Gas-solid adsorption

Solid-gas Adsorption Solid aerosol, adsorption, catalysis, corrosion, diffusion, surface energy, thin films, permeation, osmosis, filtration, oxidation, charge transfer, condensation and nucleation... 

The objectives of this paper are to demonstrate how monolayer adsorption isotherms can be obtained on carbon fiber surfaces by inverse gas chromatography (IGC), and to compare results of solid/gas adsorption with those of solid/Uquid wetting. This information is correlated with independent assessments of surface chemical functionality provided by wet chemical titrations and x—ray photoelectron spectroscopy (XPS). 

Granulation properties are mainly dependent on the size and surface area of particles and granules (24,25) The surface area of a granule or particle can also affect the dissolution rate of a solid. Gas adsorption is the most common method to determine surface area, although liquid penetration methods have also been proposed (26). In one of the methods developed by Brunauer, Emmet, and Teller, called the BET method (27), an inert gas is adsorbed onto the surface of a solid at low temperature and then desorbed at room temperature (1). Either nitrogen or krypton is used as the adsorbate, and helium is usually used as a carrier gas for the adsorbate. Various concentrations of adsorbate in carrier gas are used in this analysis to determine the volume of gas that is adsorbed in a monolayer on to the solid. Eq. 2.1 is used to determine this value... 

The solid-gas interface and the important topics of physical adsorption, chemisorption, and catalysis are addressed in Chapters XVI-XVIII. These subjects marry fundamental molecular studies with problems of great practical importance. Again the emphasis is on the basic aspects of the problems and those areas where modeling complements experiment. 

There is always some degree of adsorption of a gas or vapor at the solid-gas interface for vapors at pressures approaching the saturation pressure, the amount of adsorption can be quite large and may approach or exceed the point of monolayer formation. This type of adsorption, that of vapors near their saturation pressure, is called physical adsorption-, the forces responsible for it are similar in nature to those acting in condensation processes in general and may be somewhat loosely termed van der Waals forces, discussed in Chapter VII. The very large volume of literature associated with this subject is covered in some detail in Chapter XVII. 

The present discussion is restricted to an introductory demonstration of how, in principle, adsorption data may be employed to determine changes in the solid-gas interfacial free energy. A typical adsorption isotherm (of the physical adsorption type) is shown in Fig. X-1. In this figure, the amount adsorbed per gram of powdered quartz is plotted against P/F, where P is the pressure of the adsorbate vapor and P is the vapor pressure of the pure liquid adsorbate. 

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. 

While a thermodynamic treatment can be developed entirely in terms of f(P,T), to apply adsorption models, it is highly desirable to know on a per square centimeter basis rather than a per gram basis or, alternatively, to know B, the fraction of surface covered. In both the physical chemistry and the applied chemistry of the solid-gas interface, the specific surface area is thus of extreme importance. 

Section 3.7, the gas adsorption method breaks down for practical reasons. Since the angle of contact of mercury with solids is 140° (see later), and therefore more than 90°, an excess pressure Ap is required to force liquid mercury into the pores of a soh d. The idea of using mercury intrusion to measure pore size appears to have been first suggested by Washburn who put forward the basic equation... 

A vast amount of research has been undertaken on adsorption phenomena and the nature of solid surfaces over the fifteen years since the first edition was published, but for the most part this work has resulted in the refinement of existing theoretical principles and experimental procedures rather than in the formulation of entirely new concepts. In spite of the acknowledged weakness of its theoretical foundations, the Brunauer-Emmett-Teller (BET) method still remains the most widely used procedure for the determination of surface area similarly, methods based on the Kelvin equation are still generally applied for the computation of mesopore size distribution from gas adsorption data. However, the more recent studies, especially those carried out on well defined surfaces, have led to a clearer understanding of the scope and limitations of these methods furthermore, the growing awareness of the importance of molecular sieve carbons and zeolites has generated considerable interest in the properties of microporous solids and the mechanism of micropore filling. 

The second edition, like the first, is addressed to those workers in academic laboratories or industrial laboratories who are not necessarily specialists in the field of gas adsorption, but whose work is concerned either directly or indirectly with the characterization of finely divided or porous solids. 

Figure 9,16 Comparison of theory with experiment for rg/a versus K. The solid line is drawn according to the theory for flexible chains in a cylindrical pore. Experimental points show some data, with pore dimensions determined by mercury penetration (circles, a = 21 nm) and gas adsorption (squares, a= 41 nm). [From W. W. Yau and C. P. yidXont, Polym. Prepr. 12 797 (1971), used with permission.]...

Adsorption The design of gas-adsorption equipment is in many ways analogous to the design of gas-absorption equipment, with a solid adsorbent replacing the liqiiid solvent (see Secs. 16 and 19). Similarity is evident in the material- and energy-balance equations as well as in the methods employed to determine the column height. The final choice, as one would expect, rests with the overall process economics. 

