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 N2 diluent at 296 K. Rate constants were determined for the following compounds: methyl formate, (1.30 ± 0.13) × 10−12; ethyl formate, (9.57 ± 1.27) × 10−12; n-propyl formate, (4.65 ± 0.47) × 10−11; and n-butyl formate, (1.12 ± 0.14) × 10−10 cm3 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.