Experimental and density functional theory comparison study of xanthate and dithiocarbamate adsorption on, sperrylite surface B. Nemutudi, S. Pikinini, P.P. Mkhonto, B. McFadzean, X. Zhang, and P.E. Ngoepe

The comparison study on adsorption of potassium normal butyl xanthate (PNBX) and sodium (nbutyl) dithiocarbamate (SNBDTC) on sperrylite mineral forms a basis in understanding the floatability improvement and paves a way for the design of collectors that may impact on a wide range of arsenide minerals. This study used a computational density functional theory (DFT) and experimental microcalorimetry approach to determine the adsorption energies of PNBX and SNBDTC collectors onto a sperrylite mineral surface. From a computational aspect, we considered the most stable surface plane of (100) surface, which had been found to give the lowest surface energy, compared to the other surface planes. It was observed that the PNBX and SNBDTC preferred to bridge on the As and Pt atoms through the S atoms. These findings showed that the collector adsorbed on the surface through both Pt and As atoms and indicated that the As atoms were significantly active in the adsorptions. We found that the adsorption energies were in the order: SNBDTC (–278.38 kJ/mol) > PNBX (–270.92 kJ/mol), indicating that the dithiocarbamate had stronger exothermic adsorption than the xanthate. From the microcalorimetry test it was also found that the SNBDTC was more exothermic than the PNBX and the adsorption energies were: SNBDTC (–473.50 kJ/mol) > PNBX (–331.13 kJ/mol). These results showed that the nitrogen atom in the SNBDTC collector had a great influence on the adsorption strength of the collector on the mineral surface. This is due to the electron deposition behaviour of nitrogen atoms compared to the electron withdrawing character of oxygen and as such the SNBDTC showed better collecting ability than the PNBX. These results paved the way for the design of collectors for sperrylite and other arsenide minerals and suggested that nitrogen in a collector may significantly improve the ability of the collector for improved recovery. Keywords: Computational modelling, microcalorimetry, SNBDTC and PNBX collectors, adsorption energies