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Copper in Hydrothermal Systems: a Thermodynamic Description of Hydroxocomplexes

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Abstract

Experimental data available in the literature on the solubility of Cu (met.) and Cu2O (cuprite) in water under hydrothermal conditions have been processed. Key experiments on the solubility of cuprite were carried out at 300°C and the saturated vapor pressure of H2O vs. pH of the solution. As a result, a set of values of thermodynamic properties for 25°C, 1 bar and the parameters of the Helgeson–Kirkham–Flowers and Akinfiev–Diamond equations of state for Cu(I) hydroxocomplexes were obtained, which make it possible to describe their behavior in a wide range of temperatures (0–600°C), pressures (1–3000 bar), and densities of aqueous fluid (0.01–1 g/cm3). As has been shown by thermodynamic modeling, Cu+ ions are prevalent in the acidic and weakly alkaline regions of the aqueous solvent over the entire temperature and pressure range studied. The effect of the neutral CuOH hydroxocomplex begins to show up in the alkaline region at T > 300°C and grows with increasing temperature. The second copper hydroxocomplex \({\text{Cu}}\left( {{\text{OH}}} \right)_{2}^{ - }\) shows up only in the strongly alkaline region, and the temperature has almost no effect on its behavior.

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REFERENCES

  1. Akinfiev, N.N. and Diamond, L.W., Thermodynamic description of aqueous nonelectrolytes at infinite dilution over a wide range of state parameters, Geochim. Cosmochim. Acta, 2003, vol. 67, no. 4, pp. 613–627. https://doi.org/10.1016/s0016-7037(02)01141-9

    Article  Google Scholar 

  2. Akinfiev, N.N. and Plyasunov, A.V., Application of the Akinfiev–Diamond equation of state to neutral hydroxides of metalloids (B(OH)3, Si(OH)4, As(OH)3) at infinite dilution in water over a wide range of the state parameters, including steam conditions, Geochim. Cosmochim. Acta, 2014, vol. 126, pp. 338–351. https://doi.org/10.1016/j.gca.2013.11.013

    Article  Google Scholar 

  3. Akinfiev, N.N, Voronin, M.V., Zotov, A.V., and Prokof’ev, V.Yu., Experimental investigation of the stability of a chloroborate complex and thermodynamic description of aqueous species in the B–Na–Cl–O–H system up to 350°C, Geochem. Int., 2006, vol. 44, no. 9, pp. 867–878.

    Article  Google Scholar 

  4. Born, M., Volumen und hydratationswarme der ionen, Zeitschr. Physik, 1920, vol. 1, pp. 45–48.

    Article  Google Scholar 

  5. Frisch, M.J., et al., Gaussian 09, Revision C.01, Wallingford CT: Gaussian, Inc., 2009.

    Google Scholar 

  6. Helgeson, H.C., Kirkham, D.H., and Flowers, G.C., Theoretical prediction of the thermodynamic behavior of aqueous electrolytes at high pressures and temperatures: IV. Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600°C and 5 kb, Am. J. Sci., 1981, vol. 291, pp. 1249–1516.

    Article  Google Scholar 

  7. Johnson, J.W., Oelkers, E.H., and Helgeson, H.C., Supcrt92: a software package for calculating the standard molal thermodynamic properties of minerals, gases, aqueous species, and reactions from 1 to 5000 bars and 0°C to 1000°C, Comp. Geosci., 1992, vol. 18, pp. 899–947.

    Article  Google Scholar 

  8. Marenich, A.V., Cramer, C.J., and Truhlar, D.G., Universal solvation model based on solute electron density and on a continuum model of the solvent defined by the bulk dielectric constant and atomic surface tensions, J. Phys. Chem. B., 2009, vol. 113, pp. 6378–6396.

    Article  Google Scholar 

  9. Messerly, R.A., Yoon, T.J., Jadrich, R.B., Currier, R.P., and Maerzke, K.A., Elucidating the temperature and density dependence of silver chloride hydration numbers in high-temperature water vapor: a first-principles molecular simulation study, Chem. Geol., vol. 594, p. 120766. https://doi.org/10.1016/j.chemgeo.2022.120766

  10. Palmer, D.A., Solubility measurements of crystalline Cu2O in aqueous solution as a function of temperature and pH, J. Solution Chem., 2011, vol. 40, pp. 1067–1093. https://doi.org/10.1007/s10953-011-9699-x

    Article  Google Scholar 

  11. Pocock, F.J. and Stewart, J.F., The Solubility of copper and Its oxides in supercritical steam, J. Eng. Power, 1963, vol. 85, no. 1, pp. 33–44. https://doi.org/10.1115/1.3675213

    Article  Google Scholar 

  12. Robie, R.A. and Hemingway, B.S., Thermodynamic properties of minerals and related substances at 298.15 and 1 bar (105 pascals) pressure and at high temperatures, U. S. Geol. Surv. Bull., 1995, no. 2131.

