Temperature- and moisture-dependent studies on alunogen and the crystal structure of meta-alunogen determined from laboratory powder diffraction data

Abstract

Starting from a synthetic sample with composition Al2(SO4)3·16.6H2O, the high-temperature- and moisture-dependent behavior of alunogen has been unraveled by TGA measurements, in situ powder X-ray diffraction as well as by gravimetric moisture sorption/desorption studies. Heating experiments using the different techniques show that alunogen undergoes a first dehydration process already starting at temperatures slightly above 40 °C. The crystalline product of the temperature-induced dehydration corresponds to the synthetic equivalent of meta-alunogen and has the following chemical composition: Al2(SO4)3·13.8H2O or Al2(SO4)3(H2O)12·1.8H2O. At 90 °C a further reaction can be monitored resulting in the formation of an X-ray amorphous material. The sequence of “amorphous humps” in the patterns persists up to 250 °C, where a re-crystallization process is indicated by a sudden appearance of a larger number of sharp Bragg peaks. Phase analysis confirmed this compound to be anhydrous Al2(SO4)3. Furthermore, meta-alunogen can be also obtained from alunogen at room temperature when stored at relative humidities (RH) lower than 20 %. The transformation is reversible, however, water sorption of meta-alunogen to alunogen and the corresponding desorption reaction show considerable hysteresis. For RH values above 80 %, deliquescence of the material was observed. Structural investigations on meta-alunogen were performed using a sample that has been stored at dry conditions (0 % RH) over phosphorus pentoxide. Powder diffraction data were acquired on an in-house high-resolution diffractometer in transmission mode using a sealed glass capillary as sample holder. Indexing resulted in a triclinic unit cell with the following lattice parameters: a = 14.353(6) Å, b = 12.490(6) Å, c = 6.092(3) Å, α = 92.656(1)°, β = 96.654(1)°, γ = 100.831(1)°, V = 1062.8(8) Å3 and Z = 2. These data correct earlier findings suggesting an orthorhombic cell. Ab-initio structure solution in space group Poverline{1}, using simulated annealing, provided a chemically meaningful structure model. The asymmetric unit of meta-alunogen contains three symmetry independent SO4-tetrahedra and two Al(H2O)6 octahedra. The polyhedra are isolated, however, linkage between them is provided by Coulomb interactions and hydrogen bonding. In addition to the water molecules which directly belong to the coordination environment of the aluminum cations there are two additional zeolitic water sites (Ow1 and Ow2). If both positions are fully occupied meta-alunogen corresponds to a 14-hydrate. Structural similarities and differences between the previously unknown structure of meta-alunogen and alunogen are discussed in detail. Since hydrous aluminum sulfates have been postulated to occur in Martian soils, our results may help identifying meta-alunogen by X-ray diffraction not only on the surface of the Earth but also using the Curiosity Rover’s ChemMin instrument.