Study On Kinetics And Mechanism Of Oxidation Of Amines By Ag(Ⅲ)

In this paper, the kinetics and mechanism of oxidation of Tetrahydrofurfurylamine and n-Butylamine by hydroxydipriodatoargentate(â…¢) were studied respectively by spectrophotometry in alkaline medium.It was testified that Ag(â…¢) existed in the form of [Ag(HIO₆)₂]^5- and [Ag(HIO₆)(OH)(H₂O)]^2- in the alkaline medium, and the latter was activation center.The kinetics of oxidation of tetrahydrofurfurylamine by diperiodatoargenate(â…¢) complex ion was studied spetrophotometrically in alkaline medium in a temperature range of 298.2-313. 2K. The reaction rate showed the first order dependence both in oxidant and tetrahydrofurfurylamine. It was found that the pseudo first order rate constant, k_obsd increases with the increase in[OH^-] and decrease with the increase in [IO₄^-] . A negative ionic strength effect was observed in the reaction.The kinetics of oxidation of n-Butylamine by diperiodatoargenate(â…¢) complex ion was studied spetrophotometrically in alkaline medium in a temperature range of 298. 2-313. 2K. The reaction rate showed the first order dependence both in oxidant and n-Butylamine. It was found that the pseudo first order rate constant, k_obsd, decrease with the increase in [IO₄^-] . A negative ionic strength effect was observed.The supposed mechanism can favorably explain the reaction results. Meanwhile, the determining-step rate constants (k) and activation parameters at 298.2K were obtained. The study on this system would provide valuable theorical foundation for the route design of organic synthesis.