VEER NARMAD SOUTH GUJARAT

UNIVERSITY, SURAT

DEPARTMENT OF CHEMISTRY
M.Sc. Semester – I
PHYSICAL CHEMISTRY
PRACTICAL SCHEME

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours

STALAGMOMETER
Aim: Determination of CMC and area per molecule of a surfactant by surface tension measurement.
Requirements: Stalagmometer, 20mM SDS solution.
Process: Wash and dry all the apparatus. Prepare 20mM SDS in double distilled water, from 20mM soln.
Prepare dilutions from 1mM to 15mM. Note down the no. of drops for solvent (no ) and similarly count the
no. Of drops for all the dilutions (n).
Observation:
1) Room temperature = _______
2) No. of drops for dist. Water solvent = no = ______
3) Surface tension of dist. Water ( γo ) = 72 dyne / cm.
Observation-table:

No. Conc. of Log C No. of drops Surface

SDS in mM n1 n2 Avg n tension γ =
(no /n )× γo
1-15mM

Graph: v  log C
Calculation:
1) From graph Log CMC =
2) CMC =
3) Slope = dγ /dlogC = AB/BC =
4) x = (1/ 2.303 RT) × (dγ /dlogC) =

Result:
1) CMC of surfactant = ______
2) Area of molecule = ______

Department of Chemistry, VNSGU

 Principle Of Stalagmometer
The stalagmometric method is one of the most common methods for measuring surface
tension. Surface tension means the tension of the surface film caused by the attraction of the
particles in the surface layer by the particles in bulk layer of the liquid, which tends to minimize
the surface area. The principle of stalagmometer is to measure the weight of drops of a fluid of
interest falling from a capillary glass tube, and thereby calculate the surface tension of the fluid.
We can determine the weight of the falling drops by counting them. From it we can determine
the surface tension.

What is Critical Micelle Concentration ( CMC ) ?

Surfactants (tensides) are organic substances, which significantly decrease the surface
tension of water at relatively low concentrations and are, at least partially, water soluble. Because
surfactants are adsorbed mainly on the surface of the solution, creating a thin monolayer, they are
called surface active substances. When dissolving them, after they reach a certain value of
concentration, molecules or ions of surfactants begin to associate and to organize themselves into
more complex units, called micelles. The characteristic concentration value, where the association
process begins, is called the critical micelle concentration and it is labeled with symbol c or
abbreviation CMC.

Principles of determination of CMC

The proportion of molecules present at the surface of a liquid and in the bulk of a liquid
depends on their concentration. At low concentrations, surfactants stay on the surface of the liquid.
Surface tension decreases as more surfactant is added to water. As the surface becomes crowded
with surfactant, additional molecules collect as micelles. This concentration is called the critical
micelle concentration (CMC) and can be found by measuring surface tension. At the CMC point,
adding more surfactant does not change the surface tension. While it is efficient to use surfactant
solutions at their lowest surface tension, it would be inefficient to use them when they have reached
CMC.

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours

CHEMICAL KINETIC
Aim : Investigate the reaction between K2S2O8 and KI at two different temperatures and
calculate the energy of activation for the reaction.
Requirements : 0.05 M K2S2O8 , 0.05 M KI , 0.004 M Na2S2O3 solution, Ice, Starch solution.
Set : (i) 50 ml of 0.05 M K2S2O8 + 50 ml of 0.05 M KI ( at room temperature )
(ii) 50 ml of 0.05 M K2S2O8 + 50 ml of 0.05 M KI ( at higher temperature )
Procedure : Calculate a and b values. Take 50 ml of 0.05 M K2S2O8 in a reagent bottle A and 50
ml 0.05 M KI in reagent bottle B now place both the solution in thermostat at room temperature.
Similarly prepare the other set and place both solution in thermostat at 50° C. After 10 minutes
drain 50 ml KI from bottle B and add it to bottle A with constant stirring and start stopwatch. After
5 minutes pipette out 10 ml of reaction mixture and drain it out in a flask containing ice and now
titrate it against 0.004 M Na2S2O3 using starch as an indicator. Note the readings at 5, 10, 15, 20,
25, 30 minutes for both the reaction mixtures.
Observation – Table :
No. Time ' t ' Burette reading
Min X ml ( a – X ) ml 1/ ( a – X ) ml K =__1 × X__
at × (a – X)
( ml-1 min-1 )
1. 5 – 30

