Kw. Oum et G. Hancock, INFRARED-EMISSION FROM THE CF3+NO2 REACTION, The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 101(14), 1997, pp. 2634-2642
The reaction of the CF3 radical with NO2 has been investigated by usin
g time-resolved FTIR emission spectroscopy. Strong infrared emission h
as been attributed to products, CF2O and FNO, excited in the nu(2) and
nu(1) modes, respectively. The direct one-step production pathway la
is suggested as a major reaction channel: CF3 + NO2 --> CF2O + FNO, De
lta H degrees(298) = -267 kJ mol(-1) (1a); --> CF2O + F + NO, Delta H
degrees(298) = -31 kJ mol(-1) (Ib). The rate constant for reaction 1 w
as measured to be (2.4 +/- 0.5) x 10(-11) cm(3) molecule(-1) s(-1). Th
e F atom formation pathway Ib is the minor channel: the relative branc
hing ratio of reactions la and Ib was estimated as 1 : 0.015. The form
ation of the FON isomer formed via a five-center intermediate is discu
ssed as a possible carrier of an unidentified emission band near 1880
cm(-1). The CF3O + NO reaction was investigated by the same technique.
Lower emission intensities from the same reaction products were obser
ved, with proportionally less vibrational excitation in the CF2O produ
ct.