Current-potential curves for a catalytic mechanism with non-Nernstian behavior

Gálvez, Jesús; Serna, Carmen; Saura, R.; Zapata, Juan

doi:10.1016/0022-0728(86)87039-5

Cited by 11 publications

(1 citation statement)

References 13 publications

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“…This value is within an experimental error from the slope of catalytic vanadium‐cupferron wave determined previously as 87 mV . Usually polarographic catalytic systems have the same slope as the wave of the catalyst itself . The most probable explanation of the value of the slope is a quasi‐reversible charge transfer in the V(III)‐V(II) system with V(II) complex acting as the catalyst of promoted cupferron reduction.…”

Section: Resultsmentioning

confidence: 99%

Electrochemical Reduction of Vanadium(V)‐Cupferron Complex, VO(cupf)₂OH

Kaplun

Ivanov

2019

Electroanalysis

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Electrochemical reduction of vanadium(V) complex with cupferron (N‐nitroso‐N‐phenylhydroxylamine), VVO(cupf)2OH, has been studied by polarography in wide potential range to verify the catalytic mechanism of electroreduction of coordinated cupferron ligand. Reduction of the complex was studied in the concentration range from 2 ⋅ 10−5 M to 10−3 M. Depending on the process conditions kinetics of catalytic reduction of coordinated cupferron is either controlled by adsorption step or governed by mixed control of diffusion and chemical reaction. Kinetic parameters of the reduction process are reported. Reduction of VVO(cupf)2OH complex is accompanied by adsorption and autoinhibition phenomena. V(II) ion in the surface bound complex of vanadium with cupferron catalyzes reduction of coordinated cupferronate ligands. In 1 mM solutions, the catalytic reduction of coordinated cupferron ligand shifts to more cathodic potentials due to formation of a monolayer of adsorbed vanadium(III)‐cupferron complexes. Reduction kinetics in the presence of tetraalkylammonium salt is consistent with multilayer cooperative adsorption of anionic vanadium(II)‐cupferron complex and tetraalkylammonium cations.

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Section: Resultsmentioning

confidence: 99%

Electrochemical Reduction of Vanadium(V)‐Cupferron Complex, VO(cupf)₂OH

Kaplun

Ivanov

2019

Electroanalysis

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Electrocatalysis‐Based Kinetics Determinations

Bănică

Ion

2000

Encyclopedia of Analytical Chemistry

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The term “electrocatalysis” denotes the catalysis of an electrochemical reaction. In accord with the general definition of catalysis1 the effect of an electrocatalyst is to increase the rate of an electrochemical reaction without modifying the overall standard Gibbs energy change in the reaction. Taking the view of Faraday's law, the rate of an electrochemical reaction is expressed by the electrolytic current. Consequently, an increase in the electrolytic current is the main result of electrocatalysis. The benefits of electrocatalysis include making possible the quantitation of the catalyst itself or of some substrate compounds that are not electrochemically active or are not generally amenable to direct electrochemical determination. An appreciable improvement in selectivity may be brought about by electrocatalysis. Additionally, appropriate engineering of catalytic layers on electrode surfaces has led to the preparation of a huge variety of chemical and biochemical sensors. However, close control of the experimental conditions (temperature, electrolyte composition) is often required when dealing with electrocatalytic processes. Usually, such requirements do not give rise to any particular difficulties.

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