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A Microkinetic Model of Calcite Step Growth
Author(s) -
Andersson M. P.,
Dobberschütz S.,
Sand K. K.,
Tobler D. J.,
De Yoreo J. J.,
Stipp S. L. S.
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201604357
Subject(s) - supersaturation , calcite , biomineralization , mineral , scaling , chemistry , limiting , saturation (graph theory) , impurity , growth rate , mineralogy , chemical engineering , thermodynamics , chemical physics , organic chemistry , physics , mechanical engineering , geometry , mathematics , combinatorics , engineering
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.