Effects of Atmospheres, Solvents and Fatty Acids on Decomposition of Cyclohexanone Peroxide

Abstract

Cyclohexanone peroxide (CYP) which was regarded as one of the intermediates of the autoxldation of cyclohexane was synthesized, and the effects of atmospheres, solvents and fatty acids on the decomposition were studied.The main decomposition product was cyclohexanone, and the decomposition rates were found to be proportional to the concentration of CYP(Figs.1 and 2).The rates of the decomposition, k, were dependent on atmospheres and solvents, i. e., the rate constant decreased in the order of nitrogeng carbon monoxideg carbon dioxideg heliumg hydrogeng airg oxygen and of acetic acid, cyclohexanoneg cyclohexanolg chlorobenzene, 1dodecanolg n-dodecaneg toluene, respectively(Table 1 and Figs.1 and 2). It should be noted that the yield of cyclohexanone was also dependenton the atmospheres.A linear relationship exists between log k and the values of (D-1)/(2D+1)(D: dielectric constants of solvents), except for n-dodecane and acetic acid(Fig.3). The activation energy for the decomposition in cyclohexanol at 80-120 C was calculated as 13.8kcal per mole(Fig.4).It was also found that the addition of the fatty acids caused the considerable acceleration of the decomposition and the rates were approximately proportional to the acidic strengths (Fig.5).The activation energy for the decomposition in n-dodecane containing 3.8 mol% propionic acid at 80-120 was calculated as 18.1kcal per mol.