Interfacial potential difference liquid interface

Although the equilibrium principle was available (equality of electrochemical potential of each ion that reversibly equilibrates across an immiscible liquid/liquid interface), the elementary theory and consequences were not explored until recently (6). To develop an interfacial potential difference (pd) at a liquid interface, two ions M, X that partition are required. However,... 

Ion transfer across phospholipid monolayers at liquid-liquid interfaces has been studied with the aim of elucidating the mechanism and kinetics of ion transport across a bilayer lipid membrane (BLM). The main advantage of using these systems is in the possibility of controlling the interfacial potential difference, which in the case of the BLM has to be inferred indirectly [141]. 

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. 

Analogous ionic systems are represented by a contact of two electrolyte solutions in immiscible liquids, which contain a common ion. Owing to its interfacial exchange the electrochemical potential of this ion is to be constant throughout the system, and it leads again to a relation for the interfacial potential difference similar to Eq. (1) (called Dorman equation this time), that is, the interface is nonpolarizable without a change of the bulk media properties. 

Electron transfer at a liquid/liquid interface is an example of an interfacial heterogeneous ET reaction occurring between a redox conple in an aqueons phase and another redox couple in an organic phase. The ET occurs either by external polarization of the interface or by the interfacial potential difference represented in equation (17.3.3.5) and schematically shown in Figure 17.3.7 (2, 6). 

Among different liquid-solid interfaces, fhe boundary between an electrolyte and a metal electrode is the one which has been most investigated in surface science. This is dictated by its importance for elecfrochemisfry and by a rich variety of interesting phenomena. In some respect the relevant processes are similar to those at the gas-solid interface. On the other hand, the electrified character of the electrolyte-solid interface resulfs in some peculiarities. One can control interface properties through external manipulation of the interfacial potential difference. All reactions that involve charge transfer respond directly to this quantity. In this section we shall consider the structure of the electric double layer which takes place at an electrolyte-solid interface and the basic principles of control for various reactions at this boundary. 

There are large cations in these cells, e.g., tetra-alkylammonium cations in the organic phase and the interfacial ion exchange involves only so-called critical ions, here X and LX ions are practically not transferred through the organic phase. Both liquid interfaces are reversible with respect to the appropriate anion, X or L. EMF is, in practice, also influenced by the diffusion potential in the organic phase, and in the case of cells of the type in Scheme 11 - by the difference of standard transfer energies of both ions (Section III.A)... 

The possibility of determination of the difference of surface potentials of solvents, see Scheme 18, among others, has been used for the investigation of Ajx between mutually saturated water and organic solvent namely nitrobenzene [57,58], nitroethane and 1,2-dichloroethane (DCE) [59], and isobutyl methyl ketone (IB) [69]. The results show a very strong influence of the added organic solvent on the surface potential of water, while the presence of water in the nonaqueous phase has practically no effect on its x potential. The information resulting from the surface potential measurements may also be used in the analysis of the interfacial structure of liquid-liquid interfaces and their dipole and zero-charge potentials [3,15,22]. 

The oscillation at a liquid liquid interface or a liquid membrane is the most popular oscillation system. Nakache and Dupeyrat [12 15] found the spontaneous oscillation of the potential difference between an aqueous solution, W, containing cetyltrimethylammo-nium chloride, CTA+CK, and nitrobenzene, NB, containing picric acid, H" Pic . They explained that the oscillation was caused by the difference between the rate of transfer of CTA controlled by the interfacial adsorption and that of Pic controlled by the diffusion, taking into consideration the dissociation of H Pic in NB. Yoshikawa and Matsubara [16] realized sustained oscillation of the potential difference and pH in a system similar to that of Nakache and Dupeyrat. They emphasized the change of the surface potential due to the formation and destruction of the monolayer of CTA" Pic at the interface. It is... 

Recent theoretical studies indicate that thermal fluctuation of a liquid/ liquid interface plays important roles in chemical/physical properties of the surface [34-39], Thermal fluctuation of a liquid surface is characterized by the wavelength of a capillary wave (A). For a macroscopic flat liquid/liquid interface with the total length of the interface of /, capillary waves with various A < / are allowed, while in the case of a droplet, A should be smaller than 2nr (Figure 1) [40], Therefore, surface phenomena should depend on the droplet size. Besides, a pressure (AP) or chemical potential difference (An) between the droplet and surrounding solution phase increases with decreasing r as predicted by the Young-Laplace equation AP = 2y/r, where y is an interfacial tension [33], These discussions indicate clearly that characteristic behavior of chemical/physical processes in droplet/solution systems is elucidated only by direct measurements of individual droplets. 

