A Combined Experimental and Theoretical Study on the Gas Phase Reaction of OH Radicals with Ethyl Propyl Ether.

Abstract

The reaction of ethyl propyl ether (EnPE) with OH radicals was studied using proton-transfer-reaction mass spectrum (PTR-MS), and the rate constant was measured at 298 K and atmospheric pressure using the relative rate method: kexp(OH+EnPE) = (1.13 ± 0.09) × 10-11 cm3 molecules-1 s-1. In addition, a parallel theoretical study was performed using the traditional transition state theory (TST) with a tunnelling effect correction in combination at M05-2X method with two basis sets, 6-311++G(d,p) and aug-cc-pVTZ. According to these calculations, H atom abstraction occurs more favorably from the methylene group adjacent to the -O- bond than from the other groups. The theoretical calculation of the total rate constant of the reaction of EnPE with OH radicals was consistent with the experimental values. The gas-phase products indicated that the major products observed were ethyl formate, ethyl propionate, propionic acid. Combined with the experimental and theoretical results, the possible reaction mechanisms were proposed and discussed. The atmospheric implications of the studied reaction are presented, and the lifetime of EnPE in the presence of OH radicals was evaluated to be approximately 1 day.