The interface between two immiscible solutions

Most of the liquid-liquid interfaces that have been studied involve water and an organic solvent such as nitrobenzene or 1,2-dichloroethane (1,2-DCE). Although these systems form stable interfaces, the solubility of one solvent in the other is usually quite high. For example, the solubility of water in 1,2-DCE is 0.11 M, and that of 1,2-DCE in water is 0.09 M. So each of the two liquid components is a fairly concentrated solution of one solvent in the other. It is therefore unlikely that the interface is sharp on a molecular level. We rather expect an extended region with a thickness of the order of a few solvent diameters, over which the concentrations of the two solvents change rapidly (see Fig. 12.1). The lower the solubility of one solvent in the other, the thinner this interfacial region should be. These expectations are supported by the indication that the dipole potentials at these interfaces seem to be small, at least near the pzc, but spectroscopic information is lacking at present. 

Many of the processes that are familiar from ordinary electrochemistry have an analog at ITIES so these form a wide field of study. We limit ourselves to a brief introduction into a few important topics thermodynamics, double-layer properties, and charge-transfer reactions. Further details can be found in several good review articles 

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As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

Heterogeneous electron reactions at liquid liquid interfaces occur in many chemical and biological systems. The interfaces between two immiscible solutions in water-nitrobenzene and water 1,2-dichloroethane are broadly used for modeling studies of kinetics of electron transfer between redox couples present in both media. The basic scheme of such a reaction is... 

Figure 12.1 Distribution of particles and charge at the interface between two immiscible solutions.

Interfacial Polymerization Interfacial polymerization is a process whereby very thin films or membranes, on the order of nanometer thickness, are produced by reacting two monomers at the interface between two immiscible solutions [199], Nanoparticles [200] and aqueous core capsules with very thin membranes have been produced using this method for drug delivery applications. 

Figure 1. Comparison of the interface between an electronically conductive electrode and a solution reduction of Fe3+) (A) and the interface between two immiscible solutions of electrolytes (ITIES) during current flow in a closed electric circuit [transport of picrate (Pi ) from nonaqueous phase (n) to water (w)] (B). (Reproduced from reference 4. Copyright 1990 American Chemical...

The interface between two immiscible solutions (e.g. water and nitrobenzene) containing dissolved species is a site of an electric potential. By measuring this potential difference at the aqueous elec-trolyte/solid electrolyte phase boundary, the phenomena taking place at the interface between two immiscible solutions or the membranes of ion-selective electrode have been studied. Changing the composition of the solutions in contact can alter this potential or applied current can alter the composition of the solutions. Thus, judicious choice of applied potential or current can be used to study the structure of the interface. Since the interface is ul-trathin (< cl nm), it cannot be observed directly. It can be, however, investigated by electrochemical or optical methods [14,... 

The first major observation of ionic current across the interface between two immiscible solutions was reported by Nernst and Riesenfeld," who in 1902, studied the transport of colored electrolytes across water-phenol-water concentration cells. However, it was only in 1974 that Gavach et al applied what we could call... 

Figure 5.3. A cellular automata model of the interface between two immiscible bquids, after the demixing process has reached an equilibrium. A solute (encircled cells) has partitioned into the two phases according to its partition coefficient...

Liquid surfaces and liquid-liquid interfaces are very common and have tremendous significance in the real world. Especially important are the interfaces between two immiscible liquid electrolyte solutions (acronym ITIES), which occur in tissues and cells of all living organisms. The usual presence of aqueous electrolyte solution as one phase of ITIES is the main reason for the electrochemical nature of such interfaces. 

A. R. Brown. Photoelectrochemical Processes at the Interface Between Two Immiscible Electrolyte Solutions. PhD Thesis, University of Edinburgh, Edinburgh, 1992. 

The theoretical results described have implications for the design of experimental approaches for the study of transfer processes across the interface between two immiscible phases. The current response in SECMIT is clearly sensitive to the relative diffusion coefficients and concentrations of a solute in the two phases and the kinetics of interfacial transfer over a wide range of values of these parameters. 

The structure of the interface between two immiscible electrolyte solutions (ITIES) has been the matter of considerable interest since the beginning of the last century [1], Typically, such a system consists of water (w) and an organic solvent (o) immiscible with it, each containing an electrolyte. Much information about the ITIES has been gained by application of techniques that involve measurements of the macroscopic properties, such as surface tension or differential capacity. The analysis of these properties in terms of various microscopic models has allowed us to draw some conclusions about the distribution and orientation of ions and neutral molecules at the ITIES. The purpose of the present chapter is to summarize the key results in this field. 

In particular, the coupling between the ion transfer and ion adsorption process has serious consequences for the evaluation of the differential capacity or the kinetic parameters from the impedance data [55]. This is the case, e.g., of the interface between two immiscible electrolyte solutions each containing a transferable ion, which adsorbs specifically on both sides of the interface. In general, the separation of the real and the imaginary terms in the complex impedance of such an ITIES is not straightforward, and the interpretation of the impedance in terms of the Randles-type equivalent circuit is not appropriate [54]. More transparent expressions are obtained when the effect of either the potential difference or the ion concentration on the specific ion adsorption is negli-... 

V. Gobry, F. Re5miond and H. H. Girault, Refinment of Ionic Partition Diagrams and Determination of Partition Coefficients of Multiprotic Compounds by Electrochemistry at the Interface between Two Immiscible Electrolyte Solutions, submitted. 

