Chemical Physics Letters, Vol.365, No.3-4, 267-278, 2002
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% (k(la) = 8.1 x 10(-13) cm(3) mol(-1) s(-1)) to 42 +/- 6% (k(lb) = 5.9 x 10(-13) cm(3) mol(-1) s(-1)). The experimentally determined IR spectrum of CH2ClOC(O)H and CH3OC(O)Cl are presented and verified with high level A initio calculations. (C) 2002 Elsevier Science B.V. All rights reserved.