Editing Azeotrope (section)

=== Pressure swing distillation ===
[[file:HiLoPressureAzeotrope.png|thumb|Azeotrope composition shift due to pressure swing]]

A hypothetical azeotrope of constituents X and Y is shown in the adjacent diagram. Two sets of curves on a phase diagram one at an arbitrarily chosen low pressure and another at an arbitrarily chosen, but higher, pressure. The composition of the azeotrope is substantially different between the high- and low-pressure plots: higher in X for the high-pressure system. The goal is to separate X in as high a concentration as possible starting from point A. At the low pressure, it is possible by progressive distillation to reach a distillate at the point, B, which is on the same side of the azeotrope as A. Successive distillation steps near the azeotropic composition exhibit very little difference in boiling temperature. If this distillate is now exposed to the high pressure, it boils at point C. From C, by progressive distillation it is possible to reach a distillate at the point D, which is on the same side of the high-pressure azeotrope as C. If that distillate is then exposed again to the low pressure, it boils at point E, which is on the opposite side of the low-pressure azeotrope to A. So, by means of the pressure swing, it is possible to cross over the low-pressure azeotrope.

When the solution is boiled at point E, the distillate is poorer in X than the residue at point E. This means that the residue is richer in X than the distillate at point E. Indeed, progressive distillation can produce a residue as rich in X as is required.

In summary:

# Low-pressure rectification (A to B)
# High-pressure rectification (C to D)
# Low-pressure stripping (E to target purity)

* Rectification: the distillate, or "tops", is retained and exhibits an increasingly lower boiling point.
* Stripping: the residue, or "bottoms", is retained and exhibits an increasingly higher boiling point.

A mixture of 5% water with 95% [[tetrahydrofuran]] is an example of an azeotrope that can be economically separated using a pressure swing: a swing in this case between 1 [[Atmosphere (unit)|atm]] and 8 [[Atmosphere (unit)|atm]]. By contrast the composition of the water to ethanol azeotrope discussed earlier is not affected enough by pressure to be easily separated using pressure swings<ref name="hilmen" /> and instead, an entrainer may be added that either modifies the azeotropic composition and exhibits [[Miscibility|immiscibility]] with one of the components, or [[extractive distillation]] may be used.<ref>Perry's Chemical Engineer's Handbook, 7th Ed. 1997</ref>