M.Sc.

PROGRAMME
PHYSICAL CHEMISTRY PRACTICALS

Laboratory Manual

Compiled by
Dr. R. Santhi, Associate Professor of Chemistry

Post Graduate and Research Department of Chemistry

Seethalakshmi Ramaswami College (Autonomous)
Affiliated to Bharathidasan University
Accredited with “A” Grade (3 rd cycle) by NAAC
Tiruchirappalli – 620 002
 M.Sc. PHYSICAL CHEMISTRY

PRACTICALS

NAME : _______________________________________

REG. No. : _______________________________________

CLASS : _______________________________________

RESEARCH AND POST GRADUATE DEPARTMENT OF CHEMISTRY

SEETHALAKSHMI RAMASWAMI COLLEGE (AUTONOMOUS)
(ACCREDITED BY NAAC)
TIRUCHIRAPPALLI – 620 002

1
 Ex. No. 1
SIMPLE EVTECDIC SYSTEM
BINARY SYSTEM OF NAPHTHALENE AND BIPHENYL
Table - 1
Weight Composition Composition Melting
S. Weight of Freezing
of % of % of - point Average
No. naphthalene point C
biphenyl naphthalene biphenyl C

Table - 2

Weight Composition Composition Melting

S. Weight of Freezing
of % of % of point Average
No. naphthalene point C
biphenyl biphenyl naphthalene C

TC

% composition

2
 PHASE RULE I

Ex.No.: 1 BINARY SYSTEM OF NAPHTHALENE AND BIPHENHYL

Aim:
To determine the eutectic temperature and eutectic composition of
Naphthalene and biphenyl.

Principle:

The pure substance has a definite melting point, but when another
substance is added o it, the melting point is lowered gradually in proportion to
the amount of the substance added. The lowest melting point gives the
eutectic temperature.

Procedure:
Pure Naphthalene and Biphenyl of known weight (~ 5g) are taken in two
different specimen tubes provided with an outer jacket. It is closed with a cork
fitted with a sensitive thermometer and stirrer. It is clamped and suspended
in a beaker containing distilled water. It is heated and the melting point is
noted. When the substance becomes homogeneous throughout, it is allowed
to cool and the temperature at which the first crystal appears is taken as the
freezing point. To the specimen tube containing naphthalene, ~ 0.5g of
biphenyl is added and heated. When the mixture becomes homogeneous
throughout, it is allowed to cool and the freezing point is first noted. After it is
completely frozen, it is heated and the melting point is noted. Similar
additions of biphenyl are made for 7 times. The freezing and melting points
are noted after each addition.
Simultaneously ~0.5g of naphthalene is added to biphenyl and the same
procedure described above is repeated. The freezing point and melting point
are noted after each addition. A graph is drawn by taking temperature along
y- axis and percentage composition along x- axis. Two straight lines are
obtained which meet at eutectic point. From the graph the eutectic
temperature and eutectic composition are noted. It has been found that the
freezing point of naphthalene decreases with the addition of biphenyl and the
freezing point of biphenyl decreases with the addition of naphthalene.

3
4
 Result:
1 The eutectic temperature of naphthalene and biphenyl = °C
2 At eutectic point i) composition of naphthalene = %
ii) Composition of biphenyl = %
3 On adding naphthalene, the freezing point of the mixture decreases / increases
4 The composition of naphthalene in the given
un-known mixture = %

5
 Ex. No. 2
COMPOUND FORMATION
Table – 1
Weight
Composition % of - Freezing Melting
Weight of m- of -
% of m- naphthyl point point Average
dinitrobenzene naphthal
dinitrobenzene amine C C
amine

Table – 2
Weight Composition
Composition Melting
of - Weight of m- % of - Freezing
% of m- point Average
naphthal dinitrobenzene naphthyl point C
dinitrobenzene C
amine amine

TC

% composition

6
 PHASE RULE I

Ex.No.: 2 BINARY SYSTEM OF NAPHTHYLAMINE

AND m-DINITROBENZENE
Aim:
To study the phase diagram of binary system of α – naphthylamine
and m – dinitrobenzene.

Principle:

The pure substance has a definite melting point, but when another
substance is added to it, the melting point is lowered gradually in
proportion to the amount of the substance added. In these systems the two
components form a compound with congruent melting point. The lowest
melting point gives the eutectic temperature. Thus there will be 2 eutectic
temperatures.

Procedure:
Pure α – naphthylamine and m – dinitrobenzene are taken in two
different specimen tubes provided with an outer jacket. It is closed with a
cork fitted with a sensitive thermometer and a stirrer. It is clamped and
suspended in a beaker containing distilled water. It is heated and the
melting point is noted. When the substance becomes homogeneous
throughout, it is allowed to cool and freezing point is noted. About ~ 0.5g
of m – dinitrobenzene is added to α – naphthylamine and heated. When the
mixture becomes homogeneous throughout, it is allowed to cool and the
temperature is noted, when the first crystal appears and it is taken as the
freezing point. After it is completely frozen, it is heated and the melting
point is noted. The whole of the substance melts and is taken as the melting
point. The average of these two temperatures is noted. Similar additions of
m – dinitrobenzene are made 7 times. The melting point and freezing points
are noted for each addition.
Simultaneously ~0.5g of α – naphthylamine is added to m –
dinitrobenzene and the same procedure described above is repeated. The
freezing point and melting point are noted after each addition.
A graph is drawn by taking temperature along y- axis and percentage
composition along x- axis. Two straight lines are obtained which meets at
eutectic point. From the graph the eutectic temperature and eutectic
composition are noted.
It has been found that the freezing point of m – dinitrobenzene
decreases with the addition of α – naphthylamine and the freezing point of
α – naphthylamine decreases with the addition of m – dinitrobenzene. The
maximum point on the graph corresponds to the melting point of compound
AB. The other two minima on the graph correspond to the two eutectic
temperatures.

7
8
Ex.No.: 2 Contd.

Result:
1. α – naphthylamine and m – dinitrobenzene forms a compound having a
congruent melting point = °C
2. The percentage composition of the compound at congruent melting
point =

3. I Eutectic temperature =
Percentage composition at the eutectic point
(i) α – naphthylamine =
(ii) m – dinitrobenzene =
II Eutectic temperature =
Percentage composition at the eutectic point
(i) α – naphthylamine =
(ii) m – dinitrobenzene =

9
Ex. No. 3
BINARY SYSTEM OF BENZOIC ACID AND CINNAMIC ACID

Graph -1

TC

% composition

Table – 1

Composition
Weight of Weight of Composition Melting
% of Freezing
Benzoic Cinnamic % of point Average
Cinnamic point C
acid acid Benzoic acid C
acid e

Table – 2
Composition
Weight of Weight of Composition Melting
% of Freezing
Benzoic Cinnamic % of point Average
Cinnamic point C
acid acid Benzoic acid C
acid e

10
 PHASE RULE – II

Ex.No.: 3 BINARY SYSTEM OF BENZOIC ACID AND

CINNAMIC ACID.
Aim:
To study the phase diagram of a binary system of Benzoic acid and
cinnamic acid.

Procedure:
Pure Benzoic acid and cinnamic acid are taken in two different specimen
tubes provided with a stirrer and outer jacket. It is clamped and suspended in a
beaker containing glycerol. It is heated and the melting point is noted. When
the substance become homogeneous throughout it is allowed to cool & the
freezing point is noted. About 0.5g of benzoic acid is added to cinnamic acid
and heated. When it becomes homogeneous it is allowed to cool and the
temperature at which the crystal appears is noted as the freezing point. After it
is completely frozen, it is heated. The temperature is noted, when whole of the
substance melts and is taken as the melting point. The average of these two
temperatures is noted. Similarly benzoic acid is added to cinnamic acid in
portions for 10 times and the experiment is repeated. The melting & the
freezing points are noted after each addition.
Simultaneously 0.5g of cinnamic acid is added to benzoic acid and the
procedure as described above is repeated. The melting and freezing points are
noted. A graph is drawn by taking temperature along y axis & the percentage
composition along x axis.

Result:
Benzoic acid and cinnamic acid form a solid solution. Addition of
Benzoic acid to cinnamic acid decreases the melting point of the latter. These
two are miscible with each other to form a solid solution which has a lower
melting point than either of the pure components.

Note : Binary system of naphthalene and –Napthol

TC

% composition

Result : naphthalene and –napthol form a continuous series of solid solution.

11
 Ex. No. 4

THREE COMPONENT SYSTEM

Volume of Volume Volume of Weight of Weight Weight % of

S. % of % of
Chloro- of H2 O Acetic Chloro- of H2 O of Acetic Chloro
No. H2 O ethanol
form (ml) (ml) acid (ml) form (g) (g) acid (g) -form

12
Ex.No.:4 THREE COMPONENT SYSTEM

Aim:
To study the phase diagram of a three component system.

