Sublimation study of BiBr3

Steady-state sublimation vapour pressures of anhydrous bismuth tribromide have been measured by the continuous gravimetric Knudsen-effusion method from 369.3 to 478.8 K. Additional effusion measurements have also been made from 435.4 to 478.6 K by the torsion—effusion method. Based on a correlation of Δ_sub H ₂₉₈ ⁰ and Δ_sub S ₂₉₈ ⁰ , a recommended p(T) equation has been obtained for BiBr₃(s) $$\alpha - {\rm B}i{\rm B}r_3 :log{\text{ }}p = - C\alpha /T - 12.294log{\text{ }}T + 5.79112 \times 10^{ - 3} {\text{ }}T + 47.173$$ with Cα=(Δ _subH ₂₉₈ ⁰ +20.6168)/1.9146×10^-2 $$\beta - {\rm B}i{\rm B}r_3 :log{\text{ }}p = - C\beta /T - 23.251log{\text{ }}T + 1.0492 \times 10^{ - 2} {\text{ }}T + 77.116$$ with Cβ=(Δ _subH ₂₉₈ ⁰ +46.2642)/1.9146×10^-2 where p is in Pa, T in Kelvin, Δ _sub H ₂₉₈ ⁰ in kJ mol^?1. Condensation coefficients and their temperature dependence have been derived from the effusion measurements.     

Kinetics of Pu(IV) reduction with tert-butylhydrazine

The rate of Pu(IV) reduction with tert-butylhydrazine in an HNO₃ solution is described by the equation-d[Pu(IV)]/dt = k[Pu(IV)]²[(CH₃)₃CN₂H ₄ ⁺ ]/[H⁺], where k = 69.4 ⊥ 3.0 l mol^?1 min^?1 at 50°C. The activation energy is E = 122 ⊥ 4 kJ mol^?1. Probable reaction mechanisms are discussed.     

Stability of the LaCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> and LuCl<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack> Ions Studied by Mass Spectrometry

The enthalpy stability of the LaCl ₄ ^? and LuCl ₄ ^? ions is assessed using high-temperature mass spectrometry. The enthalpy of Cl^? detachment is determined to be Δ_rH⁰(298.15 K) = 332 ± 10 kJ/mol for LaCl ₄ ^? and 359 ± 10 kJ/mol for LuCl ₄ ^? .     

Mechanism of cerium(III) oxidation with ozone in sulfuric acid solutions

The kinetics of Ce(III) oxidation with ozone in 0.1–3.2 M H₂SO₄ solutions was studied by spectrophotometry. The reaction follows the first-order rate law with respect to each reactant. The rate constant k slightly increases with an increase in the acid concentration, which is associated with an increase in the O₃/O ₃ ^? oxidation potential. The activation energy in the range 17–35°C is 46 kJ mol^?1. With excess Ce(III), the stoichiometric coefficient Δ[Ce(IV)]/Δ[O₃] increases from 1.6 to 2 in going from 0.1 to 1–3.2 M H₂SO₄. The extent of the Ce(III) oxidation is 78% in 0.1 M H₂SO₄ and reaches 82% in 1 M H₂SO₄. The ozonation involves the reactions Ce(III) + O₃ → Ce(IV) + O ₃ ^? , O ₃ ^? + H⁺ → HO₃, HO₃ → OH + O₂, OH + HSO ₄ ^? → H₂O + SO ₄ ^? , OH + Ce(III) → OH^? + Ce(IV), and SO ₄ ^? + Ce(III) → SO_4/2? + Ce(IV). Low stoichiometric coefficient of the Ce(III) oxidation is associated with the hydrolysis of Ce(IV). The excited Ce(IV) ion arising from oxidation of Ce(III) with OH radical forms with the hydrolyzed Ce(IV) ion a dimer whose decomposition yields Ce(III) and H₂O₂. After the ozonation termination, Ce(IV) is relatively stable in sulfuric acid solution, with only 5–7% of Ce(IV) disappearing in 24 h.     

