Determination of kinetic parameters from steady-state microdisk voltammograms

Galus, Zb́igniew; Gołaś, Janusz; Osteryoun, Janet

doi:10.1021/j100316a021

Cited by 47 publications

(12 citation statements)

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“…For BHDC concentrations higher than 0.016 M the systems behave as quasi-reversible. The theory for a quasi-reversible reaction developed for a micro-electrode operating in the steady state regime (eqn (6)) 49 was used for the polarization curves for [BHDC] > 0.016 M:…”

Section: Steady-state Voltammograms Characterizationmentioning

confidence: 99%

Droplet–droplet interactions investigated using a combination of electrochemical and dynamic light scattering techniques. The case of water/BHDC/benzene:n-heptane system

et al. 2015

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In this contribution the electrochemistry of [Fe(CN)6](4-/3-) as the probe molecule was investigated in benzyl-n-hexadecyldimethylammonium chloride (BHDC) reverse micelles (RMs) varying the composition of the external solvent (benzene:n-heptane mixtures) and the surfactant concentration, at a fixed water content and probe concentration. The electrochemical and dynamic light scattering results show that in water/BHDC/benzene:n-heptane systems the aggregate sizes increase on increasing BHDC concentration. This behavior was unexpected since it is known that for water/BHDC/benzene RM systems keeping the water content constant and the surfactant concentration below 0.2 M, the droplet sizes are independent of the concentration of the surfactant. We explain the results considering that on changing the external solvent to benzene:n-heptane mixtures, RMs tend to associate in clusters and equilibrium between free RMs and droplet clusters is established. A model is presented which, using electrochemical and dynamic light scattering data, allows calculating the aggregation number of the RMs, the number of RMs that form the droplet clusters and the standard electron transfer heterogeneous rate constant.

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Section: Steady-state Voltammograms Characterizationmentioning

confidence: 99%

Droplet–droplet interactions investigated using a combination of electrochemical and dynamic light scattering techniques. The case of water/BHDC/benzene:n-heptane system

et al. 2015

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“…As reported by Galus et al [42], steady-state voltammogram could be used to determine the heterogeneous electron transfer rate constant k s . When the oxidized form only is present initially in the solution, the voltammetric response of a quasi-reversible reduction reaction under steady-state conditions on a microdisk electrode is given as follows (see Appendix A):…”

Section: Resultsmentioning

confidence: 96%

“…Galus et al [42] derived Eq. (A.1) to determine k s from steady-state microdisk voltammograms of a oxidation process assuming that the reduced form only is present initially in the solution:…”

Section: Appendix Amentioning

confidence: 99%

Kinetic studies of dioxygen and superoxide ion in acetonitrile at gold electrodes using ultrafast cyclic voltammetry

Guo¹,

Lin²

2005

Journal of Electroanalytical Chemistry

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“…Three types of j – E responses with respect to the diffusion state are available, namely, the transient response, pseudo steady-state response, and steady-state response called the polarization curve . For the one-electron process, all of the j – E responses can be easily deciphered based on the Bulter–Volmer equation, and even the Nernst equation in reversible cases, to obtain the intrinsic relationship between j and E . Half-wave potential ( E 1/2 ) is derived in this case, being employed as an approximation of the standard potential to reveal the potential feature .…”

Section: Introductionmentioning

confidence: 99%

Derivative-Extremum Analysis Principle for Irreversible Electrode Reactions: Feature Parameter Extractions from Polarization Curves

Yin

Liu

2019

J. Phys. Chem. C

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To ascertain the kinetic information of an irreversible electrode reaction, we extract two parameters of half-wave potential (E 1/2 ) and peak value (PV) from the polarization curve through a derivative-extremum analysis. The E 1/2 and PV are demonstrated to be two feature parameters corresponding to a special kinetic state, with electron transfer and reactant mass transport reaching a balance. This definition covers the characteristics of the inflection point in the polarization curve and the peak point in the derivative curve. A set of equations centering on E 1/2 and PV are derived serving to disclose their significances in irreversible case and are verified by oxalic acid oxidation, nitrite oxidation, and oxygen reduction reaction. It is clarified that the E 1/2 in the irreversible case is dominated by the standard potential and standard rate constant and characterizes the potential feature. Meanwhile, PV is an activation feature parameter associated with the activation rate driven by overpotential. Thus, a derivative-extremum analysis principle toward irreversible reactions is formed, providing an electrochemical insight for understanding the half-wave potential and enabling quantitative investigation of kinetic features and convenient parameter estimations in the irreversible electrochemical matrix.

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Determination of kinetic parameters from steady-state microdisk voltammograms

Cited by 47 publications

References 1 publication

Droplet–droplet interactions investigated using a combination of electrochemical and dynamic light scattering techniques. The case of water/BHDC/benzene:n-heptane system

Droplet–droplet interactions investigated using a combination of electrochemical and dynamic light scattering techniques. The case of water/BHDC/benzene:n-heptane system

Kinetic studies of dioxygen and superoxide ion in acetonitrile at gold electrodes using ultrafast cyclic voltammetry

Derivative-Extremum Analysis Principle for Irreversible Electrode Reactions: Feature Parameter Extractions from Polarization Curves

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