Bond homolysis in high-temperature fluids
- National Bureau of Standards, Washington, DC
Rate constants for the homolysis of 1,2-diphenylethane have been determined in tetralin, in dodecahydrotriphenylene, and in the gas phase at temperatures above 350/sup 0/C. The least-squares-derived Arrhenius expression for this reaction in the gas phase is k/sub 1//s/sup -1/ = 10/sup (15.25+-0.15)-(62.31+-0.50)/theta (theta = 0.004576T/K) and is consistent with available thermokinetic data. In liquid tetralin up to its critical temperature and in liquid dodecahydrotriphenylene Arrhenius parameters for this reaction were found to be distinctly higher than gas-phase values, and rate constants to be somewhat lower. These differences between gas- and liquid-phase kinetics are attributed to recombination of nascent free radicals in solution (the cage effect), the probability of which decreases with decreasing viscosity.
- OSTI ID:
- 6417558
- Journal Information:
- J. Am. Chem. Soc.; (United States), Vol. 104:24
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
BIBENZYL
DECOMPOSITION
CHEMICAL BONDS
EXPERIMENTAL DATA
HIGH TEMPERATURE
RADICALS
REACTION KINETICS
TETRALIN
TRIPHENYLENE
AROMATICS
CHEMICAL REACTIONS
CONDENSED AROMATICS
DATA
HYDROCARBONS
INFORMATION
KINETICS
NUMERICAL DATA
ORGANIC COMPOUNDS
010405* - Coal
Lignite
& Peat- Hydrogenation & Liquefaction
400301 - Organic Chemistry- Chemical & Physicochemical Properties- (-1987)