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Synthèse et étude des propriétés structurales, magnétiques et chimiques de ferrates (IV), (V) et (VI) alcalins

Abstract : Synthesis, magnetic and chemical properties of alkaline ferrate (IV), (V) and (VI) have been investigated. The first part of this report is devoted to the study of the K-Fe -O system. After a bibliographical review of potassium oxides, the syntheses carried out by., solid-state reaction between KO2 and an iron oxide have showed that it is possible to synthesise K2FeO4 at 350°C under atmospheric pressure of oxygen, or at 450°C in a sealed "Pyrex" tube. Ferrate (V) was only detected in some of mixtures, the oxidation step (IV) was never found. The study of the Na-Fe -O system lead to evidence the existence of sodium ferrate (IV) Na4FeO4. This phase crystallises in the triclinic system and belong to the Na4MO4 series (M = transition element). In this compound, iron is in a tetrahedral site. Na4FeO4 is aritiferromagnetic below 16 K. The study of the magnetic structure shows that the exchange interactions may form via Fe-O-Na-O-Fe superexchange ways. Na4FeO4 is the first example of material which stabilises Fe (IV) in a tetrahedral site. With our experimental conditions, it was not possible to stabilise the oxidation step (VI), whereas a ferrate (V) could be detected while operating in presence of oxygen generated in-situ in the sealed Pyrex tube or in presence of hydroxide. The study of the Na-K-Fe-O system evidenced the existence of the oxidation step (V) in a compound with the K2NaFeO4 formula. Isotypic with K2NaMnO4, iron (V) is tetrahedrally co-ordinated. Paramagnetic until 6 K, the Mössbauer parameters ofthis Fe (V) high spin have been specified for the first time. The optimization of the synthesis of ferrate (VI) by electrochemical way is also described. Ferrate (IV) and (V) di sproportionate to give Fe (VI) and Fe (III). The last part of this work is devoted to the chemical propel1ies of ferrate (VI) which has potential industrial applications in the field of energy and environment.
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http://docnum.univ-lorraine.fr/prive/SCD_T_2000_0132_JEANNOT.pdf
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Submitted on : Thursday, March 29, 2018 - 10:39:03 AM
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Cécile Jeannot. Synthèse et étude des propriétés structurales, magnétiques et chimiques de ferrates (IV), (V) et (VI) alcalins. Autre [cond-mat.other]. Université Henri Poincaré - Nancy 1, 2000. Français. ⟨NNT : 2000NAN10132⟩. ⟨tel-01746496⟩

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