B SC Practical Chemistry Gugale PDF

A Book Of
PRACTICAL
CHEMISTRY
T.Y.B.Sc. Chemistry : CH-347, CH-348, CH-349
As Per New Revised Syllabus of Savitribai Phule Pune University
With Effect from June 2015
Dr. G. S. Gugale
Head & Associate Professor,
Dept. of Chemistry,
H. V. Desai College, PUNE
Dr. A. V. Nagawade Dr. R. A. Pawar

Associate Professor, Dept. of Chemistry, Associate Professor, Dept. of Chemistry
Ahmednagar College, Baburaoji Gholap College,
AHMEDNAGAR. Sangvi, PUNE.
Dr. S. S. Jadhav Dr. V. D. Bobade

Vice-Principal, Head & Associate Professor, Associate Professor, Dept. of Chemistry,
New Arts, Commerce and Science College, H.P.T. Arts, R.Y.K. Science College,
AHMEDNAGAR. NASHIK.
Dr. A. D. Natu Dr. D. R. Thube

Ex. Head, Dept. of Chemistry, Head, PG Dept. of Chemistry,
Abasaheb Garware College, New Arts, Commerce & Science College,
PUNE. Parner, AHMEDNAGAR.
Dr. P. C. Mhaske Dr. L. K. Nikam

Associate Professor, Associate Professor, Dept. of Chemistry,
Dept. of Chemistry Baburaoji Gholap College,
S. P. College, PUNE. Sangvi, PUNE.
Price ` 240.00
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T.Y.B.Sc. : Practical Chemistry ISBN 978-93-51645-84-9
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Preface …
It gives us an immense pleasure to place this “Text Book of Practical Chemistry” in

the hands of T.Y.B.Sc. students. The Book has been written according to the revised
semester pattern of Savitribai Phule Pune University implemented from June 2015.
The book is divided into three sections : (i) Physical, (ii) Inorganic, (iii) Organic
Chemistry Practicals. An attempt is made to give appropriate theoretical background of
each experiment. Procedures, observation tables and calculations are made more simple.
At the end of each experiment, viva-voce questions are given for practice.
All the experiments are written keeping in view the specification of learning
objectives. Micro techniques, double burette methods are adopted wherever possible.
Sincere efforts are made to make the practicals more simple.
We feel that the book will be very useful to the students during their regular
practicals as well as at the time of examination.
We are thankful to Mr. Dineshbhai Furia and Mr. Jignesh Furia for taking keen
interest in publishing this book.
We are also thankful to staff of Nirali Prakashan especially, Mr. Ilyas Shaikh, Mr. Kiran
Velankar and Mrs. Anjali Muley for completing this book on time.
We are also thankful to Marketing staff especially, Mr. Nilesh Deshmukh and others
for coordinating the matter well in time.
Suggestions for improving the book will be highly appreciated.
Authors
Contents …
Physical Chemistry Practicals
CH - 347
Group A
1. Chemical Kinetics (Any Five)
1. To study the effect of concentration of the reactants on the rate of …7
hydrolysis of an ester.
2. To compare the relative strength of HCl and H2SO4 by studying the kinetics …9
of hydrolysis of an ester.
3. To compare the relative strength of HCl and H2SO4 by studying the kinetics … 12
of inversion of cane sugar using Polarimeter.
4. To study the kinetics of iodination of acetone. … 17
5. To determine the first order velocity constant of the decomposition of … 20
hydrogen peroxide by volume determination of oxygen.
6. To determine the energy of activation of the reaction between potassium … 23
iodide and potassium persulphate.
7. To determine the order of reaction between K2S2O8 and KI by half-life … 27
method.
2. Viscosity
8. To determine the molecular weight of a high polymer by using solutions of … 32
different concentrations.
3. Adsorption :
9. To investigate the adsorption of oxalic acid/acetic acid by activated … 39
charcoal and test the validity of Freundlich/Langmuir isotherm.
4. Phenol-Water System
10. To study the effect of addition of salt on critical solution temperature of … 43
phenol-water system.
5. Transport Number
11. To determine the transport number of cation by moving boundary method. … 47
6. Refractometry (Any Two)
1. To determine the specific refractivities of the given liquids A and B and … 55
their mixture and hence determine the percentage composition of their
mixture C.
2. To determine the molecular refractivity of the given liquids A, B, C and D. … 57
3. To determine the molar refraction of homologues methyl, ethyl and propyl … 59
alcohol and show the constancy contribution to the molar refraction by
−CH2 group.
Group B
1. Colorimetry (Any Two)
1. Determination of λmax and concentration of unknown solution of KMnO4 in … 63
2 N H2SO4.
2. Determination of λmax and concentration of unknown solution of CuSO4. … 64
3. To titrate Cu2+ ions with EDTA photometrically. … 68
4. To determine the indicator constant of methyl red indicator. … 70
2. Potentiometry (Any Three)
1. To prepare standard 0.2 M Na2HPO4 and 0.1 M citric acid solution, hence … 80
prepare four different buffer solutions using them. Determine the pKa value
of these and unknown solutions.
2. To determine the concentrations of strong acid and weak acid present in the … 83
mixture by titrating with strong base.
3. To determine the formal redox potential of Fe2+/Fe3+ system … 86
potentiometrically.
4. To determine the amount of NaCl in the given solution by potentiometric … 90
titration against silver nitrate.
5. To determine the amount of Cl− and Br− from the given halide mixture by … 93
titrating with silver nitrate solution.
3. pH Metry (Any Two)
1. To determine the degree of hydrolysis of aniline hydrochloride. … 101
2. To determine the pKa value of given weak acid by pH-metric titration with … 103
strong base.
3. To determine the dissociation constant of oxalic acid by pH-metric titration … 105
with strong base.
4. To determine pH of various mixtures of sodium acetate and acetic acid in … 108
aqueous solution and hence to find the dissociation of acetic acid.
4. Radioactivity (Any One)
1. To determine plateau voltage of the given GM counter. … 113
2. To determine the resolving time of GM counter. … 115
3. To determine Emax of beta particles. … 116
5. Conductometry (Any Two)
1. To determine the cell constant of the given cell using 0.01 M KCl solution … 124
and hence determine dissociation constant of a given monobasic weak acid.
2. To estimate the amount of lead present in the given solution of lead nitrate … 128
by conductometric titration with sodium sulphate.
3. To investigate the conductometric titration of any one of the following : … 131
(a) Strong acid against strong base. … 131
(b) Strong acid against weak base. … 132
(c) Strong base against weak acid. … 134
(d) Weak acid against weak base. … 135
Appendices … 139
Inorganic Chemistry Practicals
CH - 348
(A) Gravimetric Estimations (Any Three)
1. Fe as Fe2O3. … 143
2. Nickel as Ni - DMG. … 145
3. Al as Aluminium oxide. … 148
4. Gravimetric estimation of Ba as BaSO4 using homogeneous precipitation … 151
method.
(B) Volumetric Estimations (Any Four)
1. Mn by Volhard’s method. … 154
−
2. Estimation ofNO2 by using KMnO4. … 159
3. Estimation of % purity of given sample of Sodium chloride. … 163
4. Analysis of Brass - Estimation of copper by Iodometry. … 166
5. Fertilizer analysis (PO4)3−. … 171
(C) Inorganic Preparations (Any Four)
1. Preparation of Hexamminenickel(II) chloride, [Ni(NH3)6]Cl2. … 176
2. Preparation of Potassium trioxalatoferrate(III) trihydrate, … 179
K3[Fe(C2O4)3].3H2O.
3. Preparation of Tetraamminecopper(II) sulphate monohydrate, … 182
[Cu(NH3)4]SO4.H2O.
4. Preparation of Manganese(III) acetylacetone [Mn(acac)3]. … 184
5. Preparation of Tris (Thiourea) Copper(I) chloride [Cu(Thiourea)3]Cl. … 186
(D) Colorimetric Estimations (Any Two)
1. Iron by thiocyanate method. … 188
2. Cobalt by using R-nitroso salt method. … 192
3. Titanium by H2O2. … 195
(E) Separation of Binary Mixture of Cations by Column Chromatography … 202
(3 Mixtures)
(One Mixture should be colourless, Zn + Al, Zn + Mg)
OR
(E) Flame Photometry Analysis (Any Three)
1. Estimation of Na by flame photometry by calibration curve method. … 208
2. Estimation by Na by flame photometry by regression method. … 211
3. Estimation of K by flame photometry by calibration curve method. … 212
4. Estimation of K by flame photometry by regression method. … 215
(F) Inorganic Qualitative Analysis
(4 Mixtures including Borates and Phosphates) … 217
Appendices … 238
Organic Chemistry Practicals
CH - 349
(A) Separation of Binary Mixtures and Qualitative Analysis
(Minimum 8 Mixtures)
(a) Solid-Solid (4 Mixtures). … 247
(b) Solid-Liquid (2 Mixtures). … 247
(c) Liquid-Liquid (2 Mixtures). … 249
Atleast one mixture from each of the following should be given : Acid-Base, Acid-Phenol,
Acid-Neutral, Phenol-Base, Phenol-Neutral, Base-Neutral, Neutral-Neutral.
(i) Separation and qualitative analysis of the binary mixtures should be carried out on
micro scale using micro scale bits.
(ii) Name and structure of the separated components of the binary mixture is not
necessary.
(iii) Students are expected to record the Type, Preliminary tests, Physical constants,
Elements and Functional groups only.
(iv) The purified samples of the separated components should be submitted.
(B) Organic Estimations (Any Four)
(1) Estimation of Acetamide. … 265
(2) Estimation of Glucose. … 268
(3) Estimation of Ethyl benzoate. … 271
(4) Determination of molecular weight of monobasic/dibasic organic acids by
volumetric methods. … 274
(C) Organic Preparations (Any Eight)
(1) Preparation of Adipic acid from Cyclohexanone (Oxidation by conc. HNO3) … 279
(2) Benzoquinone from Hydroquinone (Oxidation by KBrO3/K2CrO3) … 280
(3) p-nitroacetanilide from Acetanilide (Nitration) … 282
(4) 2-Naphthyl methyl ether from 2-naphthol (Methylation by DMS, NaOH) … 283
(5) Hippuric acid by Glycine (Benzoylation) … 285
(6) p-iodonitrobenzene from p-nitroaniline (Sandmeyer reaction) … 286
(7) Benzoic acid from Ethyl benzoate (Ester hydrolysis) … 288
(8) p-Bromoacetanilide from Acetanilide (Bromination) … 289
(9) Paracetamol from p-Hydroxyaniline (Acetylation) … 290
(10) Ethyl benzene from Acetophenone (Wolff Kishner reduction) … 292
Appendices … 295
−−−
Course - I
CH-347
PHYSICAL CHEMISTRY
PRACTICALS
1
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Chemical Kinetics
STRUCTURE OF PRACTICAL EXAMINATION
COURSE – I
CH – 347
Physical Chemistry Practicals
Marks
Q.1 One Experiment from Group – A 35
Q.2 One Experiment from Group – B 35
Q.3 Oral 10
2
(GROUP - A)
1…
Chemical Kinetics
(Any Five)
Introduction :
Thermodynamic parameters like free energy, entropy, heat of reaction etc. give an idea
about the direction of chemical reaction. Chemical kinetics deals with measurement of rate
and mechanism of chemical reaction and factors affecting it. All the reactions cannot be
studied at normal laboratory conditions because some of the reactions are so slow that
months or years are required for their completion. The reactions having moderate rates are
studied in ordinary laboratory conditions.
Rate of Reaction :
The rate of a chemical reaction mainly depends on nature, concentration and
temperature of the reactants. Kinetic studies are generally carried out at constant
temperature (except in the determination of energy of activation). A desired composition of
reactants is mixed to start the reaction and reaction is monitored for the decrease in
concentration of reacting substance or the increase in product concentration as a function of
time. The rate of the reaction is change in concentration per unit time of reactants or
products. During the course of reaction, concentration of reactant decreases. The rate of a
chemical reaction is always a positive quantity. Change in the concentration of a reactant is
negative quantity (decrease). Thus when rate is expressed in terms of reactant concentration,
negative sign is used and when concentration of product is used for this purpose, sign is
positive.
The rate of reaction represented by –dC/dt where dC is small change in concentration at
infinitesimally small time interval dt. Negative sign indicates that concentration decreases as
time passes.
Order of reaction : It is the sum of all the exponents to which the concentration terms
are raised in the rate equation. Thus when rate of reaction is given by
dC n n n
− = k ⋅ C1 1 ⋅ C2 2 ⋅ C3 3 …
dt
where, k = constant, and C1, C2, C3 etc. are concentrations of reactants 1, 2, 3, etc. then
order of reaction = n1 + n2 + n3 + …
3
Molecularity of reaction : Molecularity of a reaction is defined as the number of

molecules or atoms of reactant taking part in a reaction.
Pseudo-molecular reaction : Whenever in a reaction order is not equal to molecularity
the reactions are called as pseudo-molecular reactions. Generally we come across
molecularity greater than one but order equal to one, such reactions are called pseudo-
unimolecular reactions.
Zero order reaction : When the rate of reaction is independent of the concentration of
the reactant then it is said to be zero order reaction. The rate expression is
Rate = k where k is a rate constant.
First order reaction : In first order reaction a single molecule reacts to give products.
These are generally decomposition reactions.
A ⎯⎯→ Product
The rate law for first order reaction is
dC
− = k ⋅ CA
dt
Let ‘a’ be the initial concentration in moles/lit of reactant ‘A.’ If ‘x’ moles/lit of ‘A’ react in
time ‘t’ then concentration of unreacted ‘A’ at time ‘t’ will be (a – x) moles/lit.
dC d(a − x)
∴ Rate = − =
dt dt
da dx
= − +
dt dt
da
but − = 0 since ‘a’ is constant
dt
dx
∴ Rate =
dt
According to law of mass action the rate of a reaction is directly proportional to the
concentration of reactant ‘A’ at an instance.
∴ Rate ∝ (a − x)
Combining above two equations,
dx
= k (a − x)
dt
where, k = rate constant
Separating the variables and integrating above equation gives the rate constant k for first
order reaction as
2.303 a
k = log
t a−x
Thus the rate constant can be calculated by determining initial concentration and change
in concentration in the course of reaction. The rate constant can be found by using graphical
method as
4
2.303 a
k = log
t a−x
a k
∴ log = ⋅t
(a − x) 2.303
⎡ a ⎤
This is a straight line equation of the form y = mx with variables ⎢ ⎥ and t.
⎣(a − x)⎦
a
Graph of log against time is a straight line passing through origin having slope.
(a − x)
k
∴ Slope (m) =
2.303
∴ Rate constant, k = 2.303 × slope
Similarly,
⎛ a ⎞ k
log ⎜ ⎟ = 2.303 ⋅ t
⎝a − x⎠
⎛ k ⎞
∴ log a − log (a − x) = ⎜ ⎟⋅t
⎝2.303⎠
⎛ k ⎞
∴ log (a − x) = ⎜− ⎟ ⋅ t + log a
⎝ 2.303⎠
Graph of log (a – x) against time ‘t’ is a straight line with negative slope.
k
Thus, slope = −
2.303
∴ Rate constant, (k) = − 2.303 × Slope
Units of rate constant k are time–1 (min–1 or sec–1).
Second Order Reaction :
In case of second order reaction there are different possibilities :
(1) Two molecules of same substance react to give products. Thus,
2A ⎯→ B + C
(2) One molecule of one substance and one molecule of other substance reacts to give
products
A + B ⎯→ C + D
Again there are two possibilities in this case :
(i) Both the reactants have same initial concentrations or
(ii) The two reactants have different initial concentration.
1. Expression for second order reaction with equal initial concentration
Let the general reaction be
5
A + B ⎯→ C + D
Let ‘a’ be the initial concentration of both the reactants ‘A’ and ‘B’ in moles/lit.
If x moles/lit of A and B react in time t, then concentration of unreacted A and B in time t will
be (a – x) moles/lit.
dx
∴ Rate = = k (a − x)2
dt
where, k = rate constant
∴ The rate constant k for second order reaction is given by,
1 ⎛ x ⎞
k = ⎜ ⎟
a ⋅ t ⎝a − x⎠
2. Expression for second order reaction with unequal initial concentration
Let the general reaction be
A + B ⎯→ Product
Let ‘a’ moles/lit be the initial concentration of ‘A’ and ‘b’ moles/lit be the initial
concentration of ‘B’.
If the part x out of ‘a’ and the part ‘x’ out of ‘b’ are consumed upto time t, then
concentration of unreacted A and B at time t will be (a – x) and (b – x) moles/lit respectively.
dx
∴ Rate = = k (a − x) (b − x)
dt
The rate constant k for second order reaction is given by equation
2.303 b (a − x)
k = log
t (a − b) a (b − x)
This equation can be rearranged to
k (a − b) b ⎛ (a − x) ⎞
t = log + log ⎜ ⎟
2.303 a ⎝(b − x)⎠
(a − x) ⎛k (a − b)⎞ b
∴ log = ⎜ ⎟ t − log a
(b − x) ⎝ 2.303 ⎠
Comparison of this equation with the equation y = mx + c, implies that this equation
represents a straight line.
(a − x)
∴ By plot the graph of log against t.
(b − x)
b
The nature of graph is a straight line with intercept log
a
k (a − b)
Slope =
2.303
2.303 × slope
∴ k =
(a − b)
−1 −1
Units of k are conc time .
6
Activation energy is an important quantity from chemical kinetics. It has been discussed
in experiment six.
Experiment No. 1
Aim :
To study the effect of concentration of reactants on the rate of hydrolysis of an ester.
Apparatus :
Stoppered bottles, burette, 5 ml pipettes, measuring cylinder, beakers, stop watch, water
bath etc.
Chemicals :
Methyl acetate, 0.5 N HCl (or 0.5 N H2SO4), 0.1 N NaOH, phenolphthalein indicator, ice
etc.
Theory :
The hydrolysis of methyl acetate in aqueous solution is very slow and is catalyzed by
strong acids like HCl or H2SO4. The hydrolysis takes place as
[H+]
CH3COOCH3 ⎯⎯→ CH3COOH + CH3OH
In this reaction, concentration of water is very high and practically remains constant
relative to methyl acetate. Therefore, the rate of reaction is determined by concentration of
methyl acetate alone. This is an example of pseudo-unimolecular reaction. The rate of this
reaction is given by
dx
= k ⋅ [CH3COOCH3]
dt
The rate constant for the first order reaction is
2.303 a
k = log
t a−x
Since acetic acid is formed during the reaction, its concentration and hence the progress
of reaction can be studied by titrating known volume of the reaction mixture with standard
alkali at suitable interval of time from the start of reaction.
Procedure :
Perform the experiment in two sets.
Set I : 5 ml methyl acetate + 100 ml 0.5 N HCl
1. Take 5 ml of methyl acetate using pipette and 100 ml 0.5 N HCl in two separate clean
and dry bottles and stopper them. Place the bottles in water bath to attain the
uniform temperature.
2. Rinse and fill a clean burette with 0.1 N NaOH solution upto the zero mark.
3. Take few pieces of crushed ice or around 40 ml ice cold water in a conical flask and
add 2 - 3 drops of phenolphthalein indicator to it.
7
4. After 10 to 15 minutes the liquids will have assumed the temperature of bath, add
HCl solution to methyl acetate (1st bottle) and shake the reaction mixture well. Start
the stop watch and note the time of mixing as zero time.
5. Immediately pipette out 5 ml of reaction mixture into a conical flask containing ice
cold water. Stopper the bottle again.
6. Titrate the reaction mixture in the conical flask against 0.1 N NaOH and record the
titration reading (T0), when faint pink colour appears and persist for 30 sec. to the
solution.
7. Shake the reaction mixture from time to time and titrate the 5 ml of reaction mixture
with NaOH at the successive intervals of 10, 20, 30, 40 and 50 minutes, (Tt).
8. Similarly carry out the experiment for set II in the same manner as in the set I. The
only difference in set two is the use of 10 ml of methyl acetate in place of 5 ml.
9. Infinite time readings : Take 25 ml of the reaction mixture in a flask. Cork it and
keep in water bath at around 500°C temperature, for 90 minutes to complete the
hydrolysis. Finally, titrate 5 ml of it against 0.1 N NaOH and record the readings as T∞.
Set II : 10 ml methyl acetate + 100 ml 0.5 N HCl
Observations :
For set I : 5 ml methyl acetate + 100 ml 0.5 N HCl
Initial reading (T0) = ……..ml
Infinite reading (T∞) = ……..ml
∴ Initial concentration of methyl acetate
a = T∞ – T0 = ………..ml
Titration
Time a
reading Tt – T 0 = x T∞ – Tt = a – x log a – x log k/min
(t) min a−x
(Tt) ml
10
20
30
40
50
Prepare similar observation table for set II.
Calculations :
(a) Rate constant (k) by calculations :
For first order reaction
2.303 a
k = log
t a−x
where, a = Initial concentration of methyl acetate
8
a – x = Amount of methyl acetate remaining unreacted at time t

Calculate the values of k for first and second set at 10, 20, 30, 40 and 50 minutes time
interval. Calculate mean value of k for each set.
(b) Rate constant (k) by graph :
(i) Plot the graph of log (a – x) against t.
−k log (a - x)
Slope =
2.303
∴ k = − 2.303 × slope
time/min
Fig. 1: log (a − x) vs. t
a
(ii) Plot the graph of log against t.
(a − x)
a
k log
(a - x)
Slope =
2.303
∴ k = 2.303 × slope time/min
a
Fig. 2: log vs. t
Q−x
Straight line nature of both the graphs indicates that the reaction of hydrolysis of methyl
acetate is first order one.
Result Table :
Set I k (min–1) Set II k (min–1)
By calculations By graph By calculations By graph
Conclusion :
k value for first and second set are nearly constant. This shows that the rate constant is
independent of initial concentration of reactant.
Experiment No. 2
Aim :
9
To compare the relative strength of HCl and H2SO4 by studying the kinetics of hydrolysis of
an ester.
Chemicals :
Methyl acetate 0.5 N HCl, 0.5 N H2SO4, 0.1 N NaOH, phenolphthalein indicator, ice cold
water etc.
Apparatus :
Stoppered bottles, pipettes, burette, measuring cylinder, beakers, stop watch, water bath
etc.
Theory :
The hydrolysis of ester is catalyzed by H+ ions.
H+
CH3COOCH3 + H2O ⎯→ CH3COOH + CH3OH
Therefore, the rate of hydrolysis increases with increase in concentration of H+ ions. If the
hydrolysis is carried out in presence of hydrochloric acid and of sulphuric acid independently,
with their equal concentrations, the rate constants for hydrolysis, kHCl and kH2SO4, depend on
the degree of dissociation of HCl and H2SO4.
The rate of hydrolysis using either of the catalyst is proportional to the concentration of
methyl acetate (reactant) and in turn to the concentration of acetic acid (product).
Experimental measurement of the rate of reaction (kHCl and kH2SO4) can be studied by
determining the amount of acetic acid formed in the course of reaction. Amount or
concentration of acetic acid formed at different time intervals can be easily determined by
titrating the definite amount of reaction mixture with standard alkali. Hence, the relative
strength can be calculated as
kHCl
Relative strength =
kH2SO4
Thus the strength of the two acids can be compared by kinetic measurements.
Procedure :
Set I : 5 ml methyl acetate + 100 ml 0.5 N HCl :
1. Take 100 ml 0.5 N HCl in a clean and dry stoppered bottle (bottle 1). In another
stoppered bottle take 5 ml methyl acetate (bottle 2).
2. Keep the bottles in a water bath for 10-15 minutes to attain the constant
temperature.
3. Fill the burette with 0.1 N NaOH solution upto the zero mark.
4. Take few pieces of crushed ice or around 30 ml ice cold water in a conical flask and
add to it 2-3 drops of phenolphthalein indicator.
5. Transfer the 100 ml 0.5 N HCl in bottle 1 to bottle 2 containing 5 ml methyl acetate.
Shake the mixture and start the stop watch. Note the time of mixing as zero time.
10
6. Immediately pipette out 5 ml reaction mixture in titration flask containing ice and
phenolphthalein indicator. (Place the bottle in water bath).
7. Shake it well and titrate with 0.1 N NaOH till faint pink colour appears and persists for
30 seconds to the solution.
8. Record the titration reading as T0.
9. Shake the reaction mixture from time to time and titrate 5 ml of reaction mixture
similarly at the successive intervals of 10, 20, 30, 40 and 50 minutes. Record the
titration readings as Tt.
10. Infinity reading (T∞) : Take 25 ml of the reaction mixture in a flask. Cork it and keep
in water bath at around 50°C temperature, for 10 minutes to complete the hydrolysis.
Finally, titrate 5 ml of it against 0.1 N NaOH and record the readings as T∞.
11. Similarly carry out the experiment for set II in the same manner as the set I. The only
difference in set two is the use of H2SO4 in place of HCl.
Set II : 5 ml methyl acetate + 100 ml 0.5 N HCl :
Observations :
Set I : 5 ml methyl acetate + 100 ml 0.5 N HCl
Initial reading (T0) = ……...ml
Infinity reading (T∞) = ………ml
Initial concentration of methyl acetate a = T∞ – T0 = ……..ml
Titration
Time (t) T∞ – T t a
reading Tt – T 0 = x log a – x log k (min–1)
min = a–x a−x
(Tt) ml
10
20
30
40
50
Prepare similar observation table for set II.

Calculations :
1. Rate constant k by calculations for first order reaction :
2.303 a
k = log
t (a − x)
where, a = Initial concentration of methyl acetate
11
(a – x) = Amount of methyl acetate remaining unreacted at time t.

Calculate the values of k for first and second set at 10, 20, 30, 40 and 50 min. intervals.
Calculate mean value of k for each set.
kHCl
∴ Relative strength =
kH2SO4
2. Rate constant (k) by graphical method :
(i) Plot the graph of log (a – x) against time for both the sets, straight line nature of
graph shows that reaction is first order.
−k
Slope =
2.303
log (a - x)
∴ −k = 2.303 × slope
time/min
Fig. 1: log (a − x) vs. t
(ii) Plot the graph of log [a/(a – x)] against time, the nature of graph is a straight line
passing through the origin.
k
Slope =
2.303
log a
∴ k = 2.303 × slope (a - x)
Find out kHCl and kH2SO4 from both the

graphs. time/min
a
Fig. 2: log vs. t
a−x
Result Table :
Sr. No. Description By calculations By graph
–1
1. Rate constant (kHCl) ……… min ……… min–1
2. Rate constant (kH2SO4) ……… min–1 ……… min–1
⎛ kHCl ⎞ ……… ………
3. Relative strength = ⎜ ⎟
⎝kH2SO4⎠
Conclusion :
For equal concentration of HCl and H2SO4, hydrochloric acid is more dissociated than
sulphuric acid.
kHCl
∴ > 1
kH2SO4
12
Experiment No. 3
Aim :
To determine the relative strength of HCl and H2SO4 by studying the kinetics of inversion of
cane sugar using polarimetry.
Apparatus :
Polarimeter, sodium lamp, stop watch, conical flask, etc.
Chemicals :
Hydrochloric acid (1 N), sulphuric acid (1 N), distilled water, sugar etc.
Theory :
Substances like cane sugar that are capable of rotating the plane polarized light are
optically active and the phenomenon is called Optical Activity. Substances that rotate the
plane of polarized light to the right are called dextro rotatory and those that rotate it to the
left are called laevo rotatory. In fact, one name for glucose, dextrose, refers to the fact that it
causes plane of polarization to rotate to the right or dexter side (clockwise). Similarly,
levulose, commonly known as fructose, causes the plane of polarization to rotate to the left
(counter-clockwise). Fructose is even more strongly laevo rotatory than glucose is dextro
rotatory. Hydrolysis of cane sugar is termed as “inversion of cane sugar” since with the
progress in hydrolysis, the sign of rotation changes from positive to negative (the conversion
causes the direction of rotation to "invert" from right to left or dextro to laevo). The amount
by which the light is rotated is known as the angle of rotation. The fall in optical rotation is
proportional to the amount of fructose formed and the amount of cane sugar hydrolyzed.
Polarimeter is the instrument used to measure the angle of rotation of a plane polarized
light. Sucrose molecule has number of asymmetric carbon atoms and can be hydrolyzed to
give glucose and fructose.
H+
C12H22O11 + H2O ⎯⎯→ C6H12O6 + C6H12O6
Cane sugar Glucose Fructose
+
The hydrolysis of cane sugar is catalyzed by H ions. Therefore, the rate of hydrolysis
increases with increase in concentration of H+ ions. If the hydrolysis is carried out in presence
of hydrochloric acid and of sulphuric acid independently, with their equal concentration, the
rate constants for hydrolysis, kHCl and kH2SO4, depend on degree of dissociation of HCl and
H2SO4.
Experimental measurement of change in optical rotation with the inversion of cane sugar
can be used to determine the rate constants kHCl and kH2SO4. Hence, the relative strength can
be calculated as
kHCl
Relative strength =
kH2SO4
13
Polarimeter :
A simple polarimeter consists of a long tube with flat glass ends, into which the sample is
placed. At each end of the tube is a Nicol prism, one is called polarizer and the other
analyzer. Polarizer is kept fixed and converts the monochromatic light into plane polarized
beam. The angle of rotation of plane polarized beam by the sample is measured by passing
monochromatic light through polarizer. This beam gets rotated as it passes through the
sample already filled in the polarimeter tube. The sample is usually prepared as a solution
where the optically active substance is dissolved in an optically inactive chemical such as
distilled water or methanol. After passing through the sample the analyzer is rotated
manually. When the analyzer is rotated to the proper angle, the maximum amount of light
will pass through and shine onto a detector (telescope).
o
0
o ,E
+90
o
90
Polarimeter tube, T o
180
Analyzer, A
Unpolarimeter light
Polarized
light
Fixed polarizer, P
Light source, S
Fig. 1
The principle of the set-up of the polarimeter consists of the light source (S), polarizer (P),
analyzer (A) with angle measuring scale and eyepiece (E). Two Nicol prisms are placed
between the source of monochromatic light, S (usually sodium lamp) and the eyepiece. Light
passes through the polarizer and gets plane polarized (vibrations are restricted to one plane
only). This plane polarized light then passes through the second Nicol prism, A, the analyzer
and reaches the eye. The field of view is observed through the telescope eyepiece (E).
However, when the axis of the analyzer is perpendicular to that of the polarizer, no light
reaches the eye. The polarizer and analyzer are arranged in such a way that no light reaches
the eye. A tube T filled with cane sugar solution is placed between the two prisms. Some light
14
can be now seen through the telescope eyepiece. The analyzer should be rotated so that
once again no light reaches the eye.
Note that some light could be seen when sugar solution was placed between the prisms
whose axes were perpendicular to each other and no light was visible originally. So what
made this light visible on the other end when neither of the two prisms had been moved ?
Light is visible only if the plane of polarization has been rotated by some way. Thus the plane
of polarization must have been rotated by cane sugar solution.
Procedure :
1. Prepare 20% sugar solution by dissolving 20 gram of sugar in about 40 ml distilled
water dilute it to 100 ml using volumetric flask. Filter the solution.
2. Take two different clean and dry conical flasks. Place 25 ml of sugar solution in one
and 25 ml of 1N HCl in other. Keep them in a thermostat at room temperature.
3. Clean and dry the polarimeter tube.
4. Fill the polarimeter tube with distilled water. Ensure that no air bubble is trapped
inside the tube.
5. Observe the field (the light passed through analyzer) through the eyepiece. The
circular field is seen either with uniform illumination or with two halves illuminated
distinctly. Rotate the analyzer and adjust it for equally illuminated halves. This reading
is added or subtracted subsequently as the case may be.
6. Make polarimeter tube empty by removing water from it.
7. Mix the two solutions in the bottles and shake well. Transfer immediately the reaction
mixture in the polarimeter tube. Keep the tube in the polarimeter jacket and close it.
Record the mixing time.
8. Rotate the analyzer and adjust it for equally illuminated halves. Note this reading as
initial or zero time reading, α0.
9. Take similar readings at the intervals of 10, 20, 30, 40 and 50 minutes and record
them as αt.
10. Infinity reading : The reaction mixture is heated at about 60 to 70°C for half an hour
for reaction to complete. It is then cooled and poured into the polarimeter tube to
measure the angle of rotation. This reading is α∞.
11. Repeat the experiment in the same manner by using 1 N H2SO4 in place of HCl.
Observation Table :
Set I = 25 ml 20% sugar solution + 25 ml 1N HCl
Initial reading (α0) =
Infinity reading (α∞) =
∴ Initial concentration (a) = α∞ – α0 = ……….
15
Time in Angle of α0 – α∞
α = α0 – αt a – x = αt – α∞ log (αt – α∞) log
min. rotation ‘αt’ αt – α∞
10
20
30
40
50
Set II : 25 ml sugar solution + 25 ml 1 N H2SO4
Prepare similar observation table for Set II.
Calculations :
(a) k by calculations :
2.303 a
k = log
t a−x
2.303 α0 − α∞
k = log
t αt − α∞
where, a, the initial concentration of sugar = α0 – α∞
a – x, the concentration of sugar at time t = αt – α∞
angle of rotation at zero time t = αt − α∞
angle of rotation at time t = αt
angle of rotation at infinite time = α∞
Calculate the rate constant, kHCl, for Set I.
Similarly calculate the rate constant, kH2SO4 for Set II.
kHCl
kH2SO4
(b) k by graph :
(i) Plot the graph of log (a − x) against t.
The nature of the graph is a straight line with
negative slope. log (at - a¥)
−k
Slope =
2.303
Time (min)
∴ k = −2.303 × slope Fig. 2
α0 − α∞
(ii) Plot the graph of log against time. Nature of graph is a straight line passing
αt − α∞
through origin.
16
k
Slope =
2.303
a0-a¥
∴ k = 2.303 × slope log a -a
t ¥
Calculate kHCl and kH2SO4 from slope of both

the graphs. Time (min)
kHCl Fig. 3
kH2SO4
Result Table :
Sr. No. Description By calculations By graph
–1
1. (kHCl) ……… min ……… min–1
2. (kH2SO4) ……… min–1 ……… min–1
3. kHCl ……… ………
Relative strength =
kH2SO4
Conclusion :
Since experimentally it is verified that relative strength is greater than one, i.e.
kHCl
> 1
kH2SO4
it indicates that hydrochloric and dissociates more than sulphuric acid under the identical set
of conditions.
Experiment No. 4
Aim :
To study the kinetics of iodination of acetone.
Apparatus :
Stoppered bottles (five), burette, pipettes, stop watch, conical flask, etc.
Chemicals :
1 M H2SO4, acetone, 0.1 M I2 in 10% KI, 1 M sodium acetate, 0.01 M sodium thiosulphate.
Theory :
Iodine reacts with acetone in the presence of acid to form iodoacetone and hydrogen
iodide.
O + O
H + -
+ I2 + H + I
C C
H3C CH3 H3C CH2I
acetone iodoacetone
17
The reaction is catalyzed by H+ ions and the rate of reaction is found to be independent
of iodine concentration.
−d[I2]
Rate = = k' [CH3COCH3]a [H+]b [I2]c
dt
Since, a very important characteristic of this reaction is that it turns out to be zero order
with respect to iodine (i.e. c = 0). This means that the rate of the reaction does not depend
on [I2] at all as [I2]0 = 1, no matter what the value of [I2] is as long as it is NOT zero. This is
consistent with the mechanism.
+
H
O O
+
H3C C CH3 + H H3C C CH3
Acetone Ion
+ OH
H
O +
+ H2O H3C C CH2 + H3O
H3C C CH3
Ion Enol
OH O I
+ -
H3C C CH2 + I2 H3C C CH2 + H + I
Enol Iodoacetone
Since the reaction is said to be zero order with respect to iodine concentration the rate
law simplifies to the equation
Rate = k' [(CH3)2C=O]a [H+]b
If acetone and acid is taken in large excess relative to [I2], then change in their
concentration will be minimal during the course of reaction. This means [CH3COCH3] and [H+]
will remain (essentially) constant. Therefore, the rate law can be written as :
−d[I2]
Rate = = k' [(CH3)2C=O]a [H+]b = constant = k
dt
A plot of [I2] versus time is relatively a straight line whose slope is the reaction rate equal
to k.
18
0.6
[I2]o
0.5
0.4
[I2] Slope = k
0.3
0.2
0.1 Slope = k
0
0 10 20 30
Time (min)
Fig. 1
Decrease in concentration of iodine in the course of reaction can be used for
determination of the order with respect to iodine. Experimentally unreacted iodine is titrated
against standard sodium thiosulphate solution using starch as a indicator. Sodium acetate or
sodium bicarbonate can be used to stop the reaction while performing the titration.
Procedure :
1. Prepare four sets of mixture solutions from stock in four stoppered bottles as given
below.
Set I II III IV
Acetone (ml) 10 10 15 15
Water (ml) 70 65 55 50
Sulphuric acid (ml) 10 10 10 10
2. Take about 100 ml iodine solution in another bottle say bottle V. Keep all these
bottles in water bath to attain uniform temperature.
3. Fill a burette with 0.01 M sodium thiosulphate solution.
4. Pipette out 10 ml of sodium acetate solution each in 4 to 5 conical flasks and keep
them ready for titrating reaction mixture.
5. After around 10 minutes add 10 ml of iodine solution from bottle by means of
pipette to bottle no. 1 and start the stop watch.
6. After three minutes, pipette out 10 ml of the reaction mixture in a conical flask
containing
10 ml of sodium acetate solution.
7. Titrate the reaction mixture against 0.01 M sodium thiosulphate solution. Add 2 ml of
starch indicator just before the solution becomes faint yellow. At the end point
solution turns blue to colourless.
8. Shake the reaction mixture from time to time and similarly titrate 10 ml of it at
successive intervals of 6, 9, 12, 15, 18 and 21 minutes. Note the titration readings in
the observation table.
19
9. Similarly carry out the reaction between acetone solution in bottle no. II, III and IV
with 15 ml, 20 ml and 25 ml of iodine solution in bottle no. V respectively and repeat
the titration procedure as mentioned in steps 4 to 8 above.
Observation Table :
Burette reading in ml
Time in min.
Set I Set II Set III Set IV
3
6
9
12
15
18
21
Calculations :
Plot the graph of titration reading against time for all four sets.
Burette reading
(ml)
I
II
III
IV
Time (min)
Fig. 2
Straight line graph with negative slope indicates that the rate of reaction is independent
of the concentration of iodine.
∴ k = − slope
Conclusion :
All the graphs are straight (and parallel) lines with same slopes (k). It proves that order of
this reaction is zero with respect to reactant iodine.
Experiment No. 5
Aim :
20
To determine the first order velocity constant of decomposition of hydrogen peroxide by

volume determination of liberated oxygen.
Apparatus :
Gas burette, conical flask, magnetic stirrer, rubber tubings, etc.
Chemicals :
0.1 M KI, 3% H2O2 solution etc.
Theory :
Hydrogen peroxide decomposes into oxygen and water spontaneously. It is an exothermic
reaction with heat of reaction ΔH° = −98.2 kJ mol−1. Rate of decomposition is dependent on
the temperature and concentration of the peroxide as well as on the pH of the reaction
medium. Decomposition occurs more rapidly in alkali. In acidic medium this reaction follows
second order kinetics, whereas in neutral medium it exhibits first order kinetics.
In neutral medium, decomposition is represented as
2H2O2 ⎯→ 2H2O2 + O2 ↑
Besides transition metals, potassium iodide catalyzes this reaction greatly.
Since the reaction is catalyzed by I− ions, the rate of reaction increases with increase in
concentration of I− ions. Elementary steps for this reaction are :
(i) H2O2 + I− ⎯→ H2O2 + IO− (slow step)
− −
(ii) IO ⎯→ I + 1/2 O2 (fast step)
H2O2 ⎯→ H2O + 1/2 O2 (overall reaction)
The progress and hence the kinetics of the reaction can be studied by measuring the
volume of oxygen liberated at different time intervals.
B
E
C
A
F
Fig. 1: Experimental set up for measurement of volume of oxygen

liberated in the reaction
Procedure :
Set I : 10 ml, 0.1 M KI + 15 ml water + 5 ml 3% H2O2
21
1. Take 10 ml of KI (0.1N) solution in the reaction flask D. Add 15 ml distilled water to it,
insert a magnetic needle and cork gently. Mount the flask on the stirrer.
2. Connect the gas burette B and burette A using a rubber tube.
3. Fill the burette with tap water and adjust the water level in gas burette B to zero level
mark by moving burette A upward down.
4. Connect open end of gas burette to reaction flask D using a glass and a rubber tube.
5. Add 5 ml 3% H2O2 solution to reaction flask and immediately cork it. Start the stop
watch. Note this time as zero time.
6. Start the stirrer. Care should be taken that oxygen leakage does not occur during the
experiment.
7. Equalize the two levels of water in two burettes after 3 minutes and measure the
volume of oxygen liberated in gas burette B. Record this volume in observation table.
8. Similarly record the volume of oxygen liberated as Vt at different time intervals
6, 9, 12, 15, 18, 21 and 24 minutes.
9. No more oxygen will be liberated when the reaction is completed, this volume of
oxygen is called as V∞.
Observations :
(i) Initial reading (V0) = ……ml
(ii) Infinity reading (V∞) = ……ml
a = V∞ – V0 = ……ml
Obs. Time t (min) Volume of (a – x) log (V∞ – Vt) k (min–1)
No. oxygen collected = V∞ – V t
Vt (ml)
1 3
2 6
3 9
4 12
5 15
6 18
7 21
8 24
Set II : 20 ml, 0.1M KI + 5 ml distilled water + 5 ml 3% H2O2
Repeat the same procedure as in Set I for the Set II and write the observations in
observation table for Set II.
Calculations :
22
1. Rate constant (k) by calculations :

The first order velocity constant is given by
equation- log (at - a¥)
2.303 V∞ − V0
k = log
t V∞ − Vt
Time (min)
2.303 a
k = log Fig. 2
t a−x
Calculate the value of k for various time intervals for both the sets. Also calculate average
rate constant (k) for each set.
2. Rate constant by graph :
Plot the graph of log (V∞ − Vt) against time t.
Nature of the graph is a straight line with negative slope.
−k
∴ Slope =
2.303
∴ k = −2.303 × slope
Calculate k from the slope for both the sets.
Result Table :
Description Set By calculations By graph
Velocity constant k I
(min–1) II
Conclusion :
Constant values of k and straight line nature of the graph proves that the reaction is of
first order.
Experiment No. 6
Aim :
To determine the energy of activation of the reaction between potassium iodide and
potassium persulphate.
Apparatus :
Stoppered bottles, burette, pipettes, stop-watch, measuring cylinder, thermostat, etc.
Chemicals :
0.1N K2S2O8, 0.1N KI, 0.002 N Na2S2O3, starch indicator, crushed ice or ice cold water etc.
Theory :
Activation energy and the pre-exponential factor A are two quantities of great
importance in kinetics. Most chemical reactions are thermally activated; their rate increases
23
with temperature. Theories of reaction rates predict that not all the colliding molecules of
reacting substances undergo chemical change. An energy barrier must be overcome in order
to transform reactants into products. This barrier is referred to as the activation energy for the
reaction. The fraction of reacting molecules that has an energy that exceeds the activation
energy is increased by increasing the temperature. This allows the reaction to proceed faster.
Thus, energy of activation is the minimum amount of energy required by the reactant
molecules to undergo chemical reaction and form the product.
The reaction between potassium persulphate and potassium iodide is a second order
reaction. The overall reaction is
K2S2O8 + 2KI ⎯→ 2K2SO4 + I2
−2 −2
or S2O8 + 2I− ⎯→ 2SO4 + I2
The reaction is first order with respect to each reactant and hence second order overall.
The reason is that the reaction occurs in two steps as represented below.
−2
(i) S2O8 + I− ⎯→ S2O8I3−
−2 2−
(ii) S2O8I3− + I− ⎯→ 2SO4 + I2
The progress of reaction can be studied by titrating the liberated iodine against the
0.002 N sodium thiosulphate using starch as an indicator.
The rate constant for the second order reaction with unequal initial concentration can be
calculated by using equation-
2.303 b (a − x)
k = log
t (a − b) a (b − x)
where a and b are initial concentrations of reactants K2S2O8 and KI, (a – x) and (b – x) are their
concentrations at time t. The above expression can be written as
2.303 ⎛ (a − x) b⎞
k = ⎜log (b − x) + log a ⎟
t (a − b) ⎝ ⎠
k × t (a − b) (a − x) b
∴ = log + log
2.303 (b − x) a
(a − x) ⎛k (a − b)⎞ b
∴ log = ⎜ ⎟ t − log a
(b − x) ⎝ 2.303 ⎠
This equation is equivalent to equation y = mx + c and thus represents a straight line.
(a − x)
If the graph of log against time ‘t’ is plotted, a straight line graph with negative
(b − x)
slope is obtained.
k (a − b)
∴ Slope =
2.303
24
2.303 × slope
∴ k =
(a −b)
Thus rate constant k can be obtained graphically.
Rate of reaction depends on temperature. Rate constants can be determined at two
different temperatures experimentally. The relationship between rate constants k1 and k2 at
temperatures T1 and T2 is given by Arrhenius equation as –
k2 Ea ⎛T2 − T1⎞
log
k1
= ⎜ ⎟
2.303 R ⎝ T1T2 ⎠
where, Ea = Energy of activation
R = Molar gas constant
Procedure :
Perform the experiment in two sets for two different temperatures.
Set I : Reaction at lower temperature (T1 K) :
1. Take 20 ml 0.1 N KI and 20 ml distilled water in a clean and stoppered bottle and
10 ml 0.1 N K2S2O8 solution and 30 ml distilled water in another stoppered bottle.
Keep these two bottles in water bath for 10-15 minutes to attain constant
temperature. Record the temperature (T°C) of the water bath.
2. Fill a clean burette with 0.002 N sodium thiosulphate.
3. When the two solutions have attained the same temperature, mix them to start the
reaction. Start the stop watch and note the mixing time as zero time.
4. Keep the reaction mixture in thermostat and shake it from time to time.
5. Keep a titration flask ready with around 30 ml crushed ice or ice-cold water.
6. Withdraw 10 ml of reaction mixture after 10 minutes from the start by pipette and
transfer it to conical flask containing ice. Titrate the liberated iodine against sodium
thiosulphate solution using starch indicator. Starch should be added near the
equivalence point i.e. when the reaction mixture becomes faint yellow during
titration.
7. Similarly titrate the reaction mixture at the interval of every 5 minutes.
8. Take seven such readings.
Observation Table :
Temperature of thermostat (t1) = …….. °C
Temperature (T1) = 273 + t1 = …… K
Time ‘t’ Volume of 0.002 N (a – x) (b – x) a−x k1 (min–1)

log
(min) Na2S2O3 (ml) (ml) (ml) b−x
25
10
15
20
25
30
35
40
Set II : Reaction at higher temperature (t1 + 10°C) :

1. Maintain the temperature of the water bath at t1 + 10°C. Record the temperature as
t2°C.
2. Repeat all the steps given in Set I in this set also. The only difference in two sets is the
temperature of water bath.
3. Prepare the separate observation table for this set.
Calculations :
1. Calculation of initial concentration of KI, (‘a’) :
Total volume of reaction mixture = 80 ml.
[(20 ml 0.1 N KI + 20 ml water) + (10 ml 0.1N K2S2O8 + 30 ml water)]
The resultant normality of KI in reaction mixture can be calculated as -
KI ≡ Reaction mixture
N1V1 = N2V2
0.1 × 2.0 = N2 × 80
∴ N2 = 0.025 N
Therefore initial concentration of KI in 10 ml of reaction mixture (in terms of 0.002 N
Na2S2O3) is as,
0.25 × 10
a =
0.002
∴ a = 125 ml
2. Calculation of initial concentration of K2S2O8, (b) :
Total volume of reaction mixture = 80 ml
The resultant normality of K2S2O8 in reaction mixture can be calculated as-
K2S2O8 ≡ Reaction mixture
N1V1 = N2V2
∴ 10 × 0.1 = N2 × 80
10 × 0.1
∴ N2 =
80
26
∴ N2 = 0.0125 N
Therefore initial concentration of K2S2O8 in 10 ml of reaction mixture (in terms of 0.002 N
Na2S2O3) is
0.0125 × 10
b =
0.002
∴ b = 62.5 ml
The rate constant k, for second order reaction with unequal initial concentration is
given by
2.303 b (a − x)
k = log
t (a − b) a (b − x)
Calculate the value of k for both the sets at the instances 10, 15, 20, 25, 30, 35 and 40
minutes.
Determine mean value of kI (at temperature T1 K) and kII (at temperature T2 K).
3. Rate constant (k) by graphical method : Set II
(a − x)
Plot the graph of log against time (t).
(b − x) (a-x) Set I
log
The nature of graph is a straight line with slope (b-x)
k (a − b)
Slope =
2.303 Time (min)
2.303 × slope Fig. 1
∴ k =
(a − b)
Thus, find kI at temperature T1 K and kII at temperature T2 K.
4. Calculation of energy of activation :
Energy of activation can be calculated by using Arrhenius equation –
kII Ea ⎡T2 − T1⎤
log
kI
= ⎢ ⎥
2.303 R ⎣ T1T2 ⎦
where T2 > T1
2.303 × R × T1 × T2 kII
∴ Ea = log
(T2 − T1) kI
where, kI is rate constant at temperature T1 and kII is rate constant at temperature T2 °K.
R = Molar gas constant = 1.987 cal degree−1 mole−1
∴ Ea = …….. cal mole−1
= …….. kcal mole−1
Thus, find energy of activation by calculation as well as by graph.
Result Table :
Description By calculations By graph Energy of activation
Rate constant (kI) …. dm3 mol–1 min–1 ….. dm3 mol–1 min–1 …… k ⋅ cal mole–1
at temperature TI K
Rate constant (kII) …. dm3 mol–1 min–1 …. dm3 mol–1 min–1 …… k ⋅ cal mole–1
27
at temperature TII K
Conclusions :
a−x
1. The value of k at a temperature T remains fairly constant and the graph of
b−x
against time t is a straight line. It indicates that reaction follows second order kinetics.
2. Activation energy of this reaction is …….. k⋅cal mole–1.
Experiment No. 7
Aim :
To determine the order of reaction between K2S2O8 and KI by half life method.
Apparatus :
Stoppered bottles, burette, pipette, conical flask, water bath, stop watch etc.
Chemicals :
0.05 N K2S2O8, 0.05 N KI, 0.005 N Na2S8O3, starch indicator, crushed ice etc.
Theory :
The reaction between potassium persulphate and potassium iodide is a second order
reaction.
The overall reaction is
K2S2O8 + 2KI ⎯→ 2K2SO4 + I2
−2 2−
or S2O8 + 2I− ⎯→ 2SO4 + I2
The reaction is first order with respect to each reactant and hence second order overall. It
is a two step reaction as represented below.
2−
(i) S2O8 + I− ⎯→ S2O8I3−
2−
(ii) S2O8I3− + I− ⎯→ 2SO4 + I2
The progress of reaction can be studied by titrating the liberated iodine against 0.002 N
sodium thiosulphate using starch as a indicator.
The rate constant for the second order reaction with equal initial concentration can be
calculated by using equation-
1 x
k2 = min−1 conc−1
t a (a − x)
Half-life period (t1/2) :
The time required for completion of half of the reaction is called the half-life period.
At half-life period t = t1/2, x = a/2.
1 1/2
∴ k2 = ×
t1/2 a (a − a/2)
28
1 1 1
∴ k2 = × =
t1/2 a a × t1/2
For third order reaction,
1
k3 = 2
a × (t1/2)
∴ In general for nth order reaction,
1
kn =
t1/2 × an−1
1
∴ Half-life period (t1/2) =
kn ⋅ an−1
1
∴ t1/2 =
kn ⋅ an−1
For nth order reaction if (t1/2)I and (t1/2)II are the times for half change with initial
concentrations, a1 and a2 then –
1
(t1/2)I = n−1
k2 ⋅ a 1
1
(t1/2)II = n−1
k2 ⋅ a 2
(t1/2)I ⎛a2⎞n−1
∴ = ⎜ ⎟
(t1/2)II ⎝a1⎠
(t1/2)I ⎛a2⎞n−1
∴ log = log ⎜ ⎟
(t1/2)II ⎝a1⎠
(t1/2)I a2
∴ log = (n − 1) log
(t1/2)II a1
log (t1/2)I − log (t1/2)II
∴ (n − 1) =
log a2 − log a1
log (t1/2)I − log (t1/2)II
∴ Order, n = 1 +
log a2 − log a1
This equation enables the experimental determination of order of a reaction. Two sets of
experiment are performed by taking equal initial concentrations of two reactants as a1 in Set I
and a2 in Set II. Half times (t1/2)I and (t1/2)II can be calculated from the rate constants for the
two sets Hence, order can be determined using the above formula.
Procedure :
Set I : 25 ml 0.05 N KI + 25 ml 0.05 N K2S2O8 + 50 ml distilled water :
29
1. Take 25 ml 0.05 N KI and 20 ml distilled water in clean stoppered bottle and 25 ml

0.05 N K2S2O8 and 25 ml distilled water in another stoppered bottle. Keep the bottles
in thermostat or water bath for 10 – 15 minutes to attain constant temperature.
2. Fill the burette with 0.05 N Na2S8O3 solution.
3. When the two solutions have attained the same temperature, mix them to start the
reaction. Start the stop watch and note the mixing time as zero time.
4. Keep the mixture in water bath and shake it from time to time.
5. Keep a titration flask ready with around 30 ml crushed ice or ice-cold water.
6. Withdraw 10 ml of reaction mixture after 10 minutes from the start by pipette and
transfer it to the conical flask containing ice. Titrate the liberated iodine against
sodium thiosulphate solution using starch indicator. Starch should be added near the
equivalence point i.e. when reaction mixture becomes faint yellow during titration.
7. Similarly titrate the reaction mixture at the interval of every 5 minutes.
8. Take seven such readings.
Observation Table :
Time ‘t’ (min) Volume of Na2S8O3 x (ml)
10
15
20
25
30
35
40
Set II : 50 ml 0.05 N KI + 50 ml 0.05 N K2S2O8 :
Repeat the experiment in the same manner as in set I except with the concentrations of
reactants mentioned above. Prepare the separate observation table for Set II.
Calculations :
1. To determine initial concentration (a) :
Set I : 25 ml 0.05 N KI + 25 ml 0.05 N K2S2O8 + 50 ml distilled water :
The two reactants KI and K2S2O8 are having equal initial concentrations. Resultant volume
of the reaction mixture is 100 ml. The resultant molarity of KI and K2S2O8 in the reaction
mixture can be calculated as –
KI (or K2S2O8) ≡ Reaction mixture
N1V1 = N2N2
∴ 0.05 × 25 = N2 × 100
30
0.05 × 25
N2 =
100
∴ N2 = 0.0125 N
∴ Initial concentration of KI or K2S2O8 in 10 ml of reaction mixture in terms of 0.005 N
Na2S8O3 would be
0.0125 × 10
a1 =
0.005
∴ a1 = 25 ml
Set II : 50 ml 0.05 N KI + 50 ml 0.05 N K2S2O8 :
The two reactants KI and K2S2O8 are having equal initial concentrations. Resultant volume
of the reaction mixture is 100 ml. The resultant molarity of KI and K2S2O8 in the reaction
mixture can be calculated as –
KI (or K2S2O8) ≡ Reaction mixture
N1V1 = N2N2
∴ 0.05 × 50 = N2 × 100
0.05 × 50
N2 =
100
∴ N2 = 0.025 N
∴ Initial concentration of KI or K2S2O8 in 10 ml of reaction mixture in terms of
0.005 N Na2S8O3 would be
0.025 × 10
a1 =
0.005
∴ a1 = 50 ml
2. To determine the half-life period of the reaction :
Plot the graph of x (burette reading) against time t for both the sets.
Set II
a0/2
x Set I
a0/2
t1/2 t1/2 time (t)

time
31
Fig. 1 : x vs. t, showing determination of half lives from initial concentrations

From graph calculate half-life periods (t1/2)I and (t1/2)II for Set I and Set II from
concentration x = a0/2. Thus order can be calculated using the equation –
log (t1/2)I log (t1/2)II
Order (n) = 1 +
log a2 − log a1
Result Table :
Order of the reaction (n ) = ..........
---
32
2…
Viscosity
Experiment No. 8
Aim:
To determine the molecular weight of high polymer using it’s solution of different
concentrations by viscometry.
Apparatus :
Ostwald’s viscometer, density bottle, stop watch, measuring cylinder, etc.
Chemicals :
Pure solvent, 0.1, 0.2, 0.3, 0.4 and 0.5% solution of polymer in given solvent.
Theory :
Viscosity is the quantity that describes a fluid's resistance to flow. Fluids resist the motion
of layers with differing velocities within them as well as to the relative motion of immersed
objects through them.
Definition of Viscosity :
“It is the property of a fluid that resists the force tending to cause the fluid to flow.”
This resistance produces a frictional force known as viscous force proportional to the area
dv
of contact, A, between the flowing regions and to the velocity gradient, .
dx
dv
F ∝ A⋅
dx
dv
∴ F = ηA⋅ … (1)
dx
The constant of proportionality is called the coefficient of viscosity, η. The coefficient of
viscosity η, is the quantitative measure of viscosity and is often called the viscosity. Presence
of short-range attractive intermolecular forces and the momentum transfer between layers of
moving molecules are the cause of the force of viscosity. The first one dominates in flow of
liquids and second one in gases. The kinetic theory of gases is successfully applied to
calculate η that manifests in the formula :
⎛ MRT ⎞1/2
η = ⎜ 3 4 2⎟ … (2)
⎝π σ N ⎠
32
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Viscosity
where, M is the molar mass, R is the gas constant, σ is the molecular diameter, and N is the
Avogadro’s number.
Viscosity co-efficient is defined as the force per unit area required to maintain the unit
difference of velocity between the two different layers of liquid which are one centimeter apart.
It is measured in terms of “poise”. Viscosity of liquid is said to be one poise, when a force of
one dyne maintains a velocity difference of one centimeter per second between two parallel
layers of liquids, which are one centimeter apart and having area of contact one square
centimeter. It is also measured in terms of milli poise, centipoise etc.
The SI unit of viscosity is the pascal second (1Pa s = 1 kg/m-s). The most common unit
of viscosity is dyne s/cm2, which is given the name poise [P] in the honor of the French
physiologist Jean Louis Poiseuille (1799-1869). Ten poise equals one pascal second [Pa s] or
a centipoise [cP].
Thus, 1 g/cm-s = dyne-seconds/cm2 = 1 pascal second = 10 poise.
Poiseuille derived the following formula for the volume, V, of a fluid of viscosity, η,
moved through a tube of length l and radius r in time t at a pressure P,
4
V ⎛ πr ⎞
= ⎜ ⎟ ΔP … (3)
t ⎝8ηl⎠
From this equation, one see that a measure of the time that a specific volume of a liquid
takes to move through a tube, with a very small diameter under a constant pressure drop is a
direct measure of the viscosity. The above equation is directly applicable to a device such as
the Ostwald viscometer to measure the viscosity. With Ostwald viscometer, a liquid between
two marks (i.e. a definite volume) is allowed to flow through a small bore capillary and the
time of flow is measured.
Factors affecting Viscosity of Liquids :
1. Strong intermolecular force of attraction resists the flow of liquids and show higher
viscosity.
2. Polar compounds have more viscosity due to stronger attractions.
3. Increase in molecular weight of liquid, results in increase in viscosity.
4. Increase in temperature increases the kinetic energy of molecules and decreases the
viscosity of the liquid. (In case of gases the trend is reversed).
5. The increase in pressure increases viscosity to small extent.
Viscosity of Polymer Solutions : Eyring’s theory shows that solution properties depend
not only on the type of constituents, but on the amount of each present. The basis for
explaining the concentration dependence of the viscosity of a polymer solution is Einstein’s
relationship for the viscosity of dilute solution of spherical particles that follows :
33
η
= 1 + 2.5 φ … (4)
η0
where, η is the viscosity of a polymer solution with molecular volume φ, η0 is the viscosity of
the pure solvent. The specific viscosity, ηsp, is the increase in the viscosity over that of the
pure solvent caused by the addition of the polymer. Specific viscosity of a polymer solution
is thus expressed as
(η − η0)
ηsp = … (5)
η0
According to the Einstein relation, Eq. (4), the specific viscosity can be related to the
concentration by equation :
3
⎛10πr ⎞
ηsp = ⎜ ⎟⋅c … (6)
⎝3m⎠ m
where, r is the radius of the “spherical” molecule, m is its mass, and cm is the concentration of
polymer solution. The concentration dependence of specific viscosity is expressed in terms of
intrinsic viscosity, [η], as :
lim
[η] = (η /c ) … (7)
cm → 0 sp m
Like other parameters extrapolated to infinite dilution (zero concentration), the intrinsic
viscosity describes the interaction of a single average polymer molecule with a bulk of
solvent. For a spherical molecule, [η] should be proportional to the molecular volume. For
many synthetic polymers in dilute solution, the chains tend to adopt a tight, ball-like
configuration in solution, the average structure of which is defined by a radius of gyration,
RG. For such molecules, one predicts that :
3
RG
[η] = K' … (8)
M
where, M is the molar mass and K' is a constant. For a polymer that adopts a random-coil
conformation, dependence of intrinsic viscosity on molar mass as is found to vary as –
[η] = KM1/2 … (9)
This generally applies to polymer solutions under certain conditions.
In practice, the dependence of intrinsic viscosity on molar mass is more accurately given
by the empirical Mark-Houwink equation :
[η] = kMα … (10)
where, k and α are two parameters that depend on the solvent and the polymer. The values
of k and α for some polymer solvent systems at 25°C are given in Table 1. Once k and α are
known for a combination of polymer and solvent and the intrinsic viscosity determined
experimentally, one may use to calculate the viscosity-average molar mass Mv of a polymer
34
material. The values of k and α for some polymer solvent systems at 25°C are given in
Table 1.
Table 1 : Mark-Houwink parameters, k and α, for various polymers and solvents
Sr. Polymer Solvent Temperature/°C k/(cm3/gm) α
No.
1. Polystyrene Toluene 25 3.7 × 10−3 0.62
2. Cellulose acetate Acetone 25 1.49 × 10−3 0.82
3. Polymethyl methacrylate Benzene 25 0.94 × 10−3 0.76
(Perspex)
4. Poly (isobutylene) Benzene 25 0.083 0.53
5. Poly (isobutylene) Toluene 25 0.087 0.56
6. Poly (isobutylene) Cyclohexane 25 0.040 0.72
7. Crape rubber Benzene 25 2.02 × 10−3 0.89
8. Polypropylene Toluene 30 0.0218 0.725
9. Polypropylene Cyclohexane 25 0.016 0.80
10. Poly (vinyl alcohol) Water 25 0.0002 0.76
Measurement of Viscosity :
The common method used for the measurement of viscosity is to measure the time of
flow of liquid through a capillary tube. According to Poiseuille equation, co-efficient of
viscosity is given by equation,
πpr4t
η = a
8Vl
V A
where p = hydrostatic pressure on the
liquid. b
r = radius of capillary C
t = time of flow of liquid
V = volume of liquid flowing l
through the capillary in time t
l = the distance travelled by the
liquid in time t (or length of B
capillary)
Fig. 1: Viscosity is measured using

