Impedance spectroscopy of an electrolytic cell limited by ohmic electrodes

Barbero, Giovanni; Batalioto, F.; Neto, A. M. Figueiredo

doi:10.1063/1.2709531

Cited by 46 publications

(53 citation statements)

References 22 publications

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“…More recently, simple versions of the equations of Macdonald, relevant to the case in which the impurities dissolved in the liquid are completely dissociated, have been discussed for several cases. [6][7][8][9][10][11][12][13][14] Our goal now is to generalize the analysis of Macdonald to the case in which the dielectric liquid contains two groups of ions. Very detailed treatments of two carrier systems exist in the liquid and solid electrochemistry.…”

Section: Theory Of Small-signal Ac Response Of a Dielectric Liquid Comentioning

confidence: 99%

Theory of small-signal ac response of a dielectric liquid containing two groups of ions

Barbero

Batalioto

Neto

2008

Applied Physics Letters

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The analysis of Macdonald for electrolytes is generalized to the case in which two groups of ions are present. We assume that the electrolyte can be considered as a dispersion of ions in a dielectric liquid, and that the ionic recombination can be neglected. We present the differential equations governing the ionic redistribution when the liquid is subjected to an external electric field, describing the simultaneous diffusion of the two groups of ions in the presence of their own space charge fields. We investigate the influence of the ions on the impedance spectroscopy of an electrolytic cell. In the analysis, we assume that each group of ions have equal mobility, the electrodes perfectly block and that the adsorption phenomena can be neglected. In this framework, it is shown that the real part of the electrical impedance of the cell has a frequency dependence presenting two plateaux, related to a type of ambipolar and free diffusion coefficients. The importance of the considered problem on the ionic characterization performed by means of the impedance spectroscopy technique was discussed.

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Section: Theory Of Small-signal Ac Response Of a Dielectric Liquid Comentioning

confidence: 99%

Theory of small-signal ac response of a dielectric liquid containing two groups of ions

Barbero

Batalioto

Neto

2008

Applied Physics Letters

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“…This is the path used manly for determining the impedance system presented in recent literature [9,[13][14][15][16][17][18]20]. It has the disadvantage that it is necessary to know all the values A, B, and C which are present in the expression (45) of the electric field E 1 ( ).…”

Section: Solving Of the System In The Own Methodsmentioning

confidence: 99%

Electrode polarization and interface effects in liquid crystal systems with mobile ions: development of a model of bipolar diffusion

Ganea

2013

Open Physics

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Abstract:The influence of mobile ions on the results of impedance spectroscopy (dielectric spectroscopy) measurements performed on a liquid crystal cell using the new mathematical model recently described was investigated. This mathematical model reformulates the fundamental equation system of continuity for mobile charge carriers and the Poisson equation using new variables. One makes the following assumptions: ions have different mobilities and diffusion coefficients, there is no generation-recombination process, the equilibrium carrier concentrations are uniform and equal each other, the electrodes are either completely blocking or blocked with adsorption-desorption processes. The final result is the analytical expression of the equivalent admittance for the system, allowing to have a clearer picture of the mobile ions and of the processes that occur at the electrode interface influencing the dielectric behavior.

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“…In particular, the parametric plot of the imaginary part versus the real one is a semicircle, whose center is on the real axis, passing for the origin of the cartesian reference frame. Several generalizations of the original model have been proposed to take into account the difference between the ions [1], the electrodes properties [4,5] and the generation/ recombination of ions [6][7][8], fractional diffusion or boundary conditions taking into account memory effects [9][10][11][12][13][14].…”

Section: Introductionmentioning

confidence: 99%

Warburg's impedance revisited

Barbero

2016

Phys. Chem. Chem. Phys.

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The derivation of Warburg's impedance presented in several books and scientific papers is reconsidered. It has been obtained by assuming that the total electric current across the sample is just due to the diffusion, and that the external potential applied to the electrode is responsible for an increase of the bulk density of charge described by Nernst's model. We show that these assumptions are not correct, and hence the proposed derivations questionable. A correct determination of the electrochemical impedance of a cell of an insulating material where are injected external charges of a given sign, when the diffusion and the displacement currents are taken into account, does not predict, in the high frequency region, for the real and imaginary parts of the impedance, the trends predicted by Warburg's impedance in the Nernstian approximation. The presented model can be generalized to the case of asymmetric cell, assuming boundary conditions physically sound.

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Impedance spectroscopy of an electrolytic cell limited by ohmic electrodes

Cited by 46 publications

References 22 publications

Theory of small-signal ac response of a dielectric liquid containing two groups of ions

Theory of small-signal ac response of a dielectric liquid containing two groups of ions

Electrode polarization and interface effects in liquid crystal systems with mobile ions: development of a model of bipolar diffusion

Warburg's impedance revisited

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