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Relationship between bond dissociation energies and activation energies for bond scission reactions
Author(s) -
Smith G. P.,
Manion J. A.,
Rossi M. J.,
Rodgers A. S.,
Golden D. M.
Publication year - 1994
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550260120
Subject(s) - chemistry , thermochemistry , bond cleavage , bond dissociation energy , dissociation (chemistry) , bond energy , kinetics , activation energy , thermodynamics , transition state , computational chemistry , transition state theory , reaction rate constant , organic chemistry , molecule , catalysis , physics , quantum mechanics
Bond dissociation energies are frequently derived from values of the high pressure activation energy for bond scission reactions. The value derived depends on the transition state structure chosen for the reaction. We consider several models of the transition state and show that the variation in derived BDE values can be quite substantial, 3 to 6 kcal/mol at the high temperatures of pyrolysis kinetics. Application of the restricted Gorin model of the transition state results in BDE values in good agreement with current thermochemistry, while the other models tested result in lower to much lower values. © 1994 John Wiley & Sons, Inc.