Towards the Equation of State for Neutral (C2H4), Polar (H2O), and Ionic ([bmim][BF4], [bmim][PF6], [pmmim][Tf2N]) Liquids

摘要

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 temperature290<T/K<350for 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 pressures0<P/MPa<200.