Porous solids adsorption

The capillary condensation theory provides a satisfactory explanation of the phenomenon of adsorption hysteresis, which is frequently observed for porous solids. Adsorption hysteresis is a term which is used when the desorption isotherm curve does not coincide with the adsorption isotherm curve (Figure 5.8). 

Rives, V., A computer program for analyzing nitrogen adsorption isotherms on porous solids, Adsorpt. Sci. Technol, 8(2), 95-104(1992). 

Adsorption may in principle occur at all surfaces its magnitude is particularly noticeable when porous solids, which have a high surface area, such as silica gel or charcoal are contacted with gases or liquids. Adsorption processes may involve either simple uni-molecular adsorbate layers or multilayers the forces which bind the adsorbate to the surface may be physical or chemical in nature. 

Many solids show marked swelling as a result of the uptake of a gas or a liquid. In certain cases involving the adsorption of a vapor by a porous solid, a linear relationship exists between the percentage of linear expansion of Ae solid and the film pressure of the adsorbed material [134, 135]. 

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. 

This description is traditional, and some further comment is in order. The flat region of the type I isotherm has never been observed up to pressures approaching this type typically is observed in chemisorption, at pressures far below P. Types II and III approach the line asymptotically experimentally, such behavior is observed for adsorption on powdered samples, and the approach toward infinite film thickness is actually due to interparticle condensation [36] (see Section X-6B), although such behavior is expected even for adsorption on a flat surface if bulk liquid adsorbate wets the adsorbent. Types FV and V specifically refer to porous solids. There is a need to recognize at least the two additional isotherm types shown in Fig. XVII-8. These are two simple types possible for adsorption on a flat surface for the case where bulk liquid adsorbate rests on the adsorbent with a finite contact angle [37, 38]. 

As a general rule, adsorbates above their critical temperatures do not give multilayer type isotherms. In such a situation, a porous absorbent behaves like any other, unless the pores are of molecular size, and at this point the distinction between adsorption and absorption dims. Below the critical temperature, multilayer formation is possible and capillary condensation can occur. These two aspects of the behavior of porous solids are discussed briefly in this section. Some lUPAC (International Union of Pure and Applied Chemistry) recommendations for the characterization of porous solids are given in Ref. 178. 

The adsorption branch of isotherms for porous solids has been variously modeled. Again, the DR equation (Eq. XVII-75) and related forms have been used [186,194]. With respect to desorption, the variety of shapes of loops of the closed variety that may be observed in practice is illustrated in Fig. XVII-29 (see also Refs. 195 and 197). 

M. Jaroniec and R. Maday, Physical Adsorption on Porous Solids, Elsevier, New York, 1988. 

One application of the grand canonical Monte Carlo simulation method is in the study ol adsorption and transport of fluids through porous solids. Mixtures of gases or liquids ca separated by the selective adsorption of one component in an appropriate porous mate The efficacy of the separation depends to a large extent upon the ability of the materit adsorb one component in the mixture much more strongly than the other component, separation may be performed over a range of temperatures and so it is useful to be to predict the adsorption isotherms of the mixtures. 

The physical adsorption of gases by non-porous solids, in the vast majority of cases, gives rise to a Type II isotherm. From the Type II isotherm of a given gas on a particular solid it is possible in principle to derive a value of the monolayer capacity of the solid, which in turn can be used to calculate the specific surface of the solid. The monolayer capacity is defined as the amount of adsorbate which can be accommodated in a completely filled, single molecular layer—a monolayer—on the surface of unit mass (1 g) of the solid. It is related to the specific surface area A, the surface area of 1 g of the solid, by the simple equation... 

If the region FGH of the isotherm represents the filling of all the pores with liquid adsorbate, then the amount adsorbed along to plateau FGH, when expressed as a volume of liquid (by use of the normal liquid density) should be the same for all adsorptives on a given porous solid. This prediction is embodied in a generalization put forward many years ago by Gurvitsch and usually known as the Gurvitsch rule. 

It follows therefore that the specific surface of a mesoporous solid can be determined by the BET method (or from Point B) in just the same way as that of a non-porous solid. It is interesting, though not really surprising, that monolayer formation occurs by the same mechanism whether the surface is wholly external (Type II isotherm) or is largely located on the walls of mesopores (Type IV isotherm). Since the adsorption field falls off fairly rapidly with distance from the surface, the building up of the monolayer should not be affected by the presence of a neighbouring surface which, as in a mesopore, is situated at a distance large compared with the size of a molecule. 

The principal aim of the second edition of this book remains the same as that of the first edition to give a critical exposition of the use of the adsorption methods for the assessment of the surface area and pore size distribution of finely divided and porous solids. 

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. 

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. 

