A MICROELECTRODE STUDY OF THE MECHANISM OF THE REACTIONS OF SILVER(II) WITH MANGANESE(II) AND CHROMIUM(III) IN SULFURIC-ACID

The variation of the steady state limiting current for the Ag(I)/Ag(II) oxidation wave with the radius of the microdisc electrode, concentration and temperature has been used to probe the kinetics and mechanisms for the reactions of silver(II) with manganese(II) and chromium(III) in 10 mol dm-3 sulphuric acid. It is shown that the current density for the silver(I) mediated oxidation of manganese(II) is controlled by the diffusion of manganese(II) to the surface except for microelectrodes with radii below 5 μm. On the other hand, the current density for the mediated oxidation of chromium(III) is determined by the rate of the Ag(II)/Cr(III) reaction over a range of conditions. In contrast to the Ag(II)/water reaction, its kinetics can be fitted to a mechanism where the initial electron transfer from Cr(III) to the Ag(II) is the rate determining step. © 1990.