Electric double layer EDL

The existence of Galvani potentials between two different conducting phases is connected with the formation of an electric double layer (EDL) at the phase boundary (i.e., of two parallel layers of charges with opposite signs, each on the surface of one of the contacting phases). It is a special feature of such an EDL that the two layers forming the double layer are a very small (molecular) distance apart, between 0.1 and 0.4nm. For this reason EDL capacitances are very high (i.e., tenths of pF/cm ). 

When an electrode is in contact with an electrolyte, the interphase as a whole is electroneutral. However, electric double layers (EDLs) with a characteristic potential distribution are formed in the interphase because of a nonuniform distribution of the charged particles. 

The electrified interface is generally referred to as the electric double layer (EDL). This name originates from the simple parallel plate capacitor model of the interface attributed to Helmholtz.1,9 In this model, the charge on the surface of the electrode is balanced by a plane of charge (in the form of nonspecifically adsorbed ions) equal in magnitude, but opposite in sign, in the solution. These ions have only a coulombic interaction with the electrode surface, and the plane they form is called the outer Helmholtz plane (OHP). Helmholtz s model assumes a linear variation of potential from the electrode to the OHP. The bulk solution begins immediately beyond the OHP and is constant in potential (see Fig. 1). 

Having chosen a particular model for the electrical properties of the interface, e.g., the TIM, it is necessary to incorporate the same model into the kinetic analysis. Just as electrical double layer (EDL) properties influence equilibrium partitioning between solid and liquid phases, they can also be expected to affect the rates of elementary reaction steps. An illustration of the effect of the EDL on adsorption/desorption reaction steps is shown schematically in Figure 7. In the case of lead ion adsorption onto a positively charged surface, the rate of adsorption is diminished and the rate of desorption enhanced relative to the case where there are no EDL effects. 

In electrochemical capacitors (or supercapacitors), energy may not be delivered via redox reactions and, thus the use of the terms anode and cathode may not be appropriate but are in common usage. By orientation of electrolyte ions at the electrolyte/electrolyte interface, so-called electrical double layers (EDLs) are formed and released, which results in a parallel movement of electrons in the external wire, that is, in the energy-delivering process. 

The state of stability under these conditions can be qualitatively described as follows. As two oil droplets approach each other, the negative charge gives rise to a repulsive effect (Figure 7.4). The repulsion will take place within the electrical double-layer (EDL) region. It can thus be seen that the magnitude of double-layer distance will decrease if the concentration of ions in the water phase increases. This is because the electrical double layer region decreases. However, in all such cases in which two bodies come closer, there exists two different kinds of forces that must be considered ... 

The ionized surfactants will stabilize O/W emulsions by imparting the surface electrical double layer (EDL). 

Electrical double-layer (edl) properties of solid polycrystalline zinc (pc-Zn) electrodes and single-crystal zinc electrodes in aqueous solution were studied in many works, which are reviewed in Refs 1, 2. 

The electrical double-layer (edl) properties pose a fundamental problem for electrochemistry because the rate and mechanism of electrochemical reactions depend on the structure of the metal-electrolyte interface. The theoretical analysis of edl structures of the solid metal electrodes is more complicated in comparison with that of liquid metal and alloys. One of the reasons is the difference in the properties of the individual faces of the metal and the influence of various defects of the surface [1]. Electrical doublelayer properties of solid polycrystalline cadmium (pc-Cd) electrodes have been studied for several decades. The dependence of these properties on temperature and electrode roughness, and the adsorption of ions and organic molecules on Cd, which were studied in aqueous and organic solvents and described in many works, were reviewed by Trasatti and Lust [2]. 

Figure 7.4. Schematic model of the Electrical Double Layer (EDL) at the metal oxide-aqueous solution interface showing elements of the Gouy-Chapman-Stern-Grahame model, including specifically adsorbed cations and non-specifically adsorbed solvated anions. The zero-plane is defined by the location of surface sites, which may be protonated or deprotonated. The inner Helmholtz plane, or [i-planc, is defined by the centers of specifically adsorbed anions and cations. The outer Helmholtz plane, d-plane, or Stern plane corresponds to the beginning of the diffuse layer of counter-ions and co-ions. Cation size has been exaggerated. Estimates of the dielectric constant of water, e, are indicated for the first and second water layers nearest the interface and for bulk water (modified after [6]).

