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LIQUID SOLUTION
Solution: A homogeneous mixture of two or more substances.

Saturated Solution: A solution that is in equilibrium with pure solid solute. No more solute
can be dissolved in it.

Parts Per Million (ppm): Mass of the solute present in one million parts (106) by mass of
the solution.

Vapour Pressure of Pure Liquid : The pressure exerted by the vapour over the liquid
surface. It increases with increase in temperature.

Vapour Pressure Lowering = P0 – P

Azeotrope: A mixture of two or more compounds which form a mixture of constant boiling
point at which the composition of the vapour is the same as that of the mixture.

Why substances dissolve in one another

1. Nature of the Substances: It is found that two substances having nearly similar
structures are soluble in each other. Ethanol and water are soluble in each other in all
proportions because of their similar structures. Ethanol has an ethyl group and water has
hydrogen atom. Water molecules are quite firmly held to each other by hydrogen bonds.
Ethanol is also hydrogen bonded but less firmly held than water. When mixed together
water and ethanol molecules attract each other because of the formation of the hydrogen
bonding.

2. Similar Molecular Structures: Benzene and toluene are soluble in each other
because both are aromatic hydrocarbons which have similar molecular structures.
Because of this similarity the interaction between a benzene and toluene molecule is same
as the interaction between a benzene molecule and another benzene molecule or between
two toluene molecules.

3. High dielectric constant of the solvent: Ionic solids dissolve in polar solvents
like water because high dielectric constant of the solvent breaks the ionic solids into
cations and anions. Thereafter they exist in solution as hydrated ions.

4. Chemical Interactions: Covalent solid dissolves in non-polar solvents like water

because the chemical interaction between the solute and the solvent molecules. In general
LIKE DISSOLVE LIKE.

Parts Per Million

mass of solute
ppm = × 106
Total mass of solution

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In case of gases, ppm refers to volumes rather than masses. 1 ppm means that 1cm3 of the
gaseous mixture is present in 1000L of solution. For example the concentration of SO2 in Delhi
has been found to be 10 ppm. This means that 10cm3 of SO2 is present in 1000 L of air.

Illustration 1: One litre of sea water weighs 1030 g and contains about 6 × 10–3g of dissolved
O2. Calculate the concentration of dissolved oxygen in ppm.
Solution: Mass of O2 in mg = 6 × 10–3g × 103 mg/g = 6mg
Mass of O 2 in mg 6
ppm of O2 in 1030 g sea water = =
Mass of sea water in kg (1030 /1000)kg
6 × 1000
= = 5.8ppm
1030

Vapour Pressure
The pressure exerted by the vapour (molecules in the vapour phase) over the surface of the liquid
at the equilibrium at given temperature is called the vapour pressure of the liquid. The vapour
pressure of the liquid depends on

1. Effect of temperature on the vapour pressure of the liquid: As

temperature of a liquid is raised, its molecules move more rapidly. This results in an
increase in their average K.E. At higher temperature, greater no. of molecules possess
energies greater than escape energy and therefore greater no. of molecules escape as
vapour. This results in increase in vapour pressure of the liquid. The temperature at which
the vapour pressure of the liquid becomes equal to the atmospheric pressure is called its
boiling point.

2. Nature of liquid: The vapour pressure of a liquid depends upon the strength of
intermolecular forces acting between its molecules. A liquid which has weaker
intermolecular forces acting between its molecules has higher tendency to escape as
vapour and therefore such a liquid has higher vapour pressure and is said to be volatile.
On the other hand, a liquid which has stronger intermolecular forces acting between its
molecules has lower tendency to escape as vapour and therefore such a liquid has lower
vapour pressure and is said to be less volatile or non volatile. For example, ethyl alcohol
has higher vapour pressure because of the weak intermolecular forces acting between its
molecules than water which has stronger intermolecular forces acting between water
molecules of volatile liquid has lower boiling point than a non-volatile liquid.

Vapour Pressure of Solution

Lowering of Vapour Pressure of a Liquid in Solution
Case 1 : When a non-volatile solute (say glucose) is dissolved in solvent (say water) to form a
solution the vapour pressure of the solution is due to the vapour pressure of the
solvent alone (water) as non-volatile solute does not evaporate. It is found that the
vapour pressure of the solution is less than that of the pure liquid (pure water).

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Case 2: When a volatile solute (say C2H5OH) is dissolved in water to form a solution, the
vapour phase consists of the vapours of both the components of the solution (both
C2H5OH and H2O). In such a case, vapour pressure of the solution is the sum of the
partial vapour pressures of each component. It is found that partial vapour pressure of
each component depends upon the molar concentration (or mole fraction) in solution
and is always less than the vapour pressure of the pure component.

Explanation: In terms of kinetic model, when a solute (volatile or non-volatile) is dissolved in

a liquid to form a solution, some of the solute particles occupy positions of solvent molecules at
the surface of the liquid and therefore the surface area available for the escape of solvent
molecules decreases. Now the no. of molecules escaping from the surface of the liquid into
vapour is less. The rate of evaporation of a liquid from its solution is thus less than that of the
pure solvent at the same temperature because of the decreased surface area. There are now, fewer
molecules in the vapour phase over the solution. As the rate of condensation is proportional to
the no. of molecules in the vapour phase, the lower rate of evaporation of the liquid is balanced
by the lower rate of condensation of the vapour and hence the vapour pressure of the liquid in
solution is known as its partial vapour pressure which is less than the vapour pressure of the pure
liquid at the same temperature. If P 0 is the vapour pressure of the pure liquid and P that of liquid
in solution., then
Lowering of vapour pressure = P° – P
Greater the no. of particles of the solute in solution greater is the lowering of vapour pressure of
the solution.
P° – P ∝ Molar concentration of particles of solute in solution.

Raoult’s Law and Vapour Pressure Of Solution

For a solution of two miscible liquids, the partial vapour pressure of each liquid is less than the
respective vapour pressure of the pure liquid because of the decrease in surface area of the liquid
from which fewer molecules go into vapour phase. Raoult’s law states that the partial vapour
pressure of a liquid is directly proportional to its mole fraction in solution.

PA ∝ X A
PA = kX A … (1)
nA
XA =
nA + nB
where PA is the partial vapour pressure of the liquid and X A is its mole fraction in solution. We
can determine the value of the proportionality constant as follows.

For pure solvent, the value of mole fraction is unity i.e. X A = 1 and the vapour pressure is equal
to the vapour pressure of the pure solvent PAo .

∴ Eq. (1) becomes

PA = k ×1 where PA = vapour pressure of liquid or solution

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k = PAo

We can write eq. (1) as

PA = X A PAo
Partial V.P of the liquid = V.P of the pure liquid × Mole fraction of the
in the solution liquid in solution

Raoult’s Law for a Solution Containing Volatile Solute

Raoult’s law states that the partial vapour pressure of a component of a solution of two miscible
liquids A and B at a given temperature is equal to the product of the vapour pressure of the pure
component at that temperature and its mole fraction in the solution.

Mathematical Expression: Let us assume that a solution has nA moles of liquid A and n B
moles of liquid B. Let PA° be the vapour pressure of the pure liquid A and PB° is the vapour
pressure of the pure liquid B.

nA
Mole fraction of A, X A =
nA + nB
nB
Mole fraction of B, X B =
nA + nB

According to Raoult’s law,

PA = PA° X A

where PA is the partial vapour pressure of liquid A in the solution

Similarly, PB = PB° X B [ PB = partial vapour pressure of B in the solution]

The total vapour pressure of an ideal solution containing components A and B is the sum of
partial vapour pressures of all the components (Dalton’s law of partial pressures)

P = PA + PB = PA° X A + PB° X B

Raoult’s Law for Solution Containing Non-Volatile Solute

Relative Lowering of vapour pressure: For a solution of a non-volatile solute in a
liquid, the vapour pressure contribution by the non-volatile solute is negligible. Therefore, the
partial vapour pressure of a solution containing a non-volatile solute is equal to the product of
vapour pressure of the pure liquid (solvent PA° ) and its mole fraction in the solution.

Let X A be the mole fraction of solvent A, then

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PA = PA° X A … (1)

If X B be the mole fraction of the solute B, then

X A + X B = 1 or X A = 1 – X B … (2)

From eq. (1) and (2)

PA = PA° (1 – X B ) = PA° – PA° X B

PA° – PA nB
°
= XB =
PA nA + nB
PA° – PA
is called relative lowering of vapour pressure
PA°
 P° – P 
Therefore, Raoult’s law states that the relative lowering of vapour pressure  A ° A  , for a non-
 PA 
volatile solute is equal to the mole fraction of the solute when the solvent alone is volatile.

Limitations of Raoult’s Law

When the solution is not dilute, there are significant interactions between solute and solvent
particles and Raoult’s law is not obeyed fully. There are +ve and –ve deviation from ideal
behaviour.

If solute molecules dissociates in solution, there are more particles in solution and therefore,
lowering of vapour pressure shows an increased effect.
+
NaCl(s) Na (aq) + Cl(aq)
–

If the solute molecules associates in solution, there are less particles in solution, and therefore
lowering of vapour pressure shows a decreased effect.
nAB (AB) n
2C6 H5 COOH (C6 H 5COOH) 2

Lowering of Vapour Pressure

Lowering of vapour pressure is a colligative property. The vapour pressure of a solvent in a
solution is less than the vapour pressure of the pure solvent at the same temperature. If PAo that of
solvent in the solution, the decrease in vapour pressure PAo – PA is called the lowering of vapour
pressure which is directly proportional to the mole fraction of the solvent in solution.

PA = X A PAo

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Higher the mole fraction of the solvent in the solution, higher is the partial vapour pressure of the
solvent.

Determination of Molecular Mass From Raoult’s Law

The measurement of relative lowering of vapour pressure of a solution affords a convenient
method for determining molecular mass of the solute. Consider a solution containing n A moles
of solvent A and n B moles of solute B.
nB WB / M B
XB = =
n A + n B WA + WB
MA MB
Eq. for relative lowering of vapour pressure can also be written as
PAo – PA nB
= XB =
PAo
nA + nB
For very dilute solution n B < < < n A
PAo – PA n B WB / M B
∴ = =
PAo n A WA / M A
MA PAo
M B = WB × ×
WA PAo – PA

Illustration 2: The vapour pressure of pure water at 37°C is 47.1 torr. What is the vapour
pressure of an aqueous solution at 37°C containing 20 g of glucose dissolved in
500 gm of water. Also calculate vapour pressure lowering.
500
Solution: n H 2O = = 27.78 mol
18
20
n(glucose) = = 0.11 mol
180
n H 2O 27.78 27.78
X H 2O = = = = 0.996
n H2 O + n (glu cose) 27.78 + 0.11 27.89
According to Raoult’s law,
PH2 O = PHo 2O X H2 O = 47.1× 0.996 = 46.9 torr
PHo 2 O – PH 2O = 47.1 – 46.9 = 0.2 torr

Illustration 3: The vapour pressure of ethyl alcohol at 25°C is 59.2 torr. The vapour pressure
of a solution of urea in ethyl alcohol is 51.3 torr. What is the molality of the
solution?
PAo – PA nB n Moles of solute
Solution: = Xsolute = = B =
PAo
n A + n B n A Moles of solvent

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59.2 – 51.3 7.9

= X solute = = 0.1334
59.2 59.2
Moles of solute m mol m mol
Molality = = =
Mass of solvent in kg 1 kg 1000 g
1000
No. of mol of solvent in 1000 gm =
46
m mol m × 46
X solute = =
1000 / 46 1000
x solute × 1000
m=
M solvent
0.1334 × 1000
Molality = = 2.9 molal.
46

Ideal Solution
An ideal solution may be defined as the one which obeys Raoult’s law over all concentration
ranges at a given temperature. The total vapour pressure of an ideal solution containing liquids A
and B is given by the following equation.

