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Kinetics of gas-phase addition reactions of methyl radicals. I. Addition to ethylene, acetylene, and benzene

✍ Scribed by Pauline M. Holt; J. Alistair Kerr

Publisher: John Wiley and Sons
Year: 1977
Tongue: English
Weight: 643 KB
Volume: 9
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550090204

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✦ Synopsis

The reactions have been studied by a mass-balance method involving the photolysis of small amounts of biacetyl in the presence of a large excess of isobutane containing a small proportion of the unsaturated substrate. The following Arrhenius parameters have been derived: Temperature Reaction E log A range (kcal/mol) (I./mol .set) ( O K ) CH3 + CzHi -+ C3H1 7 . 3 f 1.0 8.32 f 0 . 5 350-500 CH3 + CsHs -+ C7H5 7 . 6 f. 1.0 8.79 f 0 . 5 372-484 CH8 + CzHs -+ C3H5 7.7 f 1.5 8.79 f 0 . 8 379-487

The results for methyl addition to ethylene are based on previous determinations by other techniques as well as the present studies. The results for methyl addition to acetylene and benzene are derived solely from the present experiments and are calculated relative to a rate constant of log kl(l./mol.sec) = 7.42 -(7.1/8) for the reference reaction (2), CHS + (CH3)&H -+ CHd + C4Ho.

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