AlF3 is soluble in HF only in the presence of KF due to the formation of:
K3[AlF3H3]
K3[AlF6]
AlH3
K[AlF3H]
Anhydrous HF is a covalent compound and a weak acid, so it does not provide enough F⁻ ions to dissolve AlF3. However, KF is an ionic compound that completely dissociates to provide a high concentration of F⁻ ions. In the presence of KF, AlF3 acts as a Lewis acid and accepts these F⁻ ions to form the soluble coordination complex, potassium hexafluoroaluminate(III). The chemical equation for this reaction is: AlF3 + 3KF → K3[AlF6].
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