Molecular masses can be calculated by measuring any of the colligative properties. The relation between colligative properties and molecular mass of the solute is based on following assumptions.
(1) The solution is dilute, so that Raoult‘s law is obeyed.
(2) The solute neither undergoes dissociation nor association in solution. In case of solutions where above assumptions are not valid we find abnormal molar masses.
(i) Association of solute molecules: Certain solutes in solution are found to associate. This eventually leads to a decrease in the number of molecular particles in the solutions. Thus, it results in a decrease in the values of colligative properties therefore higher values are obtained for molecular masses than normal values for unassociated molecules.
(ii) Dissociation of solute molecules: A number of electrolytes dissociate in solution to give two or more particles (ions). Therefore, the number of solute particles, in solutions of such substances, is more than the expected value therefore molecular masses of such substances as calculated from colligative properties will be less than their normal values.
