Ionic Mass Transfer and Concentration Polarization at Rotating Electrodes

I .. Rates of ionic mass transfer at nickel electrodes rotating about their axes In the center of stationary electrodes were studied using the ferri-ferrocyanide oouple In alkaline solutions. A general mass transfer correlation was found to apply equally well to the dissolution rates of rotating solids and to the rates of ionlo mass transfer at rotating electrodes. This correlation takes into account the physioal properties of the system as well as geometric and hydro dynamic factors. The correlation enables the prediction of limiting currents and concentration polarisation at rotating electrodes under a wide range of conditions. The nature of the polarisation involved in the reduotion of Fe(CNfe~» and the oxidation of Fe(CN#* was also Investigated. The polarisation was found to depend strongly on the presence of "electrode poisons." With freshly prepared solutions, under exclusion of light and with eathodlcally treated nickel electrodes relatively small ehesdcal polarisations were determined. For rotational speeds not exceeding Reynolds number 11,000, the chemical polarisation was found to be negligicle in comparison with the concentration polarisation* Under such conditions the ferro-ferrioyanide oouple can be conveniently used to obtain mass transfer rates for various hydrodynamic conditions, or, conversely, to verify the validity of mass transfer equations by a comparison of experimental .and calculated values of limiting currents and concentration polarisation. The rotating electrode model was found to be most suitable for studying the nature of eleotrolytio polarisation phenomena on aocount of the uniformity of the current distribution as well as of the hydrodynamio diffusion laver at the electrode surfsee.