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The Kinetics of Calcite Growth: Interpreting Chemical Affinity-Based Rate Laws Through the Lens of Direct Observation

Published online by Cambridge University Press:  14 March 2011

Henry H. Teng ,
Patricia M. Dove  and
James J. De Yoreo
Henry H. Teng
Affiliation:
Department of GeologyGeorge Washington University, Washington, D.C. 20052
Patricia M. Dove
Affiliation:
Department of Geological Sciences Virginia Polytechnic Institute and State University Blacksburg, VA 24061
James J. De Yoreo
Affiliation:
Department of Chemistry and Materials Science Lawrence Livermore National Laboratory Livermore, CA 94550
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Abstract

Chemical affinity-based rate laws are used across the geochemical and materials communities to quantify mineral/material corrosion and growth kinetics. These rate expressions are founded in assumptions regarding reaction mechanism with little evidence for surface processes. Using Atomic Force Microscopy (AFM), this study demonstrates the dependence of growth kinetics upon the structures of dislocation sources. In situ observations show that the dominant mode of growth occurs by hillock development initiated at complex sources. Derivations of surface process-based rate expressions show a complex dependence of rate on chemical affinity. This dependence is approximated by second order affinity-based rate laws only under the special conditions that 1) growth proceeds by development of single sourced spirals and 2) growth occurs at very near equilibrium conditions where spiral formation is the only operative mechanism. This suggests that growth experiments that measure temporal changes in solution chemistry yield a composite rate that arises from the contributions of the different hillock types. Hence, chemical affinity-based rate laws do not generally give meaningful interpretations of growth mechanism. By combining direct observations with macroscopic methods that monitor temporal changes in solution chemistry, rate laws with greater predictive capabilities may be possible.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 620: Symposium M – Morphology & Dynamics of Crystal Surfaces in Complex… , 2000 , M2.6.1
Copyright
Copyright © Materials Research Society 2000

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