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Reactions of Alkoxy Radicals. II. The Absolute Rate Constant for the Combination of t-Butoxy Radicals 1

โœ Scribed by Carlsson, D. J.; Howard, J. A.; Ingold, K. U.


Book ID
127106606
Publisher
American Chemical Society
Year
1966
Tongue
English
Weight
261 KB
Volume
88
Category
Article
ISSN
0002-7863

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## Abstract The rate constant for __tert__โ€butyl radical recombination has been measured near 700ยฐK by the veryโ€lowโ€pressure pyrolysis (VLPP) technique and was found to be 10^8.8ยฑ0.3^ __M__^โˆ’1^ยทsec^โˆ’1^ with neglibible temperature dependence. The thermochemical parameters for __tert__๏ฃฟbutyl radicals

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An absolute value of k, of ethyl radicals at 860 f 17ยฐK 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 860ยฐK. An error of as much as a factor of 2 in k, would be surprising, but possible. The value of lO'OM-'