Kinetics and reaction mechanism of hydroxyl radical reaction with methyl formate

Abstract

Ab initia molecular orbital theory has been used to examine the kinetics and mechanism for the reaction of hydroxyl radical with methyl formate. From the ab initia parameters the room temperature rate constant is calculated and found to be in good agreement with the experimental determination. It is found tliat 86% of the reaction proceeds via abstraction of the carbonyl hydrogen from methyl formate by hydroxyl radical, resulting in the formation of CH3OCO radical. CH3OCO is expected to oxidize to formaldehyde and carbon dioxide under tropospheric conditions. © 1999 American Chemical Society.