The thermal decomposition of CH3Cl using the Cl-atom absorption method and the bimolecular rate constant for O + CH3 (1609-2002 K) with a pyrolysis photolysis-shock tube technique

Article abstract of DOI:10.1063/1.464019

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 x 10¹⁰ x exp(-27 838 K/T) s^-1 describes the experimental results to within +/- 29percent at the one standard deviation level.The bimolecular rate experiment has then been carried out over the temperature range 1609-2002 using mixtures of SO2 (49.9 ppm) and CH3Cl (5.14 and 8.2 ppm) in Ar.The techniques 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 x 10^-10 cm³ molecule^-1 s^-1.Reactions (1) and (2) are both theoretically discussed.

Full text of DOI:10.1063/1.464019

The thermal decomposition of CH3Cl using the Clatom absorption method and the
bimolecular rate constant for O+CH3 (1609–2002 K) with a pyrolysis photolysis
shock tube technique
K. P. Lim and J. V. Michael
Citation: The Journal of Chemical Physics 98, 3919 (1993); doi: 10.1063/1.464019
View online: http://dx.doi.org/10.1063/1.464019
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/98/5?ver=pdfcov
Published by the AIP Publishing
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