On the structures of X- and Y-type zeolites. Structural changes within the cavities of Na-X during dehydration

Samples of partially dehydrated and dehydrated Na-X were examined structurally by X-ray diffraction methods, revealing the progressive structural changes which occur as water is removed. In general, the total number of Na atoms in the small pore region remains unchanged by dehydration (ca. 18 per unit cell), as does the total number (non-mobile) in the 12-ring and site III regions (ca. 39). The site II population, however, is more than doubled by dehydration, from about 12 to about 25 Na, accounting for most of the loss from the mobile phase. The 12-ring sites, which in hydrated samples appear to comprise pairs of centrosymmetrically related [Na(H₂O)₂]⁺ units, rearrange during dehydration, with site III becoming an important location of Na atoms. At intermediate levels of dehydration, the remaining localized water molecules in the 12-ring region are found in a variety of associations with Na atoms, including perhaps as [Na(H₂O)₅]⁺ units whose Na atom occupies site III. In a sample containing H₃O⁺ ions as well as Na⁺ as counter ions, site II was found to have a very low occupancy.