Explain why the colligative properties may not apply to solutions containing volatile solutes.

The colligative properties really depend on the escaping tendency of solvent molecules from the liquid phase. You will recall that the vapor pressure is a direct measure of escaping tendency, so we can use these terms more or less interchangeably.

The tendency of molecules to escape from a liquid phase into the gas phase depends in part on how much of an increase in entropy can be achieved in doing so. Evaporation of solvent molecules from the liquid always leads to a large increase in entropy because of the greater volume occupied by the molecules in the gaseous state. But if the liquid solvent is initially “diluted“ with solute, its entropy is already larger to start with, so the amount by which it can increase on entering the gas phase will be less. There will accordingly be less tendency for the solvent molecules to enter the gas phase, and so the vapor pressure of the solution diminishes as the concentration of solute increases and that of solvent decreases.

Explanation: