Electrode impedance without a priori separation of double-layer charging and faradaic process

Holub, Karel; Tessari, G.; Delahay, Paul

doi:10.1021/j100867a034

Cited by 77 publications

(25 citation statements)

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“…Inspection of [5] shows that as a -~ 0 (i.e., as %he potential dependence of adsorption becomes negligible), then [5] can be written RT ZF(S) = nFio 1…”

Section: Negligible Adsorption Potential Dependencementioning

confidence: 99%

“…In addition, as a --> 0, qr0 -> 0 as thermodynamics requires (13) for the conditions under which [3] is valid, and [6] reduces to Zc(s) = 1/qEs [8] Comparison of [5] and [6] with [7] and [8] shows that in the latter cases Ze depends only on charge transferred across the interface (i.e., represents solely a faradaic process), while Zc does not require faradaic current. In contrast, the former cases show how the faradaic and charging processes are intercoupled.…”

Section: Negligible Adsorption Potential Dependencementioning

confidence: 99%

“…Equation [1] can be misleading, as has recently been pointed out (4)(5)(6)(7)(8)(9)(10)(11), since both partial currents may contain double-layer and faradaic parameters if strong reactant adsorption is present. However, their expression in terms of s to develop impedance clearly shows how coupling may or may not exist and allows some interesting and usable limiting cases to be determined, which heretofore do not appear to have been described.…”

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confidence: 99%

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Laplace Plane Analysis of the Impedance of Faradaic and Nonfaradaic Electrode Processes

Pilla¹

1971

J. Electrochem. Soc.

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A unified theory of the impedance of electrode processes is presented. It is shown that the expression of impedance in terms of the Laplace variable, s, permits all cases of interest to be treated. The basic equations developed allow a finite rate for both charge transfer and adsorption, as well as mass transport, in a system of uniform potential distribution. The question of coupling of faradic and charging currents is treated in detail.The use of impedance as a characteristic function of electrochemical systems has long been recognized (1, 2). It was recently pointed out (3) that its expression in terms of the Laplace transform variable, s, enables impedance to be considered as a real (s ~ a) or complex (s ~ j~) function allowing both less ambiguity in mechanism detection and an increased frequency range to be achieved.The necessary quantities can be obtained by starting with the following general relationwhere it(s) is the faradaic current (i.e., that which involves the passage of charge across the interface) and ic(s) is the interfacial charging current (i.e., that which does not require the passage of charge across the interface). Equation [1] can be misleading, as has recently been pointed out (4-11), since both partial currents may contain double-layer and faradaic parameters if strong reactant adsorption is present. However, their expression in terms of s to develop impedance clearly shows how coupling may or may not exist and allows some interesting and usable limiting cases to be determined, which heretofore do not appear to have been described. General TheoryTo illustrate ~his approach, it will be assumed that only the oxidized species need be taken into account (e.g., metal-metal ion electrode). Extension to any number of electroactive species is a trivial matter.The quantities if(s) and ic(S) in [1] must first be written in explicit form. For the former, the most general approach would be to express it in terms of the appropriate independent variables. Since the treatment below will assume finite kinetics for both charge transfer and adsorption, it is rigorous to pick both Co and r0 as well as E for these variables. However, since the (linearized) rate expression given below for r0 allows its dependence on Co (as well as E) to be established, it is sufficient to use only Co and E to describe if(s). (Note that this does not require Co and r0 to be in equilibrium.) It is to be remembered, nevertheless, that the variation of Co at the interface can in fact be obtained only if both charge transfer and adsorption (finite or otherwise) are taken into account. For the purposes of this study, the standard tinearized rate expression is employed realizing, however, that the most general form for it(s) does in fact consist in its expansion involving the well-known partial derivative coefficients. Note that, in the latter case, the parameters are lumped in such a way that the frequency variation of Co is no longer separable from either the dependence of if on E (i.e., charge transfer) or on Co. In order to expre...

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“…Inspection of [5] shows that as a -~ 0 (i.e., as %he potential dependence of adsorption becomes negligible), then [5] can be written RT ZF(S) = nFio 1…”

Section: Negligible Adsorption Potential Dependencementioning

confidence: 99%

Section: Negligible Adsorption Potential Dependencementioning

confidence: 99%

mentioning

confidence: 99%

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Laplace Plane Analysis of the Impedance of Faradaic and Nonfaradaic Electrode Processes

Pilla¹

1971

J. Electrochem. Soc.

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“…The classical theories have been developed for understanding electrode kinetics [42,47,46,40,41,48,38,[43][44][45]39,37], coupling of ion transport in the electrolyte phase either to the Faradaic charge transfer reaction or double layer capacitive charging. Delahay Vector (x, y, z) r…”

Section: Introductionmentioning

confidence: 99%

Generalization of Randles-Ershler admittance for an arbitrary topography electrode: application to random finite fractal roughness

Kant

Singh

2015

Electrochimica Acta

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“…Impedance expressions for the non-reversible case have also been derived [18,19]. They are very complex and it is hard to describe the implications generally.…”

Section: ) Implications For Various Techniques (I) Ac Techniquesmentioning

confidence: 99%

Some basic views on the influence of reactant adsorption on wave shapes in d.c., a.c. and linear sweep voltammetry

Sluyters‐Rehbach

Sluyters

1975

Journal of Electroanalytical Chemistry

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A comprehensive discussion is presented of the basic views and quantitative expressions which are needed to understand the influence of adsorption of electroactive species on the shapes of the waves in d.c. polarography, a.c. polarography and linear sweep voltammetry. It is shown that it is either the non-stationary nature of the techniques or the nonstationary nature of the electrode surface area (or both) which shows up the influence of adsorption.

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Electrode impedance without a priori separation of double-layer charging and faradaic process

Cited by 77 publications

References 0 publications

Laplace Plane Analysis of the Impedance of Faradaic and Nonfaradaic Electrode Processes

Laplace Plane Analysis of the Impedance of Faradaic and Nonfaradaic Electrode Processes

Generalization of Randles-Ershler admittance for an arbitrary topography electrode: application to random finite fractal roughness

Some basic views on the influence of reactant adsorption on wave shapes in d.c., a.c. and linear sweep voltammetry

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