Asymmetric criticality in weakly compressible liquid mixtures

The thermodynamics of asymmetric liquid-liquid criticality is updated by incorporating pressure effects into the complete-scaling formulation earlier developed for incompressible liquid mixtures [C. A. Cerdeiriña et al. Chem. Phys. Lett. 424, 414 (2006); J. T. Wang et al. Phys. Rev. E 77, 031127 (2008)]. Specifically, we show that pressure mixing enters into weakly compressible liquid mixtures as a consequence of the pressure dependence of the critical parameters. The theory is used to analyze experimental coexistence-curve data in the mole fraction–temperature, density-temperature, and partial density–temperature planes for a large number of binary liquid mixtures. It is shown how the asymmetry coefficients in the scaling fields are related to the difference in molecular volumes of the two liquid components. The work resolves the question of the so-called “best order parameter” discussed in the literature during the past decades.