Chemical kinetics study of 1,3-butadiene + HȮ2; implications for combustion modeling and simulation

Abstract

Detailed reaction kinetics for the system of 1,3-butadiene + hydroperoxyl radical (HȮ2) and its application in combustion modeling have been investigated in this work. Zero-point energy (ZPE) corrected potential energy surfaces (PESs) for the title reactions have been obtained using high-level ab initio electronic structure methods of ROCCSD(T)/CBS//BHandHLYP/6–311++G(d,p), and the energies relative to the reactants for all stationary points were used in the kinetic calculations. Pressure- and temperature-dependent rate constants for each individual reaction pathway have been calculated by solving the Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) implemented in the Master Equation System Solver (MESS) program. The bimolecular pathways forming vinyl oxirane, (CYOC)CC, and hydroxyl radical (ȮH) from the reactants are found to be dominant in the temperature range of 800–2000 K below 1 atm, and keep competitive when temperature is higher than 1000 K at 100 atm. At elevated pressures, the stabilizations of the two entrance channels forming radicals of 1-hydroperoxy-3-buten-2-yl (C4H61–3OOH4) and 3-butenyl-2-peroxy (C4H71-OO3) are more important than the formation of bimolecular products (CYOC)CC + ȮH at temperatures below 1000 K. Temperature-dependent thermochemical properties for important species on the PESs of 1,3-butadiene + HȮ2 have also been calculated. The kinetics and thermochemistry data for the title reaction system calculated in this work have been incorporated into AramcoMech 3.0 mechanism and their influence on the performance of AramcoMech 3.0 in simulating the combustion properties of 1,3-butadiene, including ignition delay times and species profiles against temperature or time, has been investigated. This is a first-time study on the reaction kinetics between HȮ2 radical and species including two double bonds.