Theoretical and experimental study of the product branching in the reaction of acetic acid with OH radicals.
Theoretical and experimental study of the product branching in the reaction of acetic acid with OH radicals.
复制标题
乙酸与OH自由基反应产物支化的理论与实验研究。
DOI：
10.1021/jp044679v
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发表时间：
2005
期刊：
影响因子：
--
通讯作者：
L. Vereecken
中科院分区：
文献类型：
--
作者：
F. De Smedt;X. Bui;T. L. Nguyen;J. Peeters;L. Vereecken
The product distribution of the reaction of acetic acid, CH(3)COOH, with hydroxyl radicals, OH, was studied experimentally and theoretically. Mass-spectrometric measurements at 290 K and 2 Torr of He of the CO(2) yield versus the loss of acetic acid yielded a branching fraction of 64 +/- 14% for the abstraction of the acidic hydrogen as follows: CH(3)COOH + OH --> CH(3)COO + H(2)O --> CH(3) + CO(2) + H(2)O. A quantum chemical and theoretical kinetic analysis showed that the abstraction of the acidic hydrogen is enhanced relative to the abstraction of -CH(3) hydrogens because of the formation of a strong pre-reactive H-bonded complex, where the H-bonds are retained in the H-abstraction transition state. The potential energy surface of the reaction is explored in detail, and the reaction products of the individual channels are identified. The theoretical product branching is found to be critically dependent on the energetic and rovibrational differences between the H-abstraction transition states.