Procedure:
Mixtures of CHCl3 and CH3COOH of varying composition are taken in a
set of iodine flasks. The bottles containing the solutions are placed in a
thermostat at room temperature for 15 minutes. Then water is run from a
burette in small quantities and after each addition the flask is shaken well.
Addition is continued till turbidity appears on shaking.
From the amount of water added and the initial amount of CHCl3 and
CH3COOH, the composition of mixture is calculated. The results are plotted in
a triangular diagram. The points obtained are joined into a smooth curve.
The triangular diagram,
(i) The vertices A,B,C of the equilateral triangle represents the 3 pure
components CHCl3, CH3COOH and H2O.
(II) Side AB represents the composition of binary system CH3COOH,
CHCl3. On the side AB, the concentration of water is zero. Similarly the
component A is absent along BC and B is absent along AC.
(III) In plotting the composition of ternary mixture 2 points are marked
on one side of the triangle representing the amount of two components and
from these points, lines are drawn parallel to the other side of the triangle. The
point of intersection gives the composition of ternary mixture.
(IV) A binodal curve is obtained by joining the experimentally
determined points.
(V) Any point outside the curve represents a one phase system, all the
three liquids (H2O, CHCl3, CH3COOH) being completely miscible with each
other.
(VI) Inside the binodal curve the system consists of two phases.

Result:
Chloroform and water are the partially miscible liquids. Only one
bimodal curve corresponding to this pair of liquids appears in the phase
diagram.

13
Ex. No. 5
COMPARISON OF STRENGTHS OF THREE ACIDS
Table – 1
Ester hydrolysis with 0.25N HCl at 33C

Burette Readings
Time in Volume of NaOH (V – Vt)
(ml) Log (V – Vt)
minutes (ml) (ml)
Initial Final

Infinite reading, V=

Table – 2
Ester hydrolysis with 0.5N HCl at 33C

Burette Readings
Time in Volume of NaOH (VD – Vt)
(ml) Log (VD – Vt)
minutes (ml) (ml)
Initial Final

Infinite reading, V=

Table – 3
Ester hydrolysis with 0.75N HCl at 33C

Burette Readings
Time in Volume of NaOH (V – Vt)
(ml) Log (V – Vt)
minutes (ml) (ml)
Initial Final

Infinite reading, V=

14
Ex. No.:5 COMPARISON OF STRENGTHS OF THREE ACIDS
Aim:
To compare the strengths of three acids.
Principle:
The hydrolysis of all esters eg., Ethyl acetate is hydrolyzed according to
the equation.
HCl
CH3COOC2H5 + H2O CH3COOH + C2H5OH
The reaction is an example of a pseudo unimolecular reaction. Although
two molecules take part in the reaction, the active mass of water does not
appreciably alter, because it is present in large excess. As the hydrolysis of an
ester by pure water is very slow, mineral acids are added to the reaction
mixture to catalyse the reaction. Since free acetic acid is produced in the
reaction, the reaction can be followed by titrating known volume of reaction
mixture with standardised alkali at regular time intervals. The amount of alkali
consumed at any time corresponds to the quantities of the ester decomposed at
that time.
Procedure:
Buretted out 100ml of N/2 HCl is into a dry conical flask. The given ester is
also taken in another conical flask. Both the conical flasks are suspended in a
water bath to attain equilibrium. After equilibrium has been attained 10ml of
the ester is pipetted out in to the conical flask containing acid. When half of the
ester is added, the stop watch is started. The contents are shaken and after 10
minutes, 5ml of the reaction mixture is pipetted out into the ice cold water to
arrest further reaction.
The liberated acid is titrated against 0.2N NaOH using phenolphthalein as
an indicator. 5ml of the reaction mixture is withdrawn at regular intervals of 10
minutes up to one hour. The remaining solution is heated in a water bath at
about 60-70°C to allow the reaction to proceed to completion. It is then cooled
to room temperature and 5ml of the reaction mixture is run into ice cold water
and titrated against 0.2N NaOH using phenolphthalein as indicator (v∞)
The experiment is repeated with 0.25N and 0.75N HCl. Log (v∞ - vt) is
plotted vs time in a graph, where vt is the volume of NaOH, needed for
neutralization at that time t. A straight line is obtained. From the slope, the rate
constant is calculated using the formula

15
 Graph – 1

Log (V-Vt
Time (mins)

Graph – 2
Log (V-Vt

Time (mins)

Graph – 3
Log (V-Vt

Time (mins)

16
Result:
1. The rate constants of the reactions by the acid of three different
concentrations are
kA [0.25N] = min-1
kB [0.50N] = min-1
kC [0.75N] = min-1

2. The ratio of the rate constants of the reactions by the acids of three

different concentrations (A : B : C) are

17
 Ex. No. 6
DETERMINATION OF ACTIVATION PARAMETER
Table – 1
Ester hydrolysis with 0.25N HCl at 31C
Burette Readings (ml) Volume of NaOH (V – Vt)
Time in minutes log (V – Vt)
Initial Final (ml) (ml)

Table – 2
Ester hydrolysis with 0.25N HCl at 37C
Burette Readings (ml) Volume of NaOH (V – Vt)
Time in minutes log (V – Vt)
Initial Final (ml) (ml)

Table – 3
Ester hydrolysis with 0.25N HCl at 45C
Burette Readings (ml) Volume of NaOH (VD – Vt)
Time in minutes log (VD – Vt)
Initial Final (ml) (ml)

Determination of activation parameter

Table – 4
T(K) 1/T x 10-3 kx10-3 log (kx10-3) 3+log k

Energy of activation, Ea = slope x 2.303 x R

= kJ mol-1
#
Enthalpy of activation, H = Ea – RT
= kJ mol-1
Free Energy of activation, G# = RT ln k B T  ln k 
 h 
= kJ mol-1
# H #  G #
Entropy of activation, S =
T
= JK-1 mol-1

k = 1.38 x 10-23
3+logK

R = 8.314
h = 6.626 x 10-34

1/T

18
Ex. No.:6
DETERMINATION OF ACTIVATION PARAMETERS
Aim:
To determine the activation parameters for the acid catalyzed
hydrolysis of ester

Principle:
Velocity constants for the hydrolysis of ester by HCl at different
temperatures are determined and the energy of activation is calculated using
the equation.

Procedure:
Buretted out 100ml of 0.25N HCl into a clean conical flask. Ethyl acetate
(ester) is also taken in another conical flask. Both the flasks are kept in a
thermostat at temperature T1, when both the flasks have attained the same
temperature, 10ml of the ester is pipetted out into the acid. A stop watch is
started at the instant when half of the ester is added. The contents are shaken
and after 10 minutes, 5ml of the reaction mixture is run into ice cold water to
arrest the reaction. The excess acid is titrated against 0.2N NaOH using
phenolphthalein as indicator. The above process is repeated at intervals of 10
minutes for an hour.
The remaining solution is heated in a water bath maintaining the
temperature 60 - 70°C for 30 minutes. It is then cooled to room temperature,
after which 5ml of the reaction mixture is run into ice cold water and titrated
against 0.2N NaOH using phenolphthalein as indicator.
The same experiment is repeated with the same acid but at two higher
temperatures such as 37°C and 45°C. The velocity constants are calculated for
the three experiments and then the energy of activation is calculated from
Arrhenius slope.

Result:
1. The energy of activation Ea = _______________ kJ mol-1
2. Enthalpy of activation _______________ kJ mol-1
3. Free energy of activation = _______________ kJ mol-1
4. Entropy of activation = _______________ JK-1 mol-1

19
Ex. No. 7
DETERMINATION OF CATALYTIC COEFFICIENT

Concentration of H+ ions Rate constant (min-1)

K = k [H+] [H+]

K
k[H+] =
 H  
k

[H+]

20
Ex. No. :7 DETERMINATION OF CATALYTIC COEFFICIENT

Aim:

To determine the catalytic coefficient.

Procedure:

Buretted out 100ml of N/2 of HCl into a clean conical flask and kept in a
water bath at room temperature. The ester is also kept for equilibrium at the
same temperature. When both have attained equilibrium, 10ml of the ester is
pipetted out into a flask containing acid, starting the stopwatch when half of
the quantity is added. Pipetted out 5ml of the reaction mixture and allowed to
run into an ice cold water containing phenolphthalein. The unreacted acid is
titrated against 0.2N NaOH. This is repeated at regular intervals of 10 minutes
up to one hour.
The remaining solution is heated in a water bath at about 60-70C to
allow the reaction to proceed to completion. It is than cooled to room
temperature and 5ml of the reaction mixture is run into ice cold water and
titrated against 0.2N NaOH.
The above procedure is repeated for two different concentration of the
same acid. Log (Vo–Vt) is plotted Vs time in a graph. From the slope of the
straight line obtained, corresponding rate constant K is calculated. By plotting
rate constant Vs hydrogen ion concentration, a straight line is got. The slope
obtained from the graph is a measure of catalytic coefficient.

Result:
The catalytic coefficient of ester hydrolysis is ________

21
 Ex. No. 8
REACTION BETWEEN POTASSIUM IODIDE AND POTASSIUM
PERSULPHATE
Table 1

Volume of
Volume of Volume of Volume
K2S2O8 (20ml)+ Time
KNO3 Water of KI 4+ log k 
Thio (10ml)+ (sec)
(ml) (ml) (ml)
Starch (5ml)

1
Calculation : 
2
 Ci Z i2
 =
 =
 =
 =
 =
 =
Graph
4 + log k

[thio]
1
2 0.00005
k  2 

dt[S2 O8 ][I ] 2  0.001 0.01 time

k = 4+logk =

k = 4+logk =

k = 4+logk =

k = 4+logk =
unknown ;
k = 4+logk =

k = 4+logk =

22
Ex. No. : 8 STUDY OF REACTION BETWEEN POTASSIUM IODIDE AND
POTASSIUM PERSULPHATE
Aim:
To study the effect of ionic strength on the kinetics of the reaction
between potassium persulphate and potassium iodide.
Principle:
0.005M Potassium persulphate, 0.2 M KNO3 , 0.05M KI, 0.0005N
thio and 1% starch solution are prepared. The reaction rate is studied for the
following set of reactants.

