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Title: Extension of structure-reactivity correlations for the hydrogen abstraction reaction by bromine atom and comparison to chlorine atom and hydroxyl radical

Abstract

Recently we presented structure-reactivity correlations for the gas-phase ambient-temperature rate constants for hydrogen abstraction from sp3-hybridized carbon by chlorine atom and hydroxyl radical (Cl•/HO• + HCR3 → HCl/HOH + •CR3); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett constants for field/inductive and resonance effects. Both these reactions are predominantly exothermic and have early transition states. Here we present a parallel treatment for Br• whose reaction is significantly endothermic with a correspondingly late transition state. In spite of lower expectations because the available data base is less extensive and much more scattered and because long temperature extrapolations are often required, the resulting least-squares fit (log k298,Br = –0.147 ΔrH –4.32 ΣF –4.28 ΣR –12.38 with r2 = 0.92) was modestly successful and useful for initial predictions. The coefficient of ΔrH was ~4-fold greater, indicative of the change from an early to a late transition state; meanwhile the sizable coefficients of ΣF and ΣR indicate the persistence of the polar effect. Although the mean unsigned deviation of 0.79 log k298 units is rather large, it must be considered in the context of a total span ofmore » over 15 log units in the data set. Lastly, the major outliers are briefly discussed.« less

Authors:
 [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1235833
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 120; Journal Issue: 2; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Poutsma, Marvin L. Extension of structure-reactivity correlations for the hydrogen abstraction reaction by bromine atom and comparison to chlorine atom and hydroxyl radical. United States: N. p., 2015. Web. https://doi.org/10.1021/acs.jpca.5b10989.
Poutsma, Marvin L. Extension of structure-reactivity correlations for the hydrogen abstraction reaction by bromine atom and comparison to chlorine atom and hydroxyl radical. United States. https://doi.org/10.1021/acs.jpca.5b10989
Poutsma, Marvin L. Mon . "Extension of structure-reactivity correlations for the hydrogen abstraction reaction by bromine atom and comparison to chlorine atom and hydroxyl radical". United States. https://doi.org/10.1021/acs.jpca.5b10989. https://www.osti.gov/servlets/purl/1235833.
@article{osti_1235833,
title = {Extension of structure-reactivity correlations for the hydrogen abstraction reaction by bromine atom and comparison to chlorine atom and hydroxyl radical},
author = {Poutsma, Marvin L.},
abstractNote = {Recently we presented structure-reactivity correlations for the gas-phase ambient-temperature rate constants for hydrogen abstraction from sp3-hybridized carbon by chlorine atom and hydroxyl radical (Cl•/HO• + HCR3 → HCl/HOH + •CR3); the reaction enthalpy effect was represented by the independent variable ΔrH and the polar effect by the independent variables F and R, the Hammett constants for field/inductive and resonance effects. Both these reactions are predominantly exothermic and have early transition states. Here we present a parallel treatment for Br• whose reaction is significantly endothermic with a correspondingly late transition state. In spite of lower expectations because the available data base is less extensive and much more scattered and because long temperature extrapolations are often required, the resulting least-squares fit (log k298,Br = –0.147 ΔrH –4.32 ΣF –4.28 ΣR –12.38 with r2 = 0.92) was modestly successful and useful for initial predictions. The coefficient of ΔrH was ~4-fold greater, indicative of the change from an early to a late transition state; meanwhile the sizable coefficients of ΣF and ΣR indicate the persistence of the polar effect. Although the mean unsigned deviation of 0.79 log k298 units is rather large, it must be considered in the context of a total span of over 15 log units in the data set. Lastly, the major outliers are briefly discussed.},
doi = {10.1021/acs.jpca.5b10989},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 2,
volume = 120,
place = {United States},
year = {2015},
month = {12}
}

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