IISER THIRUVANANTHAPURAM

School of Chemistry

Semester II Physical Chemistry Laboratory Manual

CHY 122

VASANTH-2025

Name:

Roll No:

1
 CHY 122-PHYSICAL CHEMISTRY PRACTICAL-SEMESTER 2

Experiment Page No.

1. Viscosity 4

2. Chemical Kinetics 9

3. Refractometry 14

4. Conductivity Measurements 19

5. Potentiometry 28

6. Distribution Law 35

7. Phase Diagrams 39

8. Solid Liquid Equilibrium 45

2
Guidelines:

1.Students should come to the lab in proper time with adequate preparation for the experiment.
2. Always carry lab note book, laboratory coat, lab shoes and goggles for working in lab.
3. Maintain silence in laboratory and listen to instructions carefully.
4. Instruments, chemicals, glass wares and other equipment used in laboratory should be placed
back at proper and specified places.

5. Never perform any experiment without proper supervision.

6.Eating, drinking, playing pranks and using mobile phones are strictly prohibited in science
lab.
7. Unused chemicals should never be put back in the original bottle. They must be disposed
out as per the guidelines given by the lab assistant.

8. Never sit on laboratory tables and floor.

9. Work areas should be kept clean and neat all times. Work surfaces are to be cleared at the
end of each laboratory activity.

10. Solid chemicals, metals, filter papers, broken glass, solvent waste and other materials
designated by the instructors are to be deposited in the proper waste containers and not in sink.

11. All students have to submit their results in the lab manual.

12. The fair records should be properly indexed and page numbered.

13. Students are expected to submit their completed records before entering the lab. Technical
delays if any should be communicated.

14. All accidents and dangerous occurrences must be reported immediately and staff in charge
of the laboratory must record all incidents in the accident book.

3
 1. VISCOSITY

All liquids flow under an applied force. When liquid flows through a tube, the liquid layer in
contact with the wall of the tube is stationary where as in the center has maximum velocity.
The intermediate layers have gradient of velocities. On account of relative motion, each layer
experiences a frictional force and behaves as if it is being dragged in backward direction, and
work has to be done to maintain the flow. This internal friction or resistance which resists the
relative motion of its parts is known as the viscosity. In stream lined motion the dragging force

due to internal resistance is proportional to the velocity gradient and to area of cintact, A,

between the moving layers of the liquid. The retarding force, F,

𝐹∝𝐴 = 𝜂𝐴 (1)

The proportionality constant 𝜂has characteristic value for a fluid at a specific temperature and
is known as the coefficient of viscosity. It may be defined as the force required for
maintaining a velocity difference of unity between two layers of the fluid at unit distance
apart and having a unit area of contact. Liquids having low coefficient of viscosity are said
to be mobile and those having high value of coefficient are termed viscous
In C.G.S system of units, the dimensions of 𝜂 are gcm-1s-1and is expressed in units of dynes
cm-2. The quantity 1 gcm-1s-1is called Poise. The SI unit of viscosity is Pascal Second.(Pa. s)
1Pa. s = 1kg m-1 s-1
The instruments which are used to measure viscosity by the flow through the capillary tube is
known as viscometer. The most common form is the Ostwald’s viscometer. It consists of a U
tube with two bulbs in each of the limbs. The right hand limb is essentially a pipette with two
definite marks above and below the bulb and a capillary at the bottom of the bulb. A definite
volume of liquid depending upon the capacity of the viscometer is introduced into the larger
bulb. The volume of the liquid should be so adjusted so that when it is forced to the right bulb
to the upper mark the lower meniscus of the left hand bulb stands at the bottom. On releasing
the liquid from the right hand bulb the meniscus fall from the upper mark to the lower mark
before the liquid stands at the same level in both the limbs. The time of flow of the liquid
between the marks is determined.

4
1.1. Determination of viscosities of liquids using Ostwald’s Viscometer

Aim:

To calculate the molecular viscosity and coefficient of viscosity of different liquids using
Ostwald viscometer

Theory:

Absolute viscosity ( ) may be measured by observing the rate of flow through capillary tubes,
and applying Poiseuille's law: According to The volume, V, of the liquid flowing through a
capillary tube of radius, r, length, l, in cms t seconds is given by Poiseiulle’s equation as
𝜋𝑟 𝑡
𝑉= 𝑃
8𝑙𝜂
Thus the determination of absolute viscosity of a liquid involves in accurate determination of
volume of liquid, radius and length of capillary, time of flow and pressure difference which is
difficult and laborious. But the relative viscosities can be easily determined taking water as
standard. This involves measurement of time of flow for equal volumes of liquids through the
capillary under pressure of its own weights.
If h is the mean difference of levels of liquid in the two limbs during the flow and 𝜌 is the
density of the liquid and force causing the liquid to flow down is ℎ𝜌 𝑔. the force which resist
this fow depends upon the dimensions of the capillary and viscosity of the liquid. Thus the time
of flow of the liquid between the two fixed marks for a given capillary is directly proportional
to the viscosity and inversely proportional to the driving force. That is
𝜂
𝑡 =
ℎ𝜌 𝑔
𝜂 is the coefficient of viscosity of the liquid. Let 𝑡 be the time of flow of the same volume of
another liquid of density 𝜌 then
𝜂
𝑡 =
ℎ𝜌 𝑔
Thus we have

5
 𝑡 𝜂 𝜌 𝜂 𝑡 𝜌
= 𝑜𝑟 =
𝑡 𝜂 𝜌 𝜂 𝑡 𝜌
Thus if absolute viscosity of one of the liquid is known, the viscosity of the other can be
determined.
/
Molecular viscosity = 𝜂 (5)
Where M, d and 𝜂 are molecular weight, density and coefficient of viscocity respectively.

Procedure:
Choose a correct viscometer for the liquid so that the time of flow is not less than 100sec, and
thoroughly clean it. Attach a piece of clean rubber tubing to the top of the capillary arm and
clamp it in a vertically in such a position that it can be viewed easily. Pipette 15 ml of distilled
water in the viscometer using a graduated pipette and suck up the water in the capillary arm of
the viscometer until the meniscus of water is above the mark. Allow the liquid to fall back by
releasing the pressure and start a stop watch when the meniscus passes the upper mark and stop
when it passes the lower mark. Record the time of flow of water. Repeat the experiment until
there is agreement within 0.2 to 0.3 sec. on 100 sec. Empty the viscometer, rinse it with little
acetone and then rinse with test liquid. Clamp the viscometer and fill the viscometer with equal
volume of the experimental liquid and determine the time of flow as before. Determine the
densities of water and the experimental liquids at the temperature of the experiment using
specific gravity bottle. Also note down the temperature at which the experiment was performed.
Calculate the viscosity of the liquid using equation.

Observation and calculation

Lab temperature = ………°c
Density of water = ………. g/cm3
Viscosity of water = ……………g/cms
Weight of empty specific gravity bottle, w1 g = ………. g

𝐖𝟑 𝐖𝟏
Density of liquid = 𝐖𝟐 𝐖𝟏
.𝝆
W1 – Weight of empty specific gravity bottle
W2 – Weight of specific gravity bottle + water
W3 - Weight of specific gravity bottle + liquid
ρ - Density of water at -----°C

6
Table 1. Density Calculation of liquids
Liquids w2 w3 w3-w1 Density, ( 𝜌1
)

Water

Nitrobenzene

Toluene

Table 2. To calculate the molecular viscosity of liquids.

