Adsorption behavior

Various functional forms for / have been proposed either as a result of empirical observation or in terms of specific models. A particularly important example of the latter is that known as the Langmuir adsorption equation [2]. By analogy with the derivation for gas adsorption (see Section XVII-3), the Langmuir model assumes the surface to consist of adsorption sites, each having an area a. All adsorbed species interact only with a site and not with each other, and adsorption is thus limited to a monolayer. Related lattice models reduce to the Langmuir model under these assumptions [3,4]. In the case of adsorption from solution, however, it seems more plausible to consider an alternative phrasing of the model. Adsorption is still limited to a monolayer, but this layer is now regarded as an ideal two-dimensional solution of equal-size solute and solvent molecules of area a. Thus lateral interactions, absent in the site picture, cancel out in the ideal solution however, in the first version is a properly of the solid lattice, while in the second it is a properly of the adsorbed species. Both models attribute differences in adsorption behavior entirely to differences in adsorbate-solid interactions. Both present adsorption as a competition between solute and solvent. 

Fig. XI-13. Adsorption isotherms for SNBS (sodium p-3-nonylbenzene sulfonate) (pH 4.1) and DPC (dodecyl pyridinium chloride) (pH 8.0) on mtile at approximately the same surface potential and NaCl concentration of O.OlAf showing the four regimes of surfactant adsorption behavior, from Ref. 175. [Reprinted with permission from Luuk K. Koopal, Ellen M. Lee, and Marcel R. Bohmer, J. Colloid Interface Science, 170, 85-97 (1995). Copyright Academic Press.]...

Many solids have foreign atoms or molecular groupings on their surfaces that are so tightly held that they do not really enter into adsorption-desorption equilibrium and so can be regarded as part of the surface structure. The partial surface oxidation of carbon blacks has been mentioned as having an important influence on their adsorptive behavior (Section X-3A) depending on conditions, the oxidized surface may be acidic or basic (see Ref. 61), and the surface pattern of the carbon rings may be affected [62]. As one other example, the chemical nature of the acidic sites of silica-alumina catalysts has been a subject of much discussion. The main question has been whether the sites represented Brpnsted (proton donor) or Lewis (electron-acceptor) acids. Hall... 

Adsorbents such as some silica gels and types of carbons and zeolites have pores of the order of molecular dimensions, that is, from several up to 10-15 A in diameter. Adsorption in such pores is not readily treated as a capillary condensation phenomenon—in fact, there is typically no hysteresis loop. What happens physically is that as multilayer adsorption develops, the pore becomes filled by a meeting of the adsorbed films from opposing walls. Pores showing this type of adsorption behavior have come to be called micropores—a conventional definition is that micropore diameters are of width not exceeding 20 A (larger pores are called mesopores), see Ref. 221a. 

Surface heterogeneity may merely be a reflection of different types of chemisorption and chemisorption sites, as in the examples of Figs. XVIII-9 and XVIII-10. The presence of various crystal planes, as in powders, leads to heterogeneous adsorption behavior the effect may vary with particle size, as in the case of O2 on Pd [107]. Heterogeneity may be deliberate many catalysts consist of combinations of active surfaces, such as bimetallic alloys. In this last case, the surface properties may be intermediate between those of the pure metals (but one component may be in surface excess as with any solution) or they may be distinctly different. In this last case, one speaks of various effects ensemble, dilution, ligand, and kinetic (see Ref. 108 for details). 

Despite the difference ia the nature of the surface, the adsorptive behavior of the molecular sieve carbons resembles that of the small pore zeoHtes. As their name implies, molecular sieve separations are possible on these adsorbents based on the differences ia adsorption rate, which, ia the extreme limit, may iavolve complete exclusion of the larger molecules from the micropores. 

In a typical amorphous adsorbent the distribution of pore size may be very wide, spanning the range from a few nanometers to perhaps one micrometer. Siace different phenomena dominate the adsorptive behavior ia different pore size ranges, lUPAC has suggested the foUowiag classification ... 

Nevertheless, each of the more popular isotherm models have been found useful for modeling adsorption behavior in particular circumstances. The following outlines many of the isotherm models presently available. Detailed discussions of derivations, assumptions, strengths, and weaknesses of these and other isotherm models are given in references 4 and 7—16. 

Fig. 3. Model of the crystal structure of the mineral mordenite showing the main channel formed by 12-membered ring and small channels which contain some of the sodium cations. Synthetic types of mordenite exhibit the adsorption behavior of a 12-membered ring, whereas the mineral does not, probably...

