The kinetics of oxidation of N-acetylphenothiazine (NAPT) by Cr(VI) in 80% acetic acid-20% water (v/v) mixture is first-order each in [NAPT] and [Cr(VI)]. The reaction is catalysed by added acid with a third-order dependence in [HCIO4], Increase in polarity of the solvent medium decreases the rate. The oxidation is insensitive to variations in ionic strength as well as added acrylamide. Oxidations of phenothiazine (PT) and N-methylphenothiazine (NMPT) under similar conditions are found to be very fast. However kinetic investigations with NMPT in an acetic acid-sodium acetate buffer show first-order dependence each in [NMPT] and [Cr(VI)] and a fractional-order dependence in [H+] in the pH range 1.80-3.09. Increase in polarity of the medium increases the rate. In both the cases, the corresponding sulphoxides are identified as oxidation products. Based on the kinetic results, mechanisms for oxidations are proposed.
Volume 132, 2020
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