Solid—solution interface, surface complexation

Various chemical surface complexation models have been developed to describe potentiometric titration and metal adsorption data at the oxide—mineral solution interface. Surface complexation models provide molecular descriptions of metal adsorption using an equilibrium approach that defines surface species, chemical reactions, mass balances, and charge balances. Thermodynamic properties such as solid-phase activity coefficients and equilibrium constants are calculated mathematically. The major advancement of the chemical surface complexation models is consideration of charge on both the adsorbate metal ion and the adsorbent surface. In addition, these models can provide insight into the stoichiometry and reactivity of adsorbed species. Application of these models to reference oxide minerals has been extensive, but their use in describing ion adsorption by clay minerals, organic materials, and soils has been more limited. 

Kallay, N. Matijevic, F. (1985) Adsorption at solid/solution interfaces. I. Interpretation of surface complexation of oxalic and citric acids with hematite. Langmuir 1 195-201... 

The TLM (Davis and Leckie, 1978) is the most complex model described in Figure 4. It is an example of an SCM. These models describe sorption within a framework similar to that used to describe reactions between metals and ligands in solutions (Kentef fll., 1988 Davis and Kent, 1990 Stumm, 1992). Reactions involving surface sites and solution species are postulated based on experimental data and theoretical principles. Mass balance, charge balance, and mass action laws are used to predict sorption as a function of solution chemistry. Different SCMs incorporate different assumptions about the nature of the solid - solution interface. These include the number of distinct surface planes where cations and anions can attach (double layer versus triple layer) and the relations between surface charge, electrical capacitance, and activity coefficients of surface species. 

Surface complexation models (SCM s) provide a rational interpretation of the physical and chemical processes of adsorption and are able to simulate adsorption in complex geochemical systems. Chemical reactions at the solid-solution interface are treated as surface complexation reactions analogous to the formation of complexes in solution. Each reaction is defined in terms of a mass action equation and an equilibrium constant. The activities of adsorbing ions are modified by a coulombic term to account for the energy required to penetrate the electrostatic-potential field extending away from the surface. Detailed information on surface complexation theory and the models that have been developed, can be found in (Stumm et al., 1976 ... 

In 1991, Johnson et al. reported one of the first NR studies of phospholipid bilayers at the solid-solution interface [46]. Although these measurements were not the first to employ NR to study molecules adsorbed at the solid-hquid interface, they did constitute the first measurements of a supported bilayer using NR. A bilayer of dimyristoylphosphatidylcholine (DMPC) was spread on a quartz surface by the fusion and rupturing of smaU unilamellar vesicles. The very smooth, singlecomponent substrate aUowed a complex model of the interface to be constructed from layers corresponding to (i) the quartz, (ii) a thin film of water on the quartz... 

Surface complexation models of the solid-solution interface share at least six common assumptions (1) surfaces can be described as planes of constant electrical potential with a specific surface site density (2) equations can be written to describe reactions between solution species and the surface sites (3) the reactants and products in these equations are at local equilibrium and their relative concentrations can be described using mass law equations (4) variable charge at the mineral surface is a direct result of chemical reactions at the surface (5) the effect of surface charge on measured equilibrium constants can be calculated and (6) the intrinsic (i.e., charge and potential independent) equilibrium constants can then be extracted from experimental measurements (Dzombak and Morel, 1990 Koretsky, 2000). 

Several models have been developed to describe reactions between aqueous ions and solid surfaces. These models tend to fall into two categories (1) empirical partitioning models, such as distribution coefficients and isotherms (e.g., Langmuir and Freundlich isotherms), and (2) surface-complexation models (e.g., constant-capacitance, diffuse-layer, or triple-layer model) that are analogous to solution complexation with corrections for the electrostatic effects at the solid-solution interface (Davis and Kent, 1990). These models have been described in numerous articles (Westall and Hohl, 1980 Morel, Yeasted, and Westall, 1981 James and Parks, 1982 Barrow, 1983 Westall, 1986 Davis and Kent, 1990 Dzombak and Morel, 1990). Travis and Etnier (1981) provided a comprehensive review of the partitioning and kinetic models typically used to define sorption of ions by soils. The reader is referred to the cited articles for details of the models. 

A general conclusion of our experimental study would be that comprehensive studies of solid-solution interfaces via ATR-IR may contribute to solving the structure of surface complexes. Furthermore, such studies may help finding ptreviously unidentified species in solution speciation schemes. Overall the interplay of surface complexation and solution complexation in this system indicates that the adsorption ptrooess may be very complex and that multi-method approaches are best suited to gain deep>er imderstanding. 

The charging mechanisms of the porous solid-liquid interface are complex, possibly including the asymmetric dipoles of water molecules residing at the solid-liquid interface, adsorption of ions, disassociation of ionic groups, charge separation, etc. The presence of surface charges will influence the distribution of nearby ions in the solution. Counter-ions (i. e., ions of opposite charge)... 

For the cation-surface site complex, (SO)2M the net electrostatic charge at a solid-solution interface, where the electrostatic charge on the Stem plane was... 

Of special interest in liquid dispersions are the surface-active agents that tend to accumulate at air/ liquid, liquid/liquid, and/or solid/liquid interfaces. Surfactants can arrange themselves to form a coherent film surrounding the dispersed droplets (in emulsions) or suspended particles (in suspensions). This process is an oriented physical adsorption. Adsorption at the interface tends to increase with increasing thermodynamic activity of the surfactant in solution until a complete monolayer is formed at the interface or until the active sites are saturated with surfactant molecules. Also, a multilayer of adsorbed surfactant molecules may occur, resulting in more complex adsorption isotherms. 

Adsorption is a physicochemical process whereby ionic and nonionic solutes become concentrated from solution at solid-liquid interfaces.3132 Adsorption and desorption are caused by interactions between and among molecules in solution and those in the structure of solid surfaces. Adsorption is a major mechanism affecting the mobility of heavy metals and toxic organic substances and is thus a major consideration when assessing transport. Because adsorption is usually fully or partly reversible (desorption), only rarely can it be considered a detoxification process for fate-assessment purposes. Although adsorption does not directly affect the toxicity of a substance, the substance may be rendered nontoxic by concurrent transformation processes such as hydrolysis and biodegradation. Many chemical and physical properties of both aqueous and solid phases affect adsorption, and the physical chemistry of the process itself is complex. For example, adsorption of one ion may result in desorption of another ion (known as ion exchange). 

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