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. However, successful application of these diagrams requires several things be kept in mind to prevent what others have termed ?gross errors? in their calculation and use. The aqueous Cu-S system is used as the basis for explaining the mass-balanced method of calculating EH-pH diagrams with the thermodynamic equilibrium software, STABCAL. This includes a breakdown of the Gibbs? Phase Rule and how it is employed in STABCAL to modify the diagrams. This methodology was then applied to the aqueous Cu-As-S system and resulting diagrams are compared against examples of those generated using the predominant-ion method. The resulting mass-balanced diagram for enargite (Cu3AsS4) is noted to compare well with spectroelectrochemical measurements using Raman spectroscopy and cyclic voltammetry.