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

Part of: Minerals, crystal structures and geochemistry - Peter Williams special issue

Published online by Cambridge University Press:  13 May 2022

D. Kirk Nordstrom Open the ORCID record for D. Kirk Nordstrom [Opens in a new window]
D. Kirk Nordstrom*
Affiliation:
United States Geological Survey, Boulder, CO 80303, USA
*
*Author for correspondence: D. Kirk Nordstrom, Email: dkn@usgs.gov
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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.

Keywords

fluoritecryolitevilliaumitefluoride mineral solubilitiesinternal consistency
Type
Article
Information
Mineralogical Magazine , Volume 86 , Issue 4 , August 2022 , pp. 652 - 660
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This is a work of the US Government and is not subject to copyright protection within the United States
Copyright
Copyright © U. S. Geological Survey, 2022. Published by Cambridge University Press on behalf of the Mineralogical Society of Great Britain and Ireland

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Footnotes

This paper is part of a thematic set that honours the contributions of Peter Williams

Associate Editor: Juraj Majzlan

References

Aghie, M. and Samaie, E. (2006) Non-ideality and ion-pairing in saturated aqueous solution of sodium fluoride at 25°C. Journal of Molecular Liquids, 126, 72–74.CrossRefGoogle Scholar
Anovitz, L.M., Hemingway, B.S., Westrum, E.F. Jr., Metz, G.W. and Essene, E.J. (1987) Heat capacity measurements for cryolite (Na3AlF6) and reactions in the system Na–Fe–Al–Si–O–F. Geochimica et Cosmochimica Acta, 51, 3087–3103.CrossRefGoogle Scholar
Aumeras, M. (1927) Étude de l'équilibre fluorure de calcium-acide chlorhydrique etendu – contribution a l'étude des équilibres ioniques. Journal de Chimie Physique, 24, 548–571.CrossRefGoogle Scholar
Bloom, P.R. and Weaver, R.M. (1982) Effect of the removal of reactive surface material on the solubility of synthetic gibbsites. Clays and Clay Minerals, 30, 281–286.CrossRefGoogle Scholar
Brown, D.W. and Roberson, C.E. (1977) Solubility of natural fluorite at 25°C. Journal of Research of the U.S. Geological Survey, 5, 509–517.Google Scholar
Buchwald, H. (1939) Solubility and dissociation of cryolite in aqueous solutions. Nord Kemikermke, 5, 259–260.Google Scholar
Butler, J.N. (1968) The standard potential of the calcium amalgam electrode. Electroanalytical Chemistry and Interfacial Chemistry, 17, 309–317.CrossRefGoogle Scholar
Carter, R.H. (1928) Solubilities of some inorganic fluorides in water at 25°C. Industrial and Engineering Chemistry, 20, 1195.CrossRefGoogle Scholar
Chase, M.W. Jr. (1998) NIST-JANAF Thermochemical Tables. American Chemical Society and American Institute of Physics, Woodbury, NY.Google Scholar
Cox, J.D., Wagman, D.D. and Medvedev, V.A. (1989) CODATA Key Values for Thermodynamics. Hemisphere Publ. Corp., New York.Google Scholar
Faridi, J. and Guendouzzi, M.E. (2015) Study of ion-pairing and thermodynamic properties of sodium fluoride in aqueous solutions at temperatures from 298.15 to 353.15 K. Journal of Solution Chemistry, 44, 2194–2207.CrossRefGoogle Scholar
Fawell, J., Bailey, K., Chilton, J., Dahi, E., Fewtrell, L. and Magara, Y. (2006) Fluoride in drinking-water. World Health Organization, IWA Publication, Seattle, USA.Google Scholar
Fovet, Y. and Gal, J.-Y. (2000) Formation constants of β 2 of calcium and magnesium fluorides at 25°C. Talanta, 53, 617–626.CrossRefGoogle Scholar
Frere, F.J. (1936) Equilibrium in fluoride systems. I. Solubility of cryolite in aqueous solutions or iron and aluminum salts at 25°C. Journal of the American Chemical Society, 58, 1695–1697.CrossRefGoogle Scholar
Garand, A. and Mucci, A. (2004) The solubility of fluorite as a function of ionic strength and solution composition at 25°C and 1 atm total pressure. Marine Chemistry, 91, 27–35.CrossRefGoogle Scholar
Gardner, G.L. and Nancollas, G.H. (1976) Kinetics of crystal growth and dissolution of calcium and magnesium fluorides. Journal of Dental Research, 55, 342–352.CrossRefGoogle ScholarPubMed