Potential differences at the interface between two immiscible electrolyte solutions (ITIES) are typical Galvani potential differences and cannot be measured directly. However, their existence follows from the properties of the electrical double layer at the ITIES (Section 4.5.3) and from the kinetics of charge transfer across the ITIES (Section 5.3.2). By means of potential differences at the ITIES or at the aqueous electrolyte-solid electrolyte phase boundary (Eq. 3.1.23), the phenomena occurring at the membranes of ion-selective electrodes (Section 6.3) can be explained. 

Electrical double layers are also characteristic of the semiconductor-electrolyte solution, solid electrolyte or insulator-electrolyte solution interface and for the interface between two immiscible electrolyte solutions (ITIES) (Section 4.5). 

For semiconductor electrodes and also for the interface between two immiscible electrolyte solutions (ITIES), the greatest part of the potential difference between the two phases is represented by the potentials of the diffuse electric layers in the two phases (see Eq. 4.5.18). The rate of the charge transfer across the compact part of the double layer then depends very little on the overall potential difference. The potential dependence of the charge transfer rate is connected with the change in concentration of the transferred species at the boundary resulting from the potentials in the diffuse layers (Eq. 4.3.5), which, of course, depend on the overall potential difference between the two phases. In the case of simple ion transfer across ITIES, the process is very rapid being, in fact, a sort of diffusion accompanied with a resolvation in the recipient phase. 

Z. Samec, E. Samcova, and H.H. Girault, Ion amperometry at the interface between two immiscible electrolyte solutions in view of realizing the amperometric ion-selective electrode. Talcmta 63, 21—32 (2004). 

This definition requires some explanation. (1) By interface we denote those regions of the two adjoining phases whose properties differ significantly from those of the bulk. These interfacial regions can be quite extended, particularly in those cases where a metal or semiconducting electrode is covered by a thin film. Sometimes the term interphase is used to indicate the spatial extention. (2) It would have been more natural to restrict the definition to the interface between an electronic and an ionic conductor only, and, indeed, this is generally what we mean by the term electrochemical interface. However, the study of the interface between two immiscible electrolyte solutions is so similar that it is natural to include it under the scope of electrochemistry. 

The previous chapters dealt with ISE systems at zero current, i.e. at equilibrium or steady-state. The properties of the interface between two immiscible electrolyte solutions (ITIES), described in sections 2.4 and 2.5, will now be used to describe a dynamic method based on the passage of electrical current across ITIES. Voltammetry at ITIES (for a survey see [3, 8, 9, 10, 11, 12,18]) is an inverse analogue of potentiometry with liquid-membrane ISEs and thus forms a suitable conclusion to this book. 

Voltammetry at the Interface Between Two Immiscible Electrolyte Solutions... 

The electrodes used in conventional polarography and voltammetry are electronic conductors such as metals, carbons or semiconductors. In an electrode reaction, an electron transfer occurs at the electrode/solution interface. Recently, however, it has become possible to measure both ion transfer and electron transfer at the interface between two immiscible electrolyte solutions (ITIES) by means of polarography and voltammetry [16]. Typical examples of the immiscible liquid-liquid interface are water/nitrobenzene (NB) and water/l,2-dichloroethane (DCE). 

Emulsions made by agitation of pure immiscible liquids are usually very unstable and break within a short time. Therefore, a surfactant, mostly termed emulsifier, is necessary for stabilisation. Emulsifiers reduce the interfacial tension and, hence, the total free energy of the interface between two immiscible phases. Furthermore, they initiate a steric or an electrostatic repulsion between the droplets and, thus, prevent coalescence. So-called macroemulsions are in general opaque and have a drop size > 400 nm. In specific cases, two immiscible liquids form transparent systems with submicroscopic droplets, and these are termed microemulsions. Generally speaking a microemulsion is formed when a micellar solution is in contact with hydrocarbon or another oil which is spontaneously solubilised. Then the micelles transform into microemulsion droplets which are thermodynamically stable and their typical size lies in the range of 5-50 nm. Furthermore bicontinuous microemulsions are also known and, sometimes, blue-white emulsions with an intermediate drop size are named miniemulsions. In certain cases they can have a quite uniform drop size distribution and only a small content of surfactant. An interesting application of this emulsion type is the encapsulation of active substances after a polymerisation step [25, 26]. 

This experiment is an example of a step-growth polymerization that takes place at the interface of two immiscible solutions. For this reaction, a diamine dissolved in water reacts with a diacid chloride that is dissolved in an organic solvent. Because neither of the monomers is soluble in the solvent containing the others reaction can occur only at die surface4 or interface between the two solutions. The product is a polyamide, either nylon-6,6 or nylon-6,10, depending upon the number of carbon atoms in the diacid chloride chosen. This activity works well either as a laboratory experiment or as a demonstration. 

By using the electrolysis at the interface between two immiscible electrolyte solutions, Marecek and Samec determined acetylcholine by a differential pulse stripping voltammetric method [23],... 

Nevertheless, an important application of electrostatic models is to the interface between two immiscible electrolyte solutions. This can be viewed as two electrolyte double layers arranged back to back. In reality, however, total immiscibility never occurs and the degree of miscibility increases with the presence of electrolyte, so that corrections to the models need to be introduced. 

Electroinactive species — Ions and neutral compounds that show no signal in electrochemical measurements. In this sense, -> supporting electrolyte ions are electroinactive at least in the potential window. However, note that whether a species is electroactive or not should depend on the electrode used and measurement conditions. For example, tetramethylammonium ion is electroinactive at conventional electrodes, but electroactive at the interface between two immiscible electrolyte solutions, where it gives a voltammetric wave for transfer across the interface. 

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