Abstract: | 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), CH3 + (CF3)2CO→; (CF3)2C(?)CH3, have been studied. Detailed analyses have shown that the principal product of the adduct radical, (CF3)2C(?)CH3, is CF3COCH3 from reaction (2), (CF3)2C(?)CH3 → CF3COCH3 + CF3. The rate constant of the addition reaction was determined to be k1(dm3/mol·s) = (1.1 ± 4.0) + 109 exp(-(3680 ± 480)/T) over the temperature range 405–450 K, based on the value k3 = 2.2 × 1010 dm3/mol·s for reaction (3), 2CH3 → C2H6. The results are discussed in relation to existing data for radical additions to carbonyl groups. |