Prediction of Gibbs free energies of formation of minerals of the alunite supergroup

Abstract

A method for the prediction of Gibbs free energies of formation for minerals belonging to the alunite family is proposed, based on an empirical parameter Δ GO = M z+(c) characterizing the oxygen affinity of the cation M z+. The Gibbs free energy of formation from constituent oxides is considered as the sum of the products of the molar fraction of an oxygen atom bound to any two cations, multiplied by the difference of oxygen affinity Δ GO = M z+(c) between any two consecutive cations. The Δ GO = M z+(c) value, using a weighing scheme involving the electronegativity of a cation in a specific site (12-fold coordination site, octahedral and tetrahedral) is assumed to be constant. It can be calculated by minimizing the difference between experimental Gibbs free energies (determined from solubility measurements) and calculated Gibbs free energies of formation from constituent oxides. Results indicate that this prediction method gives values within 0.5% of the experimentally measured values. The relationships between Δ GO = M z+(alunite) corresponding to the electronegativity of a cation in either dodecahedral sites, octahedral sites or tetrahedral sites and known as Δ GO = M z+(aq) were determined, thereby allowing the prediction of the electronegativity of rare earth metal ions and trivalent ions in dodecahedral sites and highly charged ions in tetrahedral sites. This allows the prediction of Gibbs free energies of formation of any minerals of the alunite supergroup (bearing various ions located in the dodecahedral and tetrahedral sites). Examples are given for hydronium jarosite and hindsalite, and the results appear excellent when compared to experimental values.