BSCCH-

BSCCH 104
B. Sc. I YEAR
LABORATORY COURSE-I
COURSE

SCHOOL OF SCIENCES
DEPARTMENT OF CHEMISTRY
UTTARAKHAND OPEN UNIVERSITY
 BSCCH-104

LABORATORY COURSE-I

SCHOOL OF SCIENCES
DEPARTMENT OF CHEMISTRY
UTTARAKHAND OPEN UNIVERSITY

Phone No. 05946-261122, 261123

Toll free No. 18001804025
Fax No. 05946-264232, E. mail info@uou.ac.in
htpp://uou.ac.in
 Board of Studies
Prof. Govind Singh Prof. B. S. Saraswat
Director, School of Sciences Professor Chemistry
Uttarakhand Open University Department of Chemistry
School of Sciences, IGNOU New Delhi
Prof S.P. S. Mehta Prof. D. S. Rawat
Professor Chemistry Professor Chemistry
Department of Chemistry Department of Chemistry
DSB Campus, Kumaun University Delhi University, Delhi
Nainital
Dr. Charu C. Pant
Programme Coordinator
Department of Chemistry
School of Sciences,
Uttarakhand Open University
Haldwani, Nainital

Programme Coordinators
Dr. Charu C. Pant Dr. Shalini Singh
Department of Chemistry Department of Chemistry
School of Sciences, School of Sciences,
Uttarakhand Open University Uttarakhand Open University
Haldwani, Nainital Haldwani, Nainital

Unit Written By: Unit No.

1. Dr. K. S. Dhami
(Retd. Professor.) 02, 03, 04, 05 & 06
Department of Chemistry
D.S.B. Campus, Kumaun University
Nainital
2. Dr. K. B. Melkani 07, 08, 09, 10 & 11
(Retd. Professor.)
Department of Chemistry
DSB Campus Kumaun University, Nainital
3. Dr. Charu C. Pant 01
Department of Chemistry
School of Sciences,
Uttarakhand Open University, Haldwani
Course Editor
Dr. N. S. Bhandari
Professor Chemistry
Department of Chemistry
S.S.J. Campus Kumaun University, Almora
Title : Laboratory Course-I
ISBN No. : 978-93-85740-56-5
Copyright : Uttarakhand Open University
Edition : 2017
Published by : Uttarakhand Open University, Haldwani, Nainital- 263139
 CONTENTS

BLOCK 1: INORGANIC CHEMISTRY LAB

Unit 1 Introduction Lab techniques: Inorganic Chemistry 1-14

Unit 2 Identification of anions 15-28
Unit 3 Identification of cations 29-53

BLOCK 2: ORGANIC CHEMISTRY LAB

Unit 4 Introduction Lab techniques: Organic Chemistry 54-60

Unit 5 Separation Techniques 61-67
Unit 6 Qualitative Analysis 68-80

BLOCK 3: PHYSICAL CHEMISTRY LAB

Unit 7 Introduction Lab Techniques: Physical Chemistry 81-92

Unit 8 Determination of surface tension 93-98
Unit 9 Determination of Viscosity 99-105
Unit 10 pH Measurement 106-110
Unit 11 Thermochemistry 111-121
LABORATORY COURSE-I BSCCH- 104

UNIT 1: INTRODUCTION LAB TECHNIQUES:

INORGANIC CHEMISTRY
CONTENTS:
1.1 Objectives
1.2 Introduction
1.3 Location of Laboratory Equipments
1.4 Laboratory Note book
1.5 Laboratory Apparatus and Operation: Heating, Evaporation, Precipitation,
Digestion Filtration, Drying and Ignition of precipitation, cooling, weighting;
1.6 Common Laboratory reagents
1.7 Laboratory Safety
1.8 Summary
1.9 Terminal questions

1.1.OBJECTIVES

This course is designed to ensure that all the students regardless of their educational
backgrounds are competent in necessary laboratory skills. These skills include but are
not limited to the use of an analytical balance, volumetric glassware, various pipettes,
performing titrimetric and spectrophotometric determinations and learning the proper
use and calibration of microscopes and centrifuges. Students should also become
familiar with using laboratory apparatus.
Use the proper laboratory techniques to do the following;
• Pour liquids from a glass-stopper bottle.
• Transfer solids from a bottle.
• Heat liquids in a beaker.
• Heat liquids in a test tube.
• Light and adjust a Bunsen burner.
• Measure to 0.1 cm with a metric ruler.
• Use a graduated cylinder to measure volume.
• Use an analytical balance to measure mass.
1.2 INTRODUCTION
Introduction to basic laboratory techniques and procedures necessary for competent
performance. Topics will include laboratory Reagents, apparatus, Glassware laboratory
safety, volumetric and gravimetric measurements, titrations, critical evaluation of data,
laboratory mathematics, preparing solutions and dilutions, and basic spectro photometric
Uttarakhand Open University Page 1
LABORATORY COURSE-I BSCCH- 104
measurements. The purpose of this experiment is to introduce several of the tools and
techniques necessary for success in this course.
Chemistry is an experimental science, and the laboratory is where you learn about “how
we know what we know about it.” The laboratory deals with the processes of scientific
inquiry that organic chemists use. It demonstrates the experimental basis of what your
textbook presents as fact. The primary goal of the laboratory is to help you understand
how Chemistry is done by actually doing it. Learning how to obtain and interpret
experimental results and draw reasonable conclusions from them is at the heart of doing
science. Your laboratory work will give you the opportunity to exercise your critical
thinking abilities, to join in the process of science.
1.3 LOCATION OF LABORATORY EQUIPMENT

(a) Chemicals and Solvents Organic and Inorganic:

Acids and Bases - under hood
Solvents - on shelves at end of benches
(b) Ovens and Refrigerators:
Each oven is designated for a specific purpose. Do not place any plastic items in the
ovens. All samples must be clearly labeled with the identity of compound, your
name and date. Ovens will be cleared weekly and improperly labeled samples will
be removed. Refrigerators. Samples must be clearly labeled.
(c) Balances:
Abuse of balances and littering of the area will not be tolerated.
1.4 LABORATORY NOTE BOOK
1.4.1. General Guideline:
1. Use a ballpoint pen (press hard if duplicate pages).Write on one side only.
2. Do not erase or use whiteout. If you make a mistake, draw a single line through
the error and write the correct entry on the top or side of it.
3. Do not remove an original page. If the entire page is incorrect, draw a single
diagonal line through the page and state the reason for this line.
4. Record all data and results (with units) directly into your notebook.
5. Do not record data on scrap paper, your hand, etc., to be transferred later.
6. Start a new page for each new experiment.
7. Write the title of the experiment, date, and your name at the top of each page.
8. Indicate if a page is continued from the previous page.
9. Never skip a space for later additions.

Uttarakhand Open University Page 2

LABORATORY COURSE-I BSCCH- 104
1.4.2. Components
A. Pre-Lab – a detailed plan of the work that you will be doing:
1. Brief statement of purpose.
2. Paragraph discussion of the safety and environmental issues (ex. waste
generation).
3. Step-by-step procedure in your own words. Be concise and complete, but do not
cop the lab manual. Use diagrams and sketches when necessary. Reference all
sources of Information.
Note: The lab manual may not be brought into the laboratory or consulted during
the laboratory session. However, the appendices are allowed.
B. Factual Record – what to record:
Keep a running account of all procedures carried out and observations made during
experimental work.
1.Record observations such as physical appearance, color, odor, and physical
properties.
2.Sketch apparatuses and label parts.
3.Use a table to record all information about reactants (see below).
4.Record all data and results, including the crude yield of products and mixtures. Use
tables when possible.
5.All of the reactants must be accounted for in the factual record. For example, if
you started with 1.0 mol of Reactant 1, you must account for the fate of all 1.0 mols
at the end of the reaction. Simply describing the isolated 0.25 mol of product at the
end (for example) will not be acceptable.
6.For calculations, show the formula and a sample calculation. If the calculation is
repeated; use a table to report your results.
7.All graphs should be constructed with a graphing program. Label all axes and
providea title for each graph.
8.Attach all spectra to your notebook, label the axes, and reference the spectra in the
procedure section.
Data Analysis/Conclusions:
Examine and discuss the accuracy and precision of your data. Is the precision
reasonable? Discuss possible systematic and random errors. Summarize the key results
and provide a conclusion. Describe any difficulties that you had. Discuss which results
are poor and provide explanations. Provide suggestions for improvement.

Uttarakhand Open University Page 3

LABORATORY COURSE-I BSCCH- 104
1.5 LABORATORY APPARATUS AND OPERATION
A. Common Laboratory Apparatus:
Beakers are useful as a reaction container or to hold liquid or solid samples. They are
also used to catch liquids from titrations and filtrates from filtering operations.

Bunsen Burners are sources of heat.

Burettes are for addition of a precise volume of liquid. The volume of liquid added can
be determined to the nearest 0.01 ml. with practice.

Clay Triangles are placed on a ring attached to a ring stand as a support for a funnel,
crucible, or evaporating dish.

Droppers are for addition of liquids drop by drop

Uttarakhand Open University Page 4

LABORATORY COURSE-I BSCCH- 104
Erlenmeyer Flasks are useful to contain reactions or to hold liquid samples. They are
also useful to catch filtrates.

Glass Funnels are for funneling liquids from one container to another or for filtering
when equipped with filter paper.

Graduated Cylinders are for measurement of an amount of liquid. The volume of

liquid can be estimated to the nearest 0.1 m with practice.

Hot Plates can also be used as sources of heat when an open flame is not desirable.

Pipets are used to dispense small quantities of liquids.

Uttarakhand Open University Page 5

LABORATORY COURSE-I BSCCH- 104
Ring stand with Rings are for holding pieces of glassware in place.

Test Tubes are for holding small samples

Test tube holders are for holding test tubes when tubes should not be touched

Volumetric Flasks are used to measure precise volumes of liquid or to make precise
dilutions.

Wash bottles are used for dispensing small quantities of distilled water.

Uttarakhand Open University Page 6

LABORATORY COURSE-I BSCCH- 104
Watch glasses are for holding small samples or for covering beakers or evaporating
dishes.

Wire Gauze on a ring supports beakers to be heated by Bunsen burners

B. Laboratory equipment:
Balances are used to determine the mass of a reagent or object.

Spectrophotometers are used to measure the absorbance or transmittance of a liquid

sample.

Fume Hoods are used to ventilate noxious or harmful gases

Uttarakhand Open University Page 7

LABORATORY COURSE-I BSCCH- 104
1.6 COMMON LABORATORY REAGENTS

Name General Description

Acetic acid An organic acid; is one of the simplest carboxylic
acids.
Acetone An organic compound: simplest example of the
ketones
Acetylene A hydrocarbon and the simplest alkyne; widely
used as a fuel and chemical building block
Ammonia Inorganic; the precursor to most nitrogen-
containing compunds; used to make fertilizer.
Ammonium hydorixde Aqueous ammonia; used in traditional qualitative
inorganic analysis
Ammonium hydoride Aqueous ammonia; used in traditional qualitative
inorganic analysis
Azobisisobutyron trile Organic compund; often used as a foamer in
plastics and rubber and as a radical initiator
Baeyer’s reagent An alkaline solution of potassium permanganate;
used in organic chemistry as a qualitive test for the
presence of unsaturation, such as double bonds;
N-Bromosuccinimide Used in radical substitution and electrophilic
addition reactions in organic chemistry
Butanone(methyl ethyl ketone) Organic compoud; similar solvent properties to
acetone but has a significantly slower evaporation
rate.
Butylated hydroxytoluene A fat soulbe organic compound that is primarily
used as an antioxidant food additive
n-Butyllithium An organolithium reagent; used as a
polymerization initiator in the production of
elastomes such as ploybutadience or styrene-
butadiene-styrene(SBS)
Carbon disfulifde A non-polar slovent; used frequently as a building
block in organic chemsitry
Carbon Toxic, and its dissolving power is low;
consequently, it has been largely
Tetrachloride Supersede by deuterated solvents
Often used for the coupling of amino acids for
Carbonylidiimidazole peptide synthesis and as a reagent in organic

Uttarakhand Open University Page 8

LABORATORY COURSE-I BSCCH- 104
synthesis
Ric ammonium nitrate An organic compund; used as an oxidising agent in
organic synthesis and as a standard oxidant in
quantitative analysis
Chloroform Organic compound; often used as CDC13
(deuterated chloroform) as a solvent for NMR
spectroscopy and as a general solvent.
Chromic acid A strong and corrosive oxidisig agent; an
intermediate in chromium plating
Chromium trioxide The acidic anhydride of chromic acid; mainly used
in chrome-plating .
Chromium trioxide The acidic anhydride of chromic acid; mainly used
in chrome-plating
Colloins reagent Used to selectivley oxidize primary alchols to an
aldehyde
Copper(I) iodide Useful in a variey of applications ranging from
organic sysnthesis to cloud seeding
Dess-martin periodinane Chemical reagent used to oxidize primary alcohols
to aldehydes and secondary alcohos to ketones
Diborance The central organic synthesis reagent for
hydroboration
Diethyl azodicarboxylate A valuable reagent but alos quite dangerous and
explodes upon heating
Diethyl ether Organic compound; a common laboraory solvent
Dihydropyran A heterocyclic compound; used as a protecting
group for alcools in organic synthesis.
Disobutlyaluminum hydride An organoaluminium compound; a redcing agent;
converts esters and nitriles to aldehydes
Diisopropyl azodicarboxylate The diisorpropyl ester of azodicarboxylic acid; a
reagent in the production of many organic
compounds
Dimethyl ether The simplest ether, a useful precursor to other
organic compounds and an aerosol propellant
Dimethylformamde Organic compound; a common solvent for
chemical reactions
Dimethylsulfide Organosulfur compund; used in petroleum refinint
and in petrochemcal production processes; a
reducing agent in ozonolysis reactions.
Dimethyl sulfoxide An organosulfur compound; an important polar

Uttarakhand Open University Page 9

LABORATORY COURSE-I BSCCH- 104
aprotic solvent that dissovles both polar and
nonpolar compounds
Dioxane A heterocyclic organic compound; classified as an
ether
Ethanol A powerful psychoactive drug; used in alcoholic
beverages, in thermometers, as a solvent, and as a
fuel.
Fehling’s reagent Used to differentiate between water-soluble
aldehyde and ketone functional groups
Fentons’ reagent A solution of hydrogen peroxide and an iron
catalyst that is used to oxidize contaminants or
waste waters.
Formaldehyde The simplest aldehyde; an important precursor to
many other chemical compounds; such as
ploymers and polyfunctional alcohols
Formic acid The simplest caroxylic acid; often used as a source
of the hydride ion
Grignard reagents The most common application is for alkylation of
aldehydes and ketones;
Hydrazine It’s a good reducing agent and is used in the wolff-
kishner reaction for reducing carbonyls to its
corresponding alkanes. Used as a foaming agent in
preparing polymer foams; also a precursor to
polymerization catalysts and pharamceuticals; also
as an oxygen scavenger in power plants.
Hydrazoic acid Used primarily for preservation of stock solutions,
and as a reagent
Hydrochloric acid A highly corrosive, strong mineral acid with many
industrail uses
Hydrofluoric acid Valued source of fluorine, precursor to numerous
pharamceuticals; highly corrosive
Hydorgen peroxide Commonly used as a bleach
Imidazole An organic compound; this aromatic heterocyclic
is a diazole and is classified as an alkaloid
Isopropyl alcohol Simplest example of a secondary alcoho; dissolves
a wide range of non-polar compounds
Lime Used in flue gas desulphurisation in power plants.
Limestone Used in Flue Gas Desulphurisation in power plants
Manganese dioxide Used as a pigment and as a precursor to other

Uttarakhand Open University Page 10

LABORATORY COURSE-I BSCCH- 104
manganese compounds; used as a reagent in
organic synthesis for the oxidiation of allylic
alcohols
Methyl tert-butyl ether A gasoline additive; also used in organic chemistry
as a relatively inexpensive solvnet.
Millon’s reagent An analytical reagent used to detect the presence
of soluble proteins
Nitric acid Highly corrosive and toxic strong acid; used for
the production of fertilizers, production of
explosives, and as acomponent of aqua regia
Osmium tetroxide In organic synthesis, is widely used to oxidise
alkenes to the vicinal diols
Oxalyl chloride Used in organic synthesis for the preparation of
acid chlorides from the corresponding carboxylic
acids
Palladium(II) acetate A catalyst for many organic reactions by
combining with many common classes of organic
compounds to form reactive adduct.
Perchloric acid A powerful oxidizing agent; readily forms
explosive mixtures; mainly used in the production
of rocket fuel
Phosphoric aicd A mineral acid with many industrial uses;
commonly used in the laboratory preparation of
hydrogen halides
Phosphorus One of the most important phosphorus chlorides; a
chlorinating reagnet.
Pentachloride Also used as a dehydrating agent for oximes which
turn them into nitriles.
Pposphorus trichloride Most important of the three phosphorus chlorides;
used to manufacture organophosphorus
compounds; used to convert primary and
secondary alcools into alkyl chlorides, or
carboxylic acids into acyl chlorides.
Phosphoryl chloride Used to make phosphate esters such as tricresyl
phosphte.
Potassium dichromate A common inorganic chemical reagent, most
commonly used as an oxidizing agent in various
laboratory and industrial applications
Potassium hydroxide A strong oxidizing agent; can be used to
quantitatively determine the total oxidisalbe
Uttarakhand Open University Page 11
LABORATORY COURSE-I BSCCH- 104
organic material in an aqueous sample. A reagent
for the synthesis of organic compounds
Raney nickel An alternative catalyst for the hydrogenation of
vegetable oils; in organic synthesis, used for
desulfurization
Silver oxide Used to prepare other silver compounds; in organic
chemsitry, used as a mild oxidizing agent.
Silver nitrate Precursor to man othe silver compounds;
commonly used in organic chemsitry to abstract
halides
Sodium amide Used in the industrial production of indigo,
hydrzine, and sodium cyanide; used for the drying
of ammonia; used as a strong base in organic
chemstiry
Sodium azide Gas-forming component in airbag systems; used in
organic synthesis to introduce the azide functional
group by displacement of halides
Sodium A versatile reducing agent; converts ketones and
aldehydes to alcohols
Sodium chlorite In organic synthesis, used for the oxidation of
aldehydes to caroxylic acids.
Sodium hydride A strong base used in organic synthesis.
Sodium hydroxide Strong base with man industrial uses; in the
laboratory, used with acids to produce the
corresponging salt, also used as an electrolyte
Sodium nitrite Used to convet amines into diazo compounds
Sulfuric acid Strong mineral acid; major industrial use it the
production of phosphoric acid
Tert-Butyl hydroperoxide Used in variety of oxidation processes,
industrially, is used as a starer of radical
polymerization
Tetrahydrofuran One of the most polar ethers; a useful solvent; its
main use is as a precursor to polymers
Tetramethylsilane The simplest tetraorganosilane; a building block in
organometallic chemistry
Thionyl chloride An inorganic compound; used in chlorination
reactions; converts carboxylic acids to acyl
chlorides
Thiophenol An organosulfur compound; the simplest aromatic
thiol
Uttarakhand Open University Page 12
LABORATORY COURSE-I BSCCH- 104
Titanium tetrachloride An intermediate in the production of tiatnium
metal and titanium dioxide
Tollens’ reagent A chemical test most commonly used to determine
whether a known carbonyl-containing compound
is an aldehyde or a ketone
Triphenylphosphine Used in the synthesis of organic and
organometallic compounds.

1.6. LABORATORY SAFETY

GENERAL SAFETY RULES:

1. The safe way is the right way to do your job. Plan your work. Follow instructions. If
you do not know how to do the experiment safely, ask your teaching assistant.
2. Be able to use all safety devices and protective equipment provided for your use and
know their location (eyewash fountain, shower, fire blanket, fire extinguisher).
3. Safety goggles must be worn at all times.
4. Do not eat or drink in the laboratory (and do not store food in the refrigerators).
Smoking in the laboratory is absolutely forbidden.
5. Horseplay in any form is dangerous and prohibited. Do not run in laboratory areas.
6. Report to your TA all unsafe conditions, unsafe acts, and "near misses" that might
cause future accidents. Report any accident or fire, no matter how trivial, to the TA.
Hazardous Chemicals:
(a) Be especially mindful of fire hazards when you or your lab neighbors are working with
flammable liquids.
(b) Hazardous Substances: Know common explosive, toxic, and carcinogen materials and
use them only with adequate safeguards.
(c) Never leave a reaction or experiment running unattended, unless you have told your
lab partners enough about it to deal with potential hazards while you are away.
(d) Keep hood and bench top areas clean and workable space maximized.
Disposal of solvents, chemicals and other materials:
Never pour solvents or reactive chemicals down a drain. Such careless handling of
flammable or toxic liquids presents a serious hazard in the laboratory. Also, never keep an
open beaker of such solvents outside a hood. Chlorinated solvents are poured into solvent
waste containers kept inside the hoods. When in doubt about how to dispose of something,
ask a TA. If drain disposal is necessary and acceptable, always flush the drain before,
during, and afterwards with a lot of water, always using the drains in the hoods. All glass
must be discarded in the specially designed containers. A dustpan and brush for broken
glass can be checked out of Lab Supplies. Spilled mercury is a special safety hazard and
should be reported to your TA for cleanup.

Uttarakhand Open University Page 13

LABORATORY COURSE-I BSCCH- 104

1.7. SUMMARY
This course introduces the nntroduction about lab techniques to students. The whole cours
material contains the following information.
• Location of laboratory equipment in the laboratory.
• General Guideline of the laboratory.
• A detailed plan of the work that students will be doing.
• Laboratory apparatus and operation.
• Common Laboratory Apparatus used in the Experiments.
• Common Laboratory Reagents used in the Experiments.
• General safety rules.
1.8. TERMINAL QUESTIONS

1. Define various precautions of Chemistry lab.

2. What is the difference between burette & graduated pipette?
3. Name of all apparatuses used.

UTTARAKHAND OPEN UNIVERSITY Page 14

LABORATORY COURSE-I BSCCH- 104

UNIT 2: IDENTIFICATION OF ANIONS

CONTENTS:
2.1 Objectives
2.2 Introduction
2.3 Classification of the anions: Anion of class I, Anion of class II, Anion of class III
2.4 Preliminary Tests for the Anions: Preliminary tests for the anions of class I, anions
of class II, and anions of class III.
2.5 Preparation of solution for identification of the anions: Preparation of water extract,
Preparation of sodium carbonate extract.
2.6 Confirmatory test for the anion: Test for the sulphide ions, sulphite ions, sulphate
ions, thiosulphate ions, nitrite ions, nitrate ions, acetate ions, , chloride ions,
bromide ions, iodide ions, oxalate ions fluoride ions, phosphate ions, and borate
ions; special test for the mixture of the anions.
2.7 Summary

2.1. OBJECTIVES
• To identify common anions in solution using simple qualitative chemical tests.
• Plan a procedure for the analysis of an unknown solution of an anion and describe
that procedure with a flow chart.
• Identify different anions using a qualitative analysis technique.
• The purpose of this experiment is to determine what anions are present in an
unknown sample. We will be looking for the common anions sulfide (S2-), sulfate
(SO42-), sulfite (SO32-), phosphate (PO43-), carbonate (CO32-), chloride (Cl-),
bromide (Br-), iodide (I-), acetate (C2H3O2-) and nitrate (NO3-).

2.2 INTRODUCTION

In this chapter, you will identify anions in unknown substances. Instead, in this lab, you
first will perform some preliminary tests using AgNO3, BaCl2, and H2SO4. In these tests,
certain groups of anions will react while other groups of anions will not react. By analyzing
the results of the first part of the experiment, you should be able to eliminate half - if not
more- of the anions as possibilities in your unknown. You will then perform confirmatory
tests for the remaining anions in question to determine whether the anions are present or
absent.
The goal of this experiment is to develop techniques for identifying unknown substances.
You will identify unknown solutions as containing one of the following: Cl-, Br-, I-, HPO42-
, or SO4 2-
UTTARAKHAND OPEN UNIVERSITY Page 15
LABORATORY COURSE-I BSCCH- 104

The inorganic qualitative analysis involves the identification of ions present in a sample.
The salt consists of anion and cation. The basis of identification is the observed chemical
behaviour of the components. The salt analysis may be systematically carried out in the
following three steps:
i) Preliminary examination
ii) Detection of anions and
iii) Detection of cations

2.3 CLASSIFICATION OF ANIONS (ACIDIC RADICALS)

The anions are provided by the acids in the process of salt formation; hence these are
generally referred to as acidic radicals. These radicals cannot be divided in the systematic
groups as has been done in the case of the cations. However, for the sake of simplicity,
these have roughly been divided into three groups depending upon their reactions with
certain regents.

Classification of acidic radicals or anions:

Group Name and formula Group Reagent Inference of the

of the Radical group
Class I Carbonate (CO32-) Dil. HCl or Gases of different
anions Sulphite (SO32-) H2SO4 (Cold or colours and
(First Sulphide (S2-) hot.) smells are
group) Acetate (CH3COO-) evolved.
Nitrite (NO2-)
Thiosulphate (S2O32-)
Class II Chloride (Cl-) Conc.H2SO4 Gases of different
anions Bromide (Br-) (hot.) colours and
(Second Iodide (I-) smells are
group) Nitrate (NO3-) evolved.
* Oxalate (C2O42-)
* Borate (BO33-)
* Fluoride (F-)
Class III Sulphate (SO42-) Barium chloride A white
anions * Phosphate (PO43-) (BaCl2) in precipitate
(Third presence of dill. appears.
group) HCl. A yellow
Ammonium precipitate
molybdate appears.
(NH4)2MoO4 in
presence of conc.

UTTARAKHAND OPEN UNIVERSITY Page 16

LABORATORY COURSE-I BSCCH- 104

HNO3.
* Interfering radicals (or anions)

2.4 PRELIMINARY TEST FOR THE ANIONS

A preliminary test for the anions is done on the basis of their class or group.
Preliminary Tests for the Anions of Class I (Group I)

The salts of these anions are decomposed by dil. H2SO4 or dil. HCl which serves as their
group reagent. These anions with their preliminary tests are summarized below.

