Chemisorption heat

When gaseous or liquid molecules adhere to thesurface of the adsorbent by means of a chemical reaction and the formation of chemical bonds, the phenomenon is called chemical adsorption or chemisorption. Heat releases of 10 to 100 kcal/g-mol are typical for chemisorption, which are much higher than the heat release for physisorption. With chemical adsorption, regeneration is often either difficult or impossible. Chemisorption usually occurs only at temperatures greater than 200 C when the activation energy is available to make or break chemical bonds. 

Exposure of silicon to atomic hydrogen increases the surface recombination velocity.111213 The free energy of formation of SiH4, the most stable of the hydrides of silicon, is only — lOKcal/mole. Since four electron pairs are shared in the formation of the molecule, the free energy of formations per Si-H bond is only -2.5 Kcal or about O.leV. Because of the weak chemisorption, heating of the silicon to temperatures above 500 C is adequate to release the hydrogen. Our model explains the increase in surface recombination velocity by the weak chemisorption of hydrogen, which may increase the density of surface states within the band gap (see Fig. 2b). 

In all physical adsorption and in most chemisorptions heat is evolved. Heat release upon spontaneous adsorption would be expected for the following reasons. There must be a descrease in the free energy of the system adsorbent-adsorbate for the spontaneous process at constant temperature and pressure, and as the adsorbate is more localized it loses some of its translational entropy and some of its rotational entropy. Thus AG and AS are both negative and since A// - AG + TAS then A/f must also be negative and therefore heat is released. 

The potential energy well for chemisorption is associated with the more familiar chemical bond, although the valence band of the solid provides many unique features, and is reviewed by Grimley [41]. The experimental distinction between physisorbed and chemisorbed states is now readily made by photoemission studies of the combined adsorbate-adsorbent system, thus (thankfully) committing the otherwise rather theological discussions of borderline cases to past history. Chemisorption heats (see ref. 42) usually lie within the range 30 < q < 600 kj mole-1 and measured adatom—adsorbent atom equilibrium distances are usually very close to those observed in solid state of molecular analogues. (Such measurements are obtained by LEED or, more accurately, by surface EXAFS.)... 

As a conclusion, from these experimental results alone, it is impossible to decide in favour of either adsorption law So, adsorption studies have to resort to other methods than purely kinetic ones in order to unravel the intricacies of an adsorbate-adsorbent system In the case in point, microcalorimetry allows to exclude at least one model,since chemisorption heat is a linear function not of the adsorbed volume, as it should be if the ELOVICH-TEMKIN model were obeyed, but of its logarithm ... 

The initial chemisorption heat of N2 could be evaluated by a semi-empirical approach, which is developed by Sacher and Reijen et from the interrelation of the initial chemisorption heat and formation heat of hydrides, nitrides, oxides. The calculated results and the measured results are shown in Table 1.17. Negative values of formation heat of nitrides listed in Table 1.17 are smaller than the corresponding chemisorption heat, but their values are parallel. It is notable that the initial chemisorption heat of N2 is 293 kJ mol on iron, while the formation heat of Fe4N is just 12.5 kJ mol , indicating that the chemisorption evolves a large amount of excess energy due to the bonding ability of surface available bonds. 

The results from adsorption on the single crystal surfaces show that there can be several binding states of adsorbed species on a certain surface and the difference of chemisorption heat may be as high as 80 kJ mol . Thus, it is impossible to give a definite value of chemisorption heat for a metal, unless for a known adsorption state or for a metal with only one definite adsorption state. ... 

The thermochemical data of all species involved and the adsorption and chemisorption heats of water. 

The adsorption of nonelectrolytes at the solid-solution interface may be viewed in terms of two somewhat different physical pictures. In the first, the adsorption is confined to a monolayer next to the surface, with the implication that succeeding layers are virtually normal bulk solution. The picture is similar to that for the chemisorption of gases (see Chapter XVIII) and arises under the assumption that solute-solid interactions decay very rapidly with distance. Unlike the chemisorption of gases, however, the heat of adsorption from solution is usually small it is more comparable with heats of solution than with chemical bond energies. 

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. 

It is not surprising, in view of the material of the preceding section, that the heat of chemisorption often varies from the degree of surface coverage. It is convenient to consider two types of explanation (actual systems involving some combination of the two). First, the surface may be heterogeneous, so that a site energy distribution is involved (Section XVII-14). As an example, the variation of the calorimetric differential heat of adsorption of H2 on ZnO is shown in Fig. 

