Kinetic study of the thermal decomposition of isocyanic acid in shock waves.
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概要
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Thermal decomposition of isocyanic acid HNCO diluted to less than 2.0 mol% in argon was studied behind incident shock waves over the temperature range 2100–2500 K. The decomposition course was followed by monitoring the light absorption of HNCO and NH(<SUP>3</SUP>Σ<SUP>−</SUP>) at 206 and 336 nm, respectively. It is confirmed that the primary step of the decomposition is a bimolecular process HNCO+Ar→NH(<SUP>3</SUP>Σ<SUP>−</SUP>)+CO+Ar, Δ<I>H</I>°<SUB>0</SUB>=337 kJ mol<SUP>−1</SUP>, with the low-pressure limit rate constants <I>k</I>=10<SUP>17.23±0.36</SUP>exp[−(402±17) kJ mol<SUP>−1</SUP>/<I>RT</I>] cm<SUP>3</SUP> mol<SUP>−1</SUP> s<SUP>−1</SUP>. The siglet-to-triplet crossing point is estimated on the basis of the RRKM low-pressure-limit rate constant calculations. The overall decomposition mechanism is suggested and its validity is confirmed by computer simulation of the time–concentration profiles of NH(<SUP>3</SUP>Σ<SUP>−</SUP>) at varying temperature.
- 公益社団法人 日本化学会の論文
著者
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Kajimoto Okitsugu
Department Of Chemistry Graduate School Of Science Kyoto University
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Okada Kazuo
Department Of Anesthesiology School Of Medicine Teikyo University
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Kondo Osamu
Department Of Anatomy Sapporo Medical College
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Fueno Takayuki
Department of Chemistry, Faculty of Engineering Science, Osaka University
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Fujikane Jiro
Department of Chemistry, Faculty of Engineering Science, Osaka University
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