Electrical double layer at the oxide solution interface

Free Energies of Electrical Double Layers at the Oxide-Solution Interface... 

The aim of this paper is not to add to the current debate but to present a simple graphical method of analysing the free energy of formation of the electrical double layer at the oxide/solution interface ( 1). This will provide a simple way of visualizing the complementary roles of chemical reactions or surface properties of... 

The main, currently used, surface complexation models (SCMs) are the constant capacitance, the diffuse double layer (DDL) or two layer, the triple layer, the four layer and the CD-MUSIC models. These models differ mainly in their descriptions of the electrical double layer at the oxide/solution interface and, in particular, in the locations of the various adsorbing species. As a result, the electrostatic equations which are used to relate surface potential to surface charge, i. e. the way the free energy of adsorption is divided into its chemical and electrostatic components, are different for each model. A further difference is the method by which the weakly bound (non specifically adsorbing see below) ions are treated. The CD-MUSIC model differs from all the others in that it attempts to take into account the nature and arrangement of the surface functional groups of the adsorbent. These models, which are fully described in a number of reviews (Westall and Hohl, 1980 Westall, 1986, 1987 James and Parks, 1982 Sparks, 1986 Schindler and Stumm, 1987 Davis and Kent, 1990 Hiemstra and Van Riemsdijk, 1996 Venema et al., 1996) are summarised here. 

The pH value at which the oxide surface carries no fixed charge, i.e. Oj = 0, is defined as the point of zero charge (PZC) . A closely related parameter, the isoelectric point (lEP), obtained from electrophoretic mobility and streaming potential data, refers to the pH value at which the electrokinetic potential equals to zero The PZC and lEP should coincide when there is no specific adsorption in the iimer region of the electric double layer at the oxide-solution interface. In the presence of the specific adsorption, the PZC and lEP values move in opposite directions as the concentration of supporting electrolyte is increased. ... 

In the active state, the dissolution of metals proceeds through the anodic transfer of metal ions across the compact electric double layer at the interface between the bare metal and the aqueous solution. In the passive state, the formation of a thin passive oxide film causes the interfadal structure to change from a simple metal/solution interface to a three-phase structure composed of the metal/fUm interface, a thin film layer, and the film/solution interface [Sato, 1976, 1990]. The rate of metal dissolution in the passive state, then, is controlled by the transfer rate of metal ions across the film/solution interface (the dissolution rate of a passive semiconductor oxide film) this rate is a function of the potential across the film/solution interface. Since the potential across the film/solution interface is constant in the stationary state of the passive oxide film (in the state of band edge level pinning), the rate of the film dissolution is independent of the electrode potential in the range of potential of the passive state. In the transpassive state, however, the potential across the film/solution interface becomes dependent on the electrode potential (in the state of Fermi level pinning), and the dissolution of the thin transpassive film depends on the electrode potential as described in Sec. 11.4.2. 

The electrical double layer at the metal oxide/electrolyte solution interface can be described by characteristic parameters such as surface charge and electrokinetic potential. Metal oxide surface charge is created by the adsorption of electrolyte ions and potential determining ions (H+ and OH-).9 This phenomenon is described by ionization and complexation reactions of surface hydroxyl groups, and each of these reactions can be characterized by suitable constants such as pKa , pKa2, pKAn and pKct. The values of the point of zero charge (pHpzc), the isoelectric point (pH ep), and all surface reaction constants for the measured oxides are collected in Table 1. 

At the beginning, the electric double layer at the solid-aqueous electrolyte solution interface was characterized by the measurements of the electrokinetic potential and stability of dispersed systems. Later, the investigations were supported by potentiometric titration of the suspension, adsorption and calorimetric measurements [2]. Now, much valuable information on the mechanism of the ion adsorption can be obtained by advanced spectroscopic methods (especially infrared ATR and diffuse spectroscopy) [3], Mosbauer spectroscopy [4] and X-ray spectroscopy [5]. Some data concerning the interface potential were obtained with MOSFET [6], and AFM [7]. An enthalpy of the reaction of the metal oxide-solution systems can be obtained by... 

The substantial parameter at the modeling of the electric double layer at metal oxide-electrolyte solution interface is a number of the hydroxyl group per surface unit of the oxide. For the titanium dioxide, although different crystalline faces form the surface [rutile 60% of the surface is formed by the face (110) whereas for anatase by (001)] the same density 12.8 of —OH group/nm2 is assumed [28]. That results from the very similar intersection of the elementary cells of the mentioned face, which have the highest density of the atoms in both oxides. 

Each element of this circuit appropriately models the specific process or phenomenon occurring in the system investigated. In the circuit shown in Fig. 13 the resistance element Rs represents corrosive environment, i.e., 0.5 M NaCl solution. The resistance representing the charge transfer through the interface associated with the process of oxidation of iron, i.e., the corrosion element, is described by R, and the electrical double layer at the interface iron -0.5M NaCl solution is characterized by a constant phase element CPEdi. The use of two constant-phase elements in an equivalent electric circuit improves the quality of model fit to... 

The current measured at the electrode surfiice in dc hydrodynamic am-perometry is the summation of several factors (1) The background (faradic) current, due to the redox reactions of impurities, solvents, etc. comprising the mobile phase (2) the signal (faradic) current, arising from the oxidation of the solute(s) of interest and (3) the charging (capacitance) current, a temporary transient which occurs whenever the cell is turned on or the potential is changed. This current charges the electrical double layer, a tiny dremical capacitor at the electrode - solution interface, to approximately the potential. 

The surfaces of oxide colloidal particles or silicate minerals in contact with aqueous solutions are charged positively or negatively by adsorption or desorption of H+ ions. An electrical double layer at solid/liquid interface is formed by adsorbing counterions from the aqueous solution to its surface (Sen and Khilar, 2009). The charge developing process on the surfaces can be represented as follows (Cornell and Schwertmann, 1998) ... 

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]).

Figure 3. Highly schematic view of the electrical double layer (EDL) at a metal oxide/aqueous solution interface showing (1) hydrated cations specifically adsorbed as inner-sphere complexes on the negatively charged mineral surface (pH > pHpzc of the metal oxide) (2) hydrated anions specifically and non-specifically adsorbed as outer-sphere complexes (3) the various planes associated with the Gouy-Chapman-Grahame-Stem model of the EDL and (4) the variation in water structure and dielectric constant (s) of water as a function of distance from the interface, (from Brown and Parks 2001, with permission)...

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