Interface, electrical phenomena

The experimental approaches in studies of interface properties are analyzed. Several electrical methods based on measurements of work function, thermopower, and electrical conductivity and their applications in studies of defect-related properties are described. Several applied aspects of interface electrical phenomena are also briefly considered. 

Because of the short lifetime of ions in gaseous atmospheres, even at low pressure, gas-phase IR measurements are limited to adsorption of neutral molecules. Electrochemical applications of the IR method offer the interesting possibility of providing data on the adsorption properties of charged particles (Secs. 8 and 9). In the electrochemical environment the applied potential allows ionic adsorbates to be studied under energetically controllable conditions. Otherwise the electrochemical double layer offers exceptional conditions to investigate the Stark effect on vibrational transitions by setting tunable electric fields of the order of 10 V cm at the interface. This phenomenon will be discussed in Sec. 10. 

While the formation of an electrical double layer at interfaces is a general phenomenon, the electrode-electrolyte solution interface will be considered... 

This chapter will be concerned with the kinetics of charge transfer across an electrically charged interface and the transport and chemical processes accompanying this phenomenon. Processes at membranes that often have analogous features will be considered in Chapter 6. The interface that is most often studied is that between an electronically conductive phase (mostly a metal electrode) and an electrolyte, and thus these systems will be dealt with first. 

Flow movement also has a relationship with the electrokinetic phenomenon, which can promote or retard the motion of the fluid constituents. Electrokinetic effects can be described as when an electrical double layer exists at an interface between a mobile phase and a stationary phase. A relative movement of the two phases can be induced by applying an electric field and, conversely, an induced relative movement of the two will give rise to a measurable potential difference.33... 

Schofield Phil. Mag. March, 1926) has recently verified this relation by direct experiment. In order to appreciate the significance of this result, it is necessary to consider in more detail the electrical potential difference V and the manner in which it arises. Instead of regarding the phenomenon from the point of view of the Gibbs equation, it has been, until recently, more usual to discuss the subject of electro-capillarity from the conceptions developed by Helmholtz and Lippmann. These views, together with the theory of electrolytic solution pressure advanced by Nemst, are not in reality incompatible with the principles of adsorption at interfaces as laid down by Gibbs. 

In these kinds of systems, the polarization phenomenon is effective at the two interfaces involved (see also Sect. 2.3.2). Specifically, in membrane systems comprising two ITIES, this behavior is achieved when the membrane contains a hydrophobic supporting electrolyte and the sample aqueous solution (the inner one) contains hydrophilic supporting electrolytes, and there is no common ion between any of the adjacent phases. In this case, the potential drop cannot be controlled individually and the processes taking place at both interfaces are linked to each other by virtue of the same electrical current intensity. 

The electrical double layer at the metal oxide/electrolyte solution interface can be described by characteristic parameters such as surface charge and electrokinetic potential. Metal oxide surface charge is created by the adsorption of electrolyte ions and potential determining ions (H+ and OH-).9 This phenomenon is described by ionization and complexation reactions of surface hydroxyl groups, and each of these reactions can be characterized by suitable constants such as pKa , pKa2, pKAn and pKct. The values of the point of zero charge (pHpzc), the isoelectric point (pH ep), and all surface reaction constants for the measured oxides are collected in Table 1. 

The principle of EDLC operation is very simple and is based on the well-known electrical or double layer phenomenon. The device operates within a potential range in which no Faradaic reactions take place, and thus the behavior is fully capacitive. Polarization of the electrodes in opposite directions leads to accumulation of opposite charges at the electrode-solution interfaces. The higher the electrode surface area and the polarity of the electrolyte solution and its ionic concentration, the higher are the capacity and energy density of these devices. The capacitance C and the accumulated electrostatic energy E stored are given by Eqs. (2) and (3), respectively [44] ... 

The static - double-layer effect has been accounted for by assuming an equilibrium ionic distribution up to the positions located close to the interface in phases w and o, respectively, presumably at the corresponding outer Helmholtz plane (-> Frumkin correction) [iii], see also -> Verwey-Niessen model. Significance of the Frumkin correction was discussed critically to show that it applies only at equilibrium, that is, in the absence of faradaic current [vi]. Instead, the dynamic Levich correction should be used if the system is not at equilibrium [vi, vii]. Theoretical description of the ion transfer has remained a matter of continuing discussion. It has not been clear whether ion transfer across ITIES is better described as an activated (Butler-Volmer) process [viii], as a mass transport (Nernst-Planck) phenomenon [ix, x], or as a combination of both [xi]. Evidence has been also provided that the Frumkin correction overestimates the effect of electric double layer [xii]. Molecular dynamics (MD) computer simulations highlighted the dynamic role of the water protrusions (fingers) and friction effects [xiii, xiv], which has been further studied theoretically [xv,xvi]. 

In the study of impedance plots, we may observe the depression of semicircles. This is the so-called semicircle rotation of the impedance. This phenomenon is associated with electrode/electrolyte interface double-layer properties. For example, the rough surface of the electrodes or porous electrodes can result in an uneven distribution of the double-layer electric field. This semicircle rotation can be explained using the equivalent circuit presented in Figure 3.10, where R is inversely proportional to the frequency CO (and b is a constant). 

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