✦ LIBER ✦

Homogeneous decomposition of vinyl ethers. The heat of formation of ethanal-2-yl

✍ Scribed by M. Rossi; D. M. Golden

Publisher: John Wiley and Sons
Year: 1979
Tongue: English
Weight: 715 KB
Volume: 11
Category: Article
ISSN: 0538-8066
DOI: 10.1002/kin.550110705

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✦ Synopsis

Abstract

The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high‐pressure rate constant for the retro‐ene reaction of ethylvinylether was fit by log k (sec^−1^) = (11.47 + 0.25) ‐ (43.4 ± 1.0)/2.303 RT at <T> = 900 K and that of t ‐ butylvinylether by log k (sec^−1^) = (12.00 ± 0.27) ‐ (38.4 ± 1.0)/2.303 RT at <T> = 800 K. No evidence for the competition of the higher energy homolytic bond‐fission process could be obtained from the experimental data. The rate constant compatible with the CO bond scission reaction in the case of benzylvinylether was log k (sec^−1^) = (16.63 ± 0.30) ‐ (53.74 ± 1.0)/2.303 RT at <T> = 750 K. Together with Δ__H__~f,300~^0^(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in Δ__H__~f,300~^0^(CH~2~CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2‐ethanalyl radical.

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