Double layer specifically adsorbed ions

Ions can be adsorbed specifically if the main contribution to their interaction with the interface (ions, dipoles) is caused by non-coulombic short-range forces. Specific adsorption caimot be explained using only the theory of diffuse double layer. Specifically adsorbed ions penetrate to the compact layer and form a compact or loose monolayer. The surface passing through the centers of specifically adsorbed ions is usually called the inner Helmholtz plane. If several kinds of specifically adsorbed ions... 

FIGURE 9.4 Schematic representation of an electrical double layer. Specifically adsorbed ions have lost (a part of) their hydration water and are in direct contact with the charged surface. At the right-hand side of the dotted line ions (-1-/-) are diffusely distributed in solution. 

Certain counterions may be held in the compact region of the double layer by forces additional to those of purely electrostatic origin, resulting in their adsorption in the Stern layer. Specifically, adsorbed ions are attracted to the surface by electrostatic and/or van der Waals forces strongly enough to overcome the thermal agitation. 

Fig. 1. The structure of the electrical double layer where Q represents the solvent CD, specifically adsorbed anions 0, anions and (D, cations. The inner Helmholtz plane (IHP) is the center of specifically adsorbed ions. The outer Helmholtz plane (OHP) is the closest point of approach for solvated cations or molecules. O, the corresponding electric potential across the double layer, is also shown.

Even in the absence of Faradaic current, ie, in the case of an ideally polarizable electrode, changing the potential of the electrode causes a transient current to flow, charging the double layer. The metal may have an excess charge near its surface to balance the charge of the specifically adsorbed ions. These two planes of charge separated by a small distance are analogous to a capacitor. Thus the electrode is analogous to a double-layer capacitance in parallel with a kinetic resistance. 

Equation (2.33) now defines the double layer in the final model of the structure of the electrolyte near the electrode specifically adsorbed ions and solvent in the IHP, solvated ions forming a plane parallel to the electrode in the OHP and a dilfuse layer of ions having an excess of ions charged opposite to that on the electrode. The excess charge density in the latter region decays exponentially with distance away from the OHP. In addition, the Stern model allows some prediction of the relative importance of the diffuse vs. Helmholtz layers as a function of concentration. Table 2.1 shows... 

Figure 1. A schematic representation of the synthesis of the electrochemical double layer in UHV a) adsorption of specifically adsorbed ions without solvent b) addition of hydration water c) completion of the inner layer d) addition of solvent multilayers, e) model for the double layer at an electrode surface in solution.

Ions with a weak solvation shell, anions in general, lose a part of or the complete solvation shell in the double layer and form a chemical bond to the metal surface. The adsorption is termed specific since the interaction occurs only for certain ions or molecules and is not related to the charge on the ion. The plane where the center of these ions are located is called the inner Helmholtz layer. In the specific adsorption, ions are chemically bound to the surface and the interaction has a covalent nature. In the case of non-specific adsorption, in which an electrostatic force binds ions to the surface, the coverage of ions is below 0.1 -0.2 ML due to electrostatic repulsion between the ions. In contrast, the coverage of specifically adsorbed ions exceeds this value, and a close-packed layer of specifically adsorbed ions is often observed. Specifically adsorbed ions are easily observed by STM [22], indicating that the junction between the electrode surface and the inner Helmholtz layer is highly... 

Partial charge transfer during adsorption is difficult to evaluate because separation of the charge transferred to the electrode and that part of the charge transferred across the double layer to give specifically adsorbed ions cannot be done through measurements of the total charge in the external circuit. Vetter and Schultze [102] defined the electrosorption valence as... 

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. 

Specifically adsorbed ions are those which are attached (albeit temporarily) to the surface by electrostatic and/or van der Waals forces strongly enough to overcome thermal agitation. They may be dehydrated, at least in the direction of the surface. The centres of any specifically adsorbed ions are located in the Stern layer - i.e. between the surface and the Stern plane. Ions with centres located beyond the Stern plane form the diffuse part of the double layer, for which the Gouy-Chapman treatment outlined in the previous section, with 0o replaced by (f/d, is considered to be applicable. 

Forming a monolayer involves displacing specifically adsorbed ions and solvent molecules from the interface, which changes the double-layer capacitance from that... 

The inner part of the double layer may include specifically adsorbed ions. In this case, the center of the specifically adsorbed ions is located between the surface and the Stem plane. Specifically adsorbed ions (e.g., surfactants) either lower or elevate the Stem potential and the zeta potential as shown in Figure 4.31. When the specific adsorption of the surface-active or polyvalent counter ions is strong, the charge sign of the Stem potential will be reversed. The Stem potential can be greater than the surface potential if the surface-active co-ions are adsorbed. The adsorption of nonionic surfactants causes the surface of shear to be moved to a much longer distance from the Stem plane. As a result, the zeta potential will be much lower than the Stem potential. 

The solvent molecules form an oriented parallel, producing an electric potential that is added to the surface potential. This layer of solvent molecules can be protruded by the specifically adsorbed ions, or inner-sphere complexed ions. In this model, the solvent molecules together with the specifically adsorbed, inner-sphere complexed ions form the inner Helmholtz layer. Some authors divide the inner Helmholtz layer into two additional layers. For example, Grahame (1950) and Conway et al. (1951) assume that the relative permittivity of water varies along the double layer. In addition, the Stern variable surface charge-variable surface potential model (Bowden et al. 1977, 1980 Barrow et al. 1980, 1981) states that hydrogen and hydroxide ions, specifically adsorbed and inner-sphere... 

When ions specifically adsorb at the interface, the excess surface charge density is divided into three parts, the charges in the two diffuse parts of the double layer, q and q, and the charge due to the specifically adsorbed ions, q° [25]. The electroneutrality condition of the entire interfacial region is... 

In fig. 3.20b specific adsorption Is also accounted for. The notion of specific adsorption has been defined In sec. 3.3. In disperse systems, its occurrence is de facto Inferred from the dependence of certain double layer properties on the natures of counter- and co-lons Generally, ions interacting specifically (non-electrostatlcally) with the surface approach it to shorter distance p < d). The plane where these specifically adsorbed ions reside is called the inner Helmholtz plane (iHp) In colloid science, the model of fig. 3.20b Is also known as the triple layer model. In this model three charges and three capacitances can be distinguished. For the two inner layer differential capacitances... 

Stern [4] introduced the concept of the nondiffuse part of the double layer for specifically adsorbed ions, the remainder being diffuse in nature this is shown schematically in Figure 7.4, where the potential is seen to drop linearly in the Stern region, and then exponentially. Grahame distinguished two types of ions in the Stern plane, namely physically adsorbed counterions (outer Helmholtz plane) and chemically adsorbed ions that lose part of their hydration shell (inner Helmholtz plane). 

The double layer extension increases with decreases in electrolyte concentration. Stem [9] introduced the concept of the nondifiuse part of the double layer for specifically adsorbed ions, the remainder being diffuse in nature. The potential... 

Stem improved the Gouy-Chapman theory of the DDL by assuming that some ions are tightly retained immediately next to colloid surfaces in a layer of specifically adsorbed or Stem- layer cations. The double layer is diffuse beyond this layer. A satisfactory approximation of the Stem model can be made by assuming that the specifically adsorbed ions quantitatively reduce the surface density of the colloid. The diffuse portion of the double layer then is assumed to develop on a colloid surface of correspondingly reduced charge density. Sample Stem-modification calculations for a series of monovalent cations are shown in Fig. 8.10, Relatively few of the... 

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