Global asymmetry of fluids and local singularity in the diameter of the coexistence curve

Abstract

By combining a measurable vapor-liquid coexistence curve and the extended van der Waals-type of equation of state (EOS) with the additional temperature-dependent coefficient, the phenomenological model of global fluid asymmetry has been developed separately for both coexisting bulk phases in the entire range of subcritical states. It is shown, in particular, that the adequate description of a liquid branch and its near-critical vicinity in terms of appropriate critical exponents and amplitudes connected by the two-scale-factor universal interrelations can be achieved. The asymmetric influence of heterophase fluctuations on the criticality of gaseous states is demonstrated. It is inherently similar to the well-known Fisher's droplet model, which corresponds to the scaling EOS too. The principle of corresponding isotherms has been formulated without any adjustable parameters. An attempt to avoid the use of a locally singular coexistence-curve diameter is proposed in the framework of two alternative models. The accurate vapor-liquid data for two fluid metals, Rb and Cs, as well as two molecular fluids, C(2)H(6) and CO(2), are reanalyzed by the above models to confirm the presumed opportunity.