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磷酸三丁酯对铋酸盐氧化镅的萃取行为

Tributylphosphate extraction behavior of bismuthate-oxidized americium.

作者信息

Mincher Bruce J, Martin Leigh R, Schmitt Nicholas C

机构信息

Idaho National Laboratory, Idaho Falls, Idaho 83415, USA.

出版信息

Inorg Chem. 2008 Aug 4;47(15):6984-9. doi: 10.1021/ic800667h. Epub 2008 Jul 2.

Abstract

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.

摘要

镅的高氧化态早已为人所知;然而,在酸性溶液中制备它们的方法有限。传统的选择,即银催化的过二硫酸盐,在硝酸浓度高于约0.3 M时并不适用。我们研究了使用铋酸钠作为酸性溶液中Am(3+)的氧化剂。室温氧化定量生成AmO₂(2+),而在80℃氧化则定量生成AmO₂(+)。通过氟化物沉淀和光谱吸光度测量验证了该方法制备氧化镅的有效性。我们使用传统的1 cm比色皿对高镅浓度进行吸光度测量,使用100 cm液体波导毛细管比色皿对低镅浓度进行测量。报告了在0.1 M硝酸中Am(3+)在503 nm、AmO₂(+)在514 nm和AmO₂(2+)在666 nm处的吸光系数。我们还使用常见的锕系元素萃取配体磷酸三丁酯(TBP)对六价镅进行了溶剂萃取实验,以便与其他六价锕系元素进行比较。与十二烷中的30%磷酸三丁酯接触会使镅还原;不过,短接触时间下仍能萃取。首次展示了在一系列硝酸浓度下TBP对AmO₂(2+)的萃取情况,发现其与铀酰、镎酰和钚酰离子的萃取情况类似。

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