Abstract
The kinetics of oxidation of d-fructose by permanganate was studied in cationic micelles of cetyltrimethyl ammonium bromide (CTAB), spectrophotometrically. An increase of [CTAB] led to an increase in the absorbance of the reaction mixture. The results indicate a very strong partitioning of the permanganate in favor of the micellar pseudo-phase. From the observed spectrophotometric data, CTAB–permanganate ion-pair formation constant ( K s) was calculated to be 2924 dm 3 mol −1. The reaction is catalyzed by the CTAB micelles. The rate constant versus [CTAB] plot has a maximum at [CTAB] ≥ 40.0 × 10 −4 mol dm −3. For [CTAB] well above the critical micelle concentration, the k obs–[CTAB] profile can be interpreted in terms of distribution of permanganate and d-fructose between water and the micelles. H 2SO 4 has inhibitory effect on the micellar catalysis. The redox reaction proceeds through the formation of water soluble colloidal MnO 2 as an intermediate in less acidic medium. The effects of externally added manganese(II) and fluoride ion are complex. On the basis of the experimental findings, a suitable mechanism consistent with the observed kinetics has been proposed.
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