The thermal unimolecular decomposition of methyl chloride behind shock waves.

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概要

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• 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<SUP>−6</SUP>–3.5×10<SUP>−5</SUP> mol cm<SUP>−3</SUP>. The decomposition rate was monitored by means of the UV absorption of the CH<SUB>3</SUB> 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 (<I>k</I><SUB>0</SUB>/[Ar] and <I>k</I><SUB>∞</SUB>) were obtained by the application of a refined RRKM theory involving a weak collision effect. Thus, the Arrhenius expressions were given as:<BR>& k_0/[Ar]=10^15.56 exp(-247 kJ mol^-1/RT) cm^3 mol^-1 s^-1,<BR>& k_∞=10^13.86 exp(-383 kJ mol^-1/RT) s^-1. <BR>The collision efficiency factor, β<SUB>c</SUB>, 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.

• 公益社団法人 日本化学会の論文

著者

• Saito Ko

  Department Of Chemistry Graduate School Of Science Hiroshima University

• Murakami Ichiro

  Department Of Electrical Engineering Faculty Of Eng. Yokohama National Univ.

• Kondo Osamu

  Department Of Anatomy Sapporo Medical College

• Murakami Ichiro

  Department of Chemistry, Faculty of Science, Hiroshima University

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