are)
(a) ambident nature of CN– H Br H Br
(b) SN2 mechanism of the reaction (a) (b)
H 3C CH3 H 2C CH3
(c) SN1 mechanism of the reaction
(d) the presence of alcohol H Br Br H
9. Which of the statement(s) is/are true, regarding (c) H2C (d) H C
CH3 CH 3
following reaction? 2

CH3
R R
Nu – – 13. Identify correct reactivity order for SN1 reaction
R' CBr R' CNu + Br
R'' R'' Cl Cl
Cl
(i) The reaction involves the formation of transition
state. (i) (ii) (iii)
N B
(ii) Higher the nucleophilic character of the nucleophile, O H H
faster will be the reaction. (a) i > ii > iii (b) ii > iii > i
(iii) The product is always optically inactive. (c) i > iii > ii (d) ii > i > iii
(a) (ii) (b) (ii) and (iii) 14. In each of the following groups, which is the strongest (best)
nucleophile?
(c) All the three (d) None of the three
10. The replacement of chlorine of chlorobenzene to give phenol (I) (1) H3C—O– (2) O–
requires drastic conditions, but the chlorine of 2, (3) H3C—S– in CH3OH
4-dinitrochlorobenzene is readily replaced since, (II) (1) OH– (2) H2O
(a) nitro groups make the aromatic ring electron rich at (3) NH2– in DMF
ortho/para positions
(b) nitro groups withdraw electrons from the meta position O–
of the aromatic ring (III) (1) (2)
O–
(c) nitro groups donate electrons at meta position
(d) nitro groups withdraw electrons from ortho/para (3) CH3O– in DMSO
positions of the aromatic ring (a) (I),3; (II),3; (III),2 (b) (I),2; (II),1; (III),3
11. Grignard reagent can’t be prepared from (c) (I),1; (II),2; (III),1 (d) (I),3; (II),1; (III),3
Cl 15. The reaction conditions leading to the best yields of C2H5Cl
are :
(a) HO Br (b)
(a) C2H6 (excess) + Cl2 ¾uv light
¾¾¾®
dark
Cl (b) C2H6 + Cl2 ¾¾ ¾ ¾ ¾ ¾¾®
room temperatur e
Cl
(c) Cl (d) (c) C2H6 + Cl2 (excess) ¾uv light
¾¾¾®

(d) C2H6 + Cl2 ¾uv light

¾¾¾®
 EBD_7374
346 CHEMISTRY

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 10 (d) 19 (a) 28 (c) 37 (a) 46 (d) 55 (d) 64 (a) 73 (d) 82 (a)
2 (b) 11 (b) 20 (b) 29 (c) 38 (b) 47 (a) 56 (d) 65 (a) 74 (b) 83 (c)
3 (c) 12 (d) 21 (d) 30 (d) 39 (a) 48 (b) 57 (c) 66 (d) 75 (a) 84 (a)
4 (c) 13 (c) 22 (c) 31 (d) 40 (a) 49 (d) 58 (b) 67 (b) 76 (c) 85 (d)
5 (c) 14 (c) 23 (a) 32 (a) 41 (c) 50 (b) 59 (a) 68 (d) 77 (b) 86 (c)
6 (d) 15 (b) 24 (d) 33 (c) 42 (a) 51 (d) 60 (d) 69 (c) 78 (d) 87 (d)
7 (b) 16 (a) 25 (d) 34 (a) 43 (c) 52 (c) 61 (d) 70 (d) 79 (b) 88 (b)
8 (a) 17 (b) 26 (b) 35 (c) 44 (c) 53 (a) 62 (a) 71 (b) 80 (a)
9 (a) 18 (a) 27 (c) 36 (c) 45 (d) 54 (d) 63 (b) 72 (c) 81 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 7 (a) 13 (b) 19 (b) 25 (a) 31 (d) 37 (b) 43 (c) 49 (b)
2 (d) 8 (c) 14 (b) 20 (d) 26 (c) 32 (c) 38 (a) 44 (a) 50 (b)
3 (a) 9 (b) 15 (c) 21 (c) 27 (d) 33 (b) 39 (c) 45 (c) 51 (c)
4 (b) 10 (a) 16 (b) 22 (a) 28 (d) 34 (b) 40 (b) 46 (b)
5 (a) 11 (b) 17 (d) 23 (a) 29 (c) 35 (a) 41 (a) 47 (d)
6 (a) 12 (a) 18 (c) 24 (b) 30 (a) 36 (a) 42 (b) 48 (b)
Exercise 3 : Try If You Can
1 (a) 3 (c) 5 (a) 7 (a) 9 (d) 11 (a) 13 (d) 15 (a)
2 (b) 4 (c) 6 (d) 8 (c) 10 (d) 12 (b, d) 14 (d)
 25 Chapter
ALCOHOLS, PHENOLS AND
ETHERS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 3 Reactions of alcohols and
AIIMS 3 phenols, cleavage of C – O bond 4.2/5 8.2
JEE Main 2 in ethers, acidity of phenols
BITSAT 3
 EBD_7374
348 CHEMISTRY
ALCOHOLS, PHENOLS AND ETHERS 349
 EBD_7374
350 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Classification and Nomenclature CH 3

|
1. Which of the following is dihydric alcohol ? 10. The IUPAC name of CH 3 - CH - CH 2 - C - CH 3 is
(a) Glycerol (b) Ethylene glycol | |
(c) Catechol (d) Resorcinol OH OH
2. An example of a compound with functional group – O – is :
(a) 1, 1-dimethyl-1, 3-butanediol
(a) acetic acid (b) methyl alcohol
(b) 2-methyl-2, 4-pentanediol
(c) diethyl ether (d) acetone
3. Butane-2-ol is (c) 4-methyl-2, 4-pentanediol
(a) primary alcohol (b) secondary alcohol (d) 1, 3, 3-trimethyl-1, 3-propanediol
(c) tertiary alcohol (d) aldehyde 11. Match the columns
4. Cresol has Column-I Column-II
(a) Alcoholic – OH (b) Phenolic – OH OH
(c) – COOH (d) – CHO
5. How many isomers of C5H11OH will be primary alcohols ? (A) (p) Quinol
(a) 5 (b) 4 (c) 2 (d) 3
6. In which of the following structures hydroxyl group is
attached to sp2 carbon atom? OH
OH OH
CH2OH CH (B) (q) Phenol
OH
(a) (b)
OH

OH CH(CH3)OH
(C) (r) Catechol
CH3
(c) (d) OH

OH
7. Which of the following is an example of unsymmetrical
ether?
(a) C2H5OC2H5 (b) C6H5OC6H5 (D) (s) Resorcinol
(c) C6H5OC2H5 (d) CH3OCH3
8. Vinyl carbinol is OH
(a) HO - CH 2 - CH = CH 2 (a) A – (q), B – (p), C – (s), D – (r)
(b) A – (r), B – (p), C – (s), D – (q)
(b) CH 3C(OH ) = CH 2
(c) A – (s), B – (q), C – (p), D – (r)
(c) CH 3 - CH = CH - OH (d) A – (q), B – (r), C – (s), D – (p)
(d) CH 3 - C(CH 2 OH) = CH 2 12. Assertion : The bond angle in alcohols is slightly less than
the tetrahedral angle.
9. Which of the following shows structure of allylic alcohol?
Reason : In alcohols, the oxygen of –OH group is attached
(i) CH 2 = CH - CH 2OH to sp3 hybridized carbon atom.
(ii) CH 2 = CH - OH (a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion.
(iii) CH 2 = CH - CH ( CH3 ) OH (b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion
(iv) CH 2 = CH - C ( CH3 )2OH (c) Assertion is correct, reason is incorrect
(a) (i), (iii) and (iv) (b) (i), (ii) and (iv) (d) Assertion is incorrect, reason is correct.
(c) (ii), (iii) and (iv) (d) (i), (ii), (iii) and (iv)
ALCOHOLS, PHENOLS AND ETHERS 351

Topic 2: Alcohols and Phenols 25. If ethanol dissolves in water, then which of the following
would be observed
13. Ethyl alcohol is industrially prepared from ethylene by (a) absorption of heat and contraction in volume
(a) Permanganate oxidation (b) emission of heat and contraction in volume
(b) Catalytic reduction (c) absorption of heat and increase in volume
(c) Absorbing in H2SO4 followed by hydrolysis (d) emission of heat and increase in volume
(d) All the three 26. Which of the following is correct ?
14. Sodium salt of benzene sulphonic acid on fusion with caustic (a) On reduction of any aldehyde, secondary alcohol is
soda gives
formed
(a) Benzene (b) Phenol
(b) Reaction of vegetable oil with H2SO4 gives glycerine
(c) Thiophenol (d) Benzoic acid
(c) Sucrose on reaction with NaCl gives invert sugar
15. Acid catalyzed hydration of alkenes except ethene leads to
the formation of (d) Alcoholic iodine gives iodoform with NaOH
(a) primary alcohol 27. Which of the following is not true in case of reaction with
(b) secondary or tertiary alcohol heated copper at 300°C?
(c) mixture of primary and secondary alcohols (a) Phenol ¾ ¾® Benzyl alcohol
(d) mixture of secondary and tertiary alcohols (b) Secondary alcohol ¾ ¾® Ketone
16. Ethyl alcohol can be prepared from Grignard reagent by the (c) Primary alcohol ¾ ¾® Aldehyde
reaction of : (d) Tertiary alcohol ¾ ¾® Olefin
(a) HCHO (b) R2CO (c) RCN (d) RCOCl
28. Match the columns
17. Isopropyl alcohol is obtained by reacting which of the
Column-I Column-II
following alkenes with concentrated H2SO4 followed by
boiling with H2O? (A) Methanol (p) Conversion of
phenol to
(a) Ethylene (b) Propylene
(c) 2-Methylpropene (d) Isoprene o-hydroxysalicylic
acid
18. Which of the following reacts with NaOH to give an alcohol?
(a) Propene (b) Butene (c) Ethanal (d) Methanal (B) Kolbe’s reaction (q) Wood spirit
19. Commercially carboxylic acids are reduced to alcohols by (C) Williamson’s (r) Heated copper at 573 K
converting them to the ______. synthesis
(a) esters (b) aldehydes (D) Conversion of 2° (s) Reaction of alkyl
(c) ketones (d) amines alcohol halide to ketone
HNO with sodium alkoxide
20. In the reaction, RNH 2 ¾¾¾¾¾
2 ® ROH + H O + C ­;
2
273-278K (a) A – (s), B – (r), C – (q), D – (p)
C is (where R = C6H5)
(b) A – (q), B – (s), C – (p), D – (r)
(a) NH3 (b) N2 (c) O2 (b) CO2
21. Alcohols of low molecular weight are (c) A – (q), B – (p), C – (s), D – (r)
(a) soluble in water (d) A – (r), B – (q), C – (p), D – (s)
(b) soluble in water on heating 29. Phenol is more acidic than alcohol because
(c) insoluble in water (a) phenol is more stable than water
(d) insoluble in all solvents (b) phenol is aromatic and alcohol is aliphatic
22. Which of the following has lowest boiling point ? (c) phenoxide ion is resonance stabilised
(a) p-Nitrophenol (b) m-Nitrophenol
(d) None of these
(c) o-Nitrophenol (d) Phenol
23. Which statement is not correct about alcohol? 30. Which one of the following compounds has the most acidic
nature?
(a) Molecular weight of alcohol is higher than water
(b) Alcohol of less no. of carbon atoms is less soluble in CH2OH OH
water than alcohol of more no. of carbon atoms (a) (b)
(c) Alcohol evaporates quickly
(d) All of the above OH
24. Which one of the following alcohols is least soluble in water?
OH CH
(a) CH 3 OH (b) C 3 H 7 OH (c) (d)
(c) C 4 H 9 OH (d) C10 H 21OH
 EBD_7374
352 CHEMISTRY

31. When ethyl alcohol reacts with acetic acid, the products 43. Which of the following compounds will react with sodium
formed are hydroxide solution in water?
(a) Sodium ethoxide + hydrogen (a) C6H5OH (b) C6H5CH2OH
(b) Ethyl acetate + water (c) (CH3)3COH (d) C2H5OH
(c) Ethyl acetate + soap 44. Which of the following is most acidic?
(d) Ethyl alcohol + water (a) Benzyl alcohol (b) Cyclohexanol
32. Which of the following compounds is oxidised to prepare (c) Phenol (d) m-Chlorophenol
methyl ethyl ketone? 45. Arrange the following in increasing order of their acidity?
(a) 2-Propanol (b) l-Butanol o–cresol(a), salicylic acid(b), phenol(c)
(c) 2-Butanol (d) t-Butyl alcohol (a) c < a < b (b) b < c < a (c) a < b < a (d) a < c < b
33. The compound which reacts fastest with Lucas reagent at 46. Which of the following statements are correct ?
room temperature is (i) Alcohols react as nucleophiles in the reactions
(a) Butan-1-ol (b) Butan-2-ol involving cleavage of O–H bond.
(c) 2-Methyl propan-1-ol (d) 2-Methylpropan-2-ol (ii) Alcohols react as electrophiles in the reactions
34. When phenol is treated with excess bromine water, it gives: involving cleavage of O–H bond.
(a) m-Bromophenol (b) o- and p-Bromophenol (iii) Alcohols react as nucleophile in the reaction involving
(c) 2, 4-Dibromophenol (d) 2, 4, 6-Tribromophenol cleavage of C–O bond.
35. When phenol is heated with CHCl3 and alcoholic KOH (iv) Alcohols react as electrophiles in the reactions
salicyladehyde is produced. This reaction is known as involving C–O bond.
(a) Rosenmund’s reaction (b) Reimer-Tiemann reaction (a) (i) only (b) (i) and (iv)
(c) Friedel-Crafts reaction (d) Sommelet reaction (c) (ii) and (iii) (d) (ii) only
36. Assertion : In Lucas test, 3º alcohols react immediately. 47. Assertion : Reimer-Tiemann reaction of phenol with CCl4 in
NaOH at 340 K gives salicylic acid as the major product.
Reason : An equimolar mixture of anhyd. ZnCl2 and conc.
HCl is called Lucas reagent. Reason : The reaction occurs through intermediate formation
of dichlorocarbene.
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion. (a) Assertion is correct, reason is correct; reason is a
(b) Assertion is correct, reason is correct; reason is not a correct explanation for assertion.
correct explanation for assertion. (b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion.
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct. (c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct.
37. Lucas test is used to differentiate between
(a) alcohol and ketone 48. Which of the following statements are correct ?
(i) In phenols, the —OH group is attached to sp 2
(b) alcohol and aromatic ketones
hybridised carbon of an aromatic ring
(c) 1°, 2° and 3° alcohols
(ii) The carbon – oxygen bond length (136 pm) in phenol
(d) None of these
is slightly more than that in methanol
38. To distinguish between salicylic acid and phenol, one can
(iii) Partial double bond character is due to the conjugation
use
of unshared electron pair of oxygen with the aromatic
(a) NaHCO3 solution (b) 5% NaOH solution ring.
(c) neutral FeCl3 (d) bromine water (iv) Phenol has sp2 hybridised state of carbon to which
39. Ethyl alcohol exhibits acidic character on reacting it with oxygen is attached.
(a) acetic acid (b) sodium metal (a) (i), (ii) and (v) (b) (i), (ii) and (iii)
(c) hydrogen chloride (d) acidic K2Cr2O7 (c) (i), (iii) and (iv) (d) (i) and (iv)
40. Phenol, when first reacts with concentrated sulphuric acid 49. Match the columns
and then with concentrated nitric acid, it gives Column-I Column-II
(a) 2, 4, 6-trinitrobenzene (b) o-nitrophenol (A) Antifreeze used in (p) Methanol
(c) p-nitrophenol (d) nitrobenzene car engine
41. 3 moles of ethanol react with one mole of phosphorus (B) Solvent used in (q) Phenol
tribromide to form 3 moles of bromoethane and one mole of perfumes
X. Which of the following is X? (C) Starting material for (r) Ethlene glycol
(a) H3PO4 (b) H3PO2 (c) HPO3 (d) H3PO3 picric acid
42. Methanol and ethanol can be distinguished by the following: (D) Wood spirit (s) Ethanol
(a) By reaction with metallic sodium (a) A – (s), B – (q), C – (p), D – (r)
(b) By reaction with caustic soda (b) A – (r), B – (s), C – (q), D – (p)
(c) By heating with iodine and washing soda (c) A – (s), B – (q), C – (r), D – (p)
(d) By heating with zinc and inorganic mineral acid (d) A – (p), B – (r), C – (q), D – (s)
ALCOHOLS, PHENOLS AND ETHERS 353

50. Which of the following statements are correct ? (a) II > IV > I > III (b) I > II > III > IV
(i) Ethanol mixed with methanol is called denatured (c) III > I > II > IV (d) IV > III > I > II
alcohol. 57. Assertion : In case of phenol, bromination takes place even
(ii) Excess of methanol in body may cause blindness. in absence of Lewis acid whereas bromination of benzene
(iii) In the body methanol is oxidised to methanoic acid. takes place in presence of Lewis acid like FeBr 3.
(iv) A methanol poisoned patient is treated by giving Reason : – OH group attached to benzene ring is highly
intravenous injections of ethanoic acid. deactivating.
(a) (i), (ii) and (iii) (b) (ii), (iii) and (iv)
(a) Assertion is correct, reason is correct; reason is a
(c) (i) and (v) (d) (i), (iii) and (iv)
correct explanation for assertion.
51. Assertion : Phenol is more reactive than benzene towards
(b) Assertion is correct, reason is correct; reason is not a
electrophilic substitution reaction.
correct explanation for assertion.
Reason : In the case of phenol, the intermediate carbocation
(c) Assertion is correct, reason is incorrect.
is more resonance stabilized.
(d) Assertion is incorrect, reason is correct.
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion. 58. Mechanism of acid catalysed hydration reaction involves
(b) Assertion is correct, reason is correct; reason is not a (i) Protonation of alkene to form carbocation by
correct explanation for assertion. electrophilic attack of H3O+
(c) Assertion is correct, reason is incorrect. (ii) Nucleophilic attack of water on carbocation.
(d) Assertion is incorrect, reason is correct. (iii) Deprotonation to form alcohol.
52. Propene, CH3CH = CH 2 can be converted into 1-propanol (a) (i) and (ii) (b) (i) and (iii)
by oxidation. Indicate which set of reagents amongst the (c) (i), (ii) and (iii) (d) (ii) and (iii)
following is ideal to effect the above conversion ?
59. Which one of the following compounds will be most readily
(a) KMnO4 (alkaline)
attacked by an electrophile ?
(b) Osmium tetraoxide (OsO4/CH2Cl2)
(a) Chlorobenzene (b) Benzene
(c) B2H6 and alk. H2O2
(d) O3/Zn (c) Phenol (d) Toluene
53. The product of the following reaction is 60. Consider the following reaction:
(i ) BH 3 / THF Zn dust CH Cl
¾¾ ¾ ¾ ¾ ¾
¾ ® Phenol ¾¾¾¾
® X ¾¾¾¾¾¾¾
3 ®Y
- Anhydrous AlCl3
(ii ) H 2 O 2 , OH
(a) 1-Pentanol (b) 2-Pentanol Alkaline KMnO
¾¾¾¾¾¾¾
4®Z
(c) Pentane (d) 1,2-Pentanediol
The product Z is
X
54. C6 H5 - CH = CHCHO ¾¾® C6 H5 CH = CHCH 2 OH . In (a) benzaldehyde (b) benzoic acid
the above sequence, X can be (c) benzene (d) toluene
(a) N2 / Ni (b) NaBH4 61. The reagent used for dehydration of an alcohol is
(c) K2Cr2O7 / H+ (d) Both (a) and (b) (a) phosphorus pentachloride
55. The hydroboration of an alkene is carried out, followed by (b) calcium chloride
oxidation with hydrogen peroxide, the alcohol so obtained (c) aluminium oxide
is achiral. Possible structure of alkene is (are) : (d) sodium chloride
(i) 2, 3– dimethylbut–2–ene. 62. The alcohol which does not give a stable compound on
(ii) 3, 4–dimethylbut –3–ene. dehydration is
(iii) 2–methyl–but–2–ene. (a) ethyl alcohol (b) methyl alcohol
(iv) 2–methylpropene. (c) n-Propyl alcohol (d) n-Butyl alcohol
(a) (i) and (iv) (b) (ii) and (iii) 63. A compound of the formula C4H10O reacts with sodium and
(c) (iii) and (iv) (d) (i) and (iii) undergoes oxidation to give a carbonyl compound which
56. Arrange the following compounds in order of decreasing does not reduce Tollen’s reagent, the original compound is
acidity : (a) Diethyl ether (b) n-Butyl alcohol
(c) Isobutyl alcohol (d) sec-Butyl alcohol
OH OH OH OH 64. In the following sequence of reactions,
P +I Mg HCHO
CH 3CH 2 OH ¾¾¾
2 ® A ¾¾¾® B ¾¾¾¾
®
ether
; ; ; ;
H O
C ¾¾¾
2 ®D
the compound D is
Cl CH3 NO2 OCH3 (a) propanal (b) butanal
(I) (II) (III) (IV) (c) n-butyl alcohol (d) n-propyl alcohol.
 EBD_7374
354 CHEMISTRY

65. Assertion : Ethyl phenyl ether on reaction with HBr forms (d) mixing of Cu(OAc) 2 and pyridine to make the
phenol and ethyl bromide. commercial alcohol unfit for drinking
Reason : Cleavage of C–O bond takes place on ethyl-
oxygen bond due to the more stable phenyl-oxygen bond. Topic 4: Ethers
(a) Assertion is correct, reason is correct; reason is a 72. Which of the following cannot be made by using
correct explanation for assertion.
Williamson’s synthesis?
(b) Assertion is correct, reason is correct; reason is not a
(a) Methoxybenzene
correct explanation for assertion.
(b) Benzyl p-nitrophenyl ether
(c) Assertion is correct, reason is incorrect.
(c) Methyl tertiary butyl ether
(d) Assertion is incorrect, reason is correct.
(d) Di-tert-butyl ether
Topic 3: Some commercially important alcohols 73. Ethanol and dimethyl ether form a pair of functional isomers.
The boiling point of ethanol is higher than that of dimethyl
66. Which enzyme converts glucose and fructose both into ether, due to the presence of
ethanol ? (a) H-bonding in ethanol
(a) Diastase (b) Invertase (b) H-bonding in dimethyl ether
(c) Zymase (d) Maltase (c) CH3 group in ethanol
67. An industrial method of preparation of methanol is : (d) CH3 group in dimethyl ether
(a) catalytic reduction of carbon monoxide in presence of 74. An ether is more volatile than an alcohol having the same
ZnO–Cr2O3 molecular formula. This is due to
(b) by reacting methane with steam at 900ºC with a nickel (a) dipolar character of ethers
catalyst (b) alcohols having resonance structures
(c) by reducing formaldehyde with lithium aluminium (c) inter-molecular hydrogen bonding in ethers
hydride (d) inter-molecular hydrogen bonding in alcohols
(d) by reacting formaldehyde with aqueous sodium 75. Which of the following has strongest hydrogen bonding?
hydroxide solution
(a) Ethyl amine (b) Ethanal
68. ‘Drinking alcohol’ is very harmful and it ruins the health.
(c) Ethyl alcohol (d) Diethyl ether
‘Drinking alcohol’ stands for
76. Oxygen atom in ether is
(a) drinking methyl alcohol
(a) very active (b) replaceable
(b) drinking ethyl alcohol
(c) comparatively inert (d) active
(c) drinking propyl alcohol
77. The ether that undergoes electrophilic substitution reactions
(d) drinking isopropyl alcohol
is
69. In the commercial manufacture of ethyl alcohol from starchy
(a) CH3OC2H5 (b) C6H5OCH3
substances by fermentation method. Which enzymes
stepwise complete the fermentation reaction (c) CH3OCH3 (d) C2H5OC2H5
(a) Diastase, maltase and zymase 78. Diethyl ether can be decomposed by heating with
(b) Maltase, zymase and invertase (a) HI (b) NaOH (c) Water (d) KMnO4
(c) Diastase, zymase and lactase 79. The major organic product in the reaction,
(d) Diastase, invertase and zymase CH3 — O — CH(CH3)2 + HI ® Product is
70. Select the incorrect statement about the fermentation. (a) ICH2OCH(CH3)2 (b) CH 3 O C(CH 3 ) 2
|
(a) When grapes are crushed, sugar and the enzyme come I
in contact and fermentation starts
(c) CH3I + (CH3)2CHOH (d) CH3OH + (CH3)2CHI
(b) Fermentation takes place in anaerobic conditions
80. An aromatic ether is not cleaved by HI even at 525 K. The
(c) Carbon monoxide is released during fermentation
compound is
(d) If air gets into fermentation mixture, the oxygen of air
(a) C6H5OCH3 (b) C6H5OC6H5
oxidises ethanol to ethanoic acid which in turn destroys
(c) C6H5OC3H7 (d) Tetrahydrofuran
the taste of alcoholic drinks
81. Assertion : ter - Butyl methyl ether is not prepared by the
71. Denaturation of alcohol is the
reaction of ter-butyl bromide with sodium methoxide.
(a) mixing of CuSO4 (a foul smelling solid) and pyridine (to
give the colour) to make the commercial alcohol unfit Reason : Sodium methoxide is a strong nucleophile.
for drinking (a) Assertion is correct, reason is correct; reason is a
(b) mixing of CuSO4 (to give the colour) and pyridine (a correct explanation for assertion.
foul smelling solid) to make the commercial alcohol unfit (b) Assertion is correct, reason is correct; reason is not a
for drinking correct explanation for assertion.
(c) mixing of Cu(OAc)2 and ammonia to make the (c) Assertion is correct, reason is incorrect.
commercial alcohol unfit for drinking (d) Assertion is incorrect, reason is correct.
ALCOHOLS, PHENOLS AND ETHERS 355

82. When 2-methoxypropane is heated with HI, in the mole ratio Which of the following compounds will be formed?
1 : 1, the major products formed are
(a) CH3 - CH - CH3 + CH 3CH 2 OH
(a) methanol and 2-iodopropane
|
(b) methyl iodide and 2-propanol CH3
(c) methyl iodide and 2-iodopropane
(d) methanol and 2-propanol (b) CH3 - CH - CH 2 OH + CH3CH3
|
83. Which of the following compounds is resistant to
CH3
nucleophilic attack by hydroxyl ions?
(a) Methyl acetate (b) Acetonitrile CH3
(c) Acetamide (d) Diethyl ether |
(c) CH3 - CH - CH 2 OH + CH3 - CH 2 - I
84. The major product of the reaction between tert-butyl chloride
and sodium ethoxide is CH3
(a) 2-methylprop-1-ene (b) 1-butene |
(d) CH3 - CH - CH 2 - I + CH3 CH 2 OH
(c) 2-butene (d) ethene
85. In Williamson synthesis if tertiary alkyl halide is used than 87. Assertion : Ethers behave as bases in the presence of
(a) ether is obtained in good yield mineral acids.
(b) ether is obtained in poor yield Reason : Due to the presence of lone pairs of electrons on
(c) alkene is the only reaction product oxygen.
(d) a mixture of alkene as a major product and ether as a (a) Assertion is correct, reason is correct; reason is a
minor product forms. correct explanation for assertion.
86. In the reaction: (b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion.
CH3
| (c) Assertion is correct, reason is incorrect.
Heated
CH3 - CH - CH 2 - O - CH 2 - CH3 + HI ¾¾¾¾ ® (d) Assertion is incorrect, reason is correct.

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 6. Which of the following compounds is aromatic alcohol?

1. Monochlorination of toluene in sunlight followed by
OH CH2OH CH2OH OH
hydrolysis with aq. NaOH yields
(a) o – cresol (b) m – cresol
(c) 2, 4 – dihydroxytoluene (d) benzyl alcohol
2. How many alcohols with molecular formula C4H10O are CH3 CH3
chiral in nature? (A) (B) (C) (D)
(a) 1 (b) 2 (c) 3 (d) 4
3. What is the correct order of reactivity of alcohols in the (a) A, B, C, D (b) A, D
following reaction? (c) B, C (d) A
ZnCl 7. Give IUPAC name of the compound given below.
R — OH + HCl ¾¾¾¾
2 ® R – Cl + H O
2
(a) 1° > 2° > 3° (b) 1° < 2° < 3° CH3 — CH — CH 2 —C H 2 — CH3
| | |
(c) 3° > 2° > 1° (d) 3° > 1° > 2° Cl OH OH
4. CH3CH2OH can be converted into CH3CHO by ........ .
(a) catalytic hydrogenation (a) 2-chloro-5-hydroxyhexane
(b) treatment with LiAlH4 (b) 2-hydroxy-5-chlorohexane
(c) treatment with pyridinium chlorochromate (c) 5-chlorohexan-2-ol
(d) treatment with KMnO4 (d) 2-chlorohexan-5-ol
5. The process of converting alkyl halides into alcohols 8. IUPAC name of m-cresol is ........... .
involves ............ . (a) 3-methylphenol (b) 3-chlorophenol
(a) addition reaction (b) substitution reaction (c) 3-methoxyphenol (d) benzene-1,3-diol
(c) dehydrohalogenation (d) rearrangement reaction
 EBD_7374
356 CHEMISTRY

9. IUPAC name of the compound CH3 —CH — OCH3 is 16. Arrange the following compounds in increasing order of
............... . | boiling point.
CH3 Propan - 1- ol, butan - 1 - ol, butan - 2 - ol, pentan - 1 - ol
(a) 1-methoxy-1methylethane
(b) 2-methoxy-2-methylethane (a) Propan-1-ol, butan-2-ol, butan-1-ol, pentan-1-ol
(c) 2-methoxypropane (b) Propan-1-ol, butan-1-ol, butan-2-ol, pentan-1-ol
(d) isopropylmethyl ether (c) Pentan-1-ol, butan-2-ol, butan-1-ol, propan-1-ol
10. Which of the following species can act as the strongest (d) Pentan-1-ol, butan-1-ol, butan-2-ol, propan-1-ol
base? Past Year MCQs
(a) –OH (b) –OR
17. Among the following sets of reactants which one produces
anisole? [AIPMT 2014, A]
–
(c) –OC H
6 5 (d) O (a) CH3CHO; RMgX
(b) C6H5OH; NaOH ; CH3I
NO2
(c) C6H5OH; neutral FeCl3
11. Which of the following compounds will react with sodium (d) C6H5–CH3; CH3COCl; AlCl3
hydroxide solution in water?
18. Which of the following will not be soluble in sodium
(a) C6H5OH (b) C6H5CH2OH hydrogen carbonate? [AIPMT 2014, S]
(c) (CH3)3COH (d) C2H5OH (a) 2, 4, 6-trinitrophenol (b) Benzoic acid
(c) o-Nitrophenol (d) Benzenesulphonic acid
12. Phenol is less acidic than ............. .
(a) ethanol (b) o - nitrophenol 19. Identify Z in the sequence of reactions: [AIPMT 2014, S]
(c) o-methylphenol (d) o-methoxyphenol 2 2 HBr/H O
2 5 C H ONa
CH3CH 2 CH=CH 2 ¾¾¾¾¾ ® Y ¾¾¾¾¾®Z
13. Which of the following is most acidic?
(a) Benzyl alcohol (b) Cyclohexanol (a) CH3—(CH2)3 —O—CH2CH3
(c) Phenol (d) m-chlorophenol (b) (CH3)2 CH2—O—CH2CH3
14. Mark the correct order of decreasing acid strength of the (c) CH3(CH2)4—O—CH3
following compounds. (d) CH3CH2—CH(CH3)—O—CH2CH3
20. Which of the following alcohols gives the best yield of
OH OH OH OH OH dialkyl ether on being heated with a trace of sulphuric acid?
[AIIMS 2014, C]
(a) 2-Pentanol (b) Cyclopentanol
OCH3 NO2 (c) 2-Methyl-2-butanol (d) 1-Pentanol
NO2 OCH3 21. The most suitable reagent for the conversion of
R - CH 2 - OH ¾¾ ® R - CHO is: [JEE M 2014, S]
(i) (ii) (iii) (iv) (v)
(a) KMnO4
(b) K2Cr2O7
(a) V > IV > II > I > III (b) II > IV > I > III > V
(c) CrO3
(c) IV > V > III > II > I (d) V > IV > III > II > I
(d) PCC (Pyridinium chlorochromate)
15. Mark the correct increasing order of reactivity of the
22. Sodium phenoxide when heated with CO2 under pressure at
following compounds with HBr/HCl.
125ºC yields a product which on acetylation produces C
CH2OH CH2OH CH2OH ONa 125°C H+
+ CO 2 ¾¾¾¾
® B ¾¾¾® C
5 atm Ac2 O

The major product C would be [JEE M 2014, A]

NO2 Cl OCOCH3 OH
(I) (II) (III)
COOH COCH3
(a) (b)
(a) I < II < III (b) II < I < III
(c) II < III < I (d) III < II < I
COCH3
ALCOHOLS, PHENOLS AND ETHERS 357

29. Which of the following is not the product of dehydration of

OH OCOCH3

COOCH3
(c) (d) OH ? [AIPMT 2015 RS, S]
COOH

23. The ionization constant of phenol is higher than that of

ethanol because : [BITSAT 2014, C] (a) (b)
(a) Phenoxide ion is bulkier than ethoxide
(b) Phenoxide ion is stronger base than ethoxide
(c) Phenoxide ion is stabilized through delocalization (c) (d)
(d) Phenoxide ion is less stable than ethoxide
24. Consider the following phenols : 30. Which of the following reagents convert propene to 1-
OH OH OH OH propanol? [AIIMS 2015, C]
(a) H2O, H2SO4 (b) Aqueous KOH
(c) MgSO4, NaBH4/H2O (d) B2H6, H2O2, OH–
NO2 31. Which of the following fact(s) explain(s) as to why p-
CH3 NO2 nitrophenol is more acidic than phenol?
(I) (II) (III) (IV) I. –I Effect of nitro group. [AIIMS 2015, C]
The decreasing order of acidity of the above phenols is
II. Greater resonance effect of p-nitrophenoxy group
[BITSAT 2014, S]
III. Steric effect of bulky nitro group
(a) III > IV > II > I (b) II > I > IV > III
(c) I > IV > II > III (d) III > IV > I > II (a) I and II (b) I and III (c) II and III (d) II alone
25. Sodium salt of benzene sulphonic acid on fusion with caustic 32. Assertion : Phenol undergo Kolbe reaction, ethanol does
soda gives [BITSAT 2014, C] not. [AIIMS 2014, 2015, C]
(a) Benzene (b) Phenol Reason : Phenoxide ion is more basic than ethoxide ion.
(c) Thiophenol (d) Benzoic acid (a) If both Assertion and Reason are correct and Reason
26. The reaction is the correct explanation of Assertion.
CH3 CH3 (b) If both Assertion and Reason are correct, but Reason
is not the correct explanation of Assertion.
CH3–C–ONa + CH3CH2Cl–—®CH3–C–O–CH2–CH3
–NaCl (c) If Assertion is correct but Reason is incorrect.
CH3 CH3 (d) If both the Assertion and Reason are incorrect.
33. Which of the following reagents would distinguish cis-
is called :- [AIPMT 2015, A]
cyclopenta-1,2-diol from the trans-isomer? [NEET 2016, S]
(a) Williamson continuous etherification process
(a) Acetone (b) Ozone
(b) Etard reaction
(c) MnO2 (d) Aluminium isopropxide
(c) Gatterman - Koch reaction
34. The reaction
(d) Williamson Synthesis
27. Reaction of phenol with chloroform in presence of dilute Å Me
NaOH Me–I
OH ¾¾® O– Na ¾¾® O
sodium hydroxide finally introduces which one of the
following functional group? [AIPMT 2015 RS, S]
Can be classified as :- [NEET 2016, A]
(a) – CH2Cl (b) – COOH (c) – CHCl2 (d) – CHO
(a) Williamson ether synthesis reaction
28. Which of the following reaction (s) can be used for the (b) Alcohol formation reaction
preparation of alkyl halides ? [AIPMT 2015 RS, A]
(c) Dehydration reaction
(I) anhy.ZnCl2
CH3CH2OH + HCl ¾¾¾¾¾ (d) Williamson alcohol synthesis reaction
®
35. ClCH2CH2OH is stronger acid than CH3CH2OH because of:
(II) CH3CH2OH + HCl ¾¾
® [AIIMS 2016, C]
(III) (CH3)3COH + HCl ¾¾
® (a) – I effect of Cl increases negative charge on O atom of
alcohol
(IV) (CH3)2CHOH + HCl ¾¾¾¾¾ anhy.ZnCl2
® (b) – I effect of Cl disperses negative charge on O atom to
(a) (I), (III) and (IV) only (b) (I) and (II) only produce more stable cation
(c) (IV) only (d) (III) and (IV) only
 EBD_7374
358 CHEMISTRY

(c) – I effect of Cl disperses negative charge on O atom to

OH OH
produce more stable anion
(d) None of these (c) O2N NO2 (d)
36. Assertion : Ethyl phenyl ether on reaction with HBr form
phenol and ethyl bromide. CH3
NO2
Reason : Cleavage of C–O bond takes place on ethyl-
oxygen bond due to the more stable phenyl-oxygen bond. 40. The heating of phenyl-methyl ethers with HI produces
[AIIMS 2016, C] [NEET 2017, S]
(a) If both Assertion and Reason are correct and Reason (a) Iodobenzene (b) Phenol
is the correct explanation of Assertion. (c) Benzene (d) Ethyl chlorides
41. Identify A and predict the type of reaction
(b) If both Assertion and Reason are correct, but Reason
[NEET 2017, A, BN]
is not the correct explanation of Assertion.
OCH3
(c) If Assertion is correct but Reason is incorrect.
(d) If both the Assertion and Reason are incorrect.
NaNH2
37. Which of the following method gives better yield of p- A
nitrophenol? [BITSAT 2016, A]
Br
dil.HNO3
(a) Phenol ¾¾¾¾® p-Nitrophenol OCH3
20°C
(i) NaNO 2 + H2SO4 , 7 - 8°C NH2
(b) Phenol ¾¾¾¾¾¾¾¾¾¾® p-Nitrophenol (a) and elimination addition reaction
(ii) HNO3
(i) NaOH
(c) Phenol ¾¾¾¾¾¾®
(ii) Conc. HNO3
OCH3
(d) None of the three.
.. .. CH3 Br
H+
38. OH
.. + O = C ® X [X] is
¾¾¾
..

(b) and cine substitution reaction

CH3
[BITSAT 2016, A]
CH3
OCH3
(a) HO C CH3

OH
(c) and cine substitution reaction
CH3
..
(b) HO .O. C CH3
H OCH3
CH3

(c) HO C C CH3
(d) and substitution reaction
OH
..
..

O NH2
CH3
42. In the reaction
(d) HO C OH
NaOH CO2 + HCl
CH3
Phenol ¾¾ ¾® (A) ¾¾¾¾®
¾ 140°
(B), here B is

39. Which one is the most acidic compound ? [NEET 2017, S] [AIIMS 2017, A]
(a) benzaldehyde (b) chlorobenzene
OH
OH (c) benzoic acid (d) salicylic acid
43. Which of the following , upon treatment with tert-BuONa
(a) (b) followed by addition of bromine water, fails to decolourize
the colour of bromine? [JEE M 2017, A]
NO2
ALCOHOLS, PHENOLS AND ETHERS 359

O C6H5 Anhydrous
AlCl
(a) (b) + CH3CH2CH2Cl ¾¾¾¾®
3

Br Br (i) O
P ¾¾¾¾®
2
+ Q+R
(ii) H3O /D
O
O
P Q R
(c) (d)
Br Br CH2CH2CH3 CHO

44. The compound A on treatment with Na gives B, and with (a) , , CH3CH2 – OH
PCl5 gives C. B and C react together to give diethyl ether.
A, B and C are in the order [NEET 2018, S]
(a) C2H5OH, C2H6, C2H5Cl CH2CH2CH3 CHO COOH
(b) C2H5OH, C2H5Cl, C2H5ONa
(b) , ,
(c) C2H5OH, C2H5ONa, C2H5Cl
(d) C2H5Cl, C2H6, C2H5OH
45. In the reaction OH
CH(CH3)2
– +
OH O Na (c) , , CH3 – CO – CH3
CHO
+ CHCl3+ NaOH ¾®
CH(CH3)2 OH
The electrophile involved is [NEET 2018, A] (d) , ,CH3CH(OH)CH3

(
(a) Dichloromethyl cation C HCl2
Å
) O
(i) HBr/D
48. ¾¾¾¾¾¾¾
® [AIIMS 2018,
Formyl cation ( C HO )
Å (ii) Conc. H2SO 4
(b)
(c) Dichlorocarbene (: CCl 2 ) S]

(d) Dichloromethyl anion CHCl 2( !

) (a)
Br
(b) Br
46. Compound A, C8H10O, is found to react with NaOI
(produced by reacting Y with NaOH) and yields a yellow
precipitate with characteristic smell. [NEET 2018, S] Br OH
A and Y are respectively
(c) (d)
(a) H3C CH2 – OH and I2 Br
49. Assertion : Ortho nitro phenol is more acidic than meta
nitro phenol.
(b) CH2 – CH2 – OH and I2
Reason : Ortho nitro phenol has more – I effect than meta
nitro phenol. [AIIMS 2018, C]
CH3 (a) If both assertion and reason are true and reason is the
correct explanation of assertion.
(c) CH3 OH and I2
(b) If both assertion and reason are true but reason is not
the correct explanation of assertion.
(c) If assertion is true but reason is false.
(d) CH – CH3 and I2 (d) If both assertion and reason are false.
50. Phenol on treatment with CO2 in the presence of NaOH
OH
followed by acidification produces compound X as the major
47. Identify the major products P, Q and R in the following product. X on treatment with (CH3CO)2O in the presence of
sequence of reactions: [NEET 2018, A] catalytic amount of H2SO4 produces : [JEE M 2018, S]
 EBD_7374
360 CHEMISTRY

(a) (b)

(a) (b)
(c) (d)

OH

NaOH CH2 = CHCH2Cl

53. [X] [Y] . Here [Y] is a
(c) (d)

[BITSAT 2018, A]
51. Phenol reacts with methyl chloroformate in the presence of (a) single compound
NaOH to form product A. A reacts with Br 2 to form product
B. A and B are respectively : [JEE M 2018, (b) mixture of two compounds
S] (c) mixture of three compounds
(d) no reaction is possible

(a) and 54. Following compounds are given:

(1) CH3CH2OH (2) CH3COCH3

CH 3 - CHOH
(3) (4) CH3OH

(b) and CH 3

Which of the above compound(s), on being warmed with

iodine solution and NaOH, will give iodoform?
(c) and [BITSAT 2018, A]
(a) (1) and (2) (b) (1), (3) and (4)
(c) only (2) (d) (1), (2) and (3)
(d) and 55. Arrange the following alcohols in increasing order of their
reactivity towards the reaction with HCl.
52. The major product formed in the following reaction is : (CH3)2CH-OH (1), (CH3)3C-OH (2), (C6H5)3C-OH (3)
[JEE M 2018, A] [BITSAT 2018, S]
(a) 1 < 2 < 3 (b) 2 < 1 < 3
(c) 3 < 1 < 2 (d) 2 < 3 < 1
ALCOHOLS, PHENOLS AND ETHERS 361

Exercise 3 : Try If You Can

1. Given are cyclohexanol (I), acetic acid (II), 2, 4, 6 – 6. Increasing order of acid strength among p-methoxyphenol,
trinitrophenol (III) and phenol (IV). In these the order of p-methylphenol and p-nitrophenol is
decreasing acidic character will be : (a) p-Nitrophenol, p-Methoxyphenol, p-Methylphenol
(a) III > II > IV > I (b) II > III > I > IV (b) p-Methylphenol, p-Methoxyphenol, p-Nitrophenol
(c) II > III > IV > I (d) III > IV > II > I (c) p-Nitrophenol, p-Methylphenol, p-Methoxyphenol.
(d) p-Methoxyphenol, p-Methylphenol, p-Nitrophenol
2. ® HO — (CH2)6 — OH, this conversion can be 7. Product C in the reaction,
Na CH I
C 2 H 5Br ¾¾NaOH
¾¾¾® A ¾¾® B ¾¾¾
3 ®C
will be
(aqueous)
achieved by
(a) propane (b) ethyl iodide
(a) O3, Zn, then LiAlH4 (c) ethane (d) ethyl methyl ether
(b) O3/H2O2, then LiAlH4 8. The structure of the compound that gives a tribromo
derivative on treatment with bromine water is
(c) cold dil. KMnO4, HlO4, then LiAlH4
CH 3 CH3
(d) All of these
OH
3. Which type of carbocation is/are formed when
(a) (b)

OH is treated with an acid? OH

(a) 1º (b) 2º CH3 CH2OH

(c) 3º (d) All the three
4. ClCH2CH2OH is stronger acid than CH3CH2OH because of: (c) (d)
(a) – I effect of Cl increases negative charge on O atom of OH
alcohol
9. Which of the following is the correct order for ease of
(b) – I effect of Cl disperses negative charge on O atom to
dehydration–
produce more stable cation
(c) – I effect of Cl disperses negative charge on O atom to OH
produce more stable anion |
CH3 - CH 2 - CH 2 - CH 2 CH3 - CH 2 - CH - CH3
(d) None of these |
5. Identify the nature of product in the following reaction (I) OH (II)
OH
OH OH
HO
– |
+K2S2O8 Product CH 2 = CH - CH - CH3
H2O
(III)
(IV)
OH OH (a) I > III > II > IV (b) IV > III > II > I
SO3H (c) IV > II > III > I (d) III > IV > II > I
(a) (b) 10. Which of the following will most readily be dehydrated in
acidic conditions ?
SO3H O OH OH
(a) || | (b) |
OH OH
OH O O
|| ||
(c) (d)
(c) | (d) |
OH OH OH
 EBD_7374
362 CHEMISTRY

11. Which of the following is most reactive towards aqueous

HBr ? OD
(a) 1-Phenyl - 2- propanol D (i) CO2
NaOH
(b) 1- Phenyl - 1- propanol 14. [Intermediate] (ii) D+ P . Here P is
(c) 3-Phenyl - 1 - propanol
(d) 2- Phenyl - 1 - propanol
12. Phenol is converted into bakelite by heating it with OD OD
formaldehyde in presence of alkali or acid. Which statement (a) HOOC D
(b) DOOC D
is true regarding this reactions ?
(a) The electrophilie in both cases is CH2 = O
+
(b) The electrophile in both cases is CH 2 = O H
OH
(c) The electrophile is CH2 = O in presence of alkali and (c) DOOC (d) Reaction not possible
+ D
CH 2 = O H in presence of acid
(d) It is a nucleophilic substitution reaction

15. Ethanol can be prepared more easily by which reaction ?

H 2SO4
13. ¾¾¾¾®
(i) CH 3 CH 2 Br + H 2 O ¾¾
® CH 3 CH 2 OH
OH
(ii) CH 3CH 2 Br + Ag 2 O (in boiling water) ¾¾
®
Which carbocation is involved in the above reaction ?
CH3CH 2OH
(a) by (i) reaction
(a) (b) (b) by (ii) reaction
+ (c) Both reactions proceed at same rate
+
(d) by none
(c) Both (d) None

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 10 (b) 19 (a) 28 (c) 37 (c) 46 (b) 55 (a) 64 (d) 73 (a) 82 (b)
2 (c) 11 (d) 20 (b) 29 (c) 38 (a) 47 (c) 56 (c) 65 (c) 74 (d) 83 (d)
3 (b) 12 (b) 21 (a) 30 (b) 39 (b) 48 (c) 57 (c) 66 (c) 75 (c) 84 (a)
4 (b) 13 (c) 22 (c) 31 (b) 40 (b) 49 (b) 58 (c) 67 (a) 76 (c) 85 (c)
5 (b) 14 (b) 23 (b) 32 (c) 41 (d) 50 (a) 59 (c) 68 (b) 77 (b) 86 (c)
6 (c) 15 (b) 24 (d) 33 (d) 42 (c) 51 (a) 60 (b) 69 (a) 78 (a) 87 (a)
7 (c) 16 (a) 25 (b) 34 (d) 43 (a) 52 (c) 61 (c) 70 (c) 79 (c)
8 (a) 17 (b) 26 (d) 35 (b) 44 (d) 53 (a) 62 (b) 71 (b) 80 (b)
9 (a) 18 (d) 27 (a) 36 (b) 45 (d) 54 (b) 63 (d) 72 (d) 81 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (d) 7 (c) 13 (d) 19 (a) 25 (b) 31 (d) 37 (b) 43 (a) 49 (b) 55 (d)
2 (a) 8 (a) 14 (b) 20 (b) 26 (d) 32 (b) 38 (d) 44 (c) 50 (a)
3 (c) 9 (c) 15 (c) 21 (d) 27 (d) 33 (a) 39 (c) 45 (c) 51 (c)
4 (c) 10 (b) 16 (a) 22 (a) 28 (a) 34 (a) 40 (b) 46 (d) 52 (d)
5 (b) 11 (a) 17 (b) 23 (c) 29 (b) 35 (d) 41 (d) 47 (c) 53 (c)
6 (c) 12 (b) 18 (c) 24 (a) 30 (a) 36 (a) 42 (b) 48 (a) 54 (a)
Exercise 3 : Try If You Can
1 (a) 3 (d) 5 (d) 7 (d) 9 (b) 11 (b) 13 (c) 15 (b)
2 (d) 4 (c) 6 (d) 8 (c) 10 (a) 12 (c) 14 (c)
 26 Chapter
ALDEHYDES, KETONES AND
CARBOXYLIC ACIDS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

8
7
6
AIPMT /NEET
5
Number of Questions

AIIMS
4
3
2
1
0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 4 Nucleophilic addition reactions of
AIIMS 3 aldehydes and ketones, chemical 4/5 9
JEE Main 3 reactions of aldehydes and ketones,
Carboxylic acids and its derivatives.
BITSAT 2
 EBD_7374
364 CHEMISTRY
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 365
 EBD_7374
366 CHEMISTRY

Exercise 1 : Topic-wise MCQs

Topic 1: Nomenclature and Structure of Carbonyl Group 7. IUPAC name of the following compound is
O
1. Choose the correct IUPAC name for
CH3 - C H - CHO H
|
CH2 -CH 3
(a) Butan - 2- aldehyde (a) 2-(2-propenyl) butanal
(b) 2- methylbutanal (b) 2-(1-propenyl) butanal
(c) 3- methylisobutyraldehyde (c) 4-formyl 4-ethyl but-2-ene
(d) 2- ethylpropanal (d) 2-ethyl pent-3-en-l-al
2. The IUPAC name of CH3COCH(CH3)2 is
(a) 2-methyl-3-butanone Topic 2: Preparation of Aldehydes and Ketones
(b) 4-methylisopropyl ketone
(c) 3-methyl-2-butanone 8. Which alkene on ozonolysis gives CH3CH2CHO and
(d) Isopropylmethyl ketone CH3CCH3
3. IUPAC name of following will be ||
O
CHO
CH3
CH3 (a) CH3CH2CH = C (b) CH3CH2CH = CHCH2CH3
CH3
(c) CH3CH2CH = CH CH3 (d) CH 3 - C = CHCH 3
|
CH3
OH 9. An aldehyde group can be present
(a) 4-formyl 3-methyl 1-hydroxy benzene
(a) in between carbon chain
(b) 4-formyl 3-methyl phenol
(b) at any position in carbon atom
(c) 4-hydroxy 2-methyl benzaldehyde
(c) only at the end of carbon chain
(d) 4-hydroxy 2-methyl carbaldehyde
4. In > C = O group sigma bond is formed by (d) at the second carbon atom of the carbon chain
(a) sp2-p-overlapping (b) sp3-p-overlapping 10. Benzaldehyde is obtained from Rosenmund’s reduction of
(c) sp-p-overlapping (d) s-p-overlapping O O
5. Which of the following is correct for carbonyl compounds?
(a) CH3 (b) X
R R d+ d–
d– d+
(a) C=O (b) C=O
R¢ R¢ O
Cl
(c) d+ d– (d) d+ d–
(c) Cl (d) OH
R–C=O R–C=O

R¢ R¢ 11. Product of the following reaction is

6. Match the columns CN
Column-I Column-II SnCl +HCl
+ 2(H) ¾¾¾¾®
2
?
(Common names) (IUPAC names) H O+ 3
(A) Cinnamaldehyde (p) Pentanal
(B) Acetophenone (q) Prop-2-enal COOH CHO
(C) Valeraldehyde (r) 4-Methylpent-3-en-2-one (a) (b)
(D) Acrolein (s) 3-Phenylprop-2-enal
(E) Mesityl oxide (t) 1-Phenylethanone
O
(a) A – (s), B – (t), C – (p), D – (q), E – (r)
NH2
(b) A – (p), B – (q), C – (s), D – (t), E – (r) C ¾ CH3
(c) A – (t), B – (s), C – (p), D – (r), E – (q) (c) (d)
(d) A – (q), B – (t), C – (r), D – (s), E – (p)
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 367

12. Find out B in the given reactions 19. Product of the following reaction is
CN MgX
AlCl3 CrO 3 in (CH 3CO) 2O
+ CH 3 – X A B dry ether
H3O+ +
+
H3O
(a) acetophenone
O
(b) benzaldehyde
(c) cyclohexyl carbaldehyde
(d) benzoic acid (a) (b) OH
13. The reaction
CHO O
AlCl3
+ CO + HCl ¾¾¾®

(c) (d)
(a) Rosenmund’s reaction (b) Stephen’s reaction
(c) Cannizzaro’s reaction (d) Gatterman-Koch reaction
14. Which aldehyde cannot be obtained by Rosenmund’s Topic 3: Physical Properties
reaction? 20. Propanal and propanone, both have same molecular
(a) CH3CHO (b) HCHO formula(C3H6O), what do you expect about their boiling
(c) CH3CH2CHO (d) All of these points?
15. The conversion PhCN ® PhCOCH 3 , can be achieved (a) Both have same boiling point
most conveniently by reaction with (b) Boiling point of propanal is higher than the boiling
point of propanone.
(a) CH3MgBr followed by hydrolysis
(c) Boiling point of propanal is lower than the boiling point
(b) I2 – NaOH, CH3I
of propanone
(c) Dil. H2SO4 followed by reaction with CH2N2 (d) Nothing can be predicted
(d) LiAlH4 followed by reaction with CH3I 21. Assertion : The boiling points of aldehydes and ketones
16. Which of the following is used to prepare ketone in good are higher than hydrocarbons and ethers of comparable
yield from acyl chloride ? molecular masses.
(a) R-MgX (b) R2Cd Reason : There is a weak molecular association in aldehydes
(c) CO + HCl (d) CrO3 and ketones arising out of the dipole-dipole interactions.
17. In the given reaction (a) Assertion is correct, reason is correct; reason is a
CH3 CHO correct explanation for assertion.
Cl2/hu H2O (b) Assertion is correct, reason is correct; reason is not a
A correct explanation for assertion.
373K
(c) Assertion is correct, reason is incorrect.
A is (d) Assertion is incorrect, reason is correct.
CH2Cl CHCl2 22. The boiling points of aldehydes and ketones lie in between
(a) (b) alkanes and alcohols of comparable masses because
(a) alkanes are polar
(b) aldehydes and ketones are non-polar
CCl3 CH3 (c) alkanes are polar and aldehydes and ketones contain
(c) (d)
Cl C = O group and lower alcohols have H-
polar
18. Which of the following statement(s) is/are true regarding
preparation of aldehydes and ketones? bonding.
(i) Both can be prepared by the oxidation of the concerned (d) alkanes are held together by weak van der Waal’s
alcohol with copper at about 250ºC. forces (being polar), aldehydes and ketones contain
(ii) Both can be prepared by the oxidation of the concerned
alcohol by Oppenauer oxidation. C = O group and held together by strong
polar
(iii) Both can be prepared by the oxidation of respective
alcohol with acidic dichromate.
dipole-dipole attraction and lower alcohols have H-
(a) (i) only (b) (ii) and (iii) bonding, which is stronger than dipole-dipole
(c) (i) and (iii) (d) All the three attraction.
 EBD_7374
368 CHEMISTRY

34. A compound does not react with 2, 4-dinitrophenylhydrazine,

Topic 4: Chemical Reactions
the compound is :
23. Less reactivity of ketone is due to (a) Acetone (b) Acetaldehdye
(a) + I inductive effect decreases positive charge on (c) CH3OH (d) CH3CH2COCH3
carbonyl carbon atom 35. Which gives lactic acid on hydrolysis after reacting with
(b) steric effect of two bulky alkyl groups HCN ?
(c) sp2 hybridised carbon atom of carbonyl carbon atom (a) HCHO (b) CH3CHO
(d) Both (a) and (b) (c) C6H5CHO (d) CH3COCH3
24. Which of the following statement is false ? 36. The most appropriate reagent to distinguish between
(a) Cannizzaro reaction is given by aldehydes in presence acetaldehyde and formaldehyde is :
of alkali (a) Fehling’s solution
(b) Aldol condensation is given by aldehydes in presence (b) Tollen’s reagent
of alkali (c) Schiff’s reagent
(c) Aldol condensation is given by aldehydes and ketones (d) Iodine in presence of base
in presence of acids 37. 2-Pentanone and 3-pentanone can be distinguished by :
(d) None of the above (a) Cannizzaro's reaction (b) Aldol condensation
25. If formaldehyde and KOH are heated, then we get (c) Iodoform reaction (d) Clemmensen's reduction
(a) methane (b) methyl alcohol 38. Cross aldol condensation occurs between
(c) ethyl formate (d) acetylene (a) two same aldehydes
26. The reagent which can be used to distinguish acetophenone (b) two same ketones
from benzophenone is (c) two different aldehydes and ketones
(a) 2,4- dinitrophenylhydrazine (d) None of these
(b) aqueous solution of NaHSO3 39. Ketone upon treatment with Grignard reagent gives
(c) benedict reagent (a) primary alcohol (b) secondary alcohol
(d) I2and Na2CO3 (c) tertiary alcohol (d) aldehyde
27. Benzaldehyde reacts with ethanoic KCN to give 40. When acetaldehyde reacts with alcohol then produce
(a) C6H5CHOHCN (b) C6H5CHOHCOC6H5 (a) Acetal (b) Ketal (c) Acetone (d) None
(c) C6H5CHOHCOOH (d) C6H5CHOHCHOHC6H5 41. The product formed in Aldol condensation is
28. Acetaldehyde reacts with semicarbazide and forms (a) a beta-hydroxy aldehyde or a beta-hydroxy ketone
semicarbazone. Its structure is (b) an alpha-hydroxy aldehyde or ketone
(a) CH3CH = NNHCON = CHCH3 (c) an alpha, beta unsaturated ester
(b) CH3CH = NNHCONH2 (d) a beta-hydroxy acid
42. Which of the following products is formed when
(c) CH 3 CH = N — N — CONH 2 benzaldehyde is treated with CH3MgBr and the addition
|
OH product so obtained is subjected to acid hydrolysis ?
(d) CH3CH = N—CONHNH2 (a) A secondary alcohol (b) A primary alcohol
29. Iodoform test is not given by (c) Phenol (d) tert-Butyl alcohol
43. During reduction of aldehydes with hydrazine and
(a) 2-Pentanone (b) Ethanol
potassium hydroxide, the first step is the formation of
(c) Ethanal (d) 3-Pentanone
30. Phenylmethyl ketone can be converted into ethylbenzene (a) R — CH — — N — NH 2 (b) R — C º N
in one step by which of the following reagents? (c) R — C— NH 2 (d) R — CH— — NH
||
(a) LiAlH4 (b) Zn-Hg/HCl O
(c) NaBH4 (d) CH3MgI 44. A and B in the following reactions are
31. Which of the following compound will show positive silver OH
HCN B
mirror test ? R–C–R' KCN A R– C
(a) HCOOH (b) CH3(CHOH)3CHO R' CH2NH2
O
(c) CH3CO(CHOH)CH3 (d) Both (a) and (b) CN
32. Aldehydes and ketones are distinguished by which of the (a) A = RR'C , B = LiAlH4
following test ? OH
(a) Lucas test OH
(b) Tollen’s test (b) A = RR'C , B = NH3
(c) KMnO4 solution (Baeyer’s test) COOH
(d) None of these CN
33. In which reaction, > C = O can be reduced to > CH2? (c) A = RR'C , B = H 3O Å
(a) Wolf-Kishner reaction (b) Reimer-Tiemann reaction OH
(c) Wurtz reaction (d) None of these (d) A = RR'CH2CN, B = NaOH
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 369

45. Which one gives positive iodoform test ? X

55. C6H5CH=CHCHO ¾¾® C6H5CH=CHCH2OH
(a) (CH 3 ) 2 CHCH 2 OH In the above sequence X can be :
(b) C 6 H 5 - OH (a) H2/Ni (b) NaBH4
H (c) K2Cr2O7/H+ (d) Both (a) and (b)
| 56. Two compounds benzyl alcohol and benzoic acid are formed
(c) CH 3 - CH 2 - C - CH 2 - CH 3 from a compound, when it is heated in the presence of
| conc.NaOH, this compound is.
OH
(a) Benzaldehyde (b) Benzylalcohol
(d) CH 3CH 2 OH
(c) Acetophenone (d) Benzophenone
46. The compound that neither forms semicarbazone nor oxime 57. Which of the following compounds will give butanone on
is oxidation with alkaline KMnO4 solution?
(a) HCHO (b) CH3COCH2Cl (a) Butan-1-ol (b) Butan-2-ol
(c) CH3CHO (d) CH3CONHCH3
(c) Both of these (d) None of these
47. Schiff’s reagent gives pink colour with
58. Read the following statements and choose the correct option
(a) acetaldehyde (b) acetone
(c) acetic acid (d) methyl acetate (i) The carbonyl carbon atom is sp2 -hybridised
48. Benzophenone can be converted into benzene by using (ii) The carbonyl carbon is an electrophilic (Lewis acid)
(a) fused alkali centre
(b) anhydrous AlCl3 (iii) The carbonyl oxygen is a nucleophilic (Lewis base)
(c) sodium amalgam in water centre
(d) acidified dichromate (iv) Carbonyl compounds are non- polar in nature.
49. In the reaction of NaHSO3 with carbonyl compounds to (a) (i), (ii) and (iv) are correct
form bisulphite product, the nucleophile is (b) (i), (ii) and (iii) are correct
(a) HSO3– (b) SO3Na (c) (ii), (iii) and (iv) are correct
(c) SO3– – (d) None of the above
(d) (ii) and (iv) are correct
50. Wolf-Kishner reduction is
(a) reduction of carbonyl compound into alcohol 59. Aldehydes are generally more reactive than ketones in
(b) reduction of carbonyl compound into alkene nucleophilic addition reactions. Which of the following
(c) reduction of carboxyl compound into alkane statements accounts for this ?
(d) reduction of nitro compound into aniline (i) Sterically, the presence of two relatively large
substituents in ketones hinders the approach of
R OR nucleophile to carbonyl carbon
51. Compound of general formula C are called (ii) Aldehydes show resonance whereas ketones do not
(iii) Electronically, the presence of two alkyl groups reduce
H OR
the electrophilicity of the carbonyl carbon more
(a) diester (b) acid anhydride effectively.
(c) hemiacetal (d) acetal (iv) Electronically carbonyl carbon atom in ketones is more
52. Imine derivatives of aldehyde and ketone is called as electrophilic than in aldehydes
(a) Schiff’s reagent (b) Fehling’s reagent (a) (i) and (iii) (b) (i) and (iv)
(c) Schiff’s base (d) Schiff’s acid (c) (ii) and (iii) (d) (ii) and (iv)
53. Which reaction is used for detecting the presence of
OH -
carbonyl group? 60. 2C6 H5CHO ¾¾¾® C6 H5CH 2OH + C6 H5COO -
(a) Reaction with hydrazine H 2O
(b) Reaction with phenylhydrazine Which of the following statements are correct regarding the
(c) Reaction with hydroxylamine above reduction of benzaldehyde to benzyl alcohol?
(d) All of the above (i) One hydrogen is coming from H2O as H+ and another
54. The difference between aldol condensation and from C6H5CHO as H–
Cannizzaro’s reaction is that: (ii) One hydrogen is coming from H2O as H– and another
(a) the former takes place in aldehydes having no from C6H5CHO as H+
a-H-atom. (iii) One hydrogen from H2O and another from C6H5CHO,
(b) the former takes place in aldehydes having no both in the form of H–
a-H-atom. (iv) The reduction is an example of disproportionation
(c) the former takes place in aldehydes having no reaction
b-H-atom. (a) (i), (ii) and (iii) (b) (i) and (iv)
(d) none of the above (c) (ii), (iii) and (iv) (d) (iii) and (iv)
 EBD_7374
370 CHEMISTRY

61. Match the columns 66. Which of the following is an example of nucleophilic
Column-I Column-II addition ?
Zn - Hg / HCl O NNH 2
(A) R - CO - CH 3 ¾¾ ¾ ¾ ¾® (p) Friedel-Craft’s
|| NH 2 NH 2 ,H + ||
R - CH 2 - CH 3 reaction (a) C 6 H 5 C CH 3 ¾¾ ¾ ¾ ¾¾® C 6 H 5 C CH 3
NaOH
(B) 2C6 H5 CHO ¾¾¾® (q) Kolbe’s reaction O OH
|| |
C6 H5 COONa + C6 H5 CH 2 OH LiAlH
(b) C6 H 5 CCH 3 ¾¾¾¾
4 ® C H CHCH
6 5 3

(C) C6 H 6 + CH 3 COCl ¾¾¾¾

Anhyd.
® (r) Clemmensen’s (c) Both (a) and (b)
AlCl3 (d) None of the two
C6 H5 COCH3 reaction 67. Match the columns
(D) C 6 H 5 OH + CO 2 + NaOH ® (s) Cannizzaro’s Column-I Column-II
HOC6 H 4COONa reaction R
(A) C = NH (p) Oxime
(a) A – (p), B – (q), C – (r), D – (s) R
(b) A – (q), B – (p), C – (r), D – (s)
R
(c) A – (r), B – (s), C – (p), D – (q)
(B) C = NOH (q) Semicarbazone
(d) A – (s), B – (r), C – (p), D – (q) R
62. Match the columns
R
Column-I Column-II
(C) C = N – NH2 (r) Imine
(Reactions) (Reagents) R
(A) Benzophenone ® (p) LiAlH4
O
Diphenylmethane
R
(B) Benzaldehyde ® (q) DIBAL–H (D) C = N – NH – C – NH 2 (s) Hydrazone
1-Phenylethanol R
(C) Cyclohexanone ® (r) Zn(Hg)/conc. HCl (a) A – (q), B – (s), C – (p), D – (r)
Cyclohexanol (b) A – (r), B – (p), C– (s), D– (q)
(D) Phenyl benzoate ® (s) CH3MgBr (c) A – (r), B – (s), C – (p), D– (q)
Benzaldehyde
(d) A – (s), B – (r), C – (q), D– (p)
(a) A – (p), B – (s), C – (r), D – (q)
68. Acetal formation is a reversible reaction
(b) A – (q), B – (s), C – (p), D – (r)
+
(c) A – (s), B – (r), C – (q), D – (p) R H R OH R'OH, H +
C = O + R'OH C
(d) A – (r), B – (s), C – (p), D – (q) H H OR'
63. Observe the following structures and pick up the correct
statement. R OR'
+ H2O
C
+ H OR'
C=O C = OH Under what conditions, the reaction can be forced to proceed
I II only in right (forward) direction ?
(a) Carbonyl carbon of I is more electrophilic than that (a) Using excess of alcohol
of II (b) Using high temperature
(b) Carbonyl carbon of I is less electrophilic than that (c) Using dilute acid and excess of alcohol
of II (d) Using dry acid and excess of alcohol
(c) Carbonyl carbon of both structures have equal 69. In the crossed Cannizzaro reaction involving HCHO as one
electrophilic character of the components
(d) It depends upon the complete structure of the (a) HCHO is always oxidised because of electronic effect
compound (b) HCHO is always oxidised because of steric effect
64. Which of the following reagent reacts in different ways with (c) both of the above statements are true
CH3CHO, HCHO and C6H5CHO ?
(d) none of the above statement is true
(a) Fehling solution (b) C6H5NHNH2
70. When ethanal reacts with propanal in the presence of a
(c) Ammonia (d) HCl
base, the number of products formed is
65. A new carbon - carbon bond is formed in
(a) 2 (b) 3 (c) 4 (d) 5
(i) Aldol condensation (ii) Kolbe’s reaction
71. Which of the following compound will undergo self aldol
(iii) Reimer-Tiemann reaction
condensation in the presence of cold dilute alkali ?
(iv) Wurtz Fittig reaction
(a) (i) and (iii) (b) (ii) and (iii) (a) CH2=CH - CHO (b) CH º C - CHO
(c) (i), (ii) and (iiv) (d) All the four (c) C 6 H 5 CHO (d) CH 3 CH 2 CHO .
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 371

72. Identify X, undergoes Cannizzaro reaction but not aldol, then possible
H3C product due to nitration is
CH MgI (a) 3–nitroacetophenone
C = O ¾¾¾¾3 ® Intermediate ¾¾¾
H 2O
®X
H3C dry ether (b) (2–nitro)–2–phenylethanal
(c) (2–nitro)–1–phenylpropan–2–one
(a) CH3OH (b) Ethyl alcohol
(d) 3–nitrobezaldehyde
(c) Methyl cyanide (d) tert-Butyl alcohol
73. An organic compound of formula, C3H6O forms phenyl Topic 5: Nomenclature and Structure of Carboxyl Group
hydrazone, but gives negative Tollen’s test. The compound is
(a) CH3CH2COCH3 (b) CH3CH2CHO 81. Which of the following best represents the structure of the
(c) CH3COCH3 (d) Both (a) and (c) carboxylate ion ?
– –
R NH3 Hydrolysis d d
74. C = O HCN (A) (B) (C) O O
R
(a) R– C (b) R – C
Compound (C) in above reaction is
O O–
(a) a-hydroxy acid (b) a-amino acid d+ d
(c) a-amino alkanol (d) a-amino b-hydroxy acid
75. Benzaldehyde is less reactive than propanal because d+
(i) the carbon atom of the carbonyl group of benzaldehyde O
is less electrophilic as in propanal. (c) R– C (d) None of these
(ii) the carbon atom of the carbonyl group of benzaldehyde O
is more electrophilic as in propanal. d+
(iii) carbonyl group in benzaldehyde is more polar due to 82. Structure of the compound whose IUPAC name is 3-ethyl-
resonance 2-hydroxy-4-methylhex-3-en-5-ynoic acid is :
(iv) carbonyl group in benzaldehyde is less polar due to OH OH
resonance
(a) (i) and (iii) (b) (i) and (iv) (a) COOH (b) COOH
(c) (i) only (d) (iv) only
76. Addition of hydrogen cyanide to aldehydes and ketones
occurs in presence of a base.The role of base is to OH
(i) catalyse the reaction COOH
(ii) generate CN– ion (c) (d) COOH
(iii) slow down the reaction OH
(iv) to stabilize the cyanohydrins
83. Match the columns
(a) (i) and (iii) (b) (i) and (ii)
Column-I Column-II
(c) (i) and (iv) (d) (ii) and (iv)
77. When benzaldehyde and acetaldehyde undergoes reaction COOH
with the 2, 4–DNP ? (A) CH2 (p) Glutaric acid
(a) Benzaldehyde reacts slowly than acetaldehyde COOH
(b) Acetaldehyde reacts slowly than benzaldehyde
(c) Both reacts equally CH2 COOH
(d) Both do not react with 2, 4-DNP (B) (q) Adipic acid
78. Suppose the reaction of compound containing ketone as CH2 COOH
functional group is carried in basic medium of NaOH. Which
(C) CH2 COOH (r) Succinic acid
of the following will one use to protect the unwanted reaction
due to presence of carbonyl moiety?
CH2
(a) NaHSO3
(b) HCN
CH2 COOH
(c) ethylene glycol and HCl
(d) None of these
79. A compound C5H10O forms orange–red precipitate upon (D) CH2 COOH (s) Malonic acid
reaction with 2,4–DNP, but does not give positive Tollen’s
test and iodoform test. Possible compound is CH2
(a) 2, 2–dimethylpropanal (b) 3–methylbutan–2–one
(c) Pentan–3–one (d) None of the above CH2
80. Nitration of the compound is carried out, this compound
gives red–orange ppt. with 2,4–DNP, this compound CH2 COOH
 EBD_7374
372 CHEMISTRY

(a) A – (q), B – (p), C – (s), D – (r) 88. In the given reaction,

(b) A – (r), B – (p), C – (s), D – (q) H O
2 ®I
(C6 H5 CO) 2 O ¾¾¾
(c) A – (s), B – (r), C – (p), D – (q)
H O
2 ® II
(d) A – (r), B – (q), C – (s), D – (p) C6 H 5 COOCOCH 3 ¾¾¾
Identify the product(s) formed in the given reaction.
Topic 6: Methods of Preparation of Carboxylic Acids I II
(a) 2 molecules of benzoic acid 2 molecules of ethanoic acid
84. R HCl gas R O CH2 (b) 2 molecules of benzoic acid 1 molecule of benzoic acid
C = O +A C + H2O and 1 molecule of ethanoic acid
R dil HCl R O CH2 (c) 1 molecule of ethanoic acid 1 molecule of benzoic acid
A is (d) 1 molecule of benzoic acid 1 molecule of butanoic acid
(a) CH3OH (b) CH3COOH 89. Select the acid(s) which cannot be prepared by Grignard
CH 2COOH CH 2OH reagent.
(c) (d) (a) Acetic acid (b) Succinic acid
CH 2COOH CH2OH (c) Formic acid (d) All of the above
90. Through which of the following reactions number of carbon
85. Which of the following can not be oxidised to give carboxylic
atoms can be increased in the chain?
acid?
(i) Grignard reaction (ii) Cannizzaro’s reaction
CH2CH2CH3 (iii) Aldol condensation (iv) HVZ reaction
CH3 Choose the correct option.
(a) (a) Only (iii) and (i) (b) Only (iii) and (ii)
(b)
(c) Only (iii) and (iv) (d) (i), (ii), (iii) and (iv)
K 2Cr2O 7+H2SO4
CH3 91. Z. Here Z is
CH3
HC CH3 C CH3
CH3 (a) HOOC
(c) (d) (b) (CH3)3CCOOH
(c) Both (a) and (b)
86. MgBr (d) HOOC COOH

(i) CO Topic 7: Physical Properties

¾¾¾¾
2®
P
(ii) H 3O Å
92. Lower carboxylic acids are soluble in water due to
(a) low molecular weight (b) hydrogen bonding
In the above reaction product 'P' is
(c) dissociation into ions (d) easy hydrolysis
CHO COOH 93. Dimerisation of carboxylic acids is due to
(a) ionic bond
(b) covalent bond
(a) (b) (c) coordinate bond
(d) intermolecular hydrogen bond
94. Boiling points of carboxylic acids are
OH (a) lower than corresponding alcohols
O (b) higher than corresponding alcohols
|| (c) equal to that of corresponding alcohols
(c) (d) C6 H5 - C - C 6 H5 (d) None of the above
Topic 8: Chemical Reaction
87. The end product B in the sequence of reactions, 95. In the anion HCOO– the two carbon-oxygen bonds are found
-
CN
R - X ¾¾¾® A ¾¾¾¾
® B is
NaOH to be of equal length. What is the reason for it?
(a) Electronic orbitals of carbon atom are hybridised
(a) an alkane (b) The C=O bond is weaker than the C–C bond
(b) a carboxylic acid (c) The anion HCOO– has two reasonating structures
(c) sodium salt of carboxylic acid (d) The anion is obtained by removal of a proton from the
(d) a ketone acid molecule
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 373

96. Carboxylic acids are more acidic than phenol and alcohol 107. Which of the following statements are false?
because of (i) No aldehyde can be prepared by the oxidation of primary
(a) intermolecular hydrogen bonding alcohol with acidic KMnO4.
(b) formation of dimers (ii) Aldehydes having a boiling point less than 100°C can
(c) highly acidic hydrogen be prepared by the oxidation of primary alcohol with
(d) resonance stabilization of their conjugate base acidic dichromate.
97. Which of the following has the maximum acidic strength ? (iii) Secondary alcohols on oxidation with PCC in
(a) o-nitrobenzoic acid (b) m-nitrobenzoic acid dichloromethane give carboxylic acids having lesser
(c) p-nitrobenzoic acid (d) p-nitrophenol number of carbon atoms
98. Which one of the following esters is obtained by the (iv) Tertiary alcohols can't be oxidised at all
esterification of propan-2-ol with ethanoic acid ? (a) (ii) and (iii) (b) (ii), (iii) and (iv)
(a) (CH3)2CHCOOCH3 (b) CH3COOCH2CH3 (c) (i), (iii) and (iv) (d) (i), (ii) and (iii)
(c) CH3COOCH(CH3)2 (d) (CH3)2CHCOOCH2CH3 108. Which of the following statement(s) is/are true regarding
99. Among the following acids which has the lowest pK a esterification of a carboxylic acid with an alcohol ?
(i) It is carried out in presence of a strong acid which acts
value?
as a catalyst.
(a) CH 3 CH 2 COOH (b) (CH3 ) 2 CH - COOH
(ii) The strong acid makes the carbonyl carbon more
(c) HCOOH (d) CH 3COOH electrophilic, and hence causes the alcohol, a strong
100. Which reagent can convert acetic acid into ethanol ? nucleophile to attack on the carbonyl carbon.
(a) Na + alcohol (b) LiAIH4 + ether (iii) The strong acid makes the carbonyl group more
(c) H2 + Pt (d) Sn + HCl electrophilic which is thus attacked easily by an
101. Benzoic acid may be converted to ethyl benzoate by reaction alcohol, a weak nucleophile.
with (iv) Esterification can be done even in absence of a strong
(a) sodium ethoxide (b) ethyl chloride acid.
(c) dry HCl—C2H5OH (d) ethanol (a) (i) and (ii) (b) (i) and (iii)
102. Benzoic acid reacts with conc. HNO3 and H2SO4 to give : (c) (i) only (d) (iv) only
(a) 3-Nitrobenzoic acid 109. Assertion : Compounds containing –CHO group are easily
(b) 4-Benzene sulphonic acid oxidised to corresponding carboxylic acids.
(c) 4-Nitrobenzoic acid Reason : Carboxylic acids can be reduced to alcohols by
(d) 2-Nitrobenzoic acid treatment with LiAlH4.
103. The yield of ester in esterification can be increased by (a) Assertion is correct, reason is correct; reason is a
CH 3 CH 2 OH + CH 3COOH ‡ˆˆ ˆˆ† correct explanation for assertion.
CH3COOCH2CH3 + H 2O (b) Assertion is correct, reason is correct; reason is not a
(a) removing water correct explanation for assertion.
(b) taking ethanol in excess (c) Assertion is correct, reason is incorrect.
(c) taking acetic acid in excess (d) Assertion is incorrect, reason is correct.
(d) all the above factors 110. Which of the following is the correct decreasing order of
104. A carboxylic acid can best be converted into acid chloride acidic strength of
by using (i) Methanoic acid (ii) Ethanoic acid
(a) PCl5 (b) SOCl2 (iii) Propanoic acid (iv) Butanoic acid
(c) HCl (d) ClCOCOCl (a) (i) > (ii) > (iii) > (iv) (b) (ii) > (iii) > (iv) > (i)
105. The strongest acid among the following is – (c) (i) > (iv) > (iii) > (ii) (d) (iv) > (i) > (iii) > (ii)
(a) Salicylic acid (b) m-hydroxybenzoic acid 111. Ethanoic acid can’t be obtained by which of the following
(c) p-hydroxybenzoic acid (d) Benzoic acid reaction ?
106. Arrange the following carboxylic acid in their decreasing (i) KCN
(i) C2 H5Cl ¾¾¾¾¾
+®
acidity. (ii) H3O

1. COOH Oxalic acid (ii)

(i) AgCN
CH3Cl ¾¾¾¾¾ ®
+
(ii) H3O
COOH KMnO / OH -
2. HOOC – CH2 – COOH Malonic acid (iii) CH 3CH = CH 2 ¾¾¾¾¾¾
4 ®
heat
3. CH2– COOH Succinic acid (i) Mg
(iv) CH3Br ¾¾¾¾¾
®
(ii) CO2
CH2– COOH (iii) H3O +

(a) 3 > 2 > 1 (b) 1 > 2 > 3 (a) (iii) and (iv) (b) (i) and (ii)
(c) 2 > 3 > 1 (d) 2 > 1 > 3 (c) (ii) and (iii) (d) (i) and (iv)
 EBD_7374
374 CHEMISTRY

112. In a set of the given reactions, acetic acid yielded a (a) FCH 2 COOH > CH 3COOH > BrCH 2 COOH >
product C. ClCH2COOH
CH C H Br (b) BrCH2COOH > ClCH2COOH > FCH2COOH > CH3COOH
CH3 COOH + PCl5 ¾¾
® A ¾¾¾®
6 6
Anh.AlCl
B ¾¾¾¾
2 5 ®C
(c) FCH2COOH > ClCH2COOH > BrCH2COOH > CH3COOH
3 Ether
(d) CH3 COOH > BrCH2 COOH > ClCH2COOH >
Product C would be FCH2COOH
C2 H 5 115. The correct order for the acidic character of the following
| carboxylic acids is
(a) CH 3 - C (OH)C 6 H 5 (b) CH 3 CH (OH) C 2 H 5
COOH
(c) CH 3 COC 6 H 5 (d) CH 3 CH (OH ) C 6 H 5 COOH COOH
113. Kolbe’s electrolytic method can be applied on OH

(i) CH 2 COONa (ii) CHCOONa

| || OH
I II
CH 2 COONa CHCOONa III
COOH COOH
(iii) C6 H5COOK (iv) CH3COOK CH3 HO OH
(a) (i), (ii) and (iv) (b) (i), (ii) and (iii)
(c) (ii), (iii) and (iv) (d) (iii) and (iv)
IV V
114. Which of the following represents the correct order of the (a) IV > I > II > III > V (b) V > II > III > I > IV
acidity in the given compounds? (c) V > II > IV > III > I (d) V > II > IV > I > III

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 3. The correct order of increasing acidic strength is ........ .
(a) phenol < ethanol < chloroacetic acid < acetic acid
1. Addition of water to alkynes occurs in acidic medium and in
(b) ethanol < phenol < chloroacetic acid < acetic acid
the presence of Hg 2+ ions as a catalyst. Which of the
(c) ethanol < phenol < acetic acid < chloroacetic acid
following products will be formed on addition of water to
(d) chloroacetic acid < acetic acid < phenol < ethanol
but - 1-yne under these conditions?
O
O ||
|| 4. Compound Ph — O — C— Ph can be prepared by the
(a) CH 3 — CH 2 — CH 2 — C— H reactions of ............ .
(a) phenol and benzoic acid in the presence of NaOH
O
|| (b) phenol and benzoyl chloride in the presence of pyridine
(b ) CH3 — CH 2 — C — CH 3 (c) phenol and benzoyl chloride in the presence of ZnCl 2
(d) phenol and benzaldehyde in the presence of palladium
O 5. The reagent which does not react with both, acetone and
|| benzaldehyde?
(c) CH3 — CH 2 — C — OH + CO 2
(a) Sodium hydrogen sulphite
O O (b) Phenyl hydrazine
|| || (c) Fehling's solution
(d) CH 3 — C— OH + H — C— H (d) Grignard reagent
2. Which of the following compounds is most reactive towards 6. Cannizzaro's reaction is not given by ........ .
nucleophilic addition reactions? CHO
O O (a) (b) CHO
|| || CH3
(a) CH 3 — C — H (b) CH3 — C — CH 3 (c) HCHO (d) CH3CHO
7. Which product is formed when the compound
O O
|| ||
(c) —C—H (d) — C — CH 3 CHO is treated with concentrated aqueous KOH
solution?
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 375

+ – Past Year MCQs

(a) KO CHO
13. Which one is most reactive towards Nucleophilic addition
O reaction? [AIPMT 2014]
|| - +
(b) C– OK + CH2OH CHO COCH3
(a) (b)
O
+ – || - + + - – + CHO CHO
(c) KO C O K+ K O OK

(c) (d)
O
|| - + –+
(d) C— O K + OK CH3 NO2

40% H SO
14. Ethanoic acid on heating with ammonia forms compound A
8. CH3 — C º CH ¾¾¾¾¾®
2 4 A which on treatment with bromine and sodium hydroxide
1% HgSO 4
gives compound B. Compound B on treatment with NaNO2/
Isomerisation
¾¾¾¾¾¾ ® CH3 — C— CH3 dil. HCl gives compound C. The compounds A, B and C
|| respectively are [AIIMS 2014, S]
O
(a) ethanamide, methanamine, methanol
structure of 'A' and type of isomerism in the above reaction
are respectively (b) propanamide, ethanamine, ethanol
(a) Prop-1-en-2-ol, metamerism (c) N-ethylpropanamide, methaneisonitrile, methanamine
(b) Prop-1-en-1-ol, tautomerism (d) ethanamine, bromoethane, ethanedia-zonium chloride
(c) Prop-2-en-2-ol, geometrical isomerism CHO
(d) Prop -1-en-2-ol, tautomerism
9. Compounds A and C in following reaction are ........... . Dil. NaOH
15. + CH3CHO ¾¾¾¾¾
® A .
(Major)
(i ) CH MgBr H SO ,D
CH 3 CHO ¾¾¾¾¾¾
( )
3 ® ( A ) ¾¾¾¾¾
2 4 ® (B)
ii H 2O

Hydroboration oxidation
(A) will be – [AIIMS 2014, A]
¾¾¾¾¾¾¾¾¾® ( C )
OH
(a) identical (b) positional isomers |
(c) functional isomers (d) optical isomers (a) C6 H5 CH - CH 2CHO (b) C6H5CH = CH – CHO
10. Which is the most suitable reagent for the following
conversion? (c) C6H5CH2CH2CHO (d) Both (b) & (c)
16. Sodium phenoxide when heated with CO2 under pressure at
O 125ºC yields a product which on acetylation produces C.
||
CH3 — CH = CH — CH 2 — C— CH 3 ¾¾
® [JEE M 2014, S]
ONa 125° H+
O + CO2 ¾¾ ¾¾
5 Atm
® A ¾¾ ¾® C
Ac2 O
||
CH3 — CH = CH — CH 2 — C — OH The major product C would be
(a) Tollen's reagent (b) Benzoyl peroxide
(c) I2 and NaOH solution (d) Sn and NaOH solution OCOCH3 OH
11. Which of the following compounds will give butanone on COOH COCH3
oxidation with alkaline KMnO4 solution? (a) (b)
(a) Butan-1-ol (b) Butan-2-ol
(c) Both (a) and (b) (d) None of these COCH3
12. In Clemmensen reduction, carbonyl compounds is treated
with ......... . OH OCOCH3
(a) zinc amalgam + HCl
(b) sodium amalgam + HCl COOCH3
(c) (d)
(c) zinc amalgan + nitric acid COOH
(d) sodium amalgam + HNO3
 EBD_7374
376 CHEMISTRY

17. In the reaction, OCOCH3

LiAlH PCl alc.KOH (a)
CH 3 COOH ¾¾¾¾ 4 ® A ¾¾¾ 5 ® B ¾¾¾¾® C

the product C is: [JEE M 2014, S] ON

2
(a) Acetaldehyde (b) Acetylene OCOCH3
(c) Ethylene (d) Acetyl chloride
18. The correct order of decreasing acid strength of (b)
H CO
trichloroacetic acid (A), trifluoroacetic acid (B), acetic acid 3
(C) and formic acid (D) is : [BITSAT 2014, S] OCOCH3
(a) B > A > D > C (b) B > D > C > A (c)
(c) A > B > C > D (d) A > C > B > D
19. The reaction, [BITSAT 2014, S] OCOCH3
CO + H O
CH3 - CH = CH 2 ¾¾¾¾¾
2
® CH3- CH - CH 3 (d)
H+ |
COOH Cl
is known as 25. In a set of reactions m-bromobenzoic acid gave a product D.
(a) Wurtz reaction Identify the product D. [AIIMS 2015, S]
(b) Koch reaction
(c) Clemmensen reduction COOH
(d) Kolbe’s reaction SOCl2 NH3 NaOH
20. An organic compound 'X' having molecular formula C5H10O B C Br2
D
yields phenyl hydrazone and gives negative response to Br
the Iodoform test and Tollen's test. It produces n-pentane
on reduction. 'X' could be :- [AIPMT 2015, S] SO2NH2 COOH
(a) 2-pentanone (b) 3-pentanone (a) (b)
(c) n-amyl alcohol (d) pentanal
Br NH2

21. Treatment of cyclopentanone =O with methyl

NH2 CONH2
lithium gives which of the following species? (c) (d)
[AIPMT 2015, C]
Br Br
(a) Cyclopentanonyl cation
(b) Cyclopentanonyl radical 26. Assertion : Benzaldehyde is more reactive than ethanol
(c) Cyclopentanonyl biradical towards nucleophilic attack.
(d) Cyclopentanonyl anion Reason : The overall effect of –I and + R effect of phenyl
22. The enolic form of ethyl acetoacetate as below has: group decreases the electron density on the carbon atom of
> C = O group in benzaldehyde. [AIIMS 2014, 2015, C]
[AIPMT 2015, S]
(a) Assertion is correct, reason is correct; reason is a
H H2 correct explanation for assertion.
H3C C O H3C C O (b) Assertion is correct, reason is correct; reason is not a
C C C C
correct explanation for assertion.
OH OC2H5 O OC2H5 (c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct.
(a) 16 sigma bonds and 1 pi - bond 27. Which compound would give 5 - keto - 2 - methylhexanal
(b) 9 sigma bonds and 2 pi - bonds upon ozonolysis ? [JEE M 2015, S]
(c) 9 sigma bonds and 1 pi - bond CH3
(d) 18 sigma bonds and 2 pi - bonds CH3
23. Reaction of a carbonyl compound with one of the following
reagents involves nucleophilic addition followed by (a) (b) H3C
elimination of water. The reagent is : [AIPMT 2015 RS, A]
(a) a Grignard reagent CH3
(b) hydrazine in presence of feebly acidic solution CH3
(c) hydrocyanic acid CH3
(d) sodium hydrogen sulphite
(c) CH3 (d)
24. Which one of the following esters gets hydrolysed most
easily under alkaline conditions? [AIPMT 2015 RS, A] CH3
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 377

28. The correct statement regarding a carbonyl compound with

a hydrogen atom on its alphacarbon, is : [NEET 2016, C] (c) and
(a) a carbonyl compound with a hydrogen atom on its alpha-
carbon never equilibrates with its corresponding enol.
(b) a carbonyl compound with a hydrgen atom on its alpha-
carbon rapidly equilibrates with its corresponding enol
and this process is known as aldehyde-ketone
(d) and
equilibration.
(c) a carbonyl compound with a hydrogen atom on its
alpha-carbon rapidly equilibrates with its
corresponding enol and this process is known as
carbonylation.
33. Consider the reactions :- [NEET 2017, A]
(d) a carbonyl compound with a hydrogen atom on its
alpha-carbon rapidly equilibrates with its Cu [Ag(NH3)2]
+

corresponding enol and this process is known as keto- X A Silver mirror

573K – OH/D
enol tautomerism. (C2H6O) observed
– OH/D
29. The product formed by the reaction of an aldehyde with a Y
O
primary amine is [NEET 2016, A]
(a) schiff base (b) ketone Nh2 – NH – C – NH2
(c) carboxylic acid (d) aromatic acid Z
30. Aldehydes that do not undergo aldol condensation are Identify A, X, Y and Z
[AIIMS 2016, C] (a) A-Methoxymethane, X-Ethanol, Y-Ethanoic acid, Z-
1. propanal 2. trichloroethanal Semicarbazide.
3. methanal 4. ethanal (b) A-Ethanal, X-Ethanol, Y-But-2-enal, Z-Semicarbazone
5. benzaldehyde (c) A-Ethanol, X-Acetaldehyde, Y- Butanone, Z- Hydrazone
(a) 3 and 4 only (b) 3 and 5 only (d) A-Methoxymethane, X-Ethanoic acid, Y-Acetate ion,
(c) 1, 2 and 3 only (d) 2, 3 and 5 only Z-hydrazine.
31. Assertion : The boiling points of aldehydes and ketones 34. Of the following, which is the product formed when
are higher than hydrocarbons and ethers of comparable cyclohexanone undergoes aldol condensation followed by
molecular masses. heating ? [NEET 2017, A]
Reason : There is a weak molecular association in aldehydes
and ketones arising out of the dipole-dipole interactions.
[AIIMS 2016, C] (a) (b)
(a) Assertion is correct, reason is correct; reason is a
correct explanation for assertion. O OH
(b) Assertion is correct, reason is correct; reason is not a
O
correct explanation for assertion.
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct. (c) (d)
32. The most likely acid-catalysed aldol condensation products
of each of the two aldehydes I and II will respectively be O O OH
[BITSAT 2016, S]
35. Aldol condensation will not be observed in
[AIIMS 2017, C]
CHO (I) and (II)
(a) chloral (b) phenylacetaldehyde
(c) hexanal (d) nitromethane
36. The reaction
(a) and
Red P
RCH 2 CH 2 COOH ¾¾¾® R - CH 2 - CH - COOH
Br2 |
Br
is called as [AIIMS 2013, 2017, C]
(a) Reimer- Tiemann reaction
(b) and (b) Hell-volhard Zelinsky reaction
(c) Cannizzaro reaction
(d) Sandmeyer reaction
 EBD_7374
378 CHEMISTRY

37. The correct sequence of reagents for the following

CH2 – OH CH2 – OH
conversion will be : [JEE M 2017, S]
(c) (d)
O HO CH3

CH2 – OH COOH

HO–CH3 O
CHO CH3
C – CH3
(a) [Ag(NH3)2]+ OH–, H+/CH3OH, CH3MgBr Br2
41. In the reaction ¾¾¾¾ ® product,
(b) CH3MgBr, H+/CH3OH, [Ag(NH3)2]+ OH– NaOH

(c) CH3MgBr, [Ag(NH3)2]+ OH–, H+/CH3OH

(d) [Ag(NH3)2]+ OH–, CH3MgBr, H+/CH3OH CH3
38. The major product obtained in the following reaction is : product is [AIIMS 2018, A]
O [JEE M 2017, S]
O O
O
C – CH2 – Br C – CH3
(a) (b)
DIBAL–H

CH3 CH2 – Br
COOH
OH O O
OH
C – CH3 Br C – CH3
(a) CHO (b) CHO (c) (d)
COOH
Br
CHO
CH3 CH3

CHO CH3
(c) (d) CHO | H2 /Pd
42. CH3– C = CH – CH2 – C – CH3 ¾¾¾¾ ®
COOH CHO ||
39. Carboxylic acids have higher boiling points than aldehydes, O
ketones and even alcohols of comparable molecular mass. No. of stereoisomers [AIIMS 2018, S]
It is due to their [NEET 2018, C] (a) 2 (b) 4 (c) 8 (d) 6
(a) Formation of intramolecular H-bonding O
(b) Formation of carboxylate ion
(c) Formation of intermolecular H-bonding 43. CH 3 NO 2
¾¾ ¾ ¾® [ A ] ¾
¾ ¾® [ B ]
(d) More extensive association of carboxylic acid via van C 2 H 5O -
der Waals force of attraction O
COOH
HONO
(i) B H ¾¾ ¾
¾®
40. ¾¾¾¾¾¾
2 6
® [AIIMS 2018, A] H+
(ii) DlBAL–H
(iii) H3OÅ Which reaction is/are involved in the above conversion?
CN [AIIMS 2018, S]
(a) Diazotisation and Beckmamn rearrangement
COOH CH2 – OH (b) Diazotisation and Robinson annulation
(a) (b) (c) Aldol condensation and diazotisation
(d) Diazotisation and pinacol type of rearrangement

CHO CHO
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 379

Exercise 3 : Try If You Can

1. When cylohexanone is treated with Na 2CO3 solution, we 7. Which of the following is an example of nucleophilic
get addition ?
O O O NNH 2
OH || NH NH ,H +
2 ¾2¾¾® C H C CH
||
(a) C 6 H 5 C CH 3 ¾¾ ¾ 6 5 3
(a) (b)
OH O OH
|| |
O (b) LiAlH 4
C 6 H 5 C CH 3 ¾¾ ¾¾® C 6 H 5 C HCH 3
OH
COOH (c) Both (a) and (b)
(c) (d) (d) None of the two
COOH
O
– ||
2. The reacion OH is an 4 ¾® Z ; Z is NH OH
O 8. CH 3 C C 2 H 5 + NaCN + NH 4 Cl ¾¾ ¾
O
CHO CH3 OH CH3 OH
example of C C
(a) (b)
(a) oxidation reaction (b) reduction C2H3 COOH C2H5 CN
(c) both (d) aldol condensation
3. When o-hydroxybenzaldehyde is heated with ethanoic CH3 NH2 CH3 CN
anhydride in presence sodium ethanoate, compound (c) C (d) C
C2H5 CN C2H5 COOH
formed during the reaction is
9. The compund having formula,
OH OH
O O
(a) (b) || ||
COOCH3 COOH CH 3 - C- CH 2 - C - OC 2 H 5
O O (a) forms dioxime
(c) (d) Both (b) and (c) (b) undergoes iodoform test
(c) both (a) and (b)
4. A new carbon - carbon bond is formed in (d) neither of the two
Aldol condensati on Kolbe' s reaction 10. Aldehydic group can be protected
I II (a) by acetal formation against alkaline oxidising agents.
Reimer - Tiemann reaction Wurtz Fittig reaction (b) by mercaptal formation against acidic oxidising agents
III IV (c) both (a) and (b)
(a) I, III (b) II, III (d) None of the above
(c) I, III, IV (d) All the four O
5. The correct stability order of the following three quinones +
H
is 11. X , most likely the compound X is
O O
O R R
O O OH OH

O (a) (b)
I II III R
R R R
(a) I > III > II (b) I = III > II
OH OH
(c) I = II > III (d) III > I > II
R R
OH - ,Cl R
6. CH 3 COCH 2 Cl ¾¾¾¾¾2®
Product P is (c) (d)
(a) ClCH2COCH2Cl (b) CH3COCHCl2
(c) both (a) and (b) (d) ClCH2COOH+CH3Cl R
 EBD_7374
380 CHEMISTRY

Ca(OH) COOH COOH

12. CH 3CHO + 4HCHO ¾¾¾¾2¾
®

1
C(CH 2 OH) 4 + (HCOO) 2 Ca (c) (d)
2
Cl
the above reaction is an example of
(a) aldol condensation Cl
(b) Cannizzaro reaction 14. Which of the followng acts as a nucleophile in the aldol
condensation of ethanal?
(c) both
(d) none (i) OH– (ii) H2O
13. Which of the following is expected to be least acidic ? (iii) –CH2CHO
(a) only (i) (b) (i) and (ii)
COOH Cl COOH (c) (i) and (iii) (d) All the three
Cl
(i) O3/ H2O
(a) (b) 15. A ; A is
(i) heat

(a) CH2(COOH)2 (b) CH3COOH

(c) HCOOH (d) HCHO

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 13 (d) 25 (b) 37 (c) 49 (c) 61 (c) 73 (d) 85 (d) 97 (a) 109 (b)
2 (c) 14 (b) 26 (d) 38 (c) 50 (c) 62 (d) 74 (b) 86 (b) 98 (c) 110 (a)
3 (c) 15 (a) 27 (b) 39 (c) 51 (d) 63 (b) 75 (b) 87 (c) 99 (c) 111 (b)
4 (a) 16 (b) 28 (b) 40 (a) 52 (c) 64 (c) 76 (b) 88 (b) 100 (b) 112 (a)
5 (b) 17 (b) 29 (d) 41 (a) 53 (d) 65 (d) 77 (a) 89 (c) 101 (c) 113 (a)
6 (a) 18 (a) 30 (b) 42 (a) 54 (a) 66 (c) 78 (c) 90 (a) 102 (a) 114 (c)
7 (d) 19 (d) 31 (d) 43 (a) 55 (b) 67 (b) 79 (c) 91 (c) 103 (d) 115 (d)
8 (a) 20 (c) 32 (b) 44 (a) 56 (a) 68 (d) 80 (d) 92 (b) 104 (d)
9 (c) 21 (a) 33 (a) 45 (d) 57 (b) 69 (c) 81 (b) 93 (d) 105 (a)
10 (b) 22 (d) 34 (c) 46 (d) 58 (b) 70 (c) 82 (a) 94 (b) 106 (b)
11 (b) 23 (d) 35 (b) 47 (a) 59 (a) 71 (d) 83 (c) 95 (c) 107 (c)
12 (b) 24 (d) 36 (d) 48 (a) 60 (b) 72 (c) 84 (d) 96 (d) 108 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 6 (d) 11 (b) 16 (a) 21 (d) 26 (d) 31 (a) 36 (b) 41 (a)
2 (a) 7 (b) 12 (a) 17 (c) 22 (d) 27 (d) 32 (b) 37 (a) 42 (a)
3 (c) 8 (d) 13 (d) 18 (a) 23 (b) 28 (d) 33 (b) 38 (b) 43 (c)
4 (b) 9 (b) 14 (a) 19 (d) 24 (a) 29 (a) 34 (a) 39 (c)
5 (c) 10 (c) 15 (b) 20 (b) 25 (c) 30 (d) 35 (a) 40 (b)
Exercise 3 : Try If You Can
1 (c) 3 (d) 5 (d) 7 (c) 9 (b) 11 (b) 13 (d) 15 (b)
2 (d) 4 (d) 6 (b) 8 (c) 10 (c) 12 (c) 14 (c)
 27 Chapter
AMINES

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Basicity of Amines, chemical
AIIMS 3 reactions of amines, reactions 3.2/5 6.9
JEE Main 2 of diazonium salts, cyanides
BITSAT 2 and isocyanides.
.
 EBD_7374
382 CHEMISTRY
AMINES 383
 EBD_7374
384 CHEMISTRY

Exercise 1 : Topic-wise MCQs

8. IUPAC name of the following compound is
Topic 1: Structure of Amines, Classification and Nomenclature
1. The total number of electrons around the nitrogen atom in
amines are NH2
(a) 8 (b) 7 (c) 4 (d) 3 Cl
2. Read the following statements and choose the correct (a) 2-chloro pentanamine
option. (b) 4-chloro pentan-1-amine
(i) Nitrogen atom in amines is sp3-hybridised. (c) 4-chloro pent-2-en-1-amine
(ii) The geometry of amines is pyramidal. (d) 2-chloro pent-3-en-5-amine
(iii) The angle C–N–C or C–N–H is slightly more than 9. Which of the following is the correct IUPAC name of the
109.5°. compound ?
(a) (i), (ii) and (iii) (b) (i) and (ii)
(c) (i) and (iii) (d) (ii) and (iii) N (CH 3 ) 2
3. A secondary amine is
(a) a compound with two carbon atoms and an –NH2
group. Cl
(b) a compound containing two –NH2 groups. Cl
(c) a compound in which hydrogens of NH3 have been
(a) 1, 2-dichloro-4-(N, N-dimethyl) aniline
replaced by two alkyl groups.
(b) Dimethyl – (3, 4-dichlorophenyl) amine
(d) a compound with an –NH2 group on carbon atom in
number two position. (c) 3, 4-dichloro - N, N-dimethyl aniline
4. The number of primary amines of formula C4H11N is : (d) N, N-dimethylamino - 3, 4-dichlorobenzene
(a) 1 (b) 3 (c) 4 (d) 2 Topic 2: Preparation of Amines
5. The IUPAC name of the compound having formula,
10. The general formula of quaternary ammonium compound is
O C CH CH2 is (a) R–NH2 (b) R3N (c) R4N+ X– (d) NH4X
11. Intermediates formed during reaction of RCONH2 with Br2
OH NH2 OH and KOH are
(a) 3-amino-hydroxy propine acid (a) RCONHBr and RNCO (b) RNHCOBr and RNCO
(b) 2-amino-propan-3-oic acid (c) RNHBr and RCONHBr (d) RCONBr2
(c) amino hydroxy propanoic acid 12. Which of the following reactions will not give a primary
(d) 2-amino-3-hydroxy propanoic acid amine?
(a) Br / KOH
6. What is the IUPAC name of the following compound ? CH 3 CONH 2 ¾¾2¾ ¾
¾®

(b) LiAlH
NH 2 CH 3CN ¾¾ ¾¾
4®

(c) LiAlH
CH 3 NC ¾¾ ¾¾
4®

(d) LiAlH
(a) 2-methyl-4-hexanamine CH 3CONH 2 ¾¾ ¾¾
4®

(b) 5-methyl-3-hexanamine 13. Propionamide on Hoffmann degradation gives –

(c) 2-methyl-4-amino hexane (a) methyl amine (b) ethyl amine
(d) 5-methyl-3-amino hexane (c) propyl amine (d) ethyl cyanide
7. The IUPAC name of diethyl isopropyl amine is 14. Secondary amines could be prepared by
(a) N, N-diethylpropan-2-amine (a) reduction of nitriles
(b) N, N-diethylpropan-1-amine (b) Hofmann bromamide reaction
(c) reduction of amides
(c) N, N-diethylisopropylamine
(d) reduction of isonitriles
(d) N, N-diethylaminopropane
AMINES 385

15. Gabriel’s phthalimide synthesis is used for the preparation (a) Assertion is correct, reason is correct; reason is a
of correct explanation for assertion.
(a) Primary aromatic amines (b) Assertion is correct, reason is correct; reason is not a
(b) Secondary amines correct explanation for assertion
(c) Primary aliphatic amines (c) Assertion is correct, reason is incorrect
(d) Tertiary amines (d) Assertion is incorrect, reason is correct.
16. Treatment of ammonia with excess of ethyl iodide will yield 24. Acetamide is treated with the following reagents separately.
(a) diethylamine Which one of these would yield methylamine?
(b) ethylamine (a) NaOH – Br2 (b) Sodalime
(c) triethylamine
(d) tetraethylammonium iodide (c) Hot conc. H 2SO4 (d) PCl5
17. For alkylation of ammonia which of the following is not 25. A primary amine is formed by an amide on treatment with
used ? bromine and alkali. The primary amine has
(a) CH3–X (b) CH3–CH2–X (a) 1 carbon atom less than amide
(c) (CH3)2CH–X (d) (CH3)3C–X (b) 1 carbon atom more than amide
18. The reduction of nitro compounds is most preferred in the (c) 1 hydrogen atom less than amide
presence of
(d) 1 hydrogen atom more than amide
(a) Pd/H2 in ethanol (b) Sn + HCl
(c) finely divided Ni (d) iron scrap and HCl. Topic 3: Physical Properties
19. An alkyl or benzyl halide on reaction with an ethanolic
solution of ammonia undergoes 26. Amines have
(a) electrophilic substitution reaction (a) Garlic odour (b) Fishy odour
(b) nucleophilic substitution reaction. (c) Jasmine odour (d) Bitter almonds odour
(c) free radical mechanism. 27. Aniline is less soluble in water than ethyl amine due to
(d) nucleophilic addition reaction. (a) resonance stablization of benzene ring
20. In the ammonolysis of alkyl halides the halogen atom is (b) resonance stabilization of anilium ion
replaced by an amino(–NH2) group which of the following (c) more hydrophobic nature of C6H5 group than C2H5
represent the correct order of reactivity of halides with group
amines. (d) more hydrophobic nature of C2H5 group than C6H5
(a) RBr > RI > RCl (b) RI > RCl > RBr group
(c) RI > RBr > RCl (d) RCl > RBr > RI 28. Which of the following is not characteristic of amines?
21. Which of the following will give primary amine only ? (a) They smell like ammonia
(i) ammonia + propylchloride (b) They are inflammable in air
(ii) potassium pthalimide + ethylchloride (c) They show the property of hydrogen bonding
(iii) potassium pthalimide + chlorobenzene (d) They are amphoteric in nature
(a) (i) and (ii) (b) (i) and (iii) 29. Which of the following statements are correct ?
(c) (ii) and (iii) (d) (i), (ii) and (iii) (i) Lower aliphatic amines are soluble in water.
22. Match the columns (ii) Solubility increases with decrease in molar mass of
Column-I Column-II amines.
(A) Gabriel phthalimide (p) C6H5CH2NH2 (iii) Higher amines are insoluble in water.
reaction
(iv) Amines are soluble in organic solvents.
(B) Reduction with (q) C6H5NH2
LiAlH4 (a) (i), (ii) and (iii) (b) (i), (iii) and (iv)
(C) Reaction with (r) C6H5CN (c) (ii), (iii) and (iv) (d) (i) and (iv)
alc. KOH + CHCl3
Topic 4: Chemical Reactions
(D) 1° Amide with (s) CH3CH2NH2
Br2 + KOH 30. Aliphatic amines are.....basic than NH3 but aromatic amines
(a) A – (p, s); B – (p, s); C – (p, q, s); D – (p, q, s) are......basic than NH3.
(b) A – (s); B – (p); C – (q); D – (p, q) (a) more, less (b) less, more
(c) A – (p, s); B – (r); C – (q); D – (s) (c) both (a) and (b) (d) None of these
(d) A – (p, q); B – (p); C – (p, q); D – (s) 31. Substitution of one alkyl group by replacing hydrogen of
23. Assertion : Only a small amount of HCl is required in the primary amines
reduction of nitro compounds with iron scrap and HCl in (a) increases the base strength
the presence of steam. (b) decreases the base strength
Reason : FeCl2 formed gets hydrolysed to release HCl during (c) remains the same
the reaction. (d) None of the above
 EBD_7374
386 CHEMISTRY

32. The correct order of basicity in amines in gaseous phase is 41. An organic amino compound reacts with aqueous nitrous
(i) C2H5NH2 (ii) CH3NH2 acid at low temperature to produce an oily nitrosoamine.
(iii) (CH3)2NH (iv) (CH3)3N The compound is
(a) (i) < (iv) < (ii) < (iii) (b) (iv) < (ii) < (iii) < (i) (a) CH3NH2 (b) CH3CH2NH2
(c) (i) < (ii) < (iii) < (iv) (d) (ii) < (iii) < (iv) < (i) (c) CH3CH2NHCH2CH3 (d) (CH3CH2)3N
33. The conjugate base of (CH3)2NH+2 is 42. Primary amines can be distinguished from secondary and
(a) (CH3)2NH (b) (CH3)2N+ tertiary amines by reacting with
(c) (CH3)3N + (d) (CH3)2N– (a) Chloroform and alcoholic KOH
34. High basicity of Me2 NH relative to Me3N in aqueous (b) Methyl iodide
solution is attributed to: (c) Chloroform alone
(a) effect of solvent (b) inductive effect of Me (d) Zinc dust
(c) shape of Me2NH (d) shape of Me3N 43. The amine that does not react with acetyl chloride is
35. The correct order of basicity of the following compounds (a) CH3NH2 (b) (CH3)2NH
(c) (CH3)3N (d) None of these
NH 2 NH 2 NH 2
44. Which of the following compounds cannot be identified
by carbylamine test?
(a) CH3CH2NH2 (b) CHCl3
A B C
(c) C6H5NH2 (d) C6H5–NH–C6H5
NO2 45. (CH3)2CHNH2 is reacted with excess acetic anhydride, the
compound formed is
(a) B > A > C (b) A > B > C
(a) (CH3)2CHNCOCH3 (b) (CH3)2CN(COCH3)2
(c) C > A > B (d) C > B > A
(c) (CH3)2CHOH (d) (CH3)2CN(COOCH3)2
36. Which of the following factors affect the basic strength of
amine? 46. In order to distinguish between C2H5–NH2 and C6H5–NH2,
which of the following reagent is useful
(i) Inductive effect
(a) Hinsberg’s reagent (b) HNO2
(ii) Steric hinderance
(iii) Solvation effect (c) CHCl3 + KOH (d) NaOH
(iv) Solubility in organic solvents. 47. Strong activating effect of –NH2 group is reduced by using
(a) (i) and (iv) (b) (i), (ii) and (iii) (a) CH3COCl (b) CH3Cl
(c) (ii) and (iii) (d) (ii) and (iv) (c) CH3ONa (d) CH3–CHO
37. Which of the following statements about primary amines is 48. When bromination of aniline is carried out by protecting
‘False’ ? –NH2. The product is
(a) Alkyl amines are stronger bases than aryl amines (a) o-bromoaniline
(b) Alkyl amines react with nitrous acid to produce (b) 2, 4, 6 tribromoaniline
alcohols (c) p-bromoaniline
(c) Aryl amines react with nitrous acid to produce phenols (d) mixture of o-and p-bromoanilines
(d) Alkyl amines are stronger bases than ammonia 49. Hinsberg’s method to separate amines is based on the
use of
38. The compound obtained by heating a mixture of a primary
amine and chloroform with ethanolic potassium hydroxide (a) benzene sulphonyl chloride
(KOH) is (b) benzene sulphonic acid
(a) an alkyl cyanide (b) a nitro compound (c) ethyl oxalate
(c) an alkyl isocyanide (d) an amide (d) acetyl chloride
50. Which of the following statements is not correct regarding
39. R - NH 2 + CH3COCl ¾¾
®A aniline ?
(excess)
(a) It is less basic than ethylamine
The product (A) will be – (b) It can be steam-distilled
(a) RNHCOCH3 (b) RN(COCH3)2 (c) It reacts with sodium to give hydrogen
+ (d) It is solub in water
(c) RN(COCH3 )3 Cl- (d) R – CONH2
51. Aniline and other arylamines are usually colourless but get
40. In the reaction,
coloured on storage due to___________.
HNO
RNH 2 ¾¾¾¾
2
® ROH + H 2O + A ­ ; A is (a) hydrolysis (b) dehydration
(a) NH3 (b) N2 (c) O2 (d) CO2 (c) reduction (d) atmospheric oxidation
AMINES 387

52. The acylation reaction of amines is carried out in presence (a) Assertion is correct, reason is correct; reason is a
of pyridine because correct explanation for assertion.
(i) pyridine is stronger base than amine. (b) Assertion is correct, reason is correct; reason is not a
(ii) pyridine is weaker base than amine. correct explanation for assertion
(iii) pyridine removes HCl formed and shifts the equilibrium (c) Assertion is correct, reason is incorrect
to the right hand side. (d) Assertion is incorrect, reason is correct.
(iv) pyridine removes HCl formed and shifts the equilibrium 58. High basicity of Me 2 NH relative to Me3N is attributed to:
to the left hand side.
(a) effect of solvent (b) inductive effect of Me
(a) (i) and (iii) (b) (ii) and (iv)
(c) (ii) and (iii) (d) (i) and (iv) (c) shape of Me2NH (d) shape of Me3N
53. N– Ethylbenzene sulphonyl amide is strongly acidic and 59. What is the decreasing order of basicity of primary,
soluble in alkali due to presence of secondary and tertiary ethylamines and NH3 ?
(a) strong electron donating sulphonyl group. (a) NH3 > C2H5 NH 2 > (C 2 H5 )2 NH > (C2H5 )3N
(b) strong electron withdrawing sulphonyl group.
(c) weak electron donating sulphonyl group. (b) (C2 H 5 )3 N > (C2 H 5 )2 NH > C2 H 5 NH 2 > NH 3
(d) weak electron withdrawing sulphonyl group. (c) (C2 H 5 ) 2 NH > C2 H5 NH 2 > (C 2 H 5 ) 3 N > NH 3
54. Arrange the following in increasing order of their basic
(d) (C2H5)2 NH > C2H5NH2 > (C2H5)3 NH > NH3
strength?
p–nitroaniline(1); m–nitroaniline (2); 2,4,6–trimethylaniline(3); 60. Arrange the following amines in the decreasing order of
3–methylanline(4). their basicity
(a) 1, 3, 2, 4 (b) 2, 3, 4, 1 NH2
(c) 3, 1, 2, 4 (d) 1, 2, 4, 3
(1) (2)
NH2 NH2

2NaNO /HCl CuBr

55. ¾¾¾¾¾¾
® (P) ¾¾¾® (Q) CH2 – CH2 – NH2
0° C HBr

The compound Q is – (3)

(a) bromobenzene (b) chlorobenzene
(c) benzyl bromide (d) benzyl chloride
(a) 1 > 3 > 2 (b) 3 > 2 > 1
56. Which of the following is/are correct regarding nitration of
aniline with conc. HNO3 and conc. H2SO4 ? (c) 1 > 2 > 3 (d) 2 > 1 > 3

NH2 NH2 NH2 3 2(CH CO) O,Pyridine

61. NH2 ¾¾¾¾¾¾¾¾® (II)
NO2
conc. HNO
(i) ¾¾¾¾¾¾
3
® +
conc. H 2SO4 (I)

(i) LiAlH
4 ® III
NO2 ¾¾¾¾¾
(ii) H2O
+ +
NH3 NH3 The basicity order of I, II and III is –
(a) III > I > II (b) I > II > III
(ii) ¾¾
® (c) III > II > I (d) II > III > I
NO2 62. The correct order of decreasing basic character is
(iii) The substitution can be explained on the basis of C 6 H 5 NH 2 C 6 H 5CH 2 NH 2
, ,
inductive effect (– I) I II
(iv) The substitution can be influenced by +M and +E ( C6 H5 )2 NH , C 6 H11 NH 2
effects. IV
III
(a) (i), (ii) and (iii) (b) (ii) and (iii)
(c) (ii) and (iv) (d) (i) and (iii) (a) II > I > III > IV (b) IV > II > I > III
57. Assertion : Nitrating mixture used for carrying out nitration (c) IV > III > II > I (d) IV > II > III > I
of benzene consists of conc. HNO3 + conc. H2SO4. 63. Aniline when treated with conc. HNO3 gives
Reason : In presence of H2SO4, HNO3 acts as a base and (a) p-Phenylenediamine (b) m-Nitroaniline
produces NO2+ ions. (c) p-Benzoquinone (d) Nitrobenzene
 EBD_7374
388 CHEMISTRY

64. Which of the following compounds is most basic? 67. Nitration of nitrobenzence is carried out product is reduced
with Fe/HCl, product so formed on reaction with HNO2 and
(a) than with H2O, forms
O2N NH2
(a) 1,3–dihydroxybenzene
(b) 3–nitrophenol
(b) CH2NH2 (c) 2– nitrophenol
(d) 1,2–dihydroxybenzene
68. A compound of molecular formulae C3H6N shows following
(c) N – COCH3 characteristics
H (i) Get dissolved in acidic medium.
(ii) Does not react with benzoyl chloride
(d) NH2 (iii) Does not give carbylamine test
(iv) Does not evolve nitrogen gas on reacting with HNO2.
NH2 Structure of the compound is
(a) trimethylamine (b) isopropylamine
65. 3 (CH CO) O
2 ® ( X ) ¾¾¾¾ HNO
3 ® (Y ) ¾¾¾ H+ (c) propylamine (d) None of these
¾¾¾¾¾¾ ® (Z )
H 2SO 4 H 2O 69. In a reaction of aniline-a coloured product C was obtained.
CH 3
Product Z of the reaction
NH2 –N

NH2 NH2 NaNO2 CH3

B C
HCl Cold
A
(a) (b)
The structure of C would be :
NO2
NO2 (a) – N = N – CH2– N –

CH3
NO2 NO2
CH3 CH3

(c) (d) –N=N–

(b)
NO2
NO2 CH3
– NH – NH – –N
NH2 (c) CH3

66. 3 CH COCl
2 Br - H O
2 ® B ¾¾¾¾
3 ®C H O+ CH3
¾¾¾¾¾
® A ¾¾¾¾¾
(d) –N=N– –N
CH3
C (major product) is –
Topic 5: Methods of Preparation of Diazonium Salts
NH2 NH2
70. Diazonium salt is obtained when aniline reacts with :
Br
(a) cold NaOH (b) NaNO2 and HCl (0–5°C)
(a) (b) (c) SnCl2 at 10°C (d) N2O at (0 – 5°C)
Br 71. In the diazotization of arylamines with sodium nitrite and
hydrochloric acid, an excess of hydrochloric acid is used
NH2 primarily to
(a) supress the concentration of free aniline available for
coupling
(c) (d) None of these
(b) supress hydrolysis of phenol
(c) ensure a stoichiometric amount of nitrous acid
Br (d) neutralise the base liberated
AMINES 389

77. Which of the following statements are correct ?

Topic 6: Properties of Diazonium Salts
(i) In Sandmeyer reaction nucleophiles like Cl –, Br– and
72. Azo dye is prepared by the coupling of phenol and CN– are indroduced in benzene ring in the presence of
(a) benzene diazonium chloride Cu+ ion
(b) o-nitroaniline (ii) In Gattermann reaction nucleophiles are introduced in
(c) benzoic acid (d) chlorobenzene benzene ring in the presence of copper powder and
HCl.
73. In the reaction sequence
(iii) The yield in Gattermann reaction is found to be better
NH2 than Sandmayer reaction.
(a) (i) and (ii) (b) (i), (ii) and (iii)
NaNO ,HCl CuCN LiAlH
¾¾¾¾¾
2 ® A ¾¾¾¾
¾ ® B ¾¾¾¾
4 ® C, (c) (ii) and (iii) (d) (i) and (iii)
0° C
78. Match the columns
Column-I Column-II
the product ‘C’ is:
(A) ArN +2 Cl- ¾¾
® ArOH (p) HBF4 / NaNO 2
(a) benzonitrile (b) benzaldehyde
(c) benzoic acid (d) benzylamine (B) ArN +2 Cl- ¾¾
® ArNO 2 (q) H2O
– (C) ArN+2 Cl- ¾¾
® ArH (r) HBF4
N2+Cl Cl
(D) ArN +2 Cl- ¾¾
® ArF (s) CH3CH2OH
74. Conc. HCl
+ Cu2Cl2 ¾¾¾¾
¾® + N2 (a) A – (q), B – (p), C – (s), D – (r)
(b) A – (s), B – (p), C – (q), D – (r)
Chlorobenzene
(c) A – (q), B – (s), C – (p), D – (r)
Above reaction is known as: (d) A – (q), B – (s), C – (r), D – (p)
(a) Strecker's reaction (b) Sandmeyer's reaction 79. Match the columns
(c) Wohl-Ziegler reaction (d) Stephen's reaction Column-I Column-II
75. Which of the following r eagents will convert (A) Benzene sulphonyl (p) Zwitter ion
p-methylbenzenediazonium chloride into p-cresol? chloride
(a) Cu powder (b) H2O (B) Sulphanilic acid (q) Hinsberg reagent
(c) H3PO2 (d) C6H5OH (C) Alkyl diazonium salts (r) Dyes
76. In the chemical reactions, (D) Aryl diazonium salts (s) Conversion to alcohols
(a) A – (s), B – (q), C – (r), D – (p)
NH2 (b) A – (q), B – (p), C – (s), D – (r)
NaNO2 HBF 4
(c) A – (r), B – (s), C – (p), D – (q)
HCl, 278 K
A B (d) A – (s), B – (p), C – (r), D – (q)
80. The reagents that can be used to convert benzenediazonium
the compounds ‘A’ and ‘B’ respectively are chloride to benzene are _________.
(a) nitrobenzene and fluorobenzene (i) SnCl2/HCl (ii) CH3CH2OH
(b) phenol and benzene (iii) H3PO2 (iv) LiAlH4
(c) benzene diazonium chloride and fluorobenzene (a) (i) and (ii) (b) (ii) and (iii)
(d) nitrobenzene and chlorobenzene (c) (iii) and (iv) (d) (i) and (iii)
 EBD_7374
390 CHEMISTRY

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 8. The source of nitrogen in Gabriel synthesis of amines
is ............ .
1. Which of the following is a 3° amine?
(a) sodium azide, NaN3
(a) 1-methylcyclohexylamine (b) sodium nitrite, NaNO2
(b) Triethylamine (c) potassium cyanide, KCN
(c) tert-butylamine (d) potassium phthalimide, C6H4(CO)2N–K+
(d) N-methylaniline 9. Amongst the given set of reactants, the most appropriate
for preparing 2° amine is ............ .
2. The correct IUPAC name for CH2 = CHCH2NHCH3 is
(a) 2° R – Br + NH3
(a) allyl methylamine
(b) 2° R – Br + NaCN followed by H2/Pt
(b) 2-amino-4-pentene
(c) 1° R – NH2 + RCHO followed by H2/Pt
(c) 4-aminopent-1ene (d) 1° R – Br(2 mol) + potassium phthalimide followed by
(d) N-methylprop-2-en-1-amine H3O+/heat
3. Amongst the following, the strongest base in aqueous 10. The best reagent for converting 2-phenylpropanamide into
medium is ............... . 2-phenylpropanamine is ............ .
(a) CH3NH2 (b) NCCH2NH2 (a) excess H2
(b) Br2 in aqueous NaOH
(c) (CH3)2NH (d) C6H5NHCH3
(c) iodine in the presence of red phosphorus
4. Which of the following is the weakest Bronsted base?
(d) LiAlH4 in ether
NH2 11. The best reagent for converting 2-phenylpropanamide into
(a) (b) N—H 1-phenylethanamine is ............... .
(a) excess H2 / Pt (b) NaOH / Br 2
(c) NaBH4 / methanol (d) LiAlH4 / ether
NH2
12. Hoffmann bromamide degradation reaction is shown
(c) (d) CH3NH2 by ............. .
(a) ArNH2 (b) ArCONH2
(c) ArNO2 (d) ArCH2NH2
5. Benzylamine may by alkylated as shown in the following
equation? 13. The correct increasing order of basic strength for the
following compounds is .............. .
C6H5CH2NH2 + R — X —® C6H5CH2NHR
Which of the following alkyl halides is best suited for this NH2 NH2 NH2
reaction through SN1 mechanism?
(a) CH3 Br (b) C6 H5 Br
(c) C6 H5CH2Br (d) C2 H5 Br
NO2 CH 3
6. Which of the following reagents would not be a good choice
(I) (II) (III)
for reducing an aryl nitro compound to an amine?
(a) H2(excess) / Pt (b) LiAlH4 in ether (a) II < III < I (b) III < I < II
(c) Fe and HCl (d) Sn and HCl (c) III < II < I (d) II < I < III
7. In order to prepare a 1° amine from an alkyl halide with 14. Methylamine reacts with HNO2 to form ........... .
simultaneous addition of one CH2 group in the carbon chain, (a) CH3 – O – N = O (b) CH3 – O – CH3
the reagent used as a source of nitrogen is .......... .
(c) CH3OH (d) CH3CHO
(a) sodium amide, NaNH2
(b) sodium azide, NaN3 15. The gas evolved when methylamine reacts with nitrous acid
is ................... .
(c) potassium cyanide, KCN
(d) potassium phthalimide, C6H4(CO)2N–K+ (a) NH3 (b) N2 (c) H2 (d) C2H6
AMINES 391

16. In the nitration of benzene using a mixture of conc. H2SO4 24. Among the following amines, the strongest Bronsted base
and conc. HNO3, the species which initiates the reaction is ............. .
is ............ .
NH2
(a) NO2 (b) NO+ (c) NO+2 (d) NO -2
17. Reduction of aromatic nitro compounds using Fe and HCl (a) (b) NH3
gives ............. .
(a) aromatic oxime (b) aromatic hydrocarbon
(c) aromatic primary amine (d) aromatic amide H H
18. The most reactive amine towards dilute hydrochloric acid is
............. . N N
(c) (d)
CH3
(a) CH3 — NH2 (b) NH
CH3 25. The correct decreasing order of basic strength of the
NH2 following species is ........... . H2O, NH3, OH–, NH -2
CH 3
(c) N – CH3 (d) (a) NH 2– > OH – > NH3 > H 2 O
CH 3
(b) OH - > NH -2 > H 2O > NH3
19. Acid anhydrides on reaction with primary amines
give ................. . (c) NH3 > H 2O > NH -2 > OH -
(a) amide (b) imide (d) H 2 O > NH3 > OH - > NH 2-
(c) secondary amine (d) imine
26. Which of the following should be most volatile?
+
- Cu/HCl
20. The reaction Ar N 2Cl ¾¾¾¾
® ArCl + N 2 + CuCl is I. CH3CH2CH2NH2 II. (CH3)3N
named as ........... . III. CH3CH2 IV. CH3CH2CH3
(a) Sandmeyer reaction (b) Gattermann reaction NH
CH3
(c) Claisen reaction (d) Carbylamine reaction
21. Best method for preparing primary amines from alkyl halides (a) II (b) IV (c) I (d) III
without changing the number of carbon atoms in the chain Past Year MCQs
is
27. In the following reaction, the product (A) [AIPMT 2014, A]
(a) Hoffmann bromamide reaction
+
(b) Gabriel phthalimide synthesis NºNCl
–
NH2
(c) Sandmeyer reaction
(d) reaction with NH3 + H+ (A) is :
¾¾®
22. Which of the following compound will not undergo azo Yellow dye
coupling reaction with benzene diazonium chloride?
(a) Aniline (b) Phenol (a) N=N–NH
(c) Anisole (d) Nitrobenzene
23. Which of the following compounds is the weakest Bronsted NH2
base?
NH2 NH2 (b) N=N

(a) (b) NH2

(c) N=N
OH OH

(c) (d) (d) N=N NH2

 EBD_7374
392 CHEMISTRY

28. Which of the following will be most stable diazonium salt (c) reduction of nitrobenzene with H2/Pd in ethanol
RN2+X– ? [AIPMT 2014, C] (d) potassium salt of phthalimide treated with
+
(a) CH3 N2 X – (b) C6H5N2+X– chlorobenzene followed by hydrolysis with aqueous
(c) CH3CH2N2 X + – (d) C6H5CH2N2+X– NaOH solution.
35. The following reaction
29. Assertion : Acetamide reacts with Br 2 in presence of
methanolic CH3ONa to form methyl N-methylcarbamate. NH2
Reason : Methyl isocyanate is formed as an intermediate + Cl
which reacts with methanol to form methyl N-
O
methylcarbamate. [AIIMS 2014, S]
(a) Assertion is correct, reason is correct; reason is a
is known by the name : [AIPMT 2015 RS, A]
correct explanation for assertion. (a) Friedel-Craft's reaction (b) Perkin's reaction
(b) Assertion is correct, reason is correct; reason is not a (c) Acetylation reaction (d) Schotten-Baumen
correct explanation for assertion 36. The electrolytic reduction of nitrobenzene in strongly acidic
(c) Assertion is correct, reason is incorrect medium produces : [AIPMT 2015, A]
(d) Assertion is incorrect, reason is correct. (a) Azoxybenzene (b) Azobenzene
30. On heating an aliphatic primary amine with chloroform and (c) Aniline (d) p-Aminophenol
ethanolic potassium hydroxide, the organic compound 37. The number of structural isomers possible from the molecular
formed is: [JEE M 2014, A] formula C3H9N is : [AIPMT 2015 RS, C]
(a) an alkanol (b) an alkanediol (a) 4 (b) 5 (c) 2 (d) 3
(c) an alkyl cyanide (d) an alkyl isocyanide 38. In the reaction [JEE M 2015, A]
31. Considering the basic strength of amines in aqueous NH2
solution, which one has the smallest pKb value?
[JEE M 2014, S] NaNO2 /HCl CuCN/KCN
(a) (CH3)2NH (b) CH3NH2 ¾¾¾¾¾
0–5°C
® D ¾¾¾¾¾D
® E + N2
(c) (CH3)3N (d) C6H5NH2
32. Which of the following does not give effervescences of
CH3
CO2 with aq. NaHCO3 solution? [BITSAT 2014, A]
the product E is :
OH
NO2 CH3
CN
(a) H2CO3 (b)
(a) (b)
NO2

CH3
OH
O2N NO2 COOH
(c) (d) None of these
(c)
33. Aniline reacts with phosgene and KOH to form
CH3
[BITSAT 2014, A]
OH O
(d) H 3C CH3
C Cl
(a) (b) 39. The carbylamine reaction is [BITSAT 2015, A]
OH OH
NHCOCl NCO CHO
(c) (d) (a) NaOH
+ CHCl3 ¾¾¾®
34. Method by which Aniline cannot be prepared is:
[AIPMT 2015 RS] NH2 N C
(a) hydrolysis of phenylisocyanide with acidic solution
(b) degradation of benzamide with bromine in alkaline (b) D
+ CHCl 3 + 3KOH ¾¾®
solution
AMINES 393

COCH3 CH2CH3 45. The correct increasing order of basic strength for the
following compounds is : [NEET 2017, C]
(c) Zn/Hg + conc.HCl
+ 4H ¾¾¾¾¾¾® NH2 NH2
NH2

(I) (II) (III)

CHO CH3OH
NO2 CH3
CHO
(d) + HCHO + NaOH ¾ ® (a) III < I < II (b) III < II < I
(c) II < I < III (d) II < III < I
OCH3 46. Which of the following are intermediates in Sandmeyer
CH3O
reaction ? [AIIMS 2017, S]
40. The correct statement regarding the basicity of arylamines (i) C6 H 5 N + º NCl - (ii) C6 H5 N+ º N
is [NEET 2016, C]
(a) Arylamines are generally less basic than alkylamines g
(iii) C 6 H 5 (iv) C6H5Cl
because the nitrogen lone-pair electrons are delocalized
(a) (ii) and (iii) (b) (i) and (iv)
by interaction with the aromatic ring p electron system.
(b) Arylamines are generally more basic than alkylamines (c) (ii) and (iv) (d) (i) and (ii)
because the nitrogen lone-pair electrons are not 47. Assertion : Aniline does not undergo Friedel-Crafts reaction.
delocalized by interaction with the aromatic ring p Reason : –NH2 group of aniline reacts with AlCl3 (Lewis
electron system. acid) to give acid-base reaction. [AIIMS 2017, C]
(c) Arylamines are generally more basic than alkylamines (a) Assertion is correct, reason is correct; reason is a
because of aryl group.
correct explanation for assertion.
(d) Arylamines are generally more basic than alkylamines,
because the nitrongen atom in arylamines is sp- (b) Assertion is correct, reason is correct; reason is not a
hybridized. correct explanation for assertion
41. Which of the following compound will not undergo azo (c) Assertion is correct, reason is incorrect
coupling reaction with benzene diazonium chloride. (d) Assertion is incorrect, reason is correct.
[AIIMS 2016, S] 48. Assertion : Aniline is better nucleophile than anilium ion.
(a) Aniline (b) Phenol Reason : Anilium ion have +ve charge. [AIIMS 2017, C]
(c) Anisole (d) Nitrobenzene
(a) Assertion is correct, reason is correct; reason is a
42. Assertion : Acylation of amines gives a monosubstituted
correct explanation for assertion.
product whereas alkylation of amines gives polysubstituted
product. (b) Assertion is correct, reason is correct; reason is not a
Reason : Acyl group sterically hinders the approach of correct explanation for assertion
further acyl groups [AIIMS 2016, C] (c) Assertion is correct, reason is incorrect
(a) Assertion is correct, reason is correct; reason is a (d) Assertion is incorrect, reason is correct.
correct explanation for assertion. 49. Which of the following compounds will form significant
(b) Assertion is correct, reason is correct; reason is not a amount of meta product during mono-nitration reaction ?
correct explanation for assertion [JEE M 2017, C]
(c) Assertion is correct, reason is incorrect
(d) Assertion is incorrect, reason is correct. OH OCOCH3
43. In the Hoffmann bromamide degradation reaction, the
number of moles of NaOH and Br 2 used per mole of amine (a) (b)
produced are : [JEE M 2016, C]
(a) Two moles of NaOH and two moles of Br 2.
(b) Four moles of NaOH and one mole of Br2. NH2 NHCOCH3
(c) One mole of NaOH and one mole of Br 2.
(d) Four moles of NaOH and two moles of Br 2. (c) (d)
44. Which of the following reactions is appropriate for converting
acetamide to methanamine ? [NEET 2017, S]
(a) Hoffmann Bromamide reaction 50. Which reagent converts nitrobenzene to N-phenylhydroxylamine?
(b) Stephens reaction [BITSAT 2017, S]
(c) Gabriels phthalimide synthesis (a) Zn/HCl (b) H2O2
(d) Carbylamine reaction (c) Zn/NH4Cl (d) LiAlH4
 EBD_7374
394 CHEMISTRY

51. Which of the following represents Schotten-Baumann NO2 NO2

reaction? [BITSAT 2017, C]
(a) formation of amides from amines and acid chlorides/ Å

NaOH (a) Å
(b)
(b) formation of amines from amides and LiAlH4
Y H Y H
(c) formation of amines from amides and Br2/NaOH
(d) formation of amides from oxime and H2SO4 NO2 NO2
52. The compound A on treatment with Na gives B, and with H
PCl5 gives C. B and C react together to give diethyl ether. Å
(c) Y (d) H
A, B and C are in the order Y Å
(a) C2H5OH, C2H6, C2H5Cl
54. Assertion : N, N-Diethylethanamine is more basic then N,
(b) C2H5OH, C2H5Cl, C2H5ONa N-Diethylethanamine. [AIIMS 2018]
(c) C2H5OH, C2H5ONa, C2H5Cl Reason : + I effect of ethyl is more than methyl.
(d) C2H5Cl, C2H6, C2H5OH (a) If both assertion and reason are true and reason is the
correct explanation of assertion.
53. Which of the following carbocations is expected to be most
(b) If both assertion and reason are true but reason is not
stable? [NEET 2018, C]
the correct explanation of assertion.
(c) If assertion is true but reason is false.
(d) If both assertion and reason are false.

