Solubility isotherms of the ternary system (LiCl + CaCl2 + H2O) were elaborately determined at T = (283.15 and 323.15) K. Several thermodynamic models were applied to represent the thermodynamic properties of this system. By comparing the predicted and experimental water activities in the ternary system, an empirical modified BET model was selected to represent the thermodynamic properties of this system. The solubility data determined in this work at T = (283.15 and 323.15) K, as well as those from the literature at other temperatures, were used for the model parameterization. A complete phase diagram of the ternary system was predicted over the temperature range from (273.15 to 323.15) K. Subsequently, the Gibbs free energy of formation of the solid phases CaCl2 . 4 H2O(s), CaCl2 . 2 H2O(s), LiCl . 2H(2)O((s)), and LiCl . CaCl2 . 5H(2)O((s)) was estimated and compared with the literature data. (C) 2008 Elsevier Ltd. All rights reserved.