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A thermochemical and kinetic analysis of the mechanisms of pyrolysis of polycyclic molecules
Author(s) -
O'Neal H. E.,
Benson Sidney W.
Publication year - 1970
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.550020602
Subject(s) - chemistry , arrhenius equation , activation energy , kinetics , kinetic energy , pyrolysis , entropy of activation , computational chemistry , thermodynamics , reaction mechanism , transition state theory , molecule , transition state , reaction rate constant , organic chemistry , catalysis , physics , quantum mechanics
The quantitative kinetics of pyrolysis of some cyclic and polycyclic compounds are examined from the point of view of biradical intermediates. Transition state methods for estimating the Arrhenius parameters of the lowest free energy biradical pathway to products in cyclic and polycyclic compound reactions are described and illustrated. A large number of the polycyclic reactions are found to have Arrhenius parameters consistent with the biradical mechanism estimates. Other reactions are found to have much faster experimental rates and must therefore be concerted. The value of activation energy and activation entropy estimates as discriminatory tests of mechanism, i.e., single step (concertedness) or consecutive step processes, is discussed.