Exercise 3 : Try If You Can

1. Nitrobenzene can be reduced to aniline by 3. Which statement is true regarding the following structure?
H 2 / Ni ..
Sn / HCl N
I II
CH3 C3H7
Zn / NaOH LiAlH4 C2H5
III IV
(a) It is a chiral molecule
(a) I, II and III (b) I and II
(b) It exists in two resolvable optically active forms
(c) I, II and IV (d) only II
(c) Both a) and b) (d) Neither a) nor b)
CH = CHNO2 4. Introduction of a methyl group in ammonia markedly
increases the basic strength of ammonia in aq. solution,
Zn/Hg introduction of the second methyl group increases only
2. ¾¾¾® Product . Here the product is
HCl marginally the basic strength of methyl amine in water.
This is due to
COCH3 (a) different type of hybridisation in the two amines
(b) protonated dimethyl amine is more solvated than
CH = CHNO2 CH = CHNH2 methyl amine
(c) protonated dimethyl amine is more solvated than the
protonated methyl amine
(a) (b)
(d) protonated dimethyl amine is less stable than the
protonated methyl amine
CH2CH3 CH2CH3
5. The correct order of decreasing basic character of the three
aliphatic primary amines is
CH2CH2NH2 CH2CH2NO2
NH2 NH2 NH2
I II III
(c) (d)
(a) I > II > III (b) III > II > I
(c) I > II » III (d) I = II º III
CH2CH3 CH2CH3
AMINES 395

6. The correct order of increasing basicity is

O
NH O ||
(i) OD - / Br
|| || 11. (CH 3 )3 C - C - NH 2 ¾¾¾¾¾¾
2®
Product P is
CH 3CH 2 NH 2 CH 3 C NH 2 CH 3 C NH 2 (ii)D2O
I II III
(a) (CH3)3 CNH2 (b) (CH3)3 CNHD
(a) II < III < I (b) I » III < II (c) (CH3)3CND2 (d) no reaction
(c) I < II < III (d) III < I < II 12. Predict the possible number of alkenes and the main alkene
7. The relative order of basic character of the following in the following reaction.
compounds is

(a) 2 and
N N
N (b) 2 and
H COCH3
I II III (c) 3 and H2 C = CH2
(d) 2 and H2C = CH2
O S
(i) CH3I
13. Product P is
N CH3 (ii) Ag 2O, heat
N N H
H H
IV V
CH3
(a) II > I > III > IV > V (b) II > III > IV > V > I (a) (b) N
(c) II > V > IV > I > III (d) II > IV > V > III > I N(CH3)2 CH3 CH3
8. In the following reaction, the reagent X should be
conc . H SO
RCOOH + [ X ] ¾¾ ¾ ¾
2 ¾
¾4 ® RNH
2 CH3
(a) NH3 (b) HN3 (c) N (d) None
(c) either of the two (d) None of the two CH3 CH3

9. Which of the following amines can be resolved into two (i) H 2O 2

enantiomers? 14. Product P is
(ii) heat
.. ..
N CH2CH3 N CH3 CH3 N(CH3)2
H CH3 H CH3
I II
..
H3C NH2 (a) N (b)
.. CH3 CH3
N C CH2CH3
CH3 H CH3
III IV (c) (d)
(a) I, IV (b) I, II
15. Which of the following is not formed as an intermediate in
(c) I, III, IV (d) III, IV
the Hofmann rearrangement?
10. In Hofmann bromamide degradation, one of the important
Br / NaOH
steps is the migration of R - CONH2 ¾¾2¾¾¾® RNH 2
(a) an alkyl group without its electron pair to electron
O H O
deficient N atom || | || .. -
(b) an alkyl group with its electron pair to electron (a) R - C - N Br (b) R - C - N - Br
.. ..
deficient O atom
(c) an alkyl group with its electron pair to electron rich N O
|| . .
atom (c) R - C - N :
(d) an alkyl group with its electron pair to electron
(d) All the three are formed
deficient N atom
 EBD_7374
396 CHEMISTRY

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (a) 9 (c) 17 (d) 25 (a) 33 (a) 41 (c) 49 (a) 57 (a) 65 (b) 73 (d)
2 (b) 10 (c) 18 (d) 26 (b) 34 (a) 42 (a) 50 (d) 58 (a) 66 (c) 74 (b)
3 (c) 11 (a) 19 (b) 27 (c) 35 (c) 43 (c) 51 (d) 59 (d) 67 (b) 75 (b)
4 (c) 12 (c) 20 (c) 28 (d) 36 (b) 44 (d) 52 (a) 60 (a) 68 (a) 76 (c)
5 (d) 13 (b) 21 (a) 29 (b) 37 (c) 45 (b) 53 (b) 61 (a) 69 (d) 77 (a)
6 (b) 14 (d) 22 (a) 30 (a) 38 (c) 46 (b) 54 (d) 62 (b) 70 (b) 78 (a)
7 (a) 15 (c) 23 (d) 31 (a) 39 (a) 47 (a) 55 (a) 63 (b) 71 (a) 79 (b)
8 (c) 16 (d) 24 (a) 32 (b) 40 (b) 48 (d) 56 (b) 64 (b) 72 (a) 80 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 7 (c) 13 (d) 19 (a) 25 (a) 31 (a) 37 (a) 43 (b) 49 (c)
2 (d) 8 (d) 14 (c) 20 (b) 26 (b) 32 (d) 38 (a) 44 (a) 50 (c)
3 (c) 9 (c) 15 (b) 21 (b) 27 (d) 33 (d) 39 (b) 45 (c) 51 (a)
4 (a) 10 (d) 16 (c) 22 (d) 28 (b) 34 (d) 40 (a) 46 (a) 52 (c)
5 (c) 11 (b) 17 (c) 23 (c) 29 (a) 35 (d) 41 (d) 47 (a) 53 (d)
6 (b) 12 (b) 18 (b) 24 (d) 30 (d) 36 (d) 42 (c) 48 (a) 54 (a)
Exercise 3 : Try If You Can
1 (b) 3 (a) 5 (a) 7 (c) 9 (d) 11 (c) 13 (b) 15 (d)
2 (b) 4 (d) 6 (d) 8 (b) 10 (d) 12 (c) 14 (d)
 28 Chapter
BIOMOLECULES

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Properties of Carbohydrates,
AIIMS 2 Proteins, Enzymes, Vitamins 3.7/5 7.3
JEE Main 2 and Nucleic acid
BITSAT 2
 EBD_7374
398 CHEMISTRY
BIOMOLECULES 399
 EBD_7374
400 CHEMISTRY

Exercise 1 : Topic-wise MCQs

9. Reduction of glucose by HI suggest that

Topic 1: Carbohydrates
(a) presence of OH groups
1. Which of the following statements is incorrect ? (b) presence of –CHO group
(a) Maltose gives two molecules of glucose only. (c) cyclic structure of glucose
(b) Cellulose and sucrose are polysaccharides. (d) six carbon atoms are arranged in straight chain
(c) Polysaccharides are not sweet in taste. 10. Which is the least stable form of glucose ?
(a) a-D-Glucose (b) b-D-Glucose
(d) Polysaccharides are also known as non-sugars.
(c) Open chain structure (d) All are equally stable
2. Which of the following properties of glucose cannot be 11. Isomerization of glucose produces
explained by its open chain structure? (a) galactose (b) fructose
(i) Glucose does not form hydrogen sulphite with NaHSO3 (c) mannose (d) allose
(ii) On oxidation with HNO3 glucose gives saccharic acid. 12. The number of chiral carbon atoms present in cyclic
(iii) Glucose is found to exist in two different crystalline structure a-D(+) glucose
forms which are named as a and b. (a) 3 (b) 4 (c) 5 (d) 6
(a) (ii) only (b) (i) and (iii) 13. The a-D glucose and b-D glucose differ from each other
(c) (ii) and (iii) (d) (i) and (ii) due to difference in carbon atom with respect to its
(a) conformation (b) configuration
3. Which of the following statements is incorrect regarding
(c) number of OH groups (d) size of hemiacetal ring
glucose?
14. Which of the following is the sweetest sugar?
(a) It is an aldohexose. (a) Sucrose (b) Glucose (c) Fructose (d) Maltose
(b) It is also known as dextrose 15. Cellulose is a polymer of
(c) It is monomer of cellulose. (a) Glucose (b) Fructose (c) Ribose (d) Sucrose
(d) It is the least abundant organic compound on earth. 16. Sucrose on hydrolysis gives
4. Glucose gives silver mirror test with Tollen’s reagent. It (a) fructose+ribose (b) glucose + fructose
shows the presence of (c) glucose+glucose (d) fructose + fructose
(a) acidic group (b) alcoholic group 17. Carbohydrates are stored in the body as
(c) ketonic group (d) aldehyde group (a) sugars (b) starch (c) glucose (d) glycogen
18. Which of the following carbohydrate does not correspond
5. The symbols D and L represent
to the general formula Cx(H2O)y ?
(a) the optical activity of compounds. (a) Glucose (b) 2-Deoxyribose
(b) the relative configuration of a particular stereoisomer. (c) Fructose (d) Arabinose
(c) the dextrorotatory nature of molecule. 19. Lactose is made of
(d) the levorotatory nature of molecule (a) a-D-glucose only
6. Glucose is found to exist in two different a and b crystalline (b) a-D-glucose and b-D-glucose
forms. These forms can be obtained by. (c) a-D-galactose and b-D-glucose
(i) The a form of glucose is obtained by crystallisation (d) b-D-galactose and b-D-glucose
from concentrated solution of glucose at 303 K. 20. Which of the following monosaccharides are present as
(ii) The b form of glucose is obtained by crystallisation five membered cyclic structure (furanose structure)?
from concentrated solution of glucose at 303 K. (i) Ribose (ii) Glucose
(iii) The b form is obtained by crystallisation from hot and (iii) Fructose (iv) Galactose
saturated aqueous solution at 371 K. (a) (i) and (ii) (b) (i) and (iii)
(iv) The a form is obtained by crystallisation from hot and (c) (iii) and (iv) (d) (ii) and (iii)
21. Invert sugar is
saturated aqueous solution at 371 K.
(a) chemically inactive form of sugar
(a) (i) and (iii) (b) (ii) and (iv)
(b) equimolecular mixture of glucose and fructose
(c) (ii) and (iii) (d) (i) only
(c) mixture of glucose and sucrose
7. When glucose reacts with bromine water, the main product (d) a variety of cane sugar
is 22. Sucrose which is dextrorotatory in nature after hydrolysis
(a) gluconic acid (b) glyceraldehyde gives glucose and fructose, among which
(c) saccharic acid (d) acetic acid (i) Glucose is laevorotatory and fructose is dextrorotatory.
8. Glucose does not react with (ii) Glucose is dextrorotatory and fructose is laevorotatory
(a) Br2/H2O (b) H2NOH (iii) The mixture is laevorotatory.
(c) HI (d) NaHSO3 (iv) Both are dextrorotatory.
BIOMOLECULES 401

(a) (i) and (iii) (b) (ii) and (iii) Which of the following statement(s) is/are true?
(c) (iii) and (iv) (d) (iii) only (a) (i) and (iii) (b) (i) and (ii)
23. Chemically amylose is a _________ with 200–1000 (c) Only (iii) (d) (i), (ii) and (iii)
a-D-(+)-glucose units held by ______ glycosidic linkage 30. Read the following statements and choose the correct–
(a) long unbranched chain, C1– C6. option?
(b) branched chain, C1 – C4. (i) Starch is a polymer of a – glucose.
(c) long unbranched chain, C1– C4. (ii) Starch consists of amylose and amylopectin.
(d) branched chain, C1– C6. (iii) Amylose is insoluble in water.
24. Amylopectin is a ________ polymer of a-D-glucose units (iv) Amylopectin is soluble in water.
in which chain is formed by _______ glycosidic linkage (a) (i) (iii) and (iv) (b) (i), (ii) and (iii)
whereas branching occurs by ________ glycosidic linkage. (c) (i) and (ii) (d) (iii) and (iv)
(a) branched chain, C1– C6, C1– C4. 31. Match the columns
(b) branched chain, C1– C4, C1– C6. Column - I Column - II
(c) unbranched chain, C1– C4, C1– C6. (Enzymes) (Reactions)
(d) unbranched chain, C1– C6, C1– C4.
(A) Invertase (p) Decomposition of urea into
25. Which of the following is incorrect about cellulose?
(a) It is a major constituent of cell wall of plant cells. NH3 and CO2
(b) It is a branched chain disaccharide (B) Maltase (q) Conversion of glucose into
(c) It is composed of only b-D-glucose units. ethyl alcohol
(d) The glycosidic linkage between two units is found (C) Pepsin (r) Hydrolysis of maltose into
between C1 of one unit and C4 of next unit. glucose
26. Read the following statements and choose the correct (D) Urease (s) Hydrolysis of cane sugar
answer? (E) Zymase (t) Hydrolysis of proteins into
(i) All monosaccharides are reducing sugars. peptides
(ii) All monosaccharides are not reducing sugars. (a) A – (s), B – (r), C – (t), D – (p), E – (q)
(iii) In disaccharides, if aldehydic or ketonic groups are (b) A – (r), B – (q), C – (s), D – (p), E – (t)
bonded, these are non– reducing sugars. (c) A – (q), B – (p), C – (r), D – (s), E – (t)
(iv) In disaccharides, if aldehydic or ketonic groups are (d) A – (s), B – (p), C – (t), D – (q), E – (r)
free, these are reducing sugars.
32. Which one of the following is the reagent used to identify
(a) (i), (iii) and (iv) (b) (ii), (iii) and (iv) glucose?
(c) (i) and (iv) (d) (ii) and (iv) (a) Neutral ferric chloride
27. Which of the following statement(s) is/are correct? (b) Chloroform and alcoholic KOH
(i) Glucose is reducing sugar (c) Ammoniacal silver nitrate
(ii) Sucrose is reducing sugar (d) Sodium ethoxide
(iii) Maltose is non reducing sugar 33. Glucose molecule reacts with 'X' number of molecules of
(iv) Lactose is reducing sugar phenylhydrazine to yield osazone. The value of 'X' is
(a) (i) and (ii) only (b) (i) and (iii) only (a) four (b) one
(c) (i) and (iv) only (d) All of these (c) two (d) three
28. Which of the following statements regarding carbohydrates 34. Assertion : D(+)– Glucose is dextrorotatory in nature.
are correct? Reason : ‘D’ represents its dextrorotatory nature.
(i) Lactose is the carbohydrate found in milk. (a) Assertion is correct, reason is correct; reason is a
(ii) More than 25 monosaccharides occur naturally. correct explanation for assertion.
(iii) Sucrose on hydrolysis gives one molecule each of (b) Assertion is correct, reason is correct; reason is not a
glucose and fructose. correct explanation for assertion
(iv) Maltose is a non-reducing sugar whereas sucrose is a (c) Assertion is correct, reason is incorrect
reducing disaccharide sugar. (d) Assertion is incorrect, reason is correct.
(a) (i), (ii) and (iii) (b) (i) and (iii) 35. In the acetylation of glucose, which group is involved in
(c) (ii), (iii) and (iv) (d) (iii) and (iv) the reaction
29. Read the following statements. (a) CHO group (b) >C = O group
(i) Pyran is a cyclic organic compound with one oxygen (c) alcoholic OH group (d) all of these
atom and five carbon atoms. 36. Select the false statement about the cyclic glucose.
(ii) The cyclic structure of glucose is correctly represented (a) If the OH group is added to CHO group it will form
by Haworth strucure. cyclic hemiacetal structure
(iii) Five membered cyclic structure of glucose is called (b) Glucose form Six-membered ring in which –OH is at
pyranose structure. C–5 position
 EBD_7374
402 CHEMISTRY

(c) Melting point of a-glucose is 423 K and of b-glucose

Topic 2: Proteins
is 419 K
42. One of essential a-amino acids is
O
(a) lysine (b) serine
1 1 1
H C OH H C HO C H (c) glycine (d) proline
H 2 OH H 2 OH H 2 OH 43. Two functional groups that are present in all amino acids are
HO 3 H O HO 3 H HO 3 H O
H 4 OH H 4 OH H 4 OH the
(d) H 56 H 56 OH H 56 (a) hydroxy, amine (b) hydroxy, amide
CH2OH CH2OH CH2OH (c) carboxyl, amino (d) carboxyl, amide
a-D(+)-glucose a-D(+)-glucose 44. Which of the following is not an optically active amino
37. Assertion : Sucrose is called an invert sugar. acid?
Reason : On hydrolysis, sucrose bring the change in the (a) Valine (b) Glycine
sign of rotation from dextro (+) to laevo(–). (c) Leucine (d) Arginine
(a) Assertion is correct, reason is correct; reason is a 45. Denaturation of proteins leads to loss of its biological
correct explanation for assertion. activity by
(b) Assertion is correct, reason is correct; reason is not a (a) Formation of amino acids
correct explanation for assertion (b) Loss of primary structure
(c) Assertion is correct, reason is incorrect (c) Loss of both primary and secondary structures
(d) Assertion is incorrect, reason is correct. (d) Loss of both secondary and tertiary structures
38. When a-D-glucose and b-D-glucose are dissolved in water 46. Amino acids generally exist in the form of Zwitter ions. This
in two separate beakers I and II respectively and allowed to means they contain
stand, then – (a) basic—NH2 group and acidic —COOH group
(a) specific rotation in beaker I will decrease while in II will +
increase upto a constant value (b) the basic— NH3 group and acidic —COO– group
(b) the specific rotation of equilibrium mixture in two (c) basic—NH2 and acidic —H+ group
beakers will be different +
(c) the equilibrium mixture in both beakers will be (d) basic –COO– group and acidic — N H 3 group
leavorotatory 47. The structural feature which distinguishes proline from
(d) the equilibrium mixture in both beakers will contain only natural a-amino acids?
cyclic form of glucose (a) Proline is optically inactive
39. Cyclic structure of fructose resembles with (b) Proline contains aromatic group
(a) pyran (b) furan (c) Proline is a dicarboxylic acid
(c) pyridine (d) oxiran (d) Proline is a secondary amine
40. Assertion : b-Glycosidic linkage is present in maltose, 48. Which one of the following structures represents the peptide
CH2OH CH2OH chain?
H O H OH H O
H H | | ||
OH H O OH H (a) - N - C - N - C - NH - C - NH -
HO H OH || | |
H OH H OH O H
Reason : Maltose is composed of two glucose units in which H H
C–1 of one glucose unit is linked to C–4 of another glucose | | | | | | | |
unit. (b) - N - C - C- C - C - N - C - C - C -
(a) Assertion is correct, reason is correct; reason is a || | | | | | |
correct explanation for assertion. O
(b) Assertion is correct, reason is correct; reason is not a H H H O
correct explanation for assertion | | | | | | ||
(c) Assertion is correct, reason is incorrect (c) - N - C- C - N - C - C - N - C - C -
| || | || |
(d) Assertion is incorrect, reason is correct. O O
41. Sucrose in water is dextro-rotatory, [a]D= + 66.4º. When
H O H
boiled with dilute HCl, the solution becomes leavo-rotatory, | | | || | | | | |
[a]D= –20º. In this process the sucrose molecule breaks into (d) - N - C- C- C - N - C- C- N- C - C- C-
| | | | | || | |
(a) L-glucose + D-fructose H O
(b) L-glucose + L-fructose 49. Simplest proteins has one peptide linkage. It is
(c) D-glucose + D-fructose (a) tripeptide (b) dipeptide
(d) D-glucose + L-fructose (c) tetrapeptide (d) oligopeptide
BIOMOLECULES 403

50. Proteins are polypeptides of (c) During denaturation 1° and 2° structures are destroyed
(a) b-amino acids (b) a-hydroxy acids but 3° structure remains intact.
(c) D-a-amino acids (d) L-a-amino acids (d) All the above statements are incorrect.
51. Globular proteins are present in 63. Which of the following indicates the order in which amino
(a) blood (b) less acids are linked together in a protein ?
(c) milk (d) all of these (a) Primary structure (b) Secondary structure
52. In fibrous proteins, polypeptide chains are held together by (c) Tertiary structure (d) Quaternary structure
(a) van der waals forces 64. Which of the following statement is not true about
(b) electrostatic forces of attraction secondary structure of protein ?
(c) hydrogen bonds
(a) The alpha helix, beta pleated sheet and beta turns are
(d) covalent bonds
examples of secondary structure of protein.
53. Which of the following is not a fibrous protein?
(b) The ability of peptide bonds to form intramolecular
(a) Keratin (b) Myosin
hydrogen bonds is important to secondary structure.
(c) Insulin (d) Both (a) and (b)
54. A polypeptide with more than hundred amino acid residues, (c) The steric influence of amino acid residues is important
having molecular mass higher than 10,000 u is called_____. to secondary structure.
(a) nucleic acid (b) hormone ( d) The hydrophilic/ hydrophobic character of amino acid
(c) protein (d) enzyme residues is important to secondary structure.
55. An insulin is a ______ which contains _____ amino acids. 65. Which of the following terms indicates to the arrangement
(a) protein, 74 (b) protein, 51 of different protein subunits in a multiprotein complex ?
(c) hormone, 51 (d) hormone, 74 (a) Primary structure (b) Secondary structure
56. Which of the following is an example of globular protein? (c) Tertiary structure (d) Quaternary structure
(a) Glycine (b) Albumin 66. Secondary structure of protein is mainly governed by
(c) Alanine (d) Both (a) and (b) (a) hydrogen bonds (b) covalent bonds
57. Which of the following is not a characteristics of fibrous (c) ionic bonds (d) disulphide bonds
proteins? 67. The secondary structure of a protein refers to
(a) In the fibrous proteins, polypeptide chains are held (a) fixed configuration of the polypeptide backbone
together by hydrogen and disulphide bonds. (b) a - helical backbone
(b) These have fibre like structure. (c) hydrophobic interactions
(c) These are generally soluble in water. (d) sequence of a - amino acids
(d) These have elongated shape.
68. Tertiary structure of protein arises due to
58. Which of the following statements is true about a peptide
(a) folding of polypeptide chain
bond (RCONHR)?
(a) It is non planar. (b) folding, coiling and bonding of polypeptide chain
(b) It is capable of forming a hydrogen bond. (c) linear sequence of amino acid in polypeptide chain
(c) The cis configuration is favoured over the trans (d) denatured proteins
configuration. 69. Coagulation of protein is known as
(d) Single bond rotation is permitted between nitrogen and (a) dehydration (b) decay
the carbonyl group. (c) deamination (d) denaturing
59. Proteins are condensation polymers of 70. Which of the following terms refers to the overall three
(a) a-amino acids (b) b-amino acids dimensional shape of a protein.
(c) a-hydroxy acids (d) b-hydroxy acids (a) Primary structure (b) Secondary structure
60. Primary structure of a protein is (c) Tertiary structure (d) Quaternary structure
(a) sequence in which a-amino acids are linked to one 71. Which of the following indicates to ‘regions of ordered
another structure within a protein’.
(b) sequence in which amino acids of one polypeptide (a) Primary structure (b) Secondary structure
chain are joined to other chain (c) Tertiary structure (d) Quaternary structure
(c) the folding patterns of polypeptide chains 72. The strongest form of intermolecular bonding that could
(d) the pattern in which the polypeptide chains are arranged be formed involving the residue of the amino acid serine is.
61. The helical structure of protein is stabilized by
(a) ionic bond
(a) dipeptide bonds (b) hydrogen bonds
(b) hydrogen bond
(c) ether bonds (d) peptide bonds
62. Which of the following statements is incorrect? (c) van der Waal’s interactions
(a) In a-helix structure a polypeptide chain forms all (d) None of the above
possible hydrogen bonds by twisting into a right 73. Which of the following protein destroys the antigen when
handed screw. it enters in body cell?
(b) In b-structure of proteins all peptide chains are (a) Antibodies (b) Insulin
stretched out to nearly maximum extension. (c) Chromoprotein (d) Phosphoprotein
 EBD_7374
404 CHEMISTRY

74. Which among the following statements are true for glycine? 82. The enzyme which hydrolyses triglycerides to fatty acids
(i) It exists in crystalline form and glycerol is called
(ii) It is optically active (a) Maltase (b) Lipase
(iii) It is soluble in water (c) Zymase (d) Pepsin
(iv) It can form Zwitter ions 83. Which one of the following, statements is incorrect about
(a) (i), (ii) and (iii) (b) (i), (ii) and (iv) enzyme catalysis?
(c) (i), (iii) and (iv) (d) (ii), (iii) and (iv) (a) Enzymes are mostly proteinous in nature.
75. Which of the following statements are correct? (b) Enzyme action is specific.
(i) Proteins on hydrolysis gives only a-amino acids. (c) Enzymes are denaturated by ultraviolet rays and at high
(ii) Gln stands for glutamic acid. temperature.
(iii) Amino acids with equal number of amino and carboxyl
(d) Enzymes are least reactive at optimum temperature.
groups are neutral.
84. Insulin production and its action in human body are
(iv) All naturally occuring a-amino acids are optically
responsible for the level of diabetes. This compound belongs
active.
(a) (i) and (iii) (b) (i), (ii) and (iv) to which of the following categories?
(c) (iii) and (iv) (d) (ii), (iii) and (iv) (a) An enzyme (b) A hormone
76. Which of the statements about "Denaturation" given below (c) A co-enzyme (d) An antibiotic
are correct ? 85. Enzymes are essential as biocatalysts. They function in
(i) Denaturation of proteins causes loss of secondary and (a) aqueous medium, temp = 30–35ºC; pH=7
tertiary structures of the proteins. (b) organic medium
(ii) Denaturation leads to the conversion of double strand (c) aqueous medium under extreme pH conditions
of DNA into single strand (d) None of these
(iii) Denaturation affects primary strucrture which gets 86. Which of the following statements is incorrect?
distorted (a) Enzymes are organic catalysts
(a) (ii) and (iii) (b) (i) and (iii) (b) Enzymes have a very large turnover number
(c) (i) and (ii) (d) (i), (ii) and (iii) (c) Enzymes action is specific
77. Assertion : At isoelectric point, the amino group do not (d) Enzymes always require a coenzyme in their catalytic
migrate under the influence of electric field. action.
Reason : At isoelectric point, amino acid exists as a zwitterion. 87. Of the following statements about enzymes which ones
(a) Assertion is correct, reason is correct; reason is a are true?
correct explanation for assertion. (i) Enzymes lack in nucleophilic groups
(b) Assertion is correct, reason is correct; reason is not a (ii) Enzymes are highly specific both in binding chiral
correct explanation for assertion substrates and in catalysing their reactions
(c) Assertion is correct, reason is incorrect (iii) Enzymes catalyse chemical reactions by lowering
(d) Assertion is incorrect, reason is correct.
the energy of activation
78. The strongest form of intermolecular bonding that could
(iv) Pepsin is a proteolytic enzyme
be formed involving the residue of the amino acid valine is
(a) (i) and (iv) (b) (i) and (iii)
(a) ionic bond
(b) hydrogen bond (c) (ii), (iii) and (iv) (d) (i)
(c) van der Waals interactions
(d) none of the above Topic 4: Vitamins
79. Which of the following molecules is capable of forming
88. Among the following vitamins the one whose deficiency
Zwitter ion?
causes rickets (bone deficiency) is :
(a) NH2CH2COOH (b) CH3CH2NH2
(c) CH3CH2COOH (d) All of these (a) Vitamin A (b) Vitamin B
(c) Vitamin D (d) Vitamin C
Topic 3: Enzymes 89. Anaemia is caused by the deficiency of vitamin
(a) B6 (b) B1 (c) B2 (d) B12
80. Which of the following is incorrect regarding enzymes?
(a) Most of them are globular proteins. 90. Vegetable oils like wheat gram oil, sunflower oil etc. are the
(b) They are very specific for a particular reaction but not good source of
for a particular substrate. (a) vitamin K (b) vitamin E
(c) They are generally named after the compound or class (c) vitamin D (d) vitamin A
of compounds upon which they work. 91. Which is a fat soluble vitamin?
(d) All the above statements are incorrect. (a) Vitamin A (b) Vitamin B6
81. Enzymes take part in a reaction and (c) Vitamin C (d) Vitamin B2
(a) decrease the rate of a chemical reaction 92. Vitamin B2, a water soluble vitamin, is also known as
(b) increase the rate of a chemical reaction (a) ascorbic acid (b) riboflavin
(c) both (a) and (b) (c) thiamine (d) pyridoxine
(d) None of these
BIOMOLECULES 405

93. Which of the following statements about vitamin B12 is Topic 5: Nucleic Acids
incorrect ?
99. The presence or absence of hydroxyl group on which carbon
(a) It has a cobalt atom
atom of sugar differentiates RNA and DNA?
(b) It also occurs in plants (a) 1st (b) 2nd
(c) It is also present in rain water (c) 3 rd (d) 4th
(d) It is needed for human body in very small amounts 100. The couplings between base units of DNA is through :
94. Which of the following statements are correct ? (a) Hydrogen bonding (b) Electrostatic bonding
(i) Vitamins A, D, E and K are insoluble in water.
(c) Covalent bonding (d) van der Waals forces
(ii) Vitamins A, D, E and K are stored in liver and adipose
101. Which of the following is correct about H-bonding in
tissues.
nucleotide?
(iii) Vitamin B and vitamin C are water soluble.
(a) A --- A and T --- T (b) G --- T and A --- C
(iv) Water soluble vitamins should not be supplied
(c) A --- G and T --- C (d) A --- T and G --- C
regularly in diet.
102. In DNA, the complimentary bases are:
(a) (i), (ii) and (iv) (b) (i), (ii) and (iii)
(a) Adenine and thymine; guanine and cytosine
(c) (i) and (iv) (d) (ii) and (iv)
(b) Adenine and thymine ; guanine and uracil
95. Match the columns
(c) Adenine and guanine; thymine and cytosine
Column - I Column - II
(d) Uracil and adenine; cytosine and guanine
(A) Vitamin B6 (p) Fat soluble
103. In DNA the linkages between different nitrogenous bases
(B) Vitamin K (q) Xerophthalmia
are :
(C) Vitamin D (r) Convulsions
(a) peptide linkage (b) phosphate linkage
(D) Vitamin A (s) Delayed blood clotting
(c) H-bonding (d) glycosidic linkage
(a) A – (p,q), B – (p,s), C – (p), D – (r)
104. DNA multiplication is called as
(b) A – (r), B – (p,s), C – (p), D – (p, q)
(a) translation (b) transduction
(c) A – (p,s), B – (r), C – (p), D – (p,q)
(c) transcription (d) replication
(d) A – (r), B – (p,s), C – (p,q), D – (p)
105. Chromosomes are made from
96. Match the columns
(a) proteins
Column - I Column - II
(b) nucleic acids
(A) Vitamin A (p) Scurvy
(c) proteins and nucleic acids
(B) Vitamin B12 (q) Hemorrhagic condition
(d) carbohydrates and nucleic acids
(C) Vitamin C (r) Sterility
106. The double helical structure of DNA was proposed by
(D) Vitamin E (s) Xerophthalmia
(a) Watson and Crick (b) Meichers
(E) Vitamin K (t) Pernicious anaemia
(c) Emil Fischer (d) Khorana
(a) A – (t), B – (s), C – (p), D – (r), E – (r)
107. a - Helix is found in
(b) A – (s), B – (t), C – (p), D – (q), E – (r)
(a) DNA (b) RNA
(c) A – (s), B – (t), C – (p), D – (r), E – (q)
(c) lipid (d) carbohydrates
(d) A – (t), B – (s), C – (p), D – (r), E – (q)
108. Which of the following compounds is responsible for the
97. Assertion : Vitamin D cannot be stored in our body
transmission of heredity characters?
Reason : Vitamin D is fat soluble vitamin and is excreted
(a) RNA (b) DNA
from the body in urine.
(c) Glucose (d) Haemoglobin
(a) Assertion is correct, reason is correct; reason is a
109. The latest discovery in cytology is that of
correct explanation for assertion.
(a) respiration (b) genetic code
(b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion (c) enzyme (d) None of these
(c) Assertion is correct, reason is incorrect 110. Energy is stored in our body in the form of
(d) Assertion is incorrect, reason is correct. (a) ATP (b) ADP
98. Vitamin C must be supplied regularly in diet because (c) fats (d) carbohydrates
(a) it is water soluble hence excreted in urine and can’t be 111. The chemical change in DNA molecule that could lead to
stored in the body synthesis of protein with an altered amino acid sequence is
called
(b) it is fat soluble hence stored in the body and cannot be
used on regular basis (a) replication (b) lipid formation
(c) it is required in a large amount by the body hence (c) cellular membrane (d) mutation
supplied regularly 112. DNA has deoxyribose, a base and the third component which is
(d) it is water soluble hence used by the body on daily (a) phosphoric acid (b) ribose
basis and is to be supplied regularly. (c) adenine (d) thymine
 EBD_7374
406 CHEMISTRY

113. The process by which synthesis of protein takes place based 118. Which of the following statements regarding DNA
on the genetic information present in m-RNA is called fingerprinting is incorrect?
(a) Translation (b) Transcription (a) It is used in forensic laboratories for identification of
(c) Replication (d) Messenger hypothesis criminals.
114. Which of the following structures represents thymine ? (b) It cannot be altered by surgery.
NH2 (c) It is different for every cell and cannot be altered by
O
any known treatment.
HN N (d) It is used to determine paternity of an individual.
(a) (b) 119. Which of the following statement(s) is/are correct?
O N O N
H H (i) Information regarding the sequence of nucleotides in
the chain of a nucleic acid is called its primary structure.
NH2 OH (ii) In secondary structure of DNA adenine forms
hydrogen bonds with guanine whereas cytosine forms
N N CH3
(c) (d) hydrogen bonds with thymine.
HO N HO N (iii) RNA molecules are of three types m-RNA, r-RNA and
t-RNA and they all perform different functions.
115. When adenine is attached to ribose sugar, it is called
(a) (ii) only (b) (i) and (iii)
adenosine. To make a nucleotide from it, it would require
(c) (ii) and (iii) (d) (iii) only
(a) oxygenation (b) addition of a base 120. In both DNA and RNA, heterocyclic base and phosphate
(c) addition of phosphate (d) hydrogenation ester linkages are at –
116. Which of the following is not present in a nucleotide?
(a) C5' and C1' respectively of the sugar molecule
(a) Guanine (b) Cytosine
(c) Adenine (d) Tyrosine (b) C1' and C5' respectively of the sugar molecule
117. The function of DNA in an organism is
(a) to assist in the synthesis of RNA molecule (c) C '2 and C5' respectively of the sugar molecule
(b) to store information of heredity characteristics (d) C5' and C '2 respectively of the sugar molecule
(c) to assist in the synthesis of proteins and polypeptides
(d) All of these

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 4. Which of the following pairs represents anomers?
1. Glycogen is a branched chain polymer of a-D glucose units
CHO CHO
in which chain is formed by C1–C4 glycosidic linkage where
H OH HO H
as branching occurs by the formation of C1–C6 glycosidic HO
HO H H
linkage. Structure of glycogen is similar to .......... . OH OH
(a) H H
(a) amylose (b) amylopectin H OH H OH
(c) cellulose (d) glucose CH2OH
CH2OH
2. Which of the following polymer is strored in the liver of
animals ?
(a) Amylose (b) Cellulose CHO CHO
(c) Amylopectin (d) Glycogen H OH HO H
3. Sucrose (Cane sugar) is a disaccharide. One molecule of HO H H OH
(b) H OH HO H
sucrose on hydrolysis gives .......... .
(a) 2 molecules of glucose H OH HO H
(b) 2 molecules of glucose + 1 molecule of fructose CH2OH CH2OH
(c) 1 molecule of glucose + 1 molecule of fructose
(d) 2 molecules of fructose
BIOMOLECULES 407

7. Which of the following acids is a vitamin?

(a) Aspartic acid (b) Ascorbic acid
H OH HO H
H (c) Adipic acid (d) Saccharic acid
H OH OH
8. Dinucleotide is obtained by joining two nucleotides together
(c) HO H O HO H O
H OH H OH by phosphodiester linkage. Between which carbon atoms
H H of pentose sugars of nucleotides are these linkages present?
CH2OH CH2OH (a) 5' and 3' (b) 1' and 5'
(c) 5' and 5' (d) 3' and 3'
9. Nucleic acids are the polymers of......
(a) nucleosides (b) nucleotides
H OH HO H
(c) bases (d) sugars
H OH HO H
10. Which of the following statements is not true about glucose?
(d) HO H O H OH O
(a) It is an aldohexose
H OH HO H
(b) On heating with HI it forms n-hexane
H H
CH2OH CH2OH (c) It is present in furanose form
(d) It does not give 2, 4-DNP test
5. Proteins are found to have two different types of secondary 11. Each polypeptide in a protein has amino acids linked with
structures viz. a-helix and b-pleated sheet structure. a-helix each other in a specific sequence. This sequence of amino
structure of protein is stabilised by: acids is said to be ......... .
(a) peptide bonds (a) primary structure of proteins
(b) van der Waal’s forces (b) secondary structure of proteins
(c) hydrogen bonds (c) tertiary structure of proteins
(d) dipole-dipole interactions (d) quateranary structure of proteins
6. In disaccharides, if the reducing groups of monosaccharides, 12. DNA and RNA contain four bases each. Which of the
i.e., aldehydic or ketonic groups are bonded, these are non- following bases is not present in RNA?
reducing sugars. Which of the following disaccharide is a (a) Adenine (b) Uracil (c) Thymine (d) Cytosine
non-reducing sugar? 13. Which of the following B group vitamins can be stored in
CH2OH CH2OH our body?
H O H H O H (a) Vitamin B1 (b) Vitamin B2
H H (c) Vitamin B6 (d) Vitamin B12
(a) OH H O OH H
OH OH 14. Which of the following bases is not present in DNA?
H OH H OH (a) Adenine (b) Thymine (c) Cytosine (d) Uracil
15. Three cyclic structures of monosaccharides are given below
CH2OH which of these are anomers.
O H O H
H HOH2C HO H
H
OH H H OH H OH HO H HO H
(b) O CH2OH
OH H OH H OH HO H O
H OH OH H HO H O HO H O H OH
H OH H OH HO H
CH2OH CH2OH H H H
O O H CH2OH CH2OH CH2OH
OH
OH
H H (i) (ii) (iii)
(c) OH H OH H
H O OH (a) I and II (b) II and III
H
H OH H OH (c) I and III (d) III is anomer of I and II
16. Which of the following reactions of glucose can be explained
CH2OH CH 2OH only by its cyclic structure?
O O OH (a) Glucose forms pentaacetate
H
OH
H H (b) Glucose reacts with hydroxylamine to form an oxime
(d) OH H OH H
H O H (c) Pentaacetate of glucose does not react with hydroxyl amine
H
(d) Glucose is oxidised by nitric acid to gluconic acid
H OH H OH
 EBD_7374
408 CHEMISTRY

17. Optical rotations of some compounds alongwith their (a) (A) is between C1 and C4, (B) and (C) are between C1
structures are given below which of them have D and C6
configuration. (b) (A) and (B) are between C1 and C4, (C) is between C1
and C6
CH2OH (c) (A) and (C) are between C1 and C4, (B) is between C1
CHO and C6
CHO
H OH C=O
(d) (A) and (C) are between C1 and C6, (B) is between C1
H OH HO H HO H
and C4
H OH H OH
CH2OH H OH H OH Past Year MCQs
CH2OH CH2OH 20. D (+) glucose reacts with hydroxylamine and yields an oxime.
(+) rotation (+) rotation (–) rotation
The structure of the oxime would be [AIPMT 2014, S]
(i) (ii) (iii)

(a) I, II, III (b) II, III (a) CH = NOH (b) CH = NOH
(c) I, II (d) III H – C – OH HO – C – H
18. Structure of disaccharide formed by glucose and fructose is
HO – C – H HO – C – H
given below. Identify anomeric carbon atoms in
monosaccharide units. HO – C – H H – C – OH
f
CH2OH H – C – OH H – C – OH
e a
O H O H
H HOH2C
e
CH2OH CH2OH
H b
d a
OH H H
OH
O CH2OH
c b c df
OH
H OH OH H

(a) 'a' carbon of glucose and 'a' carbon of fructose (c) CH = NOH (d) CH = NOH
(b) 'a' carbon of glucose and 'e' carbon of fructose HO – C – H H – C – OH
(c) 'a' carbon of glucose and 'b' carbon of fructose
(d) 'f ' carbon of glucose and 'f ' carbon of fructose H – C – OH HO – C – H
19. Three structures are given below in which two glucose units HO – C – H H – C – OH
are linked. Which of these linkages between glucose units
are between C1 and C4 and which linkages are between C1 H – C – OH H – C – OH
and C6?
CH2OH CH2OH
CH2OH CH2OH
H O H O OH
H H 21. Which of the following hormones is produced under the
(A)
OH H OH H condition of stress which stimulates glycogenolysis in the
OH O H
H
liver of human beings? [AIPMT 2014, C]
H OH H OH
(a) Thyroxin (b) Insulin
(I)
(c) Adrenaline (d) Estradiol
CH2OH CH2OH 22. For osazone formation, the effective structural unit necessary is
H O H O OH
H H [AIIMS 2014, S]
OH H H
(C) OH H
HO H (a) CH2OCH3 (b) CH 2OH
OH CH2OH O H | |
H OH CO CO
O (B) O |
|
H
H
CH2 OH H
H O H HO H
H (c) CH 2OH (d) CHO
H OH | |
OH H
OH OH (III) CHOCH 3 CHOCH 3
| |
H OH
(II)
BIOMOLECULES 409

23. Assertion : Glucose and fructose give the same osazone. (a) The sugar component in RNA is arabinose and the
Reason : During osazone formation stereochemistry only at sugar component in DNA is 2'-deoxyribose.
C1 and C2 is destroyed. [AIIMS 2014, C] (b) The sugar component in RNA is ribose and the sugar
(a) Assertion is correct, reason is correct; reason is a component in DNA is 2'-deoxyribose.
correct explanation for assertion. (c) The sugar component in RNA is arabinose
(b) Assertion is correct, reason is correct; reason is not a (d) The sugar component in RNA is 2'-deoxyribose and
correct explanation for assertion the sugar component in DNA is arabinose
(c) Assertion is correct, reason is incorrect 33. Which one of the following statements is correct?
(d) Assertion is incorrect, reason is correct. [AIIMS 2016, C]
24. Which one of the following bases is not present in DNA? (a) All amino acids except lysine are optically active
[JEE M 2014, C] (b) All amino acids are optically active
(a) Quinoline (b) Adenine (c) All amino acids except glycine are optically active
(c) Cytosine (d) Thymine (d) All amino acids except glutamic acids are optically
25. Which functional group participates in disulphide bond active
formation in proteins? [BITSAT 2014, A] 34. Assertion : Vitamin D cannot be stored in our body
(a) Thioester (b) Thioether Reason : Vitamin D is fat soluble vitamin and is excreted
(c) Thiol (d) Thiolactone from the body in urine. [AIIMS 2016, C]
26. Which of the statements about "Denaturation" given below (a) Assertion is correct, reason is correct; reason is a
are correct ? [AIIMS 2015, C] correct explanation for assertion.
(A) Denaturation of proteins causes loss of secondary and (b) Assertion is correct, reason is correct; reason is not a
tertiary structures of the protein. correct explanation for assertion
(B) Denturation leads to the conversion of double strand (c) Assertion is correct, reason is incorrect
of DNA into single strand (d) Assertion is incorrect, reason is correct.
(C) Denaturation affects primary structure which gets 35. Thiol group is present in : [JEE M 2016, C]
distorted
(a) Cysteine (b) Methionine
Options :
(c) Cytosine (d) Cystine
(a) (B) and (C) (b) (A) and (C)
36. What will happen when D-(+)-glucose is treated with
(c) (A) and (B) (d) (A), (B) and (C)
methanolic —HCl followed by Tollens’ reagent ?
27. Which of the vitamins given below is water soluble ?
(a) A black ppt. will be formed [BITSAT 2016, A]
[JEE M 2015, C]
(b) A red ppt. will be formed
(a) Vitamin E (b) Vitamin K
(c) A green colour will appear
(c) Vitamin C (d) Vitamin D
(d) No characteristic colour or ppt. will be formed.
28. A sequence of how many nucleotides in messenger RNA
37. Fructose on reduction gives a mixture of two alcohols which
makes a codon for an amino acid? [BITSAT 2015, S]
are related as [BITSAT 2016, A]
(a) Three (b) Four (c) One (d) Two
(a) diastereomers (b) epimers
29. The metal present in vitamin B12 is [BITSAT 2015, C]
(c) both (a) and (b) (d) anomers
(a) magnesium (b) cobalt
38. Which of the following statements is not correct :
(c) copper (d) zinc
[NEET 2017, C]
30. Which one given below is a non-reducing sugar?
(a) Ovalbumin is a simple food reserve in egg-white
[NEET 2016, C]
(b) Blood proteins thrombin and fibrinogen are involved
(a) Maltose (b) Lactose
in blood clotting
(c) Glucose (d) Sucrose
(c) Denaturation makes the proteins more active
31. In a protein molecule various amino acids are linked together
(d) Insulin maintains sugar level in the blood of a human
by [NEET 2016, S]
body
(a) a-glycosidic bond (b) b-glycosidic bond
39. a - D-(+)-glucose and b-D-(+)-glucose are[AIIMS 2017, S]
(c) peptide bond (d) dative bond
32. The correct statement regarding RNA and DNA, respectively (a) conformers (b) epimers
is [NEET 2016, S] (c) anomers (d) enatiomers
 EBD_7374
410 CHEMISTRY

40. Which of the following compounds will behave as a reducing (a) Aniline (b) Acetanilide
sugar in an aqueous KOH solution? [JEE M 2017, A] (c) Glycine (d) Benzoic acid
45. Structure of guanine is [AIIMS 2018, S]
HOH2C O CH2OH
NH2 O
(a) HO OCOCH
3
HC N N C NH
OH
(a) HC C (b) HC
C C
N O N N NH2
H H
HOH2C O CH2OH

(b) HO
O
OH H3C
(c) C N H (d) None
HC C
HOH2C O CH2OH N O
H
(c) HO OCH
3
46. Assertion : Proteins are made up of a-amino acids.
OH Reason : During denaturation, secondary and tertiary
structures of proteins are destroyed. [AIIMS 2018, C]
(a) Assertion is correct, reason is correct; reason is a
HOH2C
correct explanation for assertion.
O CH2OCH3
(b) Assertion is correct, reason is correct; reason is not a
(d) OH correct explanation for assertion
OH (c) Assertion is correct, reason is incorrect
OH
(d) Assertion is incorrect, reason is correct.
41. Which one of the following is an amine hormone ? 47. Glucose on prolonged heating with HI gives :
(a) Thyroxine (b) Oxypurin [BITSAT 2017, A] [JEE M 2018, S]
(c) Insulin (d) Progesterone (a) n-Hexane (b) 1- Hexene
42. Which has glycosidic linkage? [BITSAT 2017, S] (c) Hexanoic acid (d) 6-iodohexanal
(a) amylopectin (b) amylase 48. The predominant form of histamine present in human blood
(c) cellulose (d) all of these is (pKa, Histidine – 6.0) [JEE M 2018, S]
43. The difference between amylose and amylopectin is H
H N
[NEET 2018, C] N +
(a) (b) +
(a) Amylopectin has 1 ® 4 a-linkage and 1 ® 6 a-linkage N
N H
(b) Amylose has 1 ® 4 a-linkage and 1® 6 b-linkage
(c) Amylose is made up of glucose and galactose
H H
(d) Amylopectin has 1 ® 4 a-linkage and 1® 6 b-linkage N N +
44. Which of the following compounds can form a zwitterion? (c) + (d)
N N
[NEET 2018, S] H
BIOMOLECULES 411

Exercise 3 : Try If You Can

5 (CH 3CO)2 O (a) The OH’s of sugars are more acidic than that of a
1. D-(+)-Glucose ¾¾¾¾¾® D-(+)-Glucose pentaacetate typical alcohol.
Which statement is true about glucose pentaacetate ? (b) The OH’s of sugars are less acidic than that of a typical
(a) It will react with phenylhydrazine but not with Tollens’ alcohol.
reagent. (c) Both have similar acidic character.
(b) It will react with Tollens’ reagent but not with (d) The OH’s of sugars are neutral while that of an alcohol
phenylhydrazine. is acidic.
6. Which of the following statement(s) is (are) true ?
(c) It will react with both of the above mentioned (i) All amino acids contain one chiral center.
reagents. (ii) Some amino acids contain one, while some contain
(d) It will react neither with phenylhydrazine nor with more chiral center or even no chiral center.
Tollens’ reagent. (iii) All amino acids found in proteins have L
configuration.
(iv) All amino acids found in proteins have 1° amino
group.
2. (a) (ii), (iii) & (iv) (b) (ii) & (iii)
(c) (i), (iii) & (iv) (d) (i) & (iv)
7. Which of the nitrogen of histidine is first protonated ?

(a) a (b) b
(c) both (d) None.
8. Histidine, a heterocyclic amino acid has following structure
at pH < 1.82,

Compounds I and II may be grouped as

(a) diastereomers (b) epimers
(c) C–2 epimers (d) all of the three.
at pH > 1.82 it should have which structure ?
3. Which of the following evolves carbon dioxide, on
oxidation with periodate ?
CH 2OH
(a)
CHO
½ ½
CHOH CO
(a) ½ (b) ½
CHOH CHOH
½ ½ (b)
CH 2OH CH 2OH

(c) Both (d) None

4. What will happen when D-(+)-glucose is treated with
methanolic –HCl followed by Tollens’ reagent? (c)
(a) A black ppt. will be formed
(b) A red ppt. will be formed
(c) A green colour will appear
(d) No characteristic colour or ppt. will be formed.
5. Which is true about the acidic character of hydroxyl groups (d)
of sugars and hydroxyl group of an alcohol?
 EBD_7374
412 CHEMISTRY

9. An electric current is passed through an aqueous solution (a) CH3COOH + CH3COCOOH

(buffered at pH = 6.0) of alanine (pI = 6.0) and ariginine (b) CH3COCOOH + CH3CHO
(pI = 10.2). The two amino acids can be separated because (c) 2 CH3COOH + HCOOH
(a) alanine migrates to anode, and arginine to cathode. (d) no reaction
(b) alanine migrates to cathode, and arginine to anode.
13. An optically pure compound A, gave an [a]25
D = +30°
,
(c) alanine does not migrate, while arginine migrates to
cathode. while a mixture of A and its enantiomer B, gave
(d) alanine does not migrate, while arginine migrates to [a]25
D = +15° . The ratio of A to B in the mixture is
anode.
(a) 1 to 3 (b) 3 to 1
10. In the following series of reactions, compound Z can be
(c) 1 to 2 (d) 2 to 1
H2 (catayst) +
Z + NH3 ¾¾¾¾¾® CH3CH ( N H3)COO– +
(a) CH3CHO (b) CH3COCH3 N H3
|
(c) CH3COCOOH (d) None of these
14. Increase in pH of the solution converts RCHCOOH to
11. a-Amino acids are +
(a) acidic due to –COOH group and basic due to –NH2 NH 2 N H3
group | |
(b) acidic due to – NH3+ group and basic due to – COO– (a) RCHCOOH (b) RCHCOO-
group. (c) Both (d) None
(c) neither acidic nor basic. 15. Glucose-D has a great tendency to be converted into cyclic
(d) none is true. isomer. Which two carbon atoms get joined through ‘O’ to
12. Identify the structures of products A and B in the following form this hemiacetal ?
reaction (a) C1 and C4 (b) C1 and C5
CH 3 COCHOHCOCH 3 ¾¾ ¾ ¾ ¾
Periodic acid
¾® A + B (c) C1 and C6 (d) C2 and C6

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (b) 13 (b) 25 (b) 37 (d) 49 (b) 61 (b) 73 (a) 85 (a) 97 (d) 109 (b)
2 (b) 14 (c) 26 (a) 38 (a) 50 (d) 62 (c) 74 (c) 86 (d) 98 (a) 110 (a)
3 (d) 15 (a) 27 (c) 39 (b) 51 (d) 63 (a) 75 (a) 87 (c) 99 (b) 111 (d)
4 (d) 16 (b) 28 (b) 40 (d) 52 (c) 64 (d) 76 (c) 88 (c) 100 (a) 112 (a)
5 (b) 17 (d) 29 (b) 41 (c) 53 (c) 65 (d) 77 (a) 89 (d) 101 (d) 113 (a)
6 (a) 18 (b) 30 (c) 42 (a) 54 (c) 66 (a) 78 (c) 90 (b) 102 (a) 114 (d)
7 (a) 19 (d) 31 (a) 43 (c) 55 (b) 67 (b) 79 (a) 91 (a) 103 (c) 115 (c)
8 (d) 20 (b) 32 (c) 44 (b) 56 (b) 68 (b) 80 (b) 92 (b) 104 (d) 116 (d)
9 (d) 21 (b) 33 (d) 45 (d) 57 (c) 69 (d) 81 (b) 93 (c) 105 (c) 117 (d)
10 (c) 22 (b) 34 (c) 46 (d) 58 (b) 70 (c) 82 (b) 94 (b) 106 (a) 118 (c)
11 (b) 23 (c) 35 (c) 47 (d) 59 (a) 71 (b) 83 (d) 95 (b) 107 (a) 119 (b)
12 (c) 24 (b) 36 (c) 48 (c) 60 (a) 72 (b) 84 (b) 96 (c) 108 (b) 120 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (b) 6 (b) 11 (a) 16 (c) 21 (c) 26 (c) 31 (c) 36 (d) 41 (a) 46 (c)
2 (d) 7 (b) 12 (c) 17 (a) 22 (b) 27 (c) 32 (b) 37 (c) 42 (d) 47 (a)
3 (c) 8 (a) 13 (d) 18 (c) 23 (a) 28 (a) 33 (c) 38 (c) 43 (a) 48 (d)
4 (c) 9 (b) 14 (d) 19 (c) 24 (a) 29 (b) 34 (d) 39 (c) 44 (c)
5 (c) 10 (c) 15 (a) 20 (d) 25 (c) 30 (d) 35 (a) 40 (a) 45 (a)
Exercise 3 : Try If You Can
1 (d) 3 (b) 5 (a) 7 (b) 9 (c) 11 (b) 13 (b) 15 (b)
2 (d) 4 (d) 6 (b) 8 (a) 10 (c) 12 (c) 14 (b)
 29 Chapter
POLYMERS

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Formation of polymers,
AIIMS 2 classification of 3.4/5 6.9
JEE Main 2 polymers
BITSAT 2
 EBD_7374
414 CHEMISTRY
POLYMERS 415
 EBD_7374
416 CHEMISTRY

Exercise 1 : Topic-wise MCQs

(a) thermoplastic (b) thermosetting plastic

Topic 1: Classification of Polymers
(c) Both (a) and (b) (d) None of these
1. Which is not true about polymers? 14. Which of the following statements is not correct for fibres?
(a) Polymers do not carry any charge (a) Fibres possess high tensile strength and high modulus.
(b) Polymers have high viscosity (b) Fibres impart crystalline nature.
(c) Polymers scatter light (c) Characteristic features of fibres are due to strong
(d) Polymers have low molecular weight intermolecular forces like hydrogen bonding.
2. Which of the following belongs to the class of natural (d) All are correct.
polymers? 15. Which of the following can be repeatedly soften on heating?
(a) Proteins (b) Cellulose (i) Polystyrene (ii) Melamine
(c) Rubber (d) All of these (iii) Polyesters (iv) Polyethylene
3. Which of the following natural products is not a polymer? (v) Neoprene
(a) DNA (b) Cellulose (a) (i) and (iii) (b) (i) and (iv)
(c) ATP (d) Insulin (c) (iii), (iv) and (v) (d) (ii) and (iv)
4. Rayon is : 16. Which of the following is a cross linked polymer?
(a) synthetic plastic (b) natural rubber (a) PVC (b) Bakelite
(c) natural silk (d) artificial silk (c) Polyethylene (d) Rubber
5. Protein is a polymer of:
17. Fibres that have good resistance to stains, chemicals,
(a) glucose (b) terephthalic acid
insects and fungi is
(c) amino acids (d) None of these
(a) Acrylic (b) Terylene
6. Natural silk is a
(c) Nylon (d) All of these
(a) polyester (b) polyamide
(c) polyacid (d) polysaccharide 18. Match the columns.
7. Which of the following is/are a semisynthetic polymers? Column-I Column-II
(a) Cellulose acetate (b) Polyvinyl chloride (A) Linear polymer (p) Melamine
(c) Cellulose nitrate (d) Both (a) and (c) (B) Semisynthetic polymer (q) Polyvinyl chloride
8. Polymer formation from monomers starts by (C) Branched chain polymer (r) LDPE
(a) condensation reaction between monomers (D) Network polymer (s) Cellulose nitrate
(b) coordinate reaction between monomers (a) A– (s), B – (q), C – (r), D – (p)
(c) conversion of monomer to monomer ions by protons (b) A– (q), B – (s), C – (r), D – (p)
(d) hydrolysis of monomers. (c) A– (q), B – (r), C – (s), D – (p)
9. On the basis of mode of formation, polymers can be (d) A– (q), B – (s), C – (p), D – (r)
classified? Topic 2: Types of Polymerisation
(a) as addition polymers only
(b) as condensation polymers only 19. Low density polythene is prepared by
(c) as copolymers (a) Free radical polymerisation
(d) both as addition and condensation polymers (b) Cationic polymerisation
10. In addition polymer monomer used is (c) Anionic polymerisation
(a) unsaturated compounds (d) Ziegler-Natta polymerisation
(b) saturated compounds 20. The monomer of teflon is
(c) bifunctional saturated compounds (a) CHF == CH2 (b) CF2 == CF2
(d) trifunctional saturated compounds (c) CHC1 == CHCl (d) CHF == CHC1
11. Which is/are true for elastomers? 21. Which of the following does not undergo addition
(a) These are synthetic polymers possessing elasticity. polymerization?
(b) These possess very weak intramolecular forces or (a) Vinylchloride
attractions between polymer chains. (b) Butadiene
(c) Vulcanised rubber is an example of elastomer. (c) Styrene
(d) All of the above (d) All of the above undergoes addition polymerizations
12. Among the following polymers the strongest molecular 22. Which of the following statements is not true about low
forces are present in
density polythene?
(a) elastomers (b) fibres
(a) Tough
(c) thermoplastics (d) thermosetting polymers
(b) Hard
13. Three dimensional molecular structure with cross links are
(c) Poor conductor of electricity
formed in the case of a
(d) Highly branched structure
POLYMERS 417

23. The monomer(s) used in the preparation of orlon, a substitute (a) addition polymerisation (b) copolymerisation
for wool is/are (c) chain polymerisation (d) homo polymerisation
(a) caprolactam (b) styrene and 1, 3-butadiene 36. Which one of the following statement is not true?
(c) tetrafluoroethene (d) acrylonitrile (a) In vulcanization the formation of sulphur bridges
24. Which of the following polymer is used for manufacturing between different chains make rubber harder and
of buckets, dustbins, pipes etc ? stronger.
(a) Low density polythene(b) High density polythene (b) Natural rubber has the trans -configuration at every
(c) Teflon (d) Polyacrylonitrile double bond.
25. Which of the following catalyst is used in preparation of (c) Buna-S is a copolymer of butadiene and styrene.
high density polythene ? (d) Natural rubber is a 1, 4 - polymer of isoprene.
(a) Peroxide catalyst (b) Ziegler - Natta catalyst 37. Which of the following is not the property of natural rubber?
(c) Wilkinson’s catalyst (d) Pd - catalyst (a) Low tensile strength
26. Which of the following statements is false? (b) High water absorption capacity
(a) Artificial silk is derived from cellulose. (c) Soft and sticky
(b) Nylon-66 is an example of elastomer. (d) High elasticity
(c) The repeat unit in natural rubber is isoprene. 38. The process involving heating of rubber with sulphur is
(d) Both starch and cellulose are polymers of glucose. called
27. Melamine plastic crockery is a copolymer of: (a) Galvanisation (b) Vulcanization
(a) HCHO and melamine (b) HCHO and ethylene (c) Bessemerisation (d) Sulphonation
39. Which of the following are examples of synthetic rubber?
(c) melamine and ethylene (d) None of these
(i) Polychloroprene (ii) polyacrylonitrile
28. Caprolactam polymerises to give
(iii) Buna-N (iv) cis-polyisoprene
(a) terylene (b) teflon (c) glyptal (d) nylon-6
(a) (i) and (iii) (b) (i) and (ii)
29. Interparticle forces present in nylon-6, 6 are
(c) (iii) and (iv) (d) (ii) and (iii)
(a) van der waal’s
40. Buna-N synthetic rubber is a copolymer of :
(b) hydrogen bonding
(a) H2C = CH – CH = CH2 and H5C6 – CH = CH2
(c) dipole-dipole interactions
(b) H2C = CH – CN and H2C = CH – CH = CH2
(d) None of these
(c) H2C = CH – CN and H 2 C = CH – C = CH 2
30. Acetic acid is added in the preparation of nylon-6 to |
(a) initiate polymerisation Cl CH3
(b) avoid polymerisation at first step |
(c) avoid oxidation (d) H 2 C = CH – C = CH 2 and H 2C = CH – CH = CH 2
(d) removal of water 41. Which of the following is not a copolymer?
31. Which of the following polymer is used for making (a) Buna–S (b) Baketite
phonograph records ? (c) Neoprene (d) Dacron
(a) Bakelite (b) Dacron (c) Teflon (d) PVC 42. Which of the following polymer is formed on reaction of
32. Dacron is a – 1,3–butadiene and acrylonitrile?
(a) crease resistant (a) Buna–S (b) Buna – N
(b) polyamide (c) Neoprene (d) Dacron
(c) addition polymer 43. Two condensation polymers are made
(d) polymer of ethylene glycol and phthalic acid (1) ethylene diamine + ethane–1, 2– dicarboxylic acid
33. The monomeric units of terylene are glycol and which of the (2) trimethylenediamine + ethane–1, 2– dicarboxylic acid
following OH if both polymers of same molecular weight are obtained
OH then which of the following statements is/are correct ?
(i) Polymer (1) is found to melt at lower temperature.
(a) (b)
(ii) Polymer (2) is found to melt at lower temperature.
OH OH (iii) H-bonding is major factor.
HO (a) (i), (ii) and (iii) (b) Only (ii)
(c) HOOC COOH (d) OH (c) (i) and (iii) (d) (ii) and (iii)
44. Which of the following statements are correct?
HO
(i) A polyamide nylon 6,6 prepared by the condensation
34. Soft drinks and baby feeding bottles are generally made up polymerisation of hexamethylene diamine with adipic
of acid is used in the manufacture of tyre cords.
(a) Polystyrene (b) Polyurethane (ii) Terylene is crease resistant and is blended with cotton
(c) Polyurea (d) Polyamide and wool fibres for various applications.
35. Polymerisation in which two or more chemically different (iii) Condensation reaction of phenol and formaldehyde
monomers take part is called: to form novolac can be catalysed either by acid or base.
 EBD_7374
418 CHEMISTRY

(iv) Melamine formaldehyde polymer is mainly used in the (a) A – (r), B – (p), C – (q), D – (t), E – (s)
manufacture of electrical switches. (b) A – (s), B – (q), C – (t), D – (r), E – (p)
(a) (i), (ii) and (iii) (b) (ii), (iii) and (iv) (c) A – (t), B – (s), C – (p), D – (q), E – (r)
(c) (iii) and (iv) (d) (ii) and (iii) (d) A – (s), B – (t), C – (r), D – (q), E – (p)
45. Which of the following statements are correct? 49. Match the columns
(i) Buna–N being resistant to the action of petrol, Column-I Column-II
lubricating oil and organic solvents is used in making (A) Polymer of styrene (p) used in making handles
of utensils and computer
oil seals.
discs
(ii) Biodegradable polymers are manufactured because of (B) Polymer of ethylene (q) used as an insulator
low chemical resistance, strength and durability of glycol and phthalic acid
conventional polymers. (C) Polymer of phenol (r) used in making paints
(iii) PHBV is a copolymer used in the manufacture of and formaldehyde and lacquers.
orthopaedic devices. (D) Polymer of vinyl (s) used in manufacture of
(iv) Nylon 2–nylon 6 is a biodegradable polymer. chloride rain coats and flooring.
(a) (i), (ii) and (iii) (b) (ii), (iii) and (iv) (a) A – (q), B – (r), C– (p), D – (s)
(c) (i), (iii) and (iv) (d) (i) and (iv) (b) A – (r), B – (q), C– (p), D – (s)
46. Match the columns. (c) A – (q), B – (p), C– (r), D – (s)
Column-I Column-II (d) A – (q), B – (r), C– (s), D – (p)
(A) Highly branched (p) Teflon 50. The polymer containing strong intermolecular forces e.g.
chemically inert polymer hydrogen bonding, is
(a) teflon (b) nylon 6, 6
used in the insulation of
(c) polystyrene (d) natural rubber
electric wires. 51. Assertion : Olefinic monomers undergo addition
(B) Linear polymer (q) Polyacrylonitrile polymerisation.
prepared in presence of Reason : Polymerisation of vinylchloride is initiated by
Al(C2H5)3 and TiCl4. peroxides/ persulphates.
(C) Corrosion resistant (r) HDPE (a) Assertion is correct, reason is correct; reason is a
polymer used in correct explanation for assertion.
manufacture of non–stick (b) Assertion is correct, reason is correct; reason is not a
surface coated utensils. correct explanation for assertion.
(D) Addition polymer (s) LDPE (c) Assertion is correct, reason is incorrect.
used as a substitute for wool. (d) Assertion is incorrect, reason is correct.
(a) A–(s), B–(r), C–(q), D–(p) 52. Among cellulose, poly (vinyl chloride), nylon and natural
(b) A–(s), B–(p), C–(r), D–(q) rubber, the polymer in which the intermolecular force of
(c) A–(s), B–(r), C–(p), D–(q) attraction is weakest is
(d) A–(r), B–(s), C–(p), D–(q) (a) nylon (b) poly (vinyl chloride)
(c) cellulose (d) natural rubber
47. Match the columns
53. Assertion : Teflon has high thermal stability and chemical
Column-I Column-II
inertness.
(A) Polyester of glycol and (p) Novalac Reason : Teflon is a thermoplastic.
phthalic acid (a) Assertion is correct, reason is correct; reason is a
(B) Copolymer of 1, 3-butadiene (q) Glyptal correct explanation for assertion.
and styrene (b) Assertion is correct, reason is correct; reason is not a
(C) Phenol and formaldehyde (r) Buna-S correct explanation for assertion.
resin (c) Assertion is correct, reason is incorrect.
(D) Polyester of glycol and (s) Buna-N (d) Assertion is incorrect, reason is correct.
terephthalic acid 54. When condensation product of hexamethylenediamine and
(E) Copolymer of 1, 3-butadiene (t) Dacron adipic acid is heated to 525K in an atmosphere of nitrogen
and acrylonitrile for about 4-5 hours, the product obtained is
(a) A – (q), B – (s), C – (p), D – (t), E – (r) (a) solid polymer of nylon 6, 6
(b) A – (q), B – (r), C – (p), D – (t), E – (s) (b) liquid polymer of nylon 6, 6
(c) A – (r), B – (p), C – (t), D – (s), E – (q) (c) gaseous polymer of nylon 6, 6
(d) A – (p), B – (s), C – (q), D – (t), E – (r) (d) liquid polymer of nylon-6
48. Match the polymers given in Column-I with their chemical 55. Assertion : Bakelite is a thermosetting polymer.
names given in Column-II Reason : Bakelite can be melted again and again without
Column-I Column-II any change.
(a) Assertion is correct, reason is correct; reason is a
(A) Nylon 6 (p) Polyvinyl chloride
correct explanation for assertion.
(B) PVC (q) Polyacrylonitrile (b) Assertion is correct, reason is correct; reason is not a
(C) Acralin (r) Polycaprolactam correct explanation for assertion.
(D) Natural rubber (s) Low density Polythene (c) Assertion is correct, reason is incorrect.
(E) LDPE (t) cis-Polyisoprene (d) Assertion is incorrect, reason is correct.
POLYMERS 419

56. Identify A, B and C in the following sequence of reactions 59. Which of the following is not correctly matched?
O O O O O
C6H5–C–O—O–C–C6H5 ® 2 C6H5–C–O ® 2A (a) Terylene –OCH2–CH2–C– –C –
A + CH2 = CH2 ¾¾
®B n

B + nCH2 = CH2 ¾¾
®C (b) Neoprene — CH 2 — C = CH — CH 2 —
C + C ¾¾ ® C6H5–(CH2– CH2)n—CH2– CH2 – CH2
Cl
CH2 –(CH2–CH2)n– C6H5 n
· ·
(a) A = C 6H5, B = C6H5 – CH2– CH 2 and O O
· (c) Nylon-6, 6 –NH–(CH2)6–NH–C–(CH2)4–C–O–n
C = C6H5 –(CH2 – CH2)n—CH2 – CH 2
· · CH3
(b) A = C6H5 CO, B = C6H5 – CH2– CH 2 and
· (d) PMMA – CH2–C
C = C6H5 –(CH2–CH2)n—CH2– CH 2 COOCH3 n
· ·
(c) A = C 6H5, B = C6H5 – CH – CH3 and Topic 3: Biodegradable Polymers
·
C = C6H5—(CH2 –CH2)n—CH2 CH 2 60. Which of the following monomers form biodegradable
· · polymers?
(d) A= C 6H5, B=C6H5 –CH2– CH 2 and (a) 3-hydroxybutanoic acid + 3-hydroxypentanoic acid
C = C6H5 –(CH2– CH2)n—C6H5 (b) Glycine + amino caproic acid
57. Assertion : In vulcanisation of rubber, sulphur cross links (c) Ethylene glycol + phthalic acid
are introduced. (d) Both (a) and (b)
Reason : Vulcanisation is a free radical initiated chain 61. The polymer which undergoes environment degradation
reaction. by microoganism is known as
(a) Assertion is correct, reason is correct; reason is a (a) chain-growth polymer
correct explanation for assertion. (b) chain step polymer
(b) Assertion is correct, reason is correct; reason is not a (c) biodegradable polymer
correct explanation for assertion. (d) non-biodegradable polymer
(c) Assertion is correct, reason is incorrect. 62. Assertion : Most of the synthetic polymers are not
(d) Assertion is incorrect, reason is correct. biodegradable.
58. Which one of the following monomers gives the polymer Reason : Polymerisation process induces toxic character in
neoprene on polymerization ? organic molecules.
(a) CF2 = CF2 (a) Assertion is correct, reason is correct; reason is a
(b) CH2 = CHCl correct explanation for assertion.
(c) CCl2 = CCl2
(b) Assertion is correct, reason is correct; reason is not a
Cl correct explanation for assertion.
|
(d) CH 2 = C — CH = CH 2
(c) Assertion is correct, reason is incorrect.
(d) Assertion is incorrect, reason is correct.

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs 4. Which of the following polymer is biodegradable?
1. Which of the following polymers of glucose is stored by (a) –( CH2 C = CH CH2 n
–(
animals?
(a) Cellulose (b) Amylose CN
(c) Amylopectin (d) Glycogen Cl
2. Which of the following is not a semisynthetic polymer? (b) –( CH2 CH = CH CH2 CH2 CH –)n
(a) cis-polyisoprene (b) Cellulose nitrate
(c) Cellulose acetate (d) Vulcanised rubber
3. The commercial name of polyacrylonitrile is ....... . (c) –( O CH CH2 C O CH CH2 C –)n
(a) dacron (b) orlon (acrilan)
(c) PVC (d) bakelite CH3 O CH2CH3 O
 EBD_7374
420 CHEMISTRY

H H O O H H O O
| | || ||
(d) –( N (CH2)6 N C (CH2)4 C –)n (c) ( N - (CH 2 )6 - N - C - (CH 2 ) 4 - C ) n
5. In which of the following polymers ethylene glycol is one OH OH
of the monomer units? CH2 CH2
(d)
(a) (OCH2 CH 2 OOC CO )n
n
10. Which of the following organic compounds polymerizes to
form the polyester Dacron? [AIPMT 2014, S]
(b) ( CH 2 — CH 2 )n (a) Propylene and para HO—(C6H4)— OH
(b) Benzoic acid and ethanol
(c) Terephthalic acid and ethylene glycol
(CH 2 CH= CH CH 2 CH CH 2 )n (d) Benzoic acid and para HO–(C6H4)—OH
(c)
11. Which compound/set of compounds is used in the
manufacture of nylon-6,6? [AIIMS 2014, S]
(d) (O CH CH 2 C O CH CH 2 C )n (a) HOOC(CH2)4 COOH + H2N(CH2)6NH2
| || | ||
CH3 O O (b) CH2 = CH–C(CH) = CH2
CH2CH 3
(c) CH2 = CH2
6. Which of the following statements is not true about low
density polyethene?
(a) Tough (d) HOOC COOH + HOCH2 – CH2OH
(b) Hard
(c) Poor conductor of electricity 12. Which one is classified as a condensation polymer?
(d) Highly branched structure [JEE M 2014, S]
CH3 CH3 (a) Dacron (b) Neoprene
| | (c) Teflon (d) Acrylonitrile
7. (O C CH2 C )n is a polymer having monomer
| | 13. Which one of the following monomers gives the polymer
CH3 CH3 neoprene on polymerization ? [BITSAT 2014, S]
units ......... . (a) CF2 = CF2 (b) CH2 = CHCl
Cl
(a) (b) |
(c) CCl2 = CCl2 (d) CH 2 = C — CH = CH 2
H 14. Biodegradable polymer which can be produced from glycine
(c) (d) and aminocaproic acid is : [AIPMT 2015, A]
H (a) PHBV (b) Buna - N
8. Which of the following polymer can be formed by using (c) Nylon 6, 6 (d) Nylon 2- nylon 6
the following monomer unit? 15. Caprolactum is used for the manufacture of :
H [AIPMT 2015 RS, S]
|
N O (a) Nylon - 6 (b) Teflon
H2C C (c) Terylene (d) Nylon - 6,6
||

16. Assertion : Bakelite is a thermosetting polymer.

H2C CH2 Reason : Bakelite can be melted again and again without
any change. [AIIMS 2015, 2016, C]
H2C CH2 (a) If both Assertion and Reason are correct and Reason
(a) Nylon-6, 6 (b) Nylon-2-nylon-6 is the correct explanation of Assertion.
(c) Melamine polymer (d) Nylon-6 (b) If both Assertion and Reason are correct, but Reason
is not the correct explanation of Assertion.
Past Year MCQs (c) If Assertion is correct but Reason is incorrect.
9. Which one of the following is an example of a thermosetting (d) If both the Assertion and Reason are incorrect.
polymer? [AIPMT 2014, S] 17. Which polymer is used in the manufacture of paints and
(a) ( CH 2 - C = CH - CH 2 ) n lacquers ? [JEE M 2015, A]
| (a) Polypropene (b) Polyvinyl chloride
Cl (c) Bakelite (d) Glyptal
(b) ( CH 2 - CH ) n 18. Polymer used in bullet proof glass is [BITSAT 2015, A]
|
Cl (a) Lexan (b) PMMA (c) Nomex (d) Kevlar
POLYMERS 421

19. Natural rubber has [NEET 2016, C] (a) If both Assertion and Reason are correct and Reason
(a) all cis-configuration is the correct explanation of Assertion.
(b) all trans-configuration (b) If both Assertion and Reason are correct, but Reason
(c) alternate cis-and trans-configuration is not the correct explanation of Assertion.
(d) random cis-and trans-configuration (c) If Assertion is correct but Reason is incorrect.
20. The repeating unit present in Nylon 6 is [AIIMS 2016, S] (d) If both the Assertion and Reason are incorrect.
(a) — [NH(CH2)6NHCO(CH2)4CO] — 25. The formation of which of the following polymers involves
(b) — [CO(CH2)5NH] — hydrolysis reaction? [JEE M 2017, A]
(c) — [CO (CH2)6NH] — (a) Nylon 6 (b) Bakelite
(d) — [CO (CH2)4NH] — (c) Nylon 6, 6 (d) Terylene
21. Which of the following statements about low density 26. Which of the following can be repeatedly soften on heating?
polythene is FALSE? [JEE M 2016, C] [BITSAT 2017, S]
(a) Its synthesis requires dioxygen or a peroxide initiator (i) Polystyrene (ii) Melamine
as a catalyst. (iii) Polyesters (iv) Polyethylene
(b) It is used in the manufacture of buckets, dustbins etc. (v) Neoprene
(c) Its synthesis requires high pressure. (a) (i) and (iii) (b) (i) and (iv)
(d) It is a poor conductor of electricity. (c) (iii), (iv) and (v) (d) (ii) and (iv)
22. Formation of polyethylene from calcium carbide takes place 27. Regarding cross-linked or network polymers, which of the
as follows [BITSAT 2016, A] following statements is incorrect? [NEET 2018, C]
CaC 2 + 2H 2 O ¾
¾® Ca (OH ) 2 + C 2 H 2 (a) They contain covalent bonds between various linear
polymer chains.
C2H2 + H2 ¾
¾® C 2 H 4 (b) They are formed from bi- and tri-functional monomers.
nC 2 H 4 ¾
¾® ( - CH 2 - CH 2 -) n (c) They contain strong covalents bonds in their polymer
The amount of polyethylene obtained from 64.1 kg of CaC2 is chains.
(a) 7 kg (b) 14 kg (c) 21 kg (d) 28 kg (d) Examples are bakelite and melamine.
23. Which one of the following is not a condensation polymer? 28. Assertion : Bakelite is formed when novolac is heated with
[AIIMS 2017, S] formaldehyde which is a thermosetting polymer.
(a) Melamine (b) Glyptal Reason : Bakelite is infusible solid mass. [AIIMS 2018, S]
(c) Dacron (d) Neoprene (a) If both assertion and reason are true and reason is the
24. Assertion : In vulcanisation of rubber, sulphur cross links correct explanation of assertion.
are introduced. (b) If both assertion and reason are true but reason is not
Reason : Vulcanisation is a free radical initiated chain the correct explanation of assertion.
reaction. [AIIMS 2017, C] (c) If assertion is true but reason is false.
(d) If both assertion and reason are false.

Exercise 3 : Try If You Can

1. [NH(CH 2 )6 NHCO(CH 2 )4 CO]n is a CH3
(a) addition polymer (b) thermosetting polymer
(c) homopolymer (d) copolymer (a) (– CH2 – C = CH – CH2 –) n
2. Which compound/set of compounds is used in the manufacture (b) (– CH2 – CH = CH – CH2 – CH – CH2 –) n
of nylon-6,6?
(a) HOOC(CH2)4COOH + H2N(CH2)6NH2 C6H5
(b) CH2 = CH–C(CH3) = CH2 (c) (– CH 2 – CH = CH – C H 2 – CH(CN) – CH 2 –) n
(c) CH2 = CH2 (d) (– C H2 – (Cl)C = CH – C H2 –) n
4. Acrilan is a hard, horny and a high melting material. Which
(d) HOOC COOH of the following represents its structure?
+ HOCH2 – CH2 OH (a) — CH2 — CH —n (b) — CH2 — CH —n
—

3. Structure of some important polymers are given. Which one

represents buna-S? Cl CN
 EBD_7374
422 CHEMISTRY

CH3 9. The polymer used in making synthetic hair wigs is made up of

(a) CH2 = CHCl (b) CH2 = CHCOOCH3

—
(c) — CH2 — CH —n (d) — CH2 — CH —n (c) C6H5CH = CH2 (d) CH2 = CH – CH=CH2

—
10. In addition polymer monomer used is
COOCH3 COOC2H5
(a) unsaturated compounds
5. The monomer of the polymer; (b) saturated compounds
CH3 CH3 (c) bifunctional saturated compounds
| (d) trifunctional saturated compounds
ÚÚÚÚÚCH 2 - C - CH 2- C + is
| 11. Which of the following statements is not correct for fibres?
CH3 CH3 (a) Fibres possess high tensile strength and high modulus.
(a) H2C = C(CH3)2 (b) CH3CH = CHCH3 (b) Fibres impart crystalline nature.
(c) CH3CH = CH2 (d) (CH3)2C = C(CH3)2 (c) Characteristic features of fibres are due to strong
6. Head-to-tail addition takes place in chain-growth intermolecular forces like hydrogen bonding.
polymerisation, when monomer is (d) All are correct.
(a) CH2 = CHPh (b) CH 2 = CH - CH = CH 2 12. Perlon is
(a) Rubber (b) Nylon-6 (c) Terylene (d) Orlon
(c) CH 2 < C , COCH3 (d) CH 2 < CH , C º N 13. Which one of the following is a chain growth polyme?
| P (a) Nucleic acid (b) Polystyrene
CH3 O (c) Protein (d) Starch
7. Select the correct statement. 14. Nylon 6,6 is a polyamide obtained by the reaction of
(a) Vinyon is a copolymer of vinyl chloride and vinyl (a) COOH(CH2)4 COOH + NH2C6H4NH2– (p)
acetate. (b) COOH(CH2)4 COOH + NH2 (CH2)6 NH2
(b) Saran is a copolymer of vinyl chloride and vinylidine (c) COOH (CH2)6 COOH + NH2 (CH2)4 NH2
chloride.
(d) COOHC6H4 COOH– (p) + NH2 (CH2)6 NH2
(c) Butyl rubber is a copolymer of isobutylene and
isoprene. CH3
(d) All of the above are correct.
15. Monomer of — C — CH2 — is
8. Which of the following has been used in the manufacture of
non-inflammable photographic films? CH3 n
(a) Cellulose nitrate (b) Cellulose xanthate (a) 2-methylpropene (b) styrene
(c) Cellulose perchlorate (d) Cellulose acetate (c) propylene (d) ethene

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (d) 8 (a) 15 (b) 22 (b) 29 (b) 36 (b) 43 (d) 50 (b) 57 (b)
2 (d) 9 (d) 16 (b) 23 (d) 30 (b) 37 (d) 44 (d) 51 (b) 58 (d)
3 (c) 10 (a) 17 (a) 24 (b) 31 (a) 38 (b) 45 (c) 52 (d) 59 (a)
4 (d) 11 (d) 18 (b) 25 (b) 32 (a) 39 (a) 46 (c) 53 (b) 60 (d)
5 (c) 12 (d) 19 (a) 26 (b) 33 (c) 40 (b) 47 (b) 54 (b) 61 (c)
6 (b) 13 (b) 20 (b) 27 (a) 34 (a) 41 (c) 48 (a) 55 (c) 62 (d)
7 (d) 14 (d) 21 (d) 28 (d) 35 (b) 42 (b) 49 (a) 56 (a)
Exercise 2 : Exemplar & Past Year MCQs
1 (d) 4 (c) 7 (a) 10 (c) 13 (d) 16 (c) 19 (a) 22 (d) 25 (a) 28 (b)
2 (a) 5 (a) 8 (d) 11 (a) 14 (d) 17 (d) 20 (b) 23 (d) 26 (b)
3 (b) 6 (d) 9 (d) 12 (a) 15 (a) 18 (b) 21 (b) 24 (b) 27 (c)
Exercise 3 : Try If You Can
1 (d) 3 (b) 5 (a) 7 (d) 9 (a) 11 (d) 13 (b) 15 (a)
2 (a) 4 (b) 6 (a) 8 (d) 10 (a) 12 (b) 14 (b)
 30 Chapter
CHEMISTRY IN EVERYDAY
LIFE

Trend
Analysis of NEET and AIIMS (Year 2010-2018)

4
Number of Questions

3 AIPMT/NEET

AIIMS
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Trend
Analysis of JEE Main and BITSAT (Year 2010-2018)

4
JEE Main
Number of Questions

3
BITSAT
2

0
2010 2011 2012 2013 2014 2015 2016 2017 2018
Year

Chapter Utility Score (CUS)

Exam Weightage Important Concepts Difficulty Level CUS (Out of 10)
NEET 2 Therapeutic action of different
AIIMS 3 drugs, Cleansing action of soaps 1/5 3
JEE Main 2 and detergents
BITSAT 2
 EBD_7374
424 CHEMISTRY
CHEMISTRY IN EVERYDAY LIFE 425
 EBD_7374
426 CHEMISTRY

Exercise 1 : Topic-wise MCQs

(ii) Drugs that mimic – Antagonists

Topic 1 : Drugs and their Classification, Drug-Target Interaction
the natural messenger by
1. The use of chemicals for treatment of diseases is called as switching on the receptor.
(a) isothermotherapy (b) angiotherapy (iii) Drugs that bind to – Agonists
(c) physiotherapy (d) chemotherapy the receptor site and inhibit
2. Which of the following method of classification of drugs is its natural function.
useful for medicinal chemists? (a) (ii) only (b) (iii) only
(a) On the basis of molecular targets. (c) (i) and (iii) (d) (ii) and (iii)
(b) On the basis of chemical structure.
(c) On the basis of drug action. Topic 2 : Therapeutic Action of Different Classes of Drugs
(d) All of these.
3. Which of the following statements is true about the catalytic H
N
activity of enzyme?
7. The drug is an
(a) Enzyme holds the substrate for a biochemical reaction.
(b) Enzyme binds substrate through a variety of N CH2
interactions such as ionic bonding, hydrogen bonding,
van der Waal’s interaction or dipole – dipole CH2 NH2
interaction. (a) Antacid (b) Analgesic
(c) Enzyme provides functional group that will attack the (c) Antimicrobial (d) Antiseptic
substrate and carry out biochemical reaction. 8. Which one of the following is employed as a tranquilizer?
(d) All of the above. (a) Naproxen (b) Tetracycline
4. Which of the following statements are incorrect about (c) Chlorpheninamine (d) Equanil
receptor proteins? 9. Terfenadine is commonly used as a/an
(i) Majority of receptor proteins are embedded in the cell (a) tranquilizer (b) antihistamine
membranes. (c) antimicrobial (d) antibiotic
(ii) The active site of receptor proteins opens on the inside 10. Which one of the following is not a tranquilizer?
region of the cell. (a) Equanil (b) Veronal
(iii) Chemical messengers are received at the binding sites (c) Salvarsan (d) Serotonin
of receptor proteins. 11. Tranquillizers are substances used for the treatment of
(iv) Shape of receptor doesn’t change during attachment (a) cancer (b) AIDS
of messenger. (c) mental diseases (d) physical disorders
(a) (i), (ii) and (iii) (b) (ii) and (iv) 12. The drug used as an antidepressant is
(c) (ii), (iii) and (iv) (d) (i) and (iv) (a) Luminol (b) Tofranil
5. Assertion : Non-competitive inhibitor inhibits the catalyic (c) Mescaline (d) Sulphadiazine
activity of enzyme by binding with its active site. 13. Barbituric acid and its derivatives are well known
Reason : Non-competitive inhibitor changes the shape of (a) antipyretics (b) analgesics
the active site in such a way that substrate can’t recognise (c) antiseptics (d) tranquillizers
it. 14. Which of the following is a hypnotic drug?
(a) Assertion is correct, reason is correct; reason is a (a) luminal (b) salol
correct explanation for assertion. (c) catechol (d) chemisol
(b) Assertion is correct, reason is correct; reason is not a 15. Aspirin is
correct explanation for assertion (a) antibiotic (b) antipyretic
(c) Assertion is correct, reason is incorrect (c) sedative (d) psychedelic
(d) Assertion is incorrect, reason is correct. 16. Sulpha drugs are used for
6. Which of the following is not correctly matched? (a) precipitating bacteria
(i) Proteins that are – Receptors (b) removing bacteria
crucial to body’s (c) decreasing the size of bacteria
communication process. (d) stopping the growth of bacteria
CHEMISTRY IN EVERYDAY LIFE 427

17. Which one among the following is not an analgesic? 30. Bithional is an example of
(a) Ibuprofen (b) Naproxen (a) disinfectant (b) antiseptic
(c) Aspirin (d) Valium (c) antibiotic (d) analgesic
18. Salol can be used as 31. Which of the following is a broad spectrum drug?
(a) antiseptic (b) antipyretic (a) Plasmoquine (b) Chloroquine
(c) analgesic (d) None of these (c) Chloramphenicol (d) D.D.T.
32. Antiseptics and disinfectants either kill or prevent growth
19. Various phenol derivatives, tincture of iodine (2 – 3%) I2
of microorganisms. Identify which of the following
in (water / alcohol) and some dyes like methylene blue are
statements is not true:
(a) antiseptics (b) disinfectants (a) Chlorine and iodine are used as strong disinfectants.
(c) analgesics (d) antipyretics (b) Dilute solutions of boric acid and hydrogen peroxide
20. Streptomycin is effective in the treatment of are strong antiseptics.
(a) tuberculosis (b) malaria (c) Disinfectants harm the living tissues.
(c) typhoid (d) cholera (d) A 0.2% solution of phenol is an antiseptic while 1%
21. An antibiotic with a broad spectrum solution acts as a disinfectant.
33. Novestrol is an
(a) kills the antibodies
(a) antibiotic (b) analgesic
(b) acts on a specific antigen (c) antacid (d) antifertility drug
(c) acts on different antigens 34. Which of the following is an essential component of sleeping
(d) acts on both the antigens and antibodies pills?
22. Which of the following is not an antiseptic drug? (a) Analgesics (b) Tranquilizers
(a) Iodoform (b) Dettol (c) Antihistamines (d) Both (b) and (c)
(c) Gammexane (d) Genatian violet 35. Which type of drugs inhibit the enzymes which catalyse
23. Veronal, a barbiturate drug is used as the degradation of noradrenaline?
(a) anaesthetic (b) sedative (a) Narcotic analgesics (b) Antacids
(c) antiseptic (d) None of these (c) Antidepressants (d) Non–narcotic analgesic.
36. Which of the following is/are example(s) of narcotic
24. A drug effective in the treatment of pneumonia, bronchitis,
analgesics?
etc, is
(a) Morphine (b) Heroin
(a) streptomycin (b) chloramphenicol
(c) Codeine (d) All of these
(c) penicillin (d) sulphaguanidine
37. Which of the following was the first effective treatment
25. Commonly used antiseptic 'Dettol' is a mixture of discovered for syphilis?
(a) o-chlorophenozylenol + terpeneol (a) Penicillin (b) Arsphenamine
(b) o-cresol + terpeneol (c) Chloramphenicol (d) Sulphanilamide
(c) phenol + terpeneol 38. Match the columns
(d) chloroxylenol + terpeneol Column-I Column-II
26. Chloroamphenicol is an : (A) Sodium perborate (p) Disinfectant
(a) antifertility drug (B) Chlorine (q) Antiseptic
(b) antihistaminic (C) Bithional (r) Milk bleaching agent
(c) antiseptic and disinfectant (D) Potassium stearate (s) Soap
(d) antibiotic-broad spectrum (a) A – (p), B – (q), C – (r), D – (s)
27. The drug which is effective in curing malaria is (b) A – (q), B – (r), C – (s), D – (p)
(a) quinine (b) aspirin (c) analgin (d) equanil (c) A – (r), B – (p), C – (q), D – (s)
28. The structure given below is known as (d) A – (s), B – (p), C – (q), D – (r)
39. Match the columns
O Column-I Column-II
P H H S CH3
CH 2 - C - NH (A) Ranitidine (p) Tranquilizer
CH3 (B) Furacine (q) Antibiotic
N COOH
O (C) Phenelzine (r) Antihistamine
H (D) Chloramphenicol (s) Antiseptic
(a) Penicillin F (b) Penicillin G (a) A – (r), B – (s), C – (p), D – (q)
(c) Penicillin K (d) Ampicillin (b) A – (s), B – (p), C – (q), D – (r)
29. Arsenic drugs are mainly used in the treatment of (c) A – (p), B – (q), C – (r), D – (s)
(a) jaundice (b) typhoid (c) syphilis (d) cholera (d) A – (q), B – (r), C – (s), D – (p)
 EBD_7374
428 CHEMISTRY

40. Assertion : Equanil is a tranquilizer. 47. Which of the following is an example of synthetic
Reason : Equanil is used to cure depression and progesterone derivative which is most widely used as
hypertension. antifertility drug?
(a) Assertion is correct, reason is correct; reason is a (a) Norethindrone (b) Novestrol
correct explanation for assertion. (c) Ethynylestradiol (d) All of these
(b) Assertion is correct, reason is correct; reason is not a
correct explanation for assertion Topic 3: Chemicals in Food
(c) Assertion is correct, reason is incorrect 48. Which is correct about saccharin?
(d) Assertion is incorrect, reason is correct. O
41. Assertion : Antiseptics are applied to living tissues.
C
Reason : Iodine is a powerful antiseptic. (a) It is NH
(a) Assertion is correct, reason is correct; reason is a SO2
correct explanation for assertion. (b) It is 600 times sweeter than sugar
(b) Assertion is correct, reason is correct; reason is not a (c) It is used as sweetening agent
correct explanation for assertion (d) All of these
(c) Assertion is correct, reason is incorrect 49. Arrange the following artificial sweeteners in increasing
(d) Assertion is incorrect, reason is correct. order of their sweetness value?
42. Among the following antihistamines, which are antacids (a) Sucralose < Saccharin < Alitame < Aspartame
(b) Aspartame < Saccharin < Sucralose < Alitame
(i) Ranitidine (ii) Brompheniramine
(c) Aspartame < Sucralose < Saccharine < Alitame
(iii) Terfenadine (iv) Cimetidine
(d) Saccharine < Aspartame < Sucralose < Alitame
(a) (i) and (iii) (b) (i), (ii) and (iv) 50. Which of the following artificial sweetener does not provide
(c) (i) and (iv) (d) (ii) and (iii) calories?
43. Select the incorrect statement. (a) Alitame (b) Aspartame
(a) Equanil is used to control depression and hypertension. (c) Sucralose (c) Both (b) and (c)
(b) Mifepristone is a synthetic steroid used as “morning 51. Structuraly biodegradable detergent should contain
after pill”. (a) normal alkyl chain (b) branched alkyl chain
(c) 0.2 percent solution of phenol is an antiseptic while its (c) phenyl side chain (d) cyclohexyl side chain
1.0 percent solution is a disinfectant. 52. Substance used for the preservation of coloured fruit juices
(d) A drug which kills the organism in the body is called is
bacteriostatic. (a) benzene (b) benzoic acid
44. Bactericidal antibiotics are those which (c) phenol (d) sodium meta bisulphite
(a) have inhibitory effect on microbes.
(b) have killing effect on microbes. Topic 4: Cleansing Agents
(c) have both inhibitory and killing effect on microbes. 53. Detergents are prepared by the action of H2SO4 on which
(d) intervene in metabolic process of microorganism. of the following?
45. Which of the following antibiotics is not correctly classified? (a) Cholesterol (b) Lauryl alcohol
Bactericidal Bacteriostatic (c) Cyclohexanol (d) p-Nitrophenol
(A) Penicillin Erythromycin 54. Sodium alkyl benzene sulphonate is used as
(B) Aminoglycosides Tetracycline (a) soap (b) fertilizers
(C) Chloramphenicol Ofloxacin (c) pesticides (d) detergents
(a) A and B (b) C only (c) B and C (d) B only 55. Which of the following represents a synthetic detergent?
(a) C15H31COOK
46. Antibiotics that are effective against Gram-positive or Gram-
(b) CH3[CH2]16COONa
negative bacteria X. Antibiotics that are effective against a
single organism or disease are Y
(c) C12H25 SO3Na
What is X and Y ?
(a) X = Broad spectrum antibiotics.
(d) None of these
Y = Narrow spectrum antibiotics.
56. Which of the following represents soap
(b) X = Broad spectrum antibiotics. (a) C17H35COOK (b) C17H35COOH
Y = Limited spectrum antibiotics. (c) C15H31COOH (d) (C17H35COO)2Ca
(c) X = Narrow spectrum antibiotics. 57. Polyethyleneglycols are used in the preparation of which
Y = Limited spectrum antibiotics. type of detergents?
(d) X = Narrow spectrum antibiotics. (a) Cationic detergents (b) Anionic detergents
Y = Broad spectrum antibiotics. (c) Non-ionic detergents (d) Soaps
CHEMISTRY IN EVERYDAY LIFE 429

58. Which of the following statement is incorrect? (a) A – (p), B – (q), C – (r), D – (s)
(a) Potassium soaps are soft to the skin than sodium soaps. (b) A – (q), B – (r), C – (p), D – (s)
(b) Shaving soaps contain ethanol to prevent rapid drying. (c) A – (r), B – (s), C – (q), D – (p)
(c) Builders like Na2CO3 and Na3PO4 make soaps act more (d) A – (p), B – (r), C – (q), D – (s)
rapidly. 60. Match the columns
(d) Hard water contains Ca2+ and Mg2+ ions which form Column -I Column -II
insoluble Ca2+ and Mg2+ soaps and separate out as (A) Toilet soap (p) Made by beating
scum. tiny air bubbles before
59. Match the columns their hardening.
Column-I Column-II (B) Transparent soap (q) Contain glycerol
+ to prevent rapid drying.
CH3
– (C) Shaving soaps (r) Prepared by
(A) CH3(CH2)15–N–CH3 Br
using better grades of
CH3 fats and oils.
(p) Dishwashing powder (D) Soaps that float in (s) Made by dissolving
water the soap in ethanol
– +
(B) CH3– (CH2)11 SO3 Na and then evaporating
excess alkali.
(q) Laundry soap (a) A – (s), B – (p), C – (q), D – (r)
(C) C17H35COO–Na+ + Na2CO3 + Rosin (b) A – (r), B – (s), C – (q), D – (p)
(r) Hair conditioners (c) A – (r), B – (q), C – (p), D – (s)
(D) CH3(CH2)16COO(CH2CH2O)nCH2CH2OH
(d) A – (q), B – (s), C – (p), D – (r)
(s) Toothpaste

Exercise 2 : Exemplar & Past Year MCQs

NCERT Exemplar MCQs (c) on the basis of molecular targets
(d) on the basis of pharmacological effect
1. Which of the following statements is not correct?
5. Which of the following statements is correct?
(a) Some antiseptics can be added to soaps
(a) Some tranquilizers function by inhibiting the enzymes
(b) Dilute solutions of some disinfectants can be used as which catalyse the degradation of noradrenaline
antiseptic
(b) Tranquilizers are narcotic drugs
(c) Disinfectants are antimicrobial drugs
(c) Tranquilizers are chemical compounds that do not
(d) Antiseptic medicines can be ingested affect the message transfer from nerve to receptor
2. Which is the correct statement about birth control pills? (d) Tranquilizers are chemical compounds that can relieve
(a) Contain estrogen only pain and fever
(b) Contain progesterone only 6. Salvarsan is arsenic containing drug which was first used
(c) Contain a mixture of estrogen and progesterone for the treatment of ............... .
derivatives (a) syphilis (b) typhoid
(d) Progesterone enhances ovulation (c) meningitis (d) dysentery
3. Which statement about aspirin is not true? 7. A narrow spectrum antibiotic is active against .......... .
(a) Aspirin belong to narcotic analgesics (a) gram positive or gram negative bacteria
(b) It is effective in relieving pain (b) gram negative bacteria only
(c) It has antiblood clotting action (c) single organism or one disease
(d) It is a neurologically active drug (d) both gram positive and gram negative bacteria
4. The most useful classfication of drugs for medicinal 8. The compound that causes general antidepressant action
chemists is .......... . on the central nervous system belong to the class of ......
(a) on the basis of chemical structure (a) analgesics (b) tranquilizers
(b) on the basis of drug action (c) narcotic analgesics (d) antihistamines
 EBD_7374
430 CHEMISTRY

9. Compound which is added to soap to impart antiseptic Past Year MCQs

properties is ..........
(a) sodium lauryl sulphate 19. Artificial sweetner which is stable under cold conditions
only is : [AIPMT 2014, A]
(b) sodium dodecylbenzenesulphonate
(a) Saccharine (b) Sucralose
(c) rosin
(c) Aspartame (d) Alitame
(d) bithional
10. Equanil is ........... 20. Assertion : The addition of BHA to butter increases its
(a) artificial sweetener (b) tranquilizer storage life from months to years.
(c) antihistamine (d) antifertility drug Reason : Butylated hydroxy anisole (BHA) is an antioxidant.
11. Which of the following enhances leathering property of [AIIMS 2014, C]
soap? (a) Assertion is correct, reason is correct; reason is a
(a) Sodium carbonate (b) Sodium rosinate correct explanation for assertion.
(c) Sodium strearate (d) Trisodium phosphate (b) Assertion is correct, reason is correct; reason is not a
12. Glycerol is added to soap. It functions .............. correct explanation for assertion
(a) as a filler (b) to increase leathering (c) Assertion is correct, reason is incorrect
(c) to prevent rapid drying (d) to make soap granules (d) Assertion is incorrect, reason is correct.
13. Which of the following is an example of liquid dishwashing 21. A broad spectrum antibiotic is [AIIMS 2014, S]
detergent? (a) paracetamol (b) penicillin
(c) aspirin (d) chloramphenicol
(a) CH3 ( CH 2 )10 — CH 2 OSO3- Na + 22. Which of the following can possibly be used as analgesic
without causing addiction and modification?
(b) C9H19 O ( CH 2 – CH 2 – O )–5 – CH 2CH2OH [BITSAT 2014, C]
(a) morphine
(c) CH 3
–
SO3 Na
+ (b) N-acetyl-para-aminophenol
(c) diazepam
+ (d) tetrahydrocatenol
CH3
| 23. Bithional is generally added to the soaps as an additive to
(d) CH3 ( CH)15 — N – CH3 Br - function as a/an [AIPMT 2015, A]
| (a) dryer (b) buffering agent
CH3 (c) antiseptic (d) softner
24. Which of the following compounds is not an antacid ?
14. Polyethyleneglycols are used in the preparation of which
[JEE M 2015, A]
type of detergents?
(a) Phenelzine (b) Ranitidine
(a) Cationic detergents
(c) Aluminium hydroxide (d) Cimetidine
(b) Anionic detergents
25. Cobalt (60) isotope is used in the treatment of :
(c) Non - ionic detergents
[BITSAT 2015, A]
(d) Soaps (a) Heart diseases (b) Skin diseases
15. Which of the following is not a target molecule for drug (c) Diabetes (d) Cancer
function in body? 26. Which of the following is an analgesic? [NEET 2016, A]
(a) Carbohydrates (b) Lipids (a) Novalgin (b) Penicillin
(c) Vitamins (d) Proteins (c) Streptomycin (d) Chloromycetin
16. Which of the following statements is not true about enzyme 27. Assertion : Tetracycline is a broad spectrum antibiotic.
inhibitors? Reason : Tetracycline is effective against a number of types
(a) Inhibit the catalytic activity of the enzyme of bacteria, large viruses and typhus fever.
(b) Prevent the binding of substrate [AIIMS 2016, C]
(c) Generally a strong covalent bond is formed between (a) Assertion is correct, reason is correct; reason is a
an inhibitor and an enzyme correct explanation for assertion.
(d) Inhibitors can be competitive or non – competitive (b) Assertion is correct, reason is correct; reason is not a
17. Which of the following chemicals can be added for correct explanation for assertion
sweetening of food items at cooking temperature and does (c) Assertion is correct, reason is incorrect
not provides calories? (d) Assertion is incorrect, reason is correct.
(a) Sucrose (b) Glucose 28. Which of the following is an anionic detergent?
(c) Aspartame (d) Sucralose [JEE M 2016, A]
18. Which of the following will not enhance nutritional value (a) Cetyltrimethyl ammonium bromide.
of food? (b) Glyceryl oleate.
(a) Minerals (b) Artificial sweetners (c) Sodium stearate.
(c) Vitamins (d) Amino acids (d) Sodium lauryl sulphate.
CHEMISTRY IN EVERYDAY LIFE 431

29. The important antioxidant used in food is (c) Assertion is correct, reason is incorrect
[BITSAT 2016, A] (d) Assertion is incorrect, reason is correct.
(a) BHT (b) BHC 32. Which of the following compounds is not an antacid ?
(c) BTX (d) All the three
[AIIMS 2017, A]
30. Mixture of chloroxylenol and terpineol acts as:
[NEET 2017, S] (a) Phenelzine (b) Ranitidine
(a) antiseptic (b) antipyretic (c) Aluminium hydroxide (d) Cimetidine
(c) antibiotic (d) analgesic 33. Which is incorrect? [AIIMS 2018, A]
31. Assertion : Sedatives are given to patients who are mentally (a) Novestrol - Antifertility
agitated and violent. (b) Serotonine - Tranquilizer
Reason : Sedatives are used to suppress the activities of (c) Narrow spectrum - Chloramphenicol
central nervous system. [AIIMS 2017, S] (d) Ranitidine - antacid
(a) Assertion is correct, reason is correct; reason is a 34. Which of the following is a diamine? [BITSAT 2018, C]
correct explanation for assertion. (a) Dopamine (b) Histamine
(b) Assertion is correct, reason is correct; reason is not a (c) Meprobamate (d) Chlorphenamine
correct explanation for assertion

Exercise 3 : Try If You Can

1. Aspirin can be prepared by the reaction of (b) morphine dibenzoate
(a) Salicyldehyde with acetic anhydride in presence of (c) morphine diacetate
H2SO4 (d) morphine monobenzoate
(b) Salicylic acid with methanol in presence of H2SO4 5. A medicine which promotes the secretion of urine is called
(c) Salicylic acid with acetic anhydride in presence of (a) uretic (b) monouretic
H2SO4 (c) diuretic (d) triuretic
(d) Cinnamic acid with acetic anhydride in presence of 6. Which is used for sterilization of water in water supply
H2SO4 system of cities?
2. The correct structure of the drug paracetamol is (a) Chlorine (b) Sulphurdioxide
OCH3 OH (c) Potassium permanganate(d) DDT
7. Which of the following is an alkaloid?
(a) Nicotine (b) Piperine
(a) (b) (c) Cocaine (d) All of these
8. End of detergents have
(a) ester group (b) sodium sulphate
CONH2 NHCOCH3 (c) aldehyde (d) amine group
9. The following compound is used as
OCH3 OH O
O – C – CH3

(c) (d)
COOH
(a) an anti-inflammatory compound
CONH2 COCH3 (b) analgesic
3. The insecticide containing 99% g – isomer of benzene (c) hypnotic
(d) antiseptic
hexachloride is known as
10. An antibiotic contains nitro group attached to aromatic
(a) lindane (b) TNT
nucleus. It is
(c) malathion (d) methoxychlor
4. Chemically heroin is (a) penicillin (b) streptomycin
(a) morphine monoacetate (c) tetracycline (d) chloramphenicol
 EBD_7374
432 CHEMISTRY

ANSWER KEYS
Exercise 1 : Topic-wise MCQs
1 (d) 7 (a) 13 (d) 19 (a) 25 (d) 31 (c) 37 (b) 43 (d) 49 (b) 55 (c)
2 (a) 8 (d) 14 (a) 20 (a) 26 (d) 32 (b) 38 (c) 44 (b) 50 (c) 56 (a)
3 (d) 9 (b) 15 (b) 21 (c) 27 (a) 33 (d) 39 (a) 45 (b) 51 (b) 57 (c)
4 (b) 10 (c) 16 (d) 22 (c) 28 (b) 34 (b) 40 (a) 46 (c) 52 (b) 58 (b)
5 (d) 11 (c) 17 (d) 23 (b) 29 (c) 35 (c) 41 (b) 47 (a) 53 (b) 59 (c)
6 (d) 12 (b) 18 (a) 24 (c) 30 (b) 36 (d) 42 (c) 48 (d) 54 (d) 60 (b)
Exercise 2 : Exemplar & Past Year MCQs
1 (d) 5 (a) 9 (d) 13 (b) 17 (d) 21 (d) 25 (d) 29 (a) 33 (c)
2 (c) 6 (a) 10 (b) 14 (c) 18 (b) 22 (b) 26 (a) 30 (a) 34 (c)
3 (a) 7 (a) 11 (b) 15 (c) 19 (c) 23 (c) 27 (a) 31 (a)
4 (c) 8 (b) 12 (c) 16 (c) 20 (a) 24 (a) 28 (d) 32 (a)
Exercise 3 : Try If You Can
1 (c) 2 (b) 3 (a) 4 (c) 5 (c) 6 (a) 7 (d) 8 (b) 9 (b) 10 (d)
 1. SOME BASIC CONCEPTS OF CHEMISTRY

Exercise - 1 12. (a)

mass of H 2 combined 4 1
1. (c) By sublimation since I2 sublimes. 13. (c) I experiment : = =
mass of O 2 combined 32 8
2. (d) It forms the basis of gravity separation.
3. (a) 1 m3 of water 106 cm3 of water mass of H 2 combined 50 1
II experiment : = =
\ Mass of 106 cm3 water mass of O 2 combined 400 8
= 106 cm3 × 1 g cm3 (Q density of H2O = 1 g cm3) Hence both law of conservation of mass and constant
composition is obeyed.
10 6 14. (c) The H : O ratio in water is fixed, irrespective of its source.
= 106 g = kg = 103 kg = 1000 kg
3 Hence it explains law of constant composition.
10
(b) Weight of normal adult man = 65 kg 15. (a) Constant proportions according to which a pure
chemical compound always contains same elements
\ Weight of 1 m3 of water is highest.
combined together in the same definite proportion of
(c) Density of Hg = 13.6 g cm–3
weight.
Volume of Hg = 10 L = 10 × 1000 = 104 cm3
16. (d) SnCl2 SnCl4
\ Weight of Hg = 13.6 × 104 = 136000 g = 136 kg 119 : 2 × 35.5 119 : 4 × 35.5
4. (d) Smallest and largest amount of energy respectively are Chlorine ratio in both compounds is
eV and L-atm. = 2 × 35.5 : 4 × 35.5 = 1 : 2
1 eV = 1.6 × 10–19 J 17. (c)
1L -atm = 101.325 J 18. (b) Law of multiple proportion. As the ratio of oxygen which
5 5 combine with fix weights of 1 g of nitrogen bears a
5. (c) °C = (°F - 32 ) = ( 41 - 32 ) = 5 °C simple whole number ratio
9 9
It will be cold. 0.57 : 1 : 12 : 1.7031 : 2 : 3
6. (a) Out of two 3.929 g is more accurate and will be reported 19. (c) According to Avogadro's law "equal volumes of all
as 3.93 after rounding off. gases contain equal number of molecules under similar
7. (d) Both Y and X are neither precise nor accurate as the conditions of temperature and pressure". Thus if 1 L of
two values in each of them are not close. With respect one gas contains N molecules, 2 L of any other gas
to X & Y, the values of Z are close & agree with the under the same conditions of temperature and pressure
true value. Hence, both precise & accurate. will contain 2N molecules.
8. (c) On calculation we find 20. (b) The number of molecules of N2 and X are same. Hence
they must have the same molecular weights.
(29.2 – 20.2)(1.79 ≥105 ) \ X is CO.
= 1.17×106
1.37 21. (c)
As the least precise number contains 3 significant 22. (d) Avogadro’s law is independent of the reactive or
figures therefore, answers should also contains 3 unreactive nature of the gases.
significant figures. According to Avogadro’s law equal volumes of gases
9. (d) We know that all non-zero digits are significant and at the same temperature and pressure should contain
the zeros at the beginning of a number are not equal number of molecules.
significant. Therefore number 161 cm, 0.161 cm and 23. (c) For statement (i) : H, O, C, N = All have different
0.0161cm have 3, 3 and 3 significant figures respectively. chemical properties.
10. (b) Given P = 0.0030 m, Q = 2.40 m & R = 3000 m. In For statement (ii) : It is true as per Dalton’s postulate.
P (0.0030) initial zeros after the decimal point are not For statement (iii) : N : O = 1 : 1 (NO)
significant. Therefore, significant figures in P(0.0030) For statement (iv) : Dalton’s postulates says, atoms
are 2. Similarly in Q (2.40) significant figures are 3 as in can neither be created nor destroyed.
this case final zero is significant. In R = (3000) all the 24. (c) Equal moles of different substances contain same
zeros are significant hence, in R significant figures are number of constituent particles but equal weights of
4 because they come from a measurement. different substances do not contain the same number
11. (a) 2.6 has two significant figures. of consituent particles.
0.260 has three significant figures. 25. (c)
0.002600 has four significant figures. 26. (b) Average atomic mass of neon
2.6000 has five significant figures. = 20 × 0.9051 + 21 × 0.0027 + 22 × 0.0922
= 20.187 u
 EBD_7374
434 CHEMISTRY

27. (a) (78.9183361) × (0.5069) + (80.916289) × (0.4931) = 79.9 41. (a) 21% of 1 litre is 0.21 litre.
28. (a) Mass of oxygen atom is 15.995 amu, becasue 1 amu 22.4 litres = 1 mole at STP
= 1.66056 × 10–24 g, hence 15.995 × value of 1 amu 0.21
give the value equal to option (a). \ 0.21 litre = = 0.0093 mol
22.4
2.824784 ´ 10-23 42. (d) At S.T.P. 22.4 litre of gas contains 6.023 × 1023 molecules
29. (d) = 14 amu \ molecules in 8.96 litre of gas
1.66056 ´ 10–24
Where 1.66056 × 10–24 is equal to one atomic mass 6.023 ´10 23 ´ 8.96
= = 24.08 ´10 22
(amu) 22.4
30. (b) 43. (b) Mass of one molecule of water
31. (a) Relative atomic mass
18
Mass of one atom of the element = 23
= 3 ´10-23 g = 3 ´10-26 kg
= th 6.023 ´10
1/12 part of the mass of one atom of Carbon - 12
44. (d) 1 molecule of CO2 has one atom of C and two atoms of
Mass of one atom of the element oxygen.
or ´ 12
mass of one atom of the C - 12 \ 1 mole of CO2 has = 6.02 × 1023 atoms of C
Now if we use 1/6 in place of 1/12 the formula becomes = 2 × 6.02 × 1023 atoms of O
Mass of one atom of element 45. (a) Given, V = 1.12 × 10–7 cm3
Relative atomic mass = ´6 22400 cm3 at NTP = 6.02 × 1023 molecules
Mass of one atom of carbon
\ Relative atomic mass decrease twice 6.02 ´ 1023
\ 1.12 × 10–7 cm3 at NTP = ´1.12 ´10-7
32. (b) Gram molecular weight of CO = 12 + 16 = 28 g 22400
6.023 × 1023 molecules of CO weight 28 g = 3.01 × 1012 molecules.
28 = 4.65 ´10-23 g 46. (b) Total atoms in 1 molecule of C12H22O11
1 molecule of CO weigh =
6.02´1023 = 12 + 22 + 11 = 45
33. (b) Molecular weight of SO2 = 32 + 2 × 16 = 64 \ Total atoms in 1 mole of C12H22O11
64 g of SO2 occupies 22.4 litre at STP = 45 × 6.02 × 1023 atoms/mol.
47. (a) Let mass of O2 = 1 g
22.4
240 g of SO2 occupies = ´ 240 = 84 litre at STP \ Mass of N2 = 4g
64
1
34. (a) 1 mol CCl4 vapour = 12 + 4 × 35.5 No. of molecules of O2 =
32
= 154 g º 22.4 L at STP 4
No. of molecules of N2 =
\ Density = 154 gL-1 = 6.875 gL-1 28
22.4 1 4 1 1
35. (b) 6.02 × 1023 molecules of CO =1mole of CO Ratio of no. of molecules = : = : = 7 : 32
32 28 32 7
6.02 × 1024 CO molecules = 10 moles CO
= 10 g atoms of O = 5 g molecules of O2 weight 50
48. (d) No. of moles = = = 0.14 mole
4.4 mol. wt . 342
36. (a) 4.4 g CO2 = = 0.1 mol CO2 (mol. wt. of CO2 = 44)
44 49. (c) Mass of 1 electron = 9.11 × 10–28 g
= 6 × 1022 molecules = 2 × 6 × 1022 atoms of O. \ Mass of 1 mole (6.02 × 1023) electrons
37. (b) 2g of H2 means one mole of H2, hence contains = 9.11 × 10–28 × 6.02 × 1023g
6.023 × 1023 molecules. Others have less than one mole, = 55 × 10–5 g = 55 × 10–5 × 103 mg = 0.55 g.
so have less no. of molecules.
1
558.5 50. (b) H2 + O ¾¾ ® H2 O
38. (a) Fe (no. of moles) = = 10 moles = 10NA atoms. 2 2
55.85 10g 64g
No. of moles in 60 g of C = 60/12 = 5 moles = 5NA atoms.
æ 10 ö æ 64 ö
39. (c) 16 g CH4 is 1 mol. Hence number of molecules ç =5 mol ÷ ç = 2 mol ÷
è2 ø è 32 ø
= Avogadro number = 6.023 × 1023. In this reaction oxygen is the limiting agent. Hence
40. (c) M. Wt of Na2SO4.10H2O is 322 g which contains 224 g amount of H2O produced depends on the amount of
oxygen. O2 taken
\ 32.2 g will contain 22.4 g oxygen. Q 0.5 mole of O2 gives H2O = 1 mol
\ 2 mole of O2 gives H2O = 4 mol
SOME BASIC CONCEPTS OF CHEMISTRY 435

51. (c) No. of molecules Mass

57. (c) Density =
44 Volume
Moles of CO2 = =1 NA
44
1gram
48 1 gram cm–3 =
Moles of O3 = =1 NA cm 3
48
8 Mass 1gram
Moles of H2 = = 4 4NA Volume = = = 1cm 3
2 Density 1gram cm -3
64
Moles of SO2 = =1 NA \ Volume occupied by 1 gram water = 1 cm3
64
or Volume occupied by
No. of molecules will be more in 8g of H2
52. (b) Molecular weight of C60H122 = (12 × 60) + 122 = 842. 6.023 ´ 1023
Therefore weight of one molecule molecules of water = 1 cm3
18
Molecular weight of C 60 H 122
= 1
Avagadro' s number [\ 1g water = moles of water]
18
842
= = 1.4 ´ 10 - 21 g Thus volume occupied by 1 molecule of water
23
6.023 ´ 10
53. (a) 1 ´ 18
= cm 3 = 3.0×10–23 cm3.
54. (d) We know that from the reaction H2 + Cl2 ® 2HCl that 6.023 ´ 10 23
the ratio of the volume of gaseous reactants and 58. (b) The number of atoms in 0.1 mole of a triatomic gas
products is in agreement with their molar ratio.The ratio
= 0.1 × 3 × 6.023 × 1023.
of H2 : Cl2 : HCl volume is 1: 1: 2 which is the same as
their molar ratio. Thus volume of gas is directly related = 1.806 × 1023
to the number of moles. Therefore, the assertion is false 59. (d) At NTP 22400 c c of N2O = 6.02 × 1023 molecules
but reason is true.
55. (a) No. of molecules in different cases 6.02 ´ 1023
\ 1 cc N2O = molecules
(a) Q 22.4 litre at STP contains 22400
= 6.023 × 1023 molecules of H2 3 ´ 6.02 ´ 10 23 1.8
15 = atoms = ´ 1022 atoms
\ 15 litre at STP contains = ´ 6.023 ´ 10 23 22400 224
22.4
= 4.03 × 1023 molecules of H2 No. of electrons in a molecule of N 2O = 7 + 7 + 8 = 22
(b) Q 22.4 litre at STP contains Hence no. of electrons
= 6.023×1023 molecules of N2
6.02 ´1023 1.32 ≥1023
5 = ´ 22 electrons <
Q 5 litre at STP contains = ´ 6.023 ´ 10 23 22400 224
22.4
60. (b) If 1020 grains are distributed in one sec, 6.023 × 1023
= 1.344 × 1023 molecules of N2
grains will be distributed in
(c) Q 2 gm of H2= 6.023×1023 molecules of H2
6.023 ´ 1023 ´ 1
0.5 = 1.673 hrs
Q 0.5 gm of H2= ´ 6.023 ´10 23 1020 ´ 60 ´ 60
2 61. (c) (a) Weight of H2 = mole × molecular wt.
= 1.505 × 1023 molecules of H2 = 0.2 × 2 = 0.4 g
(d) Similarly 10 g of O2 gas 23
(b) 6.023 × 10 = 1 mole
10 Thus 6.023 × 1022 = 0.1 mole
= ´ 6.023 ´ 10 23 molecules of O2
32 Weight of N2 = 0.1 × 28 = 2.8 g
= 1.88 × 1023 molecules of O2 (c) Weight of silver = 0.1 g
Thus (a) will have maximum number of molecules
(d) Weight of oxygen = 32 × 0.1 = 3.2 g
56. (d) 1 Mole of Mg3(PO4)2 contains 8 mole of oxygen atoms
\ 8 mole of oxygen atoms º 1 mole of Mg3(PO4)2 62. (a) Empirical formula of compound = CH2
1 Molecular mass of the compound = 42
0.25 mole of oxygen atom º ´ 0.25 mole of Mg3(PO4)2 \ n = 42/14 = 3
8
= 3.125 × 10–2 mole of Mg3(PO4)2 \ Hence molecular formula = C3H6
 EBD_7374
436 CHEMISTRY

63. (a) Molecular mass = 80

Molecular formulae = n (C2H2N)
Atomic Atomic Simple
= 2 (C2H2N) æç n =
Element Percentage 80 ö
weight ratio ratio ÷ = C4H4N2
è 40 ø
38.71 3.23 68. (b) Let 100 g of compound be there.
C 38.71 12 = 3.23 =1
12 3.23
77.43g
9.67 9.67 Number of moles of C = = 6.44
H 9.67 1 = 9.67 =3 12.01g / mol
1 3.23
7.53g
100 - 51.62 3.23 Number of moles of H = = 7.47
O (38.71 + 9.67) 16 = 3.23 =1 1.008g / mol
= 51.62 16 3.23
15.05
Number of moles of N = = 1.075
14.00g / mol
Thus empirical formula is CH3O. 1.074 is the smallest value, division by it gives a ratio
64. (c) Percentage R.N.A Simplest ratio of C : H : N
9 3 = 5.9 : 6.9 : 1
C 9 = 3 =6:7:1
12 4
Empirical formula = C6H7N
1 Empirical formula weight = 6 × 12 + 7 + 14 = 93
H 1 =1 4
1 Molecular mass
n= =1
3.5 1 Empirial formula weight
N 3.5 = 1
14 4 Molecular formula = 1 × C6H7N = C6H7N
Empirical formula = C3H4N 69. (b) The equation for the formation of Al 2O3 can be
(C3H4N)n = 108 represented as
(12 × 3 + 4 × 1 + 14)n = 108 2Al + 3 / 2O 2 ¾¾® Al2 O3
2 moles 1.5 moles 1 mole
(54)n = 108 Thus, 1 mole of alumina is obtained by the reaction of
108 1.5 moles of oxygen and 2 moles of aluminium. Thus,
n= =2 the amount of aluminium
54
\ molecular formula = C6 H8N2 = 2 × 27 g = 54 g. [mol. mass of Al = 27]
65. (c) The acid with empirical formula CH2O2 is formic acid, 70. (b) Mg + 2 HCl ® MgCl 2 + H 2 ­
HCOOH. 1 mole 1 mole
66. (d) Q 18 gm, H2O contains = 2 gm H 1 1 1
mole mole (12g of Mg = mol )
2 2 2
2
\ 0.72 gm H2O contains = ´ 0.72 gm = 0.08 gm H 71. (a) We know that
18
Q 44 gm CO2 contains = 12 gm C N2 + 3H2 ® 2NH3
28 g 6g 34 g
12
\ 3.08 gm CO2 contains = ´ 3.08 = 0.84 gm C 14 g 3g 17 g
44 Here given H2 is 3 kg and N2 is 20 kg but 3 kg of H2 can
0.84 0.08
\ C:H= : = 0.07 : 0.08 = 7 : 8 only react with 14 g of N2 and thus the obtained NH3
12 1 will be of 17 kg.
\ Empirical formula = C7H8 72. (d) 2H2 + O2 ¾¾® 2H2O
67. (a) Let 100 g of compound be there.
4g 32g 36g
35 4kg 32 kg 36kg
Number of moles of Nitrogen = = 2.5
14 73. (c) C2H4 + 3 O2 ¾
¾® 2CO2 + 2H2O
5 28 g 96 g
Number of moles of Hydrogen = = 4.9 Q 28 g of C2H4 undergo complete combustion by
1.008
= 96 g of O2
60 \ 2.8 kg of C2H4 undergo complete combustion by
Number of moles of Carbon = = 4.9
12.01 = 9.6 kg of O2.
Since 2.5 is the smallest value division by it give ratio 74. (c) According to stoichiometry they should react as follow
N:H:C 4NH 3 + 5O 2 ¾¾ ® 4NO + 6H 2 O
1 : 1.96 : 1.96 4 mole of NH3 requires 5 mole of O2.
=1:2:2
5
Empirical formula = C2H2N 1 mole of NH3 requires = = 1.25 mole of O2.
Empirical formula weight = 2 × 12 + 2 + 14 = 40 4
Hence O2 is consumed completely.
SOME BASIC CONCEPTS OF CHEMISTRY 437

Wt. of substance = No. of moles × Molecular mass

Equivalent mass
75. (a) Molarity = Normality × = 0.205 × 197.3 = 40.5 g
Molecular mass 85. (a) Fe2O3 + 3CO ® 2Fe + 3CO2
M 1 vol. 3 vol. 2 vol. 3 vol.
= 0.2 ´ = 0.1 M 1 mol. 3 mol. 2 mol. 3 mol.
2´ M (Q vol% = mol%)
76. (a) Normality One gram mol of any gas occupies 22.4 litre at NTP.1
Molarity =
Replaceable hydrogen atom mol of Fe2O3 requires 3 mol of CO for its reduction i.e.,
1 mol of Fe2O3 requires 3 × 22.4 litre or 67.2 dm3 CO to
Q H2SO4 is dibasic acid.
get itself reduced.
\ Molar solution of H2SO4 = N/2 H2SO4
77. (b) Given N1 = 10N, V1 = 10 ml, N2 = 0.1N, V2 = ? 163
86. (a) C57H110O6 + O2 ® 57CO2 + 55H2O
N1V1 = N2V2 2
or 10 × 10 = 0.1 × V2 890 gram of fat produces 990 gram of H2O
10 ´ 10
or V2 = , V2 = 1000 ml 450 gram fat produces æç
990 ö
0.1 ´ 450 ÷
Volume of water to be added è 890 ø
= V2 – V1 = 1000 – 10 = 990 ml. = 500.56 g of H2O
Mass of solute 500.56g
78. (b) ppm = ´ 106 Moles of H2O = = 27.80
Mass of solution 18g mol
6 ´ 10 –3 26g
\ ppm = ´ 10 6 = 6. 87. (d) nC = = 2.16
1000 12 g/mol
79. (a) 5 M H2SO4 = 10 N H2SO4,
(Q Basicity of H2SO4 = 2) 20 g
nO2 = = 0.625
N1V1 = N2V2, 32 g/mol
10 × 1 = N2 × 10 or N2 = 1 N
O2 will be a limiting reagent in reaction (i)
6.02 ´ 1020
80. (b) Moles of urea present in 100 mL of sol.= 60g
6.02 ´ 10 23 nN 2 = = 2.14
28g/mol
6.02 ´ 1020 ´ 1000
\M = = 0.01M nH 2 = 40
6.02 ´ 1023 ´ 100
[Q M = Moles of solute present in 1L of solution] According to balanced equation,
81. (b) From the molarity equation. 1 mol of N2 requires 3 mole of N2
M1V1 + M2V2 = MV 2.14 mol of N2 require 6.42 mol of N2
N2 will be a limiting reagent in reaction (ii)
Let M be the molarity of final mixture,
M1V1 + M 2V2 100g
M= where V = V1 + V2 nP4 = = 0.86 nO2 = 6.25
V 4 ´ 31
According to balanced equation
480 ´ 1.5 + 520 ´ 1.2
M = = 1.344 M 1 mol of P4 require 3 mol of O2
480 + 520 0.86 mol of P4 require 2.58 mol of O2
82. (c) So option (d) is correct.
So P4 is a limiting reagent in reaction (iii)
83. (c) BaCO3 ® BaO + CO 2 88. (a) From molarity equation
197 gm
M1V1 + M2V2 = MV(total)
Q197 gm of BaCO3 released carbon dioxide
= 22.4 litre at STP 10 200 210
2´ + 0.5 ´ = M´
1000 1000 1000
22.4
\ 1 gm of BaCO3 released carbon dioxide = litre 120 = M × 210
197
\ 9.85 gm of BaCO3 released carbon dioxide 120
= 0.57 M
M=
210
22.4
= ´ 9.85 = 1.12 litre 89. (a) 1 ppm = 1 mg / 1 litre (for liquids)
197 4 ppm = 4 mg / 1 litre
84. (b) Ba(OH)2 + CO2 ¾¾
® BaCO3 + H2 O 1 litre contains 4 mg of fluoride ions
n mol n mol
4
n mol Ba(OH)2 = n mol BaCO3 10 ml contains ´ 10 = 0.04 mg
1000
\ 0.205 mol Ba (OH) 2 º 0.205 mol BaCO3
 EBD_7374
438 CHEMISTRY

0.04g 5. (d) number of atoms = No. of moles × NA

Number of moles of fluoride = 4
19g / mol
Moles of 4 g He = = 1 mol Þ NA atoms
= 2.10 × 10–3 4
No. of moles of solute 46
90. (a) Molarity (M) = 46 g Na = = 2 mol Þ 2 NA atoms
Volume of solution in litres 23
Molarity µ nsolute 0.40
25 0.40 g Ca = = 0.1 mol Þ 0.1 NA atoms
nNaOH = = 0.625 40
40
25 12
nLiOH = = 1.04 12 g He = = 3 mol Þ 3 NA atoms
24 4
25 i.e.12 g He contains greatest number of atoms.
nAl(OH)3 = = 0.32 6. (c) In the given question, 0.9 g L–1 means that 1000 mL
(17 + 3 ´17)
(or 1L) solution contains 0.9 g of glucose.
25 Molecular mass of glucose (C6H12O6) = 180 u
nKOH = = 0.45
(39 + 17)
0.9
nB(OH)3 = 25 \ Number of moles of glucose = =0.005 M
= 0.403 180
(11 + 17 ´ 3)
= 5×10–3 mol glucose
Exercise - 2 Hence, 1000 mL or 1L solution contains 0.005 mole
glucose or the molarity of glucose is 0.005 M.
1. (b) Average of readings of student A Moles of solute
7. (d) Molality (m) =
=
3.01 + 2.99
= 3.00 Mass of solvent ( in kg )
2 Q Molecular weight of HCl = 36.5 g
Average of readings of student B
18.25
3.05 + 2.95 \ Moles of HCl = = 0.5
= = 3.00 36.5
2
Correct reading = 3.00 0.5 ´ 1000
m= =1m
Since, average value in both the cases is close to the 500
correct value. Hence, readings of both are accurate. 8. (a) Number of millimoles of H2SO4.
Readings of student A differ only by 0.02 and also = molarity × volume in mL
close to the correct reading hence, readings are precise = 0.02 × 100 = 2 millimoles
too. But readings of student B differ by 0.1 and hence = 2 × 10–3 mol
are not precise. Number of molecules = Number of moles × NA.
2. (c) The relation between the temperatures on two scales = 2 × 10–3 × 6.022 × 1023
is given by the following relationship : = 12.044 × 1020 molecules
9. (b) Molecular mass of CO2 = 44 g
9
°F = T °C + 32 Q 44 g of CO2 contain C = 12 g atoms of carbon
5
12
5 200 - 32 \ % of C in CO2 = ´ 100 = 27.27%
\ T °C = ( °F - 32) ´ = ´5 44
9 9 i.e. mass percent of carbon in CO2 is 27.27%.
168 ´ 5 10. (c) Empirical formula mass of CH2O = 30
Þ T°C = = 93.3 °C Molecular mass = 180 (Given)
9
Molecular mass 180
weight ´ 1000 n= = =6
3. (c) Molarity = Empirical formula mass 30
molecular weight ´ volume ( mL)
\ Molecular formula = n × empirical formula
5.85 ´ 1000 = 6 × CH2O
= = 0.2 mol L–1
58.5 ´ 500 = C6H12O6
4. (b) For dilution, a general formula is 11. (a) For a solution, Mass = volume × density
M1 V1 = M2 V2 = 1.5 mL × 3.12 g mL– 1= 4.68 g
(Before dilution) (After dilution) The digit 1.5 has only two significant figures, so the
500 × 5M = 1500 × M2 answer must also be limited to two significant figure.
So it is rounded off to 4.7 g.
5
M2 = = 1.66 M
3
SOME BASIC CONCEPTS OF CHEMISTRY 439

12. (c) The properties of a compound are quite different from 20. (c) Formation of CO and CO2 illustrates the law of multiple
the properties of constituent elements. e.g., ammonia proportion that is constant mass of C reacts with
is a compound containing hydrogen and nitrogen different masses of oxygen. These masses here bears
combined together in a fixed proportion. But the simple ratio of 1 : 2.
properties of ammonia are completely different from 21. (a) Ratio of weight of gases = wH2 : wO2 = 1 : 4
its constituents, hydrogen and nitrogen. 1 4
Ratio of moles of gases = n H2 : nO2 = :
13. (a) According to the law of conservation of mass, 2 32
Total mass of reactants = Total mass of products
1 32
14. (b) In this equation \ Molar Ratio = ´ = 4 :1
2 4
C3H8 (g) + O 2 (g) ¾¾
® CO 2 (g) + H 2O (g)
44g 32g 44g 18g 22. (d) MgCO3 ¾¾
↑ MgO ∗ CO 2
i.e. mass of reactants ¹ mass of products 84 g of MgCO3 form 40 g of MgO
Hence, law of conservation of mass is not obeyed.
15. (b) In CO2, 12 parts by mass of carbon combine with 32 40≥ 20
\ 20g of MgCO3 form g of MgO
parts by mass of oxygen while in CO, 12 parts by mass 84
of carbon combine with 16 parts by mass of oxygen. = 9.52 g of MgO
Therefore, the masses of oxygen combine with a fixed
Since 8.0 g of MgO is formed
mass of carbon (12 parts) in CO2 and CO are 32 and 16
respectively. These masses of oxygen bear a simple 8
ratio of 32 : 16 or 2 : 1 to each other. Purity of sample < ≥100 = 84.0%
9.52
This is an example of law of multiple proportion.
23. (d) No. of moles of water
16. (a) H2 + Cl2 ¾® 2HCl In 1.8 g of H2O = 0.1 moles
t=0 22.4 lit 11.2 lit 0
t = 0 or 1 mole 0.5 mole 0 In 18 g of H2O = 1 moles
at time t 0 (1 – 0.5) 0.5 × 2 1 mole contain 6.022 × 1023 molecules of water
= 0.5 = 1 mole
therefore maximum number of molecules is in 18 moles
1 of water.
17. (a) Initially Mg + O2 ¾® MgO
1g 2 24. (b) If 6.022 × 1023 changes to 6.022 × 1020/mol than this
0.56 would change mass of one mole of carbon.
1 0.56 25. (c) 50 ml of 16.9% solution of AgNO3
or mole mole
24 32 æ 16.9 ö
0.0416 mole 0.0175 mole ç 100 ´ 50 ÷ = 8.45 g of Ag NO3
è ø
(0.0416 – 2 × 0.0175) (2 × 0.0175) mole = 0.0066 mole
\ Mass of Mg = 0.0066 × 24 8.45g
nmole =
= 0.158 » 0.16g (107.8 + 14 + 16 ´ 3) g / mol
18. (c) No. of molecules
æ 8.45 g ö
44 =ç
è 169.8g / mol ÷ø
= 0.0497 moles
Moles of CO2 = =1 NA
44
50 ml of 5.8% solution of NaCl contain
48
Moles of O3 = =1 NA
48 æ 5.8 ö
NaCl = ç ´ 50 ÷ = 2.9 g
8 è 100 ø
Moles of H2 = = 4 4NA
2
2.9g
64 nNaCl = = 0.0495 moles
Moles of SO2 = =1 NA (23 + 35.5) g/ mol
64
w AgNO3 + NaCl ® AgCl¯ + Na + Cl –
19. (b) Number of moles of O 2 = 1 mole 1 mole 1 mole
32
\ 0.049 mole 0.049 mole 0.049 mole of AgCl
4w w
Number of moles of N 2 = =
28 7 w
n= ® w = (nAgCl) × Molecular Mass
M
\ Ratio = w : w = 7 : 32 = (0.049) × (107.8 + 35.5)
32 7
= 7.02 g
 EBD_7374
440 CHEMISTRY

26. (b) The atomic weight of sulphur =32 33. (b) Given N1 = 10N, V1 = 10 ml, N2 = 0.1N, V2 = ?
In SCl2 valency of sulphur = 2 N1V1 = N 2 V2
32 or 10 × 10 = 0.1 × V2
So equivalent mass of sulphur = = 16
2 10 ´ 10
27. (b) 2 mole of water softner require 1 mole of Ca 2+ ion or V2 = , V2 = 1000 ml
0.1
1 Volume of water to be added
So, 1 mole of water softner require mole of Ca2+ ion = V2 – V1 = 1000 – 10 = 990 ml.
2
34. (c) Equal moles of different substances contain same
1 1 number of constituent particles but equal weights of
Thus, = mol / g will be maximum uptake
2 ´ 206 412 different substances do not contain the same number
28. (c) Exa = 1018 of consituent particles.
29. (a) Mass of 6.023 × 1023 atoms of oxygen = 16 g 35. (c) Percentage (by mass) of elements given in the body of
Mass of one atom of oxygen a healthy human adult is :-
16 Oxygen = 61.4%, Carbon = 22.9%,
= = 2.66 ´ 10 -23 g Hydrogen = 10.0% and Nitrogen = 2.6%
6.023 ´ 10 23
Mass of 6.023 × 1023 atoms of nitrogen = 14 g Q Total weight of person = 75 kg
Mass of one atom of nitrogen 10
\ Mass due to 1H is = 75 ´ = 7.5 kg
14 100
= 23
= 2.32 ´ 10 -23 g
6.023 ´ 10 If 1H atoms are replaced by 2H atoms.
Mass of 1 × 10–10 mole of oxygen = 16 × 10–10 Mass gain by person would be = 7.5 kg
Mass of 1 mole of copper = 63 g 36. (b) Given chemical eqn
Mass of 1 mole of oxygen = 16 g M2CO3 + 2HCl ® 2MCl + H2O + CO2
Mass of 1 × 10–10 mole of copper = 63 × 1 × 10–10 1g 0.01186 mole
= 63 × 10–10 from the balanced chemical eqn.
So, the order of increasing mass is nM2CO3 = nCO2
II < I < III < IV.
1
æ 4x + y ö y = 0.01186
30. (d) CxHy(g) + ç ÷ O2(g) ® xCO2(g) + H2O(l) M 2 CO3
è 4 ø 2
1
20 \ M 2 CO3 =
Volume of O2 used = 375 ´ = 75 mL 0.01186
100
Þ M = 84.3 g/mol
\ From the reaction of combustion
37. (a) Given, mass ratio is C:H:O (6:1:24) so, molar ratio will
4x + y be 6/12:1/1:24/16 = 1:2:3
1 mL CxHy requires = mL O2
4 therefore, HO-(C=O)-OH has molar ratio 1:2:3
38. (c) M1V1 = M2V2
æ 4x + y ö
15 mL = 15 ç ÷ = 75 (0.025 M) (0.050 L) = (M2) (0.025 L)
è 4 ø
M2 = 0.05 M
So, 4x + y = 20
x= 3 but, there are 2 H’s per H2SO4 so [H2SO4] = 0.025 M
H2SO4
y= 8 39. (d) HCOOH ¾¾¾¾® CO + H2O
Dehydrating
\ C3H8 will be the formula of hydro carbon agent [H 2O absorbed
31. (a) Let the amount of Na2CO3 present in the mixture be x by H 2SO 4]
2.3 1
g . Na2SO4 will not react with H2SO4. Then At start = = 0 0
46 20
(moles)
x 20 ´ 0.1 ´ 10 1 1
= \ x = 1.06 g Final moles 0
53 1000 20 20
H2SO4
\ Percentage of Na2CO3 H2C2O4 ¾¾¾® CO + CO2 + H2O
1.06 ´ 100 [H 2O absorbed
= = 84.8% by H 2SO 4]
1.25 4.5 1
At start = = 0 0 0
26 90 20
32. (c) Wt. of NH3 = 26 g = g eq = 1.53 g eq (moles)
1 1 1
17 Final moles 0
Vol. of soln. = 100 mc = 0.1 L 20 20 20
1.53 CO2 is absorbed by KOH.
\ Normality = = 15.3 N
0.1
SOME BASIC CONCEPTS OF CHEMISTRY 441

So the remaning product is only CO. 44. (a) Molar mass of Pb(NO3)2 = 25 × 0.15
Moles of CO formed from both reactions = 3.75m. moles
1 1 1
= + = 1
20 20 10 Molar mass of Al2 (SO4 )3 = ´ 3.75 = M ´ 20
Left mass of CO = moles × molar mass 3
1 M = 0.0625 = 6.25 × 10–2 M
= ´ 28 = 2.8 g 45. (c) This is Avogadro’s hypothesis.
10
40. (a) According to this, equal volume of all gases contain
(1) Mass of water = 18 × 1 = 18 g equal no. of molecules under similar condition of
18 temperature and pressure.
Molecules of water = mole × NA = N = NA
18 A
(2) Molecules of water = mole × NA
Exercise - 3

0.18 1. (a) 0.478 mL = 0.478 g of water; 109 g water contain 0.10 g

= N = 10–2 NA
18 A CHCl3
(3) Molecules of water = mole × NA = 10–3 NA 0.1
\ 0.478 g water contain ´ 0.478 g CHCl3
0.00224 109
(4) Moles of water = = 10–4
22.4
0.1 0.478
Molecules of water = mole × NA = 10–4 NA \ n CHCl3 = ´
41. (a) A + 2HCl ® ACl2 + H2 109 119.5
x x 0.1 0.478
mole = \ No. of molecules = ´ ´ NA
15 15 9 119.5
10
B+ 2 HCl ® BCl 2 + H 2
= 4 × 10–13 × NA
2-x 2-x 2. (a) 14 g of N3– ions have = 8NA valence electrons.
mole =
30 30 8N A
2-x 2.24 1 4.2 g of N3– ions have < ≥ 4.2 < 2.4 N A
x 14
Mole of H2 = + = =
15 30 22.4 10 3. (d) Volume of gold foil = 25 × 40 × 0.25 mm3
x x 1 1 = 250 × 10–3 cm3
– = –
15 30 10 15 Mass of gold foil = 19.32 × 250 × 10–3 g
x = 1 gm = 4.83 g
42. (b) Na2CO3 + HCl —® NaHCO3 + NaCl 4.83
No. of gold atoms = ´ NA
NaHCO3 + HCl —® NaCl + H2O + CO2 197
From the above reactios E is clearly true that 2 moles of = 1.47 × 1022
HCl are required for complete neutralisation of Na2CO3.
Further the titre value using methyl orange n Solute
4. (d) M= ´ 1000 ....(1)
corresponds to complete neutralisation of Na2CO3; the Vol. of solution ( in mL )
titre value using phenolphthalein corresponds only to
the neutralisation of Na2CO3 to NaHCO3, i.e., half of nSolute
the value required by Na2CO3 solution. Hence S is also m= ´ 1000 ....(2)
Weight of solvent ( in g )
true. But E is not the correct explanation of S.
12x 6 n Solute
43. (c) = ; 2x = y for given organic compound (C H O ) m= ´ 1000
y 1 x y z Weight of solvent ( in g ) - wt of solute ( in g )
æ yö y
Cx H y (g) + ç x + ÷ O2 (g) ¾¾ ® xCO2 (g) + H 2O(l) M ´ vol. of solution ( in mL ) ´ 1000
è 4ø 2 m=
Number of oxygen atom in CxHyOz = z 1000 ´ ( wt of solution ( in g ) - wt of solute ( in g ) )
Number of oxygen atom required for CxHy combustion is
æ yö æ yö M ´ 1000
çè x + 4 ÷ø ´ 2 = çè 2x + 2 ÷ø m= -
Density of solution ( g / mL) ´ 1000
1æ yö y
So z = ç 2x + ÷ ; z = x + wt of solute ´ MSolute ´ 1000
2è 2ø 4
2x 3x 3x M Solute ´ volume of solution ( in mL )
z= x+ = ; x : 2x :
4 2 2
2:4 :3 M ´ 1000
m=
Hence empirical formula of compound is C2H4O3. p ´ 1000 - M. MSolute
 EBD_7374
442 CHEMISTRY

5. (a) Molar mass of Pb(NO3)2 = 25 × 0.15 2

= 3.75m. moles mol of Q = ´6 = 4
3
1 A is limiting reactant. Hence, mol of P = 1.5 and mol of
Molar mass of Al2 (SO4 )3 = ´ 3.75 = M ´ 20 Q=3
3
M = 0.0625 = 6.25 × 10–2 M 28
11. (b) Mol. of solute in 100 g solution = =1
28
28
6. (c) Molarity = = 2.5 M
11.2 Mol. of water in 100 g solution = 100 - 28 = 4
1000 mL of solution contain 2.5 mole H2O2 molality, 18
1
2.5 Mol. fraction of solute = = 0. 2 ;
m= ´ 1000 = 2.15 m 1+ 4
1250 - 85
Molality = 1´ 1000 = 125
7. (d) Cr2 O27 - + 6Fe2+ (n = 1) (Mohr 's salt) + 14H + 72 9
® 2Cr 3+ + 6Fe 3+ + 7H 2 O
¾¾ 12. (a) m-moles of HCl = 20 × 0.1= 2
Equivalent of Fe2+ = moles of Mohr's salt = equivalents 2
m-moles of MgO reacted with HCl = Þ1
of K2Cr2O7 1
= 500 × 10–3 × 6 × 1 = 3.0 mass of MgO present = 1 × 40 mg
Hence, mole per cent of Mohr's salt
40
3 \ % of MgO = ´ 100 = 12.5%
= ´100 = 75 320
4 13. (b) m-eq. of FeSO4.7H2O in 1 litre
8. (d) 2C 6 H 6 + 15O 2 (g ) ® 12 CO 2 (g ) + 6 H 2 O( g ) æ 1000 ö
2 ( 78) 15( 32) = 20 × 0.02 × 5 × ç ÷ = 80
è 25 ø
Q156 gm of benzene required oxygen = 15 × 22.4 litre
15 ´ 22.4 W
\1 gm of benzene required oxygen = litre \ ´ 1 ´ 1000 = 80 Þ W = 22.24
156 278
\ 39 gm of benzene required oxygen mass % of FeSO4.7H2O in given sample
15 ´ 22.4 ´ 39 22.24
= = 84.0 litre = ´ 100 = 69.5
156 32
PM dRT 2.28 ´ 0.0821 ´ 300 14. (a) Equivalents of KOH used by oil
9. (c) d = ÞM= =
RT P 1 = [25 × 0.40 – 8.5 × 0.28 × 2] × 10–3
Þ Moles of KOH used = 5.24 × 10–3
= 56.15 g/mol Þ Mass of KOH used in milligrams
85.7 14.3 = 5.24 × 10–3 × 56 × 1000 = 223.44
E.F. = : = 7.14 :14.3 = 1: 2; \ E.F is CH2; 223.44
12 1 \ Saponification number =
M.F = (CH2)n 2
= 146.72
56.15
where n = ; 4;
12 + 2 V ´ 45 (800 - V) ´ 20 800 ´ 29.875
15. (c) + =
\ M.F is C4H8 100 100 100
1 9V V
10. (d) For 3 mol of A : mol of P = ´ 3 = 1.5; mol of Þ + 160 - = 239 Þ V = 316
2 20 5
2
P= ´3 = 3
2
For 2 mol of B : mol of P = 2 ; mol of Q = 2 × 2 = 4
1
For 6 mol of C : mol of P = ´ 6 = 2;
3
 2. STRUCTURE OF ATOM

23. (d) Atomic number is equal to number of protons or

Exercise - 1
number of electrons. Thus if two species have
1. (b) different atomic number they must contain different
2. (b) Cathode rays are never electromagnetic waves. number of protons and electrons. Number of neutrons
3. (c) 4. (c) = Atomic mass – Atomic number. Therefore due to
5. (c) The electrical discharge through the gases could be difference of atomic numbers two species also have
observed only at low pressure and high voltage. different number of neutrons.
6. (b) The cathode rays (negatively charged particles 24. (a)
stream) originates from cathode and move towards 25. (b) Isotopes have same atomic number. Isobars have
anode. same mass number, whereas isoelectronic species
have same number of electrons although the (A) has
7. (b) Millikan determined the value of charge on the electron
same number of electrons but the protons they carry
by using oil drop experiment. are same while in case of isolelectronic species
8. (d) Proton is the nucleus of H-atom (H-atom devoid of its number of protons they carry are different.
electron) 26. (c)
9. (c) As the neutron is a chargeless particle, hence, the beam 27. (d) Atomic number = No. of protons = 8
of neutrons is not deflected by electrical or magnetic Mass number = No. of protons + No. of neutrons
field. = 8 + 8 = 16
10. (a) James Chadwick in 1932 discovered the neutrons. Since the no. of electrons are two more than the no. of
11. (c) protons, hence, it is a binegative species. Thus, the
e 0 species is 16 O82 -.
12. (d) for (i) neutron = =0
m 1
28. (a)
2 c
(ii) a-particle = = 0.5 n1 =
4 29. (d)
ll
1 c c
(iii) proton = = 1 n2 = =
1 l 2 3l1
1 n -n
(iv) electron = = 1837 % change in frequency = 2 1 ´ 100
1 1837 n1
13. (b) N3– , the amount of deviation depends upon the c c 2c
- - ´ 100
magnitude of negative charge on the particle. 3l1 l1 3l1
14. (d) The lesser is the mass of particle, greater is the = ´ 100 =
c c
deflection. l1 l1
15. (c) Deuterium and an a-particle have identical values of = – 66%
e/m. 30. (a) Energy is always absorbed or emitted in whole number
16. (c) Rutherford’s a-ray scattering experiment first showed or multiples of quantum.
the existence of a small positivily charged entity in the
hc c
centre of atom, called nucleus. 31. (d) E = hn = or l =
17. (d) The nucleus occupies much smaller volume compared l n
3 ´108
to the volume of the atom. Þl= = 3.75 ´10 -8 m
15
18. (a) All positive ions are deposited at small part. (nucleus 8 ´10
of atom). In nanometer l = 3.75× 10 nm
19. (d) Electrons are revolving around the nucleus, and which is closest to 4 × 101 nm
centrifugal force is balancing the force of attraction. 32. (c) K.E. of emitted electron
This was explained by Rutherford. = hv - hv0 (i.e. smaller than hv ).
20. (c) 40 contains 22 neutrons and 40 contains 19
18Ar 21Sc 33. (a) At a frequency n > n0, the ejected electrons come out
neutrons. The number of neutrons = (A – Z) with certain kinetic energy.
21. (b) Number of p = number of e– = 89 and neutrons 34. (c)
231 – 89 = 142. 35. (b) For statement (ii) there is no time lag between striking
22. (d) 35 and 37 are isotopes, so they will have of light beam and the ejection of electrons. Kinetic
17 Cl 17 Cl
energy of ejected electron depends on the frequency
same chemical properties. of incident radiation.
 EBD_7374
444 CHEMISTRY

36. (b) For n = 5, we have

37. (c) e/m waves shown in figure A has higher wavelength 5h 2.5h
in comparison to e/m waves shown in figure B. Angular momentum of electron = =
2p p
Thus these waves also differ in frequency and 44. (b) 45. (d)
c 46. (a) Radius of nth orbit = r1 n2 . (for H-atom)
energy. n =
l 47. (a) For hydrogen atom (n) = 1 (due to ground state)
l1 Radius of hydrogen atom (r) = 0.53 Å.
Atomic number of Li (Z) = 3.
hc
(A) Þ E1 = 2 2
l1 Radius of Li2+ ion = r1 ´ n = 0.53 ´ (1) = 0.17
Z 3
48. (c) Energy of an electron in Bohr's orbit is given by the

l2 13.6
relationship. E n = - eV.
(B) Þ E2 =
hc n2
l2 -1312
49. (b) We know that En = kJ mol-1
n2
l1 > l2 Þ E1 < E2 -1312
38. (d) E = hn n2 = kJ mol -1
–328
æcö n=4 (Fourth Bohr orbit)
and n=ç ÷
èlø -1312
Given E 4 = = –82 kJ mol–1
na = 1015, nb = 1014, 42
nc = 1017, nd = 0.85 × 1015
and ne = 10 × 1015, 13.6Z 2
50. (d) For H atom, E n = - eV
n2
hc
39. (c) Energy of a photon, E = For second orbit, n = 2
l Z = At. no. = 1 (for hydrogen)
6.6 ´10-34 (Js) ´ 3 ´108 (ms-1 ) 13.6 ´ (1)2 -13.6
= = 6× 10–19 J \ E2 = - = eV
-9 2 4
331.3 ´10 (m) (2)
No. of photons emitted per second -13.6 ´1.6 ´ 10-19 -19
= J = -5.44 ´ 10 J
600 (J) 4
= =1021
6 ´ 10 -9 (J) -E
51. (a) Energy of an electron En = 0
1 2 n2
40. (a) mn = hn - hn0 For energy level (n = 2)
2
13.6 -13.6
1 En = - = = -3.4 eV.
Þ mn 2 = h ( n - n 0 ) (2) 2 4
2
52. (a) H,He+ and Li2+ are single electron species thus show
2h similar line spectra.
Þ n= (n - n 0 ) 53. (c)
m
54. (c) Vth stationary state, as radii of stationary state is given
41. (c) Since the energy difference between two consecutive
as rn = n2 × a0 Þ n = 5
Bohr orbits is quantized and the energy of higher orbit
is more than that of lower orbit, so an electron from one 1 æ 1 1 ö
55. (c) = Rç 2 - 2 ÷
Bohr stationary orbit can go to next higher orbit by l è n1 n2 ø
absorption of electromagnetic radiation of particular
1 æ1 1 ö
wavelength or frequency. = 1.097 ´ 107 ç - ÷ = 1.097 ´107 m -1
42. (d) For a Bohr atom, angular momentum M of the electron l è1 ¥ ø

=
nh
. l = 91.15 ´ 10 -9 m » 91nm
2p
1 é1 1ù
43. (b) Angular momentum of an electron in n th orbit is given 56. (c) n= ´ IE ´ ê 2 - 2 ú
by h ëê n1 n2 ûú
nh
mvr = 2.18 ´ 10-18 é1 1 ù
2p = ´ê - ú 15 -1
6.625 ´ 10 -34 ë1 16 û = 3.08 ´ 10 s
STRUCTURE OF ATOM 445

Given, r1 = 5 r2, n1 = 5, n2 = 4
æ 1 1 ö
57. (c) D E for two energy levels = 21.79 ç - ÷ J/atom me ´ v1 ´ 5r2 5
ç n2 n2 ÷ =
è 1 2 ø
me ´ v2 ´ r2 4
58. (c) Energy of photon obtained from the transition n = 6 to
n = 5 will have least energy. v1 5 1
Þ = = = 1: 4
æ 1 1 ö v2 4 ´ 5 4
DE = 13.6Z 2 ç -
2 2 ÷
è n1 n 2 ø 69. (b) Z = 3 for Li2+ ions
1 é1 1 ù 52.9 ´ n2
59. (a) u= = Rê 2 – 2 ú So rn = pm
l ë n1 n2 û Z
For second line in lyman series n = 3, Z = 3
n2 = 3 52.9 ´ ( 3)
2
rn = pm
1 é1 1 ù é1 1 ù 8R 3
\ = Rê 2 - 2 ú = Rê – ú =
l ë1 3 û ë1 9 û 9 = 158.7 pm
60. (d) The shortest wavelength in hydrogen spectrum of Also, linear momentum (mv) = 7.3 × 10–34 kg ms–1
Lyman series is given by formula : Then angular momentum will be
w = (mv) × r
1 RH RH 109678 = (7.3 × 10–34 kg ms–1) (158.7 pm)
= = 2 =
l n2 1 1 = 7.3 × 10–34 kg ms–1 × (158.7 × 10–12 m)
Þ l = 9.117 × 10 cm
–6 = 11.58 × 10–48 kg m2 s–1
= 911.7 × 10–10 m = 911.7 Å. = 11.58 × 10–45 g m2s–1
61. (b) 70. (d) Given : Radius of hydrogen atom = 0.530 Å, Number of
62. (c) Bohr model can explain spectrum of any atom or ion excited state (n) = 2 and atomic number of hydrogen
containing one electron only (that is H-like species) atom (Z) = 1. We know that the Bohr radius.
63. (d) Uncertainty principle which was given by Heisenberg n2 (2)2
and not Bohr’s postulate. (r ) = ´ Radius of atom = ´ 0.530
Z 1
64. (d) Bohr’s model can be applied to one electron system
only. = 4 ´ 0.530 = 2.12 Å
Z2
65. (b) Bohr model can only explain one electron system 71. (c) Energy of electron in 2nd orbit of Li+2 = -13.6
n2
66. (c) (i) Beyond a certain wavelength the line spectrum - 13.6 ´ (3) 2
becomes band spectrum. = = –30.6 eV
(ii) For Balmer series n1 = 2 (2) 2
(iii) For calculation of longest wavelength use nearest Energy required = 0 – (–30.6) = 30.6 eV
value of n2. Hence for longest wavelength in 72. (d) Except Al3+ all contain one electron and Bohr’s model
Balmer series of hydrogen spectrum, could explain the spectra for one electron system,
n1 = 2 & n2 = 3. Bohr’s model was not able to explain the spectra of
67. (a) Both assertion and reason are true and reason is the multielectron system.
correct explanation of assertion. 73. (a) l = h/mv ; for the same velocity, l varies inversely with
the mass of the particle.
n2 h2 n2
Radius, rn = = ´ 0.529Å.rn
4pe 2 mZ Z h 6.6 ´10-34
74. (d) l= = = 10-33 m
For first orbit of H-atom mv 60 ´ 10 -3 ´ 10
n=1 75. (d) Given DE = 4.4 × 10–4 J , l = ?
(1)2 hc 6.6 ´ 10 -34 ´ 3 ´ 108
r1 = ´ 0.529Å = 0.529Å l= = = 4.5 ´ 10 -22 m
1 DE 4.4 ´ 10 - 4
68. (d) From the expression of Bohr’s theory, we know that h h
76. (c) We know that l = ; \m =
h mv vl
me v1r1 = n1 The velocity of photon (v) = 3 × 108 m sec–1
2p
l = 1.54 ´10-8 cm = 1.54 ´10 -10 meter
h
& me v 2 r2 = n2
2p 6.626 ´ 10-34 Js
\m =
me v1r1 n1 h 2p 1.54 ´ 10 -10 m ´ 3 ´ 108 m sec -1
= ´ = 1.4285 ´ 10 -32 kg
me v2 r2 n2 2p h
 EBD_7374
446 CHEMISTRY

ch c 1 2
77. (b) E = hn = ; and n = KE = mv
l l 2
3.0 ´108 KE1 m1 v12 9 æ 4 ö 16
2
8 ´1015 = = ´ = ´ç ÷ =
l 2
KE2 m2 v2 1 è 9 ø 9
3.0 ´ 108
\ l= = 0.37 ´ 10 -7 = 37.5 ´ 10-9 m » 4 ´ 101 nm 86. (a) Given mass of an electron(m) = 9.1´10 -28 g;
8 ´ 1015
h Velocity of electron (v ) = 3 ´ 104 cm/s;
78. (b) l=
mv Accuracy in velocity = 0.001% = 0.001 ;
h = 6.6 × 10–34 J/s 100
Actual velocity of the electron
m = 1000 kg
0.001
36 ´103 (Dv ) = 3 ´10 4 ´ = 0.3 cm/s .
v = 36 km/hr = m/sec = 10 m/sec 100
60 ´ 60 Planck’s constant (h) = 6.626×10–27erg-sec.
6.6 ´ 10-34 \ Uncertainty in the position of the electron
\ l= = 6.6 ´ 10-38 m
6.626´10,27 ´ 7
3
10 ´ 10 h
( Dx ) = <
79. (d) Heisenberg's uncertainty Principle is applicable to any 4pmDv 4´ 22´ (9.1´10,28 ) ´ 0.3
moving object. =1.93 cm
h
80. (d) By Heisenberg uncertainty Principle Dx ´ Dp = 87. (a) Dp = mDv
(which is constant) 4p
Substituting the given values of Dx and m, we get
As Dx for electron and helium atom is same thus 1×10–18 g cm s–1 = 9×10–28 g × Dv
momentum of electron and helium will also be same
therefore the momentum of helium atom is equal to 1´ 10 -18
or Dv =
5 × 10–26 kg. m.s–1. 9 ´ 10-28
81. (b) Dx.Dv value will be large for object of smallest mass = 1.1 × 109 cm s–1 ; 1×109 cm s–1
and is therefore the most significant for calculating i.e. option (a) is correct.
uncertainity. 88. (b) According to Heisenberg uncertainty principle.
82. (d) The asseration is false but the reason is true exact h h
position and exact momentum of an electron can never Dx.mDv = Dx =
4p 4 pm Dv
be determined according to Heisenberg’s uncertainty
principle. Even not with the help of electron microscope 600 ´ 0.005
Here Dv = = 0.03
because when electron beam of electron microscope 100
strikes the target electron of atom, the impact causes 6.6 ´ 10 -34
the change in velocity and position of electron. So, Dx =
83. (c) The wavelengths of elements decreases with increase 4 ´ 3.14 ´ 9.1´ 10-31 ´ 0.03
= 1.92 × 10–3 meter
æ h ö 89. (b) Magnetic quantum no. represents the orientation of
in their mass. çQ l = ÷
è mv ø atomic orbitals in an atom. For example px, py & pz have
84. (d) Given, vA = 0.1 ms–1 and vB = 0.05 ms–1 also, mB = 5mA orientation along X-axis, Y-axis & Z-axis
h 90. (b) The sub-shell are 3d, 4d, 4p and 4s, 4d has highest
de-Broglie wavelength, l = energy as n + l value is maximum for this.
mv
91. (a) The possible quantum numbers for 4f electron are
l h / m Av A mB vB
\ A = = 1
l B h / mB vB m Av A n = 4, l = 3, m = – 3, –2 –1, 0, 1 , 2 , 3 and s = ±
2
5mA ´ 0.05 Of various possiblities only option (a) is possible.
= = 5 ´ 0.5 = 2.5 = 5 / 2 92. (b) n = 4 represents 4th orbit
mA ´ 0.1
l = 3 represents f subshell
\ lA : lB = 5 : 2 m = – 2 represents orientation of f-orbital
h
85. (d) de Broglie wavelength l = s = 1/2 represents direction of spin of electron.
mv \ The orbital is 4f.
l1 m2 v2 1 1 v2
= ; = ´ 93. (b) For 4d orbitals, n = 4, l = 2
l 2 m1v1 4 9 v1
v2 9 é For s orbital l = 0 ù
=
v1 4 ê For p orbital l = 1 ú
v1 4 ê ú
= êë For d orbital l = 2 úû
v2 9
STRUCTURE OF ATOM 447

m = –2, –1, 0, +1 or + 2 111. (d) The number of sub shell is (2 l + 1). The maximum
1 1 number of electrons in the sub shell is 2 (2 l + 1)
s = + and - = (4 l + 2).
2 2
112. (b)
1
Thus choice b having n = 4, l = 2, d = 1 and s = is 5p 4f 6s 5d
2
correct. (n + l) 5+ 1 4+ 3 6 + 05 + 2
94. (c) n = 2, l = 1 means 2p–orbital. Electrons that can be 6 7 6 7
accommodated = 6 as p sub-shell has 3 orbital and Hence the order is 5p < 6s < 4f < 5d
each orbital contains 2 electrons. 113. (d)
95. (b) m = – l to +l, through zero thus for l = 2, values of m will 114. (d) The d-orbital represented by option (d) will become
be – 2, –1, 0, + 1, + 2. completely filled after gaining an electron. Therefore
Therefore for l = 2, m cannot have the value –3. option (d) is correct.
96. (c) (a) n = 3, l = 0 means 3s-orbital and n + l = 3 115. (c) 116. (a)
117. (a) For n = 5, l may be 0, 1, 2, 3 or 4
(b) n = 3, l = 1 means 3p-orbital n + l = 4
For l = 4, m = 2l + 1 = 2 × 4 + 1 = 9
(c) n = 3, l = 2 means 3d-orbital n + l = 5 = –4, – 3, – 2, –1, 0, +1, +2, +3, +4
(d) n = 4, l = 0 means 4s-orbital n + l = 4 1
Increasing order of energy among these orbitals is For m = 0, s = +
2
3s < 3p < 4s < 3d
Hence, (a) is correct option.
\ 3d has highest energy..
(b) For any value of n, the value of l cannot be equal or
97. (b) Value of l = 0 ..........(n – 1) greater than value of n, hence it is incorrect.
l cannot be equal to n. (c) For l = 0, m = 0 hence it is incorrect.
98. (b) For n = 5, l = n – 1 = 5 – 1 = 4 (d) The value of s can never be zero. Thus this option is
m = 2l + 1 = 2(4) + 1 = 9 also incorrect.
Sum of values of l and m = 9 + 4 = 13 118. (c) Possible values of l and m depend upon the value of n
99. (a) Quantum number n = 3, l = 2, m = +2 represent an l = 0 to (n – 1)
orbital with m = –l to + l through zero
s =±
1
2 ( 3d xy or 3d 2 2 )
x -y
1
s = + and -
2
1
2
which is possible only for one electron. Thus for n = 3,
100. (d) The orbitals which have same energy are called l may be 0, 1 or 2; but not 3
degenerate orbitals eg. px , p y and pz . m may be –2, –1, 0, +1 or +2
101. (b) 1 1
s may be + or -
102. (a) As n – l – 1 = 5 or 8 – l – 1 = 5 Þ l = 2. 2 2
103. (b) According to given information n = 5 and l = 3. 119. (b)
104. (a) The number of allowed orbitals are given by n 2. 120. (c) First four orbitals contain four lobes, while fifth orbital
Thus when n = 5 consists of only two lobes. The lobes of dxy orbital lie
(5)2 = 25 between x and y axis. Similarly in the case of dyz and
105. (d) We know that atomic number of gadolinium is 64. dzx. their lobes lie between yz and zx axis respectively.
Therefore the electronic configuration of gadolinium Four lobes of d 2 2 orbital are lying along x and y
x -y
is [Xe] 4f 7 5d1 6s2. Because the half filled and fully
axis while two lobes of d orbital are lying along z-
filled orbitals are more stable. z2
106. (c) Fe2+ (26 – 2 = 24) = 1s2 2s2 2p6 3s2 3p6 4s0 3d 6 hence no. axis.
of d electrons retained is 6. [Two 4s electron are Exercise - 2
removed]
107. (b) This configuration represents ground state electronic 1. (c) The concept of electrons move in a circular path of
configuration of Cr. fixed energy called orbits was given by Bohr and not
1s2 2s2 2p6 3s23p63d 5 4s1 derived from Rutherford's scattering experiment.
108. (d) This is as per the definition of Pauli’s exclusion principle. 2. (b) The correct configuration for copper (z = 29) should
109. (b) Electronic configuration of Cu (29) is 1s2 2s2 2p6 3s2 3p6 be 1s22s22p63s23p63d104s1. Due to extra stability of
3d 10 4s1 and not 1s2, 2s2 2p6 3s2 3p6 3d 94s2 due to extra fully filled orbital of d-subshell, the last electron enter
stability of fully filled orbitals. into d-orbital instead of s-orbital.
3. (d) The probability density of electrons in 2s orbital first
110. (b) According to Aufbau principle, the orbital of lower
increases then decreases and after that it increases
energy (2s) should be fully filled before the filling of
again as distance increases from nucleus.
orbital of higher energy starts.
 EBD_7374
448 CHEMISTRY

4. (d) The characteristics of cathode rays do not depend 17. (a) Given: n = 3, l = 1, m = 0
upon the material of electrodes and the nature of the Hence orbital is 3p
gas present in the cathode ray tube.
–1 0 +1
5. (b) The mass of electron is very small as compared to the
mass of the neutron.
Mass of electron = 9.1 × 10–31 kg hence the number of orbital identified by m = 0 can be
Mass of neutron = 1.67 × 10–27 kg one only.
6. (a) J. J. Thomson, in 1898, proposed plum pudding model
of atom. An important feature of this model is that the hc 6.63 ´ 10 - 34 ´ 3 ´ 108
mass of the atom is assumed to be uniformly 18. (d) E = =
l 45 ´ 10 - 9
distributed over the atom. This model was able to
explain the overall neutrality of the atom. = 4.42 × 10– 18 J
7. (d) Isobars have the same mass number (i.e., sum of 19. (c) Series limit is the last line of the series, i.e. n2 = ¥.
protons and neutrons) but different atomic number
1 é 1 1 ù é 1 1 ù R
(i.e., number of protons) e.g., 26Fe58 and 27Ni58 are \u = =Rê 2 - 2ú=Rê 2 - 2ú= 2
isobars. l ëê n1 n 2 úû ëê n1 ¥ úû n1
8. (d) For hydrogen atom (1s) = number of radial nodes
=n–l–1 1 09677.76
Q u = 12186.3 =
Number of radial nodes for 3p orbital = 3 – 1 – 1 = 1 n12
9. (c) Number of angular nodes = l
l = 2 for d-orbital 109677.76
\ Number of angular nodes = 2 Þ n12 = = 9 Þ n1 = 3
12186.3
10. (b) The important implications of Heisenberg uncertainty
\ The line belongs to Paschen series.
principle is that it rules out existence of definite paths 20. (a) The electronic configuration of Rubidium (Rb = 37) is
or trajectories of electrons and other similar particles.
11. (c) Total number of orbitals associated with n th shell = n2 1s 2 2s 2 2 p 6 3s 2 3 p 6 3d 10 4s 2 4 p 6 5s1
\ Total number of orbitals associated with third shell Since last electron enters in 5s orbital
= (3)2 = 9
h 1
12. (a) Orbital angular momentum, mvr = l ( l + 1) Hence n = 5, l = 0, m = 0, s = ±
2p 2
Hence, it depends only on 'l', l can have values ranging 21. (d) l = 3 means f-subshell. Maximum no. of electrons = 4l
from 0 to (n – 1). + 2 = 4 × 3 + 2 = 14
13. (c) The fractional atomic mass (35.5) of chlorine is due to 22. (c) Energy of an electron at infinite distance from the
the fact that in ordinary chlorine atom, Cl-37 and Cl-35 nucleus is zero. As an electron approaches the nucleus,
are present in the ratio of 1 : 3. the electron attraction increases and hence the energy
\ Average atomic mass of Cl of electron decreases and thus becomes negative. Thus
as the value of n decreases, i.e. lower the orbit is, more
3 ´ 35 + 1´ 37
= = 35.5 amu negative is the energy of the electron in it.
4
14. (b) 24Cr = [Ar]3d
5, 4s1 Cr3+ = [Ar]3d3 –13.6 Z2
[Ar]3d6, 4s2 Fe3+ = [Ar]3d5 23. (a) Total energy = eV
26Fe = n2
25Mn= [Ar]3d5, 4s2 Mn2+ = [Ar]3d5
Co = [Ar]3d7, 4s2 Co3+ = [Ar]3d6 where n = 2, 3, 4 ....
27
Sc = [Ar]3d 1, 4s2 Sc3+ = [Ar] Putting n = 2
21
Thus, Fe 3+ and Mn 2+ have the same electronic -13.6
ET = = -3.4eV
configuration. 4
15. (d) For the two electrons of 2s orbital, the value of ms is 24. (d) Two electrons occupying the same orbital should have
1 1 opposite spins i.e. they differ in spin quantum number.
between + and -
2 2 é1
1 1 ù
16. (b) From de-Broglie equation wavelength, 25. (d) For He+ ion, = Z2 R ê 2 - 2 ú
h l ëê n1 n 2 úû
l=
mv 1
( 2 )2 R éê
For same speed of different particles, l µ 1 1 ù 3R
m 2
- ú= 4
ë2 42 û
As h is constant, greater the mass of matter waves,
lesser is wavelength and vice-versa. Among these é1
1 1 ù
matter waves, alpha particle (He2+ ) has higher mass, For hydrogen atom, =Rê 2 - 2ú
therefore, shortest wavelength. l ëê n1 n 2 ûú
STRUCTURE OF ATOM 449

36. (d) The threshold frequency is the minimum frequency

3R é1 1 ù 1 1 3
= R ê 2 - 2 ú or 2 - 2 = required for the ejection of electron from the metal
4 ëê 1
n n 2ú
û n1 n 2
4 surface.
n1 = 1 and n2 = 2. h 6.6 ´ 10 -34
37. (c) l = = = 2 ´ 10 -10 m = 2 Å
26. (b) As electron of charge 'e' is passed through 'V' volt, p 3.3 ´ 10-24
kinetic energy of electron will be eV
h Exercise - 3
Wavelength of electron wave (l) = r
2m.K .E 3/2 -
1 æ 1ö a0
1. (b) y= = e
h h p çè a 0 ÷ø
l= Þ\ = 2meV
2meV l Hence, y 2 is maximum at r = 0, but 4pr2y 2 is minimum at
r = 0.
27. (d) When m = – 3, l = 3, \ n = 4. 1 æ ö
2. (d) = R H Z2 ç 1 - 1 ÷
28. (d) For Balmer n 1 = 2 and n2 = 3; l çn 2 n 2÷
è 1 2 ø
æ 1 1 ö 5R
n = R çç - ÷÷ = cm -1 To calculate shortest wavelength take n 2 = ¥ and
2
è2 32 ø 36 longest wavelength take nearest value of n 2 .
29. (c) For hydrogen like atoms energy of 2s-orbital and For H-atom,
2p-orbital is equal. 1
30. (a) The lines falling in the visible region comprise Balmer , n 2 = ¥ , Z = 1, n1 = 1
l shortest
series. Hence the third line would be n1 =2, n 2 = 5 i.e. 1
5 ® 2. \ = RH (Lyman series)
x
31. (d) Radius of nth Bohr orbit in H-atom 1
= 0.53 n2Å For l for Li 2+ , Z = 3, n1 = 2, n 2
Radius of IInd Bohr orbit = 0.53 × (2)2 longest
= 2.12 Å = 3 (Balmer series)
32. (a) For a given orbital with principal quantum number (n) 1 1 æ 1 1 ö 5
= × 3 2 çç 2 - 2 ÷÷ =
and azimuthal quantum number (l), number of radial l longest x è2 3 ø 4x
nodes = (n - l - 1) 4x
for 3s orbital: n = 3 and l = 0 \ l longest =
\ number of radial nodes = 3 – 0 – 1 = 2 5
3. (a) Total number of spectral lines given by
for 2p orbital: n = 2 and l = 1
\ number of radial nodes = 2 – 1 – 1 = 0 1
[ n - 1] ´ n = 15; \ n = 6
13.6Z 2 2
33. (d) For H atom, En = - eV Thus, electron is excited upto 6th energy level from
n2 ground state. Therefore,
For 2nd orbit, n = 2, Z = 1 (For H)
1 é1 1ù 35
13.6 ´ (1) 2 -13.6 = R H ê - ú = 109737 ´ ;
\ E2 = - = eV l ë12 2
6 û 36
(2) 2 4 l = 9.373 × 10–6 cm = 937.3 Å
-13.6 ´1.6 ´ 10-19 -19
4. (d) Energy of photon corresponding to second line of
= J = -5.44 ´ 10 J Balmer series for Li2+ ion
4
2é 1 1ù
34. (d) Angular speed is
V
. Vn µ
1
and rn µ n 2 . = (13.6 ) ´ (3 ) ê 2 - 2 ú
r n ë2 4 û
\ Angular speed is inversely proportional to n 27
= 13.6 ´
35. (b) From first line of Balmer series 16
Energy needed to eject electron from n = 2 level in
1 æ 1 1 ö
= RHZ2 ç – ÷ H-atom;
λ ç n2 n2 ÷
è 1 2 ø
2 é 1 1 ù 13.6
= 13.6 ´ 1 ´ ê 2 - 2 ú Þ
1 æ 1 1 ö ë2 ¥ û 4
= 1.09 ´ 107 ´ 12 ç - ÷
l è2 2
32 ø K.E. of ejected electron
(transition 3 ® 2) 9 ´ 3 13.6 æ 27 - 4 ö
l = 654 nm = 13.6 ´ - = 13.6 ´ ç ÷
16 4 è 16 ø
Þ 19.55 eV
 EBD_7374
450 CHEMISTRY

5. (a) From de-Broglie equation,

2 ´ 0.4063 ´ 10 -22
h T=
l= ; 3 ´ 1.38 ´ 10 -23
2Vem = 0.19 × 10
h = 1.9 » 2
l= (for proton)
2Vem p 11. (a) There is only one type of transition from n = 2 to
n = 1 and hence emitted radiation will constitute only
h one frequency.
l= (for Li 3+ ) (Q mLi = 9 mp.)
2V3em Li 12. (c) As per Einstein's equation of photoelectric effect
hn = hno + K.E.
l Li3+ 2Vem p 1 1 hc hc
\ = = \ mn 2 = hn - hno = -
lp 6Vem p ´ 9 3 3 2 l lo

hc 2hc æ 1 1 ö
6. (d) E=n n2 = ç - ÷;
l m è l lo ø
2 ´ 10-17 1240 eV.nm 1/2
Þ -19
eV = n ´ é 2hc æ 1 1 öù
1.6 ´ 10 595.2 nm n=ê ç - ÷ú
Þ n = 60 ëê m è l lo øûú
7. (b) Let wavelength of particle be x
1/2
x é 2hc æ l o - l ö ù
So, velocity (v) = Þ ê ç ÷ú
100 ëê m è ll o ø ûú
h h ´ 100 13. (c)
l= ; x=
mv m´x 14. (c) n1 + n2 = 4 ............. (i) n2 - n1 = 2 ........... (ii)
n1 = 1, n2 = 3
h h
x 2 = 100 or x = 10
m m æ 1 1ö
2
u = RH Z ç 2 - 2 ÷
8. (a) è n1 n2 ø
9. (a) The energy of an orbital is given by (n + l). In (D) and
(E), (n + l) value is (3 + 2) = 5, hence they will have same é1 1 ù
= RH ´ 32 ´ ê - ú = 8 RH
energy, since here n values are also same. ë11 32 û
(h = 6.63 × 10–34 Js)
10. (b) l = 76.3 nm = 76.3 × 10–9 m 1
h 2
15. (a) We know l = and K.E. = mv
h h 6.62 ´ 10 -34 mv 2
l= , P= =
P l 76.3 ´ 10-9 From the above relation, we get
P = 0.086 × 10–25
hv
1 1 1 2 K.E. =
K.E = mv 2 = (mv)2 = P 2l
2 2m 2m
é 1 2 ù
K.E =
P 2 (0.086 ´ 10-25 ) 2
= êQ K.E. = 2 mv ú
2m 2 ´ 9.1 ´ 10 -31 ê ú
ê \ mv = 2K.E. ; l = hv or K.E. =
hv ú
7.396 ´ 10-53 êë v 2K.E. 2l úû
=
18.2 ´ 10-31 Since K.E. for two particles is same, so l µ v
= 0.4063 × 10–22 J
i.e., option (a)
3
k BT = K.E = 0.4063 ´ 10 -22 J
2
 3. CLASSIFICATION OF ELEMENTS AND PERIODICITY IN
PROPERTIES

Exercise - 1 24. (c)

25. (b) Its valence shell has 5 electrons (ns2, np3). It belongs
1. (c) Periodic classification of elements follow a logical to 5th group of the periodic table.
consequence of electronic configuration of atoms 26. (d) Barium has atomic number 56. It is an alkaline earth
which is used to examine the physical and chemical metal i.e., found in s-block.
properties of the elements. 27. (c)
2. (c) According to Dobereneir’s triad the atomic mass of Br 28. (c) Element with Z = 33
will be average of the atomic masses of Cl & I
2 2 6 2 6 10 2 3
35.5 + 127 (1s 2 s p 3s p d 4 s p ) lies in fifth (or 15th) group.
= = 81.25 29. (b)
2
30. (c) Elements (a), (b) and (d) belong to the same group
3. (a)
since each one of them has two electrons in the s sub
4. (b) Lothar Meyer plotted the physical properties such as
shell. In contrast, element (c) has seven electrons in
atomic volume, melting point and boiling point against
the valence shell and hence does not lie in the same
atomic weight and obtained a periodically repeated
group in which elements (a), (b) and (d) lie.
pattern.
31. (c)
5. (a) 6. (c)
32. (b) Na and Cl both belongs to III period.
7. (b) Correct order is Dobereiner, Chancourtois, Newlands,
33. (b) 34. (b)
Mendeleev.
8. (d) Chloride formulas 35. (b) 1s 2 , 2s 2 2 p6 , 3s 2 3 p 4
1442443
(i) Eka-Aluminium = GaCl3(ECl3) ¯
(ii) Eka-Silicon = GeCl4(ECl4)
Number of shell = 3
Mendeleev arranged elements in horizontal rows and
(Principal quantum number)
vertical columns of a table in order to their increasing
Number of period = 3
atomic weights.
Valence electrons = 6 i.e., 2 + 4
9. (b) 10. (b)
Number of group = 16
11. (a) Iodine with lower atomic weight than that of tellurium
36. (a) Metallic character decreases down group and increases
(group VI) was placed in group VII along with fluorine,
along a period.
chlorine, bromine because of similarities in properties.
37. (b) Cu, Ag and Au are coinage metals. They belong to group
12. (d) Oxides of Eka-Aluminium = Ga2O3
IB (d-block) of periodic table.
Oxides of Eka-Silicon = SiO2
Melting point of Eka-Aluminium = Low (302 K) 38. (b) 39. (b)
Melting point of Eka-Silicon = High (1231 K) 40. (b) Non-metals are mainly placed in p-block elements.
13. (c) Moseley discovered that atomic number is more 41. (b) Non-metallic character increases on moving from left
fundamental property than atomic mass. to right in a period.
14. (d) 6th period consists of 32 elements. 42. (d) In fourth period filling up of 3d orbital becomes
15. (b) energetically favourable before the 4p orbital is filled.
16. (a) Atomic number (Z) = 120 43. (c) 44. (d) 45. (d)
IUPAC name = Unbinilium 46. (c) He (1s2) should be placed along with s-block elements
Symbol = Ubn because of its electronic configuration but it has a
17. (b) Element with atomic number 104 was named by completely filled valence shell and as a result it exhibits
American society as Rutherfordium and Kurchatovium properties of noble gases, thus it is placed along with
by soviet society. noble gases (ns2, np6).
18. (c) Digit Name 47. (d) Neptunium and plutonium like actinium and
1 un protoactinium are also found in pitch.
4 quad 48. (a) Seventh period includes most of the man-made radio-
Using above notation IUPAC name of element 114 is active elements.
Ununquadium. 49. (a) Atomic number of the given element is 15 and it
19. (b) 20. (b) 21. (b) belongs to 5th group. Therefore atomic number of the
22. (a) Both assertion and reason are true and reason is the element below the above element
correct explanation of assertion. = 15 + 18 = 33.
23. (c) Halogens are most electronegative elements i.e., they 50. (b) These are characteristic properties of d-block elements.
are likely to form anions most readily. 51. (b) 52. (b) 53. (b) 54. (c) 55. (d)
 EBD_7374
452 CHEMISTRY

