On the capacity of liquid-liquid interfaces

Pereira, Carlos M.; Schmickler, Wolfgang; Silva, A.F.; Sousa, M. J. Lemos de

doi:10.1016/s0009-2614(97)00159-0

Cited by 52 publications

(47 citation statements)

References 14 publications

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“…These two views result in two very different chemical environments for molecules at the interface. Interfacial tension and electrical capacitance measurements at the interface between two electrolyte solutions have provided arguments both for and against the sharp interfacial region 128,[230][231][232][233][234][235][236][237] .…”

Section: Fundamental Studiesmentioning

confidence: 99%

Interface Between Two Immiscible Liquid Electrolytes: A Review

Vanýsek

Ramírez²

2008

J. Chil. Chem. Soc.

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Section: Fundamental Studiesmentioning

confidence: 99%

Interface Between Two Immiscible Liquid Electrolytes: A Review

Vanýsek

Ramírez²

2008

J. Chil. Chem. Soc.

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“…2(b)). The typical absolute values of the effect lie in the observed interval [8]. They depend strongly on the cutoff (Fig.…”

Section: Resultsmentioning

confidence: 81%

“…However, in spite of the importance of the electrical properties of these interfaces, the experimental data are still limited [1,2,[4][5][6][7], and there is no unambiguous picture for their interpretation. For instance, the treatment of interfacial capacitance in terms of the capacitance of two 'back-toback' Gouy-Chapman double layers works fairly well for some liquid/liquid combinations, while it fails for the majority of others [8]. This discrepancy has stimulated theoretical works, which go beyond the classical Gouy -Chapman scheme including the ion pairing at the interface and the 'mixed boundary layer' [8,9].…”

Section: Introductionmentioning

confidence: 99%

“…For instance, the treatment of interfacial capacitance in terms of the capacitance of two 'back-toback' Gouy-Chapman double layers works fairly well for some liquid/liquid combinations, while it fails for the majority of others [8]. This discrepancy has stimulated theoretical works, which go beyond the classical Gouy -Chapman scheme including the ion pairing at the interface and the 'mixed boundary layer' [8,9].…”

Section: Introductionmentioning

confidence: 99%

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Effect of capillary waves on the double layer capacitance of the interface between two immiscible electrolytes

Daikhin

Kornyshev

Urbakh

1999

Electrochimica Acta

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The effect of capillary waves on the double layer capacitance of the interface between two immiscible electrolytes has been studied. We have found that a corrugation of the interface due to capillary waves leads to an increase in the capacitance, as compared with the Gouy-Chapman result for a flat interface. The theory offers a concept of a roughness function, R 0 , which determines the deviation of capacitance from the Gouy -Chapman result. R 0 is a function of Debye lengths of the two immiscible electrolytes. Analytical expression for the roughness function has been derived which shows a strong dependence of R 0 on the interfacial tension and the dielectric constants of contacting solutions. Predictions amenable to experimental tests have been discussed.

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“…13,14,21 Daikhin and co-authors modeled ion penetration across the interface by using a free energy profile of ion transfer that varied smoothly through the interface. 22,23 In spite of many studies of ITIES that utilized impedance spectroscopy and interfacial tension measurements, these techniques did not lead to a detailed understanding of the interfacial ion distribution.…”

mentioning

confidence: 99%

Ion Distributions at Electrified Water-Organic Interfaces: PB-PMF Calculations and Impedance Spectroscopy Measurements

Hou

Luo

et al. 2015

J. Electrochem. Soc.

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The interface between two immiscible electrolyte solutions consisting of alkali chlorides in water and the organic electrolyte BTPPATPFB in 1,2-dichloroethane is characterized with X-ray reflectivity, interfacial tension and impedance spectroscopy measurements over a range of applied voltage between the bulk solutions. X-ray reflectivity probes the interfacial ion distribution on the sub-nanometer length scale, whereas interfacial tension and impedance spectroscopy characterize quantities such as interfacial excess charge and differential capacitance that represent integrations over the interfacial ion distribution. Predictions of interfacial ion distributions by the recently introduced PB-PMF method, which combines Poisson's equation with ion potentials of mean force, provide excellent agreement, within one to two experimental standard deviations, with both X-ray reflectivity and interfacial tension measurements. However, the agreement with the differential capacitance measured by impedance spectroscopy, and modeled by the Randles equivalent circuit, is not as good. Values of measured and calculated differential capacitance can deviate by as much as 20% for applied electric potential differences larger than approximately ±100 mV. These comparisons indicate that our understanding of the ion distributions that underlie these measurements is adequate, but that further understanding of the modeling of impedance spectroscopy data is required for quantitative agreement at larger applied electric potential differences. Ion distributions at interfaces underlie many electrochemical and biological processes, including electron and ion transfer across biomembranes and liquid interfaces, phase transfer catalysis and solvent extraction. The interface between two immiscible electrolyte solutions (ITIES) has been used as a model system to study ion and electron transfer across liquid-liquid interfaces by electrochemical techniques.1,2 These techniques characterize the interfacial ion distribution in terms of integrated properties such as interfacial excess charge or differential capacitance, which can be calculated by integrating the ion distribution over the spatial coordinate perpendicular to the interface.The differential capacitance of ITIES has been widely investigated.3-5 Impedance spectroscopy data for ITIES are often modeled by the Randles equivalent circuit to yield the interfacial differential capacitance. 6 Although this model is convenient in many circumstances, its limitations have been discussed in the literature. For example, Samec and co-authors reported limited agreement between the results from interfacial tension and impedance spectroscopy measurements of the interface between aqueous and 1,2-dichloroethane (DCE) electrolyte solutions and suggested that the Randles equivalent circuit might be at fault at high electric potential differences. 7,8 Impedance spectroscopy studies of ITIES have measured interfacial differential capacitance that depends on the nature of the ions. 4,[9][10][11][12][13][14] Interfac...

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On the capacity of liquid-liquid interfaces

Cited by 52 publications

References 14 publications

Interface Between Two Immiscible Liquid Electrolytes: A Review

Interface Between Two Immiscible Liquid Electrolytes: A Review

Effect of capillary waves on the double layer capacitance of the interface between two immiscible electrolytes

Ion Distributions at Electrified Water-Organic Interfaces: PB-PMF Calculations and Impedance Spectroscopy Measurements

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