The transport of uncharged electroactive probes, 1,1‘-ferrocenedimethanol and 4-hydroxy-TEMPO, and electroactive cations, Tl+, was studied in polyacrylate hydrogels using steady-state voltammetry at platinum and mercury film microelectrodes. It was found that, for concentrations of polymer less than 1.5%, the diffusion coefficient of uncharged probes does not differ significantly from that observed in aqueous solutions without a polymeric network. For the probe cation, strong electrostatic interactions were observed between Tl+ and anionic polymeric networks; those interactions resulted in a significant decrease in the diffusivity of Tl+ cations. Experimental data for Tl+ transport in sodium polyacrylate gels were compared with predictions of Manning's theory for polyelectrolyte solutions. Electrostatic interactions between Tl+ and anionic polyacrylate three-dimensional gel network were found stronger than those predicted for solutions of an equivalent polyelectrolyte. Electrostatic effects for gels were found even stronger when Tl+ cations served as counterions in thallium polyacrylate gels; the transport of Tl+ counterion was more suppressed in those gels than for a Tl+ probe in sodium polyacrylate, especially for small values of charge separation distance in polymeric units. The mobility of a counterion forming a gel, Na+, was also studied using conductance measurements, and appropriate expressions for conductivity as a function of poly(acrylic acid) neutralization degree were developed based on Manning's line charge model. Experimental conductivity data for Na+ agreed with predictions of the model.

A new method for the determination of the diffusion coefficients of both the substrate, DS, and the product, DP, of an electrode process has been developed. The method proposed is based on the analysis of the transient currents and can be applied to some reactions of the type SzS = PzP + ne and, in contrast to the concept based on the steady-state current, to any ratio of the concentrations of supporting electrolyte and substrate. The diffusion coefficients can be evaluated sequentially from the two parts of the double-potential step chronoamperogram, since the magnitude of the normalized chronoamperometric current of the first step depends on the DS value, while that of the second step is controlled by both DS and DP values. The corresponding, easy-to-use equations and procedures are given in the paper. The equations were derived on the basis of the numerical simulation data. The proposed methods of determination of diffusion coefficients for the substrates and products have been examined experimentally with the charged and uncharged ferrocene derivatives under diffusional and mixed diffusion-migration conditions. Only the chronoamperometric DS values obtained for the substrates could be compared to those determined from the steady-state diffusional current. It was found that for the systems investigated the agreement between these two methods was good. In this limited comparison, the standard deviations for the transient techniques were slightly larger than those obtained for the excess supporting electrolyte steady-state voltammetry.

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Very-thin layers of ionic liquids are formed at microelectrode surfaces during electrolysis of undiluted redox liquids containing only supporting electrolyte at a low concentration. The layers consist of ionic product and counterion coming from supporting electrolyte. Formation of ionic−liquid layer leads to increased viscosity, changes in activity coefficients, and thus to changes in diffusion coefficients of all species involved in the electrode process. This engenders also a specific type of convection. Exchange of one supporting electrolyte for another may change dramatically the physicochemical properties of the generated ionic layer and, in consequence, the magnitude of the electrochemical response of an undiluted substance. A computational model for predicting the phenomena mentioned above is presented. An important step in the model is extension of the concentration dependence of diffusivities to concentrations corresponding to ionic liquids. The calculations done have shown a substantial influence of counterion volume on the electrochemical behavior of undiluted redox liquids even if the counterions are present at a very-low concentration. The consequences of changing supporting electrolyte concentration are also included in the model. The theoretical predictions were compared with experimental data obtained for undiluted nitrobenzene and methanol. The model can be used for both transient and steady-state responses.