Ostwald’s viscometer
Ostwald’s viscometer is a U-shape tube with two bulbs A and B and a capillary C. The
volume V of liquid between marks ‘a’ and ‘b’ of bulb ‘A’ is allowed to pass through capillary B
(having length l) and time of flow is measured.
35
In practice a liquid of known viscosity and density is used to calibrate the Ostwald
viscometer. Then for any other liquid
η1 p1 ⋅ t1
= … (11)
η2 p2 ⋅ t2
Same viscometer being used in the experiment, equation (10) reduces to equation (11).
As pressure of liquid is directly proportional to density (ρ) of liquid,
η1 ρ1 ⋅ t1
=
η2 ρ2 ⋅ t2
Molecular weight of polymer is very high and ranges from 5,000 to 2,00,000. The
molecular weight of each polymer molecule depends on the degree of polymerization i.e. the
number of repeating units in the polymer molecule. By comparing the viscosity coefficients
of solvent and polymer solution, the molecular weight of high polymer can be determined
using equation :
(η/η0 − 1)
= k ⋅ Mα
C
where, M = molecular weight of polymer
C = concentration of polymer in gram per 100 ml of solution
η = viscosity of solution
η0 = viscosity of pure solvent
k = constant for a given polymer for particular solvent and temperature
α = a constant that is a function of geometry of polymer molecule
⎡ η − 1⎤ = η = specific viscosity
But, ⎢η ⎥ sp
⎣ 0 ⎦
ηsp
∴ = kMα
C
This equation is valid for dilute solution only (concentration less than 1%). Since ηsp is
directly proportional to the concentration (C) of the polymer in the solution, the plot of ηsp/C
against C is a straight line. The intercept of this straight line on y-axis gives the intrinsic
viscosity [η].
2.303 η
Similarly plot of log against C gives a straight line with y intercept [η].
C η0
The intrinsic viscosity [η] is defined by the relations
lim ηsp lim 2.303 η
[η] = = log
C→0 C C→0 C η0
Knowing the intrinsic viscosity the molecular weight is determined by Mark-Houwink
equation
[η] = kMα
∴ log [η] = log k + α log M
36
(log [η] – log k)

∴ α = log M
⎛log [η] – log k⎞

∴ Mol. wt. (M) = Antilog ⎜ ⎟
⎝ α ⎠
Procedure :
(A) Measurement of Flow Time for Solvent :
1. Take a clean dry Ostwald viscometer and clamp it in a perfectly vertical position to an
iron stand. (Clean and dry the viscometer by running a few millilitres of acetone
through it. Drain the acetone and aspirate for about a minute to evaporate all the
acetone.)
2. Suspend the viscometer into a large beaker of water.
3. Pipette sufficient quantity of solvent of known density into the viscometer (bulb B)
and allow time for the liquid to equilibrate to the temperature of the bath.
4. Then suck the liquid level up above the upper mark ‘a’ on the bulb A. (A pipette bulb
may be used to pull the liquid up).
5. Allow the solvent to run back down and start the stop watch/timer exactly as the
meniscus passes the upper mark “a”.
6. Stop the stop watch just as the meniscus passes the lower mark “b”. Repeat at least
twice. Your flow times should agree to within ± 0.4 seconds.
7. Record the observations as shown in the observation table.
(B) Determination of Time of Flow for the Solution of Polymer :
1. Introduce sufficient quantity of 0.1% polymer solution in viscometer.
2. Determine the flow times as measured for solvent above.
3. Similarly, find the flow time for 0.2, 0.3, 0.4 and 0.5% polymer solutions.
Record the observations in observation table.
Observations :
Part A : Solvent
Time of flow (seconds) Mean time of flow
Solvent
1 2 3 t0 (seconds)
37
Part B : Polymer Solution

Conc. of Flow time t t η η ηsp 2.303 η
= = 1 = ηsp log
Polymer t0 η0 η0 C C η0
1 2 3 Mean
% Time
0.1
0.2
0.3
0.4
0.5
Calculations :
Plot the graph of ηsp/C against concentration C. Extrapolate to find intercept on y axis as
intrinsic viscosity [η].
Graph :
2.303 h
hsp/C log h
[n] C o [n]
Concentration Concentration
Fig. 2
2.303 η
Similarly plot the graph of log against concentration C.
C η0
The intrinsic viscosity is determined by extrapolating the straight line to zero
concentration.
Thus, knowing [η], k and α, the molecular weight (M) is calculated using equation :
⎛log [η] – log k⎞
M = antilog ⎜ ⎟
⎝ α ⎠
Result Table :
1. Intrinsic viscosity [η] ………poise
2. Molecular weight of given polymer ………
38
---
39
3…
Adsorption
Experiment No. 9
Aim:
To investigate the adsorption of oxalic acid/acetic acid by activated charcoal and test the
validity of Freundlich and Langmuir isotherm.
Apparatus :
Five stoppered bottles, burette, pipettes, conical flasks etc.
Chemicals :
0.5 N oxalic acid, 0.5 N acetic acid, 0.1 N sodium hydroxide solution, phenolphthalein
indicator, powdered activated charcoal, etc.
Theory :
The molecular forces at the surface of liquid as well as solid are in a state of imbalance.
As a result exposed solid and liquid surfaces tend to satisfy their residual forces by attracting
gases or dissolved substances from an adjacent gas or liquid and retaining them on surfaces.
This phenomenon of concentration of substances on the surface of liquid or solid is called as
‘adsorption’. Thus adsorption is a surface phenomenon. The extent of adsorption mainly
depends on temperature, pressure, area of adsorbent etc. A substance that has been or is to
be adsorbed on a surface is said to be adsorbate. A substance having capacity or tendency to
adsorb another substance is called as ‘adsorbent’.
Adsorption Isotherm :
Adsorption is usually described through isotherms. The relation between the amount of
substance adsorbed by an adsorbent and the equilibrium concentration (or pressure in case
of gas) at constant temperature is called adsorption isotherm. Adsorption phenomenon is
divided into two types :
(1) Physical adsorption and (2) Chemical adsorption.
In 1909, Freundlich gave an empirical expression representing the isothermal variation of
pressure with adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent. This
equation is known as Freundlich Adsorption Isotherm or simply Freundlich Isotherm.
x
= kP1/n
m
For solutions, equation takes the form
x
= KC1/n (for solution)
m
39
where, x = mass of gas or solute adsorbed

m = mass of adsorbent
P = equilibrium pressure of adsorbate
C = concentration of the solute in gram moles per litre.
K and n are constants whose values depend upon adsorbent and gas or solute at
particular temperature.
Taking logarithm on both sides, above equation becomes
x 1
log = log C + log K
m n
This equation represents the straight line. The graph of log x/m against log C is a straight
line, with slope = 1/n and y intercept log K. Slope can give the value of n since, n = 1/slope
Adsorption Isotherm
x
m log x/m
Saturation pressure (PS) log K
P log C
(a) (b)
Fig. 1: Freundlich Isotherms

The straight line nature is observed at lower concentrations. Deviations are marked at
higher concentration. Freundlich Isotherms failed to predict value of adsorption at higher
concentration /pressure.
Langmuir Adsorption Isotherm :
In 1916, Langmuir proposed another adsorption isotherm known as Langmuir Adsorption
Isotherm. For the adsorption of solute from solution on solids Langmuir isotherm is
x aC
=
m 1 + bC
where, a and b are constants. Rearranging above equation
C b 1
= ⋅C+
x/m a a
C b
Graph of against concentration is a straight line with slope = and y intercept equal
x/m a
1
to .
a
40
Slope = b/a
C
x/m y intercept = 1/a
Concentration
Fig. 2
Procedure :
1. Take five clean stoppered bottles and label them as 1 to 5.
2. Add oxalic acid solution and distilled water to these bottles as per the following
chart.
Amount of
Bottle No. ml. of 0.5 N oxalic acid ml. of water
activated charcoal
1 50 00 1 gm
2 40 10 1 gm
3 30 20 1 gm
4 20 30 1 gm
5 10 40 1 gm
3. Weigh and add 1.00 gram of the activated charcoal to each of the bottle.
4. Stopper the bottles, place them in water bath and shake well for 30 minutes from
time to time.
5. Mean while titrate 10 ml oxalic acid against 0.1 N NaOH solution using
phenolphthalein indicator to determine the initial concentration of acid. Record it
as ‘V’.
6. After 30 minutes filter the solution from each bottle in separate flask. Titrate 10 ml of
the filtrate from each bottle with 0.1 N NaOH. Take three readings for each bottle
and note the mean as Ce, the equilibrium concentration.
Prepare observation table as given below :
(i) Weight of charcoal, (m) = 1.00 gm.
(ii) Volume of 0.1 N NaOH required (burette reading) for 10 ml. of oxalic acid,
(V) =.…..ml.
41
ml. of NaOH required for ∴ ml. of NaOH required

10 ml of acid in bottles for 50 ml of acid in bottles
Obs log
After Before After C log C x x/m
No. Before (x/m)
adsorption adsorption adsorption
adsorption
(B.R.) (C0) (Ce)
1 V =…….. V1 =…..… 5V =…..… 5V1 =…..…
2 4/5V =…….. V2 =…..… 4V =…..… 5V2 =…..…
3 3/5V =…….. V3 =…..… 3V =…..… 5V3 =…..…
4 2/5V =…..… V4 =…..… 2V =…..… 5V4 =…..…
5 1/5V =…….. V5 =…..… V =…….. 5V5 =…..…
Calculations :
Equilibrium concentration of oxalic acid in gram equivalent per litre,
Ce × Total volume of acid solution × Eq. wt. of acid Ce × 50 × 63
C= =
1000 1000
(C0 − Ce) × 50 × 63
Amount of acid adsorbed, x =
1000
Plot the graph of log x/m against log Ce. A straight line graph indicates the validity of
Freundlich equation in the adsorption of oxalic acid by activated charcoal. Find the value of
K and n.
Ce
Validity of Langmuir adsorption isotherm can be tested by plotting against Ce.
x/m
A straight line graph is in agreement with Langmuir adsorption isotherm. Calculate the
constants a and b.
Result Table :
Obs. No. Symbol Values
1 K
2 N
3 a
4 b
Conclusion :
Straight line nature of both the graphs indicates the validity of Freundlich and Langmuir
adsorption isotherm.
---
42
4…
Phenol-Water System
Experiment No. 10
Aim :
To study the effect of addition of salt on critical solution temperature of phenol-water
system.
Apparatus :
Hard glass test tube, stirrer, thermometer, water bath, 10 ml measuring cylinder etc.
Chemicals :
Pure phenol, distilled water, 0.1 M KCl.
Theory :
The solubility of liquid in liquid is an important part of solution chemistry. Miscibility is
the property of liquids to mix in all proportions, forming a homogeneous solution. Water and
ethanol, for example, are miscible since they mix in all proportions. By contrast, substances
are said to be immiscible if they do not form a solution, in all the proportions. For example,
diethyl ether is fairly soluble in water. These solvents are not soluble in all the proportions.
Hence they are immiscible. Liquids tend to be immiscible when attractions between like
molecules are much stronger than attractions between mixed pairs.
When two liquids are mixed together, one of the following cases may arise :
(a) the two liquids are completely miscible at all proportions forming one homogeneous
solution e.g. water and ethanol.
(b) the two liquids are partially miscible forming either one or two liquid phases,
depending on their composition in the mixture. e.g. phenol and water.
(c) the two liquids are immiscible forming always two distinct phases irrespective of
composition e.g. water and carbon tetrachloride (CCl4).
The mutual solubility of partially miscible liquids usually increases with temperature. This
miscibility temperature is different for different compositions of the mixture. The highest
miscibility temperature is called the “critical solution temperature”. Above this temperature,
all compositions of this mixture are completely miscible. For some liquid pairs such as ether
and water, the mutual solubility decreases with temperature. For such systems the lowest
miscibility temperature is called the “critical solution temperature”. Below this temperature,
all compositions of this mixture are completely miscible.
43
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Phenol-Water System
There are certain liquid pairs like nicotine and water, which have upper as well as lower
critical solution temperature. Liquid pairs like ethyl acetate and water or chloroform and
water does not have upper or/and lower critical solution temperature. Such systems are
called as systems without critical solution temperature or incomplete systems.
A solute soluble in one of the two liquids increases the critical solution temperature if
present in partially miscible liquids in equilibrium. For example, addition of small amount of
KCl, increases critical solution temperature of phenol-water system. KCl is soluble in water
only and not in phenol. If the solute is soluble in both the liquids the critical solution
temperature decreases. For example, presence of succinic acid in phenol-water system
decreases the critical solution temperature. The change in critical solution temperature is
found to be linearly proportional to the percentage of solute.
N.B. : Phenol is highly corrosive. Avoid its contact with skin. Phenol sticks to measuring
cylinder and bottle from outside and may come in contact with skin.
Procedure :
Set I :
1. Measure 9.5 ml of phenol into the hard glass tube (boiling tube). Fill a burette with
distilled water and add 6 ml water into the tube containing phenol.
2. Fix the thermometer and stirrer and mount the tube in a water bath (water in a
beaker) placed on tripod stand. Turbidity (cloudiness) appears on stirring the
solution.
3. Heat it with mild stirring until the turbidity disappears. Note the temperature as
mixing temperature at which turbidity just disappears.
4. Now cool the tube in a second water bath with mild stirring until the turbidity
reappears. Once again note the temperature.
5. Similarly prepare phenol-water mixtures of various compositions in the hard glass
tube as given in the observation table below. Record their mixing and separation
temperatures in the same way as given in steps 3 and 4.
6. Prepare 0.1 M KCl salt solution mixture of various compositions as before and find
the mutual solubility of each mixture.
Set II :
1. Repeat the procedure in Set I except with 0.1 M KCl salt solution in place of water.
Note the mutual solubility temperatures for mixtures of various compositions.
2. Tabulate the result as follows.
44
Observation Table : Density of salt solution = 1.09 g/ml.

Set I : Phenol - Water system
Amount of Amount of % Phenol % Miscibility temperature (°C)
Phenol (g) Water (g) Water disappear appear average
10 (9.5 ml) 6
10 8
10 12
10 15
5 (4.8 ml) 5
5 10
2.5 (2.4 ml) 15
2.5 20
2.5 25
Set II : Phenol - Salt solution
Amount of Amount of 0.1 M % % Miscibility temperature (°C)
Phenol (g) KCl solution (g) Phenol Water disappear appear average
10 (9.5 ml) 6
10 8
10 12
10 15
5 (4.8 ml) 5
5 10
2.5 (2.4 ml) 15
2.5 20
2.5 25
Calculations :
Weight of phenol
% phenol =
Weight of phenol + Weight of water
Weight of water
% phenol =
Weight of water + Weight of phenol
Weight of salt
% phenol =
Weight of salt + Weight of phenol
Plot the graph of mutual solubility temperature against % of phenol (composition) for
two sets. Use the same graph paper.
45
tC
II
P=1
tC
I
Temperature
P=2
Critical composition
0% % Phenol
Fig. 1: Mixing temperature vs. Composition curves (P → phases)
Temperature corresponding to the maxima on the parabolic curve gives the upper critical
solution temperature.
Find the increase in critical solution temperature due to addition of salt.
Increase in critical solution temperature = (tCII – tCI) °C.
Result Table :
1. Critical solution temperature of phenol-salt system (tCII) = ……... °C.
2. Critical solution temperature of phenol-water system (tCI) = ……. °C.
3. Increase in critical solution temperature (tCII – tCI) = ……….. °C.

4. Percentage of phenol at critical solution temperature = ..….... %.
Conclusion :
Liquids tend to be immiscible when attractions between like molecules are much
stronger than attractions between mixed pairs. Presence of a salt modifies these interactions.
Presence of KCl in phenol-water system delays the miscibility. Increase in critical solution
temperature in this system indicates that the phenol-water attractions are weakened due to
presence of salt.
---
46
5…
Transport Number
Experiment No. 11
Aim :
To determine the transport number of cation by moving boundary method.
Theory :
In a solution of an electrolyte the current is carried by the ions. As a result the
concentration of the electrolyte changes. The equivalent amounts of positive and negative
ions are discharged at respective electrodes. But the velocity with which the positive and
negative ion move is different. Consequently the amount of electricity carried by cation in
one direction is different from that carried by anions in opposite direction. These two
amounts are in the ratio of the mobilities of cations (u+) and anion (u−) respectively. The total
current passing through the solution is proportional to the sum of ionic mobilities (u+ + u−).
The fraction carried by cation and anion is given by the equations
u+ u−
t+ = and t− =
u+ + u− u+ + u−
These fractions are called as transport number of cation (t+) and transport number of
anion (t−). These numbers can be determined by Hittorf’s method and moving boundary
method.
Moving Boundary Method : _
A sharp boundary is formed in a
tube between solutions of two salts
having a common ion say H+Cl− and b
+ -
b
H Cl
Li+Cl−. The position of the boundary is
a a
observed by the colour of the methyl Li
+
Cl
-
orange. Now a potential gradient is

set up along the tube by applying +
voltage across the electrodes situated
at the ends of the tube. The current Fig. 1: Basis of the moving boundary method
will flow by the migration of cation for determination of transport number
towards the cathode and anions towards the anode. At the boundary the H+ and Li+ ions will
move the same direction and hence the boundary will be observed to move. The tube is
graduated so that the volume V swept through in time t(s) during the passage of QC of
47
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Transport Number
electricity can be determined. The amount of charge carried by H+ ions across any section bb
in HCl solution is equal to the number of moles of H+ ions, which would have passed that
section (CV) multiplied by charge carried by each mole (96500 C). Hence, the fraction of the
current carried by H ions (t+) is given by
C × V × 96500
t+ =
Q
where, C = Concentration
V = Volume swept
Q = Number of coulombs passed through the solution
If current passing through the tube is kept constant, then above equation becomes
CF dv
t+ = ×
1000 × I dt
where, C = Concentration of H+ ion
F = Faraday
I = Current
dv
= the slope of the volume versus time curve
dt
Apparatus :
Glass assembly as shown in Fig. 2.
Chemicals :
0.1 N HCl solution, methyl orange indicator, LiCl solution.
_
Cathode + Anode
G E
D
I
A
LiCl
B
F
C
H
48
Fig. 2: Apparatus for determination of transport number of HCl

by moving boundary method
Procedure :
1. Rinse the cleaned apparatus twice with HCl solution and fill it with the same acid
solution containing methyl orange indicator.
2. Insert the stopper G and close the stopcock A.
3. Pour off HCl solution from E and clean this part with distilled water. Fill E with LiCl
solution.
4. Insert the anode assembly as shown in figure above.
5. Keep the whole apparatus in glass sided water bath.
6. Connect the cathode and anode to the source.
7. Open fully the stopcock very slowly.
8. Switch on the current of 10 mA at once and bring the boundary in the calibrated
volume rapidly.
9. Reduce the current and keep it constant between 2-5 mA by adjusting the
potentiometer.
10. Start the stop-watch as soon as the boundary reaches the first graduation on the
tube BC.
11. Record the volume swept by the boundary and time till the boundary reaches the
bottom of the tube.
Observations :
Obs. No. Volume on tube BC Volume swept/ml Time/second
1.
2.
3.
4.
5.
Graph :
Plot the graph of volume swept (ml)
against time (s). If the current is kept
constant, the graph is a straight line as
Volume swept / ml
shown in Fig. 3.
dv
Find the slope of the line i.e. .
dt
time / s
49
Fig. 3: Plot of volume swept in ml against

time in second
Calculations :
Calculate transport number of cation by using the equation
96500 × C dv
t+ = ×
1000 × I dt
Result :
t+ = ……….
VIVA VOCE
1. Define transport number of the cation (t+).
2. Define transport number of the anion (t−).
3. State different methods used for the measurement of transport number.
4. State the equation for transport number determination by moving boundary method.
---
50
6…
Refractometry
(Any Two)
Refraction :
When a ray of light travels from one medium into another its velocity changes. This
causes the wave to change its direction. This change of direction as waves pass from one
material into another is called refraction.
The Refractive Index :
The refractive index 'n' of a substance is defined as
Vv
n =
V
where, Vv is the velocity of light in vacuum and V is the velocity of light in the substance.
Assuming that velocity of light in air is essentially same as that in vacuum, then refractive
index of air is one. Light slows down when it enters form air into a substance so that the
refractive index of the substance is always greater than one. In other words, when light
passes from the rarer medium into the denser medium it bends towards the normal. This
bending of light is called refraction.
Snell’s Law :
Snell's law is the simple formula used to Normal
P
calculate the refraction of light when travelling n1
between two media of different refractive indices.
q1
In the diagram, two media of refractive indices
Interface
n1 and n2, meet at an interface (horizontal line) O
and n2 > n1 and the light has a low velocity within q2
the second medium. n2
A light ray PO in the upper less denser

Q
medium strikes the interface or point ‘O’. A
vertical line drawn from O at right angles to the Fig. 1
interface is called normal.
The angle between the incident ray PO and the normal is called angle of incidence θ1.
The light ray continues through the interface into the denser medium on the lower side
51
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Refractometry
shown by the ray OQ. The angle between the ray OQ and the normal is θ2 and is called angle
of refraction.
Snell"s law gives the relation between θ1 and θ2 as
n1 sin θ1 = n2 sin θ2
sin θ1 n2
or =
sin θ2 n1
It should be noted that for the case of θ1 = 0 (a ray perpendicular to the interface, the
value of θ2 = 0 irrespective of values of n1 and n2). That is a ray hitting the interface at right
angles and passing into another medium never bent. The above law is also valid for light
travelling from a dense to a less dense medium. A qualitative rule to determine the direction
of refraction is that the ray in the denser medium is always closer to the normal.
When a ray of light passes from a dense to a less dense medium i.e. n1 > n2, the angle of
refraction becomes 90° for a particular angle of incidence (called critical angle, θcrit). If the
angle of incidence is farther increased there will be no refraction but the light is completely
reflected into the first medium, this phenomenon is known as total internal reflection.
Critical angle for a pair of media can be defined as the angle of incidence for which the
angle of refraction is 90° when light travels from a dense to a less dense medium.
By Snell's law,
sin θ1 n2
=
sin θ2 n1
When θ1 = θcrit, θ2 = 90° and sin 90° = 1.
sin θcrit n2 n2 sin θcrit
Therefore, = or sin−1 = = Acrit
sin 90 n1 n1 1
n2 ⎛n2⎞
Therefore, Acrit = sin−1 or arc sin ⎜ ⎟
n1 ⎝n1⎠
n2
The equation θcrit = sin−1 is frequently used to find out the refractive indices of liquids
n1
using refractometers.
Measurement of Refractive Index :
Following are the different types of refractometers used for determination of refractive
indices of liquids.
(i) Pulfrich refractometer – accuracy of measurement : 0.00002
(ii) Immersion refractometer − accuracy of measurement : 0.00004
(iii) Abbe refractometer – accuracy of measurement : 0.00002.
52
The most commonly used refractometer is the Abbe refractometer. The schematic of
which is shown in Fig. 2.
E
1 E = Eye piece
2
T S = Refractive index scale
T = Telescope
K P = Prism box (with split prisms)
S
M = Adjustable mirror
P
F = Adjustment screw
F
K = Compensating system screw
X X = Field view when setting is complete
M
Fig. 2: Abbe refractometer-schematic

The Abbe refractometer measures refractive indices from 1.30 to 1.70 with accuracy of
measurement to 0.0002. It requires only a few drops of liquids for measurement. The optical
parts of Abbe refractometer are shown in the labelled diagram. For measurement of
refractive index of sodium-D line, light is used.
The liquid whose index is to be measured is spread on the lower split prism. The prism
box is closed and tightly locked. The mirror is directed to reflect light from lamp on to the
prism. The light emerging from the prism is received by the fixed telescope after moving the
arc to which index scale is attached. The field of view may initially show blue or red fringes
dividing a grey or dark zone on one side and a white zone on the other side. The dispersed
light is neutralised by rotating the compensative prisms (prism box) and line demarking the
grey zone and white zone is made sharp and made to coincide with the crossing of the lines
in the field view. This adjustment indicates the critical angle condition and the scale reads the
refractive index. The refractive index is read from the scale.
Specific and Molar Refraction :
(i) The specific refraction r, is defined by the equation
n2 − 1 1
r = ×
n2 + 1 ρ
n = refractive index, ρ = density of liquid
(ii) The molar refraction, RM is defined by the equation
53
n2 − 1 M
RM = × =r×M
n2 + 1 ρ
where, M is molecular weight of the liquid. The molar refraction R is constitutive and additive
property. The molar refraction [R]AB of a mixture of A and B liquids is the sum of the
contributions of the separate components A and B i.e.
[R]A, B = XA[R]A + XB[R]B
where, XA and XB are mole fractions of A and B respectively, and [R]A and [R]B are molar
refractions of A and B respectively.
2
nA,B − 1 ⎡XAMA + XBMB⎤
Also, RA, B = 2 ⎢ ⎥
n +2 ⎣
A,B
ρA,B ⎦
where, nA, B and ρA, B are refractive index and density of mixture AB.
Mixture Law :
The percentage of A and B in their mixture is given by the mixture law as
rA, B × 100 = rAPA + rB (100 − PA)
where, rA, rB and rA,B are specific refractivities of liquids A, B and their mixture AB respectively.
PA is percentage of A, PB = (100 − PA) is percentage of B in the mixture.
The molar refraction is an additive as well as a constitutive property. Every constituent
atom of the molecule makes a definite contribution to the molar refraction. The double
bonds, triple bonds etc. also contribute to the total molar refraction.
Contribution of −CH2 group to the molar refraction of successive members of
homologous series :
The successive members of homologous series like (i) methanol, ethanol, n-propanol,
n-butanol and (ii) methyl acetate, ethyl acetate, propyl acetate differ by a CHO2 group.
Therefore, the difference in molar refraction of successive members of the series must be
same and should give the contribution of −CH2 group and it is found to be so. The following
table of experimental values proves this.
Table 1
Homologous series Molar refraction Contribution of −CH2

R (Na-D line) group, ΔR
Methanol, CH3OH 8.213 −
Ethanol CH3CH2OH 12.74 4.522
54
n-propanol, CH3CH2CH2OH 17.415 4.675
n-Butanol CH3CH2CH2CH2OH 22.130 4.615

Density and refractive indices of some liquids are given below :
Table 2
Liquid Refractive index ‘n’ Density ρ, gm ml−1
Acetone 1.3588 0.785
Aniline 1.5861 1.022
Benzene 1.5011 0.874
n-Butyl acetate 1.3940 0.882
Carbon tetrachloride 1.4601 1.584
Chlorobenzene 1.5241 1.106
Chloroform 1.4460 1.480
Cyclohexane 1.4266 0.714
Ethanol 1.3611 0.785
Ethyl acetate 1.3723 0.900
Ethyl ether 1.3526 0.714
Hexane 1.3751 0.655
Methanol 1.3288 0.787
n-propyl acetate 1.3820 0.889
Toluene 1.4961 0.774
Methyl acetate 1.3610 0.932
Water 1.330 1.00
Experiment No. 1
Aim :
To determine the specific refractivities of given liquids A and B and hence to determine the
percentage composition of liquid mixture C containing A and B.
Apparatus :
Abbe refractometer, specific gravity bottles, droppers etc.
Chemicals :
Given pure liquids A and B and the following mixtures of A and B prepared to weight to
weight ratio.
Mixture C : Unknown
Mixture D : 20 %A + 80 %B
Mixture E : 40 %A + 60 %B
Mixture F : 60 %A + 40 %B
Mixture G : 80 %A + 20 %B
Procedure :
55
As described in the previous experiment of refractometry, determine densities and

specific refractivities of pure liquids A and B as well as their different mixtures.
Record your observations as follows.
Observation Table :
(I) Determination of densities of liquids :
Weight of empty specific gravity bottle (W1) = ………. g
Obs. Liquid Weight of sp. gr. Weight of liquid Density
No. mixture bottle + liquid W2 g W2 − W1 = W3 gm ρ = W3/W4 g ml−1
1. A
2. B
3. C
4. D
5. E
6. F
7. G
8. Water W4
(II) Refractive index measurement :
Specific
Obs. Composition of Density ρ refractivity
Liquid Refractive index
No. mixture gm l−1 n2 − 1 1
r= ×
n2 + 2 ρ
I II III Mean
1. A 100 %A + 0 %B
2. B 0 %A + 100 %B
3. C Unknown
4. D 20 %A + 80 %B
5. E 40 %A + 60 %B
6. F 60 %A + 40 %B
7. G 80 %A + 20 %B
Calculations :
n2 − 1 1
Calculate specific refractivity, r = 2 ×
n +2 ρ
Graph :
56
Plot a graph of specific refractivity

against percentage of A.
From the graph find the % of A r rc
corresponding to the specific refractivity
of unknown C.
%B = 100 − %A Unknown
Mixture Law : composition
100 (rC − rB) 0 20 40 60 80 100

PA = and PB = 100 − PA
(rA − rB) % of A
Fig. 1
where, rA, rB and rC are specific refractivities of %A, 100%B and unknown composition
respectively.
Result Table :
Percentage composition of mixture C.
Graphical Method Mixture Law
%A= %A=
%B= %B=
Experiment No. 2
Aim :
To determine molecular refractivity of given liquids A, B, C and D.
Apparatus :
Abbe refractometer, specific gravity bottle, beakers etc.
Chemicals :
Given pure liquids A, B, C and D.
[The liquids can be carbon tetrachloride, chloroform, methyl acetate, ethyl acetate,
benzene, methanol, ethanol, n-hexane, propanol etc.]
Procedure :
(A) Measurement of Refractive Index of liquids A, B, C and D :
1. Open the prism box of the refractometer. Clean the prism surfaces by wiping gently
with cotton moistened with alcohol. Then wipe with dry cotton plug.
2. Spread the given liquid A by putting few drops of liquid on the surface of the lower
prism and immediately close the prism box and tighten it with the locking screw.
3. Adjust the mirror below the prism box so that the light from the light source enters
the prism box. The illumination can be seen through eyepiece 1.
4. Move the arc to which index scale is attached, till light emerging from the prism is
received by the telescope.
57
5. The field of view is divided by a grey or dark zone on one side and white zone on the
other side with blue or red fringes. Fringes are due to dispersion of light.
6. To neutralise the dispersion of light rotate the compensator prism using
compensating system screw till the line demarking grey zone and white zone become
sharp.
7. Rotate the prism box till the sharp line dividing grey and
white zone coincides crossing of lines in the field view.
8. Read the refractive index from the scale through eyepiece 2.
9. In a similar way find refractive indices of liquids B, C and D. Field view
Fig. 1
(B) Measurement of Density of liquids A, B, C and D :
1. Take a specific gravity bottle of 10.0 ml or 15.0 ml capacity. Wash the bottle with
water and then with acetone and dry the bottle.
2. Weigh accurately the empty specific gravity bottle with the stopper (W1 gms).
3. Fill the bottle with the liquid A to the rim and place the stopper, weigh the bottle
again.
4. Remove the liquid A, wash the bottle again and rinse it with a small quantity of
acetone and dry it. Fill it with liquid B and find the weight of bottle again.
5. In a similar way weigh the bottle with liquids C and D. Find the weights of liquids
A, B, C, D.
6. Now fill the dry bottle with water and find the weight of water.
7. Find the density of liquids.
Weight of liquid
Density of liquid = ρ =
Weight of same volume of water
Observation Table :
Obs. Liquid Weight of sp. gr. Weight of liquid Density =
No. bottle + liquid (W2) W3 = W 2 − W 1 g Wt. of liquid
Wt. of same vol. of water
ρ = W3/W4
1. A
2. B
3. C
4. D
5. Water W4
(I) Density Measurements :
Weight of empty specific gravity bottle = (W1) = ………. g.
(II) Refractive Index Measurements :
58
Refractive Index ‘n’

Obs. No. Liquid Mean ‘n’
I II III
1. A
2. B
3. C
4. D
Calculations :
1. Specific Refraction :
n2 − 1 1
Specific refraction r = ×
n2 + 2 ρ
2. Molar Refraction :
n2 − 1 M
R = ×
n2 + 2 ρ
Ask for the molecular weights of liquids A, B, C and D.
Result Table :
Liquids A B C D
Molar
Refraction RM
Experiment No. 3
Aim :
To determine the molar refraction of methyl, ethyl, propyl alcohol and to show the
constancy contribution to the molar refraction made by −CH2 group.
Apparatus :
Abbe refractometer, light source, beaker etc.
Chemicals :
Methyl, ethyl and n-propyl alcohol.
Procedure :
As in the previous experiment of refractometry find the densities and refractive indices of
liquids methyl, ethyl and n-propyl alcohol. Record the observations in the table given below.
Find the specific and molar refraction values of the liquids. Find the contribution made by
−CH2 group to the molar refraction of the liquids.
Observation Table :
(I) Measurement of Density :
Obs. Liquid Weight of sp. Weight of liquid Density
No. gr. bottle + W3 = W 2 − W1 ρ = W3/W4
liquid, W2 g gm gm l−1
1. Methyl alcohol (CH3OH)
2. Ethyl alcohol
(CH3CH2OH)
59
3. n-propyl alcohol
CH3CH2CH2OH
4. Water W4
(II) Refractivity Measurements :
Obs. Liquid Mole- Refractive index Density Specific Molar
−1
No. cular ‘n’ ρ gm l refractivity refraction
wt. I II III Mean n2 − 1 1 RM = r.M
r= 2 ×
M n +2 ρ
1. CH3OH 32
2. CH3CH2OH 46
3. CH3CH2CH2OH 60
Weight of empty specific gravity bottle = (W1) = ………. g
(III) Calculations :
n2 − 1 1
1. Specific refraction r = 2 ×
n +2 ρ
2. Molar refraction = r × molecular weight (M)
3. ΔR, the contribution of CH2 group to R.
Find :
ΔR1 = RCH3CH2OH − RCH3OH
and ΔR2 = RCH3CH2CH2OH − RCH3CH2OH
ΔR1 = ΔR2 = Contribution of CH2 group to the molar refraction of
homologous alcohol.
Result Table :
Liquid Molar Refraction ΔR Contribution of
RM −CH2 group
1. Methyl alcohol (CH3OH)
2. Ethyl alcohol (CH3CH2OH)
3. n-propyl alcohol (CH3CH2CH2OH)
VIVA VOCE
1. What is refraction ?
2. Define refractive index.
3. State and explain Snell's law.
4. What is total internal reflection ?
5. What happens when angle of incidence exceeds the critical angle ?
6. What is critical angle ?
7. Define specific refractivity and molar refraction.
8. Give the relation between specific refraction and refractive index ?
9. What is the effect of temperature on specific and molar refraction ?
10. Explain how the molar refraction is useful in elucidating structure of organic
compounds.
11. What is an additive and a constitutive property ?
60
12. Explain with examples how molar refraction is an additive as well as a constitutive
property.
13. Define density and specific gravity of a substance.
14. How will you determine the density of a liquid ?
15. What is mixture law in terms of percentage of individual components ?
16. What is the expression for molar refraction of a mixture of two liquids in terms of
molar refractions of the two liquids ?
17. Give Gladstone and Dale equation of molar refraction of a liquid ?
18. What is Lorenz and Lorentz equation of molar refraction ?
19. How you will determine contribution of methylene group in homologous alcohol and
esters ?
20. Will the contribution of methylene group is same for both homologous series of
alcohol and esters ?
---
61
(GROUP – B)
1…
Colorimetry
(Any Two)
Theory :
The variation of intensity of colour of a solution with the change in the concentration of
the coloured solute forms the basis of colorimetric analysis. The intensity of the colour of a
substance can be measured by determining the fraction of particular wavelength of light
absorbed by it.
The advantage of colorimetric determination is that, this method is much more rapid
than those involving volumetric or gravimetric methods. Also it is applicable to the
determination of small amounts of substances in a material, i.e. less than 1 percent.
Fundamental Laws of Colorimetric Measurement :
When light of intensity I o , passes
Is
through a solution, some of the radiation is
scattered or reflected by the walls of the
container and by the suspended particles
in the solution (Is), some is absorbed (Ia)
Io Ia It
and remaining is transmitted (It), i.e. Io =
Is + Ia + It. Since, the colorimetric methods
are based on the relation between the
amount of light absorbed and the Is
concentration of the absorbing material.
Fig. 1: The distribution of incident light
Therefore, it is necessary to eliminate Is, so
passing through a cell containing a solution
that a measurement of Io and It will be
sufficient to determine Ia. In colorimetric
determinations, the amount of light scattered is not eliminated, but it is kept constant by
using cells that have identical optical properties while measuring Io and It. The important laws
of photochemistry are the Lambert’s law, Beer’s law and combination of these two, and is
called as Lambert - Beer’s law.
Lambert’s Law :
The rate of decrease in the intensity of a monochromatic light passing through a
transparent medium, with the thickness or optical path-length of the medium is proportional to
the intensity of the incident light.
61
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Colorimetry
dI
Thus, − = kI
dl
where, I = Intensity of the light
l = Thickness of the medium
k = Constant and is characteristic of the medium
By solving the above differential equation we obtain the following relation
I0
ln = kl, Intensity of incident light = I0
It
It = I0e−kl, Intensity of transmitted light = It
In general, this law have the simple relation i.e. optical density or absorbance ∝ thickness
of the light absorbing medium.
But this law is not sufficient to find out the concentration of solute in the solution.
Beer’s Law :
In a path of constant length, equal fractions of incident radiation are absorbed by equal
changes in the concentration of the light absorbing material. Thus,
dI
− = kI
dC
I0
ln = kC
It
Thus, the short form of this law is given as
Optical density or absorbance ∝ concentration.
In order to find out the concentration of coloured solute in given solutions, it is necessary
to consider both laws simultaneously. Thus, the combination of Beer’s law and the Lambert’s
law gives suitable form of the equation where both i.e. thickness of the absorbing material
and its concentration is considered.
I0
Thus, ln = alC
I
I0
A or D = ∈.C.l = log = − log T
I
where ‘C’ is the concentration of the solute and ∈ is a constant characteristic of the
solute. When ‘C’ is expressed as mol dm−3, the constant ∈ is called the molar absorption
coefficient, or molar extinction coefficient or molar absorptivity.
The important terms involved in it are as follows :
1. Radiant Power (P) : It is the rate at which energy in a beam of radiation arrives at
some fixed point. It is also called as intensity (I).
2. Transmittance (T) : It is the ratio of intensity of transmitted radiation (It) to that of
intensity of incident radiation (Io).
It
T =
I0
It does not have any unit.
62
3. Absorbance (A) : It is also called optical density. It is the log to the base 10 of the
intensity of incident radiation to that of the intensity of transmitted radiation. Thus,
I0
A = log
It
It does not have any unit.
4. Molar absorptivity (∈) : It is the absorbance of a solution divided by the product of
its optical path l (in centimeter) and molar concentration, C, of the absorbing molecules or
ions.
A
∈ = lit mole−1 cm−1
l⋅C
This property is also known as molar extinction coefficient.
+++
+ +
Monochromatic
lamp
Concave Collimating Slit Filter Cuvette Slit Photocell and recorder

mirror lens (S1) (S2)
Fig. 2: Single beam photoelectric colorimeter

A simple single beam photocolorimeter consists of the components as shown in
Fig. 2. Now-a-days digital colorimeters are used in laboratories, which are very easy to
operate. But with these colorimeters we read only optical density. The transmittance is found
out by using the equation
O.D. = − log T
Experiment No. 1
Aim :
Determine the λmax and concentration of unknown solution of KMnO4 in 2 N H2SO4
solution.
Apparatus :
Colorimeter, filters, 50 ml volumetric flasks, micropipette, beakers, measuring cylinder etc.
Chemicals :
0.01 N KMnO4 stock solution, 2 N H2SO4, distilled water, unknown KMnO4 solution.
63
This experiment is also performed in three parts :

Part A :
Preparation of different concentrations of KMnO4 solutions. First clean the glasswares
properly. Label the volumetric flask from 1 to 8. The different concentrations of KMnO4 are
prepared by using the relation N1V1 = N2V2.
Preparation of solutions :
Flask Conc. of Amount of 2 N H2SO4 Distilled Total final
No. KMnO4 0.01 N added water added volume
solution (N) KMnO4 taken (ml) (ml) (ml)
for dilution
(ml)
1. 0.0005 2.5 25 22.5 50
2. 0.0010 5.0 25 20.0 50
3. 0.0015 7.5 25 17.5 50
4. 0.0020 10.0 25 15.0 50
5. 0.0025 12.5 25 12.5 50
6. 0.0040 20.0 25 5.0 50
7. Unknown given volume 25 upto the mark 50
8. Reference − 25 25 50
Part B & Part C : Procedure, graphs, calculations and results refer the previous
experiment.
Experiment No. 2
Aim :
Determine the λmax and concentration of unknown solution of copper sulphate.
Chemicals :
1. 0.01 M CuSO4 stock solution.
2. Unknown CuSO4 solution.
3. Liquor ammonia.
4. Distilled water.
Apparatus :
1. Colorimeter
2. 50 ml capacity calibrated eight volumetric flasks.
3. Micropipette.
4. Measuring cylinder.
Procedure :
The experiment is carried out in three parts as follows :
64
Part A :
−
Preparation of different concentration of CuSO4 − NH3 complex solutions from the given
0.01 M CuSO4 stock solution.
The glasswares i.e. volumetric flask, beaker, measuring cylinder, which are required for
the experiment were properly cleaned with tap water. The volumetric flasks should be
labelled with numbers one to eight. By using the 0.01 M CuSO4 stock solution the lower
concentrations i.e. 0.006 M, 0.005 M, 0.004 M, 0.003 M, 0.002 M and 0.001 M were prepared
by using the equation N1V1 = N2V2. Thus, in order to prepare 0.006 M and 50 ml solution
from 0.01 M CuSO4 stock solution, the volume to be taken is calculated as follows :
Old (Stock) New (Stock) N1 = 0.01 M
N1V1 = N2V2 V1 = ?
0.01 × V1 = 0.006 × 50 N2 = 0.006 M
V2 = 50 ml
0.006 × 50
∴ V1 = = 30 ml.
0.01
Thus, to prepare 0.006 M and 50 ml solution, 30 ml of stock solution should be
withdrawn and diluted to 50 ml by adding distilled water. i.e. (30 ml 0.01 M stock solution +
20 ml distilled water). Thus, all the solutions were prepared by using same method and are
summarised in the following tabular form.
Preparation of solutions :
Flask Conc. of CuSO4 0.01 M CuSO4 Liquor NH3 Distilled Total volume
No. solution solution taken added water after dilution
M for dilution (ml) (ml) (ml)
1. 0.006 30 12 08 50
2. 0.005 25 12 13 50
3. 0.004 20 12 18 50
4. 0.003 15 12 23 50
5. 0.002 10 12 28 50
6. 0.001 05 12 33 50
7. Unknown given volume 12 upto the 50
mark
8. Reference − 12 38 50
These solutions are prepared in calibrated 50 ml capacity volumetric flask. The solutions
should be shaken well to make them homogeneous. For the preparation of solution, same
measuring cylinder and micropipette should be used throughout the experiment. Thus the
stock solution, liquor ammonia and distilled water should be taken by using same measuring
cylinder and micropipette.
65
Part B : Determination of λmax :

The photoelectric colorimeter is having inbuilt 6 to 8 filters. From these filters, one proper
filter is to be selected. To perform this experiment a blank solution (reference) is prepared by
diluting 12 ml of liquor ammonia to 50 ml using distilled water. From the prepared solutions
the one having highest concentration i.e. 0.006 M is used for this part. Suppose filter no. 1 is
inserted at the proper place. The reference solution is placed in the cell and the instrument is
made on. With the help of zero adjustment knob, the optical density is made zero. Then the
reference solution is removed and the cuvette having 0.006 M solution is inserted at that
place. Waiting for few minutes constant optical density is recorded. Thus, same procedure is
repeated for all the filters and wavelength and optical density is recorded. The wavelength is
plotted against the optical density and from the graph, the filter which is showing maximum
optical density is called as the λmax and is used for the next part.
Observation Table : For λmax
Filter No. Wavelength λ in nm Optical density
1. 450
2. 470
3. 520
4. 540
5. 570
6. 600
7. 620
8. 670
Part C : To find out the O.D. and %T for the known and the unknown solution :
(Using Digital Colorimeter)
1. Insert the filter having λmax in proper place. If inbuilt filter system is there, then adjust
the λmax filter (wavelength) in the light path with the help of filter knob.
2. Rinse the cuvette with reference solution and fill it with the same solution upto the
mark. The outer surface of the cuvette is cleaned with filter paper and is inserted at
the sample cuvette.
3. The instrument is made on. On the display it shows reading. With the help of zero
adjustment knob it is adjusted to read zero optical density. Then this zero adjustment
knob is kept undisturbed throughout the experiment. Now the reference solution is
removed. The cuvette is washed with distilled water and rinsed with the 0.006 M
solution. Then it is filled upto the mark with 0.006 M solution. Clean it from outside
and keep it in the sample cuvette. Make the instrument on wait for few minutes and
record the constant optical density. Repeat the same procedure for remaining
solutions as well as unknown. Report the observations in the observation table as
follow.
66
Observation Table :
Flask No. Concentration Absorbance or % Transmission
in moles/lit. Optical density
1. 0.006
2. 0.005
3. 0.004
4. 0.003
5. 0.002
6. 0.001
7. Unknown
Graphs :
From the observations, plot the following graphs :
(a) Wavelength against optical density.
(b) Optical density against concentration.
(c) % Transmission against concentration.
1.0 1.0 100
0.8 0.8 80
O.D. 0.6 O.D. 0.6 % T 60
0.4 0.4 40
lmax
0.2 0.2 20
Unknown Unknown
100 200 300 400 500 600 700

0.002 0.004 0.006 0.002 0.004 0.006
Wavelength (nm) Concentration (M) Concentration (M)
(a) (b) (c)
Fig. 1
Knowing the optical density and % T of unknown solution, the corresponding
concentration is easily obtained from graphs (b) and (c).
Result Table :
Sr. No. Description Value with units

1. The λmax of the test solution = ………. nm.
2. Conc. of unknown solution from graph (b) = ………. moles/l
3. Conc. of unknown solution from graph (c) = ………. moles/l
67
Experiment No. 3
Aim :
To determine the amount of copper present in the given solution of copper sulphate by
colorimetric titration method using standard solution of EDTA.
Apparatus :
Colorimeter and accessories, volumetric flasks, burette etc.
Theory :
-
HOOCH2C CH2COO
+
HN CH2 CH2N H
-
OOCH2C CH2COOH
Ethylenediamine tetraacetic acid (H2A) is a strong complexing agent and forms
complexes with various metal ions. It is usually used as its disodium salt, Na2H2A. It forms
complexes with copper (II) and many other ions in 1 : 1 mole ratio. The quantitative
estimation of Cu(II) is possible with photometric measurements at a particular wavelength.
The copper – EDTA complex absorbs in the visible region more strongly at wavelength of its
λmax. Known amount of copper solution is taken for estimation and solution of EDTA is added
with the help of burette. The absorbance is noted at 660 nm for each addition of EDTA. The
absorbance goes on increasing with increase in concentration of Cu-EDTA complex upto the
equivalence point. The total Cu ions turn into equivalent amount of Cu-EDTA complex at the
equivalence point giving maximum absorbance. After the equivalence point further addition
of EDTA gives limiting value of absorbance.
Chemicals :
0.05 M (approximate) CuSO4, 0.1 M EDTA, acetate buffer of pH 2.2 − 2.4, (add 1 molar
solution of hydrochloric acid to 350 ml of a solution of sodium acetate of 1 molar
concentration until the pH of the mixture is 2.2 measured by pH meter).
Procedure :
The experiment is carried out in two parts :
Part A : Determination of λmax of Cu-EDTA Complex :
Take 10 ml of 0.05 M (approximate) copper sulphate solution and 20 ml acetate buffer
solution and add 8 ml of 0.1 M EDTA solution to it. Shake the solution and use this for the
determination of λmax of Cu-EDTA complex (use water as blank). Repeat the same procedure
as in previous Experiment No. 2 and find out the λmax.
Part B : Estimation of Copper :
1. Pipette out 10 ml of given solution of copper sulphate in a conical flask and add
20 ml acetate buffer solution and 50 ml water in it.
2. Fill the burette with 0.1 M solution of EDTA. From the burette add 0.5 ml of EDTA into
the conical flask and shake the solution. From this solution take sufficient quantity
into the properly cleaned cuvette and find out its absorbance at λmax, which is
adjusted to read zero optical density by taking water as a blank.
68
3. Transfer the solution from the cuvette back into the conical flask and further add into
it again 0.5 ml of EDTA solution from burette. Shake well and again take it in the
same cuvette upto the mark and find the absorbance of the solution as above. Thus
continue the same procedure upto 2 ml of the burette reading.
4. After 2 ml of burette reading carry on the titration by adding 0.2 ml of EDTA solution
at a time. After the equivalence point constant readings of absorbance are obtained.
Continue the addition till 5-6 fairly constant readings are recorded.
Observation Table : The filter used for the experiment. i.e. λmax = …… nm.
Observation No. ml of 0.1 M EDTA added Absorbance
1. 0.5
2. 1.0
3. 1.5
4. 2.0
5. 2.2
6. 2.4
7. 2.6
8. 2.8
9. 3.0
10. 3.2
11. 3.4
12. 3.6
Graph :
Plot a graph of absorbance against ml of EDTA added. The intersection of two lines gives
equivalence point of the titration. Let it be ‘X’ ml.
1.0
0.9
0.8
0.7
0.6
O.D.
0.5
0.4
0.3
0.2
0.1 X ml
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

ml of 0.1 M EDTA added
Fig. 1
69
Calculations :
1000 ml 1 M EDTA = 63.54 g of Cu2+
1000 ml 0.1 M EDTA = 6.354 g of Cu2+
6.354 × 'X'
‘X’ ml 0.1 M EDTA = g of Cu2+
1000
= ‘W’ g.
10 ml of given solution of CuSO4 contains W g of Cu2+.
∴ 1000 ml of given solution of CuSO4 contains (100 × W) g of Cu2+.
Result Table :
1. λmax of Cu-EDTA complex solution = ………. nm.
2+
2. Concentration of Cu in the given solution = ………. g l−1
Experiment No. 4
Aim :
To determine the indicator constant of methyl red indicator.
Theory :
The acid-base indicator is a substance which varies in colour with the pH of the solution.
It possesses the properties of weak acid or weak base, in some form or the other. According
to the Bronsted concept of acids and bases, the acidic and basic forms of indictor will exist in
the following equilibrium in aqueous solution.
InA + H2O ≡
H3O+ + InB
(acid form) (basic form)
The forms InA and InB have different colours because one of them has a tautomeric form
of different colour existing in equilibrium with it. The equilibrium constant of the above
equilibrium can be written as −
[InB] [H3O+]
KIn =
[InA]
neglecting the activity coefficient terms, KIn is called the indicator constant. Thus, the above
equation can be written as −
[InB]
pH = pKIn + log … (1)
[InA]
Since the intensity of the colour of a solution is a proportional to the concentration of the
substance responsible for the colour. The above equation can be written as
Colour due to alkaline (basic) form
pH = pKIn + log … (2)
Colour due to acidic form
When colour due to the alkaline form predominates over the colour due to the acidic
form ([InB] >> [InA]), the solution has the colour of the alkaline form of the indicator and
vice-versa. Over a certain range of pH, neither of the colours predominates. This range of pH
is called the indicator range and generally lies between pKIn − 1 and pKIn + 1.
70
Now to evaluate the indicator constant, consider the acid-base indicator methyl red. The
methyl red have the acidic form (HMR) and basic form (MR−) as given below.
HMR ≡ MR− + H+
+
N(CH3)2 N(CH3)2 N(CH3)2
N N N
+
+ +H
NH NH N
- - -
COO COO COO
Acid form Basic form
HMR (Red) MR (Yellow)
The dissociation constant K, of this equilibrium between acid form and base form is given
by using equation (1).
[MR−]
pH = pK + log
[HMR]
In this above equation if [MR−] = [HMR] the equation reduces to
pK = pH
From the above discussion, the determination of pK can be done as follows.
The [HMR] and [MR−] have strong absorption peaks in the visible region. Series of
solutions having known pH (between 2 to 10) are prepared and equal amount of methyl red
is added to each of these solutions. The colour intensity of these solutions depends upon the
degree of dissociation which in turn depends on pH of the solution. The solution having low
pH values have red colour while those having higher pH values shows yellow colour. The
solution having pH in between shows intermediate colour between red and vellow. The
absorbances of solutions are determined as a function of pH at proper wavelength. The point
of inflection represents [MR−] = [HMR] and the pH at this situation is pK.
Apparatus :
Colorimeter with filters, pH meter, burettes, 50 ml volumetric flasks (12), calibrated micro
pipette, hard glass test tubes (12), etc.
Chemicals :
Methyl red solution, (Dissolve 20 mg of methyl red in 60 ml of ethanol and dilute to
100 ml by water), 0.2 M disodium hydrogen phosphate, 0.1 M citric acid.
Procedure :
The experiment is performed in three parts as follows :
71
Part A : Preparation of solutions :

1. Clean all the 50 ml capacity volumetric flasks and label them from 1 to 12.
2. Clean two burettes of 50 ml capacity and fill them by 0.2 M Na2HPO4 and 0.1 M citric
acid solution.
3. To prepare the buffer solutions from Na2HPO4 and citric acid in the labelled
volumetric flasks, use the following table :
Flask No. Expected pH 0.2 M Na2HPO4 (ml) 0.1 M citric acid (ml)
1. 3.4 11.40 28.60
2. 3.8 14.20 25.80
3. 4.2 16.56 23.44
4. 4.6 18.70 21.30
5. 5.0 20.60 19.40
6. 5.4 22.30 17.70
7. 5.8 24.18 15.82
8. 6.2 26.44 13.56
9. 6.6 29.10 10.90
10. 7.0 32.94 7.06
11. 7.4 36.34 3.66
12. 8.0 38.90 1.10
4. The hard glass test tubes should be properly cleaned and labelled as 1 to 12. From
the above solutions withdraw 10 ml from each flask and place into the hard glass test
tubes respectively.
5. With the help of micro pipette add one ml of indicator in each of the test tubes and
shake well.
Part B : Determination of pH of buffer solutions :
The buffer solutions prepared in volumetric flask are labelled 1 to 12, their pH is
determined with the help of pH meter as follows :
1. Standardize the pH meter by using standard 0.05 M potassium hydrogen phthalate
solution (as explained in pH metre experiment).
2. Take sufficient amount of buffer solution from flask No.1 in a beaker and dip in it the
combined glass and calomel electrode. Wait for few minutes and record the constant
pH of the solution.
3. Repeat the same procedure for remaining solutions and report their readings as
observed pH of solutions.
Part C : Determination of absorbance :
1. First find out the λmax by using the procedure given in the previous experiment.
Usually for methyl red, blue green filter (490-520 nm) is used.
2. In digital colorimeter inbuilt filters are there, so adjust the filter. In a clean cuvette
take buffer solution from flask no.1 as blank upto the mark. Make cuvette dry and
clean from outside with the help of filter paper and insert it into the sample
compartment.
72
3. Make the instrument on and adjust zero optical density.