56. (c) Number of elements in each period is twice the number 79. (d) Helium (He) 1s2 ® Highest ionisation
of atomic orbitals available in the energy level that is energy due to noble gas
being filled. in nature.
57. (a) By observing principal quantum number (n). Orbital Fluorine (F) 1s2, 2s22p3 ® High electronegativity
(s, p, d, f ) and equating no. of e–’s we are able to find in nature due to small
the period, block and group of element in periodic table. size and –1 oxidation
58. (b) Correct order of ionic size is Sn > Ce > Yb > Lu. state.
59. (c) On moving down in a group atomic radii increases due Rubidium (Rb) ® Most electronegative
to successive addition of extra shell hence element due to large
O < S < Se atomic size.
Further As is in group 15 having one less electron in its Lithium (Li) ® Strongest reducing
p orbital hence have higher atomic radii than group 16 agent due to small size
elements. and positive oxidation
i.e., O < S < Se < As state (+1)
60. (a) 80. (b) Second ionization enthalpy will be higher than the first
61. (c) Isoelectronic ions have same number of electrons. ionization enthalpy but lower than the third ionization
62. (a) Continuous increase as no. of shells increases down enthalpy.
the group. 81. (c)
63. (d) The size of an anion will be larger than that of the parent 82. (b) A. Li+ < Al2+ < Mg2+ < K+
atom because the addition of one or more electron(s) The cation with the greater positive charge will
would result in increased repulsion among the electrons have a smaller radius because of the greater
and a decrease in effective nuclear charge. attraction of the electrons to the nucleus. Anion
with the greater negative charge will have the
64. (b) K + ® K 2 + + e - . Since e– is to be removed from stable
larger radius.
configuration.
65. (a) IE1 is always less than IE2. 1
Positive charge µ
66. (a) 2 2 6 2 ionic radius
Mg = 1s 2 s 2 p 3s
Negative charge µ ionic radius
After removing of 2 electron, the magnesium acquired
B. Greater positive charge, increases effective nuclear
noble gas configuration hence removing of 3rd electron
will require large amount of energy. charge in case of isoelectronic species. While for
67. (d) ns1 configuration and lesser IE. same group elements effective nuclear charge
decreases down the groups.
68. (b) As I.E. of Mg is more
C. Cl > F > Br > I
69. (a) The halogen (group-17) and the chalcogens
electron affinity of Cl is highest in halogen family.
(group-16) are two groups of elements having highly
D. F > Cl > Br > I
negative electron gain enthalpies.
70. (b) O < S < F < Cl electronegativity of fluorine (F) is higher than Cl,
Electron gain enthalpy –141, –200, – 333, – 349 kJ mol–1 Br and I.
83. (b) In case of halogens covalent radius is considered this
71. (a)
bond is formed by overlapping of electron clouds;
72. (d) Noble gases have positive values of electron gain
while noble gases remain monoatomic, in this case
enthalpy because the anion is higher in energy than
only way to obtain radius is through van der Waal
the isolated atom and electron.
73. (a) Within a group, electron gain enthalpy becomes less radii.
negative down a group. However, adding an electron 84. (c) Covalent radius is radius of an atom in its bound state
i.e., in fluorine it is half of distance between two
to the 2p-orbital leads to greater repulsion than adding
covalently bonded fluorine atoms; van der Waal radii
an electron to the larger 3p-orbital. Hence, phosphorus
is one-half of the distance between the nuclei of two
has the least negative electron gain enthalpy.
identical non-bonded isolated atoms. These atoms are
74. (a)
75. (a) Electronegativity values of given elements are as attracted toward each other through weak van der
follows: Waal’s force hence van der Waal radii are very large.
85. (c) All the given species are isoelectronic. In case of
Be – 1.5 (I) Mg – 1.2 (IV)
isoelectronic species ionic radii increases with increase
O – 3.5 (II) N – 3.0 (III)
in negative charge on anions.
i.e. II > III > I > IV
86. (c) I represents Li, II represents K
76. (b) It is electronic configuration of alkali metal. Hence it
will form basic oxide. III represents Br, IV represents I
77. (d) V represents He
So, amongst these, II represents most reactive metal
78. (b) On passing from left to right in a period acidic character
and V represents least reactive non-metal.
of the normal oxides of the elements increases with
87. (b) 88. (b) 89. (c)
increase in electronegativity.
CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES 453

90. (b) In the isoelectronic species, all isoelectronic anions However, the electron gain enthalpy of F is less
belong to the same period and cations to the next negative than that of Cl due to its small size. Thus, the
period. negative electron gain enthalpy among halogens
91. (c) Atomic size generally decreases along a period. follows the order :
92. (c) Electron affinity of 9F is less than that of 17Cl F < Cl > Br > I
93. (b) Fully filled electronic configuration. 8. (c) As each period starts with the filling of electrons in a
94. (c) The increase in the electronegativities across a period new principal quantum number, so, the period number
is accompanied by an increase in non-metallic in the long form of the periodic table refers to the
properties (or decrease in metallic properties) of maximum principal quantum number (n) of any element
elements. in the period.
95. (b) On moving along the period, ionization enthalpy 9. (c) The elements in which electrons are filled in 4f-orbital
increases. are called lanthanoids. Lanthanoids consist of
In second period, the order of ionization enthalpy elements from Z = 58 (cerium) to 71 (lutetium).
should be as follows : 10. (d) Generally, cations are smaller in size while anions are
F > O > N. bigger in size than the neutral atom.
But N has half-filled structure, therefore, it is more 11. (c) O2– has noble gas configuration and isoelectronic with
stable than O. That is why its ionization enthalpy is neon but its formation is unfavourable due to strong
higher than O. Thus, the correct order of IE is electronic repulsion between the negatively charged
F > N > O. O– ion and the electron being added.
96. (d) With the exception of lithium and beryllium compounds Thus, the electron repulsion will be more than the
of s-block elements are predominantly ionic. stability gained by achieving noble gas configuration.
97. (d) All the given species contains 10 e– each i.e. 12. (c) The element with atomic number 57 belongs to d-block
isoelectronic. element as the last electron enters into the 5d-orbital
For isoelectronic species anion having high negative against the aufbau principle. This anomalous behaviour
charge is largest in size and the cation having high can be explained on the basis of greater stability of
positive charge is smallest. the xenon (inert gas) core.
98. (c) Assertion is true but reason is false. After barium (Z = 56), the addition of the next electron
Electronegativity refers to the tendency of atom to should occur in 4f-orbital in accordance with aufbau
attract bonding electrons. principle. This will however, tend to destabilize the
xenon core (Z = 54), [Kr] (4d10 4f 0 5s2 5p6 5d0) since
Exercise - 2
the 4f-orbitals lie inside the core.
1. (b) In case of isoelectronic species Therefore, the 57th electron prefers to enter 5d-orbital
1 which lies outside the xenon core and whose energy
ionic radii µ is only slightly higher than that of 4f-orbital.
atomic number
Thus, the outer electronic configuration of
\ The correct order of increasing ionic radii will be : La(Z = 57) is 5d1 6s2 rather than the expected 4f 1 6s2.
Ionic radii Mg 2+ < Na + < F- < O 2- 13. (c) Each period starts with the filling of electrons in a new
principal energy shell. Therefore, 6th period starts with
Atomic number (12) (11) (9) (8 )
the filling of 6s-orbital and ends when 6p-orbitals are
2. (d) Elements with atomic number, Z = 90 to 103 are called completely filled.
actinoids. Terbium belongs to lanthanoids. Thus, the outermost electronic configuration of the
3. (a) For a given shell, screening effect decreases in the last element of the p-block in the 6th period is
order : s > p > d > f. represented by 6s2 4f 14 5d10 6p6 or 4f 14 5d10 6s2 6p6.
4. (a) Electronic configuration for the given elements will be : 14. (c) The long form of the periodic table contain element
Na = [Ne]3s1, Mg = [Ne]3s2, Al = [Ne]3s23p1, with atomic number 1 to 118.
Si = [Ne] 3s23p2 15. (a) The fifth period begins with Rb (Z = 37) and ends at
Ionisation enthalpy increases along a period but I.E Xe (Z = 54). Thus, the element with Z = 43 lies in the
of Mg is higher than Al because of completely filled 3s 5th period. Since, the 4th period has 18 elements, thus,
orbital in Mg. the atomic number of the element which lies
5. (c) The electronic configuration of Gd (Z = 64) is immediately above the element with atomic number 43
[Xe] 4f 7 5d1 6s2. will be 43 – 18 = 25.
6. (c) In case of transition element, the order of filling of The electronic configuration of the element with
electrons in various orbital is 3p < 4s < 3d. Thus, 3d Z = 25 is
orbital is filled only when 4s orbital gets completely filled. 1s2 2s2 2p6 3s2 3p6 3d 5 4s2 (i.e., Mn).
7. (c) As we move in a group from Cl to I, the electron gain 16. (b) The elements with atomic numbers 35(36 – 1),
enthalpy (i.e., energy released in electron gain) become 53( 54 – 1) and 85(86 – 1), lie in a group before noble
less and less negative due to corresponding increase gases, i.e., belongs to halogens (group 17).
in the atomic size.
 EBD_7374
454 CHEMISTRY

17. (a) Electronic configuration of given elements indicate that The correct order of electron affinity is: I < Br < F < Cl
A is a noble gas (i.e., Ne), B is oxygen, C is sodium Halogens have high electron affinities which decreases
metal and D is fluorine. on moving down the group. However, fluorine has
(i) Noble gases have no tendency to gain electrons lower value than chlorine which is due to its small size
since all their orbitals are completely filled. and repulsion between the electron added and electrons
\ element A will have the least electron gain already present.
enthalpy. 29. (c) As we move along the period, the atomic size decreases
(ii) Element D has one electron less and element B due to increase in nuclear charge. Therefore, it is more
has two electrons less than the corresponding difficult to remove electron from an atom. Hence the
noble gas configuration, hence, element D will sequence of first ionization enthalpy in decreasing order
is
have the highest electron gain enthalpy in
F > N > C > Be > B
comparison to element B.
But ionization enthalpy of boron is less as compared
(iii) Since, element C has one electron in the s-orbital
to beryllium because first electron in boron is to be
and need one more electron to complete its removed from p-orbital while in beryllium, it is to be
configuration, therefore, electron gain enthalpy removed from s-orbital.
of C is less than that of element B. So, we can As s-orbital is closer to nucleus in comparison to p-orbital
conclude that the electron gain enthalpies of the thus energy required to remove an electron from s-
four elements increases in the order : A < C < B < orbital is greater.
D. 30. (b) Alkali metals have the lowest ionization energy in each
18. (N) All options are incorrect. period on the other hand Sc is a d-block element.
19. (c) Transition metals have smaller atomic radii and higher
20. (b) An isoelectronic species having highest positive nuclear charge leading to high ionisation energy.
charge among given species has smallest size. 31. (b) Closed shell (Ne), half filled (P) and completely filled
2 1 2 4 configuration (Mg) are the cause of higher value of I.E.
21. (c) The element A is ns p and B is ns p . They can 32. (a) Z = 114 belong to Group 14, carbon family
form compound of the type A 2 B3 . Electronic configuration = [Rn]5f 146d107s27p2
33. (a) According to the law of triads the atomic wt of the
22. (b) In isoelectronic species the radius decrease with
middle element is arithmatic mean of I and III.
increase in nuclear charge hence increasing order of
radius is At.wt of Cl + At. wt of I
At wt of Br =
Ca2+ < K+ < Ar 2
23. (a) Incoming electrons occupies the smaller n = 2 shell, 34. (a) Isoelectronic species have same no. of electrons.
also negative charge on oxygen (O–) is another factor ions O2– F– Na+ Mg2+
due to which incoming electron feel repulsion. 8+2 9 + 1 11 – 1 12 – 2
Hence electron repulsion outweigh the stability gained No. of e– = 10 10 10 10
by achieving noble gas configuration. \ O2–, F–, Na+ , Mg2+ are isoelectronic
24. (c) In a period the value of ionisation potential increases 35. (a) Mg can form basic carbonate like
from left to right with breaks where the atoms have 3MgCO3 . Mg(OH)2 . 3H2O
some what stable configuration. In this case N has half while Li can form only carbonate (Li2CO3) not basic
filled stable orbital. Hence has highest ionisation carbonate.
energy. Thus the correct order is 36. (b) The right sequence of I.E1 of
B < C < O < N not B < C < N < O Li < B < Be < C.
25. (a) Both assertion and reason are correct and reason is 37. (b) It is difficult to remove an electron from a positively
correct explanation of assertion. charged ion than a neutral atom. Hence IE2 > IE1 i.e.,
assertion is true. Smaller is the ionization enthalpy
26. (a) For isoelectronic species, size of anion increases as
(energy) more easily the element will lose the electron.
negative charge increases. Thus the correct order is
Reason is not the explanation of Assertion.
27. (b) Electronic configuration of element with atomic number
38. (d) The smaller the atomic size, larger is the value of
118 will be [Rn]5f146d10 7s27p6. Since its elctronic ionisation potential. Further the atoms having half filled
configuration in the outer most orbit (ns2np6) resemble or fully filled orbitals are comparatively more stable,
with that of inert or noble gases, therefore it will be hence more energy is required to remove the electron
noble gas element. from such atoms.
28. (b) The correct order is B < C < O < N
Generally ionisation energy increases across a period. Exercise - 3
But here first I.E. of O is less than the first I.E. of N. This
is due to the half-filled 2p orbital in N(1s2, 2s2, 2p3) which 1. (b) Let us consider the opposite process :
is more stable than the 2p orbital in O (1s2, 2s2, 2p4). (a) F(g) + e - ¾¾
® F- (g) ; DH1
CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES 455

i.e. 1 mole realease energy

(b) ® P - (g) ; DH2
P(g) + e - ¾¾ = 3.7 × 23.06 kcal
\ Energy released
(c) S(g) + e - ¾¾
® S- (g) ; DH3
1
= ´ 3.7 ´ 23.06 kcal = 2.4 kcal
35.5
(d) Cl(g) + e - ¾¾
® Cl - (g) ; DH4
9. (d) As the size increases, the basic nature of oxides
Order of energy releases is : DH4 > DH1 > DH3 > DH2 changes to acidic nature i.e., acidic nature increases.
-
® P(g) + e - requires least energy..
So, P (g) ¾¾ SO 2 > P 2 O 3 > SiO 2 > Al 2 O 3
2. (d) For option (a) and (b) use (z/e) concept for isoelectronic Acidic Weak Amphoteric
acidic
species.
In option (c) size of neutral atom is greater than its SO2 and P2O3 are acidic as their corresponding acids
cation. H2SO3 and H3PO3 are strong acids.
In option (d) Se2– and As3– are related with 4th period,
10. (d) Successive electron affinity always decrease
while Ba2+ and Cs+ related with 6th period (these are
+e
not isoelectronic species). O ¾¾® O - DHeg = ( -) ve
3. (b) Ionization energy is not the only the criteria for the
+e
stability of an oxidation state. O - ¾¾® O2 - DHeg = ( + ) ve
4. (a) IE1 is always less than IE2.
+ 2e
5. (d) ® O2-
O ¾¾¾ DH eg (Total) = ( + ) ve
W : Phosphorus Y : Oxygen X : Sulphur Z : Chlorine
Electronegativity O > Cl > S > P Catenation : S > P > O > Cl
Thus, O2– will show most positive DHeg, while O2+ will
Electron Affinity : Cl > O > S > P Oxygen exhibits covalency of two only show most negative value due to small size.
6. (a) The electronegativity difference between M1 and O is
0.1, which indicates M1– O bond will be covalent, since 11. (b) Electronegativity of an atom = IE + EA where IE and
O–H bond having more ionic character thus bond will 2 ´ 62.5
–1
EA are in k cal mol .
break and H+ ions gets release and acidic solution is
formed and whereas difference between 12. (b) Mg2+ and O2– ions have higher charge, and size of Li +
electronegativity of M2 -O is 2.3, thus, M2–OH bond and F– are smaller than K+ and Br – .
will break. Hence, solution will be basic in nature.
[IE + EA]
7. (d) O(g) + 2e - ® O2 - , DH = 603kJ mol-1 ......(i); 13. (c) Electronegativity = 0.374 + 0.17
2
O(g) + e - ® O - , DH = -141 kJ mol–1 ......(ii)
(i) - (ii) gives : [17.42 + 3.45]
= 0.374 + 0.17 = 4.07
2
O- (g) + e - ® O 2 - (g),
14. (b) The third period element Cl has large size and vacant
DH = 603 - (-141) = 744kJ mol–1 3d orbitals, which can accommodate incoming electron
1 easily compare to second period element (F).
8. (d) Number of moles =
35.5 So order is F (g) < Cl (g).
Given, 1 eV = 23.06 kcal mol–1 15. (b) He (Z = 2) is a noble gas and has highest I.E. The I.E. of
3.7 eV = 3.7 × 23.06 kcal mol–1 Be (Z = 4) is more than that of Li (Z = 3)
 EBD_7374
456 CHEMISTRY

4. CHEMICAL BONDING AND MOLECULAR STRUCTURE

Exercise - 1 1
Formal charge on O2 = 6 – 4 – (4) = 0
2
1. (d) The evolution of various theories of valence and the
interpretation of the nature of chemical bonds have 1
Formal charge on O3 = 6 – 6 – × 3 = –1
closely been related to the developments in the 2
understanding of structure of atom, electronic Hence, correct representation of O3 is
configuration of elements and Periodic Table. (+1)
2. (b) Kossel and Lewis provide some logical explanation

:
O
of valence which was based on the intertness of
(0) (–1)

: :
: :
noble gases. O O:
3. (b) Langmuir (1919) refined the Lewis postulations by
abandoning the idea of the stationary cubical .. .. .. .. ..
arrangement of the octet, and by introducing the 11. (d) O .. S .. O
.. ..
term covalent bond.
4. (b) Electrovalent bond is formed as a result of electrostatic
Total no. of valence electron around sulphur in SO2 is
attraction between the positive and negative ions.
10 while in case of other molecules total no. of 8
5. (d) When a metal for example Na combines with a non
electrons are present in each.
metal e.g., Cl2. Following reaction occurs
12. (b) The compounds in which octet of central atom is
2Na + Cl 2 ¾¾ ® 2NaCl incomplete are known as electron deficient
In this process Na loses one electron to form Na+ and compounds. Hence B2H6 is a electron deficient
Cl accepts one electron to form Cl– compound.
® Na + + e-
Na ¾¾ 13. (a) PCl5 does not follow octet rule, it has 10 electrons in its
Cl + e - ¾¾
® Cl - valence shell.
Therefore, in this process Cl gain electrons and hence 14. (a) Atoms combine either by transfer of valence electrons
its size increases. from one atom to another or by sharing of valence
6. (c) Each combining atom contributes at least one electrons to have an octet in their valence shell.
electron to the shared pair. 15. (a)
7. (a) All Lewis representation of the molecules NH3, O3 and 16. (c) Sulphur forms many compounds in which the octet
HNO3 given in question are correct. rule is obeyed. For example SCl2 has an octet of
8. (a) The lowest energy structure is the one with the electrons around it.
smallest formal charges on the atoms. 17. (b) Ionic bonds will be formed more easily between
9. (c) Bond order between P – O elements with comparatively low ionization enthalpies
no. of bonds in all possible direction 5 and elements with comparatively high negative value
= = = 1.25
total no. of resonating structures 4 of electron gain enthalpy.
18. (a) In ionic solids, the sum of the electron gain enthalpy
O O
– and the ionization enthalpy may be positive but still
– – – the crystal structure gets stabilized due to the energy
O P O O P O
released in the formation of the crystal lattice.
O
–
–
O
–
–
19. (d) Lattice enthalpy is required to completely separate
O O one mole of a solid ionic compound into gaseous
–
O P O
– –
O P O constituent ions.
– 20. (c) Higher the difference in electronegativity between the
O O
two atoms, more will be electrovalent character of the
3 bond. Among given choices, calcium and hydrogen
Formal charge on oxygen = - = - 0.75 have maximum difference in their electronegativities.
4
21. (b) For compounds containing cations of same charge,
1
lattice energy increases as the size of the cation
:

O
10. (a) decrease. Thus, NaF has highest lattice energy. The
2 3
size of cations is in the order Na+ < K+ < Rb+ < Cs+
: :
: :

O O:
22. (b) The stability of the ionic bond depends upon the lattice
1 energy which is expected to be more between Mg and
Formal charge on O1 = 6 – 2 – (6) = +1
2 F due to +2 charge on Mg atom.
CHEMICAL BONDING AND MOLECULAR STRUCTURE 457

23. (c) CH2Cl2 is polar while CCl4 is non-polar because in CCl4

24. (d) According to Fajan's rule : net dipole moment cancels.
1 42. (c) CCl4 and BF3 being symmetrical have zero dipole
Covalent character µ moment. H2O, CHCl3 and NH3 have dipole moments of
size of cation
1.84 D, 1.01 D and 1.46 D respectively. Thus among the
µ size of anion
given molecules H2O has highest dipole moment.
Among the given species order of size of cations
43. (c) As difference of electronegativity increases % ionic
N3+ < O2+ < Pb2+ < Ba2+
character increases and covalent character decreases
order of size of anions O2– > Cl–.
i.e., electronegativity difference decreases covalent
Hence the order of covalent character is
character increases.
NCl3 > Cl2O > PbCl2 > BaCl2 Further greater the charge on the cation and smaller
BaCl2 is most ionic in nature. the size more will be its polarising power. Hence
25. (d) Assertion is false but reason is true. covalent character increases.
The greater the lattice enthalpy, more stable is the ionic 44. (d) In case of anions having same charge as the size of
compound. anion increases, polarisibility of anion also increases.
26. (d) Bond lengths are measured by spectroscopic, X-ray 45. (a) A gaseous HCl molecule has hydrogen and chlorine
diffraction and electron diffraction techniques. linked by a covalent bond. Here electronegativity of
27. (c) The covalent radius is measured approximately as chlorine is greater than that of hydrogen. Due to this
the radius of an atom’s core which is in contact with the shared pair of electron is more attracted towards
the core of an adjacent atom in a bonded situation. chlorine. Thus, chlorine end of molecule has higher
28. (d) All of the given statements are correct. electron density and becomes slightly negative and
29. (b) Both NO2 and O3 have angular shape and hence will the hydrogen and slightly positive. Hence the covalent
have net dipole moment. bond in HCl has a polar character as shown below
30. (c) Both representation of resonating structures in + -
molecules of CO2 and CO2– d d
3 are correct.
31. (c) I and II structure shown above constitute the H Cl
cannonical structure. III structure represents the 46. (b) O = C = O
structure of O3 more accurately. This is also called 47. (b) Covalent radius is half of the distance between atoms
resonance hybrid. in bonding state, while van der Waal radius is half of
32. (a) The molecule does not exist for a certain fraction of the distance between atoms in its non bonding state.
time in one cannonical form and for other fractions 48. (a) The correct order of dipole moments of HF, H2S and
of time in other cannonical forms. H2O us
33. (c) The dipole moment of symmetrical molecules is zero. HF < H2S < H2O
49. (d)
F 50. (b) Hybridisation is sp3 and shape pyramidal.
|
| B F
F F :
|

Triangular planar (symmetrical molecule)

34. (b) 51. (c)
35. (c) According to Fajan's rule, smaller size and greater Br F
charge on cation favour the formation of partial
covalent character in ionic bonds. :
36. (a) According to Fajan’s rule, as the charge on the cation F
increases, and size decreases, its tendency to polarise
the anion increases. This brings more and more In BrF3, both bond pairs as well as lone pairs of
covalent nature to electrovalent compounds. Hence electrons are present. Due to the presence of lone pairs
AlCl3 shows maximum covalent character. of electrons (lp) in the valence shell, the bond angle is
37. (d) The electronegativity difference is maximum in O—H contracted and the molecule takes the T-shape. This
bond hence O—H bond length is the smallest among is due to greater repulsion between two lone pairs or
the given set. between a lone pair and a bond pair than between the
two bond pairs.
d+ d-
52. (a) The number of lone pairs of electrons on central atom
38. (a) C-F
in various given species are
Because difference between electronegativity of Species Number of lone pairs on
carbon and flourine is highest. central atom
39. (c) In case of SF6 resultant dipole moment is zero while all IF7 nil
other possess dipole moment. IF5 1
40. (c) ClF3 2
41. (d) Assertion is false but reason is true. XeF2 3
 EBD_7374
460 CHEMISTRY

A = charge on anion PF5 Þ sp3d

1 BCl3 Þ sp2
So, Hybridisation (in ClF3) = [7 + 3 - 0 + 0] = 5 C2H6 Þ sp3
2 101. (b) Hybridisation of the central atom in compound is given
Þ sp3d Hybridisation by
92. (a) Hybridisation of carbon in CH 3+ is sp2 and in CH4 its
hybridisation is sp3 1
H= [V + M - C + A]
2
93. (c) (a) CH 2 = C = CH 2
where V = No. of valency electrons in central metal
sp 2 sp sp 2
atom,
+ M = No. of monovalent atoms surrounding the central
(b) CH3 — CH = CH— CH 2 atom,
sp3 sp 2 sp 2 sp 2
C = charge on cation and A = charge on anion
+
(c) CH3 — C º C— CH 2 1
sp sp · For NO -2 , H = [5 + 0 - 0 + 1] = 3
sp3 sp 2 2
sp2 hybridisation
(d) CH3 — CH = CH— CH 2–
2 2 1
sp3 sp sp sp 3 · For SF4, H = [6 + 4 - 0 + 0] = 5
2
Note : Carbocations and carboanions are sp2 and sp3
hybridised respectively. sp3d hybridisation
94. (c) I3– has sp3d hybridisation and has linear structure 1
· For PF6–, H = [5 + 6 - 0 + 1] = 6
– 2
I
: sp3d2 hybridisation.
: I : So, option (a) is correct choice.
102. (a) XeF4 having one lone pair of electron show distorted
I pentagonal bipyramidal shape and sp3d3 hybridisation.
95. (c) 103. (c) Let amount of compound = 100 g

sp2 hybridisation 92.3

No. of moles of C = = 7.69 = 7.7
12
For AlCl 3 7.7
No. of moles of H = = 7.7
(excited state) 1
Cl Cl Cl Empirical formula = CH
Empirical formula mass = 12 + 1 = 13 g/mol
sp3d 2 hybridisation Molecular mass = 52 g/mol
52
3– n = =4
For [Al2Cl6] 13
(excited state) \ Molecular foumula = Empirical formula × 4
Cl Cl Cl Cl– Cl– Cl–
= C4H4
Possible structures
96. (a) Only those d orbitals whose lobes are directed along
X, Y and Z directions hybridise with s and p orbitals. H H
sp sp H H
In other three d orbitals namely dxy, dyz and dxz, the C C C C H C C C C
H H, H,
lobes are at an angle of 45° from both axis, hence the 2 2
sp 2
sp 2 sp sp sp sp
extent of their overlap with s and p orbitals is much
lesser than d and d orbitals. H H
x 2 - y2 z2
sp2 C C sp2
97. (a) According to VSEPR theory, trigonal bipyramidal
geometry results from sp3d or dsp3 hybridisation. H C C H
dsp2 hybridisation results in square planar geometry,
while d2sp3 leads to octahedral shape. sp2 sp2

98. (c) H3C- CH = C = CH - CH3 104. (c) Molecular orbital theory was given by Mulliken.
sp 3
sp 2 sp sp 2
sp 3 105. (c)
106. (d) For oxygen correct increasing order is
99. (d) Statement (d) is incorrect. s1s < s*1s < s2s < s*2s < s2pz < (p2px = p2py) <
100. (a) SF6 Þ sp3d 2 (p*2px= p*2py) < s*2pz
CHEMICAL BONDING AND MOLECULAR STRUCTURE 459

75. (b) Sigma bond is stronger than p-bond. The electrons in Xe + number of monovalent atoms surrounding charge
the p bond are loosely held. The bond is easily broken on cation + charge or an ion]
and is more reactive than s -bond. Energy released 1
during sigma bond formation is always more than p In XeF6 = [8 + 6 – 0 + 0] = 7 i.e. sp3d3 hybridizaiton.
bond because of greater extent of overlapping 2
76. (a) Both assertion and reason are true and reason is the In case of SF6, Sulphur is sp3d2 hybridized.
correct explanation of assertion. In case of BrF5.Bromine atom has seven valence
pi bonds are formed by the overlapping of p-p orbitals electrons and 5 are contributed by the fluorine atoms.
perpendicular to their axis i.e., sidewise overlap. \ Total number of electron pairs in valence shell of central
77. (c) Option (c) represents zero overlapping. 7+5
78. (d) The strength of a bond depends upon the extent of atom = =6
2
overlapping. s-s and s-p overlapping results in the Number of shared pairs = 5
formation of s bond but extent of overlapping along Number of one pairs = 1
internuclear axis is more in case of s-s overlapping than The molecule is square pyramidal.
in s-p. p-p overlapping may result in s bond if In PCl5, P is sp3d hybridised. i.e. the correct answer is
overlapping takes place along internuclear axis or may XeF6 or option (c)
result in p–bond if sideways overlapping takes place. 83. (a) For linear arrangement of atoms the hybridisation
In any case the extent of overlapping is lesser in p - p should be sp(linear shape, 180° angle). Only H2S has
than that of the other two, s-s and s-p. Hence the correct sp3-hybridization and hence has angular shape while
order is C2H2, BeH2 and CO2 all involve sp - hybridization and
s-s>s-p>p-p hence have linear arrangement of atoms.
79. (a) Bond angle increases with increase in s-character of 84. (b) BF3 involves sp2-hybridization.
hybridised orbital. The table given below shows the
hybridised orbitals, their % s-chatracter and bond sp 3 sp sp sp 3
angles. 85. (b) H3C — C º C — CH3
linear
Hybridised % s-character Bond
86. (b) Equilateral or triangular planar shape involves sp2
orbitals angle
hybridization.
sp3 25 109.5°
87. (b) In CH3 CH2OH underlined C is forming 4 σ bonds,
sp2 33 120°
hence sp3 hybridisation. In others it is sp2 hybridised
sp 50 180°
80. (d) The hybridisation in a molecule is given by (due to 3 σ bonds).
88. (a) Each sp3-hybrid orbital has 25% s-character and 75%
1 p-character.
H = [V + M - C + A] .......(1)
2 89. (d)
where V = no. of valency e– in central atom sp 2 sp sp 2
M = no. of monovalent atoms around central atom 90. (a) CH 2 = C = CH 2
C = charge on cation, A = charge on anion
For NH3; V = 5, M = 3, C = 0, A = 0 sp3
Putting these values in (1), we get sp3 sp3
1 sp3 sp3
H = [5 + 3 - 0 + 0] = 4 sp 3
2
For H = 4, the hybridisation in molecule is sp3. sp3 sp 2 sp 2 sp3
81. (d) Hybridisaiton of SO42– ion is given by CH 3 - CH = CH - CH 3
1 sp sp sp sp
H = [V + M + A– C] HC º C - C º CH
2
Where V = valency of central metal atom sp 2 sp 2 sp 2 sp 2
M = no. of monovalent atoms surrounding central metal CH 2 = CH - CH = CH 2
atom. 1, 3-butadiene
A = charge on anion, C = charge on cation 91. (d) Hybridisation present in a molecule can be find out by
For SO2–
4 ; V = 6, M = 0, A = 2, C = 0
the following formula.
1 1
\ H= [6 + 0 + 2 – 0] = 4 H= (V + M - C + A)
2 2
i.e., sp3 hybridisation and tetrahedral shape. Where V = No. of electrons in valence shell of central
82. (c) In case of Xenon compounds atom
1 M = No. of singly charged atoms
Hybridization = [No. of valence electrons of C = charge on cation
2
 EBD_7374
460 CHEMISTRY

A = charge on anion PF5 Þ sp3d

1 BCl3 Þ sp2
So, Hybridisation (in ClF3) = [7 + 3 - 0 + 0] = 5 C2H6 Þ sp3
2 101. (b) Hybridisation of the central atom in compound is given
Þ sp3d Hybridisation by
92. (a) Hybridisation of carbon in CH 3+ is sp2 and in CH4 its
hybridisation is sp3 1
H= [V + M - C + A]
2
93. (c) (a) CH 2 = C = CH 2
where V = No. of valency electrons in central metal
sp 2 sp sp 2
atom,
+ M = No. of monovalent atoms surrounding the central
(b) CH3 — CH = CH— CH 2 atom,
sp3 sp 2 sp 2 sp 2
C = charge on cation and A = charge on anion
+
(c) CH3 — C º C— CH 2 1
sp sp · For NO -2 , H = [5 + 0 - 0 + 1] = 3
sp3 sp 2 2
sp2 hybridisation
(d) CH3 — CH = CH— CH 2–
2 2 1
sp3 sp sp sp 3 · For SF4, H = [6 + 4 - 0 + 0] = 5
2
Note : Carbocations and carboanions are sp2 and sp3
hybridised respectively. sp3d hybridisation
94. (c) I3– has sp3d hybridisation and has linear structure 1
· For PF6–, H = [5 + 6 - 0 + 1] = 6
– 2
I
: sp3d2 hybridisation.
: I : So, option (a) is correct choice.
102. (a) XeF4 having one lone pair of electron show distorted
I pentagonal bipyramidal shape and sp3d3 hybridisation.
95. (c) 103. (c) Let amount of compound = 100 g

sp2 hybridisation 92.3

No. of moles of C = = 7.69 = 7.7
12
For AlCl 3 7.7
No. of moles of H = = 7.7
(excited state) 1
Cl Cl Cl Empirical formula = CH
Empirical formula mass = 12 + 1 = 13 g/mol
sp3d 2 hybridisation Molecular mass = 52 g/mol
52
3– n = =4
For [Al2Cl6] 13
(excited state) \ Molecular foumula = Empirical formula × 4
Cl Cl Cl Cl– Cl– Cl–
= C4H4
Possible structures
96. (a) Only those d orbitals whose lobes are directed along
X, Y and Z directions hybridise with s and p orbitals. H H
sp sp H H
In other three d orbitals namely dxy, dyz and dxz, the C C C C H C C C C
H H, H,
lobes are at an angle of 45° from both axis, hence the 2 2
sp 2
sp 2 sp sp sp sp
extent of their overlap with s and p orbitals is much
lesser than d and d orbitals. H H
x 2 - y2 z2
sp2 C C sp2
97. (a) According to VSEPR theory, trigonal bipyramidal
geometry results from sp3d or dsp3 hybridisation. H C C H
dsp2 hybridisation results in square planar geometry,
while d2sp3 leads to octahedral shape. sp2 sp2

98. (c) H3C- CH = C = CH - CH3 104. (c) Molecular orbital theory was given by Mulliken.
sp 3
sp 2 sp sp 2
sp 3 105. (c)
106. (d) For oxygen correct increasing order is
99. (d) Statement (d) is incorrect. s1s < s*1s < s2s < s*2s < s2pz < (p2px = p2py) <
100. (a) SF6 Þ sp3d 2 (p*2px= p*2py) < s*2pz
CHEMICAL BONDING AND MOLECULAR STRUCTURE 461

107. (a)
no of possible resonating structures
108. (a) Both assertion and reason are true and reason is the = 1.5.
correct explanation of assertion. 2
Helium molecule is formed by linking two helium atoms. 119. (c) N 2 + = 7 + 7 – 1 = 13 electrons
Both have 1s orbitals. These will combine to form two Configuration is
molecular orbitals s (1s) and s* (1s). Four available
electrons are accommodated as s (1s)2 and s* (1s)2. s1s 2 , s *1s 2 , s2s 2 , s * 2s 2 , p2 p x 2 =
109. (b)
110. (b) One bonding M.O. and one anti-bonding M.O. = p2 p y 2 , s2 p1z
111. (d) Molecules having unpaired electrons show Bond order =
paramagnetism.
1 æ No. of e- s in bonding - No. of e -s in antibonding ö
112. (b) Atomic orbital is monocentric because an electron in
it is influenced by one nucleus. While molecular 2 çè molecular orbital molecular orbital ÷
ø
orbital is polycentric as it is influenced by two or 1 1
more nuclei depending upon the number of atoms in = (9 - 4) = ´ 5 = 2.5
2 2
the molecule. 120. (a)
113. (c) 121. (a, b) The molecular orbital structures of C2 and N2 are
114. (b) Atomic orbitals having same or nearly same energy
will not combine if they do not have the same N2 = s1s 2 s *1s2 s2s 2 s *2s 2 s2 px2p2 py2 p2 pz2
symmetry. 2pz orbital of one atom cannot combine C2 = s1s 2 s *1s 2 s2s 2 s * 2s 2 p2 py 2p2Pz2
with 2px or 2py orbital of other atom because of their
Both N2 and C2 have paired electrons, hence they are
different symmetries.
diamagnetic.
115. (c) The electron density in a bonding molecular orbital
is located between the nuclei of the bonded atoms 122. (d) H +2 : (s 1s1)
because of which the repulsion between the nuclei is 1 1
Bond order = (1 - 0) =
very less while in case of an antibonding molecular 2 2
orbital, most of the electron density is located away H -2 : (s1s 2 ) (s*1s1 )
from the space between the nuclei.
Electrons placed in a bonding molecular orbital tend 1 1
Bond order = (2 - 1) =
to hold the nuclei together and stabilise a molecule. 2 2
116. (c) M.O. electronic configuration of CN– is s1s2 s*1s2 s2s2 The bond order of H +2 and H 2- are same but H +2 is more
s*2s2p2px2 p2py2 s2pz2 stable than H 2- . In H 2- the antibonding orbital is filled
with 1 electron so this causes instability.
\ B.O. = 10 – 4 = 3 123. (b) The removal of an electron from a diatomic molecule
2
may increase the bond order as in the conversion
M.O. electronic configuration of O2– is
+
s1s2 s*1s2s2s2s*2s2s2pz2p2px2 O2 (2) ¾¾® O 2 ( 2 .5) or decrease the bond order as in
p2py2 p*2px2p*2py1 ¾® N +2 ( 2.5), As a result,
the conversion, N 2 (3.0) ¾
10 – 7
\ B.O. = = 1.5 the bond energy may increase or decrease. Thus,
2 statement (b) is incorrect.
M.O. electronic configuration of CN+
s1s2 s*1s2 s2s2 s*2s2p2px2 p2py2 s2pz1 124. (b) O2 : s1s 2 , s*1s 2 , s 2s 2 , s* 2 s 2 , s 2 p z2 ,
9–4
\ B.O. = = 2.5 ìïp 2 p 2x ìïp* 2 p1x
2 í , í * 1
2
M.O. electronic configuration of NO+ is ïîp 2 p y ïîp 2 p y
s1s2 s*1s2 s2s2 s*2s2s2pz2 p2px2 p2py2
10 – 4 10 - 6
\ B.O. = =2 Bond order = =2
2 2
\ CN– and NO+ have bond order equal to 3 (two unpaired electrons in antibonding molecular orbital)
1 ì 2 ì * 1
117. (c) B.O. = [N b - N a ] = 0 ; cannot exist 2 ï p 2 p x , ï p 2 px
2 O +2 2 * 2 2
: s1s , s 1s , s 2s , s 2s * 2
, s2 pz , í 2 í * 0
ïîp 2 p y , ïî p 2 p y
118. (c) Benzene has the following resonance structures–
10 - 5
¬
¾® Bond order = = 2. 5
2
(One unpaired electron in antibonding molecular orbital)
Hence, its bond order is
 EBD_7374
462 CHEMISTRY

in the presence of no. of anti-bonding electron.

Hence O2 as well as O +2 both are paramagnetic, and
Higher the no. of anti-bonding electron lower is the
bond order of O +2 is greater than that of O2. stability hence the correct order is H2 > Li2 > B2
131. (a) Molecular orbital electronic configuration of these
125. (d) As the bond order decreases, bond length increases species are :
Bond order
No. of bonding e -s - No. of antibonding e -s O-2 (17e- ) = s1s 2 , s *1s 2 , s2s 2 , s *2s 2 , s2 pz2 ,
=
2 p2 px2 = p2 p2y , p *2 px2 = p2* p1y
For N2, electronic configuration is
s1s 2 < s*1s 2 < s2s 2 < s* 2s 2 < (p2 px2 = p2 p 2y ) < 2 p 2z O2 (16e - ) = s1s 2 , s *1s 2 , s2 s 2 , s * 2s 2 , s2 p z2 ,

10 - 4 p2 px2 = p2 p 2y , p *2 p1x = p * 2 p1y

(i) Bond order of N2 = =3
2
O22 - (18e - ) = s1s 2 , s *1s 2 , s2 s 2 , s * 2 s 2 , s 2 p z2 ,
9-4
(ii) Bond order of N +2 = = 2.5
2 p2 px2 = p2 p 2y , p *2 px2 = p *2 p 2y
8-4 Hence number of antibonding electrons are 7, 6 and 8
(iii) Bond order of N 22+ = =2
2 respectively.
Hence, order of Bond length will be, 132. (d) s2b s *a2 sb2 s*2 2 2 1 +
a (pb = p b ) sb (N 2 = 13electrons)

N 2 < N 2+ < N 2+ it contains one unpaired electron hence paramagnetic.

133. (a) Molecular orbital configuration of
126. (c) According to molecular orbital theory, bond order of
Li2 is 1 , while in all other cases bond order is 0, so N 2– 2 2 2 2
2 = s1s s *1s s2 s s * 2 s -
they do not exist. Li2 molecules are known to exist in
the vapour phase. ìï p 2 px2 ìï p * 2 p1x
127. (b) í s2 p2z í
2 1
128. (d) In this configuration, there are four completely filled ïîp 2 p y ïîp * 2 p y
bonding molecular orbitals and one completely filled 10 – 6
antibonding molecular orbital. So that Nb = 8 and Bond order = =2
2
Na = 2 . ìp2 px2 ìï p * 2 p1x
N 2– = s1s 2 s *1s 2 s2 s 2s * 2 s 2 ï
í s2 pz2 í
1 1 2 0
\ Bond order = ( N b - N a ) = (8 - 2) = 3.
2 2 îïp2 p y ïî p *2 p y
10 - 5
129. (d) On calculating bond order of species given in question Bond order = = 2.5
2
ì 2
C2 = 2 C22- = 3 2 2 2 2 ïp2 px
N 2 = s1s s *1s s 2 s s * 2 s í , s 2 pz2
2
B+2 = 0.5 B2 = 1 ïîp 2 p y
10 – 4
Bond order = =3
Li2+ = 0.5 Li2 = 1 2
\ The correct order is = N 2– –
2 < N2 < N2
N +2 = 2.5 N2 = 3
134. (c) H-bonding is maximum in the solid state and
O2 = 2.0 O 2- = 1.5 minimum in gaseous state.
135. (c) H2O shows intermolecular hydrogen bonding while
1 o-nitrophenol shows intramolecular H-bonding.
Bond length µ
Bond order 136. (a)
\ O -2 > O2 137. (c) Ice has many hydrogen bonds which give rise to cage
130. (N) None of the given option is correct. like structure of water molecules. This, structure
The molecular orbital configuration of the given possess larger volume and thus makes the density of
molecules is ice low.
H2 = s1s2 (no electron anti-bonding) 138. (b) Methanol and ethanol are soluble because of the
Li2 = s1s2 s*1s2 s2s2(two anti-bonding electrons) hydrogen bonding.
139. (d) F—H----F bond is shortest, because with the increase
1
{ 1
B2 = s1s2 s*1s2 s2s2 s*2s2 p2p y = p2pz } of electronegativity and decrease in size of the atom to
(4 anti-bonding electrons) which hydrogen is linked, the strength of the hydrogen
Though the bond order of all the species are same (B.O bond increases.
= 1) but stability is different. This is due to difference 140. (a) Hydrogen bonding is possible only in compounds
having hydrogen attached with F, O or N.
CHEMICAL BONDING AND MOLECULAR STRUCTURE 463

C2 H 5 - OH CH 3 - O - CH 3 3. (b) Applying the formula to find the hybridisation of

(H-bonding possible) (H-bonding not possible) central atom (nitrogen) :
1
O O [No. of valence e – of central atom +
|| || 2
CH3 - C - CH 3 CH 3 - C - H no. of monovalent atoms attached to it +
(H-bonding not possible) (H-bonding not possible)
(–ve) charge if any – (+ve) charge if any]
O 1
For, NO2+ = [5 + 0 + 0 – 1] = 2 Þ sp-hybridised
141. (a) N ( Intermolecular 2
O hydrogen bonding) 1
OH NO3– = [5 + 0 + 1 – 0] = 3 Þ sp2-hybridised
2
O-nitrophenol 1
NH4+ = [5 + 4 + 0 – 1] = 4 Þ sp3-hybridised
142. (c) The b.p. of p-nitrophenol is higher than that of 2
o-nitrophenol because in p-nitrophenol there is 4. (b) Strength of H-bonding is in the order :
intermolecular H-bonding but in o-nitrophenol it is HF > H2O > NH3
intramolecular H-bonding. Also, each H2O molecule is linked to four other H2O
143. (b) The strength of the interactions follows the order molecules through H-bonds while each HF molecule is
vander Waal’s < hydrogen – bonding < dipole-dipole linked only to two other HF molecules.
< covalent. Hence, decreasing order of b.p. will be : H2O > HF >
144. (c) ortho-Nitrophenol has intramolecular H-bonding NH3
In PO34- ion, formal charge on each O-atom of P – O
.
. . OH 5. (c)
. O and para-nitrophenol has
Total charge 3
||

. N bond = = - = - 0.75
O Number of O atom 4
intermolecular H-bonding. 6. (d) In NO3– ion,
145. (d) Hydrogen bonding increases the boiling point of number of bond pairs (or shared pairs) = 4
compound. number of lone pairs = 0
146. (b) Both assertion and reason are true but reason is not
the correct explanation of assertion. 7. (a) BH -4 Þ 4 bond pairs and 0 lone pair ® sp3 hybridised.
Water is excellent solvent because it has high value of \ Tetrahedral geometry
dielectric constant. Due to high value of dielectric 8. (c) The correct structure of the given compound will be as
constant, the electrostatic force of attraction between follows :
the ions decrease and these ions get separated and H H
ultimately get solvated by the solvent molecules.
H H
147. (b)
148. (a) Hydrogen bond is formed when hydrogen is attached
with the atom which is highly electronegative and
H H
having small radius.
149. (c) B, C and D form intermolecular hydrogen bonding while H H
A form intramolecular hydrogen bonding due to Now, there are 5 p-bonds and 19 s-bonds are present
proximity of oxygen and hydrogen. in the above molecule.
150. (c) Each H2O molecule can form two H-bonds through 9. (c) The electronic configuration of the given molecules
H-atoms and two H-bonds through two lp of e–s on are :
O-atom.
N +2 = s1s 2 , s *1s 2 , s2 s 2 , s * 2s 2 , p 2 px2 = pp 2y , s 2 p1z ;
Exercise - 2
1 unpaired e–
1. (b) BF4- and NH +4 both the species are tetrahedral and
O2 = s1s 2 , s *1s 2 , s2s2 , s * 2s 2 , s2 p2z , p2 px2 » p2 p2y ,
sp3hybridised.
2. (c) CO2 being symmetrical has zero dipole moment. p * 2 p1x » p * 2 p1y ; 2 unpaired e–s
Amongst HI, SO2 and H2O. H2O exhibit the highest
dipole moment as the central atom in H2O contains 2 O22- = s1s 2 , s *1s2 , s2s 2 , s * 2s 2 , s2 pz2 , p2 p2x » p2 p2y ,
lone pairs.
..
p*2 px2 » p*2 p 2y ; no unpaired e–s
..

O
..

S
H—I H H O O
m = 0.38D m = 1.84 D m = 1.84 D B2 = s1s 2 , s *1s 2 , s2s 2 , s * 2s 2 , p 2 p1x » p 2 p1y ;
2 unpaired e–s
 EBD_7374
464 CHEMISTRY

10. (c) XeF4 Þ square planar, all bonds are equal. 2-2
B.O = =0
BF4- Þ tetrahedral, all bonds are equal. 2
H Now, He+2 = s1s 2 , s *1s1
H
C2H4 Þ C=C , C = C bond is not equal to
H
H
C – H bond. 2 -1
B.O = = 0.5
SiF4 Þ tetrahedral, all bonds are equal. 2
11. (b) HCl, HI and H2S do not from H-bonds. Only H2O forms As the bond order is not zero, He2+ molecule is
hydrogen bonds and each H2O molecule is linked with expected to exist.
four H2O molecules. (c) N2 (7 + 7 = 14) = s1s2, s*1s2, s2s2, s*2s2,
H p 2 px2 » p 2 p2y , s 2 pz2
H
O
O
10 - 4
H
H H H
B.O = =3
2
O
Thus, dinitrogen (N2 ) molecule contain triple bond
H H H H
O O and as bond order = 3 while no molecule of second
period have more than double bond. Thus, bond
strength of N 2 its maximum amongst the
12. (d) The given electronic configuration shows that the
homonuclear diatomic molecules belonging to the
element belongs to d-block of the periodic table and
second period.
known to be a transition element. In transition elements,
(d) The correct order of energies of molecular orbitals
electrons of ns and (n – 1)d subshell take part in bond
in N2 molecule is
formation.
s1s < s*1s < s2s < s*2s < (p2px ; p2py ) < s2pz
13. (b) For sp2 hybridisation, generally the geometry is usually
< p*2px » p*2py < s*2pz
taken to be triangular planar.
20. (b) E.C of O2 :
Y
s1s2, s*1s2, s2s2, s*2s2, s 2 p 2z , p 2 px2 » p 2 p2y ,

120° p *2 p1x » p *2 p1y

X
1 1
B.O = ( N b - Na ) = (10 - 6 ) = 2
2 2
Y Y
Thus, bond angle should be 120°. E.C of O+2 :
14. (a) The given electronic configuration of A shows that it
is a noble gas because the octet is complete and hence s1s 2 , s *1s 2 , s2 s 2 , s * 2s 2 , s 2 p z2 , p 2 px2 » p2 p 2y ,
it will be the stable form.
15. (b) The electronic configuration of C represent chlorine. p *2 p1x » p *2 p0y
Its stable form is Cl2 i.e., C2.
1
16. (d) The electronic configuration show that B represents B.O = (10 - 5) = 2.5
phosphorus and C represents chlorine. The stable 2
compound formed will be PCl3 i.e., BC3. E.C of O-2 :
17. (b) The bond between B and C will be covalent as both B
and C are non-metal atoms. s1s 2 , s *1s 2 , s2 s 2 , s * 2s 2 , s 2 p z2 , p 2 px2 » p2 p 2y ,
18. (a) The correct increasing order of energies of molecular
orbitals of N2 is : p *2 px2 » p * 2 p1y
s1s < s*1s < s2s < s*2s < (p2px » p2py ) < s2pz < (p*2px
; p*2py ) < s*2pz 1
Bond order = (10 - 7 ) = 1.5
19. (d) (a) Be2 = s1s2, s*1s2, s1s2, s* 2s2 2
1 Hence, the correct order of bond order will be :
(B.O) = [Number of bonding electrons (Nb ) –
2 O -2 < O 2 < O2+ .
Number of anti-bonding electrons Na ]
21. (a) Out of the given electronic configuration 2s22p5
4-4 represents fluorine which is the most electronegative
= =0
2 element while 3s23p5, 4s24p5 and 5s25p5 represents
Bond order of Be2 is zero thus, it does not exist. chlorine, bromine and iodine respectively.
(b) He2 = s1s2, s*1s2
CHEMICAL BONDING AND MOLECULAR STRUCTURE 465

22. (b) The electronic configuration of (b) and (d) have exactly +

:
Nd
half-filled p-orbitals but (b) being smaller in size than pyramidal d- F F d- and m ¹ 0 hence it is polar..
(d) will have the highest ionisation enthalpy. F d-
23. (b) Be2+ = (4 – 2) = 2
is isoelectronic with Li+ (3 – 1 = 2) 32. (c) O +2 ion - Total number of electrons (16 – 1) = 15.
Since both have same number of electrons in their Electronic configuration
outermost shell. σ1s 2 < σ*1s 2 < σ2s 2 < σ* 2s 2 < σ2p 2x
24. (c) Dipole moment of NH3 > NF3
< π2 p 2y = π2 pz2 < π* 2 p1y
d+
d –.
. N
N N b - Na 10 - 5 5 1
Bond order = = = =2
2 2 2 2
–F F
d+H H (d ) F –
(d )
H –
(d ) O2– (Super oxide ion): Total number of electrons
m = 1.4 D m = 0.23 D (16 + 1) = 17 . Electronic configuration
(F is more electronegative than N)
σ1s2 < σ*1s 2 < σ2s 2 < σ* 2s 2 < σ2 p x2
1
25. (b) Hybridization of NO3– = (5 + 0 + 1 - 0) < π2 p 2y = π2 p2z < π* 2 p 2y = π* 2 p1z
2
Bond order
6 2
= = 3 = sp hence geometry is trigonal planner.. (Nb - Na ) 10 - 7 3 1
2 = = = =1
NO2– (nitrite ion) also has sp2 hybridization and gives 2 2 2 2
a trigonal planner geometry but because there are only O+22 ion: Total number of electrons = (16 – 2) = 14
two outer atoms, the molecular geometry is bent with Electronic configuration
Ð120º bond angles. s1s2 < s*1s2 < s2s2 < s*2s2 < s2px2 < p2py2 = p2pz2
26. (c) LiCl is a covalent compound. Due to the large size of
the anion (Cl–) its effective nuclear charge lessens and (N b – Na ) 10 – 4 6
Bond order = = = =3
its valence shell is held less tightly towards its nucleus. 2 2 2
Here, assertion is correct but reason is incorrect. So bond order: O2– < O+2 < O22+
27. (d) 33. (c) ClO3– and SO2–3 both have same number of electrons
28. (a) Nitric oxide is paramagnetic in the gaseous state (42) and central atom in each being sp3 hybridised.
because of the presence of one unpaired electron in its Both are having one lone pair on central atom hence
outermost shell. they are pyramidal.
The electronic configuration of NO is 34. (a) Oxygen molecule (O2) - Total number of electrons = 16
and electronic configuration is
σ12s σ1*2s σ 22 s σ *2 2 2 2 *1
2 s σ 2 p z π 2 p x =π 2 p y π 2 p x
σ1s 2 < σ*1s 2 < σ2s 2 < σ* 2 s 2 < σ2 p2x

29. (d) H < π2 p 2y = π2 pz2 < π* 2 p1y = π* 2 p1z

O O
H N b - N a 10 - 6 4
Bond order = = = =2
2 2 2
H
S S O +2 ion - Total number of electrons (16 – 1) = 15.
Electronic configuration
H
In both the molecules the bond moments are not σ1s 2 < σ*1s 2 < σ2s 2 < σ* 2 s 2 < σ2 p2x
canceling with each other and hence the molecules
has a resultant dipole and hence the molecule is polar. < π2 p 2y = π2 pz2 < π* 2 p1y

30. (d) BF4- hybridisation sp3, tetrahedral structure. NH +4 N b - Na 10 - 5 5 1

Bond order = = = =2
hybridisation sp3, tetrahedral structure. 2 2 2 2
d- O2– (Super oxide ion) Total number of electrons
F d + d-
31. (d) The shape of BF3 is trigonal planar B – F and (16 + 1) = 17 . Electronic configuration
d- F
m = 0 hence it is non polar. The shape of NF3 is
 EBD_7374
466 CHEMISTRY

41. (b) CH4 NH3 H2O

σ1s 2 < σ*1s 2 < σ2s 2 < σ* 2 s 2 < σ2 p x2
H
< π2 p 2y = π2 pz2 < π* 2 p1y = π* 2 p1z
C 109°28' N
(Nb - Na ) 10 - 7 3 1 H H H 107°H
Bond order = = = =1 H H
2 2 2 2
Tetrahedral Trigonal pyramidal
35. (b) NO2+ has sp hybridisation so it is linear with bond
angle = 180°.
O O
H 104.5° H
36. (a) Xe Bent
O O O Note: The geometry of H2 O should have been
tetrahedral if there are all bond pairs. But due to presence
Number of s bonds = 4 of two lone pairs the shape is distorted tetrahedral.
Number of p bonds = 4 Hence bond angle reduced to 104.5° from 109.5°.
37. (a) According to molecular orbital theory as bond order 42. (a) According to VSEPR theory order of repulsion in
decreases stability of the molecule decreases between lp – lp, lp – bp and bp – bp is as under
1 lp – lp > lp – bp > bp – bp
Bond order = (N – N a) 43. (c) Xenon undergo sp3 hybridization.
2 b

1
Bond order for O+2 = (10- 5) = 2.5
2 5s 5p

1 (ground
Bond order for O 2 = (10 - 6) = 2 state)
2
5d
1
Bond order for O -2 = (10 - 7) = 1.5
2
5s 5p
2- 1
Bond order for O2 = (10 - 8) = 1.0
2 (third excited
hence the correct order is state)
5d
O+2 > O 2 > O2– > O 2–
2 In the fourth excited state xenon atom, has 8 unpaired
38. (d) XeF4, XeO4 electrons
O
F F Xe
Xe 5s 5p
O O
F F O
(Square planar) (Tetrahedral)
5d
39. (b) List I List II One s and three p orbital undergo sp3 hybridization.
Compound Structure Four sp3 hybrid orbitals form four s bonds with oxygen
(A) ClF3 T-shaped atoms. They are ssp3 – p. Four pp– dp bonds are also
(B) PCl5 Trigonal bipyramidal formed with oxygen atoms by the unpaired electrons.
(C) IF5 Square pyramidal 44. (c) M.O. electronic configuration of CN– is
(D) CCl4 Tetrahedral s1s2 s*1s2 s2s2 s*2s2p2px2 p2py2 s2pz2
(E) XeF4 Square planar 10 – 4
40. (a) In P4 molecule, the four sp3-hybridised phosphorous \ B.O. = =3
2
atoms lie at the corners of a regular tetrahedron with
M.O. electronic configuration of O2– is
ÐPPP = 60°.
s1s2 s*1s2s2s2s*2s2s2pz2p2px2 p2py2 p*2p 2xp*2py1
In S8 molecule S-S-S angle is 107° rings.
10 – 7
S 2m \ B.O. = = 1.5
21 S S 2
S S M.O. electronic configuration of CN+
107°
s1s2 s*1s2 s2s2 s*2s2p2px2 p2py2 s2pz1
S
S S
CHEMICAL BONDING AND MOLECULAR STRUCTURE 467

9–4 atoms. Formal charge

\ B.O. = = 2.5 = –3/4 = – 0.75.
2
48. (b) CN– and CO have same no. of electrons and have same
M.O. electronic configuration of NO+ is
bond order equal to 3.
s1s2 s*1s2 s2s2 s*2s2s2pz2 p2px2 p2py2
49. (b) IBr–2, XeF2
10 – 4 Total number of valence electrons are equal in both the
\ B.O. = =3
2 species and both the species exhibit linear shape.
\ CN– and NO+ have bond order equal to 3 50. (c) BCl3 is trigonal planar and hence the bond angle is
120°.
Cl
45. (a) While the lone pairs are localised on the central atom,
each bonded pair is shared between two atoms. As a 120°
B
result, the lone pair electrons in a molecule occupy
Cl Cl
more space as compared to the bonding pairs of
electrons. This results in greater repulsion between 51. (d) According to Fajan's rule :
lone pairs of electrons as compared to the lone pair - 1
Covalent character µ
bond pair and bond pair - bond pair repulsions. size of cation
Hence (b) is the correct option. µ size of anion
1 Among the given species order of size of cations
46. (c) Hybridization (H) = [no. of valence electrons of N3+ < O2+ < Pb2+ < Ba2+
2
central atom + no. of Monovalent atoms attached to it order of size of anions O2– > Cl–.
Hence the order of covalent character is
+ (–ve charge if any) – (+ve charge if any)]
NCl3 > Cl2O > PbCl2 > BaCl2
1 BaCl2 is least covalent in nature.
NO2+ = [5 + 0 + 0 - 1] = 2 i.e. sp hybridisation
2 52. (b)
1 (a) NO ® one unpaired electron is present in p* molecular
NO–2 = [5 + 0 + 1 - 0] = 3 i.e. sp2 hybridisation orbit hence paramagnetic.
2
(b) CO ® s12s , s1*2s , s22s , s*2 2 2 2
2 s , p 2 px , p 2 p y , s 2 p z
1
NO–3 = [5 + 0 + 1 - 0] = 3 i.e. sp2 hybridisation
2 no unpaired electron hence diamagnetic.
The lewis structure of NO2 shows a bent molecular 2 *2 2 *2 2 2 2 *1 *1
geometry with trigonal planar electron pair geometry (c) O2 ® s1s , s1s , s2 s , s2 s , s2 p z , p2 px , p2 p y , p2 px , p2 p y
hence the hybridization will be sp2. two unpaired electron hence paramagnetic.
2 *2 2 *2 1 1
(d) B2 ® s1s , s1s , s2s , s2s , p2 p , p2 p
N x y
B2 contains two unpaired electrons hence paramagnetic
53. (b) Ionic bonding is non directional, whereas covalent
O O bonding is directional. So, CO2 is directional.
54. (b) Bond length decreases with an increase in bond order.
3- 3-
é O ù é O ù Therefore, the order of bond length in these species
ê | ú ê | ú is O2+ < O2-> O2 < O22- (bond order - O2+ = 2.5, O2 =2,
47. (c) ê O - P - Oú « êO - P = Oú «
O2- =1.5, O22- =1)
ê || ú ê | ú
ë O û ë O û 55. (b) The structure of ClF3 is

3- 3- F
é O ù é O ù
ê || ú ê | ú
êO - P - Oú « êO = P - Oú F Cl
ê | ú ê | ú
ë O û ë O û
F
No. of bonds The number of lone pair of electrons on central Cl is 2.
Bond order =
No. of Resonating structures 56. (b) NO : (s1s)2, (s*1s)2, (s2s)2,(s*2s)2,(s2pz)2,
(p2px)2 = (p2py)2,(p*2px)1 = (p*2py)0
5
= = 1.25 10 - 5
4 B.O. = = 2.5
Three unit negative charge is being shared by four O 2
CN– : (s1s)2, (s*1s)2, (s2s)2,(s*2s)2,
(p2px)2 = (p2py)2, (s2pz)2
 EBD_7374
468 CHEMISTRY

Thus the correct increasing order is

10 - 4
B.O. = =3 IF7 < IF5 < ClF3 < XeF2
2 0 1 2 3
CN : (s1s)2, (s*1s)2, (s2s)2,(s*2s)2,
(p2px)2 = (p2py)2,(s2pz)1 64. (b) O2 : s1s 2 , s*1s 2 , s 2s 2 , s* 2 s 2 , s 2 p z2 ,
9-4 ìïp 2 p 2x ìïp* 2 p1x
B.O. = = 2.5
2 í , í * 1
2
CN+ : (s1s)2, (s*1s)2, (s2s)2,(s*2s)2, îïp 2 p y îïp 2 p y
(p2px)2 = (p2py)2
10 - 6
8-4 Bond order = =2
B.O. = =2 2
2
(two unpaired electrons in antibonding molecular orbital)
Hence, option (2) should be the right answer.
57. (c) BF3 ® Trigonal planar ìïp 2 p x2 , ìï p* 2 p1x
O +2 : s1s 2 , s*1s 2 , s 2s 2 , s* 2s 2 , s 2 p 2z , í 2 í *
ICl3 ® T shape ïîp 2 p y , ïî p 2 p y
0

58. (a) Oxygen molucules (O2) :

O2 : (s1s)2 (s*1s)2 (s2s)2 (s*2s)2 (s2pz)2 (p2p2x = p2p2y) 10 - 5
Bond order = = 2. 5
(p*2p1x = p*2p1y) 2
59. (b) Sulphur has five electron pairs whose arrangemnet (One unpaired electron in antibonding molecular orbital)
should be trigonal bipyramidal according to VSEPR Hence O2 as well as O +2 both are paramagnetic, and
theory. Two structures are possible.
bond order of O +2 is greater than that of O2.
F
F F Exercise - 3
F– S – F S
1. (b) H3C.C º C.CH3 symmetrical and linear. Hence D.M. ( m ) = 0.
F F F
(a) (b) 2. (c) In nitrogen molecule, both the nitrogen atoms have
Ione pair in the axial Ione pair in the equatorial same electronegativity. So it has zero polarity and
position (there l.p.-b.p. position (two l.p.-b.p
repulsion at 90°) repulsions)
hence less tendency to break away and form ions.

60. (c)
I 3. (b) (i)

I 5 4 3
B.O. = B.O. = B.O. =
4 3 2
I s

\ Total number of lone pair of electrons is Þ 9 (ii) as % s-character ¯ bond angle ¯

61. (d) The electronic configuration of H 2–
2 is
Þ(s1s2), (s*1s)2 (iii) higher s-character Þ stronger bond.
Nb - Na 2 - 2 4. (c) The electronic configuration of As is
Bond order = = =0 10 1 1
2 2 s 4 p x 4 p1y 4 p1z 4d 1
As = [Ar]3d 4144 424443
Hence H 2– 2 does not exist, due to zero bond order.. ¯ sp3d hybridisation
62. (c) KCl is ionic compound while other are covalent Thus the hybridisation involved in the AsF5 molecule
compounds. is trigonal bipyramidal. So, the hybrid orbitals used
63. (a) The number of lone pairs of electrons on central atom are s, px, py, pz, d 2 .
z
in various given species are
Species Number of lone pairs on 5. (b)
central atom –
IF7 nil F F
Xe F
IF5 1 (a) XeF5-
ClF3 2 F F
XeF2 3
CHEMICAL BONDING AND MOLECULAR STRUCTURE 469

Number of atoms in ‘X-Y’ plane = 6 Mag. Behaviour = Paramagnetic

F For NO+
Total no. of electrons = 14
F F
B.O = 3
S
(b) SF6 Mag. Behaviour = Diamagnetic
F F
10. (c) 11. (b)
F
12. (b) B.O. of CN–, CN and CN+ are 3, 2.5 and 2 respectively.
Number of atoms in (X-Y) plane = 5
F 13. (c) (a) The S-atom in the excited state (3s 2 3 p3 3d 1 ) has
F F
sp3 hybridization - ( sp3 )2 ( sp3 )1 ( sp3 )1 3d 1 . The three
(c) IF7 I F
F hybrid orbitals form three (S-O) s -bonds and the 3d
F
pure orbital gives (S-O) p -bond.
F
Number of atoms in (X-Y) plane = 6 (b) In PO 34- , P-atom in its excited state (3s1 3 p 3 3d 1 ) is
F Cl sp3 hybridized. Four hybrid orbitals forms (P-O)
O Cl s-bonds whereas 3d1 gives (P-O) p -bond.
6. (d) Xe P Cl
(c) In NO 3- , N-atom is sp 2 hybridized as
O Cl
F Cl
( sp 2 )2 (sp 2 )1 ( sp 2 )1 2 p1z
3-atoms 4-atoms
+
Completely filled sp2 hybrid orbital on N-atom donates
H an electron pair to the vacant 2p orbital of O atom to
F F form dative bond. Other two hybrid orbitals form (N-O)
As Xe
F F s -bonds. The pure 2 p1z orbital forms (N-O) p -bond.
H H
H
(d) In XeOF4, Xe-atom in its excited state (5s 2 5 p3 5d 3 ) is
3-atoms 5-atoms
Maximum atoms that ® 3 4 3 5
sp3 d 2 hybridized. The singly filled five hybrid orbitals
can lie in a plane
form s -bonds with 4F atoms and O atom. The pure 5d
7. (b) dx 2 - y2 + py ( side wise overlap ) ® Non - bonding. orbital forms p -bond with 2p orbital of O-atom.
8. (c) 14. (a) Its conjugate base (i.e. NH3) is most stable.
9. (a) For NO 15. (d) It is most appropriate because in it the formal charge is
Total no. of electrons = 15 zero on all the atoms.
B.O = 2.5
 EBD_7374
470 CHEMISTRY

5. STATES OF MATTER

Exercise - 1 or P2 = 750 ´ 600 = 900 mm of Hg

500
1. (c) Attractive forces between an ion and a dipole are known Therefore increase of pressure = (900 – 750) = 150 mm
as ion - dipole forces and these are not van der Waals of Hg
forces. 17. (a)
2. (d) Fritz London explained the concept of dispersion force. 18. (b) The lowest hypothetical or imaginary temperature at
3. (a) Dipole-dipole interaction is stronger than the London which gases are supposed to occupy zero volume is
forces but is weaker than ion-ion interaction because called absolute zero.
only partial charges are involved e.g., HCl molecules. 19. (b) Given initial volume (V1) = 500 mL ; Initial temperature
The attractive force decreases with the increase of (T1) = 27ºC = 300 K and final temperature (T2) = –5ºC
distance between the dipoles. = 268 K.
4. (b) This type of attractive force operates between the polar From Charle’s law :
molecules having permanent dipole and the molecules
lacking permanent dipole. V1 V2 500 V2
= or =
HCl is polar (m ¹ 0) and He is non polar (m = 0), thus T1 T2 300 268
gives dipole-induced dipole interaction. Where V2 = New volume of gas
5. (c) Nobel gases has no intermolecular forces due to
inertness. 500
V2 = ´ 268 = 446.66 mL
6. (a) 300
7. (d) All of the given statements are correct for hydrogen 20. (c) At any given pressure, graph of volume vs temperature
bond. (in °C) is a straight line and on extending to zero volume
8. (c) In case of HCl molecules their is dipole-dipole each line intercepts the temperature axis at – 273.15° C.
interaction which is stronger than London forces as 21. (b)
in case of SF6. Now between HCl and NaCl the ion-
æ MP ö
ion interaction present in NaCl is far more stronger 22. (a) dµ p, Boyle’s law, ç d = ÷ . At sea level pressure is
than dipole-dipole interaction of HCl. è RT ø
9. (c) Gases have much lower density than the solids and more, hence density of air is more.
liquids. 23. (b) P1V1 = P2V2
10. (a) Gases expand and occupy all the space available to 760 × 500 = P2 × 200.
them because there is no force of attraction between
760 ´ 500
the particles of a gas at ordinary temperature and P2 = = 1900 mm Hg
pressure. 200
11. (d) 24. (d) Given, P1 = 15 atm, P2 = 60 atm
12. (c) Gaseous state of substance has the maximum thermal V1 = 76 cm3, V2 = 20.5 cm3.
energy. If the gas is an ideal gas, then according to Boyle's law,
13. (c) Gases do not have definite shape and volume. Their it must follow the equation,
volume is equal to the volume of the container. P1V1 = P2V2
14. (c) Robert Boyle made first reliable measurement on P1 × V1 = 15 × 76 = 1140
properties of gases. P2 × V2 = 60 × 20.5 = 1230
\P1V1 ¹ P2 V2
15. (c)
®

P P \ The gas behaves non-ideally.

The given information is not sufficient to comment on
other statements.
V® 1/V ® 25. (d) The mathematical relationship between pressure and
Curve I Curve III temperature was given by Gay Lussac's law.
Both these graphs represents Boyle's law. 26. (a) V1 = 2 L, T2 = (26.1 + 273) K = 299.1 K, V2 = ?
16. (a) Given initial volume (V1) = 600 c.c.; Initial pressure T1 = (23.4 + 273) K = 296.4 K
(P1) = 750 mm of Hg and final volume (V2) = 500 c.c. V V VT
according to Boyle’s law, From Charle's law, 1 = 2 Þ V2 = 1 2
T1 T2 T1
P1V1 = P2V2
or 750 × 600 = P2 × 500 2L ´ 299.1K
Þ V2 = = 2L ´1.009 = 2.018 L
296.4K
STATES OF MATTER 471

27. (c)
V1 V2 42. (a) Given nCO = n N2
= at const. pressure
T1 T2
PCO + PN2 = 1 atm
22.4 V2 Partial pressure of a gas = mole fraction of gas × total
Þ = , V2 = 30.6 litre
273 373 pressure
28. (d) According to Boyle’s law at constant temperature, n N2 n N2 1
\ PN2 = ´1 = ´1 = = 0.5 atm.
1 n CO + n N2 2n N2 2
Vµ or PV = constant
P 43. (a) Given
29. (a) Applying Boyle's law P1V1 = P2V2 for both gases P1 = 1.5 bar, T1 = 273 + 15 = 288 K, V1 = V
500 200 P2 = 1.0 bar ,T1 = 273 + 25 = 298K, V2 = ?
´ 400 = P ´ 3 Þ P = P1V1 P2 V2
1000 3 =
T1 T2
666.6 400
600 ´ = P¢ ´ 3 Þ P¢ = 1.5 ´ V 1 ´ V2
1000 3 =
288 298
200 400 600 V2 = 1.55 V i.e., volume of bubble will be almost 1.6 time
Þ PT = P + P¢ = + = = 200 torr to initial volume of bubble.
3 3 3
30. (b) According to Boyle's law, PV = constant 44. (a) Partial pressure = total pressure × mole fraction
\ log P + logV = constant 64
Moles of oxygen = =2
logP = – logV + constant 32
Hence, the plot of log P vs logV is straight line with 60
Moles of neon = =3
negative slope. 20
2 2
Mole fraction of oxygen = =
2+3 5
2
logP PO2 = ´ 10 = 4 bar
5
logV 3 3
Mole fraction of neon = =
31. (a) At STP molar volume of an ideal gas or a combination 2+3 5
of ideal gases is 22.71098 L mol–1. 3
PNe = ´ 10 = 6 bar
32. (d) 44 g at STP occupies volume 22.4 litre which is molecular 5
mass of CO2. Molecular mass occupies 22.4 litre at STP. 45. (d) Value of gas constant depends only upon units of
33. (b) An ideal gas obeys the gas laws under all experimental measurement.
conditions. 46. (a) Given conditions
34. (c) In the equation PV = nRT, n moles of the gas have V1 = 16.4 L, V2 = 5 L
volume V. P1 = 1.5 atm, P2 = 4.1 atm
35. (b) R = 0.082 litre atm K–1 mol–1 . T1 = 273 + 27 = 300 K,
T2 = 273 + 227 = 500 K
m
36. (d) PV = nRT = RT P1V1 nT
M Applying gas equation, = 1 1
P2 V2 n 2 T2
m PM
or PM = RT = dRT Þ d = n1 PVT
V RT = 1 1 1
n 2 P2 V2 T2
PV T 760 546
37. (c) V2 = 1 1 1 = ´ ´ 273 = 691.6 ml 1.5 ´16.4 ´ 500 2
T1 P2 600 273 \ =
4.1 ´ 5 ´ 300 1
38. (a) Total moles 47. (d) On applying Dalton's law,
4 2 Partial pressure of a component
= + = 1.125; PV = nRT
32 2 = Mole fraction × Total pressure
Þ P = 1.125 ´ 0.0821 ´ 273 Given, mass of N2 = 56 g, mass of O2 = 96 g
Total pressure = 10 atm
P = 25.215 atm
39. (a) 56 n 96
nN 2 = = 2, 02 = =3
40. (b) Because H2 and Cl2 gases may react with each other to 28 32
produce HCl gas hence Dalton’s law is not applicable.
nN 2 2
nRT 6 ´ 8.314 ´ 402 XN 2 = = = 0.4,
41. (d) P = = ; 41648 Pa n N 2 + nO 2 2+3
V 16.02 0.03
 EBD_7374
472 CHEMISTRY

nO 2 3 54. (a) From ideal gas equation, PV = nRT

XO 2 = = = 0.6
n N 2 + nO 2 2+3 æmö RT
PV = ç ÷ RT or M = m
\ PN = 0.4 × 10 = 4 atm, PO = 0.6 × 10 = 6 atm èMø PV
2 2
48. (d) From the ideal gas equation : Let the molecular wt. of A and B be MA and MB
respectively.
PV = nRT
RT 3 ´ RT
PV 3170×10-3 Then MA = 2 1 ´ V ; M B 0.5 ´ V
or n = = = 1.27 × 10–3
RT 8.314×300
M
A 2RT 0.5V 2 ´ 0.5 1
49. (d) All the gases occupy the available volume and will \ M = V ´ 3RT = 3
=
3
form homogeneous mixture. B

50. (a) Since atmospheric pressure remain constant Therefore, the ratio MA : MB = 1 : 3
V1 V2 V1 2800 m3 PA VA 8 ´12 96
= = 55. (c) Moles of A, (n A) = = =
Þ RT RT RT
T1 T2 298 K 372 K
V1 = 2243 m3 PB VB 8 ´ 5 40
Moles of B, (n B) = = =
2800 m3 volume of inflated balloon. RT RT RT
Mass of air in inflated ballon = 2800 m3 × 0.94 kg m–3 Total pressure × total volume = (nA + nB) × RT
= 2632 kg 1
Keeping the volume same = 2800 m3 p ´ (12 + 8) = (96 + 40)RT
RT
The mass of air, which occupies it with density
(1.2 kg/m3) is 2800 × 1.2 = 3360 kg P = 6.8
Amount of air which had been escaped = 3360 – 2632 Partial pressure of A = P × mole fraction of A
= 728 kg æ 96 96 + 40 ö
= 6.8 ç ÷
16 1 è RT RT ø
51. (d) n of O 2 = =
32 2 = 4.8 atm
3 Partial pressure of B = 6.8 – 4.8 = 2 atm.
n of H 2 =
2 70.6 g
56. (d) Number of moles of O2 = = 2.21 mole
3 1
Total no. of moles = + = 2 32 g mol -1
2 2

V=
nRT 2 ´ .082 ´ 273
= = 44.8L = 44800 mL Number of moles of Ne = 167.5 g = 8.375 mole
P 1 20g mol -1
PM 2.21
52. (b) d =
RT Mole fraction of O2 = = 0.21 mole
2.21 + 8.375
It means density of gas is directly proportional to
Mole fraction of Ne = 1 – 0.21 = 0.79
pressure and inversely proportional to temperature.
Partial pressure of a gas = Mole fraction × total pressure
Density of neon will be maximum at highest pressure
and lowest temperature. Partial pressure of O2 = 0.21 × 25 = 5.25 bar
Partial pressure of Ne = 0.79 × 25 = 19.75 bar
53. (a) Given weight of empty glass vessel = 50 g
Weight of vessel filled with liquid = 144 g 57. (a) Extent of diffusion H2 > CH4 > SO2 because rate of
\ Weight of liquid = 144 – 50 = 94 g. 1
Volume of liquid = Mass/density = 94/0.47 diffusion µ
molar mass
= 200 mL = 200 × 10–3 L. Order of partial pressure after diffusion is
Given, pressure of ideal gas = 760 mm Hg = 1 atm
Temperature = 300 K pSO 2 > pCH 4 > pH 2
R = 0.0821 L atm K–1 mol–1 58. (c) Number of moles, temperature and volume are same.
Mass of ideal gas = 50.5 – 50 = 0.5 g 59. (b) According to kinetic theory the gas molecules are in a
According to ideal gas equation, state of constant rapid motion in all possible directions
w colloiding in a random manner with one another and
PV = nRT = RT with the walls of the container and between two
M
successive collisions molecules travel in a straight line
0.5 path but show haphazard motion due to collisions.
1 × 200 × 10–3 = ´ 0.0821´ 300
60. (c) Given statement explain the great compressibility of
M
gases.
0.5 ´ 0.0821´ 300 61. (b) Particles of a gas are always in constant and random
M= = 61.575
200 ´10 –3 motion. If the particles were at rest and occupy fixed
STATES OF MATTER 473

positions, then a gas would have a fixed shape which 79. (a) For statement (iii), we can move down from G towards
is not observed. D by lowering the temperature.
62. (d) Kinetic theory of gases proves all the given gas laws. For statement (iv), we get liquid as soon as we cross
63. (d) Molecules move very fast in all directions in a straight point H.
line by colliding with each other but with different 80. (b) At 1 atm pressure boiling temperature is called normal
velocity. boiling point. If pressure is 1 bar than the boiling point
64. (b) At low temperature and high pressure. is called standard boiling point of the liquid.
65. (a) In van der waal’s equation ‘b’ is for volume correction 81. (c) At high altitude atmospheric pressure is low.
82. (b) 1 bar pressure is slightly less than 1atm pressure.
æ a ö æ a ö
66. (c) ç P + 2 ÷ (V – b) = RT; Here ç P + 2 ÷ represents 83. (d) A substance exists as a liquid above its m. p. and below
è V ø è V ø its b. p.
the intermolecular forces. 84. (a) The kinetic energy of molecules in gaseous state is
67. (b) more than those in the liquid state as the molecules in
(i) At very large molar volume gaseous state can move freely (with higher speed) as
compared in liquid state.
a
P+ » P and Vm - b = Vm 85. (a)
Vm2 86. (d) All these phenomena are caused by surface tension.
(iii) According to van der Waal’s equation 'a' and 'b' are 87. (b) 88. (b)
independent of temperature. 89. (c) Due to intermolecular H-bonding the surface tension
of H2O is more than other liquid. One H2O molecule is
n 2a PV 2 joined with 4 another H2O molecule through H–bond.
68. (a) P= ; a = = atm dm 6 mol –2
V2 n2 Hydrogen bonding is in order H2O > C2H5OH > CH3OH.
69. (c) Easily liquefiable gases have greater intermolecular 90. (a) Boiling point of water is 100°C whereas evaporation of
forces which is represented by high value of 'a'. The water into water vapours occurs at room temperature.
greater the value of 'a' more will be liquefiability. 91. (a) As intermolecular forces are least in case of petrol.
So, the order is Q < S < P < R. Thus, it has highest rate of evaporation.
70. (d) 92. (c) The correct order of viscosity of the given liquids is
dimethyl ether < methyl alcohol < water < glycerol.
æ a ö a 93. (d)
71. (c) çP + 2 ÷ (V – b) = RT at high pressure V 2 can be
è V ø 94. (a) Since surface tension depends on the attractive
forces between the molecules, and hydrogen bonding
a special type of dipole-dipole interactions in (b), (c)
neglected
and (d) which is stronger than London forces of
PV – Pb = RT and PV = RT + Pb
attraction in hexane.
PV Pb 95. (c)
=1+
RT RT 96. (a) Force is required to maintain the flow of layer which
is inversely proportional to the area of contact of
Pb layer therefore flow in B is greater than that in A as
Z=1+ ; Z > 1 at high pressure
RT the area of contact is greater in A. Also viscosity of
the fluid decreases with increase in temperature
an 2 therefore liquid flow increases.
72. (a) For statement (ii), Preal = Pideal -
V2 97. (b) As the intermolecular forces of attraction decrease
For statement (iii), value of 'a' is independent of with the rise in temperature, the surface tension of a
temperature and pressure. liquid, thus, decreases with increase in temperature.
73. (c) Due to small size of these species (H2 and He)
intermolecular interactions (van der Waal forces) are Exercise - 2
very low, therefore it is difficult to compress these. 1. (c) At high altitude pressure is low hence boiling point is
74. (d) CO2 has highest critical temperature of 304.2 K
low due to which things take more time to cook.
However, in a pressure cooker, pressure is increased
75. (d) In the ideal gas, the intermolecular forces of attraction
and hence, boiling point increases. Thus, in a pressure
are negligible and hence it cannot be liquefied. cooker food get cook faster i.e. a less period of time.
76. (d) Above Boyle point, real gases show positive deviation 2. (b) The property of surface tension explain the spherical
from ideality and Z values are greater than one. shape of rain droplets. Surface tension tries to decrease
77. (c)
the surface area of the liquid to the minimum. The rain
78. (c) More will be critical temperature easier is the liquifaction
droplets are spherical because for a given volume, a
of the gas. Hence correct order will be
sphere has minimum surface area.
He < H2 < N2 < O2
 EBD_7374
474 CHEMISTRY

3. (c) According to Boyle’s law at a particular temperature, 11. (a) For ideal gas PV = constant at all pressures. Therefore,
PV = constant only B represents ideal gas.
Thus, P1V1 = P2V2 = P3V3 = P4V4 12. (c) Kinetic energy of the molecules of liquid increases with
As V1 > V2 > V3 > V4 increase of temperature, which can overcome the
Therefore, P1 < P2 < P3 < P4 intermolecular forces. Hence, the liquid starts flowing.
4. (c) London dispersion force is a temporary attractive force In other words the viscosity of a liquid decrease with
that results when the electrons in two adjacent atom increase in temperature.
occupy position that makes the atoms form temporary 13. (b) The surface tension of liquids generally decreases with
dipoles. The energy of interaction varies as increase of temperature and becomes zero at the critical
1 temperature. This is due to the fact that with increase
. of temperature, the kinetic energy of the molecules
( distance between two interacting particles )6 increases and therefore, the intermolecular attraction
Larger or more complex are the molecules, greater is decreases.
the magnitude of London forces. This is obviously 14. (c) According to Avogadro’s law "At same temperature
due to the fact that the large electron clouds are easily and pressure
distorted or polarised. Hence, greater the polarisability Volume µ no. of moles"
of the interacting particles, greater is the magnitude of w w w
the interaction energy. n H2 = ; n O 2 = ; n CH 4 =
2 32 16
5. (c) Dipole-dipole forces act between the molecules
possessing permanent dipole and ends of dipoles Q VH : VO : VCH = n H 2 : n O 2 : n CH 4
2 2 4
possess 'partial charges'. Partial charges present on
ends of a dipole are always less than the unit electronic w w w
= : : = 16 : 1 : 2
charge. 2 32 16
6. (c) Let the number of moles of dihydrogen and dioxygen
1
be 1 and 4. 15. (b) Rate of diffusion µ
Molecular mass
4
Mole fraction of O2 = Q Molecular mass of HCl > Molecular mass of NH3
5
\ HCl diffuses at slower rate and white ammonium
Partial pressure of O2 = Mole fraction of O2 × total chloride is first formed near HCl bottle.
pressure of mixture 16. (d) CO2 has highest critical temperature of 304.2 K
4 PV
= ´ 1 atm 17. (b) Compressibility factor (Z) =
5 RT
= 0.8 atm = 0.8 × 105 Nm–2 = 8 × 104 Nm–2 (For one mole of real gas)
7. (a) From Gay-Lussac's law, at constant volume, as the van der Waals equation
temperature is increased, pressure increases.
8. (d) Higher the critical temperature, more easily is the gas a
(P + )(V - b) = RT
get liquified. Hence, order of liquefaction starting with V2
the gas liquefying first will be : O2, N2, H2, He. At low pressure, volume is very large and hence
9. (b) The SI unit of viscosity coefficient (h) in Nm–2 s or correction term b can be neglected in comparison to
Nsm–2. very large volume of V.
dv i.e. V - b » V
As we know that, f = hA
dx æ a ö
where, f = force ç P + 2 ÷ V = RT
è V ø
h = viscosity coefficient
a
PV + = RT
dv V
= velocity gradient
dx a
PV = RT -
Substitute SI units of f = N, dx = m, A = m2 and v = ms–1 V
in above equation, we get, PV a
= 1-
N´m RT VRT
h= -1
= Nm -2s
2
m ´ ms a
Hence, Z = 1 -
Hence, the SI unit of h is Nsm–2 VRT
10. (a) Among all the four cities Shimla has the lowest 18. (c)
atmospheric pressure. Since lower the atmospheric 19. (a) At high temperature and low pressure.
pressure, lower is the boiling point. Thus, at Shimla 20. (d) By ideal gas equation
liquid will boil first.
STATES OF MATTER 475

P1V = n1RT Vµn

Hence in the given case.
n1 µ P1 and n 2 µ P2 Initial moles and final moles are equal (nT)i = (n T)f
n1 P1 n 170 Pi V Pi V Pf V Pf V
= Þ 1 = = 0.30 + = +
n 2 P2 n 2 570 RT1 RT1 RT1 RT2
21. (b) Hydrogen bond is a type of strong electrostatic dipole- Pi Pf Pf
2 = +
dipole interaction and dependent on the inverse cube T1 T1 T2
of distance between the molecular ion-dipole interaction
2 Pi T2
1 Pf =
µ . T1 + T2
r3 27. (b)
22. (c) P(V–b) = RT
3 3 8.313
Þ PV – Pb = RT KE = kT = ´ ´ 298 = 6.17 ´ 10 -21 J .
2 2 6.023 ´ 1023
PV Pb
Þ = +1
RT RT (Average Kinetic energy KE = 3 kT = 3 R T
2 2 N
Pb
Þ Z =1 +
RT 3RT
28. (c) r µ U and U =
Hence Z > 1 at all pressures. M
This means , repulsive tendencies will be dominant when rN
interatomic distance are small. r1 T1M 2 2 T1 ´ 64
\ = or r = = 1.625
This means, interatomic potential is never negative but r2 T2 M1 SO2 323 ´ 28
becomes positive at small interatomic distances.
or T1 = 373 K
23. (a) Given, n H 2 = n O 2 and t H 2 = t O2
PV m
According to Graham's law of diffusion for two different 29. (c) n= =
RT M
gases.
MPV 34 ´ 2 ´ 100
m= = = 282.68g
rH 2 v /t MO 2 32 RT 0.082 ´ 293
= 1 1 Þ = 30. (a)
rO2 v 2 / t 2 MH 2 2
P
31. (d) = constant (Gay Lussac's law)
1/ 2 T
= 16 = 4 P P
1/ x Þ 1 = 2 Þ P1T2 = P2T1
T1 T2
x PV = constant
=4
2 P1V1 = P2V2 [Boyle's law]
\x=8 32. (c) In real gas equation,
\ Fraction of O2 = 1/8 van der waal constant (a) µ forces of attraction.
24. (d) Given, P1 = 15 atm, P2 = 60 atm 33. (a) van der waal constant ‘a’, signifies intermolecular
forces of attraction.
V1 = 76 cm3, V2 = 20.5 cm3.
Higher is the value of ‘a’, easier will be the liquefaction
If the gas is an ideal gas, then according to Boyle's law, of gas.
it must follow the equation,
P1V1 = P2V2 æ an2 ö
34. (d) ç P + 2 ÷ (V) = nRT
P1 × V1 = 15 × 76 = 1140 ç V ÷ø
è
P2 × V2 = 60 × 20.5 = 1230
æ 2ö
\P1V1 ¹ P2 V2 ç P + 1.4 ´ 1 ÷ (0.1) = 1 × 0.082 × 300
\ The gas behaves non-ideally. ç ( 0.1)2 ÷ø
è
The given information is not sufficient to comment on P + 140 = 246 atm
other statements. P = 106 atm
25. (a) 35. (b)
26. (a) For a given mass of an ideal gas, the volume and amount 36. (c) Z can be greater than 1 or less than 1. Non - ideal gases
(moles) of the gas are directly proportional if the exert less pressure than expected due to backward pull
temperature and pressure are constant. i.e by other molecules.
 EBD_7374
476 CHEMISTRY

37. (d) van der Waals’s constant b = 4 times the actual volume
Vi (273 + 28.0)
of 1 mole molecules = 4 VN0 = 3.21´ 105 Pa ´ ´
1.03Vi (273 - 5.00)
Exercise - 3
= 3.50 ´105 Pa
m
1. (c) Gas equation is PV = RT ...(i) 3
M 8. (c) PO = ´ PT ;
2 10
P m 2 After removing 2 mole of O2,
Again V = 1 R. T ...(ii)
2 M 3
1
Divide (i) by (ii) P 'O = ´ PT
10
2
m 3 Decrease in partial pressure of O2
2= ´
m1 2
3PT PT
3 -
1
\ m1 = m . Gas escaped is then = m = 10 8 ´ 100
4 4 3PT
2. (a) If n is the total number of moles of gas and n 1 moles are 10
in the larger sphere and n2 moles in the smaller sphere. = 58.33 %
Then n = n1 + n2 and pV = nRT 9. (d) The given equation is cubic equation in the variable V
pV p¢ V p¢ V and, therefore, for a single value of P and T, there should
= + be three values of V, all of which may be real or one real
RT1 RT1 2RT2
and two imaginary.
2pT2 At Tc there values of V become identical.
p¢ =
2T2 + T1 10. (c) Molar mass ­ , ‘a’ increases
3. (d) By ideal gas equation, size of molecule ­ ,‘b’ increase
1 = n1RT
PV b(L/mol) a(bar. L2/mol2)
H2 ® 0.02661 CH4 ® 2.25
n1 µ P1 and n2 µ P2
He ® 0.0237 O2 ® 1.36
n1 P1 n 170 O2 ® 0.03183 H2 ® 0.244
= Þ 1 = = 0.30
n2 P2 n2 570 CO2 ® 0.04267
4. (c) Mass of 1 L of vapour = volume × density 3 3000 ´ 2
= 1000 × 0.0006 = 0.6 g 11. (d) K = n T RT Þ n T =
2 3 ´ 250 ´ 8.314
mass 0.6
V of liquid water = = = 0.6 cm3 3
density 1 3 ´ 103 = n T ´ 8.314 ´ 250
2
1
5. (b) n, T same hence P µ ,
V x 30 - x 2
+ =
V1 = 1000 cm3 20 40 8.314
V2 = p (10)2 × 10 = 1000 p cm3 % Ne = 28.3
4 4 12. (c) For ideal gas PV = nRT
V3 = p (10)3 = p 1000 cm3
3 3 Volume of 1 mole gas at 1 atm pressure and 273 K
\ Pressure of the gas is minimum in (III) container, is 22.4 L and at 300 K and 1 atm pressure volume
Pressure of the gas is maximum in (I), = 24.63 L.
The ratio of pressure in II and III container is 4 : 3
3 ´ 8.21
6. (c) Draw a line at constant P parallel to volume axis. Take 13. (c) nAB = = 1;
0.0821 ´ 300
volume corresponding to each temperature.
From volume axis, V1 > V2 > V3 1 ´ 8.21
Hence, T1 > T2 > T3. nB2 = = 0.25
0.0821 ´ 400
7. (c) Because the number of moles is constant. 2AB + B2 ® 2AB2
Pi Vi Pf Vf PVT Initial moles 1 0.25
= ; Pf = i i f After reaction 0.5 0.5
Ti Tf Vf Ti
Pressure of flask = PAB × (8.21 + 8.21)
Pi Vi Tf = 0.5 × 0.0821 × 250
Pf =
Vf Ti = PAB = 0.625 atm
STATES OF MATTER 477

60 Total volume of the gas available at STP conditions is

14. (b) Vc = = 75cm3 mol–1;
0.80 p1V1 T0 (20cm)(2.82L) æ 273K ö 3
V= = = =ç ÷ = 51.324L = 51324 cm
T1 P0 (300K) è 1 atm ø
Vc
b= = 25cm3 mol–1; = 0.25 L mol–1 When the balloons are being filled, the pressure in the
3
cylinder will decrease. We can continue filling from the
8a cylinder till the pressure within the cylinder is also 1 atm. At
\ Tc =
27Rb this stage, the volume of 2820 cm3 of the gas will remain
4 ´ 105 2.45 within the cylinder.
= = 5.76 gL-1 Hence, Volume of the gas which can be transferred to
821 0.425
balloons will be = 51324 cm3 – 2820 cm3 = 48504 cm3
Þ a = 3.375
Number of balloons that can be filled up
15. (d) We have,
48504 cm 3
4 3 æ 4 öæ 22 öæ 21cm ö3 = 10 balloons
Volume of balloon = pr = ç ÷ç ÷ç ÷ = 4851 cm
3
4851 cm3 / balloon
3 è 3 øè 7 øè 2 ø
 EBD_7374
478 CHEMISTRY

6. THERMODYNAMICS

Exercise - 1 19. (d) The difference between DH and DU is not usually

significant for systems consisting of only solids or
1. (b) The laws of thermodynamics deal with energy changes liquids. Solids and liquids do not suffer any significant
of macroscopic systems involving a large number of volume changes upon heating. The difference,
molecules rather than microscopic systems containing however, becomes significant when gases are
a few molecules. involved.
2. (c) Closed system can exchange energy and not matter 20. (b)
with surroundings. Pressure cooker provides closed 21. (b) DH = DE + PDV, for solid and liquid,
system. DV = or DH = DE + Dn RT, for solids and liquids Dn = 0.
3. (b) We can describe the state of a gas by quoting its 22. (c) During isothermal expansion of an ideal gas,
pressure (P), volume (V), temperature (T ), amount (n)
D T = 0. Now H = E + PV
etc.
4. (d) We know that q (heat) and work (w) are not state Q DH = DE + D ( PV )
functions but (q + w) is a state function. H – TS (i.e. G) \ D H = D E + D (nRT); T);
is also a state functions. Thus II and III are not state Thus if D T = 0., DH = DE
functions so the correct answer is option (d). i.e., remain unaffected
5. (c) Internal energy and molar enthalpy are state functions. 23. (d) We know that
Work (reversible or irreversible) is a path function. DH = DE + PDV
6. (c) 7. (d) In the reactions, H2 + Br 2 ® 2HBr there is no
8. (c) Values of state functions depend only on the state of change in volume or DV = 0
the system and not on how it is reached. So, DH = DE for this reaction
9. (a) DE =DQ–W
1 1
For adiabatic expansion, DQ = 0 24. (b) Dn = - ; DH = DE - RT ; Þ DE > D H
Þ DE = –W 2 2
25. (a) Q = –W if DE = 0
The negative sign shows decrease in Internal energy,
26. (c)
which is equal to the work done on the system by the
27. (b) In an isothermal process change in internal energy (DE)
surroundings.
is zero (as it is a function of temperature).
10. (a) It is fact that absolute values of internal energy of
\ According to first law of thermodynamics
substances cannot be determined. It is also true that it
Q Q + W = DE. Hence Q = –W (if DE = 0)
is not possible to determine exact values of constitutent
If a system undergoes a change in which internal energy
energies of a substance.
of the system remains constant (i.e. DE = 0) then –W =
11. (d) The positive sign expresses when work is done on the
Q. This means that work done by the system equals
system. Similarly, negative sign expresses when work
the heat absorbed by the system.
is done by the system
28. (a) A – (p), B – (s), C – (r), D – (q)
12. (d) Mathematical expression of first law of
Expansion of a gas in vacuum (pext = 0) is called free
thermodynamics
expansion.
DE = q + w, DE is a state function.
For isothermal irreversible change
13. (d) When work is done by the system, DU = q – W
q = –W = pext(Vf – Vi)
for isothermal reversible change
14. (c) It may involve increase or decrease in temperature of
q = – W = nRT ln (Vf/Vi)
the system. Systems in which such processes occur,
= 2.303 nRT log Vf/Vi
are thermally insulated from the surroundings.
For adiabatic change, q = 0, DU = Wad
15. (a) The shaded area shows work done on an ideal gas in a
29. (c) DH = DE + DnRT
cylinder when it is compressed by a constant external
pressure Dn = 3 – (1 + 5)
16. (b) As volume is constant hence work done in this proces = 3 – 6 = –3
is zero hence heat supplied is equal to change in DH - DE = (-3RT )
internal energy. 30. (b) DH = DU + DnRT for N 2 + 3H 2 ¾ ¾® 2 NH 3
17. (c) For isothermal reversible expansion. Dng = 2 – 4 = – 2
V \ D H = D U - 2 RT or D U = D H+ 2R T \ D U > D H
w = –nRT ln 2
V 31. (a) Mass independent properties (molar conductivity and
18. (c) W = -PDV = -105 (1 ´ 10 -2 - 1 ´ 10-3 ) = -900J electromotive force) are intensive properties. Resistance
THERMODYNAMICS 479

and heat capacity are mass dependent, hence extensive For 180 kg of water, no. of moles of water
properties.
32. (a) Volume depends upon mass. Hence it is extensive 180 ´ 103 g
= = 104 g moles
property. 18g / mol
33. (d) The magnitude of the heat capacity depends on the
J
size, composition and nature of the system. q p = 75.32 ´ 10 4 moles
34. (d) As DH = DE + DngRT mol
if np < nr; D ng = np – nr = – ve. = 753.2 × 103 J = 753.2 kJ
DH for ATP = 7 kcal / mol
Hence D H < D E.
= 7 × 4.184 kJ/mol
V2 = 29.2 kJ/mol
35. (a) q = –W = 2.303nRTlog
V1 6.022 × 1023 molecules of ATP produce = 29.2 kJ
36. (a) The properties whose magnitude depends upon the 29.2 kJ produced from 6.022 × 1023 molecules
quantity of matter present in the system are called 75.8
extensive properties eg, internal energy. 753.2 kJ produced from 6.022 × 1023 ×
29.2
37. (c) For a cyclic process the net change in the internal = 1.5 × 1025 molecules
energy is zero because the change in internal energy 42. (a) 18gm of water at 100oC
does not depend on the path. 10gm of Cu at 25oC is added.
reversible path

o
B 100 C
A

qp = Cp, m dT
irreversible path
J 18g
38. (a) –Wirreversible = Pext (V2 – V1) = 75.32 ´ ´ (373 - 298) K
K mol 18g / mol
= 10 atm (2L – 1L)
= 10 atm – L J
= 75.32 × 75 K
V2 K
–Wreversible = ò Pex dv = 5.649 × 103 J
V1 If now 10g of copper is added Cp, m = 24.47 J/ mol K
Amount of heat gained by Cu
V2
= 2.303 nRT log V J 10g
1
= 24.47 ´ (373 – 298) K
K mol 63g / mol
2 = 291.3 J
= 1 ´ 2.303 ´ 0.0821 atm–L /K /mol × log Heat lost by water = 291.30 J
1
= 16.96 atm–L J
– 291.30 J = 75.32 ´ (T2 - 373K )
Wreversible 16.96 K
= = 1.69 » 1.7
Wirreversible 10.00 Þ –3.947 K = T2 –373 K
Þ T2 = 369.05 K
39. (c) In a reversible process the work done is greater than in
43. (b) 1 calorie = 4.184 joule
irreversible process. Hence the heat absorbed in
reversible process would be greater than in the latter 5
case. So Tf (rev.) < Tf (irr.). CP 2 R 5
= = = 1.67
40. (b) The mass and volume depend upon the quantity of 44. (d) CV 3
R 3
matter so these are extensive properties while ratio of 2
mass to its volume does not depend upon the quantity 45. (c) Given Cp = 75 JK–1 mol–1
of matter so this ratio is an extensive property. 100
n= mole , Q = 1000 J DT = ?
41. (a) q p = DH = Cp dT 18
J
Þ q p = 75.32 ´ (299 - 298) K Q = nCpDT Þ DT = 1000 ´ 18 = 2.4 K
K mol 100 ´ 75
J 46. (a) In case of electric fan electrical energy is converted
Þ q p = 75.32
K mol into mechanical energy and in case of heater, electrical
 EBD_7374
480 CHEMISTRY

energy is converted into heat energy. Therefore, these 58. (a) H2O (l ) ® H2O (g)
follow the first law of thermodynamics. DHvap = 40.79 kJ/mol
47. (b) The coefficients in a balanced thermo-chemical DH = DU + DngRT
equation refer to the number of moles (not to molecules) Þ 40.79 kJ/mol = DU + (1) (8.314 JK–1 mol–1) (373 K)
of reactants and products involved in the reaction.
48. (b) Enthalpy of formation of C2H4,CO2 and H2O are 52, – æ 8.314 ´ 373 ö
Þ DUo = çè 40.79 kJ/mol - 1000
kJ / mol ÷
ø
394 and – 286 kJ/ mol respectively. (Given)
The reaction is = (40.79 – 3.10) kJ/mol
C 2 H 4 + 3O 2 ® 2CO 2 + 2H 2 O. kJ
change in enthalpy, = 37.69
mol
( DH) = DH products - DH reactants Internal energy change for 36 g of water
= 2 ´ (-394) + 2 ´ (-286) - (52 + 0) kJ 36g
= – 1412 kJ/ mol. = 37.69 ´
mol 18g / mol
49. (b)
50. (c) The value of enthalpy of neutralisation of weak acid DU = 75.98 kJ
by strong base is less than 57.1 kJ. This is due to the 59. (d) 4NO 2 (g) + O 2 (g) ® 2N 2 O5 (g), D r H = – 111 kJ
reason that the part of energy liberated during
combination of H+ and OH+ ions is utilised in the – 54 kJ
ionisation of weak acid. DH '
1 1 2N 2 O5 (s)
51. (b) H 2 + Cl2 ¾¾ ® HCl
2 2 – 111 – 54 = D H'
DH HCl = å
B.E. of reactant D H' = – 165 kJ
- å B.E. of products 60. (a) To calculate average enthalpy of C – H bond in
methane following informations are needed
1 1 1 (i) dissociation energy of H2 i.e.
-90 = ´ 430 + + ´ 240 - B.E. of HCl
2 2 2 1
\ B.E. of HCl = 215 + 120 + 90 H 2 (g) ¾¾ ® H(g); DH = x ( suppose )
= 425 kJ mol–1 2
52. (b) Enthalpy of reaction (ii) Sublimation energy of C(graphite) to C(g)
= B.E(Reactant)– B.E(Product) C(graphite) ¾¾ ® C(g); DH = y (Suppose )
Given
= éë B.E (C= C) + 4 B.E.(C–H) + B.E.(H - H) ùû
® CH 4 (g); DH = 75 kJ mol -1
C(graphite) + 2H 2 (g) ¾¾
- éë B.E.(C - C) + 6 B.E.(C - H) ùû 61. (b)
62. (a) Conc. of HCl = 0.25 mole
= [606.1 + (4 × 410.5) + 431.37)] – [336.49 + (6 × 410.5)]
Conc. of NaOH = 0.25 mole
= –120.0 kJ mol–1
Heat of neutralization of strong acid by strong base
53. (a) Fe2O3(s)+ CO(g) ¾¾ ® 2FeO(s)+ CO2(g) = – 57.1 kJ
D H = –26.8 + 33.0 = + 6.2 kJ HCl + NaOH ¾ ¾® NaCl + H2O – 57.1kJ
54. (d) When a solid melts, increase in enthalpy is observed. 1 mole of HCl neutralise 1 mole of NaOH, heat evolved
55. (b) C 2 H 4 + 3O 2 ® 2CO 2 + 2H 2O. = 57.1 kJ
Change in enthalpy, \ 0.25 mole of HCl neutralise 0.25 mole of NaOH
DH = DH products - DH reactants \ Heat evolved = 57.1 × 0.25 = 14.275 kJ
63. (c)
= 2 ´ (-394) + 2 ´ (-286) - (52 + 0) 64. (a) C 2 H 5 OH(l) + 3O 2 (g) ¾¾ ® 2CO2 (g) + 3H 2 O(l)
= –1412 kJ/ mol. Bomb calorimeter gives DU of the reaction
56. (a) Hess’s law is used for calculating enthalpy of reaction. Given, DU = –1364.47 kJ mol–1
57. (c) The standard enthalpy of reaction is the enthalpy Dng = – 1
change for a reaction when all the participating
1 ´ 8.314 ´ 298
substances are in their standard states. The standard DH = DU + DngRT = -1364.47 -
state of a substance at a specified temperature is its 1000
pure form at 1 bar. For example, the standard state of = – 1366.93 kJ mol–1
liquid ethanol at 298 K is pure liquid ethanol at 1 bar. 65. (a) H 2O (l) H 2O (g) + Q
Standard state of solid ion at 500 K is pure iron at 1 bar. D E = 37558 J / mol
The standard conditions are denoted by adding the D E = 37.56 kJ mol–1
superscript d - to the symbol DH e.g., -DH d- .
THERMODYNAMICS 481

66. (d) This reaction shows the formation of H2O, and the X2 When DH < 0 and DS < 0 then DG will be negative at
represents the enthalpy of formation of H2O because low temperatures (positive at high temperature) and
as the definition suggests that the enthalpy of formation the reaction will be spontaneous.
is the heat evolved or absorbed when one mole of 81. (d) Since the process is at equilibrium DG = 0 for DG = 0,
substance is formed from its constituent atoms. they should be DH > 0, DS > 0.
67. (b) For the equation 82. (c) DS has negative value if number of gaseous moles
B 2 H 6 (g) + 3O 2 (g) ¾¾
® B 2 O 3 (g) + 3H 2 O(g) decreases during a reaction, Dng = –ve
Eqs. (i) + 3 (ii) + 3 (iii) – (iv) For the reaction
DH = – 1273 + 3(–286) + 3(44) – 36 2SO2 + O2 ® 2SO3
= – 1273 – 858 + 132 – 36 Dng = 2 – 3 = –1
= – 2035 kJ/mol 83. (b)
68. (d) A process is spontaneous only when there is decrease in 84. (b) Both assertion and reason are true but reason is not
the value of free energy, i.e., DG is –ve. the correct explanation of assertion.
69. (a) If DGsystem = 0 the system has attained equilibrium is For a process to be spontaneous DG must be negative.
right choice. DG = DH – TDS
In it alternative (d) is most confusing as when DG > 0, Exothermic process (DH is negative) is non-
the process may be spontaneous when it is coupled spontaneous if DS is negative and temperature is high
with a reaction which has DG < 0 and total DG is because in such condition T DS > DH .
negative, so right answer is (a). ( DG = DH - T DS = + tive ). When temperature is
70. (b) Spontaneity of reaction depends on tendency to
acquire minimum energy state and maximum decreased, T DS < DH (DG = DH - T DS = - tive)
randomness. For a spontaneous process in an isolated and so the reaction becomes spontaneous.
system the change in entropy is positive. 85. (a) DG = -RT ln K eq : Normal body temperature = 37oC
71. (d) D G is negative for a spontaneous process.
72. (a) Crystallization of sucrose solution. Entropy is a kJ J
Þ - 50 = 8.314 ´ 310 lnK eq
measure of randomness during the crystallisation of mol K mol
sucrose solution liquid state is changing into solid
state hence entropy decreases. Þ 19.39 = lnKeq
73. (b) For the reaction
Þ K eq = 2.6 ´ 108
PCl5 (g) ƒ PCl3 (g) + Cl2 (g)
86. (b) DG = DH – TDS
The reaction given is an example of decomposition DG = – TDS (when DH = 0 and DS = +ve)
reaction and we know that decomposition reactions
DG = –ve
are endothermic in nature, i.e, DH > 0.
Further 87. (a) For spontaneous reaction, dS > 0 and dG should be
Dn = (1 + 1) – 1= + 1 negative i.e. < 0.
Hence more number of molecules are present in products 88. (a) DG° = DH° – TDS°
which shows more randomness i.e. DS > 0 (DS is For a spontaneous reaction DG° < 0
positive) DH °
74. (b) For the reaction or DH° – TDS° < 0 Þ T >
DS°
2ZnS ® 2Zn + S2 ; DG1º = 293 kJ..........(1)
2Zn + O2 ®2ZnO ; DG2º = – 480 kJ ..........(2) 179.3 ´ 103
S2 + 2 O2 ®2SO2 ; DG3º = – 544 kJ .........(3) Þ T> > 1117.9K » 1118K
160.2
DGº for the reaction
2ZnS + 3 O2 ®2ZnO + 2SO2 1atm
ˆˆˆˆ†
H 2 O( l ) ‡ˆˆˆ
89. (d) ˆ H2O(g)
can be obtained by adding eqn. (1), (2) and (3)
Þ DGº = 293 – 480 – 544 = – 731 kJ DH = 40630 J mol –1
75. (a) Third law of Thermodynamics. DS = 108.8 JK–1 mol –1
76. (d)
q DG = DH - T DS When DG = 0,
77. (a) DS = DH - T DS = 0
T
q¾ ¾® required heat per mole DH 40630 J mol-1
T¾ ¾® constant absolute temperatur e T = DS = 108.8 J mol-1 = 373.4 K.
Unit of entropy is JK–1 mol–1
90. (c) For a spontaneous reaction
78. (a) For a spontaneous process, DS total is always positive.
DG(–ve), which is possible if DS = +ve, DH = +ve
79. (b) The factor TDS increases with increase in temperature.
and TDS > DH [As DG = DH – TDS]
80. (d) We know that DG = DH – TDS
 EBD_7374
482 CHEMISTRY

Exercise - 2 9. (c) During the process of freezing, energy is released which

is absorbed by the surroundings.
1. (c) Thermodynamics deals with the energy change, - q rev
feasibility and extent of a reaction, but not with the \ DSsys =
T
rate and mechanism of a process.
2. (c) For a closed vessel made of copper, there will be no q rev
exchange of matter between the system and the DSsurr = i.e., on freezing, entropy of the system
T
surroundings but energy exchange can occur through decreases and of surrounding increases.
its walls. 10. (c)
3. (d) The state of a gas can be described by quoting the (a) C (graphite) + O2 (g) ® CO2 (g); DrH = x kJ mol–1 … (i)
relationship between pressure, volume, temperature and
1
amount. The ideal gas equation is (b) C (graphite) + O 2 (g) ® CO (g); D r H = y kJ mol –1
PV = nRT 2
4. (c) Specific heat is an intensive property which depends … (ii)
On subtracting eqn (i) & (ii) we get
only on the nature of the gas. Hence, if the volume of
1
gas is reduced to half from its original volume the CO ( g ) + O 2 ( g ) ® CO 2 ( g ) ; D r H = z kJ mol -1
specific heat will remain constant. 2
5. (c) The complete combustion of one mole of butane is Hence, x – y = z or x = y + z
represented by 11. (c) x > y because same bonds are formed in reaction (1)
13 and (2) but no bonds are broken in reaction (1) whereas
C4 H10 ( g ) + O 2 ( g ) ® 4CO2 ( g ) + 5H 2 O ( l ) in reaction (2) bonds in the reactant molecules are
2
Dc H should be negative and have a value of 2658 kJ mol–1. broken. As energy is absorbed when bonds are broken,
6. (b) DfH° = Df U° + DngRT energy released in reaction (1) is greater than that in
For the reaction, Df H° reaction (2).
C(s) + 2H2(g) ® CH4(g) 12. (c) Enthalpy of formation can be positive or negative.
Df H° = 1 – 2 = –1 For example :
\ Df H° = DU – 1 × RT C+ O2 ® CO2 is exothermic whereas, C+ 2S ® CS2 is
\ Df H° < Df U° endothermic.
7. (c) For free expansion, W = 0 ; and 13. (a) Enthalpy of sublimation of a substance is equal to
For Adiabatic process, q = 0 enthalpy of fusion + enthalpy of vaporisation.
According to first law of thermodynamics, Sublimation is, direct conversion of solid to vapour.
DU = q + W = 0 Writing in two steps, we have solid ® liquid ® vapour
Since there is no change in DU hence, temperature solid ® liquid requires enthalpy of fusion
change will be zero i.e., DT = 0 liquid ® vapour requires enthalpy of vaporisation
8. (b) Area under the curve is always greater in irreversible 14. (b) DG gives a criterion for spontaneity at constant
compression than that in reversible compression which pressure and temperature.
can be seen from given figure. (i) If DG is negative (< 0), the process is spontaneous.
(ii) If DG is positive (> 0), the process is non-
spontaneous.
(iii) If DG is zero then reaction is at equilibrium.
P 15. (b) For adsorption DS < 0 and for a spontaneous change
DG = – ve
hence DH should be highly negative which is clear
from the equation
Vf Volume (V) Vi DG = DH – TDS
= – DH – T(– DS) = – DH + TDS
Irreversible compression
So if DH is highly negative DG will also
be (– ve)
16. (b) Given DU = 2.1 k cal., DS = 20 cal. K– 1
T = 300 K
P Q DH = DU + DngRT
Putting the values given in the equation
2
DH = 2.1 + 2 ´ ´ 300
1000
Vf Volume (V) Vi = 2.1 + 1.2 = 3.3 k cal.
Now, DG = DH – TDS
Reversible compression
THERMODYNAMICS 483

20 27. (c) DG = DH – T · DS
= 3.3 - 300 ´ = - 2.7 kcal For a spontaneous reaction DG = –ve (always)
1000
which is possible only if
17. (a) 2H 2 O 2 (l ) ¾¾
↑ 2H 2O(l ) ∗ O 2 ( g ) ΧH < ? DH < 0 and DS > 0
ΧH < [2≥ΧH f of H 2O(l ) ∗ (ΧHf of O2 ) \ spontaneous at all temperatures.
,(2≥ΧHf of H 2O2 (l ))] 28. (b) DH is given by
= [(2 ´ -286) + (0) - (2 ´ -188)] DH = DU + Dn g RT
= [-572 + 376] = -196 kJ / mol 1 When Dn g = 0 , DH = DU
18. (c) Assertion is true but reason is false.
DH = DE + ngRT When Dn g ¹ 0, DH ¹ DU
Dng = (1 + 3) – 2 DH > DE.
If the value of Dng is less than one then DH < DE. For C2 H 4 (g) + H 2 (g) ¾¾
® C2 H 6 (g)
19. (a) C 2 H 5 OH(l) + 3O 2 (g) ® 2CO (g) + 3H O(l) Dn g = 1 - 2 = -1
2 2
Bomb calorimeter gives DU of the reaction 29. (b) We are given,
Given, DU = –1364.47 kJ mol–1
Dng = – 1 15
C6 H 6 (l ) + O2 (g) ® 6CO2 (g) + 3H 2 O(l )
DH = DU + DngRT 2
1 ´ 8.314 ´ 298 DH = -3270 kJ mol -1 … (i)
= -1364.47 - = – 1366.93 kJ mol–
1000
C(gr) + O 2 (g) ® CO2 (g),
20. (a) The greater the negative value of heat of neutralisation,
more is the strength of the acid. Hence, DH = -394 kJ mol-1 …(ii)
HCOOH > CH 3COOH > H 2S > HCN
1
21. (a) Given: DH = 186.5 kJ mol -1 H 2 (g) + O2 (g) ® H 2 O(l ),
2
B. pt of water
= 100°C = 100 + 273 = 373K DH = -286 kJ mol -1 …(iii)
Entropy change, Formation of C6H6
DH 186.5 KJ mol -1 6C(gr) + 3H 2 (g) ®
DS = =
T 373K
= 0.5 kJ mol -1K -1 C6 H 6 (l ); DH = ? …(iv)

22. (a) C + O2 ® CO2 + 393.5 kJ/mol By multiplying eq. (ii) with 6 and eq. (iii) with 3 and
12g 44g adding we get,
44g is formed from 12g of carbon 3
6C(gr) + 6O 2 (g) + 3 H 2 (g) + O 2 (g)
12 ´ 35.2 2
35.2g is formed from g of C ® 6CO 2 ( g ) + 6 H 2 O(l )
44
= 9.6 g of C = 9.6/12 = 0.8 mole DH = 6(-394) + 3( -286)
1 mole release heat 393.5 kJ
= (-2364) + (-858)
0.8 mole release heat = 393.5 × 0.8
= 314.8 kJ » 315 kg = -3222 kJ/mol
23. (b) For combustion reaction, DH is negative, Now, by substracting eq. (i) from (v) we get
Dn = (16 + 18) – ( 25 + 2 ) =+7, so DS is + ve, reaction is 6C(gr) + 3H 2 (g) ® C 6 H 6 (l )
spontaneous, hence DG is –ve. DH = -3222 - (-3270) = +48 kJ / mol
24. (a) I 2 ( s ) + Cl2 ( g ) ¾¾
® 2ICl( g ) 30. (b) Given
DrH = [DH(I2(s) ® I2(g)) + DHI–I C(s) + O2(g) ® CO2(g); DH = –393.5 kJ mol–1 …(i)
+ DHCl–Cl] – [DHI – Cl] 1
= 151.0 + 242.3 + 62.76 –2 × 211.3 = 33.46 CO(g) + O (g) ® CO2(g); DH = –283.5 kJ mol–1 …(ii)
2 2
33.46 \ Heat of formation of CO = eqn(i) – eqn(ii)
Χf H↓(ICl) < < 16.73 kJ / mol
2 = –393.5 – (–283.5)
25. (d) DG = DH – TDS; DG is positive for a reaction to be non- = –110 kJ
spontaneous when DH is positive and DS is negative. 31. (c) Applying Hess’s Law;
26. (c) The third law helps to calculate the absolute entropies 1
D f H° = D sub H + Ddiss H + I.E. + E.A + D lattice H
of pure substances at different temperature. 2
 EBD_7374
484 CHEMISTRY

– 617 = 161 + 520 + 77 + E.A. + (– 1047) 1 1

E.A. = –617 + 289 = –328 kJ mol–1 39. (b) Dn = - ; D H = DE - RT ; Þ D E > D H
2 2
\ electron affinity of fluorine
40. (d) Let B.E of x2, y2 and xy are x kJ mol–1,
= –328 kJ mol–1
0.5 x kJ mol–1 and x kJ mol–1 respectively
32. (b) At equilibrium DG = 0
Hence, DG = DH – TeDS = 0 1 1
x 2 + y2 ® xy; DH = –200 kJ mol –1
ΧH 2 2
\ DH = TeDS or Te <
ΧS DH = –200 = S (B.E)Reactants – S(B.E)Product
For a spontaneous reaction
DG must be negative which is possible only if DH – é1 1 ù
TDS < 0 = ê ´ (x) + ´ (0.5x) ú – [1 ´ (x)]
ë 2 2 û
ΧH
\ DH < TDS or T = ; Te ; T On solving, x = 800 kJ mol–1
ΧS
33. (b) The system is in isolated state. 41. (d) DStotal = DSsys + DSsurr > 0
Q For an adiabatic process, q = 0 DH
surr
- D S sys
DSsurr = =
DU = q + w T T
\ DU = w Q Heat lost by system = Heat gained
= –pDV by surrounding vice versa.
= –2.5 atm × (4.5 – 2.5) L æ - DHsys ö
= –2.5 × 2 L-atm DStotal = DSsys + ç ÷
è T ø
= –5 × 101.3 J Entropy of universe always increases for spontane-
= –506.5 J » –505J
ous process.
34. (a) Given DH 35.5 kJ mol–1
DS = 83.6 JK–1 mol–1 V2
Q DG = DH – TDS 42. (b) w = nRT ln V
1
For a reaction to be spontaneous, DG = –ve
4 x
i.e., DH < TDS RT ln = 3RT ln
2 2
DH 35.5 ´ 103 Jmol -1 æ xö
3
\ T> = ln 2 = ln ç ÷
DS 83.6 JK -1 è 2ø
So, the given reaction will be spontaneous at x3 = 16
1 2
T > 425 K
x = (16 ) 3 = 4 3
35. (c) Given Cp = 75 JK–1 mol–1
100 15
n= mole , Q = 1000 J DT = ? 43. (d) C 6 H 6 (l) + O 2 (g) ® 6CO 2 (g) + 3H 2 O(l)
18 2
Dng = 6 – 7.5 = –1.5
Q = nCpDT Þ DT = 1000 ´ 18 = 2.4 K (Dng = change in gaseous mole)
100 ´ 75 DU or DE = – 3263.9 kJ
DH = DU + Dng RT
36. (b) DH = S é DH f° products ù -S éê DH f° reactants ùú Dng = –1.5
ëê úû ë û
R = 8.314 JK–1 mol–1
DH° = [ D H f° (CO)(g) + DH f° (H 2 O)(g)] – T = 298 K
So DH = –3263.9 + (–1.5)8.314 ×10–3 × 298
[DH f° (CO 2 )(g) + DH f° (H 2 )(g)] = –3267.6 kJ
= [– 110.5 + ( – 241.8)]– [– 393.5 + 0] = 41.2 kJ – DH° DS°
44. (a) The relation is : ln k = +
37. (c) From 1st law of thermodynamics RT R
DU = q + w DH = –ve exothermic reaction
For adiabatic process : – DH °
slope = = + ve
q=0 R
\ DU = w So from graph, line should be A and B.
1atm
38. (a) DG = DH – TDS 45. ˆˆˆˆ†
(d) H 2 O( l ) ‡ˆˆˆ ˆ H2O(g)
For a reaction to be spontaneous,
DH = 40630 J mol –1
DG = –ve i.e., DH < TDS
DS = 108.8 JK–1 mol –1
DH 35.5 ´ 103 Jmol -1 DG = DH - T DS When DG = 0,
\T> =
DS 83.6 JK -1 DH - T DS = 0
So, the given reaction will be spontaneous at T > 425 K DH 40630 J mol-1
T = DS = 108.8 J mol-1 = 373.4 K
THERMODYNAMICS 485

Exercise - 3 1 atm = 105 × 1.013 Pa

Þ P < 10.952≥103 ≥1.013≥105 Pa
1. (c) No intramolecular force act between gaseous molecule.
2. (c) DH = (n1Cp,m + n2Cp,m ) DT = 11.094 × 108 Pa
1 2 8. (d) DG° = – RT ln KP; KP = (2x)2 X = 4x3
æ 7 ö
= ç 0.5 ´ R + 0.5 ´ 4 R ÷ ( -100 ) DG° = – RT ln (4X3)
è 2 ø DG° = – RT ln 4 – 3RT ln X
= – 375 R 9. (d) DH needed for change = DHheating + DHvaporisation
3. (c) w = – Pext (Vf – Vi) = 50 ´ 103 ´ 1 ´ 90 + 540 ´ 50 ´ 103
æ 60 ´10-3 40 ´10-3 100 ´10-3 ö = 31500 ´ 103 cal
31500 ´ 103 ´ 100
= -105 ç + - ÷ DH actually needed =
ç 0.60 1000 1000 ÷ø 60
è
(Since only 60% of heat is used to do so)
= – 105 (100 × 10–3 + 0.04 × 10–3 – 0.1 × 10–3) Now 368 ´ 103 cal heat is given on combustion by 22.4
|w| = 9994 J litre C2H6
1
4. (a) N 2 (g ) + O 2 ® N 2 O(g ) 31500 ´ 103 ´ 100
2 \ heat is given by
.-. + ..
60
1
N º N(g) + ( O = O ) ® N. . = N = O. . (g)
2 22.4 ´ 31500 ´ 103 ´ 100
=
DH f o = [Energy required for breaking of bonds ] 60 ´ 368 ´ 103
- [Energy released for forming of bonds] = 3.196 ´ 103 litre
= 3.196 m3
1 10. (b) For the reaction
= ( DH ( N º N ) + DH ( O =O ) - ( DH N =N + DH N =O ) 2 ZnS ® 2 Zn + S2 ; DG1º = 293 kJ ..........(1)
2
1 2 Zn + O2 ® 2 ZnO ; DG2º = –480 kJ ..........(2)
= (946 +´ 498) - (418 + 607) =170 kJ mol -1 S2 + 2 O2 ® 2 SO2 ; DG3º = –544 kJ .........(3)
2
DGº for the reaction
Resonance energy = 170 - 82 = 88 kJ mol -1
2 ZnS + 3 O2 ®2 ZnO + 2 SO2
5. (b) DHS-S + 2DH H -S = 239 2DH H -S = 175
can be obtained by adding eqn. (1), (2) and (3)
Hence, DHS-S = 239 - 175 = 64 kcal mol -1 Þ DGº = 293 – 480 – 544 = – 731 kJ
Then, DH for 8S(g ) ® S8(g ) is 8 × (–64) = –512k cal 11. (b) 12. (d)
13. (b) Use the relation Cp – Cv = R
P1 P2
6. (c) At constant volume, = 14. (d) Let x mole of KOH be neutralized by the strong acid
T1 T2
HA. Then, moles neutralized by HB = 1 – x
300 3
Þ P2 = 1´ = Hence, – 13.7 × x + (– 12.7) × (1 – x) = – 13.5
200 2 x 0.8
Þ x = 0.8; = =4
and V1 = 24.63 L 1 - x 0.2
for single phase 15. (d) In case of dissociation of CH4, the dissociation energy
Q dG = Vdp - SdT is equal to the energy required to break four C – H
(
DG = VDP - ò 2 + 10-2 T dT ) H
|
æ 10-2 ´ 50, 000 ö bonds (H - C - H)
= 1231.5 - 200 - ç ÷
ç 2 ÷ |
è ø H
= 781.5 J
360
7. (b) DG = – PDV = Work done \ C – H bond energy = = 90
DV is the change in molar volume in the conversion of 4
graphite to diamond. H H
| |
æ 12 12 ö In case of dissociation of C2H6 (H - C - C - H)
DV = ç - ´ 10-3 L = -1.708 ´ 10-3 L
è 3.31 2.25 ÷ø | |
H H
Work done = –(–1.708 × 10–3) × P × 101.3 J
1895 Jmol–1 = – (– 1.708 × 10–3) × P × 101.3J 6 C – H bonds and one C – C bond break
\ C – C bond energy = 620 – 6 × 90
1895J mol –1 3 = 620 – 540
\P = = 10.952 ´ 10 atm = 80 k cal/mol
1.708 ´ 10-3 ´ 101.3
 EBD_7374
486 CHEMISTRY

7. EQUILIBRIUM

Exercise - 1 2 ´ 10 -3 ´ 3 ´ 10 -3
Kc = =6
1. (c) 2. (b) (10-3 ) 2
3. (a) A reaction is said to be in equilibrium when rate of
forward reaction is equal to the rate of backward [AB]2
15. ˆˆ† 2AB
(c) A2 + B2 ‡ˆˆ Kc =
reaction. [A 2 ][B2 ]
4. (b) The reaction mixtures starting either with H2 or D2
reach equilibrium with the same composition, except (2.8 ´ 10-3 ) 2 (2.8) 2
that D2 and ND3 are present instead of H2 and NH3. Kc = = = 0.62
3 ´ 10-3 ´ 4.2 ´ 10 -3 3 ´ 4.2
5. (c) When the watch glass is open to the atmosphere, the
16. (b) For the reaction
rate of evaporation remains constant but the molecules
are dispersed into large volume of the room. As a CaCO3 (s) ƒ CaO (s) + CO2 (g)
consequence the rate of condensation from vapour to On the basis of the stoichiometric equation, we can
liquid state is much less than the rate of evaporation. write,
6. (c) Kc = [CaO(s)] [CO2(g)/[CaCO3(s)]
7. (b) At equilibrium, the rate of forward and backward Since [CaCO3(s)] and [CaO(s)] are both constant,
reactions is equal. therefore modified equilibrium constant for the thermal
8. (a) Equilibrium can be attained by either side of the decomposition of calcium carbonate will be
reactions of equilibrium. K´c = [CO2(g)]
9. (b) (A) Liquid ‡ˆˆ ˆˆ† Vapour equilibrium exists at the Kp = [pCO (g)]
2
boiling point. 17. ˆˆ† C, Dn = 1 - 2 = -1
(a) For A + B ‡ˆˆ
(B) Solid ‡ˆˆ ˆˆ† Liquid equilibrium exists at the
melting point. Dn -1
é mol ù é mol ù
(C) Solid ‡ˆˆ ˆˆ† Vapour equilibrium exists at the Unit of K c = ê ú = ê litre ú
ë litre û ë û
sublimation point. –1
= Litre mol
(D) Solute ‡ˆˆˆˆ† Solute (solution) equilibrium exists
18. (d) 2C(s) +O2 (g) ƒ 2CO2 (g)
in a saturated solution.
10. (a) Dn = 2 – 1 = + 1
11. (c) N2 + 3H2 ‡ˆˆˆˆ† 2NH \ Kc and Kp are not equal.
3
\ K = [NH3]2 / [N2] [H2]3 .... (i) 2
PCO 4´ 4
1 3 19. (c) Kp = ; Kp = = 8; C(s) = 1;
N2 + H 2 ‡ˆˆ ˆˆ† NH3 PCO
2
2
2 2
[NH3 ] The concentration of solids and liquids are taken as
\ K' = .... (ii) unity.
[N 2 ]1/2 [H 2 ]3/2
g Dn
Dividing equation (i) by equation (ii), we get 20. (c) As Kp = Kc (RT)
K' = K Here Dng = 1
12. (d) Rate constant of forward reaction (Kf) = 1.1 × 10–2 and So, Kp = Kc when RT = 1
rate constant of backward reaction (Kb) = 1.5 × 10–3 Thus T = 12.5 K
per minute. 21. (b) C(s) + CO2(g) ¾® 2CO(g)
Apply law of mass action,
-2
Equilibrium constant (Kc) = K f = 1.1 ´ 10 = 7.33 2
Kb 1.5 ´ 10 -3 (PCO )2 (10PCO2 )
KP = or 63 =
13. (c) A + B ˆˆ†
‡ˆˆ C + D PCO2 PCO2
At eqm. x x 2x 2x (Given KP = 65) and PCO = 10PCO2
2x.2 x
Kc = =4 100(PCO2 )2
x .x or 63 = or 63 = 100 PCO2
PCO2
14. ˆˆ† B + C
(b) Given reaction, 2A ‡ˆˆ
[B][C] 63
Kc = PCO2 = = 0.63 atm
[A]2 100
EQUILIBRIUM 487

PCO = 10PCO2 = 10 × 0.63 = 6.3 atm 29. (b) PCl5 ƒ PCl3 + Cl2
1 1 1
Ptotal = PCO2 + PCO = 0.63 + 6.3 = 6.93 atm. Moles at
2 2 2
22. (c) Using the relation KP = KC. (RT)Dn, we get equilibrium
1 1 1
Mole fraction
KP 3 3 3
= (RT)Dn at equilibrium
KC P P P
KP Partial pressure
Thus K will be highest for the reaction having 3 3 3
C at equilibrium
highest value of Dn. P P
´
The Dn values for various reactions are P
Kp = 3 3 =
P/3 3
æ 1ö 1 30. (b) For the reaction
(a) Dn = 1– ç1 + ÷ = –
è 2ø 2
2AB2 (g) ƒ 2AB(g) + B2 (g)
(b) Dn = 2 – (1 + 1) = 0 at equi 2(1- x) 2x x
(c) Dn = (1 +1) – 1= 1
(d) Dn = (2 + 4) – (7 + 2) = – 3
Kc =
[ AB]2 [ B2 ] or Kc =
(2x) 2 ´ x
Thus maximum value of Dn = 1
23. (b) 3Fe(s) + 4H2O (steam) Fe3O4 (s) + 4 H2 (g)
[AB2 ]2 {2(1 - x)}2
= x3 [(1–x) can be neglected in denominator (1– x) ; 1]
4
(pH2 ) The partial pressure at equilibrium are calculated on
Kp = only gaseous products and reactants. the basis of total number of moles at equilibrium.
(pH 2O ) 4
Total number of moles
Ni(CO)4 [CO]2 = 2 (1–x) + 2x + x = (2 + x)
24. (a) K1 = ; K = 2(1 - x)
[CO 2 ]2 2 [CO2 ] \ PAB2= ´ P where P is the total pressure.
(2 + x)
[Ni(CO) 4 ]
K= 2x x
[CO]4 PAB = ´ P , PB = ´P
(2 + x) 2 (2 + x)
2 Since x is very small so can be neglected in denominator
[Ni(CO)4 ] æ [CO2 ] ö
K= 2 × çç 2÷
÷ Thus, we get
[CO2 ] è [CO] ø PAB2 = (1 – x) × P PAB = x × P
K1 x
K= PB = ´ P
2 2
K 22
(PAB ) 2 (PB2 )
[Ni(CO) 4 ] mol l-1 Now, K P =
25. (a) K= = = (mol l -1)-3 (PAB2 ) 2
[CO]4 (mol l -1)4 x
26. (b) ˆˆ† PCl3 ∗ Cl2
PCl5 ‡ˆˆ (x)2 ´ P2 .P ´
= 2
a (1,x) ax ax
(1 - x)2 ´ P 2
a = 2, x = 0.4, V = 2 L
x 3 .P3
2(1 - 0.4) = [\ 1 – x ; 1 ]
\ [ PCl5 ] = = 0.6 mol L-1 2 ´ 1 ´ P2
2 1
x 3 .P 2.K p æ 2K p ö 3
2 ´ 0.4
[ PCl3 ] = [ Cl2 ] = 2 = 0.4 mol L-1 =
2
or x3 =
P
or x = ç
è P ø
÷

31. ˆˆ† 2NH 3 ( g ) + CO 2 ( g )

(b) NH 2 COONH 4 ( s ) ‡ˆˆ
\ K c = 0.4 ´ 0.4 = 0.267
0.6 ( PNH3 )2 ´ ( PCO2 )
27. (c) Reaction (c) can be obtained by adding reactions (a) KP = = (PNH3 )2 ´ (PCO2 )
PNH 2COONH 4 (s )
and (b) therefore K3 = K1. K2
Hence (c) is the correct answer. As evident by the reaction, NH3 and CO2 are formed
Kp in molar ratio of 2 : 1. Thus if P is the total pressure of
28. (d) K c = the system at equilibrium, then
(RT) Dn 2´ P 1´ P
PNH3 = PCO2 =
1.44 ´ 10 -5 3 3
= (R in L. atm. K–1 mole–1).
(0.082 ´ 773) -2 æ 2P ö P 4 P3
2
KP = ç ÷ ´ = 27
è 3 ø 3
 EBD_7374
488 CHEMISTRY

Given KP = 2.9 × 10–5 ˆˆˆ†

K2
(II) 2NO 2 ‡ˆˆˆ N 2 + 2O 2
-5 4P3
\ 2.9 ´ 10 = [N 2 ] [O2 ]2
27 K2 = ...(ii)
-5
2.9 ´ 10 ´ 27 [NO 2 ]2
P3 =
4 1
1 (III) ˆˆˆ
K3
NO2 ‡ˆˆˆ† N2 + O2
2
æ 2.9 ´ 10 -5 ´ 27 ö 3
P=ç [N 2 ]1/2 [O2 ]
–2
÷ = 5.82 × 10 atm
è 4 ø K3 =
32. (c) Given reaction are [NO 2 ]
X ƒ Y+Z ..... (i) [N 2 ][O 2 ]2
and A ƒ 2B .... (ii)
\ ( K3 )2 = ...(iii)
[NO2 ]2
Let the total pressure for reaction (i) and (ii) be P1 and \ from equations (i), (ii) and (iii)
P2 respectively, then
1 1
KP1 9 K1 = =
= (given) K 2 ( K3 )2
KP 1
2 34. (a) Kp = Kc(RT)Dn
After dissociation, 35. (d) Equilibrium constant (K) is independent of
X ƒ Y + Z concentrations of reactions and products.
36. (b) Reaction proceed forward according to Le-chatelier’s
At equilibrium (1– a) a a
principle.
[Let 1 mole of X dissociate with a as degree of
37. (b)
dissociation ]
38. (d) For reaction to proceed from right to left
Total number of moles = 1– a + a + a
= (1+ a) Q > K c i.e the reaction will be fast in backward direction
i.e rb > rf.
æ 1- a ö æ a ö
Thus PX = ç ÷ . P1 ; PY = ç ÷ P1 ; 39. (a) Equilibrium constant is not effected by change in
è 1+ a ø è 1+ a ø conditions like P and V. These changes can change
æ a ö only the time required to attain equilibrium.
PZ = ç ÷ .P1 40. (b) The equilibrium constant helps in predicting the
è 1+ a ø direction in which a given reaction will proceed at any
æ a ö a stage. For this purpose, we calculate the reaction
\ KP = ç .P ´ .
1 è 1 + a ÷ø 1 (1 + a ) quotient Q. The reaction quotient Q (Qc with molar
concentration and Qp with partial pressures) is defined
æ1- a ö in the same way as the equilibrium constant Kc except
P1 / ç ÷ .P1 ... (i) that the concentrations in Qc are not necessary
è1+ a ø equilibrium values.
Similarly for A ƒ 2B 41. (a) For Dn = 0, no effect of pressure.
At equilibrium (1– a) 2a 42. (c) Both (a) and (b) are correct for the equation,
We have, -
d
K = e -D G /RT
2
æ 2a P2 ö æ 1 - a ö 43. ˆˆ† Liquid
(d) Solid ‡ˆˆ
K P2 = ç ÷ /ç ÷ P2 ...(ii) It is an endothermic process. So when temperature is
è 1+ a ø è1 +a ø
raised, more liquid is formed. Hence adding heat will
Dividing (i) by (ii), we get shift the equilbrium in the forward direction.
KP1 a 2 .P1 K P1 1 P1 44. (d)
= or = . 45. (c) As in this no. of moles are increasing hence low pressure
KP2 4a 2 .P2 K P2 4 P2
will favour the forward direction.
1 P é KP1 9ù Dn = (1 + 1) – 1 = 1
or 9 = . 1 ê\ = ú 46. (b) The most favourable conditions are :
4 P2 ëê KP2 1 ûú
(i) High pressure (Dn < 0)
P 36 (ii) Low temperature (Exothermic reaction)
or 1 = or P1 : P2 = 36 : 1
P2 1 (iii) Catalyst Fe is presence of Mo.
ˆˆˆ
K1
† 47. (d) According to Le-chatelier's principle whenever a
33. (b) (I) N 2 + 2O 2 ‡ˆˆ ˆ 2NO 2 constraint is applied to a system in equilibrium, the
[NO 2 ]2 system tends to readjust so as to nullify the effect of
K1 = ...(i)
[N 2 ][O 2 ]2 the constraint.
EQUILIBRIUM 489
- -
48. (a) Meltin g of ice involve absorption of heat i.e ® H 3 PO 4 + O 2 -
(iii) H 2 PO 4 + OH ¾¾
endothermic hence high temperature favour the process. base1 acid 2 acid1 base2
Further for a given mass volume of water is less than Hence only in (ii) reaction H2PO4– is acting as an acid.
ice thus high pressure favour the process. High 65. (b) The value of ionic product of water changes with the
pressure and high temperature convert ice into liquid. temperature.
49. (c) The backward reaction is not favoured at high pressure. 66. (b)
50. (d) A 2 (g) + B2 (g) 3C(g) D(g) 67. (c) On dilution [H+] = 10–6 M = 10–6 mol
step-1 step-2 Now dissociation of water cannot be neglected,
since the steps 1 and 2 are exothermic hence low Total [H+] = 10–6 + 10–7 = 11 × 10–7
temprature will favour both the reactions. In step - 1 pH = –log [H+]
moles are increasing hence low pressure will favour it. = –log (11× 10–7) = 5.98
In step 2 moles are decreasing, hence high pressure 68. (d) Q pH = 1 ; H+ = 10–1 = 0.1 M
will favour it. pH = 2 ; H+ = 10–2 = 0.01 M
51. (a) If the volume is kept constant and an inert gas such as \ M1 = 0.1 V1 = 1
argon is added which does not take part in the reaction, M2 = 0.01 V2 = ?
the equilibrium remains undisturbed. It is because the From
addition of an inert gas at constant volume does not M1V1 = M2V2
change the partial pressure or the molar concentration 0.1 × 1 = 0.01 × V2
of the substance involved in the reaction. The reaction V2 = 10 litres
quotient changes only if the added gas is reactant or \ Volume of water added = 10 – 1 = 9 litres
product involved in the reaction. 69. (b) Given [OH–] = 10–3
52. (a) The reaction given is an exothermic reaction thus \ pOH = 3
according to Le-chatalier’s principle lowering of Q pH + pOH = 14
temperature, addition of F2 and / or Cl2 favour the \ pH = 14 – 3 = 11
forward direction and hence the production of ClF3 70. (a) Given [H3O+] = 1 × 10–10 M
53. (d) at 25º [H3O+] [OH–] = 10–14
54. (b) An equilibrium constant does not give any information 10 -14
about the rate at which the equilibrium is reached. \ [OH - ] = = 10-4
-10
55. (d) Base accepts protons and acid donates protons. 10
56. (b) Because NH3 after losing a proton (H+) gives NH2– -4
Now, [OH - ] = 10 - pOH = 10
NH3 + H2O ‡ˆˆ ˆˆ† NH – + H O +
2 3 \ pOH = 4
(Conjugate acid-base pair differ only by a proton) 71. (a) Molarity (M) = 10M. HCl is a strong acid and it is
57. (d) (CH3)3 B - is an electron deficient, thus behave as a completely dissociated in aqueous solutions as : HCl
lewis acid. ˆˆ† H+(10) + Cl–.
(10) ‡ˆˆ
58. (c) Lewis acid is that compound which have electron So, for every moles of HCl, there is one H+. Therefore
deficiency. eg. BF3, SnCl2. [H+] = [HCl] or [H+] = 10.
59. (c) Boron in B2H6 is electron deficient pH = – log[H+] = – log [10] = – 1.
60. (c) HSO4– accepts a proton to form H2SO4. 4
Thus H2SO4 is the conjugate acid of HSO4–. 72. (d) No. of moles of NaOH = = 0.1
+
40
+H
HSO -4 ¾¾¾® H 2SO4 [Molecular weight of NaOH = 40]
base conjugate acid –
No. of moles of OH = 0.1
of HSO-4 0.1
61. (b) HClO4 is a strong acid Concentration of OH– = = 0.1mol / L
1 litre
HNO2 is a weak acid. As we know that, [ H + ] [OH - ] = 10 -14
NH2– is a very good proton acceptor and thus, it is a
base. \ [H + ] = 10 -13 (Q OH – = 10 –1 )
H2SO4 is a strong acid hence its conjugate base (HSO4–) 73. (c) Strong base has higher tendency to accept the proton.
will be a weak base. Increasing order of base and hence the order of
62. (a) Bronsted base is a substance which accepts proton. In accepting tendency of proton is
option (a), H2O is accepting proton, i.e., acting as a base. I- < HS- < NH3 < RNH 2
63. (c)
74. (a) Given Ka = 1.00×10–5, C= 0.100 mol
64. (a) (i) H 3PO 4 + H 2 O ¾¾ ® H 3O + + H 2 PO 4- for a weak electrolyte,
acid1 base2 acid 2 base1
degree of dissociation
(ii) H 2 PO-4 + H 2O ¾¾
® HPO42- + H3O+ Ka 1´ 10 –5
acid1 base 2 base1 acid2 (a) = = = 10 -2 = 1%
C 0.100
 EBD_7374
490 CHEMISTRY

75. (b) HA ¾® H+ + A– 2
æ 1.34 ö
83. (a) K = ca 2 = 0.1 ´ ç = 1.8 ´ 10 -5
è 100 ÷ø
+ -
[H ][A ]
Ka = , Q [H+] = 10–pH
[HA] 84. (b) [H3O]+ for a solution having pH = 3 is given by
\ [H+] = 10–5 ; and at equilibrium [H+] = [A– ] [H3O]+ = 1×10–3 moles/litre
10-5 ´ 10-5 [\ [H3O]+ = 10–pH]
\ Ka = = 2 ´ 10-8 Similarly for solution having pH = 4,
0.0015
[H3O]+ = 1 × 10–4 moles/ litre and for pH = 5
Ka 2 ´ 10-8 [H3O+] = 1×10–5 moles/ litre
a= = = 4 ´ 10-6 = 2 ´ 10-3
C .005 Let the volume of each solution in mixture be IL, then
Percentage ionization = 0.2 total volume of mixture solution L = (1 + 1 + 1) L = 3L
76. (c) M1V1 = M2V2 Total [H3 O] + ion present in mixture solution
1 × 0.10 = M2 × 100 = (10–3 + 10–4 + 10–5) moles
M2 = 0.001 = 10–3 Then [H3O]+ ion concentration of mixture solution
BOH ‡ˆˆ ˆˆˆ† +
ˆ B + OH
- 10 -3 + 10 -4 + 10-5 0.00111
C 0 0 = M= M
C(1- a ) C a Ca 3 3
= 0.00037 M = 3.7 ×10–4 M.
Ca ´ Ca
Kb = 85. (c) In aqueous solution BA(salt) hydrolyses to give
C(1 - a)
BA + H2O ‡ˆˆ ˆˆ† BOH + HA
Kb = Ca2 (Q1 - a » 1) Base acid
a = Kb / C Now pH is given by
Kb 1 1 1
[OH- ] = C a = ´ C = K bC pH = pK w + pKa - pK b
C 2 2 2
substituting given values, we get
= 10-5 ´10- 3 = 10- 4 1
\ pH + pOH = 14 pH = (14 + 4.80 - 4.78) = 7.01
2
\ pH = 14 – 4 = 10
86. (c) Kw depends upon temperature as it is an equilibrium
77. (b) Acidic strength µ K a constant.
78. (d) Given Kb = 1.0 × 10–12 87. (c) Due to common ion effect addition of NH4Cl in group
[BOH] = 0.01 M [OH] = ? (III) suppresses the ionisation of NH4OH with the result
concentration of OH– decreases.
BOH ‡ˆˆˆˆ† B+ + OH -
t =0 c 0 0 88. (c) Solubility of weak electrolyte decreases in solvent
teq C (1- x ) Cx Cx having common ion. So solubility of AgI in NaI solution
is less than in pure water because of common ion effect.
C 2 x2 Cx 2 0.01x 2 89. (b) CH3COOH is weak acid while NaOH is strong base, so
Kb = = Þ 1.0 × 10–12 =
C (1 - x) (1 - x) (1 - x ) one equivalent of NaOH can not be neutralized with
On calculation, we get, x = 1.0 × 10 –5 one equivalent of CH3COOH. Hence the solution of one
Now, [OH–] = Cx = 0.01 × 10–5 = 1 × 10–7mol L–1 equivalent of each does not have pH value as 7. Its pH
79. (b) pKa = –log Ka will be towards basic side as NaOH is a strong base
Smaller the value of pKa, stronger will be acid hence conc. of OH– will be more than the conc. of H+.
\ Acid having pKa value of 10–8 is strongest acid. 90. (a) IVth group needs higher S2– ion concentration. In
80. (d) [Cu(H2O)4]2+ + 4NH3 [Cu(NH3)4]2+ + 4H2O presence of HCl, the dissociation of H2S decreases
hence produces less amount of sulphide ions due
involves lose and gain of electrons. H2O is coordinated to common ion effect, thus HCl decreases the
to Cu by donating electrons (LHS). It is then removed
solubility of H2S which is sufficient to precipitate
by withdrawing electrons.
IInd group radicals.
91. (c) Number of meq. of the acid = 0.04 × 100 = 4
a1 K a1 3.14 ´ 10-4
81. (b) = = = 4 :1 Number of meq. of the base = 0.02 × 100 = 2
a2 K a2 1.96 ´ 10-5 \ Number of meq. of the acid left on mixing = 4 – 2 = 2
Total volume of the solution = 200 mL
[H3O + ][F- ] \ No. of meq of the acid present in 1000 mL of the
82. (c) Ka = ...(i)
[HF] solution = 10
or No. of eq. of the acid in 1000 mL of the solution
[HF][OH - ]
Kb = ...(ii) 10
[F- ] = = 0.01
1000
From (i) and (ii), KaKb = [H3O+][OH–]=Kw Since the acid is monobasic and completely ionises in
(ionic product of water) solution
EQUILIBRIUM 491

0.01 N HCl = 0.01 M HCl

1.5×10 –5 1
Thus [H + ] = 0.01 = –10
= ´ 105 = 3.33 ´ 10 4
4.5×10 3
\ pH = – log (0.01) = – (– 2) = 2
92. (a) Kw at 25°C = 1 × 10–14 wt. of solute per litre of solution
96. (d) As, molarity, =
At 25ºC Mol. wt. of solute
Kw = [H+] [OH–] = 10–14 1000
At 100°C (given) Molarity of H2O = mole/litre
18
Kw = [H+] [OH–] = 55 × 10–14
H2O ƒ H+ + OH–
Q for a neutral solution
[H+]= [OH–] c (1 – a) ca ca
\ [H+]2 = 55 × 10–14 ca 2
or [H+] = (55 × 10–14)1/2 Thus, K a = = ca 2 = 1.8 × 10–14
1- a
Q pH = – log [H+] 97. (c) For weak acid dissociation equilibria, degree of
On taking log on both side dissociation a is given as :
– log [H+] = –log (55 × 10–14)1/2
1 Ka Ka
pH = – log 55 + 7 log10 a= \ %a = 100
2 C C
pH = – 0.87 + 7
[H + ][A - ] [H + ]ca [H + ]a
= 6.13 Also, K a = = =
– + [HA] c (1 - a ) (1 - a)
93. (c) CH3COOH CH3COO + H
a
[CH 3COO - ][H + ] log K a = log H + + log
Ka = 1- a
[CH 3COOH ] 1- a
Given that, or pK a = pH + log
a
[CH 3 COO - ] = [H + ] = 3.4 ´ 10 -4 M pK a - pH = log
1- a
Ka for CH3COOH = 1.7 × 10–5 a
CH3COOH is weak acid, so in it [CH3COOH] is equal to 1- a
= 10pK a -pH
initial concentration. Hence a
(3.4 ´ 10-4 )(3.4 ´10 -4 ) or, 1 = 10 pK a - pH + 1
1.7 ´10 -5 =
[CH 3 COOH ] a
1
\ a=
3.4 ´ 10 -4 ´ 3.4 ´ 10 -4 [1 + 10pKa - pH ]
[ CH 3 COOH ] =
1.7 ´ 10 -5 98. (c) Bond energy being directly related to bond strength
= 6.8 × 10–3M increases with increase in bond strength
94. (c) Higher the value of Ka lower will be the value of pKa i.e.
higher will be the acidic nature. Further since é salt ù
99. (d) For acidic buffer pH = pKa + log ê ú
CN–, F– and NO2– are conjugate base of the acids HCN, ë acid û
HF and HNO2 respectively hence the correct order of
base strength will be éA- ù
ë û
F– < NO2– < CN– or pH = pK a + log
(Q stronger the acid weaker will be its conjugate base)
[ HA ]
95. (c) Given, CH3COOH ƒ CH3COO– + H+ ; Given pKa = 4.5 and acid is 50% ionised.
[HA] = [A–] (when acid is 50% ionised)
Ka1 , = 1.5 × 10– 5 ....(i) \ pH = pKa + log 1
\ pH = pKa = 4.5
HCN ƒ H++ CN–; K a 2 = 4.5 × 10–10 pOH = 14 – pH = 14 – 4.5 = 9.5
or H+ + CN– ƒ HCN; 100. (b) Given [NH3] = 0.3 M, [NH4+] = 0.2 M, Kb = 1.8 × 10–5.
1 1 [salt]
K 'a 2 = = ...(ii) pOH = pK b + log [pKb = –log Kb;
K a 2 4.5 ´ 10–10 [base]
\ From (i) and (ii), we find that the equilibrium constant pKb = –log 1.8 × 10–5]
(Ka) for the reaction, \ pKb = 4.74
CN– + CH3COOH ƒ CH3COO– + HCN, is 0.2
= 4.74 + log = 4.74 + 0.3010 – 0.4771 = 4.56
K a = K a1 ´ K a' 2 0.3
pH = 14 – 4.56 = 9.43
 EBD_7374
492 CHEMISTRY

[OH–] = 10–2
é Salt ù
101. (d) pH = pKa+ log ê ú 2s = 10–2
ë Acid û
10-2
s=
log é H = log Ka – log é Salt ù
+ù
2
ë û ê Acid ú
ë û Ksp = 4s3
3
+ é Acid ù æ 10 -2 ö
log éë H ùû = log Ka + log ê ú = 4´ç
ë Salt û ÷
è 2 ø
= 5 × 10 –7
é H + ù = K é Acid ù
ë û aê ú 109. (b) Ksp = [Fe3+].[3OH–]
ë Salt û So molar solubility of Fe3+ = s and [3OH–] = 3s
0.1
-5 Fe(OH)3 ƒ Fe 3+ + 3OH -
= 1.8 × 10 = 9 × 10 -6 M
´
0.2 [s] [3s]
102. (d) HNO2 is a weak acid and NaNO2 is salt of that weak 1.0 ×10–38 = [s] [3s]3
acid and strong base (NaOH). 1.0 ×10–38 = s4 × 27
103. (a) Lets take an example of an acidic buffer CH3COOH and 1.0 ´ 10-38
CH3COONa. s4 =
27
CH3COOH CH3COO – + H + ;
s4 = 3.703×10–40
CH3COONa CH3COO– + Na+
when few drops of HCl are added to this buffer, the H+ 1
of HCl immediatly combine with CH3COO– ions to form (
s = 3.703 ´ 10 -40 ) 4 = 1.386 × 10–10
undissociated acetic acid molecules. Thus there will
110. (c) Let binary electrolyte be AB
be no appreciable change in its pH value. Like wise if
few drops of NaOH are added, the OH – ions will ˆˆ† A + + B-
AB ‡ˆˆ
s s s
combine with H+ ions to form unionised water molecule.
Thus pH of solution will remain constant. Hence, solubility product of AB
ˆˆ† Cr 3+ (aq.) + 3OH - (aq.)
104. (b) Cr(OH)3 (s) ‡ˆˆ Ksp = [A+] [B–]
s 3s s = [s.] [s] Þ s = s½
(s) (3s)3 = Ksp 111. (a) Ksp of As2S3 is less than ZnS. In acid medium ionisation
of H2S is suppresed (common ion effect) and Ksp of
27 s 4 = K sp ZnS does not exceed.
112. (a) Given Na2CO3 = 1.0 × 10–4 M
1/ 4 1/ 4
æ K sp ö æ 1.6 ´ 10-30 ö \ [CO32 – ] = 1.0 × 10–4 M
s=ç =ç ÷
è 27 ÷ø è 27 ø
i.e. S = 1.0 × 10–4 M
At equilibrium
105. (b) Mg(OH) 2 ‡ˆˆˆˆ† Mg ++ + 2 OH - [Ba2+] [CO32 –] = Ksp of BaCO3
Ksp = [Mg++][OH–]2 K sp 5.1 ´ 10 -9
1.0 × 10–11 = 10–3 × [OH–]2 [Ba2+] = = = 5.1 × 10–5 M
[CO32 - ] 1.0 ´ 10 -4
10,11
[OH, ] < < 10,4 113. (d) Total volume = 100 mL
10,3 1.0
[acid] = 10 mL ´ = 0.1
\ pOH = 4 100
\ pH + pOH = 14 0.5
[salt] = 20 mL ´ = 0.1
\ pH = 10 100
106. (d) pH or [H+] of a buffer does not change with dilution. [ salt ]
pH of acidic buffer = pK a + log acid
107. (b) Solubility product is the product of ionic concentration [ ]
in a saturated solution of an electrolyte at a given
temperature. 0.1
= 4.76 + log = 4.76
108. (b) Given pH = 12 0.1
or [H+] = 10–12 114. (b) ˆˆ† Ag∗ ∗ Br,
AgBr ‡ˆˆ
Since, [H+] [OH–] = 10–14
Ksp = [Ag+] [Br–]
-14 For precipitation to occur
10
\ [OH–] = = 10–2 Ionic product > Solubility product
10-12
K sp 5´10,13
Ba(OH)2 Ba 2+ + 2OH [Br, ] < < < 10,11
s 2s [Ag ∗ ] 0.05
EQUILIBRIUM 493

i.e., precipitation just starts when 10–11 moles of KBr the acidic strength increases from H2O to H2Te, thus pH
is added to 1l AgNO3 solution decreases and hence the correct order of pHs is
\ Number of moles of Br– needed from pH1 > pH2 > pH3 > pH4.
KBr = 10–11
\ Mass of KBr = 10–11 × 120 = 1.2 × 10–9 g Exercise - 2
115. (d) MX ‡ˆˆˆˆ† M + + X - (Where s is the solubility) 1. (d) Relationship between Kc and Kp is given as :
s s
Kp = Kc (RT)Dn
Then Ksp = s 2 or s = K sp where, Dn = (number of moles of gaseous products) –
↑ M 2∗
Similarly for MX 2 ¾¾ ∗ 2X , (number of moles of gaseous reactants)
For given reaction,
s 2s ˆˆ† NH 3 (g) + HCl (g)
NH 4 Cl (s) ‡ˆˆ
1
Dn = 2 – 0 = 2
é K sp ù 3
K sp = s ´ (2 s ) 2 = 4 s3 or s=ê ú 2. (d) The relationship between DG° and K is :
ë 4 û DG° = –RT ln K
ˆˆ† 3M + + X -3 When G° > 0 it implies DG° must be positive, which will
and for M 3 X ‡ˆˆ
3s s be possible when Kc is negative i.e., Kc < 1.
3. (c) At the stage of equilibria physical processes does not stop
1
but forward and reverse process occur at the same rate.
é Ksp ù 4
Ksp = (3s )3 ´ s = 27 s 4 or s = ê ú 4. (b) For the given reaction,
ë 27 û ˆˆ† PCl3 + Cl2
PCl5 ‡ˆˆ
From the given values of Ksp for MX, MX 2 and At 500 K in a closed container,
M3 X, we can find the solubilities of those salts at [PCl5] = 0.8 × 10–3 mol L–1
temperature, T. [PCl3] = 1.2 × 10–3 mol L–1
[Cl2] = 1.2 × 10–3 mol L–1
Solubility of MX < 4≥10,8 < 2≥10,4
1 Kc =
[ PCl3 ][ Cl2 ] = (1.2 ´10-3 ) ´ (1.2 ´10-3 )
1
é 3.2 ≥10,14 ù 3 é 32 ,15 ù 3
[ PCl5 ] (0.8 ´10 -3 )
Solubility of MX 2 < êê ú
ú or ê ≥10 ú
êë 4 úû = 1.8 ´ 10-3
ëê 4 úû
2+
1
5. (b) ˆˆ† ëé Fe (SCN ) ûù
Fe3+ + SCN - ‡ˆˆ
= éê8≥10,15 ùú 3 or 2≥10 ,5
ë û (Red)
When oxalic acid is added to a solution containing
1
é 2.7 ≥10,15 ù 4 iron (III) nitrate and potassium thiocynate then,
Solubility of M 3 X < êê ú
ú
equilibrium shifts towards backward direction and
ëê 27 ûú intensity of red colour decreases.
1
Oxalic acid reacts with Fe3+ ions to form a stable
= éê10,16 ùú 4 or 10–4 complex ion [Fe (C 2O4)3]3–. Thus, decreasing the
ë û concentration of Fe3+ ions.
Thus the solubilities are in the order MX > M3 X> MX2 6. (a) For the given reaction,
i.e the correct answer is (d). ˆˆ†
[CO(H 2O)6 ]3+ ( aq ) + 4Cl - ( aq ) ‡ˆˆ
116. (c) Ksp = [Ag+] [Cl–]
Pink
1.8 × 10–10 = [Ag+] [0.1]
[Ag+] = 1.8 × 10–9 M [COCl4 ]2- ( aq ) + 6H2 O ( l )
Ksp = [Pb+2] [Cl–]2 Blue

1.7 × 10–5 = [Pb+2] [0.1]2 Equilibrium shifts to backward direction on cooling

[Pb+2] = 1.7 × 10–3 M where as on heating, it shifts to forward direction. Thus,
117. (a) The pOH of a buffer consisting of NH3 (i.e. NH4OH) reaction is endothermic.i.e., DH > 0.
and salt NH4Cl (salt) is given by the equation 7. (c) pH of neutral water at 25°C = 7.0
At 25°C, [H+] = [OH–] = 10–7 and
pOH = pKb + log
[ammonia]
= 5.0 + log
[ 0.1] Kw = [H+] [OH – ] = 10–14
[salt] [1.0] On heating, Kw increases, i.e., [H+] [OH–] > 10–14
= 5.0 – log 10 = 5 – 1 = 4.0 As [H+] = [OH–]
\ [H+]2 > 10–14.
\ pH = 14 – pOH = 14 – 4.0 = 10
118. (a) The solution formed from isomolar solutions of sodium or, [H+] > 10–7 M
oxide, sodium sulphide, sodium selenide and sodium \ pH < 7
telluride are H2O, H2S, H2Se and H2Te, respectively. As As temperature increases, pH of pure water decreases
hence, it will become less than 7 at 60°C.
 EBD_7374
494 CHEMISTRY

8. (d) With the increase in acidity or Ka value of the given 15. (a) DG° = –RT ln K
acids pH decreases, hence the order of pH value of At the stage of half completion of the reaction,
the acids will be : [A] = [B]
hypochlorous acid < acetic acid < formic acid Therefore, K = 1
As we know that
(3.8 ´10-8 ) (1.74 ´10-5 ) (1.8 ´ 10-4 )
9. (a) For the reaction, DGs = - RT ln K
ˆˆ† H + + HS-
H 2S ‡ˆˆ \ DG – = 0
ˆˆ† 2NH 3 ( g )
In the reaction N 2 (g) + 3H 2 ( g ) ‡ˆˆ
[ H + ][ HS- ] 16. (a)
K a1 = … (i)
[ H 2S ] If the total pressure at which the equilibrium is
established, is increased without changing the
For the reaction, temperature, K will remain same but the equilibrium
ˆˆ† H + + S2 -
HS- ‡ˆˆ concentration will change.
[ H + ] [S2- ] 17. (b) The order of boiling point of compounds given is
Ka2 = … (ii) Water > acetone > ether
[ HS- ] Lower the boiling point, higher is the vapour pressure
of the solvent. Hence, the correct order of vapour
[ H + ] 2 [ S2 - ] pressure will be
K a3 = … (iii)
[ H 2 S] Water < acetone < ether
1 1
Hence, K a3 = K a1 ´ K a 2 18. For the reaction, ˆˆ† HI ( g )
H 2 ( g ) + I 2 ( g ) ‡ˆˆ
2 2
10. (c) According to GN Lewis an acid is a species which
accepts an electron pair and base which donates an [ HI ]
Kc = =5
electron pair. Since BF3 is an electron deficient species,
hence, it is a Lewis acid.
[ H 2 ] [ I2 ]1/ 2
1/ 2

11. (c) When the concentration of weak base (NH4OH) is Thus, for the reaction,
higher than the strong acid (HCl) a mixture of weak 2HI(g) ƒ H2(g) + I2(g)
base and its conjugate acid is obtained, which acts as
basic buffer. K c¢ =
[ H2 ][ I2 ]
[ HI ]2
NH4OH + HCl ¾® NH4Cl + H2O
Initially 0.1 M 0.05 M 0 2 2
æ 1 ö æ 1ö 1
K¢c = ç K ÷ = çè 5 ÷ø = 25 = 0.04
After reaction 0.05 M 0 0.05 M è cø
12. (d) AgCl, react with aqueous ammonia to form a complex, 19. (d) Addition of inert gas at constant volume does not affect
[Ag(NH3)2]+ Cl–. any equilibrium.
13. (a) Given, Ka = 1.74 × 10–5 20. (d) Given reaction is exothermic reaction. Hence according
Concentration CH3COOH (C) = 0.01 mol dm–3 to Le-Chatelier's principle low temperature favours the
[ H+ ] = K a .C forward reaction and on increasing pressure
equilibrium will shift, towards lesser number of moles
= 1.74 ´ 10-5 ´ 0.01 = 4.17 ´ 10 -4 i.e. forward direction.
pH = – log [H+] 21. (a) In exothermic reactions on increasing temperature value
= – log (4.17 × 10–4) = 3.4 of Kp decreases
14. (c) Given Ka for CH3COOH = 1.8 × 10–5 \ Kp > Kp¢ (Assuming T1 < T2)
Kb for NH4OH = 1.8 × 10–5. 22. (c) Na2CO3 is a salt of strong base (NaOH) and weak acid
Ammonium acetate is a salt of weak acid and weak base. For (H2CO3). On hydrolysis this salt will produce strongly
such salts basic solution. i.e. pH will be highest (pH > 7) for this
1 sotluion. Others are combination of
pH = 7 +
2
( pK a - pK b ) KCl = Strong acid + Strong base
® neutral solution (pH » 7)
é - log1.8 ´ 10 -5 ùû - éë - log1.8 ´ 10 -5 ùû
= 7+ ë NaCl = Strong acid + Strong base
2 ® neutral solution (pH » 7)
4.74 - 4.74 CuSO4 = Strong acid + wake base
= 7+ = 7.00 ® Acidic solution (pH < 7)
2
EQUILIBRIUM 495

23. (b) DG = – 2.303 log K AgCl

here K = [Ag+]2 [CO3– –] = Ksp Ksp = [Ag+] [Cl–] = 1.8 × 10–10
\ 63.3 × 10– 3 = – 2.303 × 8.314× 298 log Ksp
1.8 ´ 10 –10
63.3 ´ 10 -3 [Ag+] =
\ log Ksp = - = - 11.09 [Cl – ]
5705.8 AgBr
\ Ksp = Antilog (– 11.09) = 8 × 10– 12 Ksp = [Ag+] [Br–] = 5.0 × 10–13
24. (c) Reaction (c) is endothermic. Electrolysis or
decomposition of H2O is endothermic in nature. 5.3 ´ 10 –13
[Ag + ] =
1 [Br – ]
25. (b) ˆˆ† SO3 (g)
SO 2 (g) + O 2 (g) ‡ˆˆ
2 AgI
Ksp = [Ag+] [I–] = 8.3 × 10–17
K P = K C (RT)x
8.3 ´ 10–17
where x = Dng = number of gaseous moles in product [Ag + ] =
[I – ]
– number of gaseous moles in reactant
If we take éë Cr2 O 4 ùû = [Cl ] = [Br ] = [I ] = 1
–2 – – –
æ 1ö 3 1
= 1 - ç1 + ÷ = 1 - = -
è 2ø 2 2 than maximum [Ag+] will be required in case of
26. (a) In exothermic reactions on increasing temperature value Ag2CrO4.
of Kp decreases 32. (a) Among the given acids, HClO4 is a very strong acid,
27. (b) Equilibrium constant for reaction: completely dissociates
\ [HA] ® 0 in this case, hence cannot be used for acidic
[Product] buffer.
K = 1.6 × 1012 =
[Reactant] 33. (c) 2A(g) + B(g) ƒ 3C(g) + D(g)
The value of K is very high so the system will contain Mole ratio 2 1 3 1
mostly products at equilibrium. Molar conc. 1 1 0 0
28. (a) N2(g) + O2(g) 2NO(g) at t = 0
Equilibrium 1– 0.5 1– 0.25 0.75 0.25
[NO]2
K< molar
[N 2 ][O 2 ] Concentration = 0.50 = 0.75
1 1 [C ]3[ D] (0.75)3 (0.25)
ˆˆ† NO
N 2 ∗ O2 ‡ˆˆ
2 2 Kc = =
[ A]2 [ B ] (0.50) 2 (0.75)
[NO]
K'< <K
12
34. (d) In biological systems buffer system of carbonic acid
[N 2 ]1 2 [O 2 ]1 2
and sodium bicarbonate is found in our blood. It maintains
29. (b) DG° = –2.30RTlog K the pH of blood to a constant value of about 7.4.
because at equilibrium DG = 0 35. (b) DG°NO(g) = 86.6 kJ/mol = 86600 J/mol
30. (a) gm eq of NaOH = 0.1 × V = 0.1V
gm eq of HCl = 0.01 × V = 0.01V G °NO2 (g) = x J/mol
gm eq of NaOH > gm eq. HCl T = 298, KP = 1.6 × 1012
hence resultant solution should be basic, hence from
DG° = – RT ln KP
the eqn
Given equation,
M1V1 – M2V2 = MV
0.1V – 0.01V = MV ˆˆ† 2NO (g)
2NO(g) + O2 (g) ‡ˆˆ 2
0.09 \ 2DG°NO2 – 2DG0NO = – R (298) ln (1.6 × 1012)
M= = 0.045 = 4.5 × 10–2
2 2DG°NO2 – 2 × 86600 = – R (298) ln (1.6 × 1012)
Now pOH = – log [OH–] 2DG°NO2 = 2 × 86600 – R (298) ln (1.6 × 1012)
= – log 4.5 × 10–2 = 1.34 1
Q pH + pOH = 14 DG°NO2 = [2 × 86600 – R(298) ln (1.6 × 1012]
\ pH = 14 – 1.34 = 12.65 2
31. (c) Ag2CrO4 = 0.5 [2 × 86600 – R (298) ln (1.6 × 1012)]
36. (d) DG° = 2494.2 J
Ksp = [Ag+]2 é Cr2 O4–2 ù = 1.1 × 10–12
ë û
ˆˆ† B + C.
2A ‡ˆˆ
1.1 ´ 10 –12 R = 8.314 J/Kl mol.
[Ag + ] =
éCr2 O4–2 ù
ë û
 EBD_7374
496 CHEMISTRY

1 1 On calculating solubility of all given compounds

[A] = , [B] = 2, [C] =
2 2 Compound Solubility
[B] [C] 2 ´ 1 2 AgCl 1´ 10-5
Q= = 2 =4
[A]2 æ 1ö AgI 1´ 10-8
çè ÷ø
2
PbCrO 4 2 ´10 -7
DG° = – 2.303 RT log KC.
Ag 2 CO3 1.26 ´10 -4
2494.2 J = – 2.303 × (8.314 J/K mol) × (300 K) log KC
\ Ag2CO3 is most soluble and AgI is least soluble.
2494.2 J
Þ log KC = – 43. (a) Ionic product of AgBr is greater than that of AgCl in
2.303 ´ 8.314 J / K mol ´ 300 K comparison with there solubility product AgBr will precipitate
Þ log KC = – 0.4341 first rather than that of AgCl.
KC = 0.37 \ Kp > Kp¢ (Assuming T1 < T2)
Q > KC. 44. (d) Given,
37. (a) According to Le-Chatelier’s principle increase in ˆˆˆ
1† +
AB ‡ˆˆ
K
ˆ A +B
-1
temperature favours the endothermic reaction while
[A + ] [B- ]
decrease in temperature favour the exothermic reaction. K1 =
[AB]
Increase in pressure shifts the equilibrium in that side in
which number of gaseous moles decreases. ˆˆˆ†
K2
AB + B- ‡ˆˆˆ AB 2-
38. (a) ClO-4 < ClO3- < ClO -2 < ClO- is the correct increasing [AB2- ]
K2 =
order of Bronsted base. With increase in the number of [AB] [B- ]
oxygen atoms in the conjugate bases, the delocalisation of
the p bond becomes more and more extended. This results Dividing K1 and K2 we get
in decrease in the electron density. Consequently basicity K1 [A + ] [B- ]2
K= =
also decreases. K2 [AB2 - ]
39. (d) Clausius – Clapeyron's equation
[A + ] K
d ln P DH v \ =
= [AB2 - ] [B- ]2
dT RT 2
45. (a) Given,
40. (b) MY ƒM+ + Y–
S S ˆˆ† C + D
A + B ‡ˆˆ
KSP = S2 = 6.2 × 10–13 No. of moles initially 1 1 1 1
At equilibrium 1–x 1–x 1+x 1+x
S = 6.2´10-13
S = 7.87 × 10–7 mol L–1 2
NY3 N3+ + 3Y– æ 1+ xö
\ Kc = ç
è 1 - x ÷ø
= 100
KSP = S × (3s)3 = 27s4 = 6.2 × 10–13
1/4 1+ x
æ 6.2 ´ 10-13 ö \ = 10
S= ç ÷ 1- x
è 27 ø On solving
S = 3.89 × 10 mol L–1
–4
x = 0.81
\ molar solubility of NY3 is more than MY in water. [D]At eqm. = 1 + x = 1 + 0.81 = 1.81
41. (b) The presence of large amount of KHSO4 will decrease
ionisation of H2SO4 that result in lesser ionisation of 46. (b) ApBq pA+ + qB –
nitric acid and lesser formation of nitronium ion [NO2+]. Sp Sq
Hence the rate of nitration will be slower. Let the solubility be S mol/liter
42. (d) The solubility equilibrium for AgI is + p – q
Thus, Ksp = [A ] [B ]
AgI (aq) ƒ Ag + ( aq ) + I- ( aq ) ;
p q p. q p+q
Ksp = [Ag+][I–] = [Sp] [Sq] = p q (S) .
Let solubility of AgI be S moles per litre,
-14
[Ag+] = S, [I–] = S Kw 1´10
47. (a) a= =
Ksp = [Ag+][I–] Ka ´ K b 1.8 ´10-5 ´ 1.8 ´ 10-5
1 × 10–16 = (S) × (S) = S2
= 0.556
1
S= (1´ 10-16 ) 2 = 1 ´10 -8
EQUILIBRIUM 497

48. (d)
2 3
K p = p B1 ´ p C1 é 0.4 ´ 20 ù RT
V= ê = 5L
ë RT úû 1.6
2 3
Again, K p = p B ´ (2p C1 )
2 52. (c) ˆˆ† 2Ag + ( aq ) + C 2O 42 - ( aq )
Ag 2 C 2 O 4 (s) ‡ˆˆ
2 3 2 3 2S S
\ p B1 ´ p C1 = PB2 ´ 8p C1
KSP = [Ag+]2 [C2O2–4 ]
p 2B1 p B1 [Ag+] = 2.2 × 10–4 M
\ = p2B2 or,, = p B2 Given that:
8 2 2 \ Concentration of C2O42– ions,
49. (b) PCl 5 PCl 3 + Cl 2 -4
at eq. 1 – a a a éë C2 O42 - ùû = 2.2 ´ 10 M
2
Total no. of moles at eq. = 1 – a + a + a = 1 + a
= 1.1 ´ 10 -4 M
a a
P´ P a 2P \ KSP = (2.2 × 10–4)2 (1.1 × 10–4)
\ Kp = 1 + a 1 + a
1- a
= = 5.324 × 10–12
P 1- a2
1+ a 53. (a) Ammonia is a weak base and a salt containing its
conjugate acid, the ammonium cation, such as NH4OH
2 Kp functions as a buffer solution when they are present
or, Kp = a P ; \ a = when 1 - a 2 = 1 together in a solution.
P
54. (b) For a gaseous phase reaction Kp and Kc are related as

50. (a) (i) ˆˆ† 2NH3 ; K1 =

N 2 + 3H 2 ‡ˆˆ
[ NH3 ] 2
K p = K c ( RT )
Dn g

[ N 2 ][ H 2 ]3 For the given reaction,

1
CO(g) + O2 ( g ) ® CO2(g)
[ NO ]2 2
(ii) ˆˆ† 2NO; K 2 =
N 2 + O 2 ‡ˆˆ 1
[ N 2 ][ O2 ] Dng = 1– (1 + 0.5) = – 0.5 or -
2
1
-
1 [H 2O] \ Kp = Kc ( RT ) 2
ˆˆ† H 2O; K 3 =
(iii) H 2 + O2 ‡ˆˆ 1
2 [H 2 ][O 2 ]1/2 Kp -
or = ( RT ) 2
Applying (II + 3 × III – I) we will get Kc
55. (b) Given
5 K
ˆˆˆ†
2NH 3 + O 2 ‡ˆˆˆ 2NO + 3H 2 O; pKa (HA) = 3.2
2 pKb (BOH) = 3.4
[ H 2O ]3 The salt (AB) given is a salt is of weak acid and weak
[ NO]2 [ H ]3 ´ [ O2 ]3/ 2
´ 2
base. Hence the pH can be calculated by the formula
K=
[ N 2 ][ O2 ] [ NH3 ]2 1
\ pH = 7 + pK a – pK b
1
2 2
[ N2 ][ H 2 ]3 1 1
= 7 + (3.2) – (3.4)
K 2 K 33 2 2
\ K= = 6.9
K1
56. (c) H2CO3 H+ + HCO3–
51. (d) Max. pressure of CO2 = Pressure of CO2 at equilibrium -
For reaction, H+ + CO3–. HCO 3 can donate and accept H+.
SrCO3(s) SrO(s) + CO2(g) 57. (a) ˆˆ† X (g); DH = - x kJ
A2 (g) + B2 (g) ‡ˆˆ 2
Kp = PCO2 = 1.6 atm = maximum pressure of CO2
volume of container at this stage. On increasing pressure equilibrium shifts in a direction
where number of moles decreases i.e. forward direction.
nRT On decreasing temperature, equilibrium shifts in
V= …(i)
P exothermic direction i.e., forward direction.
Since container is sealed and reaction was not earlier So, high pressure and low temperature favours
at equilibrium. maximum formation of product.
\ n = constant. 58. (a) Solubility of BaSO4 = 2.42 × 10–3 gL–1
PV 0.4 ´ 20 2.42 ´ 10-3
n= = …(ii) \s= = 1.038 ´ 10-5 mol L-1
RT RT 233
Put equation (ii) in equation (i) Ksp = s2 = (1.038 × 10–5)2= 1.08 × 10–10 mol2 L–2
 EBD_7374
498 CHEMISTRY

1 Concentration of SO42– in Ba2– solution

59. (c) Meq. of HCl = 75 ´ ´ 1 = 15 M1V1 = M2V2
5
1 × 50 = M2 × 500
1
Meq. of NaOH = 25 ´ ´ 1 = 5 1
5 M2 =
Meq. of HCl in resulting solution = 10 10
Molarity of [H+] in resulting mixture For just precipitation
10 1 I.P = Ksp
= =
100 10 [Ba2+] [SO42–] = Ksp(BaSO4)
é1ù
pH = –log[H+] = –log ê ú = 1.0 1
ë 10 û [Ba2+] × = 10–10
60. (d) 61. (b) 10
62. (b) CH3COOK is a salt of weak acid (CH3COOH) and strong [Ba2+] = 10–9 M in 500 mL solution
base (KOH) Thus [Ba2+] in original solution (450 mL)
CH3COOK + H2O ¾¾ Þ M1 × 450 = 10–9 × 500
® CH 3 COOH + KOH
Weak acid Strong base [ where M1 = molarity in original solution]
Hence nature of solution is basic 500
63. (b) M1 = ´ 10 –9 = 1.11 ´ 10 -9 M
450
A + ˆˆ† 2C
2 B ‡ˆˆ 65. (d) DG° = – RT ln KP; KP = (2X)2 X = 4X3
DG° = – RT ln (4X3)
Initial mole 2 2 0
DG° = – RT ln 4 – 3RT ln X
At equilibrum mole 2- x 2 - 2 x 2x 66. (b)
2x = 1; x = 1/2 = 0.5 (i) HCl ¾¾ ® H + + Cl -
1.5 1 1 0.1 M 0.1 M
1.5 1 1
Equilibrium conc. \ [H+] = 0.1 M
10 10 10 pH = – log [H+] = – log 0.1 = 1
2 (ii) NaCl is a salt of strong acid and strong base so it is not
é1ù hydrolysed and hence its pH is 7.
Kc =
[ C] 2
=
êë10 úû
= 6.67 (iii) NH4Cl + H2O ‡ˆˆˆˆ† NH OH + HCl
4
2 2
[ A ]2 [ B]2 é1.5 ù é 1 ù \ The solution is acidic and its pH is less than that of
êë 10 úû êë10 úû 0.1 M HCl.
(iv) NaCN + H2O ‡ˆˆ ˆˆ† NaOH + HCN
[C ]c [ D ]d
64. (d) aA + bB c C + dD, Qc = \ The solution is basic and its pH is more than that of
[ A]a [ B ]b 0.1 M HCl.
If Qc > Kc, reaction will proceed in the direction of \ Correct order for increase in pH is
reactants HCl < NH4Cl < NaCl < NaCN.
If Qc < Kc, reaction will move in direction of products.
If Qc = Kc, the reaction mixture is already at 67. (d) N 2 O5 ˆˆ† N 2O3 + O 2
‡ˆˆ
equilibrium. 4– x x–y x+y
66. (b) [H2S] = 0.10 M ˆˆ† N 2O + O 2
[HCl] = 0.20 M ; [H+] = 0.2 M
N 2 O3 ‡ˆˆ
x–y y y+x
ˆˆ† HS– + H + K1 = 1.0 ´ 10 –7
(i) H 2S ‡ˆˆ Q [ O2 ] = x + y = 2.5
ˆˆ† S2– + 2H –
(ii) HS ‡ˆˆ = K1 × K2 for N2O5 Kc = [N2O5] [O2] / [N2O5]
= 1.2 × 10–20
( x + y )( x - y )
and 2.5 =
1.2 ´ 10–20 ´ [H 2S] 4-x
Hence [S2–] = \
[H + ]2 x = 2.166

1.2 ´ 10–20 ´ 10–1

[ N 2O5 ] = 4 – x = 1.846
= =3× 10–20 M
4 ´ 10 -2 Exercise - 3
67. (c)
1. (b) Kc =
[ NO2 ]
2
1M + Final
Na2SO4 Ba
2+
¾® Solution [ N 2 O4 ]
50 mL 450 mL 500 mL If [ NO 2 ] ® at y-axis
EQUILIBRIUM 499

lower hydrate or anhydrous salt as dehydrating agent.

