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A Systematic Theoretical Kinetics Analysis for the Waddington Mechanism in the Low-Temperature Oxidation of Butene and Butanol Isomers

Yang Li, Qian Zhao, Yingjia Zhang, Zuohua Huang, S. Mani Sarathy

2020The Journal of Physical Chemistry A17 citationsDOIOpen Access PDF

Abstract

solvers, the barrier height difference among all isomerization and dissociation reactions was about 2 and 0.5 kcal/mol, respectively, resulting in less than 50%, and a factor of 2-10 differences for the predicted rate coefficients of the two reaction types, respectively. Comparing the two kinetic solvers, the rate constants of the isomerization reactions showed less than a 32% difference, while the rate of one dissociation reaction (P1 ↔ WDT12) exhibited 1-2 orders of magnitude discrepancy. Compared with results from the literature, both reaction rate coefficients (R4 and R5 reaction systems) and species' thermochemistry (all closed shell molecules and open shell radicals R4 and R5) showed good agreement with the corresponding values obtained from the literature. All calculated results can be directly used for the chemical kinetic model development of butene and butanol isomer oxidation.

Topics & Concepts

ChemistryIsomerizationReaction rate constantThermochemistryThermodynamicsDissociation (chemistry)Ab initioPhysical chemistryKineticsComputational chemistryTransition state theoryReaction rateReaction mechanismEquilibrium constantChemical kineticsOrganic chemistryCatalysisPhysicsQuantum mechanicsFree Radicals and AntioxidantsCatalysis and Oxidation ReactionsCatalytic Processes in Materials Science
A Systematic Theoretical Kinetics Analysis for the Waddington Mechanism in the Low-Temperature Oxidation of Butene and Butanol Isomers | Litcius