MANUAL FOR M.Sc.

(previous)

Physical Chemistry Practicals

1
Experiment: 1
ACID CATALYZED HYDROLYSIS OF METHYL ACETATE

Aim:
To compare the strength of acids by studying the kinetics of ester hydrolysis of methyl
acetate, catalyzed by acids.

Apparatus:
Conical flask, burette, pipette-10ml, beakers, plastic trough, copper water bath,
iodination flask, measuring cylinder-100ml.

Chemicals:
1M HCl, 2M HCl, 0.5M NaOH, Methyl acetate, phenolphthalein, .

Principle:
Esters get hydrolyzed in aqueous medium. The reaction is very slow and can be
enhanced in presence of a strong acid like HCl. The reaction can be expressed by the equation:

H+
CH3COOCH3 + H2O ---------------> CH3COOH + CH3OH

The reaction can be followed by volumetric estimation of acetic acid formed in the course of
reaction by strong base. The reaction is first order with respect to methyl acetate since the
concentration of water is taken in large excess. Hence the reaction is a pseudo first order
reaction and the rate constant can be calculated by using the equation:

k = 2.303 log (V∞ - V0)

t (V∞ - Vt)

Where k is first order rate constant, V 0 is volume of sodium hydroxide required by

the reaction mixture initially; V t is volume of sodium hydroxide required by reaction mixture at
that particular instant of time,
& V∞ is the infinite reading.

Procedure:
Take 100 ml of 1M HCl in a clean iodination flask and place it in a water bath to attain
room temperature. Fill the burette with 0.5 M NaOH solution. Now add 10 ml of pure methyl
acetate to the iodination flask containing HCl solution and shake the solution gently.
Immediately note the time and pipette out 10 ml of the reaction mixture into a clean conical flask
containing 50 ml of ice cold water(see that there remains pieces of ice till the end of the titration)
in order to quench the reaction. Now add two drops of phenolphthalein indicator and titrate
against 0.5M NaOH solution until a pale pink color just persists. Repeat the titration with 10 ml
of the reaction mixture for every 10 minutes of time interval up to 60 minutes & tabulate the
results.

Heat the remaining reaction mixture in a water bath at 60ºc for about 20 minutes. Cool
it to room temperature and pipette out 10 ml of the reaction mixture into a clean conical flask
containing 50 ml of distilled water and 2 drops of phenolphthalein indicator. Titrate this against
0.5M NaOH and note the titer value as V∞.

2
Note:
Repeat the whole experiment with 2M HCl and compare the rate constant with respect to
the strengths of acids.

Calculations: Calculate the rate constant k for the both the reactions using first order rate
equation. The ratio of rate constants is proportional to the strength of the acids.

Graph:
Plot a graph by taking log (V∞ - V0) / (V∞ - Vt) on Y-axis and time on X-axis.
A straight line passing through origin is obtained and its slope is equal to k/2.303.

log(V∞-V0)/(V∞-Vt)
Slope = ∆y/∆x = k/2.303

Time (min)

Hence k =slope × 2.303, Units = min-|

Tabular column:

S.No TIME Vol. of (V∞-vt) (V∞-V0)/(V∞-Vt) Log(V∞-V0)/(V∞-Vt) K

(Min). NaOH (a-x) (min-|)

Result:
The rate constant for the hydrolysis of methyl acetate using
1N HCl: 1) experimentally ------ 2) by graph ---------
2N HCl: 1) experimentally ------ 2) by graph ---------

The ratio of the strengths of the acid was found to be:

3
Experiment: 2
POTASSIUM PER SULPHATE–POTASSIUM IODIDE REACTION

AIM:
To determine the over all order rate constant for the reaction between potassium
persulphate potassium iodide.

Apparatus:
Conical flask–2 No., burette, pipette–10ml, iodination flask, watch glass

Chemicals:
0.05M K2S2O8, 0.1M KI, 0.01MNa2S2O3, starch solution

Principle:
The reaction between potassium per sulphate and potassium iodide may be represented
by the equation:

K2S2O8 + 2 KI --------------------> 2K2SO4 + I2

During the reaction iodine is liberated and the progress of the reaction can be followed
by titrating the liberated Iodine against standard hypo solution at definite intervals of time. The
volume of sodium thiosulphate consumed by the reaction mixture is proportional to the amount
of iodine liberated in the course of time.
This is a second order reaction where equal concentrations of reactants are taken. The reaction
between the liberated I2 &hypo solution is given by the equation:

2Na2S2O3 + I2 ------------- Na2S4O6 + 2NaI

Procedure:
Take 50 ml of 0.1M KI in a clean reagent bottle and place it in a water bath to attain
room temperature. Fill the burette with 0.01 M sodium thiosulphate solution. Now add 50 ml of
0.05M K2S2O8 to the reagent bottle and immediately note the time and gently shake the mixture.
After 10 minutes pipette out 10 ml of the reaction mixture in to a clean conical flask containing
50 ml of ice cold water (see that there remains pieces of ice till the end of the titration) and 1ml
of starch indicator. Titrate this mixture against 0.01M sodium thiosulphate solution until the blue
colour just disappears, note volume of sodium thiosulphate consumed by the reaction mixture
as Vt. Repeat the titration in the same manner for every 10 minutes of time interval. Take 6
readings and the titer values corresponds to the amount of I2 liberated in the course of reaction.

To obtain the initial concentration of K 2S2O8, the following procedure is adapted.

During the early part of the reaction (say before 20 minutes) pipette out 10 ml of the reaction
mixture into another conical flask and add 1gm of solid KI to it. Cover the conical flask with a
watch glass and place it in the dark for 1 hour. After 1hour add 50 ml of ice cold water, starch
indicator and titrate this mixture against 0.01MNa2S2O3 and note the titer value as ‘a’.

The rate constant for this reaction can be obtained from the equation:

k = x / t a*(a-x) lit mol-1 min-1.

4
 Graph:
Plot a graph by taking x/ (a-x) on Y–axis and time on x axis. A straight line passing
through origin is obtained. The slope of the straight line is equal to ‘Ka*’. Hence slope divided by
‘a*’ gives the value of 2nd order rate constant K.

x/ (a-x)

time

Where a*is initial concentration of I 2 in moles/liter and which corresponds to the initial
concentration of the reaction and can be calculated from the titer value ‘a’ by following the
equation:

I2 + 2Na2S2O3 ---------------- 2NaI + Na2S4O6.

M1 V1 = M2 V2
n1 n2

S.No. Time Vol. of hypo (a-x) x/(a-x) k = x/t a* (a-x).

x (ml)

Result:
The over all order rate constant for the reaction between potassium persulphate and
potassium iodide reaction is: _______________

5
Experiment: 3

INDIVIDUAL ORDER BY ISOLATION METHOD

DETERMINATION OF THE ORDER OF REACTION WITH RESPECT TO POTASSIUM

IODIDE BY ISOLATION METHOD
Aim:
To determine the order of the reaction with respect to KI in the reaction between K2S2O8
and KI

Apparatus:
Conical flask–2, burette, pipette–10 ml, reagent bottle, watch glass

Chemicals:
10ml of 0.1 M KI, 90ml of 0.05M k2S2O8, M/100 Hypo solution

Principle:
The order of the reaction with respect to KI can be obtained by Ostwald’s isolation method,
according to which the experiment is performed by taking all the reactants except one in excess.
The reactant which is not taken in excess is said to be isolated and the order of the reaction with
respect to the isolated species can be determined. The reaction can be followed by titrating the
liberated iodine against standard hypo solution (Na2S2O3) at different intervals of the time.
The reaction between potassium persulphate and KI can be represented by

K2S2O8 + 2 KI --------------------> 2K2SO4 + I2

Procedure:
Take 90ml of0.05M potassium per sulfate in a reagent bottle and add 10ml of
potassium iodide to the flask and stopper the flask and start the stopwatch immediately. After 10
min. pipette out 10 ml of the reaction mixture into a clean conical flask containing 50ml of ice
cold water. Add 1-2ml of starch indicator and titrate against M/100 Hypo solution and note the
end point at the first disappearance of blue colour. Repeat the above procedure for every 10min
for about 6 readings. The titre value corresponds to ‘x’

For initial conc. ‘a’ during the early part of the reaction pipette out 10 ml of reaction
mixture into a conical flask and cover it with a watch glass and keep it in dark. After an hour
wash the lower part of the watch glass with test tube full of distilled water into the conical flask
and titrate against standard hypo solution using starch as an indicator. The end point
corresponds to initial concentration ‘a’.

