A method has been worked out for the reproducible preparation of Green Rust substances involving SO42-, Cl-, Br-, and I- anions. The chemical composition of the substances prepared has been followed in dependence on the synthesis conditions. The powder X-ray and electron diffraction patterns and infrared and Moessbauer spectra have been measured and discussed.
Oxidation of FeSO4 by air oxygen has been studied in aqueous solutions of constant acidity. The effect of various reaction conditions (of acidity, temperature, concentration of FeSO4, and of the air flow through the suspension) on the yield of various modifications of ferric oxide-hydroxides in the product mixture is described and the mechanism of the process is discussed. Reaction products prepared in the neutral and weakly alkaline solutions contain predominantly lepidocrocite (γ-FeOOH), amorphous Fe2O3.n H2O (ferrihydrite), at higher pH values also goethite (α-FeOOH) is formed. Their mutual ratios depend strongly on the solution acidity.
The kinetics of the reaction between α-Fe2O3 and K2CO3 have been investigated over the temperature range 600 to 800 °C, and the phase composition of the products has been determined. The reaction follows the rate law α = 1 - exp (-kτn). At molar ratios K : Fe 1, KFeO2 is the only product. At K : Fe 1, initially formed KFeO2 reacts with hematite to yield K2Fe4O7. The latter phase has been assigned a cubic structure with a = 1.681 ± 0.003 nm. based on X-ray powder diffraction patterns and Mossbauer spectra, the structure of K2Fe4O7 is proposed to be a cubic close-packed array of oxygen atoms, part of these being replaced by potassium atoms, with Fe atoms occupying the octahedral interstices.
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