Differential Capacity of Mercury in Aqueous Sodium Fluoride Solutions. I. Effect of Concentration at 25°

Grahame, David C.

doi:10.1021/ja01648a014

Cited by 295 publications

(99 citation statements)

References 6 publications

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“…Thus the obtained solution of [9] (which justifies Grahame's parametrizations) is appropriate for moderate concentration [39] and in the range around zcp determined by [40]. Taking for estimates an aqueous solution (z, -5 A, L, --7 A) of 1-1 electrolyte, we come to the restrictions jol << 10 pC/cm2, c << 1 M. These values belong to the typical range of charges and concentratiolls in electrochemical experiments.…”

Section: On the Criterion Of The Validity Of [31]mentioning

confidence: 66%

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Nonlocal dielectric response of the electrode/solvent interface in the double layer problem

Kornyshev¹,

Воротынцев²

1981

Can. J. Chem.

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This paper is dedicated to Dr. Sam Leuine on the occasion of his 70th birthday A. A. KORNYSHEV and M. A. VOROTYNTSEV. Can. J. Chem. 59,2031Chem. 59, (1981. A theory of the double layer in the electrolyte solution near the electrode surface is formulated in terms of the most general description of the electrodelsolvent interface, the ionic plasma being treated in the Poisson-Boltzmann approximation. As a result, the differential capacitance of the electrochemical contact is calculated. In the case of low ionic concentrations (50.1 M) it takes the form: C-' = CGC-l + CI-l, where the CGc is the Gouy-Chapman nonlinear differential capacitance and C* is a "constant" capacitance, not depending on the concentration, but possessing a possible dependence on the charge of the electrode. The "compact layer" capacitance C* is expressed through a unified nonlocal dielectric function of the electrode-solvent system. This may be considered as a formal approval of Grahame's parametrization of experimental data. But the physical meaning of the compact layer capacity is reconsidered subject to the relation obtained with the nonlocal dielectric function. The latter reflects the electronic structure of the metal and the structure of the solvent in contact. Thereby, the possible reasons for the dependence of the "compact layer" capacity on the nature of the electrode, solvent, and the interaction between them are revealed. A generalization of the results on the case of a more general description of ionic plasma is discussed. Chem. 59,2031Chem. 59, (1981. On formule une thkorie de la double couche dans une solution electrolytique au voisinage de la surface d'une electrode en fonction de la description la plus gknerale de I'interface electrode/solvant alors qu'on traite le plasma ionique par l'approximation de Poisson-Boltzmann. 11 en resulte que l'on peut calculer la capacite differentielle du contact electrochimique. Dans le cas des faibles concentrations ioniques (<,o,I M), elle prend la forme C-I = CG,-l + C*-( OG CGC est la capacite differentielle non lineaire de Gouy-Chapman et C* est une capacite constante independante de la concentration qui peut eventuellement dependre de la charge sur l'electrode. On exprime la capacitk de la "couche compacte" C* au moyen d'une fonction dielectrique non locale unifike du systeme electrode-solvant. On peut considkrer ceci comme une confirmation formelle de la transposition des donnees experimentales en parametre qui a etC faite par Grahame. Toutefois, on a reconsidere la signification physique de la capacite de la couche compacte, en fonction de la relation obtenue avec la fonction dielectrique non locale. Cette derniere reflete la structure electronique du metal et la structure du solvant qui est en contact. On trouve aussi les diverses raisons qui pourraient expliquer pourquoi la capacite de la "couche compacte" depend de la nature de I'electrode, du solvant et de I'interaction entre-eux. On discute de la generalisation des resultats dans le cas d'une description plus generale d'un plasma...

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Section: On the Criterion Of The Validity Of [31]mentioning

confidence: 66%

“…For larger o, the sum in [37] can be estimated in the light of [28] by Thus [37] is reduced to At the same time the simplification of the external solution also implied the inequality [39].…”

Section: On the Criterion Of The Validity Of [31]mentioning

confidence: 99%

Nonlocal dielectric response of the electrode/solvent interface in the double layer problem

Kornyshev¹,

Воротынцев²

1981

Can. J. Chem.

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“…Solutions of NaF=0.100 M were studied extensively, initially by Grahame [20] and more recently, by Foresti et al [14]. Copper ions and oxygen were chosen as electroactive 'contaminants' in such experiments.…”

Section: Resultsmentioning

confidence: 99%

Determination of the surface charge density of a mercury electrode by extrusion: a new method for correction of the faradaic component

Brito

Angnes

Brett

et al. 1999

Journal of Electroanalytical Chemistry

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The accurate determination of the surface charge density at the mercury solution interface by the method of extrusion of mercury drops is impaired by the faradaic current caused by traces of electroactive species. This paper describes a new design of a hanging mercury drop electrode with accurate control of the extruded electrode area, to within 0.1%, together with a new and reliable procedure for correction of the faradaic current. The procedure is based on first obtaining the correction parameters in the presence of increasing amounts of electroactive species and then using these parameters for correction of the faradaic component so as to obtain the surface charge density of the electrode. Implementation of the method with a microcomputer controlled system provides automatic acquisition of corrected electrode charge density values as a function of the electrode potential. The results obtained with this new method are in excellent agreement with those obtained by other methods, as illustrated for aqueous sodium fluoride solution.

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“…[49,62] Electrostatic gating through an insulating pore is known, [55,63] and this is important in the theory of reverse osmosis membranes. [52,64] However, experimental demonstrations of capacitance dips due to these effects are often difficult, or difficult to generalize; [65] specifically adsorbed ions and nonuniform surface potentials can obscure such effects. Another possible effect is that ions excited into the diffuse layer could contribute to conductivity.…”

Section: Premisementioning

confidence: 99%

Optimized nanoporous materials.

Langham¹,

Jacobs²,

Ong³

et al. 2009

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Nanoporous materials have maximum practical surface areas for electrical charge storage; every point in an electrode is within a few atoms of an interface at which charge can be stored. Metal-electrolyte interfaces make best use of surface area in porous materials. However, ion transport through long, narrow pores is slow. We seek to understand and optimize the tradeoff between capacity and transport. Modeling and measurements of nanoporous gold electrodes has allowed us to determine design principles, including the fact that these materials can deplete salt from the electrolyte, increasing resistance. We have developed fabrication techniques to demonstrate architectures inspired by these principles that may overcome identified obstacles. A key concept is that electrodes should be as close together as possible; this is likely to involve an interpenetrating pore structure. However, this may prove extremely challenging to fabricate at the finest scales; a hierarchically porous structure can be a worthy compromise.

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Differential Capacity of Mercury in Aqueous Sodium Fluoride Solutions. I. Effect of Concentration at 25°

Cited by 295 publications

References 6 publications

Nonlocal dielectric response of the electrode/solvent interface in the double layer problem

Nonlocal dielectric response of the electrode/solvent interface in the double layer problem

Determination of the surface charge density of a mercury electrode by extrusion: a new method for correction of the faradaic component

Optimized nanoporous materials.

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