Thermodynamics of complex chemical equilibria in surfactant mixtures

Abstract

A thermodynamic approach was developed to predict the precipitation conditions of surfactants using the solubility product relationship between surfactant monomer concentrations, in order to calculate the monomer-precipitate equilibrium. This approach provides an explicit equation which predicts the amount of solid phase which forms in any surfactant mixture. All calculations of the total change in Gibbs energy (ΔG) were performed for concentrations of both surfactants that were below their CMC values. The elaborated ΔG-pH diagrams offer the possibility to determine the areas of thermodynamic stability of the solid phases depending on the chemical composition and acidity of the studied system. It was shown that with increasing concentration of the surfactant and the metal ion, the range of precipitate formation, either as slightly soluble salt or as slightly soluble acid, was extended by a few pH units in all cases.