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Hindered adsorbed layers completely filling the nanopores must causesignificant deviations from the classical BET isotherms for multimolecularadsorption of vapor in porous solids. Since the point of transition from freeto hindered adsorption moves into narrower nanopores as the pore vapor pressure(or humidity) decreases, the area of the surface of multimolecular adsorptionlayer exposed to vapor gets modified by an area reduction factor that decreaseswith increasing thickness of the layer, and thus also with increasing vaporpressure. The area reduction factor does not affect the rates of directadsorption or condensation from the vapor, which represent a local process, butimposes a lateral constraint on the total area and volume of the free portionof the adsorption layer in direct contact with vapor. Assuming a power-law forthe dependence of the area reduction factor on the number of molecular layers,one can express the modified isotherm in terms of logarithmic orpolylogarithmic (a.k.a Jonqui\`ere) functions. Comparisons with some publishedexperimentally obtained isotherms show that the present modification of the BETtheory for hindered adsorption goes in the right direction. Detailedcalibration of the theory and an extension for indirect communication of vapormolecules with the molecules adsorbed in nanopores less than a few nm wide willrequire further research.

Direct Multilayer Adsorption of Vapor in Solids with Multiscale Porosity and Hindered Adsorbed Layers in Nanopores