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The preferential transport of cupric and ferric ions through a cation exchange membrane was studied in chloride solutions with electrodialysis at constant electric field operation. Citric acid was used as a complexing agent in metal ion solution in order to increase the permselectivity of metal ions. The preferential transport behavior depends on the stoichiometric ratio of citric acid to metal ions, the pH value of solution and effective applied voltages, but is slightly affected by the flow rate of solution. Based on the Nernst-Planck equation and interfacial quasi-equilibrium, the theoretical results obtained from numerical calculation are in agreement with the experimental data while the effective applied voltages <1.5 V, and the stoichiometric ratio of citric acid to metal ions <0.7.

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