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    Mariana Lizeth

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    CHAPTER 1 Introduction 1.1. Importance of adsorption 1.2. Historical aspects 1.3. General definitions and terminology 1.4, Physisorption and chemisorption 1.5. Adsorption interactions oe 1.6. Mobility of adsorbed molecules 1.7. Energetics of physisorption 1.8. Types of adsorption isotherms 1.8.1. Physisorption of gases 1.8.2. Chemisorption of gases 1.8.3. Adsorption from solution . 1.9, Molecular modelling of adsorption 1.9.1. Intermolecular potential functions . 1.9.2. Molecular simulation ‘Monte Carlo (MC) simulation Molecular dynamics (MD) . 1.93. Density functional theory (DFT) 1.1. Importance of Adsorption Adsorption occurs whenever a solid surface is exposed to a gas or liquid: it is defined as the enrichment of material or increase in the density of the fluid in the vicinity of an interface. Under certain conditions, there is an appreciable enhancement in the concentration of a particular component and the overall effect is then dependent on the extent of the interfacial area. For this reason, all industrial adsorbents have large specific surface areas (generally well in excess of 100m? g~) and are therefore highly porous or composed of very fine particles Adsorption is of great technological importance. Thus, some adsorbents are used on a large scale as desiccants, catalysts or catalyst supports; others are used for the separation of gases, the purification of liquids, pollution control or for respiratory protection, In addition, adsorption phenomena play a vital role in many solid state reactions and biological mechanisms. ‘Another reason for the widespread use of adsorption techniques is the importance ‘now attached to the characterization of the surface properties and texture of fine powders such as pigments, fillers and cements. Similarly, adsorption measurements are undertaken in many academic and industrial laboratories on porous materials 2 ADSORPTION BY POWDERS AND POROUS SOLIDS such as clays, ceramics and membranes. In particular, gas adsorption has become one of the most widely used procedures for determining the surface area and pore size distribution of a diverse range of powders and porous materials. The older types of industrial adsorbents (e.g. activated carbons and silica gels) are generally non-crystalline and their surface and pore structures therefore tend to be ill-defined and difficult to characterize. There is, however, a growing number of adsorbents having intracrystalline pore structures (e.g. zeolites and aluminophos- phates). Great interest is being shown in the design of other new materials having pores of well-defined size and shape. 1.2. Historical Aspects Various phenomena which we now associate with adsorption were known in antiquity. The adsorbent properties of such materials as clay, sand and wood charcoal ‘were utilized by the ancient Egyptians, Greeks andl Romans (Robens, 1994). These applications were wide-ranging and included the desalination of water, the clarifica- tion of fat and oil and the treatment of many diseases. Tt has long been known that certain forms of charcoal can take up large volumes of gs. The earliest quantitative studies appear to have been made by Scheele in 1773 and independently by Priestley in 1775 and the Abbé Fontana in 1777 (Deitz, 1944; Forrester and Giles, 1971). The decolorizing properties of charcoal were first inves- tigated by the Russian chemist Lowitz in 1785. The exothermal nature of gas adsorp- tion was noted by de Saussure in 1814 and the first measurements of the heat of adsorption of various gases on charcoal were published by Favre in 1854, who spoke ‘of the wetting of solids by gases. However, it was not until 1881 that the first attempts were made by Chappuis and Kayser to relate the amount of gas adsorbed to the pres- sure. In that year, Kayser introduced the term adsorption and over the next few years the terms isotherm and isothermal curve were applied to the results of adsorption ‘measurements made at constant temperature (see Forrester and Giles, 1971). Tt was observed by Leslie in 1802 that heat was produced when liquid was added to a powder. The heat evolved by the immersion of dry sand in water was described by Pouillet in 1822. This exothermic phenomenon became known in France as the “Pouillet effect’. Gore (1894) recognized that the amount of heat was related to the surface area of the powder, while Gurvich (1915) suggested that it was also ‘dependent on the polarity of the liquid and the nature of the powder. ‘The first recorded isotherms of adsorption from solution were probably those reported by van Bemmelen in 1881 (Forrester and Giles, 1972). In his investigations of the ‘absorptive’ power of soils, van Bemmelen noted the importance of the col- loidal structure and drew attention to the relevance of the final state (i.e. equilibrium concentration) of the solution in contact with