Molecular
viscosity
Liquids Time of flow(s) Mean Coefficient of
viscosity 𝑴 𝟐/𝟑
s 𝜼
𝜼𝟏 𝒕𝟏 𝝆𝟏 𝒅
=
𝜼𝟐 𝒕𝟐 𝝆𝟐 gcmsmol-2/3

1 2 3 g/cms

Water

Nitrobemzene

Toluene

1.2. Determination of the composition of the given mixture of nitrobenzene and toluene
Aim:

To find the coefficient of viscosity of unknown composition using Ostwald viscometer

Theory:

When two different liquids are mixed the change in viscosity depends upon composition of the
mixture. The different mixtures required different time to flow through fixed distance of a
capillary. A graph is plotted with time of flow along Y – axis and composition along x- axis.
A curve is obtained. From the curve the composition of the given solution is obtained by
locating and marking the point on the curve, corresponding to its measured time of flow.

Procedure:
Solutions of different composition are prepared by mixing nitrobenzene and toluene in different
compositions. The time of flow of each solution is noted by means of Ostwald’s viscometer.
Then time of flow of the given mixture is also determined. A graph is plotted with time of flow

7
along Y – axis and composition along x- axis. A curve is obtained. From the curve the
composition of the given solution is obtained by locating and marking the point on the curve,
corresponding to its measured time of flow.

Table 3. To calculate the coefficient viscosity of different composition

Time of flow(s) Mean of time
Sl. Vol. of Vol. of of flow
Composition
No. nitrobenzene toluene
1 2
1 10
2 20
3 30
4 40
5 50
6 60
7 70
8 80
9 90
10 unknown

Report :

i. Molecular Viscosity of

1. Nitrobenzene = ………………….. gcmsmol-2/3

2. Toluene = ………………….. gcmsmol-2/3

ii. Composition of the unknown mixture =

8
 2. CHEMICAL KINETICS

The rate of chemical reaction depends upon various experimental conditions such as the
concentration of the reactants, temperature, presence of the catalyst, etc. it is the study of the
rates of chemical reaction and the influence of various conditions that forms the subject matter
of chemical kinetics. By rate of reaction we mean the change in concentration of a reactant (or
a product) in a given period of time. This might, for example, be over a short period of time
anywhere during the reaction, or it might be at an instant of time (or corresponding
concentration of a reactant).

𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛
𝑟𝑎𝑡𝑒 𝑜𝑓𝑎 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 =
𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑡𝑖𝑚𝑒

Chemists need to understand chemical kinetics so that industrial reactions can be controlled
and their mechanisms understood. It also helps them to make predictions about important
reactions such as those that occur between gases in the atmosphere. During the reaction, the
rate at any instant of time can be determined by measuring the gradient of the tangent to the
curve at that time. This also corresponds to the rate at an instant of concentration. If the rate is
measured at a range of instants of concentration during the experiment, rate against
Concentration graph can be plotted.

According to law of mass action rate is directly proportional to the active mass of the reactants.
In dilute solutions the active mass can be equal to concentration. Thus
𝑟𝑎𝑡𝑒 ∝ 𝑎𝑐𝑡𝑖𝑣𝑒 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 𝑜𝑟

𝑟𝑎𝑡𝑒 ∝ 𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛

𝑟𝑎𝑡𝑒 = 𝑘[𝑐𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛]

This expression is called a rate equation, where k is called the rate constant. n can be any real
number. If n=1, is called a first order reaction. n=2, or n=3 are called second order and third
order reaction respectively.

Determination of Rate Constant and Activation Energy

Aim:
i. To determine the rate constant of the hydrolysis of ester by sodium hydroxide at
different temperature
ii. To determine the activation energy

9
2.1 The rate constant of hydrolysis of methyl acetate catalyzed 0.5M hydrochloric acid.

Theory:
Methyl acetate is hydrolyzed to give methyl alcohol and acetic acid
[ ]
𝐶𝐻 𝐶𝑂𝑂𝐶𝐻3 + 𝐻 𝑂 ⎯ 𝐶𝐻 𝐶𝑂𝑂𝐻 + 𝐶𝐻 𝑂𝐻

The reaction is catalyzed by hydrogen ions. In dilute aqueous solution of the ester,
concentration of water being large excess; practically it remains constant during the reaction.
The concentration of hydrogen ion which catalyzes remains constant. Thus the rate of the
reaction is dependent only on the concentration of ester, ie.
𝜕[𝐶𝐻 𝐶𝑂𝑂𝐶𝐻 ]
𝑟= − = 𝑘[𝐶𝐻 𝐶𝑂𝑂𝐶𝐻 ]
𝜕𝑡

Rate constant k is calculated using equation (8)

.
𝑘= 𝑙𝑛 = 𝑙𝑜𝑔 (8)
where ‘a’ is the initial concentration of the ester, (𝑎 − 𝑥) is the concentration of the ester after
the time interval 𝑡 𝑠𝑒𝑐. Since acetic acid is produced as a result of hydrolysis, the kinetics of
reaction can be followed by withdrawing a fixed volume of the reaction mixture from time to
time and titrating with standard alkali. The titer value is equivalent to the sum of the acid used
as the catalyst and the acetic acid formed during the reaction. The difference of titer values at
any time after the commencement of the reaction and that of the at the commencement of the
reaction gives the acetic acid formed and hence the amount of methyl acetate hydrolyzed at
that instant. Let 𝑣 , 𝑣 𝑎𝑛𝑑 𝑣 are the titer values at infinite time, at time t and at the
commencement of the experiment then
𝑣 − 𝑣 is proportional to initial concentration ‘a’ of ester
𝑣 − 𝑣 is proportional to concentration(𝑎 − 𝑥) of ester

. ( )
therefore rate constant 𝑘= 𝑙𝑜𝑔 ( )

( )
A graph is plotted t (abscissa) versus 𝑙𝑜𝑔 ( )
and obtain the value of 𝑘 from the slope,
𝑘/2.303

10
Procedure:

Take 100 mL of 0.5 M hydrochloric acid in 250 mL stoppered regent bottle and keep in water
bath of required temperature. Fill the burette with 0.1M NaOH previously rinsing it with the
solution. Take 3-4 250 mL conical flask containing 25ml water and few ice cubes. Pipette out
5 mL of methyl acetate into the bottle after temperature equilibrium is attained. Start a stop
watch when the pipette is half drained. Stir the solution very well and immediately pipette out
5 mL of the mixture into one of the conical flasks. Add 2 drops of phenolphthalein indicator
solution and titrate it against NaOH taken in the burette. Note the titer value which corresponds
to 𝑉 . Pipette out 5 mL of the acid-ester mixture into the conical flask containing ice at time
intervals 5,10,20, 30,40,50 and 60 minute time interval and titrate against the standard alkali.
The titer values correspond to𝑉 . Allow the remaining mixture to remain for 48 hours or heat
the solution for 2 hours over a boiling water bath. Titrate 5 mL of the solution against the
standard alkali as before. (Ice need not be added). The titer value corresponds to 𝑉 . Much time
can be saved if 25 mL of the mixture is placed in well stoppered small flask at about 800C after
taking the first or second reading in a water bath for one hour. Repeat the experiment at
different temperature at 400C to calculate the energy of activation of the reaction.

