Sorption equilibria, isotherm models

In conclusion, the different shapes of isotherms describing equilibrium distributions of a contaminant, between geosorbents and aqueous or gaseous phases, depend on the sorption mechanism involved and the associated sorption energy. At low contaminant concentration, all models reduce to essentially linear correlation. At higher contaminant concentration, when sorption isotherms deviate from linearity, an appropriate isotherm model should be used to describe the retention process. 

The results of experimental studies of the sorption and diffusion of light hydrocarbons and some other simple nonpolar molecules in type-A zeolites are summarized and compared with reported data for similar molecules in H-chabazite. Henry s law constants and equilibrium isotherms for both zeolites are interpreted in terms of a simple theoretical model. Zeolitic diffusivitiesy measured over small differential concentration steps, show a pronounced increase with sorbate concentration. This effect can be accounted for by the nonlinearity of the isotherms and the intrinsic mobilities are essentially independent of concentration. Activation energies for diffusion, calculated from the temperature dependence of the intrinsic mobilitieSy show a clear correlation with critical diameter. For the simpler moleculeSy transition state theory gives a quantitative prediction of the experimental diffusivity. 

Geochemical models of sorption and desorption must be developed from this work and incorporated into transport models that predict radionuclide migration. A frequently used, simple sorption (or desorption) model is the empirical distribution coefficient, Kj. This quantity is simply the equilibrium concentration of sorbed radionuclide divided by the equilibrium concentration of radionuclide in solution. Values of Kd can be used to calculate a retardation factor, R, which is used in solute transport equations to predict radionuclide migration in groundwater. The calculations assume instantaneous sorption, a linear sorption isotherm, and single-valued adsorption-desorption isotherms. These assumptions have been shown to be erroneous for solute sorption in several groundwater-soil systems (1-2). A more accurate description of radionuclide sorption is an isothermal equation such as the Freundlich equation ... 

Sorption of organic contaminants onto aquifer solids is frequently described as a partitioning process, where the hydrophobic organic compound partitions into natural organic material associated with the aquifer solids [8]. Sorption can be characterized as either an equilibrium or rate-limited phenomenon. Equilibrium sorption can be modeled as either a linear or non-linear process. Equilibrium sorption may be assumed when the flow of groundwater and other processes affecting contaminant transport are slow compared to the rate of sorption. In this event the sorption of the contaminant can be considered instantaneous. If we assume equilibrium sorption, the relationship between sorbed and aqueous contaminant concentrations may be described by a sorption isotherm. 

Equilibrium between solution and adsorbed or sorbed phases is a condition commonly used to evaluate adsorption or sorption processes in soils or soil-clay minerals. As previously stated, equilibrium is defined as the point at which the rate of the forward reaction equals the rate of the reverse reaction. Two major techniques commonly used to model soil adsorption or sorption equilibrium processes are (1) the Freundlich approach and (2) the Langmuir approach. Both involve adsorption or sorption isotherms. A sorption isotherm describes the relationship between the dissolved concentration of a given chemical species (adsorbate) in units of micrograms per liter (pg L 1), milligrams per liter (mg L-1), microequivalents per liter (pequiv L-1), or millimoles per liter (mmol L-1), and the sorbed quantity of the same species by the solid phase (adsorbent) in units of adsorbate per unit mass of adsorbent (solid) (e.g., pg kg-1, mg kg-1, peq kg-1, or mmol kg 1) at equilibrium under constant pressure and temperature. Sorption isotherms have been classified into four types, depending on their general shape (Fig. 4.13) ... 

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. 

Sorbed pesticides are not available for transport, but if water having lower pesticide concentration moves through the soil layer, pesticide is desorbed from the soil surface until a new equihbrium is reached. Thus, the kinetics of sorption and desorption relative to the water conductivity rates determine the actual rate of pesticide transport. At high rates of water flow, chances are greater that sorption and desorption reactions may not reach equilibrium (64). Nonequihbrium models may describe sorption and desorption better under these circumstances. The prediction of herbicide concentration in the soil solution is further compHcated by hysteresis in the sorption—desorption isotherms. Both sorption and dispersion contribute to the substantial retention of herbicide found behind the initial front in typical breakthrough curves and to the depth distribution of residues. 

Equilibrium sorption isotherms heats of sorption, and diffusivities have been calculated for carbon dioxide in type A zeolites, using an idealized model of the molecular potential field. Good agreement with practical results are obtained for heats of sorption, but results are poor for equilibrium isotherms, and the simple approximation used for diffusivity is quite inadequate. Nevertheless, useful insight is obtained on the basic assumptions. 

Sorption Kinetics. The adsorption and desorption data were analyzed in terms of a model based on the following main assumptions. Micropore diffusion within the sieve crystals is the rate-controlling process. Diffusion may be described by Fick s law for spherical particle geometry with a constant micropore diffusivity. The helium present in the system is inert and plays no direct role in the sorption or diffusion process. Sorption occurs under isothermal conditions. Sorption equilibrium is maintained at the crystal surface, which is subjected to a step change in gas composition. These assumptions lead to the following relation for the amount of ethane adsorbed or desorbed by a single particle as a function of time (Crank, 4). 

Natural surfaces generally are too complex to be characterized as having uniform solute interaction energies, however. It is therefore not unexpected that sorption equilibrium data for natural soils and sediments are rarely described adequately by the Langmuir model. Such data are commonly described more satisfactorily by the empirical Freundlich isotherm model, which has the form... 

