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Kinetics and mechanism of oxidation of fumarate, acrylate, cinnamate, and maleate anions by hexavalent manganese in aqueous alkaline medium
Author(s) -
Sreenivasulu P. V.,
Adinarayana M.,
Sethuram B.,
Rao T. Navaneeth
Publication year - 1985
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550170908
Subject(s) - chemistry , disproportionation , kinetics , substrate (aquarium) , acrylate , aqueous solution , reaction rate constant , manganese , inorganic chemistry , reactivity (psychology) , polymer chemistry , organic chemistry , catalysis , physics , oceanography , polymer , monomer , quantum mechanics , geology , medicine , alternative medicine , pathology
Abstract 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 → cinnamate → maleate. The reactions followed Michaelis–Menten kinetics suggesting the formation of a cyclic intermediate between Mn(VI) 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 1/ k obs versus 1/[substrate]. Activation parameters are also presented and discussed. A convenient iodometric method is reported for the estimation of Mn(VI).