1966 Volume 39 Issue 10 Pages 2187-2190
The ion association of hexacyanoferrate(III) and hexacyanoferrate(II) anions with univalent or bivalent cations in aqueous solutions has been studied by the measurement of the infrared absorption band due to the C≡N stretching vibrations. All the solutions measured in which ion-pairs with hexacyanoferrates(III) predominated gave an absorption maximum at 2121 cm−1, and those in which ion-pairs with hexacyanoferrates(II) predominated, at 2020 cm−1, although hexacyanoferrates(III) and hexacyanoferrates(II) of potassium and alkaline earth metals gave different spectra from each other in solid state. No difference in absorption band obtained with different solutions was supported by the distance between two ions in ion-pair, which was estimated from the structures of hexacyanoferrate(III) and hexacyanoferrate(II) ions and the closest approach of the ion-pair; this indicates that there is no direct interaction between the complex anion and the cation, but one or more water molecules interpose between the two ions.
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