Electric double layer formation mechanism

Thus the theory of change in the water structure on the mineral particle surface is close to the theory of the electric double layer with the difference that in the first case the water acts as an electrolyte and mechanisms intensifying the process of the electric double layer formation are not the electric fields but the thermodynamic ones (temperature and pressure). 

Some emphasis is given in the first two chapters to show that complex formation equilibria permit to predict quantitatively the extent of adsorption of H+, OH , of metal ions and ligands as a function of pH, solution variables and of surface characteristics. Although the surface chemistry of hydrous oxides is somewhat similar to that of reversible electrodes the charge development and sorption mechanism for oxides and other mineral surfaces are different. Charge development on hydrous oxides often results from coordinative interactions at the oxide surface. The surface coordinative model describes quantitatively how surface charge develops, and permits to incorporate the central features of the Electric Double Layer theory, above all the Gouy-Chapman diffuse double layer model. 

Electroanalytical chemists and others are concerned not only with the application of new and classical techniques to analytical problems, but also with the fundamental theoretical principles upon which these techniques are based. Electroanalytical techniques are proving useful in such diverse fields as electro-organic synthesis, fuel cell studies, and radical ion formation, as well as with such problems as the kinetics and mechanisms of electrode reactions, and the effects of electrode surface phenomena, adsorption, and the electrical double layer on electrode reactions. 

When particles or large molecules make contact with water or an aqueous solution, the polarity of the solvent promotes the formation of an electrically charged interface. The accumulation of charge can result from at least three mechanisms (a) ionization of acid and/or base groups on the particle s surface (b) the adsorption of anions, cations, ampholytes, and/or protons and (c) dissolution of ion-pairs that are discrete subunits of the crystalline particle, such as calcium-oxalate and calcium-phosphate complexes that are building blocks of kidney stone and bone crystal, respectively. The electric charging of the surface also influences how other solutes, ions, and water molecules are attracted to that surface. These interactions and the random thermal motion of ionic and polar solvent molecules establishes a diffuse part of what is termed the electric double layer, with the surface being the other part of this double layer. 

Similar to the findings in other electrical property studies, correlations may be drawn between electrical and mechanical data, but the large effects of conduction and ion double-layer formation mask such correlations in the present case. 

I) (re-) formation of an electrical double layer. Range x" mechanisms conduction and diffusion ... 

Electrolysis of carbonyl compounds provides pinacols, alcohols or hydrocarbons, depending on the conditions, such as pH, the nature of the electrode, and its potential. Fundamental studies have been carried out on the mechanisms of hydrocarbon formation using acetone as a substrate. Although several electrodes, such as Cd, Pt, Pb or Zn, are recommended, carbonyl compounds, including aryl and alkyl derivatives, require strong aqueous acidic media for reduction to the hydrocarbons. The mechanism of the electrolytic reduction is probably similar to that of Clemmensen reduction, which starts from anion radical formation by one-electron transfer, as indicated in Scheme 3. The difference is that electrolytic reduction takes place in an electric double layer, rather than on the surface of the zinc metal. 

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... 

Such heteropolyanions are rather voluminous and thus, much more polarizable. In the vicinity of the cathode in the electric double layer, this anion is strongly polarized and finally disintegrated into smaller species, from which consecutive molybdenum deposition takes place. The X-ray diffraction analysis of the solid deposit on the top closure and furnace wall proved that the deposit consists of pure K2SiF6, which supports the assumption on the formation of the above-mentioned heteropolyanions. Unfortunately, the authors did not study the mechanism of the cathodic process in this system. 

The adsorption of ions and the formation of the electric double layer at water/oxide interface are the physical phenomena the importance of which in life and technology can hardly be overestimated. So, no surprise that the mechanism of the formation of the electric double layer at water/oxide interfaces has been studied thoroughly in hundreds of papers and it would take far too long to review even the most fundamental of them. Various techniques have been used to measure proton and accompanying ion adsorption on the outermost surface oxygens of oxides. The most popular of these techniques are potentiometric titration and (-potential measurements. Then, radiometric methods allow the adsorption of individual ions to be monitored. 