Garvin, D., Parker, V.B. and White, H.J. Jr. (1987) CODATA Thermodynamic Tables: Selection for some compounds of calcium and related mixtures: A prototype set of tables. Hemisphere Publishing Corporation, New York.Google Scholar
Hamer, W.J. and Wu, Y.C. (1972) Osmotic coefficients and mean activity coefficients of uni-univalent electrolytes in water at 25 °C. Journal of Physical and Chemical Reference Data, 1, 1047–1100.CrossRefGoogle Scholar
Heller, K.E., Eklund, S.A. and Burt, A.B. (2007) Dental caries and dental fluorosis at varying water fluoride concentrations. Journal of Public Health Dentistry, 57, 136–143.CrossRefGoogle Scholar
Hem, J.D. (1968) Graphical methods for studies of aqueous aluminum hydroxide, fluoride, and sulfate complexes. U.S. Geological Survey Water-Supply Paper, 1927-B. US Geological Survey, Reston, Virginia, USA.Google Scholar
Hem, J.D. and Roberson, C.E. (1967) Form and stability of aluminum hydroxide complexes in dilute solution. U.S. Geological Survey Water-Supply Paper, 1827-A. US Geological Survey, Reston, Virginia, USA.Google Scholar
Hemingway, B.S. and Robie, R.A. (1977) The entropy and Gibbs free energy of formation of the aluminum ion. Geochimica et Cosmochimica Acta, 41, 1402–1404.CrossRefGoogle Scholar
Henry, R.L. (2018) Low temperature aqueous solubility of fluorite at temperatures of 5, 25, and 50 °C and ionic strengths up to 0.72. MSc Thesis, Colorado School of Mines, Golden, Colorado, USA.Google Scholar
Hernández-Luis, F., Galleguillos, H.R. and Vázquez, M.V. (2004) Activity coefficients of NaF in (glucose + water) and (sucrose + water) mixtures at 298.15 K. Journal of Chemical Thermodynamics, 36, 957–964.CrossRefGoogle Scholar
Hückel, E. (1925) The theory of concentrated aqueous solutions of strong electrolytes. Physikalische Zeitschrift, 26, 93–147.Google Scholar
Ivett, R.W. and Vries, T.D. (1941) The lead amalgam–lead fluoride electrode and thermodynamic properties of aqueous sodium fluoride solutions. Journal of the American Chemical Society, 63, 2821–2825.CrossRefGoogle Scholar
Jakusewski, B. and Taniewska-Osinska, S. (1962) Standard electrode potentials of alkaline earth metals in methanol. Roczniki Chemii, 36, 329–334.Google Scholar
Jensen, A.T. (1937) Über die Ausscheidung von Calciumfluorid aus übersättigten Lösungen. Zeitschrifte für physikalische Chemie, A180, 93–116.CrossRefGoogle Scholar
Knowles-Van Cappellen, V.L., Van Cappellen, P. and Tiller, C.L. (1997) Probing the charge of reactive sites at the mineral-water interface: Effect of ionic strength on crystal growth kinetics of fluorite. Geochimica et Cosmochimica Acta, 61, 1871–1877.CrossRefGoogle Scholar
Köhl, A.F. (1926) Beitrag zur analytische Bestimmung des Fluors [Contribution to the analytical determination of fluoride]. PhD Dissertation, ETH Zürich, Switzerland.Google Scholar
Kohlrausch, F. (1908) Über gesättigte wässerige Lösungen schwerlöslicher Salze. II Teil: Die gelösten Mengen mit ihrem Temperaturgang [Saturated aqueous solutions of sparingly soluble salts. Part II. The solubilities and their change with temperature]. Zeitschrifte für physikalische Chemie, 64, 129–169.CrossRefGoogle Scholar
Kurovskaya, N.A. and Malinin, S.D. (1983) The solubility of CaF2 in aqueous CaCl2-HCl-NaCl solutions at 25–200 °C and determination of CaF2 activity product. Geochemistry International, 20, 13–27.Google Scholar
Larsen, M.J. and Ravnholt, G. (1994) Dissolution of various calcium fluoride preparations in inorganic solutions and in stimulated human saliva. Caries Research, 28, 447–454.CrossRefGoogle ScholarPubMed
Latimer, W.M. (1952) Oxidation Potentials. 2nd ed. Prentice-Hall, Englewood Cliffs, New Jersey, USA.Google Scholar
Lewis, G.N. and Kraus, C.A. (1910) The potential of the sodium electrode. Journal of the American Chemical Society, 32, 1459–1468.CrossRefGoogle Scholar
Lewis, G.N. and Randall, M. (1923) Thermodynamics. McGraw-Hill, New York.Google Scholar
Li, H., Wang, S. and Zeng, D. (2017) Solubility and ionic interaction of the CaF2–CaSO4–H2O system at 298.1 K. Journal of Solution Chemistry, 46, 1941–1947.CrossRefGoogle Scholar
