Citation: 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 Physico-Chimica Sinica, ;2016, 32(12): 2898-2904. doi: 10.3866/PKU.WHXB201609142 shu

Reaction Mechanism of Criegee Intermediate CH₃CHOO with H₂O and the Acid Catalytic Effect

School of Chemistry and Chemical Engineering, Shaanxi Normal University, Key Laboratory for Macromolecular Science of Shaanxi Province, Xi'an 710119, P. R. China

Received Date: 18 July 2016
Revised Date: 13 September 2016

Fund Project: 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).

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 (pK_a=15.7), formic acid (pK_a=3.75) and oxalic acid (pK_a=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.
- Criegee intermediate,
- CH₃CHOO,
- Acid catalysis,
- Addition reaction
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Reaction Mechanism of Criegee Intermediate CH₃CHOO with H₂O and the Acid Catalytic Effect