Reaction mechanism and kinetics of Criegee intermediate and hydroperoxymethyl formate

Maofa Ge , Meifang Chen , Shengrui Tong , Zhen Wang , Weiran Li , Yanyong Xu , Sufan Wang


Received October 16, 2020,Revised , Accepted December 25, 2020, Available online January 15, 2021

Volume 33,2021,Pages 128-137

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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