2.5.2 Non-ideal Solutions

Fig.2.6 The vapour pressures of two component systems as a function of composition (a) a solution that shows positive deviation from Raoult’s law and (b) a solution that shows negative deviation from Raoult’s law.

The cause for these deviations lie in the nature of interactions at the molecular level. In case of positive deviation from Raoult’s law, A-B interactions are weaker than those between A-A or B-B, i.e., in this case the intermolecular attractive forces between the solute-solvent molecules are weaker than those between the solute-solute and solvent-solvent molecules. This means that in such solutions, molecules of A (or B) will find it easier to escape than in pure state. This will increase the vapour pressure and result in positive deviation. Mixtures of ethanol and acetone behave in this manner. In pure ethanol, molecules are hydrogen bonded. On adding acetone, its molecules get in between the host molecules and break some of the hydrogen bonds between them. Due to weakening of interactions, the solution shows positive deviation from Raoult’s law [Fig. 2.6 (a)]. In a solution formed by adding carbon disulphide to acetone, the dipolar interactions between solute-solvent molecules are weaker than the respective interactions among the solute-solute and solvent-solvent molecules. This solution also shows positive deviation.

This decreases the escaping tendency of molecules for each component and consequently the vapour pressure decreases resulting in negative deviation from Raoult’s law [Fig. 2.6. (b)].

Some liquids on mixing, form azeotropes which are binary mixtures having the same composition in liquid and vapour phase and boil at a constant temperature. In such cases, it is not possible to separate the components by fractional distillation. There are two types of azeotropes called minimum boiling azeotrope and maximum boiling azeotrope. The solutions which show a large positive deviation from Raoult’s law form minimum boiling azeotrope at a specific composition. For example, ethanol-water mixture (obtained by fermentation of sugars) on fractional distillation gives a solution containing approximately 95% by volume of ethanol. Once this composition, known as azeotrope composition, has been achieved, the liquid and vapour have the same composition, and no further separation occurs.

The solutions that show large negative deviation from Raoult’s law form maximum boiling azeotrope at a specific composition. Nitric acid and water is an example of this class of azeotrope. This azeotrope has the approximate composition, 68% nitric acid and 32% water by mass, with a boiling point of 393.5 K.