Interfaces between two electrolytes

One of the features found at interfaces between two electrolytes (a) and ( 3) is the development of a Galvani potential, between the phases. This potential difference is a component of the total OCV of the galvanic cell [see Eq. (2.13)]. In the case of similar electrolytes, it is called the diffusion potential and can be determined, in contrast to potential differences across interfaces between dissimilar electrolytes. 

Electrochemistry is the study of structures and processes at the interface between an electronic conductor (the electrode) and an ionic conductor (the electrolyte) or at the interface between two electrolytes. 

As Schmickler states [3], Electrochemistiy is the study of structures and processes at the interface between an electronic conductor (the electrode) and an ionic conductor (the electrolyte) or at the interface between two electrolytes . The electrode/electrolyte or electrolyte/electrolyte interface is the region whose properties differ from the two adjoining phases, and/or the place where reactant adsorption and electrochemical reactions occur. Commonly, it is recognized as the interface between an electronic conductor (e.g., metals and semiconductors) and an ionic conductor (e.g., electrolyte solutions, molten salts, and solid electrolytes), known as an electrochemical interface. In a narrow region of an electrode/electrolyte interface, an electrical double layer (EDL) exists. The EDL is believed to be extremely thin, and is an important component of the interface. 

Suppose one could create an interface between two electrolyte phases across which only a single ion could penetrate. A selectively permeable membrane might be used as a separator to accomplish this end. Equation 2.3.34 would still apply but it could be simplified by recognizing that the transference number for the permeating ion is unity, while that for every other ion is zero. If both electrolytes are in a common solvent, one obtains by integration... 

A Galvani potential difference can form not only across the interface electrode/ electrolyte solution but also across the interface between two electrolyte solutions. There is usually a fine-pored wall (made of sintered glass or ceramic), a so-called diaphragm, to stabilize the phase boundary so that the solutions do not mix too... 

Electrochemical systems convert chemical and electrical energy through charge-transfer reactions. These reactions occur at the interface between two phases. Consequendy, an electrochemical ceU contains multiple phases, and surface phenomena are important. Electrochemical processes are sometimes divided into two categories electrolytic, where energy is supplied to the system, eg, the electrolysis of water and the production of aluminum and galvanic, where electrical energy is obtained from the system, eg, batteries (qv) and fuel cells (qv). 

True equilibrium cannot be established at the interface between two different electrolytes, since ions can be transferred by diffusion. Hence, in thermodynamic calculations concerning such cells, one often uses corrected OCV, % ... 

It is typical that in Eq. (3.23) for the EMF, all terms containing the chemical potential of electrons in the electrodes cancel in pairs, since they are contained in the expressions for the Galvani potentials, both at the interface with the electrolyte and at the interface with the other electrode. This is due to the fact that the overall current-producing reaction comprises the transfer of electrons across the interface between two metals in addition to the electrode reactions. 

For interfaces between liquid electrolytes, we can distinguish three cases (1) interfaces between similar electrolytes, (2) interfaces between dissimilar but miscible electrolytes, and (3) interfaces between immiscible electrolytes. In the first case the two electrolytes have the same solvent (medium), but they differ in the nature and/or concentration of solutes. In the second case the interface separates dissimilar media (e.g., solutions in water and ethanol). An example for the third case is a system consisting of salt solutions in water and nitrobenzene. The interface between immiscible dissimilar liquid electrolytes is discussed in more detail in Chapter 32. 

In topochemical reactions all steps, including that of nucleation of the new phase, occur exclusively at the interface between two solid phases, one being the reactant and the other the product. As the reaction proceeds, this interface gradually advances in the direction of the reactant. In electrochemical systems, topochemical reactions are possible only when the reactant or product is porous enough to enable access of reacting species from the solution to each reaction site. The number of examples electrochemical reactions known to follow a truly topochemical mechanism is very limited. One of these examples are the reactions occurring at the silver (positive) electrode of silver-zinc storage batteries (with alkaline electrolyte) ... 

An interface between two immiscible electrolyte solutions (ITIES) is formed between two liqnid solvents of a low mutual miscibility (typically, <1% by weight), each containing an electrolyte. One of these solvents is usually water and the other one is a polar organic solvent of a moderate or high relative dielectric constant (permittivity). The latter requirement is a condition for at least partial dissociation of dissolved electrolyte(s) into ions, which thus can ensure the electric conductivity of the liquid phase. A list of the solvents commonly used in electrochemical measurements at ITIES is given in Table 32.1. 

ITIES interface between two immiscible electrolyte solutions... 

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 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-... 

ITIES interface between two immiscible electrolyte solutions K tautomeric equilibrium constant between the zwitterionic and the neutral forms of a compound... 

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). 

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