Overvoltage at Oxidation-Reduction Electrodes

Petrocelli, J. V.; Paolucci, A. A.

doi:10.1149/1.2778208

Cited by 22 publications

(20 citation statements)

References 3 publications

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“…79 mV/decade was obtained in the entire potential range for all rotation rates. This slope is analogous that obtained by Petrocelli and Paolucci [26] for the oxidation of potassium ferricyanide in NaOH on platinum. This implies that the initial electron transfer is the rate-limiting step of this reaction.…”

Section: Rotating Disk Electrodesupporting

confidence: 88%

Electrochemical studies of ferrocene in a lithium ion conducting organic carbonate electrolyte

Laoire¹,

Plichta²,

Hendrickson³

et al. 2009

Electrochimica Acta

109

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Section: Rotating Disk Electrodesupporting

confidence: 88%

Electrochemical studies of ferrocene in a lithium ion conducting organic carbonate electrolyte

Laoire¹,

Plichta²,

Hendrickson³

et al. 2009

Electrochimica Acta

109

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“…The apparent standard rate constants for the ferroferricyanide couple on NiO (Li) are considerably slower than on metals such as platinum and gold even at low pH values where protonation of the ferrocyanide leads to less reversibility [see e.g., (17)(18)(19)(20)(21)(22)(23)]. …”

Section: Science and Technologymentioning

confidence: 99%

Redox Couple Behavior on Lithiated Nickel Oxide Electrodes

Tench

Yeager²

1974

J. Electrochem. Soc.

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The rotating electrode technique has been used to study the kinetics of various redox couples [Fe(CN)64-/Fe(CN)63-, Fe2+/Fe 3+, Cr2+/Cr 3+, and quinone/hydroquinone] on mosaic lithiated nickel oxide electrodes in sulfate solutions. At potentials cathodic to the flatband potential, the redox reactions are very inhibited. At potentials anodic to the flatband potential, the oxidation of the ferrocyanide ion exhibits a transfer coefficient of ~ : 1/2 with an apparent standard rate constant approximately two orders of magnitude smaller than on Pt. The other couples exhibit abnormal transfer coefficients under these conditions, probably because of specific adsorption on the oxide electrode surface. The kinetics of various redox reactions have been examined on lithiated mosaic nickel oxide electrodes with the objective of comparing the behavior of these couples on this compound semiconductor with that on metals. With NiO(Li) electrodes, the heterogeneous electron transfer is expected to involve rather localized valency states within the electrode phase [i.e., Ni 2+ (3d s) and Ni ~+ (3d 7) ] rather than the wide bands * Electrochemical Society Active Member. ~Present address: Fritz-Haber ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 35.8.11.2 Downloaded on 2015-06-26 to IP Vol. 121, No. 3 REDOX COUPLE BEHAVIOR ON NiO ELECTRODES 319 ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 35.8.11.2 Downloaded on 2015-06-26 to IP

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“…[8] holds for such a system with two distinct partial processes, the measurable potential (V) for the case of no externally applied current (i~ = 0, "spontaneous" corrosion) is given by Such might be the case for the hydrogen-evolutiontype corrosion of a metal.…”

Section: Rate and Potential In Simple Polyelectrode Systemsmentioning

confidence: 99%

“…[8]), in order to relate the rates of partial processes to the measurable potential (V), cancel out in the result of Eq. Terms in (A~b~e~ --~b), which appear in the definitions of Q~ and Qo (cf.…”

Section: O~a~ a -~-Aex V Ota~k A 7[-o~c)t Cmentioning

confidence: 99%

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Kinetic Studies on Corrosion Systems

Posey¹

1959

J. Electrochem. Soc.

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Electrochemical kinetics has been applied to the case of corroding polyelectrodes under activation control for the situation where the rates of partial processes vary over the surface of an electrode. Explicit expressions have been derived for rate and potential in the simplest polyelectrode systems. The kinetics of galvanic couples under activation control has been derived with emphasis on the significance of measurable quantities. The use of steady-state polarizability measurements, potentiostatic measurements, and galvanostatic measurements in the study of polyelectrode systems has been outlined.Numerous investigators have contributed to the foundations ~ and experimental applications of electrochemical kinetics and comprehensive reviews of this work have been published (4-6). Much of the existing theory treats the case of a single over-all reaction under activation controF at an electrodesolution interphase [e.g., a metal-metal ion equilibrium, or a redox reaction at an inert electrode (8)], and one of the most general treatments of such a system' has been presented by Parsons (9). Wagner and Traud (10), Kimball (11), and Audubert (12) have been among the few to examine corrosion systems from a systematic kinetic viewpoint. However, in the study of some of the more complex electrochemical situations, such as those occurring in many corrosion systems, there appears to be a need for a more extensive treatment suitable for interpreting the phenomenology. In the present report, an elementary electrochemical kinetic treatment of twophase polyelectrode systems ~ and galvanic couples under activation control has been developed, and the application of the theory to the analysis of corroding polyelectrodcs has been outlined for several types of steady-state measurements. The results of an experimental investigation on a particular polyelectrode system will be presented in a subsequent report.' Operated by Union Carbide Corporation for the U. S. Atomic Energy Commission.-9 The source equations of electrochemical kinetics may be found in the works of Butler (1), Bowden and Rideal (2), and Erdey-Gruz and Volmer (3). ~Use of the term, activation control, here corresponds to the sense of the designation, "Durchtrittstiberspannung," as employed by Vetter (7) to distinguish between cases where the charge transfer step in an electrochemical reaction or partial process is ratedetermining and those where the higher activation energy of a precursor step or a subsequent step in the reaction determines the rate.' The designation, system, is used-here to refer to an electrode plus its liquid environment.~The term, polyelectrode, as used here, refers to the situation where more than one chemicalIy distinct individual or partial process is occurring at the same electrode-solution interphase. The term, two-phase polyelcctrode system, denotes a metallic polyeleetrode in contact with a nonmetallic environment in the liquid state. The case of intervention of a third phase (e.g., an oxide film) between metal and solution is not considered...

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Overvoltage at Oxidation-Reduction Electrodes

Cited by 22 publications

References 3 publications

Electrochemical studies of ferrocene in a lithium ion conducting organic carbonate electrolyte

Electrochemical studies of ferrocene in a lithium ion conducting organic carbonate electrolyte

Redox Couple Behavior on Lithiated Nickel Oxide Electrodes

Kinetic Studies on Corrosion Systems

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