Ionic liquids are potential solvents for liquid extraction processes; thermodynamic modeling of liquid-liquid equilibrium (LLE) data is essential for the optimization and operation of these processes. Therefore, ternary LLE data in systems involving ionic liquids have been investigated by several years. In most of the cases, the thermodynamic modeling of these systems has been made using the NRTL model; in some cases, the UNIQUAC model has also been used. The structural parameters of UNIQUAC for ionic liquids have been determined either by empirical correlations or, more recently, through quantum mechanics calculation. This work is a continuation of a recent paper, in which the structural group volume and area parameters for the group-contribution UNIFAC method have been calculated for five ionic liquids following the quantum mechanics approach. In order to optimize the molecular geometry and to calculate the area and volume, the Density Functional Theory (DFT) and the Polarizable Continuum Method (PCM) were used, respectively. The obtained parameters were used to correlate LLE data for fifteen ternary systems, totalizing 155 tie-lines. New interaction parameters were also estimated between the solvent and the ionic liquid functional groups. The results are very satisfactory, with root mean square deviations 0.0037 between experimental and calculated equilibrium mole fractions. (c) 2010 Elsevier B.V. All rights reserved.