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The kinetics of the addition of alkyl radicals to carbonyl groups. Part I. The addition of methyl radicals to hexafluoroacetone in the gas phase. The formation of the hexafluoro‐ t ‐butoxy radical
Author(s) -
Drew Roger M.,
Kerr J. Alistair
Publication year - 1983
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.550150307
Subject(s) - chemistry , hexafluoroacetone , radical , kinetics , adduct , gas phase , reaction rate constant , medicinal chemistry , alkyl , benzoyl peroxide , addition reaction , halogen , peroxide , activation energy , photochemistry , organic chemistry , catalysis , polymer , physics , quantum mechanics , polymerization
By pyrolyzing di‐ t ‐butyl peroxide over the temperature range of 405–450 K in the presence of hexafluoroacetone the kinetics of the addition reaction (1), CH 3 + (CF 3 ) 2 CO→; (CF 3 ) 2 C(Ȯ)CH 3 , have been studied. Detailed analyses have shown that the principal product of the adduct radical, (CF 3 ) 2 C(Ȯ)CH 3 , is CF 3 COCH 3 from reaction (2), (CF 3 ) 2 C(Ȯ)CH 3 → CF 3 COCH 3 + CF 3 . The rate constant of the addition reaction was determined to be k 1 (dm 3 /mol·s) = (1.1 ± 4.0) + 10 9 exp(‐(3680 ± 480)/ T ) over the temperature range 405–450 K, based on the value k 3 = 2.2 × 10 10 dm 3 /mol·s for reaction (3), 2CH 3 → C 2 H 6 . The results are discussed in relation to existing data for radical additions to carbonyl groups.