Facilitated ion transfer reactions across oil|water interfaces

Reymond, Frédéric; Lagger, Grégoire; Carrupt, Pierre‐Alain; Girault, Hubert H.

doi:10.1016/s0022-0728(97)00428-2

Cited by 110 publications

(158 citation statements)

References 34 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%

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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“…Reymond et al 11 mentioned that not only the metal-ligand complex but also the free metallic ion moves across the interface at the high voltage when the metallic ion is in excess. Figure 2 shows i-E curves for the transfer of metal-HQ complex across water/DCE interface, when various metals are contained in the aqueous phase.…”

Section: Resultsmentioning

confidence: 99%

“…Reymond et al 10 developed an analytical method which used the half-wave potential, assuming that the diffusion coefficients are constant, and reported the complex stoichiometry (ratio of metallic ion to ligand) was related to concentrations of metallic ion and ligand. Furthermore, Reymond et al 11 derived the theoretical expressions of the half-wave potential for transfer mechanisms by interfacial complexation/decomplexation (TIC/TID mechanism), by organic phase complexation (TOC mechanism) and by aqueous phase complexation (ACT mechanism). They reported that the complex of Pb(II) and 1,4,7,10-tetrathiacyclododecane (TTCD) had the multiple stoichiometries of 1:1 and 1:2 (metallic ion to ligand) in the transfer across water/1,2-dichloroethane (DCE) interface.…”

Section: Introductionmentioning

confidence: 99%

Studies on Electrochemical Solvent Extraction of Metal Ions at Water/1,2-dichloroethane Interface

2001

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Solvent extraction is one significant method to separate many kinds of metals. The solvent extraction involves the process by which a metal complex moves from aqueous phase to organic phase. The electrochemical study has been applied to the investigation of the interface between two immiscible electrolyte solutions (ITIES) because of the following advantages. An ionic transfer reaction rate at the interface can be controlled easily by the interfacial potential difference (or current). Therefore, it is possible to carry the metal complex across ITIES by the electrochemical driving force when the metal complex has an electrical charge. Freiser et al. [1][2][3][4][5] studied the transfer of the metallic ions which moved across the liquid/liquid interface by using voltammetry. investigated the ion transfer across the water/nitrobenzene interface by electrochemical methods, and discussed the reaction parameters for various cation transfers. Reymond et al. 10 developed an analytical method which used the half-wave potential, assuming that the diffusion coefficients are constant, and reported the complex stoichiometry (ratio of metallic ion to ligand) was related to concentrations of metallic ion and ligand. Furthermore, Reymond et al. 11 derived the theoretical expressions of the half-wave potential for transfer mechanisms by interfacial complexation/decomplexation (TIC/TID mechanism), by organic phase complexation (TOC mechanism) and by aqueous phase complexation (ACT mechanism). They reported that the complex of Pb(II) and 1,4,7,10-tetrathiacyclododecane (TTCD) had the multiple stoichiometries of 1:1 and 1:2 (metallic ion to ligand) in the transfer across water/1,2-dichloroethane (DCE) interface. Liu et al. 12 measured the voltammograms for transfer of Cd(II), Mg(II), Co(II), Zn(II), Cu(II) and Ni(II) across ITIES by using an ascending water electrode (AWE) and a stationary water electrode (SWE) system.Itagaki et al. 13 applied an electrochemical impedance spectroscopy (EIS) to the analysis of the solvent extraction of some metals. They examined the rate of solvent extraction and the correlation of the extraction rate and the distribution constant. The EIS discriminates the elementary steps in the solvent extraction, namely, the diffusion in aqueous and organic phases, and the charge transfer across ITIES. The authors 14 discussed the charge transfer mechanism of Mn(II) extracted by HQ into DCE by EIS, and showed that the measurement of EIS gave the rate constant and the interfacial capacitance. The authors 15,16 extended this method to analyses of the solvent extraction of Co(II) and Ni(II). In the previous work, 16 the Ni(II) species extracted by electrochemical driving force were confirmed by the in-situ determination of absorbance by spectrophotometry with an optical fiber system. Aprahamian et al. 17 and Watanabe et al. 18 measured rate constants of solvent extraction at the liquid/liquid interface by accelerating extraction rate with high-speed solvent stirring. Contrary to this, the rate constant at a stati...

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Facilitated ion transfer reactions across oil|water interfaces

Cited by 110 publications

References 34 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

Studies on Electrochemical Solvent Extraction of Metal Ions at Water/1,2-dichloroethane Interface

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