Catalysis adsorption isotherms

Influence of the Adsorption Isotherm on the Kinetics of Heterogeneous Catalysis... 

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... 

Given the complexity of the pore structure in high-surface-area catalysts, six types of adsorption isotherms have been identified according to a classification advanced by IUPAC 145-481. Out of these six, only four are usually found in catalysis ... 

In his consideration of the nature of catalysis Berzelius had assumed the catalyst played no part in the actual reaction. Studies on nonenzyme catalysis, and especially the roles of finely divided metals, such as platinum, seemed to substantiate this—a view apparently consistent with the concept of the adsorption isotherm introduced by Langmuir (1916). 

Cranston, R. W. and Inkley, F. A. Advances in Catalysis 9 (1957) 143. The determination of pore structures from nitrogen adsorption isotherms. 

CI2 evolution reaction, 38 56 electrochemical desorption, 38 53-54 electrode kinetics, 38 55-56 factors that determine, 38 55 ketone reduction, 38 56-57 Langmuir adsorption isotherm, 38 52 recombination desorption, 38 53 surface reaction-order factor, 38 52 Temkin and Frumkin isotherm, 38 53 real-area factor, 38 57-58 regular heterogeneous catalysis, 38 10-16 anodic oxidation of ammonia, 38 13 binding energy quantification, 38 15-16 Haber-Bosch atrunonia synthesis, 38 12-13... 

When the functional form of the correlation is suggested by theory, there is a great deal more confidence that the correlation can be extrapolated into regions of P that have no experimental data, and can be used for other families of compounds other than the training set S. Examples of theory-suggested functional forms include the van der Waals equation of state for gases, the Langmuir isotherm for adsorption and catalysis, and the Clausius-Clapeyron equation for the vapor pressure of liquids. 

The Brunauer-Emmett-Teller (or BET) adsorption isotherm applies only to the physisorption of vapours but it is important to heterogeneous catalysis because of its use for the determination of the surface areas of solids. The isotherm is given by the following equation,... 

Significantly later, foreign scientists reached a similar conclusion regarding the Freundlich isotherm. In the USSR, a theory of adsorption on an inhomogeneous surface was developed independently by M. I. Temkin of the Karpov Physico-Chemical Institute in connection with electrochemical research by Academician A. N. Frumkin. M. I. Temkin s work on a logarithmic isotherm was cited in [74] and published in [75]. The theory of adsorption and catalysis on an inhomogeneous surface was especially extensively developed by S. Z. Roginskii. 

This paper by Ya.B. was translated and published, with a few changes, in the collection Statistical phenomena in heterogeneous systems, 1 which was devoted especially to the theory of non-uniform surfaces and to statistical phenomena in adsorption and catalysis. In the review article by V. I. Levin in this collection the priority of Ya.B. s article in statistical research on the theory of adsorption and catalysis is emphasized. The article also cites articles by other authors who came to similar conclusions, but later than Ya.B. The significance of Ya.B. s work for the theory of catalysis is elucidated in detail in S. Z. Roginskii s book, Adsorption and Catalysis on a Non-Uniform Surface. 2 After this a summary of this paper by Ya.B. has entered into the majority of monographs and textbooks on catalysis. Thus, in the course of Thomas and Thomas3 the derivation of the adsorption isotherm on a non-uniform surface is given in full and referred to as classical. 

This empirical equation of the adsorption isotherm, giving the relationship between 6 and the pressure, excellently represents many characteristics of chemisorption. Equation (72) is introduced by Frumkin and Slygin (366), who derived it from their electrochemical investigations on hydrogen electrodes. The equation has played an extensive role in the successful theory of ammonia catalysis of Temkin (367) and it has in literature been termed the Temkin equation (368), although Temkin himself and other Russian investigators call it the logarithmic adsorption isotherm. 

Catalysis offers numerous examples of the simultaneous chemisorption of different molecules or atoms. The extremely important problems of poisoning, of promoting and of selective catalysis depend on this phenomenon. In the past numerical estimations of the relative amounts that will be bound by chemisorption in equilibrium were mostly based on the assumption that Langmuir s adsorption isotherm would be valid. In such a case the following equation is easily derived ... 

In some cases, adsorption of analyte can be followed by a chemical reaction. The Langmuir-Hinshelwood (LH) and power-law models have been used successfully in describing the kinetics of a broad range of gas-solid reaction systems [105,106]. The LH model, developed to describe interactions between dissimilar adsorbates in the context of heterogeneous catalysis [107], assumes that gas adsorption follows a Langmuir isotherm and that the adsorbates are sufficiently mobile so that they equilibrate with one another on the surface on a time scale that is rapid compared to desorpticm. The power-law model assumes a Fre-undlich adsorption isotherm. Bodi models assume that the surface reaction is first-order with respect to the reactant gas, and that surface coverage asymptotically approaches a mmiolayer widi increasing gas concentration. 

