The electrochemistry of oxide ions was studied in molten LiF ‐ BeF 2 ‐ ZrF 4 [65.6‐29.4‐5.0 mole percent (m/o)] and LiF ‐ BeF 2 ‐ ThF 4 (72‐16‐12 m/o) at gold, iridium, and glassy carbon electrodes in the temperature interval 500°–710°C. Well‐defined and reproducible voltammograms could be obtained only at gold electrodes. Cyclic voltammetric and chronopotentiometric results indicate the following electrochemical reaction pathway O 2 − = O + 2 e O + O = O 2 O + O 2 − = O 2 2 − Some evidence for adsorption of O 2 was obtained. O 2 2 − ions are oxidized further producing a voltammetric postwave which increases with Na 2 O 2 additions. O 2 2 − ions gradually decompose in these media; this decomposition is more rapid in Zr(IV)‐containing melts as compared to the Th(IV)‐containing melts. NaO 2 additions result in the same voltammetric results as obtained upon the addition of Na 2 O 2 , indicating that O 2 − ions are more unstable in these melts than in the previously studied LiF ‐ NaF ‐ KF eutectic. The results obtained provide the basis for an in situ electrochemical determination of small amounts of dissolved oxide.
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Manning et al. (1977) studied this question.