P = PA + PB = PAo X A + PBo X B

An example of a nearly ideal solution is toluene-benzene solution. In an ideal solution of two

components A and B, all attractive forces between A and B molecules or between A and A
molecules or between B and B molecules (A–B, A–A and B–B) must be identical so that the
escaping tendency of an A or B molecule is independent of whether it is surrounded by A
molecules, B, molecules or varying proportions of A and B molecules. The escaping tendency of
pure liquid A in solution remains the same. Similarly the escaping tendency of B remains the
same. Liquids form ideal solution only when they have nearly same molecular size and related
constitution so that they have similar molecular environment in the pure state as well as in
solution. A perfect ideal solution is rare but many liquids form nearly ideal solution. Liquid
heptane and hexane also form an ideal solution because the interaction between a hexane
molecule and another hexane molecule is the same as the interaction between two heptane
molecules other examples of ideal solutions are:

Ethyl bromide + ethyl iodide

Benzene + toluene
Chlorobenzene + bromobenzene

Dilute solutions are found to obey Raoult’s law and thus behave as an ideal solution.

Conditions for Forming Ideal Solution: Two liquids on mixing form an ideal solution
only when

1. both have similar structures and polarity so that they have similar molecular environment.

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2. both have similar molecular sizes.

3. both have identical intermolecular forces.

Characteristics Of Ideal Solution: Mixing of two substances results in an ideal solution

only when:
1. They obey Raoult’s Law

2. ∆H mixing = 0 ⇒ that is no heat is absorbed or released during dissolution

3. ∆Vmixing = 0 ⇒ that is the total volume of the solution is equal to the sum of the volume of
the pure liquids mixed to form the solution.

Graphical Representation of Vapour Pressure of Ideal Solutions: Figure shows

the relationship between partial vapour pressure and mole fraction of an ideal solution at constant
temperature.
1. Straight line I represents the plot of vapour pressure of liquid A (PA ) and its mole
fraction (X A ) . According to Raoult’s law this should be a straight line when

XA = 0 PA = 0
X A = 1, PA = PAo
When mole fraction of liquid A is X A = 1 , the liquid A is pure and its vapour pressure is
equal to PAo as shown by line (I)

2. Straight line II represents the plot of partial vapour o o

P = PA + PB III PBo
pressure of liquid (B) PB and its mole fraction (X B ) .
II
PAo
According to Raoult’s law, this should be a straight line. I

when

XB = 0 PB = 0 VP

X B = 1, PB = PBo XA = 1
XB = 0
Mole fraction XA = 0
XB = 1

When mole fraction of liquid B is X B = 1 , the liquid B

is pure and its vapour pressure is equal to PBo as shown
by
line (II).

3. Straight line (III) represents the total vapour pressure, P, of the solution for any
composition and is given by the sum of the partial vapour pressure of liquids of A and B.

P = PA + PB

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Line (III) is obtained by joining point PAo and PBo . Line (III) also indicates that for an ideal
solution, the vapour pressures at various compositions of solutions are intermediate
between the value PAo and PBo and that these vapour pressure’s lie on the straight line
joining points PAo and PBo .

Non-Ideal Solutions
Solutions which do not obey Raoult’s law over all concentration ranges at constant temperature
are called non-ideal solutions. Non-ideal solution form with a change in volume and enthalpy,
∆H mixing and ∆Vmixing do not have zero values. The plot of the total pressure of the solution versus
mole fraction is not a straight line but a curve with a +ve or –ve deviation because

PA ≠ PAo X A and PB ≠ PBo X B

Types of Non-Ideal Solutions

1. Non ideal solutions showing +ve deviation
2. Non ideal solutions showing –ve deviation.

Positive Deviation from Raoult’s Law: In a solution showing +ve deviation, the
vapour pressure of the solution is higher than that of an ideal solution of the same
composition. This is because the partial vapour pressure of each liquid is higher than would be
expected on the basis of Raoult’s law. The reason for solutions showing non-ideal behaviour is
that the liquids have different molecular environments in solution. In a solution showing +ve
deviation the attractive forces between molecules of A and B is less than between A – A
molecules or between B – B molecules. Thus the escaping tendencies of the molecules, as
measured by the vapour pressure of the liquids. The partial vapour pressure of the liquids, will be
greater in either of the pure liquids. The partial vapour pressure of each liquid is thus greater than
expected on the basis of Raoult’s law. For a solution showing +ve deviation from ideality, ∆H is
+ve i.e., heat is absorbed during the formation of the solution because chemical bonds are broken
and the new bonds formed are weaker and there is thus increase in volume i.e. ∆Vmixing is +ve for
a solution with +ve deviation.
1. The liquids do not obey Raoult’s law in solution i.e.,
PA > PAo X A and PB > PBo X B
2. ∆H mixing is +ve (Heat is absorbed)

3. ∆Vmixing is +ve i.e., volume of the solution formed is more than the sum of the volumes of

A and B mixed.

Solution of ethanol and cyclohexane show the deviation from ideality. In pure ethanol, ethanol
molecules are hydrogen bonded i.e., there are strong attractive forces between ethanol molecule
in liquid ethanol. When liquid cyclohexane is added to ethanol the cyclohexane molecules get in

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between the ethanol molecules and thus break up the H-bonds. This reduces the ethanol ethanol
intermolecular attractions and thus escaping tendency of the ethanol molecules increases. This
makes the partial vapour pressure of ethanol higher than that expected if the solution was ideal.
Therefore solution of ethanol and cyclohexanes show non ideal behaviour with +ve deviation
from Raoult’s law.
δ+ δ– δ+ δ– δ+ δ– δ+ δ–
H O H O H O H O

C2 H 5 C2 H 5 C2 H5 C2 H 5

C6 H12 C6 H12 C6 H12

Examples: Ethanol – water, ether-acetone, CS2 -acetone, CCl4 -methanol, acetone – benzene,
CCl4 - CHCl3 .

Graphical Representation of Vapour Pressure of a Non-Ideal Solution

Showing Positive Deviation: Figure shows the relationship between partial vapour
pressures and mole fraction of a non-ideal solution showing +ve deviation.
1. The plot of partial vapour pressure of liquid A and its PA = PA + P B
III
mole fraction is not a straight line but is a curve I
showing the deviation from Raoult’s law P
A=
PA > PAo X A
VP
of
VP C
2H
5O
H
II (A
of )
P
=V
PB

2. The plot of partial vapour pressure of liquid B and its XA = 1

Mole fraction XA = 0
XB = 0 XB = 1
mole fraction is also not a straight line but is a curve
(II) showing +ve deviation from Raoult’s law.
PB > PBo X B

3. The curve III indicates the total vapour pressure of the solution for any composition. For
the deviation, the total vapour pressure is more than the sum of partial vapour pressure of
liquids A and B if they form ideal solution.
PA > PAo X A + PBo X B .

Negative Deviation from Raoult’s Law: In a solution showing –ve deviation from ideal
behaviour, the vapour pressure of the solution is lower than that of an ideal solution of the same
composition. This is because the partial vapour pressure of each liquid is less than that would be
expected on the basis of Raoult’s law. In such a solution of liquid A and B showing –ve
deviation, the attractive forces between molecules of A and B is greater than that between A – A
molecules or B – B molecules (formation of stronger bonds). Thus the escaping tendencies of
both the liquids are lowered and hence their partial vapour pressures are also lower than expected
if it obeyed Raoult’s law. For a solution showing negative deviation i.e., heat is liberated during
formation of such solutions because the new bonds formed are stronger and there is decrease in

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volume, i.e., volume of solution is less than the sum of the volumes of individual liquids A and
B. For a solution with negative deviation.

1. The liquid do not obey Raoult’s law in solution

PA < PAo X A , PB < PBo X B

2. ∆H mixing is –ve ⇒ heat is liberated.

3. ∆Vmixing is –ve ⇒ volume decreases.

Solution of chloroform and acetone show –ve deviation from ideal behaviour. When CHCl3 and
CH3COCH 3 are mixed together to form a solution, hydrogen bonding occurs between the
molecules of CHCl3 and CH3COCH 3 . There are new stronger attractive forces between
chloroform and acetone molecules compared with the attractive forces between CHCl3 — CHCl3
molecules and CH3COCH 3 – CH3COCH 3 molecules.

The stronger attractive forces decreases the escaping tendencies of both the chloroform and
acetone molecules and make the partial vapour pressure of each liquid less than that based on
Raoult’s law. Therefore, the total vapour pressure of the solution would be less than that
predicted by Raoult’s law and the solution thus shows –ve deviation from ideality.
Cl
CH 3
Cl C H O=C
CH 3
Cl

Examples: Methanol – Acetic acid and water- HNO3 Graphical representation of vapour
pressure of non ideal solution showing –ve deviation: figure shows the relationship between
partial vapour pressure and mole fraction of a non ideal solution showing –ve deviation.

1. The plot of partial vapour pressure of liquid A and its

mole fraction is not a straight line but it is a curve (I)
showing negative deviation from ideality. III
P = PA + PB
PA < PAo X A VP II

2. The plot of partial vapour pressure of liquid B is not a

straight line but is a curve (II) showing negative I
deviation from ideality.
XA = 1 Mole fraction XA = 0
XB = 0 XB = 1
PB < P X B
o
B

3. Curve (III) indicates the total vapour pressure of the solution for any composition. For -ve
deviation, the total vapour pressure of solution is less than the sum of partial vapour
pressures of liquids A and B if they form ideal solution.

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Azeotropes
The non-ideal solution showing large deviations from Raoult’s law can not be purified by
distillation. Whatever the initial composition of the solution. Heating changes its composition
until at a constant temperature where the composition of the mixture of the liquids and the vapour
is also constant. The distillation does not change its composition further. A solution at certain
composition which continues to boil at constant temperature without change in the composition
of the solution and its vapour is called an AZEOTROPE or constant boiling mixture. Azeotropes
are of two types:

1. Azeotropes with Max. vapour pressure and Min. BP : When liquid in a

solution do not have great chemical affinity for each other (+ve deviation from ideality)
their higher escape tendencies increase the vapour pressure much more than expected on
the basis of Raoult’s law. In many cases, the deviations are so extreme as to lead to a
maximum in the curve. The point of maximum vapour pressure means that the bp at this
composition will be minimum and constant.

Example of Minimum Boiling Azeotrope

Components Boiling point (K)
A B Mass% of B A B Azeoterope
H 2O C2 H5 OH 95.57 373 351.3 351.10
H 2O C3 H 7 OH 71.69 373 370.0 350.72
CHCl3 C2 H5 OH 67.00 334 351.3 332.30

2. Azeotropes with Min. vapour pressure and Max. bp : When liquids in

solution form chemical bonds (–ve deviation from ideality), their escape tendencies and
hence the vapour pressure decreases than expected on the basis of Raoult’s law. In many
cases, the maximum in the temperature composition curve is obtained. The point of
minimum vapour pressure in the curve means that the bp of this composition will be max.
and constant.

Examples of Max. Boiling Azeotrope

Components Boiling point (K)
A B Mass% of B A B Azeoterope

H 2O HCl 20.3 373 188 383

H 2O HNO3 58.0 373 359 393.5

H 2O HClO 4 71.6 373 383 476

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Colligative Properties
The property of a solution which depends upon the fraction of solute particles and solvent
particles and not upon the chemical nature of solute is called a colligative property.

1. Lowering of vapour pressure

2. Elevation of Boiling point
3. Depression of Freezing point
4. Osmotic Pressure
Greater the no. of particles of solute in solution, greater is the extent to which colligative property
is affected.

