New Insights into Electrochemical Processes at the Chalcopyrite Electrode/Solution Interface

"Atmospheric leaching of chalcopyrite in sulfuric acid solutions is a slow process due to the mineral’s passivation. We have investigated the nature of the passive film in this work. Electrochemical reduction and oxidation of chalcopyrite over the potential range of -0.5 to 1.2 VSHE were investigated in 0.5 M sulfuric acid solution (pH 0.3) at 25 ºC by multicyclic voltammetry and open circuit potential measurement. The influence of scan limits on the evolution of current peaks was studied with both stationary and rotating electrodes. It was observed that the anodic oxidation of chalcopyrite begins at potentials above 0.6 VSHE, most likely by preferential dissolution of iron atoms over copper atoms. The selective electro-dissolution process results in formation of a metal-deficient sulfide passive film (i.e. Cu1- xFe1-yS2, y > x). The passive film dissolves at 0.9 VSHE. Elemental sulfur is one of the products of chalcopyrite dissolution above 1.0 VSHE. Cathodic reactions within the potential region of 0.1 to 0.6 VSHE and anodic reactions at potentials lower that 0.5 VSHE are associated with at least one soluble species from solution. The soluble species involved in the cathodic reactions are likely ferric and cupric, while the soluble species involved in the anodic reactions is likely H2Saq."