The membrane permselectivities of several bilayer perfluorinated ionomer chlor‐alkali membranes have been measured using a sodium ion radiotracer method with an automated laboratory electrolysis cell. The influence of solution concentrations, electrode‐membrane gap, and solution mixing were evaluated for membranes which differed with regard to fabric reinforcement and surface smoothness. Results indicate that these cell and membrane‐related factors all influence membrane permselectivity in an operating cell, with certain practical consequences. The underlying reasons for this complex behavior are discussed.
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