Kinetics
and mechanism of the reaction of OH with CH3C(O)CH3 have been studied by discharge-flow experiments
and CCSD(T) quantum chemical computations. In the experiments, the rate coefficient for the overall
reaction, OH + CH3C(O)CH3
→ products (1), and the branching ratio for the specific reaction
channel OH + CH3C(O)CH3
→ CH2C(O)CH3
+ H2O (1a) have been determined to be k1
= (1.04 ± 0.03) × 1011 cm3
mol−1
s−1 and Γ1a
=
k1a/k1
= 0.50 ± 0.04, respectively (T
= 298 K). Two different reaction pathways have been characterized
by ab initio calculations. Both H atom abstraction and OH addition to the CO group have been
found to occur through hydrogen bonded OH···CH3C(O)CH3 complexes. Most of our results support recent findings
(M. Wollenhaupt, S. A. Carl, A. Horowitz and J. N. Crowley, J. Phys. Chem. A, 2000, 104, 2695; M. Wollenhaupt
and J. N. Crowley, J. Phys. Chem. A, 2000, 104, 6429) but contradictions
remain
concerning the mechanism of this atmospherically important reaction.
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