A thermochemical and kinetic analysis of the mechanisms of pyrolysis of polycyclic molecules
- 1 November 1970
- journal article
- research article
- Published by Wiley in International Journal of Chemical Kinetics
- Vol. 2 (6) , 423-456
- https://doi.org/10.1002/kin.550020602
Abstract
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.Keywords
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