Lattice vibration spectra. Part XCV. Infrared spectroscopic studies on the iron oxide hydroxides goethite (α), akaganéite (β), lepidocrocite (γ), and feroxyhite (δ)

Abstract

Infrared spectra (IR, FIR, DRIFT, 90 and 295 K) and DSC measurements of the various polymorphs of iron oxide hydroxide, viz. goethite (α), akaganéite (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 OHOH hydrogen bonds of lepidocrocite, for example, compared to that of the OHO 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) (v_OH = 2950 cm⁻¹, 295 K), α-MnO(OH) (v_OH = 2686 cm⁻¹), and α-FeO(OH) (v_OH = 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 akaganéite than those of the other polymorphs. This is obviously due to the Cl⁻ ion impurities present in this compound.