Abstract
Flory's partition function for pure liquids is extended to binary mixtures using the two-fluid theory of mixtures and local compositions to allow for non-randomness and to take into account changes in molecular rotation and vibration which accompany the mixing process. This extension requires only two binary parameters: one for potential energy and the other for liquid structure (packing of molecules). For associated and/or solvated solutions, a chemical contribution is required to represent the mixture's Gibbs energy. Calculated activity coefficients agree well with experiment. For engineering work, this molecular theory offers no significant advantages over phenomenological equations now in common use. The theory, however, contributes toward the molecular understanding required to establish a truly satisfactory description of liquid mixtures.
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