Fundamental Studies on the Current-Voltage. Curve in Polarography. III. The Equation for the Current-Voltage Curve of the Complex Ion—Especially for the Irreversible Wave
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概要
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The fundamental equations for the current-voltage curve of the complex ion, especially for the irreversible type, have been derived under the assumption that the over-all oxidation-reduction proccess at the electrode surface follows the mechanism represented by (1)∼(4). Moreover, the two cases, of which one is based on the assumption that the decomposition-rate is much larger than the rate of the diffusion, and the other corresponds to the case when the relation between the two rates is reverse, have been discussed and it has been pointed that the limiting current of the former is the same as the diffusion current, bat the limiting current of the latter corresponds to the kinetic current. It has been concluded that, if the electrode process is activation-controlled, the wave which has many properties of the irreversible one appears. The meaning of the half-wave potential of such a wave has been analyzed, and from the results it has been found that the value of the half-wave potential would be the parameter for the degree of difficulty of the oxidation-reduction process of the complex ion, even if the corresponding wave is irreversible. It should be noted here, that all the discussion cited above rests on the fact that the complex-forming substance exists in a sufficient quantity.<BR>It is likely that the treatment for the oxidation-reduction reaction of the complex ion is essentially the same as for the discussion about the organic compounds.
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