4. Remove the cuvette, wash it with distilled water. Now take the solution from hard
glass test tube No. 1 into the cuvette upto the mark. Clean it from outside and insert
it into the sample compartment, make the instrument on, wait for few minutes and
record the constant optical density.
5. Repeat the same procedure for remaining solutions of the hard glass test tube.
Report the observations in the tabular form as follows :
Observation Table :
Solution Observed Absorbance %T ΔA ΔpH ΔA Mean pH
from Test pH A ΔpH
Tube
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Graphs :
ΔA
(i) Absorbance against observed pH, (ii) against mean pH.
ΔpH
0.9
0.8
0.7 -
[MR ]
0.6 =1
[HMR]
DA
Absorbance 0.5 DpH
(A) 0.4
0.3
0.2
0.1
pH = pKa
1 2 3 4 5 6 7 8 9 10
Observed pH
Mean pH
Fig. 1
73
Calculations :
From the graph, the pH value at the inflection or at peak position is equal to pKa.
Knowing the pKa, Ka is obtained as Ka = − log pKa. Thus, the value of dissociation constant Ka
of the indicator is obtained.
Result Table :
1. The λmax of indicator solution. = ………. nm.
2. pKa of the indicator methyl red. = ……….
3. Ka of the indicator methyl red. = ……….
VIVA VOCE
1. Define Beer's and Lambert's law.
2. What is optical density ? What is its unit ?
3. Define the terms :
(i) Radiant power, (ii) Transmittance, (iii) Molar extinction coefficient.
4. What are the different components of single beam colorimeter ?
5. What is the relationship between O.D. and concentration and why ?
6. What is meant by λmax ? Why is it necsessary to determine it ?
7. 'Beer-Lambert's law is applicable to dilute solutions only, explain.
8. Which equation is used to prepare the solution having lower concentration than that
of given stock solution ?
9. In colorimetric estimation of CuSO4 solution, liquor ammonia is added in the
preparation of solution. Why ?
10. How the percent T is obtained from measured O.D. ?
11. Why 2 N H2SO4 is added in the preparation of dilute solutions of KMnO4 ?
12. What is the structural formula of EDTA ?
13. Why the acetate buffer of pH 2.2 - 2.4 is added ?
14. Why there is no change in O.D. after the equivalence point ?
15. Define the indicator constant.
16. Define the indicator range. Give the limiting value of indicator range.
17. What is the nature of absorbance against pH graph and why ?
---
74
2…
Potentiometry
(Any Three)
Theory :
In potentiometry, electromotive force (E.M.F.) of cells and electrode potentials of single
electrodes are measured. Potentiometry has wide range of applications in analytical,
inorganic and physical chemistry.
Electrochemical cells :
Electrochemical cells are used to convert (i) electrical energy to chemical energy and
(ii) chemical energy to electrical energy. A cell is basically an arrangement of two electrodes
dipping in an electrolyte solution, capable of generating electricity due to chemical change
within the cell, or of producing chemical change due to passage of electricity through the
cell.
A cell in which electrical energy is converted into chemical energy is called electrolytic
cell. In such a cell, a non-spontaneous reaction is made to occur by passage of electricity
through the electrolyte. Oxidation and reduction reactions are forced to occur.
A cell in which chemical change generates electricity is called a galvanic or voltaic cell.
In such a cell, spontaneous oxidation and reduction reactions occur producing electricity.
These cells are formed by combining two single electrodes through a porous partition or a
salt bridge.
An electrode in an electrolyte is called a single electrode. At every single electrode there
exists a potential difference called single electrode potential. When two such electrodes
differing in their potential are combined and connected, a spontaneous flow of electrons
takes place generating electricity. This difference in electrode potential of the two electrodes
is called electromotive force (E.M.F.).
Measurement of Electrode Potential :
Electrode potential of different electrodes are measured with reference to standard
hydrogen electrode which is a primary standard electrode. Due to difficulties in construction
of hydrogen electrode, secondary reference electrodes such as calomel electrodes are
commonly used.
75
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Potentiometry
Calomel Electrode :
This secondary reference electrode essentially consists a paste of mercury-mercurous
chloride (Hg2Cl2) and potassium chloride solution of specified concentration as shown in
Fig. 1.
The electrode is represented as
Pt⏐Hg⏐Hg2Cl2(s)⏐KCl(satd.)
The reaction at the electrode is
Hg2Cl2(s) + 2eσ ≡ −
2Hg(l) + 2Cl(satd.)
This electrode is reversible to Cl− ions. The potential of

the electrode depends on concentration of KCl solution
used. The electrode potential at any given temperature ‘t’,
with different concentrations of KCl are given below :
0.1 N KCl E = 0.3338 − 7 × 10−5 (t − 25) Pt
−4
1.0 N KCl E = 0.2800 − 2.4 × 10 KCl solution (saturated)
−4
Saturated KCl l2 = 0.2415 − 7.6 × 10
Hg
Calomel electrode with saturated KCl solution is most
Paste of Hg + Hg2Cl2(s)
convenient to use because of ease of replacing the
solution.
Nernst Equation :
KCl crystals
The single electrode potential of an electrode where
the reaction Mn+ + ne− → M (metal ions in equilibrium
with the metal) occurs is given by the Nernst equation Ceramic disc or
sintered glass disc
o 2.303 RT aM
Ered = Ered − log Fig. 1
F aMn+
o
where, Ered and Ered are the reduction potential and standard reduction potential of the metal,
respectively; R is the molar gas constant, n is the number of electrons involved in the reaction
at the electrode, F is faraday the unit of electricity, aM and aMn+ are the activities of metal and
metal ion respectively. Activity of all metals is taken as one and therefore Nernst equation
becomes
o 2.303 RT 1 o 2.303 RT
Ered = Ered − log = Ered + log aMn+
nF aMn+ nF
Measurement of Cell E.M.F. using Potentiometer :
The potentiometer used for e.m.f. measurements operate on Poggendorff’s
compensation principle. In this method, an unknown e.m.f. is opposed by another e.m.f. till
they are balanced. The circuit diagram of potentiometer is as shown below.
76
P
_ +
C C'
A B
S G
K
_
+
X
Fig. 2
AB is a stretched wire of uniform cross-section usually one meter in length. P, S and X are
the storage cell, standard cell and unknown cell respectively. At any given time only two
sources of E.M.F. are in circuit P and either S or X. P, S and X are connected in such a way
that, their e.m.f.’s oppose each other.
There is a provision to take either S or X in the circuit. The E.M.F. of P is greater than
E.M.F. of S or X. K is the tap key. G, the galvanometer is connected through a sliding contact
which can be moved along AB. The e.m.f. of P is uniformly distributed over the entire length
of wire AB. First the standard cell is brought into circuit and the sliding contact is moved
along AB till at a point C' no current flows through the circuit (indicated by no deflection in
the galvanometer). At this point the bridge is said to be balanced. The potential drop across
AC' is balanced by E.M.F. of standard cell.
i.e. ES ∝ length AC'
Then standard cell is taken out of the circuit and unknown cell whose e.m.f. is to be
measured is brought in the circuit. The sliding contact is again moved along AB till the bridge
is balanced at point C. The potential drop across AC is balanced by E.M.F. of unknown cell X.
i.e. EX ∝ length AC
EX AC
Therefore, =
ES AC'
AC
or EX = E S ×
AC'
Knowing ES and measuring lengths AC and AC’, EX, E.M.F. of unknown cell can be
determined.
Standard Cell :
The standard cell used in measurement of e.m.f. of unknown cells by potentiometry is the
saturated Weston standard cell. The requirements to be met by a standard cell are (i) its
e.m.f. must be reproducible and constant with time, (ii) it should be reversible and should not
be subject to permanent damage due to passage of current through it and (iii) its
temperature coefficient of e.m.f. should be small. The cadmium Weston standard cell satisfies
77
all above requirements. The cell is shown in following figure, when the cell operates the
following reversible reaction takes place.
Cd(s) + Hg2SO4(s) + 8/3 H2O(l) ≡ CdSO4 ⋅ 8/3 H2O(s) + 2Hg(l)
The potential of the cell at 20°C is 1.01830 volt and at 25°C is 1.01807.
Sealing wax
Cork
Saturated CdSO4 solution
Hg + Hg2SO4 CdSO4 8/3 H2O crystals

Hg Cd Amalgam
Fig. 3
Potentiometric Titrations :
The variation of electrode potential with concentration of ions is used as an indicator in
potentiometric titrations. The potentiometric method is applicable to a wide range of
titrations including titrations of highly coloured solutions where visual indicators are useless.
Indicator Electrodes :
For the electrode, a metal and a solution of its own ions Mn+ + neσ ≡ M, the electrode
potential is given by,
2.303 RT
E = E° + log aM+n
nF
For dilute solutions the activity can be replaced by molar concentration i.e.
2.303 RT
E = E° + log Cm+n … (1)
nF
The electrode potential of oxidation-reduction system (where platinum is used as
electrode), the electrode reaction is
Oxidized form + ne ≡ Reduced form and the electrode potential is given by,
2.303 RT Cox
E = E° + log … (2)
nF Cred
where, Cox and Cred are molar concentrations of oxidized and reduced forms respectively. The
electrode potential depends on concentration of both the oxidized form and reduced form.
78
From the above two equations it is clear that the change in electrode potential reflects a
Cox
change in Cm+ or .
Cred
This forms the basis of potentiometric titration. It is impossible to determine E on its own,
the indicating electrode is combined with a reference electrode such as calomel electrode.
The potential of reference electrode does not change during titration.
Salt Bridge : Salt bridge is used to connect the reference electrode with the indicator
electrode in the test solution. The salt bridge is a inverted U shaped tube as shown in Fig. 4.
Stop cock
Agar - Agar + KNO3
Sintered glass disc
Fig. 4
The two ends of U tube are fitted with sintered glass discs of fine porosity. The bridge is
filled with jelly of agar-agar and an electrolyte such as KCl, KNO3, NaNO3 etc.
The positive and negative ions of these salts have nearly same mobility, and hence the
junction potential is minimized.
Titration Cell :
The cell used in potentiometric titration is prepared by combining a reference electrode
and an indicator electrode through a salt bridge.
Typical cells in acid-base titration are –
1. Pt⏐Hg⏐Hg2Cl2(s)⏐Sat. KCl⏐Salt Bridge⏐quinhydrone⏐Pt.
2. Pt⏐H2⏐H+⏐Salt Bridge⏐Sat. KCl⏐Hg2Cl2(s)⏐Hg⏐Pt.
Some of the commonly employed indicator electrodes are :
Ag⏐AgCl⏐Cl−, Pt⏐Fe2+, Fe3+ and Pt⏐quinhydrone, H+.
79
Quinhydrone Electrode :
Quinhydrone is a equimolar mixture of quinine and hydroquinone. The reaction that
occurs is
OH O
+
+ 2H + 2e
OH O
The above reaction can be represented by general equation
QH2 ≡ Q + 2H+ + e
The platinum wire is dipped into a saturated solution of quinhydrone to obtain this
electrode.
The electrode potential of quinhydrone electrode depends on concentration of H+ ions.
o
Its standard potential at any given temperature is given by Ered = − 0.6994 + 0.0007 (t − 25)
o
volt and at 25°C, Ered = − 0.6994 volt.
Experiment No. 1
Aim :
To prepare standard 0.2 M Na2HPO4 and standard 0.1 M citric acid solution and to prepare
four different buffer solutions using them. Determine the pKa value of these and unknown
solution.
Apparatus :
Potentiometer, calomel electrode, platinum electrode, cadmium Weston standard cell,
250 ml standard flask, burette etc.
Chemicals :
Disodium hydrogen phosphate (Na2HPO4.12H2O), citric acid, quinhydrone powder,
0.05 M potassium hydrogen phthalate (pH = 4) solution (solution A) and two given unknown
buffer solutions F and G.
Procedure :
(A) Preparation of standard 0.2 M Na2HPO4 and 0.1 M citric acid solutions :
(i) 0.2 M Na2HPO4 :
Na2HPO4.12H2O molecular weight is 358.2. Therefore, to prepare 250 ml of 0.2 M
Na2HPO4 solution, the quantity required is 17.91 gms.
Accurately weigh 17.91 g of Na2HPO4.12H2O and prepare 250 ml solution in standard
250 ml flask, using distilled water.
(ii) 0.1 M citric acid solution, molecular weight is 192.1 (anhydrous) :
Therefore to prepare 250 ml 0.1 M citric acid solution accurately weigh 4.8025 g of
citric acid and prepare 250 ml solution of it in a standard 250 ml flask, using distilled
water.
80
(iii) Preparation of buffer solutions :

Using above 0.2 M Na2HPO4 and 0.1 M citric acid solutions, prepare four buffer
solutions B, C, D and E as given in the following table.
Buffer Solution Table :
0.2 M Na2HPO4.12H2O (17.91 g/250 ml) + 0.1 M citric acid (anhydrous) (4.8025 g/250 ml).
Buffer solution Volume of 0.2 M Volume of 0.1 M
Na2HPO4.12H2O in ml citric acid in ml
B 10.3 39.7
C 25.8 24.2
D 41.2 08.8
E 48.6 01.4
(B) Standardization of Potentiometer :
(i) Connect the Weston standard cell (E = 1.0185 V) to the potentiometer.
(ii) Standardize the potentiometer. After doing this do not disturb the position of
standardization knobs on your potentiometer throughout the experiment.
(C) Determination of ECalomel : Set up the cell
Pt⏐Hg⏐Hg2Cl2(s)⏐Cl−⏐⏐ H+, quinhydrone⏐Pt+
calomel (Satd) pH = 4
indicator electrode
1. Take about 50 ml of 0.05 M (pH = 4) solution of potassium hydrogen phthalate in
small beaker. Add quinhydrone powder into it till the solution is saturated with it.
Stir well.
2. Place platinum and calomel electrodes into the solution. Connect platinum electrode
to the positively marked terminal on the potentiometer and calomel to the negatively
marked terminal.
3. Record the e.m.f. of this cell as Eobs.
(D) Determination of pH of buffer solutions :
1. Take about 50 ml of the buffer solution B prepared in a small beaker. Add
quinhydrone powder till it is saturated with it. Stir well.
2. Place platinum and calomel electrodes into the solution. Connect platinum electrode
to the positively marked terminal and calomel electrode to the negatively marked
terminal on the potentiometer.
3. Determine the e.m.f. of the cell.
4. In a similar way find e.m.f. of the buffer solutions C, D, E and given unknown solutions
F and G.
5. Record the room temperature as t°C.
81
Observation Table :
1. Room temperature = (t) = ……….. °C.
2. E.M.F. of 0.05 M potassium hydrogen phthalate (solution A) = ……….. volt.
Buffer E.M.F., volts
B
C
D
E
F
G
(E) Calculations :
Calculation of Ecalomel :
o o
EQ − Ecal − Eobs EQ − Ecal − Eobs
pH = =
RT 0.0001984 × T
2.303
F
o
EQ = 0.699 volts, T = t + 273
0.699 − Ecal − Eobs
∴ pH =
0.0001984 × (t + 273)
Using pH of 0.05 M potassium hydrogen phthalate (pH = 4) and its E.M.F. = Eobs find Ecal.
0.699 − Ecal − Eobs of solution A
∴ 4 =
0.0001984 × (t + 273)
Find Ecalomel, ∴ Ecalomel = ………..
(F) Calculation of pH of buffer solutions :
0.699 − Ecalomel − Eobs
pH =
0.0001984 × (t + 273)
Substitute the value of Ecal calculated above and Eobs = E.M.F. of buffer solutions A, B, C,
D, E, F and G and calculate pH of the respective solution.
Result Table :
Buffer pH
B
C
D
E
F
G
82
Experiment No. 2
Aim :
To determine the pKa value of given monobasic weak acid by potentiometric titration.
Theory :
A weak monobasic acid dissociates as
HA ≡ H+ + A−
[H+] [A−]
and dissociation constant Ka =
[HA]
[HA]
∴ [H+] = Ka
[A−]
where [H+], [HA] and [A−] are all equilibrium concentrations. Taking − log of both sides,
we get
[HA]
−log [H+] = − log Ka − log −
[A ]
[HA] [A−]
∴ pH = pKa − log − = pKa + log when acid is half neutralised, [A−] = [HA]
[A ] [HA]
[A−]
∴ log = 0 and hence pH = pKa
[HA]
Therefore, during the course of titration, when the acid is half neutralised, its pH = pKa.
From pKa value, Ka dissociation constant can be calculated. Therefore, if we are able to find
pH or [H+] ion concentration, when the acid is half neutralised we can determine dissociation
constant of the weak acid. The quinhydrone electrode can be used as an indicator electrode
in acid-base titration to find H+ ion concentration.
Apparatus :
Potentiometer, Standard cell, Platinum electrode, Calomel electrode etc.
Chemicals :
0.1 N (approximate) acetic acid solution.
0.5 N (exact) NaOH solution, quinhydrone powder etc.
Procedure :
(A) Standardization of Potentiometer :
Connect the standard cell (E = 1.0185 volt, Weston cell) to the potentiometer and
standardize the potentiometer to 1.0185 volts. After standardization do not disturb the
positions of standardization knobs of your potentiometer.
(B) Potentiometric Titration :
For the acid-base titration set up the cell as follows :
Pt⏐Hg⏐Hg2Cl2(s)⏐Cl−⏐⏐ H+, quinhydrone⏐Pt
Calomel Acetic acid 10 ml
83
1. In a small beaker (100 ml capacity) take 10.0 ml 0.1 N acetic acid and add about
40.0 ml distilled water. To this solution add quinhydrone powder till a saturated
solution of it is obtained. Stir the solution well.
2. Dip a calomel and a platinum electrode into the solution, connect the calomel
electrode to negatively marked terminal and platinum to positively marked terminal
of potentiometer.
4. Add 0.2 ml of 0.5 N NaOH from the burette, stir the solution. And measure the e.m.f.
of the cell.
Microburette
To potentiometer
_
Pt +
0.5 N
NaOH
Calomel
Iron stand
0.1 N acetic
acid + 40 ml water
saturated with
quinhydrone powder
Magnetic stirrer
Fig. 1
5. In a similar way add 0.2 ml NaOH each time and measure the e.m.f. of the cell every
time and record the observations in the observation table.
6. Measure cell e.m.f. till the end point exceeds by about 1.0 ml (i.e. one ml after you
notice a sharp change in e.m.f.). The potentiometer shows negative e.m.f. Take
2-3 negative readings and stop the titration.
7. Plot graph of :
(i) E.M.F. against ml of NaOH added and
ΔE
(ii) against mean V of NaOH
ΔV
Plot both graphs on the same graph paper.
ΔE is the difference in two successive e.m.f. readings.
ΔV is difference in two successive additions i.e. 0.2 ml of NaOH and mean V is the
mean of two successive additions of NaOH.
84
8. From the graph of e.m.f. against ml of NaOH added, find the neutralization point of
the titration.
ΔE
9. From the graph against mean V of NaOH, find e.m.f. at half neutralization point.
ΔV
(C) Determination of Ecalomel :
1. Wash the calomel and platinum electrodes.
2. In a small beaker take about 50 ml of 0.05 M potassium hydrogen phthalate (pH = 4)
solution. Add quinhydrone powder till the solution is saturated with it. Stir well.
3. Dip calomel and platinum electrodes into the solution and connect them to
negatively and positively marked terminals respectively.
4. Determine the e.m.f. of the cell, Eobs.
Observation Table :
Obs. ml of 0.5 N E.M.F. ΔE ΔV ΔE Mean V
No. NaOH added (volts) (volts) (ml) ΔV (ml)
(volt/ml)
1 0 E1 − − − −
2 0.2 E2 E1 − E2 0.2 0.1
3 0.4 E3 E2 − E3 0.2 0.3
4 0.6 E4 E3 − E4 0.2 0.5
− − E5 E4 − E5 − −
− − − − − −
− − − − − −
− − − − − −
− − − − − −
− − − − − −
3.0
Graphs :
DE
E1/2 DV
E.M.F.
Half eq. Equivalence
pt. point x
x
2
+
_
0.5 N ml of Mean V
NaOH added
Mean V
Fig. 2
85
Calculations :
Calculation of Ecalomel :
Using Eobs of 0.05 M potassium hydrogen phthalate (pH = 4) solution find Ecalomel using
the expression
o
EQ − Ecal − Eobs o
pH = , E = 0.699 volts given
0.0001984 × (t + 273) Q
0.699 − Ecal − Eobs pot. hy. phthalate
∴ 4 =
0.0001984 × (t + 273)
∴ Ecal = ……….. volts
Calculation of pKa of acetic acid :
ΔE
1. From graph of e.m.f. vs. ml of 0.5 N NaOH added and vs. mean V
ΔV
(i) Neutralization point = x = ……….. ml
x
(ii) Half neutralization point = = ……….. ml
2
1
(iii) E1/2 e.m.f. at neutralization point = ……….. volts.
2
1
pKa = pH at neutralization point
2
o
EQ − Ecal − E1/2
pH =
0.0001984 × (t + 273)
pKa = ………..
1. E.M.F. of calomel electrode e.g. Ecal = ………. volt
2. Neutralization point = ………. ml
1
3. E1/2 e.m.f. at neutralization point = ………. volt
2
4. pKa = ……….
Experiment No. 3
Aim :
To determine the formal redox potential of Fe2+, Fe3+ system potentiometrically.
Theory :
Consider the following cell involving redox electrode Pt⏐Fe2+, Fe3+,
Pt⏐Hg⏐Hg2Cl2(s)⏐Cl−⏐⏐Fe2+, Fe3+⏐Pt
Calomel
The cell e.m.f. is given by
ECell = EFe2+, Fe3+ − ECal
86
o 2.303 RT
Now, EFe2+, Fe3+ = E + log Fe3+, Fe2+
Fe2+, Fe3+ F
⎡ o 2.303 RT ⎤
∴ ECell = ⎢ E 2+ 3+ + log Fe3+, Fe2+ ⎥ − ECal
⎣
Fe , Fe F ⎦
The electrode potential of Fe2+, Fe3+ system depends on concentration of Fe2+ and Fe3+.
If we add KMnO4 in Pt/Fe2+, Fe3 half cell, concentration of Fe2+ decreases and Fe3+
increases by the reaction
−
5Fe2+ + MnO4 + 8H+ ⎯→ 5Fe3+ + Mn2+ + 4H2O
3+
⎡Fe ⎤
and the ratio ⎢ 2+⎥ increases and cell e.m.f. increases.
⎣Fe ⎦
Now near end point there is a sudden decrease of Fe2+ ion and therefore e.m.f. sharply
increases. The above reaction involves H+ and electrode potential also depends on H+.
Therefore, to avoid the change in H+, the titration is carried out with large excess of
H2SO4 (2M). At half equivalence point, [Fe2+] = [Fe3+] then,
[Ecell]1/2 neutralization point = EFe2+, Fe3+ − Ecal
o
∴ E = (Ecell)1/2 neutralization point + Ecalomel
Fe2+, Fe3+
Eformal redox = Ecell at 1/2 neutralization point + Ecalomel

Apparatus :
Potentiometer, calomel electrode, platinum electrode, standard cell etc.
Chemicals :
0.05 M potassium hydrogen phthalate, 0.01 N ferrous ammonium sulphate, 0.05 N
KMnO4.
Procedure :
Connect the Weston standard cell (E = 1.0185 V) to your potentiometer, standardize the
potentiometer to 1.0185 volts using fine and course knobs on your potentiometer. After
doing this do not disturb these knobs throughout the experiment.
(B) Determination of Ecalomel :
1. Take 50 ml of 0.05 N potassium hydrogen phthalate in a small beaker. Add
quinhydrone powder till saturated with it. Stir the solution using a magnetic stirrer.
2. Dip a platinum and a calomel electrode. Connect calomel and platinum electrodes to
the terminal marked as positive and negative respectively on the potentiometer.
3. Find e.m.f. of the cell Eobs for 0.05 N potassium hydrogen phthalate solution.
87
(C) Redox Titration :

Set up the cell as shown in Fig. 1.
Microburette
0.05 N KMnO4
To potentiometer
_
+
Platinum electrode
Calomel
electrode
10 ml 0.01 N Ferrous
Ammonium Sulphate
+ 40 ml 2N H2SO4
Iron
stand
Magnetic stirrer
Fig. 1
Pt⏐Hg⏐Hg2Cl2(s)⏐KCl⏐⏐ Fe2+, Fe3+⏐Pt
calomel (satd)
1. In a small beaker take 10 ml 0.01 N ferrous ammonium sulphate and add about 40 ml
2 N H2SO4 solution to it.
2. Dip calomel and platinum electrodes in the solution.
3. Connect platinum electrode and calomel electrode to the terminals marked positive
and negative respectively on the potentiometer. Stir the solution. Measure e.m.f. of
the cell.
4. Add 0.2 ml 0.05 N KMnO4 solution from the microburette in the ferrous ammonium
sulphate solution, stir the solution. Measure the e.m.f. of the cell.
5. In a similar way take e.m.f. measurements each time adding 0.2 ml of KMnO4 solution
till the end point exceeds by about one ml (indicated by sharp change in e.m.f.).
6. Plot the graphs
ΔE
(i) E.M.F. against ml of KMnO4 added and (ii) against mean V of KMnO4 added.
ΔV
ΔE
7. From the graph of against mean V, find equivalence point.
ΔV
8. From the graph of e.m.f. against ml of KMnO4 added, find E1/2 e.m.f. at half
equivalence point.
88
Observation Table :
(i) E.M.F. of 0.05 N potassium hydrogen phthalate cell = ………. volts.
(ii) Room temperature = ………. °C.
No. KMnO4 (volts) (volts) (ml) ΔV (ml)
added (volt/ml)
1 0.0 E1 − − − −
2 0.2 E2 E2 − E1 0.2 0.1
3 0.4 E3 E3 − E2 0.2 0.3
4 0.6 E4 E4 − E3 0.2 0.5
− − − − − −
− − − − − −
− − − − − −
− − − − − −
− − − − − −
− − − − − −
16 3.0
Graphs :
E.M.F.
DE
DV
Equivalence
E1/2 point x
Half eq. pt. x/2
ml of KMnO4 Mean V
Fig. 2
∴ Equivalence point = ……….
and E1/2 e.m.f. at half equivalence point = ……….
Calculations :
1. Determination of Ecalomel :
o
EQ − Ecal − Eobs
pH =
0.0001984 (t + 273)
o
EQ = 0.699 volt and t = Room temperature
89
Using pH = 4 for solution of 0.05 M potassium hydrogen

phthalate and its Eobs, find Ecal.
0.699 − Ecal − Eobs
∴ 4 =
0.0001984 (t + 273)
∴ Ecalomel = ………… volts.
2. Formal Redox Potential :
o
E = E1/2 + Ecal
Fe2+, Fe3+
Result Table :
1. Ecalomel = ………. volt
2. Equivalence point = ………. ml
3. E1/2 e.m.f. at 1/2 equivalence point = ………. volt
o
4. o = ………. volt
Eformal = E
Fe2+, Fe3+
Experiment No. 4
Aim :
To determine the amount of sodium chloride in the given solution by potentiometric
titration against silver nitrate solution.
Theory :
Consider the following concentration cell :
−
Ag⏐AgNO3⏐Salt Bridge⏐AgNO3⏐Ag+
C1 C2
The cell e.m.f. is due to difference in concentration of silver nitrate in the two half cells.
If we add sodium chloride in say right hand side half cell the following reaction takes place.
AgNO3 + NaCl → AgCl ↓ + NaNO3
A precipitate of silver chloride is obtained. As a result the concentration C2 decreases and
the electrode potential undergoes a change and as a consequence the cell e.m.f. changes.
This change in cell e.m.f. corresponds to the amount of sodium chloride added. This provides
a basis for the potentiometric titration of AgNO3 against NaCl.
Apparatus :
Potentiometer, silver electrodes, KNO3 or NaNO3 or NaNO2 salt bridge, standard cell etc.
Chemicals :
0.01 N AgNO3, 0.05 N (approximate) NaCl.
Procedure :
(A) Standardization of Potentiometer : Connect the Weston standard cell (E = 1.01850
volts) to the potentiometer and standardize the potentiometer using knobs on your
potentiometer to 1.0185 volts. After this do not disturb the knobs till the experiment is over.
90
(B) Titration of AgNO3 with NaCl :

Microburette
To potentiometer
_ + 0.05 M NaCl
Salt bridge
Ag
Ag
Iron
stand
10 ml. 0.01 M
20 ml. AgNO3 + 40 ml.
0.01 M
distilled water
AgNO3
Magnetic stirrer
Fig. 1
Set up the following cell :
−
Ag AgNO3 NaNO2 AgNO3 Ag+
20 ml Salt bridge 10 ml 0.01 M
0.01 M + 40 ml distilled water
1. In a small beaker take 10 ml 0.01 M AgNO3 and add about 40 ml distilled water and
this is the half cell in which titration is carried out.
2. In another small beaker take about 20 ml 0.01 M AgNO3 solution.
3. Place two silver electrodes in the two beakers.
4. Connect the two half cells (beakers) using a NaNO2 or KNO3 or NaNO3 bridge.
(Do not use KCl salt bridge because diffusion of Cl− ions from salt bridge will
precipitate silver chloride. NaNO2 salt bridge is preferable because it quickly forms a
gel with agar-agar or gelatine.]
5. Connect the silver electrode in the titration flask to the positive terminal and the
other silver electrode to the negative terminal of the potentiometer.
7. Add 0.2 ml of 0.05 M NaCl solution into the titration flask. Stir the solution using a
magnetic stirrer. A precipitate of silver chloride is obtained. Find e.m.f. of the cell.
8. In a similar way add 0.2 ml of 0.05 M NaCl every time and find the e.m.f. of the cell.
9. Take e.m.f. measurement till the equivalent point exceeds by about one ml (upto
3.0 ml addition of NaCl). Report the observations in the observation table.
ΔE
10. Plot the graphs – (i) E.M.F. vs. ml of NaCl added and (ii) against mean V of NaCl
ΔV
added.
91
ΔE
11. From the graph against mean V, find the neutralization point.
ΔV
Observation Table :
No. NaCl added (volts) (volts) (ml) ΔV (ml)
(volts/ml)
1 0 − − − −
2 0.2 0.2 0.1
3 0.4 0.2 0.3
4 0.6 0.2 0.5
− − − − − −
− − − − − −
− − − − − −
− − − − − −
− − − − − −
− − − − − −
16 3.0 2.9
ΔE is the difference between two successive e.m.f. values and ΔV is the difference
between two successive additions of NaCl. Mean V is the mean of two successive additions of
NaCl.
Graphs :
E E
DE
DV
Equivalence
point (V1)
ml of AgNO3 added ml of AgNO3 added Mean V

(I) (II) (III)
Fig. 2
Depending on the concentrations C1 and C2 in the two cell you may get graph of type I
or type II.
92
Calculations :
ΔE
From the graph versus mean V find the equivalence point, that is amount of NaCl
ΔV
required to react with 10.0 ml 0.01 M AgNO3 (V1).
(i) Normality of NaCl :
NaCl = AgNO3
N1V1 = N2V2
N1 × V1 = 0.01 × 10
0.01 × 10
∴ N1 = g. equi. l−1
V1
(ii) Strength of NaCl :
Strength = Normality × Equivalent weight
= N1 × 58.5 g l−1
(iii) Amount of NaCl in 10.0 ml given solution
10
= N1 × 58.5 × g
1000
Result Table :
1. Equivalence point or amount of NaCl (0.05 N) = = ………. ml
required to precipitate AgCl completely.
2. Exact normality of NaCl = ………. g equi. l−1
3. Strength of NaCl solution = ………. g l−1
4. Amount of NaCl in 10 ml of given NaCl solution = ………. g.
Experiment No. 5
Aim :
To determine the amount of chloride and bromide from their mixture by potentiometric
titration with silver nitrate solution.
Theory :
When silver nitrate is added to a solution of mixture of chloride and bromide, silver ions
react with solution of Cl− and Br− ions to form AgCl and AgBr. Though both are sparingly
soluble salts the solubility of AgBr is less than solubility of AgCl. Therefore, first precipitation
of AgBr occurs. After the complete precipitation of AgBr, the precipitation of AgCl begins.
This forms the basis for titration of halide mixture against silver nitrate solution
potentiometrically. The cell used in this titration is
−
Pt⏐Hg⏐Hg2Cl2(s)⏐(satd.) KCl ⏐⏐ Halide solution (Br−, Cl−)⏐Ag+
calomel electrode
93
ΔE
The plots of e.m.f. vs. ml of AgNO3 added and against mean V show two equivalence
ΔV
points corresponding to complete precipitation of AgBr and AgCl respectively. From these
amounts of chloride and bromide present in the mixture can be determined.
Apparatus :
Potentiometer, standard cell, calomel and silver electrodes, microburette etc.
Chemicals :
Given halide mixture (0.01 approximate equinormal mixture of Cl− and Br− ions), 0.01 N
AgNO3 solution.
Procedure :
Connect the standard cell (Weston) to the potentiometer and standardize the
potentiometer to 1.0185 volts using the fine and course adjustment knobs on the
potentiometer. After this do not disturb the standardization knobs throughout the
experiment.
(B) Titration :
1. In a small beaker take 10 ml of the given halide mixture containing Cl− and Br−. Add
about 40 ml distilled water. Stir the solution using a magnetic stirrer.
2. Dip a silver and a calomel electrode into the solution. Connect the calomel electrode
to negatively marked terminal and silver electrode to positively marked terminal of
the potentiometer.
3. Measure the e.m.f. of the cell.
4. Add 0.5 ml of 0.01 N AgNO3 solution into the halide mixture, stir the solution well
and measure e.m.f. of the cell.
5. In a similar way take measurement of e.m.f. values every time adding 0.5 ml AgNO3
till the total equivalence point exceeds by about 4.0 ml (Take about
25 measurements). Report the readings in the observation table as below.
6. Plot the graphs :
(i) E.M.F. vs. ml of AgNO3 added.
ΔE
(ii) against mean V of AgNO3 added.
ΔV
7. From the graphs find the amount of AgNO3 required for complete precipitation of
AgBr and AgCl.
94
Observation Table :
No. AgNO3 E (volts) (ml) ΔV (ml)
added (volts) (volt/ml)
1 0 E1 − − − −
2 0.5 E2 E1 − E2 0.5 0.25
3 1.0 E3 E2 − E3 0.5 0.75
4 1.5 E4 E3 − E4 0.5 1.25
5 2.0 E5 E4 − E5 0.5 1.75
− − − − − −
− − − − − −
− − − − − −
− − − − − −
− − − − − −
14.0 0.5
Graphs :
Br
Cl
DE
DV
E.M.F.
+
_ ml of AgNO3 V1 V2
Mean V
Fig. 1
ΔE
From the graph against mean V :
ΔV
1. Amount of AgNO3 0.01 N required for complete precipitation of Br− = V1 ml.
2. Amount of AgNO3 0.01 N required for complete precipitation of Cl− = (V2 − V1) ml.
Calculations :
1. Calculation of bromide present in the mixture :
Atomic weight of bromide = 79.9
−
AgNO3 + Br− = AgBr ↓ + NO3
1 mole 1 mole ppt.
∴ 1000 ml 1 N AgNO3 ≡ 1 N Br−
= 79.9 g Br−
95
∴ 1000 ml 0.01 N AgNO3 = 0.799 g Br−

∴ V1 ml of 0.01 N AgNO3 = ?
0.799 × V1
= g Br−
1000
= X (say)
−
X gms of Br present in 10 ml of given solution
1000 × X
∴ Br− present in 1 litre solution = = 100 X g l−1
10
2. Amount of Cl− : Atomic weight of chloride = 35.5
−
AgNO3 + Cl− ⎯→ AgCl ↓ + NO3
1 mole 1 mole
1000 ml 1 N AgNO3 ≡ 1 N Cl−
= 35.5 g Cl−
∴ 1000 ml 0.01 N AgNO3 = 0.355 g Cl−
0.355 × (V2 − V1)
∴ (V2 − V1) ml 0.01 N AgNO3 = g Cl−
1000
= Y say
−
Amount of Cl per litre
10 ml solution contains Y gms of Cl−
∴ 1000 ml solution contains 100 × Y g Cl−
Result Table :
1. Equivalence point of Br− (V1) = ………. ml
−
2. Equivalence point of Cl (V2 − V1) = ………. ml
− −1
3. Amount of Br in g l = ………. g l−1
4. Amount of Cl− in g l− = ………. g l−1
VIVA VOCE
1. What is a cell ?
2. Define electrolytic and galvanic cells.
3. What is a single electrode ?
4. What is single electrode potential ?
5. What is half cell ? How two half cells are combined to form a cell ?
6. What is solution pressure and osmotic pressure ?
7. Single electrode potential depends on which factors ?
8. Give the Nernst equation for single electrode potential.
96
9. Define oxidation and reduction potential.

10. How the cells are represented ?
11. How will you represent a silver electrode in a silver nitrate solution ?
12. Mention the different types of electrodes.
13. What are the conventions used in the representation of a cell ?
14. A cell is formed by combining calomel electrode with standard hydrogen electrode
using KCl salt bridge. How you will represent it ?
15. What is a primary standard and a secondary standard electrode ?
16. What is a reference electrode ?
17. What is an indicator electrode ?
18. Explain the construction and working of standard hydrogen electrode.
19. Mention the different types of cells.
20. What is a quinhydrone electrode ? Explain how it is useful in acid-base titrations.
21. What is a concentration cell ?
22. What is a cell with and without transference ?
23. What is junction potential ? How it is minimized ?
24. What is salt bridge ? What are its advantages ?
25. Which electrolytes are used in salt bridges ?
26. Explain the construction and working of calomel electrode.
27. What is a standard cell ?
28. Why a potentiometer is standardized ?
29. What is a potentiometer ?
30. Why a voltmeter is not used instead of potentiometer, in e.m.f. measurements of a
cell ?
31. Explain the working of Cadmium Weston cell. What is its e.m.f. at 25°C ?
32. What is e.m.f. series and what are its applications ?
33. What is standard electrode potential ?
34. What is e.m.f. of a cell ?
35. Give the dependance of e.m.f. on temperature.
36. What is a potentiometric titration ?
37. What are the different types of potentiometric titration ?
97
38. The following cell is used in an acid-base titration.

+
Pt⏐H2⏐H(1M)⏐⏐ H+, quinhydrone⏐Pt
(1 atm)
Identify the indicator electrode.
39. What is a redox electrode ?
40. What are the advantages of potentiometric titrations ?
41. What is the accuracy of determination of equivalence point in a potentiometric
titration compared to a conventional volumetric titration ?
42. Explain the potentiometric titration curve of an acid against a base ?
ΔE
43. Why a peak is obtained at the equivalence point in the plot of against mean V ?
ΔV
44. Why pH = pKa at half neutralization point ?
45. How will you determine half neutralization point ?
46. How will you find pH at half neutralization point ?
47. What is the sign convention of e.m.f. ?
48. Which expression you use in calculating Ecal in a potentiometric titration of pKa
determination ?
49. Explain now pH of a solution is determined by using potentiometric method ?
50. What is buffer solution ?
51. How pH of buffer solutions are determined using potentiometer ?
52. Give Henderson equation of pH of a buffer solution.
53. Which electrodes you will use in precipitation titration of AgNO3 against Na2SO4 ?
54. Can you determine pK1 and pK2 of a dibasic weak acid using potentiometric
titration ?
55. pK1 and pK2 should differ by what amount so that two peaks are obtained in the plot
ΔE
of against mean V ?
ΔV
56. A tribasic acid H3PO4 is titrated against NaOH potentiometrically. What is the nature
of the graph of e.m.f. against ml of NaOH added ?
---
98
3…
pH Metry
(Any Two)
Theory :
The acidity and basicity of a solution is measured in terms of pH and pOH. For dilute
solutions the concentration of acids or bases such as 0.1 or 10−1 M, 0.01 or 10−2 M or 10−3 M
solution involve negative exponents. Sorenson suggested a convenient method to express
hydrogen ion concentration without involving negative exponents. He defined the terms pH
and pH scale. Mathematically pH is defined as –
1
pH = log10 = − log [H+]
[H+]
1
and pOH = log = − log [OH−]
[OH−]
For any aqueous solution [H+] [OH−] = Kw ionic product of water. Taking negative
logarithm to base 10 of both sides, we get
− log10 [H+] − log10 [OH−] = − log10 Kw
or pH + pOH = − log10 Kw
at 25°C Kw ionic product of water = 10−14
Therefore, at 25°C,
pH + pOH = − log 10−14
or pH + pOH = 14
In water, [H−] = [OH−]
∴ [H+] [OH−] = 10−14 at 25° C
or [H+] = 10−7 = [OH−]
∴ pH of water = − log 10−7 = 7 = pOH
∴ For neutral solutions, pH = pOH = 7
For acidic solution, [H+] = 10−7
∴ pH is less than 7 from above definition
For bases, pOH is greater than 7 or pH is less than 7.
∴ Thus,
(i) pH < 7, pOH > 7 Solution is acidic
(ii) pH > 7, pOH < 7 Solution is basic
99
T.Y.B.Sc. Practical Chemistry (Physical Practicals) pH Metry
(iii) pH = pOH = 7 Solution is neutral

Now by above definition when [H+] = 1 gm mole l−1, then pH = 0 and hence pOH = 14.
Similarly, when [OH−] = 1 gm mole l−1, pOH = 0 and pH = 14.
∴ pH range from 0 to 14 is taken as a pH scale for dilute solutions.
pH ⎯→ 0 7 14
Scale Acidic Neutral Basic
Measurement of pH : The pH values of acidic or basic solutions are conveniently
measured by using pH meter. The electrodes used in pH metry are glass electrode and
calomel electrodes.
Glass Electrode : When a glass surface is in
contact with acidic solution, some potential
difference exists between glass surface and the
solution. The magnitude of this potential
difference depends on the nature of the glass
and H+ ion concentration of the solution. If two
solutions differing in their [H+] ion concentration
i.e. of different pH are put on the two sides of
Ag or Pt wire
the glass surface a potential difference is

established. If the pH of one of the two solutions
is kept constant then potential developed
Ag-AgCl(s) electrode
depends only on the pH of the other solution.

Thin walled
This is the principle used in glass electrode. 0.1 M HCl glass bulb
solution
In the simplest form, the glass electrode
consists of a tube connected to a thin walled Fig. 1: Schematic of glass electrode
glass bulb with high conductivity.
The bulb contains a solution of constant hydrogen ion concentration and an electrode of
definite potential such as silver chloride electrode in 0.1 M HCl solution. The bulb is inserted
in the experimental solution whose pH− is to be measured. This electrode can be expressed
as
Ag⏐AgCl(s), 0.1 M HCl⏐glass⏐experimental solution
The commonly used reference electrode in combination with glass electrode is calomel
electrode.
The cell used for pH measurements is represented as
Ag⏐AgCl(s)⏐Glass⏐Experimental solution⏐Cl−⏐Hg2Cl2⏐Hg
0.1 M HCl
Glass electrode Calomel electrode
100
The potential of such a cell can be measured using potentiometer and hence the pH of
the solution.
Experiment No. 1
Aim :
To determine the degree of hydrolysis of aniline hydrochloride by pH metric method.
Theory :
Aniline hydrochloride is a salt of a strong acid and a weak base. It hydrolyses as
C6H5NH3Cl ≡ +
C6H5NH3 + Cl−
+
C6H5NH3 + H2O ≡ C6H5NH2 + H3O+
The hydrolysis constant Kh of the reaction is given by,
[C6H5NH2] [H3O+]
Kh = +
[C6H5NH3 ]
h2C
=
1−h
Kh ≈ h2C
where, ‘h’ is degree of hydrolysis and C is concentration in moles/lit.
At equilibrium, if [H3O+] = [H+] = hC.
∴ If [H3O+] = hC is measured then h and Kh can be determined.
Apparatus :
pH meter, glass electrode, calomel electrode, burette etc.
Chemicals :
Aniline hydrochloride powder, 0.05 M potassium hydrogen phthalate solution (pH = 4)
etc.
[A] Standardization of pH meter :

Wash the glass and calomel electrodes with distilled water.
1. In a small beaker take about 50 ml. of 0.05 M potassium hydrogen phthalate solution.
2. Dip a calomel and a glass electrode into the solution. Ensure that the bulb of glass
electrode is completely dipped into the solution. Connect the two electrodes to the
proper terminals of pH meter.
3. Adjust the temperature knob to room temperature. Put the pH range selector switch
on 0-7 pH range side, if it is there with pH meter.
4. Adjust the course and fine standardization knobs so that pH meter reads the pH = 4.
After this adjustment do not disturb the standardization knobs throughout the
experiment.
[B] Preparation of aniline hydrochloride solutions :
101
1. Prepare aniline hydrochloride solution by dissolving accurately weighed 1.295 g of

aniline hydrochloride in water and diluting it to 100 ml. using a 100 ml. volumetric
flask.
2. From 0.1 M aniline hydrochloride solution prepare the following solutions :
(i) Take 50 ml of 0.1 M aniline hydrochloride solution using 25 ml pipette and dilute
to 100 ml by distilled water, which is 0.05 M aniline hydrochloride.
(ii) 0.025 M Aniline hydrochloride : Take 50 ml of 0.05 M aniline hydrochloride and
dilute to 100 ml by distilled water.
(iii) 0.0125 M Aniline hydrochloride : Take 50.0 ml of 0.025 M aniline hydrochloride
and dilute to 100 ml by distilled water.
(iv) 0.00625 M Aniline hydrochloride : Take 50 ml of 0.0125 M aniline
hydrochloride and dilute to 100 ml by distilled water.
[C] Determination of pH of aniline hydrochloride solutions :
1. Take 50 ml of 0.1 M aniline hydrochloride in a small beaker.
2. Wash the glass and calomel electrodes with distilled water and then dip into aniline
hydrochloride solution. Ensure that the bulb of glass electrode is completely
immersed in the solution.
3. Keep the temperature knob at room temperature value.
4. Put pH selector switch at 0-7 pH range.
5. Find the pH of the solution.
6. In a similar way find pH of remaining aniline hydrochloride solutions. Record the
reading of pH of all solutions in the observation table as below.
Observation Table :
Obs. Conc. of pH Degree of Hydrolysis Average
No. aniline hydrolysis ‘h’ constant value of Kh
hydrochloride Kh
mol l−1
1. 0.1
2. 0.05
3. 0.025
4. 0.0125
5. 0.00625
Calculations :
h2C
Hydrolysis constant Kh = = h2C ( 1−h 1)
1−h
⎛Kh⎞1/2
∴ h = ⎜ ⎟
⎝C⎠
102
Kh
Now, [H+] = hC = C × = KhC = (KhC)1/2
C
pH = − log [H+]
= − log hC = − log (KhC)1/2
1 1
∴ pH = − log Kh − log C
2 2
∴ 2 × pH = − log Kh − log C
or log Kh = − 2 × pH − log C
or Kh = antilog [−2 pH − log C]
Substituting the value of pH and C of the solutions of aniline hydrochloride, find Kh. Find
average Kh.
Now, Kh = h2C
Substituting the values of Kh and C, find h of each of the solution of aniline
hydrochloride.
Result Table :
Hydrolysis constant of aniline hydrochloride = ….
Experiment No. 2
Aim :
To determine the pKa value of weak acid by pH metric titration with a strong base.
Theory :
A weak acid HA ionizes as HA ≡ H+ + A− and its dissociation constant Ka is given by
[H+] [A−]
Ka = .
[HA]
[H+], [A−] and [HA] are equilibrium concentrations of the respective species.
[HA]
∴ [H+] = Ka −
[A ]
[HA]
∴ log [H+] = log Ka + log
[A−]
[A−]
or − log [H+] = − log Ka + log
[HA]
[A−]
or pH = pKa + log
[HA]
at half neutralization point, [HA] = [A−] and hence at half neutralization point, pH = pKa.
Therefore, by finding pH of the solution when the solution in the cell is half neutralized
pKa can be calculated. This forms the basis for determination of pKa by pH metry. By
performing pH metric titration neutralization point is determined graphically and hence the
half neutralization point.
103
Apparatus :
pH meter, glass electrode, calomel electrode, burette, beaker etc.
Chemicals :
0.1 N acetic acid, 0.5 M NaOH, 0.05 M potassium hydrogen phthalate (pH = 4) solution.
Procedure :
1. Using 0.05 M potassium hydrogen phthalate (pH = 4) solution standardize the pH
meter as described in the previous experiment of pH metry.
2. Take 10.0 ml of 0.1 M acetic acid in a small beaker. Add about 40 ml distilled water.
Stir the solution well.
3. Dip calomel and glass electrodes into the solution. Ensure that the bulb of the glass
electrode dips completely in the solution. Connect the glass and calomel electrodes
to the proper terminals of the pH meter.
4. Adjust the temperature selector switch to room temperature value.
5. Turn the pH selector switch to pH 0 - 7 range.
6. Find the pH of the solution.
7. Add 0.2 ml of 0.5 M NaOH into the acid solution. Stir the solution and find the pH.
8. In a similar way find pH values of solution by adding 0.2 ml alliquotes of 0.5 M NaOH
each till the neutralization point exceeds by about one ml (upto 3.0 ml addition of
NaOH). Report the readings in the observation table.
ΔpH
9. Plot the graphs : (i) pH against ml of NaOH added and (ii) against mean V of
ΔV
NaOH added. Find neutralization point and pH at half neutralization point which is
equal to pKa.
Observation Table :
Obs. 0.5 M NaOH pH ΔpH ΔV (ml) ΔpH Mean V

No. added (ml) ΔV (ml)
1 0 pH1 − − − −
2 0.2 pH2 pH2 − pH1 0.2 0.1
3 0.4 pH3 pH3 − pH2 0.2 0.3
4 0.6 pH4 pH4 − pH3 0.2 0.5
5 − − − − 0.7
− − − − − −
− − − − − −
104
− − − − − −
− − − − − −
16 3.0 −
Graphs :
pH
DpH
DV
pH at half
neutralization
point Half neutralization point
x/2 x Neutralization point

ml of NaOH added
Mean V
Fig. 1
Calculations :
ΔpH
From the graph of against mean V, find the neutralization point. From the graph of
ΔV
pH against ml of NaOH added, find pH at half neutralization point which is equal to pKa.
pH at half neutralization point = pKa
Result Table :
pKa of given weak acid = ……….
Experiment No. 3
Aim :
To determine the dissociation constant of oxalic acid by pH metric titration with a strong
base.
Theory :
Oxalic acid HOOC − COOH is a dibasic acid and ionizes in two steps as
1. COOH COO−
⏐ K1 ⏐ + H+
⎯→
COOH COOH
K1 is dissociation constant of first ionization.
2. COO− COO−
⏐ K2 ⏐ + H+
⎯→ −
COOH COO
105
K2 is dissociation constant of second ionization. The ionization of oxalic acid is

characterized by two different ionization constants K1 and K2. It is observed that for oxalic
K1
acid > 104 and when the solution of oxalic acid is titrated against NaOH solution, the
K2
titration curve will show two pronounced inflections.
K1
If < 104 the titration curve shows only one inflection. This is true for all dibasic acids.
K2
For tribasic acids which ionize in three steps there are three ionization constants K1, K2
and K3.
K1 K2
1. If < 104 and < 104 only one inflection is observed in the titration curve.
K2 K3
K1 K2
2. If > 104 and < 104, two inflections are observed.
K2 K3
K1 K2
3. If > 104 and > 104, three pronounced inflections are observed in the titration
K2 K3
curve. Thus, in order to find values of ionization constants in which different steps are
involved in polybasic acids, the ionization constants should differ by large amount
(104 times).
K1
Now, in oxalic acid, > 104.
K2
COOH COO−
Therefore, two pronounced inflections are obtained, one when ⏐ ⎯→ ⏐ + H+
COOH COOH
COO−
the ionized species ⏐ itself behaves as weak acid and undergoes further ionization with
COOH
ionization constant K2. pH-metry offers a very convenient method to obtain K1 and K2 of
oxalic acid.
Apparatus :
pH-meter, glass electrode, calomel electrode etc.
Chemicals :
0.05 N oxalic acid, 0.2 N NaOH, 0.05 M potassium hydrogen phthalate (pH = 4 solution).
Procedure : (A) Standardization of pH meter :
Standardize the pH-meter using 0.05 M potassium hydrogen phthalate (pH = 4) solution
as described in the first experiment of pH-metry.
(B) Titration :
1. Take 10.0 ml of 0.05 N oxalic acid in a beaker and add about 40 ml distilled water
into it, stir the solution and as described in previous experiment, measure pH of the
solution using pH meter.
106
2. Add 0.2 ml of 0.2 N NaOH into the oxalic acid solution, stir the solution and measure
pH of the solution.
3. In a similar way go on adding 0.2 ml of 0.2 N NaOH each time and measure pH of the
solution every time upto 4.0 ml total addition of NaOH (i.e. end point exceeds by
about 1.5 ml). Report the readings in the observation table as shown below.
ΔpH
4. Plot the graphs : (i) pH against ml of NaOH added, (ii) against mean V.
ΔV
5. From the graph, find two neutralization points corresponding to two ionization
constants K1 and K2.
Observation Table :
Obs. 0.2 N NaOH pH ΔpH ΔV (ml) ΔpH Mean V
No. added (ml) ΔV (ml)
1 0 pH1 − − − −
2 0.2 pH2 pH2 − pH1 0.2 0.1
3 0.4 pH3 pH3 − pH2 0.2 0.3
4 0.6 pH4 pH4 − pH3 0.2 0.5
− − − − − −
− − − − − −
− − − − − −
− − − − − −
4.0 − − 0.2 3.9
Graphs :
(pH2)1/2
DpH
DV
pH
(pH1)1/2 1/2(V2 - V1) V1 V2
ml of NaOH added Mean V

1/2V1
Fig. 1
ΔpH
From the graph of versus mean V, find :
ΔV
107
1. V1 the amount of NaOH for the complete dissociation of the first −COOH group K1.
2. (V2 − V1) the amount of NaOH required for complete ionization of second −COOH
group.
3. From the graph of pH against ml of NaOH added find (pH1)1/2 = pK1 for ionization
and (pH2)1/2 = pK2 for the second ionization as shown in the above plot.
Result Table :
1. pK1 of oxalic acid = ……….
2. pK2 of oxalic acid = ……….
Experiment No. 4
Aim :
To determine the pH of various mixtures of sodium acetate and acetic acid in aqueous
solutions and hence to find the dissociation constant of acetic acid.
Theory :
The mixture of sodium acetate and acetic acid in aqueous solution is a buffer solution.
Buffer solutions are the solutions which resist a sudden change in pH due to addition of
small amounts of strong acid or base. An acidic buffer is a mixture of a weak acid and its salt
with a strong base. A basic buffer is a mixture of a weak base and its salt with strong acid.
For example,
CH3COOH + CH3COONa is an acidic buffer and NH4Cl + NH4OH is a basic buffer.
The pH of an acidic buffer HA + BA is given by the Henderson equation which is
[Salt]
pH = pKa + log
[Acid]
[Salt]
According to the equation, the pH of an acidic buffer depends on the ratio
[Acid]
because pKa is constant. pH of any solution can be accurately determined by pH meter and
[Salt]
if the ratio is known the dissociation constant can be calculated.
[Acid]
Apparatus :
pH meter, glass electrode, calomel electrode, 50 ml volumetric flasks etc.
Chemicals :
0.1 M acetic acid, 0.1 M sodium acetate, 0.05 M potassium hydrogen phthalate solution.
Procedure :
(A) Prepare the following buffer solutions using 0.1 M acetic acid and 0.1 M sodium
acetate solutions :
Buffer solution ml of 0.1 M ml of 0.1 M
Acetic Acid Sodium Acetate
A 47.5 2.5
108
B 45 5.0
C 40 10.0
D 35 15.0
E 30 20.0
F 25 25.0
G 20 30
H 15 35
I 10 40
J 7.5 42.5
K 5.0 45.0
L 2.5 47.5
(B) Standardization of pH meter, as explained in the previous experiment. Standardize
the pH meter using 0.05 M potassium hydrogen phthalate (pH = 4) solution :
(C) Measurement of pH of buffer solutions :
1. In a small beaker take the buffer solution A. Dip the calomel and glass electrode after
washing and ensure that the bulb of the glass electrode is immersed completely in
the solution.
2. Adjust the temperature selector switch at room temperature value.
3. Put the pH-range selector switch at 0 - 7 pH-range.
4. Determine pH of the solution A.
5. In a similar way find pH of remaining buffer solutions.
Observation Table :
Sol. ml of 0.1 M ml of 0.1 M Conc. of Conc. of [Salt] pH
log
No. Acetic Acid Sodium Acetate Acid Salt [Acid]
[Acid] [Salt]
A 47.5 2.5 0.95 0.005 − 1.2787
B 45 5.0 0.09 0.01 − 0.9542
C 40 10.0 0.08 0.02 − 0.6020
D 35 15.0 0.07 0.03 − 0.368
E 30 20.0 0.06 0.04 − 0.1761
F 25 25 0.05 0.05 0.00
G 20 30 0.04 0.07 0.3680
H 15 35 0.03 0.07 0.3680
I 10 40 0.02 0.08 0.6021
J 7.5 42.5 0.015 0.085 0.7533
K 5.0 45.5 0.01 0.09 0.9542
L 2.5 47.5 0.005 0.095 1.2787
Calculations :
1. Calculation of concentration of acid in buffers :
47.5 ml 0.1 M acetic acid is diluted to 50 ml (Total volume).
109
47.5 × 0.1
∴ [Acid] = = 0.95
50
2.5 ml 0.1 M sodium acetate is diluted to 50 ml (Total volume).
2.5 × 0.1
∴ [Salt] = = 0.05
50
In a similar way, calculate the value of [Acid] and [Salt] for the remaining solutions.
Calculated values are given in the observation table.
Graph :
[Salt]
Plot a graph of pH against log .
[Acid]
pH
[Salt]
pH = pKa + log
[Acid]
[Salt] pH = pKa
when, [Salt] = [Acid], log =0
[Acid]
_
∴ pH = pKa [salt]
+
log
Find the intercept of y-axis which gives the value of pKa. [acid]
− log Ka= pKa Fig. 1
∴ log Ka = − pKa
∴ Ka = antilog [−pKa]
Result Table :
Dissociation constant of acetic acid (Ka) = ……….
VIVA VOCE
1. Define pH and pOH.
2. Why pH of 0.1 N HCl solution and 0.1 N acetic acid are not same ?
3. What expression you will use to find pH of a weak monobasic acid ?
4. Prove the relation pH + pOH = 14.
5. What is ionic product of water ?
6. What is the pH range of acidic and basic solutions ?
7. What is the pH scale ?
8. What is the pH of 0.001 N HCl ?
9. What is the pH of 0.01 N H2SO4 and 0.01 M H2SO4 ?
10. What is Ostwald’s dilution law ?
11. What is the expression for [H+] ions of a weak acid in terms of degree of ionization
and dissociation constant ?
12. What is basicity of an acid ? Explain with examples.
13. What is the expression of pH of a buffer solution ?
110
14. What different methods you will employ to determine pH of a solution ?

