The interpretation of pore dimensions based on physical ad-desorption analyses is central to the characterization of pore network structure. Several approaches have been proposed and are commonly employed in the analysis of physical adsorption and/or desorption to deduce the dimensions of the porous network. These approaches assume either theoretical (e.g., BET, the Halsey equation as interpreted by Pierce et al., or the more recent analyses of microporosity) or "standard" isotherms as model(s) for the sequential calculations required in estimating the pore network dimensions. Subsequent representation of the pore dimensions and the relationship between these distributions in dimension and other experimental parameters (such as catalytic activity, adsorptivity or transport); thus, depend explicitly on the model employed in the analyses. Each instrument currently available for the measurement of porous solid structure by sorption employs the same specific models for the relationship between the volume ad-desorbed and the dimensions of the porous network that is being characterized.
This paper analyzes the interpretation of porous dimensions based on the sequential calculations required in the analyses. A new approach is proposed which is based on a modification to current practices reflecting Halsey's original theory for the thickness of the adsorbed layer (as a function of P/Po). Further, the calculations of the incremental changes in the exposed surface area are discussed as they relate to pore network structure. A method is proposed to infer the differences in pore shape. Sorption data are analyzed by these new approaches, and these analyses will be compared with those approaches currently employed. Analyses based on these modified approaches provide a dramatically more consistent interpretation of the sorption data and the corresponding pore network structures.