A faradaic impedance study of the electrochemical reduction of Cd(II) ions from aqueous 1 M (KF+KCl) mixed electrolyte solutions at the dropping mercury electrode

Bongenaar, C.P.M.; Remijnse, A. G.; Temmerman, E.; Sluyters‐Rehbach, M.; Sluyters, J.H.

doi:10.1016/s0022-0728(80)80036-2

Cited by 22 publications

(2 citation statements)

References 8 publications

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“…13, its rate constant increasing with increasing pH. In this case, the relation between the apparent diffusion coefficient calculated from uti and its correct value obtained from the limiting current is [21] D;'&, = 4D;'9(1 + L-1'2)2 (25) where L contains the information on the homogeneous reaction as defined in the Appendix. With eqn.…”

Section: Phmentioning

confidence: 97%

Analysis of the interfacial admittance in the case of a two-step two-electron electrode reaction with a diffusing intermediate, with application to the reduction of pyrazine

Rueda

Sluyters‐Rehbach

Sluyters

1987

Journal of Electroanalytical Chemistry and Interfacial Electroc

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A critical evaluation is presented of the analysis of impedance or admittance data in the case of an electrode reaction proceeding by two consecutive one-electron transfers with a stable, solution-soluble intermediate. It is shown that the expression for this case, as derived by Armstrong and Firman, has four limiting forms that have the same frequency dependence as the expression describing a single charge+ transfer reaction ("pseudo-&mlles behaviour"). Also, the conditions for another simplification, which leads to quarter circles in the complex plane diagram ("Armstrong's equivalent circuit"), are considered. It follows that the special case, where the quarter circle is in the negative quadrant, cannot occur when the system is dc reversible or at equilibrium. For dc irreversible systems, this phenomenon can show up under rather narrow conditions. In addition, it is found that, if these limiting cases are not fulfiied, the general equation often has a frequency dependence that within the practically useful frequency range is hardly distinguishable from that of the single charge-transfer case ("apparent Randles behaviour"). Consequently, the presence of the consecutive mechanism has to be detected from the dc potential dependence of the admittance parameters rather than from the frequency dependence. Finally, it is shown that the general expression corresponds to an equivalent circuit consisting of five elements which, however, have no sensible physical meaning.These views are applied to the reduction of pyraxine at a DME from 1 M aqueous NaClO, solutions of pH 4.8, 5.4 and 6.1. Although only one wave is observed in the dc polarogram, the potential dependence of the transfer resistance and the Warburg coefficient (found as parameters in a case of "apparent Randles behaviour") indicates two consecutive oneelectron transfers. The standard rate constants and the transfer coefficients of these two electron transfers are calculated, as well as the rate constant of a homogeneous chemical reaction following the second electron transfer. It is concluded that slow protonation steps largely determine the kinetics of the electron transfers.The reactants are found to be weakly adsorbed in contrast with the strong adsorption found earlier in strongly acidic solutions.l Dedicated to the memory of Don Smith.

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Section: Phmentioning

confidence: 97%

Analysis of the interfacial admittance in the case of a two-step two-electron electrode reaction with a diffusing intermediate, with application to the reduction of pyrazine

Rueda

Sluyters‐Rehbach

Sluyters

1987

Journal of Electroanalytical Chemistry and Interfacial Electroc

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“…The reduction of Cd(II) ions at the dropping mercury electrode (DME) has been widely used to test models for electrode reactions. Nowadays, some characteristics of the process seem well established, as the CEE mechanism (C: chemical reaction, E: electron transfer) [1][2][3][4], but other questions remain unsolved when adsorption or complexation is present [5][6][7][8][9]. The catalytic effect or inhibition by organic substances could introduce changes in the mechanism or only influence values of the parameters and velocity constants.…”

Section: Introductionmentioning

confidence: 99%

Reduction of Cd(II) Ions in the Presence of Tetraethylammonium Cations. Adsorption Effect on the Electrode Process

Torrent‐Burgués

2021

Electrochem

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The effect of the adsorption of tetraethylammonium (TEA) cations, which present both ionic and organic characteristics, on the reduction of Cd(II) ions have been studied from dc and ac measurements at the dropping mercury electrode. The resistance to the charge transfer (Rct) and Warburg coefficient (σ) parameters have been determined through impedance measurements. Thus, the global velocity constant has been obtained. The reduction process of Cd(II) in perchloric media is reversible and is affected by the adsorption of TEA cations, especially at high TEA concentrations. Values of E1/2, half wave potential, and DO, diffusion coefficient, obtained from both dc and ac measurements agree. The velocity constants show a decrease as TEA concentration increases, with values ranging from 0.6 to 0.01 cm·s−1. The inhibitory effect of TEA adsorption on the electrode process and the relationship between electrode coverage, θ, and velocity constants, K, using several isotherm equations, have been discussed. The best fit was obtained with the equation K = 0K(1 − θ)a with an a value close to three, indicating a blocking effect and electrostatic repulsion due to TEA.

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Electrochemistry of Cadmium

Stroka

Maksymiuk

Galus

2006

Encyclopedia of Electrochemistry

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The sections in this article are Double‐layer Properties of Cadmium Electrodes Electrochemical Properties and Kinetics of the Cd ( II )/ Cd ( Hg ) Systems Electrochemistry in Aqueous Solutions Kinetics of Simple Ions Influence of a Catalyst Influence of Inhibitors Electrochemistry in Mixed and Nonaqueous Solvents Electrochemical Properties of the Cadmium Complexes Determination of Stability Constants Electrochemical Preparation of Cadmium Complexes Preparation and Electrochemical Properties of Cadmium Chalcogenides CdS CdSe Cd Te Properties of Cadmium Intermetallic Compounds Cadmium Underpotential Deposition and Electrodeposition on Solid Electrodes Deposition of Cd on Cadmium Electrode Electrodeposition of Cd on Other Solid Substrates Gold Platinum Silver Copper Silicon Other Substrates Passivation and Corrosion of Cadmium Passivation of Cadmium Electrode Corrosion of Cadmium Applied Electrochemistry Batteries Cadmium–Mercuric Oxide Primary Cells Cadmium–Nickel Oxide ( Ni – Cd ) Secondary Cells Cadmium–Silver Oxide Secondary Cells Application in Electrochemical Sensors Potentiometric Sensors Amperometric‐voltammetric Sensors

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A faradaic impedance study of the electrochemical reduction of Cd(II) ions from aqueous 1 M (KF+KCl) mixed electrolyte solutions at the dropping mercury electrode

Cited by 22 publications

References 8 publications

Analysis of the interfacial admittance in the case of a two-step two-electron electrode reaction with a diffusing intermediate, with application to the reduction of pyrazine

Analysis of the interfacial admittance in the case of a two-step two-electron electrode reaction with a diffusing intermediate, with application to the reduction of pyrazine

Reduction of Cd(II) Ions in the Presence of Tetraethylammonium Cations. Adsorption Effect on the Electrode Process

Electrochemistry of Cadmium

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