[ N 2O4 ] ® at x-axis Hence, Z2SO4.
Þ y = Kc.x2 8. (b) 2NOBr (g) 2NO (g) + Br2 (g)
Parabolic curve
6P 2P P
2. (c) CaCO3(s) ƒ CaO (s) + CO2(g)
9 9 9
K = PCO2 = 1 atm (given) Since total pressure is P.
6 P 2P P
8400 8400 So, + + =P
\ By ln Kp = 7 – Þ 0= 7- [ln 1 = 0] 9 9 9 2
T T æ 2P ö P
2
p NO ´ p Br2 ç ÷ ´
8400 \ Kp = = è 9 ø 9
ÞT= = 1200 K = (1200 – 273) = 927 °C p 2N O B r 2
7 æ 6P ö
ç ÷
3. (c) PCl5(g) PCl3(g) + Cl2(g) è 9 ø
1–x x x Kp 1
\ =
Total moles after dissociation P 81
1–x+x+ x=1+x 9. (a) Since D2 has similar chemical properties as H2 so upon
mixing, NH2D and NHD2 are formed.
æ x ö
p
PCl 3
= mole fraction of PCl3 × Total pressure = ç ÷P 10. (b) For exothermic reaction yield ­ as temperature ¯
è1+ x ø
i.e., T1 > T2 > T3
ˆˆ† NH3 (g) + H 2S(g) 11. (c) DrG° = 0 – 77.1 × 2 = – 154.2 kJ/mol
4. (a) NH 4 HS(s) ‡ˆˆ
2
Start 0.5 atm 0 atm éH+ ù
At equib. 0.5 + x atm x atm
Q= ë û
Then 0.5 + x + x = 2x + 0.5 = 0.84 (given) 2
Þ x = 0.17 atm. PH2 . é Ag + ù
ë û
p NH3 = 0.5 + 0.17 = 0.67 atm ; p H 2S = 0.17 atm
10-6
= = 2 ´ 104
( )
2
K = p NH3 ´ pH 2S = 0.67 ´ 0.17 = 0.1139 = 0.11 atm
0.5 ´ 10-10
5. (a) Sb 2 S3 ( s ) + 3H 2 ( g ) ¬¾
¾¾
¾® 2Sb ( s ) + 3H 2S ( g ) DG = DrG° + RT ln Q
0.01 – a
2+
0.01 – 3a
+
2a 3a
DrG = – 154.2 +
(
8.314 ´ 300 ln 2 ´104 )
H 2S + Pb ¾¾ ® PbS + 2H 1000
no. of moles of PbS formed = – 129.5 kJ/mol
1.19
= = 0.005 mole 12. (a) Dn = 2 – 1 = 1
238 That is, with the decrease of pressure, reaction shifts
é 0.005 ù æ .01 - 005 ö
At eqm [ H 2 ] = ê ú =ç ÷; towards right, i.e. proportions of NO2 increases. Statement
ë 250 û è 250 ø (a) is correct.
3
æ 0.005 ö
Kc = ç ÷ =1 13. (d) Ag (+aq) + 2 NH 3( aq) +
[Ag(NH3 )2 ](aq)
è 0.005 ø
1
6. (c) 2AB3 (g) ƒ A 2 (g) + 3B2 (g) Instability constant =
formation constant
Initial 8 0 0
K 2.0 ´ 10-2
8 - 2a a 3a = r = = 2.0 ´ 10-8
At eqm. Kf 1.0 ´ 10 6
1 1 1
Since volume = 1 dm3 = 1 L 14. (c) The two Ksp values do not differ very much. So it is a
At eq. [A2] = 2 mol = a case of simultaneous equilibria, where the concentration
\ [AB3] = 8 – 2 × 2 = 4 M of any species can not be neglected.
[A2] = 2 M 2
[B2] = 3 × 2 = 6 M éSr 2+ ù é F- ù K sp
ë ûë û = SrF2 7.9 ´ 10-10
= = 1.128
K=
[ B2 ]3 [ A 2 ] = 6 ´ 6 ´ 6 ´ 2 = 27 mol-2L-2 éSr 2+ ù é CO32 - ù Ksp
ë ûë û SrCO
2
7.0 ´ 10-10

[ AB3 ]2 4´4
\ [F- ]2 = 1.28 = 1.128 × 1.2 × 10–3
1/4 -11 1/4 -3
7. (c) (i) pH 2O = K p = (8.1 ´ 10 ) = 3.0 ´ 10 atm = 13.5 × 10–4
p H 2 O = (K P )1/5 = (3.2 ´ 10 -9 )1/5 = 2.0 ´ 10 -2 atm
\ [F - ] = (13.5 × 10–4)1/2
(ii) = 3.674 × 10–2 » 3.7 × 10–2 M.
(iii) pH 2O = (K p )1/10 = (1.0 ´ 10 -30 )1/10 = 1.0 ´ 10 -3 atm 15. (b) pH = 9 ; [H+ ] = 10-9 ;[OH- ] = 10-5 ;
Smaller is the equilibrium pH 2O , more effective will be the [Mg ++ ] = 1´10 -3 ;[Mg++ ][OH- ]2 = 1´10-13
given Ksp of Mg(OH ) 2 = 8.9 ´10 -12 which is more than
1 ´ 10 -13 . Hence Mg(OH)2 will not precipitate
 EBD_7374
500 CHEMISTRY

8. REDOX REACTIONS

Exercise - 1 16. (c) K[Co(CO) 4 ]

1. (c) Given reaction is oxidation reaction due to removal of Let O.N. of Co be x then
electropositive element potassium from potassium 1 × ( + 1) + x + 4× (0) = 0
ferrocyanide. for K for Co for CO
Χ
2. (d) 2Na(s) ∗ H 2 (g) ¾¾↑ 2NaH(s) \ O.N. of Co is = –1
With the careful application of the concept of
17. (d) (NH4)2 SO4 is split into ions. NH +4 . Let O.N. of N be x
electronegativity only S we can find that sodium is
oxidised and hydrogen is reduced. then, 1 × (x) + 4 × (+1) = 1 \ x = –3
3. (b) Oxidation reaction (loss of 2e–)
H +1
– +1 |
2Na(s) + S(s) ¾®(Na+)2S (s) 18. (c) H – C 22+- – Cl -1 O.N. of C is zero
|
Reduction (gain of 2e–)
reaction Cl - 1
4. (a) O.N. of Mn in MnO –4 is +7 and in Mn 2+ it is +2. The 19. (d) O.N. of Fe in (a), (b), (c) and (d) respectively are : +3,
difference is of 5 electrons. +2, +2 and 0.
loss of 10e - 20. (d) OsO4
5. (c) N -2 4 H +4 4 ¾¾¾¾¾® N +2 6 Y; Let O.N. of Os be x then 1 × (x) + 4(–2) = 0
N
O.N.of N changes from – 2 to +3 \ x=8
6. (b) Blue colour of the solution disappear due to formation 21. (a) Fe(CO)5 is metal carbonyl, hence O.N. of Fe is zero.
of Zn 2+. 22. (c) O.N. of Mn in K2MnO4 is +6
7. (d) NO3- ¾¾® N 2 H 4 So, for reduction of 1 mole of 23. (d) MnO 4– (O.S. of Mn +7); Cr (CN) 36 – (O.S. of Cr +3),
+5 -2
NO3– number of electrons required is 7. NiF62 – (O.S. of Ni +4) and CrO2Cl2 (O.S. of Cr +6)
8. (b) 24. (a) Ox. no. of Cr on both side is + 6.
Oxidation loss of 2e– 25. (b) O.N. of iodine in I3- is –1/3
9. (a)
26. (b) The method of representing oxidation number by a
Zn(s) + Cu2+(aq) Zn2+ (aq) + Cu(s) Roman numeral within the paranthesis represents Stock
notation.
Reduction gain of 2e– 27. (c) Carbon has the maximum oxidation state of + 4, therefore
carbon dioxide (CO2) cannot act as a reducing agent.
10. (d) Reduction potential of Cu(II) is greater than that of
Zn(II) and Al(III) thus can be easily replaced by these 28. (b) Let the oxidation no. of Fe in Fe3O 4 = x
ions. Moreover solution of copper is blue in color. \ 3x + (– 2 × 4) = 0 or 3x = 8
∗2 ,1 ∗1 ∗6 ,2 ∗2 ∗6 , 2 ∗1 ,1 8
11. (c) Ba O2 ∗ H 2 S O4 ¾¾
↑ Ba S O4 ∗ H 2 O2 \ x=
3
In this reaction, none of the elements undergoes a change 29. (c) Let oxidation state of oxygen in OF2 = x
in oxidation number or valency. \ x + ( – 1 × 2) = 0
12. (c) Oxidation number of oxygen in OF2 = + 2. \ x= +2
-1 30. (d) In H2O2 : Þ 2 × (+1) + 2 × x = 0 Þ x = –1
In KO2 =
2 In CO2 : Þ 4 + 2x = 0 Þ x = –2
13. (d) Oxidation number of hydrogen when it is bonded to
In H2O : Þ 2 × (+1) + x = 0 Þ x = –2
metals in binary compounds is –1
In F2O : Þ 2 × (–1) + x = 0 Þ x = +2
14. (a) Let x = oxidation no. of Cr in K2Cr2O7.
31. (a) Let the oxidation state of S be x.
\ (2 × 1) + (2 × x) + 7 (– 2) = 0
S4O 62– Þ 4x – 12 = – 2 Þ 4x = 10 Þ x = 10/4 = 2.5
or 2 + 2x – 14 = 0 or x = + 6.
15. (a) (i) Oxidation state of element in its free state is zero. 32. (c) Species O.N.
(ii) Sum of oxidation states of all atoms in compound is Cl – –1
zero. ClO4– +7
ClO– +1
O.N. of S in S8 = 0; O.N. of S in S2F2 = + 1;
MnO4– +7
O.N. of S in H2S = –2;
In ClO– chlorine is in +1 oxidation state which can be
REDOX REACTIONS 501

increased or decreased thus it acts as an oxidising or 44. (c)

reducing agent. 45. (b) Phosphorus, sulphur and chlorine disproportionate in
In other given species the underlined elements are either the alkaline medium.
in their minimum or maximum oxidation state. Χ
46. (b) 2H 2 O ¾¾↑ 2H 2 ∗ O 2
33. (b) In KMnO4 : Let O.N. of Mn be x
Þ +1 + x + 4(–2) = 0 Þ x = +7 There is decomposition of H2O molecule into H2 and O2.
47. (a) H+ ions are added to the expression on the appropriate
In K2Cr2O7 : Let O.N. of Cr be x
side so that the total ionic charges of reactants and
Þ 2(1) + 2x + 7(–2) = 0 Þ x = +6
products become equal.
34. (d) The element is Ti (At. no. 22). Electronic configuration 48. (d) Since reaction is occuring in basic medium therefore
is 1s2, 2s2p6, 3s2p6d2, 4s2. the energy level of 3d and 4s 2OH– are added on right side.
is very close. It can have Ti4+ O.S.
35. (a) CuO Þ +2 2MnO -4 (aq) + Br– (aq) ¾¾ ®
MnO2 Þ +4 2MnO2(s) + Br O3– (aq) + 2OH–(aq)
HAuCl4 Þ +3 Now, hydrogen atoms balanced by adding one H2O
Tl2O Þ +1 molecule to the left side
36. (b) 2MnO -4 (aq) + Br - (aq) + H 2 O(l) ¾¾
®
37. (c) Calculating the oxidation state of nitrogen in given
molecules; 2MnO2(s) + BrO 3- (aq) + 2 OH - (aq)
Oxidation state of N in NH3 is 49. (c) The balanced equation :
x + 3 × (+ 1) = 0 or x = – 3 2 NH 3 + OCl - ¾
¾® N 2 H 4 + Cl - + H 2 O
Oxidation state on N in NaNO3 is 50. (b) The balanced equation is
1 + x + 3 × (– 2) = 0 or x = + 5 2C2 H6 + 7O2 ® 4CO 2 + 6H 2O.
Oxidation state of N in NaN3 is Ratio of the coefficients of CO2 and H2O is 4 : 6 or 2 : 3.
1 51. (a) 2MnO 4– + 5H 2 O 2 + 6H + ® 2Mn 2 + + 5O 2 + 8H 2 O.
+ 1 + 3x = 0 or x = –
3 52. (d) 8KMnO 4 + 3NH 3 ¾¾ ® 8MnO 2 + 3KNO 3 + 5KOH
Oxidation state of N in Mg3N2 is
3 × 2 + 2x = 0 or x = –3 +2H 2O
Thus 3 molecules (i.e. NH3, NaN3 and Mg3N2 have Reduction
53. (b)
nitrogen in negative oxidation state.
38. (b) Oxidation no. of O are + 2, 0, – 1/2 and – 1 respectively 2Fe 3+ + Sn 2 + ® 2Fe 2 + + Sn 4 +
39. (d) PO3–
4 = x + 4 (– 2) = – 3; x – 8 = – 3; x = + 5 Oxidation
54. (c) On balancing the given reaction, we find
SO 2–
4 = x + 4 (– 2) = – 2; x – 8 = – 2; x = + 6 3Na2HAsO3 + NaBrO3 + 6HCl
¾¾® 6NaCl + 3H3AsO4 + NaBr
Cr2 O72– = 2x + 7 (– 2) = – 2; 2x – 14 = – 2; 55. (c)
2x =12; x = + 6 o +5 –1
40. (c) F2 being most electronegative element cannot exhibit ¾® ClO 3 + yCl- + 3H 2 O
x Cl 2 + 6 H –¾
–1
any positive oxidation state.
In ClO –4 chlorine is present in its highest oxidation on balancing the eq we get
state i.e +7. Therefore it does not show 3Cl2 + 6OH - ¾¾ ¾® ClO 3- + 5Cl- + 3H 2 O
disproportionation reaction. 56. (b) H2O2 is strong oxidizing than I2, reduction potential of
41. (c) A reaction, in which a substance undergoes H2O2 is greater than that of I2.
simultaneous oxidation and reduction, is called 57. (b)
disproportionation reaction. In these reactions, the 58. (b) Decomposition of calcium carbonate is not a redox
same substance simultaneously acts as an oxidising reaction.
agent and as a reducing agent. Here Cl undergoes 59. (b) On reaction with hot and concentrated alkali a mixture
simultaneous oxidation and reduction. of chloride and chlorate is formed
2KOH + Cl 2 ® KCl + KOCl + H 2O. Hot
0 -1 +1 3Cl2 + 3 NaOH(excess) ¾¾¾ ® -1 +5
42. (d) In disproportionation reaction, one element of a 5NaCl + NaClO3 + 3H 2O
compound will simultaneously get reduced and 60. (d) In (i) and (ii) both P and S are in highest oxidation
oxidised. In ClO-4 , oxidation number of Cl is + 7 and it state. In (iii) and (iv) ; P has oxidation state of +4 which
- can be oxidized to +5 state, while in case of NH3 nitrogen
can not increase it further. So, ClO 4 will not get oxidised
and so will not undergo disporportionation reaction. has oxidation state of –3 which can be oxidised.
61. (c) The redox reaction involve loss or gain of electron(s)
43. (d) 3Br2 + 6CO32 – + 3H 2 O ® 5Br – + BrO3– + 6HCO 3– i.e. change in oxidation state. Given reaction is not a
O.N. of Br2 changes from 0 to –1 and +5 redox reaction as this reaction involves no change in
hence it is reduced as well as oxidised. oxidation state of reactant or product.
 EBD_7374
502 CHEMISTRY

62. (b) During disproportionation same compound undergo 70. (a) Higher the value of reduction potential higher will be
simultaneous oxidation reduction. the oxidising power whereas the lower the value of
Oxidation reduction potential higher will be the reducing power.
71. (c) The redox couple with maximum reduction potential
- + -1 +5
will be best oxidising agent and with minimum reduction
3HO Cl ¾
¾® 2HCl+ HClO 3
potential will be best reducing agent.
Reduction 72. (a) Since oxidation potential of Zn is highest hence
63. (a) ClO3- ¾¾
® Cl02 strongest reducing agent.
x - 6 = -1 x =0 73. (a) Fe Al Br
0.77 –1.66 1.08 E°Red
x = +5 x = 0 ( x = oxidation number ) –0.77 1.66 –1.08 E°Oxi
Molecular mass Hence, reducing power Al > Fe2+ > Br–
Equivalent mass =
Oxidation number 74. (d) More the negative reduction potential, more is the
84.45 tendency to lose electron. The reducing power
= = 16.89
5 increases as the standard reduction potential becomes
64. (c) On balancing the given equations, we get more and more negative.
2MnO 4– + 5C 2 O 42– + 16H + ¾¾ ® 2Mn 2+ Thus, Li is the strongest reducing agent as the standard
reduction potential of Li+/ Li is most negative, –3.05 V.
+10CO 2 + 8H 2O
75. (a) Lower the value of reduction potential higher will be
So, x = 2, y = 5 & z = 16
65. (a) Given reaction is reducing power hence the correct order will be
Mn2+ < Cl– < Cr3+ < Cr
IO3- + aI - + bH + ¾¾ ® cH 2 O + dI 2
76. (d) 77. (d)
Ist half reaction 78. (a) Standard electrode potential i.e. reduction potential of
I - ¾¾ ® I2 ...(i) A is minimum (–3.05V) i.e. its oxidation potential is
–1 0 (oxidation) maximum which implies ‘A’ is most reactive chemically.
IInd half reaction 79. (a) 80. (a)
IO 3- ¾¾ ® I2 ...(ii)
+5 0 (reduction) Exercise - 2
On balancing equation (ii) we have 1. (d) Following are the examples of redox reaction
Red
10e - + 2IO3- + 12H + ¾¾ ® I 2 + 6H 2O ...(iii)
Now, balance equation (i) CuO + H 2 ¾¾
® Cu + H 2 O
(a)
2I - ¾¾ ® I 2 + 2e - ....(iv)
Oxi Oxi
Multiply eqn (iv) by 5 and add it to eqn (iii), we get
2IO 3- + 10I - + 12H + ¾¾ ® 6I 2 + 6H 2 O Fe2 O3 + 3CO ¾¾
® 2Fe + 3CO2
(b)
or, IO3- + 5I - + 6H + ¾¾ ® 3I 2 + 3H 2 O
Red
Hence a = 5, b = 6, c = 3, d = 3 Red
66. (a) Both Fe(ii) and S(iv) in SO32 - can be oxidised to Fe(iii) and
(c) 2K + F2 ¾¾
® 2KF
(SO4)2– respectively hence (3/5)×0.5 =0.3 moles /litre. Oxi
é MnO-4 + 5e - + 8H + ® Mn 2 + + 4H 2O ù ´ 3 Option (d) is not an example of redox reaction as there
ë û 5 is no change in oxidation number of any of the reactants.
Fe2+ ¾¾ ® Fe3+ + le– 2. (d) Since the redox couple Ag +/Ag has the highest
SO32- ¾¾ ® SO 24 - + 2e- positive value of E o 0.80 V, therefore, Ag+ is the
8 24 + strongest oxidising agent.
MnO -4 + H + Fe2 + + SO32 - 3. (d) Given that E– values of
5 5 Br2/Br– = + 1.09 V
`
® 3Mn 2 + + 4H 2 O + Fe3+ + SO 24-
¾¾ Ag+ / Ag(s) = 0.80 V
Cu2+/Cu(s) = + 0.34V
67. (b) If one uses HCl, HBr or HI, to make acidic medium for I2 (s) / I– = + 0.54 V
KMnO4 than all the halide ion can be oxidized as the Br2 /Br – = 1.09 V
reduction potential of KMnO4 is very high in acidic The E– values show that copper will reduce Br 2, if the
medium, while in case of H2SO4, sulphur is already in E° of the following redox reaction is positive.
its highest oxidation state cannot be further oxidized. The electrode reactions will be
68. (b) Strongest oxidising agent = Ag+/Ag(s)
Cu ® Cu 2 + + 2e - ; E° = -0.34V
Weakest oxidising agent = Mg2+/Mg(s)
69. (a) More is E°RP, more is the tendency to get itself reduced Br2 + 2e - ® 2Br - ; E° = +1.09 V
or more is oxidising power.
Cu + Br2 ® CuBr2 ; E° = + 0.75 V
REDOX REACTIONS 503

–
Since, E of the overall reaction is positive, therefore, 11. (c) Fluorine is the strongest oxidising agent. It does not
Cu can reduce Br2. show positive oxidation state hence it does not
4. (d) disproportionate.
(a) 2Fe3+ + 2e– ® 2Fe2+; E° = + 0.77 V 12. (a) O.N. of Mn in MnO –4 is +7 and in Mn 2+ it is +2. The
2I– ® I2 + 2e–; E° = – 0.54 V difference is of 5 electrons.
2Fe3+ + 2I– ® 2Fe2+ + I2; E°cell = + 0.23 V
(b) Cu ®Cu2+ + 2e–; E° = – 0.34 V 13. (d) PO3–
4 = x + 4 (– 2) = – 3; x – 8 = – 3; x = + 5
2Ag+ + 2e– ® 2Ag; E° = + 0.80 V
Cu + 2Ag+ ® Cu2+ +2Ag; E° = + 0.46 V SO 2–
4 = x + 4 (– 2) = – 2; x – 8 = – 2; x = + 6

(c) 2Fe3+ + 2e - ® 2Fe2 + ; E° = + 0.77V Cr2 O72– = 2x + 7 (– 2) = – 2; 2x – 14 = – 2;

Cu ® Cu 2 + + 2e - ; E° = - 0.34 V 2x =12; x = + 6
14. (c) Species O.N.
2Fe3+ + Cu ® 2Fe 2 + + Cu 2 + ; E° = + 0.43V Cl – –1
(d) Ag ® Ag+ + e–; E° = – 0.80 V ClO4– +7
Fe3+ + e– ® Fe2+; E° = + 0.77 V ClO– +1
Ag + Fe3+ ® Ag+ + Fe2+; E° = – 0.03 V MnO4 – +7
This reaction is not feasible since E°cell is negative. NO3– +5
+2 0 2.5 In ClO– chlorine is in +1 oxidation state which can be
5. (a) 2 S 2 O32- ( aq ) + I 2 (s ) ® S4 O62- ( aq ) + 2I - ( aq ) increased or decreased thus it acts as an oxidising or
+2 0 reducing agent.
S2 O32- ( aq ) + 2 Br2 ( l ) + 5H 2 O ( l ) ¾¾
® In other given species the underlined elements are either
+6
2 S O 24- ( aq ) + 4Br - ( aq ) + 10H + ( aq ) in their minimum or maximum oxidation state.
15. (d) Since reaction is occuring in basic medium therefore
Hence, bromine is a stronger oxidising agent than I2,
2OH– are added on right side.
as it oxidises S of S2 O32 - to SO 24 - whereas I2 oxidises
2MnO -4 (aq) + Br– (aq) ¾¾ ®
it only into S4 O62 - ion.
6. (a) Oxidation number of hydrogen is not always +1. It is +1 in 2MnO2(s) + BrO–3 (aq) + 2OH–(aq)
hydrogen halides, –1 in hydrides and zero in H2 molecule. Now, hydrogen atoms can be balanced by adding
7. (b) Split NH4NO3 into two ions NH +4 and NO3- . Now one H2O molecule to the left side
calculate the oxidation number of nitrogen in the two 2MnO 4- (aq) + Br - (aq) + H 2 O(l) ¾¾
®
species. + 2MnO2(s) + BrO 3- (aq) + 2 OH - (aq)
Let, oxidation number of N in N H 4 is x.
Þ x + (4 × 1) = +1 16. (a) In the reaction
or x + 4 = + 1 or x = – 3 Oxidation
+4 +1 +6 0
Let, oxidation number of N in NO3-
is y XeF4 + O2F2 ® XeF6 + O2
Þ y + (3 × – 2) = – 1 or y – 6 = – 1 or y = + 5 Reduction
8. (a) Calculating the oxidation number of central atom in
+7 +2
the given species. 17. (b) ® Mn2+; 5e – gain
Mn O 4– ¾¾ ...(i)
+3 +5 +6 +7
Cr O -2 , Cl O 3- , Cr O 24 - , MnO 4- +3 +4
9. (d) Highest oxidation number of any transition element is C2O 42– ¾¾ ® CO2 ; 2e - loss ...(ii)
the sum of (n – 1) d-electrons and ns electrons. Hence, Multiplying (i) by 2 and (ii) by 5 to balance e–
2+
large the number of electrons in the 3d-orbitals, higher 2 MnO 4– + 5 C 2 O 2– ® 2 Mn + 10 CO2
4 ¾¾
is the maximum oxidation number.
10. (d) Reactions in which the same substance undergo On balancing charge;
oxidation as well as reduction are called 2 MnO 4– + 5 C2 O 42– + 16 H + ¾¾
®
disproportionation reactions. Writing the O.N. of each
element above its symbol in the given reactions. 2 Mn 2 + + 10 CO 2 + 8 H 2 O
In reaction (d), N is both oxidised as well as reduced
18. (c) (i) [Cr(H 2 O)6 ]Cl3 :
since the O. N. of N increases from +4 in NO2 to +5 in
x + 6 × 0 + (–1) × 3 =0
NO3- and decreases from +4 in NO2 to +3 in NO2- .
oxidation x =+3
(ii) [Cr(C6H6)2]:
+4 +3 +5
NO2 + 2OH - ¾¾
® NO-2 + NO-3 + H2O y+ 2× 0 = 0
y=0
reduction
 EBD_7374
504 CHEMISTRY

(iii) K2[Cr(CN)2(O)2 (O2)(NH3)] : HNO 3 + 8H ¾

¾® NH 3 + 3H 2 O
2 × 1 + z + 2 × (–1) + 2 × (–2) + (–2) + 0 = 0
z = +6 NH 3 + HNO 3 ¾
¾® NH 4 NO 3
The oxidation states of Cr is given compounds are 4Zn+10HNO 3 ¾¾
® 4Zn(NO 3 ) 2 +NH 4 NO 3 +3H 2 O
+3, 0 and + 6 respectively.
Zn is on the top position of hydrogen in electrochemical
Exercise - 3 series. So Zn displaces H2 from dilute H2SO4 and HCl
with liberation of H2.
1. (d)
Zn + H2SO4 ¾® ZnSO4 + H2
I. Cs ¾¾ ® Cs+ + e - (Oxidation) ù 8. (d)
ú
( )
+2
- – 1
( ) ú é +3 0
1- ù
H 2 O + e ¾¾ ® OH + H 2 Reduction ú (a) -1 ´ 2
2 û ëê Co N H3 5 Cl úû Cl 2
Hence, redox reaction. NH3 : x + 3 = 0 Þ x = –3; Oxidation State of N = –3
(b) NH2OH : x + 3 – 2 = 0 Þ x = –1
II. e - + Cu 2+ ¾¾ ® Cu+ ( Reduction )ù Oxidation state of N = –1
ú
ú (c) (N2H5)2+1 × 2SO42– :
2I ¾¾ ® I 2 + 2e - (Oxidation) û N2H5+ : 2x + 5 = + 1 Þ x = – 2
Hence, redox reaction. Oxidation number of N = –2
III. NH +4 ¾¾
® NH3 (No change in oxidation number) (d)
+2×3 –3´2
x = -3 Mg 3 N 2 : Oxidation state of N = –3
x =-3
Hence, reaction is not a redox reaction. 9. (c)
IV. No change in the oxidation number of either Fe2+ or
CN– in both reactant and product; hence, reaction is (a) ( NH ) S O
+1
4 2 2 8
2-
not a redox reaction. \ Oxidation state of S = + 6
2. (d) II, III and IV are redox reactions.
3. (d) Intermolecular redox reaction involves oxidation of one (Since S2 O82 - has one peroxide bond)
molecule and reduction of the other molecule like in (b) Oxidation state of Os = +8
redox reactions.
(c) Oxidation state of S in H 2SO5 = +6
+3 -5 +5 +2
As 2 S3 + H NO3 ¾¾
® H3 As O4 + H 2SO4 + NO (Since it has one peroxide bond)
(d) K1+ O21–, oxidation state of O = –1/2
+6 +6 10. (a) S2O62– : 2x – 12 = –2 Þ x = 5
4. (c) CrO 24- ¾¾
® Cr2O72- SO32– : x – 6 = –2 Þ x = 4
Since oxidation state of Cr in both reactant and product S2O42– : 2x – 8 = –2 Þ x = 3
is same. 11. (c) SO42– cannot be oxidised since the oxidation state (+6)
5. (a) Oxidation state of C in CO32– is +4, which is maximum. of S is highest.
So, it will not be oxidised. 12. (c) SO2 is an oxidising agent.
4e– + SO2 ¾¾ ® S
-1´2
6. (c) Ba 2+ ( H 2 PO2 )2 : H 2 PO 2- : 2 + x - 4 = -1 64
Equivalent of SO2 = = 16.
Þ x = +1 4
\ Oxidation state of P = + 1 13. (b) Reaction II is disproportionation, while I, III and IV
7. (d) Zinc gives H2 gas with dil H2SO4/HCl but not with are not.
HNO3 because in HNO3, NO3– ion is reduced and give 14. (c) (a) and (b) are disproportionation reactions.
NH4 NO 3 , N 2O, NO and NO 2 (based upon the (c) is an oxidation reaction.
concentration of HNO3) 2H - ¾¾ ® H 2 + 2e -
[ Zn + 2HNO 3 ¾
¾® Zn ( NO 3 ) 2 + 2H] ´ 4 15. (a) Since oxidation potential of Zn is highest hence
(nearly 6%) strongest reducing agent.
 9. HYDROGEN

Exercise - 1 17. cobalt

(b) CO(g) + 2H2(g) ¾¾¾¾ ® CH3OH(l)
catalyst
1. (c) Hydrogen behaves as a metal at very high pressure.
18. (c) Hydrogen is not used in the synthesis of hydroquinone
2. (d) Hydrogen is a non-metal while all other members of
and tartaric acid.
group 1 (alkali metals) are metals.
19. (c) Hydrogenation occurs in presence of nickel as a
3. (c) In metal hydrides the O.S. of hydrogen –1 otherwise it
catalyst.
is +1.
20. (d) H2 will not reduce heated Al2O3. As Al is more electro-
4. (a) Number of neutrons in protium, deuterium and tritium
positive than hydrogen. therefore, its oxide will not be
respectively is = 0, 1 and 2
reduced by hydrogen.
5. (b) The only pollutant in combustion of dihydrogen is
21. (c) Mixture of CO and H2 is used in synthesis of
oxides of dinitrogen (due to the presence of dinitrogen
methanol and a number of hydrocarbons due to this
as impurity with dihydrogen).
reason it is also called syn gas.
6. (d) It is for the first time in the history of India that a pilot
22. (d) Almost all elements except noble gases, forms
project using dihydrogen as fuel was launched in
hydrides.
October 2005 for running automobiles. Initially 5% H2
23. (c) Melts of ionic hydrides conduct electricity and
has been mixed in CNG for use in four wheeler vehicles.
liberate dihydrogen gas at anode.
7. (a) Due to extremely small size of H+ as compared to
24. (c) Fire due to action of water on saline hydrides cannot
normal atomic and ionic size H+ does not exist freely.
be extinguished with water or CO2. These hydrides
8. (c) Except method given in statement (iii) all other are
can reduce CO2 at high temperature to produce O2.
commercial methods for production of dihydrogen.
25. (b) Electron deficient hydride = B2H6
9. (d) Zn+ 2NaOH ¾¾ ® Na2ZnO2 + H2
Electron precise = CH4
(Sodium zincate)
Electron rich = NH3 and HF
10. (d) Carbon dioxide formed in water gas shift reaction is
26. (d)
removed by scrubbing with sodium arsenite solution.
27. (d) Metal hydride + H2O ® Metal hydroxide + H2
11. (c) Fe + dil. H 2SO 4 ® FeSO 4 + H 2 ­ 28. (d) Due to its covalent nature MgH2 is Polymeric in nature.
29. (c) Ionic hydrides give the basic solution when it reacts
3Fe + 4H 2 O ® Fe 3O 4 + 4H 2 ­
with water, e.g.,
Steam
LiH + H2O ¾® LiOH + H2
Cu + dil. HCl ® No reaction
30. (d) d- and f-block elements form metallic hydride.
Copper does not evolve H2 from acid as it is below
While p-block elements form covalent hydrides, s-block
hydrogen in electrochemical series.
elements except Be and Mg form ionic hydrides.
2Na ∗ 2C 2 H 5OH ↑ 2C 2H 5ONa ∗ H 2 ← Hydrides of Be, Mg, Cu, Zn, Ca and Hg are intermediate
12. (a) Mg + dil. HNO 3 ® Mg( NO 3 ) 2 + H 2 (Mg and Mn hydride.
give H2 with dil. HNO3) excess
31. (b) LiH + AlCl3 ¾¾ ® (AlH3)n ¾¾¾¾ ® Li[AlH 4 ]
LiH
catalyst Lithuim aluminium hydride is a most useful organic
13. (b) CO + H 2 + H 2O ¾¾¾® CO 2 + 2H2
reducing agent. It reduces functional groups but does
water gas
not attack double bonds.
14. (a) Zinc has no action on cold water. 32. (a) Polarity of bond depends on difference in electronegativity
15. (a) Cu + 4HNO3(conc.) ¾® Cu(NO3)2 + 2NO2 + 2H2O of the two concerned atoms. H2O is more polar than
H2S because oxygen (in O–H) is more electronegative
® C2 H 5 O - Na + + 1 / 2H 2 ­
C 2 H 5 OH + Na ¾¾ than sulphur (in S–H).
Mg + 2H 2 O(steam) ¾¾
® Mg(OH) 2 + H 2 ­ 33. (c) Tanks of metal alloy like NaNi5, Ti – TiH2, Mg – MgH2
etc., are used for storage of dihydrogen in small
® C6 H 5 O - Na + + 1 / 2H 2 ­
C6 H 5 OH + Na ¾¾ quantities.

NaH + H 2 O ¾¾ ® NaOH + H 2 ­ 34. (b) H - (aq) + H 2 O(l) ¾¾

® OH - (aq) + H 2 (g)
base 1 acid 1 base 2 acid2
16. (d) Very pure hydrogen can be prepared by the action of
water on sodium hydride. In this reaction H–
acts as bronsted base as it accepts
NaH + H2O ¾¾ ® NaOH + H2 one proton (H+) from H2O and for H2.
(very pure Hydrogen)
 EBD_7374
506 CHEMISTRY

35. (c) The unusual properties of water in the condensed phase 51. (a) H2SO4 + BaO2 ® BaSO4 + H2O2
(liquid an solid states) are due to the presence of extensive 52. (d) MnO2 , PbO2 and BaO will not give H2O2 with HCl.
hydrogen bonding between the water molecules. MnO2 and PbO2 will give Cl2 and BaO will react with
36. (c) The high boiling point of water is due to H-bonding. HCl to give BaCl2 and water.
37. (b) Due to high dielectric constant, water acts as a good 53. (c) 30 vol of H2O 2 means one volume of H2O 2 on
solvent therefore it is also called a universal solvent. decomposition will give 30 volume of oxygen.
38. (b) In the structure of ice each molecule of H2O is
vol. strength
surrounded by three H2O molecules in hexagonal honey 54. (a) Normality of H2O2 =
comb manner which results an open cage like structure. 5.6
As a result there are a number of 'hole' or open spaces. Volume of normal (1N) H2O2 solution = 5.6 volumes.
In such a structure lesser number of molecules are \ Volume of strength of 1.5 N H2O2
packed per ml. When ice melts a large no. of hydrogen = 1.5 × 5.6 = 8.4 volumes.
bonds are broken. The molecules therefore move into 68 ´ 10
55. (b) Strength of 10V H2O2 = ´ 100 = 3.035%
the holes or open spaces and come closer to each other 22400
than they were in solid state. This result sharp increase H
in the density. Therefore ice has lower density than 56. (b) O–O is the true structure of H2O2.
water. H
39. (a) We know that due to polar nature, water molecules are 57. (b)
held together by intermolecular hydrogen bonds. The
58. (a) H 2O 2 ® H 2 O + [O]
structure of ice is open with large number of vacant
weak acid
spaces, therfore the density of ice is less than water.
40. (b) Two ice cubes stick to each other due to H-bonding. 59. (b) H 2 O2 + [O] ¾Oxidation
¾¾¾ ¾® H 2 O + O 2 ­
41. (d) Sodium is most electropositive element among those 60. (b) The value of dipole moment of H2O2 is 2.1 D, which
given. suggest the structure of H2O2 cannot be planar.
2Na + 2H 2O ¾¾¾¾¾¾ ® 2NaOH + H 2 An open-book structure is suggested for H2O2 in which
Room temp. O – H bonds lie in different plane.
42. (b) Temporary hardness is due to presence of bicarbonates 61. (a) In the following reaction H2O2 acts as a reducing agent.
of calcium and magnesium and permanent hardness is PbO2(s) + H2O2 (aq) ® PbO(s) + H2O(l) + O2 (g)
due to the sulphates and chlorides of both of calcium 62. (a) As H2O2 is loosing electrons so it is acting as reducing
and magnesium. agent.
43. (a) The complex salt of metaphosphoric acid sodium
63. (c) H2S is oxidised to S by H2O2.
hexametaphosphate (NaPO3)6, is known as calgon. It
is represented as Na2[Na4(PO3)6] 64. (d) H2O2 does not have basic properties.
44. (c) Polyphosphates (sodium hexametaphosphates, sodium 65. (b, d) HOCl(aq) + H 2 O 2 (aq) ¾¾®
tripolyphosphate or STPP) form soluble complexes with H 3O + (aq) + Cl- (aq) + O 2 (g)
Ca2+, Mg2+ present in hard water.
I 2 (s) + H 2 O 2 (aq) + 2OH - (aq) ¾¾
®
45. (b)
46. (a) This method is known as Clark's process. In this method 2I - (aq) + 2H 2 O(l ) + O 2 (g)
temporary hardness is removed by adding lime water 66. (a) Option (a) represents oxidising action of H2O2 in
acidic medium.
or milk of lime. 67. (d) H2O2 is not used as a moderator in nuclear reactors.
Ca(OH) 2 + Ca(HCO3 )2 ¾¾
® 2CaCO3 ¯ +2H 2 O 68. (d) Decomposition of H2O2 can be accelerated by finely
ppt. divided metals such as Ag, Au, Pt, Co, Fe etc.
47. (a) 2C17H35COONa(aq) + M2+ (aq) ¾¾® 69. (d) Although H2O2 is a better polar solvent than H2O.
(C17H35COO)2M¯ (M = Ca or Mg) + 2Na+(aq) However it cannot be used as such because of the
48. (d) Many salts can be crystallised as hydrated salts from strong auto-oxidation ability.
an aqueous solutions such an association of water is 70. (d) H2O2 show all these properties.
of different types viz., 71. (d) Dihedral angle of H2O2 in gas phase is 111.5° and in
(i) Coordinated water e.g., [Cr(H2O)6]3+ 3Cl– solid phase it is 90.2°
(ii) Interstitial water e.g., BaCl2 . 2H2O 72. (a)
(iii) Hydrogen-bonded water electrolysis
73. (b) 2HSO4– (aq) ¾¾¾¾¾ ® HO3SOOSO3H(aq)
e.g., [Cu(H2O)4]4+ SO2–4. H2O in CuSO4.5H2O
49. (b) Hydrolysis
¾¾¾¾¾ ® 2HSO -4 (aq) + 2H+(aq) + H2O2(aq)
50. (c) Assertion is correct reason is incorrect.
Correct reason : Calgon forms soluble complexes with 74. (a) CaC2 + 2D 2 O ® C 2 D 2 + Ca(OD) 2
Ca2+ and Mg2+ in which properties of these ions are 75. (b) D2O is used in nuclear reactors as moderator.
marked. 76. (b) Al4C3 + D2O ® 3CD4 + 4Al(OD)3
HYDROGEN 507

77. (c) Heavy water is formed by the combination of heavier

Reduction
isotope (1H2 or D) with oxygen.
- + -1 0 -2
2D 2 + O 2 ® 2D 2 O 8. (c) 2I + 2H + H 2O 2 ¾¾
® I2 + 2H 2 O
Heavy water Oxidation
78. (d) H2O absorbs neutrons more than D 2O and this
decreases the number of neutrons for the fission Here H2O2 oxidises I– to I2, hence behaves as oxidising
process. agent.
79. (a) D2O actually has higher freezing point (3.8°C) than 9. (b) The given below reaction show the reducing action in
water H2O (0°C) basic medium.
80. (d) Reduction

Exercise - 2 –1
I20 + H 2 O2 + 2OH - ¾¾
® 2I- + 2H 2 O + O20
1. (b) Hydrogen like halogens accept an electron readily to
achieve nearest inert gas configuration. Oxidation
2. (d) H+ ion always get associated with other atoms or 10. (c) Hydrogen peroxide acts as an oxidising as well as
molecules because loss of an electron from hydrogen reducing agent in both acidic and alkaline media.
atom results in a nucleus of very small size as compared 11. (c) The production of syn gas or synthesis gas from coal
to other atoms or ion. Due to small size it cannot exist is called coal gasification.
free.
C ( s ) + H 2 O ( g ) ¾¾¾¾ ® CO ( g ) + H 2 ( g )
1270 K
3. (b) The stability of hydrides decreases from Li to Cs. It is
Coal Steam Ni 1442443
because of the fact that M-H bond becomes weaker Syn gas
due to increase in size of alkali metals down the group.
Hence, ionic character increases as the size of the atom In order to increase the production of hydrogen steam
increases i.e., the correct order of increasing ionic is added to carbon monoxide of the syn gas in the
character is presence of iron chromate as a catalyst at 673 K.
CO ( g ) + H 2 O ( g ) ¾¾¾¾¾¾® CO 2 ( g ) + H 2 (g )
LiH < NaH < KH < RbH < CsH 4 FaCrO . 673 K
4. (d) Electron-precise hydrides are the type of hydrides in
which the number of electrons present is equal to the CO2 is removed by scrubbing with a solution of sodium
number of electrons required. arsenite.
5. (c) The radioactive isotope of hydrogen is tritium. Its half 12. (d) Na 2 O 2 + dil. H 2SO 4 ¾¾
® Na 2SO 4 + H 2 O 2
life is about 12.32 years.
13. (b) Hydrogen peroxide is manufactured by electrolysis of
Reduction 50% sulphuric acid followed by distillation. The
-1 -1 0 -2 distillate is 30% hydrogen peroxide. The first product
6. (b) (i) H 2 O2 + 2HI ¾¾
® I2 + 2H 2 O of electrolysis is peroxy disulphuric acid.
Oxidation 2H2SO4 ----® 2H+ + HSO4–
Here H2O2 oxidises HI into I2 hence, behaves as an 2HSO 4- ( aq ) ¾¾¾¾¾® H 2 S2 O8 + 2e -
Electrolysis
oxidising agent.
® 2H 2 SO 4 + H 2 O 2 ( aq )
H2S2O8 + 2H2O ¾¾
Reduction
+1 -1 0 14. (d) The water gas is a combination of carbon and
+ -
(ii) HOCl + H 2 O 2 ¾¾
® H 3O + Cl + O 2 hydrogen. It is used in manufacturing of methanol.
Oxidation
CO ( g ) + 2H 2 ( g ) ¾¾¾¾
Cobalt
® CH3OH ( l)
Here, H2O2 reduces HOCl to Cl, thus, behaves as Catalyst
reducing agent. 15. (a) Bicarbonates, chlorides and sulphates of Ca and Mg
7. (b) Oxides such as BaO2, Na2O2 etc; which contain are responsible for the hardness of water.
peroxide linkage on treatment with dilute H2SO4 give 16. (c) Sodium hexametaphosphate also known as Calgon is
H2O2 but dioxides such as PbO2, MnO2, TiO2 do not used.
give H2O2 on treatment with dilute H2SO4.
BaO2 .8H 2 O (s ) + H 2SO 4 ( aq ) ¾¾
® 2CaCl 2 + Na 6 P6O18 or Na 2 éë Na 4 ( PO3 ) 6 ùû ®
Hydrated barium
peroxide
( From hard
water ) Sodium
hexametaphosphate

BaSO 4 (s) + H 2 O 2 (aq ) + 8H 2O (l )

Na 2 éë Ca 2 ( PO3 )6 ùû + 4NaCl
Hydrogen
peroxide Complex Salt
 EBD_7374
508 CHEMISTRY

17. (a) Elements of group 7, 8 and 9 of d-block do not form CuO + 2H ® Cu + H2O
hydrides at all. The inability of metals of group 7, 8 and 27. (c) Melts of ionic hydrides conduct electricity and liberate
9 of periodic table to form hydrides is referred to as dihydrogen gas at anode.
hydrides gap of d-block. In these compounds H atoms 28. (a) There is extensive intermolecular hydrogen bonding
are supposed to occupy interstitial position in the metal in the condensed phase instead of intramolecular
lattices. They are also called non-stoichiometric H-bonding.
hydrides. 29. (b) Na zeolite + CaCl 2 ® Ca zeolite + 2NaCl
18. (a) Only one element of group 6, i.e., Cr forms hydride. 30. (c)
Oxidation 31. (b) 2H 2 O 2 ¾
¾® 2H 2 O + O 2
+1 –1 0, –2 0 From equation, it is clear that 22400 ml O2 is formed
19. (a) (i) H2O2 + O3 H2O + 2O2 by 68 gm of H2O2
10 ml O2 is formed by
Reduction 68
´ 10 = 0.0303gm H 2 O2
22400
Oxidation

+1 –1 +1, –2 0 +1 –2 0
(ii) H2O2 + Ag2O 2Ag + H2O + O2 100 ml = 3.03 gm

Reduction +2
32. (c) (i) [Fe (CN)6 ]4 - + H 2 O 2
Hence in both the reactions H2O2 is acting as an
reducing agent. H+
20. (d) Both assertion and reason are false. +3
HOF bond angle in HFOis lesser than that of HOCl [Fe (CN)6 ]3- + H 2 O
bond angle in HClO. Oxygen is more electronegative +3
than all halogens except fluorine. (ii) [Fe (CN)6 ]3- + H 2O 2
21. (d) The reducing agent loses electron during redox reaction
i.e. oxidises itself. OH–

–1 –2 +2
(a) H 2O 2 + 2H + + 2e - ¾¾
® 2H 2O (Re d.) [Fe(CN)6 ]4 - + O2 + H 2O
–1 0 33. (b)
(b) ® O 2 + 2H + + 2e- (Ox.)
H 2O 2 ¾¾
–1 –2 Exercise - 3
(c) H 2O 2 + 2e - ¾¾
® 2OH - (Re d.)
–1 0
H 2O 2 + 2OH - ¾¾
® O2 + H 2O + 2e - (Ox.)
1. (b) 2H 2SO 4 ® 2H + + 2HSO -4
(d)
22. (d) The stability of alkali metal hydrides decreases from Li At Cathode : 2H + + 2e - ® H 2­
to Cs. It is due to the fact that M–H bonds become
At Anode : 2HSO -4 ¾¾
® H 2S2 O 8 + 2e -
weaker with increase in size of alkali metals as we move
down the group from Li to Cs. Thus the order of stability peroxy
disulphuric
of hydrides is
acid
LiH > NaH > KH > RbH > CsH
2. (a) A fusion reaction between hydrogen nuclei is difficult
i.e. option (d) is correct answer.
because positively charged nuclei repel each other.
23. (a) However, at very high temperatures of the order of 10 6
24. (c) H2O2 has oxidizing and reducing properties both. to 107 K, the nuclei may have sufficient energy to
25. (a) This method is known as Clark's process. In this method overcome the repulsive forces and thus fuse. This is
temporary hardness is removed by adding lime water why, fusion reactions are also called thermonuclear
or milk of lime. reactions.
® 2CaCO3 ¯ +2H 2 O
Ca(OH) 2 + Ca(HCO 3 ) 2 ¾¾ 3. (a) 2 Na + 2H 2 O ® 2 NaOH + H 2 ­
ppt. 'A ' 'C' ' B'
26. (a, d) Among the three isotopes of hydrogen, Protium (1H1) Zn + 2 NaOH ® Na 2 ZnO 2 + H 2 ­
is most common. It is an energetic reducing agent. It 'D ' 'C' 'B'
reduces oxides, chlorides and sulphides of certain
metals and produce free metals at ordinary temperature. Zn + dil. H 2SO 4 ® ZnSO 4 + H 2 ­
'D ' 'B'
HYDROGEN 509

Na produces golden yellow colour with smokeless flame 11. (a) Volume of O2 at STP
of Bunsen burner. = 100 mL × 11.2 mL volume strength
4. (a) Zn + H2SO4 ® ZnSO4 + H2 = 1120 mL of O2 at STP
Zn + 2NaOH ® Na2ZnO2 + H2 Since 1 N = 5.6 volume strength of H2O2
\ Ratio of volumes of H2 evolved is 1 : 1 2 N = 11.2 volume strength of H2O2
5. (a) Pure para form can be obtained at low temperature (20K) Volume of O2 produced by H2O2 = 1120 mL
but pure ortho form is very difficult to obtain.
Same volume of O2 will be produced by KMnO4 i.e.
6. (a) As Na+ ions in sodium zeolite are replaced by Ca2+
1120 mL.
and Mg2+ ions present in hard water, these two ions
will not be present. Total volume of O2 produced = 2240 mL = 2.24 L
7. (a) 12. (b) MnO4– + 5e– ® Mn2+ (acidic)
8. (b) H - (aq)+ H 2 O(l) ¾¾ ® OH - (aq)+ H 2 (g) MnO4– + 3e– ® MnO2 (basic)
base 1 acid 1 base 2 acid2 100 mL H2O2 º 100 × 5N MnO4– º V × 3N MnO2
In this reaction H–
acts as Bronsted base as it accepts
one proton (H+) from H2O and forms H2. 500
N= mL
3
W2 ´ 1000
9. (a) N= 13. (d) N of H2O2 = Volume strength/5.6 = x /5.6
E.w 2 ´ VmL
mEq. of H2O2 = mEq. of MnO4–
34 ´1000 200 \ N1V1 º N2V2
= =
17 ´ 1120 12
x 1
1 N of H2O2 = 5.6 vol strength ´ 10 mL = ´10 mL
5.6 0.56
200 200 \ x = '10' volume strength
N of H 2 O2 = 5.6 ´ = 10 vol strength
12 12 14. (c) 1 N = 5.6 vol
10. (d) H2O2 º KI º I2 Þ Normalities of two solutions are 1 N and 2 N
mEq of H2O2 = 5 × N
1´ 1 + 1´ 2 3
Normality of mixture = = = 1.5 N
Weight 1 +1 2
mEq of I2 = ´ 1000
E.w
3 16.8
Volume strength = ´ 5.6 = = 8.4 vol
1.27 2 2
´ 1000 = 10 mEq
127 15. (b) mEq of MnO4– º mEq of H2O2
I2 = M.w = 254 M
10 ´ ´ 5 º mEq of H2O2
M.w 254 5
E.w = = = 127
2 2 Þ 10 mEq º mEq of H2O2
\ mEq of H2O2 = mEq of I2
34
5 × N = 10 \ N = 2 Weight of H2O2 = 10 × 10–3 × × 0.17 = 0.2 g
2
1 N of H2O2 = 1.7% of H2O2
2 N of H2O2 = 3.4% H2O2 100
Weight of impure H2O2 = ´ 0.17 = 0.2 g
85
 EBD_7374
510 CHEMISTRY

10. THE s-BLOCK ELEMENTS

16. (d) Amongst alkali metal Li ions are highly hydrated.

Excercise - 1
17. (a) All the given elements react with oxygen to form oxides
1. (c) Francium is highly radioactive. but only Li also react with nitrogen to form Li3N.
2. (b) Alkali metals readily lose electron to give monovalent 18. (c) Because KO2 not only provides O2 but also removes
M+ ion. Hence they are never found in free state in nature. 1CO2 as follows
3. (a) Na ® Na+ + e– ; IE of Na = + ve 4KO2 + 2CO2 ® 2K 2 CO3 + 3O 2
Na+ + e– ® Na ; E.A. of Na+ = – ve
4KO 2 + 4CO 2 + 2H 2 O ® KHCO3 + 3O 2
Both are equal but opposite in nature
4. (a) Within a group, ionic radius increases with increase in 19. (a)
atomic number. The melting points decrease down the 20. (a) Since the ionization energies of alkali metals decrease
group due to weakening of metallic bond. The down the group, the ionic character and consequently
electronegativity and the 1st ionization energy also basic property of their hydroxides increases in the same
decreases down the group. order, i.e. from LiOH to CsOH.
5. (d) Li, Na, K are lighter than water but Rb is heavier than 21. (c) With the same anion, smaller the size of the cation,
water. higher is the lattice energy. The correct order of size of
6. (a) cations is –
7. (b) Sodium metal on burning in air gives sodium peroxide. Na+ < K+ < Rb+ < Cs+
8. (c) All the alkali metals when heated with oxygen form Hence, the lattice energy of NaF will be maximum.
different types of oxides for example lithium forms i.e., NaF.
lithium oxide (Li2O), sodium forms sodium peroxide 22. (c) As Cs+ ion has larger size than Li+ and I– has larger
(Na2O2), while K, Rb and Cs form their respective size than F–, therefore maximum distance between
superoxides. centres of cations and anions is in CsI.
1 23. (a) Larger cation (K+) develops less polarisation in anion
2Li + O2 ® Li 2O and thus KI has more ionic nature and more soluble in water.
2
9. (d) Smaller the size of cation higher is its hydration energy 24. (c)
and lesser is its ionic mobility hence the correct order 25. (b) During the dissolution of alkali metal hydrides energy
is Li+ < Na+ < K+ < Rb+ is released in large amount, i.e., it is exothermic in nature.
10. (b) Both Ca and CaH2 produce H2 gas with water. 26. (d) (a) and (b) forms corresponding hydroxides (NaOH
and LiOH) in aqueous solution
Ca + 2H 2 O ¾¾ ® Ca(OH) 2 + H 2 ­
M 2 O + H 2O ¾¾ ® 2M + + 2OH - (M = Na or Li)
CaH 2 + 2H 2 O ¾¾
® Ca(OH) 2 + 2H 2 ­ Therefore reaction of HI with (a), (b) and (c) is simply
11. (d) The basic character and stability of hydrides decrease a neutralization reaction, while aqueous solution of
down the group. (d) form H2O2 which act as oxidizing agent, hence
12. (a) For a given metal, order of stability of halides is convert Iodide to Iodine( I2).
MF > MCl > MBr > MI Na 2O 2 + 2H 2 O ¾¾ ® 2Na + + 2OH - + H 2 O 2
13. (a) A reducing agent is a substance which can loose
electron and hence a reducing agent should have low 27. (d) LiI is more soluble as the degree of covalent character
ionisation energy. Now since ionisation energy is high due to larger size of anion i.e., iodide ion by
decreases from Li to Cs, the reducing property should greater polarization of lithium cation.
increase from Li to Cs. The only exception to this is 28. (a) 4LiNO3 ® 2Li 2 O + 4NO 2 + O 2
lithium. This is because the net process of converting 29. (c) 4LiNO3 ® 2H2O + 4NO2 + O2
an atom to an ion takes place in 3 steps. 2 NaNO3 ® 2NaNO2 + O2
(i) M(s) ® M(g) DH = Sublimation energy 30. (b) Li is much softer than the other group I metals. Actually
(ii) M(g) ® M+(g) + e– DH = Ionisation energy Li is harder then other alkali metals.
(iii) M+(g)+H2O ® M+ (aq) DH = Hydration energy 31. (b) Lithium although has most negative E d- value reacts
The large amount of energy liberated in hydration of Li less vigorously with water than other alkali metals
(because of its small size) makes the overall DH negative. due to its small size and very high hydration energy.
This accounts for the higher oxidation potential of 32. (c) Li due to highest hydration energy among the alkali
lithium i.e., its high reducing power. metals is the strongest reducing agent.
14. (d) Lithium with lead is used to make white metal. 33. (a) Lithium carbonate is unstable to heat; lithium being
15. (b) Liquid sodium is used as a coolant in fast breeder very small in size polarises a large CO32 - ion leading
nuclear reactors. to the formation of more stable Li2O and CO2.
THE s-BLOCK ELEMENTS 511

34. (c) The atom becomes larger on descending the group, so All alkali metals decompose water with the evolution
the bonds becomes weaker (metallic bond), the of hydrogen.
cohesive force/energy decreases and accordingly Ca + 2H 2 O ¾¾® C a(OH) 2 + H 2 ­
melting point also decreases.
Sr + 2H 2O ¾¾® Sr(OH) 2 + H 2 ­
35. (a) The ionisation potential value of lithium is maximum
among alkali metals i.e., its tendency to ionise to give Be + 2H2O ¾¾® No reaction
Li+ ions should be the minimum i.e. Li should be the Ca, Sr, Ba and Ra decompose cold water readily with
evolution of hydrogen. Mg decomposes boiling water
poorest reducing agent. But, lithium is the strongest
but Be is not attacked by water even at high
reducing agent in aq. solution. This is due to the largest
temperatures as its oxidation potential is lower than
value of hydration energy of Li+ ions.
36. (a) Li+ has maximum degree of hydration among other the other members.
56. (b) Electrons in Mg due to its small size are tightly bound
alkali metals.
so they cannot be excited by the flame.
37. (c) NH 4 HCO 3 + NaCl ¾
¾® NaHCO 3 ¯ + NH 4 Cl 57. (d) All the given statements are correct.
Brine Sod. bicarbonate ppt. 58. (d) Both assertion and reason are false.
38. (a) CO2 and NH3 formed are reused (See Solvay process) Radium is the rarest of all s-block elements comprising
39. (a) NH3 is recovered when the solution containing only 10–10 percent of igneous rocks. Francium (s-block
NH4Cl is treated with Ca(OH)2 member) is radioactive; its long lived isotope 223Fr
2NH4Cl + Ca(OH)2 ® 2NH3 + CaCl2 + H2O ahs a half life of only 21 minutes.
40. (b) 59. (d) Because of larger size and smaller nuclear charge, alkali
41. (d) Sodium sulphate, calcium chloride and magnesium metals have low ionization potential relative to alkaline
chloride are present as impurities in crude sodium earth metals.
chloride. 60. (d) The IInd ionisation potential of Na is higher than Mg
42. (b) Na metal is manufactured by electrolysis of fused NaCl because it requires more energy to remove an electron
by two methods. from a saturated shell or stable (fully filled) orbital.
I
(i) Castner's process 11 Na ¾ ¾® 1s 2 , 2s 2 2p 6 , 3s1 ¾ ¾®
(ii) Down's process II
In both the above processes electrolysis of fused 1s 2 , 2s 2 2 p 6 , 3s 0 ¾¾®
sodium chloride produces Na at cathode. 1s 2 , 2s 2 2p5 , 3s 0
2NaOH ‡ˆˆˆˆ† 2Na + + OH - I
12 Mg ¾ ¾® 1s 2 , 2s 2 2p 6 , 3s 2 ¾
¾®
at cathode 2Na + 2e - ¾¾
+
® 2Na
II
at anode 4OH - ¾¾ ® 2H 2 O + O 2 + 4e 1s , 2s 2p , 3s ¾¾® 1s 2 , 2s 2 2p 6 , 3s 0
2 2 6 1

43. (a) Baking powder has starch, NaHCO3 and Ca(H2PO2)2. Here Na-I < Mg-I and Na-II > Mg-II.
44. (a) 61. (c) As we go from group I element to group II element in a
45. (c) NaCl (brine), NH 3 and CO 2 are raw materials. CaCO3 period, an extra electron is added in same shell which
results in increase in nuclear charge due to which force
is source of CO 2 .
of attraction by the nucleus increases and hence ionic
46. (c) Alkali metals have large size. When they are heated in radii decreases and consequently I.E. increases.
the flame of Bunsen burner, the electrons present in 62. (b) BaF2 > MgF2 > CaF2
the valence shell move from lower energy level to higher 63. (d) For a compoud to be soluble, the hydration energy
energy level by absorption of heat from the flame. must exceed lattice energy. For Gp.II hydroxides
When they come back to the ground state, they emit (Mg(OH)2, Sr(OH)2, Ca(OH)2, Ba(OH)2, lattice energy
the extra energy in the form of visible light to provide decrease more rapidly than the hydration energy & so
colour to the flame. their solubility increases down the group. Ba(OH)2>
47. (c) Within a period, the size decreases from left to right, Sr(OH)2 > Ca(OH)2 > Mg(OH)2
i.e., Na > Mg > Li > Be. Atomic size increases down the 64. (a) Be(OH)2 is amphoteric while Ca(OH)2, Sr(OH)2 and
group. Ba(OH)2 are all basic.
48. (d) 49. (d) 50. (d) 51. (c) 65. (a) Because of small atomic size and high I.E. Be forms
52. (d) Barium is most electropostive element among those covalent chloride.
given. Hence it is most reactive. 66. (a) As we move down the group, the lattice energies of
53. (d) K and Mg, both form oxides carbonates remain approximately the same. However
K + O 2 ® KO 2 ;2 Mg + O 2 ® 2 MgO the hydration energies of the metal cation decreases
Mg form nitride also 3Mg + N 2 ® Mg 3 N 2 from Be2+ to Ba2+, hence the solubilities of carbonates
K does not form nitride. of the alkaline earth metal decrease down the group
54. (a) mainly due to decreasing hydration energies of the
55. (b) 2Na + 2H 2 O ¾¾® 2NaOH + H 2 ­ cations from Be2+ to Ba2+.
67. (a) As the basicity of metal hydroxides increases down
2K + 2H 2O ¾¾® 2KOH + H 2 ­ the group from Be to Ba, the thermal stability of their
 EBD_7374
512 CHEMISTRY

carbonates also increases in the same order. Further the ratio of lime (CaO) to the total of the oxides of
group 1 compounds are more thermally stable than silicon (SiO2), aluminium (Al2O3) and iron (Fe2O3)
group 2 because their hydroxide are much basic than should be as close as possible to 2.
group 2 hydroxides therefore, the order of thermal 89. (c) Radium is used in treatment of cancer.
stability is 90. (c)
BeCO3 < MgCO3< CaCO3< K2CO3. 91. (b) Quick lime is used for the manufacture of dyestuffs.
68. (a) In alkaline earth metals ionic size increases down the Plaster of Paris is used for setting of fractured bones.
group. The lattice energy remains constant because Slaked lime is used for the manufacture of bleaching
sulphate ion is so large, so that small change in cationic powder.
sizes do not make any difference. On moving down the Limestone is a constituent of chewing gum.
group the degree of hydration of metal ions decreases 92. (d) When cold calcium hydroxide reacts with chlorine, then
very much leading to decrease in solubility bleaching powder is obtained.
\ BeSO 4 > MgSO 4 > CaSO 4 > SrSO 4 > BaSO 4 3Ca(OH) 2 + 2Cl 2
slaked lim e
69. (d) All alkaline earth metal oxides except BeO are basic ¾¾
® Ca(OCl)2 .Ca(OH) 2 .CaCl 2 .2H 2 O
in nature. BeO is amphoteric in nature. Bleaching powder
Hydrated halides of Ca, Sr and Ba on heating 93. (c) Monovalent sodium and potassium ions and divalent
undergo dehydration while corresponding hydrated magnesium and calcium ions are found in large
proportions in biological fluids.
halides of Be and Mg on heating suffer hydrolysis.
94. (a) The calcium concentration in plasma is regulated at
70. (c) Calcium carbonate on thermal decomposition gives CaO about 100 mgL–1. It is maintained by two hormones :
(Basic oxide) and CO2 (Acidic oxide) calcitonin and parathyroid hormone.
D
CaCO 3 CaO + CO 2­ 95. (b)
Basic oxide Acidic oxide
96. (b) Potassium ions are the most abundant cations within
cell fluids.
71. (c) 2NaO2 + 2H2O ® 2NaOH + H2O2 + O 97. (a)
72. (b) O 24 - ion is not possible and K 2O4 is unknown .
Exercise - 2
73. (a) Lattice energy decreases more rapidly than hydration
energy for alkaline earth metal hydroxides. On moving 1. (d) Alkali metals have low melting and boiling points. The
down a group\ solubility of their hydroxides increases. melting point of alkali metals decreases from Li to Cs
74. (a) Mg burns in CO2 to give MgO and C. as cohesive force decreases with increase in atomic size.
75. (d) Down the group solubility of sulphate decreases. Thus 2. (a) The reactivity of alkali metals with water increases on
Ba2+ ions will precipitate out most easily. moving down the group from Li to Cs due to increase
76. (a) BeF2 is highly soluble in water due to the high in electropositive character.
hydration enthalpy of the small Be2+ ion. 3. (c) Reducing character is measured by tendency of an
77. (d) Be(OH)2 is amphoteric, but the hydroxides of other element to lose electron in aqueous solution. Higher
alkaline earth metals are basic. The basic strength the negative E°RP value, greater is the ability to lose
increases gradually. electrons.
78. (b) The Be(OH)2 and Al(OH)3 are amphoteric in nature. E°RP depends on:
79. (a) (i) enthalpy of sublimation
80. (a) Because of high value of ionisation enthalpy and small (ii) ionisation of enthalpy
size it forms compound which are highly covalent in (iii) enthalpy of hydration
nature, hence, it get hydrolysed easily. Thus, in aqueous medium, order of reactivity of alkali
81. (a) Gypsum is CaSO4.2H2O metals is Na < K < Rb < Cs < Li. E°RP value of Li is least
1 (–3.04 V) among all alkali metals.
82. (d) Plaster of Paris (CaSO4 . H2O) on making paste with The formation of Li+ (aq) from Li involves following
2
little water sets to a hard mass due to formation of steps:
gypsum (CaSO4.2H2O). Sublimation
(i) Li(s) ¾¾¾¾¾® Li(g);
1 3 DHs = Enthalpy of sublimation
CaSO4 . H O + H2O ® CaSO4.2H2O + Heat -e -
2 2 2 Gypsum
(ii) Li(g) ¾¾¾ ® Li+ (g); IE1 = Ionisation enthalpy
+
® Li + (aq); DHn = Enthalpy of hydration
Plaster of Paris
(iii) Li (g) ¾¾
83. (d) 84. (c) 85. (c)
For alkali metals, enthalpies of sublimation are almost
86. (b) CaCO 3 + 2HCl ¾¾ ® 2CaCl2 + H 2O + CO 2 same. IE 1 value of Li is positive & highest and
hydration enthalpy is negative and maximum for
87. (a) During setting of cement, silicates and aluminates of
smallest Li+ which makes it strongest reducing agent.
calcium are hydrated. Hydration is an exothermic process. 4. (d) BaCO3 is thermally most stable due to the small size of
Therefore setting of cement is exothermic process. resulting oxide ion. As the atomic number increases
88. (d) For a good quality cement, the ratio of silica (SiO2) the stability of the metal ion decreases hence, stability
to alumina (Al2O3) should be between 2.5 and 4 and of carbonates increases.
THE s-BLOCK ELEMENTS 513

5. (a) BeCO3 is unstable due to high polarising power of hydration of calcium aluminates and silicates.
smallest Be2+ ion. Also, it shows reversible reaction, 14. (a) On heating plaster of Paris at certain temperature, it
because of more stability of oxide formed. Hence, BeCO3 forms anhydrous calcium sulphate which is known to
has least stability and it is stable only in CO2 atmosphere. be dead burnt plaster and has no setting property as it
6. (a) The basic character of the given hydroxides increases absorbs water very slowly.
down the group due to decrease in ionization 1 200°C 1100° C
enthalpies. On moving down the group, the ionic size CaSO 4 . H 2O ¾¾¾¾ ® CaSO4 ¾¾¾¾ ® CaO + SO3
2 ( Anhydrous)
increases, so M–O bond in metal hydroxides gets
weaker and easily gives OH– in the solution and I.E. 15. (c) Slaked lime [Ca(OH)2] is sparingly soluble in water and
further decreases. Hence, Mg(OH)2 will be least basic. it forms a suspension of slaked lime in water which is
The order of basicity will be: called milk of lime and a clear solution obtained after
Mg(OH)2 < Ca(OH)2 < Sr(OH)2 < Ba(OH)2 the suspension settles is known as lime water.
7. (a) Ethanol is a covalent compound and only a compound 16. (a) Except Be, all alkaline earth metals form hydrides (MH2)
which has more covalent character can be dissolved in on directly heating with H2. BeH2 can't be prepared by
it. Also the group ionic character increases and direct heating but it can be prepared by the action of
beryllium halide have covalent character due to its small LiAlH4 on BeCl2.
size and high effective nuclear charge. Hence, among 2BeCl2 + LiAlH 4 ® 2BeH 2 + LiCl + AlCl3
the given halides, BeCl2 can be soluble in ethanol.
8. (c) On moving down the group from Li to Rb increased 17. (d) On heating washing soda, it loses its water of
screening effect makes the removal of electron easier. crystallisation. Above 373 K, it becomes completely
Thus, the order of decreasing ionization enthalpy will anhydrous white powder called soda ash.
be: Li > Na > K > Rb Above 373K
Na 2CO3.10H 2O ¾¾¾¾¾¾
® Na 2CO3
9. (b) Among fluorides, the order of solubility is LiF < NaF Washing soda Soda ash
< KF < RbF < CsF. On moving down the group solubility ( Anhydrous form)
increases because lattice energy decreases.
18. (b) Calcium gives brick red coloured flame. Also, calcium
Also, LiF exhibit very high lattice energy.
nitrate on heating decomposes into calcium oxide and
10. (a) Be(OH)2 is an amphoteric hydroxide thus gets dissolve
evolution of a mixture of NO2 and O2 takes place.
both in acids and alkalies.
2Ca(NO3)2 ® 2CaO + 4NO2 + O2
Basic nature : brown coloured gas
Be ( OH )2 + 2HCl ¾¾ ® BeCl 2 + 2H 2 O 19. (a) Ca(OH)2 is used in the manufacture of bleaching
Acidic nature: powder.
Be ( OH ) 2 + 2NaOH ¾¾ ® Na 2 BeO 2 + 2H 2 O Cold
2Ca ( OH )2 + 2Cl2 ¾¾¾ ® CaCl2 + Ca(OCl) 2 + 2H 2 O
Sodium beryllate Slaked Bleaching
11. (a) Sodium carbonate can be synthesised by Solvay lime powder
ammonia soda process. 20. (c) To recover NH3 in Solvay process Ca(OH)2 is used.
The reactions involved in the process are : On passing CO2 through Ca(OH)2, it turns milky due
NH3 + H 2O + CO2 ¾¾
® NH 4 HCO3 to the formation of CaCO3. Also, Ca(OH)2 is used for
Ammonium bicarbonate white washing due to its disinfectant nature.
NaCl + NH 4 HCO3 ¾¾
® NaHCO3 ¯ + NH 4Cl Ca(OH)2 + CO2 ® CaCO3¯+ H2O
Sodium bicarbonate 21. (d) Chlorides of alkaline earth metals are hydrated salts.
D Due to their hygroscopic nature, they can be used as a
2NaHCO3 ¾¾
® Na 2 CO3 + H 2O + CO 2
Sodium carbonate
dehydrating agent and can absorb moisture from air.
NH3 is recovered from NH4 HCO3 and NH4Cl Extent of hydration decreases from Ca to Ba.
D 22. (a) (Na2O2 + HCl) is commercially known as oxone and is
NH 4 HCO3 ¾¾® NH 3 + H 2 O + CO 2
used for bleaching of delicate fibres.
2NH 4 Cl + Ca ( OH ) 2 ® 2NH3 + CaCl 2 + 2H 2O 23. (c) Assertion is correct. Reason is incorrect.
Ammonium chloride Ammonia Calcium chloride
12. (a) Alkali metals dissolve in liquid NH3 giving deep blue 24. (d) BeSO 4 > MgSO 4 > CaSO 4 > SrSO 4 > BaSO 4
coloured solution. 25. (d) Amongst alkali metals, Cs is most reactive because of
+
® éë Na ( NH3 ) x ùû + e- ( NH3 ) y
Na + ( x + y) NH3 ¾¾ its lowest IE.
Ammoniated cation Ammoniated electron 26. (b) K+ ion is a constituent of sodium pump.
When light fall on the solution, the ammoniated 27. (d) Solubility of alkaline earth metal sulphates decreases
electrons get excite to higher energy level by absorbing down the group due decrease in hydration energy.
certain wavelength and transmit blue colour. MgSO 4 > CaSO4 > SrSO 4 > BaSO 4
13. (b) Gypsum (CaSO4.2H2O) is added to cement to increase
its setting time so that it gets sufficiently hardened. Hydration Solubility
energy
Setting of cement is an exothermic process and involves
 EBD_7374
514 CHEMISTRY

28. (c) Carbonates becomes more thermally stable down the 5. (b) Na 2CO3 + 2SO2 + H 2O ® 2NaHSO3 + CO 2
group, therefore MgCO3 will leave CO2 easily. (A)
29. (b) Lithophone is BaSO4 + ZnS, which is a white paint. 2NaHSO3 + Na 2 CO3 ® 2Na 2SO3 + H 2O + CO 2
30. (c) ( A) ( B)
31. (a) Lithium does not form peroxide. Heat
2Na 2SO3 + S ¾¾¾® 2Na 2S2 O3
32. (b) On heating with excess of air Li, Na and K forms (B) (C)
following oxides Na 2S2O3 + AgNO3 ® Ag 2S+ H 2SO4
4 Li + O2 ¾® 2Li2O (D )
Lithium monoxide
D
575 K 6. (d) ZnCl2 + 2NaHCO3 ¾¾® Zn ( HCO3 )2 + 2NaCl
2Na + O2 ¾¾¾® Na2O2 ( A)
Sodium peroxide
D
K + O2 ¾® KO2 Zn ( HCO3 )2 ¾¾
® ZnCO3 + H 2 O + CO 2 ­
Potassium superoxide (A ) ( B) ( C)
33. (a) Lithium carbonate is unstable to heat; lithium being
ZnCO3 + 2NaOH ® Na 2 ZnO2 + 2H 2 O
very small in size polarises a large CO32 - ion leading (B) ( D)
to the formation of more stable Li2O and CO2. 7. (d)
34. (c) There are four chief minerals present in a Portland 8. (b) Basic character increases down the group due to
cement tricalcium silicate (Ca3SiO5), dicalcium silicate increase in polarity of M–OH bond.
(Ca2SiO4), tricalcium aluminate (Ca3Al2O6) and calcium 9. (a)
alumino-ferrite (Ca4AlnFe2-nO7). 10. (c) MgSO4 is the only alkaline earth metal sulphate which
35. (d) CaSO4 is soluble in water and for solubility hydration energy
36. (b) In metals moving down the group metallic character should be greater than lattice energy.
increases, so basic nature increases hence most acidic 11. (b) Permanent hardness of water is due to chlorides and
will be BeO. sulphates of calcium and magnesium i.e CaCl2, CaSO4,
BeO < MgO < CaO < BaO
¾¾¾¾¾¾¾¾¾¾ ® MgCl2 and MgSO4.
increasingbasic character
37. (c) Element (X) electronic configuration
12. (b) X heat CO2 + Residue
Solid
1s2 2s2 2p3 H 2O
So, valency of X will be 3. boil
¬¾¾¾¾2¾ Y
Valency of Mg is 2. excess CO
Z
Formula of compound formed by Mg and X will be Clear solution
Mg3X2. The given properties coincide with CaCO3
38. (a) BeH2 < CaH2 < BaH2 heat
Smaller the size of cation, more will be its polarising CaCO3 ¾¾¾¾¾¾¾® CO2 + CaO
power. Hence BeH2 will be least ionic. Residue
boil 'X '
39. (a) Calcium gives brick red colour and barium gives
apple green colour in flame test. H 2O
40. (b) The Be(OH)2 and Al(OH)3 are amphoteric in nature.
excess
Ca(HCO3 ) ¬¾¾¾¾¾¾¾ Ca(OH)2
2 CO2
Exercise - 3 'Z' 'Y'
1. (b) As the size of alkali metal ion increases, lattice enthalpy 13. (c) Ca and CaH2 both react with H2O to form H2 gas,
decreases and hence the stability of the corresponding Ca + 2 H 2 O ¾
¾® Ca ( OH ) 2 + H 2
metal hydride decreases.
CaH 2 + 2H 2 O ¾¾® Ca (OH ) 2 + 2 H 2
2. (a) The crystal structures of NaHCO3 and KHCO3 both
show hydrogen bonding but are different. In NaHCO3, whereas
the HCO3– ions are linked into an infinite chain, while K gives H2 while KO2 gives O2 and H2O2
in KHCO3, a dimeric anion is formed. 2K + 2 H2O ¾ ¾® 2KOH + H2
3. (b) Due to strong packing of Li+ and F– ion, lattice energy 2KO2 + 2H 2O ¾¾
® 2KOH + O2 + H 2O2
of LiF is higher than its hydration energy. Similarly, Na gives H2 while Na2 O2 gives H2O2
4. (a) Basic strength of the oxides increases in the order 2 Na + 2 H 2 O ¾
¾® 2 NaOH + H 2
Li2O < Na2O < K2O < Rb2O < Cs2O. The increase in
basic strength is due to the decrease in I.E. and increase Na 2 O 2 + 2H 2 O ¾
¾® 2 NaOH + H 2 O 2
in electropositive character. Likewise Ba gives H2 while BaO2 gives H2O2
The melting points of the halides decrease in the order Ba + 2 H2O ¾ ¾® Ba (OH)2 + H2
NaF > NaCl > NaBr > NaI, as the size of the halide ion BaO2 + 2H2O ¾ ¾® Ba (OH)2 + H2 O2
increases. The decrease in melting point is due to 14. (a) Setting of cement is exothermic process which develops
increase in the covalent character with increase in the interlocking crystals of hydrated silicates
size of anion according to Fajan's rule. 15. (b)
 11. THE p-BLOCK ELEMENTS (GROUP 13 AND 14)
27. (d) 28. (b) 29. (b) 30. (c) 31. (b) 32. (b)
Exercise - 1
33. (c) The correct formula of inorganic benzene is B3N3H6 so
1. (b) Aluminium does not occur in the free state in nature (d) is incorrect statement
but is most abundant metal in the earth’s crust. OH
|
2. (b) The order of ionisation enthalpies, as expected, is Boric acid (H3BO3 or B - OH ) is a lewis acid so (a) is
DiH1 < DiH2 < DiH3. |
3. (c) 4. (b) OH
incorrect statement.
5. (a) Due to its small size and high ionization energy boron
The coordination number exhibited by beryllium is 4
does not form B3+ ion.
and not 6 so statement (b) is incorrect.
6. (b) Thallium shows different (+1 and +3) oxidation states
Both BeCl2 and AlCl3 exhibit bridged structures in solid
because of inert pair effect.
state so (c) is correct statement.
7. (c) Because Tl5+ does not exist
8. (c) Cl m Cl Cl Cl Cl
2p
9. (b) Down the group basic character of oxides increases. 20
Be 98° Be 263 pm Be Be
B2O3 - Acidc 82°
Al2O3 - Amphoteric Cl Cl Cl Cl Cl
Ga2O3 - Amphoteric
In2O3 - Basic Cl Cl Cl
Tl2O3 - Basic
Al Al
10. (c) Aluminium chloride in acidified aqueous solution
forms octahedral [Al(H2O)6]3+ ion. Cl Cl Cl
11. (b) 12. (a) 13. (a) 34. (a) H3BO3 is a weak monobasic acid.
14. (d) B(OH)3 is acid because it can take OH– ions. 35. (d)
H3BO3 or B(OH)3 + OH– ® B(OH) -4 36. (d) Boron nitride (BN) is known as inorganic graphite. The
most stable form is hexagonal one. It has layered
15. (a) B2O3 is acidic and Al2O3 is amphoteric.
structure similar to graphite.
16. (b) 2Al(s) + 2NaOH(aq) + 6H2O(l) ®
2Na+[Al(OH)4]–(aq) + 3H2 (g) N N+
–
17. (c) Atomic radius of gallium is less than that of aluminium. + B
B– –B
18. (d) The order of strength of Lewis acid character for boron
halides is, BF3 < BCl3 < BBr3 < BI3 (due to back bonding)
N+ +N N
19. (a) – +
20. (d) It is pp – pp back bonding involving B and F. The –B B B– –B
smaller atoms show more back bonding.
21. (b) BCl3 forms [B(OH)4]– in which B is sp3 hybridized and +N N N+ +N
+ –
have +3 oxidation state. B– –B B
22. (a) Higher boranes are also spontaneously flammable in
air. N+ +N N
– +
D
23. (b) Na2B4O7. 10 H2O ¾¾¾¾ ® Na2B4O7 B B–
-10H 2O
D
Na 2 B4O7 ¾¾
® 2 NaBO2 + B2 O3 Boron nitride – Inorganic graphite
anhydrous sod.metaborate Boric anhydride 37. (b) 100°C 160°C
H 3 BO 3 ¾¾ ¾® HBO 2 ¾¾ ¾®
CuO + B2 O3 ¾¾
® Cu(BO 2 )2
cupric meta borate(Blue beed) H 2 B4 O 7 + H 2O ¾
¾® 2 B 2 O 3 + H 2 O
24. (d) H3BO3 acts as a Lewis acid and accepts OH– ions to 38. (c) H
form [B(OH)4]–
B
25. (c) H3BO3 on heating at 373 K yields metaboric acid (HBO2) H–N N–H
373K
H3BO3 ¾¾¾® HBO2 + H 2O H–B B–H
D
metaboricacid N
(orthorombic form)
26. (b) In Boric acid each B atom is sp2 hybridized and contains H
BO 33- units which are held together by hydrogen bonds. Inorganic benzene, B 3N 3H 6
It is isoelectronic and isostructural with benzene.
 EBD_7374
516 CHEMISTRY

39. (d) In diborane (B2H6) structure there are four 2c-2e– bonds 56. (a) The stability of dihalides (MX2) increases down the
and two 3c–2e– bonds (see structure of diborane). group. Except C and Si, the other members form dihalides.
Structure of B 2H6 : 57. (b) SiO2 is acidic oxide.
Hb 58. (d) Reluctance of valence shell electrons to participate in
Ht •• Ht bonding is called inert pair effect. The stability of lower
oxidation state (+2 for group 14 element) increases on
B B going down the group. So the correct order is
SiX2 < GeX2 < SnX2 < PbX2
Ht •• Ht 59. (a) The stability of +2 O.S. follows the order
Hb Pb2+ > Sn2+ > Ge2+
excess NH
(d) B2H6 + NH3 ¾¾¾¾¾¾¾
3 ® Hence reducing power Ge > Sn > Pb
40. low temperature B2H6.2NH3
60. (d) Si and Ge are semiconductors and are used in making
Diborane with ammonia gives B2H6.2NH3 that is transistors.
formulated as [BH2(NH3)]+[BH4]– which when heated 61. (b) Both Ge and Si are extensively used as semiconductors.
to 473K decomposes to give borazole. Semiconductors are solids where there is only a small
H H H difference in energy, called band gap, between the filled
41. (d) B 97°83° B valency band of electrons and a conduction band since
H H H the band gap of Ge is less than Si, it is a better element
B is sp3 hybridized to be used as semiconductor.
Only 12 bonding electrons available 62. (b) Ge4+ is more stable than Ge2+. Hence GeCl4 is more
BHB angle is 83° not 180°. stable than GeCl2
D D 63. (d) Carbon halides are not hydrolysed due to absence of
42. (c) Na2B4O7.10H2O ¾¾ ® Na2B4O7 ¾¾ ® d-orbitals. On the other hand SiCl4 is easily hydrolysed
(i) 2NaBO2 + B2O3 (ii) (iii) due to the availability of d-orbitals in Si.
Na2B4O7 + 7H2O ¾¾ ® 4H3BO3 + 2NaOH SiX4 + 2H2O ® SiO2 + 4HX
(iv) (v)
64. (d) In nature Pb4+ is strong oxidant and I– is strong
43. (a) When borax is heated in a Bunsen burner flame with reductant. Hence PbI4 cannot exist.
CoO on a loop of platinum wire a blue coloured
65. (b) F and Cl are more oxidising in nature and can achieve
Co(BO2)2 bead is formed.
Pb in (IV) O.S. but Br 2 and I2 can not achieve Pb in
44. (b) The hybridizations of B in H3BO3 is sp2.
(IV) O.S. secondly Pb4+ is strong in oxidising nature
45. (c) Diborane is produced on industrial scale by the
and in its presence, Br– and I– can not exist.
reaction of BF3 with sodium hydride.
66. (c) Lead pipes are readily corroded by water containing
46. (c) When diborane is hydrolysed one can get both
organic acids.
orthoboric acid and H2.
B2H6 + 6H2O ® 2H3BO3 + 6H2 67. (b) 2Pb + 2H 2O + O 2 ® 2Pb(OH) 2
47. (c) Due to the low density of aluminium it is useful for 68. (a) Carbon does not contain d-orbital hence it cannot
food packaging. expand its octet.
48. (d) 69. (d) Ge(II) tends to acquire Ge (IV) state by loss of electrons.
49. (a) The use of aluminium and its compounds for domestic Hence it is reducing in nature. Pb (IV) tends to acquire
purposes is now reduced considerably because of their Pb (II) O.S. by gain of electrons. Hence it is oxidising in
toxic nature. nature. This is due to inert pair effect.
50. (c) CO2, SiO2 are acidic, CaO is basic and SnO2 is 70. (c) CO2 forms carbonic acid H2CO3, when dissolved in water,
amphoteric. CO is neutral, whereas other two GeO2 and SnO2 are solids.
51. (b) The inert pair effect is most prominent in the heavier 71. (a) Lead in +2 oxidation is stable while Sn and C are both
members of the group. Inert pair effect increases as we stable in +4 oxidation.
move the group down the group.
72. (c) Pb with dil HCl forms protective coating of PbCl2
52. (c) Inert pair effect increases down the group. Hence for
Pb2+ , O.S. is most stable. 73. (a) PbI4 does not exist because Pb–I bond initially
53. (d) PbO2 is a strong oxidising agent and is produced in formed during the reaction does not release enough
situ in lead storage batteries. The anode is oxidized to energy to unpair 6s2 electrons and excite one of them
PbO2 and cathode is reduced to spongy Pb. to higher orbital to have four unpaired electrons
54. (d) The thermal stability of tetrahalides decreases in order around lead atom.
CX4 > SiX4 > GeX4 > SnX4 and in terms of same metal 74. (c) Due to non-availability of vacant d-orbitals, it cannot
with different halides is in order of exceed its coordination number more than four. Thus
MF4 > MCl4 > MBr4 > MI4. carbon never forms complexes e.g., [CCl6]2– deos not
55. (a) Since bond energy of C-F >C-Cl > C-Br > C-I exist but [SiCl6]2– exists.
Hence CF4 is most stable. 75. (d) The more the bond energy, the more is the catenation.
THE p-BLOCK ELEMENTS (GROUP 13 AND 14) 517

76. (d) The order of tendency of catenation for elements of C Ga exists as liquid from 30°C upto 2000°C and hence, it
family is is used in high temperature measurement.
C >> Si > Ge » Sn > Pb 2. (a) Alkaline earth metals (Mg, Ca, Ba) form ionic chloride
77. (b) Buckminster fullerene is C60. The molecule has shape whereas aluminium form covalent chloride. Despite of
of soccer ball. sharing electrons with chlorine, the octet of aluminium
78. (b) In fullerene each carbon atom is bonded to three other is incomplete. To complete the octet, it needs electrons
carbon atoms and is sp2 hybridised. and thus, acts as a Lewis acid.
79. (d) In graphite, each carbon is sp2 -hybridized and the 3.
-
(a) Structure of B ( OH )4 is
single occupied unhybridized p-orbitals of C-atoms
overlap side wise to give p -electron cloud which is OH
| s
delocalized and thus the electrons are spread out
HO B OH

|
between the structure. |
80. (a) Graphite sp3, \ % s character = 33% OH
Diamond sp3, \ % s character = 25% 4 bond pair + 0 lone pair
81. (b) 82. (c) 83. (a) Hybridisation — sp3
84. (d) Diamond and crystalline silicon are isomorphous. Geometry —Tetrahedral
85. (a) 4. (a) On moving down the group the acidic nature of oxides
86. (b) Quartz is crystalline form of silica. changes from acidic to basic through amphoteric
87. (b) 6 HF + SiO 2 ® H 2SiF6 + 2 H 2 O
B2 O3 , Al2 O3 and Ga 2O3 , In 2 O3 and Tl 2O 3
88. (a) Producer gas is a fuel gas and is mixture of CO and N2. { 14442444 3 144 42444 3
More acidic Amphoteric Basic
89. (b) In silica (SiO2); each Si atom is surrounded by four less basic
oxygen atom. 5. (a) Among these elements boron has the lowest atomic
— —

— —

— —

— —

number. It has atomic number 5 and do not have vacant

— Si — O —Si — O — Si — O —Si — d-orbital. Boron can show maximum coordination
number of 4. The element M in the complex ion
O O O O
MF63- has a coordination number of six. Hence, B can
—

— Si — O —Si — O — Si — O —Si — not form complex of the type MF63- .

—

6. (c) Boric acid is a monobasic weak acid. It does not liberate

O O O O
H+ ion but accepts electrons from OH– ion.
— —

— —

— —

— —

-
— Si — O —Si — O — Si — O —Si — H3BO3+ H2O ¾® B ( OH )4 + H+
7. (b) The tendency of forming long open or closed chains
Structure of SiO 2 by combination of some atoms in themselves is known
Only Si – O bonds exist and no Si = O. as catenation. The tendency of catenation is maximum
90. (b) R 3SiCl + HOH ® R 3SiOH + HCl in carbon and decreases on moving down the group.
C > > Si > Ge » Sn > Pb
R 3SiOH + HOSiR 3 ® R 3Si - O - SiR 3 + H 2O This is due to high bond energy of C — C bonds. On
91. (a) Water gas is CO + H2. moving down the group, atomic size increases and
92. (c) CO is essential constituent of almost all fuel gases. electronegativity decreases, hence, tendency to show
93. (c) CO2 is incombustible and non supporter of combustion. catenation decreases.
94. (b) CO react with haemoglobin, forms carboxy haemoglobin 8. (c) Silicon has a strong tendency to form polymers like
and stopes the supply of O2 silicones. The chain length of silicon polymer can be
95. (b) Carbon dioxide is not a poisonous gas. controlled by adding (CH3)3SiCl which block the ends
96. (a) Being biocompatible silicones are used in surgical as shown below
and cosmetic plants.
CH3 CH3
97. (b) ZSM – 5 type of zeolite is used to convert alcohols | |
directly into gasoline. n HO — Si — OH + Cl — Si — CH3
98. (d) | |
99. (b) Coal gas is a mixture of H2 + CO + N2 + CH4 CH3 CH3
100. (d) H2CO3/HCO3– buffer system help to maintain pH of –HCl Polymerisation
blood between 7.26 to 7.42.
CH3 CH3
Exercise - 2 | |
— O — Si — O — Si — CH3
1. (c) Among these elements, in gallium, the crystal structure | |
is different which suggests that Ga consists of almost CH3 CH3
discrete Ga2 molecule, so its melting point is lowest. Silicone
 EBD_7374
518 CHEMISTRY

9. (d) On moving down a group the ionization enthalpies character decreases from Ge (I) to Pb (II). i.e., Germanium
generally decreases due to increase in atomic size and salts are strongest reducing agent and Pb(II) salt the
screening effect which is more than to compensate weakest. Ge is much less abundant than tin in nature.
the effect of increase in nuclear charge. Consequently hence Sn (II) salts are widely used as reducing agent.
the electron becomes less and less tightly held by the 14. (c) Carbon dioxide can be obtained as a solid in the form
nucleus as we move down the group. The sharp of dry ice allowing the liquified CO2 to expand rapidly.
decrease in ionization enthalpy from B to Al is due to It is used to maintain the low temperature in laboratory.
increase in size. In case of Ga, there are 10 d-electrons Dry ice is solid CO2
in its inner electronic configuration. Since the 15. (b) Cement is obtained by combining a material rich in
d-electrons shield the nuclear charge less effectively lime (CaO) with other material like silica SiO2 alongwith
than the s & p electrons, the outer electron are held the oxides of aluminium, iron and magnesium. The
strongly by the nucleus. As a result the ionization average composition of cement is
enthalpy increases slightly inspite of the increase in CaO (50 – 60%)
atomic size as we move from Al to Ga. The similar SiO2 (20 – 25%)
increase is also observed from In to Tl, which is due to Al2O3 (5 – 10%)
presence of 14f electrons in inner electronic Fe2O3 (1 – 2%)
configuration of Tl which has poor shielding effect. SO2 (1 – 2%)
10. (b) In diborane, there are 12 valence electrons, three from MgO (2 – 3)%
each boron atoms and six from the six hydrogen atoms.
Thus, it contains elements of group 2(Ca), group
The structure of B2H6 can be represented as
13 (Al) and group 14 (Si).
H H H 16. (a) Silica on heating with carbon at elevated temperature,
gives carborundum (silicon carbide)
D
B B SiO 2 + 3C ¾¾
® SiC + 2CO
carborundum
Carborundum is a very hard substance.
H H H 17. (c) Assertion is true because lower oxidation state
Bonding in diborane becomes more & more stable for heavier elements in
p-block due to inert pair effect. Hence Reason is false.
The four terminal hydrogen atoms and two boron 18. (b) Lower oxidation state become more stable on moving
atoms lie in the same plane. These four terminal B-H down the group
bonds are regular 3C-2e– bonds. Above and below the Al < Ga < ln < Tl
plane, there are two bridging hydrogen atoms. Each
19. (d) The correct sequence of increasing basic strength is
boron atom forms four bonds even though it has only
B2O3 < Al2O3 < Ga2O3 < In2O3 < Tl2O3
three electrons. The terminal B — H bonds are regular
bonds but the bridge B — H bonds are different. 20. (d) Chemically borax is sodium tetraborate decahydrate
Each bridge hydrogen is bonded to the two boron and it has the formula Na2B4O7.10H2O.
atoms only by sharing of two electrons. Such covalent 21. (b) More the oxidation state of the central atom (metal)
bond is called banana bond. more is its acidity. Hence SeO2 (O. S. of Se = +4) is
11. (a) (i) Reaction of ammonia with diborane gives acidic. Further for a given O.S., the basic character of
initially B 2 H6 .2NH 3 which is represented as the oxides increases with the increasing size of the
[BH2(NH3)2]+[BH4]– which on further heating gives central atom. Thus Al2O3 and Sb2O3 are amphoteric
borazine, B3N3H6 also called borazole. and Bi2O3 is basic.
22. (c) Normal glass is calcium alkali silicate glass made by
473 K
3B2 H 6 + 6NH3 ¾¾¾® 2B3 N 3 H 6 + 12H 2 fusing the alkali metal carbonate, CaCO3 and SiO2.
Diborane Barozole 23. (a) Gallium (Ga) is soft , silvery metal. Its melting point is
(X) (Y)
30ºC. This metal expands by 3.1% when it solidifies and
inorganic benzene hence, it should not be stored in glass or metal containers.
(ii) Diborane can be prepared by the reaction of 24. (b) BF3 has planar and symmetrical structure thus as a
BF3 with lithium aluminium hydride in diethyl ether. result the resultant of two bond moments, being equal
4BF3 + 3LiAIH4 ¾® 2B2H6 + 3AIF3 + 3LiF and opposite to the third, cancels out and hence
12. (b) Quartz, is a crystalline forms of silica. Quartz is molecule possess zero dipole moment.
extensively used as a piezoelectric material. F
13. (d) Sn and Pb can show two oxidation states i.e. +2 and
+4. These elements in +4 oxidation state behave as
oxidising agent, where as in +2 oxidation state behave
F B ;m=0
as reducing agent. The stability of +2 oxidation state
increases on moving down in a group i.e., reducing F
THE p-BLOCK ELEMENTS (GROUP 13 AND 14) 519

25. (c) Magnesium hydrosilicate forms base of talcum powder. Al OH 33 + NaOH

Al(OH) aq ¾¾
NaOH (aq) ® é[Al(OH
Al OH4)(H
4 2HO)O
2)
– ù

26. (d) Inertness of ns2 electrons of the valence shell to (aq) + Na+ (aq)
participate in bonding on moving down the group in 5. (c) 6. (c)
heavier p-block elements is called inert pair effect.
As a result, Pb(II) is more stable than Pb(IV) 7. (d)
Sn(IV) is more stable than Sn(II) \ Pb(IV) is easily
reduced to Pb(II) and can acts as an oxidising agent
whereas Sn(II) is easily oxidised to Sn(IV) and can acts
as a reducing agent.
27. (c) Atomic radius of gallium is less than that of
aluminium.
28. (c)
29. (d) MF63-
Boron belongs to 2nd period and it does not have
vacant d-orbital.
30. (a) K2SO4.Cr2(SO4)324H2O (chrome alum)
31. (a) Both assertion and reason are correct and reason is
correct explanation of assertion. Total No. oxygen atoms per silicon atom
32. (d) BCl3 & AlCl3 both have vacant p-orbital and incomplete
1 1 1
octet. So they act as Lewis acid. = + + + 1 = 2.5
2 2 2
NaOH
33. (c) Al + 3H 2 O ¾¾¾® Al(OH)3 ¯+ 3 / 2H 2 (g)
(X) \ Formula Si 2 O52 - .
White gelatinous ppt.
8. (d) 2CaF2 + SiO 2 + H 2 SO 4 ¾¾
®
¯
[Soluble in excess of NaOH hydrolysis
SiF4 + H2 O + CaSO 4 ¾¾¾¾¾ ® CaSiF6
and form Na[Al(OH)4]
D
9. (c) SnCl 2 + 2 NaOH ® Sn (OH) 2 + 2 NaCl
2Al(OH) 3 ¾¾
® Al 2O 3 + 3H 2O
(used as adsorbent in Sn (OH) 2 + 2 NaOH ® Na 2SnO 2 + 2H 2O
chromatography)
10. (a) R3SiCl on hydrolysis forms only a dimer.
Thus, metal is Al. R3SiOH + HOSiR3 ® R3Si – O – SiR3.
34. (c) ns2 np1 is the electronic configuration of III A period.
X2O3(Al2O3) is an amphoteric oxide. 11. (d) Pb3 O 4 + 4HNO3 ® 2Pb(NO 3 ) 2 + PbO2 ¯ + H 2 O
Pb3O4 + H 2O2 + 6HNO3 ® 3Pb(NO3 ) 2 + O2 + 4H2 O
Exercise - 3 12. (a) The water repellency arises because a silicone chain is
surrounded by organic side groups and looks like an alkane
1. (b) Na 2 B4 O7 + H 2 O ® 2Na éë B ( OH )4 ùû + 2H 3BO3 from the outside.
Salt with strong Weak acid 13. (a, b, c, d)
base D
(a) Mg3B2 + H3PO 4 ¾¾® B2 H 6
dissociation +
2. (c) ® éë AlCl 2 ( H 2O )4 ùû
AlCl3 .6H 2 O ¾¾¾¾¾¾ (b) BX 3 + LiAlH 4 ¾¾¾¾¾
ether
X = F, Cl, Br
® B2H 6 + Li(AlX 4 )
-
+ éë AlCl 4 ( H 2 O )2 ùû (c) BF3 (g) + NaH ¾¾¾¾
180 °C
® B2 H 6 (g) + 6NaF
In diglyme
3. (d) Borax ¾¾¾
HCl
® H 3 BO 3 (d) 2NaBH 4 + I2 ¾¾¾¾¾® B 2H 6 + H 2 + 2NaI
solution

Al 14. (c, d)
B2O3 ¾¾® B ( crystalline ) Mg2Si + H2SO4 ® mixture of silanes (SiH4, Si2H6, Si3H8, etc)
D
SiCl4 + Li[AlH4] ® SiH4 + AlCl3 + LiCl
Mg
® B ( Amorphous )
B2O3 ¾¾¾ CH3SiCl3 + CH3MgCl ® (CH3)2 SiCl2 + MgCl2
D
® ( CH 3 ) SiCl 2
Cu catalyst
- Si + 2CH3Cl ¾¾¾¾¾¾
4. (c) Al(OH)3 dissolves in NaOH solution to give Al ( OH )4 280 - 300°C 2

ion which is supposed to have the octahedral complex 15. (d) Mg2C3 consists of C34 - type of anionic part.
species [Al(OH)4(H2O)2]– in aqueous solution.
 EBD_7374
520 CHEMISTRY

12. ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES &

TECHNIQUES
Exercise - 1 CH 3
|
1. (c) A carbon having an sp hybrid orbital with 50% CH 3 C HCH 2 CH 2CH 3
s-character is more electronegative than carbon (d )
atoms having sp2 and sp3 hybrid orbitals with 33%
and 25% s-character respectively. 9. (b)
In CH2 C CHCH3 10. (c) The correct name is 3 - methylbutan - 2 - ol
Number of s bonds : 11. (b) The compound is a derivative of butane.
sC – C = 3, s C – H = 6, total = 6 + 3 = 9 12. (b) The compound contains longest chain of 6C atoms
Number of p bonds = 2 and amino group. Hence it is an alkanamine.
13. (d) The compound is an ester. Its IUPAC name is derived
CH3 CH3
3| sp from alkyl alkanoate.
sp sp 2 sp 3 | 14. (d) The compound is an aldehyde containing longest chain
2. (d) CH3 C CH = CH CH — C º C H
7 6| 5 4 3 2 1 of 6 C-atoms and side chains.
CH3
Cl
x |
3. (c) See the number of s bonds formed by C in each case. 1 23
15. (c) CH3 — C — CH3
x x x x |
In HCOOH , (H 2 N) 2CO and CH 3C HO,C forms 3s
CH3
bonds and 1 p bond, hybridisation is sp 2 . In
2-chloro-2-methyl propane
x x
(CH 3 )3C OH , C forms 4s bonds, hence hybridisation 16. (a)
is sp3 17. (d) (CH 3 ) 2 CHCH 2CH 2 -
3-methylbutyl group
H H H
| | | Ketonic group
4. (b) H - C - C = C- C- C- H ;
| | | | | 4 3 2 1
H H H H H 18. (a) CH3 CH CO CH3
2 - Pentene
CH3 methyl group
No. of s bonds = 14, No. of p bond = 1
5. (b) Correct order of decreasing priority is 3-methyl-2-butanone
– COOH, – SO3H, – COOR, – OH.
6. (b) 19. (a) CH3
7. (d) 2, 2,3-trimethyl pentane 1
|
32
1° 1° H3C- C - CH3
CH3 CH3 |
1° 2° | | 1° CH3
H3C - H 2 C - CH - C - CH 3 Neopentane
3° | 4° or 2, 2- Dimethylpropane
CH3
1° 20. (b)
CH3 CH3 21. (b) The compound is a derivative of benzoic acid. The
| | positions of substituents attached to benzene nucleus
8. (d) CH 3 - C - C - CH 2 CH 3 are represented by number of C-atoms and not by ortho,
| |
CH3 CH3 meta and para.
(a ) 22. (c)
23. (d) The correct name of the given compound is
CH3 CH3 CH3 2, 5, 6 -trimethyloctane
| | | 24. (a) It is derivative of ethanamide having N-phenyl group.
CH 3 – C – CH 2 CH 3 CH C - C HCH CH 25. (b) The compound contains longest chain of 5C - atoms
| 3 2 3
|
CH3 CH3 and e of ene is retained as the suffix name starts with constant
( b) 26. (d) The compound contains longest chain of 3 C - atoms
(c ) and three -COOH groups and one -OH group attached
to it (latest convention).
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 521

27. (b) Structures (a), (c) and (d) have the same molecular +
formula (C6H12O) while (b) has C6H10O as molecular CH2 CH2 CH2 CH2
formula Å Å
28. (b) 2, 2, 4, 4 - Tetramethylhexane has 10 carbon atoms,
only 4-isopropylheptane has also 10 carbon atoms so
these two are isomers. Å
29. (a) 30. (c) 31. (a) 32. (b) 33. (d) 34. (c) Resonating structures of benzyl carbocation
35. (b) The two isomers differ in the position of the double bond so
they are called position isomers.
whereas in alkyl carbocations dispersal of positive
36. (a) 37. (c) charge on different hydrogen atoms is due to
38. (c) C5H10 has 1º degree of unsaturation since the isomers hyperconjugation hence the correct order of stability
are acyclic, all of these are alkenes. For writing the will be
Å
isomers, first introduce the double bond at different CH2
possible positions, and then consider the possibility
Å Å
of branching in the alkyl group. > CH 2 = CH - C H 2 > CH3 - CH 2 - CH 2
CH3CH2CH2CH =CH2 CH3CH2CH=CHCH3 Allyl Propyl
1-pentene (i) 2-pentene, (cis,- trans) (ii), (iii) Benzyl
45. (b) Structure (b) is a 3º carbocation, while (a) is 2º and (c)
CH3 CH3 and (d) are 1º carbocations; thus (b) is the most stable.
| |
CH 3- CH - CH = CH 2 CH 3 CH 2 C = CH 2 46. (a)
47. (a) Higher the possibility of delocalisation, greater is its
3-methyl-1-butene, (iv ) 2-methyl-1-butene, (v)
+
CH3 stability; in C6 H5CHC6 H5 , +ve charge can delocalise
|
over two benzene rings.
CH 3 - C = CHCH 3
48. (d) The organic reaction which proceed through
2-methyl-2-butene, (vi) heterolytic bond cleavage are called ionic or
39. (b) 40. (d) heteropolar or just polar reactions.
41. (c) Metamerism shown among compounds of the same 49. (b) Methyl carbanion is sp3 hybridised, with three bond
functional group. pairs and one lone pair same is the case with NH3.
42. (b) The order of stability of carbocations is :
+ + + Cl
(CH 3 )3 C > (CH3 )2 CH > CH3 – – – –
50. (b) C Cl > C6H5CH2 > (CH3)2 CH > (CH3)3C
43. (a) Carbocation are electron deficient species. More the Cl
number of alkyl groups attached to it, more will be –ve charge –M effect +I effect of CH 3 group
highly dispersed delocalises intensifies the –ve charge
stability due to + I effect. –ve charge
due to – I effect
+
CH3 ®- C -¬ CH3 51. (b) Homolytic fission of the C – C bond gives free radicals
| in which carbon is sp2- hybridised.
­ >
52. (c)
CH3
53. (b) The order of stability of free radicals
3°carbocation
(+vecharge dispersed to maximum extent) • • • •
(9 hyperconjugative H's)
(C6 H 5 ) 3 C > (C 6 H 5 ) 2 CH > (CH 3 ) 3 C > (CH 3 ) 2 C H
The stabilisation of first two is due to resonance and
+ + last two is due to inductive effect.
CH3 ®- C– H > CH3CH2 ®- CH2 54. (b) Free radicals are stabilized by hyperconjugation, thus
| 1° carbocation
­ (+ve charge least dispersed) 3° free radicals having maximum number of
CH2CH3 (2 hyper. H's) hyperconjugative structures are the most stable, and
2° carbocation primary free radical the least.
(5 hyper. H's) .
55. (b) C6 H5CHCH3 is a 2º benzylic free radical, hence
Alternatively, above order of stability order can be stabilized most due to resonance.
explained in terms of hyperconjugation. 56. (d) Order of stability of free radicals is
44. (d) Higher stability of allyl and aryl substituted methyl g
carbocation is due to dispersal of positive charge due 3° > 2° > 1° > C H3
to resonance 57. (c) The strength of nucleophile depends upon the nature
of alkyl group R on which nucleophile has to attack
+ +
CH 2 = CH - C H 2 ¬¾® CH 2 - CH = CH 2 and also on the nature of solvent. The order of strength
Resonating structures of allyl carbocation of nucleophiles follows the order :
CN– > I– > C6H5O– > OH– > Br– > Cl–
 EBD_7374
522 CHEMISTRY

58. (c) 59. (d) of ethanol is an example of elimination reaction.

60. (b) Electrophiles are electron deficient or positively charged Conc
species. C2 H5 OH ¾¾¾¾
® CH 2 = CH 2 + H 2 O .
H 2SO4
61. (d) BF3 and R3C – X are electrophiles while (CH3)3N and 73. (a)
C2H5O– are nucleophiles 74. (c) – CH3 is an electron donating group.
62. (b) –CH3 group has +I effect, as number of –CH3 group 75. (c)
increases, the inductive effect increases. 76. (d) Resonance structures have the same number of
63. (d) Due to – I effect of the – CHO group, oxygen acquires- unpaired electrons. However, they differ in the way of
d - charge and the terminal carbon acquires d + charge. distribution of electrons.
d+ d- 77. (c) Resonance effect is the polarity produced in the
CH2 = CH – C = O
molecule by the interactions of two p – bonds or
H between a p – bond and a lone pair of electrons
64. (c) All resonating structures should have same number present on an adjacent atom.
of electron pairs. 78. (b) – I group destablises carbocation and since inductive
65. (b) Only structure (b) has a conjugated system, which is effect decreases with increasing length of carbon chain.
necessary for resonance. Therefore (b) is the correct option.
66. (a) It is fact that aniline is better nucleophile than anilium 79. (d) –NO2 group, being strong electron-withdrawing,
ion. Anilium ion has +ve charge, which reduces the disperses the –ve charge, hence stabilizes the
tendency to donate lone pair of electron C6 H5 NH3+ . concerned carbanion.
Anilium ion
80. (b) In the presence of UV rays or energy, by boiling chlorine,
free radical is generated which attacks the methyl carbon
67. (b) – OH shows + R effect while C = O shows – R atom of the toluene.
effect. CH3 CH2
¾®D
68. (d) +H
69. (b)
70. (b) The stability of carbocation on the basis of hyper- benzyl free radical
hn
conjugation can be explained as hyperconjugation Cl 2 ¾¾® 2Cl•
stabilises the carbocation because electron density •CH CH2Cl
from the adjacent p-bond helps in dispersing the
2 •
+ Cl
positive charge.
+ + 81. (c) Cl– is the best leaving group among the given option.
H H H H H H H H
| |+ | + | | | | 82. (a) Nucleophilicity increases down the periodic table.
H - C- C « H - C = C « H C = C « H - C = C
| | | | | | | I - > Br - > Cl - > F-
H H H H H H H+ H 83. (b) H 2 C = CHCl is capable of showing resonance which
In general greater the number of alkyl groups attached
to a positively charged carbon atom, the greater is the develops a partial double bond character on C–Cl bond,
hyperconjugation interaction and stabilisation of the thereby making it less reactive toward nucleophilic
cation. Thus, we have the following relative stability substitution.
gg _
of carbocation. H 2 C = CH - Cl gg H 2C - CH = Cl +
gg
CH3
| + + + 84. (d) CH 3 - Br ® + CH3 + Br -
CH3 - C + > (CH3 ) 2 CH > CH3 CH 2 > CH3 g g
| CH 3 - Cl ® CH 3 + Cl
CH3
Hence, stability of carbocation is directly proportional 85. (b) Among the given compounds naphthelene is volatile
to number of alkyl group directly attached to but benzoic acid is non-volatile (it forms a dimer). So,
carbocation. the best method for their separation is sublimation,
71. (b) Stability order of different alkyl carbocations on the which is applicable to compounds which can be
basis of hyperconjugation is : converted directly into the vapour phase from its solid
3° > 2° > 1° > methyl state on heating and back to the solid state on cooling.
In t-butyl cation, the C-atom bearing the positive charge Hence it is the most appropriate method.
is attached to three methyl groups therefore it possesss 86. (d)
nine a-hydrogens. It will give maximum nine 87. (b) If there is a small difference (10 or less) in the boiling
hyperconjugative structures leading to maximum points of liquids fractional distillation is used, e.g.
stability. acetone b.p. 329 K and methanol b.p. 338 K.
72. (b) In elimination reactions one or two molecules are lost 88. (a) Fractional distillation is used for the distillation of
from the substrate to form a multiple bond. Dehydration petroleum. This method is used for separating a mixture
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 523

of two or more miscible, volatile liquids having close NaCN + AgNO 3 ¾

¾® NaNO 3 + AgCN ¯
(less than 40 degrees) boiling points. (For example, a White
mixture of acetone, b.p., 56°C and methanol, b.p. 65°C) NaCl + AgNO3 ¾¾
® NaNO3 + AgCl ¯
89. (c) Glycerol decomposes at its boiling point, hence it White
should be purified by distillation under reduced boil
pressure. Na 2S + 2HNO 3 ¾¾
¾® 2 NaNO 3 + H 2S ­
90. (c) boil
NaCN + HNO 3 ¾¾
¾® NaNO 3 + HCN ­
91. (a) The latest technique for the purification of organic 107. (d)
compounds is chromatography. These are of various 108. (d) Kjeldahl method is not applicable to any of the given
types like column, paper and gas-chromatography. compounds. As nitrogen of these compounds does
92. (d) Both silica gel and alumina are used as adsorbents not change to ammonium sulphate on heating with
in adsorption chromatography. conc. H2SO4.
93. (a) Chromatography paper contains water trapped in it, 109. (b)
which acts as the stationary phase. 110. (b) In Kjeldahl’s method nitrogen is converted into
94. (c) Th e mixture of sugars is a h omogenous one. (NH4)2 SO4, then to NH3
Homogeneous mixtures of a solvent and one or more 111. (d) To increase the bpt of H2SO4,K2SO4 is added
solutes (dissolved substances) are often separated by
chromatography. Chromatography works to separate 1.4 ´ N ´ V
112. (b) N% =
a mixture because the components of a mixture wt.of organic compound
distribute themselves differently when they are in
contact with a “two phase system”. One phase is 1.4 ´ 29 ´1/ 5
= = 16.24%
stationary and the other is moving or mobile. The 0.5
stationary phase may be a solid packed in a tube or a 32 0.233
piece of paper. The mobile phase may be liquid of 113. (b) % of S = ´ ´ 100 = 10 %
233 0.32
gaseous.
95. (b) 96. (b) 62 wt . of Mg 2 P2 O 7
114. (b) Percentage of P = × × 100
97. (b) Fractional distillation method is used if the difference 222 wt. of compound
in boiling points of two liquids is not much.
62 1.332
98. (a) 99. (a) = × × 100 = 13.33%
100. (d) The boiling point of o-nitrophenol is less than para- 222 2.79
nitrophenol due to presence of intramolecular hydrogen 115. (a) % of element Relative Simple ratio
bonding. Since p-nitrophenol is less volatile than no. of atoms
o-nitrophenol due to presence of inter molecular
38.8
hydrogen bonding hence they can be separated by C 38.8 = 3.2 1
steam distillation. 12
101. (b) 16
102. (b) Hydrazine (NH2NH2) does not contain carbon and H 16.0 = 16.0 5
1
hence on fusion with Na metal, it cannot form NaCN;
consequently hydrazine does not show Lassaigne’s 45.28
N 45.28 = 3.2 1
test for nitrogen. 14
103. (a) Prussian blue Fe 4 [Fe(CN) 6 ]3 is formed in Lassaigne \ Emphirical formula = CH5N
test for nitrogen. 116. (b) K 2SO 4 raises bpt. and CuSO 4 acts as catalyst.
3Na 4 [Fe(CN)6 + Fe 3+
¾¾
® 117. (d) When organic compound contains nitrogen, upon
combustion it will produce oxides of nitrogen soluble
Fe 4 [Fe(CN) 4 ]3 + 12Na + in KOH solution. The copper will convert them into
Prussian blue N2
104. (c)
105. (d) To convert covalent compounds into ionic compounds 2NO + 2Cu ¾
¾® 2CuO + N 2
such as NaCN, Na2S, NaX, etc. 2 NO 2 + 4Cu ¾ ¾® 4CuO + N 2 etc.
106. (b) Na2S and NaCN, formed during fusion with metallic
Halogens will be removed as AgX. In case of sulphur
sodium, must be removed before adding AgNO 3,
otherwise black ppt. due to Na2S or white precipitate SO 2 formed will be removed as PbSO 4 .
due to AgCN will be formed and thus white precipitate 118. (c)
of AgCl will not be identified easily. 119. (d) The compounds with odd number of N-atoms have
Na 2S + 2AgNO3 ¾
¾® 2NaNO3 + Ag 2S ¯ odd masses and with even number of N-atoms have
Black even masses. This is “nitrogen rule”.
 EBD_7374
524 CHEMISTRY

120. (b) Percentage of N in a compound volatile. Thus, steam distillation technique is a suitable
method for the extraction of essential oils.
1.4 ´ Normality of acid ´ Volume of acid used
= 7. (d) Thin layer chromatography (TLC) involves separation
Mass of the substance taken of substances of a mixture over a thin layer of an
Given, 0.5 M H2SO4 is used. adsorbent coated on a glass plate.
Normality = Molarity × n A thin layer of an adsorbent is spread over a glass
Mol.mass 98 plate and glass plate is placed in an eluant. As eluant
where n = = =2 rises, components of the mixture move up along with
Eq.mass 49 the eluant to different distances depending on their
\ Normality = 0.5 × 2 = 1 N H2SO4 degree of adsorption and separation takes place.
Volume of acid used to neutralise NH3 = 10 cm3 Therefore, TLC technique will give the best results in
Mass of organic compound taken = 0.25 g identifying the different types of ink used at different
1.4 ´ 1´ 10 places in the documents.
\ %N = = 56. 8. (b) Partition chromatography is based on continuous
0.25
differential partitioning of components of a mixture
Exercise - 2 between stationary and mobile phases. Paper
chromatography is a type of partition chromatography.
CH3 9. (a) Stability of the given cations can be understood by
7 6 5 4| 3 2 1 the following structures:
1. (a) CH3 – CH2 – CH2 – C – CH – CH2 – CH3
| | + + ..
CH3C2H5 CH3 CH CH3 ; CH3 - C H - O
. . - CH3 ;
(I) (II)
3-ethyl-4, 4-dimethyl heptane + I – effect of the two Strong + R – effect of – OCH3
methyl groups stabilises group stabilises the carbocation
O O the carbocation
5 || 3 2 1 ||
2. (d) CH3 -4C - CH 2 - CH 2 - C - OH +
4-oxopentanoic acid CH 3 - C H - CH 2 ®- OCH 3
(III)
Note : Carboxylic acid (—COOH) has more priority - I effect of -OCH 3 group
destabilises the carbocation
than ketone ( C= O).
Hence, the correct order of decreasing stability of
3. (b) Cl carbocation will be : II > I > III
1 NO2 10. (b) 4 3
2
H3C — CH — CH — CH3
| |
3 5 CH 2 CH2
4 2
| |
CH3 6 CH3 1 CH3
3, 4-dimethylhexane
1-chloro-4 -methyl-2 -nitrobenzene
For tri or higher substituted benzene derivatives, the 11. (a) Electronegativity of Cl, Br, C and Mg follows the order
compounds are named by identifying substituent Cl > Br > C > Mg, thus chlorine has the greatest –I-
positions on the ring by following the lowest locant effect and disperse the positive charge on ‘C’ atom
rule. most effectively.
4. (c) Electronegativity of carbon atom depends on its state Hence, *CH3 — CH2 — Cl has the greatest positive
of hybridisation. More the s-character more will be the charge.
electronegativity. 12. (d) In all the given ionic species, the negative charge is
sp3 < sp2 < sp dispersed which stabilises them. Here, the negative
s-character : 25% 33% 50% charge is dispersed by two factors, i.e., +R-effect of
Thus, sp-carbon (CH3 – CH2 – C º *CH) has the highest the carboxylate ion (conjugation) and – I-effect of the
electronegativity. halogens.
5. (c) Two or more compounds having the same molecular As it can be clearly seen in the given structures, that
formula but different functional groups are called +R-effect is common in all the four species, therefore,
functional isomers. Functional isomer of alcohol is overall dispersal of negative charge depends upon
ether, aldehyde is ketone and cyanide is isocyanide. the number of halogen atoms and their
But alkyl halides do not show functional isomerism. electronegativity. Since, Fluorine has the highest
6. (d) Essential oils are insoluble in water and have high electronegativity and two F-atoms are present in option
vapour pressure at 373K but are miscible with water (d), thus, dispersal of negative charge will be maximum
vapour in vapour phase, it means these are steam in it, thus it is most stable.
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 525

–
O O Cl CH2 CH2
F || F

—
–
CH C—O CH C—
—O º (1) Cl (2)
F F
Cl
F O
CH C – CH2 CH
F O
Note : In structure (a), methyl group increases the Cl (3) (4)
density on C-atom. 18. (a) H H
13. (c) When an electrophile attacks CH3 – CH = CH2, there C C
are two possibilities of an intermediate formed: Cl CHOHCOOH
Å cis
+
CH3 – CH = CH2 + H ® CH3 – C H – CH3
H CHOHCOOH
C C
(2°carbocation) Cl H
+ Å trans
CH3 – CH = CH2 + H CH 3 - CH 2 - CH 2
Geometric isomers
(1° carbocation) COOH
As 2° carbocation is more stable than 1° carbocation
thus first addition is more feasible. C
Note : Stability of carbocations is the basis of H CH CH
Markownikoff's rule. HO
Cl
14. (b) Arrow denotes the direction of movement of electrons.
Å COOH
CH 3 - Br ¾¾ ® CH 3 + Br
Since, Br is more electronegative than carbon, hence HClC HC C
H
heterolytic fission occurs in such a way that CH3 gets
OH
a positive charge and Br gets a negative charge.
15. (b) Addition of HCl to an alkene takes place in two steps Optical isomers
as follows: O O
Step I : p-bonds creates an electron cloud, electrophile
(H+) from H — Cl attacks the electron cloud and a CH C C OCH3 , CH3 C C C OH
carbocation is formed.
Cl OH Cl OH
+
C—
+ Functional isomers
H —C C—C
—

H
H
(carbocation) H2C C C COOH, H2C C CH COOH
Step II : The chloride ion attacks the carbocation
formed. Cl OH Cl OH
Position isomers
Å – 19. (c) Assertion is true but reason is false. NH4Cl suppresses
C — C + Cl C—C the ionisation of NH4OH due to common ion effect and
| | |
H so ions of third group get precipitated as their
Cl H
hydroxides.
16. (d) Out of the given four compounds only (iv) compound 20. (d) In both the molecules the bond moments are not
is chiral and hence only this compound will undergo canceling with each other and hence the molecules
racemisation. has a resultant dipole and hence the molecule is polar.
17. (b) In diphenylmethane monochlorination at following 21. (b) –CH3 group has +I effect, as number of –CH3 group
positions will produce structured isomers increases, the inductive effect increases.
22. (c)
CH2 23. (c) Four different Substituent, only one chiral centre.
Hence only enantiomers are possible.
24. (c) All of these compounds show tautomerism
1 25. (a) Nucleophile is a species that provide electron while
2 3 4 species which are deficient of electrons are termed as
lewis acid, hence nucleophiles are usually lewis bases.
 EBD_7374
526 CHEMISTRY

26. (b) Only structure (III) has H in conjugation with free Na 2S + 2HNO3 ¾¾
® 2NaNO 3 + H 2S ­
radical. If cyanide and sulphide ions are not decomposed, they
So, hyperconjugation is possible in (III) only. will react with silver nitrate and hence will interfere
27. (b) p bond is transferred after leaving Cl– with the test.
+
CH3 – CH=CHCH2 — Cl CH3 – CH=CH—CH2
NaCN + AgNO3 ¾¾
® AgCN + NaNO3
+ Silver
CH3—CH—CH=CH 2 cyanide
(White ppt.)
28. (a)
O
Na 2S + 2AgNO3 ¾¾
® Ag 2S + 2NaNO3
(a) CH = CH – OH CH2 – CH Silver
sulphide
enol form keto form (Black ppt.)