Take a small amount of salt or mixture in a dry test tube and add 5-6 ml of dil. H2SO4 or
dil. HCl. Observe the reaction taking place in the test tube. If there is no reaction, heat the
contents of the test tube gently and observe the sound, colour and odour of the gas evolved.
From the observation, guess the presence of the anion according to the following table:

S. No. Anion Experiment Observation Inference

1. Carbonate anion On conducting *Brisk CO32- may
(CO32-) the above effervescence be present.
experiment with with evolution of
dil. acids in cold colourless,
or on heating. odourless gases
(CO2).
2. Sulphite anion In the above If the colorless (SO32-)
(SO32-) experiment. gas with may be
suffocating present.
odour of burning
sulphur is
evolved (SO2)
3. Sulphide anion On conducting ** Evolution of (S2-) may
(S2-) the above colourless gas be present.
experiment. with smell of
rotten eggs
occurs (H2S)
4. Nitrite anion (NO2- In the above ***Brown fumes NO2- may
) experiment. with pungent be present.
odour
(NO2) are
evolved.
5. Thiosulphate anion On conducting If the colorless (S2O32-) is
(S2O32-) the above gas with expected
experiment. suffocating odour to be

UTTARAKHAND OPEN UNIVERSITY Page 17

LABORATORY COURSE-I BSCCH- 104

is evolved and present.

solution in test
tube becomes
yellowish white
with turbidity.
6. Acetate anion The same Small of vinegar (CH3COO-
(CH3COO-) experiment as is noticed without ) is
has been given evolution of any expected
above is gas (CH3COOH) to be
conducted and present.
thus
Note:

* Basic carbonates of Pb and Bi do not evolve CO2 with effervescence, but do so

gradually.

**Many sulphides, e.g. those of Ag, Hg, As, Co and Ni do not decompose on heating
with dil. HCl or dil. H2SO4. Therefore, the salt or mixture is heated with conc. HCl alone or
with little zinc to observe the evolution of H2S. If no H2S smell is noticed, the above
sulphides are taken as absent.

***All nitrites are soluble in water. The liberated NO2 gas turns FeSO4 solution black.

Preliminary Tests for the Anions of class II (group II).

The group reagent for the anions of this class is conc. H2SO4, i.e., the salts of these anions
are readily decomposed by conc. H2SO4- After performing the preliminary tests of the
anions of group I or class I, take a small amount of the salt or mixture in a separate dry test
tube and add conc. H2SO4(2-3ml). then heat gently for some time. Observe the reactions
occurring in the test tube as well as the gases evolved according to the following table.

S. Anion Experiment Observation Inference

No.
1. Chloride anion In the above Colorless pungent (Cl-) may
(Cl-) experiment, gas (HCl) is evolved be present.
2. Bromide anion In the above Red brown gas (Br2) Br- is
(Br-) experiment, is evolved and expected.
solution becomes
orange.
3. Iodide anion (I-) On conducting the Dark violet fumes (I-) May
above reaction. (I2) are observed be present.
4. Nitrate anion In the above * Pungent light (NO3-)

UTTARAKHAND OPEN UNIVERSITY Page 18

LABORATORY COURSE-I BSCCH- 104

(NO3-) reaction. brown gas (NO2) is may be

evolved. present.
5. Oxalate On conducting the **colorless, (C2 O42-)
anion above experiment odourless gas is is
2-
(C2 O4 ) (strong heating), evolved which burns expected
with blue flame at
the mouth of the test
tube on bringing a
burning stick near
the mouth
6. Fluoride anion On strong heating White pungent (F-) is
(F-) the contents of the smelling gas is expected
test tube. evolved and test tube
becomes greasy
7. Borate anion The borates are not decomposed by only conc. H2SO4 but
(BO33-) in presence of ethyl alcohol or CaCl2, they give
compounds which can easily be detected. It will be
discussed latter.
Note: * All nitrates are soluble in water.

**Oxalates of K+ and NH4+ are soluble in water. Ferrous oxalate is sparingly soluble. All
other oxalates are insoluble.

2.5 PREPARATION OF SOLUTION FOR IDENTIFICATION

OF THE ANIONS
For the identification of the anion(s) in the salt or the mixture, the anion (s) must be
brought in solution, i.e., in free state so that the anion (s) may give suitable tests with the
suitable regent (s). Many salts are soluble in water to give free anions and cations in
solution, e.g. most of the ammonium salts and those of alkali metals are soluble. All
nitrites, nitrates, acetates and many halides are also soluble in water. In the aqueous
solution many anions can be detected. It is usually better to bring the anion (s) into the
solution as soluble sodium salts by preparing soda or sodium carbonate extract which is
obtained after boiling the salt or mixture with an excess of sodium carbonate solution.
Preparation of Soda Extract:
Mix one part of the solid salt or mixture with 3 parts by weight of sodium carbonate and
10-12 ml. distilled water (mineral free) and boil for about 8-10 minutes in a beaker or
comical flask. Filter the contents while hot. The filtrate, known as soda extract, is used for
detecting (or testing) most of the anions. The residue left on the filter paper may be
dissolved in water or dil. HCl and tested for basic radicals whose salts are insoluble both in
dil. and conc. HCl.
UTTARAKHAND OPEN UNIVERSITY Page 19
LABORATORY COURSE-I BSCCH- 104

The excess sodium carbonate taken reacts with salts or mixture of the salts whereby the
anions or acidic radicals are converted to their corresponding sodium salts which are water
soluble and can be filtered off. Thus the anions come down in the filtrate along with the
excess of sodium carbonate. The cations or the basic radicals are converted into their
corresponding carbonates almost all of which are insoluble in water and therefore remain as
residue on the filter paper along with unchanged salts (amm. carbonate is soluble).

Let X represents the basic radical (cation) and Y the acidic radical (anion) of any salt.
When such a salt (XY) is heated with excess of sodium carbonate, the following reactions
take place:

XY+Na2CO3 XCO3+Na2Y (X and Y are bivalent radicals) e.g.

SnCl2+Na2CO3 SnCO3+2NaCl (Soda extract)

CaC2O4+ Na2CO3 CaCO3+Na2C2O4 (Soda extract)

The filtrate so obtained after neutralization with suitable acid, can be used to detect certain
anions. The acid is to be added in excess till bubbles cease to evolve. This indicates the
complete neutralization of the solution (soda extract). The common anions which can be
identified easily using soda extract along with the acid used for its neutralization and the
reagent added for the identification are given in the following table:

Anion Experiment observation Inference

Cl-, Br-, I- dil. HNO3 AgNO3 soln. AgCl: white ppt,
AgBr: light yellow
ppt., AgI-yellow ppt.
NO3- dil. H2SO4 Freshly prepared Brown ring of FeSO4.
FeSO4 solution NO compd. results.
SO42- dil. HCl BaCl2 soln. BaSO4: White ppt.
C2O42- dil. CH3COOH CaCl2 soln. CaC2O4: White ppt.
CH3COO- dil. HCl Neutral FeCl3 Basic ferric acetate:
solution. brownish red ppt.
PO43- dil. HNO3 Conc.HNO3+(NH4)2 Canary yellow ppt.
MoO4, heated and
cooled.
Here,
Column 1 represents the acidic radicals whose sodium salts are found in the extract.
Column 2 gives the acid to be added for neutralizing the excess of sodium carbonate.
Column 3 contains the names of the reagents added for the identification.
Column4 represents the characteristic changes which are observed during identification of
the said anions.
Following are the advantages of preparing soda extract:
UTTARAKHAND OPEN UNIVERSITY Page 20
LABORATORY COURSE-I BSCCH- 104

(i) It removes the basic radicals which may interfere in the systematic identification of the
anions, by converting them into insoluble metal carbonates.
(ii) The identification of anions becomes easier in the case of compounds insoluble in
water and dil. acids.
(iii) It helps in the identification of certain basic radicals (cations) of compounds insoluble
in water, conc. HCl, HNO3, etc. For example: BaSO4, SrSO4, etc.
Precaution: Na2CO3 used in the preparation of soda extract should be pure, free from
chloride and sulphate which are generally present as impurities.
Note: Carbonate ion (CO32-) is not detected by this method because it already comes from
sodium carbonate. Hence it should be detected in the solid salt or mixture.

2.6 CONFIRMATORY TESTS FOR THE ANIONS

The presence of the anions in the salt or mixture is confirmed after the preliminary tests
have been done. The confirmatory test for various anions is carried out as follows:

1. CO32- anion:
It the colourless gas evolved during the preliminary test is passed into lime water*, it turns
milky due to the formation of calcium carbonate, CaCO3. If passing CO2 is continued for a
long time (excess), milky colour disappears, i.e., becomes soluble due to the formation of
calcium bicarbonate, Ca (HCO3)2. This confirms the presence of CO32 ion.
Note. SO32- ion also gives the same test Hence the presence CO32- ion is confirmed after
testing for SO32- ion. It is better to test both CO32- and SO32- ions simultaneously.
2. SO32- anion:
(i)If the colorless gas evolved during the preliminary test is brought in contract with
the filter paper moistened with acidified potassium dichromate, solution**, the
paper turns green.
(ii)Take 1ml. soda extract, add to it acetic acid in excess to make it neutral. Then add
to it BaCl2 solution and filter. To the filtrate, add bromine water and heat, white
precipitate of BaSO4 is obtained. These tests confirm the presence of SO32- ion.
2-
3. S anion:
(i) If the colorless gas evolved during the preliminary test turns filter paper dipped in
lead acetate solution black on bringing it at the mouth of test tube, it confirms the
presence of S2- ion.
(ii)Take 1 ml. soda extract and add to it few drops of sodium nitroprusside, the
solution becomes violet, again confirming the presence of S2—ion.
4. NO2-anion:
(i) If the brown gas evolved during the preliminary test turns paper dipped in starch
+ KI solution blue, presence of NO2- ion is confirmed.

UTTARAKHAND OPEN UNIVERSITY Page 21

LABORATORY COURSE-I BSCCH- 104

(ii) Add 2-3 drops of KI and starch solution in the test tube during the preliminary
test, deep blue or violet color if appears, it again confirms the presence of NO2-
ion.
2-
5. S2O3 anion:
(i)If SO32-, S2- or SO42- is present, shake a portion of the soda extract with CdCO3 or
PbCO3 and then with Sr (NO3)2 solution. Filter and discard the precipitate if
formed. Use filtrate for the detection of thio sulphate ion. If S2-,SO32-, or SO42- is
absent, use the water extract for testing S2O32-. The mixture
solution+AgNO3→white precipitate. This ppt. is unstable and decomposes on
warming or on addition of HCl into black Ag2S through colour change from
yellow to brown and finally black.
(ii)Soda extract of the substance + iodine solution → decolorization of iodine
solution confirms the presence of S2O32- anion.
6. CH3COO- anion:
(i) A water extract of the substance gives blood-red colour in cold with neutral
ferric chloride, solution, confirming the presence of acetate ion.
(ii) On rubbing the substance + oxalic acid (few crystals) + water (few drops)
between the fingers, smell of vinegar is noticed again confirming the presence of
acetate ion.
(iii)Solution of the substance + a little ethyl alcohol + a little conc. H2SO4 + heat
gently → fruity smell is noticed (of ethyl acetate).
Note. *Method of passing CO2 gas into water: If the delivery tube is available, insert its
two ends with corks in the sample tube and line water tube (Delivery tube must be
dipped in lime water) and heat the contents of sample (mix.+acid) tuble. Otherwise
collect the evolved CO2 in a test tube which just fits in the mouth of sample tube. After
heating the sample tube, close the mouth of the second test tube with the thumb and add
line water to it to check the presence or thumb and add line water to it to check the
presence or absence of CO2 gas.
**Preparation of acidified K2Cr2O7 solution: Take approx. 1gm. of K2Cr2O7 crystals and
dissolve in 5ml. water, then add 2-3ml. dil. H2SO4. This is acidified dichromate solution.
***The shelf FeCl3 contains free HCl in small amount due to hydrolysis of FeCl3. Add a
very dilute solution of NH4OH drop wise to a little FeCl3 solution taken in a test tube
and shaking after each addition till a permanent precipitate is formed. Now boil the
contents of the test tube and filter. The filtrate is known as neutral ferric chloride.
7. Cl- anion:
(i) On bringing a glass rod dipped in NH4OH near the mouth of the test-tube during
the preliminary test, white dense fumes of NH4Cl are formed.
(ii) On heating the given mixture with conc. H2SO4 and MnO2, greenish yellow,
pungent smelling gas (Cl2) is evolved.
(iii) Soda extract+dil. HNO3+AgNO3 solution→ a white precipitate (AgCl) is
formed which is soluble in NH4OH solution.
UTTARAKHAND OPEN UNIVERSITY Page 22
LABORATORY COURSE-I BSCCH- 104

(iv) Chromyl chloride test: Heat a small amount of the mixture, add to it soild
K2Cr2O7 (3 times of mixture) and conc. H2SO4. Orange-yellow vapors of
chromyl chloride (CrO2Cl2) are evolved and are collected in a test-tube
containing NaOH. This is acidified with CH3COOH and treated with lead acetate
solution. A yellow precipitate of lead chromate (PbCrO4) is formed.
All these tests confirm the presence of Cl- ion.
Note. The chromyl chloride test does not respond in case of chlorides of Ag, Hg, Pb and
Sn. In such cases, it can be performed by the residue obtained on evaporating 5 ml. of soda
extract.
8. Br- anion:
(i) On heating the given salt or mixture with a little MnO2 and conc. H2SO4, red-
brown vapours of Br2 are evolved.
(ii) Soda extract+dil. HNO3+AgNO3 solution→ a pale yellow precipitate is formed
(Ag Br) which is partially soluble in NH4OH.
(iii) Soda extrac+ a little dil. HNO3 (to neutralise)+ few drops of chloroform or
CCl4+ Cl2 water or conc. HNO3 + Shake →chloroform or CCl4 layer (lower)
becomes yellow or orange These tests confirm the presence of Br- ion.
9. I- anion:
(i) Given salt or mixture+ MnO2+conc. H2SO4+heat→violet vapours (I2) in excess
are evolved which turn the paper dipped in starch solution blue.
(ii) Soda extract+dil. HNO3+AgNO3 solution→yellow precipitate of AgI is formed
which is insoluble in NH4OH solution.
(iii) Soda extract+ a little HNO3(dil.) (to neutralize)+ few drops of CHCl3or
CCl4+conc. HNO3 or Cl2 water+ shake well→layer of organic liquid becomes
pink or violet These tests confirm the presence of I- ion.

10. NO3- anion:

(i)On heating the salt or mixture with copper turnings and conc. H2SO4, deep brown
fumes (NO2) are evolved in excess but the solution does not become yellow or
pink.
(ii)Aqueous extract or solution of the salt or mixture in dil. HCl + freshly prepared
solution of FeSO4+shake well+add gradually conc. H2SO4 by the side of the test
tube→a brown ring of FeSO4. NO is formed at the junction of two liquids (This
is called ring test)
The above tests confirm the presence of NO3- ion.
11. C2O42- anion:
(i)Take soda extract of the salt or mixture in a test tube, acidify it with excess of
CH3COOH and then add CaCl2 solution. A white precipitate of CaC2O4 is
formed. Dissolve the precipitate in dil. H2SO4 and warm it. To the warm

UTTARAKHAND OPEN UNIVERSITY Page 23

LABORATORY COURSE-I BSCCH- 104

solution, add few drops of KMnO4 solution and shake, pink colour of KMnO4
solution disappears.
(ii)Take a little salt or mixture in a test-tube, add dil. H2SO4 and heat till
effervescence ceases to appear. Add a pinch of MnO2 and heat again.
Effervescence due to evolving CO2 reappears.
The above tests confirm the presence of C2O42- ion.
12. F- anion:
(i) Take a little salt or mixture with some sand in a test tube, add conc. H2SO4 to it
and heat, bring a glass rod moistened with water at the mouth of the test tube. A
waxy white deposit on the glass rod is obtained (NH4Cl and HgCl2 also leave a
white deposit on the rod but this deposit is crystalline and not waxy).
After performing this test the contents of the test tube should not be thrown in
the sink without cooling and diluting.
(ii)Soda extract+CH3COOH (to neutralise) + CaCl2 solution + shake → white
precipitate appears after sometime. To the precipitate add dil.
H2SO4+heat+KMnO4 solution → pink color of KMnO4 is not discharged.
These tests confirm the presence of F- ion.
13. BO33- anion:
(i)Take a little salt or mixture in a porcelain dish, add a little conc. H2SO4 just to
make the paste of the substance, 1/2ml. of ethyl alcohol or methylated spirit well
by a glass rod and ignite →a green edged flame is developed (copper and barium
salts also give the same test and interfere in the detection of BO33- ion by this
test. Hence test should be performed in a test tube instead of porcelain dish and
the vapours evolved after heating should be burnt at the mouth of the test-tube).
(ii) Make a paste of little mixture + calcium fluoride (CaF2) with a little conc.
H2SO4. Take a portion of this paste with a thin glass rod or Pt-wire and bring it
near the edge of the flame (do not introduce the paste into the flame)→green
flame is obtained (Cu & Ba-salts do not interfere).
These tests confirm the presence of BO33- ion.
14. SO42- anion:
Take the solution of the substance in dil. HNO3 or soda extract + dil. HCl. Add
BaCl2 solution. A curdy white precipitate is formed (BaSO4) which is insoluble
in all the conc. acids. This confirms the presence of SO42- ion.
15. PO43- anion:
(i)Boil a little substance with conc. HNO3 and add ammonium molybdate solution to
it, boil again and cool. A canary yellow precipitate is formed which is soluble in
ammonium and alkali hydroxides.
(ii)This ion can also be tested in the soda extract as has already been given above
These are the confirmatory tests for PO43- ion.
(iii)

UTTARAKHAND OPEN UNIVERSITY Page 24

LABORATORY COURSE-I BSCCH- 104

Reactions Involved:

Carbonate : Na2CO3 + 2 HCl → 2NaCl + H2O + CO2 ↑

anion (CO32-) Ca (OH)2 + CO2 → CaCO3 ↓ + H2O
White (milky)

CaCO3 + H2O + CO2 → Ca (HCO3)2 (Soluble)

excess

SalphiteNa2SO3+2HCl→2NaCl+H2O+SO2 ↑
anion (SO32-)Ca(OH)2 + SO2→ CaSO3 (Milky) + H2O
K2Cr2O7 + H2SO4+3SO2→K2SO4+ Cr2(SO4) (Green)+H2O

SulphideFeS+H2SO4→H2S ↑ + FeSO4
anion (S2-) (CH3COO)2 Pb + H2S→PbS (black) ↓ + 2CH3 COOH
Na2S+Na2 [Fe(NO)(CN)5]→Na4[Fe(NOS)(CN)5]
Sod. Nitroprusside
(Violet Complex)

Nitrite 2NaNO2 + H2SO4 → Na2SO4 + 2HNO2

-
anion (NO2 ) 3HNO2→HNO3 + 2NO ↑ + H2O
2NO + O2 → 2NO2 ↑ (Brown)
2KI + 2NO2 → 2KNO2 + I2
I2 + starch → Starch-Iodide (Blue)
Ring test:
FeSO4+NO → FeSO4. NO (Brown ring)
Thiosulphate: Na2S2O3 + 2AgNO3 → Ag2S2O3 ↓ (white) + 2NaNO3
anion (S2O32-) Ag2S2O3+ H2O → Ag2S ↓ (Black) + H2SO4
2Na2 S2 O3 + I2 → 2NaI + Na2S4O6 (tetrathionate)
Acetate:
2CH3COONa + H2SO4→ 2CH3COOH (vinegar smell) + Na2SO4
Anion (CH3COO-)
3CH3COOH + FeCl3 → (CH3COO)3 Fe (Blood red color) + 3NaCl

Chloride anion (Cl-)

NaCl + H2SO4 → NaHSO4 + HCl (pungent gas)

HCl + NH4OH → NH4Cl ↑ (white fumes) + H2O

2NaCl + MnO2 + 3H2SO4 → 2NaHSO4 + MnSO4 + 2H2O + Cl2 ↑

UTTARAKHAND OPEN UNIVERSITY Page 25

LABORATORY COURSE-I BSCCH- 104

(greenish yellow gas)

NaCl + Ag NO3 → AgCl ↓ (ppt) + NaNO3
AgCl ↓ + 2NH4OH → Ag (NH3)2 Cl (soluble) + 2H2O

Bromide: K Br + H2SO4 → KHSO4 + HBr

anion (Br-) 2HBr + H2SO4→ Br2↑(reddish brown vapours)+ SO2↑ + 2H2O
2KBr + MnO2 + 3H2 SO4 → 2KHSO4 + MnSO4 + 2H2O + Br2 ↑
Na Br + AgNO3 → Ag Br ↓ (Light yellow ppt.)+Na NO3
2 NaBr + 4 HNO3 → Br2↑ + 2NaNO3 + 2NO2 ↑ + 2H2O
2HBr + Cl2 → Br2 ↑ + 2HCl
Br2 + CHCl3 or CCl4 → Orange yellow colour (Br2 dissolves)

Iodide NaI + H2 SO4 → NaHSO4 + HI

anion (I-) 2HI + H2SO4 → I2 ↑ (Violet vapours) + SO2 ↑ + 2H2O
2 NaI + MnO2 + 3H2SO4 → I2 ↑ + 2NaHSO4 + MnSO4 + 2H2O
I2 + starch → starch – iodide (Blue)
NaI + AgNO3 →AgI ↓ (yellow ppt.) + NaNO3
2NaI + Cl2 → 2 NaCl + I2
2NaI + 4HNO3 →I2 ↑ + 2NaNO3 + 2NO2 ↑ + 2H2O
I2 + CHCl3 or CCl4 → Pink or purple color (I2 dissolves)

Nitrate: NaNO3 + H2SO4 → NaHSO4 + HNO3

Anion (NO-3) 4 HNO3 → 4 NO2 ↑ (Brown fumes)+ O2 ↑ + 2H2O
3Cu + 8HNO3 → 3 Cu (NO3)2 + 2NO ↑ + 4 H2O
2 NO + O2 → 2 NO2 ↑ (Brown)
Ring Test: 6 FeSO4+2 HNO3 + 2 H2SO4 → 3 Fe2 (SO4)3 + 4 H2O + 2NO↑
FeSO4 + NO → FeSO4. NO (Brown ring)
Oxalate : Na2C2O4 + 2H2SO4 → 2NaHSO4 + H2O +CO2 ↑ + CO ↑
2-
anion (C2O4 ): 2CO + O2 → 2CO2
Na2C2O4 + CaCl2 → CaC2O4 ↓ (white ppt.) + 2NaCl
Ca C2 O4 + H2 SO4 → Ca SO4 + H2 C2O4 (oxalic acid)
2 KMnO4 + 3 H2SO4 + 5 H2C2O4 → K2SO4+ 2 MnSO4 + 10 CO2 ↑ + 8 H2O
Na2C2O4 + MnO2 + 2 H2SO4 → Na2 SO4 + MnSO4 + 2 H2O + 2 CO2 ↑

Fluoride: 2 NaF + H2 SO4 → Na2 SO4 + 2 HF ↑ →

Anion (F-) Si O2 + 4 HF → Si F4 + 2 H2O →
3 Si F4 + 3 H2O → 2 H2 Si F6 + H2Si O3 (white deposit)

UTTARAKHAND OPEN UNIVERSITY Page 26

LABORATORY COURSE-I BSCCH- 104

Borate: Na3BO3 + 3 H2SO4 → 3 NaHSO4 + H3 BO3 (Boric acid)

3-
Anion (BO3 ) H3 BO3+ C2H5OH → (C2H5)3 BO3 ↑ (ethyl borate) + 3 H2O
CaF2 + H2SO4 → Ca SO4 + 2HF
Na3 BO3 + 3 H2 SO4 → 3 Na HSO4 + H3 BO3
2 H3 BO3 → B2 O3+ 3 H2O
B2 O3 + 6 HF → 2 BF3 (burns with green flame)+ 3 H2O

Sulphate Na2 SO4 + BaCl2 → Ba SO4 (white ppt) +2 NaCl

anion (SO42-)

Phosphate Na3 PO4 + 3 HNO3 → H3 PO4 + 3 NaNO3

3-
anion (PO4 ) H3PO4 + 12 (NH4)2 Mo O4 + 21 HNO3 →
(NH4)3 PO4 12 Mo O3 ↓ + 12 H2O + 21 NH4 NO3.
(amm, phospho molybdate - canary yellow ppt.)

Special Tests for the Mixtures of Anions (Combinations).