Graph : (i) 1 / ( a – X ) against time ‘t’ (ii) log K against 1 / T

Calculation :
1) Activation energy Ea = 2.303 R T1 × T2 log ( K2 / K1 )
( T2 – T1 )
Result :
1) Rate constants from calculation K1 = ________ ml-1 min-1
2) Rate constants from graph K2 = ________ ml-1 min-1
3) Ea from calculation = ________Kcal
4) Ea from graph = ________Kcal

Department of Chemistry, VNSGU

 CHEMICAL KINETICS : THE STUDY OF REACTION BETWEEN K2S2O8 AND KI
In this experiment, you will study a reaction that proceeds at an easily measured rate at room
temperature:
S2O82- + 2I- 2SO42- + I2
persulfate iodide sulfate iodine

In the first part of the experiment, the rate equation will be determined by investigating the effect
of the concentration of the reactants on the rate of the persulfate-iodide reaction. In the second part, the
activation energy will be calculated by studying the effects of temperature change and addition of a catalyst
on the reaction system.

In this experiment, we study the kinetics of the reaction between persulfate S2O82- and iodide I-
ions:

S2O82 + 2I  2SO42 + I2 (1)

persulfate iodide sulfate iodine

Rates of reaction are measured by either following the appearance of a product or the disappearance
of a reactant. In this experiment, the rate of consumption of the iodine will be measured to determine the
rate of the reaction. As reaction (1) runs, the amount of iodine (I2) produced from it will be followed using
reaction (2):

2S2O32 + I2  S4O62 + 2I- (2)

thiosulfate iodine tetrathionate iodide

The iodine produced from the persulfate-iodide reaction (1) is immediately reduced back to iodide
by thiosulfate ions (2). A known amount of thiosulfate ions will be added to the reaction vessel which will
in turn consume iodine as it is produced. This continues until all the thiosulfate has been converted to
tetrathionate, whereupon free iodine will start to form in the solution via reaction (1). Because we know the
amount of thiosulfate we added, we can determine the amount of iodine produced from reaction (1)
stoichiometrically. When all the thiosulfate is consumed, free iodine starts to form in solution. By measuring
the time taken for the known amount of thiosulfate to be consumed, the rate of production of iodine during
that time can be calculated.
The color of the iodine formed might be intense enough that it can act as its own indicator; however,
for better results, you will add starch, which produces a deep blue starch – iodine complex:

I2 + (C6H10O5)n • H2O  blue complex (3)

iodine starch

In summary, iodide (I-) and persulfate ions (S2O82-) react to produce iodine (I2) and sulfate (SO42-) in
reaction (1). This iodine is immediately consumed by the thiosulfate ions (S2O32-) in a pathway described
by reaction (2). As soon as all of the S2O32- ions are consumed, the excess iodine produced in (1) is free to
react with starch, turning the solution blue (3). The amount of thiosulfate ions added tells us how much
iodine had been produced in the time taken for the reaction to turn blue.

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours

VISCOMETRY
AIM : Determine molecular weight of a given polymer sample by dilute solution Viscometry.

Requirements : Viscometer ( Size – 1 ), Polyvinyl Alcohol Polymer Solution, Solvent.

Procedure : Prepare five dilutions of given polymer sample. Measure flow time for pure solvent and five
diluted polymer solutions. Repeat experiment twice and take mean. Record the results in following
observation table.

Observation :
1) Flow time of solvent ( to ) = i) _______ ii) _______ iii) _______

Observation – table :

No. Concentration Flow time of ηrel = ηsp = ηred =

% solution t / to t / to – 1 ηsp / C
(t)
1. 0.2 – 1.0 %

Graph : Plot graph of ηsp / C  Concentration and determination [ η ] intrinsic viscosity.

Calculation :
1) Calculate Molecular weight using η = KMα

Result :
1) Molecular weight of given polymer sample = __________

Department of Chemistry, VNSGU

What is Viscosity ?
Viscosity is a measure of a fluid’s resistance to flow. It denotes the resistance of a fluid to change
in shape or movement of neighboring portions with respect to one another. A viscometer is an instrument
used to measure the viscosity of a fluid. Various types of glass capillary viscometers, especially Ubbelohde-
type glass capillary viscometers, are used for the determination of the intrinsic viscosity and other polymer
parameters.
Intrinsic viscosity determination is used in the field of polymer chemistry, a chemistry sub –
discipline which deals with the synthesis of polymers as well as the analysis of a polymer’s structure and
properties. The intrinsic viscosity is used to classify polymers and helps to identify the applications that
specific polymers can be used for.

