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研究了H~+、N0_3~-对在μ=3的Pu(IV)高氯酸溶液中的光化学行为的影响,证明NO_3~-对光氧化有较大的影响。在63℃和μ=3时,对Pu(IV)的热歧化与歧化过程中紫外光的作用进行了比较,结果表明紫外光照射有利于歧化反应的进行,其反应浓度商分别为避光时在[H~+]为1.0、1.5、2.0和3.0mol/L时的2.2×10~2,4.15×10~2,1.98×10~2和3.16×10~2倍。研究了甲醇、乙醇、UO_2~(2+)和Fe~(3+)对Pu(IV)在HNO_3溶液中光化学行为的影响。发现Fe~(3+)的加入可使Pu(NI)量显著减少,当[Fe~(3+)]≥0.038mol/L时,可使Pu(VI)的生成量由> 80%降低到<10%。对Fe~(3+)抑制Pu(VI)生成的机理进行了初步探讨。
The effect of H ~ + and N0 ~ 3 ~ - on the photochemical behavior of Pu (IV) perchloric acid solution with μ = 3 was studied. It was found that NO_3 ~ - had a great influence on the photooxidation. At 63 ℃ and μ = 3, the effects of UV on the disproportionation of Pu (IV) were compared. The results show that UV irradiation favors the disproportionation reaction, and the reaction concentrations are respectively at darkness 2.2 × 10 ~ 2, 4.15 × 10 ~ 2, 1.98 × 10 ~ 2, and 3.16 × 10 ~ 2 times at [H ~ +] of 1.0, 1.5, 2.0 and 3.0 mol / L. The effects of methanol, ethanol, UO 2 2+ and Fe 3+ on the photochemical behavior of Pu (IV) in HNO 3 solution were studied. It was found that the amount of Pu (VI) can be reduced from> 80% when [Fe ~ (3 +)] ≥0.038mol / L when Fe ~ (3+) <10%. The formation mechanism of Pu (VI) by Fe ~ (3+) was preliminarily discussed.