LAUSR

HYPOTHESIS Vapor adsorption experiments are widely used to assess pore size distributions, but the large hysteresis sometimes observed between sorption and desorption isotherms remains difficult to interpret. Such hysteresis is influenced pore network connectivity, which has previously been modeled by percolation on infinite lattices. Our hypothesis is that percolation occurs instead through finite networks of micropores connecting accessible macropores, always exposed to the outside environment. THEORY We derive a general formula for sorption/desorption isotherms that introduces a simple measure of hierarchical pore connectivity - the fraction of always exposed pores. The model thus accounts for "small world" connections in finite-size percolation, while also incorporating other hysteresis mechanisms, in single-pore filling, liquid insertion into the solid matrix, and cavitation. FINDINGS Our formula is able to fit and interpret both primary and scanning sorption/desorption isotherms for a variety of adsorbates (noble gases, water, and organics) and porous materials (cement pastes, dental enamels, porous glasses, carbon black and nanotubes), including cases with broad pore-size distributions and large hysteresis. It allows quantification of the prevalence of percolating macropores in the material, even though these pores are never filled during the sorption experiments. A distinct bump in sorption isotherms is explained as a lowering of the barrier to nucleation of the vapor phase with a universal temperature scaling.