2. An azeotrope or a constant boiling mixture is a
mixture of two or more liquids whose proportions
cannot be altered by simple distillation.
This happens because, when an azeotrope is boiled,
the vapour has the same proportions of constituents
as the unboiled mixture.
3.
4. Minimum Boiling Azeotropes
Each azeotrope has a characteristic boiling point. The
boiling point of an azeotrope is less than the boiling
point temperatures of any of its constituents is a
Minimum boiling azeotrope.
5. 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 vapour composition
above the liquid at a
given temperature.
Above the top trace,
only the vapour is in
equilibrium.
6. 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.
7. 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.
8.
9. Maximum Boiling Azeotropes
Each azeotrope has a characteristic boiling point. The
boiling point of an azeotrope is more than the boiling
point temperatures of any of its constituents is a
Maximum boiling azeotrope.
10. The diagram on the right shows a negative azeotrope of
hypothetical 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
11. 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
12. 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.