15. What is the pH of 0.1 N NaOH ?
---
111
4…
Radioactivity
(Any One)
Theory :
Certain elements which emit α, β or γ radiations spontaneously at any temperature and
pressure are known as radioactive elements and the phenomenon is called as Radioactivity.
During the radioactive disintegration process, the original radioactive element transforms
into another element which may or may not be radioactive. The initial radioactive element is
called as parent while the new element that is formed is called daughter. Usually the heavy
particles like α are emitted by radio elements having mass number greater than 210. While
the lighter particles alike β+ or β− are emitted by lighter as well as heavier elements. From the
behaviour of ion pairs in the electric field different regions have been observed. Thus in the
ionization chamber region and proportional region the counters which are working are used
to measure α particle. In the Geiger-Muller region in which G.M. counter works and used to
measure the β particles.
Geiger-Muller Counter :
_
+ To high voltage
source and counter
Tungsten wire (anode)

Argon 80 mm pressure Copper cylinder (cathode)
+ quenching agent 20 mm
pressure Glass or quartz outer jacket
Glass bead
Thin mica window

-2
(2-3 mg cm thick)
Radioactive source
Source holder
Stand
Lead castle
Fig. 1
Principle :
Gases get ionized when α, β or γ radiations are allowed to pass through them.
111
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Radioactivity
Construction :
It consists of a copper tube which acts as cathode and fused inside the glass or quartz
tube. The diameter of this tube is 2 cm, while is 10 cm in length. At the centre of tube is a
thin tungsten wire which acts as anode. The tube is completely evacuated and filled with
argon gas 80 mm of Hg pressure and quenchers like ethyl iodide or halogens at 20 mm of
Hg pressure. At the other end of the tube there is a thin mica window through which the
β particles are allowed to enter inside the tube. The G.M. tube is kept inside the thick lead
castle to minimize the background counts. Usually the G.M. tube is mounted on a stand
having number of groves to keep radioactive sample infront of the G.M. tube. The
experimental set up of G.M. counter is shown in Fig. 1.
Working :
When the β particle enters inside the G.M. tube through the window, it produces
ionization in the gas resulting in the production of ion pairs. Due to the application of high
potential the electrons are quickly attracted towards the anode. The electrons produce
secondary ionisation which is called as Townsend avalanches. The electrons in the avalanches
will be collected by the anode, living behind the positive ions sheath which has a low
mobility. The discharge takes place at the electrodes and electric pulse is registered.
Under the influence of high applied voltage, the electrons reach the central anode in
about 5 × 10−7 sec, after their generation. The positive ions move very slowly and cluster
around the central wire. These positive ions reduce the potential gradient much below the
one required for gas multiplication, the counter therefore becomes insensitive. The positive
ions react with cathode in about 100 to 500 µsec. after their generation. Till they reach the
cathode, the counter is insensitive and is not in a position to register a pulse of current. The
period of time, after registering the ionization event, during which the counter is not in a
position to register another such event, is called the dead time of the counter. During dead
time, the counter recovers and becomes ready to register another ionization event.
The positive ion sheath in non self quenching tubes gradually travels towards the
cathode and the positive ions combine with electrons from the cathode. The neutralized
positive ions come to the ground state emitting photons. The liberated photons strike the
filling gas molecules like that of argon and ionise the filling gas molecules to form ion pairs.
Thus unless these photoelectrons are stopped, they again give rise to Townsend avalanche
process by acceleration towards the anode and the discharge process goes into cycle, which
is unwanted for efficient Geiger counting. The multiple discharge in the G.M. counter can be
prevented by addition of filling gas as quenching agent and are, the ethyl alcohol, ethyl
iodide or halogens. A positive ion of the filling gas in trying to reach the cathode strikes
quenching gas molecules. Because of the difference in ionization potentials the charge is
transferred to quench the gas molecules. The neutralised ion emits the excess energy
photon. The quenching gas molecules absorb these radiations getting themselves
dissociated. The quenching gas ions which are formed in the process of exchange of charge
with the filling gas, positive ions go to the cathode surface and get neutralized by capturing
an electron from the cathode surface. Its excess energy is utilized to dissociate the quenching
molecule.
112
The radioactive gases present in the atmosphere as well as due to the cosmic radiations
the G.M. counter will show some counts. Thus the G.M. counter without keeping any
radioactive source infront of the G.M. tube shows some counts. These counts are called as
background counts. In order to minimize the background counts the G.M. tube is kept inside
the thick lead castle. In order to get the actual counts the background counts are to be
subtracted from the observed counts.
⎡Corrected counts⎤ ⎡Observed counts⎤ ⎡Background counts⎤
Thus, ⎢ ⎥=⎢ ⎥−⎢ ⎥
⎣ per min ⎦ ⎣ per min ⎦ ⎣ per min ⎦
Experiment No. 1
Aim :
To determine the plateau voltage of the given G.M. counter.
Theory :
The behaviour of ion pairs in an electric
field shows that as the applied potential
increases the counts per minute go on
increasing. (Refer Fig. 1). For the counting of
β particles in the Geiger region it is observed
C.P.M.
that in a particular voltage region the
number of counts per minute are found to
be constant. Thus in the graph of CPM Geiger plateau
against the applied potential the curve has
Working potential
nearly flat portion and is known as plateau
region. This region is small for α particles Applied voltage
because of their great specific ionization Fig. 1: Plot of applied voltage Vs. C.P.M.
while for β particles it is greater because of their lower specific ionization. The pulse
rate increases with the applied voltage. After a particular voltage the pulse rate becomes
independent of the applied voltage.
This voltage is being called Geiger threshold. The range of voltage over which the pulse
rate is independent of the applied voltage is called Geiger plateau. The mid point of this
Geiger plateau region and the corresponding applied voltage is taken as the working
potential of the. G.M. tube. The main advantage of G.M. counter is large size of current
pulses. The amplification is therefore unnecessary.
Apparatus and Instruments :
Geiger-Muller tube, Geiger counting system, radioactive source, lead castle, stand,
radioactive source holder etc.
Procedure :
The G.M. tube is mounted on a stand and is kept inside the thick lead castle. The G.M.
tube is connected to the counting system properly. The voltage knob of the counter is kept
on the minimum and the counter is made on. The system is allowed to warm up at least five
minutes.
113
1. Set up the timer for 3 minutes and the paralysis time knob on 250 μsec. position.
2. With the help of source holder keep the radioactive source infront of the G.M. tube at
a fixed position in a definite groove of the stand.
3. Now apply the minimum voltage say 100 volts and press the reset button and then
press the start button. Record the counts for three minutes. Take at least three trials
and record it in the observation table.
4. Increase the voltage by 30 volts. Press the reset and then start button. Again record
the counts for three minutes. Take three trials. This process is repeated till the plateau
and a small part of the rising portion of characteristic curve is reached. Do not
increase the potential above 1500 volts for old G.M. tubes (now-a-days G.M. tubes
are having working potential upto 700 volts). For these tubes do not increase the
potential above 900 volts otherwise G.M. tube will be damaged. Slowly bring the high
voltage to the minimum, then switch off high voltage as well as mains.
In this experiment the counts for three minutes are recorded and it is found that there
may be large variation in counts for the same applied potential. Therefore mean counts per
minute are calculated.
Observation Table :
Counts for three minutes Counts
Voltage
Obs. No. I II III Average per
applied (V)
minute
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
Graph :
Plot the graph of CPM against applied voltage. From the graph note the plateau region.
Find out the mid-point of plateau region and the voltage corresponding to it, is the working
potential of G.M. counter.
Result Table :
Sr. No. Description Value with unit
1. Plateau voltage of the G.M. ………. volts
counter
114
Experiment No. 2
Aim :
To determine the resolving time of the given G.M. counter.
Instruments and Apparatus :
G.M. counter system, two nearly equal and strong radioactive sources, lead castle, stand
etc.
Procedure :
Connect the G.M. counter system to the high voltage source. Keep the voltage knob of
the counter on minimum. Make the mains on and allow the system to warm up for at least
5 minutes. Mean while set up the timer as well as paralysis time (250 µs, 500 µs) to any
desired value with the help of respective knobs. After five minutes of warming period set up
the voltage knob equal to the working potential of G.M. tube as noted in the previous
experiment.
1. Now first find out the background counts for 5 minutes and hence obtain the
background counts per minute.
2. From the two selected radioactive sources call any one as S1 and the remaining as S2.
Take the source S1 on a sample holder the position 1 and keep it infront of the G.M.
tube on the definite groove of the stand in the lead castle. Record the counts for two
minutes. Take three trials and find out the counts per minute. Let it be R1.
3. Remove the source S1, keep the source S2, at the position number 2, on the sample
holder (planchet). Now keep the holder having source S2 in the same position as S1 in
the definite groove in the lead castle. Measure the counts for two minutes. Take two
trials and report counts per minute. Let it be R2.
4. Keep the source S1 at position number 1 and source S2 at position number 2 on the
planchet. Keep the planchet along with the sources in the same groove in the lead
castle. Measure the counts for two minutes. Take two trials and find out the counts
per minute (R1,2).
S1 2 1 S2 S1 S2
Planchet
Fig. 1
Observation Table :
Sr. No. Description Value
1. Background counts per minute = RB = ……….
2. Counts per minute for source S1' = R1 = ……….
3. Counts per minute for source S2' = R2 = ……….
4. Counts per minute for S1 and S2 together = R1, 2 = ……….
115
Calculations :
R1 + R2 − R1, 2 − RB
Resolving time T =
(R1, 2)2 − (R1) − (R2)2
Express the resolving time T in microseconds.
Result :
Sr. No. Description Value with
units
1. Resolving time of the G.M. counter … microseconds
Experiment No. 3
Aim :
To determine the Emax of β particles.
Theory :
Majority of radioactive elements emit β particles. β particles are the electrons having
negative charge. The particles are very tiny having negligible mass and so high penetration
power and low specific ionization. The β particles emitted by some radioactive source have
various energies i.e. from few millivolt to 3.15 MeV. Thus the maximum energy associated
with β particles can be find out by performing this simple experiment. In this experiment, the
absorption of β particles is studied by placing radioactive source infront of G.M. tube and
recording the counting rate with suitable thickness of absorbing material inserted between
the source and the counter. The aluminium foils are used most frequently as an absorber.
The maximum range of β particles can be obtained in terms of mg cm−2 of aluminium using
the following relation
Rmax = 543 Emax − 160
Rmax + 160 Thickness range + 160
Emax = = MeV
543 543
Apparatus :
G.M. counter, β emitting source, Aluminium absorbers of various thickness.
Procedure :
Do the connection and all settings as explained in the previous experiment and then
apply the plateau voltage (or the working potential of G.M. tube) as obtained in the earlier
experiment to the G.M. counter.
1. With the help of planchet keep the β emitting radioactive source in a suitable groove
in the lead castle. Record the counts for two minutes. Take at least two trials and then
convert into counts per minute.
2. With the help of absorber holder keep the thinnest aluminium absorber in the groove
above the source. Again measure counts for two minutes. Take two trials and convert
into counts per minute.
116
3. Repeat the same procedure for all the aluminium absorbers, as well as make some
combinations of the absorbers. Report the observations in the observation table as
follows :
Observation Table :
Source = ………. Working Plateau Voltage = ………. volts
Sr. Filter or Thickness Counts for two minutes Counts log

No. Absorber of the per min. C.P.M.
I Trial II Trial Average
No. filter C.P.M.
(mg cm−2)
1.
2.
3.
4.
5.
6.
7.
8.
Graph :
Plot the graph of log CPM against the thickness of the absorber.
log CPM
Rb
Rmax
Absorber thickness
-2
(mg cm )
Fig. 1
From the graph obtained find Rmax and then calculate Emax by using the equation
Rmax + 160
Emax = MeV
543
117
Result :
Sr. No. Description Value with
units
1. Range of β particles, Rmax ….. mg cm−2
2. Emax of β particles ….. MeV
VIVA VOCE
1. Define the term Radioactivity.
2. Which particles are emitted by radioactive elements ?
3. What is the principle of G.M. counter ?
4. Define specific ionization.
5. What is the use of thick lead castle ?
6. Why is it necessary to measure the background counts ?
7. Define dead time and resolving time of G.M counter.
8. Explain the terms plateau region and plateau voltage.
9. The plateau region of β is larger than α particles, explain.
10. Which is the equation to determine the resolving time ?
11. Explain the meaning of the terms Emax and Rmax.
12. What is the relation to find out Emax of β particles ?
---
118
5…
Conductometry
(Any Two)
Conductivity of Electrolytes :
The solutions of electrolytes conduct electricity through ions. In the solution, the
electrons are carried by migration of positive and negative ions toward the electrodes under
the influence of an applied potential. The solvents which are poor conductors of electricity
are used for the preparation of solutions of electrolytes so that the conductivity of electrolyte
solution is almost entirely due to ions obtained from the ionization of the electrolytes. Water
is the best solvent for conductivity measurements. Like metallic conductors, the electrolyte
solutions obey Ohm’s law.
Ohm’s Law :
The resistance of an uniform column of electrolyte placed between two parallel
electrodes of cross-sectional area, ‘A’ square centimeter and separated by a distance of
‘l’ centimeter is given by
l
R ∝
A
l
or R = ρ×
A
The constant of proportionality ρ is called as specific resistance.
When l = 1 cm and A = 1 cm2, then R = ρ.
Therefore, the specific resistance is defined as the resistance of one centimeter cube of
conducting medium. The specific resistance is measured in unit ohm cm.
Conductance :
The reciprocal of R is called conductance and is measured in ohm−1.
Conductivity or Specific Conductance (σ) :
The reciprocal of ρ, the specific resistance is called specific conductance or simply the
conductivity.
1
Conductivity or specific conductance σ = ρ
l
Using Ohm’s law R = ρ we get,
A
1 1 A
Conductance = =ρ×
R l
119
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Conductometry
A
Conductance = σ
l
A
∴ Conductance = Specific conductance ×
l
l
For electrolytic conductance, the ratio i.e. the ratio of distance between the electrodes,
A
l and area of cross-section, A is called cell constant.
1
Therefore, Conductance = Specific conductance × .
Cell constant
Specific conductance or conductivity is measured in ohm−1 cm−1, the specific conductance
of strong and weak electrolytes increases with concentration of the electrolytes. This is due to
increase in number of ions per unit volume of the solution. Concentration of solutions are
measured in terms of moles per litre or gram equivalent per litre. Taking this into account
two more quantities called molar conductivity and equivalent conductivity are defined. Both
of these are properties of the conducting medium.
Molecular or Molar Conductivity μ :
It is defined as the conductivity of a volume of solution containing one gram mole of
electrolyte placed between two electrodes one centimeter apart and large enough to contain
all the solution. Molecular conductivity is given by the expression
1000 × σ
μ = =σ×V
C
where, C is concentration of electrolyte in moles per litre and V is the volume of solution
containing one mole of electrolyte. Molecular conductivity is measured in ohm−1 cm2.
Equivalent Conductivity, ^ :
It is defined as the conductivity of a volume of solution containing one gram equivalent
of electrolyte placed between two electrodes one centimeter apart and large enough to
contain all the solution.
Equivalent conductivity is given by the expression :
1000 × σ
^ = C
=σ×V
where, C is the concentration of electrolyte in gram equivalents per litre of solution and V is
the volume of solution containing one gram equivalent of electrolyte. Equivalent conductivity
is measured in ohm−1 cm2.
According to Faraday’s laws in electrolytic conductance, the amount of substances
liberated in equivalent conductivity is more commonly used.
Equivalent conductance decreases with concentration for both strong and weak
1
electrolytes because decrease in ^ due to the term is more than increase in ^ due to
C
increase in specific conductivity.
120
The equivalent conductance is given by the equation,

1000 × Specific conductance (σ)
^ = C
where, C is concentration of electrolytes in gram equivalents per litre of the solution.
Equivalent conductance decreases with concentration for both strong and weak
electrolytes or in other words increases with dilution. This is because the increase in σ with
1
concentration is more than compensated by the decrease in term with concentration.
C
Equivalent Conductance at Infinite Dilution :
For both strong and weak electrolytes, equivalent conductance increases with dilution
and reaches a limiting value at zero concentration of electrolytes. This limiting value is called
as equivalent conductance at infinite dilution represented by the symbol ^0.
For strong electrolytes the ^ is calculated by graphical method using the Kohlrausch
equation for dilute solutions.
^ = ^0 − b C
For weak electrolyte the ^0 value is calculated by using Kohlrausch law of independent
migration of ions. This law states that at infinite dilution, the dissociation of electrolyte is
complete and each ion moves independently of the other ion and makes a definite
contribution to the equivalent conductance at infinite dilution. This definite contribution by
each ion is called equivalent ionic conductance at infinity dilution. Therefore, Kohlrausch law
of independent migration of ions can be stated mathematically as
0 0
^0 = l+ + l−
0 0
where, l+ and l− are equivalent ionic conductances at infinite dilution of positive and negative
ions respectively.
The Degree of Dissociation and Conductance :
The equivalent conductance ^ at any dilution is due to dissociation of electrolyte at that
dilution and ^0 value at infinite dilution is due to complete dissociation of electrolyte.
^
Therefore, the ratio represents the degree of dissociation.
^0
Further, for weak electrolyte, the dissociation constant is given by the expression
α2 C
K =
1−α
By measuring ^ and ^0, the degree of dissociation α and hence dissociation constant of
weak electrolyte can be determined.
121
Measurement of Conductance :
Resistance and conductance of electrolytic solution are measured by using Wheatstone
Bridge method.
Wheatstone Bridge Circuit :
c
ab - A wire of uniform cross-section
Rx Rs Rx - The unknown resistance

G
I1 Rs - Variable known resistance
R1 d R2
a b d - Sliding contact
I2
I E - Battery
E
G - Galvanometer
Fig. 1
At point b, the current I from the battery is divided into two currents I1 and I2. The sliding
contact ‘d’ is moved along ab till the point d is found when no current flows through the
galvanometer. The bridge is said to be balanced. The points d and c are at the same potential
when the bridge is balanced. The potential drops from b to d and b to c are equal and
so also the potential drops from d to a and c to a are equal i.e.
RSI1 = R2I2 and RXI1 = R1I2
⎛R1⎞
From these two equations, we get RX = RS × ⎜ ⎟ .
⎝R2⎠
R1 and R2 are proportional to lengths ad and db and can be measured. Hence,
RX unknown resistance can be measured.
For measurement of resistance of electrolyte solutions, the following modifications are
necessary in the Wheatstone bridge method.
(i) Direct current cannot be used because it causes electrolysis and concentration
changes occur at the electrodes. To avoid this alternating current (A.C.) is used. The
products of electrolysis obtained during the passage of first half cycle of the
alternating current are almost completely eliminated by the subsequent second half
cycle of the alternating current. That is alternating current eliminates polarisation.
(ii) With the use of alternating current, the balancing of the bridge is sharpened by
putting a variable condenser (capacity) across the standard resistance.
(iii) As a.c. is used instead of galvanometer as detector, a cathode ray oscilloscope or any
other suitable device is employed.
122
Pt Pt
Pt Pt
(a) (b)
Pt
Pt
(c) Dipping type (d) Dipping type

Fig. 2
The use of alternating current eliminates the polarisation. But following two factors must
be taken into account to completely eliminate polarisation.
(a) The electrode must not dissolve. Therefore inert metal like platinum as electrode
should be used.
(b) The surface area of the electrode should be large. For this purpose, platinised
platinum electrodes are used and are called platinum black electrodes. By electrolysis
method platinum in the form of fine platinum particles are adsorbed over the surface
of platinum electrodes, thereby increasing the surface area to a large extent.
Preparation of Solutions :
All theoretical relations developed in electrolytic conductance are for dilute solutions of
electrolytes. Therefore while doing conductivity measurements, dilute solutions are to be
used. Therefore all solutions are to be prepared carefully using accurately weighed quantities
of electrolytes. All glass apparatus used in conductivity experiments must be made of
resistance glass such as jena, pyrex or quartz.
Conductivity cells :
Depending on the type and accuracy of measurement conductivity cell of different
shapes and sizes are used. Basically all conductivity cells are made of resistance glass such as
pyrex and contain two parallel platinised platinum electrodes. The distance between the
electrodes is measured by measuring resistance of a solution of known specific conductance.
The different types of cells used are shown in Fig. 2.
123
For solutions of high conductance the cell with large distance between the two
electrodes, cell a, is used; for solution of low conductance, cell with small distance between
the electrodes, cell b, c and d are used.
Conductivity water :
Water, which is usually used as solvent for conductivity measurement must be of good
purity. The specific conductance of electrolyte cannot always be equal to (specific
conductance of solution) − (specific conductance of water), the specially prepared water
called conductivity water should be used. The conductivity water should not have specific
conductance greater than 3 × 10−6 ohm−1 cm−1. The tap water and deionised water show
specific conductance more than 10−6 and hence should not be used.
Conductivity water is obtained by mixing double glass distilled water with small amount
of KMnO4 and NaOH and then the mixture is redistilled with a tall reflux, alkali trap, and
condenser. The first and last fraction of distillate is rejected. The middle fraction shows
conductance of less than 1 × 10−6 ohm−1 cm−1. The middle fraction is collected and stoppered
immediately to avoid contamination of carbon dioxide.
Temperature Control :
Conductance depends on temperature, therefore, conductance measurements are made
keeping temperature constant using a thermostat.
Experiment No. 1
Aim :
To determine the cell constant of the given cell using 0.01 M KCl solution and hence
determine the dissociation constant of given weak monobasic acid.
Apparatus :
Conductivity bridge, magnetic stirrer, beaker (100 ml), standard flasks 50 ml or 100 ml
etc.
Procedure :
(I) Determination of cell constant of the given cell :
1. Wash the electrodes of given conductivity cell first with conductivity water and then
with 0.01 M KCl.
2. In a small beaker (100 ml) take about 50 ml of 0.01 M KCl solution. Place the cell into
the solution. The electrodes of the cell should completely dip into the solution.
3. Place the conductivity cell setup into a thermostat at a constant temperature either at
25°C or at 30°C.
4. Connect the electrodes of the cell to the conductivity bridge and find the
conductance or resistance of the solution.
(II) Determination of conductance of 0.1 N acetic acid :
1. Wash the electrodes of the conductivity cell first with conductivity water and then
with 0.1 N acetic acid. During both washing take care that the position of the
electrodes is not distributed.
124
2. Place the cell in 0.1 N acetic acid solution (about 50 ml), see that the electrodes
immerse completely into the solution. Place this setup in a thermostat at a constant
temperature either at 25°C or at 30°C.
3. Connect the conductivity cell to the conductivity bridge and find conductance or
resistance of 0.1 N acetic acid.
4. Now prepare 0.05 N, 0.025 N, 0.0125 N acetic acid solutions and measure
conductance of each of these solutions.
Preparation of 0.05 N, 0.025 N and 0.0125 N acetic acid solution :
1. 0.05 N Acetic acid solution : Take 50 ml of 0.1 N acetic acid solution and dilute to
100 ml in a 100 ml volumetric flask using conductivity water.
2. 0.025 N Acetic acid solution : Take 50 ml of 0.05 N acetic acid prepared above and
dilute to 100 ml using conductivity water.
3. 0.0125 N Acetic acid solution : Take 50 ml of 0.025 N acetic acid and dilute to
100 ml using conductivity water.
Observations :
1. Temperature of water bath = ………… °C
2. Conductance of 0.01 M KCl solution = ………… ohm−1
OR
2. Resistance of 0.01 M KCl solution = ………… ohm
3. Given that specific conductance of 0.01 M KCl solution
= 0.001412 ohm−1 cm−1 at 25°C
= 0.001552 ohm−1 cm−1 at 30°C
4. Given that equivalent conductivity of acetic acid at infinite dilution
−1 2
^0 = 390.8 ohm cm
Observation Table :
Sr. No. Concentration of acetic Conductance in ohm−1
acid
1. 0.1 N
2. 0.05 N
3. 0.025 N
4. 0.0125 N
Calculations :
(I) Cell constant of given cell :
Specific conductivity of 0.01 M KCl
Cell constant =
Conductance of 0.01 M KCl
125
(II) Determination of dissociation constant Ka of acetic acid :

(i) Specific conductivity of acetic acid = Cell constant × Conductance
1000 × Specific conductance
(ii) Equivalent conductance ^ = C
C = 0.1 for 0.1 N acetic acid
= 0.05 for 0.05 N acetic acid and so on
^
(iii) Degree of dissociation, α =
^0
α2C
(iv) Dissociation constant Ka =
1−α
Using the above four steps calculate dissociation constant of acetic acid. Tabulate the
results as below.
Result Table :
(i) Cell constant of the given cell = ……….. cm−1.
Conc. of Conductance Specific Equivalent Degree of Dissociation
acetic acid ohm−1 conductance conductance dissociation constant
−1 2
ohm−1 cm−1 ^ ohm cm α Ka
0.1 N
0.05 N
0.025 N
0.0125 N
CONDUCTOMETRIC TITRATION
End point of various titrations can be determined using conductivity measurements.
A titration where end point is determined by conductance measurement is called
conductometric titration.
Addition of one electrolyte solution into another electrolyte solution will result in change
of conductance because of change in volume and possible ionic reactions.
Now consider the addition of dilute solution of electrolyte (A+ B−) to another dilute
solution of electrolyte (C+ D−). If the change in volume is negligible and temperature is kept
constant then
(a) If there is no chemical reaction, then conductance of CD gradually increases on the
addition of AB due to increase in number of ions.
(b) If there is an ionic reaction to produce either only slightly ionised or insoluble
substance represented as
A+ B− + C+ D− ⎯→ A+ D− + CB
126
Then there is marked change in conductance at the equivalence point. From the above
equation it is clear that when solution of AB is added to CD, C+ ion is replaced by A+ ion. The
ionic conductances of different ions are different and conductance may increase or decrease
depending on the mobility values of A+ and C+.
If the ionic mobility of A+ is greater than ionic mobility of C+ then conductance increases
and if ionic mobility of A+ is less than C+ then conductance decreases. This is the basic
principle of any conductometric titration.
As an illustration let us consider the following titrations :
(1) Titration of a strong acid against a strong base and
(2) A precipitation titration of a solution of lead nitrate against sodium sulphate solution.
1. Titration of a strong acid against a strong base :
NaOH + HCl → NaCl + H2O
Na+ + OH− + H+ + Cl− → Na+ + Cl− + H2O
When NaOH solution is added to HCl solution, H+ ion in solution is replaced by Na+ ion.
The mobility or ion conductance of H+ ion is more than mobility or ion conductance of Na+
ion. A high mobile cation is replaced by a less mobile cation and conductance of the solution
decreases. This decrease in conductance takes place with every addition of NaOH solution till
HCl solution or H+ ions are present in the solution. When neutralisation is complete, that is all
the H+ ions are replaced by Na+ ions, further addition of NaOH increases conductance due to
presence of excess of OH− ions. If a graph of volume of NaOH added against conductance is
plotted, we get two straight lines in V shape intersecting at equivalence point as shown
below.
Conductance
Equivalence point
ml of NaOH added
Fig. 1
2. Precipitation titration between Pb(NO3)2 and Na2SO4 solution :
When a dilute solution of Na2SO4 is added to another dilution of Pb(NO3)2, the following
reaction occurs :
Na2SO4 + Pb(NO3)2 → PbSO4 ↓ + 2NaNO3 or
−2 −2 −
2Na+ + SO4 + Pb+2 + 2NO3 → PbSO4 ↓ + 2Na+ + 2NO3
ppt
127
As Na2SO4 solution is added high mobile Pb+2 ion is replaced by two Na+ less mobile
ions, resulting in slight decrease of conductance. When the reaction is complete, that is all
Pb+2 ions are replaced by Na+ ions, the further addition of Na2SO4 results in increase in
−2
conductance owing to the presence of excess of SO4 ions. Therefore, before equivalence
point there is slight decrease in conductance and after equivalence point there is a sharp
increase in conductance. A graph of ml of Na2SO4 against conductance consists of two lines
intersecting at equivalence point.
During conductometric titrations, to avoid large volume changes due to addition of one
electrolyte solution into another solution, the titrant (the solution in burette) must be at least
5 times stronger than the other solution.
Experiment No. 2
Aim :
To estimate the amount of lead present in the given solution of lead nitrate by
conductometric titration with sodium sulphate.
Apparatus :
Conductivity bridge, conductivity cell, microburette of capacity 5 or 10.0 ml, magnetic
stirrer, breaker, pipette etc.
Chemicals :
0.1 N (approximate) Pb(NO3)2 solution, 0.5 N Na2SO4 solution, conductivity water.
Procedure :
1. Wash the electrodes of conductivity cell with conductivity water and then rinse them
with 0.1 N Pb(NO3)2 solution.
2. Take 10.0 ml of 0.1 N Pb(NO3)2 in a small beaker of capacity not more than 100 ml.
Add about 40 to 50 ml of conductivity water and dip a conductivity cell into the
solution. The electrodes should be completely immersed into the solution. Put a
magnetic needle.
3. Place the beaker with the solution with conductivity cell on a magnetic stirrer and stir
the solution for few minutes.
4. Connect the conductivity cell to the conductivity bridge and determine the
conductance or resistance of 0.1 N Pb(NO3)2 solution. Set up the apparatus as shown
in Fig. 1.
5. Fill a microburette with 0.5 N Na2SO4 solution.
6. From burette add 0.2 ml of Na2SO4 solution into the lead nitrate solution and stir the
solution. Observe the formation of lead sulphate precipitate. Determine the
conductance or resistance of the solution.
128
0.5 N Na2SO4 Microburette
Conductometer
Conductivity
cell
10 ml 0.1 N Pb(NO3)2 + 50 ml
conductivity water Iron
stand
Magnetic needle
Magnetic stirrer
Fig. 1
7. In a similar way add 0.2 ml of sodium sulphate solution each time and determine
conductance or resistance of the solution after sufficient stirring of the solution every
time. Determine the conductance or resistance till the equivalence point exceeds by
about one ml. (That is take readings of conductance upto 3.0 ml addition of Na2SO4
solution).
8. Plot a graph of conductance against ml of Na2SO4 added.
9. From the graph find the equivalence point.
Observation Table :
Sr. No. ml of 0.5 N Na2SO4 added Conductance in mho
1. 0
2. 0.2
3. 0.4
: …
: …
: …
: 3.0
129
Graph :
Conductance
Equivalence point
ml of Na2SO4 added
Fig. 2
Calculations :
1. Calculate exact normality of Pb(NO3)2
Pb(NO3)2 ≡ Na2SO4
N1V1 = N2V2
N1 × 10 = 0.5 × V2 (V2 from graph)
0.5 × V2
∴ N1 =
10
2. Strength of Pb(NO3)2 solution :
Strength = Normality × Equivalent weight
= N1 × 165.6 gL−1
3. Amount of lead in 10 ml 0.1 N solution
Atomic weight of Pb = 207.2
1000 ml 1 N Pb(NO3)2 solution ≡ 207.2 g Pb
10 × N1 × 207.2
10 ml 0.1 N Pb(NO3)2 solution = g Pb
1000
Result Table :
2. Exact normality of Pb(NO3)2 solution = ………. N
3. Strength of Pb(NO3)2 solution = ………. g l−1
4. Amount of lead in 10 ml 0.1 N Pb(NO3)2 = ………. gm
130
Experiment No. 3 (A)

Aim :
To investigate the conductometric titration of a strong acid against a strong base.
Apparatus :
Conductivity bridge, conductivity cell, magnetic stirrer, microburette etc.
Chemicals :
0.01 N (approximate) HCl solution, 0.05 N NaOH solution, conductivity water.
Procedure :
1. Take 10.0 ml of 0.1 N HCl in a small beaker, add about 40 ml of conductivity water.
2. Dip a conductivity cell into the solution and ensure that the electrodes of the cell are
completely immersed into the solution. Put a magnetic needle into it and place the
electrode assembly on a magnetic stirrer. Stir the solution well.
3. Connect the electrodes to the conductivity bridge and measure conductance or
resistance of 0.1 N HCl solution.
4. From the burette add 0.2 ml. of 0.05 N NaOH into the HCl solution and stir the
solution. Measure the conductance of the solution.
5. In a similar way add 0.2 ml of 0.05 N NaOH solution each time and every time
measure the conductance. Take conductance readings till the equivalence point
exceeds by one ml i.e. take readings upto addition of 3.0 ml NaOH.
6. Plot a graph of conductance against ml of 0.05 N NaOH added. From the graph find
neutralization point and hence find exact normality of HCl solution.
Observation Table :
Sr. No. ml. of 0.05 N NaOH added Conductance, ohm−1
1. 0
2. 0.2
3. 0.4
4. 0.6
:
16
131
Graph :
Conductance
Neutralization point (V2)
ml of NaOH added
Fig. 1
Calculations :
1. Exact normality of HCl solution
HCl ≡ NaOH
N1V1 = N2V2 (from graph)
N1 × 10 = 0.05 × V2
0.05 × V2
N1 =
10
∴ Exact normality of given HCl = …………
2. Strength of HCl = Normality × Equivalent weight
= N1 × 36.5 g l−1
Result Table :
1. Neutralization or Equivalence point = ………. ml
2. Exact normality of given HCl solution = ………. g equi−1
3. Strength of given HCl solution = ………. g/litre.
Experiment No. 3 (B)

Aim :
To investigate the conductometric titration of a strong acid against a weak base.
Apparatus :
Conductivity bridge, conductivity cell, microburette, magnetic stirrer, burette, beaker etc.
Chemicals :
0.1 N (approx.) HCl solution, 0.5 N NH4OH, conductivity water.
Procedure :
1. In a small beaker take 10.0 ml of 0.1 N HCl solution and add about 40 ml conductivity
water to it. Stir the solution by keeping the beaker on a magnetic stirrer.
132
2. Dip the given conductivity cell into the solution of HCl. Ensure that the electrodes
immerse completely into the solution.
3. Connect the cell to the conductivity bridge and measure the conductance or
resistance of the solution.
4. Add 0.2 ml of NH4OH from a microburette into the HCl solution. Stir the solution and
measure conductance or resistance of the solution.
5. In a similar way add 0.2 ml of 0.5 N NH4OH each time and every time measure the
conductance of the solution.
6. Plot a graph of conductance against ml of NH4OH added.
7. From the graph find the neutralization point of the titration.
Observation Table :
Obs. No. ml of 0.5 N NH4OH added Conductivity, ohm−1
1. 0
2. 0.2
3. 0.4
4. 0.6
: :
16 3.0
Graph :
Conductance
Equivalence point (V2)
ml of NH4OH added
Fig. 1
Calculations :
1. Exact normality of HCl
HCl = NH4OH
N1V1 = N2V2
N1 × 10 = 0.5 × V2 (from graph)
0.5 × V2
∴ N1 =
10
2. Strength of HCl solution = Normality × Equivalent weight
= N1 × 36.5 g l−1
133
Result Table :
1. Equivalence point from graph = ………. ml
2. Exact normality of the given HCl solution = ………. g equi−1
3. Strength of given HCl solution = ………. g/litre.
Experiment No. 3 (C)

Aim :
To investigate the conductometric titration of a strong base against a weak acid.
Apparatus :
Conductivity bridge, dip type conductivity cell, microburette, beaker etc.
Chemicals :
0.01 N (approx.) acetic acid, 0.05 N NaOH.
Procedure :
1. Take 10 ml of 0.01 N acetic acid in a small beaker and add about 40 ml conductivity
water. Put a magnetic needle and place the beaker on a magnetic stirrer.
2. Dip a conductivity cell into the solution, ensure that the electrodes of the cell are
completely immersed in the solution. Stir the solution.
3. Connect the cell to conductivity bridge and measure conductance of acetic acid
solution.
4. Add 0.2 ml of 0.05 N NaOH into the acetic acid solution. Stir the solution and find
conductance of the solution.
5. In a similar way take titration readings adding 0.2 ml of 0.05 N NaOH each time till
the end point exceed by about one ml.
6. Plot a graph of conductance against ml of NaOH added.
7. From the graph find the equivalence point and hence find the normality and strength
of given acetic acid solution.
Reactions :
CH3COOH + NaOH → CH3COONa + H2O
CH3COOH + Na+ + OH− → CH3COO− + Na+ + H2O
Observation Table :
Obs. ml. of 0.05 N NaOH added Conductance, ohm−1
No.
1. 0
2. 0.2
3. 0.4
4. 0.6
: :
16 3.0
134
Graph :
Conductance
ml of 0.05 N NaOH added

Fig. 1
Calculations :
1. Exact normality of acetic acid
Acetic acid ≡ NaOH
N1V1 = N2V2
N1 × 10 = 0.05 × V2
0.05 × V2
N1 =
10
2. Strength of given acetic acid = Normality × Equivalent weight
= N1 × 60 g l−1
Result Table :
2. Exact normality = ………. g equi−1
3. Strength of acetic acid = ………. g/litre.
Experiment No. 3 (D)

Aim :
To investigate the conductometric titration of a weak acid against a weak base.
Apparatus :
Conductivity bridge, dip type conductivity cell, microburette, beaker etc.
Chemicals :
0.1 N (approx.) acetic acid, 0.5 N NH4OH, conductivity water.
Procedure :
1. Take 10 ml of 0.1 N (approximate) acetic acid in a small beaker. Add about 40 ml
conductivity water. Put a magnetic needle. Place the beaker on a magnetic stirrer.
135
2. Dip the given conductivity cell into the acetic acid solution ensuring that the
electrodes are completely immersed into the solution. Stir the solution.
3. Connect the conductivity cell to the conductivity bridge and measure resistance or
conductance of acetic acid solution.
4. Add 0.2 ml of 0.5 N NH4OH into the acid solution, stir the solution and measure the
conductivity or resistance of the solution.
5. In a similar way, measure conductivity by adding 0.2 ml NH4OH each time till the
equivalent point exceeds by about one ml.
6. Plot a graph of conductance against ml of NH4OH added.
7. From the graph find the equivalence point and hence find the exact normality and
strength of given acetic acid solution.
Reaction :
+ +
CH3COOH + NH4 + OH− → CH3COO− + NH4 + H2O
Observation Table :
Obs. No. ml. of 0.5 N NH4OH added Conductance, ohm−1
1. 0
2. 0.2
3. 0.4
4. 0.6
: :
16 3.0
Graph :
Conductance
ml of NH4OH added
Fig. 1
136
Calculations :
1. Exact normality of given acid solution
Acetic acid = NH4OH
N1V1 = N2V2
N1 × 10 = 0.5 × V2
0.5 × V2
∴ N1 =
10
2. Strength of given acid solution = Normality × Equivalent weight
= N1 × 60 g l−1
Result Table :
2. Exact normality of given acetic acid solution = ………. g equi−1
3. Strength of given acetic acid solution = ………. g l−1
VIVA VOCE
1. What is a strong and a weak electrolyte ?
2. What is Ohm’s law ?
3. What is conductance ?
4. Why solutions of electrolytes show conductance ?
5. Define specific resistance, specific conductance.
6. Define Ohm.
7. In which unit conductance is measured ?
8. Explain how resistance of a conductor is measured using Wheatstone bridge.
9. Why direct current is not used in determination of conductance ?
10. Explain the variation of specific conductance with concentration.
11. What is conductivity cell ?
12. What is cell constant ?
13. Why inert electrodes like platinum are used for conductance measurements ?
14. What is a null point ?
15. What is equivalent conductance ?
16. Explain the variation of equivalent conductance with concentration.
17. What is the effect of temperature on conductance ?
18. How equivalent conductance of strong and weak electrolytes is measured ?
19. Can you use the Kohlrausch equation for the determination of equivalent
conductance at infinite dilution of a weak electrolyte ?
137
20. What is equivalent conductance at infinite dilution ?

21. Explain how you will find ^0 of weak electrolytes.
22. State Kohlrausch law of independent migration of ions.
23. Give the expressions to find (i) specific conductance, (ii) equivalent conductance and
degree of dissociation.
24. What is conductivity water ? And why it is required for conductivity measurements ?
25. What are the different types of cells used in conductivity measurements ?
26. Which type of conductivity cell will you use (i) for solution of low conductance and
(ii) for solution of high conductance ?
27. How conductivity water is obtained ?
28. State Ostwald’s dilution law.
29. What is conductometric titration ?
30. What are the advantages of conductometric titrations ?
31. Is equivalence point obtained by a conductometric titration is more accurate as
compared to a conventional volumetric titration ? True or False.
32. Explain the nature of titration curves of following conductometric titrations :
(a) Strong acid and strong base, (b) Strong acid and weak base,
(c) Weak acid and strong base,
(d) Weak acid and strong base and precipitation titration of Pb(NO3)2 vs. Na2SO4 ?
33. What is ionic mobility ?
34. Can you titrate a mixture of a strong and a weak acid with a strong base ? If yes, how
you will find the equivalent points for strong acid and weak acid neutralization ?
35. How will you determine dissociation constant of a weak acid by conductivity
measurement ?
36. Give the factors that affect conductance of a solution.
37. Why platinum electrode used in conductivity cells is coated with platinum black ?
38. How platinum electrode is platinised ?
---
138
Appendices
Appendix - I : K and α values of polymer :
Polymer Solvent K at 25°°C α at 25°°C

−4
1. Polyvinyl alcohol Water 2.0 × 10 0.76
−3
2. Crape rubber Benzene 9.40 × 10 0.76
−4
3. Cellulose acetate (Table Tennis Ball) Acetone 1.49 × 10 0.82
−1
4. Polystyrene (yellow rubber Toluene 3.7 × 10 0.62
used in shoes)
Appendix - II : Densities and refractive index of liquids :
Liquid Refractive index n at 15°°C Density, g ml−1 at 15°°C

Benzene 1.5014 (at 20°C) 0.8794 (at 20°C)
Chloroform 1.4486 (at 20°C) 1.4985
Carbon tetrachloride 1.4631 1.595
Methyl alcohol 1.3312 0.7952
Ethyl alcohol 1.3620 0.7881
Toluene 1.500 0.8715
Chlorobenzene 1.5248 (at 20°C) 1.066 (at 20°C)
Bromobenzene 1.5598 1.4991
Acetone 1.3588 (at 20°C) 0.792 (at 20°C)
Appendix - III : Transition temperature :
Substance Transition temperature

Na2SO4, 10H2O 32.38°C
Na2CO3, 10H2O 32.22°C
NaBr, 2H2O 50.7°C
Appendix - IV : Dissociation constants of acids at 25°°C :
Substance Ka at 25°°C
Acetic acid 1.75 × 10−5
Benzoic acid 6.3 × 10−6
Monochloroacetic acid 1.4 × 10−3
Oxalic acid 6.5 × 10−2
Propionic acid 1.4 × 10−5
Formic acid 1.7 × 10−4
( 139 )
T.Y.B.Sc. Practical Chemistry (Physical Practicals) Appendices
Salicylic acid 1.06 × 10−3
Appendix - V : Liquids and boiling points :
Substance Boiling point Density (20°°C)

(normal)
Chlorobenzene 132°C 1.107
Bromobenzene 155 − 156°C 1.500
Nitrobenzene 210.9°C 1.980
Appendix - VI : Vapour pressure of water and temperature in.
Temp./ 0.0 0.2 0.4 0.6 0.8 Temp./ 0.0 0.2

°C °C
85 433.6 437.0 440.0 440.0 447.5 94 610.9 615.42
86 450.9 454.4 458.0 461.6 456.2 95 633.9 638.60
87 468.7 472.4 476.0 479.8 483.4 96 657.62 662.5
88 487.1 491.0 494.7 498.5 502.2 97 682.10 687.0
89 506.0 510.0 513.9 517.8 521.8 98 707.30 712.4
90 525.8 529.77 533.8 537.9 542.0 99 733.24 738.5
91 546.1 550.20 554.4 558.5 562.8 100 760.00 765.5
92 567.00 571.26 575.6 579.9 584.2
93 588.60 593 597.4 601.9 606.4
Appendix - VII : Specific conductance of 0.01 M KCl :
Temperature 20 21 22 23 24
Specific 0.001278 0.001305 0.001335 0.001359 0.001380
conductivity
Structure of Practical Examination Marks
1. One Experiment from Group – A 35
2. One Experiment from Group – B 35
3. Oral 10
✍ ✍ ✍
140
Course - I
CH-348
INORGANIC CHEMISTRY
PRACTICALS
141
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Gravimetric Estimations

COURSE – I
CH – 348
Inorganic Chemistry Practicals
Experiments Marks
Q.1. Qualitative Analysis (Compulsory Experiment) 35
OR
Gravimetric Experiment* 30
Q.2. Volumetric Experiment (20 marks) 35
Preparation (10 marks)
OR
Flame Photometry (20 marks)
OR
Column Chromatography (20 marks)
OR
Colorimetric Estimation (25 marks)
Q.3. Oral 10
142
(A) Gravimetric Estimations

(Any Three)
Experiment No. 1
Fe as Fe2O3
Aim :
Gravimetric estimation of iron (Fe) as ferric oxide (Fe2O3) from ferrous ammonium sulphate.
Principle :
Ferrous is oxidized to ferric state by boiling with concentrated HNO3, then it is
precipitated as ferric hydroxide (red precipitate) with ammonium hydroxide. This precipitate
can be filtered through Whatman filter paper No. 41. Ferric hydroxide on ignition gives ferric
oxide.
Reactions :
6FeSO4 + 3H2SO4 + 2HNO3 ⎯→ 3Fe2(SO4)3 + 2NO + 4H2O
Fe2(SO4)3 + 6NH4OH ⎯→ 2Fe(OH)3 ↓ + 3(NH4)2SO4
Δ
2Fe(OH)3 ⎯→ Fe2O3 + 3H2O
Requirements :
(i) Ferrous ammonium sulphate solution → Given
(ii) Dil. H2SO4 (2N) → 10 ml
(iii) Conc. HNO3 → 3 – 4 ml
(iv) Ammonium nitrate solution (2%) → for washing
(v) Ammonium chloride → 1 gm
(vi) 1 : 1 ammonia
(vii) Silica crucible
(viii) Whatman filter paper No. 41.
Procedure :
1. Dilute the given solution of ferrous ammonium sulphate (FAS) with distilled water
upto the mark in a 250 ml volumetric flask and shake well.
2. Pipette out 50 ml of this diluted solution in a 250 ml beaker. To this add two test
tubes distilled water.
3. Add 10 ml diluted H2SO4 and heat upto boiling.
4. Then add 3-4 ml conc. HNO3, boil for 5 minutes. At this state ferrous is oxidized to
ferric state.
5. To this boiling solution add 1 gm NH4Cl. Stir with glass rod.
143
6. Then add 1 : 1 ammonia solution. The precipitation is of ferric hydroxide

(red precipitate). Add slight excess ammonia solution. Then boil the solution for
5 minutes, allow the precipitate to settle.
7. Filter the solution through Whatman filter paper No. 41. Transfer all the precipitate
over the filter paper.
8. Wash the precipitate with hot 2% ammonium nitrate for 3 - 4 times. Then wash with
hot water till the filtrate is free from chloride and sulphate radicals.
9. Dry the precipitate of Fe(OH)3 in oven or on metal cone. Ignite the precipitate along
with the filter paper in a previously weighed silica crucible.
10. Heat the crucible along with the precipitate at 700 - 800°C in an electric furnace for
about 45 minutes.
11. Cool the crucible and weigh it. Repeat the process of heating till a constant weight is
obtained.
12. Difference in two weights give the weight of residue (Fe2O3). Let it be ‘X’ gms.
13. Calculate the amount of FeSO4(NH4)2SO4 ⋅ 6H2O (Mohr’s salt) in the given solution.
Observation Table :
Sr. No. Description Symbol Weight
1. Weight of empty crucible W1 = ………. gms
2. Weight of crucible + Residue W2 = ………. gms
3. Weight of residue (Fe2O3) (W2 − W1) ‘X’ = ………. gms
Calculations :
50 ml diluted solution contains = ‘X’ gms of Fe2O3
∴ 250 ml diluted solution contains = ‘X’ × 5 gms of Fe2O3
= ‘Y’ gms of Fe2O3
From equation, Fe2O3 = 2[FeSO4(NH4)2SO4 ⋅ 6H2O] ≡ 2Fe
159.7 784 11.70
1. To find out quantity of ferrous ammonium sulphate in the given solution :
159.7 gms of Fe2O3 obtained from = 784 gms of FAS.
784
∴ ‘Y’ gms of Fe2O3 will be obtained from = × ‘Y’ gms of FAS.
159.7
= 4.909 × ‘Y’ gms of FAS
= …… Z gms of FAS
2. To find out amount of Fe in the given solution :
159.70 g Fe2O3 ≡ 111.70 gm Fe
∴ Y g Fe2O3 ≡ ?
144
111.70 × Y
= gms Fe
159.70
= 0.6994 × Y gms Fe
= ‘B’ gms Fe
Result Table :
Sr. Description Value
No.
1. 50 ml of diluted solution gave ‘X’ ….. gms of Fe2O3
2. 100 ml of diluted solution gave ‘Y’ ….. gms of Fe2O3
3. Quantity of FeSO4(NH4)2SO4 ⋅ 6H2O (Mohr’s ‘Z’ ….. gms
salt) in the given solution
4. Quantity of Fe in the given solution ‘B’ ….. gms
VIVA VOCE
1. What is gravimetric analysis ?
2. What type of crucible is used in gravimetric estimation of Fe as Fe2O3 ? Why ?
3. Which filter paper is used for filteration ?
4. What is the use of dessicator ?
5. What is present in dessicator ? What is its role ?
6. Why the precipitation of Fe(OH)3 is washed with ammonium nitrate solution ?
7. What do you mean by filteration by decantation ?
8. What is used for precipitation of ferric hydroxide ? Why ?
9. List various operations involved in gravimetric analysis.
10. How Fe2+ is converted into Fe3+ ?
11. Why HNO3 is added to the diluted FAS solution ?
Experiment No. 2
Nickel as Ni-DMG
Aim :
Gravimetric estimation of nickel as nickel dimethyl glyoxamate.
Principle :
145
To a slight acidic solution of nickel, if we add alcoholic solution of dimethyl glyoxamate

and slight excess of ammonia then pinkish red precipitate of nickel dimethyl glyoxamate is
formed. It can be filtered and weighed directly.
Dimethyl glyoxime reagent is a bidentate ligand, nickel has coordination numbers 4 and
6. Here two molecules of reagent combine with one molecule of nickel, forming a square
planar geometry.
Reaction :
Heat
Ni2+ + 2H2 DMG ⎯⎯⎯→ Ni(HDMG)2 + 2H+
50°C
H
O O
CH3 C N N C CH3
CH3 C N OH
2+ Heat Ni
Ni +
at 60ºC
CH3 C N OH
CH3 C N N C CH3
O
O
H
DMG Nickel dimethyl glyoxamate

(Ni-DMG)
Requirements :
(i) NiSO4 ⋅ 7H2O solution → given
(ii) Tartaric acid → 5 gms
(iii) 1 : 1 HCl → 5 ml
(iv) 2% dimethyl glyoxamine (alcoholic) → 20 ml
(v) 1 : 1 ammonia
(vi) Gooch crucible (G4)
(vii) Oven.
Procedure :
1. Dilute the given solution of nickel sulphate with distilled water upto the mark in a
250 ml volumetric flask and shake well.
2. Pipette out 50 ml of this diluted solution in a 250 ml beaker. To this add two test
tubes distilled water.
3. Then add 5 gms of tartaric acid and 5 ml of 1 : 1 HCl till the solution is alkaline and
pinkish red precipitate of nickel dimethyl glyoxamate is obtained.
4. Heat the solution on water bath for about 30 minutes. Allow the precipitate to settle
and cool to room temperature.
146
5. Filter the precipitate through previously weighed Gooch crucible (G4).

6. Wash the precipitate with cold distilled water till the filtrate is free from chloride
radical (tested with AgNO3 solution).
7. Dry the precipitate to 150°C in a oven for about one hour.
8. Allow it to cool and weigh the residue as nickel dimethyl glyoxamate.
9. Calculate the amount of NiSO4 ⋅ 7H2O and the quantity of nickel in the given solution.
Observation Table :
Obs. No. Description Symbol Weight
1. Weight of empty crucible W1 = ………. gms
2. Weight of Gooch crucible + Residue W2 = ………. gms
3. Weight of residue (W2 − W1) ‘X’ = ………. gms
Calculations :
50 ml diluted solution gives = ‘X’ gms of Ni-DMG
∴ 250 ml diluted solution gives = ‘X’ × 5 gms of Ni-DMG
= ‘Y’ gms of Ni-DMG
From equation, NiSO4 ⋅ 7H2O ≡ Ni − (C4H7O2N2)2 ≡ Ni
280.87 289.19 58.71
1. Estimation of nickel :
289.19 gms of Ni-DMG solution = 58.71 gms of Ni
58.71
∴ Y gms of Ni-DMG contains = × Y gms of Ni
289.19
= 0.2330 × ‘Y’ gms of Ni.
2. Estimation of NiSO4 ⋅ 7H2O in the given solution :
289.19 gms of Ni-DMG contains = 280.87 gms of NiSO4 ⋅ 7H2O
280.87
∴ ‘Y’ gms of Ni-DMG contains = × ‘Y’ gms
289.19
= 0.9716 × Y gms
= ‘Z’ gms of NiSO4 ⋅ 7H2O
3. To find out quantity of Ni in the solution :
288.71 gm of Ni-DMG ≡ 58.71 gms of Ni
58.71 × Y
∴ ‘Y’ gm of Ni-DMG ≡ gms of Ni
288.71
= 0.2034 × Y gms of Ni
= ‘B’ gms of Ni
Result Table :
147

1. 50 ml of diluted solution gave X = ….. gms of Ni-DMG
2. Quantity of nickel in the given solution Y = ….. gms
3. Quantity of NiSO4 ⋅ 7H2O in the given Z = ….. gms
solution
4. Quantity of Ni in the given solution B = ….. gms
VIVA VOCE
1. Which crucible is used for filteration ?
2. What is Gooch crucible ?
3. What is DMG ? Draw its structure.
4. What type of ligand the DMG is ?
5. What do you mean by ligand ?
6. What are polydentate ligands ?
7. Write the reaction of Ni2+ with DMG.
8. Why DMG is bidentate ligand ?
9. What is the coordination number of Ni2+ in Ni-DMG complex ?
10. What is the geometry of Ni-DMG complex ?
11. Why the precipitate of Ni(H DMG)2 kept in oven and not ignited ?
Experiment No. 3
Al as Aluminium Oxide
Aim :
To determine the amount of aluminium gravimetrically as Al2O3.
Principle :
Aluminium is precipitated as aluminium hydroxide by ammonia solution in the presence
of ammonium chloride. The gelatinous precipitate of aluminium hydroxide is washed with a
solution of strong electrolyte subjected to strong ignition and finally weighed as Al2O3.
Reactions :
(1) Al3+ + NH4Cl + NH4OH ⎯→ Al(OH)3 ↓
Δ
(2) 2Al(OH)3 ⎯→ Al2O3 + 3H2O ↑.
Theory :
The gravimetric estimation of Al as Al2O3 must be done following several precautions.
Aluminium hydroxide is amphoteric in nature. It is a bulky, gelatinous precipitate, appreciably
in ammonia but practically insoluble in the presence of ammonium salts. The precipitation of
Al(OH)3 commences in approximately pH 4 and is complete when the pH lies between
148
6.5 and 7.5. The required pH can be controlled by adding ammonium chloride before adding
ammonium hydroxide which creates buffering effect and also help the coagulation of the
initially colloidal precipitate. The addition of ammonium chloride controls the hydroxide
concentration. It also reduces the co-precipitation of divalent cations like Ca2+ and Mg2+ and
some other cations. Excess of ammonia should not be added because prolong boiling is
required to remove excess of ammonia which also makes the precipitate obtained by
precipitation in hot solution. The precipitate cannot be washed with hot water because
aluminium hydroxide is readily peptised and will pass through the filter paper. It is washed
with 2% solution of ammonium nitrate which avoids sol formation. This precipitate is
hygroscopic and hence high temperature (1200°C) is necessary for the rapid dehydration of
aluminium hydroxide to aluminium oxide. For this reason, the precipitate ignited in a rapid
weighing without undue exposure to atmosphere is essential as freshly ignited alumina is
extremely hygroscopic.
Requirements :
(i) Ammonium aluminium sulphate (alum) solution (Give 10 to 50 ml) given in a 100 ml
volumetric flask.
(ii) Ammonium chloride
(iii) 1 : 1 ammonia
(iv) Methyl red indicator (0.2% alcoholic solution)
(v) Silica crucible
(vi) Ammonium nitrate
(vii) Whatman filter paper No. 41.
Procedure :
1. Dilute the given solution of ammonium aluminium sulphate [(NH4)2SO4 ⋅ Al2(SO4)3 ⋅
24H2O] with distilled water upto the mark in a 100 ml volumetric flask. Shake the flask
and take out all the solution in a clean 250 ml beaker.
2. Take by a burette 25 ml of this diluted solution in a 250 ml beaker. Add 50 ml
distilled water to it by a measuring cylinder.
3. Add one gram ammonium chloride to it.
4. Add 2 to 3 drops of methyl red indicator. The solution turns red.
5. Heat the solution just to boiling.
6. Add 1 : 1 ammonia solution drop by drop to precipitate Al as Al(OH)3 till the colour of
the solution becomes distinct yellow. Avoid excess addition of ammonia solution.
A white gelatinous precipitate of Al(OH)3 is obtained.
7. Boil the solution for two minutes.
149
8. Filter the hot solution containing the precipitate of Al(OH)3 through Whatman filter
paper No. 41 by decantation method. Then transfer the precipitate carefully to the
filter paper.
9. Wash the beaker and the precipitate with hot 2% ammonium nitrate solution; use
about 10 ml wash liquid at a time. Wash the precipitate till it is free from sulphate
ion. The fresh filtrate, during washing finally should not give a precipitate with barium
nitrate. This confirms the removal of sulphate ion on the precipitate.
10. Dry the precipitate with the filter paper on a metallic cone or in an oven.
11. Ignite the precipitate along with ashless filter paper in previously weighed silica
crucible. Heat the crucible with the filter paper at about 1200°C on a pipe clay
triangle for half an hour without the lid and for 15 minutes with lid partially open. The
residue of Al(OH)2 is converted to Al2O3.
12. Transfer the crucible and lid to the desiccator when it is warm. Allow it to cool in the
dessicator when it is warm. Allow it to cool.
13. When cool, quickly weigh the crucible and lid along with the residue of Al2O3. Find
the weight of Al2O3 residue.
Reactions :
Al2(SO4)3 + 6NH4OH ⎯→ 2Al(OH)3 ↓ + 3(NH4)2SO4
Δ
2Al(OH)3 ⎯→ Al2O3 + 3H2O ↓
Observation Table :
Sr. No. Description Symbol Weight
1. Weight of empty silica crucible + lid W1 = ………. gms

2. Weight of crucible + lid + Al2O3 residue W2 = ………. gms
3. Weight of Al2O3 residue (W2 − W1) ‘X’ = ………. gms
Calculations :
25 ml diluted solution of ammonium
≡ X g of Al2O3
aluminium sulphate
∴ 100 ml diluted solution of ammonium
≡ 4 × g of Al2O3
aluminium sulphate
≡ Y g of Al2O3
1. To find out the quantity of ammonium aluminium sulphate in the given
solution :
From the equation,
150
(NH4)2SO4 ⋅ Al2(SO4)3 ⋅ 24H2O ≡ Al2O3 ≡ 2Al

906 ≡ 102 ≡ 54
102 g of Al2O3 ≡ 906 g of (NH4)2SO4 ⋅ Al2(SO4)3 ⋅ 24H2O
906
∴ Y g of Al2O3 ≡ × Y g of (NH4)2SO4 ⋅ Al2(SO4)3 ⋅ 24H2O
102
≡ 8.88 × Y g
≡ Z g of (NH4)2SO4 ⋅ Al2(SO4)3 ⋅ 24H2O
2. To find out the quantity of aluminium in the given solution :
102 g of Al2O3 ≡ 54 g of Al
54
∴ Y g of Al2O3 ≡ × Y g of Al
102
≡ 0.5294 × Y g of Al
≡ B g of Al
Result Table :
1. 25 ml of diluted solution of alum gave X ….. g of Al2O3
2. Quantity of alum in the given solution Z ….. gms
3. Quantity of aluminium in the given B ….. gms
solution
VIVA VOCE
1. Give the reaction involved in gravimetric estimation of Al as Al2O3.
2. Which filter paper is used in this gravimetric estimation ? Why ?
3. What is the nature of precipitate in this experiment ?
4. What is the role of NH4Cl in gravimetric estimation of Al as Al2O3 ?
5. Why hot solution is used for precipitation ?
6. Washing with hot water is never done in this experiment. Why ?
Experiment No. 4
Ba as BaSO4
Aim :
Gravimetric estimation of barium as barium sulphate by using sulphamic acid.
(Homogeneous precipitation technique).
Principle :
151
Sulphamic acid is hydrolysed to ammonium sulphate above 60°C. Barium (Ba+2)

2−
combines with sulphate ion (SO4 ) and barium sulphate is precipitated slowly. This type of
precipitation minimizes coprecipitation and thus impurities are reduced. Similarly precipitate
is compact and granular as precipitation is slow and through the solution. This precipitate
can be filtered through Whatman filter paper No. 42 and weighed as BaSO4.
Reactions :
Boil + 2−
NH2SO3H + H2O ⎯⎯⎯→ NH4 + SO4 + H+
2−
Ba2+ + SO4 ⎯⎯⎯→ BaSO4 ↓ (white precipitate)
Requirements :
(i) BaCl2 ⋅ 2H2O solution → given
(ii) Sulphamic acid → 5 gm
(iii) Whatman filter paper No. 42
(iv) Silica crucible, watch glass
(v) Oven furnace etc.
Procedure :
1. Dilute the given solution of BaCl2 ⋅ 2H2O with distilled water upto the mark in a
250 ml volumetric flask and shake well.
2. Pipette out 50 ml of this diluted solution in 250 ml beaker. To this add two test tubes
distilled water.
3. Then add 5 gm of sulphamic acid, stir with glass rod.
4. Cover the beaker with glass. Heat slowly on an sand bath for about 30 minutes.
5. The white precipitate of BaSO4 settles at the bottom.
6. Filter the precipitate through Whatman filter paper No. 42. Then wash the precipitate
with hot distilled water, till the filtrate is free from chloride and sulphate radicals.
7. Dry the precipitate in a oven and finally ignite it in a previously weighed silica
crucible.
8. Heat the crucible along with the precipitate at 700 - 800°C in an electric furnace for
about 30 minutes.
9. Cool the crucible and weigh it. Repeat the process of heating till a constant weight is
obtained.
10. Difference in two weights is the weight of BaSO4. Let it be ‘X’ gms.
11. Calculate the amount of BaCl2 ⋅ 2H2O in the given solution.
Observation Table :
Obs. No. Description Symbol Weight
1. Weight of empty silica crucible W1 = ………. gms
152
2. Weight of crucible + residue (BaSO4) W2 = ………. gms

3. Weight of residue (W2 − W1) ‘X’ = ………. gms
Calculations :
Since 50 ml diluted solution gives = ‘X’ gms of BaSO4
∴ 250 ml diluted solution gives = ‘X’ × 5 gms of BaSO4
= ‘Y’ gms of BaSO4
From equation, BaSO4 ≡ BaCl2 ⋅ 2H2O ≡ Ba
233.36 244.36 137.36
1. Quantity of BaCl2 ⋅ 2H2O in the given solution :
∴ 233.36 gms of BaSO4 obtained from = 244.36 gms of BaCl2 ⋅ 2H2O
244.36
∴ ‘Y’ gms of BaSO4 = × ‘Y’ gms of BaCl2 ⋅ 2H2O
233.36
= 1.047 × ‘Y’ gms of BaCl2 ⋅ 2H2O
= ………. Z gms of BaCl2 ⋅ 2H2O
2. To find out the amount of Ba in the given solution :
233.36 gm of BaSO4 ≡ 137.36 gms of Ba
137.36 × Y
∴ Y gm of BaSO4 ≡ gms of Ba
233.36
≡ 0.5886 gm × Y gms of Ba
≡ B gms of Ba
Result Table :
1. 50 ml of diluted solution gave X = ….. gms of BaSO4
2. Quantity of BaCl2 ⋅ 2H2O in the given Z = ….. gms
solution
3. Quantity of Ba in the given solution B = ….. gms
VIVA VOCE
1. Which filter paper is used in this experiment ?
2. Which crucible is used ?
3. How Ba is precipitated ?
4. What do you mean by precipitation from homogeneous solution ?
5. How sulphamic acid is used in this experiment ?
153
6. What are the advantages of precipitation from homogeneous solutions in

comparison to conventional method of precipitation ?
7. What is gravimetric analysis ?
8. What is quantitative analysis ?
9. How the quantity of Ba2+ present in the solution is calculated ?
---
154
(B) Volumetric Estimations
(Any Four)
Introduction :
The term volumetric analysis (or called as titrimetric analysis) refers to quantitative
analysis carried out by determining the volume of a solution of accurately known
concentration which is required to react quantitatively with a measured volume of solution of
the substance to be determined. The solution of accurately known strength is called the
standard solution. The weight of the substance to be determined is calculated from the
volume of standard solution used and the chemical equation and relative molecular masses
of the reacting compounds.
It is one of the used analytical techniques. It is simple, rapid and good accuracy can be
obtained from it.
The process of adding the standard solution until the reaction is just complete is termed
as a titration, and the substance to be determined is titrant. The most important point in the
process of titration is the determination of the end point, that is, the point at which the
reaction is just completed. To determine the end point of a reaction, we use certain chemicals
by which the change of colour indicates that the reaction is completed. Such chemicals are
called indicators.
Experiment No. 1
Manganese (Mn) by Volhard’s Method
Aim :
To determine the amount of manganese (Mn) volumetrically by Volhard's method.
Principle :
The details of standardization of KMnO4 solution is already studied in S.Y.B.Sc. Volhard's
method for determination of manganese is based on the principle that when warm solution
of manganese (here manganese sulphate) is titrated with standard solution of KMnO4 the
−
dark brown precipitate of manganese dioxide is obtained in the flask. Thus, MnO4 ions are
reduced to MnO2 and Mn2+ (manganous) ions are oxidized to MnO2. This can be observed in
the following reaction :
2KMnO4 + 3MnSO4 + 2H2O → K2SO4 + 5MnO2 ↓ + 2H2SO4
−
i.e. 2MnO4 + 3Mn2+ + 2H2O → K2SO4 + 5MnO2 ↓ + 4H+.
The precipitate that is hydrated manganese oxide is acidic in nature which absorbs
manganese hydroxide and prevent complete oxidation. To avoid this difficulty, Volhard
introduced the use of ZnO paste. Following are the functions of zinc oxide paste :
1. It settles the MnO2 precipitate quickly.
154
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Volumetric Estimations
2. It neutralises excess of H2SO4.