Thermodynamics of lutetium uranosilicate

The standard enthalpy of formation of crystalline Lu(HSiUO₆)₃ · 10H₂O at 298.15 K, ?10668.0±16.0 kJ mol^?1, and the standard enthalpy of its dehydration were determined by reaction calorimetry. The heat capacity of this compound in the range 80–300 K was measured by adiabatic vacuum calorimetry, and its thermodynamic functions were calculated. The standard entropy of formation at 298.15 K is ?3812.9±1.2 J mol^?1 K^?1, and the standard Gibbs energy of formation at 298.15 K, ?9531.0±16.5 kJ mol^?1. The standard thermodynamic functions of the reactions of the synthesis of lutetium uranosilicate were calculated and discussed.     

Complexation of hexavalent U,Np, and Pu with cyclopropanecarboxylate anions. Crystal structure of the uranyl complexes {[UO2(bipy)(cpc)]2O2} and [UO2(cpc)2(H2O)2] (bipy = 2,2′-Bipyridine,cpc− = cyclopropanecarboxylate anion)

The complexation of hexavalent U, Np, and Pu with cyclopropanecarboxylate anions, cpc^?, in aqueous solutions was studied. The stepwise concentration stability constants of the complexes PuO₂(cpc) _i ^2?i (i = 1, 2, 3) are as follows: logK _1,2,3 = 2.63 ± 0.20, 1.61 ± 0.20, 1.43 ± 0.20, respectively; the overall concentration stability constant of the complex PuO₂(cpc) ₃ ^? is logβ₃ = 5.67 ± 0.60. The complexing properties of the cpc^? anion are very close to those of butyrate and isobutyrate anions. Two crystalline uranyl compounds were synthesized: {[UO₂(bipy)(cpc)]₂O₂} (bipy = 2,2′-bipyridine) and [UO₂(cpc)₂(H₂O)₂]. The specific feature of the first complex is that it contains peroxide ion. Its appearance may be due to the formation of the cationic moiety via hydrolytic uranyl dimer. The second compound forms a 3D structure, with the complexes linked via hydrogen bonds.     

Behavior of Pu(VI) and Np(VI) in malonate solutions

Complexation of PuO ₂ ²⁺ in solutions containing malonate anions C₃H₂O ₄ ^2? (L^2?) is studied by spectrophotometry. Mono-and bimalonate complexes are formed. The monomalonate complex was isolated as PuO₂L · 3H₂O. It is isostructural to UO₂L · 3H₂O and forms rhombic crystals with the unit cell parameters a = 9.078(2), b = 7.526(2), and c = 6.2005(15) Å, space group Pmn2₁. The electronic absorption spectrum of the monomalonate complex is characterized by a strong band at 843 nm. In malonate solutions, Pu(VI) is slowly reduced to the pentavalent state even in the cold. The reduction of Np(VI) is considerably faster and more sensitive to increasing temperature. Some kinetic features of the reduction are discussed.     

Kinetics of Reactions of Np and Pu Ions with Hydrazine Derivatives: XVIII. Reaction between Np(V) and Hydroxyethylhydrazine

The Np(V) reduction with hydroxyethylhydrazine is described by the equation −d[Np(V)]/dt = k ₁[Np(V)][HOC₂H₄N₂H ₄ ⁺ ] + k ₂[Np(V)][Np(IV][H⁺]^1.8, reflecting its main and autocatalytic pathways. The rate constants are k ₁ = 0.31±0.04 l mol⁻¹ min⁻¹ and k ₂ = 4.04±0.11 l^2.8 mol^−2.8 min⁻¹ at 80°C and ionic strength μ = 4. The activation energies are E ₁ = 90±6 and E ₂ = 116±4 kJ mol⁻¹, respectively. The autocatalytic pathway is limited by the reaction between hydroxyethyldiazenium ions, HOC₂H₄N₂H ₂ ⁺ and protonated Np(V) ions. __________ Translated from Radiokhimiya, Vol. 47, No. 2, 2005, pp. 150–153. Original Russian Text Copyright ? 2005 by V. Koltunov, Baranov, G. Koltunov.     

