PHYSICO-CHEMICAL EXPERIMENTS

COMMERCIAL ANALYSIS

Experiment - 1
Aim: To carry out assay of commercial sample of aspirin using phenol red as an indicator.
Given: 0.5 N HCl (approximate), Succinic acid, Phenol red and phenolphthalein indicators.

Principle: Aspirin (acetyl salicylic acid) is a weak acid, when treated with strong
alkali like NaOH at higher temperature, it undergoes the following reaction:

CH3COOC6H4COOH + 2 NaOH HOC6H4COONa + CH3COONa + H2O

It is possible to determine the amount of alkali consumed by aspirin using back titration
method with standardized HCl solution.

NaOH + HCl NaCl + H2O

Therefore one molecule of aspirin is equivalent to one molecule of HCl.

Procedure:
Part I: Standardization of NaOH solution

1) Dissolve 0.590 g of succinic acid in minimum quantity of water and dilute up to 100
cm3 with the help of standard measuring flask. This is 0.1 N succinic acid.
2) Pipette out 10 cm3 of it in a conical flask and titrate against supplied 0.5 N NaOH from
the burette using phenolphthalein as an indicator. End point is colorless to pink.
Let the constant titer reading be ‘z’ cm3.

Part II: Estimation of Aspirin

1) Pipette out 25 cm3 of standardized solution of NaOH in a conical flask labeled as A.

Likewise, pipette out 25 cm3 of standardized solution of NaOH in a conical flask
labeled as B.
2) In a conical flask labeled B, add accurately weighed sample of aspirin (about 0.4 g to
0.5 g) and shake the flask carefully.
3) Heat both the conical flasks on a water bath for 10 to 15 minutes with occasional
shaking.
4) Cool solution in each flask at room temperature.
5) Add 3-4 drops of phenol red indicator in conical flask labeled A and titrate it against
approximate 0.5 N HCl solution from burette. End point is red to yellow.
Let the titration reading be ‘y’cm3.
6) Now add 3-4 drops of phenol red indictor in conical flask labeled B and titrate
similarly.
Let this titration reading be ‘x’ cm3.
7) Repeat the above steps to get constant titer readings for the same weight of sample.

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Observation Tables –
Part I: Standardization of NaOH solution

Obs. Volume of Burette readings for …………… N Constant

No. ……………… ……………………….solution titre
solution in the Initial Final Difference reading (z)
flask (in cm3) (in cm3) (in cm3) (in cm3) (in cm3)

1.
2.
3.

Part II: Estimation of Aspirin

Obs. Weight of Burette reading of ………..N of HCl solution

No. Aspirin in ‘g’ Blank titration ‘y’ cm3 Back titration ‘x’ cm3
1.
2.
3.

Calculation:
Standardization of NaOH : NaOH against Succinic acid
N1V1 = N 2 V2
N 2 V2
N1 =
V1
0.1×10
N1 =
z
N1 = A = ......N
Normality of HCl: HCl against NaOH
N1V1 = N 2 V2
N 2 V2
N1 =
V1
A × 25
N1 =
y
N1 = B = ......N
From the stoichiometry of reaction:
∴ 1 cm3 of 0.5 N HCl ≡ 0.04504 g of Aspirin
(y-x) cm3 of B N HCl = (y - x) B × 0.04504
0.5
= ……………..g of Aspirin

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 Results:
1) Volume of ‘A’ N HCl required corresponding to the amount of NaOH reacted with
aspirin (y-x) = …………………..cm3.
2) Amount of Aspirin present in given sample = ……………….g.
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POTENTIOMETRY

Experiment – 2

Aim: To determine standard E.M.F. of the cell, standard free energy change and equilibrium
constant the cell reaction of the cell, setup by coupling Ag/AgNO3 and Cu/CuSO4
electrode.
Given: 0.1 M AgNO3, 0.1 M CuSO4, Cu-Ag electrodes, salt bridge, and potentiometer.

Procedure:

1) Standardize the potentiometer with built in standard cell of 1.018 V.

2) Prepare 0.05 M AgNO3, 0.05 M CuSO4 solutions (25 cm3 of 0.1M solution + 25 cm3
of distilled water) and 0.01 M AgNO3, 0.01 M CuSO4 solutions (10 cm3 of 0.1M solution
+ 90 cm3 of distilled water).
3) Take about 25 cm3 of CuSO4 and 25 cm3 of AgNO3 solutions in two small beakers
as per the observation table and place Cu and Ag electrode in the respective solutions.
4) Put salt bridge to connect the two solutions, connect Cu electrode to the negative terminal
of potentiometer and Ag electrode to the positive terminal.
5) Record the readings in observation table.

