Types of adsorption

Adsorption phenomena significantly influence the rate of electrode reactions. The heterogeneous nature of electrode reactions determines that energetics and local activities of reacting species in the vicinity of the electrode may be different from those in the bulk solution, even when mass transport limitations can be regarded as negligible. The structure and properties of the electrode—solution interface then play a key role in the adsorption of electroactive as well as electroinactive surface active substances (SAS) at electrodes. 

Since the electrolyte is a condensed phase, adsorption at electrodes, unlike at the solid—gas phase interface, is a process of replacement of specifically adsorbed solvent molecules or ions at the interface. 

The high electrical field across the interface and localized in a small distance as a consequence of the high capacitance of the electrode-solution interface also affects the adsorption phenomena considerably. Mutual interaction of adsorbed ions and dipoles is possible at the electrochemical interface. 

Parsons distinguishes four limiting cases of adsorption at electrodes with the real situations often crossing the classification boundaries [94] (a) purely electrostatic adsorption, (b) specific ionic adsorption, (c) adsorption of uncharged species (but including dipoles) and (d) chemisorption. 

Purely electrostatic adsorption has been described by the Gouy— Chapman theory [21, 22] as described in Sect. 2.3 and involves the less specific interaction with the electrode due to its state of charge. 

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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 Unction of this chapter is to summarize some of the general approaches to the determination of the physical and chemical state in both of the types of adsorption systems described. 

As also noted in the preceding chapter, it is customary to divide adsorption into two broad classes, namely, physical adsorption and chemisorption. Physical adsorption equilibrium is very rapid in attainment (except when limited by mass transport rates in the gas phase or within a porous adsorbent) and is reversible, the adsorbate being removable without change by lowering the pressure (there may be hysteresis in the case of a porous solid). It is supposed that this type of adsorption occurs as a result of the same type of relatively nonspecific intermolecular forces that are responsible for the condensation of a vapor to a liquid, and in physical adsorption the heat of adsorption should be in the range of heats of condensation. Physical adsorption is usually important only for gases below their critical temperature, that is, for vapors. 

As is made evident in the next section, there is no sharp dividing line between these two types of adsorption, although the extremes are easily distinguishable. It is true that most of the experimental work has tended to cluster at these extremes, but this is more a reflection of practical interests and of human nature than of anything else. At any rate, although this chapter is ostensibly devoted to physical adsorption, much of the material can be applied to chemisorption as well. For the moment, we do assume that the adsorption process is reversible in the sense that equilibrium is reached and that on desorption the adsorbate is recovered unchanged. 

Fig. XVII-7. Brunauer s five types of adsorption isotherms. (From Ref. 34.)...

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. 

Still another type of adsorption system is that in which either a proton transfer occurs between the adsorbent site and the adsorbate or a Lewis acid-base type of reaction occurs. An important group of solids having acid sites is that of the various silica-aluminas, widely used as cracking catalysts. The sites center on surface aluminum ions but could be either proton donor (Brpnsted acid) or Lewis acid in type. The type of site can be distinguished by infrared spectroscopy, since an adsorbed base, such as ammonia or pyridine, should be either in the ammonium or pyridinium ion form or in coordinated form. The type of data obtainable is illustrated in Fig. XVIII-20, which shows a portion of the infrared spectrum of pyridine adsorbed on a Mo(IV)-Al203 catalyst. In the presence of some surface water both Lewis and Brpnsted types of adsorbed pyridine are seen, as marked in the figure. Thus the features at 1450 and 1620 cm are attributed to pyridine bound to Lewis acid sites, while those at 1540... 

Figure Al.7.9. Schematic diagram illustrating three types of adsorption sites.

There is much room for further study of various importaut categories of materials oue promiueut example is oxides aud other compouuds (carbides, nitrides,. . . ) another is all types of adsorption on oxides and other compounds. 

The balance between these different types of bonds has a strong bearing on the resulting ordering or disordering of the surface. For adsorbates, the relative strength of adsorbate-substrate and adsorbate-adsorbate interactions is particularly important. Wlien adsorbate-substrate interactions dominate, well ordered overlayer structures are induced that are arranged in a superlattice, i.e. a periodicity which is closely related to that of the substrate lattice one then speaks of commensurate overlayers. This results from the tendency for each adsorbate to seek out the same type of adsorption site on the surface, which means that all adsorbates attempt to bond in the same maimer to substrate atoms. 

Fig. I.l The five types of adsorption isotherm, I to V, in the classification of Brunauer, Deming, Deming and Teller (BDDT), together with Type VI, the stepped isotherm.

