A MANUAL FOR

B.Sc.II CHEMISTRY

PHYSICAL EXERCISES
CONTENTS
Paper-No. -IX - Non -Instrumental
Paper-No. -X II - Instrumental

Name of Student : _____________________________ Roll.No.:__________

By

Dr. Umakant Chanshetti

M.Sc. M. Phil. Ph. D.

Principal,

JAWAHAR ARTS, SCIENCE & COMMERCE COLLEGE,

ANADUR, DIST: OSMANABAD
B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 1
 Practical Physical Chemistry- B.Sc. II
Index
Sr.
Name of Experiment Page
No.
Non Instrumental Experiments
Phase Diagram
1. To determine the critical solution temperature and composition of two partially 02
miscible liquids i.e. Phenol and Water.
Solubility (Thermochemistry)
2. To determine solubility of benzoic acid at different temperature & determine ΔH 04
of dissolution process.
Partition Coefficient-I
3. To study the distribution of Benzoic Acid between Benzene & Water at room 07
temperature & show the molecular state of Benzoic Acid in Benzene.
Partition Coefficient-II
4. To determine the equilibrium constant for the reaction KI + I2 → KI3 by partition 10
coefficient method.
Viscosity
5. To determine the molecular weight of higher polymer using its solution of different 13
concentration.
Chemical Kinetics.
6. 16
To investigate the kinetics of iodination of acetone.
Heat of Neutralization (Thermochemistry)
7. 19
To determine the heat of neutralization of HCl and NaOH using calorimeter.
Heat of Ionisation
8. 22
To determine the heat of Ionisation (Hi) of weak acid.
Instrumental Experiments
Conductometer – I
9. To determine normality & strength of strong acid in gram per liter by using strong 24
base Conductometrically.
Conductometer – II
10. To determine normality & strength of weak acid in gram per liter 26
by using strong base Conductometrically.
PH – Meter
11. 28
To determine normality & strength of HCl using 0.1 NaOH solution PH -metrically
Potentiometer.
12. To determine the normality and strength in gm/lit of HCl with 0.1 N NaOH using 30
quinhydron electrode Potentiometrycally.
Polarimeter
13. To determine the specific rotation and concentration of given cane sugar solution by 33
Polarimeter.
Colorimeter- I [Lambert-Beer’s law]
14. To verify Beers-Lamberts law using various dilution of KMnO4 solution & to find 36
out λ max & concentration of KMnO 4 in unknown solution colorimetrically.
Colorimeter-II [Indicator Constant]
15. 39
To determine indicator constant of a given Methyl Red indicator colorimetrically.
Refractometer
16. To determine the specific refractivity’s of the given liquid A and B 43
& determine percentage composition of the mixture C of liquid A and B.
B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 2
 Non Instrumental Experiment
1. Phase Diagram
Aim: To determine the critical solution temperature and composition of two
partially miscible liquids i.e. Phenol and Water.

Theory: Phenol- Water system has an upper critical solution temperature. If phase rule is
applied to phenol-water system, it is found that the system has two degrees of
freedom (invariant) as –

F = C - P +2
F=2-2+2=2
Where, C is the number of components i.e. phenol and water, P is the number of
phase which are two in the system.
Since the system is having two degrees of freedom i.e. pressure and
temperature, if. The pressure is fixed; temperature alone will define the system
completely
When phenol and water are shaken together, two layers separate, one is
the separated solution of phenol on water in phenol. As the temperature is
increased, the two phases will be mutual soluble. This miscible temperature i.e.
Critical Solution Temperature at which Phenol & Water merge into each other. If
the composition is plotted against miscible temperature (CST), a curve will be
obtained. The maxima of the curve correspond to the critical solution temperature.

Apparatus: Hard glass test tube, thermometer, stirrer etc.

Chemicals: phenol; distilled water.

Procedure: The following steps are involved in it-

1) Take thoroughly cleaned and dried nine hard glass test tubes and number them
as 1 to 9. Take 1,2,3,4,5,6,7,8 and add 9,8,7,6,5,4,3,2,1 ml distilled water to 1
to 9 respectively in each test tube.
2) Arrange the apparatus with test tube no.1 as shown in figure 3. And stir the
mixture which will be turbid Heat the both & continuously stir the mixture at
which the turbidity disappears and a clear solution is obtained.
3) Remove the test tube from water to cool slowly, stir the mixture slowly and
note the temperature at which turbidity reappears. The mean of the above two
temperature give temperature of complete miscibility for that composition of
the mixture.
4) Similarly determine the temperature of miscibility for other solutions.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 3

Observations Table:

Sr. Volume Volume Composition Miscibility temp

No. of of of Turbidity Turbidity Mean
phenol water % phenol disappears disappears toC
in ml in ml t1oC t2oC
1 9 10
1

2 2 8 20

3 3 7 30

4 4 6 40

5 5 5 50

6 4 60
6

7 7 3 70

8 8 2 80

9 1 90
9

Graph:
The percentage composition of phenol is plotted on X- axis against the miscibility
temperature (t oc) on the Y-axis. The Y Co-ordinate of the maximum point on the
graph corresponds to the critical solution temperature (Tc) and the corresponding
point on X- co-ordinate given the critical composition.

-------CST
Result:
The critical Solution of phenol-water system = -------- o c
The critical composition of phenol-water system is = _______ %

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 4

 2. Solubility

Aim:- To determine solubility of benzoic acid at different temperature & determine

ΔH of dissolution process.
Theory: - When a solute is dissolved in a solvent, the heat is either absorbed or evolved.
When 1 gm mole of solute is dissolved in excess of this solvent, the further
addition of solute does not affect the change in heat.
The effect of temperature on solubility of the given solute is given by vant
Hoff’s equation.

Where, S is solubility in moles per liter and ΔH is heat of solution.

On integrating the above equation,
We have.
Log S. = + const. --------( 1).
Equation (1) is just similar to equation of straight line i.e. y = mx + c.
Thus if the graph of log S against is plotted, it is a straight line with negative
slope. From it, calculate the heat of solution i.e. ΔH. Similarly the heat is of
solution ΔH at only two different temperatures can also be calculated by using a
formula.

ΔH = 2.303R log

Where,
S1 = Solubility of solute at temp T1.
& S2 = Solubility of solute at temp T2.

Normality can be calculated by using the formula----

N=
The Solubility i.e. Strength can be calculated by using formula---------
Strength (S1) = N X Equivalent Weight of Benzoic Acid i.e. (122)

Chemicals: - Benzoic acid, NaOH, phenolphthalein, indicator, distilled, water etc.

Apparatus: - Beaker, burette, pipette, funnel, 1/10th thermometer, thermostat or water bath
etc.
B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 5
Procedure:- Maintain the temperature of thermostat or water bath of 30oC, take 100 ml water
in a beaker place it in thermostat, add slowly solid benzoic acid in a beaker with
constant stirring, as solid benzoic acid remains undissolved then filter the solution
in a clear beaker & cover it with watch glass [outside of the thermostat].
Now pipette out 10 ml of this filtrate in a conical flask. Add to it 2-3 drops
of phenolphthalein indicator & then titrate this with 0.05N NaOH solution. Take
2-3 reading & record the constant burette readings. The end point is colorless to
pink.
Repeat the same procedure for the temp 40oC to 50oC to 60oC. Determine
the normality of saturated solution and solubility i.e. strength of benzoic acid in
each case.

Result: - 1. Heat of dissolution, ΔH by calculation -------------------Cal / mole

2. Heat of dissolution, ΔH by graphical method ---------------- Cal / mole

Observation table:-

Temp of Burette Reading

Temp 1/T
o (To) K Mean Normality Strength Log S
C o K-1 I II III
C + 273 B.R.
30 303 0.0032
40 313 0.0031
50 323 0.0031
60 333 0.0030

Calculation:-
1) Normality can be calculated by using the formula----

N=
2) The Solubility i.e. Strength (S) can be calculated by using formula---------
Strength (S) = N X Equivalent Weight of Benzoic Acid i.e. (122)

3) Log S2/S1 = + Constant

Log S2/S1 =

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 6

 Log S2/S1 =

Log = x

ΔH = 2.303R Log

Graph: - Log S. = + constant.

