Theoretical study on the nitrate radical oxidation of methyl vinyl ether

Abstract

This study investigates the nitrate radical oxidation of methyl vinyl ether (CH2CHOCH3, MVE) by quantum chemical methods. The oxidation initiates with the formation of open-cyclic NO3-adducts, followed by a series of unimolecular decomposition or bimolecular reactions. Kinetic data suggest that pressure and temperature have strong influence on the environmental fate of MVE. Under atmospheric condition, methyl formate, formaldehyde and NO2 are the main products by association with O2/NO. At low pressure (<50Torr) 2-methoxyoxirane and NO2 are main products by decomposition. Total rate coefficient of the bimolecular reaction exhibits negative dependence on temperature (200–300K) and positive dependence on pressure (1–7600Torr). The calculated rate coefficient (7.09×10−13cm3molecule−1s−1) is in well agreement with experimental data at 293K and 760Torr.