Influence of surface phenomena on the impedance response of a rotating disk electrode

Orazem, Mark E.; Durbha, Madhav; Deslouis, C.; Takenouti, H.; Tribollet, Bernard

doi:10.1016/s0013-4686(99)00156-5

Cited by 21 publications

(20 citation statements)

References 32 publications

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“…Analysis of the raw data obtained for the above conditions revealed variations of the steady potential up to 10% during the acquisition. This may be due to partial blockage of the platinum surface by adsorption of hexacyanoferrate ions or their decomposition products, or to non-uniform distributions of current and potential at the electrode [11].…”

Section: Methodsmentioning

confidence: 99%

“…The global impedance depends on the generalised capacitance Q and parameter n. The two of them were determined by fitting of the experimental impedance, Z, to the model predictions: theoretical impedanceẐ was deduced fromẑ taking into account the geometrical area of the disc electrode. For the same couple (redox system-electrode material) n varies from 0.8 to 1 according to [15] and the generalized capacitance was reported to be near 20 lX À1 s n cm À2 [11]. Fitting was conducted by minimisation of the relative deviations of the real and imaginary components, Z 0 and Z 00 , respectively.…”

Section: Fitting Of Experimental Datamentioning

confidence: 99%

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Impedance of a rotating disc electrode with a reversible reaction

Boillot

Didierjean

Lapicque

2004

Journal of Applied Electrochemistry

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This paper presents a model of electrode impedance for the case of a fast reversible reaction. The various contributions of the impedance were analysed with particular emphasis on the charge transfer resistance: this resistance was shown to be also dependent on mass transfer phenomena. For the case of significant mass transfer control, the diameter of the high-frequency loop increases with the absolute value of the overpotential. The various physicochemical parameters involved in the expression for impedance were determined through previous measurements. The impedance model was validated by experimental measurements carried out with the hexacyanoferrate (II)-(III) couple on a Pt RDE. List of symbolsD diffusion coefficient (m 2 s À1 ) E potential (V) F faradaic constant = 96 487 C mol À1 f F=ðRTÞ(V À1 ) i current density (A m À2 ) i 0 exchange current density (A m À2 ) I current (A) j imaginary number ( j 2 ¼ À1) m average of the relative deviation n constant phase element (CPE) parameter N number of frequencies in spectra Q specific generalised capacitance (X À1 s n cm À2 ) r specific resistance (X m 2 ) R gas constant (8.314 J K À1 mol À1 ) R resistance (X) R e cell resistance (X) s Laplace variable (s À1 ) t time (s) T temperature (K) x distance from the electrode surface (m) [X] concentration of species X (mol m À3 ) z specific impedance (X m À2 ) Z impedance (X) Z 0 real part of the impedance (X) Z 00 imaginary part of the impedance (X)Greek symbols a charge transfer coefficient d thickness of the diffusion layer (m) g electrode overpotential (V) q density of the solution (kg m À3 ) m kinematic viscosity of the solution (m 2 s À1 ) x signal pulsation (rad s À1 ) X angular velocity of the electrode (rad s À1 )

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Section: Methodsmentioning

confidence: 99%

Section: Fitting Of Experimental Datamentioning

confidence: 99%

Impedance of a rotating disc electrode with a reversible reaction

Boillot

Didierjean

Lapicque

2004

Journal of Applied Electrochemistry

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“…The error analysis approach was used to facilitate development of interpretation models for PANI free-standing polyaniline membranes [3] and to establish a model for interpreting impedance data for corrosion of cast iron in drinking water [4]. The error analysis was combined with development of mathematical models [5] to demonstrate the influence of current distribution and poisoning on the impedance response associated with the reduction of ferricyanide on a platinum rotating disk electrode [6]. The error analysis facilitated discrimination among mathematical models for convective diffusion to a disk electrode under a submerged impinging jet for corrosion of steel in brines containing CO 2 [7].…”

Section: Introductionmentioning

confidence: 99%

A systematic approach toward error structure identification for impedance spectroscopy

Orazem

2004

Journal of Electroanalytical Chemistry

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“…The finding that the standard deviations of the real and imaginary parts of the impedance were equal for systems that satisfied the Kramers-Kronig relations was verified both experimentally and analytically. 4,12,13 Nevertheless, Macdonald and Piterbarg suggested that the equality of standard deviation in the stochastic errors in the real and imaginary impedance observed by Orazem et al 4,10,[12][13][14][15][16][17] was ''probably associated with the specifics of the frequency response analyzer used and unlikely to be an intrinsic property of immittance spectroscopy measurements.'' 18 It is important to note that the observations reported by Orazem et al were obtained using frequency response analyzer ͑FRA͒ instrumentation.…”

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confidence: 99%

On the Error Structure of Impedance Measurements

Carson

Orazem

Crisalle

et al. 2003

J. Electrochem. Soc.

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A new paradigm is introduced for the investigation of errors in frequency-domain measurements. The propagation of errors from time-domain measurements to the desired complex variables in the frequency domain was analyzed for the frequency response analysis ͑FRA͒ algorithm, one of two techniques commonly used for spectroscopy measurements. Errors in the frequency domain were found to be normally distributed, even when the errors in the time-domain were not normally distributed and when the measurement technique introduced bias errors. For additive errors in time-domain signals, the errors in the real and imaginary impedance were found to be uncorrelated, and the variances of the real and imaginary parts of the complex impedance were equal. The equality of variances was realized except for cases where the time-domain signals contained proportional errors. The statistical characteristics of the results were in good agreement with experimental observations. Weighted complex nonlinear regression techniques are typically used to extract information from electrochemical impedance data. The error structure of the measurement is used implicitly in regression analysis and has a significant influence on the quality and amount of information that can be extracted from impedance data. The variance of the stochastic error can be incorporated explicitly into the weighting strategy for the regression and can provide a means for determining whether observed features lie outside the noise level of the measurement. The stochastic errors can also influence the use of the Kramers-Kronig relations for determining the internal consistency of the data.For the purposes of the discussion presented here, the errors in an impedance measurement are expressed in terms of the difference between the observed value Z ob () and a model value Z mod () aswhere res represents the residual error, fit () is the systematic error that can be attributed to inadequacies of the model, bias () represents the systematic experimental bias error that cannot be attributed to model inadequacies, and stoch () is the stochastic error with expectation E͕ stoch ()͖ ϭ 0. The experimental bias errors, as referred to here, may be caused by a nonstationary behavior or by instrumental artifacts.Typically, the impedance is a strong function of frequency and can vary over several orders of magnitude through the experimentally accessible frequency range. The stochastic errors of the impedance measurement are strongly heteroskedastic, which means that the variance of the stochastic errors is also a strong function of frequency. 1-4 Selection of an appropriate weighting strategy is, therefore, critical for interpretation of data.A distinction is drawn, in the present work, between stochastic errors that are randomly distributed about a mean value of zero, errors caused by the lack of fit of a model, and experimental bias errors. The problem of interpretation of impedance data is therefore defined as consisting of two parts, one of identification of experimental errors, which ...

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Influence of surface phenomena on the impedance response of a rotating disk electrode

Cited by 21 publications

References 32 publications

Impedance of a rotating disc electrode with a reversible reaction

Impedance of a rotating disc electrode with a reversible reaction

A systematic approach toward error structure identification for impedance spectroscopy

On the Error Structure of Impedance Measurements

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