Factors that Affect the Colligative Property: To be more accurate, the colligative
property depends upon the fraction of solute and solvent particles in solution.
i) Nature of the solvent
ii) Independent of the nature of the solute
iii) Extent of association and dissociation of solute particles in solution.

Lowering of Vapour Pressure: Lowering of vapour pressure is a colligative property. The

vapour pressure of a solvent in solution is less than the vapour pressure of the pure solvent at the
same temperature. If PAo is the vapour pressure of the pure solvent and PA that of the solvent in
solution, the decrease in vapour pressure PAo – PA is called the lowering of vapour pressure which
is directly proportional to the mole fraction of the solute in solution.

PA = X A PAo

Higher the mole fraction of solvent in solution, higher is the partial vapour pressure of the
solvent.
Vapour pressure lowering of a solution has already been explained under Raoult’ Law. It was
derived that the relative lowering of vapour pressure is given by the equation
PAo – PA nB
= XB =
PAo
nA + nB

Measurement of Relative Lowering of Vapour Pressure

Ostwald and Walker Method: In this method a stream of dry air is bubbled successively
through (i) the solution (ii) the solvent and (iii) a reagent, that can absorb the vapour of the
solvent. As the solvent is usually water, the reagent is generally anhydrous CaCl 2 .

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dry air

CaCl2 2
CaCl

∝∝ weight ∝
∝ pp –−pp CaCl2 U-tube gain in weight ∝ p0
0
Solution loss Solution
Solution in weight
loss in weight p p Solvent
Solvent
Solution
loss in in
loss weight 0 CaCl U-tube 0

The first three bulbs contain a weighed amount of the solution under examination and the next
three bulbs contain a weighed amount of the pure solvent A weighed amount of anhydrous
CaCl 2 is taken in the set of U-tube at the end.

All the bulbs must be kept at the same temperature and air must be bubbled gradually to ensure
that it gets saturated with the vapours in each bulb.
The dry air, as it passes through the solution, takes up an amount of vapour which is proportional
to the vapour pressure of the solution at the prevailing temperature. This moist air passes through
water (solvent), it takes up a further amount of vapour which is proportional to the difference in
vapour pressure of the pure solvent and the solution. It is evident that
Loss in mass of solution ∝ P
Loss in mass of solvent ∝ P0 – P
(Loss in mass of solution + loss in mass of solvent) ∝ P o – P + P ∝ P o
or (gain in weight of CaCl2)

Where P o is vapour pressure of pure solvent, P is vapour pressure of solution. The CaCl 2 tubes
are weighed at the end of the experiment. The gain in mass should be equal to the total loss in
weight of the solution and the solvent which, in turn is proportional to P o as shown above.
In other words,
Loss in mass of solvent Po – P
=
Gain in mass of CaCl2 tube Po

Thus, knowing the loss in mass of the solvent and gain in the mass of the CaCl 2 tubes, it is
possible to calculate the lowering of vapour pressure.

Composition of the vapour The composition of the liquid and the vapour that are in mutual
equilibrium are not necessarily the same, the common sense suggest that the vapour pressure
should be richer in more volatile component.

The total vapour pressure PT can also be related to the mole fraction YA and YB of the two
components in the vapour phase

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PA PB
YA = and YB = … (1)
PT PT
or PA = YA PT
X A PAo = YA PT … (2)
and X B P = YB PT
o
B … (3)

We know that
PT = PA + PB
= PAo X A + PBo X B Q XA + XB = 1
= P (1 – X B ) + P X B
o
A
o
B XA = 1 – XB
PT = P – P X B + P X B
o
A
o
A
o
B

or PT – PAo = X B (PBo – PAo )

PT – PAo
XB = … (4)
PBo – PAo

Putting the value of X B in eq. (3)

PT – PAo o
PB = YB PT … (5)
PBo – PAo
PAo PBo
PT = … (6)
PBo + (PAo – PBo ) YB
1 PBo + (PAo – PBo ) YB PBo + PAo YB – PBo YB 1 YB YB
or = = = + –
PT PAo PBo PAo PBo PAo PBo PAo
Elevation of Boiling Point: The boiling point of a
liquid is the temperature at which its vapour pressure
Solution
becomes equal to the atmospheric pressure. When the Pure solvent
1 atm
atmospheric pressure is 1 atm, boiling point is called the
Vapour pressure

normal boiling point. The vapour pressure of a liquid

E
decreases when a non-volatile solute is dissolved in it. The F
decreased vapour-pressure means that the solution would
have to be heated to a higher temperature so that its vapour
pressure becomes equal to the atmospheric pressure. In other Tb0 Tbs
Temperture
words, the boiling point of the solution Tb is higher than the
boiling point of the pure solvent Tb0. The difference Tsb – Tb0 Plot of variation of vapour pressure elevation
of boiling point.
is called the boiling point elevation.
Boiling point elevation = Tb – Tb0
It is found that the elevation of boiling point is directly proportional to the number of moles of
the solute in a given amount of the solvent (m).
∆T ∝ m or ∆Tb = K b ⋅ m

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where m is the molality of the solution and Kb is a constant for a given solvent known as boiling-
point elevation constant or molal boiling point elevation constant or ebullioscopic constant of
solution.

Illustration 3: Estimate the boiling point of a solution of 25.0g of urea NH2CONH2 plus 25.0g
of thiourea NH2CSNH2 in 500g of chloroform, CHCl3. The boiling point of pure
chloroform is 61.2°C, Kb of chloroform = 3.63 Km–1.
Solution: Molecular mass of urea, NH2CONH2
= 2 × amu N + 1amu C + 1amu O + 4 × amu H
= 2 × 14 + 12 + 16 +4 × 1 = 60 g/mol
Molecular mass of Thiourea, NH2CSNH2
= 2 × amu N + 1amu C + 1amu S + 4 × amu H
= 2 × 14 + 12 + 32 + 4 × 1 = 76 g/mol
Mass of urea 25.0g
Moles of urea = = = 0.42mol
Molecular mass of urea 60g / mol
25.0
Moles of thiourea = = 0.33mol
76 g/mol
Moles of solute 0.75mol
Molality, m = = = 1.50m
Mass of solvent in kg (500g /1000g)kg
∆Tb = Tb – Tb0 = Kb⋅m = 3.63 K m–1 × 1.50m = 5.44K = 5.445°C
Tb = 5.445°C + Tb0 = 5.445°C + 61.2°C = 66.645°C

Molal Elevation Constant or Ebullioscopic Constant: When molality of the

solution is 1m, (1 mole of the solute is dissolved in 1 kg of the solvent) the above equation
reduces to

∆Tb = K b × 1m = K b
This indicates that molal elevation constant of a liquid (Kb) is equal to elevation of boiling point
when molality of the solution is 1 m. The unit of Kb is Km–1. K (mol/kg)–1 = K kg mol–1.
Molal elevation constant is characteristic of a particular solvent and can be calculated from the
thermodynamical relationship.
RTb2
Kb =
1000L v
where R is molar gas constant, Tb is the boiling point of the solvent on Kelvin scale and Lv the
latent heat of vaporization of solvent in calories per gram.
2 × (373) 2
For water Kb = = 0.515
1000 × 540

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Depression in Freezing Point: The freezing point of Solid solvent lvent

so
a liquid is the temperature at which it begins to freeze and the
crystallized solid and liquid are in equilibrium. At freezing solution

point, the vapour pressure of the solid is equal to the vapour

pressure of the liquid. When a dilute solution is cooled to

Vapour pressure
freezing point, it is assumed that crystals of pure solvent
always separate out first. The vapour pressure of a liquid
s 0
decreases when a non-volatile solute is dissolved in it. Temperature
T T f f

Therefore, a solid liquid equilibrium exists only at a

Plot of variation of vapour pressure of a
temperature lower than the freezing point of the pure solvent. solution with temperature and depression in
In other words, for a solid to have the same vapour freezing point.
pressure as that of the solution, the freezing point should lower down. If Tf0 is the freezing point
of the pure solvent and Tf that of the solution, the difference Tf0 – Tsf is called the freezing point
depression.
Freezing point depression = Tf0 – Tsf
It is found that the depression in freezing point is directly proportional to the number of moles of
the solute in a solute given amount of the solvent.
∆Tf = Kf⋅m
where m is the molality of the solution and Kf is a constant for a given solvent known as molal
depression constant or cryoscopic constant.
Kf is characteristic of a particular solvent and can be calculated from the thermodynamical
relationship.
0.002Tf2
Kf =
Lf
where Tf is the freezing point of solvent in absolute scale and Lf the latent heat of fusion in
calories per gram of the solvent. For water,
0.002 × (273) 2
Kf = = 1.86
80

Illustration 4: What is the percent by mass of iodine needed to reduce the freezing point of
benzene to 3.5°C? The freezing point and cryoscopic constant of pure benzene
are 5.5°C and 5.12 K/m respectively.
Solution: ∆Tf = Tf0 – Tf = Kfm
5.5°C – 3.5°C = 5.12 K/m × m
2
m= = 0.39m
5.12
∴ Mass of iodine needed for 1000g of benzene = m × molecular mass of iodine I2
= 0.39 mol/kg × 254 g/mol = 99.06 g/kg
∴ 1000g + 99.06g solution contains 99.06g I2

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99.06g × 100
100g solution contains = 9.01%
1099.06g

Osmosis: Spontaneous flow of solvent molecules through a semipermeable membrane from a

pure solvent to the solution (or from a dilute solution to a concentrated solution) is termed as
osmosis.

Osmotic Pressure (π): The hydrostatic pressure built up on the solution which just stops
osmosis. Alternatively, it may be defined as the pressure which must be applied to the
concentrated solution in order to stop osmosis.

For dilute solutions π = CRT = hρg

Where C is the total molar concentration of all the free species present in the solution, h is the
height developed by the column of the concentrated solution and ρ is the density of the solution
in the column. On the basis of osmotic pressure, the solutions can be classified in three classes.

Isotonic solutions: Two solutions having same osmotic pressures at same temperature.
(This implies C1 = C2).

Hypertonic and Hypotonic Solution: When two solutions are being compared, then the
solution with higher osmotic pressure is termed as hypertonic. The solution with lower osmotic
pressure is termed as hypotonic.

Osmotic pressures can be determined quite accurately, hence it is used in the determination of
molecular weights of large proteins and similar substances.

Reverse Osmosis: If a pressure greater than the osmotic pressure is applied on the
concentrated solution, the solvent starts to flow from concentrated solution to dilute solution (or
pure solvent). This is reverse osmosis. One of its chief uses is desalination of sea water to get
pure drinking water.

Abnormal Molecular Masses (Colligative Molality)

Vapour pressure lowering, boiling point elevation, freezing point depression and osmotic
pressure are colligative properties which depend upon the fraction of solute and solvent particles
in solution and not upon the chemical nature of the solute. We have also learnt that colligative
properties afford excellent methods for determining molecular masses of solutes. The molecular
mass of sodium chloride is 58.5 g/mol but the molecular mass obtained by using a colligative
property is 29.25 g/mol. This is half of the normal molecular mass of sodium chloride and is
therefore called abnormal molecular mass. Why is it so? This is because the colligative property
depends upon the number of solute particles in solution. Sodium chloride is a strong electrolyte
and ionizes completely in solution to form sodium ions, Na+, and chloride ions, Cl–.

