Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale

Icenhower, Jonathan P.

doi:10.1007/s10498-015-9266-y

Title: Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale

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Abstract

Transition-state theory (TST) is a successful theory for understanding many different types of reactions, but its application to mineral-water systems has not been successful, especially as the system approaches saturation with respect to a rate-limiting phase. A number of investigators have proposed alternate frameworks for using the kinetic rate data to construct models of dissolution, including Truesdale (Aquat Geochem, 2015; this issue). This alternate approach has been resisted, in spite of self-evident discrepancies between TST expectations and the data. The failure of TST under certain circumstances is a result of the presence of metastable intermediaries or reaction layers that form on the surface of reacting solids, and these phenomena are not anticipated by the current theory. Furthermore, alternate approaches, such as the shrinking object model advocated by Truesdale, represent a potentially important avenue for advancing the science of dissolution kinetics.

Authors:

Icenhower, Jonathan P. ^[1]

Sandia National Labs., Carlsbad, NM (United States)

Publication Date:: Tue Jun 23 00:00:00 EDT 2015

Research Org.:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1235350

Report Number(s):: SAND-2015-1162J
Journal ID: ISSN 1380-6165; 567067

Grant/Contract Number:: AC04-94AL85000

Resource Type:: Accepted Manuscript

Journal Name:: Aquatic Geochemistry

Additional Journal Information:: Journal Volume: 21; Journal Issue: 5; Journal ID: ISSN 1380-6165

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; transition-state theory; dissolution kinetics; calcite; ACC

Citation Formats


                    Icenhower, Jonathan P. Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale.  United States: N. p., 2015. 
Web.  doi:10.1007/s10498-015-9266-y.

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                    Icenhower, Jonathan P. Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale.  United States.  https://doi.org/10.1007/s10498-015-9266-y

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                    Icenhower, Jonathan P. Tue .  
"Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale".  United States.  https://doi.org/10.1007/s10498-015-9266-y.  https://www.osti.gov/servlets/purl/1235350.

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@article{osti_1235350,

  title        = {Empirical kinetics and their role in elucidating the utility of transition-state theory to mineral–water reactions. A comment upon, ''Evidence and Potential Implications of Exponential Tails to Concentration Versus Time Plots for the Batch Dissolution of Calcite'' by V. W. Truesdale},

  author       = {Icenhower, Jonathan P.},

  abstractNote = {Transition-state theory (TST) is a successful theory for understanding many different types of reactions, but its application to mineral-water systems has not been successful, especially as the system approaches saturation with respect to a rate-limiting phase. A number of investigators have proposed alternate frameworks for using the kinetic rate data to construct models of dissolution, including Truesdale (Aquat Geochem, 2015; this issue). This alternate approach has been resisted, in spite of self-evident discrepancies between TST expectations and the data. The failure of TST under certain circumstances is a result of the presence of metastable intermediaries or reaction layers that form on the surface of reacting solids, and these phenomena are not anticipated by the current theory. Furthermore, alternate approaches, such as the shrinking object model advocated by Truesdale, represent a potentially important avenue for advancing the science of dissolution kinetics.},

  doi          = {10.1007/s10498-015-9266-y},

  journal      = {Aquatic Geochemistry},

  number       = 5,

  volume       = 21,

  place        = {United States},

  year         = {Tue Jun 23 00:00:00 EDT 2015},

  month        = {Tue Jun 23 00:00:00 EDT 2015}

}

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