Potentiometric determination of the standard potential of the As(V)/As(III) couple.
The potential of the As(V)/As(III) half-cell was measured at 25 degrees with a glass electrode as reference electrode in order to eliminate the liquid-junction potential. Rapid and reproducible values could be obtained only in the presence of iodide, which increases the rate of electron-exchange between the two oxidation states of arsenic, but only at hydrogen-ion concentrations higher than about 0.5M. Extrapolation to zero ionic strength was therefore required to obtain the standard potential. A value of 573 +/- 2 mV was calculated for the half-reaction AsO(OH)(3) + 2e(-) + 2H(+) right harpoon over left harpoon As(OH)(3) + H(2)O.
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Dipartimento di Chimica Generale dell'Universita' di Pavia, V. Taramelli 12, 27100 Pavia, Italy.