Atmospheric chemistry of FCOx radicals: Kinetic and mechanistic study of the FC(O)O2 + NO2 reaction

Abstract

AbstractA pulse radiolysis system was used to study the kinetics of the reaction of FC(O)O2 radicals with NO2. By monitoring the rate of the decay of NO2 using its absorption at 400 nm the reaction rate constant was determined to be (5.5 ± 0.6) × 10−12 cm3 molecule−1 s−1 at 296 K and 500–1000 mbar pressure of SF6 diluent. A long path length Fourier transform infrared spectrometer was used to investigate the thermal stability of the product FC(O)O2NO2. The rate of thermal decomposition of FC(O)O2NO2 was independent of the total pressure of N2 diluent over the range 100–700 torr and was fit by the expression k−3 = 6.0 × 1016 exp(−14150/T) s−1. The results are discussed in the context of the atmospheric chemistry of FCOx radicals. © 1995 John Wiley & Sons, Inc.