NaCl(s) + aq → Na+(aq) + Cl–(aq)

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This equation shows that 1 mole of sodium chloride provides 1 mole of Na+ ions and 1 mole of
Cl– ions. The solution, therefore contains 2 moles of solute particles because Na+ and Cl–
ions behave as independent solute particles. The molal boiling point elevation of water is 0.52
Km–1. If we dissolve 1 mole of sodium chloride (1m) in 1000g water, the boiling point elevation
should be 0.52 K. But experimental measurement shows it to be 1.04K, i.e., double of the
expected value. As the magnitude of the colligative effect is determined by the concentration of
solute particles in solution, the result shows that sodium chloride solution has 2 moles of solute
particles. We thus find that the effective molality of a solute which ionizes in solution is
different from the molality (m) of the solution. The effective molality of a solute is called
colligative molality and is denoted by the symbol, mc. We can express this result as an equation
by writing.

Colligative molality = i × Molality

m c = im

where i is the number of particles per formula unit that occur in solution. The value of ‘i’ for
NaCl is 2 and ‘i’ for CaCl2 is 3 because 1 mole CaCl2 provides 3 moles of solute particles: 1
mole of Ca2+ ions and 2 moles of Cl– ions. A 1 m CaCl2 solution has therefore colligative
molality of 3 m and boiling point elevation of solution will be three times, i.e. 0.52 K × 3 = 1.56
K. We know that the osmotic pressure of 1 m solution at 0°C is 22.4 atm. The osmotic pressure
of 1 m NaCl at 0°C is 2 × 22.4 atm = 44.8 atm because the colligative molality of sodium
chloride is 2m. We can express these results as

In general,

Colligative property expected theoretically Moles of solute dissolved

=
Colligative property observed experimentally Mole of solute actually present after dissocaition or association

The relation between molality and molecular mass of a solute is

Mass of solute
m=
Molecular mass of solute × Mass of solvent in kg

The molecular mass of a solute is inversely proportional to its molality. If

colligative molality is 2 m, the calculated molecular mass is one-half of the actual molecular
mass of the solute. If colligative molality is 3 m, the calculated molecular mass is one third of the
actual molecular mass of the solute. The molecular mass of benzoic acid is 122 g/mol. But the
molecular mass of benzoic acid dissolved in benzene is found to be 244 g/mol by using a
colligative property. Benzoic acid associates to form a dimer and therefore its colligative molality
is one-half of the molality of benzoic acid. As molecular mass of a solute is inversely
proportional to molality, the molecular mass of benzoic acid determined using a colligative
property is double the actual molecular mass of benzoic acid. We can summarize the results as:

1. The extent of dissociation and colligative property. A solute dissociates

completely or partially in solution makes available more particles than would otherwise
be present in solution and therefore, a colligative property shows an increased effect. For

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example, molecular masses obtained of strong acids, bases and salts are much less than
their normal values. As an example, one particle of potassium chloride on dissociation in
water gives two particles, K+ and Cl– and therefore, the molecular mass obtained by a
colligative property is half of its normal molecular mass.
K + Cl(s)
−
+ nH 2O  +
→ K (aq −
) + Cl (aq )
1 mol 1mol 1 mol

2. The extent of association and colligative O H O

property: A solute that associates in solution provides H5C 6 C 6H5
less particles that would otherwise be present in solution
O H O
and therefore, the colligative property shows the
A dimer of benzoic acid
decreased effect. For example, benzoic acid in benzene
is found to have molecular mass which is just twice its
normal molecular mass. It is found that compounds
which are capable of forming hydrogen bonds, e.g.,
phenols, carboxylic aids, alcohols: because of
association show decreased effect of colligative
property.

Van’t Hoff Factor

In 1886, Van’t Hoff, Jacobus Henricus (Dutch chemist, 1859,-1911) introduced a factor ‘i’
known as Van’t Hoff factor to express the extent to association or dissociation of a solute in
solution. Van’t Hoff factor may be defined as the ratio of normal molecular mass of the solute to
the observed molecular mass using a colligative property.
Normal molecular Mass (M) Moles of solute actually present in solution
i= =
Observed Molecualr Mass (M C ) Moles of solute dissolved
Effective Molality Colligative Molality
= =
Molality Molality

i) For association of a solute, i is less than unity: The value of ‘i’ to be 0.5
indicates that two molecules of solute associate to form a dimer. If the value of ‘i’ is
slightly less than unity, say 0.91, this indicates that there are strong intermolecular forces
between molecules of a solute in solution.

ii) For dissociation of a solute, i is greater than unity: If ‘i’ for a solute is 2,
this indicates that a solute molecule ionizes in solution to give 2 particles. If ‘i’ for a
solute is 3, a solute molecule ionizes in solution to give 3 particles (e.g. CaCl2, K2SO4).
The value of ‘i’ for concentrated KCl solution is slightly less than two which indicates
that KCl does not ionize fully in concentrated solution and its degree of dissociation is
therefore less than 1. There are strong attractive forces between positively charged K+
ions and negatively charged Cl– ions and a fraction of ions act together as ion-pairs. For
dilute KCl solution, ‘i’ has a value of 2 indicating that the strength of attractive forces
decreases with dilute and the electrolyte dissociates completely.

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Calculation of Van’t Hoff Factor: The Van’t Hoff factor for a solute can be calculated
by the following modified equations:

(i) ∆Tf = iKfm; (ii) ∆Tb = iKbm; (iii) π = iCRT

where C is molarity of the solution.

i) Degree of Dissociation and Colligative Property:

An nA
No. of moles dissolved 1 mol 0
No. of moles after dissociation 1–α nα
Total number of moles present in solution = (1 – α) + nα
Moles of solute actually present in solution
Van’t Hoff factor, i =
Moles of solute dissolved
(1 − α) + nα i −1
= = 1 + (n − 1)α or α =
1 n −1

ii) Degree of Association and Colligative Property: Let n moles of the solute,
A, associate to form (A)n. If α is the degree of association.

nA An
No. of moles dissolved 1 mol 0
No. of moles after association 1–α α/n
Total number of moles present in solution = (1 – α) + α/n
  1 
i = 1 − α 1 −  
  n 
i −1 n
Hence α = = (i − 1) ×
1
−1 1− n
n

Illustration 5: A solution is prepared by dissolving 26.3g of CdSO4 in 1000g water. The

depression in freezing point of solution was found to be 0.284K. Calculate the
Van’t Hoff factor. The cryoscopic constant of water is 1.86K kg solvent mol–1-
solute.
Solution: Molecular mass CdSO4 = 112.4 +32 + 4 × 16 = 208.4 g/mol
Mass CdSO4
Molality CdSO4 =
Molecular mass CdSO4 × Mass solvent in kg
26.3g
= = 0.216m
 1000 
(208.4g / mol) ×  kg 
 1000 
∆Tf 0.284K
∆Tf = iKfm or i = = = 1.21
K f m 1.86K / m × 0.126m

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Illustration 6: Three particles of a solute, A, associate in benzene to form species A3. Calculate
the freezing point of 0.25 molal solution. The degree of association of solute A is
found to be 0.80. the freezing point of benzene and its cryoscopic constant are
5.5°C and 5.12 Km–1 respectively.

Solution: 3A → A3
No. of moles dissolved 3 0
No. of moles after dissociation m(1–α) mα/3
Total moles present after dissociation
α  α  2α   3 − 2 × 0.8 
= m(1 − α) + m = m 1 − α +  = m  1 −  = 0.25m   = 0.177m
3  3  3   3 
∆Tf = Kfm or Tf – Tf = 5.12 Km × 0.117 m = 0.6
0 –1

Tf = Tf0 – 0.6°C = 5.5°C – 0.6°C = 4.9°C

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Solved Problems
Objective

Problem 1: The ratio of the value of any colligative property for KCl solution to that for
sugar is nearly ----- times.
(a) 1 (b) 0.5
(c) 2 (d) 2.5

Exp. colligative property no.of particle furnished by KCl

Solution: iKCl= = =2
Normal colligative property no. of particles before dissociation
isugar = 1
∴(c)

Problem 2: Osmotic pressure of blood is 7.65 atm at 310 K. An aqueous solution of glucose
that will be isotonic with blood is ----- wt/ vol.
(a) 5.41% (b) 3.54%
(c) 4.53% (d) 53.4%

Solution: We know πV = nRT for glucose and blood;

If isotonic, πglucose = πblood
W
Thus, 7.65 × V = × 0.0821 × 310
180
W
∴ = 54.1 g/ lit = 5.41 % (wt/vol)
V
∴ (a)

Problem 3: The Van’t Hoff factor for 0.1 M La (NO3)3 solution is found to be 2.74 the
percentage dissociation of the salt is
(a) 85% (b) 58%
(c) 65.8% (d) 56.8%

Solution: La (NO3)3 La+3 + 2NO3−

1–α α 3α
i = 1 + 3α
2.74 = 1 + 3α
α = 0.58
percentage dissociation = 58%
∴ (b)

Problem 4: The vapour pressure of pure benzene at 50°C is 268 torr. How many mol of
non-volatile solute per mol of benzene is required to prepare a solution of
benzene having a vapour pressure of 167 torr at 50°C

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(a) 0.377 (b) 0.605

(c) 0.623 (d) 0.395

Solution: P = PBo X B
167
XB = = 0.623
268
Xsolute = 1 – XB = 0.377
∴ (a)

Problem 5: Maximum freezing point will be for 1 molal solution of, assuming equal
ionization in each case
(a) [Fe(H2O)6]Cl3 (b) [Fe(H2O)5Cl]Cl2 . H2O
(c) [Fe(H2O)4Cl2]Cl . 2H2O (d) [Fe(H2O)3Cl3] . 3H2O

Solution: Larger the value of ‘i’

Smaller the f.p. (d) in a case of non electrolytes, i = 1

Problem 6: 1.0 molal aqueous solution of an electrolyte X3Y2 is 25% ionized. The boiling
point of the solution is (Kb for H2O = 0.52 K kg/mol)
(a) 375.5 K (b) 374.04 K
(c) 377.12 K (d) 373.25 K

Solution: X 3 Y2 3X 2+ + 2Y
2α
3−

1− α 3α

i = 1 + 4α
=1 + 4(0.25) = 2
∆Tb = i Kb M = 2 ×0.52 × 1.0 = 1.04
Boiling point of the solution = 374.04 K
∴ (b)

Problem 7: Equal amounts of a solute are dissolved in equal amounts of two solvents A and
B. The relative lowering of vapour pressure for the solution A has twice the
relative lowering of vapour pressure for the solution B. If MA and MB are the
molecular weights of solvents A and B respectively, then for dilute solution of A
and B, with solute.
M
(a) MA = MB (b) M A = B
2
(c) MA = 4MB (d) MA = 2MB

 P o − Ps  n  P o − Ps  n
Solution:  Po  = and  o  =
  A NA  P B NB

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 P o − Ps 
 Po 
∴ o  A = N B = w B × M A = M A or MA
= 2 ∴ MA = 2MB
 P − Ps  NA MB w A MB MB
 Po 
 B
∴ (d)
–1
Problem 8: The molal boiling point constant of water is 0.573°C Kg mole . When 0.1 mole
of glucose is dissolved in 1000 gm of water, the solution boils under atmospheric
pressure at
(a) 100 . 513°C (b) 100 . 0573°C
(c) 100 . 256°C (d) 101 . 025°C

Solution: ∆Tb = KbM

2.573 × 0.1 = 0.0573°C
B.P. of the solution = B.P. of pure solvent + ∆Tb
= 100 + 0.0573 = 100.0573°C
∴ (b)

Problem 9: The relationship between osmotic pressure at 273 K when 10 gm glucose (P1),
10 gm urea (P2) and 10 g sucrose (P3) are dissolved in 250 ml of water is
(a) P1 > P2 > P3 (b) P3 > P1 > P2
(c) P2 > P1 > P3 (d) P2 > P3 > P1

n w
Solution: π = CRT = RT or π = RT
v M×v
1
πα
M
M. wt. of glucose, sucrose and urea in the order urea < glucose < sucrose
∴ π in the order urea > glucose > sucrose

Problem 10: FeCl3 on reaction with K4(Fe(CN)6] in aqueous solution gives blue colour.
These are separated by a semi permeable membrane AB. Due to osmosis there is
0.01 M FeCl3
0.1 M K4 [Fe(CN)6]

Side X Side Y

(a) blue colour formation in side x

(b) blue colour formation in side y
(c) blue colour formation in both sides
(d) no blue colour formation

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Solution: Due to osmosis, solvent (i.e., water) from y side migrates towards x side. Since
solute (i.e.) FeCl3 is not migrating, there is no blue colour formation.

