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The gas phase reaction of CF 3 radicals with C 6 F 5 H in the temperature range 373–658 K
Author(s) -
Lane S. I.,
Oexler E. V.,
Staricco E. H.
Publication year - 1991
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.550230502
Subject(s) - radical , chemistry , reaction rate constant , benzene , photodissociation , atmospheric temperature range , gas phase , analytical chemistry (journal) , photochemistry , thermodynamics , kinetics , organic chemistry , physics , quantum mechanics
Abstract CF 3 radicals were generated by the photolysis of perfluoroacetic anhydride. In the presence of pentafluorobenzene, the CF 3 radicals react according to the following mechanism:It was found that the addition reaction (3) becomes reversible above ca. 453 K. The addition rate parameters have been revised and they satisfactorily agree with those reported previously. At temperatures higher than 593 K, only true H‐abstraction occurs. The rate constant k H for reaction (5) is given by:\documentclass{article}\pagestyle{empty}\begin{document}$$ \log [(k_{\rm H} /k_c^{1/2}){\rm mol}^{- 1/2} \,{\rm cm}^{{\rm 3/2}} \,{\rm s}^{{\rm - 1/2}}]\, = \,(4.34\, \pm \,0.43)\, - \,(59,00\, \pm \,2.62)/\theta $$\end{document}where θ = 2.303 RT kJmol −1 and k c is the rate constant for combination of CF 3 radicals. The reactions of CF 3 with benzene and pentafluorobenzene are compared.