3. It avoids the formation of KMnO4.
4. If Fe impurities are present in the solution it forms zinc ferrites. Thus the interference
of Fe is masked.
5. It avoids the formation of manganous acid. Thus precipitation of manganous
manganite is prevented.
Hint : Potassium permanganate attacks organic matter. So burette with rubber tubing
and pinch cock cannot be used. The strength of potassium permanganate is altered if it is
kept in contact with rubber for long time. So the burette used in permanganate titration
must be glass stoppered.
Chemicals :
(i) 0.05 N (approximate) KMnO4
(ii) Given unknown solution of manganese (MnSO4)
(iii) A.R. grade oxalic acid
(iv) Zinc oxide paste
(v) 2 N HNO3.
Procedure :
This experiment is performed in the following three parts :
Part A : Preparation of standard solution of oxalic acid (0.05 N) :
1000 ml 1 N oxalic acid solution contains 63 g H2C2O4 ⋅ 2H2O.
1000 ml 0.1 N oxalic acid solution contains 6.3 g H2C2O4 ⋅ 2H2O.
∴ 100 ml 0.05 N oxalic acid solution contains 0.315 g H2C2O4 ⋅ 2H2O.
1. Weigh accurately 0.315 g of A.R. grade oxalic acid crystals on watch glass.
2. Transfer it in a clean beaker and rinse the watch glass with distilled water.
3. Stir the solution with glass rod and dissolve the crystals. Pour the solution into 100 ml
volumetric flask.
4. Dilute the solution with distilled water upto the mark.
5. Take out all the solution in a clean beaker to make homogeneous solution. This is
0.05 N oxalic acid solution.
−
6. Use this solution for standardization of given KMnO4 solution.
Part B : Standardization of KMnO4 solution :
1. Fill the burette No.1 with 0.05 N (approximate) KMnO4 solution.
2. Fill the burette No.2 with standard 0.05 N oxalic acid solution.
3. Take 9 ml of oxalic acid solution from burette No.2 in a 100 ml conical flask. Call this
volume as V2 ml.
4. Add to it 1/2 test tube (10 ml) of 2 N (dilute) H2SO4.
155
5. Heat the solution on a wire gauze to about 60°C to 70°C (as indicated by
condensation of water vapours on cooler part of conical flask).
6. Titrate this hot solution of oxalic acid against KMnO4 solution, added slowly (drop by
drop) from burette No.1 with constant shaking of the flask.
7. Continue the addition of KMnO4 till the solution in the conical flask becomes
permanently faint pink. Record the burette reading and call this as X1 ml.
8. Add to the same conical flask 1 ml solution of 0.05 N oxalic acid from burette No. 2.
Heat the flask again so that solution in the flask acquires a temperature of about
60 - 70°C and solution becomes colourless.
9. Add KMnO4 solution from burette No.1 till a permanent faint pink colour appears to
the solution. Record the burette reading and call this as X2 ml.
10. To the same solution in the conical flask add 1 ml solution of 0.05 N oxalic acid from
burette No. 2 (See that the solution in the flask is hot, if not, heat it again to
60 - 70°C). The pink colour disappears.
11. Add KMnO4 solution from burette No. 1 till a faint permanent pink colour appears to
the solution. Call this reading as X3 ml.
Part C : Estimation of Manganese :
1. Dilute the given solution of manganese sulphate to 100 ml with distilled water in a
volumetric flask. Take out whole solution in a beaker and stir it well.
2. Fill the burette No.1 with standardized KMnO4 solution.
3. Clean the burette No. 2 and fill it with diluted MnSO4 solution.
4. Take 9 ml of diluted MnSO4 solution from burette No. 2 in a 100 ml conical flask. Call
this volume as V2 ml.
5. Add to it 1/2 test tube of ZnO paste. Also add one test tube of water.
6. Heat the solution on wire gauze to about 60°C and add 2 - 3 drops of 2 N HNO3
solution (which promotes the settling of the precipitate of MnO2 at the bottom).
7. Titrate this hot solution with standardized KMnO4 solution from burette No. 1 with
constant shaking.
8. Continue the addition of KMnO4 till the supernatant solution in the conical flask
becomes faint pink which persists even after vigorous shaking. Record the burette
reading and call this as Y1 ml.
9. Add to the same conical flask 1 ml solution of MnSO4 from burette No. 2 with
constant shaking. The pink colour disappears. Heat the solution on water bath to
60°C.
10. Add KMnO4 from burette No. 1 till a faint pink colour appears to the supernatant
solution. Record the burette reading and call this as Y2 ml.
11. To the same solution in the conical flask add 1 ml solution of KMnO4 from burette
No. 2. The pink colour disappears. Heat the solution on water bath to 60°C.
156
12. Add KMnO4 solution from burette No. 1 till faint pink colour appears to the
supernatant solution. Record the burette reading and call this as Y3 ml.
Note : During the titration, allow the precipitate to settle down and observe the colour of the
supernatant solution against white background at each addition.
Observation Table :
Part B : Standardization of KMnO4 solution.
To find : Exact normality of KMnO4 solution
Burette 1 : KMnO4 solution (approximate 0.05 N)
Burette 2 : Oxalic acid solution (0.05 N exact)
Indicator : KMnO4 (self indicator)
End point : Colourless to pink
Reaction :
2KMnO4 + 3H2SO4 + 5H2C2O4 → K2SO4 + 2MnSO4 + 8H2O + 10CO2 ↑
Obs. No. Burette 1 Burette 2 Normality

X ml V2 ml 0.05 × V2
N=
X
1. X1 = ….. 9.0 0.05 × 9

N1 =
X1
2. X2 = ….. 9 + 1 = 10.0 0.05 × 10

N2 =
X2
3. X3 = ….. 10 + 1 = 11.0 0.05 × 11

N3 =
X3
N1 + N2 + N3
Mean Normality N4 = = .......... N
3
∴ Exact normality of KMnO4 = N4 = …… N

Part C : Estimation of Manganese.
Given : KMnO4
To find : Amount of Mn in the given solution.
Burette - 1 : KMnO4 solution.
Burette - 2 : MnSO4 solution
157
Indicator : KMnO4 self indicator.

End Point : Faint pink colour to supernant solution.
Reaction :
2KMnO4 + 3MnSO4 + 2H2O ⎯→ K2SO4 + 5MnO2↓ + 2H2SO4
Burette - 1 (KMnO4) Y1 ml Y2 ml Y3 ml
Burette - 2 (MnSO4) 9 ml 10 ml 11 ml
To calculate the amount of Mn :
We have reaction,
2KMnO4 + 3MnSO4 + 2H2O ⎯→ K2SO4 + 5MnO2↓ + 2H2SO4
2 moles of KMnO4 ≡ 3 moles of Mn
3
∴ 1 mole of KMnO4 ≡ moles of Mn
2
3 1
1N KMnO4 = × moles of Mn
2 5
1
(Since 1 g equivalent of KMnO4 = mol. wt. of KMnO4)
5
3
= × 54.94 gm Mn
10
= 16.48 g Mn
1000 ml 1 N KMnO4 = 16.48 g Mn
∴ 1 ml 0.05 N KMnO4 = 0.000824 g Mn
0.000824 × N4 × Y1
∴ Y1 ml of N4 KMnO4 = = A1 g Mn
0.05
0.000824 × N4 × Y2
Similarly, Y2 ml of N4 KMnO4 = = A2 g Mn
0.05
0.000824 × N5 × Y3
and Y3 ml of N4 KMnO4 = = A3 g Mn
0.05
Now, 9 ml diluted solution contains A1 g Mn
∴ 100 ml diluted solution contain B1 g Mn
Similarly, 10 ml diluted solution contain A2 g Mn
and 11 ml diluted solution contain A3 g Mn
158
B1 + B2 + B3
Mean = = B g Mn
3
Thus, amount of Mn in 100 ml diluted solution = B g Mn
Result Table :
1. Exact normality of KMnO4 solution = N4 ………. N
2. The amount of Mn in the given solution = B ………. g
VIVA VOCE
1. Explain the term 'Volumetric analysis'.
2. Define the terms : Standardization, titration, standard solution.
3. What do you mean by normal solution ?
4. How 1 g equivalent of Mn is calculated ?
5. How 100 ml 0.05 N oxalic acid solution is prepared ?
6. What are the functions of ZnO paste in the estimation of manganese ?
7. Why ZnO paste is added in the estimation of manganese ?
8. What is normal solution ? How will you prepare 0.01 N solution of oxalic acid ?
9. Why this method is called Volhard's method ?
Experiment No. 2
−
Estimation of NO2 using KMnO4
Aim :
To determine the amount of nitrite from a given salt by titrating it against a standard
solution of 0.05 N KMnO4.
Theory:
An acidified solution of sodium nitrite is oxidized by potassium permanganate to nitrate:
− + − 2+ −
2MnO4(aq) + 6H(aq) + 5NO2(aq) → 2Mn(aq) + 5NO3(aq) + 3H2O(l)
The nitrite solution cannot be titrated with permanganate solution from a burette in the
usual way, because, as soon as it is acidified, the nitrous acid formed begins to decompose.
2NaNO2(aq) + H2SO4(aq) → Na2SO4(aq) + 2HNO2(aq)
3HNO2(aq) → HNO3 + H2O(l) + 2NO(g)
Thus, the nitrite solution is placed in the burette and is added, SLOWLY and with constant
swirling to an acidified solution of potassium permanganate.
Chemicals :
(i) Na2C2O4 (0.025 N exact).
159
(ii) KMnO4 solution (approximate 0.025 N).

(iii) KNO2.
(iv) H2SO4 (2 N).
Procedure :
This experiment is performed in the following three parts :
Part A : Preparation of standard solution of sodium oxalate (MW = 134) (0.025 N) :
1000 ml 1 N oxalic acid solution contains 67 g Na2C2O4.
1000 ml 0.1 N oxalic acid solution contains 6.7 g Na2C2O4.
∴ 100 ml 0.025 N oxalic acid solution contains 0.1675 g Na2C2O4.
7. Weigh accurately 0.1675 g of A.R. grade sodium oxalate crystals on watch glass.
volumetric flask.
11. Take out all the solution in a clean beaker to make homogeneous solution. This is
0.025 N oxalic acid solution.
12. Use this solution for standardization of given KMnO4 solution.
Part B : Standardization of KMnO4 solution :
12. Fill the burette No. 1 with 0.025 N (approximate) KMnO4 solution.
13. Fill the burette No. 2 with standard 0.025 N sodium oxalate solution.
14. Take 9 ml of sodium oxalate solution from burette No. 2 in a 100 ml conical flask.
Call this volume as V2 ml.
15. Add to it 1/2 test tube (10 ml) of 2 N (dilute) H2SO4.
16. Heat the solution on wire gauze to about 70-80°C. Titrate this hot solution of oxalic
acid against KMnO4 solution, added slowly (drop by drop) from burette No. 1 with
constant shaking of the flask.
17. Continue the addition of KMnO4 till the solution in the conical flask changes from
colourless to permanently faint pink. Record the burette reading and call this as
‘X1’ ml.
18. Add to the same conical flask 1 ml solution of 0.025 N sodium oxalate from burette
No. 2. Heat the flask again so that solution in the flask acquires a temperature of
about 70-80°C and solution becomes colourless.
19. Add KMnO4 solution from burette No.1 till a permanent faint pink colour appears to
the solution. Record the burette reading and call this as X2 ml.
160
20. To the same solution in the conical flask add 1 ml solution of 0.025 N sodium oxalate
from burette No. 2 (See that the solution in the flask is hot, if not, heat it again to
70-80°C). The pink colour disappears.
21. Add KMnO4 solution from burette No. 1 till a faint permanent pink colour appears to
the solution. Call this reading as X3 ml.
Part C : Estimation of Nitrite from the given solution :
1. Weigh accurately 0.200 g (W) of sodium nitrite and dissolve it in a small quantity of
distilled water.
2. Dilute the above solution to prepare 100 ml of sodium nitrite solution using
volumetric flask .
3. Fill burette No. 1 with diluted sodium nitrite solution and burette No. 2 with
potassium permanganate solution.
4. Pipette out 10 ml potassium permanganate solution from burette No. 2 into a conical
flask. Add 10 ml (1/2 test tube) dilute sulphuric acid (2 N) to acidify the nitrate
solution.
5. Titrate this acidified potassium permanganate solution by the addition of the sodium
nitrite solution from burette No. 1 slowly and with continual stirring till the pink
colour is just disappeared. Record this reading as Y1 ml.
6. Similarly perform two more titrations to obtain at least two concordant results.
(difference < 0.2 ml). Record these as Y2 and Y3 respectively.
7. Find out the quantity of nitrite present in the sample of given sodium nitrite.
Remarks:
1. The end-point of this reaction is not very sharp. Be careful not to use too much titrant.
2. The normality of KMnO4 stated in this manual is only an approximate value. Do not use
this for calculations.
Observation Table : Part B : Standardization of KMnO4 solution.
To find : Exact normality of KMnO4 solution
Burette 1 : KMnO4 solution (~ 0.025 N) Burette 2 : Sodium oxalate (0.025 N)
Indicator : KMnO4 (self-indicator) End point : Colourless to pink
Reaction :
2 KMnO4 + 5 Na2C2O4 + 8 H2SO4 → K2SO4 + 2 MnSO4 + 5 Na2SO4 + 10 CO2 + 8H2O
‘X’ ml V2 ml N = 0.025 × V2
X
1. X1 = ….. 9.0 N1 = 0.025 × 9
161
X1
2. X2 = ….. 9 + 1 = 10.0 N2 = 0.025 × 10
X2
3. X3 = ….. 10 + 1 = 11.0 N3 = 0.025 × 11
X3
Calculations:
1. To calculate exact normality of KMnO4:
N1 + N2 + N3
Mean Normality N4 = = .......... N
3
∴ Hence, the exact normality of KMnO4 is ………..(N4) N.

Observation Table: Part C: Estimation of Nitrite from Sodium nitrite.
To find : Amount of nitrite from sodium nitrite.
Burette 1 : Sodium nitrite Burette 2 : KMnO4 solution (accurate N4)
Indicator : KMnO4 (self-indicator) End point: Pink to colourless
Reaction:
− − −
2MnO4 + 5NO2 + 6H+ → 2Mn2+ + 5NO3 + 3H2O
Obs. No. Burette 1 Burette 2 Constant Burette
‘Y’ ml V2 ml Reading (CBR)
1. Y1 = ….. 10
2. Y2 = ….. 10 ‘Y’ ml
3. Y3 = ….. 10
Calculations:
2. To calculate amount of nitrite:
− − −
2 MnO4 + 5 NO2 + 6 H+ → 2 Mn2+ + 5 NO3 + 3 H2O
−
2 moles of KMnO4 ≡ 5 moles of NO2
−
1 mole of KMnO4 = 5/2 moles of NO2
−
1 N KMnO4 ≡ 5/2 × 1/5 moles of NO2
(As 1 g equiv. of KMnO4 = 1/5 Mol. wt. of KMnO4)
− −
= 5/10 × 46.00 g NO2 = 23 g NO2
−
As 1000 ml 1 N KMnO4 ≡ 23 g NO2
162
Y1 × N4 × 23 −
∴ Y ml of N4 KMnO4 = = ‘A’ g NO2
1000 × 1
−
As 10 ml diluted solution contains ‘A’ g of NO2
100 × A −
∴ 100 ml diluted solution contains = = 10 × ‘A’ = ‘B’ g of NO2
10
−
∴ Hence, the amount of nitrite present in the given sample = ……… ‘B’ g of NO2
3. To calculate percentage of nitrite:
As W grams of sodium nitrite sample contains ‘B’ grams of nitrite
100 × 'B' −
∴ 100 grams of sodium nitrite sample contains = = …… (Z) % of NO2
W
Result Table :
1. Exact normality of KMnO4 N4 = ………. N
2. 10 ml KMnO4 solution required Y = ………. ml of sodium

nitrite solution
3. Amount of nitrite in the given solution B = …….. g
4. Amount of nitrite in the given solution ‘Z’ = …….. %
VIVA VOCE
1. Explain the term 'Volumetric analysis'.
2. Define the terms : Standardization, Titration, Standard solution.
3. What do you mean by normal solution ?
4. Calculate the equivalent weight of KMnO4 in this reaction.
5. How 100 ml 0.025 N sodium oxalate solution is prepared ?
6. What is the type of this titration ?
7. Why KMnO4 is not titrated directly?
Experiment No. 3
Percentage Purity of NaCl
Aim :
Estimation of percentage purity of given sample of sodium chloride.
Principle :
Sodium chloride reacts quantitatively with silver nitrate as per the following equation :
AgNO3 + NaCl → AgCl + NaNO3
163
169.89 58.5
So the purity of sodium chloride is determined by titrating it with standard silver nitrate
solution. The titration is carried out in neutral cold solution using precipitation or adsorption
indicator. This method is known as Mohr’s method of estimation.
169.89 g AgNO3 ≡ 58.5 g NaCl
So, 1000 ml 1 N solution of AgNO3 ≡ 58.5 g NaCl
∴ 1 ml 1 N solution of AgNO3 ≡ 0.085 g NaCl
Chemicals :
(i) Sodium chloride sample
(ii) 0.05 N silver nitrate solution
(iii) 5% potassium chromate solution
Procedure :
1. Weigh accurately 0.5 g of sodium chloride on a watch glass. Record the weight as
'W' g.
2. Transfer this weighed sample in 100 ml beaker. Rinse the watch glass. Dissolve the
crystals in about 50 ml distilled water.
3. Transfer the resulting solution carefully in 100 ml volumetric flask. Rinse the beaker
with distilled water. Dilute the solution upto the mark with distilled water. Take out all
the solution in a beaker.
4. Fill the burette No. 1 with standard 0.05 N solution of AgNO3.
5. Fill the burette No. 2 with sodium chloride solution.
6. Take 9 ml sodium chloride solution in a 100 ml conical flask.
7. To this add about 3 - 4 drops of 5% potassium chromate solution.
8. Titrate this solution with standard silver nitrate solution from burette No. 1 with
swirling the conical flask until the brick red colour formed by each drop begins to
disappear more slowly indicating the most of the chloride has been precipitated.
9. Make the addition dropwise towards the end and finish the titration when faint brick
red colour appears in the precipitate which persists even after brisk shaking. The
precipitate will also coagulate suddenly at this point. Record the burette reading and
call this as X1 ml.
10. To the same solution in the conical flask add 1 ml solution of NaCl from burette
No. 2. Shake the flask, brick red colour disappears.
11. Add AgNO3 solution from burette No. 1 with swirling the conical flask. Make the
addition dropwise and finish the titration when faint brick red colour appears in the
164
precipitate which persist even after brisk shaking. Record the burette reading and call
this as X2 ml.
12. To the same solution in the conical flask add 1 ml solution of NaCl from burette
No. 2. Shake the flask, brick red colour disappears.
13. Add AgNO3 solution from burette No. 1 with swirling the conical flask. Make the
addition dropwise and finish the titration when faint brick red colour appears in the
precipitate which persist even after brisk shaking. Record the burette reading and call
this as X3 ml.
Note :
1. The above method can be employed for the determination of KCl, NH4Cl, KBr in
neutral solutions.
2. Burette with rubber tube should not be used as the rubber may react with silver
nitrate solution.
3. Silver nitrate addition should be very slow. It should not be added in large amounts
at a time.
4. All solutions required for this practical should be prepared in distilled water only.
Rinse all the apparatus required with distilled water.
Observation Table :
Burette 1 : Standard 0.05 N AgNO3 solution
Burette 2 : Diluted solution of NaCl
Indicator : 5% potassium chromate solution
End point : Colourless to faint brick red
Obs. No. Burette 1 Burette 2

Y ml V2 ml
1. X1 = 9.0
2. X2 = 9 + 1 = 10.0
3. X3 = 10 + 1 = 11.0
Mean burette reading 1 Mean burette reading 2

X1 + X2 + X3 9 + 10 + 11
= = X ……. ml = = 10 ml
3 3
Calculations :
1. To calculate amount of NaCl in the solution :
1 ml 1 N solution of AgNO3 ≡ 0.0585 g NaCl
165
0.0585 × 0.05 × X
∴ X ml 0.05 N solution AgNO3 ≡
1
0.00292 × X = Y g of NaCl
∴ 10 ml diluted NaCl solution = Y g of NaCl
∴ 100 ml diluted NaCl solution = Y × 10 g NaCl
= Z g NaCl
The amount of NaCl in the solution = Z = …….. g.
2. To calculate purity of NaCl sample :
W g sample = Z g NaCl
Z × 100
∴ 100 g sample = = ………. % NaCl
W
= Percentage purity of NaCl
Result Table :
1. Weight of NaCl sample taken W = ………. g
2. Amount of AgNO3 required for 10 ml X = ………. ml
diluted NaCl solution
3. Percentage purity of NaCl = ………. %
VIVA VOCE
1. What will happen if some one use tap water for preparation of solutions ?
2. Why the burette with rubber tube is not advisable ?
3. In which class will you classify the Mohr’s method of titration ?
4. What are adsorption indicators ?
5. Is it possible to have a situation like Z > W ? Justify your answer.
6. What impurities do you expect in the NaCl sample collected from sea water ?
Experiment No. 4
Analysis of Brass
Aim :
To determine the amount of copper from brass iodometrically.
Principle :
Brass is an alloy which consists of mostly copper (50 to 90%) and zinc (20 to 40%) along
with small amounts of lead (0 to 2 %), tin (0 to 6 %) and iron (0 to 1%).
The experiment consists of dissolving a known quantity of brass in nitric acid, removing
the nitrate by fuming with sulphuric acid.
166
Copper from the brass may be iodometrically determined while zinc is determined
gravimetrically as Zn2P2O7. In iodometric determination, Cu ions liberate iodine from KI and
the liberated I2 is titrated against standard thiosulphate solution.
When the brass sample is dissolved in nitric acid, the copper is brought into solution in
the form of cupric ions. The Cu2+ ions are reducible by iodide. Then the Cu2+ can be
titrimetrically determined by the iodometric method.
2Cu2+ + 4I− → 2CuI + I2
− −
2S2O3 + I2 → S4O6 + 2I−
−
Cu ≡ I ≡ S2O3
Chemicals :
(i) K2Cr2O7 crystals
(ii) Na2S2O3 solution (approximate 0.05 N)
(iii) 5% KI solution
(iv) Starch indicator
(v) 1 : 1 HNO3
(vi) 2 N NaOH
(vii) 2 N CH3COOH
(viii) Brass sample.
Procedure :
Part A : Preparation of standard solution of 0.05 N K2Cr2O7 (Eq. wt. 49) :
1000 ml 1 N K2Cr2O7 solution ≡ 49 g of K2Cr2O7
∴ 100 ml 0.05 N K2Cr2O7 solution ≡ 0.245 g of K2Cr2O7
1. Weigh accurately 0.245 g of A.R. grade K2Cr2O7 crystals on a watch glass.
2. Transfer the weighed crystals carefully in a clean 100 ml beaker and rinse the watch
glass with distilled water. Stir the solution with glass rod and dissolve the crystals.
3. Pour this solution in a clean 100 ml volumetric flask. Add carefully little water and
dilute upto the mark.
4. Take out the solution in a clean beaker.
5. This becomes 0.05 N K2Cr2O7 solution. This solution is used for standardization of
Na2S2O3 solution.
Part B : Standardization of Na2S2O3 solution :
1. Fill the burette No. 1 with 0.05 N (approximate) Na2S2O3 solution.
2. Fill the burette No. 2 with 0.05 N K2Cr2O7 solution.
3. Take 9 ml K2Cr2O7 solution from burette No. 2 in a 100 ml conical flask or stoppered
bottle. Call this volume as V2 ml.
167
4. Add 3 ml concentrated HCl and add 10 ml 5% KI solution. Shake the flask/bottle well
and keep it for five minutes.
5. Titrate the liberated iodine with Na2S2O3 solution till a pale yellow colour appears.
Then add 1 - 2 ml starch indicator. The solution will become blue in colour. Continue
the titration.
6. The end point of the titration is recorded when colour changes from dark blue to
green. (there is sudden change in colour). Call this burette reading as X1 ml.
7. To the same flask/bottle add 1 ml of 0.05 N K2Cr2O7 from burette No. 2 (need not
add any indicator now). The solution turns blue.
8. Titrate this against Na2S2O3 solution from burette No. 1 till the colour of the solution
changes from blue to green. Record this reading as X2 ml.
9. To the same flask/bottle add 1 ml of 0.05 N K2Cr2O7 by burette No. 2 (do not add any
indicator). The solution turns blue.
10. Titrate this against Na2S2O3 solution from burette No. 1 till the colour of the solution
changes from blue to green. Record this reading as ‘X3' ml.
11. From the burette readings X1, X2 and X3 find out the normality of Na2S2O3 solution.
Part C : Preparation of brass solution :
1. Weigh accurately about 0.2 g of given brass sample on a watch glass. Call this as W g.
2. Transfer it carefully to 100 ml conical flask. Add about 15 ml of 1:1 HNO3 by a
measuring cylinder. Cover the flask with stem cut glass funnel and heat it on wire
gauze at low flame.
3. Dissolve the alloy (brass sample) completely and then cool the solution. To this cold
solution add 10 ml water and 5 ml conc. H2SO4 to remove the excess of HNO3. Boil
the solution to eliminate brown fumes. (Heat the solution till white fumes are
evolved).
4. If the solution is clear, transfer it carefully to 100 ml volumetric flask and dilute upto
the mark with distilled water. (If the solution is not clear, then filter it through
Whatmann filter paper No. 42. Wash the residue with water. Collect the filtrate and
washings and dilute to 100 ml).
5. Take out whole solution in a beaker and stir well.
Part D : Iodometric determination of copper :
1. Fill the burette No. 1 with standardized thiosulphate solution.
2. Fill the burette No. 2 with diluted solution of brass. Take 10 ml of this solution in a
stoppered bottle.
3. Add to it 2 N NaOH solution till slight turbidity is obtained. Dissolve this turbidity by
adding drop by drop 2 N acetic acid. Shake the bottle well. Add 2 to 3 drops of acetic
acid in excess.
168
4. Add 10 ml of 5% KI solution by means of measuring cylinder.

5. Titrate the liberated iodine with Na2S2O3 solution from burette No. 1 till the colour of
the solution becomes pale yellow.
6. Then add 1 to 2 ml freshly prepared starch indicator. The solution becomes blue.
7. Continue the titration. The end point of the titration is recorded when colour changes
from dark blue to colourless. Record this reading as Y1 ml.
8. Take two more readings by repeating step No. 2 to 7 and record the constant burette
reading.
9. From this reading determine the amount of copper in the given sample of brass.
Observation Table :
Part B : Standardization of Na2S2O3 solution
To find : Exact normality of Na2S2O3 solution
Burette 1 : 0.05 N (approximate) Na2S2O3 solution
Burette 2 : 0.05 N (exact) K2Cr2O7
Indicator : Starch solution (freshly prepared)
End point : Blue to green.
Equations :
1. K2Cr2O7 + 6KI + 14HCl → 8KCl + 2CrCl3 + 7H2O + 3I2 ↑
2. 2Na2S2O3 + I2 → Na2S4O6 + 2NaI
X ml V2 ml 0.05 × V2
N=
X
1. X1 = ….. 9.0 0.05 × 9

N1 =
X1
2. X2 = ….. 9 + 1 = 10.0 0.05 × 10

N2 =
X2
3. X3 = ….. 10 + 1 = 11.0 0.05 × 11

N3 =
X3
N1 + N2 + N3
Mean normality N4 = = .......... N
3
Exact normality of Na2S2O3 = N4 = ………. N
Part D : Estimation of Copper
To find : Amount of copper in the brass sample
169
Burette 1 : Standardized Na2S2O3 solution

Burette 2 : Diluted brass solution
Indicator : Starch solution (freshly prepared)
End point : Blue to colourless.
Reactions : 2CuSO4 + 4KI → 2CuI2 + 2K2SO4
2CuI2 → Cu2I2 + I2
2CuSO4 + 4KI → Cu2I2 ↓ + 2K2SO4 + I2 ↑
Liberated I2 is titrated against Na2S2O3.
I2 + Na2S2O3 → 2NaI + Na2S4O6
Readings Pilot Reading Constant B.R.
Burette Reading, ml
ml ml
I II III
Final
Initial 0.00 0.00 0.00 0.00 ‘Y’ ml
Difference
Calculations :
1. To calculate amount of copper in the solution :
2CuSO4 ⋅ 5H2O ≡ I2 ≡ 2Na2S2O3 ⋅ 5H2O = 2Cu
∴ Na2S2O3 ⋅ 5H2O ≡ Cu.
248 ≡ 63.5 g
100 ml 1 N Na2S2O3 ≡ 63.5 g Cu
Y × N4 × 63.5
∴ ‘Y’ ml N4 Na2S2O3 ≡ = A g of Cu
1000 × 1
10 ml diluted solution of brass contains A g Cu
∴ 100 ml diluted solution of brass contains A × 10 = B g Cu
2. To calculate percentage of copper in the brass sample :
W g of brass sample = B g of copper
∴ 100 g of brass sample = ?
100 × B
= = ………. % of copper
W
Result Table :
1. Weight of the brass sample taken W = ………. g
2. Exact normality of Na2S2O3 solution N4 = ………. N
3. Volume of 0.05 N Na2S2O3 solution Y = ………. ml
required to titrate 10 ml diluted solution of
brass
170
4. Amount of Cu in the 100 ml solution B = ………. B g

5. Percent of Cu in brass alloy = ………. %
VIVA VOCE
1. Why always excess of KI is used for iodometric titrations ?
2. Why should fresh solution of starch be used ?
3. Write the chemical equations involved in this analysis.
4. What are the major and minor constituents of brass alloy ?
5. What is the principle of estimation of Cu in brass ? Explain with chemical equations.
6. What is iodometry and iodimetry ?
7. What is the role of K2Cr2O7 solution in this titration ?
Experiment No. 5
Aim :
To determine the amount of Phosphate (PO4)3− from fertilizer sample by volumetric
method.
Principle :
When solution of phosphate is treated with excess ammonium molybdate in the
presence of concentrated nitric acid then formation of yellow precipitate of ammonium
molybdo-phosphate [(NH4)3 ⋅ PO4 ⋅ 12 MoO3] take place. Precipitate is filtered using
Whatman filter paper - 42 and then washed till free from acid. The washed precipitate of
ammonium molybdophosphate gives rise to the formation of Na2MoO4, Na2HPO4, H2O and
NH3. This solution is boiled to evolve excess of ammonia present in the solution and then
excess NaOH is back titrated with standard HCl solution using phenolphthalein indicator.
From amount of NaOH required for dissolution of ammonium molybdophosphate
(phosphate as P2O5) in the precipitate was calculated using the following equation.
Equation :
1000 ml 1 N NaOH ≡ 3.088 g P2O5
Chemicals :
(i) Conc. HNO3
(ii) 1 N NaOH
(iii) 0.1 N HCl
(iv) 3% ammonium molybdate
(v) 0.1 N potassium hydrogen phthalate
Apparatus :
(i) Beakers
(ii) Conical flask
171
(iii) Volumetric flask

(iv) Burette
(v) Funnel
(vi) Whatman paper - 42
Procedure :
Part A: Preparation of standard solution of potassium hydrogen phthalate, KHP (0.1 N):
1. Weigh accurately 2.045 g of A.R. grade potassium hydrogen phthalate crystals on
watch glass.
volumetric flask.
5. This is 0.1 N KHP solution. Use this solution for standardization of given NaOH
solution.
Part B : Standardization of NaOH solution :
1. Fill the burette No. 1 with 0.1 N KHP solution.
2. Fill the burette No. 2 with diluted NaOH (10 ml 1 N NaOH is diluted to 100 ml)
solution (0.1 N approximate).
3. Take 9 ml NaOH solution from burette No. 2 in a 150 ml conical flask.
4. Add 2 - 3 drops of phenolphthalein indicator. The solution becomes pink in colour.
5. Titrate this solution against 0.1 N KHP solution from burette No. 1, till pink colour just
disappears. Call this burette reading as X1’ ml.
6. To the same flask add 1 ml of 0.1 N NaOH from burette No. 2. The solution turns
pink.
7. Titrate this against 0.1 N KHP solution from burette No. 1 till the colour just
disappears. Record this reading as ‘X2’ ml.
8. To the same solution in conical flask add 1 ml of NaOH solution from burette No. 2.
The solution turns pink.
9. Titrate this solution against 0.1 N KHP from burette No. 1 till the colour of solution
disappears. Record this reading as ‘X3’ ml.
10. From the burette readings X1, X2 and X3, find out the normality of NaOH solution as
N1, N2 and N3.
Part C : Precipitation of phosphate as ammonium molybdophosphate from fertilizer
sample :
172
1. Weigh accurately about 0.2 - 0.3 g of fertilizer (DAP) sample on a watch glass. Call
this as ‘W’g.
2. Transfer it carefully in 100 ml conical flask. Add about 50 ml distilled water and 2 ml
conc. HNO3.
3. If necessary, filter and wash the residue with 10 ml distilled water.
4. Heat the filtrate upto 40°C, to it add 3 ml conc. HNO3 and then add 3% ammonium
molybdate solution, till complete precipitation of phosphate take place.
5. Then add 5 ml excess 3% ammonium molybdate.
6. Keep this precipitate in hot condition for 20 - 30 minutes. Filter this precipitate
through Whatman filter paper 42 and wash with 1% ammonium nitrate, till free from
acid.
3−
Part D : Back titration : Estimation of phosphate, PO4 :
1. Dissolve the above precipitate by dropwise addition of 20 ml 1 N NaOH solution on
the filter paper. After complete dissolution of the precipitate, wash the Whatman
filter paper with 20 ml hot distilled water.
2. Boil this solution for 10 minutes, so that complete evolution of NH3 takes place from
the solution.
3. Cool the solution to room temperature and then dilute this to 100 ml in volumetric
flask.
4. Fill the burette No. 1 with 0.1 N HCl solution.
5. Fill the burette No. 2 with above diluted solution.
6. Take 10 ml of diluted solution of fertilizer sample from burette No. 2 in a 100 ml
conical flask.
8. Titrate this solution against 0.1 N HCl from burette No. 1, till pink colour disappears.
9. This is the end point of titration. Record this reading as first burette reading.
10. Take two more readings by repeating step 6 to 8 and record the constant burette
reading as ‘Y’ ml.
Part E : Blank titration :
1. Take 0.1 N HCl solution in burette No. 1.
2. Take diluted solution of NaOH (Dilute 20 ml 1 N NaOH to 100 ml in volumetric flask)
in burette No. 2.
3. Take 10 ml of this NaOH solution in a 100 ml conical flask from burette No. 2.
173
5. Titrate this solution against 0.1 N HCl from burette No. 1, till pink colour disappears.
6. This is the end point of titration. Record this reading.
7. Take two more readings by repeating step 3 to 5 and record the constant burette
reading as ‘Z’ ml.
Observation Table :
Part B : Standardization of NaOH solution
Burette 1 : 0.1 N KHP (Potassium hydrogen phthalate)
Burette 2 : Diluted NaOH solution
To find : Exact normality of NaOH solution
Indicator : Phenolphthalein
End point : Pink to colourless
Obs. No. Burette 1 Burette 2 0.1 × V
Normality, N =
X ml ‘V’ ml X
1. X1 = ….. 9.0 0.1 × 9
N1 =
X1
2. X2 = ….. 9 + 1 = 10.0 0.1 × 10
N2 =
X2
3. X3 = ….. 10 + 1 = 11.0 0.1 × 11
N3 =
X3
N1 + N2 + N4
Mean Normality, N4 = = …… N
3
Part E : Blank titration
Burette 1 : 0.1 N HCl
Burette 2 : Diluted NaOH solution
Readings Pilot Reading Constant Burette Reading
Burette Readings, ml
ml (C.B.R.) ml
I II III
Final
Initial 0.00 0.00 0.00 0.00 Y = …… ml
Difference
174
3−
Part D : Back titration : Estimation of phosphate, PO4
Burette 1 : 0.1 N HCl
Burette 2 : Diluted molybdate solution
Readings Pilot Reading Constant Burette Reading
Burette Readings, ml
ml (C.B.R.) ml
I II III
Final
Initial 0.00 0.00 0.00 0.00 Z = …… ml
Difference
Calculations :
3−
(1) To find out the amount of phosphate (PO4 ) from given fertilizer sample:
1000 ml 1 N NaOH = 3.088 g P2O5
∴ (Blank - Back) i.e. (Y − Z) ml ‘N4’ N NaOH = ? g P2O5
(Y − Z) × N4 × 3.088
=
1 × 1000
= A = …… g of P2O5
10 ml diluted solution = ‘A’ = g of P2O5
∴ 100 ml diluted solution = A × 10 = ‘B’ = g of P2O5
= B = …… g of P2O5
(2) To calculate the percentage of phosphate in the fertilizer sample :
“W’ g of fertilizer sample = ‘B’ g of P2O5
∴ 100 g of fertilizer sample = ?
100 × B
=
W
= …… % of P2O5
Result Table :
1. Weight of fertilizer sample taken W = ………. g
2. Exact normality of NaOH solution N4 = ………. N
3. Amount of phosphate in the 100 ml B = ………. g
solution
4. Percent of phosphate in the given fertilizer = ………. %
175
sample in the form of P2O5
−−−
176
(C) Inorganic Preparations
(Any Four)
Introduction :
Inorganic preparation includes preparation of a double salt and three coordination
complexes. Coordination complexes differ from the double salts. The combination of two
different single salts which crystallizes together as a single substance is known as double
salt. Double salt does not loose identity of individual ions in solid and in aqueous solution
(i.e. they give characteristic tests for their individual ions).
Coordination complexes consist of a complex ion formed by combination of metal ion
and ligands. Here ligands are bounded to central metal ion by a coordinate linkage. These
complex ions may have positive or negative charge and are soluble in water. In complexes,
metal ions lose their identity in solution and solid state. These complexes do not undergo
dissociation in aqueous solution.
Experiment No. 1
Preparation of Hexamminenickel(II) Chloride [Ni(NH3)6]Cl2
Aim :
To prepare hexamminenickel(II) chloride.
Principle :
The nature as well as strength of the ligand is one of the important factors that
determines the formation and stability of a metal complex. A stronger ligand can replace a
weaker ligand from a metal centre. Therefore, ammonia can easily replace OH− or H2O from a
metal centre (as NH3 is a stronger ligand than OH− or H2O). Similarly, ethylenediamine can
replace ammonia because it is more stronger than ammonia.
[Ni(NH3)6]Cl2 is an octahedral complex having purple colour. When nickel chloride
hexahydrate, NiCl2 ⋅ 6H2O is dissolved in water, hexaquo complex of nickel is formed. Upon
addition of ammonia initially there may be formation of nickel hydroxide (indicated by
formation of green ppt.) which further reacts with ammonia to give ammine complex. This
reaction depends on the stoichiometry of the reactants and if excess ammonia is not used
following mixtures of products with varying composition may be obtained. For example,
[Ni(NH3)5(H2O)]Cl2,
[Ni(NH3)3(H2O)3]Cl2,
176
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Inorganic Preparations
[Ni(NH3)5Cl]Cl etc.
NH3
H3N NH3
Ni Cl2
H3N NH3
NH3
Structure of [Ni(NH3)6]2+Cl2
The complex can be prepared by taking nickel chloride hexahydrate as a water solution
to which excess of ammonia is added. The colour of the solution changes from pale dark
green to purple. Upon cooling the reaction mixture in an ice bath [Ni(NH3)6]2+, complex will
be precipitated out as purple coloured crystals. The structure of the complex is as shown in
the structure above.
Chemicals :
(i) Nickel chloride hexahydrate NiCl2 ⋅ 6H2O.
(ii) Liquor ammonia (sp. gr. 0.9).
Apparatus :
100 ml beakers, Buchner funnel, glass rod, ice bath.
Procedure :
1. Weigh about 1.5 g of nickel chloride hexahydrate. Transfer it in a 100 ml beaker.
2. Dissolve the solid in minimum quantity of water (about 4 ml).
3. Take 4 ml of concentrated aqueous ammonia in another beaker and fill it in burette.
4. Add the ammonia slowly to a rapidly stirred solution of the nickel chloride using
burette.
5. Colour of the solution is found to change from pale green to intense violet (if not,
add more ammonia).
6. Allow the solution to stand at room temperature for five minutes, and then cool it in
an ice bath without disturbance for about 20 minutes.
7. If violet crystals of [Ni(NH3)6]Cl2 are not formed, try to crystallize it by gently
scratching the sides of the beaker with a glass rod.
8. Filter the crystals and wash the product with concentrated ammonia solution (5 ml).
9. Dry the crystals by pressing it between filter papers. (Do not expose the product to
IR lamp).
177
10. Record the yield of the dried product and calculate % yield.
Chemical Reactions :
NiCl2 ⋅ 6H2O + H2O → [Ni(H2O)6]Cl2
[Ni(H2O)6]Cl2 + 6NH3 → [Ni(NH3)6]Cl2 + 6H2O
Observations :
Weight of the dried product = X = ………. g
Calculations :
(i) Theoretical yield of the complex :
NiCl2 ⋅ 6H2O = [Ni(NH3)6]Cl2
237.6 g of salt = 231.6 g of complex
∴ 1.5 = ?
1.5 × 231.6
= = 1.46 g
237.6
∴ Theoretical yield of the complex = 1.46 g
(ii) Percent practical yield of the complex :
Theoretical yield of the complex is 1.46 g.
∴ 1.46 g product = 100% yield
∴ X g product = ?
X × 100
= = ………… % yield of the complex
1.46
Result Table :
1. Practical yield of the complex = X = ……….. g
2. Theoretical yield of the complex = 1.46 gm = ………. 1.46 gm
3. % Practical yield of the complex = ……….. %
4. Colour of the complex Purple
VIVA VOCE
1. What are the factors that decide the strength of ligand ?
2. Arrange the following ligands in the order of increasing strength :
2−
I−, OH−, C2O4 , en, CN−, NCS−, H2O, Py, NH3, CO.
3. How will you determine the formation of correct complex ?
4. What is your opinion about the stability of the complex ?
178
5. Explain the change in colours observed during this preparation.
Experiment No. 2
Preparation of Potassium trioxalatoferrate(III) trihydrate,
K3[Fe(C2O4)3] ⋅ 3H2O
Aim :
To prepare potassium trioxalatoferrate(III) trihydrate and its purity determination by
estimation of oxalate using permanganometry.
Principle :
Iron forms octahedral complexes with monodentate and bidentate ligands. The oxalate
ion is a bidentate ligand which acts as a chelating agent and forms a stable ring around the
central metal ion in a metal chelate. This ring structure is called a chelate and formation of
such a ring structure is called chelation. Chelated complexes are more stable than simple
complexes formed by monodentate ligands, because dissociation of complex involves
breaking of two bonds rather than one bond per ligand molecule.
The preparation of K3[Fe(C2O4)3] involves two steps. Step one is a preparation of ferrous
oxalate from ferrous ammonium sulphate and step two is the conversion of ferrous oxalate
to potassium trioxalato ferrate (III) trihydrate. During this conversion hydrogen peroxide
works as oxidizing agent i.e. to oxidize Fe(II) to Fe(III). It is water soluble complex. Thus, on
addition of alcohol to the solution containing complex, formation of green crystals of
trioxalato ferrate (III) complex takes place in solution.
O O:
C
C
O O:
2−
Structure of C2O4 ligand
2−
Oxalate ion (C2O4 ) is a bidentate ligand i.e. one ion of it forms two coordinate bonds
with central metal ion as shown in the figure above.
In the present complex three such oxalate ions form a stable complex (chelate) with
Fe3+ ion as shown in structure below.
179
O
O
C
C
O O
O O C
K3 Fe 3H2O
O O C
O
O
C
C
O
O
Structure of K3[Fe(C2O4)3] ⋅ 3H2O

Chemicals :
(i) Ferrous ammonium sulphate.
(ii) Oxalic acid.
(iii) Potassium oxalate monohydrate.
(iv) Hydrogen peroxide.
(v) Ethanol.
(vi) Acetone.
Apparatus :
100 ml beaker, Buchner funnel, conical flask, burettes.
Procedure :
Step I : Preparation of iron (II) oxalate :
1. Dissolve 3.75 g of ferrous ammonium sulphate in 15 ml warm distilled water. Acidify
the resulting solution by adding 3-4 drops of concentrated sulphuric acid so that
solution becomes clear.
2. Add 20 ml 10% oxalic acid solution with constant rapid stirring to the above clear
solution.
3. Heat the reaction mixture gently and cautiously to boiling and then allow the yellow
precipitate of ferrous oxalate to settle.
4. Remove the precipitate by filtration on Buchner funnel. Wash it thoroughly with hot
distilled water and finally with acetone.
5. Allow the product to dry and then use it for the preparation of potassium trioxalato-
ferrate(III) trihydrate.
Step II : Preparation of potassium trioxalatoferrate(III) trihydrate :
1. Add the above precipitate of ferrous oxalate in a warm solution of potassium oxalate
(2.5 g in 15 ml of distilled water).
180
2. Add slowly 30% hydrogen peroxide (about 6.0 ml). Stir the solution and maintain its
temperature upto 40°C. At this stage ferric hydroxide is formed. Ferrous ion is
oxidized to ferric ion.
3. Dissolve the precipitate by heating the solution to boiling and add 3 ml 10% oxalic
acid solution. Further add small amount of 10% oxalic acid (1-2 ml) dropwise until
precipitate just dissolves. (During addition of oxalic acid solution should be
maintained near to boiling.)
4. Filter the hot solution, collect the filtrate in a china dish and boil the solution to
reduce the volume upto 10-15 ml. Stop heating, cool the solution and add 15 ml
ethyl alcohol to the filtrate. Dissolve any crystal formed by gentle heating on water
bath (Caution : Alcohol is inflammable) and keep the solution in dark for
crystallization. Now keep the dish in powdered ice for 5 minutes to complete
crystallization.
5. Remove the bright green crystals formed by filtration on Buchner funnel. Wash with
1 : 1 alcohol and finally with acetone.
6. Dry the product in air (complex is photosensitive and should not be exposed to light)
and record the yield. Call this as X g.
Chemical Reactions :
Fe2+ + H2C2O4 ⎯→ FeC2O4 + 2H+
6FeC2O4 + 6K2C2O4 + 3H2O2 ⎯→ 4K3[Fe(C2O4)3] + 2Fe(OH)3
2Fe(OH)3 + 3H2C2O4 + 3K2C2O4 ⎯→ 2K3[Fe(C2O4)3] ⋅ 3H2O + 3H2O
Observations :
Weight of the dried complex = X = .......... g
Calculations :
1. Theoretical yield of the complex :
(NH4)2Fe(SO4)2 ⋅ 6H2O ≡ K3[Fe(C2O4)3] ⋅ 3H2O
391.85 g of salt ≡ 490.85 g of complex
∴ 3.75 = ?
3.75 × 490.85
= 4.7 g
391.85
∴ Theoretical yield of the complex = 4.7 g
2. Percent practical yield of the complex :
Since, 4.7 g of the complex = 100% yield
∴ X g of the complex = ?
X × 100
= ……….. %
4.7
Result Table :
1. Colour of the complex Bright green
181
2. Practical yield of the complex ‘X’ = ………. g

3. Percent practical yield of the complex = ………. %
VIVA VOCE
1. What are the different types of ligands ?
2. How oxalate ion interact with metal ion ?
3. What do you mean by chelate ? Comment on stability of chelate.
4. What are polydentate ligands ?
5. What are other reagents that can be used for the standardization of KMnO4 ?
6. Explain the mechanism of self-indicator action of KMnO4.
7. What is the role of ethyl alcohol in this preparation ?
8. What is the type of titration in this experiment ?
9. What are different types of titrations ?
Experiment No. 3
Preparation of Tetramminecopper(II) sulphate monohydrate,
[Cu(NH3)4]SO4 ⋅ H2O
Aim :
Preparation of tetramminecopper(II) sulphate monohydrate [Cu(NH3)4]SO4⋅H2O and
estimation of copper iodometrically.
Principle :
When the aqueous ammonia is added in a solution of copper sulphate, ammonia
molecules coordinate with copper ion (Cu2+ metal ion) and forms a square planar complex
[Cu(NH3)4]SO4 ⋅ H2O as shown in structure below.
The complex is soluble in water but insoluble in alcohol. Therefore, the complex is
precipitated by addition of ethanol to the aqueous solution of the complex and cooling in ice
bath. After cooling formation of dark blue coloured crystals takes place in solution which are
removed by filteration.
As complex is soluble in water, its solution can be prepared easily. Hence, Cu2+ ions in the
solution can be estimated by iodometry.
NH3
:
H3N : Cu : NH3 SO4 H2O

:
NH3
Structure of [Cu(NH3)4]SO4 ⋅ H2O

Chemicals :
182
(i) Copper sulphate = 1.5 g.

(ii) Liquor ammonia = 5 ml.
(iii) Rectified spirit = 5 ml.
Procedure :
1. Add 1.5 g finely powdered copper sulphate in 10 ml distilled water in a beaker and
dissolve it completely (warm if necessary).
2. Add about 5 ml liquor ammonia (1 ml at a time) to the cooled solution of copper
sulphate with constant stirring. First a bluish white precipitate is formed which
dissolves further on addition of ammonia and finally the solution becomes dark blue.
Add little excess of liquor ammonia, if necessary.
3. Cool this solution in a water bath and add about 5 ml rectified spirit slowly with the
help of burette with constant stirring.
4. Keep the beaker in ice cold water and continue the stirring. Since the crystals (dark
blue) of tetramminecopper(II) sulphate are insoluble in alcohol, they get crystallize
out and settle at the bottom.
5. If the supernatant solution is dark blue in colour then add more rectified spirit with
stirring and cool it well.
6. Filter the complex on Buchner funnel. Wash the crystals with little amount of ethyl
alcohol. (Never wash the crystals with water as they are soluble in water).
7. Dry the crystals in a desiccator, weigh and record the yield.
Chemical Reaction :
CuSO4 ⋅ 5H2O + 4NH3 ⎯→ [Cu(NH3)4]SO4 ⋅ H2O + 4H2O
Observation :
Weight of the dried product = X = ……….. g
Calculations :
1. Theoretical yield of the complex :
CuSO4 ⋅ 5H2O ≡ [Cu(NH3)4]SO4 ⋅ H2O
249.6 g of salt ≡ 245.6 g of complex
∴ 1.5 g of salt ≡ 1.476 g of complex
∴ Theoretical yield of complex = 1.476 g
2. Percent practical yield of the complex :
Theoretical yield of the complex is 1.476 g
∴ 1.476 g of the complex ≡ 100% yield
X × 100
∴ ‘X’ g of product ≡ ? = = ……….. % yield
1.476
∴ % practical yield of complex = ……….. g
Result Table :
183
1. Colour of the complex Dark blue

2. Practical yield of the complex X = ………. g
3. % yield of the complex = ………. %
VIVA VOCE
1. What do you mean by coordinate bond and coordinate complex ?
2. Why coordinate complexes are coloured in nature ?
3. Draw the structure of [Cu(NH3)4]SO4 ⋅ H2O.
4. What is the difference between double salt and coordinate complex ?
5. Explain the hybridization in this complex and hence explain the geometry.
6. What are the types of ligand ?
Experiment No. 4
Aim :
Preparation of Manganese(III) acetylacetone, [Mn(acac)3].
Principle :
Manganese shows variable oxidation states in compounds (+II to +VII). Manganese(III)
complexes are comparatively stable. Manganese forms octahedral complexes with
acetylacetone ligand. The acetylacetone is a bidentate ligand which acts as a chelating agent
and forms a stable ring around the central metal ion in a metal chelate. Chelates are more
stable than simple complexes.
Complex can be prepared by taking manganese(II) chloride (MnCl2 ⋅ 4H2O) as a water
soluble salt.
This Mn(II) chloride solution is oxidised with KMnO4 in the presence of acetyl acetone
producing the brown coloured [Mn(acac)3] complex.
Chemicals :
(i) Manganese(II) chloride (MnCl2 ⋅ 4H2O) = 1.05 g
(ii) Sodium acetate (CH3COONa) = 2.80 g
(iii) Acetylacetone (CH3COCH2COCH3) = 4 ml
(iv) Potassium permanganate (KMnO4) = 0.22 g
Apparatus :
100 and 50 ml beakers, glass rod, micro-pipette etc.
Procedure :
1. Weigh about 1.05 g of manganese(II) chloride tetrahydrate on watch glass. Transfer it
in a 100 ml beaker. Dissolve the solid in 60 ml water.
184
2. Weigh 0.22 g KMnO4 on a watch glass. Dissolve it in 25 ml distilled water in 50 ml

beaker.
3. Weigh 2.8 g sodium acetate trihydrate on a watch glass. Dissolve it in 15 ml distilled
water in a separate 50 ml beaker.
4. Add the acetylacetone (4 ml) slowly by constant stirring in manganese chloride
solution using micro-pipette or dropper.
5. Add dropwise solution of KMnO4 to the above solution with constant stirring.
6. Stirring is continued for another 5 minutes. Here KMnO4 acts as an oxidising agent.
7. Add solution of sodium acetate dropwise with constant stirring. (Sodium acetate
maintains the pH of the solution upto 5).
8. Heat the above solution near to boiling (do not boil) for 10 minutes.
9. Cool the reaction mixture to room temperature.
10. Filter the brown crystals and the product distilled water.
11. Dry the crystals by pressing between filter papers. Then transfer the solid into a
porcelain dish. Dry it in under IR lamp for at least 30 minutes.
12. Record the yield of the complex and calculate % yield of [Mn(acac)3] complex.
Reaction :
pH = 5
4MnCl2 + KMnO4 + 15 CH3.CO.CH2COCH3 ⎯⎯⎯→ = 7 HCl + KCl + 5Mn(CH3COCHCOCH3)3 + 4H2O
Structure of the Complex :
H3C H
C C
CH3 acac
O O
C CH3
C C O O O O
H C Mn OR Mn acac
C O O O O
O C CH3 O
CH3 acac
C
H3C C
H
Acetyl acetone = acac
Fig. 1
Calculations :
(i) Theoretical yield :
Reactant Product (complex)
4 MnCl2 ⋅ 4 H2O ≡ 5[Mn(CH3COCHCOCH3)3]
792 g ≡ 1760 g
792 g MnCl2 ⋅ 4H2O = 1760 g of [Mn(acac)3] complex
185
∴ 1.05 g MnCl2 ⋅ 4H2O = 2.33 g of complex

(ii) Practical yield of the complex = ‘W’ = …… g complex
(iii) % Practical yield of the complex :
2.33 g of complex = 100% yield
W × 100
∴ ‘W’ g of complex = % yield
2.33
= …… % Practical yield
Result Table :
1. Colour of the complex Dark brown
2. Practical yield of the complex W = ………. g
3. Theoretical yield 2.33 g
4. % Practical yield of the complex …… %
Experiment No. 5
Aim :
Preparation of Tris (Thiourea) Copper(I) chloride, [Cu(Thiourea)3]Cl.
Principle :
Cu(I) forms stable octahedral complex with thiourea. The complex has a Cu(I) as a central
metal ion is surrounded by three coordinating molecules of thiourea forming octahedral
complex. This is a chelate complex. Thiourea forms coordinate bonds to Cu(I) ion through
nitrogen atom. Copper(I) compounds and complexes are usually colourless. The soluble
compounds of Cu(I) are unstable in aqueous solution, since they disproportionate to Cu2+
and Cu ions as
2Cu+ → Cu2+ + Cu
Chemicals :
(i) Thiourea, [(NH4)2CS] = 3.2 g
(ii) Copper powder or turnings = 0.7 g
(iii) conc. HCl = 6 ml
(iv) Acetone.
Apparatus : 100 ml beakers, glass rod, water bath, etc.
Procedure :
1. Weigh 3.2 g of thiourea. Transfer it in 100 ml beaker.
2. Dissolve the solid in about 15 ml of distilled water.
186
3. Add to the above solution 0.7 g copper turnings or powder, then add 3 ml of
conc. HCl.
4. Heat the above solution on water bath. Copper turnings dissolve with liberation of
hydrogen gas. Add water to maintain constant level in the flask. (Do not boil the
solution.)
5. Then filter the above solution through a funnel using ordinary filter paper while hot
and allow it to cool slowly. White opaque crystals will form.
6. Filter the crystals using Buchner funnel and wash with little acetone.
7. Allow the crystals to air dry and record the yield. Call it as ‘W’ g.
8. Calculate % practical yield of the complex.
Chemical Reaction :
conc. HCl
Cu + 3(NH2)2CS ⎯⎯⎯⎯→ [Cu((NH2)2CS)3]Cl + H+
H2O
Structure of the complex :
NH2 C S
H2N NH2
S C Cu Cl
H2N NH2
H2N C S
Fig. 1
Calculations :
(i) Theoretical yield of the complex :
Starting material Finished product
Cu(powder) ≡ [Cu((NH2)2CS)3] ⋅ Cl
63.54 g 263.5 g
63.54 g of Cu ≡ 263.5 g complex
∴ 0.7 g of Cu = 2.9 g complex
(ii) Practical yield of the complex = ‘W’ g = …… g
(iii) % Practical yield of the complex :
2.9 g complex = 100% practical yield of the complex
W × 100
∴ ‘W’ g complex = %
2.9
= …… % practical yield of the complex
Result Table :
1. Colour of the complex White opaque
187
2. Practical yield of the complex W = ………. g