( )
Plot t (abscissa) versus 𝑙𝑜𝑔 ( )
and obtain the value of 𝑘 from the slope, 𝑘/2.303
Temperature of the reaction mixture = 300C

Time Titer (𝑉 − 𝑉 ) 2.303 (𝑉 − 𝑉 )

(𝑉 − 𝑉 ) (𝑉 − 𝑉 ) 𝑙𝑜𝑔 𝑘= 𝑙𝑜𝑔
(min) value (𝑉 − 𝑉 ) 𝑡 (𝑉 − 𝑉 )

10

20

30

40

50

60

Average 𝑘

11
Temperature of the reaction mixture = 400C
Time Titer (𝑉 − 𝑉 ) 2.303 (𝑉 − 𝑉 )
(𝑉 − 𝑉 ) (𝑉 − 𝑉 ) 𝑙𝑜𝑔 𝑘= 𝑙𝑜𝑔
(min) value (𝑉 − 𝑉 ) 𝑡 (𝑉 − 𝑉 )

10

20

30

40

50

60

Average 𝑘

2.2. Calculation of the energy of activation(𝑬𝒂 ) of the reaction

𝑘 𝐸 1 1
𝑙𝑜𝑔 =− −
𝑘 2.303 𝑅 𝑇 𝑇

𝐸 𝑇 −𝑇
=
19.147 𝑇 𝑇

(T1 and T2 are the temperature in Kelvin)

12
Report:

i. Rate constant at 300C

(a) From calculation =
(b) From graph =

ii. Rate constant at 400C

(a) From calculation =
(b) From graph =

iii. Energy of activation of the reaction =

13
 3. REFRACTOMETRY

The measurement of refractive index and optical activity of compounds, liquids and
solution of solids is of great importance as these provides valuable information regarding the
molecular structure, purity and composition of binary mixtures. Refractometry is the method
of measuring substances' refractive index. A refractometer is the instrument used to measure
refractive index (n). Although refractometers are best known for measuring liquids, they are
also used to measure gases and solids; such as glass and gemstones.
The speed of light in a vacuum is always the same, but when light moves through any
other medium it travels more slowly since it is constantly being absorbed and reemitted by the
atoms in the material. The ratio of the speed of light in a vacuum to the speed of light in another
substance is defined as the index of refraction (n) of the substance.
𝑟𝑒𝑓𝑟𝑎𝑐𝑡𝑖𝑣𝑒 𝑖𝑛𝑑𝑒𝑥 (𝑛)𝑜𝑓𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 = (1)
Whenever light changes speed as it crosses a boundary from one medium into another
its direction of travel also changes, i.e., it is refracted (Figure 1). (In the special case of the light
traveling perpendicular to the boundary there is no change in direction upon entering the new
medium.) The relationship between light's speed in the two mediums (vA and vB), the angles of
incidence (qA) and refraction (qB) and the refractive indexes of the two mediums (nA and nB) is
shown below:
= = (2)

3.1. Calculation of molar refraction of water, acetone, aniline, nitrobenzene and toluene

Aim:
i.To determine the molar refraction of pure liquids

Theory:
By measuring the angle of refraction, and knowing the index of refraction of the layer that is
in contact with the sample, it is possible to determine the refractive index of the sample quite
accurately.

𝑟= . ( 3)
Where n is the refractive index, ρ is the density and r is the specific refractivity or specific
refraction. Molar refractivity or molar refraction [R] is the product of specific refractivity and
molecular weight. Thus
[R] = ( )
.( ) (4)
where M is the molecular weight of the substance. Molar refraction of a compound, which
depends only on the wavelength, is additive and constitutive property. It is thus possible to
work out the refraction equivalent of atoms, groups and radicals and bonds by determining the

14
molar refraction of large number of compounds. The experimental determination of molar
refraction is of utmost importance in elucidating the molecular structure.

Procedure:
Measure the refractive index of given liquids using Abbe refractometer and tabulate the result
in the following table

0
Temperature of the experiment = C
Refractive index of water at this temperature = (from literature)

Liquid Refractive Mean* Density Molecular n2(square of Molar

index n [ρ] mass refractive refractivity [R]
index)
𝑛 −1 𝑀
[R = .( )
(𝑛 + 2) 𝜌

Water

Acetone

Aniline

Nitro
benzene

Toluene

𝐖𝟑 𝐖𝟏
Density of liquid = 𝐖𝟐 𝐖𝟏
.𝝆

W1 – Weight of empty specific gravity bottle

W2 – Weight of specific gravity bottle + water
W3 - Weight of specific gravity bottle + liquid

Density Calculation of liquids

Weight of empty specific gravity bottle =
ρ - Density of water at ……….°C =

15
 Density=
Liquids w2 w3 w3-w1 w2-w1
( )
𝜌

Water - -

Acetone -

Aniline -

Nitro -
benzene
Toluene -

3.2. Determination of refractive index of KCl solutions of different concentration and

unknown composition

Aim:

To determine the unknown concentration of given KCl

Theory:
Composition of a solution of a solid substance in a liquid may be determined from the
refractometric measurements. In this method refractive indices of a series of solutions of known
compositions, determined experimentally, are plotted against composition and a calibration
curve is drawn. The composition of an unknown solution is then read from the graph measuring
the refractive index.

composition

16
Procedure:
Prepare different solutions containing 0.5,1, 2, 3, 4,5 and 6 g of KCl in 50 ml standard flask.
Measure the refractive index of the solutions. Also determine the refractive index of unknown
composition. Plot a graph between refractive index and composition of the solution. From the
calibration curve, the composition of unknown solution can also determine using its refractive
index.

Weight of KCl Composition of the

Refractive Index Mean (n)
(g) solution

0.5

1.5

2.5

3.5

unknown

17
Report

i. Molar refraction of
1. Acetone =
2. Aniline =
3. Nitro benzene =
4. Toluene =

ii. Composition of the unknown solution: =

18
 4. CONDUCTIVITY MEASUREMENTS
The ease of flow of electric current through a body is called its conductance. In metallic
conductors it is caused by the movement of electrons, while in electrolytic solutions it is caused
by applied electrical field. Conductometry measures electrolytic conductivity or resistance of
the solution located between two electrodes. This property of the solutes is the result of the ion
movement under the influence of the electric field applied. Only ionizable molecules
(electrolytes) conduct electric current. The magnitude of the conductivity depends on the
amount of ions presented in the solution. The electrolyte kind, its concentration and
temperature affects both conductivity and specific conductance.