Li, H., Wang, S. and Zeng, D. (2018) Experimental measurement of the solid-liquid equilibrium of the systems MF2 + H2O (M = Mg, Ca, Zn) from 298.15 to 353.15 K. Journal of Chemical and Engineering Data, 63, 1733–1736.CrossRefGoogle Scholar
Luo, Q., Wang, S., Zeng, D. and Wang, Y. (2019) Solubility phase equilibrium of the quaternary reciprocal system Ca2+, Mn2+//F–, SO42– + H2O at 298.15 K. Journal of Chemical and Engineering Data, 64, 1834–1839.CrossRefGoogle Scholar
Macaskill, J.B. and Bates, R.G. (1977) Solubility product constant of calcium fluoride. Journal of Physical Chemistry, 81, 496–498.CrossRefGoogle Scholar
Macdonald, R.W. and North, N.A. (1974) The effect of pressure on the solubility of CaCO3, CaF2, and SrSO4 in water. Canadian Journal of Chemistry, 52, 3181–3186.CrossRefGoogle Scholar
Majer, V. and Stulik, K. (1982) A study of the stability of alkaline-earth metal complexes with fluoride and chloride ions at various temperatures by potentiometry with ion-selective electrodes. Talanta, 29, 145–148.CrossRefGoogle ScholarPubMed
May, P.M. and Murray, K. (2001) Database of chemical reactions designed to achieve thermodynamic consistency automatically. Journal of Chemical and Engineering Data, 46, 1035–1040.CrossRefGoogle Scholar
Millero, F.J. and Pierrot, D. (1998) A chemical equilibrium model for natural waters. Aquatic Geochemistry, 4, 153–199.CrossRefGoogle Scholar
Mockrin, I. (1950) Additions and corrections: Frere (1936) Equilibrium in fluoride systems. I. Solubility of cryolite in aqueous solutions of iron and aluminum salts. Journal of the American Chemical Society, 72, 5801.Google Scholar
Nordstrom, D.K. and Campbell, K.M. (2014) Modeling low-temperature geochemical processes. Pp. 27–68 in: Surface and Ground Water, Weathering, and Soils (Drever, J.I., editor). Elsevier, New York.Google Scholar
Nordstrom, D.K. and Jenne, E.A. (1977) Fluorite solubility equilibria in selected geothermal waters. Geochimica et Cosmochimica Acta, 41, 175–188.CrossRefGoogle Scholar
Nordstrom, D.K. and May, H.M. (1996) Aqueous equilibrium data for mononuclear aluminum species. Pp. 39–80 in: The Environmental Chemistry of Aluminum (Sposito, G., editor). 2nd edition, CRC Press, Baca Raton, Florida, USA.Google Scholar
Nordstrom, D.K. and Munoz, J.L. (1994) Geochemical Thermodynamics. 2nd ed. Blackwell Scientific Publications, Boston, USA.Google Scholar
Nordstrom, D.K. and Nicholson, A. (2017) Geochemical Modeling for Mine Site Characterization and Remediation. Society for Mining, Metallurgy & Exploration, Englewood, Colorado, USA.Google Scholar
Nordstrom, D.K., Plummer, L.N., Langmuir, D., Busenberg, E., May, H.M., Jones, B.F. and Parkhurst, D.L. (1990) Revised chemical equilibrium data for major water-mineral reactions and their limitations. American Chemical Society Symposium Series, 416, 398–413.CrossRefGoogle Scholar
Nuttall, R.L., Churney, K.L. and Kilday, M.V. (1978) The enthalpy of formation of MoF6(l) by solution calorimetry. Journal of Research of the National Bureau of Standards, 83, 335–345.CrossRefGoogle ScholarPubMed
Oelkers, E.H., Benezeth, P. and Pokrovski, G.S. (2009) Thermodynamic databases for water-rock interaction. Pp. 1–46 in: Thermodynamics and Kinetics of Water-Rock Interaction (Oelkers, E.H. and Schott, J., editors). Mineralogical Society of America and Geochemical Society, Chantilly, Virginia, USA.CrossRefGoogle Scholar
Ogorodova, L.N., Kiseleva, I.A. and Shuriga, T.N. (1989) Enthalpies of formation and phase transformation of cryolite. Geokhimiya, 8, 1180–1183.Google Scholar
Palmer, D.A. and Wesolowski, D.J. (1992) Aluminum speciation and equilibria in aqueous solution: II. The solubility of gibbsite in acidic sodium chloride solutions from 30 to 70 °C. Geochimica et Cosmochimica Acta, 56, 1093–1111.CrossRefGoogle Scholar
Pan, H.-B. and Darvell, B.W. (2007) Solubility of calcium fluoride and fluorapatite by solid titration. Archives of Oral Biology, 52, 861–868.CrossRefGoogle ScholarPubMed
Parkhurst, D.L. and Appelo, C.A.J. (1999) User's guide to PHREEQC (Version 2) – a computer program for speciation, batch-reaction, one-dimensional transport, and inverse geochemical calculations. USGS Water-Resources. Investigations Report, 99–4259, 312 pp, US Geological Survey, Reston, Virginia, USA.Google Scholar
