抄録
The effect of migration on the limiting current was analyzed by use of the numerical method. The analysis was conducted for two cases, the transient current at a cylindrical electrode and the steady current at a rotating disk electrode. The result of the present analysis for the rotating disk electrode was compared with the approximate analysis of Gordon et al., where the former showed a greater migration effect than the latter. The diffusivities of ferricyanide and ferrocyanide ions in dilute solution with KOH supporting electrolyte were measured by both the unsteady-state and the steady-state methods at 30°C. The concentrations of Fe(CN)63- and Fe(CN)64- were 0.02 to 0.2 kmol/m3, and that of KOH was constant at 1.0 kmol/m3. The diffusivities obtained from both methods coincided well with each other, and also with the available results by many other investigators for equimolar ferricyanide and ferrocyanide ion solutions.