The nature of the electrical double layer (EDL) at metal (hydr)oxide surfaces will be reviewed next, including a discussion of the classical models of this interfacial region, drawing from Refs. [105-111] and its variation with solution conditions, particularly pH and ionic strength. 

Reaction 5.1 is meant to represent a nonspecific electrostatic interaction (presumably responsible for double-layer charge accumulation) Reaction 5.2 symbolizes specific adsorption (e.g., ion/dipole interaction) Reaction 5.3 represents electron transfer across the double layer. Together, these three reactions in fact symbolize the entire field of carbon electrochemistry electric double layer (EDL) formation (see Section 5.3.3), electrosorption (see Section 5.3.4), and oxidation/reduction processes (see Section 5.3.5). The authors did not discuss what exactly >C, represents, and they did not attempt to clarify how and why, for example, the quinone surface groups (represented by >CxO) sometimes engage in proton transfer only and other times in electron transfer as well. In this chapter, the available literature is scrutinized and the current state of knowledge on carbon surface (electrochemistry is assessed in search of answers to such questions. 

As shown in Figure 8.2, when the system is connected to a power supply, the surface of the electrodes is charged and attracts the ions of opposite charge. The ions are stored in an electrical double layer (EDL) at the surface of electrodes (Figure 8.5). Each electrode is equivalent to a capacitor with capacity given by the classical formula (Equation 8.4) [7] ... 

When one first thinks of the electrical double layer (edl) one imagines the description conceived by the originators, Debye and Huckel [2], Gouy and Chapman [3], Verwey and Overbeek [1], of a sharp and well-defined boundary between two phases. One of the phases usually being an aqueous medium in which a strong electrolyte is dissolved to a molar concentration of cs. The other phase is usually a solid, impermeable to either the electrolyte... 

An electrical double layer (edl) existing on the solid-solution interface is essentially connected with the surface properties of the system. The amount of accumulated charge influences the adsorption of ions and molecules. In the latter case it also influences the configuration of the adsorbed species. On the other hand, the adsorption of the ions and molecules varies surface properties of the interface (functional groups) and thus, the distribution of the charge in the interfacial region. The existence of the electric charge at the interface influences the dispersed system stability. 

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. 

In electrokinetic phenomena such as electroacoustics, theoretical models need to consider the induced movement of charge within the electrical double layer (EDL), the surface current , Is, as well as the interaction of the outer portion of the double layer with the applied signal (acoustic or electric field) and with the liquid medium. Hydrodynamic flows generate surface current as liquid moving relative to the particle... 

Polarization of electrical double layer (EDL) in response to applied acoustic or electric field... 

Electrical Double Layer. In order to model the structure of the electrical double layer (EDL) of oxide colloids, it is necessary to formulate 1) the reactions which result in the formation of surface charge (cTq), and 2) the potential and charge relationships in the interfacial region. It has been generally assumed that surface charge (O ), defined experimentally by the net uptake of protons by the surface, results from simple ionization of oxide surface sites (5, 11 12, 13), i.e.. 

For the processing of ceramics in liquids, it is important to introduce repulsive forces to overcome attractive van der Waals forces. One type of force is the so-called electric double layer (EDL) force. Some books refer to this force as electrostatic force. To avoid confusion, the term EDL force is used throughout this chapter to clearly show that the physics of particles in liquids strongly differs from particles in air, where electrostatic forces apply that follow Coulombs law. This section describes the chemistry in the development of surface charges on particles and the physics equation that governs the forces. 

FIGURE 11.5 Electric double layer (EDL). In this example the surface selectively adsorbs negative ions and a second layer is formed from the counter ions. 

Electric Double Layer. The electric double layer (EDL) consists of the charged surface and a neutralizing excess of counterions over co-ions, distributed near the surface (see Figure 12). The EDL can be viewed as being composed of two layers ... 

Several mechanisms of interaction between particles of solids are known [3]. Mechanical adhesion is achieved by flowing a metal into the support pores. The molecular mechanism of adhesion is based on the Van der Waals forces or hydrogen bonds, and the chemical mechanism on the chemical interaction of the metal particles with the support. The electric theory relates adhesion to the formation of an electric double layer (EDL) at the adhesive-substrate interface. Finally, the diffusion mechanism implies interpenetration of the molecules and atoms of the interacting phases, which results in the interface blurring. These insights into the nature of adhesion can be revealed in the papers about the interaction of transition metal... 

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