Raman spectrometric studies of actinide(V) and -(VI) complexes in aqueous sodium carbonate solution and of solid sodium actinide(V) carbonate compounds
Raman spectrometric studies of actinide(V) and -(VI) complexes in aqueous sodium carbonate solution and of solid sodium actinide(V) carbonate compounds
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碳酸钠水溶液中锕系元素 (V) 和-(VI) 络合物以及固体锕系元素 (V) 碳酸钠化合物的拉曼光谱研究
DOI：
10.1021/ic00152a015
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发表时间：
1983
影响因子：
4.6
通讯作者：
G. Begun
中科院分区：
文献类型：
--
作者：
C. Madic;D. Hobart;G. Begun
在2M(Na/SUB_2/CO/SUB_3/)水溶液中，获得了所有吖系元素(V)(P_a除外)及其络合物的拉曼光谱。在Np(Np)(VI)、Pu(Pu)(VI)和Am(Am)(VI)中观察到了共振拉曼效应，并发现这与相应的电子光谱中观察到的电荷转移带的位置以及在碳酸盐溶液中的(VI)/Ac(V)对的形式电势有关。在铀(U(VI))的拉曼光谱中没有观察到共振效应。在碳酸盐溶液中，MO/sub2//sup2+/基团的对称伸缩频率(nu/sub1/)与酸性非络合溶液相比发生了移动，并随所考虑的榄系元素原子序数的增加而规律性地降低。相反，在碳酸盐溶液中，吖系元素(V)的MO/sub2//sup+/基团的nu/sub1/频率并不随其原子序数的增加而变化。与酸性溶液中的v/sub1/频率相比，在碳酸盐溶液中，Np(V)的nu/sub1/频率发生了较小的负移，而Am(V)的nu/sub1/频率发生了正移。得到了Na/sub3/MO/sub2/(CO/sub3/)/sub2/固体化合物M=Np，Pu，Am的拉曼光谱MO/sub2//sup+/离子的nu/sub1/more频率随榄系元素原子序数的增加而线性下降，且高于MO/sub2//sup+/离子的相应值。在非致密介质和碳酸盐介质中，(V)和-(VI)之间的行为差异可能与(V)氧化的氧和水分子之间可能的氢键有关。12位数字，3个表格。
Raman spectra of all the actinide(V) (except protactinium (Pa)) and actinide(VI) complexes in 2 M(sodium carbonate Na/sub 2/CO/sub 3/) solutions have been obtained. A resonance Raman effect was observed for neptunium(Np)(VI), plutonium(Pu)(VI), and americium(Am)(VI) and found to be related to the position of the charge-transfer bands observed in the corresponding electronic spectra and to the formal potential of actinide(VI)/actinide(V) couples in carbonate solution. No resonance effect was observed in the Raman spectrum of uranium (U(VI)). The symmetric stretching frequency (nu/sub 1/) of the MO/sub 2//sup 2 +/ group was shifted in carbonate solutions as compared to acidic noncomplexing solutions and decreased regularly with an increase in the atomic number of the actinide considered. In contrast, the nu/sub 1/ frequencies of the MO/sub 2//sup +/ group for actinide(V) species in carbonate solutions did not vary as the atomic number of the actinide increased. In comparison to the v/sub 1/ frequencies in acidic solutions, in carbonate solution a small negative shift was observed for nu/sub 1/ of Np(V) and a positive shift was obtained for nu/sub 1/ of Am(V). The Raman spectra of Na/sub 3/MO/sub 2/(CO/sub 3/)/sub 2/ solid compounds were obtained for M = Np, Pu, and Am. The nu/sub 1/more » frequencies of the MO/sub 2//sup +/ ions decreased linearly with increasing atomic number of the actinide and were higher than the corresponding values for aqueous MO/sub 2//sup +/ ions. The differences in behavior observed between actinide(V) and -(VI) species in noncompexing media and in carbonate media may be related to possible hydrogen bonding between the oxygen of the actinide(V) oxycation and water molecules. 12 figures, 3 tables.« less