Volume 104 Equilibria and Dynamics of Gas Adsorption on Heterogeneous Solid Surfaces edited by W. Rudzihski, W.A. Steele and G. Zgrablich Volume 105 Progress in Zeolite and Microporous Materials... 

Activated carbon in particular is very versatile as a filter media because it not only can physically separate out suspended solids, but it can adsorb materials. The adsorption process occurs at solid-solid, gas-solid, gas-liquid, liquid-liquid, or... 

W. Rudzinski, G. Zgrablich, eds. Equilibria dynamics of gas adsorption on heterogeneous solid surfaces. In Studies in Surface Science and Catalysis, Vol 104. Amsterdam Elsevier, 1997. 

Most surface area measurements are based on the interpretation of the low temperature equilibrium adsorption of nitrogen or of krypton on the solid using the BET theory [33,269,276—278]. There is an extensive literature devoted to area determinations from gas adsorption data. Estimates of surfaces may also be obtained from electron micrographs, X-ray diffraction line broadening [279] and changes in the catalytic activity of the solid phase [ 280]. 

In the near future, the possible synthesis of nanotubes with solid-gas potential will be more favorable to adsorption. The effect of hydrogen overpressure on the stability of adsorbed Ha needs to be verified in the near future. The high-purity nanotube produced by laser vaporization, catalytic decomposition, or other techniques should be investigated. It is noteworthy that the synthesis of the SWNT with defined diameters and distances between the walls is difficult to perform at present, but future synthesis routes will allow more... 

Much of the pioneering work which led to the discovery of efficient catalysts for modern Industrial catalytic processes was performed at a time when advanced analytical Instrumentation was not available. Insights Into catalytic phenomena were achieved through gas adsorption, molecular reaction probes, and macroscopic kinetic measurements. Although Sabatier postulated the existence of unstable reaction Intermediates at the turn of this century. It was not until the 1950 s that such species were actually observed on solid surfaces by Elschens and co-workers (2.) using Infrared spectroscopy. Today, scientists have the luxury of using a multitude of sophisticated surface analytical techniques to study catalytic phenomena on a molecular level. Nevertheless, kinetic measurements using chemically specific probe molecules are still the... 

D. H. Everett 1967, (Adsorption hysteresis), in The Solid-gas Interface, ed. E. Alison Flood, Marcel Dekker, New York. 

Equilibria and Dynamics of Gas Adsorption on Heterogeneous Solid Surfaces... 

The adsorption of inert gases onto solid materials represents the most widely used method for the determination of surface area, although other methods are available [6,7]. The BET method, developed by Brunauer, Emmett, and Teller [8], is generally used for gas adsorption surface area measurements. 

The intrinsic dissolution rates of pharmaceutical solids may be calculated from the dissolution rate and wetted surface area using Eq. (36) or (37). For powdered solids, two common methods are available the powder intrinsic dissolution rate method, and the disc intrinsic dissolution rate method. In the former method, the initial dissolution rate of one gram of powder is determined by a batch-type procedure as illustrated in Fig. 13A. The initial wetted surface area of one gram of powder is assumed to equal the specific surface area determined by an established dry procedure, such as monolayer gas adsorption by the Brunauer, Emmett, and Teller (BET) procedure [110]. 

In general, the BET equation fits adsorption data quite well over the relative pressure range 0.05-0.35, but it predicts considerably more adsorption at higher relative pressures than is experimentally observed. This is consistent with an assumption built into the BET derivation that an infinite number of layers are adsorbed at a relative pressure of unity. Application of the BET equation to nonpolar gas adsorption results is carried out quite frequently to obtain estimates of the specific surface area of solid samples. By assuming a cross-sectional area for the adsorbate molecule, one can use Wm to calculate specific surface area by the following relationship ... 

In the last two sections the formal theory of surface thermodynamics is used to describe material characteristics. The effect of interfaces on some important heterogeneous phase equilibria is summarized in Section 6.2. Here the focus is on the effect of the curvature of the interface. In Section 6.3 adsorption is covered. Physical and chemical adsorption and the effect of interface or surface energies on the segregation of chemical species in the interfacial region are covered. Of special importance again are solid-gas or liquid-gas interfaces and adsorption isotherms, and the thermodynamics of physically adsorbed species is here the main focus. 

The book Principles of Adsorption and Reaction on Solid Surfaces by Richard I. Masel, Wiley, New York, 1996, concentrates on mechanistic detail and adsorption at the solid-gas interface, but, within its self-imposed limitations, it is a superb book. 

Gas separation membranes, conducting polymer applications, 7 539 Gas-solid chromatography, adsorption,... 

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