Isothermal titration calorimetry and density functional theory comparison study of xanthate, dithiophosphate and dithiocarbamate adsorption on pyrite surfaces M.G. Mulaudzi, J Taguta, B. McFadzean, and P.E. Ngoepe

Computational modelling methods and isothermal titration calorimetry (ITC) were employed to investigate the interaction of a pyrite surface with thiol collectors. Modelling work was conducted in the presence and absence of water. Microcalorimetry was employed to investigate the resultant energy of interaction pyrite as a result of mineral-collector interactions. Sodium ethyl xanthate (SEX), diethyldithiocarbamate (DTC) and diethyl dithiophosphate (DTP) were investigated in this study. The results showed that the calculated surface energies and morphologies for FeS2 showed that (100) and (111) are the most stable surfaces. The morphology also indicated the appearance of the (100) and (111) surface facets and no presence of others. The calculated adsorption energies between thiol collectors and the pyrite surface were always more exothermic than the experimentally determined ones. When comparing different ligand types with the same alkyl chain length, the heat of adsorption of diethyl-DTC was greater than that of ethyl xanthate and diethyl-DTP for pyrite. Experimentally, the diethyl DTP barely adsorbed onto the pyrite surface and this may be due to a different mechanism of action. In computational calculations, water adsorption was found to reduce the reactivity of the Fe atom for the interaction with thiol collectors, and bring the adsorption energies closer to the magnitude of the experimental values. Keywords: Computational modelling, microcalorimetry, experimental and thiol collectors, adsorption energies