Voltammetric Study of Fe Ions in M2O-M'O-SiO2(M: alkali metal, M': alkaline-earth metal) Glass Melts

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  • NISHIMURA Ryuichi
    Department of Applied Chemistry, Faculty of Engineering, Ehime University
  • YAMASHITA Hiroshi
    Department of Applied Chemistry, Faculty of Engineering, Ehime University
  • MAEKAWA Takashi
    Department of Applied Chemistry, Faculty of Engineering, Ehime University

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  • M<sub>2</sub>O-M′O-SiO<sub>2</sub>(M:アルカリ金属,M′:アルカリ土類金属)ガラス融液中の鉄イオンのボルタンメトリー

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The half-wave potentials of the reduction of Fe3+ in 16M2O (M: Li, Na, K and Cs)·10M′O (M′: Mg, Ca, Sr and Ba)·74SiO2 glass melts were examined by differential pulse voltammetry. In all melts, the half-wave potential shifted to the positive side with increasing temperature. The equilibrium of Fe3+/Fe2+ moved toward the reduced side with increasing temperature. The replacement of Li+ ions by larger alkali ions resulted in a positive shift of the half-wave potentials. On the other hand, the smaller the ionic radius of the alkaline-earth metal ion, the larger the half-wave potential. The Fe3+/Fe2+ equilibrium was mainly affected by the stability of the Fe3+-complex and the basicity of the melts. Variations in the kinds of alkali and alkaline-earth metal ions influenced the stability of the complex and the basicity of the melts, respectively. The half-wave potential moved toward the positive side (45mV at 1473K) when the atmosphere over the melts was changed from pure oxygen gas to air; thus, the reversibility of Pt: O2 reference electrode was confirmed.<br>

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