Pulsed laser photolysis vacuum UV laser-induced fluorescence kinetic study of the reactions of Cl(2P3/2) atoms with ethyl formate, n-propyl formate, and n-butyl formate

Cl(2P3/2) atoms were produced by photolysis of Cl2 at 351 nm in the presence of alkyl formates and monitored by LIF spectroscopy at 134.72 nm. Rate coefficients of k(Cl + C2H5OC(O)H) = (9.5 ± 0.3)×10−12, k(Cl + n-C3H7OC(O)H) = (4.5 ± 0.3) × 10−11 and k(Cl + n-C4H9OC(O)H) = (1.2 ± 0.1) × 10−10 cm3 molecule−1 s−1 were determined at 295 ± 2 K in 6–7 Torr of Ar diluent. These values are 15–30% lower than reported in a previous pulsed laser photolysis resonance fluorescence study. The discrepancy may reflect complications arising from the fact that the time scales for chlorine atom loss and regeneration were not sufficiently decoupled in the previous study.