Colligative properties

1. Define or explain the following terms :

(a) Colligative Properties (Greek colligatus = Collected together).

Dilute solutions containing non-volatile solute exhibit the following properties :

Raoult’s law
The relative lowering of the vapour pressure of a dilute solution is equal to the mole fraction of the solute
present in dilute solution.
The vapour pressure of a pure solvent is decreased when a non-volatile solute is dissolved in it.
If p is the vapour pressure of the solvent and ps that of the solution, the lowering of vapour pressure
is (p – ps).
P − Ps
Relative Lowering of Vapour Pressure =
P
P − Ps n
Raoult’s Law can be expressed mathematically in the form: =
P n+N
where n = number of moles or molecules of solute
N = number of moles or molecules of solvent.

2. Derive Roult’s Law from lowering of vapour pressure.

The vapour pressure of the pure solvent is caused by the number of molecules evaporating from its
surface. When a nonvolatile solute is dissolved in solution, the presence of solute molecules in the surface
blocks a fraction of the surface where no evaporation can take place.
 Figure:Lowering of vapour pressure by a nonvolatile solute. The particles of the solute block the escape of
solvent molecules from the surface of the solution.

This causes the lowering of the vapour pressure. The vapour pressure of the solution is, therefore, determined by the
number of molecules of the solvent present at any time in the surface which is proportional to the mole fraction.

N
That is, Ps ∞ where N = moles of solvent and n = moles of solute.
n+N

N
Or Ps = k ……………….(1) k is proportionally constant
n+N

N N
In case of pure solvent n = 0 and hence mole fraction of solvent = = =1
n+N 0+N
Now from eq. 1 the vapour pressure p = k
N
Therefore the eq. 1 assumes the form Ps = P
n+N

Ps N
=
P n+N

Ps N
Or, 1 − =1−
P n+N

P − Ps n
Or, = , this is Roult’s law.
P n+N

Problem : Calculate the vapour pressure lowering caused by the addition of 100 g of sucrose (mol mass = 342)
to 1000 g of water if the vapour pressure of pure water at 25°C is 23.8 mm Hg.
Elevation of boiling point:
When a liquid is heated, its vapour pressure rises and when it equals the atmospheric pressure, the liquid
boils. The addition of a non volatile solute lowers the vapour pressure and consequently elevates the
boiling point as the solution has to be heated to a higher temperature to make its vapour pressure become
equal to atmospheric pressure. If Tb is the boiling point of the solvent and T is the boiling point of the
solution, the difference in the boiling points (ΔT) is called the elevation of boiling point. T-Tb = ΔT

Relation between Boiling point elevation and vapour pressure lowering

The vapour pressure curves of the pure solvent, and solutions (1) and (2) with different concentrations of
solute are shown in Fig.2

Fig.2: Ostwald
-Walker method
of
measuring the relative lowering of vapour pressure.

For dilute solutions, the curves BD and CE are parallel and straight lines approximately. Therefore

AB AD T1 − Tb P − P1
for similar triangles ACE and ABD, we have = or =
AC AE T2 − Tb P − P2

where p – p1 and p – p2 are lowering of vapour pressure for solution 1 and solution 2 respectively. Hence
the elevation of boiling point is directly proportional to the lowering of vapour pressure.
Or, ΔT α P-Ps

Freezing point depression /relation between freezing point depression and vapour-pressure
lowering

The vapour pressure of a pure liquid changes with temperature as shown by the curve ABC, in Fig. 3.
There is a sharp break at B where, in fact, the freezing-point curve commences. Thus the point B
corresponds to the freezing point of pure solvent, Tf. The vapour pressure curve of a solution (solution 1)
of a nonvolatile solute in the same solvent is also shown in Fig.3 It is similar to the vapour pressure curve
of the pure solvent and meets the freezing point curve at F, indicating that T1is the freezing point of the
solution. The difference of the freezing point of the pure solvent and the solution is referred to as the
Depression of freezing point. It is represented by the symbol ΔT or ΔTf .

Tf − T1 = ∆ T
 Fig. 3: Relation between lowering of vapour-pressure and depression of freezing point.

When more of the solute is added to the solution 1, we get a more concentrated solution (solution 2.)
The vapour pressure of solution 2 meets the freezing-point at C, indicating a further lowering of freezing
point to T2. For dilute solutions FD and CE are approximately parallel straight lines and BC is also a
DF BD Tf − T1 P − P1
=
straight line. Since the triangles BDF and BEC are similar, or, =
EC BE Tf − T1 P − P2
where p1 and p2 are vapour pressure of solution 1 and solution 2 respectively. Hence depression of
freezing point is directly proportional to the lowering of vapour pressure. Or ΔT α P-Ps