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This work discusses the applicability of polyaniline-modified cation exchange membranes for the separation of monovalent/divalent cations by electrodialysis. A novel method of membrane modification directly in the electrodialysis unit is used to prepare permselective membranes. Complex characterization of the membranes before and after modification allows revealing the influence of membrane matrix on the modification efficiency. The characterization of the membranes includes determination of the diffusion permeability, specific conductivity and current–voltage curves in HCl, NaCl and CaCl2 solutions, as well as transport-structural parameters of the extended three-wire model. The characterization results are used to predict the influence of the modification on membrane permselectivity. The competitive mass transfer of singly and doubly charged cations in the electrodialysis process is investigated in underlimiting and overlimiting currents. Electrodialysis desalination of a solution containing Na+/Ca2+ or H+/Ca2+ cations shows that the modification leads to an increase in membrane permselectivity to single-charged cations due to the repulsion of Ca2+ ions from the positively charged membrane surface. The permselectivity of the polyaniline-modified perfluorinated membrane to H+ in the mixture of H+/Ca2+ cations is observed in all current regimes.

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The conductivity, diffusion, and electroosmotic permeability of composites, obtained in different conditions of polyaniline synthesis on the surface or in volume of perfluorinated MF-4SK membrane, were studied. The oxidative polymerization of aniline was carried out in static conditions in mixture of monomer and oxidant solutions, in concentration field by method of successive diffusion of polymerization solutions through the membrane in water, and in an external electrical field. The concentration of polymerization solutions, the type of electron acceptors, duration of synthesis, and current density were varied to obtain a set of composites. The certain advantages of every method of polyaniline chemical template synthesis were revealed to prepare the materials with required set of the electrotransport characteristics.