Reaktionsschritte der elektrochemischen Phasengrenzreaktion

Lorenz, W.J.; Salié, G.

doi:10.1524/zpch.1961.29.5_6.390

Cited by 52 publications

(4 citation statements)

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“…It is well known that in the sixties of the previous century Lorenz and co-workers [2][3][4][5][6] suggested that a purely electrostatic bond between the ion and the metal is not a reality, and that, in specific adsorption, there is a degree of charge transfer tantamount to covalent bonding. This suggestion raises the possibility that equations in surface thermodynamics whereby the surface charge is related to the amount adsorbed on the assumption that the charge on the adsorbed ion is the same as the charge it maintains while in solution are not correct.…”

Section: The "Electric" State Of Adsorbed Species: Partial Charge Tramentioning

confidence: 99%

Double-layer phenomena in electrochemistry: Controversial views on some fundamental notions related to electrified interfaces

Horányi

Ланг

2006

Journal of Colloid and Interface Science

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Section: The "Electric" State Of Adsorbed Species: Partial Charge Tramentioning

confidence: 99%

Double-layer phenomena in electrochemistry: Controversial views on some fundamental notions related to electrified interfaces

Horányi

Ланг

2006

Journal of Colloid and Interface Science

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“…The roots of the problem go back to the early 1960's when Lorenz and co-workers have suggested [29][30][31][32][33][34] that a purely electrostatic bond between the ion and the metal is not a reality, and that, in case of specific adsorption, there is a degree of charge transfer, i.e., electrons are shared by atoms, like in covalent bonding. This suggestion raises the possibility that the charge on the adsorbed ion is not the same as the charge it carries in the solution phase, and equations in surface thermodynamics in which the chemical amount of adsorbed ions is related to the surface charge may be incorrect.…”

Section: The Problem Of Electrosorption Valency and Partial Charge Trmentioning

confidence: 99%

Some Questionable Approaches in Interfacial Electrochemistry—The Charged State of Adsorbed Species and Their Involvement in Redox Processes

Ланг

2020

Electrochem

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On the basis of a survey on the relevant literature it can be stated that some views and approaches concerning the charged state of adsorbed species and the charge transfer processes occurring with them are far from being unambiguous even in some respect they contradict fundamental physical and physicochemical principles. The meaning of the electrosorption valency, the misleading formulation of the Gibbs adsorption equation, and the interpretation of redox processes occurring with adsorbed species, is discussed in detail. It has been concluded that although the electrosorption valency of an adsorbed species as usually defined is an extra-thermodynamic and self-contradictory concept, experimental determined formal partial charge numbers can be a useful tool for scientists investigating adsorption phenomena, since the observed deviation between its value and the charge number of the same species in the solution phase unequivocally indicates a non-simple mechanism of the adsorption process, which should be taken into account in theoretical interpretation of the experimental data. It has been emphasized that the evaluation of voltammetric curves obtained in the presence of adsorbed redox partners requires a cautious analysis of the accompanying chemical transformations. In the framework of a critical analysis it is demonstrated that probably one of the most important sources of the misinterpretations and misunderstandings is the inadequate approach to the concept of electrode charge. The possibility of a general and straightforward presentation of the Gibbs adsorption equation has also been discussed.

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“…In the further transformation of the main initial equations we used the concept of partial charge transfer [18][19][20][21][22][23][24][25][26][27][28]. The full current I through the electrode/electrolyte interface in non-steady-state regime consists of two components: the charge transfer current I F and the (capacitive) charging current dq/dt:…”

Section: Model Of Charge-transfer Oxidation Reaction Complicated Withmentioning

confidence: 99%

Polarization complex-plane plot of impedance for two-stage charge-transfer reaction complicated with an intermediate adsorption (by example of benzene oxidation at boron-doped diamond electrode)

Елкин

Krotova

Pleskov

2014

Electrochimica Acta

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Reaktionsschritte der elektrochemischen Phasengrenzreaktion

Cited by 52 publications

References 0 publications

Double-layer phenomena in electrochemistry: Controversial views on some fundamental notions related to electrified interfaces

Double-layer phenomena in electrochemistry: Controversial views on some fundamental notions related to electrified interfaces

Some Questionable Approaches in Interfacial Electrochemistry—The Charged State of Adsorbed Species and Their Involvement in Redox Processes

Polarization complex-plane plot of impedance for two-stage charge-transfer reaction complicated with an intermediate adsorption (by example of benzene oxidation at boron-doped diamond electrode)

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