Most investigators regard CuFeS2 as having the formal oxidation states of Cu+Fe3+(S2-)(2). However, the spectroscopic characterisation of chalcopyrite is clearly influenced by the considerable degree of covalency between S and both Fe and Cu. The poor cleavage of CuFeS2 results in conchoidal surfaces. Reconstruction of the fractured surfaces to form, from what was previously bulk S2-, a mixture of surface S2-, S-2(2) and S-n(2-)(or metal deficient sulfide) takes place. Oxidation of chalcopyrite in air (i.e. 0.2 atm of O-2 equilibrated with atmospheric water vapour) results in a Fe(III)-O-OH surface layer on top of a Cu rich sulfide layer overlying the bulk chalcopyrite with the formation of Cu(II) and Fe(III) sulfate, and Cu(I)-O on prolonged oxidation. Cu2O and Cu2S-like species have also been proposed to form on exposure of chalcopyrite to air. S-2(2-), S-n(2-) and S-0 form on the chalcopyrite surface upon aqueous leaching. The latter two of these species along with a jarosite-like species are frequently proposed to result in surface leaching passivation. However, some investigators have reported the formation of S sufficiently porous to allow ion transportation to and from the chalcopyrite surface. Moreover, under some conditions both Si-2,Si-- and S were observed to increase in surface concentration for the duration of the leach with no resulting passivation. The effect of a number of oxidants, e.g. O-2, H2O2, Cu2+, Cr6+ and Fe3+, has been examined. However, this is often accompanied by poor control of leach parameters, principally pH and Eh. Nevertheless, there is general agreement in the literature that chalcopyrite leaching is significantly affected by solution redox potential with an optimum Eh range suggesting the participation of leach steps that involve both oxidation and reduction. Three kinetic models have generally been suggested by researchers to be applicable: diffusion, chemical reaction and a mixed model containing diffusion and chemical components which occur at different stages of leaching. Passivation effects, due to surface diffusion rate control, may be affected by leach conditions such as pH or Eh. However, only initial conditions are generally described and these parameters are not controlled in most studies. However, at fixed pH, Eh and temperature, it appears most likely that leaching in sulfuric acid media in the presence of added Fe3+ is surface reaction rate controlled with some initial period, depending on leach conditions, where the leach rate is surface layer diffusion controlled. Although bioleaching of some copper ores has been adopted by industry, bioleaching has yet to be applied to predominantly chalcopyrite ores due to the slow resulting leach rates. Mixed microbial strains usually yield higher leach rates, as compared to single strains, as different bacterial strains are able to adapt to the changing leach conditions throughout the leach process. As for chemical leaching, passivation is also observed on bioleaching with jarosite being likely to be the main contributor. In summary, whilst much has been observed at the macro-scale regarding the chalcopyrite leach process it is clear that interpretation of these phenomena is hampered by lack of understanding at the molecular or atomic scale. Three primary questions that require elucidation, before the overall mechanism can be understood are: 1. How does the surface of chalcopyrite interact with solution or air borne oxidants? 2. How does the nature of these oxidants affect the surface products formed? 3. What determines whether the surface formed will be passivating or not? These can only realistically be tackled by the application of near atomic-scale analytical approaches, which may include quantum chemical modelling, PEEM/SPEM, TEM, AFM etc. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.
