Thermal decomposition of benzyl iodide and of benzyl radicals in shock waves

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

DOI:https://doi.org/10.1021/j100328a020· OSTI ID:5992210

Mueller-Markgraf, W; Troe, J

The thermal decomposition of benzyl iodide into benzyl radicals + I was studied in shock waves by UV absorption spectroscopy. Rate constants k/sub 1/ = 10/sup 14.78/ exp(/minus/181 kJ mol/sup /minus/1//RT) s/sup /minus/1/ for the dissociation, and k/sub 2/ = 10/sup 13.70/ cm/sup 3/ mol/sup /minus/1/ s/sup /minus/1/ for the reverse recombination of benzyl radicals and iodine atoms, were derived over the range 750 less than or equal to T less than or equal to 950 K. For the subsequent recombination of the formed benzyl radicals to dibenzyl, a rate constant k/sub 7/ = 10/sup 12.60/(T/1000 K)/sup 0.4/ cm/sup 3/ mol/sup /minus/1/ s/sup /minus/1/ was obtained together with a dibenzyl dissociation rate constant of k/sub 8/ = 10/sup 14.9/ exp(-250 kJ mol/sup /minus/1//RT) s/sup /minus/1/ (temperature range 900 less than or equal to T less than or equal to 1500 K). The UV absorption spectra and dissociation rate constants k/sub 11/ of benzyl radicals were then studied from 1250 up to 1900 K. k/sub 11/ is represented as the sum k/sub 9/ + k/sub 10/ with k/sub 9/ = 10/sup 10.22/exp(-187 kJ mol/sup /minus/1//RT) s/sup /minus/1/ and k/sub 10/ = 10/sup 15.30/ exp(-349.6 kJ mol/sup /minus/1//RT) s/sup /minus/1/. The spectroscopic and kinetic properties at high temperatures of benzyl radicals derived from several different precursor molecules agree.

• Research Organization: Universitaet Goettingen (Germany, F.R.)
• OSTI ID: 5992210
• 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
02 PETROLEUM
BENZYL RADICALS
PYROLYSIS
IODINATED AROMATIC HYDROCARBONS
ABSORPTION SPECTROSCOPY
CHEMICAL REACTION KINETICS
DISSOCIATION
EXPERIMENTAL DATA
SHOCK WAVES
ULTRAVIOLET SPECTRA
AROMATICS
ARYL RADICALS
CHEMICAL REACTIONS
DATA
DECOMPOSITION
HALOGENATED AROMATIC HYDROCARBONS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
RADICALS
REACTION KINETICS
SPECTRA
SPECTROSCOPY
THERMOCHEMICAL PROCESSES
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