Development of a new equation of state for mixed salt and mixed solvent systems, and application to vapour–liquid and solid (hydrate)–vapour–liquid equilibrium calculations

Abstract

An equation of state that can be used for phase equilibrium and other thermodynamic property calculations at high pressures is developed for systems that contain aqueous solutions of strong electrolytes and molecular species. The proposed equation of state is based upon contributions to the Helmholtz free energy from a non-electrolyte term and three electrolyte terms. The non-electrolyte term comes from the Trebble–Bishnoi equation of state and the electrolyte terms consist of a Born energy term, a mean spherical approximation term and a newly developed hydration term. The application of the proposed equation of state to aqueous systems containing mixed salts and mixed solvents is illustrated by calculating the vapour–liquid equilibrium (VLE) and solid (Clathrate hydrate)–vapour–liquid equilibrium (SVLE) conditions for several systems. The solubility of CO2 in salt water systems is examined at elevated pressures. As well, the new equation of state is used in conjunction with the model of van der Waals and Platteeuw to predict the SVLE conditions for gas hydrate forming systems in the presence of single salts, mixed salts and a mixture of aqueous salts and methanol. It is found that the new equation of state is able to accurately represent the experimental data over a wide range of pressure, temperature and salt concentration.