LONG PATH FOURIER-TRANSFORM INFRARED SPECTROSCOPIC STUDY OF THE REACTIONS OF CF3OO AND CF3O RADICALS WITH NO2

Mechanisms of the reactions of CF3OO and CF3O radicals with NO2 have been studied using the long path FTIR method in the visible (lambda greater-than-or-equal-to 400 nm) photolysis of CF3NO in the presence of excess NO2 (in mTorr range) in 700 Torr of air at 297 +/- 2 K. In the early stage of the photolysis, the predominant F-containing product detected was CF3OONO2 formed via the addition reaction CF3OO + NO2 (+M) <-- --> CF3OONO2 (+M). Addition of excess NO to the above irradiated mixture in the dark led to the loss of CF3OONO2 and concomitant production of CF3ONO2, FNO2, and CF2O, consistent with the occurrence of CF3OO + NO --> CF3O + NO2 followed by the addition reaction CF3O + NO2 (+M) --> CF3ONO2 (+M) (greater-than-or-equal-to 90%) and the F-transfer reaction CF3O + NO2 --> CF2O + FNO2 (less-than-or-equal-to 10%). An alternative decomposition channel of CF3OONO2 to yield CF2O and FNO2 as reported in the literature was not observed in the present study.