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Stability of Anionic Complexes in Halide Melts of Bivalent Metals

Stability of Anionic Complexes in Halide Melts of Bivalent Metals The effect of volume variation at the possible dissociation equilibria of (MX4)2– anionic complexes in halide melts of bivalent metals are analyzed in terms of the mean-sphere approximation (MSA) of the statistical theory. Within the framework of the simplified model of charged hard spheres of different diameters and valences, the complete system of equilibrium equations is obtained, i.e., equations of the law of mass action and equations of state. This system makes possible self-correlated calculations of both the equilibrium concentration of autocomplexes and the melt density. It is shown that the simplest approximation of the complex diameter as the treble diameter of simple ions overestimates the effects of volume variations when considering dissociation. Taking into account the superposition of spheres makes it possible to describe the smoother volume variations with the temperature. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Russian Journal of Electrochemistry Springer Journals

Stability of Anionic Complexes in Halide Melts of Bivalent Metals

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Publisher
Springer Journals
Copyright
Copyright © 2018 by Pleiades Publishing, Ltd.
Subject
Chemistry; Electrochemistry; Physical Chemistry
ISSN
1023-1935
eISSN
1608-3342
DOI
10.1134/S1023193518050087
Publisher site
See Article on Publisher Site

Abstract

The effect of volume variation at the possible dissociation equilibria of (MX4)2– anionic complexes in halide melts of bivalent metals are analyzed in terms of the mean-sphere approximation (MSA) of the statistical theory. Within the framework of the simplified model of charged hard spheres of different diameters and valences, the complete system of equilibrium equations is obtained, i.e., equations of the law of mass action and equations of state. This system makes possible self-correlated calculations of both the equilibrium concentration of autocomplexes and the melt density. It is shown that the simplest approximation of the complex diameter as the treble diameter of simple ions overestimates the effects of volume variations when considering dissociation. Taking into account the superposition of spheres makes it possible to describe the smoother volume variations with the temperature.

Journal

Russian Journal of Electrochemistry – Springer Journals

Published: Jun 1, 2018

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