Interaction of H 2O with (CuS) n, (Cu 2S) n, and (ZnS) n small clusters ( n = 1–4, 6): relation to the aggregation characteristics of metal sulfides at aqueous solutions Original Paper First Online: 31 August 2019 Abstract
The interaction of H
2O onto small CuS, Cu 2S, and ZnS clusters was theoretically studied by Density Functional Theory computations to get insights into the aggregation characteristics of metal sulfides at aqueous solutions. The results show the charge-controlled interactions with polarized solvent molecules are favored on the ZnS clusters compared with CuS and Cu 2S clusters. Moreover, the chemical adsorption of H 2O molecules is energetically favored onto ZnS clusters with higher interaction energies of up to 35.4 kcal/mol compared with CuS and Cu 2S clusters (up to 31.3 kcal/mol), where the stability of H 2O adsorption decreases as the size of the clusters increases. However, thermochemical analysis shows that the adsorption of H 2O on copper sulfides is not a spontaneous process at room temperature. Additionally, the electrostatic energy of H 2O onto the Cu 2S and CuS clusters is lower than that associated with the H 2O–H 2O interactions, suggesting that copper precipitates prefer to bind between them at early stages of the precipitation process due to an unfavorable solvent-solute interaction. Dispersion forces play a relative key role in the interaction of water on copper sulfides, while for zinc sulfide clusters, the adsorption energy is slightly influenced by dispersion contributions. Accordingly, the aggregation of zinc sulfides in a water environment is expected to be lower compared with copper sulfides, and where the aggregation characteristics are not determined by the binding energy of the sulfides, but of the ability to interact with the solvent molecules. These statements were confirmed by experimental optical microscopy analysis and settling tests during precipitation processes in water. Therefore, this work allows proposing a simple strategy to study the aggregation characteristics of metal sulfides, which turns useful for use in hydrometallurgical applications. Keywords DFT calculations Metal sulfide precipitates Hydrometallurgy Clusters
This paper belongs to Topical Collection QUITEL 2018 (44th Congress of Theoretical Chemists of Latin Expression)
Electronic supplementary material
The online version of this article (
) contains supplementary material, which is available to authorized users. https://doi.org/10.1007/s00894-019-4161-x Notes Acknowledgments
D.C-A acknowledges the computational resources through the CONICYT/FONDEQUIP project EQM180180. H.E and RRF acknowledge the FONDEF/IDeA Program, FONDEF/CONICYT 2017+ID17I10021. Powered@NLHPC: This research was partially supported by the supercomputing infrastructure of NLHPC (ECM-02).
This work received financial support from the CONICYT/FONDECYT 11170289.
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The authors declare that there are no competing interests.
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