3. Theoretical yield of the complex 2.9 g
4. % practical yield of the complex …… %
---
188
(D) Colorimetric Estimations
(Any Two)
Introduction :
Colorimetric estimation deals with the measurement of colour intensity. It is instrumental
method of quantitative analysis. The colour of a compound is due to absorption of light
waves of certain wavelengths. If a solution does not absorb light, it is transparent and
colourless. Colorimetry is connected with the determination of the concentration of coloured
substances by measurement of the relative absorption of light with respect to a known
concentration of the substance. When visible radiations of definite wavelength are passed
through coloured solution, then some of the radiations are absorbed by solution and
remaining are transmitted through solution. The extent to which absorption of light takes
place depends on the concentration of solution. This is the basic principle of colorimetry.
Colorimeter is used for measuring absorption in visible region i.e. colorimetric analysis is
concerned with visible region with wavelength between 400 nm to 800 nm. The
concentration of metals which gives rise to formation of coloured, soluble compound or
complex with reagent (ligand) can be determined by colorimetric methods. In these
estimations, a particular wavelength of light is passed through a solution of known and
unknown concentration under similar conditions. This particular wavelength is called λmax.
Thus, λmax is the wavelength at which the solution shows maximum absorbance.
The advantage of colorimetric analysis is that it requires much less time, it is more
accurate and highly sensitive method than usual chemical analysis. Colorimeter is useful for
the determination of constituents which are present in quantities less than 1 or 2 %. For the
laws of colorimetry, refer the colorimetric experiments of physical chemistry.
Experiment No. 1
Determination of Iron
Aim :
To determine the concentration of given unknown solution of Fe(III) using ammonium
thiocyanate at 540 mμ by colorimetric method.
Principle :
Fe(II) ion does not react with thiocyanate. But Fe(III) ion reacts with thiocyanate to give a
series of intensely blood-red coloured complexes. The formation of series of complexes
depends upon the concentration of thiocyanate ion. At very low concentration of thiocyanate
the predominant coloured species is [Fe(SCN)]2+.
Thus, Fe3+ + 6 SCN− → [Fe(SCN)6]3−
188
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Colorimetric Estimations
blood-red colour
This blood-red coloured solution gives maximum absorbance at 540 nm. The absorbance
is directly proportional to concentration, hence absorbance is measured at 540 nm and by
graphical method concentration of unknown is determined.
At 0.1 M thiocyanate concentration, the coloured species is mainly [Fe(SCN)2]+. At very
high concentration of thiocyanate the species is [Fe(SCN)6]3−.
In colorimetric determination, a large excess of thiocyanate should be used, since this
increases the intensity and also the stability of the colour. Strong acids (HCl or HNO3 with
concentration of 0.05 M to 0.5 M) should be present to suppress the hydrolysis of Fe(III)
ions as,
Fe3+ + 3H2O ≡ Fe(OH)3 + 3H+
which gives rise to formation of small amount of Fe(OH)3.
Generally, sulphuric acid is not used because sulphate ions have a tendency to form
complexes with Fe(III) ions.
The elements like zinc, cadmium, mercury, bismuth, molybdenum, uranium, titanium,
cobalt, nickel, copper and silver, interfere during the analysis. Stannous (Sn2+) and mercurous
2+
(Hg2 ) salts if present, should be converted into stannic (Sn4+) and mercuric (Hg2+) salts,
otherwise the colour is destroyed. Fluorides, oxalates, phosphates, arsenates and tartarates
interfere, since they form fairly stable complexes with Fe(III) ions. The influence of phosphates
and arsenates is reduced by the presence of comparatively high concentration of acid.
When large quantities of interfering substances are present then generally one of the
following procedure is used.
(i) Iron is separated by precipitation with a slight excess of ammonia solution and
dissolving the precipitate in dil. HCl.
(ii) The ferric thiocyanate is extracted three times either with pure ether or better, with a
mixture of amyl alcohol and pure ether in the ratio 5 : 2. The organic layer is used for
the colour comparison.
Chemicals :
Fe(III) unknown solution, conc. HCl and HNO3, 20% ammonium thiocyanate, H2O2,
distilled water.
Apparatus :
Colorimeter, volumetric flask (25 ml), 50 ml beaker (11), water bath, measuring cylinder,
burette.
Preparation :
(A) Preparation of standard solution (stock solution) of ferric ion (conc. 1 mg/ml) :
This known solution is prepared by using either of the following methods.
Method - 1 : Dissolve 7.022 g of A.R. ferric ammonium sulphate in 100 ml of distilled
water and 50 ml of 1 : 5 H2SO4. Then add dropwisely a dilute solution of KMnO4 (1%) using
189
burette until a slight pink colouration remains after stirring well. Dilute to 1 litre with distilled
water and shake well. Concentration of solution is 1 mg/ml Fe.
Method - 2 : Dissolve 8.64 g of A.R. ferric ammonium sulphate in little distilled water,
add 100 ml of A.R. conc. HCl and dilute to 1 litre with distilled water. Concentration of
solution is 1 mg/ml Fe.
A solution of Fe(III) with known concentration (0.1 mg/ml of Fe) is prepared by diluting
ten times the stock solution of 1 mg/ml concentration i.e. 10 ml is diluted to 100 ml.
(Distribute 8 to 12 ml of stock solution (conc. 1 mg/ml) in 100 ml volumetric flask as an
unknown solution.)
Procedure :
(A) Preparation of a set of known iron (III) solution (0.1 mg/ml) :
1. Take 1 to 5 numbered clean and dry 50 ml beakers.
2. Fill Fe(III) solution of known concentration (0.1 mg/ml) in burette.
(Do not forget to rinse the burette before filling of solution.)
3. Take 25 ml volumetric flask and add 1 ml solution of known concentration of iron (III)
(0.1 mg/ml) from the burette.
4. Add 1.5 ml 1 : 1 HCl solution to the above flask and then add 0.5 ml 3% H2O2 using
common burette.
5. Add 10 ml distilled water using measuring cylinder to this flask.
6. Add 2.5 ml 20% NH4SCN solution to the above flask using common burette. Dilute
the solution upto the mark using distilled water, shake well. Transfer the solution to
50 ml beaker numbered 1.
7. Similarly prepare the solution for set of 2 ml, 3 ml, 4 ml and 5 ml by repeating the
procedure from 3 to 6 and using same volumetric flask of 25 ml capacity and transfer
the solutions to 50 ml beakers numbered 2 to 5.
Important Note :
Record absorbance within 30 minutes after addition of thiocyanate solution.
(B) Preparation of a set of unknown iron (III) solution (1 mg/ml) :
1. Dilute the given unknown iron (III) solution to 100 ml with distilled water in a 100 ml
volumetric flask and shake well.
2. Take 6 to 10 numbered clean and dry 50 ml beakers.
3. Fill the diluted Fe(III) solution of unknown concentration in a burette.
4. Take 25 ml volumetric flask and add 1 ml diluted unknown Fe(III) solution from the
burette.
5. Add 1.5 ml 1 : 1 HCl solution to the above flask and then add 0.5 ml 3% H2O2 by
means of common burette.
6. Add 10 ml distilled water using measuring cylinder to this flask.
190
7. Add 2.5 ml 20% NH4SCN solution with the help of common burette and dilute the
solution upto the mark using distilled water, shake well. Transfer the solution to 50 ml
beaker numbered 6.
8. Similarly, prepare the solutions for set of 2 ml, 3 ml, 4 ml and 5 ml by repeating the
procedure from 4 to 6 and using same volumetric flask. Transfer the solutions to
50 ml beakers numbered 7 to 10.
(C) Preparation of a blank solution :
Take 25 ml clean and dry volumetric flask, add to it 1.5 ml of 1 : 1 A.R. HCl followed by
0.5 ml 3% H2O2 solution. Then add to it 2.5 ml 20% NH4SCN solution and dilute upto the
mark with distilled water, shake well. Transfer this solution to beaker number 11. Use this as a
blank solution.
(D) Measurement of absorbance :
1. To measure the O.D. use filter of wavelength 540 nm.
2. Set 100% transmittance or zero optical density for blank solution.
3. Then measure the optical density of each known and unknown solution.
Observation Table :
(i) Filter used = 540 nm.
(ii) Concentration of known solution = 0.1 mg/ml of Fe(III).
Beaker Known Fe(III) O.D. for Beaker Unknown Fe(III) O.D. for
No. solution (ml) known No. solution (ml) unknown
1 6
2 7
3 8
4 9
5 10
Graph :
Plot a graph of optical density (absorbance)
against ml of known and unknown Fe(III) solution
on the same graph paper. From the graph find out
O.D.
wn the concentration of the given unknown solution.

k no
Un
b a
ml of Fe(III) solution
Fig. 1
Calculation :
Calculate the concentration of unknown solution by graphical and by calculation method.
(i) By graphical method :
191
b
Amount of Fe(III) = × Concentration of known × 25
a
ml of known
= × 0.1 × 25 = ………. mg
ml of unknown
(ii) By calculation method :
Concentration of unknown O.D. of unknown
=
Concentration of known O.D. of known
O.D. of unknown
∴ Concentration of unknown = × Concentration of known × 25 = …. mg
O.D. of known
Using above formula calculate the concentration of unknown for five flasks and take their
mean.
Result Table :
By graph By calculations
Amount of Fe(III) in the .......... mg ………. mg
given solution
Experiment No. 2
Determination of Cobalt
Aim :
To determine the concentration of a given unknown cobalt solution using R-nitroso salt at
520 mμ by colorimetric method.
Principle :
The colorimetric determination of cobalt using R-nitroso salt is based on the principle
that when the hot solution of cobalt is treated with aqueous solution of R-nitroso salt in
presence of sodium acetate it produces red coloured solution due to formation of complex
[Co (R-nitroso salt)3]. R-nitroso salt (1-nitroso-2-naphthol 4, 6-disulphonate) is a bidentate
ligand. Cobalt has co-ordination number six. Therefore, three molecules of reagent combine
with ion forming red coloured cobalt complex having octahedral structure.
Co
ONO ONO
OH o OH
60 C
3
3+
Co
SO3Na SO3Na
SO3Na SO3Na
3
Along with cobalt other metals like Cu, Fe, Cr, Ni also form a complex with R-nitroso salt
but complexes are decomposed by addition of 1 : 2 HNO3 except with cobalt complex.
192
Dilution is done with distilled water. The intensity of colour of solution depends upon
concentration of cobalt. The absorbance (O.D.) of known and unknown solutions are
measured by colorimeter. By comparing the absorbance (O.D.) of known and unknown
graphically the concentration of unknown cobalt solution is determined.
Apparatus :
Colorimeter, 1 to 11 numbered 50 ml beakers, 25 ml volumetric flask, burettes etc.
Chemicals :
(i) Known cobalt solution = 0.1 mg/ml of cobalt.
(ii) Unknown cobalt solution = Given in 100 ml volumetric flask (1 mg/ml. Give 8 to
12 ml).
(iii) 1% aqueous R-nitroso salt solution (freshly prepared).
(iv) 50% sodium acetate solution.
(v) 1 : 2 HNO3 solution.
Procedure :
(A) Preparation of a set for known cobalt solution :
1. Take 1 to 5 numbered clean 50 ml beakers.
2. Fill the solution of known cobalt concentration (0.1 mg/ml) in burette.
3. Add 1, 2, 3, 4 and 5 ml solution of known concentration of cobalt (0.1 mg/ml) from
burette to beakers numbered 1 to 5.
4. Add 2.5 ml of 50% sodium acetate solution and 2.5 ml 1% R-nitroso salt solution.
5. Heat these beakers on a boiling water bath for 5 minutes. Cool and add 2.5 ml
1 : 2 HNO3 using burette to each of these beakers.
6. Again heat these beakers on boiling water bath for 5 minutes. Red coloured complex
is formed. Cool the beakers.
7. Transfer the solution from beaker to 25 ml volumetric flask. Wash the beaker with few
ml distilled water and transfer to volumetric flask and finally dilute it with distilled
water upto the mark.
8. Transfer the solutions again to 50 ml beakers marked 1 to 5.
(B) Preparation of a set for unknown cobalt solution :
1. Dilute the given unknown solution of cobalt with distilled water in 100 ml volumetric
flask (supplied) and shake well and fill it in burette.
2. Take 6 to 10 numbered beakers.
3. Add with the help of burette 1 ml, 2 ml, 3 ml, 4 ml and 5 ml of diluted unknown
cobalt solution in the respective beakers.
4. Add 2.5 ml of 50% sodium acetate solution and 2.5 ml 1% R-nitroso salt solution.
5. Heat these beakers on a boiling water bath for 5 minutes. Cool and add 2.5 ml 1 : 2
HNO3 using burette to each of these beakers.
193
6. Again heat these beakers on boiling water bath for 5 minutes. Red coloured complex
is formed. Cool the beakers.
7. Transfer the solution from beaker to 25 ml volumetric flask. Wash the beaker with few
ml distilled water and transfer to volumetric flask and finally dilute it with distilled
water upto the mark.
8. Transfer the solutions again to the 50 ml beakers numbered 6 to 10.
(C) Preparation of blank solution :
In a 50 ml beaker (No. 11) take 2.5 ml of 50% sodium acetate solution + 2.5 ml of 1%
R-nitroso salt solution. Heat the beakers on water bath for 5 minutes. Cool and add 2.5 ml
1 : 2 HNO3 solution, again heat for 5 minutes. Cool and transfer the solution from beaker to
25 ml volumetric flask. Dilute to 25 ml with distilled water. Transfer this solution again to
50 ml beaker numbered 11. Use this solution as a blank solution.
(D) Measurement of absorbance :
1. To measure O.D. of [Co(R-nitroso salt)3] complex solution, use 520 nm filter.
3. Then measure the optical density of each known and each unknown solution.
Observation Table :
(i) Concentration of known cobalt solution = 0.1 mg/ml.
(ii) Filter used = 520 nm.
Beaker Known Co O.D. for Beaker Unknown Co O.D. for
1 6
2 7
3 8
4 9
5 10
Graph :
against ml of known and unknown cobalt solution
on the same graph paper. From the graph find out
the concentration of the given unknown solution.
O.D.
n
now
Unk
b a
ml of cobalt solution
Fig. 1
194
Calculations :
b
Amount of Co = × Concentration of known × 25
a
ml of known
= × 0.1 × 25 = ………. mg
ml of unknown
=
O.D. of unknown
O.D. of known
Using above formula calculate the concentration of unknown for five flasks and take the
mean.
Result Table :
Amount of cobalt in the .......... mg ………. mg
given solution
Experiment No. 3
Determination of Titanium
Aim :
To determine the concentration of a given unknown titanium solution using H2O2 by
colorimetric method.
Principle :
The determination of titanium is based on the principle that when an acidic solution of
Ti(IV) is treated with H2O2 it produces yellow coloured complex. The intensity of yellow colour
is proportional to the amount of titanium (IV) present in the solution. The reaction occurs in
strongly acid solution with excess H2O2 as,
Ti(SO4)2 + H2O2 ≡ H2[TiO2(SO4)2]
Colourless Yellow
This yellow coloured solution gives maximum absorbance at 440 nm. Dilution of solution
is done with 2N H2SO4 only. The absorbance on colorimeter is measured for known and
unknown solutions. The concentration of unknown solution is determined by graphical
method.
Chemicals :
(i) Known titanium solution = 1 mg/ml of TiO2.
195
(ii) Unknown titanium solution − (Given in 100 ml volumetric flask) 5 mg/ml TiO2
(Give 13 to 18 ml).
(iii) 3% H2O2.
(iv) 2N H2SO4.
Apparatus :
Colorimeter, 25 ml volumetric flask, 50 ml beakers numbered from 1 to 11.
Procedure :
(A) Preparation of set for known Ti solution :
1. Take 1 to 5 numbered clean and dry beakers.
2. Fill Ti solution of known concentration in burette.
3. Take 25 ml volumetric flask and add 1 ml solution of known concentration of
Ti (0.1 mg/ml) from the burette.
4. Add 1.5 ml of 3% H2O2 solution by a burette to the above volumetric flask.
5. Dilute the solution in flask with 2N H2SO4 upto the mark, shake well and transfer the
solution into 50 ml beaker.
procedure from 3 to 5 and using same volumetric flask.
7. Transfer the solutions to 50 ml beakers numbered 2 to 5.
(B) Preparation of set for unknown Ti solution :
1. Dilute the given unknown solution of titanium with 2 N H2SO4 in a 100 ml volumetric
flask (supplied) and shake well.
2. Take 6 to 10 numbered 50 ml beakers.
3. Fill the diluted titanium solution of unknown concentration in burette.
4. Take 25 ml volumetric flask and add 1 ml diluted unknown Ti solution from the
burette.
5. Add 1.5 ml of 3% H2O2 solution by a burette to the above volumetric flask.
6. Dilute the solution in flask with 2 N H2SO4 upto the mark, shake well and transfer the
solution into 50 ml beaker numbered 6.
procedure from 4 to 6 and using same volumetric flask.
8. Transfer the solutions to 50 ml beakers numbered 7 to 10.
(C) Preparation of a blank solution :
196
Take 25 ml volumetric flask and add to it 1.5 ml 3% H2O2. Dilute it upto the mark with 2N
H2SO4. Shake well and transfer the solution to beaker numbered 11. Use this solution as a
blank solution.
(D) Measurement of optical density :
1. To measure O.D. of Ti(IV) solution use blue filter (440 nm).
3. Measure the O.D. of each known and unknown solution.
Observation Table :
(i) Concentration of known titanium solution : 1 mg/ml of TiO2.
(ii) Filter used = 440 nm.
Beaker Known Ti O.D. for Beaker Unknown Ti O.D. for

1 6
2 7
3 8
4 9
5 10
Graph :
against ml of known and unknown titanium
O.D.
ow
n solution on the same graph paper. From the graph
kn
Un
find out the concentration of the given unknown
b a solution.
ml of Ti solution
Fig. 1
Calculations :
Calculate the concentration of unknown solution by graphical and by calculation method.
b
Amount of Ti = × Concentration of known × 25
a
ml of known
= × 0.1 × 25 = ………. mg
ml of unknown
197

=
O.D. of unknown
O.D. of known
Using above formula calculate the concentration of unknown for five flasks and take the
mean.
Result Table :
Amount of titanium in the .......... mg ………. mg
given solution
VIVA VOCE
1. What are the regions of electromagnetic spectrum ?
2. Explain Radiant energy, Radiant power, Transmittance, Absorbance, Absorptivity and
Molar absorptivity.
3. Define : Lambert’s law, Beer’s law, Lambert-Beer’s law.
4. How Lambert-Beer’s law is varied ?
5. Give the construction and working of a simple colorimeter.
6. Describe essential parts of a colorimeter.
7. How Lambert-Beer’s law is used in quantitative analysis ?
8. What are the various detectors used in visible region ? Describe them.
9. Explain the differences between :
(a) Colorimeter and Spectrophotometer. (b) Absorbance and Absorptivity.
10. Describe the various applications of colorimetry.
11. What are light filters ? Explain the absorption filters. Comment on the choice of a
suitable filter.
12. What are the disadvantages of filter photometers ? How are they removed ?
13. What are photo-electric cells ?
14. Give reasons for deviation from Lambert-Beer’s law.
15. What are the advantages of colorimetric analysis ?
16. What is the relationship between absorbance and percentage transmission ?
198
17. What do you understand by λmax ?

18. What are the units used to describe the wavelength ?
19. What are the units of absorptivity and molar absorptivity ?
20. Explain the concept of additivity of absorbance.
21. What do you mean by complementary colour ?
22. What is monochromator ?
23. What are the series of complexes formed by Fe+3 ion with SCN− ion ?
24. Why a strong acid should be present in the colorimetric estimation of Fe+3 ?
25. What is the filter used in the colorimetric estimation of Fe+3 with SCN− ion ?
26. What is the colour produced by Fe+3 ion with SCN− ion ? Why does the colour fade
away after sometime ?
27. How will you determine the concentration of unknown solution of Fe+3 by graphical
method in colorimetric estimation ?
28. Which colour is produced by cobalt solution with aqueous solution of R-nitroso salt.
29. Draw the octahedral structure of cobalt complex with R-nitroso salt.
30. What is the use of 1 : 2 HNO3 in this estimation ?
31. What is the concentration of unknown cobalt solution ? Which filter we have used for
estimation of cobalt ?
32. How is the amount of unknown cobalt calculated by calculation method ?
33. Which colour is produced when titanium reacts with H2O2 ?
34. What is the concentration of the standard (known) titanium solution ? Which filter
you have used for estimation of titanium ?
35. How is amount of unknown titanium calculated by calculation method ?
36. Write the structure of complex formed by R-nitroso salt with cobalt.
---
199
(E) Column Chromatograpy
(Three Mixtures)
[One Mixture should be Colourless]
Separation of Binary Mixture of Cations by Column Chromatography
Introduction :
In all chromatographic methods there are two phases, one stationary and other mobile.
Separation depends upon the relative movements of these two phases. Chromatography
methods may be classified according to the nature of the stationary phase, which may be
solid or liquid. If stationary phase is solid, the method is known as adsorption
chromatography. If the stationary phase is liquid, the method is known as partition
chromatography. Since in each case the mobile phase may be either liquid or a gas. There
are in all four types of chromatographic systems.
Chromatography
Partition Adsorption
Liquid Stationary Phase Solid Stationary Phase
1. 2. 3. 4.
Liquid mobile phase Gaseous mobile phase Liquid mobile phase Gaseous mobile phase
Liquid-liquid Gas-liquid Liquid-solid Gas-solid
Chromatography Chromatography Chromatography Chromatography
e.g. Paper chromatography e.g. TLC, Ion exchange
Column Chromatography is one of the best methods used for separation of components
of mixtures based on the partition. This method uses suitable substance as a stationary phase
or support. Although this method is time consuming, we can get the constituents in highly
pure form.
The separation of components from a given mixture (inorganic cations) by using cellulose
column is mostly partition chromatography. In this technique, we use two solvents (liquid
phase) such as acetone and HCl − H2O. The separation of mixture is done between the two
phases.
(i) Aqueous phase (Stationary phase)
(ii) Organic solvents - acetone phase (Mobile phase)
In partition chromatography one of the two solvents is held on a column as a stationary
phase. Generally silica gel is used for separation of organic mixtures, while powder is used for
separation of inorganic mixtures.
The method depends on the separation of components of a mixture between water held
on the column and non-polar solvents (or less polar than water) percolating down the
column. The more hydrophilic components having more affinity for water are held at the top
200
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Column Chromatography
of the column, while more hydrophobic components being soluble in less polar medium
move down the column and are eluted (removed) first.
In the present syllabus we have to separate following binary mixtures by column
chromatography. Out of these at least one colourless mixture is to be separated.
(a) Fe+3 + Al3+
(b) Co2+ + Ni+2
(c) Cu+2 + Ni+2
(d) Cu+2 + Al+3
(e) Zn2+ + Al3+
(f) Zn2+ + Mg2+
Sample
Cotton or
Glass wool
Adsorbent
Glass column
or
Burette
Cotton or
Glass wool
Eluate
Fig. 1: Typical chromatographic column

Metal ion reacts with HCl and forms chloride complexes and such complex moves along
with the solvent acetone first, The metal ion which does not move with acetone is collected
afterwards by using 1 M HCl.
It is found by experiment that Fe+3, Co+2, Cu2+ and Zn2+ move with acetone and will be
collected first. While Al+3, Ni+2 and Mg+2 are eluted by using 1 M HCl as a second fraction.
201
We know that Rf values of Fe+3, Co+2, Cu+2, Zn2+ are higher than those of Al+3, Ni+2, Mg+2.
Therefore, from the binary mixture we shall first get Fe+3, Co+2, Cu+2 and Zn+2 components.
Experiment No. 1
Aim :
From the given mixture separate the cations by column chromatography using cellulose.
Apparatus :
Glass column (30 cm long and 3 cm in diameter), 25 ml glass burette with glass stopper,
100 ml conical flasks, glass wool, cotton plug, filter paper etc.
Chemicals :
(i) A mixture of two cations (given in test tube).
(ii) Organic solvent, 2% HCl - Acetone (2 ml pure conc. HCl and 98 ml distilled acetone)
(iii) 1 M HCl (second solvent) - 20 to 30 ml
(iv) Cellulose powder - 4 g
Principle :
In column chromatography, the stationary phase is a finely divided solids like cellulose,
silica or alumina. A column is prepared by carefully packing this solid material in a long glass
column or a burette. A typical column is shown in Fig. 1 of previous experiment.
A sample solution is placed in a small volume at the top of the column. The components
of the sample are adsorbed over the column material. The adsorbed components are eluted
with a suitable solvent (mobile phase) which is called as eluant. The less strongly adsorbed
components are eluated first and more strongly adsorbed components are eluated later.
Thus, separation is effected. The process is called elution and the liquid collected after
eluation is called eluate. The eluate is further analysed qualitatively.
Procedure :
[A] Preparation of Cellulose Column :
1. Take 25 ml glass burette and clean with little amount of acetone and dry it before
use.
2. Take 4 g of cellulose powder in 100 ml beaker and add to it 25 ml acetone to form a
slurry. Stir with glass rod.
3. Place a small glass wool or cotton pad at the bottom of the burette with the help of
long glass rod.
4. Close the tap and clamp the burette in a vertical position, transfer the slurry to the
burette.
202
5. Cellulose will settle on the glass wool (cotton).

6. Prepare a uniform column of 15 - 20 cm in length, without any air gap.
7. Cover the column with little cotton plug.
8. Open the tap of the burette and allow a little solvent to flow and close the tap again.
9. Observe that there will be some solvent 2 cm above the top level of cellulose.
Precaution : The column should not become dry.
10. Now use this column for separation of cations.
[B] Loading of the Mixture :
1. Open the tap of the burette and allow the solvent to flow down.
2. Immediately pour the given sample (3 ml) solution to the column, and get a uniform
layer. Rinse the test tube with 2% HCl acetone mixture.
3. Add 5 - 10 ml solvent and keep a clean conical flask below the burette to collect the
first component of the mixture.
4. The rate of flow of the solvent should be very slow.
5. As the solvent passes through, various components will pass through with different
rates and after some time separate out into two coloured bands or zones, if both
cations are coloured.
6. This process is known as development of the column.
[C] Separation of Bands :
1. The first component is collected in a conical flask using 2% HCl. Acetone solvent, till
the first band disappears completely. It will require 20 ml of solvent.
2. The second component is collected in another dry conical flask (100 ml) using 1M
HCl as second solvent, till the second component is completely removed from the
column, it will require about 20 ml 1 M HCl.
[Hint : (i) For Fe+3/Al3+ mixture only one band is observed (ii) For Co+2/ Ni2+ and
Cu+2 mixture two bands are seen.]
3. For Zn2+ and Mg2+ mixture, no bands are observed.
However, sometimes one cation gives two different coloured bands due to formation of
two different complexes e.g. CoCl3 ⋅ 2H2O is pink and CoCl3 ⋅ H2O is blue. So formation of
colour band cannot be taken as a sure test for separation.
[D] Concentration of the Components :
After separation of two components, concentrate the first fraction by heating on steam
bath, so the acetone will be evaporated off and we get concentrated solution of
corresponding metal chlorides.
Concentrate the second fraction by heating on a wire gauze till the final volume becomes
10 to 15 ml.
203
(Note : Student should show the two separated and concentrated components to the
examiner.)
[E] Identification of Cations :
After separation and concentration of two cations, confirm them by performing following
spot tests.
[I] First fraction : Fe+3, Co+3, Cu2+, Zn2+
(a) Tests for Fe+3 :
1. Take 2 drops of the solution in a test tube and 1 - 2 drops of distilled HCl + 1 ml 3%
H2O2 + 1 - 2 drops of KCNS or NH4CNS (1%) ⎯→ Red colour, therefore Fe+3 is
present and confirmed.
2. Take 2 drops of solution in a test tube + 2 drops of K4[Fe(CN)6] ⎯→ Blue colour,
therefore Fe+3 is present and confirmed.
3. Place a drop of solution on a filter paper, add a drop of phenanthroline reagent
(0.1 % aq.) ⎯→ Red colour, therefore Fe+3 is present and confirmed.
(b) Tests for Co+2 :
1. Take 2 drops of the solution in a test tube + 2 drops of α nitroso [β-naphthol (1% in
50 % acetic acid)] ⎯→ Red brown colour, therefore Co+2 is present and confirmed.
2. 1 drop of the solution on a test paper + 1 drop of sodium acetate (50% aq.)
+ 1 drop of R-nitroso salt (1% aq.) ⎯→ Red spot, therefore Co+2 is present and
confirmed.
3. Take 1 drop of the solution in a test tube. Add few drops of acetone + 2 drops of
acetone + 2 drops of NH4CNS ⎯→ Blue or bluish green colour, therefore Co+2 is
4. Place a drop of the solution on a test paper. Add two drops of rubeanic acid and one
drop of benzidine. Expose to ammonia vapours ⎯→ Orange yellow colour, therefore
Co+2 present and confirmed.
5. Place a drop of the solution on a filter paper. Add five drops of saturated solution of
NH4CNS ⎯→ A green to blue colour which changes to pink on dilution, therefore
Co+2 present and confirmed.
(c) Tests for Cu+2 :
1. 2 drops of solution in a test tube + 5 drops of dilute acetic acid + 4 drops of
K4[Fe(CN)6] ⎯→ A chocolate red precipitate, therefore Cu+2 present and confirmed.
2. Place a drop of the solution on a test paper. Add few drops of alcoholic solution of
rubeanic acid and expose to ammonia vapours ⎯→ Olive green colour, therefore
Cu+2 present and confirmed.
3. Place a drop of the solution on a test paper, add one drop of rubeanic acid and one
drop of benzidine. Expose to ammonia vapours ⎯→ Grey green colour, therefore
Cu+2 present and confirmed.
204
4. Take a drop of the solution in a test tube, add 2 drops of cupron and a drop of
NH4OH ⎯→ Green colour, therefore Cu+2 present and confirmed.
(d) Tests for Zn :
1. Take two drops of solution. Add few drops of acetic acid and pass H2S ⎯→ White
precipitate. Then Zn is present.
2. Two drops of solution + Few drops of acetic acid + 4 drops of K3[Fe(CN)6] + Few
drops of diphenylamine in acetic acid ⎯→ Green precipitate. Zn is present and
confirmed.
3. Few drops of solution + Few drops of dil. HNO3 + Few drops of Co(NO3)2 solution.
Heat to dryness ⎯→ A green mass is obtained. Then zinc is present and confirmed.
[II] Second Fraction : Al+3, Ni2+, Mg2+
(a) Tests for Al+3 :
1. 1 drop of the solution on a test paper. Dry the spot under I.R. lamp + 1 drop of
alizarin reagent (1% aq.) and expose to ammonia ⎯→ Violet colour around the spot,
therefore Al3+ present and confirmed.
2. 2 ml of the solution in a test tube + 1 ml dil. HCl + 4 ml 1:1 Ammonia (solution
should become alkaline). Heat to boiling ⎯→ White gelatinous precipitate of Al(OH)3
is formed, therefore Al3+ present and confirmed.
(b) Tests for Ni2+ :
1. 1 drop of the solution on a test paper + 1 drop of dimethyl glyoxime and exposed to
ammonia ⎯→ Red colour, therefore Ni+2 present and confirmed.
2. 1 drop of the solution on a test paper + 1 drop of saturated solution of rubeanic acid
in ethanol and expose to ammonia ⎯→ Violet colour, therefore Ni+2 present and
confirmed.
3. Take 2-3 drops of the solution in a test tube. Add 2 drops of α-nitroso β-naphthol
solution ⎯→ Brown precipitate soluble in dil. HCl, therefore Ni+2 present and
confirmed.
4. Place a drop of the solution on a test paper. Add a drop of rubeanic acid and a drop
of benzidine. Expose to ammonia vapours ⎯→ Blue coloured spot, therefore Ni+2
(c) Tests for Mg2+ :
1. Two drops of solution on watch glass + 2 drops of titan yellow solution + 2 drops of
dil. NaOH solution ⎯→ a rose red colour or precipitate ⎯→ Then Mg2+ is present.
2. Two drops of solution + Hypoiodite reagent ⎯→ A reddish brown precipitate
confirms the presence of Mg2+.
205
[Hypoiodite reagent : NaOH solution + Equal amount of KI solution + Iodine solution

till the solution becomes just yellow].
3. 2 drops of solution + 3 drops of NH4OH solution + 2 drops of Na2HPO4 solution →
white ppt. confirms the presence of Mg2+.
Result Table :
Fractions collected Amount of fraction Cation present
concentrated
(i) First fraction ........ ml
(ii) Second fraction ........ ml
VIVA VOCE
1. What do you mean by chromatography ?
2. What are different types of chromatographic methods ?
3. What is column chromatography ? What is its principle ?
4. What is the principle behind separation of a mixture by column chromatography ?
5. What is stationary phase and mobile phase in column chromatography ?
6. What is the role of cotton plug in column chromatography ?
7. Give one confirmatory test for Fe+3, Co+2, Cu+2, Zn2+ and Al3+, Ni2+, Mg2+.
8. What is meant by elution ? What are the different solvents used for elution ?
9. What is meant by eluate ?
10. What is meant by eluant ?
11. What do you mean by column chromatography ?
12. What is Rf value ?
---
206
(E) Flame Photometry Analysis
(Any Three Experiments)
Introduction :
Flame photometry is the instrumental method of analysis and used for analysis of limited
elements mainly Li+, Na+, K+ and Ca2+. Ca2+ can be analysed by gravimetric or volumetric
methods of analysis, but there is no any other suitable method of analysis for Li+, Na+ and K+.
Na+, K+ and Ca2+ from soil, drinking water, from food samples, from blood, from fertilizers,
etc. is analysed by this method. This method of estimation is highly sensitive and even can be
applied at 1 ppm level accurately.
The typical flame photometer consists of sample inlet system (nebulizer), burner (and fuel
gas), detector and read out device.
Flame Photodetector
Filter
Amplifier
and
Readout
Lens
Burner
Oxidant
Fuel gas
Mixing chamber
Nebuliser Analyte
solution
To drain
Fig. 1: Flame photometer
+ + + 2+
Sample of Li , Na , K and Ca ions in solution form is used for analysis. The solid sample
is disintegrated by suitable method such as acid digestion, or microwave digestion diluted to
suitable volume and used for analysis. The concentration of these ions in analyte solution
should be less than 100 ppm and typically in the range from 1 to 25 ppm. All reagents used
for flame photometric analysis should be free off these ions or alternatively ‘atomic
spectroscopic grade’ reagents must be utilized. By flame photometry one element can be
detected in presence of another without interference.
In a typical flame photometric analysis, a solution containing analyte is aspirated into the
burner in the form of fine mist. This process is called nebulisation. In the flame, the solvent
evaporates due to heating, leaving behind finely divided solid particles of analyte salt. In the
207
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Flame Photometry Analysis
flame, due to high temperature, salt particles are converted to gaseous state molecules.
Then, gaseous state molecules auto decompose to atoms by redox reaction.
Δ 1
e.g. NaCl(g) ⎯→ Na(g) + Cl2(g)
2
1
Na+ + 1e− → Na(g) and Cl− → Cl + e−
2 2 (g)
The atoms in flame absorb heat energy and are excited from ground state to excited
state (3s orbital to 3p orbital). Excited state of atom is highly unstable. Thus, the excited
atoms return to a ground state with emission of energy. This energy is emitted in the form of
electromagnetic radiations of characteristic wavelength. Emitted wavelength is a
characteristic of the element. The intensity of the emitted radiation from the flame is then
determined. Intensity of emitted radiations can be related to the concentration of the analyte
ions in the solution. At sufficiently low concentration, intensity of emitted radiation is directly
proportional to the concentration of Na+ ions in the analyte solution.
Experiment No. 1
Estimation of Sodium (Na)
Aim:
To determine the concentration of given unknown samples of Sodium (Na) by flame
photometry using calibration curve method.
Principle:
In a typical flame photometric analysis of Na+, a solution containing Na+ is aspirated into
the burner and dispersed into the flame as a fine spray. This process is called nebulisation. In
the flame, the solvent evaporates first, leaving finely divided solid particles of NaCl which
move to hottest region of the flame where gaseous Na atoms and Na+ ions are produced.
The atoms are excited from ground state to excited state (3s orbital to
3p orbital) by absorbing energy from the flame. Excited state of atom is highly unstable.
Thus, the excited atoms return to a ground state with the emission of energy. This energy is
emitted in the form of electromagnetic radiations of characteristic wavelength i.e. 586 nm.
This wavelength is a characteristic of the Na. The intensity of the emitted radiation from the
flame is then determined. Intensity of emitted radiations can be related to the concentration
of the Na+ ions in the solution. At sufficiently low concentration, intensity of emitted
radiation is directly proportional to the concentration of Na+ ions in the analyte solution.
Chemicals:
A. R. grade Sodium chloride (NaCl), Distilled water.
Apparatus:
Burette, Graduated pipette, Beakers (250 ml, 50 ml – 6 beakers), volumetric flask
(100 ml, 25 ml).
208
(Note: All solutions must be prepared in glass distilled water. Before use all glass apparatus
must be rinsed with distilled water.)
Procedure:
Part A: Preparation of standard solution (stock solution) of Na+ (100 ppm):
Prepare Na+ stock standard solution of 100 ppm 250 ml from A.R. grade NaCl. 100 ppm
Na+ means 100 mg Na+ ions in 1000 ml solution. Thus, 250 ml solution will require
25 mg Na+ i.e. 0.025 g Na+ (1 ppm = 1 mg Na+/ltr.).
58.5 g NaCl = 23 g Na+.
Therefore, ‘X’ g NaCl = 0.025 g Na+
0.025 × 58.5
Therefore, X = = 0.06358 g NaCl
23
Thus, weigh 0.064 g i.e. 64 mg NaCl and prepare 250 ml solution in volumetric flask with
distilled water.
Part B: Preparation of series working standard solutions and unknown samples of Na+:
Prepare series working standard solutions of 4, 8, 12, 16 and 20 ppm by using following
procedure.
1. Take 1 to 5 numbered clean and dry 25 ml volumetric flasks.
2. Fill Na+ stock solution of known concentration in burette (100 ppm).
3. Take out 1, 2, 3, 4 and 5 ml standard of 100 ppm by burette in 1 to 5 numbered 25 ml
volumetric flasks. Dilute these solutions upto the mark with distilled water. Transfer
4. Prepare two unknown samples of Na+, the concentration of these samples should be
less than 20 ppm. These samples are used for flame photometric analysis to find out
the amount of Na+.
Part C: Measurement of intensity of flame by using Flame Photometer:
1. Switch ON the power of apparatus. Ignite the burner. Set sodium filter. Properly
adjust the flame of the flame photometer. For this purpose follow the instructions
given in the manual.
2. Aspirate distilled water in flame and set zero using respective ‘setting knob’.
3. Now aspirate 20 ppm standard solution of Na+ for calibration process. For this
standard solution adjust intensity such as 20 or 40 or 60 or 80. Use standardization
knob for this purpose.
209
4. Record the intensity of flame for all Na+ standards and unknown sample solutions
one by one. Aspirate distilled water after every reading. Tabulate the recorded
observations.
Observation Table:
Solution Conc. of Na+ Intensity of flame

in ppm for Na+ solutions
Standard-1 4
Standard-2 8
Standard-3 12
Standard-4 16
Standard-5 20
Sample-1 Unknown
Sample-2 Unknown
Graph:
Plot a graph of concentration of Na+ against flame intensity.
80
2
70 R = 0.987
60
Intensity of flame
50
40
30
20 ppm of
sample
10
0
0 4 8 12 16 20 24 28
Concentration of Na(I), ppm
Fig. 1
Calculations:
By using calibration curve method: Use calibration curve method for calculation of
concentration of sample. Plot a graph of concentration of Na+ (x-axis) against flame intensity
(y-axis). Place perpendicular from the intensity axis to the plot and then extend to
concentration axis. From the point of intercept obtain the concentration of Na+ in the given
solution.
210
Result Table :
Sample-1 Sample-2
Amount of Na+ in the given sample of water
----------- ppm --------------- ppm
Experiment No. 2
Aim:
To determine the concentration of given unknown samples of Sodium (Na) by flame
photometry using least square (regression analysis) method.
Principle, Chemicals, Procedure is same as that of Experiment No. 1 (Flame Photometer
Analysis of sodium), only method of calculation is different.
Perform the same procedure as per given in the Experiment No. 1.
Observation Table:
Solution Conc. of Na+ in Flame intensity
ppm (xi) (yi)
Standard-1 x1 = 4 y1 =
Sample-1 Unknown
Sample-2 Unknown
Calculation by least square method: There are two assumptions in the least-square
method.
1. The linear relationship actually exists between measured response (y-axis value) and
standard analyte concentration. The mathematical relationship describing this
assumption is called as regression model which is given by the following equation:
y = ax + b, where ‘a’ is slope and ‘b’ is intercept to y-axis.
2. Any deviation from the individual point from the straight line arises from the error in
the measurement i.e. we assure that there is no error in the x value of the point. Both
these assumptions are appropriate for many analytical methods. But whenever there
is significant uncertainty in the x data, then basic least-squares method do not give
rise straight line.
The calculations are as follows:
The slope of line is given by the following equation:
211
n ∑ xi yi − ∑ xi ∑ yi
a = 2
n ∑ xi − (∑ xi)2
where, n = 5 (number of data points),
xi = value of individual concentration in ppm (x1 to x5)
yi = value of individual flame intensities (y1 to y5)
∑ xi = (4 + 8 + 12 + 16 + 20),
∑ yi = sum of flame intensities for five readings of standards
2
∑ xi = 42 + 82 + 122 + 162 + 202,
2
∑ yi = make a square of each flame intensity and then take sum.
(∑ xi)2 = (4 + 8 + 12 + 16 + 20)2,
n ∑ xi yi = 5[(x1 y1) + (x2 y2) + (x3 y3) + (x4 y4) + (x5 y5)]
b = −y + a−x
where, −x = (4 + 8 + 12 + 16 + 20)
5
− (sum of flame intensities of five standards)

y =
5
From slope. concentration of sample is calculated.
and, y = flame intensity of sample, x = concentration of sample, ppm (to be calculated).
Regression of the line can be calculated by the following equation:
r =
2 2
[n ∑ xi − (∑ xi)2] [n ∑ yi − (∑ yi)2]
r is called as regression of line. This value indicates the linearity of line. For 100% linearity
of five standard readings, the value of r is ±1. Practically this value is expressed as r2 and is
1 for 100% linearity. Experimentally this value should be greater than 0.95. If this value is less
than 0.95 then we can say that there exists large error in the determination of flame
intensities. Such readings cannot be accepted for calculations.
Result Table :
Sample-1 Sample-2
Amount of Na+ in the given sample of water
----------- ppm ---------- ppm
Experiment No. 3
Estimation of Potassium
Aim:
212
To determine the concentration of given unknown samples of Potassium (K) by flame

photometry using calibration curve method.
Principle :
In a typical flame photometric analysis of K+, a solution containing K+ is aspirated into the
burner and dispersed into the flame as a fine spray. This process is called nebulisation. In the
flame, the solvent evaporates first, leaving finely divided solid particles of KCl which move to
hottest region of the flame where gaseous K atoms and K+ ions are produced. The atoms are
excited from ground state to excited state (3s orbital to 3p orbital) by absorbing energy from
the flame. Excited state of atom is highly unstable. Thus, the excited atoms return to a
ground state with the emission of energy. This energy is emitted in the form of
electromagnetic radiations of characteristic wavelength i.e. 586 nm. This wavelength is a
characteristic of K. The intensity of the emitted radiation from the flame is then determined.
Intensity of emitted radiations can be related to the concentration of K+ ions in the solution.
At sufficiently low concentration, intensity of emitted radiation is directly proportional to the
concentration of K+ ions in the analyte solution.
Chemicals:
A.R. Grade Potassium chloride (KCl), Distilled water.
Apparatus:
Burette, Graduated pipette, Beakers (250 ml, 50 ml – 6 beakers), Volumetric flask (100 ml,
25 ml).
(Note: All solutions must be prepared in glass distilled water. Before use all glass apparatus
must be rinsed with distilled water.)
Procedure:
Part A: Preparation of standard solution (stock solution) of Na+ (100 ppm):
Prepare K+ stock standard solution of 100 ppm 250 ml from A.R. grade KCl. 100 ppm
K means 100 mg K+ ions in 1000 ml solution. Thus, 250 ml solution will require 25 mg K+
+
i.e. 0.025 g K+ (1 ppm = 1 mg Na+/ltr.).

73.58 g KCl = 38.08 g K+.
Therefore, ‘x’ g KCl = 0.025 g K+
0.025 × 73.58
Therefore, x = = 0.0489 g KCl
38.08
Thus, weigh 0.0489 g i.e. 49 mg KCl and prepare 250 ml solution in the volumetric flask
with distilled water.
Part B: Preparation of series of working standard solutions and unknown samples
of K+:
Prepare series working standard solutions of 4, 8, 12, 16 and 20 ppm using following
procedure.
5. Take 1 to 5 numbered clean and dry 25 ml volumetric flasks.
6. Fill K+ stock solution of known concentration in burette (100 ppm).
213
7. Take out 1, 2, 3, 4 and 5 ml standard of 100 ppm by burette in 1 to 5 numbered 25 ml

volumetric flasks. Dilute these solutions upto the mark with distilled water. Transfer
8. Prepared two unknown samples of K+, the concentration of these samples should be
less than 20 ppm. These samples are used for the flame photometric analysis to find
out amount of K+.
Part C: Measurement of intensity of flame by using Flame Photometer:
1. Switch ON the power of apparatus. Ignite the burner. Set sodium filter. Properly
adjust the flame of the flame photometer. For this purpose follow the instructions
given in the manual.
2. Aspirate distilled water in the flame and set zero using respective ‘setting knob’.
3. Now aspirate 20 ppm standard solution of K+ for calibration process. For this
standard solution adjust intensity such as 20 or 40 or 60 or 80. Use standardization
knob for this purpose.
4. Record the intensity of flame for all K+ standards and unknown sample solutions one
by one. Aspirate distilled water after every reading. Tabulate the recorded
observations.
Observation Table:
Solution Conc. of K+ in Intensity of flame
ppm for K+ solutions
Standard-1 4
Standard-2 8
Standard-3 12
Standard-4 16
Standard-5 20
Sample-1 Unknown
Sample-2 Unknown
Graph:
Plot a graph of concentration of K+ against flame intensity.
80
2
70 R = 0.987
60
Intensity of flame
50
40
30
20 ppm of
sample
10
0
0 4 8 12 16 20 24 28
Concentration of K(I), ppm
214
Fig. 1
Calculations:
By using calibration curve method: Use calibration curve method for calculation of
concentration of sample. Plot a graph concentration of K+ (x-axis) against flame intensity (y-
axis). Place perpendicular from the intensity axis to the plot and then extend to concentration
axis. From point of intercept obtain the concentration of K+ in the given solution.
Result Table :
Sample - 1 Sample - 2
Amount of K+ in the given sample of water
----------- ppm ---------- ppm
Test your Knowledge
1. Give the emitted wavelength by excited Na atoms in flame. What is the colour of
Na flame?
2. Give the emitted wavelength by excited K atoms in flame. What is the colour of
K flame?
3. Why distilled water must be used for analysis of metal by flame photometry?
4. Give the equation for number of atoms in the excited state. Calculate fraction of
excited state Na atoms in the flame of temperature 800°C.
5. What is the effect of drop size on flame temperature and atomization?
6. Why transition metals are not analyzed by flame emission spectroscopy?
Experiment No. 4
Estimation of K
Aim:
To determine the concentration of given unknown samples of Potassium (K) by flame
photometry using least square (regression analysis) method.
Principle, Chemicals, Procedure is same as that of Experiment No. 3 (Flame Photometer
Analysis of Potassium), only method of calculation is different.
Perform the same procedure as per given in the Experiment No. 3.
Observation Table:
Solution Conc. of K+ in Flame intensity
ppm (xi) (yi)
Sample-1 Unknown
Sample-2 Unknown
215
Calculation by least square method:

There are two assumptions in the least-squares method.
3. The linear relationship actually exists between measured response (y-axis value) and
standard analyte concentration. The mathematical relationship describing this
assumption is called as regression model which is given by following equation:
4. Any deviation from the individual point from the straight line arises from the error in
the measurement i.e. we assure that there is no error in the x value of the point. Both
these assumptions are appropriate for many analytical methods. But whenever there
is significant uncertainty in the x data, then basic least-squares method do not give
rise straight line.
The calculations are as follows:
The slope of line is given by following equation:
a = 2
n ∑ xi − (∑ xi)2
where, n = 5 (number of data points)
xi = value of individual concentration in ppm (x1 to x5)
yi = value of individual flame intensities (y1 to y5)
∑ xi = (4 + 8 + 12 + 16 + 20),
∑ yi = sum of flame intensities for five readings of standards
2
∑ xi = 42 + 82 + 122 + 162 + 202,
2
∑ yi = make a square of each flame intensity and then take sum.
(∑ xi)2 = (4 + 8 + 12 + 16 + 20)2,
n ∑ xi yi = 5[(x1 y1) + (x2 y2) + (x3 y3) + (x4 y4) + (x5 y5)]
b = −y + a−x
where, −x = (4 + 8 + 12 + 16 + 20)
5
− (sum of flame intensities of five standards)
y =
5
From slope concentration of sample is calculated.
and, y = flame intensity of sample, x = concentration of sample, ppm (to be calculated).
Regression of the line can be calculated by following equation:
r=
2 2
[n ∑ xi − (∑ xi)2] [n ∑ yi − (∑ yi)2]
r is called as regression of line. This value indicates the linearity of line. For 100% linearity
of five standard readings the value of r is ±1. Practically this value is expressed as r2 and is
1 for 100% linearity. Experimentally this value should be greater than 0.95. If this value is less
216
than 0.95 then we can say that there exists large error in the determination of flame
intensities. Such readings cannot be accepted for calculations.
Result Table :
Sample-1 Sample-2
Amount of K+ in the given sample of water
----------- ppm --------------- ppm
---
217
(F) Inorganic Qualitative Analysis
(Four Mixtures)
The detection or identification of individual elements or ions entering into the
composition of a substance constitutes the task of qualitative analysis.
Qualitative analysis is of enormous, scientific and practical importance. It is a science
dealing with the various methods for investigating substances and their transformations.
It also plays an important role in branches of science allied to chemistry, mineralogy,
geology, physiology, microbiology, as well as in medicine, agriculture and technology. In
almost every scientific research work dealing in one way or another with chemical
phenomena, the investigator has to make use of the qualitative methods of analytical
chemistry.
According to the amount of substance used for analytical reactions, qualitative analysis is
distinguished into four categories.
1. Macro Qualitative Analysis :
In this method, large quantities of an unknown substance (0.5 to 1.0 g) or solution
(20 - 50 ml) are used. The reactions are carried out in ordinary test tubes (10 - 20 ml in
capacity), beakers or flasks. Precipitates are separated by filtration through filter paper.
Analyst requires large quantities of reagents and hence it is non-economic.
2. Micro Qualitative Analysis :
Very small quantity (few mg) of substance or (about a millilitre) solution is used to carry
out this analysis. Only highly sensitive reactions are employed, which permit detection of
individual constituents by the fractional method even if they are present in small amounts.
Such reactions are carried out either by micro crystalloscopic method (using microscope
slides) or by the drop method (using spot tests).
3. Semimicro Qualitative Analysis :
It ranks between macro and micro method of qualitative analysis mentioned above. The
amount of substance used is about 50 mg of solid or 1 ml of solution. This method is more
advantageous over macro analysis, because it gives quick and reliable results and also needs
small amounts of reagents. It is more economic than the macro method. For these reasons,
it is generally employed commonly in laboratory work.
4. Ultramicro Qualitative Analysis :
It is employed when the substance to be analysed is available in very small amount (less
than 1 mg). In this method, all the analytical operations are performed under the microscope.
217
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Inorganic Qualitative Analysis
The qualitative scheme of analysis given here is concerned with the methods of
qualitative analysis of inorganic substances only. Before going to the analysis, students
should refer the following important instructions.
INSTRUCTIONS :
(a) Dry Tests : These tests are performed directly with the given solid (dry) substance
and the appropriate reagent by heating them to a desired temperature.
1. Use clean and perfectly dry test tube.
2. Heat the test tube on blue flame of the burner.
3. Observe the changes upon heating very carefully.
4. Do not throw the contents of the test tube in basin, unless the test tube is cooled.
5. Make sure that all the necessary test papers are ready with you before heating the
substance. Moisten the test papers (blue and red litmus, turmeric paper, starch paper
etc.) before using them.
6. To prepare starch iodide paper just immerse a piece of starch paper in potassium
iodide solution.
7. Do not place hot test tube or beaker directly on your table, make use of asbestos
sheet.
8. Replace the reagent bottles after use at their original place in reagent rack.
9. Read the complete test before performing it.
10. Record your observations according to the sequence given in the scheme.
(b) Wet Tests :
1. Prepare a solution of a given substance in a suitable solvent. Solution should not be
turbid one.
2. Use small fractions of this solution for every test. Large volumes need more reagents
for precipitation and also take more time for filtration.
3. Strictly follow the instructions given for each test (e.g. instructions regarding pH,
temperature etc.)
4. If solutions are colourless, label them to avoid confusion during analysis.
5. Do not throw any solution, till the completion of analysis.
6. Once a particular group is detected, precipitate it completely, filter it and use it for
group analysis.
7. Analyse the group to find out basic radical and confirm it.
8. Use water solution only for detection and identification of group VI radicals.
SCHEME OF INORGANIC QUALITATIVE ANALYSIS :
The systematic procedure of the analysis of a given mixture involves following steps :
(a) Preliminary tests
(b) Dry tests for basic radicals
(c) Dry tests for acidic radicals
218
(d) Preparation of solution

(e) Wet test for basic radicals and their confirmatory tests.
(f) Wet test for acidic radicals and their confirmatory tests.
(A) PRELIMINARY TESTS :
Observation Inference
1. Colour
(a) Blue Hydrated copper salts and anhydrous cobalt
salt.
(b) Bluish green or green Chromium, nickel, copper and ferrous salts.
(c) Yellow Chromates or salts like PbO, HgO, Bi2O3,
FePO4, CdS, As2O3 etc.
(d) Orange or red Dichromates and Sb2S3.
(e) Pink or flesh Cobalt or manganese salts.
(f) Black Oxides of Cu2+, Mn2+, sulphides of Fe3+, Sb3+,
Ni2+.
(g) White/colourless Al, Zn, Ca, Sr, Mg, Na, K, NH4 salts.
(h) Coloured Coloured radicals like Cu2+, Mn2+, Fe3+ etc.
and coloured powders like HgO, PbO.
2. Nature/Appearance
(a) Crystalline All soluble salts i.e. salts of Na, K and NH4 or
2− − −
salt with Cl−, Br−, I−, SO4 , NO2 , NO3 .
A E A A E A A E A
(b) Amorphous Insoluble salts containing CO3 , S2−, PO4 , A

2−
E A
3−
A E A
3− 2−
BO3A E ,O .
A
(c) Hygroscopic Nitrate salts.

(B) DRY TESTS FOR BASIC RADICALS (CATIONS) :
3. Heating in a Dry Test Tube :
Take a little quantity of the given mixture in a dry test tube. Heat it strongly and observe
the change which takes place during heating (more than one observation may be taken).
(a) Decrepitation, i.e. cracking noise Crystalline salts like NaCl, KBr, Pb(NO3)2,
Ba(NO3)2 etc.
(b) Substance fuses Alkali salts, nitrates of alkaline earth metals.
219
(c) Water vapour condenses on the cooler The water is due to (i) hygroscopic salts,
part of the test tube. (ii) water of crystallisation, (iii) decompo-
sition of hydroxides.
(d) Change in colour
(Contd.)
Original
Colour On heating On cooling
White Yellow White Zn salts
White Brown Brown Cd salts
White Yellow Brown Pb and Bi salts
Coloured Black Black Salts of Cu, Fe, Cr, Mn, Co, Ni
White White White Salts of Ca, Ba, Sr, Al, Mg.
(e) Formation of sublimate NH4 salts and HgCl2, As2O3, Sb2O3
(f) Evolution of a gas

1. Colourless and odourless gas igniting a Nitrates, chromates and oxides like HgO
glowing splinter i.e. O2 gas.
2. Colourless and odourless gas turning Carbonates

freshly prepared lime water milky
i.e. CO2 gas.
3. Colourless gas with pungent odour, Ammonium salts

turning moist turmeric paper red
i.e. NH3 gas.
4. Colourless gas turning dichromate Sulphate and certain sulphides like PbS
paper green i.e. SO2 gas.
5. Brown fumes, i.e. NO2 or Br2 gas. Nitrates or bromides (Br2 turns starch paper
yellow)
6. Violet fumes i.e. I2 gas turns starch Iodides
paper blue black.
4. Heating in a Charcoal Cavity :
Prepare a small cavity on a piece of charcoal. Place a little quantity of mixture
(Given mixture + Na2CO3 in the ratio 2 : 1). Place a drop of water on it and heat it with the
reducing (yellow) flame using blow pipe.
220
White infusible residue obtained Coloured residue obtained

(Ca, Sr, Ba, Zn, Al salts) (Transition metal salts)
↓ (Cu2+, Fe2+, Fe3+, Mn2+ etc.)
Perform cobalt nitrate test as follows :
Moisten the white infusible residue with one or two drops of cobalt nitrate solution and
heat it again on oxidising flame (blue) using blow pipe.
If residue turns
Blue Green Pink Gray

... Al salts Zn salts Mg salts Ba, Sr, Ca salts
(Hint : Generally, white/colourless mixtures give white infusible residue on charcoal

cavity, while coloured mixtures give coloured residue.)
5. Action of NaOH :
Take small amount of the mixture in a test tube and add a little amount of dilute NaOH
solution to it. Heat to boiling. Hold the moist turmeric paper at the mouth of the test tube
+
without touching the test tube. If the paper turns red, NH4 may be present.
A
E
A
(C) DRY TESTS FOR ACIDIC RADICALS (ANIONS) :
6. Action of Dilute HCl :
Take small quantity of the mixture in a test tube, add dilute HCl and heat gently.
(a) Brisk effervescence of CO2 gas turning CO2− (Carbonate)
3 A E A
freshly prepared lime water milky.

