ISSN:
0538-8066
Keywords:
Chemistry
;
Physical Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
1,2-Butadiene diluted with Ar was heated behind reflected shock waves over the temperature and the total density range of 1100-1600 K and 1.36 × 10-5 - 1.75 × 10-5 mol/cm3. The major products were 1,3-butadiene, 1-butyne, 2-butyne, vinylacetylene, diacetylene, allene, propyne, C2H6, C2H4, CH4, and benzene, which were analyzed by gas chromatography. The UV kinetic absorption spectroscopy at 230 nm showed that 1,2-butadiene rapidly isomerizes to 1,3-butadiene from the initial stage of the reaction above 1200 K. In order to interpret the formation of 1,3-butadiene, 1-butyne, and 2-butyne, it was necessary to include the parallel isomerizations of 1,2-butadiene to these isomers. The present data were successfuly modeled with a 82 reaction mechanism. From the modeling, rate constant expressions were derived for the isomerization 1,2-butadiene = 1,3-butadiene to be k3 = 2.5 × 1013 exp(-63 kcal/RT) s-1 and for the decomposition 1,2-butadiene = C3H3 + CH3 to be k6 = 2.0 × 1015 exp(-75 kcal/RT) s-1, where the activation energies, 63 kcal/mol and 75 kcal/mol, were assumed. These rate constants are only applicable under the present experimental conditions, 1100-1600 K and 1.23-2.30 atm. © 1995 John Wiley & Sons, Inc.
Additional Material:
6 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/kin.550270404
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