Kinetic modeling of benzene decomposition near 1000 K: The effects of toluene impurity

Brioukov, M.; Park, Jeanie; Lin, Ming‐Chang

doi:10.1002/(sici)1097-4601(1999)31:8<577::aid-kin7>3.3.co;2-b

Cited by 5 publications

(7 citation statements)

References 10 publications

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“…Until now, all experimental and theoretical studies ,,− have reported biphenyl as the only product of reactions and . Additionally, Manion et al has reported the rate constant for the reverse reaction (–1).…”

Section: Introductionmentioning

confidence: 99%

Novel Products from C₆H₅ + C₆H₆/C₆H₅ Reactions

2011

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To date only one product, biphenyl, has been reported to be produced from C(6)H(5) + C(6)H(6)/C(6)H(5) reactions. In this study, we have investigated some unique products of C(6)H(5) + C(6)H(6)/C(6)H(5) reactions via both experimental observation and theoretical modeling. In the experimental study, gas-phase reaction products produced from the pyrolysis of selected aromatics and aromatic/acetylene mixtures were detected by an in situ technique, vacuum ultraviolet (VUV) single photon ionization (SPI) time-of-flight mass spectrometry (TOFMS). The mass spectra revealed a remarkable correlation in mass peaks at m/z = 154 {C(12)H(10) (biphenyl)} and m/z = 152 {C(12)H(8) (?)}. It also demonstrated an unexpected correlation among the HACA (hydrogen abstraction and acetylene addition) products at m/z = 78, 102, 128, 152, and 176. The analysis of formation routes of products suggested the contribution of some other isomers in addition to a well-known candidate, acenaphthylene, in the mass peak at m/z = 152 (C(12)H(8)). Considering the difficulties of identifying the contributing isomers from an observed mass number peak, quantum chemical calculations for the above-mentioned reactions were performed. As a result, cyclopenta[a]indene, as-indacene, s-indacene, biphenylene, acenaphthylene, and naphthalene appeared as novel products, produced from the possible channels of C(6)H(5) + C(6)H(6)/C(6)H(5) reactions rather than from their previously reported formation pathways. The most notable point is the production of acenaphthylene and naphthalene from C(6)H(5) + C(6)H(6)/C(6)H(5) reactions via the PAC (phenyl addition-cyclization) mechanism because, until now, both of them have been thought to be formed via the HACA routes. In this way, this study has paved the way for exploring alternative paths for other inefficient HACA routes using the PAC mechanism.

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Section: Introductionmentioning

confidence: 99%

Novel Products from C₆H₅ + C₆H₆/C₆H₅ Reactions

2011

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“…The reaction kinetics of the C 6 H 5 radical with a wide variety of reactants have been investigated by cavity ringdown spectroscopy , and laser flash photolysis techniques . The reaction kinetics ,,, of phenyl with the diatomics: HBr, O 2 , NO, and H 2 , have been reported.…”

Section: Introductionmentioning

confidence: 99%

The Infrared Spectrum of the Matrix-Isolated Phenyl Radical

et al. 2001

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We have measured the infrared absorption spectrum of C(6)H(5), /X (2)A(1), in an Ar matrix at 10 K. The experimental frequencies (cm(-)(1)) and polarizations follow. a(1) modes: 3086, 3072, 3037, 1581, 1441, 1154, 1027, 997, 976, 605; b(1) modes: 972, 874, 706, 657, 416; b(2) modes: 3071, 3060, 1624, 1432, 1321, 1283, 1159, 1063, and 587. Three different methods have been used for the production of the phenyl radicals. Infrared absorption spectra of five deuterated isotopomers, C(6)D(5), p-C(6)H(4)D, p-C(6)HD(4), o-C(6)H(4)D, and m-C(6)H(4)D, were recorded to compare experimental frequency shifts with calculated (UB3LYP/cc-pVDZ) harmonic frequency shifts. The use of CO(2) or NO as internal standards enabled the experimental determination of absolute infrared intensities. The linear dichroism was measured with photooriented samples to establish experimental polarizations of each vibrational band. True gas-phase vibrational frequencies were estimated by considering the gas-to-matrix shifts and matrix inhomogeneous line broadening. The phenyl radical matrix frequencies listed above are within +/-1% of the gas-phase vibrational frequencies. The C(6)H(5) frequencies from this paper supersede our earlier values reported in J. Am. Chem. Soc. 1996, 118, 7400-7401. See also: http://ellison.colorado.edu/phenyl.

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“…At low temperatures, primary reactions of the pyrolysis of benzene are rather simple. 31 The only reaction of unimolecular initiation is the breaking of a C-H bond (bond energy of 110.9 kcal mol -1 ). Breaking of a benzylic C-C bond of benzene is very difficult because of the high energy of this type of bond (120.8 kcal mol -1 ).…”

Section: Discussionmentioning

confidence: 99%

Thermal Decomposition of Norbornane (bicyclo[2.2.1]heptane) Dissolved in Benzene: Experimental Study and Mechanism Investigation

et al. 2007

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The thermal decomposition of norbornane (dissolved in benzene) has been studied in a jet stirred reactor at temperatures between 873 and 973 K, at residence times ranging from 1 to 4 s and at atmospheric pressure, leading to conversions from 0.04 to 22.6%. 25 reaction products were identified and quantified by gas chromatography, amongst which the main ones are hydrogen, ethylene and 1,3-cyclopentadiene.A mechanism investigation of the thermal decomposition of the norbornane -benzene binary mixture has been performed. Reactions involved in the mechanism have been reviewed: unimolecular initiations 1 by C-C bond scission of norbornane, fate of the generated diradicals, reactions of transfer and propagation of norbornyl radicals, reactions of benzene and cross-coupling reactions.

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Kinetic modeling of benzene decomposition near 1000 K: The effects of toluene impurity

Cited by 5 publications

References 10 publications

Novel Products from C₆H₅ + C₆H₆/C₆H₅ Reactions

Novel Products from C₆H₅ + C₆H₆/C₆H₅ Reactions

The Infrared Spectrum of the Matrix-Isolated Phenyl Radical

Thermal Decomposition of Norbornane (bicyclo[2.2.1]heptane) Dissolved in Benzene: Experimental Study and Mechanism Investigation

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Kinetic modeling of benzene decomposition near 1000 K: The effects of toluene impurity

Cited by 5 publications

References 10 publications

Novel Products from C6H5 + C6H6/C6H5 Reactions

Novel Products from C6H5 + C6H6/C6H5 Reactions

The Infrared Spectrum of the Matrix-Isolated Phenyl Radical

Thermal Decomposition of Norbornane (bicyclo[2.2.1]heptane) Dissolved in Benzene: Experimental Study and Mechanism Investigation

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Novel Products from C₆H₅ + C₆H₆/C₆H₅ Reactions

Novel Products from C₆H₅ + C₆H₆/C₆H₅ Reactions