Spectroscopic method for the kinetics of Ag (I) catalysed oxidation of phenethylalcohol(PA) by PDP in aqueous nitric acid medium has been reported under different conditions. The reaction is followed spectrophotometrically by measuring the decrease in absorbance of PDP at 350nm to 360nm. The rates show first order dependence on [PDP] and the rate constants evaluated at different [PDP] are found to be almost the same. Increase in [Ag (I)] has linear relation with the rate of oxidation and order in [Ag (I)] has been found to be fractional. Variation in ionic strength of the medium has significant effect on the rate of reaction. The rates of the reaction have been measured at different temperatures and the activation parameters for all the substrates computed. The rates increase in the order –NO2 < -Cl < -H < -CH3 < -OCH3 of para substituted phenethyl alcohols. Hammett's plot of log kobs versus σ is found to be valid. The correlation between enthalapies and free energies of activation is reasonably linear with an isokinetic temperature of 425K to 432K.The rate constant k obeys corresponding equation, k=Q.e –ΔE#/RT.eΔs#/R. Ea increases with introduction of electron-withdrawing groups into the benzene ring. Electron withdrawing groups increases chemical reactivity decreases. The introduction of electron-releasing groups lowers the Ea for the reaction. The reactions were sluggish under ordinary conditions. However, in the presence of Ag (I) catalyst these substrates underwent Oxidation at Kinetically measurable speed. Hence, it is thought worthwhile to study Oxidation of and its substituted derivatives in the presence of Ag(I) PDP in aqueous HNO3medium.
