A Theoretical and Computational Analysis of the Methyl-Vinyl + O2 Reaction and Its Effects on Propene Combustion
datasetposted on 07.11.2017, 00:00 by Xi Chen, C. Franklin Goldsmith
A detailed analysis of the reaction of CH3CCH2 and CH3CHCH with molecular oxygen is presented. The C3H5O2 potential energy surface was characterized using a combination of electronic structure methods. The majority of the stationary points on the PES was determined at the CCSD(T)-F12a/cc-pVTZ-F12//B2PLYPD3/cc-pVTZ level of theory, with the remaining transition states computed using multireference methods. Microcanonical rate theory and the master equation are used to determine the temperature- and pressure-dependent rate coefficients for each reaction channel. The main product channels are CH2O + CH3CO for CH3CCH2 and CH3CHO + CHO for CH3CHCH. The rate constants for these two reactions at 1 atm are k = 9.03 × 1022 × T–3.21 × exp–2162/T and 1.50 × 1019 × T–2.10 × exp–1260/T cm–3 mol–1 s–1, respectively. In contrast to C2H3 + O2, the methyl-vinyl + O2 reactions remain chain propagating, even at high temperatures. The new rate coefficients were implemented in a detailed mechanism taken from the literature. These changes have a modest effect on the ignition delay time and laminar flame speeds for propene combustion.
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O 2 Reactionchain propagatingrate constantsPropene Combustionenergy surfaceignition delay timepressure-dependent rate coefficientsComputational AnalysisCH 3CHOMicrocanonical rate theoryCH 2 Orate coefficientslaminar flame speedsC 2 H 3O 2 reactionsPESCH 3 COCCSDproduct channels1 atmmultireference methodstransition statesstructure methodsO 2CH 3 CCH 2reaction channelpropene combustionmaster equationC 3 H 5 O 2CH 3 CHCH