Experimental and theoretical studies of the reaction between CF3 and NO2 at 298 K

The title reaction has been studied by pulse radiolysis combined with time-resolved infrared diode laser spectroscopy. The kinetics of CF3 were analysed taking into account the two competing reactions CF3+ CF3+M → C2F6+M (1) and CF3+NO2 → CF2O+FNO (2a). Based on studies of the yield and kinetics of CF3 we determined values of the absorption cross section, σ(CF3)=(1.96±0.20)×10−17 cm2 molecule−1 at 1263.567 cm−1 and the bimolecular rate constant, k1=(1.04±0.12)×10−11 cm3 molecule−1 s−1 with a bath gas pressure of 20 mbar at 298 K. Reaction (2a) was studied under pseudo-first-order conditions and the value of k2a=(1.53±0.20)×10−11 cm3 molecule−1 s−1 was found to be independent of bath gas pressure in the range 4–22 mbar. Based on the characteristic absorption spectra of the products, the branching ratio of reaction (2a) was found to be 0.95.