DILUTE SOLUTION VISCOMETRY

Dilute solution viscometry is a well-known analytical technique in polymer chemistry for

characterizing polymers in solution. The technique is based on the fact that dissolving a polymer in a solvent
increases the viscosity of the final polymer solution. The increase of viscosity depends on the temperature,
the type of polymer and solvent, the concentration of the polymer, and the molar mass of the polymer.
Generally, it can be said that the higher the molar mass of a polymer, the higher the viscosity of the polymer
solution will be.

The viscosity of the pure solvent and the viscosity of the polymer solution (polymer dissolved in
solvent) are set in relation to each other, which leads to a relative viscosity value. From this basic parameter
various polymer parameters can be calculated as shown in Figure given below.

The flow behavior of the polymer solution is highly dependent on the molecular structure of the
polymer as well as on interactions of the molecules with each other in solution. As the molecular
interactions decrease with decreasing concentrations, viscosity measurements are carried out with very
dilute solutions. A solution free of any interactions between the polymer molecules could only be reached
in the state of the “ideal dilute solution”. In this “ideal dilute solution” the concentration approaches zero
meaning that the polymer molecules are isolated from each other and only interact with the solvent
molecules. However, this state can never be reached in reality and therefore small polymer interactions
have to be considered. Both the calculation of the reduced and the inherent viscosity require the
concentration value and therefore the intrinsic viscosity is an important parameter as it is an extrapolation
to a theoretical zero concentration.
Inherent Viscosity
𝑡
Relative Viscosity 𝑡0 ηrel
ηrel = 𝒕
𝒕 ηinh = ln = ln
𝑐 𝑐
𝟎

Specific Viscosity
𝒕−𝒕 Intrinsic Viscosity
ηsp = 𝒕 𝟎 = ηrel – 1
𝟎

Reduced viscosity
𝒕−𝒕 η𝑠𝑝
ηred = 𝒕 𝟎 = 𝒄
𝟎∗𝒄

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours
COLORIMETRY
Aim : Calculate the molar absorptivity of each of the given two solutions ( A ) and ( B ) and
also find out the concentration of supplied unknown solution colorimetrically.
Requirements: 0.001 M KMnO4 solution, 0.01 M K2Cr2O7 solution.
Procedure : Determine the λmax for both given stock solution. Prepare five dilutions for each given
solution. Measure absorbance of each dilution at their respective λmax. Find out the concentration
of unknown solution from the graph. Calculate molar absorptivity for both the solutions.
Observation – table :
λmax for KMnO4 λmax for K2Cr2O7
Wavelength Absorbance Wavelength Absorbance
420 – 700 nm 420 – 700 nm

For KMnO4 at _______ nm For K2Cr2O7 at _______nm

Concentration ( M ) Absorbance Concentration ( M ) Absorbance
0.0001 M 0.001 M
0.0002 M 0.002 M
0.0003 M 0.003 M
0.0004 M 0.004 M
0.0005M 0.005 M
Unknown Unknown
Graph : Absorbance  concentration
Calculation :
1) Molar absorptivity of KMnO4 = slope = _______lit./mol cm.
2) Molar absorptivity of K2Cr2O7 = slope = ______lit./ mol cm.
Results :
1) Concentration of given unknown solution of KMnO4 = ________ M.
2) Concentration of given unknown solution of K2Cr2O7 = ________ M.
3) Molar absorptivity of KMnO4 = _______lit./mol cm.
4) Molar absorptivity of K2Cr2O7 = ______lit./ mol cm.

Department of Chemistry, VNSGU

 Colorimetric Method : To determine concentration of
unknown solution
In physical and analytical chemistry, colorimetry is a technique used to determine the
concentration of colored compounds in solution. A colorimeter is a device used to test the
concentration of a solution by measuring its absorbance of a specific wavelength of light

What is Beer – Lambert Law ??

