Current passage across the electrode/membrane/solution system. Part 2: steady-state diffusion-migration current. Ternary electrolyte

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A recently proposed express method for experimental determination of diffusion coefficients of electroactive ions inside membrane and their distribution coefficients at the membrane/solution interface (Russ. J. Electrochem., 2022, 58, 1103) is based on interpretation of the measured non-stationary current across the system: electrode/membrane/electrolyte solution after a potential step with the use of theoretical expressions for the time dependence of the current, including the steady-state regime. In previous publications, the application of this method to study the bromide anion transport across membrane is carried out under conditions of the selective permeability (permselectivity) of the membrane for non-electroactive counter-ions where the electric field intensity inside it is suppressed by their high concentration so that the movement of electroactive co-ions (bromide anions), having a much lower concentration inside the membrane, takes place via the pure diffusion mechanism, for which solutions are available in an analytical form. If the concentrations of electroactive co-ions and background counter-ions inside the membrane are comparable between one another their transport occurs under the influence of both diffusion and migration contributions to their fluxes. In particular, such a situation takes place in a ternary system of monovalent ions where both ions of the background electrolyte M+ and A–, as well as the electroactive anion X, penetrate into the membrane from the external solution, their concentrations inside the membrane being comparable to each other. The paper has derived analytical expressions for the steady-state distributions of the concentrations of all ionic components and of the electric field inside the membrane as a function of the amplitude of the passing direct current and of the ion concentrations in the bulk solution, as well as for the intensity of the limiting diffusion-migration current. In particular, it has been shown that at a low concentration of co-ions at the membrane/electrolyte solution interface (compared to the concentration of fixed charged groups of the membrane (Xm << Cf), the migration contribution to the flux of electroactive ions can be neglected so that the formulas derived in this work for the ternary electrolyte are reduced approximately to the corresponding expressions for the pure diffusional transport. If the opposite condition is fulfilled (Xm / Cf>>1), migration contributions to ion fluxes lead to a modification of the expression for the limiting diffusion-migration current.

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M. Vorotyntsev

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

编辑信件的主要联系方式.
Email: mivo2010@yandex.com
俄罗斯联邦, Moscow

P. Zader

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: mivo2010@yandex.com
俄罗斯联邦, Moscow

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