Specific surfaces adsorption data

Fig. 11 Surface fractal dimensions ds on atomic length scales of furnace blacks and graphitized blacks in dependence of specific surface. The data are obtained from nitrogen adsorption isotherms in the multilayer regime...

A variety of experimental data has been found to fit the Langmuir equation reasonably well. Data are generally plotted according to the linear form, Eq. XVn-9, to obtain the constants b and n from the best fitting straight line. The specific surface area, E, can then be obtained from Eq. XVII-10. A widely used practice is to take to be the molecular area of the adsorbate, estimated from liquid or solid adsorbate densities. On the other hand, the Langmuir model is cast around the concept of adsorption sites, whose spacing one would suppose to be characteristic of the adsorbent. See Section XVII-5B for an additional discussion of the problem. 

Figure Bl.22.1. Reflection-absorption IR spectra (RAIRS) from palladium flat surfaces in the presence of a 1 X 10 Torr 1 1 NO CO mixture at 200 K. Data are shown here for tluee different surfaces, namely, for Pd (100) (bottom) and Pd(l 11) (middle) single crystals and for palladium particles (about 500 A m diameter) deposited on a 100 A diick Si02 film grown on top of a Mo(l 10) single crystal. These experiments illustrate how RAIRS titration experiments can be used for the identification of specific surface sites in supported catalysts. On Pd(lOO) CO and NO each adsorbs on twofold sites, as indicated by their stretching bands at about 1970 and 1670 cm, respectively. On Pd(l 11), on the other hand, the main IR peaks are seen around 1745 for NO (on-top adsorption) and about 1915 for CO (tlueefold coordination). Using those two spectra as references, the data from the supported Pd system can be analysed to obtain estimates of the relative fractions of (100) and (111) planes exposed in the metal particles [26].

At the point where capillary condensation commences in the finest mesopores, the walls of the whole mesopore system are already coated with an adsorbed film of area A, say. The quantity A comprises the area of the core walls and is less than the specific surface A (unless the pores happen to be parallel-sided slits). When capillary condensation takes place within a pore, the film-gas interface in that pore is destroyed, and when the pore system is completely filled with capillary condensate (e.g. at F in Fig. 3.1) the whole of the film-gas interface will have disappeared. It should therefore be possible to determine the area by suitable treatment of the adsorption data for the region of the isotherm where capillary condensation is occurring. 

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. 

Adequate description of many catalysts will require a large number of bits of data since they are usually rather complicated materials rather than simple chemicals. Attempts at tMs were just beginning by ICC 1, but now, one expects authors to give specific surface areas and some details of the porosity of their catalysts. Automation of the former tedious point by point measiirement of the N2 adsorption isotherm has greatly facilitated this. 

However, the surface tension data that would confirm the specific adsorption of hydrophilic and semihydrophobic ions are lacking. Absence of the specific ion adsorption in these cases is corroborated by the analysis of the surface tension data for the nonpolar-... 

In general, the BET equation fits adsorption data quite well over the relative pressure range 0.05-0.35, but it predicts considerably more adsorption at higher relative pressures than is experimentally observed. This is consistent with an assumption built into the BET derivation that an infinite number of layers are adsorbed at a relative pressure of unity. Application of the BET equation to nonpolar gas adsorption results is carried out quite frequently to obtain estimates of the specific surface area of solid samples. By assuming a cross-sectional area for the adsorbate molecule, one can use Wm to calculate specific surface area by the following relationship ... 

Data for the adsorption of nitrogen on silica-alumina tabulated. V is in cc/g at STP. Find the specific surface by problem P6.01.02. 

Calculate C and the specific surface area As of a material from the nitrogen adsorption isotherm according to the BET equation from the data points given in the figure. Use the ideal gas equation to convert the adsorbed volumes into moles (STP indicates that the volumes adsorbed are given for standard temperature and pressure, i.e., 273 K and 101.3 kPa). 

Prior to nitrogen adsorption experiment to determine surface properties, ACC sample was degassed at 130°C under vacuum (up to 10 torr) for 12 h. The adsorption data were obtained at the Central Laboratory of Middle East Technical University (METU) with a Quantachrome Autosoib-l-C/MS apparatus over a relative pressure ranging from 10" to 1. The BET specific surface area, total pore volume, micropore volume, mesopore volume, and pore size distribution, PSD, of ACC were yielded by using the software of the apparatus. 

