Oxidation of Alcohols by Cerium(IV). II. Oxidation of Methanol by Ceric Sulfate

The oxidation of methanol by cerie sulfate in sulfuric acid solutions was studied in the temperature range 40∼70°C. The rate of oxidation depended directly on the concentration of cerium(IV) and methanol. At constant ionic strength the rate was directly dependent on the concentration of sulfuric acid. But when the ionic strength is not maintained, the rate changes inversely with sulfuric acid. At constant acid concentration, a negative salt effect is observed. The reaction occurs without the intermediate formation of a complex. The activation energy was derived to be 26300 cal. mol−1. It has been shown that the mechanism of Waters for the oxidation of α-hydroxyacids by manganese pyrophosphate can be used to explain the present data.