Surface thermodynamics reconsidered. Derivation of the Gokhshtein relations from the Gibbs potential and a new approach to surface stress

Fletcher, Stephen

doi:10.1007/s10008-013-2287-9

Cited by 7 publications

(11 citation statements)

References 20 publications

(13 reference statements)

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“…and an electrical potential difference E between two electrodes e.g., between phase α if it is an electronic conductor and a reference electrode (ref. [8]. {reference [14] in the present work}) When the reference electrode is in equilibrium with a cation (anion) in phase β, E is given the subscript + (−).…”

Section: On the Alternative Formulations Of The Gibbs Adsorption Equamentioning

confidence: 99%

“…Even after many years of disputes, a consensus regarding the different approaches is still being sought. Some of these issues have been discussed recently in excellent articles and reviews [6][7][8][9][10]. When considering which model is most appropriate to apply to the solid/liquid interfaces, one may argue that the results of the theoretical work can be proved experimentally.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: On the Alternative Formulations Of The Gibbs Adsorption Equamentioning

confidence: 99%

Section: Introductionmentioning

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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“…Unfortunately, for electrodes containing electronically conducting solid phase(s), the correct thermodynamic treatment of the interface is not straightforward, and the thermodynamic theory of solid/liquid interfaces cannot be regarded as entirely correct [2][3][4][5][6][7][8][9][10]. On the other hand, the measurement of surface parameters at the electrified solid/liquid interface is difficult, and the measuring methods are not without their limitations [11][12][13].…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, the measurement of surface parameters at the electrified solid/liquid interface is difficult, and the measuring methods are not without their limitations [11][12][13]. Some of these issues have been discussed recently in excellent articles and reviews [5][6][7][8]14]. The basic concepts of the Gibbs model of interfaces are summarized, e.g., in refs [2,11,15].…”

Section: Introductionmentioning

confidence: 99%

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Some remarks to the derivation of the “generalized Lippmann equation”

Ланг

2020

J Solid State Electrochem

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In the present communication, an attempt is made to demonstrate (once again) some of the problems with the derivation of the “generalized Lippmann equation” considered to be valid by many researchers for solid electrodes and to address the problems in the framework of the Gibbs model of the interface by using only the basic principles of thermodynamics. By surveying the relevant literature, it has been shown that during the derivation of the equation, it was completely ignored that the Gibbs-Duhem equation (i.e., the electrocapillary equation) is a mathematical consequence which follows directly from the homogeneous degree one property of the corresponding thermodynamic potential function; consequently, the resulting expression cannot be correct. Some alternative approaches have also been considered. The adequacy of the open system and the partly closed system approach has been critically discussed, together with the possibility of introducing new thermodynamic potential functions.

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Comment on “On the ‘simple check’ of electrocapillarity” by AY Gokhshtein

Gutman

2014

J Solid State Electrochem

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Surface thermodynamics reconsidered. Derivation of the Gokhshtein relations from the Gibbs potential and a new approach to surface stress

Cited by 7 publications

References 20 publications

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

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

Some remarks to the derivation of the “generalized Lippmann equation”

Comment on “On the ‘simple check’ of electrocapillarity” by AY Gokhshtein

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