Sorption mechanism

A variety of mechanisms or forces can attract organic chemicals to a soil surface and retain them there. For a given chemical, or family of chemicals, several of these mechanisms may operate in the bonding of the chemical to the soil. For any given chemical, an increase in polarity, number of functional groups, and ionic nature of the chemical can increase the number of potential sorption mechanisms for the chemical. 

In general, three basic kinds of sorption mechanisms for trace elements in geologic aqueous systems can be distinguished (56). Due to non-specific forces of attraction between sorbent and the solute, a physical adsorption may occur. This sorption mechanism results in the binding of species from the solution in several consecutive layers on exposed solid surfaces. This would be a rapid non-selec-tive and reversible process, fairly independent of nuclide concentration and only little dependent on ion exchange capacity of the solid. 

In fact, one of the major applications of chitosan and some of its many derivatives is based on its ability to bind precious, heavy and toxic metal ions. Another article reviews the various classes of chitosan derivatives and compares their ion-binding abihties under varying conditions, as well as the analytical methods to analyze them, the sorption mechanism, and structural analysis of the metal complexes. Data are also presented exhaustively in tabular form with reference to each individual metal ion and the types of compounds that complex with it under various conditions, to help reach conclusions regarding the comparative efficacy of various classes of compounds [112]. 

Sorption mechanisms of Hg(II) by the nonliving biomass of Potamogeton natans was also elucidated using chemical and instrumental analyses including atomic absorption, electron microscopy, and x-ray energy dispersion analyses. The results showed a high maximum adsorption of Hg(II) (180 mg/g), which took place over the entire biomass surface. Nevertheless, there were spots on the surface where apparent multilayer sorption of Hg(II) occurred. The minimum concentration of Hg(II) in solution that can be removed appears to be about 4-5 mg/L.117... 

Ion exchange (an important sorption mechanism for inorganics) is viewed as an exchange with some other ion that initially occupies the adsorption site on the solid. For example, for metals (M+ +) in clay the exchanged ion is often calcium. 

In lc there are other sorption mechanisms that can cause separation, depending on whether we choose to use a liquid or a solid as the stationary phase, or what kind of solid we use. Liquid-liquid chromatography (11c) uses a liquid stationary phase coated onto a finely divided inert solid support. Separation here is due to differences in the partition coefficients of solutes between the stationary liquid and the liquid mobile phase. In normal phase 11c the stationary phase is relatively polar and the mobile phase relatively non-polar, whilst... 

Hi) Distribution is best (the other two are different kinds of sorption mechanism and are too specific). 

Navarro, R., Guzman, J., Saucedo, I., Revilla, J. and Guibal, E. (2003) Recovery of metal ions by chitosan sorption mechanisms and influence of metal speciation. Macromolecular Bioscience,... 

Jaynes WF, Vance GF (1999) Sorption of benzene, toluene, ethylbenzene and xylene (BTEX) compounds by hectorite clays exchanged with aromatic organic cations. Clays Clay Miner 47 358-365 Johnston CT, De Oliveira MF, Teppen BJ, Sheng G, Boyd SA (2001) Spectroscopic study of nitroaromatic-smectite sorption mechanisms. Environ Sci Technol 35 4767-4772... 

If the step is only equilibrium controlled, a lumped analysis of both fluid and solid phase is possible and the corresponding nonlinear wavefront analysis is straight forward too. Analysis of propagation speed data yield information about the relevant equilibrium sorption mechanism (7). The different form of the transients when a reaction step has been stimulated, is discussed in the Appendix. 

Pr q/Pro = 5,0 are relevant sorption effects of CO- but not of H2 thus only the 1 wavefronts represent rather tne shift conversion). Therefore it seems conceivable that there are two different mechanisms which participate in the CO shift conversion which is also in agreement with the established two different sorption mechanisms for 1 0 and with the transient behavior, depicted on Figure 6. 

Matousek J. Sorption-mechanical principle in skin decontamination. In Sohns T., Voicu V.A. (Eds.) NBC Risks Current Capabilities and Future Perspectives for Protection. Kluwer Academic Publishers, Dordrecht - Boston - London 1999, pp 265-269. 

The process whereby a solute is transferred from a mobile to a stationary phase is called sorption. Chromatographic techniques are based on four different sorption mechanisms, namely surface adsorption, partition, ion-... 

The use of HPLC in all its forms is growing steadily and may eventually exceed that of GC. This is because all four sorption mechanisms can be exploited and the technique is well suited to a very wide range of compound types including ionic, polymeric and labile materials. The most appropriate choice of mode of HPLC for a given separation problem is based on the relative molecular mass, solubility characteristics and polarity of the compounds to be separated and a guide to this is given in Figure 4.43. 

