Abstract: The kinetics of the gas-phase thermal isomerization of epoxypropane has been studied over the temperature range 1045-1175 K in a single-pulse shock tube. Uni-molecular isomerizations to propionaldehyde, acetone, methyl vinyl ether and allylol account for about 65% of the primary reactions which occur by first order, homoge-neous, non-radical processes. Secondary reactions, that make quantitative determina-tion of the individual rate constants difficult, were reduced by the addition of radi-cal scavenger nitric oxide.
k_(propionaldehyde)(s~(-1))=10~(14.3)exp(-262 kJmol~(-1)/RT)
k_(acetone)(s~(-1))=10~(14.0)exp(-268 kJmol~(-1)/RT)
k_(methylvinyl ether)(s~(-1))=10~(13.4)exp(-264 kJmol~(-1)/RT)
k_(allylol)(s~(-1))=10~(13.9)exp(-275 kJmol~(-1)/RT)
A biradical mechanism for the isomerization of epoxypropane has been preferred. It adequately exlained kinetic observations. The RRKM theory of unimolecular reactions was applied to explain the thermal isomerization of epoxypropane.