An absolute value of k, of ethyl radicals at 860 f 17°K of 4.5 X l o 9 M-l.sec-' was determined under VLPP conditions, where the value of k,/k," should be about M. Thus k,"(M-'.sec-') -10' 0 at 860°K. An error of as much as a factor of 2 in k, would be surprising, but possible. The value of lO'OM-'
An absolute measurement of the rate constant for t-butyl radical combination
✍ Scribed by K. Y. Choo; P. C. Beadle; L. W. Piszkiewicz; D. M. Golden
- Publisher
- John Wiley and Sons
- Year
- 1976
- Tongue
- English
- Weight
- 584 KB
- Volume
- 8
- Category
- Article
- ISSN
- 0538-8066
No coin nor oath required. For personal study only.
✦ Synopsis
Abstract
The rate constant for tert‐butyl radical recombination has been measured near 700°K by the very‐low‐pressure pyrolysis (VLPP) technique and was found to be 10^8.8±0.3^ M^−1^·sec^−1^ with neglibible temperature dependence. The thermochemical parameters for __tert__butyl radicals were varied within reasonable limits to bring into agreement the data for the decomposition of 2,2,3,3‐tetramethyl butane and the recombination of tert‐butyl radicals. The revised thermochemistry also makes the gas‐phase results and liquid‐phase results compatible.
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