Kinetics and mechanistic approach to the chromic acid oxidation of l-tryptophan with a spectral detection of chromium(III) product

Abstract

The kinetics of chromic acid oxidation of l-tryptophan in H2SO4 medium at a constant ionic strength of 0.6moldm−3and at 25°C have been investigated spectrophotometrically. The reaction exhibits a 3:2 stoichiometry (tryptophan:chromic acid). The reaction shows a first order dependence on [chromic acid], a fractional-first order dependence on [tryptophan] and fractional-second order dependence on [acid]. Increasing ionic strength and dielectric constant had no significant effect on the oxidation rate. The final oxidation products of tryptophan were identified as the corresponding aldehyde (indole-3-acetaldehyde), ammonium ion and carbon dioxide. A spectral evidence for the formation of chromium(III) product was obtained. The experimental results suggest formation of an intermediate complex between the protonated tryptophan and chromic acid which decomposes in the rate-determining step to yield the products. The mechanism of such reaction has been proposed. The thermodynamic parameters with respect to the first step of the suggested mechanism were evaluated and discussed.