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Experimental and kinetic modeling investigation on 2,5-hexanedione oxidation in a jet-stirred reactor

机译:Experimental and kinetic modeling investigation on 2,5-hexanedione oxidation in a jet-stirred reactor

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摘要

Unique resonance stabilization features of R and QOOH radicals of 2,5-hexanedioneCH _3 C( = O)CH _2 CH _2 C( = O)CH _3 facilitated the investigation on the roles of carbonyl group in the oxidationof ketones. This work presents the first study on the speciation from the oxidation of 2,5-hexanedione. Afuel-lean ( φ= 0.5) 2,5-hexanedione/O _2 /Ar mixture was investigated in a jet-stirred reactor (JSR) operatedat atmospheric pressure, over a temperature range of 60 0–90 0 K. Synchrotron vacuum ultravioletphotoionization mass spectrometry was employed to acquire detailed speciation information. A detailedkinetic mechanism was proposed based on the “reaction classes” strategy and validated against thecurrent measurements. No obvious low-temperature reactivity was observed under the investigatedconditions, and the reason was attributed to the unfavored ROO = QOOH isomerization reactions of bothtwo RO _2 radicals, while the energetically favored HO _2 -elimination reactions produce inert HO _2 radicalsin the low-temperature regime. β-scission reactions dominate the consumption of fuel radicals. Theprediction of fuel reactivity strongly depends on the reactions involving the small hydrocarbon speciesand H-atom abstraction reactions. The competition between the reaction pair of CH _3 + HO _2 = CH _3 O + OHand CH _3 + HO _2 = CH 4 + O _2 is the most influential factor for the fuel reactivity in the studied temperatureregimes. Based on the experimental observations and kinetic modeling analyses, fuel consumption andmajor intermediates formation pathways in 2,5-hexanedione were illustrated.

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