Oxide-solution interface constant capacitance model

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 site binding model based on reactions (1), (2), (14) and (15), often called surface complexation model (SCM), was, beside the simple site binding models (for example two layer model or constant capacitance model) readily applied to a description of the edl on the metal oxide-electrolyte solution interface. Reactions (14) and (15) describe the adsorption of so-called back-... 

Figure 10,18 Schematic plot of surface species and charge (a) and potential ) relationships versus distance from the surface (at the zero plane) used in the constant capacitance (CC) and the diffuse-layer (DL) models. The capacitance, C is held constant in the CC model. The potential is the same at the zero and d planes in the diffuse-layer model i/fj). Reprinted from Adv. Colloid Interface Sci. 12, J. C. Westall and H. Hohl, A comparison of electrostatic models for the oxide/solution interface, pp. 265-294, Copyright 1980 with kind permission of Elsevier Science-NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands.

Constant Capacitance Model The constant capacitance model of the oxide-solution interface (Schindler et al., 1976 Stumm et al., 1980) contains the following assumptions ... 

Macroscopic experiments allow determination of the capacitances, potentials, and binding constants by fitting titration data to a particular model of the surface complexation reaction [105,106,110-121] however, this approach does not allow direct microscopic determination of the inter-layer spacing or the dielectric constant in the inter-layer region. While discrimination between inner-sphere and outer-sphere sorption complexes may be presumed from macroscopic experiments [122,123], direct determination of the structure and nature of surface complexes and the structure of the diffuse layer is not possible by these methods alone [40,124]. Nor is it clear that ideas from the chemistry of isolated species in solution (e.g., outer-vs. inner-sphere complexes) are directly transferable to the surface layer or if additional short- to mid-range structural ordering is important. Instead, in situ (in the presence of bulk water) molecular-scale probes such as X-ray absorption fine structure spectroscopy (XAFS) and X-ray standing wave (XSW) methods are needed to provide this information (see Section 3.4). To date, however, there have been very few molecular-scale experimental studies of the EDL at the metal oxide-aqueous solution interface (see, e.g., [125,126]). 

The method developed here for the description of chemical equilibria including adsorption on charged surfaces was applied to interpret phosphate adsorption on iron oxide (9), and to study electrical double-layer properties in simple electrolytes (6), and adsorption of metal ions on iron oxide (10). The mathematical formulation was combined with a procedure for determining constants from experimental data in a comparison of four different models for the surface/solution interface a constant-capacitance double-layer model, a diffuse double-layer model, the triplelayer model described here, and the Stem model (11). The reader is referred to the Literature Cited for an elaboration on the applications. 

---