『Abstract
The natural weathering rates of primary minerals are often orders
of magnitude lower than the rates of mineral dissolution measured
in laboratory experiments. Primary dissolution rates are thought
to be determined by the rate of secondary mineral precipitation,
and in this paper we present a new approach to quantify the role
played by interfacial energy, crystal size, and degree of supersaturation
on precipitation kinetics in a population of crystals growing
in a supersaturated fluid. We demonstrate that net mineral precipitation
rates in systems that are close to equilibrium, and which possess
a large number of micron and nanometer scale crystals, can be
much lower than the rates predicted by standard kinetic equations.
Moreover, when crystals are small enough, net dissolution dominates
even when the system is supersaturated with respect to large crystals
so that the standard reaction rate models used to describe bulk
rates will no longer apply. Importantly, secondary minerals that
form from the incongruent dissolution of primary phases are often
submicron in size and field conditions are often far closer to
equilibrium than those typically encountered in laboratory experiments.
Thus, we propose that standard kinetic models - which ignore interfacial
energy effects in small crystals - may be unsuitable to describe
reaction kinetics in weathering systems.
Keywords: Reaction kinetics; Interfacial free energy; Crysalization;
Precipitation』
1. Introduction
2. Theory
2.1. Dependence of weathering rates on secondary mineral
precipitation
2.2. Kinetic theory and interfacial energy effects
2.3. Quantifying the effect of interfacial energy on precipitation
rates
3. Results and discussion
3.1. Assessing the impact of interfacial energy on reaction
rates
3.2. Relationship between field rates and laboratory kinetics
4. Concluding remarks
Acknowledgments
Appendix A. Evolving crystal size populations
References