Colligative Properties

3. Depression of freezing point

The freezing point of a substance is the temperature at which solid and liquid states coexist
i.e. the two states have same vapour pressure. When a non volatile solute is added to the
solvent, the vapour pressure of the solution is lowered. Now both phases will have the same
vapour pressure at a lower temperature. Hence a depression in freezing point is observed.

The curves AB and BC represent the vapour pressure curves of the liquid solvent and the
solid solvent respectively. At point B, the vapour pressures of both phases are equal. The
corresponding temperature is the normal freezing point 𝑇𝑓 of the pure solvent.

When a non volatile solute is added to the solvent, vapour of the solution is lowered. This is
represented by the curve DEF. This curve meets the vapour pressure curve of the solid at
′
point F. The corresponding temperature 𝑇𝑓 is lower than the normal freezing point 𝑇𝑓 of
the pure solvent. Hence freezing point of the solution is lowered.

Suppose a pure liquid solvent is in equilibrium with the solid solvent at the normal freezing
point 𝑇𝑓 . At equilibrium –

𝜇1 0 𝑙 = 𝜇1 0 𝑠

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 decreased from 𝑇𝑓 to 𝑇𝑓 ′ . Suppose under the new
conditions –

𝜇1 𝑙 = 𝜇1 𝑠

𝑑𝜇1 𝑙 = 𝑑𝜇1 𝑠 ……. 1

Page 1
 Colligative Properties

But 𝜇1 𝑙 = 𝑓 𝑇, 𝑥1

and 𝜇1 𝑠 = 𝑓 𝑇

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

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

𝜕𝜇1 𝑠
𝑎𝑛𝑑 𝑑𝜇1 𝑠 = 𝑑𝑇
𝜕𝑇 𝑃

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

𝜕𝜇1 𝑙 𝜕𝜇1 𝑙 𝜕𝜇1 𝑠

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 𝑠 𝑑𝑇
𝑥1

𝑅𝑇 𝑑 𝑙𝑛 𝑥1 = 𝑆1 𝑙 − 𝑆1 𝑠 𝑑𝑇

∆ 𝑆𝑓𝑢𝑠 ∆ 𝐻𝑓𝑢𝑠
𝑑 𝑙𝑛 𝑥1 = 𝑑𝑇 = 𝑑𝑇
𝑅𝑇 𝑅𝑇 2

Where ∆ 𝑆𝑓𝑢𝑠 and ∆ 𝐻𝑓𝑢𝑠 are the partial molar entropy and enthalpy changes of fusion
respectively. Now integrating between proper limits we get –

𝑥1 𝑇𝑓 ′ ∆ 𝐻𝑓𝑢𝑠
𝑑 𝑙𝑛 𝑥1 = 𝑑𝑇
1 𝑇𝑓 𝑅𝑇 2

∆ 𝐻𝑓𝑢𝑠 1 1 ∆ 𝐻𝑓𝑢𝑠 𝑇𝑓 − 𝑇𝑓 ′
𝑙𝑛 𝑥1 = − ′ − 𝑇 = −
𝑅 𝑇𝑓 𝑓 𝑅 𝑇𝑓 𝑇𝑓 ′

Page 2
 Colligative Properties

If 𝑥2 is the mole fraction of the solute and 𝑇𝑓 ≅ 𝑇𝑓 ′ , then for dilute solutions –

∆ 𝐻𝑓𝑢𝑠 ∆𝑇𝑓
𝑙𝑛 1 − 𝑥2 = − 𝑥2 = −
𝑅 𝑇𝑓 2

𝑹𝑻𝒇 𝟐
∆𝑻𝒇 = 𝒙𝟐
∆ 𝑯𝒇𝒖𝒔

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

𝑅𝑇𝑓 2 𝑤2 𝑀1 × 1000
∴ ∆𝑇𝑓 =
∆ 𝐻𝑓𝑢𝑠 𝑤1 𝑀2 × 1000

𝑅𝑇𝑓 2 𝑀1
= 𝑚 𝑤ℎ𝑒𝑟𝑒 𝑚 = 𝑚𝑜𝑙𝑎𝑙𝑖𝑡𝑦
∆ 𝐻𝑓𝑢𝑠 1000

𝑅𝑇𝑓 2 𝑚
=
∆ 𝐻𝑓𝑢𝑠 𝑀1 1000

𝑹𝑻𝒇 𝟐
∆𝑻𝒇 = 𝒎 = 𝑲𝒇 𝒎
𝟏𝟎𝟎𝟎 𝒍𝒇

Where 𝑙𝑓 is the latent heat of fusion per gram of solvent and 𝐾𝑓 is called the molal cryoscopic
constant or molal depression constant.