The electrolytic conductance C of a medium is equal to the reciprocal of its electrical resistance
R in ohms:

𝟏
𝐂=
𝐑
Ohm’s Law states that the current I (amperes) flowing in a conductor is directly proportional
to the applied electromotive force E (volts) and inversely proportional to the resistance, R
(ohms) of the conductor:

𝐄
𝐈= or 𝐈 = 𝐄𝐂
𝐑

Conductance

The movement of ions through its solution to electrodes is known as conductance. When
electrodes are placed in a solution, the cations are attracted to the negatively-charged cathode
while the anions move towards the positively-charged anode. This conductance may be
affected by changes in ionic concentration and differs between compounds.

For a strong electrolyte, there is complete dissociation into mobile ions. At infinite dilution,
the distance between neighboring ions is significant; therefore, only the effect of the applied
electric field is experienced by individual ions. However, in a concentrated solution, each ion
is surrounded by other ions. The ions are close enough to be influenced by both the electric
field applied by the electrodes as well as that by their surrounding ions.

19
In this experiment, the conductance of NaCl and CH3COOH is measured. NaCl, being an ionic
salt, dissociates completely in water to produce Na+ and Cl- ions. Due to a high concentration
of mobile ions, it has significant conductance. On the other hand, CH3COOH is a weak acid
which only partially ionises in water; hence, its conductance is weaker than that of NaCl.

4.1 Determination of Degree of Ionization of Weak Electrolytes

Aim:

To determine the degree of ionization and dissociation constant of weak electrolyte

Theory:

For dilute solutions of strong electrolytes, the equivalent conductance is a linear function of
the square root of the concentration. This is in accordance to Kohlrausch’s Law,
Ʌ=Ʌ0 - b√C
where Ʌ is the conductance of the salt, Ʌ0 is the molar conductivity of salt C, its concentration
and b is the coefficient related to stoichiometry of the electrolyte.

At infinite dilution, the equivalent conductance of strong electrolyte, NaCl approaches a

definite value. The extrapolation of graph allows the conductance at infinite dilution, Ʌ0, to be
calculated.

However, this may not be done for a weak electrolyte. In the case of CH3COOH, the equivalent
conductance at infinite dilution cannot be extrapolated to a definite value. Thus, for the weak
CH3COOH acid, the value of Ʌ may be obtained from a knowledge of the values for Ʌ0 for
HCl, NaCl and Na+CH3COO-, according to the equation,
Λo CH3COOH = Λo HCl + Λo CH3COO-Na+ - Λo NaCl.

20
After calculating the conductance of the acid, its dissociation constant may be determined.
Weak electrolytes such as acetic acid, do not dissociate completely in solution. Instead, there
is an equilibrium between ions and associated electrolyte

CH3COOH + H2O ↔ CH3COO- + H3O+

Equilibrium concentration c(1-) c c

𝐂𝛂2
𝐊𝐚 =
𝟏−𝛂
Hence, according to the above equation, the acid dissociation constant may be determined.

Procedure:

Measurement of conductance of CH3COOH and NaCl

Rinse the cell several times with conductivity water and measure the conductance (< 2 μS). A
series of solutions of acetic acid and sodium chloride are prepared at different concentrations
from the given stock solution. The conductance of each solution is measured using
conductometer.
Table1:Calculation of equivalent conductance of acetic acid

[CH3COOH] √[CH3COOH] Recorded Specific Equivalent Conductance,

Conductivity, Conductance,
(Equiv) (equiv½) G (µS)
𝛋∗𝟏𝟎𝟎𝟎
Ʌ=
κ = G*cell constant [𝐂𝐇𝟑𝐂𝐎𝐎𝐇]

(µS cm-1) mS cm2equiv-1

0.0005

0.001

0.005

0.01

0.05

21
Table2:Calculation of equivalent conductance of Sodium chloride

[NaCl] √[NaCl] Recorded Specific Equivalent

(Equiv) (equiv½) Conductivity, G Conductance, Conductance,
(µS)
κ = G*cell Ʌ=
𝛋∗𝟏𝟎𝟎𝟎
[𝑵𝒂𝑪𝒍]
constant

(µS cm-1) mS cm2equiv-1

0.0005

0.001

0.005

0.01

0.05

By plotting Λ against square root of concentration, the equivalent conductance at infinite

dilution Λo for strong electrolyte NaCl can be obtained from the graph.

From the graph, since the y-intercept = ……….

Λo NaCl =………... mScm2equiv-1

= …………. Scm2equiv-1

Λ0HR = Λ0HCl +Λ0NaR -Λ0NaCl

In this experiment, the value of equivalent conductance at infinite dilution, Λo of HCl and
Na(CH3COO) are not determined. Hence, the literature values at 250C will be used.

CH3COONa = 91.00 S cm2 equiv-1

HCl = 426.16 S cm2 equiv-1
Using the equation, Λo CH3COOH = Λo HCl + Λo CH3COO-Na+ - Λo NaCl

= ………………… S cm2 equiv-1

22
Table 3: Calculate degree of dissociation and dissociation constant for all concentrations

[CH3COOH] Equivalent Degree of Apparent

Conductance, Λ dissociation, dissociation
M (mS cm2equiv-1) constant, K=
α = Λ /Λo –

0.0005

0.001

0.005

0.01

0.05

4.2 Titration Strong acid and weak acid against a strong base

Aim:

To determine the strength of strong and weak acids using conductometric titrations

Theory:

The principle of conductometric titration is based on the fact that during the titration,one of the
ions is replaced by the other and invariably these two ions differ in the ionic conductivity with
the result that conductivity of the solution varies during the course of titration.
The equivalence point can be located graphically by plotting the changes of conductance as a
function of the volume of the added titrant.

The most important advantages of this method are that it can be used for determination of:
– turbid and highly coloured solutions,
– very dilute solutions,
– reaction which is not complete and where there is no suitable indicator, e.g. reaction between
weak acid and weak base.

23
Precaution to be considered in conductometric titrations:
1. Upon carrying on titration the titrant used should be at least 10 times concentrated as the
solution to be determined, e.g. on determination of 0.01 M hydrochloric acid the titrant sodium
hydroxide should be at least 0.1 M. By this way dilution that takes place during titration is
minimum and this is necessary because conductivity decreases with dilution.
2. Avoid the presence of ions which will not take part in the reaction, such as the presence of
buffer or concentrated acids. These ions will increase the initial conductivity and its change
during the titration will be comparatively small and can not be accurately observed.
3. The method is suitable for detection of end point in neutralization, complexation and
precipitation reactions but not redox reaction, as there is no electron transfer at the electrode
surface.

i. Strong Acid with a Strong Base: (HCl with NaOH)

Before NaOH is added, the conductance is high due to the presence of highly mobile
hydrogen ions. When the base is added, the conductance decreases due to the replacement of
hydrogen ions by the added cation as H+ ions react with OH- ions to form undissociated water.
This decrease in the conductance continues till the equivalence point. At the equivalence
point, the solution contains only NaCl. After the equivalence point, the conductance increases
due to the high conductivity of electrolytes (Fig. 1).

