Lattice vibration spectra. Part XCV. Infrared spectroscopic studies on the iron oxide hydroxides goethite (α), akaganéite (β), lepidocrocite (γ), and feroxyhite (δ)
| Autor: | B. Weckler, H.D. Lutz |
|---|---|
| Rok vydání: | 1998 |
| Předmět: |
Goethite
Chemistry Hydrogen bond Metal ions in aqueous solution Thermal decomposition Inorganic chemistry Infrared spectroscopy General Chemistry Crystal structure engineering.material Inorganic Chemistry Crystallography chemistry.chemical_compound visual_art visual_art.visual_art_medium engineering Hydroxide Lepidocrocite |
| Zdroj: | European Journal of Solid State and Inorganic Chemistry. 35:531-544 |
| ISSN: | 0992-4361 |
| DOI: | 10.1016/s0992-4361(99)80017-4 |
| Popis: | Infrared spectra (IR, FIR, DRIFT, 90 and 295 K) and DSC measurements of the various polymorphs of iron oxide hydroxide, viz. goethite (α), akaganeite (β), lepidocrocite (γ), and feroxyhite (δ), and of deuterated specimens are reported. They are discussed with respect to the crystal structures proposed in the literature, the hydrogen bonds present, the energies of the OH stretching, OH bending (librational), and translational modes, and their thermal decomposition. From the two space groups proposed for β- and γ-FeO(OH), the groups I4/m and Cmc21, respectively, seem to be more reliable. The disorder of the OH− ions of γ-FeO(OH) has not been confirmed in contrast to that of δ-FeO(OH). The intraionic O(H,D) distances of γ- and δ-FeO(OH) derived from neutron powder diffraction studies have to be doubted. The greater strength of the OHOH hydrogen bonds of lepidocrocite, for example, compared to that of the OHO hydrogen bonds of goethite despite the larger hydrogen bond acceptor capability of O2− is due to the strong cooperativity of the hydrogen bonds of the γ-polymorph. The extremely different strength of the hydrogen bonds of isostructural α-AlO(OH) (vOH = 2950 cm−1, 295 K), α-MnO(OH) (vOH = 2686 cm−1), and α-FeO(OH) (vOH = 3130 cm−1) is caused by the different synergetic effect of the metal ions involved, especially that of Mn3+ due to its Jahn-Teller behaviour. The decomposition temperatures and heats of the various FeO(OH) modifications as well as the halfwidths of the DSC peaks evidence a much faster decomposition rate of akaganeite than those of the other polymorphs. This is obviously due to the Cl− ion impurities present in this compound. |
| Databáze: | OpenAIRE |
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