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.
Despite considerable effort of experimentalists no reliable vapor-liquid coexistence at very small pressures and liquid-solid coexistence at high pressures have been until now observed in the working range of temperature 290<T/K<350 for ionic liquids. The measurements of high-pressure properties in low-temperature stable liquid are relatively scarce while the strong influence of their consistency on the phase equilibrium prediction is obvious. In this work we discuss the applicability of fluctuational-thermodynamic methodology and respective equation of state to correlate the properties of any (neutral, polar, ionic) liquids since our ultimate goal is the simple reference predictive model to describe vapor-liquid, liquid-liquid, and liquid-solid equilibria of mixtures containing above components. It is shown that the inconsistencies among existing volumetric measurements and the strong dependence of the mechanical and, especially, caloric derived properties on the shape of the functions chosen to fit the experimental data can be resolved in the framework of fluctuational-thermodynamic equation of state. To illustrate its results the comparison with the known experimental data for [bmim][BF4] and [bmim][PF6] as well as with the lattice-fluid equation of state and the methodology of thermodynamic integration is represented. It corroborates the thermodynamic consistency of predictions and excellent correlation of derived properties over the wide range of pressures 0<P/MPa<200.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.