Adsorption methods

An excellent example of work of this type is given by the investigations of Benson and co-workers [127, 128]. They found, for example, a value of = 276 ergs/cm for sodium chloride. Accurate calorimetry is required since there is only a few calories per mole difference between the heats of solution of coarse and finely divided material. The surface area of the latter may be determined by means of the BET gas adsorption method (see Section XVII-5). 

Sing K S W 1998 Adsorption methods for the oharaoterization of porous materials Adv. Colloid Interface Sci. 76/77 3-11... 

For practical reasons, the application of the adsorption method to the study of surface area and porosity has to be limited to bodies which are either very finely divided or possess an extensive pore system. It is helpful to consider the case of finely divided bodies first. 

An interesting example of a large specific surface which is wholly external in nature is provided by a dispersed aerosol composed of fine particles free of cracks and fissures. As soon as the aerosol settles out, of course, its particles come into contact with one another and form aggregates but if the particles are spherical, more particularly if the material is hard, the particle-to-particle contacts will be very small in area the interparticulate junctions will then be so weak that many of them will become broken apart during mechanical handling, or be prized open by the film of adsorbate during an adsorption experiment. In favourable cases the flocculated specimen may have so open a structure that it behaves, as far as its adsorptive properties are concerned, as a completely non-porous material. Solids of this kind are of importance because of their relevance to standard adsorption isotherms (cf. Section 2.12) which play a fundamental role in procedures for the evaluation of specific surface area and pore size distribution by adsorption methods. 

One of the most important uses of specific surface determination is for the estimation of the particles size of finely divided solids the inverse relationship between these two properties has already been dealt with at some length. The adsorption method is particularly relevant to powders having particle sizes below about 1 pm, where methods based on the optical microscope are inapplicable. If, as is usually the case, the powder has a raiige of particle sizes, the specific surface will lead to a mean particle size directly, whereas in any microscopic method, whether optical or electron-optical, a large number of particles, constituting a representative sample, would have to be examined and the mean size then calculated. 

The degree of uncertainty of 10 per cent or more, inseparable from estimates of specific surface from adsorption isotherms, even those of nitrogen, may seem disappointing. In fact, however, attainment of this level of accuracy is a notable achievement in a field where, prior to the development of the BET method, even the order of magnitude of the specific surface of highly disperse solids was in doubt. The adsorption method still provides the only means of determining the specific surface of a mass of non-... 

Section 3.7, the gas adsorption method breaks down for practical reasons. Since the angle of contact of mercury with solids is 140° (see later), and therefore more than 90°, an excess pressure Ap is required to force liquid mercury into the pores of a soh d. The idea of using mercury intrusion to measure pore size appears to have been first suggested by Washburn who put forward the basic equation... 

Since in practice the lower limit of mercury porosimetry is around 35 A, and the upper limit of the gas adsorption method is in the region 100-200 A (cf. p. 133) the two methods need to be used in conjunction if the complete curve of total pore volume against pore radius is to be obtained. 

Whereas at the lower end of its range mercury porosimetry overlaps with the gas adsorption method, at its upper end it overlaps with photomicrography. An instructive example is provided by the work of Dullien and his associates on samples of sandstone. By stereological measurements they were able to arrive at a curve of pore size distribution, which was extremely broad and extended to very coarse macropores the size distribution from mercury porosimetry on the other hand was quite narrow and showed a sharp peak at a much lower figure, 10nm (Fig. 3.31). The apparent contradiction is readily explained in terms of wide cavities which are revealed by photomicrography, and are entered through narrower constrictions which are shown up by mercury porosimetry. 

Fig. 4.13 The pre-adsorption method (a) adsorption isotherms of nitrogen at 77 K on a sample of Mogul I carbon black charged with different amounts x of pre-adsorbed nonane. Values ofx (mg g (A) 63 (B)48 (C) 29 (D) 16 (E) 0. (See Table 4.5.) (Some points at low pressures omitted for the sake of clarity.)...

These procedures proposed by Dubinin and by Stoeckli arc, as yet, in the pioneer stage. Before they can be regarded as established as a means of evaluating pore size distribution, a wide-ranging study is needed, involving model micropore systems contained in a variety of chemical substances. The relationship between the structural constant B and the actual dimensions of the micropores, together with their distribution, would have to be demonstrated. The micropore volume would need to be evaluated independently from the known structure of the solid, or by the nonane pre-adsorption method, or with the aid of a range of molecular probes. 

As remarked on p. 214, the validity of the nonane pre-adsorption method when adsorptives other than nitrogen are employed for determination of the isotherms, has been examined by Tayyab. Two organic adsorptives, /i-hexane and carbon tetrachloride, which could be used at or near room temperature, were selected and the adsorbents were the ammonium salts of... 

