Layer Helmholtz compact

The traditional treatment of a double layer at electrode-electrolyte interfaces is based on its separation into two series contributions the compact ( Helmholtz ) layer and the diffusive ( dif ) layer, so that the inverse capacitance is... 

When a metal electrode is placed in an electrolyte solution, an equilibrium difference usually becomes established between the metal and solution. Equilibrium is reached when the electrons left in the metal contribute to the formation of a layer of ions whose charge is equal and opposite to that of the cations in solution at the interface. The positive charges of cations in the solution and the negative charges of electrons in the metal electrode form the electrical double layer [4]. The solution side of the double layer is made up of several layers as shown in Fig. 2.7. The inner layer, which is closest to the electrode, consists of solvent and other ions, which are called specifically adsorbed ions. This inner layer is called the compact Helmholtz layer, and the locus of the electrical centers of this inner layer is called the inner Helmholtz plane, which is at a distance of di from the metal electrode surface. The solvated ion can approach the electrode only to a distance d2. The locus of the centers of the nearest solvated ion is called the outer Helmholtz plane. The interaction of the solvated ion with metal electrode only involves electrostatic force and is independent of the chemical properties of the ions. These ions are called non-specifically adsorbed ions. These ions are distributed in the 3D region called diffusion layer whose thickness depends on the ionic concentration in the electrolyte. The structure of the double layer affects the rate of electrode reactions. 

There is no such effect for uncharged species (Zi = 0) and not in cases of a high concentration of supporting electrolyte. In the latter case the whole potential drop is in the compact Helmholtz layer [there is no diffuse double layer, ( 0]. 

The Stern Model is a combination of the Helmholtz and Gouy-Chapman models (Figure 3.47). The potential difference between the metal and the solution is comprised of two terms A h. due to the compact Helmholtz layer and A0gc, due to the diffuse Gouy-Chapman layer. 

In general, the Helmholtz layer can be treated as a linear capacitor. In a theoretical model of the electric double-layer, the compact Helmholtz layer is generally treated as an ideal capacitor with a fixed thickness (d), and its capacitance is considered unchanging with the potential drop across it. Therefore, fhe capacifance of fhe Helmholtz layer can be treated as a constant if fhe femperafure, fhe dielectric constant of the electrolyte solution inside the compact layer, and its thickness are fixed. However, if the specific ion adsorpfion happened on the electrode surface, the dielectric constant of the electrolyte solution inside the compact layer may be affected, leading to non-linear behavior of the Helmholtz layer. This will be discussed more in a later section. 

Total double-layer capacitance is composed of a series combination of the compact Helmholtz layer and the diffuse-layer capacitances as ... 

The thickness of the compact Helmholtz layer (L 1-2 ran) is approximately equal to the length of closest proximity where the discharging ions can approach the interface. For aqueous media with relative permittivity e = 80 and a 2 nm thick Helmholtz layer, fiF/cm. While the Helm-... 

Helmholtz and diffuse-layer capacitances due to the presence of supporting electrolyte but not electroactive species discharged at e electrode. The bulk-resistance parameter due to migration remains the same in both representations. In the kinetic representation the double-layer capacitance (that is, the capacitance between the electrode and both supporting electrolyte and electroactive species in diffuse and Helmholtz layers) and the charge-transfer resistance (due to electroactive species in the compact Helmholtz layer) are replaced by the reaction capacitance in parallel with the reaction resistance... 

The inner layer (closest to the electrode), known as the inner Helmholtz plane (IHP), contains solvent molecules and specifically adsorbed ions (which are not hilly solvated). It is defined by the locus of points for the specifically adsorbed ions. The next layer, the outer Helmholtz plane (OHP), reflects the imaginary plane passing through the center of solvated ions at then closest approach to the surface. The solvated ions are nonspecifically adsorbed and are attracted to the surface by long-range coulombic forces. Both Helmholtz layers represent the compact layer. Such a compact layer of charges is strongly held by the electrode and can survive even when the electrode is pulled out of the solution. The Helmholtz model does not take into account the thermal motion of ions, which loosens them from the compact layer. 

The diffuse layer of excess electrons and holes in solids is called the space charge layer and the diffuse layer of excess hydrated ions in aqueous solution is simply called the diffuse layer and occasionally called the Gouy layer [Gouy, 1917]. The middle layer of adsorbed water moleciiles, between the diffuse layer on the aqueous solution side and the space charge layer on the soUd side, is called the compact or the inner layer. This compact or inner layer is also called the Helmholtz layer [Helmholtz, 1879] or the Stem layer [Stem, 1924] the plane of the closest approach of hydrated ions to the solid surface is called the outer Helmholtz plane (OHP) [Graham, 1947]. 

Fig. 5-8. Diffuse charge layer on the solution side of metal electrode M = electrode metal S = aqueous solution HL = compact layer (Helmholtz layer) DL = diffuse charge layer x distance from the outer Helmholtz plane (OHP).

Chemisorption of anions at the electrode interface involves dehydration of hydrated anions followed by adsorption of dehydrated anions which, then, penetrate into the compact double layer to contact the interface directly, this result is called the contact adsorption or specific adsorption. The plane of the contact adsorption of dehydrated anions is occasionally called the inner Helmholtz plane... 

Ionic contact adsorption on metallic electrodes alters the potential profile across the compact layer at constant electrode potential. If anions are adsorbed on the metal electrode at positive potentials, the adsorption-induced dipole generates a potential across the inner Helmholtz layer (IHL) as illustrated in Fig. 5-29. The electric field in the outer part (OHL) of the compact layer, as a result, becomes dififerent fi om and frequently opposite to that in the inner part (IHL) of the compact layer. 

Fig. 9-1. Potential energy profile for transferring metal ions across an interface of metal electrode M/S py. = metal ion level (electrochemical potential) x = distance fiom an interface au. = real potential of interfacial metal ions = real potential of hydrated metal ions - compact layer (Helmholtz layer) V = outer potential of solution S, curve 1 = potential energy of interfadal metallic ions curve 2 = potential energy of hydrated metal ions.

The simplest model of the structure of the metal-solution interphase is the Helmholtz compact double-layer model (1879). According to this model, all the excess charge... 

Electrode-solution interface. The tightly adsorbed inner layer (also called the compact, Helmholtz, or Stem layer) may include solvent and any solute molecules. Cations in the inner layer do not completely balance the charge of the electrode. Therefore, excess cations are required in the diffuse part of the double layer for charge balance. 

The simplest model of the structure of the metal-solution interphase is the Helmholtz compact double-layer model (1879). According to this model, all the excess charge on the solution side of the interphase, qs. is lined up in the same plane at a fixed distance away from the electrode, the Helmholtz plane (Fig. 4.4). This fixed distance xH is determined by the hydration sphere of the ions. It is defined as the plane of the centers of the hydrated ions. All excess charge on the metal, qM, is located at the metal surface. 

What is the "correct" value of the thickness of the parallel plate capacitor in Eq. 3G. This may be seen by reference to Fig. 6G(a), which shows the surface of a negatively charged electrode covered with a layer of water molecules. The distance of closest approach of a cation is the sum of the diameter of a water molecule (0.27 nm) and its own hydrated radius. For the latter we can use the so-called Stokes radii, calculated from electrolytic conductivity data, which are in the range of 0.2-0.3 nm for most ions. Thus, the thickness of the compact double layer (i.e., the distance of the outer Helmholtz plane from the metal) is 0.47-0.57 nm. 

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