Sousa et al [5.76, 5.77] modeled a CMR utilizing a dense catalytic polymeric membrane for an equilibrium limited elementary gas phase reaction of the type ttaA +abB acC +adD. The model considers well-stirred retentate and permeate sides, isothermal operation, Fickian transport across the membrane with constant diffusivities, and a linear sorption equilibrium between the bulk and membrane phases. The conversion enhancement over the thermodynamic equilibrium value corresponding to equimolar feed conditions is studied for three different cases An > 0, An = 0, and An < 0, where An = (ac + ad) -(aa + ab). Souza et al [5.76, 5.77] conclude that the conversion can be significantly enhanced, when the diffusion coefficients of the products are higher than those of the reactants and/or the sorption coefficients are lower, the degree of enhancement affected strongly by An and the Thiele modulus. They report that performance of a dense polymeric membrane CMR depends on both the sorption and diffusion coefficients but in a different way, so the study of such a reactor should not be based on overall component permeabilities. 

Fundamentals of sorption and sorption kinetics by zeohtes are described and analyzed in the first Chapter which was written by D. M. Ruthven. It includes the treatment of the sorption equilibrium in microporous sohds as described by basic laws as well as the discussion of appropriate models such as the Ideal Langmuir Model for mono- and multi-component systems, the Dual-Site Langmuir Model, the Unilan and Toth Model, and the Simphfied Statistical Model. Similarly, the Gibbs Adsorption Isotherm, the Dubinin-Polanyi Theory, and the Ideal Adsorbed Solution Theory are discussed. With respect to sorption kinetics, the cases of self-diffusion and transport diffusion are discriminated, their relationship is analyzed and, in this context, the Maxwell-Stefan Model discussed. Finally, basic aspects of measurements of micropore diffusion both under equilibrium and non-equilibrium conditions are elucidated. The important role of micropore diffusion in separation and catalytic processes is illustrated. 

The equilibrium sorption isotherms are one of the most important data to understand the mechanism of the sorption. They describe the ratio between the quantity of sorbate retained by the sorbent and that remaining in the solution at the constant temperature at equilibrium and are important from both theoretical and practical points of view. The parameters obtained from the isotherm models provide important information not only about the sorption mechanisms but also about the surface properties and affinities of the sorbent. The best known adsorption models in the linearized form for the single-solute systems are ... 

The data of Loukidou et al. (2004) for the equilibrium biosorption of chromium (VI) by Aeromonas caviae particles were well described by the Langmuir and Freundlich isotherms. Sorption rates estimated from pseudo second-order kinetics were in satisfactory agreement with experimental data. The results of XAFS study on the sorption of Cd by B. subtilis were generally in accord with existing surface complexation models (Boyanov et al. 2003). Intrinsic metal sorption constants were obtained by correcting the apparent sorption constants by the Boltzmann factor. A 1 2 metal-ligand stoichiometry provides the best fit to the experimental data with log K values of 6.0 0.2 for Sr(II) and 6.2 0.2 for Ba(II). 

Loukidou et al. (2005) fitted the data for the equilibrium sorption of Cd from aqueous solutions by Aeromonas caviae to the Langmuir and Freundlich isotherms. They also conducted, a detailed analysis of sorption rates to validate several kinetic models. A suitable kinetic equation was derived, assuming that biosorption is chemically controlled. The so-called pseudo second-order rate expression could satisfactorily describe the experimental data. The adsorption data of Zn on soil bacterium Pseudomonas putida were fit with the van Bemmelen-Freundlich model (Toner et al. 2005). 

In many early experiments, hysteresis was observed for highly hydrophobic compounds such as PCBs (79, 80). Since the time to reach equilibrium can be quite long for strongly hydrophobic compounds, a solute may have never reached equilibrium during the sorption isotherm experiment. Consequently, Kj would be underestimated, which leads to the discrepancy between the sorption and desorption coefficients that was attributed to hysteresis. The case for hysteresis being an artifact is supported by recent data for tetrachlorobenzene (log K = 4.7), illustrating that sorption and desorption require approximately two days to reach equilibrium with approximately equal time constants (78). Finally, the diffusion model is consistent with the observation that the extent of hysteresis was inversely related to particle size (81). 

The basic assumptions for application of graphic isotherm and regression equations are that the data be derived under equilibrium conditions, constant temperature, and minimal fixation effects, and the data can be modeled as a regression function. The equations are valid only within the experimental concentration ranges used to determine the sorption. 

Of the various equilibrium and non-equilibrium sorption isotherms or sorption characteristics models, the most popular are the Langmuir and Freundlich models. The correct modeling of an adsorbate undergoing both transport and adsorption through a clay soil-solid system necessitates the selection of an adsorption isotherm or characteristic model which best suits the given system. The use of an improper or inappropriate adsorption model will greatly affect the... 

Equilibrium considerations alone may partly explain the nonlinear sorption isotherm, i.e., when n in the Freundlich model (Eq. 8) is less than unity, intraparticle retardation will increase as the concentration inside the particle declines. However, in some studies it appears that the concentration dependence is steeper than expected based on equilibrium nonlinearity. 

It is important to differentiate between the two different types of sorption/ desorption tests (i. e.,batch and column-leaching), and the sorption characteristics determined from one should not be confused with the other. Sorption isotherms obtained with batch equilibrium tests are applied mainly to solid suspensions. The physical model, assumed with this situation, is one of a completely dispersed solid particle system, where all solid particle surfaces are exposed and available for interactions with the contaminants of concern. In contrast, column-leaching tests are performed with intact solid samples, and the sorption characteristics obtained from them are the results of contaminant interactions with a structured system where not all-solid particle surfaces are exposed or available for interactions with the contaminants. 

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