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Thermal isomerization and decomposition of 1,2‐butadiene in shock waves
Author(s) -
Hidaka Yoshiaki,
Higashihara Tetsuo,
Ninomiya Natsuhiko,
Oki Takashi,
Kawano Hiroyuki
Publication year - 1995
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550270404
Subject(s) - chemistry , isomerization , 1,3 butadiene , reaction rate constant , thermal decomposition , propyne , allene , diacetylene , benzene , decomposition , photochemistry , standard enthalpy of formation , analytical chemistry (journal) , medicinal chemistry , kinetics , organic chemistry , catalysis , polymerization , physics , polymer , quantum mechanics
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/cm 3 . The major products were 1,3‐butadiene, 1‐butyne, 2‐butyne, vinylacetylene, diacetylene, allene, propyne, C 2 H 6 , C 2 H 4 , CH 4 , 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 k 3 = 2.5 × 10 13 exp(−63 kcal/ RT ) s −1 and for the decomposition 1,2‐butadiene = C 3 H 3 + CH 3 to be k 6 = 2.0 × 10 15 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.