Partanen, J.I. (2011) Re-evaluation of the thermodynamic activity quantities in aqueous solutions of silver nitrate, alkali metal fluorides and nitrites, and dihydrogen phosphate, dihydrogen arsenate, and thiocyanate salts with sodium and potassium at 25°C. Journal of Chemical and Engineering Data, 56, 2044–2062.CrossRefGoogle Scholar
Payne, J.H. (1937) The solubility of lithium and sodium fluorides. Journal of the American Chemical Society, 59, 947.CrossRefGoogle Scholar
Prud'homme, M. (1911) Sur la solubilité des sels difficilement solubles. Journal de Chimie Physique, 9, 519–537.CrossRefGoogle Scholar
Reynolds, J.G. and Belsher, J.D. (2017) A review of sodium fluoride in water. Journal of Chemical and Engineering Data, 62, 1743–1748.CrossRefGoogle Scholar
Roberson, C.E. and Hem, J.D. (1968) Activity product constant of cryolite at 25 °C and one atmosphere using selective-ion electrodes to estimate sodium and fluoride activities. Geochimica et Cosmochimica Acta, 32, 1343–1351.CrossRefGoogle Scholar
Roberson, C.E. and Hem, J.D. (1973) Solubility of cryolite at 25 °C and 1 atmosphere pressure. Journal of Research of the U.S. Geological Survey, 1, 482–485.Google Scholar
Robie, R.A. and Hemingway, B. (1995) Thermodynamic properties of minerals and related substances at 298.15 K and 1 bar (105 pascals) pressure and higher temperatures. U.S. Geological Survey Bulletin, 2131.Google Scholar
Robinson, R.A. (1941) The activity coefficients of sodium and potassium fluorides at 25° from isopiestic vapor pressure measurements. Journal of the American Chemical Society, 63, 628–629.CrossRefGoogle Scholar
Robinson, R.A. and Stokes, R.H. (1955) Electrolyte Solutions. Butterworths, London.Google Scholar
Shock, E.L. and Helgeson, H.C. (1988) Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000 °C. Geochimica et Cosmochimica Acta, 52, 2009–2036.CrossRefGoogle Scholar
Smyshlyaev, S.I. and Edeleva, N.P. (1962) Determination of solubility of minerals. I. The solubility product of fluorite. Izvestiya Vysshikh Uchebnykh Zavedenii, Khimiya i Khimicheskaya Tekhnologiya, 5, 871–874.Google Scholar
Street, J.J. and Elwali, A.M.O. (1983) Fluoride solubility in limed acid sandy soils. Soil Science Society of America Journal, 47, 483–485.CrossRefGoogle Scholar
Taghikhani, V., Modarress, H. and Vera, J.H. (2000) Measurement and correlation of the individual ionic activity coefficients of aqueous of aqueous electrolyte solutions oof KF, NaF and KBr. The Canadian Journal of Chemical Engineering, 78, 175–181.CrossRefGoogle Scholar
Tananaev, I.V. and Talipov, S. (1939) Solubility of fluorides of alkali metals. Zhurnal Obschei Khimiya, USSR, 9, 1155–1157.Google Scholar
Tananaev, I.V. and Vinogradova, A.D. (1957) Composition and stability of some fluoaluminates in solution. Zhurnal Neorganicheskoi Khimii, 2, 2455–2467.Google Scholar
Treadwell, W.D. and Köhl, A. (1926) Ein Beitrag zur analytischen Bestimmung des Fluorions. Helvetia Chimica Acta, 9, 470–485.CrossRefGoogle Scholar
Wagman, D.D., Evans, W.H., Parker, V.B., Schuman, P.H., Halow, I., Bailey, S.M., Churney, K.L. and Nuttall, R.L. (1982) The NBS tables of chemical thermodynamic properties: selected values for inorganic and C1 and C2 organic substances in SI units. Journal of Physical and Chemical Reference Data, 11, 1–392.Google Scholar
Zamorano-Santander, W. (1985) Thermodynamics of ion association in aqueous fluoride solutions. Determination of stability constants for (NaF), (MgF)+, and CaF+ ion pairs, Master of Science Thesis, Chemistry, Eastern Illinois University.Google Scholar
Zhang, N., Tang, J., Luo, Q., Wang, S. and Zeng, D. (2021) Computational and solubility equilibrium experimental insight into Ca2+-fluoride complexation and their dissociation behaviors in aqueous solutions: implication for the association constant measured using fluoride ion selective electrodes. Physical Chemistry and Chemical Physics, 23, 24711–24725.CrossRefGoogle ScholarPubMed
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