The liquid metal mercury-solution interface presents the advantage that it approaches closest to an ideal polarizable interface and, therefore, it adopts the potential difference applied between it and a non-polarizable interface. For this reason, the mercury-solution interface has been extensively selected to carry out measurements of the surface tension dependence on the applied potential. In the case of other metal-solution interfaces, the thermodynamic study is much more complex since the changes in the interfacial area are determined by the increase of the number of surface atoms (plastic deformation) or by the increase of the interatomic lattice spacing (elastic deformation) [2, 4]. 

Interface between two liquid solvents — Two liquid solvents can be miscible (e.g., water and ethanol) partially miscible (e.g., water and propylene carbonate), or immiscible (e.g., water and nitrobenzene). Mutual miscibility of the two solvents is connected with the energy of interaction between the solvent molecules, which also determines the width of the phase boundary where the composition varies (Figure) [i]. Molecular dynamic simulation [ii], neutron reflection [iii], vibrational sum frequency spectroscopy [iv], and synchrotron X-ray reflectivity [v] studies have demonstrated that the width of the boundary between two immiscible solvents comprises a contribution from thermally excited capillary waves and intrinsic interfacial structure. Computer calculations and experimental data support the view that the interface between two solvents of very low miscibility is molecularly sharp but with rough protrusions of one solvent into the other (capillary waves), while increasing solvent miscibility leads to the formation of a mixed solvent layer (Figure). In the presence of an electrolyte in both solvent phases, an electrical potential difference can be established at the interface. In the case of two electrolytes with different but constant composition and dissolved in the same solvent, a liquid junction potential is temporarily formed. Equilibrium partition of ions at the - interface between two immiscible electrolyte solutions gives rise to the ion transfer potential, or to the distribution potential, which can be described by the equivalent two-phase Nernst relationship. See also - ion transfer at liquid-liquid interfaces. 

Quantum phenomena at the vacuum interface have been postulated in analogy with known effects at physico-chemical interfaces. To be consistent, special properties of the latter are therefore implied. A physical interface is the boundary surface that separates two phases in contact. These phases could be two solid phases, two liquid phases, solid-liquid, solid-gas or liquid-gas phases. What they all have in common is a potential difference between the two bulk phases. In order to establish equilibrium at the interface it is necessary that rearrangement occurs on both sides of the interface over a narrow region. Chemical effects within the interfacial zone are unique and responsible for the importance of surfaces in chemical systems. At the most fundamental level the special properties of surfaces relate to the difference between isolated elementary entities and the same entities in a bulk medium, or condensed phase. 

Since these interfaces are usually constructed of charged detergents a diffuse electrical double layer is produced and the interfacial boundary can be characterized by a surface potential. Consequently, electrostatic as well as hydrophilic and hydrophobic interactions of the interfacial system can be designed. In this report we will review our achievements in organizing photosensitized electron transfer reactions in different microenvironments such as bilayer membranes and water-in-oil microemulsions.In addition, a novel solid-liquid interface, provided by colloidal Si02 particles in an aqueous medium will be discussed as a means of controlling photosensitized electron transfer reactions. 

For practical reasons the capillary rise technique is rarely used for the measurement of interfacial (rather than surface) tensions large amounts of the two liquids are needed and there are suitable and convenient alternatives. An exception to this is the measurement of the Interfacial tension between mercury and (mostly) aqueous solutions at various potential differences applied across the liquid-liquid interface. Such measurements are done in a so-called Lippmann capillary electrometer, already described in the chapter on electric double layers (fig. 11.3.47). 

Two more results support the hypothesis of the electrostatic potential at the ice/water interface the existence of the well-pronounced free energy minimum for the Cl- ion close to the Gibbs dividing surface (Fig. 13), and the behaviour of the unconstrained Na+ and Cl- ions on the liquid side of the ice/water interface shown in Fig. 9, when for long times the Cl- ion showed a tendency to be attracted to the ice/water interface, while Na+ ion at different positions with respect to the ice/water interface ended up on the liquid side of ice/water interface. Calculations of the surface potential of the water/vapor interface arise from work by Wilson, Pohorille and Pratt [57, 58], but for the ice/water interface no such reports have appeared, even though the existence of such an interfacial potential would be very helpful in addressing the Workman-Reynolds effect [21, 23],... 

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