Utility of Mass-Balanced EH-pH Diagrams II: Stoichiometry of Cu-As-S-H2O System (bd7284b8-7fb9-4367-afdc-4788bfdb0889)

"In Part I, Gibbs’ phase rule was applied to mass-balanced EH-pH diagrams for the Cu-As-S-H2O system. The 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 with 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. IntroductionA comprehensive thermodynamic review has been conducted on the aqueous copper-arsenic-sulfur (Cu- As-S) system (Gow et al., 2014, 2015a, 2016b; Gow, Huang and Young, 2016c). Data on the free energies of more than 100 species were collected from various authors, and thermodynamic databases collated to produce mass-balanced EH-pH diagrams using the thermodynamic equilibrium calculation software STABCAL (Huang, 2014). The full database is listed and discussed in Gow et al. (2015a). 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., 2015a), acid conditions (Gow et al., 2014) and alkaline sulfide leaching conditions (Gow et al., 2015b).In the present study, additional mass-balanced EH-pH diagrams were generated by changing the Cu-As-S stoichiometry from enargite (Cu3AsS4) to tennantite (Cu12As4S13), sinnerite (Cu6As4S9) and lautite (CuAsS). Regions for the thermodynamically stable species were 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."