Composition of Liquid and Vapour in Equilibrium:

The total vapour pressure P is the sum of the two partial pressures, i.e., P = p1 + p2;

Hence, since N2 is equal to 1 – N1. Therefore, P = N1 p1□ + N2 p2□

P = N1 p1□ + (1 – N1) p2□
P = N1 p1□ + p2□ – N1 p2□
P = N1 p1□ – N1 p2□ + p2□
P = p2□ + N1 (p1□ – p2□) ----- (1)
so that the total vapour pressure also varies in a linear manner with the mole fraction of either component in the
liquid phase.

The composition of the vapour phase in equilibrium with any liquid solution is readily derived from the fact that
the number of moles (or the mole fraction) of each constituent in the vapour must be proportional to its partial
pressure, assuming the vapour to behave as an ideal gas. If N′1 and N′2 represent the mole fractions of the two
components in the vapour, then

N′1 𝑝1 N1 𝑝1□
= = ----- (2)
N′2 𝑝2 N2 𝑝2□

provided Raoult’s law is applicable.

By replacing N′2 by 1 – N′1 ; and N2 by 1 – N1 in equation (2), and then combining it with equation (1) so as to
eliminate N1, it follows that

𝑝1□ 𝑝2□
P= ----- (3)
𝑝□
1 − N′1 (𝑝1□ − 𝑝2□ )

From this result it is possible to calculate the total vapour pressure P for any value N′1, the mole fraction of the
constituent 1 in the vapour. It is evident from equation (3) that the total vapour pressure is not a linear function
of the mole fraction composition of the vapour, although it is such a function of the composition of the liquid
phase, in the case of an ideal solution. By utilizing either equation (1) or (3) it is possible to plot the variation of
the total pressure with the mole fraction of either constituent of the vapour.