Enthalpy of Adsorption of MBT, MBO and MBI and Modified MBT onto Pyrite Surfaces: A Computational and Experimental Approach

The adsorption of heterocyclic collectors such 2-mercaptobenzothiazole (MBT), 2-mercaptobenzoxazole (MBO), 2-mercaptobenzimidazole (MBI) and their derivatives on pyrite form a basis in understanding the flotation reactivity that may be applicable in a wide range of sulphide minerals. This study uses a computational and experimental approach to determine the heat of adsorption of MBT, MBO, MBI and modified MBT collectors onto pyrite surfaces. Computational calculations found that the adsorption energies were in the order: MBO > MBI > MBT. The heterocyclic collectors were adsorbed in their thiolate form on the surface. In the case of the pyrite (100) surface, the MBT adsorbed through the exocyclic sulphur atom, while MBO and MBI adsorbed through the exocyclic sulphur and N atoms onto the 5-coordinated Fe atom. The (111) surface was found to be more reactive and different adsorption mechanisms were predicted, where the MBT exocyclic sulphur atom bridged on the 5- coordinated Fe and surface 2-coordinated sulphur atoms, while the N atom adsorbed on the 5-coordinated Fe atom. In the case of MBO and MBI, dissociation of the exocyclic sulphur atom from the collector occurred with subsequent interaction with the surface 5-cordinated Fe and 2-coordinated S atoms. This resulted in the collector carbon atom adsorbing on the surface 2-coordinated S atom, while the N atom adsorbed on the 5-coordinated Fe atom. The adsorption of the modified MBT was found to be more exothermic than the MBT, which showed that introduction of a –CS2 group on the exocyclic sulphur atom improved the affinity of MBT on the surface, and was thus a better flotation collector. The computational results were supported by experimental enthalpy of adsorption measurements and microflotation tests. The chemistry of the heterocyclic thioamides is complicated by the fact that they can exist in a number of tautomeric and ionic forms at different pH’s. This is discussed in relation to the flotation and calorimetric data.