Above equation is just similar to equation of straight line i.e. y = mx + c. Thus if

the graph of log S against is plotted, it is a straight line with negative slope. From it, calculate
the heat of dissolution i.e. ΔH.

Log S

1/T

Result: - 1. Heat of dissolution ΔH by calculation is --------------- Cal / mole.

2. Heat of dissolution ΔH by graphical method is ----------------Cal / mole.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 7

 3. Partition Coefficient-I

Aim: - To study the distribution of Benzoic Acid between Benzene & Water at room
temperature & show the molecular state of Benzoic Acid in Benzene.
OR
Determine the partition coefficient of Benzoic Acid in Benzene-Water system.
Theory: - The carboxylic acid like benzoic acid, succinic acid has a tendency to dimerize in
non–polar solvents like Benzene, Toluene etc. The dimerization take place
through hydrogen bonding, therefore the distribution of the acids in water & non
polar solvent do not obey the distribution law = [K = C1 / C2]
Benzoic acid associate in benzene to give a dimer.

2 C6H5 COOH → (C6H5COOH) 2

Benzoic acid Dimer.

When a solute associate in Benzene and Water, the phase distribution or

partition coefficient (K) is given by

K = =

C org = 0.1 x B.R / 5 C aq. = .

The value of ‘n’ can be determined by hit & trial method giving different values
of n i.e. 1,2,3,4 etc. so as to obtain constants value obtains of K.
Alternatively ‘n’ value be determined by the following method from the above
equation, we have.
Log K + log Caq = 1/n log. Corg.
Log Caq = 1/n log Corg – log K
This in an equation of straight line hence a plot graph of log Caq (y - axis)
against log Corg (x - axis) must be a straight line with slope equal to 1/n & the
intercept equal to – log K.
Chemical: - Benzoic acid, 0.1N NaOH, pure benzene, phenolphthalein etc.
Apparatus: - Stoppered bottles, burette, pipette beakers, conical flasks etc.
Producer:-
1. Take four stoppered bottles & label them as 1,2,3,4 etc. & in each bottles
place 50 ml of distilled water & 50 ml of benzene.
2. Weigh 1,2,3,4 gm of benzoic acid & transfer these amounts to bottle numbers
1,2,3,4 respectively.
3. Shake the bottles for an hour.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 8

 4. Allow the mixture to stand for some time, two layers will be separated. The
upper layer will be benzene layer which is called organic layer & the lower
layer is of water, which is known as aqueous layer.
5. Pipette out 5 ml of benzene layer from first bottle in a conical flask and to it
add about 20 ml of distilled water, shake vigorously & titrate against 0.1 N
NaOH using phenolphthalein as an indicator. Take three constant readings for
the upper benzene layer & take their mean. Similarly titrate 5 ml of benzene
layer from other bottles using same NaOH solution.
6. Remove the lower aqueous layers of bottle into separate beaker or bottle by
separating funnel. Titrate 10 ml of aqueous layer of each bottle against 0.1 N
NaOH. Take three readings for each bottle & take their respective mean.
7.
Result :- The value of n =
Hence, benzoic acid exists as dimer.

Observation Table:-

Volume of 0.1 N NaOH Volume of 0.1 N

layer Caq.
Bottle No.

Log Corg.
Conc. of
Conc. of

Log Caq
aqueous
benzene

for 5ml benzene layer NaOH for 10 ml Corg

layer

(organic layer) aqueous layer

I II III Mean I II III Mean C aq.
1. 1. 1.
1. 9.6 8.3 8.3 1.6 0.16 0.40 0.17 23.5
5 6 6
15. 2. 2. 2.
2. 15 15 2.3 0.3 0.574 0.023 23.78
3 2 3 3
25. 25. 25. 2.
3. 3 3 3 0.514 0.714 0.030 23.8
7 6 7 7
30. 3. 3. 3.
4. 30 30 3.3 0.6 0.77 0.030 23.45
5 3 3 4

Calculation:-
1) Concentration of organic layer ( Corg.) 2) Concentration of aqueous layer (Caq.)
N1V1 = N2V2 N1V1 = N2V2
N1 = N2V2/V1 N1 = N2V2/V1
Corg.= 0.1xB.R./5 Caq..= 0.1xB.R./10
3) Partition Coefficient (K)

K=
Caq.
B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 9
 Graph:-
Plot a graph of log Caq against log Corg, from this ‘n’ value be determined
by the following method from the above equation, we have.
Log K + log Caq = 1/n log. Corg.
Log Caq = 1/n log Corg – log K
This in an equation of straight line hence a plot graph of log Caq (y - axis)
against log Corg (x - axis) must be a straight line with slope equal to 1/n & the
intercept equal to – log K.

Log Caq Slop= 1/n

Intercept= -log K

Log Corg

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 10

 4. Partition Coefficient-II
Aim: To determine the equilibrium constant for the reaction KI + I2 → KI3 by
partition coefficient method.

Theory: The equilibrium constant of this reaction, KI + I2 KI3 is given as

K=

In order to determine the equilibrium constant, the active concentrations of the

products and the reactants i.e. KI3, KI and I2 must be determined. To do it, we
make use of the distribution coefficient of iodine in carbon tetra chloride and
water. IF water is added to a solution of iodine in carbon tetra chloride iodine will
distribute itself in both the aqueous and CCl4 (Organic) layers after some time.
The distribution coefficient (Kd) of iodine between CCl4 and water may be written
as Kd =

By the knowledge of Kd (I2), concentration of Iodine [I2] in water layer may be

calculated if concentration of [I2] in the CCl4 layer is known. This will be made
use of in finding the equilibrium constant K for the reaction KI + I 2 KI3 as
given above.

Apparatus: Glass stoppered bottles, pipettes, burette, conical flasks, thermostat etc.
Chemicals: Iodine, CCl4, KI, Na2S2O3 and distilled water etc.
Procedure: The procedure of it involves two steps:
I) Determination of partition or distribution coefficient (Kd).
II) Determination of equilibrium constant K with the help of Kd i.e. partition
coefficient so the following steps are taken.
I) Determination of partition or distribution coefficient Kd.
1) Prepare a nearly saturated solution of I2 in CCl4 by dissolving 4-5 gm of
iodine in 150 ml of CCl4.
2) Take 30 ml, 40 ml and 50 ml of above I2 solution in three bottles namely 30%,
40% & 50% respectively, to these bottles make the volume 50 ml by adding
CCl4 i.e. add 20 ml, 10 ml & 0 ml of CCl4 to 30% , 40% & 50% bottle
respectively.
3) Now add 50ml of water to each bottle to make volume 100 ml. Shake
vigorously for 30 minutes and then allow standing for half an hour.
4) Separate two layers by using the separating funnel.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 11

 5) Pipette out 10 ml of water layer of bottle 1 and titrate it against 0.01 N
thiosulphate (hypo) solution using starch as an indicator repeat the same for
other water layers.
6) Now, pipette out 10 ml of CCl4 layer of bottle 1 and titrate it against 0.05 N
thiosulphate (hypo) solution using starch as an indicator. Repeat the same for
other CCl4 layers.
7) Similar experiment is performed using 0.1N solution of KI in place of water
and prepares 30%, 40% and 50% solution as above.
8) The I2 in two layers / is titrate i.e. KI layer and CCl4 layer against 0.05N
thiosulphate , (hypo) solution using starch solution as an indicator
9) The concentration of I2 in KI & CCl4 layers can be calculated and substituting
the values of C1, Cx, Cy and D in equation

K=

Where, Cx = the total concentration of iodine in aqueous layer.

