U0_2(NO_3)_2-TBP体系的光化学研究
STUDIES ON THE PHOTOCHEMICAL REDUCTION OF UO_2(NO_3)_2 IN 30%TBP-KEROSENE SOLUTION
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摘要: 用Ar~+激光器的488nm单色光研究了UO_2(NO_3)_2-30%TBP-煤油体系中U(Ⅵ)的光化学行为。实验表明:光照后TBP有机相内含有还原生成的U(Ⅳ)和TBP的主要降解产物DBP和丁醛;生成U(Ⅳ)的量子产额与酸度、温度、TBP浓度有关。光照合0.1mol/l U(Ⅵ),0.2mol/l HNO_3的30%TBP-煤油溶液时U(Ⅳ)的量子产额为0.18。温度大于30℃光照时,会产生显著量的亚硝酸。亚硝酸的生成量与光照功率和U(Ⅵ)的浓度成正比,当酸度大于0.1mol/l时,其量随酸度增加而减少。还初步探讨了U(Ⅵ)在TBP中光化还原的机理。Abstract: Photochemical reduction of UO2(NO3)2 and production of HNO2 in 30% TBP-kerosene solution are investigated using an argon ion laser with 488 nm monochromic beam, and the effects of some, factors on quantum yield have also been studied. The main degradation products of TBP in photochemical process are detected as DBP and butyl aldehyde,and nitrous acid is also found in TBP organic solution at higher temperature (greater than 30℃). The quantity of nitrous acid is proportional to the power of light and concentration of uranyl nitrate and decreases with the increase of concentration of nitric acid at higher acidity. Possible mechanisms of the photochemical reaction are proposed.