DFT Study on Reactivity of Different Neutral Flotation Collectors with Cu, Zn and Pb Metal Ions in Solution

Computational chemistry methods, such as density functional theory (DFT), are powerful tools to quantify reagent-mineral interactions encountered in sulphide mineral flotation. A quantitative relationship between theoretically calculated parameters based on chemical structure of collectors and their reactivity with different metals/minerals can provide valuable insights for design and development of more powerful and tailor-made reagents offering enhanced metal/mineral selectivity. DFT calculations at B3LYP/6-311++G(3df,3pd) level were employed to elucidate the reactivity of neutral sulphide collector reagents, including thionocarbamates (TC), thioureas (TU), xanthogen-formates (XF), dialkyldithiocarbamates (DTC) and dialkyltrithiocarbonates (TTC) with different heavy metal ions (Cu2+, Zn2+ and Pb2+) in solution. The extent of delocalization of lone pair electrons of heteroatoms (attached directly to C in C=S) over C=S group was found to be the dominant factor in determining the collector’s reactivity. Order of reactivity was established as: TU > TC > XF > DTC > TTC. All the collectors showed superior affinity towards copper followed by lead. Unidentate binding was observed through sulphur atom except for xanthogen-formate for which bidentate binding mode was observed. Effect of nature of substituent groups at N and/or O atom on reactivity of thionocarbamate and thiourea was also investigated. The results obtained through DFT calculations are consistent with the experimental data reported in literature.