1.

Solution and Colligative Properties

Solution:
i. A solution is defined as a homogeneous mixture of two or more
substances whose composition can be varied within certain limits.
ii. The dissolved substance may be present as individual molecules or ions
throughout the other substance. Every solution contains solvent and one
or more solutes.
iii. The component in which solution formation takes place and which
constitutes larger proportion of a solution is called the solvent.
iv. The other component which dissolves and constitutes smaller proportion
of a solution is called the solute.
v. The extent to which a substance dissolves in another substance depends
on the nature of the solute and solvent, temperature and pressure.
vi. The effect of pressure is important for solutions which involve gases.
vii. The effect of temperature is usually very pronounced and depends upon
the heat of solution.
viii. Solutions containing two, three and four components are termed as
binary, tertiary and quaternary solutions respectively.

Types of solution:
Gaseous solution
i. Gas in Gas Air, mixture of non reacting gases and vapours
ii. Liquid in Gas Chloroform mixed with nitrogen gas
iii. Solid in Gas I2 in air

Liquid solution
i. Gas in Liquid CO2 dissolved in H2O
ii. Liquid in Liquid Ethyl alcohol in water
iii. Solid in Liquid Sugar in water

Solid solution
i. Gas in Solid H2 gas in palladium metal
ii. Liquid in Solid Amalgam of Hg with sodium
iii. Solid in Solid Alloys, Copper in gold, Brass

Concentration of Solution:
The amount of solute dissolved in a unit volume of solvent is termed as
concentration of solution.
Solution with low concentrations of solute are called dilute solutions and
those containing relatively high concentrations are called concentrated solutions.
Polar substances are soluble in polar solvents (salt in water) and non
polar substances are soluble in non polar solvents (naphthalene in benzene)
[ ‘like dissolves like’ rule of solubility ]

Colligative properties:
The properties of solution which depend on only the number of solute
particles in a solution and do not depend on its nature are called colligative
properties.
e.g.
i. relative lowering of vapour pressure
ii. elevation of boiling point,
iii. depression of freezing point and
iv. osmotic pressure.

Vapour pressure of liquids

All liquids exhibit tendency for evaporation(volatile liquids). When the
vessel containing liquid is closed, the process of evaporation continues.
The molecules of the liquid escaping from the surface of liquid remain in
the container above the surface of the liquid.
These molecules of vapour along with the gas molecules are in continuous
random motion; they collide with each other, with the walls of the container and
also with the surface of the liquid and return to the liquid state. This reverse
phenomenon is called condensation.
After some interval of time, an equilibrium is established between two
phases of the substance, when the rate of evaporation equals the rate of
condensation.
Vapour pressure of a liquid is the pressure exerted by the vapours in
equilibrium with the liquid at a particular temperature.

Vapour pressure lowering:

i. The vapour pressure of a liquid solvent is lowered when a non volatile
solute is dissolved in it to form a solution.
ii. This is due to fact that in case of pure solvent, its surface area is
completely occupied by volatile solvent molecules.
iii. While in case of solution of non volatile solute, its surface area is not
completely available for volatile solvent; partly it is occupied by non-
volatile solute.
 Hence the rate of evaporation will be less as compared to that of pure
solvent and vapour pressure of solution is lower than that of the pure
solvent.

Experiment:
Consider that there are three beakers numbered 1, 2, and 3 containing 100
3
cm each of pure solvent, 1M CuSO4 solution and 2M CuSO4 solution respectively.
The three beakers are placed in airtight desiccators, so that at constant
temperature, in solvent from all the three beakers, equilibrium of evaporation and
condensation is attained.
At equilibrium it is observed that solvent in beaker no.1 evaporates
completely and it is empty.
Concentration of CuSO4 solution does not change in beaker no. 2 ; volume
of solution remains almost same.
However in case of beaker no. 3 the condensation of solvent takes place;
volume of solution becomes almost 200cm3 and concentration of solution
becomes almost 1M which is almost equal to concentration of solution in beaker
no. 2
The experimental results suggest that vapour pressure of pure solvent water
is maximum, that of 2M CuSO4 solution is minimum and that of 1M CuSO4 is
intermediate.
Hence there is lowering of vapour pressure of solvent in solution of non
volatile solute. If p1° is the vapour pressure of pure solvent and p is the vapour
pressure of the solution of non-volatile solute in the same solvent, then p¿ p1°
and the lowering of vapour pressure,
∆ p = p1° −¿ p

The difference between vapour pressure of pure solvent and the vapour
pressure of solvent from solution is called vapour pressure lowering.

