What is azeotropy?

The term azeotrope means “nonboiling by any means” (Greek: a - non, zeo - boil, tropos - way/mean),
and denotes a mixture of two or more components where the equilibrium vapor and liquid
compositions are equal at a given pressure and temperature. More specifically, the vapor has the same
composition as the liquid and the mixture boils at a temperature other than that of the pure
components’ boiling points. Azeotropes have sometimes been mistaken for single components because
they boil at a constant temperature. However, for an azeotrope a variation in pressure changes not only
the boiling temperature, but also the composition of the mixture, and this easily distinguishes it from a
pure component.

The mixture whose composition corresponds to an extremal point is called an azeotrope. If at the
equilibrium temperature the liquid mixture is homogeneous, the azeotrope is a homoazeotrope. If the
vapor phase coexists with two liquid phases, it is a heteroazeotrope. Systems which do not form
azeotropes are called zeotropic .

Physical phenomena leading to nonideality and azeotropy

Azeotropy is merely a characteristic of the highly nonlinear phase equilibria of mixtures with strong
molecular interactions. Azeotropes are formed due to differences in intermolecular forces of attraction
among the mixture components (hydrogen bounding and others). The particular deviation from ideality
is determined by the balance between the physiochemical forces between identical and different
components. Briefly, we have three groups:

1. Positive deviation from Raoult’s law:

The components “dislike” each other. The attraction between identical molecules (A-A and B-B) is
stronger than between different molecules (A-B). This may cause the formation of a minimum-boiling
azeotrope and heterogeneity.

2. Negative deviation from Raoult’s law:

The components “like” each other. The attraction between different molecules (A-B) is the strongest.
This may cause the formation of a maximum-boiling azeotrope.

3. Ideal mixture obeys Raoult’s law:

The components have similar physiochemical properties. The intermolecular forces between identical
and different molecules (A-A, B-B and A-B) are equal .

The tendency of a mixture to form an azeotrope depends on two factors:

 the difference in the pure component boiling points,

 the degree of nonideality
(Horsley, 1973; King, 1980).

The closer the boiling points of the pure components and the less ideal mixture, the greater the
likelihood of an azeotrope. A heuristic rule is given in Perry and Chilton (1973) that azeotropes occur
infrequently between compounds whose boiling points differ by more than about 30 o C. An important
exception to this rule is heteroazeotropic mixtures where the components may have a large difference
in the boiling points of the pure components, and still exhibit strong nonideality and immiscibility
regions. In heterogeneous mixtures the different components may even repel each other. This is why
only minimum-boiling heteroazeotropes occur in nature.

Ideal or nearly ideal behavior is encountered in mixtures formed by closely related chemical substances
such as heptane and hexane, or butyl alcohol and hexyl alcohol. However, there are exceptions to this
heuristic rule as well. If there is a point in the composition space in which the vapor pressures of the two
components are equal at a given temperature (in the region of the normal boiling-points of the pure
components), this may correspond to an azeotropic point which is called a Bancroft point, illustrated in
Figure 2.5. This is referred to as Bancroft’s rule (Malesinkski, 1965). The intermolecular forces in the
mixture may be similar, but the mixture still exhibits an azeotropic behavior.

Separation of azeotropes :

Most liquid mixtures of organic components form nonideal systems. The presence of some specific
groups, particularly polar groups (oxygen, nitrogen, chlorine and fluorine), often results in the formation
of azeotropes. Binary homoazeotropes (at least the ones that are not pressure sensitive) are impossible
to separate by ordinary distillation, but may be effectively separated by membrane-distillation hybrids
or distillation methods where a third component is added to the system. Analysis of ternary VL(L)E
diagrams is an efficient tool to predict feasible separations for entrainer-addition distillation processes.
Simplest approaches are sufficient if used properly. We distinguish between three different entrainer-
addition distillation methods depending on the properties of the entrainer and the organization of the
column flows and the following conclusions can be made:

Homogeneous azeotropic distillation:

(ordinary distillation of homoazeotropic mixtures) Only a few VLE diagram structures of the resulting
ternary system of original mixture and entrainer are possible to separate by ordinary distillation
(sequence of single-feed columns). The separation schemes are complex and may be very energy
intensive, or may have multiplicities.
Heteroazeotropic distillation :

Several VLLE diagram structures that involves one or more heteroazeotropes are possible to separate by
ordinary distillation combined with decantation. The separation schemes are fairly simple, but the range
of feasible entrainers is rather limited.

Extractive distillation :

Extractive distillation is the most general distillation method for separating homoazeotropic mixtures.
The scheme is not sensitive to the type of original mixture as there is a broad range of feasible
entrainers. The process is not limited to homogeneous entrainers, and heteroextractive distillation-
decanter hybrids may be applied with success.

Insights into to the thermodynamic behavior of azeotropic mixtures is fundamental for the development
of separation system involving azeotropic mixtures. This is an incentive to consider the powerful tool of
graphical VLE representation in more detail.