Fig. 1. Conductometric titration of strong acid (HCl) vs. strong base (NaOH)

24
ii. Weak Acid with a Strong Base: (CH3COOH with NaOH)

Initially a slight decrease in the conductance is caused by binding a small amount of

hydrogen ions, originating from dissociation of acetic acid, into water molecules. Next, the
gradual conductance increase is connected with the substitution of the weakly dissociated
acetic acid by the well dissociated sodium acetate. After the equivalence point has been
reached, the conductance increases significantly due to the increasing concentration of
electrolytes (Fig. 2).

Fig. 2. Conductometric titration of weak acid (CH3COOH) vs. strong base (NaOH)

Procedure:

Perform the conductometric titration of the following systems:

– titration of HCl vs. NaOH,
– titration of CH3COOH vs. NaOH,

Place a known volume (20 mL) of the solution be titrated in a 100 mL beaker. Add 20 mL
distilled water. Immerse the conductivity cell in the solution and measure the conductance of
the solution. Add 1 mL each of the titrant from a burette. Stir the solution very well and measure
the conductance of the solution. Continue the titration and measuring the conductance at least
five additions after the end point (minimum value). Plot a graph between volume of the titrating
solution and the conductance as the ordinate. Extrapolate the straight line portions of the
titration curve to meet and drop a perpendicular to the ordinate to get the volume of the titrant.

25
 NaOH X HCl CH3COOH X HCl

Volume(mL) Conductivity Volume(mL) Conductivity

26
Report

1. Dissociation constant of Acetic acid, Experiment =

2.Concentration of HCl =

3.Concentration of Acetic acid =

27
 5. POTENTIOMETRY
When the pair of electrodes are placed in the sample solution or analyte, it shows the potential
difference between two electrodes by the addition of the titrant or by the change in the
concentration of ions.

The two electrodes are named reference electrodes and indicator electrodes. The reference
electrode is the electrode that maintains its potential and remains stable when dipped into a
sample solution. An indicator electrode is an electrode that responds to variation in the potential
of analyte solution. A salt bridge is used to prevent interference of the analyte with the reference
electrode.

Charge can flow in a material under the influence of an external electric field. Eventually, the
internal field due to the repositioned charge cancels the external electric field resulting in zero
current flow. To maintain a potential drop (and flow of charge) requires an external energy
source, ie. emf (electro motive force) The emf has three components: the electrode potentials
of the two electrodes (E1 and E2) and the diffusion potential (Ed). Diffusion potential is a
potential arising from different rates of diffusion of ions at the interface of two dissimilar fluids,
a junction potential. It is also known as liquid junction potential (EL).
E cell = E1 + E2 + EL (1)
For electrochemical measurements galvanic cells consisting of reversible electrodes should be
used. For these systems, the electrode potentials can be given by the Nernst-Peters equation.
𝐸 = 𝐸∘ − 𝑙𝑛 (2)
where R is the general gas constant (8.314 J.mol-1K-1), T is the temperature in Kelvin, F is
known as Faraday’s constant (9.65×104 C/mol), aox. and ared. are the activities of the oxidized
and reduced forms, n is the number of electrons in the half cell reaction, Eo is the standard
electrode potential. At 298K substituting values for R and F we have
.
𝐸= 𝐸 − 𝑙𝑜𝑔 (3)
Consider the electrode reaction 𝑀( ) + 𝑛𝑒 → 𝑀( ) then electrode potential is given by
. [ ]
𝐸= 𝐸 − 𝑙𝑜𝑔 [ (4)
( )]

For pure solid [M(s)] = 1 therefore

.
𝐸= 𝐸 − 𝑙𝑜𝑔 [ (5)
( )]

From the above equation, it is concluded that

(i) E increases as [𝑀( ) ] is increased
(ii) The electrode potential (E) decreases as temperature is increased.

Advantages:
(a) Potentiometric titrations are applicable to wide range of reactions, provided an appropriate
indicator electrode is available. The method is of particular use in titration of highly coloured
solutions where indicator cannot be used.

28
(b) The determination of the equivalence point by this method depends on a series of
independent observations rather than one judgment. Thus the method gives very reliable
results.
(c) Extremely dilute solutions may also be used for the titrations.
(d) It is possible to carry out a stepwise titration of polybasic acids and mixture of acids.

5.1. Determination of single electrode potential

Aim:
To determine the single electrode potential of copper and zinc

Theory:
It is impossible to measure absolute value of single electrode potential because neither
oxidation nor reduction takes place independently. It is possible to measure the potential
difference between two electrodes with help of a potentiometer. In other words, we can
measure electrode potential with reference to reference electrode. For this purpose calomel
electrorde is considered.
Calomel electrode is used as a secondary reference electrode. Calomel electrode consists of a
tube at the bottom of which a small amount of mercury is placed. It is covered with a paste of
mercurous chloride (Hg2Cl2). A solution of potassium chloride is then placed over the paste. A
platinum wire dipping into the mercury layer is used for making electrical contact. The
electrode reaction when the electrode acts as cathode is
1
𝐻𝑔 𝐶𝑙 ( ) + 𝑒 ⇌ 𝐻𝑔 + 𝐶𝑙
2
And its potential is given by
𝐸 = 𝐸 − 𝑙𝑛𝑎 (6)
Thus the potential of the calomel electrode depends on the activity of the chloride ions (𝑎 ). It
has been found that the potential of calomel electrode varies with concentration of the
potassium chloride solution used. The reduction potential of calomel electrode at 298K for
various concentrations of KCl are given below.
[KCl] Saturated 1.0 N 0.1 N

Electrode potential in volt 0.242 0.281 0.334

To obtain the potential of any other electrode it is combined with the calomel electrode and the
emf of the resulting cell is measured. Knowing the cell emf and electrode potential of the
calomel electrode the potential of the other electrode can be calculated.

Procedure:
Prepare 0.1N, 0.01N and 0.001N of zinc sulphate and copper sulphate solutions.
Dip the copper electrode and calomel electrode in copper sulphate solution and measure the
emf. After the measurement, clean the electrodes with water and measure the emf of zinc
electrode by dipping in the zinc sulphate solution.

29
Table 1: Electrode potential of copper and zinc electrode

Electrode potential 0.1N 0.01N 0.001N

Measured
Copper
Calculated

Measured
Zinc
Calculated

Report:

Electrode potential of copper electrode at 0.1N =

at 0.01N =
at 0.001N =

Electrode potential of zinc electrode at 0.1N =

at 0.01N =
at 0.001N =

5.2. Verification of Nernst Equation and Oxidation- Reduction Titration

Aim:
To verify the Nernst equation

Theory:
The variation of potential of an electrode with the concentration of ions with which it is in
equilibrium may be used as an indicator in volumetric analysis. The method is applicable to
wide range of titrations, provided an appropriate electrode is available. An indicator electrode
(Pt electrode) indicates the electrode potential with the change in concentration of ions to be
titrated. Single electrode potential cannot be measured. Hence the indicator electrode is coupled
with a reference electrode, the potential of which remains constant during the course of the
titration, to form an electrochemical cell, and the variation of the cell potential measured with
the addition of the titrant. The e.m.f. of the cell plotted against the volume of the titrant to
obtain a curve. The point of inflection in the curve gives the equivalence point. It may be noted
that the change in e.m.f. is very much rapid near the equivalence point. The general form of
titration curves is the same for all potentiometric titrations. However, the sharpness of the
inflection point and the symmetry of the curve on its sides depend on the nature of the titrant.
When the titration curve does not show a sharp inflection point, the exact location of the point

30
of inflection is difficult. The precise end point may be obtained by differential method where
∆
∆
values i.e. change in e.m.f. resulting from the successive addition of the titrant is plotted
against the volume of the reagent added. The maximum of the differential curve thus obtained
corresponds to the equivalence point of the titration.
In carrying out the titrations, the reagent is added in small amounts and the mixture is
stirred thoroughly. In order to obtain the graph in the neighbourhood of the equivalence point
with greater precision, the titrant must be added in smaller and smaller amounts as equivalence
point approaches.

