A Kinetic and Mechanistic Study on the Oxidation of Hydroxy Acids by N-Bromophthalimide in the Presence of a Micellar System

摘要

The kinetics of oxidation of some α-hydroxy acids viz. Tartaric acid (TA) and Malic acid (MA) by N-bromophthalimide (NBP) were studied in the presence of a cationic surfactant, cetyltrimethylammonium bromide (CTAB), in perchloric acid medium at 313 K. The oxidation of TA and MA by N-bromophthalimide in the presence of CTAB is faster than in the absence of surfactant. The rate of oxidation of hydroxy acids was found to be in the order: TA > MA. First order kinetics with respect to NBP was observed in the oxidation of both hydroxy acids. The kinetics results indicate that the first order kinetics in hydroxy acids at lower concentrations tends towards a zero order at its higher concentrations. Inverse fractional order in [H+] and [phthalimide] were noted throughout its tenfold variation. With a progressive increase in [CTAB], the rate of reaction increased, reaches a maximum value and then constancy in k Ψ was observed. Variation of [Hg(OAc)2] and ionic strength (μ) of the medium did not bring about any significant change in the rate of reaction. The applicability of different kinetic models viz. the Piszkiewicz cooperative model, the Raghvan and Srinivasan model, and the Menger–Portnoy model were tested to explain the observed micellar effects. The effect of [CTAB] on the activation parameters was explored to rationalize the micellar effect. The values of rate constants observed at four different temperatures were utilized to calculate the activation parameters. A suitable mechanism consistent with the experimental findings has been proposed. The index of cooperativity and the micelle binding constant have been calculated.