(i) 20ml of K2S2O8,10ml of thio, 5ml of starch,20ml of KI and 45ml of

water.
(ii) 20ml of K2S2O8, 10ml of thio, 5ml of starch, 20ml of KI, 35ml of
water and 10ml of KNO3.
(III) 20ml of K2S2O8, 10ml of thio, 5ml of starch, 20ml of KI, 30ml of
water and 15ml of KNO3.
(IV) 20ml of K2S2O8, 10ml of thio, 5ml of starch, 20ml of KI, 25ml of
water and 20ml of KNO3.
(v) 20ml of K2S2O8, 10ml of thio, 5ml of starch, 20ml of KI, 20ml of
water and 25ml of KNO3.
(vi) 20ml of K2S2O8, 10ml of thio, 5ml of starch, 20ml of KI, 15ml of
water and 30ml of KNO3.
(vii)20ml of K2S2O8, 10ml of thio, 5ml of starch, 20ml of KI, 10ml of
water and 35ml of KNO3.

In a clean two stoppered conical flask, the solutions as in (i)

except KI are mixed and it is kept in a constant temperature bath for
10minutes. The KI solution is also thermostated. Pipetted out 20ml of KI into
the conical flask containing the mixed solution. The stopwatch is started, when
half of it is added. As soon as the blue colour appears the stopwatch is stopped
and time is noted. The experiment is repeated by taking the composition as
given in (ii), (iii), (iv), (v), (vi) and (vii). Similar experiments are carried out
with unknown KNO3.
= K [ S2O82-] [I-]

K
By substituting the noted time, the rate constant is calculated. A graph
is drawn by plotting log kvs  . From the graph, the unknown concentration
of KNO3 is determined. This linear plot of log kvs  indicates that the
Bronsted – Bjerrum equation is obeyed.
Result:
The concentration of unknown KNO3 are
a) M
b) M
23
Ex. No. 9
IODINATION OF ACETONE

Graph 1

absorbance
Time (mins)
Graph 2
absorbance

Time (mins)

Graph 3
absorbance

Time (mins)

Graph 4
absorbance

Time (mins)
Table 1
Time Absorbance
(min) I II III IV

24
Ex. No. : 9
IODINATION OF ACETONE
Aim:
To study the reaction of iodination of acetone.

Principle:
The process of the reaction between acetone and iodine can conveniently
be followed colorimetrically making use of the fact that the presence of iodine,
mainly as trioxide ion [IO3- ] imparts reddish brown colour to the reaction
mixture. The colour fades to pale yellow as the reaction proceeds due to the
consumption of iodine. Isolation method can be used conveniently taking both
acetone and the acid in large excess. The order of the reaction is one each with
respect to acetone & the acid and zero with respect to iodine.

Procedure:
Diluted 10ml of pure acetone to 100ml and mixed each of acetone
solution, 0.5M H2SO4 and water. Added 10ml of iodine solution started the
stop watch. The wavelength is set at 530nm in colorimeter. Transferred the
reaction mixture into the Erma tube and recorded the absorbance using water
as the blank at suitable intervals of time. Repeated the experiments with the
composition of reaction mixture listed below.

I II III IV
Acetone (ml) 5 10 5 5
0.01M I2 solution (ml) 10 10 5 10
0.5M H2SO4 (ml) 5 5 5 10
Water (ml) 5 0 10 0

Plotted the absorbance Vs time for different reaction mixtures. The plots
are linear with a constant slope showing the reaction to be zero order with
respect to iodine.

Result:
Rate constant (I) = ______ min-1dm3mol-1
Rate constant (II) = ______ min-1dm3mol-1
Rate constant (III) = ______ min-1dm3mol-1
Rate constant (IV) = ______ min-1dm3mol-1

The rate constant (II) is twice that of rate constant (I), when acetone
concentration is doubled. The rate constant (III) is approximately equal to the
rate constant (I), when iodine concentration is doubled. The rate constant (IV)
is twice as that of rate constant (I) when sulphuric acid concentration is
doubled. Hence the reaction is first order each respect to acetone and sulphuric
acid and zeroth order with respect to iodine.

25
Ex. No. 10

Concentration Angle of rotation Specific rotation

5%

10%

15%

20%

25%

a x100
Specific rotation    
cxl
Angle of rotation

Concentration

26
 POLARIMETRY
Ex.No.:10 DETERMINATION SPECIFIC ROTATION

Aim:
To determine the specific rotation of glucose using polarimeter.
Principle:
When a substance rotates the plane of polarized light to the right,
it is called dextro rotatory and when it rotates the plane to the left, it is
called laevorotatory. The angle of rotation depends upon the nature of
the substance, the temperature and the wave length of the light used. The
ax100
result is usually expressed as   where ‘’ is the specific
cxl
rotation, ‘a’ is the observed angle of rotation, ‘l’ is the length of the
column in decimeter and ‘c’ is the concentration in g /100 c.cs.
Procedure
Distilled water is taken in the observation tube and the disc is
rotated till the two halves are of equal intensity and the reading was
noted. Then about 10% solution of glucose is prepared by weighing
exactly. This solution is taken in the observation tube. Then the disc
was adjusted for the same colour and the reading is noted. The difference
between the two gives the angle of rotation. From this value specific
rotation is calculated.
The experiment is repeated with solutions of concentration 5%,
15%, 20% and 25%. A graph is drawn taking concentration in X-axis
and angle of rotation in Y-axis.
Result
1. There is a linear relationship between concentration and angle of rotation.
2. The specific rotation of unknown glucose solution is
A= B=

27
 Ex. No. 11
1N Hydrochloric acid
1 2 3 4 5 6 7
2.303
log log k  log10   0    
Time in Angle of
o –  t –  tn 
minutes rotation 0   t  
 log10   t     
0
10
20
30
40
50
60

Average =

N/2 Hydrochloric acid

2.303
Time in Angle of k=  log10  0      log10  t    
o –  t –  tn
minutes rotation

0
10
20
30
40
50
60

Average =

Rate constant for 1N HCl

Analytical value = Ratio of Strengths =
Rate constant for N/2 HCl

= =

28
 POLARIMETRY

Ex.No.: 11 DETERMINATION OF RELATIVE STRENGTHS OF TWO

ACIDS
Aim:
To determine the relative strengths of 1N hydrochloric acid and
N/2 hydrochloric acid.
Principle:
The inversion of cane sugar is a first order reaction, the velocity
of which is accelerated by acids to a degree which is approximately
proportional to the concentration of hydrogen atoms. This reaction is
successfully employed to compare the strengths of acids. If  0 Is the

angle of rotation at the commencement of the reaction,  is the final

angle of rotation of the complete inversion of sugar present at time tn.
Hence in accordance with the law of unimolecular reaction, we have the
velocity constant k by the equation,
2.303
k  log10  0      log10  t    
tn
Procedure
A 10% solution of cane sugar is prepared. The normal solution
and N/2 solution of hydrochloric acid are prepared. Then 25ml of cane
sugar solution is mixed with 25ml of 1N hydrochloric acid and a stop
watch is started when half of the acid is added. After thorough mixing of
the solutions, the polarimeter tube is filled with the mixture and
immediately placed in the polarimeter and the readings are noted for
every ten minutes. The final reading is taken after heating to 60 - 70C
over a water bath for an hour. The solution is cooled to the room
temperature, the polarimeter tube is filled with the solution and then the
reading is noted. The same experiment is repeated with N/2 hydrochloric
acid. The velocity constant was calculated in the two cases. The ratio of
the velocity constants gives the relative strengths of two acids.

29
 N/2 Hydrochloric acid

log (t - )

Time (mins)

1N Hydrochloric acid
log (t - )

Time (mins)

30
Result

The ratio of the strengths of the two acids

1. Analytical value =
2. Graphical value =

31
Ex. No. 12
ADSORPTION ISOTHERM

Standardization of KMnO4

0.1N Oxalic acid Vs KMnO4

Volume of Volume of
Sl. Burette Reading Indicator
Oxalic acid KMnO4 (ml)
No.
(ml) Initial Final

Volume of Oxalic acid =

Strength of Oxalic acid =
Volume of KMnO4 =
Strength of KMnO4 =

Oxalic acid Vs KMnO4

Volume of
Bottle Volume Burette Reading Indicator
NaOH (ml)
No. Taken (ml)
Initial Final

Calculation :

i. Concentration of oxalic acid after absorption Ce (1) =

ii. Concentration of oxalic acid after adsorption Ce (2) =

iii. Concentration of oxalic acid after adsorption Ce (3) =

iv. Concentration of oxalic acid after adsorption Ce (4) =

v. Concentration of oxalic acid after adsorption Ce (5) =

vi. Concentration of oxalic acid after adsorption Ce (6) =

32
Ex. No.: 12 ADSORPTION ISOTHERM
Aim:
(i) To study the adsorption of oxalic acid on activated charcoal and to
Verify (a) Freundlich adsorption isotherm and (b) Langmuir adsorption
isotherm.
(ii) To determine the strength of unknown oxalic acid using Freundlich
adsorption.
Principle:
The amount of the substance adsorbed decreases with rise of
temperature. Since all adsorption processes are exothermic, the amount
adsorbed at any temperature is proportional to the concentration owing to the
general saturation on the surface. Freundlich isotherm is x = kc1/n