The cell can be represented as

Cu CuSO4(aq) AgNO3(aq) Ag

The cell reaction:

Cu + 2 Ag+ Cu2+ + 2 Ag
Observation Table:

Obs. CuSO4 Activity AgNO3 Activity EMF Std. EMF

No. conc. Co-eff. conc. Co-eff. (Ecell) (E°cell)
a1  m1 1 a2  m2 2
(m1) ( 1) (m2) ( 2) Volt Volt

1. 0.10 M 0.160 0.10 M 0.733

2. 0.05 M 0.216 0.05 M 0.790
3. 0.01 M 0.400 0.01 M 0.900
4. 0.10 M 0.160 0.05 M 0.790
5. 0.05 M 0.216 0.10 M 0.733

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 Calculations: Standard EMF of the cell
Cu 2+   Ag 
2
0 2.303RT
E=E - log
Cu   Ag + 
2
nF

2.303RT Cu 2+ 
 E=E - 0
log 2
nF  Ag + 

 E = E0 -
0.05916
log
 m1γ1 
m2 γ2 
2
2

E0 = E +
0.05916
log
 m1γ1  =.......... V
 m2 γ2 
2
2
2) Standard Free Energy Change:
G 0 = - nFE0
ΔG 0 = - 2×96500 × E0 =........joule
3) Equilibrium Constant
0.05916
ΔE 0 = log K
2
 2 × E0 
K = Antilog  
 0.05916 
RESULTS:
1. Mean Ecell of the cell = ……………….Volt
2. Standard free energy change (∆G°) = ………….. joule
3. Equilibrium constant (K) = ………………………
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CONDUCTOMETRY
Experiment – 3

Aim: To verify Ostwald’s dilution law by determining the equivalent conductance

of acetic acid at different concentrations.
Given: KCl (solid), 0.1N acetic acid solution.
Theory:
Ostwald’s dilution law states that degree of dissociation of a weak electrolyte is
inversely proportional to square root of its concentration or directly proportional to
square root of its dilution of the solution.
The degree of dissociation of a weak electrolyte at a given concentration can be
determined by taking the ratio of equivalent conductances or molar conductances of
electrolyte at the given concentration and equivalent conductances or molar
conductances of electrolyte at infinite dilution.


0

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Procedure: Part I: Determination of cell constant of the conductivity cell

1) Prepare 0.1N KCl by dissolving 0.745 g of it in100 cm3 of solution.

2) Rinse the conductivity cell and a beaker first with distilled water and then with a
small quantity of 0.1N KCl solution.
3) Place the conductivity cell (clamped vertical) in the beaker and fill it with sufficient
amount of 0.1N KCl solution till the electrodes are fully immersed.
4) Standardize the conductometer using built in standard conductance.
5) Connect the terminals of the conductivity cell to the conductometer and determine
the conductance of the KCl solution, using this value obtain the cell constant of the
conductivity cell.

Part II: Determination of the equivalent conductance of the various

concentrations of acetic acid solution
1) Prepare different dilutions of acetic acid solutions in 100 cm3 measuring flasks as
follows:
(i) 0.05 N acetic acid: pipette out 50 cm3 of 0.1N acetic acid and dilute it to 100 cm3
(ii) 0.025 N acetic acid: pipette out 50 cm3 of 0.05 N acetic acid and dilute it to 100 cm3
(iii) 0.0125 N acetic acid: pipette out 50 cm3 of 0.025 N acetic acid and dilute it to 100 cm3
(iv) 0.00625 N acetic acid: pipette out 50 cm3 of 0.0125 N acetic acid and dilute it to 100cm3
2) Rinse the conductivity cell and a 50 cm3 of beaker with distilled water and then with
0.1 N acetic acid solution.
3) Take about 25 cm3 to 30 cm3 of 0.1 N acetic acid in the beaker and dip the cell into
it. Determine the conductance of this solution.
4) Determine the conductance of remaining concentrations of acetic acid solution as
per step 2) and 3).

