Thermochemical approximations for sulfosalts

Most sulfosalts may be regarded as intermediate phases on joins between simple sulfide components (e.g., all lead sulfbismuthinides lie on the PbS-Bi ₂ S ₃ join). Many of the structures are characterized by subunits whose individual structures are similar to those of the component simple sulfides (e.g., galena-like and stibnite-like layers in the lead sulfantimonides). Therefore, as a first approximation one may estimate the properties of many sulfosalts in terms of mixtures of the simple sulfides.Recent work has shown that the free energy of reaction from the end-member sulfides, delta G _m , for more than 20 sulfosalts is usually less negative than the hypothetical ideal free energy of mixing and that the standard free energy of formation, delta G degrees , per gram atom of sulfur in the formula may be represented as:delta G degrees = (N _a delta G _a degrees + . . . N _i delta G _i [degree) + (1.2 + or - 0.8)(N _a RT ln N _a + . . . N _i RT ln N _i )where N _i is the mole fraction of the i-th simple sulfide component, R is the gas constant, and T is temperature in kelvins. The first term is far larger than the second. Estimates made for compounds in which the structural environment for the metals is quite different from that in the end-member sulfides, e.g., enargite, are subject to the greatest uncertainty.The estimated free energies may permit prediction of solubilities to a precision sufficient for many purposes, e.g., for H. C. Helgeson's computer-modeled hydrothermal systems. One may introduce some predictive capability into experimental design and anticipate some aspects of phase diagrams. This is especially true for redox reactions such as the behavior of proustite in the oxidized zone or the partial reduction of jamesonite to antimony + galena + pyrrhotite. However, other aspects, such as the prediction of the configuration of joins, e.g., PbS-As ₂ S ₃ , requires greater precision than the present rough estimates.