A chemical pathway perspective on the kinetics of low-temperature ignition of propane

摘要

The chemistry of low-temperature ignition in propane/air mixtures is analyzed using a recently developed pathway representation of the chemical kinetics. The "Sum Over Histories Representation" allows time dependent kinetic observables to be computed using an expansion over global chemical pathways that follow chemical moieties as they move through a complex reaction network. This methodology assigns probabilities to complete chemical pathways through which specific intermediate or product species are generated. The growth of the radical pool during the ignition process is analyzed by enumerating chemical pathways that constitute catalytic cycles, in particular the catalyzed production of the highly reactive OH-radical. In addition to the well-known reaction route followed in low-temperature ignition of hydrocarbons which involves the QOOH and keto-hydroperoxide species, we have explicitly identified several other cycles that are responsible for most of the remaining OH-production. (C) 2019 The Combustion Institute. Published by Elsevier Inc. All rights reserved.