`Plot a graph between the e.m.f. of the cell and the volume (abscissa) of the alkali added. The
∆
point of the inflection in the curve gives the end point. Also plot ∆ against V (abscissa): the
maximum of the gives the equivalence point.

A redox electrode consists of an inert electrode e.g. Pt or Au immersed in mixed solution

containing both oxidized and reduced form of a molecule or ions. The inert metal acts as an
electron reservoir. The electrons in the reservoir are used up if some of the oxidized form
changes to reduced form or flow into the reservoir if reverse happen. A simple example of this
type of redox system is
Fe3+ + e- Fe2+
The electrode potential is given by
2.3031𝑅𝑇 𝑎
𝐸= 𝐸 − 𝑙𝑜𝑔
𝑛𝐹 𝑎
The potential of the electrode depends on 𝑙𝑜𝑔
Initially Fe3+ is present in infinitesimal amount, which increases when solution is titrated
against oxidizing agent. This results in a rapid change in e.m.f. at equivalent point. After the
end point the e.m.f. of the cell depends on the oxidizing agent.

31
Procedure:
Pipette out 20ml of the ferrous ammonium sulphate solution in 100ml beaker. Add 20 ml of
6N sulphuric acid. Introduce a calomel electrode and a platinum electrode into the solution and
measure the e.m.f. of the cell. . The cell is represented as,

Hg Hg2Cl2 Fe3+,Fe2+ Pt

Add 1ml of the oxidizing agent to the cell and stir the mixture very well and measure the e.m.f.
of the cell. Continue the titration to get the approximate end point. Let it be V1 ml of the
solution. Pipette out 20ml of the ferrous sulphate solution and add 20ml 6N sulphuric acid and
introduce the calomel electrode and pt electrode and measure the e.m.f. of the cell. With
continuous stirring add (V1 – 1) ml of the oxidizing agent. Measure the e.m.f. of cell. Now add
0.1ml of the oxidizing agent mix well and record the e.m.f. continue the titration till the volume
∆
of the oxidizing agent added is (V1 + 1) ml. Plot e.m.f. E and ∆ against the volume of the titrant
and determine the equivalence point V0 from the curves. The e.m.f. of the cell at where
(𝐶 𝐶 ) will be 𝐸 − 𝐸 . Hence standard reduction potential of ferric- ferrous system
is calculated.
From the experimental results determine and plot 𝑙𝑜𝑔 (abscissa) against E. The
intercept of the linear graph on the ordinate gives 𝐸 − 𝐸 (𝐸 = 0.334𝑉). Hence calculate
. .
E0. The slope of the straight line is = ; hence calculate the value of n.

Volume of Volume of
EMF EMF
titrant added titrant added

32
Volume of titrant ΔE
EMF ΔE ΔV
added ΔV

33
 Volume of Weight of Fe2+ Weight of Fe3+ Fe3+/Fe2+ Log E Fe3+/Fe2+
K2Cr2O7 corresponding corresponding to (Fe3+/Fe2+)
to Vol. of Vol. of
K2Cr2O7 K2Cr2O7 (based
(based on on equivalent)
equivalent)

Report:

Standard reduction potential of ferric-ferrous system =

The value of n in the cell =

Concentration of Mohrs salt =

34
 6. DISTRIBUTION LAW

If a system made up of two immiscible liquids and a third substance added to the system such
that the third substance is soluble in both the solvents, then added substance will distribute
itself between the two liquids in a definite manner depending upon its solubility. At
equilibrium the ratio of concentrations (activities) of the solute in the same molecular state
in the two liquids is constant at a given temperature. This fact is known as distribution or
partition law, and is independent of the total amount of the solute dissolved and any other
molecular species.

If C1 (a1) and C2 (a2) are the concentrations (activities) of the solute in two solvents when
equilibrium is reached, then at constant temperature
= = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (𝐾) (1)
The constant K is called Partition coefficient or distribution constant.

Determination of Partition Coefficient and Equilibrium Constant

Aim:
i. To determine the partition/distribution coefficient of iodine between an
organic solvent and water
ii. To determine the equilibrium constant of the reaction KI + I2⇌ KI3

6.1 Partition coefficient of iodine between water and cyclohexane

Theory:

If a solute is shaken up with two immiscible solvents, it will distribute itself between two
solvents in such a way that the ratio of the concentration of the solute in the two solvents is a
constant, provided the solute exists in the same molecular state in both solvents.

Here the molecular state of iodine as I2 in both the solvents (organic liquid and water) is the
same and the partition coefficient is practically independent of concentration in dilute solutions.
The distribution law in the simplest form is applied. Thus, if Corg and Caq are the concentrations
of iodine in organic liquid and aqueous layers, then we have
= 𝐾 (𝑝𝑎𝑟𝑡𝑖𝑡𝑖𝑜𝑛 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡) (2)

Procedure:
(1) Take three 250mL clean bottles and number them1-3.
(2) Pipette out 25, 20and 15mL of the given saturated solution of iodine in cyclohexane solution
into a clean and properly labelled 250mL glass stoppered reagent bottles. Also pipette out 0, 5
and 10mL of cyclohexane into the bottles and 100 mL of water to each of the bottles and stopper
them tightly.

35
(3) Shake the bottles for 20 minutes to attain equilibrium. Keep these bottles in a water bath
for 10 minutes to attain the room temperature. On standing, the contents of each bottle separate
into two layers, the lower is water layer and the upper one cyclohexane.
(4) Prepare 250 mL of 0.05M sodium thiosulphate solution and a dilute a portion in a
volumetric flask as to get 250 mL 0.01M sodium thiosulphate
(5) Carefully pipette out 5 mL of the organic layer into an iodine flask, add 10 mL 10% KI and
titrate it with 0.05M Na2S2O3 using starch as the indicator. Similarly titrate 10 mL of the
aqueous solution against 0.01M using starch as the indicator.
(6) Similarly analyze the organic layer and the aqueous layers for other bottles.
(7) Calculate the concentration of iodine in carbon tetrachloride and aqueous layer. Then
calculate the ratio Corg/Caq for each bottle and take the average. This gives the distribution
coefficient of I2 between cyclohexane and water.