Problem 11: A weak electrolyte, AB, is 5% dissociated in aqueous solution. What is the
freezing point of a 0.100 molal aqueous solution of AB? Kf for water is 1.86
deg/molal.
(a) –3.8°C (b) –0.1953°C
(c) –1.7°C (d) – 0.78°C

5
Solution: Degree of dissociation, α, AB = = 0.05
100
AB → A+ + B–
No. of moles dissolved m 0 0
No. of moles after dissociation m(1 – α) mα mα
After dissociation 0.1(1 – 0.05) 0.1 × 0.05 0.1 × 0.05
Total moles = Molality = 0.1 (1 – 0.05) + 0.1 × 0.05 + 0.1 × 0.05
= 0.095 + 0.005 + 0.005 = 0.105m
∆Tf = Kfm or Tf0 – Tf = 1.86 K/m × 0.105m = 0.1953 deg
Tf = 0°C – 0.1953 = –0.1953°C
∴ (b)

Problem 12: Calculate the boiling point of a one molar aqueous solution
(density = 1.04 g mL–1) of potassium chloride, Kb for water = 0.52 kg mol–1.
Atomic masses of K = 39, Cl = 35.5
(a) 107.28°C (b) 103.68°C
(c) 101.078°C (d) None of these

Solution: Volume of solution = 1000,

Mass of the solution = V × d = 1000 mL × 1.04 g/mL = 1040g
Amount of solute in 1000 mL solution = 1 M
= 1 M × Molecular Mass = 1M × 74.5g/mol = 74.5g
Mass of water = Mass of solution – Mass of KCl = 1040g – 74.5g = 965.5g
Moles of solute 1 mol
Molality of the solution = m = = = 1.0357
Mass of solvent in kg (965.5/1000)kg
∆Tb = i .Kb.m = 2 × 0.52 K kg mol–1 × 1.0357 = 1.078°C
Boiling point of the solution = 100°C + 1.078°C = 101.078°C
∴ (c)

Problem 13: The vapour pressure of a solvent decreased by 10 mm Hg when a non volatile
solute was added to the solvent. The mole fraction of solute in solution is 0.2,
what would be mole fraction of the solvent if decrease in vapour pressure is 20
mm of Hg.
(a) 0.8 (b) 0.6
(c) 0.4 (d) 0.2

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Solution: Po – Ps = Po × mole fraction of solute; 10 = Po × 0.2

Again, 20 = Po × mole fraction solute
Hence, n = 0.4, so, mole fraction of solvent = 1 – 0.4 = 0.6
∴ (b)
–1
Problem 14: The molal freezing point constant for water is 1.86 K. molarlity . If 34.2 g of
cane sugar (C12H22O11) are dissolved in 1000g of water, the solution will
freeze at
(a) –1.86°C (b) 1.86°C
(c) –3.92°C (d) 2.42°C

1000 × K f × w 1000 × 1.86 × 34.2

Solution: ∆Tf = = = 1.86°
MW 100 × 342
∴Tf = 0 – 1.86 = –1.86° C
∴ (a)

Problem 15: 20 g of a binary electrolyte (mol.wt. = 100) are dissolved in 500 g of water. The
freezing point of the solution is –0.74°C, Kf = 1.86 K.molality–1. The degree of
ionisation of the electrolyte is
(a) 50% (b) 75%
(c) 100% (d) 0

1000 × K f × w 100 × 1.86 × 20

Solution: ∆Tf = ∴ 0.74 = ⇒ M = 100
M×W M × 500
Normal mol.wt 100
Now, =1+α=
exp. mol.wt. 100
So, α = 0 ∴ (d)

Problem 16: Y g of non - volatile organic substance of molecular mass M is dissolved in 250g
benzene. Molal elevation constant of benzene is Kb. Elevation in its boiling point
is given by
M 4 K bY
(a) (b)
K bY M
KY KY
(c) b (d) b
4M M

1000 × K b × Y 4K b Y
Solution: ∆T = =
250 × M M
∴ (b)

Problem 17: The values of observed and calculated molecular weights of silver nitrate are
92.64 and 170 respectively. The degree of dissociation of silver nitrate is
(a) 60% (b) 83.5%
(c) 46.7% (d) 60.23%

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Normal mol.wt
Solution: i for AgNO3 = =1+α
Observed mol.wt.
170
α= – 1 = 0.835 = 83.5 %
92.64
∴ (b)

Problem 18: At 40°C, the vapour pressures in torr, of methyl alcohol - ethy alcohol solution
is represented by the equation. P = 119XA + 135 where XA is mole fraction of
PA
methyl alcohol, then the value of Lim is
X A →1 XA
(a) 254 torr (b) 135 torr
(c) 119 torr (d) 140 torr

PA
Solution: P = 119XA + 135; Lim = 119 + 135 = 254
X A →1 XA
∴ (a)

Problem 19: The amount of ice that will separate on cooling a solution containing 50g of
ethylene glycol in 200g water to –9.3°C is : [Kf = 1.86 K molality–1]
(a) 38.71 g (b) 38.71 mg
(c) 42 g (d) 42 mg

1000 × K f × w
Solution: ∆T =
W×M
1000 × 1.86 × 50
or 9.3 =
62 × W
∴ W = 161.29
∴ Ice separated = 200 – 161.29 = 38.71 g
∴ (a)

Problem 20: The freezing point of aqueous solution contains 5% by mass urea, 1.0% by mass
KCl and 10% by mass of glucose is : ( K f H2O = 1.86K molality–1)
(a) 290.2 K (b) 285.5 K
(c) 269.93 K (d) 250 K

Solution: ∆Tf = ∆Tf for glucose + ∆Tf for KCl + ∆Tf for urea
1000 × 1.86 × 10 1000 × 1.86 × 1 × 2 1000 × 1.86 × 5
= + + = 3.069°
100 × 180 74.5 × 100 100 × 60
∴ freezing point = 273 – 3.069 = 269 .93 K
∴ (c)

Multiple choice Questions

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Problem 21: Which of the following aqueous solutions produce the same osmotic pressure
(a) 0.1 M NaCl solution
(b) 0.1 M glucose solution
(c) 0.6 g urea in 100 ml solution
(d) 1.0 g of a non-electrolyte solute (X) in 50 ml solution (Molar mass of X =
200)

Solution : (b, c, d)

Problem 22: What does not change on changing temperature

(a) Mole fraction (b) Normality
(c) Molality (d) none of these

Solution : (a, c)

Problem 23: Which of the following aqueous solution are isotonic (R = 0.082 atm K-1 mol-1)
(a) 0.01 M glucose
(b) 0.01 M NaNO3
(c) 500 ml solution containing 0.3 g urea
(d) 0.04 N HCl

Solution : (a, c)

Problem 24: In the depression of freezing point experiment, it is found that the
(a) Vapour pressure of the solution is less than that of pure solvent
(b) Vapour pressure of the solution is more than that of pure solvent
(c) Only solute molecules solidify at the freezing point
(d) Only solvent molecules solidify at the freezing point.

Solution : (a, d) The depression of freezing point is less than that of pure solvent and only
solvent molecules solidify at the freezing point.

Subjective

Problem 1: The freezing point depression of a 0.109 M aq. solution of formic acid is –
0.21°C. Calculate the equilibrium constant for the reaction,
HCOOH (aq) H+ (aq) + HCOO– (aq)
Kf for water = 1.86 kg mol–1 K
Solution: From question
∆Tf = 0.21°C
Molality of solution = 0.109 m
The reaction is
HCOOH (aq) H+(aq) + HCOO– (aq)
Initially moles C 0 0
Moles after dissociation (1–α)C αC αC

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(1 − α) × C + α × C + α × C
i= = 1 + α, where α = degree of dissociation
1× C
As we know,
∆Tf = Kf × i × Cm
0.21 = 1.86 × (1+α) × 0.109 ( in very dilute solution molarity and molality can be
taken as same)
0.21
∴ 1+α = = 1.0358
1.86 × 0.109
or, α = 0.0358 = 0.036
∴ [HCOOH] = (1–α) × C = (1–0.036) × C = 0.964 ×C
[H+] = α × C = 0.036 × C, [HCOO–] = 0.036 ×C
[H + ][HCOO− ] 0.036 × C × 0.036 × C
Ka = = = 1.34 × 10–3 ×C mol lit–1
[HCOOH] 0.964 × C
= 1.34 × 10–3 × 0.109
Ka = 1.46 × 10–4

Problem 2: The freezing point of a solution of acetic acid (mole fraction is 0.02) in benzene
is 277.4 K. Acetic acid exists partly as a dimer
2A A2. Calculate equilibrium constant for dimerisation. Freezing point of
benzene is 278.4 K and (Kf for benzene is 5)
Solution: Let acetic acid = A
Benzene = B
Assume, α part of A forms dimer
2A A2
1 0 initially moles
1–α α/2 moles after dimer is formed
∴i=
(1 − α ) + α 2 = 1 – α/2
1
Mol. fraction of A = xA = 0.02
Mol. fraction of B = xB = 0.98
x A 1000 0.02 1000
Molality of A in B = × = × = 0.262 mol kg–1 of Benzene
mB XB 78 0.98
Since, ∆Tf = Kf × i × molality
278.4–277.4 = 5 × i × 0.262
or, 1 = 5 × i × 0.262
1
i= = 0.763
5 × 0.262
1– α/2 = 0.763 ⇒ α = 0.47

Hence the molality of A after dimer is formed = (1–α) × initial molality

= (1 – 0.48) × initial molality = 0.52 × 0.262
Molality of A2 after dimer is formed

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α 0.48
= × molality = × 0.262 = 0.24 × 0.26 = 0.06288
2 2
The equilibrium constant
Keq =
[A ]
2
=
0.06288
= 3.39 kg mol–1
[A]
2 2
(0.13624)

Problem 3: A milimolar solution of pottassium ferricyanide is 70% dissociated at 27°C.

