Understanding Sorption Mechanisms Directly from Isotherms.

Currently, more than 100 isotherm models coexist for the six IUPAC isotherm types. However, no mechanistic insights can be reached when several models, each claiming a different mechanism, fit an experimental isotherm equally well. More frequently, popular isotherm models [such as the site-specific models like Langmuir, Brunauer-Emmett-Teller (BET), and Guggenheim-Anderson-de Boer (GAB)] have been applied to real and complex systems that break their basic assumptions. To overcome such conundrums, we establish a universal approach to model all isotherm types, attributing the difference to the sorbate-sorbate and sorbate-surface interactions in a systematic manner. We have generalized the language of the traditional sorption models (such as the monolayer capacity and the BET constant) to the model-free concepts of partitioning and association coefficients that can be applied across the isotherm types. Through such a generalization, the apparent contradictions, caused by applying the site-specific models alongside with cross-sectional area of sorbates for the purpose of surface area determination, can be eliminated straightforwardly.