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The kinetics of the addition of alkyl radicals to carbonyl groups. II. The addition of methyl radicals to trifluoroacetone in the gas phase. The formation reaction of the trifluoro-t-butoxy radical

✍ Scribed by J. Alistair Kerr; J. Paul Wright

Publisher
John Wiley and Sons
Year
1984
Tongue
English
Weight
364 KB
Volume
16
Category
Article
ISSN
0538-8066

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✦ Synopsis

By photolyzing azomethane over the temperature range 331-491 K in the presence of trifluoroacetone the kinetics of the addition reaction (11, CH3 + CF3COCH3 + CF,C(O)(CH, )z have been studied. Detailed analyses have shown that the principal product of the adduct radical, CF3C(0)(CH3)2, is CH,COCH, from reaction ( -2), CF3C(0)(CH3), + CH,COCH, + CF,. The rate constant of the addition reaction has been determined to be k,(dm3/mol s) = (4.5 * 1.4) x lo' exp( -(3370 ? 120)/T) over the temperature range 331-491 K, based on the value k, = 2.2 x 10'' dm3/mol s for the reaction (31, 2CH3 + CzHs. The results are discussed in relation to existing data for radical additions to >C=O groups.

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