Rate coefficients for 1,2-dimethyl-allyl + HO2/O2 and the implications for 2-methyl-2-butene combustion
| Autor: | Erjiang Hu, Geyuan Yin, Xi Chen, Zuohua Huang, Claude Franklin Goldsmith |
|---|---|
| Rok vydání: | 2021 |
| Předmět: |
Work (thermodynamics)
Materials science 010304 chemical physics General Chemical Engineering Thermal decomposition General Physics and Astronomy Energy Engineering and Power Technology Thermodynamics 02 engineering and technology General Chemistry Combustion 01 natural sciences Decomposition Transition state Fuel Technology 020401 chemical engineering 0103 physical sciences Master equation Reactivity (chemistry) 0204 chemical engineering Isomerization |
| Zdroj: | Combustion and Flame. 230:111433 |
| ISSN: | 0010-2180 |
| DOI: | 10.1016/j.combustflame.2021.111433 |
| Popis: | A detail investigation is presented on the reaction of 1,2-dimethyl-allyl with HO2, including bimolecular reactions of aC5H9-c with HO2, thermal decomposition reactions of aC5H9OOH, and the subsequent decomposition and isomerization reactions of C5H9O based on theoretical work. In addition, the reaction of aC5H9-c with O2 and the resulting peroxy-radical chemistry is presented. The majority of the stationary points are obtained at CCSD(T)-F12/cc-pVTZ-F12//M06–2X/6–311G(d,p) level, with barrierless reaction and some transition states using multireference method. Microcanonical rate theory and the master equation are used to determine the temperature- and pressure-dependent rate coefficients, as implemented in a RRKM/ME code. Uncertainty analysis for energy barrier and ∆Edown were conducted. The newly developed submechanisms for the reactions of 1,2-dimethyl-allyl with HO2 and O2 are added to a previous literature model for 2-methy-butene. The results show that at low pressure/high temperature, the reaction aC5H9-c with HO2 would directly decompose to aC5H9O + OH, which, though technically a chain propagating reaction, and significantly increases the reactivity of the system. The updated mechanism is in much better agreement with the available experimental data. |
| Databáze: | OpenAIRE |
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