1.Carbonate and Oxalate.
If given as a combination in a mixture, decompose carbonate anion completely by
dil. H2SO4 (oxalate remains unaffected and then add MnO2. If effervescence
appears again, it indicates the presence of oxalate which can be confirmed by
decolorization of KMnO4 solution.
2.Carbonate and Sulphite.
Carbonates and sulphites both are decomposed by dil. H2SO4 to give CO2, and SO2
gases which give white ppt. with lime water. But sulphite only (SO2) reacts with
pot. dichromate in presence of dil. H2SO4 to change the colour from light yellow to
green [Cr2 (SO4)3].
3.Sulphide, Sulphite and Sulphate.
Sulphide can be tested with sod. nitroprusside solution. Where, sulphite and
sulphate do not interfere. If all the three anions are given together, remove sulpide
by Pb CO3 or Cd CO3 as Pb S (black) or CdS (yellow). Filter and add dil. HCl and
BaCl2 solution to the filtrate to give white ppt. of BaSO4, filter again and boil the
filtrate with conc. HNO3 or bromine water to oxidize sulphite to sulphate [Na2SO3 +
O (from HNO3 or Br2 water] which can be tested with BaCl2 solution (white ppt.
BaSO4 appears again).
4.Chloride, Bromide and Iodide.
Chloride is tested by chromyl chloride test where bromide and iodide do not
interfere. Bromide and iodide given together are tested by organic layer test.
Acidify one ml. soda extract with dil. HCl or dil. H2SO4, add few drops of CHCl3 or
CCl4 followed by freshly prepared chlorine water drop by drop while shaking. If
organic layer is pink or violet, iodide is confirmed. Continue adding excess of

UTTARAKHAND OPEN UNIVERSITY Page 27

LABORATORY COURSE-I BSCCH- 104

chlorine water with vigorous shaking. If organic layer becomes orange brown or
yellow, bromide is also confirmed.
5.Nitrite and Nitrate.
If nitrite gives positive test as given above, decompose it by urea or NH4Cl as
below:
NaNO2 + H2SO4 → NaHSO4 + HNO2
(NH2)2 CO + 2 HNO2 → 2 N2 ↑ + 3 H2O + CO2 ↑
NaNO2 + NH4Cl → NaCl + N2 ↑ + 2 H2O
Now reduce nitrate using zinc and dil. H2SO4 to nitrite and test it by KI and starch
solution as given below:
Zn + H2SO4 → ZnSO4 + 2H
NaNO3 + 2H → NaNO2 + H2O (rest as given above)
6.Nitrite and Iodide.
If both are preset in the mixture, add conc. H2SO4 to it heat and then add starch
solution. Blue color of starch iodide confirms the presence of both anions.
7.Nitrate and Bromide.
Reduce nitrate to nitrite by zinc and dil. H2SO4 and test as usual.
Confirm bromide by organic layer as usual.
8.Nitrate and Iodide.
Reduce nitrate to nitrite and then nitrite and iodide can be tested by starch solution
(blue). Iodide can also be detected by organic layer test.
The reactions of the tests for combination of acidic readicals or mixtures of anions
are the same as given above. Therefore the reactions involved in the tests can be
referred to the above.

2.7 SUMMARY
This unit gives the classification of anions (Acidic Radicals). Preliminary test are given for
the identification of class I, class II and class III anions. Basic carbonates of Pb and Bi do
not evolve CO2 with effervescence, but do so gradually. Many sulphides, e.g. those of Ag,
Hg, As, Co and Ni do not decompose on heating with dil. HCl or dil. H2SO4 . Oxalates
of K+ and NH4+ are soluble in water. Soda extract preparation should be used to prepare to
prepare solution of anions. It is is obtained after boiling the salt or mixture with an excess
of sodium carbonate solution. Na2CO3 used in the preparation of soda extract should be
pure, free from chloride and sulphate which are generally present as impurities. Carbonate
ion (CO32-) is not detected by this method because it already comes from sodium carbonate.
Hence it should be detected in the solid salt or mixture.

UTTARAKHAND OPEN UNIVERSITY Page 28

LABORATORY COURSE-I BSCCH- 104

UNIT 3: IDENTIFICATION OF CATION (KNOWN)

CONTENTS:
3.1 Objectives
3.2 Introduction
3.3 Classification of the cation into Analytical groups
3.4 Solubility and solubility product: Relation between Solubility and Solubility
products.
3.5 The common ion effect; complex formation
3.6 The separation of Cations in to analytical Groups: The precipitation of Group I
cations, the separation of Group II cation from Group IV Cations, The Precipitation
of Group III Cations, The Precipitation of Group V Cations.
3.7 Preliminary Investigation of the Sample
3.8 Preparation of solution for the analysis of Cations
3.9 Separation of cation into Analytical Groups
3.10 Analysis of the cations of Analytical Group I: Separation and Identificationof the
cations of Analytical Group I
3.11 Analysis of the cations of analytical Group II: Separation of Analytical Group II in
to group IIA and Group IIB, Separation of the Cations of group IIA, Separation of
the Cations of group IIB, Identification of the cations of Group II
3.12 Analysis of the cations of analytical Group III: Separation and Identification of the
cations of analytical Group III.
3.13 Analysis of the cations of analytical Group IV: Separation and identification of the
cations of Analytical group IV.
3.14 Analysis of the cations of analytical Group V: Separation and identification of the
cations of Analytical group V.
3.15 Analysis of the Cations of analytical group VI
3.16 Chemical reactions involved in the test of basic radicals
3.17 Summary
3.1. OBJECTIVES
•To separate different cations in aqueous mixtures using selective precipitation and to
confirm their identities using chemical tests.
•To classification of the cation into Analytical groups.
•Preliminary Investigation of the Sample.
•To preparation of solution for the analysis of Cations.
•Separation of cation into Analytical Groups.
•Analysis of the cations of Analytical Group I,II, III, IV, V VI and zero group.

UTTARAKHAND OPEN UNIVERSITY Page 29

LABORATORY COURSE-I BSCCH- 104

3.2. INTRODUCTION
Qualitative analysis involves the identification of the substances in a mixture. When
chemical methods are used in the identification of mixtures of metal cations, these ions are
usually separated before identification can occur. After they have been separated,
identification of each cation depends on the observation of a characteristic chemical
reaction. Solubility equilibria and complex-ion equilibria play crucial roles in the
separations and subsequent identifications.
3.3 CLASSIFICATION OF CATIONS INTO ANALYTICAL
GROUPS

The cations (or the basic radicals) have been classified into seven groups, viz. from zero, I
to VI group according to their nature to form the precipitate with various reagents. Because
no single reagent is available which could form precipitate with all the cations, hence they
have been classified into groups and the cations of each group give precipitate with a
particular reagent called group regent.
3.4 SOLUBILITY AND SOLUBILITY PRODUCT
In the simple terms if a substance dissolves in a solvent, it is said to be soluble (more
accurately solute) and the resulting mixture is known as solution (may be unsaturated or
saturated). This tendency of a solute to get dissolved in a solvent is called, in a general
sense, its solubility. The solubility depends on the nature of both the solute (substance) and
the solvent. It is more accurately defined as “the number of grams of the substance
which is dissolved in 100 grams of the solvent in a saturated solution at a given
temperature.

The solubility of a solid substance in a given solvent depends mainly on the temperature
and very slightly on the pressure. For most solid substances, it increases with increasing
temperature, e.g., solubility of AgNO3 increases rapidly but that of NaCl increases slowly.
The change in solubility with changing temperature is usually expressed by means of
solubility curves(plots of the number of grams of solute dissolved in 100 grams of solvent
along ordinate against the temperature along abscissa) There are also some substances
whose solubility decreases with rising temperature, e.g. Li2CO3, NaOH, etc.

Solubility Product and Precipitation.

When a sparingly soluble substance, say AB, is kept in contact with water for sometime at
a definite temperature, the following equilibrium is established:

AB ⇌ AB ⇌ A+ + B- and [A+] [B-] = K (from law of mass action)

Solid Dissolves Ions [AB]

UTTARAKHAND OPEN UNIVERSITY Page 30

LABORATORY COURSE-I BSCCH- 104

The concentration of the unionised [AB] is constant at a given temperature if excess of AB

is present. Hence, [A+] [B-] = K [AB] = constant. Therefore, “In equilibrium, the product
of the ionic concentration is constant at a given temperature. This constant product,
[A+] [B-], is called the solubility product (Ks)”. When the ionic product exceeds the
solubility product, the solution is super saturated and precipitation occurs but if the ionic
product is less than the solubility product, the solution is unsaturated and precipitation does
not occur. This is called theory of precipitation. This can also be represented as
Ionic product < solubility product, Ks, the salt dissolves.

Ionic product > solubility product, Ks precipitation takes place.

Relation between Solubility and Solubility Product.

The solubility of a sparingly soluble substance (electrolyte) of 1:1 can be calculated using
the principle of the solubility product. Let it be AB.

Ks (AB) = [A+] [B-]

If [A+] = [B-] = s moles per liter

Ks (AB) = s.s = s2

Or s =

Where s = solubility of AB in moles per liter and Ks (AB) is the solubility product
of AB.

But for the substances (electrolytes) or 1:2 or 2:1 type, i.e., AB2 or A2 B type

Ks = s x (2s)2 or (2s)2 x s = 4s2

∴s= moles per liter

3.5 THE COMMON ION EFFECT

The phenomenon of lowering the degree of ionisation of a weak electrolyte substance by
adding to its solution a solution of strong electrolyte having a common ion and thus
decreasing the concentration of the ion other than the common ion of the weak electrolyte
is known as Common ion effect. For example, NH4OH, a weak base (electrolyte)
dissociates in solution as NH4OH ⇌ NH4+ + OH-

On applying the law of mass action [NH4+] [OH-] =K [NH4OH] = constant, on adding
strong electrolyte, NH4 Cl, NH4Cl ⇌ NH4+ + Cl-, NH4+ ions are added to the solution. Thus
the concentration of NH4+ ions coming both from NH4Cl and NH4OH (common ion)

UTTARAKHAND OPEN UNIVERSITY Page 31

LABORATORY COURSE-I BSCCH- 104

increases but K remains constant at any given temperature. As a result, the value of
[NH4OH] must increase thereby decreasing the value of [OH-]. This indicates that the
degree of ionisation of NH4OH is decreased by the addition of NH4Cl which furnishes the
common ion, NH4+. Similarly the ionisation of H2S, a weak electrolyte, is diminished in the
presence of HCl, a strong electrolyte, giving common H+ ions.

The principle of common ion effect is of immense importance in qualitative analysis

because this provides a valuable method for controlling the concentration of the ions
furnished by a weak electrolyte. The common examples are: precipitation of second group
radicals as sulphides using H2S in presence of HCl and that of fourth group cations as
sulphides in presence of NH4OH. Similarly precipitation of third group cations as
hydroxides using NH4OH in presence of NH4Cl. The detailed account will be given in the
respective groups.

Complex Formation.

Complex ion formation is of great importance in qualitative analysis (i) to dissolve a

precipitate alone or from a mixture of two or more (ii) to check the precipitation of a
particular cation by complex ion formation. For example,

(a) AgCl is soluble in ammonia solution due to the formation of the complex ion, [Ag
(NH3)2]+.

Ag+ + 2 NH3 → [Ag (NH3)2]+.

This capacity of Ag+ ion is utilized in its separation from Pb2+ and Hg22+ ion.

(b) Separation of Cu2+ and Cd2+ ions is also based on the complex formation tendency with
CN- ions from KCN solution: K3 [Cu (CN)4] and K2 [Cd (CN)4]. Of the two complex ions
[Cu (CN)4]3- and [Cd(CH)4]2-, the value of instability constant for copper complex ion is
less than cadmium comlex ion and hence more Cd2+ ions are available in the solution than
Cu2+ ions. In presence of H2S gas, CdS (yellow ppt) is formed but copper ion remains
unaffected.

[Cd (CN)4]2- ⇌ Cd2+ + 4CN- and H2S ⇌ 2H+ + S2-

Cd2+ + S2- ⇌ CdS (yellow ppt.).

3.6 SEPARATION OF CATIONS INTO GROUPS

(i) Precipitation of group I cations. The cations of group I are precipitated as insoluble
chlorides in the presence of dil. HCl.

UTTARAKHAND OPEN UNIVERSITY Page 32

LABORATORY COURSE-I BSCCH- 104

(ii) Separation of group II cations from group IV cations. The cations of both these
groups are precipitated as sulphides but in different media, group II cations are precipitated
in acidic medium (HCl) and those of group IV in basic medium (NH4OH). As has already
been stated, the precipitation of sulphides can occur only when [M2+] [S2-] exceeds the
solubility product of the sulphide, MS at given temperature,

i.e. [M2+] [S2-] > KS

In presence of HCl, due to common H+ ions, the ionisation of H2S is suppressed thereby
giving less concentration of S2- ions in solution. Under this condition, the ionic product of
metal and sulphide ions only exceeds the solubility product of sulphides of group II cations
(such metal sulphides have low values of solublility products) and as a result these
sulphides are precipitated. The solubility product values for sulphides of group IV cations
being high are not surpassed by ionic product and these cations remain in the filtrate. These
cations are then precipitated as sulphides in presence of excess S2- ions in basic medium,
i.e., NH4OH.

(iii) Precipitation of group III cations. The group III cations are precipitated as
hydroxides with the help of NH4OH in the presence of NH4Cl. NH4Cl suppresses the
ionisation of NH4OH thereby giving less OH- ions in solution, just sufficient to precipitate
the group III cations and keeping higher group, i.e. IV, V & VI, cations in solution. This
happens because of the low values of solubility products of the hydroxides of group III
cations which are surpassed by ionic products of [OH-] and [M3+].

(iv) Precipitation of group V cations. These cations are precipitated as carbonates using
(NH4)2CO3 in presence of NH4OH when Mg remains in solution.

3.7 PRELIMINARY INVESTIGATION OF THE SAMPLE

Basic radicals or cations in a sample can be tested by two types of tests:

(1)Dry tests, (2) Wet tests.

(1)Dry tests: These are the preliminary tests and include the following:
(a)Dry heating test
(b)Flame test
(c)Borax bead test
(d)Cobalt nitrate test
(e)Charcoal cavity test
(f)Microcosmic bead test

Of these, flame test, borax bead test, cobalt nitrate test and charcoal cavity test are more
important and impart more valuable information about the cations in the sample under
investigation.

UTTARAKHAND OPEN UNIVERSITY Page 33

LABORATORY COURSE-I BSCCH- 104

(b) Flame test. Chlorides of certain metals when heated strongly using a loop of Pt-wire
cleaned by conc. HCl, are volatilized easily in non-lumious flames of bunsen burner and
their vapours become incandescent in the flame. The salt or group ppt. is picked by Pt-wire
loop and kept into the edge of non-luminous flame. The imparted colour by the metals can
be observed by naked eye:

Na – golden yellow, K-violet, Cu-bluish green,

Ca – brick or dull red, Sr – crimson red, Ba- apple green.

(C) Borax bead test. This test is performed mainly for the coloured substances and
sometimes for white substances leaving coloured residue on dry heating.

The loop at the tip of the Pt-wire is heated in the flame, then dipped into borax powder,
heated again strongly till borax swells up and finally converted into a transparent glassy
bead. This bead is touched with the substance or group ppt. heated strongly in non-
luminous flame and then in luminous flame, and color is observed.

Cation Non-luminous flame Luminous flame (reducing)

(Oxidising)
Copper green or light blue red or colorless
Iron Yellow bottle green
Chromium Green Green
Cobalt deep blue deep blue
Nickel light brown Black
Manganese Violet Colorless

Chemistry of borax bead test: On strongly heating borax transforms into glassy bead:

Na2B4O7 10H2O Na2 B4O7 → B2O3 + 2NaBO2 (glassy bead)

B2O3 combines with basic oxides to form meta borates which have characteristic
colours.

(d) Cobalt nitrate test. Cobalt nitrate on heating is decomposed to CoO which combines
with certain metallic and non-metalic oxides to give colored compounds. The powdered
substance or mixture is mixed with an equal amount of solid Na2CO3 placed in a charcoal
cavity, moistened with water and heated with the help of blow pipe. It is then moistened
with few drops of cobalt nitrate and heated again. The color of the residue indicates the
radical.

Blue- Al3+, PO43-, BO33-

UTTARAKHAND OPEN UNIVERSITY Page 34

LABORATORY COURSE-I BSCCH- 104

Green- Zn2+

Dirty blue-green- Sn2+

Pink- Mg2+

Example. Zn SO4 Na2CO3 → Zn CO3 + Na2 SO4

ZnCO3 → ZnO + CO2 ↑

2CO (NO3)2 →2Co O + 4 NO2 ↑ + O2↑

Zn O + Co O → Zn O. Co O ⇌ Co Zn O2

(e) Charcoal cavity test. In this test, the powdered sample is mixed with an equal amount
of solid Na2CO3, placed in a charcoal cavity, moistened with water and strongly heated in a
reducing flame by means of blow pipe. From the color of the bead or deposit round the
cavity (incrustation), cation/metal is identified.

Hot residueCold residueInference

Yellow WhiteZn

Reddish brownreddish brownCd

Brown yellowPb

Orange yellowBi

Yellow whiteSn

White whiteAs, Al, Mg, Ca, Ba

Red RedCu

Black whiteFe, Co, Ni, Mn

(2) Wet tests. These are most important tests and are performed to confirm the presence of
almost all the cations. The first step for the wet tests is the preparation of the original
solution.

3.8 METHODS FOR THE PREPARATION OF ORIGINAL

SOLUTION
The solution that contains all the cations is known as original solution. It can be prepared as
follows:

UTTARAKHAND OPEN UNIVERSITY Page 35

LABORATORY COURSE-I BSCCH- 104

(i) A little of the mixture sample is boiled with water with shaking. If does not dissolve
then,
(ii) Mixture is boiled with dil. HCl. Still if does not dissolve then,
(iii) About 1gm mixture is boiled with 5ml. conc. HCl in 100ml beaker for a while,
diluted with water and boiled again. Mostly the mixture is dissolved and solution
becomes transparent.
(iv) If the mixture is insoluble in conc. HCl, then solubility should be observed in least
quantity of dil. HNO3, then conc. HNO3 and finally in aqua regia.
(v) If the solution is made in HNO3 or aqua regia, it has to be evaporated to dryness and
dry residue is dissolved in dil. HCl or water after boiling. Sulphuric acid is never
used as a solvent as it precipitates Ba, Sr, Ca & Pb as sulphates which are insoluble
even in aqua regia.
3.9 SEPARATION OF CATIONS INTO ANALYTICAL GROUPS
On the basis of solubility product and reagents, the cations are divided into the following
six groups:
1. First group: Pb2+, Ag+, Hg22+ (ous)
2. Second group A : Pb2+, Cu2+, Bi3+, Cd2+, Hg2+ (ic)
B : As3+, Sb3+, Sn2+ + (ous), Sn4+ (ic)
3. Third group: Al3+, Cr3+, Fe3+
4. Fourth group: Ni2+, Co2+, Zn2+ Mn2+
5. Fifth group: Ba2+, Sr2+, Ca2+
6. Sixth group: Mg2+

Zero group is also there containing NH4+ ion.

The cations, group reagents and salts precipitated along with their colors are summarized
below:

5. Fifth group:

6. Sixth group:

Zero groups are also there containing ion.

The cations, group reagents and salts precipitated along with their colors are summarized
below:

S.No. Group Group Radiclas Group Salt Colour of the

Reagent Reprecipitated precipitate

1. First Ag+, Pb++, Hg2 Dil. HCl (Chlorides) White ppt.

Group (ous) AgCl,

UTTARAKHAND OPEN UNIVERSITY Page 36

LABORATORY COURSE-I BSCCH- 104

AgCl, PbCl2,
HgCl2

2. Second Pb++, Hg++ (ic.) Dil. (Sulphides) Black ppt.

group Bi+++, Cu+++, Cd++, HCL+ (Sometimes
Sb+++, Sn++, Sn+++, red ppt.)
Sn++++(ic), As+++
3. Third After (Hydroxides) White ppt.
group removing Al( ) Brown ppt.
boil Fe( Green ppt.
the solution
with
4. Fourth Iiird Group (sulphides) White or state
group Zns ppt.
Chocoloate-
pink ppt. Black
ppt. White ppt.
5. Fifth Boil off (Carbonates) Black ppt.
group and BaCO3, White ppt.
then add CaCO3,
SrCO3

6. Sixth & (Phosphate) White

Group ( ) crystalline ppt.
and
shake well.
Fifth
Group
(Phosphate
) Filtrate+

Solution

Important Hints for proceeding with the tests of Basic Radicals

(i) Group reagents should be added in systematic order.

(ii) A little excess of the group reagent must be added to ensure the complete
precipitation fot he group radicals.

UTTARAKHAND OPEN UNIVERSITY Page 37

LABORATORY COURSE-I BSCCH- 104

(iii) Solution in every group, if after adding group reagent is heated, granular
precipitate is obtained.

(iv) The volume of the solution should not be unnecessarily increased at any step. If the
volume of solution at any stage has become too large (in spite of great precautions)
do not throw any a portion. Put it in a dish, and evaporate it to a small volume.

(v) There are radicals also, among them and are

examined by flame test and for radical, special test is performed.

(vi) Group reagent is added to original solution one after another, till the ppt. in any
group is obtained. The ppt. shows the presence of any radical in that group. The
complete precipitation of the radical in that group should be judged by adding
sufficient amount of the group reagent otherwise it will create a great disturbance in
the usual analysis of the subsequent group radicals.

(vii) Hydrogen sulphide is a very important gas reagent for the precipitation of IInd and
IV th group radicals. It is prepared in the Kipp’s apparatus by the action of dil.
on ferrous sulphide. Through the kipps apparatus continuous supply of the
gas is available. See fig ahead.

3.10 ANALYSIS OF THE CATIONS OF ANALYTICAL GROUP I

Analysis of first group (silver group)
A white ppt. is obtained after the addition of dil. HCL to the original solution. It is filtered
and washed with water and then boiled with 5-10 ml water. Filter and keep the filtrate for
II group.

Note: If solution is prepared in dil. HCL, 1 st group is considered to be absent.It is not

necessary that there should be complete precipitation of metallic ions of a particular
group by means of that group reagent before proceeding of the next group. Mercuous salts
are partially oxidized to mercuric salts and so are precipitate as mercuric sulphide also.

Analysis of second group

This group is divided in two groups:

(i)II nd A group(copper Group)

(ii)IInd B group ( arsenic group)

II A copper Group:

Copper Group consists of

UTTARAKHAND OPEN UNIVERSITY Page 38

LABORATORY COURSE-I BSCCH- 104

In this group H2S is passed in a little portion of the 1st group filtrate. If precipitate does not
come, then it should be diluted with water, warmed and then H2S is passed in the rest of the
solution. It is faltered and washed well with H2S water. The filtrate is kept for III group.
Different radicals give the following coloured precipitates.

Hgs Black(sometimes Cds Yello

red) w
Pbs Black(or Brown) Yello
w
Brown Yello
w
CuS Black(or Brown) Orang
e
Yellow ammonium sulphide contains excess of sulphur dissolved in colourles ammonium
sulphide solution and is expressed as ( )

The washed precipitate is warmed with a little yellow ammonium sulphide solution and
filtered.

Residue Filtrate

(II A Group) (II B Group)

Hg(ic), Pb, Bi, Cu, Cd As, Sb, Sn (ous), Sn(ic)

3.11 ANALYSIS OF THE CATIONS OF GROUP II

II A copper group- Residue is washed with water and then treated with 50%
boiled cooled and filtered.

Black residue Filtrate: It may contain the nitrates of Pb, Bi, Cu. Take a little part of it
add dil.
It may be HgS. H2SO4 . If a white ppt. appears then add alcohol and dil. H2SO4 to the
Dissolve it in aqua whole filtrate and filter.
regia and evaporate White residue Filtrate: It may contain Bi, Cu and Cd as
it to almost dryness. It may contain nitrate. Add to it excess of NH4OH and
Add water and Dissolve this filter:
divide it in two parts residue in conc. White Filtrate: It may contain Cu and
(i) To first part add Solution of residue: It Cd. If it is bule Cu is there if it is
SnCl2 Soln white or CH3COONH4 and may be colourless Cu is absent. First

UTTARAKHAND OPEN UNIVERSITY Page 39

LABORATORY COURSE-I BSCCH- 104

grey ppt (II) To add K2CrO4 Bi(OH)3. Method:

second part add Cu yellow ppt pb Dissolve (i)To first part add ch3cooh in
turnings whitish (Lead) confirmed. the residue excess K4 Fe(CN)6 brown
deposti on Cu Hg++ in the least coloured ppt. Cu++
confirmed. quantity of (copper)confirmed.
conc. HCl (ii) To second part add KCN soin.
divide it in Till the filtrate becomes colourless.
two parts: (I) Now pass H2S yellow ppt. Cd++
To first part (cadrnium) confirmed.
add excess Second method: Add. conc. HCl
of water and pass H2S and filter.
white ppt. Filtrate:
(II) To Dilute it and
second part pass H2S
add. Sod again yellow
stannite ppt.
soln. black Black residue: (cadmium)co
ppt. Cu++ (Copper) nfirmed.
(Bismuth confirmed.
confirmed)

(iii) To third part add 1 c.c. of

conc. HCl
and FeSO4 soln. and filter.

Residue Filtrate: Dilute

Cu++ (copper) it with water and
confirmed. pas H2S gas
yellow ppt.
++
Cd (Cadmium)
confirmed.

3.12 ANALYSIS OF THE CATIONS OF ANALYTICAL GROUP III

IIB Arsenic Group

Dilute the filtrate with water obtained after treating the second group ppt. with yellow
ammonium sulphide and dil. HCl (in excess). A coloured ppt. indicates the presence of
arsenic group but if a white ppt. is obtained it shows the absence of arsenic group radicals
and reject it. Fiter the ppt. and boil it with conc. HCI and filter.
Yellow residue: Filtrate :
It may be As2S3. Dissolve It may contain chlorides of Sb and Sr which may be
it in conc. HNO3and add confirmed by two different methods.
UTTARAKHAND OPEN UNIVERSITY Page 40
LABORATORY COURSE-I BSCCH- 104

ammonium molybdate First Method:

solution and heat Yellow Make the filtrate just alkaline by adding NH4OH soln.
ppt. As+++(Arsenic) Add 1-2 gms. solid oxalic acid boil and pass H2S gas. Filter
Confirmed. if a ppt. is obtained.
Orange residue: Filtrate:
It may be Sb2S3: It may contain Sn. To it add
Dissolve it in least quantity NH4OH to make it alkaline
of conc. HCl Dilute it with and pass H2S gas
water white ppt. or Dirty yellow ppt.
turbidity. Sn+++ (Stannic) confirmed
Sb+++ (Antimony)
confirmed.
Second Method:
To the filtrate add iron filling and heat for five minutes and
filter.
Black residue: Filtrate
+++
Sb (Antimony It may contain SnCl2. To it
confirmed.) add HgCl2 Soln.
White or gray ppt. Sn++
(Stannous) confirmed.