Calculate the rate constant for the above reaction using first order rate equation given as
follows:
k= 2.303/t * log(a/(a-x))

6
Graph:
Plot the graph by taking log a/ (a-x) on y-axis and time on x-axis. A straight line passing
through origin is obtained. The slope of the straight line multiplied by 2.303 gives the rate
constant.

log (a/(a-x))
Slope = k/2.303

Time

Time volume of a-x a/(a-x) log(a/(a-x)) k= 2.303/t

hypo log(a/(a-x))

Result:
The order of the reaction with respect to kI is first order since a straight line passing
through origin is obtained when log (a/ (a-x)) vs time is plotted and the rate constant of the
reaction is = ------------

7
Experiment: 4
INDIVIDUAL ORDER BY INITIAL RATE METHOD

DETERMINATION OF ORDER OF THE REACTION WITH RESPECT TO [S2O82-] BY INITIAL

RATE METHOD

Aim:
To determine the order of the reaction with respect to [S2O82-] by initial rate method

Chemicals:

M/20 k2S2O8, M/20 k2So4, M/10 KI, M/100 Hypo starch solution

Apparatus:

Reagent bottle, burette, pipette, conical flask, stops watch.

Principle:

The order of the reaction with respect to particular reactant can be measured by taking the other
reactants in excess. (Here except S2O82-all the other reactants are taken in excess).
This is called isolation method. The method of initial rate is also used for the determination of
order of the reaction.
As the reaction precedes the conc of product increases and some times may alter the
rate during the course of reaction usually the first 10% of the course of reaction is regarded as
uncomplicated.

The reaction between K2S2O8 and KI can be given as

K2S2O8 + 2 KI --------------------> 2K2SO4 + I2

The rate equation can be given as Rate = k * Cn

log rate = log k + n log C

(or) n = (log r2 – log r1) ÷ (log c2 – log c1)

Procedure:
Prepare 0.05 M K2So4 solution, 0.05 M K2S2O8 solution and 0.1 M KI solution. Prepare
the following sets of the reaction mixture.

Set no Vol. M/20 K2So4 Vol. M/20 K2S2O8 Vol.M/10 of kI

Set I 20ml 40ml 40ml
Set II 30 30 40
Set III 40 20 40
Set VI 50 10 40

8
 Prepare the first set of the reaction mixture by taking K 2So4, K2S2O8 in a reagent bottle then
add KI solution, and immediately start the stopwatch. Stir the flask and keep it aside. After every
5min pipette out 10ml of the reaction mixture into a clean conical flask containing 50ml of ice
cold water and titrate against M/100 hypo solution using starch as an indicator. Repeat the
above procedure 6 times for every 5 min till 30 min.
Repeat the above procedure for the other three sets of reaction mixture.

Graph:
Plot 4 different graphs by taking time on x-axis and V t on y-axis for each set. Join the
points. A parabolic curve is obtained. To this curve draw tangents at initial points using a mirror
and find slope to this tangents. The slopes of the tangent correspond to the rate of the reaction.

Plot another graph by taking log rate on y-axis and log [S 2O82-] on x-axis. A straight line with an
intercept is obtained. The slope of the straight line gives the order of the reaction.

Also the order of the reaction (n) can be calculated by using the above given formula

n=(order)

Vt log rate

time log[S2O82-]

Result: The order of the reaction with respect to K2S2O8 in the reaction between S2O82- & I- by
initial rate method is ______________

9
Experiment: 5
STOICHIOMETRY
DETERMINATION OF THE STOICHIOMETRY OF A GIVEN REACTION

Aim:
To determine the stoichiometry for the reaction between potassium per sulphate and
potassium iodide

Apparatus:
Conical flask, burette, pipette, beaker, reagent bottle
Chemicals:
M/60, potassium dichromate, 10% KI solution, conc Hcl, 0.1M hypo and starch solution,
Potassium per sulfate

Principle:
Principle involves the estimation of iodine liberated when a definite amount of persulphate
is allowed to react with excess potassium iodide solution.
Let ‘a’ moles of persulphate react with ‘b’ moles of KI to give products. The ratio of b/a is
determined by taking a known molarity persulphate solution added to excess KI. The reaction
mixture is kept over night and the molarity of I2 is determined from which the ratio is determined.
The reaction between per sulphate and iodide is represented by:

a S2O82- + b I- I2 + SO42-.

Procedure:
Part I:
Preparation of standard K2S2O8 and KI:
Weigh accurately about 0.5 gm of K2S2O8 and 2 gm of KI in a clean iodination flask.
Measure accurately 250ml of distilled water and add to the iodination flask and stopper it. Keep
the flask in dark for one day.

Part II:
Standardization of hypo solution:
Weigh accurately about 0.49 gm of K 2Cr2O7 in a 100ml standard flask and make it up to
the mark with distilled water. Shake the solution well. Fill the burette with given hypo solution.
Pipette out 20ml of potassium dichromate solution into a clean conical flask, add 3ml of
concentrated HCl and one test tube full of 10% KI solution. Cover it with a watch glass and
place it in dark for 5 min. After 5 min wash the lower side of the watch glass with distilled water
into the conical flask. Titrate the liberated I 2 gas against the hypo sol. The colour changes to
light brown colour, now add 2ml of starch indicator and continue the titration till the blue colour
just disappears and green colour is obtained. Note down the burette reading and repeat the
titration until the concurrent readings are obtained. Calculate the molarity of hypo solution. The
reaction between I- and dichromate is represented by the equation:

6I- + Cr2O72- + 14H+ 2Cr+3 + 3I2 + 7 H2O.

Part III:

10
Estimation of I2 in the reaction mixture:
Pipette out 40 ml of the reaction mixture which has been kept in dark over night. Add
3ml of starch indicator and titrate it against the standardized hypo solution. The end point is
detected by the appearance of colourless solution. Repeat the titration for concurrent readings
and find the concentration of I2 liberated.

I2 + 2Na2S2O3 2NaI + Na2S4O6

Calculations:
i) Calculate the concentration of potassium persulphate using the equation for molarity.

ii) Calculate the concentration of hypo solution in the second step

iii) Using the concentration of hypo calculate the concentration of iodine in the reaction mixture.

iv) Now multiply the concentration of iodine by 2 to get the concentration of iodide.

v) Now the ratio of iodide to persulphate concentration gives the stoichiometric ratio of the
reactants.

Result:
The stoichiometric ratio of iodide to persulphate is--------------

11
Experiment: 6 DISTRIBUTION STUDIES

DETERMINATION OF DISTRIBUTION COEFFICIENT OF ACETIC ACID BETWEEN N-

BUTANOL AND WATER

Aim:
To determine the distribution coefficient or partition coefficient of acetic acid between n-
butanol and water

Chemicals:
5% Acetic acid, 0.1 N NaOH, n-butanol, Phenolphthalein indicator

Apparatus:
Reagent bottle, conical flasks, burette, 10ml pipettes, measuring cylinder

Principle:
When a common solute is added to a system of two immiscible liquids in both of which it
is soluble at a given temperature. Then the solute distributes itself between the two solvents in
such a way that the ratio of its concentration in the two solvents is independent of the amount of
solute distributed between the two phases.

Concentration of I2 in CCl4 layer

KD = Concentration of I2 in H2O layer

KD = Corg /Caq
.
KD is known as partition or distribution coefficient.

Procedure:
Take a clean reagent bottle and take 50ml of n-butanol and 50ml of 5%acetic acid. Now
cork the bottle and shake it well with out spilling of the solution for about 10 minutes. Now open
the cork and keep the bottle aside for 5 minutes with out distributing so that the two layers
separate out. Fill the burette with 0.1M NaOH and clamp it to the stand.
Now pipette out 10ml of the upper layer (org) layer into a clean conical flask and add 2 to
3 drops of Phenolphthalein indicator and titrate against 0.1 M NaOH until the solution turns to
pale pink colour. The solution must be shaked vigorously during the titration, and note the titer
value as vorg. Now pipette out 10ml of lower layer with another pipette into a clean conical flask
and add 2 to 3 drops of phenolphthalein and titrate against 0.1 M NaOH. Note the end point at
vaq.
Now add 10 ml of n-butanol and 10ml of distilled water to the reagent bottle and shake it
for about 5 min and allow it to settle. Repeat the above titration for both the layers and note
down another set of readings. Repeat the above procedure for three more sets of readings.
Calculate the distribution coefficient for each set of readings.

12
Graph:
Plot a graph by taking C aq on x-axis and Corg on Y-axis . A straight line passing through
origin is obtained. The slope of the straight line will be equal to partition coefficient.

Corg
Slope=KD

Caq

S.No. Volume of 0.1M Volume of 0.1 M corg caq K = corg/caq

sodium hydroxide for sodium hydroxide for
aqueous layer organic layer

Result:
The distribution coefficient for the distribution of acetic acid between n- butanol and water is
__________ temperature ___________ 0C

13
Experiment: 7
DETERMINATION OF DISTRIBUTION COEFFICIENT OF I2 BETWEEN CCL4 AND H2O

Aim:
To determine the partition coefficient or distribution coefficient of I2 between CCl4 and
H2O

Apparatus:
Reagent bottle, 2 burettes, 2 pipettes, conical flask

Chemicals:
Saturated solution of I2 in CCl4, distilled water M/20, M/600 sodium thiosulphate solution
and starch solution

Principle:

When a common solute is added to a system of two immiscible liquids in both of which it
is soluble at a given temperature. Then the solute distributes itself between the two solvents in
such a way that the ratio of its concentration in the two solvents is independent of the amount of
solute distributed between the two phases. I2 gets distributed itself between CCl4 and H2O
separately. The partition coefficient can be determined by titrating against hypo solution.