Procedure:
Accurately known weights of charcoal are taken in six pyrex bottles
and 100ml of oxalic acid is added to one of the bottles. Similarly 100ml each
of 0.4N, 0.3N, 0.2N and 0.1N oxalic acid are added in to the other bottles.
Oxalic acid unknown strength is taken in the sixth bottle. All of them are kept
in an electrical shaker for half an hour.
Approximately 0.2N potassium permanganate is prepared and
standardized with oxalic acid of known strength. After half an hour, the bottles
are removed and allowed to settle. Then it is filtered, 10ml of the solution is
pipetted out, 15ml of dil. H2SO4 is added, heated to bearable warmth and
titrated vs standardized KMnO4 . This is repeated with other bottles. From the
titration value Ce, the concentration at equilibrium is calculated. Co is the initial
concentration, Co - Ce is amount of acid that is adsorbed by m grams of
charcoal which is added at the beginning. Here x/m is the amount of acid
adsorbed by 1 gram of charcoal that was added at the beginning. A graph is
drawn taking log x/m in the y axis and log Ce on the x axis. A linear plot
obtained shows applicability of the Freundlich adsorption. The slopes and the
intercept of the plot gives 1/n and logk respectively. For the unknown, log x/m
value is calculated from the graph and hence x is determined.
Langmuir’s adsorption equation is tested by plotting values
(ordinate) Versus Ce (abscissa). A linear plot obtained shows the applicability
of the isotherm.
Result:
(i) Adsorption of oxalic acid on charcoal obeys both Freundlich and
Langmuir adsorption.
(ii) The unknown concentration of oxalic acid
(a)_________M (b)_______M

(iii) 1/n = ____________

(iv) log k = ___________

33
Adsorption of oxalic acid on activated charcoal

Bottle Amount of X=(Co - Ce) ce

Co Ce x/m 2+log x/m 2+log Ce
No. Charcoal (ml) x 6.005 x/m

Langmuir adsorption :
Ce
(i) = =
x
m

Ce
(ii) = =
x
m

Ce
(iii) = =
x
m

Ce
(iv) = =
x
m

Ce
(v) = =
x
m

Graph – 1

ce
x/m

x/m

Graph – 2

2+log x/m

2+log Ce

34
35
Ex. No. 13
TITRATION OF HYDROCHLORIC ACID VS SODIUM HYDROXIDE
Volume of NaOH Conductance Volume of NaOH Conductance
(ml) (m.mho) (ml) (m.mho)

Volume of NaOH =

Strength of NaOH =

Volume of HCl =

Strength of HCl =
Conductance
(m.mho)

Volume of NaoH (ml)

36
 CONDUCTOMETRY

Ex.No.:13 TITRATION OF HYDROCHLORIC ACID VS SODIUM

HYDROXIDE
Aim:
To determine the concentration of hydrochloric acid by conductometric
titration.

Principle:
According to Kohlrausch law, the electrical conductivity of a solution
depends upon the number of ions present and their mobility. So conductivity
measurements can be employed to find the end point of acid, alkali and other
type of titrations. Let us consider the titration of strong acid like HCl vs strong
base like NaOH.
A known volume of HCl is taken In the conductivity cell. A known
volume of NaOH is added and after each addition the conductance is
determined. The conductance of the solution is plotted vs the volume of alkali
added. Two straight lines are obtained. The point of intersection is the end
point and the volume of alkali corresponding to this point is the volume
required to neutralize the known volume of the acid. Before the addition of
alkali the conductivity is due to the presence of H+ and Cl- ions.
The conductance is mainly due to the H+ ions which have very high
mobility. As alkali is added the H+ ions are removed as feebly ionized water
molecules. The conductivity of the solution decreases due to replacement of
H+ ions by slow moving Na+ ions. Once the end point is reached, after the
neutralization, there will be an increase in conductance due to increase in
concentration of OH- ions because the OH- ions have the high mobility. The
point of minimum conductivity will therefore be the end point of the titration.

Procedure:
Pipetted out 40ml of 0.02 N HCl into a 150 ml beaker so that the
electrodes are completely immersed in the solution. Sodium hydroxide
solution of strength 0.1 N is added in 0.5ml portions. The solution is stirred
well and allowed to attain equilibrium. The conductance is noted and is
plotted vs the volume of NaOH added. The point of intersection of two
straight lines gives the end point.

Result:
The strength of Hydrochloric acid is _____________ N.

37
Ex. No. 14

TITRATION OF ACETIC ACID Vs SODIUM HYDROXIDE

Volume of NaOH Conductance Volume of NaOH Conductance

(ml) (m.mho) (ml) (m.mho)

Volume of Sodium hydroxide =

Strength of Sodium hydroxide =

Volume of acetic acid =

Strength of acetic acid =

Conductance (m.mho)

Volume of NaoH

38
Ex.No.:14 TITRATION OF ACETIC ACID Vs SODIUM
HYDROXIDE
Aim:
To determine the strength of acetic acid by conductometric titration.

Procedure:
Pipetted out 40ml of given acetic acid into a 150ml beaker so that the
electrodes are completely immersed in the solution. A saturated solution of
NaOH (0.1N) is added in 0.5ml portions. The solution is stirred well and
allowed to attain equilibrium. The conductance is noted and plotted vs the
volume of NaOH added. The point of intersection corresponds to the volume
of NaOH required to neutralize the solution. From the point of intersection of
two straight lines, the end point is noted and then the strength of acid is
calculated.

Result:
The strength of acetic acid is ______________ N.

39
Ex. No. 15
TITRATION OF MIXTURE OF ACIDS Vs SODIUM HYDROXIDE
Volume of NaOH Conductance Volume of NaOH Conductance
(ml) (m.mho) (ml) (m.mho)

Volume of Sodium hydroxide =

Strength of Sodium hydroxide =
Volume of HCl =
Strength of HCl =
Volume of sodium hydroxide =
Strength of sodium hydroxide =
Volume of acetic acid =
Strength of acetic acid =
Conductance
(m.mho)

Volume of NaOH (ml)

40
Ex.No.: 15 TITRATION OF MIXTURE OF ACIDS VS SODIUM
HYDROXIDE

Aim:
To determine the strength of HCl and CH3COOH using NaOH by
conduction metric titration.

Procedure:
Pipetted out 40ml of given mixture of acetic acid and HCl into a
conductivity cell containing electrodes which are fully immersed in the
solution. A standardized solution of strength of 0.1N is taken in a burette and
added in 0.5ml portions. The solution is stirred well and allowed to attain
equilibrium. The conductance is measured and it is plotted Vs the volume of
NaOH added. Three straight lines are obtained and the points of intersection
give the end points.

Result:
(i) The strength of Hydrochloric acid in the given mixture = ___________ N
(ii) The strength of Acetic acid in the given mixture = ___________ N

41
Ex. No. 16

TITRATION OF BARIUM CHLORIDE Vs MAGNESIUM SULPHATE

Conductance (m.mho)

Volume of MgSO4

Volume of NaOH (ml) Conductance

(m.mho)

Volume of barium chloride =

Strength of barium chloride =

Volume of MgSO4 =

Strength of MgSO4 =

42
Ex.No.:16 TITRATION OF BARIUMCHLORIDE VS MAGNESIUM
SULPHATE
Aim:
To determine the strength of barium chloride conductometrically by
titrating with magnesium sulphate.

Procedure:
Pipetted out 40ml of given BaCl2 into a clean dry beaker and the
conductivity cell should completely be immersed in the solution. 0.1N MgSO4
is taken in the burette and added in 0.5ml portions. The solution is stirred well
after each addition and allowed to attain equilibrium. The conductance is
noted. Then the conductance is plotted Vs the volume of MgSO4 added. Two
straight lines with different slopes are obtained. The point of intersection
gives the equivalence point from which the strength of barium chloride can be
calculated.

Result:
The strength of barium chloride = ______________ N

43
Ex. No. 17

STRONG ELECTROLYTE – VERIFICATION OF ONSAGER’S THEORY

k x 1000

Conductance C
S. No. Concentration of NaCl (N) C
(m.mho) x 10 -3 (mho cm2)
gequ-1

Calculation :

1)  =

2)  =

3)  =

4)  =

5)  =

6)  =

44
Ex.No.:17 STRONG ELECTROLYTE – VERIFICATION OF
ONSAGER’S THEORY
Aim:
To determine the equivalent conductance of strong electrolyte and to
verify the validity of Onsager’s equation as limiting law of infinite dilution.

Principle:
A solution of strong electrolyte of known strength is prepared and the
conductivity is measured for the solutions of concentrations ranging from
0.1N. Onsager’s equation is λc = λ - (A + B λ) . λc and λ∞ are the equivalent
conductances at concentration ‘c’ and at infinite dilution respectively. A =
0.2273 and B = 59.79 for uni-univalent electrolyte. From the plot of λc vs ,

λ is obtained by extrapolating the line to = 0. The slope is determined

and compared with the value got from Onsager’s equation.

