A general isomorphism approach to thermodynamic and transport properties of binary fluid mixtures near critical points

Abstract

A general isomorphism approach to critical phenomena in binary fluid mixtures that may exhibit complex critical-line behavior is developed by relating the two relevant scaling fields to linear combinations of three physical field variables. These physical field variables are related to the temperature and chemical potentials of the two components. The proposed approach includes crossover from vapor-liquid critical behavior to liquid-liquid critical behavior and incorporates also the critical behavior near other special points on critical loci. It is shown that the key factor which determines the apparent behavior of the thermodynamic and transport properties of near-critical mixtures is the shape of the critical locus. The number of system-dependent coefficients that determine the asymptotic critical behavior is elucidated. The choice of zero-points of entropy and energy in binary mixtures is also discussed. The approach provides a powerful tool for predicting thermodynamic and transport properties of fluid mixtures in the critical region.