Cy = the concentration of iodine in CCl4 (organic) layer.
C1 = the total concentration of KI in aqueous layer
D = the distribution coefficient between CCl4 and water
Observations:

I) Determination of distribution coefficient (Kd)

ml of 0.05 N hypo soln ml of 0.1N hypo soln for Concn. Concn.

Concn. for 10 ml CCl4 layer 10 ml H2O layer of I2 in of I2 in
of CCl4 H2O
solution I II III Mean I II III Mean layer layer (D)
Corg CH2O
50%
40%
30%

II) Determination of equilibrium constant (K)

ml of 0.05 N hypo soln ml of 0.05N hypo soln Concn. of Concn.

Concn.
for 10 ml CCl4 layer for 10 ml H2O layer I2 in of I2 in
of K
Mean Mean CCl4 KI(H2O)
solution I II III I II III
[Y] [X] layer layer
50%
40%
30%

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 12

Calculation:

I) Calculate Kd i.e. D = distribution coefficient from the formula –

II) Calculate K i.e. Equilibrium constant.

a) Now from 50% solution:
1) Total concentration of KI in H2O layer i.e. C1

(Equivalent weight of KI = 166)

2) Total concentration of iodine in aqueous layer i.e. Cx is given by---

N1V1 = N2V2
N1 X 10 = 0.05 X (MBR) (x)
N1 =
(Equivalent of weight of iodine = 127)
3) Total concentration of iodine in CCl4 layer i.e. Cy is given by_____
N1V1 = N2V2
N1 X 10 = 0.05 X 127 X (MBR) (x)
N1 =

Hence K1 =

b) Similarly from 40% solution- Cx and Cy values will be calculated as in

previous case
K2 =
c) From 30% solution
K3 =
Mean equilibrium constant –
K=

Result:

The value of equilibrium constant K =-------------- by distribution coefficient

method.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 13

 5. Viscosity
Aim: - To determine the molecular weight of polymer using its solution of different
concentration by viscosity measurements.
Theory: - the viscosity of a high polymer solution is related to the molecular weight of the
Polymer by the Staudinger equation as follows.
[ ] = KMa
Where [ ] is the intrinsic viscosity and M is the average molecular weight of the
polymer, K and ‘a’ are the constants for given solvent polymer system.
If the absolute viscosity of the solution is and that of the solvent is ,

the relative viscosity is given by .

If the times of flow for solution and solvents are t and t o, then

The densities of solution and solvents are very close, since the polymer
solutions used in the experiment are very dilute, their densities will be
approximately equal to that of solvent.

Relative viscosity,

The specific Viscosity,

Then the reduced viscosity will be given by

Where, C is the concentration of polymer in gm/100 ml of solvent.

Intrinsic viscosity [ ] which is related the molecular weight of polymer

can be obtained by ploting against concentration C, a straight line will be

obtained which on extrapolation to C = O; the intercept is the intrinsic viscosity.
Thus the molecular weight of a polymer can be determined from
viscometric measurements using Schrodinger equation, provided K and a
are known. [ ] = K Ma
The values of K and a for some polymer – solvent systems are given in table at
25oC
Polymer Solvent K a
-4
Polystyrene Toluene 3.7 X 10 0.62
-4
Poly isobutylene Toluene 3.6 X 10 0.64
-4
Poly vinyl alcohol Water 2.0 X 10 0.76
-4
Cellulose Acetate Acetone 1.49 X 10 0.82

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 14

Apparatus: - Ostwald’s viscometer, Specific Gravity bottle, pipette, stop, volumetric, flasks
Chemicals: - Polymer i.e. polyvinyl alcohol, distilled water,

Procedure:-
This method involves the preparation of a series of the polymer say polyvinyl alcohol in
suitable solvent say water and the measurement of their viscosity by Ostwald’s
viscometer.
1) Weigh accurately 1 gm of polymer sample (polyvinyl alcohol ) and transfer in
a beaker containing about 70 ml solvent (water) and warm it with constant
stirring cool and transfer the solution in 100 ml standard volumetric flask,
wash the washing into the volumetric flask then dilute up to the mark, keep
solutions in thermostat at 25oc. This is 1% solution which can be used as stock
solution.
2) Form this stock solution, prepare 0.8, 0.6, 0.4, 0.2 and 0.1 (gm / 100ml)
solution and keep them in the same thermostat at 25oc.
3) Determine the time of flow of solvent i.e. water say to. Similarly determine
the time of flow of each solution say t.
Observation:-
1) Time of how of the solvent (water) = to = ------------- sec
2) Density of the solvent = = ------------ gm/cc
Observation Table:-
Part- I

Time of flow (second)

Solvent t0 Mean Time t0 (second)
1 2 3
Water
Part- II
Time of flow for
Conc of Relative Viscosity Reduced Viscosity
Polymer solution Specific Viscosity
Polymer
(t)
C
1 2 3 Mean
0.1
0.2
0.4
0.6
0.8
1.0

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 15

Calculations:-
Calculate the relative viscosity

The specific viscosity

The reduced viscosity

Graph :-
Plot a graph against Concentration and from the intercept of
straight line (at C = O) , calculate intrinsic viscosity Then by using the
Schrodinger equation calculate the molecular weight of polymer i.e.
polyvinyl alcohol, taking the known values of the constant K and a
[ ] = K Ma
log [ ] = a log M + log K

[ ]= Intrinsic Viscosity

Concentration ( C )

Thus knowing the value of [ ] i.e. intrinsic viscosity of the given

Polymer from the graph and the constants K and a (given), the molecular
weight of high polymer can be calculated by using formula….
[ ] = K Ma
log [ ] = a log M + log K

Result: The molecular weight of given Polymer is-----------------

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 16

 6. Chemical Kinetics
Aim:- To investigate the kinetics of iodination of acetone.
Theory:- Iodine reacts with aqueous acetone in presence of acid ( which acts as catalyst) to
form mono iodoacetone.
CH3COCH3 + I2 CH3COCH2I + HI.
The reaction is catalyzed by hydrogen ions and rate of reaction found to be
Independent of iodine concentration.

Rate = = K [Acetone] [Acid (H+)]

If concentration of acetone & acid is constant on these are in excess, rate const.
K is const. It means observed rate d [I2] /dt is independent of iodine concentration
& the reaction is said to be zero order with respect to I2 concentration.
It is interesting to see mechanism which simply keto form converts into
enol form in presence of H+ ions.

It reacts with water molecule with removed of proton

How iodine reacts with these enol form & converts into acetonlyl iodine.

The free iodine is then titrated against standard sodium thiosulphate solution
using starch as an indicator.
The reaction in which keto form is converted to enol is slow and rate
determining step, hence in this reaction kinetics and order of reaction is zero with
respect to iodine (I2).
Apparatus: - Burette, Pipettes, Conical flasks, Stoppered bottles, Stopwatch, Measuring
cylinder etc.
Chemicals :- Acetone, 2 N H2SO4, 0.1 M I2 in 10% KI, 0.01 M Sodium thiosulphate solution,
1M Sodium acetate or 1M NaHCO3, Starch indicator etc.
Procedure:-
1. Prepare four sets of mixture of Acetone, water and Sulphuric acid in four
clean bottles as shown below.
Bottles No →
1 2 3 4
Chemicals ↓
Acetone 10 10 15 15
Water 70 65 55 60
Sulphuric Acid 10 10 10 15