(b) O O cannot tautomerise 37. (a) Me + –

Br ionisation +Br
Me
(A)
(c) O OH O, OH
Me Me
ionisation Me
O keto form O OH OH + + Br –
enol form Br
(B)
(d) O OH , OH
Me
ionisation Me –
Me + Br
O O OH Me +
enol form Br
keto form
(C)
29. (d)
H Since SN1 reactions involve the formation of carbocation
| as intermediate in the rate determining step, more is the
30. (c) H3C — C = CH — CH 2 stability of carbocation higher will be the reactivity of
| alkyl halides towards SN1 route. Now we know that
Ph
stability of carbocations follows the order : 3° > 2° > 1°,
1- Phenyl-2-butene so SN1 reactivity should also follow the same order.
The two groups around each of the doubly bonded 3° > 2° > 1° > Methyl (SN1 reactivity)
carbon are different. Hence this compound can show 38. (b) A rapid umbrella type inversion rapidly converts the
cis-and trans-isomerism. structure III to its enantiomer; hence the two
31. (d) compound (d) is nonaromatic and hence least enantiomers are not separable.
reasonance stabilized whereas other three are aromatic.
32. (d) Anthracene is purified by sublimation. In sublimation, CH3
a solid is converted directly into gaseous state on 1 2 3 4 5
39. (c) H3C— C— CH2— CH— CH3
heating without passing through liquid phase.
33. (b) compound (b) is optically active due to absence of
CH3 CH3
plane of symmetry and center of symmetry.
34. (d) In staggered conformation any two hydrogen atoms C1 and C5 are 1°, C3 is 2°, C4 is 3°, and C2 is 4°.
on adjacent carbon atoms are as far apart as possible 40. (d) 41. (c)
there by minimising repulsion between the electron 42. (c) It is correct statement that NF3 is a weaker ligand than
clouds of s-bonds of two non-bonded H-atomic N(CH3) 3, the reason is that fluorine is highly
(torsional strain) electronegative therefore, it with draw electrons from
35. (d) CH3— C º C– nitrogen atom. Hence, the lone pair of nitrogen atom
No. of s bp - 1 ù
cannot be ligated. While N(CH3)3 is a strong ligand
û 2 and hybridisation is sp. because CH3 is electron releasing group.
lp -1
43. (d)
36. (b) If the organic compound also contains nitrogen or 44. (b) Since S N1 reactions involve the formation of
sulphur, the Lassaigne's extract on boiling with dil. carbocation as intermediate in the rate determining
HNO3 decomposes sodium cyanide or sodium sulphide step, more is the stability of carbocation higher will be
formed during fusion. the reactivity of alkyl halides towards SN1 route.
NaCN + HNO 3 ¾¾
® NaNO3 + HCN ­
Hence correct order is II < I < III
ORGANIC CHEMISTRY–SOME BASIC PRINCIPLES & TECHNIQUES 527

45. (c) Meso compounds are characterized by an internal

plane of symmetry that renders them achiral.
46. (a) A compound is said to exhibit optical isomerism if it 55. (a) 1 3
2
contains atleast one chiral carbon atom, which is an
atom bonded to 4 different atoms or groups. HO
IUPAC name – 3, 3-Dimethyl -1 cyclohexanol
CH3 56. (b) The compound has two similar assymmetric
|
(CH3 )2 CH - C* - CH 2 CH3 C-atoms. It has plane of symmetry and exists in meso
| form.
H
sp2 sp2 sp sp
47. (b) CH2 = CH – C CH plane of symmetry
48. (a) – I effect increases on increasing electronegativity of
atom. So, correct order of – I effect is
–NH2 < – OR < – F. meso - 2, 3 Dichlorobutane
*Most appropriate answer is option (1), however
option (2) may also be correct answer.
Exercise - 3
1. (a)
OH
OH 1 OH
6 5 4
49. (a) 4 2 OH 4 4 2 4
2. (a) 5 5 2 15 1 2
1 3 3 1 3 3 3
O 2
OH
5-Hydroxy cyclohex-3-en-1-one
50. (b) The stronger the base the more is the nucleophilic char- OH 1 3 1 2
acter and vice versa. Basic chartacter : 3 2 4 3
OH 4 2
4
1 2 1
H2S > C2H5OH > H2O > PhOH OH
3
OH
Hence the nucleophilic character :
All have different IUPAC names. Thus, none of identical.
HS– > C2H5O– > OH– > PhO–
51. (c)
a
a
H5C2 H
H H 3. (c)
C=C C=C (6a -H)
&
H C2H5 H5C2 C2H5 a
a
trans-3-Hexene cis-3-Hexene
µ=0 µ>0 4. (a) Meso compounds are those having 2 or more chiral
centers along with symmetry./
M.P. of trans-isomer high than cis-isomer.
52. (d) ’
53. (c) Order of basic nature of compounds depend on electron O POS
(1) (2) O
donating tendency. * *
O O ’
The compound (ii) is least basic among all given
compounds due to sp2 hybridization of nitrogen atom. POS O
Meso
Compound (iii) is most basic in given compounds due
to resonance. one nitrogen carry negative charge and 5. (a) 1, 3 and 4 compounds are 3-ethyl-4-methyl hexane.
its conjugate acid have two equivalent resonating 6. (c) CH3 H
structure. Secondary amine (iv) is more basic than
primary amine (i). C=C H
54. (c) The strength of nucleophile depends upon the nature
CH3 C
of alkyl group R on which nucleophile has to attack
and also on the nature of solvent. The order of strength CH 3 COOH
of nucleophiles follows the order :
CN– > I– > C6H5O– > OH– > Br– > Cl– It has chiral asymmetric carbon atom (marked *) so it
shows optical isomerism. Two groups attaced to C = C
 EBD_7374
528 CHEMISTRY

are same (–CH3), so it does not show geometrical 12. (c) In resonance, only the group which is coplanar with
isomerism. the skeleton can participate in resonance, in case the
7. (a) Stability of carbocation µ no. of µ–H present on group is out of plane of the ring (skeleton), it can’t
carbocation. participate in resonance.
··+
O +
O I O O I O
8. (c) It has complete octet for all atoms. + + + +
N N N N

9. (d)
..
In option (d), the N Me
–O
O– –O
O–
2 group is out of the plane of
the benzene ring due to the presence of two bulky + +
N N
–CMe3 groups. Hence the lone pair of electrons on N O O– –O O–
is not delocalised. 2,4,6 – Trinitroiodobenzene
Å (Picryl iodide)
10. (b) Carboxylic acids are stronger acids than - NH 3
Here only the p- nitro group is involved in resonance
because the corresponding conjugate base (–COO–)
with the benzene, the two o-nitro groups do not
is more stable than –NH2. Hence Y is the strongest
participate in resonance as they are pushed out of
acid. Since – NH3+ has – I effect (acid enhancing) which
the plane of the ring by bulky iodine atom, hence the
decreases with distance, therefore, effect is more
C–N bond length of the o-nitro groups is very close
pronounced in Z than in X. As a result, Z is more acidic
to C–N single bond. Thus a = b >c.
than X. Hence the true option is Y > Z > X.
11. (b) In general, the weaker the base, the better is its leaving O 1 NHCH3
tendency. Basic character of the species, in turn can be 13. (c) 2' 2 4
3
ascertained by knowing the acidic character of the Cl 5
1'
corresponding conjugate acids. O
N-Methyl -2-(2'-chloroethyl) -3-keto-4-pentenamide
F3CSO 2OH > H3C SO2OH
14. (b)

Va IVa O
- ||
aq. OH
15. (c) CH 3CH 2 CCl 2 CH 3 ¾¾ ¾¾® CH 3 CH 2 C CH 3
> H3 O+ > HF > NH 3 [X ] [Y ]
III a Ia IIa
 13. HYDROCARBONS

Exercise - 1 10. (d)

11. (a) Complete combustion of all organic compounds leads
1. (c) Pentane (C5H12) exists as three chain isomers to formation of CO2 + H2O.
CH3CH 2CH 2CH 2CH3 CH3 - CH - CH 2 - CH3 12. (b) During cracking higher hydrocarbons (liquid) are
n -pentane | converted to lower gaseous hydrocarbons.
CH3 13. (c) n-Alkanes on heating with anhydrous aluminium
2 -methylbutane (iso pentane) chloride and hydrogen chloride gas isomerise to
branched chain alkanes.
CH3 14. (c) A conformation is defined as the relative arrangement
| of atoms or groups around a central atom, obtained by
H3C - C - CH3
| the free rotation of one part of the molecule with respect
CH3 to rest of the molecule. For a complete rotation of 360º,
one part may rotate through any degree say 0.1º, 0.5º,
2,3-dimethylpropane (neo pentane)
1º etc. giving rise to infinite number of relative
2. (c) 3. (d)
arrangements of group (atom) around a central atom,
4. (d) CH4, C2H6 and C3H8 can have only one structure but
keeping other part fixed.
C4H10 can have more than one structure. Possible
15. (d) Spatial arrangements of atoms which can be converted
structures of C4H10 are following
around a C – C single bond are called conformations or
H H H H conformers or rotamers.
213 4
H C C C C H 2-Methylpropane (isobutane) 16. (c) In methane carbon atom is sp3 hybridized.
H H H H 17. (b) Dihydrogen gas adds to alkenes and alkynes in the
(b.p.261 K)
presence of finely divided catalysts like platinum,
Butane (n- butane), (b.p. 273 K) palladium or nickel to form alkanes. These metals
H H H adsorb dihydrogen gas on their surfaces and activate
1 2 3
H C C C H the hydrogen-hydrogen bond. Platinum and palladium
catalyse the reaction at room temperature but relatively
H H C HH higher temperature and pressure are required with nickel
H catalyst.
5. (a) When alkyl halide is treated with sodium metal in 18. (b) For statement (iii), fluorination is too violent to be
presence of ether, alkane is obtained, this reaction is controlled. For statement (iv), iodination is very slow
called as Wurtz reaction. and reversible reaction. It can be carried out in the
dry ether presence of oxidizing agents like HIO3 or HNO3
R – X + 2Na + X – R' ¾¾¾¾® R - R '+2 NaBr
ˆˆ† CH3I + HI
CH 4 + I2 ‡ˆˆ
dry ether
CH3–Br + 2Na+Br–CH3 ¾¾¾¾®
5 HI + HIO3 ® 3I 2 + 3H 2 O
CH 3 - CH 3 + 2 NaBr 19. (c) Pyrolysis and cracking are same process.
6. (c) Other three methods can be used for the preparation of 20. (b) Rotation around a C-C single bond is not completely
alkane having at least two carbon atoms. free. It is hindered by a small energy barrier of 1-20 kJ
7. (b) Sodium salts of carboxylic acids on heating with soda mol-1 due to weak repulsive interaction between the
lime (mixture of sodium hydroxide and calcium oxide) give adjacent bonds. Such a type of repulsive interaction is
alkanes containing one carbon atom less than the called torsional strain.
carboxylic acid. This process of elimination of carbon 21. (b) Eclipsed form has maximum torsional strain, while
dioxide from a carboxylic acid is known as decarboxylation staggered form has the least.
CH3COO - Na + + NaOH ¾¾¾
CaO
® CH 4 + Na 2CO3 Pt/Pd/ Ni
D 22. (a) CH 2 = CH 2 + H 2 ¾¾¾¾¾
® CH3 - CH3
Sodium ethanoate Methane Ethene Ethane
hv
8. (a) •
Cl2 ¾¾¾¾¾¾® 2Cl
Chain initiation Zn, H +
CH3 CH3 - Cl + H 2 ¾¾¾¾
® CH 4 + HCl
| Chloromethane Methane
9. (d) Neo-pentane, H3C - C - CH3 , has only 1° hydrogen dry ether
| CH3Br + 2Na + BrCH3 ¾¾¾¾® CH3 - CH3 + 2NaBr
CH3 Bromomethane Ethane
and hence gives only one monochloro derivative. - + CaO
CH 3COO Na + NaOH ¾¾¾ ® CH 4 + Na 2 CO3
D
 EBD_7374
530 CHEMISTRY

23. (c) Br
24. (b) The assertion that chlorination of CH4 does not take |
place in dark is correct because it is a free radical alc. KOH
36. (d) CH3– CH – CH2 – CH3
reaction and free radicals are obtained in presence of 2-Bromobutane
sun light. +
CH3–CH–CH2–CH3
25. (b) Iodination is reversible since formed HI is a strong
reducing agent and reduces the alkyl iodide back to –H+
H3C H
alkane. CH4 + I2 ƒ CH3I + HI C=C
Iodination can be done only in presence of strong H CH3
trans-2-butene
oxidising agents like iodic acid which destroys the
hydriodic acid. conc. H SO
26. (a) Given 37. (c) C2 H5 OH ¾¾¾¾¾¾
2 4® C H + H O
2 4 2
KMnO4
Cl 2 alc./KOH O3 /H2 O
A ¾¾¾ ® B ¾¾¾¾¾ ® C ¾¾¾¾ ® CH 2O Note : If ethyl alcohol is taken in excess and the reaction
Hydrocarbon is carried out at a temperature of 433-443 K diethyl ether
Since hydrocarbon C give only CH2O, on ozonolysis, is formed.
C should be CH2 = CH2 hence going backward A should conc. H SO
2 4 ® C H OC H + H O
2C2 H5OH ¾¾¾¾¾¾ 2 5 2 5
433-443 K 2
be ethane. Thus the reactions are (excess)
Cl 2 / hn 38. (a) Peroxide effect is observed only in case of HBr.
CH 3CH 3 ¾¾¾¾® CH 3CH 2Cl alc. ...
(A) (B) KOH Therefore, addition of HCl to propene even in the
presence of benzoyl peroxide occurs according to
CH 2= CH 2 ¾O / H2O
¾3 ¾ ¾® HCHO
(C ) D ( D) Markovnikov’s rule :
HCl
CH3 CH3 - CH = CH 2 ¾¾¾¾¾¾®
(C6 H5CO)2 O 2
½
27. (b) CH3 — C— CH3 CH 3 - CHCl - CH 3
½ 39. (b) Markonikov’s way of addition :
CH3
A + B-
2,2-Dimethyl propane CH 3 - CH = CH 2 ¾¾¾¾ ® CH3 - CH - CH 2
All hydrogen atoms are equivalent in 2, | |
2-dimethylpropan e. So it forms only one B A
monochlorinated product. 40. (d) Since given alkene on ozonolysis gives 2 moles of
28. (d) 29. (a) propanone hence alkene should have a double bond
30. (a) Since b (from bromo) comes earlier in alphabetical order between two equivalent C atoms i.e. the formula should
than c (from chloro), the correct name should be 2, 3- be
dibromo-1, 4-dichlorobutene-2 and not 1,4-dichloro- H3C CH3
C C +O3 ¾¾¾¾
Zn/H 2O
®
2, 3-dibromobutene-2. H3C CH3
31. (d) Alkenes having double bonds with two different 2, 3-dimethyl but-2-ene
groups on each end of the double bond show O
geometrical isomerism. A2b2c2, A2b2cd, A2bcde. ½½
2CH3 —C—CH3
Br Br Propanone
C C 1,2-dibromopropene 41. (d) In presence of peroxide, HBr adds on alkenes in anti–
H CH3
markovnikov’s way, thus
Br Br Peroxide
H3CCH = CH 2 + HBr ¾¾¾¾® H3CCH 2CH 2 Br
C C 2,3-dibromobut-2-ene
H3C CH3 Pr opene n - propyl bromide
Kharasch observed that the addition of HBr to
32. (b) The two isomers differ in the position of the double unsymmetrical alkene in the presence of organic
bond so they are called position isomers.
peroxides follows an opposite course to that suggested
33. (a) As sketched in the above question , C5H10 may be by Markownikoff . This is termed anti-Markownikoff
monosubstituted as in (i) and (iv), disubstituted as in or peroxide effect.
(ii), (iii) and (v) and trisubstituted as in (vi) 42. (b) We know that in case of an unsymmetrical alkene there
34. (c) The condition for geometrical isomerism is is the possibility of forming two products. In such cases
a a a e the formation of major product is decided on the basis
C=C or C=C of Markownikoffs rule which is rationalized in terms of
b b b d
stability of the intermediate carbocation. Also
35. (c)
remember that 3° carbocation is more stable than 2°
HYDROCARBONS 531

carbocation and 2° carbocation is more stable than 1°

carbocation. H H
R H | |
H3C
| | CH – CH = CH2 C=C + H X ¾¾
® R -C-C-H
H3C 3– methyl-1-butene H
H
CH3 + |
CH – CH – CH (1°) H
CH3 |
|
2 2
+
+H Markownikoff’s rule is based on the stability of
CH3 +
| CH – CH – CH3 (2°) carbocations (3° > 2° > 1° > methyl).
|

CH3 48. (d) Completing the sequence of given reactions,

Of the two possibilities 2° carbocation is more stable O
so the product of the r eaction expected was CH 3 – CH = CH - CH 3 ¾¾3¾
®
predominantly one formed by 2° carbocation i.e. O
Ch3 – CH – CH – CH 3 Zn / H O
| | CH3– CH CH – CH3 ¾¾¾¾®
2

CH 3 Br
i.e. 2– Bromo-3-methylbutane O O
However some electrophilic addition reaction form ‘A’
products that are clearly not the result of the addition (ozonide)
of electrophile to the sp2 carbon bonded to the most 2CH3CHO+ H 2 O + ZnO
hydrogens and the addition of a nucleophile to the 'B '
other sp2 carbon. 49. (c) The given molecular formula suggests that the aldehyde
In the above cases the addition of HBr to 3-methyl-1- formed will be acetaldehyde hence the alkene will be
butene the two products formed are shown below. CH3CH = CHCH3
2- butene
CH3 (i) ¾¾® O3
|
CH3 – CH – CH = CH2 + HBr (ii) Zx/H2O
2CH3CHO
CH3 CH3 50. (a) The addition of HBr to symmetrical alkenes is not
| |
Ch3 – CH – CH – CH3 + CH3 – C – CH2 – CH3 affected by the presence or absence of peroxide.
| |
Br Br 51. (d) CH 2 = CH 2 + KMnO4 ¾OH
¾¾®
2-Bromo-3-methylbutane 2-Bromo-2-methylbutane
CH2 - CH 2
In this case the major product formed is 2- bromo-2- | | + MnO 2 + KOH
methylbutane i.e. option (b) is correct answer. OH OH
(Note: The unexpected product results from a Glycol
rearrangement of 2° carbocation to 3°. Please note that
52. (b) When unsymmetrical unsaturated hydrocarbon reacts
all carbocations do not rearrange.
with unsymmetrical reagent, then negative part of
43. (c) Alkenes combine with hydrogen under pressure and
reagents attacks that carbon which has less H-atom.
in presence of a catalyst (Ni, Pt or Pd) and form alkanes.
[Markownikoff's rule]
H / Pd I
Butene - 1 ¾¾2¾ ¾® Butane
400°C
|
44. (a) Alkenes are unsaturated hydrocarbon having double CH 3 - CH = CH 2 + HI ¾¾ ¾ ¾® CH 3 - CH - CH 3
bond so generally gives addition reactions. Propene-2 2-Iodopropane
45. (c) CCl
46. (d) A doubly bonded carbon atom having an alkyl group 53. (a) CH 2 = CH 2 + Br2 ¾¾¾
4 ® CH - CH
2 2
is oxidised to aldehyde which is further oxidised to | |
Br Br
carboxylic acid.
1, 2-dibromo ethane
(i) KMnO 4 ,OH - 54. (c) By adding bromine water to a solution, if the colour of
CH3CH 2CH = CH CH3 ¾¾¾¾¾¾¾
+
®
(ii) H bromine water decolourises then the compound is
CH3CHO + CH3CH 2CHO unsaturated. This is a confirmatory test for unsaturation.
¯ ¯ Conc. H SO
CH3COOH CH3CH 2COOH 55. (b) CH 3 - CH = CH 2 + H 2 O ¾¾¾¾¾¾¾
2 4 ®
Markonikoff's rule
47. (c) According to Markownikoff’s rule, "in case of addition
of an unsymmetrical reagent (H– X), the positive part CH 3 - CH - CH3
|
get attached to the C which is least substituted or which OH
bears larger number of hydrogen atoms." Isopropyl alcohol
 EBD_7374
532 CHEMISTRY

56. (b) For statement (ii), Alkenes are also known as olefins. 64. (c) In compounds
For statement (iv), Carbon–Carbon double bond in
CH3 CH3
alkene consists of one sigma and one pi bond.
H s H
C C
H H first has more dipole moment than second.
57. (a) For statement (i), cis form of alkenes have significant Therefore its boiling point will be higher. Melting point
dipole moment whereas dipole moment of trans form is depends on symmetry therefore I has higher melting
almost zero. For statement (iv), due to different point than II. Steric crowding in I is more than II
arrangements of atoms or groups in space cis and trans therefore I is more stable than II.
isomers differ in their properties like melting point, 65. (b)
boiling point, dipole moment, solubility etc. 66. (a) When 3, 3 dimethyl 2-butanol is heated with H2SO4
the major product obtained is 2, 3 dimethyl 2-butene.
58. (a) Pd/C
CH º CH + H 2 ¾¾¾® CH 2 = CH 2 CH3
Ethyne Ethene |
Conc.H SO
H H H H CH3 - CH - C - CH3 ¾¾¾¾¾¾
2 4®
b a
alc.KOH | |
H C C H ¾¾¾¾ D
® C =C OH CH3
3,3- Dimethyl 2-butanol
H X H H
CH3 CH3
(X = Cl, Br, I) +
CH3 – CH – C – CH3 CH3 – CH – C – CH3
CH 2 Br - CH 2 Br + Zn ¾¾
® CH 2 = CH 2 + ZnBr2 + OH2 CH3 CH3
H H CH3 CH3
b a +
Conc.H 2SO 4
H C C H ¾¾¾¾¾¾ ® CH 2 = CH 2 + H2 O CH3 – CH – C – CH3 CH3 – C = C – CH3
D
H OH Ethene CH3 CH3
Ethanol 2, 3 dimethyl -2-butene

59. (a) This reaction follows anti Markownikoff rule 67. (d) Addition of hydrogen halide to alkene is an example of
electrophilic addition involving carbocations as
Peroxide
CH3CH2CH = CH2 + HBr ¾¾¾ ¾↑ intermediates.
CH3 CH2 CH2 CH2 Br HBr
In this reaction anti Markownikoff’s addition is CH3 CH CH2 ¾ ¾ ¾® CH3 —CH—CH3
explained on the basis of the fact that in the presence
in absence of
peroxide
½
peroxides, Addition takes place via free radical Br
(Markownikoff addition)
mechanism rather than the ionic mechanism. 68. (b) CH 2 = CH - Cl + HCl ¾¾® CH 3CHCl 2
60. (d) The two hydrogen atoms on first carbon and the two
Addition of HCl takes place according to
H-atoms on the third carbon atom lie in perpendicular
Markownikoff’s rule. (H goes to C which is least
planes. The central carbon atom is sp-hybridized while
substituted)
terminal carbon atoms are sp2-hybridized
61. (a) The p bond is formed by the sideways overlapping of CH 2 CH3 H2 O
two p-orbitals of the two carbon atoms. 69. (a) P + H 2SO4 ® | ¾¾¾ ®
CH 2 CH 2 HSO 4
The molecular plane does not have any p electron
density as the p-orbitals are perpendicular to the plane CH3
containing the ethene molecule. The nodal plane in the | + H 2SO 4
p-bond of ethene is located in the molecular plane. CH 2OH
62. (c) Except ethyl alcohol, no other primary alcohol can be
63. (b) Stability of an alkene depends upon the heat of prepared by this method as the addition of H2SO4
hydrogenation of an alkene. The heat of hydration is follows Markownikoff’s rule. Generally secondary and
the standard enthalpy change in hydrogenation of on tertiary alcohols are obtained.
alkene. The lower the heat of hydrogenation of an 70. (c)
alkene higher will be stability. 71. (d) Nature of halogen atom and the alkyl group both
Order of stability Heat of hydrogenation determine rate of reaction.
(kJ/mol) 72. (c) When both double and triple bonds are present, then
trans-2-butene – 115.5 triple bond is considered as the principal group.
cis-2-butene – 119.6 and CH3 - CH = CH - C º CH
1-butene – 126.8 respectively. 5 4 3 2 1
HYDROCARBONS 533

73. (b) Three alkynes are possible for the formula C5H8.
H3C H3C
CH3CH2CH2C º CH
CH 3
85. (a) 3CH 3 - C º CH ¾¾
®
{
– C º CH
CH3 ¾ CH
H3C

CH3CH2C º CCH3
CH3 CH CH3
74. (c) On heating an ethylene chloride (1, 1 dichloro ethane)
with alcoholic potash followed by sodamide alkyne is C C
obtained
alc.KOH
R - CH 2 - CCl 2 - R ¾¾¾¾® R - CH = CCl - R CH CH
NaNH 2
¾¾¾¾ ®R - C º C - R C
75. (c) CaC2 + 2H2O ¾
¾® HC º CH + Ca (OH)2
Calcium Acetylene
carbide CH3
76. (d) Among isomeric alkanes, the straight chain isomer Mesitylene or 1, 3, 5-trimethyl benzene
has higher boiling point than the branched chain
isomer. The greater the branching of the chain, the Lindlar's
lower is the boiling point. Further due to the presence 86. (b) CH º CH + H 2 ¾¾¾¾¾
® CH 2 = CH 2
Acetyle Catalyst
Ethylene
of p electrons, these molecules are slightly polar and Pd. BaSO4
hence have higher boiling points than the Ni
corrosponding alkanes. 87. (d) Addition – CH º CH + 3H 2 ¾¾® CH 3 - CH 3
77. (a) Terminal alkyenes give a white precipitate easily on Substitution –
reaction with ammonical silver nitrate solution. 1
dil H 2SO 4
® CH º C - Na + + H 2
CH º CH + Na ¾¾
78. (b) CH º CH + H 2 O ¾¾¾¾¾¾ ® 2
HgSO 4 .60° C Polymerization –
[CH 2 = CHOH] ¾¾
® CH3CHO hot Cu tube
3CH º CH ¾¾¾¾¾¾® C6 H 6
unstable Polymerization
Benzene
79. (b) HCl
CH º CH + HCl ® CH 2 = CH - Cl ¾¾¾
® Br
Cl |
CH3 – CH 88. (b) CH3C º CH + 2HBr ¾¾
® CH3 - C - CH3
Cl |
1, 1-Dichloroethane
Br
80. (b) Alkynes having terminal –C º H react with Na in
89. (b)
liquid ammonia to yield H2 gas.
90. (b) Thin film of polyacetylene can be used as electrodes in
Na in
CH3CH 2 C º CH ¾¾¾¾¾
® batteries. These films are good conductors, lighter and
liquid NH 3
cheaper than the metal conductors.
1
CH3CH 2C º C – Na + + H 2 ( g ) 91. (b) For statement (ii), alkynes on reduction with Pd/C form
2 cis-alkenes. For statement (iv), propyne on reduction
81. (a) Acetylene reacts with the other three as: with Pd/C forms propene. Propene does not show
CH2 geometrical isomerism. Only those compounds show
Na
CH º CNa CH º CH +HCl geometrical isomerism which have two different atoms
liq. NH3
CHCl or groups attached to each carbon atom.
CH CH3 CH3 H
C C
CHCl CHCl2 H H
Propene
[AgNO3+NH4OH] 92. (a) (i) HC º C - CH 2 - CH 2 - CH 2 - CH3
CH º CH AgCºCAg + NH 4NO 3
white ppt. Hex -1- yne
(ii) CH3 - C º C - CH 2 - CH 2 - CH3
82. (c) 83. (d)
Hex -2 - yne
40% H SO
84. (c) CH3 - C º CH + H 2O ¾¾¾¾¾®
2 4
(iii) CH3 - CH 2 - C º C - CH 2 - CH3
1% HgSO4
Hex -3- yne
Rearrangement
CH3 - C = CH 2 ¾¾¾¾¾¾® CH3 - C - CH3 (iv) HC º C - CH - CH 2 - CH3
| P |
OH O CH3
Acetone 3- Methylpent -1-yne
 EBD_7374
534 CHEMISTRY

(v) HC º C - CH 2 - CH - CH3 102. (a) This is an example of decarboxylation reaction.

| COONa
CH3
4- Methylpent -1-yne
NaOH + CaO
(vi) CH3 - C º C - CH - CH3 + Na2CO3
|
CH3 103. (a) Y = –COOH because it is meta directing group while
4- Methylpent -2-yne –NH2, – OH and –Cl are o and p directing groups.
CH3 NO2 NO2
|
(vii) HC º C - C - CH 3
HNO 3 Br2
| 104. (a)
CH3 H 2SO 4 FeBr3
Br
3,3- Dimethylbut-1-yne
93. (a) Ethylene has restricted rotation, acetylene has no 105. (c) Cl exhibits –I effect and +M effect.
rotation, hexachloroethane has more rotation than
Ni
ethylene but less than ethane because of greater size + 3H2 ¾¾®
of the substituent (chlorine) in hexachloroethane than 106. (b)
Benzene Cyclohexane
in ethane (substituent is hydrogen).
94. (a) The acidity of acetylene or 1–alkyne can be explained 107. (d)
on the basis of molecular orbital concept according to CH3
which formation of C—H bond in acetylene involves
sp-hybridised carbon atom. Now since s electrons are anhydrous AlCl
108. (c) + CH3Cl ¾¾¾¾¾¾
¾3® + HCl
closer to the nucleus than p electrons, the electrons
present in a bond having more s character will be
correspondingly more closer to the nucleus. 109. (b) Benzene can be obtained by polymerisation of
Thus owing to high s character of the C—H bond in acetylene.
alkynes (s = 50%), the electrons constituting this bond
Red hot tube
are more strongly held by the carbon nucleus i.e., the 3HC º CH ¾¾¾¾¾®
500°C
acetylenic carbon atom or the sp orbital acts as more
electronegative species than the sp2 and sp3 with the 110. (a) This is an example of Friedel - Craft alkylation.
result the hydrogen present on such a carbon atom 111. (d)
(ºC—H) can be easily removed as a proton. O O
95. (a) Only terminal alkynes show acidic nature. Ethyne is O
O
more acidic than propyne. But-2-yne is not acidic as it 112. (c) + O3 O
does not contain any hydrogen attached to sp O
O
hybridised carbon. O O
96. (a) Benzene triozonide
97. (c) Due to the maximum percentage of s character (50%), 113. (b) Friedel- Craft reaction occurs in presence of an attacking
the sp hybridised orbitals of carbon atoms in ethyne reagent which is an electrophile (AlCl3).
molecules have highest electronegativity; hence, these 114. (a) According to experimental evidences, electrophilic
attract the shared electron pair of the C-H bond of substitution reactions are supposed to proceed via the
ethyne to a greater extent than that of the sp 2 following three steps:
hybridised orbitals of carbon in ethene and the sp3 (1) Generation of the electrophile
hybridised orbital of carbon in ethane. Thus in ethyne, (2) Formation of carbocation intermediate
hydrogen atoms can be liberated as protons more easily (3) Removal of proton from the carbocation intermediate
as compared to ethene and ethane. 115. (b)
98. (c) They have a relatively high percentage of carbon. H
.. ∗ ,
99. (c) HO3SO , H ∗ H , O .. , NO 2 H,O .. , NO2 ∗ HSO 4
100. (c) Benzene does not show addition reactions like other
unsaturated h ydrocarbons. However, it show H
Å
+
substitution reactions. Due to resonance all the C – C H -O
.. - NO 2 H 2 O + NO 2
bonds have the same nature, which is possible because
Protonated Nitronium ion
of the cyclic delocalisation of p -electrons in benzene.
nitric acid
Monosubstitution will give only a single product. In the process of generation of nitronium ion, sulphuric
101. (d) Benzene can be obtained by all the compounds given. acid serves as an acid and nitric acid as a base.
HYDROCARBONS 535

116. (a) p-Electrons of benzene rings are delocalised throughout

Exercise - 2
the molecule. This makes the molecule very stable. The
stability resists breaking of double bonds for addition. 1. (d) We know that, as the number of carbon atom increases,
117. (d) Polynuclear hydrocarbons are not produced in human boiling point increases while boiling point decreases
body by any biochemical reaction However, when they with branching.
enter into human body they undergo various 2, 2-dimethyl propane, CH3
biochemical reactions which finally damage DNA and |
cause cancer. H3C – C – CH3
118. (a) (A) C6H 6 + Cl 2 ¾¾¾®
AlCl3
C6H5Cl |
(Benzene) (Chlorobenzene)
CH3
AlCl3 b.pt = 282.5 K
(B) C6 H6 + CH3Cl ¾¾¾® C6H5CH3 + HCl
(Toluene) n – pentane, b.pt = 309.1 K
(C) C6 H 6 + CH 3 COCl ¾¾
® C6 H 5COCH3 + HCl 2-methyl butane, H3 C — H 2 C — HC — CH3
Methyl phenyl |
ketone CH3
KMnO
(D) C6 H5 - CH3 ¾¾¾¾
4 ® C H COOH
6 5
b.pt = 301 K
NaOH
(Toulene) n-butane, b.pt = 273 K
119. (d) 120. (a) 2. (a) Reactivity of halogens decreases with decrease in
121. (c) (4n + 2)p electrons and planar structure are the essential electronegativity which decreases down the group.
conditions for aromaticity. Hence the order of reactivity of alkanes with halogens
122. (c) In arenes, p electrons are delocalised, hence arenes do is
not undergo addition reactions easily. Aromatic F2 > Cl2 > Br2 > I2.
compounds (arenes) are highly stable and show Also with I2, the reaction is too slow that it requires a
resonance. eg. benzene is the simplest example. catalyst.
123. (d) In benzene due to delocalisation of p - electrons, all the 3. (b) The reactivity of halogens with alkanes follows the
C – C bond lengths are equal as each C– C bond has order : F2 > Cl2 > Br2 > I2. Further, the reactivity of
some double bond character and thus the bond length reduction of alkyl halides with Zn & dilute HCl
is between single and double bond, i.e., between C2H6 increases as the strength of C – X (X = F, Cl , Br, I)
and C2H4. bond decreases. Hence, reduction of alkyl halide with
124. (d) It has delocalised p orbitals. Zn and dilute HCl follows the order :
125. (c) Benzene has 12 s and 3 p bonds. R – I > R – Br > R – Cl.
\ Ratio of s bonds to p bonds = 12/3 = 4 4. (a) The correct IUPAC name of the alkane will be :
126. (d) Presence of 6p orbitals, each containing one
unpaired electron in a six membered cyclic structure
is in accordance with Huckel rule of aromaticity. H3C - CH 2 - C H - CH 2 - CH2 - C H - CH2 - CH3
|3 4 5 6| 7 8
127. (a) 2
CH CH2
Cl 1 |
CH3 CH3 CH3

Cl2, anly AlCl 3 (Subtitution)

+ HCl
3, 6-diethyl -2-methyloctane.
3Cl2, sunlight (Addition) Cl 5. (a) 1-butene is an unsymmetrical alkene and will follow
Cl Cl Markownikoff's rule to give major product.
Benzene
CH3 - CH 2 - CH = CH 2 + H - Br ¾¾ ®
Cl I-Butene
Cl
Cl
128. (b) –Cl group is o-, p-directing due to +R effect ; however + H – Br +
it is deactivating due to strong –I effect of Cl (difference
H
from other o-, p-directing groups which are activating). minor more stable (2°)
The net result is that chlorobenzene undergoes o, p- product(s) trigonal planar
substitution, but with difficulty carbocation
129. (b) C6 H5COOH + NaOH ® C6H 5COONa + H 2O H H Br s
(X) +
distill
C6 H5OH + Zn ¾¾¾® C6H 6 + ZnO
(Y) Br Br
130. (a) Huckel rule is not obeyed. It has only four electrons.
Racemic mixtures
Further it does not have continous conjugation. (major products)
 EBD_7374
536 CHEMISTRY

6. (d) In option (d), a carbon with double bond has two same
functional groups (CH3) attached to it. The rotation 16. (a) CH3 CH3
around carbon will not produce a new compound. CH3 – C – Cl + 2Na + Cl – C – CH3
Hence, geometrical isomerism is not possible.
7. (c) Lesser the bond energy of hydrogen halide more will CH3 CH3
t-Butyl chloride
be its reactivity. Hence, the order of reactivity of given

Wurtz
Rxn
compounds with propene will be HI > HBr > HCl.
8. (b) + I-effect decreases the stability of carbanion. Since, –
CH3 group shows + I-effect, therefore, it intensifies CH3 CH3 CH3 CH3
the negative charge and hence destabilises the CH3 – C – C –CH2Cl CH – C – C – CH3
3
Mono
carbanion (A) relative to (B). CH3CH3 Chlorination CH3 CH3
Also, sp hybridised carbanion is more stabilised than
sp3.
CH º C - > CH3 — C º C - > CH3 — CH 2
17. (b) CH3C = C - CH3
| |
( B )sp ( A )sp ( C )sp3 CH3 CH3
Hence, the order of decreasing stability will be : B > A > C 2,3-Dimethyl-2-butene
9. (d) Alkyl halides on heating with alcoholic KOH eliminates
halogen from a-carbon atom and hydrogen is (CH3)2CH – CH – CH = CH2 contain 7 carbon atoms
|
eliminated from b-carbon atom to form an alkene. CH3
3°b- carbon
CH3 CH3
(A) CH3 — CH — CH 2 Br
| CH3 – C – CH = CH2+ H +
CH3 – C – CH +– CH3
CH3
(A) CH3 CH3
1°b-carbon Rearrangement
(B) CH3 — CH 2 — Br
CH3
2°b - carbon CH3 CH3 CH3
(C) CH3 — CH2 — CH2 — Br
C=C CH3 – C – C
CH3 CH3 + CH3
More the number of B-substituents (alkyl groups) more H
stable alkene will be formed on b-elimination, more will 2, 3 - dimethyl – 2 - butene (Stable 3° carbocation)
18. (c) 1-chloro-1-methylcyclohexane.
be the reactivity. Thus the correct order is A > C > B
10. (c) During incomplete combustion of alkanes with CH3
insufficient amount of air carbon black is formed which Cl
is used in the manufacture of ink, printer ink, black
pigments and as filters.

CH 4 ( g ) + O2 ( g ) ¾¾¾¾¾
Incomplete
® C ( s ) + 2H 2O ( l ) CH3
combustion
Carbon black
CH2 CH3
Cl
11. (b) The combustion reaction of ethylene is –
+ H – Cl + Cl
5
C2 H 2 + O2 ® 2CO2 + H 2 O
2 CH3 CH3 CH3
Both HC CH and CO2 have sp hybridization. H
Cl
H
12. (c) When non-terminal alkynes are heated with NaNH2 in + H – Cl + Cl
an inert solvent, the triple bond migrates to the end
carbon atom.
13. (c) The assertion that trans-2 butene reacts with Br 2 to H3C
product meso-2, 3-dibromobutane is correct but it does 19. (d) H3C
O3 O=C
not involve syn-addition of Br 2. CH3 Zn + H2O
CH3
14. (c) (4n + 2)p electrons and planar structure are the essential OHC
conditions for aromaticity. 5-Keto-3-methylhexanal
Cl
|
15. (c) 2Cl - C - CH3 + 6Ag ® CH3C º CCH3 + 6Ag Cl 20. (a) No. of double bonds = 4
| 2-Butyne No. of p bond electrons
Cl = 2 × no. of double bond
1,1,1-Trichloroethane
=2× 4=8
HYDROCARBONS 537

21. (a) Enthalpy of hydrogenation

1 • Br •
µ CH3CH 2CHBr CH 2 ¬¾¾
¾ CH3CH 2 CH=CH 2
stability of alkene 1° free radical
(less stable)
\ III > II > I
VO
22. (b) 2C6 H 6 (g) + 9O 2 (g) ¾¾¾
2 5¾
® Br• • •
410°C ¾¾¾
® CH3CH 2 C HCH 2 Br
® CH 3CH 2 C HCH 2 Br
O 2° free radical 2° free radical
(more stable) (more stable)
CH—C 26. (d) When 1, 3-dimethylcyclopentene is heated with ozone
O + 4CO2(g) + 4H2O(g)
and then with zinc and acetic acid, oxidative cleavage
CH—C
leads to keto - aldehyde.
O CH3 CH3
Maleic anhydride O
23. (d) (i) O - 78° C
24. (d) Br2 in CCl4 (a), Br2 in CH3COOH (b) and alk. KMnO4 (c) ¾¾ ¾3¾ ¾ ¾ ¾ ® O C–H
(ii) Zn- CH 3COOH
will react with all unsaturated compounds, i.e., 1, 3 and
4 while ammonical AgNO3 (d) reacts only with terminal CH3 CH3
alkynes, i.e., 3 and hence 3 can be distinguished from
1, 2 and 4 by. ammonical AgNO3 (d).
O O
25. (c) Here assertion is correct but reasoning is incorect. In || ||
presence of peroxide, addition of HBr on alkenes takes CH3 — C— CH 2 — CH 2 — CH— C— H
place via free radicals; here two free radical are formed, |
2° free radical, being more stable, governs the CH3
product. 5-Keto-2-methylhexanal
+
27. (a) HCº CH ¾¾¾¾¾¾¾¾¾¾¾
NaNH 3 2
2 ® HCº CNa ¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾ H C –CH - Br
® HC º C – CH 2 – CH3
liq. NH3
(X)
1-Butyne NaNH2 liq. NH3
+
3 2 H C - CH – Br
H3 C – CH 2 – Cº C – CH 2 – CH3 ¬¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾¾
¾ H3 C – CH 2 – C º C N a
3-Hexyne (Y)

28. (a) The addition of HBr takes place according to anti-

Br HO
Markovnikoff’s rule in presence of peroxide for NBS H2O/K2CO3
unsymmetrical alkenes.
The addition of HBr to symmetrical alkenes is not
affected by the presence or absence of peroxide.
29. (d) 32. (d) D 2SO 4 transfers D +, an electrophile, to form
30. (d) +
hexadeuterobenzene.
CH2 – CH – CH3
+
33. (c) Catalytic hydrogenation of alkynes gives cis-alkene
sp 3 CH = CH – CH + Cl – Cl More stable intermediate
2 3
which in turn adds deuterium atoms in presence of H2
+ again in cis-manner forming meso-2, 3-dideuterobutane.
CH2 – CH – CH3
34. (c) There is no change in bond angles and bond lengths
Cl in the conformations of ethane.
+ – 35. (a) Correct order is
CH2 – CH – CH3 OH CH2 – CH – CH3
H - C º C - H > H3C - C º C - H > H 2C = CH 2 > CH3 - CH3
Cl Cl OH
31. (d) N – bromosuccinimide results into bromination at allylic
and benzylic positions
( Two acidic
hydrogens ) ( One acidic
hydrogen )
36. (c) Hydration of alkynes give ketones.
OH
NBS/hv
H3 C - C º CH ¾ ¾
® H3C - C = CH 2
(A)
O
Tautomerism
H3 C - C - CH3
(B)

More stable
 EBD_7374
538 CHEMISTRY

1%HgSO CH MgX CCl3 CH3

37. (c) HC º CH ¾¾¾ ¾
¾4 ® CH CHO ¾¾ ¾
3
3 ¾
¾®
20%H 2SO4 [A ] H 2O
Zn
¾¾®
HCl
[O]
CH 3CHOHCH 3 ¾¾®
¾ CH 3COCH 3 Br Br
[ B] Acetone [C] m-Bromotoluene
38. (d) A doubly bonded carbon atom having an alkyl group 44. (b) Ph – CH2 – CH2 – C º C – CH3
is oxidised to aldehyde which is further oxidised to
carboxylic acid. Ph – CH2 – CH2 CH3
Na/NH
¾¾¾¾
3® C= C
(i) KMnO ,OH -
CH3CH 2CH = CH CH3 ¾¾¾¾¾¾¾
4
+
® H H
(ii) H
CH3CHO + CH3CH 2CHO (A)
¯ ¯ Ph – CH(Cl) – CH2
CH3COOH CH3CH 2COOH Cl /hv H
¾¾¾¾
2 ® C= C
39. (c) Benzene has a uniform C – C bond distance of 139 H CH3
pm, a value intermediate between the C – C single.
(B)
(154 pm) and C = C double (134 pm) bonds.
40. (d) If two chirality centres are created as a result of an Na/NH3(l) is Birch reduction which reduces only
addition reaction four stereoisomers can be obtained alkyne into trans alkene and Cl2/hv is free radical sub-
as products. stitution reaction.
45. (d) It is diamagnetic substance so weakly repelled.
H3C CH3
HBr Na/liq.NH
C = C ¾ –¾ ¾®
H2 O
46. (c) ¾¾¾¾¾¾ 3
®
Birch reduction
H C2H5
cis-3, methyl pent-2-ene COOH
Br CH3 CH2 – CH3
| | ( KMnO4 )
CH3 – CH – CH – CH2 – CH3 ¾¾¾¾¾ ®
* * 47. (d) KOH
2, Bromo, 3-methyl pentane
(2 chiral centre) (B)
CH3 CH3
COOH COOC2H5
H Br Br H
Br2 C H OH
¾¾¾¾®
2 5
+
H CH3 H3C H FeCl3 H
Br Br
(C) (D)
C2H5 C2H5
Exercise - 3
(I) (II)
1. (c)
CH3 CH3 2. (a) Bromine is more selective
\ abstract that hydrogen which forms stable free- radical
Br H H Br CH3
.
H CH3 H3C H
\ (3° free-radical) is most stable.
C2H5 C2H5
(III) (IV)
CH3
41. (c) Note that in structures 1 and 2, every two adjacent 3. (b) Cumulative dienes.
hydrogen atoms are at maximum possible distance from 4. (b) Formation of carbocation is the rate determining step more
each other (staggered conformation). the stable carbocation more is the reactivity toward HBr.
Br Na
CH3 + CH3 +
42. (c) CH 4 ¾¾¾
2 ® CH – Br ¾¾¾
3 ® CH 3 – CH 3 C CH3 > C CH3 >
hv ether
(less than four 'C') CH3O CH3
(b) (a)
CH3 CCl3 resonance stabilized (9a)
CH3 +
43. (a) 3Cl2 Br2 C CH3
¾¾®
D
¾¾®
Fe CH3OCH2
(c)
(–1)
HYDROCARBONS 539

5. (d) Rate of electrophilic addition µ Nucleophilicity of CH3 - CO

(O)
alkene µ stability of carbocation, so order IV > I > II > III. | + H 2O 2 ¾¾¾ ®
CH3CH 2 CO
H2 Ethylmehylglyoxal
6. (a) CH3 CH2 CH CH CH2 CH3 Platinum CH3COOH + CH3CH2COOH
CH3 CH2 CH2 CH2 CH2 Acetic acid Propionic acid
HBr The glyoxal formed as an intermediate is oxidised by H2O2
CH3 to give the acids.`
CH3 CH2 CH CH2 CH2 CH3
+1
Br
7. (b) Addition on triple bond takes place by the syn-addition 9. (d) (Individual ring are aromatic)

of hydrogen in presence of poisoned palladium

catalyst. –1
Since the configuration of the double bond already
present is cis, the compound formed will have a plane 10. (c) Cl2/hv Þ Free radical mechanism
of symmetry and hence optically inactive. Cl2/AlCl3 Þ Electrophilic aromatic substituion.
According to Baker-Nathan effect, hyperconjugation
Me H dominates over inductive effect.
Me
Me H Me
Me Hence ortho-position of methly group has more e–
H density for EAS.
H 11. (d) For a compound to be aromatic it must have
Me H (4n + 2) pe– where n is an integer. (III) have 8 and
H H (VI) have 4e–. Hence are Antiaromatic

8. (b) O
CH 3 - C º C - CH 2 - CH 3 ¾¾3 ® + Br
O + –
2H2O H Br
CH3 – C – C – CH2 – CH3 12. (b)
O O
Pentyne ozonide OH OH OH
Benzyl cabocation
(more stable)
13. (c) Here hydration occurs in anti-Markovnikov’s way because of electron-withdrawing nature of –COOH which destabilises
carbocation I more than the II.
+ + +
H
HC C – COOH H2C = C COOH or HC = CH COOH
I (+ve charge II (+ve charge
more intensified) less intensified)
– More stable
+ OH
HC CH – COOH HC = CH – COOH OHC – CH2 – COOH
II OH
14. (d) The intermediate s complex II is much more stable than III which is equally stable to I.
CH 3 CH3 CH3
E E E
H >> H » H
+ + +
CH 3
CH 3
II III I
Two resonating structures are 3° Only one resonating structure Only one resonating
carbocation (most stable) is 3° carbocation is 3° carbocation
15. (d) Compound in which all hydrogen atoms are equivalent will form one monochloro derivative, which is (d) here
CH3
(a) CH 3 (CH 2 ) 6 CH 3 (b) CH CHCH2(CH2)3CH3
3
CH3 CH3 CH3 CH3
| | | |
(c) CH 3 C CH 2 C HCH 3 (d) CH 3 - C - C - CH 3
| | |
CH3 CH3 CH3
 EBD_7374
540 CHEMISTRY

14. ENVIRONMENTAL CHEMISTRY

Exercise - 1 NO + O 3 ¾ ¾® NO 2 + O2
O3 + h u ¾ ¾® O 2 + O
1. (d) DDT causes air, water and soil pollution. NO 2 + O ¾ ¾® NO + O 2
2. (d) DDT is a non-biodegradable pollutant. 2 O3 + h u ¾¾® 3 O 2 (Net reaction)
3. (c) Troposphere contains water vapour. The presence of oxides of nitrogen increase the
4. (b) High concentration of SO2 leads to stiffness of decomposition of O3.
flower buds. hn •
5. (b) CO2 is generally not regarded as pollutant. 29. (c) CF2 Cl 2 ¾¾® CF2 Cl + Cl
• •
6. (c) CO and oxides of Nitrogen are poisnous gases present Cl + O3 ¾ ¾® Cl O + O 2
in automobile exhaust gases. 30. (a) In antarctica ozone depletion is due to formation of
7. (b) Nitric oxide (NO) which may be produced at the ground acrolein.
level due to human activity or natural sources or is 31. (d) Ozone absorbs U.V. radiations harmful to human life.
produced in large amounts in the exhaust gases by the 32. (d) 33. (d)
engine of supersonic transport planes and introduced 34. (a) Classical smog is also called reducing smog.
directly into the stratosphere. 35. (a) 36. (b) 37. (c)
NO + O3 ¾® NO2 + O2 38. (d) London smog is formed in morning during winter.
8. (d) CO is highly toxic and impairs respiration. CO combine 39. (a) PSCs react with chlorine nitrate and HCl to give HOCl
with haemoglobin of blood and reduces its O2 carrying 40. (a)
capacity. 41. (a) NO and freons are responsible for ozone depletion.
9. (d) 42. (d)
10. (a) Radiation coming from sun or outerspace have high 43. (c) H2, He and ionic oxygen are present in exosphere.
energy or short wavelength, which are allowed to enter 44. (a) The presence of particulate matter in polluted air
by green house gases. However, radiation emitted by catalyses the oxidation of SO2 to SO3
earth is in infrared region, having long wavelength, are 45. (b)
reflected back by the envelope of green house gases. 46. (b) At high altitudes when lightening strikes dinitrogen
11. (a) Green house gases such as CO2, ozone, methane, the and dioxygen combine to form oxides of nitrogen.
chlorofluorocarbon compounds and water vapour form 47. (a) The average residence time of NO is 4 days.
a thick cover around the earth which prevents the IR and Cl2.
rays emitted by the earth to escape. It gradually leads 48. (c)
to increase in temperature of atmosphere. 49. (d) 3CH4 + 2O3 ® 3CH2= O + 3H2O
12. (a) CO2 is a green house gas. Formaldehyde
13. (d) CH2 == CHCH == O; CH3COONO2
14. (d) Acid rain contains H2SO4 > HNO3> HCl. Acrolein Peroxyacetyl nitrate (PAN)
15. (d) 50. (d) Minamata is caused by Hg poisoning.
16. (b) Large amounts of CH4 are released in paddy fields, 51. (c) 52. (c) 53. (a) 54. (b)
coal mines and by fossil fuels. 55. (b) Eutrophication is a natural process which literally means
17. (a) 18. (b) well nourished or enriched. It is a natural state in many
19. (a) Smog is caused by oxides of sulphur and nitrogen. lakes and ponds which have a rich supply of nutrients.
20. (a) 21. (a) 22. (a) 23. (c) 24. (b) 25. (d) Eutrophication become excessive, however when
26. (a) PAH (Poly Aromatic Hydrocarbon) abnormally high amount of nutrient from sewage,
27. (c) Usually catalytic converters are used in the fertilizers, animal wastage and detergent, enter streams
automobiles, which prevent the release of nitrogen and lakes causes excessive growth or blooms of
oxide and hydrocarbons to the atmosphere. Certain microorganisms. With increasing eutrophication, the
plants e.g., Pinus, Juniparus. Quercus, Pyrus and diversity of the phytoplankton community of a lake
Vitis can metabolise nitrogen oxide and therefore, increases and the lake finally becomes dominated by
their plantation could help in this matter. blue - green algae.
28. (c) The ozone layer, existing between 20 to 35 km above 56. (b) Sewage water is purified by micro-organisms.
the earth’s surface, shield the earth from the harmful 57. (c) Water is often treated with Cl2 to kill germs.
U. V. radiations from the sun. 58. (d) Decrease in D.O causes death of fish.
Depletion of ozone is caused by oxides of nitrogen 59. (b) Strength of sewage or degree of water pollution is
N 2O + h u ¾ ¾® NO + N measured in terms of BOD (Biochemical oxygen
reactive nitric oxide demand) value.
ENVIRONMENTAL CHEMISTRY 541

60. (d) 90. (b) Ethanal is commerically prepared by one step oxidation
61. (b) The ideal value of DO for growth of fishes is 8 mg/L. 7 of ethene in the presence of ionic catalyst in
mg/L is desirable range, below this value fishes get aqueous medium with an yield of 90%.
susceptible to disease. A value of 2 mg/L or below is Catalyst
lethal for fishes. CH2 = CH2 + O2 ¾¾¾¾¾¾
Pb(II)| Cu(II)
® CH3CHO
62. (b) Water pollution is mainly caused by industrial wastes, (in water)
sewage, insecticide, herbicides, etc.
63. (d) Addition of phosphate fertilizers to water leads to Exercise - 2
nutrient enrichment (eutrophication). 1. (a) Those gases which absorb sunlight near the earth's
64. (a) BOD of pond is connected with microbes and organic surface and then radiates back to the earth are called
matter. green house gases.
65. (d) Carbon dioxide, water vapour, methane, ozone, oxides
66. (a) Eutrophication causes reduction in D.O of nitrogen, chlorofluoro carbons (CFCs) etc; are green
67. (d) For statement (iii), Methemoglobinemia (blue baby house gases. CO is not a green house gas.
syndrome) is caused due to excess of nitrate in 2. (c) The smog which is formed in presence of sunlight is
drinking water. called photochemical smog. The main components of
For statement (iv), Excessive sulphate (> 500 ppm) in the photochemical smog results from the action of
drinking water causes laxative effect, otherwise at sunlight on unsaturated hydrocarbons and nitrogen
moderate levels it is harmless. oxides produced by automobiles and factories.
68. (c) 3. (a) Classical smog occurs in cold humid climate. It is a
69. (b) Domestic sewage constitute biodegradable pollutants. mixture of smoke, fog and sulphur dioxide.
70. (a) The F– ions make the enamel on teeth much harder 4. (a) Water considered to be clean if it has BOD less than
by converting hydroxyapatite, [3(Ca 3(PO 4)] 2. 5 ppm whereas highly polluted water has BOD more
Ca(OH)2]. the enamel on the surface of the teeth, into than 17 ppm.
much harder fluorapatite, [3(Ca3(PO4)2. CaF2]. Therefore, water having BOD less than 5 ppm is rich in
71. (c) The excess of fluorine in water causes fluorosis. The dissolved oxygen.
symptoms of fluorosis are mottling of teeth (yellowish 5. (a) O3 is responsible for greenhouse effect. Its contribution
streaks) and abnormal bones liable to fracture etc. It is is about 8%.
an example of endemic disease. 6. (c) The large population of bacteria decomposes organic
72. (b) matter present in water. They consume oxygen
73. (c) Because they are very sensitive to sulphur dioxide and dissolved in water. Hence, oxygen from water
in cities the amount of SO2 is high so lichen do not decreases. It is harmful for aquatic life.
grow in cities. 7. (b) Photochemical smog has high concentration of oxidants
74. (a) 75. (d) 76. (c) 77. (d) such as O3, organic oxidant and is therefore called as
78. (b) Pesticides and synthetic fertilizers pollute the soil. oxidising agent.
79. (a) Lower trophic level has lower toxins deposition than 8. (b) The lowest region of the atmosphere in which human
higher trophic level. beings along with other organisms live is called
80. (c) 81. (a) 82. (a) troposhere. It extends upto the height of ~ 10 km from
83. (b) Thermal pollution is caused by power plants. Power sea level. Troposphere is a turbulent, dusty zone
plant requires a larger quantity of water for cooling. containing air, much water vapour and clouds.
The water after cooling is left in the water body. The 9. (a) Nitrogen and oxygen do not react with each other at
temperature of left water is generally very high and normal temperature. At high altitude when lightning
affects aquatic life. strikes, they combine to form oxides of nitrogen.
84. (a) 85. (a) 3000° C
86. (b) This represents a great step forward for green chemistry. N 2 ( g ) + O 2 ( g ) ¾¾¾¾® 2NO ( g )
87. (d) All the given statements are true for about waste 10. (c) Hydrocarbons present in atmosphere combine with
recycling. oxygen atom produced by the photolysis of NO2 to
88. (b) Green chemistry may be defined as the programme of form highly reactive intermediate called free radical.
developing new chemical products and chemical Free radical initiates a series of reaction.
processes or making improvements in the already Peroxyacetyl nitrates are formed, which can be said as
existing compounds and processes so as to make less secondary pollutants.
harmful to human health and environment. This means .
Hydrocarbon + O ® RCO (free radicals)
the same as to reduce the use and production of
hazardous chemicals. .
RCO + O2 ® RCO3
89. (b) Replacement of earlier used tetra-chloroethene as
solvent for dry cleaning by liquid CO2 results in less RCO3g + NO2 ® RCO3 NO 2
harm to ground water. Peroxyacetyl nitrate
 EBD_7374
542 CHEMISTRY

11. (c) Ozone hole is thinning of ozone layer of stratosphere 22. (a) The maximum limit of nitrate in drinking water is
at some place. NO and chlorofluorocarbon have been 50 ppm. Excess nitrate in drinking water can cause
found to be the most responsible for depleting the disease such as methemoglobinemia ('blue baby'
ozone layer. syndrome).
12. (d) Using plastic cans for neatly storing substances will 23. (a) Microorganisms present in the soil is a sink for CO.
not come under green chemistry. The plastic materials 24. (c) Above 2 ppm concentration of F– in drinking water
are non-biodegradable. cause brown mottling of teeth.
13. (d) The oxidised hydrocarbons and ozone in presence of 25. (c) Photochemical smog does not involve SO2.
humidity cause photochemical smong. 26. (a) Nitrous oxide (N2O) occurs naturally in environment.
Hydrocarbons + O2, NO2, NO, O, O3 ® Peroxides, In automobile engine, when fuel is burnt dinitrogen
formaldehyde, peroxyacetyl-nitrate (PAN), acrodein etc. and dioxygen combine to yield NO and NO2.
Hence chlorofluoro carbons are not common
27. (c) [3Ca 3 (PO4 ) 2 .Ca(OH) 2 ] + 2F – ¾¾
®
component of photochemical smog. (drinking
water
14. (d) upto1ppm)
15. (a) Normal rain water has pH 5.6 Thunderstorm results in
the formation NO and HNO3 which lowers the pH. [3Ca 3 (PO4 ) 2 .CaF2 ]+ 2OH –
16. (d) Ozone layer acts as a shield and does not allow (Harder teeth
enamel)
ultraviolet radiation from sun to reach earth. It does
not prevent infra-red radiation from sun to reach earth, 28. (c) The ozone layer, existing between 20 to 35 km above
thus option (d) is wrong statement and so it is the the earth’s surface, shield the earth from the harmful
correct answer. U. V. radiations from the sun.
Depletion of ozone is caused by oxides of nitrogen
17. (b) SPM (Suspended Particulate Matter) is defined as
particles floating in the air with a diameter below 10 N 2O + h u ¾ ¾® NO + N
mm. Studies have shown that high SPM reactive nitric oxide
concentrations in the air can have a detrimental NO + O 3 ¾ ¾® NO 2 + O2
impact on respiratory organs. SPM is generated O3 + h u ¾ ¾® O 2 + O
from natural sources (e.g., volcanoes or dust storms) NO 2 + O ¾ ¾® NO + O 2
and human activities (vehicles, incinerators and 2 O3 + h u ¾¾® 3 O 2 (Net reaction)
industrial plants). The presence of oxides of nitrogen increase the
SPM Other aerosols decomposition of O3.
Less than 10 mm Less than 100 mm
Exercise - 3
Tend to float longer in Tend to settle fairly
Air due to small size due to comparative 1. (a)
quickly heaviness 2. (d) Tetrachloroethylene is widely used for dry-cleaning
Catalytic converters is a device designed to reduce fabrics and metal degreasing operations.
the amount of emissions from automobiles. The 3. (b) CFC > N2O > CH4 > CO2
current (so-called three-way) systems use a heated 4. (a)
metal catalyst to reduce the emissions of carbon 5. (d) In coming years, when the ozone layer will become
monoxide (CO), hydrocarbons, and nitric oxide (NO), thinner or will have hole, ultraviolet radiations will come
all of which contribute to the formation of directly to the earth that will cause cancer especially
photochemical smog. In an automobile’s exhaust related to skin like, melanoma.
system, a catalytic converter provides an 6. (d) 7. (c) 8. (d) 9. (d)
environment for a chemical reaction where unburned 10. (a) Water sample is reported to be highly polluted if BOD
hydrocarbons completely combust. value of sample is more than 17 ppm.
11. (b) In cold water, dissolved oxygen can reach a
18. (a) Nitrogen and oxygen in air do not react to form oxides
concentration upto 10 ppm, whereas oxygen in air is
of nitrogen in atmosphere because the reaction be-
about 200, 000 ppm.
tween nitrogen and oxygen requires high temperature.
12. (a) BOD of pond is connected with microbes and organic
19. (c) The high concentration of hydrocarbon pollutants in matter.
atmosphere causes cancer. 13. (b) Pesticides and synthetic fertilizers pollute the soil.
20. (c) NO pollutant is the main product of automobiles 14. (a) Lower trophic level has lower toxins deposition than
exhaust. higher trophic level.
21. (c) The irritant red haze in the traffic and congested places
15. (d) Lead
is due to the presence of oxides of nitrogen.
 15. THE SOLID STATE

Exercise - 1 æ 1ö
\ n = ç8 ´ ÷ + 1 = 2
è 8ø
1. (b) Crystalline solids are anisotropic in nature that is some
of their physical properties like electrical resistance or The fcc cell consists of 8 atoms at the eight corners
refractive index show different values when measured and one atom at each of the six faces. This atom at the
along different directions in the same crystals. face is shared by two unit cells.
2. (a) In crystalline solid there is perfect arrangement of the 1 æ 1ö
\n = 8´ + ç6´ ÷ = 4
constituent particles only at 0 K. As the temperature 8 è 2ø
increases the chance that a lattice site may be 1
22. (d) In a unit cell, W atoms at the corner = ´ 8 = 1
unoccupied by an ion increases. As the number of 8
defects increases with temperature solid changes into 1
liquid. O-atoms at the centre of edges = ´ 12 = 3
4
3. (b) Amorphous solids are isotropic, because these Na-atoms at the centre of the cube = 1
substances show same properties in all directions. W : O : Na = 1 : 3 : 1
4. (c) Glass is amorphous solid. Hence, formula = NaWO3
5. (c) Amorphous silicon is used as best photovoltaic
material available for conversion of sunlight into 1
23. (a) Number of A atoms = ´8 =1
electricity. 8
6. (c) Quartz glass is an example of amorphous solid and
1
crystalline solids are anisotropic in nature. Number of B atoms = ´6 = 3
7. (a) 8. (a) 2
9. (b) Among the given crystals, only silicon exists as a \ Formula AB3
covalent solid. It has diamond like structure. 1 1 1
10. (c) Covalent bond force 24. (b) A : B : C = ´8: ´ 2: ´ 4 = 1 : 1 : 2
8 2 2
11. (b) In graphite, the electrons are spread out between the
25. (a) Given: Atoms are present in the corners of cube = A
sheets.
and atom present at body centre = B. We know that a
12. (d) 13. (d)
cubic unit cell has 8 corners. Therefore contribution of
14. (b)
1
15. (a) Potassium crystallises in bcc lattice. each atom at the corner = . Since number of atoms
8
16. (b) For tetragonal a = b ¹ c , a = b = g = 90° 1
per unit cell is 8, therefore total contribution = 8 ´ = 1 .
17. (c) 8
18. (a) There are two atoms in a bcc unit cell. We also know that atoms in the body centre, therefore
So, number of atoms in 12.08 × 1023 unit cells number of atoms per unit cell = 1. Thus formula of the
= 2 × 12.08 × 1023 = 24.16 × 1023 atoms. compound is AB.
19. (d) Total number of atoms per unit cell for a face centered 26. (b) hcp is a closed packed arrangement in which the unit
cubic unit is 4. cell is hexagonal and coordination number is 12.
The atom at the body center completely belongs to 27. (b) Metals such as copper and silver crystallise in fcc
the unit cell in which it is present. structure while metals Mg and Zn crystallise in hcp
20. (a) Diamond is like ZnS. In diamond cubic unit cell, there structure.
are eight corner atoms, six face centered atoms and 28. (d)
four more atoms inside the structure. 29. (a) 30. (c)
Number of atoms present in a diamond cubic cell 31. (d) It represents ccp arrangement.
32. (a) 33. (d)
1 1
= 8´ ∗ 6´ ∗ 4 < 8 34. (d) Tetrahedral holes are smaller in size than octahedral
8 2
holes. Cations usually occupy less space than anions.
(corners) (face (inside 35. (a)
centered) body) 36. (d) Number of atoms per unit cell = 1
21. (d) The bcc cell consists of 8 atoms at the corners and one a
atom at centre. Contribution of each atom at each corner Atoms touch each other along edges. Hence r =
2
1 ( r = radius of atom and a = edge length)
is equal to .
8
 EBD_7374
544 CHEMISTRY

4 3 ZM
pr 44. (b) r=
3 p NA V
Therefore % fraction = =
(2 r )3 6
rN A V 8.92 ´ 6.02 ´ 1023 ´ (362)3 ´10-30
37. (b) Packing fraction is defined as the ratio of the volume Z= =
of the unit cell that is occupied by the spheres to the M 63.55
total volume of the unit cell. =4
P.F. for cpp and bcc are 0.74 and 0.68 respectively. \ It has fcc unit cell
So, the free space in ccp and bcc are 26% & 32% ZM
45. (a) For b.c.c., Z = 2, Now, d = and V = a3
respectively. NV
38. (b) In AB AB packing spheres occupy 74%. 26% is empty. 2 ´ 56
\ d= = 7.92 g ml–1
39. (a) For bcc lattice body diagonal = a 3 . (6.02 ´10 ) ´ (2.861´10-8 )3
23

The distance between the two oppositely charged ions Z´ M 2 ´ 100

a 46. (b) r= =
= 3 NA ´ a 3 6.023 ´ 10 23 ´ (400 ´ 10 -10 ) 3
2
387 ´ 1.732 = 5.188 g / cm 3
= = 335pm 3
2 d1 (a 2 )3 z1 æ 3 ö 4
40. (b) = ´ = ´ = 1.46
d 2 (a1 )3 z 2 çè 3.5 ÷ø 2
47. (c)

41. (a) 48. (a) Following generalization can be easily derived for
various types of lattice arrangements in cubic cells
between the edge length (a) of the cell and r the radius
of the sphere.
a
For simple cubic : a = 2r or r =
2
For body centred cubic :
Let radius of the sphere = r
Area occupied by sphere in hexagonal close packing 4 3
a= r or r = a
æ1 ö 3 4
pr 2 + 6 ´ ç ´ pr 2 ÷ = 2pr 2 For face centred cubic :
è 6 ø
é 3 ù 1
a = 2 2 r or r = a
Area of hexagonal = 6 ´ ê ´ (2r)2 ú 2 2
ë 4 û Thus the ratio of radii of spheres for these will be
3
= 6´ ´ 4r 2 simple : bcc : fcc
4 1
= 6 3 ´ r2 a 3
= : a: a
2pr 2 2 4 2 2
% occupied by = ´ 100 i.e. option (a) is correct answer.
6 ´ 3 ´ r2
49. (a) In fcc structure one unit cell consist 4 atoms, hence
2 ´ 3.14 density × a3 = The mass of four atoms
= ´ 100 = 60.43%
6´ 3 = 8.92 × (3.608 × 10–8)3
42. (b) For body centred cubic lattice Z = 2 = 4.18 × 10–22
Atomic mass of unit cell = 133 + 80 = 213 a.m.u ZM
Volume of cell = (436.6 × 10–10)3 cm3 50. (a) r =
NA V
ZM 2 ´ 213
Density, r = 3 = rNA V 2 ´ 6 ´ 1023 ´ (5 ´10-8 )3
a NA -
(436.6 ´ 10 10 )3 ´ 6.02 ´ 1023 Z= =
3
M 75
= 8.50 g/cm Z = 2, which represents bcc structure
43. (d) For bcc, d = 3 a or a = 2d = 2 ´ 4.52 = 5.219Å 3 3
2 3 1.732 \ r= a= ´ 5 = 2.165Å = 216.5 pm
= 522 pm 4 4
z´ M
» 217 pm
r= 3
a ´ N A ´10 -30 r ´ a3 ´ N A ´ 10-30
51. (d) M=
2 ´ 39 Z
=
(522) ´ (6.023 ´1023 ) ´ 10 -30
3
10 ´ (100)3 ´ 6.02 ´ 1023 ´ 10 -30
= = 15.05
= 0.91g / cm3 = 910 kg m -3 4
THE SOLID STATE 545

62. (c) AgBr exhibit Frenkel defect.

6.02 ´1023 63. (b) When equal number of cations (Na +) and anions (Cl–) are
\ Number of atoms in 100 g = ´100
15.05 missing from their regular lattice positions, we have
= 4 × 1025 Schottky defect.
52. (b) The volume of the unit cell 64. (c) Frenkel defect is due to dislocation of ion from its usual
= (2.88 Å)3 = 23.9 × 10–24 cm3. lattice site to interstitial position.
The volume of 100 g of the metal 65. (c) 66. (a)
m 100 67. (d) LiCl crystals are pink because its anionic sites are
= = = 13.9 cm3 -
r 7.20 occupied by unpaired eonline . Zinc oxide shows metal
Number of unit cells in this volume excess defect due to presence of extra cations at
13.9 cm3 interstitial sites.
= = 5.82 × 1023 68. (a)
23.9 ´ 10 -24 cm3
53. (b) Density is given by 69. (d) Excess of lithium makes LiCl crystal pink.
70. (a) Schottky defect is due to missing of equal number of
Z´M cations and anions.
d= ; where Z = number of formula units present
N A a3 71. (d) When insulators (non metal atoms) interact to form a
in unit cell, which is 4 for fcc solid, their atomic orbitals mix to form two bunch of
a = edge length of unit cell. M = Molecular mass orbitals, separated by a large band gap. Electrons cannot
therefore be promoted to an empty level, where they
4´ M could move freely.
2.72 = (Q 1pm = 10 -10 cm)
23
(
6.02 ´ 10 ´ 404 ´ 10 )
-10 3 72.
73.
(b)
(d) For n-type, impurity added to silicon should have more
2.72 ´ 6.02 ´ (404)3 than 4 valence electrons.
M= = 26.99 = 27 gm mole–1 74. (d) Extrinsic semiconductor
4 ´107
75. (a) MnO2
54. (d) Ionic solids must always maintain electrical neutrality. 76. (c) Rhenium oxide ReO3 is like metallic copper in
Ionic solids show vacancy or interstitial defects as conductivity.
Frenkel and Schottky defect. 77. (d) 78. (b)
55. (d) When electrons are trapped in anion vacancies, these 79. (d) Ferrimagnetism is observed when the magentic
are called F-centre. moments of the domains in the substance are aligned
in parallel and antiparallel directions in unequal
numbers.
+ve –ve
e– ion ion 80. (b) Due to release of electrons, the crystal can conducts
electricity but conductivity is not as high as that of metals.
F- centre in crystal Its conductivity is very low and because conduction
is due to electrons so it is n-type semiconductor, also
56. (d) If in an ionic crystal of the type A+, B–, equal number of excitation of these electron give rise to yellow color in
cations and anions are missing from their lattice sites crystal.
so that the electrical neutrality is maintained. The defect 81. (c) CrO2 is a ferromagnetic whereas O2 is paramagnetic.
is called Schottky defect. 82. (c)
57. (d) The appearance of colour in solid alkali metal halide is 83. (a) In case of semiconductors, the gap between valence
due to presence of F-centre found as defect in the band and the conduction band is small and therefore
crystal structure. some of the electrons may jump from valence band to
58. (b) More is the Schottky defect in crystal more is the conduction band and thus on increasing temperature
decrease in density. conductivity is also increased.
59. (c) Frenkel and Schottky defects are crystal defects. It 84. (a) BaTlO3
arises due to dislodgement of cation or anion from their 85. (d) Ferrimagnetic substance become para-magnetic on
places in the crystal lattice. heating. This is due to randomisation of spins on
60. (a) In stoichiometric Frenkel defects occurs in those heating.
compound which have 86. (b) Out of the given substances, only Li has high electrical
(i) Low C.N. and thermal conductivity as Li is a metallic solid.
(ii) Large difference in size of cations and anions 87. (d)
61. (b) Transition metals exhibit this defect due to metal
deficiency, the compound obtained ar e non Exercise - 2
stoichiometric e.g. It is difficult to prepare ferrous oxide 1. (b) At low temperature existence of a substance in the
with the ideal composition of FeO what we actually solid state is due to slow molecular motion and strong
obtain is Fe0.95O or FexO with x = 0.93 to 0.96 cohesive forces.
 EBD_7374
546 CHEMISTRY

2. (b) Crystalline solid is anisotropic in nature as it shows When lattice site is occupied by electron, this type of
different physical properties such as electrical defect is known as metal excess defect.
resistance, refractive index in different directions. 19. (b) For the formation of p-type semiconductors, group 13
3. (b) Quartz glass (SiO2) is an amorphous solid due to its elements are doped with group 14 elements, which
short range order of constituent particles. creates a hole in a molecule but the molecule as a whole
4. (d) Substances which have domain structure are remain neutral.
oppositely oriented and cancel each other's magnetic 20. (d) To get a n – type semiconductor from silicon, it should
field are known as antiferromagnetic substances. be doped with a substance with valency 5.
5. (a) Since, quartz glass is an amorphous solid having short e.g., silicon is doped with phosphorus to form a
range order of constituents. Hence, value of refractive n – type semiconductor.
index is same in all directions, measurable and not to 21. (b) In a fcc unit cell 8 tetrahedral voids are present at the
be equal to zero always. centre of each 8 smaller cube of the unit cell.

.. .. .. . ..
6. (d) Amorphous solids are isotropic in nature and any of Eight tetrahedral voids
its physical property will be same in all direction. per fcc unit cell
7. (b) Crystalline solids has a regular arrangement of 1 2
constituent particles observed over a long distance in 3

. .. . .
4
the crystal lattice due to which they exhibit sharp

.
melting point.
8. (a) Iodine molecules belongs to a class of non – polar Tetrahedral
molecular solids in which constituents molecule are void

9. (c)

10. (c)
held together by London or dispersion forces.
Diamond is a giant molecule in which constituent atoms
are held together by covalent bonds.
Iodine is a non–polar molecular solid and a non–
.. . 7
5 6
8
Each cube contain one tetrahedral
void at its body centre

conductor of electricity. Water is a hydrogen bonded Number of octahedral voids present = 4

molecular solid in which H and O are held together by Number of tetrahedral voids present = 8
polar covalent bond and each water molecule is held 22. (a) In AgBr, both Ag+ and Br– ions are absent from the
together by hydrogen bonding. Also, due to its non- lattice causing Schottky defect. Also, Ag+ ions are
ionic nature, it also behaves as a non-conductor of mobile so they have a tendency to move from their
electricity. lattice site to interstitial site which causes Frenkel
11. (a) Ionic solids get easily dissociated into its ions in defect.
molten state and show high electrical conductivity. 23. (b) As, packing efficiency for hcp or ccp is calculated to
12. (b) In graphite, each carbon is sp2 hybridised having one be 74%, it is maximum among all type of crystals.
free electron and due to the presence of free electrons 24. (c) Packing efficiency for bcc arrangement is 68% which
graphite behaves as a good conductor of electricity. represents total filled space in the unit cell. Hence
13. (c) Certain metal oxides like VO2, VO3 and TiO3 etc. show empty space in a bcc arrangement will be 100 – 68
metallic or insulating property depending upon = 32%.
temperature which is due to variation in energy gap 25. (d) Hexagonal close packing can be diagramatically
between conduction band and valence band. represented as :
14. (d) Metal oxides like CrO2, TiO and ReO3 show electrical
conductivity similar to metals while SiO2, MgO and B
SO2 do not show electrical properties. A
B
15. (c) Each lattice point in a pure crystal is either an atom or
A
molecule or ion which are joined together by a straight
line to bring out geometry of lattice in pure crystal We can see that lst layer (A) and 4th layer (B) are not
constituents which are arranged in fixed stoichiometric exactly aligned.
ratio. 26. (a) In NaCl crystal Cl– ions are present at fcc lattice points
16. (d) Graphite is a covalent solid which is made up of carbon and face centre and Na+ occupies all the octahedral
atoms covalently bonded to three carbon atoms. As, voids of the unit cell.
the formation of covalent bond occurs throughout the Thus, coordination number of Na+ and Cl– is 6.
crystal hence, it is a type of network solid. Also due to the 27. (c) Coordination number in a square closed packed
presence of free electrons graphite is a conducting solid. structure in 2-D must be equal to 4 as shown :
17. (a) When smaller ion (usually a cation) is dislocated from
its normal site in crystal and move to interstitial site, it A
is known as Frenkel defect. A
18. (b) Schottky defect is observed in crystal when equal A
A
number of cations and anions are missing from the
lattice. Square closedclosed
Cubic packedstructure
structure
THE SOLID STATE 547

28. (d) When electron rich or electron deficient impurity is

added to a perfect crystal it introduces electronic defect
Conduction band
in it.
Empty
29. (b) Sillicon doped with electron rich impurity to form a Empty
band
n – type semiconductor. band
Forbidden zone
30. (b) Ferromagnetic substances can be permanently (Large energy gap) Small energy gap

Energy
magnetised by applying magnetic field and they will Filled
exhibit the magnetic properties even after the removal Overlapping band
of magnetic field. band bands
31. (d) The fraction of octahedral or tetrahedral voids Metal Insulator Semiconductor
occupied depends upon the radii of the ions present at Value of k 10 4 – 107 10 – 20 – 10
–10 10– 6 to 10 4
the lattice points. As we know the radii of octahedral (in W – 1 m– 1)

or tetrahedral void is related to radii of atoms (r) as

Hence, correct order of conductivity in solids is :
Radius of octahedral void (Ro) = 0.414 r
kmetals >> kinsulators < ksemiconductors
Radius of tetrahedral void (Rt) = 0.225 r
Where, r = radius of bigger atom involved 38. (d) For bcc lattice body diagonal = a 3
32. (a) When a ferromagnetic substance is placed in a magnetic The distance between the body centered atom and one
field it becomes a permanent magnet because all the corner atom in cube will be
domains get oriented in the direction of magnetic field
3a
even after the removal of applied magnetic field. =
2
33. (b) Packing efficiency in different types of unit cells is as
follows : 39. (b) For each central atom there are two tetrahedral voids in
AgI crystal. The number of Ag+ ion is equal to number
of I–ion. It means only 50% of the void will be occupied
Unit cell Packing efficiency
by Ag+ ion.
fcc 74% 40. (a) All magnetically ordered solids (ferromagnetic,
bcc 68% ferrimagnetic and antiferromagnetic solids) transform
Simple cubic 52% to the paramagnetic state at high temperature due to
the randomisation of spins.
Thus, the correct order of packing efficiency is: fcc
(74%) > bcc (68%) > simple cubic (52%). 41. (c)
34. (a) Frenkel defect is also known as dislocation defect
because in this defect atoms present in crystal lattice
are dislocated to interstitial site.
35. (d) In the cubic close packing the unit cell has 8 tetrahedral
voids are located at each eight smaller cube of an unit
cell.
36. (a) Edge lengths for different types of unit cells are given Relation between radius of cation, anion and edge
as : length of the cube

Types of unit cell Edge length 2r + 2r = 3a

Cs+ Cl-
fcc 2 2r
4 3a
bcc r r +r =
Cs+ Cl -
2
3
Simple cubic 2r 42. (b) CsI3 dissociates as
CsI3 ® Cs+ + I3–
37. (a) Conductivity of metal, insulator and semiconductors
2a 1.41 ´ 361
can be represented in the terms of k (Kappa) which 43. (a) For fcc : r = = = 127 pm
depends upon energy gap between valence band and 4 4
conduction band. 44. (d) Number of atoms per unit cell
= 8 × (1/8) + 1 = 2
3a
r=
4
 EBD_7374
548 CHEMISTRY

54. (d) For a fcc unit cell

4
2 ´ pr 3 2a
3 r=
Packing Fraction (P.F.) =
(4r / 3)3 4
2a a
\ closest distance (2r) = =
3p 4 2
= = 0.68
8 55. (b) In bcc structure,
% P.F. = 68% ; % of vacant space no. of atoms at corner = 1/8 × 8 = 1
= 100 – 68 = 32% no. of atom at body centre = 1
45. (a) ZnS has cubic close packed (ccp) structure. The S2– therefore, total no of atom per unit cell = 2.
ions are present at the corners of the cube and at the 4r
centre of each face. Zinc ions occupy half of the 56. (d) For bcc lattice : Z = 2, a =
3
tetrahedral sites. Each zinc ion is surrounded by four
sulphide ions which are disposed towards the corners For fcc lattice : Z = 4, a = 2 2r
of a regular tetrahedron. Similarly, S2– ion is surrounded æ ZM ö
by four Zn 2+ ions. çç 3 ÷÷
d25 °C è NA a øbcc
46. (c) Tetrahedral void is so called because it is surrounded \ =
by four spheres tetrahedrally while octahedral void is d900 °C æ ZM ö
so called because it is surrounded by six spheres çç 3 ÷÷
octahedrally. è NA a øfcc
47. (c) In bcc the atoms touch along body diagonal 3
2 æ 2 2r ö 3 3
\ 2r + 2r = 3a = ç ÷ =
4 4r 4 2
ç ÷
3a 3 ´ 4.29 è 3 ø
\ r= = = 1.857Å 57. (b) Assertion and reason, both are correct. Reason is
4 4
48. (b) Graphite is covalent solid. not the correct explanation of assertion.
49. (c) C6H6 is diamagnetic (i – 5) The correct reason for Schottky defect is loss of equal
CrO2 is ferromagnetic (ii – 3) number of cations and anions from lattice sites. Here
MnO is antiferromagnetic (iii – 1) we are only giving examples of such solids in which
Fe3O4 is ferrimagnetic (iv – 2) this defect is observed.
Fe3+ is paramagnetic with 5 unpaired electron (v – 4) 1
58. (d) The number of A ions per unit cell = ´12 (corners)
50. (c) The hcp arrangement of atoms occupies 74% of the 6
available space and thus has 26% vacant space. 1
+ ´ 2 (end centres) + 3 (in the body)
Z´ M 2
51. (d) r = , Number of octahedral voids per unit cell = 1× 6 = 6.
No ´ a3
Number of cations (C) per unit cell
Z ´ 27 2
2.7 = = ´6 = 4
6.02 ´ 10 23 ´ ( 4.05) 3 ´ 10 -24 3
Formula : C4 A6 or C2 A3
\ Z=4 59. (c)
Hence it is face centred cubic unit lattice. ZM Z ´120
60. (b) d = Þ 6.25 =
( )
Again 4r = a 2 = 5.727 Å 3 3
N Aa 6 ´1023 ´ 4 ´10-8
\ r = 1.432 Å
52. (a) The number of Fe 3+ ions replacing x Fe2+ ions = 2 x Exercise - 3
3
vacancies of cations 1. (c) CaO has higher lattice energy because of higher charge
on Ca2+ and O2–, which results in higher attraction. KI is
2x
=x– = x /3 more soluble in water because of low lattice energy and
3 higher hydration energy. Clearly (c) is wrong because CaO
But x/3 = 1 – 0.94 = 0.06, has higher melting point as compared to KI.
x = 0.06 × 3 = 0.18 = 18%
1 1
53. (c) In bcc the atoms touch along body diagonal 2. (c) No. of Cu = 8 ´ + 6 ´ = 4
8 2
\ 2r + 2r = 3a
1
No. of Ag = 12 ´ = 3
3a 3 ´ 4.29 4
\ r= = = 1.857Å No. of Au = 1
4 4
Cu4Ag3Au1
THE SOLID STATE 549

Area occupied by effective circles zM w

3. (d) Packing effieincy = 9. (b) d =
Area of square N Aa 3
2pr 2 2pr 2 Z = 4, a = 3.5 × 10–8 cm, Mw = 59
= ´ 100 = ´ 100 = p ´100 = 78.54% 10. (c) rc 0.066
= = 0.47
L2 2( 2 r )2 4 ra 0.140
C D So, cation (Mg2+) fitted in octahedral holes of O2– are present
4. (a)
B at fcc lattice point.
11. (d) ln Be2C3; Be+ = In tetrahedral voids
a

A E
AB = a (nearest)
(next - nearest) Be+ =
BD = 2a 2–
(next - next - nearest) C3 =
CE = 3a
5. (d) Effective no. of atoms of B present in a unit cell = 2
Total volume of B unoccupied by A in a unit cell
4
(
= 2 ´ R3 - r3 ´ p
3
)
r = radius of A C 32 - = In FCC arrangement (Lattice point at corner + at each face centre)
R = radius of B Therefore, coordination number of Be+ = 4
7pR 3 æ Rö And coordination number of C 32 - = 8.
= çQ r = ÷
3 è 2ø 12. (d) Number of atoms = NA
Volume of unit cell = a3
3 NA
æ 4R ö Þ Number of unit cells =
Þ ç
è 3ø
÷ =
64 3
3 3
R Q 3a = 4R ( ) [Q 4 atoms in each unit cell]
4
3
7pR NA
3 7p 3 Volume of 1 mol lattice = × Volume of unit cell
Desired ratio Þ = 4
64 3 64
R 6.023 × 1023
3 3 = × (400 × 10– 12)3 m3
6. (a) Effective number of remaining 4
= 9.64 mL
é 1 1 ù 13
Cl– = 4 - ê 2 ´ + ú = 3
ë 8 2û 4 13. (b) For bcc, r = a
Effective number of Na+ = 4 4
Occupied volume Edge length not covered by atom = a – 2r
Packing Fraction =
Total volume 3 é2– 3 ù
=a–2× a = aê ú
13 4 3 4 4 ë 2 û
´ pr- + 4 ´ pr+3
= 4 3 3 é2– 3ù
3 aê ú
8(r+ + r- )
ë 2 û
7. (a) Zeff for fcc = 4 and for bcc = 2/unit cell \ % of fraction not covered = × 100
a
dg Z eff (fcc) æ abcc ö
3 = 0.134 × 100 = 13.4%
dfcc
= = ×ç
è afcc ÷ø
db 14. (c) Among the three options KCl, NaCl and MgCl2 , the
d bcc Zeff (bcc)
3
size of anion is same. So larger the cation, larger will be the
4 æ 290 ö cation/anion ratio i.e., KCl will have larger cation/anion ratio
= ×ç ÷ = 0.9788
2 è 386 ø among the three. So, we left with two options KCl and CaF2 .
Z ´ Mw Among these two CaF2 will have maximum value of cation/
8. (d) Density (d) = eff
NA ´ a 3 anion ratio because decrease in ionic radii of anion from Cl–
(For antifluorite, Zeff = 4/unit cell) to F– does not overcome the effect of decrease in ionic radii
of cation from K+ to Ca2+.
4 ´ [ 23 ´ 2 +16]
d= 1
15. (a) Number of A atoms = ´ 8 =1
6 ´10 ´ (100 ´10-10 cm)3
23
8
1
é1Pm = 10-12 m = 10-10 cm ù Number of B atoms = ´ 6 = 3
ë û 2
= 414.16 g cm–3 \ Formula AB3
 EBD_7374
550 CHEMISTRY

16. SOLUTIONS
11. (a) For HCl
Exercise - 1
M = N = 0.1
1. (c) In homogeneous mixtures composition and properties N1V1 = N2V2 ; 25 × N1 = 0.1 × 35
both are uniform throughout the mixture. 0.1 ´ 35 0.1 ´ 35
2. (b) Density = 1.17 gm/cc (Given) N1 = ;\M = = 0.07 .
25 25 ´ 2
Mass 12. (b) 1 molal solution means 1 mole of solute dissolved in
As d <
Volume 1000 gm solvent.
volume = 1cc \ mass = d = 1.17g \ nsolute = 1 wsolvent = 1000 gm
No. of moles 1.17 ´1000 1000
Molarity < < \ nsolvent = = 55.56
Volume in litre 36.5 ´1 18
1
1170 xsolute = = 0.0177
< =32.05M 1 + 55.56
36.5 13. (d) H3PO4 is tribasic so N = 3M = 3 × 1N = 3N.
3. (c) From molarity equation 14. (c) N1V1 + N2V2 = NV
M1V1 + M2V2 = M3(V1 + V2) 4x + 10 (1 – x) = 6 × 1; –6x = –4 ; x = 0.67
1× 2.5 + 0.5 × 3 = M3 × 5.5 Thus 0.67 litre of 4N HCl
4 1 – x = 1 – 0.67 = 0.33 litre of 10 N HCl
M3 < < 0.73M
5.5
Molarity
4. (b) Relation between molality and mole fraction is 15. (c) Molality (m)
Molarity ´ Molecular mass
1000 ´ x2 1000 ´ .2 Density -
m= = = 3.2 1000
x1M1 0.8 ´ 78
18
Thus, X (m) = 3.2 = = 500
18 ´ 98
Number of moles 1.8 -
5. (c) Molarity = 1000
Volume of solution (L) 16. (d) No. of millimoles = 500 × 0.2 = 100
Mass 1000 Thus, molarity of diluted solution
Moles of water = = = 55.6
Molar mass 18 100
=
55.6 700
Molarity = = 55.6
1 (Molarity = No. of moles L–1 = No. of millimoles mL–1)
6. (b) Q 10 g glucose is dissolved in = 100 ml solution. = 0.1428 M
\ 180 g (g mole) is dissolved in
100 wt ´1000
= ´ 180 = 1800 ml = 1.8 L 17. (d) Molarity (M) =
10 mol. wt. ´ vol (ml)
Mass of solute
7. (d) ppm = ´ 106
Mass of solution wt. 1000
2= ´
10 63 250
\ ppm = ´ 106 = 10 ppm
106 wt. =
63
gm
No. of moles of solute = 5 = 2 M 2
8. (b) Molarity =
Volume in litres 2.5 100
wt. of 70% acid = ´ 31.5 = 45 g
9. (b) One molal solution means one mole of solute is present 70
in 1 kg (1000 g) solvent 18. (b) More than theoretical weight since impurity will not
i.e., mole of solute = 1 contribute.
1000 g 1000
Mole of solvent (H2O) = = 19. (c) Applying the law of equivalence,
18g 18
N1V1 + N 2V2 + N3V3 = N RVR
1 18
Mole fraction of solute = = = 0.018. N N N
æ 1000 ö 1008 ´ 50 + ´ 30 + ´ 10 = N R ´ 1000
ç1 + ÷ 10 3 2
è 18 ø
5 N + 10 N + 5 N = 1000 ´ N R
10. (d) NV = N1V1 + N2V2 + N3V3
N
1 1 1 Þ NR =
or, 1000N = 1 ´ 5 + ´ 20 + ´ 30 or N = . 50
2 3 40
SOLUTIONS 551

20. (a) Given w = 10 g Mol. mass = 40 33. (d)

Weight of solvent = 1250 × 0.8 g = 10000 g = 1 kg 34. (a) According to Henry’s law at a constant temperature,
the solubility of a gas in a liquid is directly proportional
10
\ molality = = 0.25 to the pressure of the gas.
40 ´ 1 35. (d) According to Henry’s law,
21. (c) In a given solution sum of all the mole fraction is unity m=k×p
i.e., given KH = 1.4 × 10–3
(a) x1 + x2 + x3 + x4 = 1 pO2 = 0.5 or
n3 p O2 = K H ´ x O2
(b) = x3
n1 + n 2 + n 3 + n 4 0.5
\ x O2 =
22. (d) 23. (d) 24. (a) 1.4 ´ 10- 3
m
25. (c) Equivalent weight of orthophosphoric acid No. of moles; n =
3 + 31 + 64 98 M
= m
(H3PO4) = 0.7 ´ 10 -4 =
3 3 32
Now 100 gm solution contains 70 gm H3PO4 m = 22.4 ´ 10 -4 g = 2.24 mg
100 70 36. (c)
litre of solution contains gm 37. (b) [Hint : If added substance dissolves, the solution is
1000 ´1.54 98 / 3
equivalent of H3PO4 unsaturated. If it does not dissolve solution is
Normality of solution saturated. If precipitation occurs solution is
supersaturated.]
70 ´ 3 38. (c)
98 70 ´ 3 39. (b) Body temperature of human beings remains constant.
= = ´ 10 ´ 1.54 = 33 N
1 98 40. (a) 41. (b)
10 ´1.54 42. (c) The partial pressure of the gas in vapour phase (p) is
proportional to the mole fraction of the gas (x).
26. (a) Mole fraction of any component A in solution
p = KH .x
No. of moles of A Where KH is Henry’s constant.
x=
Total No. of moles of solution 43. (d) To increase the solubility of CO2 in soft drinks and
soda water, the bottle is sealed under high pressure.
As total no. of moles of solution > No. of moles of A
44. (d) Scuba divers must cope with high concentrations of
Thus x can never be equal to one or zero.
dissolved gases while breathing air at high pressure
27. (b) An increase in temperature of the solution increases
underwater. Increased pressure increases the solubility
the solubility of a solid solute.
of atmospheric gases in blood. When the divers come
The amount of solute that dissolve depends on what
towards surface, the pressure gradually decreases.
type of solute it is.
This releases the dissolved gases and leads to the
For solids and liquid solutes, changes in pressure have
formation of bubbles of nitrogen in the blood. This
practically no effect on solubility.
blocks capillaries and creates a medical condition
28. (b) Number of solute particles going into solution will be
known as bends, which are painful and dangerous to
equal to the solute particles separating out and a state
life. To avoid bends, as well as, the toxic effects of
of dynamic equilibrium is reached.
high concentrations of nitrogen in the blood, the tanks
solute + solvent solution.
used by scuba divers are filled with air diluted with helium
i.e., rate of dissolution = rate of crystallization.
(11.7% helium, 56.2% nitrogen and 32.1% oxygen).
29. (d) The maximum amount of solute dissolved in a
45. (a) At high altitudes the partial pressure of oxygen is less
given amount of solvent is its solubility.
than that at the ground level. This leads to low
30. (d)
concentrations of oxygen in the blood and tissues of
31. (b) According to Le-chateliers principle, for an exother
people living at high altitudes or climbers. Low blood
mic reaction (DH< 0) increase in temperature decreases
oxygen causes climbers to become weak and unable
the solubility.
to think clearly, symptoms of a condition known as
32. (c) On increasing the pressure over the solution phase
anoxia.
by compressing the gas to a smaller volume (in fig b)
46. (c) Solubility of gases increase with decrease of temperature.
increase the number of gaseous particles per unit
47. (d) According to Henry’s law the mass of a gas dissolved
volume over the solution and also the rate at which
per unit volume of solvent is proportional to the
the gaseous particles are striking the surface of
pressure of the gas at constant temperature m = K p i.e.
solution to enter it. The solubility of the gas will
as the solubility increases, value of Henry’s law
increase until a new equilibrium is reached resulting in
constant decreases. Since CO2 is most soluble in water
an increase in the pressure of a gas above the solution
among the given set of gases. Therefore CO2 has the
and thus its solubility increases.
lowest value of Henry’s law constant.
 EBD_7374
552 CHEMISTRY

48. (d) Let the mass of methane and oxygen = m gm.

Mole fraction of O2 55. (b) Moles of glucose = 18 = 0.1
180
Moles of O2
=
Moles of O 2 + Moles of CH 4 Moles of water = 178.2 = 9.9
18
m / 32 m / 32 1 Total moles = 0.1 + 9.9 = 10
= = =
m / 32 + m /16 3m / 32 3
Partial pressure of O2 = Total pressure × mole fraction pH2O = Mole fraction × Total pressure = 9.9 ´ 760
10
1 1 = 752.4 Torr
of O2 , PO2 = P × = P
3 3 56. (d) p = pAxA + pBxB
49. (a) kH = 100 kbar = 105 bar, p = 1 bar = pAxA + pB (1 – xA)
p = k H × xA Þ pAxA + pB – pBxA
p 1 Þ pB+ xA (pA – pB)
xA = = = 10-5 57. (d) 1% solution contains 1 g of the solute in 100 g of
k H 100 ´ 103
solution.
1000 Osmotic pressure, p = CRT
Moles of water = = 55.5
18 The value of R and T is same for all the solute however,
Weight of water = 1000 g (Q 1000 mL = 1000 g) all of them undergo 100% dissociation
x \ pµ i×C
Mole fraction = 10–5 = iKCl = 2, iNaCl = 2, iBaCl2 = 3 and iurea = 1.
55.5 + x
As 55.5 >>> x, thus neglecting x from denominator nKCl = 1/74.5
1/ 74.5
x CKCl = ´ 1000 = 0.13
10 -5 = Þ x = 55.5 ´ 10 -5 moles 100
55.5 or pKCl = 2 × 0.13 = 0.26
or 0.555 millimoles.
50. (a) % of N2 in atmosphere = 78.9% 1
nNaCl=
% of O2 in atmosphere = 20.95% 58.5
Partial pressure of N2 = 0.789 atm = 0.799 bar
1/ 58.5
Partial pressure of O2 = 0.2095 atm = 0.212 bar C NaCl = ´ 1000 = 0.17
100
According to Henry’s law,
\ pNaCl = 2 × 0.17 = 0.34
0.212
P = (K H )O2 x Þ = x O2 = 6.08 ´10 -6 n BaCl2 =
1
(34.86 ´1000) 208.4
0.799
P = (K H ) N 2 x Þ = x N 2 = 1.0447 ´ 10 -5 CBaCl2 =
1/ 208.4
´ 1000 = 0.048
(76.48 ´ 1000) 100
æ n O2 ö æ n N2 ö or p BaCl2 = 3 ´ 0.048 = 0.14
Þ ç ÷:ç ÷
ç n O + nH O + n N ÷ ç n O + nH O + n N ÷ 1
è 2 2 2 ø è 2 2 2 ø n urea =
60
Þ x O2 : x N 2
1/ 60
Curea = ´ 1000 = 0.16
6.08 ´ 10 -6 :1.04 ´10 -5 100
= 1 : 1.71 \ purea = 1 × 0.16 = 0.16
51. (c)
52. (a) For example, decrease in the vapour pressure of water \ pBaCl2 < purea < pKCl < pNaCl
by adding 1.0 mol of sucrose to one kg of water is or III < IV < I < II
nearly similar to that produced by adding 1.0 mol of
urea to the same quantity of water at the same 58. (b) pA° = ? , Given p B° = 200 mm of Hg, xA = 0.6,
temperature. xB = 1 – 0.6 = 0.4, P = 290 of Hg
53. (d)
54. (a) Given V.PP = 80 torr P = PA + PB = PA°x A + PB°xB
V.PQ = 60 torr Þ 290 = PA° × 0.6 + 200 × 0.4 \ p°A = 350 mm of Hg.
Ptotal = V·PP × xp + V·Pq × xq
59. (b) p = p° x + p° x
total A A B B
é 3 2ù
= ê80 ´ + 60 ´ ú = 16 × 3 + 12 × 2 1
550 = pA° ´ + pB° ´
3
ë 5 5û
4 4
Ptotal = 48 + 24 = 72 torr ° ° ...(i)
pA + 3 pB = 550 ´ 4
SOLUTIONS 553

In second case 70. (b) Positive deviations are shown by such solutions in which
1 4 solvent-solvent and solute-solute interactions are stronger
ptotal = pA° ´ + pB° ´ than the solute-solvent interactions. In such solution, the
5 5
interactions among molecules becomes weaker. Therefore
° °
pA + 4 pB = 560 ´ 5 ...(ii)
their escaping tendency increases which results in the
Subtract (i) from (ii) increase in their partial vapour pressures.
\ p° = 560 ´ 5 - 550 ´ 4 = 600
B
In pure methanol th ere exists intermolecular
H–bonding.
Q pA° = 400
---O – H--- O—H --- O—H---
60. (a) Total vapour pressure = vapour pressure of pure | | |
benzene + vapour pressure of toluene CH3 CH3 CH3
= 100 + 50 = 150 mm
On adding benzene, its molecules come between
We know,
ethanol molecules there by breaking H-bonds which
P° = P´ x
C6 H 6 C 6H 6 weaken intermolecular forces. This results in increase
100 = 150 ´ x C6H6 in vapour pressure.
71. (a) Acetone and chloroform shows negative deviation from
100 Raoult's law when these are mixed, the hydrogen
xC6 H 6 = = 0.67
150 bonding takes place between the two molecular species
61. (c) The vapour pressure of a liquid increases with increase due to which escaping tendency of either liquid molecules
of temperature. becomes less and boiling point of solution increases.
62. (a) According to idea of Raoult’s law “partial pressure of 72. (b) For this solution intermolecular interactions between
one of the component is proportional to mole fraction n-heptane and ethanol are weaker than n-heptane-n-
of that component in the solution.” heptane & ethanol-ethanol interactions hence the
P < P1↓ x1 ∗ P2↓ x 2 solution of n-heptane and ethanol is non-ideal and
shows positive deviation from Raoult’s law.
600 = 450 x1 + 700 x2
73. (d) Azeotropic mixture is constant boiling mixture, it is not
4.5 x1 + 7x2 = 6
possible to separate the components of azeotropic
Q x1 + x2 = 1
mixture by boiling.
\ x1 = 0.6 x2 = 0.4
74. (c)
Þ x1 = 0.4, x2 = 0.6
75. (a) Minimum boiling azeotrope is formed by solution
63. (a) The solutions (liquid mixture) which boils at constant
showing positive deviation. e.g. acetone – ethanol.
temperature and can distil as such without any change
76. (b) 77. (b)
in composition are called azeotropes.
78. (a) According to Raoult’s law,
Solution of HNO3 and H2O will form maximum boiling
PT = xAp°A + xBp°B
point azeotrope. Maximum boiling azeotropes show
negative deviation from Raoult’s law. Given, = PT1 500 mm Hg
Composition (%) Boiling Point nA = 1 and nB = 2 \ xA = 1/3 and xB = 2/3
HNO 3 68 .0 359 K
1 2
H 2O 32 .0 373 K Þ 500 = p°A + p°B
3 3
Boiling point of the azeotrope of these two solutions is
393.5 K. Þ 1500 = p°A + 2p°B ...(i)
64. (c) These two components A and B follows the condition Also given Qn that one more mole of B is added to the
of Raoult’s law if the force of attraction between A and B solution, the pressure of the ideal solution increases
is equal to the force of attraction between A and A or B by 25 mm Hg.
and B. \ PT2 = 500 + 25 = 525 mm Hg
65. (c) For an ideal solution, DH = 0 , DV = 0
Also, nB = 3 \ xA = 1/4 and xB = 3/4
Hence, option (c) is incorrect.
66. (d) C2H5I and C2H5OH form non-ideal solution. 1 3
525 = p°A = p°B ...(ii)
67. (d) 4 4
68. (a) On adding acetone, its molecules get in between the
2100 = PA° + 3PB° Subtract (i) and (ii),
host molecules and break some of the hydrogen bonds
between them. Due to weakening of interactions, the p°B = 600 mm Hg
solution shows positive deviation from Raoult's law. p°A + 2p°B = 1500 Þ p°A = 300 mm Hg.
69. (d) A solution containing A and B components shows 79. (b) According to Raoult's law, the relative lowering in
negative deviation when A–A and B–B interactions vapour pressure of a dilute solution is equal to the mole
are weaker than that of A–B interactions. For such fraction of the solute present in the solution.
solutions. p° - p n
= Mole fraction of solute =
DH = –ve and DV = –ve p n+ N
 EBD_7374
554 CHEMISTRY

80. (a) Given vapour pressure of pure solvent

(P°) = 121.8 mm Hg; Weight of solute (w) = 15 g 0.1´ ps
or 17.5 – ps = or ps = 17.325 mm Hg.
Weight of solvent (W) = 250 g; Vapour pressure of 9.9
solution (P) = 120.2 mm Hg and Molecular weight of Hence (a) is correct answer.
solvent (M) = 78 86. (c) Osmotic pressure is a colligative property.
From Raoult’s law 87. (c) DTb = Kb ´ m
o
P -P
w M Elevation in boiling point is a colligative property,
=
= ´ which depends upon the no. of particles
Po m W
(concentration of solution). Thus greater the number
121.8 - 120.2 15 78
= ´ of particles, greater is the elevation in boiling point
121.8 m 250 and hence greater will be its boiling point.
15 ´ 78 121.8 Na2SO4 ƒ 2Na+ + SO42–
or m= ´ = 356.2
250 1.6 Since Na2SO4 has maximum number of particles (c)
P° - P n2 hence has maximum boiling point.
81. (d) =
P° n1 + n2 0.1 ´180 ´100
88. (c) Kb = =1 K / m
1.8 ´1000
640 - 600 2.5 x
= 89. (b) DTb = Kb × i × m
640 39 78 Where DTb = Elevation in boiling point
640 ´ 78 ´ 2.5 Kb = molal elevation constant
x= = 80 i = vant Hoff factor
39 ´ 40
82. (c) According to Raoult's law \ D Tb µ molality..
p° - p 90. (a) DTf = i × Kf × m
= xB Van't Hoff factor, i = 2 for NaCl, m = 0.01
p°
é .2 1ù hence DTf = 0.02 Kf which is maximum in the present
ê xB = Mole fraction of solute = .2 + .8 = 5 ú case.
ê ú Hence DTf is maximum or freezing point is minimum.
ë p = 60 mm of Hg û
K f ´ W2 ´1000 1 1000
p° - p 1 91. (c) DT = K f m = = 5.12 ´ ´ = 0.4K
= or 4 p° = ( p) ´ 5 M 2W1 250 51.2
p° 5
+
60≥5 92. (d) ( HX H + X - , i = 1.3); DTf = Kf × m × i
Þ p° < < 75mm of Hg 1- 0.3 0. 3 0.3
4
DTf = 1.85 × 0.2 × 1.3 = 0.481º C
P o - Ps n w M
83. (c) = = ´ \ Tf = T f° - DT f = 0 – 0.481ºC = – 0.481ºC
o N m W
P
12 18 93. (b) Benzoic acid exists as dimer in benzene.
0.1 = ´
m 108 94. (b) DT f = K f ´ m = 1.86 ´ 0.5 = 0.93°C; T f = -0.93°C
12 ´ 18 95. (d) Addition of solute to water decreases the freezing point
m= = 20
0.1 ´ 108 of water (pure solvent).
\ When 1% lead nitrate (solute) is added to water, the
é P° - P ù w 2 M1
84. (b) êë P° úû ´ 100 = M ´ w ´ 100 = 10 freezing point of water will be below 0°C.
2 1
1000W2 1.86×1000×68.5
w 2 18 96. (a) DT f = K f = = 0.372
´ ´ 100 = 10 or w2 = 60 g M 2W1 342×1000
60 180
Tf = T °f –DTf
Thus, 60 g of the solute must be added to 180 g of Tf = – 0.372°C
water so that the vapour pressure of water is lowered 97. (b) Blood cells neither swell nor shrink in isotonic solution.
by 10%. As isotonic solutions have equal concentration
85. (a) The vapour pressure of a solution of glucose in water therefore there is no flow of solvent occurs and hence
can be calculated using the relation solvent neither enters nor flow out of the blood cells.
p° - ps Moles of glucose in solution 98. (a) Isotonic solutions have same molar concentration at
= given temperature provided the Van't Hoff factor (i) is
ps Moles of water in solution
same.
17.5 - ps 18/180 99. (a) The solution which provide same number of ions are
or = [Q p° = 17.5 ] isotonic.
ps 178.2/18 Ca (NO3)2 ¾¾ ® Ca2+ + 2 NO3–
SOLUTIONS 555

Total ions produced = 3 p° - p No. of moles of solute

Na2SO4 ¾¾ ® 2 Na+ + SO42– =
p° No. of moles of solvent
Total ions produced = 3
\ 0.1 M Ca (NO3)2 and 0.1 M Na2SO4 are isotonic.
DTb = Kb × m
100. (d) Osmotic pressure is a colligative property. Hence Number of moles of the solute
m= ´ 1000
resulting osmotic pressure of the solution is given by Mass of solvent in grams
pT = p1 + p2 + p3 ..........
Number of moles of the solute
pT = 1.64 + 2.46 = 4.10 atm. DTb = K b ´ × 1000
101. (c) Isotonic solutions have same osmotic pressure Mass of solvent in grams
pglucose = punknown solute Number of moles of solute
m1 m 2 5 2 DTb ´ Mass of solvent in grams
\ = or = Þ M 2 = 72 =
M1 M 2 180 M 2 K b ´ 1000
102. (a) As both the solutions are isotonic hence there is no 2 ´100
= = 0.26,
net movement of the solvent occurs through the 0.76 ´1000
semipermeable membrane between two solutions. 100
103. (d) Colligative properties depends upon the no. of particles. Number of moles of solvent = = 5.56
18
Since methanol is non electrolyte hence cannot be
considered. From equation (i) we get, 760 - p = 0.26
104. (a) 105. (d) 760 5.56
106. (b) According to Raoult's law On solving, p = 724.46 » 724
109. (d) (100 + DTb) – (0 – DTf) = 105
Dp n DTb + DTf = 5
= (mole fraction of solute)
p° n + N m (kb + kf) = 5
10 5 5
= 0.2 \ p° = 50 mm of Hg m= i.e., moles in 1000 g water
p° 2.37 2.37
For other solution of same solvent 5
20 n (or) moles in 100 g water
= (Mole fraction of solute) 2.37 ´ 10
p° n + N
5
\ Wt. of sucrose = ´ 342 = 72g
20 2.37 ´10
Þ = Mole fraction of solute
50 110. (b) Given kb = x K kg mol–1
Þ Mole fraction of solute = 0.4 DTb = kb × m
As mole fraction of solute + mole fraction of solvent = 1 \ y= x × m
Hence, mole fraction of solvent = 1 – 0.4 = 0.6
y
107. (b) Relative lowering of vapour pressure is given by : m=
x
P ° – Ps w/m
= We know
P° w/ m +W / M DTf = kf × m
where, P° = vapour pressure of pure solvent
On substituting value of m,
Ps = vapour pressure of solution
w = mass of solute yz
DTt =
m = molecular mass of solute x
W = mass of solvent 111. (d) Mass of non-volatile solute = 1g
M = molecular mass of solvent Molar mass of solute = 250g mol–1
For dilute solution Mass of benzene = 51.2g, Kf = 5.12 K kg mol–1
121.8 - 120.2 15 / m 15 78
Þ = = ´ = 1.3 ´ 10-2 K f ´ 1000 ´ w 2
121.8 250 / 78 m 250 DTf =
M 2 ´ w1
Þ m = 356.265
108. (a) From Raoult law where, w2= mass of the solute
M2 = molar mass of solute
p° – p
w1 = mass of the solvent
p°
5.12 ´ 1000 ´ 1
No.of moles of solute On substituting given values, DT f =
= 51.2 ´ 250
No. of moles of solvent+ No. of moles of solute
When the concentration of solute is much lower than \ DTf = 0.4K
the concentration of solvent,
 EBD_7374
556 CHEMISTRY

112. (c) If compound dissociates in solvent i > 1 and on 2. (d) Dissolution of sugar in water will be most rapid when
association i < 1. powdered sugar is dissolved in hot water because in
113. (a) Van’t Hoff equation is powdered form it can easily insert in the vacancies of
pV = inRT water particle.
For depression in freezing point. Also, dissolution of sugar in water is an endothermic
D Tf = i × Kf × m process. So it is favourable at high temperature.
For elevation in boiling point. 3. (c)
D Tb = i × Kb × m 4. (b) When solute gets precipitated in the solution, then
For lowering of vapour pressure, the solution is known as supersaturated solution.
5. (c) Maximum amount of solid that can be dissolved in a
°
Psolvent - Psolution æ n ö
= iç specified amount of a given solvent does not depend
÷.
P° è N +nø upon pressure. The reason is solid and liquid are highly
solvent
incompressible and practically remain unaffected by
114. (d) change in pressure.
115. (c) Na2SO4 ¾¾
® 2Na+ + SO 24- 6. (b) At high altitude, the partial pressure of oxygen is less
Mol. before dissociation 1 0 0 than at the ground level. This decreased atmospheric
Mol. after dissociation 1 – a 2a 1a pressure causes release of oxygen from blood. Hence
people living at high altitude have low concentration
i = 1 - a + 2a + a = 1 + 2a
of oxygen in the blood and tissues.
116. (d) The salt that ionises to least extent will have highest
7. (a) Mixture of methanol and acetone show a positive
freezing point. [ i.e., minimum DTf ]
deviation from Raoult’s law. Molecules in pure
117. (a) Concentration of particles in CaCl2 solution will be
methanol are hydrogen bonded. On adding acetone,
maximum as i = 3 for CaCl2 and i = 2 for KCl.
its molecules enters in between the host molecules
Glucose and Urea do not dissociate into ions, as they
and break some of the hydrogen bonds between them.
are nonelectrolytes.
Therefore, the intermolecular attractive forces between
118. (a) K4[Fe(CN)6] and Al2(SO4)3 both dissociates to give 5
the solute-solvent molecules are weaker than those
ions or i = 5
between the solute-solute an d solvent-solvent
K4 [Fe(CN)6] ‡ˆˆˆˆ† 4K+ + [Fe(CN)6]4–
molecules.
ˆˆ† 2Al3+ + 3SO 2–
and Al 2 (SO 4 )3 ‡ˆˆ 4 Other three remaining options will show negative
deviation.
No. of particles after ionisation 8. (b) Colligative properties depend upon number of solute
119. (a) (i) i =
No. of particles before ionisation particles in solution irrespective of their nature.
9. (b) Colligative properties depends upon the number of
(ii) DTb = i × Kb × m
particles. As we know greater the value of van't Hoff
¾® Cu2+ + 2Cl-
CuCl2 ¾ factor higher will be elevation in boiling point and hence
1 0 0 higher will be the boiling point of solution. Among the
(1-a) a 2a given solution 1.0M Na2SO4 have highest no. of
particles i.e highest value of ‘i’.
1 + 2a
i= , i = 1 + 2a Hence, 1.0 M Na2SO4 has highest value of boiling
1 point.
Assuming 100% ionization
10. (a) DTb = Kbm elevation in boiling point
So, i = 1 + 2 = 3
13.44 DTb
DTb = 3 ´ 0.52 ´ 0.1 = 0.156 » 0.16 [m = = 0.1] Kb =
134.4 m
120. (d) DTf = i.k f .m ; DTb = i.k b .m unit of DTb K
Unit of Kb = =
DTf k f
unit of m molality
= K
DTb k b
= = K mol-1 kg
-1
DTf = 0 - ( -0.186°C) = 0.186°C mol kg
11. (c) DTf = iKf m i.e., depression in freezing point is directly
0.186 1.86 0.52 ´ 0.186
= Þ DTb = = 0.052 related to van't Hoff factor (i). Glucose is a non-
DTb 0.52 1.86 electrolyte hence will remain undissociated. Hence for
Exercise - 2 glucose value of i is 1 whereas for MgCl 2 value of i is 3.
Hence, depression in freezing point of MgCl2 is about
1. (a) According to Henry's law partial pressure of a gas in 3 times of glucose.
the solution is proportional to the mole fraction of gas 12. (d) When an unripe mango is placed in a concentrated salt
in the solution. solution to prepare pickle then mango loose water due
p = KHx ; KH = (Henry's constant) to osmosis and get shrivel.
SOLUTIONS 557

13. (a) Osmotic pressure (p) = CRT. 24. (d) As we know, M1V1 = M2V2
For concentrated solution C has higher value than On putting values, we get
dilute solution. 0.02 × 4 L = M2 × 5L
Hence, as concentration of solution increases osmotic
0.08
pressure also increase. M2 = = 0.016 M
5
14. (a) The value of molal depression constant, Kf depends
upon nature of solvent. Therefore two different 25. (a) At specific composition methanol-acetone mixture will
solutions of sucrose of same molality prepared in form minimum boiling azeotrope and will show positive
different solvents will have different depression in deviation. This is due to weaker A — B interaction
freezing point. than A — A and B — B interaction.
15. (b) Number of total ions present in the solution is known 26. (c) Value of KH depends upon nature of gases dissolved
as van't Hoff factors (i). in water. Higher the value of KH at a given temperature
for KCl, i= 2 the lower is the solubility of the gas in the liquid.
for NaCl, i= 2 Hence, correct order is :
for K2SO4, i= 3 Ar < CO2 < CH4 < HCHO.
16. (b) In reverse osmosis, solvent molecules move through 27. (c) Colligative properties µ no. of particles. Since Al2(SO4)3
a semipermeable membrane from a region of higher contains maximum number of particles, hence will have
concentration of solute to lower concentration. the largest value of freezing point depression.
17. (a) The value of Henry's constant (KH) increases with 28. (a) Depression in freezing point µ No. of particles.
increase in temperature. (when concentration of different solutions is equal)
18. (b) According to Henry's law
Al 2 (SO4 )3 provides five ions on ionisation
pµx
Þ p = KHx ¾® 2 Al 3+ + 3SO 42 –
Al 2 (SO 4 ) 3 ¾
As value of KH rises solubility of gases decreases. while KCl provides two ions
19. (b) If a pressure higher than the osmotic pressure is applied
on the solution, the solvent will flow from the solution ↑ K ∗ ∗ Cl,
KCl ¾¾
into the pure solvent through the semi-permeable C6H12O6 and C12H22O11 are not ionised so they have
membrane. This process is called reverse osmosis. single particle in solution.
Thus, in this case, if a pressure greater than osmotic Hence, Al2(SO4)3 have maximum value of depression
pressure is applied on piston (B). Water will move from in freezing point or lowest freezing point.
side (B) to side (A).
20. (c) As van’t hoff factor depends only on no. of dissociated 10
29. (a) Molar concentration of urea = per dm3
ions. Hence, i will be independent on concentration of 60
solutions. Molar concentration of volatile solute solution
21. (b) A mixture of bromoethane and chloroethane is an
example of ideal solution. For an ideal solution, the 5 50
= per 100 ml. or, per dm3
A — A or B — B type intermolecular interaction is M M
nearly equal to A — B type interaction.
For solution of same concentration
Chloroform and acetone mixture is an example of
non-ideal solution having negative deviation while or, isotonic solution at same temperature
ethanol-acetone mixture shows positive deviation.
10 50
22. (a) On adding salt to water to make the salt solution the = or, M = 300 g mol–1
vapour pressure of solution gets lowered. This is due 60 M
to the decrease in surface covered by solvent molecule 30. (a) p = i CRT
which leads to decrease in number of solvent molecule
pC H OH = 1 × 0.500 × R × T = 0.5 RT
escaping from the surface corresponding to pure 2 5
solvent. pMg (PO4)2 = 5 × 0.100 × R × T = 0.5 RT
3
Hence, vapour pressure also get reduces. pKBr = 2 × 0.250 × R × T = 0.5 RT
23. (a) If two liquids A and B form minimum boiling azeotrope pNa PO4 = 4 × 0.125 × RT = 0.5 RT
at some specific composition then A — B interactions 3
Since the osmotic pressure of all the given solutions is
are weaker than those of A — A and B — B. Because in
case of positive deviation, we get minimum boiling equal. Hence all are isotonic solution.
azeotropes whereas in case of negative deviation we 31. (d) The correct order of solublity of sulphides is Na2S >
get maximum boiling azeotropes. ZnS > CuS
 EBD_7374
558 CHEMISTRY

32. ¾¾
® 4K+ + [Fe(CN)6]–
(c) K4[Fe(CN)6] ¬¾ 1.86
¾ = 0.18 × = 0.654°C
0.512
and Al2(SO4)3 ® 2Al3+ + 3SO2–
4 As the Freezing Point of pure water is 0°C,
\ van’t Hoff factor is 5 for both Al 2 (SO4)3 and DTf = 0 –Tf
K4[Fe(CN)6] 0.654 = 0 – Tf
33. (d) DTb = iKb m \ Tf = – 0.654
Thus the freezing point of solution will be – 0.654°C.
Given, (DTb)x > (DTb)y
38. (c) Let the weight of acetic acid initially be w1 in 50 ml of
\ ix Kb m > iyKb m 0.060 N solution.
(Kb is same for same solvent)
ix > iy w 1 ´ 1000
N= (Normality = 0.06 N)
So, x is undergoing dissociation in water. M.wt . ´ 50
34. (a) For an ideal solution DSmix > 0 w1 ´ 1000
0.06 =
W 1 60 ´ 50
35. (d) Molality < ≥
M V(kg) 0.06 ´ 60 ´ 50
Þ w1 = = 0.18 g = 180 mg.
1000
n
< (where n solute = W/M) After an hour, the strength of acetic acid = 0.042 N
V(kg) so, let the weight of acetic acid be w2
n w 2 ´1000
1.00 m < i.e., 1 mole in 1 kg of water N=
V(kg) 60 ´ 50
Moles of 1 kg H2O w 2 ´ 1000
0.042 =
1000g 3000
< < 55.55 mole
18g / mol Þ w2 = 0.126 g = 126 mg
So amount of acetic acid adsorbed per 3g
Moles of solute = 1
= 180 – 126 mg = 54 mg
Mole fraction
Amount of acetic acid adsorbed per g
nsolute 1
< < 54
n solute ∗ n water (1 ∗ 55.55) = = 18mg
3
= 0.01768 = 0.0177 39. (d) Using relation,
36. (b) According to Raoult's law
p° - ps w 2 M1
Dp n =
= (mole fraction of solute) ps w1M 2
p° n + N
where w1, M1 = mass in g and mol. mass of solvent
10 w2, M2 = mass in g and mol. mass of solute
= 0.2 \ p° = 50 mm of Hg
p° Let M2 = x
For other solution of same solvent p° = 185 torr
ps = 183 torr
20 n
= (Mole fraction of solute) 185 - 183 1.2 ´ 58
p° n + N = (Mol. mass of acetone = 58)
183 100 x
20 x = 64
Þ = Mole fraction of solute
50 \ Molar mass of substance = 64
Þ Mole fraction of solute = 0.4 40. (a) Let us consider that A is benzene and B is toluene
As mole fraction of solute + mole fraction of solvent = 1 1 : 1 molar mixture of A and B
Hence, mole fraction of solvent = 1 – 0.4 = 0.6 1 1
37. (b) As DTf = Kf. m \ xA = and xB =
DTb = Kb. m 2 2

DT f DT Total pressure of solution (P) = PAo xA + PBoxB

Hence, we have m = = b
Kf Kb 1 1
P = 12.8 × + 3.85 × = 8.325 kPa
Kf 2 2
or DT f = DTb
Kb 1
P o
x 12.8 ´
Þ [DTb = 100.18 - 100 = 0.18°C] YA = A A = 2 = 0.768
P 8.325
SOLUTIONS 559

\ yB = 1 – yA = 1 – 0.768 = 0.232 46. (a) Molarity depends on the volume of a solution which
so, the vapour will contain higher percentage of can be changed with change in temperature.
benzene. 47. (d) Colligative properties depends upon the no. of particles.
Since methanol is non electrolyte hence cannot be
æ P°- Ps ö n W1 M 2
41. (a) çç ÷
÷= = ´ considered.
è P° ø N M1 W2 48. (b)
Where, W1 = wt of solute 49. (a) Raoult’s law becomes special case of Henry’s law when
W2 = wt of solvent KH become equal to p ↓.
1
M1 = Mass of solute
50. (d) In benzene
M2 = Mass of solvent
2CH3COOH ƒ (CH3COOH)2
at 100°C, P° = 760 mm
1–a a/2
760 - 732 6.5 ´18 i = 1 – a + a/2 = 1 – a/2
=
760 M1 ´ 100 Here a is degree of association
DTf = iKfm
M1 = 31.75 g mol–1
W1 ´1000 æ 0.2 ö
çè ÷
DTb = m × Kb =
M1 ´ W2
× Kb æ aö 60 ø
0.45 = ç1 – ÷ (5.12)
è 2ø 20
0.52 ´ 6.5 ´1000 1000
DTb = = 1.06°C
31.75 ´100
a
\ boiling point of solution 1– = 0.527
= 100°C + 1.06°C = 101°C 2
42. (d) DTf = Kf × m a = 0.945
% degree of association = 94.6%
1000 ´ K f ´ w 2 ( solute ) 51. (d) p = CRT = n/VRT
M=
DTf ´ w1 ( solvent )
1 8.314 ´ 300
p= ´
1000 ´ 1.86 ´ 1.8 1.6 ´10 5 0.8
= Þ M = 180
0.465 ´ 40
= 103 × 1.94 Pa
Molecular formula = (empirical formula)n (R = 8.314 × 103 Pa LK–1 mol–1)
Molecular mass 180 52. (d) Compounds Number of particles (i)
n= = =6
Empirical formula mass 30 (b) [Co(H2O)5Cl]Cl2.H2O 3
(c) [Co(H2O)4Cl2]Cl.2H2O 2
Molecular formula = (CH2O)6 = C6H12O6.
(d) [Co(H2O)3Cl3].3H2O 1
43. (c) Both the solute and solvent will form the vapours but
(a) [Co(H2O)6]Cl3 4
vapour phase will become richer in the more volatile
component. DTf µ i where DTf = (Tf - Tf¢ )
44. (a) According to Raoult's Law Remember, the greater the no. of particles, the lower
P° - Ps WB ´ M A will be the freezing point. Compound (d) will have the
= …(i) highest freezing point due to least no of particle.
Ps M B ´ WA
0.616 /154
Here P° = Vapour pressure of pure solvent, 53. (d) DTb =Kb.m Þ 3.63 ´ ´1000;
Ps = Vapour pressure of solution 15
WB = Mass of solute, WA = Mass of solvent Tb = 61.7 + 0.968
MB = Molar mass of solute, MA = Molar Mass of Þ 62.67°C
solvent 54. (b) pH = 2
Vapour pressure of pure water at 100° C (by assumption [H+] = 0.01 M = Cx = 0.1x
= 760 torr) x = 0.1
By substituting values in equation (i) we get, i = 1 + x = 1.1
760 - Ps 18 ´18 n
= π=i RT = iMRT = 1.1 ´ 0.1RT = 0.11RT
Ps 180 ´178.2
…(ii) V
On solving (ii) we get Exercise - 3
Ps = 752.4 torr
45. (c) Kf (molal depression constant) only depends on the 1. (b) For an ideal solution, DHmixing = 0
nature of the solvent and is independent of the DH = DH1 + DH2 + DH3 (According to Hess's law)
concentration of the solution. i.e., for ideal solutions, there is no change in magnitude
of the attractive forces in the two components present.
 EBD_7374
560 CHEMISTRY

2. (d) Solution X is unsaturated so v.p. will be more, solution

Moles after dissociation
Y and Z are saturated so v.p. of Y = v.p. of Z and 2 gm of Von't Hoff Factor (i) =
solute would be present in form of solid in system Z. Moles before dissociation
(1 - x ) + 2 x + x
PA P° x PB° x B =
3. (a) yA = Þ A A and yB = ; 1
P P P
Na2SO4 is ionised 81.5%
y A PA° x A 4 1 xA means x = 0.815
= ´ Þ = ´
yB PB° x B 3 3 (1 - x A ) (1 - 0.815) + 2 ´ 0.815 + 0.815
= = 2.63.
1
4 1
xA = or x B = Observed molarity
5 5 i=
Calculated molarity
p A p°A x A x' p°
4. (c) x ¢A = = Þ A = A < 1 (since the liquid 2.054
p p xA p Þ 2.63 = = 45.07 g.
0.0352
´1000
A is less volatile, poA < P ) x

P° - P n n 5 5
5. (b) = » (for very dilute solution) 10. (c) Moles of urea = ; moles of fructose = ;
P° n+N N 60 180
n n 5
2´ = moles of sucrose = ;
NA NB 342
Þ MB = 2MA
5 5
6. (b) AlCl3 furnishes more ions than CaCl2 and thus possess moles of KCl(effective) = 2 ´ =
higher boiling point i.e., T1 > T2. 74.5 37.25
7. (b) 11. (b) Total V.P.
3- 2 3
ˆˆ† 3K + + é Fe ( CN ) ù
K3 éë Fe ( CN )6 ùû ‡ˆˆ = PAº X A + PBº X B = 100 ´
+ 150 ´ = 130 torr
ë 6û 5 5
At t = 0 1 0 0 The observed vapour pressure is smaller than that
After ionisa tion (1 – a) 3a a calculated from Raoult’s law (negative deviation).
i = 1+3a Hence, interactions A – B > A – A or B – B.
M normal 12. (d) Only solvent molecules and not the solute molecules
Since, i = ;
M abnormal or ions can pass through the semipermeable
membrane. Hence , Fe3+ and CNS– ions do not come
1 + 3a M normal in contact on either side.
\ =
1 Mabnormal DT f (normal) = K f m = 1.86 ´ 0.01 = 0.0186 ;
13. (c)
8. (d) Only solvent molecules can passed through SPM so
only dilution is possible. ΔT f (obs) 0.0205
9. (c) Molarity (experimental) i= = = 1.10 = 1 + a ; a = 0. 1
ΔT f (nor) 0.0186
DT f 3.82
= = = 2.054 mol/1000 g solvent
Kf 1.86 Ca 2 0.01´ 0.12 1
Ka = = = ´10 -3 ;
1- a 1 - 0.1 9
mole of solute
Molarity (theartical) = ´ 1000
wt. of solventing(g) Kw
Kb = = 1.0 ´10 -14 ´ 9 ´103 = 9 ´ 10 -11
Ka
5 g /142 g / mole
= ´ 1000
x 14. (b) Super cooled liquid has temperature below its freezing
Na 2SO 4 ¾¾
® 2Na +
+ SO 42 - point. On commencement of freezing, the latent heat
Moles before of freezing evolves causing the temperature to rise to
dissociation 1 0 0 F.Pt. (temperature of liquid-solid equilibrium).
Moles after 15. (d) mKf = DTf has the units of temperature . Van’t Hoff
dissociation 1–x 2x x
factor, i, is dimensionless quantity.
 17. ELECTROCHEMISTRY

Exercise - 1 18. (a) Higher the value of reduction potential higher will be
the oxidising power whereas the lower the value of
1. (a) Anode has negative polarity. reduction potential higher will be the reducing power.
2. (b) 19. (b) Follow ECS, A will replace B.
3. (d) When both the electrodes are kept in the same solution
20. (c) Gold having higher E oRe d and oxidises Fe ¾¾
® Fe2+ .
there will be no requirement of salt bridge.
4. (d) 0.0591
21. (d) E° = log K
5. (b) The cell in which Cu and Zn rods are dipped in its n
solution is called Daniel cell. Here, n = 2, E ° = 0.295
6. (c) The magnitude of the electrode potential of a metal is a 2 ´ 0.295
measure of its relative tendency to loose or gain \ log K = = 9.98 » 10 or K = 1010
0.0591
electrons. i.e., it is a measure of the relative tendency
to undergo oxidation (loss of electrons) or reduction 0.059 1
22. (a) E = E° - log +
(gain of electrons). n [H ]
M ® M n + + ne - (oxidation potential)
M n + + ne - ® M (reduction potential) 0.059 1
= 0- log -4 = -0.236V
7. (b) 2AgCl(s) + H 2 (g) ® 2HCl(aq) + 2Ag(s) 1 10
The activities of solids and liquids are taken as unity RT
o
and at low concentrations, the activity of a solute is 23. (d) Ecell = Ecell - ln Q
nF
approximated to its molarity.
The cell reaction will be At equilibrium,
Ecell = 0 and Q = Kc
Pt(s) | H 2 (g),1bar | H + (aq)1M | AgCl(aq)1M | Ag(s)
o
8. (d) Cu is anode and Ag+ is cathode.
\ Ecell ¹ Ecell
24. (c) The E°cell is given by
9. (d) Calomel electrode is used as reference electrode.
10. (b) Given ESn +4 Sn +2 = + 0.15 V 0.0591
E°cell = log Keq
n
E Cr+ 3 Cr = – 0.74 V 0.0591
\ 0.591 = log Keq
1
E °cell = E ox
° + E °red
0.591
= 0.74 + 0.15 or log Keq = = 10
= 0.89 V 0.0591
or Keq = 1 × 10 10
11. (d) E°Cell = E°OP + E°RP
25. (b) For the given cell
= 0.76 + 0.314 = 1.10 V
12. (d) According to an accepted convention anode is written 0.059V [Zn 2 + ( aq )]
on the left side and cathode on the right while Ecell = E°cell - log
2 [Cu 2 + ( aq)]
representing the galvanic cell.
13. (a) Salt bridge allows the flow of current by completing The cell potential will decreases with increase in
circuit. No current will flow and voltage will drop to [Zn 2+ (aq)] and will increases with increase in
zero, if salt bridge is removed. [Cu2+(aq)].
14. (d) In electrolytic cell the flow of electrons is from anode 26. (b) Cell reaction is, Zn + Cu 2 + ® Zn 2 + + Cu
to cathode through internal supply. 2+
15. (c) ° - RT ln [Zn ]
Ecell = Ecell
16. (b) Without losing its concentration ZnCl2 solution cannot nF [Cu 2+ ]
kept in contact with Al because Al is more reactive é ( Zn 2 + ) ù
than Zn due to its highly negative electrode reduction Greater the factor ê ú , less is the EMF
2+
potential. ëê (Cu ) ûú
17. (c) As the value of standard reduction potential decreases Hence E1 > E2
the reducing power increases i.e., 27. (b) For Zn2+ ® Zn
Z > X > Y E 2+ = E ° 2+ -
2.303RT
log
[ Zn ]
( -3.0) ( -1.2) ( +0.5) Zn /Zn Zn /Zn nF é Zn 2+ ù
ë û
 EBD_7374
562 CHEMISTRY

0.06 1 A3+ + 3e– ––––® A ;

= -0.76 - log = -0.76 - 0.03 DG3 = DG1 + DG2
2 [ 0.1] –3FE° = –Fy2 + 2Fy1
E = -0.79V –3FE° = –F (y2 – 2y1)
Zn 2 + /Zn
28. (d) emf will decrease. y2 - 2 y1
E° =
29. (c) DG° = -nFE°; E° = -DG° ; 3
nF 36. (c) 2 Cu + ¾¾
® Cu 2+ + Cu
-(-50.61kJ)
E° = = 0.26V 2 e - + Cu 2 + ¾¾
® Cu ; E1º = 0.34V; ... (i)
2 ´ 96500 ´ 10-3
º
30. (c) Because reduction potential of water is higher than e- + Cu 2+ ¾¾® Cu + ; E2 = 0.15V; ... (ii)
that of Na+ so H2 will be evolved and no reduction of
Cu + + e- ® Cu; E3º = ? ... (iii)
metal ions occurs.
Now, DG1º = -nFE1º = -2 ´ 0.34F
31. (b) E↓ 2∗ 4∗ < ,0.15V = E↓ 2∗ 2∗ < ,0.92
Sn / Sn Hg 2 / Hg
DG2º = -1 ´ 0.15F , DG3º = -1 ´ E3º F
Hence, Sn 2+ is stronger reducing agent than Hg 22 + . Again, DG1º = DG2º + DG3º
32. (a) The value of E ↓ for given metal ions are Þ -0.68F = -0.15F - E3º F
M 2∗ M

E↓ < ,1.18 V, Þ E3º = 0.68 - 0.15 = 0.53V

2∗
Mn Mn
º
Ecell º
= Ecathode (Cu + / Cu) - Eanode
º
(Cu +2 / Cu + )
E↓ 2∗ < ,0.9 V,
Cr Cr = 0.53 – 0.15 = 0.38 V.
E↓ < ,0.44 V and Zn( s) ∗ 2H∗ (aq) Zn 2∗ (aq) ∗ H 2 ( g )
Fe2∗ Fe 37. (a)
E↓ < ,0.28 V. [Zn 2 + ][H 2 ]
Co 2∗ Co 0.059
Ecell = E °cell - log
Th e correct order of E ↓ 2∗ values without 2 [H + ]2
M M
considering negative sign would be Addition of H2SO4 will increase [H+]and Ecell will also
Mn2+ > Cr 2+ > Fe2+ > Co2+. increase and the equilibrium will shift towards RHS.
38. (c) Using the relation,
0.591
33. (d)
o
E red = E red + log[M n + ] 2.303RT 0.0591
n E°cell = log Kc = log Kc
Lower the concentration of Mn+, lower is the reduction nF n
potential. 0.0591
Hence order of reduction potential is : \ 0.295 V = log K c
2
Q> R>S >P
34. (a) Cell reaction 2 ´ 0.295
or log Kc = = 10
1 0.0591
cathode : H 2O(l) + O2 ( g ) + 2e - ¾¾ ® 2OH - ( aq) or Kc = 1 × 1010
2
39. (a) Apply Nernst equation to the reaction
anode : H 2 ( g ) ¾¾ ® 2H + ( aq ) + 2e- Pb + Sn2+ ® Pb2+ + Sn
–––––––––––––––––––––––––––––––––––––––– 0.059 [Sn 2+ ]
1 or E° + log = Ecell
® 2H + (aq) + 2OH - (aq)
H 2 O(l) + O 2 ( g ) + H 2 ( g ) ¾¾ 2 [Pb 2 + ]
2 [Sn 2 + ] 0.01 ´ 2
Also we have or log = = 0.3 (Q Ecell = 0)
1 o [Pb 2 + ] 0.059
H 2 ( g ) + O 2 ( g ) ¾¾ ® H 2O(l) ; DG f = -237.2 kJ / mol
2 [Sn 2+ ]
+ - or = antilog (0.3)
H 2 O( l) ¾¾
® H ( aq ) + OH ( aq ); DG° = 80 kJ / mol [Pb 2 + ]
Hence for cell reaction 40. (d) Ecell = 0; when cell is completely discharged.
DG° = -237.2 + (2 ´ 80) = -77.20 kJ / mol
æ é Zn 2 + ù ö
0.059
DG° 77200 Ecell = E°cell - log ç ë û÷
\ E° = - = = 0.40 V 2 ç é 2+ ù ÷
nF 2 ´ 96500 ç Cu ÷
èë ûø
35. (b) (i) A3+ + e– ––––® A2+, DG1 = – 1 F y2 æ é Zn 2 + ù ö
0.059
(ii) A2+ + 2e– ––––® A, DG2 = –2F(–y1) = 2Fy1 or 0 = 1.1 - log ç ë û÷
2 ç é 2+ ù ÷
ç Cu ÷
Add, (i) and (ii), we get èë ûø
ELECTROCHEMISTRY 563

æ é Zn 2+ ù ö C = 0.1M
log ç ë û ÷ = 2 ´1.1 = 37.3 1000
ç é 2+ ù ÷ 0.059
ç Cu ÷
Ùm = (6.3 × 10–2 ohm–1 cm–1) ×
èë ûø (0.1mol / cm3 )
= 6.3 × 10–2 × 104 ohm–1cm2 mol–1
é Zn 2+ ù
ë û = 1037.3 = 630 ohm–1 cm2 mol–1
\ 49. (d) ohm–1 cm–1
éCu 2+ ù
ë û 50. (a) The specific conductance increases with concentration.
41. (a) The Half cell reaction is Zn 2+ + 2e - ¾¾
® Zn . The number of ions per cm–3 increase with increase of
0.059 1 concentration.
o
E cell = E cell - log 51. (c) Correct matching for pair (iii) will be
2 [Zn ++ ] [G (conductance) – siemens or ohm–1(S).]
= - 0.763 - 0.059 log 1 = -0.822V 52. (d) Conductivity does not depend upon mass or weight
2 0.01 of material.
Eoxi = 0.822 V 53. (d)
42. (d) + - 54. (c) (i) represents weak electrolyte
2H + 2e ¾
¾® H 2
(ii) represents strong electrolyte.
0.059 1 55. ¥
(b) L HCl = 426.2 (i)
E Re d = E oRed - log + 2 ;
n [H ] L¥
AcONa = 91.0 (ii)
0.059 1 L¥
E Re d = 0 - log ; ERed = –0.059 V,, NaCl = 126.5 (iii)
2 (0.1) 2 ¥
L AcOH = (i) + (ii) - (iii)
Eoxi = 0.059 V.
43. (c) When the concentration of all reacting species kept = [426.2 + 91.0 - 126.5] = 390.7
unity, then Ecell = E°cell and the given relation will 56. (d) Kohlrausch’s Law states that at infinite dilution, each
ion migrates independent of its co-ion and contributes
become to the total equivalent conductance of an electrolyte a
D r G = -nFE°cell definite share which depends only on its own nature.
44. (d) Molarity = 0.01 M ; Resistance = 40 ohm; From this definition we can see that option (d) is the
l ,1 correct answer.
Cell constant < 0.4cm .
A 57. (c) Conductivity of an electrolyte depends on the mobility
Specific conductivity (k ) of ions and concentration of ions. The motion of an
cell constant 0.4 ionic species in an electric field is retarded by the
= = = 0.01 ohm -1 cm -1 oppositely charged ions due to their interionic
resistance 40
1000k attraction. On dilution, concentration of electrolyte
Molar conductance ( Ù m ) = decreases and the retarding influence of oppositely
Molarity
charged ions decreases. Therefore mobility of ions
1000 ´ 0.01
= = 10 ohm cm 2 mol-1
3 -1
increases.
.01
45. (b) Specific conductance of the solution (k) = 0.012 58. (d) L °CH3COOH = L°CH3COONa + L°HCl - L °NaCl
ohm–1 cm–1 and resistance (R) = 55 ohm.
Cell constant = Specific conductance × Observed = 91 + 425.9 – 126.4 = 390.5 S cm2mol–1
resistance 59. (b) L° + L ° - = 248 ´ 10 -4 Sm 2 mol-1
Na + OH
= 0.012 × 55= 0.66 cm–1.
46. (b) ohm–1 cm2 (geq)–1 L° + L° = 126 ´ 10 -4 Sm 2 mol -1
Na + Cl -
1000 1 l 1000 L° + L° = 280 ´ 10 -4 S m 2 mol-1
47. (a) L eq = k ´ = ´ ´ Ba 2 + 2Cl -
N R a N
Now, L°Ba(OH)2 = L°BaCl2 + 2L °NaOH - 2L °NaCl
1 1000 1 1000
= ´ cell constant ´ = ´ 0.88 ´ L°Ba(OH) = 280 ´ 10-4 + 2 ´ 248 ´ 10-4 - 2 ´ 126 ´ 10-4
2
R N 220 0.01
2
= 400 mho cm g eq –1 L °Ba(OH) 2 = 524 ´ 10- 4 Sm 2 mol- 1.
48. (c) Molar conductance of solution is related to specific LM 9.54
conductance as follows : 60. (b) a = ¥ = = 0.04008 = 4.008 %.
LM 238

Ùm = k ´ 1000 ....(a)
61. (d) Cell constant = l/a
Unit = m/m2 = m–1.
C
where C is molar concentration. 62. (d) Larger the size, lower the speed.
Putting k = 6.3 × 10–2 ohm–1 cm–1 and L¥ 2 -1
63. (a) m = 57 + 73 = 130 Scm mol
 EBD_7374
564 CHEMISTRY

64. (b) We know, R µ l or R =r æç l ö÷ , where proportionality R=

0.4 ´ 1000
= 500 Ohms
A è Aø 8 ´ 0.1
constant r is called resistivity. If l = 1m and A = 1m2, 71. (d) Charge on Mg and Ca ion is greater than that of Na and
then R = r i.e., Resistance = Resistivity.. K, so Mg and Ca ions possess higher conductivity,
65. (d) The specific conductivity decreases while equivalent also solvation of metal ion decreases as we move down
and molar conductivities increase with dilution. the group, hence conductivity increases)
66. (b) Here, R = 31.6 ohm 72. (d) The conductivity of electrolytic solution depends
upon all of the given factors.
1 1
\ Conductance = = ohm -1 = 0.0316 ohm–1 73. (b) At anode :
R 31.6 1
ˆˆ† H 2 O + O2
2 HO – ‡ˆˆ
Specific conductance = conductance × cell constant. 2
= 0.0316 ohm–1 × 0.367 cm–1 74. (b) Given current (i) = 0.5 amp;
= 0.0116 ohm–1 cm–1 Time (t) = 100 minutes × 60 = 6000 sec
Now, molar concentration = 0.5M (given) Equivalent weight of silver nitrate (E) = 108.
= 0.5 × 10–3 mole cm–3 According to Faraday's first law of electrolysis
k 0.0116 Eit 108 ´ 0.5 ´ 6000
\ Molar conductance = = W= = = 3.3575 g.
C 0.5 ´ 10 -3 96500 96500
= 23.2 S cm2 mol–1 75. (d) 1 mole of e– = 1F = 96500 C
67. (b) According to Kohlrausch’s law, molar conductivity of 27g of Al is deposited by 3 × 96500 C
weak electrolyte acetic acid (CH3COOH) can be 5120 g of Al will be deposited by
calculated as follows:
3 ´ 96500 ´ 5120
(
LoCH3COOH = LoCH3COONa + LoHCl - L oNaCl ) =
27
= 5.49 ´ 10 7 C

\ Value of L o NaCl should also be known for 76. (c) Electrorefining and electroplating are done by
electrolysis.
calculating value of LoCH 3COOH .
77. (d) WA WB 1.6 Wt. of Ag
1 l = ; =
68. (a) k = ´ EA EB 8 108
R A
\ Wt . of Ag = 21.6 g
1 l
1.3 = ´ 78. (b) Cu+2 + 2e– ® Cu (s)
50 A
2 × 96500 C 63.6g
l
= 65m-1 63.6
A 9650 C will deposit = ´ 9650 = 3.18 g
2 ´ 96500
k ´ 1000
L= 79. (a) Charge = 0.2 × 1 Faraday
molarity
= 0.2 × 96500 coulombs
[molarity is in moles/litre but 1000 is used to convert = 19300 = 1.93 × 104 coulombs
liter into cm3]
æ 1 ö 80. (d) Ag + + e - ¾¾
® Ag
çè ´ 65 m -1 ÷ ´ 1000 cm 3
260 ø 96500 coulombs deposit = 108 g of Ag
=
0.4 moles 108
\ 965 coulombs deposit = ´ 965 = 1.08 g Ag
650 m-1 1 96500
= ´ m3
260 ´ 4 mol 1000 81. (d) C 6 H 5 NO 2 ∗ 6H ∗ ∗ 6e, ¾ ¾
↑ C 6 H 5 NH 2 ∗ 2H 2 O
= 6.25 × 10–4 S m2 mol–1
123
69. (b) L° for CH3COOH E C6 H 5 NO 2 (eq.wt) < < 20.5
6
= l°CH COO- + l °Na + +l °H+ + l Cl
°
- -l
°
Na +
°
- l Cl -

°
3
°
w ≥96500
= l CH3COO - + l H+ Number of coulombs required =
Eq. wt
= 90 + 425 – 125 = 390 mho cm2 mol–1.
Lc 12.3≥ 96500
Degree of dissociation (a) = °m =
7.8
= 0.02 < < 57900 C
20.5
L m 390
82. (a) According to Faraday law's of electrolysis, amount of
70. (d) L C = L 0 ´ a = 8 electricity required to deposit 1 mole of metal
1 l 1000 = 96500 C = 1 F
LC = ´ ´
R A N i.e., for deposition of 108g Ag electricity required = 1 F
ELECTROCHEMISTRY 565

83. (a) For deposition of silver, reaction is 96. (a) Electrolysis of these (i), (ii) and (iii) salt release Chlorine
Ag+ + e– ¾¾ ® Ag which is yellowish in colour while Br2 is reddish brown
1 mol of Ag will be deposited by in colour
= 1 F = 96500 C = 9.65 × 104 C 97. (b) Electronic conductance decreases with increase in
Since 1 equivalent weight of Ag is also equal to the temperature whereas electrolytic conductance
weight of its 1 mol, hence 1 equivalent weight of Ag increases with increase in temperature as no. of ions
will be deposited by = 9.65 × 104 C or charge carr iers increases with increase in
84. (b) A current of 96500 coulombs liberate 1 mole of O2. temperature.
Þ 96500 C liberates = 22.4 L of O2 at NTP 98. (a) Gold is an inert metal. Electrodes made up of inert
metals does not participate in chemical reaction.
22.4
Þ 9650 C liberates < ≥ 9650 99. (a) 2H+ + 2e– ¾ ¾ ↑ H2
96500
2 22400
= 2.24 L of O2 at NTP EH (Eq. wt) = =1 g = < 11200 ml (STP)
2 2
56
85. (b) Fe2+ + 2e - ® Fe; E Fe = = 28 96500≥112
2 Total charge passed = < 965
1 Faraday liberates = 28 g of Fe 11200
3 Faraday liberates = 3 × 28 = 84 g Q = It = 965
86. (c) 965
87. (d) Charge (Coulombs) pass per second = 10–6 I= < 1amp.
965
number of electrons passed per second
100. (c) Using Faraday’s second law of electrolysis,
10 -6
= = 6.24 ´ 1012 Weight of Cu deposited Equ. wt. of Cu
1.602 ´ 10 -19 =
Weight of Ag deposited Equ. wt. of Ag
88. (d)
89. (d) Charge on one mole of electrons = 96500 C. w Cu 63.5 1
90. (a) When platinum electrodes are dipped in dilute solution Þ = ´
0.18 2 108
H2SO4 than H2 is evolved at cathode.
91. (b) In electrolysis of NaCl when Pt electrode is taken then 63.5 ´ 18
Þ wCu = = 0.0529 g.
H2 liberated at cathode while with Hg cathode it forms 2 ´108 ´ 100
sodium amalgam because more voltage is required to 101. (c) According to the definition 1 F or 96500 C is the charge
reduce H+ at Hg than Pt. carried by 1 mol of electrons when water is electrolysed
92. (a) When molten or fused NaCl is electrolysed, it yields 2H2O ¾¾ ® 4H+ + O2 + 4e–
metallic sodium and gaseous chlorine. Reactions So, 4 Faraday of electricity liberate = 32 g of O2.
involved are as follows: Thus 1 Faraday of electricity liberate
NaCl (s) ¾® Na+ (l) + Cl– (l)
32
Na+ + e– ¾® Na (l) (at cathode) = g of O2 = 8 g of O2
Cl– (l) ¾® Cl (g) + e– (at anode) 4
Cl (g) + Cl(g) ¾® Cl2 (g) 102. (b) ˆˆ† H∗ ∗ OH,
H 2O ‡ˆˆ
93. (b) Pt4+ + 4e–—® Pt
4F electricity is required to deposit 1 mole of Pt. 1
H∗ ∗ e, ¾¾ ↑ H2
\ 0.80 F of electricity will deposit 2
= 1/4 × 0.80 moles of Pt = 0.20 mol. \ 0.5 mole of H2 is liberated by 1 F = 96500 C
94. (d) 1F ® 11.2 L Cl2 at STP 0.01 mole of H2 will be liberated by
9.65 ´ 5 ´ 60 ´ 60 96500
\ No. of Faradays = = 1.8 = ≥ 0.01 = 1930 C
96500 0.5
\ Vol. of Cl2 = 1.8 × 11.2 L = 20.16 Q=I ×t
95. (b) W = Zit Q 1930 C
where Z = Electrochemical equivalent t< < < 19.3≥10 4 sec
I 10 ≥10,3 A
63
Eq. wt. of copper = = 31.5 1
2 103. (b) At Anode, Cl - ® Cl + e -
2 2
31.5
Z= 35.5 ´ 2
96500 Equivalent wt. of chlorine (ECl2 ) = = 35.5
2
31.5
W = Zit = ´ 1.5 ´ 10 ´ 60 = 0.2938g ECl2 ´ I ´ t 35.5 ´ 2 ´ 30 ´ 60
96500 WCl2 = = = 1.32 g.
96500 96500
 EBD_7374
566 CHEMISTRY

W Q application of external current.

104. (a) By Faraday's 1st Law of electrolysis, < Saline water is highly conducting and hence accelerates
E 96500
(where Q = it = charge of ion ) the formation of rust.
We know that no. of gram equivalent 117. (b) Magnesium provides cathodic protection and prevent
rusting or corrosion.
W it 1 ´ 965 1 118. (c) Mercury cell being primary in nature can be used only
= = = =
E 96500 96500 100 once.
(where i= 1 A, t = 16×60+5 = 965 sec.) 119. (c)
Since, we know that 120. (d) Fuel cells produce electricity with an efficiency of about
1 70% compared to thermal plants whose efficiency is
Normality = No. of gram equivalent 100 = 0.01 N about 40%.
=
Volume (in litre) 1 121. (c) Reaction occurring at anode
105. (b) Quantity of charge passed = 0.5 × 30 × 60 = 900 coulomb 2Fe ( s ) ¾¾ ® 2Fe2 + + 4e -
900 coulomb will deposit = 0.2964g of copper Reaction occuring at cathode
O 2 ( g ) + 4H + ( aq ) + 4e- ¾¾
® 2H 2 O
\ 96500 coulomb will deposit
Discharge
0.2964 ˆˆˆˆˆˆ†
ˆ
122. (d) Pb + PbO2 + 2H 2SO 4 ‡ˆˆˆˆˆˆ
ˆ 2PbSO4 + 2H 2 O.
= ´ 96500 = 31.75 g of copper Recharge
900 Sulphuric acid is consumed on discharging.
Thus, 31.75 is the eq. mass of copper
123. (d) This is because zinc has higher oxidation potential than
At. mass = Eq. mass × Valency
Ni, Cu and Sn. The process of coating of iron surface
63.56 = 31.75 × x
with zinc is known as galvanization. Galvanized iron
x = + 2.
sheets maintain their lustre due to the formation of
106. (a) The charge carried by 1 mole of electrons is one faraday.
protective layer of basic zinc carbonate.
Thus for a reaction
124. (c) At cathode reduction occurs according to following
M n + + ne - ¾¾ ®M reaction.
nF = 1 mole of M +4 +3
Al3+ + 3e- ¾¾
® Al MnO 2 + NH +4 + e - ¾¾
® MnO ( OH ) + NH3
3F 1 mol
1F 1/3 mol
Exercise-2
Cu 2+ + 2e - ¾¾
® Cu
2F 1 mol 1. (c) Standard electrode potential of copper electrode can
1F 1/2 mol
be calculated by constructing a concentration cell
Na + + e - ¾¾
® Na composed of two half cell reactions in which
1F 1 mol
concentration of species on left hand and right hand
The mole ratio of Al, Cu and Na deposited at the
side are unity.
1 1
respective cathode is : :1 or 2 : 3 : 6.
3 2 Pt ( s) | H 2 ( g,1 bar ) | | H + ( aq., 1 M ) || Cu 2 + ( aq, 1 M ) | Cu
107. (b) Total of 6 electrons are required to form 2 moles of Cr 3+ 144444424444443 144424443
Oxidation half cell Reduction half cell
therefore to form 1 mole 3F of charge is required.
108. (b) During charging, the lead storage battery behaves like 2. Electrode potential for Mg electrode varies according to
an electrolytic cell. So, at anode the reaction is the equation :
0.059 1
® PbO 2 + 4H + + SO 42 - + 2e -
PbSO 4 + 2H 2 O ¾¾ E 2+ = E° 2 + - log
Mg /Mg Mg /Mg 2 [Mg 2+ ]
109. (c) 2NH 4 Cl + Zn ® 2NH 3 + ZnCl 2 + H 2 ­ . 0.059
E 2+ = E° 2 + + log [Mg 2+ ]
110. (b) In H 2 - O 2 fuel cell, the combustion of H2 occurs to Mg /Mg Mg /Mg 2
0.059
create potential difference between the two electrodes. E 2+ = log [Mg 2 + ] + E° 2 +
111. (d) Primary cells are those cells, in which the reaction Mg /Mg 2 Mg /Mg
occurs only once and after use over a period of time, it This equation represents equation of straight line.
becomes dead and cannot be reused again. e.g., 0.059
Hence intercept (c) = E°Mg 2 + / Mg and slope =
Leclanche cell and mercury cell. 2
112. (c) The electrolyte used in Leclanche cell is moist paste of Thus, equation can be diagrammatically represented as:
NH4Cl and ZnCl2.
113. (c)
114. (b) H2 – O2 fuel cell supply power for pressure.
®

115. (d) Prevention of corrosion by zinc coating is called E

Mg 2+ / Mg
galvanization.
116. (a) Cathodic protection is best method to prevent iron from
rusting. In this method iron is made cathode by log [Mg2+] ®
ELECTROCHEMISTRY 567

3. (c) Ecell is an intensive property as it is independent of Net reaction:

the mass of species but DrG of cell reaction is an 2PbSO4 (s) + 2H2O ® Pb(s) + PbO2(s) + 4H+ (aq.) +
extensive property because this depends upon mass 2SO42– (aq.)
of species.
L ° m( NH = l° °
4. (b) Cell emf is the difference between the electrode 16. (b) 4Cl) ( NH 4+ ) + l ( Cl– ) ...(i)
potential of two electrodes when no current is drawn
through the cell. L °m ( NaOH ) = l °( + l (°
Na + ) OH + )
...(ii)
5. (d) Inert electrode does not participate in redox reaction
and acts only as source or sink for electrons. It L °m ( NaCl) = l °( + l °(
Na + ) Cl– )
...(iii)
provides surface either for oxidation or for reduction
reaction. On adding (i) & (ii) and subtract (iii), we get :
6. (c) If an external opposite potential is applied on the L °m( NH + L °m( NaOH ) - L °m ( NaCl) = L °m( NH OH )
galvanic cell and increased slowly. It is observed that 4Cl ) 4

the reaction continues to take place till the opposing 17. (d) In the electrolysis of aqueous NaCl, following
voltage reaches the value 1.1V. At this stage no current reactions are possible at anode.
flow through the cell. Any further increase in the 1
external potential restarts the reaction but in the At anode; Cl - ( aq ) ¾¾
® Cl2 ( g ) + e - ;
2
opposite direction.
Hence, now the cell will behave like an electrolytic cell. E°cell = 1.36V
7. (c) Greater the solvation of ions of an electrolyte lesser
will be the electrical conductivity of the solution. ® O 2 ( g ) + 4H + ( aq ) + 4e - ;
At cathode; 2H 2 O ( l ) ¾¾
8. (b) Among the given options chromium has highest
negative value of E° hence, it is the most strongest E°cell = -1.23 V
reducing agent. The reaction at anode with lower value of E° is preferred
9. (c) Higher the positive value of standard reduction and therefore water should get oxidised in preference
potential of metal ion higher will be its oxidising to Cl–(aq) . However on account of overpotential of
capacity. oxygen reaction (d) is preferred.
Since, E° has highest positive value ( +6) ( +7)
MnO4- / Mn 2 +
18. (c) Mn O 24 - ¾® MnO 4- + e -
hence it is the strongest oxidising agent. 0.1 mole
10. (b) On moving down in electrochemical series reducing Quantity of electricity required = 0.1F
power decreases as the value of electrode potential = 0.1 × 96500 = 9650 C
decreases. 19. (d) wO = nO × 32
2 2
11. (d) E° has highest positive value. So Mn 2+
MnO4- / Mn 2 + 5600
wO = ´ 32 = 8g = 1 equivalent of O2
is most stable ion in its reduced form. 2 22400
E° = 1 equivalent of Ag = 108 g
12. (d) Cr3+ / Cr has the lowest value of SRP. Hence, Cr 3+ is
20. (b) The more the reduction potential, the more is the
the most stable oxidised species. deposition of metals at cathode. Cation having E° value
+3e
13. (c) Al3+ ( aq ) ¾¾¾ ® Al ( s) less than – 0.83 V (reduction potential of H 2 O ) will
Hence, total 3F is required. not deposit from aqueous solution.
21. (d) The specific conductivity decreases while equivalent
l
14. (d) Cell constant (G) = and molar conductivities increase with dilution.
A 22. (a) At cathode : Cu2+(aq) + 2e– ® Cu(s)
where l = length of object and A = area of cross section (Reduction)
Since, l and A remain constant for any particular object At anode : Cu(s) ® Cu2+(aq) + 2e–
hence value of cell constant always remains constant. (Oxidation)
15. (a) When the lead storage battery is recharged the 23. (a) Given for 0.2 M solution
reaction occurring on cell is reversed and PbSO4 (s) R = 50 W
on anode and cathode is converted into Pb and PbO2 k = 1.4 S m–1 = 1.4 × 10–2 S cm–1
respectively
l 1 l l
The electrode reactions are as follows Now, R = ρ = ´ Þ = R ´ κ = 50 ´ 1.4 ´ 10-2
Anode reaction: a κ a a
PbSO4 (s) +2e– ® Pb(s) + SO42– (aq) (Reduction) For 0.5 M solution
Cathode reaction: R = 280 W
PbSO4 (s) + 2H2O ® PbO2(s) + SO42– + 4H+ + 2e– κ=?
(Oxidation)
 EBD_7374
568 CHEMISTRY

l ,0.059
= 50 ´ 1.4 ´ 10 -2 Accordingly Ered. < log ∗
1
a n [H ]
l 1 l
Þ R=ρ = ´ = 0.059 log 10–7
a κ a
1 i.e., 0.059 × (–7) = – 0.41 volt.
Þ κ= ´ 50 ´ 1.4 ´ 10 -2
280 32. (d) Cu 2+ + 2e – ¾¾ ® Cu
1
= ´ 70 ´ 10-2 = 2.5 × 10–3 S cm–1 2F i.e. 2 × 96500 C deposit Cu = 1 mole = 63.5 g
280
-nFE cell
κ ´ 1000 2.5 ´ 10 -3 ´ 1000 33. (a) Efficiency of fuel cell is: h = ´ 100
Now, L m = = DH
M 0.5 34. (b) The mass of the substance deposited when one
= 5 S cm2 mol–1 = 5 × 10–4 S m2 mol–1 Faraday of charge is passed through its solution is
24. (c) According to Debye Huckle onsager equation, equal to gram equivalent weight.
λC = λ¥ - B C 35. (a) 2H+(aq) + 2e– ® H2(g)
0.0591 PH2
25. (a) (a) Mn 2 + + 2e - ® Mn; E 0 = -1.18 V; ... (i) \ E = E0 – log
2 [ H + ]2
(b) Mn 3+ + e ® Mn 2 + ; E0 = -1.51 V; ... (ii) PH 2
0 = 0 – 0.0295 log
Now multiplying equation (ii) by two and subtracting (10-7 )2
from equation (i) PH 2
3Mn 2+ ® Mn + + 2Mn 3+ ;
(10-7 )2 = 1
E 0 = E Ox. + E Red. = – 1.18 + (– 1.51) = – 2.69 V PH2 = 10–14 atm
(–ve value of EMF (i.e. DG = +ve) shows that the
reaction is non-spontaneous) 36. (b) Eocell = Ecathode
o o
- Eanode o
= Eright o
- Eleft
26. (b) Ca is a reactive metal and extraction of reactive metal is
not possible by electrolysis of aq. salt solution. E ocell = 0.25 - 0.52 = -0.27V
27. (d) 37. (b) Galvanization is the process by which zinc is coated
over corrosive (easily rusted) metals to prevent them
28. (c) 2 Cu + ¾¾
® Cu +2 + Cu from corrosion.
38. (c) Anode :
2 e - + Cu +2 ¾
¾® Cu ; E1º = 0.34V; ...(i)
CuSO 4 / Pt.
e - + Cu + 2 ¾
¾® Cu + ; E º2 = 0.15V; ...(ii) 1
H2O ¾ ¾® 2H + + O 2 + 2e -
2
Cu + + e - ® Cu; E3º = ? ... (iii) CuSO 4 / Cu

Now, DG1º = -nFE1º = -2 ´ 0.34F Cu(s) ¾ ¾® Cu 2 + (aq) + 2e -

KCl/Pt
DG º2 = -1´ 0.15F , DG 3º = -1´ E 3º F 2Cl - ¾ ¾® Cl 2 (aq) + 2e -
Cathode :
Again, DG1º = DG º2 + DG 3º
Cu 2 + (aq) + 2e - ¾
¾® Cu(s) (pH = decrease)
2+ -
Þ -0.68F = -0.15F - E3º F Cu (aq) + 2e ¾ ¾® Cu(s) (pH = constant)

º 2 H 2 O + 2e - ¾
¾® H 2 + 2OH - (aq) (pH = increase)
0 Þ E3 = 0.68 - 0.15 = 0.53V
39. (c) The reaction
E ºcell º
= E cathode (Cu + / Cu) 2 Cu + (aq) ¾
¾® Cu(s) + Cu 2+ (aq)
- º
E anode (Cu +2 +
/ Cu )
0.0592 [Cu 2+ ]
= 0.53 – 0.15 = 0.38 V. E cell = E°cell – log
1 [Cu + ]2
29. (b) HCl completely dissociates to give H+ and Cl - ions,
hence act as very good electrolyte. While others are At equilibrium E cell = 0
non- electrolytes. \ E°cell = 0.0592 log K c
30. (d) A device that converts energy of combustion of fuels,
directly into electrical energy is known as fuel cell. 0.52 – 0.16
or, log K c =
31. (c) pH changes from 0 to 7. 0.0592
\ [H+] changes from 1 to 10–7 M. 6
\ K c = 1.2 ´ 10
ELECTROCHEMISTRY 569

40. (b) The oxidation potential nFE°

log K =
1 2.303 RT
µ and reduction potential
Concentration of ions nFE°
= 0.4342 ........ (i)
µ concentration of ions. The cell voltage can be RT
increased by decreasing the concentration of ions nFE°
around anode or by increasing the concentration of ln K =
RT
ions around cathode nFE °
41. (c) Li+ being smallest, has maximum charge density. ....... (ii)
K = e RT
\ Li+ is most heavily hydrated among all alkali metal ions.
Effective size of Li+ in aqueous solution is therefore, o 0.059 1.10 ´ 2
49. (b) E cell = log K c or = log K c
largest. So, moves slowest under electric field. 2 0.059
42. (b) For cell,
\ K c = 1.9 ´1037
Zn|ZnSO4(0.01 M) || CuSO4(1.0 M)|Cu

2.303RT log [ Zn 2+ ] 50. (c) l m =

1000k 1000 ´ 3.75 ´ 10 -4
= = 3.75;
E cell = E°cell -
nF [ Cu 2+ ] 0.1 0.1
lm 3.75
2.303RT ( 0.01) a= = = 1.5 ´ 10-2 ;
\ E1 = E°cell - ´ log l¥ 250
2´ F 1 m
When concentrations are changed for ZnSO4 and Ka = Ca2 = 0.1 ×(1.5 ×10 –2)2 = 2.25 ×10–5
CuSO4, we can write 51. (c) Calculate E°cell corresponding to each compound
undergoing disproportionation reaction. The reaction
2.303RT 1
E2 = E°cell - ´ log for which E°cell comes out + ve is spontaneous.
2F 0.01 HBrO ¾® Br2 E° = 1.595 V, SRP (cathode)
\ E1 > E2 HBrO ¾® BrO 3– E° = –1.5 V, SOP (anode)
43. (c) From the given data we find Fe3+ is strongest oxidising
agent. More the positive value of E°, more is the 2HBrO ¾® Br2 + BrO 3–
tendency to get oxidized. Thus correct option is (c). E°cell = SRP (cathode) – SRP (anode)
44. (d) Here n = 4, and [H+] = 10– 3 (as pH = 3) = 1.595 – 1.5
Applying Nernst equation = 0.095 V
0.059 [Fe 2 + ]2 E°cell > 0 Þ DG° < 0 [spontaneous]
E = Eº – log
n [H + ]4 (pO 2 ) k ´ 1000
52. (d) Molar conductivity Ù m =
M
0.059 (10-3 )2 M = Molarity
= 1.67 - log k = specific conductivity
4 (10-3 ) 4 ´ 0.1
1 1 l
0.059 k= ×´ cell constant; = ×
< 1.67 , log107 R R A
4
= 1.67 – 0.103 = 1.567 1 1cm
= ´
45. (a) E° = 1.51V 5 ´10 W 100 cm 2
3
MnO 4– /Mn 2 +
-6
E° = 1.36V = 2 ´10 W -1cm -1 orScm -1
Cl2 /Cl –
2 ´10-6 ´1000 2
E° = 1.33V = ;= S cm2 mole–1
Cr2 O72– /Cr3+ 0.1 100
E° = – 0.74 53. (a)
Cr 3 + /Cr 54. (c) We know DG° = – nFE°
Since Cr3+ is having least reducing potential, so Cr is
DG°
the best reducing agent. \ E° = -
46. (a) nF
47. (a) More is E↓RP , more is the tendency to get itself reduced 237.2 ´ 1000J
=+ = 1.23 V [Q n = 2]
or more is oxidising power. 2 ´ 96500
48. (c) DG = –2.303 RT log K 55. (c) B2 H 6 + 3O 2 ® B2 O3 + 3H 2O
–nFE° = –2.303 RT log K
Moles of B2H6 = 27.6/27.6 = 1.0
 EBD_7374
570 CHEMISTRY

moles of O2 required = 3x moles of B2H6 = 3 × 1.0 = 3 4. (d) For spontaneous E° > 0,

I´t minimum possible spontaneous E° = 0.28 V
= moles of O2 × 4 C
96500 5. ˆˆ† Co 2 + ( aq ) , Q = 2
(b) Co 2 + ( aq ) ‡ˆˆ
C1 C2 C1
100 ´ t 3 ´ 4 ´ 96500 11580
= 3´4 ; t = sec. = = 3.2 h C2
96500 100 3600
If < 1, D G < 0
C1
W q
56. (a) By Faraday's Ist Law, =
E 96500 6. (c) 2Mn 2 + ¾¾
® 2Mn 3+ + 2e - , DG1°
(where q = it = charge of ion)
we know that no of equivalent Mn 2+ + 2e - ® Mn, DG°2
=
W
=
it
=
1´ 965
=
1 3Mn 2+ ( aq ) ® Mn (s ) + 2Mn 3+ ( aq )
E 96500 96500 100
– 2 × F × E°3 = – 2 ×F × [–1.51] – 2 × F × (–1.185)
(where i = 1 A, t = 16×60+5 = 965 sec.)
Since, we know that E3° = -2.695
1 0.0591
no. of equivalent 100 E°3 = + log K eq ; K eq ; 6.3 ´10-92 .
Normality = = 2
Volume (in litre) 1
æ dE ö
= 0.01 N 7. (c) DS = nF ç ÷ Þ 2 ´ 96500 ´ 1.5 ´ 10 -4
è dT ø p
57. (d) No. of moles of
Þ 28.95 J/K mol
+15 ´ 60 ´1.25 ´10 -3 1 8. (a) It is a concentration cell, therefore, E°cell = 0.
Ag = ´
96, 500 1 1
= 0.0116 × 10–3 pH of WA = (pKa – log c)
2
-5 1
\ éë Ag + ùû = 1.16 ´ 10 = 1.16 ´ 10 -4 = (4.74 – log 10– 3) = 3.87
100 2
1000
pH of NaOH = 14 – 3 = 11
\ E = – 0.059 (pHc – pHa)
= – 0.059 (11 – 3.87) = – 0.42 V
Exercise-3
k k
1. (b) For this cell, reaction is; Zn + Fe2+ ® Zn2+ + Fe 9. (c) Lm = ´ 1000; ( x + y) = ´ 1000
M M
0.0591 c 0.0591 c
E = E° - log 1 ; E° = E + log 1 1000 ´ k
n c2 n c2 Þ M=
( x + y)
0.0591 10 -2
E° = 0.2905 + log -3 = 0.32 V. k ´ 1000 ´ 188
2 10 Solubility (in gL–1) =
0.0591 x+y
E° = log K eq 10. (a) (Eq. = Charge on the ion/Total charge)
2
0.32 ´ 2 0.32 1 1 1
log K eq = = [K+] = mole × 2 = mole = Eq.
0.0591 0.0295 8 4 4
0.32 6 3
\ K eq = 10 0.0295 . [Al3+] = = Eq.
8 4
2. (b) In electrolysis of NaCl when Pt electrode is taken, then 8
H2 liberated at cathode, while with Hg cathode it forms [SO42–] = = 1 Eq.
sodium amalgam because more voltage is required to 8
reduce H+ at Hg than at Pt. Leq° K2SO4.Al2(SO4)3.24H2O
3. (c) A cation having highest reduction potential
will be reduced first and so on. However, Mg 2+ = leq° (K+) + leq° (Al3+) + leq° (SO42–)
in aqueous solution will not be reduced
æ E° ö. 1 3
<E = × 73.5 + 149 × + 85.8 × 1
çè Mg 2 + / Mg 1
H2 O / H 2 + OH - ÷
ø
Instead water 4 4
2
would be reduced in preference. = 18.375 + 111.75 + 85.8
= 215.92
ELECTROCHEMISTRY 571

11. (c) Total charge = 2 Subtracting Eqs. (i) from (iii),

Charge on the ion ®Fe3+ + 3e-;

Fe ¾¾ - DG °3 = 3E°3F
Number of equivalent of ion =
Total charge
®Fe2+ + 2e-;
Fe ¾¾ - DG1° = 2E1°F
COO– 2 ...(iv)
\ Eq of | = =1 Fe2 + ¾¾
® Fe3+ + e - ; -DG °3 + DG1° = 3E°3F - 2E1°F
COO – 2 Comparing Eqs. (ii) and (iv)

1 1 -DG °2 = -DG°3 + DG1° = 3E3° F - 2E1°F

Eq of Na+ = , Eq of K+ =
2 2 + E°2F = 3E°3F - 2E1°F
COONa 2E1° + E°2
\ l°eq | \ E °3 = or 3E 3° = 2E1° + E °2
COOK 3

15. (c) ®In + ; E1° = -0.42 V ...(i)

Given, In3+ + 2e- ¾¾
COO– 1 1
= l°eq | + l° Na + + l° K+ In 2+ + e- ¾¾
°
®In + ; E 2 = -0.40 V ...(ii)
2 2
COO– By subtracting Eq. (ii) from Eq. (i) a third half-cell reaction
can be obtained as:
50 73
= 74 + + = 135.5 ohm–1 cm2 eq–1 é where E° ´ 1 ´ F = E° ´ 2 ´ F - E ° ´ 1 ´ F ù
2 2 3 1 2
ê ú
12. (b) Upto equivalence point highly mobile H+ get replaced ê or E° = 2 ´ ( -0.42 ) - 1 ´ ( -0.40 ) ú
ê 3 ú
by much less mobile K+ ions. Hence resistance of solu-
ê = -0.44 V ú
tion increases. After equivalence point resistance de- ë û
creases due to unreacted K+ and highly mobile OH–
°
ions. In3+ + e- ¾¾
® In 2+ ; E3 = -0.44 V
13. (d) Al(s ) + 3Ag + (aq) ¾¾
® Al3+ ( aq) + 3Ag( s) For the reactions: Cu 2+ + e- ¾¾
®Cu + ; E°4 = 0.15

[Al3+ ] 0. 1 In 2+ ¾¾
°
® In3+ + e- ; E3 = +0.44
Q= = = 10 2
[Ag + ]3 0.13
The net redox change: Cu 2 + + In 2 + ¾¾ ® Cu + + In3+ ;
log10 Q = log10 102 = 2 log10 10 = 2
E° cell = E°4+ E°3 = 0.15 + 0.44 = 0.59 V
14. (a) ®Fe2+ + 2e-;
Fe ¾¾ - DG1° = 2E1°F ...(i)
° 0.059
Also E cell = log K C
1
Fe2+ ¾¾
® Fe3+ + e- ; - DG°2 = E°2F ...(ii)
0.059
0.59 = log K C \ K C = 1010
®Fe3+ + 3e-;
Fe ¾¾ - DG °3 = 3E°3F ...(iii) 1
 EBD_7374
572 CHEMISTRY