(b) Evolution of colourless H2S gas having S2− (Sulphide)
smell of rotten eggs and turning lead
acetate paper black.
221
−
(c) Brownish fumes acidic to litmus, NO2 (Nitrite)A E A
NO2 gas.
7. Action of MnO2 + Conc. H2SO4 : Mix small quantity of mixture with a pinch of MnO2 in
a test tube. Add 1-2 ml of concentrated H2SO4 and heat cautiously.
(Hint : Until you don't see coloured fumes, do not test with any test paper.)
(a) Greenish yellow, Cl2 gas is evolved Cl− (Chloride)

which turns blue litmus paper red and
then bleaches it. It also turns starch
iodide paper blue.
(b) Brown fumes of Br2 gas evolved which Br− (Bromide)

turns starch iodide paper blue and
starch paper yellow and fluorescent
paper red.
(c) Violet vapours of I2 evolved turning I− (Iodide)

starch paper blue.
(d) No coloured fumes. Halides may be absent.
8. Nitrate Test :
Take little quantity of mixture in a test tube, add conc. H2SO4 and heat gently, if brown
−
fumes are seen then add copper filings and heat. If intense brown fumes increases then NO3 A E
may be present.
A
9. Phosphate Test :
Take a little mixture in a dry clean test tube. Add to it concentrated HNO3 and boil well to
dissolve the mixture. To this hot solution now add excess of ammonium molybdate solution.
3−
If canary yellow precipitate is obtained, PO4 i.e. phosphate may be present.
A
E
A
(Hint : Many times only yellow colouration is obtained, which may not be a precipitate.
If it is a precipitate, it should settle at the bottom of test tube on keeping for few minutes.)
10. Borate Test :
222
Take a little mixture in a porcelain dish. Add to it a drop of concentrated H2SO4 and two
drops of ethyl alcohol. Mix well with the help of glass rod and make a paste of this mixture.
Take thin paste on glass rod and hold it in the flame. If a green edged flame of ethyl borate is
3−
observed, BO3 , i.e. Borate may be present.
A
E
A
(Hint : Both phosphate and borate are never given in the mixture, therefore any one of
these two may be present in the given mixture. However, sometimes both phosphate and
borate may not be present.)
(D) PREPARATION OF A SOLUTION OF THE GIVEN MIXTURE :
Prepare only 10 - 15 ml of solution (1 test tube) :
(a) Solution in water : Take a little quantity of the mixture in a test tube and add to it
about 1/3rd test tube of water and boil. If the mixture dissolves completely, the components
of the mixture are water soluble. In such a case, the aqueous solution of the mixture is used
to detect the basic radicals.
(b) Solution in dilute HCl : If the mixture is not completely soluble in water, add about
2 - 4 ml of dilute HCl (2N) and boil. If the mixture dissolves completely, use this solution for
further analysis. If gas like CO2 or H2S is evolved, boil the solution till it is free from H2S or
CO2.
(c) Solution in conc. HCl : Take a little quantity of given mixture in a test tube and add
3 ml of concentrated HCl to it. Boil well till evolution of CO2 and H2S is completed. Dilute this
solution and use it for further analysis.
(d) If the given mixture is insoluble in dil. and conc. HCl, then use the following
solvents in the order given as dil. HNO3, conc. HNO3 and aqua regia (mix. of conc. HCl and
HNO3 3 : 1).
Mixture partly soluble in water : Take a little quantity of mixture in a test tube and add
to it about 3 - 4 ml water and boil, if mixture is partly soluble then filter or centrifuge. Collect
the filtrate and residue and analyse them separately to find the basic radicals.
Principles of Precipitation (Solubility Product) :
As quantitative analysis involves the precipitation of a radical into its insoluble salt,
qualitative analysis mainly depends on solubility product principle and chemical reaction can
be explained by it.
In a saturated solution of an insoluble binary electrolyte e.g. MA (where M = cation and
A = anion), the ionic product of M and that of A, at a given temperature remains constant
and is called the 'solubility product' and is denoted by Ksp of MA.
Ionic Product : It is the product of ionic concentration of ions.
The precipitation will occur when the ionic product exceeds the solubility product.
Hence,
223
1. Ionic product > Solubility product → Precipitation (supersaturated solution)

2. Ionic product < Solubility product → No precipitation (unsaturated solution)
3. Ionic product = Solubility product → No precipitation (saturated solution)
In a solution containing M+ ion, the concentration of A− is made very high, the insoluble
salt MA will be precipitated and concentration of M+ will be gently reduced, because as
[A−] increases, [M+] must decrease to bring ionic product equal to solubility product.
In a similar way, A− can be completely precipitated from its solution by increasing the
concentration of M+.
224
225
ANALYSIS OF BASIC RADICALS

Separation of Basic radicals into group
Original solution + dil. HCl
O.S.* + dil. HCl (warm), pass H2S gas
O.S./Filtrate : If group II present, boil well to expel H2S completely and

then
(a) Take 2 drops of filtrate on the tile + K3[Fe(CN)]6. If blue colour Fe2+
present.
(b) If Fe2+ is present add 2 - 3 ml of conc. HNO3 in the filtrate and boil
well so that Fe2+ is oxidised to Fe3+.
Precipitate (c) This solution + NH4Cl (solid) + 1 : 1 Ammonia (NH4OH) till alkaline to
(white) litmus.
Group I is O.S./Filtrate* + NH4Cl (Solid) + 1:1 Ammonia (NH4OH) till
present
alkaline + H2S
Ag+, Hg+,
Precipitate Filtrate boil well to expel H2S completely
Pb2+.
(coloured) O.S./Filtrate** + NH4Cl (solid) +
If present
Group II is 1 : 1 Ammonia + (NH4)2CO3
See Pg. 226
present
Precipitate Filtrate + NH4Cl (solid)
Hg2+, Pb2+,
Group III A
Bi2+, Cu2+, + 1 : 1 Ammonia +
is present Na2HPO4
Cd2+, As3+, Precipitate
3+ 2+
Sb , Sn ,
Fe2+, Fe3+, If no ppt
Sn4+. Group III B Precipitate
3+
Al , Cr . 3+ Precipitate upto
If present is present (white) Group V
If present (white)
See Pg. 226 Zn2+, Mn2+,
See Pg. 230 Group IV is Group V or only one
Co2+, Ni2+. If
present present is group is
present 2+
See Pg. 231 Ca2+, Ba2+, Mg detected,
2+ then
Sr If present
If present See Page 232 Group VI
See Pg. 231 is present

NH , K+,
+
4
A A
Na+. If
present
See Page
233
* Use fairly dilute solution for testing of Group II and III B.
* Use concentrated solution for testing of Group IV.
226
SEPARATION TABLE FOR GROUP I :
Transfer the ppt. of group I metal chloride in a porcelain dish, add 5 ml water, boil it well.
Filter when hot. If ppt. dissolves, only filtrate is obtained.
Residue Filtrate
Add to the residue 5 ml of conc. NH4OH. It may contain PbCl2
Warm and filter. 1. Filtrate + K2CrO4 solution. If yellow ppt.
Residue Filtrate Pb2+ present.
Residue + aquaregia Acidify the filtrate with 2. Filtrate + KI solution. If yellow ppt. of
HCl : HNO (3 : 1) boil dilute HNO . If white PbI2 soluble on heating and reappears
3 3
and add SnCl2. If black ppt. of AgCl is formed, as golden crystals on cooling.
ppt., then Hg+ present then Ag+ present. 3. Filtrate + dilute H2SO4 : If white ppt.
and confirmed. C.T. filtrate + KI then Pb2+ present and confirmed.
solution. If yellow ppt.,

then Ag+ is confirmed.
SEPARATION TABLE FOR GROUP II :

Transfer the ppt. of group II metal sulphide into a porcelain dish and add 5 ml of yellow
ammonium sulphide (NH4)2SX and 1 - 2 ml of NaOH. Heat it to 60°C for about 5 minutes.
If ppt. dissolves only filtrate is obtained and group II B is present. Acidify the solution by
adding
conc. HCl, yellow or orange ppt is obtained.
(Use separation table for group II B on page no. 228).
If ppt. does not dissolve group II A is present. [If white or dirty white ppt. is obtained,
then it is a ppt. of excess of sulphur. Therefore, it should be rejected i.e. II B group absent.]
(Use separation table for group II A as given below.)
SEPARATION TABLE FOR GROUP II A :
Transfer the ppt. of II A group metal sulphides into porcelain dish. Add 2 - 3 ml of
conc. HNO3. Boil for 2 - 3 minutes. Filter or centrifuge. If ppt. dissolves only filtrate is
obtained.
227
Residue Filtrate
Black ppt. HgS. Filtrate contains nitrates of Pb, Bi, Cu, Cd. To a small portion add
Dissolve the residue in dil. H2SO4. If white ppt is obtained, it indicates the presence of
aquaregia (HCl + HNO3 Pb++. So to the whole solution add dil. H2SO4. Filter or centrifuge.
3 : 1) by boiling, dilute
with water.
C.T. Residue Filtrate

(i) Solution + SnCl2 It is white ppt. of It may contain sulphates or nitrates of
solution white or grey PbSO4. Boil the Bi, Cu, Cd. Add 1 : 1 ammonia in excess.
ppt. confirms the residue with strong Filter or centrifuge.
presence of Hg2+. solution of
(ii) Solution + KI if ammonium acetate to Residue Filtrate

yellow ppt. of HgI2. get solution. It is white ppt. of If filtrate is blue,
2+
Hg present and C.T. Bi(OH)3. Wash with Cu2+ may be
confirmed. (i) This solution + water. Dissolve it in present. (C.T.)
acetic acid + dil HCl. (i) To a small
K2CrO4. If yellow (i) Solution + excess portion add dil.
ppt. of PbCrO4 is water, if white ppt. acetic acid then
obtained, Pb2+ of BiOCl is add potassium
may be present. obtained then ferrocyanide
(ii) Solution + KI if
3+
Bi is present. solution. If a
yellow ppt. is (ii) 1 ml solution + chocolate red
obtained, Pb2+ is 10% Thiourea ppt. then Cu2+
confirmed. solution if intense present and
yellow colour or confirmed.
ppt is obtained (ii) To the other
3+
then Bi is part add
confirmed. K2CrO4
solution. A light
yellow ppt. of
CdCrO4 is
obtained. Cd++
present and
confirmed.
228
SEPARATION TABLE FOR GROUP II B :

Transfer the ppt. of Group II B metal sulphide into a porcelain dish and add 5 ml
conc. HCl and boil for 5 minutes. Filter or centrifuge.
Residue Filtrate
Residue may be yellow As2S3. Boil It may contain complexes of Sb and Sn. Neutralise it
the residue with conc. HNO3 and with diluted NH4OH. Add solid oxalic acid and heat,
dilute with H2O to get solution. pass H2S gas.
C.T. Residue Filtrate
(i) Solution + ammonium molyb- Orange coloured ppt. of It may contain a complex
date, if yellow ppt. then As3+ Sb2S3. Dissolve it in conc. of Sn and oxalic acid.
present. HCl. Expel H2S, add Zn and
(ii) Solution + Mg(NO3)2, if white C.T. : dilute HCl. Sn is
ppt. is obtained, then As 3+
(i) Dilute a small portion precipitated. Dissolve it
present and confirmed. of it with water. If in conc. HCl to get
white turbidity of solution :
SbOCl, then Sb3+ (i) Solution + HgCl2
present. solution. If white ppt.
(ii) Solution + of Hg2Cl2, then Sn2+
Rhodamine B. If red present and
colour is seen and (ii) Solution + dilute I2
(iii) Solution + KI + solution. If I2
pyridine. If coloured
decolourises, then
solution, then Sb3+
Sn2+ present and
present and
confirmed.
confirmed.
REMOVAL OF INTERFERING ANIONS :
Phosphate and borate ions interfere in the detection of group of cation from III A to V
due to formation of their insoluble borates and phosphates in the alkaline medium.
For example, if given mixture contains Ni3(PO4)2 that is nickel phosphate, its original solution
is prepared in acid like HCl.
∴ Ni3(PO4)2 + 6HCl ⎯→ 3NiCl2 + 2H3PO4
Thus, original solution contains Ni2+ ions along with phosphoric acid. When this solution
is tested for presence of group III A (which is not present, as Ni2+ is present in III B) by adding
NH4Cl and NH4OH, following reaction takes place.
3NiCl2 + 2H3PO4 + 6NH4OH ⎯→ Ni3(PO4)2 ↓ + 6NH4Cl + 6H2O
A precipitate of nickel phosphate is obtained, which leads to conclusion of presence of
group III A which is not actually present. Similar type of misleading reaction is observed when
borate is present. Thus when phosphate or borate is present they must be removed before
the detection of group III A from the solution.
229
Removal of Phosphate - (If present) :

1. If group I and II are absent then use the original solution.
2. If group II is present, precipitate it completely and filter, use filtrate of group II for the
removal of phosphate after expelling H2S gas by boiling the filtrate.
3. Test for Fe2+ : Take one drop of filtrate/O.S. on porcelain tile, mix a drop of
potassium ferricyanide solution → If blue colour or precipitate is seen, Fe2+ is present.
4. If Fe2+ is present add to the filtrate or O.S. 2 - 3 ml of concentrated HNO3 and boil so
that Fe2+ is oxidised to Fe3+.
5. Use this solution for removal of phosphate as follows :
To the solution add 1 g of NH4Cl, warm and then add 1:1 NH3 until a slight turbidity
is obtained and persist even after stirring. This means solution is alkaline and
turbidity is due to either hydroxides of III A group metals or phosphates of III B, IV
and V. Now add 10 ml of sodium acetate buffer solution and stir well.
If turbidity persist or If turbidity dissolves

increases, III A group present. completely, phosphates of
Stir the ppt. and filter. III A, IV, V group present
ppt. (Residue) contains Filtrate contains phosphate

hydroxides of Fe, Cr, Al. of III B, IV, V group
Use it for the analysis of
group III A. Page No. 230
Add neutral FeCl3 solution till

phosphate is precipitated and
solution acquires brownish
red colour. Boil and filter.
Filtrate contains III B, ppt. (Residue)

IV, V group chlorides Discard the ppt.
and excess of FeCl3 . of FePO4
Add to the filtrate NH4Cl
solid + 1 : 1 NH3 till alkaline
Reddish brown ppt. of Fe(OH)3 is obtained. Boil and filter, discard the ppt. of Fe(OH)3 and
concentrate the filtrate (reduce the volume) and use for detection of III B, IV and V group
according to the chart given on Page No. 225.
230
Removal of Borate (If present) :

1. If group II is present, precipitate it completely by passing H2S gas. Filtrate the
precipitate and boil the filtrate to expel H2S completely (test with lead acetate paper).
Then use it for removal of borate.
2. If group I and II are absent, then use original solution.
3. Removal of borate. Take O.S/filtrate from group II in a porcelain dish, add to it
3 ml conc. HCl and 5 ml ethyl alcohol and boil. Repeat this procedure till test for
borate is negative (no green edged flame on igniting the solution). Then use this
solution for detection of group III A onwards according to chart given on Page
No. 225.
SEPARATION TABLE FOR GROUP III A :
Transfer the ppt. of Group IIIA metal hydroxide in a evaporating dish + 4 ml NaOH +
2 ml H2O2, boil and filter. If ppt. dissolves completely only filtrate is obtained.
Residue Filtrate
It may contain Fe(OH)2 and MnO2 x H2O. The filtrate contains NaAlO2 (colourless)
Divide the residue into two parts. and Na2CrO4 (yellow). It is divided into two
Part I : parts.
Dissolve 1st part of the residue in conc. Part I :
HNO3 and add to it a pinch of PbO2. Boil If the colour of the filtrate is yellow,
3+
gently for 2 to 3 minutes, dilute with water Cr may be present :
and allow to settle. If violet colouration of (a) Acidify with dilute CH3COOH and then
HMnO4 (permanganic acid) then Mn2+ added lead acetate solution. If yellow
present and confirmed. ppt. of PbCrO4, then Cr3+ present.
Part II : (b) Neutralise the yellow solution by
Dissolve the second part in hot dilute CH3COOH and add AgNO3 solution. If a
HCl and divide the solution into two parts : brick red ppt. of Ag2CrO4, then Cr3+
(a) Solution + Ammonium thiocyanate
(NH4SCN) solution. If deep blood red
Part II :
colouration, then Fe3+ present. (a) If filtrate is colourless acidify with HCl.
(b) Solution + Potassium ferrocyanide Then add NH4OH till the solution is
K4[Fe(CN)6], if a deep blue colouration,
alkaline. Heat to boiling. If white
then Fe3+ confirmed. gelatinous ppt. of Al(OH)3 formed, then
Al3+ present.
(b) Alizarin Test : A drop of Alizarin on the
test paper + 1 drop of filtrate. Hold the
paper over bottle of ammonia. If a violet
red colour is seen, then Al3+ present and
confirmed.
231
SEPARATION TABLE FOR GROUP III B :

Transfer the ppt. of group IIIB sulphide into a porcelain dish and add to it about 5 - 7 ml
of dil. HCl. Stir well and allow to stand for five minutes. Filter the solution.
Residue Filtrate
The black residue may be of NiS or It may contain MnCl2 and ZnCl2. Boil the solution to
CoS. Dissolve the ppt. in conc. HCl expel H2S. Add excess of NaOH solution. Filter.
and add a few crystals of KClO3
Residue Filtrate
(or in aquaregia). Boil the excess
It is white residue It may contain Na2ZnO2.
of acid and evaporate to dryness.
turning brown due (1) Acidify the solution by
Cool it and extract the solid with
to atmospheric oxi- acetic acid and then pass
5 ml of water. Divide this solution
dation. Dissolve H2S gas. If white ppt., then
into three parts.
this ppt. in conc. Zn2+ present.
Tests for Co2+ : HNO3 + a pinch of
(2) Acidify the solution by
(1) To a portion of the solution add PbO2, boil and
acetic acid. Add 4 drops of
solid NH4Cl and ammonia till dilute with the
K3[Fe(CN)6] solution →
alkaline and add K4[Fe(CN)6]. If water. If violet
Green ppt.
red solution or reddish brown colouration, then
ppt. on heating, then Co2+ Mn2+ present and (3) Acidify the solution with
present. dil. HNO3 and add a few
confirmed.
drops of Co(NO3)2 solution.
(2) Two drops of solution on a
watch glass + one crystal of Heat to dryness. If a green
Na2S2O3. If blue colour around mass, then Zn2+ present and
the crystal is seen then Co2+ confirmed.
(3) To a portion of the solution add
solid NH4Cl and ammonia till
alkaline. Then add excess of
dimethyl glyoxime. If scarlet red
ppt. then Ni2+ present and
confirmed.
SEPARATION TABLE FOR GROUP IV :

Transfer the ppt. of group IV metal carbonate in a porcelain dish and dissolve it in
dil. acetic acid. Boil to expel CO2. The solution thus formed is called as acetate solution.
1. Take 2 ml acetate solution. Boil it + K2CrO4 if yellow ppt. then Ba2+ present.
232
2. If Ba2+ is present, add little excess of K2CrO4 solution to the whole solution. Boil and
filter and proceed for residue below.
3. If Ba2+ is absent, then test the acetate solution for Sr and Ca (filtrate).
Residue Filtrate
Wash yellow residue of BaCrO4 It may contain Sr and Ca acetate. Add excess of
with water. Dissolve it in about 3 ml ammonium sulphate solution and heat to boiling.
conc. HCl. Solution of BaCl2 is Allow to stand for 5 minutes. Filter.
obtained : Residue Filtrate
(1) If this solution is heated on a (1) It is a ppt. of SrSO4. (1) Concentrate the
platinum wire, it imparts a Add 2 to 3 drops of solution. Then add
green colour to the flame. conc. HCl and take it ammonium oxalate
on a platinum wire. It (NH4)2C2O4 solution.
(2) To this solution add dilute
imparts a crimson If white ppt. of
H2SO4, if white ppt. of BaSO4,
colour to the flame. CaC2O4, then Ca2+
then Ba2+ present.
(2) Dissolve the residue in present.
(3) Solution + ammonium oxalate conc. HCl. Take a drop (2) Prepare a very con-
(NH4)2C2O4 solution, if white of it on a paper and centrated solution
ppt. of BaC2O4 then Ba2+ add a drop of sodium and add one drop of
present and confirmed. rhodizonate solution. conc. HCl to it. This
If brownish red solution imparts a
coloured spot, then red colour to the
Sr2+ present and flame, then Ca2+
confirmed. present and
confirmed.
ANALYSIS OF GROUP V :
Transfer the ppt. of group V in a test tube and dissolve it in a little dil. H2SO4. Use this
solution for C.T. of Mg2+.
C.T. for Mg2+ :
1. 2 drops of solution on watch glass + 2 drops of titan yellow solution + 4 drops of
dil. NaOH solution, a rose red colour or ppt.
2. Hypoiodate reagent + 2 drops of above solution, if reddish brown ppt. of Mg(OI)2
then Mg2+ present and confirmed.
(Hypoiodate reagent : NaOH solution + equal amount of KI solution + Iodine
solution till solution becomes just yellow.)
233
SEPARATION TABLE FOR GROUP VI :

(i) Use water solution only.
+
(ii) Test the water solution for NH4 , Na+ and K+ as follows : A E A
+
(1) Test for NH4 A E :
A
Water solution + NaOH boil, if evolution of NH3 gas which turns moist turmeric paper
+
red, NH4 present.
A E A
+
C.T. for NH4 : Nessler's reagent + water solution, if brown ppt. or colouration is seen,
A E A
+
then NH4 A E confirmed.
A
(Nessler's reagent : 2 drops of HgCl2 + KI solution till the scarlet red ppt. first formed
and then dissolves. Then add equal amount of NaOH.)
(2) Test for Na+ and K+ :
Water solution + Sodium cobaltinitrite : Na3[Co(NO2)6]
If yellow ppt. If no yellow ppt.

then K+ present then Na+ present
A E A A E
C.T. for K+ : (i) Water solution + Picric acid. Rub the inner side of the test tube with glass
rod, if yellow ppt. of potassium picrate then K+ confirmed.
(ii) Water solution + perchloric acid, if white ppt. then K+ confirmed.
C.T. for Na+ : Water solution + Potassium pyroantimonate (K2H2Sb2O7) if white ppt. then
Na+ confirmed.
(Hint : Generally sodium (Na+) is not given in the mixture.)
DETECTION OF ACIDIC RADICALS (ANIONS) :
2− 3− 3−
Acidic radicals like CO3 , S2−, PO4 , BO3 are easily detected during the dry tests for
A E A A E A A E A
−
anions. Halides (Cl , Br , I ) and nitrate − − −
(NO3 A E ) may also be detected in dry tests if the tests for
A
2−
them are carried out carefully. There is no separate dry test for SO4 . Presence of acidic A E A
radicals are further confirmed by wet tests.

If the mixture is water soluble, then its water solution (WS) is used for the detection of
acidic radicals. If the mixture is insoluble in water, sodium carbonate extract and neutral
extract are used for the detection of acidic radicals. These extracts are prepared as follows :
Preparation of sodium carbonate extract : This is required only when mixture is water
insoluble.
234
The sodium carbonate extract is prepared to convert the water insoluble anions like
2− 2−
S , CO3 to their sodium salts which are soluble in water. Take about 0.1 g of mixture and
A E A
about 0.2 g of solid pure sodium carbonate in a beaker. Add about 1/2 test tube of distilled
water and boil for about 2 minutes. Cool and filter. Discard the residue. The filtrate is called
as sodium carbonate extract.
Preparation of neutral extract : A part of sodium carbonate extract is neutralised by
adding few drops of dil HNO3 till solution becomes acidic and then NH4OH till solution
becomes just alkaline. (Use litmus paper to check acidity and alkalinity.) Boil the solution to
remove excess of NH3 and CO2 and cool. The resulting solution is called neutral extract (NS).
(Hint : Use water solution only for the detection of acidic radicals if mixture is water
soluble. Do not prepare sodium carbonate extract and neutral extract.)
3−
If mixture is water insoluble, use neutral extract only for the detection of halides, PO4 , A
E
A
3− 2− − −
BO3 A E and
A SO4 ,
A
E
A while use sodium carbonate extract only for the detection of S2−, NO2 A E ,
A NO3 A E
etc.
A
Before you proceed for the wet tests of anions, check the results of dry tests and see
which tests are positive.
Tests Observation Inference
(1) Neutral solution (N.S.)/ (a) Curdy white ppt insoluble Cl− present
Water solution (W.S.) + in dil. HNO3 but soluble in
AgNO3 solution. NH4OH
(b) Pale yellow ppt. soluble in Br− present
liquor ammonia
(c) Yellow ppt. insoluble in I− present
dil. HNO3 and also in
NH4OH
(d) Yellow ppt. soluble in 3−
PO4 present
dil. HNO3
A E A
(e) White ppt. soluble in 3−

BO3 present
dil. HNO3
A E A
(2) Neutral solution or Water White ppt. insoluble in 2−

SO4 present
solution + Ba(NO3)2 dil. HNO3.
A E A
solution.
(3) Sodium carbonate extract + Black ppt. soluble in HNO3 S2− present
Lead acetate.
235
−
(4) Sodium carbonate extract Brown coloured solution NO2 present
A E A
or W.S. + dil. acetic acid +

FeSO4 solution.
−
(5) Sodium carbonate extract Brown ring at the junction of NO3 present
A E A
or W.S. + conc. H2SO4 (cool two layers.

thoroughly) + FeSO4
solution dropwise from the
sides of the test tube.
(6) Little mixture + dil. HNO3. Effervescence of CO2 gas 2−
CO3 present
A E A
CONFIRMATORY TESTS FOR ANIONS :

1. Chloride (Cl−) :
Chromyl Chloride Test : Little of mixture (or 2 ml water extract) + little solid K2Cr2O7
and few drops of conc. H2SO4 in a test tube. Heat gently, and pass the evolved gas
into another test tube containing lead acetate solution. If yellow ppt. of lead
chromate is formed, then Cl− is confirmed.
2. Bromide (Br−) :
Water solution + Chlorine water + Chloroform. Shake well. If brown colour to the
chloroform layer (at the bottom) then Br− is confirmed.
3. Iodide (I−) :
Water solution + Chlorine water + Chloroform. Shake well. If violet colour to the
chloroform layer (at the bottom), then I− is confirmed.
( ):
2−
4. Sulphate SO4 A E A
(a) Lead acetate test : Water solution + Lead acetate solution. If white ppt. of
2−
PbSO4, SO4 is confirmed.
A E A
OR
(b) Sodium rhodizonate test : Place a drop of freshly prepared 5% aqueous
solution of sodium rhodizonate on a test paper and add to it a drop of BaCl2
solution.
A red ppt. is formed. Then add a drop of aqueous solution of the given mixture
2−
on red spot. If red ppt. disappears, SO4 is confirmed.
A E A
5. Sulphide (S2−) :
Sodium nitroprusside test : Take 1 ml of water extract in a test tube, add 2 drops of
NaOH solution. Then add 2 drops of sodium nitroprusside reagent solution.
If violet colouration, then S2− is confirmed.
236
−
6. Nitrite (NO2 ) : A E A
(a) Little of the mixture (or 2 ml water extract) + 1 drop of dil. CH3COOH + Pinch of
thiourea. Shake well and add few drops of aqueous FeCl3 solution. If red
−
colouration, NO2 is confirmed. A E A
OR
−
(b) Mixture + dil. H2SO4 and warm. If brown fumes of NO2 gas, then NO2 is A E A
confirmed.
−
7. Nitrate (NO3 ) : A E A
Brown ring test : Take 1 ml of water solution and acidify it with conc. H2SO4. Cool
the solution. To this solution add a saturated solution of FeSO4 from the sides of the
test tube. If a brown ring at the junction of two layers is formed due to FeSO4.NO
−
complex, then NO3 is confirmed. A E A
2−
8. Carbonate ):
(CO3 A E A
(a) Little of the mixture + 1 ml dil. H2SO4. If effervescence of CO2 (colourless gas)
2−
which turns lime water milky, CO3 is confirmed. A E A
3− 3−
(Hint : No confirmatory test for PO4
and BO3 is required because their presence is A E A A E A
confirmed during dry tests for acidic radicals only.)

TEST FOR ANIONS IN PRESENCE OF EACH OTHER :
−
1. Nitrate in the presence of bromide : (NO3 and Br−). Acidify the water solution with A E A
dil. H2SO4. Add to this solution ammonical silver sulphate to precipitate bromide as AgBr.
−
Filter the ppt. and test the filtrate for NO3 . A E A
RESULT:
Basic Radicals (positive) Acidic Radicals (negative)
1. 1.
2. 2.
VIVA VOCE
1. What is qualitative analysis ? How it differs from quantitative analysis ?
2. What are the different types of qualitative analysis ?
3. What is dry test for ammonium ?
4. What is the use of turmeric paper ?
5. For what test you use starch iodide paper ?
6. What is dry test for chloride ?
7. What is cobalt nitrate test ? When it is performed ?
8. What quantity of original solution you require ? How will you prepare it ?
9. What is solubility product and ionic product ?
237
10. What basic radicals are present in group III A ?

11. What are the group reagents for testing group III B ?
12. Why concentrated solution is required for testing group IV ?
13. What is C.T. for Ni2+ ?
14. What is Nessler's reagent ?
15. What is hypoiodate reagent ?
16. How will you test presence of Cl−, Br− and I− ?
2−
17. What is the test for CO3 ? A E A
18. What is chromyl chloride test ?

−
19. What is C.T. for NO3 ?
A E A
20. Which acidic radical is not detected in dry test ?

21. What is aqua-regia ? Where it is used ?
22. When sodium carbonate extract is required ?
23. What is neutral extract ?
24. What are interfering anions ?
25. Why phosphate is to be removed before testing presence of group III A ?
26. Why borate is removed from the solution ?
27. How borate is removed from the solution ?
28. What is the test for phosphate ?
29. How we detect presence of borate ?
30. What is brown ring test ? How it is performed ?
---
238
Appendices
STOCK SOLUTIONS
(A) Gravimetric Estimations :
1. Ferrous ammonium sulphate solution : Weigh 80.0 g of Ferrous ammonium
sulphate. Transfer it to a 250 ml beaker. Add 100 ml distilled water and stir the solution to
dissolve the salt. Add 2 ml concentrated H2SO4 to avoid hydrolysis and precipitation of iron.
Transfer this clear solution to a 250 ml volumetric flask and dilute it upto the mark with
distilled water. (Give only 10 - 15 ml of this solution for estimation in a 100 ml volumetric
flask.)
2. Nickel sulphate solution : Weigh 6.25 g NiSO4.7H2O. Transfer it to a 250 ml beaker.
Add 100 ml distilled water and stir the solution to dissolve the salt. Add little concentrated
H2SO4 (few drops) to make clear solution. Transfer this clear solution to a 250 ml volumetric
flask and dilute it upto the mark with distilled water. (Give only 10 - 15 ml of this solution for
estimation in a 100 ml volumetric flask.)
3. 1% alcoholic solution of DMG : Dissolve 0.25 g of dimethyl glyoxime in 100 ml ethyl
alcohol. Transfer this solution to 250 ml volumetric flask and dilute upto the mark with ethyl
alcohol.
4. Ammonium aluminium sulphate solution : Weigh 75.0 g of ammonium aluminium
sulphate [(NH4)2SO4.Al2(SO4)3.24H2O]. Transfer it to a 250 ml. beaker. Add 100 ml distilled
water and stir the solution to dissolve the salt. Add little concentrated H2SO4 (few drops) to
make clear solution. Transfer this clear solution to a 250 ml volumetric flask and dilute it upto
the mark with distilled water. (Give only 10 - 15 ml of this solution for estimation in a 100 ml
volumetric flask.)
5. Barium chloride solution : Weigh 11.0 g of BaCl2.2H2O. Transfer it to a 250 ml.
beaker. Add 100 ml distilled water and stir the solution to dissolve the salt. Add little
concentrated HCl (few drops) to make clear solution. Transfer this clear solution to a 250 ml
volumetric flask and dilute it upto the mark with distilled water. (Give only 10 - 15 ml of this
solution for estimation in a 100 ml volumetric flask.)
(B) Volumetric Estimations :
1. Mn by Volhard's Method :
(a) 0.05 N KMnO4 solution : Weigh 1.58 g of KMnO4. Transfer it to a 250 ml beaker.
Add 100 ml distilled water to dissolve the solid. Transfer the resulting solution to a
1000 ml volumetric flask and dilute upto the mark with distilled water.
238
T.Y.B.Sc. Practical Chemistry (Inorganic Practicals) Appendices
(b) Manganese stock solution : Weigh 6.336 g of MnSO4.H2O. Transfer it to a 250 ml.
beaker. Add 100 ml distilled water and stir the solution to dissolve the salt. Add little
concentrated H2SO4 (few drops) to make clear solution. Transfer this clear solution to
a 250 ml volumetric flask and dilute it upto the mark with distilled water. (Give only
10 ml of this solution for estimation in a 100 ml volumetric flask).
3−
2. Estimation of phosphate (PO4 ) from fertilizer :
(a) 1 N NaOH : 40 g of NaOH dissolved in 1000 ml water, dilute to 1000 ml with distilled
water.
(b) 3% ammonium molybdate solution : Dissolve 15 g ammonium molybdate in
500 ml distilled water.
3. Analysis of Brass :
(a) 0.05 N sodium thiosulphate solution : Weigh 12.5 g of Na2S2O3 ⋅ 5H2O. Transfer it
to a 250 ml beaker. Add 100 ml distilled water and stir the solution to dissolve the
solid. Transfer this clear solution to a 1000 ml volumetric flask and dilute it upto the
mark with distilled water.
(b) 2 N NaOH solution : Weigh 80.0 g of NaOH. Transfer it to a 250 ml. beaker. Add
100 ml distilled water and stir the solution to dissolve the salt. Transfer this clear
solution to a 1000 ml volumetric flask and dilute it upto the mark with distilled water.
(c) 2 N acetic acid : Accurately measure 118.0 ml of glacial acetic acid. Carefully transfer
it to 1000 ml volumetric flask. Add distilled water to make upto the mark that is final
volume of 1000 ml.
(d) 5 % KI solution : Weigh 12.5 g of KI. Transfer it to 250 ml beaker. Add about 100 ml
distilled water. Dissolve the salt and transfer this clear solution to a 250 ml volumetric
flask. Dilute the solution upto the mark with distilled water.
4. % Purity of Sodium Chloride :
(a) 0.05 N silver nitrate solution : Weigh 8.494 g of AgNO3. Transfer it to a 250 ml
beaker. Add 100 ml distilled water and stir the solution to dissolve the solid. Transfer
this clear solution to a 1000 ml volumetric flask and dilute it upto the mark with
distilled water.
(b) 5 % potassium chromate solution : Weigh 5.0 g of K2CrO4. Dissolve it in little
distilled water and dilute it to 100 ml with distilled water.
239
(C) Inorganic Preparations :

1. Potassium Trioxalato Ferrate :
(a) 10% oxalic acid : Weigh 25.0 g of H2C2O4 ⋅ 2H2O. Transfer it to a 250 ml. beaker. Add
100 ml distilled water and stir the solution to dissolve the solid. Transfer this clear
solution to a 250 ml volumetric flask and dilute it upto the mark with distilled water.
(b) 0.05 N KMnO4 solution : As given under the experiment Manganese by Volhard's
method.
(c) 2 N H2SO4 : Accurately, measure 56.0 ml of concentrated sulphuric acid. Take about
500 ml of distilled water in a 1000 ml volumetric flask. Add above measured sulphuric
acid slowly into the volumetric flask with constant stirring. Finally dilute the contents
of the flask with distilled water upto the mark.
2. Tetramine Copper (II) Sulphate :
As given under the experiment Analysis of Brass.
3. Potash Alum :
(a) 0.01 M zinc sulphate solution : Weigh 2.87 g of ZnSO4 ⋅ 7H2O. Transfer it to a
250 ml beaker. Add 100 ml distilled water and stir the solution to dissolve the solid.
Transfer this clear solution to a 1000 ml volumetric flask and dilute it upto the mark
(b) 0.01 M EDTA : Weigh 3.722 g of EDTA. Transfer it to a 250 ml beaker. Add 100 ml
distilled water and stir the solution to dissolve the solid. Transfer this clear solution to
a 1000 ml volumetric flask and dilute it upto the mark with distilled water.
(c) Eriochrome black T-indicator : Weigh 0.2 g of indicator powder. Add to it 15 ml
triethanolamine and dilute it by adding 5 ml ethyl alcohol. Stir well to dissolve the
powder. Store in an indicator bottle.
(D) Colorimetric Estimations :
1. Estimation of Iron :
(a) Unknown iron solution : 8.64 g ferric ammonium sulphate + 100 ml conc. HCl dilute
to 1 litre with distilled water (concentration 1 mg/ml).
(b) Known iron solution : Take 100 ml unknown iron solution, dilute to 1 litre with
distilled water (concentration 0.1 mg/ml).
2. Estimation of Cobalt :
(a) Unknown cobalt solution : 2.018 g cobaltous chloride in one litre distilled water
(concentration 1 mg/ml). [Give 6 to 9 ml stock solution in a 100 ml volumetric flask].
(b) Known cobalt solution : Take 100 ml unknown cobalt solution and dilute it to 1 litre
with distilled water (concentration 0.1 mg/ml).
240
3. Estimation of Titanium :
(a) Unknown titanium solution : 11.045 g of potassium titanyl oxalate + 23 g
(NH4)2SO4 + 250 ml concentrated H2SO4 boil, cool and dilute to one litre with distilled
water (concentration 5 mg/ml). [Give 15 to 20 ml stock solution in a 100 ml
volumetric flask].
(b) Known titanium solution : Take 200 ml of unknown titanium solution and dilute to
1 litre with 2 N H2SO4 (concentration 1 mg/ml).
4. Estimation of Iron by Solvent Extraction :
(a) Known Fe3+ solution : Weigh 0.86 g of ferric ammonium on a watch glass. Transfer it
to 250 ml beaker, add 50 ml and stir the solution to dissolve the salt. And 1 ml
concentrated H2SO4 to it to avoid hydrolysis and precipitation of Fe3+ as Fe(OH)3.
If solution is not clear add few drops of H2SO4, to make it clear. Transfer this clear
solution to a 1000 ml volumetric flask and dilute upto the mark with distilled water.
This solution contains 0.1 mg of Fe3+ per ml of the solution.
(b) Unknown Fe3+ solution : Weigh 1.08 g of ferric ammonium sulphate on a watch
glass. Transfer it to 250 ml beaker add 50 ml distilled water and stir the solution to
dissolve the salt. And 1 ml concentrated H2SO4 to it to avoid hydrolysis and
precipitation of Fe3+ as Fe(OH)3. If solution is not clear add few drops of H2SO4 to
make it clear. Transfer this clear solution to a 1000 ml volumetric flask and dilute upto
the mark with distilled water. This solution contains 0.125 mg of Fe+3, per ml of the
solution.
(c) 6% 8-hydroxyquinoline solution : Weigh 60 g of 8-hydroxyquinoline on a watch
glass. Transfer it to a 250 ml beaker. Add 100 ml chloroform and stir the solution well
to dissolve 8-hydroxyquinoline. Transfer the clear solution to a 1000 ml volumetric
flask and dilute it upto the mark with chloroform. This is 6% solution of
8-hydroxyquinoline.
(E) Column Chromatography :
(a) Ferric ion solution : 13.5 g FeCl3 ⋅ 2H2O + 20 ml conc. HCl. Dissolve and dilute it to
100 ml with distilled water.
(b) Cobalt solution : 8 g CoCl2 ⋅ 6H2O + 20 ml conc. HCl. Dissolve and dilute it to 100 ml
(c) Copper solution : 11.2 g CuSO4 ⋅ 5H2O + 20 ml conc. HCl. Dissolve and dilute it to
241
(d) Zinc solution : 7.9 g ZnSO4 ⋅ 7H2O + 10 ml conc. HCl. Dissolve and dilute it to 100 ml
(e) Aluminium solution : 27.9 g Al2(SO4)3 ⋅ 18H2O + 20 ml conc. HCl. Dissolve and dilute
it to 100 ml with distilled water.
(f) Nickel solution : 4.42 g NiSO4 ⋅ 7H2O + 10 ml conc. HCl. Dissolve and dilute it to
SOLUTIONS
(C) Inorganic Preparations – Solutions for Volumetric Analysis :
1. 0.05 N KMnO4 : Dissolve 1.58 g A.R. grade KMnO4 in 500 ml distilled water and
dilute to 1 litre.
2. 0.05 N HCl : Dilute 5 ml conc. HCl to 1 litre with distilled water.
3. 0.025 N Na2S2O3 : Dissolve 6.25 g Na2S2O3 in 500 ml distilled water and dilute to
1 litre.
4. 0.01 M EDTA : Dissolve 3.72 g of disodium salt of EDTA in 500 ml distilled water and
finally dilute to 1 litre.
(D) Colorimetry :
(1) Colorimetric Estimation of Iron :
(i) Iron (III) solution of unknown concentration (1 mg/ml) : Dissolve 7.022 g of A.R.
ferric ammonium sulphate Fe2(SO4)3 ⋅ (NH4)2SO4 ⋅ 24H2O in 100 ml distilled water.
Add 100 ml of A.R. grade HCl and dilute it to 1 litre using distilled water. This gives
solution of concentration 1 mg/ml of Fe. (Give 8–12 ml of this solution in 100 ml
volumetric flask to student.)
(ii) Iron (II) solution of known concentration (0.1 mg/ml) : Take 10 ml of Fe(III)
solution of 1 mg/ml concentration in 100 ml volumetric flask and dilute it to 100 ml.
This gives solution of 0.1 mg/ml concentration.
(iii) 1 : 1 HCl : Take 50 ml A.R. HCl and dilute it to 100 ml in volumetric flask.
(iv) 3% H2O2 solution : Take 10 ml of 100 volume H2O2 and dilute it to 100 ml in
volumetric flask.
(v) 20% NH4SCN solution : Dissolve 20 gm of ammonium thiocyanate in distilled water
and dilute it to 100 ml in volumetric flask.
(2) Colorimetric Estimation of Cobalt :
(i) Cobalt solution of unknown concentration (1 mg/ml) : Dissolve 2.018 gm of
cobaltous chloride CoCl2 ⋅ 6H2O in 50 ml distilled water and dilute it to 1 litre. This
gives concentration 1 mg/ml of cobalt. (Give 8 - 12 ml solution to student as an
unknown.)
242
(ii) Cobalt solution of known concentration (0.1 mg/ml) : Take 10 ml of cobalt

solution of 1 mg/ml and dilute it to 100 ml in volumetric flask. This gives
concentration 0.1 mg/ml of cobalt.
(iii) 50% sodium acetate solution : Dissolve 50 g sodium acetate in 50 ml distilled water
and dilute it to 100 ml in volumetric flask.
(iv) 1% R-nitroso salt solution : Dissolve 1 g R-nitroso salt in 50 ml distilled water and
dilute it to 100 ml in volumetric flask.
(v) 1 : 2 HNO3 solution : Dissolve 33 ml conc. HNO3 in 50 ml distilled water and dilute
to 100 ml in volumetric flask.
(3) Colorimetric Estimation of Titanium :
(i) Titanium solution of unknown concentration (5 mg/ml) : Take 2.76 g of
potassium titanyl oxalate, K2TiO(C2O4)2 ⋅ 2H2O and 5.75 g of ammonium sulphate,
(NH4)2SO4. Add carefully 62 ml of conc. H2SO4 to it. Boil, cool and dilute to 250 ml
with distilled water. This gives concentration 5 mg/ml. (Give 13 to 18 ml of this
solution to students as an unknown.)
(ii) Titanium solution of known concentration (1 mg/ml) : Take 50 ml of titanium
5 mg/ml solution and dilute it to 250 ml using volumetric flask. This gives
concentration of 1 mg/ml of titanium.
(iii) 3% H2O2 : (As above).
(iv) 2 N H2SO4 : Dilute 57 ml conc. H2SO4 to 1 litre.
(4) Solvent Extraction of Iron and Colorimetric Estimation :
(i) Iron (III) solution of unknown concentration (1.5 mg/ml) : Dissolve 12.96 g of
A.R. grade ferric ammonium sulphate, Fe2(SO4)3 ⋅ Al2(SO4)3 ⋅ 24H2O in 100 ml distilled
water and add 25 ml conc. HCl. Dilute the contents to 1 litre in volumetric flask using
distilled water. This gives concentration 1.5 mg/ml. (Give 13 – 18 ml of this solution to
students as an unknown.)
(ii) Iron (III) solution of known concentration (0.1 mg/ml) : Dilute 6.7 ml 1.5 mg/ml
iron solution to 100 ml in volumetric flask. This gives 0.1 mg/ml concentration of iron.
(iii) 6% 8-hydroxyquinoline in chloroform : Dissolve 6 g of 8-hydroxyquinoline in 40 ml
chloroform and dilute it to 100 ml using chloroform.
243
Column Chromatography :
(a) Ferric ion solution : 13.5 g FeCl3 ⋅ 2H2O + 20 ml concentrated HCl. Dissolve and
dilute it to 100 ml with distilled water.
(b) Cobalt solution : 8 g CoCl2 ⋅ 6H2O + 20 ml concentrated HCl. Dissolve and dilute it
to 100 ml with distilled water.
(c) Copper solution : 11.2 g CuSO4 ⋅ 5H2O + 20 ml concentrated HCl. Dissolve and
dilute it to 100 ml with distilled water.
(d) Zinc solution : 7.9 g ZnSO4 ⋅ 7H2O + 10 ml concentrated HCl. Dissolve and dilute it
to 100 ml with distilled water.
(e) Aluminium solution : 27.9 g Al2(SO4)3⋅18H2O + 20 ml concentrated HCl. Dissolve
and dilute it to 100 ml distilled water.
(f) Nickel solution : 4.42 g NiSO4 ⋅ 7H2O + 10 ml concentrated HCl. Dissolve and dilute
it to 100 ml distilled water.
---
244
Course - I
CH-349
ORGANIC CHEMISTRY
PRACTICALS
245
T.Y.B.Sc. Practical Chemistry (Organic Practicals) Separation of Binary Mixtures ….

COURSE – I
CH – 347
Organic Chemistry Practicals

Marks
Q.1. Binary Mixture Separation and Qualitative Analysis 40
Q.2. Organic Estimations/Preparations 30
Q.3. Oral 10
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(A) Separation of Binary Mixtures and

Qualitative Analysis
(Minimum 8 Mixtures)
In S.Y.B.Sc., we have learnt the qualitative analysis of single organic compound. This year
we are going to learn the separation of binary mixture and individual analysis of each
component of the binary mixture.
Systematic Qualitative Analysis of a binary mixture involves following steps :
1. Determination of the type of the binary mixture.
2. Separation of the binary mixture into two components.
3. Re-crystallization of the individual components.
4. Individual analysis of the two components :
(a) Detection of saturation/unsaturation.
(b) Detection of aliphatic/aromatic character.
(c) Detection of elements.
(d) Detection of functional group.
(e) Determination of melting/boiling point.
The nature of the binary mixture can be solid-solid, solid-liquid or liquid-liquid.
(a) Solid-solid mixture [4 Mixtures] :
If the nature of the given binary mixture is solid-solid, it is necessary to find out the type
of the mixture, then separate into individual components using chemical method. The
principle behind the chemical separation is to solubalize only one of the components in one
of the reagents i.e. 10% NaHCO3, 2 N NaOH or 2N HCl. The other insoluble component is
then separated by simple filtration.
(b) Solid-liquid mixture [2 Mixtures] or
(c) Liquid-liquid mixture [2 Mixtures]:
If the nature of the binary mixture is solid-liquid, the liquid component (usually low
boiling) is first separated by simple distillation. In case of liquid-liquid the low boiling
247
(or volatile) component is separated by distillation. The type of the individual components is
then determined.
1. Determination of Type :
To determine the type of the solid-solid binary mixture, following scheme is followed :
Binary mixture (200 mg)
+ 10% NaHCO3 (1 ml), shake

then filter
Filtrate Residue
wash with water
+ 2N HCl then add 2 N NaOH (1 ml)
shake, then filter
If ppt is obtained
acid is present
Filtrate Residue
+ 2 N HCl wash with water

then add 2 N HCl or 1 : 1 HCl
(1 ml), shake, then
If ppt is obtained filter
phenol is present
Filtrate Residue
It is neutral
+ 2 N NaOH
If ppt is obtained
base is present
Conclusion :
The type of the given mixture is _________________.
2. (A) Separation of Solid-Solid mixture :
Six types of solid-solid mixtures can be divided into three groups :
Group I : Acid-Phenol, Acid-Base and Acid-Neutral
Group II : Phenol-Base and Phenol-Neutral
Group III : Base-Neutral
Separation of Group I (Acid-Phenol, Acid-Base or Acid-Neutral) :
Take all the mixture in a beaker and add 10% NaHCO3 (20 ml), stir well till all the
effervescence of CO2 stops. (Add more NaHCO3 if required). Then filter it and wash the
residue (residue is either phenol, base or neutral component) with water and re-crystallize it
248
from aqueous ethanol. Cool the filtrate and acidify it with 2 N HCl (Check with blue litmus
paper). Filter the precipitated acid on a Buchner funnel. Dry and re-crystallize it from hot
water or aqueous ethanol.
Separation of Group II (Phenol-Base or Phenol-Neutral) :
Take all the mixture in a beaker and add to 2 N NaOH (20 ml), stir well till (Add more
NaOH if required). Then filter it and wash the residue (residue is base or neutral component)
with water and re-crystallize it from aqueous ethanol. Cool the filtrate and acidify it with
2 N HCl (Check with blue litmus paper). Filter the precipitated phenol on a Buchner funnel.
Dry and re-crystallize it from aqueous ethanol.
Separation of Group III (Base-Neutral) :
Take all the mixture in a beaker and add to 2 N HCl (20 ml), stir well till (Add more HCl if
required). Then filter it and wash the residue (neutral component) with water and
recrystallize it from aqueous ethanol. Cool the filtrate and make it alkaline with 2 N NaOH
(Check with red litmus paper). Filter the precipitated base on a Buchner funnel. Dry and
recrystallize it from aqueous ethanol.
2. (B) Separation of Solid-Liquid or Liquid-Liquid mixture :
Solid-liquid mixture could be
(a) Solid + Non-volatile liquid or
(b) Solid + Volatile liquid.
Liquid-liquid mixture can be
(a) Volatile + Non-Volatile or
(b) Non-volatile − Non-volatile.
The solid-liquid mixture could appear as a heterogeneous mixture (solid is immiscible in
liquid) or homogeneous mixture (the solid is miscible in liquid). To find out whether the
homogeneous mixture is a solid-liquid or liquid-liquid mixture, place few drops of the
mixture on a watch glass and blow it with mouth, if solid is obtained then the nature of the
mixture is solid-liquid, otherwise it is a liquid-liquid mixture.
Volatility of one component : To find whether one liquid component is volatile or not,
place few drops of the mixture in a sodium fusion tube and place a capillary with open
mouth dipped in the fusion tube (sealed at the top). Heat the sodium fusion tube on a
boiling water bath. If continuous bubbles start appearing then one component is volatile.
Separation of solid-liquid or liquid-liquid mixture (when one component is volatile) :
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Place the mixture in a round bottom flask (25 ml) with a porcelain piece. Place the
Hickman head and the water condenser as shown in Fig. 1.
Water condenser
Rubber tube
pipette
Water
Hickman head
Pure liquid
Distillation flask
Water bath
Binary mixture
Fig. 1
Heat the flask on a boiling water bath till all the volatile component is collected in the
groove of the Hickman head. Collect this volatile component with the help of a Pasteur
pipette in a vial (Seal it or keep it in ice-bath so the volatile liquid does not evaporate). Pour
the residual liquid of the round bottom flask in a beaker and allow it to evaporate, so that
any volatile component still left gets evaporated. The residue could separate as a solid or a
liquid depending on the nature of the mixture.
Note : Two volatile components mixture cannot be given, as they cannot be separated
by simple distillation method.
(1) Type determination of volatile liquid : Before determining the type of volatile
liquid, check its miscibility in water, by mixing few drops of liquid with few drops of water in a
test tube.
If it is immiscible in water, then follow the procedure for type determination as given in
(1) for solid-solid mixture. Note that the individual component will not precipitate out during
regeneration from the filtrate (as it is a liquid) but it will separate as an oil which in turn can
be separated out using a Pasteur pipette.
(2) Type determination of water miscible liquids : If the liquid to be analysed is
miscible in water, then for the determination of type of this liquid, we cannot use the
procedure given in (1), because the reagents used are aqueous reagents in which the water
miscible liquid will not separate as an oil. In such cases, following procedure is adopted.
Sr. No. Test Observation Inference
1. Litmus test* Blue litmus turns red. Liquid is acidic or
phenolic.
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2. Liquid + 2-3 drops of Red litmus turns red. Liquid is basic.

neutral FeCl3. Blue/Green/Violet colour. Liquid is phenolic.
*To test with litmus paper, dip the end of a small glass rod into the liquid and then gently
touch the litmus paper with the rod. Do not dip the litmus paper into the solution.
If both of the above tests are negative then the given liquid is Neutral in nature.
Many volatile liquids are neutral in nature.
Separation of liquid-liquid mixture (both liquids are non-volatile) : Follow the
procedure for type determination as given in (1) for solid-solid mixture. For separation, follow
the procedure given in 2 (A).
Note : The individual components do not precipitate out during regeneration from the
filtrate (as they are liquids) but they separate out as oils which in turn are separated out using
Pasteur pipette.
Individual Analysis of Acid, Phenol, Base and Neutral Component :
1. Determination of saturation/unsaturation :
An unsaturated compound is one which has multiple bonds : double or triple bond.
These multiple bonds give characteristic electrophilic addition reactions as well as oxidation
reactions.
Note : Aromatic ring, even though contains alternate double bonds, is a saturated
compound as it does not give electrophilic addition reaction. Aromatic ring gives
electrophilic substitution reactions.
The presence of unsaturation is determined by following two tests :
(a) Br2 in CCl4 test
(b) Baeyer’s test or KMnO4 test.
Both these tests have to be performed with care to arrive at any conclusion.
Test Observation Inference
1. Take 1 ml Br2 in CCl4 in a (a) if brown colour of bromine Compound is saturated
small test tube, add a does not disappear.
little amount of given (b) if brown colour disappears Compound is saturated
substance in CCl4 with with precipitation of solid
shaking and hold a glass in the test tube and white
rod dipped in NH3 on the fumes on the glass rod.
mouth of the test tube. (c) if brown color disappears
Compound is unsaturated
with no white fumes on the
glass rod.
251
Br
R R CCl4 R R
C C + Br2 C C
R' R' R' R'
Br
Alkene Brown
colour Dibromo derivative
Brown colour disappears
2. Baeyer’s test : Take a (a) Pink colour of KMnO4 Compound is unsaturated
little amount of given disappears
substance in a small test (b) No decolourization. Compound is saturated
tube + 10% NaHCO3
(1 ml) + dil. KMnO4
(5 drops) with shaking.
R R R R
C C + Alk. KMnO4 C C + MnO2 + 2 KOH
R' R' R' R'
Pink OH OH
Alkene colour Dihydroxy derivative Brown
Conclusion :
The given organic compound is ___________. (Saturated/Unsaturated)
2. Determination of Aliphatic/Aromatic Nature :
Heat a little substance on a (a) No sooty flame Compound is aliphatic
clean copper gauze (b) Sooty flame Compound is aromatic
Conclusion :
The given organic compound is ___________. (Aliphatic/Aromatic)
3. Detection of Elements :
Organic compounds always contain C and H, while O may or may not be present, hence
written inside the braces. It is often valuable to determine the existence of other elements N,
S, halogens, as the knowledge of the elemental composition is essential for the selection of
appropriate classification tests for functional groups. The detection of these elements is done
by sodium fusion test (Lassaigne’s test).
Sodium Fusion Test :
1. Place a small size (wheat size) of freshly cut sodium metal in a Borosil or Pyrex glass
dry test tube (10 × 80 mm).
2. Heat the test tube until the sodium metal melts and turns into a silver ball. Place
small amount of the given solid compound onto the sodium metal without touching
252
the side of the test tube. [Note : The amount of compound should be less than the
amount of sodium]
Note : If the compound is liquid, add one drop using capillary. If the compound is
low boiling liquid then mix small amount of powdered sucrose with it prior to its
addition into the test tube.
3. Heat the lower part of the test tube gently to initiate the reaction (reaction of sodium
metal with the given compound) and then to red hot for 1 min.
4. Cool the test tube and add few drops of ethanol to dissolve any unreacted sodium.
Repeat adding ethanol until no further bubbles of hydrogen gas are evolved.
5. Add 2 ml of distilled water to this solution, again heat and then filter using pasture
pipette fitted with a cotton plug.
Use this sodium fusion filtrate to test for the presence of sulphur, nitrogen or halogens.
Test for Sulphur :
1. Place 1 drop of sodium Black precipitate Sulphur present
fusion extract on a porcelain
tile + 1 drop acetic acid +
2 drops 1% lead acetate
solution
2Na + S → Na2S
σρ
Na2S + 2CH3COOH → 2CH3COONa + H2S
(CH3COO)2Pb + H2S → PbS↓ + 2CH3COOH
Black ppt.
2. Place 1 drop of sodium Deep blue-violet color Sulphur present
fusion extract on a porcelain
tile + 2 drops of 2% sodium
nitroprusside solution
2Na + S → Na2S
Na2S + Na2[Fe(CN)5NO] → Na4[Fe(CN)5NOS]
Sodium nitroprusside Violet colour
Test for Nitrogen :
Place 1 drop of sodium Prussian blue or bluish green Nitrogen present
fusion extract on a porcelain color
tile + 1 drop 2 N NaOH. To
this add a pinch of FeSO4
crystals (green colored) and
mix it with glass rod. Then
253
add 1 drop of dil. H2SO4 or

HCl.
Na + C + N → NaCN
FeSO4 + 6 NaCN → Na4[Fe(CN)6] + Na2SO4
Sodium ferrocyanide
3Na4[Fe(CN)6] + 2Fe2(SO4)3 → Fe4[Fe(CN)6]3 + 6Na2SO4
Ferric ferrocyanide
Prussian blue colour
Test for Nitrogen and Sulphur together :
Sodium fusion extract and Blood red colour Nitrogen and sulphur both
few drops of FeCl3 solution present.
Na + C + N + S → NaCNS
FeCl3 + 3NaCNS → Fe(CNS)3 + 3NaCl
Blood red colour
Test for Halogens :
1. Place 20 drops of sodium White/ yellow precipitate Halogens present
fusion extract in a small
test tube + 1 drop conc.
HNO3. Then add few
drops of AgNO3 solution.
dil. HNO3
NaX + AgNO3 ⎯⎯⎯⎯→ AgX↓ + NaNO3
ppt.
2. Place 20 drops of sodium (i) CHCl3 layer colourless Chlorine is present
fusion extract + dil HNO3
(4 drops). To this add
(ii) CHCl3 layer brown Bromine is present
CHCl3 (20 drops) +
freshly prepared Cl2
water (10 drops). Shake (iii) CHCl3 layer violet Iodine is present
well and allow to stand
CCl4
NaBr + Cl2 2 NaCl + Br2 (Brown colour)
CCl4
NaI + Cl2 2 NaCl + I2 (Violet colour)
Conclusion :
254
The given organic compound has ___________ elements. (N, S, Halogens)

Once the type and elements of given organic compound is known, organic compounds
can be classified into four groups for their functional group detection.
Group I : Compounds containing C, H, (O)
Group II : Compounds containing C, H, (O) and N
Group III : Compounds containing C, H, (O), N and S
Group IV : Compounds containing C, H, (O), Halogens
4. Detection of Functional Groups :
Group I : Compounds containing C, H, (O)
If the type is Acid [Check for –COOH, −OH, −CO−, −COOR functional groups]
If the type is Phenol [Check for –OH, −CO−, −COOR functional groups]
If the compound is Neutral [Check for –CO−, −COOR, carbohydrate functional groups]
Group II : Compounds containing C, H, (O) and N
If the type is Acid [Check for –COOH, −OH, −CO−, −COOR, −NH2 (−NHR, −NR2), −NO2,
−CONH2, −NHCOCH3 functional groups]
If the type is Phenol [Check for –OH, –CO–, –COOR, –NH2 (–NHR, –NR2), –NO2,
–CONH2, –NHCOCH3 functional groups]
If the type is Base [Check for –CO–, –COOR, –NH2 (–NHR, –NR2), –NO2 functional groups]
If the compound is Neutral [Check for –CO–, –COOR, –NO2, –CONH2, –NHCOCH3
functional groups]
Group III : Compounds containing C, H, (O), N and S
If the type is Acid [Check for –COOH, –OH, –CO–, –COOR, –NH2 (–NHR, –NR2), –NO2,
If the type is Phenol [Check for –OH, –CO–, –COOR, –NH2 (–NHR, –NR2), –NO2,
If the type is Base [Check for –CO–, –COOR, –NH2 (–NHR, –NR2), –NO2 functional groups]
If the compound is Neutral [Check for –CO–, –COOR, –NO2, –CONH2, –NHCOCH3
functional groups].
Note : There are no separate tests for sulphur containing functional groups. Sulphur can
exist as –SO3H (sulphonic acid) or –CS–NH2 (thioamide) . These functional groups give the
same test as given by –COOH and –CO–NH2 respectively.
Group IV : Compounds containing C, H, (O) and Halogens
If the type is Acid [Check for –COOH, –OH, –CO–, –COOR, –X functional groups]
If the type is Phenol [Check for –OH, –CO–, –COOR, –X functional groups]
If the compound is Neutral [Check for –CO–, –COOR, –X functional groups]
Individual functional group tests :
255

1. For acid (–COOH) Substance dissolves with Acid is present and
group : effervescence of CO2 and confirmed.
Take 1 ml of 10% reappears by adding
NaHCO3 in a small test conc. HCl
tube, add a pinch of
given substance without
shaking
O O O
HCl
+ NaHCO3 + CO2 + NaCl
C C C
R OH R O Na R OH
Acid Water soluble salt Acid ppt.

2. For phenolic (–OH) Blue / green / violet colour or Phenol is confirmed.
group : red brown colour
Take a pinch of the given
compound + 1 ml of
alcohol + 2-3 drops of
aq. FeCl3.
3 ArOH + aq. FeCl3 ⎯⎯→ Fe(OAr)3 + 3HCl

Blue/Green/Violet
or Red brown colour

3. Carbonyl (–CO–) group : Yellow or red precipitate Carbonyl group confirmed
Take a pinch of the given
compound + 1 ml of
alcohol + 2-3 drops of
2.4-DNP reagent
O R
H
+ O2N NH-NH2 O2N N-N = C
C
R R' R'
NO2 NO2
Aldehyde 2, 4-DNP Yellow or Red ppt.
or Ketone
Tests for Aldehydes :
(a) Tollen’s test :
256
Given compound Silver gets deposited on the Aldehyde group present

(5-6 drops) + Tollen’s inner walls of the tube (silver
reagent (1 ml) in a small test mirror formation)
tube. Warm gently on water
bath for 5 min. (Note : The
test tube should be washed
with conc. HNO3 and
distilled water prior to this
test).
O
+ 2 [Ag(NH3)]2+ + 3OH Ar-COO + 2H2O + 2Ag + 4NH3
C Tollen's Black
Ar H reagent ppt.
Aldehyde
(b) Fehling’s test :

Given compound Red precipitate of Cu2O Aldehyde group present
(5-6 drops) + Fehling’s (Ar/R–CHO)
solutions A and B (1 ml) in a
small test tube. Warm
gently on water bath for
2 min.
O
2 NaOH
+ 2 Cu(OH)2 citrate Ar-COO Na citrate + Cu2O + H2O
C -3 H2O
Fehling's Red
Ar H reagent ppt.
Aldehyde
(c) Schiff’s reagent test :

Given compound Pink colour develops in the Aldehyde group present
(5-6 drops) + Schiff’s organic layer
reagent (0.5 ml) in a small
test tube.
H2N
SO3H O
-2H2O R
H2N NH2 + 2 C N-CH
C + 2H2SO3
R H SO3H
Aldehyde
R
CH-HN
NH2 HO3S
Schiff's reagent (colourless) Pink
257
If aldehyde group is absent assume the compound has ketone group.

