Utility of Mass-Balanced EH-PH Diagrams II: Stoichiometry of Cu-As-S-H2O System

"Previously, Gibbs’ phase rule was applied to mass-balanced EH-pH diagrams for the Cu-As-S-H2O system. Diagrams were generated using the stoichiometry of enargite as a basis. In this study, the calculations were expanded to cover the stoichiometries of three other Cu-As-S minerals (tennantite, sinnerite, and lautite) and compared to enargite. Stability regions within the resulting EH-pH diagrams were found to change with stoichiometry such that a particular mineral would predominate if its stoichiometry was used in the calculation. Solution speciation was also found to vary, with thioarsenate being the best example. This stoichiometric effect helps to explain results reported in the literature and would be difficult to realize if it were not for mass-balanced calculations. INTRODUCTION A comprehensive thermodynamic review has recently been conducted on the aqueous copper-arsenic-sulfur system (Gow et al., 2014a-d). The free energies of over 100 species were collected from various authors and thermodynamic databases to produce mass-balanced EH-pH diagrams, using the thermodynamic equilibrium calculation software, STABCAL (Huang, 2014). The full database was listed and discussed by Gow et al. (2014A). Resulting diagrams were generated for enargite and confirmed with Raman spectroscopy using bulk mineral electrodes in order to identify reactions spectroelectrochemically. Theoretical calculations agreed well with the experimental results under alkaline conditions (Gow et al., 2014a), acid conditions (Gow et al., 2014b), and alkaline sulfide leaching conditions (Gow et al., 2014c). In this study, additional mass-balanced EH-pH diagrams are generated by changing the copper-arsenic-sulfur stoichiometry from enargite (Cu3AsS4) to tennantite (Cu12As4S13), sinnerite (Cu6As4S9) and lautite (CuAsS). Regions for the thermodynamically stable species are shown to change with the four different mineral compositions. Potential leach conditions, both for co-dissolution and selective dissolution techniques, were examined for differences in predominant species according to changing copper-to-arsenic ratios, sulfur compositions, and sulfur oxidation states."