KD = Concentration Of I2 in CCl4 layer

Concentration Of I2 in H2O layer

Procedure:
Take 50ml of I 2 in CCl4 and 50ml of H2O in a clean reagent bottle. Shake the bottle for
about 10 minutes and allow it to settle for 5 minutes. The two layer get separated the lower layer
is considered as CCl4 layer and upper layer as aqueous layer. Now 10ml of upper layer is
pipetted out into a clean conical flask. Titrate the upper layer with M/600 hypo solution using
starch as an indicator. The end point can be detected when the blue color just disappears. Note
the titer value as Vaq. Now pipette out 10ml of lower layer (CCl 4) into another conical flask and
titrate it against M/20 hypo solution. The end point is detected when the blue colour just
disappears and the note titer value as Vorg.

Now add 10 ml of distilled water and 10ml of pure carbon tetra chloride to the reagent
bottle and shake the bottle for few minutes and allow it to settle for 10 minutes to attain the
equilibrium repeat the titration of both the layers and note the end points. Repeat the whole
procedure for both the layers for three more sets of readings and tabulate the titer values and
calculate the concentration of I2 in both the layers and tabulate the results.

2Na2S2O3 + I2 ------------- Na2S4O6 + 2NaI

Graph:
Plot a graph by taking Corg on y-axis and Caq on x-axis. A straight line passing
thorough origin is obtained. Slope of the straight line is equal to partition coefficient.

14
 Corg

Caq

S.No. Volume of hypo for Volume of hypo for corg caq K = corg/caq
CCl4 layer Aqueous. layer

Result:
The distribution coefficient for the distribution of iodine between carbon tetra chloride and water
is ___________ temperature ___________0C

15
Experiment: 8
DETERMINATION OF EQUILIBRIUM CONSTANT BY STUDYING DISTRIBUTION OF I2
BETWEEN CCL4 AND AQUEOUS KI

Aim:
To determine the distribution coefficient of I2 between CCl4 and aqueous KI

Apparatus: Reagent bottles -5, burettes, 2 pipettes, conical flask.

Chemicals: Standard solution of I2 in CCl4, distilled water M/20 hypo solution,

starch solution 0.1M KI

Principle:
I2 distributes between carbon tetra chloride and potassium iodide. The solubility of I 2 in
the aqueous layer is due to the formation of KI3 complex. The solubility I2 increases with
increase in concentration of KI. The partition study experiment can be used for the evaluation
equilibrium constant. The reversible reaction is given by the equation:

KI + I2 KI3

According to law of mass action the eq. constant K is given by

[KI3]

Keq [KI]=[I 2 [KI] [I2]

where [KI3] ,[KI], [I2] represent the equilibrium concentration in a single aqueous solution.
The equilibrium condition may be investigated by studying the distribution of I 2 between
organic solvent and water followed by a similar study of distribution of I 2 between the same
organic solvent and an aqueous solution of KI. KD determined from the former experiment
(distribution of iodine between carbon tetra chloride and water) given by the equation below is
used for evaluating the equilibrium constant Keq.

KD = Corg / Caq
Where Corg & Caq are the concentrations of free iodine in organic & aqueous layers

In a similar study using CCl4 & aqueous KI, Caq will be the total concentration of I2, i.e.
concentration of free I2 as well as concentration of KI3. So therefore free [I2] can be given by:
 Concentration of free iodine [I2] = C2/KD.
 Concentration of combined iodine i.e.
[KI3] = C1 – [I2].
 Concentration of free [KI] = C3 – {C1 – [I2]}.

Where C1 is the concentrationI2 in aqueous layer,

C2 is the concentration of I2 in CCl4 layer,
C3 is the initial concentration of KI.

Therefore by knowing the values of [KI],[I2],[KI3] equilibrium constant can be evaluated.

16
Procedure:
Take 5 clean reagent bottles and number them from 1-5.Prepare the following solution
mixtures:
Bottle No. 1 2 3 4 5
1/3rd dil. Sol. Of 25 25 25 25 25
I2 in CCl4
0.1M KI 25 20 15 10 5
Distilled water 0 5 10 15 20

Now stopper all the bottles and shake each bottle in a rotatory motion for 10 min. And keep it
aside to attain equilibrium. Fill the burette with 0.05 M hypo solution. Now pipette out 10ml of the
upper layer (KI layer) from bottle no. 1 into a clean conical flask and add 1 ml of starch solution
and titrate it against hypo solution. Note the titer value as v aq. Now pipette out 10ml of the lower
layer (CCl4 layer) into another conical flask and add 1ml of starch solution and titrate it against
0.05 molar hypo solution. Note the titer value as vorg. Now repeat the same procedure for other
bottles and tabulate the results.
Calculation:
KD = Corg / Caq
 Concentration of free iodine [I2] = C2/KD.
 Concentration of combined iodine i.e.
[KI3] = C1 – [I2].
 Concentration of free [KI] = C3 – {C1 – [I2]}.

Where C1 is the concentrationI2 in aqueous layer,

C2 is the concentration of I2 in CCl4 layer,
C3 is the initial concentration of KI.

Therefore by knowing the values of [KI],[I 2],[KI3] equilibrium constant can be evaluated by using
the above given formula.
Graph:
Plot a graph by taking C aq/Corg on y-axis and [KI] on x-axis. A straight line passing through
origin is obtained.

Caq/Corg

[KI]

Note: Finding slope is not necessary.

Bottle no. Vorg Vaq Corg Caq Caq/Corg [ KI ]

17
Result:
A graph is plotted between partition coefficient and [KI]
The equilibrium constant for the above equilibrium is given by Keq = ---------

Experiment: 9
ADSORPTION
Aim:
To verify the adsorption isotherm for the adsorption of acetic acid on animal charcoal

Apparatus:
Reagent bottles-5, burette, funnel, watmann paper no. 41, pipette, conical flask.

Chemicals:
0.2N acetic acid, 0.1N NaOH, charcoal 1gm, phenolphthalein

Principle:
Freundlich proposed a relation between the amount of solute adsorbed on a definite
amount adsorbent and the equilibrium concentration of the adsorbate in the solution. According
to which
x/m = k Ce1/n
where x = amount of solute adsorbed
m= mass of the adsorbent
Ce= equilibrium concentration of adsorbate
K = constant.
n = no. of layers of acetic acid adsorbed to the surface layer of charcoal.

In general, 1/n is less than 1 and taking logarithm for the above equation we get

log(x/m) = log k + 1/n log Ce

Procedure:
Take 5 clean reagent bottles and number them 1-5. Prepare the following solution
mixtures.

Bottle no. Vol of 0.1M acetic acid Water Charcoal in gm

1 50ml 0ml 1
2 40ml 10ml 1
3 30ml 20ml 1
4 20ml 30ml 1
5 10ml 40ml 1

Now stopper each bottle and shake the bottles in a rotatory motion for about 10 min and allow
them to stand for at least 1 hour. In the mean time fill the burette with 0.1N NaOH solution.
Pipette out 10ml of stock 0.1M acetic acid solution into a clean conical flask and add 1 or 2
drops of phenolphthalein indicator and titrate it against sodium hydroxide solution. The end point
is noted when a faint pink colour is observed. After 1 hour filter the contents of each bottle
separately through a watmann filter paper no. 41. While filtering reject the first 5ml of the filtrate
and collect the rest. Wait until the filtration is complete and pipette out 10ml of the filtrate in to a

18
clean conical flask and titrate it against with 0.1N NaOH by adding 1-2 drops of phenolphthalein
indicator. The end point is noted when a faint pink colour is observed.
Repeat the procedure with the filtrate of other bottles and tabulate the results.

Graph:
Plot a graph by taking log(x/m) on y-axis and log(C e) on x-axis. A straight line cutting y-axis
is obtained. The slope of the straight line is equal to 1/n and the intercept is equal to log(k).

log(x/m)
log (k)
Slope=1/n

log(Ce)

Calculations:

The initial concentration (Ci) of acetic acid in each bottle can be obtained as follows:

Bottle no. Volume of acetic Initial concentration(Ci)

acid
1 50 50/50 × Cstock acetic acid
2 40 40/50 × Cstock acetic acid
3 30 30/50 × Cstock acetic acid
4 20 20/50 × Cstock acetic acid
5 10 10/50 × Cstock acetic acid

Bottle Initial Vol of N/10 Equilibrium X=(Ci – log(x/m) log(Ce)

no. conc(Ci) NaOH(after concentration Ce)/20
adsorption) (Ce)

Result:
The Freundlich adsorption isotherm is verified.