Find out the osmotic pressure of the solution.
1
Solution: Given, concentration of solution = C = M = 10–3M
1000
K3[Fe(CN)6] → 3K+ + [Fe(CN)6]–3
Initially moles 1 0 0
Moles after dissociation 1-α 3α α
70
Where α = degree of dissociation = 70% = = 0.7
100
Total moles of after dissociation = (1–α) + 3α + α = 1+ 3α
1 + 3α
∴i=
1
i = 1+3α = 1+(3× 0.7) = 3.1
Since osmotic pressure
π = iCRT
∴ π = 3.1 × 10–3 × 0.0821 × 300
= 0.31 × 3 × 0.0821 atm = 0.07635 atm

Problem 4: If the solution of mercuric cyanide of strength 3 g / L has an osmotic pressure

0.3092 × 105 Nm–2 at 298 K, what is the apparent molecular weight and degree
of dissociation of Hg(CN)2?
(Hg = 200.61, C = 12 , N = 14)

Solution: Let the apparent molecular weight = mo

n
Osmotic pressure = π = ×RT
v
w 1
= × × RT
mo v
3 × 10−3 1
or, 0.3092 × 105 = × −3 × 8.314 × 298
mo 10
∴ mo = 240.2 × 10 kg
–3

Since,
number of particles after dissociation normal mol. w t.
=
number of particles before dissociation observed mol. wt.
∴ Hg(CN)2 Hg++ + 2CN–

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1–α α 2α
∴ Number of particles after dissociation
= (1 – α) + α + 2α
= 1 + 2α
1 + 2α 252.61× 10 −3
i.e., =
1 240.2 × 10 − 3
∴ α = 0.02457 or 2.4567 %
–1
Problem 5: If the apparent degree of ionization of KCl (KCl = 74.5 gm mol ) in water at
290K is 0.86. Calculate the mass of KCl which must be made up to 1 dm3 of
aqueous solution so as to produce the same osmotic pressure as the 4.0%
solution of glucose at that temperature.,
Solution: Due to ionization of KCl
KCl → K+ + Cl–
Initial moles 1 0 0
Moles after dissociation 1–α α α
∴i=
(1 − α ) + α + α = 1+ α
1
From question, degree of ionization = α = 0.86
∴ i = 1+ 0.86 = 1.86
For Osmotic pressure of glucose,
For 4% glucose solution,
Weight of glucose = 40 gm
Volume of solution = V = 1L = 1dm3
Molecular weight of glucose C6H12O6= m = 180
1
∴ πglucose = n × × RT, where πglucose = osmotic pressure of glucose
v
w 1 40 1
= × ×R×T= × × RT
m v 180 1
1
Similarly , πKCl = i × n × × RT
v
1 w 1 w1 1
= 1.86 × n × ×RT= 1.86 × 1 × × RT = 1.86 × × ×RT
v m1 v 74.5 1
As both solutions are isotonic
∴πKCl = πglucose
w1 40
1.86 × × RT = × RT
74.5 180
40 0.5
∴ W1 = × = 8.9 gm
180 m
Problem 6: The freezing point of an aqueous solution of KCN containing
0.1892 mol kg–1 of solvent was found to be – 0.704°C. On adding 0.095 mol of

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Hg(CN)2, the freezing point of the solution was found to be – 0.530°C. If the
complex – formation takes place according to the following equation.
Hg(CN)2 + nKCN Kn [Hg(CN)n+2].
What is the formula of the complex ?
Kf(H2O) is 1.86 kg mol–1 K.

Solution: ∆Tf (KCN solution) = 0.704°C

molality of KCN solution = 0.1892
i = (1 + x)
∆Tf = Kf × m × i
∆Tf 0.704
i = (1 + x) = = = 2.0
K f × m 1.86 × 0.1892
This gives x = 1, indicating 100% ionization of KCN
∆Tf of the complex = 0.530
Molality of Hg(CN)2 = 0.095 mol kg–1
Kn [Hg(CN)n+2] nK+ + [Hg(CN)n+2]–
1 0 0 ….. initially moles
1– α nα α ….. moles after dissociation
here i = (1–α) + nα + α = 1+nα
Qα=1
∴ i = 1+ n
∆Tf = Kf × i × molality
0.503 = 1.86 × I × 0.095
0.503
i= ≈ 3
1.86 × 0.095
1+ n = 3 or, n = 2
Hence, the complex is K2[Hg(CN)4]

Problem 7: Ethylene dibromide (C2H4Br2) and 1,2–dibromopropane (C3H6Br2) forms a

series of ideal solution over the whole range of composition. At 85°C, the
vapour pressure of these pure liquids are 173 mmHg and 127mm Hg
respectively.
10 gm of ethylene dibromide is dissolved in 80 gm of 1,2 – dibromo–propane.
Calculate the partial pressures of each components and the total pressure of the
solution at 85°C.
Calculate the composition of vapour in equilibrium with the above solution and
express as mole fraction of ethylene dibromide
What would be the mole fraction of 1,2 dibromopropane in solution with 50:50
mole mixture in the vapour.

Solution: Let C2H4Br2 = A, ∴ mA = 24+4 + 160, where mA= molecular weight of A

mB = molecular weight of B and B is
C3H6Br2 = mB = 36 + 6+ 160 = 202

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wA 10
Moles of A, nA = = = 0.053
mA 188
w 80
Moles of B, nB = B = = 0.396
mB 202
nB 0.396
XB = = = 0.882
nA + nB 0.053 + 0.396
∴ xA + xB = 1
∴ xA = 1 – 0.882 = 0.118
a) We know, total pressure
PT = PA + PB Where PA, PB are partial pressures of A and B respectively.
= PAo ⋅ X A + PBo ⋅ X B , where PAo , PBo are partial pressures of pure component
of A and B.
PT = 173 × 0.118 + 127 × 0.882
= 20.42 + 112.014
= 132.43mm Hg
Here partial pressure of A, PA = 20.42 mm Hg
Here partial pressure of B, PB = 112.014 mm Hg.

b) Mole fraction of ethylene dibromide in the vapour

partial pressure of A 20.42
YA = = = 0.154
Total pressure 132.43

c) In vapour phase
nA: nB = 50:50
∴YA = 0.5, YB = 0.5

Problem 8: Calculate the molecular weight of cellulose acetate if its 0.5% (wt./vol) solution
in acetone (sp. gr. = 0.9) shows an osmotic rise of 23 mm against pure acetone
at 27°C.

Solution: 0.5% (wt. / vol) solution means 0.5 gm of cellulose acetate is dissolved in 100 ml
solution.
Osmotic pressure = 23 mm of pure acetone
2.3 × 0.9
π = 2.3 Cm of pure acetone = cm of Hg = 0.1522 cm of Hg
13.6
0.1522
π = atm = 0.002 atm
76
Let the molecular weight of the cellulose acetate be M
0.5
Here, number of mole of cellulose acetate (n) =
M
Volume = v = 100 ml = 0.1 lit
R = 0.082 lit atm mol–1 K–1, T = ( 27 + 273) = 300 K

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n 0.5 1
Osmotic pressure (π) = ×RT ⇒ 0.002 = × × 0.0821 × 300
v M 0.1
∴ M = 61575

Problem 9: 1kg of an aqueous solution of Sucrose is cooled and maintained at –4°C. How
much ice will be separated out if the molality of the solution is 0.75? Kf (H2O) =
1.86 Kg mol–1K.

Solution: Sucrose is a non–electrolyte,

Hence i = 1
Molecular weight of sucrose (C12H22O11) = m = 342 gm mol–1
Molality of the solution = 0.75 m = 0.75 mol kg–1 solvent
= 0.75 × 342 gm Sucrose per kg solvent = 256.5 gm Sucrose per kg solvent
hence, weight of 1 molal solution = 1000 + 256.5 = 1256.5 gm
256.5
Sucrose present in 1 kg solution = × 1000 = 204.14 gm
1256.5
Weight of solvent (H2O) present in 1 kg solution = 1000– 204.14 = 795.86 gm
Since depression in freezing point
w 1000
∆Tf = Kf × i × × , Where W = weight of solvent
m W
204.14 1000
w = weight of the solute or, 4 = 1.86 × 1 × ×
342 W
∴ W = 277.55 gm
i.e., weight of solvent required to maintain this solution at – 4°C is
W = 277.55
Hence rest weight of H2O will convert into ice.
Hence amount of ice formed = 795.86 – 277.55 = 518.31 gm

Problem 10: River water is found to contain 11.7% NaCl, 9.5% MgCl2, and 8.4%. NaHCO3
by weight of solution. Calculate its normal boiling point assuming 90%
ionization of NaCl, 70% ionization of MgCl2 and 50% ionization of NaHCO3
(Kb for water = 0.52)

11.7
Solution: nNaCl = = 0.2
58.5
9.5
n MgCl2 = = 0.1
95
8.4
n NaHCO3 = = 0.1
84
iNaCl = 1+ α = 1+ 0.9 = 1.9
i MgCl2 = 1 + 2α = 1+ 0.7 × 2 = 2.4
i NaHCO3 = 1+ 2α = 1+ 0.5 × 2 = 2.0
Weight of solvent = 100 – (11.7 + 9.5 + 8.4) = 70.4 g

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(i NaCl × n NaCl + i MgCl2 × n MgCl2 + i NaHCO3 × n NaHCO3 ) × K b × 1000

∆Tb =
Weight of solvent
(1.9 × 0.2 + 2.4 × 0.1 + 2 × 0.1) × 0.52 × 1000
= = 5.94°C
70.4
∴ Boiling point of solution = 100 + 5.94 = 105.95°C

Problem 11: An aqueous solution containing 288 gm of a non–volalite compound having the
stochiometric composition CxH2xOx in 90 gm water boils at 101.24°C at 1.00
atmospheric pressure . What is the molecular formula?
Kb(H2O) = 0.512 K mol–1 kg
Tb (H2O) = 100°C
Solution: Elevation in B.P. = 101.24 – 100 = 1.24°C
Since solute is non volatile
Since the elevation in boiling point is
∆Tb = Kb × i × molality
w 1000
= Kb × 1× ×
m W
288 1000
1.24 = 0.512 × ×
m 90
∴ m = 1321.2 gm mol–1
m = mol.wt. of solute
molar mass of CxH2xOx = 12x + 1 × 2x + 16x = 30x
∴ 30x = 1321.2
∴ x = 44
Hence the molecular formula is = C44H88O44

Problem 12: 30 ml of CH3OH ( d = 0.7980 gm Cm–3) and 70 ml of H2O (d = 0.9984 gm

cm–3) are mixed at 25°C to form a solution of density 0.9575 gm cm–3. Calculate
the freezing point of the solution. Kf (H2O) is 1.86 Kg mol–1 K. Also calculate its
molarity

Solution: Weight of CH3OH (w1) = 30cm3 × 0.7980 gm/cm3 = 23.94 gm

Weight of solvent (H2O) (w2) = 70 cm3 × 0.9984 gm cm3 = 69.888 gm
w1 1000
∴ molality of solution = ×
m1 w 2
23.94 1000
Where m1 = molecular weight of CH3OH = 32 = × = 10.7046 m
32 69.88
As we know that
Depression in freezing point , ∆Tf = Kf × i × molality,
for CH3OH, i = 1
∆Tf = 1.86 × 10.7046°C = 19.91°C
Freezing point of the solution = 0– 19.91°C = –19.91°C
Weight of solution = weight of solute + weight of solvent

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= 23.94 + 69.888 = 93.828 gm

wt. of the solution 93.828
volume of the solution = = = 97.99 ml
density of the solution 0.95751
w 1000 23.94 1000
molarity of solution = 1 × = × mol lit–1 = 7.63 M
m1 V(in ml) 32 97.99

Problem 13: A complex is represented as CoCl3.xNH3. Its 0.1 m solution in aqueous solution
shows ∆Tf = 0.558° Kf(H2O) = 1.86 mol–1 K and assume 100% ionization and
co–ordination number of Co(III) is six . What is the complex?

