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Thermal decomposition of 1-butyne in shock waves

✍ Scribed by Yoshiaki Hidaka; Tetsuo Higashihara; Takashi Oki; Hiroyuki Kawano

Publisher: John Wiley and Sons
Year: 1995
Tongue: English
Weight: 553 KB
Volume: 27
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550270403

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✦ Synopsis

1-Butyne diluted with Ar was heated behind reflected shock waves over the temperature range of 1100-1600 K and the total density range of 1.36 X 10-5-1.75 X mol/cm3. Reaction products were analyzed by gas-chromatography. The progress of the reaction was followed by IR laser kinetic absorption spectroscopy. The products were CHI, CzH2, C&, C2H6, allene, propyne, C4H2, vinylacetylene, 1,2butadiene, 1,3-butadiene, and benzene. The present data were successfully modeled with a 80 reaction mechanism. 1-Butyne was found to isomerize to 1,2-butadiene. The initial decomposition was dominated by 1-butyne -+ C3H3 + CH3 under these conditions. Rate constant expressions were derived for the decomposition to be k7 = 3.0 X 1015 exp(-75800 cal/RT) sK1 and for the isomerization to be k4 = 2.5 X 1013 exp(-65000 cal/RT) s-l. The activation energy 75.8 kcal/mol was cited from literature value and the activation energy 65 kcal/mol was assumed. These rate constant expressions are applicable under the present experimental conditions, 1100-1600 K and 1.23-2.30 atm.

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