Ion distributions at the nitrobenzene–water interface electrified by a common ion

Luo, Guangming; Málková, Šárka; Yoon, Jaesung; Schultz, David G.; Lin, Binhua; Meron, Mati; Benjamin, Ilan; Vanýsek, Petr; Schlossman, Mark L.

doi:10.1016/j.jelechem.2006.03.051

Cited by 46 publications

(78 citation statements)

References 85 publications

(169 reference statements)

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“…It has been found that while the mean-field Poisson-Boltzmann framework provides a generally good description for the ion profiles that matches well with experimental results obtained by x-ray structural measurements, the linearized Guoy-Chapman approximation is insufficient for most general cases (24). For completeness, we will now illustrate the solution to the Poisson-Boltzmann equation for the case when the membrane across the two dielectric media is charged (polarizable), including the particular interesting case of the neutral (non-polarizable) interface.…”

Section: Case Study Definedsupporting

confidence: 59%

Adsorption Profiles and Solvation of Ions at Liquid-Liquid Interfaces and Membranes

Kung¹,

Solis²,

Cruz³

2011

Application of Thermodynamics to Biological and Materials Science

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Section: Case Study Definedsupporting

confidence: 59%

Adsorption Profiles and Solvation of Ions at Liquid-Liquid Interfaces and Membranes

Kung¹,

Solis²,

Cruz³

2011

Application of Thermodynamics to Biological and Materials Science

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“…As a result of the higher relative permittivity of nitrobenzene (e r = 34.8) and the lower range of electric potential (jΔϕ max j = 0:277 V), the correlation coupling strength in those experiments was small (Γ ≈ 0.7), and it was shown that the effect of correlations was negligible (13). However, the reflectivity data in Fig.…”

Section: Discussionmentioning

confidence: 86%

“…This theory predicts the ion number density profiles nðzÞ, which are then used to calculate electron density profiles ρðzÞ (12,13). X-ray reflectivity is determined from ρðzÞ by use of the Parratt algorithm (14).…”

Section: Resultsmentioning

confidence: 99%

“…Earlier X-ray reflectivity studies showed that ion distributions at the liquid/liquid interface can be modeled accurately by a PB equation that has been modified to include ion-solvent interactions when ion-ion correlations are negligible (12,13). Excellent agreement was obtained between experiment and theory, without adjustable parameters, when ion-solvent interactions near the interface were modeled by a molecular dynamics simulation of the potential of mean force of a single ion in the vicinity of the interface between pure solvents (12,13). Here, we will show that ion-ion correlations, in addition to ion-solvent interactions, are required to explain the data in Fig.…”

Section: Resultsmentioning

confidence: 99%

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Tuning ion correlations at an electrified soft interface

Laanait

Mihaylov

Hou

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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101

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Ion distributions play a central role in various settings-from biology, where they mediate the electrostatic interactions between charged biomolecules in solution, to energy storage devices, where they influence the charging properties of supercapacitors. These distributions are determined by interactions dictated by the chemical properties of the ions and their environment as well as the long-range nature of the electrostatic force. Recent theoretical and computational studies have explored the role of correlations between ions, which have been suggested to underlie a number of counterintuitive results, such as like-charge attraction. However, the interdependency between ion correlations and other interactions that ions experience in solution complicates the connection between physical models of ion correlations and the experimental investigation of ion distributions. We exploit the properties of the liquid/liquid interface to vary the coupling strength Γ of ion-ion correlations from weak to strong while monitoring their influence on ion distributions at the nanometer scale with X-ray reflectivity and the macroscopic scale with interfacial tension measurements. These data are in agreement with the predictions of a parameterfree density functional theory that includes ion-ion correlations and ion-solvent interactions over the entire range of experimentally tunable correlation coupling strengths (from 0.8 to 3.7). This study provides evidence for a sharply defined electrical double layer for large coupling strengths in contrast to the diffuse distributions predicted by mean field theory, thereby confirming a common prediction of many ion correlation models. The reported findings represent a significant advance in elucidating the nature and role of ion correlations in charged soft matter.liquid surface scattering | ion density profile | surface excess charge | Poisson-Boltzmann | Debye-Hückel hole T he works by Gouy (1) and Chapman (2) introduced the Poisson-Boltzmann (PB) equation to describe the distribution of ions and the accompanying variation of electric potential at the interface between a charged planar electrode and an electrolyte solution (1, 2). This seminal theory considered point-like ions interacting through their mean electric field in a continuum solvent but neglected both chemically specific ion-solvent interactions and correlations between ions. Specific ion interactions are exemplified by the well-known Hofmeister series (3). The study of ion correlations has been motivated by observations of the reentrant condensation of DNA (4) and proteins (5) in solution, in which like-charged biomolecules aggregate in the presence of multivalent ions, and reports of charge reversal in colloidal suspensions, in which the sign of the screened charge on a colloid can be changed by varying the surrounding electrolyte solution (6, 7).Correlations between ions that are caused by their electrostatic interactions are expected to be important when the average electrostatic interaction energy between neighboring ions...

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“…Recently, Schlossman and coworkers [184][185][186][187] have used synchrotron X-ray reflectivity to study ion distribution at the liquid|liquid interface between a nitrobenzene solution of tetrabutylammonium tetraphenylborate and a water solution of tetrabutylammonium bromide. These structural measurements are well described by the ion distributions predicted by a version of the Poisson-Boltzmann equation that explicitly includes a free energy profile for ion transfer across the interface.…”

Section: Other Techniquesmentioning

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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Ion distributions at the nitrobenzene–water interface electrified by a common ion

Cited by 46 publications

References 85 publications

Adsorption Profiles and Solvation of Ions at Liquid-Liquid Interfaces and Membranes

Adsorption Profiles and Solvation of Ions at Liquid-Liquid Interfaces and Membranes

Tuning ion correlations at an electrified soft interface

Simple Ion Transfer at Liquid|Liquid Interfaces

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