Abstract
Anodic or cathodic processes in which protons are released or consumed, respectively, lead to local pH changes at the electrode surface. The phenomenon is important in several branches of metal finishing, in corrosion, electro-organic synthesis and other branches of applied electrochemistry, as well as being a factor which can invalidate mechanistic investigations. The concept of ‘pHs’ (near-surface pH) is examined, as are the experimental techniques which have been used to measure it. Many of these are inherently weak. Published results are shown to be largely discrepant, both in respect of the magnitude of the effect and even its incidence. Attempts to treat the phenomenon theoretically are briefly summarized.
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