Kinetics of chemically activated isobutane and neopentane from the 4358- and 3660-å photolyses of diazomethane with propane and isobutane

R. L. Johnson, W. L. Hase, J. W. Simons

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Abstract

The results of a study of chemically activated isobutane and neopentane produced by excited singlet-state methylene radical insertion into the secondary and tertiary C-H bonds of propane and isobutane, respectively, are reported. The methylene radicals were produced at two energies by the 4358- and 3660-Å photolyses of diazomethane. The measured decomposition rates for the energized isobutane are 1.9×107 and 3.6×10 7 sec-1 in the 4358- and 3660-Å photolysis systems, respectively, and for the energized neopentane are 4.4×106 and 6.8×106 sec-1 in the 4358- and 3660-Å photolysis systems, respectively. These rates correlate well via RRKM theoretical calculations with thermal A factors in the range of 10 16.3-1016.9 sec-1 for isobutane and 10 16.5-1016.9 sec-1 for neopentane.

Original languageEnglish
Pages (from-to)3911-3919
Number of pages9
JournalThe Journal of Chemical Physics
Volume52
Issue number8
DOIs
StatePublished - 1970

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