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 17

 2. Keep these bottles in water bath to attain the same (uniform) temperature.
Also place the solution of 0.1 M I2 solution in the same water bath to attain
the bath temperature.
3. Fill the burette with 0.01 Na2S2O3 solution
4. Pipette out 10 ml 1 M sodium acetate solution (or 1 M NaHCO3 solution) to
each of the six or seven clean conical flasks to quench the reaction before the
titration.
5. After the solutions in water bath have reached a same temperature of bath (15-
20 minutes), transfer 10 ml of 0.1 M I2 solution by means of pipette to bottle
number 1 and start the stopwatch. Mix the contents well with gentle stirring,
wait for three minutes.
6. After three minute pipette out 10 ml of reaction mixture from bottle number 1
and transfer in a conical flask which already containing 10 ml of sodium
acetate ( or sodium bicarbonate) solution. Add about 4-6 drops of starch
indicator & titrate the unconsumed Iodine in the reaction against Na2S2O3
7. Shake the reaction mixture from time to time. Repeat the titration using 10 ml
of reaction mixture after successive intervals of 6, 9, 12, 15 and 18 minutes
from time of mixing.
8. Similarly add 15, 20 & 10 ml of iodine solution successively in bottle No. 2, 3
and 4 and repeat the procedure as mentioned above.
Hints: - 1. Shake the reaction mixture time to time.
2. Keep the reaction mixture closely stoppered.
3. Keep the reaction mixture in the water bath,
4. During titration add 2-3 drops of starch solution (indicator) only near
the end point. (This is a stage during the addition of 0.01 Na2S2O3
solutions to a reaction mixture when the iodine color fades to yellow.)

Observation Table:-
Temperature of water bath = -------------- 0C
Time (t) in Burette reading (ml) (Titrant volume)
minutes Set-1 Set- 2 Set- 3 Set- 4
3
6
9
12
15
18

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 18

Graph:- Plot a graph of titrant volume (Burette Reading) against time, for these four sets.
These plots will be straight lines slopping down with constant value of slopes (K).

The straightness of lines indicates a

constant slope and constant rate of
the reaction. The reactant changing
concentration significantly is in case
B. R. of iodine and since the rate of the
reaction does not decrease as iodine
concentration decreases, it is
independent iodine concentration.
Order of reaction in respect of
iodine is thus zero.
Time (min)

Result :-
1. The value of K =
2. The order of reaction. =
i.e. the kinetics of iodination of acetone is ______________

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 19

 7. Heat of Naturalization
Aim: To determine the heat of neutralization of HCl and NaOH using calorimeter.
Theory:
Heat of neutralization is defined as the amount of heat evolved when one gram
equivalent of as acid neutralizes one gram equivalent of base in dilute solution.
The heat of neutralization is actively the heat given out in the union of H+
and OH-along with the heat accompanying dissociation of acid or base.
HCl H+ + Cl-
NaOH Na+ + OH-
Na+ + OH- + H+ + Cl- Na+ + Cl- + H2O
H+ + OH- H2O – 13.7 Kcals
So heat of neutralization can be regarded as consisting of combination of
hydrogen and hydroxide ion to form unionized water.
Apparatus: Calorimeter, pipette, beaker, thermometer etc.
Chemicals: 0.25 N HCl solution, 0.25 N NaOH solution, distilled water etc.
Procedure: It involves two steps:
I) Determination of water equivalent of the calorimeter.
II) Determination he heat of neutralization of HCl by NaOH
I) Determination of water equivalent of the calorimeter.
1) Take 50ml of distilled water in the clean and dried flask of calorimeter Wait
for same time so that water attains the room temperature. Note this
temperature ( t1oc)
2) Take another 50 ml of distilled water in beaker and heat it to a temperature of
about 15oc above the room temperature. Note the temperature ( t 2oc)
3) Pout immediately the hot water into the calorimeter containing cold water, stir
the mixture. The temperature of cold water gradually rises Note the maximum
temperature reached i.e. ( t3oc)
4) Calculate water equivalent W of the calorimeter,
II) Determination Heat of neutralization of HCl by NaOH:
1) Prepare exactly 0.25N HCl and 0.25 N NaOH solutions in distilled water by
quantitative method. Standardize these solutions by usual procedure.
2) Wash and dry the calorimeter. Take 50 ml of 0.25 NaOH solutions in the
calorimeter. Note down the temperature for every minute for about 5 minute
with constant stirring; say i.e. t NaOHoc
3) Take 50 ml of 0.25 HCl solutions in a beaker. Note down the temperature for
every minute for about 5 minutes with constant stirring say i.e. t HCloc
4) Take the mean temperature of HCl and NaOH solution i.e. t 4oc
5) Now pour the acid solution immediately into the base in calorimeter and stir it
constantly. Note the exact time of mixing and record the temperature for every
B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 20
 minute for about 7-10 minutes. After every minute the temperature falls
uniformly.
6) After the experiment, test the mixture with a drop of phenolphthalein to check
whether the acid base has been completely neutralized.
7) Since in the neutralization process heat is evolved, the temperature first rises
rapidly, then slowly begins to fall due to the heat loses by radiation. Due to
the loss of heat the highest temperature recorded will be slightly less than the
obtained, if no losses of heat took place. A temperature correction is therefore
necessary to get correct rise in temperature, which can be done as follows:
A temperature correction:
Plot the temperature against time and draw the graph as shown in fig. in this fig. the
temperature of acid and base are shown to be rising slowly, but the reverse may also be found.
Draw a perpendicular at the time of mixing (say of minute). The points at which the
perpendicular meets the straight lines of acid and alkali will give the temperature t 4 and t4 of the
acid and alkali at the time of mixing Draw a straight line through points where the temperature
begins to fall regularly. Extrapolate the line back to cut the perpendicular. The point of
intersection given the correct highest temperature t 5, which would have been obtained if no loss
of heat occurred due to radiation

t5

Temp t4

t4

Time in min.

Observation:
I) Determination of water equivalent of calorimeter.
1) Volume of cold water = V1 = 50 ml
2) Temperature of cold water = t 1oc = _____ oc
3) Volume of hot water = V2 = 50ml
4) Temperature of hot water = t2oc =______oc
5) Final temperature after mixing hot and cold water in calorimeter t 3oc= __ oc

II) Determination of heat of neutralization of HCl & NaOH

1) Volume of 0.25N HCl = V3 = 50 ml
2) Volume of 0.25N NaOH = V4 = 50ml
3) Mean temperature recorded for HCl & NaOH = t4oc = _____ oc

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 21

Calculations:
I) Determination of water equivalent (W) :
Heat evolved or given out by hot water = Heat gained or absorbed by cold water +
Heat gained or absorbed by calorimeter

(mass x sp. Heat x fall in temperature) =) mass x sp. heat rise in temperature) +
(water equivalent rise in temperature)
Mass = volume X density
For water Density & specific heat is considered as unity i.e. 1,
Hence volume of water = mass therefore,
50(t2-t3) = 50(t3-t1) + W (t3-t1)
W= cal.
Where, W is water equivalent of calorimeter.
II) Determination of Heat of neutralization:
If Q is the amount of heat evolved during the reaction, then we have.
[Heat evolved during the reaction] = [Heat gained or absorbed by NaOH solution]
+ [Heat gained or absorbed by HCl solution] + [Heat gained or a absorbed by
calorimeter]
Q = (volume X rise in temp. of NaOH) + (volume of HCl + rise in temp) + (water
equivalent C rise in temp)
Q = 50 (t5 – t4) + 50 (t5-t4) + W (t5-t4)
Q = (50+50+W) (t 5-t4)
Q = (100 + W) (t 5-t4)
The Q cals of heat evolved when 0.25N HCl i.e. 1/16 gm equivalent of mole in
neutralized by equal amount of NaOH.

Result: The heat of neutralization of an acid HCl and base NaOH = ____ calories.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 22

 8. Heat of Ionisation

Aim: To determine the heat of Ionisation (Hi) of weak acid.

