1973 Volume 46 Issue 9 Pages 2780-2784
The rate of oxidation of cyclohexanone catalyzed by manganese salt increases remarkably in the presence of acetic acid, and is about one hundred times as high as the limiting rate of oxidation kp2(RH)2/2kt. However, manganese concentration does not affect the rate of oxidation much in a wide range. The oxidation of cyclohexanone by manganic ion should be the rate determining step, since the rate of oxidation, which is of first order in cyclohexanone but independent of manganous ion, corresponds to the rate of oxygen absorption of cyclohexanone with the same manganese concentration. The oxidation of cyclohexanone by manganic ion seems to proceed through enol intermediates, since the rate of oxidation increases in the presence of alkali acetates. The rate equation including enolization step and the subsequent oxidation of enol intermediate with manganic ion agrees with the experimental results. A remarkable synergistic effect of metal salts was observed in a mixture of manganese and cobalt. The oxidation products were also analyzed and discussed.
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