THE ROLE OF H_3O~+ IN THE CRYSTAL STRUCTURE OF ILLITE

摘要

In spite of decades of research on the subject, the crystal structure of illite is still poorly understood. The purpose of this study was to address this problem by investigating the nature of the interlayer content in illite IMt-2 from Silver Hill, Montana, using analytical transmission electron microscopy (ATEM), thermogravimetry (TG), and X-ray powder diffraction (XRPD) analyses. The ATEM data, together with literature and TG results, yielded the formula K_(0.70)Na_(0.01)(H_2O)_(0.42) (Al_(1.53)Fe_(0.06)~(2+)Fe_(0.19)~(3+)Mg_(0.28))_(Σ=2.06)(Si_(3.44)Al_(0.56))O_(10)(OH)_2 or, assuming the presence of H_3O~+, K_(0.69)Na_(0.01)(H_3O)_(0.28)~+(Al_(1.47)Fe_(0.06)~(2+)Fe_(0.19)~(3+)Mg_(0.28))_(Σ =1.99)(Si_(3.40)Al_(0.60))O_(10)(OH)_2. The first formula indicates surplus interlayer and octahedral species, whereas the second shows no excess. The XRPD data were refined by Rietveld techniques, down to an R_p factor of 10.48-13.8%. The mineral composition consists largely of illite-2M_1, illite-1M, and minor quartz. Although the refinement accuracy is limited by the intrinsic poor quality diffraction of the illites, the partially refined model is consistent with the chemical composition; in particular, attempts to introduce octahedral cations in excess of 2 were fruitless. All the results support the simple structural model, by which the illite structure strictly corresponds to a dioctahedral mica with H_3O~+ replacing K. As a consequence, the crystalchemical formula of illites should be calculated on the basis of six tetrahedral plus octahedral cations.