An Empirical Model of the Gibbs Free Energy for Solutions of NaCl and CaCl2 of Arbitrary Concentration at Temperatures from 423.15 K to 623.15 K under Vapor Saturation Pressure

Abstract

An empirical model for the concentration dependence of the Gibbs free energy for solutions of chlorides of alkaline and alkaline earth metals in water is proposed. A simple analytical form of the Gibbs free energy makes it possible to obtain the equations of state for salt solutions that are equally accurate in the entire range of salt concentrations, from dilute solutions to solubility limits. The high accuracy of the thermodynamic description of solutions of high and intermediate concentration is ensured by the presence in the equation for the Gibbs free energy of two terms related to the Margules decomposition of the Gibbs free energy. Our form of the Gibbs free energy also contains a term that reproduces the thermodynamic behavior of solutions of electrolytes, which ensures high accuracy of the proposed model at low salt concentrations in the solution. Using the model, the equations of state for aqueous solutions of NaCl and CaCl₂ at water vapor pressure in the temperature ranges of 423.15 K–573.15 K and 423.15 K–623.15 K were obtained, which corresponds to the parameters of ore-bearing solutions participating in the formation of low-temperature hydrothermal ore deposits.