Abstract
The dependence of the anomalous codeposition of iron-nickel alloys on the pH at the cathode surface is investigated. An equation is derived to evaluate the surface pH as a function of bulk pH, rate of hydrogen evolution, buffer concentration, and diffusion conditions. The results obtained on rotating disk electrodes show that anomalous codeposition is due to a suppression of nickel discharge and that suppression occurs only when the surface pH is high enough to cause hydroxide formation. A type of mechanism is proposed by which the adsorption of ferrous hydroxide suppresses the deposition of nickel but permits a high rate of iron discharge. Experimental results which support this mechanism are discussed. This type of mechanism could be of general importance for other systems exhibiting anomalous codeposition. © 1965, The Electrochemical Society, Inc. All rights reserved.