Synthesis and crystal structure of americium(V) dichromate, Cs3AmO2(Cr2O7)2·H2O

A new Am(V) chromate complex with outer-sphere cesium cation, Cs₃AmO₂(Cr₂O₇)₂·H₂O, was prepared from aqueous solution. Its composition and structure were determined by single crystal X-ray diffraction. The Am(V) atom has coordination surrounding in the form of a distorted pentagonal bipyramid with the O atoms of the AmO ₂ ⁺ group in apical positions. The equator of the bipyramid is formed by the O atoms of four dichromate groups and of the water molecule. The mean bond lengths (Å) are as follows: Am=O 1.802(5), Am-O(Cr₂O₇) 2.443(6), and Am-O_w 2.519(6). The Am(V) pentagonal bipyramids are combined via bidentate bridging Cr₂O ₇ ^2? anions into infinite chains [AmO₂(Cr₂O₇)₂H₂O] _n ^3? arranged in layers parallel to the series of diagonal planes (111). A system of hydrogen bonds links the chains in a layer and the layers with each other. The Cs cations are arranged between the layers, forming cationic interlayers.     

Reduction of Np(VI) and Pu(VI) with anions of some substituted carboxylic acids

The reaction of Np(VI) with organic acid anions in solutions containing lithium salts of tartaric, malic, α-aminoglutaric, and trihydroxyglutaric acids was studied. Changes in the solution spectra show that Np(VI) forms complexes with organic acid anions, which is followed by the reduction of Np(VI) to Np(V). Similar processes occur in solutions containing Pu(VI) and sodium phenylglycolate or ammonium salicylate. In weakly acidic solutions, the loss of the Np(VI) and Pu(VI) concentrations is a linear function of time. The possible mechanism of the redox reactions was suggested.     

Construction of the welded body of vehicles from aluminium alloys

The theory of thermal processes, developed by N.N. Rykalin, is used for calculating the cooling rate, the temperature in heating and the width of quenched grooves in surface quenching with the electric arc. The results confirm that high-quality surface quenching of the components can be carried out without additional cooling of the surface with water.     

Influence of conditions on the potential of the couple of nonoxygenated U5+/U4+ ions bound in complexes with the P2W17O 6110? and SiW11O 398? anions

The formal potential of the couple of nonoxygenated U⁵⁺/U⁴⁺ ions bound in complexes with unsaturated heteropoly anions (HPAs) P₂W₁₇O₆₁¹⁰⁻ (I) and SiW_{11 O39}⁸⁻ (II) in 0–1 M NaNO₃ and 1 M (NaCl + HCl) in the range of pH 0.7–4.7 was measured. In 1 M NaNO₃ solutions at pH 4.7–3.0 for I and 4.3–3.9 for II, the formal potentials are constant: 0.820 and 0.730 V, respectively. They preserve approximately the same value with a decrease in pH to 0.7 in 1 M (NaCl + HCl). The potential noticeably decreases with a decrease in the NaNO₃ or NaCl concentration from 1 M to 0 (pH 4.1–4.7): to 0.09 and 0.05–0.06 V for I and II, respectively. Approximate constancy of the potential of the U⁵⁺/U⁴⁺ couple with a decrease in pH to 1 and lower distinguishes this couple from the M⁴⁺/M³⁺ couples (M = Ce, Am, Bk) whose potential appreciably grows with increasing acidity. This is due to the fact that the U⁵⁺ and M⁴⁺ ions in acid solutions remain in the form of complexes with the ratio M: HPA = 1: 2, whereas the M³⁺ ions pass into the form of 1: 1 complexes. Thus, variation of the formal potentials of all the M ^{n + 1}/M ⁿ⁺ couples in the presence of H⁺ and Na⁺ ions is associated with variation of the stability constants of the complexes M(HPA)₂, which, in turn, is caused by interaction of single-charged ions with HPA. However, the H⁺ and Na⁺ ions interact with HPA by different mechanisms and therefore affect the potential of the U⁵⁺/U⁴⁺ couple differently. Original Russian Text ? V.P. Shilov, A.B. Yusov, A.M. Fedoseev, Ph. Moisy, 2008, published in Radiokhimiya, 2008, Vol. 50, No. 5, pp. 393–396.     

Redox equilibrium U(VI) + 2Ce(III) ? U(IV) + 2Ce(IV) in the presence of unsaturated heteropoly anions P2W17O 6110? and SiW11O 398?

The equilibrium of the reaction U(VI) + 2Ce(III) ⇄ U(IV) + 2Ce(IV) in the presence of unsalurated heleropoly compounds K₁₀P₂W₁₇O₆₁ and K₈SiW₁₁O₃₉ in 0.01–1.0 M HClO₄ solutions (ionic strength 1) was studied. The potential of the Ce(IV)/Ce(III) couple in K₈SiW₁₁O₃₉ solutions was measured, from which the overall stability constants β₂^IV of the complexes U^IV(SiW₁₁O₃₉)₂¹²⁻, equal to 10^23.8 and 10^19.8 in 0.1 M HClO₄ + 0.9 M NaClO₄ and in 1.0 M HClO₄, respectively, were calculated. Under the same conditions, for the complex U^IV(P₂W₁₇O₆₁)₂¹⁶⁻ β₂^IV = 10^23.2 and 10^18.5 (the latter value was obtained by extrapolation or data for 0.1 M HClO₄ + 0.9 M NaClO₄ solution). Original Russian Text ? V.P. Shilov. A.B. Yusov, M.N. Sokohva. A.M. Fedoseev, 2008, published in Radiokhimiya, 2008, Vol. 50. No. 3, pp. 203–208.