The evolution of surface layers formed during chalcopyrite leaching

Chalcopyrite (CuFeS₂) leaching in perchloric acid (HClO₄) at an initial pH of one and a temperature of 85 °C has been examined. The rate of leaching of Cu and Fe increased progressively over the duration of the experiment. The Cu leach rate was initially greater (up to 24 h) but thereafter the leach rates for Cu and Fe were approximately equal. After 313 h 81% Cu release was achieved at which time the leach experiment was terminated. Only 25% of the available S was released into solution during the leaching process. Surface speciation over the duration of the leach was examined using X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy (SEM). As a result, a three-step reaction pathway is proposed. The first oxidation step involves the release of Cu and Fe into solution and the polymerisation of monosulfide (S^2-) to polysulfide S_n^{2 -}. The subsequent reduction step does not result in the release of cations to solution but does result in the reformation of surface S^2- and other short chain polysulfides, which then on further oxidation restructure to form crystalline elemental sulfur (S⁰). This final oxidation step is accompanied by further cation release.