The composition and instability constants of +3 oxalate complex ions

Journal of Nuclear Energy (1954) Pub Date : 1959-06-01 DOI:10.1016/0891-3919(59)90132-3

A.D. Gel′man, N.N. Matorina, A.I. Moskvin

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Abstract

The solubility of Pu₂(C_2O₄)₃·9H₂O in aqueous K₂C₂O₄ solutions of from 0·01 to 2·4 M was determined at 20°C and constant onic strength. It was established that Pu⁺³ forms complexes in these solutions. The solubility data show the following complex ions in this concentration range: [Pu(C₂O₄)₂]⁻, [PU(C₂O₄)₃]⁻³ and [PU(C₂O₄)₄]⁻⁵ with overall instability constants of 4·9 × 10⁻¹⁰, 4·10 × 10-10, and 11·9 ×x 10⁻¹¹ respectively. The solubility of PU₂(C₂O₄)₃·9H₂O in 0·07 to 0·7 M aqueous (NH₄) 2 C204 solutions at 70°C was also determined. Under these conditions, the complex ions formed were shown to be [PU(C₂O₄)₂]⁻, [Pu(C₂O₄)₃]⁻³ and [PU(C₂O₄)₄]⁻⁵. The calculated overall instability constants are 11·6 × 10⁻⁹, 5·6 × 10⁻⁹ and 2·5 x 10⁻⁹ respectively. Heats of formation of the Pu⁺³ oxalate complex ions were calculated for the reaction Pu⁺³ + nC₂O₄⁻² 2 : [Pu(C₂O₄)_n]³⁻²ⁿ. ΔQ for [PU(C₂O₄)₂]⁻ is 1300 cal, for [PU(C₂O₄)₃]⁻³ 1200 cal and for [Pu(C₂O₄)₄]⁻⁵ 1300 cal.

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草酸+3络合离子的组成及不稳定常数

测定了Pu2(C2O4) 3.9h2o在0.01 ~ 2.4 M K2C2O4水溶液中的溶解度。结果表明，Pu+3在这些溶液中形成络合物。溶解度数据表明，该浓度范围内的络合离子为[Pu(C2O4)2]−、[Pu(C2O4) 3]−3和[Pu(C2O4) 4]−5，总体不稳定常数分别为4.9 × 10−10、4.10 × 10-10和11.9 ×x 10−11。测定了PU2(C2O4) 3.9h2o在0.7 ~ 0.7 M NH4 - 2c204水溶液中70℃的溶解度。在此条件下形成的络合离子为[PU(C2O4)2]−、[PU(C2O4) 3]−3和[PU(C2O4)4]−5。计算得到的总不稳定常数分别为11.6 × 10−9、5.6 × 10−9和2.5 × 10−9。计算了Pu+3 + nC2O4−22 2:[Pu(C2O4)n]3−2n反应中Pu+3草酸盐络合离子的生成热。[PU(C2O4)2]−为1300卡，[PU(C2O4)3]−3为1200卡，[PU(C2O4) 4]−5为1300卡。

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Journal of Nuclear Energy (1954)

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