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Azeotrope

physical science Maturity 9-11 Next article →

An azeotrope is a special type of liquid mixture. It consists of two or more liquids that cannot be separated by simple distillation. In a normal mixture, boiling the liquid creates a vapor with a different composition than the liquid itself. This difference allows scientists to collect different substances through repeated boiling and cooling. However, an azeotrope behaves differently. When an azeotrope boils, the resulting vapor has the exact same proportions of ingredients as the unboiled liquid. Because the composition remains constant during this process, these mixtures are often called constant boiling point mixtures.

positiveAzeotropePhaseDiagram
positiveAzeotropePhaseDiagram

The mechanism of an azeotrope is best understood through vapor-liquid equilibrium. This describes the balance between the liquid phase and the vapor phase at a specific temperature. In a phase diagram, we can track how temperature and composition change during boiling. For a positive azeotrope, the boiling point curve reaches a minimum point. At this specific composition, the liquid curve and the vapor curve touch. If you attempt to distill a mixture that is not yet at the azeotropic composition, the vapor will become richer in one component. However, as you repeat the process, you will only ever move closer to the azeotropic point, never past it.

positiveAzeotropePhaseDiagram
positiveAzeotropePhaseDiagram

Scientists classify azeotropes into two primary types based on their boiling points. A positive azeotrope, also known as a minimum boiling mixture, boils at a temperature lower than any of its individual parts. A well-known example is a mixture of ethanol and water. Pure ethanol boils at 78.4 °C, and pure water boils at 100 °C. Yet, a mixture containing 95.63% ethanol and 4.37% water boils at only 78.2 °C.

Positive Azeotrope
Positive Azeotrope

Conversely, a negative azeotrope, or maximum boiling mixture, boils at a temperature higher than any of its individual constituents. For instance, a mixture of 20.2% hydrochloric acid and 79.8% water boils at 110 °C. This is significantly higher than the boiling point of water at 100 °C or hydrogen chloride at −85 °C.

negativeAzeotropePhaseDiagram
negativeAzeotropePhaseDiagram

Beyond these two types, more complex systems exist. A double azeotrope is a system that contains both a minimum and a maximum boiling point. One example of this is a mixture of benzene and hexafluorobenzene.

Benzene+Hexafluorobenzene (Double Azeotrope)
Benzene+Hexafluorobenzene (Double Azeotrope)

There are also saddle azeotropes, which only occur in systems with three or more liquids. These mixtures do not fit into the positive or negative categories because their boiling point falls between the boiling points of the individual components. A known example is a ternary azeotrope made of 30% acetone, 47% chloroform, and 23% methanol, which boils at 57.5 °C.

Saddle Azeotrope
Saddle Azeotrope

The term "azeotrope" has a specific history in chemistry. It was coined in 1911 by English chemists John Wade and Richard William Merriman. The name is derived from Greek roots. The prefix "a-" means "no," "zein" means "to boil," and "tropos" means "turning." Together, the word literally means "no change on boiling." The chemists created this term to replace much longer, more cumbersome descriptions like "mixtures having a minimum or maximum boiling point."

negativeAzeotropePhaseDiagram
negativeAzeotropePhaseDiagram

Some azeotropes are categorized by how well the liquids mix together. If the liquids are completely miscible, meaning they mix perfectly in all proportions, it is a homogeneous azeotrope. However, if the components do not mix completely, they form a heterogeneous azeotrope, or heteroazeotrope. In these cases, the mixture will separate into two distinct liquid layers. For example, chloroform and water can form two layers when shaken and left to stand. If you boil this heteroazeotrope, the vapor will always have a fixed ratio of 97.0% chloroform and 3.0% water.

HeteroazeotropePhaseDiagram
HeteroazeotropePhaseDiagram

Understanding these properties is vital for industrial and technical applications. Engineers must know the pressure, temperature, and composition behavior of mixtures to manage chemical processes. Azeotropes are particularly useful when trying to separate "zeotropic" mixtures, which are substances that do not form azeotropes. For example, separating pure acetic acid from water is very difficult using only distillation. To solve this, engineers can add ethyl acetate as an "entrainer." The ethyl acetate forms an azeotrope with water that boils at 70.4 °C. By distilling this new mixture away, the worker can leave nearly pure acetic acid behind in the container.

Drawing4-azeo
Drawing4-azeo
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🖼️ Images & Media (11)
File:VLEIsoropanolWaterAzeotrope.svg
VLEIsoropanolWaterAzeotrope.svg
File:Positive Azeotrope.png
Positive Azeotrope.png
File:positiveAzeotropePhaseDiagram.png
positiveAzeotropePhaseDiagram.png
File:Negative Azeotrope.png
Negative Azeotrope.png
File:negativeAzeotropePhaseDiagram.png
negativeAzeotropePhaseDiagram.png
File:Benzene+Hexafluorobenzene (Double Azeotrope).png
Benzene+Hexafluorobenzene (Double Azeotrope).png
File:Saddle Azeotrope.png
Saddle Azeotrope.png
File:HeteroazeotropePhaseDiagram.svg
HeteroazeotropePhaseDiagram.svg
File:Drawing4-azeo.png
Drawing4-azeo.png
File:RaoultDeviationPressureDiagram-en.svg
RaoultDeviationPressureDiagram-en.svg
File:HiLoPressureAzeotrope.png
HiLoPressureAzeotrope.png
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