19
Experiment: 10
DETERMINATION OF PHYSICAL CONSTANTS
VISCOSITY
Aim: To determine the viscosity of the given liquids using Ostwald viscometer
Apparatus: Ostwald viscometer, clamp, beakers
Chemicals: Benzene, carbon tetra chloride, n-hexane
Principle:
Viscosity is a property of fluids which determine their rate of flow, the liquid molecules in
a tube experience an internal resistance to flow. The relative motion of adjacent layers of the
liquid is opposed by an internal friction which resists the sliding of the cylinders. This internal
friction or internal resistance is known as viscosity of the liquid.
The coefficient of viscosity is defined as the force that must be exerted between two
parallel layers of unit area and a unit distance apart, in order to maintain the unit velocity of
streaming of one layer past the other.
Poisulle derived the fundamental equation as below:
η =  r4tp/8Vl
η coefficient of viscosity to the volume V of the liquid which will flow through a narrow tube of
length l and radius r in the time t under the influence of driving pressure p.
the above equation can be reduced as :
η2/ η1 = p1t1/p2t2
the hydrostatic pressure is directly proportional to the density of the liquid.
Therefore η2/ η1 = d1t1/d2t2

Procedure
The Ostwald’s viscometer consists of a fine bore capillary tube a bulb A at its upper end
and a U tube and a bulb B at the lower end. There are two marks x and y on the tube above
and below the bulb A. Clean the viscometer thoroughly with distilled water followed by chromic
acid and again with distilled water. Set the viscometer vertically and introduce a measured
volume of given organic liquid into the large bulb B. Now suck the liquid up into the bulb A
through a rubber tube attached to the up to a level higher than mark x (see the fig). Now allow
the liquid to flow freely through the capillary. Start the stop clock when the liquid reaches the
mark x and note the time when it reaches mark y. repeat the same procedure for concurrent
readings. Repeat the same procedure by taking exactly the same volume of distilled water.
Knowing the densities of given organic liquid and water, co-eff. of viscosity of water the η
value for the organic liquid can be calculated.

SNO liquid Time of Time of Mean Co-eff. of Literature %error

flow in flow in (t1+t2)/ viscosity (η) Value
sec (t1) sec (t2) 2 (milli Poise)
%error
N butyl 29.48
alcohol
Carbon 9.70
tetra
chloride
benzene 6.50

Note: 1 milli poise = 0.001 poise = 1×10-1 m N s m-2.

Result: Coefficient of viscosity of the given liquids

temperature---------0C

20
Experiment: 11 Determination of physical constants
Surface tension
Aim: To determine the surface tension of the given liquids using stalagnometer

Apparatus: Stalagmometer, clamp, rubber tubes weight box.

Chemicals:
Benzene, carbon tetra chloride, n-hexane,
Principle:
All the molecules in a liquid are held together by force of attraction and this causes the
surface of the liquid to behave like a stretched skin. Surface tension is the result of the force of
attraction b/n the molecules present on the surface.
It is the force of acting per unit length of the surface of the surface of the liquid.
The formation of drops depends on the surface tension of the liquid and all liquids will not
give same number of drops from same volume of liquid.
The surface tension of a given liquid can be evaluated by using the equation
η2 = n1× d2
η1 n2 × d1.

where η2 = is the surface tension of the given liquid.

η1 = is the surface tension of water.
n1 = is the no. of drops for water.
n2 = is the no. drops for the given liquid.
d1 = is the density of water.
d2 = is the density of the given liquid.
Procedure:
Description of stalagmometer:
It consists of a fine capillary tube with a bulb at the centre. The upper end of the tube is
fitted with a rubber tube which is used to suck the liquid. The lower end of the tube consists of a
fine capillary bore. The upper and lower end of the bulb contains two marks say A and B.
Clean the stalagmometer thoroughly with distilled water followed by chromic acid and
again with distilled water. Now suck the distilled water through the upper end slight above the
mark A and tighten the rubber tube with a pinch cock. Clamp the stalagmometer and release the
pinch cock. Count the number of drops till the liquid reaches the lower mark B. repeat the
procedure and measure the no. of drops and the mean of the readings is taken into account.
Now discard water and dry the tube by using dry air current or in the oven. Repeat the
procedure with the other given liquids and tabulate the results. Knowing the density values of
the respective liquids calculate the surface tension using the above given formula.

SNO liquid NO. of No. of Mean Surface Literature %error

drops(n1) drops(n2) (n1+n2)/2 tension(η) Value.
Dynes/cm
N butyl 24.6
alcohol
Carbon 26.12
tetra
chloride
benzene 28.25

Note: 1 dyne/cm = 1 milli Newton per metre.

(CGS) (SI)

21
Result: surface tension of the given liquids:

INSTRUMENTATION

22
 CONDUCTOMETRIC TITRATIONS

Experiment: 1

DETERMINATION OF THE STRENGTH OF GIVEN STRONG ACID USING A STANDARD

BASE BY CONDUCTOMETRIC TITRATION
Aim:
To determine the strength of given strong acid using a standard base by conductometric
titration.

Apparatus: Beaker- 250ml, pipette – 20ml, burette, conductivity meter, conductivity cell.

Chemicals: 0. 1M HCl, 0. 5 M NaOH, distilled water.

Principle:
According to Kohlraush’s law the electrical conductance of a solution depends up on the
number of ions present and their ionic mobilities. Consider the titration of strong acid like HCl
and strong base like NaOH:
The reaction can be shown as below:
[H+ +Cl-] + [Na+ + OH-] ------------- [Na+ + Cl-] +H2O.
Before the addition of base, the conductance of the solution is high due to the presence of fast
moving H+ ions. When alkali is added to the strong acid the hydrogen ions are removed by
hydroxyl ions to form unionized water molecule. As a result the conductance of the solution
decreases and reaches a minimum value at the equivalence point after the equivalence point
each addition of alkali increases the conductance due to fast moving hydroxyl ions.

Procedure:
Pipette out 40ml of 0.1M HCl into a clean 250ml beaker and add 40ml of distilled water
and dip the conductivity cell and connect it to the conductivity meter. Fill the burette with 0.5M
NaOH solution. Now add 1.0 ml 0.5M NaOH to the beaker containing 0.1M HCl each time and
note the conductance of the solution. The conductance of the solution will be initially high and
decreases on further additions of the base and reaches a minimum value at the equivalence
point. After the equivalence point is reached, further additions of strong base will increase the
conductance of the solution due to fast moving hydroxyl ions.

Graph:
Plot a graph by taking volume of NaOH on x-axis and conductance of the solution on y-
axis. Two straight lines intersecting at a point is obtained. The intersection point of the two lines
gives the equivalence point.

From this equivalence point calculate the concentration of the given acid

23
 Conductance
Volume of NaOH
required for
neutralization of HCl

Volume of NaOH in ml

S.No. Vol of NaOH( in ml ) Conductance of solution(m mohs)

Result:
The volume of 0.5M NaOH required for the neutralization of given HCl is-------
The strength of strong acid is-------------

24
Experiment: 2

DETERMINATION OF THE STRENGTH OF GIVEN WEAK ACID USING A STANDARD BASE

BY CONDUCTOMETRIC TITRATION

Aim:
To determine the strength of given weak acid using a standard base by conductometric
titration.

Apparatus:
Beaker- 250ml, pipette – 20ml, burette, conductivity meter, conductivity cell.
Chemicals:
0.1M acetic acid, 0.5M NaOH, distilled water.
Principle:
According to Kohlraush’s law the electrical conductance of a solution depends up on the
number of ions present and their ionic mobilities.
Consider the titration of weak acid like acetic acid and strong base like NaOH: The reaction can
be shown as below:

[CH3COO H] + [Na+ + OH-] ------------- [CH3COO- Na+] +H2O.

In the titration of weak acid against strong base, the initial conductance of the solution
will be very low due to the presence of feebly ionized acetic acid. On addition of sodium
hydroxide to the acid solution the highly ionized sodium acetate is formed. Initially the acetate
ions tend to suppress the ionization acetic acid still further due to common ion effect. Further
addition of strong base, slightly increases the conductance of the solution until the equivalence
point is reached. Later additions of NaOH will sharply increase the conductance of the solution.

Procedure:
Pipette out 40ml of 0.1M CH 3COOH into a clean 250ml beaker and add 40ml of distilled
water and dip the conductivity cell and connect it to the conductivity meter and note the initial
conductance of the solution. Fill the burette with 0.5M NaOH solution. Now add 1.0 ml of 0.5M
NaOH to the beaker containing 0.1M CH3COO H every time and note the conductance of the
solution on stirring. The conductance of the solution will be initially very low due to the presence
of feebly ionized acetic acid. On further additions of the base will slightly increase the
conductance of the solution until the equivalence point is reached. After the equivalence point is
reached, further additions of base will sharply increase the conductance of the solution due to
fast moving hydroxyl ions.

Graph:
Plot a graph by taking volume of NaOH on x-axis and conductance of the solution on y-
axis. Two straight lines intersecting at a point is obtained. The intersection point corresponds to
volume of NaOH required for the neutralization of weak acid.

25
 Conductance
Neutralization
Point.

Volume of NaOH in ml

SNo. Vol of NaOH(ml) Conductance (mΩ-1)

Result:
The volume of 0.5M NaOH required for the neutralization of given acetic acid is-------
The strength of weak acid is-------------

26
Experiment:3
Determination of the strength of acids in a given mixture by conductometric titration using
standard sodium hydroxide

Aim:
To determine the strength of acids in a given mixture by conductometric titration using
standard sodium hydroxide

Apparatus: Beaker- 250ml, pipette – 20ml, burette, conductivity meter, conductivity cell.

