The entropy of liquid mixtures: II. Deviations from Raoult's law in mixtures containing large, flexible molecules

This is the authors' abstract. We don't add key points for this paper.

With the use of the model of the liquid developed in a previous article A. J. Staverman and J. H. van Santen, Rec. trav. chim. 60 , 76 (1941). a calculation is made. of the entropy of a liquid mixture consisting of small, stiff molecules and large, flexible ones. It is shown that in such mixtures negative deviations from Raoult's law will appear, even when the heat of mixing is zero. From measurements of the heat of mixing and of the solubility of hentriacontane, heptacosane, palmitone and myristone with cyclohexane, together with ebullioscopic measurements of Berger G. Berger, Rec. trav. chim. 57 , 1029 (1938). , the theoretical considerations are confirmed.