Thus we see that ∆𝑇𝑓 is proportional to the molality of the solution i.e. number of solute
particles per 1000 gm of the solvent. So it is a colligative property. This implies that if
equimolecular amounts of different solutes are dissolved in the same amount of a given
solvent separately, ∆𝑇𝑓 will be the same in each case.

4. Osmosis and osmotic pressure 𝝅

If a pure solvent and its solution are kept separated by a semi permeable membrane, only the
solvent molecules will pass through the membrane into the solution until the chemical
potential of the solvent becomes equal in the two chambers. This process is known as
osmosis.
The diffusion of the solvent into the solution can be stopped by applying a pressure over the
solution. The osmotic pressure 𝜋 of a solution is defined as the pressure which must be

Page 3
 Colligative Properties

applied on the solution to prevent osmosis, when the solution is separated from the pure
solvent by a semipermeable membrane.

Thermodynamic derivation of osmotic pressure

Initially in both sides of the semipermeable membrane, there is pure
solvent whose chemical potential is 𝜇1 0 . The pressure over the solvent is
𝑃0 . Then some solute is added to the left hand side. As a result, chemical
potential of the solvent decreases. In the resulting solution, mole fractions
of the solvent and the solute are 𝑥1 and 𝑥2 respectively. Now the solvent
will pass from right hand side to the solution. To prevent this flow,
pressure over the solution is increased to 𝑃. So the chemical potential of
the solvent in the solution also increases to 𝜇1 say. The temperature is
kept constant throughout the experiment. At equilibrium

𝜇1 𝐿𝐻𝑆 = 𝜇1 0 𝑅𝐻𝑆

𝑑𝜇1 𝐿𝐻𝑆 = 𝑑𝜇1 0 𝑅𝐻𝑆 = 0

But 𝜇1 𝐿𝐻𝑆 = 𝑓 𝑃, 𝑥1

𝜕𝜇1 𝐿𝐻𝑆 𝜕𝜇1 𝐿𝐻𝑆

∴ 𝑑𝜇1 𝐿𝐻𝑆 = 𝑑𝑃 + 𝑑𝑥1 = 0 … … . (1)
𝜕𝑃 𝑇,𝑥 1
𝜕𝑥1 𝑇,𝑃

If the solution behaves ideally, 𝜇1 𝐿𝐻𝑆 = 𝜇1 0 𝐿𝐻𝑆 + 𝑅𝑇 𝑙𝑛 𝑥1

𝜕𝜇1 𝐿𝐻𝑆 𝑅𝑇
∴ =
𝜕𝑥1 𝑇,𝑃
𝑥1

𝜕𝜇
Also we know that = 𝑉 = molar volume
𝜕𝑃 𝑇

Hence equation (1) can be written as –

𝑅𝑇
𝑉1 𝑑𝑃 + = 0
𝑥1

𝑅𝑇
𝑑𝑃 = − 𝑑 𝑙𝑛𝑥1
𝑉1

Integrating between proper limits –

Page 4
 Colligative Properties

𝑃 𝑥1
𝑅𝑇
𝑑𝑃 = − 𝑑 𝑙𝑛𝑥1
𝑃0 1 𝑉1

Since liquids are rather incompressible, 𝑉1 may taken as constant. Then –

𝑅𝑇 𝑅𝑇
𝑃 − 𝑃0 = − 𝑙𝑛 𝑥1 = − 𝑙𝑛 1 − 𝑥2
𝑉1 𝑉1

In dilute solutions, 𝑥2 ≪ 1 and 𝑙𝑛 1 − 𝑥2 = − 𝑥2

𝑅𝑇
∴ Osmotic pressure 𝜋 = 𝑃 − 𝑃0 = 𝑥2
𝑉1

If 𝑛1 and 𝑛2 are the number of moles of the solvent and solute respectively, then –

𝑅𝑇 𝑛2 𝑅𝑇 𝑛2
𝜋 = ≅
𝑉1 𝑛1 + 𝑛2 𝑉1 𝑛1

For dilute solutions, 𝑛2 is very small. So volume of solution V = 𝑛1 𝑉1 + 𝑛2 𝑉2

≅ 𝑛1 𝑉1

𝑅𝑇
∴ 𝜋 = 𝑛
𝑉 2

𝜋 = 𝐶𝑅𝑇

Where 𝐶 is the molar concentration of the solute. This is known as van’t Hoff law of osmotic
pressure.

Page 5