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Rate constant for the reaction of CH3C(O)CH2 radical with HBr and its thermochemical implication

✍ Scribed by Edit Farkas; Gergely Kovács; István Szilágyi; Sándor Dóbé; Tibor Bérces; Ferenc Márta

Publisher
John Wiley and Sons
Year
2005
Tongue
English
Weight
102 KB
Volume
38
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The fast flow method with laser induced fluorescence detection of CH~3~C(O)CH~2~ was employed to obtain the rate constant of k~1~ (298 K) = (1.83 ± 0.12 (1σ)) × 10^10^ cm^3^ mol^−1^ s^−1^ for the reaction CH~3~C(O)CH~2~ + HBr ↔ CH~3~C(O)CH~3~ + Br (1, −1). The observed reduced reactivity compared with n‐alkyl or alkoxyl radicals can be attributed to the partial resonance stabilization of the acetonyl radical. An application of k~1~ in a third law estimation provides Δ~f~H(CH~3~C(O)CH~2~) values of −24 kJ mol^−1^ and −28 kJ mol^−1^ depending on the rate constants available for reaction (‐1) from the literature. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 38: 32–37, 2006

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