Atmospheric insight into the reaction mechanism and kinetics of isopropenyl methyl ether (i-PME) initiated by OH radicals and subsequent oxidation of product radicals

Abstract

Studies on primary gas-phase reactions of emitted saturated and unsaturated ethers with oxidants and subsequent secondary reactions of product radicals with O2 in the presence of NO are important in their atmospheric chemical processes. To accomplish these findings, we have examined the chemistry of OH-initiated oxidation of isopropenyl methyl ether (i-PME) CH3C(CH2)OCH3 by electronic structure ca using density functional theory. Our energetic calculations show that OH additions to carbon-carbon double bonds of i-PME are more favorable reaction pathways than H-abstraction reactions from the various CH sites of the titled molecule. The rate constant values which are obtained from the transition state theory also signify that OH-addition reactions have faster reaction rates than H-abstraction reactions. Our calculated total rate constant of the reaction is found 9.90 × 10−11 cm3 molecule−1 s−1. The percentage branching ratio calculations imply that OH-addition reactions have 98.09% contribution in the total rate constant. The atmospheric lifetime of i-PME is found to be 2.8 h. Further, we have identified 2-hydroxy-2-methoxypropanol, methyl acetate, methy-1,2-hydroxyacetate and 1-hydroxypropane-2-one, 1,2-dihydroxypropan-2-yl format, 2-hydroxyacetic acid, acetic acid, and formaldehyde from the secondary oxidation of product radicals.