Given: NaOH ‘Z’ N; HCl ‘Z’ N; CH3COOH ‘Z’ N (Z= 0.5 N or 1 N)

Procedure:
Perform the expt. in 2 parts.
PART A

Determination of Heat of Neutralisation using strong Acid (HCl) and strong Base (NaOH)

1) Take 100 ml of strong acid in a clean polythene bottle using a measuring cylinder.
2) Take 100 ml of strong base in another polythene bottle using a clean measuring cylinder.
3) Keep both the bottles in a water bath for about 10 min. to attain a steady temp.
4) Record Initial temp. of Acid (t 1OC) when the bottle is in the water bath.
5) Clean the thermometer and take Initial temp. of the base (t 2OC) keeping the bottle in the water
bath.
6) Take both the bottles out of the water bath. Add Acid to the Base quickly and carefully. Stir
well and measure the maximum temp. of the mixture (t 3OC).
7) Note down the Rise in temp. (t)
8) Ask for the value of ‘Z’ and calculate (H1) i.e. Heat of Neutralisation of strong Acid and
strong Base.
PART B
Determination of Heat of Neutralisation using weak Acid (CH3COOH) and strong Base
(NaOH)

Similarly find out Rise in temp (t) using CH3COOH and NaOH.
Calculate Heat of Neutralisation of Weak Acid and Strong Base (H2)
Then calculate Heat of Ionisation of Weak Acid (Hi)

HEAT OF IONISATION
OBSERVATIONS

TABLE A : HCl and NaOH Z = ___________ N W = __________ cal.

Vol. of Acid Temp. of Temp. of Initial Max. Temp Rise in H.N. H1
+ Base ml Acid t1OC Base t2OC Temp. of Mixt. Temp.
t 1+ t 2 / 2 = t3OC. t3 – t = – Joules
t OC tOC

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 23

 TABLE B : CH3COOH and NaOH Z = ___________ N W = __________ cal.

Vol. of Acid Temp. of Temp. of Initial Max. Temp Rise in H.N. H1
+ Base ml Acid t1OC Base t2OC Temp. of Mixt. Temp.
t 1+ t 2 / 2 = t3OC. t3 – t =
t OC tOC – Joules

CALCULATIONS

Part A Part B

1) Heat evolved = Q = t (200 + W) 1) Heat evolved = Q = t (200 + W)

= _____ cal. = _____ cal.

2) Heat of Neutralisation 2) Heat of Neutralisation

10 x Q 10 x Q
H1 = ––––––– H2 = –––––––
Z Z
= =
= – (_____) cal. = – (_____) cal.

HEAT OF IONISATION OF WEAK ACID

Heat of Ionisation Hi = H2 – H1 = H2 – H1

= –( ) – (– )
= –( ) + (– )
= +( ) cal.
Result :
1) H1 = –( ) Cal. = Joules. 1 cal. = 4.184 Joules.
2) H2 = –( ) Cal. = Joules.
3) Hi = +( ) Cal. = Joules.
Reactions :

Part A Part B

HCl + NaOH –––– NaCl + H2O CH3COOH CH3COO– + H+ – q cal.

H+ + Cl– + Na+ + OH– –– Na+ + Cl– + H2O CH3COO– + H+ + Na+ + OH– ––
CH3COO– + Na+ + H2O

i.e. H+ + OH– ––– H2O + Q i.e. H+ + OH– ––– H2O + Q.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 24
 Instrumental Experiments
1. Conductometer – I

Aim:- To determine normality & strength of strong acid in gram per liter
by using strong base Conductometrically.
Theory :- Electrical conductivity depends upon the number of ions present & then
ionic mobility’s, when an acid in titrated with NaOH the conductance will
go on changing & when the acid is just neutralized i.e. at the equivalence
point, the solution will contain only NaOH. When excess of NaOH added
to the solution it will contain NaCl + NaOH. The conductance will go on
increasing it is due to produce of free OH- ions of NaOH.
Thus on plotting a graph of conductance versus volume of titrate (volume
of NaOH) added two branches of straight lines may be obtained. The
point of intersection of two lines will give end point or equivalence point.

Apparatus: - Conductometer, conductivity cell, beaker, micro burette, pipette etc.

Chemicals: - HCl, NaOH, Distilled water etc.
Procedure:-
i) Rinse & fill the burette with 0.1 N NaOH solutions.
ii) Pipette out 5 or 10 ml of given HCl solution in a clean 100 ml
beaker.
iii) Add about 50 ml of distilled water to it, due to addition of water
the mobility of ions increases.
iv) Dip the conductivity cell in the beaker & connect it to
Conductometer.
v) Record the initial conductivity of HCl; it is at ‘o’ ml of NaOH.
vi) Now add 0.5 ml of NaOH solution form burette to the beaker and
stir the solution.
vii) Record the the conductivity of HCl at 0.5 ml addition of NaOH.
viii) Repeat the same & record the conductance with successive
addition of 0.5 ml NaOH up to 10 ml or 20 ml of NaOH added.
ix) Find out the equivalence or end point of the acid base titration by
plotting the graph of observed conductance against the volume of
NaOH added.
In burette – 0.1 NaOH solution.
By pipette – conductivity cell (5 or 10 ml) of HCl + 50 ml distilled water.
Result:-
1) End point =
2) Normality of HCl = N
3) Strength of HCl = gm/lit
B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 25
 Observation Table:-

Sr. Volume NaOH Added Observed Conductance

No. in ml in Mhos x 10-3
1 0
Calculation:-
2 0.5
3 1.0
4 1.5 1. Normality of strong acid i.e. HCl.
5 2.0 HCl Vs NaOH.
6 2.5 N1 V1 = N2V2
7 3.0 N1 =
8 3.5
9 4.0 N1 =
10 4.5
11 5.0 N1 = --------------- N
12 5.5 Normality of strong acid = N.
13 6.0
14 6.5 2. Strength of acid :-
15 7.0 = Normality X Equivalent Weight of HCl
16 7.5 = N1 X 36.5
17 8.0
Strength of acid = gm/lit
18 8.5
19 9.0
20 9.5
21 10.0

Graph:-
Plot a graph of conductance versus volume of titrate (volume of NaOH) added two branches
of straight lines may be obtained. The point of intersection of two lines will give end point
or equivalence point.

Cond
Ώ

End point

Volume of NaOH added X

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 26

 2. Conductometer – II
Aim:- To determine normality & strength of weak acid in gram per liter
by using strong base Conductometrically.
Theory:- Consider the titration of acetic acid [CH3COOH] with sodium hydroxide
[NaOH]

. + Na+OH- CH3COO-Na+ + H+OH-

Weak Acid Strong Base Salt Water.
It is titration of weak acid with strong base. The salt obtained sodium
acetate is a strong electrolyte at the beginning of the titration. The acid
solution has low conductivity because acetic acid is weak acid & may not
dissociate completely therefore there are less H + ions available to
contribute the conductivity value.
When small amount of NaOH is added to the acetic acid solution
the conductivity decrease initially & then increases slowly by further
addition of NaOH. At the point the solution will contain only sodium ions
& acetate ions [CH3COO-] after end point conductivity rises rapidly
because of addition of strong alkali (NaOH).
Apparatus: - Conductometer, conductivity cell, beaker, micro burette, pipette etc.
Chemicals: - Acetic acid, NaOH, distilled water etc
Procedure:-
i. Rinse & fill the burette with given standard NaOH solution.
ii. Pipette out 5 or 10 ml of given acetic acid solution in a clean 100 ml beaker.
iii. Add about 50 ml of distilled water to it, due to addition of water the mobility
of ions increases.
iv. Deep the conductivity cell in a beaker & connect it to conductormeter.
v. Record the initial conductivity of acetic acid; it is at ‘o’ ml of NaOH.
vi. Now add. 0.5 ml of NaOH solution. from burette to the beaker, stir the
solution.
vii. Record the conductivity of acetic acid at 0.5 ml of added NaOH.
viii. Initially the observed conductance slightly goes on increases with
every addition of 0.5 ml NaOH to the acetic acid.
ix. Repeat the same procedure & record the conductance with successive
addition of 0.5 ml NaOH up to 10 or 20 ml of NaOH added.
x. Find out the equivalence or end point of the acid base titration by plotting the
graph of observed conductance against the volume of NaOH added.

