The dissolution mechanism of chalcopyrite, and the potential range in which its passivation phenomenon takes place, were studied on carbon paste electrodes with chalcopyrite (99.46% purity, +300 mesh, 53 mu m size) (CPE-CP) in 1.7 mol/dm(3) H2SO4. A sequence of anodic potential pulses was applied to the CPE-CP to characterize its electrochemical behavior. Copper ions, dissolved by the potential pulses, were determined using a mercury film electrode (MFE) and the anodic stripping voltammetry (ASV) on a vitreous carbon disk. In addition, the modified surface of CPE-CP was characterized, before and after the potential pulses, by cyclic voltammetry (CV). The characterization of the final surface state of each electrochemically modified CPE-CP and the amount of dissolved copper showed five potential regions where the chalcopyrite dissolution mechanism changed. The initial dissolution occurs at 0.615 V <= E-anod < 1.015 V versus SHE forming a non-stoichiometric polysulfide (Cu1-xFe1-sS2-t). The absence of copper ions in the solution indicates a passive sulfide. However, at 1.015 V <= E-anod < 1.085 V versus SHE, the passive product decomposes forming porous layers of non-stoichiometric polysulfide (Cu1-xFe1-yS2-z) that allow the diffusional transport of charged species and the dissolution of the mineral. In the region of 1.085 V <= E-anod < 1.165 V versus SHE, formation covellite (CuS) was identified. At E > 1.165 V versus SHE, CuS is unstable and gives rise to complete dissolution of the chalcopyrite. Due to the experimental conditions, the mineral dissolution is inhibited by possible jarosite precipitation. (c) 2006 Elsevier Ltd. All rights reserved.