The Beer-Lambert law (or Beer's law) is the linear relationship between absorbance and
concentration of an absorbing species. The general Beer-Lambert law is usually written as:

A = a( ) * b * c

Where A is the measured absorbance, a( ) is a wavelength-dependent absorptivity

coefficient, b is the path length, and c is the analyte concentration. When working in concentration
units of molarity, the Beer-Lambert law is written as:

A= *b*c

Where is the wavelength-dependent molar absorptivity coefficient with units of lit mol-1cm-1.

When a chemical species absorbs visible light, electrons in the normal ground state are raised to a
higher energy excited state. The difference in energy between the two states of the absorbing
species is equal to the energy of the light quantum absorbed. As a beam of monochromatic light,
i.e., light of a single wavelength, passes through an absorbing solution, the intensity of the light
decreases as photons are removed from the beam. It is reasonable to assume that the more light-
absorbing entities there are in the light path and the more light quanta there are available to begin
with, the greater is the amount of light that will be absorbed. We can express this in equation form
as

Total quanta absorbed/sec (light intensity) (number of absorbing entities)

In order to evaluate this expression for the light which is absorbed from a light beam whose cross
section is 1 cm2 as it passes through a very thin layer of solution dx, as in Fig. 1, we define

Light intensity = I = quanta/cm2sec

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time: 3 ½ Hours

POTENTIOMETRY
Aim: Find out the amount of ferrous sulfate / ferrous ammonium sulfate in given flask
potentiometrically using 0.1 N Cerric Sulfate solution.
Requirements: Platinum electrode, calomel electrode, NH4NO3 salt bridge, 0.1 N Cerric
Ammonium Sulfate solution prepared in 2N H2SO4.
Procedure: Dilute the given unknown solution up to 250 ml in a SMF. Take exactly 50 ml of the
diluted solution and determine the EMF of the solution using a potentiometer. Add a small amount
of known volume of Cerric salt solution to it, stir the solution and determine the EMF of the
solution. Repeat the experiment by adding 0.1 ml of Cerric salt solution near the equivalence point.
Continue the experiment beyond the equivalence point. Determine the equivalence point from the
graph obtained using the recorded data.
Observation – table:
No. Volume of E.M.F.
Cerric Solution E ΔE ΔV ΔE / ΔV
( V ml ) Volt
1. 0.0 ml
2. 1.0 – 10.0 ml
Graph: (i) E.M.F.  Volume (ii) ΔE / ΔV  Volume
Calculation:
1) Normality of Unknown solution = NF.A.S. = NC.A.S × VC.A.S
VF.A.S
2) Amount of given unknown solution = NF.A.S. × 250 × M.W of F.A.S
1000
3) From the plot (2) note the exact volume of cerric solution (say V1 ml) required for the
complete neutralization.
4) From the plot (1) read the E.M.F of the solution at V1/2 which gives the value of E1/2.
5) EFRP = Ecell + Ecal = E1/2 + 0.2415
Result:
1) Volume of Cerric Sulfate solution used for the equivalence point = ______ ml.
2) Normality of given unknown solution = ______ N
3) Amount of Ferrous Sulfate in the given measuring flask = _______ gm / 250 ml.
4) EFRP = _______ V.

Department of Chemistry, VNSGU

 An Oxidation‐Reduction Titration: The Reaction of Fe2+ and Ce4+:
Potentiometry is the method to find the concentration of solute in a given solution by
measuring the potential between two electrodes. As name suggests, potentiometric titration
involves the measurement of the potential of indicator electrode and reference electrode. It gives
more accurate and precise results than other titrations in which different reagents are used as
indicators. The first potentiometric titration was carried out by Robert Behrend in 1893.

A titration, as you recall, is a convenient method of learning more about a solution by

reacting it with a second solution of known molar concentration. There are a number of ways to
measure the progress of a titration. The method used in this experiment is called a potentiometric
titration, in which the electric potential of a reaction is monitored. All acid‐base titrations that are
measured by a pH probe are potentiometric; thus, this method is not as unusual as it may seem.

You will conduct an oxidation‐reduction reaction in this experiment in order to determine

the amount of iron (II) ions in a solid sample of ferrous ammonium sulfate hexahydrate,
(NH4)2Fe(SO4)2•6H2O. The oxidizing agent for the sample will be ammonium cerium (IV) nitrate,
(NH4)2Ce(NO3)6. The net ionic equation for the reaction is shown below.