In either equation, /c is given by Eq. (16-84) for parallel pore and surface diffusion or by Eq. (16-85) for a bidispersed particle. For nearly linear isotherms (0.7 < R < 1.5), the same linear addition of resistance can be used as a good approximation to predict the adsorption behavior of packed beds, since solutions for all mechanisms are nearly identical. With a highly favorable isotherm (R 0), however, the rate at each point is controlled by the resistance that is locally greater, and the principle of additivity of resistances breaks down. For approximate calculations with intermediate values of R, an overall transport parameter for use with the LDF approximation can be calculated from the following relationship for sohd diffusion and film resistance in series... 

Axial Dispersion Effects In adsorption bed calculations, axial dispersion effects are typically accounted for by the axial diffusionhke term in the bed conservation equations [Eqs. (16-51) and (16-52)]. For nearly linear isotherms (0.5 < R < 1.5), the combined effects of axial dispersion and mass-transfer resistances on the adsorption behavior of packed beds can be expressed approximately in terms of an apparent rate coefficient for use with a fluid-phase driving force (column 1, Table 16-12) ... 

The resulting adsorption behavior in an unsteady-state fixed bed adsorber is illustrated in Fig. 7 [32], As the gas stream enters the carbon bed, which is initially free of adsorbate, the adsorbate is rapidly adsorbed, and the gas is essentially free of adsorbate as it continues through the carbon bed. As the adsorbent at the inlet... 

Based on the gas adsorption behavior, Ko-zawa and Yamashita proposed a hypothesis [20, 21] that the cross—section of the fine pores of EMD is a cavity shape as shown in Fig. 16. The cross-section of the pore by computer calculation is a circle (Fig. 16A). Nobody knows the real shape of the cross-section as yet. Kozawa s belief in the cavity shape (Fig. 16B) is based on the results of experiments involving the oxygen adsorbed and desorbed from the pore walls [20]. 

Examinations of the connection between the chemical structure of alkylaryl sulfates and their physical-chemical properties show that solubility, aggregations and adsorption behavior, foam behavior and consistency are determined by the following structural elements the length of the alkyl chain, the position at which the benzene ring is connected to the alkyl chain, and the substitution pattern of the benzene ring [187,188]. 

The influence of the presence of alcohols on the CMC is also well known. In 1943 Miles and Shedlovsky [117] studied the effect of dodecanol on the surface tension of solutions of sodium dodecyl sulfate detecting a significant decrease of the surface tension and a displacement of the CMC toward lower surfactant concentrations. Schwuger studied the influence of different alcohols, such as hexanol, octanol, and decanol, on the surface tension of sodium hexa-decyl sulfate [118]. The effect of dodecyl alcohol on the surface tension, CMC, and adsorption behavior of sodium dodecyl sulfate was studied in detail by Batina et al. [119]. 

The adsorption behavior of homologous sodium alcohol sulfates at the interface can be characterized by the adsorption isotherms. However, the adsorption parameters of these isotherms are very sensitive to impurities present in the surfactant. Wiinstneck et al. [145] determined the equilibrium values of... 

As shown in Fig. 10, the plots of this equation for the binding energy are strong, i.e., >4 shows an S-shaped bend. Such adsorption behavior... 

The effect of temperature on adsorption was also stndied. At low temperatnre (i.e., near 0°C) adsorption proceeds very slowly, while at high temperatnre (40°C) the snrface coverage varies strongly from sample to sample, indicating side effects snch as partial desorption. Final valnes of always approached 30%, independent of the temperatnre. The effects of concentration and temperature on the surface coverage are clearly not compatible with a description of the adsorption behavior by Fangmnir s eqnation. 

Our laboratory has investigated adsorption behavior at air/water and Hg/water interfaces, the adsorption potentials caused by the aliphatic nitriles," dinitriles,monoalkyl ethers" dialkylethers" propalgyl alcohol, and dimethysulfoxide. The influence of the relative positions of two OH groups using the isomeric butanodiols has been also studied. ... 

The adsorption of a component j in a given system depends on temperature T and on the component s concentration, Cyj, in the bulk phase. The overall adsorption equation can be written as Aj =f(T, Cyj). The relation between adsorption and the adsorbate s bulk concentration (or pressure, in the case of gases) at constant temperature is called the adsorption isotherm the relation between adsorption and temperature at constant concentration is called the adsorption isobar. From the shape of the adsorption isotherms, the adsorption behavior can be interpreted. In the case of monolayer adsorption, the isotherms are usually written in the form 9 =f(Cyj). (The subscript j is dropped in what follows.)... 

Herteto E, Climent V, Feliu JM. 2000. On the different adsorption behavior of bismuth, sulfur, selenium and tellurium on a Pt(775) stepped surface. Electrochem Cotnmun 2 ... 

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