The separation operation called distillation utilizes vapor and liquid phases at essentially

the same temperature and pressure for the coexisting zones.

For a binary mixture, pressure and temperature fix the equilibrium vapor and liquid
compositions.
For other binary systems, one of the components is more volatile over only a part of the
composition range. Acetic acid-water system is one of these types. Acetic acid is more volatile
than water, in a certain range of concentration. Above these concentrations, volatility is reversed.
Such mixtures are known as azeotropic mixtures, and the composition in which the reversal
occurs, which is the composition in which vapor and liquid compositions are equal, is the
azeotropic composition, or azeotrope. The azeotropic liquid may be homogeneous or
heterogeneous (two immiscible liquid phases). Non azeotrope forming mixtures can be separated
by simple distillation into two essentially pure products. By contrast, simple distillation of
azeotropic mixtures will at best yield the azeotrope and one essentially pure species.
(Perrys Chemical Engineering Handbook, 8th edition, 13-5, 6, Distillation)
Don W. Green, Robert H. Perry
Copyright 2008 McGraw Hill Companies Inc.