Kinetic Analysis of the Transitory Overshooting of the H+ Concentration in the Cation-exchange Membrane System

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Overshooting with respect to the H+ concentration was studied quantitatively. Systems of two species of cation and one species of anion were studied for example, the 0.2 M-NaCl (initial, s-side) : Collodion-Polystyrene sulfonic acid membrane: 0.02 M-NaCl+0.002 M-HC1 (1-side, constant). The volume of the 1-side solution was greatly larger than that of the s-side solution. The composition of the former was not altered measurably by the transport of ions across the membrane. Because the cation-exchange membrane used was not highly selective, both cation and anion were permeable. The final composition of the s-side solution became equal to the composition of the 1-side solution. In the course of changes toward the final equilibrium, the H+ or HCl concentration temporarily reached far above the final value. An analytical interpretation with two parameters was given, in which the concentration of the most slowly movable ion in the membrane, Cl−, was assumed to decrease monotonously. Moreover, the concentration of next slowly movable ion, Na+, was assumed to change as a result of the force which tends to bring the system toward the imaginary Donnan equilibrium. The Na+concentration at the imaginary Donnan equilibrium toward which the s-side solution is approaching at any given instant was obtained as follows. The (H+ concentration)/(Na+ concentration) ratio at the equilibrium is the same as the corresponding ratio in the 1-side. Moreover, the total concentration of H+ and Na+ at the imaginary Donnan equilibrium is equal to the existing Cl− concentration in the s-side solution.
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Kinetic Analysis of the Transitory Overshooting of the H<SUP>+</SUP> Concentration in the Cation-exchange Membrane System

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