COSMO-RS-PDHS: A new predictive model for aqueous electrolytes solutions

Abstract

This work introduces a new tool able to predict water activities and activity coefficients of electrolytes in binary {water–electrolyte} systems. In mixtures containing electrolytes, the system is characterized by the presence of both molecular and ionic species, resulting in three different types of interactions: ion–ion, molecule–molecule and ion–molecule.Ion–ion interactions are governed by electrostatic forces between ions that have a much longer range than other intermolecular forces. The long range interactions between ions are taken in account by the Pitzer term based on the Debye–Hückel theory.Molecule–molecule and ion–molecule interaction forces are known to be short-range in nature. To determine short range mean activity coefficients of salts in {water–electrolyte} binary mixtures, a chemical treatment of ions solvation is combined with the predictive power of the COSMO-RS model. The main originality of this work resides in this chemical treatment model that provides the thermodynamic relations which enable to determine the equilibrium properties of the real solution {water–salt}, knowing those of a hypothetical mixture containing water and hydrated clusters.The resulting model called “COSMO-RS-PDHS” predicts results that are in good agreement with experimental data.