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Rate constant for the reaction of CH 3 C(O)CH 2 radical with HBr and its thermochemical implication
Author(s) -
Farkas Edit,
Kovács Gergely,
Szilágyi István,
Dóbé Sándor,
Bérces Tibor,
Márta Ferenc
Publication year - 2006
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.20135
Subject(s) - chemistry , reaction rate constant , radical , reactivity (psychology) , alkyl , medicinal chemistry , analytical chemistry (journal) , kinetics , organic chemistry , medicine , physics , alternative medicine , pathology , quantum mechanics
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 o 298 (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