Oxydation Entraînée des Hydrocarbures. III. Influence des Alcools

Abstract

AbstractIn the oxidation of cyclohexane in the liquid phase by molecular oxygen, under the pressure of 11 kg. cm−2, at about a temperature of 150°C and in the presence of 50 ppm by weight in cobalt, the influence of the products of reaction on the rate of oxydation of cyclohexane was studied at different concentrations. The cyclohexanol and cyclohexanone have an accelerating effect while on the other hand, adipic acid reduces the rate of transformation.In using certain aliphatic alcohols such as ethanol, n‐ propanol and the isomers of butyl alcohol under different initial concentrations, an accelerating effect was observed, and more particularly with the t‐butanol.In their presence, the rate of reaction is ten times increased for concentrations of alcohol being less than 0.4 mol. l−1. From the schematized, in the liquid phase, competitive oxidation reactions of two substances, by autoinitiated catalysis, an expression of the rate of oxidation of cyclohexane in the mixture was derived. The rate of oxidation of cyclohexane observed when additives are present, is in general twice as higher, than the calculated maximum rate. This divergence is interpreted as an increase in the degree of branching of chains of reactions, following the addition of the additive.