Ce4+ (aq) + Fe2+ (aq) → Ce3+ (aq) + Fe3+(aq)

This experiment illustrates the electrical nature of chemical reactions, and offers practice
with a process for observing and measuring an oxidation‐reduction reaction.

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time: 3 ½ Hours

pH- METRY (MONOBASIC)

Aim: Determine the dissociation constant of a given monobasic acid by pH metry.
Requirements: pH meter, 0.1 N NaOH solution, monobasic solution, glass and calomel electrodes, micro
burette and standard buffer solution.
Procedure: Calibrate pH meter with standard buffer solution. Dilute the given solution up to 250 ml with
distilled water. Take exactly 50 ml of the diluted solution in a beaker. Determine the pH by means of pH
meter. Add a known amount of 0.1 N NaOH solution from micro burette and measure pH. Continue the
experiment till neutralization is completed.
Observation – table:

No. Volume of
0.1 N NaOH Observed pH ΔpH ΔV ΔpH / ΔV
added in ml
1. 0.0 ml
2. 1.0 – 10.0 ml

Graph: (i) pH  Volume (ii) ΔpH / ΔV  Volume

Calculation:
1) From the plot pH against V note the volume of NaOH (say V1 ml) required for the first
neutralization. From the plot (1) for monobasic acid read the pH of the solution at V1/2 = V01 ,
this pKa1.
2) Ka1 = antilog of ( - pka1 )
Results:
1) pKa1 = ________
2) Ka1 = ________

Department of Chemistry, VNSGU

 Determination of Dissociation constant of a monobasic acid

When a weak acid is dissolved in water, it breaks apart or dissociates to a slight extent. A
proton from the acid is donated to a water molecule. The equations for the equilibrium and the
equilibrium constant expression are as follows:
HA + H2O ⇋ H3O+ + A-

[𝐻3 𝑂+ ][𝐴− ]
Ka =
[𝐻𝐴]

Where, A- represents the anion of the weak acid and the square brackets indicate molar
concentrations of the species. For most weak acids the percent of acid that dissociates is less than
5%. The value of the equilibrium constant, Ka, indicates to what extent the reaction occurs. The
greater the value of Ka, the stronger the acid, and the greater the amount of dissociation. Polyprotic
acids contain more than one ionizable hydrogen. The dissociation process occurs stepwise, and
there is an equilibrium constant for each of the steps. The second reaction always occurs to a much
smaller extent than the first, so Ka2 is always a smaller value than Kal.
H2A + H2O  H3O+ + HA-
HA- + H2O  H3O+ + A2-
−
[𝐻3 𝑂 + ][𝐻𝐴− ] [𝐻3 𝑂 + ][𝐴2 ]
Ka1 = Ka2 =
[𝐻2 𝑂] [𝐻𝐴− ]

This experiment is designed to determine the Ka and pKa values of a number of weak acids. Acetic
acid, HC2H3O2, will be used as an example for the experimental procedure. When acetic acid is
dissolved in water, an equilibrium exists in which a mixture of acetic acid, hydronium ions, and
acetate ions will all be present:

CH3COOH + H2O  H3O+ + CH3COO-

Acetic acid and acetate ions are conjugate acid-base pairs. A conjugate acid is a substance
that has one more proton in its structure than its corresponding conjugate base. This combination
also results from a mixture of a weak acid, acetic acid, and its salt, sodium acetate. The equilibrium
constant expression is:

[𝐻3 𝑂 + ][𝐶𝐻3 𝐶𝑂𝑂 − ]

Ka = [𝐶𝐻3 𝐶𝑂𝑂𝐻]

If a solution contains equal concentrations of CH3COOH and CH3COO- ,these

concentration terms cancel out in the above equation so that Ka = [H3O+] = 1.8 x 10-5, and pH =
pKa = 4.74. You will prepare solutions in which the concentrations of acid and its anion are equal.
The value of the pH of the solution will then equal the pKa for the acid.

