Modeling of the thermodynamic properties of aqueous ionic liquid solutions with an equation of state for square-well chain fluid with variable range

International audience; A new thermodynamic model based on an equation of state for square-well chain fluid with variable range (SWCF-VR) is proposed to describe the thermodynamic properties of aqueous solutions of ionic liquids. In this approach the electrostatic interactions are characterized via the mean spherical approximation and the ionic associations between the cations and anions of the ionic liquid are considered through the shield-sticky approach. The liquid densities, osmotic coefficients, and vapor pressures of aqueous solutions of nine ionic liquids (ILs) containing [Cxmim][Br] (x = 2, 6), [C 4mim][BF4] and [Cxmim][MSO4] (x=1, 3, 4) have been modeled with the new model. Two ionic parameters for each anion and three for each cation of the ionic liquids were adjusted to experimental liquid densities and osmotic coefficients, and the corresponding average deviations are only 0.87% and 2.49%, respectively. Using the same ionic parameters, the vapor pressures of ionic liquid solutions are accurately predicted. The predicted equilibrium constants of the ionic association between the cations and anions of ILs in water were consistent with experimental observations. © 2011 American Chemical Society.