The dehydration process in the zeolite laumontite: a real-time synchrotron X-ray powder diffraction study

The dehydration process of the natural zeolite laumontite Ca₄Si₁₆Al₈O₄₈ · 18 H₂O has been studied in situ by means of powder diffraction and X-ray synchrotron radiation. Powder diffraction profiles suitable for Rietveld refinements were accumulated in time intervals of 5 minutes using a position sensitive detector (CPS-120 by INEL), while the temperature increased in steps of about 5 K. The synchronization of accumulation time and temperature plateau allowed collection of 62 temperature-resolved powder patterns in the range 310–584 K, whose analysis produced a dynamic picture of the laumontite structure response to dehydration. The first zeolitic water molecules diffusing out of the channels are those not bonded to the Ca cations and located in the W(1) site, whose occupancy drops smoothly to 10% during heating to 349 K, while the sample in the capillary is still submerged in water. The remaining W(1) and 60% of W(5) water molecules are expelled rather sharply at about 370 K. At this temperature all remaining water submerging the powder crystallites is lost, the structure contains about 13 water molecules/cell, and the crystal structure is that of leonhardite. On continued heating 80% of the water molecules from the W(2) site are lost between 420 and 480 K, while a small amount of the diffusing water is reinserted in the W(5) site. The occupancy factor of the W(8) site decreases starting at 480 K, and reaches a maximum loss of 20% at 584 K. The combined occupancy of the Ca-coordinated W (2) and W (8) water sites never falls much below two, so that the Ca cations in the channels, which are bonded to four framework oxygen atoms, are nearly six-coordinated in the explored temperature range. The water loss is accompanied by large changes in the unit cell dimensions. Except at 367 K, where the excess surrounding water is leaving, all changes in cell dimensions are gradual. The loss of the hydrogen bonded W(1) and W(5) water molecules is related to most of the unit cell volume reduction below 370 K, as shown by the contraction of the a-, b- and c-axes and the increase in the monoclinic angle. Loss of the Ca-coordinated W(2) and W(8) water molecules has a small effect on the unit cell volume as the continued contraction of the a- and c-axes is counter-balanced by a large expansion in the b-axis and a decrease in the monoclinic β angle.