EPR Study of Uranium(V) Species in Photo-and Electrolytic Reduction Processes of UO2(NO3)2-2TBP.

Abstract

Abstract Electron Paramagnetic Resonance (EPR) and optical spectra of uranium(V) species were observed in both processes of photo- and electrolytic reduction of UO2(NO3)2-2tributylphosphate (TBP) in 80%TBP-n-dodecane solution. The formation of U(V) species was detected by an optical spectrum (λmax: 770, 970 and 1,420 nm). EPR signal with the value of ff-factor –2.3 and a linewidth of approximately 1,100 Gs was observed during the electrolytic reduction. On the other hand, during the photoreduction the signal with the value of fil-factor –1.94 was observed and there was found a superhyperfine structure with the intensity ratio of 1:2:1, that is caused by the superhyperfine coupling with nuclear spin, I=1/2, of the strongly coordinated 31P to the central uranium through oxygen atom. The superhyperfine coupling constant was estimated to be 27 Gs. Moreover, the signal with the value of g-factor –2.00 due to an organic radical was observed. The residue after the thermo-gravimetric analysis of UO2(NO3)2-2TBP wa...