Procedure:
Potassium chloride solutions of the following concentrations 0.01N,
0.02N, 0.04N, 0.06N, 0.08N and 0.1N are prepared. The solutions are taken in
a conductivity cell one by one and the respective specific conductances are

measured. From this, the equivalent conductance can be

calculated. λc is plotted against . The value of λ∞ is obtained by

extrapolating to = 0. The slope is compared with that obtained from

Onsager’s equation.
Result:
The equivalent conductance of Potassium chloride at infinite dilution is
found to be λ = _____________ohm-1 cm2 g equ -1.
Onsager’s slope = _____________ohm-1 g equ-1.

45
Ex. No. 18

WEAK ELECTROLYTE – DISSOCIATION CONSTANT OF WEAK

ELECTROLYTE – VERIFICATION OF OSTWALD’S DILUTION LAW

Concentration
S. Conductance  2C
of CH2COOH c(mho.m2) C ka  x103
No. (m.mho) 1- 
(N)

Average =
TC

46
Ex.No.:18 DISSOCIATION CONSTANT OF A WEAK ACID
Aim:
To verify Ostwald’s dilution law and to determine the equivalent
conductance of acetic acid and its dissociation constant.
Principle:
The equivalent conductance of any electrolytes is defined as the
conducting power of all the ions produced by 1 gm equivalent of the
electrolyte. The equivalent conductance of the solution depends upon the
number and rate of migration of anions and cations. The experiment
indicates that equivalent conductance increases with dilution. This would
arise either from an increase in the number of individual ions (or) from
the speed of ions. The ionic mobilities are independent of concentration
so that λ is proportional to the number of ions present at different
concentrations. The equivalent conductance at a particular concentration
is a measure of degree of dissociation α = . Arrhenius theory is
applicable only for weak electrolytes. For such solutions conductivity
measurements are used to obtain the degree of dissociation and hence the
dissociation constant.
Thus for acid of different normality the specific conductance and
hence the value of dissociation constant at different concentrations are
calculated λc is plotted vs . According to Ostwald’s dilution law
2
α c/(1- α) = ka , where ka is dissociation constant, α is the degree of
dissociation and c is the concentration. The Thermodynamic dissociation
constant is give by
x

= classical x
According to Debye – Huckel limiting law,
- log = - A | Z+ Z- |
where is ionic strength
A = 0.509
Procedure:
Acetic acid of the following normalities 0.1N, 0.08N, 0.06N,
0.04N, 0.02N and 0.01N are pipetted out in a dry conductivity cell one
by one and the conductivity cell is immersed in the solution. The
respective value for the conductance is obtained. The specific
conductance and equivalent conductance of each of these solution are
calculated from these values of λc and λ∞ can be calculated.
Α = λc / λ∞ and a plot of λc vs are noted.
Result:
Dissociation constant of Acetic acid is ------------ mol dm-3

47
 Ex. No. 19

ALKALINE HYDROLYSIS OF ESTER

Co  C t
C t  C

slope
k2 
0.01

Time (mins)

Time (min) Conductance (m.mho) Co  C t 1 Co  C t

ka  ka 
C t  C 0.01t C t  C 

C =

Co =

Co  C t
= k2 (0.01)t
C t  C

slope = 0.01 k2

slope
k2 =
0.01

48
Ex.No.:19 ALKALINE HYDROLYSIS OF ETHYL ACETATE

Aim:
To study the alkaline hydrolysis of ethyl acetate.

Procedure:
Exactly N/100 solution of sodium acetate and N/100 solution of NaOH
are prepared. The conductance of each solution is determined. This
corresponds to the final and initial conductances of the reaction respectively
20ml of N/20 NaOH and 5ml of 0.02N ethyl acetate are pipetted out into a
clean 100ml standard flask and diluted up to the mark, so that the solution
becomes 0.01N. The conductance of the solution is determined at the intervals
of 4 minutes.
k= where, x is the amount of reactant that has reacted at

time t, ( a-x) is the amount of reactant that remains unreacted at time ‘t’ and a
is the initial concentration of the reactant. If co is the initial concentration and
ct is the concentration given at time t, then the concentration at time t is x equal
to (ct - c∞). c∞ is the conductivity of sodium acetate (N/10) and co being the
conductivity of the N/100 NaOH at time ‘t’.
k=

1  Co  C t 
= . 
0.01  C t  C 

A graph is drawn by plotting on y- axis and ‘t’ on x- axis. The

slope being equal to 0.1k2. From this k2 can be calculated.

Result:
(i) The reaction was found to be second order.
(ii) The second order rate constant of the reaction.
(a) Graphical value = ______ dm3mol -1min-1
(b) Analytical value =______ dm3mol -1min-1

49
Ex. No. 20

SOLUBILITY OF SPARINGLY SOLUBLE SALT

Specific conductance of conductivity water =

Specific conductance of I filtrate =

Specific conductance of II filtrate =

Specific conductance of III filtrate =

Specific conductance of saturated solution of a salt =

Solubility product =

Equivalent conductance at infinite dilution =

k x1000
Solubility of the given sparingly soluble salt =


50
Ex.No.:20 SOLUBILITY OF A SPARINGLY SOLUBLE SALT BY
CONDUCTOMETRIC METHOD
Aim:
To determine the solubility of a given sparingly soluble salt - ________ .

Principle:

The conductivity method is applicable for determining the

concentration of a saturated solution of a sparingly soluble salt, provided the
salt is not hydrolyzed and solubility is not too high. Using Kohlrausch’s law, λ∞
is calculated from ionic conductances of individual ions.

Procedure:
The conductivity of water is first determined. The given salt is
precipitated by slow addition of suitable reagent. The precipitate is digested
on a steam bath for 30 minutes and washed with conductivity water. It is
centrifuged several times and centrifugate is discarded. The precipitate is
taken in a bottle and added conductivity water and shaken mechanically for
half an hour. Then filtered in to the beaker containing the conductivity cell.
The conductivity of the solution is noted. The experiment is repeated until
constant values are obtained. From the conductivity of water and conductivity
of saturated solution, the solubility was calculated using the formulae
S= where S is the solubility of a given salt in g. and k is the
specific conductance at infinite dilution.

Result:
The solubility of the given sparingly soluble salt = ………………….g.eq/lit

51
Ex. No. 21
TITRATION OF MIXTURE OF SODIUM ACETATE AND ACETIC ACID
VS SODIUM HYDROXIDE
Volume of NaOH Conductance Volume of NaOH Conductance
(ml) (m.mho) (ml) (m.mho)

Calculation :

Volume of NaOH =

Strength of NaOH =

Volume of mixture =

Strength of CH3OOH =
Conductance
(m.mho)

Volume of NaOH (ml)

52
Ex.No.:21 TITRATION OF CH3COONa and CH3COOH VS NaOH

Aim:
To determine the strength of CH3COOH conductometrically by titrating
the mixture of CH3COOH and CH3COONa vs NaOH.

Procedure:
40ml of the mixture of CH3COOH and CH3COONA is taken in a
conductivity cell, so that the electrode is completely immersed in the solution.
A standard solution of NaOH is taken in the burette and added in 0.5ml
portions. The solution is stirred well after each addition and allowed to attain
equilibrium. The conductance is measured using digital conductivity bridge.
The conductance is plotted against volume of NaOH. The equivalence point is
the point of intersection. The equivalence point corresponding to the volume
of NaOH required to neutralize CH3COONA. Hence from this value it is
possible to calculate the strength of CH3COOH.

Result:
The strength of CH3COOH = _________ N

53
Ex. No. 22

TITRATION OF MIXTURE OF HCl AND AMMONIUM CHLORIDE VS

SODIUM HYDROXIDE

Volume of NaOH (ml) Conductance (m.mho)

Calculation:

Volume of NaOH =

Strength of NaOH =

Volume of mixture =

Strength of HCl =

Volume of NaOH =

Strength of NaOH =

Volume of mixture =

Strength of NH4Cl =

=
Conductance m.mho)

Volume of NaOH (ml)

54
Ex.No.:22 TITRATION OF MIXTURE OF HCl and NH4Cl VS NaOH

Aim:
To determine the strength of NH4Cl and HCl conductometrically by
titrating with NaOH.

Procedure:
40ml of given mixture of NH4Cl and HCl is taken in a conductivity cell, so
that the electrode is completely immersed in the solution. A standard solution
of NaOH is taken in the burette and added in 0.5ml portions. The solution is
stirred well after each addition and allowed to attain equilibrium. The
conductance is measured using digital conductivity bridge. The conductance is
plotted against volume of NaOH. The equivalence point is the point of
intersection. The equivalence point corresponding to the volume of NaOH
required to neutralize HCl. Hence from this value it is possible to calculate the
strength of HCl.

Result:
(i) The strength of NH4Cl in the mixture = _________ N
(ii) The strength of HCl in the mixture = _________ N

55
Ex. No. 23

TITRATION OF SODIUM ACETATE VS HYDROCHLORIC ACID

Volume of HCl Conductance Volume of HCl Conductance
(ml) (m.mho) (ml) (m.mho)

Calculation :

Volume of HCl =

Strength of HCl =

Volume of CH3COONa =

Strength of CH3COONa =

=
Conductance
(m.mho)

56 Volume of HCl (ml)

Ex.No.:23 TITRATION OF CH3COONa VS HCl

Aim:
To determine the strength of CH3COONa by titrating with HCl.

Procedure:
Pipetted out 40ml of 0.1N in to clean beaker so that the electrode is
completely immersed in the solution. An appropriate solution of 0.5N HCl is
taken in the burette and added in 0.5ml portions. The solution is stirred well
after each addition and allowed to attain equilibrium. The conductance is
measured using digital conductivity bridge and the conductance was plotted
against volume of HCl added. Two straight lines with different slopes are
obtained. The point of intersection gives the equivalence point from which
the strength can be calculated.

