3958-66-5Relevant articles and documents
Rate Constants of the Reactions of CF3O2, i-C3H7O2 and t-C4H9O2 with NO
Peeters, J.,Vertommen, J.,Langhans, I.
, p. 431 - 436 (2007/10/02)
The kinetics of the title reactions have been studied at T = 290 K and p = 2 Torr He using the fast-flow technique combined with molecular-beam sampling mass spectrometry. - In our novel approach, the total rate constant k1 of RO2 + NO -> RO + NO2/RONO2 is determined from the shape of the NO2-growth profile.The validity of the method is demonstrated by the nearly identical results for k1(CF3O2 + NO) obtained from CF3O2-decays: k1 = (1.54 +/- 0.35)*10-11 and from NO2-growths: k1 = (1.51 +/- 0.4)*10-11 cm3 s-1, in excellent agreement also with previous determinations. - Rate coefficient data of alkylperoxy + NO reactions, derived from NO2-profiles, are reported for i-C3H7O2 + NO: k1 = (5.0 +/- 1.2)*10-12 and for t-C4H9O2 + NO: k1 = (4.0 +/- 1.1)*10-12 cm3 s-1.Our results, in combination with literature values for smaller peroxy radicals, indicate a marked decrease of the rate coefficient with increasing CH3-substitution.Including data on haloalkyl- and acetylperoxy reactions, the reactivity of RO2 towards NO is shown to correlate with the electron acceptor/donor properties of substituents on the α-carbon.Atmospheric Chemistry / Chemical Kinetics / Elementary Reactions / Mass Spectrometry / Radicals
