900. The reactions of phenyl radicals from the photolysis of acetophenone and the strength of the C–H bond in benzene

Duncan, F. J.; Trotman‐Dickenson, A. F.

doi:10.1039/jr9620004672

Cited by 34 publications

(30 citation statements)

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“…In this work, we measure the rate constants for C 6 H 5 reactions with 2-methylpropane (isobutane, hereafter denoted as C 4 H 10 ), 2,3-dimethylbutane (di-isopropyl, C 6 H 14 ) and 2,3,4-trimethylpentane (C 8 H 18 ). Among these gas-phase reactions, only the rate constant for the isobutane reaction has been reported [14]. This result was obtained by the conventional relative rate method and will be compared with our directly determined value later.…”

Section: Introductionmentioning

confidence: 97%

Kinetics of C6H5 radical reactions with 2-methylpropane, 2,3-dimethylbutane and 2,3,4-trimethylpentane

Park

Gheyas

Lin

1999

Int. J. Chem. Kinet.

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The absolute bimolecular rate constants for the reactions of C 6 H 5 with 2-methylpropane, 2,3-dimethylbutane and 2,3,4-trimethylpentane have been measured by cavity ringdown spectrometry at temperatures between 290 and 500 K. For 2-methylpropane, additional measurements were performed with the pulsed laser photolysis/mass spectrometry, extending the temperature range to 972 K. The reactions were found to be dominated by the abstraction of a tertiary C-H bond from the molecular reactant, resulting in the production of a tertiary alkyl radical:

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Section: Introductionmentioning

confidence: 97%

Kinetics of C6H5 radical reactions with 2-methylpropane, 2,3-dimethylbutane and 2,3,4-trimethylpentane

Park

Gheyas

Lin

1999

Int. J. Chem. Kinet.

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“…This is suggested by the fact that the hydrogen atom abstraction by the phenyl radical from isobutane requires the activation energy (6.7 kcal/mole). 8 Thus, in the presence of ethane, the reaction of ethyl radicals with benzyl radicals should result in the formation of toluene and ethylene, or n-propylbenzene. Ethyl radicals form ethane, ethylene, or n-butane.…”

Section: Formation Mechanism Of the Productsmentioning

confidence: 99%

“…Since butene is produced from two reactions [(7) and (8)J, the yield of butene by the disproportionation reaction between butyl radicals only [Reaction (8) ] is obtained subtracting the yield of toluene [equal to the yield of butene from Reaction (7) only] from the total yield of butene. The ratio for ethyl radicals is obtained by the same procedure.…”

Section: Disproportionation and Recombinationmentioning

confidence: 99%

Photolysis of Benzyl Chloride Vapor in the Presence of Ethane or n-Butane

Ichimura

Mori

1972

The Journal of Chemical Physics

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Benzyl chloride vapor has been photolyzed in the presence of ethane or n-butane at 184.9, 206.2, and 253.7 nm. Pressure, wavelength, and temperature effects on the quantum yields of products were examined. Benzyl chloride was found to photodecompose predominantly to a benzyl radical and a chlorine atom. The chlorine atoms abstract the hydrogen atom from ethane or n-butane to form ethyl or butyl radicals. The reaction of these radicals with benzyl radicals results in the formation of various products. The quantum yield of the initial photodecomposition of the C-Cl bond in benzyl chloride at 184.9 nm (at zero n-butane pressure) was obtained to be 0.9. The initial photodecomposition rate constant of benzyl chloride at 184.9 nm has been estimated. The ratio between disproportionation and recombination reaction rate constants of radicals has also been obtained.

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“…The dissociation energy of the C-H bond in benzene is around 102 kcal/mol [24], lower than that of C-H bond in 4-CB of 110 kcal/mol. The typical dioxin precursors, such as MCBz and 2-CP, have been studied to gain insights into the mechanism of PCDD/F formation in fires [25][26][27].…”

Section: Voc Analysismentioning

confidence: 99%

Formation of Chlorinated Dibenzo-p-dioxins and Dibenzofurans (CDD/F) and Their Precursors in Oxidation of 4-Chlorobiphenyl

Hou¹,

Dlugogorski²,

Altarawneh³

et al. 2013

Proceedings of the Seventh International Seminar Fire and Explosion Hazards

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Formation of Chlorinated Dibenzo-p-dioxins and Dibenzofurans (CDD/F) and Their Precursors in Oxidation of 4-Chlorobiphenyl ABSTRACTThis study investigates the gas-phase thermal oxidation of 4-chlorobiphenyl (4-CB) over a temperature range of 300 to 700 °C, under conditions similar to those occurring in fires and open burning of waste. The experiments deployed an isothermal flow reactor made of high purity quartz and equipped with a sample collection system to adsorb volatile and semi-volatile organic compounds (VOC/SVOC), the latter included chlorinated dibenzo-p-dioxins and dibenzofurans (CDD/F). The analysis was performed by gas chromatography-quadrupole mass spectrometry (GC-QMS) and GCion trap MS/MS (GC-ITMS/MS), for VOC and SVOC, respectively. Under oxidative conditions, the thermal degradation of 4-CB produced VOC species; mainly, naphathelene, styrene, and benzaldehyde. Selected ion monitoring (SIM), performed on the GC-QMS instrument, confirmed the formation of minor species, such as chlorophenols (CP) and chlorobenzenes (CBz), first observed to form in experiments conducted around 500 °C. The trace analysis by GC-ITMS/MS identified mono and dichlorinated isomers of CDD/F (dioxins), with monochlorodibenzofurans (MCDF) as the dominant homologue group. We observed the formation of 3-chlorodibenzofuran at temperature as low as 300 °C, possibly by direct oxidation of 4-CB by singlet oxygen ( 1 Δ g ) generated on the walls of the quartz reactor, or by catalytic oxidation of 4-CB by the transition metals remaining in the high purity quarts at sub-ppm levels. Other CDD/F form in gas-phase reactions at temperature in excess of 600 °C.

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900. The reactions of phenyl radicals from the photolysis of acetophenone and the strength of the C–H bond in benzene

Cited by 34 publications

References 0 publications

Kinetics of C6H5 radical reactions with 2-methylpropane, 2,3-dimethylbutane and 2,3,4-trimethylpentane

Kinetics of C6H5 radical reactions with 2-methylpropane, 2,3-dimethylbutane and 2,3,4-trimethylpentane

Photolysis of Benzyl Chloride Vapor in the Presence of Ethane or n-Butane

Formation of Chlorinated Dibenzo-p-dioxins and Dibenzofurans (CDD/F) and Their Precursors in Oxidation of 4-Chlorobiphenyl

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