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Reaction mechanism and kinetics of Criegee intermediate and hydroperoxymethyl formate
Meifang Chen1, Shengrui Tong2, Zhen Wang3
1College of Chemistry and Material Science, Anhui Normal University, Wuhu 241000, China; State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Chinese Academy of Sciences Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
Abstract:
The reaction mechanism and kinetics of the simplest Criegee intermediate CH2OO reaction with hydroperoxymethyl formate (HPMF) was investigated at high-level quantum chemistry calculations. HPMF has two reactive functional groups, -C(O)OH and -OOH. The calculated results of thermodynamic data and rate constants indicated that the insertion reactions of CH2OO with -OOH group of HPMF were more favorable than the reactions of CH2OO with -C(O)OH group. The calculated overall rate constant was 2.33 × 10-13 cm3/(molecule⋅sec) at 298 K and the rate constants decreased as the temperature increased from 200 to 480 K. In addition, we also proved the polymerization reaction mechanism between CH2OO and -OOH of HPMF. This theoretical study interpreted the previous experimental results, and supplied the structures of the intermediate products that couldn't be detected during the experiment.
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