It is established that the rates of solvent exchange at interfaces correlate with the rates of a number of mineral reactions, including growth, dissolution and ion sorption. To test if solvent exchange is limiting these rates, quasi-elastic neutron scattering (QENS) is used here to benchmark classical molecular dynamics (CMD) simulations of water bound to nanoparticulate calcite. Four distributions of solvent exchanges are found with residence times of 8.9 ps for water bound to calcium sites, 14 ps for that bound to carbonate sites and 16.7 and 85.1 ps for two bound waters in a shared calcium-carbonate conformation. By comparing rates and activation energies, it is found that solvent exchange limits reaction rates neither for growth nor dissolution, likely due to the necessity to form intermediate states during ion sorption. However, solvent exchange forms the ceiling for reaction rates and yields insight into more complex reaction pathways.

Central European Institute of Technology Masaryk University Kamenice 5 625 00 Brno Czech Republic

Chemical Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA

Computer Science and Mathematics Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA

Department of Chemical Engineering Columbia University New York NY 10027 USA

Neutron Sciences Division Oak Ridge National Laboratory Oak Ridge TN 37831 USA

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