In-Situ Investigation Of Sulfide Mineral Surface Oxidation Under Controlled Potential By Combined Atomic Force Microscopy And Chronoamperometry

The surface oxidation of sulfide minerals in aqueous solutions is an important sub-process in sulfide flotation and hydrometallurgy, but a full understanding of the oxidation process and products is still lacking. Many oxidation pathways and products involving elemental sulfur, metal polysulfide, metal-deficient sulfide and sulfate have been proposed, confirmed and argued. In this paper we provide further insight into the surface electrochemical behaviour of galena in aqueous solutions. For this research we have developed a novel experimental system, that combines chronoamperometry and AC-mode AFM surface imaging, which allows for in-situ, synchronized electrochemical control and examination of oxidative surface morphology. At pH4, the morphology of elemental sulfur (detected by ex-situ Cryo-XPS) formed on the oxidizing galena surface depends on the electrochemical potential pathway. In multi-step chronoamperometry (i.e. four potential steps from 0 mV to + 350 mV) the sulfur forms as nanoscopic domains, whereas in single-step chronoamperometry (i.e. one potential step from 0 mV to + 350 mV) sulfur forms as a heterogeneous layer. In each case the oxidation is controlled so that the number of electrons (coulombs) passed per unit area is the same, therefore the amount of sulfur produced is also the same. The differences in morphology with electrochemical potential pathway are explained using a nucleation and growth model. The formation of sulfur on the surface increased both advancing and receding contact angle of galena, but the morphological changes induced by different electrochemical potential pathways did not significantly alter the hydrophobicity of the surface. Keywords: galena, lead sulfide, oxidation, Atomic Force Microscopy, electrochemistry, collectorless flotation, hydrophobic