Gas-phase oxidation of hexene-1

Abstract An investigation has been made of the oxidation of hexene-1 at 263°C. The unusual form of dependency of reaction rate on hydrocarbon pressure obtained when the maximum rate of pressure change is used as a measure of reaction rate is explained by the fact that much of the oxygen is consumed before the maximum rate of pressure change is attained. This, and the observation that the maximum rate of oxygen consumption exhibits a different dependence on hexene concentration compared with the maximum rate of pressure change confirm that maximum rate of pressure change is an invalid measure of reaction rate. Analyses have been made for certain intermediates and products throughout the course of the reaction, and it has been possible to explain many of the experimental features in terms of ideas previously propounded. A decrease in pressure which in many experiments precedes the rapid increase in pressure is attributed to polymerization reactions which predominated over oxidative degradations in the early stages of the reaction, particularly when the olefin is present in excess.