Sina Ghasemi; Sima Mohammadnejad; Mohammad Reza Khalesi
Abstract
The adsorption of gold and copper cyanide complexes on the activated carbon is investigated using the Density Functional Theory (DFT). In order to represent the activated carbon, two fullerene-like model (presenting structural defect sites) and a simple graphene layer containing different functional ...
Read More
The adsorption of gold and copper cyanide complexes on the activated carbon is investigated using the Density Functional Theory (DFT). In order to represent the activated carbon, two fullerene-like model (presenting structural defect sites) and a simple graphene layer containing different functional groups (presenting chemical active sites) are employed. The structural defect sites show a much lower adsorption tendency toward all the cyano complexes comparing to the chemical active sites. The interaction energy for all of the complexes with structural defect sites (concave) is very low. However, the graphene layer with unsaturated active sites displays the highest level of interaction almost for all the complexes except Cu(CN)4-3. The effect of oxygen functional groups on the graphite edges shows a crucial role in the selectivity of gold adsorption over copper complexes. It has increased adsorption energy for Cu(CN)2- in the presence of OH and COOH, and has decreased adsorption energy for Au(CN)2- by OH and increased by COOH. The study results elucidate the lower selectivity for adsorption of gold over copper cyanides by high oxygen content activated carbon. The energy levels of the HOMO and LUMO orbitals show adsorption of unpaired cyanide anions on the activated carbon surface occurs by electron transfer from the complex to the adsorbent and adsorption onto the activated carbon edges by transferring electrons from the absorbent to the complex. The result has clearly demonstrated that the functional groups increase the adsorption tendency for both the gold (only COOH) and copper complexes (OH and COOH) but deteriorate the selectivity of gold over copper cyanides.
D. Alavi; S. Mohammadnejad; Seyed M. J. Koleini
Abstract
In this work, the mechanism of zinc hydroxide and ammine complexation in caustic and ammonia leaching is investigated by molecular modelling using the density functional theory method. The speciation of zinc complexes is defined based on the thermodynamic data and Pourbiax diagrams. The mechanism of ...
Read More
In this work, the mechanism of zinc hydroxide and ammine complexation in caustic and ammonia leaching is investigated by molecular modelling using the density functional theory method. The speciation of zinc complexes is defined based on the thermodynamic data and Pourbiax diagrams. The mechanism of Zn+2 complexation by hydroxide and ammine ligands is simulated by molecular modeling. The structure of reactants in the form of individual clusters is modelled using the density function theory. In order to compare the hydroxide and ammine species structures, the geometry studies are carried out as well. The ammoniacal salt effectiveness to improve the dissolution and stability of the ammine species is studied. The ligand single molecule interaction with a smithsonite molecule is done for a better understanding. Molecular modeling show that the zinc hydroxide species are more stable based on the higher reaction free energies. The reaction free energies decrease by adding the OH- and NH3 ions to the complexes from -30.12 kcal/mol to -16.943 kcal/mol, and -22.590 kcal/mol to 66.516 kcal/mol, respectively. The Zn-OH bonds are shorter than Zn-NH3, and the ammine species show more regular structures in comparison with the hydroxide structures. The change of free energies in the presence of ammoniacal salts indicate that the sulfate ions can significantly improve the dissolution of zinc oxide in ammonia. The smithsonite interaction with ammonia and hydroxide reveal that hydroxide ions lead to a higher interaction energy than ammonia (-36.396 vs. -28.238), which is consistent with the higher stability of hydroxide species. The results obtained well-explain the experimental results obtained before, and can be effectively used to optimize the alkaline leaching of zinc oxide ore.
