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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

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:
 [1]
  1. Sandia National Labs., Carlsbad, NM (United States)
Publication Date:
OSTI Identifier:
1235350
Report Number(s):
SAND--2015-1162J
Journal ID: ISSN 1380-6165; 567067
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Aquatic Geochemistry
Additional Journal Information:
Journal Volume: 21; Journal Issue: 5; Journal ID: ISSN 1380-6165
Research Org:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY transition-state theory; dissolution kinetics; calcite; ACC