the soil. A number of solute-solid isotherms were determined over the next 20 years including those for the uptake of iodine and various dyes by charcoal and other adsorbents, but many of the investigators still believed that the process involved Penetration into the solid structure, Freundlich, in 1907, was one of the first to (CHAPTER 1. INTRODUCTION 3 appreciate the role of the solid surface. He proposed a general mathematical relation for the isotherm, which we now refer to as the Freundlich adsorption equation, In 1909 MeBain reported that the uptake of hydrogen by carbon appeared to occur in two stages: a rapid process of adsorption appeared to be followed by a slow process of absorption into the interior of the solid. McBain coined the term sorption to cover both phenomena. In recent years it has been found convenient to use ‘sorp- tion’ when itis not possible to make a clear distinction between the stages of uptake, and also to use it to denote the penetration of molecules into very narrow pores (Barrer, 1978) During the early years ofthe twentieth century, various quantitative investigations of gas adsorption were undertaken. The most important advances in the theoretical interpretation of gas adsorption data were made by Zsigmondy, Polanyi and Langmuir: their ideas set the scene for much of the research undertaken over the past 80 years. In 1911 Zsigmondy pointed out that the condensation of a vapour can occur in very narrow pores at pressures well below the normal vapour pressure of the bulk liquid. This explanation was given forthe large uptake of water vapour by silica gel and was based on an extension of a concept originally put forward by Thomson (Lord Kelvin) in 1871. Itisnow generally accepted that capillary condensation does play an impor- tant role in the physisorption by porous solids, but that the original theory of Zsigmondy cannot be applied to pores of molecular dimensions. ‘The theory proposed by Polanyi in 1914 was developed from an older idea of long- range attractive forces emanating from the solid surface. The adsorbed layer was pic- tured as a thick compressed film of decreasing density with increase in distance from the surface. The original ‘potential theory’ did not give an equation for the adsorption isotherm, but instead provided a means of establishing a ‘characteristic curve’ ~ relating adsorption potential to amount adsorbed ~ for a given system, In spite ofits initial appeal, it soon became apparent that the principles underlying the potential theory were not consistent with the emerging treatment of intermolecular forces. However, more recently the concept of a characteristic curve has been modified and adopted by Dubinin and his co-workers in their theory of micropore filling. ‘The year 1916 brought a radical change in the approach to surface science. In that year the first of Langmuir’s monumental papers appeared (1916, 1917, 1918). Lord Rayleigh’s carlier conclusion that certain films of polar oils on water were one ‘molecule thick had not received the attention it deserved and Langmuir’s great con- tribution was to bring together all the available evidence to support the unifying concept of the monomolecular layer (the monolayer). He proposed that adsorption on. both liquid and solid surfaces normally involved the formation of ¢ monomolecular layer. In retrospect it is not surprising that the advent of the Langmuir theory produced a renaissance in surface science. Langmuir’s work on gas adsorption and insoluble monolayers prepared the way for more progress to be made in the interpretation of adsorption from solution data. In the light of the Langmuir theory, it seemed logical to suppose that the plateau of a solute isotherm represented monolayer completion and that the monolayer capacity could be derived by application of the Langmuir equation. 4 ADSORPTION BY POWDERS AND POROUS SOLIDS Another important stage in the history of gas adsorption was the work of Brunauer and Emmett, which preceded the publication of the Brunauer-Emmett~Teller (BET) theory in 1938, In 1934 Emmett and Brunauer made their first attempt to use low- temperature adsorption of nitrogen to determine the surface area of an iron synthetic ammonia catalyst. They noted that the adsorption isotherms of a number of gases, measured at temperatures at, or near, their respective boiling points, were all S-shaped with certain distinctive features. Others, including Langmuir, had recog- nized that this type of adsorption was not always restricted to monolayer coverage and an empirical approach was adopted by Emmett and Brunauer (1937) to ascertain the stage at which the multilayer adsorption began. They eventually decided that completion of the monolayer was characterized by the beginning ofthe middle nearly linear section of the adsorption isotherm (designated Point B — see Figure 1.7). The surface area was then evaluated from the amount adsorbed at Point B by making the further assumption that the completed