Physical adsorption reversible process

Heats of adsorption are due to three fundamental processes, physical adsorption, reversible chemisorption, and irreversible chemisorption. Physical adsorption can be attributed to van der Waals forces (dispersion forces). Reversible and irreversible chemisorption are due to bond formation between the adsorbent and the adsorbate. Generally heats of adsorption less than 10-15 kcal/mole are considered due to physical adsorption alone, although some physical adsorption processes may exceed these values. Any chemisorption process generally involves all three processes so that the heat of adsorption value reflects the sum of the average contribution of each. The interaction of transition metals with unsaturated compounds is attributed by most authors, at least in part, to chemisorption. 

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. 

Most adsorption processes are exothermic (AH is negative). Adsorption processes involving nonspecific interactions are referred to as physical adsorption, a relatively weak, reversible interaction. Processes with stronger interactions (electron transfer) are termed chemisorption. Chemisorption is often irreversible and has higher heat of adsorption than physical adsorption. Most dispersants function by chemisorption, in contrast to surfactants, which... 

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. 

Many organic electrode processes require the adsorption of the electroactive species at the electrode surface before the electron transfer can occur. This adsorption may take the form of physical or reversible chemical adsorption, as has been commonly observed at a mercury/water interface, or it may take the form of irreversible, dissociative chemical adsorption where bond fracture occurs during the adsorption process and often leads to the complete destruction of the molecule. This latter t q)e of adsorption is particularly prevalent at metals in the platinum group and accounts for their activity as heterogeneous catalysts and as... 

Some deactivation processes are reversible. Deactivation by physical adsorption occurs whenever there is a gas-phase impurity that is below its critical point. It can be reversed by eliminating the impurity from the feed stream. This form of deactivation is better modeled using a site-competition model that includes the impurities—e.g., any of Equations (10.18)-(10.21)— rather than using the effectiveness factor. Water may be included in the reaction mixture so that the water-gas shift reaction will minimize the formation of coke. Off-line decoking can be... 

A third empirical criterion is based on the effect of temperature on the amount adsorbed. For physical adsorption the amount of gas adsorbed always decreases monotonically as the temperature is increased. Significant amounts of physical adsorption should not occur at temperatures in excess of the normal boiling point at the operating pressure. Appreciable chemisorption can occur at temperatures above the boiling point and even above the critical temperature of the material. Because chemisorption can be an activated process that takes place at a slow rate, it may be difficult to determine the amount of chemisorption corresponding to true equilibrium. Moreover, the process may not be reversible. It is also possible for two or more types of chemisorption or for chemical and physical adsorption to occur simultaneously on the same surface. These facts make it difficult to generalize with regard to the effect of temperature on the amount adsorbed. Different behavior will be observed for different adsorbent-adsorbate systems. 

Physical adsorption is a readily reversible process, and alternate adsorption and desorption stages can be carried out repeatedly without changing the character of the surface or the adsorbate. Chemisorption may or may not be reversible. Often one species may be adsorbed and a second desorbed. Oxygen adsorbed on charcoal at room temperature is held very strongly, and high temperatures are necessary to accomplish the desorption. CO and/or C02 are the species that are removed from the surface. Chemical changes like these are prima facie evidence that chemisorption has occurred. 

The actual adsorption of vapor molecules takes place mainly on the surface of internal passages within the adsorbent particles, since that is where most of the available surface exists. The adsorption process may be either physical or chemical in nature. Physical adsorption is a readily reversible process that occurs as a result of the physical attraction between the gas molecules and the molecules of the solid surface. If the gas-solid intermolecular attraction is greater than the intermolecular attractions in the gas phase, the gas will condense on the solid surface, even though its pressure is lower than its vapor pressure at the prevailing temperature. For example, the equilibrium adsorption pressure of acetone on activated carbon may, under some conditions, be as little as 150 to 1,100 of the equilibrium vapor pressure at... 

Reversible physical adsorption of hydrophobic pollutants with dissolved-phase and solid-phase HS (i. e., DPm and SPm, respectively) is a well established and fundamental interaction affecting the equilibrium distribution and rate of an organic pollutant between soil/sediment, water, and air [82,181-184]. There has been - and still is - continuing literature discussion regarding the physical association of hydrophobic organic pollutants with sediment and soil involving a process of adsorption or partitioning [77,103,108,113,130,185-188]. 

Physical adsorption is fully reversible, enabling both the adsorption and desorption processes to be studied. 

The three types of adsorption are (1) physical, (2) chemical, and (3) exchange adsorption. Especially important to the success of in situ treatment by Fe° are the soil characteristics, which affect soil sorptive behavior such as mineralogy, permeability, porosity texture, surface qualities, and pH. Physical adsorption is due to van der Waal s forces between molecules where the adsorbed molecule is not fixed on the solid surface but is free to move over the surface and may condense and form several superimposed layers. An important characteristic of physical adsorption is its reversibility. On the other hand, chemical adsorption is a result of much stronger forces with a layer forming, usually of one molecule thickness, where the molecules do not move. It is normally not reversible and must be removed by heat. The exchange adsorption and ion exchange process involves adsorption by electrical attraction between the adsorbate and the surface (Rulkens, 1998). 

The attainment of physical adsorption equilibrium is usually rapid, since there is no activation energy involved, and (apart from complications introduced by capillary condensation) the process is readily reversible. Multilayer physical adsorption is possible, and at... 

Only monomolecular chemisorbed layers are possible. Chemisorption is a specific process which may require an activation energy and may, therefore, be relatively slow and not readily reversible. The nature of physical adsorption and chemisorption is illustrated by the schematic potential energy curves shown in Figure 5.2 for the adsorption of a diatomic gas X2 on a metal M. 

In general, two types of adsorption are distinguished, physical adsorption and chemisorption, which depend on the type of interaction established between the adsorbent and the adsorptive. In a chemisorption process, specific chemical interactions between the adsorbent and the adsorptive occur, and the process is not reversible. On the other hand, physical adsorption includes attractive dispersion forces and, at very short distances, repulsive forces, as well as contribution from polarization and electrostatic forces between permanent electrical moments and the electrical field of the solid, if the adsorptive or the adsorbent has a polar nature. In this case, the process is fully reversible (or almost reversible). Thus, the overall interaction energy ( >(z) of a molecule of adsorptive at a distance z from the surface of the adsorbent is given by the general expression... 

Sorption is a surface phenomenon determined by the surface charges and those of the ions surrounding it. One or more of the following mechanisms can be involved in the removal of species by sorption (i) mechanical entrapment, (ii) absorption, (iii) physical sorption, or (iv) chemical sorption on the surface of the solid particle. Physical adsorption (which is weaker than its chemical counterpart) occurs through Van der Waals forces and it is generally reversible and instantaneous. On the other hand, chemical adsorption or chemisorption occurs through the formation of chemical bonds at specific sites. This is closely related to ion exchange processes and complexation. 

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