红外光谱法测定U(Ⅳ)、U(Ⅵ)-磷酸三烃酯络合物的同位素位移及平衡常数的计算

CALCULATION OF THE EQUILIBRIUM CON-STANTS OF U(Ⅳ)-U(Ⅵ) ELECTRON EXCHANGE REACTIONS FROM ISOTOPE SHIFTS OF TRI-ALKYL PHOSPHATE SOLID CHLORO COMPLE-XES MEASURED BY I. R. SPECTRA

摘要: 本文用红外光谱技术测定了UCl_4、UO_2Cl_2与三种磷酸三烃酯(TMP、TEP、TBP)固体络合物的同位素位移。据此,计算了U(Ⅳ)-U(Ⅵ)电子交换反应的平衡常数。并讨论了配位体对同位素位移效应的影响。

Abstract: The isotope frequency shifts of the uranous and uranyl chloro solid complexes with three kind of trialkyl phosphate (TMP, TEP, TBP) are measured by I. R. spectrometry. The isotope shifts of uranyl chloro solid complexes are 0.87-1.18 cm-1 and the value from theoretical calculation is 0.70 cm-1. The isotope shifts of uranous complexes are 0.05-0.18 cm-1, and the calculated value is 0.16 cm-1.From the above data the equilibrium constants of the U(Ⅳ)-U(Ⅵ) electron exchange reactions are obtained in the range of 1.0013-1.0018 for these systems.The influence of the donor ligands on the effect of isotope shift is discussed.