Colligative Properties

1. Lowering of vapour pressure of solutions

Let us consider a solution obtained by dissolving 𝑛2 mole of a nonvolatile solute in 𝑛1 mole
of a volatile solvent. In the solution, the mole fractions of the solvent and solute are 𝑥1 and 𝑥2
respectively. Therefore –

𝑛1 𝑛2
𝑥1 = and 𝑥2 =
𝑛1 + 𝑛2 𝑛1 + 𝑛2

If 𝑝1 is the vapour pressure of the solvent over the solution, then according to Raoult’s law –

𝑝1 = 𝑥1 𝑝1 0

Where 𝑝1 0 is the vapour pressure of the pure solvent. Since the solute is nonvolatile, vapour
pressure of the solution is -

𝑝𝑠 = 𝑝1 = 𝑥1 𝑝1 0

𝑝𝑠
= 𝑥1 = 1 − 𝑥2
𝑝1 0

𝑝𝑠
1− = 𝑥2
𝑝1 0

𝑝1 0 − 𝑝𝑠 𝑛2
= 𝑥2 =
𝑝1 0 𝑛1 + 𝑛2

For a dilute solution, 𝑛2 ≫ 𝑛1 . Then -

𝑝1 0 − 𝑝𝑠 𝑛2
=
𝑝1 0 𝑛1

Here 𝑝1 0 − 𝑝𝑠 gives the lowering of vapour pressure due to the addition of the solute and
𝑝 1 0 −𝑝 𝑠
is called the relative lowering of vapour pressure.
𝑝1 0

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 Colligative Properties

Measurement of vapour pressure lowering by Ostwald-Walker method

A stream of dry air is slowly passed through a previously weighed series of bulbs containing
the solution. Air takes up vapour from the solution until it is saturated up to the vapour
pressure of the solution at that temperature i.e. 𝑝1 . Then the bulbs are weighed again. The
loss of weight in this compartment 𝑤1 is proportional to 𝑝1 i.e.

𝑤1 ∝ 𝑝1

𝑤1 = 𝑘𝑝1 𝑘 = 𝑝𝑟𝑜𝑝𝑜𝑟𝑡𝑜𝑜𝑛𝑎𝑙𝑖𝑡𝑦 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

The air, already saturated up to pressure 𝑝1 , is then passed through another series of
previously weighed bulbs containing pure solvent. Since the vapour pressure of the pure
solvent 𝑝1 0 is greater than 𝑝1 , the air will take up some more vapour from the pure
solvent until it gets saturated to 𝑝1 0 . If the corresponding loss in weight is 𝑤2 , then

𝑤2 ∝ 𝑝1 0 − 𝑝1

𝑤2 = 𝑘 𝑝1 0 − 𝑝1

Finally the air is passed through a previously weighed series of U-tubes containing an
absorbent for the vapour of the solvent e.g. anhydrous 𝐶𝑎𝐶𝑙2 for water. The increase in
weight of the U-tubes is proportional to 𝑤1 + 𝑤2 . Therefore

𝑤1 + 𝑤2 ∝ 𝑝1 0

𝑤1 + 𝑤2 = 𝑘𝑝1 0

𝑝1 0 − 𝑝𝑠 𝑤2 𝑘 𝑤2
Hence = =
𝑝1 0 𝑤1 + 𝑤2 𝑘 𝑤1 + 𝑤2

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 Colligative Properties

1. Elevation of boiling point

Suppose a pure solvent is in equilibrium with its vapour at the boiling temperature 𝑇𝑏 under
a constant pressure (usually one atmosphere). At equilibrium –

𝜇1 0 𝑙 = 𝜇1 0 𝑣

Then a non-volatile solute is added to it. As a result, chemical potential of the solvent
decreases. Mole fraction of the solvent in the resulting solution is 𝑥1 say. The equilibrium is
re-established when the temperature is increased from 𝑇𝑏 to 𝑇𝑏 ′ . Suppose under the new
conditions –

𝜇1 𝑙 = 𝜇1 𝑣

𝑑𝜇1 𝑙 = 𝑑𝜇1 𝑣 ……. 1

But 𝜇1 𝑙 = 𝑓 𝑇, 𝑥1

and 𝜇1 𝑣 = 𝑓 𝑇

Here pressure is assumed to be constant because boiling is considered.

