The Absolute Measurement of Rate Constants for Some Kay Reactions Involving Free Radicals

A new method has been developed for the determination of absolute rate constants for the recombination of free radicals. The method is an extension of the very low-pressure (VLPP) technique and was applied to the study of the recombination of ethyl radicals and of isopropyl radicals. Application of...

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Bibliographic Details
Main Authors: Beadle,Peter C, Perona,Michael J, Golden,David M
Format: Report
Language:English
Subjects:
AZO COMPOUNDS
DECOMPOSITION
FREE RADICALS
GASES
ORGANIC NITROGEN COMPOUNDS
PEROXIDES
PEROXY ORGANIC COMPOUNDS
Physical Chemistry
PYROLYSIS
REACTION KINETICS
RECOMBINATION REACTIONS
SURFACES
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Summary:A new method has been developed for the determination of absolute rate constants for the recombination of free radicals. The method is an extension of the very low-pressure (VLPP) technique and was applied to the study of the recombination of ethyl radicals and of isopropyl radicals. Application of the method required a preliminary study of the decomposition of certain radical sources under VLPP conditions. The radical sources studied were di-t-amyl peroxide, azoethane, azoisopropane, and 2,2'-azoisobutane. In the case of the azo compounds, the flow dependence of k(uni) was used to estimate collisional efficiencies. The radical recombination studies yielded preliminary high pressure absolute rate constants. It was found that both ethyl radical and isopropyl radicals are removed by a first-order wall process. The rate constant for this process was found to be dependent on the nature of the wall. (Author)