P P Jegatheesan
Articles written in Journal of Chemical Sciences
Volume 104 Issue 1 February 1992 pp 67-76 Physical and Theoretical
Kinetics and mechanism of oxidation of N-substituted phenothiazines by chromium(VI)
K Pitchumani V Subramanian P P Jegatheesan C Srinivasan
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 135, 2023
All articles
Continuous Article Publishing mode
Click here for Editorial Note on CAP Mode
© 2023-2024 Indian Academy of Sciences, Bengaluru.