Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
The Thermal Unimolecular Decomposition of Methyl Chloride behind Shock Waves
Osamu KondoKo SaitoIchiro Murakami
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1980 Volume 53 Issue 8 Pages 2133-2140

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Abstract

The thermal decomposition of methyl chloride diluted in Ar has been studied behind shock waves over the temperature range between 1680 and 2430 K and the total density range of 2.0×10−6–3.5×10−5 mol cm−3. The decomposition rate was monitored by means of the UV absorption of the CH3 radical produced. The initiation reaction was found to be the C–Cl bond fission; the process proceeded in the fall-off region under the present experimental conditions. From the fall-off data, low- and high-pressure rate constants (k0/[Ar] and k) were obtained by the application of a refined RRKM theory involving a weak collision effect. Thus, the Arrhenius expressions were given as:
& k_0/[Ar]=10^15.56 exp(-247 kJ mol^-1/RT) cm^3 mol^-1 s^-1,
& k_∞=10^13.86 exp(-383 kJ mol^-1/RT) s^-1.
The collision efficiency factor, βc, was obtained as 0.02 at the mean temperature of the experiment by comparing the low-pressure rate constant with the strong collision-rate constant. The high-pressure rate constant was well explained by the maximum free-energy criterion presented by Quack and Troe.

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