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Issue 30, 2019
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Theoretical investigation on the reaction mechanism and kinetics of a Criegee intermediate with ethylene and acetylene

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Abstract

The detailed reaction mechanism of the Criegee intermediate CH2OO with ethylene and acetylene has been investigated by using the HL//M06-2X/AUG-cc-pVTZ method. The 1,3-cycloaddition of CH2OO to the unsaturated bond of ethylene or acetylene forms a five-membered ring adduct. For the reaction of CH2OO with ethylene, the subsequent ring-opening, H-shift isomerization and decomposition result in the formation of ethenol + HCHO and acetaldehyde + HCHO, and for the reaction of CH2OO with acetylene, the adduct proceeds via ring-opening and H-shift isomerization forming malonaldehyde. The calculated overall rate constant increases in the temperature range of 200–500 K, and at 298 K, it is 3.91 × 10−15 cm3 molecule−1 s−1 for the CH2OO + C2H4 reaction and 1.27 × 10−16 cm3 molecule−1 s−1 for the CH2OO + C2H2 reaction. The product branching ratio of the CH2OO + C2H4 reaction is pressure dependent, and the adduct tends to decompose to ethenol + HCHO and acetaldehyde + HCHO at lower pressures and higher temperatures. For the CH2OO + C2H2 reaction, the adduct isomerizes completely to malonaldehyde in the temperature range of 200–500 K and the pressure range of 100–1000 Torr.

Graphical abstract: Theoretical investigation on the reaction mechanism and kinetics of a Criegee intermediate with ethylene and acetylene

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Publication details

The article was received on 10 May 2019, accepted on 08 Jul 2019 and first published on 09 Jul 2019


Article type: Paper
DOI: 10.1039/C9CP02644D
Phys. Chem. Chem. Phys., 2019,21, 16583-16590

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    Theoretical investigation on the reaction mechanism and kinetics of a Criegee intermediate with ethylene and acetylene

    C. Sun, B. Xu, L. Lv and S. Zhang, Phys. Chem. Chem. Phys., 2019, 21, 16583
    DOI: 10.1039/C9CP02644D

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