Ion association at liquid|liquid interfaces

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

doi:10.1016/s0022-0728(97)00283-0

Cited by 62 publications

(43 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The experimental conditions used in this work are described in detail in preceding papers [22,23]. Briefly the current measured during cyclic voltammetry is by convention taken positive for the crossing of a positive charge from the water to the oil phase.…”

Section: Methodsmentioning

confidence: 99%

Ag+ transfer across the water/1,2-dichloroethane interface facilitated by complex formation with tetraphenylborate derivatives

Caçote

Pereira

Tomaszewski

et al. 2004

Electrochimica Acta

Self Cite

View full text Add to dashboard Cite

The assisted transfer of silver ion, Ag + , by complexation of Ag + with the tetrakis(4-chlorophenyl)borate (TPBCl − ) anion was studied at the interface between two immiscible electrolyte solutions (ITIES).The elucidation of the interfacial mechanisms employed the cyclic voltammetry technique applied to macro and micro liquid/liquid interfaces. This procedure allowed to identify Ag + as the species which is transferred at the liquid/liquid interface and also the formation of an 1:2 metal:ligand complex when TPBCl − is in excess. The value for the formal transfer potential of silver(I) from aqueous to 1,2-dichloroethane was evaluated and the association constant for the [Ag(TPBCl) 2 ]− complex was determined.

show abstract

Section: Methodsmentioning

confidence: 99%

Ag+ transfer across the water/1,2-dichloroethane interface facilitated by complex formation with tetraphenylborate derivatives

Caçote

Pereira

Tomaszewski

et al. 2004

Electrochimica Acta

Self Cite

View full text Add to dashboard Cite

show abstract

“…However, molecular dynamics simulations mainly focus on the neat molecular interface with only a few ions being considered. Computer simulation has been extended to more complex systems by the use of the lattice gas model, which is a rather useful theoretical approach to model the space charge regions at the interface [23][24][25][26][27]. The use of this model allowed the computation of charge transfer, specific ion adsorption, and ion pairing processes, as well as of the interfacial structure.…”

Section: Introductionmentioning

confidence: 99%

Simulations of the adsorption of ionic species at polarisable liquid∣liquid interfaces

Eugster

2005

Journal of Electroanalytical Chemistry

View full text Add to dashboard Cite

The adsorption of ions at the interface between two immiscible electrolyte solutions (ITIES) is primarily controlled by the potential distribution across the interface, which in turn is influenced by the adsorption process. In the present paper, we simulate the effect of the adsorption of charged species on the charge distribution at the ITIES based on the classical description of the interface employing the Gouy-Chapman model. The inner layer is considered as a charged plane, where the ionic adsorption takes place. The potential at this plane is determined by the electro-neutrality condition. Various adsorption isotherms are considered, including potential dependent isotherms based on the Langmuir and Frumkin adsorption models. The potential distribution and the charge density profile are derived by solving the Poisson-Boltzman equation numerically. We show that the charge distribution in the interfacial region is significantly affected by the adsorption of ionic species. Under certain conditions, the adsorption results in a nonmonotonic potential distribution with a potential trap at the interface.

show abstract

“…1-18͒ as has that of electron transfers [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] and of various liquid/liquid interfacial properties. [37][38][39][40][41][42][43][44][45][46][47][48] In the present article several factors are considered in formulating a theory of ion transfer across these interfaces. There have been a number of theories of the ion transfer, [49][50][51][52][53][54][55] as well as computer-based insight, [56][57][58][59][60][61][62][63][64][65][66] and we draw upon some of these studies.…”

Section: Introductionmentioning

confidence: 99%

On the theory of ion transfer rates across the interface of two immiscible liquids

Marcus

2000

The Journal of Chemical Physics

View full text Add to dashboard Cite

Ion transfer across the interface of two immiscible liquids involves a mechanism for initiating desolvation from the first liquid, A, and concerted solvation by the second, B. In the present article a mechanism is considered in which this initiation is facilitated by the ion attaching itself to the tip of a solvent protrusion of B into A. ͑Protrusions have been observed in computer simulations and termed ''fingers'' or ''cones.''͒ It is presumed that the most effective protrusion represents a balance between two opposing effects: the more convex the protrusion the less probable the ion/ protrusion formation but also the less the resistance to extrusion of the intervening liquid between the ion and the surface. An analogy of the latter to hydrodynamics is noted, namely, the more convex the surface the less the frictional force it exerts on the approaching ion. After diffusion in coordinate and solvation space across the interfacial region, the final detachment of the ion from solvent A is assumed to occur from a protrusion of A into B. Existing data on ion transfer rates are discussed, including the question of diffusion vs kinetic control. Computer simulations that correspond to the experimental conditions in realistic liquids for measurement of the electrochemical exchange current rate constant k 0 are suggested. They can be used to test specific theoretical features. With a suitable choice of systems the need ͑and a major barrier to the simulations͒ for having a base electrolyte in such simulations can be bypassed. An experiment for the real-time observation of an ion leaving the interface is also suggested.

show abstract

Ion association at liquid|liquid interfaces

Cited by 62 publications

References 6 publications

Ag+ transfer across the water/1,2-dichloroethane interface facilitated by complex formation with tetraphenylborate derivatives

Ag+ transfer across the water/1,2-dichloroethane interface facilitated by complex formation with tetraphenylborate derivatives

Simulations of the adsorption of ionic species at polarisable liquid∣liquid interfaces

On the theory of ion transfer rates across the interface of two immiscible liquids

Contact Info

Product

Resources

About