Result:
The strength of CH3COONa = ------------ N

57
Ex. No. 24

TITRATION OF MIXTURE OF SODIUM ACETATE

AND ACETIC ACID VS HYDROCHLORIC ACID

Conductance (m.mho)

Volume of HCl (ml)

Volume of HCl (ml) Conductance (m.mkho)

Calculation :

Volume of HCl =

Strength of HCl =

Volume of mixture =

Strength of CH3COONa =

58
Ex.No.:24 TITRATION OF CH3COONa and CH3COOH VS HCl

Aim:
To determine the strength of CH3COONa conductometrically by titrating
the mixture of the CH3COOH and CH3COONa with HCl.

Procedure:
40ml of the mixture of CH3COOH and CH3COONa is taken in a
conductivity cell, so that the electrode is completely immersed in the solution.
A standard solution of 0.5N HCl is taken in the burette and added in 0.5ml
portions. The solution is stirred well after each addition and allowed to attain
equilibrium. The conductance is measured using digital conductivity bridge.
The conductance is plotted against volume of HCl. The equivalence point is
the point of intersection. The equivalence point corresponding to the volume
of HCl required to neutralise CH3COONa. Hence from this value it is possible
to calculate the strength of CH3COONa.

Result:
The strength of CH3COONa = ___________ N

59
Ex. No. 25
TITRATION OF MIXTURE OF AMMONIUM HYDROXIDE
AND SODIUM HYDROXIDE VS HYDROCHLORIC ACID
Volume of HCl Conductance Volume of HCl Conductance
(ml) (m.mho) (ml) (m.mho)

Calculation :

Volume of HCl = Volume of HCl =

Strength of HCl = Strength of HCl =

Volume of mixture = Volume of mixture =

Strength of NaOH = Strength of NH4OH =

= =
Conductance
(m.mho)

Volume of HCl (ml)

60
Ex.No.:25 TITRATION OF MIXTURE OF NaOH and NH4OH VS HCl

Aim:
To determine the strength of NaOH and NH4OH conductometrically by
titrating the mixture with HCl.

Procedure:
40ml of given mixture of NH4OH and NaOH were taken in a conductivity
cell, so that the electrode is completely immersed in the solution. A standard
solution of HCl is taken in the burette and added in 0.5ml portions. The
solution is stirred well after each addition and allowed to attain equilibrium.
The conductance is measured using digital conductivity bridge. The
conductance is plotted against volume of HCl. The equivalence point is the
point of intersection. The equivalence point corresponding to the volume of
HCl required to neutralize NaOH. Hence from this value it is possible to
calculate the strength of NH4OH and NaOH.

Result:
(i) The strength of NaOH = ___________ N
(ii) The strength of NH4OH in the mixture = __________ N

61
Ex. No. 26
TITRATION OF HYDROCHLORIC ACID VS SODIUM HYDROXIDE
Rough Titration
Volume Volume Volume
EMF EMF EMF
of NaOH E of NaOH E of NaOH E
(V) (V) (V)
(ml) (ml) (ml)

Fair Titration
Volume
Volume
of EMF Mean EMF Mean
E E/V of NaOH E E/V
NaOH (V) volume (V) volume
(ml)
(ml)

Calculation :
Volume of Sodium hydroxide = Strength of sodium hydroxide =
Volume of Hydrochloric acid = Strength of Hydrochloric acid =
Graph – 1 Graph – 2

EMF E
(v)
V
62
Volume of NaOH Mean volume
 POTENTIOMETRY

Ex.No.:26 TITRATION OF HYDROCHLORIC ACID VS SODIUM HYDROXIDE

Aim:
To determine the strength of hydrochloric acid potentiometrically by
titration with sodium hydroxide.

Principle:

The end point of the neutralization titration may be found by direct

measurement of the emf of the solution after each addition of alkali to acid.
The change of emf for the addition of a given amount of titrant is maximum at
the equivalence point and so the later can be identified.
The potential of any hydrogen electrode is given by
E = E° - 0.059 log The change in electrode potential or the emf of a
cell made up of the hydrogen and a standard electrode is thus proportional to
the change in pH during titration. At the end point is maximum, where
is the change in potential (or) emf resulting from the addition of a definite
volume (eg. 0.1ml) of titrant. The accuracy with which this point can be
deducted depends on the magnitude of the inflexion in the pH neutralization
curve.

Procedure:
An approximately 0.05N HCl is prepared, 10ml of which is pipetted out
in to a beaker. A pinch of quinhydrone is added. A platinum electrode is
dipped into the solution and it is connected to reference electrode (Saturated
calomel electrode). A standard solution of (0.05N) sodium hydroxide is taken
in aburette and added in 1 cc portions. Emf is measured and the range of
equivalence point is noted. The exact end point is found out by noting the emf
value for each addition of 1 cc portion of the titrant and nearing the
equivalence point 0.5cc, 0.2cc and 0.1cc portions. The following graphs are
drawn.
1. The value of emt Vs Volume of NaOH
E
2. The value of Vs mean volume of NaOH
V
Result:
The strength of hydrochloric acid is ____________ N

63
 Ex. No. 27
TITRATION OF ACETIC ACID VS SODIUM HYDROXIDE
Rough Titration
Volume Volume Volume
EMF EMF EMF
of NaOH E of NaOH E of NaOH E
(V) (V) (V)
(ml) (ml) (ml)

Fair Titration
Volume
Volume
of EMF Mean EMF Mean
E E/V of NaOH E E/V
NaOH (V) volume (V) volume
(ml)
(ml)

Calculation :
Volume of Sodium hydroxide = Strength of sodium hydroxide =
Volume of acetic acid = Strength of acetic acid =
Graph – 1 Graph – 2

EMF E
(v)
V

64
Volume of NaOH
Mean volume
Ex.No.:27 TITRATION OF ACETIC ACID VS SODIUM HYDROXIDE

Aim:
To determine the strength of acetic acid potentiometrically by titration
with sodium hydroxide.

Procedure:
An approximately 0.05N CH3COOH is prepared, 10ml of which is
pipetted out in to a beaker. A pinch of quinhydrone is added. A platinum
electrode is dipped into the solution and it is connected to reference electrode
(Saturated calomel electrode). A standardized solution of (0.05N) sodium
hydroxide is taken in burette and added in 1 cc portions. From the emf value
the range of equivalence point is noted. The exact end point is found out by
noting the emf value for each addition of 1 cc portion of the titrant and nearing
the equivalence point 0.5cc, 0.2cc and 0.1cc portions. The solution is stirred
well after each addition and the corresponding emf is noted.
The following graphs are drawn.
(i) The value of emf vs volume of NaOH.
(ii) The value of vs mean value of NaOH.

Result:
The strength of given acetic acid = ____________ N

65
 Ex. No. 28
TITRATION OF MIXTURE OF ACIDS VS STRONG BASE (NaOH)
Rough Titration
Volume Volume Volume
EMF EMF EMF
of NaOH E of NaOH E of NaOH E
(V) (V) (V)
(ml) (ml) (ml)

Fair Titration
Volume
Volume
of EMF Mean EMF Mean
E E/V of NaOH E E/V
NaOH (V) volume (V) volume
(ml)
(ml)

Calculation :
Volume of Sodium hydroxide = Strength of sodium hydroxide =
Volume of hydrochloric acid = Strength of hydrochloric acid =
Volume of Sodium hydroxide = Strength of sodium hydroxide =
Volume of acetic acid + HCl = Strength of acetic acid =
Graph – 1 Graph – 2

EMF
(v)
E
V
66
Volume of NaOH (ml) Mean volume
Ex.No.:28 TITRATION OF MIXTURE OF ACIDS VS
SODIUM HYDROXIDE

Aim:
To determine the strength of hydrochloric acid and CH3COOH in a
mixture potentiometrically by titration with sodium hydroxide.

Procedure:
An approximately 10ml of the given mixture is pipetted out in to a
beaker. A platinum electrode is dipped into the solution. A pinch of
quinhydrone is added. A reference electrode is also placed in a beaker. Both
are connected to potentiometer. A saturated solution of (0.1N) sodium
hydroxide is taken in the burette and added to the solution in 1cc portions. The
corresponding emf values are noted from the emf values. The exact end point is
noted from the emf value for each addition of 1 cc portion of the titrant and
nearing the equivalence point corresponding to the 2 acids of the emf values,
was noted for the addition of 0.5cc, 0.2cc and 0.1cc portions of the titrant.
The following two graphs are drawn.
(i) The value of emf vs volume of NaOH added.
(ii) The value of vs mean volume of NaOH.

The first equivalence point corresponds to the neutralization of

hydrochloric acid. The second equivalence point corresponds to that of mixture
of hydrochloric acid and acetic acid.

Result:
(i) The strength of given acetic acid in the given mixture = ________ N
(ii) The strength of HCl in the given mixture = __________ N

67
Ex. No. 29

TITRATION OF FAS VS POTASSIUM DICHROMATE

Graph – 1

EMF
(v)

Volume of NaOH (ml)

Graph – 2

E
V

Mean volume

E/V Mean volume

Volume of K2Cr2O7 (ml) EMF (v)
(mv/mL) (ml)

Calculation :

Volume of potassium permanganate =

Strength of potassium permanganate =

Volume of FAS =

Strength of FAS =

68
Ex.No.:29 TITRATION OF FERROUS AMMONIUM
SULPHATE VS K2 Cr2 O7

Aim:
To determine the strength of Ferrous ammonium sulphate
potentiometrically by titrating with potassium dichromate.

