The modified quasi-chemical model: Part II. Multicomponent solutions

TLDR: In this article, the modified quasi-chemical model in the pair approximation for short-range ordering (SRO) in liquids is extended to multicomponent solutions and an improved general functional form for "ternary terms" in the excess Gibbs energy expression is proposed, related to the effect of a third component upon the binary pair interaction energies.

Abstract: Further improvements to the modified quasi-chemical model in the pair approximation for shortrange ordering (SRO) in liquids are extended to multicomponent solutions. The energy of pair formation may be expanded in terms of the pair fractions or in terms of the component fractions, and coordination numbers are permitted to vary with composition. The model permits complete freedom of choice to treat any ternary subsystem with a symmetric or an asymmetric model. An improved general functional form for “ternary terms” in the excess Gibbs energy expression is proposed. These terms are related to the effect of a third component upon the binary pair interaction energies. It is shown how binary subsystems that have been optimized with the quasi-chemical model can be combined in the same multicomponent Gibbs energy equation with binary subsystems that have been optimized with a random-mixing Bragg-Williams model and a polynomial expression for the excess Gibbs energy. This is of much practical importance in the development of large databases for multicomponent solutions. The model also applies to SRO in solid solutions as a special case, when the number of lattice sites and coordination numbers are constant.