RATE AND MECHANISM OF OXIDATION OF BENZYL ALCOHOL WITH OXYGEN IN AQUEOUS-SOLUTIONS OF PERCHLORIC-ACID IN THE PRESENCE OF SODIUM-NITRITE

It is shown that the rate laws for the oxidation of benzyl alcohol change markedly, depending on the concentration of HClO4 and the partial pressure of oxygen in the system. On the basis of the rate laws, a mechanism is proposed for the oxidation of benzyl alcohol to benzaldehyde. It is established that the electron transfer in this process is effected by the catalytic, NO+/NO system. Depending on conditions, the limiting step can be the liquid-phase reaction of a benzyl alcohol molecule with the nitrosonium ion or the gas-phase reaction of nitrogen(II) oxide with oxygen. Equations are obtained describing the rate laws of the reaction.