Kinetics of the gas phase reactions of chlorine atoms with a series of formates

Relative rate techniques were used to study the reactivity of Cl atoms with a series of formates in 700 Torr of N-2 diluent at 296 K. Rate constants were determined for the following compounds: methyl formate, (1.30 +/- 0.13) x 10(-12); ethyl formate, (9.57 +/- 1.27) x 10(-12); n-propyl formate, (4.65 +/- 0.47) x 10(-11); and n-butyl formate, (1.12 +/- 0.14) x 10(-10) cm(3) molecule(-1) s(-1). These results are consistent with previous relative rate studies but are approximately 20-30% lower than the results from an absolute rate study of the reactivity of chlorine atoms towards esters. Likely explanations for the discrepancy are discussed. (c) 2006 Elsevier B.V. All rights reserved.