Physisorption, first observations

In adsorption from solution, physisorption is far more common than chemisorption, although the latter is sometimes possible. Solute adsorption is usually restricted to a monomolecular layer, since the solid-solute interactions, although strong enough to compete successfully with solid-solvent interactions in the first adsorbed monolayer, do not do so in subsequent monolayers, because the interaction is screened by the solvent molecules. Thus, multilayer adsorption has only rarely been observed in a number of cases, and identified, when the number of adsorbate molecules exceeds the number of mono-layer molecules possible on the total adsorbent surface area. However, this analysis cannot be applied to polymer adsorption, because it is generally impossible to determine the surface area of a monomolecular layer of a polymer adsorbed flat on the solid surface. This is because the adsorbed polymer can only be anchored to the surface at a few points, with the remainder of the polymer in the form of loops and ends moving more or less freely in the liquid phase. 

In type VI, an initial adsorption step may be observed if a chemisorption occurs along with physisorption, however the chemisorption portion should be somewhat irreversible and subsequent isotherms will differ from the first measured isotherm. The units on the abscissa in these figures are arbitrary. Today they are usually in mmol g f... 

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