A Microkinetic Model of Calcite Step Growth
Corresponding Author
Prof. Dr. M. P. Andersson
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorDr. S. Dobberschütz
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorDr. K. K. Sand
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352 USA
Search for more papers by this authorDr. D. J. Tobler
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorProf. Dr. J. J. De Yoreo
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352 USA
Departments of Materials Science and Engineering and of Chemistry, University of Washington, Seattle, WA, 98195 USA
Search for more papers by this authorProf. Dr. S. L. S. Stipp
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorCorresponding Author
Prof. Dr. M. P. Andersson
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorDr. S. Dobberschütz
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorDr. K. K. Sand
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352 USA
Search for more papers by this authorDr. D. J. Tobler
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorProf. Dr. J. J. De Yoreo
Physical Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352 USA
Departments of Materials Science and Engineering and of Chemistry, University of Washington, Seattle, WA, 98195 USA
Search for more papers by this authorProf. Dr. S. L. S. Stipp
Nano-Science Center, Department of Chemistry, University of Copenhagen, Denmark
Search for more papers by this authorAbstract
In spite of decades of research, mineral growth models based on ion attachment and detachment rates fail to predict behavior beyond a narrow range of conditions. Here we present a microkinetic model that accurately reproduces calcite growth over a very wide range of published experimental data for solution composition, saturation index, pH and impurities. We demonstrate that polynuclear complexes play a central role in mineral growth at high supersaturation and that a classical complexation model is sufficient to reproduce measured rates. Dehydration of the attaching species, not the mineral surface, is rate limiting. Density functional theory supports our conclusions. The model provides new insights into the molecular mechanisms of mineral growth that control biomineralization, mineral scaling and industrial material synthesis.
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