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本文研究了H~+、NO_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,其反应浓度商比避光时在〔H~+〕为1.0、1.5、2.0和3.0mol/L时分别为2.2×01~2;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(Ⅵ)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。
In this paper, the effects of H ~ + and NO_3 ~ on the photochemical behavior of Pu (Ⅳ) perchloric acid solutions with μ = 3 were studied. It is proved that NO_3 ~ - has a great influence on photooxidation. At 63 ℃ and μ = 3, the effect of UV on the disproportionation of Pu (Ⅳ) during the disproportionation of Pu (Ⅳ) was compared. The results show that UV irradiation favors the disproportionation reaction, 2.2 ~ 01 ~ 2, 4.15 × 10 ~ 2, 1.98 × 10 ~ 2 and 3.16 × 10 ~ 2 times when [H ~ +] was 1.0, 1.5, 2.0 and 3.0 mol / L respectively. 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 is found that the amount of Pu (Ⅵ) can be reduced from> 80% when the content of Fe 3+ is more than 0.038mol / L <10%. The formation mechanism of Pu (Ⅵ) by Fe ~ (3+) was preliminarily discussed.