High-resolution sorption studies of argon and nitrogen on large crystals of microporous zeolite ZSM-5

High resolution adsorption (HRADS) with argon and nitrogen at 77 K were performed on large crystals of zeolite ZSM-5 using a novel volumetric device. Multi-step isotherms for both adsorptives could be observed for the first time. The micropore filling was followed by low temperature microcalorimetry. Exothermic heats of adsorption were found to be correlated with steps in the adsorption isotherms. Based on results from atom-atom potential energy calculations (AAP) as well as from independent model building it is shown that 24 kinetic adsorbate molecules can be situated in a ZSM-5 unit cell. Localized adsorption is presented as possible filling mechanisms. Experimental results are reasonably interpreted assuming primary filling of narrow channels and secondary adsorption in the wider channel intersections. At least for nitrogen there is evidence for a transition of fluid-like to a solid-like adsorbate phase.