ANALYSIS OF THIRD GROUP

Boil off H2S completely (test with lead acetate paper for this) from filtrate of the second
group and concentrate it. Boil it again with 1 c.c. of conc. HNO3 as to convert all ferrous
salt (if present) to ferric salt; otherwise ferrous hydroxide will not be completely
precipitated in this group and thus will interfere in IVth group giving a black precipitate of
Fes. Then after cooling add NH4CL and NH4OH ( in excess) till the solution distinctly
smells of ammonia.
Filter and wash the precipitate with water and keep the filtrate for IVth group. Dissolve the
ppt. in 2 c.c. of H2O2 or in excess of Br2water + NaOH2, boil* it and filter. Boiling at this
stage is essential since this ensures the complete oxidation of Fe++ to Fe+++
Fe(OH)3 – Brown ppt.
Al(OH)3 – White ppt.
Cr(OH)3 - Green or light bluish green ppt.

Residue : Filtrate :
Brown ppt . it may contain It may contain NaAlO2 and NaCr4. if it is yellow
Fe(OH)3 or MnO(OH). Na2CrO4 will be there otherwise NaAIO2 may be
there. Divide it in two parts.

UTTARAKHAND OPEN UNIVERSITY Page 41

LABORATORY COURSE-I BSCCH- 104

Divide the precipitate in two (a) First part To the part add
parts: CH3COOH + ( CH3COOH)2 NH4CI and boil
(i) ppt. +conc. Pb White gelatinous
HNO3 + PbO2 Boil and cool Yellow ppt. ppt. Al+++
By adding a little water (b)Second part + AgNO3 (Alumunium)
+++
Light, pink, violet colour Brick red ppt. Cr confirmed.
Mn++ (Manganese) confirmed. (Chromium) confirmed.
(ii) Dissolve the precipitate in
dil. HNO3 or dill. HCI and
divide it in two parts:
)To first part add K4[Fe(CN)6]
deep blue colour or ppt.
(b) To second part add
ammonium Sulphocyanide
Blood red colour Fe+++(Ferric)
Confirmed.
Notes:
(i)H2S should be completely removed before adding conc. HNO3; otherwise it will be
oxidized into H2SO4; and thus will precipitate the Vth group radicals as sulphates.
(ii)Sometimes Mn also precipitates as MnO.OH(Brown ppt.) in this group so its test
becomes necessary.
(iii) After boiling off H2S addition of conc. HNO3 is essential so as to convert all
ferrous salts into ferric salts.
(iv) Addition of NH4Cl before NH4OH is absolutely essential otherwise the basic
radicals of IVth and Vth groups will precipitate out as hydroxide in this group.
(v)Interfering radicals should be removed before proceeding in this group.
(vi) H2S should be passed in hot solution. At higher temperatures sulphides precipitated
are granular and easy to filter.
3.13 ANALYSIS OF THE CATIONS OF ANALYTICAL GROUP IV

ANALYSIS OF FOURTH GROUP

Some of the characteristics of the basic radicals of this fourth group are tabulated as
follows:
Form of the Nickel (NI++) Cobalt (Co++) Zinc (Zn++) Manganese
salt (Mn++)
Sulphide Black (NIS) Black (CoS) White or Grey Light
Green- Green Pink Pink (ZnS) White Pink(MnS)
Colourless White
Colouriess
Light pink, pink

UTTARAKHAND OPEN UNIVERSITY Page 42

LABORATORY COURSE-I BSCCH- 104

violet.
Pass H2S continuously in the hot ammonical filtrate of II group. Formation of the
precipitate shows the presence of fourth group. Filter and wash the ppt. and keep the filtrate
for fifth group.
Different radicals give the following coloured precipitates:
NIS Black ZnS White or
grey
CoS Black MnS Light pink
Notes:
(i)H2S must be passed in hot solution otherwise ZnS and MnS will from colloidal
solution.
(ii)H2S should not be passed for a very long time otherwise NiS and MnS will turn into
colloidal solution.
Ppt. is treated with dill. HCI and filtered:
Residue: Filtrate:
It may contain NiS and CoS. Dissolve it in it may contain MnCl2 and ZnCl2. Boil off
aqua-regia(3HCI+ HNO3) and evaporate to H2S, and add excess of NaOH and filter.
dryness+ water and divide it in number of
parts.
To one part (i)To one part add NH4OH Residue Filtrate:
and NH4OH (in excess) + CH3COOH White turning brown It may contain
(in excess) + (in excess) + KNO2 due to oxidation. zinc. Pass H2S
dimethyl solution. Yellow (i) Dissolve the residue in the filtrate.
++
glyoxime crystalline ppt. Co in conc. HNO3 and add A white grey
Scarlet red (Cobalt) Confirmed. PbO2. Boil for 2-3 ppt. Zn++
ppt. (ii) To other part in a minutes and dilute with (Zinc)
++
Ni (Nickel) porcelain dish + NaHCO3 water Pink or violet confirmed.
Confirmed solid (in excess) + Br2 colour.
water. Shake for some Mn++(manganese)
time Apple green confirmed.
++
colour (in cold) Co (ii) Residue + oxidizing
(Cobalt) confirmed. fusion mixture (KNO3+
Apple green colour in cold Na2CO3).
changing to black on Heat strongly on a
++
heating Co (Cobalt) porceian piece green
and Ni++ (Nickel) both mass is obtained which
confirmed. dissolves to give pink
solution Mn++
(Manganese) confirmed.

UTTARAKHAND OPEN UNIVERSITY Page 43

LABORATORY COURSE-I BSCCH- 104

3.14 ANALYSIS OF THE CATIONS OF ANALYTICAL GROUP V

After boiling off H2S, concentrate the fourth group titlrate to one-third (1/3) of its original
volume. Then add NH4OHand (NH4)2CO3 (never boil at this state.) Formation of white
precipitate shows the presence of fifth group. Filter and was the ppt. keep the filtrate for the
radicals of sixth group. Dissolve the precipitate in least quantity of acetic acid and boil for a
few minutes. Take a small part of this soln. and add. K2CrO4 soln. If a yellow ppt appears,
heat the whole solution with excess of K2CrO2 so as to precipitate barium completely. If no
ppt. appears on adding K2CrO4 soln, then do not add K2CrO4 solution to the whole soln.
Now proceed as follows:
Residue: Yellow ppt. BaCrO4. Ba++ It may contain (CH3COO)2 and CH3COO) Ca.
(Barium) confirmed. To it add (NH4)2SO4 solution in excess and
boil it filter it.
Filtrate: it may contain Residue: White
ca. to it add (NH4)2C2O4 ppt. (SrSO4) Sr++
soln. white ppt. Ca++ (strontium)
(calcium) confirmed. confirmed.
Notes:

(1) It is better to use saturated solution of (NH4) 2SO4 to detect Sr++ radical. After
addition of the reagent, wait for few minutes to see if a precipitate of SrSO4 is
obtained.

(2) Sometimes calcium does not get precipitated in its group due to the formation of
Ca(HCO3)2 on addition of (NH4)2 CO3 to the concentrated filtrate of IVth group.
As Ca(HCO3)2 is soluble and it passess into the filtrate of Vth group. Hence filtrate
of Vth group must be tested for calcium before proceeding to VIth group.

(3) They are tested in the order BSC(Barium, strontium, Calcium).

3.15 ANALYSIS OF THE CATIONS OF ANALYTICAL GROUP

VI

Heat the fifth groups filtrate with ammonium oxalate and discard the precipitate, if comes.
Add 2-3 c.c. of NH4OH and excess of sodium phosphate (Na2HPO4) to the filtrate. Shake
the solution with a glass rod. After a few minutes a white crystalline precipitate results.
Mg++(Magnesium) confirmed.
Analysis of ammonium (NH4+) Radical (zero group)

UTTARAKHAND OPEN UNIVERSITY Page 44

LABORATORY COURSE-I BSCCH- 104

(1) Heat a little mixture with 2-3 c.c NaOH in a test tube. A characteristic smell of
(NH3) is obtained. On bringing a glass rod dippedin conc. HCl at the mouth of the
test tube , enormous white fumes are produced.

(2) On adding Nessler’s regent to the solution of the mixture →brown color of ppt. is
obtained. This test is extremely sensitive and characteristic.

Note. Nesster’s reagent is prepared by adding KI to Hg Cl2 solution until the red ppt
(HgI2) formed, is dissolved. It is mixed with NaOH solution.

CHEMICAL REACTIONS INVOLVED IN THE TEST OF

BASIC RADICALS
First Group: Lead ( Pb++ ), Silver( Ag+ ) Mercurous (Hg2++) and lead (Pb++).

Mercurous (Hg++):

UTTARAKHAND OPEN UNIVERSITY Page 45

LABORATORY COURSE-I BSCCH- 104

Second Group : Mercuric (Hg++), Lead(Pb++), Bismuth(Bi++), Copper(Cu++),

Cadmium(Cd++), Arsenic(As+++), Antimony(Sb+++), Tin (Sn++, Sn+++)

Sometimes, in second group, white or a light yellow ppt. is observed which is due to
sulphur precipitated from H2S by excess of HNO3 or osther oxidizing agents e.g. (NO2-,
SO3--, Fe+++). The ppt. should be rejected.

UTTARAKHAND OPEN UNIVERSITY Page 46

LABORATORY COURSE-I BSCCH- 104

2BiCl3 + 3Na2SnO2 + NaOH 2Bi + 3Na2SnO3 + 6NaCl + 3H2O

UTTARAKHAND OPEN UNIVERSITY Page 47

LABORATORY COURSE-I BSCCH- 104

Thus when H2S is passed through a solution containing these complexes, solubility product
of CdS only is exceed and therefore it gets precipitated.

UTTARAKHAND OPEN UNIVERSITY Page 48

LABORATORY COURSE-I BSCCH- 104

Arsenic (As+++):
AsCl3 + 3H2S As2S3 + 6HCl
Yello ppt.
As2S3 + 3(NH4)2S2 3(NH4)3AsS3
Ammonium thio arsenite

As2S3 + 6NH4Cl +3H2S

3(NH4)3AsS3 + 6HCl
Ammonium thio arsenite Yello ppt
As2S3 dissolves in nitric acid forming arenic acid(H3AsO4)

H3AsO4 + 12(NH4)2MoO4 + 21HNO3 (NH4)3AsO4.12MoO3 + 21NH4NO3 +12H2O

Yello ppt
Antimony (Sb+++): Ammonium arsenomolybdate
3SbCl3 + 3H2S SbS3 + 6HCl
Orange ppt.

SbS3 + 3(NH4)2S2 2(NH4)3SbS3

SbS3 + 3(NH4)2S2 2(NH4)3SbS4 + S

Ammonium thio-antimonate

2(NH4)3SbS4 + 6HCl Sb2S3 + 6NH4Cl + 3H2S

2(NH4)3SbS4 + 6HCl Sb2S5 + 6NH4Cl + 3H2S

SbS3 + 6HCl 2SbCl3 + 3H2S

SbS5 + 6HCl 2SbCl3 + 3H2S + 2S

SbCl3 + H2O SbOCl + 2HCl

Milky(Antomony
oxychloride)
Tin (Sn++,Sn++++):

SnCl2 + H2S SnS + 2HCl

Brown ppt.
SnCl4 + 2H2S SnS2 + 4HCl
SnS- Insoluble in ordinary amm. sulphide but soluble in yello amm. sulphide.
SnS2- Soluble in ordinary amm. sulphide
SnS + (NH4)2S2 (NH4)2SnS2
SnS2 + (NH4)2S (NH4)2SnS2
Amm. thio-stannate
(NH4)2 SnS3 + 2HCl SnS2 + 2NH4Cl + H2S
SnS2 + 4HCl SnCl4 + 2H2S

SnCl4 + Fe SnCl2 + FeCl2

2HgCl2 + SnCl2 Hg2Cl2 + SnCl4
White ppt.

UTTARAKHAND OPEN UNIVERSITY Page 49

LABORATORY COURSE-I BSCCH- 104

Hg2Cl2 + SnCl2 2Hg + SnCl2

Third Group
IRON, ALLMINIUM, CHROMIUM
Fe+++, Al+++, Cr+++
In the third group ferrous salts(Fe ) areoxidized to ferric salts (Fe+++) by boiling it with few drops of con.
++

HNO3.
2FeCl2 + 8HNO3 2Fe(NO3)3 + 4HCl + 2NO2 + 2H2O

Iron (Fe+++):
FeCl3 + 3NH4OH Fe(OH)3 + 3NH4Cl
Brown ppt.
Fe(OH)3 + 3HCl FeCl3 + 3H2O

2FeCl3 + 6NH4CNS Fe[Fe(CNS)6]3 + 12KCl

Ammo. thiocyanate Ferric sulphocyanide
Blood red colour
4FeCl3 + 3K4[Fe(CN)6] Fe[Fe(CNS)6]3 + 12KCl
Pot. ferrocyanide Ferric ferrocyanide
Deep blue colour
Aluminium (Al+++):
AlCl3 + 3NH4OH Al(OH)3 + NH4Cl
White ppt.

Al(OH)3 + NaOH NaAlO3 + 2H2O

NaAlO3 + NH4Cl + H2O Al(OH)3 + NH3 + NaCl

Chromium (Cr+++):
2CrCl3 + 3NH4OH Cr(OH)3 + 3NH4Cl
Green ppt.
Cr(OH)3 + 4NaOH + 3H2O2 2Na2CrO4 + 8H2O

2NaOH + Br2 NaBr + NaOBr + H2O

Cr(OH)3 + 4NaOH 3H2O2 Na2CrO4 5H2O 3NaBr

Na2CrO4 + (CH3COO)2Pb PbCrO4 + 2CH3COONa

Yello ppt.
Fourth group
ZINC, MAGNASIUM, COBALT
Zinc (Zn++)
ZnCl2 + H2S ZnS + 2HCl
White grey ppt.
ZnS + 2HCl ZnCl2 2H2S
ZnCl2 + 2NaOH Zn(OH)2 + 2NaCl
White ppt.
Zn(OH)2 + 2NaOH Na2ZnO2 + 2HCl

UTTARAKHAND OPEN UNIVERSITY Page 50

LABORATORY COURSE-I BSCCH- 104

Test of Co and Ni with NaHCO3-Br2 water (Palit's test):

When the solution of cobalt and nickel salt is treated with excess of sodium bicarbonate,
cobalt forms a pink coloured complex sodium cobalto-carbonate. Which on treated with
bromine wateris oxidised to green coloured sodium cobalti--carbonate. Nickel does not

UTTARAKHAND OPEN UNIVERSITY Page 51

LABORATORY COURSE-I BSCCH- 104

form a complex with NaHCO3 but on heating with bromine water, it is oxidised to black
nickelic oxide.

UTTARAKHAND OPEN UNIVERSITY Page 52

LABORATORY COURSE-I BSCCH- 104

Sixth group
Magnesium (Mg2+):

Mg(NO3)2+Na2HPO4+NH4OH→Mg(NH4)PO4↓+ 2NaNO3 (white ppt.) +H2O

zero group:
Ammonium (NH4+)

NH4Cl+ NaOH →NaCl + H2O + NH3 ↑

NH3 + HCl →NH4 Cl (white fumes)

SUMMARY

The purpose of this lab is to identify the cations present in an unknown solution.
Qualitative analysis was used to identify the substances present in the unknown solution.
Qualitative analysis is used by reacting the unknown solution with a number of different
reagents.

UTTARAKHAND OPEN UNIVERSITY Page 53

LABORATORY COURSE-I BSCCH- 104

UNIT 4: INTRODUCTION LAB TECHNIQUES:

ORGANIC CHEMISTRY
CONTENTS:
4.1 Objectives
4.2 Introduction
4.3 Determination of melting point
4.4 Determination of melting point (Naphthalene, Urea, Benzoic acid, Succinic acid etc.)
4.5 Determination of boiling point and Distillation
4.1(Toluene, Ethanol, Propanol, ethyl acetate)
4.6 Crystallization
4.7 Sublimation (Camphor, Phthalic acid, Succinic acid)
4.8 Summary

4.1 OBJECTIVES

In this chapter students learn the following objectives.

•To determine the melting point procedure.
•Determination of boiling point and Distillation.
•To determine the process of Crystallisation.
•To determine the sublimation of camphor, phthalic acid and succinic acid.

4.2 INTRODUCTION

The purpose of the first part of the laboratory course is to introduce you to many of the
techniques used to purify and separate compounds. Melting point and to a much lesser
extent, boiling point is one important way of establishing whether the desired purification.
Melting point is the temperature at which a solid and liquid exist in equilibrium with each
other at a given pressure, or it is the temperature at which a solid begins to change to a
liquid under a pressure of one atmosphere. The boiling point of a liquid is that temperature
at which the vapour pressure of the liquid equals the atmospheric pressure.
Crystallization is a separation technique that is used to separate. a solid that has dissolved
in a liquid and made a solution. Sublimation is the transition of a substance directly from
the solid to the gas phase without passing through the intermediate liquid phase
4.3 DETERMINATION OF MELTING POINT

This is the most important and significant step in the identification of a solid organic
compound or to test the purity of a given solid organic compound. The experiment is
UTTARAKHAND OPEN UNIVERSITY Page 54
LABORATORY COURSE-I BSCCH- 104

usually carried out by capillary tube method using Thiele’s tube (fig. 4.3.1) or most
conveniently using the flask and test tube (fig. 4.3.2) available in every chemistry lab. In
actual practice, a small quantity of the organic substance whose melting point is to be
determined is finely powdered between the pieces of filter paper or on a porous plate with
the help of a spatula and introduced in a glass capillary tube closed at one end by heating in
a Bunsen flame. The material is picked by gentle tapping the capillary on the table, the
capillary is then attached to the lower end of the thermometer with its sealed end down.
The thermometer is then placed in a thiele’s tube or test tube containing conc. H2SO4 or
paraffin oil in such a way that the liquid covers the filled length of the capillary and the
open end of the capillary remains above the surface of the liquid (to avoid the entry of the
liquid into the capillary). The test tube (in the flask and test tube method) in turn, is placed
in a flask containing the same bath liquid as in the test tube as shown in fig. 4.1.2 The flask
is gently heated and the burner is removed from time to time so that the slow steady rise in
temperature is maintained and this rise in the temperature is observed carefully. The
temperature at which the solid substance melts completely and becomes almost transparent
is recorded. This is the melting point of the organic solid substance used. Traces of
impurities or moisture considerably lower the melting point. Hence the solid organic
compound taken for the determination of melting point should be pure and dry.

Mixed Melting Point.

The mixed melting point is determined to establish the purity of known organic
compounds. A small amount of the compound under investigation is mixed with a little of
se pure compound from the laboratory and the melting point of such a mixture is
determined in the usual manner. If the value of the melting point of the mixture is the same
as that of the pure compound then the compound under investigation is pure but if the value
of its melting point is lower than that of the pure compound, the compound taken is impure.
Thus this technique not only helps in the identification of an organic compound but also in
establishing the purity of known organic compound.

UTTARAKHAND OPEN UNIVERSITY Page 55

LABORATORY COURSE-I BSCCH- 104

Fig. 4.3.1 D. of Melting point by Fig. 4.3.2 Determination of melting point by

Thiele’s method flask and test tube method

4.4 DETERMINATION OF MELTING POINT OF

NAPHTHALENE, UREA, BENZOIC ACID, SUCCINIC ACID
ETC

Melting point of compounds given below is measured by using any of above procedure
given in point 4.3.
(i)Naphthalene. It sublimes on heating, m.p. 800C.
(ii)Urea, m.p. 1320C.
(iii)Benzoic acid, m.p. 1210C.
(iv)Succinic acid. It also sublimes on heating, m.p. 1850C

4.5 DETERMINATION OF BOILING POINT

The boiling point of a liquid may be recorded in either of the two ways depending on the
availability of the appliances.
(a)First Method.
A few drops or a little liquid whose boiling point has to be determined is taken in a
ignition tube. A capillary tube sealed at the upper and is put inside the ignition tube and the
latter is attached to the lower part of the thermometer with the help of a rubber thread. The
thermometer along with the ignition tube is placed inside a pyrex test tube in such a way
that the liquid inside the ignition tube is covered by conc. H2SO4 taken in the test tube as

UTTARAKHAND OPEN UNIVERSITY Page 56

LABORATORY COURSE-I BSCCH- 104

shown in fig. 4.5.1 below. The test tube is heated slowly and the rise of bubbles inside the
capillary is carefully observed. The temperature at which a regular and speedy stream of
bubbles begins to escape is recorded and is taken as the boiling point of the given liquid.
(b)Second Method.
The simple apparatus for the determination of boiling point by this method is shown below
in fig. 4.5.2 (a) & (b). The liquid whose boiling point is to be determined is taken in a
distillation flask or sometimes in a hard glass tube having two holes in the cork. Some
pumice stone or porcelain pieces are added to avoid bumping. A thermometer is fitted in
the flask or glass tube through a cork. The delivery tube of the flask or a bent glass tube
corked with the glass tube is connected to a water condenser if available (or the vapours of
the liquid can also be collected in a long test tube).
The thermometer is adjusted about one cm. above the surface the liquid. The flask or glass
tube is heated very gently using a burner. Heating should be very carefully regulated so that
the temperature rises slowly and boiling takes place gently. The liquid begins to distil over
after sometimes and the bulk of the liquid distils over within a certain temperature range
which remains almost constant throughout the distillation. At this moment a rapid stream of
bubbles starts issuing from the liquid. This constant temperature is the boiling point of the
liquid.

Distillation: It is a mixed process of vaporization (heating) and condensation (Cooling) of

a liquid substance. The boiling point determination by the second method involves this
process.

The distillation method is useful in purifying the given liquid in addition to determining the
boiling point. Now a days, the boiling point is usually determined by using the hard glass
tube method (Fig. 4.5.2) (b).

Fig. 4.5.1 Fig. 4.5.2 (a) Fig. 4.5.2 (b)

UTTARAKHAND OPEN UNIVERSITY Page 57

LABORATORY COURSE-I BSCCH- 104

4.5 DETERMINATION OF BOILING POINT

Boiling point of compounds given below is measured by using any of above procedure
given in point 4.4.
(1) Toluene, b. p. 1100C.
(2) Ethanol, b. p. 780C.
(3) Propanol (iso), b. p. 830C
(4) Ethyl acetate, b.p. 770C

4.6 CRYSTALLIZATION
The formation of crystals from the solution of a compound as a result of reduction in the
solvent volume or temperature is called crystallization. The separation and purification of
the crystalline compounds are usually carried out by using crystallization methods which
are based on the difference in the solubilities of the substances in a solvent. There are two
main crystallization methods available for the separation and purification of solid
organic compounds: (i) simple crystallization and (2) fractional crystallization.

(1)Simple crystallization.

The purification and separation of an organic compound is carried out by this method if an
impurity of small amount of insoluble substance or the small amount (less than 5%) of a
soluble substance is present.
Procedure:
The given impure organic compound is powdered and dissolved in suitable hot solvent just
sufficient to dissolve the whole solute in a beaker. The hot saturated solution (mixture) is
then quickly filtered through a filter paper placed in a glass funnel enclosed with a hot
water jacket (fig. 4.6.1). The hot water keeps the solution hot and prevents crystallization
during filtration. The insoluble and suspended impurities remain on the filter paper and a
clear filtrate is collected in the beaker placed below the funnel.
The hot filtrate is allowed to cool undisturbed at room temperature. After sometime, the
substance is obtained as crystals leaving behind the impurities in the mother liquor. Now
the crystals are separated from the mother liquor by filtration using filter paper with the
help of a Buchner funnel and suction pump (fig. 4.6.2). The crystals are again dissolved in
the minimum amount hot solvent and are allowed to crystallize on cooling. This process if
repeated two or more times, crystals of the compound are obtained in pure form.

UTTARAKHAND OPEN UNIVERSITY Page 58

LABORATORY COURSE-I BSCCH- 104

Fig. 4.6.1 Fig. 4.6.2

`Fig. 4.6.3
The crystals are now dried by pressing between folds of filter paper and finally over
anhydrous calcium chloride in a vacuum desiccators (fig. 4.6.3).
(2)Fractional crystallization.
When the organic compound and the impurities present in it are both soluble in the solvent
and their relative amounts are larger, their separation and purification are carried out by
fractional crystallization method. Fractional crystallization is the process in which the
crystallization procedures are repeated several times to separate the substances from their
mixture solution.
The principle of the fractional crystallization is based on the fact that if the two substances
are dissolved in minimum amount of a hot solvent and the solution is allowed to cool, then
that substance is crystallized first whose amount is more than that required to saturate the
solvent at room temperature. The procedure adopted at various steps is the same as that
discussed in simple crystallization method.

UTTARAKHAND OPEN UNIVERSITY Page 59

LABORATORY COURSE-I BSCCH- 104

4.7 SUBLIMATION
This method is used in the purification of those solids which on heating sublime or distil
over directly as vapours or in gaseous form without getting converted into the liquid state.
The vapours or gases, in turn, are converted directly to the solid form on cooling without
changing into liquid state (fig. 4.7). This solid obtained as a result of cooling of the vapours
or gases is called sublimate.

Naphthalene, camphor, Phthalic acid and succinic acid are purified by this
method.

Fig. 4.7 Sublimation

4.8 SUMMARY
The melting point of a solid is the temperature at which it changes state from solid to liquid
at atmospheric pressure. At the melting point the solid and liquid phase exists in
equilibrium. The melting point of a substance depends on pressure and is usually specified
at standard pressure. The boiling point of a substance is the temperature at which the vapor
pressure of the liquid equals the pressure surrounding the liquid and the liquid changes into
a vapor. The boiling point of a liquid varies depending upon the surrounding environmental
pressure. Crystallization is also a chemical solid–liquid separation technique, in which
mass transfer of a solute from the liquid solution to a pure solid crystalline phase occurs.
When anything solid turns into a gas without first becoming liquid is called sublimation.

