Uranium complexes, hydrogen peroxide

Because of the ease of oxidation of protactinium(IV) and uranium(IV), peroxides and peroxo complexes are limited to their higher oxidation states. The compounds M04"JcH20 precipitated from dilute acid solutions of neptunium(IV) and plutonium(IV) by hydrogen peroxide appear to be actinide(IV) compounds. Soluble intermediates of the type [Pu( U-02)2Pu]4+ are formed at low hydrogen peroxide concentrations. 

Recovery of vanadium with peroxygens involves both oxidation and com-plexation. In solution, conversion of lower oxidation states into vanadium(V) allows separation by solvent extraction (Figure 6.18).269 This chemistry can be used for vanadium by-products in uranium extractions. With hydrogen peroxide, vanadium(IV) is not oxidized in acidic solution, but rather in alkaline conditions, e.g. 60 °C at pH 9 (Figure 6.19).270 Use of excess hydrogen peroxide readily forms peroxo complexes and this is of value in selective dissolution of vanadium from secondary sources. 

In the reduction stripping process uranium(IV) in the raw wet process acid is oxidized to uranium(Vl) by treatment with sodium chlorate, hydrogen peroxide or air at 60 to 70°C, the uranium(VI) formed being extracted with trioctylphosphine oxide/di-(2-ethylhexyl)phosphate in kerosene and the resulting solution finally reductively stripped repeatedly with aqueous iron(II) solutions. This results in an enrichment by a factor of 40. After oxidation of the stripped solution with sodium chlorate or ambient oxygen and renewed extraction of the uranium(VI) formed with trioctylphosphine oxide/di-(2-ethylhexyl)phosphate, the phosphoric acid is removed from the organic phase by washing. The uranium(Vl) is then stripped with ammonium carbonate and precipitated as the ammonium diuranyl-tricarbonato-complex. This is filtered off, washed and calcined. 

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