New BET-like models for heterogeneous adsorption in microporous adsorbents

The paper presents a package of isotherm equations for heterogeneous adsorption aimed at the analysis of pore structure of sub- and microporous materials. One considers adsorption of small nearly spherical molecules in irregular pores of molecular size. The generalized BET theory is exploited respecting restrictions for multilayer adsorption (LBET approach). The model is based on thermodynamic relationships expressing changes of internal energy and configurational entropy due to the process. The adsorption energy is evaluated by using the Berthelot rule, and corrected with a factor Za representing a fraction of effective contacts enabling full adsorbent–adsorbate interaction. Side adsorbate–adsorbate interactions are neglected and constrained multilayer adsorption is considered. One assumes the values for Za to be uniformly distributed over the first layer adsorption sites within a range depending on the pore size. New models make it possible to obtain information on structure of pores and adsorption mechanisms on the basis of adsorption isotherms of small molecule adsorbates. Exemplary results of new models application for adsorption of CO2 and CH4 in an activated carbon are discussed.