UTTARAKHAND OPEN UNIVERSITY Page 60

LABORATORY COURSE-I BSCCH- 104

UNIT 5: SEPARATION TECHNIQUES

CONTENTS:
5.1 Objectives
5.2 Introduction
5.3 Simple distillation Methods
5.4 Solvent Extraction Method
5.5 Summary
5.1 OBJECTIVES

In this chapter students learn the following objectives.

•To know that mixtures are composed of constituents which are not combined?

•To apply methods of distillation, to separate mixtures.

•To understand the terms filtrate, residue, filtration, distil, distillate.

•To know that distillation can be used to separate a liquid from the solids which are
dissolved in it and that it is a process of evaporation and condensation.

•To know the process of solvent Extraction method.

5.2 INTRODUCTION
A separation process is a method to achieve any phenomenon that converts a mixture of
chemical substance into two or more distinct product mixtures, which may be referred to as
mixture. at least one of which is enriched in one or more of the mixture's constituents. In
some cases, a separation may fully divide the mixture into its pure constituents. Separations
differ in chemical properties or physical properties such as size, shape, mass, density, or
chemical affinity, between the constituents of a mixture. They are often classified
according to the particular differences they use to achieve separation.. There are many
methods that one can use to separate one substance from another. The method that one
would choose will be dependent on the physical properties of the substances involved.
Solvent extraction is a very useful process for the separation and isolation of compounds
from mixtures. Simple distillation is a procedure by which two liquids with different
boiling points can be separated. Simple distillation (the procedure outlined below) can be
used effectively to separate liquids that have at least fifty degrees difference in their boiling
points.

UTTARAKHAND OPEN UNIVERSITY Page 61

LABORATORY COURSE-I BSCCH- 104

5.3 SIMPLE DISTILLATION METHODS

Organic liquids are generally purified by employing distillation methods. As has already
been stated that the process of conversion of liquid into vapours by heating followed by the
cooling of the vapours to convert back to the liquid is called distillation. Thus, this process
involves both the evaporation and the condensation procedures. There are many methods
available for distillation of liquids which depend on the nature of the liquids and the
impurities present in them.
1. Simple Distillation When the liquid contains soluble impurities of non-volatile
substances, it is purified by the simple distillation method. The liquid must have volatile
nature. The impure liquid is heated in a distillation flask. The liquid is vapourised and the
vapours are allowed to pass through a water condenser when they condense and the
distillate is collected in a receiver. Thus gradually the whole liquid is vapouriesd and
condensed and non-volatile impuries are left behind in the distillation flask (fig. 5.3.1).

At the same time, when there is large difference between the boiling points of two miscible
liquids such as a mixture of benzene, b. p. 800C and nitro benzene, b.p. 2110C, they are also
separated by simple distillation method because in such cases distillation of fractions again
and again for few repetitions, pure fractions can be obtained.

2. Fractional Distillation
This method is employed for the purification of a liquid containing the impurities of other
volatile liquids or for the separation of two or more liquids having different boiling points
from a mixture. Thus fractional distillation is based on the difference of boiling points of
the liquids contained in the sample.

In the fractional distillation process, the mixtures of volatile liquids are heated slowly in the
special distillation apparatus (fig 5.3.2) and the liquid fractions obtained as distillates in the
suitable temperature ranges are collected in separate receiver flasks. This affects the partial
separation of constituents of the mixture. The fractions obtained first contain higher amount
of low boiling point liquid and the last fractions contain the excess of high boiling point
liquid. The fractions obtained are again distilled to get purer fractions than obtained earlier.
This process is repeated again and again to obtain the pure liquids.

In the apparatus used for factional distillation, the flask is attached with a fractionating
column the upper end of which is connected with a water condenser which in turn is
attached with the receiver flask. In the fractionating column, the process of vapourisation
and condensation of the fractions occurs automatically thereby separating the constituents
and the fractions need not to be distilled again and again.

The fractionating column is a long glass tube which has many obstructions. These
obstructions increase the surface area for cooling of vapours. When the liquid mixture is

UTTARAKHAND OPEN UNIVERSITY Page 62

LABORATORY COURSE-I BSCCH- 104

heated slowly, the liquids are vapourised and the vapours enter the fractionating column.
As these vapours move upwards in the column, less volatile or high boiling point liquid
component is condensed (liquefied) and comes down the column. This liquid comes in
contract with up moving vapours and further condenses the less volatile liquid component
thus bringing it down to the distillation flack. The vapours of more volatile or low boiling
point liquid component move upwards and escape through the condenser pipe where they
are condensed (liquefied). The process is repeated several times with the liquid remaining
in the distillation flack and that collected in the receiver. This makes effective separation of
the components of a liquid mixture.

This method is employed to separate the components of a liquid mixture having closer
boiling points such as that of benzene, b.p. 800C and toluene, b.p. 1100C and also to purify
the liquids.

Fig. 5.3.1 Apparatus for simple distillation Fig. 5.3.2 Fractional distillation
apparatus
3. Steam Distillation
The organic liquids or solids which are immiscible in water and steam volatile, are purified
by steam distillation method, for example: aniline, nitrobenzene, chlorobenzene,
benzaldehyde, o-nitrophenol, etc. The essential oils are also extracted from flowers and
plants by this method.

In this method impure organic liquid is mixed with some water and is heated in the
distillation flask. To this hot mixture is passed the steam from steam generator. At the
boiling point of the mixture, both water and organic liquid are vapourised together and the
vapours are condensed after passing through the water condenser. The distillate is collected
in the receiver as the two layers. Water and the organic liquid are separated by the
separating funnel

UTTARAKHAND OPEN UNIVERSITY Page 63

 LABORATORY COURSE-I BSCCH- 104

Fig. 5.3.3 steam distillation apparatus.

(1) Distillation Under Reduced Pressure

This method is employed for the purification of the liquids which are decomposed at or
before their boiling points. By reducing the atmospheric pressure the liquid boils at lower
temperature then its normal boiling point and distils without decomposing. The apparatus
used in the method is shown in fig. 5.3.4 below. The distillation is carried out using Claisen
flask. For example, glycerine is purified by this method. Glycerine decomposes at its
normal boiling point (2900C). At 10-12 mm pressure, glycerine boils at 1800C and does not
decompose.

UTTARAKHAND OPEN UNIVERSITY Page 64

LABORATORY COURSE-I BSCCH- 104

Fig. 5.3.4 Distillation under reduced pressure (apparatus)

5.4 SOLVENT EXTRACTION METHOD

This is a recent or modern method of separation and has much in common with fractional
distillation. This technique involves the partition or distribution of a solute between two
immiscible liquids in contact with each other. It furnishes clean separation in a short span
of time and uses simple apparatus.

The process of solvent extraction is generally employed either for the isolation of dissolved
substances from solutions or from solid mixtures or for the removal of undesired soluble
impurities from the mixtures. The principle of solvent extraction is based on the
distribution law. According to this law if a solute is soluble in both of two immiscible
liquids in contact with each other, the solute will distribute itself between the two liquids so
that the ratio of concentrations in them is a constant, expressed as Kd = Co/Cw where Kd is
distribution (or partition) coefficient, Co and Cw are concentrations of extractable species
in organic and water layers. Sometimes the equation D = Mo/Mw is also used where D =
distribution, Mo and Mw are molar concentrations of the species in organic and water
layers.

UTTARAKHAND OPEN UNIVERSITY Page 65

 LABORATORY COURSE-I BSCCH- 104

The efficiency of extraction is of interest in the extraction processes under a given set of
conditions. Thus the use of the percent of extraction (%E) is more meaningful than either
Kd or D which is expreseed as % E = 100D/D+ , where Vw and Vo are volumes of water
and organic phases.

Extraction Techniques

There are various methods employed for the extraction:

(1) Batch Extraction.

This is the most common type of extraction technique in which the organic liquid is added
to the solution to be extracted in a separating funnel. After agitation for sufficient length of
time, the layers are allowed to separate. Now the top is opened and the lower heavier layer
is drained out of the stop-cock. If more extractions are required and the lower layer is the
organic layer, a second portion of the organic liquid is added and process is repeated. If the
organic liquid is present in the upper layer, the aqueous layer is transferred to a second
separation funnel and a second portion of the organic liquid is added. The process is
repeated as many times as required to ensure satisfactory separation. The efficiency of
batch separation can be obtained as given earlier. This method has been modified for more
effective separation which involves multiple batch extractions called continuous extraction
method. This method employs separate equipments for extraction using organic liquids
lighter or heavier than water.
(2) Back extraction or stripping.
The extracted material, after it is extracted into organic layer, is usually returned to water
for the analytical procedure to be used in the determination. This is known as back
extraction or stripping. For the systems sensitive to pH, usually the practice is to agitate the
organic solution with an aqueous solution which has been adjusted to a pH value which is
below the pH range in which the material (generally metal) is extracted into the organic
phase. In some cases, the organic liquid having the solute is agitated with an aqueous
solution having a complexing agent which reacts with metals to form metal complexes that
are more soluble in water than in the organic liquid used in the extraction.

(3) Counter-Current extraction.

In a true counter-current extraction, the two immiscible liquids contact each other as they
flow through one another in opposite directions. Such extraction procedures have been
found to be very efficient because fresh extractant is brought into contact with the solute
depleted phase and the solute enriched extractant is brought into contact with fresh aqueous
solution. The amount of solute in either phase after any number of contact steps can be
calculated. Various devices have been proposed for carrying out the counter-current
extractions.

UTTARAKHAND OPEN UNIVERSITY Page 66

 LABORATORY COURSE-I BSCCH- 104

(4) Extraction of Solids.

Although the extraction or leaching of solids is not a true liquid-partitioning process, it is
an important example of an extraction phenomenon. In the simplest procedure, the solid is
covered with the liquid and after agitation for a suitable time period, the liquid and solid are
separated by decantation, centrifugation or filtration. Most continuous extraction
procedures for solids utilize the soxhlet extractor which allows the extraction in less time
and can work unobserved for a long time.
The solvent extraction method is widely used nowadays for the separations and
determination of metals. For example, ferric ion can be extracted from aqueous solution
with a 1% solution of 8-hydroxyquinoline in chloroform by double extraction. The optical
density of chloroform layer is determined by using a spectrophotometer. The process is
repeated with further portion of the reagent and optical density is measured again.
Similarly, it is also possible to determine uranium as 8-hydroxy quinolate in the presence of
some EDTA at pH 8.8. The EDTA masks the interfering ions such as Fe3+, Al3+, etc. Now
the optical density is determined as usual.
Likewise, by using suitable organic reagents, various metal ions can be estimated, e.g., (i)
D. of nickel as nickel dimethylglyoximate complex, (ii) D. of molybdenum as Mo-
thiocyanate complex, (iii) D. of lead by dithizone method, etc.

5.5 SUMMARY
Solvent extraction is a method to separate compounds based on their relative solubilities in
two different immiscible liquids, usually water and an organic solvent. It is an extraction of
a substance from one liquid into another liquid phase. Simple distillation is a procedure by
which two liquids with different boiling points can be separated. Simple distillation can be
used effectively to separate liquids that have at least fifty degrees difference in their boiling
points. Separation of a liquid mixture into fractions differing in boiling point by means of
distillation, typically using a fractionating column is called fractional . Distillation of a
liquid in a current of steam, used especially to purify liquids that are not very volatile and
are immiscible with water called steam distillation.

UTTARAKHAND OPEN UNIVERSITY Page 67

LABORATORY COURSE-I BSCCH- 104

UNIT 6: QUALITATIVE ANALYSIS

CONTENTS:
6.1 Objectives
6.2 Introduction
6.3 Detection of N, S, Halogens
6.4 Functional group identification with known samples
6.7 Summary

6.1 OBJECTIVES

In this chapter students learn the following objectives.

•To detect nitrogen, sulphur and halogen in given mixture.
•To identify functional groups with known samples.
6.2 INTRODUCTION

Qualitative analysis of an organic compound refers to the detection of the elements present
in a compound. The most common elements present in an organic compound are carbon,
hydrogen, oxygen, nitrogen, halogen and sulphur. Sometimes, elements such as phosphorus
and some metals may also be present. Therefore, qualitative analysis is limited to the
detection of only a small number of elements usually present in organic compounds.

6.3 DETECTION OF N, S AND HALOGENS

In organic compounds the most commonly occurring elements are nitrogen (N), sulphur (S)
and halogens along with carbon (C), hydrogen (H) and oxygen (O). In the identification of
an organic compound N, S and halogens are detected before the functional groups are to be
looked for. This is done by Lassaigne’s Test in which these elements are converted into
ionisable inorganic substances. This is because these elements along with the others are
covalently linked in the organic compounds and do not respond to ionic reactions. This
may be accomplished by fusing the substance with metallic sodium in an ignition tube.
Thus N, S and halogens are converted to sodium cyanide, suphide and halides respectively.
If N and S both are present in the same compound these are converted into NaCNS
(thiocyanate).
In the Lassaigne’s test, sodium extract is first prepared as follows: A sodium metal piece is
dried by pressing between the folds of a filter paper. It is then introduced into a clean
ignition tube and covered by pouring the given substance into the tube. The ignition tube is
first heated very gently in the flame holding it by means of a pair of tongs, taken it away
from the flame and heated again. This process is repeated three to four times till the bottom

UTTARAKHAND OPEN UNIVERSITY Page 68

 LABORATORY COURSE-I BSCCH- 104

of tube becomes red hot and reaction begins. The red hot ignition tube is plunged into a
beaker or porcelain dish containing about 10 to 15 ml. distilled water. The contents are
stirred and allowed the remaining sodium to react with water. The mixture is boiled for five
minutes and filtered. This filtrate is known as Lassaigne’s solution or sodium extract which
should be colourless and transparent. Otherwise the fusion is repeated with larger piece of
sodium and sodium extract is prepared as above. The conversion of the elements into ionic
form occurs as follows:

Na+C+ N→NaCN ⇌ Na+ + CN-

2Na + S → Na2S ⇌ 2Na+ + S2-

2Na + X2 → 2NaX ⇌ 2Na+ + 2X- (X =Cl, Br, I)

(1) Detection of Nitrogen.

About 2 ml. of sodium extract is treated with 3-4 drops of fresh and saturated solution of
FeSO4 followed by 2-3 drops of NaOH. The contents are boiled for two minutes. Then the
solution is cooled and 2 ml. of dil. H2SO4 are added to it to dissolve the precipitate of
ferrous hydroxide if formed and make the solution acidic. Then added 2-3 drops of FeCl3
solution. Formation of Prussian blue or greenish blue precipitate or colouration indicates
the presence of nitrogen. The reactions involved are given below:

Fe SO4 + 2NaOH → Fe (OH)2 ↓ + Na2SO4

Fe SO4 + 6NaCN → Na4 [Fe(CN)6] + 2NaOH

3Na4 [Fe(CN)6] + 4FeCl3 →Fe4 [Fe(CN)6]3(Prussian blue) +12NaCl

In the presence of N and S both in the compound, the above test gives blood red colour as
follows:
Na + C + N + S → Na CNS
3Na CNS + Fe Cl3 → Fe (CNS)3 (blood red) + 3NaCl
Ferric sulphocyanide
(2) Detection of Sulphur.
(1) 2ml. of freshly prepared sodium nitropursside solution (colourless) are added to
1ml. of sodium extract. A violet or purple colour is developed confirming the
presence of sulphur, Na2S + Na2 [Fe(CN)5 NO]→Na4 [Fe(CN)5 NOS] (violet
colour).
(2) Alternately, to 2ml. of sodium extract acidified with acetic acid is added 2ml. of
lead acetate solution, a black precipitate of PbS if formed, it also indicates the
presence of sulphur.

UTTARAKHAND OPEN UNIVERSITY Page 69

LABORATORY COURSE-I BSCCH- 104

Na2S + (CH3COO)2 Pb PbS(Black ppt.) + 2CH3COO Na

Acid

(3) Detection of Halogens.

The halogens (Cl, Br, I) present in an organic compound are detected in two ways:
(i) By silver nitrate test. - This is done as follows: 2ml. of sodium extract is boiled
with 1ml. conc. HNO3 and then AgNO3 is added to it:
(a)White curdy precipitate is formed; soluble in NH4OH-Cl is present.
(b)Pale (light) yellow precipitate appears; partially soluble in NH4OH-Br is present.
(c)Yellow precipitate is formed, insoluble in NH4OH-I is present.

Na Cl + Ag NO3 →Ag Cl ↓ (White ppt.) + NaNO3

Ag Cl + 2NH4OH → [Ag (NH3)2]Cl (soluble) + 2H2O

Na Br + Ag NO3 → Ag Br ↓ (light yellow ppt.) + NaNO3

Ag Br + 2NH4 OH → [Ag (NH3)2 Br] (partially soluble) + 2H2O

NaI + Ag NO3 → Ag I ↓ (Yellow ppt) + NaNO3

AgI + NH4 OH → insoluble

(ii) By chloroform test. - 2ml. of sodium extract are acidified with dil. HNO3, then
added 2-3 drops of chloroform or CCl4, followed by chlorine water shaking first gently
and then vigorously, if chloroform layer turns pale-brown-bromine is present but if it
turns purple or violet iodine is present.
2NaBr +Cl2 → 2NaCl + Br2
Br2 + CHCl3 → Pale- brown colour.
2 Nai + Cl2 → 2NaCl + I2
I2 + CHCl3 → purple or violet colour.

6.4 IDENTIFICATION OF FUNCTIONAL GROUPS

Organic compounds may be regarded as the derivatives of hydrocarbons having different
functional groups in place of one or more hydrogen atoms. Their characteristic properties
and reactions are largely due to the presence of functional groups present in them. Correct
detection of functional groups in the organic compounds leads to a very reasonable and
accurate identification of those compounds.

For the sake of convenience all the organic compounds are divided into four types
depending upon the presence or absence of N, S and halogens. After detecting the elements

UTTARAKHAND OPEN UNIVERSITY Page 70

LABORATORY COURSE-I BSCCH- 104

by Lassaigne’s test, it is advised to perform further tests as per the types I, II, III or IV
whichever be suitable according to the presence of the special elements in the compounds.

Type I : Compounds containing C and H with or without oxygen.

S.N. Experiment Observation Inference

1.(a) On treatment of the compound Brisk effervescence Acids
with NaHCO3 solution appears

(b) On treating of the compound Blue litmus turns red Acids

with blue litmus,
2. On adding ceric ammonium Red colouration is Alcohols
nitrate solution to the compound, observed
3.(a) Two drops of FeCl3 are added to Typical colour Phenols
an aqueous of alcoholic solution changes are observed
of the compound,
Phthalein test is performed, Positive result is
(b) observed Phenols
4. The compound is heated with Red priapitate is Aldehydes or
Fehling’s solution or Benedict’s formed reducing
solution, sugars
5. The compound is treated with Pink colouration is Aldehydes
Schiff’s solution. observed.
6. On Shaking the compound with White precipitate is Aldehydes or
sodium bisulphite solution, formed. Ketones
7. The compound is treated with Red colouration Methyl
alkaline sodium nitroprusside appears Ketones
solution,

8. Molisch’s test is performed, Result is positive Sugars

9. On heating the compound with Pink colour is slowly Esters

dil. NaOH solution containing a discharged
drop of phenolphthalein
10. On heating the compound with (i) Soluble Aromatic or
fuming H2SO4, unsaturated
hydrocarbons
(ii) Insoluble Saturated
aliphatic
hydrocarbons
or ethers

UTTARAKHAND OPEN UNIVERSITY Page 71

LABORATORY COURSE-I BSCCH- 104

Type II: Compounds containing C, H and halogens with or without oxygen.

S.N. Experiment Observation Inference

1. On boiling the (i) White ppt. soluble in Chloro compounds
compound with NH4OH
alcoholic AgNO3,
(ii) Ligth yellow ppt. Bromo compounds
Partially soluble in
NH4OH

(iii) Deep yellow ppt. Iodo compounds

insoluble in NH4OH
2. If the compound is (i) Soluble Aromatic or
heated with fuming unsaturated alkyl
H2SO4, halides

(ii) Insoluble Saturated aliphatic

alkyl halides

Type III. : Compounds containing C, H and N with or without oxygen.

S.N. Experiment Observation Inference

1. The compound is boiled Smell of ammonia is Amides

with aq. NaOH, noticed

2. The compound is treated (i) Brisk effervescence Amides, amino

with dil. HCl followed occurs acids, primary
by NaNO2 drowse in amines or urea
cold, (ii) Brown or green ppt. is
formed

(iii) Blue colouration

appears

3. On treating the above Bright orange-red dye in Aromatic primary

contents with alkaline β formed amines
- naphthol solution ,

UTTARAKHAND OPEN UNIVERSITY Page 72

LABORATORY COURSE-I BSCCH- 104

4. The compound is boiled Yellow colouration Nitro phenols or

with water, nitro compounds

5. The compound is boiled Grey precipitate is formed Nitro compounds

with zinc dust and aq.
NH4Cl, filtered and
filtrate is treated with
Tollen’s regent,

Type IV (A) : Compounds containing C, H and S with or without oxygen.

S.N. Experiment Observation Inference

1. To the aq. solution of the Violet or red colour is Sulphonic acids of

substance is added few observed phenols or hydrdro
drops of FeCl3 solution, carbons

2. Equal quantities of Disagreeable garlic like Sulphones

substance and animal odour is noticed
charcoal are mixed and
filled one third of the
ignition tube with it and
heated,

(B): Compounds containing C, H, S and N with or without oxygen.

S.N. Experiment Observation Inference

1. 2ml. of NaOH solution Brown or black colour or Thioureas

are added to a trace of precipitate appears
the substance in a test
tube, heated to boiling,
cooled and added 2 drops
of aq. lead acetate,

2. A trace of the substance (i) If colour changes to Test (a) given below
is dissolved in 2ml. of red. is performed
water by boiling in a test
tube and a piece of blue (ii) If no change in Test (b) is performed
litmus paper is colour as given below

UTTARAKHAND OPEN UNIVERSITY Page 73

LABORATORY COURSE-I BSCCH- 104

introduced in it,

(a) A trace of the substance Red colouration appears Amino sulphonic

is dissolved in 3ml. of acids
dil. HCl, cooled in ice
cold water and added
3ml. of 2% sodium
nitrite solution and then
4ml. of alkaline β
naphthol solution

(b) 5 drops of conc. H2SO4 Colour changes to blue Sulphonamide or

are added to a trace of and smell of NH3 is saccharin
substance and heated noticed
gently for few minutes,
cooled and diluted with
2ml. water. Then added
flakes of NaOH and a
piece of moistened red
litmus paper is brought
near the mouth of the test
tube,

Confirmation of Functional Groups.

The functional groups are then confirmed by normal and sometimes by performing some
special test.
1.Carboxylic acid group (-COOH).
(i) Litmus paper test. If the blue litmus paper or solution is added to the aq. solution or
suspension of the compound, it turns red.
(ii) Sodium bicarbonate test. If a small amount of the compound is added to about
3ml. of saturated sodium bicarbonate solution, brisk effervescence is noticed.
(iii) Fluorescence test. 0.2gm. of organic compound is heated gently with 0.5gm. of
resorcinol and few drops of conc. H2SO4 in a hard test tube for two minutes, cooled
and poured the contents into a beaker containing NaOH diluted largly with water.
Intense green fluorescence is formed indicating the presence of 1,2 or ortho
dicarboxylic group (i.e. phthalic acid)
(iv) Ester formation. A small quantity of the substance is heated with ethyl alcohol
and a little conc. H2SO4, cooled and poured in a tube containing water. A fruity
smell due to the formation of an ester indicates the presence of carboxylic group.

UTTARAKHAND OPEN UNIVERSITY Page 74

LABORATORY COURSE-I BSCCH- 104

(v) Ferric chloride test. 0.5gm. of the acid is neutralised with excess of ammonia in a
boiling test tube, the solution is boiled to remove excess of ammonia, cooled and
added few drops of neutral FeCl3 solution:
If reddish brown precipitate is formed: aliphatic carboxylic acids; Buff ppt. is formed:
Aromatic acids and certain dibasic acids; If violet colour appears: Aromatic hydroxy acids

Note. Phenols and α-naphthylamine also produce colour with FeCl3.

2. Alcoholic –OH group.

(i) Ceric ammonium nitrate test. 2drops of the organic substance are treated with
0.5ml. of ceric ammonium nitrate solution, then diluted with 2ml. water. A red
colouration is observed.

(ii) Sodium test. About 2ml. of the compound are taken in a test tube, added to it a
piece of anhyd. CaCl2 to absorb any water if present. The clear liquid is transferred
to another dry test tube and added to it a dry piece of sodium. The effervescence
appears due to liberation of hydrogen.

Distinction among primary, secondary and tertiary alcohols.

If 2ml. of the compound is treated with about 5ml. of Lucas reagent (8 gm of anhyd, Zn Cl2
in 5ml. conc. HCl) and shaken, an insoluble layer at once is formed by a tertiary alcohol,
cloudiness within 4-5 minutes appears in case of a secondary alcohol and the solution
remains clear for a primary alcohol.

2. Phenolic –OH group.

(i)Ferric chloride test. On adding 2-3 drops of ferric chloride to 2ml. of aqueous or
alcoholic solution of the compound, a green, blue or violet colour shows the
presence of phenolic –OH group but nitro phenols do not show this test.
Exceptions. α-naphthylamine and benzoic acid also respond to this test as follows:

α - naphthylamine -blue colour

Benzoic acid-buff coloured ppt.

