Abstract
A recent topic in the discussion of fluoride mixtures containing AlF<sub>3</sub> is the possible existence of the complex AlF<sub>5</sub><sup>2-</sup>. The dissociation schemes in question are the following: AlF<sub>6</sub><sup>3−</sup> = AlF<sub>5</sub><sup>2−</sup> + F<sup>−</sup> (Ia) AlF<sub>5</sub><sup>2−</sup> = AlF<sub>4</sub><sup>−</sup> + F<sup>−</sup> (Ib) or AlF<sub>6</sub><sup>3−</sup> = AlF<sub>4</sub><sup>−</sup> + 2F<sup>−</sup> (II) The question is whether reaction II is sufficient to describe the molten mixture of <i>MF</i>-AlF<sub>3</sub> (where <i>M</i> = Li<sup>+</sup>, Na<sup>+</sup>, and K<sup>+</sup>) or whether reactions Ia and Ib are required. Our examination of the evidence accumulated so far shows that experimental data are not conclusive.
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