Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories

Mineral growth and dissolution are often treated as occurring via a single reversible process that governs the rate of reaction. We show that multiple distinct intermediate states can occur during both growth and dissolution. Specifically, we used metadynamics, a method for efficiently exploring the...

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Main Authors: Stack, A., Raiteri, Paolo, Gale, Julian
Format: Journal Article
Published: The American Chemical Society 2012
Online Access:http://hdl.handle.net/20.500.11937/44964
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author Stack, A.
Raiteri, Paolo
Gale, Julian
author_facet Stack, A.
Raiteri, Paolo
Gale, Julian
author_sort Stack, A.
building Curtin Institutional Repository
collection Online Access
description Mineral growth and dissolution are often treated as occurring via a single reversible process that governs the rate of reaction. We show that multiple distinct intermediate states can occur during both growth and dissolution. Specifically, we used metadynamics, a method for efficiently exploring the free-energy landscape of a system, coupled to umbrella sampling and reactive flux calculations to examine the mechanism and rates of attachment and detachment of a barium ion onto a stepped barite (BaSO4) surface. The activation energies calculated for the rate-limiting reactions, which are different for attachment and detachment, precisely match those measured experimentally during both growth and dissolution. These results can potentially explain anomalous non-steady-state mineral reaction rates observed experimentally and will enable the design of more efficient growth inhibitors and facilitate an understanding of the effect of impurities.
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publishDate 2012
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spelling curtin-20.500.11937-449642017-09-13T15:57:41Z Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories Stack, A. Raiteri, Paolo Gale, Julian Mineral growth and dissolution are often treated as occurring via a single reversible process that governs the rate of reaction. We show that multiple distinct intermediate states can occur during both growth and dissolution. Specifically, we used metadynamics, a method for efficiently exploring the free-energy landscape of a system, coupled to umbrella sampling and reactive flux calculations to examine the mechanism and rates of attachment and detachment of a barium ion onto a stepped barite (BaSO4) surface. The activation energies calculated for the rate-limiting reactions, which are different for attachment and detachment, precisely match those measured experimentally during both growth and dissolution. These results can potentially explain anomalous non-steady-state mineral reaction rates observed experimentally and will enable the design of more efficient growth inhibitors and facilitate an understanding of the effect of impurities. 2012 Journal Article http://hdl.handle.net/20.500.11937/44964 10.1021/ja204714k The American Chemical Society restricted
spellingShingle Stack, A.
Raiteri, Paolo
Gale, Julian
Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories
title Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories
title_full Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories
title_fullStr Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories
title_full_unstemmed Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories
title_short Accurate Rates of the Complex Mechanisms for Growth and Dissolution of Minerals Using a Combination of Rare-Event Theories
title_sort accurate rates of the complex mechanisms for growth and dissolution of minerals using a combination of rare-event theories
url http://hdl.handle.net/20.500.11937/44964