(d) Iodoform test :
Given compound + NaOH Yellow precipitate Methyl ketone present
(2 ml) + I2 solution (5 ml) (CH3–CO–)
and then heat
O I2 O
+ NaOH CHI3 +
C C
H3C R R O Na
Methyl ketone Iodoform

4. Ester (–COOR) group :
(a) Phenolphthalein test : Pink colour disappears Ester group is present
To a very dilute NaOH
solution add 1 drop of
phenolphthalein to obtain
very faint pink color. (Note :
If the pink colour is very
dark, dilute it with water till
faint pink colour is
obtained). To this add 2-3
drops of the given
compound and heat it.
O O
D
+ [NaOH + Phenolphthalein] + R'-OH + Phenolphthalein
C C
R OR' Pink colour R O Na Colourless
Ester
(b) Hydroxamic test :
Substance + alcoholic Red-violet colour develops Ester group is confirmed
NH2OH.HCl + 10% NaOH
(till alkaline). Heat to boil,
cool and neutralize with
dil. HCl. Then add 1-2 drops
of FeCl3.
NaOH
(i) RCOOR’ + NH2OH.HCl ⎯⎯⎯→ R−CO−NH−OH + R’−OH + NaCl + H2O
258
R O
(ii) 3R−CO−NH−OH + FeCl3
⎯⎯→
Hydroxamic acid Fe
+ 3HCl
HN
3
O
Red-violet colour

5. Carbohydrate group :
(a) Molish test : Violet red colouration at the Carbohydrate present
Compound + 3-4 drops of junction of the two layers
α-naphthol in alcohol. Shake
and then add 5 drops of
conc. H2SO4 from the walls of
the tube.
OH O
H
CHO C CH2OH
H2SO4 (CHOH)4
(CHOH)4 +
CH2OH
Glucose a-Naphthol Violet-red colour
(b) Compound + conc. H2SO4: Charring of the substance Carbohydrate present
Cn(H2O)n + H2SO4 → nC + nH2O

Charcoal
Hydrocarbons (Water insoluble liquid or solid)

If none of the above functional group is present then the given compound is
hydrocarbon.
6. Nitro (–NO2) group :

(a) Neutral reduction test : Black or grey precipitate Nitro group present.
Compound + 1ml of alcohol
+ 6 drops CaCl2 + pinch of
Zn dust. Heat to boiling for
at least 4 minutes and then
filter into Tollen’s reagent.
259
NO2 NHOH NO
CaCl2/Zn Tollen's
+ Ag + NH3 + H2O
-H2O reagent
Black
ppt.
Hydroxylamine
(b) Ferrous hydroxide test :

Compound + freshly Red-brown precipitate Nitro group is confirmed
prepared 5% ferrous
ammonium sulphate
solution + 1 drop of
dil. H2SO4 + excess of KOH.
Shake the tube quickly
Ar-NO2 + 6 Fe(OH)2 + 4 H2O Ar-NH2 + 6 Fe(OH)3
Blue Brown
colour
7. Test for Primary/ (i) Yellow solid appears. Secondary amine present
Secondary/Tertiary (ii) Red colouration which Tertiary amine present and
amines : turns green solid on confirmed
Take a pinch of the given addition of NaOH
compound + few drops of (iii) No colouration but on
Primary amine present and
conc. H2SO4. Add excess of addition of β-naphthol in confirmed
NaNO2 solution. NaOH gives orange
dyestuff
HONO
(i) C6H5NHR C6H5 N N O
(NaNO2 + H2SO4)
R
Secondary Yellow oil (N-Nitroso compound)
amine or solid
R R
(i) HONO
(ii) C6H5N N C6H4 N O
R (ii) NaOH R
Green ppt. (p-Nitroso compound)
Tertiary
amine N N C6H5
OH
HONO b-Naphthol
(iii) C6H5NH2 C6H5-N N
(NaNO2 + H2SO4) in NaOH
Primary amine Orange dye
260
8. Anilide (−NHCOCH3) group :

Given compound + few drops of
conc. HCl. Boil for 3 min, then cool Orange dyestuff Anilide present
and add excess of NaNO2 solution.
Then add β-naphthol in NaOH
D
(i) Ar-NH-CO-R + HCl Ar-NH2 + R-COO Na
Primary
amine
N N Ar
OH
HONO b-Naphthol
(ii) Ar-NH2 Ar-N NCl
(NaNO2 + HCl) in NaOH
Primary amine Orange dye
9. Amide/Thioamide
(–CO–NH2/–CSNH2) group : Evolution of NH3 which Amide present
Compound + NaOH (1 ml) and turns moist turmeric paper
boil well. red
X X
D
+ NaOH + NH3
C C
R NH2 R O Na
X = O, Amide
X = S, Thioamide
10. Halogen (–X) group : (i) Precipitate Aliphatic halogen

Compound + NaOH (1 ml) compound
and boil well. Neutralize (ii) No precipitate
with HNO3 and add AgNO3 Aromatic halogen
solution. compound
261
i) R-X + NaOH R-OH + NaX

HNO3
ii) NaX + AgNO3 AgX + NaNO3
X = Cl White
= Br Yellowish white
=I Yellow/Violet
5. Determination of Melting/Boiling Point :

(A) Melting Point :
Melting point is defined as the temperature at which the thermal energy of the particles
overcomes the inter crystalline forces of attraction which holds them together.
Procedure for determining the melting point :
1. Fill the capillary, sealed at one end, with powdered sample by gently tapping the
capillary on the table.
2. Repeat this procedure till sufficient quantity is present in the capillary.
3. Attach the capillary to the thermometer with the help of a thread such that the lower
end of the capillary and the thermometer bulb are at the same level.
4. Insert the thermometer in the Thiele’s tube such that only the thermometer bulb is
dipped inside the paraffin oil.
5. Heat the lower side arm of the Thiele’s tube with the help of the burner (blue flame)
slowly back and forth. If the heating is too fast remove the burner for few seconds,
and then resume heating.
6. The rate of heating should be low near the melting point (about 1°C/min).
7. Record the exact melting point of the compound.
262
Capillary Sealed capillary Sealed capillary Sealed capillary

(i) (ii) with compound attached to the
(iii) thermometer
(iv)
Thermometer
attached with capillary
Thiele's tube
Paraffin oil
Burner
(B) Boiling Point :

Boiling point is defined as the temperature at which the vapour pressure of the liquid
becomes equal to the atmospheric pressure.
Procedure for determining the boiling point :
263
Sealed capillary Sodium fusion Capillary inserted Sodium fusion

(i) tube with liquid with open end tube attached to the
compound dipped in the liquid thermometer
(ii) (iii) (iv)
1. Take a sodium fusion tube and add few drops of the liquid sample into it.
2. Seal one end of the capillary and insert it in the fusion tube with its open end dipped
in the liquid.
3. Tie this assembly to the thermometer with the help of a thread such that the lower
end of the sodium fusion tube and the thermometer bulb are at the same level.
4. Insert the thermometer in the Thiele’s tube such that only the thermometer bulb is
dipped inside the paraffin oil.
5. Heat the lower side arm of the Thiele’s tube with the help of the burner (blue flame)
slowly back and forth. If the heating is too fast remove the burner for few seconds,
and then resume heating.
6. Stop heating and record the temperature when vigorous, continuous bubbling starts.
(If the bubbling is not continuous then continue heating). Continue looking at the
fusion tube till the last bubble comes out. At this point the liquid rises in the capillary.
Record this temperature as the boiling point.
7. Repeat this procedure till constant boiling point is recorded.
Result Table :
Sr. No. Description Component 1 Component 2
1. Nature of the given binary mixture
2. Type of the given substance
3. Aliphatic/Aromatic
4. Saturation/Unsaturation
5. Elements
6. Functional groups
7. Melting / boiling point
VIVA VOCE
264
1. What is organic qualitative analysis ?

2. What are the four main types of organic compounds ?
3. In solid - solid binary mixture, Neutral-neutral type is not given. Why ?
4. What is the principle of binary mixture separation ?
5. How will you separate the following mixtures ?
(a) Acid-phenol (b) Acid-base
(c) Acid-neutral (d) Phenol-base
(e) Phenol-base (f) Base-neutral
6. Why acid-phenol mixture is not separated by using 10% NaOH solution ?
7. After separation of mixture why is it essential to purify the individual components ?
8. What do you mean by volatile liquid ? How is it detected ?
9. NaCl and CHCl3 both contain Cl but AgNO3 gives precipitate with NaCl but not with
CHCl3. Why ?
10. Why do aromatic compounds burn with sooty flame ?
11. How will you detect the presence of S, N, and halogen in an organic compound ?
12. What happens to the organic compound when it is fused with sodium metal ?
13. How will you separate solid-liquid mixture ?
14. Why sodium metal is kept under kerosene ?
15. Can potassium, lithium or magnesium be used instead of sodium in making
Lessaigne’s reagent ?
16. What are the functional group tests for the following groups :
(a) Carboxylic (b) Phenolic
(c) Primary amine (d) Secondary amine
(e) Tertiary amine (f) Ester
(g) Anilide (h) Amide
(i) Nitro (j) Carbonyl
(k) Aldehyde (l) Ketone
(m) Methyl ketone.
---
265
(B) Organic Estimations
(Any Four)
Experiment No. 1
Estimation of Acetamide
Aim :
To determine the amount of amide (acetamide) in the given solution.
Principle :
Amides are carboxylic acid derivatives when it is heated with alkali it undergoes
hydrolysis to form the salts of carboxylic acids with evolution of ammonia gas.
Acetamide also on hydrolysis by an alkali forms the salts of carboxylic acids with
evolution of ammonia gas. For estimation (i.e. to find out the amount of acetamide) a known
amount of standard alkali (NaOH or KOH) is added to acetamide solution. After hydrolysis
the unused alkali is determined by titrating it against a standard 0.05 N HCl solution.
The amount of acetamide present in the given sample solution is estimated by measuring
the volume of alkali required for hydrolysis in terms of 0.05 N HCl solution.
Reactions :
General reaction
Hydrolysis
RCONH2 + KOH ⎯⎯⎯⎯⎯→ RCOOK + NH3 ↑
Reactions with acetamide
1. Back titration :
Hydrolysis
CH3CONH2 + KOH ⎯⎯⎯⎯⎯→ CH3COOK + NH3 ↑
Acetamide (Excess) Potassium acetate
2. Blank titration :
KOH + HCl ⎯⎯→ KCl + H2O
(Unreacted)
Chemicals :
(i) Acetamide solution (10-15 ml) (unknown concentration)
(ii) 0.5 N KOH
(iii) 0.05 N HCl (exact)
(iv) Phenolphthalein indicator.
265
T.Y.B.Sc. Practical Chemistry (Organic Practicals) Organic Estimations
Procedure :
Part I : Back Titration :
1. Transfer the given acetamide solution in the 150 ml conical flask. Add 10 ml 0.5 N
KOH solution by means of common burette to the given solution of acetamide and
one test tube of water.
2. Add one porcelain piece in the flask (used for even heating). Place funnel in the
mouth of the flask and heat it on a sand bath (one hour) till the evolution of
ammonia is complete (as tested by turmeric paper, it should not turn red).
3. Then cool the flask and dilute the contents to 100 ml in volumetric flask with distilled
water. Mix it well and fill this diluted solution in the burette No. 1.
4. Fill the burette No. 2 with 0.05 N HCl (exact).
5. Take exactly 9 ml of diluted acetamide solution in a conical flask from burette No. 1.
Add one test tube of distilled water and two drops of phenolphthalein indicator. Pink
colour is developed.
6. Titrate it against 0.05 N HCl (exact) solution from burette No. 2 till the pink colour
disappears. Note down the burette reading as Y1 ml.
7. To the same conical flask add 1 ml of diluted acetamide solution from burette No. 1
and titrate it against 0.05 N HCl (exact) solution from burette No. 2 till the pink colour
8. Again to the same conical flask add 1 ml of diluted acetamide solution from burette
No. 1 and titrate it against 0.05 N HCl (exact) solution from burette No. 2 till the pink
colour disappears. Note down the burette reading as Y3 ml.
Procedure :
Part II : Blank Titration :
1. Take 10 ml of 0.5 N KOH (approx.) solution from the common burette and dilute to
100 ml in a 100 ml volumetric flask. And fill in burette No. 1 again. This will form the
0.05 N KOH solution.
2. Fill the burette No. 2 by 0.05 N HCl (exact).
3. Take exactly 9 ml of 0.05 N KOH solution in a conical flask from burette No. 1. Add
one test tube of distilled water and two drops of phenolphthalein indicator. Pink
disappears. Note down the burette reading as X1 ml.
5. To the same conical flask add 1 ml of 0.05 N KOH solution from burette No. 1 and
titrate it against 0.05 N HCl (exact) solution from burette No. 2 till the pink colour
6. Again to the same conical flask add 1 ml of 0.05 N KOH solution from burette No. 1
266
Observation Table :
Burette No. 1 : Diluted acetamide solution Burette No. 2 : 0.05 N HCl
Indicator : Phenolphthalein End point : Pink to colourless
Reading (B.R.) ml
Reading Mean B.R. (ml)
I II III
Burette No. 1 9 ml 10 ml 11 ml 10 ml
(acetamide solution)
Burette No. 2 (HCl) Y1 + Y 2 + Y3
Y=
Y1 = …… ml Y2 = …… ml Y3 = …… ml 3
Y = …… ml.
Burette No. 1 : 0.05 N KOH solution Burette No. 2 : 0.05 N HCl
Reading (B.R.) ml
I II III
Burette No. 1 (KOH) 9 ml 10 ml 11 ml 10 ml
Burette No. 2 (HCl) X1 = …… ml X2 = …… ml X3 = …… ml X1 + X2 + X3
X=
3
X = …… ml.
Calculations :
Volume of KOH required for 10 ml of dil. acetamide solution in terms of
0.05 N HCl = x − y = …… ml
Hydrolysis
RCONH2 + KOH ⎯⎯⎯⎯→ RCOOK + NH3↑ and
KOH + HCl ⎯⎯⎯⎯→ KCl + H2O
According to reactions :
1 mole of KOH = 1 mole of acetamide
1000 ml 1 N KOH = 59 gms of acetamide
i.e. 1000 ml 1 N HCl = 59 gms of acetamide
0.05 × 59
So, 1 ml 0.05 N HCl = = 0.00295 gms of acetamide.
1000
(X − Y) ml 0.05 N HCl = (X − Y) × 0.00295 g of acetamide
= ‘A’ gms of acetamide
i.e. 10 ml diluted solution contains = ‘A’ gms of acetamide
100 ml diluted solution contains = (A × 10) = Z gms of acetamide
267
Result Table :
1. Volume of 0.05 N HCl (exact) required for blank titration. X = …….. ml
2. Volume of 0.05 N HCl (exact) required for back titration. Y = …….. ml
3. Volume of KOH used by 10 ml of diluted solution in terms of (X − Y) = …… ml
0.05 N HCl (exact)
4. Amount of acetamide in the given solution ‘Z’ = …….. gms.
Experiment No. 2
Estimation of Glucose
Aim :
To determine the amount of glucose in the given solution by hypoiodite method.
Reactions :
I2 + Na2CO3 NaI + NaOI + CO2
Sodium hypoiodide
CHO COOH
(CHOH)4 + NaOI (CHOH)4 + NaI
CH2OH CH2OH
Glucose Gluconic acid
NaOI + NaI + 2HCl 2NaCl + H2O + I2

(Unreacted)
I2 + 2Na2S2O3 2NaI + Na2S4O6

Principle :
Glucose has an aldehydic functional group and it is a reducing sugar. Iodine in Na2CO3
solution produces excess NaOI. This oxidizes quantitatively glucose into gluconic acid.
On acidifying the reaction mixture with HCl, the unreacted NaOI liberates free iodine which
can be titrated against standard Na2S2O3 solution using starch indicator.
Requirements :
1. Glucose solution given in a 100 ml measuring flask.
2. 0.05 N Na2S2O3 solution.
3. 0.05 N I2 solution.
4. 15% Na2S2O3 solution.
5. 1 N HCl.
6. Starch solution.
268
Procedure :
Part I : Back Titration
1. Fill the burette-1 with 0.05 N Na2S2O3 solution.
2. Fill the burette-2 with 0.05 N I2 solution.
3. Dilute the given glucose solution with distilled water upto the mark in a 100 ml
measuring flask and fill this diluted solution in burette-3.
4. Take three 250 ml stoppered bottles and number them as 1, 2 and 3.
5. Take 10 ml of diluted glucose solution by using burette - 3 into a bottle No. 1. Add
5 ml of 15% Na2CO3 solution by measuring cylinder. Add to it 10 ml of 0.05 N
I2 solution from burette-2. Similarly prepare other two bottles and shake well.
6. Keep these three bottles for 30 minutes in dark for the completion of reaction.
7. After 30 minutes, take out bottle-1 and add 10 ml of 1 N HCl by a cylinder and shake
well. The solution becomes orange red due to liberation of I2.
8. Titrate the liberated iodine slowly against 0.05 N Na2S2O3 from burette-1 till the
solution becomes faint yellow.
9. Then add 1 ml of starch indicator, blue color will be developed, add more 0.05 N
Na2S2O3 dropwise from the burette-1 till blue color disappears. Record the burette
reading (Y1).
10. Similarly, take reading for other two bottles and record the readings (Y2 and Y3).
Part II : Blank Titration
1. Take 10 ml of 0.05 N I2 solution from burette - 2 in a stoppered bottle. Add 5 ml of
15% Na2CO3 solution by measuring cylinder and one test tube of distilled water.
(Do not wait for 30 minutes).
2. Then add 10 ml of 1 N HCl by a cylinder and shake well. The solution becomes
orange red due to liberation of I2.
3. Titrate the liberated iodine slowly against 0.05 N Na2S2O3 from burette-1 till the
solution becomes faint yellow.
4. Then add 1 ml of starch indicator, blue colour will be developed, add more 0.05 N
Na2S2O3 dropwise from the burette-1 till blue colour disappears. Record the burette
reading (X1).
5. Similarly, repeat the procedure twice and record the readings (X2 and X3).
269
Observation Table :
Burette No. 1 : 0.05 N Na2S2O3 solution Burette No. 2 : 0.05 N I2
Indicator : Starch solution End point : Blue to colourless
Readings I II III C.B.R.
Burette-2 0.05 N I2 10 ml 10 ml 10 ml
Burette-1 0.05 N Na2S2O3 Y1 = …… ml Y2 = …… ml Y3 = …… ml Y = …… ml
Burette No. 1 : 0.05 N Na2S2O3 solution Burette No. 2 : 0.05 N I2
Indicator : Starch solution End point : Disappearance of blue colour
Readings I II III C.B.R.
Burette-2 0.05 N I2 10 ml 10 ml 10 ml
Burette-1 0.05 N Na2S2O3 X1 = …… ml X2 = …… ml X3 = …… ml X = …… ml
Volume of iodine consumed in terms of 0.05 N Na2S2O3 solution for 10 ml of diluted
glucose solution.
2Na2S2O3 ≡ I2 ≡ Glucose
Calculations :
From the reactions,
2 moles of Na2S2O3 = 1 mole of glucose
= 180 gms of glucose
So, 1000 ml 1 N Na2S2O3 = 90 gms of glucose
So, 1 ml 0.05 N Na2S2O3 = 0.0045 gms of glucose
So, (X − Y) ml 0.05 N Na2S2O3 = (X − Y) 0.0045 gms of glucose
= ………. ‘A’ gms of glucose
Thus 10 ml diluted solution of glucose contains = ‘A’ gms of glucose
So, 100 ml diluted solution of glucose contains = A × 10 = Z gms of glucose
Result Table :
1. Volume of 0.05 N Na2S2O3 for blank titration X = ………. ml
2. Volume of 0.05 N Na2S2O3 for back titration Y = ………. ml
3. Volume of iodine consumed in terms of 0.05 N (X − Y) = ………. ml
Na2S2O3 solution for 10 ml of diluted glucose solution
4. Amount of glucose in the given solution Z = ………. g
270
Experiment No. 3
Estimation of Ethyl Benzoate
Aim :
To determine the amount of ester (ethyl benzoate) in the given solution.
Principle :
Esters are also carboxylic acid derivatives, when it is heated with alkali it undergoes
hydrolysis to form the salts of carboxylic acids and alcohol. The ease of reaction depends on
the solubility of esters. Water-soluble esters are generally hydrolyzed by aqueous alkali and
water insoluble esters by alcoholic alkali. Ethyl benzoate is insoluble in water.
Ethyl benzoate on hydrolysis by an alcoholic alkali (NaOH or KOH) gives benzoate salts
and alcohol. For estimation (i.e. to find out the amount of ethyl benzoate), a known amount
of standard alkali (NaOH or KOH) is added to ethyl benzoate solution. After hydrolysis the
unused alkali is determined by titrating it against a standard 0.05 N HCl solution.
The amount of ethyl benzoate present in the given sample solution is estimated by
measuring the volume of alkali required for hydrolysis in terms of 0.05 N HCl solution.
Reactions :
General reaction
Hydrolysis
RCOOR' + KOH ⎯⎯⎯⎯⎯→ RCOOK + R'OH
Reactions with ethyl benzoate
1. Back titration :
Hydrolysis
C6H5COOC2H5 + Alc. KOH ⎯⎯⎯⎯⎯→ C6H5COOK + C2H5OH
Ethyl benzoate (Excess) Potassium benzoate
2. Blank titration :
Alc. KOH + HCl ⎯⎯→ KCl + H2O
(Unreacted)
Chemicals :
(i) Unknown ethyl benzoate solution (10-15 ml)
(ii) 0.5 N alcoholic KOH (approx.)
(iii) 0.05 N HCl (exact)
271
Procedure :
1. Transfer the given ethyl benzoate solution in 100 ml R.B. flask. Add to it 10 ml
0.5 N alcoholic KOH solution by means of common burette.
2. Add one porcelain piece in the R.B. flask (used for even heating). Attach water
condenser to the flask and heat it on a water bath for one hour.
3. Then cool the flask and dilute the contents to 100 ml in volumetric flask with distilled
water. Mix it well and fill this diluted solution in the burette No. 1.
4. Fill the burette No. 2 by 0.05 N HCl (exact).
5. Take exactly 9 ml of diluted benzoate solution in a conical flask from burette No. 1.
Add one test tube of distilled water and two drops of phenolphthalein indicator. Pink
7. To the same conical flask add 1 ml of diluted benzoate solution from burette No. 1
8. Again to the same conical flask add 1 ml of diluted benzoate solution from burette
No. 1 and titrate it against 0.05 N HCl (exact) solution from burette No. 2 till the pink
colour disappears. Note down the burette reading as Y3 ml.
1. Take 10 ml of 0.5 N KOH (approx) solution from the common burette and dilute to
100 ml in a 100 ml volumetric flask. And fill in burette No. 1 again. This will form the
0.05 N KOH solution.
2. Fill the burette No. 2 with 0.05 N HCl (exact).
3. Take exactly 9 ml of 0.05 N KOH solution in a conical flask from burette No. 1. Add
one test tube of distilled water and two drops of phenolphthalein indicator. Pink
5. To the same conical flask add 1 ml of 0.05 N KOH solution from burette No. 1 and
titrate it against 0.05 N HCl (exact) solution from burette No. 2 till the pink colour
6. Again to the same conical flask add 1 ml of 0.05 N KOH solution from burette No. 1
272
Observation Table :
Burette No. 1 : Diluted ethyl benzoate solution Burette No. 2 : 0.05 N HCl
Reading (B.R.) ml
I II III
(benzoate solution)
Y1 + Y 2 + Y3
Y=
Burette No. 2 (HCl) Y1 = …… ml Y2 = …… ml Y3 = …… ml 3
Y = …… ml.
Burette No. 1 : 0.05 N KOH solution Burette No. 2 : 0.05 N HCl
Reading (B.R.) ml
I II III
Burette No. 1 (KOH) 9 ml 10 ml 11 ml 10 ml
X1 + X2 + X3
X=
Burette No. 2 (HCl) X1 = …… ml X2 = …… ml X3 = …… ml 3
X = …… ml.
Calculations :
Amount of KOH used by 10 ml of diluted ethyl benzoate solution in terms of 0.05 N
HCl = (x − y) = …… ml
Hydrolysis
RCOOR' + alc. KOH ⎯⎯⎯⎯→ RCOOK + H2O
KOH + HCl ⎯⎯⎯⎯→ KCl + H2O
According to reactions :
1 mole of KOH = 1 mole of ethyl benzoate
1000 ml 1 N KOH = 150 gms of ethyl benzoate
i.e. 1000 ml 1 N HCl = 150 gms of ethyl benzoate
0.05 × 150
So, 1 ml 0.05 N HCl = = 0.0075 gms of ethyl benzoate.
1000
(X − Y) ml 0.05 N HCl = (X − Y) × 0.0075 g of ethyl benzoate
= ‘A’ gms of ethyl benzoate
i.e. 10 ml diluted solution contains = ‘A’ gms of ethyl benzoate
100 ml diluted solution contains = (A × 10) = Z gms of ethyl benzoate
273
Result Table :
1. Amount of 0.05 N HCl (exact) required for blank titration X = …….. ml
2. Amount of 0.05 N HCl (exact) required for back titration Y = …….. ml
3. Amount of KOH used by 10 ml of diluted solution in terms of (X − Y) = …… ml
0.05 N HCl (exact)
4. Amount of acetamide in the given solution ‘Z’ = …….. gms.
Experiment No. 4
Molecular Weight of Monobasic/Dibasic Organic Acid
Aim :
Determination of molecular weight of given monobasic/dibasic acid by volumetric method.
Principle :
The molecular weight of a compound is the weight of one molecule of it, as compared
to the weight of hydrogen as one. The methods commonly employed for the determination
of molecular weight of organic substances are physical and chemical methods.
The determination of molecular weight of an organic acid is usually carried out by two
methods :
(i) The volumetric method.
(ii) The silver salt method.
The volumetric method is based upon the neutralization of a weighed amount of the acid
by a standard alkali. The equivalent weight as well as molecular weight of organic acid can be
determined by this method provided that basicity is known.
Reactions :
For monobasic acid
R⎯COOH + NaOH ⎯⎯→ R⎯COONa + H2O
For dibasic acid
COOH + 2NaOH ⎯⎯→ COONa + 2H2O
⏐ ⏐
COOH COONa
When basicity of acid is given, its molecular weight can be calculated from its equivalent
weight, e.g.
For monobasic acid,
Molecular weight = Basicity × Equivalent weight = 1 × Equivalent weight.
For dibasic acid,
Molecular weight = Basicity × Equivalent weight = 2 × Equivalent weight.
274
Chemicals :
(i) Monobasic/dibasic acid sample solution in 100 ml volumetric flask
(ii) 0.05 N NaOH (approx.)
(iii) Potassium hydrogen phthalate
Procedure :
Part I : Preparation of 0.05 N potassium hydrogen phthalate :
Weigh accurately 1.02 g of A.R. grade potassium hydrogen phthalate. Dissolve it in little
amount of water. Transfer it carefully to 100 ml volumetric flask. Dilute it upto the mark with
distilled water. Pour the whole solution in a beaker.
Part II : Standardization of 0.05 N NaOH :
1. Fill the burette No. 1 with 0.05 N NaOH.
2. Fill the burette No. 2 with 0.05 N K-H-Phthalate.
3. Take exactly 9 ml 0.05 N K-H-Phthalate solution in a conical flask from burette No. 2.
Add one test tube of distilled water and two drops of phenolphthalein indicator.
4. Titrate it against 0.05 N NaOH solution from burette No. 1 till the faint pink colour
appears. Note down the burette reading as X1 ml.
5. To the same conical flask add 1 ml of 0.05 N K-H-Phthalate solution from burette
No. 2 and titrate it against 0.05 N NaOH solution from burette No. 1 till the pink
colour appears. Note down the burette reading as X2 ml.
6. Again to the same conical flask add 1 ml of 0.05 N K-H-Phthalate solution from
burette No. 2 and titrate it against 0.05 N NaOH solution from burette No. 1 till the
pink color appears. Note down the burette reading as X3 ml.
Part III : Determination of molecular weight of monobasic/dibasic acid :
1. Dilute the given acid solution upto the mark with distilled water.
2. Fill the burette No. 1 with 0.05 N NaOH.
3. Fill the burette No. 2 with diluted acid solution.
4. Take exactly 9 ml diluted acid solution in a conical flask from burette No. 2. Add one
test tube of distilled water and two drops of phenolphthalein indicator.
5. Titrate it against 0.05 N NaOH solution from burette No. 1 till the faint pink colour
appears. Note down the burette reading as Y1 ml.
6. To the same conical flask add 1 ml of diluted acid solution from burette No. 2 and
titrate it against 0.05 N NaOH solution from burette No. 1 till the pink colour appears.
Note down the burette reading as Y2 ml.
7. Again to the same conical flask add 1 ml of diluted acid solution from burette No. 2
and titrate it against 0.05 N NaOH solution from burette No. 1 till the pink colour
appears. Note down the burette reading as Y3 ml.
Observation Table :
Part II : Standardization of 0.05 N NaOH
Burette No. 1 : 0.05 N NaOH solution Burette No. 2 : 0.05 N K-H-Phthalate
Indicator : Phenolphthalein End point : Colourless to pink
275
Reading (B.R.) ml
I II III
(K-H-phthalate)
X1 + X2 + X3
X=
Burette No. 1 (NaOH) X1 = …… ml X2 = …… ml X3 = …… ml 3
X = …… ml.
Let the constant burette reading be ‘X’ ml.
Part III : Determination of Molecular Weight of Monobasic/Dibasic Acid :
Burette No. 1 : 0.05 N NaOH solution Burette No. 2 : Diluted acid solution
Indicator : Phenolphthalein End point : Colourless to pink
Reading (B.R.) ml
I II III
(Diluted acid solution)
Burette No. 1 (NaOH) Y1 + Y 2 + Y3
Y=
Y1 = …… ml Y2 = …… ml Y3 = …… ml 3
Y = …… ml.
Let the constant burette reading be ‘Y’ ml.
Calculations :
1. To find the exact normality of NaOH :
NaOH = C8H5O4K (K-H-Phthalate)
N1V1 = N2V2
N1 × (C.B.R. = X) = 0.05 × 10
0.05 × 10
N1 = = ………. N
X
Exact normality of NaOH = N1 = ………. N
2. The strength of given acid is calculated as follows :
W = Weight of acid present in the given solution
[Ask for the weight (W) of acid to the examiner]
Volume of the alkali used for complete neutralization of the acid solution = Y ml.
Normality of alkali solution = N1
Then we can write,
W
Y ml of alkali (NaOH) solution having normality N1 = gms acid.
10
[Since W gms. of acid is present in 100 ml of diluted solution]
1000 ml of alkali solution having normality
W × 1000
N = gms of acid.
Y × N1 × 10
276
We know that,
1000 ml of 1 N alkali solution = 1 gm equivalent of alkali.
Since acids and alkalies (bases) neutralize each other in equivalent proportions,
W × 1000
hence, 1 gm Equivalent of acid = gms of acid.
Y × N1 × 10
W × 1000
So, Equivalent weight of an acid (Z) = gms of acid.
Y × N1 × 10
3. The molecular weight of an acid :
[Ask for the basicity of acid to the examiner]
Now molecular weight = Equivalent weight × Basicity = Z × Basicity
For monobasic acid : Molecular weight = Equivalent weight = M1 gms
For dibasic acid : Molecular weight = 2 × Equivalent weight = 2 × Z = M2.
Result Table :
1. Amount of NaOH required for 10 ml of 0.05 N potassium X = …….. ml
hydrogen phthalate
2. Amount of NaOH required for 10 ml of given acid solution Y = …….. N
3. Exact normality of NaOH N1 = …… N
4. Molecular weight of given acid
VIVA VOCE
1. How will you prepare (a) 0.05 N KOH, (b) 0.05 N NaOH, (c) 0.05 N HCl ?
2. What is the difference between normal solution and molar solution ?
3. How to check the completion of hydrolysis of acetamide by NaOH solution ?
4. Write the reaction of (a) hydrolysis of acetamide by NaOH, (b) hydrolysis of ethyl
benzoate with aqueous KOH.
5. What is the principle of estimation of ethyl benzoate ?
6. What is standard solution ? Why standardization of NaOH is required ? Which
compound is used to standardize NaOH solution ?
7. Explain the terms : (a) Monobasic acid, (b) Dibasic acid, (c) Tribasic acid. Give one
example of each type of acid.
8. Write the relation between molecular weight and equivalent weight.
9. How will you prepare (a) 0.05 N and 0.02 N potassium hydrogen phthalate, (b) 0.02 N
and 0.05 N NaOH solution ?
10. What is the structure of glucose ? Why glucose is a reducing sugar?
11. Write the reaction of titration of iodine against Na2S2O3.
12. What is the reaction of glucose with sodium hypoiodide.
13. How will you prepare 0.05 N, 0.1 N and 1 N I2 solution ?
14. In iodometric titration after addition of Na2CO3 and I2 solution in glucose solution,
the reaction bottles are kept in dark for 30 minutes, why ?
---
277
(C) Organic Preparations
(Any Eight)
Experiment No. 1
Organic Preparations
Aim:
To study the oxidation reaction.
Experiment:
Preparation of Adipic acid from Cyclohexanone.
Principle:
Cyclohexanone can be readily oxidized to adipic acid by using concentrated nitric acid as
oxidizing agent.
Reaction:
O
conc. HNO3 COOH

COOH
Cyclohexanone Adipic acid
Chemicals:
(i) Cyclohexanone = 0.5 ml
(ii) Conc. HNO3 = 2.5 ml
(iii) Distilled water = 1.5 ml
Procedure:
Place 2.5 ml of conc. HNO3 in 25 ml round bottom flask. To this add 1.5 ml distilled water
and 0.5 ml cyclohexanone dropwise so that the temperature does not rise above 85°C. After
the addition is over reflux on a wire gauze for half an hour. Cool the flask in ice bath, filter
the product on Buchner funnel. Record the practical yield and re-crystallize from hot water.
Re-crystallization:
Take the crude product and water (5 ml) in a beaker and dissolve by heating on a water
bath. Filter the hot solution and cool the filtrate. Filter, dry and record the melting point and
TLC (using toluene as a solvent).
Calculations: (i) Theoretical yield:
Cyclohexanone (C6H10O) ≡ Adipic acid (C6H10O4)
98g ≡ 146g
278
T.Y.B.Sc. Practical Chemistry (Organic Practicals) Organic Preparations
Therefore, 0.5g ≡ 0.74g

(ii) Practical yield = ‘A’ g
(iii) Practical % yield:
Since, 0.74 g of product = 100% yield
A × 100
Therefore, ‘A’ g = = …… %
0.74
Result Table:
Practical yield …… g
M.P. of adipic acid …… °C
Practical % yield …… %
Rf value of adipic acid ……
Solvent used for TLC ……
Note:
Cyclohexanone do not show any spot on TLC
Experiment No. 2
Aim:
To study the oxidation reaction.
Experiment:
Preparation of Quinone (p-Benzoquinone) from Hydroquinone.
Principle:
Hydroquinone can be readily oxidized to quinone by using oxidizing agent like
potassium dichromate and conc. H2SO4 or KBrO3.
Reaction:
OH O
K2Cr2O7/conc. H2SO4
or KBrO3
OH O
Hydroquinone Quinone
Chemicals:
(i) Hydroquinone = 0.5 g
(ii) Potassium dichromate = 1.0 g
(iii) conc. H2SO4 = 1 ml
279
(iv) Distilled water = 15 ml

Procedure:
Take 0.5 g hydroquinone and 5 ml distilled water in a beaker (25 ml). Heat on a wire
gauze to obtain a clear solution. Take 1 g potassium dichromate (K2Cr2O7) in a conical flask
and dissolve in 10 ml water and add 1 ml conc. H2SO4. Shake and cool the conical flask in ice
water. To this ice cold solution add hydroquinone solution (prepared above) dropwise over a
period of 30 minutes with constant shaking. Do not allow the temperature to rise above
20oC. After complete addition, continue shaking for further 10 minutes. Yellow crystals of
quinone separate out. Filter on a Buchner funnel and dry it well. (Note: Do not wash with
water as the product is water soluble). Record the practical yield and re-crystallize from ethyl
alcohol.
OR
Chemicals:
(i) Hydroquinone = 0.5 g
(ii) Potassium bromate = 0.4 g
(iii) conc. H2SO4 = 1 ml
(iv) Distilled water = 10 ml
Procedure:
Take 0.5 g hydroquinone, 5 ml distilled water and 0.4 g potassium bromate (KBrO3) in a
beaker (25 ml). Heat on a wire gauze to obtain a clear solution. Cool the beaker and add
1 ml conc. H2SO4 dropwise with constant shaking. Cool the beaker in ice water. Yellow
crystals of quinone separate out. Filter on a Buchner funnel and dry it well. (Note: Do not
wash with water as the product is water soluble). Record the practical yield and re-crystallize
from ethyl alcohol.
Re-crystallization:
Dissolve the crude product in minimum amount of ethyl alcohol in a beaker by heating
on a water bath. Filter the hot solution and cool the filtrate. The yellow needles of quinone
separate out. Filter, dry and record the melting point and TLC (using toluene as a solvent).
Calculations: (i) Theoretical yield:
Hydroquinone (C6H6O2) ≡ Quinone (C6H4O2)
110 g ≡ 108 g
Therefore, 0.5 g ≡ 0.49 g
Since 0.49 g of product = 100% yield
280
A × 100
0.49
Result Table:
M.P. of quinone …… °C
Rf value of hydroquinone ……
Rf value of quinone ……
Experiment No. 3
Aim:
To study the aromatic electrophilic substitution reaction.
Experiment:
Preparation of p-nitro acetanilide from acetanilide.
Principle:
Aromatic compounds can be conveniently nitrated by the use of the nitrating mixture,
which is normally a mixture of concentrated nitric acid and concentrated sulphuric acid. The
function of sulphuric acid is to convert nitric acid into a highly reactive, electrophilic,
+
nitronium ion, NO2 , which is the effective nitrating agent. Nitration of activated aromatic
compounds is carried out under milder condition whereas deactivated rings require drastic
conditions. Activating groups are o, p-directing, while deactivating groups are m-directing for
electrophilic substitution.
Reaction:
+ −
HNO3 + 2H2SO4 ⎯→ NO2 + H3O+ + 2HSO4
NHCOCH3 NHCOCH3
conc. HNO3
conc. H2SO4
NO2
Acetanilide p-Nitro acetanilide
Chemicals:
(i) Acetanilide = 0.5 g
(ii) conc. HNO3 = 0.25 ml
281
(iii) conc. H2SO4 = 1.2 ml

(iv) Glacial acetic acid = 0.6 ml
Procedure:
Take 0.5 g acetanilide in 0.6 ml glacial acetic acid and add 1 ml conc. H2SO4 in a beaker.
Cool the mixture in ice salt bath (5-10°C). To this add a mixture of 0.2 ml conc. H2SO4 and
0.25 ml conc. HNO3 dropwise. Maintain the temperature below 10°C during addition. After
addition is over allow the mixture to attain room temperature and leave it for 30 minutes.
Pour the mixture on to crushed ice (20 g) with stirring. Filter the separated product and wash
with cold water. Dry the product, record the practical yield and re-crystallize it.
Re-crystallization:
on a water bath. Filter the hot solution and cool the filtrate. The crystals of the product
separate out. Filter, dry and record the melting point and TLC (using toluene as solvent).
Calculations:
(i) Theoretical yield:
Acetanilide (C8H9ON) ≡ p-Nitro acetanilide (C8H8O3N2)
135 g ≡ 180 g
A × 100
0.66
Result Table:
1. Practical Yield …… g
2. M.P. of p-nitro acetanilide …… °C
3. Practical % yield …… %
4. Rf value of acetanilide ……
5. Rf value of p-nitro acetanilide ……
6. Solvent used for TLC ……
Experiment No. 4
Aim:
To study the etherification reaction.
Experiment:
Preparation of 2-naphthyl methyl ether from 2-naphthol.
282
Principle:
Phenols can be methylated to give methyl ethers. Methylation can be done either by
using diazomethane or dimethyl sulphate in alkaline medium.
Reaction:
OH Dimethyl sulphate OCH3
NaOH
2-Naphthol 2-Naphthyl methyl ether

Chemicals:
(i) 2-Naphthol = 0.5 g
(ii) Dimethyl sulphate = 0.35 ml
(iii) NaOH = 0.2 g
Procedure:
Take 0.5 g 2-naphthol and 0.2 g NaOH in 5 ml distilled water in a beaker (25 ml). Heat on
a wire gauze to obtain a clear solution. Cool the solution (10-15°C) and then add 0.35 ml
dimethyl sulphate drop wise. After the addition is over, warm the mixture for one hour at
70-80oC and then cool. Filter the product and wash it with 10% sodium hydroxide solution
and then with water. Dry the product, record the practical yield and re-crystallize it.
Re-crystallization:
on a water bath. Filter the hot solution and cool the filtrate. Filter the white crystals of the
product. Dry and record the melting point and TLC (using toluene as solvent).
Calculations:
2-Naphthol (C10H8O) ≡ 2-Naphthyl methyl ether (C11H10O)
144 g ≡ 158 g
A × 100
0.54
Result Table:
M.P. of 2-naphthyl methyl ether …… °C
283
Rf value of 2-naphthol ……
Rf value of 2-naphthyl methyl ether ……
Experiment No. 5
Aim:
To study the benzoylation reaction.
Experiment:
Preparation of Benzoyl glycine (Hippuric acid) from Glycine.
Principle:
The hydroxy and amino functions can be easily benzoylated using Benzoyl chloride in
aqueous alkaline conditions. This reaction is known as Schotten-Baumann reaction.
Reaction:
O
COOH PhCOCl N COOH

H2N
NaOH or KOH H
Glycine Benzoyl glycine

(Hippuric acid)
Chemicals:
(i) Glycine = 0.5 g
(ii) Benzoyl chloride = 0.9 ml
(iii) NaOH = 1.34 g in 14 ml water
(iv) conc. HCl
(v) CCl4 = 30 ml
Procedure:
Dissolve 0.5 g of glycine in 5 ml of 10% NaOH solution in a 25 ml conical flask. Add
0.9 ml of benzoyl chloride in five portions to the solution. Stopper the flask and shake
vigorously after each addition until all the benzoyl chloride is reacted. Transfer the solution to
a beaker and add few grams of ice and add conc. HCl slowly with stirring until the solution is
acidic to litmus paper. Filter the crystalline precipitate of the product on a Buchner funnel,
wash with cold water and drain well. Place the solid in a conical flask with 10 ml CCl4 and boil
gently for 10 min. Allow the mixture to cool slightly, filter under gentle suction and wash with
10-20 ml CCl4. Record the practical yield and re-crystallize it.
Re-crystallization:
284
Dissolve the crude product from boiling water (5 ml), with addition of decolorizing
charcoal if necessary, filter the hot solution and cool the filtrate. The crystals of the product
separate out. Filter, dry and record the melting point and TLC [using Butanal : acetic acid:
water (4 : 1 : 1) as solvent or CHCl3:methanol (9 : 1) or toluene].
Calculations:
Glycine (C2H5O2N) ≡ Benzoyl glycine (C9H9O3N)
75 g ≡ 179 g
A × 100
1.19
Result Table:
1. Practical yield …… g
2. M.P. of benzoyl glycine …… °C
4. Rf value of glycine ……
5. Rf value of benzoyl glycine ……
Experiment No. 6
Aim:
To study the aromatic substitution reaction (replacement of diazo group, Sandmeyer
reaction).
Experiment:
Preparation of p-Iodo nitrobenzene from p-Nitro aniline.
Principle:
Diazonium salts undergo a large number of reactions in which the diazo group is lost as
molecular nitrogen and is replaced by variety of other groups (e.g. OH, I, Br, Cl, F, CN, NO2, H,
SO2H, Ar) which become attached to the aromatic ring.
Reaction:
285
NH2 Cl N N I
NaNO2 KI
HCl
NO2 NO2 NO2

p-Nitro aniline Diazonium salt p-Iodo nitrobenzene
Chemicals:
(i) p-Nitro aniline = 0.5 g
(ii) NaNO2 = 0.25 g
(iii) conc. H2SO4 = 0.41 ml
(iv) KI = 1 g
Procedure:
Take 0.5 g p-nitro aniline, 0.41 ml conc. H2SO4 and 3 ml water in a conical flask. Stir it well
and cool to 0-5°C. Add a cold solution of 0.25 g NaNO2 in 0.75 ml distilled water to the
above solution. Filter the resultant cold solution, and add the filtrate with stirring to a
solution of 1 g KI in 3 ml water taken in a beaker. Filter the product separated out and wash
it with water. Dry the product, record the practical yield and re-crystallize it.
Re-crystallization:
on a water bath. Filter the hot solution and cool the filtrate. The shiny brown crystals of
p-iodo nitro benzene separate out. Filter, dry and record the melting point and TLC (using
toluene as a solvent).
Calculations:
p-Nitro aniline (C6H6O2N) ≡ p-iodo nitro benzene (C6H4O2NI)
124 g ≡ 202 g
202 × 0.5
Therefore, 0.5 g ≡ g = 0.81 g
124
A × 100
0.81
Result Table:
286
2. M.P. of p-iodo nitrobenzene …… °C
4. Rf value of p-nitro aniline ……
5. Rf value of p-iodo nitrobenzene ……
Experiment No. 7
Aim:
To study the ester hydrolysis.
Experiment:
Preparation of Benzoic acid from Ethyl benzoate.
Principle:
Esters can be hydrolyzed either under basic or acidic conditions. Aqueous KOH or NaOH
readily hydrolyze the esters into salts of acids from which the acids are liberated by
acidification. The acid hydrolysis of esters using HCl or H2SO4 directly yields the
corresponding acids.
Reaction:
O O
C2H5
O (i) aq. NaOH OH
(ii) HCl + EtOH
Ethyl benzoate Benzoic acid

Chemicals:
(i) Ethyl benzoate = 0.5 ml
(ii) 10% NaOH = 7 ml
(iii) dil. HCl
Procedure:
Take 0.5 ml ethyl benzoate, 7 ml 10% NaOH in a round 25 ml bottom flask fitted with
water condenser. Boil the mixture for at least 1 h. Disappearance of the ester layer confirms
the completion of the reaction. Cool the mixture by adding small amount of ice and then
add dil. HCl with stirring until the solution is acidic to litmus. Filter the product separated out
and wash it with water. Dry the product, record the practical yield and re-crystallize it.
Re-crystallization:
287
Take the crude product and water (10 ml) in a beaker and dissolve by heating on a wire
gauze. Filter the hot solution and cool the filtrate. The shiny white crystals of benzoic acid
separate out. Filter, dry and record the melting point and TLC (using toluene as solvent).
Calculations:
Ethyl benzoate (C6H6O2N) ≡ Benzoic acid (C6H4O2NI)
150 g ≡ 122 g
122 × 0.5
Therefore, 0.5 g ≡ g = 0.4 g
150
A × 100
0.4
Result Table:
2. M.P. of benzoic acid …… °C
4. Rf value of ethyl benzoate ……
5. Rf value of benzoic acid ……
Experiment No. 8
Aim:
To study the aromatic electrophilic substitution reaction.
Experiment:
Preparation of p-Bromo acetanilide from Acetanilide.
Principle:
Aromatic compounds can be conveniently brominated by the use of brominating agent,
which is normally a solution of bromine in acetic acid. Bromination of activated aromatic
compounds usually give 2, 4, 6-tribromo derivatives while moderately activating group like
anilide give preferably the para bromo product.
Reaction:
288
NHCOCH3 NHCOCH3
Bromine
AcOH
Br
Acetanilide p-Bromo acetanilide
Chemicals:
(i) Acetanilide = 0.5 g
(ii) 25% (w/v) Bromine in AcOH = 2.5 ml
Procedure:
Dissolve 0.5 g acetanilide in 0.6 ml glacial acetic acid and add 2.5 ml bromine solution in
acetic acid (25% w/v). Shake the mixture for 1 h. After 1 h, pour the mixture on to crushed ice
(20 g) with stirring. Filter the separated product and wash with cold water. Dry the product,
record the practical yield and re-crystallize it.
Re-crystallization:
on a water bath. Filter the hot solution and cool the filtrate. The crystals of the product
separate out. Filter, dry and record the melting point and TLC (using toluene as a solvent).
Calculations:
Acetanilide (C8H9ON) ≡ p-Bromo acetanilide (C8H8ONBr)
135 g ≡ 214 g
A × 100
79
Result Table:
2. M.P. of p-bromo acetanilide …… °C
4. Rf value of acetanilide ……
5. Rf value of p-bromo acetanilide ……
289
Experiment No. 9
Aim:
To study the acetylation reaction.
Experiment:
Preparation of Paracetamol from p-Hydroxy aniline.
Principle:
The hydroxy and amino functions both can be easily acetylated using acetic anhydride or
acetyl chloride. However, amino function being more nucleophilic than hydroxy function, can
be acetylated selectively using acetic anhydride under neutral conditions.
Reaction:
NH2 NHCOCH3
(CH3CO)2O
Water
OH OH
p-Hydroxyaniline Paracetamol
Chemicals:
(i) p-Hydroxy aniline = 0.5 g
(ii) Acetic anhydride = 0.6 ml
Procedure:
Suspend 0.5 g p-hydroxy aniline in 3.0 ml water and add 1.2 ml acetic anhydride. Shake
the mixture vigorously and warm on water bath till the solid dissolves. After 10 min, cool,
filter the solid acetyl derivative and wash with cold water. Dry the product, record the
practical yield and re-crystallize it.
Re-crystallization:
Dissolve the crude product in water (10 ml) in a beaker by heating on a water bath. Filter
the hot solution and cool the filtrate. The crystals of the product separate out. Filter, dry and
record the melting point and TLC (using toluene as a solvent).
Calculations:
p-Hydroxy aniline (C6H7ON) ≡ Paracetamol (C8H9O2N)
109 g ≡ 151 g
290
A × 100
0.69
Result Table:
2. M.P. of paracetamol …… °C
4. Rf value of p-hydroxy aniline ……
5. Rf value of paracetamol ……
Experiment No. 10
Aim:
To study the carbonyl reduction reaction.
Experiment:
Preparation of Ethyl benzene from Acetophenone.
Principle:
The carbonyl function can be completely reduced to methylene under acidic, basic or
neutral conditions. Amongst these the most common methods are Clemmensen’s reduction,
Wolf Kishner reduction and Mozingo reduction. The reduction of carbonyl group using
hydrazine in basic medium using KOH is called as Wolf-Kishner reduction.
Reaction:
O CH3
NH2NH2.H2O
KOH
Acetophenone Ethyl benzene
Chemicals:
(i) Acetophenone = 1.0 ml
(ii) 90% Hydrazine hydrate = 2 ml
(iii) KOH = 1.1 g
(iv) Ethylene glycol = 10 ml
(v) Diethyl ether = 20 ml
Procedure:
291
Place 0.5 ml acetophenone, 5.0 ml ethylene glycol and 1.0 ml of 90% hydrazine hydrate
solution and 1.1 g KOH pellets in a round bottom flask fitted with water condenser. Warm
the reaction mixture of boiling water bath till KOH dissolves and then reflux for 1 h on wire
gauze. Distill using Hickmann head till the temperature is 175oC. Keep the distillate and again
reflux for 2 h. Cool this and extract twice with 10 ml ether. Combine the ether extracts with
the distillate removed earlier and dry over sodium sulphate, decant and evaporate the ether.
Re-distillation:
Distill the residual compound and record the boiling point and TLC (using toluene as a
solvent).
Note: Ethyl benzene will not show spot on TLC. Formation of the product can be
confirmed by negative 2, 4-DNP test.
Calculations:
Acetophenone (C8H8O) ≡ Ethyl benzene (C8H10)
120 g ≡ 106 g
A × 100
0.44
Result Table:
2. B.P. of ethyl benzene …… °C
4. Rf value of acetophenone ……
Note: Ethyl benzene will not show spot on TLC.
VIVA VOCE
1. What is oxidation? Mention four oxidizing agents.
2. Give one oxidation reaction (a) in which hydrogens are removed, (b) in which oxygen
is added, (c) in which electrons are removed.
3. How will you distinguish hydroquinone from quinone (a) by chemical method,
(b) by spectroscopy ?
4. What is electrophilic aromatic substitution reaction?
5. Diazotization is carried out at low temperature. Why?
6. Sulphuric acid is preferred over hydrochloric acid in the preparation of diazonium
salt. Why?
292
7. Acidic pH is maintained in the reaction involving replacement of diazonium group.

Why?
8. What is Sandmeyer reaction?
9. What is the role of sulphuric acid in the nitrating mixture?
10. p-Nitro aniline is not prepared by nitration of aniline. Why?
11. Electron withdrawing groups are meta directing in electrophilic substitution reactions.
Why?
12. What are the various reagents used for methylation reaction?
13. Why NH2 undergoes acetylation in preference to hydroxyl group?
14. What are the different methods for reducing carbonyl group to methylene group?
15. Ester hydrolysis is carried out preferably under basic conditions. Explain.
---
293
Appendices
STOCK SOLUTIONS
1. Acetamide Solution :
Dissolve 25 g acetamide in 200 ml water and dilute to one litre.
(Give 10-15 ml in conical flask for estimation)
2. Ethyl Benzoate Solution :
Dissolve 60 ml ethyl benzoate in 200 ml alcohol and dilute to one litre by ethyl alcohol.
(Give 10-15 ml in conical or R.B. flask for estimation)
3. Oil Solution :
Dissolve 100 g of castor oil in ethyl alcohol (200 ml) and dilute to one litre by ethyl
alcohol. (CHCl3 or CCl4 can be used instead of ethyl alcohol).
Give 10 to 15 ml in measuring flask for estimation)
4. Monobasic or Dibasic Acid Solution :
Dissolve 47.5 ml acetic acid or 50 g of oxalic acid in 200 ml water and dilute to one litre
by water.
(Give 10-15 ml for estimation in measuring flask)
5. Wij’s Solution (Iodine-monochloride Solution) :
Two methods :
(a) Dissolve 13 g of iodine powder in 750 ml acetic acid in R.B. flask. (Warm water bath if
necessary using air condenser). Pass slow stream of dry Cl2 gas till colour changes to
clear orange. This is Wij’s solution. It should be stored in well stoppered amber colour
bottle and keep in dark cool place. (Do not keep the solution for more than 3 days.)
(b) Dissolve 25 g I2 in 500 ml ethyl alcohol and 30 g HgCl2 in 500 ml ethyl alcohol. Mix
these solutions and keep for 12 hours in an amber colour bottle.
6. Glucose Solution :
Dissolve 25 g. glucose in 200 ml water and dilute it to one litre by water.
(Give 10-15 ml for estimation in measuring flask)
Other Solutions :
1. 0.5 N KOH : 28 g in one litre water.
2. 0.5 N alcoholic KOH : 28 g in one litre alcohol.
3. 0.05 N NaOH : 2 g NaOH in one litre water.
4. 0.05 N Na2S2O3 : 12.4 g Na2S2O3 in one litre water.
5. 10% KI : 10 g KI in 100 ml water.
6. 1 N HCl : 100 ml conc. HCl diluted to one litre by water.
( 293 )
T.Y.B.Sc. Practical Chemistry (Organic Practicals) Appendices
7. 0.05 N HCl : 5 ml conc. HCl diluted to one litre by water.

8. 0.05 N I2 : 6.35 g I2 and 15 g KI in 10 ml water.
Stirr well, go on adding water with stirring till iodine dissolves completely. Dilute the
solution to one litre by water.
9. Schiff’s reagent : Dissolve 0.2 g of rosaniline in 100 ml water. Pass SO2 gas till the
solution becomes colourless (pink colour vanishes).
Indicators :
1. Phenolphthalein : Dissolve 1 g phenolphthalein in 500 ml ethyl alcohol and dilute to
one litre by water.
2. Starch : Take 1 g starch and make a paste with water. Add this slowly to 200 ml
boiling water. Boil further for few minutes and allow to cool.
List of Organic Mixtures :
(a) Solid - Solid :
1. Benzoic acid + Acetanilide 2. Benzoic acid + Naphthalene
3. Benzoic acid + β-naphthol 4. Benzoic acid + m-dinitrobenzene
5. Benzoic acid + p-nitroaniline 6. Cinnamic acid + α-naphthol
7. Cinnamic acid + Anthracene 8. Cinnamic acid + β-naphthol
9. Cinnamic acid + m-nitroaniline 10. Salicylic acid + Acetanilide
11. Salicylic acid + α-naphthol 12. Salicylic acid + m-dinitrobenzene
13. Aspirin + Naphthalene 14. Aspirin + β-naphthol
15. Aspirin + Acetanilide 16. β-naphthol + Naphthalene
17. β-naphthol + m-dinitrobenzene 18. β-naphthol + p-toluidine
19. β-naphthol + Acetanilide 20. phthalic acid + p-toluidine
21. o-nitrophenol + Anthracene 22. p-nitrophenol + m-dinitroaniline
23. α-naphthol + m-dinitrobenzene 24. α-naphthol + m-nitroaniline
25. o-nitrophenol + p-nitroaniline 26. p-toluidine + Naphthalene
27. p-toluidine + Acetanilide 28. p-nitroaniline + m-dinitrobenzene
29. m-nitroaniline + Naphthalene 30. m-nitroaniline + Anthracene
(b) Solid - Liquid :
31. Acetone + Oxalic acid 32. Acetone + Acetanilide
33. Chloroform + Naphthalene 34. Chloroform + m-dinitrobenzene
35. Ethylmethyl ketone + urea 36. Chloroform + m-nitroaniline
294
37. Acetone + Acetamide 38. Chloroform + Acetanilide

(c) Liquid - Liquid :
39. Chloroform + Chlorobenzene 40. Ethyl acetate + Nitrobenzene
41. Acetone + Aniline 42. Chloroform + Dimethylaniline
43. Methylacetate + Acetophenone 44. Ethylmethyl ketone + Chlorobenzene
USEFUL DATA
Atomic Numbers and Atomic Weights of Elements
Element Symbol At. At. Wt. Element Symbol At. At. Wt.
No. No.
Actinium Ac 89 227 Einsteinium Es 99 254
Aluminium Al 13 26.9815 Erbium Er 68 167.36
Americium Am 95 243 Europium Eu 63 151.96
Antimony Sb 51 121.75 Fermium Fm 100 257
Argon Ar 18 39.948 Fluorine F 9 18.9984
Arsenic As 33 74.9216 Francium F 87 223
Astatine At 85 210 Gadolinium Gd 64 157.25
Barium Ba 56 137.34 Gallium Ga 31 69.72
Berkelium Bk 97 247 Germanium Ge 32 72.59
Berylium Be 4 9.0122 Gold Au 79 196.9665
Bismuth Bi 83 208.9804 Hafnium Hf 72 178.49
Boron B 5 10.81 Helium He 2 4.0026
Bromine Br 35 79.904 Holmium Ho 67 164.9304
Cadmium Cd 48 112.40 Hydrogen H 1 1.0079
Calcium Ca 20 40.08 Indium In 49 114.82

Californium Cf 98 251 Iodine I 53 126.9045
Carbon C 6 12.011 Iridium Ir 77 192.22
Cerium Ce 58 140.12 Iron Fe 26 55.847
Cesium Cs 55 132.9054 Krypton Kr 36 83.80
Chromium Cr 24 51.996 Lawrencium Lr 103 260
295
Cobalt Co 27 58.9332 Lead Pb 82 207.2

(Contd.)
Element Symbol At. At. Wt. Element Symbol At. At. Wt.
No. No.
Copper Cu 29 63.546 Lithium Li 3 6.941
Curium Cm 96 247 Lutetium Lu 71 174.97
Dysprosium Dy 66 162.50 Magnesium Mg 12 24.305
Manganese Mn 25 54.9380 Ruthenium Ru 44 101.07
Mendelevium Md 101 256 Samarium Sm 62 150.4
Mercury Hg 80 200.59 Terbium Tb 65 158.9254
Molybdenum Mo 42 95.94 Scandium Sc 21 44.9559
Neodymium Nd 60 144.24 Selenium Se 34 78.96
Neon Ne 10 20.183 Silicon Si 14 28.086
Neptunium Np 93 237.0482 Silver Ag 47 107.868
Nickel Ni 28 58.71 Sodium Na 11 22.9898
Niobium Nb 41 92.9064 Strontium Sr 38 87.62
Nitrogen N 7 14.0017 Sulphur S 16 32.06
Nobelium No 102 255 Tantalum Ta 73 180.9479
Osmium Os 76 190.2 Technetium Tc 43 99
Oxygen O 8 15.9994 Tellurium Te 52 127.60
Palladium Pd 15 30.9738 Thallium Tl 81 204.37
Platinum Pt 78 195.09 Thorium Th 90 232.0381
Plutonium Pu 94 242 Thulium Tm 69 168.9342
Polonium Po 84 210 Tin Sn 50 118.69
Potassium K 19 39.08 Titanium Ti 22 47.90
Praseodymium Pr 59 140.9077 Tungsten W 74 183.85
Promethium Pm 61 147 Uranium U 92 238.029
Protactinium Pa 91 231.0359 Vanadium V 23 50.9414
Radium Ra 88 226.0254 Xenon Xe 54 131.30
Radon Rn 86 222 Ytterbium Yb 70 173.04
Rhenium Re 75 186.207 Yttrium Y 39 88.9059
Rhodium Rh 45 102.9055 Zinc Zn 30 65.38
Rubidium Rb 37 85.4678 Zirconium Zr 40 91.22
296
Chlorine Cl 17 35.453 Lanthanum La 57 138.9055

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297

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A Book Of

Dr. A. V. Nagawade Dr. R. A. Pawar

Dr. S. S. Jadhav Dr. V. D. Bobade

Dr. A. D. Natu Dr. D. R. Thube

Dr. P. C. Mhaske Dr. L. K. Nikam

Published By : (−ve) Printed By :

It gives us an immense pleasure to place this “Text Book of Practical Chemistry” in

Suggestions for improving the book will be highly appreciated.

STRUCTURE OF PRACTICAL EXAMINATION

Physical Chemistry Practicals

Molecularity of reaction : Molecularity of a reaction is defined as the number of

a – x = Amount of methyl acetate remaining unreacted at time t

Prepare similar observation table for set II.

(a – x) = Amount of methyl acetate remaining unreacted at time t.

Find out kHCl and kH2SO4 from both the

Calculate kHCl and kH2SO4 from slope of both

To determine the first order velocity constant of decomposition of hydrogen peroxide by

Fig. 1: Experimental set up for measurement of volume of oxygen

1. Rate constant (k) by calculations :

Time ‘t’ Volume of 0.002 N (a – x) (b – x) a−x k1 (min–1)

Set II : Reaction at higher temperature (t1 + 10°C) :

1. Take 25 ml 0.05 N KI and 20 ml distilled water in clean stoppered bottle and 25 ml

t1/2 t1/2 time (t)

Fig. 1 : x vs. t, showing determination of half lives from initial concentrations

Fig. 1: Viscosity is measured using

(log [η] – log k)

⎛log [η] – log k⎞

Part B : Polymer Solution

2. Molecular weight of given polymer ………

where, x = mass of gas or solute adsorbed

Saturation pressure (PS) log K

Fig. 1: Freundlich Isotherms

ml. of NaOH required for ∴ ml. of NaOH required

Observation Table : Density of salt solution = 1.09 g/ml.

2. Critical solution temperature of phenol-water system (tCI) = ……. °C.

3. Increase in critical solution temperature (tCII – tCI) = ……….. °C.

orange. Now a potential gradient is

Fig. 2: Apparatus for determination of transport number of HCl

Fig. 3: Plot of volume swept in ml against

A light ray PO in the upper less denser

Fig. 2: Abbe refractometer-schematic

Homologous series Molar refraction Contribution of −CH2

Methanol, CH3OH 8.213 −

Ethanol CH3CH2OH 12.74 4.522

n-propanol, CH3CH2CH2OH 17.415 4.675

n-Butanol CH3CH2CH2CH2OH 22.130 4.615

As described in the previous experiment of refractometry, determine densities and

Plot a graph of specific refractivity

100 (rC − rB) 0 20 40 60 80 100

Refractive Index ‘n’

Concave Collimating Slit Filter Cuvette Slit Photocell and recorder

Fig. 2: Single beam photoelectric colorimeter

This experiment is also performed in three parts :

Part B : Determination of λmax :

1.0 1.0 100

O.D. 0.6 O.D. 0.6 % T 60

100 200 300 400 500 600 700

Sr. No. Description Value with units

2. Conc. of unknown solution from graph (b) = ………. moles/l

3. Conc. of unknown solution from graph (c) = ………. moles/l

0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

Part A : Preparation of solutions :

3. Make the instrument on and adjust zero optical density.