Utility of mass-balanced EH-pH diagrams I – Applications of Gibbs’ Phase Rule (847c4bd5-2740-4d34-8334-8ba5e7ee5d93)

"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.IntroductionInnovation in the field of processing arsenicbearing copper ores has been of particular interest. Copper arsenic sulfosalt minerals such as enargite (Cu3AsS4) and tennanite (Cu12As4S13) are now frequently prevalent in ore bodies as the oxide and easily leachable sulfides become harder to find. These minerals, unless pretreated somehow, concentrate in copper sulfide flotation processes, in turn concentrating the arsenic levels. Increasing environmental restrictions on arsenic content for smelters makes the hydrometallurgical processing of these concentrates more favorable. While enargite is considered one of the more refractory copper sulfides, more so than chalcopyrite (CuFeS2), there are still several methods, both industrially proven and in development, that are capable of processing these ore types. Alkaline sulfide leaching can be used as a pretreatment method to solubilize arsenic selectively (Delfini et al., 2003; Anderson and Twidwell, 2008; Tongamp, Takasaki and Shibayama, 2010a, 2010b), or the entire metal content can be leached using acid-type leaches such as acidified ferric sulfate (Dutrizac, 1981; Hackl et al., 1995; Klauber, 2008), or the chloride assisted, CESL (McDonald and Muir, 2007) or nitrogen species catalyzed (Anderson, 2003) processes can be used.As development of these leaching technologies proceed, it is also important to develop an understanding of the mineral thermodynamics. To date, there are numerous studies on the Cu-Fe-S-H2O system, particularly as it relates to chalcopyrite leaching, yet few studies have done on the Cu-As-S-H2O system. Computer-generated EH-pH diagrams have been employed to illustrate the importance of thermodynamic calculations in providing insight into such a system."