18. CHEMICAL KINETICS

16. (d) order of reaction may be zero, whole number or fractional.
Exercise - 1
17. (b) 2 NO (g) + Cl2(g) ƒ 2 NOCl(g)
1. (b) 2. (c) Rate = k [NO]2 [Cl]
3. (a) If we write rate of reaction in terms of concentration of The value of rate constant can be increased by
NH3 and H2,then increasing the temperature.
Rate of reaction 18. (a) For a zero order reaction.
1 d[ NH 3 ] 1 d[H 2 ] rate =k[A]º i.e. rate = k
= =-
2 dt 3 dt hence unit of k = M.sec–1
d[ NH 3 ] 2 d[H 2 ] For a first order reaction.
So, =- rate = k [A]
dt 3 dt
k = M.sec–1/M = sec–1
4. (d) 5. (c) 6. (a) 7. (b) 8. (c) 9. (d) 19. (d) The reaction involving two different reactant can never
10. (a) Average rate depends upon the chan ge in be unimolecular.
concentration of reactants or products and the time
20. (b) For reaction 3A ¾ ¾® B + C
taken for that change to occur. Average rate cannot be
If it is zero order reaction r = k [A]0, i.e the rate remains
used to predict the rate of a reaction at a particular
same at any concentration of 'A'. i.e independent upon
instant as it would be constant for the time interval for concentration of A.
which it is calculated. So, to express the rate at a 21. (c) k = (mol lit –1 ) 1–n time –1 . For given reaction
particular moment of time we determine the n = 2. \ k = mol–1 lit sec–1
instantaneous rate. It is obtained when we consider 22. (b) Velocity constant ‘k’ is characteristic constant of a
the average rate at the smallest time interval say dt ( i.e. reaction and depends only on temperature and catalyst.
when it approaches zero). 23. (b) Given dx/dt = 2.400 × 10–5 mol litre–1 sec–1
k = 3.10 × 10–5 sec–1
1 d[Br - ] 1 d[Br2 ] For first order reaction
11. (c) - =
5 dt 3 dt 2N 2 O 5 ¾¾
® 2NO 2 + O 2
- dx
d[Br2 ] 3 d[Br ] = k [N 2 O 5 ]
\ =- dt
dt 5 dt or 2.4 × 10–5 = 3.0 × 10–5 [N2O5]
12. (b) Rate of disappearance of reactants = Rate of appearance
2.4 ´ 10 -5
of products or [N2O5] = = 0.8 mol. litre–1
3.0 ´ 10 -5
1 d(N 2 O5 ) 1 d(NO2 ) d(O 2 ) 24. (c) Rate1 = k [A]n [B]m; Rate2 = k [2A]n [½B]m
- = =
2 dt 4 dt dt
1 1 Rate 2 k [2A]n [½B]m
k(N 2 O5 ) = k ¢ (N 2 O5 ) = k ¢¢ (N 2 O5 ) \ = = [2]n [½]m = 2n.2–m = 2n–m
2 4 Rate1 k [A]n [B]m
k k¢
= = k ¢¢ 25. (a) 2A + B ¾ ¾® A2B
2 4
k r1 = k[A]2 [B] ...(i)
k¢ = 2k, k ¢¢ = éBù
2 When, [A] = [2A], [B] = ê ú
13. (d) As the slowest step is the rate determining step thus ë2û
the mechanism B will be more consistent with the given 2 éBù 2 [B]
r2 = k [ 2A ] ê ú = k 4[A]
information also because it involve one molecule of H2 ë2û 2
and one molecule of ICl it can expressed as
r = k [H2][ICl] (
= k 2[A]2[B] = 2r1 Q r1 = k[A] [B]
2
)
Which shows that the reaction is first order w.r.t. both \ Rate of reaction is increased two times.
H2 & ICl. 26. (c) Let us consider a reaction,
14. (c) Rate of reaction does not remain constant during the x X + y Y ¾¾ ® aA+bB
complete reaction because rate depends upon the rate = [X]x [Y]y
concentration of reactants which decreases with time. It is given that order of reaction w.r.t. component Y is
15. (a) k remains constant at constant temperature and CO zero.
does not effect the rate of reaction. Hence, rate = [X]x
i.e., rate becomes independent of the concentration of Y.
CHEMICAL KINETICS 573

27. (a) Rate = k[A]° A + B2 ¾

¾® AB + B (Slow )
Unit of k = mol L–1 sec–1
Rate law = k[A][B 2 ] put value of [A] from Ist reaction
1 since A is intermediate k[A 2 ] = A
28. (c) N 2 O ¾¾® N 2 + O2
2
\ Rate law equation = K k[A 2 ][B2 ]
dx
µ [N 2 O]1 1 3
dt \ Order = +1 =
i.e. order of reaction = 1 2 2
29. (d) If rate = k[A]x [B]y [C]z 39. (d) From 1st and 2nd sets of data - no change in rate is
From first two given data observed with the change in concentration of ‘C’. So
8.08 × 10–3 = k [0.2]x [0.1]y [0.02]z .... (i) the order with respect to ‘C’ is zero.
2.01 × 10–3 = k [0.1]x [0.2]y [0.02]z .... (ii) From 1st and 4th sets of data
Divide (1) by (2) we get, 4 = 2x (1/2)y Dividing eq. (4) by eq. (1)
Similarly, from second and third data
(9)y (9)z = 3 1.25 ´ 10 -3 é 0.005 ù
x
2y + 2z = 1 . =ê
5.0 ´ 10 -3 ë 0.010 úû
From first and fourth data 4z = 8 = 23
2z = 3. So z = 3/2, y = – 1, x = 1 or 0.25 = (0.5)x or (0.5)2 = (0.5)x
30. (a) Given r = k [A]3/2 [B]–1/2 \ x=2
3 -1 2 The order with respect to ‘A’ is 2 from the 1st and 3rd
Order = 3/2 – 1/2 = = =1
2 2 sets of data dividing eq. (1) by eq. (3)
31. (b) The order w.r.t. I2 is zero because the rate is not
5.0 ´ 10-3
dependent on the concentration of I2. y
é 0.005 ù
=ê
ë 0.010 úû
32. (c) As we know that, units of rate constant.
1.0 ´ 10- 2
= (unit of conc.)1–n (unit of time)–1
= (mol L–1)1–n (sec)–1 or (0.5)1 = (0.5)y Þ y = 1
On comparing these units with the given units of rate The order with respect to ‘B’ is 1
constant, we get So the order with respective the reactants A, B and C is
(mol L–1)1–n (sec)–1 = L mol–1 sec–1
2, 1 and 0.
Þ Ln–1 mol1–n sec–1 = L mol–1 sec–1 40. (c) The rate of reaction is never negative. Minus sign used
On comparing the powers, we get in expressing the rate only shows that the concentration
n–1=1 Þ n=2 of the reactant is decreasing.
So, reaction is of second order.
33. (d) In case of (II) and (III), keeping concentration of [A] 41. (c) For zero order reaction,
constant, when the concentration of [B] is doubled, rate, r = k[R]°
the rate quadruples. Hence it is second order with
respect to B. In case of I & IV Keeping the concentration dR
Þ =k
of [B] constant. when the concentration of [A] is dt
increased four times, rate also increases four times. Þ R = kt + R0
Hence, the order with respect to A is one. hence where R0 is the concentration of reactant at time t = 0.
Thus [R] increases with time
Rate = k [A] [B]2
42. (a) Plots of conc. [A] Vs time, t
34. (b) Fast Slow
O 3 ¾¾
¾® O 2 + O; O + O 3 ¾¾¾® 2O 2
Zero First
[O 2 ][O]
k= (I) Rate = k' [O3][O] put [O] from (I) order order
1 1
log [A]

[O 3 ] [A] Second Third

[ A] [ A]2
k '[O 3 ]K[O 3 ] order order
r= = k[O 3 ]2 [O 2 ]- 1 t t t
[O 2 ]
Note intermediates are never represented in rate law 1
43. (d) t1/2 µ
equation. a2
35. (c) 1
36. (a) For given reaction x and y may or may not be equal to We know that t1/ 2 µ n -1
a
p and q respectively. i.e. n = 3
37. (a) Thus reaction is of 3rd order.
38. (d) A 2 + B 2 ¾¾® 2AB ; 44. (a) For a zero order reaction
a
A2 ¾
¾® A + A ( Fast ); t1/ 2 =
2k
 EBD_7374
574 CHEMISTRY

45. (a) t1/2 = 4s T = 16s 2.303 a 2.303 100

t= log = log
T16 k (a - x ) 0.0433 50
n= = =4 (\ T = n × t½)
t1/ 2 4 2.303
= log 2 = 16 min
æ1ö n
æ1ö 4 0.0433
0.12
[ A] < [ A]o çç ÷÷÷ < 0.12≥çç ÷÷÷ < < 0.0075 M 51. (d) Unit of k for Ist order reaction is (Time)–1
çè 2 ø çè 2 ø 16
2.303 1 2.303 4
Where [A] o = initial concentration an d [A] 52. (c) t1/ 4 = log = log
= concentration left after time t k 3/ 4 k 3
46. (b) A ® B For a first order reaction 2.303 2.303
= (log 4 - log 3) = (2 log 2 - log 3)
Given a = 0.8 mol, (a – x) = 0.8 – 0.6 = 0.2 k k
2.303 0.8 2.303 0.29
k= log or k = 2.303 log 4 = (2 ´ 0.301 - 0.4771) =
1 0.2 k k
again a = 0.9, a – x = 0.9 – 0.675 = 0.225 53. (b) Since doubling the concentration of B does not change
2.303 0.9 half life, the reaction is of 1st order w.r.t. B.
k= log Order of reaction with respect to A = 1 because rate of
t 0.225
reaction doubles when concentration of A is doubled
2.303 keeping concentration of B constant.
2.303log 4 = log 4
t \ Order of reaction = 1 + 1 = 2 and units of second
Hence t = 1 hour order reaction are L mol–1 sec–1.
47. (b) For a first order reaction, A ® products 2.303 a
54. (a) t = log
r k a-x
r = k[A] or k =
[A] 2.303 2.303
or t = log a - log(a - x)
1.5 ´ 10-2 k k
Þk = = 3 × 10–2
0.5 n -1 n -1
(t1/ 2 )1 æ a2 ö 120 æ 4 ´ 10-2 ö
0.693 0.693 55. (c) = ; =ç ÷ ;n = 2
Further, t1/ 2 = = = 23.1 (t1/ 2 )2 çè a1 ÷ø 240 è 8 ´ 10-2 ø
k 3 ´ 10-2
0.693 56. (N) None of the given options is correct.
48. (c) For first order reaction, k = The given reaction is : 2X + Y —® Z
t1/ 2
d[X] d[Z]
where k = rate constant – =
2dt dt
t1/2 = half life period = 480 sec.
\ Rate of formation of Z is half of the rate of
0.693 disappearance of X.
\ k = = 1.44 × 10–3 sec–1
480
-d[X] -d[Y]
n
=
æ 1ö 2dt dt
49. (c) [A] = [A]0 ç ÷ Rate of disappearrance of X is not equal to rate of
è 2ø
disappearance of Y.
where [A]0 = initial concentration 57. (d) Overall order = sum of orders w.r.t each reactant.
n Let the order be x and y for G and H respectively
1 æ 1ö
= 1ç ÷ ; n = 3 [G]mole [H]mole rate(mole
8 è 2ø Exp.No.
litre-1 litre -1 litre- time -1 )
0.693
t1/ 2 = = 100 sec 1 a b r
6.9 ´ 10-3
2 2a 2b 8r
\ T = n ´ t1/ 2 = 3 × 100 = 300 sec. 3 2a b 2r
50. (b) Given: 75% reaction gets completed in 32 min Q For (1) and (3), the rate is doubled when conc. of
2.303 a 2.303 100 G is doubled keeping that of H constant i.e.,
Thus, k = log = log
t (a - x ) 32 (100 - 75) rate µ [G] \ x = 1
2.303 From (2) and (3), y = 2
= log 4 = 0.0433 min–1
32 \ Overall order is 3.
Now we can use this value of k to get the value of time 58. (a) As doubling the initial conc. doubles the rate of
required for 50% completion of reaction reaction, order =1
CHEMICAL KINETICS 575

65. (d) The integrated rate equations are different for the
59. (c) Rate law : - d [ A] = k [ A]x [ B ] y reactions of different reaction orders. We shall
dt determine these equations only for zero and first order
Doubling [A], rate is doubled. Hence 2x = 2, x =1 chemical reactions.
d [ A]
Similarly y = 1; - = k [ A][ B ] 66. (a) N 2 O 5 ¾Slow
¾¾® NO 2 + NO 3
dt
rate 2.0 ´ 10 -4 N 2 O 5 ¾Fast
¾¾® 3NO 2 + O 2
k= = =1 First step is the rate determining step.
[ A][ B ] 1 ´ 10 -2 ´ 2 ´ 10 -2
[R]0
(rate)2 k (2[ A])(2[b]) 67. (a) For a first order reaction log varies linearly with
= =4 [R]
(rate)1 k[ A][ B ]
time as shown below.
60. (d) For a zero order reaction,
t1/2 µ a0 (initial concentration or initial pressure)
(t1/2)1 µ P1
(t1/2)2 µ P2 slop = k/2.303

[R]0
[R]
( t1/2 )2 P2 ( t1/2 )2 16

log
= , =
( t1/2 )1 P1 45 4
0
Time
16 68. (a) Rewriting the given data for the reaction
(t1/2)2 = ´ 45 = 180 min
4 H+
61. (a) Given initial concentration (a) = 2.00 M; Time taken (t) CH 3COCH 3 ( aq ) + Br2 ( aq ) ¾¾®
= 200 min and final concentration (a – x) = 0.15 M. CH3COCH 2 Br(aq) + H + ( aq) + Br - ( aq)
For a first order reaction rate constant,
S. Initial concent Initialconcentr Initialconcentr Rate of
2.303 a 2.303 2.00 No. -ration of -ation of Br2 -ation of H + disappearance
k= log = log CH3COCH3
t a-x 200 0.15 in M in M of Br2 in Ms -1
in M d dx
2.303 -2 -1 i.e. - [Br2 ]or
= ´ (0.301 + 0.824) = 1.29 ´ 10 min . dt dt
200
Further
1 0.30 0.05 0.05 5.7 ´ 10 -5
2 0.30 0.10 0.05 5.7 ´ 10 -5
0.693 0.693 3 0.30 0.10 0.10 1.2 ´ 10-4
(t1/ 2 ) = = = 53.72 min .
k 1.29 ´ 10-2 4 0.40 0.05 0.20 3.1 ´ 10-4
62. (d) t1/2 = 5 years, T = 15 years hence total number of half Actually this reaction is autocatalyzed and involves
complex calculation for concentration terms.
life periods = 15 = 3 . We can look at the above results in a simple way to
5
find the dependence of reaction rate (i.e., rate of
64 disappearance of Br2).
\ Amount left = = 8g
( 2) 3 From data (1) and (2) in which concentration of
CH3COCH3 and H+ remain unchanged and only the
concentration of Br 2 is doubled, there is no change in
Slope = - k / 2.303 rate of reaction. It means the rate of reaction is
independent of concentration of Br2.
63. (b) Again from (2) and (3) in which (CH3CO CH3) and (Br2)
log C
remain constant but H+ increases from 0.05 M to 0.10
i.e. doubled, the rate of reaction changes from 5.7×10–5
t to 1.2 × 10–4 (or 12 × 10–5), thus it also becomes almost
doubled. It shows that rate of reaction is directly
64. (b) Let x torr of C2H4O decompose after 20 min. Then, proportional to [H+]. From (3) and (4), the rate should
80 – x + 2x =120 ; x = 40 torr = 50% of initial pressure. have doubled due to increase in conc of [H+] from 0.10
Hence t1/2 = 20 min. For 75% reaction, fraction left M to 0.20 M but the rate has changed from 1.2× 10–4 to
25 1 æ 1 ö
2 3.1×10–4. This is due to change in concentration of
= = =ç ÷ CH3COCH3 from 0.30 M to 0.40 M. Thus the rate is
100 4 è 2 ø
directly proportional to [CH3 COCH3]. We now get
No. of half lives = 2. Time needed for 75% reaction., rate = k [CH3COCH3]1[Br2]0[H+]1
2 × 20 = 40 min = k [CH3COCH3][H+].
 EBD_7374
576 CHEMISTRY

69. (a) If a reactant is present in excess, order with respect to If reaction is exothermic, DH = - ve , Ea(b) > Ea( f )
that reactant is zero.
70. (b) In Haber’s process, ammonia is manufactured from N2 If reaction is endothermic, DH = + ve Ea(b) < Ea( f )
and H2 using iron as catalyst with molybdenum as
80. (c)
promoter at high temperature and pressure
81. (c) The rate constant doubles for 10º C rise in temperature.
Fe O (catalyst) For 20º C rise, the rate constant will be 4 times
N 2 + 3H 2 ¾¾¾¾¾¾¾¾¾
2 3 ® 2NH3
Mo(catalytic promoter) \ k1 = 4k2 or k2 = 0.25 K1
k2 Ea æ 1 1ö Ea 1
71. (b) log = ç - ÷ 82. (d) k = Ae - Ea / RT log k = log A – .
k1 2.303R è T1 T2 ø 2.303R T
Ea é 1 1 ù -Ea
log 2 = - Equation of straight line slope = .
2.303 ´ 8.314 ë 293 308 úû
ê 2.303R
Ea 15 83. (c)
0.3 = × 84. (a) Threshold Energy = Energy of activation + Internal
2.303 ´ 8.314 293 ´ 308
energy
0.3 ´ 2.303 ´ 8.314 ´ 293 ´ 308 85. (c) For the exothermic reaction the energy of products is
Ea = .
15 always less than the reactants. If Ea is the energy of
= 34673 J mole–1 = 34.7 J mole–1 activation for the forward reaction, the energy of
activation for backward reaction is E a + DH
72. (b) DH = Ea f - Ea b = 0 86. (b) According to Arrhenius equation, k = Ae–Ea/RT
73. (d) The activation energy depends upon the nature of \ when Ea = 0, k = A
chemical bonds undergoing rupture during chemical Also ln k us 1/T is a straight line with slope = –Ea/R.
reaction and is independent of enthalpies of reactants \ Statements (ii) and (v) are correct.
and products. 87. (d) The relevant expressions are as follows.
E a /RT
74. (b) k = Ae– DH 1
lnk = ln A – Ea/RT log Kp = - +I
R T
For ln k vs 1/T log [X] = log [X]0 + kt
ln A = intercept P/T = constant (V constant)
– Ea/R = slope = –2 × 104 K PV = constant (T constant)
\ Ea = 8.3 × 2 × 104 J mol–1
88. (c)
= 16.6 × 104 J mol–1 or 166 kJ mol–1
r æ T2 -T1 ö æ 100 -10 ö
75. (a) As per Arrhenius equation (k = Ae - Ea / RT ) , the rate 100°C çè
10 ø
÷ çè
10 ø
÷
89. (b) =2 =2 = 29 = 512 (where 2 is
r
constant increases exponentially with temperature. 10°C
76. (b) For a reversible reaction,
temperature coefficient of reaction)
DH = Ea (forward) – Ea (backward)
DH = 150 – 260 = –110 kJ mol–1 Ea
90. (d) log k = log A - …(1)
2.303RT
77. (b) In equation k = Ae - Ea / RT ; A = Frequency factor
k = velocity constant, R = gas constant and Ea = energy 1
Also given log k = 6.0 - (2000) …(2)
of activation T
On comparing equations, (1) and (2)
E T -T
(a) 2.303log 2 = a éê 2 1 ùú
k
78. log A = 6.0 Þ A = 106 s–1
k1 R ë T1T2 û
Ea
= 2000 ;
k 9.0 ´103 é 308 - 298 ù and 2.303 R
log 2 =
k1 2.303 ´ 2 êë 308 ´ 298 úû ÞEa = 2000 × 2.303 × 8.314 = 38.29 kJ mol–1
k2 91. (b) We know more will be activation energy lesser will be
= 1.63; k 2 = 1.63k1;
k1 rate constant. Thus if E1 > E2 then k1< k2. As temperature
k -k increases, it will effect both rates in similar way.
Increase in k1 = 2 1 ´ 100
k1 1
92. (b) A graph plotted between log k vs for calculating
1.63k1 - k1 T
= ´ 100 = 63.0% activation energy is shown as
k1
79. (b) DH = Ea( f ) - Ea (b)
Thus energy of activation for reverse reaction depend log k
upon whether r eaction is exothermic or
endothermic. 1/T
CHEMICAL KINETICS 577

from Arrhenius equation 2. (c) The heat absorbed or evolved during the reaction
Ea remains unchanged in presence of catalyst as there is
log k = log A - no change in stability of reactant and product.
2.303 RT
93. (b) T2 = T (say), T1 = 25°C = 298K, 3. (b) Arrhenius equation relates activation energy of a
chemical reaction with rate constant of a reaction at
Ea = 104.4 kJ mol–1 = 104.4 × 103 J mol–1 two different temperatures.
k1=3 × 10 –4, k2 = ?, æk ö E é1 1 ù
ln ç 1 ÷ = a ê - ú
log
k2
=
Ea é 1 1 ù
-
è k2 ø R ë T1 T2 û
k1 2.303 R êë T1 T2 úû 4. (a) The minimum energy required to convert reactant
molecules into product molecules.
k2 104.4 ´ 103 J mol-1 é 1 1ù i.e. Activation energy = E1 + E2
log = -
3 ´10 -4 2.303 ´ (8.314 J K -1mol-1) êë 298 T úû Energy of product is greater than the reactants so less
stable.
1 5. (b) A(g) ¾® B(g) + C(g)
As T® ¥, ®0
T Initially pi 0 0
k2 104.4 ´ 103 J mol -1 At time t pi – x x x
\ log = Total pressue at equilibrium, pt = pi – x + x + x = pi + x
3 ´ 10-4 2.303 ´ 8.314 ´ 298
For first order reaction x = pt – pi
k2 k2 2.303 p
log -4
= 18.297, -4
= 1.98 ´ 1018 k= log i
3 ´ 10 3 ´ 10 t pi - x
k2 = (1.98 ´ 10 ) ´ (3 ´ 10-4 ) = 6 ´ 1014 s -1
18 2.303 pi
= log
94. (b) For 10°C rise of temperature the rate is almost doubled. t pi - ( p t - p i )
- Ea / RT 2.303 pi
95. (c) k1 = A1e 1 .........(i) = log
t 2pi - p t
-E / RT
k2 = A2e a2 ........(ii) 6. (a) According to Arrhenius equation, k = A e - E a / RT

( )
On dividing eqn (i) from eqn. (ii)
Ea
-
k1 A1 Taking log on both side ln k = ln A e RT
= ( Ea2 - Ea1 ) / RT ........(iii)
k2 A2 Ea
ln k = ln A -
Given Ea2 = 2Ea1 RT
On substituting this value in eqn. (iii) Ea 1
ln k = - ´ + ln A
E / RT R T
k1 = k 2 A ´ e a1 - Ea
96. (b) 97. (b) From the graph, it is clear that slope = and
R
98. (a) If a reactant is present in excess, order with respect to intercept = ln A.
that reactant is zero. 7. (c) Zn + dil. HCl ¾¾ ® ZnCl 2 + H 2 ­
99. (c) 100. (a)
101. (c) Applicable to bimolecular reactions. Rate of reaction
102. (a) Change in concentration of H 2 V3 - 0 V3
= = =
103. (b) For a 10 K rise in temperature, collision frequency Change in time 40 - 0 40
increases merely by 1 to 2% but the number of
effective collisions increases by 100 to 200%. 8. (d) As per Arrhenius equation k = A e - Ea / RT
104. (c) 105. (b) 106. (a) So, k µ e - Ea
107. (b) When the temperature is increased, energy in form of 1
-
heat is supplied which increases the kinetic energy of kµe T
the reacting molecules. This will increase the number
µ eT
of collisions and ultimately the rate of reaction will be These relations show that rate constant increases with
enhanced. decreasing activation energy and increasing
108. (d) 109. (d) temperature.
110. (d) All the statements are correct. 9. (c) Order of reaction may or may not be equal to sum of
stoichiometric coefficients of reactants in the balanced
Exercise - 2 chemical equation.
1. (c) The role of a catalyst is to change the activation energy 10. (b) Instantaneous rate of reaction
of reaction. Change in volume
= Time interval close to 40s
 EBD_7374
578 CHEMISTRY

V4 - V2 V - V2 é1ù
2
é1ù
y
rinst ( 20s ) = incorrect, correct is 5
50 - 30 50 - 30 êë 2 úû = êë 2 úû
11. (a) Concentration of reactant decreases with passage of y= 2
time, so rate of reaction decreases because rate
x y
changes with change in concentration of reactant or Rate of exp.1 [0.30] [ 0.30 ]
product with time. =
Rate of exp. 3 [ 0.60]x [ 0.30 ]y
12. (c) 5Br - ( aq ) + BrO3- ( aq ) + 6H + ( aq ) ® 3Br2 ( aq ) + 3H 2O ( l )
x y
Rate law expression as 0.10 é 0.30 ù é 0.30 ù
=
0.20 êë 0.60 úû ëê 0.30 ûú
1 D [ Br - ] D é BrO3- ùû -1 D [ H + ] +1 D [ Br2 ]
- =- ë = = 1 é1ù
x
5 Dt Dt 6 Dt 3 Dt = ê ú [1]
y
2 ë2û
D [ Br ] D é BrO3 ùû -5 D [ H ]
- - +
Þ– =- ë = 1 é1ù
x
Dt Dt 6 Dt =êë 2 úû
D [ Br - ] 5 D [ H + ]
2
Þ = i.e., x=1
Dt 6 Dt \ Rate = k [A]x[B]y
13. (a) Ea(F.R.) + DH = Ea(B.R.)
Rate = k [A]1[B]2
DH = – ve
Activated complex 18. (b) Catalyst does not change Gibbs free energy because
Gibbs free energy is related to concentration of reactant
& product which is not changed by catalyst.
19. (b) Pseudo first order reaction is a chemical reaction in
Ea(B.R.) which rate of reaction depends upon concentration of
Energy

Ea(F.R.) only one reactant while concentration of another

reactant has no effect on rate of reaction.
DH 20. (b) A ® B
As time increases concentration of reactant decreases
and concentration of product increases exponentially.
Reaction coordinate
21. (b) For first order reaction,
14. (b) Rate of reaction w.r.t B is of first order
0.693
R1 = k [A] [B] Rate = kA'0 = .A 0
t1 2
when concentration of reactant 'B' is doubled then rate
(R2) will be : A0
For zero order reaction, Rate = kA00 =
R2= k [A] [2B] 2t1 2
R2= 2k [A] [B] Ratio in rates = 2 × 0.693
R2 = 2 R1
d [C ]
15. (c) In collision theory of reaction rates the key factors 22. (d) Let rate of reaction = = k[A]x [B]y
which determine whether a particular collision will t
result in a reaction is the energy of collision and the Now from the given data
orientation of the collision. 1.2 × 10 – 3 = k [0.1]x[0.1]y .....(i)
16. (d) The time in which the concentration of a reactant is 1.2 × 10 – 3 = k [0.1]x[0.2]y .....(ii)
reduced to half of its original value is called half-life 2.4 × 10 – 3 = k [0.2]x[0.1]y .....(iii)
period of the reaction. Dividing equation (i) by (ii)
But it is impossible to perform 100% of the reaction. 1.2 ´10-3 k[0.1]x [0.1] y
Because substance never reacts completely as in every Þ =
half-life, 50% of the substance reacts. So, time taken 1.2 ´10-3 k [0.1]x [0.2] y
for 100% completion of a reaction is infinite. We find, y = 0
17. (b) r = k [A]x[B]y Now dividing equation (i) by (iii)
x y
Rate of exp.1 [0.30 ] [ 0.30] 1.2 ´10-3 k[0.1]x [0.1] y
= Þ =
Rate of exp. 2 [ 0.30 ]x [ 0.60] y 2.4 ´10-3 k [0.2]x [0.1] y
y
0.10 [ 0.30 ] We find, x = 1
=
0.40 [ 0.60]y d [C ]
Hence = k[ A]1 [ B ]0
y dt
1 é1ù
=
4 êë 2 úû
CHEMICAL KINETICS 579

23. (a) The increase in pressure shows the increase in conc. \ The concentration of reactants will exponentially
of Z. Rate of appearance of decreases with time.
32. (a) Unit of rate constant for second order reaction is
120 - 100
Z= = 4 mm min–1 L mol–1 sec–1.
5 33. (a) For a first order reaction
Rate of disappearance of X2 = 2 × rate of appearance of 2.303 ( a - x1 )
Z = 2 × 4 mm min–1 = 8 mm min–1 K = t - t log a - x
24. (d) For two parallel reactions ( 2 1 ) ( 2 )
kaverage = k1 + k2 2.303 æ 0.04 ö
K= ( log ç ÷
= 1.26 × 10–4 + 3.8 × 10–5 20 - 10 ) è 0.03 ø
= 1.64 × 10–4sec–1 2.303 ´ 0.1249
K=
10
kB
The fractional yield of B = 0.6932 2.303 ´ 0.1249
k av =
t1/2 10
1.26 ´ 10 - 4 0.6932 ´ 10
= = 0.7683 = 76.83 % t1/2 = = 24.1 sec
2.303 ´ 0.1249
1.64 ´ 10 - 4
34. (d) A catalyst provides an alternative route for the reaction
The fractional yield of with a lower activation energy.
kC 3.8 ´ 10 - 5 35. (d)
C= = 36. (a) k remains constant at constant temperature and CO
k av 1.64 ´ 10 - 4 does not effect the rate of reaction.
= 0.2317 = 23.17 %
25. (d) Rate constant k = 0.6 × 10–3 mole per second. (unit 1
37. (d) H2O2(aq) ® H2O(aq) + O (g)
mole per second shows zero order reaction) 2 2
For a zero order reaction For a first order reaction
[A] = [A]0 – kt
2.303 a
and [A0] – [A] = [B] = kt k= log
= 0.6 × 10–3 × 20 × 60 = 0.72 M t (a - x)

0.693 Given a = 0.5, (a – x) = 0.125, t = 50 min

26. (a) t1/ 2 =
k 2.303 0.5
\ k= log
For first order t 1/2 is independent of initial 50 0.125
concentration of reactant. = 2.78 ´ 10–2 min–1
27. (b) Arrhenius equation r = k[H2O2] = 2.78 ´ 10–2 ´ 0.05
Ea = 1.386 ´ 10–3 mol min–1
K=A.e - E a /RT Þ ln K = ln A – Now
RT
–E a d [ H 2O2 ] d [ H 2 O ] 2d [O2 ]
slope = - = =
R dt dt dt
so, activation energy of reaction can be determined 2d [O2 ] d [ H 2 O2 ]
\ =-
1 dt dt
from the slope of ln K vs d [O2 ] 1 d[H 2 O 2 ]
T
\ = ´
28. (a) Let the rate law be r =k [A]x[B]y dt 2 dt
0.10 [0.024]x [0.035] y 1.386 ´10-3
Divide (3) by (1) = = = 6.93 ´ 10–4 mol min–1
0.10 [0.012]x [0.035] y 2
\ 1 = [2]x, x = 0 38. (d) For P, if t50% = x
0.80 [0.024]x [0.070] y then t75% = 2x
Divide (2) by (3) = This is true only for first order reaction.
0.10 [0.024]x [0.035]y
So, order with respect to P is 1.
\ 8 = (2)y , y = 3 Further the graph shows that concentration of Q
Hence rate equation, R = k[A]0[B]3 =k[B]3 decreases with time. So rate, with respect to Q, remains
29. (b) According to Arrhenius equation, k = Ae–Ea / RT constant. Hence, it is zero order wrt Q.
When Ea = 0, k = A. So, overall order is 1+ 0 = 1
30. (c) Reactions of higher order (>3) are very rare due to very 39. (d) Since the slow step is the rate determining step hence
less chances of many molecules to undergo effective if we consider option (A) we find
collisions.
Rate = k [ Cl2 ][ H 2S]
31. (b) For a first order reaction [A] = [A0]e–kt
 EBD_7374
580 CHEMISTRY

Now if we consider option (B) we find nFE°

= 0.4342 ........ (i)
Rate = k [ Cl2 ] éë HS ùû
- RT
...(i)
nFE°
For equation, ln K =
ˆˆ† H+ + HS–
H2S ‡ˆˆ RT
nFE °
é H + ù é HS- ù K = e RT
....... (ii)
K = ë ûë û
H 2S dX
43. (a) Rate expression = k[ A]m [ B ]n shows that the total
- K [ H 2 S] dt
or éë HS ùû = order of reaction is m + n + 0 = m + n
H+
As the rate of reaction is independent of concentration
Substituting this value in equation (i) we find of C, i.e., the order with respect to C is zero. This is the

Rate = k [ Cl2 ] K
[ H 2S] = k ' [ Cl2 ][ H 2S] reason that C does not figure in the rate expression.
44. (d) From arrhenius equation,
H+
éH+ ù
ë û – Ea
Thus slow step should involve 1 molecule of Cl2 and 1 k = A.e RT
molecule of H2S. –E a /RT
hence only , mechanism (A) is consistent with the given so, k1 = A.e 1 .....(1)
rate equation. –E a / RT
40. (c) The overall reaction rate depends on the rate of the k 2 = A.e 2 .....(2)
slowest step. (E a – Ea )
i.e., Overall rate = Rate of slowest step (ii) 1 2
k2
= k[X][Y2] … (1) On dividing equation (2)/(1) Þ =e RT
k1
k = rate constant
Assuming step (i) to be reversible, its equilibrium æ k ö Ea – Ea 2 10, 000
constant, ln ç 2 ÷ = 1 = =4
k
è 1ø RT 8.314 ´ 300
[ X ]2 45. (b) Rate1= k [A]x[B]y ... (1)
k eq = Þ [ X ] = k eq [ X 2 ] ;
2
[ X2 ] Rate1
= k [A]x [2B]y ... (2)
1 4
1
or Rate1 = 4k[A]x[2B]y
[ X] = 2
k eq [ X2 ] 2 … (2)
From (1) and (2) we get
From eq (1) and (2)
k[A]x [B]y
1 1 = k[A]x[2B]y
4
Rate = kk eq 2 [ ] [ Y2 ]
X2 2
[B]y
1 3 = [2B] y
Overall order = + 1 = = 1.5 4
2 2
41. (a) Half life for a first order reaction, y
1 æ 2B ö 1
or =ç ÷ Þ = 2y or (2)–2 = 2y
0.693 4 è Bø 4
t1/2 =
K y = –2.
0.693 3
sec . 46. (a) The order of reaction is and molecularity is 2.
So, t1/2 = -2 2
10
47. (b) (t1/2)1st order = Independent of concentration
Also, for the reduction of 20 g or reactant to 5 g, two
half lives will be required. 1
(t1/2)2nd order µ
\ For 20 g of the reactant to reduce to 5g, time taken, [A]o
0.693 48. (c) For a first order reaction,
t=2× -2
sec = 138.6 sec.
10 2.303 a
K= log
42. (c) DG = –2.303 RT log K t a - x
–nFE° = –2.303 RT log K 2.303 100
nFE° = log
log K = 60 100 - 80
2.303 RT
CHEMICAL KINETICS 581

2.303 On substituting the given value

100
= log
60 20 dI2 4.56 ´ 10 -3 ´ 5
= 0.0268 \ = = 1.14 × 10–2 M/s
dt 2
0.693 2. (b) Use the formula:
Now, t 1 = = 25.85
0.268 2.303 V0
2
49. (b) In presence of catalyst : t= log V
k t
k2 A Ea –Ea1 V0
log = log 2 + 2 1
k1 A1 2.3RΤ = ln V
k t
A2 2RT A
log 1 = log – ln 2 =2 1 25mL
A1 2.3RΤ A1 = –2 –1 ln
4.5 ´10 min 5mL
50. (a) CH3 CHO ¾¾
® CH 4 + CO log e 5
= min
Generally r µ (a – x)m 4.5×10 – 2
r1 = 1 torr sec–1, when 5% reacted 3. (d) (a – x ) = ae–kt or At = A0e–kt where At = (a – x) = conc.
r2 = 0.5 torr sec–1, when 33 % reacted of reactant remained after time = t
(a - x1 ) = 0.95(unreacted) A0 = a = Initial concentration of reactant when t = 0
(a - x 2 ) = 0.67(unreacted) a 1 1
4. (d) t100% = = min = ´ 60 sec = 100 sec.
k 0.6 0.6
m m
r1 é (a - x1 ) ù 1 æ 0.95 ö Reaction will be finish in 100 sec., so concentration of
=ê ú ; =ç ÷ B will reach maximum value 2 M after 100 sec.
r2 ë (a - x 2 ) û 0.5 è 0.67 ø
n -1
2 = (1.41)m Þ 2 = ( 2)m (t1/2 )1 æ a 2 ö log(t1 / t 2 )
5. (c) =ç ÷ ; n =1 +
Þm=2 (t1/2 )2 è a1 ø log (a2 / a1 )
51. (a) The intersection point indicates the half life of the re-
0.693 2.303 a
actant A when it is converted to B. 6. (b) k= min -1 = log or
52. (b) T1 = 273 + 25 = 298 K 45 t99.9% a - 0.999a
T2 = 273 + 60 = 333 K
2.303 ´ 45
t99.9% = log103 = 448 min » 7.5 hrs
k Ea æ T2 – T1 ö 0.693
log 2 = ç ÷
k1 2.3 R è T1T2 ø 2.303 a
7. (b) k= log
t (a - x )
k2 Ea æ T2 – T1 ö
or loge = ç ÷ (a – x) is the concentration left after 100 sec.
k1 R è T1T2 ø
2.303 0.29
2.7 ´ 10-3 = log
2.1 ´ 10 – 2 Ea æ 35 ö 100 ( a - x)
loge = çè 333 ´ 298 ÷ø
1.5 ´ 10 –3 R 0.27 0.29 0.29
Þ = log Þ 0.117 = log
2.303 ( a - x) (a - x )
298 ´ 333 21
\ Ea = × R × loge Þ (a – x) = 0.22 M.
35 1.5
2000
-
Exercise - 3 8. (d) Given, k1 = 1016.e T

1000
-
dMnO-4 and k2 = 1015.e T
1. (b) Given - = 4.56 × 10–3 Ms–1
dt when k1 and k2 are equal at any temperature T, we
have
1 dMnO4 – 4.56 ´10-3
From the reaction given, - = Ms-1 2000 1000
2 dt 2 - -
1016.e T 15
= 10 .e T

1 dMnO -4 1 dI 2 2000 1000

- = - -
2 dt 5 dt 15 15
or 10 ´ 10 .e T
= 10 .e T

5 dMnO -4 dI 2 -
2000
-
1000
\ - = T T
2 dt dt or 10.e =e
 EBD_7374
582 CHEMISTRY

2000 1000 æ E forward ö

or ln 10 - =-
T T ç (A ®B) ÷ 2 x
ç ÷= =
2000 1000 ç E backward ÷ 3 -40 + x
or ln 10 = - è (B®A) ø
T T
Þ –80 + 2x = 3x
1000 Þ x = –80 kJ/mol for forward
or 2.303 log 10 =
T For backward = –40 + (–80) = –120 kJ/mol
or 2.303 ×1×T=1000 [ \ log 10= 1] Because activation energy cannot be negative
1000 so, for forward reaction Ea = 80 kJ/mol
or T = K for backward reaction Ea = 120 kJ/mol
2.303
11. (b) In accordance with Arrhenius equation.
9. (c) First step is slow (require more activation energy)
second step is fast (less activation energy) and overall 12. (c) k = Ae - Ea / RT ; when T ® ¥, k = A
reaction exothermic, so product energy level should 13. (d)
be less as compared to reactants.
0.693 0.693
14. (c) k= = min -1 ;
10. (a) t1/ 2 150.5
E a = x kJ/mol
2.303 100 2.303 ´ 150.5 100
t= log = log
k 100 - 40 0.693 60
= 111 minutes
– 40 kJ/mol
15. (d)
 19. SURFACE CHEMISTRY

Exercise - 1 1
at low pressure =1
n
1. (a) On increasing temperature physical adsorption of a
x
gas on surface of solid decreases. Solid adsorb greater \ µ P1
amount of gas at lower temperature. m
2. (a) Chemical adsorption involves formation of monolayer. 1
at high pressure =0
3. (a) Chemisorption involves strong chemical forces. n
4. (d) In physisorption, gas molecules are held on the solid x
µ P°
surface by weak van der Waal’s forces. m
5. (b) i.e., the value of n varies between 0 to 1.
6. (d) Adsorption is accompanied by evolution of heat as 13. (b) The gases having higher values for critical temperature
the residual forces acting along the surface of are easily liquified and are adsorbed to the greater
adsorbent decrease i.e., adsorption is accompanied by extent. CO2 has highest critical temperature of 304K.
decrease in enthalpy. 14. (b) According to Freundlich equation.
7. (b) The more readily soluble and easily liquefiable gases x x
µ p1/ n or = Kp1/ n
such as NH3, HCl and SO2 are adsorbed more than the m m
so called permanent gases like O2. This is due to the x x 1
van der Waals or intermolecular forces which are or log = log Kp1/ n or log = log K + log p
m m n
involved in adsorption.
15. (a) On increasing temperature adsorption of a gas on
8. (c) Adsorption is an exothermic process i.e. DH of
surface of solid decreases. Solid adsorb greater amount
adsorption is always negative. When a gas is adsorbed,
of substances at lower temperature.
the freedom of movement of its molecules becomes
16. (a) For adsorption to occur DG = –ve as in adsorption
restricted i.e. DS is negative. Hence adsorption
DH = –ve, DS = –ve. –TDS is positive for adsorption.
accompanied by decrease in enthalpy as well as
17. (c)
decrease in entropy of the system.
18. (c) Assertion is true, reason is false. When several lines
9. (d) The heat evolved in physisorption is quite low varying
generally between 20-40 kJ mol–1. 1
have the same value of , then the lines by which
10. (d) According to Freundlich adsorption isotherm. n
At intermediate pressure, extent of adsorption their adsorption isotherms can be represented will be
x x 1 parallel and will not meet at a point.
= kP1/ n or log = log k + log P 19. (c) Adsorption is an exothermic process, hence DH will
m m n
always be negative.
20. (c) Physical adsorption involves weak forces, physical in
1 nature with small heat of adsorption. Thus low
pe
= n temperature and high pressure favours physical
S lo adsorption.
m

21. (b) The adsorption of methylene blue on activated

x

charcoal is an example of physiosorption which is

log

exothermic, multilayer and does not have energy barrier.

22. (d) Freundlich’s isothermal adsorption equation can be
given as
Intercept = log k x
= kp1/n
log P m
x 1 x 1 1
plot of log vs log P is linear with slope = log = log k + log p; slope = = 0
m n m n n
11. (d) x
Thus, = kp0
12. (a) According to Freundlich adsorption isotherm m
1 23. (d) Assertion is false but Reason is true. The enthalpy
x of chemisorption is of the order of 40 - 400 kJmol –1
= kP n
m while for physical adsorption it is of the order of
20 - 40 kJmol–1.
 EBD_7374
584 CHEMISTRY

24. (c) Both adsorption and absorption can take place Emulsion Liquid Liquid
simultaneously. The term sorption is used to describe Foam Gas Liquid
both the processes. 49. (d) Emulsions are liquid-liquid colloidal systems, Generally
25. (d) For a reaction in equilibrium, the increase in rate of one of the two liquids is water.
reaction in forward direction by catalyst increases the 50. (b) Butter is an example of gel.
concentration of product(s) and thus the rate of 51. (d) Air is a homogeneous mixture of gases, mainly nitrogen
backward reaction also increases with the same and oxygen.
magnitude and allow the equilibrium to be achieved 52. (c) When the dispersed phase and dispersion medium both
quickly. are liquid, the colloidal system is called as an emulsion
26. (d) The catalytic poisons decrease the activity of the like milk, vasnishing cream etc.
catalyst because they are preferentially adsorbed on 53. (b) Cloud consists of fine droplets of water suspended in
the surface of catalyst. air.
27. (a) A catalyst increases the rate of reaction by decreasing
the activation energy.
54. (a) Polar head
28. (c) Active charcoal has more adsorption power due to
Non-polar tail
greater surface area. (micelle)
29. (c) Adsorption theory is applied to heterogeneous
catalysis.
30. (b) Catalyst decreases the activation energy of the reaction 55. (a) Surface tension of lyophilic sols is lower than water
by forming an intermediate product. So no of molecules (dispersion medium).
having activation energy increases hence rate of 56. (b) Gum is lyophilic colloid.
reaction increases. 57. (c) Lyophobic colloids are irreversible colloids. They are
31. (c) A catalyst can affect reversible reaction by attaining protected by lyophilic colloids.
equilibria in both directions. 58. (c) Example of multimolecular colloid system is a gold
32. (d) In acid hydrolysis of methyl acetate all are present in dispersed in water.
one phase (liquid). 59. (a) On shaking with the dispersion medium, colloids
33. (d) Enzymes are specific biological catalysts possessing directly form the colloidal sol. Hence they are called
well - defined active sites. intrinsic colloids. i.e., glue.
34. (d) Enzymes are biological catalysts and enhance the rate 60. (d) Sodium stearate is a soap. Soaps and detergents are
of biochemical reactions. surface agents which when dissolved in a medium,
35. (c) Hydrolysis of urea can be represented as follows forms aggregated particles, called associated colloids.
Urease
61. (d) The formation of micelles takes place only above a
H 2 N - C - NH 2 + H 2O ¾¾¾¾® 2NH3 + CO 2 particular temperature called kraft temperature (TK).
|| (enzyme)
O 62. (b) Electrolytes are used for neutralising charge on
Since it involves biological catalyst (enzyme) so it is colloidal particles.
an example of biochemical catalysis. 63. (c) The osmotic pressure of sea water is 25 atm at 15°C.
36. (d) Efficiency of catalysing property of a catalyst is When pressure greater than 26 atm is applied on sea
inversely proportional to activation energy. water separated by a rigid emipermeable membrane,
37. (b) Molybdenum acts as a promoter for iron which is used pure water is obtained.
as a catalyst in Haber’s process. 64. (a) Blood is purified by dialysis
38. (c) Second step involves adsorption of reactant molecules 65. (d) The use of membrane for separating colloidal particles
on the surface of the catalyst. is termed as dialysis. Hence it is clear that colloidal
39. (a) particle cannot pass through animal membrane. Hence
40. (c) Zeolites are found in nature as well as synthesised for only solvent molecules and ions (in case of
catalytic selectivity. electrodialysis) can diffuse.
41. (a) 66. (d) Electrolytic (Ionic) impurities can be most easily
42. (a) removed on application of electric field.
43. (d) Enzymes are most reactive at optimum temperature. The 67. (d) The separation of colloidal particles of molecular
optimum temperature for enzyme activity lies between dimension is known as dialysis. It is a purification
40°C to 60°C. method of colloid.
44. (a) Milk is a emulsion in which liquid is dispersed in liquid. 68. (d)
45. (c) Size of colloidal particles is 10–5 - 10–7 cm. 69. (c) Colloidal gold is prepared by Bredig's arc method.
46. (d) Mist is a colloid (aerosol) in which liquid is dispersed 70. (b) Peptisation is disintegration of colloidal aggregate.
in gas. 71. (c) According to this law the coagulating effect of an ion
47. (c) Alloy is an example of solid solution. on dispersed phase of opposite charge increases with
48. (b) Colloid Dispersed phase Dispersion medium the increase in valency of the ion. The precipitating
Sol Solid Liquid
Gel Liquid Solid
SURFACE CHEMISTRY 585

power of Al3+ , Ba++, Na+ ions is in order Al3+ > Ba2+ > 96. (c)
Na+. 97. (b) Brownian movement is zig zag motion of sol particles.
72. (a) Tyndall effect is shown by sols. 98. (d) Tannin used in leather industry contains negatively
73. (c) It is due to impact of molecules of dispersion medium charged colloidal particles.
on the colloidal particles. 99. (b) Eosin dye, sol of charcoal, As2S3 and copper sol are
74. (b) example of negatively charged sol.
75. (b) The size of colloidal particles is between 1 nm and 1000 100. (d) Argyrol is used as an eye lotion.
nm i.e., it is not always greater than 100 nm. So (b) is Antimony is used in Kalazar.
not a property of colloidal solution. All others are the Collidal gold is used in intramuscular injection.
properties of colloidal solution. Milk of magnesia is used in the stomach disorder.
76. (c) 101. (a) Colligative properties depend upon number of
77. (c) Sugar forms homogeneous solution hence no Tyndall particles.
effect is exhibited. 102. (c) Emulsion show the tyndall effect.
78. (d) 79. (c) 80. (d) 103. (c) Protein is an emulsifying agent for O/W emulsion.
81. (a) Soap lather is a colloid containing gas as a dispersed 104. (d) 1005. (a) 106. (a) 107. (a)
phase and liquid as a dispersion medium.
82. (a) Chlorophyll. Smoke is an example of solid-gas colloid Exercise-2
system Ruby glass is an example of solid-solid colloid 1. (c) In homogeneous catalysis reactant and catalyst have
system. Milk is an liquid -liquid colloid system. same phase so homogeneous catalysis can not occur
83. (c) Starch molecules have colloidal dimensions whereas at the inertface of phases
NaCl, glucose and Ba(NO3)2 are crystalloids and soluble 2. (b) Equilibrium DG = 0
in water. DH – TDS = 0
84. (d) Cetyl trimethyl ammonium bromide, DH = TDS
[C16 H33 (CH3 )3 N + Br - ] is a cationic micelle. 3. (d) Gas-gas interface can not be obtained as gases are
completely miscible in nature.
85. (d) Linseed oil, lanolin and glycogen attract water hence
4. (c) When both absorption and adsorption occur it is called
contain a hydrophilic structure but rubber does not
attract water and thus does not contain a hydrophobic sorption
structure. + + + +
86. (c)
+ + + + + +

+ + + + + +
+ + + +
87. (a) Multimolecular colloids consist of aggregates of atoms + + + +
or small molecules. Sulphur sol is an example of + + + + adsorption
multimolecular colloids + + + +
88. (b) Bredig’s arc method is suitable for the preparation of + + + +
colloidal solution of metals like gold, silver, platinum + + + +
absorption
etc. An arc is struck between the metal electrode under sorption
the surface of water containing some stabilzing agent
5. (b) In physisorption particles are attached to the surface
such as a trace of KOH. However, Fe does not react
by weak van der Waal's force of attraction so on
with alkalies that is why it is not obtained by Bredig’s-
increasing temperature they get desorbed.
arc method.
6. (a) When amount of adsorbate increases the interaction
89. (d) Colloidal solutions are not purified by electrophoresis. of adsorbate adsorbent increases which lead to
Movement of colloidal particles under the influence of
increase in adsorption.
electric field is called electrophoresis. So, it can make
7. (a) Enthalpy change during adsorption is negative. As in
easier. Electrophoresis is the property of colloids not
adsorption, there is decrease in residual forces of the
the purification method.
surface which result in decrease in surface energy in
90. (a) Proteins are coagulated by some heavy metal ions like
form of heat.
Ag+, Hg2+ and Pb2+. 8. (d) Adsorbate get adsorbed on the adsorbent surface by
91. (a)
weak van der Waal's force of attraction in
92. (d) Al(OH)3 is a positive sol so salt having anion with
physisorption. Rise in temperature will break the
maximum negative charged (i.e. phosphate ion) will be
interaction between adsorbate and adsorbent so
most effective in coagulation.
adsorbate particles get desorbed.
93. (a) Colloid of liquid in liquid is called emulsion. Colloid of
9. (b) With increase in temperature physisorption changes
liquid in solid is gel. to chemisorption, because energy of activation of
94. (b)
adsorbate particles increases which lead to formation
95. (b) When oppositely charged sols are mixed their charges
of chemical bond.
are neutralised. Both sols may be partially or completely
10. (a) The extent of van der Waal's interaction between
precipitated.
absorbate and adsorbent is constant for all gases.
 EBD_7374
586 CHEMISTRY

11. (b) Absorption is a bulk phenomena in which particles A

goes to the bulk instead of residing only to surface. A |
12. (d) Critical temperature of gases is directly proportional ® B ®
B
to the extent of adsorption.
13. (a) Reaction in which catalyst and reactant/product is in
different phase then it is known as heterogeneous catalysis. (iii) (iv)
14. (b) At high concentration of soap in water, soap particles
present in the solution get associated and it leads to A
the formation of associated colloid. |
15. (b) Tyndall effect is a characteristic of colloidal solution, B
as aqueous solution of soap above cmc form a colloidal
solution. (v)
16. (c) Lyophobic sol can be protected by addition of lyophilic
22. (c) River water is a colloidal solution of clay and sea. Water
sol as lyophobic sols are readily precipitated on
contains various electrolytes. When river water comes
addition of small amount of electrolytes or shaking, or
in contact with sea water, then the electrolytes present
heating hence they are made stable by adding lyophillic
in sea water coagulate the suspended colloidal
sol which stabilises the lyophobic sols.
particles which ultimately settle down at the point of
17. (d) Peptisation is a process in which by addition of a
contact.
suitable peptising agent precipitate gets converted into
23. (c) According to the Freundlich adsorption iotherm
colloidal solution. 1
18. (b) According to Hardy-Schulze law, greater the charge x
on anion greater will be its coagulating power. = kp n
m
Electrolytes Anionic part Charge on anion x æ 1ö
Taking log on both side log = ç ÷ log p + log k
2– m è nø
Na 2S S 2
This equation is comparable with straight line equation,
Na 3 PO4 PO3–
4 3 y = mx + c, where m represents slope of the line and c
represents intercept on y axis.
Na 2 SO4 SO42– 2
–
NaCl Cl 1
Here PO3– 4 have highest charge. Hence, PO4 have
3–
log x /m

highest coagulating power. Slope = 1/n

19. (d) Sol is a colloidal system in which solid substance is a
dispersed phase and a liquid is a dispersion medium log k (intercept)
e.g., aint cell fluids etc.
log p
In paints solid colouring particles are dissolved in
liquid dispersion medium. 24. (d) Absorption of ionic species from solution is not
20. (b) The value of colligative properties of colloidal solution responsible for the presence of electric charge on the
are of small order in comparison to those of true sol particles. Charge on the sol particles is due to
solutions of same concentration because colloidal (i) electrons capture by sol particles during electro
particles are comparatively less in number. dispersion of metal.
21. (b) The Correct sequence of steps is I ® III ® II ® IV ® V (ii) preferential adsorption of ionic species from
Each step represents a meaningful process as follows solution.
I ® adsorption of A and B on surface (iii) formation of Helmholtz electrical double layer.
III ® II interaction between A and B to form 25. (b) Above figure represent adsorption of yellowish brown
intermediate colour of raw sugar by animal charcoal.
III ® IV starting desorption of A–B Here, aqueous solution of raw sugar is filtered by using
IV ® V complete desorption animal charcoal. Yellowish brown colour of raw sugar
is adsorbed and filterate is colourles which gives white
A colour on cystallisation. Hence, this phenomenon is
A adsorption.
® ® 26. (b) For adsorption DS < 0 and for a spontaneous change
B DG = – ve
B hence DH should be highly negative which is clear
(i) (ii) from the equation
DG = DH – TDS
SURFACE CHEMISTRY 587

= – DH – T(– DS) = – DH + TDS are ionic which can undergo dissociation to give
So if DH is highly negative DG will also be (– ve) oppositely charged ions and thus can be separated.
27. (d) Tyndall effect is optical property, whereas other 38. (d) Assertion is false but Reason is true. The enthalpyof
properties are electrical properties. Hence dependent chemisorption is of the order of 40 - 400 kJmol–1 while
on the charge on colloids for physical adsorption it is of the order of 20 - 40 kJmol–1.
28. (a) Since the sol particles migrate towards cathode, they 39. (b)
are positively charged. Hence, anions would be 40. (d) According to Hardy Schulze rule, coagulating power
effective in coagulation. Greater is the valence of of an ion depends on both magnitude and sign of the
effective ion, smaller will be its coagulating value. charge on the ion.
29. (b) At isoelectric point there is no migration of dispersed 41. (b) When charge gets neutralized by addition of some elec-
phase in an electric field. trolyte. It is called coagulation.
30. (c) For a protective colloid lesser the value of gold number 42. (d)
more will be the protective power. Thus the correct 43. (b) According to Freundlich equation,
order of protective power of A, B, C and D is x x
µ p1/ n or = Kp1/ n
Þ (A) < (C) < (B) < (D) m m
Gold number 0.50 0.10 0.01 0.005 x x 1
Hence (c) is the correct answer or log = log Kp1/ n or log = log K + log p
m m n
31. (c)
32. (b) Adsorption is spontaneous process, therefore change 44. (b) Given reactions shows that the selectivity of different
in the free energy (DG) for the process is negative. catalysts for some reactants is different.
According to Gibbs's Helmholtz eqn. Exercise-3
DG = DH – TDS
DS is negative because adhering of gas molecules to ¾®
the surface lowers the randomness.
\ DG can be –ve only when DH is –ve. x
33. (a) Fog is a colloidal system having dispersed phase as 1. (a)
m
liquid and dispersion medium as gas.
P ¾®
34. (a) Colloidal antimony is used in curing kala-azar.
35. (a) According to Freundlich adsorption isotherm
3.6
x 1 2. (c) Mass of O2 per gram of adsorbent = =3
1.2
log = log K + log p
m n
3
Thus if a graph is plotted between log(x/m) and log p, No. of moles of O2 per gram of adsorbent =
a straight line will be obtained 32
Volume of O2 per gram of adsorbent
n
1/
¾®

= 3 0.0821 ´ 273
pe = ´ = 2.10
s lo 32 1
log x/m

3. (b) DH < 0, DS < 0, DG < 0

4. (a) Temp­ Extent of adsorption ¯
Intercept = log K 5. (b) Mass of acetic acid adsorbed by 2 g charcoal
= 100 × 10–3 × (0.6 – 0.5) × 60
log p ¾®
The slope of the line is equal to 1/n and the intercept x 0.6
Þ 0.6; = Þ 0.3
on log x/m axis will correspond to log K. m 2
36. (a) A catalyst speeds up both forward and backward 6. (c) Mass of oxalic acid adsorbed by 10 g charcoal
reaction with the same rate.
= 200 ´ 10 -3 (0.5 - 0.4) ´ 90 = 1.8 g
So, equilibrium constant is not affected by the presence
of a catalyst at any given temperature. x 1 .8
37. (c) Electrodialysis involves movement of ions towards = = 0 .18
m 10
oppositely charged electrodes.
Urea being a covalent compound does not dissociate 7. (b) AgNO3 + KI ® AgI ( s ) + KNO3
¾¾
to give ions and hence it cannot be removed by 5 × 10–3 10 × 10–3
electrodialysis.However all the other given compounds 0 5 × 10–3 5 × 10–3
 EBD_7374
588 CHEMISTRY

AgI ( s ) + I- ¾¾
® AgI : I- Radius of gold sol particle
Negative charge colloids. = 10 nm = 10 × 10–7 cm = 10–6 cm
8. (a) AgNO3 + KI ® AgI + KNO3 4 3
Volume of gol sol particle = pr
excess 3
AgI + Ag+ ® AgI
9. (b) Smaller is the 'gold number' of protective colloid, greater 4 22
= ´ ´ (10 -6 ) 3 = 4.19 × 10–18 cm3
is its protective power. 3 7
10. (b) When oppositely charged sols are mixed their charges \ No. of gold sol particles in 1 × 10–5 cm3
are neutralised. Both sols may be partially or completely
precipitated. 1 ´ 10-5
= = 2.38 ´ 1012
11. (c) As colloidal particles move towards anode so these 4.19 ´ 10 -18
particles are negatively charged and coagulated by
\ No. of gold sol particles in one mm3
cations of electrolyte.
According to Hardy Schulze rule, 2.38 ´ 1012
= = 2.38 ´ 106
Coagulation power µ Charge on ion 106
\ Order of coagulation power is Al3+ > Ba2+ > Na+
14. (a) Calcium and magnesium salts in hard water form
Coagulation power of AlCl3 insoluble salts of higher fatty acids.
12. (c)
Coagulation power of NaCl
2C17 H 33 COONa(aq.) + Ca 2+ (aq.) (Hard water) ¾¾
®
Coagulation value of NaCl
=
Coagulation value of AlCl3 (C17 H33 COO) 2 Ca(s) + 2Na + (aq.)
15. (b) In first case the given compounds have same anion
52 but different cations having different charge hence they
= = 559.13 » 560
0.093 will precipitate negatively charged sol i.e. ‘A’.
13. (d) Volume of gold dispersed in 1 L water In second case the given compounds have similar
Mass 1.9 ´ 10 - 4 g cation but different anion with different charge. Hence
= = = 1 × 10–5 cm3 they will precipitate positively charged sol. i.e. ‘B’.
Density 19 g cm -3
 20. GENERAL PRINCIPLES AND PROCESSES OF ISOLATION
OF ELEMENTS
24. (c) Assertion is true but reason is false.
Exercise - 1
Oxide ores being heavier than the earthy or rocky
1. (a) Argentite or silver glance (Ag 2S) is an ore of Ag. gangue particles, settle down while lighter impurities
are washed away.
2. (a) Cinnabar (HgS) is an ore of Hg. 25. (d) Assertion is false but reason is true. Leaching is a
3. (a) Bauxite ore of aluminium is Al 2 O3.2H 2O . process of concentration.
4. (a) 26. (c) Malachite is CuCO3 . Cu(OH)2 it is ore of copper.
5. (b) Al is most abundant metal on the surface of the earth. 27. (a) (a) Zinc Calamine is ZnCO3
6. (c) Carborundum - SiC (b) Silver Ilmenite is FeTiO3
Epsomite or Epsom salt - MgSO4.7H2O (c) Magnesium Cassiterite is SnO2
Cassiterite - SnO2 (d) Tin Azurite is
Spodumene - Ore of lithium [2CuCO3.Cu (OH)2]
7. (a) Chalcopyrite : CuFeS2 28. (c) Cuprite : Cu2O; Chalcocite : Cu2S; Chalcopyrite : CuFeS2;
Fool's gold : FeS2 Malachite: Cu(OH)2.CuCO3. We see that CuFeS2
Carnalite : KMgCl3.6H2O contains both Cu and Fe.
Bauxite : Al2O3.2H2O 29. (b) Except chromium all the given metals exists as their
8. (c) Haematite is Fe2O3. Thus it is the ore of iron (Fe). sulphides.
9. (c) Azurite is a basic carbonate ore of copper. Zn exists as zinc blende ZnS.
2CuCO3. Cu(OH)2 Silver exists as silver glance Ag2S.
10. (d) Fe3O4 – Magnetite Iron exists as iron pyrites FeS2.
CuCO3·Cu(OH)2 – Malachite Mercury exists as mercuric sulphide HgS.
Pyrolusite – MnO2 and Cassiterite – SnO2. 30. (a) MnO2 is pyrolusite (oxide ore).
11. (a) The formula of magnetite is Fe3O4. 31. (d) Leaching is the selective dissolution of the desired
12. (c) mineral leaving behind the impurities in a suitable
13. (c) Zincite is ZnO. dissolving agent e.g.,
14. (c) Galena is PbS and thus purified by froth floatation method. Argentitie or Silver glance, Ag2S is an ore of silver.
Froth flotation method is used to concentrate sulphide Silver is extracted from argentite by the mac-Arthur
ores. This method is based on the fact that the surface and Forest process (leaching process).
of sulphide ores is preferentially wetted by oils while Ag 2S + 4NaCN ® 2Na[Ag ( CN )2 ] + Na 2S
that of gangue is preferentially wetted by water. 4Au + 8KCN + 2H 2O + O 2 ® 4K[Au ( CN )2 ] + 4KOH
15. (b) Cassiterite contains the magnetic impurities of FeSO 4 32. (a) To remove moisture and non-metallic impurities like S,
and thus concentrated by electromagnetic separation. P and As are oxidised and are removed as volatile
16. (d) Cyanide process is used in the metallurgy of Ag substances.
2Ag 2S + 8 NaCN + O 2 + 2 H 2 O ¾ ¾® S8 + 8O 2 ® 8SO 2 ­ ; P4 + 5O2 ® P4 O10 ­
4 Na[ Ag (CN ) 2 ] + 4 NaOH + 2S 4As + 3O2 ® 2As2O3 ­
¾® Na 2 [ Zn (CN ) 4 ] + 2 Ag ¯
2 Na [ Ag ( CN ) 2 ] + Zn ¾ 33. (c) In this process sulphide ores are converted into oxide
17. (a) ores.
18. (b) Leaching is a process used for concentration of ore. In 2ZnS + 3O2 ® 2ZnO + 2SO2­
this process, a powdered ore is treated with a suitable 34. (b) Flux + Gangue ® Slag
reagent (such as acids, bases or other chemicals) which 35. (a) Calcination is heating ore in absence of air to remove
can selectively dissolve the ore, but not the impurities. moisture and volatile impurities. Carbonate ores
19. (a) Ag is leached by cyanide process. decomposed to corresponding oxides as a result of
20. (c) Pyrolusite is MnO2. Hence not concentrated by froth calcination.
floatation process. 36. (d) Calcination is a process of heating a substance to a
21. (c) Froth reduces the surface tension of water and the high temperature but below the melting or fusion point,
solution forms froth. causing loss of moisture, reduction or oxidation and
22. (a) Froth flotation process is based on wetting properties dissociation into simpler substances.
of ore particles. 37. (b) Since silica is acidic impurity the flux must be basic.
23. (a) For example, Ag2S is converted into Na[Ag(CN)2]. CaO + SiO2 ® CaSiO3
When Zn is added, Ag is displaced. 38. (b) To remove acidic impurities basic flux is added which
is CaCO3.
 EBD_7374
590 CHEMISTRY

39. (d) Decomposition of carbonates and hydrated oxides. 64. (d) Ellingham diagrams are based on thermodynamic
40. (d) 2CuO + CuS ® 3Cu + SO 2 (Self - reduction) concepts. It does not tell anything about the kinetics
41. (b) of the reduction process.
42. (b) In the graph of DrG° vs T for formation of oxides, the 65. (d) For a spontaneous reaction , D Gº must be negative
Cu2O line is almost at the top. So, it is quite easy to and it can be possible only in this case when x < y
reduce oxide ores of copper directly to the metal by 66. (b) The two equation are:
heating with coke both the lines of C, CO and C, CO2 4 2
Al(s) + O 2 (g) ® Al2 O3 (s), D f Gº = -827kJ mol -1
are at much lower temperature (500 - 600 K). 3 3
Cu 2 O + C ¾¾ ® 2Cu + CO … (1)
4 2
43. (d) Cr(s) + O 2 (g) ® Cr2 O3 (s), D f Gº = -540kJ mol -1
44. (c) Ellingham diagram normally consists of plots of DfGº 3 3
… (2)
Vs T for the formation of oxides of elements.
Subtracting equation (ii) from equation (i) we have,
45. (c)
46. (b) Fe2 O3 + 3CO ® 2Fe + 3CO 2 4 2 2 4
Al(s) + Cr2O3 (s) ® Al 2O 3 (s) + Cr(s),
47. (c) 3 3 3 3
48. (c) In blast furnace at about 1270 K, calcium carbonate is D r G° = -287kJ mol-1
almost completely decomposed to give CaO which acts 67. (a) FeO is capable forming slag with SiO2
as a flux and combines with SiO2 present as impurity
(gangue) in the ore to form calcium silicate (fusible SiO 2 + FeO ® FeSiO 3
slag) 68. (a) In blast furnace Fe2O3 is finally reduced to Fe at 993°C
CaO(s) (basic flux) + SiO2 (s) (acidic flux) ¾¾® 69. (c) The iron obtained from blast furnace is pig iron with
CaSiO3 (s) (slag) 4% carbon and impurities like S, P, Mn etc., in small
49. (b) These are the substances which can withstand very amount.
high temperature without melting or becoming soft. 70. (c) Because Na is very reactive and cannot be extracted
50. (b) Extraction of Zn from ZnS (Zinc blende) is achieved by by means of the reduction by C, CO etc. So it is extracted
roasting followed by reduction with carbon. by electrolysis.
71. (c)
2ZnS + 3O2 ¾¾ ® 2ZnO + 2SO2
72. (c) Fused alumina (Al2O3) is a bad conductor of electricity.
ZnO + C ¾¾ ® Zn + CO Therefore, cryolite (Na3AlF6) and fluorspar (CaF2) are
51. (d) Decomposition of carbonates and hydrated oxides. added to purified alumina which not only make alumina
52. (b) Aluminothermite process involves reduction of oxides a good conductor of electricity but also reduce the
which are not satisfactorily reduced by carbon such as melting point of the mixture to around 1140 K.
Fe2O3, Mn3O4, Cr 2O3, etc. to metals with aluminium. 73. (a) 74. (a) 75. (a)
Cr2 O3 + 2Al ® Al 2 O 3 + 2Cr DH = - ve 76. (b) The reactions involved in cyanide extraction process
53. (d) Blister-Copper contains 1 – 2 % impurities. It is are :
obtained after Bessemerisation of crude copper. Ag 2 S + 4NaCN ® 2Na [Ag(CN)2] + Na2S
54. (a) (argentite)
55. (b) Pig iron contains 4% carbon and many impurities in 4Na2S + 5O 2 + 2H2O ® 2Na2SO4 + 4NaOH + 2S
smaller amount. Oxiding
agent
56. (d)
2Na[Ag(CN)2] + Zn ® Na2 [Zn(CN)4] + 2 Ag ¯
57. (b) Ellingham diagram represents plot between DG and T (reducing
therefore with increase in temperature phase change agent)
Gas ® Liquid is not possible. Ellingham diagram does 77. (c) Extraction of non-metals are based on oxidation. For
not give any information about kinetics of the reduction example extraction of chlorine from brine.
reaction. 2Cl–(aq) + 2H2O(l) ® 2OH–(aq) + H2(g) + Cl2(g)
58. (c) 59. (a) 78. (b) For each kg of Al produced, about 0.5 kg of carbon
60. (a) Both assertion and reason are correct and reason is anode is burnt away.
the correct explanation of assertion. 79. (a)
61. (d) 62. (b) 523K 1700K
80. (a) Ti + 2I2 ¾¾¾® TiI4 ¾¾¾¾
® Ti + 2I 2
63. (d) The sulphide ore is roasted to oxide before reduction Volatile Pure metal
because the DGof of most of the sulphides are greater Stable compound
than those of CS2 and H2S, therefore neither C nor H 81. (c) Liquation process, Mond’s process and, van Arkel
can reduce metal sulphide to metal. Further, the standard process these are the refining processes that are applied
free energies of formation of oxide are much less than depending upon the nature of the metal under treatment
those of SO2. Hence oxidation of metal sulphides to and nature of the impurities whereas amalgamation
metal oxide is thermodynamically favourable. process is used for the extraction of noble metals like
gold, silver, etc, from native ores. The metal is recovered
GENERAL PRINCIPLES AND PROCESSES OF ISOLATION OF ELEMENTS 591

from the amalgam by subjecting it to distillation, where 6. (c) In the extraction of copper from its sulphide ore, the
the mercury distils over leaving behind the metal. metal is formed according to the reaction given :
Hg-vapours 1 1
Ore + Hg ® Amalgam Distilled Cu 2 O + Cu 2S ¾¾ ® 3Cu + SO 2
2 2
Metal 7. (a) Possible reactions occuring at anode are :
82. (b) Zr and Ti are purified by van Arkel method.
1
870K
Zr(s ) + 2I2 ( g ) ¾¾¾® ZrI4 ( g ) (i) Cl - ( aq ) ¾¾
® Cl2 ( g ) + e - ; Escell = 1.36 V
2
2075K
ZrI4 ( g ) ¾¾¾¾¾¾¾
® Zr(s ) + 2I 2 ( g ) ® O2 (g) + 4H+ + 4e– ; Escell = 1.23 V
(ii) 2H2O(l) ¾¾
Tugsten filament
523K
Ti(s) + 2I2(s) ¾¾¾ ® TiI4(g) The reaction at anode with lower value of Es is
preferred and therefore water should get oxidised in
1700K
preference to Cl– (aq). However, Cl2 is produced instead
of O2. This unexpected result is explained on the basis
Ti(s) + 2I2(g) of the fact that water needs greater voltage for oxidation
Pure titanium to O2 than that needed for oxidation of Cl– ions to Cl2.
83. (d) Si obtained by reduction of SiCl4 with H2 is further So reaction (i) is taking place at anode.
purified by zone refining method to get Si of very high 8. (b) In metallurgy of aluminium, graphite anode is oxidised
purity. Silicon is purified by zone-refining process to CO and CO2 and this process is known as Hall-
because the impurities present in it are more soluble in Heroult process.
the liquid phase than in the solid phase. The electrolytic reactions the process are :
84. (c) At cathode : Al3+ (melt) + 3e– ¾¾ ® Al(l)
85. (b) Zinc dust is used as a reducing agent in the manufacture At anode : C(s) +O2– (melt) ¾¾ ® CO (g) + 2e–
of dye-stuffs, paints etc. C(s) + 2O2– (melt) ¾¾ ® CO2 (g) + 4e–
86. (b) 9. (a) Two metals which are generally purified by using
87. (d) Na reacts vigorously with water (exothermic process ) electrolytic refining are copper and zinc.
88. (b) During the process of electrolytic refining of copper 10. (a) In the process of extraction of Ag and Au involving
Ag and Au are obtained as anode mud. leaching with cyanide ion, the metal can be recovered
89. (d) by displacement of Ag/Au by some other metal in the
90. (b) Cyanide process is for gold (A - s); floatation process complex ion. Reactions involved in the process are as
- pine oil (B - q); Electrolytic reduction - Al (C - r); Zone follows :
refining -Ge (D - p). 4 Au (s) + 8CN– (aq) + 2 H2O (aq) + O2 (g) ¾¾ ®
91. (d) Metals of high purity are obtained by zone refining 4 [Au (CN)2]– (aq) + 4 OH– (aq)
e.g., silicon, germanium, boron, gallium, indium. -
92. (b) During electrolytic refining of copper electrolyte used 2 éë Au ( CN ) 2 ùû ( aq ) + Zn (s ) ¾¾
®
is acidified solution of copper sulphate.
2-
93. (a) Wrought iron is used in making anchors, wires, bolts 2Au ( s ) + éë Zn ( CN ) 4 ùû ( aq )
chains and agricultural implements.
94. (b) 95. (a) 96. (a) 11. (d) Above point A : Df G°(C,CO) < Df G°(Fe, FeO)
Therefore, reduction of FeO by carbon occurs above
Exercise - 2 point A.
12. (a) Gibbs free energy change for the formation of CO2
1. (a) Chlorine extraction by electrolysis can be represented from CO has lesser value than Gibbs free energy change
as :- for the formation of FeO (below point A). As a result ,
2H2O(l) + 2Cl–(aq) ® H2(g) + Cl2(g) + 2OH–(aq) FeO will be reduced by CO below point A.
So, the oxidation of Cl– to Cl2 occurs. 13. (a) DG curve for the formation of CO2 and FeO intersect
2. (c) Copper matte contains sulphide of copper (I) and each other at point D thus, net reduction of FeO with
iron (II). CO is zero.
1 1 14. (b) On electrolysis of aqueous solution of s-block elements
3. (d) Cu 2 O + Cu 2S ¾¾ ® 3Cu + SO 2
2 2 H2 gas discharge at cathode.
In this given reaction, copper is reduced by itself hence - 1
it is known as auto-reduction. At cathode: H 2O + e ® H 2 + OH -
2
4. (a) The most abundant elements are aluminium (8.3% by
15. (b) Metal nitrates are highly soluble in water and are very
weight) and iron (4.2% by weight).
stable for e.g. NaNO3 and KNO3.
5. (b) The principle behind zone refining is that the impurities
16. (a) Highly electropositive metals like Al, K, Na etc. are
are more soluble in molten state than in solid state of
extracted by the electrolytic reduction.
the metal.
 EBD_7374
592 CHEMISTRY

zone refining method is used for obtaining metals of 31. (c) Assertion is correct, reason is incorrect. For sulphide
high purity e.g. Ge ores generally froth floatation process is used.
Froth flotation process is suitable for sulphide ores
Cyanide process is used for the extraction of gold. Exercise - 3
17. (b) In the metallurgy of aluminium, purified Al2O3 is mixed 1. (c) Zn is extracted from its sulphide ore by roasting
with Na3AlF6 or CaF2 which lowers the melting point followed by carbon reduction Hg, Pb and Cu are
of the mix and brings conductivity. extracted by self reduction from their sulphide ores.
18. (a) Silver, copper and lead are commonly found in earth's
SnCl2 + HgCl2 ¾¾
® SnCl4 + Hg
crust as Ag2S (silver glance), CuFeS2 (copper pyrites) 2. (b)
and PbS (galena). ( 2) ( 2)
XCl YCl ( XCl4 ) ( Y)
19. (d) Ti – van-Arkel method D 1
Si – Zone refining method HgO + ¾¾¾¾® Hg + O2
> 400°C 2
Al – Bauxite (Al2O3) HgS : Cinnabar
Pb – Cerussite (PbCO3) 3. (a) 4. (a)
20. (b) Semiconductor materials like Si and Ge are usually 5. (b) From given reactions, Free energy of the reaction :
purified by zone refining. Zone refining is based on D
the principle of fractional crystallisation i.e. difference ZnO ( g ) + C ( s ) ¾¾¾¾® Zn ( g ) + CO ( g ) ,
1000°C
in solubilities of impurities in solid and molten states is negative.
of metal, so that the zones of impurities are formed
1
and finally removed. 6. (c) C ( s ) + O2( g ) ® CO( g ) ; DS increases. Hence, as
21. (c) 2 Cu2S (s) + 3O2 (g) ® 2Cu2O(s) + 2SO2(g) 2
The unchanged Cu2S, mixed with Cu2O and heated the temperature increases, TDS increases and hence
strongly in absence of air DG (DH – TDS) decreases. In other words, the slope of
the curve for formation of CO decreases. However, for
2 Cu2S + 2Cu2O ® 6Cu + SO2
all other oxides, it increases.
22. (a) Froth floatation method is mainly applicable for 7. (a) The more stable CO2 has higher enthalpy of formation
sulphide ores. than CS2.
Malachite ore : Cu(OH)2 . CuCO3 8. (d)
Magnetite ore : Fe3O4 9. (b)
Siderite ore : FeCO3 (I) Mond's process
Galena ore : PbS (Sulphide Ore) 50°C 200°C
23. (c) Ni + 4CO ¾¾¾® éë Ni ( CO )4 ùû ¾¾¾¾ ® Ni + 4CO ­
Im pure Pure
24. (c) Zn being more reactive than Ag and Au, displaces them. Volatile
complex
Leaching
4Ag + 8NaCN + 2H2O + O2 ¾¾¾¾® (II) Removal of lead poisoning
4Na[Ag(CN)2] + 4NaOH 2-
Sodium dicyanoargentate (I)
ˆˆ† éë Pb ( EDTA )ùû
Pb2 + + EDTA 4- ‡ˆˆ
Soluble
(III) Cyanide process for extraction of silver
Soluble cyanide compound can be treated with Zn to
1
give metal by displacement. ˆˆ†
2Ag + 4NaCN + H 2 O + O2 ‡ˆˆ
Displacement 2
2Na[Ag(CN)2] + Zn ¾¾¾¾¾¾ ®
Na2[Zn(CN)4] + 2Ag¯ 2Na éë Ag ( CN ) 2 ùû + 2NaOH
25. (b) (IV) Separation of ZnS from galena by using depressant in
26. (b) Both assertion and reason are true but reason is not froth flotation process
the correct explanation of assertion. Non fusible mass 10. (b)
present in ore in mixing with suitable flux are fused 11. (a) Zone refining is based on the difference in solubility of
which are then reduced by coke to give free metal. impurities in molten and solid state of the metal. This
27. (a) Zinc metal which has a more negative electrode method is used for obtaining metals of very high purity.
potential than iron will provide electrons in preference 12. (c) When an ore containing gold is treated with KCN
solution. (cyanide process for extraction of gold), a
of the iron, and therefore corrodes first. Only when all
soluble complex of gold is formed.
the zinc has been oxidised, the iron start to rust.
28. (c) Because Na is very reactive and cannot be extracted 13. (b) CuSO 4 Cu 2 + + SO 24 -
by means of the reduction by C, CO etc. So it is extracted
by electrolysis. H2O H + + OH -
29. (d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii) At cathode : Cu 2 + + 2e - ® Cu
30. (d) Mg has more – DG° value than alumina. So it will be in
the lower part of Ellingham diagram. Metals which At anode : 4OH - ® 2H 2 O + O 2 + 4e -
have more – DG° value can reduce those metal oxides 14. (d) Na reacts vigorously with water (exothermic process )
which have less – DG° value. 15. (d)
 21. p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18)
Exercise - 1 25. (a) N2O is used as anaesthetic
26. (c) 2NO + O 2 ® 2 NO 2 brown
1. (d) Ionic radii increases down the group
2. (b) In case of nitrogen, d-orbitals are not available. Pt . gauge
27. (a) 4NH 3 + 5O 2 ¾¾¾¾® 4NO + 6H 2 O
3. (a) Collectively these elements are called pnicogens and
28. (b) The slow decomposition of HNO3 is represented by
their compound pniconides. the eqn.
4. (d) Metallic character increases down the group, Bi is most 4HNO3 ® 4NO2 + 2H2O + O2
metallic (yellow-brown)
5. (d) Bismuth forms metallic bonds in elemental state. 29. (d) For nitrogen, only NF3 is known to be stable.
6. (a) –3, +3, +5 30. (c) BiH3 is the strongest reducing agent while NH3 is the
7. (d) N2 molecule contains triple bond between N atoms weakest reducing agent.
having very high dissociation energy (946 kJ mol–1)
O
due to which it is relatively inactive. O

=
8. (a) Nitrogen due to small size is able to show pp-pp lateral 31. (d) NºN® O N–N =

=
overlap forming N º N, rest elements due to bigger size (i) (ii) O
are not able to show pp-pp lateral overlap. O O
9. (c) Catenation tendency is higher in phosphorus when O O
N–O–N ®

= ®

= ®
N–N ®
compared with other elements of same group.

=
O

=
10. (c) Nitrogen form N2 (i.e. NN) but phosphorus form P4, O O O
(iii) (iv)
because in P2, pp — pp bonding is present which is a
weaker bonding. 32. (d) 4 Zn + 10 HNO3 (dil.) ® 4 Zn(NO3)2 + 5H2O + N2O
11. (d) The cause of inert nature of N2 is the presence of Zn + 4 HNO3 (conc.) ® Zn(NO3)2 + 2H2O + 2NO2
triple bond 33. (a) Both white and red phosphorus are not soluble in CS2
12. (b) only white phosphorus is soluble in CS2.
Heat 34. (a) Except (a) all other properties are shown by white
13. (d) NH 4 Cl + NaNO 2 ¾¾¾¾
® NH 4 NO 2
- NaCl
phosphorous.
Heat
¾¾¾® N 2 + 2H 2O. 35. (b) White phosphorus on heating readily catches fire in
14. (a) Oxide in which central atom has higher charge and more air to give dense white fumes of P4O10.
electronegativity is more acidic, i.e.
N2O5 > N2O4 > P2O5 > As2O3. P4 + 5O2 ¾¾ ® P4O10.
15. (a) Order of dipole moment 36. (c) Ca3P2 + 6H2O ® 3Ca(OH)2 + 2PH3 ; i.e 2 moles of
NH3 > PH3 > AsH3 > SbH3 phosphine are produced from one mole of calcium
(Based upon electronegativity) phosphide.
16. (c) As the size of central atom increases the lone pair of 37. (d) PH3 is not obtained when metaphosphoric acid is
electrons occupies a larger volume. In other words heated.
electron density on the central atom decreases and 38. (a) The combustibility of PH3 is due to presence of P2H4.
consequently its tendency to donate a pair of electrons The pure PH3 is not combustible.
decreases along with basic character from NH3 to BiH3.
600°C
17. (b) Liquid ammonia has high vapour pressure which is 39. (d) 2H 3 PO 4 ¾¾ ¾
¾® 2 HPO 3
- 2H 2O
lowered down by cooling, otherwise the liquid will bump.
18. (c) By Haber’s process D
40. P2O5 + 3H 2O ¾¾® 2H3 PO4
(d)
19. (a) Only nitrates of heavy metals and lithium decompose
on heating to produce NO2. 41. (b) Orthophosphoric acid, H 3PO 4 contains three P – OH
20. (d) N2O3, N2O4 and N2O5 are acidic oxides. Only N2O is bonds and is therefore, tribasic.
neutral oxide. O
21. (d) NO2 is reddish brown coloured gas. Rest of the oxides ||
are colourless. P
| OH
|

22. (c) In N2O (nitrous oxide) two N atoms are covalently

OH
bonded through triple bond
orthophosphoric acid
[ N º N ¾¾® O ]
42. (b) PCl3 + H2O ¾¾® POCl3 + 2HCl
23. (b) FeSO 4 + NO ® FeSO 4 .NO POCl3 + 3H2O ¾¾® H3PO4 + 3HCl
24. (b)
 EBD_7374
594 CHEMISTRY

43. (c) Structure of hypophosphorous acid O O

H
| (d) P (e) P
H-O- P ® O HO OH
| H OH
H OH OH
Two H-atoms are attached to P atom. H 3PO 4 H3PO3
44. (c) In cyclic metaphosporic acid number of P–O–P bonds The H–atom of the –OH group is ionisable whereas H–
is three. atom which is directly linked to P–atom is non-ionisable.
O OH
Thus H3PO3 is dibasic acid.
P
O O 52. (a) Pyrophosphorous acid (H4P2O5) is a dibasic acid as it
O O contains two P—OH bonds.
P P O O
O OH
HO ½½ ½½
45. (d) H—P—O—P—H
½ ½
46. (b) O OH OH
53. (b) Formula of cyclotrimetaphosphoric acid is (HPO3)3
bridging P bridging Oxidation state of ‘P’ is 3(+ 1 + x + 3 (– 2)) = 0
O x+ –6+1 =0 Þ x= +5
O 54. (a) O O
O
HO — P — P — OH
P O
HO OH
O P Hypophosphoric acid
O
O P O OH OH
bridging
O bridging O P O P O
oxygen
OH OH
Pyrophosphoric acid
O
HO O OH
47. (b) H P H Hypophosphorous acid (H3PO2) is a P P
O O O
O Metaphosphoric acid
H O
monobasic acid. i.e., it has only one ionisable hydrogen HO P OH
atom or one OH is present.
1 OH
48. (c) Hybridisation in PCl5 = (5 + 5 + 0 - 0) = 5 sp3d Orthophosphoric acid
2
55. (b) 56. (b)
49. (c) H5P5O15 (HPO3)5. It is metaphosphoric acid which is a
57. (c) At higher temperatures, dinitrogen combines with metals
cyclic phosphate.
to form ionic nitrides.
50. (b) H4P2O5 is pyrophosphorous acid it contains P–O–P
58. (b) With the decrease in the electronegativity of central
bond
atom the bond angle decreases
51. (d) Structures of given oxyacids are following
59. (b) CuSO 4 + 4 NH 3 ® [Cu ( NH 3 ) 4 ] SO 4
O O
Blue complex due to Cu(NH 3 ) 2 +
4
P P 60. (b) 2NO + N2O4 ¾¾¾ 250K
® 2N O
2 3
(a) HO O OH 61. (b) The slow decomposition of HNO3 is represented by
OH OH the eqn.
H4P2O7 4HNO3 ® 4NO2 + 2H2O + O2
(yellow-brown)
O
O 62. (a) 63. (a)
64. (a) We know that empirical formula of hypophosphorus
P acid is H3PO2. In this only one ionisable hydrogen
(b) (c) HO P O
HO H atom is present i.e. it is monobasic. Therefore option
HPO3
H (a) is correct structural formula of it.
H3PO2
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 595

65. (c) [Fe(H2O)5NO]2+ ion is formed 89. (d) 90. (c)

66. (b) NO2 and N2O4 has + 4 oxidation state for nitrogen. 91. (c) It is H2SO5.
67. (c) 3CuSO4 + 2PH3 ® Cu3P2 + 3H2SO4 92. (c) HO.SO 2OH + 2PCl5 ® ClSO2Cl + 2POCl3 + 2HCl
3HgCl2 + 2PH3 ® Hg3P2 + 6HCl
Sulphuryl chloride
68. (a)
69. (a) Both assertion and reason are true and reason is the 93. (c) Å Å
correct explanation of assertion. O O
M + HNO3 ¾¾
® MNO3 + H O O– –O O
(metal) (conc.) (metal nitrate) (nascent hydrogen)
Ozone is diamagnetic in nature (due to presence of
2HNO3 + 2H ¾¾
® 2NO2 + 2H 2O paired electron) and both the O – O bond length are
(nascent hydrogen)
equal. It has a bent structure.
70. (b) 71. (a)
94. (c) Bond angle of H2S (92°) < H2O (104°31). As the
72. (a) H2O (due to intermolecular H - bonding)
electronegativity of the central atom decreases, bond
73. (b) Oxygen being more electronegative
angle decreases. In the present case, S is less
74. (a) SnO2 is an amphoteric oxide because it reacts with acids
as well as with bases to form corresponding salts. electronegative than oxygen. Thus bond pairs in H2S
SnO2 + 2H2SO4(conc) ¾¾ are more away from the central atom than in H2O and
® Sn(SO4)2 + 2H2O
SnO2 + 2NaOH ¾¾ thus repulsive forces between bond pairs are smaller
® Na2SnO3 + H2O
75. (d) All hexafluorides of group 16 elements are gaseous in producing smaller bond angle.
nature. 95. (c) Air is liquified by making use of the joule-Thompson
76. (b) Oxygen can be prepared by heating oxides of Hg, Pb, effect (cooling by expansion of the gas) Water vapour
Ag, Mn and Ba. and CO2 are removed by solidification. The remaining
D major constituents of liquid air i.e., liquid oxygen and
2HgO ¾¾® 2Hg + O2 liquid nitrogen are separated by means of fractional
77. (c) In KMnO4 manganese is already present in its highest distillation (b.p. of O2 = –183°C : b. P. of N2 = – 195.8°C)
possible oxidation state i.e. +7.So no further oxidation 96. (d) SH–bond is weaker than, O–H bond. Hence H2S will
is possible. furnish more H+ ions
D 97. (a)
78. (b) 2KMnO 4 ¾¾® K 2 MnO4 + 4MnO 2 + O 2
79. (d) 2Ag2O (s) ® 4Ag (s) + O2 (g) 98. (d) Ionisation potential decreases down the group.
2Pb3O4 (s) ® 6PbO (s) + O2 (g) 99. (a)
2PbO2 (s) ® 2PbO (s) + O2 (g) 100. (c) The electron gain enthalpy order for halogens is
80. (a) Mn2O7 is an acidic oxide. BaO and Na2O are basic Cl > F > Br > I
oxides while N2O is a neutral oxides. Due to small size of fluorine the extra electron to be
81. (c) It is 8 added feels more electron-electron repulsion. Therefore
82. (c) S2 is paramagnetic. It contains two unpaired electrons fluorine has less value for electron affinity than chlorine.
in the antibonding p* orbital 101. (d)
V2O5
102. (a) Reactivity follows the order F > Cl > Br > I
83. (a) 2SO2(g) + O2(g) ¾¾¾® 2SO3(g) 103. (d)
O O 104. (b) Except ionisation potential other factors are true to
=

84. (b) O = S–O–O–S=O explain the oxidising (strong) behaviour of F2 .

105. (b)
OH OH
Peroxodisulphuric acid
106. (d) Fluorine exhibit -ve oxidation state
(H2S2O8) 0 +1 -1
85. (b) Conc. H2SO4 is a strong dehydrating agent due to 107. (b) H 2 O + Br2 ¾¾ ® HOBr + HBr
which carbohydrates becomes charred on reaction with Thus here oxidation number of Br increases from 0 to
conc. H2SO4 acid. +1 and also decreases from 0 to –1. Thus it is oxidised
86. (b) The key step in the manufacture of H2SO4 is catalystic as well as reduced.
oxidation of SO2 with O2 to give SO3 in presence of V2O5. 108. (d) Since all the halogens have a strong tendency to accept
87. (a) In SO3, sp2 hybridisation electrons. Therefore halogens act as strong oxidising
88. (d) Caro’s acid is H 2SO 5 which contains one agents and their oxidising power decreases from
S – O – O – H peroxy linkage. It is also known as fluorine to iodine.
permonosulphuric acids. 109. (b) On moving from top to bottom of halogen group the
O bond dissociation energy of hydrogen halides
|| decreases and so the heat of formation of halogen acids
H – O – O – S – OH also decreases.
|| 110. (c) Volatile character HCl > HBr >HI > HF
O 111. (d) Due to hydrogen bonding HF is a liquid
Caro's acid
 EBD_7374
596 CHEMISTRY

112. (d) Bleaching action of chlorine is due to oxidation in H-F H - Cl H - Br H-I

presence of moisture. 135kcal mol-1 103kcal mol-1 87 kcal mol-1 71kcal mol-1
Cl 2 + H 2O ® HCl + HClO
129. (c) MI > MBr > MCl > MF. As the size of the anion
HClO ® HCl + O
decreases covalent character also decreases.
Colouring matter + | O | ® Colourless matter
113. (b) Cl2 + 2NaOH ® NaCl + NaClO + H2O 130. (a) Metal halides with higher oxidation state are more
(cold & dil)
covalent than the one in lower oxidation state.
3Cl2 + 6NaOH ® 5NaCl + NaClO3 + 3H2O 131. (c) 2F2 (g) + 2H2O (l) ® 4H+ (aq) + 4F– (aq) + O2 (g)
(hot & conc.) Cl2 (g) + 2H2O (l) ® HCl (aq) + HOCl
114. (a) 2NaOH + Cl2 ® NaCl + NaOCl + H 2 O +1 +5 -1
132. (d) NaClO ¾¾ ® NaClO3 + 2NaCl All statements are
hence Cl- and OCl-
correct as evident from the reaction
115. (d) MnO2 or KMnO4 with conc HCl give Cl2.
+7 +2 133. (b) 2KMnO 4 + 16HCl ® 2KCl + 2MnCl 2 + 8H 2 O + 5Cl 2
116. (d) 2 KMnO 4 + 16HCl ® 2 MnCl 2 + 2 KCl + 8H 2 O + 5Cl 2 134. (d) Electronic configuration of He is 1s2
O.S of Mn changes from +7 to +2 hence reduction 135. (b) Ionization potential of inert gases is highest in periodic
occurs and Cl2 is formed. table due to stable electronic configuration.
117. (d) 6CaOCl 2 ® Ca (ClO3 ) 2 + 5CaCl 2 136. (a) Ionisation energy decreases as we move away from
It is autooxidation. nucleus due to less electrostatic attraction between
118. (d) HCl acid at 25º C is a gas and polar in nature electrons and nucleus
119. (d) In gaseous state the HCl is covalent in nature while in 137. (a) The smaller the size the least is the polarisability
138. (c) The differentiating electron enter in s subshell in case
aqueous solution it ionises to give H+ and C l ions
of He, hence it is s- block element. Its electronic
120. (d) As the oxidation state of the central halogen atom configuration l s2 makes it inert in nature hence it is
increases, the halogen-oxygen bond becomes more and placed with inert gases.
more covalent. As a result the thermal stability of the 139. (c) Ar is the most abundant in atmosphere
oxoacid increases. Thus, HClO4 is most stable to heat,
140. (d) Due to weak van der Waal’s forces, He has lowest
whereas HClO is least stable to heat.
boiling point
121. (c) The bond energy of interhalogen compounds is less
than the bond energy of halogens. 141. (d) The larger the size the more is the polarisiability
122. (d) Interhalogen compounds are not highly volatile 142. (d) He was observed in the spectrum of the sun
143. (d) Electron gain enthalpy for noble gases is positive and
0 -1 +5
123. (b) 6NaOH + 3Cl 2 ¾¾ ® 5NaCl + NaCl O3 + 3H 2O it becomes less positive with increase in size of atom.
124. (c) 6NaOH + 3Cl2 ® 5NaCl + NaClO3 + 3H2O Value of electron gain enthalpy
(hot and conc.) He – 48 kJ mol–1, Ne – 116 kJ mol–1
125. (b) Physical state of iodine is different from other halogens Ar, Kr – 96 kJ mol–1, Xe – 77 kJ mol–1
as iodine is solid, bromine is a liquid whereas fluorine Hence, Ne has highest positive electron gain enthalpy.
and chlorine are gases. 144. (b)
126. (d) 145. (b) The shape of XeO3 is Trigonal Pyramidal.
127. (c) From the given options we find option (a) is correct. The
oxidising power of halogens follow the order
F2 > Cl2 > Br2 > I2. Option (b) is incorrect because it in Xe (Trigonal Pyramidal Structure)
O O
not the correct order of electron gain enthalpy of O
halogens. 146. (c) Solubility increases from He to Rn
The correct order is Cl2 > F2 > Br2 > I2. The low value 147. (d) Xe forms maximum compounds hence it is most
of F2 than Cl2 is due to its small size. reactive
Option (c) is incorrect. The correct order of bond 148. (b) Noble gases exhibit low chemical activity
dissociation energies of halogens is
149. (d)
Cl2 > Br2 > F2 > I2.
150. (b) In XeOF4, Xenon is sp3d 2 hybridised and has one lone
Option (d) is correct. It is the correct order of
pair of electrons.
electronegativity values of halogens. Thus option (b)
and (c) are incorrect. 151. (c) XeF6 + 3H2O ¾¾ ® XeO3 + 6HF
128. (c) The H–X bond strength decreases from HF to HI. i.e. \ Complete hydrolysis of XeF6 gives XeO3 (an
HF > HCl > HBr > HI. Thus HF is most stable while HI explosive).
is least stable. The decreasing stability of the hydrogen 152. (d) The products of the concerned reaction react each
halide is also reflected in the values of dissociation other forming back the reactants.
energy of the H–X bond XeF6 + 3H 2 O ¾¾ ® XeO3 + 6HF .
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 597

F situated on the plane and the fluoride atoms are on the

top and bottom. F
O

153. (c) XeF2 : Xe O Xe

O
F
F 165. (a) As size increases, van der Waal's forces of attraction
3lp
between noble gas atoms also increases. Consequently,
ease of their liquefaction increases.
F F 166. (c) Argon is used in high temperature welding and other
XeF4 : operations which require a non-oxidising atmosphere
Xe
and the absence of nitrogen.
F F 167. (b) Neon gives a distinct reddish glow when used in either
low-voltage neon glow lamps or in high voltage
2lp discharge tube.
F 168. (c) Helium is twice as heavy as hydrogen it is inflammable
F but not lighter than hydrogen. Helium has the lowest
melting and boiling point of any element which makes
XeF6 : F liquid helium an ideal coolant for many extremely low
Xe F
temperature application such as super conducting
magnet and cryogenic research where temperature
F F close to absolute zero are needed. He is used in gas
cooled atomic reactors as a heat transfer agent.
169. (c) Coloured discharge tubes mainly contain Neon
XeO3 : 170. (a) Breathing mixture is (O2 + He)
Xe 171. (a) Mixture of (He + O2) is used for asthma patient
172. (b) 173. (c)
O O 174. (c) For statement (iii) preparation of XeF2 requires Xe in
O
excess amount
1lp
673K,1 bar
Hence XeF2 has maximum no. of lone pairs of electrons. Xe ( g ) + F2( g ) ¾¾¾¾¾® XeF2( s )
154. (d) XeO2F2 has trigonal bipyramidal geometry, but due to ( excess )
presence of lone pair of electrons on equitorial position, For statements (iv)
its actual shape is see-saw.
2XeF2(s) + 2H2O(l) ¾¾ ® 2Xe(g) + 4HF(aq) + O2(g)
F
O 6XeF4 + 12H2O ¾¾ ® 4Xe + XeO3 + 24HF + 3O2
Xe XeF6 + 3H2O ¾¾ ® XeO3 + 6HF
175. (d) 176. (a)
O 177. (c) 2XeF6 + SiO 2 ® SiF4 + 2XeOF4
F
155. (b) XeF4 + H 2O ® 2HF + XeOF2 178. (c) Xenon undergo sp3 hybridization.
156. (a) No compound of He as yet been reported (ground
157. (a) No compound of Ar as yet been reported with F2 state)
5s 5p 5d
158. (c) XeF6 + 3H 2 O ® 6HF + XeO 3
(third excited
159. (b) XeOF4 square pyramidal state)
160. (b) XeF4 is planar 5s 5p 5d
161. (a) In XeO3 the hybridisation is sp3 In the fourth excited state xenon atom, has 8 unpaired
162. (a) XeF2 XeF4 XeF6 electrons
Valence electrons of Xe 8 8 8
Electrons involved 2 4 6
in bond formation 5s 5p 5d
One s and three p orbital undergo sp3 hybridization.
Lone pairs left 3 2 1
163. (c) He is obtained during radioactive decay Four sp3 hybrid orbitals form four s bonds with oxygen
164. (b) The hybridization of XeO3F2 is sp3d and its structure atoms. They are ssp3 – p. Four pp– dp bonds are also
is trigonal bipyramidal in which oxygen atoms are formed with oxygen atoms by the unpaired electrons.
 EBD_7374
598 CHEMISTRY

H3PO4 has 3 – OH groups i.e., three ionisable H-atoms

Exercise - 2
and hence it forms three series of salts: NaH2PO4,
1. (c) Hydrogen iodide (HI) is stronger reducing agent than Na2HPO4 and Na3PO4
H2SO4. Hence, it reduces H2SO4 to SO2 and itself 10. (c) The acids which contain P–H bond have strong
oxidises to I2. reducing properties. Thus, H3PO2 is a strong reducing
H2SO4 + 2HI –® SO2 + I2 + 2H2O agent due to the presence of two P — H bonds and
(Violet one —OH group
colour) O
2. (b) When H2S gas is passed through an aqueous solution ||
of copper sulphate acidified with dil. HCl a black ppt. P H
of CuS is obtained. H OH
Hypophosphorus acid
dil. HCl
CuSO 4 + H 2S ¾¾¾¾
® CuS + H 2SO 4 11. (b) On heating, lead nitrate produces brown coloured
black ppt
nitrogen dioxide (NO2) and lead (II) oxide.
On boiling CuS with dil. HNO3 it forms a blue coloured D
2Pb ( NO3 )2 ¾¾® 4NO2 + 2PbO + O 2
solution and the following reactions occur
3CuS + 8HNO3 –® 3Cu(NO3)2 + 2NO + 3S + 4H2O 12. (a) Nitrogen does not show allotropy due to its small size
2+ and high electronegativity. The N–N bond is weak
+
Cu 2aq + 4NH3 ( aq ) ® éë Cu ( NH3 ) 4 ùû due to high inter–electronic repulsions among non-
( )
(Deep blue solution) bonding electrons due to the small bond distance.
Hence it does not show allotropy.
3. (c) O O H 13. (c) Maximum covalency of nitrogen is 4 in which one electron
P is from s-orbital and 3 electrons are from p-orbitals.
O O
O O Hence, total four electrons are available for bonding.
14. (a) The single N — N bond is weaker than the single
P P P — P bond. This is why phosphorus show allotropy
H O O O H but nitrogen does not.
i.e, 3 double and 12 single Bonds 15. (a) When freshly prepared solution of FeSO4 is added to
4. (c) Among carbon, nitrogen, phosphorus and boron only an aqueous solution containing NO3- ion, it leads to
phosphorus has vacant d-orbital h ence only the formation of a brown coloured complex. This is
phosphorus has the ability to form pp – dp bonding. known as brown ring test for nitrate ion.
5. (a) Both CO32 - and NO3- have same number of electrons. NO3- + 3Fe2+ + 4H+ –® NO + 3Fe3+ + 2H2O
2+ 2+
éFe ( H2 O) ù + NO –® éFe ( H 2O ) ( NO ) ù + H2O
CO32 - = 6 + 8 × 3 +2 = 32 ë 6û ë 5 û
Brown ring
NO3- = 7 + 8 × 3 + 1 = 32 16. (b) The only well characterised compound having + 5
Hence, CO32 - and NO3- are isoelectronic. Also, both oxidation state of Bi is BiF5. It is due to smaller size
have same type of hybridization (sp2) and have trigonal and high electronegativity of fluorine.
planar structure. Hence, they are also isostructural. 17. (a) On heating ammonium dichromate and barium azide
6. (a) On moving down the group size of halogen atom both produces N2 gas separately.
increases hence the H–X bond length increases. As a
result, bond dissociation enthalpy decreases. ( NH 4 )2Cr2 O 7 ¾¾
D
® N 2 + 4H 2 O + Cr2 O3
Hence, the correct order of bond enthalpy is : Ba ( N3 )2 –® Ba + 3N2
H – F > H – Cl > H – Br > H – I.
Pt / Rh gauge catalyst
7. (d) On moving down the group size of central atom 18. (a) 4NH3 + 5O2 ¾¾¾¾¾¾¾¾® 4NO(g)+ 6H O (l)
500K, 9 bar 2
increases thus bond length of E—H bond increases
\ Two moles of NH3 will produce 2 moles of NO on
and bond dissociation energy decreases. Hence,
catalytic oxidation.
reducing nature increases in the order : NH3 < PH3 <
19. (c) Let oxidation state of P in NaH2PO2 is x.
AsH3 < SbH3
1+2×1+x+2×–2=0
8. (c) White phosphorus on reaction with NaOH solution in
1+2+x–4=0
the presence of inert atmosphere of CO2 produces
+x–1=0
phosphine gas which is less basic than NH3.
x=+1
P4 + 3NaOH + 3H 2 O –® PH3 + 3 NaH 2 PO 2 20. (c) SF4 has sea-saw shape as shown below:
(Sodium hypophosphite)
..
9. (c) Structure of H3PO4 is
O
|| F S F
P
HO OH F F
OH
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 599

It has trigonal bipyramidal geometry having sp3d 32. (a) The acids which contain P-H bond have strong
hybridisation. reducing properties. Thus H3PO2 acid is good reducing
21. (c) Carbon on oxidation with H2SO4 produces two types agent as it contains two P–H bonds and reduces, for
of oxides CO2 and SO2. example, AgNO3 to metallic silver.
C + 2H2SO4 (conc) –® CO2 + 2SO2 + 2H2O 4 AgNO3 + 2H2O + H3PO2 —®
22. (a) MnO2 reacts with HCl to produce greenish yellow 4Ag + 4HNO3 + H3PO4
coloured gas of Cl2. 33. (c) SO2 is widely used in food and drinks industries for its
property as a preservative and antioxidant while NO2
MnO2 + 4HCl –® MnCl2 + 2H2O + Cl2
( Black ) (greenish is not used as food preservative.
yellow gas) 34. (d) OF 2; among the following O and F, F is more
Cl2 on further treatment with NH3 produces NCl3. electronegative than oxygen.
So OF2 cannot be called oxide because in that case O is
-3 +3
N H3 + 3Cl2 –® NCl3 + 3HCl in +2 oxidation state which is not possible, so OF2 is
called oxygen difluoride.
Hence, NH3 (– 3) changes to NCl3 (+ 3). 35. (b) Th e H-bondin g is present in HF due to high
23. (c) Bertlett had taken O+2 Pt F6- as a base compound electronegativity of fluorine atom while H-bonding is
not present in HI, HBr and HCl.
because O2 and Xe both have almost same ionisation
36. (c) Helium is twice as heavy as hydrogen it is inflammable
enthalpy.
but not lighter than hydrogen. Helium has the lowest
24. (d) In solid state PCl5 exists as an ionic solid with the
melting and boiling point of any element which makes
cation [PCl 4]+ (tetrahedral) and the anion [PCl 6]–
(octahedral). liquid helium an ideal coolant for many extremely low
temperature application such as super conducting
Cl + magnet and cryogenic research where temperature
Cl
Cl Cl close to absolute zero are needed. He is used in gas
P P cooled atomic reactors as a heat transfer agent.
Cl Cl Cl Cl 37. (b) 38. (d)
Cl Cl 39. (a) For isoelectronic species, size of anion increases as
– +
[PCl6] [PCl4] negative charge increases. Thus the correct order is
tetrahedral
octahedral
N 3- > O 2 - > F -
25. (c) Greater the SRP value, higher will be the oxidising (1.71) (1.40) (1.36)
power. Hence the correct order of oxidising power is: 40. (b) ICl
BrO 4- > IO4- > ClO4- Order of reactivity of halogens
26. (b) Isoelectronic pair have same number of electrons
Cl2 > Br2 > I2
Total number of electrons for the given compounds :
But the interhalogen compounds are generally more
BrO2– BrF2+ reactive than halogens (except F2), since the bond
= = 52 = = 52
35 + 2 ´ 8 + 1 35 + 9 ´ 2 – 1 between two dissimilar electronegative elements is
ICl 2 ClO2 BrF weaker than the bond between two similar atoms i.e, X – X
41. (c) Nitrogen and oxgen in air do not react to form oxides of
53 + 2 ´ 17 = 87 17 + 16 = 33 35 + 9 = 44 nitrogen in atmosphere because the reaction between
CN – O3 nitrogen and oxygen requires high temperature.
6 + 7 + 1 = 14 8 ´ 3 = 24 42. (b) Xe. As we move down the group, the melting and boiling
points show a regular increase due to corresponding
27. (a) The weakening of M—H bond with increase in size of
increase in the magnitude of their van Der Waal forces
M (where M = S, Se, Te) explains the acid character of
of attraction as the size of the atom increases.
hydrides. Since on moving down the group atomic size
increases hence bond length increases and hence 43. (b) Xe + F2 ¾673 K
¾¾® XeF2
removal tendency of H also increases. 2 :1
673K
28. (c) Br2 reacts with NaI only to get I2. Xe + 2F2 ¾¾¾® XeF4
2NaI + Br2 ® 2NaBr + I2 5 - 6Atm
29. (c) Acidic strength increases as the oxidation number of 1:5 573K
Xe + 3F2 ¾¾ ¾¾¾® XeF6
central atom increases. 50- 60 Atm
Hence acidic strength order is 1 : 20
(+7) (+5) (+3) (+1) XeF3 is not possible.
HClO4 > HClO3 > HClO2 > HClO 44. (c) Order of basic character is NH3 > PH3 > AsH3 > SbH3.
30. (c) I2 gives blue colour with starch. Basic-character decreases down the group from N to
31. (c) Fluorine, since it is the most electronegative element. Bi due to increase in atomic size.
 EBD_7374
600 CHEMISTRY

45. (b) Phosphinic acid as shown in structure below has one

(iii) 2NH2Cl + CaO ¾¾
® 2NH3 + CaCl2 + H2O
P—OH bond thus it is monobasic or monoprotic By product
O
53. (b) Nitrous oxide (i.e., N2O) is the laughing gas.
P
O O O
H OH (Monoprotic)
H 54. (a) –
O –S–S–S–S–O S
Phosphonic acid as shown in structure has two P–OH S O
bonds thus it is dibasic or diprotic O O O
O S4 O6 2 - S2 O32 -
P
(Diprotic acid)
55. (a) XX' ® Linear (e.g. ClF, BrF)
H OH XX3' ® T-Shape (e.g. ClF3, BrF3)
OH XX5' ® Square pyramidal (e.g. BrF5 IF5)
46. (a) CaC2 + N2 ® Ca(CN)2 + C
XX7' ® Pentagonal bipyramidal (e.g. IF7)
47. (b) Bond dissociation enthalpy decreases as the bond
56. (a) NF 5 does n ot exist because N does not form
distance increases from F2 to I2. This is due to increase
pentahalides due to the absence of d-orbital in its
in the size of the atom, on moving from F to I.
valence shell. While P, As and Sb form pentahalides of
F – F bond dissociation enthalpy is smaller then Cl – Cl
the general formula MX5 (where, M = P, As and Sb)
and even smaller than Br – Br. This is because F atom
due to the presence of vacant d-orbitals in their
is very small and hence the three lone pairs of electrons
respective valence shell.
on each F atom repel the bond pair holding the F-atoms
57. (a) Both have peroxy linkage
in F2 molecules.
58. (b) Both Assertion and Reason are true but reason is not
The increasing order of bond dissociation enthalphy
the correct explanation of assertion. Greater the number
is I2 < F2 < Br2 < Cl2 of negative atoms present in the oxy-acid make the
48. (a) XeF6 XeO3 acid stronger. In general, the strengths of acids that
F have general formula (HO)m ZOn can be related to the
F value of n. As the value of n increases, acidic character
also increases. The negative atoms draw electrons away
Xe from the Z-atom and make it more positive. The Z-atom,
F Xe F therefore, becomes more effective in withdrawing
O O electron density away from the oxygen atom that
O bonded to hydrogen. In turn, the electrons of H – O
F F
bond are drawn more strongly away from the H-atom.
1L.P. 1 L.P. The net effect makes it easier from the proton release
distorted octahedral Pyramidal and increases the acid a strength.
XeO4 XeF4 59. (c) Cl2 + NaOH ® NaCl + NaClO + H2O
[cold and dilute]
F F 60. (b) PH5 does not exist because d-orbital of ‘P’ interacts
O
F F with s-orbital of H. Bond formed is not stable and not
Xe
Xe energetically favorable. It depends on size and
F F F F orientation of interaction.
1 L.P. 61. (c) Compound O.S. of N
Square pyramidal 2 L.P.
Square planar N2O +1
49. (a) NO +2
50. (c) 2F2 (g) + 2H2O (l) ® 4H+ (aq) + 4F– (aq) + O2 (g) NO2 +4
Cl2 (g) + 2H2O (l) ® HCl (aq) + HOCl NO3– +5
51. (c) Phosphorous acid contain P in +3 oxidation state. NH4+ –3
Acid Formula Oxidation state Therefore increasing order of oxidation state of N is:
of Phosphorous NH +4 < N2O < NO < NO2 < NO 3- .
Pyrophosphorous acid H4P2O5 +3 +5 +2 0 -3
Pyrophosphoric acid H4P2O7 +5 62. (a) HNO3 , NO, N2 , NH4Cl
Orthophosphorous acid H3PO3 +3 63. (d) Due to high electronegativity and small size, F forms
Hypophosphoric acid H4P2O6 +4 only one oxoacid, HOF known as fluoric (I) acid.
Oxidation number of F is +1 in HOF.
52. (c) CaCl2 is produced as a by product in solvay ammonia 64. (a) He gas is used as cooling agent in super conducting
process. magnet.
(i) NaCl + CO2 + NH3 + H2O ¾¾ ®
NaHCO3 + NH4Cl 65. (c) Pb3O4 + HNO3 ® PbO2 (solid) + Pb(NO3)2 + H2O but
(ii) CaCO3 ¾¾ ® CO2 + CaO Pb+2 is more stable.
p-BLOCK ELEMENTS (GROUP 15, 16, 17 AND 18) 601

66. (a) CCl4 having no vacant d-orbital does not undergo According to L.P – L.P > L.P – B.P > B.P – B.P repulsion,
hydrolysis the correct order of s-s bond length will be : x1 > x2 > x3
In a particular period, on going left to right the order of
extent of hydrolysis increases. heat
7. (c) S + 3F2 ¾¾¾
® SF6
D (Yellow powder) 'X '
67. (d) (b) (NH 4 )2 Cr2 O7 ¾¾ ® Cr2O3 + N 2 + 4H 2O
D heat
(c) NH 4 NO2 ¾¾ ® N 2 + 2H 2 O 3SCl2 + 4NaF ¾¾¾
® SF4 + S2Cl 2 + 4NaCl
'Y '
D
(d) (NH 4 ) 2 SO4 ¾¾ ® 2NH 3 + H 2SO4
8. (b) The halate used in fireworks and safety matches in
D
(a) Ba(N 3 ) 2 ¾¾ ® Ba + 3N 2 KClO3. Thus the gas is Cl2
NH3 is evolved in case of (d) . 3Cl2 + 6KOH ® KClO3 + 5KCl + 3H2O
68. (d) chalcogens are defined as ore-forming elements. Cl2 is greenish yellow gas.
69. (c) Catenation tendency is higher in phosphorus when 9. (b) CuSO4 + 2KI ® CuI2 + K2SO4
compared with other elements of same group.
2CuI2 ® Cu 2I2 ¯ + I2 ­
Exercise - 3 White ppt Brown

1. (a) NH4ClO4 + HNO3 ® HClO4 + NH4NO3

(x) I2 + 2Na 2S2 O3 ® Na 2S4 O6 + 2NaI
Colourless
NH4NO3 ¾¾ D
® N2O + 2H2O
(y) 10. (c) ® M + éëXeF5- ùû
MF + XeF4 ¾¾
2. (d) K 2Cr2O7 + H 2SO4 + 3SO2 ®
K 2SO 4 + Cr2 (SO4 )3 + H 2O sp3d3, Pentagonal planar
Green 11. (a)
3. (a) ¾¾¾¾¾¾
Li (s) + N 2 (g) ¬¾¾¾¾® 2Li3 N (s) 12. (a) (X) is borax, Na2B4O7.10H2O
high
temperature
(i) Na 2 B 4O 7 + 7H 2O 2NaOH + 4H3BO3
Li 3 N + 3H 2 O ¾¾
® 3LiOH + NH 3 (Strong) (Weak)
Base acid
CuSO 4 + 4NH3 ¾¾
® [Cu(NH3 ) 4 ]SO4
deep blue compound Due to presence of NaOH, the aqueous solution
4. (a) HCl, HNO3 and H2SO4 form azeotrope at 20%, 68% is alkaline to litmus.
and 98% respectively by mass of acid.
Therefore, HCl contains » 20/100 = 1/5 Heat
(ii) Na 2 B4 O7 .10H 2O ¾¾¾
® Na 2 B4O7
HNO3 contains » 68/100 » 2/3 (swells)
H2SO4 contains » 98/100 » 3/3
Thus, ordinary strong solution of HCl, HNO3 and + 10H 2 O ¾¾
® 2NaBO2 + B2O3
Glassy bead
H2SO4 contains roughly 1/5, 2/3 and 3/3 fractions of
pure acid and water respectively. (iii) Na 2 B4 O 7 + H 2SO 4 + 5H 2 O ¾¾
®
5. (a) Inorganic compound + SO2 in aq. medium ® (A) Na 2SO 4 + 4H 3 BO 3
(A) + Na2CO3 ® (B) white crystals
(B) + S ® (C) (Used in photography) 13. (d) In other reactions, oxygen is evolved but in reaction
Na 2CO3 + 2SO2 + H 2O ® 2NaHSO 4 + CO 2 with SO2, all oxygen is used up in the process of
(A) oxidation and no oxygen gas is evolved.
2NaHSO 4 + Na 2CO3 ® 2Na 2SO3 + H 2 O + CO 2 3SO 2 + O 3 ¾
¾® 3SO 3
( B)
Na 2SO3 + S ® Na 2S2O3 14. (c) Both the methods (a) and (b) can be used.
(C) When passed through freezing mixture the P2H4
O present condenses and pure PH3 is obtained.
O O When passed through HI, PH3 is absorbed forming
S X1 S X2
PH4I.PH4I when treated with KOH (aq) yields pure
6. (a) O S O S
O O phosphine.
O
O PH 3 + HI ¾¾
® PH 4 I
S X3
O S PH 4 I + KOH(aq) ¾¾
® KI + H 2 O + PH 3 ­
O 15. (a) Amatol is 80% NH4NO3 + 20% TNT
O
 EBD_7374
602 CHEMISTRY

22. THE d-AND f–BLOCK ELEMENTS

Excercise - 1 12. (a) Mn7+ = 25 – 7 = 18e– = [Ar]

\ 0 unpaired electrons.
1. (c) General electronic configuration of transition elements 13. (a) The outermost electronic configuration of Fe is
is ( n - 1) d 1 -10 ns1 - 2 Fe = [Ar] 3d6 4s2
2. (b) Atomic no. of Ni = 28 Fe2+ = [Ar] 3d6 4s0
Ni (Ground state) = 1s2, 2s2, 2p6, 3s2, 3p6, 3d 8, 4s2,
2 2 6 2 6 8 0
Ni 2 + = 1s , 2s , 2p , 3s , 3p , 3d , 4s
3d Since Fe2+ has 4 unpaired electrons it is paramagnetic
in nature.
Zn = [Ar] 3d10 4s2 —— no unpaired e–
\ It has 2 unpaired electrons Hg2+ = [Ar] 4f 14 5d10 —— no unpaired e–
3. (c) Cerium (Ce) belongs to lanthanide series and is member Ti4+ = [Ar] 3d0 4s0 —— no unpaired e–
of inner-transition metals. 14. (c) Due to d 5 configuration, Mn has exactly half filled
4. (c) Mn3+ = [Ar]3d4 d-orbitals. As a result the electronic configuration is
= [Ar] stable means 3d electrons are more tightly held by the
nucleus and this reduces the delocalization of electrons
Number of unpaired electrons = 4
Cr3+ = [Ar]3d3 resulting in weaker metallic bonding.
15. (d) The minimum oxidation state in transition metal is equal
= [Ar] to the number of electrons in 4s shell and the maximum
No. of unpaired electrons = 3 oxidation state is equal to the sum of the 4s and 3d electrons.
V3+ = [Ar]3d2 Ti = [Ar] 3d24s2
= [Ar] Hence minimum oxidation state is +2 and maximum
oxidation state is +4. Thus the common oxidation states
No. of unpaired electrons = 2
of Ti are +2, +3 and +4
5. (a)
16. (a) Os shows maximum oxidation state of +8.
6. (b) Zn + [Ar]3d10 4s1,Fe 2+ [Ar]3d 6 4s0 , Ni + [Ar]3d 8 4s1, 17. (c) Due to lanthanide contraction, the size of Zr and Hf
(atom and ions) become nearly similar.
Cu + [Ar]3d104s0 ; 18. (a)
Fe 2+ contain maximum number of unpaired electrons. 19. (d) Fe3+ is easily hydrolysed than Fe2+ due to more
positive charge.
7. (b) Cr (24) = 1s 2 , 2 s2 2 p 6 , 3s 2 3 p 6 , 3d 5 , 4 s1 , 20. (d) (n – 1)d 5ns2 attains the maximum O.S. of + 7.
3+ 21. (a) The ionisation energies increase with increase in atomic
8. (d) Ni : [Ar] 3d 7
number. However, the trend is some irregular among d-
Mn3+ : [Ar] 3d 4 block elements. On the basis of electronic configuration, the
Fe3+ : [Ar] 3d 5 Zn : 1s 2 2s 2 p 6 3s 2 p6 d 10 4s 2
Fe : 1s 2 2s 2 p 6 3s 2 p 6 d 6 4s 2
Co3+ : [Ar] 3d 6
9. (c) Cu : 1s 2 2s 2 p6 3s 2 p 6 d 10 4s1
10. (c) Zn, Cd, Hg do not show properties of transition Cr : 1s 2 2s 2 p6 3s 2 p 6 d 5 4s1
elements hence they are known as non typical IE1 follows the order : Zn > Fe > Cu > Cr
transition elements. 22. (a) In a period on moving from left to right, ionic radii
11. (c) The outer electronic configuration of the given ions is as decreases.
d s (a) So order of cationic radii is
Ti2+ Cr2+ > Mn2+ > Fe2+ > Ni2+ and
(b) Sc > Ti > Cr > Mn (correct order of atomic radii)
d s
(c) For unpaired electrons
Fe2+ Mn 2+ (Five) > Ni 2+ (Two)
d s
< Co 2 + (Three) < Fe2 + (Four)
Cr+ (d) For unpaired electrons >
d s
Fe2+ (Four) > Co2+ (Three) >
Cu+
Ni2+ (Two) > Cu 2+ (One)
THE d-AND f–BLOCK ELEMENTS 603

23. (b) 30Zn and 80Hg have their d orbitals completely filled 40. (b)
so they do not show any variable valency. 41. (d) Ti4+ (3d0) and Zn2+ (3d10) are colourless.
24. (a) Highest O.S. by Mn (+7) 42. (c)
25. (d) Sc does not show variable valency. 43. (b) 2Fe3+ + 2I– ¾¾ 2+
® 2Fe + I2
26. (d)
27. (a) Zn, Cd and Hg due to presence of completely filled 2Fe 2+ + S2 O82 - ¾¾
® 2Fe3+ + 2SO 24 -
d-orbitals in ground state as well as in their common 44. (c) Only Cu in its +2 oxidation state is able to oxidizes the
oxidation states are not regarded as a transition metals I– to I2
3+
but they are studied along with the transition metals. 45. (b) La : 54 e– = [Xe]
28. (a) The +7 oxidation state of Mn is not represented in Ti : 19 e– = [Ar] 3 d 1 (Coloured)
3+
simple halides but MnO3F is known
Lu 3+ : 68 e– = [Xe] 4 f 14
29. (d) For chromium ion + 3 oxidation state is most stable.
30. (c) The melting points of the transition element first rise to Sc3+ : 18 e– = [Ar]
a maximum and then fall as the atomic number increases 46. (b) (i) Outer electronic configuration of Mn is 3d 54s2 and
manganese have abnormally low melting point. hence exhibits +7 oxidation state.
31. (a) Mn2+ –5 unpaired electrons (ii) Zinc does not form coloured ions as it has
Fe2+ – 4 unpaired electrons completely filled 3d104s7 configuration.
Ti++ – 2 unpaired electrons (iii) In [CoF6]3–, Co3+ is a d7 system. Fluoride is a
Cr++ – 4 unpaired electrons weak field ligand and hence does not cause pairing
Hence maximum no. of unpaired electron is present in of electrons.
Mn++. Co3+ ­¯ ­¯ ­ ­ ­ ; Paramagnetic
Magnetic moment µ number of unpaired electrons
(iv) Sc can form a maximum of +3 oxidation state as it
32. (d) E ° 3+ 2 + = – 0.41 V E °Fe3+ / Fe 2 + = + 0.77 V has an outer electronic configuration of 3d14s2.
Cr / Cr
E ° 3+ 2 + = + 1.57 V,, E ° 3+ 2 + = + 1.97 V (v) Zn exhibits only +2 oxidation state as this O.S. is
Mn / Mn Co / Co
the most stable one.
33. (d) Magetic moment m = n (n + 2 ) where n = number of 47. (d)
48. (d) The electronic configuration of different species given
unpaired electrons 15 = n(n + 2 ) \ n = 3 in the question are
2+
34. (b) 22 Ti :1s 2 2 s 2 p 6 3s 2 p 6 d 2
3+
35. (a) Sc3+® 3d 04s 0 23 V :1s 2 2 s 2 p 6 3s 2 p 6 d 2
4+
24 Cr :1s 2 2 s 2 p 6 3s 2 p 6 d 2
Fe2+® 3d 6 4s 0 5+
25 Mn :1s 2 2 s 2 p 6 3s 2 p 6 d 2
Ti3+® 3d 14s 0 49. (a) Given magnetic moment of transition metal
= n ( n + 2) = 5.92
Mn2+ ® 3d 5 4s 0
i.e., n = 5
In Sc3+ there is/are no unpaired electrons. So the
Number of unpaired electrons in Mn2+ = 5
aqueous solution of Sc3+ will be colourless.
Number of unpaired electrons in Ti3+ = 1
36. (a) Transition elements form coloured ions due to d-d
Number of unpaired electrons in Cr3+ = 3
transitions. In the presence of ligands, there is splitting
Number of unpaired electrons in Cu2+ = 1
of energy levels of d-orbitals. They no longer remain
Number of unpaired electrons in Co2+ = 3
degenerated. So, electronic transition may occur
between two d-orbitals. The required amount of energy Thus Mn2+ have magnetic moment = 5.92 BM
to do this is obtained by absorption of light of a 50. (d) Sc3+ : 1s2, 2s2p6, 3s2p6d0, 4s0; no unpaired electron.
particular wavelength in the region of visible light. Cu+ : 1s2, 2s2p6, 3s2p6d 10, 4s0; no unpaired electron.
37. (c) The transition metals and their compounds are used as Ni2+: 1s2, 2s2p6, 3s2p6d 8, 4s0;
catalysts. Because of the variable oxidation states they unpaired electrons are present.
may form intermediate compound with one of the Ti3+ : 1s2, 2s2p6, 3s2p6d 1, 4s 0;
readtants. These intermediate provides a new path with unpaired electron is present
low activation energy. V2O5 + SO2 ® V2O4 + SO3 Co2+ : 1s2, 2s2p6, 3s2p6d 7, 4s0;
2V2O4+ O2 ® 2V2O5 unpaired electrons are present
38. (b) Cu 2+ [ Ar ] 3d 9 , Ti 4 + [ Ar ] 3d 0 , Co 2+ [ Ar ] 3d 7 , So from the given options the only correct combination
is Ni2+ and Ti3+.
Fe 2 + [Ar ] 3d 6 51. (d) The ions with unpaired electrons are coloured and
1, 3, 4 are coloured ions hence the answer is b. those with paired electrons are colourless.
39. (c) If non metal is added to the interstital site the metal
becomes less malleable due to formation of covalent Zn 2 + = 1s 2, 2s2p6, 3s2 p6 d10
(No. of e - s = 28)
bond between metal and non metal
 EBD_7374
604 CHEMISTRY

Cr 3+ = 1s 2, 2s2p6, 3s2 p6 d3 68. (b) 69. (a)

-
(No. of e s = 21) 70. (a) The green colour appears due to the formation of
Cr3+ion
Ni 2 + = 1s2, 2s2p6, 3s2 p6 d8
(No. of e - s = 26) Cr2 O72– + 3SO32– + 8H + ¾¾
® 3SO 2– 3+
4 + 2Cr + 4H 2 O
Thus Zn , Cr 3+ and Ni 2+ have zero, 3 and 2
2+
71. (b) Na2Cr2O7 is hygroscopic.
unpaired electrons respectively. 72. (c) Mn2O7 ® acidic
(d) In Cu [ Ar ] 3d there is no unpaired electron,
+ 10
52. CrO ® basic
Cu 2 + [ Ar ] 3d 9 contains one unpaired electron hence V2O4 ® amphoteric
coloured. Cr2O3 ® amphoteric
53. (d) V2+ – violet, V3+ – green V4+ – blue 73. (b) 2MnO2 + 4KOH + O2 ¾¾ ® 2K 2 MnO4 + 2H 2O
dark green
Fe2+ – green Fe3+ – yellow
74. (b) 5Fe2+ + MnO-4 +8H+ ¾¾
® Mn2+ +4H2O + 5Fe3+
+4 +4 +5 +6
54. (b) VO2+ ; Ti O2+ < VO2+ < Cr O24- 5NO -2 + 2MnO 4- + 6H + ¾® 2Mn 2+ + 5NO 3- + 3H 2O
55. (b) 75. (d) As the oxidation state increases the acidity increases.
76. (d) If KMnO4 was added slowly than option a was correct,
56. (a) Cr2 O 72– + 2OH – ¾¾ ® 2CrO 42 - + H 2 O but at a moment due to addition of large amount of
Hence CrO 24- ion is obtained. KMnO4, reduction of whole KMnO4 added does not
57. (b) CrO3 + 2NaOH ® Na 2CrO 4 + H 2 O take place, it also react with Mn2+ which had formed
2- - + in the solution to give MnO2.
58. (a) Cr2O 7 + 6I + 14H ¾¾ ® 3I 2 + 7H2 O + 2Cr 3+ 2MnO4 + 3Mn2+ + 2H2O ¾¾ ® 5MnO2 + 4H+
oxidation state of Cr is +3. 77. (b) Down the group metallic character increases hence
2–
tendency to loose electron increases.
59. (d) O O 78. (c) I– is converted to IO3- by neutral or faintly alkaline
MnO 4- as shown below..
Cr Cr 2MnO -4 + H 2 O + I - ¾¾ ® 2MnO 2 + 2OH - + IO 3-
OO O 79. (c) A regular decrease in the size of the atoms and ions in
O O lanthanoid series from La3+ to Lu3+ is called lanthanide
Dichromate ion
contraction. The similarity in size of the atoms of Zr
There are six equivalent Cr — O bonds and one and Hf is due to the lanthanide contraction.
Cr — O — Cr bond. 80. (b) In lanthanides, there is poorer shielding of 5d electrons
60. (c) Solid potassium dichromate when heated with by 4 f electrons resulting in greater attraction of the
concentrated sulphuric acid and a soluble chloride nucleus over 5 d electrons and contraction of the atomic
gives orange red vapours of a volatile oily liquid radii.
CrO2Cl2 81. (d) On going from left to right in lanthanoid series ionic,
K2Cr2O7 + 4NaCl + 6H2SO4 size decreases i.e.
¾® 2KHSO4 + 4NaHSO4 + 2CrO2Cl2 Ce3+ > Tb3+ > Er3+ > Lu3+.
chromyl chloride 82. (d)
61. (c) Mn2O7 is acidic, V2O5 is amphoteric acid and CrO is 83. (c) Lanthanide contraction results into decrease in atomic
basic. and ionic radii.
62. (a) CrO2 is amphoteric in nature 84. (a)
63. (b) In neutral or faintly alkaline medium thiosulphate is 85. (a) 4f orbital is nearer to nucleus as compared to 5 f orbital
quantitatively oxidized by KMnO4 to SO42– therefore, shielding of 4 f is more than 5 f.
8KMnO4 + 3Na2S2O3 + H2O ¾® 86. (d)
3K2SO4 + 8MnO2 + 3Na2SO4 + 2KOH 87. (c) In lanthanide series there is a regular decrease in the
64. (b) HCl and SO2 are reducing agents and can reduce atomic as well as ionic radii of trivalent ions (M3+) as
MnO4–. CO2 which is neither oxidising and nor the atomic number increases. Although the atomic radii
reducing will provide only acidic medium. It can shift do show some irregularities but ionic radii decreases
reaction in forward direction and reaction can go to from La(103 pm) to Lu (86pm). Y3+ belong to second
completion. transition series there fore have greater ionic radii then
65. (c) In laboratory, manganese (II) ion salt is oxidised to other ions of third transition series.
permagnate ion in aqueous solution by peroxodisulphate. 88. (c) Sm2+(Z = 62)
2Mn 2+ + S2O82- + 8H 2O ® 2MnO-4 + 10SO42- + 16H + [Xe]4f6 6s2 – 6 unpaired e– Eu2+(Z = 63)
peroxodisulphate ion [Xe]4f7 6s2 – 7 unpaired e– Yb2+(Z = 70)
66. (a) Pyrolusite (It is MnO 2 ) [Xe]4f14 6s2 – 0 unpaired e– Ce2+(Z = 58)
67. (c) In acid medium MnO-4 + 8H + + 5e - ® Mn 2+ + 4H 2O [Xe]4f1 5d1 6s2 – 2 unpaired e–
(O.S. of Mn changes form +7 to +2) Only Yb2+ is diamagnetic.
THE d-AND f–BLOCK ELEMENTS 605

89. (c) Ac (89) = [Rn] [6d1] [7s2]

90. (b) The main reason for exhibiting larger number of Configuration No. of Unpaired e – s
oxidation states by actinoids as compared to 3d 7 3
lanthanoids is lesser energy difference between 5 f and
6d orbitals as compared to that between 4f and 5d 3d5 5
orbitals. 8
3d 2
In case of actinoids we can remove electrons from 5f as 2
3d 2
well as from d and due to this actinoids exhibit larger
number of oxidation state than lanthanoids. 7. (b) Lanthanoids show common oxidation state of +3.
91. (d) 8. (a) The reaction in which oxidation as well as reduction
92. (b) As a result of lanthanide contraction Zr 4+ and Hf4+ of same metal occur is known as disproportionation
possess almost the same ionic radii. Ce4+ is an reaction.
oxidising agent. Ce4+ gains electron to acquire more Oxidation
2+
stable Ce3+state. La(OH)3 is the most basic among Cu
+
Cu + Cu
lanthanide hydroxides. Reduction
93. (d) 94. (c) 95. (a) 96. (d) 9. (d) Mn2+ acts as autocatalyst.
97. (d) Mischmetal is an alloy which contains rare earth
elements (94-95%), iron (5%) and traces of sulphur, 2MnO-4 + 16H+ + 5C2O42- ® 2Mn 2+ + 10CO2 + 8H2O
carbon, silicon, calcium and aluminium. It is used in 10. (c) Tm ; Thulium Z = 69 do not belong to actinoid series.
gas lighters, tracer bullets and shells. 11. (a) Reaction KMnO4 with sulphide ions in acidic medium
98. (c) Gun metal is an alloy of Cu, Zn and Sn. It contains 88% is as follows :
Cu, 10% Sn and 2% Zn. 2KMnO4 + 3H2SO4 ® K2SO4 + 2MnSO4 + 3H2O + 5[O]
99. (b) Brass is an alloy of Cu and Zn H 2 S+ [ O ] ® H 2 O + S] ´ 5
100. (b) Cu, Ag and Au are called coinage metals. 2KMnO 4 + 3H 2 SO 4 + 5H 2S® K 2SO 4 + 2MnSO 4 + 8H 2 O + 5S
101. (b) Bronze is an alloy of Cu and Sn. 5 moles of S2– ions react with 2 moles of KMnO4 thus,
102. (b) Bronze - 10% Sn, 90% Cu
2
(Sn is a non transition element) 1 mole of S2– ion will react with moles of KMnO4.
103. (d) PdCl2 is used as a catalyst in Wacker’s process. 5
104. (a) Steel is an alloy of Fe and C (non-metal). Interstitial 12. (a) Amphoteric oxide react with alkalies as well as acids.
alkali
V2O5 ¾¾¾ 3-
compounds are chemically inert. ® VO4
acid
V2O5 ¾¾¾ +
Exercise - 2 ® VO 4
acid
Cr2O3 ¾¾¾ 3+
1. (b) Electronic configuration of X3+ is [Ar]3d5 ® [Cr(H2O)6]
Atomic number of X = 18 + 5 + 3 = 26 Cr2O3 ¾¾¾ alkali –
® [CrO2]
2. (a) Anion carrying a higher charge and smaller size is
13. (a) The E.C. of gadolinium is :
associated with greater lattice and hydration energy
Gd = [Xe]4f 75d16s2
but it is expected on the basis of electronic.
14. (d) Interstitial compounds are chemicaly inter.
configuration Cu+ should be more stable because it
has completely filled orbitals. But the lattice and 15. (b) Spin only magnetic moment ( m ) = n ( n + 2 ) BM
hydration energy factors dominate and as a result Cu2+
is more stable. = 3 ( 3 + 2 ) = 15
3. (d) Along the period, decrease in metallic radius is coupled
= 3.87 BM
with increase in atomic mass therefore results in
16. (c) When alkaline KMnO4 oxidising agent is treated with
increase in density of metal. Hence, Cu will exhibit
highest density. KI, iodide ion is oxidised to IO3- .
4. (b) CuF2 is coloured in solid state because Cu(II) has d9 2KMnO4 + H2O + KI ® 2MnO2 + 2KOH + KIO3
configuration thus, due to the presence of unpaired 17. (a) Copper lies below hydrogen in the electrochemical
electron, it exists as a coloured salts. series and hence does not liberate H2 from acids.
5. (a) The compound formed can be explained by the 18. (c) As mentioned in the reaction below Sn 2+ changes to
following reaction : Sn4+ :
2KMnO4 + 2H2SO4 (conc.) ® Mn2O7 + 2KHSO4 + H2O Oxidation
Cr2+6 O72 - + 14H + + 3Sn 2+ ® 2Cr3+ + 3Sn 4+ + 7H 2 O
(green oily)
6. (b) Greater the number of unpaired electrons, higher will Reduction
be the value of magnetic moment.
19. (d) In covalent compounds fluorine can form only single
bond while oxygen forms double bond.
 EBD_7374
606 CHEMISTRY

20. (c) Zr and Hf possess almost same atomic and ionic radii
32. (d) Orbital angular momentum = l (l + 1).h
because of lanthanoid contraction. Hence they exhibit
similar properties. For d-orbital l=2
21. (b) HCl is not used in oxidation reactions of KMnO4 in angular momentum = 2(2 + 1)h = 6h
acidic medium because KMnO4 + HCl produce nascent
oxygen which will partly oxidise HCl to Cl2. So the end 33. (d) (n + l) rule can be used. Titanium is a multi electron system
point will not be correct in the titration. (n + l)
22. (a) The shape of f-orbitals is very much diffused and they 3s < 3p < 4s < 3d
have poor shielding effect. The effective nuclear charge ¯ ¯ ¯ ¯
increases which causes the contraction in the size of (3 + 0) (3 + 1) (4 + 0) (3 + 2)
electron charge cloud. This contraction in size is quite || || || ||
regular and known as lanthanoid contraction. 3 4 4 5
23. (c) Both are reducing agents. If (n + l) values are same, than value of "n" has to be
24. (c) The structure of CrO5 is considered.
O 34. (b) Formation of Fe(CO)5 from Fe involves no change in
O
oxidation state of iron.
Cr 35. (a) Considering the same moles of compounds Fe2+ SO2–
4
O O ( +6)
only Fe2+ is oxidised by KMnO4. SO2– 4 in which
O
sulphur is in highest oxidation state cannot be oxidised.
Hence CrO5 has two proxy linkage.
Now suppose the oxi. no. of Cr is x then Fe 2 + SO32– ¾¾
® Fe 2+
x + (– 1 × 4) + (– 2) = 0 (+4) (+6)
2– 2– –
\ x = +6 SO3 —® SO4 + 2e
25. (b) 2 KMnO4 + 3H2SO4 + 5H2O2 ¾®
Sulphur can be oxidised to (+6) i.e to SO 2–
4
K2SO4 + 2MnSO4 + 8H2O + 5O2
i.e. Mn2+ ion and O2. ® Fe 2+
In FeC 2 O 4 ¾¾
26. (d) 3Fe + 2O2 ¾¾
® Fe3O4
D Carbon can be oxidised to (+4) i.e to CO2
(+3)
600°C Nitrogen can be
Fe3O4 + CO ¾¾¾® 3FeO + CO2 Fe(NO 2 ) 2 ¾¾ ® Fe2 + + 2NO2
–
oxidised to (+5)
700°C
FeO + CO ¾¾¾® Fe + CO2 ¯ – – state
2NO3 + 2e
27. (b) The complex [CoCl(NH3 )5 ]+ decomposes under ­
acidic medium, so (+5)
36. (b) Due to lanthanoid contraction atomic radii of Zr and Hf
[CoCl(NH3 )5 ]+ + 5H + ¾¾ ® Co 2 + + 5NH +4 + Cl - is almost similar.
28. (d) Most of the transition metal compounds (ionic as well 37. (c) Gd (64) = [Xe]4f7 5d1 6s2
as covalent) are coloured both in the solid state and in 38. (b) As a result of lanthanoid contraction change in ionic
aqueous solution in contrast to the compounds of s radii on going from elements of 4d to 5d transition
and p-block elements due to the presence of incomplete series is very small. Thus chemical properties of 4d
d-subshell. and 5d series of transition elements are similar.
29. (a) Fe3+ ion can be detected by K4[Fe(CN)6] 39. (b) Due to larger surface area and variable valencies to
form intermediate absorbed complex easily, transition
4Fe 3+
+ 3K 4 éë Fe ( CN )6 ùû ¾¾
®
metals are used as catalysts.
40. (d) (A) - (ii), (B) - (i), (C) - (iv), (D) - (iii)
Fe 4 éë Fe ( CN ) 6 ùû + 12K + 41. (a) L ® M charge transfer spectra. KMnO4 is colored
3
30. (d) Magnetic moment = 2.84 B.M. This indicates that 2 because it absorbs light in the visible range of
unpaired electrons are present. electromagnetic radiation. The permanganate ion is the
source of color, as a ligand to metal, (L ® M) charge
For Ni2+ = 4s0 3d8 transfer takes place between oxygen's p orbitals and
the empty d-orbitals on the metal. This charge transfer
Number of unpaired electrons (n) = 2 takes place when a photon of light is absorbed, which
Hence Ni2+ gives magnetic moment 2.84 B.M. leads to the purple color of the compound.
31. (a) Fe+2 = 3d6 (number of ‘d’ electrons = 6) 42. (a) Am shows maximum number of oxidation states,
In Cl = 1s2 2s2 2p6 3s2 3p5 + 3, + 4, + 5, + 6
total p electrons = 11, which are not equal to number of 43. (a) 40 elements are present in d-block.
‘d’ electrons in Fe+2 44. (d) K2Cr2O7 + SO2 + H2SO4 ¾®
p-electrons in Ne = 1s2 2s2 2p6 = 6 K2SO4 + Cr 2(SO4)3 + H2O
s-electrons in Mg = 1s2 2s2 2p6 3s2 = 6 green colour
THE d-AND f–BLOCK ELEMENTS 607

45. (a) Less active metals like Cu, Ag etc. react with conc. 56. (d) Although ZnO is an amphoteric oxide but in given
acid and form nitrate and nitrogen dioxide. reaction.
46. (d) Eu (63) = [Xe] 4 f 7 6s2 (A) ZnO + Na2O ¾® Na2ZnO2
Gd (64) = [Xe] 4 f 7 5d1 6s2
acid base salt
Tb (65) = [Xe] 4 f 9 6s2
47. (b) As a result of lanthanide contraction Zr 4+ and Hf4+ (B) ZnO + CO2 ¾® ZnCO3
possess almost the same ionic radii. Ce4+ is an base acid salt
oxidising agent. Ce4+ gains electron to acquire more 57. (a) Control rods slowdown the motion of neutrons and
stable Ce3+state. La(OH)3 is the most basic among help in controlling the rate of fission. Cadmium is
lanthanide hydroxides. efficient for this purpose.
48. (b) The magnetic moment values are lesser than the
theoreticaly predicted values due to the fact that 5f 58. (c) CrO2–
4 Cr6+ diamagnetic
electrons of actinides are less effectively shielded
which results in quenching of orbital contribution. Cr2O72– Cr6+ diamagnetic
49. (c) Reaction of Zn with dil. HNO3
4Zn + 10HNO3(dil.) ¾® 4Zn(NO3)2 + 5H2O + N2O MnO4– Mn7+ diamagnetic
(Zn reacts
differently with MnO 2–
4 Mn6+ paramagnetic
very dilute HNO3)
Reaction of Zn with conc. HNO3
Zn + 4HNO3(conc.) ¾® Zn(NO3)2 + 2H2O + 2NO2 Thus unpaired electron is present, so d–d transition is
50. (d) Out of all the four given metallic oxides CrO2 is attracted possible.
by magnetic field very strongly. The effect persists
even when the magnetic field is removed. Thus CrO2 is
metallic and ferromagnetic in nature.
51. (a)
(a) V = 3d 3 4s 2 ; V2+ = 3d 3 = 3 unpaired electrons Before After
Cr = 3d 5 4s 1 ; Cr 2+ = 3d 4 = 4 unpaired electrons transition transition
Mn = 3d 54s2 ; 59. (a) Co3+ = [Ar] 3d 6 , unpaired e–(n) = 4
Mn2+ = 3d 5 = 5 unpaired electrons Spin magnetic moment
Fe = 3d 6 4s 2 ; Fe2+ = 3d 6 = 4 unpaired electrons
Hence the correct order of paramagnetic behaviour = 4(4 + 2) = 24 B.M.
V2+ < Cr 2+ = Fe2+ < Mn2+ Cr3+ = [Ar] 3d 3 , unpaired e–(n) = 3
(b) For the same oxidation state, the ionic radii generally Spin magnetic moment
decreases as the atomic number increases in a
particular transition series. hence the order is = 3(3 + 2) = 15 B.M.
Mn2+ > Fe2+ > Co2+ > Ni2+ Fe3+ = [Ar] 3d 5 , unpaired e–(n) = 5
(c) In solution, the stability of the compound depends
Spin magnetic moment = 5(5 + 2) = 35 B.M.
upon electrode potentials, SEP of the transitions metal
ions are given as Ni2+ = [Ar] 3d 8 , unpaired e–(n) = 2
Co3+ / Co = + 1.97, Fe3+ / Fe = + 0.77 ; Spin magnetic moment = 2(2 + 2) = 8 B.M.
Cr3+ / Cr2+ = – 0.41, Sc 3+ is highly stable as it does not 60. (c) M+2 ® 23e–
show + 2 O. S. M ® 25e– (It should be Mn)
(d) Sc – (+ 2), (+ 3)
Ti – (+ 2), (+ 3), (+ 4) 3d54s2 m= 5(5 + 2) = 35 = 5.9
Cr – (+ 1), (+ 2), (+ 3), (+ 4), (+ 5), (+ 6) 61. (a) MnO4– is stable in acidic medium,
Mn – (+ 2), (+ 3), (+ 4), (+ 5), (+ 6), (+ 7) MnO 42– disproportionates, CrO 42– converts into
i.e. Sc < Ti < Cr < Mn Cr2O72– and FeO42– decomposes.
52. (b) Most of the Ln 3+ compounds except La3+ and Lu3+ are 62. (c) AgNO3 ® Ag is not decomposed by H2O at room tem-
coloured due to the presence of f-electrons. perature but reduces to silver in presence of light and
53. (a) Potassium permanganate has a purple colour. When reducing agent like glucose.
sulphur dioxide reacts with potassium permanganate 63. (b) CuS ® Black
the solution decolourises. SnS ® Brown
SO2 + 2KMnO4 + 2H2O ® 2H2SO4 + 2MnSO4 + K2SO4 CdS ® Yellow
54. (b) Minimum or comparable energy gap between 5f, 6d Sb2S3 ® Orange
and 7s subshell makes electron excitation easier, hence ZnS ® White
there is a greater range of oxidation states in actinoids. NiS ® Black
55. (c) The assertion is correct but the reason is false. Actually 64. (c) Thorium can show normally + 3 oxidation state whereas
transition metal show variable valency due to very small Mn and Cr can show large number of O.S., Np belong
difference between the ns2 and (n – 1)d electrons. to 5f series and shows variable O.S.
 EBD_7374
608 CHEMISTRY

Exercise - 3 11. (b) 2CuSO 4 + K 4 [ Fe (CN ) 6 ] ¾

¾®
Cu 2 [ Fe (CN ) 6 ] + 2 K 2SO 4
1. (b) The colour exhibited by transition metal ions is due to
the presence of unpaired electrons in d-orbitals which Chocolate ppt.
permits the d - d excitation of electrons. 12. (c) The magnetic moment (m) of a species is related to its
number of unpaired electrons (n) in form of following
In TiF62– ,– Ti is in + 4 O.S. ; 3d0 – colourless expressions.
In CoF63– –, Co is in + 3 O.S ; 3d5 – coloured m = n( n + 2) B.M
In Cu2Cl2– Cu is in +1 O.S. ; 3d10 – colourless The number of unpaired electrons in the given pairs
are as follows:
In NiCl2– 8
4 – Ni is in + 2 O.S ; 3d – coloured
Fe2 + = 1s 2 , 2s 2 2 p 6 ,3s 2 3 p6 3d 6
2. (a) The order of basic character of the transition metal
monoxide is TiO > VO > CrO > FeO because basic 3d
character of oxides decreases with increase in atomic or Thus here n = 4.
number.
3. (c) (a), (b) and (d) are correct statements. Fe3+ = 1s 2 ,2 s 2 2 p6 ,3s 2 3 p6 3d 5
(c) There is drop in enthalpy of atomization at
manganese because of half filled stable electronic 3d
configuration leading to less mobilisation of electrons. or Thus here n = 5.
This results in weaker metallic bonds.
4. (a) Due to the formation of Cr 3+ from Cr2O72– and the + +
solution turns green. && :
NO or N = O n =0
xx
dil. HNO NaOH ´ ..
5. (c) Zn ¾¾¾¾¾
3 ® Zn(ZO ) ¾¾¾¾
3 2 ® Zn(OH) 2 NO or ´´ N —
—O: n =1
(M) aq.
Colourless White ppt.
solution The given combinations differ in the number of
unpaired electrons. Hence these can be differentiated
® Na 2 [ Zn ( OH )4 ] ¾¾¾
Excess H S
¾¾¾¾ 2 ® ZnS by the measurement on the solid state magnetic moment
NaOH White ppt.
Soluble of nitroprusside ion.

6.
D
(c) 2MnO2 + 2K 2 CO3 + O2 ¾¾® 2K 2 MnO4 + 2CO2 ­ 13. (c) 2Au 3+ + 6e - ¾¾
® 2Au, DG° = - 6 ´ 1.52F ......(i)
green
(X) (air) (Y) 3Au 3+ + 6e - ¾¾
® 3Au + , DG° = -6 ´ 1.36F ......(ii)
For the reaction
2K 2 MnO4 + Cl2 ¾¾
® 2KMnO 4 + 2KCl 3Au + ¾¾
® 2Au + Au 3+ , ΔG° = (i) – (ii)
(Y) (Z) Pink
= 8.16 F – 9.12 F = – 0.96 F (negative)

7. (a) CuSO 4 (aq.) ¾¾¾

H S
2 ® 2CuS ¾¾¾¾
®
KCN 14. (a) Hg 2 Cl2 + NH 4 OH ¾¾
®
Black ppt. Excess 'X'
(M)
H 2N
[Cu(CN)4 (N)]3+ + (CN) 2 ­ Cl
Hg + Hg + NH4Cl + 2H2O
(O)
Black ppt

8. (b) Ag 2 S + 4 NaCN + 2O 2 ® 2 Na [Ag (CN )2 ]+ Na 2SO 4 H 2N

HgCl 2 + 2NH 4 OH ¾¾
® Hg + NH4Cl + 2H2O
X is S and Y is O2. 'Y' Cl
White ppt
9. (b) E º = 1.33 V; E º = – 0.11 V
Cr2O 72 - /Cr 3+ CrO 2 - / Cr 3+ 15. (c) Smaller is the ionization energy of a metal to give a
4
10. (a) The +4 oxidation state of cerium is also known in particular oxidation state, greater will be thermodyramic
solution. stability of that oxidation state.
 23. COORDINATION COMPOUNDS

23. (b) IUPAC name is Potassium trioxalatoaluminate (III).

Exercise - 1 24. (a) Chlorodiaquatriamminecobalt (III) chloride is
1. (c) [CoCl( NH 3 )3 (H 2O) 2 ]Cl 2 .
2. (d) Co (NH3)5 Cl3 [Co(NH3)5Cl]+2 + 2Cl- 25. (c) K 3[Fe(CN ) 6 ] is Potassium hexacyanoferrate (III).
\ Structure is [Co (NH3)5 Cl] Cl2. 26. (b) [Co(ONO)(NH3)5]Cl2
pentaamminenitrito-N-cobalt (III) chloride
Now [Co(NH3 ) 5 Cl]Cl 2 + 2AgNO3 ¾¾
®
27. (d) [Co(H2O)4(NH3)2]Cl3
[Co(NH3 )5 Cl](NO3 )2 + 2AgCl = Diamminetetraaquacobalt (III) chloride.
3. (b) It is a double salt: 28. (d) Chemical formula of iron (III) hexacynaoferrate (II) is
Fe4[Fe(CN)6]3
FeSO 4 .( NH 4 )2 SO 4 .6H 2 O ¾¾
® 29. (a) Pt(NH3)2Cl2 is a disubstituted complex and shows only
Fe2 + + 2SO24 - + 2NH +4 cis-& trans-isomers
Cl NH3 H3N Cl
4. (c) The coordination number of central metal atom in a
complex is equal to number of monovalent ligands,
Pt Pt
twice the number of bidentate ligands and so on,
around the metal ion bonded by coordinate bonds. NH3 Cl NH3
Cl
Hence coordination number = no. of s bonds formed cis trans
by metals with ligands
30. (c) [Cr(SCN ) 2 ( NH 3 ) 4 ]+ shows linkage, geometrical and
5. +
(d) Oxidation state of Cr in [Cr ( NH 3 ) 4 Cl 2 ] .
optical isomerism. Hence produces maximum no. of
Let it be x, 1 × x + 4 × 0 + 2 × (–1) = 1 Therefore x =3. isomers.
6. (d) [EDTA]4– is a hexadentate ligand, because it has six 31. (a) MA3B3 – 2 geometrical isomers
donor atoms and donate 6 pairs of electrons to central
metal atom in the complex. MA2B4 – 2 geometrical isomers
7. (a) Salt may be complex salt. Metal atom present in the MA4B2 – 2 geometrical isomers
coordination sphere appears in the form of complex The complexes of general formula MA6 and MA5B
ion and not as simple cation having octahedral geometry do not show geometrical
8. (d) 9. (c) 10. (d) isomerism.
11. (c) Ambident ligand has two donor atoms, either of two 32. (b) The chemical formula of Pentaminenitrochromium (III)
can form a coordinate bond.
chloride is
12. (c)
13. (c) Na+ is not a ligand. éCr ( NH3 ) NO2 ù Cl2
14. (b) ë 5 û
15. (b) O2 is a bidentate ligand. It can exist in following two structures
16. (b) 17. (a) 18. (c) é Cr ( NH 3 ) NO 2 ù Cl2 and
19. (c) It is correct statement that NF3 is a weaker ligand than ë 5 û
N(CH3) 3, the reason is that fluorine is highly é Cr ( NH3 ) ONO ù Cl 2
electronegative therefore, it with draw electrons from ë 5 û
nitrogen atom. Hence, the lone pair of nitrogen atom Therefore the type of isomerism found in this
cannot be ligated. While N(CH3)3 is a strong ligand compound is linkage isomerism as nitro group is linked
because CH3 is electron releasing group. through N as –NO2 or through O as – ONO.
20. (c) As it forms two moles of silver chloride thus it has two
33. (b)
moles of ionisable Cl.
34. (c) cis-[Co(en)2Cl2]+: cis-[M(aa)2b2] can show optical
[Co(NH 3 )5 NO 2 ]Cl2 ® [Co(NH 3 ) 5 NO 2 ]2+ + 2Cl - isomerism.
2Cl - + 2AgNO3 ® 2AgCl + 2NO 3- 35. (a)
21. (b) Pt Cl2.2NH3= [Pt(NH3)2Cl2] 36. (a) The octahedral coordination compounds of the type
CoCl3.4NH3= [Co(NH3)4Cl2] Cl MA3B3 exhibit fac-mer isomerism.
NiCl2.6H2O = [Ni(H2O)6]Cl2. 37. (c) Coordination isomerism occurs when cationic and
22. (b) Since complex compound gives 2 moles of AgCl on
anionic complexes of different metal ions are present in
treatment with AgNO3.
\ most probable structure is (b). a salt. The two isomers differ in the distribution of
 EBD_7374
610 CHEMISTRY

ligands in cation and anion e.g., 52. (d) A – (p), B – (r), C – (s), D – (q)
[Co (NH3)6] [Cr (CN)6] is an isomer of [Co (CN)6] 53. (c) [CuCl2{(O = C(NH2)2}2]
[Cr (NH3)6] 54. (b) Non superimposable mirror images are called optical
38. (a) Complexes of the type MABCD may exist in three isomers and may be described as “chiral’. They are
isomeric forms. also called enantiomers and rotate plane polarised light
A B A C A C in opposite directions.

