Azeotrope


An azeotrope or a constant heating point mixture is a mixture of two or more liquids whose proportions cannot be changed by simple distillation. This happens because when an azeotrope is boiled, the vapour has the same proportions of constituents as the unboiled mixture. Knowing an azeotrope's behavior is important for distillation.
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, or greater than the boiling point of any of its constituents. 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, but other important thermophysical properties are also strongly influenced by azeotropy, including the surface tension and transport properties.

Etymology

The term azeotrope is derived from the Greek words ζέειν and τρόπος with the prefix α- 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 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 consisting of 95.63% ethanol and 4.37% water, 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 system and is cooled to point C, where it condenses. The resulting liquid 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.

Negative azeotropes

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. In general, a negative azeotrope boils at a higher temperature than any other ratio of its constituents. Negative azeotropes are also called maximum boiling mixtures or pressure minimum azeotropes. An example of a negative azeotrope is hydrochloric acid at a concentration of 20.2% and 79.8% water. Hydrogen chloride boils at −85 °C and water at 100 °C, but the azeotrope boils at 110 °C, which is higher than either of its constituents. The maximum boiling point of any hydrochloric acid solution is 110 °C. Other examples:
The adjacent diagram shows a negative azeotrope of ideal constituents, X and Y. Again the bottom trace illustrates the boiling temperature at various compositions, and again, below the bottom trace the mixture must be entirely liquid phase. The top trace again illustrates the condensation temperature of various compositions, and again, above the top trace the mixture must be entirely vapor phase. The point, A, shown here is a boiling point with a composition chosen very near to the azeotrope. The vapor is collected at the same temperature at point B. That vapor is cooled, condensed, and collected at point C. Because this example is a negative azeotrope rather than a positive one, the distillate is farther from the azeotrope than the original liquid mixture at point A was. So the distillate is poorer in constituent X and richer in constituent Y than the original mixture. Because this process has removed a greater fraction of Y from the liquid than it had originally, the residue must be poorer in Y and richer in X after distillation than before.
If the point, A had been chosen to the right of the azeotrope rather than to the left, the distillate at point C would be farther to the right than A, which is to say that the distillate would be richer in X and poorer in Y than the original mixture. So in this case too, the distillate moves away from the azeotrope and the residue moves toward it. This is characteristic of negative azeotropes. No amount of distillation, however, can make either the distillate or the residue arrive on the opposite side of the azeotrope from the original mixture. This is characteristic of all azeotropes.

Double azeotropes

Also more complex azeotropes exist, which comprise both a minimum-boiling and a maximum-boiling point. Such a system is called a double azeotrope, and will have two azeotropic compositions and boiling points. An example is water and N-methylethylenediamine as well as benzene and hexafluorobenzene.

Complex systems

Some azeotropes fit into neither the positive nor negative categories. The best known of these is the ternary azeotrope formed by 30% acetone, 47% chloroform, and 23% methanol, which boils at 57.5 °C. Each pair of these constituents forms a binary azeotrope, but chloroform/methanol and acetone/methanol both form positive azeotropes while chloroform/acetone forms a negative azeotrope. The resulting ternary azeotrope is neither positive nor negative. Its boiling point falls between the boiling points of acetone and chloroform, so it is neither a maximum nor a minimum boiling point. This type of system is called a saddle azeotrope. Only systems of three or more constituents can form saddle azeotropes.

Miscibility and zeotropy

If the constituents of a mixture are completely miscible in all proportions with each other, the type of azeotrope is called a homogeneous azeotrope. Homogeneous azeotropes can be of the low-boiling or high-boiling azeotropic type. For example, any amount of ethanol can be mixed with any amount of water to form a homogeneous solution.
If the components of a mixture are not completely miscible, an azeotrope can be found inside the miscibility gap. This type of azeotrope is called a heterogeneous azeotrope or heteroazeotrope. A heteroazeotropic distillation will have two liquid phases. Heterogeneous azeotropes are only known in combination with temperature-minimum azeotropic behavior. For example, if equal volumes of chloroform and water are shaken together and then left to stand, the liquid will separate into two layers. Analysis of the layers shows that the top layer is mostly water with a small amount of chloroform dissolved in it, and the bottom layer is mostly chloroform with a small amount of water dissolved in it. If the two layers are heated together, the system of layers will boil at 53.3 °C, which is lower than either the boiling point of chloroform or the boiling point of water. The vapor will consist of 97.0% chloroform and 3.0% water regardless of how much of each liquid layer is present provided both layers are indeed present. If the vapor is re-condensed, the layers will reform in the condensate, and will do so in a fixed ratio, which in this case is 4.4% of the volume in the top layer and 95.6% in the bottom layer.
Combinations of solvents that do not form an azeotrope when mixed in any proportion are said to be zeotropic. Azeotropes are useful in separating zeotropic mixtures. An example is zeotropic acetic acid and water. It is very difficult to separate out pure acetic acid : progressive distillations produce drier solutions, but each further distillation becomes less effective at removing the remaining water. Distilling the solution to dry acetic acid is therefore economically impractical. But ethyl acetate forms an azeotrope with water that boils at 70.4 °C. By adding ethyl acetate as an entrainer, it is possible to distill away the azeotrope and leave nearly pure acetic acid as the residue.