Utility of mass-balanced EH-pH diagrams I — Applications of Gibbs’ Phase Rule

EH-pH diagrams are useful tools in understanding how mineral surfaces react in solution and particularly how aqueous conditions can be changed to enhance mineral leaching processes. Successful application of these diagrams, however, requires that several considerations be kept in mind to prevent what had been termed as “gross errors” in their calculation and use. In this paper, the aqueous Cu-S system is used as the basis for explaining the mass-balanced method of calculating EH-pH diagrams with the STABCAL thermodynamic equilibrium software. A breakdown of the Gibbs’ Phase Rule and how it is used in STABCAL to modify the diagrams is included. The methodology was applied to the aqueous Cu-As-S system, and resulting diagrams were compared against examples of those generated using the predominant-ion method. The complexity of such diagrams increases with every additional component, and competition between species becomes more apparent, as can be seen by curvature in the resulting mass-balanced diagrams. The complete diagram for enargite (Cu3AsS4) is shown. It compares well with spectroelectrochemical measurements from Raman spectroscopy and cyclic voltammetry studies.