Polarographic Behaviour of the Hexa-ammine-chromium(III) Ion: Role of Hydrogen Ions

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HEXA-AMMINECHROMIUM(III) ion in acetate buffer solutions is reduced at the dropping mercury electrode, and gives two polarographic waves. The first wave, which is well defined, is considered to be a one-electron reduction of Cr(III) to Cr(II)1. Its half-wave potential at 25° C was found to be -0.970 V versus saturated calomel electrode in 0.1 M acetate buffer solution which contained 0.9 M potassium chloride and 0.005 per cent gelatin (Fig. 1, curve a). The limiting current of this wave was diffusion-controlled and proportional to the concentration of the complex ion up to 5 mM. Both the half-wave potential and the diffusion current remained constant when the pH was varied from 4.5 to 5.45. No change was observed when potassium chloride was replaced by ammonium chloride at the constant ionic strength. The plot of log ī/(īd - ī) versus E, where ī means the average current, īd the average diffusion current, and E, the potential of the dropping mercury electrode, gave a straight line with a reciprocal slope of 64 mV, whereas the examinations with Kalousek's circuit and alternating current polarograph showed that this wave has nearly irreversible character.

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