The Thermodynamic Theory of Electrocapillarity<sup>1</sup>

Grahame, David C.; Whitney, Robert B.

doi:10.1021/ja01259a017

Cited by 71 publications

(32 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…2c and 7c remain congruent with respect to qa over the whole experimental range and the values of Ti,. calculated at lo-' M and 25°C agree within less than 1.5% with the data derived from a single electrolyte system (24). A plot of Ti, versus AE is shown in Fig.…”

Section: Comparison Of Adsorption Isotherms At 25ocsupporting

confidence: 69%

The surface phase at the ideal polarized mercury electrode. IV. Determination of molar entropies of adsorption of specifically adsorbed halide ions

Charles¹,

Mulenga²,

Jenard³

et al. 1981

Can. J. Chem.

View full text Add to dashboard Cite

Differential capacitances are measured as a function of temperature at the ideal polarized Hg electrode in systems of mixed sodium halides at ionic strength J = 10−1 mol kg−1. A quasi-thermodynamic treatment is presented according to which excess entropies of adsorption in the inner layer are determined. The formation entropy of the inner layer and the water and ion molar entropies of adsorption are presented for a range of moderate and small ionic surface coverages.

show abstract

Section: Comparison Of Adsorption Isotherms At 25ocsupporting

confidence: 69%

The surface phase at the ideal polarized mercury electrode. IV. Determination of molar entropies of adsorption of specifically adsorbed halide ions

Charles¹,

Mulenga²,

Jenard³

et al. 1981

Can. J. Chem.

View full text Add to dashboard Cite

show abstract

“…This quantity, which is the variable conjugate to V, requires a change of V with A held constant and thus a change in (b --a). According to (12) it is defined as…”

Section: (3) Surface Tension Pressure and Chemical Potentialmentioning

confidence: 99%

“…Let us write the relation (5) for a particle of type s, denoting by ρ s (Z 1 Ω 1 ) the probability of finding a particle of type s at R 1 with orientation Ω 1 By changing the integration variable from R 12 to --R 12 , noting that ∂u sr /∂Z 12 = --∂u sr /∂(--Z 12 ), one sees that contribution to the integral of the second term in square brackets gives the negative of that of the first, and…”

Section: Appendixmentioning

confidence: 99%

Thermodynamics and statistical mechanics of the ideally polarisable electrode Gibbs isotherm and surface tension

Badiali

1978

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

A definition of the ideally polarisable electrode which allows a general statistical mechanical treatment is given, comparisons with the usual thermodynamic approach being made. It is shown that, with this definition, the system behaves as a pure capacitance to an imposed alternating potential of sufficiently low frequency. The equilibrium states of the system are described by the grand canonical distribution. Thermodynamic functions, given in terms of the grand canonical partition function, can be computed in molecular terms: In particular, general expressions for the surface tension and the pressure are obtained, and compared to those proposed by various authors. The separation of the pressure into electrical and nonelectrical parts is analyzed. Expressions are given for the electrochemical potentials of charged and of dipolar species. With these microscopic definitions, the Gibbs adsorption isotherms and the Lippmann equation are derived. For several simple models, including that of Gouy and Chapman for an ionic solution and a metal electrode, these relations are explicitly considered. The inadmissability, in a coherent model, of reducing the solvent to a medium of fixed dielectric constant, is emphasized. IntroductionThe ideally polarisable electrode (IPE) is the simplest electrochemical system. In spite of its ideality, it is possible to approach it experimentally, at least in a limited range of potential, in the mercury drop electrode. Because of this, the system has been the subject of many studies, which are summarized and discussed in the standard works on electrochemistry [1--4].From thermodynamic reasoning, one can show that certain quantities characteristic of the interface, such as the electrode charge or the amounts of adsorbed substances, are accessible through studies of the surface tension of the IPE as a function of parameters like the potential difference across the system or the chemical potentials of the various components. On the other hand, several authors have attempted to define the surface tension o directly, in terms of the mechanical equilibrium of the interface [5--10]. Various expressions have [End of page 151] been proposed for o. In a study of the interface between an electrolytic solution and its vapor, Buff [11] showed that the thermodynamic and mechanical approaches yield the same microscopic expression for o. Our study of the IPE is in part along these lines.In the first part of this work, we define precisely the system and its surroundings (measurement cell). Subsequently, we derive the Gibbs adsorption isotherm by statistical mechanical methods (grand partition function). This procedure affords microscopic definitions of the various intensive quantities which characterize the interface. Subsequently, we compare the expression for the surface tension with those proposed in the literature.

show abstract

“…Many theoretical works have been performed on the electrocapillary phenomena based on the well-known Lippmann equation [3], which was originally developed for a perfectly conducting fluid such as mercury. Several efforts have been made to extend this theory [4]. There are basically two different approaches: the free-energy based approach and the electromechanical approach.…”

Section: Introductionmentioning

confidence: 99%

Ion size effects on the osmotic pressure and electrocapillarity in a nanoslit: Symmetric and asymmetric ion sizes

Rajni

Kang

2016

Phys. Rev. E

View full text Add to dashboard Cite

We analyze the effect of asymmetric finite ion size in nanoconfinement in the view of osmotic pressure and electrocapillarity. When the confinement width becomes comparable with the Debye length, the overlapped electric double layer is significantly deformed by the steric effects. We derive the osmotic pressure from the modified Poisson-Boltzmann equation in a nanoslit to examine the deviation from the ideal osmotic pressure and the repulsive force on the wall considering the asymmetry of ion sizes. Then the electrocapillarity due to the steric effect is investigated under constant potential condition with the flat interface assumption. Later, the deformation by the electrocapillarity is also considered in the first order approximation.

show abstract

The Thermodynamic Theory of Electrocapillarity¹

Cited by 71 publications

References 0 publications

The surface phase at the ideal polarized mercury electrode. IV. Determination of molar entropies of adsorption of specifically adsorbed halide ions

The surface phase at the ideal polarized mercury electrode. IV. Determination of molar entropies of adsorption of specifically adsorbed halide ions

Thermodynamics and statistical mechanics of the ideally polarisable electrode Gibbs isotherm and surface tension

Ion size effects on the osmotic pressure and electrocapillarity in a nanoslit: Symmetric and asymmetric ion sizes

Contact Info

Product

Resources

About

The Thermodynamic Theory of Electrocapillarity1

Cited by 71 publications

References 0 publications

The surface phase at the ideal polarized mercury electrode. IV. Determination of molar entropies of adsorption of specifically adsorbed halide ions

The surface phase at the ideal polarized mercury electrode. IV. Determination of molar entropies of adsorption of specifically adsorbed halide ions

Thermodynamics and statistical mechanics of the ideally polarisable electrode Gibbs isotherm and surface tension

Ion size effects on the osmotic pressure and electrocapillarity in a nanoslit: Symmetric and asymmetric ion sizes

Contact Info

Product

Resources

About

The Thermodynamic Theory of Electrocapillarity¹