| Abstract: | We have studied the oxidation of benzyl alcohols by nitrous and nitric acid in sulfuric acid media. The oxidation by nitrous acid is rapid and has an activation energy of 10.6 ± 0.8 kcal mol?1. A Hammett plot of logk2 vs. σ+ is linear with a ρ value of ?1.4. The oxidation by nitric acid in sulfuric acid media is autocatalytic. From the kinetic and product analyses, it is concluded that a common oxidant, the nitrosonium ion is involved when either nitrous or nitric acid is used. A mechanism is proposed which involves the abstraction of hydride from the alcohols as the rate determining step. It is demonstrated that the autoxidation of the alcohols is catalyzed by nitrous acid or nitric oxide. |
