Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium

✍ Scribed by P. V. Sreenivasulu; M. Adinarayana; B. Sethuram; T. Navaneeth Rao

• Publisher: John Wiley and Sons
• Year: 1985
• Tongue: English
• Weight: 291 KB
• Volume: 17
• Category: Article
• ISSN: 0538-8066
• DOI: 10.1002/kin.550170908

✦ Synopsis

Kinetics of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese has been studied in aqueous alkaline medium. The order in [oxidant] was unity while that in [substrate] was fractional. The order of reactivity of anions is fumarate -+ acrylate --f cinnamate + maleate. The reactions followed Michaelis-Menten kinetics suggesting the formation of a cyclic intermediate between Mn(V1) and the substrate followed by its disproportionation in a slow step. The equilibrium constant ( K ) for the preequilibrium step and the rate constant (k) for the slow disproportionation step have been calculated from the intercept and the slope values of the linear plot of l/kOb, versus l/[substrate]. Activation parameters are also presented and discussed. A convenient iodometric method is reported for the estimation of Mn(V1).