Although there are several methods for analysis of nitrogen physisorption data, the most commonly used is BET surface area. Because for microporous materials the boundary conditions for multilayer adsorption are not fulfilled, the calculated BET surface area has no physical meaning. Such data should be considered proportional to the total micropore volume rather than the specific surface area. The Tplot method can be used to calculate the micropore volume and the mesopore... 

Ammonia TPD is very simple and versatile. The use of propylamine as a probe molecule is starting to gain some popularity since it decomposes at the acid site to form ammonia and propene directly. This eliminates issues with surface adsorption observed with ammonia. The conversion of the TPD data into acid strength distribution can be influenced by the heating rate and can be subjective based on the selection of desorption temperatures for categorizing acid strength. Since basic molecules can adsorb on both Bronsted and Lewis acid sites, the TPD data may not necessarily be relevant for the specific catalytic reaction of interest because of the inability to distinguish between Bronsted and Lewis acid sites. 

The estimation of the surface area of finely divided solid particles from solution adsorption studies is subject to many of the same considerations as in the case of gas adsorption, but with the added complication that larger molecules are involved whose surface orientation and pore penetrability may be uncertain. A first condition is that a definite adsorption model is obeyed, which in practice means that area determination data are valid within the simple Langmuir Equation 5.23 relation. The constant rate is found, for example, from a plot of the data, according to Equation 5.23, and the specific surface area then follows from Equations 5.21 and 5.22. The surface area of the adsorbent is generally found easily in the literature. 

The N2 adsorption (with BFT and BJH methods) results listed in Table 5.2 showed that the zeolite surface area and pore volume were apparently increased after CP treatment. For example, compared with DASY(0.0) the specific surface area of SOYO-S3 increased by 53 m /g from 618 to 671 m /g, and the pore volume increased from 0.352 to 0.393 mL/g. In addition, DTA analysis data listed in Table 5.2 showed that the thermal stability of the zeolite was further improved. 

The global thermodynamic approach used in the above sections is insensitive to details at the atomic level and can only yield a gross characterization of the surface. Properties such as the specific surface area and the presence or absence of pores can be determined using the above approach since only the average surface —not atomic details —is involved. The existence of a distribution of surface energy sites can also be inferred from adsorption data, but the method falls short when it comes to specifics about this distribution. Observations on an atomic scale are needed to learn more about the details of the surface structure. Such observations comprise the subject matter of the last two sections of the chapter. 

Since it is relatively easy to fit experimental adsorption data to a theoretical equation, there is some controversy as to what constitutes a satisfactory description of adsorption. From a practical point of view, any theory that permits the amount of material adsorbed to be related to the specific surface area of the adsorbent and that correctly predicts how this adsorption varies with temperature may be regarded as a success. From a theoretical point of view, what is desired is to describe adsorption in terms of molecular properties, particularly in terms of an equation of state for the adsorbed material, where the latter is regarded as a two-dimensional state of matter. 

With monolayer adsorption, we saw how the saturation limit could be related to the specific surface area of the adsorbent. The BET equation permits us to extract from multilayer adsorption data (by means of Equation (77)) the volume of adsorbed gas that would saturate the surface if the adsorption were limited to a monolayer. Therefore Vm may be interpreted in the same manner that the limiting value of the ordinate is handled in the case of monolayer adsorption. Since it is traditional to express both V and Vm in cubic centimeters at STP per gram, we write (see Equation (7.72))... 

Data for calcined samples dioo - XRD (100) interplanar spacing, Sbet - BET specific surface area, V, - total pore volume, Vp - primary mesopore volume, Sex - external surface area, wkjs - primary mesopore diameter. Data for uncalcined samples mreS due - mass percent of residue at 1263 K, mSdir - mass decrease in the temperature range of the surfactant decomposition and desorption of the decomposition products (between about 373 and 623 K). Notes a - no peak on XRD spectrum, d,0o cannot be evaluated, b - no linear region on the Os-plot, which would be suitable for the Vp and Sex evaluation. XRD and adsorption data (except for those for HR-A2 sample) taken from Refs. 24 and 26. Thermogravimetric data for DS-AD taken from Ref. 19. 

Another significant application of GC is in the area of the preparation of pure substances or narrow fractions as standards for further investigations. GC also is utilized on an industrial scale for process monitoring. In adsorption studies, it can be used to determine specific surface areas (30,31). A novel use is its utilization to carry out elemental analyses of organic components (32). Distillation curves may also be plotted from gas chromatographic data. 

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