Chemicals: 0.1M HCl, 0.1M acetic acid, 0.5M NaOH, distilled water.

Principle:
According to Kohlraush’s law the electrical conductance of a solution depends up on the
number of ions present and their ionic mobilities. In the titration of mixture of acids against
strong base, the ionization of weak acid (CH 3COOH) remains suppressed in the presence of
strong acid because of common ion effect. Hence initially only the strong acid is neutralized.
The neutralization of weak acid will commence only when HCl is completely neutralized.
Therefore the initial conductance of the solution will be high due to fast moving hydrogen
ions corresponding to the strong acid. On each addition of base, the conductance of the solution
decreases and reaches a minimum value. On further addition of base, there will be slight
increase in the conductance of the solution until the equivalence point is reached. Further
addition of base will increase the conductance of the solution.

Procedure:
pipette out 40ml of 0.1M HCL and 40ml of 0.1M CH 3COOH into a clean 250ml beaker
and add 40ml of distilled water and dip the conductivity cell and connect it to the conductivity
meter and note the conductance of the solution. Fill the burette with 0.5M NaOH solution. Now
add1.0 ml of 0.5M NaOH to the beaker containing the acid mixture and note the conductance of
the solution. The conductance of the solution will be initially very high due to the presence of
fast moving hydrogen ions corresponding to HCl. On each addition of sodium hydroxide the
conductance of the solution decreases and reaches a minimum value which corresponds to the
equivalence point of strong acid.

Further addition of base NaOH increases the conductance of the solution slightly due
to the presence of feebly ionized hydrogen ions corresponding to acetic acid until equivalence
point is reached. Now later additions of the base after equivalence point will rapidly increase the
conductance of the solution due to fast moving hydroxyl ions corresponding to the base.

Graph:
Plot a graph by taking volume of NaOH added on x-axis and conductance of the
solution on y-axis. Two inflection points are obtained, the former corresponds to the strong acid
(Hcl) and the later corresponds to the weak acid (acetic acid).

27
 Conductance

X1 Y1

Volume of NaOH in ml.

X1 = volume of NaOH required for the neutralization of HCl.

Y1 = total volume of NaOH required for the neutralization of acid mixture.

Volume of NaOH required

for the neutralization of acetic acid =
Y1- X1

Result:
The equivalence point for the neutralization of 40 ml of strong acid by 0.5 M sodium
hydroxide is -------

The equivalence point for the neutralization of 40 ml of weak acid by 0.5 M sodium
hydroxide is-----------
The strength of given acids in the mixture is -------

28
 Experiment:4 Determination of cell constant

Aim:
To determine the cell constant for a given cell at room temperature
Apparatus:
Beaker, Pipette, Standard flask-100ml, Weight box
Chemicals:
N/10 KCl solution

Principle:
Cell constant for a cell is defined as the constant factor which stands for the ratio of the
specific conductance of a solution and its measured conductance in the cell.
Specific conductance / measured conductance = Cell constant

Or Specific conductance = measured conductance × Cell constant.

Since for any conductor the resistance R = ρ l/a
Taking reciprocals 1/R = 1/ ρ × a/l
Or 1/ ρ = 1/R×l/a
Therefore specific conductance = conductance × l/a
Therefore cell constant = l/a
Procedure:
Prepare 0.1M KCl solution by weighing accurately 0.7455 gm of KCl into a clean 100ml
standard flask. From this 0.1M KCl solution prepare 40ml each of 0.05M, 0.02M, 0.01 M, and
0.001M KCl solutions. Take about 40 ml of each solution in to a clean and dry 100ml beaker
and dip the conductivity cell and make necessary connections. Measure the conductance of
each solution and note down.

Note: The specific conductance values of KCl at different concentrations:

Concentration of KCl Specific

conductance(25ºc)
0.1 0.01288
0.02 0.002765
0.01 0.001314

The Cell constant is calculated by using the formula given.

Result:
The cell constant was observed to be -----

29
 Experiment:5
VERIFICATION OF OSTWALD’S DILUTION LAW BY DETERMINING THE
DISSOCIATION CONSTANT OF A WEAK ACID
Aim:
To verify Ostwald’s dilution law by determining the dissociation constant of a weak acid
(acetic acid).

Apparatus:
Burette, conical flask, pipettes, standard flask, conductivity cell conductivity meter, and
beaker

Chemicals:
0.05M oxalic acid, 0.1M NaOH, 0.1M acetic acid, double distilled water.

Principle:

Weak acids and weak bases exist in a state of equilibrium in their aqueous solution. Consider
a weak mono basic acid which partially dissociates in its aqueous sol. There exists equilibrium
between ionized and unionized forms of acid as shown below:

HA H + + A-

If CHA is the concentration of the electrolyte and ‘α’ is the degree of dissociation, then at
equilibrium various concentration terms are given by

CHA = C (1- α), CH+ =C α, C A- =C α. α= Λc/Λ0

Where Λc is the conductance at dilution C, Λ0 is the conductance at infinite dilution.
According to law of mass action K is given by:

K = C α2 / (1- α).
This is known as Ostwald’s dilution law for weak electrolytes and can be verified by
substituting the concentration of weak acid and degree of dissociation (α) in the above equation.
If K comes out to be a constant then the law is verified.

Procedure:

Preparation of 0.05M oxalic acid:

Weigh accurately about 0.63 gm of oxalic acid and transfer it into a 100ml standard flask
and make it up to the mark with double distilled water. Shake it thoroughly for uniform
concentration.

Standardization of NaOH:
Pipette out 10 ml of the oxalic acid in to a clean conical flask; add 1-2 drops of
phenolphthalein indicator. Titrate it against given sodium hydroxide until a pale pink colour is
obtained and the end point is noted. Repeat the titration for concurrent readings and calculate
the concentration of NaOH.

Standardization of acetic acid:

30
 Pipette out 10 ml of the given acetic acid in to a clean conical flask and add 2-4 drops
of phenolphthalein indicator and titrate it against standardized NaOH until a pale pink colour just
persists. Note down the end point and repeat the titration for concurrent readings and calculate
the molarity of given acetic acid.
Now prepare 0.05 Molar acetic acid from the standardized acetic acid into a
100ml standard flask. Pipette out 40ml of 0.05M acetic acid solution into a clean 100ml beaker.
Dip the conductivity cell into the beaker and make necessary connections and note the
conductance of the solution. Now pipette out 20ml of acetic acid from the beaker and discard it.
Add 20ml of distilled water to the beaker and stir the solution. This makes the concentration of
the solution diluted to half. Measure the conductance of the resulting solution. Similarly measure
the conductance of M/80, M/160, M/320, M/640 concentrations and tabulate the results. Using
the formula calculate the dissociation constant K a for each solution and calculate the average
value.

Graph:
Plot a graph by taking α 2 / (1- α) on Y- axis and 1/C on X-axis. A straight line passing
through origin is obtained. The slope of the straight line will be equal to dissociation constant Ka.

α2 / (1- α)
Slope = Ka.

1/C
Result:
The Ostwald’S dilution law is verified and the dissociation constant of acetic acid is found
to be Ka = --------

31
Experiment: 6
Determination of hydrolysis constant of aniline hydro chloride.

Aim:
To determine the degree of hydrolysis and hydrolysis constant of aniline hydro chloride.
Apparatus:
100ml beaker, pipettes, conductivity meter and conductivity cell.
Chemicals:
Aniline hydrochloride, aniline and distilled water.
Principle:
This is applicable only for salts made of weak acid and a strong base or weak base and
strong acid. Consider aniline hydrochloride made from strong acid and weak base. When it is
dissolved in water, it hydrolyses as :

C6H5NH3Cl + H2O C6H5NH3OH + HCl

C (1- h) C (h) C (h)
The equilibrium concentrations of C6H5NH3Cl, C6H5NH3OH, and HCl are given as above. Where
h is the degree of hydrolysis and C is the concentration.
Now the electrical conductance of the above equilibrium mixture will be the sum of the
conductances partly due to the ionized but un hydrolysed salt and partly due to the hydrolysed
salt which yields the ionized strong acid and partially unionized weak base. In this case, the
conductance due to C6H5NH3OH may be neglected. Thus, if the equivalent conductance of the
above equilibrium solution is determined experimentally it will be the sum of the conductances
1- h gm-eq. of unhydrolysed aniline hydrochloride and h gm-eq. of Hcl.
Therefore, Λ = (1- h) Λc + Λ0 Hcl(h). Where Λ0 Hcl is conductance of hydrochloric acid at infinite
dilution and Λc is equivalent conductance of unhydrolysed salt, and is determined by adding
excess aniline to the solution. This excess addition will suppress the hydrolysis of aniline
hydrochloride to an extent that the equivalent conductance of the solution mixture is taken as Λc.
Thus the determination of degree of hydrolysis requires the measurement of conductance of the
salt solution before and after the addition of excess aniline.

