Evaluation for internal consistency in the thermodynamic network involving fluorite, cryolite and villiaumite solubilities and aqueous species at 25°C and 1 bar

Abstract

Thermodynamic data are constrained by the interrelated thermodynamic equations in addition to the observational measurements and their uncertainties. The consequence is a network of thermodynamic properties that can be evaluated for their internal consistency. In this study, three fluoride minerals that can cause high fluoride concentrations in groundwaters are evaluated for their solubilities and their internal thermodynamic consistency with calorimetric, isopiestic and electrochemical measurements: fluorite, CaF2, cryolite, Na3AlF6, and villiaumite, NaF. This evaluation involves the three solids and 13 aqueous species, the free ions of Ca2+, Na+, Al3+ and F–, and the hydroxido and fluorido complexes of Al3+, and the CaF+ ion pair. For the fluorite–cryolite–villiaumite–aqueous species network, the number of components is minimal, and the solubility studies are mostly of high quality. Re-evaluations of original data using PHREEQC helps to broaden the quantitative evaluation of thermodynamic properties and to resolve apparent discrepancies. A check on this thermodynamic network shows that through a careful appraisal of the literature, a highly consistent set of values can be derived. The resultant infinite-dilution solubility-product constants at 25°C and 1 bar are: for fluorite solubility, logKsp = –10.57 ± 0.08; for cryolite solubility, logKsp = –33.9 ± 0.2; and for villiaumite solubility, logKsp = –0.4981 ± 0.003.

Minerals, crystal structures and geochemistry

“…‘Isotopic exchange of oxygen, sulfur, hydrogen and copper between aqueous phase and the copper minerals brochantite, libethenite and olivenite' by Juraj Majzlan, Ryan Mathur, Rastislav Milovsky and Stanislava Milovská presents the fractionation factor determined for the isotopes of oxygen, hydrogen, sulfur or carbon for the aforementioned minerals and their corresponding aqueous solutions, at temperatures between 30 and 70°C (Majzlan et al ., 2022). D. Kirk Nordstrom, in ‘Evaluation for internal consistency in the thermodynamic network involving fluorite, cryolite, and villiaumite solubilities and aqueous species, at 25°C and 1 bar', evaluates the published values of thermodynamic quantities, for their internal consistency, and calculates reliable values for the solubility constants and Gibbs energy of the solubility reactions of fluorite (CaF 2 ), cryolite (Na 3 AlF 6 ) and villiaumite (NaF) (Nordstrom, 2022).…”