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sorbed increases. For small uptakes, the isosteric heat may decrease rather strongly with the amount adsorbed. This would be an indication that there are some local intracrystalline positions where the guest molecules are preferentially sorbed more exothermally than in the rest of the intracrystalline volume. The measurement of adsorption isotherms at different temperatures permits the calculation of the heat of adsorption as a function of surface coverage. When experimental data are reported as a set of adsorption isotherms for a particular gas- adsorbent system, the isosteric heat of adsorption is usually calculated (Bajusz and Goodwin, 1997). The isosteric heat of adsorption can be calculated from a series of isotherms by application of the Clausius-Claperyron equation as follows: d ln P ∆ H a d s = R d ( 1 T ) (1) n Using the data from nitrogen adsorption isotherms measured at 50 C, 25 C, and 0 C (shown in Figure 9), the isosteric heats of adsorption were determined by evaluating the slope of a plot of ln(P) versus (1/T) at several coverages. The plots of ln(PN2) versus (1/T) at several coverages for Li94.5Na1.5-LSX (top) and Li94.2Ag1.1Na0.7-LSX (bottom) are shown in Figure 10. The isosteric heats of adsorption at different coverages were calculated for each of these materials and are shown in Figure 11. The plots are shown as the heat of adsorption (in kcal/mol) versus coverage in molecules of adsorbate per cavity (based on 5.7 cavities per unit cell (Breck, 1984)). From the plots of the heats of nitrogen adsorption, one can see that the isosteric heat of adsorption for N2 on Li94.2Ag1.1Na0.7- LSX is quite high ( 8 kcal/mol) at low coverages, but immediately drops sharply to become nearly horizontal. This is very similar to that of the near-fully exchanged Ag- LSX and indicates the presence of local sites where the N2 is preferentially sorbed more 100PDF Image | PSA USING SUPERIOR ADSORBENTS
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