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azeotropic distillation[¦āz·ē·a‚trō·pik ‚dis·tə′lā·shən]
Any of several processes by which liquid mixtures containing azeotropes may be separated into their pure components with the aid of an additional substance (called the entrainer, the solvent, or the mass separating agent) to facilitate the distillation. Distillation is a separation technique that exploits the fact that when a liquid is partially vaporized the compositions of the two phases are different. By separating the phases, and repeating the procedure, it is often possible to separate the original mixture completely. However, many mixtures exhibit special states, known as azeotropes, at which the composition, temperature, and pressure of the liquid phase become equal to those of the vapor phase. Thus, further separation by conventional distillation is no longer possible. By adding a carefully selected entrainer to the mixture, it is often possible to “break” the azeotrope and thereby achieve the desired separation.
Entrainers fall into at least four distinct categories that may be identified by the way in which they make the separation possible. These categories are: (1) liquid entrainers that do not induce liquid-phase separation, used in homogeneous azeotropic distillations, of which classical extractive distillation is a special case; (2) liquid entrainers that do induce a liquid-phase separation, used in heterogeneous azeotropic distillations; (3) entrainers that react with one of the components; and (4) entrainers that dissociate ionically, that is, salts. See Salt-effect distillation
Within each of these categories, not all entrainers will make the separation possible, that is, not all entrainers will break the azeotrope. In order to determine whether a given entrainer is feasible, a schematic representation known as a residue curve map for a mixture undergoing simple distillation is created. The path of liquid compositions starting from some initial point is the residue curve. The collection of all such curves for a given mixture is known as a residue curve map (see illustration). These maps contain exactly the same information as the corresponding phase diagram for the mixture, but they represent it in such a way that it is more useful for understanding and designing distillation systems.
Mixtures that do not contain azeotropes have residue curve maps that all look the same. The presence of even one binary azeotrope destroys the structure. If the mixture contains a single minimum-boiling binary azeotrope, three residue curve maps are possible, depending on whether the azeotrope is between the lowest- and highest-boiling components, between the intermediate- and highest-boiling components, or between the intermediate- and lowest-boiling components.
Nonazeotropic mixtures may be separated into their pure components by using a sequence of distillation columns because there are no distillation boundaries to get in the way. The situation is quite different when azeotropes are present, as can be seen from the illustration. It is possible to separate mixtures that have residue curve maps similar to those shown in illus. a and c by straightforward sequences of distillation columns. This is because these maps do not have any distillation boundaries. These, and other feasible separations for more complex mixtures, are referred to collectively as homogeneous azeotropic distillations. Without exploiting some other effect (such as changing the pressure from column to column), it is impossible to separate mixtures that have residue curve maps like illus. b.
A large number of mixtures have residue curve maps similar to illus. c, and therefore the corresponding distillation is given the special name extractive distillation.
Heterogeneous entrainers cause liquid-liquid phase separations to occur in such a way that the composition of each phase lies on either side of a distillation boundary. In this way, the entrainer allows the separation to “jump” over a boundary that would otherwise be impassable.