Result: 1. End point = -------------

2. Normality of acetic acid = ------------- N.
3. Strength of acetic acid = ------------ gm/lit.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 27

Observation:-
1) In Burette – 0.1 NaOH Solution.
2) By pipette – 5 or 10 ml of CH3COOH + 50ml distilled water.
Observation Table:-

Sr. Volume NaOH Added Observed Conductance Calculation:-

No. in ml in Mhos x 10-3
1 0 1. Normality of weak acid
2 0.5
i.e. CH3-COOH
3 1.0
CH3COOH Vs NaOH
4 1.5
5 2.0 N1 =
6 2.5
= ------------- N
7 3.0
8 3.5
9 4.0 2. Strength of acid
10 4.5 Strength of acid=
11 5.0 Normality X eq. wt. of CH3COOH
12 5.5 = ----------- X 60
13 6.0 = ----------- gm/lit
14 6.5
15 7.0
16 7.5
17 8.0
18 8.5
19 9.0
20 9.5
21 10.0
Graph:-Plot a graph of conductance versus volume of titrate (volume of NaOH) added two
branches of straight lines may be obtained. The point of intersection of two lines will give end
point or equivalence point.

Cond
Ώ
End point

Volumes of NaOH added X

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 28

 3. pH-Meter

Aim:- To determine normality & strength of HCl using 0.1 NaOH solution PH -
metrically

Theory: - Depending upon the capacity of forming H+ ions in the solution, the acid is called
strong if it dissociates completely or weak acid if it partially dissociate in the
solution.
HA H+ + A-

K=
K = dissociation constant.
It is convenient to express K in the form of its’ negative logarithm.
i.e. log ka = pka.
According to Henderson’s equation
PH = pKa + log
PH = - log H+
If acid solution is titrated against strong alkali, acid is converted into salt, when
half amount of acid in neutralized.
[Salt] = [Acid]
Log1 = 0
PH = Pka
Apparatus:- PH meter with glass & Calomel electrode, beaker, micropipette, burette etc.
Chemicals:- 0.1N NaOH, HCl, quinhydron powder, distilled water etc.
Procedure:-

1. Pipette out 5 ml or 10 ml of HCl solution in to 100 ml beaker, to it add 40-50

ml of distilled water.
2. Connect glass & calomel electrode to pH meter & dip in beaker & record the
pH.
3. Fill the micro burette with 0.1 N NaOH solutions.
4. Titrate the HCl solution with 0.1 N NaOH & record the PH values for every
addition of 0.5 ml alkalis.
5. Plot the graph of PH against volume of NaOH added and find end point of acid
from half equivalence point.
6. To find the exact end point plot the graph with differentiate values i.e. Δ pH/
ΔV against volume of NaOH added, from its peak draw a perpendicular on X-
axis.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 29

Calculation:-

1. Normality of strong acid i.e. HCl

HCl Vs NaOH
N1 = ------------- (I)

N1= ------------N

2. Strength of HCl = Normality of HCl X equivalent .wt of HCl

= N1 X 36.5
Strength of HCl = ----------- gm / lit.

Result:-

1. Normality of HCl = ---------N.

2. Strength of HCl = ---------- gm/lit
Observation:
i) In burette: NaOH solution.
ii) In conical flask: 5 or 10 ml HCl solution + 40ml of distilled water.
Graph

PH Δ PH
ΔV

Volume of NaOH added

Volume of NaOH added

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 30

 4. Potentiometer
Aim:- To determine the normality and strength in gm/lit of HCl with 0.1 N NaOH
using quinhydron electrode Potentiometrycally.

Theory:- Simple acid solution cannot produce potential difference between two electrodes
and there is no change of potential if acid solution is titrated with standard alkali.
To convert this system into reversible redox system, quinhydron powder is added
in acid solution.

Quinhydron powder is a compound which in aqueous solution forms

equimolar quantities of Quinone (Q) Hydroquinone (QH2) by following the
reaction.

Q + 2H+ + 2e- QH2

Platinum electrode is used for this half-cell and connected to make complete cell.

The cell can be represented as ------

Calomel electrode Quinhydron Platinum electrode

-
Hg. Hg2Cl2 KCl (satu) Quinhydron H+ Pt+

The E.M.F. of the cell is given by---

EObs = ERight - Eleft

EObs = E0 – 2.303 RT PH / F - Ecalomel

EObs = E0 – Ecalomel – 0.0591 PH

0.0591 PH = E0 – Ecalomel – EObs

0.0591 PH = 0.699 – 0.242 – EObs

PH = 0.456 - EObs
0.0591

Apparatus:- Potentiometer with calomel and platinum electrode, Burette, Pipette, Beaker,
magnetic stirrer etc.

Chemicals:- Hydrochloric acid (0.1 N), 0.1 N NaOH solution, quinhydron powder, distilled
water etc.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 31

Procedure:-
1. Rinse & fill the burette up to zero mark with standard 0.1 N NaOH solution.
2. Pipette out 5 ml or 10 ml of acid solution (HCl) in a 100 ml beaker. Add 40-
50 ml of distilled water to it and a pinch of (about 100 mg) quinhydron
powder. Stir it vigorously and keep it on stirring stand.
3. Connect the electrode, as Platinum electrode (Hydrogen electrode) to positive
pole (Anode) and calomel electrode to negative pole (Cathode) and dip them
into a beaker containing acid and quinhydron solution.
4. Note down the E.M.F. of solution containing Q QH2 ions at every 0.5 ml
addition of 0.1 N NaOH solutions from burette. Take readings up to 10 or 20
ml addition of 0.1 N NaOH solution.
5. At the equivalence point E.M.F. increases suddenly.
6. Plot a graph, E.M.F. against volume of NaOH added and also plot a graph of
7. Δ E
ΔV against volume of NaOH added and find the point from graph.
Observation:-
In burette: 01 N NaOH solution.
In Conical flask: - 5 ml or 10 ml of HCl solution + 40-50 ml of Distilled water +
100 mg of quinhydron powder.
Observation Table:-
Sr. Volume of Observed ΔE ΔV ΔE
No. NaOH added (V) E.M.F. (E) ΔV
1 0 0.0
2 0.5 0.5
3 1.0 0.5
4 1.5 0.5
5 2.0 0.5
6 2.5 0.5
7 3.0 0.5
8 3.5 0.5
9 4.0 0.5
10 4.5 0.5
11 5.0 0.5
12 5.5 0.5
13 6.0 0.5
14 6.5 0.5
15 7.0 0.5
16 7.5 0.5
17 8.0 0.5
18 8.5 0.5
19 9.0 0.5
20 9.5 0.5
21 10.0 0.5

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 32

Calculation:-

1. Normality of strong acid i.e. HCl.

HCl Vs NaOH
N1V1 = N2V2
N1 = (I)
2. Strength of acid :-
3. Normality X Eq. Wt. of HCl (36.5)
Graph:-

I] Plot a graph of E.M.F. against (V) i.e. volume of 0.1 N NaOH added.

II] Plot a graph of Δ E

ΔV against (V) i.e. volume of 0.1 N NaOH added.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 33

 5. Polarimeter

Aim:- To determine the specific rotation and concentration of given cane sugar
solution by Polarimeter.

