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Measurement of the pore-size distribution (PSD) via gas adsorption and the so-called "kernel method" is a widely used characterization technique for rigid adsorbents. Yet, standard techniques and analytical equipment are not appropriate to characterize the emerging class of flexible adsorbents that deform in response to the stress imparted by an adsorbate gas, as the PSD is a characteristic of the material that varies with the gas pressure and any other external stresses. Here, we derive the PSD for a flexible adsorbent using statistical mechanics in the osmotic ensemble to draw analogy to the kernel method for rigid materials. The resultant PSD is a function of the ensemble constraints including all imposed stresses and, most importantly, the deformation free energy of the adsorbent material. Consequently, a pressure-dependent PSD is a descriptor of the deformation characteristics of an adsorbent and may be the basis of future material characterization techniques. We discuss how, given a technique for resolving pressure-dependent PSDs, the present statistical mechanical theory could enable a new generation of analytical tools that measure and characterize certain intrinsic material properties of flexible adsorbents via otherwise simple adsorption experiments.

adsorption

Relationship between pore-size distribution and flexibility of adsorbent materials: statistical mechanics and future material characterization techniques