Fe-modified zeolites (ferrierite and MFI) were prepared by four impregnation methods followed by calcination and tested as catalysts in oxidative dehydrogenation of ethane by nitrous oxide at 350 degrees C. The Fe cationic and Fe oxidic species were identified by combination of UV-Vis spectroscopy and voltammetry. Monomeric or dimeric Fe ions have only UV absorption bands and some of them evolve voltammetrically identifiable [Fe(OH)(x)]((3-x)+) ions in contact with acetic acid-sodium acetate buffer. Fe oxide nanoclusters characterised by UV band at about 28,000 cm(-1) are not detected by voltammetry under chosen conditions because they are situated inside the zeolite channels. Amorphous, nanocrystalline, and crystalline Fe(III) oxides were distinguished sensitively by their specific voltammetric reduction peaks at potentials -0.1 to -0.8 V/SCE in acetate buffer (pH 4.7) and by phase-specific electron pair transitions responsible for Vis absorption band centred at 17,500-21,000 cm(-1). The proposed method to differentiation between these ferric oxides is novel in materials analysis and solid state speciation. The monomeric and dimeric ferric ions are active in oxidative dehydrogenation of ethane to ethene with selectivity about 40-60% under used conditions, while Fe oxide nanoclusters are too active and over-oxidise ethane and/or ethene to C, CO and CO(2). Oppositely to general expectations, ferric oxides are indifferent in the catalytic reaction and do not decrease reaction selectivity. (C) 2010 Elsevier B.V. All rights reserved.