Sorption model, various, discussion

The second modeling approach discussed in this section presents an overview of the fundamentals of quantitative structure-activity relationships (i.e., QSARs [102-130]) and quantitative structure-property relationships (i.e., QSPRs [131-139]). It will show how such an approach can be used in order to estimate and predict sorption/desorption coefficients of various organic pollutants in environmental systems. 

A characteristic feature associated with pore condensation is the occurrence of sorption hysteresis, i.e pore evaporation occurs usually at a lower p/po compared to the condensation process. The details of this hysteresis loop depend on the thermodynamic state of the pore fluid and on the texture of adsorbents, i.e. the presence of a pore network. An empirical classification of common types of sorption hysteresis, which reflects a widely accepted correlation between the shape of the hysteresis loop and the geometry and texture of the mesoporous adsorbent was published by lUPAC [10]. However, detailed effects of these various factors on the hysteresis loop are not fully understood. In the literature mainly two models are discussed, which both contribute to the understanding of sorption hysteresis [8] (i) single pore model. hysteresis is considered as an intrinsic property of the phase transition in a single pore, reflecting the existence of metastable gas-states, (ii) neiM ork model hysteresis is explained as a consequence of the interconnectivity of a real porous network with a wide distribution of pore sizes. 

An important and recently reported issue, namely slow sorption/desorption rates, their causes at the intra-particle level of various solid phases, and how these phenomena relate to contaminant transport, bio availability, and remediation, is also discussed and evaluated. A case study showing the environmental impact of solid waste materials which are mainly complex organic mixtures and/or their reuse/recycling as highway construction and repair materials is presented and evaluated from the point of view of sorption/desorption behavior and data modeling. 

The main objectives of this chapter are to (1) review the different modeling techniques used for sorption/desorption processes of organic pollutants with various solid phases, (2) discuss the kinetics of such processes with some insight into the interpretation of kinetic data, (3) describe the different sorption/ desorption experimental techniques, with estimates of the transport parameters from the data of laboratory tests, (4) discuss a recently reported issue regarding slow sorption/desorption behavior of organic pollutants, and finally (5) present a case study about the environmental impact of solid waste materials/complex... 

The following sections show various sorption isotherms that can be used to model single pollutant/leachate component system adsorption. In addition some predictive models for multi-pollutants/leachate(s) component solutions are also summarized and discussed. 

While first-order models have been used widely to describe the kinetics of solid phase sorption/desorption processes, a number of other models have been employed. These include various ordered equations such as zero-order, second-order, fractional-order, Elovich, power function or fractional power, and parabolic diffusion models. A brief discussion of these models will be provided the final forms of the equations are given in Table 2. 

Other modeling efforts include soil acidification models of the macroscopic type that account for the process of S04 sorption in different ways. These approaches, which assume equilibrium conditions to prevail, include the adsorption isotherm, solubility product, and anion exchange. Prenzel (1994) discussed the various limitations of the above approaches in their capability to account for changes in pH. Recently, Fumoto and Sverdrup (2000) used a constant capacitance approach to describe the pH dependency of S04 sorption isotherms in an andisol. Other modeling efforts of S04 isotherms were reported by Gustafsson (1995) in a spodosol. Such isotherm models are of the equilibrium type and include linear and Temkin types of models. 

The different solid-fluid interaction models and the various types and sizes of the sorbent media particles, as well as the purpose of a sorption operation, separation, purihcation, and so on, led to the development of a variety of processes, along with the required equipment types. These processes are associated with the main interaction models discussed earlier adsorption, ion exchange, and chromatography. 

Surfactants influence electrokinetic remediation in various ways. They adsorb to soils and alter their surface properties, and as a result, EOF and sorption of hydro-phobic organics to the soils are affected. Surfactants also increase the aqueous phase concentration of organics via micellar solubilization. Depending on the type of surfactants, micelles, and therefore organic contaminants within the micelles, may be transported toward the anode or cathode. A simphfied conceptual model of a surfactant-enhanced electrokinetic process is presented in Figure 11.1. The effects of surfactants on these processes are discussed below in more detail. 

Yawalkar et al. (2001) has developed a model for a three-phase reactor based on the use of a dense polymeric composite membrane containing discrete cubic zeolite particles (Fig. 4.5) for the epoxidation reaction of alkene. Catalytic particles of the same size are assumed vdth a cubic shape and uniformly dispersed across the polymer membrane cross-section. Effects of various parameters, such as peroxide and alkene concentration in liquid phase, sorption coefficient of the membrane for peroxide and alkene, membrane-catalyst distribution coefficient for peroxide and alkene and catalyst loading, have been studied. The results have been discussed in terms of a peroxide effidency defined as the ratio of flux of peroxide through the membrane utilized for alkene oxidation to the total flux of organic peroxide through the membrane. The paper aimed to show that, by using an organophilic dense membrane and the catalysts confined in the polymeric matrix, the oxidant concentration (in that reaction peroxides) can be controlled on the active site with an improvement of the peroxide efficiency and selectivity to desired products. 

Section 4 treats the thermodynamic aspects of the hydrogen sorption. The treatment includes the van t Hoff relationship between plateau pressure and heat and entropy of formation, the validity of the van t Hoff relationship close to the critical point, the maximum hydrogen capacity, and the extension of the Lacher and Rees description to multiplateau isotherms. Also discussed are various models that relate the hydrogen sorption to other physical properties of the intermetallics such as formation enthalpy, elastic properties and interstitial hole sizes. 

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