Azeotrope

An azeotrope or a constant boiling mixture is a mixture of two or more liquids whose proportions cannot be altered by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture.

Because their composition is unchanged by distillation, azeotropes are also called (especially in older texts) constant boiling mixtures. The word azeotrope is derived from the Greek words ζέειν (boil) and τρόπος (turning) combined with the prefix α- (no) to give the overall meaning, "no change on boiling". The term "azeotrope" was coined in 1911 by English chemist John Wade (1864–1912) and Richard William Merriman.

Many azeotropic mixtures of pairs of compounds are known, and many azeotropes of three or more compounds are also known. In such a case it is not possible to separate the components by fractional distillation. There are two types of azeotropes: minimum boiling azeotrope and maximum boiling azeotrope. A solution that shows greater positive deviation from Raoult's law forms a minimum boiling azeotrope at a specific composition. For example, an ethanol-water mixture (obtained by fermentation of sugars) on fractional distillation yields a solution containing approximately 95% by volume of ethanol. Once this composition has been achieved, the liquid and vapour have the same composition, and no further separation occurs. A solution that shows large negative deviation from Raoult's law forms a maximum boiling azeotrope at a specific composition. Nitric acid and water is an example of this class of azeotrope. This azeotrope has an approximate composition of 68% nitric acid and 32% water by mass, with a boiling point of 393.5 K.

Each azeotrope has a characteristic boiling point. The boiling point of an azeotrope is either less than the boiling point temperatures of any of its constituents (a positive azeotrope), or greater than the boiling point of any of its constituents (a negative azeotrope).

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