Abstract

Abstract The Dubinin-Radushkevich (D-R) equation of adsorption predicts a Rayleigh distribution of adsorption free energy with adsorption (micropore) volume. Only when this distribution is present in microporous solids will a completely linear D-R plot result. Adsorption data of carbon dioxide at 195°K and nitrogen and argon at 77°K on various microporous polymer carbons are interpreted in terms of the D-R equation and distributions of free energy with pore volume. In no case is the complete Rayleigh distribution found to apply and corresponding deviations from linear D-R plots occur. Highly activated carbons show a bimodal distribution of free-energy values to nitrogen and argon at 77°K, but not to CO 2 at 195°K. Tentative suggestions for this behavior are presented.

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