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Molecular Dynamics Evaluation of Dielectric Constant Mixing Rules for H2O–CO2 at Geologic Conditions

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Abstract

Modeling of mineral reaction equilibria and aqueous-phase speciation of C–O–H fluids requires the dielectric constant of the fluid mixture, which is not known from experiment and is typically estimated by some rule for mixing pure component values. In order to evaluate different proposed mixing rules, we use molecular dynamics simulation to calculate the dielectric constant of a model H2O–CO2 mixture at temperatures of 700 and 1000 K at pressures up to 3 GPa. We find that theoretically based mixing rules that depend on combining the molar polarizations of the pure fluids systematically overestimate the dielectric constant of the mixture, as would be expected for mixtures of nonpolar and strongly polar components. The commonly used semiempirical mixing rule due to Looyenga works well for this system at the lower pressures studied but somewhat underestimates the dielectric constant at higher pressures and densities, especially at the water-rich end of the composition range.

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Acknowledgments

We thank Dr. Matthieu Galvez for bringing this problem to our attention and for helpful comments during the course of the work.

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Authors and Affiliations

  1. Chemical Sciences Division, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD, 20899, USA

    Raymond D. Mountain

  2. Applied Chemicals and Materials Division, National Institute of Standards and Technology, 325 Broadway, Boulder, CO, 80305, USA

    Allan H. Harvey

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  1. Raymond D. Mountain
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  2. Allan H. Harvey
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Correspondence to Allan H. Harvey.

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Mountain, R.D., Harvey, A.H. Molecular Dynamics Evaluation of Dielectric Constant Mixing Rules for H2O–CO2 at Geologic Conditions. J Solution Chem 44, 2179–2193 (2015). https://doi.org/10.1007/s10953-015-0401-6

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  • DOI: https://doi.org/10.1007/s10953-015-0401-6

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