Observation and Calculation:

PART I : Determination of cell constant
Conductance of 0.1N KCl solution = ……………..S
Specific Conductance of 0.1N KCl = ……………..S cm-1

Specific conductance of 0.1 N KCl ( S cm-1) at different experimental temperatures

Temperature (K) Specific Conductance

297 0.01264
298 0.01288
299 0.01313
300 0.01337
301 0.01362
302 0.01387
303 0.01412

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 Specific conductance of 0.1N KCl 1
Cell Constant   ______ cm
Conductance of 0.1N KCl

PART II:

Cell Constant = …………………….cm-1

Equivalent conductance at infinite dilution of acetic acid (Λ0) = 390.7 S cm2 g eq-1

Observation Table: I
Concentration Conductance Sp. Conductance Eq. conductance
g eq.dm-3 C0 (S) κ = C0 x Cell constant 1000

(c) Scm-1 c
2
Scm /g eq
0.1
0.05
0.025
0.0125
0.00625

Observation Table: II

Concentration Degree of dissociation Dissociation constant

g eq.dm-3   2c
 Ka 
(c) 0 1

0.1
0.05
0.025
0.0125
0.00625

Mean Ka = …………………….
Results:
1) Cell constant = ……………………. cm-1
2) Dissociation constant = ……………………..

Conclusion:
1) The degree of dissociation increases with dilution.
2) Since the value of Dissociation Constant [Ka] is fairly constant. Ostwald’s Dilution Law
is verified.

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 pH METRY

Experiment – 4

Aim: To Titrate a weak acid against strong base pH-metrically and to obtain pKa value
of the acid from titration curve.
Given: Weak acid solution, 0.1N NaOH, Buffer solution of pH 4 and pH 7.

Theory:
When an acid is titrated v/s NaOH its pH shows a large change towards its end point. This
makes it easy to identify the end point of the titration graphically. When acetic acid is
titrated v/s NaOH, sodium acetate is formed as a product. This sodium acetate along
with unreacted acetic acid forms an acidic buffer mixture. According to Henderson’s
Equation for acidic buffer solution,

pH  pK a  log
 salt 
 acid 
at half neutralization point, the pH of the buffer becomes equal to the pK a of acetic acid
because at half neutralization point, [salt] = [acid]. Thus,
pH = pKa
Procedure:

1) Standardize the given pH meter by dipping the Glass electrode first in distilled water
(pH =7) and then with buffer solution (pH = 4).
2) Dilute the given acid solution to 100 cm3 in a measuring flask and pipette out 10 cm3 of
diluted solution in a 100 cm3 clean beaker.
3) Wash the glass electrode with water and clean it with soft tissue paper. Adjust it properly
in the solution of beaker but ensure that it does not touch the bottom or inner walls of
the beaker.
4) Add minimum amount of water (should not be more than 20 cm3) to dip the electrode
properly in the solution.
5) Fill the burette with 0.1 N NaOH solution and clamp it above the beaker.
6) Turn the knob of pH meter to ‘read’ mode and record the value of pH of the solution
(whenever glass electrode is out of the solution, please, ensure that knob is on ‘standby’
mode).
7) Add 0.5 cm3 of burette solution at a time, stir it and record the value of pH.
8) Continue to take the reading after each addition till the pH = 11.

Observations :
Obs. Volume of …….N pH ∆pH ΔpH ΔV
No. NaOH from burette
(cm3)

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Plot graphs of
(i) pH v/s volume of NaOH
pH
(ii) V v/s volume of NaOH

(i) (ii)

pH ∆pH/∆V

pKa

Vx/2 Vx Vx
Volume of NaOH Volume of NaOH

Calculations:
Volume of 0.1 N NaOH required for the equivalence point = Vx =.……..cm3
The normality of diluted acid solution can be calculated as follows:
N1V1  N 2V2

N1 N 2V2
V1
 'B' N
The normality of the given diluted acid solution = B =……………N

Determination of pKa value of acid: According to Henderson’s Equation,

pH  pK a  log
 salt 
 acid 
But at Half neutralization point, [salt] = [acid]
∴ At half value of Vx ( i .e., V x / 2 ) , from graph pH = pKa = …………….
∴ Ka = Antilog (- pKa)

Results:
1) Volume 0.1N NaOH required for neutralization (Vx) = ………….cm3
2) Normality of the diluted acid solution = B = …………………….N
3) pKa value of the weak acid (pH at half Vx) = ……………………
4) Dissociation constant of weak acid (Ka) = …………………….
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 COLORIMETRY

Experiment – 5

Aim: To determine λmax of Potassium permanganate and to determine the

concentration of unknown Potassium permanganate solution using this value of λmax.

Given: 0.1N KMnO4 (0.316 g dissolved in 100 cm3 of solution), six 100 cm3 standard
measuring flasks, 250 cm3 measuring flask, and wash bottle.

Theory:
Beer-Lambert law conveys that intensity of light that is transmitted by a coloured
transparent/ translucent solution is dependent on the concentration of the solution and the
path length it covers while passing through the solution. The greater the concentration of
the solution, lesser is the intensity of light that is transmitted through the solution [Beer’s
Law]. Also, greater the path length that the light covers, lesser is the intensity of light
that is transmitted [Lambert’s Law]. λmax is the wavelength at which maximum
absorption of light takes place by a given solution. It is the characteristic of a solution at a
given temperature.