Procedure:
A standard solution of 0.05N K2Cr2O7 is taken in the burette. 10 ml of
approximately 0.05N Ferrous ammonium sulphate is taken in the beaker and
about 10ml of dilute H2SO4 is added. A platinum electrode is dipped in the
solution and reference electrode is also placed in the beaker. Both are
connected to potentiometer.
The K2Cr2O7 solution is added from the burette in 1ml portions to fix the
range of equivalence point. It is followed by fair titration by adding 0.5ml,
0.2ml and 0.1ml, so that the equivalence point can be determined.
The following two graphs are drawn.
(i) The value of emf vs volume of K2Cr2O7.
(ii) The value of vs mean volume of K2Cr2O7.

Result:
The strength of Ferrous ammonium sulphate = ------------- N

69
Ex. No. 30

TITRATION OF POTASSIUM CHLORIDE VS SILVER NITRATE

E/V Mean volume

Volume of AgNO3 (ml) EMF (v)
(mv/mL) (ml)

Calculation :

Volume of silver nitrate =

Strength of silver nitrate =

Volume of Potassium chloride =

Strength of Potassium chloride =

Graph – 1

EMF
(v)

Volume of NaOH (ml)

Graph – 2

E
V

Mean volume

70
Ex.No.:30 TITRATION OF KCl Vs AgNO3

Aim:
To determine the strength of KCl potentiometrically by titration with
AgNO3.
Cell construction: Pt / Hg, Hg2Cl2, kCl (salt)// Ag+, Ag

Procedure:
Approximately 0.05N KCl is prepared, 10 ml of which is pipetted out
into beaker and is covered with brown paper. A silver electrode is dipped into
the solution and also a reference electrode is placed in the beaker. Both are
connected to potentiometer.
0.05N AgNO3 solution is taken in the burette. Added this in 1ml portions
and 0.5ml, 0.2ml and 0.1ml towards the end point. The solution is stirred well
after each addition and the emf is noted. An approximate titration is carried
out to fix the equivalence point followed by fair titration.
The following two graphs are drawn.
(i) The value of emf vs volume of AgNO3.

(ii) The value of vs mean volume of AgNO3.

Result:
The strength of given KCl is = _____________ N

71
Ex. No. 31
DETERMINATION OF DISSOCIATION CONTANT OF WEAK
ELECTROLYTE
pH 
E 0
Q  E cal  E obs  96500
2.303 RT

pH log salt  pH
log salt 
 acid  acid  Graph

pKa

E0Q =0.6900 – 0.0017 (t-25) log

salt 
acid 
Ecal = 0.2420 – 0.0007 (t-25)
Eobs = emf values corresponding to the volume of NaOH from Rough titration.

log
salt  = log
V
where
acid   Vn  V 
V = volume of alkali added
Vn = Volume of alkali at the equivalence point from faire titration.

pH = pKa + log
salt  log
salt  = log
V
acid  acid   Vn  V 
pKa = pH - log
salt  V – Vol. of alkali added
acid 
Vn – Equilance pt from fair titration
Calculation
1. Half neutralisation 3. 2/3 neutralisation
pH = pKa + log 1 / 2  log  2 / 3 = log 2
1 / 2  1/ 3
pH = pKa pKa = pH – log 2
pKa = – log Ka – log Ka = pH – log 2
Ka = Ka =
1 4. 1/4 neutralisation
2. neutralisation 3 
3 log  4   log 3
 14 
log 1 / 3 = log (1/2) pKa = pH – log (1/3)
 2 / 3 – log Ka = pH – log (1/3)
pKa = pH – log (1/2)– log Ka = Ka =
Ka =
5. 3/4 neutralisation
log  34   log 3
1 
 4
pKa = pH – log 3
– log Ka = pH – log 3 Ka =

72
Ex.No.:31 DISSOCIATION CONSTANT OF A WEAK
ACID
Aim:
To determine the dissociation constant of a weak acid using
quinhydrone electrode.

Principle:

According to Henderson equation, the pH corresponding to half

neutralization point equals Pka, from which ka can be calculated. Thus it
becomes essential to measure the pH of solution. This can be done using
quinhydrone electrode where potential depends upon hydrogen ion
concentration.

E = E°Q - ln = E°Q + 2.303 pH

from which pH can be calculated, hence ka is calculated from Pka.

Procedure:
Pipetted out 10ml of 0.1N CH3COOH in to a 100ml beaker. A pinch of
quinhydrone is added. A platinum electrode is dipped into it and the calomel
electrode is used as reference electrode. Both are connected to
potentiometer. To this, standardized solution of (0.1N) sodium hydroxide is
added in portions from the burette and the corresponding emf is measured.
The solution is stirred after each addition.
The following two graphs are drawn.
(i) The value of emf vs volume of NaOH added.

(ii) The value of vs mean volume of NaOH.

The emf of the cell at half neutralization is determined from the graph.
As the emf was known the ph can be calculated from the equation.

73
Ex. No. 31 Contd.

pH = [ Ecal - E°Q - Eobs] F / 2.303RT

A graph is drawn taking pH on the y-axis and log

salt  on the x-axis.
acid 
(i) At half neutralization pH = pka – log ka .
Therefore the dissociation constant ka can be calculated.
(ii) The dissociation constant at ¾, 1/3, ¼, and 2/3 neutralisation is
calculated.

Result:
The dissociation constant of CH3COOH IS
(i) At 1/2 neutralization = ---------- mol/dm3
(ii) At 1/3 neutralization = ---------- mol/dm3
(iii) At 2/3 neutralization = ---------- mol/dm3
(iv) At 1/4 neutralization = ---------- mol/dm3
(v) At 3/4 neutralization = ---------- mol/dm3
The dissociation constant of acetic acid = ---------- mol/dm3

74
Ex. No. 32
SOLUBILITY OF SPARINGLY SOLUBLE SALT (CHEMICAL CELL)

a) 0.1M KCl

Eobs = E Ag 
/ Ag
 E cal

E Ag 
/Ag
= E obs +E cal

RT
E Ag 
/Ag
= E  Ag  / Ag  ln a Ag  E cal  E obs

nF

E cal = 0.2422 – 0.00076 (t – 25)

t = Room Temp.

2.30 3RT
log a Ag   E cal  E obs  E Ag 
/Ag
nF

F  E cal  E obs  E Ag  / Ag 

log a Ag  
2.303RT

a Ag   x  _______

E Ag  / Ag = 0.7990v

R = 8.314 J/K

F = 96500

T = Room temp in K

K S AgCl = a Ag a Cl
 

= x.CCl .  Cl
 

= x . 0.1 x 0.8

Ks =

S = Ks

b. 0.01 M KCl

Same calculation

75
Ex.No.:32 DETERMINATION OF SOLUBILITY OF
SPARINGLY SOLUBLE SALT BY
POTENTIOMETIC METHOD – CHEMICAL CELL

Aim:
To determine the solubility of a sparingly soluble salt (AgNO3) using
chemical cell.
calomel 0.1M KCl, AgNO3 /Ag

Procedure:
The electrode Ag / AgNO3 (s) KCl (0.1N) is constructed. It is coupled with
saturated calomel electrode using a salt bridge (KNO3). The emf of cell is
measured using potentiometer. The value of the solubility product (ks) is
calculated using the equation,

Eobs = Ecalomel = EAg+/AgNO3 = E°Ag+/ AgNO3 = - ln aAg

Solubility of silver chloride can be calculated from ks using

Ks = a Ag  a Cl

ks = S moles / litre

Result:
Solubility of AgCl at room temperature using 0.1N KCl and 0.1N AgNO3
is _________________ mol/ dm3

76
Ex. No. 33

SOLUBILITY OF SPARINGLY SOLUBLE SALT

(CONCENTRATION CELL)

Concentration Cell :

a) 0.1 M AgNO3 & 0.1 M KCl Eobs = ___________

2.303RT (a Ag  ) 2
E obs = log
F (a Ag  )1

(a Ag  ) 2
= 0.0591 log
(a Ag  )1

a Ag 
1
– activity of Ag  in 0.1 M KCl saturated with AgNO3

a Ag 
 2
– activity Ag  in 0.1 M AgNO3 solution

a Ag 
 2
= 0.1 x 0.8

a Ag 
(1)
= ________________

a Cl 1M   0.1x0.755


Ks = a Ag (1) a Cl (1)

S= ks = m/dm3.

77
Ex.No.: 33 DETERMINATION OF SOLUBILITY OF SPARINGLY
SOLUBLE SALT – CONCENTRATION CELL

Aim:
To determine the solubility of a sparingly soluble salt (AgNO3) using
concentration cell.

