Kinetics of the Reactions of CF3O Radicals with CO and H2O

Article abstract of DOI:10.1021/j100016a041

The techniques of pulsed laser photolysis/pulsed laser-induced fluorescence and discharge flow/chemical ionization mass spectroscopy have been employed to study the reactions CF3O + H2O -> CF3OH + OH and CF3O + CO (+M) -> products (+M).No reaction could be observed between CF3O and H2O at both 298 and 381 K, yielding upper limits of k₃(298 K) 3(381 K) 3 molecule^-1 s^-1.The rate coefficient, k₄, for the reaction of CF3O with CO was observed to be dependent upon pressure, analogous to the OH + CO reaction.The high-pressure limiting rate coefficient was found to exhibit a weak positive temperature dependence with k_4infinite(298 K) = (6.8 +/- 1.2) x 1E-14 cm³ molecule^-1 s^-1.A limit of 3 molecule^-1 s^-1 for the pressure independent pathway was also obtained and a limit of 3 molecule^-1 s^-1 was determined for the bimolecular path yielding CF3 and CO2 as products, both at 298 K.Information on the OH + CF3OOCF3, OH + CF3O, and CF3OO + CO reactions and on the products of the 248 nm photolysis of CF3OOCF3 was also obtained.The atmospheric implications of the results are discussed.