Procedure:
Prepare N/32 aniline hydrochloride solution in a 250ml standard flask. Take 40ml of this
solution in a 100ml beaker and note the conductance of the solution. Pipette out 20ml of the
solution from beaker and discard it. Add 20ml of distilled water to the beaker stir the solution
and note the conductance. Repeat the procedure for 3 more times i.e., for N/64, N/128, N/256,
N/512 dilutions.
Repeat the first part of the experiment by adding 1ml of pure aniline to the 40ml of initial
solution and note the conductance of the solution. Discard 20ml of the solution from beaker and
add 20ml of distilled water and few drops of pure aniline and note the conductance. Repeat the
procedure for the above given dilutions.

Graph:
Plot a graph by taking h 2/ (1- h) on y-axis and 1/C on x-axis. A straight line passing
through origin is obtained. The slope of the straight line gives the hydrolysis constant Kh of
aniline hydrochloride.

32
 h2/ (1- h) Slope= Kh

1/C

Conc Conductance Sp.conduct Eq.conduct h h2/(1- h) Kh

With Without With Without With without
aniline aniline aniline

Result:
The hydrolysis constant of aniline hydrochloride was found to be ------.

Note: Λ0 (HCl) = 392.5, 400.5, 406.2, 410.2, 413.10, for respective dilutions.
Experiment:7
Determination of solubility product of sparingly soluble salt by using conductometer.
Aim:
To determine the solubility product of sparingly soluble salt by using conductometer.
Apparatus:
Beaker 100ml, Conductivity meter, Conductivity cell.
Chemicals:
0.1M KCl, 0.1M AgNO3, double distilled water.
Principle:
Conductivity measurements may be employed advantageously for the determination of
solubilities of sparingly soluble salts like AgCl, BaSO 4, and PbSO4 e.t.c. the solubilities of such
salts can not be determined accurately by chemical methods.
As the solubility of such salts is very low, a very small amount of salt gets dissolved in
water and can be regarded as to be present at infinite dilution.
Thus equivalent conductance Λ may be taken as equivalent conductance at infinite dilution Λ∞.
Therefore, Λ∞ = Λ0a + Λ0c.

Λ0a = ionic conductance of anion and Λ0c = ionic conductance of cation of the ions of the salt
at the given temperature.
Supposing the solubility of salt is S gm-eq/ lit, then volume which will contain one gm-
eq of the salt will be 1000/S ml. now the eq- conductance at a definite dilution is given by
Λv = specific conductance × volume containing 1 gm-eq of solute in ml.
Therefore, Λv = Λ∞ = k × 1000/S.
From this equation S can be calculated. The value of solubility product for a binary
electrolyte is given by
Ksp = S × S = S2.

33
Procedure:
Prepare M/10 potassium chloride solution in to a 100ml standard flask using conductivity
water. Pipette out 40 ml of 0.1M KCl solution into a clean 100ml beaker. Now add 3-4 drops of
silver nitrate solution and stir the beaker with a glass rod. Dip the conductivity cell into the
beaker and make necessary connections and measure the conductance of the solution and
note down as observed conductance. Also measure the conductance of double distilled water.

Calculation:
True conductance = observed conductance – conductance of water.

Specific conductance (k) = cell constant × observed conductance.

Solubility S = 1000 k/ Λ∞ where Λ∞ = 138.5 ohm-1 cm2 eq-1.

Ksp = [Ag+] [Cl-]

= S × S = S2.

Result:
The solubility product of a sparingly soluble salt like AgCl is found to be = ---

34
 Colorimetry

Experiment: 8
Verification of Beer’s law using copper sulphate/ potassium permanganate

Aim:
To verify Beer’s law using copper sulphate or potassium permanganate
Colorimetrically
Apparatus:
Standard flask-100ml, graduated pipettes, cuvettes, colorimeter.
Chemicals:
0.1M copper sulphate.
Principle:
According to Beer’s law when a monochromatic light is passed through a medium
(solution), the rate of decrease in the intensity of incident radiation with the distance traveled is
directly proportional to the initial intensity and concentration of the substance absorbing light.
Therefore, -dI/dx α IC
-dI/dx = k IC
-dI/I = k Cdx
on integration, [ln I] I0 I = [kCx]0x
log (I0 /I) = k/2.303 c x.
A = ε c x. ε =k/2.303.
Where A= absorbance, C = concentration, x = path length,
ε = molar extinction coefficient.

Procedure:
Prepare a solution of 0.1 M copper sulphate solution. Calibrate the colorimeter by the
following methods:
i) Firstly insert the dummy or black cuvette and set the instrument for 0%
transmittance, since the black body does not allow any radiation to pass through.
ii) Now place a glass cuvette containing distilled water in to the colorimeter - hose
and set the instrument for 100% transmittance, since the cuvette acts as
transparent body and allows all the radiation to pass through.
[In some instruments, the instrument is set for 0% transmittance and we need to set for
100% transmittance by the above process]
After calibrating the instrument set the instrument for filterNo.1set it to 100% transmittance
using distilled water. Take 0.1 MCuSO 4 solution into another cuvette, wipe out the outer surface
of the cuvette and place it into the colorimeter and close the shutter and note the reading in
terms optical density. Repeat the procedure for all the other filters and tabulate the result. The
filter no. which gives maximum optical density but less than 1 is chosen for further
measurements. The filter corresponds to the band of wave lengths for copper sulphate it is
670nm i.e., filter no 7.
Now set the colorimeter at filter no 7 and prepare the following concentrations of copper
sulphate:

Vol of 1.0ml 2.0ml 3.0ml 4.0ml 5.0ml 6.0ml 7.0ml 8.0ml 9.0ml
CuSO4
Vol of 9.0ml 8.0ml 7.0ml 6.0ml 5.0ml 4.0ml 3.0ml 2.0ml 1.0ml

35
 H2O
The optical densities of the given solutions are measured by calibrating the instrument
for 100% transmittance and tabulate the results.
Graph:
Plot a graph by taking optical density on y-axis and concentration on x-axis. A straight line
passing through origin is obtained, the slope of the gives the molar extinction coefficient of
copper sulphate.

Optical density

slope = ε

Concentration of CuSO4

SNO. Vol of 0.1 M VOL of H2O Optical Concentration

CuSO4(ml) (ml) Density

Result:
A straight line passing through origin is obtained. Hence beer’s is verified.
The molar extinction coefficient of copper sulphate is found to be –

Note: Similar procedure can be followed for potassium permanganate by preparing 100ml of
5×10-4M KMnO4.

36
 POTENTIOMETRY
Experiment: 9
DETERMINATION OF THE STRENGTH OF THE GIVEN STRONG ACID BY STANDARD
BASE USING POTENTIOMETER.
Aim:
To determine the strength of given strong acid by standard base using potentiometer .
Apparatus:
Beaker 100ml, burette, pipette – 10ml, potentiometer, platinum electrode, saturated
calomel electrode.
Chemicals:
0.1MHCl, 0.1M NaOH, quinhydrone.
Principle:
In these titrations the potential of the indicator electrode changes as the concentration of
the ions to which it is responsive changes. To measure the changes the indicator electrode is
coupled with another suitable electrode using a salt bridge. It should be noted that the potential
of the later electrode (calomel) remains unchanged during the progress of the reaction.
Cell representation:
Hg/ Hg2Cl2(s)/ KCl || Q, QH2 /Pt.

EQH2 = E0Q – 2.303 RT/nF pH.

= E0Q + 2.303 RT/nF log [H+].
Therefore, EQ decreases logarithmically as the concentration of H+ decreases and
decrease in the [H+] depends on the volume of the titrant added.
[H+ +Cl-] + [Na+ + OH-] ------------- [Na+ + Cl- + H2O
Procedure:
Pipette out 10ml of 0.1M HCl into a clean 100ml beaker (volume enough to dip the
electrode into the solution). Add a pinch of quinhydrone electrode to saturate the solution and
dip the platinum electrode. The solution is kept in contact with the saturated calomel electrode
using a salt bridge. The terminals of the electrode are connected appropriately to the bridge.
Now add the alkali to the acid in 1ml lots. Stir well the solution after each addition and note
the potential of the cell and find out the approximate volume of sodium hydroxide required for
neutralization of acid. This is a rough titration
Repeat the titration by adding 1ml of NaOH every time initially. Stir the solution and note
the EMF of the solution every time. Near the equivalence point, restrict the addition of NaOH to
0.1ml lots take the readings until 20ml of titrant is added and tabulate the results.

37
Graph:
Plot a graph by taking cell EMF on y-axis and volume of NaOH on x- axis. A curve showing
inflexion at the equivalence point is obtained.
Plot another graph by taking ΔE/ΔV on y-axis and volume of NaOH on x-axis.

