Calcite Dissolution Kinetics

Abstract

We compare the canonical treatment of calcite’s dissolution rate from the literature in a closed system, particle batch reactor, with the alternative approach suggested by Truesdale (Aquat Geochem, 2015). We show that the decay of rate over time can be understood in terms of the evolution and distribution of reactive sites on the surface of these particles. We also emphasize that interpretation of observed rates must not exclude the fundamental role of crystal defects, whose importance is already implicitly reflected in the common form of rate laws in geochemistry. The empirical behavior of overall rate in closed systems, such as those described by Truesdale, may thus reflect relationships between defect centers and the generation of steps over the calcite surface (previously documented for silicates), such that below a critical free energy limit, there is insufficient driving force to open hollow cores and thus a loss of reaction mechanism. Dissolution in this very-near-equilibrium regime will be dependent on the distribution of extant steps and the energetics of new kink site nucleation. However, these sensitivities are complicated in the case of particle systems by grain boundaries, edges, corners, and other terminations. Such discontinuities constitute a defect class whose overall kinetic importance will be strongly tied to particle diameter and which can act independently of the internal strain field imposed by screw and edge dislocations.