An experimental study of the mechanism and branching ratio for the reaction between methyl formate and chlorine atoms

FTIR spectroscopy/UV laser flash photolysis has been used to examine the reaction of chlorine atoms with methyl formate (CH3OC(O)H) at 296 K. The reaction has two possible branches; extraction of a methyl hydrogen or the carbonyl hydrogen. Measurements of the product yields indicate that abstraction of the carbonyl hydrogen is favored over the methyl hydrogen by 58±6% (k1a=8.1×10−13 cm3 mol−1 s−1) to 42±6% (k1b=5.9×10−13 cm3 mol−1 s−1). The experimentally determined IR spectrum of CH2ClOC(O)H and CH3OC(O)Cl are presented and verified with high level ab initio calculations.