On the stability of (MX6)(3-) complexes in halide melts of three-valent metals

摘要

The effects of volume change at dissociation equilibrium of possible anion complexes of the (MX6)(3-) type in halide melts of trivalent metals MX3 within the statistical thermodynamics based on the MSA approximation were analysed. With the help of a simplified Akdeniz-Tosi model of a mixture of charged hard spheres of different diameters and valencies, we obtained the full system of equilibrium equations including the mass action law (MAL) and the equation of state (EoS). It was shown that the simplest approximation of the complex diameter as a tripled diameter of simple ions leads to a significant overestimation of the effects of volume changes at dissociation. It was found that the complex dissociation should be accompanied by a significant increase in density in a narrow temperature interval. It can be associated with the specific manifestation of electrolytic dissociation in the case of the trivalent metal halides' auto-complexation.