Hierarchical Study of the Reactions of Hydrogen Atoms with Alkenes: A Theoretical Study of the Reactions of Hydrogen Atoms with C(2)-C(4) Alkenes.

The present study complements our previous studies of the reactions of hydrogen atoms with C(5) alkene species including 1- and 2-pentene and the branched isomers (2-methyl-1-butene, 2-methyl-2-butene, and 3-methyl-1-butene), by studying the reactions of hydrogen atoms with C(2)-C(4) alkenes (ethylene, propene, 1- and 2-butene, and isobutene). The aim of the current work is to develop a hierarchical set of rate constants for Ḣ atom addition reactions to C(2)-C(5) alkenes, both linear and branched, which can be used in the development of chemical kinetic models. High-pressure limiting and pressure-dependent rate constants are calculated using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory and a one-dimensional master equation (ME). Rate constant recommendations for Ḣ atom addition and abstraction reactions in addition to alkyl radical decomposition reactions are also proposed and provide a useful tool for use in mechanisms of larger alkenes for which calculations do not exist. Additionally, validation of our theoretical results with single-pulse shock-tube pyrolysis experiments is carried out. An improvement in species mole fraction predictions for alkene pyrolysis is observed, showing the relevance of the present study.