Statistical theory of individual ionic activity coefficients of electrolytes with multiple - Charged ions including seawater

Based on methods of statistical mechanics for the calculation of individual activity coefficients for electrolytic solutions we present analytical nonlinear extensions of the standard Debye - Huckel and Mean-Spherical approximations. These extensions, so - called DHX and MSX approximations, respectively, generalize the exact results from cluster theory and are given for the model of charged hard spheres with non - additive contact distances. The flexibility of the fully analytical model which is able to reflect e.g. cationic solvation effects and allows the treatment of ionic activities in a 6-component seawater model. Denoting by e the elementary charge, DHX and MSX include in the third order, e(6), the Poirier effects of asymmetry of ion charges, and in the fourth order, e(8), as well as in higher orders, weak association effects which are relevant for electrolytes with multivalent ions. Following the Justice method, weak association effects are treated in a semi - chemical description avoiding mass - action laws. An extrapolation of the theory of individual activities to a description of individual conductivities is proposed. (C) 2021 Published by Elsevier B.V.

Automated summary

Based on statistical mechanics methods, this study presents analytical nonlinear extensions of the Debye-Huckel and Mean-Spherical approximations for the calculation of individual activity coefficients in electrolytic solutions. The DHX and MSX approximations generalize the results from cluster theory and can handle various effects such as cationic solvation and weak association effects in multivalent ions.