Cl Cl
M M M
Cl Cl

D C D B B D en Co Co en
(I) (II) (III)

Similarly, [Pt (py) (NH3) BrCl] may exist in three isomeric

form in which en en
M = Pt, A = Py, B = NH3, C = Br, D = Cl.
55. (a) The given compound may have linkage isomerism due
39. (a) Complexes with dsp2 hybridisation are square planar.
to presence of NO2 group which may be in the form
So, [PtCl4]2– is square planar in shape.
–NO2 or –ONO.
40. (b) Option (b) shows optical isomerism [Co(en)3]3+
It may have ionisation isomerism due to presence of
3+ 3+
two ionisable group –NO 2 & –Cl. It may have
en en
geometrical isomerism in the form of cis-trans form as
follows :
en Co Co en [Co(NH3)4Cl(NO2)]NO2 & [Co(NH3) (NO2)2]Cl
––– Ionisation isomers.
en
en [Co(NH3)5(NO2)2]Cl & [Co(NH3)5(ONO)2]Cl
d–form Mirror –form ––– Linkage isomers
NO2 NO2
Complexes of Zn++ cannot show optical isomerism as
they are tetrahedral complexes with plane of symmetry. H3N H3N
NH3 NO2
3+
[Co(H2 O)4 (en)] have two planes of symmetry Co Co
hence it is also optically inactive. NH3 NH3 NH3 NH3
[Zn(en)2]2+ cannot show optical isomerism
41. (b) Ionisation isomer of [Cr(H 2 O) 4Cl(NO 2 )]Cl is NO2 NH3
[Cr(H2O)4Cl2]NO2. Trans-form Cis-form
42. (c) Ma 2b2c 2 can show both optical & geometrical Geometrical isomers
isomerism. 56. (a) Geometrical isomerism is possible only in square planar
43. (d) [Pt(en)2Cl2] is a complex of the type M(AA)2 B2 which complexes of the type MA2B2 and MA2BC and for
is octahedral Such compounds exhibit optical and octahedral complexes of the type MA4B2 and MA4BC.
geometrical isomerism both Hence only (ii) will show geometrical isomerism.
44. (a) [Co(NH3)3(NO2)3] is of the type MA3B3. They give 57. (a)
two geometrical Isomers 58. (b) Geometrical isomers of following type of square
45. (c) Square planar complex of the formula Mabcd give three planar complexes is possible. Ma2b2 type, Ma2bc
geometrical isomers type and Mabcd type.
46. (b) 59. (b) Non –superimposable mirror images are optically
47. (d) The complex ion [Cr(SCN)2(NH3)4]2+ can exhibit active, hence rotate plane polarized light.
geometrical and linkage isomerism
48. (c) [PtCl2(NH3)4]Br2 and [PtBr2(NH3)4]Cl2 are ionisation a a
isomers
49. (c) Octahedral complex of the type MA5B do not show M M
geometrical isomerism d
b d b
50. (c) Similarity between optical and geometrical isomerism c c
is that both are included in stereo isomerism
whatever angle of molecule
51. (b) Given compound shows meridional isomerism.
COORDINATION COMPOUNDS 611

60. (c) Complex is not superimposable on its mirror image

67. (a) Co3+ :
hence optically active i.e., rotate plane polarized light.
[Co(CN)6]3– :
180°
CN– is a strong field ligand and it causes pairing of
3+ 3+ electrons as a result number of unpaired electrons in
en en Co3+ becomes zero and hence it has lowest value of
paramagnetic behaviour.
en Co Co en 68. (a) Sc = [Ar] 3d 1, 4s2
Oxidation state of Sc in [Sc(H2O)6]3+ is Sc3+
en en
180° Sc3+ = [Ar] 3d 0, 4s0.
cannot be Q It does not have unpaired electron
superimposed en 3+ \ Sc3+ is diamagnetic and colourless.
non-superimposable 69. (c) In Na2[CdCl4], Cd has oxidation state +2.
en Co
en So, its electronic configuration is 4d105s0
or all the 4d orbitals are fully filled.
Hence, there will be no d-d transition. So, it is
colourless.
61. (c) Ni(CO)4 Ni(PPh3)2Cl2 70. (c)
O.S. Ni0 Ni2+
71. (a) [ Ni(CN)4 ]2- : Number of unpaired electrons = 0
E.C. [Ar]3d 84s2 [Ar]3d 84s0
Pairing of e– No pairing of e– [Cr(NH3 )6 ]3+ : Number of unpaired electrons = 3
Hybridization sp3 (tetrahedral) sp3 (tetrahedral)
[ Fe(H 2 O)6 ]2+ : Number of unpaired electrons = 4
62. (c) [Cr(NH3)6]Cl3 is an inner orbital complex, because in
this complex inner d-orbital is used for hybridisation
(d2sp3)
[ Ni(H 2O)6 ]2+ : Number of unpaired electrons = 2
63. (b) 72. (a) [Ni(NH3)6]2+

No. of Ni 2+ = 3d 8, according to CFT = t 62g eg2 therefore,

Atom/Ion Configuration Magnetic
Complex unpaired
electrons nature hybridisation is sp3d 2 and complex is paramagnetic.
3d 4s 4p 73. (a)
2+ 8
Ni (d )
2–
2 74. (b) [Co(C2O4 )3]3– is dimagnetic as oxalate is a strong ligand
[NiCl4]
2 causing pairing of 3d electrons in Co3+ thereby leading
sp 3 to d2sp3 hybridisation.
2–
[Ni(CN)4] 0
Rearrangement dsp
2 3d 4s 4p
Orbitals of
Ni (d 8s2) 2
[Ni(CO)4] Co3+ ion
0
3d 4s 4p
Rearrangement
sp
3
d 2sp 3 hybridised
oribitals of Co3+
64. (b) As in [NiCl4]–2 chloride ion being a weak ligand is not
able to pair the electrons in d orbital. d 2sp3 hybrid
65. (d) Cr3+ has 4s0 3d 3 electronic configuration with 3 unpaired
electrons, hence paramagnetic. In other cases pairing 75. (d) Nickel in Ni(CO)4 is sp3 hybridised therefore geometry
of d-electrons take place in presence of strong field of Ni(CO)4 is tetrahedral whereas in [Ni(CN)4]2– nickel
ligands such as CO or CN–. is dsp2 hybridised therefore geometry of [Ni(CN)4]2– is
In Cr(CO)6 molecule 12 electrons are contributed by square planar.
CO group and it contain no odd electron 76. (c) [Mn(CN) 6] 3– and [Fe(CN) 6 ] 3– are inner orbital
66. (b) CN– is a strong field ligand as it is a pseudohalide ion. complexes and paramagnetic while [Co(C2O4)3]3– is
These ions are strong coordinating ligands and hence
diamagnetic in nature.
have the tendency to form s-bond (from the pseudo
77. (d)
halide to the metal) and p-bond (from the metal to
pseudo halide) 78. (a) Cl– is a weak field ligand.
 EBD_7374
612 CHEMISTRY

79. (a) In octahedral complex the magnitude of Do will be 91. (d)

highest in a complex having strongest ligand. Out of 92. (d) Crystal field splitting energy increases with increase in
the given ligands CN– is strongest. So, Do will be ligand field strength i.e., with increase in no. of ‘en’
highest for [Co(CN)6]3–. Thus option (a) is correct. groups and wavelength of absorbed light decrease with
80. (a) Ligands can be arranged in a series in the orders of increase in ligand field strength
increasing field strength as given below : \ [Ni(H2O)4(en)]2+(aq) will absorb light of higher
Weak field ligands : wavelength i.e., Red.
[Ni(en)3]2+ will absorb light of lower wavelength i.e.,
I- < Br - < S2 - < SCN < Cl - < N3- , F - blue-green and [Ni(H2O)4(en)2]2+ will absorb yellow
< Urea, OH– < oxalate orange light.
Strong field ligands 93. (a) Both Assertion and Reason are true and Reason is the
-- - correct explanation of statement-1. [Sc(H2O6]3+ has no
O < H 2O < NCS < EDTA < Py, NH3 <
unpaired electron in its d subshell and thus d–d
en = SO3– < bipy, Phen < NO2- < CH3- transition is not possible whereas [Ti(H2O)6]3+ has one
unpaired electron in its d subshell which gives rise to
< C6 H 5- < CN - < CO d–d transition to impart colour.
Such a series is termed as spectrochemical series. It is 94. (d) Hybridisation
an experimentally determined series based on the
absorption of light by complexes with different ligands. [Fe(CN)6 ]4 -,[Mn(CN)6 ]4 - ,
81. (d) CN– is a strong field ligand and form low spin d 2 sp3 d 2 sp3
complexes thus Do > P.
82. (c) CO is a strong field ligand and for strong field ligands [Co(NH 3 ] 3+ ,[Ni(NH 3 ) 6 ] 2+
Do > P. d 2 sp 3 sp 3d 2
83. (a)
Hence [ Ni( NH 3 ) 6 ]2 + is outer orbital complex.
84. (d) Magnetic moment can be calculated by using the
relation n(n + 2)B.M. Where n = number of electrons 95. (c) Cr2+ d4 4
and B.M. is Bohr magneton.
\ 5.9 = n(n + 2) Mn2+ d5 5
\ n=5
85. (a) Triethoxyaluminium has no Al – C linkage Fe2+ d6 4
O - CH 2 CH 3
Al Co2+ d7 3
O - CH 2 CH 3
Minimum paramagnetic behaviour = [Co (H 2O) 6 ] 2+
O - CH 2 CH 3
96. (b) In carbonyls O.S. of metal is zero
86. (d) Due to some backbonding by sidewise overlapping In [Ni(CO)4], the oxidation state of nickel is zero. Its
between d-orbitals of metal and p-orbital of carbon, configuration in Ni(CO)4 is
the Fe–C bond in Fe(CO)5 has both s and p character.
87. (a) Ni(CO)4. The O. S. of Ni is Zero. Electronic configuration 3d 4s 4p
is [Ar] 3d8 4s2 4p0 . In presence of strong ligand CO [Ni(CO)4] ;
the paring of electrons take place and electronic
configuration will be [Ar] 3d10 4s0 4p0. Hence unpaired sp 3 hybridisation
electrons is zero .
88. (d) Fe(CO) 5 (Z=26) O. S. of Fe is zero . Electronic In [Ni(CN)4]2– the oxidation state of Ni is 2+ and its
configuaration is [Ar]] 3d6, 4s24p0. After pairing of configuration is
electrons of d and s orbitals, we have one d atomic 3d 4s 4p
2
orbital empty. C. N. is 5 so hybridisation is dsp3 which [Ni(CN)4]
is trigonal bipyramidal.
89. (b) Complexes of Ma 3B3 type shows fac– meridional
dsp 2 hybridisation
isomerism.
Solvate isomerism is refered to as a hydrate isomerism Thus the hybridisations of nickel in these compounds
when solvent is water. are sp3 and dsp2 respectively.
90. (b) [Ti(H 2O)6 ]3+ gives violet colour if light Hence (b) is the correct answer.
97. (d) d 5 –––– strong ligand field
corresponding to the energy of blue-green region of
wavelength 498 nm is absorbed by it.
Irrespective of prediction of crystal field theory on t2g eg
the basis of experimental observation shows that
anionic ligands are found at the low end of the m = n(n + 2) = 3 = 1.73 B.M.
spectrochemical series. d 3–– in weak as well as in strong field
COORDINATION COMPOUNDS 613

105. (d)
106. (b) b = K1K2K3K4
t2g eg
log b = log (K1 K2 K3 K4)
m = 3(5) = 15 = 3.87 B.M.
log b = logK1 + logK2 + logK3 + logK4
d 4– in weak ligand field
logK3 = 11.9– (3.20 + 2.0 + 4.0)
logK3 = 2.7
t2g eg 107. (a) 108. (a)
109. (b) CN– is coordinated to cobalt as the ligand and
m = 4(4+2) = 24 = 4.89 coordinated compounds have different properties
d 4– in strong ligand field than the individual species.
1 [X][Y]3
110. (a) Overall stability constant = =
t2g eg K1K 2 K 3 [XY3 ]

m = 2(4) = 8 = 2.82. Exercise - 2

98. (d) In case of diamagnetic complexes the electrons are
paired. In case of Ni (CO)4 3d orbital is fully filled give 1. (b) Higher the value of log K, higher will be stability of
rise to sp3 hybridisation while in case of [Ni(CN)4]2– complex compound formed.
nickel is in +2 oxidation state, so one d-orbital is vacant 2. (c) Strength of ligand increases as crystal field splitting
give rise to dsp2 hybridization which is square planar energy increases.
in nature. Ligand strength order : CN– > NH3 > H2O
99. (d) Number of unpaired electrons in [MnCl 6]3– and As energy separation increases, wavelength
[Mn(CN)6]3– respectively are 4 and 2 decreases. Thus, the correct order is :
\ Magnetic moment will respectively be 4.8 and 2.8 [Co(H2O)6]3+ > [Co(NH3)6]3+ > [Co(CN)6]3–
[MnCl6]3– is sp3d2 hybridised and [Mn(CN)6]3– will be 3. (b) In above reaction, when 0.1 mol CoCl3 (NH3)5 is treated
d2sp3 hybridised. with excess of AgNO3, 0.2 mol of AgCl are obtained
100. (b) Since Cr3+ in the complex has unpaired electrons in the thus, there must be two free chloride ions in the
d orbital, hence it will absorb visible light and will be solution of electrolyte as one mole of AgNO 3
coloured precipitates one mole of chloride. So, molecular formula
Ti = [Ar]3d 2 4 s2 ; Ti4 + = 3d 0 of complex will be [Co(NH3)5 Cl] Cl2 and electrolytic
Cr = [Ar] 3d 4s ;5 1 Cr3+ = 3d 3
10 2
solution must contain [Co(NH3)5Cl]2+ and two Cl– as
Zn= [Ar] 3d 4s ; Zn2+= 3d 10 constituent ions. Thus, it is 1 : 2 electrolyte.
Sc = [Ar] 3d 4s ;1 2 Sc3+ = 3d 0
2Å
101. (b) 6
d – t2g 2, 2, 2 0,0 (in low spin) éCo( NH3 )5 Clù Cl2 ® éCo( NH3 )5 Clù (aq) + 2Cl - (aq)
eg ë û ë û
C.F.S.E = – 0.4 × 6D0 + 3P 4. (d) 1 mole of AgNO3 precipitates one free chloride ion
12 (Cl–). Here, 3 moles of AgCl are precipitated by excess
= - D + 3P of AgNO3. Hence, there must be three free Cl– ions.
5 0 So, the formula of the complex can be [Cr(H2O)6]Cl3
102. (a) As positive charge on the central metal atom increases, 5. (a) Ligands present in the compound are
the less readily the metal can donate electron density (i) NH3
into the p* orbitals of CO ligand (donation of electron (ii) Cl (chlorido; di prefixed to represent two ligands.)
density into p* orbitals of CO result in weakening of The oxidation number of platinum in the compound is
C – O bond). Hence, the C – O bond would be strongest
2. Hence, correct IUPAC name is
in [Mn(CO)6]+.
Diamminedichloridoplantinum (II)
103. (a) Structure of [Co2(CO)8] 6. (c) Ligand which chelates the metal ion are known as
O chelating ligand. Here, only oxalate ion is a chelating
ligand. Hence, it stabilises coordination compound by
CO C CO chelating Fe3+ ion.
7. (a) [Cr(H2O)4Cl2]+ shows geometrical isomerism. The
CO Co Co CO possible geometrical isomers are
CO C CO Cl Cl
H2O H2O H2O Cl
O
Cr Cr
Total M – C bonds = 10, Total M – M bonds = 1
H2O H2O H2O H2O
ˆˆ† ML4 , larger
104. (b) For the reaction of the type M + 4L ‡ˆˆ H2O
Cl
the stability constant, the higher the proportion of ML4 trans-isomer cis-isomer
that exists in solution.
 EBD_7374
614 CHEMISTRY

8. (c) Relation between CFSE of octahedral and tetrahedral 15. (b) Due to d 5 configuration CFSE is zero.
4 16. (b)
complexes is D t = Do 17. (d) In the given complex we have two bidentate ligands
9 (i.e en and C2O4), so coordination number of E is 6
(2 × 2 + 1 × 2 = 6)
According to question, D o = 18, 000cm –1
Let the oxidation state of E in complex be x, then
4 4 [x + (–2) = 1] or x – 2 = 1
\ Dt =D o = ´ 18, 000cm –1 or x = + 3, so its oxidation state is + 3
9 9
Thus option (d) is correct.
= 4 × 2,000 cm–1 = 8,000 cm–1 18. (b) CO bond strength is reciprocal to the extent of back
9. (a) NCS (thiocyanate) can bind to the metal ion in two donation involved in synergic bonding.
ways : 19. (d) Fe2+ has electronic configuration
M ¬ NCS or M ® SNC 3d 4s
Thus, coordination compounds [Pd(C6H5)2 (SCN)2] due to strong
and [Pd(C6H5)2 (NSC)2] are linkage isomers.
10. (d) Isomers are the compounds having same molecular ligand
formula but different structural formula. [Co(SO4)2 Ni has electronic configuration
(NH3)5] Br and [Co(SO4)(NH3)5]Cl do not have same 3d 4s
molecular formula. Hence, they are not isomers. due to strong
11. (a) Chelating ligand has two or more donor atoms to a
single metal ion e.g., ligand
Ni2+ has electronic configuration
NH2 3d 4s
O NH2 CH2 due to strong

C O CH2 ligand
CH2 3+
Co has electronic configuration
C O C O NH2 3d 4s
O
O No pairing of electrons
Oxalato Glycinato Ethane-1, 2 diamine 3-
due to weak ligand hence éëCoF6 ùû is paramagnetic.
Here (¬) denotes binding site.
S 20. (a) Reason is the correct explanation of Assertion.
|| .. – 21. (b) B
|| |....–
S O
.. ..|

O .. O V G
Thiosulphato ( S2O32- ) is not a chelating ligand
because geometrically it is not favourable for S2 O32- R Y
to chelate a metal ion.
12. (b) Ligand should have a pair of electron which is loosely O
held and form a M – L bond. For a given metal ion, weak field ligands create a complex
e.g., :N O, NH2CH2CH2NH2, :CO, with smaller D, which will absorbs light of longer l and
:

:
:
||

+ thus lower frequency. Conversely, stronger field ligands

Amongst the species given NH 4 does not have any create a larger D, absorb light of shorter l and thus
pair of electron. higher v i.e. higher energy.
So, it is not expected to be a ligand. Red < Yellow < Green < Blue
13. (b) The compounds having same molecular formula but l = 650 nm 570 nm 490 nm 450 nm
differ in ligands inside & outside the coordination So order of ligand strength is
sphere are solvate (hydration) isomers. L1 < L3 < L2 < L4
Coordin ation compound [Cr (H 2 O) 6 ]Cl 3 and 22. (b) The complex [CoCl(NH3 )5 ]+ decomposes under
[Cr(H2O)5Cl] H2O × Cl2 are solvate isomers, because
water is exchanged by chloride ion. This is why both acidic medium, so
of them show different colour on exposure to sunlight. ® Co 2+ + 5NH 4 + + Cl -
[CoCl(NH3 )5 ]+ + 5H + ¾¾
14. (c) Ligands (based on priority) present are :
(i) NH3 23. (c) Number of unpaired electrons in central atom
(ii) Cl s [Fe(CN)6 ]4- ,[CoCl4 ]2- ,[MnCl 4 ]2 -
(iii) NO s 2 zero three five
So, IUPAC name will be Diamminechloridonitrito-N- The greater the number of unpaired electrons, the
platinum (II). higher the value of magnetic moment
COORDINATION COMPOUNDS 615

24. (d) CoCl3 . 3NH3 will not give test for chloride ions with source of color, as a ligand to metal, (L ® M) charge
silver nitrate due to absence of ionisable chloride atoms. transfer takes place between oxygen's p orbitals and
CoCl3 . 3NH3 Þ [Co(NH3)3 Cl3] the empty d-orbitals on the metal. This charge transfer
AgNO 3 takes place when a photon of light is absorbed, which
[Co(NH3)3 Cl3] ¾¾¾¾ ® no ppt leads to the purple color of the compound.
25. (a) [M (en)2 (C2O4)] Cl 34. (d) CoCl3.5NH3.H2O is pink in colour
C2 O24 - = bidentate ligand, carry – 2 charge 35. (c) Complex compounds contains two different metallic
en = bidentate ligand, carry 0 charge elements but give test only for one of them. Because
\ M carry+ 3 charge; coordination number = 6 complex ions such as [Fe (CN)6]4– of K4 [Fe (CN)6], do
\ Sum = + 3 + 6 = 9 not dissociate into Fe2+ and CN– ions.
26. (d) Hexacyanidoferrate (III) ion.
36. (a) EDTA is hexadentate ligand
27. (c) [Co (en)2 Cl2] Cl – –
OOCH2C •• •• CH2 – COO
Cl N N – CH2 – CH2– N
–
N N OOCH2C CH2 – COO–
N N
Co and Co 37. (b) Zeise’s salt is common name of
N N N Cl K[Pt Cl3(h2 = C2H4)]
Cl Cl 38. (c) [Fe(CO)4]2–
trans cis Since metal atom is carrying maximum –ve charge
(I) (II) therefore it would show maximum synergic bonding as
Mirror image of (II) a resultant C—O bond length would be maximum.
N 39. (b) CuSO 4 + 4NH 3 ® [Cu(NH3 ) 4 ]SO 4
N 2+
N Blue complex due to [Cu(NH 3 ) 4 ]
Co
Cl N 40. (d) When excess of AgNO3 and BaCl2 are added to solution
X.
Cl
28. (d) In [Co(CN)6]–3, O.N. of Co is +3 [Co(NH3 )5 Br]Cl2 + 2AgNO3 ®
\ Co+3 = 3d 6 4s0 1mole 2 moles
CN– is a strong field ligand 0.02 mole
\ Pairing of electrons occurs so in this complex [Co(NH3 ) 5 Br](NO3 ) 2 + 2AgCl(ppt.)(Y)
no unpaired electron is present and it is low spin 1mole 2moles
complex. 0.02 ´ 2 = 0.04 mole
\ Sum = 3 + 6 = 9
29. (c) The chlorophyll molecule plays an important role in [Co(NH3 )5 Cl]SO 4 + BaCl2 ®
photosynthesis, contain porphyrin ring and the metal 1mole
0.02mole
Mg not Ca.
[Co(NH3 )5 Cl]Cl 2 + BaSO 4 (ppt.) (Z)
30. (a) [Co(NH3)5CO3]ClO4. Six monodentate ligands are 1mole
attached to Co hence C. N. of Co = 6; 0.02mole
O. N. = x + 5 × (0) + 1 × (–2) + 1× (–1) = 0 41. (d) Optical isomerism occurs when a molecule is non-
\ x = + 3 ; electronic configuration of Co3+[Ar] 3d64s0 super imposable with its mirror image hence the complex
hence number of d electrons is 6. All d-electrons are cis-[Co(en)2Cl2]Cl is optically active.
paired due to strong ligand hence unpaired electron is + +
zero. en en
31. (c) Cl Cl
32. (d) Square planar complexes of type M[ABCD] form three
Co Co
isomers. Their position may be obtained by fixing the
position of one ligand and placing at the trans position Cl Cl
any one of the remaining three ligands one by one. en en
HOH 2N Cl HOH 2N Cis-d-isomer Mirror Cis-l-isomer
NH3
42. (d) Complex
Pt Pt
Configuration Metal ion Magnetic
py NH3 py Cl moment
trans cis
m= n(n + 2)
HOH 2N
NH3
(a) [Cr(H2O)6]2+ Cr2+ d4 24
Pt
(b) [Fe(H2O)6]2+ Fe2+ d6 24
Cl
cis
py (c) [CoCl4]2– Co2+ 15 d7
33. (a) L ® M charge transfer spectra. KMnO4 is colored (d) [Mn(H2O)6]2+ Mn 2+ d 5 35
because it absorbs light in the visible range of Since (a) and (b), each has 4 unpaired electron they will
electromagnetic radiation. The permanganate ion is the have same magnetic moment.
 EBD_7374
616 CHEMISTRY

43. (a) The complex chlorodiaquatriammine cobalt (III) chloride

can have the structure [CoCl(NH3)3(H2O)2]Cl2 en en
44. (d) The electronic configuration of Fe2+ is [Ar] 3d6. Since
CN is strong field ligand d electrons are paired. In
Ni(CO)4 O. S. of Ni is zero, electronic configuration is en Co Co en
[Ar]3d8 4s2. In presence of CO it is [Ar] 3d10 4s0,
electrons are paired. Electronic configuration of Ni2+
[Ar]3d8 4s0, due to CN– ligand all electrons are paired. en en
Co3+ is [Ar] 3d 6 since F is weak ligand hence 3+ 3+
[Co(en)3] [Co(en)3]
paramagnetic. (dextro) Mirror
(laevo)
45. (b) In a solution containing HgCl2, I2 and I–, both HgCl2
and I2 compete for I–. The two optically active isomers are collectivity called
Since formation constant of [HgI4]2– is very large enantiomers.
(1.9 × 1030) as compared with I3 (Kf = 700) 51. (b) Both Assertion and Reason are true but Reason is not
\ I– will preferentially combine with HgCl2. the correct explanation of statement-1. [Fe(CN)6]3– is
HgCl2 + 2I– ® HgI2 ¯ + 2Cl– weakly paramagnetic as it has unpaired electrons while
Red ppt [Fe(CN)6]2– has no unpaired electron.
HgI2 + 2I- ® [ HgI 4 ]
2- \ It is diamagnetic.
soluble Molarity ´ Volume(mL)
52. (d) Moles of complex =
1000
46. (b) [ ] AgNO3
Co(NH3 )6 Cl3 ¾¾¾¾ ® 3 mole of AgCl
100 ´ 0.1
= = 0.01 mole
[Co(NH3 )5 Cl] Cl2 ¾¾¾¾
AgNO3
® 2 mole of AgCl 1000
Moles of ions precipitated with excess of
[Co(NH3 )4 Cl2 ]Cl ¾¾¾¾
AgNO3
®1 mole of AgCl 1.2 ´ 1022
Complexes are respectively [Co(NH 3 ) 6 Cl 3 , AgNO3 = = 0.02 moles
6.02 ´ 1023
[Co(NH3)5Cl]Cl2 and [Co(NH3)4Cl2]Cl
0.01 × n = 0.02
47. (d) The order of the ligand in the spectrochemical series is:
\ n =2
H2O < NH3 < en It means 2Cl– ions present in ionization sphere
Hence, the wavelength of the light observed will be in \ complex is [Co(H2O)5Cl]Cl2.H2O
the order 53. (c) Among these ligands, ‘F’ is a weak field ligand, makes
[Co(H2O)6]3+ < [Co(NH3)6]3+ < [Co(en)3]3+ only high spin complexes which has sp 3 d 2
Thus, wavelength absorbed will be in the opposite hybridization.
order
i.e., [Co(en)3]3+, [Co(NH3)6]3+, [Co(H2O)6]3+ 54. (b) In Ni(CO) 4 ; [ Ni ( Cl ) 4 ] - 2 ; [ Zn ( NH 3 ) 4 ] + 2 , all the
48. (b) In the complex [Mn(CN)6]3–, O.S. of Mn is + 3 central atoms have sp 3 hybridisation, while in
E.C. of Mn3+ ® 3d4 [ Ni(CN) 4 ]- 2 , its central atom has dsp2 hybridisation
3d 4s 4p
due to strong field ligand (CN - ) . Hence [ Ni(CN ) 4 ] - 2
has square planar structure.
The presence of a strong field ligand CN– causes pairing 55. (b) Fe(CO)5
of electrons. EAN = Z – O.N. + 2(C.N.) = 26 – 0 + 2(5)
= 26 + 10 = 36
Only one central metal atom/ion is present and it
follows EAN rule, so it is mononuclear.
d 2sp 3 56. (a) In the given complex, the CN of Co is 6, and the complex
As, coordination number of Mn = 6, so it will form an has octahedral geometry.
octahedral complex.
\ [Mn(CN)6]3– = Cl en

´´ ´´ ´´ ´´ ´´ ´´ en Co en Co en
Cl
d 2sp 3 Cl Cl
49. (a) Grignard's reagent (RMgX) is a s-bonded trans (optically inactive) cis (optically active)
organometallic compound.
50. (d) The optical isomers are pair of molecules which are 57. (b) Ni(28) : [Ar]3d8 4s2
non superimposable mirror images of each other. Q CO is a strong field ligand, so unpaired electrons get
paired. Hence, configuration would be:
COORDINATION COMPOUNDS 617

63. (a)

Exercise - 3
sp3–hybridisation
1. (b) [CoBr3(H2O)3] It does not exhibit hydrate isomerism.
2. (b) Ni2+ (aq) with DMG (dimethylglyoxime) form square
planar complex which is optically inactive. While
[Co(EDTA)]–, [Zn(gly)2]2+ and [Pt(en)3]4+ are optically
CO CO CO CO
active as they do not have P.O.S.
For, four ‘CO’ligands hybridisation would be sp3 and
2+
thus the complex would be diamagnetic and of 3. (b) X = éë Ni ( en ) ( NH3 )4 ùû neither G.I. nor OI
tetrahedral geometry. 2+
Y = éë Ni ( en )2 ( NH3 )2 ùû G. I as well as OI
58. (d) [Cr(H2O)6]+3 + 6NH3 ® [Cr(NH3)6]+3 + 6H2O
Cr+3 show six C.N. with NH3 Z = [ Ni ( en )3 ]2 + does not show G.I. while show OI
2+
59. (a) Oxidation state of Cr in éë Cr ( H 2 O )6 ùû is + 2. 4. (a) Magnetic moment indicates that there are three
Electronic configuration of Cr unpaired electrons present in chromium. These must
= (Ar)18 4s1 3d 5 be present in lower energy orbitals which are 3dxy,
3dyz and 3dxz.
Electonic configuration of Cr 2+ = (Ar)16 3d 4
5. (b) The two possible isomers for the given octahedral
H2O is a weak field ligand. complex are [M(NH3)5 SO4] Cl and [M(NH3)5 Cl] SO4.
CFSE value [- 0.4n t 2g + 0.6n eg ]D0 + nP They respectively give chloride ion (indicated by
= [ -0.4 ´ 3 + 0.6 ´1] D 0 + 0 = – 0.6 D0 precipitation with BaCl2) and SO4 ion (indicated by
3+ precipitation with AgNO3). Hence the type of isomerism
Oxidation state of Cr in éë Cr ( H 2 O )6 ùû is + 3 exhibited by the complex is ionization isomerism.
Electronic configuration of Cr3+ = (Ar)16 3d 3
3+ 6. (c) [Co ( CO )4 ] ® Paramagnetic, dsp2 (square planer)
CFSE value of éë Cr ( H 2 O )6 ùû
7. (c) As number of stable rings increases stability of
= éëê -0.4n t 2g + 0.6n e g ùûú D 0 + nP complex compound also increases due to chelation
effect.
= [ -0.4 ´ 3 + 0] D0 + 0
Number of rings in [ Ni ( en )2 ] + = 2
2
= – 1.2 D0
Number of rings in éë Ni ( dmg )2 ùû = 4
60. (b) NH3
Br– Br
– 8. (a) Symmetrically filled t2g and eg are those, which contain
NH3 H3N NH3 equal distribution of electrons.
Co3+ 3+
Br
–
NH3 Co
H3N NH3 [FeF3]3– º º eg ìïequal distribution of ü
ï
NH3
íelectrons in orbitals
–
Br ý
Cis º º º t 2g ïî t 2g and eg ïþ
–
–NH3 +Br Trans
–
–NH3 +Br [Mn(CN)6]4– eg unequal
Br
–
NH3 distribution
– – NH3 t 2g of electrons
Br NH3 Br– NH3 Br NH3
– Co 3+
Co3+ Co
3+ in orbitals
– –
Br NH3 Br Br– Br Br
–

[CoF6]3– eg
NH3 NH3 NH3
unequal
facial meridionial Only meridionial t 2g distribution
61. (c) Be is the only group 2 element that does not form a of electrons
stable complex with [EDTA]4–. Mg2+ and Ca2+ have the
[Co(NH3)6]2+ eg unequal
greatest tendency to form complexes with [EDTA]4–. distribution
: t 2g of electrons
62. (a) Co3+ in orbitals
9. (c)
[Co(CN)6]3– : (a) Geometry of complexes ® Both square planer
CN– is a strong field ligand and it causes pairing of (b) Hybridisation of central metal cation ® dsp2
electrons; as a result number of unpaired electrons in (c) Magnetic behaviour [Cu(en) 2)]2 ® Paramagnetic;
Co3+ becomes zero and hence it has lowest value of [Ni(dmg)2] ® Diamagnetic
paramagnetic behaviour. (d) Number of stereoisomers = 0
 EBD_7374
618 CHEMISTRY

11. (c) In both states (paramagnetic and diamagnetic) of the

10. (c) Complex No. of electrons No. of unpaired given complex, Ni exists as Ni2+ whose electronic
in outer d electron (s) configuration is [Ar] 3d 84s0.
3d 4s 4p
orbital
3– 5 – Ni2+ :
[Fe(CN)6] 3d 1 (CN causes
pairing of electrons) sp3
In the above paramagnetic state, geometry of the
[Co(NH3)6]
3+
3d
6 0 complex is sp3 giving tetrahedral geometry.
The diamagnetic state is achieved by pairing of
[Co(oxal.)3]
3–
3d
6 0 electrons in 3d orbital.
[Ni(H2 O)6 ]
2+
3d
8 2 3d 4s 4p
2– 8 –
[Pt(CN)4 ] 5d 0 (CN causes
pairing of electrons)
2+ 10 0 dsp2
[Zn(H2 O)6] 3d
Thus the geometry of the complex will be dsp2 giving
Thus L, M, O and P are diamagnetic. square planar geometry.

12. (a)

M.M. No. of unpaired electron Oxidation state

3d
Complex (A) 4.89 BM 4 Co ® 3d 6 +3

3d
Complex (B) 7.89 BM 3 Co ® 3d 7 +2

3d
Complex (C) 0.0 BM 0 Co ® 3d 6 +3

3-
13. (c) Fe3+ in éë Fe ( CN 6 )ùû Þ low and high spin complex is applicable for d4 to d7
configuration
3d 4s 4p
Mn2+ in [ Mn ( CN )6 ]4 -

3d 4s 4p
d 2 sp3

Þ low spin complex µ = 1.732 BM

Ni in [Ni(CO)4] d2 sp3

3d 4s 4p Þ low spin complex µ = 1.732 BM

µ=0 14. (d) In complexes [Rh(H2O6)]3+ and [Co(H2O)6]3+, central
metal cations have same oxidation state as well as same
sp3 ligands and they fall in same group, but D 0 of

3+
[Rh(H2O)]63+ > D0 of [Co(H2O)]63+ because Rh3+ has
Cr3+ in éë Cr ( NH3 )6 ùû high Zeff value than CO3+.
3d 4s 4p 15. (b) éë Ti ( H 2O )6 ùû Cl 4
Coordination number 6 Þ octahedral complex
Ti is in +4 oxidations state Þ no unpaired electrons
d 2 sp3
Þ magnetic moment = 0 B.M.
 24. HALOALKANES AND HALOARENES
Exercise - 1 2°
9. (a) In isopropyl chloride CH3 - CH - CH3 , chlorine atom
|
1. (b) CH 2 Cl CHCl 2 Cl
| | is attached to 2° carbon atom.
CH 2 Cl CH3
10. (d)
(vic-dihalide) (gem-dihalide)
UV light
2. (b) In alkyl halides halogen atom(s) is attached to sp3 11. (b) RH + Cl 2 ¾¾¾¾® RCl + HCl
hybridised carbon atom. Oxidation No. of Cl is decreasing from 0 (in Cl2) to –1
3. (c) In allylic halides hydrogen atom is bonded to sp3 (in RCl)
hybridized carbon atom. Whereas in vinylic halide,
12. (d) Ethylene dichloride can be prepared by adding HCl to
hydrogen atom is bonded to sp2 hybridized carbon
ethylene glycol (CH2OH. CH2OH).
atom.
CH3CHCl2 CH 2 - CH 2
| | 13. Pyridine RCl + SO ­ + HCl­
(c) R – OH + SOCl2 ¾¾¾¾¾ ® 2
Ethylidene chloride Cl Cl SO2 and HCl being gases escape leaving behind pure
(gem-dihalide) Ethylene dichloride (vic-dihalide)
alkyl halide.
Cl 14. (c)
1 +
NH2 N º NCl– Cl
2
4. (c)
HNO /HCl Cu Cl
3 Br ¾¾¾¾®
2
¾¾¾¾¾¾¾®
2 2
(Diazotization) Sandmeyer’s reaction
5. (c) The compound is C3H 6Cl 2 and the number of possible
acetone
isomeric compunds is 5 15. (b) R-X + NaI ¾¾¾¾
® R -I + NaX ¯
asymmetric carbon atom Soluble in

H H H R-X + NaI (CH3OH,¾¾¾¾

Me 2CO) ® R -I + NaX ¯
H H H
| | | | | | Insoluble in
(CH 3OH, Me 2CO)
H-C-C-C-H H - C - C*- C - H
| | | | | | (where X = Cl or Br)
Cl H Cl Cl Cl H CS
16. (a) CH3COOAg + Br2 ¾¾¾
2 ® CH Br + AgBr + CO
3 2
(d-l-pair)
17. (b) This method is not applicable for the preparation of
H H H H Cl H
| | | | | | aryl halides because the C–O bond in phenol has a
Cl - C - C - C - H H - C-C-C -H partial double bond character and is difficult to break
| | | | | | being stronger than a single bond.
Cl H H H Cl H 18. (a) Aryl chlorides and bromides can be easily prepared
6. (d) 4-Bromobut-l-ene is not an allylic halide by electrophilic substitution of arenes with chlorine
and bromine respectively in the presence of Lewis acid
BrH 2 C —CH 2 —CH==CH 2
catalysis like iron or iron (III) chloride.
4 -Bromobut -1-ene
The ortho and para isomers can be easily separated
1 due to large difference in their melting points.
CH 3
| Reactions with iodine are reversible in nature and
7. (b) H 3C - 2C - Cl require the presence of an oxidising agent (HNO3,
| HIO4) to oxidise the HI formed during iodination.
3 CH
3 Fluoro compounds are not prepared by this method
IUPAC name : 2-Chloro-2-methylpropane. due to high reactivity of fluorine.
Br 19. (a) Alkyl iodides are often prepared by the reaction of
| alkyl chlorides/bromides with NaI in dry acetone. This
8. (a) CH3CH2C = CH – Cl reaction is known as Finkelstein reaction.
4 3 2
2-Bromo-1-chloro but-1-ene R - X + NaI ¾¾ ® R - I + NaX
X = Cl, Br
 EBD_7374
620 CHEMISTRY

NaCl or NaBr thus formed is precipitated in dry acetone. Boiling points of isomeric dihalobenzenes are very
It facilitates the forword reaction according to Le nearly the same. However, the para-isomers are high
Chatelier’s principle. The synthesis of alkyl fluorides melting as compared to their ortho and meta-isomers.
is best accomplished by heating an alkyl chloride/ It is due to symmetry of para-isomers that fits in crystal
bromide in the presence of a metallic fluoride such as lattice better as compared to ortho- and meta-isomers.
AgF, Hg2F2, CoF2 or SbF3. The reaction is termed as Cl Cl Cl
Swarts reaction. Cl
H 3C - Br + AgF ¾¾ ® H 3C - F + AgBr
20. (b) Chlorine atom is highly reactive so it will react with Cl
all types of hydrogen available while the Br atom is
Cl
highly selective so it will react with that hydrogen
which gives the highly stabilized tertiary alkyl radical b.p/K 453 446 448
so only one product is formed. m.p.K 256 249 323
+ 26. (b) CH3Cl has higher dipole moment than CH3F due to
NH2 N2 Cl– much longer C–Cl bond length than the C–F bond.
• The much longer bond length of the C–Cl bond
Na NO + HCl HBF
21. (d) ¾¾¾¾2¾¾¾® ¾¾¾
4®
outweighs th e effect produced by lower
0 -5º diazotisation
electronegativity of Cl than that of F.
N2+BF4– F 27. (c) SN1 reactions involve the formation of carbocations,
hence higher the stability of carbocation, more will be
D reactivity of the parent alkyl halide. Thus tertiary
¾¾¾¾¾¾¾® + BF3+ N2
(Balz-Schiemann
reaction)
carbocation formed from (c) is stabilized by two phenyl
Benzene diazonium groups and one methyl group, hence most stable.
tetrafluoroborate
22. (c) For the same alkyl group, the boiling points of alkyl Dry
28. (c) CH3 CH 2 I + Mg ¾¾¾® CH3CH 2 MgI
halides decrease in the order : ether
Ethyl magnesium iodide
RI > RBr > RCl > RF 29. (c) More stable the carbocation, more reactive will be the
This is because with the increase in size and mass of
parent alkyl halide towards SN1 reaction.
halogen atom, the magnitude of van der Waal's forces
3° > Benzyl > Allyl > 2° > 1° > methyl
increases.
30. (d) SN1 reaction involves carbocation which are planar (sp2
23. (a) Boiling point of CH3I is 42°C which indicates that it is hybridised) and thus can be attacked on either face of
liquid at room temperature. CH3 I is larger molecule so the carbon.
it has stronger vander Waal’s force of attraction than 31. (d) Weaker the C–X bond, greater is the reactivity.
others. 32. (a) 1° Alkyl halides (having least steric hindrance at
24. (d) Para-dichlorobenzene has most symmetrical structure a-carbon atom) are most reactive towards SN2 reaction.
than others. It is found as crystalline lattice form, 33. (c) Isopropyl chloride, being 2° alkyl halides, can undergo
therefore, it has highest melting point (52°C) due to SN1 as well as SN2 mechanism.
symmetrical structure. 34. (a) Due to steric hindrance tertiary alkyl halide do not react
Cl by SN2 mechanism they react by SN1 mechanism. SN2
mechanisam is followed in case of primary and
secondary alkyl halides of
CH3 – X > CH3 – CH2X > (CH3)2 – CH.X > (CH3)3– C–X
H
Cl |
35. (c) H3C - CH 2 - C*- CH3
25. (d) The boiling points of isomeric haloalkanes decrease |
with increase in branching. For example, 2-bromo-2- Cl
methylpropane has the lowest boiling point among
the three isomers. The compound containing a chiral carbon atom (a
carbon atom attached to four different atoms is optically
CH3
| active.
CH3 CH 2CH 2 CH 2 Br CH3CH 2CH CH3 H3C - C - CH3 36. (c) Diastereomers since they have different melting points,
| |
Br Br boiling points, solubilities etc.
b . p . / K 375 364 346 37. (a)
HALOALKANES AND HALOARENES 621

38. (b) The compound has two similar asymmetric 46. (d) CH 3 CH 2 CH 2 Br + Mg ¾¾
® CH3CH2CH2MgBr
C-atoms. It has plane of symmetry and exist in meso (Propyl bromide)
form. CH3CH 2CH 2 MgBr + H2O ¾¾
® CH3CH2CH3 +
OH

Plane of symmetry Mg
Br
CH3 CH3
meso - 2, 3 - Dichlorobutane
47. (a) CH3 – C – Cl + 2Na + Cl – C – CH3
39. (a) Compounds having chiral carbon atom are optically
active. CH3 CH3
t-Butyl chloride

Wurtz
H

Rxn
|
CH3 - C* - COOH (* is chiral carbon atom) CH3 CH3 CH3 CH3
|
Cl CH3 – C – C –CH2Cl Mono
CH3– C – C – CH3
CH3CH3 clorination
CH3 CH
40. (a) A mixture of equal amounts of the two enantiomers is 3
48. (b) The order of atomic size of halogens decreases in the
called a racemic mixture.
order I > Br > Cl > F. On moving down a group, atomic
41. (c)
size increases. Further the bond length of C-X bond
42. (a) Although all the three compounds can be used for decreases in the order
preparing Grignard reagents, diethyl ether is C – I > C – Br > C – Cl > C – F
considered as the best because it provides electron and hence the bond dissociation energy decreases in
pairs to Mg of the reagent fully for coordination, in the order
case of C6H5OCH3 and C6H5N(CH3)2 electron pair on R – F > R – Cl > R – Br > R – I
O and N are partialy delocalised over the benzene and hence R – I, being a weakest bond, breaks most easily.
hence are less available for coordination with Mg. hence R – I is most reactive.
R O(C2H5)2 49. (d) Except (d) all contain abstractable proton
Mg 50. (b) C6 H 5 Cl ¾¾¾
Mg
® C6 H 5 MgCl
X O(C2H5)2 CH 3CH 2OH
¾¾¾¾¾¾ ® C6 H6 + CH3CH 2 OMgCl
43. (c) Potassium ethoxide is a strong base, and 2- bromo- CH 3
pentane is a 2º bromide, so elimination raction predomi- |
Anhyd.
nates 51. (d) C6 H 6 + CH3CH 2 CH 2Cl ¾¾¾¾ ® C6 H 5 - CH - CH 3
AlCl3 Isopropyl benzene
OC2 H 5-
CH 3 CH (Br )CH 2 CH 2 CH 3 ¾¾ ¾¾® 52. (c) Due to resonance in chlorobenzene.
53. (a) N-Phenylacetanilide, C6H5N(C6H5)COCH3,
CH 3CH = CHCH 2 CH 3 + CH 2 = CHCH 2 CH 2 CH 3 precipitates out to a complex with anhydrous AlCl3.
Pentene - 2(major) trans Pentene -1(minor) 54. (d) More the stability of the carbocation, higher will be the
Since trans- alkene is more stable than cis. Thus reactivity of the parent chloride. Allyl chloride > Vinyl
trans-pentene -2 is the main product. chloride > Chlorobenzene
44. (c) Wurtz reaction : It involves the interaction of two 55. (d) Due to resonance, the electron density increases more
molecules of an alkyl halide (preferably bromide or at ortho- and para-positions than at meta-positions.
iodide) with metallic sodium in presence of dry ether to Further, the halogen atom because of its – I effect has
form symmetrical alkanes containing double the number some tendency to withdraw electrons from the benzene
of carbon atoms present in the alkyl halide. For example, ring. As a result, the ring gets somewhat deactivated
Dry ether as compared to benzene and hence the electrophilic
R - X + 2Na + X - R ¾¾¾¾® R - R + 2NaX
Alkyl halide Alkane substitution reactions in haloarenes occur slowly and
require more drastic conditions as compared to those
Br in benzene.
|
45. (d) alc KOH
CH 3 - CH - CH 2 - CH 3 ¾¾¾¾® 56. (d) Chloropicrin is nitrochloroform. It is obtained by the
nitration of chloroform with HNO3.
CH 2 = CH - CH 2 - CH 3 HCCl 3 ¾¾ ¾
¾
HNO
3 ® O NCCl
2 3
In this reaction both hydrogen and halogen atom has Chloroform Chloropicr in
been removed so it is known as dehydro halogenation Chloropicrin is a liquid, poisonous and used as an
reaction. insecticide and a war gas.
 EBD_7374
622 CHEMISTRY

57. (c) CH 3C(Br) = CHCH 2 CH 3 + CH 3CH = C(Br)CH 2 CH 3

58. (b) SN2 reaction follow a 2nd order kinetic ie the rate (I) (II)
depends upon the concentration of both the reactants,
Each one of these will exist as a pair of geometrical
where in SN1 reactions rate depends only upon the
isomers. Thus, there are two structural and four
concentration of only one reactant.
configurational isomers.
The order of reactivity order of alkyl halides for SN1
64. (a)
reaction 3° > 2° > 1° and for SN2 reactions 3° < 2° < 1°
+ –
59. (a) In SN1 reactions step 1 is slow and reversible and the Me Br ionisation +Br
Me
slowest step is the rate determining step
(A)
60. (d) tert-Alkyl halides undergo SN1 reactions, hence they
involve the formation of quite stable carbocations, and Me Me
ionisation Me
not the transition state. In S N 1 reactions, the + + Br –
Br
nucleophile is not involved in rate determining (first)
(B)
step, hence its stronger or weaker nature does not
influence the reaction rate. In SN1, the product has Me
more percentage of the inverted configuration than the ionisation Me –
Me + Br
Me +
retained configuration, i.e. only partial racemization Br
takes place, hence the product will be having some (C)
optical activity. Since SN1 reactions involve the formation of carbo-
61. (d) Chlorination of n-butane takes place via free radical cation as intermediate in the rate determining step,
more is the stability of carbocation higher will be the
hn • •
formation i.e., Cl2 ¾¾® Cl + Cl reactivity of alkyl halides towards SN1 route. Now we
Cl / hn know that stability of carbocations follows the order :
CH3 — CH2 — CH2 — CH3¾¾2¾¾® 3° > 2° > 1°, so SN1 reactivity should also follow the
same order.
CH3 CH3 3° > 2° > 1° > Methyl (SN1 reactivity)
65. (a) A strong nucleophile favours the SN2 reaction and a
H — C — Cl + Cl — C — H weak nucleophile favours the SN1 reaction.
First reaction is SN1 reaction because C2H5OH is used
C2H5 C2H5
d l
as solvent which is a weak nucleophile.
Second reaction is SN2 reaction because C2H5O– is
Racemic mixture
50% d form + 50% l form
strong nucleophile.
Cl• may attack on either side and give a racemic mixture 66. (d) SN2 reaction is favoured by small groups on the carbon
of 2-chlorobutane which contain 50% d form and 50% atom attached to halogen.
l-form. SN2 reaction is shown to maximum extent by primary
62. (a) First draw possible different structures obtained on halides. The only primary halides given is CH3Cl so
monochlorination of 2-methylbutane, the correct answer is (d).
CH3CH(CH3)CH2CH3. 67. (b) Since SN1 reaction involves the formation of carboca-
tion as intermediate in the rate determining step. More
CH3 CH3
| | stable the carbocation, more is the reactivity of the
*
(i) ClCH 2 - C HCH 2 CH3 (ii) CH3 - C - CH 2 CH3 halide toward SN1 route. As we know that the stability
| of the carbocations decreases in the order :
Cl Benzyl > 2º > 1°.
Optically active Optically inactive Hence the correct order of stability is
III > II > I
CH3 Cl CH3
| |* | 68. (d) —NO2 group is electron attractive group, so it is able
(iii) CH3 - CH - CH CH3 (iv) CH 3 - CH - CH 2 CH2Cl to deactivate the benzene ring.
Optically active Optically inactive Cl
Thus structures (i) and (iii) are optically active, each NO2
has one chiral carbon; so each structure will give one
enantiomeric pair; thus total enantiomeric pairs will be
two. NO2
63. (b) Addition of HBr of 2-pentyne gives two structural hence withdrawl of electrons from ortho and para
isomers (I) and (II) position cause easy removal of –Cl atom due to
HBr development of +ve charge on o- and p positions.
CH 3 - C º C - CH 2 CH3 ¾¾¾
®
HALOALKANES AND HALOARENES 623

69. (c) 85. (d) Exposure of carbon tetrachloride causes liver cancer in
70. (d) CCl4 vapours are non-inflammable (i.e. do not catch humans. The most common effects are dizziness, light
fire). Hence used as fire extinguishers under the name headedness, nausea and vomiting which cause
pyrene. permanent damage to nerve cells. In severe cases,
71. (b) these effects can lead rapidly to stupor, coma,
72. (c) Tetrachloromethane (carbon tetrachloride) is also used unconsciousness or death.
as feedstock in the synthesis of chlorofluorocarbons 86. (c) In stratosphere freon is able, to initiate radical chain
and other pharmaceutical manufacturing and general reactions that can upset the natural ozone balance.
solvents etc. 87. (d) CCl4 is used as a fire extinguisher. The dense, non
73. (d) Dichloromethane is widely used as solvent as a paint combustible vapours cover the burning substance and
remover, as a propellant in aerosols and as a process prevents the availability of oxygen around burning
solvent in the manufacture of drugs. It is also used as
material.
a metal cleansing and finishing solvent.
88. (b) Chloramphenicol, produced by soil microorganism is
74. (b) Haloforms (CHX3) are trihalogen derivatives of
very effective for the treatment of typhoid fever. Our
methane.
body produces iodine containing hormone thyroxine,
Example : Chloroform CHCl3.
the deficiency of which causes a disease called goiter.
75. (a) Chloroform is an organic compound which does not
Synthetic halogen compounds, viz chloroquine is used
ionise in water. Since it can not provide Cl–, therefore,
it is not precipitated with AgNO3. for the treatment of malaria; halothane is used as an
76. (c) 77. (b) 78. (d) 79. (b) anaesthetic during surgery. Certain fully fluorinated
compounds are being considered as potential blood
Cl substitutes in surgery.

80. (a) CCl3CH

Cl Exercise - 2

(DDT) 1. (b) Alchols and halogen acid react through S N 1

81. (b) Carbon tetrachloride rises to atmosphere and deplete mechanism.
the ozone layer. This depletion of ozone layer increases +
CH3 —CH 2 —CH 2 —OH ® CH3 —CH2 —CH+ OH -
exposure of UV rays to human being which lead to
increase of skin cancer, eye diseases and disorder with In this case, 1° carbocation is formed. It is least stable.
discruption of the immune system. So, here SN2 mechanism is followed. In this S N2
82. (a) Cl Cl Cl Cl mechanism a transition state is observed in which
C + [O] Light and air
¾¾¾¾® C a - carbon is linked with two nucleophilies.
Cl H Cl OH + –
Chloroform CH3— CH2 — CH — OH ® CH3— CH2 — CH — OH
Cl | |
HCl + C=O CH3 CH3
Phosgene
Cl 2º Carbocation (more stable than 1º carbocation)
Phosgene is an extremely poisonous gas.
83. (c) Triiodomethane (CHI3) when comes in contact with CH3 CH3
organic matter decomposes easily to free iodine which | |+ –
has antiseptic property. CH3— CH2 — C — OH ® H3C — CH2 — C + OH
oxidation | |
84. (a) CH3CH 2OH + Cl2 ¾ ¾¾¾¾® CH3CHO + 2HCl CH3 CH3
Ethanol Ethanal 3° carbocation (most stable)

CH3CHO + 3Cl2 ¾¾® CCl3CHO + 3HCl

Greater the stability of carbocation, greater will be the
Ethanal Chloral
possibilities of attack of X– ion on the carbocation.
2CCl3CHO + Ca(OH)2 ¾¾®
Order of stability of carbocation is : 3° > 2° > 1.
2CHCl3 (HCOO) 2 Ca So order of reactivity will be C > B > A.
+ Cal. formate
Chloroform
2. (d) Reaction of alcohols with conc. HCl at room
CH3COCH3 + 3Cl2 ¾¾® CCl3COCH3 + 3HCl temperature follows SN1 mechanism.
Acetone Trichloroacetone The attack of nucleophile to the carbocation is possible
2CCl3CO.CH3 + Ca(OH)2 ¾¾® only on stable carbocation as at room temperature only
2CHCl3 + (CH3COO)2Ca 3° carbocation is stable.
 EBD_7374
624 CHEMISTRY

Step I ·
CH3 CH3 CH3 – CH2 – C H – CH3 + Cl2 ®
| | – Cl
CH3 CH 2 C OH ® CH3 CH2 CÅ + OH | ·
| | CH3 – CH2 – CH – CH3 – C l
CH3 CH3 Step 3 :
Step II · ·
CH3 — CH 2 — CH 2 — C H 2 + C l ®
CH3 CH3
|r s | CH3CH 2 CH 2 CH 2 Cl
CH3 — CH2 — C + Cl ® H3C — CH2 — C—Cl
| | · ·
CH3 CH3 CH3 - CH 2 - C H - CH3 + Cl ®
3. (a) Sand meyer’s Reaction Cl
|
+ CH3CH2 CH – CH3
NH3 N2Cl Cl 7. (a) Density is directly related to molecular mass. More the
NaNO2 + HCl
¾¾¾¾¾ ® Cu 2 Cl2
¾¾¾
® +N2 molecular mass, more will be the density of the
273-278 K
compound. The order of molecular mass is
(Y) benzene < chlorobenzene < dichlorobenzene <
4. (b) bromochlorbenzene
FeCl3 r s r s 8. (c) Greater the surface area, greater will be the boiling point
Cl – Cl Cl – Cl – FeCl3 Cl + FeCl4
of a compound. Surface area decreases with increases
CH3 in branching.
CH3 CH3
r s H Increasing order of boiling point
+ Cl – Cl – FeCl3 rds
Cl or Å CH3
r H3C
H Cl H3C C CH3 < CH — CH2Br
H3C
Br
CH3 CH3 < CH3CH 2 CH 2CH 2 Br
H 9. (b) Carbon atom in which all four valencies are different is
+ Cl or + known as Asymmetrical/chiral.
10. (a) Enantiomers are the steroismers which are related to
H Cl
each other as non – superimposable mirror images.
The enantiomer of molecule (A) is
FeCls
4 FeCls
4
Mirror

CH3 CH3 H H
Cl CH3 H3C
C C
H5C2 Br Br C2H5
Cl
As electrophile Cl+ attacks on electron rich benzene
11. (b) Halides in which two halogen atoms are present on the
ring and substitutes hydrogen. So, the reaction is
electrophilic substitution reaction. two adjacent carbon atoms are known as vic - dihalides.
5. (a) Halogen exchange reactions are those reactions in which H
| CH 2 — CH 2
one hailde replaces another (Finkelstein reaction).
Cl — C— Cl | |
6. (a) It is a substitution reaction which involves the | Cl Cl
replacement of 1° and 2° hydrogen of alkanes by H
1, 2 - dichloroethane
chlorine. It occurs in presence of ultraviolet light. Dichloromethane
UV ·
Step 1 : Cl — Cl ¾¾¾
®2Cl H Cl
light | | Cl
· H — C— C — H |
C l + CH3 — CH 2 — CH 2 — CH3 ¾¾
® | | C H 2 — CH = CH 3
H Cl
· Allyl chloride
CH3CH 2 CH 2 — C H 2 + HCl Ethylidene chloride
Step 2 : 12. (a) Compounds in which the halogen atom is bonded to
· sp3 hybridised carbon atom next to carbon carbon-
CH3 — CH 2 — CH 2 — C H 2 + Cl2 ¾¾
®
· double bond are known as allyl halides.
CH3 — CH 2 — CH 2 — CH 2 Cl + C l CH3 CH = CHC ( Br ) ( CH3 ) 2
HALOALKANES AND HALOARENES 625

- Å
13. (b) ® [ AlCl 4 ] + Cl+
AlCl3 + Cl2 ¾¾ 23. (a) In C6H5CH2Br carbocation is C6 H5 C H 2 which is
Cl stable due to resonance.
+
+ Cl
Chlorobenzene CH3
14. (b) If halogen atoms present on the same carbon atom Å
CH 2 Å CH 2 CH2 CH2
then they are known as gem – dihalides or alkylidene
halides. Å Å
15. (c) Addition of HCl takes place in accordance with
Markownikoff's rule.
CH2
CH2 — CH — CH2 CH2 — CH — CH3
+
Cl
+ HCl
24. (b) If carbon atom has all four valencies with four different
16. (b) It would prefer to undergo SN2 reaction. groups then it is called as asymmetric/chiral carbon.
SN2 reactions occur if there is less steric crowding on 25. (a) All those compounds which follow SN1 mechanism
a - carbon of alkyl halide. In case of primary aklyl during nucleophilic subsitution reaction will give
halides, steric crowding is very less. So, it would prefer racemic mixture.
to undergo SN2 reaction. Order of reactivity of alkyl halides for SN1.
17. (d) All compounds are tertiary alkyl but bond formed 3° > 2° > 1° CH3 X
between carbon and iodine (C — I) is weakest bond
due to higher difference in size of carbon and iodine. Thus, CH3 — CH — Br contains a 2° carbon so
|
18. (c) IUPAC name C 2 H5
2 1
CH3 — CH — CH2 — Br gives a racemic product.
3
| 26. (c) The substitution is faster if the electron withdrawing
CH2 group is at ortho and para position because electron
|
CH3 density is high at these positions as chlorine is electron
4 donating group which increase electron density at
1-bromo-2 methylbutane ortho and para position. Therefore, it has partial double
bond character, and is not easy to break.
Br
| In compound (ii) and (iii) both has one electron
19. (b) H3 C— H 2 C— H C — C H 2 — C H3 withdrawing group but in compound (ii) electron
1 2 3 4 5 withdrawing (— NO2) group is present at ortho
IUPAC name is 3-bromopentane. position, so rate of reaction in compound (ii) is more
20. (d) Toluene react with chlorine in presence of iron and in than that of (iii) while (i) has no electron withdrawing
absence of light, by substitution on benzene ring. group.
27. (d) If electron releasing group is present at ortho or para
CH3 CH3 CH3
position it decreases the rate of nucleophilic
Cl substitution reaction. In compound (iii) electron
Fe
+ Cl2 ¾¾® + releasing group is present at meta position w.r.t.
Toluene
chlorine, so the impact is nothing but in compound (ii)
o-chlorotoluene
Cl it is present at ortho position.
p-chlorotoluene 28. (d) If electron withdrawing group is present at ortho and
para position then the nucleophilic substitution
21. (c) CH3Cl + NH3 ® CH3 NH 2 + HCl reaction rate increases.
Excess Methanamine 29. (c) If electron releasing group is present at ortho and para
22. (a) Carbon in which four bonds are different is known as position w.r.t. to chlorine it decreases the rate of
Chiral carbon. nucleophilic substitution reaction.
1 2 3 4 30. (a) Greater the surface area, greater will be the
H3C — CH — CH2— CH3 intermolecular forces of attraction and intermolecular
|
Br forces of attraction is directly proportional to boiling
(2- bromobutane) point. Surface area is larger for larger size of halogen.
 EBD_7374
626 CHEMISTRY

31. (d) Boiling point is directly proportional to size of the 37. (b) In SN1 reaction, carbocation a planar species as
molecule. All contains same halogen atom but different intermediate is formed.
hydrocarbon part. Larger the different hydrocarbon
part larger the boiling point. R1
Nu
32. (c) Methyl group is ortho para directing but due to steric Å
hind rance effect, generated by two CH3 groups C R3
substitution will not take place on position (I). Hence Nu
R2
only two products are possible.
So attack from below or above the plane can take place.
CH3
If 50% attack below and above the plane of carbocation
III I take place than 100% racemization occurs but it may
not be highly probable.
II CH3 i.e. if inversion occurs more than retention leading to
i.e. CH3 CH3 partial racemization.
38. (a) NaCl + AgNO3¾¾ ® AgCl
Br2
(White)
FeBr3
CH3Cl does not give ppt. NaBr and NaI give yellow
CH3 CH3 and dark yellow ppt. respectively.
Br
39. (c) CHCl3 is stored in dark bottles to prevent oxidation of
(A)
CHCl3 in presence of sunlight.
CH3 40. (b) Alkyl fluorides are more conveniently prepared by
Br
heating suitable chloro – or bromo-alkanes with organic
+ fluorides such as AsF3, SbF3, CoF2, AgF, Hg2F2 etc.
This reaction is called swarts reaction.
CH3
CH 3Br + AgF ¾¾
® CH 3 F + AgBr
33. (b) aq. KOH
CH 3CH 2 CH 2 Br ¾¾¾¾® 2CH3CH 2 Cl + Hg 2 F2 ¾¾ ® 2CH 3CH 2 F + Hg 2Cl 2
Al O
41. (a) Due to dipole-dipole interaction the boiling point of
CH 3CH 2 CH 2 OH ¾¾¾¾
2 3®
alkyl halide is higher as compared to corresponding
heat alkanes.
Cl / H O
42. (b) (1) CH3CH2CH2–Br + KOH
CH 3 CH = CH 2 ¾¾2¾ ¾
2¾® CH .CHOH .CH Cl
3 2 ® CH3CH=CH2 + KBr + H2O
34. (b) Steric congestion around the carbon atom undergoing This is dehydrohalogenation reaction which is an
the inversion process will slow down the SN2 reaction, example of elimination reaction.
hence lesser the congestion, faster will be the reaction.
(2) H3C CH3 H3C CH3
So, the order is
C + KOH ® C + KBr
CH3Cl > CH3CH2Cl > (CH3)2CH Cl > (CH3)3CCl
35. (a) Gammexane is C6H6Cl6 or (6, 6, 6). It is a saturated Br OH
compound so no double bond is there in it.
Replacement of Br– by OH– is substitution reaction
Cl H
Cl thus it is a nucleophilic substitution reaction.
H
H Cl
Cl Br
H
(3) + Br2 ®
H Cl
Cl H Br
36. (a) Tertiary butyl chloride will give the most stable tertiary
Above reaction involves addition of Br2 across double
carbonium ion among the other given compounds
bond. Thus it is called addition reaction.
H3C – H3C 43. (c) Alkyl halides give polyalkylation products.
Cl +
C Cl C 44. (a) When tert -alkyl halides are used in Williamson
H3C H3C synthesis elimination occurs rather than substitution
CH3 CH3
t-butyl carbonium ion
resulting into formation of alkene. Here alkoxide ion
abstract one of the b-hydrogen atom along with acting
as a nucleophile.
HALOALKANES AND HALOARENES 627

Br CH3 CH3 CH3 Cl

|
Br
(iii) CH3 – C – CH2 – CH3 ¾¾
®
45. (c) , , , |
OCH3 Å
Br Br CH3 – C – CH2 – CH3
|
46. (b) Alkyl fluorides are more conveniently prepared by OCH3
heating suitable chloro – or bromo-alkanes with organic
fluorides such as AsF3, SbF3, CoF2, AgF, Hg2F2 etc.
This reaction is called Swarts reaction. (iv) C H3 – C H2 – C H2 – Cl ¾¾
®
Å
CH 3Br + AgF ¾¾
® CH 3 F + AgBr CH3 – CH2 – CH2

2CH3CH 2 Cl + Hg 2 F2 ¾¾
® Exercise - 3
2CH3CH 2 F + Hg 2Cl2
1
47. (d) Assertion is false, because aryl halides do not undergo 1. (a) Rate of SN2 µ Steric crowding near to reaction centre .
nucleophilic substitution under ordinary conditions.
This is due to resonance, because of which the carbon– O O
chlorine bond acquires partial double bond character,
2. (b) CF3 S O > Ph S O > CH3 COO > PhO
hence it becomes shorter and stronger and thus cannot
be replaced by nucleophiles. Also, Reason is false O O
L.G. Ability
because SN2 reactions proceeds with inversion of
configuration. 3. (c) SN2 and SN1 same, if CÅ not rearrange.
48. (b) Elimination reaction is highly favoured if –
d+
d MgBr D
4. (c) ¾¾® ;
(a) Bulkier base is used
(b) Higher temperature is used
Hence in given reaction biomolecular elimination Br
heat favours elimination.
reaction provides major product. 5. (a) Primary halide < Secondary halide < Tertiary halide.
Br H 6. (d) Addition product is formed by anti-Markownikoff's
rule.
C6H5 t-BuOK 7. (a)
C6H5
1, 2 elimination

H H 8. (c) CH 3 CH = CHCH 2 Cl ¾¾ ¾
¾-
®
(- Cl )
–t
O Bu + +
é ù
®êCH 3 CH = CH C H 2 « CH 3 C H - CH = CH 2 ú
C6H5 ë û
+ t-BuOH + Br CN
C6H5 |
CN -
¾¾¾® CH 3CH = CHCH 2 CN + CH 3 C H CH = CH 2

49. (b)
OMe
¾¾¾® + NaBr + MeOH 9. (d) tert-Alkyl halides undergo S 1 reactions, hence they
N
MeOH
involve the formation of quite stable carbocations, and
(dehydrohalogenation reaction) not the transition state. In S 1 reactions, the
N
50. (b) nucleophile is not involved in rate determining (first)
51. (c) Rate of SN 1 a stability of carbocation step, hence its stronger or weaker nature does not
a +I, +M, HC effect influence the reaction rate. In SN1, the product has
(i) CH3 – CH – CH2 – CH3 ¾¾
® more percentage of the inverted configuration than the
| retained configuration, i.e. only partial racemization
Cl takes place, hence the product will be having some
Å optical activity.
CH3 – CH – CH2 – CH3 10. (d) —NO2 group is electron attractive group, so it is able
to deactivate the benzene ring.
(ii) Ph – CH2 – CH – CH3 ¾¾
®
| hence withdrawl of electrons from ortho and para
Cl Å position cause easy removal of –Cl atom due to
Ph – CH2 – CH – CH3 development of +ve charge on o- and p positions.
 EBD_7374
628 CHEMISTRY

11. (a)
12. (b, d) 13. (d)
+ + +

(a) H2/Ni O N –I B
* –I max
H H
H Br H Br Aromatic Aromatic Anti-aromatic
H2/Ni
(b)
(Optically inactive) 14. (d)
15. (a) Chlorination beyond monochlorination during the
preparation of alkyl halides in presence of UV light can be
(c) H2C H2/Ni H3C
CH3 * CH3 suppressed by taking alkane in excess.

CH3 CH3

H2/Ni
(d) H 2C CH3 H 3C CH 3
 25. ALCOHOLS, PHENOLS AND ETHERS

th e tetrahedr al an gle (109°-28¢). The correct

Exercise - 1
explanations. It is due to the repulsion between the
1. (b) Glycols are dihydric alcohols (having two hydroxyl unshared electron pairs of oxygen.
groups). Ethylene glycol is the first member of this 13. (c) Ethylene is passed into concentrated sulphuric acid at
series. 75–80°C under pressure when a mixture of ethyl
hydrogen sulphate is formed. Which on heating ethyl
CH 2 OH alcohol.
| 100°C
CH 2 OH H 2 C = CH 2 + H 2 SO4 ¾¾¾¾
® C 2 H 5 HSO 4
Ethylene glycol Ethylene
D
2. (c) Ethers contain the functional group – O – ¾¾¾
® C 2 H 5 OH + H 2 SO 4
H 2O
3. (b) CH3CH2CH(OH)CH3 is a secondary alcohol
4. (b) Cresol has phenolic group – OH SO 3 - Na + O - Na +
5. (b) Four primary alcohols of C5H11OH are possible. These
14. (b) NaOH + Na2SO3.H2O
are:
300°
(i) CH 3 CH 2 CH 2 CH 2 CH 2 OH
(ii) CH 3 CH 2 - CH - CH 2 OH HCl
| OH
CH 3
(iii) CH 3 - CH - CH 2CH 2 OH + NaCl
|
CH 3 15. (b)
CH 3 H
H |
| |
(iv) CH 3 - C - CH 2 OH CH3MgBr H C OMgBr

|
|
16. (a) H C = O ¾¾¾ ¾¾® |
|

|
CH 3 CH3
H
6. (c) In this structure –OH group is directly attached to |
H 3O +
double bonded carbon atom i.e. sp2 hybridized carbon ¾¾¾ ¾® H C OH
|

|
atom. |
7. (c) If two groups attached to the oxygen atom are different CH 3
then ethers are known as unsymmetrical or mixed 17. (b) Since the compound is formed by hydration of an
ethers. alkene, to get the structure of alkene remove a molecule
8. (a) Methyl alcohol (CH3OH) is also known as carbinol. of water from the alcohol.
Hence vinyl carbinol is CH2 = CH – CH2OH. -H O
CH3 C H CH3 ¾¾¾
2 ¾
® CH 2 = CHCH3
9. (a) CH 2 = CH - OH represents vinylic alcohol. In vinylic |
OH
alcohols, – OH group is attached to sp2 hybridized Isopropyl alcohol Propylene
carbon whereas in allylic alcohols, – OH group is 18. (d) The aldehydes which do not have a -hydrogen atom
attached to sp3 hybridized carbon. react with NaOH when half of molecules are reduced to
CH 3 alcohol and other half of molecules are oxidised to acid
5 4 3 |2 1 (Cannizzaro reaction).
10. (b) C H 3 – CH – CH 2 – C – CH 3
| | 2 HCHO ¾¾® CH 3OH + HCOONa
OH OH Methanol Methyl alcohol Sod. formate
2-Methyl-2, 4-pentanediol. 19. (a) Commercially, acids are reduced to alcohols by
11. (d) converting them to the esters, followed by their
:O : reduction using hydrogen in the presence of catalyst
12. (b) The bond angle in alcohols is slightly less than
C H (catalytic hydrogenation).
 EBD_7374
630 CHEMISTRY

R'OH H 28. (c)

RCOOH ¾¾®
+
RCOOR ¢ ¾¾¾
2 ® RCH OH + R ¢OH
2
H Catalyst
O– O O
20. (b) A diazonium salt is formed by treating an aromatic –
primary amine with nitrous acid (NaNO2 + HCl) at

..
29. (c) etc.
273-278 K. Diazonium salts are hydrolysed to phenols
. .–
by warming with water or by treating with dilute acids.
Resonance stabilisation of phenoxide ion
(conjugate base of phenol)
NH2 N2 Cl OH Conjugate base of ethyl alcohol, i.e., C2H5O– does not
H2O
show resonance.
NaNO2
+HCl Warm + N2 + HCl 30. (b) Phenol is most acidic because its conjugate base is
stabilised due to resonance, while the rest three
Aniline Benzene diazonium compounds are alcohols, hence, their corrosponding
chloride
conjugate bases do not exhibit resonance.
21. (a) The lower alcohols are readily soluble in water and the 31. (b) C 2 H 5 OH + CH 3 COOH ¾¾ ® CH 3COO.C 2 H 5 + H 2 O
solubility decreases with the increase in molecular 32. (c) Secondary alcohols oxidise to produce ketones.
weight. The solubility of alcohols in water can be
explained due to the formation of hydrogen bond ( O)
CH3CHOHCH2CH3 ¾¾
¾® CH3COCH2CH3
between the highly polarised —OH groups present 2-Butanol Ethyl methyl ketone
both in alcohol and water.
33. (d) The rates of reaction with Lucas reagent follows the
22. (c) o-Nitrophenol has intramolecular H-bonding. order.
23. (b) The solubility of alcohols depend on number of 3° alcohol > 2° alcohol > 1° alcohol
C-atoms of alcohols. The solubility of alcohols in water since carbocations are formed as intermediate, more
decreases with the increase in number of C-atoms of stable the carbocation, higher will be the reactivity of
alcohol. As resulting molecular weight increases, the the parent compound (alcohol). 2-Methylpropan-2-ol
polar nature of O – H bond decreases and hence generates a 3º carbocation, so it will react fastest; other
strength of hydrogen bond decreases. three generates either 1º or 2º carbocations.
24. (d) Solubility of alcohol in water decreases with increase CH3
|
in molecular mass due to increase in water repelling H+
CH3 - C - OH ¾¾¾ ®
alkyl part in alcohol. |
25. (b) When ethanol dissolves in water then there is emission CH3
of heat and contraction in volume. 2-Methyl-2-propanol

26. (d) C 2 H 5OH + 4I 2 + 6NaOH ¾¾ ® CH3 CH3

| - |
CHI 3 ¯+ HCOONa + 5NaI + 5H 2 O Å Br
CH3 - C ¾¾¾® CH3 - C - Br
Iodoform | |
27. (a) When primary (1°) alcohols are treated with copper at CH3 CH3
300°C, then aldehydes are obtained by dehydrogenation
of alcohols. Similarly secondary (2°) alcohols form ketone 34. (d) OH OH
and alkene is obtained by dehydration of tertiary (3°) - | Br Br
alcohols. But phenol does not respond to this test. 3Br2 (aq.)

Cu
R - CH 2 - CH2 - OH ¾¾® R - CH 2 - CHO + H 2
1° Alcohol 300°C Aldehyde Br
H 2, 4,6-Tribromophenol
| Cu
R – C – OH ¾¾¾®
300°C
R – C – R + H2 Note : The –OH group in phenol, being activating
|
R O group, facilitates substitution in the o- and p-positions.
2° Alcohol Ketone OH OH
CH3 CHCl2
| Cu 35. (b)
R – C – OH ¾¾¾® R - C = CH 2 + H2O + CHCl3
300°C
| |
CH3 CH 3
3° Alcohol Alkene OH OH
CH(OH)2 CHO
Cu
C 6 H 5 – OH ¾¾¾®
300°C
No reaction 2KOH
–H2O
ALCOHOLS, PHENOLS AND ETHERS 631

This set of reactions is known as Reimer-Tiemann destablises it hence decreases ionization of parent
reaction. phenol, therefore decreases acidity. While electron
36. (b) The correct explanation is : In Lucas test, tertiary donating groups (–NO2, –COOH, –CHO etc.) increases
alcohols react immediately because of the formation of acidity.
the more stable tertiary carbocations. 46. (b) Alcohols are versatile compounds. They react both
37. (c) Lucas test is used to distinguish between 1°, 2° and 3° as nucleophiles and electrophiles. The bond between
alcohols. Lucas reagent is anhy. ZnCl2 and HCl. O—H is broken when alcohols react as nucleophiles.
3° alcohol + Lucas reagent ¾ ¾® turbidity immediately Alcohols as nucleophiles
2° alcohol + Lucas reagent ¾ ¾® turbidity after
5 minutes H
.. – C – ® R–O– C– +H
R –+O +
1° alcohol + Lucas reagent ¾¾® No turbidity at (i) R–O–H+ +C –
room temperature.
38. (a) OH OH (ii) The bond between C — O is broken when they
react as electrophiles. Protonated alcohols react
COOH in this manner.
Salicyclic acid Phenol
(evolves CO 2 with NaHCO3) (No reaction with NaHCO3)
Protonated alcohols as electrophiles
39. (b) Other options are acids, only Na metal is a base. + +
40. (b) Phenol on reaction with conc. H2SO4 gives a mixture R - CH 2 - OH + H ¾¾
®R - CH 2 -OH 2
of o- and p- products (i.e., –SO3H group, occupies
o-, p- position). At room temperature o-product is more +
stable, which on treatment with conc. HNO3 will yield Br – + CH2 – OH2 Br – CH2 + H2O
o-nitrophenol.
R R
OH OH OH
SO3H 47. (c) The correct reason is : Nucleophilic attack of phenolate
Conc. H SO
¾¾¾¾®
2 4
+ ion through the ortho-carbon atom occurs on CCl4 (a
neutral electrophile) to form an intermediate which on
SO3H
o-product p-product hydrolysis gives salicylic acid (ArSE reaction).
At room temperature o-product is more stable 48. (c) The C — O bond length (136 pm) in phenol is slightly
less than that in methanol (142 pm).
OH OH
SO3H NO2 49. (b)
Conc. HNO3
50. (a) A methanol poisoned patient is treated by giving
o- nitrophenol
intravenous injection of ethanol.
51. (a) R is the correct explanation of A. Due to +M effect of
..
41. (d) 3C 2 H 5 OH + PBr3 ¾
¾® 3C 2 H 5 Br + H 3 PO 3 -O
.. H , its intermediate carbocation is more stable than
[X ]
the one in benzene.
42. (c) Methanol and ethanol can be distinguished by heating 52. (c) KMnO4 (alkaline) and OsO4 / CH2Cl2 are used for
with iodine and washing soda hydroxylation of double bond while O3 /Zn is used for
I ozonolysis. Therefore, the right option is (c), i.e.,
C 2 H 5 OH ¾¾¾¾®
2 CHI 3 + HCOONa
Na 2 CO 3 3CH 3CH = CH 2 BH in THF
¾¾3¾¾ ¾® (CH 3CH 2 CH 2 )3 B
Iodoform
(yellow ppt)
3H O
¾¾2¾¾
2®
NaOH
3CH 3CH 2CH 2OH + H3BO3
+ NaI + 2NaOH + H 2O
1-propanol

CH3OH ¾¾¾¾
I2
® No reaction 53. (a) Hydroboration-oxidation leads to anti-Markownikoff’s
Na 2CO3 hydration, thus
This is also called iodoform test. (i) BH /THF OH
¾ ¾¾3¾ ¾®
–
43. (a) 44. (d) (ii) H2O2/OH

OH OH OH 1-Pentanol

CH3 COOH 54. (b) NaBH4 and LiAlH4 attack only carbonyl group and
45. (d) reduce it into alcohol group.
NaBH
o-Cresol (a) Salicylic acid (b) Phenol (c) C6 H5 - CH = CHCHO ¾¾¾¾
4®

Electron releasing groups (–CH3, –OCH3, –NCH3 etc) Cinnamic aldehyde

intensify the negative charge of phenoxide ion, i.e., C6 H 5 - CH = CH.CH 2OH
Cinnamyl alcohol
 EBD_7374
632 CHEMISTRY

55. (a) In case of (ii) and (iii), the alcohol so obtained contains OH
carbon which is attached to four different groups i.e.,
chiral carbon while in case of (i) and (iv) achiral alcohol Zn CH Cl
60. (b) ¾¾® ¾ ¾¾
3
¾®
anhy AlCl3
is obtained.
56. (c) Electron withdrawing substituents like –NO2, Cl Phenol X
CH3 COOH
increase the acidity of phenol while electron releasing
substituents like – CH3, – OCH3 decrease acidity. hence
alk
the correct order of acidity will be
KMnO 4
OH OH OH OH Y Z
Al2O3 Al2O3
61. (c) CH 2 = CH 2 ¬¾¾¾ ¾ CH 3CH 2 OH ¾¾¾¾ ® CH 3CH 2OCH 2CH 3
650 K 525 K
> > >
® CH 3CH 2 OCH 2 CH 3
62. (b) Dehydration of CH3OH gives carbene (methylene), an
NO2 Cl CH3 OCH3 unstable intermediate.
III I II IV H SO
2 4 ®[: CH ]+ H O
CH3OH ¾¾¾¾ 2 2
(–M, –I) (–I > +M) (+I, + HC) (+ M)
Carbene
57. (c) The usual halogenation of benzene takes place in the 63. (d) Since the compound (C4H10O) reacts with sodium, it
presence of a Lewis acid, such as FeBr3, which polarises must be alcohol (option b, c, or d). As it is oxidised to
the halogen molecule. In case of phenol, the carbonyl compound which does not reduce Tollen’s
polarisation of bromine molecule takes place even in reagent, the carbonyl compound should be a ketone
the absence of Lewis acid. It is due to the highly and thus C4H10O should be a secondary alcohol, i.e.
activating effect of –OH group attached to the benzene sec-butyl alcohol; other two given alcohols are 1º.
ring. P + I2 Mg
64. (d) CH3CH 2 OH ¾¾¾ ® CH3CH 2 I ¾¾¾®
58. (c) The mechanism of the reaction involves the following ether
A
three steps: CH 2 CH 3
Step 1: Protonation of alkene to form carbocation by HCHO
|
CH3CH 2 MgI ¾¾¾¾ ® H - C - OMgI
electrophilic attack of H3O+
(B) |
H2O + H+ ® H3O+ H
(C)
H H CH 2CH3
H + +
|
C=C + H — .O. — H ® — C — C + H2O H2 O
¾¾¾ ® H - C - OH
H |
H
Step 2: Nucleophilic attack of water on carbocation. (D)
n - Propylalcohol
H H H 65. (c) Alkyl aryl ethers are cleaved at the alkyl-oxygen bond
+ + due to the more stable aryl-oxygen bond. The reaction
—C—C + H2O ® — C — C — O — H
yields phenol and alkyl halide
H H O–R OH
Step 3: Deprotonation to form an alcohol.
.. +H–X +R–X
H H H OH
..

+ .. + Ethers with two different alkyl groups are also cleaved

— C — C — O — H + H2O ® — C — C — +H3 O in the same manner.
H H R - O - R '+ HX ® R - X + R '- OH
66. (c) Glucose and fructose obtained by hydrolysis of
59. (c) Due to strong electron-donating effect of the OH group, sucrose, are converted into alcohol by enzyme zymase.
the electron density in phenol is much higher than that
zymase
in toluene, benzene and chlorobenzene and hence C 6 H12 O 6 ¾¾ ¾
¾® 2C 2 H 5 OH + 2CO 2
phenol is readily attacked by the electrophile.
Cr O – ZnO
CO + H2 + H2 ¾ ¾¾ ¾ ® CH3OH
2 3
67. (a)
300ºC
water gas Methanol
ALCOHOLS, PHENOLS AND ETHERS 633

68. (b)
Diastase
Od -
69. (a) 2(C6 H10O5 ) n + nH 2O ¾¾¾¾¾¾¾¾¾
(from germinated barley)
® ÷÷ d+ d-
Starch CH3 - C - OCH3 CH3 - C º N
nC12 H 22 O11 d+
Maltose

Maltase
C12 H 22 O11 + H 2 O ¾¾¾¾¾ ® 2C6 H12 O6 ..
(from yeast)
Glucose C2H5 - O
. . - C 2 H5

Zymase
C6 H12 O 6 ¾¾¾¾¾® 2C 2 H 5 OH + 2CO 2 84. (a) In Williamson’s synthesis the reaction of alkyl halides
(from yeast)
70. (c) The quantity of sugar increases and yeast grows on with sodium alkoxides give ethers. However, if the alkyl
the outer skin as grapes ripen. When grapes are halide is 3°, it undergoes elimination to give an alkene.
crushed, sugar and the enzyme come in contact and CH3
| +–
fermentation starts. Fermentation takes place in H3C – C – Cl + NaOC2H5 D
anaerobic contidions i.e., in absence of air, CO2 is |
released during fermentation. If air gets in to CH3
fermentation mixture, the oxygen of air oxidises ethanol tert-Butyl chloride Sod. ethoxide
to ethanoic acid which in turn destroys the taste of CH2
||
alcoholic drinks. CH3 – C – CH3 + C2H5OH + NaBr
71. (b) The commercial alcohol is made unfit for drinking by
2-Methyl-1-propene
mixing in it some copper sulphate (to give it colour) 85. (c) If a tertiary alkyl halide is used, an alkene is the only
and pyridine (a foul smelling liquid). It is known as reaction product and no ether is formed. For example,
denaturation of alcohol. the reaction of CH3ONa with (CH3)3C–Br gives
72. (d) The two components should be (CH3) 3CONa + exclusively 2-methylpropene.
(CH3)3CBr. However, tert-alkyl halides tend to undergo
elimination reaction rather than substitution leading to CH3
the formation of an alkene, Me2C = CH2 | + –
CH3 - C - Br + NaO – CH3 ¾¾¾
®

: :
73. (a) Due to H-bonding, the boiling point of ethanol is much
higher than that of the isomeric diethyl ether. |
CH3
74. (d) Due to inter-molecular hydrogen bonding in alcohols
boiling point of alcohols is much higher than ether.
CH3 - C = CH 2 + NaBr + CH 3OH
75. (c) 76. (c) |
77. (b) Only alkyl aryl ethers e.g., C6H5OCH3 undergoes CH3
electrophilic substitution reactions. 2-Methylpropene
78. (a) Ethers are readily cleaved by HI as follows : It is because alkoxides are not only nucleophiles but
+
strong bases as well. They react with alkyl halides
+
R – O – R ˆˆ† R – O – R ¾¾® ROH + RI.
H I –
leading to elimination reactions.
| 86. (c) In the cleavage of mixed ethers having two different
H alkyl groups, the alcohol and alkyl iodide formed
79. (c) In case of unsymmetrical ethers, the site of cleavage depends on the nature of alkyl groups. When primary
depends on the nature of alkyl group e.g., or secondary alkyl groups are present, it is the lower
alkyl group that forms alkyl iodide therefore
373K
CH 3O - CH(CH3 ) 2 + HI ¾¾¾® CH 3I + (CH3 )2CHOH CH 3 - CH - CH 2 - O - CH 2 - CH 3 + HI ¾¾®
D
Methyl Isopropyl |
iodide alcohol CH3
The alkyl halide is always formed from the smaller alkyl CH3
group. |
80. (b) Due to greater electronegativity of sp2-hybridized CH3 - CH - CH 2 OH + CH3CH 2 I
carbon atoms of the benzene ring, diaryl ethers are not 87. (a) R is the correct explanation of A.
attacked by nucleophiles like I–.
81. (b) Exercise - 2
CH3 CH3 1. (d) CH3 CH2Cl CH2OH
82. (b)
CHOCH3 + HI CH3I + CHOH
CH3 CH3
Cl aq NaOH
2-Propanol ¾¾¾¾
2
® ¾¾¾¾¾
®
sunlight
83. (d) Diethyl ether, being a Lewis base, is not attacked by
nucleophiles, while all others contain electrophilic carbon, Toluene Benzyl chloride Benzyl alcohol
hence attacked by nucleophiles like OH– ions.
 EBD_7374
634 CHEMISTRY

2. (a) Following are the three possible isomers of butanol. CH3

(i) CH3CH 2 — CH 2 — CH 2OH 3
2
Butan - 1 - ol 1

no chiral carbon. m-cresol

OH
* Here – OH is the functional group and the methyl
(ii) CH3 CH2 CH CH3 is substituents. Hence the IUPAC name is 3-
methylphenol.
OH
9. (c) 3 2
Butan –2 – ol
H3C — CH — OCH3
1-Chiral Carbon |
1
(iii) CH3 CH3

IUPAC name of the above compund is 2-

H3C C CH3
methoxypropane.
10. (b) Weakest acid has the strongest conjugate base.
OH
Among all these acids, ROH is the weakest acid.
2 – methylpropan – 2 – ol Therefore, the strongest base is RO– .
No Chiral Carbon 11. (a) Phenol being more acidic in nature reacts with sodium
3. (c) HCl + An. ZnCl2 is known as lucas reagent. It is used hydroxide solution and by the loss of one proton, it
to determine degree of an alcohol. give phenoxides ion. This phenoxide ion is resonance
The reaction follow nucleophilic substitution reaction stabilised.
in which — OH group is replaced by — Cl. In this OH ONa
reaction carbocation is formed as intermediate. Higher
the stability of intermediate carbocation higher will be
the reactivity of reactant molecule. Since 3° carbocation +NaOH +H2O
is more stable than 2° carbocation as well as 1°
carbocation. 12. (b) Presence of electron withdrawing group at ortho
Hence, the order of reactivity of alcohols is 3° > 2° > 1°. position increase the acidic strength. In o-nitrophenol,
4. (c) Less powerful oxidizing agent, Pyridinium nitro group is present at ortho position. On the other

( )
hand, in o-methylphenol and in o-methoxyphenol,
+ -
chlorochromate C5 H 5 N HCl C rO3 oxidises electron releasing group (—CH3, —OCH3) are present.
primary alcohols to aldehydes. Presence of these groups at ortho & Para positions of
phenol decreases the acidic strength of phenols. So,
PCC
CH3CH 2 OH ¾¾¾
® CH3CHO phenol is less acidic than o-nitrohenol.
Ethanol Ethanal 13. (d) Presence of electron withdrawing group increases the
acidic strength. So, m-chlorophenol is most acidic
5. (b) The process of conversion of alkyl halides into among all the given compounds.
alcohols involves substitution reaction. 14. (b) Electron withdrawing substituents increase the acidic
OH - strength of phenols. so, p-nitrophenol (II) and
R — X ¾¾¾® R — OH
m-nitrophenol (IV) are stronger acid than Phenol (I). If
Alkyl halide Alcohol
— NO2 group is present at p-position, then it exerts
6. (c) Compound (A) i.e., phenol and compound (D) i.e., a both — I and — R effect but if it is present at meta
derivative of phenol cannot be considered as aromatic position, then it exerts only–I effect. Therefore,
alcohol. p-nitrophenol is stronger than m-nitrophenol.
On the other hand. In compounds (B) and (C), — OH On the other hand, electron releasing substituents
group is bonded to sp3 hybridised carbon which inturn decreases the acidic strength of phenol. If — OCH3 group
is bonded to benzene ring. Hence, are considered as is present at meta position, it will exert – I effect only.
aromatic. But, if it is present at para position, it will exert + R
6 5 4 3 2 1 effect. Thus, m - methoxy phenol is more acidic than
7. (c) CH3 CH CH2 CH2 CH CH3 p- methoxy phenol. Hence, the correct order of
decreasing acidic strength will be : II > IV > I > III > V.
Cl OH 15. (c) Nucleophilic substitution reactions depends upon the
5-chlorohexan-2-ol stability of carbocation. As, presence of electron
with drawing group decreases the stability of
8. (a) The structure of m – cresol is
carbocation in compound (II) and (III). Therefore, will
ALCOHOLS, PHENOLS AND ETHERS 635

give less stable carbocation than (I). 23. (c) The acidic nature of phenol is due to the formation of
Now NO2 group is a stronger EWG than — Cl. stable phenoxide ion in solution
+
Thus, NO2 — C6H5 — C H 2 will be less stable than ˆˆ† C6 H 5 O - + H 3O +
C6 H5OH + H 2O ‡ˆˆ
+ Phenoxide ion
Cl — C6H5 — C H 2 The phenoxide ion is stable due to resonance.
Hence, the order of reactivity of carbocatiors will be: O– O O
+ +
n + –
••
O2 N C H 2 < Cl C H2 < C H2
16. (a) With increase in molecular mass boiling point ••
–
increases. Thus the b.p. of pentan-1-ol will be more
than other given compounds. Now, among isomeric OH O– O
alcohols 1° alcohols will have higher boiling points
d d
– –

than 2° alcohols due of higher surface area. ••

–
Hence, increasing order of b.pts. will be
Propan-1-ol < butan-2-ol < butan-1-ol < pentan-1-ol. d
–

The negative charge is delocalized in the benzene ring

17. (b) Phenols react with alkyl halides in alkaline medium to
which is a stabilizing factor in the phenoxide ion and
form ethers. Therefore, increase in acidity of phenol. wheras no resonance is
OH OCH3 possible in alkoxide ions (RO–) derived from alcohol.
The negative charge is localized on oxygen atom. Thus,
(i) NaOH alcohols are not acidic.
(ii) CH3I 24. (a) Electron withdrawing group (–NO2) increases the
18. (c) o-nitrophenol will not be soluble in NaHCO3. Due to acidity while electron releasing group (–CH3, –H)
intramolecular hydrogen bonding hydrogen on OH is decreases acidity. Also effect will be more if functional group
is present at para position then ortho and meta position.
strongly bound. So it can not be have as an acid and
can not react with sodium bicarbonate. SO 3 - Na + O - Na +
HBr/H2O 2
CH 3 CH 2 CH CH 2 NaOH
(Peroxide effect) 25. (b) + Na 2SO 3 + H 2 O
19. (a) CH3 CH2 CH2 CH2 300°
(Y)
Br
HCl

CH3
(CH2)3 O CH2 CH3 OH
(Z)
20. (b) Vinyl alcohol, CH2=CHOH, monomer of polyvinyl + NaCl
alcohol exists mainly as CH3CHO; hence polyvinyl
alcohol is best prepared by the alkaline hydrolysis of 26. (d) Williamson synthesis is one of the best methods for
polyvinyl acetate which in turn is prepared by the the preparation of symmetrical and unsymmetrical
polymerisation of vinyl acetate. ethers. In this method, an alkyl halide is allowed to
21. (d) An excellent reagent for oxidation of 1° alcohols to react with sodium alkoxide.
aldehydes is PCC.
PCC d
-
R - CH 2 - OH ¾¾¾
® R - CHO 27. (d) CHCl3 + NaOH ƒ : CCl3 + H 2 O
ONa OH d
- d
-
22. (a) + CO2 ¾¾
® : CCl3 ¾¾
® : CCl2 + Cl
COONa – –
O O Cl
Sodium
Phenoxide Cl C
– Cl + H O
H2SO4 + :C 2 –
O Cl – OH
|| – –
O - C - CH3 OH O O
(CH CO) O C=O CCl2
¬¾¾¾¾¾
3 2 ¾
OH
–

COOH COOH H – 2HCl H

Aspirin Salicylic acid
(Acetyl Salicylate)
Therefore functional group – CHO is introduced.
+ CH3COOH
 EBD_7374
636 CHEMISTRY

28. (a) ZnCl2 is a lewis acid and interact with alcohol. 31. (d) 1-pentanol
Å
Primary alcohols readily form ether when heated with
CH 3 — CH 2OH + ZnCl 2 ® R — O— ZnCl 2 conc. H2SO4.
| 32. (b) On using ter-butyl bromide and sodium ethoxide as
H
reactants, the major product would be 2-methylpropene
(R = CH3 — CH 2 —) (I)
and ethanol (elimination reaction).
Å
, ΢
R — O— ZnCl2 ® R Å + [HOZnCl 2 ]O CH3 CH3
|
| |
H CH3 — C — Br + CH3ONa ¾¾
® CH3 — C = CH 2
(I) |
CH3
Carbocation is formed as intermediate in the SN1
mechanism which these reaction undergoes.
33. (a)
In the absence of ZnCl 2 formation of primary 34. (a) This is an example of Williamson ether synthesis
carbocation is difficult which is the case with (ii) while reaction in which sodium alkoxide reacts with alkyl
(i) undergoes reaction. halide and gives ether.
(iii) Tertiary carbocation casily formed due to the stability. 6 CH3 - CH = CH 2 ¾¾¾®
2 6 B H
35. (d)
ether, 0°C
OH Propene
|
CH3 — C — CH3 ¾¾
® H O
2(CH3CH 2 CH 2 )3B ¾¾¾®
2 2
| OH -
CH3
6CH 3CH 2 CH 2 OH + 2H 3 BO 3
Å Propanol
CH3 — C — CH3 + H 2 O
| 36. (a) Ethers have lone pair on oxygen, so they behave as
CH3 Lewis base. It forms salt known as oxonium salt with
(iv) In the presence of ZnCl2, 2° carbocation is formed from acids.
(CH3 ) 2 — C— OH R R
| + – + –
H O : + H Cl ¾
¾® O H Cl
R R
Å
i.e., CH3 — C H— CH3
OH OH OH
29. (b) OH +H ®
Å
O—H
Å
37. (b) NaNO2, H2SO4
¾¾¾¾¾¾®
HNO3
¾¾®
H 7–8°C

¯ H NO NO2
Phenol p-Nitrosophenol p-Nitrophenol
Å
¬
H Thus here, oxidation of phenol is minimised by forming
p-nitrosophenol.
¬

¯
H3 C .. H3 C H3 C Å ..
38. (d) Å Å
C=O +H .. – H ¬¾®
C= O C– O
.. – H
..

H3 C H3 C H3 C
30. (a) Reaction involved is given as :
CH3 CH 3 CH3 CH3 +
½ HCl ½ .. ..
CH 3 —C—OH ¾¾¾® CH 3 —C—Cl H3 C – C – OH
.. H3 C – C – O.. – H
½ ZnCl 2 ½ H
CH3 CH 3
(A) (B) ¬¾¾ ¬¾¾

CH3 O
.. +O O
..
..

..

..

alc. KOH ½ H H H
¾¾¾® CH3 —C H+
½½
CH 2
ALCOHOLS, PHENOLS AND ETHERS 637
CH3
CH3 O O
+
Å OH tert - BuONa
H3C OH2 H3C C 43. (a) ¾¾ ¾ ¾ ¾
®
C
H Br O-tBu
O H
(fails to decolorise the
colour of bromine)
due to unsaturation
OH OH Products formed in option (2), (3) and (4) decolorises bromine
solution due to presence of double bond.
CH3
| Na –
44. (c) C2H5OH ¾¾® C2H5O Na
+
HO C OH
| (A) (B)
CH3
PCl5
39. (c) Electron withdrawing – NO2 group has very strong –I
and –R effects so, compound 3 will be most acidic. C2H5Cl
40. (b) When Ar – O – R ethers are reacted with HI, they are (C)
– S 2
cleaved at weaker O – R bond to give phenol and alkyl C2H5O Na+ + C2H5Cl ¾¾®
N
C2H5OC2H5
iodide. (B) (C)
O – CH3 OH So the correct option is (3)
HI –
+ CH3I 45. (c) CHCl3 + NaOH ¾® CCl3 + H2O

¾®
– Cl (a-elimination)
: CCl2 dichlorocarbene
(electrophile)
41. (d) OCH3 OCH3
46. (d) Haloform reaction is shown by compound having
H CH3 – C – or CH3 – CH –
NH 2 || | Group
O OH
Br Br
NaOI
¾¾¾¾®
CH – CH3 or
OCH3 | NaOH + I 2
OH
– +
C – ONa + CHI3
|| Yellow
O ppt.
Benzyne 47. (c) Mechanism :
AlCl
CH 3 – CH 2 – CH 2 – Cl ¾¾¾®
3
+ –
OCH3 CH3 – CH 2 – CH 2 + AlCl4
NH 2 1° Carbocation
OCH3
a CH3 – CH – CH3
(Less stable) + –
NH2 ESR H
OCH3 OCH3 ¬¾¾¾ CH 3 CH CH3 shift
2° Carbocation
b (P)
H — NH2
CH3
CH3 – CH – CH3 CH3–C– O– O–H
NH2 NH 2 O +
(More stable) ¾¾®
D
2 H3O
D
More stable as –ve charge is close to electron Cumene Cumene
(P) hydroperoxide
withdrawing group.
Also, incoming nucleophile gets attached on same 'C' OH
O
on which 'Br' (Leaving group) was present.
+ CH3 – C– CH3
\ not a cine substitution reaction
42. (b) Phenol Acetone
(Q) (R)
 EBD_7374
638 CHEMISTRY

48. (a)
–
49. (b) Ortho nitrophenol is more acidic than meta nitro phe- OH O O O
nol because at ortho position NO2 group show both – :–
53. (c)
M & –I effect but at meta, –NO2 group show only – I
.–.
effect.
CH 2 = CHCH2Cl

(i) CO ,NaOH
50. (a) ¾¾¾¾¾¾ 2
®
(ii) Acidification
OCH2CH = CH2 OH OH
Kolbe reaction
Salicylic acid CH2CH = CH2
(X) +
+

CH2CH = CH2
conc. H 2SO 4
+ (CH 3CO) 2 O ¾¾¾¾¾
®
(Acylation reaction) 54. (a) Alkylhalide formation in the reaction of alcohol with
(X) HCl undergoes SN1 reaction in which formation of
the carbocation as intermediate occurs. Stability of
carbocation is greatest for (C6H5)3C+ due to resonance
effect, and stability of tertiary carbocation is greater
than the secondary carbocation hence the option (a)
Aspirin shows the correct order.
(non-narcotic analgesic)
55. (d) Among the given compounds only CH3OH does not
give iodoform reaction.
NaOH
51. (c) + Cl – C – O – Me ¾¾¾® Exercise - 3
||
O 1. (a)
2. (d)

O3 CHO LiAlH4 CH2 OH

Zn + H2O
CHO CH2 OH
(A)

O3/H2O2 COOH LAH CH2 OH

COOH CH2 OH
Cold dil. OH
+ Br2 ¾ ¾® + HBr KMnO4 HIO4 CHO
CHO
(A) Br OH
(B) LAH CH2OH
CH2OH

+
+
52. (d) ¾ ¾® H +
OH OH2
3. (d)
+
–CH3OH
–H2O CH2

+
1º carbocation
(least stable)

1,2–alkyl 1,2–alkyl +
shift + shift
2º carbocation 3º carbocation
(more stable) (most stable)
ALCOHOLS, PHENOLS AND ETHERS 639

4. (c) ClCH 2 CH 2 OH is stronger acid than CH3CH 2 OH due to

> CH2 = CH - CH = CH2 > CH3CH = CHCH 3 > CH3 CH 2CH = CH 2
– I effect of Cl.
From IV From III From II From I
® Cl -¬ CH 2 CH 2 O - + H +
Cl -¬ CH 2 CH 2 OH ¾¾ most stable conjugated more substituted Least stable
Stronger acid - ve charge on O alkene (terminal alkene)
dispersed, hence 10. (a) The compound which produces more stable conjugate
conjugate base stable
alkene will be most readily dehydrated in acidic
conditions.
® CH3 ®- CH 2 O - + H +
CH3CH 2 OH ¾¾ Thus (a) and (c) can be the choice. Further, the
Weaker acid - ve charge intensified, carbocation from (a) is more stable than the carbocation
hence conjugate from (c), hence (a) is more readily dehydrated.
base unstable
O O
5. (d) Oxidation of phenol by K2S2O8 is an example of Elbs +
persulphate oxidation. +
6. (d) Electron donating groups (– OCH3, – CH3 etc.) tend to From (a) stable From (c) unstable due to
+ve charge on adjacent C atom
decrease and electron withdrawing groups (– NO2, –
Cl) tend to increase the acidic character of phenols. 11. (b) It is a nucleophilic substitution reaction, 1-phenyl -1-
Since – OCH3 is more powerful electron-donating group propanol will be most reactive because of formation of
more stable benzyl type of carbocation.
than – CH3 group, therefore, p-methylphenol is
slightly more acidic that p-methoxyphenol, while p- OH OH
nitrophenol is the strongest acid. Thus, option (d),
C6H5CH2CHCH3 C6H5CHCH2CH3
i.e. p-methoxyphenol, p-methylphenol, p-nitrophenol is
1–phenyl–2–propanol 1–phenyl–1–propanol
correct.
7. (d) C6H 5
C6H 5CH2CH2CH2OH
OH OH CH3CHCH 2OH
Br 3–phenyl–1–propanol
Br 2–phenyl–1–propanol
Br / H O
8. (c) ¾ ¾2¾ ¾
2¾®
12. (c) Condensation of phenol with formaldehyde is an
CH3 CH3
electrophilic substitution reaction. Base converts
Br phenol into phenoxide ion which, being more reactive,
reacts easily with CH2 = O (a weak electrophile).
9. (b) The ease of dehydration can be determined by seeing
the stability of carbocation as intermediate. O
– O
H
Å d+ d– –
CH 3 - CH 2 - CH 2 - CH 2 + H2C = O CH2O
(I)

Å –
CH 3 - CH 2 - CH - CH 3 O
(II) H 2O CH2OH

Å Å
CH 2 = CH - CH - CH3 In presence of acid, CH2 = O (a weak electrophile) is
(III)
+
(IV) protonated to CH2 = O H (a strong electrophile) which
(IV) is most stable due to resonance followed by (III) easily reacts with phenol (a weak nucleophile).
which is allylic carbocation. Next is (II) as it is a +
OH
secondary carbocation and least stable is (I) as it is a OH
primary carbocation. H
+
Alternatively, ease of dehydration can be determined + CH2 = OH ¾® CH2OH
from the stability of the product formed.
OH
H O
CH2OH
2
¾®
 EBD_7374
640 CHEMISTRY

OH OH
–
D OOC D DOOC D
13. (c) ¬¾® ¾¾
® D+
¾®
+
+

3° 3° allylic (more stable) 15. (b) Heavy metal ions, particularly Ag+, catalyse S N1
– reaction because of presence of empty orbital.
OD O
+ +
14. (c) H D H D CH3 CH2Br + Ag [CH3CH 2 .... X .... Ag]
NaOH
¾¾® ¬¾
® slow + OH –
¾® CH3CH 2 ¾¾® CH3CH 2OH
(–AgX) from H 2O

O O
–
H.. D CO 2 – H D
¾® OOC ¾®
(C-D is stronger than C – H)
 26. ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

27. (b) When benzaldehyde is refluxed with aqueous alcoholic

Exercise - 1
potassium cyanide, two molecules of benzaldehyde
2 1
condense together to form benzoin
1. (b) CH3 – CH – CHO H O
3 4 KCN (alc.)
CH2 – CH3 —C +C—
D
O H
O CH3
1 2 || 3| 4 H O
2. (c) CH 3 - C - C H - CH 3 — C– C —
3-methyl-2-butanone
OH
CH3CH2 – C – CH – CH3 Benzoin

O CH3 O
(- H O )
3. (c) 4. (a) 28. (b) CH3–C=O + H2N–NH–C–NH2 ¾ ¾ ¾
2 ¾®

5. (b) O is more electronegative than C. H

6. (a) 7. (d) O
8. (a) H CH3 H O CH3– CH=N–NH–C–NH2
CH3
O3
CH 3– CH 2– C C CH3– CH 2– C– C Acetaldehyde semicarbazone
CH3 29. (d) Iodoform test is exhibited by ethyl alcohol, acetaldehyde,
CH3 O O acetone, methyl ketone and those alcohols which
O O possess CH3CH(OH)-group. As 3-pentanone does not
CH 3– C – CH 3 + CH3 – CH2 – CHO (–H O) contain CH3CO - group, therefore it does not give
2
9. (c) 10. (b) 11. (b) 12. (b) 13. (d) iodoform test.
14. (b) Formyl chloride is unstable at room temperature.
O
15. (a) Alkanenitriles (other than methanenitrile) benzonitrile
give ketones with Grignard reagents. C–CH3 CH2–CH3
16. (b)
30. (b) Zn-Hg/HCl
CH3 CHCl2 CHO ¾¾¾¾¾®
Cl2/hu H2O
17. (b) 373 K
Phenyl methyl Ethyl
Toluene Benzal chloride Benzaldehyde ketone benzene
18. (a) Primary alcohols on oxidation give carboxylic acids as This reaction is known as Clemmensen's reduction.
the final product, of course through aldehydes.
31. (d) Compounds having – CHO group reduce Tollen’s
Oppenauer oxidation involves oxidation of 2º alcohols
reagent to silver mirror. It is called silver mirror test.
to ketones, and not for the oxidation of 1º alcohols.
19. (d) O O
20. (c) Propanone has symmetrical structure. || ||
H - C - OH CH3 - (CHOH) 3 - C - H
21. (a) 22. (d) 23. (d)
24. (d) Cannizzaro reaction is given by aldehydes having no (a) (b)
a-hydrogen atom in the presence of conc. alkali, aldol O
condensation is given by aldehydes and ketones
having at least one a-atom in presence of alkali or in Both (a) and (b) have – C – H group so both of them
presence of acids give positive silver mirror test.
25. (b) Aldehydes containing no a-hydrogen atom on 32. (b) Tollen’s reagent is ammonical AgNO3. Aldehydes form
warming with 50% NaOH or KOH undergo silver mirror with it and ketones do not show any
disproportionation i.e. self oxidation - reduction known change. So Tollen’s reagent is used to distinguish
as Cannizzaro’s reaction. between aldehydes and ketones.
50% NaOH
2 HCHO ¾¾ ¾ ¾¾® HCOONa + CH 3OH 33. (a) Wolf- Kishner reduction
(i) NH2 – NH2 H
26. (d) I2 and Na2CO3 react with acetophenone (C6H5COCH3) C=O C
to give yellow ppt. of CHI 3 but benzophenone (ii) KOH H
(C6H5COC6H5) does not and hence can be used to 34. (c) Only aldehydes and ketones react with
distinguish between them. 2, 4-dinitrophenylhydrazine.
 EBD_7374
642 CHEMISTRY

O OH 40. (a) When acetaldehyde is treated with alcohol in the

|| HCN
| presence of dry HCl , then acetal is formed
35. (b) CH3 - C - H ¾¾¾® CH3 - C - H CH 3 OR
Acetaldehyde | CH 3
CN C= O + ROH ¾dry HCl
¾ ¾¾® C
OH H H OH
| Hemiacetal
Hydrolysis
¾¾¾¾¾® CH3 - C - H
|
CH 3 OR
COOH
ROH
Lactic acid H2O C
+
36. (d) HCHO does not undergo iodoform test, while H OR
acetaldehyde undergoes iodoform test (I2 in presence Acetal
of base) to form yellow precipitate of iodoform. 41. (a) Aldehydes and ketones having at least one a-hydrogen
37. (c) Iodoform test is given by compounds which have atom in presence of dilute alkali give b-hydroxy
CH3CO group. aldehyde or b-hydroxy ketone
O O OH
||
CH 3 - CH 2 - CH 2 - C - CH 3 dil. NaOH
CH3 – C + HCH2CHO CH3 – C + CH2 – CHO
2-Pentanone
H H
O Acetaldehyde Aldol
||
CH 3 - CH 2 - C - CH 2 - CH 3 D
CH3 – CH = CH.CHO
3-Pentanone –H2O
Crotonaldehyde
Q 2-pentanone has CH3CO group, so it gives iodoform
42. (a) Aldehydes, other than formaldehyde, when treated
test, while 3-pentanone does not have CH3CO group,
with RMgX give 2º alcohols.
so it does not give iodoform test.
38. (c) In cross aldol condensation aromatic aldehydes or O
ketones (with or without a-hydrogen) react with 43. (a) R C H + NH2 NH2 R C N NH2
aldehydes, ketones or esters having a-hydrogen atoms H
in the presence of dilute alkali to form a b-unsaturated Aldehyde Hydrazine Aldehyde hydrazone
carbonyl compound.
Example, O OH
|| |
HCN
OH - 44. (a) R– C –R ¢ ¾¾¾® R-– C — CN
(i) C6 H5CHO + CH3CHO ¾¾¾® KCN |
Benzaldehyde Acetaldehyde R ¢ (A)
C6 H5CHOHCH 2 CHO
OH
– H2O |
Reduction by
¾¾¾¾¾¾
® R – C – CH 2 NH 2
C6 H 5 CH = CHCHO LiAlH 4 (B) |
Cinnamaldehyde R¢
CH3 O 45. (d) Iodoform test is given by compounds having CH3CO–
| P group or secondary alcohols having CH3– as one of
(ii) C6 H 5 - C = O + H 3C - C - C 6 H 5 alkyl groups, i.e., CH3CHOHR or CH3CH2OH because
Acetophenone it is readily oxidised by halogen (present in reagent) to
CH3 O H
| P |
Aluminium
¾¾¾¾¾® C6 H5 - C = CH - C - C 6 H5 CH3CHO which has CH3 - C = O group.
t-butoxide
Dyprnone
46. (d)
R R OMgX 47. (a) Aldehydes (e.g. CH3CHO) restore the pink colour of
39. (c) C = O + R'MgX C Schiff’s reagent.
R R R' fusion
48. (a) C 6 H 5 COC 6 H 5 + KOH ¾¾¾¾
®
HOH
C6 H 6 + C 6 H 5COO - K +
R
R C – OH + Mg(OH)X 49. (c) The nucleophile is SO32 – not HSO3– , SO3Na
R' 50. (c) Wolf-Kishner reduction is reduction of carboxyl
3° Alcohol compound into alkane.
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 643

51. (d) 52. (c) Reimer-Tiemann reaction :

53. (d) These reactions lead to replacement of oxygen atom New C–C bond
of carbonyl group to form hydrazones and oximes. OH OH
54. (a) Cannizzaro’s reaction is shown by aldehydes lacking CHO
CHCl3
a-H-atom. Aldol condensation reactions are shown ¾ ¾® + 3KCl + 2H2O
3KOH
by aldehydes having a-H-atoms.
55. (b) NaBH4 selectively reduces the aldehyde group to Wurtz Fittig reaction :
alcohol without affecting double bond in an organic
compound. So, X is NaBH4. H3CCl + 2Na + Cl Na
¾¾®
NaBH
C6 H5 CH = CHCHO ¾¾¾¾ 4®

C6 H5 CH = CHCH2OH
H3C + 2NaCl
56. (a) Benzaldehyde undergoes Cannizzaro reaction, which
forms benzoic acid and benzylalcohol as the product.
New C–C bond
57. (b) 66. (c) (a)
58. (b) Carbonyl compounds have substantial dipole moments + +
and are polar in nature. The high polarity of the C = O + H2NNH2
H
C – OH
H
C = NNH2
carbonyl group is due to resonance.
59. (a) Aldehydes are generally more reactive than ketones in NHNH2
nucleophilic addition reactions due to steric and (b) In the reduction of carbonyl group with LiAlH4 or
electronic reasons. Sterically, the presence of two NaBH4, a hydride ion is transferred from the metal
relatively large substituents in ketones hinders the to the carbonyl carbon (nucleophilic addition).
approach of nucleophile to carbonyl carbon than in H
aldehydes having only one such substituent. – –
Electronically, aldehydes are more reactive than C = O + H– AlH3 C – OAlH3
ketones because two alkyl groups reduce the
67. (b)
electrophilicity of the carbonyl carbon more effectively
68. (d) Being reversible reaction, the backward reaction i.e.
than in former.
acetal -hemiacetal step can be restricted by minimizing
60. (b) The hydrogen atom that is added to the carbonyl water content, i.e. by using dry HCl. The step hemiacetal
carbon of the aldehyde in the reduction is derived - aldehyde can be restricted by using excess of alcohol.
directly from the other aldehyde molecule as a hydride 69. (c) First step in Cannizzaro reaction is the nucleophilic
ion. The second hydrogen that is added to the addition of OH– on the carbonyl carbon.
negatively charged oxygen is coming from the solvent H H
(consult mechanism of Cannizzaro reaction). Oxidation –
OH –
of one molecule of the compound at the expense of R–C=O (fast) R–C–O
other molecule of the same compound is known as OH
disproportionation. Higher the electron deficiency on cabonyl carbon, more
61. (c) 62. (d) easier will be the attack of the nucleophile
63. (b) In structure II, presence of positive charge on oxygen (OH–) on its carbon. Futher, the attack of OH– on the
causes the displacement of p electrons toward oxygen, carbonyl carbon is more easy in case of HCHO because
making carbon more electron deficient than that in its carbon is least hindered having two hydrogens
unprotonated carbonyl group. (steric effect). Thus the intermediate I is formed very
64. (c) With ammonia, HCHO forms hexamethylenetetramine, easily which donates hydride ion to another aldehyde
CH3 CHO gives acetaldehydeammonia addition and thus itself oxidised.
product, while C6H5CHO gives hydrobenzamide. H
65. (d) Aldol condensation : |
H - C = O + OH -
Ist
¾step
¾®
OH New C–C bond Easier because of electronic
OH
– and steric effects
2CH3CHO ¾¾® H3C–C–CH2CHO
H H H H
Kolbe reaction : – R–C=O –
H–C–O 2nd Step
H–C=O +R–C –O
ONa OH New C–C bond (slow)
COOH OH OH H
CO 2,140ºC I
Pressure
 EBD_7374
644 CHEMISTRY

70. (c) 2CH3CHO ¾ ¾® 1st Product, 77. (a) Because of resonance in benzaldehyde which is not
possible in case of acetaldehyde, the positive charge
2 CH 3 CH 2 CHO ¾¾® 2 nd Product
on the carbonyl carbon decreases and hence there is
a
® 3rd Product;
CH3CH 2CHO + CH3CHO ¾¾ decrease in reactivity.
a 78. (c) Acetal formed upon reaction of ethylene glycol and
th HCl, which is unaffected by base hence unwanted
CH3 C H 2 CHO + CH 3CHO ¾¾ ® 4 Product
71. (d) Aldehydes which contain a-hydrogen on a saturated reaction does not occur due to presence of carbonyl
carbon, i.e., CH3CH2CHO undergo aldol condensation. group.
79. (c) 2, 2-Dimethyl propanal gives Tollen’s test and
H CH3
| | 3-methylbutan-2-one gives iodoform test.
CH3CH 2 – C = O + H - C - CHO 80. (d)
Propanal |a
81. (b) Both C–O bonds are identical and each O possesses
H
partial negative charge.
H CH3
b| a|
OH
OH -
¾¾¾® CH3CH 2 - C - CHCHO
| 3 1
OH 82. (a) H3C 2 COOH
3-Hydroxy-2-methylpentanal 6 4
5 CH3
72. (c) H3 C d- d+
IUPAC name of the structure is 3-ethyl-2-hydroxy
C = O + CH 3 - MgI ¾¾® -4-methylhex-3-en-5-ynoic acid.
H 3C 83. (c) 84. (d)
85. (d) Primary and secondary alkyl groups are oxidised to
H3 C give carboxylic acid, while tertiary alkyl group remains
H OH H2O
C O MgI ¾¾¾® unaffected.
H3 C 86. (b) Grignard reagent forms addition product with bubbled
CH3 carbon dioxide which on hydrolysis with HCl yields
CH3 benzoic acid.
|
H3C- C-OH + Mg(OH)I O
|
CH3 MgBr C OMgBr
+
(i) CO2 H3O
Tert butyl
alcohol

73. (d) Ketones do not respond to Tollen’s test. Aldehydes

respond to Tollen’s test. O
74. (b) R R OH C O H
HCN NH3
C = O ¾¾® C ¾¾®
R R CN + Mg(OH)Br

NH2 NH2 'P'

R R
HOH Benzoic acid
C C -
CN NaOH
R CN R COOH 87. (c) R - X ¾¾ ¾® R - CN ¾¾¾¾
® RCOONa
75. (b) The carbon atom of the carbonyl group of benzaldehyde A B
is less electrophilic than carbon atom of the carbonyl H O
group present in propanal. The polarity of the carbonyl 88. (b) (C6 H5CO)2 O ¾¾¾
2 ® 2C H – COOH
6 5
Benzoic anhydride Benzoic acid
group is reduced in benzaldehyde due to resonance
and hence it is less reactive than propanal. H O
C6H 5COOCOCH3 ¾¾¾
2 ® C H COOH + CH COOH
6 5 3
76. (b) Aldehydes and ketones react with hydrogen cyanide Bezoyl ethanoic Benzoic acid Ethanoic acid
(HCN) to yield cyanohydrins. This reaction occurs very anhydride
slowly with pure HCN. Therefore, it is catalysed by a 89. (c) Formic acid cannot be prepared by Grignard reagent.
base and the generated cyanide ion (CN– ) being a
90. (a) Grignard reagents and nitriles are useful for converting
stronger nucleophile readily adds to carbonyl
alkyl halide into carboxylic acids having one carbon
compounds to yield corresponding cyanohydrins
atom more than that present in alkyl halides.
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 645

91. (c) An alkyl group attached to benzene ring can be 103. (d) The yield of product in a reversible reaction can be
oxidised only when it contains at least one a-hydrogen increased by (i) removing one of the products, (ii)
atom. Thus here –CH3 group is oxidised and Me3C– taking either of the reactant in excess.
group not. However, Me3C– group may cause oxidation
104. (d) Use of SOCl 2 and ClCOCOCl forms gaseous by-
of the benzene ring to –COOH.
products which can be easily removed, giving better
92. (b) 93. (d) yield of RCOCl. Further, oxalyl chaloride is particularly
94. (b) Due to intermolecular H-bonding. easy to use becasue any excess of it can be easily
95. (c) evaporated due to its low b.p. (62ºC)
96. (d) In carboxylates (conjugate base of carboxylic acids), O O O
resonance is more significant because the two || || ||
resonating structures are similar, while in phenoxide, R - C - OH + Cl - C - C - Cl ¾¾
®
the resonating structures are not equivalent, alkoxide
O
ions do not show resonance. ||
R - C - Cl + HCl ­ + CO ­ +CO 2 ­
97. (a)
105. (a) Salicylic acid, because it stabilizes the corresponding
O CH3
|| | salicylate ion by intramolecular H-bonding.
98. (c) CH 3 - C - OH + HO– CHCH 3 ¾¾
® 106. (b)
Ethanoic acid Propan-2-ol
107. (c) If the aldehyde has a boiling point less than 100°C, it
O CH3 can be prepared by the oxidation of 1° alcohols with
|| | regular oxidising agents like acidic permanganate or
CH3 - C - O– CHCH3 dichromate. Since the aldehyde has a lower boiling point
than the alcohol, it is distilled off as soon as it is formed
99. (c) pKa = –logKa; HCOOH is the strongest acid and hence
; so further oxidation to a carboxylic acid is minimized.
it has the highest Ka or lowest pKa value.
100. (b) LiAlH4 in presence of ether can be used to convert 108. (b) First two steps of the esterification make the question
acetic acid into ethanol. clear.

ether
CH3COOH + 3LiAlH4 ¾¾¾® O OH
+

+
Acetic acid H R–O–H
CH3 — C — OH CH3 — C — OH
[CH3CH2O]4AlLi + 2LiAlO2 + 4H2 Protonated acid
(carbonyl C is more
+ electrophilic than
[CH3CH2O]4AlLi ¾H
¾
¾® CH3CH2OH that of parent acid)
Etha nol

COOH COOC2H5 OH
R–O–H
CH — C — OH CH3 — C — OH
101. (c) HCl
+ C2H5OH ¾¾®
dry + H2O Protonated acid +
Ethanol HO R

This process is known as esterification. 109. (b)

102. (a) –COOH group when attached to benzene ring
110. (a) An electron releasing substituent (+I) intensify the
deactivates the ring and substitution occurs at
negative charge on the anion resulting in the decrease
m-position. (HNO3 + H2SO4) is a source of + NO2
of stability and thus decreases the acidity of the acid.
(electrophile) which attacks at m-position.
Hence acid character decreases as the + I-effect of the
COOH alkyl group increases as
COOH
CH3– < CH3CH2– < CH3CH2CH2– < CH3CH2CH2CH2–
H2SO4
+ HNO3 ¾¾¾¾ ® Hence the order becomes : (i) > (ii) > (iii) > (iv)
NO2
111. (b)
3-Nitrobenzoic acid
 EBD_7374
646 CHEMISTRY

COCH3
C 6H 6
112. (a) CH3COOH +PCl5 ¾¾® CH3COCl Anhyd. AlCl3
[A]

OH OMgBr
H+ MgBrC2H5
C2H5 – C – CH3 C2H5 – C – CH3
ether (hydrolysis)

(C)

113. (a)
Exercise-2
114. (c) Electron withdrawing substituent (like halogen, —NO2,
C6H5 etc.) would disperse the negative charge and 1. (b) But-1-yne on reaction with water in presence of Hg2+
hence stabilise the carboxylate ion and thus increases ions as a catalyst produces butan-2-one.
acidity of the parent acid. On the other hand, CH2 CH Hg2+ CH2 CH2
electron-releasing substituents would intensify the ¾¾®
H2 O CH3 C
negative charge, destabilise the carboxylate ion and CH3 C
thus decrease acidity of the parent acid. But–1–yne OH
Electronegativity decreases in order Tautomerism CH2 CH3
¾¾¾¾¾¾ ®
F > Cl > Br
CH3 C
and hence –I effect also decreases in the same order,
therefore the correct option is O
Butan-2-one
[FCH2COOH > ClCH2COOH > BrCH2COOH > 2. (a) The carbonyl group in ketones being influenced by
CH3COOH] two alkyl group is less reactive than in aldehydes
115. (d) V is most stable because its anion is stabilized to a where the carbonyl group is under the influence of
greater extent through H – bonding with H atom of OH one alkyl group only. As the number of alkyl group
present on both ortho-positions ; followed by II in increases both the +I effect and the steric hinderance
which one OH group is present. Compound IV comes get increases preventing the attack of nucleophile.
next to II because here –OCH3 group is present in ortho Now among benzaldehyde and acetaldehyde former
position which although is not capable of forming is less electrophilic than carbon atom of carbonyl group
H–bonding yet more acidic than p-HOC6H4COOH (III) present in ethanal. The polarity of carbonyl group is
due to ortho effect. Compound III is less acidic than reduced in benzaldehyde due to resonance hence it is
benzoic acid because of electron-releasing group in less reactive than ethanal.
the para position. Thus 3. (c) Due to the electron withdrawing characteristic of –Cl,
chloroacetic acid is more acidic than acetic acid further,
COOH COOH in phenol phenoxide ion obtained on ionisation of
HO OH OH phenol is stabilised due to resonance where as no
> > such stabilisation occurs in case of ethanol. Hence
phenol is stronger acid than ethanol. Thus acidic
V II
strength increases in the order.
ethanol < phenol < acetic acid < chloro acetic acid
4. (b) Compound Ph — COO — Ph can be prepared by the
COOH COOH COOH reaction of phenol & benzoyl chloride
OCH3 O
||
> > O C
OH || O
IV I Cl N
OH +
III
Phenol Benzoyl
chloride
This an example of Schotten-Baumann reaction.
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 647

5. (c) Acetone and benzaldehyde both do not react with 12. (a) Clemmensen reduction is used to convert carbonyl
Fehling's solution. group as follows
6. (d) Cannizzaro reaction is given by those aldehydes which Zn (Hg )+ HCl
C = O ¾¾¾¾¾¾ ® CH2
have absence of a-hydrogen atom. So, CH3CHO will
not give Cannizzaro reaction. Zinc amalgam and HCl act as reagent in this reaction.
13. (d) Any substituent in the carbonyl compound that
7. (b) Benzaldehyde having no a-hydrogen on reaction with increases the positive charge on the carbonyl carbon
aqueous KOH solution undergo Cannizzaro reaction will increase reactivity towards nucleophilic addition.
and produces benzyl alcohol and potassium benzoate.
NH
14. (a) CH 3COOH ¾¾¾
3 ® CH CONH
3 2
–+ Ethanoic acid
D
(A)
CHO CH2OH COOK
Ethanamide

Br / NaOH NaNO /dil.HCl

KOH (aq ) ¾¾¾¾¾
2 ® CH3 NH 2 ¾¾¾¾¾¾¾
2 ® CH 3OH
¾¾¾¾¾ ® + (B) (C)
benzaldehyde Benzyl Potassium Methanamine Methanol
alcohol benzoate 15. (b) Aldol formed in aromatic aldehydes itself loses water
8. (d) Chemical reaction can be shown as molecule without heating because double bond formed
is more stable due to conjugation with benzene ring.
OH H C 6 H 5 CH=CHCHO is commonly known as
| |
40% H 2SO4 cinnamaldehyde.
CH3 — C º CH ¾¾¾¾¾® CH3 — C = C H
1% HgSO4
Propyne Prop-1-en-2-ol O
||
O OH O - C - CH3
||
Keto-enol tautomerism
¾¾¾¾¾¾¾¾¾ ® CH3 — C— CH 3 16. (a) A = B=
Acetone
COONa COOH
9. (b) Chemical reaction can be shown as Aspirin
( i ) CH 3MgBr (Acetyl salicylate)
H SO ,D
CH3CHO ¾¾( ii¾ ¾¾¾
) H 2O
® CH3 — CH— OH ¾¾ 2¾ ¾
4
¾®
Ethanal | Dehydration LiA1H PCl
17. (c) 4 ® CH CH OH ¾¾¾
CH3 COOH ¾¾¾¾ 5®
CH3 3 2
(A)
Propan-2-ol
(A) alc.
CH3CH2Cl ¾¾¾
KOH
® CH2 = CH2
Hydroboration (B) (C)
CH3 — C = CH2 CH3 — CH2 — CH2OH
| propan -1-ol
18. (a) CF3 COOH > CCl3 COOH > HCOOH > CH3COOH
H (Ka order)
Propene
(C)
The halogenated fatty acids are much stronger acids
(B) than the parent fatty acid and more over the acidity
10. (c) among the halogenated fatty acid increases almost
proportionely with the increase in electronegativity of
O the halogen present. Further formic acid having no alkyl
|| group is more acidic than acetic acid.
I2 / NaOH solution
CH3 — CH = CH — CH 2 — C— CH 3 ¾¾¾¾¾¾¾ ¾® OH
( Iodoform reaction ) +
H –H O
Hex - 4 - en - 2 - one CHO ¾ ¾® CHO ¾ ¾®
2

19. (d)
O I
|| OH
CH3 — CH = CH — CH 2 — C— OH CHO
–H O
CHO
CHO
Pent -3-en -1-oic acid or CHO

11. (b) 2° alcohols on oxidation with alkaline KMnO4 solution

Conjugated system (stable)
produce ketones.

[O ] CH3 2 .
¾¾¾¾®
KMnO 4
O
OH Butan-2-one It does not lose water because the double bond so
Butan-2-ol
formed will be isolated.
(2° alcohol)
 EBD_7374
648 CHEMISTRY

20. (b) It does not give iodoform test due to absence of group. and then with zinc and acetic acid, oxidative cleavage
It also does, not give Tollen’s test. leads to keto - aldehyde.
On reduction it gives n-pentane
CH3 CH3
reduction
H3C—CH2—C—CH2—CH3 ¾¾¾¾® O
Zn-Hg/HCl O3,- 78° C
(i)
¾¾¾¾¾¾¾ ® O C–H
O (ii) Zn- CH 3COOH
CH 3—CH 2—CH2—CH 2—CH 3
n-pentane CH3 CH3
21. (d)
5- keto – 2 – methylhexanal
22. (d) Enolic form of ethyl acetoacetate has 18 sigma and 2
28. (d) Keto-enol tautomerism is possible only in those
pi-bonds as shown below:
aldehydes and ketones which have at least one a-
H H hydrogen atom, which can convert the ketonic group to
s s s
the enolic group.
s s s
H C C p C s
C p
O 29. (a) Schiff base is formed when 1° amine reacts with
s s H H aldehydes.
s
H Os H s s
s R R
Os C C H H+
s
s
s C = O + R' — NH 2 ¾¾¾ ® C = N – R'
H H H H
Aldehyde primary amine Schiff base
30. (d) Structures of given aldehydes
O
|| CH 3CH 2 CHO
H+
23. (b) R — C— R ¢ + NH 2 — NH 2 ¾¾¾
® propanal
Cl3CCHO
NH2 trichloroethanal
OH N HCHO
methanal
H2O
R—C—R¢ ¾¾¾¾¾ ® R—C—R¢ CH 3CHO
Elimination
ethanal
NH—NH2
(Addition)
CHO
While in all other case no elimination take place.
24. (a) Among the substituent attached to the benzene ring, benzaldehyde
–NO2 group is the most electron withdrawing, thus Trichloroethanal, methanal and benzaldehyde do not
withdraws electron density from carbonyl carbon thus undergo aldol condensation. Aldol condensation is not
facilitate the attack of OH– ion. given by aldehydes and ketones which do not contain
a-hydrogen atom(s).
O 31. (a)
COOH C – Cl 32. (b)
33. (b) Since 'A' gives positive silver mirror test therefore, it
25. (c) SOCl2 must be an aldehyde of a-Hydroxyketone. Also,
reaction with OH– i.e., aldol condensation (by assuming
Br Br alkali to be dilute) indicates that A is aldehyde as aldol
reaction of ketones is reversible and carried out in
O NH2 special apparatus. It indicates that A is an aldehyde
C NH2 CH 3 - CHO CH3 CH2OH
(A) (X)
NH 3 NaOH
¾¾ ¾® O
+Br2
Br Br CH3 - CH = N - NH - C - NH 2 CH3 - CH = CH - CHO
(Z) (Y)
26. (d) Benzaldehyde is less reactive than ethanol towards Semicarbazone But-2-enal
nucleophilic attack. The combined effect of –I and +R
effect of phenyl group is electron donating which O O
increases the electron density on the carbon atom of H –
the > C = O in benzaldehyde. (i) OH
¾¾®
+ H
||

34. (a) (ii) D

27. (d) When 1, 3-dimethylcyclopentene is heated with ozone
O
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 649

35. (a) only those compounds which have a-H give Aldol 38. (b) DIBAL-H is an electrophilic reducing agent. It reduces
condensation both ester and carboxylic group into an aldehyde at
O low temperature.
a || a O
(a) Cl3C CH (b) C 6 H 5 C H 2 CHO O OH O
(no a-H) (a-H)
a DIBAL - H
¾¾ ¾ ¾® H
(c) C 4H9 C H 2 CHO (d) CH3NO2
(a-H) CHO
CO2H
36. (b) 39. (c) Carboxylic acids have higher boiling points than
aldehydes, ketones and even alcohols of comparable
O O
molecular mass.
37. (a) H+/CH3OH
This is due to more extensive association through
[Ag(NH3)2]OH
intermolecular H-bonding.
Tollens reagent (esterification)
O ¼¼¼H O
CHO CO2H R C C R
HO CH3 O
O H ¼¼¼O
CH 3MgBr,

H+/CH3OH
H3C – C – CH3
C
OH O OCH3 40. (b)

O O O
C – CH3 C – CH2– + Br – Br C – CH2 – Br
Br
41. (a) ¾¾¾¾
2 ®
¾¾
®
NaOH

CH3 CH3 CH3

a-Halogenation of carbonyl compund by Br 2 in presence of alkali medium.

42. (a) CH3– C = CH – CH2 – C – CH3

| || Exercise-3
CH3 O 1. (c) It is an example of intramolecular aldol condensation
H /Pd/C
¾¾¾¾®
2 CH3– CH – CH2 – CH2 – CH – CH3
| | O O O
CH3 OH – O
OH
Total number of stereo isomers = 2 OH
O 2. (d) It is an example of intramolecular aldol condensation.
HO CH 2 NO 2
The carbon atom labelled as a acts as a nucleophile.
CH NO (i ) reduction
43. (c) ¾¾ ¾
3 ¾
¾2®
¾¾¾ ¾ ¾
¾®
C 2 H 5O - (ii ) diazotisat ion a
–
O OH O
+ H H
HO CH 2 - N º N O
O O
OH

–H2O
+ O
HO C H2 O
- N2 H+
¾¾¾® ¾¾ ¾¾ ¾ ¾
¾®
( Pinacol type of
rearrangement )
 EBD_7374
650 CHEMISTRY

–
OH O
d
(CH3CO)2O O d
–
3. (d) CH 3COONa d
+
d
+ O
(Perkin reaction)
CHO O O > >
o-Hydroxybenzaldehyde
O
III I II
OH OH O O
C=O 6. (b) The reaction is a part of haloform reaction.

O O
|| ||
4. (d) Aldol condensation : OH - –
CH3 - C - CH 2Cl ¾¾¾® CH3 - C - CHCl
C HCl
OH New C–C bond I
– O
OH ||
2CH3CHO H3C–C–CH2CHO -
or C H 2 - C - CH 2 Cl
H II
However, – I effect of –Cl makes the H’s of CH2Cl more
Kolbe reaction :
acidic, hence I is more likely to be formed.
ONa
ONa OH New C–C bond O
COOH ||
CO
CO2,140ºC
,140ºC H 3 C - C - CH 2 Cl
Pressure
Pressure
O O
|| ||
OH- - Cl2
Cl ¾¾¾® H3C - C - C H - Cl ¾¾¾
® H3C - C - CHCl2
OH
7. (c) (a)
CHCl3
Reimer-Tiemann reaction : + +
3KOH H H
C = O + H2NNH2 C – OH C = NNH2
NHNH2
New C–C bond
OH (b) In the reduction of carbonyl group with LiAlH4 or
CHO NaBH4, a hydride ion is transferred from the metal
CHCl to the carbonyl carbon (nuclephilic addition)
+ 3KCl + 2H2O
3KOH
H
Wurtz Fittig reaction : – –
C = O + H– AlH3 C – OAlH3
Na
H3CCl + 2Na + Cl 8. (c)
CH3 NH3 CH3 OH –H O CH3
2
C = O ¾¾® C ¾¾® C = NH
H3C + 2NaCl C2H5 C2H5 NH2 C2H5
–
New C–C bond – CH3 NH H O CH3 NH2
CN
¾® C ¾¾®
2
C
5. (d) The keto group has considerable resonance energy ;
C2H5 CN C2H5 CN
hence more the number of keto groups in a compound,
higher is its stability. However, here all the three 9. (b) The – CO part of the – COOC2H5 does not undergo
compounds have same (two) number of keto groups. nucleophilic addition, because it is not electron
Compound II is least stable because two adjacent keto deficient.
groups destabilize the molecule due to positive charge
O O
on the adjacent carbon atoms. Relative stability of I ..
and III can be ascertained by the stability of their fully CH3 C CH2 – C – OC
. . 2H5
reduced forms (phenols), since fully reduced form of
III has two benzene rings, it will be more stable than O O-
the I whose reduced form has only one benzene ring. || | +
Thus ¬¾® CH 3 - C - CH 2 - C = O
. . C2H 5
ALDEHYDES, KETONES AND CARBOXYLIC ACIDS 651

10. (c) Acetals are stable to OH–, while mercaptals are stable to H+.
11. (b) Reaction of 4,4-dialkylcyclohexadienone with an acid to form phenol with the migration of one of the alkyl groups to the
adjacent carbon is known as dienone-phenol rearrangement.

O OH OH OH OH
+
H+ migration of –H +
¾¾® ¬¾® ¾¾¾¾¾®
: R– R ¾®
+
+ H R
R R R R R R R R
–
migration of :R is due to ease with which 2°
carbocation is converted to 3°

12. (c) First three HCHO molecules react with acetaldehyde via crossed aldol condensation, while the fourth HCHO molecule
reacts via crossed Cannizzaro reaction.

O
||
Ca ( OH ) HCHO , Ca ( OH )
CH 3CHO + H - C- H ¾ ¾ ¾ ¾
¾2 ® CH 2 OH . CH 2 CHO ¾¾ ¾ ¾ ¾ ¾¾
2
®
Methanal ( crossed aldol ) ( crossed aldol )
Ethanal ( Two a - H )
(3 a - hydrogen ) ( no a - H ) condensation
.

CH2OH CH2OH
HCHO, Ca(OH) 2 HCHO, Ca(OH) 2 1
CH – CH2OH ¾¾¾¾¾¾®
(crossed aldol)
HOH2C – C – CH2OH ¾¾¾¾¾¾¾¾¾® C(CH 2OH) 4 + (HCOO ) 2 Ca
(crossed Cannizzaro) 2
CHO CHO
(1 a – H) (No a –H)

13. (d)
14. (c) OH– and –CH2CHO act as nucleophile in the first two steps.

O- OH
- | |
OH - CH3CHO H 2O
¾¾¾® CH3 CH
CH3 CHO ¾¾¾® C H 2CHO ¾¾¾¾¾
® CH 3C H
| (as an acid) |
CH 2CHO CH2CHO

O3, H2O CHO (O) COOH heat

15. (b) 2 CH2 CH2 CH3COOH
CHO COOH
 EBD_7374
652 CHEMISTRY

27. AMINES

Exercise - 1
O
1. (a)
2. (b) The fourth orbital of nitrogen in all amines contains an RX / DMF RNH 2
unshared pair of electrons. Due to the presence of NR
SN 2 reaction
unshared pair of electrons, the angle C–N–E, (where E
is C or H) is less than 109.5°. O
3. (c) RNH 2 R 2 NH R3N N-alkyl phthalimide
Primary amine Secondary amine Tertiary amine
4. (c) 1° amines have –NH2 group in their structure, 4 primary O
amines are possible for C4H11N.
OH
CH 3 - CH 2 - CH 2 - CH 2 NH 2 CH 3 - CH 2 - CH - CH 3 + H 2N - R
| OH Primary
NH 2 amine
(i) (ii) O
Phthalic acid
CH3 CH3
| | 16. (d) 17. (d)
CH3 - C - CH 2 - NH 2 CH3 - C - CH3 18. (d) Reduction with iron scrap and hydrochloric acid is
| | preferred because FeCl2 formed gets hydrolysed to
H NH 2
release hydrochloric acid during the reaction. Thus,
(iii) (iv) only a small amount of hydrochloric acid is required
5. (d) to initiate the reaction.
6. (b) The compound contains longest chain of 6C atoms 19. (b) 20. (c) 21. (a) 22. (a) 23. (d)
and amino group. Hence it is an alkanamine.
NaOH
24. (a) CH3CONH2 ¾¾¾¾ ® CH3 NH 2
CH3 C2H5 Br2
7. (a)
HC – N Hofmann bromamide reaction

CH3 C2H5 25. (a) The reaction is Hoffmann bromamide reaction

N, N- Diethylpropan - 2-amine O
||
8. (c) R - C - NH 2 + Br2 + 4NaOH ¾¾
®
9. (c) The compound is derivative of aniline.
10. (c) 11. (a) R - NH 2 + 2NaBr + Na 2CO3 + 2H 2O
12. (c) CH3NC (methyl isocyanide) on reduction with LiAlH4 O
gives secondary amine R – NH2 contains one carbon less than ||
O R - C - NH 2
|| 26. (b) Amines possess fishy smell.
13. (b) CH 3 - CH 2 - C - NH 2 + Br2 + KOH
gg 27. (c)
D
¾¾® CH3 - CH 2 - NH 2 28. (d) Amines are basic in nature
R - N ® C ¾¾¾® RNH - CH3
4[H] 29. (b) Lower aliphatic amines are soluble in water solubility
14. (d)
alkyl isocyanide secondary amine decreases with increase in molar mass of amines.
Higher amines are essentially insoluble in water.
O O 30. (a)
31. (a) Secondary amine is more basic than primary amine.
KOH
NK 32. (b) (CH3)3N < CH3NH2 < (CH3)2 NH < C2H5NH2
15. (c) NH
33. (a)
34. (a) Secondary amines are more basic than tertiary amines
O O due to stabilisation of 2° amine by hydrogen bonding
Phthalimide N-Potassium phthalimide with solvent molecule.
(a nucleophile)
AMINES 653

35. (c) Aliphatic amines are more basic than aromatic amines. electron withdrawing groups like –NO2, –SO3H,
Resonance decreases the basic character due to –COOH, –X decrease it.
delocalisation of shared pair of electrons on nitrogen
within benzene nucleus. Further electron withdrawing Å .. –
NH2 N º NCl
if (–NO2) decreases basicity.
36. (b) 55. (a) NaNO /HCl
2
¾¾¾¾¾¾
®
37. (c) Aryl amines produce diazonium salts on treatment with 0°C
nitrous acid Diazotisation
38. (c) We know that
Br
CH3CH 2 NH 2 ∗ CHCl3 ∗ 3KOH ¾¾↑
CH3CH2 NC ∗ 3KCl ∗ 3H 2O CuBr/HBr
¾¾¾¾¾
®
In this reaction, bad smelling compound ethyl Sandmeyer reaction
isocyanide (CH 3CH 2 NC) is produced. This equation
56. (b)
is known as carbylamine reaction.
39. (a) Acylation occurs in one step only because lone pair of 57. (a) HNO3 + 2H 2SO4 2HSO4- + NO2+ + H3 O+
nitrogen is delocalized with acyl group.
58. (a) Secondary amines are more basic than tertiary amines
O O–
due to stabilisation of 2° amine by hydrogen bonding
..
R – NH – C – CH 3 R – NH – C – CH 3 with solvent molecule.
HNO 59. (d) All aliphatic amines are stronger bases than NH3 and
40. (b) RNH2 ¾¾¾¾
2®
ROH + H2O + N2 ­ among different ethylamines order of basictity is
(A) (B) (C) 2° > 1° > 3°. Thus, the correct order is (d) i.e.,
41. (c) Since the organic amino compound on reaction with (C2H5)2 NH > C2H5NH2 > (C2H5)3N > NH3
nitrous acid at low temperature produces an oily This anomolous behaviour of tertiary ethyl amine is
nitrosoamine so the organic amino compound is a due to steric factors i.e., crowding of alkyl groups cover
secondary aliphatic amine.
nitrogen atom from all sides and thus makes the
Note : This reaction is used as a test for aliphatic amines
approach and bonding by a lewis acid relatively difficult
since no other class of amines liberates N2 gas on
which results the maximum steric strain in tertiary
treatment with HNO2.
amines. The electrons are there but the path is blocked
42. (a) 1° amines (aliphatic and aromatic) react with
resulting the reduction in its basicity.
CHCl3/KOH to yield isocyanide (foul smelling) This is
60. (a)
known as carbylamine test which is not given by 2°
and 3° amines.
61. (a) 3 2 (CH CO) O,Pyridine
43. (c) The compounds containing active H-atoms (H atoms NH2 ¾¾¾¾¾¾¾¾®
attached to N, O or S) react with CH3COCl to form
acetyl derivatives. (I)
44. (d) 45. (b) 46. (b) 47. (a) 48. (d)
49. (a) Hinsberg’s method is based on the use of benzene 4® (i) LiAlH
NH – C – CH3 ¾¾¾¾¾
sulphonyl chloride. (ii) H 2 O
50. (d) Aniline is insoluble in water, because its –NH2 group (II) O
can’t form H- bond with water due to bulky phenyl
group.
51. (d) NH – CH2 – CH3
52. (a) Pyridine is a stronger base than the amine, pyridine (III)
removes HCl formed in acylation reaction of amines
III > I > II
and shifts the equilibrium to the right hand side.
Amine (a 1° aromatic amine) (> C = 0 gp. causes
53. (b) The hydrogen attached to nitrogen in sulphonamide delocalisatrons of
is strongly acidic due to the presence of strong electrons on N)
electron withdrawing sulphonyl group. Hence, it is 62. (b) Greater the delocalisation of electron pair on N, lesser
soluble in alkali. is its availability for protonation leading to lesser basic
54. (d) In case of substituted aniline, electron releasing groups character.
like –OCH3, –CH3 increase basic strength whereas
 EBD_7374
654 CHEMISTRY

..
: NH2 CH2NH2 NH2
NH – CO – CH3

HNO
¾¾¾¾
3® H O∗
> > H 2SO 4 ¾¾3 ¾↑

IV II NO2
Delocalisation not Delocalisation not NO2
possible, cyclohexyl gp. possible, phenyl gp. is [Y] [Z]
is electron-releasing electron-withdrawing
NH2
H
:NH2 :N
66. (c) 3 CH COCl
¾¾¾¾¾
®

>
O O
I III
Delocalisation possible, more
in III than in I. Further C6H5– gp. is NH – C – CH3 NH – C – CH3
electron-withdrawing

63. (b) Although – NH2 group is o,p - directing but in presence Br - H O

2 2 ®
¾¾¾¾¾
of conc. HNO3 it undergoes protonation to form –
+
N H3 which, being electron - deficient, becomes Br
m- directing. (A) (B)

+ NH2
: NH2 NH3
conc. HNO3 conc. HNO3 H O+
3 ®
¾¾ ¾¾¾® ¾¾ ¾¾¾® ¾¾¾¾

– NH2 group is – NH3+ group is

o, p - directing m - directing
Br
+
N H3 (C)
67. (b)

NO2 NO2 NO2 NO2

Protonated
m - nitroaniline
HNO3 Fe/HCl
H2SO4
NO2 NH2
64. (b) CH2–NH2 compound is most basic due to
HNO2
localized lone pair of electrons on nitrogen atom while
other compounds have delocalized lone pair of
NO2 NO2
electrons.

NH2 NH – CO – CH3 –N2

H2 O + –
(CH3CO)2 O OH N2Cl
65. (b) ¾¾¾¾¾¾ ®

68. (a) It is a tertiary amine hence shows above observations.