ΔE/ΔV
EMF

volume of NaOH . volume of NaOH

SNO. Vol of NaOH EMF (mv) ΔE/ΔV

Result:
The volume of 0.1 M sodium hydroxide required for the neutralization of 10 ml of given strong
acid is:
The strength of the given acid is: ----

38
 Experiment:10 DETERMINATION OF THE STRENGTH OF THE GIVEN WEAK ACID BY
STANDARD BASE USING POTENTIOMETER.
.

Aim:
To determine the neutralization point for the titration between weak acid and strong base.
Apparatus:
Beaker 100ml, burette, pipette, potentiometer, platinum electrode, saturated calomel
electrode, salt bridge.
Chemicals:
0.1M CH3COOH, 0.1M NaOH, quinhydrone.
Principle:
In these titrations the potential of the indicator electrode changes as the concentration of
the ions to which it is responsive changes. To measure the changes the indicator electrode is
coupled with another suitable electrode using a salt bridge. It should be noted that the potential
of the later electrode (calomel) remains unchanged during the progress of the reaction.
Cell representation:
Hg/ Hg2Cl2(s)/ KCl || Q,QH+2 /Pt.

EQH2 = E0Q – 2.303 RT/nF pH.

= E0Q + 2.303 RT/nF log [H+].
Therefore, EQ decreases logarithmically as the concentration of H+ decreases and
decrease in the [H+] depends on the volume of the titrant added.
[CH3COOH] + [Na+ + OH-] ------------- CH3COONa +H2O.
Procedure:
Pipette out 10ml of given acetic acid into a clean 100ml beaker add distilled
water(volume enough to dip the electrode into the solution).Add a pinch of quinhydrone
electrode to saturate the solution and dip the indicator electrode. The solution is kept in contact
with the saturated calomel electrode using a salt bridge. The terminals of the electrode are
connected appropriately to the bridge.
Now add the alkali to the acid in 1ml lots. Stir well the solution after each addition and the
cell EMF is noted after each addition and find out the approximate volume of sodium hydroxide
required for neutralization of acid. This is a rough titration
Repeat the titration by taking same volume of given acid and by adding 1ml of NaOH
every time initially. Stir the solution and note the EMF of the solution. Near the equivalence
point, restrict the addition of NaOH to 0.1ml lots and after the neutralization point add iml of the
base and take the readings until 20ml of titrant is delivered and tabulate the results.
Graph:
Plot a graph by taking cell EMF on y-axis and volume of NaOH on x- axis. A curve showing
inflexion at the equivalence point is obtained.

39
 Plot another graph by taking ΔE/ΔV on y-axis and volume of NaOH on x-axis.

ΔE/ΔV
EMF

Volume of NaOH . Volume of NaOH .

Result:
The volume of 0.1 M sodium hydroxide required for the neutralization of 10 ml of given strong
acid is:
The strength of the given acid is: ----

40
Experiment:
Determination of dissociation constant of weak acid like acetic acid.

The dissociation of a weak electrolyte can be given as:

CH3COO- + H+ CH3COOH
K = [CH3COOH] / [CH3COO-] [H+]
Cell representation:
Hg/ Hg2Cl2(s)/ KCl || Q,QH+2 /Pt.
Ecell = Eright - Eleft
Ecell = E Q/ QH2 - ESCE
E Q/ QH2 = E0 Q/ QH2 –0.05916log[CH3COOH] / [CH3COO-] [H+]
At half neutralization the concentration of [CH3COO-] is equal to [CH3COOH].
Therefore
E Q/ QH2 = E0 Q/ QH2 – 0.05916 log 1/[H+]
Hence
Ecell = E0 Q/ QH2 + 0.05916 log [H+] - ESCE
Where
log [H+] = - pH,
ESCE = 0.242V &
E0 Q/ QH2 =0.7000V

Ecell = 0.7000 - 0.242 - {0.05916 pH}

= 0.458 - 0.05916 pH
pH = 0.458 - Ecell / 0.05916

pH = pKa {at half neutralization}

Therefore
pKa = 0.458 - Ecell / 0.05916
pKa = - log Ka
Hence Ka = 10-pKa

41
 Experiment:11
Titration of dibasic acid against strong base.
Aim:
To determine the neutralization point for the titration of dibasic acid against strong base.
To determine the dissociation constant of the acid corresponding to the two protons.
Apparatus:
Potentiometer, calomel electrode, platinum electrode, potassium chloride salt
bridge.beaker-100ml.
Chemicals:
0.1m malonic acid, 0.1M NaOH, Quinhydrone.
Principle:
In these titrations the potential of the indicator electrode changes as the concentration of
the ions to which it is responsive changes. To measure the changes the indicator electrode is
coupled with another suitable electrode using a salt bridge. It should be noted that the potential
of the later electrode (calomel) remains unchanged during the progress of the reaction.

Cell representation:
Hg/ Hg2Cl2(s)/ KCl || Q,Q+H2 /Pt.

E Q /QH2 = E0 Q/QH2– 2.303 RT/nF pH.

= E0Q/QH2 + 2.303 RT/nF log [H+].
Therefore, E Q /QH2 decreases logarithmically as the concentration of H+ decreases and
decrease in the [H+] depends on the volume of the titrant added. The dibasic acid acts in the
same manner as the mixture of two acids. Two inflexion points for individual dissociation stages
are well marked; each dissociation stage is treated as a separate mono basic acid.
Procedure:
Prepare 0.1M malonic acid. Take 40ml of the acid into a clean 250ml beaker and add a
pinch of quinhydrone so as to saturate the solution. Dip the Pt electrode and couple it with
saturated calomel electrode and make appropriate connections.
Now add alkali from the burette to the acid in 1ml lots, stir well and note the EMF after
each addition and find out the approximate end point corresponding to the two protons. This is
the rough titration. Repeat the titration by adding 1ml of the base initially. Restrict the addition of
the base to 0.1ml lot near the end points corresponding to the two protons and note the EMF of
the solution.
Graph:
Plot a graph by taking EMF of the sol on y-axis and volume of the base added on x-axis. A
curve showing two inflexions is obtained, the former shows the neutralization of first proton and
the later shows the neutralization of second proton.

42
 Another plot is drawn by taking ΔE/ΔV on y-axis and volume of base on x-axis. A curve
showing two peaks corresponding to the neutralization of two protons is obtained. The former is
due to 1st proton and the later is due to the 2nd.

EMF

Volume of NaOH

Result :
The neutralization point for the first proton is:
The neutralization point for the second proton is:
The dissociation constant for the 1st proton is
The dissociation constant for the 2nd proton is

REDOX TITRATIONS

43
Experiment:12 Titration of ferrous ammonium sulphate with potassium dichromate

Aim: To determine the equivalence point for the titration between ferrous ammonium sulphate
and potassium dichromate.
Apparatus: Potentiometer, calomel electrode, platinum electrode, potassium chloride salt
bridge, beaker-100ml.
Chemicals: 0.1Mferrous ammonium sulphate (FAS) , M/60 K2Cr2O7 , conc sulphuric acid,
ortho phosphoric acid.

Principle:
Here the electrode potential depends on the concentration of H+ ions besides the
concentration of Fe+2 and Fe+3. therefore to avoid the effect of change in the [H +] on the
electrode potential, this titration is carried out in presence of large excess of [H +]. Hence the cell
potential depends on[Fe+2]/[Fe+3] ratio.
Cell reaction:
Cr2O72- + 14H+ + 6e- ------------------ 2Cr+3 + 7H2O.
6Fe+2 ------------------- 6Fe+3 +6e-.
Cell set up:
Hg/Hg2Cl2/ KCl || Fe+2/ Fe+3/ Pt.
Procedure:
Prepare 0.1M ferrous ammonium sulphate and pipette out 10ml of it into a 100ml clean
beaker. Add 5ml of conc sulphuric acid and 3ml of ortho phosphoric acid using a graduated
pipette. Dip the platinum electrode and salt bridge and couple it with saturated calomel
electrode and make appropriate connections. Now fill the burette with 0.1 n potassium di
chromate solution and add to FAS in 1ml lots, stir the solution and note the emf value and find
out the approximate end point.
Now repeat the titration and restrict the addition of dichromate to 0.1ml lots near, at and
after the end point. Note the corresponding EMF values until 25ml of the titrant is delivered
Graph:
Plot a graph by taking volume of di chromate on x-axis and EMF on y-axis. A curve
showing the inflection at the end point is obtained.
Plot another graph by taking ΔE/ΔV on y-axis and Volume of K 2Cr2O7 on x-axis. A curve
showing a peak at corresponding end point is obtained.

EMF ΔE/ΔV

Volume of K2Cr2O7 Volume of K2Cr2O7

Result:
The equivalence point for the titration of FAS against K2Cr2O7is-----.
Precipitation titration.

44
Experiment: 13 Titration of potassium chloride vs silver nitrate.
Aim:
To determine the neutralization point for the titration of potassium chloride with silver nitrate.
Apparatus:
Potentiometer, calomel electrode, silver electrode, Ammonium nitrate salt bridge.beaker-
100ml.
Chemicals:
0.1M KCl, 0.1M AgNO3 solution.
Principle:
Here potassium chloride is taken in the beaker and Ag electrode is dipped. The Ag - AgCl
system is considered as an indicator electrode. On addition of AgNO 3 , the concentration of Ag+
ion increases, at the same time the chloride ion concentration increases due to the formation of
silver chloride precipitate, as a result the potential of the solution increases. When silver
electrode is used, the initial potential measurements will be unstable due to unsteady
equilibrium. We get an ascending curve when EMF vs vol of KCl is plotted.
The cell reaction can be represented by
Ag+ + e- Ag(s).
Cl- Cl + e-.