Procedure:
The electrode Ag / AgNO3 (s) KCl (0.1N) is constructed. It is coupled with
AgNO3/Ag, (0.1N) through salt bridge (KNO3). The emf of cell is measured
using potentiometer. The value of the solubility product (ks) is calculated using
the equation,

2.303RT (a Ag  ) 2
Eobs = log
F (a Ag  )1

Solubility of silver chloride can be calculated from ks using

Ks = a Ag a Cl

= s moles / litre

Result:
Solubility of AgCl at room temperature using 0.1N KCl and 0.1N AgNO3

is ____________ mol/ dm3

78
 C++ PROGRAMME
Ex. No. 1
/*conversion of celsius to fahrenheit*/
#include<iostream.h>
#include<conio.h>
void main()
{
float fahrenheit,celsius;
clrscr();
cout<<"12PCH001:"<<endl;
cout<<"give the value of the celsius"<<endl;
cin>>celsius;
cout<<"celsius="<<celsius<<endl;
fahrenheit=1.8*celsius+32;
cout<<"fahrenheit="<<fahrenheit;
cout<<"\n give the value of fahrenheit\n"<<endl;
cin>>fahrenheit;
cout<<"fahrenheit="<<fahrenheit<<endl;
celsius=(fahrenheit-32)/1.8;
cout<<"celsius="<<celsius;
}

Ex. No. 2
/*computation of normality, molarity, molality*/
#include<iostream.h>
#include<conio.h>
void main()
{
float n,m,M;
float wt,mwt,eqwt,wtsol,wtlit;
clrscr;
cout<<"12PCH001:"<<endl;
cout<<"Give the value of wt"<<endl;
cin>>wt;
cout<<"Give the value of mwt"<<endl;
cin>>mwt;
cout<<"Give the value of eqwt"<<endl;
cin>>eqwt;
cout<<"Give the value of wtsol"<<endl;
cin>>wtsol;
cout<<"Give the value of wtlit"<<endl;
cin>>wtlit;
n=wtlit/eqwt;
M=wtlit/mwt;
m=(wt/mwt)*(1000/wtsol);
cout<<"normality="<<n<<endl;
cout<<"molarity="<<M<<endl;
cout<<"molality="<<m<<endl;
}

79
Ex. No. 3
/*To calculate activation parmeters at a given temperature*/
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
float Ea,H,S,T,K,logK,Arrslope;
clrscr();
cout<<"12PCH001:"<<endl;
cout<<"give the value of Arrslope"<<endl;
cin>>Arrslope;
cout<<"give the value of T"<<endl;
cin>>T;
cout<<"give the value of K"<<endl;
cin>>K;
Ea=Arrslope*2.303*8.314;
H=Ea-(8.314*T);
S=19.147*(logK-12.7856+(H/5610.11));
cout<<"Activation energy="<<Ea<<endl;
cout<<"enthalpy of activation ="<<H<<endl;
cout<<"entropy of activation ="<<S<<endl;
}

Ex. No. 4
/*To compute reduced mass and force constant*/
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
float m1,m2,p,w,c,k;
double reducedmass;
clrscr();
cout<<"12PCH001:"<<endl;
cout<<"Give the value of m1"<<endl;
cin>>m1;
cout<<"Give the value of m2"<<endl;
cin>>m2;
cout<<"Give the value of w"<<endl;
cin>>w;
cout<<"Give the value of c"<<endl;
cin>>c;
p=(m1*m2)/(m1+m2);
reducedmass=p/6.02323;
k=4*3.14*3.14*w*w*c*c*reducedmass;
cout<<"force constant="<<k<<endl;
cout<<"raducedmass="<<reducedmass;
}
80
Ex. No. 5
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
float c,z1,z2,iostr,a1,a2,z1,z2,x1,x2;
char electro[10];
clrscr();
cout<<"12PCH001"<<endl;
cout<<"Enter the name of the electrolyte"<<endl;
cin>>electro;
cout<<"Give the value of concentration of the ions"<<endl;
cin>>c;
cout<<"Give the charges of the ions"<<endl;
cin>>z1;
cin>>z2;
Z1=z1*z1;
Z2=z2*z2;
iostr=(c*(Z1+Z2))/2;
cout<<"give the value of activation of ions"<<endl;
cin>>a1;
cin>>a2;
x1=a1/c;
x2=a2/c;
cout<<"ionic strength="<<iostr<<endl;
cout<<"activity coefficient of ion1="<<x1<<endl;
cout<<"activity coefficient of ion2="<<x2<<endl;
}

81
Ex. No. 6
/*A program to obtain d spacing in a cubic crystral*/
#include<iostream.h>
#include<conio.h>
#include<math.h>
void main()
{
int h,k,l;
float d1,d2,d3,x1;
clrscr();
cout<<"12PCH001"<<endl;
cout<<"give the value ofh,k,l"<<endl;
cin>>h>>k>>l;
/*
cout<<"h=1"<<endl;
cout<<"k=0"<<endl;
cout<<"l=0"<<endl;*/
x1=(h*h+k*k+l*l);
d1=(100/sqrt(x1))/100;
cout<<"d100="<<d1<<endl;
cout<<"give the value of h,k,l"<<endl;
cin>>h>>k>>l;
/*
cout<<"h=1"<<endl;
cout<<"k=1"<<endl;
cout<<"l=0"<<endl;
*/
d2=(100/sqrt(h*h+k*k+l*l))/100;
cout<<"d110="<<d2<<endl;
cout<<"given the value of h,k,l"<<endl;
cin>>h>>k>>l;
/*
cout<<"h=1"<<endl;
cout<<"k=1"<<endl;
cout<<"l=1"<<endl;
*/
d3=(100/sqrt(h*h+k*k+l*l))/100;
cout<<"d11="<<d3<<endl;
double a=1.0/sqrt(2);
double b=1.0/sqrt(3);
cout<<"a is:"<<a<<endl;
cout<<"b is:"<<b<<endl;
cout<<"d1 is:"<<d1<<endl;
cout<<"d2 is:"<<d2<<endl;
cout<<"d1 is:"<<d3<<endl;
if((d1==1.0)&&(d2==a)&&(d3==b))

82
{
cout<<"crystal type=simple cubic"<<endl;
}
}/*else
{
if(d1==1&&d2==2/sqrt(2)&&d3==1/sqrt(3))
{
cout<<"crystal type=bcc"<<endl;
}else
{
if(d1==1&&d2==1/sqrt(2)&&d3==2/sqrt(3))
cout<<"crystal type=fcc"<<endl;
}
}*/

83
 MOPAC PROGRAMME

Ex. No. 7

AM1 CHARGE=0 GNORM=0.1 BONDS GEO-OK VECTORS DENSITY

Hydrogen 12PCH001

H
H 1.1 1 1

Ex. No. 8

AM1 CHARGE=0 GNORM=0.1 BONDS GEO-OK VECTORS DENSITY

Boron 12PCH001 triflouride

B
Cl 1.1 1 1 1
Cl 1.1 1 120 1 1 1 2 1
Cl 1.1 1 120 1 180 1 1 2 3

Ex. No. 9
AM1 CHARGE=0 GNORM=0.1 BONDS GEO-OK VECTORS DENSITY
Ammonia 12PCH001

N
H 1.1 1 1
H 1.1 1 109 1 1 2
H 1.1 1 109 1 120 1 2 3

Ex. No. 10
AM1 CHARGE=0 GNORM=0.1 BONDS GEO-OK VECTORS DENSITY
Methane 12PCH001

C
H 1 1 1
H 1 1 120 1 1 2
H 1 1 120 1 109 1 1 3 2
H 1 1 120 1 109 1 1 4 3

84
Ex. No. 11
AM1 CHARGE=0 GNORM=0.1 BONDS GEO-OK VECTORS DENSITY
Ethane 12PCH001

C
C 1.54 1 1
H 1.09 1 110 0 2 1
H 1.09 0 110 0 120 0 2 1 3
H 1.09 0 110 0 240 0 2 1 3
H 1.09 0 110 0 60 0 1 2 3
H 1.09 0 110 0 180 0 1 2 3
H 1.09 0 110 0 300 0 1 2 3

Ex. No. 12
AM1 CHARGE=0 GNORM=0.1 BONDS GEO-OK VECTORS DENSITY
ETHYLENE 12PCH001

C
C 1.34 1 1
H 1.09 1 122 1 1 2
H 1.09 0 122 0 180.0 1 2 1 3
H 1.09 0 122 0 0.0 1 1 2 3
H 1.09 0 122 0 180.0 1 1 2 3

Ex. No. 13

AM1 CHARGE=0 GNORM=0.1 BONDS GEO-OK VECTORS DENSITY

Acetylene 12PCH001

H
C 1.0 1 1
C 1.2 1 180 1 2 1
H 1.0 1 180 1 180 1 3 2 1

85
 INSTRUCTIONS
(C++ Programming)
Desktop Turbo C++
File  New Type the program
Alt F9 compile
File  save as  save the programme. (Name Reg.No. Program No.cpp)
(eg. SASI10I.cpp)
* Be in the program window
* Control F9
* Give the Input, Output will appear.
* Enter program window will appear.
Window (option at the top)

Output
(output will appear)
* click print screen button in the keyboard (No change will be appear).
* click start button in the keyboard.
* select run option and then go to notepad.
* A new window will appear.
* Now type control+V (output will paste)
* Now go to file  save as  give name for your output
(like name Reg. No. prgm. No. output). (SASI10I.cpp)

86
 WINMOPAC

Desktop  Shortcut to WINMOPAC


Type the program

File  Save As (give name register no. name of the molecule program no.)

Be in the program window


Options

Set parameter

AM1

Apply

View

Run MOPAC

Brief result (output will appear)

File (in the same window)

Save as (give name reg. no. program no. output)

87