Thermal decomposition of toluene: a comparison of thermal and laser-photochemical activation experiments

Journal Article · Thu Aug 25 04:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100328a021· OSTI ID:6253311

Brouwer, L D; Mueller-Markgraf, W; Troe, J

The thermal decomposition of toluene has been reinvestigated in shock waves detecting toluene, benzyl radicals, and benzyl fragment concentrations by UV absorption spectroscopy in the range 190-320 nm. The experiments are interpreted in terms of a dominant toluene dissociation into benzyl radicals + H fragments with a rate constant k/sub 1/ = 10/sup 15.45/plus minus/0.2/ exp(-(371.9 /plus minus/ 10) kJ mol/sup /minus/1//RT) s/sup /minus/1/ (at (Ar) = (2.6 /plus minus/ 0.4) /times/ 10/sup /minus/4/ mol cm/sup /minus/3/) and in terms of a faster benzyl fragmentation which is in agreement with experiments on other benzyl sources. The derived thermally average rate constants of toluene dissociation k/sub 1/ are consistent with specific rate constants k(E,J) from laser excitation experiments. Similarly, the nature of the dominant product channel is consistently identified in thermal and photochemical experiments, ruling out a recently discussed dominance of fragmentation into the phenyl + methyl channel.

• Research Organization: Universitaet Goettingen (Germany, F.R.)
• OSTI ID: 6253311
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Journal Issue: 17 Vol. 92:17; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

02 PETROLEUM
025000 -- Petroleum-- Combustion
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400800* -- Combustion
Pyrolysis
& High-Temperature Chemistry
ALKYLATED AROMATICS
AROMATICS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
DISSOCIATION
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
KINETICS
LASERS
NUMERICAL DATA
ORGANIC COMPOUNDS
PHOTOCHEMICAL REACTIONS
PYROLYSIS
REACTION KINETICS
THERMOCHEMICAL PROCESSES
TOLUENE