Vol. of 0.05M Vol. of 0.01M Con. of I2 in Con. of I2 in Partition

thio for 5mL thio for 10mL the aqueous the coefficient
Bottle
cyclohexane aqueous layer layer cyclohexane
No.
layer moles/liter layer
moles/liter

Mean

6.2 Determination the equilibrium constant of the reaction KI + I2⇌ KI3 by distribution
method

Theory:
Distribution law holds good to molecular species common to both the phases. To a moderately
concentrated iodide solution KI is added, it combines with iodide ion to form tri-iodide ion.
Thus in aqueous KI solution containing iodine, we the chemical equilibrium
𝐾𝐼 + 𝐼 ⇌ 𝐾𝐼
In dilute solution the equilibrium constant of the reaction is
⌊ ⌋ [ ]
𝐾= ⌊ ⌋⌊ ⌋
or 𝐾 = [ ][ ]
(3)
Since molecular iodine is soluble in both the aqueous and organic phases, it obeys the
distribution law. KI and KI3 are insoluble in organic phase as they are electrolytes. The
knowledge of partition coefficient of iodine between cyclohexane and water will enables us to
determine the equilibrium concentration of free iodine in aqueous KI solution in equilibrium

36
 with cyclohexane, provided the concentration of iodine in cyclohexane is determined. If this is
subtracted from the total concentration of I2 in aqueous KI layer, the concentration of iodine
that combines and hence the concentration of KI3 formed will be obtained. The difference of
the initial concentration of KI and that of KI3 gives the equilibrium concentration of KI.
Knowing values of [I2], [KI] and [KI3] in aqueous KI layer equilibrium constant can be
calculated.

Procedure:
(1) Take three 250mL clean bottles and number them 4-6.
(2) To bottles 4, 5 and 6 add 25, 20 and 15 mL of saturated solution of iodine in cyclohexane
and 0, 5, and 10 ml of pure cyclohexane and 100mL 0.1M KI solution. Stopper the bottles
tightly.
(3) Shake all bottles vigorously for 20 minutes and suspend them in a water bath of required
temperature. Leave the bottles in a water bath of constant temperature for about 10 minutes to
attain the temperature of the bath.
(4) Remove 10mL aqueous layer from the first bottle and titrate with 0.01M thio using starch
as the indicator.
(5) Remove 5mL of the organic layer using a pipette into a clean iodine flask. Add 10 mL 10%
KI solution and titrate against 0.05 M thio.
(6) Similarly titrate the organic and aqueous layers of bottles 5 and 6.

2 S2O3 2– + I3 – = S4O6 2– + 3 I–

Bottle Volume of Volume of 0.01M Conc. of I2 in the Conc. of I2 in the Conc. Free
No. 0.05M thio for thio for 10mL aqueous layer cyclohexane layer iodine in
5mL aqueous layer C1moles/liter C2moles/liter aqueous
cyclohexane layer C2/D*
layer

6
*D is the partition coefficient

37
Determination of equilibrium constant:

For K1(Bottle No. 4),

[I2] = C2 / D = ..............

[KI3] = C1(C2 / D) = …………….

[KI] = C  [C1 (C2 / D)] = …………....

So equilibrium constant ,K1 = [KI3] / ( [I2][K I] )

=..............................

Similarly find for Bottle no. 5(K2) and 6(K3) .

So average value of equilibrium constant is = ( K1+ K2+ K3 ) / 3 =...........

Report:

i. Partition Coefficient of iodine between water and cyclohexane =

ii. Equilibrium constant of the reaction 𝐾𝐼 + 𝐼 ⇌ 𝐾𝐼 at …….0C =

38
 7.PHASE DIAGRAMS

Phenol Water System

The liquid- liquid system falls under three categories as (i) Completely miscible system,
(ii) Partially miscible system and (iii) completely immiscible system. In this experiment we
study the partially miscible system namely Phenol- Water system.

If we add phenol to water it will be soluble up to a certain limit and this solubility value will
increase with increase in temperature.similarly,if we add water to phenol same phenomena will
be observed . The number of homogeneous, mechanically separable and physically distinct
parts of a heterogeneous system is known as the number of phases, P, of the system. each phase
is separated from other phases by a physical boundary. When an equilibrium exists between a
number of phases under external controlling conditions such as temperature, pressure, and
concentration, the following relationship holds good
F = C-P + 2
where P = number of Phases in equilibrium, C = number of Components in the system, and F
= number of degrees of Freedom. This equation is called the Phase Rule, which relates the
phases,components and degrees of freedom of the system.
The mutual solubility curves can be obtained in two ways. (i) Analytical method: In this method
two liquids are shaken together in a thermostat until equilibrium is reached. The two conjugate
layers obtained are analyzed by appropriate physical or chemical method. In this way solubility
of each liquid into the other in a series of temperature is obtained. (ii) Synthetic method: the
known amount of the two substances is heated in glass tube and the temperature is determined
at which single homogeneous solution is obtained. Taking different known amount of the two
liquids and determining the temperature of complete miscibility, the solubility curve maybe
obtained.

39
Determine the Mutual Solubility Curve of Phenol and Water System

Aim:

(i) To determine the mutual solubility curve of phenol and water and hence the
consolute point.
(ii) To determine the critical solution temperature of phenol and water in presence of
(i)sodium chloride (ii) naphthalene and (iii) succinic acid.
Theory:

When phenol is shaken with water, a definite amount of phenol dissolves in water and a definite
amount of water dissolves in phenol; and the two liquid solutions, called conjugate layer are
obtained. The composition of these two layers is independent of the quantities of the liquid
mixed, but depends upon the temperature of the system. One of these layer is a saturated
solution of phenol in water and the other that of water in phenol. Thus at each temperature there
will be two solubilities, one phenol in water and the other for water in phenol. When the
temperature is increased there will be state where the two liquids become completely miscible
and this temperature is called the critical solution temperature or consolute point. A known
amount of the two liquids are heated slowly, and the temperature is recorded at which the two
layers just disappear. The temperature is once more determined at the appearance of the
turbidity as the system is cooled. The mean of the two temperatures gives the miscibility
temperature of the two liquid systems in the given proportions.

The presence of impurity affects the critical solution temperature. If the impurity is soluble in
one of the two liquids the consolute point is raised where it is lowered in the case of impurity
is soluble in both the liquids.

40
A graph is plotted miscibility temperature (ordinate) against composition (abscissa). The
smooth curve will be parabola in shape and the maximum of which gives the critical solution
temperature of the system.

Procedure

Calculate the densities of given sample of phenol and water. Fill phenol and water in two
burettes. Take thoroughly cleaned and dried hard glass test tube. Add 2ml of phenol (calculate
the weight from density). Add 0.5ml water and weight of water added is obtained from its
density. Calculate the weight percentage of phenol in the mixture.
Insert the thermometer and a stir into the test tubes and suspend in a beaker containing water.
Heat the water in the beaker slowly with constant stirring so as to have uniform temperature.
Stir well the phenol solution and record the temperature when the turbidity just disappears .
Remove the source of heating and allow the water in the beaker to cool slowly with constant
stirring. Record the temperature when the turbidity begins to appear. The average of the two
readings gives the temperature of complete miscibility of the two liquids.
Add 0.5ml water and calculate the percentage of phenol. Determine the temperature of
complete miscibility of the liquid system. Repeat the process by adding 1,2,………..15 ml of
water. In each case determine the miscibility temperature.
Plot a graph between the miscibility temperatures (ordinate) and composition of the solution
in percentage (abscissa). A smooth curve of parabolic shape is obtained and the maximum of
which gives the critical solution temperature of phenol- water system. Find the composition of
phenol corresponding to the critical solution temperature.

