Local compositions in thermodynamic excess functions for liquid mixtures

A critical discussion is given of the use of local compositions for representation of excess Gibbs energies of liquid mixtures. A new equation is derived, based on Scott's two‐liquid model and on an assumption of nonrandomness similar to that used by Wilson. For the same activity coefficients at infinite dilution, the Gibbs energy of mixing is calculated with the new equation as well as the equations of van Laar, Wilson, and Heil; these four equations give similar results for mixtures of moderate nonideality but they differ appreciably for strongly nonideal systems, especially for those with limited miscibility. The new equation contains a nonrandomness parameter α₁₂ which makes it applicable to a large variety of mixtures. By proper selection of α₁₂, the new equation gives an excellent representation of many types of liquid mixtures while other local composition equations appear to be limited to specific types. Consideration is given to prediction of ternary vapor‐liquid and ternary liquid‐liquid equilibria based on binary data alone.