Procedure:
PART I: Determination of λmax

1) Pipette out 5 cm3 of 0.1N KMnO4 [0.02 M KMnO4] solution in a 250 cm3 measuring
flask and dilute it with distilled water up to the mark. Shake the flask thoroughly, this
is 0.002 N KMnO4 [0.0004 M = 4 x 10-4 M KMnO4] solution.
2) Prepare the following solutions from 0.002 N KMnO4 solution using numbered 100
cm3 of standard measuring flasks.

Sr. No. Volume of 0.002 N Volume of distilled Concentration of

KMnO4 in cm3 water in cm3 Mn2+ ions
[ mol/dm3]
1 10 90 04 x 10-5
2 20 80 08 x 10-5
3 30 70 12 x 10-5
4 40 60 16 x 10-5
5 50 50 20 x 10-5
6 Unknown ------ ----------

3) Adjust the blank to zero absorbance of the colorimeter with distilled water filled in
cuvette.

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4) Rinse the cuvette thoroughly with solution No. (3) and fill it with solution.
5) Measure the absorbance at this wavelength (minimum value available in the instrument).
6) Change the filter of colorimeter and repeat steps (3), (4) and (5) at all the wavelengths
available.
7) Plot the graph of ‘Absorbance’ against ‘wavelength’ to obtain λmax (in nm).

PART II : Determination of unknown concentration

1) Fix the filter to λmax value as obtained from PART I.

2) Starting with solution No. (1), note the absorbance of all the solutions as per the procedure
of steps(3), (4) and (5) of PART I.

Observation Table I : Determination of λmax

Obs.No. Wavelength Absorbance or O.D.
λ
(nm)

Observation Table II: Determination of unknown concentration

Obs. No. Concentration of KMnO4 Absorbance or

(mol dm-3) O.D

1 04 x 10-5
2 08 x 10-5
3 12 x 10-5
4 16 x 10-5
5 20 x 10-5
6 Unknown

Plot graphs of:

(i) Absorbance v/s wavelength
(ii) Absorbance v/s concentration

(i) (ii)

Absorbance Absorbance

unknown conc.

wavelength concentration

50
Results:
1) Observed value of λmax. of KMnO4 = ………….nm
2) Concentration of KMnO4/MnO4- in the unknown solution = ………mol dm-3.

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VISCOMETRY

Experiment – 6

Aim: To find the concentration of the given mixture, consisting of two liquids A
and B, by viscosity measurement.
Given: Oswald’s Viscometer, pipette, stop watch, rubber bulb, liquid A and B.

Theory:
The viscometer most commonly used for comparing viscosities of liquids is the
Oswald’s Viscometer. In its operation different liquids are taken in exactly the same
volume. This is essential so that height of liquid column creating pressure heads are
equal and then the pressure head will be directly proportional to the densities of the
respective liquids. For solutions of 2 liquids, by plotting the values of viscosities
or time of flows of solutions against their concentrations, we get a curve from
which the concentration of the unknown solution is determined. Curves of various
solutions are sagged, i.e. fall below the straight line connecting the viscosities of their
components.

Procedure:

1) Prepare a number of solutions by mixing 2 liquids A and B in different proportions

(10%, 20%, 30%, 40%, 50% 60%, 70%,80%, 90% with respect to’ A’ by volume)
as shown in the table below.

2) Determine the time of flow of each of the mixtures

through the capillary of an Ostwald’s viscometer. Take 3 readings
for every solution.

3) Determine the time of flow of the unknown mixture.

4) Plot the graph of Time of flow v/s concentration of ‘A’ in the

mixture. From the plot determine the composition of the unknown
mixture.

51
Precautions:

1) The viscometer should be held vertical while performing the experiment.

2) The temperature should be maintained constant, as the viscosity is greatly influenced by
temperature.
3) Same volume of water and the liquid should be taken in the viscometer

Observation Table:

Average
Volume of Volume of Percentage Percentage Time of flow time of
A B of A in the of B in the (in seconds) flow
(in cm3) (in cm3) mixture mixture
t1 t2 t3
(in sec.)
0 20 0% 100%
2 18 10% 90%
4 16 20% 80%
6 14 30% 70%
10 10 50% 50%
14 06 70% 30%
18 02 90% 10%
20 0 100% 0%
Unknown Unknown ………. ………..

Result:

The composition of the given mixture is …………..% A and…..…% B

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