Theory:- The apparatus consist of two nickel prism mounted on the axis of instrument, the
first prism known as Polarizer which is fixed & second prism known as Analyser
which can be rotated about the axis of the instrument. In between these two nickel
prisms a tube is placed. This tube is used for keeping the sugar solution whose
specific rotation is to be determined. Now when a beam of monochromatic light is
passed through the tube without containing the liquid, light gets polarized by the
first nickel prism & the come on the second prism which is rotated slowly as to
cut out light completely. The reading at this point of the scale corresponds to zero
reading. If, now glass tube containing optically active liquid is placed between
these prisms is rotated plane of polarize light to a certain angle & hence to get
dark field of view again, the analyzer will have to be rotated through the same
angle, the angle is measured with the help of graduated scale.
The angle of rotation caused by an optically active compound depends
upon the path length through which the light passes, wavelength of the light used,
temperature, nature of the solvent and the concentration of the solution. When all
the factors except concentration are kept constant, the angle of rotation depends
on the only concentration. As concentration increases, the angle of rotation
increases. Therefore a calibration curve can be prepared by plotting the the angle
of rotation against concentration of a series of solutions. From this curve, the
concentration of unknown solution can be determined by measuring its angle of
rotation.
Apparatus:- Polarimeter, Sodium lamp, Standard flask, Beakers, Funnel etc.
Chemicals: Pure sample of cane sugar, Distilled water etc.
Procedure:-
I) Determination of zero point
1. Clean the polarimeter tube with chromic acid then with distilled water and
remove any air bubble in the tube is driven into the bulb provided in the
middle of the tube. Tightly fit with metal cap.
2. Dry the exposed surface of the tube and its cap and place it in the instrument
between the polarizer and analyzer till the field of view are nearly matched.
Now with the help of the fine adjustment, set the analyzer for best matching.
When two halves match they have a grey color. Record the reading of the
scale as zero reading, for both the Vernier’s on the scale (1800 apart) to
remove the error. Take several readings of the zero position and take the

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 34

 average of these readings. This zero reading must be added to or subtracted
from the readings of the optically active substances as the case requires.
II) Determination of angle of rotation

1. Weigh accurately 20 gm of pure cane sugar crystals [dextrose] on a clean

watch glass. Dissolve it in 100 ml of distilled water. This will be 20% sugar
solution. If this 20% prepared sugar solution is not clear or turbid then filters
it with filter paper. Use this solution as a stock solution [20% conc. Sugar
solution].
2. From this stock solution prepare 2%, 4%, 6%, 8%, 10%, 12% and 14%
percentage of sugar solution by using this stock solution and distilled water
having total volume of 25 or 50 ml as shown in observation table.
3. Rinse the polarimeter tube with20% solution and fill up with it and remove
any bubble in the tube.
4. Place the tube in the Polarimeter.
5. Rotate the analyzer to get uniform illumination of both the halves in the field
of view. Note the reading. Now add or subtract the zero reading as required.
Then take average of these two angles of rotation.
6. Similarly measure the angle of rotation for other solutions and also for given
unknown solution of cane sugar.
7. Plot the graph between angle of rotation (on Y-Axis) and the concentration
(on X-Axis). It will be straight line.
Observations:
1. Temperature at the time of experiment = ------------ 0C.
2. Length of the Polarimeter tube = ι = --------------- cm.
Observation Table:

Sr. % of Sugar Angle of Rotation Specific Rotation

No. Solution (α) [α]tD
(C)
1 2
2 4
3 6
4 8
5 10
6 12
7 14
8 20
9 Unknown

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 35

Calculations:

The specific rotation is calculated by the formula-

[α]tD = 100 x α
Cxι

Where, C = Concentration of the substance in gm per 100 ml of the solution.

α = Angle of rotation,
ι = Length of the Polarimeter tube.
Graph:
Plot the graph of angle of rotation against concentration. Which is straight line, from this
determine the concentration of unknown solution.

Unknown concentration

Conc. ( C )

Result:

1. The specific rotation of unknown solution is -------------------------.

2. The concentration of unknown solution is ---------------.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 36

 6. Colorimeter-I
Aim: - To verify Beers-Lamberts law using various dilution of KMnO4 solution & to
find out λ max & concentration of KMnO4 in unknown solution
colorimetrically.
Theory - The law states that, “When a beam of monochromatic light passes through a
colored solution, the rate of decrease of intensity of radiation with thickness of
absorbing solution is directly proportional to the intensity of incident light &
concentration of the solution.

Optical Density (O.D.) = log Io / I = ϵ c t ……. t= 1 cm.

Optical Density (O.D.) = ϵ c

Hence, plot a graph of Optical Density (O.D.) against concentration C.

The straight lie will pass through origin with slope= molar extinction coefficient €
the Beer’s law is valid only for dilute solution on & straight line deviates if
concentration.

Apparatus – Colorimeter with cell, standard flasks, breakers etc.

Chemical – 0.01N KMnO4 solution, distilled water etc.

Procedure - 1) Prepare 0.1 N solution of KMnO4 by dissolving 0.316 gm of KMnO4 crystal in

100 m of distilled water. Hence prepare 0.01N solution using this stock solution

2) Prepare 0.0001, 0.0002, 0.0004, 0.0005, 0.0006, 0.0008, 0.001 & 0.002 N
solution of KMnO4 using 0.01N solution

3) Find out the λ max by using 0.0005 N KMnO4 solutions.

4) By fixing the λ max, record the O.D. of each solution.

Result :- λ Max = & Concentration = for unknown solution.

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 37

Observation Table –

I) Selection of λ max by using 0.0005 N II) Determination of Optical Density by

KMnO4 solution fixing λ max

Sr. Wave Optional Sr. Concentration Optical

No. length Density No. of Density
λ (O.D.) KMnO4 (O.D.)
1. solution
2. 1. 0.0001
3. 2. 0.0002
4. 3. 0.0004
5. 4. 0.0005
6. 5. 0.0006
7. 6. 0.0008
7. 0.001
8. 0.002
9. Unknown
solution
of KMnO4

Graph:- Plot a graph of Optical

Density (O.D.) against
concentration C.

O.D.

The straight lie will pass through

origin with slope = molar
extinction coefficient €

------------- Concentration

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 38

 Calculations:

i) To determine molar extinction coefficient – plot a graph of O.D Vs concentration

of KMnO4 the nature of the graph is straight line passing through origin find
out the slope of straight line . Slope = Molar extinction coefficient (€)

ii) To test the validity of Beer ‘law – The straight line deviate of O.D. of higher
concentration is plotted on the same graph. The point of deviation on the
straight line given the knowledge of validity. Of means that Beer’s law is
valid only up to that concentration for KMnO4

iii) To determine the concentration of unknown – by fixing the same λ max, note
down the O.D. value of unknown solution. The value of O.D. is plotted on Y-
Axis & draw parallels to X-Axis, so that it intersect the straight line at a
particular point. Drop of perpendicular from that point X-Axis which given
the concentration of unknown solution.

Result - 1) λ Max = ______________

2) Concentration for unknown solution = ________

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 39

 7. Colorimeter-II
Aim: - To determine indicator constant of a given Methyl Red indicator
colorimetrically.

Theory: The pK and hence dissociation constant (K) of an acid-base indicator can be
determined colorimetrically. Consider an acid-base indicator methyl red to illustrate the method.
The acidic (HMR) and basic (MR-) forms of methyl red are given below-
+
N(CH3)2 N-(CH3)2 N(CH3)2

N N N + H+
+
NH NH N

NH

COO- COO- COO-

Acid form Basic form

HMR (Red) MR- (Yellow)

In short HMR MR- + H+

On applying the law of mass action, the dissociation constant K of the above equilibrium
between acid form and base form is defined by the expression-

K= [H+] [MR- ]
[HMR]

Therefore, log K = log [H+] + log [MR- ]

[HMR]
-log K = -log [H ] - log [MR- ]
+

[HMR]
pK= pH - log [MR- ] as pK= -log K and pH= -log [H+]
[HMR]
-]
In the above equation if [MR = [HMR] then equation reduces to, pK = pH

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 40

From the above consideration, the determination of pK involves the following steps-
Both HMR and MR- exhibit strong absorption peaks in the visible portion of electro-
magnetic spectrum. A series of solutions of known pH (between 2 to 10) are prepared and equal
amount of methyl red is added to each of these solutions. The color intensity of indicator in an
aqueous solution depends upon the degree of dissociation which is dependent upon pH of the
medium. The solution of lower pH values exhibit red color to the solution and those to higher pH
shows yellow color. Some solutions, having in between these pH values, shows intermediate
color between red and yellow. The absorbances of the solutions are determined as a function of
pH at appropriate wavelength. The of inflection represent [MR- ] = [HMR] and the pH at this
point is pK. The dissociation constant (K) of the indicator can be determined using relation
pK= -log K.

