2006
DOI: 10.1021/jp0623802
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Abstract: To better understand the thermal decomposition of polycyclanes, the pyrolysis of tricyclodecane has been studied in a jet-stirred reactor at temperatures from 848 to 933 K, for residence times between 0.5 and 6 s and at atmospheric pressure, corresponding to a conversion between 0.01% and 25%. The main products of the reaction are hydrogen, methane, ethylene, ethane, propene, 1,3-cyclopentadiene, cyclopentene, benzene, 1,5-hexadiene, toluene, and 3-cyclopentylcyclopentene. A primary mechanism containing all th… Show more

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Cited by 79 publications
(135 citation statements)
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References 36 publications
(126 reference statements)
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“…While the concerted retro-Diels-Alder mechanism is possible, we only observe intermediates along a stepwise retro-decomposition pathway. This production of ethylene is consistent with experimental observations, 4,5,7,8,12 but there is no experimental evidence for a cyclooctadiene intermediate, which could be attributed to its reactivity under pyrolysis conditions. Indeed, this is consistent with ReaxFF simulations at higher temperatures, where we find that cyclooctadiene undergoes ring opening and further decomposition in <1 ps.…”
Section: Resultssupporting
confidence: 91%
See 1 more Smart Citation
“…While the concerted retro-Diels-Alder mechanism is possible, we only observe intermediates along a stepwise retro-decomposition pathway. This production of ethylene is consistent with experimental observations, 4,5,7,8,12 but there is no experimental evidence for a cyclooctadiene intermediate, which could be attributed to its reactivity under pyrolysis conditions. Indeed, this is consistent with ReaxFF simulations at higher temperatures, where we find that cyclooctadiene undergoes ring opening and further decomposition in <1 ps.…”
Section: Resultssupporting
confidence: 91%
“…7,8 Thermal decomposition, catalytic cracking, and shock tube studies have provided insight into the overall chemistry of JP-10 decomposition, but the details of the initiation reactions and the high-temperature chemistry are still not well-established. 1,4,5,[7][8][9][10][11][12][13][14] The products observed experimentally from the thermal decomposition of JP-10 are summarized from the literature in Table 1. The pyrolysis products common to all of the experiments are benzene and cyclopentadiene (CPD), but there is no agreement on whether the formation of these products results from primary or secondary chemistry.…”
Section: Introductionmentioning
confidence: 99%
“…Although studies [1][2][3][4][5][6][7][8][9][10][11] have been conducted to investigate the physical properties and catalytic cracking of JP-10 at various temperatures and pressures by means of spectroscopic, gas chromatographic, and mass spectrometric analyses, the high-temperature thermal decomposition chemistry of JP-10 is still not well understood.…”
Section: Introductionmentioning
confidence: 99%
“…We estimate approximately five collisions (A = 9 × 10 13 cm 3 (mol s) −1 ) and a small barrier (E a = 1.5), for the electronic state crossing, collision of diradical with bath gas, or chemical activation of diradical in association reaction with O 2 , as there is ∼35 kcal mol The intramolecular hydrogen transfer reactions were estimated from literature calculations on fourto six-membered ring-opened systems [1] at the CBS-QB3 level, and a computational study on the thermal decomposition of tricyclodecane [14]. The rate constants for the unimolecular β-scission reactions have been estimated from a literature evaluation of the experimental data on β-scission reactions of hydrocarbons [15].…”
Section: Kineticsmentioning
confidence: 99%