Kinetics of Technetium Reactions: XV. Tc(IV) Oxidation with Persulfate Ions in HClO<Subscript>4</Subscript> Solution

Tc(IV) is oxidized with persulfate ions in HClO₄ solution by reactions with both S₂O ₈ ²⁻ ion and product of its thermal decomposition, Caro acid, H₂SO⁵. The reaction rate at 35°C and solution ionic strength μ = 1 is described by the equation d[Tc(IV)]/dt = k ₁[Tc(IV)][S₂O ₈ ²⁻ ] + k ₃[Tc(IV)][HSO ₅ ⁻ ]/[H⁺], where k ₁ = 0.88±0.04 l mol⁻¹ min⁻¹ and k ₃ = 110±5 min⁻¹. With increasing ionic strength to μ = 2, both rate constants decrease (k ₁ = 0.58±0.08 l mol⁻¹ min⁻¹ and k ₃ = 52±2 min⁻¹ at 35°C). The activation energy of the overall reaction is 77.7±8.1 kJ mol⁻¹. The mechanisms of both reactions are discussed. __________ Translated from Radiokhimiya, Vol. 47, No. 2, 2005, pp. 145–149. Original Russian Text Copyright ? 2005 by V. Koltunov, Gomonova, G. Koltunov.     

Thermodynamics of calcium uranosilicate

The standard enthalpy of formation at 298.15 K of crystalline α-Ca(HSiUO₆)₂ · 5H₂O (?6781.0 ± 9.5 kJ mol^?1) was determined by reaction calorimetry. The heat capacity in the range of 80–300 K was measured by adiabatic vacuum calorimetry, and the thermodynamic functions of this compound were evaluated. The standard entropy of formation (?1978.6±1.2 J mol^?1 K^?1) and the Gibbs free energy of formation (6191.0±10.0 kJ mol^?1) at 298.15 K were calculated. The standard thermodynamic functions of reactions of calcium uranosilicate synthesis were analyzed.     

Mechanism of Np(VI) oxidation with ozone in alkaline solutions

Bubbling of an ozone-oxygen mixture containing 0.1?C0.5 vol % O₃ at a rate of 15?C20 l h^?1 through 13 ml of a 2 × 10^?5?1 × 10^?4 M solution of Np(VI) in 0.1 and 1 M LiOH leads to the formation of Np(VII). The initial rate increases approximately in proportion to [Np(VI)] and [O ₃ ^gas ]^0.5. Up to 80% of Np(VI) is oxidized at maximum. At the O₃ concentration in the gas phase increased to 1?C4 vol %, Np(VI) is oxidized completely. Under the same conditions, Np(VI) in a concentration of (1?C5) × 10^?3 M is oxidized to almost 100%. Analysis of published data and additional experiments on the reaction of O₃ with Np(VI) ions in LiOH solutions allow a conclusion that the ozonation involves the reactions O₃ + OH^? = HO ₂ ^? + O₂, O₃ + HO ₂ ^? + OH^? = O ₃ ^? + O ₂ ^? + H₂O, and O₃ + O ₂ ^? = O ₃ ^? + O₂, followed by O ₃ ^? + NpO₂(OH) ₄ ^2? = O₂ + NpO₄(OH) ₂ ^3? + H₂O. In addition, HO ₂ ^? reduces Np(VII) and Np(VI) and reacts with O ₃ ^? . Certain contribution is made by the reaction Np(VI) + O₃ = Np(VII) + O ₃ ^? . The dependence of the Np(VII) accumulation rate on [O ₃ ^gas ]^0.5 was interpreted in terms of the concept of a heterogeneous-catalytic process.     

Low-temperature heat capacity and thermodynamic functions of GaTe

The heat capacity of GaTe is measured from 6.8 to 337.95 K using adiabatic calorimetry. The results are used to calculate the heat capacity, entropy, enthalpy increment, and reduced Gibbs energy of GaTe in the temperature range 10–320 K under standard conditions. The 298.15-K thermodynamic properties of GaTe are C _p ⁰ (298.15 K) = 48.96 ± 0.10 J/(K mol), S ⁰(298.15 K) = 81.30 ± 0.16 J/(K mol), H ⁰(298.15 K) ? H ⁰(0 K) = 10.84 ± 0.02 kJ/mol, and Φ⁰(298.15 K) = 44.95 ± 0.09 J/(K mol).     