Fig. XVIII-13. Activation energies of adsorption and desorption and heat of chemisorption for nitrogen on a single promoted, intensively reduced iron catalyst Q is calculated from Q = Edes - ads- (From Ref. 130.)...

We consider first some experimental observations. In general, the initial heats of adsorption on metals tend to follow a common pattern, similar for such common adsorbates as hydrogen, nitrogen, ammonia, carbon monoxide, and ethylene. The usual order of decreasing Q values is Ta > W > Cr > Fe > Ni > Rh > Cu > Au a traditional illustration may be found in Refs. 81, 84, and 165. It appears, first, that transition metals are the most active ones in chemisorption and, second, that the activity correlates with the percent of d character in the metallic bond. What appears to be involved is the ability of a metal to use d orbitals in forming an adsorption bond. An old but still illustrative example is shown in Fig. XVIII-17, for the case of ethylene hydrogenation. 

Sequences such as the above allow the formulation of rate laws but do not reveal molecular details such as the nature of the transition states involved. Molecular orbital analyses can help, as in Ref. 270 it is expected, for example, that increased strength of the metal—CO bond means decreased C=0 bond strength, which should facilitate process XVIII-55. The complexity of the situation is indicated in Fig. XVIII-24, however, which shows catalytic activity to go through a maximum with increasing heat of chemisorption of CO. Temperature-programmed reaction studies show the presence of more than one kind of site [99,1(K),283], and ESDIAD data show both the location and the orientation of adsorbed CO (on Pt) to vary with coverage [284]. 

Chemisorption is always an exothennic process. By convention, tire heat of adsorption, has a positive... 

When a molecule adsorbs to a surface, it can remain intact or it may dissociate. Dissociative chemisorption is conmion for many types of molecules, particularly if all of the electrons in the molecule are tied up so that there are no electrons available for bonding to the surface without dissociation. Often, a molecule will dissociate upon adsorption, and then recombine and desorb intact when the sample is heated. In this case, dissociative chemisorption can be detected with TPD by employing isotopically labelled molecules. If mixing occurs during the adsorption/desorption sequence, it indicates that the mitial adsorption was dissociative. 

The saturation coverage during chemisorption on a clean transition-metal surface is controlled by the fonnation of a chemical bond at a specific site [5] and not necessarily by the area of the molecule. In addition, in this case, the heat of chemisorption of the first monolayer is substantially higher than for the second and subsequent layers where adsorption is via weaker van der Waals interactions. Chemisorption is often usefLil for measuring the area of a specific component of a multi-component surface, for example, the area of small metal particles adsorbed onto a high-surface-area support [6], but not for measuring the total area of the sample. Surface areas measured using this method are specific to the molecule that chemisorbs on the surface. Carbon monoxide titration is therefore often used to define the number of sites available on a supported metal catalyst. In order to measure the total surface area, adsorbates must be selected that interact relatively weakly with the substrate so that the area occupied by each adsorbent is dominated by intennolecular interactions and the area occupied by each molecule is approximately defined by van der Waals radii. This... 

In writing the present book our aim has been to give a critical exposition of the use of adsorption data for the evaluation of the surface area and the pore size distribution of finely divided and porous solids. The major part of the book is devoted to the Brunauer-Emmett-Teller (BET) method for the determination of specific surface, and the use of the Kelvin equation for the calculation of pore size distribution but due attention has also been given to other well known methods for the estimation of surface area from adsorption measurements, viz. those based on adsorption from solution, on heat of immersion, on chemisorption, and on the application of the Gibbs adsorption equation to gaseous adsorption. 

Regardless of method, desorption is never complete. Adsorbent capacity is always less following regeneration than it is on initial loading of adsorbent. Some adsorbable materials undergo chemisorption they chemically combine with the adsorbent. An example is the Reinluft process (52) for removing SO2 from flue gas on activated carbon. The SO2 is attached to the carbon as sulfuric acid. Desorption occurs only upon heating to 370°C a mixture of CO2, evolved from the chemically bound carbon, and SO2 are driven off. 

Hydrogen gas chemisorbs on the surface of many metals in an important step for many catalytic reactions. A method for estimating the heat of hydrogen chemisorption on transition metals has been developed (67). These values and metal—hydrogen bond energies for 21 transition metals are available (67). 

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