Hierarchical study of the reactions of hydrogen atoms with alkenes: A theoretical study of the reactions of hydrogen atoms with C2–C4 alkenes

Power, Jennifer
Somers, Kieran P.
Nagaraja, Shashank S.
Curran, Henry J.
Power, Jennifer, Somers, Kieran P., Nagaraja, Shashank S., & Curran, Henry J. (2021). Hierarchical Study of the Reactions of Hydrogen Atoms with Alkenes: A Theoretical Study of the Reactions of Hydrogen Atoms with C2–C4 Alkenes. The Journal of Physical Chemistry A, 125(23), 5124-5145. doi: 10.1021/acs.jpca.1c03168
The present study complements our previous studies of the reactions of hydrogen atoms with C5 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 C2¿C4 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 ¿ atom addition reactions to C2¿C5 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 ¿ 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.
American Chemical Society
Publisher DOI
Attribution 4.0 International (CC BY 4.0)