Higher oxidation states of americium have long been known; however, options for their preparation in acidic solution are limited. The conventional choice, silver-catalyzed peroxydisulfate, is not useful at nitric acid concentrations above about 0.3 M. We investigated the use of sodium bismuthate as an oxidant for Am (3+) in acidic solution. Room-temperature oxidation produced AmO 2 (2+) quantitatively, whereas oxidation at 80 degrees C produced AmO 2 (+) quantitatively. The efficacy of the method for the production of oxidized americium was verified by fluoride precipitation and by spectroscopic absorbance measurements. We performed absorbance measurements using a conventional 1 cm cell for high americium concentrations and a 100 cm liquid waveguide capillary cell for low americium concentrations. Extinction coefficients for the absorbance of Am (3+) at 503 nm, AmO 2 (+) at 514 nm, and AmO 2 (2+) at 666 nm in 0.1 M nitric acid are reported. We also performed solvent extraction experiments with the hexavalent americium using the common actinide extraction ligand tributyl phosphate (TBP) for comparison to the other hexavalent actinides. Contact with 30% tributyl phosphate in dodecane reduced americium; it was nevertheless extracted using short contact times. The TBP extraction of AmO 2 (2+) over a range of nitric acid concentrations is shown for the first time and was found to be analogous to that of uranyl, neptunyl, and plutonyl ions.
Recently, efforts towards closing the nuclear fuel cycle have considered oxidizing americium to a hexavalent, linear-dioxo cation for co-recovery with hexavalent U, Np, and Pu from molar nitric acid using solvating extraction ligands such as tri-n-butyl phosphate or diamyl amylphosphonate. This work assesses solvent extraction recovery of sodium bismuthate oxidized americium by N,N-di-(2-ethylhexyl)butyramide (DEHBA), N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA), and N,N-dihexyloctanamide (DHOA). Extraction efficiency between the monoamides was found to increase in the order of DEHiBA < DHOA < DEHBA. For all monoamides, oxidized americium extraction was less than 50% from 4 M HNO 3 and below.Extraction efficiency above 50% was obtained using concentrations of 5 M HNO 3 or higher.The DEHBA extractant provided the highest distribution value of 5.4 at 7 M HNO 3 . Distribution values were found to be stable for up to 45 seconds aqueous/organic phase mixing times and indicated decreased reduction of hexavalent americium relative to separations completed with 2 organophosphorus extractants. The simultaneous co-extraction of U, Np, Pu, and Am was demonstrated using DEHiBA, and was found to decrease with increasing atomic number (D U > D Np > D Pu > D Am ). Interestingly, a break in recovery was observed where ligher actinides, U and Np, were better recovered relative to the heavier actinides, Pu and Am, in this study. This observation seems to be related to differences in the extracted metal complex for light actinides
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