Immiscible liquid electrolytes

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. 

Immiscible liquid electrolytes -> interface between two immiscible electrolyte solutions... 

Recent progress and main problems of the study of electrochemical equilibrium properties are reviewed for interfaces between two immiscible liquid electrolyte solutions. The discussed properties are mainly described in terms of the Galvani, Volta, zero charge, and surface (dipolar) potentials at the liquid-liquid interfaces and free liquid surfaces. Different galvanic and voltaic cells with liquid-liquid, mainly water-nitrobenzene interfaces, are described. These interfaces may be polarizable or reversible with respect to one or several ions simultaneously. 

Fig. 1.2.3. Experimental arrangement for measuring the transfer of ions between two immiscible liquid electrolyte solutions...

Stripping Voltammetry at Two Immiscible Liquid Electrolyte Solutions... 

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. 

Spherical microparticles are more difficult to manufacture and can be prepared by several methods. One method prepares silica hydrogel beads by emulsification of a silica sol in an immiscible organic liquid [20,21,24,25]. To promote gelling a silica hydrosol, prepared as before, is dispersed into small droplets in a iater immiscible liquid and the temperature, pH, and/or electrolyte concentration adjusted to promote solidification. Over time the liquid droplets become increasingly viscous and solidify as a coherent assembly of particles in bead form. The hydrogel beads are then dehydrated to porous, spherical, silica beads. An alternative approach is based on the agglutination of a silica sol by coacervation [25-27], Urea and formaldehyde are polymerized at low pH in the presence of colloidal silica. Coacervatec liquid... 

Reynolds excepts from the general validity of Antonow s rule the tension of mercury and amalgams against certain electrolytes and immiscible liquids which react chemically. It is clear that the rule would be difficult to verify satisfactorily in the latter case with mercury in contact with aqueous solutions (or with water) the apparent deviation from the rule is. probably to be accounted for by consideration of the electro-capillary effects (Oh. vn). 

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). 

Marcus has recently returned to this problem [133] and, by analogy with the problem of donor-acceptor electron transfer at the interface between two immiscible liquids, has derived the following expression for ka, the heterogeneous rate constant for electron transfer from a semiconductor to a species in a contacting electrolyte ... 

Electrophoresis — Movement of charged particles (e.g., ions, colloidal particles, dispersions of suspended solid particles, emulsions of suspended immiscible liquid droplets) in an electric field. The speed depends on the size of the particle, as well as the -> viscosity, -> dielectric permittivity, and the -> ionic strength of the solution, and it is directly proportional to the applied electric field. In analytical as well as in synthetic chemistry electrophoresis has been employed to separate species based on different speeds attained in an experimental setup. In a typical setup the sample is put onto a mobile phase (dilute electrolyte solution) filled, e.g., into a capillary or soaked into a paper strip. At the ends of the strip connectors to an electrical power supply (providing voltages up to several hundred volts) are placed. Depending on their polarity and mobility the charged particles move to one of the electrodes, according to the attained speed they are sorted and separated. (See also - Tiselius, - electrophoretic effect, - zetapotential). 

Multiphase system — An inhomogeneous system consists of two or more phases of one or more substances. In electrochemistry, where all processes occur at the interface thus all measurement systems must contain at least two - phases. In common understanding so-called multi-phase systems contain more than two phases. Good examples of such systems are -> electrode contacting a solid phase (immobilized at the electrode electroactive material or heterogeneous -> amalgams) and electrolyte solution, and an electrode that remains in contact with two immiscible liquids [i]. All phenomena appearing in such multi-phase systems are usually more complicated and additional effects as - interphase formation and -> mass transport often combined with - ion transfer must be taken into account [ii]. 

Oil-water interface — Interface formed between a water-immiscible liquid (oil) and water. In electrochemistry, when - electrolytes are dissolved in both phases, it is also often called the - interface between two immiscible electrolyte solutions (ITIES). 

Surface activity — is -> activity of a species i adsorbed (see -> adsorption) on the electrode or activity of species accumulated in the interfacial region between two immiscible liquids (see interface between two immiscible electrolyte solutions). Surface activity is related to the activity of species in the bulk of the solution as follows af = a exp where af and a is the activity of... 

Many examples exist of interfaces formed between two immiscible liquids. A well-known one is the interface between a long-chain hydrocarbon, for example, dodecane, and water, which is commonly known as the oil water interface. Dodecane and water are immiscible because the hydrocarbon phase is nonpolar. Liquid liquid interfaces are also formed between water and organic liquids with polar groups such as octanol and heptanoic acid, which also have rather long hydrocarbon chains. The polar liquid nitrobenzene, which has a relative permittivity of 35, is also immiscible with water. Another well-known system is the mercury polar liquid interface. This has been studied extensively, especially for aqueous electrolyte solutions. However, the mercury polar liquid interface is also an example of a metal solution interface which was considered in the previous section. The discussion here is limited to liquids with relative dielectric permittivities falling in the range 1-200, and systems which have poor conductivities as pure liquids. 

The interface between two immiscible liquids is used as a characteristic boundary for study of charge equilibrium, adsorption, and transport. Interfacial potential differences across the liquid-liquid boundary are explained theoretically and documented in experimental studies with fluorescent, potential-sensitive dyes. The results show that the presence of an inert salt or a physiological electrolyte is essential for the function of the dyes. Impedance measurements are used for studies of bovine serum albumin (BSA) adsorption on the interface. Methods for determination of liquid-liquid capacitance influenced by the presence of BSA are shown. The potential of zero charge of the interface was obtained for 0-200 ppm of BSA. The impedance behavior is also discussed as a function of pH. A recent new approach, using a microinterface for interfacial ion transport, is outlined. 

Interfaces between two immiscible solutions with dissolved electrolytes, which are most interesting to workers in several disciplines, cover theoretical physical electrochemistry and analytical applications for sensor design. These interfaces are used in interpretation of processes that occur in biological membranes and in biological systems. The interface between two immiscible electrolyte solutions was studied for the first time at least 100 years ago by Nemst (I), who performed the experiments that provide the theoretical basis for current potentiometric and voltammetric studies of interfaces. In 1963, Blank and Feig (2) suggested that an interface between two immiscible liquids could be used as a model (at least as a crude approximation) for... 

The structure of surfactants determines considerably their behaviour at the interface between two immiscible liquids which differ considerably in their polarity. In practice, water or an aqueous electrolyte solution are most frequently considered as a polar phase, and hydrocarbons or their mixtures, e.g. oil fractions, as an apolar phase. In this connection, substances practically completely soluble in water are ascribed to the so-called water-soluble surfactants . Typical anionics are, depending on the polar group type, alkali metal salts, with a hydrocarbon tail of a length of C 2—C 8 Magnesium salts of alkyl ethoxysulphates are also partly soluble. Bivalent and trivalent metal derivatives of the same anionics are typically ascribed to oil-soluble surfactants. 

Redox reactions at the interface between immiscible liquids fall into two classes. The first class includes spontaneous processes that occur in the absence of external electromagnetic fields [16-77]. This type of redox transformation has been investigated in bioenergetics, model membrane systems and at oil/water interfaces [78-99]. Redox reactions in the second class occur at the interface between immiscible electrolytes when external electrical fields are applied to the interface, and under these conditions interfacial charge-transfer reactions take place at controlled interfacial potentials [100-139]. 

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