When used in direct soil analysis, XRF suffers from the fact that it is largely a surface phenomenon. For this reason, only surface elements will be determined. However, because it is a surface phenomenon, it has been extensively used to study sorption on the surfaces of soil components. An extensive list of investigations using XRF to investigate various sorption mechanisms is given in the text by Sparks [33],... 

Five material were chosen for the following tests to include different sorption mechanisms as well as different active phases. 

Some emphasis is given in the first two chapters to show that complex formation equilibria permit to predict quantitatively the extent of adsorption of H+, OH , of metal ions and ligands as a function of pH, solution variables and of surface characteristics. Although the surface chemistry of hydrous oxides is somewhat similar to that of reversible electrodes the charge development and sorption mechanism for oxides and other mineral surfaces are different. Charge development on hydrous oxides often results from coordinative interactions at the oxide surface. The surface coordinative model describes quantitatively how surface charge develops, and permits to incorporate the central features of the Electric Double Layer theory, above all the Gouy-Chapman diffuse double layer model. 

Fig. 4.18 shows the result of Cd2+ adsorption on illite in presence of Ca2+ (Comans, 1987). The data are fitted by Freundlich isotherms after an equilibration time of 54 days. It was shown in the experiments leading to these isotherms that adsorption approaches equilibrium faster than desorption. Comans has also used 109Cd to assess the isotope exchange he showed that at equilibrium (7-8 weeks equilibration time) the isotopic exchangeabilities are approximately 100 % i.e., all adsorbed Cd2+ is apparently in kinetic equilibrium with the solution. The available data do not allow a definite conclusion on the specific sorption mechanism. 

Fig. 6.10 shows idealized isotherms (at constant pH) for cation binding to an oxide surface. In the case of cation binding, onto a solid hydrous oxide, a metal hydroxide may precipitate and may form at the surface prior to their formation in bulk solution and thus contribute to the total apparent "sorption". The contribution of surface precipitation to the overall sorption increases as the sorbate/sorbent ratio is increased. At very high ratios, surface precipitation may become the dominant "apparent" sorption mechanism. Isotherms showing reversals as shown by e have been observed in studies of phosphate sorption by calcite (Freeman and Rowell, 1981). 

Spectroscopic techniques may provide the least ambiguous methods for verification of actual sorption mechanisms. Zeltner et al. (Chapter 8) have applied FTIR (Fourier Transform Infrared) spectroscopy and microcalorimetric titrations in a study of the adsorption of salicylic acid by goethite these techniques provide new information on the structure of organic acid complexes formed at the goethite-water interface. Ambe et al. (Chapter 19) present the results of an emission Mossbauer spectroscopic study of sorbed Co(II) and Sb(V). Although Mossbauer spectroscopy can only be used for a few chemical elements, the technique provides detailed information about the molecular bonding of sorbed species and may be used to differentiate between adsorption and surface precipitation. 

Measurements of the chemical composition of an aqueous solution phase are interpreted commonly to provide experimental evidence for either adsorption or surface precipitation mechanisms in sorption processes. The conceptual aspects of these measurements vis-a-vis their usefulness in distinguishing adsorption from precipitation phenomena are reviewed critically. It is concluded that the inherently macroscopic, indirect nature of the data produced by such measurements limit their applicability to determine sorption mechanisms in a fundamental way. Surface spectroscopy (optical or magnetic resonance), although not a fully developed experimental technique for aqueous colloidal systems, appears to offer the best hope for a truly molecular-level probe of the interfacial region that can discriminate among the structures that arise there from diverse chemical conditions. 

Solubility and kinetics methods for distinguishing adsorption from surface precipitation suffer from the fundamental weakness of being macroscopic approaches that do not involve a direct examination of the solid phase. Information about the composition of an aqueous solution phase is not sufficient to permit a clear inference of a sorption mechanism because the aqueous solution phase does not determine uniquely the nature of its contiguous solid phases, even at equilibrium (49). Perhaps more important is the fact that adsorption and surface precipitation are essentially molecular concepts on which strictly macroscopic approaches can provide no unambiguous data (12, 21). Molecular concepts can be studied only by molecular methods. 

Gratitude is expressed to Drs. M. E. Essington, C. T. Johnston, and R. L. Mikkelson for helpful written discussions of sorption mechanisms. The undertaking of this review was supported in part by Grant No. 1461-82 from BARD — The United States-Israel Binational Agricultural Research and Development Fund. 

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