Reduction of U(VI) in laser liquids POCl3-SnCl4-235UO 2 2+ -Nd3+

U(IV) is irreversibly accumulated during synthesis of laser liquids POCl₃-SnCl₄-²³⁵UO ₂ ²⁺ -Nd³⁺ prepared from various initial Nd(III) and U(VI) compounds, irrespective of the way of their introduction. The rate of U(IV) accumulation in POCl₃-SnCl₄-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions increases with increasing UO ₂ ²⁺ and Nd³⁺ concentrations; for laser liquids with the Nd³⁺ luminescence lifetime τ > 150 μs the observed rate constant of U(IV) accumulation by the second-order reaction k ₂[U⁴⁺] is equal to (3 ± 1) × 10^?5 1 mol^?1 s^?1 at T = 380 K. U(IV) is accumulated during storage of POCl₃-SnCl₄-²³⁵UO ₂ ²⁺ -Nd³⁺ solutions in hermetically sealed glass cells at room temperature and upon irradiation of solutions by xenon lamp light in the spectral region of UO ₂ ²⁺ absorption. The U(VI) reduction proceeds by chemical and photochemical activation of uranyl with formation of stable U⁴⁺ complexes with dichlorophosphate ions and also with Nd³⁺. Deactivation of the uranyl ion excitation with proton-and chlorine-containing impurities prevents U(VI) reduction.     

Low-temperature heat capacity and thermodynamic functions of Ga2Te3

The heat capacity of Ga₂Te₃ is measured from 9 to 310 K using adiabatic calorimetry. The smoothed heat capacity data are used to evaluate temperature-dependent thermodynamic functions (entropy, enthalpy increment, and reduced Gibbs energy) of Ga₂Te₃. Its thermodynamic properties under standard conditions are C _p ⁰ (298.15 K) = 119.3 ± 0.2 J/(K mol), S ⁰(298.15 K) = 209.8 ± 0.4 J/(K mol), H ⁰(298.15 K) ? H ⁰(0) = 27.19 ± 0.05 kJ/mol, and Φ⁰(298.15 K) = 118.6 ± 0.2 J/(K mol). The Debye characteristic temperature of Ga₂Te₃ evaluated from the heat capacity data is 280 ± 20 K.     

Thermodynamics of Ba2Sm2/3UO6

The standard enthalpy of formation of crystalline Ba₂Sm_2/3UO₆ at 298.15 K, ?3040.0±7.5 kJ mol^?1, was determined by reaction calorimetry. The heat capacity of the compound in the range 80–300 K was measured by adiabatic vacuum calorimetry, and its thermodynamic functions were calculated. Its standard entropy of formation at 298.15 K is ?592.5±1.0 J mol^?1 K^?1, and the Gibbs energy of formation at 298.15 K, ?2863.5±8.0 kJ mol^?1. The standard thermodynamic functions of the reactions of the Ba₂Sm_2/3UO₆ synthesis were calculated and discussed.     

Synthesis and adsorption properties of nanosized Mg-Al layered double hydroxides with Cl−, NO 3 − or SO 4 2− as interlayer anion

Nanosized Mg-Al layered double hydroxides (LDHs) with Cl^?, NO ₃ ^? or SO ₄ ^2? as the interlayer anion have been synthesized by a modified coprecipitation method. The obtained LDHs were confirmed to be composed of a single phase and to be highly substituted by Al (Mg/Al ratio ～1.9). The abilities of the LDHs to adsorb several harmful anions (F^?, CrO ₄ ^2? , HAsO ₄ ^2? and HSeO^3?) in aqueous solution were studied. The LDHs exhibit high adsorption abilities. The amount of adsorption onto the LDHs differed between the starting interlayer anions, and decreased in the following order of the interlayer anions: NO ₃ ^? > Cl^? > SO ₄ ^2? . The NO₃-formed Mg-Al LDH reached a CrO ₄ ^2? adsorption equilibrium state within only 30 min, much faster than those in previous reports. Thus, the nanocrystallized, highly Al substituted phase of the NO₃-formed Mg-Al LDH is found to markedly enhance the anion adsorption ability.     