(ii) Liebermann’s test. A little amount of the compound is fused with a crystal of
sodium nitrite in a tube, the mixture is cooled and to it added 1ml. conc. H2SO4, a
deep green to blue solution is formed which turns red when poured in large excess
of water. The red aqueous solution again becomes deep green or blue if made
alkaline with NaOH.
(iii) Azo-dye formation. 2drops of aniline are treated with 0.5ml. conc. HCl in a test
tube, diluted with water and cooled in a freezing bath, then added dil. NaNO2
solution while shaking. This diazotized solution is poured to that of phenol in

UTTARAKHAND OPEN UNIVERSITY Page 75

 LABORATORY COURSE-I BSCCH- 104

excess of 2N-NaOH solution. Formation of a dye or orange or red colour indicates

the phenolic group.
(iv) Phthalein test. 0.5gm. of compound is heated with 1gm. phthalic anhydride and
2drops of conc. H2SO4 for 1minute, cooled and made alkaline with dil. NaOH
solution. If few drops of this alkaline liquid are poured in 20ml. water,
characteristic colour appears due to phenolic group:
Phenol, O-Cresol-red colour
Catechol, m-Cresol-blue colour
Resorcinol-fluorescent green
p-Cresol-no colouration
Hydroquinone-deep blue
α – Naphthol-green
β – Naphthol-light green
3. Aldehyde group (-CHO)
(i) Test with Schiff’s reagent. 5-6 drops of liquid or (0.1gm) of compound are added to
2ml. of the reagent, contents are shaken vigorously, a deep red or violet colour after
waiting for 2-3 minutes. (no heating)
(ii) Test with Tollen’s regent. 0.1gm. of solid or 0.1ml. of liquid compound is added to
2ml. of Tollen’s reagent, warmed and allowed to stand for 2-3 minutes when a
silver mirror or a grey precipitate is formed.
(iii) Test with Fehling’s solution. 0.1gm. of soid or 0.2ml. of liquid compound is
added to 5ml. of fehling’s solution and the mixture is boiled when red precipitate is
formed.
(iv) Test with Benedict’s solution. 0.1gm. of the compound is boiled with 2-3ml. of
Benedict’s solution for few minutes while a red yellow precipitate appears.
The compounds can be quickly guessed by the following points:
(a)Smell of bitter almonds – benzaldehyde
(b)If bad pungent odour is there, NaOH is added to the liquid compound and shaken
(i)Brown resin formed – acetaldehyde
(ii)No such change – formaldehyde
4. Ketone group (>C = O).
(i) 2,4- Dinitrophenyl hydrazine test. 2drops of the substance are added to about 2ml.
of the reagent solution, shaken vigorously and heated if necessary, when a yellow or
orange red precipitate separates out.
(ii) Sodium bisulphite test. 0.2gm. or 0.3ml of the compound is added to 1ml. of
saturated sodium bisulphite solution and shaken vigorously, a white precipitate is
formed.
(iii) Sodium nitroprusside test. 0.1gm. of solid or 0.2ml. of liquid compound is added
to 2ml. of aq. sodium nitroprusside solution and contents are made alkaline with 2-3
drops of sodium hydroxide, a red or purple colour appears (benzophenone does not
respond to this test).
UTTARAKHAND OPEN UNIVERSITY Page 76
 LABORATORY COURSE-I BSCCH- 104

Note:The first two tests, i.e. with 2,4 dinitrophenyl hydrazine and sodium bisulphite, are
also given by aldehydes but the difference is that ketones do not respond to the tests with
Tollen’s reagent, Fehling’s solution, Schiff’s solution, etc.

5. Ester group (RCOOR’).

All the esters possess fruity smell.
(i) Phenolphthalein test. To 3ml. of the compound are added 2-3 drops of very dilute
NaOH solution followed by a drop of phenolphthalein and heated gently, the pink colour
is gradually discharged (due to hydrolysis of ester).
6. Carbohydrate.
(i)Molisch’s test. To 1ml. aqueous suspension of compound are added 2drops of 10%
alcoholic solution of α – naphthol and shaken well. Now added carefully 2ml. of conc.
H2SO4 along the side of the test tube, a reddish-violet ring is formed at the junction of two
layers in case of carbohydrate.
In the Molisch’s test 8ml. conc. HCl is added in place of conc. H2SO4 and the solution is
boiled, a violet colour is produced immediately for sucrose or fructose but glucose gives
this colour after 1-2 minutes of continuous boiling.
(ii)Sulphuric acid test. A small amount of the powdered compound is treated with 1ml.
cold conc. H2SO4, colour varying from yellow, brown and black appears.
(iii)Test with Tollen’s reagent. 0.1gm. of the compound is added to 2ml. of Tollen’s
reagent and heated gently, a silver mirror is obtained inside the wall of the vessel.
(iv)Test with Fehling’s solution or Benedict’s solution. 1ml. of the aq. solution of the
compound is boiled with 2ml. of Fehling’s solution or Benedict’s solution for two minutes,
red precipitate is formed in case of reducing sugars. If the mixture with Benedict’s solution
remains blue or only slight turbidity appears then sucrose is present.
7. Hydrocarbon and Ether.
If the compound does not respond to any above test, it may be suspected to be either a
hydrocarbon or ether. Ethers are soluble in phosphoric acid while hydrocarbons are
rendered insoluble. All ethers are sweet smelling. Liquid benzene and toluene have
characteristic sweet petrol like odour.
i. Feigl’s test for ethers. 1-2ml. of ether are taken in a boiling tube and its mouth is covered
with a filter paper moistened with a mixture of cupric acetate and benzidine
hydrochloride solution. On heating to boiling, a deep blue colour appears on filter paper
due to the formation of benzidine blue due to the ether group.
ii. To 0.5 ml. of the compound is added 1ml. of iodine solution in CS2 and shaken well the
purple colour of CS2 layer changes due to ether group.
iii. 1ml. of compound is mixed with 4ml. of glacial acetic acid and 1ml. conc. H2SO4, heated
under reflux condenser for about 5 minutes, cooled well and extracted with benzene
purple colour appears due to ether group (This test can be applied only when ester group
is absent, otherwise not). If the above tests are negative, then the compound is a
hydrocarbon.

UTTARAKHAND OPEN UNIVERSITY Page 77

 LABORATORY COURSE-I BSCCH- 104

8. Halogen containing compound.

(i) Alcoholic silver nitrate test. A little amount of the compound is heated with 2ml. of
alcoholic silver nitrate solution for a few minutes and the observed the following:
(a)Formation of a precipitate indicates the presence of aliphatic or reactive halogen.
(b)No precipitate indicates the presence of halogen atom attached to benzene nucleus
(but 1-chloro-2, 4-dinitro benzene does not respond to this test).

Quick guess.

(a)If the Cl-containing compound is solid, aliphatic and crystalline containing –CHO group, it
is chloral-hydrate.
(b)Cl-containing compound is aromatic solid, colourless and crystalline with characteristic
smell, it is p-dichlorobenzene.
9.Amide group (-CONH2)
(i) Sodium hydroxide test. 0.2gm. of the compound is heated with 4ml. of aq. NaOH,
ammonia gas is evolved due to amide group.
(ii) Nitrous acid group. To 0.2gm. of substance is added 2ml. dil. HCl followed by 2ml.
of 2% aq. NaNO2 and shaken, brisk effervescence due to the evolution of nitrogen indicates
amide group.
(iii) Hydroxylamine hydrochloride test. In a test tube 0.2gm of the compound, 0.2gm of
hydroxylamine hydrochloride and 2ml. ethyl alcohol are taken, boiled for five minutes,
cooled and added few drops of FeCl3. Blue-red colour appears indicating an aliphatic
amide.
(iv) To the aq. solution of the compound are added 7-8 drops of 6% H2O2 and heated
nearly to boiling, cooled and added 1-2 drops of 5% FeCl3 solution, Bluish red colour
appears in cold within 2mintues or a brown colour on warming shows the presence of an
aromatic amide.

(Quick test: Compound is dissolved in water by heating cooled and added 1ml. conc.
HNO3

(a)Crystalline ppt formed -urea

(b)No ppt. and aliphatic-acetamide
(c)No ppt. and aromatic -benzamide)
10.Amine groups (-NH2, > NH and≡ N).
(a)Primary amine.
(i)Nitrous acid test. 0.2gm. of the compound is dissolved in 10ml. dil. HCl and cooled.
Now added 10% aq. NaNO2 solution, brisk effervescence appears-aliphatic primary amine.
(ii)Carbylamine test. A mixture of 2 drops of the compound, 2drops of chloroform and
2ml. of alcoholic caustic potash (KOH) is boiled. An intolerable offensive odour of
carbylamine indicates a primary amine.

UTTARAKHAND OPEN UNIVERSITY Page 78

LABORATORY COURSE-I BSCCH- 104

(iii)Diazotisation test. About 0.2gm. of the compound is dissolved in dil. HCl, cooled and
added to it 10% aq. NaNO2 This is poured into a beaker containing 10% alkaline β –
naphthol, a bright orange-red dye appears-aromatic primary amine
(iv)Rimini test. To about 0.3gm. of the compound taken in a test tube are added 5ml. water,
1ml. acetone and a few drops of sodium nitroprusside, allowed to stand for 2minutes: a
violet red colour appears for aliphatic primary amines.
(b)Secondary amine.
(i)Nitrous acid test. Ice cold dil. HCl is added to a solution of 1% aq. NaNO2. This solution
is added gradually to the solution of compound in HCl (0.5gm. in l0ml. HCl). An oily dark
coloured liquid or low melting solid is formed due to aliphatic or aromatic secondary
amine.
(ii)Libermann’s nitroso test. In the above test, if 1ml. conc. H2SO4 is added cautiously to
the reaction mixture, a blue colouration which changes to red on dilution with water and
blue or green with aq. alkali confirms the secondary amine.
(c)Tertiary amine.
(i)Nitrous acid test. Ice cold dil. HCl is added to 1% aq. NaNO2. To this solution is added
gradually 0.2gm. of the compound in 10ml. dil. HCl:
(a)If there is no reaction-tertiary aliphatic amine.
(b)If green or brown coloured salt is produced-aromatic tertiary amine.
11.Nitro group (-NO2).
Almost all nitro compounds are light yellow or yellow in colour.
(i)Sodium hydroxide test. A small amount of the compound is shaken with 2ml. of NaOH
solution, yellow, intense yellow or orange colour is produced due to nitro group.
(ii)Zinc-ammonium chloride test. A small amount of the substance is boiled with 5ml. of
5% alcohol, 0.2gm. each of NH4Cl and zinc dust, cooled, filtered and added to the filtrate 2
ml. of Tollen’s reagent. On heating, a black grey precipitate is formed due to nitro
compounds.
(iii)Azo-dye test. 0.1gm. of the substance is heated with 0.5ml. conc. HCl and 2-3 small
pieces of metallic tin for 3-4 minutes, filtered, cooled and added 3ml. of aq. NaNO2
solution. This is poured into a beaker containing alkaline β naphthol solution. An orange
red dye is formed.
12.Sulphonic acid group (-SO3H).
The compound having sulphonic acid group gives positive test for S element.
(i)Sodium bicarbonate test. A little amount of the compound is added to a few ml. of aq.
NaHCO3 and the contents are stirred. Brisk effervescence of CO2 and positive test of
element S confirms the sulphonic acid group.
(ii)Fusion test. Equal amounts of the compound and solid NaOH/KOH are fused and
treated with dilute mineral acid. A penetrating smell of SO2 is noticed. The gas if passed
into acidic K2Cr2O7 solution, green colour is developed.

UTTARAKHAND OPEN UNIVERSITY Page 79

LABORATORY COURSE-I BSCCH- 104

6.7 SUMMARY
Detection of nitrogen (N), sulphur (S), and halogens (X) is done by Lassaigne’s Test in
which these elements are converted into ionisable inorganic substances. This can be done
by fusing the substance with metallic sodium in an ignition tube. On fusion with sodium N,
S, and halogens are converted to sodium cyanide, sulphide and halides respectively. If N
and S both are present in the same compound these are converted into NaCNS
(thiocyanate). Functional groups are specific atoms, ions, or groups of atoms having
consistent properties. For the sake of convenience all the organic compounds are divided
into four types depending upon the presence or absence of N, S and halogens. After
detecting the elements by Lassaigne’s test, it is advised to perform further tests as per the
types I, II, III or IV whichever be suitable according to the presence of the special elements
in the compounds. The functional groups are then confirmed by normal and sometimes by
performing some special test.

UTTARAKHAND OPEN UNIVERSITY Page 80

LABORATORY COURSE-I BSCCH- 104

UNIT 7: INTRODUCTION LAB TECHNIQUES:

PHYSICAL CHEMISTRY
CONTENTS:
7.1 Objectives
7.2 Introduction
7.3 Use of Apparatus: Pipette, Burette, Volumetric flask, Balance, Use of Burner-
7.4 Types of Flames (Luminous flame, Non luminous flame)
7.5 Introduction to Instruments
7.5.1 Colorimeter
7.5.2 Conductometer
7.6 Solubility and Standard solutions
7.7 Data Analysis and Error Calculation
7.8 Graph Plotting
7.9 Safety measures and First Aid
1.10. Summary
7.1 OBJECTIVES
In this chapter students learn the following objectives.
•Students will learn how to carry out independent experimental work in a laboratory
setting while investigating a research problem, utilize appropriate instrumentation and
techniques.
•Become familiar with different volumetric measurements and use laboratory apparatus
correctly.
•Interpret experimental results and draw reasonable conclusions and write them properly.
•Apply safety rules in the practice of laboratory investigations.

7.2 INTRODUCTION
Behavior of matter: Chemistry is concerned with the composition, structure and
properties of matter. Anything which occupies space and has mass is known as matter.
Matter can exists in three states solid, liquid and gas.

Solutions: Solvent, solute and solution

Solvent: The liquid which allows the solute to dissolve in it to form a solution is called
solvent.

Solute: The substance which dissolves in a solvent is called a solute.

UTTARAKHAND OPEN UNIVERSITY Page 81

 LABORATORY COURSE-I BSCCH- 104

Solution: A homogenous mixture of a solute in solvent is called solution.

If the amount of solute is relatively small compared to the amount of solvent is called a
dilute solution.

A solution in which the amount of solute is relatively large compared to the amount of
solvent is considered concentrated solution.

7.3 USE OF APPARATUS: PIPETTE, BURETTE,

VOLUMETRIC FLASK, BALANCE, USE OF BURNER
In chemistry experiments the glassware used is pipette, burette, test tube, boiling tube,
beaker, measuring flask, conical flask, graduated cylinder, funnel steam bath etc. For
measuring fixed amount of a liquid either pipette or burette (sometimes graduated
cylinders) are used. For titration purposes conical flask is used it may be 100 ml or 250 ml
balance is used for weighing purposes. Now a day’s electrical balance is used.

Bunsen burner:
Bunsen burner is shown in fig 7.1. To get steady blue flame proceed as follows

Fig 7.1 Bunsen burner

(i)Find the round knob controlling the needle valve which is at the base of the burner. Turn it
clockwise to stop the flow of gas completely. If your burner does not have a needle valve
the gas flow has to be regulated at the bench stopcock (fig 7.1).
(ii)There is a movable collar at the base of the burner which controls air flow. Now see that all
the holes are closed (i.e. no air gets in).
(iii)Connect the burner to the bench stopcock by some tubing and turn the bench valve fallen.
The bench valve handle should be parallel to the outlet (fig 7.1).
(iv)Now, slowly open the needle valve. You may be just able to hear some gas escaping. Light
the burner. Mind your face. Don’t look down at the burner as you open the valve.

UTTARAKHAND OPEN UNIVERSITY Page 82

 LABORATORY COURSE-I BSCCH- 104

(v)You will get a wavy yellow flame, something you don’t really want. But at least it will light.
Now open the air collar a little, the yellow disappears a blue flame forms. This is what you
want.
(vi)Now adjust the needle valve and collar for a steady blue flame.

7.4.TYPES OF FLAMES
7.4.1 Oxidising and reducing flame
Oxidizing flame is produced by placing nozzle of the blowpipe about one third within the
flame and blowing vigorously in a manner so as to cause the extreme tip of the flame to act
on the substance under examination.

Fig 7.2 oxidizing and reducing flame

Reducing flame is produced by blowing gently the flame with a mouth blowpipe, the
nozzle of which of which kept just outside the flame in a manner so that the inner cone of
the flame acts upon the substance under examination.

7.4.2 Luminous and Non luminous flames

A luminous flame is burning flame which is brightly visible. Much of its output is in the
form of visible light, as well as heat or light in the non-visible wavelengths. A luminous
flame is a bright, light emitting, usually yellow flame. For example, if you light a match
and watch it burn, this is luminous flame. One of the most familiar instances of a luminous
flame is produced by a Bunsen burner. This burner has a controllable air supply and a
constant gas jet: when the air supply is reduced, a highly luminous, and thus visible, orange
‘safety flame’ is produced. For heating work, the air inlet is open and the burner produces a
much hotter blue flame.

A non-luminous flame is a flame in which the fuel is undergoing complete, or near

complete combustion. A non-luminous flame (as the name implies) is much darker than a
luminous flame and does not emit as much light. The colour is generally blue and the flame

UTTARAKHAND OPEN UNIVERSITY Page 83

LABORATORY COURSE-I BSCCH- 104

temperature is much higher than a non-luminous flame. One can easily adjust a Bunsen
burner or propane torch to make a non-luminous flame.

7.5 INTRODUCTION TO INSTRUMENTS

7.5.1Calorimeter
For the measurement of heat of various reactions, a thermos flask or a calorimeter is used.
A calorimeter suitable for general experiments with solutions may be constructed by
loosely packing the space between two large boiling tubes or two beakers with cotton wool.
The modern vacuum flask has the merit of very good insulation, but the narrowed neck of
the ordinary of thermos type prevents the use of an efficient stirrer, and if mixing

Fig 7.3 calorimeter

is done by shaking, the water equivalent has absurd values. An unsilvered, straight sided
Dewar flask (fig 7.3). Avoids this serious disadvantages without serious loss of heat
insulation.

7.5.2Conductivity bridge
An electric current flowing through an electrolyte is governed by Ohm’s law. According to
Ohm’s law the current strength (I) is directly proportional to the difference of potential (E)
between the two ends of the conductor through which the current is flowing, thus
mathematically.

I E

or I= KE or IR=E

UTTARAKHAND OPEN UNIVERSITY Page 84

LABORATORY COURSE-I BSCCH- 104

where R and K are constants. The ratio E/I is the resistance of the circuit to the passage of
electric current and so the constant R is known as resistance. The K is known as
conductance.

The conductance of a substance i.e., its power of conducting an electric current, is thus
reciprocal of resistance.

Measurement of conductivity of a solution

The resistance of a conductor is measured by means of Wheatstone bridge. When a direct
current is passed through solution, the following difficulties arise.

1. The electrodes are polarized i.e., the products of the electrolysis accumulate on them.

2. The passage of current involves the decomposition of a portion of the solute, so the
concentration of this substance changes during the passage of electric current.

Fig 7.4 Conductivity Bridge (Wheatstone bridge)

To remove these difficulties we use alternating current in place of direct current. It is

obtained in the laboratory from the secondary coil of small induction coil. In this case
galvanometer is replaced by a head phone the arrangement is shown in fig 7.4

7.6 SOLUBILITY
Different solution dissolve to different extent in the same mass of solvent, i.e., they have
different solubilities. Solubilities is thus the ability of a salute to dissolve in a particular
solvent. To obtain a uniform result, the amount of solvent is fixed, it is 100 gm and the
solution should be saturated at a particular temperature.

UTTARAKHAND OPEN UNIVERSITY Page 85

LABORATORY COURSE-I BSCCH- 104

Hence solubility of a solute at t0C

x100 = x100

Thus if we say solubility of cane sugar is x at t0C, means x gm of solute are dissolved
in 100 g of solvent at t0C.
Standard solution:
The solution of accurately known concentration is known as standard solution. It contains
accurately known amount of substance in unit volume of solution. It may be in terms of
molarity, molality, normality, mole fraction or percentage compostion.

Preparation of standard solution

Standard solution may be prepared by any of the following two methods.

(1)By direct weighing.

(2)By titration.

(1)By direct weighing:

The standard solution of certain substances can be prepared, provided they are available in
pure state, by weighing a definite amount of the substance, dissolving in a suitable solvent,
usually water and making up the solution to known volume.
The amount of substance to be weighed is calculated keeping in view the ultimate volume
of desired normality of the solution. Such substance whose standard solution can be
prepared by direct weighing are called primary standard substances. In practice, it is often
more convenient to prepare a little more concentration solution than it is actually required.
This is then diluted with distilled water until the solution of desired normality is obtained.
The extent to which the solution is to be diluted is calculated from the normality equation.
N1V1 = N2V2
Where N1= Original normality
V1= Original volume taken
N2= Required normality
V2= Volume after dilution
Then V2= N1V1/N2 and the volume of water to be added to the volume V1=(V2-V1) ml.
standard solution of oxalic acid can be prepared by this method.
2. By titration:
This is an indirect method employed for the preparation of standard solution of those
substances which are not available in a state of purity, sodium hydroxide, mineral acids and
many other substances. In such case a little more concentrated solution then is ultimately
required, is first prepared. This solution is then standardised by titration against a solution
of pure substance and of known concentration. Thus the normality of the solution to be

UTTARAKHAND OPEN UNIVERSITY Page 86

LABORATORY COURSE-I BSCCH- 104

prepared is known, from which solution of desired normality is prepared by dilution with
distilled water.
Primary standards:
There are certain substances whose standard solution can be prepared by directly weighing
the known amount of substance available in a state of purity, in a suitable solvent usually
water and making up the solution to a definite volume. Such substances are called primary
standards. Therefore, a primary standard is a solid substance which is used for the direct
standardsation of a given solution. The volume of the given solution required to react with
the dissolved standard gives a measure of normality of the solution. Only a few substances
are available as primary standards because a primary standard is required to fulfill certain
requirements.
Requirement of primary standard:
A primary standard must fulfill the following conditions:

(i) It should be easily available in a state of purity.

(ii) It must be easy to obtain, to purify, to dry and to preserve it in pure state.
(iii) It must be of definite known composition and capable of reacting quantitatively and
in a known way with a solution to be standardized.
(iv) Its composition should remain unchanged during storage and in air during weighing
i.e., it should not be hygroscopic or efflorescent nor oxidized by air affected by
carbon- dioxide.
(v) It should have high equivalent weight, to minimize weighing errors.

For example if you have to prepare N/10 oxalic acid solution in 250 ml you weigh 1.5750
gm and transfer the weighed oxalic acid into a 250 ml measuring flask, dissolve it in water
and make the volume 250 ml. Its normality will be N/10. It is primary standard.
In contrast suppose you have to prepare N/5 sodium hydroxide solution in 250 ml. if you
weigh 2 gm and dissolve it in 250 ml, the normality will be not be N/5 it will be much less
than that, because if you are weighing 2 gm and dissolving it in 250 ml flask, by the time
you pour the weighed amount into measuring flask it hydrolyses and the dissolved amount
becomes much less than 2 gm.
If you have to prepare exactly N/5 NaOH solution in 250 ml, weigh excess of sodium
hydroxide say approximately 3 gm and dissolve in 250 ml. To know its exact strength
titrate it against standard oxalic acid solution.
At this stage you will get the exact strength of NaOH solution (from N1V1 (oxalic acid)=
N2V2 (NaOH).

Suppose you get the strength of NaOH solution equal to N/3. Now for preparing N/5 NaOH
solution in 250 ml the following formula is used

N1V1 = N2V2

UTTARAKHAND OPEN UNIVERSITY Page 87

LABORATORY COURSE-I BSCCH- 104

N/5.x250 = N/3. x1

X1= 250x3/5 = 150 ml

That means 150 ml of N/3 sodium hydroxide is poured into 250 ml measuring flask and
make up to the volume to 250 ml by adding 100 ml of water. This solution is now standard
solution of sodium hydroxide of strength N/5.

Density:

The density or specific gravity of a liquid is defined as its mass per unit volume. We use
the term density at a given temperature; it means the relative density at that temperature
with respect to density of water. It is measured with the help of density bottle (fig 7.5).

Fig 7.5 Density bottle

Equivalent weight:

Equivalent weight of a substance is most commonly defined as the number of parts by

weight of which combines or displaces 1.0078 parts by weight of hydrogen or 8 parts by
weight of oxygen.

This definition of equivalent weight though very simple and covers most of the reactions,
but is very difficult to give such a definition of equivalent weight which covers all the
reactions. Equivalent weight varies with the type of reaction. Therefore, a compound may
possess different equivalent weights in different chemical reactions and under different
experimental conditions.

The gram equivalent weight of a substance is the equivalent weight expressed in grams.

From the above discussion it is clear that the equivalent weight of a compound can be
decided only after considering the reaction which it undergoes.

Equivalent weight of an acid is that weight of an acid which contains one replaceable
hydrogen i.e., 1.0078 gm of hydrogen.

UTTARAKHAND OPEN UNIVERSITY Page 88

LABORATORY COURSE-I BSCCH- 104

Eq wt. of an acid

Thus oxalic acid (COOH)22H2O is dibasic acid its equivalent weight will be

= Mol. Wt. of oxalic acid/basicity of oxalic acid

= 166/2

= 63

7.7DATA ANALYSIS AND ERROR CALCULATON

If you have performed the experiment and obtained the results calculate the error. Compare
it with the exact one. Suppose in a particular experiment the surface tension of the supplied
liquid say benzene is obtained 27.90 dynes/cm at 200C. from standard table you know the
value of surface tension at 200C for benzene is 28.88 dynes/cm. in this case the percentage
error will be x100. =3.40 %

Types of errors:

Two main types of errors can affect the accuracy of a measured quantity, these are

(a)Determinate and
(b)Indeterminate errors

Determinate errors – determinate errors are those that are determinable and can be either
avoided or corrected. They may be constant, as in the case of uncelebrated weight that is
used in all weighings or may be variable but of such a nature that they can be accounted for
any correction. The determinate errors can be generally classified as

(i) Instrumental errors

(ii) Operative errors
(iii) Errors of the method

(i) Instrumental errors:

These errors are common to all instruments as each one has a limited accuracy. The
manufacturer of the instrument generally provides the table quoting the reliability of the
results in the respective ranges. It should be kept in mind that the calibration of the
instrument in one range may not be valid of the entire range. In the case of volumetric
analysis, the glass apparatus like burette, pipette and measuring flask are calibrated. If the

UTTARAKHAND OPEN UNIVERSITY Page 89

LABORATORY COURSE-I BSCCH- 104

working temperature is different, the volume measured may be incorrect. The chemist has
to consider all these errors which may be introduced during experiments.

