The second virial coefficients of mixed polar vapours

Abstract

The second virial coefficients of binary mixtures of chloroform with methyl formate, n-propyl formate, methyl acetate, ethyl acetate and diethylamine have been measured in a ‘Boyle’s law apparatus’ at temperatures between 50 and 95 °C. The measured values are consistently higher than predicted by the theory of corresponding states, and a quantitative interpretation is proposed, based on the hypothesis that the esters and amine are partially dimerized and are involved in association with the chloroform by hydrogen bonding. A linear relation is shown to exist between the heats and entropies of association for the various mixtures, and the theoretical significance of this is discussed. There is some evidence that hydrogen bonds are formed through the alkoxyl oxygen by formate esters and through the carbonyl oxygen by acetate esters. The paper includes data on the second virial coefficient for the pure esters and for ethyl formate and methyl propionate.