Interaction of tetravalent actinides and Np(V) with some hydroxy carboxylic acids

Interaction of actinides(IV) with hydroxyisobutyric acid (HHIB) in aqueous solutions and in the course of crystallization of solid compounds was studied. The complexes ML _n ^(4-n)+ (M = U, Np, Pu; L^? is hydroxyisobutyrate anion; n = 1, 2, 3) exist in solution. Their apparent stepwise stability constants K?? _i were measured, and the overall concentration stability constants ??₃ of the complexes ML ₃ ⁺ were calculated. For U(IV) and Np(IV), log??₃ is close to 13.3?C13.4, and for Pu(IV), log??₃ = 14.5 ± 0.9 (ionic strength I = 0.1?C0.3). In the course of crystallization in air, complexes of U(IV) with hydroxyisobutyric acid, as well as those with citric acid, undergo oxidative degradation, which can be accompanied by complete oxidation of U(IV). The crystalline compounds formed in the process are oxalates of U(IV) or U(VI). The complexation of Np(V) with HHIB was studied. NpO ₂ ⁺ forms with HHIB the complexes NpO₂L and NpO₂L ₂ ^? . Their concentration stability constants are logK ₁ = 2.04 ± 0.15 and logK ₂ = 0.71 ± 0.10 (I = 0.4), i.e., log??₂ = 2.75 ± 0.25.     

Sorption of 131I− and 131IO 3 − from aqueous solution on nickel hydroxide at 20°C

Sorption of ¹³¹I^? and ¹³¹IO ₃ ^? from aqueous solution on solid Ni(OH)₂ at 20°C was studied. It was found that in sorption from aqueous solution, after 120-min contact of the liquid and solid phases at V/m = 500 ml g^?1, with an increase in the concentration of I^? and IO ₃ ^? from 10^?5 to 10^?3 M the distribution coefficients K _d decrease from 16.4 to 5.3 ml g^?1 for ¹³¹I^? and from 113.6 to 30.8 ml g^?1 for ¹³¹IO ₃ ^? . The influence of various anions (Cl^?, NO ₃ ^? , SO ₄ ^2? , and BO ₃ ^3? ) on sorption of ¹³¹I^? and ¹³¹IO ₃ ^? from aqueous solution on solid Ni(OH)₂ was studied. It was found that, with an increase in the concentration of these ions from 10^?5 to 10^?1 M, the distribution coefficients K _d of ¹³¹I^? and ¹³¹IO ₃ ^? decrease by a factor of 3–10.     

Possibility of generation of octavalent curium in the gas phase in the form of volatile tetraoxide CmO4

Experiments based on gas thermochromatography were performed with the aim to search for volatile tetraoxide CmO₄ in the products of thermal oxidation of microamounts of CmH_2–3. The carrier gas was He, and the reagent gas was O₂. At their equimolar ratio, the zone of deposition of volatile Cm species at negative temperatures, centered at ?80°C, was detected on the quartz column surface. The thermochromatographic peaks formed by plutonium tetraoxide and by the volatile Cm species are similar in shape. The enthalpy of adsorption of this species on the quartz surface was calculated to be ?47 ± 12 kJ mol^?1. The data obtained are compared to the results of previous experiments with PuH_2–3. The chemical behavior of the volatile Cm species at decreased O₂ concentration in the carrier gas (1 and 5%) was studied. It resembles the previously studied behavior of PuO₄ under similar conditions. It was concluded that the volatile Cm species has the formula CmO₄.     

A single crystal X-ray diffraction study of Na4(UO2)4(i-C4H9COO)11(NO3)·3H2O

Synthesis and the results of IR and single crystal X-ray diffraction study of Na₄(UO₂)₄(i-C₄H₉COO)₁₁·(NO₃)·3H₂O are reported. The crystals are monoclinic; the unit cell parameters at 100 K are as follows: a = 13.697(2), b = 20.285(3), c = 15.991(3) Å, β = 103.760(3)°, space group P2₁, Z = 2, R = 0.0650. The uraniumcontaining structural units are mononuclear moieties [UO₂(i-C₄H₉COO)₃]^? and [UO₂(NO₃)(i-C₄H₉COO)₂]^?, belonging to crystal-chemical group AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = i-C₄H₉COO^? and NO ₃ ^? ) of uranyl complexes. The IR data are consistent with the results of the single crystal X-ray diffraction study. The influence of the carboxylate ligand volume on the structure of Na[UO₂L₃]·nH₂O crystals (L = acetate, n-butyrate, isovalerate ion) is analyzed.