Diffusion effects at microhole supported liquid/liquid interfaces

Wilke, Stefan; Zerihun, Tadesse

doi:10.1016/s0013-4686(98)00147-9

Cited by 55 publications

(64 citation statements)

References 17 publications

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“…Besides the standard experimental arrangement for studying the ion transfer at the interface of immiscible electrolyte solutions (ITIES) based on a four electrode configuration [3][4][5][6][7], in recent years a few attempts have been made to utilize a three electrode arrangement to assess both the ion and the electron transfer processes across the L j L interface. Anson and co-workers [8][9][10][11][12][13] used a solid graphite electrode, the surface of which is completely covered with a thin film of an organic liquid containing an electroactive probe and immersed in an aqueous electrolyte (see Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Square-wave thin-film voltammetry: influence of uncompensated resistance and charge transfer kinetics

Mirčeski

Gulaboski

Scholz

2004

Journal of Electroanalytical Chemistry

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An electrode reaction occurring in a thin-film having a low electrical conductivity was considered under conditions of squarewave voltammetry (SWV). The ohmic polarization of the system owing to the low conductivity of the film is represented by the complex resistance parameter defined as, where R X is the resistance of the film, S is the electrode surface area, f is the SW frequency and the other symbols have their usual meanings. The influence of the thickness of the film is given by the thickness parameterwhere L is the thickness of the layer, and D is the diffusion coefficient. For a thin film (K 6 0:949) the dimensionless net-peak current of a reversible electrode reaction depends parabolically on the resistance parameter, exhibiting a well-developed maximum. A detailed study of this phenomenon revealed that it resembles the charge transfer kinetics effect as well as the property known as a ''quasireversible maximum'' that is typical for an adsorption complicated electrode reaction. The theoretically predicted properties of the SW response are illustrated by experiments with iodine, decamethylferrocene, and azobenzene at the three-phase electrode system. This methodology [Electrochem. Commun. 2 (2000) 112] consists of a single droplet of an organic water immiscible solvent containing an electroactive probe that is attached to the surface of a graphite electrode and immersed in an aqueous electrolyte solution. A good agreement between theory and experiment indicates that the SW voltammetric response of the three-phase electrode system exhibits properties of an electrode reaction occurring under limiting diffusion conditions.

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Section: Introductionmentioning

confidence: 99%

Square-wave thin-film voltammetry: influence of uncompensated resistance and charge transfer kinetics

Mirčeski

Gulaboski

Scholz

2004

Journal of Electroanalytical Chemistry

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“…They are often correlated with biological and pharmacological activity, such as adsorption, cell membrane permeability and hydrophobic binding. 4,5 Although large and significant progress has been achieved in the last decade, [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] standard Gibbs energies of transfer of many common inorganic ions are still not available. 6 One reason for this situation are the limitations of the four-electrode technique.…”

Section: Introductionmentioning

confidence: 99%

“…As a consequence, in some cases less reliable data have been reported in the literature, with values of DG falling close to the end of the potential window. Recent modifications in the four-electrode technique allowed an expansion of the potential window in ITIES experiments by measurements at microhole interfaces [7][8][9][10][11][12] or indirectly by coupling of chemical equilibria in both phases. 7,[17][18][19][20] However, the non-polarizability of some organic solvents (e.g.…”

Section: Introductionmentioning

confidence: 99%

“…they are more reliable. 2,[6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22] The electrochemical technique introduced by one of us 24 and successfully applied to a number of systems [25][26][27][28][29] explores a so called '' three-phase electrode '' and conventional threeelectrode instrumentation. With this technique standard Gibbs energies for the water/nitrobenzene system can be determined in the range from À41 to +37 kJ mol À1 , 28 without coupling of solution equilibria.…”

Section: Introductionmentioning

confidence: 99%

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Standard Gibbs energies of transfer of halogenate and pseudohalogenate ions, halogen substituted acetates, and cycloalkyl carboxylate anions at the water|nitrobenzene interface

Gulaboski

Riedl

Scholz

2003

Phys. Chem. Chem. Phys.

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The previously introduced three-phase electrode technique was used to determine the Gibbs energies of transfer of ClO 3 Cl,Br,I), and cycloalkyl carboxylate anions ((CH 2 ) n COO À , n ¼ 3,. . .,7) at the water|nitrobenzene interface. Whereas the data for the small inorganic ions can easily be understood in terms of ion-dipole interactions, the data of the organic ions need consideration of charge delocalisation and its effect on the enthalpy and entropy of solvation.

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“…The transfer across the water|nitrobenzene interface has been studied in the following anions: octoate [201] dodecylsulfate [201,202]; picrate [98,[201][202][203][204][205][206][207][208][209][210][211][212][213][214][215] [250]. A huge number of cations have also been measured in the water|nitrobenzene interface: tetrabutylammonium (TBA + ) [15,19,210,212,213,217,230,[255][256][257][258][259][260]; tetraethylammonium (TEA + ) [19-21, 98, 202, 208-214, 218, 222, 254, 256, 259-266]; tetrapropylammonium (TPrA + ) [19,208,211,213,218,255,256,259,263]; tetramethylammonium (TMA + ) [20, 37, 84, 98, 202, 208-214, 218, 222, 230, 257, 259, 260, 262, 263, 266-269]; tetrapentylammonium (TPenA + ) [224,…”

Section: Water|nitrobenzene Interfacementioning

confidence: 99%

Simple Ion Transfer at Liquid|Liquid Interfaces

Vallejo

Ovejero

Fernández

et al. 2012

International Journal of Electrochemistry

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The main aspects related to the charge transfer reactions occurring at the interface between two immiscible electrolyte solutions (ITIES) are described. The particular topics to be discussed involve simple ion transfer. Focus is given on theoretical approaches, numerical simulations, and experimental methodologies. Concerning the theoretical procedures, different computational simulations related to simple ion transfer are reviewed. The main conclusions drawn from the most accepted models are described and analyzed in regard to their relevance for explaining different aspects of ion transfer. We describe numerical simulations implementing different approaches for solving the differential equations associated with the mass transport and charge transfer. These numerical simulations are correlated with selected experimental results; their usefulness in designing new experiments is summarized. Finally, many practical applications can be envisaged regarding the determination of physicochemical properties, electroanalysis, drug lipophilicity, and phase-transfer catalysis.

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Diffusion effects at microhole supported liquid/liquid interfaces

Cited by 55 publications

References 17 publications

Square-wave thin-film voltammetry: influence of uncompensated resistance and charge transfer kinetics

Square-wave thin-film voltammetry: influence of uncompensated resistance and charge transfer kinetics

Standard Gibbs energies of transfer of halogenate and pseudohalogenate ions, halogen substituted acetates, and cycloalkyl carboxylate anions at the water|nitrobenzene interface

Simple Ion Transfer at Liquid|Liquid Interfaces

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