Oleum and Sulfuric Acid as Reaction Media: The Actinide Examples UO2(S2O7)‐lt (low temperature), UO2(S2O7)‐ht (high temperature), UO2(HSO4)2, An(SO4)2 (An = Th, U), Th4(HSO4)2(SO4)7 and Th(HSO4)2(SO4)
Oleum and Sulfuric Acid as Reaction Media: The Actinide Examples UO2(S2O7)‐lt (low temperature), UO2(S2O7)‐ht (high temperature), UO2(HSO4)2, An(SO4)2 (An = Th, U), Th4(HSO4)2(SO4)7 and Th(HSO4)2(SO4)
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发烟硫酸和硫酸作为反应介质：锕系元素示例 UO2(S2O7)‐lt（低温）、UO2(S2O7)‐ht（高温）、UO2(HSO4)2、An(SO4)2 (An = Th, U )、Th4(HSO4)2(SO4)7 和 Th(HSO4)2(SO4)
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
M. Wickleder
中科院分区：
文献类型：
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作者：
U. Betke;M. Wickleder
通过 UO2(CH3COO)2·2H2O 与硫酸/三氧化硫混合物在密封玻璃安瓿中反应合成了新的硫酸铀。二硫酸盐 UO2(S2O7) 的两种多晶型物 [低温 (lt)：三斜晶系，P, Z = 2, a = 647.8(1) pm, b = 684.2(1) pm, c = 800.1(1) pm, α = 87.31(2)°, β = 78.37(2)°, γ = 75.34(2)°, V = 0.33605(9) nm3;高温 (ht)：斜方晶系，Pca21，Z = 8，a = 1080.21(2) pm，b = 814.74(1) pm，c = 1655.63(3) pm，V = 1.45710(4) nm3] 和硫酸氢盐 UO2(HSO4)2 [单斜晶系，P21/n，Z = 4，a = 779(3) pm, b = 815.39(3) pm, c = 1285.77(5) pm, β = 103.700(1)°, V = 0.79428(5) nm3] 含有众所周知的线性 [UO2]2+ 离子形式的六价铀。 U周围的五角双锥配位球由二硫酸根和硫酸氢根离子完成，将铀酰基团连接成三维网络。乙酸双氧铀与硫酸在足够高的温度 (300 °C) 下反应，在 U(SO4)2 [斜方晶系，Pbca，Z = 8，a = 940.11(2) pm，b = 898.13(2) pm，c = 1349.09(3) pm，V = 绿板分离下将铀还原为四价形式1.13909(4) nm3]。 U(SO4)2 中的 U4+ 离子处于八个单齿硫酸盐四面体的方形反棱镜配位中。通过硫酸处理 ThO2，硫酸钍（氢）盐 Th(SO4)2 [斜方晶系，Pbca，Z = 8，a = 953.74(3) pm，b = 911.49(3) pm，c = 1365.02(4) pm，V = 1.18665(6) nm3]， Th4(HSO4)2(SO4)7 [四方晶系，I2d，Z = 4，a = 1327.7(2) pm，c = 1362.8(2) pm，V = 2.402.3(6) nm3] 和 Th(HSO4)2(SO4) [三斜晶系，P，Z = 2，a = 576.18(2) pm，b =可以得到896.11(3) pm, c = 948.58(3) pm, α = 65.387(2)°, β = 87.838(2)°, γ = 88.917(2)°, V = 0.44495(3) nm3]。虽然 Th(SO4)2 与各自的铀化合物是同型的，但两种硫酸氢盐都含有九重配位钍，形成三重封顶的三棱柱。 Th(HSO4)2(SO4)的结构可以描述为UCl3结构类型的扭曲变体。
New uranium sulfates have been synthesised by the reaction of UO2(CH3COO)2·2H2O with sulfuric acid/sulfur trioxide mixtures in sealed glass ampoules. Both polymorphs of the disulfate UO2(S2O7) [low temperature (lt): triclinic, P, Z = 2, a = 647.8(1) pm, b = 684.2(1) pm, c = 800.1(1) pm, α = 87.31(2)°, β = 78.37(2)°, γ = 75.34(2)°, V = 0.33605(9) nm3; high temperature (ht): orthorhombic, Pca21, Z = 8, a = 1080.21(2) pm, b = 814.74(1) pm, c = 1655.63(3) pm, V = 1.45710(4) nm3] and the hydrogensulfate UO2(HSO4)2 [monoclinic, P21/n, Z = 4, a = 779(3) pm, b = 815.39(3) pm, c = 1285.77(5) pm, β = 103.700(1)°, V = 0.79428(5) nm3] contain hexavalent uranium in the form of the well-known linear [UO2]2+ ion. The pentagonal bipyramidal coordination sphere around U is completed by disulfate and hydrogensulfate ions, which connect the uranyl groups to a three-dimensional network. Reaction of uranyl acetate with sulfuric acid at sufficiently high temperature (300 °C) leads to a reduction of uranium to the tetravalent form under separation of green plates of U(SO4)2 [orthorhombic, Pbca, Z = 8, a = 940.11(2) pm, b = 898.13(2) pm, c = 1349.09(3) pm, V = 1.13909(4) nm3]. The U4+ ions in U(SO4)2 are in a square antiprismatic coordination of eight monodentate sulfate tetrahedra. By treatment of ThO2 with sulfuric acid, the thorium (hydrogen)sulfates Th(SO4)2 [orthorhombic, Pbca, Z = 8, a = 953.74(3) pm, b = 911.49(3) pm, c = 1365.02(4) pm, V = 1.18665(6) nm3], Th4(HSO4)2(SO4)7 [tetragonal, I2d, Z = 4, a = 1327.7(2) pm, c = 1362.8(2) pm, V = 2.402.3(6) nm3] and Th(HSO4)2(SO4) [triclinic, P, Z = 2, a = 576.18(2) pm, b = 896.11(3) pm, c = 948.58(3) pm, α = 65.387(2)°, β = 87.838(2)°, γ = 88.917(2)°, V = 0.44495(3) nm3] could be obtained. Whereas Th(SO4)2 is isotypic with the respective uranium compound, both hydrogensulfates contain ninefold-coordinated thorium to form a triple-capped trigonal prism. The structure of Th(HSO4)2(SO4) can be described as a distorted variant of the UCl3 structure type.