A novel coupling of electrochemical impedance spectroscopy with atomic emission spectroelectrochemistry: Application to the open circuit dissolution of zinc

Shkirskiy, Viacheslav; Ogle, K.

doi:10.1016/j.electacta.2015.03.171

Cited by 17 publications

(30 citation statements)

References 29 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This can be due to two factors: the 25 Hz frequency may be above the threshold frequency of the system, and therefore, no nonlinear effects would be generated at this frequency even for very large perturbation amplitudes; or the noise at this frequency may be so high that it would completely mask the nonlinear effects for all the perturbation amplitudes. The ℘ curve for = 25 was fitted to the linear behaviour zone model given by equation (21), and the obtained fit is represented in figure 10. The obtained fitted model corresponds with the linear model for = 25 .…”

Section: Transitionsmentioning

confidence: 99%

“…This feature makes the technique suitable for a large range of applications. This explains why it has been widely used in electrochemical related fields as fuel cells [6][7][8][9][10][11][12], batteries [13][14][15][16][17][18], corrosion [19][20][21][22][23], coatings [24][25][26], electrochemical sensors [27][28] and supercapacitors [29][30][31][32]. This electrochemical technique has also been used in fields that are not traditionally related to electrochemistry as biochemical assays [33][34][35][36], oncology [37][38][39] and immunology [40][41], amongst others.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Harmonic analysis based method for linearity assessment and noise quantification in electrochemical impedance spectroscopy measurements: Theoretical formulation and experimental validation for Tafelian systems

Giner-Sanz

Ortega

Pérez-Herranz

2016

Electrochimica Acta

View full text Add to dashboard Cite

ElsevierGiner-Sanz, JJ.; Ortega Navarro, EM.; Pérez-Herranz, V. (2016). Harmonic analysis based method for linearity assessment and noise quantification in electrochemical impedance spectroscopy measurements: Theoretical formulation and experimental validation for Tafelian systems. Abstract:Electrochemical Impedance Spectroscopy (EIS) is an electrochemical measurement technique that has been applied to a broad range of applications. Three conditions must be fulfilled in order to obtain valid EIS measurements: causality, linearity and stationarity. The non fulfilment of any of these conditions may lead to distorted and biased EIS spectra. Consequently, the verification of the four fundamental conditions is mandatory before accepting any results extracted from an EIS spectrum. In this work, a harmonic analysis based method for linearity assessment and noise quantification in EIS measurements is presented, and validated both from an experimental point of view and from a theoretical point of view, for Tafelian systems. It was shown that the presented method was able to quantitatively assess the nonlinearity of the system; and to quantify and characterize the noise. Moreover, the presented method is able to determine the threshold frequency of the system above which the system does not present significant nonlinear effects even for very large perturbation amplitudes.

show abstract

Section: Transitionsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Harmonic analysis based method for linearity assessment and noise quantification in electrochemical impedance spectroscopy measurements: Theoretical formulation and experimental validation for Tafelian systems

Giner-Sanz

Ortega

Pérez-Herranz

2016

Electrochimica Acta

View full text Add to dashboard Cite

show abstract

“…This electrochemical technique was first introduced in wet-electrochemistry in the late sixties of last century; and then, during the seventies, it was adopted by the solid state researchers [41]. Today, EIS is widely used in both, liquid systems [42][43] and solid systems [44][45].…”

Section: Introductionmentioning

confidence: 99%

Application of a Montecarlo based quantitative Kramers-Kronig test for linearity assessment of EIS measurements

Giner-Sanz

Ortega

Pérez-Herranz

2016

Electrochimica Acta

View full text Add to dashboard Cite

Electrochemical Impedance Spectroscopy (EIS) is a very powerful tool to study the behaviour of electrochemical systems. Three conditions must be fulfilled during EIS measurements: causality, linearity, and stability. If any of these conditions is not achieved, then the conclusions obtained from the analysis of the measured spectra may be biased, or even misguided. For this reason, the verification of the compliance of these conditions is critical before accepting any analysis performed on an experimental spectrum. In a previous work, an experimental spectrum quantitative validation technique based on Kramers-Kronig relations was presented. The validation method consists in a Kramers-Kronig (KK) validation test, by equivalent electrical circuit fitting, coupled with a Montecarlo error propagation method. The validation technique builds a consistency region for a given confidence level that allows to discriminate between the individual points of the EIS spectrum that are consistent with the four fundamental hypotheses, and the inconsistent ones. The aim of this work is to validate experimentally if the quantitative validation technique is able to detect nonlinearities. In order to achieve this goal, the EIS spectrum of a markedly nonlinear system was measured experimentally using different perturbation amplitudes. The validation technique was applied to each one of the measured spectra. The method successfully managed to identify large nonlinearities; but did not detect slight ones.