Take thoroughly cleaned and dried hard glass test tube. Add 2ml of phenol. Add 0.05ml water
and weight of water added is obtained from its density. Add 0.01g of impurity. Calculate the

41
weight percentage of phenol in the mixture. Repeat the above procedure to determine the
consolute point.
Take thoroughly cleaned and dried hard glass test tube. Add 2ml of phenol. TA will add water
and to phenol and will give the unknown composition.. Repeat the above procedure to
determine the consolute point. Calculate the unknown composition from graph.

Observation and Calculation

Density Calculation

Lab temperature = °C

Density of water at temperature …….. =

Weight of empty specific gravity bottle, w1gram = g

Weight of specific gravity bottle+water, w2 gram = g

Weight of empty sp.gravity bottle+phenol , w3gram = g

Weight of water,(w2-w1)gram = g

Weight of phenol,(w3-w1)gram = g

Density of phenol = ( )
𝜌1 =

42
Table 1. Composition miscibility temperature data of phenol-water system
Vol.of Composition of phenol Temp. at Temp. at Mean
water which which temperature
𝒘𝒕. 𝒐𝒇 𝒑𝒉𝒆𝒏𝒐𝒍
𝒘𝒕. 𝒐𝒇 𝒑𝒉𝒆𝒏𝒐𝒍 + 𝒘𝒕. 𝒐𝒇 𝒘𝒂𝒕𝒆𝒓
𝑿 𝟏𝟎𝟎 turbidity turbidity
disappears appears

0.5

10

11

12

13

14

15

Unknown

43
Table 2. Composition miscibility temperature data of phenol-water system with impurity
Weight of the impurity (…………………………..) =

Vol.of Composition of phenol Temp at which Temp. at which Mean

water turbidity turbidity temperature
disappears appears

Report

1. Critical solution temperature of phenol- water system =

2. Composition phenol at the critical solution temperature =
3. Critical solution temperature of phenol- water system on addition of impurity =

44
 8. SOLID LQUID EQUILIBRIUM

Solid and liquid can exist in equilibrium at the freezing point. When a homogeneous binary
liquid is cooled freezing point is reached when the solid phase separates out. The difference in
freezing point of the pure liquid and binary liquid is the depression in freezing point. The
depression in freezing point is proportional to the mole fraction of the solute in the binary
mixture. Thus
∆𝑇 = 𝑘 𝑚 = 𝑘 (1)
where ‘n’ and ‘N’ are number of moles of solute and the solvent. In dilute solution ‘n’ is
negligibly small compared N and hence equation (1) takes the form
/
∆𝑇 = 𝑘 =𝑘 /
(2)
where 𝑤 , 𝑀 are the weight and molecular weight of the solute and 𝑤 , 𝑀 are the weight and
molecular weight of the solvent ‘k’ is known as the freezing point constant or the cryoscopy
constant. It is theoretically defined as the depression of the freezing point of the solution
containing 1 g mole of the solute in 1 gram of the solvent. For practical purpose the molal
depression constant or the cryoscopic constant of the solvent is defined as the depression of
freezing point which would produce by dissolving 1 gram mole of solute in 1000g of the
solvent.
Molal depression constant kf of a solvent can be determined by thermodynamic equation
𝑘 = (3)
where 𝐿 is the latent heat of fusion of the solid solvent. If 𝐿 is expressed in Jg-1 and R in JK-1
mol-1 then 𝑘 kg mol-1. 𝑘 is experimentally determined by finding out the depression in
freezing point of a solution, produced by dissolving a known amount ‘w’ gram of the solute in
a known amount ‘W’ gram of the solvent.

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The freezing points of the solution and the solvent are determined by thermal analysis method.
The method consists in cooling of a molten mixture of the components and a graph known as
cooling curve between temperature and time is drawn. The cooling curve is continuous curve
as long as there is no phase change during cooling. When solid starts separating, the rate of
cooling is decreased due to liberation of heat. In consequence, the cooling curve exhibits a
break at the freezing point. Sometimes the separation of the solid phase does not occur at the
actual freezing point of the liquid phase. The liquid phase may cool below its freezing point
and is known as the super cooled liquid. When a solid stats separating from the super cooled
liquid the temperature rises to the freezing point. According the phase rule the system becomes
invariant at freezing point, and hence the entire liquid will freeze at a constant temperature.
The cooling curve will thus show a temperature halt at the freezing point.

8.1 Determine molal depression constant of α-naphthol

Procedure:
Take clean and dried boiling tube, a stirrer a sensitive thermometer and a two hold cork. Weigh
the empty boiling tube. Add about 5 g of pure α-naphthol into the boiling tube and record the
weight. The difference in weight gives the weight of naphthalene. Close the boiling tube with
a two holed cork. Through one of the holes introduce the thermometer and a stirrer through the
other. Heat the tube and the content in an oil bath. The solid gets melted completely and a clear
liquid is obtained. Remove it from the water bath and keep inside a jacket which prevents
sudden cooling. Stir the content very well and note the temperature at every 15 seconds.
Plot a graph of temperature (ordinate) against time and obtain the cooling curve. From the
break of the cooling curve determine the melting point of pure α-naphthol. Now add about
0.25g (accurately weighed) of impurity and mix it thoroughly with the solvent α-naphthol in
the same boiling tube. Heat the tube in the water bath till a clear liquid is obtained. Obtain a
cooling curve as before and determine the melting point of the solution

From the freezing point of the pure solvent and the solution evaluate the depression in freezing
point and hence calculate the cryoscopic constant of α-naphthol using following equation
∆
𝐾 = (4)

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8.2 Determination of molecular weight of solute.
Procedure:
Repeat experiment (a) using a solute whose molecular to be determined. From the cooling
curves determine the melting point of the pure solvent and the solution and hence the
depression in melting point. Calculate the molecular weight of the solute using the equation:
𝑀 = ∆
(5)

Temperature
Time 5g α-naphthol + 5g α-naphthol +
5g α-naphthol
0.25g impurity 0.25g unknown

Calculation:
Determination of Kf
∆𝑇𝑀 𝑤
𝐾 =
1000𝑤
Weight of solvent , w1 =
Freezing point of solvent ,T =

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Molecular weight of solute, M2 =
Weight of solute, w2 =
Freezing point of solvent+solute ,T1 =
ΔT = T- T1 =

Kf =

Determination of Molecular weight of unknown solute

1000𝑘 𝑤
𝑀 =
𝑤 ∆𝑇
Weight of unknown taken,w2 =
Freezing point of solvent+unknown ,T2 =
ΔT = T- T2 =
M2 =

Report:
i. Molal depression constant of α-naphthol =
ii. Molecular weight of the given solute =

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