Berkelium redox speciation

被引：50

作者：

Antonio, MR ^{[1
]}

Williams, CW ^{[1
]}

Soderholm, L ^{[1
]}

机构：

[1] Argonne Natl Lab, Div Chem, Argonne, IL 60439 USA

来源：

RADIOCHIMICA ACTA | 2002年 / 90卷 / 12期

关键词：

aquo ion; berkelium; EXAFS; hydration; Nernst analysis; spectroelectrochemistry; XANES;

D O I：

10.1524/ract.2002.90.12_2002.851

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The inner-sphere hydration environments of the Bk3+ . nH(2)O and Bk4+ - n' H2O aquo ions in 1 M HClO4 were determined and are viewed in the context of other 5 f (actinide) and 4f (lanthanide) aquo ions. The formal potential of the Bk4+/Bk3+ redox couple and the reorganization of the hydration sphere, in terms of the average Bk-OH2 interatomic distances and number of coordinated water molecules (n and n'), were determined through in situ X-ray absorption spectroelectrochemistry. The participation of H2O in the electrochemical conversion and the rearrangement of the hydration environment upon reduction-oxidation are summarized in the equation: [Bk(OH2)(8)](4+) + H2O + e(-) reversible arrow [Bk(OH2)(9)](3+) . The change of hydration about Bk-249 between the trivalent and tetravalent states is believed to reflect predominantly steric factors related to the difference of ionic radii, rather than electronic or bonding influences.

引用

页码：851 / 856

页数：6

共 33 条

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[2]

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