Abstract
Abstract1‐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 × 10−5−1.75 × 10−5 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 CH4, C2H2, C2H4, C2H6, allene, propyne, C4H2, vinylacetyiene, 1,2‐ butadiene, 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 × 1015 exp(−75800 cal/RT) s−1 and for the isomerization to be k4 = 2.5 × 1013 exp(−65000 cal/RT) s−1. 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. © 1995 John Wiley & Sons, Inc.
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