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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

✍ Scribed by Roger M. Drew; J. Alistair Kerr

Publisher
John Wiley and Sons
Year
1983
Tongue
English
Weight
509 KB
Volume
15
Category
Article
ISSN
0538-8066

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✦ Synopsis

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 (l), CH3 + (CF3)zCO + (CF3)&(O)CH3, have been studied. Detailed analyses have shown that the principal product of the adduct radical, (CF3)&(O)CH3, is CF3COCH3 from reaction (2), (CF~)ZC(O)CH~ -CF3COCH3 + CF3. The rate constant of the addition reaction was determined to be kl(dm3/mol-s) = (1.1 f 4.0) X lo9 exp(-(3680 f 480)/T) over the temperature range 405450 K, based on the value k 3 = 2.2 X 1Olo dm3/mol.s for reaction (3), 2CH3 -CzHe. The results are discussed in relation to existing data for radical additions to carhonyl groups.

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