An Experimental and Computational Study of the Kinetics and Mechanism of the Reaction of Methyl Formate with Cl Atoms

Ab initio molecular orbital theory has been used to examine the kinetics and mechanism for the reaction of chlorine atoms with methyl formate. From the ab initio parameters, the room-temperature rate constant is calculated and found to be in reasonable agreement with the experimental determination. It is found that 90% of the reaction proceeds via abstraction of the carbonyl hydrogen from methyl formate by chlorine atoms, resulting in the formation of CH 3 OCO radical.