monolayer was in a close-packed state. In 1938 the publication of the BET theory appeared to provide a sound basis for the identification of Point B as the stage of monolayer completion and the onset of multilayer adsorption It would be difficult to overestimate the historical importance of the BET theory since for over 50 years it has attracted an enormous amount of attention (Davis, 1991), Indeed, the BET method is now accepted as a standard procedure for the determination of the surface area of a wide range of fine powders and porous. ‘materials. On the other hand, itis generally recognized that the theory is based on an oversimplified model of multilayer adsorption and that the reliability of the BET ‘method is questionable unless certain conditions are fulfilled. ‘There was a growing awareness in the early 1930s that a distinction could be made between physical adsorption (ie. physisorption) in which the van der Waals interac- tions are involved and chemical adsorption (ie. chemisorption) in which the adsorbed molecules are attached by chemical bonding. Taylor (1932) introduced the concept of ‘activated adsorption” which, by analogy with the familiar idea of an energy of activation in chemical kinetics, attempted to explain the marked increase in rate of adsorption with rise in temperature in terms of surface bond formation. The activated adsorption theory aroused a good deal of early criticism and withthe sub- sequent improvement of high vacuum techniques it was established that chemisorp- tion of certain gases can take place very rapidly on clean metal surfaces. However, there are other chemisorption systems which do appear to exhibit some features of activated adsorption. In his 1916 paper, Langmuir had stated that with highly porous adsorbents such as charcoal ‘it is impossible to know definitely the area on which the adsorption takes place’ and that ‘there are some spaces in which a molecule would be closely sur- rounded by carbon atoms on nearly all sides’. He concluded that equations derived for plane surfaces were not applicable to adsorption by charcoal. Unfortunately, these observations have been overlooked by many investigators, who have applied the simple Langmuir monolayer equation to adsorption data obtained with zeolites and activated carbons. ‘The significance of Langmuir’s comments was appreciated, however, by Dubinin (CHAPTER 1. INTRODUCTION and his co-workers in Moscow, who put forward additional evidence to show that the ‘mechanism of physisorption in very narrow pores is not the same as that in wider pores: or on the open surface. Dubinin argued that the ‘micropores’ are filled at low relative pressure by a volume-filing process. By studying a wide range of activated carbons, he identified three groups of pores of different width: micropores, transi- tional pores (now termed mesopores) and macropores. This classification has been refined (see Table 1.3), but the principles remain the same as those adopted by Dubinin (1960). ‘Another Russian scientist who played a leading role in the advancement of the understanding of adsorption mechanisms was A.V. Kiselev. With the help of a large team of co-workers and by making a systematic investigation of various well-defined adsorbents (notably oxides, carbons and zeolites), Kiselev was able to demonstrate that certain specific interactions were involved in the adsorption of polar molecules ‘on polar or ionic surfaces. At the same time, in the UK the specificity of physisorp- tion was under investigation by Barrer — especially in the context of his pioneering work on the properties ofthe molecular sieve zeolites. In an early discussion of the adsorption of gases by solids, Rideal (1932) had stressed the fundamental importance of the nature and extent of the solid surface and. hhad pointed out that it was necessary to evaluate the accessible area rather than the “true” specific area. Many attempts have been made to check the accuracy of the values of surface area derived from adsorption data (in particular from the BET theory), but the concept of surface area still remains problematical. In attempting to assess the magnitude of the surface area of a fine powder or porous solid, one is faced with a similar problem to that of a cartographer required to evaluate a coastal perime- ter. Obviously, the answer must depend on the scale of the map and the manner in ‘which the measurement is made. In recent years much attention has been given to the application of fractal analysis to surface science. The early work of Mandelbrot (1975) explored the replication of structure on an increasingly finer scale, i. the quality of self-similarity. As applied to physisorption, fractal analysis appears to provide a generalized link between the monolayer capacity and the molecular area without the requirement of an absolute surface area. In principle, this approach is attractive, although in practice itis depen-

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