Kinetic and mechanistic study of the pressure and temperature dependence of the reaction CH3O+NO

Sensitizing effects of NOx on CH4 oxidation at high pressure

“…The reaction with NO follows either a disproportionation pathway to HNO + CH 2 O (R4) or an association path to CH 3 ONO (R5). The preferred rate expressions are taken from the study by Caralp et al [84], who interpreted their own measurements of the overall rate of NO + CH 3 O and data from the literature [85][86][87][88] in terms of a multichannel RRKM analysis. The potential energy surface calculations indicated that the disproportionation reaction (R4) occurs simultaneously by direct Habstraction at the nitrogen atom of NO and by formation of the adduct CH 3 ONO * followed by rearrangement and bond cleavage to HNO + CH 2 O.…”

Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species

“…The preferred values are based on the extensive work by Caralp et al (1998) which includes and supersedes the earlier results from Frost and Smith (1990), McCaulley et al (1990) and Daële et al (1995) as well as by Ohmori et al (1993) in the middle of the falloff curve. The results are represented in the form of k=k 1 ([M])+k 2 , where k 1 (M) is based on k 01 such as preferred here, k ∞1 such as given below and F c =exp(-T /900) for M=He, Ar and N 2 .…”

“…The recommended value is from the most extensive study by Caralp et al (1998) which supersedes and includes earlier work. The results are in accord with an RRKM modelling of the chemical activation system.…”

“…The preferred value of the rate coefficient at 298 K is the average of the room-temperature rate coefficients of Shibuya et al (1977), , , Timonen et al (1988), Stief et al (1990), Dóbé et al (1995), , Ninomiya et al (2000) and . Taken together, the temperature-dependent studies of , Timonen et al (1988), Stief et al (1990) and suggest that the rate coefficient of this reaction has a slight negative temperature dependence over the range 200 to 298 K and possibly a small positive temperature dependence above 300 K. However, within the measurement uncertainties the rate coefficient can be considered to be independent of temperature over the range 200-400 K. (b) Measurement of the rate coefficient ratio for k(CH 3 CO+Cl 2 )/k(CH 3 CO+O 2 )=7.9±0.5 at 930 mbar total pressure.…”

Kinetics of the reaction of OH radicals with CH3OH and CD3OD studied by laser photolysis coupled to high repetition rate laser induced fluorescence

“…We have therefore upgraded the classical LIF set-up, employed in our laboratory for many years [3][4][5], with the new high repetition rate laser. We have used this to measure the rate constants of the reactions of hydroxyl radicals with methanol and its deuterated homologue.…”