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours

pH-METRY (DIBASIC)
Aim: Determine the dissociation constant of a given dibasic acid by pH metry.
Requirements: pH meter, 0.1 N NaOH solution, Dibasic solution, glass and calomel electrodes, micro
burette and standard buffer solution.
Procedure: Calibrate pH meter with standard buffer solution. Dilute the given solution up to 250 ml with
distilled water. Take exactly 50 ml of the diluted solution in a beaker. Determine the pH by means of pH
meter. Add a known amount of 0.1 N NaOH solution from micro burette and measure pH. Continue the
experiment till neutralization is completed.
Observation – table:

No. Volume of
0.1 N NaOH Observed pH ΔpH ΔV ΔpH / ΔV
added in ml
1. 0.0 ml
2. 1.0 – 10.0 ml

Graph: (i) pH  Volume (ii) ΔpH / ΔV  Volume

Calculation:
3) From the plot pH against V note the volume of NaOH (say V1 ml) required for the first
neutralization, and V2 for second neutralization. From the plot ( 1) for dibasic acid read the pH of
the solution at V1/2 = V01 , this pKa1 and for V02 = V1 + ½ ( V2 – V1 ) gives pKa2.
4) Ka1 = antilog of ( - pKa1 )
5) Ka2 = antilog of ( - pKa2 )
Results:
3) pKa1 = ________
4) Ka1 = ________
5) pKa2 = ________
6) Ka2 = ________

Department of Chemistry, VNSGU

 Determination of Dissociation constant of Dibasic acid

When a weak acid is dissolved in water, it breaks apart or dissociates to a slight extent. A
proton from the acid is donated to a water molecule. The equations for the equilibrium and the
equilibrium constant expression are as follows:

HA + H2O  H3O+ + A-
[𝐻3 𝑂+ ][𝐴− ]
Ka =
[𝐻𝐴]

Where A- represents the anion of the weak acid and the square brackets indicate molar
concentrations of the species. For most weak acids the percent of acid that dissociates is less than
5%. The value of the equilibrium constant, Ka, indicates to what extent the reaction occurs. The
greater the value of Ka, the stronger the acid, and the greater the amount of dissociation. Polyprotic
acids contain more than one ionizable hydrogen. The dissociation process occurs stepwise, and
there is an equilibrium constant for each of the steps. The second reaction always occurs to a much
smaller extent than the first, so Ka2 is always a smaller value than Kal.

H2A + H2O  H3O+ + HA-

HA- + H2O  H3O+ + A2-
−
[𝐻3 𝑂 + ][𝐻𝐴− ] [𝐻3 𝑂 + ][𝐴2 ]
Ka1 = Ka2 =
[𝐻2 𝑂] [𝐻𝐴− ]
This experiment is designed to determine the Ka and pKa values of a number of weak acids.
Some of the substances tested will be salts of diprotic acids that still contain one ionizable
hydrogen. For example, NaHSO4 ionizes in solution forming Na+ and HSO4-. The HSO4- then
reacts with water in the equilibrium:

HSO4 - + H2O  H3O+ + SO42-

−
[𝐻3 𝑂+ ][𝑆𝑂42 ]
Ka = −
[𝐻𝑆𝑂4 ]

The value of Ka that is found when equal concentrations of HSO4- and SO42- are in
solution is Ka2 for sulfuric acid.

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours

PHASE DIAGRAM
Aim : Construct phase diagram of a given three component system.
Requirements : Water, Acetic Acid, Chloroform, glass stoppered test – tubes.
Procedure : Wash and dry the test – tubes. Mix 1,2,3,4,5,6,7,8,9 ml of acetic acid and
9,8,7,6,5,4,3,2,1 ml of Chloroform in stoppered small test – tubes numbered from 1 to 9 and shake
properly. Take first test – tube and add distilled water to it drop by drop from micro – burette.
Shake the mixture well after addition of each drop and continue the addition of drop of water just
until the appearance of turbidity due to the formation of two layers. Note down the amount of
water added to the test – tube in ml. Similarly, repeat the experiment for rest of the test – tubes.
Collect densities of the components from standard text – book at appropriate temperature. Find out
weight of each component in each bottle by using formula ( density = weight / volume ).
Density : A ( water ) = 1.00 g/ml , B ( acetic acid ) = 1.05 g/ml, C ( Chloroform ) = 1.476 g/ml.

