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Chemistry Supplemental Modules (Physical and Theoretical Chemistry) Physical
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Azeotropes
Last updatedJun 6, 2019
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Debye-H�ckel Theory
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An azeotrope is a mixture that exhibits the same concentration in the vapor phase
and the liquid phase. This is in contrast to ideal solutions with one component
typically more volatile than the other; this is how we use distillation to separate
materials. If the mixture forms an azeotrope, the vapor and the liquid
concentrations are the same, which preventing separation via this approach.

Introduction
Azeotropes are a mixture of at least two different liquids. Their mixture can
either have a higher boiling point than either of the components or they can have a
lower boiling point. Azeotropes occur when fraction of the liquids cannot be
altered by distillation. Typically when dealing with mixtures, components can be
extracted out of solutions by means of Fractional Distillation, or essentially
repeated distillation in stages (hence the idea of 'fractional'). The more volatile
component tends to vaporize and is collected separately while the least volatile
component remains in the distillation container and ultimately, the result is two
pure, separate solutions.

Ideal Solutions vs. Azeotropes

Ideal solutions are uniform mixtures of components that have physical properties
connected to their pure components. These solutions are supported by Raoult�s law
stating that interactions between molecules of solute and molecules of solvent are
the same as those molecules each are by themselves. An example of ideal solutions
would be benzene and toluene. Azeotropes fail to conform to this idea because, when
boiling, the component ratio of unvaporized solution is equal to that of the
vaporized solution. So an azeotrope can be defined as a solution whose vapor has
the same composition its liquid. As you can imagine, it is extremely difficult to
distil this type of substance. In fact, the most concentrated form of ethanol, an
azeotrope, is around 95.6% ethanol by weight because pure ethanol is basically
nonexistent.

Azeotropes exist in solution at a boiling point specific for that component. This
is best represented graphically and the phase diagram of a maximum-boiling point
azeotrope can be seen in the following figure. The point Z represents where the
azeotrope exists at a certain boiling point. Imagine that at point Z, the A-B
solution is 64% B by mass while component A is water. If that same solution
contained any less than 64%, the solution would then be water + the azeotrope.
Conversely, if it were to be greater than 64% then the solution would be component
B + the azeotrope. This demonstrates that an azeotrope can only exist at one
temperature because any higher or lower temperature would result in a different
concentration of component A or B.

Also, a maximum-boiling point azeotrope is said to be a negative azeotrope because

the boiling point of the azeotrope itself is higher than the boiling point of its
components. As you can imagine, a positive azeotrope would have a lower boiling
point than any of its components.

EXAMPLE 1

If pure ethanol has a boiling point of 78.3 �C and its azeotrope has a boiling
point of 78.174 �C, what would its graph look like?

SOLUTION

Since the azeotrope BP < pure ethanol BP, the azeotrope is a positive azeotrope and
would have a graph that looks like the above figure upside-down (U shaped).

References
Petrucci, Harwood, Herring, Madura. General Chemistry: Principles & Modern
Applications, Ninth Ed. Upper Saddle River, NJ: Pearson Education, Inc., 2007.
Brady, James E. General Chemistry: Principles & Structure, Fifth Edition. Jamaica,
NY: John Wiley & Sons., 1990.
Contributors
Megan Doyle
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