Abstract

The properties and stability of the S₂O₈^2– ion and mechanisms of its reaction with ions of f-elements in aqueous solutions in a wide range of pH values are considered. S₂O₈^2– are converted to SO₄ ion radicals. The decomposition is accelerated by Н⁺, ОН^–, Ag⁺, Co²⁺ ions, and others. The decomposition in solutions with [H⁺] > 0.5 or [OH^–] > 0.5 M yields monoperoxysulfuric acid, with its hydrolysis generating Н₂О₂. The SO₄^– radicals oxidize ions of f-elements and convert ОН^– and СО₃^2– ions to oxidizing radicals ОН and СО₃^– and transform H₂PO₄^– and NO₃^– ions into reducing compounds. In aerated alkaline solutions, the ОН radicals are transformed to ion-radicals О₃^–,which oxidize Np(VI), Pu(VI), and Am(VI) to the heptavalent state. In weakly acidic solutions of heteropolycompounds, SO₄^– radicals transform Tb(III), Am(III), Cm(III), Cf(III) to the tetravalent state. The mixture of Ag⁺ and S₂O₈^2– is used to oxidize Np(VI) to Np(VII) in an alkaline medium, Pu⁴⁺ to PuO₂²⁺ in acid solutions, Am(III) to Am(IV) in Н₃РО₄ solutions and in the presence of heteropolycompounds in 5 M HNO₃ or 3 M H₂SO₄ solutions, Am³⁺ to AmO₂²⁺ in acid solutions. The decomposition of S₂O₈^2– into radicals occurs under exposure to light or radiation. The reactions of oxidation of f-element ions by SO₄^– radicals occur by the zeroth-order rate law. To one more group of reactions belongs the interaction of S₂O₈^2– with NpO₂⁺, Pu³⁺, Am³⁺ ions. The reactions occur with a first-order rate with respect to the f-ion. In the case of U⁴⁺, Np⁴⁺ in acid media and, Pu(IV) in a solution of K₂СО₃, complexes of these ions with S₂O₈^2– are formed. The complexes decompose by the first-order rate law. Studies are planned of studying reactions involving S₂O₈^2– and ions of f-elements, including those in fluoride solutions containing actinides and fission products, and reactions of SO₄^– radicals at low temperatures to give actinides in higher oxidation state.

中文翻译：

---

f元素化学中的过硫酸根离子

摘要

在宽的pH值范围内，考虑了S ₂ O ₈ ^2-离子的性质和稳定性以及其与f元素离子反应的机理。S ₂ O ₈ ^2–被转化为SO ₄离子自由基。分解是通过Н加速⁺，ОН ^- ，银⁺，钴²⁺离子，以及其他。与[H在溶液中的分解⁺ ]> 0.5或[OH ^- ]> 0.5M的产生monoperoxysulfuric酸，以其水解生成Н ₂ О ₂。SO ₄ ^–自由基氧化的f-元素的离子和转换ОН ^-和СО _3根^2-离子氧化自由基ОН和СО ₃ ^-和变换ħ ₂ PO ₄ ^-和NO ₃ ^-离子进入还原化合物。在充气碱性溶液中，ОН自由基转化为离子基О ₃ ^- ，其中Np个氧化（VI），普（VI），和AM（VI）到七价状态。在杂多的弱酸性溶液，SO ₄ ^-的基团变换铽（III），AM（III），CM（III），CF（III），以四价态。Ag ⁺和S ₂ O ₈ ^2–的混合物用于在碱性介质中，普来氧化的NP（VI）与NP（VII）⁴⁺到的PuO ₂ ²⁺在酸性溶液中，AM（III）至AM（IV）在Н _3个РО _4个解决方案，并在存在杂多化合物在5 M HNO ₃或3 MH ₂ SO ₄溶液中，在酸性溶液中从Am ³⁺到AmO ₂ ²⁺。S ₂ O ₈ ^2–分解为自由基会在暴露于光或辐射下发生。的氧化反应˚F -元素离子通过SO ₄ ^-自由基根据零阶速率定律发生。S ₂ O ₈ ^2–与NpO ₂ ⁺，Pu ³⁺，Am ³⁺离子的相互作用属于另一类反应。该反应以相对于f-离子的一级速率发生。在U的情况下⁴⁺，NP ⁴⁺在酸性介质中在K的溶液和，普（IV）₂ СО ₃，这些离子与S的络合物₂ ö ₈ ^2-形成。配合物通过一阶速率定律分解。计划进行研究以研究涉及S ₂ O _8的反应^2-和离子的f-元件，包括那些在含有锕系元素和裂变产物氟化物溶液，和SO的反应₄ ^-基团在低温下，得到处于较高氧化态锕系元素。