Abstract
Covalent nitrate bonding in TBP solutions of nitric acid and metal nitrates shifts the nitrate absorption band ( λ max 303 mμ for nitrate ion in aqueous media) to lower wavelengths. In TBP, the spectrum of lithium nitrate is the same as that in water, whereas nitric acid has λ max at 273 mμ; other metal nitrates show intermediate shifts in the order LiNO 3 < Mg(NO 3) 2 < Ca(NO 3) 2 < Al(NO 3) 3 < La(NO 3) 3 < Th(NO 3) 4 < HNO 3. Ionic nitrate in TBP phases containing uranyl nitrate promotes the formation of the trinitrato uranyl complex, and the extent to which the latter is formed by the above mentioned series of nitrate solutions corresponds to the increase of covalency indicated by the spectral shifts.
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