On the other hand, kinetics of reactions occiuring on a solid surface, that is, catalysis or photocatalysis, must be significantly different. There may be two representative extreme cases. One is so-called a diffusion controlled process, in which siuface reactions and the following detachment process occur very rapidly to give a negligible surface concentration of adsorbed molecules, and the overall rate coincides with the rate of adsorption of substrate molecules. In this case, the overall rate is proportional to concentration of the substrate in a solution or gas phase (bulk), that is, first-order kinetics is observed IS). The other extreme case is so-called surface-reaction limited, in which surface adsorption is kept in equilibrium during the reaction amd the overall rate coincides with the rate of reaction occurring on the surface, that is, reaction of e and h+ with surface-adsorbed substrate (l9). Under these conditions, the overall rate is not proportional to concentration of the substrate in the bulk unless the adsorption isotherm obeys a Henry-type equation, in which the amount of adsorption is proportional to concentration in the bulk (20). In the former case, the rate... 

It has been concluded that, for most cases, catalysis over zeolites occurs within the intracrystalline voids. Strong supporting evidence for this was provided by Weisz (71), who compared the rates of dehydration of 2-butanol over Linde lOX and 5A zeolites at relatively high temperatures and low conversion. The rate constant per unit volume of 5A was 1/lOO-l/lOOOth that for lOX, a magnitude consistent with the ratio of available surface areas for the external area of 1-5/x-sized 5A crystals and for lOX, where the internal surface area was available to the alcohol. The strong driving force for occlusion within the intracrystalline zeolite voids is exemplified by the rapid adsorption kinetics and rectangular adsorption isotherms observed for molecules whose dimensions are not close to those of the entry pores. 

Of course, other types of adsorption isotherms commonly represent the adsorption processes in heterogeneous catalysis, for example, the Freundlich isotherm and, especially in electrode processes, the Temkin and Frumkin isotherms (99). In the latter case... 

The reactants from the gas adsorb to bond to active sites on the catalyst surface as molecules or dissociated atoms. The rate of adsorption is proportional to the partial pressure of reactants and to the fraction of uncovered surface sites tf. More than one type of active site can be present. The adsorption isotherms such as the Langmuir isotherm relate the partial pressure of an adsorbed species to its surface coverage, and the form of this relationship is indicative of the type of adsorption process taking place (see, for more details, Masel, Chemical Kinetics and Catalysis, Wiley, 2001). 

J.D.F. Ramsay, P.J. Russell and S.W. Swanton, Gel precipitated oxide gels with controlled porosity-Determination of structure by small angle neutron scattering and adsorption isotherms measurements, in F. Rodriguez-Reinoso, J. Rouquerol, K.S.W. Sing and K.K. Unger (Eds.), Characterization of Porous Solids II, Studies in Surface Science and Catalysis Vol. 62, Proc. of the lUPAC Symposium (COPS II), Alicante, Spain, May 1990, Elsevier, Amsterdam, 1991, pp. 257-265. 

Adsorption isotherms. Adsorption is an important facet of kinetics of heterogeneous catalysis. Adsorption isotherms, showing the equilibrium concentration of a species on a solid as a function of the concentration in the contacting fluid at constant temperature, may have different shapes, usually classified as Types I through V [18] (see Figure 2.4). 

Because amino groups act autocatalytically (15-17) in the presence of water, for acid catalysis an excess of HC1 was used to overcompensate the formation of -NH3+C1 . In these cases, the gels were washed with methanol and water until no Cl" could be detected in the filtrate. How far the incorporation of amino groups into silica could affect the adsorption of acid components was of interest. Lactic acid and a sulfonic acid (a commercially available dye named Telon Light Yellow) were chosen as test components (18). In Figure 7 the adsorption isotherm of lactic acid is shown. Unmodified Si02 does not have remarkable adsorption in aqueous solution under these circumstances. The result shows the effect of the amino modification quite clearly, because the lactic acid load of the adsorbent is remarkable, and it is difficult to adsorb small water-soluble molecules in an aqueous environment. 

An excellent application of LEED not requiring detailed understanding of diffracted intensities is the study of diffusion of adsorbed atoms into the substrate bulk. Conversely, segregation at a surface of atoms previously dissolved in the substrate lattice can be observed too. These processes, bulk solution and precipitation at a surface, are ultimately controlled by the Gibbs adsorption isotherm which determines equilibrium concentration at the interface. Atoms from the gas phase can contribute to such surface equilibria also. Distribution of foreign atoms between surface and bulk may be important in catalysis (393). 

In catalysis the reasons for all kinetic behaviour lie in the behaviour of surface coverage by the reactants. This means that the kinetics of certain catalytic reactions -and the catalytic oxidation of CO via a bimolecular surface reaction is one of than - do not depend directly on gas phase concentrations. To understand Figures 12.1 and 12.2 we need to examine the behaviour of 6co and dca as expressed by equations 12.4 and 12.5. It is only by understanding the behaviour of the fractions of surface covered by adsorbed species that an understanding of any catalytic reaction can be gained. Since at present there is no way to measure the adsorption isotherms of reacting species at high temperatures, we need a reliable mechanistic rate expression to examine this aspect of the reaction. An appropriate mechanistic rate expression will permit us to reliably simulate the behaviour of the isotherms from kinetic data. 

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