The relative lowering of vapour pressure:

The relative lowering of vapour pressure for the given solution is the ratio
of vapour pressure lowering solvent from solution to the vapour pressure of pure
∆p p 1 °− p
solvent. Thus relative lowering of vapour pressure = p ° =
p1 °
.
1

Raoult’s law:
The partial vapour pressure of any volatile component of a solution is the
product of vapour pressure of that pure component and the mole fraction of the
component in the solution.
 Consider a solution containing two volatile components A1 and A2 with
the mole fractions x1 and x2 respectively.
Let p1 ° and p2 ° be the vapour pressures of the pure components A1 and A2
respectively. According to Raoult’s law, p1 and p2 of two components is given by,

p1= p1 ° x 1 and p2= p2 ° x 2

and total vapour pressure pT of solution of two volatile components is the

sum of partial vapour pressures of two components.
Hence, pT = p1 + p 2 = p1 ° x 1 + p 2 ° x 2

For binary solutions, x 1+ x2=1∨x 2=1−x 1

Hence, pT = p1 ° x 1+ p2 ° (1−x 1)
¿ p1 ° x 1+ p 2 °− p2 ° x 1

pT = p2 ° + ( p1 °− p2 ° ) x 1

The solution which obeys Raoult’s law over the entire range of
concentration is called ideal solution.

Raoult’s law for a solution of non-volatile solute:

Consider a solution of two components A1 and A2 with mole fractions x1 and

x2 respectively. Here, component A2 is non-volatile, hence does not evaporate
and does not contribute to the total vapour pressure of solution. The vapour
pressure of pure component A1 is p1 ° and that of the component A2 is p2 ° =0.
Hence, vapour pressure of solution will be vapour pressure, p of solvent
alone in solution and is obtained by substituting p2 ° =0 in eq.

pT = p2 ° + ( p1 °− p2 ° ) x 1

∴ p= p 2 ° + ( p1 ° −p 2 ° ) x 1 ;
as p2 ° =0

p=0+ ( p1 ° −0 ) x 1
i.e. p= p1 ° x 1
For two component solution, x 1+ x2=1∨x 2=1−x 1
∴ x 1< 1 & p1 ° < p1 ° x 1
 ∴ p< p1 °

The lowering of vapour pressure ∆ p=p 1 °− p

¿ p1 ° −p 1 ° x1
¿ p1 ° (1−x 1)

But 1−x 1=x 2

Hence, ∆ p=p 1 ° x 2

This shows that lowering of vapour pressure depends on nature of pure

solvent and concentration of solute in mole fraction.

Now the relative lowering of vapour pressure is given by,

∆ p p 1 °− p p1 ° x 2
= = =x 2
p1° p1 ° p1°

Hence, relative lowering of vapour pressure¿ x 2

The equation shows that relative lowering of vapour pressure is a colligative

property as it depends only on concentration of the non-volatile solute.

Molar mass of solute and relative lowering of vapour pressure:

Let W2 g of solute of molar mass M2 be dissolved in W1 g of solvent of
molar mass M1. Hence no. of moles of solvent, n 1 and no. of moles of solute n 2 in
solution are given as
W1 W2
n1 = and n2 =
M1 M2

The mole fraction of solute, x 2 is given by

n2 W 2/ M 2
x 2= =
n1 +n2 W 1 / M 1 +W 2 /M 2

∆ p p 1 °− p
Combining above equation and equation
p1°
=
p1 °
;

∆ p p 1 °− p W 2 /M 2
= =x 2=
p1° p1 ° W 1 / M 1+ W 2 / M 2
For dilute solutions n1 ≫ n2. Hence, n2 may be neglected in comparison with n1 in
equation.

∆ p n2 W 2 /M 2 W 2 M 1
∴ = = =
p 1 ° n1 W 1 /M 1 W 1 M 2