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Kinetics of gas‐phase addition reactions of methyl radicals. I. Addition to ethylene, acetylene, and benzene
Author(s) -
Holt Pauline M.,
Kerr J. Alistair
Publication year - 1977
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.550090204
Subject(s) - chemistry , isobutane , acetylene , ethylene , arrhenius equation , benzene , radical , reaction rate constant , gas phase , atmospheric temperature range , medicinal chemistry , photodissociation , kinetics , photochemistry , analytical chemistry (journal) , activation energy , organic chemistry , catalysis , thermodynamics , physics , quantum mechanics
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: TextTemperatureE log A range Reaction (kcal/mol) (1./mol·sec) (°K)ĊH 3 + C 2 H 4 → Ċ 3 H 7 7.3 ± 1.0 8.32 ± 0.5 350 – 500 ĊH 3 + C 2 H 2 → Ċ 3 H 5 7.7 ± 1.5 8.79 ± 0.8 379 – 487 ĊH 3 + C 6 H 6 → C 7 H 9 7.6 ± 1.0 8.79 ± 0.5 372 – 484The 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 k 2 (l./mol·sec) = 7.42 ‐ (7.1/θ) for the reference reaction (2), ·H 3 + (CH 3 ) 3 CH → CH 4 + · 4 H 9 .