The recent literature on the kinetics of water‐rock interactions is reviewed. The data are then extended to provide a quantitative framework for the description of weathering and alteration. The available experimental data on dissolution of silicates verifies quantitatively the usual mineral stability series in sedimentary petrology. The rate of hydration of carbonic acid is shown to be a possible limiting factor in water‐rock interactions. The framework is developed to enable use of laboratory dissolution experimental results and thermodynamics to arrive at a rate law applicable up to equilibrium and therefore applicable to natural systems. The kinetic justification for the significance of a water‐rock ratio is discussed. With a proper treatment of fluid flow, the equations are applied to the weathering profile leading to the development of bauxites from nepheline syenites.
A formulation based on defect-generated dissolution stepwaves of the variation of dissolution rate with the degree of undersaturation is validated by near-atomic-scale observations of surfaces, Monte Carlo simulations, and experimental bulk dissolution rates. The dissolution stepwaves emanating from etch pits provide a train of steps similar to those of a spiral but with different behavior. Their role in accounting for the bulk dissolution rate of crystals provides a conceptual framework for mineral dissolution far from equilibrium. Furthermore, the law extends research to conditions closer to equilibrium and predicts a nonlinear decrease in the rate of dissolution as equilibrium is approached, which has implications for understanding artificial and natural processes involving solid-fluid reactions.
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