The oxidation of carbohydrazide by the 12-tungstocobaltate(III) ion in acidic medium: Kinetics and mechanism

  • Mehrotra M
  • Mehrotra R
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Abstract

The redox reaction between the 12-tungstocobaltate(III) ion and carbohydrazide is first order with respect to both the oxidant and the substrate. The observed pseudo first-order rate constant, kobs, is retarded by increasing the concentrations of H+and alkali metal ion (Li+, Na+and K+). There is a linear correlation between the kobsand the concentrations of carbohydrazide and H+ion, but the plots of kobsagainst the concentrations of the alkali metal ions is non-linear. However, the same data is applicable to the Davies equation for the effect of the ionic strength on the kobs. Complex formation between the 12-tungstocobaltate(III) ion and carbohydrazide is indicated by optical density measurements, which increased with increasing H+concentration in the reaction mixture. This indicated that+H3NNHCONHNH2probably formed a complex with the 12-tungstocobaltate(III) ion. A suitable mechanism involving deprotonation of the complex and subsequent decomposition of the deprotonated complex as the rate limiting step is suggested. © 2008 Elsevier Ltd. All rights reserved.

Author-supplied keywords

  • 12-Tunstocobaltate(III) ion
  • Carbohydrazide
  • Kinetics
  • Mechanism
  • Oxidation of carbohydrazide
  • Redox reactions

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