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A Simple G-Excess Model for Concentrated Aqueous Electrolyte Solutions

Author:
Macias-Salinas, Ricardo  


Journal:
JOURNAL OF CHEMICAL AND ENGINEERING DATA


Issue Date:
2019


Abstract(summary):

A simple yet accurate thermodynamic model was developed here to represent the nonideal behavior of single electrolytes in water at very high molalities and within a wide temperature range. The present model was obtained from an analytical expression of the excess Gibbs free energy (G-excess) which comprises three major contributions; in this context, a chemical term in the model handles the most predominant short-range ion solvent interactions by means of a chemical equilibrium approach based on a stepwise ion solvation, whereas another term in the model of physical nature also contributes in describing the aforementioned interactions by incorporating a simple Margules equation, and last, a continuum-solvent term given by the explicit mean-spherical-approximation (MSA) expression serves to account for long-range ion ion forces. The resulting G-excess model was applied to the representation of experimental mean ionic activity coefficients and osmotic coefficients of various representative aqueous electrolyte solutions: AgNO3, CaCl2, HCl, HClO4, HF, HNO3, KF, KOH, LiBr, LiCl, LiNO3, NaCNS, NaOH, NH4NO3, ZnBr2, and ZnCl2 salts in water at 25 degrees C (and from 0 up to 300 degrees C only in the case of KOH) and at high concentrations (up to 83.263 M). The results indicated a very good agreement between the experimental calculated using the present G-excess model for the majority of the electrolyte solutions considered here.


Page:
2193---2206


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