Interaction parameters and (solid + liquid) equilibria calculation for KCl-H2O-HCl-C2H5OH, K2SO4-H2O-H2SO4 and K2SO4-H2O-C2H5OH mixed solvent-electrolyte systems

This work deals with the prediction and experimental measurements of the (solid + liquid) equilibrium (SLE) in acid medium for industrial purposes. Specific systems including KCl-ethanol-water-HCl and K2SO4-water-H2SO4 were analyzed. At first, a critical discussion of SLE calculations was given, based on the well-known UNIQUAC extended and LIQUAC models. Two new proposals were derived, considering the explicit necessity of a new reference state for SLE calculations for the studied (solvents + acid) mixtures. The solubility of KCl in water-ethanol-HCl mixed solvents was measured in the temperature range of 300.15 to 315.15 K using an analytical gravimetric method. These results combined with some other experimental data reported in the open literature let us to propose a set of parameters for the new models. They included the interaction parameters between ethanol and the H+ ion. The prediction capability of the new models, for calculations in acid medium, was illustrated. Experimentally, it was observed that the (K2SO4 + water + H2SO4) system presented the unusual behavior of increasing K2SO4 solubility with an increase in the sulfuric acid concentration. This was accurately predicted by the newly proposed models.