ART. 281 - On the Distillation of Binary Mixtures

Summary

At various times during the past twenty years I have turned my attention to the theory of distillation, and have made experiments upon a question, as to which information seemed to be almost entirely lacking, viz., the relation between the strengths of liquid and vapour which are in equilibrium with one another when a binary mixture is subjected to distillation. In order to be intelligible I must set forth a little in detail some matters which are now fairly well known and understood, although they were not so at the time when my notes were written.

Distillation of a Pure Liquid

The temperature of the saturated vapour just over the liquid depends upon the pressure. If the end of the condenser-tube, e.g., of the Liebig type, be open, the pressure is of necessity nearly atmospheric. Suppose that in this tube a piston, moving freely, separates pure vapour from pure air. Then the whole wall of the condenser on the vapour side is almost at boiling-point. If we imagine the piston removed, the air and vapour may mix, and it is now the total pressure which is atmospheric. Wherever the temperature is below boiling there must be admixture of air sufficient to bring up the pressure.

Two or more Liquids which press independently

This is the case of liquids like water and bisulphide of carbon whose vapour-pressures are simply added. So long as the number of ingredients remains unchanged, the composition of the vapour rising from the boiling mixture is a function of the temperature (or total pressure) only.