The Characteristic Isotherm and Related Concepts

The relatively uniform success of these various plots suggests that, except as modified by changes in I, the shape of the isotherm in the multilayer region tends to be characteristic of the adsorbate and independent of the nature of the 

The curve of Fig. XVII-15 is essentially a characteristic curve of the Polanyi theory, but in the form plotted in might better be called a characteristic isotherm. Furthermore, as would be expected from the Polanyi theory, if the data for a given adsorbate are plotted with RTln P/f ) as the abscissa instead of just ln(P/P ), then a nearly invariant shape is obtained for different temperatures. The plot might then be called the characteristic adsorption curve. 

The existence of this situation (for nonporous solids) explains why the ratio test discussed above and exemplified by the data in Table XVII-3 works so well. Essentially, any isotherm fitting data in the multilayer region must contain a parameter that will be found to be proportional to surface area. In fact, this observation explains the success of Ae point B method (as in Fig. XVII-7) and other single-point methods, since for any P/P value in the characteristic isotherm region, the measured n is related to the surface area of the solid by a proportionality constant that is independent of the nature of the solid. 

The characteristic isotherm concept was elaborated by de Boer and coworkers [90]. By accepting a reference from a BET fit to a standard system and assuming a density for the adsorbed film, one may convert n/rim to film thickness t. The characteristic isotherm for a given adsorbate may then be plotted as t versus P/P. For any new system, one reads t from the standard r-curve and n from the new isotherm, for various P/P values. De Boer and co-work-ers t values are given in Table XVII-4. A plot of t versus n should be linear if the experimental isotherm has the same shape as the reference characteristic isotherm, and the slope gives E  

The existence of a characteristic isothenn for each adsorbate is encouraging 

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