Application of the RRKM Theory to Energized Ethylene Formed in the Vacuum-ultraviolet Photolysis of <I>n</I>-Paraffins
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概要
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The Rice-Ramsperger-Kassel-Marcus treatment has been applied to the energized ethylene produced in the vacuum-ultraviolet photolysis of C<SUB>2</SUB>H<SUB>6</SUB>, C<SUB>2</SUB>D<SUB>6</SUB>, C<SUB>3</SUB>H<SUB>8</SUB>, C<SUB>3</SUB>D<SUB>8</SUB>, <I>n</I>-C<SUB>4</SUB>H<SUB>10</SUB> and <I>n</I>-C<SUB>4</SUB>D<SUB>10</SUB>. The energy spread in the energized ethylene has been evaluated assuming modified statistical distribution of liberated energy among fragment species. The calculated nonequilibrium unimolecular decomposition rate constant for the process C<SUB>2</SUB>H<SUB>4</SUB>(C<SUB>2</SUB>D<SUB>4</SUB>)→C<SUB>2</SUB>H<SUB>2</SUB>(C<SUB>2</SUB>D<SUB>2</SUB>)+H<SUB>2</SUB>(D<SUB>2</SUB>) could satisfactorily reproduce the experimental pressure dependence of ethylene to acetylene ratio. Non-statistical kinetic energy <I>E</I><SUB>k</SUB> seems to appear for the primary decomposition of the <I>n</I>-paraffins. Its value ranges from zero for the elimination of methane and ethane from propane and <I>n</I>-butane, respectively, at 147.0 nm to about 25 kcal mol<SUP>−1</SUP> for the elimination of hydrogen from ethane at 123.6 nm.
- 公益社団法人 日本化学会の論文
著者
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Obi Kinichi
Department Of Chemical And Biological Sciences Japan Women's University
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Tanaka Ikuzo
Department of Chemistry, Tokyo Institute of Technology
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Akimoto Hajime
Department of Chemistry, Tokyo Institute of Technology
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