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Calculation of mass transfer among minerals and aqueous solutions as a function of time and surface area in geochemical processes. I. computational approach

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Abstract

Equations representing conservation of mass and charge, partial and local equilibrium constraints, and effective surface area as a function of reaction progress can be combined with a numerical integration computer routine and the rate equations proposed by Aagaard and Helgeson (1977, 1982)to predict quantitatively the consequences of irreversible reactions among minerals and aqueous solutions as a function of time and surface area in geochemical processes. Including provision for changing relative rates for several minerals reacting simultaneously with an aqueous solution affords a more realistic description of interphase mass transfer than has been achieved in the past. Computer experiments indicate that reactions among minerals and acid aqueous solutions in geochemical processes take place over relatively short periods of time and that the rate of change is controlled by the pH of the aqueous phase, either directly through formation of activated complexes on the surfaces of the reactant minerals, or indirectly through the dependence on pH of the chemical affinities of the overall reactions. As solution pH increases, the chemical affinities of the hydrolysis reactions decrease dramatically. As a consequence, early incongruent reaction products form much more rapidly than those produced or destroyed in later stages of reaction progress, where reaction rates become proportional to the chemical affinities of the overall hydrolysis reactions. Under these conditions, quasistatic states may persist for long periods of geologic time and result in spatial differences in fluid composition corresponding to different degrees of progress toward overall equilibrium.

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  1. Department of Geology and Geophysics, University of California, 94720, Berkeley, California, USA

    Harold C. Helgeson & William M. Murphy

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  1. Harold C. Helgeson
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  2. William M. Murphy
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Helgeson, H.C., Murphy, W.M. Calculation of mass transfer among minerals and aqueous solutions as a function of time and surface area in geochemical processes. I. computational approach. Mathematical Geology 15, 109–130 (1983). https://doi.org/10.1007/BF01030078

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