Kinetics and mechanism of oxidation of aliphatic alcohols by N-chloronicotinamide in aqueous acetic acid medium

Kinetics of oxidation of five aliphatic alcohols viz. n-butanol, n-propanol, n-pentanol, propan-2-ol and butan-2-ol by newly developed oxidant N-chloronicotinamide (NCN) in aqueous acetic acid medium in presence of HClO4 and NaCl have been investigated. The observed rate of oxidation is first-order with respect to oxidant (NCN) and fractional-order with respect to alcohol. A decrease in the dielectric constant of the medium increases the rate. Addition of nicotinamide (NA), has a retarding effect on the rate of oxidation. The corresponding aldehydes and ketones are the major products of oxidation of primary and secondary alcohols respectively. From the effect of temperature on the reaction rate, the Arrhenius and the activation parameters have been calculated. A suitable mechanism has been proposed and a rate law explaining the experimental results is derived.