Since this book is dedicated to the dynamic properties of surfactant adsorption layers it would be useful to give a overview of their typical properties. Subsequent chapters will give a more detailed description of the structure of a surfactant adsorption layer and its formation, models and experiments of adsorption kinetics, the composition of the electrical double layer, and the effect of dynamic adsorption layers on different flow processes. We will show that the kinetics of adsorption/desorption is not only determined by the diffusion law, but in selected cases also by other mechanisms, electrostatic repulsion for example. This mechanism has been studied intensively by Dukhin (1980). Moreover, electrostatic retardation can effect hydrodynamic retardation of systems with moving bubbles and droplets carrying adsorption layers (Dukhin 1993). Before starting with the theoretical foundation of the complicated relationships of nonequilibrium adsorption layers, this introduction presents only the basic principles of the chemistry of surfactants and their actions on the properties of adsorption layers. 

Another difference lies in the role of electric double-layer repulsion, which is often a key factor in stabilizing aqueous foams with ionic surfactants. The adsorption of ionic surfactant at the liquid surface leads to the formation of a charged surface and a diffuse layer of counterions. As the foam lamellae thin because of the drainage of liquid, these counterions begin to repel each other and retard further thinning. Because ionization is not possible in nonpolar solvents, this double-layer mechanism is not operative in nonpolar foams. 

In summary, electrochemical promotion may be regarded as catalysis in an electric double layer controlled by current or potential application. The necessary condition to achieve electrochemical promotion is the formation of a double layer at the catalyst/gas interface by the mechanism of ion backspillover from the solid electrolyte support. This may occur over a wide range of conditions. The most important experimental parameters, which favor electrochemical promotion are the following long tpb (porous catalyst), moderate diffusion length (thin catalyst film), and adequate temperature range,... 

The proposed model of two-stage process is well supported by the cyclic voltammetric experiments presented in Section III.4. The fast reversible stage, attributed to formation of an electric double layer at the catalyst/gas interface via backspillover of promoters, has been discussed in detail in Section III.5. To explain the slow irreversible pretreatment. This phenomenon is called permanent electrochemical promotion or permanent NEMCA effect. The similarity between the regions of rate increase and decrease indicates that similar mechanisms are involved during current application and interruption, but the enhancement of the open-circuit rate indicates that the electrochemical promotion of the Ir02 catalyst is not reversible. This behavior of an oxide catalyst is different from that of a metal catalyst for which the electrochemical promotion is usually reversible. ... 

At least two of the recognized mechanisms for the formation of electrical double layers (Hunter, elal. 1981 Russel etal., 1989) are relevant to LB film depositions (1) ionization of carboxylic acid group and amphoteric acid groups on solid surfaces, and (2) differences between the affinities of two phases for ions or ionizable species. The latter mechanism includes the uneven distribution of anions and cations between two immiscible phases, the differential adsorption of ions from an electrolyte solution to a solid surface, and the differential solution of one ion over the other from a crystal lattice. Since the solid-liquid and the film-liquid interfaces are flat, large surfaces and since both have a large, solid-like concentration, the analysis that follows applies to both interfaces. For an interface conformed by a thin film of an amphiphilic compound with the hydrophilic end of the molecule in contact with the water subphase, the equilibrium of charges is based on pH and subphase concentration. The effect of pH is highlighted by the definition of the of the carboxylic acid ... 

The interaction forces and potentials between two charged surfaces in an electrolyte are fundamental to the analysis of colloidal systems and are associated with the formation of electrical double layers (EDLs) in vicinity of the solid surfaces. The charged surfaces typically interact across a solution that contains a reservoir of ions, as a consequence of the dissociation of the electrolyte that is already present. In colloid and interfacial sciences, the EDL interaction potential, coupled with the van der Waals interaction potential, leads to the fimdamental understanding of inter-siuface interaction mechanisms, based on the Derjaguin-Landau-Verwey-Overbeek (DLVO) theory [1]. In practice, the considerable variations in the EDL interaction, brought about by the variations in electrolytic concentration of the dispersing medium, pH of the medium, and the siuface chemistry, lead to a diverse natiue of the colloidal behavior. A fundamental understanding of the physics of EDL interactions, therefore, is of prime importance in... 

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