Azeotropic Distillation

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Azeotropic Distillation of water and ethanol by Harold van Schevensteen

The process of simple distillation is a method of separating mixtures based on their differences in volatility in a boiling liquid mixture. We find out, however, that using this process, a mixture of water and ethanol cannot be separated fully. The latter can only be purified to approximately 96%.

To get to this point, we go through a process whereby through distillation, we reduce the proportion of water in the mixture and increase that of ethanol. For example, if we were to distill a 50/50 mixture of ethanol and water, the distillate would be 80% ethanol and 20% water. Distilling this new mixture produces a mixture of 87% ethanol and 13% water. This goes on until we reach a ratio of 95.63% ethanol and 4.37% water, at which we reach a point called the azeotropic point of the mixture.

At this stage, the mixture is called a positive azeotrope, which is defined when the ratio of the constituents cannot be further changed by simple distillation. This occurs because any further boiling of the mixture will result in a vapour who’s ratio of constituents is the same as the original mixture.

The closer we get to this point, the lower the boiling point of the mixture as a whole. Ethanol has a boiling temperature of 78.4°C and water one of 100°C. When we have reached the azeotropic point, the mixture as a whole boils at a temperature of 78.2°C. Any further distillation will see the azeotrope boil at a temperature which is lower than any of it’s constituents. This introduces a problem for any further attempt to purify the ethanol (>96%), as we will see the azeotrope evaporates before the ethanol does.

This difficulty led some early scientists to believe that azeotropes were actually compounds of their constituents. This however proves not to be true as a compounds’ molecular composition…...

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