%0 Journal Article
%T Towards the Equation of State for Neutral (C2H4), Polar (H2O), and Ionic ([bmim][BF4], [bmim][PF6], [pmmim][Tf2N]) Liquids
%A Vitaly B. Rogankov
%A Valeriy I. Levchenko
%J Journal of Thermodynamics
%D 2014
%I Hindawi Publishing Corporation
%R 10.1155/2014/496835
%X 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 / 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 /. 1. Introduction Behavior of low-melting organic salts or ionic liquids (ILs) [1¨C6] in the region of phase transitions is qualitatively similar to that either for high-temperature nonorganic molten salts or long-hydrocarbon-chain organic solvents and, even, for polymer systems. Such characteristic features as negligible vapor pressure , undefined critical parameters , , for vapor-liquid ()-transition, split of liquid-solid (l,s)-boundary onto melting and freezing branches, existence of glassy states make the problem of metastability to be quite complex but vital for many potential uses of ILs. In particular, thermodynamic modeling and computer simulation of the phase behavior in mixtures formed by ILs with water and low-molecular organic solvents such as ethylene can be of great importance for the further tuning of their operational parameters. If one proceeds from a pure to a mixed fluid, it is especially advantageous to develop the same format of reference equation of state (EOS) and the common format of reference pair potential (RPP) for each component and mixture. As a first step toward consistent
%U http://www.hindawi.com/journals/jther/2014/496835/