Thin layer spectroelectrochemistry of a regenerative mechanism

Jarbawi, Tafeedah B.; Heineman, William R.

doi:10.1016/0022-0728(82)85028-6

Cited by 8 publications

(1 citation statement)

References 19 publications

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“…[1][2][3][4] This method has been used to study mechanisms and/or to determine kinetic and thermodynamic parameters of electrochemical reactions. [5][6][7][8][9] The thinlayer spectroelectrochemical measurement is directly related to the faradaic current without interference of diffusion and nonfaradaic currents such as charging current. From potential-controlled spectroelectrochemical experiments, a set of potential-spectrum data is commonly obtained.…”

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confidence: 99%

A Double Logarithmic Method in Thin‐Layer Spectroelectrochemistry for Distinction among Mechanisms of an Irreversible Electrochemical Process

Zhu

Cheng

Dong

1999

J. Electrochem. Soc.

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There are many electrochemical systems showing irreversible behavior. It is interesting to find a suitable method for studying the complex mechanism of an irreversible process. Among several available methods, thin-layer spectroelectrochemistry is the simplest and most convenient if the species studied has a relatively large change in spectrum during the electrochemical process. Thin-layer spectroelectrochemistry combined with potential-control techniques can offer a time window of 30-3000 s for a thin-layer cell with 0.02 cm thickness, which is long enough to monitor an electrochemical reaction with standard heterogeneous electron-transfer rate constants of k 0 < 10 Ϫ5 cm s Ϫ1 , or coupled chemical reactions with rate constants of 10 Ϫ2 < k < 10 Ϫ4 s Ϫ1 (for first-order reactions). 1-4 This method has been used to study mechanisms and/or to determine kinetic and thermodynamic parameters of electrochemical reactions. 5-9 The thinlayer spectroelectrochemical measurement is directly related to the faradaic current without interference of diffusion and nonfaradaic currents such as charging current. From potential-controlled spectroelectrochemical experiments, a set of potential-spectrum data is commonly obtained. How to extract some important information for a complex electrochemical process from the limited experimental data is an interesting topic, especially for future development of spectroelectrochemistry. A well-known method is the Nernstian plot, which gives out thermodynamic parameters of E 0 Ј and n for a simple electrochemical process, but for a complex electrochemical process it cannot always show a straight line depending on the mechanism of the process. 10-13 Meites used a linearization method 14,15 to simplify a complex electrochemical process and extracted some mechanism information from the current-time data of potential-controlled experiments. Nowadays the nonlinear regression method has been commonly used to obtain some information about the mechanism of a complex electrochemical process, 16 but sometimes it is difficult to carry out, especially for multiple-parameter nonlinear regression based on a small amount of experimental data (commonly 10-15 data points). It is significant to find a simple method to extract some important information from a set of limited experimenta data of a complex process. If the mathematical model for a complex process is too difficult to describe analytically or a set of experimental data cannot be described with a suitable mathematical formula, then numerical analysis is very useful. In the present paper, a double logarithmic method has been adopted based on the combination of linearization with theoretical treatment for an electrochemical irreversible process in thin-layer spectroelectrochemical experiments. The numerical analysis shows that this method offers a simple and useful way to deal with potential-controlled thin-layer spectroelectrochemical data for distinguishing different mechanisms and also for determining some thermodynamic parameters of the process. Wi...

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confidence: 99%

A Double Logarithmic Method in Thin‐Layer Spectroelectrochemistry for Distinction among Mechanisms of an Irreversible Electrochemical Process

Zhu

Cheng

Dong

1999

J. Electrochem. Soc.

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Ultraviolet/Visible Spectroelectrochemistry

Scherson

Tolmachev

Stefan

2000

Encyclopedia of Analytical Chemistry

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This article reviews the field of solution‐phase ultraviolet/visible (UV/VIS) absorption spectroelectrochemistry and its application to problems in thermodynamics, kinetics, and mass transport, with emphasis on both experimental and theoretical aspects. Examples are provided for transmission in thin layer and semi‐infinite media, using optically transparent electrodes, and external and internal reflection in quiescent media. Also illustrated is the coupling of UV/VIS spectroscopy to systems under forced convection, such as rotating disk and channel electrodes, under steady state and transient conditions. Attention is also focused on spatially resolved spectroelectrochemistry for the imaging of diffusion and reaction layers. The last section is devoted to the more complex and particularly powerful modulation techniques involving diffraction, refraction and absorption in stagnant media and in the presence of convective flow. Factors that limit the sensitivity and spatial and temporal resolution of UV/VIS absorption spectroelectrochemistry, as well as its future prospects in analytical chemistry are briefly discussed.

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New anaerobic thin-layer spectroelectrochemical cell

Jarbawi¹,

Stankovich²

1994

Analytica Chimica Acta

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Thin layer spectroelectrochemistry of a regenerative mechanism

Cited by 8 publications

References 19 publications

A Double Logarithmic Method in Thin‐Layer Spectroelectrochemistry for Distinction among Mechanisms of an Irreversible Electrochemical Process

A Double Logarithmic Method in Thin‐Layer Spectroelectrochemistry for Distinction among Mechanisms of an Irreversible Electrochemical Process

Ultraviolet/Visible Spectroelectrochemistry

New anaerobic thin-layer spectroelectrochemical cell

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