(ii) Operative errors:

These include personal errors and can be reduced by experience and in case of the analyst
in the physical manipulations involved operations in which these errors may occur include
transfer of solutions, effervescence and bumping during sample dissolution, incomplete
drying of samples etc. These are difficult to correct for personal errors which may also be
introduced due to physical disability, like colour blindness which may make in correct
judgment of colour. Other personal errors include mathematical errors in calculations.

(iii) Errors of methods:

These are most serious errors of an analyst. Most of the errors discussed above can be
minimized or corrected for, but the errors that are inherent in the method can not be
changed unless the conditions of the determination are changed

(b) Indeterminate errors:

The second type of errors includes the determinate errors, generally accidental or random
errors. They are revealed by small difference in successive measurements made by the
same analyst under virtually identical conditions. These errors cannot be predicted or
determined. These accidental errors will follow a random distribution, thus mathematical
law of probability can be applied to arrive at some conclusion regarding the most probable
results of a series of some conclusion regarding the most probable results of a series of
measurements. To give a simple example, an analyst reads incorrectly, the instrument panel
reading in pH meter or spectrophotometer. He notes down this reading which is used in
calculations based on this reading. The error is random and each observation is isolated and
unique.

7.8 GRAPH PLOTTING

While plotting a graph, scale should be chosen so that entire picture is easily obtained from
the graph sheet. Both the axes should be clearly indicated which is which. The scale on
both the axes should be mentioned in the graph sheet. If you have been asked to determine
some property by means of graph, then plot that property along x-axis as shown in fig 7.6.
suppose you have to determine the composition of the given mixture of two liquids A and
B by viscosity measurements than plot the time of flow along y- axis and concentration of
A or B along x-axis as shown in fig 7.6. A perpendicular is drawn from that point on the x-
axis, from which the composition of unknown solution can be read directly.

UTTARAKHAND OPEN UNIVERSITY Page 90

LABORATORY COURSE-I BSCCH- 104

Fig 7.6 Graph plotting

7.9 SAFETY PRACTICES

General: Never work in the laboratory alone. Avoid unnecessary flames. Check the area
near you for volatile substances before lighting a burner.
Chemicals:
Handle every chemical with care. Avoid contact with skin and clothing. Wipe up spills
immediately, especially near the balances and reagent shelf. Replace caps on bottles as
soon as possible. Do not use an organic solvent to wash a chemical from the skin as this
may actually increase the rate of absorption of the chemical through the skin. Avoid the
inhalation of organic vapours, particularly aromatic solvents and chlorinated solvents. Take
care in smelling chemicals and do not taste them unless instructed to do so.
Disposal of chemicals:
Small quantities of non hazardous water soluble substances can be flushed down and drain
with the large quantity of water. Hazardous waste, non hazardous solid waste, organic
solvents and halogenated organic waste should be placed in the four containers provided.
Fire:
Burning clothing: Prevent the person from running and fanning the flames. Rolling the
person on the floor will help extinguing the flames and prevent inhalation of the flames. If
a safety shower is nearby hold the person under the shower until the flames are
extinguished and chemical washed away. Do not use a fire blanket if the shower is nearby.
Remove contaminated clothing. Wrap the person in a blanket to avoid shock. Get prompt

UTTARAKHAND OPEN UNIVERSITY Page 91

LABORATORY COURSE-I BSCCH- 104

medical attention. Be very careful using carbon dioxide extinguisher (the person may
smother).
Burning reagents:
Extinguish all nearby burners and remove compitable material and solvents.use a dry
chemical or carbondioxide fire extinguisher directed at the base of the flame. Do not use
water.
Burns, either thermal or chemical:
Flush the burned area with water for at least 15 minutes. Resume if pain returns. Wash off
chemicals with a mild detergent and water. No neutralizing chemicals. Creams, lotions or
salves be applied. If chemicals are spilled on a person on a large area quickly remove the
contaminated clothing while condor the safety shower. Get prompt medical attention.
Chemicals in the eye:
Flush the eye with copious amount of water for 15 minutes by placing the injured person
face up on the floor and pouring water in the open eye. Hold the eye open to wash behind
the eyelids. After fifteen minutes of washing obtain prompt medical attention.
Cuts: Minor cuts.
This type of cut is common in the laboratory and usually arises from broken glass. Wash
the cut, remove any pieces of glass, and apply pressure to stop the bleedings. Get medical
attention.
Major cuts:
If blood is spurting, place a pad directly on the wound. Apply firm pressure, wrap the
injured to avoid shock, get immediate medical attention. Never use a tourniquet.
Poisons:
Call the immediate emergency number, which is normally 108.
7.10 SUMMARY

Laboratory glassware refers to a variety of equipment, traditionally made of glass, used for
scientific experiments and other work in science, especially in chemistry. pipette, burette,
test tube, boiling tube, beaker, measuring flask, conical flask, graduated cylinder, funnel
steam bath etc. are used in chemistry lab experiments. For measuring fixed amount of a
liquid either pipette or burette (sometimes graduated cylinders) are used. For titration
purposes conical flask is used it may be 100 ml or 250 ml balance is used for weighing
purposes. For the measurement of heat of various reactions, a thermos flask or a
calorimeter is used. The resistance of a conductor is measured by means of Wheatstone
bridge. Density can be measured with the help of density bottle.

UTTARAKHAND OPEN UNIVERSITY Page 92

LABORATORY COURSE-I BSCCH- 104

UNIT 8: DETERMINATION OF SURFACE TENSION

CONTENTS:
8.1 Objective
8.2 Introduction
8.3 Organic liquid (alcohol)
8.4 Determination of composition of solvent mixture
8.5 Summary
8.1 OBJECTIVES

In this chapter students learn the following objectives.

• Objective of this chapter is to provide students with a concise and succinct detail on
the basic fundamentals of the surface tension.
• Explain the use of stalagmometer and density bottle.
• Describe how to determine the surface tension of given liquid.
• Explain the determination of composition of solvent mixture.
• Explain the precaution taken during experiment.

8.2 INTRODUCTION
“The force in dynes action on the surface of at right angles to any line of unit length” As
we all know the surface of the liquid remains in a state of tension because the molecules
which are present in it are being constantly subjected to inward pull because of the
unbalanced forces.

Fig 8.1 Surface tension is caused by the net inward pull on the surface molecules.

A molecular on the bulk is attracted from all sides hence net force on the molecule is new
but this is not the case for a molecule which is situated at the surface. The surface

UTTARAKHAND OPEN UNIVERSITY Page 93

LABORATORY COURSE-I BSCCH- 104

molecules are pulled sideways by the surrounding molecules. Since the sideway forces are
equal and opposite, fig 8.1 in magnitude so they cancel each other. But the inward pull is
there. Thus the tension at the surface is known as surface tension.

The surface tension is represented by the symbol γ, since it is a force; its unit is dynes per
centimeter.

Apparatus: Stalagmometer, thermometer, density bottle, balance, beaker etc.

When liquid is allowed to how through the stalgmemeter then γαw. That is weight (w) of
liquid falling.

Fig 8.2 Stalagmometer

From a capillary tube held vertical, is approximately proportional to surface tension of the
liquid. Hence if surface tensions of two liquids be γ1 and γ2 and w1 and w2 be the mean
weights of their drops falling from the same capillary tube,

Then

γ1/γ2 = w1/w2

the drop falls out from the capillary when its weight becomes equal to 2πrγ, where r is
radius of the capillary tube

Stalagmometer:

The instrument used for determining surface tension in the laboratory is known as
stalagmometer. It consists of a pipette with a capillary outflow tube, the end of which is
flattened out. This is done to give a larger droping surface. The surface is carefully ground
flat and polished. There are two marks, one just above the bulb and the other is just below
(x and y) fig 8.2 precautions while using stalagmometer:
UTTARAKHAND OPEN UNIVERSITY Page 94
LABORATORY COURSE-I BSCCH- 104

The stalagmometer should be carefully washed with a solution of chromic acid and with
distilled water to remove grease like things. Finally it is washed with alcohol and dried.
The tip of the lower end should not come in contact with hand, desk or some other thing,
otherwise it will be contaminated with a trace of grease. Even slight traces of grease may
alter the size of the drops, hence their number. Also the stalagmometer should be held
vertical and not shaken, otherwise the drop will fall out even before attaining maximum
size.
You must also keep in mind that the rate of flow of the liquid through the tip of
stalagmometer should not be fast. It should be about 12-18 drops per minute. If the rate of
flow is greater, then it can be decreased by attaching a piece of rubber tubing with a screw
pinch cock to the open end and adjusting the pressure, so that only 12-18 drops fall out per
minute.
Once this adjustment of pressure is done, it should be kept unchanged during the whole
experiment.
The stalagmometer is washed with solution of chronic acid, then with water and finally
with alcohol and dried. The rubber tubing with a screw pinch cock on it is used to regulate
the flow of liquid by limiting the influx of flow of air.
Fill the stalagmometer with water dipping it in a beaker containing water and sucking till
the water rises above the mark x (fig 8.2). Now bring the level of water to mark x. open the
pinch cock and adjust it so that the rate of flow of drops is about 12-18 drops per minute.
When this is adjusted, refill the stalagmometer with distilled water as above and without
changing the pressure i.e. does not disturb the pinch cock throughout the experiment. Then
start counting number of drops when meniscus passes the upper mark x and stop when it
just crosses the lower mark y. repeat the procedure 3-4 times.
Now remove the rubber tubing from the stalagmometer and rinse it with the experimental
liquid. Now fill the stalagmometer with the liquid. Adjust the pinch cock again so that 12-
18 drops fallout per minute and count the number of drops for the flow of liquid from x to
y. Repeat the process 3-4 times.
8.3 EXERCISE (ORGANIC LIQUID, ALCOHOL)
Object: To determine the surface tension of the given liquid (alcohol) by drop weight
method
Method: The liquid whose surface tension is to be determined is sucked from the rubber
tubing above the mark x and number of drops are counted when the liquid level moves
from x to y. suppose the volume of the liquid from x to y is V and number of drops formed
in this volume V are n then volume of one drop will be V/n1 and weight of one drop W1=
x d1 where d1 is density of the liquid.
The same procedure is adopted for water. In case of water if in the volume V i.e. when
water level moves from x to y if n2 number of drops are formed and density of water if d2
then weight of one drop of water will be W2= d2

UTTARAKHAND OPEN UNIVERSITY Page 95

LABORATORY COURSE-I BSCCH- 104

Hence W1/W2 = γ1/γ2 = V/n1.d1/V/n2.d2

= n2d1/n1d2
So γ1= γ2
This is the formula used for calculating surface tension of a liquid. The density of the liquid
and water are measured by density bottle and γ2 surface tension of water is taken from
standard table.
Determination of density:
Density of a liquid is mass per unit volume. It is measured by using density bottle (fig 8.3).
For measuring density of a liquid the density bottle is washed with chromic acid solution
and then with distilled water and finally with alcohol. It is then dried. The density bottle is
then weighed. It is then filled with distilled water and again weighed. It is then emptied of
water, washed with alcohol and dried. The density bottle is then filled with experimental
liquid and weighed again.
Observations:
Room temperature= t0C
Weight of empty density bottle= w1 gm
Weight of density bottle and water = w2 gm
Weight of density bottle and liquid= w3 gm

S. No. liquid no of Mean

drops value
1 1
water 2 n1=
3
1
2 Liquid 2 n2=
3

Calculations:

Hence surface tension of liquid

γ2= γ1
Surface tension of water can be had from standard table.

UTTARAKHAND OPEN UNIVERSITY Page 96

LABORATORY COURSE-I BSCCH- 104

Result: The surface tension of the given liquid is dynes/cm at t0C.

Precautions:
1. The stalagmometer should be washed properly with chromic acid
water and finally with alcohol
2. The stalagmometer should be held vertically.
3. The tip of the stalagmometer should not come in contact with hands or working table.
4. The drops should be allowed to fall off from stalagmometer tip under their own weight
and should not be pushed away by kinetic flow.
5. The rate of flow of liquid be 12-18 drops per minute.
8.4 EXERCISE (DETERMINATION OF COMPOSITION OF
SOLVENT MIXTURE)
Object: To determine the composition of the given mixture of two components A and B.
Apparatus: Stalagmometer, thermometer, balance density bottle, beakers etc.
Theory:
A number of solutions of A and B are prepared. Suppose we have to determine the
composition of sucrose solution. Then prepare sucrose solution of different concentration
say 10 gm of sucrose and 90 gm water i.e. 10% of sucrose solution, 20 gm of sucrose and
80 gm of water i.e. 20% of sucrose solution and so on. Now number of drops in each is
determined as usual. A graph is then plotted between no of drops (or surface tension) and
concentration of one liquid say water (A). the number of drops of the unknown mixture is
also determined. It’s composition can be determined from the graph.
Procedure: Prepare 5%, 10%, 15%, 20%, 25%, 30% mixture of sucrose in water in
beakers. Wash the stalagmometer with chronic acid solution. Then with water and finally
with alcohol and dried. Attach a small piece of clean rubber tube to the upper end of the
stalagmometer. The rubber tubing with a screw pinch cock on it is used to regulate the flow
of liquid, by limiting the flux of air.
Now fill the stalagmomete with say first with 5% solution of sucrose by dipping it in a
beaker containing the 5% solution and sucking till the solution rises above the mark x. now
bring the level of solution to the x. open the pinch cock and adjust it so that the rate of flow
of drops is about 12-18 drops per minute. When it is adjusted, refill the stagmometer with
5% solution without changing the pressure. Now start counting the drops when meniscus
passes from the upper mark x and stop when it just crosses the lower mark y. Repeat this
process for 5% solution 3-4 times.
Now the rubber tubing is removed from the stalagmometer and rinse with 10% solution.
Now repeat the process you have followed for 5% solution. Apply the same procedure for
all the solutions prepared above and count the number of drops for each solution. The
number of drops of unknown solution is also counted.
Observation:
Room temperature = t0C

UTTARAKHAND OPEN UNIVERSITY Page 97

 LABORATORY COURSE-I BSCCH- 104

Sl. Composition of Mixture water B No of drops

No Sucrose (A)
1 5% 95%
2 10% 90%
3 15% 85%
4 20% 80%
5 25% 75%
6 30% 70%

Table 8.1

Calculations: Plot of a graph between composition of sucrose A (X-axis) and number of

drops Y-axix. The point corresponding to the number of drops of the unknown composition
is found. From that point draw a perpendicular on the composition axis, the value will give
the required concentration.

Result: The percentage composition of the given mixture is = % of A (in this case sucrose)
and % of B (water).

Precautions:1. The stalagmometer should be washed properly with chromic acid water and
finally with alcohol
2. The stalagmometer should be held vertically.
3. The tip of the stalagmometer should not come in contact with hands or working table.
4. The drops should be allowed to fall off from stalagmometer tip under their own weight
and should not be pushed away by kinetic flow.
5. The rate of flow of liquid be 12-18 drops per minute.

Viva voce

1.Define surface tension?

2.Unit of surface tension?
3.What is the effect of temperature on surface tension?
4.Why stalagmometer should be kept vertical during the experiment?
5.What is the relation between surface tension and intermolecular attractional forces?
6.How density of a liquid is measured?

UTTARAKHAND OPEN UNIVERSITY Page 98

LABORATORY COURSE-I BSCCH- 104

UNIT 9: DETERMINATION OF VISCOSITY

CONTENTS:
9.1 Objectives
9.2 Introduction
9.3 Cane sugar solution or Glycerol (more than 5%)
9.4 Detergent /Determination of CMS (Critical micelle concentration)
9.5 Summary
9.1 OBJECTIVES

In this chapter students will learn the following objectives.

• Objective of this chapter is to provide students with a concise and succinct detail on
the basic fundamentals of the viscosity.
• Explain the use of Ostwald’s viscometer and principal.
• Describe how to determine the viscosity of given liquid like cane sugar solution .
• Determine the composition of the given mixture consisting of two liquids A & B
by viscometer.
•Explain the various precautions taken during experiment.
9.2 INTRODUCTION

Some liquids like water, alcohol move very fast, on the other hand liquids like honey,
glycerol etc move very slowly. The property of the liquid which determines its flow is
termed as viscosity. Thus we can say that viscosity is a property of liquid which retards its
flow.
When temperature is applied to the liquid its intermolecular attractions forces are
weakened, because kinetic energy of molecules increases. As viscosity depends on
intermolecular forces, hence by the application of temperature viscosity decreases.

The unit of viscosity is poise. Scientist Poiseuille, who did pioneer work in the field of
viscosity, to honour him unit of viscosity is poise. Smaller unit of viscosity are centipoise
and millpoise. Viscosity is represented as η (eita).

Coefficient of viscosity:

If a liquid is allowed to flow on a surface each layer moves parallel to its adjacent layer
without intermixing. The unparallel flow of layers is called turbulent flow. In the laminar
flow the force F required to maintain a steady difference v between velocities of two
adjacent layers is directly proportional to v, and area A of the surface of contact of two
layer and inversely proportional to distance x between them. Hence

UTTARAKHAND OPEN UNIVERSITY Page 99

LABORATORY COURSE-I BSCCH- 104

F A.v/x

or F= η Av/x

Here η is called coefficient of viscosity of the liquid if A= 1 sq. cm., v=1 cm/sec and x=1
cm then F=η. Hence η is defined as the force necessary to maintain a velocity difference of
unity between two adjacent parallel layers of liquid, one cm apart and having area of
surface of contact unity.

The pressure p at any instant driving the liquid of coefficient of viscosity η through the
capillary tube depends upon the difference of the height h, in the levels of liquid in the two
limbs, the density d and the gravitational force g.

that is p hdg

from equation 9.1

η p.t

η hdgt

If η1 and η2 be the viscosities of the two liquids under study and d1 and d2 be their
respective densities and t1 and t2 be the respective time of flow the same volume

Then η1 g1d1t1

And η2 gd2 t2

Since same apparatus is used for both the liquids

Thus by determining the densities and the time of flow of the two liquids, the
coefficient of viscosity of one of them can be easily calculated, provided the coefficient of
viscosity of the other liquid is known.

Description of the apparatus:

Ostwald’s viscometer: The apparatus generally used for the determination of coefficient
of the viscosity of liquid is known as Ostwald’s viscometer as it was designed by Ostwald.
It is shown in fig 9.1.

UTTARAKHAND OPEN UNIVERSITY Page 100

LABORATORY COURSE-I BSCCH- 104

Fig 9.1 Ostwald’s viscometer

The viscometer consists of a capillary tube connected at its upper part with a bulb A and at
its lower part with a wider U-tube provided with a bulb B. Two marks x and y are etched
on the capillary tube above and below the bulb A.
Cleaning of viscometer:

The viscometer should be cleaned thoroughly so that there are no obstructions in the
capillary tube. It must be free from any greasy material. The viscometer is cleaned with
chromic acid by filling with the acid which is prepared by reaction between potassium
chromate and concentrated sulphuric acid.

The acid solution is kept in the viscometer for some hours. It is washed with water then
with alcohol. It is then dried.

Density of the liquid is measured with the help of density bottle. Density of the
liquid is mass per unit volume. The density at a given temperature means the relative
density at that temperature with respect to the density of water. For all practical purposes,
the density of water is taken to be unity at all temperatures.

9.3 EXERCISE CANE SUGAR SOLUTION OR GLYCEROL

(MORE THAN 5%)
Object: To determine viscosity of the given liquid (say cane sugar solution) at room
temperature.
Apparatus: Viscometer, unknown liquid, stop watch, distilled water, density bottle, pipette
etc.

Formula used: ηl = (dltl /dw tw) ηw

UTTARAKHAND OPEN UNIVERSITY Page 101

LABORATORY COURSE-I BSCCH- 104

Where ηl dltl are coefficient of viscosity, density and time of flow respectively of the
experimental liquid and ηw, dw and tw are coefficient of viscosity, density and time of flow
respectively of water.

Procedure: Clean the viscometer with chromic acid then wash with distilled water. It is
finally washed with alcohol and then dried. A sufficient volume of distilled water is
introduced by pipette in bulb B so that bend-portion of tube and half or little more than half
of bulb B are filled up. Now suck up water until it rises above the mark x above the bulb A.
Now bring water to touch the mark x and hold it there by placing your index finger at the
top of the narrow limb. Remove your finger and start the stop watch. Stop it as soon as
water touches the mark y. Repeat this process 3-4 times and take the mean value. The
viscometer is kept in a thermostat for 10-15 minutes before the mean value, so that the
contents acquire the room temperature.

Now remove water from the viscometer and dry it. Introduce in bulb B some cane sugar
solution and rinse the viscometer. Now fill the viscometer with the experimental liquid and
keep it also in the thermostat for 10-15 minutes, so that cane sugar solution attains room
temperature. Note the time during the flow of solution between the marks x and y. Repeat
the process 3-4 times and take the mean value.

Wash the density bottle and dry it. First weight it empty. Then fill it with water and finally
with cane sugar solution and weight it both the times. Note the room temperature, by
recording the temperature of water in the thermostat.

Observations:

1.Room temperature = t0
2.Time of flow between x and y

Sl No. Water Cane sugar solution

Time of flow mean Time of flow Mean
1
2 tw te
3
4

9.3 Density of cane sugar solution and water.

Weight of empty density bottle = w1 gm

Weight of density + water = w2 gm
Weight of density bottle + cane sugar solution = w3 gm

UTTARAKHAND OPEN UNIVERSITY Page 102

LABORATORY COURSE-I BSCCH- 104

Calculation: Weight of water = w2-w1 gm

Weight of cane sugar solution= w3-w1 gm
Density of glycol = weight of glycol/weight of water x density of water dw
= weight of glycol/weight of water = (w3-w1) /(w2-w1)
As density of water dw =1
Coefficient of viscosity of glycol
ηl = (dl tl) / (dw tw) ηw

Now the viscosity of water ηw at t0C from standard table, and substitute in the above
expression, the value of ηl is calculated.
Result:The coefficient of viscosity of the given liquid at t0C is poise.
Precautions:
1. Viscosity must be kept in vertical position.
2.Some volume of water and glycol should be taken in the viscometer.
3. Observe accurately when the meniscus of glycol and water just passing the upper and
lower marks (x and y).
4. Before performing the experiment viscometer should be properly cleaned as described
before.

9.4 EXERCISE
Object: To determine the composition of the given mixture consisting of two liquids A &
B by viscometer.
Apparatus: Ostwald viscometer, density bottle, thermostat, thermometer, stop watch,
beakers etc.
Theory: By plotting the values of time of flow of solution against their concentrations, we
get a curve from which the concentrate of unknown solution is determined.
Procedure:The viscometer is thoroughly cleaned so that there are no obstructions in the
capillary tube. It must be free from any greasy material. The viscometer is first cleaned by
first keeping it filled with a solution of chromic acid, which is prepared by the reaction
between potassium dichromate and sulphuric acid, for some hours. It is then washed with
distilled water and finally with alcohol. It is then dried.
Now prepare a number of solutions by mixing the two liquids A and B in different
proportions. The solutions are made up with 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20%,
10% of A by volume. (90 ml of A and 10 ml of B in first case, 80 ml of A and 20 ml of B
in the second case and so on.) The time of flow of each solution noted by means of
Ostwald’s viscometer, by allowing the solution to flow from x-mark to y- mark. Repeat this
process 3 & 4 times and take the mean value. Before noting the time, the viscometer is kept
in a thermostat for 10.to15 minutes, so that the contents acquire the room temperature. The
time of flow for the unknown solution is also measured, as usual.

UTTARAKHAND OPEN UNIVERSITY Page 103

LABORATORY COURSE-I BSCCH- 104

If we are to calculate the viscosity of the liquids then the density of each solution and that
of unknown solution is also determined.

Observations: Room temperature = t0C

Sl. No. Percentage of components Time of flow in secs
A B

1 90 10
2 80 20
3 70 30
4 60 40
5 50 50
6 40 60
7 30 70
8 20 80
9 10 90
10 Unknown
solution

Fig 9.2 strength of unknown solution

Conclusions:
A curve is plotted between the concentration of one component say A and time of flow in
seconds. You will see that a straight line is obtained (fig 9.2). The composition of
unknown solution is calculated by locating and marking the point on the straight line

UTTARAKHAND OPEN UNIVERSITY Page 104

LABORATORY COURSE-I BSCCH- 104

corresponding to its measured time of flow. A perpendicular is drawn from that point on
the concentration axis, from which the composition of unknown solution can be read
directly.
Result: The composition of given mixture is ……..% of A and ……..% of B
Precautions:
Viscosity must be kept in vertical position.
5.Same volume of liquids should be taken in the viscometer.
6.Observe accurately when the meniscus just passing the upper and lower marks (x and y).
7.Before performing the experiment viscometer should be properly cleaned as described
before.
Viva–Voce

1.Define the term coefficient?

2.What is the unit of coefficient of viscosity?
3.Why relative viscosity has no unit?
4.What is the effect of temperature on coefficient of viscosity? If decreases why?
5.Why unit of viscosity is poise?

UTTARAKHAND OPEN UNIVERSITY Page 105

LABORATORY COURSE-I BSCCH- 104

UNIT 10: pH MEASUREMENT

CONTENTS:
10.1 Objectives
10.2 Introduction
10.3 Measurement of pH of simple solution (aq. Strong acid/ strong base or weak acid /
weak base at different dilution)
10.4 Summary
10.1 OBJECTIVES
In this chapter students learn the following objectives.

• Objective of this chapter is to provide students with a concise and succinct detail
on the basic fundamentals of the pH.

• Explain the methods of determination of pH.

• Explain the use of various indicators.

• Describe how to measurement the pH of simple solution (aq. Strong acid/ strong base
or weak acid / weak base at different dilution).

• Explain the various precautions taken during experiment.

10.2 INTRODUCTION
pH value

Sorenson (1909) expressed the hydrogen ion concentration in solution in term of a number
called pH which can be defined as the logarithm of reciprocal of hydrogen ion
concentration.

