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ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2016,Vol.32>> Issue(12)>> 2898-2904     doi: 10.3866/PKU.WHXB201609142         中文摘要
Reaction Mechanism of Criegee Intermediate CH3CHOO with H2O and the Acid Catalytic Effect
GAO Zhi-Fang, ZHOU Li-Ting, WANG Wei-Na, LIU Feng-Yi, WANG Wen-Liang
School of Chemistry and Chemical Engineering, Shaanxi Normal University, Key Laboratory for Macromolecular Science of Shaanxi Province, Xi'an 710119, P. R. China
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The catalytic effect of H2O and six kinds of organic acids (e.g., formic acid) on the reaction of CH3CHOO with H2O is studied at the CCSD(T)//B3LYP/6-311+G(d,p) level. The results reveal that two possible channels exist as the double proton transfer and addition, of which the latter dominates for the non-catalytic reactions. For the additions, the OH of water is added to the α-C of CH3CHOO, and the H atoms migrate to the end oxygen atoms. Catalysts such as H2O and organic acid can form a hydrogen-bonded complex with CH3CHOO, which promotes the H transfer and thus significantly reduces the elementary reaction energy barrier and apparent activation energy when compared with that of the non-catalytic reaction. The catalytic effect is proportional to the strength of the organic acids. For example, for the formation of syn-HAHP catalyzed by H2O (pKa=15.7), formic acid (pKa=3.75) and oxalic acid (pKa=1.23), the energy barrier is reduced from 69.12 to 40.78, 18.88 and 10.61 kJ·mol-1, respectively. In addition, the non-catalytic reaction has a positive activation energy, whereas the catalytic reactions have an negative apparent activation energy.



Keywords: Criegee intermediate   CH3CHOO   Acid catalysis   Addition reaction  
Received: 2016-07-18 Accepted: 2016-09-13 Publication Date (Web): 2016-09-14
Corresponding Authors: WANG Wen-Liang Email: wlwang@snnu.edu.cn

Fund: The project was supported by the National Natural Science Foundation of China (21473108, 21473107), Fundamental Research Funds for Shaanxi Innovative Team of Key Science and Technology, China (2013KCT-17), and Fundamental Research Funds for the Central Universities, China (JK201601005).

Cite this article: GAO Zhi-Fang, ZHOU Li-Ting, WANG Wei-Na, LIU Feng-Yi, WANG Wen-Liang. Reaction Mechanism of Criegee Intermediate CH3CHOO with H2O and the Acid Catalytic Effect[J]. Acta Phys. -Chim. Sin., 2016,32 (12): 2898-2904.    doi: 10.3866/PKU.WHXB201609142

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