Abstract
The factors resulting in the superselectivity of Nafion perfluorosulfonic membranes in contact with NaCl solutions are investigated by means of a set of experimental measurements: zero-current membrane potential, determination of the amount of sorbed electrolyte, co-ion and counter-ion self-diffusion fluxes, co-ion fluxes under a constant current and membrane electrical conductance. The influence of swelling is pointed out by comparing the results obtained with two samples of the same membrane, one in the expanded form after boiling and the other remaining untreated. The amount of sorbed electrolyte is higher in expanded membranes, but as the swelling increases by the same ratio, the molality of the sorbed electrolyte remains unchanged. The loss of superselectivity associated with greater swelling is due to a decrease in the ratio of the mobility of counter-ion over co-ion.
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