It follows that the applicability of the nonane pre-adsorption method for the evaluation of microporosity is restricted to adsorptives such as nitrogen which are used at temperatures far below ambient and which have negligible solubility in soUd or liquid nonane. 

If a Type I isotherm exhibits a nearly constant adsorption at high relative pressure, the micropore volume is given by the amount adsorbed (converted to a liquid volume) in the plateau region, since the mesopore volume and the external surface are both relatively small. In the more usual case where the Type I isotherm has a finite slope at high relative pressures, both the external area and the micropore volume can be evaluated by the a,-method provided that a standard isotherm on a suitable non-porous reference solid is available. Alternatively, the nonane pre-adsorption method may be used in appropriate cases to separate the processes of micropore filling and surface coverage. At present, however, there is no reliable procedure for the computation of micropore size distribution from a single isotherm but if the size extends down to micropores of molecular dimensions, adsorptive molecules of selected size can be employed as molecular probes. 

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. 

Liquid-phase adsorption methods are widely used for quaUty control and specification purposes. The adsorption of iodine from potassium iodide solution is the standard ASTM method D1510-83 (2). The surface area is expressed as the iodine number whose units are milligrams of iodine adsorbed per gram of carbon. It is quite fortuitous that the values of iodine numbers turn out to be about the same as the values for surface areas in square meters per gram by nitrogen adsorption for nonporous carbon blacks. 

Hydrogen Liquefaction. Hydrogen can be produced from caustic—chlorine electrolytic cells, by decomposition of ammonia or methanol, or by steam—methane reforming. Hydrogen recovered by these methods must be further purified prior to Hquefaction. This is generally achieved by utilizing pressure swing adsorption methods whereby impurities are adsorbed on a soHd adsorbent. 

The raw material at this plant is natural gas supplied by the El Paso Natural Gas Company from a nearby pumping station. In each process train, gas is compressed to 850 psig, dehydrated by an adsorption method to remove 100% of the water, then passed through a refrigeration unit to lower the temperature to -60°F. A separator removes liquids upstream of the turboexpander. 

Tanahashi, I., Yoshida, A. and Nishino, A., Characterization of activated carbon fiber cloths for electric double layer capacitors by adsorption method. Carbon, 1991, 29(7), 1033 1037. 

SO as to end the air mixture to adsorber No. 2. The system is then fully automatic. Solvents which have been successfully recovered by the activated carbon adsorption method include methanol, ethanol, butanol, chlorinated hydrocarbons including perchlorethylene, which boils at 121 C (250 °F), ethyl ether, isopropyl ether, the acetates up to amyl acetate, benzene, toluene, xylene, mineral spirits, naphtha, gasoline, acetone, methyl ethyl ketone, hexane, carbon disulfide, and others. 

Surface Area Measurements. For a discussion of procs used see above under Fisher Sub-Siever and Nitrogen Adsorption. For AP, the Fisher Sub-Siever is most suitable for samples having surface areas from 0.05 to 0.46sqm/g, and the Nitrogen Adsorption method for finer mat, up to 30000 sqcm/cc (Ref 49)... 

It is important to distinguish clearly between the surface area of a decomposing solid [i.e. aggregate external boundaries of both reactant and product(s)] measured by adsorption methods and the effective area of the active reaction interface which, in most systems, is an internal structure. The area of the contact zone is of fundamental significance in kinetic studies since its determination would allow the Arrhenius pre-exponential term to be expressed in dimensions of area"1 (as in catalysis). This parameter is, however, inaccessible to direct measurement. Estimates from microscopy cannot identify all those regions which participate in reaction or ascertain the effective roughness factor of observed interfaces. Preferential dissolution of either reactant or product in a suitable solvent prior to area measurement may result in sintering [286]. The problems of identify-... 

Galvani, measurability of, 7 Potential distribution in passivation, 229 Potential formation as a variation of thickness with passive film, 225 Potential of zero charge, 1, 5-6, 189-192 accuracy of determination, 19 and the adsorption method, 39 at the air-solution interface (Nikitas), 30 and alloys, 142... 

Fig. 3. Plot to calculate surface fractal dimension by nitrogen adsorption method.

Bernard Manowitz, Treatment and Disposal of Wastes in Nuclear Chemical Technology George A. Sofer and Harold C. Weingartner, High Vacuum Technology Theodore Vermeulen, Separation by Adsorption Methods Sherman S. Weidenbaum, Mixing of Solids... 

The same resin was used for the purification via downstream processing of carminic acid, the natural colorant extracted from cochineal. By a direct adsorption method, a crude extract was applied on the polymeric bed gel and the adsorption kinetics studied using elution with hydrochloric acid and ethanol. The desorbed pure carminic acid concentrated under vacuum yielded a final product that complied with Codex Alimentarius requirements and FAO/OMS norms. 

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