Specific adsorption electrical double-layer structure

As shown in the Figure, electro capillary curves are affected by - specific adsorption of ions (here, anions) at the electrode surface. Additionally, they are influenced by the - space charge region of the electrical double layer. Thus, electrocapillary curves as well as capacitance curves provide useful information on the electrical double-layer structure of electrode surfaces. 

The subsequent three chapters are devoted to the electric double-layer structure at the interface between immiscible electrolytes examined by the electrocapillary curves method (Prof. Senda and coauthors) and by measurement of the electric double-layer capacity (Dr. Samec and Dr. Mare ek) as well as to the investigation of the Galvani and Volta potentials in the above-mentioned systems (Prof. Koczorowski). These chapters will be of interest to many electrochemists since the results obtained here are comparable with the thoroughly studied metal/electrolyte solution interface. An insignificant potential shift in the compact layer at the interface between immiscible electrolytes in the absence of specific ion adsorption - this is the main conclusion arrived at by the authors of Chaps. 4 and 5. Chapter 6 deals with the scale of potentials in a system of immiscible electrolytes and the thermodynamic relation between the distribution coefficients and the Volta potentials. 

Fig. 4.1 Structure of the electric double layer and electric potential distribution at (A) a metal-electrolyte solution interface, (B) a semiconductor-electrolyte solution interface and (C) an interface of two immiscible electrolyte solutions (ITIES) in the absence of specific adsorption. The region between the electrode and the outer Helmholtz plane (OHP, at the distance jc2 from the electrode) contains a layer of oriented solvent molecules while in the Verwey and Niessen model of ITIES (C) this layer is absent...

At present it is impossible to formulate an exact theory of the structure of the electrical double layer, even in the simple case where no specific adsorption occurs. This is partly because of the lack of experimental data (e.g. on the permittivity in electric fields of up to 109 V m"1) and partly because even the largest computers are incapable of carrying out such a task. The analysis of a system where an electrically charged metal in which the positions of the ions in the lattice are known (the situation is more complicated with liquid metals) is in contact with an electrolyte solution should include the effect of the electrical field on the permittivity of the solvent, its structure and electrolyte ion concentrations in the vicinity of the interface, and, at the same time, the effect of varying ion concentrations on the structure and the permittivity of the solvent. Because of the unsolved difficulties in the solution of this problem, simplifying models must be employed the electrical double layer is divided into three regions that interact only electrostatically, i.e. the electrode itself, the compact layer and the diffuse layer. 

At the next level we also take specific adsorption of ions into account (Fig. 4.6). Specifically adsorbed ions bind tightly at a short distance. This distance characterizes the inner Helmholtz plane. In reality all models can only describe certain aspects of the electric double layer. A good model for the structure of many metallic surfaces in an aqueous medium is shown in Fig. 4.6. The metal itself is negatively charged. This can be due to an applied potential or due to the dissolution of metal cations. Often anions bind relatively strongly, and with a certain specificity, to metal surfaces. Water molecules show a distinct preferential orientation and thus a strongly reduced permittivity. They determine the inner Helmholtz plane. 

At the interface between O and W, the presence of the electrical double layers on both sides of the interface also causes the variation of y with Aq<. In the absence of the specific adsorption of ions at the interface, the Gouy-Chapman theory satisfactorily describes the double-layer structure at the interface between two immiscible electrolyte soultions [20,21]. For the diffuse part of the double layer for a z z electrolyte of concentration c in the phase W whose permittivity is e, the Gouy-Chapman theory [22,23] gives an expression... 

Although this book significantly differs from the earlier Colloid Chemistry textbook, it nevertheless focuses on the specifics of educational and research work carried out at the Colloid Chemistry Division at the Chemistry Department of MSU. Many results presented in this book represent the art developed in the laboratories of the Colloid Chemistry Division, in the Laboratory of Physical-Chemical Mechanics (headed by E.D. Shchukin since 1967) of the Institute of Physical Chemistry of the Russian Academy of Science, and in other research institutions and industrial laboratories under the guidance of the authors and with their direct participation. Special attention is devoted in the book to the broad capabilities that the use of surfactants offers for controlling the properties and behavior of disperse systems and various materials due to the specific physico-chemical interactions taking place at interfaces. At the same time the authors made every effort to avoid duplication of material traditionally covered in textbooks on physical chemistry, electrochemistry, polymer chemistry, etc. These include adsorption from the gas phase on solid surfaces (by microporous adsorbents), the structure of the dense part of the electrical double layer, electrocapillary phenomena, specific properties of polymer colloids, and some other areas. 

The results of these calculations imply that none of the ions would be contact adsorbed when no specific interactions between ions and metal are taken into account in the model. The Li+ ion, believed to be nonspecifically adsorbing, would be able to approach the surface more closely than the anions, mostly because of its small size, which allows it to penetrate the surface layers without displacing water molecules. The simulation results thus indirectly demonstrate the importance of specific chemical interactions for realistic models of the electric double layer. Apparently, also some specific features of the hydration shell structure of the ions must be taken into consideration in order to fully understand the adsorption of ions. 

Typically, a supercapacitor is composed of two electrodes dipped in an electrolyte solution with a suitable separator. It is generally accepted that the energy storage mechanism of supercapacitors can be classified into electrical double layer capacitors (EDLCs) and pseudocapacitors (Fig. 6.1A) (Jost et al., 2014). In EDLCs, the charge storage is based on a reversible ion adsorption from an electrolyte onto electrodes with high specific surface areas to form a double layer structure. The capacitance comes from the pure electrostatic... 

Surface-activate ions of the supporting electrolyte not only change the chemical potential of the organic substance in the solution, but also effect the structure of the electric double layer, increasing or decreasing the adsorption of orgainc molecules. Thus, in the presence of anions, which decrease the mutual repulsion between the adsorbed cations of [(C3H7)4N] the adsorption of the latter cations increases. At the same time, the specific adsorption of Br and I anions decreases the adsorption of ethyl alcohol, phenol and of the salicylate anion [3]. 

At the solid-liquid interface in soils, the specific distribution of cations and anions should be considered, as well as possible changes in the structure of water. The distribution of ions at the interface is determined by the electrical double layer. The structure and properties of water near the interface are governed by adsorption forces. The major contributor to interfacial effects in the soil system is the clay fraction because of the large total surface area per unit weight of clay particles. 

The fundamental electrochemical event, that is, electron transfer, occurs at the electrode surface. Peculiarities of electrochemical reactions include an electrical field, which in a special way complicates the phenomena of adsorption and desorption at the surface. The first layer of the solution, which is in contact with the electrode, possesses a specific structure. It is important for charged particles that the orientation of medium molecules in the vicinity of the electrode produces a decrease in dielectric permeability in the compact part of the double layer (Damaskin and Kryshtalik 1984). 

Specific adsorption of anions can give rise to unconventional temperature dependence of Tafel slopes on account of the temperature dependence of the ion adsorption and consequent changes of the structure and electric potential profile across the double layer where the transition state is established. 

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