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Redox reactions of K3[Fe(CN)6] during mechanochemically stimulated phase transitions of AlOOH
(2011)
Thermally induced redox reactions of K3[Fe(CN)6] (1) were investigated for a broad temperature range by thermal methods and structure analytical methods (ESR and Mößbauer spectroscopy, X-ray Powder diffraction and XANES). Based on the influence of the mechanically activated and transforming matrices 2 and 3, redox processes can be tuned to form doped Al2O3 systems which contain either isolated Fe3+ centres or redox active phases and precursors like (Al1-xFex)2O3 (4), (Al3-xFex)O4 (5), Fe3O4, Fe2O3 and Fe0. The phase Fe3C and the chemically reactive C-species were detected during the reaction of 1. The final composition of the doped products of α-Al2O3 is mainly influenced by the chemical nature of the Fe doping component, the applied temperature and time regime, and the composition of the gas phase (N2, N2/O2 or N2/H2). From the solid state chemistry point of view it is interesting that the transforming matrix (2 and 3) possesses both oxidative and protective properties and that the incorporation of the Fe species can be performed systematically.
Radical species like CO-2,CO-3, SO-2, and SO-3 can be created by exposing natural and synthetic calcium carbonates to sunlight or to the light of a Hg(Xe) lamp. This poses as a risk for ESR dating of these materials, because the radicals formed by light exposure cannot be distinguished from those generated by radioactivity. Furthermore, paramagnetic centers like SO-2, electrons trapped near Zn2+ or Cd2+ ions, surface defects, and radicals with g?=2.0040, can be bleached in ?-irradiated samples by light and show conversion effects.