It would be difficult to over-estimate the extent to which the BET method has contributed to the development of those branches of physical chemistry such as heterogeneous catalysis, adsorption or particle size estimation, which involve finely divided or porous solids in all of these fields the BET surface area is a household phrase. But it is perhaps the very breadth of its scope which has led to a somewhat uncritical application of the method as a kind of infallible yardstick, and to a lack of appreciation of the nature of its basic assumptions or of the circumstances under which it may, or may not, be expected to yield a reliable result. This is particularly true of those solids which contain very fine pores and give rise to Langmuir-type isotherms, for the BET procedure may then give quite erroneous values for the surface area. If the pores are rather larger—tens to hundreds of Angstroms in width—the pore size distribution may be calculated from the adsorption isotherm of a vapour with the aid of the Kelvin equation, and within recent years a number of detailed procedures for carrying out the calculation have been put forward but all too often the limitations on the validity of the results, and the difficulty of interpretation in terms of the actual solid, tend to be insufficiently stressed or even entirely overlooked. And in the time-honoured method for the estimation of surface area from measurements of adsorption from solution, the complications introduced by... 

In liquid-solid adsorption chromatography (LSC) the column packing also serves as the stationary phase. In Tswett s original work the stationary phase was finely divided CaCOa, but modern columns employ porous 3-10-)J,m particles of silica or alumina. Since the stationary phase is polar, the mobile phase is usually a nonpolar or moderately polar solvent. Typical mobile phases include hexane, isooctane, and methylene chloride. The usual order of elution, from shorter to longer retention times, is... 

Diffusion in porous solids is usually the most important factor con-troUing mass transfer in adsorption, ion exchange, drying, heterogeneous catalysis, leaching, and many other applications. Some of the... 

Certain highly porous solid materials selectively adsorb certain molecules. Examples are silica gel for separation of aromatics from other hydrocarbons, and activated charcoal for removing liquid components from gases. Adsorption is analogous to absorption, but the principles are different. Layers of adsorbed material, only a few molecules thick, are formed on the extensive interior area of the adsorbent - possibly as large as 50,000 sq. ft./lb of material. 

F. Rouquerol, J. Rouquerol, K. Sing, Adsorption by Powders and Porous Solids, Academic Press, London, 1999. 

Conventional bulk measurements of adsorption are performed by determining the amount of gas adsorbed at equilibrium as a function of pressure, at a constant temperature [23-25], These bulk adsorption isotherms are commonly analyzed using a kinetic theory for multilayer adsorption developed in 1938 by Brunauer, Emmett and Teller (the BET Theory) [23]. BET adsorption isotherms are a common material science technique for surface area analysis of porous solids, and also permit calculation of adsorption energy and fractional surface coverage. While more advanced analysis methods, such as Density Functional Theory, have been developed in recent years, BET remains a mainstay of material science, and is the recommended method for the experimental measurement of pore surface area. This is largely due to the clear physical meaning of its principal assumptions, and its ability to handle the primary effects of adsorbate-adsorbate and adsorbate-substrate interactions. 

Massonne, J. et al., Angew. Chem. (Intern. Ed.), 1966, 5, 317 Adsorption of nitrogen trifluoride on to activated granular charcoal at — 100°C caused an explosion, attributed to the heat of adsorption not being dissipated on the porous solid and causing decomposition to nitrogen and carbon tetrafluoride. No reaction occurs at +100°C in a flow system, but incandescence occurs at 150°C. 

Adsorption by Powders and Porous Solids by Rouquerol, Rouquerol, and Sing [1]... 

The advantage of equation 17.14 is that it may be fitted to all known shapes of adsorption isotherm. In 1938, a classification of isotherms was proposed which consisted of the five shapes shown in Figure 17.5 which is taken from the work of Brunauer et alSu Only gas-solid systems provide examples of all the shapes, and not all occur frequently. It is not possible to predict the shape of an isotherm for a given system, although it has been observed that some shapes are often associated with a particular adsorbent or adsorbate properties. Charcoal, with pores just a few molecules in diameter, almost always gives a Type I isotherm. A non-porous solid is likely to give a Type II isotherm. If the cohesive forces between adsorbate molecules are greater than the adhesive forces between adsorbate and adsorbent, a Type V isotherm is likely to be obtained for a porous adsorbent and a Type III isotherm for a non-porous one. 

Emmett, P. H. Advances in Colloid Science 1 (1942) 1. The measurement of the surface areas of finely divided or porous solids by low temperature adsorption isotherms. 

From these results, it can be concluded that hydrogen adsorption at 77K and at pressures up to 4 MPa requires porous solids with a very high micropore volume, such as chemically activated carbons. At these adsorption conditions, micropore size distribution does not play an important role, contrary to what happened at room temperature. 

Liquid phase zeoHtic separation includes two main events adsorption and desorption. Adsorption of an adsorbate (liquid component being adsorbed by solid) onto zeolitic adsorbent is dictated by the characteristics of the adsorbate-adsorbent interaction. A zeolitic adsorbent is a crystalline porous solid having particular characteristics (see Chapter 2). When immersed in a liquid mixture, the porous... 

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