Integrating Computational Modeling with Experimental Enthalpy of Adsorption: A Xanthate-Pyrite System

"The theoretical technique of computational modeling and the experimental determination of the enthalpy of adsorption of a ligand molecule onto a mineral surface deliver the same output parameters and, therefore, complement each other in investigating the affinity of different ligand types for mineral surfaces.This study ran parallel experimental tests and computational calculations to determine the enthalpy of adsorption of a series of increasing chain length xanthates onto a pyrite surface. The outcomes showed that, while the absolute energy values were different, the trends were similar. Both computational and experimental approaches showed that the extent of the interaction of the xanthate molecule increases with increasing carbon chain length. The computational values were larger than the experimental values, which could be explained, in part, by the addition of water to the computational system, which resulted in a decrease in the heat of adsorption on the (100) surface, compared to the adsorption of the collector in a vacuum. The computational method showed that, in the case of the pyrite (100) surface, the most exothermic reaction was obtained when the two xanthate sulfur atoms bridged two pyrite 5-coordinated iron atoms. The (111) surface was found to be more reactive and different adsorption mechanisms were predicted for each of the C2, C3, C4 and C5 chain length xanthates.The experimentally determined exothermic increase in heat of adsorption for the addition of each CH2 group was found to be -8.17 kJ/mol. The contribution of the thiol head group was -34.9 kJ/mol. Previous studies on self-assembled monolayers have shown that these values are compatible with lateral interactions between CH2 groups and the exclusion of water. This study provides a rigorous experimental and computational approach which is intended to afford confidence in modelled data for the screening of new ligands for flotation processes.INTRODUCTIONComputational modelling is a fast and cost-effective method of screening collector molecules for the efficacy of their adsorption onto mineral surfaces. However, it is desirable to measure the computational outputs against experimental outputs to check for congruency. Computational modelling and experimental microcalorimetry both deliver the same output parameter: the energy of adsorption of the molecule onto the solid surface. These techniques are therefore ideally suited to complement one another in investigating the affinity of the interaction between collector molecules and mineral surfaces."