ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Rate constants for the thermal decomposition of CH3Cl and the atom–radical reaction O+CH3 have been measured in shock tube experiments. The decomposition of CH3Cl, at three loading pressures, has been carried out between 1663–2059 K with mixtures that varied from 1.25 to 24.9 ppm in Ar. The first-order rate constant k1=1.21×1010 ×exp(−27 838 K/T) s−1 describes the experimental results to within ±29% at the one standard deviation level. The bimolecular rate experiment has then been carried out over the temperature range 1609–2002 K using mixtures of SO2 (49.9 ppm) and CH3Cl (5.14 and 8.2 ppm) in Ar. The technique first involves allowing the thermal decomposition to proceed forming CH3 radicals, and this is then followed by delayed photolysis of SO2 forming the O-atom species. This new method is called the pyrolysis photolysis-shock tube (PyPh-ST) technique. A reaction mechanism had to be used to simulate the measured O-atom profiles for the various experimental conditions, and the bimolecular rate constant was found to be temperature independent with a value of k2=1.4×10−10 cm3 molecule−1 s−1. Reactions (1) and (2) are both theoretically discussed.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.464019
