Answer to Question #291951 in Physical Chemistry for Dhanush

Question

Draw and explain the vapour pressure curve of a solution showing positive deviation from Raoult's law

Answer 1

Raoult’s law states that at a given temperature, the vapour pressure of a solution containing non volatile solute is directly proportional the mole fraction of the solvent.

Non ideal solutions show positive and negative deviations from ideal behaviour.

Non ideal solutions showing positive deviations from Raoult’s law-

A solution is said to show positive deviation from Raoult’s Law when at any composition, its vapour pressure is higher than that given by Raoult’s Law.

The positive deviation is shown by those liquid pairs in which the A-B molecular interaction forces are weaker than the corresponding A-A or B-B molecular interaction forces. When the A-B molecular interaction forces are weaker, then molecules of liquid A find it easier to escape as compared to pure solution thereby increasing the vapour pressure of solution.

As a result, each component of solution has a partial vapour pressure greater than expected on the basis of Raoult’s law. This is called positive deviations from Raoult’s law, that is P_A>P_A^oX_A and P_B>P_B^oX_B

∆_mixH [Change in Enthalpy] is positive because energy is required to break A-A & B-B attractive forces. Hence it is an endothermic process.

Examples of liquid Pairs:

1. Water + methanol

2. Water + ethanol

3. Acetone + benzene

4. Carbon tetrachloride + benzene

The graph of vapour pressure and mole fraction for liquids showing positive deviation from Raoult’s Law is shown below:

From the diagram it is clear that the composition curve of such a solution lies above the composition curve obtained on basis of Raoult’s Law.