𝜕𝜇1 𝑙 𝜕𝜇1 𝑙
Therefore, 𝑑𝜇1 𝑙 = 𝑑𝑇 + 𝑑𝑥1
𝜕𝑇 𝑃,𝑥 1
𝜕𝑥1 𝑃,𝑇

𝜕𝜇1 𝑣
𝑎𝑛𝑑 𝑑𝜇1 𝑣 = 𝑑𝑇
𝜕𝑇 𝑃

Substituting the values of 𝑑𝜇1 𝑙 and 𝑑𝜇1 𝑣 in equation (1) we get –

𝜕𝜇1 𝑙 𝜕𝜇1 𝑙 𝜕𝜇1 𝑣

𝑑𝑇 + 𝑑𝑥1 = 𝑑𝑇 … … . (2)
𝜕𝑇 𝑃,𝑥 1
𝜕𝑥1 𝑃,𝑇
𝜕𝑇 𝑃

Again 𝜇1 𝑙 = 𝜇1 0 𝑙 + 𝑅𝑇 𝑙𝑛 𝑥1

𝜕𝜇1 𝑙 𝑅𝑇
= … … . (3)
𝜕𝑥1 𝑃,𝑇
𝑥1

𝜕𝜇
Also we know that = −𝑆 ……. 4
𝜕𝑇 𝑃

Using (3) and (4) from (2) we get –

𝑑𝑥1
− 𝑆1 𝑙 𝑑𝑇 + 𝑅𝑇 = − 𝑆1 𝑣 𝑑𝑇
𝑥1

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 Colligative Properties

𝑆1 𝑣 − 𝑆1 𝑙 𝑑𝑇 = − 𝑅𝑇 𝑑 𝑙𝑛 𝑥1

∆ 𝑆𝑣𝑎𝑝 𝑑𝑇 = − 𝑅𝑇 𝑑 𝑙𝑛 𝑥1

∆ 𝑆𝑣𝑎𝑝 ∆ 𝐻𝑣𝑎𝑝
𝑑 𝑙𝑛 𝑥1 = − 𝑑𝑇 = − 𝑑𝑇
𝑅𝑇 𝑅𝑇 2

Where ∆ 𝑆𝑣𝑎𝑝 and ∆ 𝐻𝑣𝑎𝑝 are the partial molar entropy and enthalpy of vapourisation
respectively. Now integrating between proper limits we get –

𝑥1 𝑇𝑏 ′ ∆ 𝐻𝑣𝑎𝑝
𝑑 𝑙𝑛 𝑥1 = − 𝑑𝑇
1 𝑇𝑏 𝑅𝑇 2

∆ 𝐻𝑣𝑎𝑝 1 1 ∆ 𝐻𝑣𝑎𝑝 𝑇𝑏 ′ − 𝑇𝑏
𝑙𝑛 𝑥1 = − = −
𝑅 𝑇𝑏 ′ 𝑇𝑏 𝑅 𝑇𝑏 𝑇𝑏 ′

If 𝑥2 is the mole fraction of the solute and 𝑇𝑏 ≅ 𝑇𝑏 ′ then for dilute solutions -

∆ 𝐻𝑣𝑎𝑝 ∆𝑇𝑏
𝑙𝑛 1 − 𝑥2 = − 𝑥2 = −
𝑅 𝑇𝑏 2

𝑹𝑻𝒃 𝟐
∆𝑻𝒃 = 𝒙𝟐
∆ 𝑯𝒗𝒂𝒑

In n, w and M terms represent the number of moles, weight and molecular weight of the
respective components, then for a dilute solution –

𝑛2 𝑛2 𝑤2 𝑀2 𝑤2 𝑀1
𝑥2 = ≅ = =
𝑛1 + 𝑛2 𝑛1 𝑤1 𝑀1 𝑤1 𝑀2

𝑅𝑇𝑏 2 𝑤2 𝑀1 × 1000
∴ ∆𝑇𝑏 =
∆ 𝐻𝑣𝑎𝑝 𝑤1 𝑀2 × 1000

𝑅𝑇𝑏 2 𝑀1
= 𝑚 𝑤ℎ𝑒𝑟𝑒 𝑚 = 𝑚𝑜𝑙𝑎𝑙𝑖𝑡𝑦
∆ 𝐻𝑣𝑎𝑝 1000

𝑅𝑇𝑏 2 𝑚
=
∆ 𝐻𝑣𝑎𝑝 𝑀1 1000

𝑹𝑻𝒃 𝟐
∆𝑻𝒃 = 𝒎 = 𝑲𝒃 𝒎
𝟏𝟎𝟎𝟎 𝒍𝒗

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 Colligative Properties

Where 𝑙𝑣 is the latent heat of vapourisation per gram of solvent and 𝐾𝑏 is called the
ebullioscopic constant or molal elevation constant.

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