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Title: A Microkinetic Model of Calcite Step Growth

Abstract

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.

Authors:
 [1];  [1];  [2];  [1];  [3];  [1]
  1. University of Copenhagen
  2. UNIVERSITY PROGRAMS
  3. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1526979
Report Number(s):
PNNL-SA-122782
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Angewandte Chemie International Edition
Additional Journal Information:
Journal Volume: 55; Journal Issue: 37
Country of Publication:
United States
Language:
English

Citation Formats

Andersson, M P., Dobberschutz, S, Sand, Karina K., Tobler, D J., De Yoreo, James J., and Stipp, S L. A Microkinetic Model of Calcite Step Growth. United States: N. p., 2016. Web. doi:10.1002/anie.201604357.
Andersson, M P., Dobberschutz, S, Sand, Karina K., Tobler, D J., De Yoreo, James J., & Stipp, S L. A Microkinetic Model of Calcite Step Growth. United States. doi:10.1002/anie.201604357.
Andersson, M P., Dobberschutz, S, Sand, Karina K., Tobler, D J., De Yoreo, James J., and Stipp, S L. Mon . "A Microkinetic Model of Calcite Step Growth". United States. doi:10.1002/anie.201604357.
@article{osti_1526979,
title = {A Microkinetic Model of Calcite Step Growth},
author = {Andersson, M P. and Dobberschutz, S and Sand, Karina K. and Tobler, D J. and De Yoreo, James J. and Stipp, S L.},
abstractNote = {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.},
doi = {10.1002/anie.201604357},
journal = {Angewandte Chemie International Edition},
number = 37,
volume = 55,
place = {United States},
year = {2016},
month = {9}
}

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