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The solubility of sphalerite (ZnS) was measured in KCl-HCl-H2O solutions at 300-600??C and 0.5-2.0 kbar. The silicate assemblage K-feldspar-muscovite (or andalusite)-quartz was used to buffer the solution to acid conditions, resulting in the total solubility reaction 2K+ + KAl2AlSi3O10(OH)2 + 6SiO2 + ZnS + nCl- = ZnCln(2-n) + 3KAlSi3O8 + H2S. (muscovite) (quartz) (sphalerite) (K-feldspar) A computer retrieval technique was used to derive average chloride ligand numbers for chlorozinc species at 0.25-2.0 molal total chloride. This technique mathematically solves for the average ligand number using a series of pertinent chemical relations at P and T. Mono- and di-chlorozinc species were found to predominate throughout the pressure-temperature-composition range investigated. The logarithms of the first and second dissociation constants for ZnCl20 were evaluated over the P-T range; for example, at 1 kbar, the values -0.41 and -1.42 were computed for the logarithm of the first dissociation constant, while -7.62 and -10.57 were computed for the logarithm of the second dissociation constant, for 400 and 500??C, respectively. Results are compared to past studies conducted at subcritical conditions and differ in that we find no evidence for more highly coordinated chloro-zinc species except possibly for ZnCl3- at 600??C, 1 and 2 kbar. Our results are consistent with electrostatic theory, which favors lower charged to neutral molecules in low dielectric-constant media. ?? 1994.
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An experimental study of zinc chloride speciation from 300 to 600 ??C and 0.5 to 2.0 kbar in buffered hydrothermal solutions