The unimolecular decomposition of cyclobutanol: Experimental and theoretical study

Article abstract of DOI:10.1002/ijch.199600035

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/cm³. 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.