  13. Rubtsova, E.A., Tagirov, B.R., et al., Joint solubility of Cu and Ag in chloride hydrothermal fluids (350–650°C, 1000–1500 bar), Geol. Ore Deposits, 2023 (in press).

  14. Shannon, R.D., Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr., vol. A32, pp. 751–767.

  15. Shock, E.L. and Helgeson, H.C., 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, Geochim. Cosmochim. Acta, 1988, vol. 52, pp. 2009–2036.

    Article  Google Scholar 

  16. Shock, E.L., Helgeson, H.C., and Sverjensky, D.A., Calculation of the thermodynamic properties of aqueous species at high pressures and temperatures: standard partial molal properties of inorganic neutral species, Geochim. Cosmochim. Acta, 1989, vol. 53, pp. 2157–2183.

    Article  Google Scholar 

  17. Shock, E.L., Sassani, D.C., Willis, M., and Sverjensky, D.A., Inorganic species in geologic fluids: correlations among standard molal thermodynamic properties of aqueous ions and hydroxide complexes, Geochim. Cosmochim. Acta, 1997, vol. 61, pp. 907–950.

    Article  Google Scholar 

  18. Shvarov, Yu.V., A suite of programs, OptimA, OptimB, OptimC, and OptimS compatible with the Unitherm database, for deriving the thermodynamic properties of aqueous species from solubility, potentiometry and spectroscopy measurements, Appl. Geochem., 2015, vol. 55, pp. 17–27.

    Article  Google Scholar 

  19. Sverjensky, D.A., Shock, E.L., and Helgeson, H.C., Prediction of thermodynamic properties of aqueous metal complexes to 1000°C and 5 kb, Geochim. Cosmochim. Acta, 1997, vol. 61, pp. 1359–1412.

    Article  Google Scholar 

  20. Tagirov, B.R., Zotov, A.V., and Akinfiev, N.N., Experimental study of dissociation of HCl from to 500°C and from 500 to 2500 bars: thermodynamic properties of HCl(aq), Geochim. Cosmochim. Acta, 1997, vol. 61, pp. 4267–4280.

    Article  Google Scholar 

  21. Tanger, IV, J.C. and Helgeson, H.C., Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: revised equations of state for standard partial molal properties of ions and electrolytes, Am. J. Sci., 1988, vol. 288, pp. 19–98.

    Article  Google Scholar 

  22. Var’yash, L.N., Experimental study of equilibrium in the Cu–Cu2O–H2O system within temperature range of 150–450°C, Geokhimiya, 1989, no. 3, pp. 412–422.

  23. Wagman, D.D. Evans, W.H., et al., The NBS tables of chemical thermodynamic properties, J. Phys. Chem. Ref. Data, 1982, vol. 11, Suppl. No. 2.

  24. Wagner, W. and Pruß A., The IAPWS formulation for the thermodynamic properties of ordinary water substances for general and scientific use, J. Phys. Chem. Ref. Data, 2002, vol. 31, pp. 387–535.

    Article  Google Scholar 

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ACKNOWLEDGMENTS

The authors are grateful to L.N. Var’yash for providing crystalline cuprite for the experiments and to S. Aksenov, who took part in the experimental work.

Funding

This work was supported by the Russian Science Foundation, grant no. 20-17-00184.

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Authors and Affiliations

  1. Institute of Geology of Ore Deposits, Petrography, Mineralogy, and Geochemistry, Russian Academy of Sciences, 119017, Moscow, Russia

    N. N. Akinfiev & A. V. Zotov

  2. Ordzhonikidze Russian State Geological Prospecting University, 117997, Moscow, Russia

    N. N. Akinfiev

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  1. N. N. Akinfiev
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  2. A. V. Zotov
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Correspondence to N. N. Akinfiev.

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Akinfiev, N.N., Zotov, A.V. Copper in Hydrothermal Systems: a Thermodynamic Description of Hydroxocomplexes. Geol. Ore Deposits 65, 1–10 (2023). https://doi.org/10.1134/S1075701523010026

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