Electrochemically Modulated Liquid−Liquid Extraction of Ions

Berduque, Alfonso; Sherburn, Amanda; Ghita, Mihaela; Dryfe, Robert A. W.; Arrigan, Damien W. M.

doi:10.1021/ac051029u

Cited by 56 publications

(68 citation statements)

References 44 publications

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“…As noted previously [15,21,29], amperometric sensors are more suitable for incorporation into FIA systems than potentiometric sensors. Amperometric sensors have the ability to alter the selectivity of ion -transfer across the interface by controlling the Galvani…”

Section: Introductionmentioning

confidence: 79%

“…At this point the flow of the solution is halted, and a stationary cyclic voltammogram (CV) of the solution is run. In this manner the cell setup and parameters used can be verified prior to each experiment [29].…”

Section: Methodsmentioning

confidence: 99%

“…The electrochemical cell used in these studies is fabricated from poly(tetrafluoroethylene) (PTFE) and is based on that employed by Berduque et al [29,31] The aqueous phase was introduced into the Teflon cell by means of a syringe pump (KD Scientific KDS200 series syringe pump) with controllable flow rates. A six-port valve (C22-3186 valve, Carl Stuart Ltd.) was used to inject samples via a 100-µL injection loop.…”

Section: Apparatusmentioning

confidence: 99%

“…The cell was filled with the aqueous phase (10 mM LiCl) and a stationary CV of the blank attained, as described in the methodology. Berduque et al [29,31] have shown that the magnitude of the TEA + transfer peak depends on the applied potential…”

Section: Model Ion Studies: Influence Of Flow Rate On Amperometric Rementioning

confidence: 99%

“…On the whole, this problem was circumvented by gellification of the organic phase with poly(vinyl) chloride (PVC) [12,14,18,20,24,[28][29][30][31][32][33] or insertion of solid porous membrane materials between the two immiscible solutions [13, 15-17, 21, 23, 25-27]. Inevitable reductions in diffusion coefficients of the analyte ions, associated with gellification of the organic phase, have not proven problematic when monitoring ion transfer by amperometric and voltammetric methods.…”

Section: Introductionmentioning

confidence: 99%

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Flow-injection amperometry at microfabricated silicon-based μ-liquid–liquid interface arrays

Scanlon

Berduque

Strutwolf

et al. 2010

Electrochimica Acta

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Geometrically regular silicon membrane-based micropore arrays were employed for defined arrays of micrometer-sized interfaces between two immiscible electrolyte solutions (µITIES).These were incorporated into a poly(tetrafluoroethylene) (PTFE) hydrodynamic cell.Electrochemistry at the µITIES array was undertaken following gellification of the organic phase using polyvinyl chloride (PVC) and flowing an aqueous phase over the array surface.

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Section: Introductionmentioning

confidence: 79%

Section: Methodsmentioning

confidence: 99%

Section: Apparatusmentioning

confidence: 99%

Section: Model Ion Studies: Influence Of Flow Rate On Amperometric Rementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Flow-injection amperometry at microfabricated silicon-based μ-liquid–liquid interface arrays

Scanlon

Berduque

Strutwolf

et al. 2010

Electrochimica Acta

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Liquid/Liquid Interfaces, Electrochemistry atUpdate based on the original article by Frédéric Reymond, Hubert H. Girault,Encyclopedia of Analytical Chemistry, © 2000, John Wiley & Sons, Ltd

Peljo

Girault

2012

Encyclopedia of Analytical Chemistry

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This article outlines the electrochemical methodology at the interface between two immiscible electrolyte solutions (ITIES). The fundamental concepts of the thermodynamics in biphasic systems are presented in order to show how ions are distributed between the two adjacent phases and hence, how a Galvani potential difference is established at an ITIES. Polarizable and nonpolarizable ITIES are then characterized, and it is further evidenced that the classical electroanalytical methodology at a solid electrode can be directly transposed to the ITIES, thereby allowing reversible charge‐transfer reactions to be easily monitored and interpreted. This theoretical approach is completed by a review of the analytical methods used at ITIES, namely cyclic voltammetry (CV), hydrodynamic methods, spectroscopic techniques, and micro‐ and nanointerfaces (which are the biphasic analogs of micro‐ and nanoelectrodes). The last part deals with the practical applications that electrochemistry at ITIES has attracted during the past decades in the development of amperometric and coulometric ion sensors and detectors, detection of macromolecules, extraction of metal ions by interfacial formation of a complex, and assessment of the properties and lipophilicity of ionizable drugs.

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Solvent Extraction: Structure of the Liquid–Liquid Interface Containing a Diamide Ligand

et al. 2016

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Knowledge of the (supra)molecular structure of an interface that contains amphiphilic ligand molecules is necessary for af ull understanding of ion transfer during solvent extraction. Even if molecular dynamics already yield some insight in the molecular configurations in solution, hardly any experimental data giving access to distributions of both extractant molecules and ions at the liquid-liquid interface exist. Here,t he combined application of X-raya nd neutron reflectivity measurements represents ak ey milestone in the deduction of the interfacial structure and potential with respect to two different lipophilic ligands.Indeed, we show for the first time that hardtrivalent cations can be repelled or attracted by the extractant-enriched interface according to the nature of the ligand.Interfaces between two immiscible liquids are ubiquitous in chemistry and biology and are the place of numerous physicochemical processes such as sorption, [1] solvation, [2] complexation. [3] Electron, [4] electrolyte, [2] molecule, [5] or colloid [6] transfer through the liquid interfaces are relevant for numerous domains like chemistry,e lectrochemistry driven solvent extraction, [7] nanoparticle synthesis, [8] or heterogeneous catalysis. [9] Discontinuities between both solvent properties yield different conformations of the solvent molecules at the interface with abreak of the bulk symmetries.This loss of entropy is often related to as pecific orientation of the molecules when they are polarizable and induces ar egion specificity for some reactions or transfer processes.T he surface tension between both phases depends on the molec-ular interactions in this region that are different to those in the respective bulk phases and each species added to one solvent, surface active or not, will modify these interactions and then the structure as well as the dynamics of the pure liquid interface.In solvent extraction using amphiphilic ligands or extractant molecules to separate ions,the ion partitioning between both immiscible phases is significantly enhanced by the extractant/ion complex formation on one side of the interface depending on the hydrophilicity or lipophilicity of the ligand. [10] Therole of complexation (metal-ligand interaction) and supramolecular aggregation of the ligands are strongly determinant in the distribution and separation factors. [11] If the former contribution is stronger and if the complex is soluble in the phase that contains the ligand, the solute transfer from one phase to the other will be fast but its recovery will be difficult. When the equilibrium between both contributions is within af ew k B T [12] then hydrodynamic or interfacial factors become preponderant and have to be taken into account. Ion extraction can be referred to as adiffusionlimited or areaction-limited process depending on the height of the energy barrier at the liquid-liquid (LL) interface. [13] Thepresent contribution shows that determination of the extractant and ion distributions across the water-oil interface can help the un...

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Electrochemically Modulated Liquid−Liquid Extraction of Ions

Cited by 56 publications

References 44 publications

Flow-injection amperometry at microfabricated silicon-based μ-liquid–liquid interface arrays

Flow-injection amperometry at microfabricated silicon-based μ-liquid–liquid interface arrays

Liquid/Liquid Interfaces, Electrochemistry atUpdate based on the original article by Frédéric Reymond, Hubert H. Girault,Encyclopedia of Analytical Chemistry, © 2000, John Wiley & Sons, Ltd

Solvent Extraction: Structure of the Liquid–Liquid Interface Containing a Diamide Ligand

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