Gas adsorption at 77 K is probably the most widely used method to characterize mesoporous adsorbents via capillary condensation. Mercury intrusion is also commonly used for the characterization of such materials with the possibility to extend the pore width distribution measurement to the macropore range. More recently water intrusion was proposed to study hydrophobic porous solids. Thermoporometry is a further characterization method, now based on the study of the solid/liquid transition. We can consider that all these methods rely on the modification of the phase diagram of a pure substance under the effect of confinement. For each of them, the equations and models derived are based either on classical thermodynamics or on statistical approaches. In most cases, the derivation of the pore width distribution is carried out with the assumption that the porous system is made up of non‐connected cylinders, whereas the actual complexity of the structure is derived from the hysteresis shape. Our aim here is to compare the four approaches above (gas adsorption, mercury intrusion, water intrusion, thermoporometry) on samples giving rise, in their gas adsorption isotherms, to the typical hysteresis loops of the IUPAC classification. Our comparison is in great part carried out after the shape of the hysteresis loops obtained with the various methods and after the information it brings on the mechanism of replacement of a phase by the other within the porous system.
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