show abstract

“…This comparison allows the determination of the rate of oxide film formation when the cathodic current is negligible, [5][6][7][8] or the determination of the cathodic current when oxide formation is negligible. 10,11 The correlation of cathodic current and dissolution rates is also important for assessing the dissolution of oxides and/or conversion coatings induced by a cathodic current. 8,9 To this end, Ogle and Weber 2 proposed a numerical convolution method that puts the electrochemical data on the same time resolution as the spectroscopic data so that a point by point comparison could be made.…”

mentioning

confidence: 99%

“…Atomic emission spectroelectrochemistry (AESEC) is an analytical technique that allows monitoring the dissolution of a large number of elements, simultaneously, in real time, during the reaction of a material with an aggressive electrolyte. References [1][2][3][4][5][6][7][8][9][10][11] describe the history, the instrumentation, and typical applications of this technique. Briefly, an inductively coupled plasma atomic emission spectrometry (ICP-AES) is used to continuously monitor the concentration of dissolved elements downstream from an electrochemical flow cell.…”

mentioning

confidence: 99%

On The Time Resolution of the Atomic Emission Spectroelectrochemistry Method

Shkirskiy

Maciel

Deconinck

et al. 2015

J. Electrochem. Soc.

Self Cite

View full text Add to dashboard Cite

The time resolution of the atomic emission spectroelectrochemical (AESEC) flow cell has been investigated by numerical simulations. The results demonstrate that the time resolution of the AESEC electrochemical flow cell may be simulated numerically based on the consideration of electrolyte flow patterns and ion transport in the cell. The residence time distribution (RTD) closely approximates a log-normal distribution for both experiment and simulation. Time resolution may be improved by increasing the flow rate, however this also leads to marked heterogeneities in the flow field near the surface. An optimum flow rate of 3 cm 3 min −1 was determined. The problem may be avoided somewhat by using a mask to cover all the surface except for a small portion near the center of the flow cell. Corrosion, dissolution and passivation occur spontaneously on the surface of metals in the presence of aggressive electrolytes. In order to accurately predict the evolution of these systems it is necessary to have real-time kinetic data so that the rate laws of the different elementary reactions may be identified. Atomic emission spectroelectrochemistry (AESEC) is an analytical technique that allows monitoring the dissolution of a large number of elements, simultaneously, in real time, during the reaction of a material with an aggressive electrolyte. References [1][2][3][4][5][6][7][8][9][10][11] describe the history, the instrumentation, and typical applications of this technique. Briefly, an inductively coupled plasma atomic emission spectrometry (ICP-AES) is used to continuously monitor the concentration of dissolved elements downstream from an electrochemical flow cell. Within the time resolution of the system, the instantaneous concentration flowing out of the cell (C M (t)) and the instantaneous dissolution rate at the working electrode/electrolyte interface (v M (t)) are directly related to each other as follows:where f e is the flow rate through the cell. The use of the technique is therefore very similar to that of a rotating ring disk electrode (RRDE) in which the electrochemical detection at the ring is replaced by the ICP-AES down stream from the flow cell. The major advantage of this technique is that we may simultaneously follow any number of species dissolving from the working electrode and usually with simplified quantification and sample preparation. On the other hand, as compared to the RRDE, AESEC has significantly lower time resolution. Several other research groups have proposed similar couplings in recent years. A quasi-identical electrochemical flow cell was used by Mercier et al. to investigate the corrosion 12 and the anodization of Al 13,14 also using ICP-AES detection. Voith et al. 15 have proposed an electrochemical flow cell using atomic absorption spectroscopy. Homozava et al. [16][17][18] and Ott et al. 19 proposed a capillary flow cell coupled to inductively coupled plasma mass spectrometer (ICP-MS) as a means of following multielement corrosion and dissolution with improved spatial resolution. Along...

show abstract

A novel coupling of electrochemical impedance spectroscopy with atomic emission spectroelectrochemistry: Application to the open circuit dissolution of zinc

Cited by 17 publications

References 29 publications

Harmonic analysis based method for linearity assessment and noise quantification in electrochemical impedance spectroscopy measurements: Theoretical formulation and experimental validation for Tafelian systems

Harmonic analysis based method for linearity assessment and noise quantification in electrochemical impedance spectroscopy measurements: Theoretical formulation and experimental validation for Tafelian systems

Application of a Montecarlo based quantitative Kramers-Kronig test for linearity assessment of EIS measurements

On The Time Resolution of the Atomic Emission Spectroelectrochemistry Method

Contact Info

Product

Resources

About