An azeotrope or a constant boiling mixture is a mixture of two or more liquids whose

proportions cannot be altered or changed by simple distillation.[1] 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 term "azeotrope" was coined in 1911
by English chemist John Wade (18641912)[2] and Richard William Merriman.[3

Positive and negative azeotropes[edit]

Positive
Azeotropic Mixture which has a higher boiling point than its constituents is
termed as positive azeotropes. For instance consider a positive azeotrope, ethanol
consisting of a concentration of around ninety-five percent and four percent of
water in terms of weight. Water boils at hundred degree Celsius, and ethanol
boils at around seventy-eight-degree Celsius, whereas azeotropes boil at around
seventy-eight-degree Celsius indicating that it has a lower boiling point than its
constituents.
Minimum-boiling or Positive azeotrope[edit]

Phase diagram of a positive azeotrope. Vertical axis is temperature, horizontal axis is composition.

The diagram on the right 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.[1] 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.

Negative Azeotropes
Azeotropic mixtures with less boiling point then its constitutions is termed as negative
azeotropes. For instance consider a negative azeotrope, hydrochloric acid consisting a
concentration of around twenty percent and seventy-nine percent of water in terms of weight.
Water boils at hundred degree Celsius and hydrochloric acid boil at around minus eight four
degree Celsius, whereas azeotropes boil at around seventy-eight degree Celsius indicating that it
has a higher boiling point than its constituents.

Maximum-boiling or Negative azeotrope[edit]

Phase diagram of a negative azeotrope. Vertical axis is temperature, horizontal axis is composition.

The diagram on the right 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 allazeotropes.

Positive azeotrope mixture of chloroform and methanol

Negative azeotrope mixture of formic acid and water

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).
A well-known example of a positive azeotrope is 95.63% ethanol and 4.37% water (by
mass).[6] 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.[7] Indeed, 78.2 C is the minimum temperature at which any
ethanol/water solution can boil at atmospheric pressure. 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.
An example of a negative azeotrope is hydrochloric acid at a concentration of 20.2% and 79.8%
water (by mass). Hydrogen chloride boils at 84 C and water at 100 C, but the azeotrope boils at
110 C, which is higher than either of its constituents. The maximum temperature at which any
hydrochloric acid solution can boil is 110 C. 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.

Deviation from Raoult's law[edit]

Raoult's law predicts the vapor pressures of ideal mixtures as a function of composition ratio..
Solvent combinations that can form azeotropes are always nonideal, and as such they deviate from
Raoult's law.
Total vapor pressure of mixtures as a function of composition at a chosen constant temperature

The diagram on the right illustrates total vapor pressure of three hypothetical mixtures of
constituents, X, and Y. The temperature throughout the plot is assumed to be constant.
The center trace is a straight line, which is what Raoult's law predicts for an ideal mixture. The top
trace illustrates a nonideal mixture that has a positive deviation from Raoult's law, where the total
combined vapor pressure of constituents, X and Y, is greater than what is predicted by Raoult's law.
The top trace deviates sufficiently that there is a point on the curve where its tangent is horizontal.
Whenever a mixture has a positive deviation and has a point at which the tangent is horizontal, the
composition at that point is a positive azeotrope.[12] At that point the total vapor pressure is at a
maximum. Likewise the bottom trace illustrates a nonideal mixture that has a negative deviation from
Raoult's law, and at the composition where tangent to the trace is horizontal there is a negative
azeotrope. This is also the point where total vapor pressure is minimum.[12]