Ag+ + Cl- AgCl(s).

Cell representation:
Hg/ Hg2Cl2(S)/ saturated KCl || Cl- / AgCl (s) / Ag.
Procedure:
Pipette out 10ml of 0.1 M KCl solution into a clean 100ml beaker. Dip the silver electrode
into the solution. Couple the system to saturated calomel electrode using a potassium nitrate or
ammonium nitrate salt bridge. Make appropriate connections with the potentiometer.
Now add silver nitrate from the burette, stir the solution vigorously and note the potential of
the solution. Detect the approximate end point. Now repeat the titration by adding 1ml of AgNO 3
initially and restrict the addition of silver nitrate at and near the end point. Note the
corresponding EMF values until 25ml of the titrant is delivered.

Graph:
Plot a graph by taking volume of AgNO 3 on x-axis and EMF on y-axis. A curve showing
an inflexion at the corresponding end point is obtained. Plot another graph by taking ΔE/ΔV on
y-axis and volume of AgNO3 on x-axis. A curve showing a peak at the end point is obtained.

EMF ΔE/ΔV

volume of AgNO3 volume of AgNO3

Result:
The equivalence point for the titration of potassium chloride against silver nitrate is
obtained as
Experiment:15. Determination of single electrode potential of silver electrode.

45
Aim:
To determine the single electrode potential of silver electrode.
Apparatus:
Potentiometer, calomel electrode, silver electrode, Ammonium nitrate salt bridge.beaker-
100ml.
Chemicals:
0.1M silver nitrate.
Procedure:
Prepare 0.1M AgNO 3 solution and pipette out 20ml of the solution into a clean 100ml
beaker. Dip the silver electrode into the solution and couple it with saturated calomel electrode
with the means of ammoniumnitrate salt bridge. Make appropriate connections and measure the
potential of the solution.
Now prepare the following dilutions: M/20, M/40,M/80, M/160, M/320, M/640 AgNO 3
solution and repeat the above procedure and measure the cell potential
The single electrode potential can be calculated as follows:
Ecell = Eright – Eleft.

Ecell= EAg/Ag+ - ESCE.

EAg/Ag+ = {E0Ag/Ag+ - 0.05916/n log(1/[Ag+])} - ESCE.
EAg/Ag+ = {E0Ag/Ag+- ESCE} - 0.05916/n log(1/[Ag+]).
n= no. of electrons=1,ESCE= 0.242V

Graph: lot a graph by taking Ecell on y-axis and log [Ag+] on x-axis.
A straight line cutting y-axis is obtained. The slope of the straight line will be equal to the value
0.05916.the intercept is equal to {E0Ag/Ag+- ESCE}.

Ecell

log [Ag+]

Result:
The single electrode potential of the silver electrode is equal to---------.

46
Experiment: 16.
Determination of solubility product of silver chloride

Aim:
To determine of solubility product of sparingly soluble salt like silver chloride.

Apparatus:
Potentiometer, calomel electrode, silver electrode, Ammonium nitrate salt bridge.beaker-
100ml.
Chemicals:
0.01M AgNO3, 0.01M KCl.
Principle:
The saturated solubility equilibrium of any sparingly soluble salt such as AgCl, is given by
AgCl Ag+ + Cl-
Where the product of activities of two ions is equal to the solubility product. This involves the
measurement of electrode potential of an electrode reversible to one of the ions of salt.
The cell setup can be given as
Ag/AgCl(s)/KCl | | AgNO 3/Ag
And the solubility product is given by
Ksp = a1 × a3
Where
a1= activity of Ag+ in 0.01 M KCl saturated with AgCl
a3= activity of Cl-
Ecell = 0.05916 log(a2/a1) where
a2 (Ag+) activity of 0.01M AgNO3 = 0.01× 0.892
therefore substituting the value of a2 in the above equation we can find out a1
Procedure:
Prepare 0.01M KCl solution. Take about 20ml of M/100 KCl solution into a beaker and add
one or two ml of AgNO 3. Now take 20ml of M/100 AgNO 3 into another beaker and dip two silver
electrodes into two beakers and make appropriate connections. Couple the system with
ammonium nitrate salt bridge. Note the EMF value.
Calculations:
E cell = 2.303 RT/nF log(a2/a1)
Ksp = a1× a3
a3 activity of chloride ion in 0.01 M KCl = [ Cl- ] γ Cl- 0.01× 0.902

Result:
The solubility product of AgCl in 0.1M solution is --------------

47
 POLARIMETRY
Experiment: 17
DETERMINATION OF SPECIFIC ROTATION OF SUCROSE, GLUCOSE, FRUCTOSE.

Aim : To determine the specific rotation of optically active compounds like sucrose, glucose and
fructose.
Apparatus: Polarimeter, sodium vapour lamp, sucrose, Polarimeter tube, graduated pipette.
Chemicals: 20% sucrose solution, distilled water.

Principle:
When a plane polarized light is allowed to pass through an optically active compound. The
compound rotates the light either clock wise or anti clock wise given by angle of rotation.
[ α ] tλ = 100 θ / l C. where l is the length of the Polarimeter tube in decimeter.
C is the concentration of optically active compound. θ is the angle of rotation in degrees.
Procedure:

Calibration of Polarimeter.
Setup a sodium vapour lamp at a distance equal to the focal length of the lens from
the end of the Polarimeter. Adjust the height of the lamp and optical axis of the instrument for
maximum illumination of polarizer. Fill the Polarimeter tube with distilled water. Avoid entry of air
bubbles into the tube. Place the tube between the polarizer and the analyzer and focus it on the
light shade boundary in the field of view. Determine the zero point of the Polarimeter by rotating
analyzer.
Prepare 20% sucrose solution and take this into the Polarimeter tube and measure
the angle of rotation at this concentration. Similarly, prepare 16%, 12%, 8%, 4% sucrose
solutions and measure their respective angle of rotations.

s.no Concentration Angle of Corrected Specific

rotation rotation rotation

Graph:
Plot a graph by taking concentration on x-axis and angle of rotation on y-axis. A straight
line passing through origin is obtained. The slope of the straight line is equal to α l / 100.

angle of rotation
Slope = α l / 100.

concentration
Result:
The specific rotation of sucrose was found to be -------

Note:
Similar procedure can be followed for determination of specific rotation of glucose and
fructose.

48
Experiment: 18
Inversion of cane sugar with 1 N and 2N HCl

Aim:
To determine the inversion of sucrose with 1N and 2N HCl.

Apparatus:
Polarimeter, sodium vapour lamp, sucrose, Polarimeter tube, graduated pipette.

Chemicals:
20% sucrose solution, distilled water, 1N and 2N HCl.

Principle:
Inversion of cane sugar in presence of acid may be represented as
C12H22O11 + H2O C6H12O6 + C6H12O6
Dextro dextro levo
The reaction is also an example of pseudo uni molecular reaction. The rate of reaction is
determined by the concentration of sucrose where the concentration of acid is kept constant. It
is represented by
dx/dt α [ sucrose ]
The progress of the reaction can be followed by noting the optical activity of the solution
with the help of Polarimeter. Cane sugar and glucose are dextro rotatory. While fructose is
strongly levo rotatory at equi molar concentrations. Hence as the reaction proceeds the optical
rotation of the solution gradually decreases from positive to zero and ultimately becomes
negative due to increase in the formation of products in the solution. Hence it is named as
inversion of cane sugar.
Procedure:
Take 30ml of 20% sucrose solution into a clean beaker and take 30ml of 1N HCl solution
in another beaker. Setup the Polarimeter. Add acid solution to sucrose stir the solution and start
the stop clock and immediately transfer the solution into Polarimeter tube and note the angle of
rotation. Note the angle of rotation of the mixture for every 10minutes of time interval without
disturbing the Polarimeter tube. After 1 hour take the remaining mixture and heat it to about 60 0
i.e., for 20 minutes on a water bath. Cool the reaction mixture and note the angle of rotation of
this mixture as the infinite reading. The rate constant can be calculated by using the following
formula
k = 2.303 / t log {(γ0 – γ ∞) / (γ t – γ ∞)}
Graph:
Plot a graph by taking log {(γ0 – γ ∞) / (γ t – γ ∞)} on y-axis and time on x-axis. A straight
line passing through origin is obtained the slope of the straight line is equal to k / 2.303.

log {(γ0 – γ ∞) / (γ t – γ ∞)}

49
 Time

Result:
The rate constant for the inversion of cane sugar with 1N HCl is -----
The rate constant for the inversion of cane sugar with 2N HCl is ----

The ratio of the strengths of the acids was found to be -------

Note:
Repeat the same procedure using 2N HCl.

50