Observation – table :
Bottle Acetic Acetic CHCl3 CHCl3 Water Water
no. acid in acid In ml weight in ml weight Weight % composition
ml weight

1. 1 ml 9 ml
2. 2 ml 8 ml
3. 3 ml 7 ml
4. 4 ml 6 ml
5. 5 ml 5 ml
6. 6 ml 4 ml
7. 7 ml 3 ml
8. 8 ml 2 ml
9. 9 ml 1 ml

Calculation :
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐴𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑
1. Wt. % composition of Acetic Acid = 𝑤𝑡.𝑜𝑓 𝐴𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑+𝑊𝑡.𝑜𝑓 𝐶ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚+𝑊𝑡. x 100
𝑜𝑓 𝑊𝑎𝑡𝑒𝑟
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝐶ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚
2. Wt. % composition of Chloroform = 𝑤𝑡.𝑜𝑓 𝐴𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑+𝑊𝑡.𝑜𝑓 𝐶ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚+𝑊𝑡. x 100
𝑜𝑓 𝑊𝑎𝑡𝑒𝑟
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑊𝑎𝑡𝑒𝑟
3. Wt. % composition of Water = 𝑤𝑡.𝑜𝑓 𝐴𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑+𝑊𝑡.𝑜𝑓 𝐶ℎ𝑙𝑜𝑟𝑜𝑓𝑜𝑟𝑚+𝑊𝑡. x 100
𝑜𝑓 𝑊𝑎𝑡𝑒𝑟

Result: The information obtained from graph Water______%, Acetic acid_______% and
Chloroform_____%

Department of Chemistry, VNSGU

 What is Phase Rule ?
According to phase rule, for a system of three components four degrees of freedom ( F = 3
– 1 + 2 = 4 ) are possible, i.e., pressure, temperature and concentration of two components can be
independently varied. In order to simplify the graphical representation of the conditions of
equilibrium, two variables ( pressure and temperature ) are fixed by taking condensed systems at
constant temperature. Two concentration terms in this manner, can be represented on planar
diagrams. Triangular diagrams are most commonly used in which pure components are represented
by the corners of an equilateral triangle. Since the sum of distances from a point inside the triangle
drawn parallel to the sides is always the same, equal to the side of the triangle, the composition of
a ternary liquid system can be shown by a point within the triangle taking the side as unity ( or
100% ) and expressing the amounts of the three components as mole fractions. Any point within
the triangle represents three components, on a side two components, and on an apex, one
component.
One of the method generally used to construct the phase diagram of three component liquid
system is to prepare several mixtures of the two miscible components , and to each of the mixtures
a known amount of the third component is added until two layers are just formed. Alternatively,
known amounts of two components ( partially miscible or immiscible ) are mixed and quantities
of the third are added until the system previously consisting of two layers becomes just
homogeneous. The quantities of the three components, for which this occurs, give one point on the
binodal curve. Thus complete binodal curve can be obtained.

20% A
P 50% B
30% C

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours

CONDUCTOMETRY
Aim : Verification of Onsager’s equation and determination of equivalent conductance at
infinite dilution of strong electrolyte.
Requirements : 0.1 N KCl , 0.1 N solution of unknown univalent electrolyte, conductometer.
Procedure : Wash and dry all apparatus. Find out the cell constant by using 0.1 M KCl solution.
Prepare five different dilutions of 0.1 N KCl and 0.1 N given unknown solution. Measure the
conductance for all diluted solutions at room temperature. Calculate equivalent conductivity for
both the solutions.
Observation :
 Room Temperature = _______ °C.
 Cell constant = specific conductance of 0.1 M KCl at room temperature
Observed conductance of 0.1 M KCl
 Conductance of water at room temperature ( Λw ) = _______
 A = 0.2273
 B = 59.78
Observation – Table : For both KCl and Unknown Solution,
No. Conc. in C1/2 Observed Correct cond. = Specific Λc = 1000 × κ
mM conductance Observed cond. - Cond. ( κ ) = C
Λw correct
cond. × cell
constant

1. 0.01 – 0.05

Graph : Λc  C1/2
Result : For both KCl and Unknown Solution,
1) The equivalent conductance of a given strong electrolyte _______ at infinite dilution at
room temperature is _______.
2) The value of slope from graph = ______.
3) The value of slope calculated using Onsager’s equation ( A Λo +B ) = ______