Mathematically it can be expressed,

pH = log10 = log10

= -log10 = - log10 CH+

For pure water

H2O = H++OH-

Ionic product of water Kw = CH+ .COH-

UTTARAKHAND OPEN UNIVERSITY Page 106

LABORATORY COURSE-I BSCCH- 104

At 250 C Kw = 10-14

So CH+ =COH- =10-7 gm. Ion /litre

And pH = -log1010-7 =7

H+ = 10-0 10-1 10-2 10-3 10--4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13 10-14

pH = 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14

acidic solution neutral alkaline solution

Hence

For neutral solution: CH+ = 10-7 and pH = 7

For acidic solution: CH+ > 10-7 and pH > 7

For alkaline solution: CH+ < 10-7 and pH< 7

Methods of determining pH
To determine pH value you can use the following methods:
(1) Conductivity method
(2) Potentiometric method
(3) Catalytic method
(4) Calorimetric method
(5) E.M.F. method
Before determining the pH value of a given solution by any method you should have some
knowledge of buffer solutions. The solution which is capable of opposing any change in its
pH caused by addition of acid, alkali or water within a certain limit are defined as buffer
solutions or in other words buffer possesses reserve acidity or alkalinity.
Buffer solution generally consist of a weak acid and one of its salt or weak base and one of
its salts, There are few cases of buffer which are composed of strong acid and one of its
salt, such as HCl + KCl . The resistance offered by buffer solution against change in its pH
is called buffer action.
Buffer solutions can be obtained by mixing fixed amount of weak acid and one of its salt
from pH value one to ten.
The pH of a buffer solution is controlled by the ratio of salt to acid or base. Hence buffer of
different pH values can be prepared by varying this ratio. In this regard the following
equations are of great importance.
(a)Buffer composed of weak base and its salt:-
pH= pKa + log10
Where Ka is dissociation constant of weak acid.
(b) Buffer composed of weak base and its salt :-
UTTARAKHAND OPEN UNIVERSITY Page 107
LABORATORY COURSE-I BSCCH- 104

pH= pKw – pKb – log10

Where Kw is ionic product of water and Kb is dissociation constant of weak base.
For example if 4.7 ml N/5 HCl is added to 25 m N/5 KCl and the mixture is diluted to 100
ml, pH of the solution will be one, Similarly if equal part of M/40 NaHCO3 and M/40
Na2CO3 are mixed its pH will be ten.
Universal indicator: It consists of a mixture of indicators which goes through a series of
colour change with pH and thus helps in selecting the appropriate indicator for determining
pH of a solution by indicator method, it tells approximate value of pH.
Calorimetric method:
The method is based on the fact that indicator changes its colour according to pH of the
solution been in which it had been added. Hence from the color variation of indicator in a
given solution , the pH can be determined.

This method employs a number of buffer solution of known pH and a suitable indicators.

At first the approximate value of pH of the given solution is determined with the universal
indicator which is a mixture of several indicators to select approximate indicator. Then a
definite amount pf appropriate indicator is added to a certain volume of the test solution
and a colour is developed which is solution then matched against the shades produced by
the same amount of the same indicator added in the same volume of a series of suitable
chosen buffer solution of known pH. The buffer solution which gives the same shade as
the test solution has the same pH.

For more accurate pH determination ( within 0.5 to 0.1 unit )indicators of short working pH
ranges are prepared so as to produce more distinct colour changes .the pH ranges of
indicators which are generally used in pH determination can be known from the following
tables :

Indicator pH-range Colour – change

Metacrisol purple 1.2 -2.8 red to yellow

Methyl violet 0.3 – 3.2 yellow to violet

Methyl orange 3.1 – 4.4 red to orange

Bromophenol blue 3.6 - 4.6 yellow to blue

Methyl red 4.2 –6.3 red to yellow

Bromocresol green 4.0 – 5.6 yellow to blue

Phenol red 6.8 – 8.4 yellow to red

UTTARAKHAND OPEN UNIVERSITY Page 108

LABORATORY COURSE-I BSCCH- 104

Phenolphthlien 8.2 – 10.0 colorless to pink

10.3 EXERCISE (MEASUREMENT OF PH OF SIMPLE

SOLUTION (AQ. STRONG ACID/ STRONG BASE OR WEAK
ACID / WEAK BASE AT DIFFERENT DILUTION)

Object- To determine the pH of the given solution by indicator method (using buffer
solutions of known pH).
Apparatus used: Test tube, indicators, pipette, burette, Test tubes etc.

Procedure:

To a small portion of the test solution, add a few drops (5 drops) of the universal indicator
and observe the color change. Then by referring to the colour chart and find the
approximate value of pH of the solution.

Let the pH as indicated by the universal indicator lies within 3.2 and 4.5 then to find out
the correct pH value, you must select an appropriate indicator having short working pH
range including the pH limit ie, 3.1 to 4.5. From the inspection of the table, the suitable
indicator will be methyl orange.

Prepare a series of buffer solutions (of known pH value differing by .1 unit covering the
pH range 3.1 to 4.5) by mixing a salt and a weak acid (or a weak base) in a definite ratio
which can be calculated by the equation described earlier.

Now arrange ten or more test tubes of same dimensions in a rack. Place in each of these in
turn 5 ml of buffer solution of definite value of pH value, ie, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7,
3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5. Mark the pH value on the test tubes. To each test tube,
add .5 ml of methyl orange solution. Observe the different shades of colour from red to
orange.

Now 5 ml of test solution in a test tube of same shape and size and 5 ml of same indicator
(methyl orange). The color produced in the test solution is then matched with the colours
produced in buffer solutions. When complete match is found, the test solution and the
corresponding buffer solution have the same pH. If complete match is not found, but the
colour lies between those of two successive standard colours then pH value will lie
between those two standards.

Precautions:

1. While preparing buffer solutions of different pH, there should be correct weighing.

2. Measurement of volume should be proper

UTTARAKHAND OPEN UNIVERSITY Page 109

LABORATORY COURSE-I BSCCH- 104

3. If pH meter is used it should be first standardized by taking a buffer of known pH.

VIVA—VOCE

1. Define pH.

2. What are buffer solutions?

3. How buffer solution maintains their pH value,

4. Why water is said to be neutral?

5. What is the equation relating hydrogen ion concentration and Ph.?

UTTARAKHAND OPEN UNIVERSITY Page 110

LABORATORY COURSE-I BSCCH- 104

UNIT 11: THERMOCHEMISTRY

CONTENTS:
11.1 Objectives
11.2 Introduction
11.3 Heat capacity
11.4 Enthalpy of solution
11.5 Enthalpy of neutralization for weak acid with strong base or weak base with strong
acid Enthalpy of ionization
11.6 Summary
11.1 OBJECTIVES

In this chapter students learn the following objectives.

• Explain basic principle of thermochemistry.
• Describe the experiment related to heat capacity measurement.
• Explain the experiment related to measurement of enthalpy of solution.
• Explain the enthalpy of neutralization for weak acid with strong base or weak base
with strong acid Enthalpy of ionization.
• Explain the various precautions taken during experiment.

11.2 INTRODUCTION

Thermochemistry is the branch of physical chemistry which deals with the heat
changed by chemical reaction.

Internal energy:
Every substance has a definite amount of energy is known as internal energy E. its exact
value cannot be determined, but the change in internal energy, E, can be accurately
measured experimentally.
E = Eproducts – Ereactants = EP - ER
When E is positive, the reaction is endothermic and when E is negative reaction is
exothermic.
The energy changes are usually expressed in calorie (cal) kilo calorie (1 kcal = 1000 cal),
Joule (J) and kilojoule.
The change in internal energy (E) is the heat change accompanying a chemical reaction at
constant volume.
The enthalpy of a system is defined as the sum of internal energy and the product of its
pressure and volume.

UTTARAKHAND OPEN UNIVERSITY Page 111

LABORATORY COURSE-I BSCCH- 104

Thus H= E+PVIt is also called heat content.

Heat capacity of a system is the heat absorbed by unit mass in raising its temperature by
one degree at a specific temperature.
Molar heat capacity of a system is defined as the amount of heat required to raise the
temperature of one mole of the substance (system) by one degree.

11.3 EXERCISE: TO DETERMINE WATER EQUIVALENT OF

CALORIMETER

A Calorimeter or a thermos flask:

For the measurement of heat of various reactions, we can suitably use a thermos flask or a
calorimeter. A calorimeter is suitable for general experiments with solutions. It may be
constructed by loosely packing the space between two large boiling tubes or two beakers
with cotton wool. Though the modern vacuum flask has merit of very good insulation, but
the narrowed neck of the ordinary thermos type prevents the use of an efficient stirrer, and
if mixing is done by shaking, the water equivalent becomes large and quite indefinite in
value.
The water equivalent or heat capacity of a calorimeter is defined s the number of calories
required to heat the calorimeter by 10C. If M is the mass of the calorimeter and S be its
specific heat then MS will be the water equivalent of the calorimeter.
An unsilvered, straight sided Dewar flask is shown in fig 11.1. It avoids the serious
diadvantage without serious loss of heat insulation. Its transparency is quite invaluable in
experiments on heat of solution etc. the vessel should be closed with a coak or rubber cock,
groved for the stirrer S, and carrying a shortwide tube t, through which passes an accurate
thermometer T having accuracy of 0.10. The thermometer is supported externally by a
retort clamp.

Fig 11.1 Devar flask

UTTARAKHAND OPEN UNIVERSITY Page 112

LABORATORY COURSE-I BSCCH- 104

The tube t should be stoppered with a plug of cotton wool and serves as inlet for the
introduction of liquids or solids into the calorimeter. The stirrer S should be quite efficient
and may be formed of bent copper or silver wise a shown in the figure. A sleeve of stout
rubber or ebonite tubing n serves as a heat insulating handle. The empty glass beaker B
placed as a shield round the calorimeter usually improves the regularity of the temperature
observations.
Apparatus: Calorimeter, thermometer, stirrer, water heater, pipette, burette, beaker
Theory: During the heat changes, the calorimeter will also take up some of heat evolved,
which should be taken into account by taking into account by determining the water
equivalent or heat capacity of the calorimeter.
If M is the mass of calorimeter and S the specific heat then water equivalent of calorimeter
will be MS.
Procedure:
Take 25 ml of distilled water in the calorimeter and record its temperature accurately to its
nearest 0.10. now heat 50-60 ml of water in a separate beaker to a temperature about 25-350
higher than the room temperature. Now pipette about 25 ml of the hot water and add it to
another beaker and read its temperature. Add this hot water quickly to the water in the
calorimeter stir the contents well with stirrer. Read the highest temperature, upto an
accuracy of 0.10 attained immediately after mixing.

Observations:

Volume of cold water taken = M1 ml.

Volume of hot water mixed= M2 ml.
Initial temperature of water = t10 C
Temperature of hot water= t20 C
Temperature of the mixed solution= t30 C

Calculations:

Heat taken by calorimeter and water = (W+M1) (t3-t1) cal.

Here W is water equivalent of calorimeter.
Specific gravity of water is taken as unity (S=1)
Heat given by the hot water = M2 (t2-t3) cal.
Heat taken up = Heat given out
(W+M1)(t3-t1) = M2 (t2-t3)
W (t3-t1) + M1 (t3-t1) = M2 (t2-t3)
W (t3-t1) = M2 (t2-t3) - M1 (t3-t1)
So W= [M2 (t2-t3) – M1 (t3-t1)]/ (t3-t1)

UTTARAKHAND OPEN UNIVERSITY Page 113

LABORATORY COURSE-I BSCCH- 104

Since t1, t2, t3, M1 and M2 are known; hence water equivalent of calorimeter can be
calculated.

Result: Water equivalent of calorimeter =

Precautions:

1. Hot water must be added to cold water and that too immediately.
2. The temperature should be accurately recorded.
3. The calorimeter should be completely insulated.
4. The glass should be of high quality and so transparent that temperature can be easily
read.

Exercise – 2

Object: To find out heat of dilution of sulphuric acid

Apparatus: calorimeter, thermometer, stirrer, beaker, pipette 5m and 25 ml water heater
etc.
Theory: we know during the heat changes, calorimeter will also take up some heat, known
as water equivalent of calorimeter. This heat must also be taken into account. If M is mass
of the calorimeter and S be its specific heat, than its water equivalent is MS.
Procedure:
Now take 25 ml of distilled water in the calorimeter and note down its temperature
to the nearest 0.10C, now pipette out exactly known quantity say 5 ml of sulphuric acid of
known strength. Now pour this acid in the calorimeter by holding the tip of the pipette
below the water surface and stir the contents of the calorimeter with the pipette itself.
Continue stirring and note the temperature. Now record the maximum temperature attained.

11.4 EXERCISE (ENTHALPY OF SOLUTION)

Object: To determine enthalpy of solution of the given substance

Apparatus: Calorimeter thermometer, stirrer, beaker, burette, pipette, water heater etc.
Theory: The quantity of heat absorbed or evolved when one gram molecule of a substance
is dissolved in a large excess of water or solvent, so that further dilution does not produce
any more heat change, is known as heat of solution.
It is most important in expressing the heat of solution to state the exact condition of the
solid substance, i.e., it contains water of crystallisation or not. The heat of solution is often
quite different in the two cases.

UTTARAKHAND OPEN UNIVERSITY Page 114

LABORATORY COURSE-I BSCCH- 104

Procedure: Take 25 ml. of distilled water in the calorimeter and record its temperature
estimating it to the nearest 0.10C. Now heat some water in a separate beaker to a
temperature about 250-350 higher than the room temperature. Now pipette out 25 ml. of hot
water and add it to another beaker and read its temperature. Add this hot water quickly to
the water in the calorimeter. Stir the contents well with a stirrer. Read the highest
temperature upto an accuracy of 0.10, attained immediately after mixing.
Now take 200 ml. of distilled water in the calorimeter. Record its temperature. Now add a
known quantity of the given substance, say KCl. and dissolve it in the water present in the
calorimeter, by means of a stirrer. Note the final temperature. Now repeat the above
procedure by taking more quantity of substance, dissolve it in the water present in the
calorimeter. If initially 1 gm of KCl was dissolved in water, now take 1.5 gm of KCl. Note
the final temperature this time also.
Observations:
For water equivalent
Volume of water taken =M1 ml.
Initial temperature of water= t10C
Volume of hot water taken= M2 ml
Temperature of hot water= t20C
Final temperature of mixing= t30C

For heat of solution:

Volume of water taken =M3 ml

Initial temperature of water = t10C
Amount of substance dissolved= W1 gm.
Final temperature after mixing the substance= t40C
Calculations:
1. For water equivalent of calorimeter
Heat taken by calorimeter and cold water
= (W+M1) (t3-t1) cal.
W is water equivalent of calorimeter, specific gravity of water is taken as
unity (s=1).
Heat given by hot water
= M2 (t2-t1)
So (W+M1) (t3-t1) = M2 (t2-t3)
So w =
2. For heat of solution:
Heat absorbed by the solution after adding the substance

UTTARAKHAND OPEN UNIVERSITY Page 115

LABORATORY COURSE-I BSCCH- 104

Heat absorbed by the substance per litre

= Q cal. (suppose)

If M is molecular weight of the substance, then heat of solution is then given by cal.
per litre.
Result: The enthalpy of solution of the given substance = cal

Precautions:

1. The temperature should be accurately recorded.

2. The hot water must be added to cold water and that too immediately.
3. The calorimeter should be completely insulated.
4. The glass should be of high quantity and so transparent that the temperature can
be read easily.
11.5 EXERCISE (ENTHALPY OF NEUTRALIZATION FOR
WEAK ACID WITH STRONG BASE OR WEAK BASE WITH
STRONG ACID ENTHALPY OF IONIZATION)

Object: To determine enthalpy of neutralisation of a weak acid by strong base. (Suppose

weak acid acetic acid is being neutralised by strong base sodium hydroxide).
Apparatus used: Calorimeter, thermometer, beakers, stirrer, pipette, burette,water heater
etc.
Theory:
The enthalpy of neutralisation is the quantity of heat evolved when one gram equivalent of
an acid is neutralised by one gram equivalent of a base. When any strong acid in dilute
solution is neutralised by any strong base in dilute solution of about the same
concentration, the heat evolved is practically a constant quantity for strong acids and bases
this quantity is 13,700 cal. this can be explained in the following way.
Strong acids and strong bases in dilute solution are almost completely ionized and
the salt formed by their union is also completely ionised. So neutralization of strong acid
say HCl by strong base say NaOH can be expressed in the following way
HCl + NaOH = NaCl + H2O + 13700 cal
orH++Cl- + Na+ + OH- = Na+ + Cl- + H2O + 13700 cal
orH+ + OH- = H2O + 13700 cal
So heat of neutralization of strong acid with strong base is nothing but heat of
formation of water from H+ ions and OH- ions. Here one gram equivalent of hydrogen ions
UTTARAKHAND OPEN UNIVERSITY Page 116
LABORATORY COURSE-I BSCCH- 104

combine with one gram equivalent of hydrogen ions, and hence heat evolved is always
13700 cal.
The enthalpy of neutralization of weak acids by strong bases or strong acids by
weak bases is less than 13700 cal. Weak acids or weak bases are not completely ionised. In
case of neutralization of weak acid by strong base (say CH3COOH by NaOH), the
incompletely ionised acid (CH3COOH) has to become ionised before the hydrogen ion can
combine with the hydrogen ion. The ionization of the weak acid usually takes place with
absorption of heat and the heat change due to ionization occurring during the reaction adds
algebraically to 13700 cal.
In the neutralisation of acitic acid by sodium hydroxide we have the following
initial condition on mixing the two solutions
NaOH + CH3COOH
Na+ + OH- + (1-α) CH3COOH + α H+ +α (CH3COO-).

Hence α is the degree of ionization of acetic acid.

As sodium acetate is completely ionized in the solution, the reaction yields Na+ +
CHCOO- + H2O
So enthalpy of neutralization of weak acid and strong base will be less than 13700
cal.

Procedure:

Take 25 ml of distilled water in the calorimeter…….

Now prepare extract 1Msolution of acetic acid and sodium hydroxide. Note down
their initial temperature .Now take 100ml of 1Msolution of acetic acid in the calorimeter
and add 100ml of 1Msolution of NaOH to it. Still well and record the maximum
temperature after mixing .If the mixture of acetic acid and sodium hydroxide are not exact
1Mthen it will be very difficult to calculate heat of neutralization, if the M of acetic acid is
more than 1M then after reacting with sodium hydroxide some acid will be there after
addition in the calorimeter. Similarly if sodium hydroxide is stronger than 1Msome alkali
will be left unreacted and the mixture in the calorimeter will be alkaline even after reaction
.So whether it is acetic acid or sodium hydroxide the solution should be exactly1M.

Observations:

1.For water equivalent :

2.Volume of (cold )water taken = M1ml
Initial temperature of water = t1C
Volume of hot water = M2ml
Temperature of hot water = t20C
Final temperature after mixing = t30C
UTTARAKHAND OPEN UNIVERSITY Page 117
LABORATORY COURSE-I BSCCH- 104

3.For heat of neutralization

Volume of 1M CH3COOH = m3ml
Volume of 1M NaOH = m4ml at
Initial temperature of either CH3COOH or NaOH = t4C
Final temperature after addition of CH3COOH and NaOH = t5c
4.Calculation:
For water equivalent calorimeter
(1)Heat taken up by calorimeter and water =( W+M1)(t3-t1) cal.
Here W is water equivalent of calorimeter.
Heat given out by hot water = M2( t2-t3)
As heat given out = heat taken up
(W+M1) (t2-t1) = M2(t2-t3)
So W = (M2(t2-t3)-M1(t3-t1))/(t3-t1)
For heat of neutralization:
Rise in temperature after mixing 100m 1MNaOH in100ml 1M NaOH in 100ml 1M
CH3COOH
= (t5-t4)C
Heat given out by the above solution
= (M3+M4+W)(t5-t4)
= Q cal.(say) (Since every term is known Q can be calculated )
Hence molar heat of neutralization
= Qx1 mole/0.1 cal.
= Qx10 cal.
Result: Molar enthalpy of neutralization of weak acid (CH3COOH) and strong base
(NaOH) is ……..……cal.

Precautions:
1.Hot water must be added to cold water and that too immediately.
2.The temperature should be accurately recorded.
3.The calorimeter should be completely insulated.
4.The glass should be of high quality and so transparent that temperature can be easily read.

For preparing 1M solution of acetic acid and 1M solution of sodium hydroxide you
will have to proceed as follows. Prepare a solution of acetic acid of approximately 1.5M in
250ml flask. To determine its strength you will have to titrate it against sodium hydroxide,
which is standardized by titrating it against standard solution of oxalic acid. Standard
solution of oxalic acid is prepared weighing certain amount and dissolving it in fixed
quantity of solvent. Once strength of NaOH has been determined it can be used as titrate
against acetic acid

UTTARAKHAND OPEN UNIVERSITY Page 118

LABORATORY COURSE-I BSCCH- 104

Exercise:
Exercise-4

Object: To determine enthalpy of ionization of weak acid (say acetic acid).

The enthalpy of neutralization of weak acid by strong base or strong acid by weak
base is less than 13700 cal.Weakacid or weak base are not completely ionized. In case of
neutralization of weak acid by strong base (say CH3COOH by NaOH ), the incompletely
ionized acid (CH3COOH)has to become ionized before the hydrogen ion can combine with
the hydroxyl ion . The ionization of the weak acid usually takes place an absorption of heat,
and the heat change due to ionization occurring during the reaction adds algebraically to
13700 cal.
In the neutralization of acetic acid by sodium hydroxide we have the following
initial condition, onmixing two solutions
NaOH +CH3COOH
Na+ + OH- + (1-α ) CH3COOH + αH+ +α(CH3COOH).
Here α is degree of ionisation of acetic acid.
Assodium acetate is completely ionized in the solution, reaction yields
Na+ + CH3COO- + H2O
So in the reaction mixture following process occur:
(1-α) gram molecule of acetic acid ionized and if His the enthalpy of ionization of
acetic acid per gram molecule, then (1-α) H is the heat change due to ionisation.
One gram equivalent of hydrogen ion combine with one gram equivalent of
hydroxyl ion giving heat of evolution of 13700 cal.
The algebraic sum of the above two quantities is heat of neutralization measured,
say H1.
That means H1=(1-α )H +13700
H =(H1 -13,700)/(1-α)
Here H is negative quantity that means ionization of acetic acid is accompanied by
absorption of heat .Hence the value of H1 will be less then13, 700 cal.

Procedure:
Measure first the enthalpy of neutralization of a normal solution of acetic acid by
normal solution of sodium hydroxide. Take the enthalpy of neutralization of strong acid
and strong base as 13,700 cal, or determine it experimentally.
Measure the degree of ionization of normal solution of acetic acid by any known
method (say conductivity method), otherwise this can be taken from standard table.
Observations:
For water equivalent of calorimeter,
Volume of water taken = M1 ml
Initial temperature of water = t10C
Volume of hot water taken =M2 ml.
UTTARAKHAND OPEN UNIVERSITY Page 119
LABORATORY COURSE-I BSCCH- 104

Temperature of hot water = t20C

Final temperature of the addition = t30C
For enthalpy of ionization
Volume of 1M CH3COOH solution =M3 ml.
Volume of 1M NaOH =M4ML
Initial temperature of acetic acid or sodium hydroxide = t40C
Final temperature on mixing of CH3COOH and NaOH = t50C
Calculation:
Water equivalent of calorimeter = (W= M2(t2-t3)-M1(t3-t1)/(t3-t1)
Rise in temperature on mixing acetic acid and sodiumhydroxide= (t5-t4)0C
Heat given by the solution=(W+M3+M4 )(t5-t4) = Q1 cal.
Molar heat of neutralization is =H1-13,700/(1-α) cal.

Result: Enthalpy of ionization of acetic acid =……………………..cal.

Precautions:
1.Hot water must be added to cold water and that too immediately.
2.The temperature should be accurately recorded.
3.The calorimeter should be completely insulated.
4.The glass should be of high quality and so transparent that temperature can be eas

Viva voce
1. What is Thermochemistry?
2. Define enthalpy of a reaction.
3. What is heat capacity?
4. Define heat of solution.
5. Define heat of neutrilisation.
6. Why heat of neutrilisation of strong acid with strong base is always 13700 cal?
7. Why heat of ionization is negative quantity?
8. Why standard solution of sodium hydroxide cannot be prepared by weighing only?
9. What is primary standard?
10.How you will determine whether neutralization is complete or not?

11.6 SUMMARY
Thermochemistry is a branch of chemistry that qualitatively and quantitatively describes the
energy changes that occur during chemical reactions. Energy is the capacity to do work.
Mechanical work is the amount of energy required to move an object a given distance when
opposed by a force. Thermal energy is due to the random motions of atoms, molecules, or
ions in a substance. The temperature of an object is a measure of the amount of thermal

UTTARAKHAND OPEN UNIVERSITY Page 120

LABORATORY COURSE-I BSCCH- 104

energy it contains. Heat (q) is the transfer of thermal energy from a hotter object to a cooler
one. Energy can take many forms; most are different varieties of potential energy (PE),
energy caused by the relative position or orientation of an object. Kinetic energy (KE) is
the energy an object possesses due to its motion. The most common units of energy are the
joule (J), defined as 1 (kg·m2)/s2, and the calorie, defined as the amount of energy needed
to raise the temperature of 1 g of water by 1°C (1 cal = 4.184 J).

REFERENCES:
1. Practical Chemistry by D. N. Bajpai, O P Pandey & S Giri, S Chand publication.
2. Advanced Practical Organic Chemistry by N K Vishnoi Vikas Publication.

3.Comprehensive Practical Organic Chemistry by V.K Ahluwalia and sunita Dhingra.

4.Text Book of Organic Practical Chemistry, A.I. Vogel.

5. Practical Physical Chemistry, J.B. Yadav.

UTTARAKHAND OPEN UNIVERSITY Page 121