Adsorption-Control Equipment If a gas stream must be treated for a short period, nsnally only one adsorption unit is necessary, provided, of course, that a sufficient time interval is available between adsorption cycles to permit regeneration. However, this is usually not the case. Since an nninternipted flow of treated gas is often required, it is necessary to employ one or more units capable of operating in this fashion. The units are designed to handle gas flows without interruption and are charac terized by their mode of contact, either staged or continuous. By far the most common type of adsorption system used to remove an objectionable pollutant from a gas stream consists of a number of fixed-bed units operating in such a sequence that the gas flow remains nninternipted. A two- or three-bed system is nsn ly... 

Physisorption occurs when, as a result of energy differences and/or electrical attractive forces (weak van der Waals forces), the adsorbate molecules become physically fastened to the adsorbent molecules. This type of adsorption is multilayered that is, each molecular layer forms on top of the previous layer with the number of layers being proportional to the contaminant concentration. More molecular layers form with higher concentrations of contaminant in solution. When a chemical compound is produced by the reaction between the adsorbed molecule and the adsorbent, chemisorption occurs. Unlike physisorption, this process is one molecule thick and irreversible... 

Types of Adsorbers Five types of adsorption equipment are used in collecting gases containing organic compounds ... 

The symmetry listed for Y is for a strong adsorbate-adsorbent interaction. The symmetry may vary with different types of adsorption. 

Figure 5.22 reveals the ability of solid state electrochemistry to create new types of adsorption on metal catalyst electrodes. Here oxygen has been supplied not from the gas phase but electrochemically, as 02 via current application for a time, denoted tj, of 1=15 pA at 673 K, i.e. at the same temperature used for gaseous O2 adsorption (Fig. 5.21). Figure 5.23 shows the effect of mixed gaseous-electrochemical adsorption. The Pt surface has been initially exposed to po2 =4x1 O 6 Torr for 1800 s (7.2 kL) followed by electrochemical O2 supply (1=15 pA) for various time periods ti shown on the figure, in order to simulate NEMCA conditions. 

Both equations are valid. The question is to find what type of adsorption isotherms for j are consistent with both equations (6.53) and (6.54). Consistency with both equations implies that... 

The next stage in the catalytic cycle is adsorption of the reactants onto the catalyst surface. There are two types of adsorption process ... 

On this Pd rich alloy (Fdgm.f == 70%) the same types of adsorption are present as on Pd. (ref.21) (Reproduced with permission from Ref.21. North-Holland Publ.Co.)... 

As the reader might have noticed, many conclusions in electrocatalysis are based on results obtained with electrochemical techniques. In situ characterization of nanoparticles with imaging and spectroscopic methods, which is performed in a number of laboratories, is invaluable for the understanding of PSEs. Identification of the types of adsorption sites on supported metal nanoparticles, as well as determination of the influence of particle size on the adsorption isotherms for oxygen, hydrogen, and anions, are required for further understanding of the fundamentals of electrocatalysis. 

Thus, as of today, there is no reliable classification of various types of adsorption. Presumably, it would be most correct to consider various types of adsorption interactions consistent with classification of chemical bonds [19]. 

At different types of adsorption isotherms plotted for adsorption of donor particles on oxides (see section 1.5) expressions (1.112) - (1.115) provide the rise in and decrease in with the growth of partial pressure of gas P, the functions themselves being different. Thus, in case of applicability of the Henry isotherm at small P we have the function oi - exp const-P becoming a power function <7s P with the rise in P which is often observed in experiments [154, 155, 169]. 

Three types of adsorption isotherms are discussed in this section ... 

As noted above, adsorption isotherms are largely derived empirically and give no information on the types of adsorption that may be involved. Scrivner and colleagues39 have developed an adsorption model for montmorillonite clay that can predict the exchange of binary and ternary ions in solution (two and three ions in the chemical system). This model would be more relevant for modeling the behavior of heavy metals that actively participate in ion-exchange reactions than for organics, in which physical adsorption is more important. 

Fixed-charge minerals such as clay are even more complex than the multiple-surface site minerals, and both ion exchange and other types of adsorption must be measured to characterize absorption reactions fully. 

Certain types of adsorption media have been shown to preferentially adsorb certain contaminants. For example, research has shown that, in some cases, coconut shell-based GAC removes MTBE better than typical coal-based GAC. In addition, synthetic resins have been developed to preferentially adsorb some oxygenates, such as TBA, that are less absorbable by GAC. Often, adsorption processes also take advantage of the biodegradability of MTBE and other oxygenates by promoting bacterial growth on the adsorption. 

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