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An indirect measurement of the absolute rate constant of the self-reaction of tert-butoxy radicals

✍ Scribed by S. King Wong

Publisher
John Wiley and Sons
Year
1981
Tongue
English
Weight
594 KB
Volume
13
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

No reliable rate constant is available for the self‐reaction of tert‐;butoxy radicals. We have set up a competition between hydrogen abstraction and self‐reaction of tert‐butoxy radicals in a flash photolysis electron spin resonance study to extract this information. Experimental values of hydrogen abstraction product radical concentrations under various hydrogen donor concentrations were then compared with theoretically calculated values with different values of 2__k__~4~ to obtain the best fit. Hydrogen donors such as cyclopentane, anisole, methyl tert‐butyl ether, and methanol were chosen for the study. A value of (1.3 ± 0.5) × 10^9^M^−1^ sec^−1^ for the rate constant of the self‐reaction of tert‐butoxy radicals has been determined at 293°K.

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