Gas-phase reactions of phenyl radicals with aromatic molecules

Journal Article · Thu Aug 25 00:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100328a026· OSTI ID:6221150

Fahr, A; Stein, S E

Relative rates of reactions of phenyl radicals with a series of aromatic and polycyclic aromatic compounds are reported. Most studies were done in static reactors at 450/degrees/C using diphenyl diketone (benzil) as the phenyl radical source. Reactions with the following molecules are reported: benzene, toluene, p-xylene, 1,3,5-trimethylbenzene, phenol, bromobenzene, naphthalene, biphenyl, anthracene, 9-methylanthracene, and triphenylene. For reactions with substituted benzenes, H abstraction is the dominant reaction. Relative rates of phenylation at different sites do not closely follow established trends for rates of radical attack. It is proposed that these deviations are primarily due to a dependence of the degree of reversibility on the specific site of phenylation. These studies also show that the rates of phenyl and H-atom migration around the ring in adduct radicals are slow relative to dissociation. Also, by use of these results to link literature rate data from high and low temperatures, a rate expression for H abstraction from p-xylene by phenyl of 10/sup 9.6/ exp(-4.4 kcal/RT) M/sup /minus/1/ s/sup /minus/1/ is derived.

• Research Organization: National Bureau of Standards, Gaithersburg, MD (USA)
• OSTI ID: 6221150
• Journal Information: J. Phys. Chem.; (United States), Vol. 92:17
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANTHRACENE
CHEMICAL REACTIONS
BENZENE
BIPHENYL
BROMINATED AROMATIC HYDROCARBONS
NAPHTHALENE
PHENOL
PHENYL RADICALS
TOLUENE
TRIPHENYLENE
XYLENES
CHEMICAL REACTION KINETICS
EXPERIMENTAL DATA
GASES
PYROLYSIS
ALKYLATED AROMATICS
AROMATICS
ARYL RADICALS
CONDENSED AROMATICS
DATA
DECOMPOSITION
FLUIDS
HALOGENATED AROMATIC HYDROCARBONS
HYDROCARBONS
HYDROXY COMPOUNDS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHENOLS
RADICALS
REACTION KINETICS
THERMOCHEMICAL PROCESSES
400201* - Chemical & Physicochemical Properties
400800 - Combustion
Pyrolysis
& High-Temperature Chemistry