What are the best methods to separate an azeotrope?

An azeotrope is a constant-boiling mixture in which the composition of the vapour is the same as that of the liquid.

Thus, the two components cannot be separated by fractional distillation.

Here are two methods that that can separate the components of an azeotropic mixture.

Azeotropic distillation

Azeotropic distillation is the addition of a third component to generate a new, lower-boiling azeotrope.

For example, ethanol and water form an azeotropic mixture that contains 95.5 % (m/m) ethanol and boils at 78.1 °C.

To get "absolute" ethanol, we can add benzene to form a new ternary isotope that contains 7.4 % water, 18.5 % ethanol, and 74.1 % benzene and boils at 64.9 °C.

On distillation, the ternary isotope boils off, leaving behind anhydrous ethanol.

Molecular Sieves

A molecular sieve is a material such as a "zeolite" with pores similar in size to small molecules, such as water.

The sieves can be regenerated by heating in a vacuum oven.