Evaluation of confinement effects in zeolites under Henryʹs adsorption regime

This paper provides a detailed thermodynamic analysis of gas/vapour adsorption in zeolites at low pressures. At these conditions, we show first that Henryʹs isotherm can be conveniently rewritten using the thermodynamic isotherm model developed in a previous study [J. Llorens, M. Pera-Titus, Description of gas adsorption on microporous materials: evaluation of energy heterogeneity, J. Colloid Interface Sci. 331, 2009, 302–311], linking the integral free energy of adsorption relative to saturation, Ψ/RT, expressed as a Kiselev integral, with the variable Z = 1/−ln(Π), being Π the relative pressure. Relevant information about sorbate confinement effects in zeolites can be inferred using strong sorbates under Henryʹs adsorption regime using the thermodynamic formulation provided here. The confining level of zeolites can be characterized by a parameter (m1), whose value depends on the zeolite framework, but remains essentially unchanged with the sorbate probe molecule and temperature. We illustrate the application of these concepts using a collection of MFI and MTW-type zeolites as model systems.