An azeotrope () or a constant heating point mixture is a mixture of two or more components in fluidic states whose proportions cannot be altered or changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Azeotropic mixture behavior is important for fluid separation processes.
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). For both positive and negative azeotropes, it is not possible to separate the components by fractional distillation and azeotropic distillation is usually used instead.
For technical applications, the pressure-temperature-composition behavior of a mixture is the most important. Yet, also other important thermophysical properties are strongly influenced by azeotropy, e.g. the surface tension and transport properties.
Some azeotropic mixtures of pairs of compounds are known, and many azeotropes of three or more compounds are also known.
Etymology
The term azeotrope is derived from the Greek words ζέειν (boil) and τρόπος (turning) with the prefix α- (no) to give the overall meaning, "no change on boiling". The term was coined in 1911 by English chemist John Wade and Richard William Merriman. Because their composition is unchanged by distillation, azeotropes are also called (especially in older texts) constant boiling point mixtures.
Types
Positive azeotropes
A solution that shows greater positive deviation from Raoult's law forms a minimum boiling azeotrope at a specific composition. In general, a positive azeotrope boils at a lower temperature than any other ratio of its constituents. Positive azeotropes are also called minimum boiling mixtures or pressure maximum azeotropes. A well-known example of a positive azeotrope is an ethanol–water mixture (obtained by fermentation of sugars) consisting of 95.63% ethanol and 4.37% water (by mass), which boils at 78.2 °C. Ethanol boils at 78.4 °C, water boils at 100 °C, but the azeotrope boils at 78.2 °C, which is lower than either of its constituents. Indeed, 78.2 °C is the minimum temperature at which any ethanol/water solution can boil at atmospheric pressure. Once this composition has been achieved, the liquid and vapour have the same composition, and no further separation occurs.
The boiling and recondensation of a mixture of two solvents are changes of chemical state; as such, they are best illustrated with a phase diagram. If the pressure is held constant, the two variable parameters are the temperature and the composition.
The adjacent diagram shows a positive azeotrope of hypothetical constituents, X and Y. The bottom trace illustrates the boiling temperature of various compositions. Below the bottom trace, only the liquid phase is in equilibrium. The top trace illustrates the vapor composition above the liquid at a given temperature. Above the top trace, only the vapor is in equilibrium. Between the two traces, liquid and vapor phases exist simultaneously in equilibrium: for example, heating a 25% X : 75% Y mixture to temperature AB would generate vapor of composition B over liquid of composition A. The azeotrope is the point on the diagram where the two curves touch. The horizontal and vertical steps show the path of repeated distillations. Point A is the boiling point of a nonazeotropic mixture. The vapor that separates at that temperature has composition B. The shape of the curves requires that the vapor at B be richer in constituent X than the liquid at point A. The vapor is physically separated from the VLE (vapor-liquid equilibrium) system and is cooled to point C, where it condenses. The resulting liquid (point C) is now richer in X than it was at point A. If the collected liquid is boiled again, it progresses to point D, and so on. The stepwise progression shows how repeated distillation can never produce a distillate that is richer in constituent X than the azeotrope. Note that starting to the right of the azeotrope point results in the same stepwise process closing in on the azeotrope point from the other direction.