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Rate constants for the decarboxylation of the t-butoxicarbonyl radical and concurring radical terminations directly obtained by kinetic ESR

✍ Scribed by D. Rüegge; H. Fischer

Publisher: John Wiley and Sons
Year: 1986
Tongue: English
Weight: 723 KB
Volume: 18
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550180202

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✦ Synopsis

Rate constants of various simultaneous reactions of t-butoxicarbonyl and t-butyl radicals generated by photolysis of t-butylpivalate in n-heptane are directly determined by kinetic electron spin resonance. The temperature dependence of the decarboxylation reaction t-BuOCO + t-Bu + CO, obeys log(k/s-') = 13.8-49.0/8 where 8 = 2.303 RT/ kJ . mol-'. The self-and cross-termination of the radicals are diffusion limited.

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✍ Hiroyuki Adachi; N. Basco; D. G. L. James 📂 Article 📅 1979 🏛 John Wiley and Sons 🌐 English ⚖ 558 KB

## Abstract Intrinsic spectral and kinetic parameters have been measured for the ethyl radical, which was formed in the gas phase by the flash photolysis of azoethane. Absolute values of the extinction coefficient ϵ(λ) were derived from complementary measurements of the yield of nitrogen and the ab