Solution: From question, molality of solution = Cm = 0.1

Depression in freezing point = ∆Tf = 0.558°C
Kf (H2O) = 1.86 kg mol–1 K–1
As we know that
∆Tf = Kf × i × m, Where i = Vant Hoff’s factor
0.558 = 1.86 × 0.1 × i
0.558
∴i= =3
0.186
or, i ≈ 3 indicates that complex ionize to form three ions since co−ordination
number is 6 hence x = 5
i.e., CoCl3.5NH3 → [Co(NH3)5Cl]++ + 2Cl–
↓ ↓
1 Cation 2 anions
So, the complex is [Co(NH3)5Cl]Cl2

Problem 14: A solution comprising 0.1 mol of naphthalene and 0.9 mol of benzene is cooled
until some benzene freezes out. The solution is then decanted off from the solid
and warmed to 353 K, where its vapour pressure is found to be 670 torr. The
freezing and normal boiling point of benzene are 278.5 K and 353 K,
respectively. Calculate the temperature to which the solution was cooled
originally and the amount of benzene that must have frozen out. Assume
conditions of ideal solution. Kf for benzene = 5K kg mole–1.
Solution: Molality of the resulting solution (i.e. after the benzene freezes out) can be
determined on the basis Raoult’s law.
(760 − 670)
X naph × 1000 760
m= = = 1.72 mol kg–1.
X benzene × 78 0.88 × 78
 1000 
Weight of benzene in the resulting solution =  × 0.1 = 58.1 g
 1.72 
Amount of benzene frozen = 0.9 × 78 – 58.1 = 12.1 g
∆Tf = Kfm = 5 × 1.72 = 8.60 K
Hence the temp to which the solution was cooled=278.5 – 8.60 = 269.9 K

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Problem 15: Find Ka, the ionization constant of tartaric acid if a 0.100 molal aqueous solution
of tartaric acid freezes at –0.205°C. Assume that only the first ionization is of
importance and that 0.1 m = 0.1M. Kf = 1.86 kg mol–1 K.

Solution: Assuming that the tartaric acid be a monobasic as AH. It ionizes as

AH A + H+
Initially conc. C 0 0
Conc. after dissociation C(1–α) Cα Cα,
C(1 − α) + Cα + Cα C(1 + α)
Here, i = , where α = degree of dissociation = = 1+α
C C
Molal concentration = 0.1
∆Tf = Kf ×Cm × i
0.205 = 1.86 × 0.1 × (1+α) ∴ α = 0.1
[A − ][H + ] Cα × Cα α 2 C
Ka = = =
[AH] C(1 − α) 1 − α
( 0.1) × 0.1
2

Ka = = 1.11 × 10–3 ∴Ka = 1.11 × 10–3

1 − 0.1

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KVPY
1. The weight percent of sucrose (formula weight = 342 g mol−1 ) in an aqueous solution is 3.42. The
density
of the solution is 1 g m L−1 , the concentration of sucrose in the solution in mol L−1 is (2013)
(A) 0.01 (B) 0.1 (C) 1.0 (D) 10

2. A dilute aqueous solution of a polymer of known molecular weight shows an elevation of boiling point
of water by 0.052 K. The molar boiling point elevation constant of water is 0.52 K kg mol−1 .
Using these data- (2007)
(A) it is possible to calculate the relative lowering of vapour pressure of water and the magnitude of
freezing
point depression, but not the osmotic pressure at 300 K.
(B) it is possible to calculate the relative lowering of vapour pressure of water, but neither the
magnitude of
freezing point depression nor the osmotic pressure at 300K.
(C) it is possible to calculate the relative lowering of vapour pressure but neither the magnitude of
freezing
point depression nor the osomotic pressure at 300 K.
(D) it is possible to calculate the relative lowering of vapour pressure and the osmotic pressure at
300K
but not the magnitude of freezing point depression.
o
3. The freezing point of pure benzene is 5.5 C. When 2.9 g of butane is dissolved in 200g of benzene,
o
the freezing point of benzene decreases to 4 C. To lower the freezing point of benzene by another
o
1.5 C, the
amount of butane that has to be added to mixture is – (2008)
(A) 5.8 g (B) 2.9 g (C) 1.5 g (D) 8.7 g

4. The boiling points of 0.01 M aqueous solution of sucrose, NaCl and CaCl2 would be (2010)
(A) The same (B) Highest for sucrose solution
(C) Highest for NaCl solution (D) Highest for CaCl2 solution

Answer Key
1:B 2:D 3:B 4:D

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Assignments (New Pattern)

SECTION – I Single Choice Questions

LEVEL – I

1. At 40°C, the vapour pressure in torr of methanol and ethanol solution is

P = 119x + 135
Where x is the mol. fraction of methanol. Hence:
(a) vapour pressure of pure methanol is 119 torr.
(b) vapour pressure of pure ethanol is 135 torr.
(c) vapour pressure of equimolar mixture of each is 127 mm
(d) mixture is completely immiscible

2. Consider following cases:

I : 2 M CH3COOH solution in benzene at 27°C where there is dimer formation to the
extent of 100%
II : 0.5 M KCl aq. Solution at 27°C, which ionizes 100%; which is/are true statement(s)?
(a) both are isotonic (b) I is hypertonic
(c) II is hypertonic (d) none is correct

3. If PA is the vapour pressure of a pure liquid A and the mol fraction of A in the mixture of
two liquids A and B is x, the partial vapour pressure of A is:
(a) (1 – x)PA (b) xPA
x (1 − x)
(c) PA (d) PA
(1 − x) X

4. When mercuric iodide is added to the aqueous solution of potassium iodide, the:
(a) freezing point is raised (b) freezing point is lowered
(c) freezing point does not change (d) boiling point does not change

5. For a dilute solution, Raoult’s law states that

(a) the lowering of vapour pressure is equal to the mole fraction of the solute
(b) the relative lowering of vapour pressure is equal to the mole fraction of the solute
(c) the relative lowering of vapour pressure is proportional to the amount of the solute in
solution.
(d) the vapour pressure of the solution is equal to the mole fraction of the solvent

6. 100 mL of liquid A was mixed with 25 mL of liquid B to give a non-ideal solution of A-B
mixture. The volume of this mixture would be
(a) 75 mL
(b) 125 mL
(c) close to 125 mL but not exceeding 125 mL
(d) just more than 125 mL.

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7. 0.01 M solution each of urea, common salt and Na2SO4 are taken. The ratio of depression
of freezing point is
(a) 1:1:1 (b) 1:2:1
(c) 1:2:3 (d) 2:2:3

8. A X molal solution of a compound in benzene has mole fraction of solute equal to 0.2.
The value of X is
(a) 14 (b) 3.2
(c) 1.4 (d) 2.

9. When mercuric iodide is added to the aqueous solution of potassium iodide, the
(a) freezing point is raised (b) freezing point does not change
(c) freezing point is lowered (d) boiling point does not change.

10. Nitrobenzene freezes at 278.98°C. 0.25 molal solution of a solute in nitrobenzene causes
freezing point depression of 2°C. K f for nitrobenzene is
(a) 2K m –1 (b) 4K m –1
(c) 8K m –1 (d) 12K m –1 .

11. The freezing point of 1 molal NaCl solution assuming NaCl to be 100% dissociated in
water is
(a) –1.86°C (b) –3.72°C
(c) + 1.86°C (d) + –3.72°C.

12. Which one of the following pairs of solution can we expect to be isotonic at the same
temperature?
(a) 0.1 M urea and 0.1 M NaCl (b) 0.1 M urea and 0.2 M MgCl 2
(c) 0.1 M NaCl and 0.1 M Na 2SO 4 (d) 0.1 M Ca(NO3 ) 2 and 0.1 M Na 2SO 4

13. Vapour pressure of a solution of 5 g of a non-electrolyte in 100 g of water at a particular

temperature is 2985 N / m 2 . The vapour pressure of pure water is 3000 N / m 2 , the
molecular weight of the solute is
(a) 60 (b) 120
(c) 180 (d) 380.

14. 0.15 g of a substance dissolved in 15 g of a solvent boiled at a temperature higher by

0.216°C than that of the pure solvent. Find out the molecular weight of the substance.
( K f for solvent is 2.16°C).
(a) 1.01 (b) 10.1
(c) 100 (d) 10.

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15. A 5% solution of cane sugar (Mol. Wt. = 342) is isotonic with 1% solution of substance
X. The molecular weight of X is
(a) 17.12 (b) 68.4
(c) 34.2 (d) 136.2.

16. Which of the following statements is correct, if the intermolecular forces in liquids A, B
and C are in the order A < B < C?
(a) B evaporates more readily than A (b) B evaporates less readily than C
(c) A and B evaporate at the same rate (d) A evaporates more readily than C

17. The vapor pressure of a solvent decreased by 10 mm of Hg when a non-volatile solute

was added to the solvent. The mole-fraction of solute in solution is 0.2. What would be
the mole-fraction of solvent if decrease in vapour pressure is 20 mm of Hg?
(a) 0.8 (b) 0.6
(c) 0.4 (d) 0.2.

18. An ideal solution was obtained by mixing methanol and ethanol. If the partial vapour
pressure of methanol and ethanol are 2.619 kPa and 4.556 kPa respectively, the
composition of vapour (in terms of mole fraction) will be
(a) 0.634 MeOH, 0.365 EtOH (b) 0.365 MeOH, 0.635 EtOH
(c) 0.574 MeOH, 0.326 EtOH (d) 0.173 MeOH, 0.827 EtOH.

19. Vapour pressure of CCl4 at 25°C is 143 mm Hg. 0.5 gm of a non-volatile solute (Mol.
Wt. 65) is dissolved in 100 ml CCl4 . Find the vapour pressure of the solution. (Density of
CCl4 = 1.58 g / cm 3 ).
(a) 141.93 mm (b) 94.39 mm
(c) 199.34 mm (d) 143.99 mm.

LEVEL – II

1. The molal elevation constant is the ratio of the elevation in B.P. to

(a) molarity (b) molality
(c) mole fraction of solute (d) mole fraction of solvent.

2. The osmotic pressure of a 5% solution of cane sugar at 150°C is (Mol. Wt. of cane
sugar = 342)
(a) 4 atm. (b) 3.4 atm.
(c) 3.55 atm. (d) 2.45 atm.

3. Which of the following compounds corresponds Van’t Hoff factor (i) to be equal to 2 for
dilute solution?
(a) K 2SO 4 (b) NaHSO4
(c) Sugar (d) MgSO 4 .

4. Which of the following solutions will have the highest boiling point?

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(a) 1% glucose (b) 1% sucrose

(c) 1% NaCl (d) 1% CaCl 2 .

5. The osmotic pressure of 1 m solution at 27°C is

(a) 2.46 atm (b) 24.6 atm
(c) 1.21 atm (d) 12.1 atm.
6. Very dilute solutions which show deviations (positive or negative) from Raoult’s law are
called
(a) ideal solutions (b) true solutions
(c) non-ideal solutions (d) colloidal solutions.

7. The relative lowering of vapour pressure is equal to the mole fraction of the solution. This
law is called
(a) Henry’s law (b) Raoult’s law
(c) Ostwald’s law (d) Arrhenius law.

8. Molal depression constant for water is 1.86°C. The freezing point of a 0.05 molal solution
of a non-electrolyte in water is
(a) –1.86°C (b) –0.93°C
(c) –0.093C (d) 0.93°C.

9. The freezing point of a 0.05 molal solution of a non-electrolyte in water is

(a) –1.86°C (b) –0.93°C
(c) –0.093°C (d) –0.93°C.

10. The freezing point of equimolal aqueous solution will be highest for
(a) C6 H 5 NH 3Cl (aniline hydrochloride) (b) Ca(NO3 ) 2
(c) La(NO3 )3 (d) C6 H12 O 6 (glucose).

SECTION – II May be more than one choice

1. Which is/are correct statements?

(a) 1 L of 1 N H3PO4 solution contains one-third of molecular weight when it is
completely neutralized by NaOH
(b) 1 L of 1 N H3PO4 solution contains 1 mol of H3PO4 when it is reduced to HPO32 −
(c) 1 L of 1 NH3PO4 solution contains 0.5 mol of H3PO4 when it is reduced to HPO32 −
(d) H3PO4 is a monobasic acid

2. For the following disproportionation reaction 5Br2 + 6OH– → 5Br– + BrO3− + 3H2O
Correct statements are:
(a) equivalent weight of Br2 when it is reduced to Br– is 80

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(b) equivalent weight of Br2 when it is oxidized to BrO3− is 16

(c) equivalent weight of Br2 in the net reaction is 96
(d) equivalent weight of Br– is 80.

