Adsorbates argon

The similarity in the adsorption behavior of krypton on the three kinds of mica surfaces suggests that the adsorption here is primarily due to dispersion forces, with very little contribution from ion-induced dipole forces. The results of Barrer and Stuart (1) for the adsorption of argon on various ion-exchanged forms of faujasite are similar. They found that while calcium, strontium, and lithium faujasite—i.e., the materials containing cations with greater polarizing power—did show heat effects correlatable with ion-induced dipole interactions, no such effects were observed with sodium, potassium, or barium zeolites. With the latter materials, they also concluded that the adsorbed argon possessed appreciable mobility. 

As an important fact, we note how the interest in investigating phase transitions in adsorbed argon has permitted the development of new techniques, such as the microcaloriraetric teehnique [122,123,128]. This teehnique permits a continuous recording of the properties as a funetion of eoverage or time. It has been shown that this procedure is very sensitive and very aeeurate. The existence of a peak on the eurve of the isosteric heats for a coverage close to a monolayer and, simultaneously, the presenee of a clear substep in the adsorption isotherms were interpreted as evidence for a two-dimensional phase transition of the monolayer, changing from a hypercritical fluid state to a localized one [122,128,129]. 

Using the BET equation and assuming the adsorbed argon molecules are two molecules thick, determine the mass of charcoal required to adsorb 5 m of argon at a temperature of... 

Deitz and Carpenter [176] found that argon and nitrogen adsorbed only... 

Calculate A52 at = 0.1 for argon at 77 K that forms a weak adsorption bond with the adsorbent, having three vibrational degrees of freedom. 

A study of Table 1.1 reveals interesting features as to the mobility of the adsorbed atoms. Thus, for an argon atom on the (100) face, the easiest path from one preferred site S to the next is over the saddle point P, so that the energy barrier which must be surmounted is (1251 — 855) or 396 X 10 J/molecule. Since the mean thermal energy kT at 78 K is only 108 J/molecule, the argon molecule will have severely limited mobility at this temperature and will spend nearly all of its time in the close vicinity of site S its adsorption will be localized. On the other hand, for helium on the... 

From these various examples, it is clear that the adsorption energy for a given kind of site can vary quite markedly from one crystal face of the adsorbent to another. For argon on solid xenon (Table 1.1), for example, the most favourable site has a o value of —1251 x 10" J on the (100) face but only -1072 on the (111) face. Such differences are in no way surprising, and they have been found also with ionic crystals. 

Fig. 2.14 The isosteric heat of adsorption ( ) of argon, nitrogen and oxygen of rutile at 95 K, plotted as a function of the amount adsorbed (expressed in cm (stp). The uptake of each gas corresponding to the completion of a monolayer is marked. Note the more rapid decrease in as the amount adsorbed approaches monolayer completion. (After Drain.)...

In their pioneer work, Brunauer and Emmett adopted the value a (Ar) = 13-8 for the molecular area of argon, by insertion of the liquid density Pi in the standard equation (2.27). The same figure was recommended by McClellan and Harnsberger " as a result of their comprehensive survey of the literature, already referred to. These workers noted that the recorded values of a (based on a (N2) = 16 2 A ) extended over the wide range 10-19 A, and concluded that the area occupied per molecule of argon in the completed monolayer varied from one adsorbent to another. 

As already mentioned, the choice of the supercooled liquid as reference state has been questioned by some workers who use the saturation vapour pressure of the solid, which is measured at the working temperature in the course of the isotherm determination. The effect of this alternative choice of p° on the value of a for argon adsorbed on a number of oxide samples, covering a wide range of surface areas, is clear from Table 2.11 the average value of is seen to be somewhat higher, i.e. 18 OA. ... 

The survey in the present section shows quite clearly that it is not possible to assign a fixed value of a to a given adsorptive, which will remain valid for its adsorption on ail adsorbents. As demonstrated in Section 2.7, nitrogen and argon would seem to provide the best approximation to a constant effective molecular area, with = 16-2 A and a, (Ar) = 16-6 A. ... 

In view of the widespread use of nitrogen and argon in surface area and porosity studies, data for the construction of the standard a,-curves for these adsorbates on hydroxylated silica, are given in Table 2.14 (p. 93) for nitrogen and in Table 2.15 for argon. From the arguments of Section 2.12, these should be adequate for other oxides such as alumina, if high accuracy is not called for. 

Calculations of the interaction energy in very fine pores are based on one or other of the standard expressions for the pair-wise interaction between atoms, already dealt with in Chapter 1. Anderson and Horlock, for example, used the Kirkwood-Miiller formulation in their calculations for argon adsorbed in slit-shaped pores of active magnesium oxide. They found that maximum enhancement of potential occurred in a pore of width 4-4 A, where its numerical value was 3-2kcalmol , as compared with 1-12, 1-0 and 1-07 kcal mol for positions over a cation, an anion and the centre of a lattice ceil, respectively, on a freely exposed (100) surface of magnesium oxide. 

It would clearly be of interest to discover how far the nonane method can be used with adsorbates other than nitrogen. A study along these lines has been carried out by Tayyab, but a discussion of his rather unexpected results is best deferred until the role of fine constrictions has been considered (p. 228). Meanwhile it may be noted that the applicability of the technique seems to be limited to adsorptives such as nitrogen or argon which have negligible solubility in solid or supercooled liquid n-nonane. 

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