Department of Chemistry, VNSGU

 Debye – Huckel Theory and it’s modification by Onsager
The Debye – Huckel theory was proposed by Peter Debye and Erich Huckel as a theoretical
explanation for departures from ideality in solutions of electrolytes. It was further modified by
Lars Onsager in 1927.
 The solute is completely dissociated; it is a strong electrolyte.
 Ions are spherical and are not polarized by the surrounding electric field. Solvation of ions
is ignored except in sofar as it determines the effective size of the ions.
 The solvent plays no role other than providing a medium of constant relative permittivity
(dielectric constant).
 It was assumed that the electric field causes the charge cloud to be distorted away from
spherical symmetry.
 There is no electrostriction.
 Individual ions surrounding a “central” ion can be represented by a statistically averaged
cloud of continues charge density, with a minimum distance of closest approach.
The last assumption means that each cation is surrounded by a spherically symmetric cloud of
other ions. The cloud has a net negative charge. Similarly each anion is surrounded by a cloud with
net positive charge.
After taking this into account, together with the specific requirements of moving ions,
Onsager was able to derive a theoretical expression to account for the empirical relation known as
Kohlrausch’s law, for the molar conductivity, Λm.

Debye – Huckel relationship shows the dependence of the electrical conductivity of an

electrolyte on its concentration. The equation is valid for highly dilute solutions of strong
electrolytes. In the simplest case, for a fully dissociated mono-monovalent electrolyte (such as
NaCl), the Onsager equation of electrical conductivity assumes the form
Λ = Λο – ( A + B Λο )√ c
Here Λ is the equivalent electrical conductivity, Λ0 is the equivalent electrical conductivity for
infinite dilution, c is the concentration in moles per liter, and
A = 82.4 / ( εT )1/2 η and B = 8.20 × 105 / ( εT )3/2
where ∊ is the dielectric constant, η is the viscosity in poises, and T is the absolute temperature
(°K). The Onsager equation of electrical conductivity was derived by L. Onsager.

Department of Chemistry, VNSGU

 VEER NARMAD SOUTH GUJARAT UNIVERSITY, SURAT.
M.Sc. Part - I EXAMINATION : APRIL/MAY 20 - OCT/NOV 20
PHYSICAL CHEMISTRY (Semester - I)
Time : 3 ½ Hours

CMC BY CONDUCTOMETRY
Aim: To determine the CMC of a surfactant (SDS) at room temperature by conductance method
and calculate free energy for micellization.

Requirements: Sodium sulphate or sodium dodecyl sulphate (SDS) C12 H25 SO4 Na.

Process: Wash and dry all apparatus. Find out cell constant if the conductometer. Prepare various
dilutions of SDS from 2mM to 12mM from given SDS solutions and determine its conductance at
room temperature.

Observation:
1. Room temperature = _________°C.
2. Cell constant = specific conductance of 0.1 M KCl at room temperature = _______
Observed conductance of 0.1 M KCl
3. Conductance of water at room temperature = ________

Observation - table:
Conc. In mM Observed Conductance Specific conductance= obs
conductance x cell constant
1-12mM

Calculation:
1) log CMC = ______

Graph: Concentration vs Specific conductance

Result:
1. From graph CMC of SDS is _________Mm.

Department of Chemistry, VNSGU

 What is Critical Micelle Concentration ??

Surfactants (tensides) are organic substances, which significantly decrease the surface
tension of water at relatively low concentrations and are, at least partially, water soluble. Because
surfactants are adsorbed mainly on the surface of the solution, creating a thin monolayer, they
are called surface active substances. When dissolving them, after they reach a certain value of
concentration, molecules or ions of surfactants begin to associate and to organize themselves
into more complex units, called micelles. The characteristic concentration value, where the
association process begins, is called the critical micelle concentration and it is labeled with
symbol c or abbreviation CMC.

Determination of CMC by Conductance measurement

In the case of ionic surfactants, the utilization of electrochemical measurements is much

more convenient, especially the measurements of the electrical conductivity of their solutions
with varying concentration. The conductometric method is based on the finding of a breaking
point on the curves, which describe the concentration dependence of conductivity. It is well-
known, that the conductivity of any solution is directly proportional to the concentration of its
ions. The point, where the micelle formation starts, is indicated on the concentration dependence
of specific conductivity (κ) as a breaking point. It is easy to find the breaking point, because it
marks a significant change the slope of the linear dependence:

κ =f(c)
The requested value of CMC is the intercept of two linear functions with mutually
different slopes ( in below given figures ).
The dependence of the molar conductivity (Λ) on the second root of concentration (c) can
be used for more precise determination of CMC of ionic surfactants ( second figure ). The
solution of surfactant used here is sodium dodecyl sulfate.

Department of Chemistry, VNSGU