3. 0
1 mol benzene (Pbenzene = 42 mm) and 2 mol toluene (Ptoluene
0
= 36mm) will have:
(a) total vapour pressure 38 mm
(b) mol fraction of vapours of benzene above liquid mixture is 7/19
(c) positive deviation from Raoult’s law
(d) negative deviation from Raoult’s law

4. Consider following solutions:

I : 1 M aq. Glucose
II : 1 M aq. Sodium chloride
III : 1 M benzoic acid in benzene
IV : 1 M ammonium phosphate
Select correct statement(s):
(a) All are isotonic solutions (b) III is hypotonic of I, II, IV
(c) I, II, IV are hypertonic of III (d) IV is hypertonic of I, II, III

5. Which is/are correct statement(s)?

(a) when mixture is less volatile, there is positive deviation from Raoult’s law
(b) when mixture is more volatile, there is negative deviation from Raoult’s law
(c) when mixture is less volatile, there is negative deviation from Raoult’s law
(d) when mixture is more volatile, there is positive devation from Raoult’s law

6. When a solute is added to a pure solvent, the

(a) vapour pressure of the solution becomes lower than that of the pure solvent
(b) rate of evaporation of the pure solvent is reduced
(c) solute does not affect the rate of condensation
(d) rate of evaporation of the solution is equal to the rate of condensation of the solution
at a lower vapour pressure than that in the case of the pure solvent

7. According to Raoult’s law the relative decrease in the solvent vapour pressure over the
solution is equal to
(a) the mole fraction of the solvent
(b) the mole fraction of the solute
(c) the number of moles of the solute
(d) i times the mole fraction of the solute which undergoes dissociation or association in
the solvent (i = van’t Hoff factor)

8. Which of the following combinations are correct for a binary solution, in which the solute
as well as the solvent are liquid?
(a) C6H6 and C6H5CH3; ∆Hsoln > 0; ∆Vsol. = 0
(b) CH3COCH3 and CHCl3; ∆Hsoln < 0; ∆Vsol < 0
(c) H2O and HCl; ∆Hsoln > 0; ∆Vsol < 0

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(d) H2O and C2H5OH; ∆Hsoln > 0; ∆Vsol > 0

9. Which of the following statements are correct for a binary solution which shows negative
deviation from Raoult’s law?
(a) The negative deviation from linearity diminishes and tends to zero as the
concentration of the solution component approaches unity
(b) When solutions form, their volumes are smaller than the sum of the volumes of their
components
(c) Heat is released during the formation of the solution
(d) Heat is evolved during the formation of the solution

10. A binary liquid (AB) shows positive deviation from Raoult’s law when
(a) p A > p 0A X liq
A
and p A > p 0B X Bliq (b) Intermolecular forces: A-A, B-B > A-B
(c) ∆Vmix > 0 (d) ∆Hmix > 0

11. The azeotropic solutions of two miscible liquids

(a) can be separated by simple distillation
(b) may show positive or negative deviation from Raoult’ law
(c) are supersaturated solutions
(d) behave like a single component and boil at a constant temperature

12. Which of the following is/are characteristics of hydrophilic solutions?

(a) High concentration of dispersed phase can be easily attained.
(b) Coagulation is reversible
(c) Viscosity and surface tension are nearly same as that of water
(d) The charge of the particle depends on the pH value of the medium; it may be positive,
negative or neutral.

13. A substance effloresces

(a) due to the formation of a crust on its crystal surface
(b) when its vapour pressure is greater than that of the water vapour in air
(c) till it melts
(d) when all of the above happen

14. In which of the following pairs of solutions will the values of the van’t Hoff factor be the
same?
(a) 0.05 M K4[Fe(CN)6] and 0.10 M FeSO4
(b) 0.10 M K4[Fe(CN)6 and 0.05 M FeSO4(NH4)2SO4.6H2O
(c) 0.20 M NaCl and 0.10 M BaCl2
(d) 0.05 M FeSO4(NH4)2SO4.6H2O and 0.02 M KCl.MgCl2 . 6H2O

15. When solute is added to a pure solvent, the

(a) vapuor pressure of the solution becomes lower than the vapors pressure of the pure
solvent

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(b) rate of evaporation of the pure solvent is reduced

(c) solute does not affect the rate of condensation
(d) none of these

16. If P0 and Ps are the vapour pressures of the solvent and its solution respectively and N1
and N2 are the mole fractions of the solvent and solute respectively, then
(a) PS = P0N2 (b) P0 – PS = P0N2
(c) PS = P0 N1 (d) (P0 – PS)/PS = N1/(N1 + N2)

17. Which of the following form ideal solution ?

(a) C6H5Cl — C6H5Br (b) C6H6 — C6H5CH3
(c) Hexane — Heptane (d) Ethanol + Cyclohexane

18. At constant temperature, the osmotic pressure of a solution is

(a) directly proportional to the concentration
(b) inversely proportional to the molecular weight of the solute
(c) directly proportional to the square of the concentration
(d) directly proportional to the square root of the concentration

19. Ideal solution is formed when its components

(a) have zero heat of mixing
(b) have zero volume change
(c) obey Raoult’s law
(d) can be converted into gases

20. In the depression of freezing point experiment, it is found that

(a) The vapour pressure of the solution is less than that of pure solvent
(b) The vapour pressure of the solution is more than that of pure solvent
(c) Only solute molecules solidify at the freezing point
(d) Only solvent molecules solidify at the freezing point

21. The colligative properties of a solution are

(a) ∝ molality
1
(b) ∝ =
molecular mass of the solute
(c) proportional to each other
(d) independent of the nature of the solute, i.e., electrolyte or non-electrolyte

SECTION – III Comprehension Type Questions

Write-up I
According to Raoult’s law (which is applicable for a mixture of volatile liquids) the
partial vapour pressure of a liquid is directly proportional to mol fraction of that

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component. Further assuming ideal behaviour for vapours and applying Dalton’s law we
can write different equations as follows:
PA = PA0 x A , PB = PB0 x B
PTotal = PA + PB = PA0 x A + PB0 x B = PB0 + (PA0 − PB0 )x A
Further mol fraction of a component in vapour phase is equal to the ratio of partial vapour
pressure to total vapour pressure of mixture.
The vapour pressure of two pure liquids A and B which form an ideal solution are 300
and 500 torr respectively at temperature T. A mixture of the vapours of A and B for
which the mol fraction of A is 0.25 is slowly compressed at temperature T.
1. The total pressure when first drop of condensate is formed will be
(a) 428 torr (b) 400 torr
(c) 388 torr (d) 358 torr

2. The pressure when only the last bubble of vapour remains will be
(a) 350 torr (b) 375 torr
(c) 525 torr (d) 450 torr

3. The mol fraction of B in the last bubble of vapour will be

(a) 0.16 (b) 0.84
(c) 0.20 (d) 0.80

Write-up II
Addition of a non-volatile solute always lower the vapour pressure of solvent, therefore, it
will be in equilibrium with solid phase at a lower pressure and hence at a lower
temperature. The difference between the freezing points of the pure solvent and its
solution is called depression of freezing point and depression in freezing point is when
1 mol of solute is dissolved in 1000 gm of solvent is called molal depression constant
(Kf) & Kf for H2O = 1.86 K mol–1kg. To understand this, a solution of 25 % (w/w)
MgCl2 containing impurity of the chloride of a trivalent metal M having atomic mass
43.5 gm (24% by weight of MgCl2) has been prepared. In this solution MgCl2 is
completely dissociated, on the other hand only 50 % dissociation of MCl3 takes place
and molality is approximately equal to molarity.

4. Total moles of solute in the solution is -

(a) 0.6 (b) 0.7
(c) 0.5 (d) 0.8

5. Depression in freezing point of the solution is -

(a) 17.36 (b) 13.02
(c) 14.88 (d) 12.42
6. If the solution is cooled to – 21.7 ºC , will it freeze out . If so what weight of ice will
formed
(a) 15 gm (b) 60 gm

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(c) 40 gm (d) 51 gm

Write-up III

III
P = PA + PB
VP II

XA = 1 Mole fraction XA = 0
XB = 0 XB = 1

The above graph represents the deviation in the vapour pressure as compared to the
expected value according to Raoult’s law.
7. In the above graph deviation is
(a) Positive (b) Negative
(c) No deviation (d) can not be predicted
8. For the negative deviation conditions required are
(a) PA < PA0 × X A ; PB < PB0 × X B (b) PA > PA0 × X A ; PB > PB0 × X B
(c) ∆Hmixing = +ve (d) ∆Vmixing = +ve

9. For the non ideal solutions the conditions are

(a) ∆Hmixing ≠ 0 or + Ve (b) PA = PA0 × XA
(c) PB = PB0 × X B (d) ∆Vmixing = 0

Write-up IV
Colligative properties of a solution depend upon the number of moles of the solute
dissolved and do not depend upon the nature of the solute. However, they are applicable
only to dilute solutions in which the solutes do not undergo any association or
dissociation. For solutes undergoing such changes, van’t Hoff introduced a factor caused
van’t Hoff factor (i). This has helped not only to explain the abnormal molecular masses
of such solutes in the solution but has also helped to calculate the degree of association or
dissociation.

10. Which of the following is a colligative property?

(a) Boiling point (b) Freezing point
(c) Osmotic pressure (d) Vapour pressure

11. During depression of freezing point in a solution, the following are in equilibrium:
(a) liquid solvent, solid solvent (b) liquid solvent, solid solute
(c) liquid solute, solid solute (d) liquid solute, solid solvent

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Write-up V
A solution of sucrose (molar mass = 342) has been prepared by dissolving 68.4g of
sucrose in one kg of water. Kf for water is 1.86 K kg mol–1 and vapour pressure of water
at 298 K is 0.024 atm.

12. The vapour pressure of the solution at 298 K will be

(a) 0.230 atm (b) 0.233 atm
(c) 0.236 atm (d) 0.0239 atm

13. The osmotic pressure of the solution at 298 K will be

(a) 4.29 atm (b) 4.49 atm
(c) 4.69 atm (d) 4.89 atm

14. The freezing point of the solution will be

(a) –0.684°C (b) –0.342°C
(c) –0.372°C (d) –0.186°C

Answers to Assignments
SECTION - I

Level - I

1. (b) 2. (a) 3. (b) 4. (b)

5. (b) 6. (c) 7. (c) 8. (b)
9. (c) 10. (c) 11. (b) 12. (d)
13. (c) 14. (c) 15. (b) 16. (d)
17. (c) 18. (b) 19. (a)

Level - II

1. (b) 2. (c) 3. (d) 4. (d)

5. (b) 6. (c) 7. (b) 8. (c)
9. (c) 10. (d)

SECTION - II

1. (a, c) 2. (a, b, c, d) 3. (a, b) 4. (b, c, d)

5. (c, d) 6. (a, b, c, d) 7. (b, d) 8. (b, d)
9. (a, b, c) 10. (a, b, c) 11. (b, d) 12. (a), (c)
13. (a, b) 14. (b, d) 15. (a, b, c) 16. (b, c)
17. (a, b, c) 18. (a, b) 19. (a, b, c) 20. (a, d)
21. (a, b, c)

LEVEL – III

1. (a) 2. (d) 3. (b) 4. (b)

5. (a) 6. (a) 7. (b) 8. (a)

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9. (a) 10. (c) 11. (a) 12. (d)

13. (d) 14. (c)

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