[X]
AMINES 655

69. (d) The reaction can be completed as follows: 74. (b) The given reaction is known as Sandmeyer’s reaction.
–
N2+Cl OH
NH2
NaNO2/HCl CH3
N2Cl + N H O
(diazotisation) CH3 75. (b) ¾ ¾2¾® + N2+HCl
‘A’ ‘B’ N, N-dimethylaniline
(Aniline) Benzene
diazonium chloride cold CH3 CH3
p-Cresol
CH3
N=N N 76. (c) Primary aromatic amines react with nitrous acid to yield
CH3 arene diazonium salts.
‘C’ cold
p-dimethylaminoazobenzene ArNH2 + NaNO2 + 2HX ¾¾¾
®
1° Aromatic amine
Ar—N = N+X– + NaX + 2H2O
thatn sp3C
Arene diazonium salt

NH2 + -
The diazonium group can be replaced by fluorine by
N2 Cl treating the diazonium salt with fluoroboric acid
NaNO ,HCl (HBF4). The precipitated diazonium fluoroborate is
70. (b) ¾¾¾¾¾
2 ↑ isolated, dried and heated until decomposition occurs
(0,5↓C)
Diazonium chloride to yield the aryl fluoride. This reaction is known as
Aniline
Balz-Schiemann reaction.
71. (a) Excess of HCl is used to convert free aniline to aniline HBF heat
Ar—N2+X– ¾¾¾®
4 Ar—N2+BF4–¯ ¾¾¾ ®
hydrochloride otherwise free aniline would undergo
Ar—F + BF3 + N2
coupling reaction with benzenediazonium chloride.
77. (a) The yield in Sandmeyer reaction is found to be better
72. (a) Azo dye is prepared by diazo coupling reaction of
than Gattermann reaction.
phenol with diazonium salt.
78. (a) 79. (b) 80. (b)
–
N+2Cl OH Exercise-2

+ ¾® N=N OH 1. (b) 3° amine is the amine in which nitrogen is attached to

three alkyl groups whether they are same or different.
Benzene
p–Hydroxyazobenzene
diazonium
:

chloride

CH3CH2 N CH2CH3
(– N = N –) group is called azo – group.
CH2CH3
+ - Triethylamine
NH2 NºNCl (3° amine)

3 2 1
73. (d) NaNO 2,HCl CuCN 2. (d) IUPAC name ofCH 2 = C HC H 2 NHCH3 is
¾ ¾¾ ¾ ®
0°C N-methylprop-2-en-1-amine.
Aniline (diazotisation) (A) 3. (c) More the hydrogen bonding more will be the basicity in
benzene gaseous phase but in aqueous solution solvation effect
diazonium chloride also play the role. By combining both the effects order
of basicity in aqueous medium is 2° > 3° > 1° > NH3. The
inductive effect comes to play when order of amines is
CN CH2NH2
same as in case of (c) & (d) where both the amines are
secondary. +I group increase the basicity and –I group
LiAlH 4
will decrease the basicity of amines.
4. (a) In aniline, lone pair of nitrogen is not available for
(B) (C) donation to the acid as it is involved in the resonance.
Cyanobenzene Benzylamine Thus, it will act as the weakest Bronsted base amongst
the given compounds.
 EBD_7374
656 CHEMISTRY

+ + + 10. (d) LiAlH4 in ether is the best reagent for converting

NH2 NH2 NH2 NH2 NH2 2-phenylpropanamide into 2-phenylpropanamine
– – because LiAlH4 will reduce carbonyl group but does
– not reduce benzene ring.
I II III IV V O
5. (c) SN1 reaction involves the formation of carbocation, so, ||
more stable carbocation will have higher reactivity NH2 NH2
towards SN1 mechanism.
LiAlH in ether
r ¾¾ ¾ 4¾ ¾ ¾®
® C6 H5 – CH 2 + Br s
C6 H5CH 2 Br ¾¾
2-phenylpropanamide 2-phenylpropanamine
Å
As C6H5 C H 2 is the most stabilised carbocation due to 11. (b) Hoffmann bromamide reaction.
resonance, hence it will be most reactive towards SN1
O
mechanism. H3C ||
NH2 CH3
H2(excess)/Pt NH2
NaOH / Br2 CH — NH2
NO2
Fe/HCl
NH2
6. (b) 2-phenylpropanamide 1-phenylethanamine

Sn/HCl NH2 12. (b) Hoffmann bromamide degradation reaction:

O NH2
||
LiAlH4/ether NH2
No reaction Br / NaOH
¾ ¾2¾ ¾ ¾® + Na2CO3 + NaBr + 2H2O
7. (c) 1° amine with increased –CH2 group can be achieved Benzamide Aniline
by following the given steps: 13. (d)
KCN Na/C2O5H
X C ºN CH2NH2 NH2 NH2 NH2
alkyl –KX
s (1° amine)
halide (Nucleophilic (reduction of CN )
substitution of
s
alkyl halide by CN ) > >
8. (d) Potassium phthalimide is the source of nitrogen in
Gabriel phthalimide synthesis. CH3 NO2
O III I II
||
C Higher the electron density towards ring, higher will be
- H 2O
CO – +
NH + KOH (alc.) R–X
NK ¾¾¾®
its basic strength. Electron donating group increases
C CO the basic strength while electron withdrawing group
|| decreases the basic strength.
O
+ –
COOH 14. (c) CH3— NH2 + HNO2 CH3 — N2 Cl
CO H + / H 2 O, D
or + RNH 2 methylamine nitrous acid
N–R
HO - / H 2 O, D
CO COOH 1° amine H2O
Phthalic acid
9. (c) Reaction can be represented as
CH3OH
Methanol
R — NH2 + RCHO [R — N = C — R]
1° amine |
H HNO 2 + –
H /Pt
2 15. (b) CH3— NH2 CH3 — N º NCl
H methylamine
| D H2 O
R—N—C—R
| |
H H CH3OH + N2­
2° amine Methanol
AMINES 657

16. (c) For the nitration of benzene, NOÅ

2 acts as an O O O
|| || ||
electrophile (electrophilic substitution reaction). (
KOH alc. ) s+ R X + -
NH ¾¾ ¾¾¾ ® NK ¾¾ ¾¾¾® N— R
Step 1: H2SO4 ¾® H+ + HSO4–
|| || ||
+ O
+ O O
Step 2: H + H – O – NO2 H 2 O + NO2
NaOH/H2O
nitronium ion
O
NO2 || s+
NO2+ ONa
R – NH2 + s+
primary amine O Na
||
17. (c) Reduction of aromatic nitro compounds gives aromatic O

1° amine. 22. (d) Diazonium cation is a weak E+ so it will not react with
NO2 compound containing electron withdrawing group.
NH2
Fe / HCl Also, NO2 group is an electron withdrawing group thus,
¾¾ ¾¾® nitrobenzene will not undergo azo coupling reaction
Aromatic Aromatic with benzene diazonium chloride.
nitro compound primary amine 23. (c) Phenol has the least tendency to accept a proton and
also exhibit acidic character due to polar O – H bond
18. (b) Reactivity of a base towards dilute HCl is directly
hence, it is a weak Bronsted base.
proportional to the strength of the base.
24. (d) Pyrrolidine will be the strongest base as the lone pair
Thus, as (CH3)2NH has the highest basic strength, so it on nitrogen are not involved in resonance and are easily
will have highest reactivity. available for the donation. So, basic strength becomes
H 3C H high.
HCl H 3C Å –
N — H ¾¾ ¾ ® N + Cl s
H 3C H 3C H N
25. (a) H H
Most basic
R Amide ion is the most basic among the given species
Å
due to the presence of negative charge and two lone
O O O NH2 O –
·· pairs of electron on nitrogen atom. The species which
|| || R – N H2 || are having lone pair of electrons are more basic than
19. (a) R O R ¾¾ ¾ ¾® R O neutral species. So, NH3 and H2O are less basic than
Acid R
anhydride NH2– and OH–. Also, nitrogen is less electronegative
than oxygen hence it can easily donate e–s.
\ The correct order of basic strength will be:
O NH2– > OH– > NH3 > H2O
|| 26. (b) On comparison to amines, hydrocarbons have lower
Å –
R—N R + R — COO boiling point, hence they are more volatile whereas
amines are having higher boiling point due to H-bonding.
H H
NH 2
O 27. (d) N 2 Cl +
.. || H
R—N R + COOH
HAmide R N=N NH 2
20. (b) Gattermann reaction:
28. (b) Arene diazonium salts are most stable among the given
Cl options because of the dispersal of +ve charge on the
N +2 Cl- benzene ring due to resonance.
Cu / HCl
¾¾ ¾ ¾® + N2 + CuCl 29. (a)
Benzene diazonium Chlorobenzene 30. (d) R – CH2 – NH2 + CHCl3 + 3KOH (alc.)
chloride Carbylamine reaction
¾¾¾¾¾¾¾¾® R – CH2 – NC + 3KCl + 3H2O
21. (b) Gabriel phthalimide synthesis is the best method of Alkyl isocynide
preparing primary amines from alkyl halides without 31. (a) Arylamines are less basic than alkyl amines and even
changing the number of carbon atoms in the chain. ammonia. This is due to resonance. In aryl amines the
lone pair of electrons on N is partly shared with the
ring and is thus less available for sharing with a proton.
 EBD_7374
658 CHEMISTRY

In alkylamines, the electron releasing alkyl group 37. (a) C3H9N

increases the electron density on nitrogen atom and CH3—CH2—CH2—NH2
thus also increases the ability of amine for protonation. CH3 – NH – CH2 – CH3.
Hence more the number of alkyl groups, higher should
CH 3 — CH — CH 3 , CH 3 —N — CH 3
be the basicity of amine. But a slight discrepancy | |
occurs in case of trimethyl amines due to steric effect. NH2 CH3
Hence the correct order is 38. (a)
(CH3 )2 NH > CH3 NH 2 > (CH3 )3 N > C6 H5 NH 2 –
32. (d) Each of them decompose aqueous solution of NaHCO3.
NH2 N2+ Cl CN
Recall that when at least two NO2– groups are present
NaNO2 /HCl CuCN/KCN
in ortho and para positions with respect to phenolic ¾¾¾¾¾¾ ® ¾¾¾¾¾®
0 -5°C D
–OH group, it becomes highly acidic and gives
effervescences of CO2 with aq. NaHCO3 solution. CH3 CH3 CH3
33. (d) C6 H5 NH 2 + COCl2 ® C6 H5 NH.COCl
39. (b) Primary amines (aromatic or aliphatic) on warming with
D chloroform and alcoholic KOH, gives carbylamine
+ HCl ¾¾® C 6 H 5 NCO + HCl
having offensive smell. This reaction is called
34. (d) Because arylhalides do not undergo nucleophilic
substitution reaction with potassium phthalimide carbylamine reaction.
easily. NH2
CH3
D
35. (d) AlCl3 + CHCl3 + 3KOH
CH3Cl
N C
(Friedel Craft’s
Reaction)
+ 3KCl + 3H2O
H
O O
C=O 40. (a) Arylamines are generally less basic than alkylamines
O Base due to following factors
+
R R (i) Due to resonance in aromatic amines.
Perkin Reaction (ii) Lower stability of anilinium ion
41. (d) 42. (c)
O O
43. (b) 4 moles of NaOH and one mole of Br2 is required during
Ar OH + HO production of one mole of amine during Hoffmann's
bromamide degradation reaction.
R R
O
O êê
OH O R – C –NH2 + Br2 + 4NaOH ®
O – C – CH3
+ CH3 – C – Cl
O
Acetylation Reaction D
44. (a) CH3 - C - NH 2 + Br2 + 4NaOH ¾¾ ®
acetamide
NH2
Cl NaOH CH3 – NH2 + 2NaBr + Na2CO3 + 3H2O
+
methanamine
O
Schotten-Baummen Reaction It is called Hoffmann Bromamide reaction.R–NH2 +
Na2CO3 + 2NaBr + 2H2O
NH – C – 45. (c) – NO2 group has strong – R effect and –CH3 shows +R
O effect.
\ Order of basic strength is
36. (d)
NH2 NH2 NH2
NO2 HN—OH NH2
Electrolytic
rearrangement < <
reduction
(Strongly acidic
medium) NO2 CH3
nitrobenzene Phenyl 46. (a) 47. (a)
hydroxylamine OH
AMINES 659

48. (a) It is fact that aniline is better nucleophile than anilium

NO2 NO2 NO2
ion. Anilium ion contain +ve charge, which reduces
the tendency to donate lone pair of electron C6 H5 NH3+ + +
¬¾® ¬¾®
(Anilium ion). H H H
Y + Y Y
49. (c) Nitration takes place in presence of concentrated
HNO3 + concentrated H2SO4. (More stable due to less e– withdrawing effect of –NO2) greater no. of
resonating structures.
In strongly acidic nitration medium, the amine is
converted into anilinium ion (– NH3+); substitution is 54. (a) KCb of H5 C 2 – N > CH 3 – N
thus controlled not by – NH2 group but by – NH3+ N, N-Diethylethanamine
group which, because of its positive charge, directs
+ I effect of C2H5-group is more than CH3- group.
the entering group to the meta-position instead of ortho,
and para.
+
Exercise-3
: NH 2 NH 3
1. (b) LiAlH4 does not reduce –NO2 group to – NH2 group.
2. (b) Amalgamated -Zn and HCl reduces carbonyl group
conc. HNO
¾conc.
¾ ¾H¾SO
¾
3
® to methylene group without affecting the double
2 4
bond. However, Zn and HCl reduces –NO2 to –NH2
– NH2 gp : o, p-directing – NH3+ gp : m-directing group.
50. (c) Reducing reagent is needed, as shown in given 3. (a) In amines, N is sp3 hybridised and thus has pyramidal
reaction. shape. In the given structure, since the three alkyl
groups are different, and the fourth corner of the
pyramid is occupied by lone pair of electrons, the
NO2
molecule is chiral. However, the two enantiomers of
Zn OH the amine are not resolvable because of their rapid
aq. NH 4Cl
interconversion through a transition state having
51. (a) Schotten-Baumann Conditions planar structure (sp2 hybridised nitrogen)
4. (d) The basic character of an amine in water is determined
O O by (i) electron availability on the N atom and (ii) the
NaOH extent of stabilization of the cation (protonated amine)
R + H2N – R¢ R due to solvation by hydrogen bonding
Cl N – R¢
H OH2
H +
H +
The use of added base to drive the equilibrium in the CH3 N H CH3 N H OH2 ;
formation of amides from amines and acid chlorides. H H OH
2
+
Methyl amine Protonated methyl amine, CH 3NH 3
Na –
52. (c) C2H5OH ¾¾® C2H5O Na
+ (Highly stabilized)

(A) (B)

H OH2
PCl5 +
H +
CH3 N H CH3 N H OH2
C2H5Cl
(C) CH3 CH3
– S 2
C2H5O Na+ + C2H5Cl ¾¾®
N
C2H5OC2H5 Dimethyl amine Protonated dimethyl amine
+
(B) (C) (Lesser stabilized than CH 3NH 3)

So the correct option is (3) 5. (a) Note the point of difference in the given compounds
53. (d) –NO2 group is meta-directing group which here lies at b-carbon. In I, II, III, the b-carbon
NO2 NO2 atoms are sp3, sp2 and sp hybridised respectively
which in turn cause the difference in their s character.
+ We know that more is the s character of an atom,
¬¾®
+ greater will be its electron-withdrawing nature. Thus
Y H Y H sp (50% s character) hybridised carbon is most
(Less stable due to more e– withdrawing effect of –NO 2) electron-withdrawing, while sp3 (25% s character) is
 EBD_7374
660 CHEMISTRY

least electron-withdrawing. Further, we know that 8. (b) Reaction is an example of Schmidt reaction in which
presence of an electron-withdrawing group decreases carboxylic acids are heated with hydrazoic acid in
basicity of an amine. Thus presence of a mineral acid to form primary amines.
conc . H SO
NH2 > NH2 > b NH2 RCOOH + HN 3 ¾¾ ¾ ¾
2 ¾
¾4 ® RNH + CO
2 2
b b
3
I (b – C sp hybridised) II (b – C sp 2) III (b – C sp) 9. (d) Most of the simple amines those having smaller alkyl
6. (d) II is most basic because delocalisation of electron (groups) can’t be resolved , although they may contain
pair leads to negative charge on N making it electron- three different alkyl groups.
rich and hence liable to be attacked by proton very 10. (d) For this one should remember that Hofmann’s
easily. Moreover, the corresponding protonated degradation involves migration to electron deficient
species is very much stable because of equivalent nitrogen atom, hence the alkyl group will migrate with
contributing structures. its bonding pair of electrons.
.. –.. O O
NH .NH
. –
H
+
.. OBr .. OH
–

CH3 C CH3 C + R C NH2 R C NHBr

.NH
. 2 NH2 Amide

II
+ O O
NH2 NH2 . –. ..
CH3 C CH3 C R C .N. Br R C N
+ ..
NH2 NH2
(note that N is electron-deficient)
Species III is least basic because of delocalisation of .. H2O 2–
O C NR RNH2+ CO3
electron pair on N, making it less available for
Alkyl isocyanate Amine
protonation. Species I lies in mid-way, thus
11. (c) Remember that in Hofmann rearrangement, the two
O original H atoms of the –CONH2 group are removed
.. .. by base (OH–) and new H’s are derived from H2O.
CH3 C NH2 < CH3CH2 NH2

III I O
||
(i) OD – /Br
(CH3 )3 C - C - NH 2 ¾¾¾¾¾®
2 (CH3 )3 C - ND2
.. (ii)D2O
NH
.. 12. (c) The given amine has three b-hydrogens, hence it can
< CH3 C NH2 form three alkenes of which least substituted (H2C = CH2)
II will be the major product (Hofmann product or
Hofmann elimination).
7. (c)
b2 b1
(i) CH3I
S b3 (ii) Ag 2O
O (from b1)
< < NHCH 2CH3 (iii) heat
.. .. ..
N N N
H H H + + H2C = CH2
No delocalisation Presence of S O is more electronegative (from b2) (from b3)
of e pair (electronegative element than S, hence further
decreases e density decreases availability
on N) of e pair on N
In Hofmann elimination H atom (in the form of proton)
3
is eliminated from that b carbon atom which has
N is sp hybridised
maximum number of H atom(s). This is due to the fact
that Hofmann elimination (an example of E2 reaction)
< <
.. .. requires anti-coplanar arrangement of the b H atom
N N and the leaving group. Further, higher the chances
C for this arrangement to remain in staggered
2 H3C O
N is sp conformation more will be the ease of elimination.
hybridised e pair on N Thus greater the number of H atom at b position,
delocalised to O
higher will be the chances for Me3N+– and H atom to
AMINES 661

remain in this particular conformation (anti-coplanar 14. (d) The reaction involves Cope eliminiation (heating of a
arragnement of Me3N+ – and H atom in staggered 3º amine oxide to form an alkene with the elimination
conformation). of a 2º hydroxylamine).
–
b OH H 2O 2
b b
13. (b) (i) CH3I
a a b H
+ C
N CH3 (ii) Ag 2O N H +
H CH3 N(CH3)2 H3C N (CH3)2
H H3C CH3 b
O–
+(CH3)2NOH 3º Amine oxide
(acts its own base)
heat
heat
N + HON (CH3)2
(Cope elimination)
H3C CH3
15. (d) All the three are formed.
 EBD_7374
662 CHEMISTRY

28. BIOMOLECULES

Exercise - 1 13. (b) a -D glucose and b–D glucose are the isomers which
differ in the orientation (configuration) of H and OH
1. (b) Sucrose is an oligosaccharide and cellulose is a groups around C1 atom.
polysaccharide.
2. (b) To explain the properties which can not be explained
by open chain structure of glucose it was proposed H —C1—OH HO —C1—H
that one of the –OH groups may add to the –CHO H —C2—OH H —C2—OH
group and forms a cyclic hemiacetal structure as shown O O
below. HO —C3—H HO —C3—H
O
H —C4—OH H —C4—OH
1
H—C—OH 1 1
HO —C—H 5 5
H —C H —C H —C
2 2 2
H OH H OH H OH 6 6
3 O 3 O CH2OH CH2OH
HO H HO 3 H HO H
a– D - Glucose b– D - Glucose
4 4 4
H OH H OH H OH
H 5 H 5 H 5 14. (c) Fructose is the sweetest sugar.
6 6 OH 6
CH2OH 15. (a) We know that cellulose (C6H12O 5) n is the chief
CH2OH CH2OH
constituent of cell walls of plants. It is the most
a – D – (+) – Glucose b – D – (+) – Glucose
abundant organic substance found in nature. It is a
3. (d) It is the most abundant organic compound on earth.
polymer of glucose with 3500 repeat units in a chain.
4. (d) Tollen’s reagent is reduced by glucose due to aldehydic
16. (b) Sucrose is a disaccharide which on hydrolysis gives
group and gives grey colour as silver metal.
one molecule of glucose (monosaccharide) and
5. (b) The letter ‘D’ or ‘L’ before the name of any compound
fructose (monosaccharide).
indicate, the relative configuration of a particular
stereoisomer. H+
C12 H 22 O11 + H 2 O ¾¾¾
® C6 H12O6 + C6 H12O6
6. (a) Sucrose Glucose Fructose
7. (a) Glucose contains an aldehyde group. It is oxidised into 17. (d) Carbohydrates are stored in the body as glycogen.
acidic group by bromine water and gluconic acid is 18. (b) CH2OHCH2CHOHCHOHCH2OH does not correspond
formed to Cx(H2O)y.
CH 2 OH - (CHOH) 4 - CHO ¾¾¾
®
[O] 19. (d) Lactose (milk sugar) is a disaccharide, it is made of
b-D-galactose and b-D-glucose
CH 2OH - (CHOH ) 4 - COOH
CH2OH
Br2 + H 2 O ¾¾ ® 2HBr + O CH2OH H O H
8. (d) Weak reagent like NaHSO3 is unable to open the chain HO O H
H OH H
and can’t react with glucose. This explains the inability OH
OH H
of glucose to form aldehyde bisulphite compound. H H H OH
9. (d) H OH
10. (c) Open chain structure is unstable and converted to cyclic. 20. (b) 21. (b)
11. (b) 22. (b) Sucrose is dextrorotatory but after hydrolysis gives
12. (c)
dextrorotatory glucose and laevorotatory fructose.
1
H OH Since the laevorotation of fructose (–92.4°) is more than
2 dextrorotation of glucose (+52.5°), the mixture is
H OH laevororatory.
O
3 23. (c) Chemically amylose is a long unbranched chain with
HO H
200-1000 a-D-(+)-glucose units held by C1-C4
4 glycosidic linkage.
H OH
5 24. (b) It is a branched chain polymer of a-D-glucose units in
H which chain is formed by C1-C4 glycosidic linkage,
CH2OH whereas branching occurs by C1-C6 glycosidic linkage.
a -D-(+) - Glucose 25. (b) Cellulose is a straight chain polysaccharide.
BIOMOLECULES 663

26. (a) 37. (d) The hydrolysis of sucrose brings about a change in
27. (c) Sucrose is non-reducing in nature. It does not contain the sign of rotation from dextro (+) to laevo (–) and the
a free aldehydic or ketonic group. Maltose is a product is named as invert sugar.
reducing sugar. 38. (a) a-D-glucose or b-D-glucose when dissolved in water
28. (b) Naturally occurring monosaccharides are 20 only. and allowed to stand, following equilibrium is stablised,
Sucrose is a non–reducing sugar, whereas maltose is a which is called mutarotation.
reducing sugar. a-D-glucose ƒ Open chain form ƒ b-D-glucose
29. (b) The six membered cyclic structure of glucose is called
pyranose structure (a or b), in analogy with pyran. (+111°) (+19°)
Pyran is a cyclic organic compound with one oxygen Specific rotation of a-form falls until a constant value
atom and five carbon atoms in the ring. The cyclic of +52.5° is reached. On the other hand, specific rotation
structure of glucose is correctly represented by of b form increases again to +52.5°. Specific rotation of
Haworth structure. Five membered cyclic structure of equilibrium mixture is 52.5°.
glucose is called furanose structure.
30. (c) Amylose is water soluble component which constitutes 6 O 1
about 15-20% of strach. Amylopectin is insoluble in 39. (b) HOH2C CH2OH
and constitutes about 80-85% of starch. 5 2
31. (a) H OH
4 3
32. (c) Glucose contains aldehyde group due to which it gives H OH
positive test with ammoniacal silver nitrate.
OH H
33. (d) We know that glucose reacts with one molecule of
a-D-(–)-Fructofuranose
phenylhydrazine to give phenylhydrazone. When
warmed with excess of phenylhydrazine, the secondary
alcoholic group adjacent to the aldehyde group is 6 O
oxidised by another molecule of phenylhydrazine to a HOH2C OH
ketonic group. With this ketonic group, the third molecule
5 2
of phenylhydrazine condenses to glucosazone. H OH
Therefore the value of X is 3 H 4 3
CH2OH
1
CHO + H2NNHC6H5 CH = NNHC6H5
OH H
CHOH CHOH b-D-(–)-Fructofuranose
warm
(CHOH)3 (CHOH)3 40. (d) Maltose is compound of two a-D - glucose units in which
C1 of one glucose is linked to C4 of another glucose
CH2OH CH2OH unit.
Glucose Glucose phenylhydrozone 6 6
CH2OH CH2OH
H2NNHC6H5 H 5 OH H 5 OH
4
H 1 O 4
H 1
OH H OH H
CH = NNHC6H5 CH = NNHC6H5 HO 3 2 3 2 OH

H2NNHC6H5 H OH H OH
C = NNHC6H5 C=O I II
– H2O
a-D-glucose a-D-glucose
(CHOH)3 (CHOH)3
41. (c) The hydrolysis of sucrose by boiling with mineral acid
CH2OH CH2OH or by enzyme invertase or sucrase produces a mixture
Glucosazone Keto compound of glucose
of equal molecules of D(+) glucose and
phenylhydrazone D(–) Fructose.
34. (c) HCl
C12H22O11 + H2O ¾¾® C6H12O6 + C6H12O6
Au.ZnCl2
35. (c) OHC.(CHOH)4.CH2OH + 5Ac2O ¾¾¾¾¾
® Sucrose D-Glucose D-Fructose
[a D]=+66.5° [aD]=+52.5° [a D]=–92°
Glucose Acetic anhydride
OHC. (CHOAc)4. CH2OAc Invert sugar, [a D]=–20°
Glucose penta-acetate or 42. (a)
Penta-acetyl glucose
43. (c) Amino acids are the compounds having one or more
36. (c) Melting point of a-glucose® 419 K and b-glucose is
amino groups and one or more carboxyl groups in the
323 K.
same molecule.
 EBD_7374
664 CHEMISTRY

44. (b) Except glycine, all other naturally occurring a- amino 62. (c) During denaturation 2° and 3° structures are destroyed
acids are optically active, since the a-carbon atom is but 1° structure remains intact.
asymmetric. 63. (a) Primary structure refers to the order of the amino acids
in a protein.
45. (d)
64. (d) The hydrophilic/ hydrophobic character of amino acid
46. (d) Zwitter ion contains both +ve and –ve charge. Proton
residues is important to tertiary structure of protein
of –COOH group is transferred to the –NH2 group. rather than to secondary structure. In secondary
—NH3+ group is acidic since it can donate a proton and structure, it is the steric size of the residues that is
—COO– group is basic since it can accept a proton. important and residues are positioned to minimise
47. (d) Proline is a secondary amine. interactions between each other and the peptide chain.
48. (c) The bond formed between two amino acids by the 65. (d) Quaternary structure refers to the overall structure of a
elimination of a water molecule is called a peptide multiprotein complex whereas primary, secondary and
linkage or bond. The peptide bond is simply another tertiary structure refer to the different structural levels
name for amide bond. of a single protein.
66. (a) The arrangement of polypeptide chains formed as a
result of hydrogen bonding is called secondary
- C OH + H — N— ¾¾
® — C– N— + H 2 O
÷÷ | || | structure of proteins.
O H O H a-Helix is formed by intramolecular H-bonding.
Carboxyl group Amine group of Peptide bond b-Pleated sheet is formed by intermolecular H-bonding.
of one amino acid other amino acid
67. (b) The secondary structure of a protein refers to the shape
The product formed by linking amino acid molecules in which a long peptide chain can exist. There are two
through peptide linkages, —CO—NH—, is called a different conformations of the peptide linkage present
in protein, these are a-helix and b-conformation. The
peptide.
a-helix always has a right handed arrangement. In
49. (b)
b-conformation, all peptide chains are streched out to
50. (d) Proteins are highly complex, natural compounds, nearly maximum extension and then laid side by side
composed of a large number of different a-amino-acids and held together by intermolecular hydrogen bonds.
joined together with peptide linkage, i.e., they are The structure resembles the pleated folds of drapery
naturally occuring polypeptides. and therefore is known as b-pleated sheet.
51. (d) All these are the examples of globular proteins. These 68. (b) In this structure of protein, atoms are highly coiled
are soluble in water. and form a spherical form.
52. (c) Polypeptide chains, in fibrous proteins, are held together 69. (d) When a protein, in its native form, is subjected to a
by disulphide and hydrogen bonds. physical change like change in temperature, or a
53. (c) Insulin is an example of globular protein. chemical change like change in pH, the native
conformation of the molecule is disrupted and proteins
54. (c) 55. (b) 56. (b)
so formed are called denaturated proteins.
57. (c) Fibrous proteins are generally insoluble in water.
The denaturation may be reversible or irreversible. The
58. (b) The NH of the amide can act as a hydrogen bond donor coagulation of egg on boiling is an example of
and the carbonyl group can act as a hydrogen bond irreversible protein denaturation.
acceptor. Statements (a), (c) and (d) are false. The However, it has been shown now that in some cases,
peptide bond has double bond character due to the the process is actually reversible. The reverse process
interaction of the nitrogen lone pair with the carbonyl is called renaturation.
group. This prevents bond rotation and makes the bond 70. (c) Tertiary structure indicates the overall structure of the
planar. The trans isomer is favoured over the cis isomer. protein.
59. (a) 71. (b)
60. (a) The sequence in which the a-amino acids are linked to 72. (b) Serine contains a hydroxyl functional group on its side
one another in a protein molecule is called its primary chain and so the strongest possible interaction will be
structure. hydrogen bonding where the hydroxyl group could
61. (b) The a-helix structure is formed when the chain of act as a hydrogen bond donor or hydrogen bond
a-amino acids coils as a right handed screw (called acceptor.
a-helix) because of the formation of hydrogen bonds 73. (a) When antigens enter into the body cells and destroy
between amide groups of the same peptide chain, i.e., them, then antibodies being proteins are synthesised
NH group in one unit is linked to carbonyl oxygen of in the body and combine with antigens and destroy
the third unit by hydrogen bonding. This hydrogen these antigens by forming inactive complexes.
bonding between different units is responsible for Therefore antibodies protein destroy antigens.
holding helix in a position. 74. (c) Glycine is optically inactive.
BIOMOLECULES 665

75. (a) Gln stands for glutamine. Except glycine, all other 96. (c) Vitamin A - Xerophthalmia
naturally occurring a–amino acids are optically active. Vitamin B12 - Pernicious anaemia
76. (c) When the proteins are subjected to the action of heat, Vitamin C - Scurvy
mineral acids or alkali, the water soluble form of globular
Vitamin E - Sterility
protein changes to water insoluble fibrous protein. This
is called denaturation of proteins. During denaturation Vitamin K - Haemorrhage
secondary and tertiary structures of protein destroyed 97. (d) Vitamin D is a fat soluble vitamin and can be stored in
but primary structures remains intact. the body since it is not excreted out of the body.
77. (a) R is the correct explanation of A. 98. (a) Vitamin C is water soluble. Therefore, it is readily
78. (c) Valine has no functional groups on its side chain. There excreted in urine and cannot be stored in our body and
is only an alkyl group and so only van der Waals is supplied regularly in diet.
interactions are possible. 99. (b) RNA has D (–) – Ribose and the DNA has 2–Deoxy
79. (a) Amino Acids are amphoteric in nature. So for it a special D (–) – ribose as the carbohydrate unit.
term is coined called Zwitter ion. 5 5
They have following structure in solution HOCH2 O OH HOCH 2 O OH
4 1 4 1
R H H H H
+ – H H H H
H3N–C–COO 3 2 3 2
OH OH OH H
H 2-Deoxy ribose
Ribose
[Zwitter Ion] From the structures it is clear that 2nd carbon in DNA
80. (b) Enzymes are highly specific for a particular reaction does not have OH group.
and also for a particular substrate.
100. (a) DNA consists of two polynucleotide chains, each chain
81. (b) Enzymes being biocatalysts can increase the rate of a
forms a right handed helical spiral with ten bases in
reaction upto 10 million times. Even very small amount
one turn of the spiral. The two chains coil to double
can accelerate a reaction.
helix and run in opposite directions held together by
82. (b) Triglycerides are lipids, hence these are hydrolysed
hydrogen bonding.
by lipases to glycerol and fatty acids.
83. (d) Enzymes are most reactive at optimum temperature. The
101. (d) O Deoxyribose-Adenine ... Thymine -Deoxyribose O
optimum temperature for enzyme activity lies between
40°C to 60°C. OH P Deoxyribose-Guanine ... Cytosine -Deoxyribose
P OH
O O
84. (b) Insulin is a biochemically active peptide hormone P P
OH OH
secreted by pancreas. O Deoxyribose-Guanine ... Cytosine -Deoxyribose O
85. (a) OH P Deoxyribose-Adenine ... Thymine -Deoxyribose
P OH
86. (d) Enzymes may or may not require a coenzyme for their
catalytic action. The hydrogen bonds are formed between the base
87. (c) (shown by dotted lines). Because of size and
88. (c) Deficiency of vitamin D causes rickets. geometrics of the bases, the only possible pairing in
89. (d) Vitamin Disease caused by deficiency DNA are between G(Guanine) and C(Cytosine) through
B6 Dermatitis three H-bonds and between A (Adenine) and T
B1 Beri-beri
(Thymine) through two H-bonds.
B2 Photophobia, glossitis
102. (a) In DNA the complimentary base are Adenine and
B12 Pernicious anaemia
thymine. Guanine and cytosine. The genetic
90. (b) Vitamin E is mainly present in vegetable oils like wheat
gram oil, sunflower oil, etc. information for cell is contained in the sequence of
91. (a) Vitamin A or retinol. bases A, T, G and C in DNA molecule.
92. (b) 103. (c) The base pairs of the two strands of DNA are linked
93. (c) It is found in liver, egg, milk, meat, and fish. Minute together through H-bonds.
amounts are probably present in all animal cells. 104. (d) DNA has the property of self - replication . It is therefore
Peculiarly, unlike other vitamins, B12 is not found in a reproducing molecule. This unique property of DNA
significant amounts in green plants. is at the root of all reproduction. Through its replication,
94. (b) Water soluble vitamins must be supplied regularly in DNA acts as the key to heredity. In the replication of
diet because they are readily excreted in urine and
DNA, the two strands of a double helix unwind and
cannot be stored (except vitamin B12) in our body.
95. (b) separate as a template for the formation of a new
complementary strand.
 EBD_7374
666 CHEMISTRY

105. (c) Each chromosome is made up of DNA tightly coiled 2. (d) Glycogen is stored in the liver, brain and muscles of
many times around proteins called histones that animals.
supports its structure. H O
3. (c) C12 H 22 O11 ¾¾¾
2 ®C H O + C H O
+ 6 12 6 6 12 6
106. (a) H
Cane sugar D( +) glucose D ( -) fructose
107. (a) DNA has double stranded a-helical structure.
4. (c) Structures having different configuration at C-1 are
108. (b) DNA is responsible for transmission of heredity
known as anomers
character.
5. (c) In a-helix structure, — NH group of one amino acid is
109. (b)
110. (a) Energy is stored in our body in the form of A.T.P. hydrogen bonded to C = O group of adjacent amino
111. (d) acid, forming a helix.
112. (a) Phosphoric acid is the third component in DNA. 6. (b) Reducing groups of glucose and fructose are involved
113. (a) Synthesis of polypeptide is known as translation. For in glycosidic bond formation 40 H2C.
this process three types of RNA are essential. 6
114. (d) The correct structure of thymine is CH2OH 1
HOCH2
H O H O H
OH 5 2 5
4
OH H 1 H HO
O 3 4 CH2OH
HO 6
N CH3 3 2
H OH OH H
a-D-glucose b-D-fructose
HO N
7. (b) Ascorbic acid is the chemical name of vitamin C.
115. (c)
8. (a) Dinucleotides are formed by phosphodiester linkage
116. (d) Tyrosine is an a-amino acid, and not a purine.
between 5' and 3' carbon atom of pentose sugar.
117. (d)
118. (c) DNA fingerprinting is same for every cell and cannot
be altered by any known treatment. O 5' end of chain
119. (b) In secondary structure of DNA adenine forms s
||
O P O CH2 Base
hydrogen bonds with thymine whereas cytosine forms |s O
hydrogen bonds with guanine. O 4' 1¢
Sugar
120. (b) In DNA and RNA heterocyclic base and phosphate 2¢
3'
ester are at C1' and C5' respectively of the sugar
molecule. O
|
HO s
N
N
O P =O
| 5 |
HO – P – O – CH 2 4¢ O N O
|| N
C Base
O C¢ 5'CH2 O
H H
H | | 4' 1¢
Sugar
C3––– C2 H 3'
| | 2¢
OH OH OH

Exercise-2 3' end of chain

1. (b) Structure of glycogen is similar to the structure of

amylopectin. 9. (b) The polymer of nucleotides in which nucleic acids are
linked together by phosphodiester linkage are known
CH2OH CH2OH
as nucleic acid.
O H O H
H
H
H
H
10. (c) Glucose is present in pyranose form,
4
O4
OH 1
O OH H 1 a-link
O CH2OH
H OH H OH
H O H
H
OH H
CH2OH HO OH
CH2OH 6 CH2
H O H H 5 O H H O H H OH
H H H
1 4 OH H 1 4 OH H 1 Pyranose means six membered ring containing oxygen.
4 OH O O O
O
a-link a-link 11. (a) Primary structure of proteins. When each polypeptide
H OH H OH H OH in a protein has amino acids linked with each other in a
Structure of amylopectine specific sequence.
BIOMOLECULES 667

12. (c) RNA does not contain thymine. 21. (c) Adrenaline is a hormone produced by adrenal glands
13. (d) Vitamin B12 can be stored in our body because it is not during high stress or exciting situations. This powerful
water soluable. hormone is part of the human body’s acute stress
14. (d) DNA does not contain uracil. response system, also called the fight or flight
15. (a) Cyclic structures of monosaccharides which differ in response.
structure at carbon -1 are known as anomers. 22. (b)
Here, I and II are anomer because they differ from each
23. (a) Reason is the correct explanation of Assertion.
other at carbon-1 only.
24. (a) DNA contains ATGC bases
16. (c) "Pentaacetate of glucose does not react with
hydroxylamine" showing absence of free CHO group. So quinoline is not present in DNA.
This can not be explained by open structure of glucose 25. (c) ˆˆ† R - S - S - R
2R - S - H ‡ˆˆ
while all other properties can be easily explained. Thiol Disulphide

CH2OH
Example :
17. (a) CHO [O]
CHO
H OH C=O
ˆˆˆ†
2HO 2C CHC H 2SH ‡ˆˆˆ ˆ
ˆ
| [H]
H OH HO H HO H NH2
H OH H OH Cysteine HO 2CCHC H 2S - SCH 2 CHC O 2 H
CH2OH H OH H OH | |
NH 2 NH2
CH2OH CH2OH
Cystine
(+) (+) (–)
(iii)
26. (c) When the proteins are subjected to the action of heat,
(i) (ii)
mineral acids or alkali, the water soluble form of globular
When OH on lowest asymmetric carbon is written at protein changes to water insoluble fibrous protein. This
right hand side, it is represented as D configuration is called denaturation of proteins. During denaturation
and when OH is written on left hand side, it is secondary and tertiary structures of protein destroyed
represented as L configuration. but primary structures remains intact.
18. (c) Carbon adjacent to oxygen atom in the cyclic structure 27. (c) Water-soluble vitamins dissolve in water and are not
of glucose or fructose is known as anomeric carbon. stored by the body. The water soluble vitamins include
6 6 the vitamin B-complex group and vitamin C.
19. (c) CH2 OH CH2 OH
5 O 5
O 28. (a) The sequence of bases in mRNA are read in a serial
H 1 (A) H H OH
H
O 4 1
order in groups of three at a time. Each triplet of
4
OH H H OH H nucleotides (having a specific sequence of bases) in
OH H
2 2
3 3
OH
known as codon. Each codon specifies one amino acid.
H OH
C1 – C4 linkage Further since, there are four bases. therefore, 43 = 64
(I) triplets or codons are possible.
6
6
CH2 OH CH2 OH 29. (b) Cobalt is present in vitamin B12.
O
H 5 O
H H 5 OH 30. (d) Sucrose is non-reducing disaccharide as the two
H H
4 1 4 1 monosaccharide units are linked through their
OH H OH H
(C) O H
OH 6 respective carbonyl groups.
3 2 CH2 OH 3 2
H OH 5 O
H OH 31. (c) Peptide bond
C 1 to C2 ® O(B) H C 1 to C2 linkage
H 1
linkage 4 OH — C — NH —
H
6
CH2 HO H ||
O 3 2
H 5 H H OH O
H 1
4
OH
OH H 32. (b) Sugar in DNA is 2-deoxyribose whereas sugar in RNA
OH
3 2 is ribose.
H OH
33. (c) With the exception of glycine all the 19 other common
(II) (III)
amino acids have a uniquely different functional group
20. (d) Glucose reacts with hydroxyl amine to form an oxime.
on the central tetrahedral alpha carbon.
CHO CH=N–OH H
H OH H OH |
HO H HO H H — C — COOH
NH 2OH
H OH ¾¾¾® H OH |
H OH H OH NH 2
Glycine
CH2 – OH CH2 – OH
D(+) glucose
 EBD_7374
668 CHEMISTRY

34. (d) Vitamin D is a fat soluble vitamin and can be stored in

the body since it is not excreted out of the body. CHO
35. (a) Among 20 naturally occuring amino acids "Cysteine" H OH
HO H
has '– SH' or thiol functional group. HI/ D
47. (a) H OH ¾¾¾¾ ®
Þ General formula of amino acid ® R– CH – COOH H OH
Reduction n-Hexane
|
NH2 CH2OH
Glucose
Þ Value of R = – CH2 – SH in Cysteine.
36. (d) Reaction of D-(+)-glucose with methanolic —HCl leads 48. (d) Structure of Histamine
to formation of methyl glucoside (C1—OH group is H
methylated) which, being acetal, is not hydrolysable
by base, so it will not respond Tollens’ reagent. N
37. (c) Ketoses on reduction produce a new chiral carbon N
leading to the formation of two isomeric alcohols which 9.75 pKa (more basic)
are diastereomeric as well as C–2 epimers.
38. (c) Due to denaturation of proteins, helix get uncoiled and \ Predominant structure of Histamine is
protein loses its biological activity. H
39. (c) Anomers are those diastereomers that differ in N +
configuration at C – 1 atom.
Since a - D - (+) - glucose and b – D – (+) glucose N
differ in configuration at C – 1 atom so they are anomers. ( Due to slightly basic nature of blood (pH = 7.35)
40. (a)
Exercise-3
HOCH2 CH2OH HOCH2 CH2OH
O O 1. (d) During acetylation of (+)-glucose, it is the C1 —OH
O ¾¾¾¾¾® aq.KOH
HO – CH3COOK HO – of the hemiacetal that is acetylated and not the C5—
O – C – CH3 O OH that forms the ring (cyclic structure). Since
OH OH equilibrium with the open-chain aldehyde is
Hemiketal prevented, the penta-acetate does not respond the
aldehydic reactions.
Ring opening

HOCH2 OH
CH2OH
positive silver Ac O
mirror
Tollen 's
¬¾¾¾ ¾ HO O ¾¾¾
2 ®
Reagent
test
OH
(a Reducing sugar) a-hydroxy ketone

41. (a) Thyroxine is an amine hormone.

42. (d) Glycosidic linkage is a type of covalent bond that joins
either two carbohydrate (sugar) molecule or one
carbohydrate to another group. All molecules show 2. (d) When structures I and II are C–2 epimers, it implies
such type of linkages. that these are epimers and diastereomers too.
43. (a) Amylose and amylopectin ar e polymers of 3. (b) A ketonic group having —OH group on both sides is
a-D-glucose, so b-link is not possible. Amylose is removed as CO2 during oxidation with periodate.
linear with 1 ® 4 a-linkage whereas amylopectin is
branched and has both 1 ® 4 and 1 ® 6 a-linkages. 4. (d) Reaction of D-(+)-glucose with methanolic –HCl leads
So option (a) should be the correct option. to formation of methyl glucoside (C1–OH group is
+ methylated) which, being acetal, is not hydrolysable
44. (c) ˆˆ† OOC – CH 2 – NH 3
HOOC – CH 2 – NH 2 ‡ˆˆ by base, so it will not respond Tollens’ reagent.
Glycine Zwitter ion
5. (a) The OH’s of sugars are more acidic than that of a
45. (a) typical alcohol because of their mutual electron-
46. (c) Correct explanation : During formation of proteins, withdrawing inductive effect.
NH2 group of one amino acid condenses with CO2H of 6. (b) Although D-alanine is a constituent of a bacterial cell
the other with elimination of a water molecule to form a walls, it is not found in proteins.
peptide bond.
BIOMOLECULES 669

7. (b) Protonation at b–N leads to imidazolium ion, which is

R R
stabilized by two equivalent resonating structures. + |
acid
+ |
¾ H3 N C HCOO-
H3 N C HCOOH ¬¾¾
b +

:
:N HN HN
H
+
R
|
:

:
base
aN N N ® H 2 N C HCOO-
¾¾¾
H H H
Equivalent resonating structures 12. (c) Compounds having two –OH groups, or –OH and –
CO, or –OH and –CHO on adjacent carbon atoms are
8. (a) On increasing the pH by adding an alkali ; H+ will be
oxidised by periodic acid. Thus
lost from — COOH.
9. (c) At the given pH (6) of the solution, alanine (pI = 6.0), O OH O
|| | ||
exists as a dipolar ion while arginine (pI = 10.2) exists 2 H IO
CH 3 - C - C H - C- CH3 ¾¾5¾¾
6®
as a cation. Hence on passing an electric current,
alanine will not migrate to any electrode, while arginine 2 H IO
will migrate to cathode. H 3 ¾¾5¾¾
6 ® CH COOH + HCOOH + CH COOH
3 3
10. (c) The resulting compound is an a-amino acid and the
15
reagent used for its synthesis are NH3 and H2/catalyst, 13. (b) ´ 100 = 50
30
so this is an example of preparation of a-amino acid
Thus the mixture is 50% optically pure. Hence the
by reductive amination for which a-keto acids are
amount of
starting compounds.
A = 50 + 25 = 75
11. (b) Amino acids exist as zwitterions in which acidic
B = 0 + 25 = 25 +
character is due to - NH 3+ and basic due to – COO– 14. (b) – COOH is a better proton donor than N H3 .
group. 15. (b) Glucose exists as glucopyranose (a six membered ring
structure) which is formed through C1 and C5.
 EBD_7374
670 CHEMISTRY

29. POLYMERS

Exercise - 1 condensation polymerisation of adipic acid and

haxamethylene diamine.
1. (d) 27. (a) Melamine plastic crockery is a copolymer of HCHO
2. (d) All these are natural polymers and exist in nature. and Melamine.
3. (c) ATP is a monomer molecule. 28. (d) 29. (b) 30. (b)
4. (d) Rayon is manufactured from regenerated cellulosic 31. (a) Bakelite is used for making phonograph records.
fiber. Rayon is produced from naturally occurring
OH OH OH
polymers and therefore it is not a truly synthetic fibre
nor is it a natural fiber. It is known by the names viscose CH2OH
–
OH
rayon and artificial silk in the textile industry. So, + HCHO +
option (d) is the correct choice.
5. (c) Protein is a natural polymer of amino acids. CH2OH
6. (b) o & p-Hydroxymethylphenol
(intermediate)
7. (d) Cellulose acetate also known as rayon and cellulose
nitrate are semisynthetic polymers.
8. (a) Polymerisation starts either by condensation or OH
OH OH
addition reactions between monomers. Condensation CH2OH
Polymerisation
polymers are formed by the combination of monomers n CH2
with the elimination of simple molecules.Whereas the – (n – 1) H 2O
addition polymers are formed by the addition of the
Linear polymer (Novalac)
monomer or monomers molecules to form a large
molecule without elimination of any thing. 32. (a) Dacron is a polyester and is the condensation polymer
9. (d) 10. (a) of ethylene glycol and terephthalic acid. It is crease
11. (d) All these are characteristics of elastomers. resistant.
12. (d) Thermosetting polymers have strongest molecular 33. (c) Terylene is made from glycol and terephthalic acid
forces. These are crosslinked polymers.
13. (b) Thermosetting plastics have three dimensional cross HO - CH 2 - CH 2 - OH and HOOC COOH
linked structure. Glycol
Terephthalic acid
14. (d) All the given statements about fibres are correct.
15. (b) Polystyrene and polyethylene belong to the category 34. (a)
of thermoplastic polymers which are capable of 35. (b) It is the definition of copolymerisation.
repeatedly softening on heating and harden on 36. (b) 37. (d) 38. (b) 39. (a)
cooling. 40. (b) Buna – N is a copolymer of butadiene
16. (b) 17. (a) (CH2= CH – CH = CH2) and acrylonitrile (CH2 = CHCN).
18. (b) A – (q), B – (s), C – (r), D – (p) 41. (c) Neoprene is a homopolymer of chloroprene.
19. (a) Ethene on free radical polymerisation gives low density
42. (b) Buna – N is obtained by copolymerisation of
polythene.
1, 3–butadiene and acrylonitrile.
20. (b) Monomer of teflon is to tetrafluoroethylene C2F4.
43. (d) Number of hydrogen bonds is greater in polymer (1)
21. (d) Vinyl chloride, butadiene and styrene being unsaturated
than in (2) as the density of amide bond is greater in (1)
undergoes addition polymerization.
therefore the chain links to each other strongly in (1)
22. (b)
than in (2) hence (1) melts at higher temperature.
23. (d) Acrylonitrile is the monomer used in the preparation of
44. (d) Nylon–6 is used in the manufacturing of tyre cords
orlon.
not nylon–6,6 this is used in making sheets, bristles
24. (b) High density polythene is used for manufacturing of
for brushes and in textile industry. Melamine –
buckets, dustbins, pipes etc.
formaldehyde polymer is used in the manufacture of
25. (b) High density polythene is formed when addition
unbreakable crockery.
polymerisation of ethene takes place in a hydrocarbon
45. (c) Biodegradable polymers are manufactured because
solvent in presence of catalyst such as Ziegler-Natta
conventional polymers are quite resistant to the
catalyst.
environmental degradation which leads to accumulation
26. (b) Nylon-6, 6 is an example of first synthetic fibre produced
of polymeric solid waste materials causing acute
from the simple molecules. It is prepared by
environmental problems.
POLYMERS 671

46. (c) A – (s), B – (r), C – (p), D – (q) Cl

47. (b) A – (q), B – (r), C – (p), D – (t), E – (s) |
48. (a) A – (r), B – (p), C – (q), D – (t), E – (s) (- CH 2 - CH = C - CH 2 - ) n
49. (a) Neoprene
(A)
Polystyrene is used as insulator. 59. (a) Terylene is prepared by condensing terephthalic acid
(B)
Glyptal a polymer of ethylene glycol and phthali acid and ethylene glycol
is used in manufacture of paints and lacquers.
(C) Bakelite, a polymer of phenol & formal dehyde is used nHOOC COOH + nHOCH2CH 2OH
for making electrical switches, handles of utensils and
Terephthalic acid Ethylene glycol
computer disc’s.
(D) PVC, a polymer of vinyl chloride is used in manufacture O O
of raincoat and flooring. || ||
50. (b) Nylon 6, 6 has amide linkage capable of forming C C – OCH 2–CH 2 – O
n
hydrogen bonding. Terylene
51. (b)
60. (d) 61. (c) 62. (d)
52. (d) Nylon and cellulose, both have intermolecular
hydrogen bonding, polyvinyl chloride has dipole-
Exercise-2
dipole interactions, while natural rubber has van der
Waal forces which are weakest. 1. (d) Glycogen is a polymer of glucose found in liver, brain
53. (b) Due to the presence of strong C–F bonds, teflon has and muscles of animals.
high thermal stability and chemical inertness. 2. (a) cis-polyisoprene is a synthetic polymer.
54. (b) The condensation polymerisation of hexamethylene 3. (b) The commercial name of polyacrylonitrile is orlon
diamine and adipic acid is done in solution form by (acrilan).
interface technique. In this liquid nylon polymer is
obtained. n CN
|
n.H 2 N - (CH 2 )6 - NH 2 + nHOOC – (CH 2 ) 4 – COOH CN ¾¾¾¾¾¾¾
® ( CH2 CH )n
Peroxide catalyst
PAN
Polymerisation
¾¾¾¾¾¾
- nH 2 O
® [-HN - ( CH 2 )6 - NHCO- ( CH 2 )4 - CO-]n
Nylon
or orlon
or acrilan
4. (c) PHBV is an example of biodergradable polymer.
55. (c) Bakelite can be heated only once.
O O HOOC COOH
56. (a) C6H5 – C – O – O – C – C6H5 ¾¾® 5. (a) n HOCH2 — CH2OH + n
O Glycol
Phthalic acid
|| g g
2C6 H5 , C, O ¾¾
↑ 2 C6 H 5 Zn (OCOCH3)2 + Sb2O3
O
||
(A) 420-460 K
¾¾¾¾¾¾¾¾® (O CH2 CH2OOC C )n
Phenyl radical –nH2O
g ·
C6 H5 ∗ CH2 < CH2 ¾¾
↑ C6 H5 , CH 2 , C H 2
(A) Terylene or dacron
· 6. (d) Low density polythene has slightly branched structure.
C6 H 5 - CH 2 - C H 2 + nCH 2 = CH 2 ¾¾
®
· CH3
C6 H 5 - (CH 2 - CH 2 )n – CH 2 - C H 2 7. (a) n CH2 = C
(C) Monomer CH3
· CH3 CH3
C6 H 5 — (CH 2 - CH 2 ) n —CH 2 - C H 2 + | |
Polymerisation
(C) ¾¾¾¾¾® ( CH2 C CH2 C )n
· | |
C6 H 5 ¾ (CH 2 – CH 2 ) n ¾ CH 2CH 2 ¾¾
® CH3 CH3
(C) Polymer
C6H5 – (CH2CH2)n – CH2CH2 – CH2CH2 – (CH2CH2)n – C6H5 H
57. (b) Vulcanisation is a process of treating natural rubber | O O
with sulphur or some compounds of sulphur under N || ||
D, Polymerisation
heat so as to modify its properties. This cross-linking 8. (d) ¾¾¾¾¾¾®
– ( n – 1)H O –[ NH — (CH2)5 — C] n
2
gives mechanical strength to the rubber. Nylon-6
Caprolactum
Cl
|
O or peroxides
9. (d)
58. (d) nCH 2 = CH - C = CH 2 ¾¾¾¾¾¾¾
2 ®
Chloroprene
 EBD_7374
672 CHEMISTRY

10. (c) polymerisation

H2C C — CH CH2 ¾¾¾¾¾¾ ®
D |
n HOCH 2CH 2OH + n HOOC COOH ¾¾® CH3
Isoprene
Ethylene glycol Terephthalic acid
CH2 CH2
O O
|| || H3C H
-( O CH 2CH2–O– C C- )n cis-polyisoprene

Terylene
20. (b) Nylon 6 is
It is resistant to mineral and organic acids. It is used for
blending with wool to provide better crease, in safety O O
½½ ½½
helmets and aircraft battery boxes. —(NH(CH 2 )5 —C— NH— (CH2)5 —C— )n
11. (a) 21. (b) High density polythene is used in the manufacture of
12. (a) Except Dacron all are additive polymers. Terephthalic housewares like buckets, dustbins, bottles, pipes etc.
acid condenses with ethylene glycol to give Dacron. Low density polythene is used for insulating electric
wires and in the manufacture of flexible pipes, toys,
coats, bottles etc.
HOOC COOH + 22. (d) The concerned chemical reactions are
(i) CaC 2 + 2H 2 O ® Ca ( OH ) 2 + C 2H2
Terephthalic acid 64 kg Ethyne , 26kg
HO – CH2 – CH2 – OH ¾¾
®
(ii) C 2 H 2 + H 2 ® C2H 4
Ethylene glycol Ethylene , 28 kg

(iii) nC2 H 2 ® [-CH 2 - CH 2 -]n

[
— CO CH2 – CH2 – O —
n
] n´28 kg
or 28 kg
n´28 kg polythene
or 28 kg

Dacron (Polyester)
Thus 64 kg of CaC2 gives 26 kg of acetylene which in
turn gives 28 kg of ethylene whose 28 kg gives 28 kg of
Cl the polymer, polythene.
|
K S O
13. (d) nCH 2 = CH - C = CH 2 ¾¾2 ¾
2¾8® 23. (d) Neoprene is an addition polymer of isoprene.
Chloropren e
Cl Cl
| |
O 2 or peroxides
-( CH 2 - CH = C - CH 2 -
)n nCH 2 = CH - C = CH 2 ¾¾¾¾¾¾ ¾ ®
Neoprene Chloroprene
14. (d) H2 N—CH2—COOH + H2 N — (CH2)5—COOH ®
æ Cl ö
Glycine Aminocapric acid ç | ÷
—çè CH 2 - C = CH - CH2 —
÷
ø
(HN—CH2—CO—NH— (CH2)5—CO) — Neoprene

Nylon-2-nylon-6 24. (b) Vulcanisation is a process of treating natural rubber

with sulphur or some compounds of sulphur under
O heat so as to modify its properties. This cross-linking
O give mechanical strength to the rubber.
NH H
15. (a) ¾¾¾® N 25. (a) Formation of Nylon-6 involves hydrolysis of
n caprolactum, (its monomer) in initial state.
Caprolactum
Nylon–6
O O
16. (c) Bakelite can be heated only once.
NH H 2O
17. (d) Glyptal is used in the manufacture of paints and H2N(CH2)5COOH
lacquers.
Caprolactam e-Amino Caproic acid
18. (b) PMMA is used in bullet proof glass
19. (a) Natural rubber is found to be a polymer of cis-isoprene O O
i.e. it is cis-polyisoprene
–(NH(CH2)5–C–NH–(CH2)5–C)–n
Polymerise
Nylon-6
POLYMERS 673

26. (b) Polystyrene and polyethylene belong to the category CH3 CH3
of thermoplastic polymers which are capable of C = CH2 C = CH2
repeatedly softening on heating and harden on CH3 CH3
cooling. H T H T
¯
27. (c) Cross-linked or network polymers are usually formed
CH3
from bi-functional and tri-functional monomers and H 3C +

–
contain strong covalent bonds between various linear C – CH2– C – CH2
H 3C

–
polymer chains like melamine, bakelite etc. CH3
28. (b) 6. (a) 7. (d)
8. (d) Cellulose acetate has been used in the manufacture of
Exercise-3 non-inflammable photographic films.
9. (a) SARAN, a polymer of vinyl chloride (CH2=CHCl) and
1. (d) The given compound is a copolymer of hexamethylene vinylidene chloride, is used for making synthetic hair
diamine and adipic acid. It is actually nylon-6, 6. wigs.
10. (a)
2. (a) 11. (d) All the given statements about fibres are correct.
12. (b) Perlon is nylon-6. It is prepared from a single monomer
CH = CH2 (caprolactam) having a potential amino group at one
end and a potential carbonyl group at other end.
Na, Heat
3. (b) nCH 2 = CH - CH = CH 2 + n 13. (b) Polystyrene is a chain growth polymer.
Polymerisation
1, 3-Butadiene
Styrene 14. (b) n HOOC(CH 2 ) 4 COOH + n H 2 N(CH 2 ) 6 NH 2
Adipic acid Hexamethylene diamine

O O
(– CH2 – CH = CH – CH2 – CH – CH2 –)n
525 K
¾¾¾¾¾¾® [– C – (CH2)4 – C –NH–(CH2)6 – NH –]n
Butadiene - Polymerisation
Styrene copolymer Nylon 6, 6
(SBR or Buna - S)
é CH3 ù
ê | ú
4. (b) Acrilan is a polyacrylonitrile ( PAN). 15. (a) Monomer of —
ê C — CH 2 ú polymer is
—
5. (a) Addition of monomers follows isoprene rule ê | ú
êë CH3 úû n

2-methylpropene.
 EBD_7374
674 CHEMISTRY

30. CHEMISTRY IN EVERYDAY LIFE

Exercise - 1 Cl OH HO Cl
1. (d) 2. (a) 3. (d) 4. (b) S
5. (d)
6. (d) Drugs that mimic the natural messenger by switching Cl Cl
Bithional
on the receptor are called agonists. While drugs that
bind to the receptor site and inhibit its natural function 31. (c) Chloramphenicol is a broad spectrum drug.
are called antagonists. [Broad spectrum antibiotics are medicines effective
7. (a) Given drug is used as antacid. against gram positive as well as gram negative bacteria,
8. (d) Equanil is an important medicine used in depression e.g., tetracycline, chloramphenicol, etc.]
and hypertension. 32. (b) Dilute solutions of boric acid and hydrogen peroxide
9. (b) Terfenadine is commonly used as antihistamine. are weak antiseptics.
10. (c) Salvarsan is an organoarsenic compound, used in the 33. (d) Novestrol is an antifertility drug.
treatment of syphilis. It was the first modern 34. (b)
chemotherapeutic agent. 35. (c) Antidepressant drugs inhibit the enzymes which
catalyse the degradation of noradrenaline.
11. (c) 12. (b) 13. (d) 36. (d)
14. (a) These drugs induce sleep and are habit forming 37. (b) Arsphenamine also known as Salvarsan was the first
common example of hypnotic drugs are luminal and effective treatment discovered for syphilis.
saconal. 38. (c) 39. (a)
15. (b) Aspirin is antipyretic i.e., a drug which is responsible 40. (a) Tranquilizers are chemicals which are used to cure
for lowering the temperature of feverish organism to mental diseases.
normal, other antipyretic drugs are paracetamol, 41. (b) Antiseptics are those chemical which kill or prevent
phenacetin. the growth of micro organism. Antiseptics do not harm
16. (d) Sulpha drugs (antibacterial and antibiotic) are group the living tissues and can be applied on cuts and
of drugs which are derivative of sulphanilamides. wounds. They help to reduce odour resulting from the
17. (d) Valium is a tranquilizer and not an analgesic. It is used bacterial decomposition in the mouth and on the body.
for treatment of stress, fatigue, mild and severe mental 42. (c)
diseases. 43. (d) Bacteriostatic drugs inhibit the growth of organism
18. (a) Salol is phenyl salicylate used as antiseptic. while bactericidal drugs kill the microorganisms.
19. (a) Antiseptic drugs cause destruction of micro-organism 44. (b) Bactericidals have killing effect on microbes, while
that produce septic disease e.g. dettol, savlon, boric bacteriostatic have inhibitory effect on microbes.
acid, phenol, iodoform, KMnO4 and some dye such as 45. (b) Chloramphenicol is bacteriostatic antibiotic, while
methylene blue, gentin violet. ofloxacin is bactericidal type antibiotic.
20. (a) It is the very effective antibiotic for tuberculosis. 46. (c) Narrow spectrum antibiotics are effective against
21. (c) Broad spectrum antibiotics act on different antigens. Gram–positive or Gram-negative bacteria. Limited
22. (c) It is an insecticide. spectrum antibiotics are effective against a single
23. (b) organism or disease.
24. (c) Penicillin is an effective medicine for pneumonia 47. (a) Norethindrone is an example of synthetic progestrone
disease. derivative most widely used as antifertility drug.
25. (d) The mixture of chloroxylenol and terpenol is dettol 48. (d) All are characteristics of Saccharin.
which is used as antiseptic. 49. (b) Artificial sweetener Sweetness value
26. (d) Chloroamphenicol is a broad spectrum antibiotic. Aspartame 100
27. (a) Substances used for the treatment of malaria are Saccharin 550
antimalarial e.g. quinine, chloroquine. Sucralose 600
28. (b) It is the known structure of penicillin G. Alitame 2000
29. (c) Arsenic drugs are used for syphilis. 50. (c) Sucralose does not provide calories.
30. (b) Bithional is a well known antiseptic, added in soaps to 51. (b) Structurally biodegradable detergents should contain
reduce odours produced by bacterial decomposition branched alkyl chain.
of organic matter of skin. 52. (b) Benzoic acid is used as preservative as sodium
benzoate.
CHEMISTRY IN EVERYDAY LIFE 675

53. (b) arsphenamine was the first effective medicine

54. (d) It is used as detergent. discovered for syphilis. Salvarsan is toxic to human
55. (c) The most widely used domestic detergent is the sodium beings, but its effect on bacteria is much greater than
dodecyl benzene sulphonate (SDS). on human being.
7. (a) Broad spectrum antibiotics are effective against a
CH3 – (CH2)11 SO3Na
wide range of gram-positive and gram-negative
bacteria whereas narrow spectrum antibiotics are
Sodium dodecyl benzene sulphonate
effective mainly penicillin- G, against gram-positive or
56. (a) Soaps are the sodium or potassium salts of higher fatty
gram-negative bacteria antibiotic is a narrow spectrum
acids e.g., C17H37COOK (Potassium stearate). These
antibiotic.
are obtained by alkaline hydrolysis of oils and fats.
The reaction is called saponification. 8. (b) Tranquilizers are a class of chemical compounds used
57. (c) for the treatment of stress and mild or even severe
58. (b) Shaving soaps contain glycerol to prevent rapid drying. mental disease.
59. (c) 60. (b) 9. (d) Bithinol is added to soaps to impart antiseptic
properties. Sodium laur ysulph ate and sodium
Exercise-2 dodecyl-benzenesulphonate are anionic detergents.
1. (d) Antiseptic is an antimicrobial drug which tends to A gum rosin added to soap to make it leather well.
inhibit the pathogenic action of microbes. They are 10. (b) Equanil is a tranquilizer.
applied to the living tissues such as wounds, cuts
ulcers and diseased skin surface. 11. (b) While preparing soaps, a gum called rosin is added
to them. It forms sodium rosinate which leathers well.
So, antiseptic medicines cannot be ingested like
antibiotics. 12. (c) Gylcerol is added to shaving soap to prevent rapid
drying.
2. (c) Birth control pills contain a mixture of synthetic
estrogen and progesterone derivatives. These are sex 13. (b) Liquid dishwashing detergents are non-ionic.
hormones. Progesterone suppresses ovulation and Mechanism of cleansing action of this type of
estrogen control the menstrual cycle. detergent is same as that of soaps. These also remove
grease and oil by micelle formation.
3. (a) Aspirin inhibits the synthesis of prostaglandins
which stimulate inflammation in the tissues and cause
pain. So, it is effective in relieving pain as it does not C 9H19 O (CH 2CH 2O)5 — CH 2CH 2OH
make a person addictive and known to be a non- Liquid dishwashing detergent
narcotic drug.
14. (c) Polyethyleneglycols are used in the preparation of
4. (c) Classification on the basis of molecular target: drug non-ionic detergents. Non-ionic detergents do not
usually interact with the biomolecules or biological contain any ion in their constitution.
macromolecules such as proteins, nucleic acids and
lipids. These are called drug tagets. Drug possessing CH3 ( CH 2 )16 COOH + HO ( CH 2 CH 2O ) n CH 2 CH 2OH
some common structural features may have the same Stearic acid Polyethylene glycol
mechanism of action on a specific drug target. This - H 2O
classification is most useful fo the medicinal chemists. ® CH3 ( CH 2 )16 COO ( CH 2 CH 2 O )n CH 2CH 2 OH
¾¾¾¾
5. (a) Due to the low level of noradrenaline in the body the 15. (c) Drugs usually interact with biomolecules such as
message transfer process becomes slow and the carbohydrates, lipids, proteins and nucleic acid. These
person suffers from depression. In such cases, are called drug targets. Vitamins are not a target
tranquilizers are used. These drugs inhibits the molecule for drug function in body.
enzymes which catalyse the degradation of
16. (c) Some drugs do not bind to the enzyme's active site
noradrenaline.
but bind to a different site of enzyme which is called
If the enzyme is inhibited, then the neurotransmitter allosteric site, which changes the shape of the active
noradrenaline is slowly metabolised and can thus site, in such a way that substrate cannot recognize it.
activate the receptor for longer periods thereby If the bond formed between an enzyme and inhibitor is
counteracting the effect of depression. a strong covalent bond and cannot be broken easily
6. (a) Paul Ehrlich first synthesised arsenic based structures the enzyme is blocked permanently. The body then
in order to produce less toxic substances for the degrades the enzyme-inh ibitor complex and
treatment of syphilis. Salvarsan also known as synthesises the new enzyme.
 EBD_7374
676 CHEMISTRY

17. (d) Sucralose is trichloro derivative of sucrose. It is stable Meprobamate -

at cooking temperture. It does not provide calories.
O O
18. (b) Artificial sweeteners are non-caloric substitutes for
sugar. They are often more sweet than sugar but do H2N O O NH2
not enhance nutritional value of food.
19. (c) Aspartame is stable under cold conditions.
20. (a) Antioxidants are the compounds that retard the action
of oxygen on the food an d th er eby help its
preservation. Cl
21. (d) 22. (b) N
23. (c) Bithionol is added to soaps to impart antiseptic
properties. Chlorphenamine - N
24. (a) Phenelzine is an antidepressant, while others are
antacids.
25. (d) Cobalt (60) isotope is used in the treatment of cancer.
26. (a) Novalgin is most widely used as analgesic. Analgesics Exercise-3
are pain releiving 1. (c) Asprin is prepared by reaction of salicylic acid with
27. (a) Broad spectrum antibiotics are those medicines which acetic anhydride in presence of H2SO4.
are effective against several different types of harmful O
micro organisms.
28. (d) Sodium lauryl sulphate (C11H23CH2OSO3– Na+) is an C – OH O O
|| ||
anionic detergent. Glyceryl oleate is a glyceryl ester of OH C C
oleic acid. Sodium stearate (C17H35COO–Na+) is a soap.
+ CH3 O CH3
Cetyltrimethyl ammonium bromide
é + ù - COOH
ê CH3 (CH 2 )15 N(CH3 )3 ú Br is a cationic detergent. OCOCH3
ë û H2SO4
¾¾ ¾¾
®
29. (a) BHT is an important antioxidant used in food.
30. (a) Dettol is a mixture of chloroxylenol and terpineol which Acetyl salicylic acid
is a very commonly known antiseptic. (Aspirin)
31. (a) A small quantity of sedative produces a feeling of
2. (b)
relaxation, calmness and drowsiness.
3. (a) Lindane or gammexane is g isomer of BHC.
32. (a) Phenelzine is an antidepressant, while others are 4. (c) 5. (c) 6. (a) 7. (d)
antacids. 8. (b) A detergent molecule consists of a large hydrocarbon
33. (c) group that is non-ionic and a sulphonate (SO3–Na+) or
34. (c) diamines are those compounds which contain two a sulphate (SO4–Na+) group that is ionic. Examples of
amino groups. detergents are sodium-n-dodecyl benzene sulphonate,
sodium dodecyl sulphate etc.
HO NH2 9. (b) It is acetyl salicylic acid i.e., aspirin, used as an analgesic
Dopamine - and antipyretic.
HO 10. (d) Chloramphenicol is
N NH2 O
||
Histamine - O2N CH - CH - NH - C – CHCl2
N | |
H Histamine (HA)
OH CH2OH
 M ck Test - 1
Time : 1 hr. Max. Marks -180

1. A hydrocarbon A on chlorination gives B which on heating

æ x ö æ x ö
with alcoholic potassium hydroxide changes into another (a) ç ÷P (b) ç ÷P
è x -1 ø è 1- x ø
hydrocarbon C. The latter decolourises Baeyer's reagent
and on ozonolysis forms formaldehyde only. A is æ x ö æ 2x ö
(c) ç ÷P (d) ç ÷P
(a) Ethane (b) Butane è x + 1ø è 1- x ø
(c) Methane (d) Ethene 6. Which of the following will not show cis-trans isomerism?
2. What is the IUPAC name of the compound ? (a) CH 3 — CH = CH — CH 3
(b) CH 3 — CH 2 — CH = CH — CH 2 — CH 3
CH(CH 3 ) 2
(c) CH3 — C = CH — CH 2 — CH3
|
CH3

(d) CH 3— CH — CH = CH — CH 2 — CH 3
(a) 1, 1 – dimethyl – 1 – cyclopentyl methane |
CH3
(b) 2 – cyclopentyl propane
7. Point out the false statement
(c) 1 – (1 – methyl) ethyl cyclopentane
(a) Brownian movement and Tyndall effect are shown by
(d) Cumene.
colloidal systems.
3. Which one of the following complexes is not expected to (b) Gold number is a measure of the protective power of a
exhibit isomerism? lyophillic colloid.
(c) The colloidal solution of a liquid in liquid is called gel.
(a) [ Ni(en)3 ]2+
2+ (d) Hardy - Schulze rule is related with coagulation.
(b) é Ni ( NH3 ) ( H 2O ) ù 8. PA and PB are the vapour pressure of pure liquid components,
ë 4 2û
A and B, respectively of an ideal binary solution. If XA
(c) é Pt ( NH3 ) Cl 2 ù
ë 2 û represents the mole fraction of component A, the total
pressure of the solution will be.
(d) é Ni ( NH3 ) Cl 2 ù
ë 2 û (a) PA + XA (PB – PA) (b) PA + XA (PA– PB)
4. The increasing order of the rate of HCN addition to (c) PB + XA (PB – PA) (d) PB + XA (PA – PB)
compound A – D is 9. In which one of the following species the central atom has
the type of hybridization which is not the same as that
(A) HCHO (B) CH3COCH3
present in the other three?
(C) PhCOCH3 (D) PhCOPh
(a) SF4 (b) I3– (c) SbCl52– (d) PCl5
(a) D < C < B < A (b) C < D < B < A
10. Which of following compound is hemiacetal?
(c) A < B < C < D (d) D < B < C < A
5. Phosphorus pentachloride dissociates as follows, in a closed HO OMe
O OH
reaction vessel
(a) (b)
ˆˆ† PCl3(g) + Cl2(g)
PCl5(g) ‡ˆˆ
If total pressure at equilibrium of the reaction mixture is P
and degree of dissociation of PCl5 is x, the partial pressure H OH

of PCl3 will be (c) (d) all of these

O
 EBD_7374
MT- 2 CHEMISTRY

11. What products are expected from the disproportionation (c) more energy difference between 5f and 6d than between
reaction of hypochlorous acid? 4f and 5d orbitals
(a) HCl and Cl2O (b) HCl and HClO3 (d) more reactive nature of the actinoids than the
(c) HClO3 and Cl2O (d) HClO2 and HClO4 lanthanoids
12. Which one of the following reactions does not form 20. Which one of the following arrangements does not give
gaseous product? the correct picture of the trends indicated against it ?
(a) PbO2 + H2O2 (a) F2 > Cl2 > Br2 > I2 : Oxidizing power
(b) Acidified KMnO4 + H2O2 (b) F2 > Cl2 > Br2 > I2 : Electron gain enthalpy
(c) F2 > Cl2 > Br2 > I2 : Bond dissociation energy
(c) Pbs + H2O2
(d) F2 > Cl2 > Br2 > I2 : Electronegativity.
(d) Cl2 + H2O2
21. The process of converting hydrated alumina into anhydrous
13. An antibiotic contains nitro group attached to aromatic alumina is called
nucleus. It is (a) roasting (b) smelting
(a) penicillin (b) streptomycin (c) dressing (d) calcination
(c) tetracycline (d) chloramphenicol 22. The rate constant of a reaction becomes equal to the
14. An ionic compound has a unit cell consisting of A ions at pre-exponential factor when
the corners of a cube and B ions on the centres of the faces (a) the absolute temperature is zero
of the cube. The empirical formula for this compound would be (b) the activation energy is infinity
(a) A 3B (b) AB3 (c) the absolute temperature is infinity
(d) the temperature in Celsius is zero.
(c) A 2B (d) AB
23. Which one of the following cyano complexes would exhibit
15. In a reaction, when the concentration of reactant is increased
the lowest value of paramagnetic behaviour ?
two times, the increase in rate of reaction was four times.
Order of reaction is : (a) [Co(CN) 6 ]3 - (b) [Fe(CN) 6 ]3 -
(a) zero (b) 1
(c) 2 (d) 3 (c) [Mn (CN) 6 ]3 - (d) [Cr (CN) 6 ]3 -
16. The cell reaction Cu + 2Ag ® Cu2+ + Ag is best represented
+
(At. no : Cr = 24, Mn = 25, Fe = 26, Co = 27)
by
24. On the basis of the following thermochemical data :
(a) Cu(s) | Cu 2+ (aq) | | Ag + (aq) | Ag(s) (Δ f G°H + (aq) = 0)

(b) Pt | Cu 2+ | | Ag + (aq) | Ag(s) H 2 O(l ) ® H + (aq) + OH – (aq); DH = 57.32 kJ

(c) Cu 2+ | Cu | | Pt | Ag 1
H2 (g)+ O2 (g) ¾¾ ® H2 O(l); ΔH=–286.20 kJ
(d) None of the above representations 2
17. Chlorine is liberated when we heat The value of enthalpy of formation of OH– ion at 25° C is:
(a) KMnO4 + NaCl (b) K2Cr2O7 + MnO2 (a) –228.88 kJ (b) +228.88 kJ
(c) Pb(NO3)2 + MnO2 (d) K2Cr2O7 + HCl (c) –343.52 kJ (d) –22.88 kJ
18. According to kinetic theory of gases, for a diatomic molecule 25. In which of the following pair both the species have sp3
(a) the pressure exerted by the gas is proportional to mean hybridization?
velocity of the molecule (a) H2S, BF3 (b) SiF4, BeH2
(b) the pressure exerted by the gas is proportional to the
(c) NF3, H2O (d) NF3, BF3
root mean velocity of the molecule
(c) the root mean square velocity of the molecule is 26. What is the product of the following reaction ?
inversely proportional to the temperature Cl
(d) the mean translational kinetic energy of the molecule
is proportional to the absolute temperature. (CH ) NLi
¾¾ ¾
3 ¾
2 ¾®
?
19. Larger number of oxidation states are exhibited by the (CH 3 ) 2 NH
actinoids than those by the lanthanoids, the main reason
being (a) N, N-dimethylaniline
(a) 4f orbitals more diffused than the 5f orbitals (b) phenyllithium (C6H5Li)
(b) lesser energy difference between 5f and 6d than (c) para-chloro-N, N-dimethylaniline
between 4f and 5d orbitals (d) meta-chloro-N, N-dimethylaniline
MOCK TEST 1 MT- 3

27. From amongst the following alcohols the one that would 33. Which of the following graph correspond to one node
react fastest with conc. HCl and anhydrous ZnCl2, is
(a) 2-Butanol (b) 2- Methylpropan-2-ol
(c) 2-Methylpropanol (d) 1- Butanol
Y Y
28. Number of moles of MnO-4 required to oxidize one mole of
ferrous oxalate completely in acidic medium will be : (a) (b)
(a) 0.6 moles (b) 0.4 moles
a0 a0
(c) 7.5 moles (d) 0.2 moles
29. Which of the following practices will not come under green
chemistry?
(a) If possible, making use of soap made of vegetable oils
instead of using synthetic detergents. Y Y
(b) Using H2O2 for bleaching purpose instead of using
chlorine based bleaching agents. (c) (d)
(c) Using bicycle for travelling small distances instead of
a0 a0
using petrol/diesel based vehicles.
(d) Using plastic cans for neatly storing substances.
30. The following alcohol is treated with conc. H2SO4, the major 34. Arrange the following ions in the order of decreasing X – O
product obtained is bond length, where X is the central atom

(a) ClO -4 ,SO 24 - , PO34- ,SiO -4

conc. H2SO4
¾¾¾¾®
(–H2O) (b) SiO 44 - , PO34- ,SO24 - , ClO-4
C6H5
OH (c) SiO 44 - , PO34- ,ClO4- ,SO42 -

(d) SiO44 - ,SO42- , PO34- , ClO-4

(a) C6H5 35. The reaction of benzyl chloride with sodium cyanide
followed by reduction with hydrogen in the presence of
H nickel gives
(a) b-Phenylethylamine (b) N-Isobutylaniline
(b) C H (c) Benzylamine (d) Aniline.
6 5
H 36. Arrange the following compounds in order of increasing
basic strength. (weakest ® strongest)
H
H O
(c) C6H5
NH2 CH2NH2 NH2 CNH2
NO2
31. The strength in volumes of a solution containing 30.36 g/L
of H2O2 is
(a) 10 V (b) 5 V 1 2 3 4
(c) 20 V (d) None of these
32. The position of some metals in the electrochemical series in (a) 4 < 2 < 1 < 3 (b) 4 < 3 < 1 < 2
decreasing electropositive character is given as (c) 4 < 1 < 3 < 2 (d) 2 < 1 < 3 < 4
37. Which of the nitrogen of histidine is first protonated ?
Mg > Al > Zn > Cu > Ag. What will happen, if a copper
spoon is used to stir a solution of aluminium nitrate ? +
b NH3
N
(a) The spoon will get coated with Al
(b) An alloy of Cu and Al is formed CH2CHCOO–
aN
(c) The solution becomes blue H
(d) There is no reaction (a) a (b) b (c) both (d) None
 EBD_7374
MT- 4 CHEMISTRY

38. Which of the following structure is similar to graphite? 42. The order of ionisation potential between He+ ion and
(a) B (b) B4C H-atom (both species are in gaseous state) is:
(c) B2H6 (d) BN (a) I. P. (He+) = I.P. (H) (b) I. P. (He+) < I.P. (H)
39. Four species are listed below: +
(c) I. P. (He ) > I.P. (H) (d) cannot be compared
i. HCO3– ii. H3 O+ 43. Which one of the following arrangements represents the
correct order of least negative to most negative electron
iii. HSO4– iv. HSO3F
gain enthalpy for C, Ca, Al, F and O?
Which one of the following is the correct sequence of their
(a) Ca < Al < C < O < F (b) Al < Ca < O < C < F
acid strength? (c) Al < O < C < Ca < F (d) C < F < O < Al < Ca
(a) iv < ii < iii < i (b) ii < iii < i < iv 44. The monomer of the polymer;
(c) i < iii < ii < iv (d) iii < i < iv < ii
40. Arrange the following in increasing order of stability CH3 CH3
+ |
+
(A) (CH3 )2 C - CH 2 CH3 (B) (CH3 )3 C ÚÚÚÚÚCH 2 - C - CH 2- C + is
|
+ + CH3 CH3
(C) (CH3 )2 CH (D) CH3 CH 2
+ CH3
(E) CH3
(a) H 2C = C (b) CH3CH = CHCH3
(a) E < D < C < B < A (b) E < D < C < A < B
CH3
(c) D < E < C < A < B (d) A < E < D < C < B
41. An organic compound A upon reacting with NH3 gives B. (c) CH3CH = CH2 (d) (CH3)2C = C(CH3)2
On heating B gives C. C in presence of KOH reacts with Br 2 45. The rate of diffusion of SO2, CO2 , PCl3 and SO3 are in the
to given CH3CH2NH2. A is : following order
(a) CH3COOH (b) CH3CH2CH2COOH (a) PCl3 > SO3 > SO2 >CO2
(c) CH3 - CH - COOH (d) CH3CH2COOH (b) CO2 > SO2 > PCl3 > SO3
| (c) SO2 > SO3 > PCl3 > CO2
CH3 (d) CO2 > SO2 > SO3 > PCl3
 M ck Test - 2
Time : 1 hr. Max. Marks -180

1. 100 ml O2 and H2 kept at same temperature and pressure. 10. Which of the following oxides is amphoteric in character?
What is true about their number of molecules (a) SnO2 (b) SiO2
(a) NO > NH (b) NO < NH (c) CO2 (d) CaO
2 2 2 2 11. Incorrect statement about PH3 is:
(c) NO = NH (d) NO + NH = 1 mole
2 2 2 2 (a) It is produced by hydrolysis of Ca3P2
2. How many joules of heat are absorbed when 70.0 grams of (b) It gives black ppt. (Cu3P2) with CuSO4 solution
water is completely vaporised at its boiling point? (c) Spontaneously burns in presence of P2H4
(a) 23,352 (b) 7,000 (d) It does not react with B2H6
(c) 15,813 (d) 158, 200 12. The IUPAC name of the compound
3. Faraday’s laws of electrolysis will fail when CH3CH = CHC º CH is
(a) temperature is increased (a) Pent-l-yn-3-ene (b) Pent-4-yn-2-ene
(b) inert electrodes are used (c) Pent-3-en-1-yne (d) Pent-2-en-4-yne
(c) a mixture of electrolytes is used 13. Butter of tin is
(d) in none of the above cases (a) SnCl4 .6H 2O (b) SnCl4 .4H 2O
4. When KMnO4 acts as an oxidising agent and ultimately (c) SnCl4 .5H 2 O (d) SnCl4 .2H 2O
forms [MnO4]2–, MnO2, Mn2O3, Mn2+ then the number of 14. In lime kiln, the reversible reaction
electrons transferred in each case respectively is CaCO3 (s) CaO (s) + CO2 (g)
(a) 4, 3, 1, 5 (b) 1, 5, 3, 7 (c) 1, 3, 4, 5 (d) 3, 5, 7, 1. proceeds to completion because
5. Iso-butyl bromide may be obtained from iso-butylene and (a) of high temperature (b) CO2 escaped out
HBr in the presence of (c) CaO is removed (d) of low temperature
(a) peroxide (b) hydroquinone 15. Rate of a reaction can be expressed by following rate
(c) diphenylamine (d) All of these expression
Rate = k[Average]2 [B], if concentration of A is increased
6. A sequence of how many nucleotides in messenger RNA
by 3 times, and concentration of B is increased by 2 times,
makes a codon for an amino acid?
how many times rate of reaction increases?
(a) Three (b) Four
(a) 9 times (b) 27 times
(c) One (d) Two
(c) 18 times (d) 8 times
7. FeS2 + O2 ® Fe2O3 + SO2
16. To prepare 3-ethylpentan-3-ol, the reagents needed are –
In the above equation, the number of electrons lost by one
(a) CH3CH2MgBr + CH3COCH2CH3
molecule of FeS2 are –
(b) CH3MgBr + CH3CH2CH2COCH2CH3
(a) 6 (b) 2
(c) CH3CH2MgBr + CH3CH2COCH2CH3
(c) 1 (d) 11
(d) CH3CH2CH2MgBr + CH3COCH2CH3
8. The enthalpies of formation of Al2O3 and Cr2O3 are –1596 kJ
and –1134 kJ respectively. DH for the reaction
2Al + Cr2 O3 ® 2Cr + Al2 O3 is 17.
H SO
2 4
¾¾¾¾ ®
(a) – 2730 kJ (b) – 462 kJ
OH
(c) – 1365 kJ (d) + 2730 kJ
9. An electrochemical cell is set up as follows : Which carbocation is involved in the above reaction ?
Pt (H2, 1 atm)/0.1 M HCl/0.1 M acetic acid/(H2, 1 atm) Pt
EMF of this cell will not be zero because
(a) the temperature is constant (a) (b)
(b) the pH of 0.1 M HCl and 0.1 M acetic acid is not the
+
same +
(c) acids used in the two compartments are different
(d) EMF of a cell depends on molarities of the acids used (c) Both (d) None
 EBD_7374
MT- 6 CHEMISTRY

18. Electrolytic reduction of nitrobenzene in weakly acidic 26. If one end of a piece of a metal is heated the other end
medium gives becomes hot after some time. This is due to
(a) N-Phenylhydroxylamine (a) Energised electrons moving to the other part of the
(b) Nitrosobenzene metal
(c) Aniline (b) resistance of the metal
(d) p-Hydroxyaniline (c) mobility of atoms, in the metal
19. In the presence of cobalt chloride (CoCl2), bleaching powder (d) minor perturbation in the energy of atoms.
decomposes to form 27. Which inert gas show abnormal behaviour on liquefaction
(a) CaCO3 and O3 (b) ClO2 and CaO (a) Xe (b) He (c) Ar (d) Kr
(c) Cl2O and CaO (d) CaCl2 and O2 28. Which of the following is correctly matched?
.. Column - I Column - II Column - III
20. CH2 – C – CH 3 and CH2 = C – CH3 are
|
||
:O (a) éëCr ( CO) 6 ùû Paramagnetic Octahedral, sp3d 2
O . .:
(a) resonating structures (b) tautomers (b) éëFe ( CO)5 ùû Paramagnetic Trigonal bipyramidal, sp3d
(c) geometrical isomers (d) optical isomers
(c) [ Co ( CO)4 ] Paramagnetic Square planar, dsp 2
21. The reaction L ¾ ¾® M is started with 10.0 g of L. After 30
and 90 minutes 5.0 g and 1.25 g of L respectively are left.
(d) [ Ni (CO )4 ] Diamagnetic Square planar, dsp2
29. Which of the following cannot be formed ?
The order of the reaction is
(a) 0 (b) 1 (a) He2+ (b) He+ (c) He (d) He2
(c) 2 (d) 3 30. Which of the following is not a characteristic of interstitial
22. The outer orbitals of C in ethene molecule can be considered compounds of transition elements?
to be hybridized to give three equivalent sp2 orbitals. The (a) The formulae of these compounds do not correspond
total number of sigma (s) and pi (p) bonds in ethene molecule to any normal oxidation state
is (b) They have melting points higher than those of pure
(a) 1 sigma (s) and 2 pi (p) bonds elements
(b) 3 sigma (s) and 2 pi (p) bonds (c) They are very hard and some compounds approach
(c) 4 sigma (s) and 1 pi (p) bonds diamond in hardness
(d) 5 sigma (s) and 1 pi (p) bonds (d) They are insulators in contrast to the transition metals
23. Which sequence represents the best synthesis of 4- 31. Placebo is often given to patients. It is
isopropylbenzonitrile? (a) an antidepressant
(b) a broad spectrum antibiotic
(CH3)2CH C N (c) a sugar pill
(d) a tonic
4-Isopropylbenzonitrile
32. Which observation(s) reflect(s) colligative properties?
(a) Benzene + (CH3)2CHCl, AlCl3; Br2, FeBr3; KCN (i) a 0.5 m NaBr solution has a higher vapour pressure
(b) Benzene + (CH3)2CHCl, AlCl3; HNO3, H2SO4; Fe, HCl; than a 0.5 m BaCl2 solution at the same temperature
NaOH; NaNO2, HCl, H2O (ii) pure water freezes at the higher temperature than pure
methanol
(c) Benzene + (CH3)2CHCl, AlCl3; HNO3, H2SO4; Fe, HCl;
NaNO2/HCl; KCN (iii) a 0.1 m NaOH solution freezes at a lower temperature
than pure water
(d) Benzene + HNO3, H2SO4; (CH3)2CHCl, AlCl3; Fe, HCl;
Choose the correct answer from the codes given below
NaNO2, HCl, H2O; CuCN
(a) (i), (ii) and (iii) (b) (i) and (ii)
24. The reaction of C6H5CH = CHCHO with NaBH4 gives (c) (ii) and (iii) (d) (i) and (iii)
(a) C6H5CH2CH2CH2OH (b) C6H5CH = CHCH2OH 33. In the commercial electrochemical process for aluminium
(c) C6H5CH2CH2CHO (d) C6H5CH2CHOHCH3 extraction the electrolyte used is
25. In Kjeldahl’s method for the estimation of nitrogen, the
(a) Al(OH )3 in NaOH solution
formula used is
1.4VW (b) An aqueous solution of Al 2 (SO 4 )3
(a) %N = (b) %N = 1.4VW
N V
VNW 1.4 VN (c) A molten mixture of Al2 O 3 and Na 3 AlF6
(c) %N = (d) %N =
1.8 W (d) A molten mixture of Al 2 O 3 and Al(OH )3
MOCK TEST 2 MT- 7

OH - OH - H+ 42. HCl
¾¾¾¾® (A) ¾¾¾¾
EtONa
®(Z) (major)
34. PhCOCHBr2 ¾¾¾® A ¾¾¾® B ¾¾¾
®C peroxide D
The compound C is –
Identify (Z) in the above sequence of reactions:
(a) PhCH(OH)CHO (b) PhCH(OH)COOH
(c) PhCOCBr2 (d) Ph - C - CH 2 - OH (a) (b)
| ||
H O O CH3
R1/2 ms–1 at
35. If urms of a gas is 30 27 °C then molar mass of (c) (d)
OEt
gas is:
(a) 0.02 kg/mol (b) 0.001 kg/mol 43. Which of the following is the incorrect statement?
(c) 0.003 kg/mol (d) 1 kg/mol (a) NaCl has 6 : 6 coordination and CsCl has 8 : 8
36. The absolute enthalpy of neutralisation of the reaction: coordination.
MgO (s) + 2HCl (aq) ¾® MgCl2 (aq) + H2O (l) will be: (b) In Na2O each oxide ion is coordinated by 8Na+ ions
(a) -57.33 kJ mol-1 and each Na+ ion by 4 oxide ions
(c) NaCl structure transform to CsCl structure on heating
(b) greater than -57.33 kJ mol- 1
(d) In CaF2 structure each F– ion is coordinated by 4 Ca2+
(c) less than -57.33 kJ mol-1 and vice-versa.
(d) 57.33 kJ mol-1 44. The property which distinguishes formic acid from acetic
37. Which of the following electrolytes is least effective in acid is
coagulating ferric hydroxide solution? (a) only ammonium salt of formic acid on heating gives
(a) KBr (b) K2SO4 amide
(c) K2CrO4 (d) K4 [Fe(CN)6] (b) when heated with alcohol/H2SO4 only acetic acid
38. Estimation of calcium and magnesium is done by forms ester
(a) EDTA (b) oxalate (c) only acetic acid forms salts with alkali
(c) Phosphate (d) none of these (d) only formic acid reduces Fehling’s solution
39. Which of the following is colourless in water? D NH3 Br2
(a) Ti3+ (b) V3+ 45. Succinic acid ¾¾ ® (A) ¾¾¾ ® (B) ¾¾¾ ® (C) ;
D KOH
(c) Cu 3+ (d) Sc3+ Product (C) will be:
40. Which is a polymer of three different monomers ?
(a) ABS (b) SBR CH2 CO2H CH2 CO2H
(c) NBR (d) Nylon-26 (a) (b)
CH2 CH2 NH2 CH2 NH2
41. Which of the following element is extracted commercially by
the electrolysis of an aqueous solution of its compound? CH2
–
CO2 K+ CH2 CO2H
(a) Chlorine (b) Bromine (c) (d)
(c) Sodium (d) Aluminium CH2 NH2 CH2 CH2 Br
 EBD_7374
MT- 8 CHEMISTRY

M ck Test - 3
Time : 1 hr. Max. Marks -180

1. Chlorination of benzene is not possible in the following 9. Which of the following has highest knocking property ?
reaction : (a) Aromatic hydrocarbons
FeCl (b) Olefins
(a) C 6 H 6 + Cl 2 ¾¾ ¾3 ® (c) Branched chain paraffins
(b) H+ (d) Straight chain paraffins
C 6 H 6 + HOCl ¾¾
¾®
10. Among the following compounds (I - III), the ease of their
ZnCl reaction with electrophiles is,
(c) C 6 H 6 + I - Cl ¾¾ ¾
¾2®

(d) AlCl
C 6 H 6 + Cl 2 ¾¾ ¾3 ® OCH3 NO2

2. Which of the following is optically inactive?

H H
H 3C Cl Cl CH3
(a) (b)
Cl CH3 H3C Cl I II III
H H
(a) II > III > I (b) III > II > I
H (c) II > I > III (d) I > II > III
H 3C Cl 11. Haemoglobin contains 0.334% of iron by weight. The
(c) (d) none of these.
H 3C Cl molecular weight of haemoglobin is approximately 67200.
H The number of iron atoms (at. wt. of Fe is 56) present in one
3. EAN of cobalt is 36 in [Co(NH3)2O2(en)Cl]. Thus, O2 is molecule of haemoglobin are
(a) dioxide (b) superoxide ion (a) 1 (b) 6
(c) peroxide ion (d) oxide (c) 4 (d) 2
4. Chromyl chloride oxidises toluene to benzaldehyde, this 12. Nessler’s reagent is
reaction is known as (a) KHgI4 (b) K2HgI4 + NH4OH
(a) Rosenmund reaction (c) K2HgI4 + KOH (d) KHgI4 + NH4OH
(b) Wurtz reaction 13. All of the following substances react with water. The pair
(c) Etard reaction that gives the same gaseous product is
(d) Fittig reaction (a) K and KO2 (b) Na and Na2O2
5. If 0.1 M of a weak acid is taken, and its percentage of degree (c) Ca and CaH2 (d) Ba and BaO2
of ionization is 1.34%, then its ionization constant will be : 14. AB; crystallizes in a body centred cubic lattice with edge
(a) 0.8 × 10–5 (b) 1.79 × 10–5 length ‘a’ equal to 387 pm. The distance between two
(c) 0.182 × 10–5 (d) none of the above oppositely charged ions in the lattice is :
6. An organic compound X (molecular formula C6H7O2N) has (a) 335 pm (b) 250 pm
six carbon atoms in a ring system, two double bonds and a (c) 200 pm (d) 300 pm
nitro group as substituent, X is 15. The reagent (s) which can be used to distinguish
(a) Homocyclic but not aromatic acetophenone from benzophenone is (are)
(b) Aromatic but not homocyclic (a) 2,4- Dinitrophenylhydrazine
(c) Homocyclic and aromatic (b) Aqueous solution of NaHSO3
(d) Heterocyclic and aromatic (c) Benedict reagent
7. Black-foot disease is caused due to groundwater (d) I2and NaOH.
contaminated with excess of 16. For the cell
(a) Nitrate (b) Fluoride
Zn | Zn 2 + (1M) || Cu 2 + (1M) | Cu, Eo is 1.10 V,,
cell
(c) Arsenic (d) Sulphur
o
8. A metal M on heating in nitrogen gas gives Y. Y on treatment Ecell2+ /Cu = 0.34V and for the cell Cu | Cu2+ (1M) || Ag+
with H2O gives a colourless gas which when passed through
o
CuSO4 solution gives a blue colour. Y is (1M) | Ag, Eocell = 0.46V hence, Ecell of the cell
(a) NH3 (b) Mg(NO3)2
(c) Mg3N2 (d) MgO Zn | Zn 2 + (1M) || Ag + (1M) | Ag is
MOCK TEST 3 MT- 9

(a) – 0.04 V (b) + 0.04 V Two sets of gases are :

(c) + 0.30 V (d) + 1.56 V (I) O2, CO2, H2 and He
17. Among the following complexes, optical activity is possible (II) CH4, O2 and H2
in
The gases given in set-I in increasing order of ‘b’ and gases
(a) [Co( NH3 ) 6 ]3+ given in set-II in decreasing order of ‘a’, are arranged below.
(b) [ Co ( H 2 O ) 2 ( NH 3 ) 2 Cl 2 ] + Select the correct order from the following :
(c) [Cr(H 2 O) 2 Cl2 ]+ (a) (I) He < H2 < CO2 < O2 (II) CH4 > H2 > O2
(d) [ Co ( CN ) 5 NC] (b) (I) O2 < He < H2 < CO2 (II) H2 > O2 > CH4
(c) (I) He < H2 < O2 < CO2 (II) CH4 > O2 > H2
18. The r.m.s velocity of hydrogen is 7 times the r.m.s velocity
(d) (I) H2 < O2 < He < CO2 (II) O2 > CH4 > H2
of nitrogen. If T is the temperature of the gas , then
25. The correct order of the decreasing ionic radii among the
(a) T(H2 ) = T(N2 ) (b) T(H2 ) > T(N 2 )
following isoelectronic species are :
(c) T(H2 ) < T(N 2 ) (d) T(H 2 ) = 7T( N 2 ) (a) Ca 2+ > K + > S2– > Cl–1
19. The correct order of ionic radii of Y3+, La3+, Eu3+ and Lu3+ is (b) Cl – > S2- > Ca 2 + > K +
(c) S2– > Cl – > K + > Ca 2+
(a) Y3+< La3+ < Eu3+< Lu3+
(b) Lu3+< Eu3+ < La3+< Y3+ (d) K + > Ca 2+ > Cl – > S 2–
26. The decreasing order of reactivity of
(c) La3+< Eu3+ < Lu3+< Y3+
m-nitrobromobenzene (I);
(d) Y3+< Lu3+ < Eu3+< La3 +
2,4,6-trinitrobromobenzene (II);
20. The pKa of an amino acid is 9.15. At what pH amino acid is
5% dissociated ? p-nitrobromobenzene (III); and
(a) 9.15 (b) 4.85 2,4-dinitrobromobenzene (IV)
(c) 9.44 (d) 7.87 towards OH– ions is
21. In the froth floatation process for the purification of ores, (a) I > II > III > IV(b) II > IV > III > I
the ore particles float because (c) IV > II > III > I(d) II > IV > I > III
(a) They are light 27. SnO2 is taken in basic medium and current is passed.
(b) Their surface is hydro dphobic i.e. not easily wetted Colloidal sol migrates towards
by water (a) anode (+ plate) (b) cathode (– plate)
(c) They bear electrostatic charge (c) both (a) and (b) (d) none of these
(d) They are insoluble 28. 0.45 g of acid of molecular weight 90 was neutralized by 20
22. T50 of first -order reaction is 10 min. Starting with 10 mol ml. of a 0.5N caustic potash. The basicity of an acid is
L–1, rate after 20 min is (a) 1 (b) 2
(a) 0.0693 mol L–1 min–1 (c) 3 (d) 4
29. Which of the following is a broad spectrum drug?
(b) 0.0693 × 2.5 mol L–1 min–1
(a) Plasmoquine (b) Chloroquine
(c) 0.0693 × 5 mol L–2 min–1
(c) Chloramphenicol (d) D.D.T.
(d) 0.0693 × 10 mol L–1 min–1
30. A compound on treatment with NaOH followed by addition
23. Pair of complexes, which do not have equal number of
of Ag NO 3 produces white precipitate at room temperature.
unpaired electron (s)?
The precipitate is soluble in NH4OH. The compound is
(a) [Co ( CO )4 ]- , [ Ni ( CN )4 ]4- identified as
(a) vinyl chloride (b) benzyl chloride
3+ 2-
(b) éë Co ( H 2 O )6 ùû , [ NiF6 ] (c) chlorobenzene (d) ethyl bromide
31. A body centered cubic lattice is made up of hollow spheres
2+ 4- of B. Spheres of solid A are present in hollow spheres of B.
(c) [ Ni ( en )3 ] , [ Cr ( CN )6 ]
Radius of A is half of radius of B. What is the ratio of total
volume of spheres of B unoccupied by A in a unit cell and
(d) [Co ( CN )6 ]4- , éëCr ( NH3 )6 ùû3+ volume of unit cell?
24. For real gases van der Waals equation is written as 7 3p 7 3
(a) (b)
æ 2ö 64 128
an
çè p + 2 ÷ø (V– nb) = nRT
V 7.p
(c) (d) None of these
where ‘a’ and ‘b’ are van der Waals constants. 24
 EBD_7374
MT- 10 CHEMISTRY

32. Equivalent conductance of an electrolyte containing NaF

at infinite dilution is 90.1 Ohm–1cm2. If NaF is replaced by NH2
KF what is the value of equivalent conductance? (I) (II)
(a) 90.1 Ohm–1cm2 (b) 111.2 Ohm–1cm2 N
H
(c) 0 (d) 222.4 Ohm–1cm2
33. The enthalpy of combustion of C6H6 is –3250 kJ, when 0.39 CH3
gm of C6H6 is burnt in excess of oxygen in an open vessel, N
the amount of heat evolved is (III) (IV)
NH2
(a) 8.32 kJ (b) 12.36 kJ
(c) 16.25 kJ (d) 20.74 kJ (a) (I) < (II) < (IV) < (III) (b) (I) < (II) < (III) < (IV)
34. In which of the following is there a consistent decrease in (c) (II) < (I) < (IV) < (III) (d) (II) < (I) < (III) < (IV)
atomic radius as the atomic number increases? 41. Benzoic acid gives benzene on being heated with X and
(a) halogens phenol gives benzene on being heated with Y. Therefore X
(b) representative elements and Y are respectively
(c) transition elements (a) Soda-lime and copper
(d) lanthanides (b) Zn dust and NaOH
35. The basicity of aniline is less than that of cyclohexylamine. (c) Zn dust and soda-lime
This is due to (d) Soda-lime and zinc dust.
(a) + R effect of —NH2 group 42. The enthalpies of the following reactions are shown below.
(b) – I effect of —NH2 group
1 1
(c) – R effect of —NH2 group H2(g) + O2(g) ® OH(g) ; DH = 42.09 kJ mol–1
2 2
(d) hyperconjugation effect
36. Consider an electrochemical cell in which the following H2(g) ® 2H(g) ; DH = 435.89 kJ mol–1
reaction occurs and predict which changes will decrease O2(g) ® 2O(g) ; DH = 495.05 kJ mol–1
the cell voltage : Calculate the O –– H bond energy for the hydroxyl radical.
Fe2+ (aq) + Ag+ (aq) ® Ag (s) + Fe3+ (aq) (a) 223.18 kJ mol–1 (b) 423.38 kJ mol–1
(c) 513.28 kJ mol –1 (d) 113.38 kJ mol–1
(I) decrease the [Ag+]
(II) increase in [Fe3+] 43. Elements X, Y and Z have atomic numbers 19, 37 and 55
(III) increase the amount of Ag respectively. Which of the following statements is true about
(a) I (b) II and III (c) II (d) I and II them ?
37. Mac Arthur process is used for the extraction of: (a) Their ionization potential would increase with
(a) Au (b) Pt increasing atomic number
(c) Cu (d) Zn (b) ‘Y’ would have an ionisation potential between those
38. H3BO2 is of ‘X’ and ‘Z’
(a) monobasic and weak Lewis acid (c) ‘Z’ would have the highest ionization potential
(b) monobasic and weak Bronsted acid (d) ‘Y’ would have the highest ionization potential.
(c) monobasic and strong Lewis acid 44. MnO 4 2– (1 mole) in n eutral aqueous medium
(d) tribasic and weak Bronsted acid disproportionates to
39. The following equilibrium constants are given: (a) 2/3 mole of MnO4– and 1/3 mole of MnO2
ˆˆ† 2NH3 ; K1
N 2 + 3H 2 ‡ˆˆ (b) 1/3 mole of MnO4– and 2/3 mole of MnO2
ˆˆ† 2NO; K 2
N2 + O2 ‡ˆˆ (c) 1/3 mole of Mn 2O7 and 1/3 mole of MnO2
(d) 2/3 mole of Mn 2O7 and 1/3 mole of MnO2
1 ˆˆ† H 2 O; K 2
H2 + O2 ‡ˆˆ 45. Formation of a solution from two components can be
2 considered as
The equilibrium constant for the oxidation of NH3 by oxygen (i) pure solvent ® separated solvent molecules, DH1
to give NO is (ii) pure solute ® separated solute molecules, DH2
K 2 K32 K 22 K3 (iii) separated solvent and solute molecules ® solution,
(a) (b) DH3
K1 K1
Solution so formed will be ideal if
K1 K 2 K 2 K33 (a) DH so ln = DH1 + DH 2 - DH 3
(b) (d)
K3 K1 (b) DH so ln = DH1 - DH 2 - DH 3
40. Among the following compounds, the increasing order of (c) DH so ln = DH 3 - DH1 - DH 2
their basic strength is : (d) DH so ln = DH1 + DH 2 + DH 3
 M ck Test - 4
Time : 1 hr. Max. Marks -180

1. The standard EMF for the cell reaction,

NO2
Zn + Cu 2 + ¾
¾® Cu + Zn 2 + is 1.1 volt at 25°C. CH = CH – CH3
The EMF for the cell reaction, when 0.1 M Cu2+ and (a)
0.1 M Zn2+ solutions are used, at 25°C is
(a) 1.10 V (b) 0.10 V
(c) –1.10 V (d) – 0.110 V
NH2
2. H3C CH3 ¾¾¾¾¾¾ CH3
® P is
(i) alc. KOH
(ii) SO2Cl2 , D
(b)
I
(a) 3-Chloropropene (b) 2-Chloropropene
(c) 1-Chloropropene (d) 1, 2-Dichloropropane
NO2
3. The electrons, identified by quantum numbers n and l, CH2 – CH2 – CH2OH
(I) n = 3, l = 2 (II) n = 5, l = 0
(c)
(III) n = 4, l = 1 (IV) n = 4, l = 2
(V) n = 4, l = 0
can be placed in order of increasing energy, as
(a) I < V < III < IV < II (b) I < V < III < II < IV NH2
CH2 – CH2 – CHO
(c) V < I < III < II < IV (d) V < I < II < III < IV
4. The electronegativity difference between N and F is greater (d)
than that between N and H yet the dipole moment of
NH3 (1.5 D) is larger than that of NF3 (0.2D). This is because
6. Molecules/ions and their magnetic properties are given
(a) in NH3 the atomic dipole and bond dipole are in the
below.
same direction whereas in NF3 these are in opposite
Molecule/ion Magnetic property
directions
(i) C6H6 (a) Antiferromagnetic
(b) in NH3 as well as NF3 the atomic dipole and bond dipole
(ii) CrO2 (b) Ferrimagnetic
are in opposite directions
(iii) MnO (c) Ferromagnetic
(c) in NH3 the atomic dipole and bond dipole are in the
(iv) Fe3O4 (d) Paramagnetic
opposite directions whereas in NF3 these are in the
(v) Fe3+ (5) Diamagnetic
same direction
The correctly matched pairs in the above is
(d) in NH3 as well as in NF3 the atomic dipole and bond
(a) i-5, ii-3, iii-2, iv-1, v-4 (b) i-3, ii-5, iii-1, iv-4, v-2
dipole are in the same direction
(c) i-5, ii-3, iii-1, iv-2, v-4 (d) i-5, ii-3, iii-1, iv-4, v-2
NO2 7. 14 g of N2 and 36 g of ozone are at the same pressure and
CH3 temperature . Their volumes will be related as
(i) NaOH
5. +CH3CHO ¾¾¾¾® [ X ] (a) 2VN = 3VO3 (b) 3VN = 2VO3
(ii) D 2 2

(c) 3VN = 4VO3 (d) 4VN = 3VO3

In this reaction, [X] will be – 2 2
 EBD_7374
MT- 12 CHEMISTRY

8. Which one of the following reactions of xenon compounds 14. The correct statement(s) regarding, (i) HClO, (ii) HClO2,
is not feasible? (iii) HClO3 and (iv) HClO4, is(are)
3 (a) The number of Cl=O bonds in (ii) and (iii) together is
(a) 3XeF4 + 6H 2 O ¾¾ ® 2Xe + XeO3 +12HF + O 2
2 two
(b) 2XeF2 + 2H 2 O ¾¾ ® 2Xe + 4HF + O 2
(b) The number of lone pairs of electrons on Cl in (ii) and
(c) XeF6 + RbF ¾¾ ® Rb[XeF7 ] (iii) together is three
(d) XeO3 + 6HF ¾¾ ® XeF6 + 3H 2 O (c) The hybridization of Cl in (iv) is sp3
9. Identify the correct statement
(d) Amongst (i) to (iv), the strongest acid is (i)
(a) Elemental sodium can be prepared and isolated by
electrolysing an aqueous solution of sodium chloride 15. Benzaldehyde reacts with ethanoic KCN to give
(b) Elemental sodium is a strong oxidising agent (a) C6H5CHOHCN (b) C6H5CH(OH)COC6H5
(c) Elemental sodium is insoluble in ammonia (c) C6H5CHOHCOOH (d) C6H5CHOHCHOHC6H5
(d) Elemental sodium is easily oxidised 16. In a closed system : A(s) 2B(g) + 3C(g) , if the partial
10. Arrange the following alcohols in order of increasing ease pressure of C is doubled, then partial pressure of B will be:
of dehydration
(a) two times the original value
CH 3CH 2 OH C 6 H 5 CH 2 OH
I II
(b) one-half of its original value

Cl 3CCH 2 OH F3CCH 2 OH 1
III IV (c) times the original value
2 2
(a) II < I < IV < III (b) IV < III < II < I
(c) IV < III < I < II (d) II < I < III < IV (d) 2 2 times its original value
11. Which of the following species is basic & reducing?
(a) SO 32 - (b) SO 24 - 17. Under the influence of an electric field, the particles in a sol
migrate towards cathode. The coagulation of the same sol is
(c) S2 O 24 - (d) HSO -4
studied using NaCl, Na2SO4 and Na3PO4 solutions. Their
12. Coordination number of Cr is six. A complex with C2 O42- , coagulating values will be in the order
(a) NaCl > Na2SO4 > Na3PO4
en and superoxide O2– will be in the ratio to make complex
(b) Na2SO4 > Na3PO4 > NaCl
-
é Cr ( C O ) , ( en ) ( O ) ù (c) Na3PO4 > Na2SO4 > NaCl
ë 2 4 x y 2 zû
(d) Na2SO4 > NaCl > Na3PO4
x y z 18. A perfect gas is found to obey the relation PV3/2 = constant. If
(a) 1 1 1 the gas is compressed to half of its volume at temperature T
(b) 1 1 2
adiabatically, the final temperature of the gas will be
(c) 1 2 2
(d) 2 1 1 (a) 2T 2 (b) 4T (c) T 2 (d) 2T
13. Which among the following is substitution reaction ?
19. Which of the following complex ions has electrons that
OMgX are symmetrically filled in both t2g and eg orbitals ?
(a) C = O + RMg X ¾
¾® C
R (a) [FeF3]3– (b) [Mn(CN)6]4–
(c) [CoF6]3– (d) [CO(NH3)6]2+
O 20. Which carbocation is the most stabilized?
O

| O ¾
¾® O +
(b) +
(a) (b)
O O +

Anhy . ZnCl
(c) R 3COH ¾¾ ¾ ¾ ¾
¾2®
Turbidity +
Conc . HCl (c) (d)
+
(d) All of the above
MOCK TEST 4 MT- 13

21. In order to refine “blister copper” it is melted in a furnace 26. Among the following, the most acidic is :
and is stirred with green logs of wood. The purpose is (a) CH3COOH (b) ClCH2COOH
(a) to expel the dissolved gases in blister copper.
(c) Cl2CHCOOH (d) Cl2CHCH2COOH
(b) to bring the impurities to surface and oxidize them.
27. The Ce (Z = 58) belongs to IIIrd group of periodic table. If it
(c) to increase the carbon content of copper.
furnish one a particle to form an element 'X', then X belongs to
(d) to reduce the metallic oxide impurities with
hydrocarbon gases liberated from the wood. (a) IIIrd group (b) IInd group
st
(c) I group (d) zero group
22. One of the equivalent energy resonance structure for formate
anion is shown below 28. The heat of sublimation of iodine is 24 cal g -1 at 50°C. If

specific heat of solid iodine and its vapour are 0.055 and
: : : :

A O
H –C
0.031cal g -1 respectively, the heat of sublimation of iodine
O:
B at 100°C is
(a) 22.8 cal g–1 (b) 25.2 cal g–1
Which C – O bond is longer ?
(a) A (c) – 22.8 cal g–1 (d) – 25.2 cal g–1

(b) B +
29. In which case the NO2 will attack at the meta position
(c) Both are equal
(d) Structure shown is not correct
CCl3 NO2
23. The colour of CuCr2O7 solution in water is green because?

(a) Cr2 O72 - ions are green

(b) Cu 2+ ions are green (i) (ii)

(c) Both Cr2O2– 2+
7 and Cu ions are green

(d) Cu2+ ions are blue and Cr2 O72 - ions are yellow +
NH 3 O–
24. Arrange the following in the order of their reactivity of SN2
reaction

(i) CH2Cl (ii) CH=CH—CH2Cl (iii) ( iv)

(iii) CH 2 = CH - CH 2Cl (a) i, ii, iii (b) ii, iv

(iv) CH 3CH 2CH 2Cl (c) ii and iii only (d) ii only
30. Identify the incorrect statement :
(a) iv > iii > i > ii (b) ii > i > iii > iv
(c) i > ii > iv > iii (d) i > iii > iv > ii (a) In (Si3O9)6–, tetrahedral SiO4 units share two oxygen
25. P4O10 is not used to dry NH3 gas because atoms.
(a) P4O10 reacts with moisture in NH3 (b) Trialkylchlorosilane on hydrolysis gives R3SiOH.
(b) P4O10 is not a drying agent (c) SiCl4 undergoes hydrolysis to give H4SiO4.
(c) P4O10 is acidic and NH3 is basic (d) (Si3O9)6– has cyclic structure.
(d) P4O10 is basic and NH3 is acidic
 EBD_7374
MT- 14 CHEMISTRY

M ck Test - 5
Time : 1 hr. Max. Marks -180

1. The structure : 7. The time taken for 90% of a first order reaction to complete
is approximately
CH3 H
(a) 1.1 times that of half-life
C C H
(b) 2.2 times that of half-life
CH3 C
COOH (c) 3.3 times that of half-life
CH3 (d) 4.4 times that of half-life
shows 8. Which of the following volume (V) - temperature (T) plots
(a) tautomerism represents the behaviour of one mole of an ideal gas at one
(b) geometrical isomerism atmospheric pressure ?
(c) optical isomerism
V(L)
(d) geometrical and optical isomerism (38.8 L, 373K)
2. Ionisation of weak acid can be calculated by the formula (22.4L,
(a)
273K)
Ka 100
(a) 100 (b)
C 1 + 10(pKa - pH) T(K)
(c) Both (a) and (b) (d) None of these
3. Which of the following will yield a mixture of V(L)
2-chlorobutene and 3-chlorobutene on treatment with HCl? (28.6 L, 373K)

(a) CH 2 = C = CH – CH3 (b) (22.4L,

273K)
(b) H 2 C = C - CH = CH 2
|
T(K)
CH3
(c) CH 2 = CH - CH = CH 2 V(L)
(30.6 L, 373K)
(d) HC º C - CH = CH 2
(22.4L,
4. The compound A on heating gives a colourless gas and a (c) 273K)
residue that is dissolved in water to obtain B. Excess of CO2
is bubbled through aqueous solution of B, C is formed which T(K)
is recovered in the solid form. Solid C on gentle heating
gives back A. The compound is
V(L)
(a) CaSO4.2H2O (b) CaCO3
(c) Na2CO3 (d) K2CO3 (22.4L,
5. The fraction of total volume occupied by the atoms present (d) 273K)
in a simple cube is (14.2 L, 373K)
T(K)
p p p p
(a) (b) (c) (d)
3 2 4 2 4 6 9. Beryllium shows diagonal relationship with aluminium.
Which of the following similarity is incorrect ?
6. The straight chain polymer (silicones) is formed by
(a) Be forms beryllates and Al forms aluminates
(a) hydrolysis of CH3SiCl 3 followed by condensation
polymerisation (b) Be(OH)2 like Al(OH)3 is basic.
(c) Be like Al is rendered passive by HNO3.
(b) hydrolysis of (CH3)4Si by addition polymerisation
(d) Be2C like Al4C3 yields methane on hydrolysis.
(c) hydrolysis of (CH3)2SiCl2 followed by condensation
polymerisation 10. Four metals and their methods of refinement are given
i. Ni, Cu, Zr, Ga
(d) hydrolysis of (CH3)3SiCl followed by condensation
ii. Electrolysis, Van Arkel process, zone refining, Mond's
polymerisation
process
MOCK TEST 5 MT- 15

Choose the right method for each : CH(OH)CH3 COCH3

(a) Ni: Electrolysis; Cu: Van Arkel process; Zr: Zone
refining; Ga: Mond's process.
(b) Ni: Mond's process; Cu: Electrolysis; Zr: Van Arkel
(a) (b)
process; Ga: Zone refining
(c) Ni: Mond's process; Cu: Van Arkel process; Zr: Zone OCH3 OCH3
refining; Ga: Electrolysis.
(d) Ni: Electrolysis; Cu: Zone refining; Zr: Van Arkel CHO COOH
process; Ga: Mond's process
11. In the synthesis of glycerol from propene, compounds
formed are (c) (d)
(a) Glycerol b-chlorohydrin and allyl chloride OCH3 OCH3
(b) Glyceryl trichloride and glycerol a-chlorohydrin 18. Which one of the following statements is FALSE?
(c) Allyl alcohol and a-chlorohydrin (a) The correct order of osmotic pressure for 0.01 M
(d) Allyl alcohol and monosodium glycerolate aqueous solution of each compound is
12. The missing reagents R1 and R2 in the following series of BaCl 2 > KCl > CH3COOH > Sucrose
reactions are (b) The osmotic pressure (p) of a solution is given by the
-
R
CH3 CH 2 Br ¾¾® 1 [ ] ¾¾®R2 CH 3 CHP + Ph 3 equation p = MRT, where M is the molarity of the
solution
(a) PhLi and Ph3P respectively
(c) Raoult’s law states that the vapour pressure of a
(b) Ph3P and PhLi respectively
component over a solution is proportional to its mole
(c) Ph3P and C2H5ONa respectively
fraction
(d) Either (2) or (3) (d) Two sucrose solutions of same molality prepared in
13. At 25°C molar conductance of 0.1 molar aqueous different solvents will have the same freezing point
solution of ammonium hydroxide is 9.54 ohm–1 cm2mol–1 and depression
at in finite dilution its molar conductance is 19. The number of S=O and S–OH bonds present in
238 ohm–1 cm2 mol–1. The degree of ionisation of ammonium peroxodisulphuric acid and pyrosulphuric acid respectively
hydroxide at the same concentration and temperature is : are :
(a) 20.800% (b) 4.008% (c) 40.800% (d) 2.080% (a) (2 and 2) and (2 and 2)
14. Red precipitate is obtained when ethanol solution of (b) (2 and 4) and (2 and 4)
dimethylglyoxime is added to ammoniacal Ni(II). Which of (c) (4 and 2) and (2 and 4)
the following statements is not true ? (d) (4 and 2) and (4 and 2)
(a) Red complex has a square planar geometry. 20. Which one of the following sets forms the biodegradable
(b) Complex has symmetrical H-bonding polymer?
(a) CH2 = CH – CN and CH2 = CH – CH = CH2
(c) Red complex has a tetrahedral geometry.
(b) H2N – CH2 – COOH and H2N–(CH2)5 – COOH
(d) Dimethylglyoxime functions as bidentate ligand. (c) HO – CH2 – CH2 – OH and
15. The ratio of number of oxygen atoms (O) in 16.0 g ozone
(O3), 28.0 g carbon monoxide (CO) and 16.0 oxygen (O2) is
HOOC COOH
(Atomic mass : C = 12, O = 16 and Avogadro’s constant
NA = 6.0 × 1023 mol–1)
(a) 3 : 1 : 2 (b) 1 : 1 : 2
(d) CH = CH2 and CH2 = CH – CH = CH2
(c) 3 : 1 : 1 (d) 1 : 1 : 1
16. The secondary structure of a protein refers to 21. When a sample of gas is compressed at constant temperature
(a) fixed configuration of the polypeptide backbone from 15 atm to 60 atm, its volume changes from 76 cm 3 to
(b) a– helical backbone 20.5 cm3. Which of the following statements are possible
(c) hydrophobic interactions explanations of this behaviour?
(d) sequence of a– amino acids. (1) The gas behaves non-ideally
(2) The gas dimerises
C N
(3) The gas is adsorbed into the vessel walls
(a) 1, 2 and 3 (b) 1 and 2 only
H O+ (c) 2 and 3 only (d) 1 only
17. + CH3MgBr Q ¾¾¾®
3 P
22. An unknown compound A has a molecular formula C4H6,
OCH3 when A is treated with an excess of Br2, a new substance B
with formula C4H6Br2 is formed. A forms a white precipitate
Product 'P' in the above reaction is
with ammonical silver nitrate solution. A may be
 EBD_7374
MT- 16 CHEMISTRY

(a) Butyne-1 (b) Butyne-2

(c) Butene-1 (d) Butene-2
Br2 /hn Alcoholic
23. Consider the following conversions : 27. ¾¾¾ ¾® Major (X) ¾¾¾¾ ® Major (Y)
KOH/D

(i) O( g ) + e - ¾¾
® O(-g ) , DH1 H—Br
¾¾¾¾
Peroxide
® Major (Z):
-
(ii) ® F(-g ) , DH 2
F( g) + e ¾¾
-
® Cl(-g ) , DH3
(iii) Cl( g ) + e ¾¾ Br
(a) (b)
- -
® O 2- , DH 4
(iv) O( g ) + e ¾¾ Br
(g )
According to given information the incorrect statement is : Br
(a) DH3 is more negative than DH1 and DH2
Br
(b) DH1 is less negative than DH2
(c) DH1, DH2 and DH3 are negative whereas DH4 is (c) (d)
positive
(d) DH1, DH3 and DH2 are negative whereas DH4 is 28. Cl 2 ( g ) + Ba ( OH )2 ¾¾
® X ( aq.) + BaCl 2 + H 2O
positive
24. DG in Ag2O ® 2 Ag + 1/2O2 at a certain temperature is X + H 2SO 4 ¾¾
® Y + BaSO 4
–10 kJ mol–1. Pick the correct statement D
(a) Ag2O decomposes to Ag and O2 Y ¾¾¾¾¾
® Z + H2O + O2
D>365K
(b) Ag and O2 combines to form Ag2O Y and Z are respectively :
(c) Reaction is in equilibrium (a) HClO4, ClO2 (b) HClO3, ClO2
(d) Reaction does not take place (c) HClO3, ClO6 (d) HClO4, Cl2O7
25. If electron, hydrogen, helium and neon nuclei are all moving H
with the velocity of light, then the wavelength associated H3C C
with these particles are in the order 29. Consider the two molecules : (I) C C CH3
(a) Electron > hydrogen > helium > neon
O O
(b) Electron > helium > hydrogen > neon
H
(c) Electron < hydrogen < helium < neon
(d) Neon < hydrogen < helium < electron H H
26. In a set of reactions p-nitrotoluene yielded a product E. H3C C CH3
(II) C C .
CH3 H
O O
Br2 Sn /HCl
¾¾¾
® B ¾¾¾¾
®C H
FeBr3
Which of the following statements about them is true ?
NO2 (a) II is capable of forming intramolecular hydrogen
NaNO CuBr bonding whereas I is not
¾¾¾¾
2 ® D ¾¾¾® E
HCl HBr (b) Both are capable of forming equally stable
The product E would be: intramolecular hydrogen bonding
CH3 CH3 (c) I is likely to form more stable intramolecular hydrogen
bonding than II
Br Br Br
(d) Both of them cannot form intramolecular hydrogen
(a) (b)
bonding
30. Which one of the following statement is not true?
Br Br
(a) In vulcanization the formation of sulphur bridges between
CH3 different chains make rubber harder and stronger.
CH2 Br
(b) Natural rubber has the trans -configuration at every
Br double bond
(c) (d) (c) Buna-S is a copolymer of butadiene and styrene
Br (d) Natural rubber is a 1, 4 - polymer of isoprene
Br
 HINTS & SOLUTIONS
MOCK TEST (1-5)
MOCK TEST - 1
ANSWER KEYS
1 (a) 6 (c) 11 (b) 16 (a) 21 (d) 26 (a) 31 (a) 36 (b) 41 (d)
2 (c) 7 (c) 12 (c) 17 (d) 22 (c) 27 (b) 32 (d) 37 (b) 42 (c)
3 (d) 8 (d) 13 (d) 18 (d) 23 (a) 28 (a) 33 (b) 38 (d) 43 (a)
4 (a) 9 (c) 14 (b) 19 (b) 24 (a) 29 (d) 34 (b) 39 (c) 44 (a)
5 (c) 10 (d) 15 (c) 20 (b, c) 25 (c) 30 (b) 35 (a) 40 (b) 45 (d)

EXPLANATIONS

1. (a) Given same carbon atom, above compound doesn’t show

Cl alc./ KOH O /H O geometrical isomerism.
A ¾¾¾
2 ® B ¾¾¾¾¾
® C ¾¾¾¾®
3 2 CH 2 O 7. (c) Liquid - liquid system is known as emulsion.
Hydrocarbon
8. (d) P = PAXA + PBXB
Since hydrocarbon C give only CH2O, on ozonolysis, = PAXA+ PB (1 – XA)
C should be CH2 = CH2 hence on going backward, A
should be ethane. Thus the reactions are Þ PAXA + PB – PBXA
Cl2 / hn alc. KOH Þ PB+XA (PA – PB)
CH3CH3 ¾¾¾¾ ® CH3CH 2 Cl ¾¾¾¾®
5+5+2
(A) (B) 9. (c) For SbCl52– , H = = 6 means sp3d 2
2
O /H2O
CH 2=CH 2 ¾¾3 ¾ ¾® HCHO
(C)
D hybridization I3– , SF4 , and PCl5 ; all have
2. (c) The cyclic portion contains more C-atoms than sp3 d hybridization.
acyclic portion. Hence it is derivative of cyclopentane.
10. (d) Hemiacetal ® presence of alcohol and ether on same
3. (d) In éë Ni ( NH3 )2 Cl 2 ùû , Ni 2 + is in sp3 hybridisation, carbon.
11. (b) During disproportionation same compound undergo
thus tetrahedral in shape. Hence the four ligands are simultaneous oxidation and reduction.
not different to exhibit optical isomerism.
Oxidation
4. (a) Addition of HCN to carbonyl compounds is
nucleophilic addition reaction. The order of reactivity - + -1 +5
of carbonyl compounds is : 3HOCl ¾
¾® 2HCl+ HClO 3
HCHO > CH3COCH3 > PhCOCH3 > PhCOPh
The lower reactivity of Ketones is due to the presence reduction
of two alkyl group which shows + I effect. The reactivity 12. (c)
of Ketones decreases as the size of alkyl group 13. (d) Chloramphenicol is
increases. O
5. (c) PCl5(g) PCl3(g) + Cl2(g) ||
O2N CH - CH - NH - C – CHCl 2
1–x x x
Total moles after dissociation | |
OH CH 2 OH
1–x+x +x =1+x
p = mole fraction of PCl3 × 1
PCl 3 14. (b) Number of A ions in the unit cell. = ´8 =1
æ x ö 8
Total pressure = ç ÷P
è1+ x ø 1
H 3C Number of B ions in the unit cell = ´6 =3
2
6. (c) C CH CH 2 CH 3 Hence empirical formula of the compound = AB3
H3C 15. (c) Since rate of reaction becomes four times on doubling
Due to the presence of two similar methyl group at concentration of reactant, it is second order reaction.
 EBD_7374
MT- 18 CHEMISTRY

16. (a) For reaction (i)

17. (d) K 2 Cr2 O 7 + conc.HCl ® Cl 2 ­
DH r = DH°f (H + aq)+DH°f (OH – aq)– DH°f (H 2 O, l)
1 mnu 2
18. (d) Pressure exerted by the gas, P = ...(i) 57.32 = 0 + DH°f (OH – , aq) – DH°f (H 2O, l) …(iii)
3 V
For reaction (ii)
Here, u = root mean square velocity
m = mass of a molecule, n = No. of molecules of the gas DH r = DH°f (H 2 O, l) –
Hence (a) & (b) are clearly wrong. 1
3RT DH°f (H2 , g) – DH°f (O 2 , g)
Again u2 = [explained from (i)] 2
M –286.20 = DH°f (H 2 O, l)
Here, M = Molecular wt. of the gas; On replacing this value in equ. (iii) we have
Hence (c) is wrong
3 57.32 = DH°f (OH – , aq) – (–286.20)
Further, Average K.E. = KT; Hence (d) is true.
2 DH°f = –286.20 + 57.32
19. (b) The main reason for exhibiting larger number of = –228.88 kJ
oxidation states by actinoids as compared to
25. (c) Applying VSEPR theory, both NF3 and H2O are sp3
lanthanoids is lesser energy difference between 5 f and
hybridized.
6d orbitals as compared to that between 4f and 5d
orbitals. Cl N(CH 3 ) 2
In case of actinoids we can remove electrons from 5f as
well as from 6d and due to this actinoids exhibit larger (CH3 )2 NH
number of oxidation state than lanthanoids. 26. (a) + (CH3 )2 NLi ¾¾¾¾¾ ® + LiCl
20. (b and c) From the various given option we find option (a)
correct. The oxidising power of halogen follow the order 27. (b) Tertiary alcohols react fastest with conc. HCl and
F2 > Cl2 > Br2 > I2. Option (b) incorrect because it in anhydrous ZnCl2 (lucas reagent) as its mechanism
not the correct order of electron gain enthalpy of proceeds through the formation of stable tertiary
halogens. carbocation.
The correct order is Cl2 > F2 > Br2 > I2. The low value Mechanism
of F2 than Cl2 is due to its small size.
CH3
Option (c) incorrect. The correct order of bond |
dissociation energies of halogens is Cl2 > Br2 > F2 > I2. Step 1 : CH3 — C — OH + H - Cl
Option (d) correct. It is the correct order of |
electronegativity values of halogens. Thus option (b) CH3
and (c) are incorrect. 2-Methylpropan-2-ol
21. (d) Al2O 3 .2H 2O ® Al 2O3 + 2H 2O is calcination. +
ˆˆ† (CH 3 )3 C — OH 2 + Cl-
‡ˆˆ
22. (c) According to Arrhenius equation, the rate constant of
reaction is given by, +
ˆˆ† (CH3 )3 C + + H 2 O
Step 2 : (CH3 )3 C - OH 2 ‡ˆˆ
k = Ae – Ea /RT
3° Carbocation
where A is pre-exponential factor, Ea is activation energy
and T is absolute temperature. + ˆˆ† (CH 3 )3 C - Cl
Step 3 : (CH3 )3 C + Cl ‡ˆˆ -

E t -Butyl chloride
when T ® ¥, a ® 0 28. (a)
RT
then k = Ae0 2KMnO4 + 3H2SO4 K2SO4 + 2MnSO4 + 3H2O + 5(O)] × 3
or k=A COO
2 Fe + 3(O) Fe2O3 + 2CO2 ]×5
23. (a) Co3+ : 3d-orbital COO
6KMnO4 + 9H2SO4 + 10 COO
[Co(CN)6]3– : 3d-orbital Fe 3K2SO4 +6MnSO4 + 9H2O
(6 moles) COO + 5Fe2O3+ 10CO2
CN– is a strong field ligand and it causes pairing of (10 moles)
electrons, as a result number of unpaired electrons in From above equation 6 moles MnO4– required to oxidise
Co3+ becomes zero and hence it has lowest value of 10 moles of oxalate.
paramagnetic behaviour. Thus number of moles of MnO4– required to oxidise
24. (a) Given, for reaction 6
one mole of oxalate = = 0.6 moles
(i) H2O (l) ¾¾ ® H + (aq.) + OH – (aq.); 10
29. (d)
DH r = 57.32 kJ
1 +
(ii) H 2 (g) + O 2 (g) ¾¾
® H 2 O(l); H
2 30. (b) C6H5 C6H5
DH r = –286.20 kJ +
OH
 MOCK TEST 1 MT- 19

+ + 39. (c) The correct order of acidic strength of the given species
H rearranges
in
C6H5
Benzyl carbocation HSO3 F > H 3 O + > HSO 4 - > HCO3-
is more stable (iv) (ii) (iii) (i)

H H (i) < (iii) < (ii) < (iv)

+ H It corresponds to choice (c) which is correct answer.
–H + CH
C6H 5 6 5 40. (b) Stability depends on number of hyperconjugative
H structures.
trans–(more stable due cis– (less stable due to bulky
to steric relief) gps. lying on same side) NH
3 ® B ¾¾ D
2 ® CH CH NH Br
41. (d) A ¾¾¾ ® C ¾¾¾¾¾ 3 2 2
(I) II KOH,(III)
31. (a) Eq. wt. of H2O2 = 17
30.36 Reaction (III) is a Hofmann bromamide reaction. Now
N= = 1.78 N
17 formation of CH3CH2NH2 is possible only from a
Volume strength = 5.6 × normality compound CH3CH2CONH2(C) which can be obtained
= 5.6 × 1.78 = 10 V from the compound CH3CH2COO– NH+4 (B).
32. (d) The metal placed below in electrochemical series does
not react with that metal salt solution whose metal is Thus (A) should be CH3CH2COOH
placed above in electrochemical series. O
33. (b) P
3 ↑ CH CH COO, NH∗
CH3CH 2 , C, OH ¾¾¾
NH
34. (b) More will be the electronegativity of X, lesser will be 3 2 4
the bond length of X-O bond. (A) (B)
NaCN H / Ni Χ
35. (a) C 6 H 5CH 2Cl ¾¾¾
¾® C 6 H 5CH 2CN ¾¾2 ¾
¾® ¾¾↑ CH 3CH 2 CONH 2
Benzyl chloride
(C)
O C 6 H 5 CH 2 CH 2 NH 2
β - Phenylethy lamine
ôô KOH Br2
36. (b) (4) Ph – C – NH 2 is weak base due to resonance. CH3CH2NH2
(3) One to –M effect of NO2 and ortho effect it is weak
base. 42. (c)
(2) Strong base because lone pair is not involved in 43. (a) As the nuclear charge increases, the force of attraction
resonance. between the nucleus and the incoming electron
37. (b) Protonation at b–N leads to imidazolium ion, which is
increases and hence the elecron gain enthalpy
stabilized by two equivalent resonating structures.
becomes more negative, hence the correct order is
b + ..
N HN HN Ca < Al < C < O < F
..

+
H 44. (a) Addition of monomers follows isoprene rule
.. .. ..
aN N N CH3 CH3
H H H C = CH2 C = CH2
Equivalent resonating structures CH3 CH3
38. (d) Boron nitride (BN) is known as inorganic graphite.
H T H T
The most stable form is hexagonal one. It has layered
structure similar to graphite. ¯
CH3
N N+ H 3C +
–

–
+ B C – CH2– C – CH2
B– –B
H 3C
–

CH3
N+ +N N
– +
–B B B– –B 1
45. (d) Rate µ . The smaller the value of M the more is the
M
+N N N+ +N
+ – rate of diffusion.
B– –B B

N+ +N N
– +
B B–
 EBD_7374
MT- 20 CHEMISTRY

MOCK TEST - 2
ANSWER KEYS
1 (c) 6 (a) 11 (d) 16 (c) 21 (b) 26 (a) 31 (c) 36 (c) 41 (a)
2 (d) 7 (d) 12 (d) 17 (c) 22 (d) 27 (b) 32 (d) 37 (a) 42 (b)
3 (d) 8 (b) 13 (c) 18 (c) 23 (c) 28 (c) 33 (c) 38 (a) 43 (c)
4 (c) 9 (b) 14 (b) 19 (d) 24 (a) 29 (d) 34 (b) 39 (d) 44 (d)
5 (a) 10 (a) 15 (c) 20 (a) 25 (d) 30 (d) 35 (d) 40 (a) 45 (c)

EXPLANATIONS

1. (c) This is Avogadro’s hypothesis. 3

8. (b) 2Al + O2 ® Al2 O3 , DH = -1596 kJ .....(i)
According to this, equal volume of all gases contain 2
equal no. of molecules under similar condition of 3
2Cr + O2 ® Cr2 O3 , DH = -1134 kJ ....(ii)
temperature and pressure. 2
By (i) –(ii)
2. (d) Q = m ´ L
2Al + Cr2O3 ® 2Cr + Al 2O3 , DH = -462 kJ.
where, L = latent heat of vapourisation of water
= 2260 kJ/kg 9. (b) It is an example of concentration cell, Ecell cannot be
zero since [H+] are different (HCl is strong and
= 2260 × 103 J/kg
CH3COOH weak acid).
Q = 70 × 10–3 × 2260 × 103 = 1,58,200 Joule
10. (a) CaO is basic as it form strong base Ca(OH)2 on reaction
3. (d)
with water.

+3 +6
CaO + H2O –––––® Ca(OH)2
– +7 – –2
– 4e
¾¾ [KMnO7 ] ¾–¾
e¾® [MnO ]
4. (c) Mn2O3 ¬¾ 4 CO2 is acidic as it dissolve in water forming unstable
– 5e
– carbonic acid.
– 3e– H2O + CO2 –––––® H2CO3
+4
Mn2+ MnO2 Silica (SiO2) is insoluble in water and acts as a very
weak acid.
HBr SnO2 is amphoteric as it reacts with both acid and
5. (a) (CH3 )2 C = CH 2 ¾¾¾
® (CH3 )2 CHCH 2 Br
Isobutylene Isobutyl bromide base.
SnO2 + 2H2SO4–––––® Sn(SO4)2 + 2H2O
Note that, here HBr is added in anti-Markownikoff’s
SnO2 + 2KOH–––––® K2SnO3 + H2O
manner, so reaction should take place in presence of
peroxide. Hydroquinone and diphenylamine are not 11. (d) PH3 (Lewis base) can react with B2H6 (Lewis acid).
12. (d) When both double and triple bonds are present, then
free-radical producing substances but scavangers.
double bond is considered as the principal group.
6. (a) The sequence of bases in mRNA are read in a serial
order in groups of three at a time. Each triplet of 13. (c) Butter of tin is SnCl4 .5H2O .
nucleotides (having a specific sequence of bases) is 14. (b) Forward reaction is favoured by removal of products.
known as codon. Each codon specifies one amino acid. 15. (c) Reaction rate = k [A]2 [B]
Further since, there are four bases, therefore, 43 = 64 Now increase conc. of A by three times and conc. of B
triplets or codons are possible. by two times. Then new rate
R2 = k [3A]2 [2B]
7. (d) In FeS2, Fe2+ is converting into Fe3+ and sulphur is
changing from –1 oxidation state to +4 oxidation state. R1 k[A]2 [B] 1 1 1
= 2
= 2´ =
R 2 k[3A] [2B] 3 2 18
There are two S– and one Fe2+ in FeS2. Thus total no.
of electrons lost in the given reaction are 11. R2 = 18 × R1
Hence rate increases by 18 times.
MOCK TEST 2 MT- 21

16. (c) 24. (a) Normally NaBH4 as well as LiAlH4 reduce only –CHO
group without effecting carbon-carbon double bond,
however when it is present in conjugation with
17. (c) ¬¾® ¾¾
® benzene ring and aldehydic group it is also reduced
+ along with the reduction of –CHO group.
+
NaBH
C6 H 5 CH = CH CHO ¾¾¾¾
4®
3° 3° allylic (more stable)
18. (c) Electrolytic reduction of nitrobenzene in weakly acidic C6 H5CH 2CH 2 CH 2 OH
medium gives aniline, whereas in strongly acidic 25. (d)
medium it gives p-hydroxyaniline 26. (a) It is due to movement of energised electrons
19. (d) 2CaOCl 2 ¾¾¾
2 CoCl
® 2CaCl 2 + O 2 (KE µ T).
27. (b)
– 28. (c) Nitrogen form N2 (i.e. N º N) but phosphorus form P4,
20. (a) CH2 — C — CH3 CH2 = C — CH3 because in P2, pp — pp bonding is present which is a
weaker bonding.
O O 1
– 29. (d) He2 Bond order = (2 - 2 ) = 0 Hence cannot be
I II 2
formed.

1 30. (d) Interstitial compounds of transition metal exhibit

21. (b) After every 30 minutes the amount is reduced to metallic conductivity.
2
therefore t1/2 is 30 minutes. In 90 minutes the amount is 31. (c)
32. (d) Colligative properties depends upon the no. of particles.
1 1 Since methanol is non electrolyte hence cannot be
reduced to i.e. n . Here n = 3. True for 1st order
8 2 considered.
reaction. 33. (c)
s
s C = C —H
s OH -
22. (d) H— 34. (b) PhCOCHBr2 ¾¾¾® PhCOCHO
p
s| |s (A)
H H
O–
OH -
OH +
¾¾¾® Ph – C – C H
¾¾® PhCH(OH)COOH
AlCl O
23. (c) + (CH3)2CHCl ¾¾¾®
3
H
(B) (C)

3RT
35. (d) U rms =
HNO3 Fe / HCl Mw
¾¾¾¾ ® ¾¾¾¾ ®
H2SO4 NaOH
36. (c) As MgO is a weak base hence some energy got
consumed to break MgO (s). Hence enthalpy is less
NO2
than –57.33 kJ mol–1.
37. (a) Smaller the charge on anion, lesser will be its
KCN
coagulating power.
NaNO2/HCl
\ KBr have Br– with least charge of – 1 on Br thus
KBr is least effective in coagulating Fe(OH)3.
NH2
38. (a) Calcium and magnesium form complexes with EDTA.
39. (d) Since Sc3+ does not contain any unpaired electron it is
colourless in water.
40. (a) ABS is acrylonitrile-butadiene-styrene rubber which
is obtained by copolymerisation of acrylonitrile,
1, 3-butadiene and styrene.
CN
 EBD_7374
MT- 22 CHEMISTRY

a red ppt of cuprous oxide but acetic acid does not

CH2 = CH + CH 2 = CH + CH2 = CHC6H5 ¾¾
® give red ppt.
| | Styrene
CN CH = CH 2
Acrylonitrile O
1,3-Butadiene
COOH D H —NH
é CH 2 - CH - CH 2 CH = CHCH 2 - CH 2 - CH —
— ù 45. (c) ¾¾®
H O
O ¾¾¾®
2
D
2
ê | | ú COOH
êë CN C6H5úû n
O
ABS rubber (A)
succinic
41. (a) Cl2 is obtained by electrolysis of (aqueous) NaCl. anhydride

42. (b) O
Cl –+
(A) (Z) Br +2 COOR
NH ¾¾¾®
KOH
43. (c) NH2
44. (d) We can distinguish between formic acid and acetic acid
O
by their action on Fehling’s solution. Formic acid gives (B)
succinamide
 MOCK TEST - 3
ANSWER KEYS
1 (b) 6 (a) 11 (c) 16 (d) 21 (b) 26 (b) 31 (d) 36 (d) 41 (d)
2 (c) 7 (c) 12 (c) 17 (b) 22 (b) 27 (a) 32 (a) 37 (a) 42 (b)
3 (c) 8 (c) 13 (c) 18 (c) 23 (d) 28 (b) 33 (c) 38 (a) 43 (b)
4 (c) 9 (d) 14 (a) 19 (b) 24 (c) 29 (c) 34 (b) 39 (d) 44 (a)
5 (c) 10 (d) 15 (d) 20 (d) 25 (c) 30 (b) 35 (a) 40 (c) 45 (d)

EXPLANATIONS

1. (b) Reaction (b) does not involve the formation of Cl+, the 9. (d) Octane number defines the knocking tendencies of
electrophile. various hydrocarbons. Higher is the octane number,
2. (c) It has centre of symmetry, so optically inactive. lesser is the knocking tendency of fuel. Experimentally
3. (c) it is observed that 2, 2, 4-trimethylpentane, a branched
chain hydrocarbon has the highest anti-knocking
CH3 CHO property. It has been given an octane number 100, while
n-heptane, a straight chain hydrocarbon has the
CrO Cl
4. (c) ¾¾¾®
2 2
highest knocking property, assigned zero octane
in CCl4
number.
Toluene Benzaldehyde
10. (d) –OCH3 activates the benzene ring. –NO2 deactivates
This reaction can not be given by aliphatic compounds. the ring. Hence the reaction of the given compounds
5. (c) Percentage of degree of ionization = 1.34% with electrophiles is in the order, I > II > III.
11. (c) Given : Percentage of the iron = 0.334%; Molecular
\ Degree of ionization (a ) = 0.0134
weight of the haemoglobin
ˆˆ† CH3 COO- + H +
CH3COOH ‡ˆˆ = 67200 and atomic weight of the iron = 56. We know
Initial 0.1 0 0 that the number of iron atoms
At equilibrium 0.1(1 – 0.0134) 0.1 ´ 0.0134 0.1 ´ 0.0134
Molecular wt. of haemoglobin ´ % of iron
<
-
[CH3COO ] [H ] + 100 ´ Atomic weight of iron
K=
[CH 3COOH] 67200 ´ 0.334
= =4
0.1 ´ 0.0134 ´ 0.0134 ´ 0.1 100 ´ 56
= 12. (c) K2HgI4 + KOH is called Nessler’s reagent. It is used for
0.1 ´ (1 - 0.0134)
the detection of NH4+ in group analysis and in
= 0.182 ´ 10 -5 quantitative determination of ammonia solution. It gives
a yellow or brown precipitate with concentrations as
NO 2
low as 1 ppm of NH3.
NO 2
6. (a) or 13. (c) Ca and CaH2 both react with H2O to form H2 gas,
Ca + 2 H 2 O ¾
¾® Ca ( OH ) 2 + H 2
Hence it is homocyclic (as the ring system is made of CaH 2 + 2H 2 O ¾
¾® Ca (OH ) 2 + 2 H 2
one type of atoms, i.e. carbon) but not aromatic.As it
does not have (4n +2)p electron required for aromaticity. whereas
7. (c) K gives H2 while KO2 gives O2 and H2O2
8. (c) 3Mg + N 2 ¾¾
® Mg3 N 2 2K + 2 H2O ¾
¾® 2KOH + H2
M
M Y
2KO2 + 2H 2O ¾¾
® 2KOH + O2 + H 2O2
M g3 N 2 + 6H 2 O ¾¾
® 3Mg(OH) 2 + 2NH3 ­
Y colourless Similarly, Na gives H2 while Na2 O2 gives H2O2
CuSO 4 + 4NH3 ¾¾
® [Cu(NH 3 ) 4 ]SO 4 2 Na + 2 H 2 O ¾
¾® 2 NaOH + H 2
Blue complex
 EBD_7374
MT- 24 CHEMISTRY

Na 2 O 2 + 2H 2 O ¾
¾® 2 NaOH + H 2 O 2 20. (d) Amino acid is 5% dissociated.
Thus, [A–] = [conjugate base] = 0.05
Likewise Ba gives H2 while BaO2 gives H2O2 [HA] = [Amino acid] = 0.95
Ba + 2 H2O ¾
¾® Ba (OH)2 + H2
[A - ]
BaO2 + 2H2O ¾
¾® Ba (OH)2 + H2 O2 pH = pKa + log
[HA]
14. (a) For BCC lattice body diagonal = a 3 .
The distance between the two oppositely charged ions æ1ö
= 9.15 + log ç ÷
è 12 ø
a
= 3
2 = 7.87
387 ´ 1.732 21. (b) In froth floatation process, ore particles float because
= = 335 pm their surface is hydrophobic i.e., not easily wetted by
2
oil.
15. (d) I2 and NaOH react with acetophenone (C6H5COCH3)
22. (b) Initial concentration = 10 mol L–1
to give yellow ppt. of CHI 3 but benzophenone
\ Conc. after 20 min (two half lives) = 2.5 mol L–1
(C6H5COC6H5) does not and hence can be used to
distinguish between them. Oxidation of methyl ketones 0.693 0.693
Now, k = =
with sodium Hypoiodite (NaOI) or (I2 + NaOH) gives t1 / 2 10 min
iodoform (CHI3) but not in case of binzophenone. or 0.0693 min–1
16. (d) Eocell = Eo + Eo 2+ first cell \ rate = k × [reactant]
Zn / Zn 2+ Cu / Ca
= 0.0693 × 2.5 mol L–1 min–1
1.10 = E o + 0.34 23. (d) [ Co(CN)6 ] 4-
Zn / Zn 2+

Eo = 0.76 V CO 2 + , d 7 , SFL
Zn / Zn 2+

Eocell = Eo + Eo second cell eg

Cu / Cu 2+ Ag + / Ag

0.46 = -0.34 + E o
Ag + / Ag D0

Eo = 0.80 V
Ag + / Ag
t2
g
For third cell –
Unpaired e =1
Eocell = Eo + Eo
Zn / Zn 2+ Ag + / Ag
3+
= 0.76 + 0.80 éë Cr ( NH3 )6 ùû
= 1.56 V
17. (b) It is optically active when two Cl atoms are in cis Cr 3+ , d 3 , SFL
position.

U H2 TH 2 ´ 28 TH2 1 eg
18. (c) = = 7 Þ =
U N2 TN 2 ´ 2 TN 2 2

Þ TN2 = 2TH 2 D0
\ TN 2 > TH 2
19. (b) The correct order of ionic radii is
t 2g
Lu3+ < Eu3+ < La 3+ < Y39
3+
At. No. 71 63 57 Unpaired e = 3
–

[In lanthanides ionic radii (M3+) decreases with increase

in atomic number. Y3+ belongs to d-block].
MOCK TEST 3 MT- 25

24. (c) Molar mass ­ , ‘a’ increases

7pR 3 æ Rö
= çQ r = ÷
size of molecule ­ ,‘b’ increase 3 è 2ø
b(L/mol) a(bar. L2/mol2) Volume of unit cell = a3
H2 ® 0.02661 CH4 ® 2.25
3
He ® 0.0237 O2 ® 1.36 æ 4R ö
O2 ® 0.03183 H2 ® 0.244
Þ ç
è 3ø
÷ =
64 3
3 3
R (Q 3a = 4R )
CO2 ® 0.04267
25. (c) Among the isoelectronic species, size increases with
7pR 3
the increase in negative charge. Thus S2– has the 7p 3
Desired ratio Þ 3 =
highest negative charge and hence largest in size 64 3 64
followed by Cl–, K+ and Ca. R
3 3
26. (b) Reactivity decreases as the number of –NO2 group
w.r.t. –Br decreases. m-Nitrobromobenzene is, however, 32. (a) Because at infinite dilution the equivalent conductance
less reactive than the p-nitrobromobenzene since the of strong electrolytes furnishing same number of ions
–NO2 group at the m-position cannot stabilize the is same.
intermediate carbanion by resonance. 15
33. (c) C6 H6 + O2 ¾¾ ® 6CO2 + 3H 2 O
27. (a) In alkaline medium SnO2 is converted into negatively 2
charged colloidal sol 1 mole º 3250 kJ
SnO 2 + 2OH - ¾¾
® SnO 32 - + H 2O 0.39
mole º 3250 ´
0.39
= 16.25 kJ
78 78
SnO 2 + SnO32 - ¾¾
® [SnO 2 ]SnO32 -
144244 3 34. (b)
anion migrates to anode 35. (a) The reason for the lesser basicity of aniline as compared
Thus, (a) to that of cyclohexylamine is +R effect of –NH2 group
28. (b) No. of equivalents of caustic sdoda (i.e., electron releasing resonance effect of – NH2 group).
= 20 × 10–3 × 0.5 = 10–2
36. (d)
0.0591 [ Fe3+ ]
\ No. of equivalents of acid = 10–2 E = E° - log
1 éë Ag + ùû [ Fe 2 + ]
Wt.of acid ´ Basicity
Also, = No. of equiv.. as Q ­ {[Ag+] ¯, [Fe3+] ­}, E¯
MW
37. (a) Mac Arthur process involves extraction of gold from
0.45 sulphide ore with the help of KCN.
Þ ´ x = 10 -2 Þ x = 2
90 38. (a) The boron atom in boric acid, H3BO3 is electron
29. (c) Chloramphenicol is a broad spectrum drug. deficient i.e., boric acid is a Lewis acid with one p-
[Broad spectrum antibiotics are medicines effective orbital vacant. There is no d-orbital of suitable energy
against gram positive as well as gram negative bacteria, in boron atom. So, it can accommodate only one
e.g., tetracycline, chloramphenicol, etc.] additional electron pair in its outermost shell.
30. (b) Halides Cl –, Br –, I – React with AgNO3 to give 39. (d) Given,
AgCl ¾¾ ® soluble in NH4OH ˆˆ† 2NH 3 ; K1
N 2 + 3H 2 ‡ˆˆ ....(i)
AgBr ¾¾ ® spraringly soluble in NH4OH ˆˆ† 2NO; K 2
N 2 + O 2 ‡ˆˆ ....(ii)
AgI ¾¾ ® Insoluble 1
H2 + ˆˆ† H 2 O; K 3
O2 ‡ˆˆ ....(iii)
and the C – Cl bond is weakest in benzyl chloride [(sp3) 2
hybridised carbon is attached to Cl] We have to calculate
31. (d) Effective no. of atoms of B present in a unit cell = 2 4NH 3 + 5O2 ¾¾
® 4NO + 6H 2O; K = ?
Total volume of B unoccupied by A in a unit cell 5
or 2NH 3 + O2 ¾¾
® 2NO + 3H 2 O
( )
4 3 3 2
= 2´ R -r ´p
3
[NO]2 [H2O]3
r = radius of A For this equation, K =
[NH3 ]2 [O2 ]5 / 2
R = radius of B
 EBD_7374
MT- 26 CHEMISTRY

[NH3 ]2 [NO]2 Unstable Thus, the correct order is

but K1 = 3
, K2 =
(II) < (I) < (IV) < (III)
[N 2 ] [H 2 ] [N 2 ] [O 2 ]
Soda -lim e (X)
[H 2O] [H 2O]3 41. (d) C6 H 5COOH ¾¾¾¾¾¾®
& K3 = or K 3 =
[H 2 ] [O 2 ]½ [H 2 ]3 [O 2 ]3 / 2
C6 H6 + Na 2CO3 + H 2O
K 2 . K 33
Now operate, Zn dust (Y)
K1 C6 H 5 OH ¾¾¾¾¾® C6 H 6 + ZnO
42. (b) We have to calculate the enthalpy of the reaction
[NO]2 [H 2 O]3 [N 2 ] [H2 ]3
= ´ . OH (g) ® O(g) + H(g)
[N 2 ] [O2 ] [H 2 ]3 [O2 ]3 / 2 [NH3 ]2
From the given reactions, this can be obtained as
[NO]2 [H 2 O]3 follows.
= =K
[NH 3 ]2 [O 2 ]5 / 2
é 1 1 ù
– ê H 2 (g) + O 2 (g) + ® OH(g) ú ; DH = –42.09 kJ mol–1
ë2 2 û
K .K 3
\ K= 2 3
K1 1 1
+ [H2(g) ® 2H(g)] ; DH = × 435.89 kJ mol–1
2 2
40. (c) (a)
NH2 1 1
+ R effect + [O (g) ®0 2O(g)]; DH = × 495.05 kJ mol–1
2 2 2
Add
the lone pair of electron is less easily available for
protonation. OH(g) ® H(g) + O(g) ; DH = 423.38 kJ mol -1

(b) 43. (b) Elements X, Y, Z with atomic numbers 19, 37, 55 lie in
+ R effect group 1 (alkali metals). On moving down a group from
the size of atoms increases; the outermost electrons
N
H become less strongly held. So the ionization energy
decreases. Therefore, IE of Y could be between those
the lone pair of electron is not available for proton.
of X and Z.
(c) More +I, less H-bonding
X Y Z
N — CH3
K (19) Rb (37) Cs (55)
+ I, H-bonding
I.E. 4.3 4.2 3.9
+I more preferred than H-bonding, is due to steric 44. (a) 3MnO4 2– + 2H 2O ® MnO 2 + 2MnO 4– + 4OH –
hindrance to H-bonding in 1° amine.
2
or MnO 2–
4 + H2O ®
(d) 3
+ I, H-bonding
1 2 4
NH2 MnO 2 + MnO 4– + OH –
3 3 3
More H-bonding, less +I effect 45. (d)
 MOCK TEST - 4

ANSWER KEYS
1 (a) 4 (a) 7 (b) 10 (c) 13 (c) 16 (c) 19 (a) 22 (c) 25 (c) 28 (a)
2 (a) 5 (a) 8 (d) 11 (a) 14 (b, c) 17 (a) 20 (c) 23 (d) 26 (c) 29 (c)
3 (c) 6 (c) 9 (d) 12 (b) 15 (b) 18 (c) 21 (d) 24 (a) 27 (b) 30 (b)

EXPLANATIONS

1. (a) Since concentration of ions is the same hence 6. (c) C6H6 is diamagnetic (i – 5)
Ecell = E°cell. CrO2 is ferromagnetic (ii – 3)
MnO is antiferromagnetic (iii – 1)
2. (a) H3C CH3 CH2 CH3
alc. KOH Fe3O4 is ferrimagnetic (iv – 2)
¾¾¾¾® CH
Fe3+ is paramagnetic with 5 unpaired electron (v – 4)
I
7. (b) At the same T and P, V µ n
SO Cl , heat
¾¾¾¾¾¾¾ 2 2
® CH = CHCH Cl
allylic substitution 2 2 14 1 1
nN 2 = = ; VN 2 µ
3. (c) Applying (n + l) rule 28 2 2
(I) n + l = 3 + 2 = 5 (II) n + l = 5 + 0 = 5
36 3 3
(III) n + l = 4 + 1 = 5 (IV) n + l = 4 + 2 = 6 nO 3 = = ; VO 3 µ
48 4 4
(V) n + l = 4 + 0 = 4
Higher the value of (n + l), more is the energy associated 2
with it. In case of same value of (n + l), the electron Hence , VN 2 / VO3 = , 3VN 2 = 2VO 3
3
with higher value of n has higher energy.
\ The order is : V < I < III < II < IV 8. (d) The products of the concerned reaction react each
4. (a) In NH3 the atomic dipole (orbital dipole due to lone other forming back the reactants.
pair) and bond dipole are in the same direction whereas XeF6 + 3H 2 O ¾¾ ® XeO3 + 6HF .
in NF3 these are in opposite direction so in the former 9. (d) Elemental sodium is easily oxidised ( has low I.P.) and
case they are added up whereas in the latter case net acts as reductant.
result is reduction of dipole moment. It has been shown 10. (c) Higher the stability of the carbocation, more easily it is
in the following figure : formed and more will be the ease of its dehydration.
Thus order of stability of the carbocations of the
corresponding alcohols is
N N
+ + + +
H H H F F F F3C CH2 < Cl3C CH 2 < H3C CH2 < C6H5CH 2
Least stable due Most stable due
NO2 NO2 to intensification to resonance
CH3 CH2 of charge
NaOH 3 CH -CHO
5. (a) ¾¾¾¾
® ¾¾¾¾¾® F3 CCH 2 OH < Cl3CCH 2 OH < H 3CCH 2 OH
-H 2O H+
< C 6 H 5 CH 2 OH (Ease of dehydration)
11. (a) A base can donate electrons hence all are bases but
OH
SO 32 - can be oxidised to SO 24 - hence it is reducing also.
NO2
CH2 – CH – CH3 NO2
CH = CH – CH3 12. (b) éë Pt ( NH3 )4 Cl 2 ùû Br2
D
¾¾
® Ionization isomer
 EBD_7374
MT- 28 CHEMISTRY

17. (a) Since the sol particles migrate towards cathode, they
éë Pt ( NH3 )4 ClBr ùû Cl. Br
are positively charged. Hence, anions would be
Geometrical isomers effective in coagulation. Greater is the valence of
effective ion, smaller will be its coagulating value.
+2 +2
NH3 NH3 3

H3N Cl Cl 18. (c) PV 2 = constant.

H3N
Pt Pt nRT
Again P =
V
H3N Cl
Cl NH3
3
NH3 NH3 nRT
\ ´ V 2 = constant (K)
Cis-isomer Trans-isomer V

1
Anhy. ZnCl2 K
13. (c) R 3COH ¾¾¾¾¾¾ ® R3CCl or, TV 2 = = K' (constant)
Conc. HCl nR
It is substitution reaction. R3CCl being insoluble in
1 1
H 2 O give turbid solution. 2 2
For two states, T1V1 = T2 V2

1
Cl 2
14. (b, c) Cl–O–H æV ö
T2 = T1çç 1 ÷÷
O OH è V2 ø
(i) (ii)
V1
O But V2 = (given)
2
Cl
Cl 1

O O O OH æ
2
ö
O OH
çV ÷
(iii) (iv) \ T2 = T1 ç 1 ÷ =T 2
ç V1 ÷ 1
Number of Cl = O bonds in (ii) and (iii) together is 3 ç ÷
è 2 ø
Number of lone pairs on Cl in (ii) and (iii) together is 3
Hybridisation of Cl in all the four is sp3 19. (a) Symmetrically filled t2g and eg are those, which contain
Strongest acid is HClO4 (iv) equal distribution of electrons.
15. (b) When benzaldehyde is refluxed with aqueous alcoholic
potassium cyanide, two molecules of benzaldehyde [FeF3]3– ­ ­ eg ìequal distribution of ü
ïelectrons in orbitals ï
condense together to form benzoin. í ý
t
­ ­ ­ 2g ïî t 2g and eg ïþ
H O
KCN (alc.)
—C +C— ¾¾¾¾®
D [Mn(CN)6]4– eg unequal
O H distribution
t 2g of electrons
H O
in orbitals
—C –C—
OH [CoF6]3– eg unequal
Benzoin
distribution
t 2g of electrons
2 3 2
16. (c) K p = p B (1) pC (1) = p B (2) pC3 (2) = p B (2)
2
(2 pC (1) )3 ;

[Co(NH3)6]2+ eg unequal
p2 1 p B (2) 1 distribution
B (2)
hence = , = t 2g of electrons
p2 8 p B (1) 2 2 in orbitals
B (1)
MOCK TEST 4 MT- 29

20. (c) + 26. (c) Cl 2CHCOOH is most acidic because it has two
chlorine at a-position.
Stabilised by extended conjugation. 27. (b) 58Ce is lanthanoid.Lanthanoids are from 57 to 71 and
21. (d) 2Cu2S + 3O2 ® 2Cu2O + 2SO2 all are present in IIIrd group. Hence 58Ce forms 56X
element on emission of one a particle which belongs
3Cu 2 O + CH 4 ® 6Cu + 2H 2 O + CO to IInd group.
(From green
logs of wood) 28. (a) DH 2 - DH1 = DCp (T2 - T1 )
22. (c) Formate ion
DH 2 - 24 = (0.031 - 0.055)(100 - 50)
O O –
H–C –1
H–C Þ DH 2 = 22.8 cal g
O – O ··+
O
Hence A, B bonds are of same length. 29. (c) It has complete octet for all atoms.
23. (d) Green colour of CuCr2O7 is due to blue colour of
30. (b) The hydrolysis of trialkylchlorosilane R3SiCl yields
Cu2+ ions and yellow colour of Cr2 O 72– ions. dimer :
24. (a) Reactivity µ stability of TS.
R R
NH3
25. (c) P4 O10 + 2H 2 O ¾¾
® 4HPO ¾¾¾® NH PO
3 4 3 R Si O Si R
basic
Acidic meta phosphoric meta ammonium
acid phosphate
R R
 EBD_7374
MT- 30 CHEMISTRY

MOCK TEST - 5

ANSWER KEYS
1 (c) 4 (b) 7 (c) 10 (b) 13 (b) 16 (b) 19 (d) 22 (a) 25 (a) 28 (c)
2 (c) 5 (d) 8 (c) 11 (a) 14 (c) 17 (b) 20 (b) 23 (d) 26 (b) 29 (c)
3 (a) 6 (c) 9 (b) 12 (d) 15 (d) 18 (d) 21 (d) 24 (a) 27 (c) 30 (b)

EXPLANATIONS

1. (c) CH3 H D
4. (b) CaCO3 (s) ¾¾
® CO 2 (g) ­ + CaO(s)
C C H (A) colourless (B)
*
CH3 C ® Ca ( OH )2 (aq)
CaO(s) + H 2O(g) ¾¾
CH3 COOH (B)

It has asymmetric carbon atom (marked *) so it shows ® Ca ( HCO3 )2 (aq)

Ca ( OH )2 (aq) + 2CO2 (g) ¾¾
optical isomerism. Two groups attached to C = C are (C)
same (–CH3), so it does not show geometrical
D
isomerism. Ca ( HCO3 )2 (s) ¾¾
® CaCO3 (s) + CO2 (s) + H 2 O(g)
2. (c) For weak acid dissociation equilibria, degree of (C) (A)
dissociation (1) is given as :
5. (d) Number of atoms per unit cell = 1
Ka Ka
a= , \ % a = 100 a
C C Atoms touch each other along edges. Hence r =
2
[H + ][A - ] [H + ]Ca [H + ]a ( r = radius of atom and a = edge length)
Also, K a = = =
[HA] C(1 - a) (1 - a ) 4 3
pr
p
a Therefore % fraction = 3 3 = = 0.52
log K a = log H + + log (2r) 6
1- a
6. (c) Hydrolysis of substituted chlorosilanes yield
1- a
or pK a = pH + log corresponding silanols which undergo polymerisation.
a
CH3 Cl H OH CH 3 OH
1- a – 2HCl Si
Si + ¾¾®
pK a - pH = log CH3 Cl H OH CH 3 OH
a
Dialkyl silandiol
1- a
= 10pK a -pH Polymerisation of dialkyl silandiol yields linear
a thermoplastic polymer.
1 CH3 CH3
or, = 10pK a - pH + 1
a
HO — Si — OH + H O — Si — OH
1 100
a= ,%a= CH3 CH3
[1 + 10pK a -pH ] é1 + 10 pKa - pH ù
ë û CH3 CH3
+
H
3. (a) CH 2 = C = CH - CH 3 ¾¾
¾® HO — Si — O — Si — OH

é + + ù
= C = CH - CH3 ¾¾¾
® êCH 2 = C - CH 2CH3 + CH 2 = CH - CHCH3 ú CH3 CH3
2
ë û 2.303 100
7. (c) t 90% = log
k 100 - 90
Cl-
¾¾¾
® CH 2 = C - CH 2CH3 + CH 2 = CH - CHCH3
| | 2.303 100
t 50% = log
Cl Cl k 100 - 50
2 -Chlorobutene 3-Chlorobutene
MOCK TEST 5 MT- 31

t 90% log10 1
= \ t 90% = 3.3t 50% = × 6.023 × 1023 molecules
t 50% log 2 2
8. (c) Find the volume by either 1
V = RT/P (PV = RT) or P1V1 = P2V2 and and match it = × 2 × 6.023 × 1023 atoms
2
with the values given in graph to find correct answer. = 6.023 × 1023 atoms
Volume of 1 mole of an ideal gas at 273 K and 1 atm Therefore, the ratio is
pressure is 22.4 L and that at 373 K and 1 atm pressure 6.023 × 1023 : 6.023 × 1023 : 6.023 × 1023
is calculated as ; i.e. 1 : 1 : 1
16. (b) The secondary structure of a protein refers to the
RT 0.082 ´ 373 shape in which a long peptide chain can exist. There
V = = = 30.58 L ; 30.6 L
P 1 are two different conformations of the peptide linkage
9. (b) Be(OH)2 and Al(OH)3 are amphoteric in nature. present in protein, these are a-helix and b-conformation.
The a-helix always has a right handed arrangement. In
10. (b) 11. (a) b-conformation all peptide chains are streched out to
12. (d) ¾® CH 3CH 2 P + Ph 3Br -
CH 3CH 2 Br + Ph 3P ¾ nearly maximum extension and then laid side by side
- + and held together by intermolecular hydrogen bonds.
C H Li or
¾¾6 ¾
5¾¾® CH 3 CH = PPh 3 ¬¾® CH 3 C H P Ph 3 The structure resembles the pleated folds of drapery
C 2 H 5ONa
and therefore is known as b-pleated sheet.
Lm 9.54 CºN
13. (b) a = = = 0.04008 = 4.008 %.
L¥ 238
m 17. (b) + CH3MgBr ¾¾
®
14. (c) Nickel ions are frequently detected by the formation
of red precipitate of the complex of nickel OCH3
dimethylglyoxime, when heated with dimethylglyoxime. H3C – C = NMgBr COCH3
+
CH3 C NOH 2+
H3O
+ Ni – Mg(OH)Br, – NH3
CH3 C NOH OCH3 OCH3
Dimethylglyoxime Q P

OH 18. (d) DTf = K f ´ m ´ i . Since Kf has different values for

O
different solvents, hence even if the molality is same
CH3 C N N C CH3 DTf will be different.
Ni
CH3 C N N C CH3 19. (d)

O OH H2S2O8 H2S2O7
Nickel dimethylglyoxime
Peroxydisulphuric Pyrosulphuric
acid acid
16
15. (d) 16.0 g O3 = mole O O O O
48 || || || ||
16 HO – S – O – O – S – OH S S
= ´ 6.023 ´ 1023 molecules || || HO || O || OH
48
O O O O
16
= 3´ ´ 6.023 ´ 1023 atoms No. of 4 4
48 S=O
= 6.023 × 1023 atoms bonds
28
28.0 g CO = mole = 1 mole No. of 2 2
28 S – OH
= 1 × 6.023 × 1023 molecules bonds
= 1 × 6.023 × 1023 atoms
20. (b) Biodegradable polymer is Nylon-2-Nylon-6 which is
= 6.023 × 1023 atoms copolymer of glycine (H2N – CH2– COOH) and
16 1 aminocaproic acid (H2N–(CH2)5 – COOH).
16.0 g O 2 = mole = mole
32 2
 EBD_7374
MT- 32 CHEMISTRY

nH2N – CH2 – COOH +

glycine nH2N – (CH2)5– COOH CH3 CH3 CH3
aminocaproic acid Br2
Br Br
Sn/HCl
26. (b)
FeBr3

NO2 NO2 NH2

O O

–( HN – CH2 – C – HN – (CH2)5 – C –) n CH3 CH3

nylon – 2 – nylon – 6 Br Br NaNO2
HBr
21. (d) Given, P1 = 15 atm, P2 = 60 atm CuBr HCl
V1 = 76 cm3, V2 = 20.5 cm3.
If the gas is an ideal gas, then according to Boyle's Br N = NCl
law, it must follow the equation,
P1V1 = P2V2
P1 × V1 = 15 × 76 = 1140 Br
P2 × V2 = 60 × 20.5 = 1230 Br
\ P1V1 ¹ P2 V2 27. (c) X = Y= Z=
\ The gas behaves non-ideally.
The given information is not sufficient to comment on 28. (c) Number of p-bonds
other statements. O O
22. (a) Conversion of C4H6 to C4H6Br 2 indicates that the || ||
compound is either butyne-1 or butyne-2. However, H 2S2 O7 = HO - S - O - S - OH
|| ||
white precipitate with ammonical silver nitrate solution O O
indicates that it is a terminal alkyne, i.e. butyne-1 and
not butyne-2. O
23. (d) Order of electron gain enthalpy : Cl > F > O ||
H 2SO4 = HO - S - OH 2
Second electron gain enthalpy for an element is always ||
positive. O
24. (a) DG = –ve means the process is spontaneous.
××
25. (a) l = h / mv ; for the same velocity, l varies inversely H 2SO3 = HO - S - OH 1
with the mass of the particle. ||
O
29. (c) Structure I has two resonance forms, which make the
hydrogen bonding more stable while II molecule has
no such resonance stabilization.

30. (b) CH3 H CH 2 CH2 CH3 H

C=C C=C C=C
CH2 CH 2 CH3 H CH2 CH2
Natural rubber
(All cis configuration)

All statements except (b) are correct.