Azeotrope:

An azeotrope is a mixture of liquids that maintains its composition and boiling

point during distillation. It is also known as an azeotropic mixture or constant
boiling point mixture. Azeotropy occurs when a mixture is boiled to produce a
vapor that has the same composition as the liquid. The term is derived by
combining the prefix "a," meaning "no," and the Greek words for boiling and
turning. The word was coined by John Wade and Richard William Merriman in
1911.

In contrast, mixtures of liquids that do not form an azeotrope under any

conditions are called zeotropic.

Types of Azeotropes:

Azeotropes may be categorized according to their number of constituents,

miscibility, or boiling points:

 Number of Constituents: If an azeotrope consists of two liquids, it is

known as a binary azeotrope. An azeotrope consisting of three liquids is
a ternary azeotropes. There are also azeotropes made of more than
three constituents.
 Heterogeneous or Homogeneous: Homogeneous azeotropes consist
of liquids that are miscible. They form a solution. Heterogeneous
azeotropes are incompletely miscible and form two liquid phases.
 Positive or Negative: A positive azeotrope or minimum-boiling
azeotrope forms when the boiling point of the mixture is lower than that
of any of its constituents. A negative azeotrope or maximum-boiling
azeotrope forms when the boiling point of the mixture is higher than that
of any of its constituents.

Examples:

 Boiling a 95 percent ethanol solution in water will produce a vapor that

is 95 percent ethanol. Distillation cannot be used to obtain higher
percentages of ethanol. Alcohol and water are miscible, so any quantity
of ethanol can be mixed with any quantity to prepare a homogeneous
solution that behaves like an azeotrope.
 Chloroform and water, on the other hand, form a heteroazeotrope. A
mixture of these two liquids will separate, forming a top layer consisting
mostly of water with a small amount of dissolved chloroform and a
bottom layer consisting mostly of chloroform with a small amount of
dissolved water. If the two layers are boiled together, the liquid will boil
at a lower temperature than either the boiling point of water or of
chloroform. The resulting vapor will consist of 97 percent chloroform
and 3 percent water, regardless of the ratio in the liquids. Condensing
 this vapor will result in layers that exhibit a fixed composition. The top
layer of the condensate will account for 4.4 percent of the volume, while
the bottom layer will account for 95.6 percent of the mixture.

Azeotrope Separation:

Since fractional distillation cannot be used to separate components of an

azeotrope, other methods must be employed:

 Pressure swing distillation applies pressure changes to change the

composition of a mixture to enrich the distillate with the desired
component.
 Another technique involves the addition of an entrainer, a substance
that alters the volatility of one of the azeotrope components. In some
cases, the entrainer reacts with a component to form a nonvolatile
compound. Distillation using an entrainer is called azeotropic distillation.
 Pervaporation involves separating components using a membrane that
is more permeable to one constituent than the other. Vapor permeation
is a related technique, using a membrane more permeable to the vapor
phase of one component than another.

Reference:

https://www.thoughtco.com/definition-of-azeotrope-605826

(26/02/2019, 10:00 PM)