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University Kakinada
Prof. K. V. Rao
Academic Advisor / Visiting Professor
School of Petroleum Courses
Azeotropes
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 .
It was Wade and Merriman who had first introduce the term
azeotrope in 1911 to designate mixtures that have a minimum
or maximum boiling point at constant pressure or,
equivalently, in the vapour pressure under isothermal
conditions. They define the azeotropy state as a stationary
point in the equilibrium T-x,y or P-x,y. 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
Figure
1:
Graphical
representations of the VLE
for the most common types
of
binary
mixtures
at
constant pressure:
a) Non-azeotropic;
b) Minimum-boiling
homoazeotrope;
c) Minimum-boiling
heteroazeotrope;
d) Maximum-boiling
azeotrope. Left: boiling
temperature
Tbp
and
condensation
temperature Tdp and the
equilibrium
mapping
vectors in T - x; y space.
Water-Ethanol
Pyridine-Water
Ethanol-Benzene
Acetic acid-Toluene
% Composition of
Boiling point
azeotrope
(pressure = 1 atm)
95.97 Ethanol
78.13oC
57.00 Pyridine
92.6oC
32.40 Ethanol
67.8oC
28.00 Acetic-acid
105.4oC
Nitric acid-Water
Acetic acid-Pyridine
Chloroform-Acetone
Hydrogen chloride-Water
% composition
of azeotrope
68% Nitric acid
65% Pyridine
80% Chloroform
79.8% Water
of
Binary
Separation
by
Changing
(Pressure-Swing Distillation)
System
Pressure
The separation of toluene (boiling point 110.8 oC) from isooctane (boiling point 99.3 oC) is difficult using conventional
distillation. Addition of phenol (boiling point 181.4 oC)
results in the formation of phenol-toluene mixture that
leaves the extractive distillation column as bottoms, while
relatively iso-octane is recovered as overhead product. The
phenol-toluene mixture is further separated in a second
column (solvent recovery column) whereby toluene appears
as distillate and the bottoms product, phenol, is recycled
back to the first column.
In the above example, when the solvent is added to the
original feed mixture it forms a new mixture with one of the
feed components by "absorbing" that component. This new
mixture has a much higher boiling point than the other feed
component that is not absorbed so that it leaves as bottoms
product from the extractive distillation column. The
unabsorbed feed component then leaves as the overhead
product.
The absence of azeotropes plus the fact that the solvent can
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