Structural characterization and chemical reactivity of synthetic Mn-goethites and hematites

Several goethites were obtained through the hydrolysis at 60 degrees C of Fe(III) solutions containing variable amounts of Mn(II) ions. The obtained samples were thermally treated at temperatures ranging from 180 to 310 degrees C until the complete phase transformation to hematite was achieved. The effect of Mn in the dehydroxylation process was investigated using X-ray diffraction (XRD) and the Rietveld refinement of XRD data together with scanning electron microscopy (SEM), differential thermogravimetric analysis (DTA) and Fourier transform infrared spectroscopy (FTIR). In all cases, the formed hematites retained the acicular shape of the precursor goethite. The dehydroxylation temperature increased with the increase of the Mn content in the parent goethite. The cell parameters of both phases decreased with the thermal treatment, however the decrease in the goethite b-parameter was more pronounced. This fact could be attributed to the distortion in the goethite structure by the presence of manganese. The band shifts in the FT-IR spectra of the goethites with different Mn substitution were analysed. The intensities of the hydroxyl vibrations were indicative of the degree of dehydroxylation. The chemical reactivity of all the samples, before and after the thermal treatment, was also studied. The kinetic experiments were carried out at 40 degrees C in 4 mol dm(-3) HCl. The acid dissolution of all Mn-goethites showed a congruent behavior indicative of a homogeneous distribution of Mn in the goethite crystals, this trend was not observed in the formed hematites presenting a high Mn content. The dissolution rate in goethites increased with the increase of Mn content, the opposite effect was observed in the corresponding hematites. The activation energy in both phases was also obtained and indicated that the Mn substitution produces an opposite effect on goethite- and hematite-phases. Different kinetic laws were applied in order to explain the dissolution behavior, but the modified first-order Kabai equation described the dissolution data best. (c) 2006 Elsevier B.V. All rights reserved.