Apparatus – Colorimeter with cell, PH- meter, hard test tubes, standard flasks, breakers etc.

Chemical – Methyl Red solution (Dissolve 20 mg of methyl red in 60 ml of ethanol and dilute to
100 ml by distilled water), 0.2 M Na2HPO4 , 0.1 M citric acid solution, distilled water etc.

Procedure: Part I: Preparation of solutions:

1. Take 12 flasks of about 50 ml capacity and label them from 1 to 12.
2. Take two burettes of 50 ml capacity and fill them by 0.2 M NaHPO 4 and 0.1 Citric acid
solution.
3. Withdraw following volumes of NaHPO4 and Citric acid solutions in the above flasks to
get desired buffer solutions.

Flask No. Expected pH 0.2 M NaHPO4 (ml) 0.1 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

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 41

 4. Take 12 hard glass test tubes and label them from 1 to 12. From the above prepared
buffer solutions, withdraw 10 ml from each and place in respective test tube.
5. Add 1 ml of indicator (with a calibrated pipette or micro burette) in each of the solution
in the test tubes and shake well.
Part II: Determination of pH of buffer solutions:
1. Standardize the pH meter using 0.05 M potassium hydrogen phthalate solution at pH=4.
2. Take buffer from flask no. 1 in a beaker so that the pH electrode is completely immersed
into the solution.
3. Repeat the same procedure for remaining solutions. Record these readings as observed
pH of the solutions.
Part III: Determination of Absorbance or Optical density:
1. Determine the λ Max value by using dense colored solution. For methyl red indicator
blue-green filter (490-500 nm) can be used.
2. Place the appropriate filter corresponding to λ Max value in the filter compartment.
3. Take the reference (blank) solution [buffer solution 1 without methyl red] in the cuvette,
clean it from outside and insert it into sample compartment.
4. Adjust meter reading to 100% transmittance with the help of course and fine set knobs.
5. Remove cuvette, wash it with distilled water. Put the solution from test-tube no. 1 in it,
clean it from outside and insert it into the sample compartment. Read the absorbance and
% transmittance of the solution on the meter scale.
6. Repeat the same for remaining solutions to record their absorbance and % transmittance
values.

Observation Table:
Solution from Observed Absorbance % ΔA Δ pH ΔA Mean pH
Test tube no. pH (A) Transmittance Δ pH
1
2
3
4
5
6
7
8
9
10
11
12

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 42

Graph: Plot the graph as i) Absorbance against pH and ii) ΔA against mean pH.
Δ pH

ΔA
A ΔpH

The point of inflection of the first plot or peak of the second plot indicates [MR - ] = [HMR] .
The pH value at these positions indicates pK value of the indicator. As pK= -log K, calculate
the value of dissociation constant K of methyl red indicator.

Results:
i) λ Max= --------------nm
ii) pK= -----------------
iii) K = ------------------

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 43

 8. Refractometer
Aim :- To determine the specific refractivity’s of the given liquid A and B
& determine percentage composition of the mixture C of liquid A and B.

Theory:- A ray of monochromatic light passing from one medium into another is refracted
or bent towards or away from the normal depending upon the optical nature of the
two media.
According to Snell’s law,
Refractive Index (η) = sin i / sin r
The refractive index depends upon the temperature, the chemical nature of the
substance and the wave length of light. If the second medium is solution,
refractive index also depends upon the concentration of the solution. So it can be
used to identify a pure substance and to determine the composition of
homogeneous transparent binary mixture.
Specific and molar refraction:
According to Gladstone and Dale,
η – 1 / d = constant (r)
Where η is the refractive index of the liquid, d is the density and r is constant.
But according to Lorentz and Lorentz,
η2 – 1 / η2 + 2 x 1/ d = Constant ( r )
gives a better constant. The value of this constant r is termed the specific
refraction of the liquid and is characteristic property of the liquid.
The molecular refractivity or molar refractivity ( R ) is given by
expression –
R = η – 1 / d x M ( According to Gladstone and Dale )
and
R = η2 – 1 / η2 + 2 x 1/ x M / d (According to Lorentz and Lorentz)
Where, M = Molecular weight of the substance.
Mixture Law:- The mixture law is given by the formula-
rx x 100 = rA P + rB ( 100 – P )
Where rx = Specific refractivity of the mixture A and B
rA = Specific refractivity of pure liquid A
rB = Specific refractivity of pure liquid B
PA = Percentage of A in the mixture
Here , PA = 100 (rx - rB ) / (rA - rB )

Material: Abbe refractometer, dropper, cotton wool, specific gravity bottle, alcohol.
Liquid A: pure liquid Mixture D: 25% A

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 44

 Liquid B: pure liquid Mixture E: 40% A
Liquid C: unknown percentage composition Mixture F: 60% A
Procedure:
1. Open the prism box by realizing the lock nut and clean gently both prism faces, with
a cotton plug moistened with acetone, so that the greasy matter present on the faces
will be removed.
2. By means of dropper, place few drops of liquid on the surface of lower prism and
close the box. A film of liquid will thus be enclosed between the two prisms.
3. Focus the cross wire of the telescope by rotating the eyepiece and adjust the mirror so
as to get the maximum illumination.
4. Move the prism box backward and forward till the field of vision becomes partly light
and partly dark. Turn the compensator screw and adjust the compensator until the
colored fringes’ in the field of vision disappear and a sharp boundary line is obtained.
5. Now rotate the prism box until sharp edge coincides with intersection of the cross
wire in the telescope. Read the refractive index directly on the scale, with accuracy.
Repeat the readings at least three times and take mean value.
6. Repeat the above procedure for all liquids one after another.
Determination of density with the help of specific gravity bottle:
Determine the density of all the liquids by using specific gravity bottle with distilled
water as the reference liquid.
Observation: Weight of empty specific gravity bottle (Y) = ………..gm

Specific gravity Wt. of liquid + Specific Wt. of liquid Density

Bottle filled with gravity bottle X gm (X-Y) gm d = (X-Y)/ W
Liquid A
Liquid B
Liquid C
Liquid D
Liquid E
Liquid F
Water W=
.

% Density Specific Refractivity

Liquid Refractive index (η)
Composition (d) (g ml-1) r = η2 – 1 / η2 + 2 x 1/ d
I II III Mean
A 100 % A
B 0% A
C Unknown
D 20% A
E 40% A
F 60 % A

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 45

Calculation:

(I) Determination of specific refractivity (r) :

r = η2 – 1 / η2 + 2 x 1/ d ml / gm

(II) Determination of percentage composition of unknown mixture (X),

Use Formula
Where PA is % composition of A in mixture
PB is % composition of B in mixture
PA = 100 (rx - rB ) / (rA - rB ) and PB = 100 - PA

Graph:
Plot a graph by plotting the specific refractivity’s against the percentage composition.

Composition of unknown mixture, X can

be obtained from point corresponding to
its specific refractivity on this curve.

% of A

Results :

Percentage composition of the mixture C:

By graphical method By mixture law

PA PB PA PB

B.Sc. II Practical Physical Chemistry, Jawahar College, Anadur Page 46