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The Unimolecular Decomposition of Cyclobutanol: Experimental and Theoretical Study
Author(s) -
Tanaka Seiji,
Tomariguchi Susumu,
Saito Ko,
Takahashi Osamu,
Tabayashi Kiyohiko
Publication year - 1996
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.199600035
Subject(s) - chemistry , acetaldehyde , decomposition , thermal decomposition , ethylene , kinetic energy , absorption (acoustics) , alcohol , vinyl alcohol , kinetics , wavelength , reaction rate constant , photochemistry , thermodynamics , organic chemistry , ethanol , catalysis , optics , physics , polymer , quantum mechanics
The thermal decomposition of cyclobutanol has been investigated behind incident and reflected shock waves at temperatures between 950 K and 1450 K in the total density region (1.5 × 10 −6 – 1.5 × 10 −5 ) mol/cm 3 . A strong absorption by an intermediate was observed at the wavelength of 193 nm. By comparing the kinetics with that of pyruvic acid, this absorption was identified to be that of vinyl alcohol. The kinetic parameters of vinyl alcohol, both for the production and the decomposition, were determined. The production rate constant was in agreement with that obtained by Back ( Can J. Chem. 1982 , 60 , 2357), who monitored the ethylene production. The total decomposition mechanism of cyclobutanol was discussed on the basis of MO calculations. It was shown that vinyl alcohol was produced through a biradical before it isomerized to acetaldehyde.