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.

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