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Kinetics of the oxidation of L-ascorbic acid by diaquatetraamminecobalt(III) in acidic aqueous solution. Application of the Fuoss model and the Marcus-Sutin cross-relationship for electron-transfer processes

AuthorsMartinez, P.; Zuluaga, J.; Noheda Marín, Pedro ; van Eldik, R.
Issue Date1992
CitationInorganica Chimica Acta 195 : 249-253 (1992)
AbstractThe kinetics of the oxidation of L-ascorbic acid by diaquatetramminecobalt(II1) was studied as a function of pH, L-ascorbic acid concentration, ionic strength and temperature using a stopped-flow technique. The rate of the process was found to be first order with respect to both redox partners, whereas the [H+] concentration showed a retarding influence. The kinetic data are interpreted in terms of rate-determining oxidation of the deprotonated ascorbate anion, for which k=(3.42+0.15) x lo-’ M-’ s-r at 25 “C, AEZf =81+6 kJ mol-’ and AS+ =1+20 J K-r mol-‘. The ion-pair formation theory of Fuoss and the Marcus-Sutin cross-relationship for electron transfer were applied to this redox process to estimate the ion-pair formation constant, the rate constant for electron transfer and the self-exchange rate constant for the Co(NH3)4(H20)~+n+ couple.
Publisher version (URL)https://doi.org/10.1016/S0020-1693(00)85320-7
Appears in Collections:(IQOG) Artículos
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