Kinetics and modeling of the thermal reaction of propene at 800 K. Part I. Pure propene

Around 800 K and at low extent of reaction, the thermal reaction of propene (initial pressures 30–200 torr) gives a very large number of products: H₂, CH₄, C₂H₄, C₂H₆, allene, C₃H₈, 1,3-C₄H₆, butenes, methylcyclopentenes, diallyl, hexenes, etc. It is shown that most of these molecules are produced in a free-radical chain mechanism. But some of them originate from a molecular or a biradical path. Allene is thus produced in a concerted four-center dehydrogenation of propene and 4-methylpent-1-ene arises from a bimolecular ene reaction. The Arrhenius parameters of these reactions have been measured and are discussed. A modeling of the concentration-time profile of the products has been performed and rate constants of many steps were evaluated and compared with literature data. © 1996 John Wiley & Sons, Inc.