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- W2023287068 abstract "In order to investigate growth mechanisms of polycyclic aromatic hydrocarbons (PAH) that can lead to solids formation in the pre-combustion environments of future high-speed aircraft, we have performed supercritical pyrolysis experiments with the model alkane fuel n-decane (critical temperature, 344.5 °C; critical pressure, 20.7 atm), to which 2-methylnaphthalene and 1-methylnaphthalene, two two-ring products of n-decane pyrolysis, have each been added as a dopant (each dopant concentration, 8.8 mg/g n-decane). The experiments are conducted in an isothermal, silica-lined stainless-steel flow reactor at 570 °C, 94.6 atm, and 133 s, conditions of incipient solids formation. Analyses of the PAH products by high-pressure liquid chromatography with diode-array ultraviolet–visible absorbance and mass-spectrometric detection reveal vast differences in the growth behavior of the two dopants. In the case of 2-methylnaphthalene, growth is virtually limited to the two- and three-ring PAH that result from 2-naphthylmethyl’s reactions with methyl, ethylene, propene, and 1-butene—all abundant in the n-decane pyrolysis environment. In the case of 1-methylnaphthalene, the methyl group’s attachment to a carbon that is just-adjacent to a “valley” carbon of the naphthalene structure permits 1-naphthylmethyl’s reaction with ethylene to form phenalene, an unstable C13H10 PAH that readily loses hydrogen to form the resonance-stabilized phenalenyl radical. This radical sets in motion a sequence for PAH growth that involves reactions of the C2–C4 1-alkenes with both phenalenyl-type radicals and arylmethyl radicals (whose methyl group is attached to a carbon that is just-adjacent to a valley carbon)—producing unsubstituted PAH and methylated PAH of successively higher ring number. As a consequence of these reactions, even though the dopant 1-methylnaphthalene undergoes only 4.5% conversion, it selectively increases (by up to a factor of four) the yields of many of n-decane’s favored four- to eight-ring PAH products—demonstrating the prevalence of the arylmethyl/alkene/phenalenyl reaction mechanism in the supercritical n-decane pyrolysis environment." @default.
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- W2023287068 date "2015-01-01" @default.
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- W2023287068 title "Reaction pathways for the growth of polycyclic aromatic hydrocarbons during the supercritical pyrolysis of n-decane, as determined from doping experiments with 1- and 2-methylnaphthalene" @default.
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- W2023287068 doi "https://doi.org/10.1016/j.proci.2014.06.129" @default.
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