Thermodynamics Research Center / ThermoML | Fluid Phase Equilibria

ABSTRACT

In order to have a better understanding on the electrostatic contribution to the thermodynamic property of ionic liquids (ILs), a two-parameter equation of state (EOS) is developed on the basis of hard sphere perturbation theory by accounting for the dispersion interaction with Cotterman et al. s EOS for L-J fluid and electrostatic interaction with mean spherical approximation (MSA) approach. The EOS is applicable for the density correlation of molecular liquids, and the resulting parameters, viz. Lennard Jones dispersive parameter a/k and soft-core diameter , can be used to predict the density of molecular mixtures and the corresponding ILs. The results indicate that the density of IL is always about 10% higher than the corresponding stoichiometric molecular mixture with which the IL is produced as an ionic adduct, for example, IL 1-methyl-3-methylimidazolium dimethylphosphate ([MMIM][DMP]) versus equimolar mixture of 1-methylimidazole (MIM) and trimethylphosphate (TMP). Furthermore, the density enhancement of ILs with respect to their corresponding stoichiometric molecular mixtures can be well represented by the electrostatic contribution among ionic species involved.