Catalytic reduction of U(VI) with formic acid in acid solutions on palladium catalysts

The kinetics of catalytic reduction of U(VI) with formic acid in H₂SO₄ solutions in the presence of Pd/SiO₂ catalysts differing in the size of nanocrystallites of the active metal was studied. A decrease in the size of supported Pd particles leads to a decrease in the specific activity of the catalyst, i.e., the catalytic centers located on large crystallites exhibit higher activity. An increase in the Pd percent content on SiO₂ leads to a decrease in the activity of the catalytic centers, which is caused by a considerable increase in the contribution of the side reaction of catalytic decomposition of HCOOH with an increase in the number of active centers in the catalyst grain. The results obtained are interpreted on the basis of the concepts of the energy nonuniformity of the surface atoms and of the reaction mechanism. The results show that the size of Pd nanocrystallites is an important factor of the selectivity of palladium catalysts in the preparation of U(IV) by catalytic reduction with formic acid.     

Plasma parameters of an electron cyclotron resonance discharge in a magnetic mirror in a quasi-gasdynamic confinement regime

An experimental investigation is made of x-ray bremsstrahlung in the 2–10 keV range of a pulsed discharge under electron cyclotron resonance conditions in a straight magnetic mirror system pumped by a high-power millimeter radiation beam. The plasma temperature and density were determined from the spectrum and intensity of the x-rays. The results indicate that a quasi-gasdynamic plasma confinement regime is achieved. Pis’ma Zh. Tekh. Fiz. 25, 90–93 (July 26, 1999)     

Catalytic decomposition of organic anions in alkaline radioactive waste: IV. Oxidation of glycolate with persulfate in the presence of Ru(III)

Oxidation of glycolate ions with Na₂S₂O₈ + RuCl₃ mixture in 0.2 M NaOH was studied by spectrophotometry. Glycolate is oxidizd to oxalate at 20–70°C. The reaction of glycolate with persulfate follows the first-order rate law with respect to [S₂O ₈ ^2? ], weakly depends on the glycolate concentration, and accelerates with increasing the Ru(III) content from 2 × 10^?5 to 1 × 10^?4 M. Further increase in the Ru(III) concentration does not affect the reaction rate. Probable reaction mechanism was considered.     

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.     

Stability of Pu(VI) and Pu(V) in aqueous formate solutions

The behavior of Pu(VI), Pu(V), and Pu(IV) in K(Li,Na)HCO₂ and HCOOH + Li(Na)HCO₂ solutions was studied by spectrophotometry. Changes in the spectra of a Pu(VI) solution, observed on adding alkali metal formates, suggest formation of Pu(VI) formate complexes. Changes in the absorption spectra of Pu(V), observed with an increase in the concentration of LiHCO₂ or NaHCO₂, suggest the appearance of Pu(V) formate complexes. The absorption spectra of Pu(IV) indicate that, in a wide range of formate concentrations, the composition of the Pu(IV) formate complexes under the examined conditions is constant. The Pu(VI) content in formate solutions decreases at a rate exceeding the rate of the Pu(VI) disappearance in 0.5–2 M HClO₄ under the action of the ²³⁹Pu α-radiation. The tendency of Pu(V) to reduction and disproportionation in formate solutions depends in a complex fashion on the formate ion concentration and kind of the alkali metal. The kinetics of the Pu(V) consumption in HCOOH + Li(Na)HCO₂ solutions was studied. The reaction starts with the formation of a Pu(V) formate complex, which interacts with Pu(V) aqua ions and Pu(V) formate complex to form dimers, with their subsequent protonation and transformation into Pu(VI) and Pu(IV).     

Nondeterministic program schemata and their relation to dynamic logic

Translated from Kibernetika, No. 3, pp. 12–18+28, May–June, 1988.     

Reaction of ozone with uranium(IV) oxalate in water

Decomposition of aqueous suspensions of uranium(IV) oxalate under the action of an ozone–oxygen mixture was studied. The process occurs in two steps. In the first step, the U(IV) oxidation with the formation of oxalic acid uranyl solutions prevails. The second step involves decomposition of oxalate ions and hydrolysis of uranyl ions. An increase in temperature accelerates the transformation of uranium(IV) oxalate into uranium(VI) hydroxide compounds. In solutions containing KBr or UO₂Br₂, the following reaction occurs: O₃ + Br^– → O₂ + BrO^–. The arising hypobromite ions and hypobromous acid oxidize uranium(IV) oxalate extremely efficiently. The possible mechanism of ozonation of aqueous uranium(IV) oxalate suspensions is discussed.     

Hydrodynamic Cell Model: General Formulation and Comparative Analysis of Different Approaches

This paper is concerned with the Cell Model method of addressing hydrodynamic flow through system of solid particles. The starting point of the analysis is the general problem formulation intended for describing a pressure driven flow through a diaphragm which can be considered as a set of representative cells having arbitrary shape and containing any number of particles. Using the general problem formulation, the hydrodynamic field inside an individual representative cell is interrelated with the applied pressure difference and the external flow velocity. To this end, four relationships containing integrals over the outer boundary of a representative cell are derived in the paper. Assuming that the representative cell is a sphere containing a single particle in the centre, the derived general relationships are transformed into outer cell boundary conditions employed in the literature by different authors. The general number of the obtained outer boundary conditions is more than the required number. Accordingly, by choosing different sets of the outer boundary conditions, different models are considered and compared with each other and with the results obtained by others for regular particle arrays. The common and different features of the hydrodynamic and electrodynamic versions of the Cell Model approaches are analyzed. Finally, it is discussed which version of the cell model gives the best approximation while describing pressure and electrically driven flows through a diaphragm and sedimentation of particles.     

The Effect of Krypton Consumption through the Accelerator Channel on Thrust Efficiency of a Morozov’s Stationary Plasma Thruster

Morozov’s stationary plasma thrusters (SPTs) operating on xenon have been successfully used in space technology for many years. At the same time, due to the high cost of xenon, now there is an increased interest in alternative working substances. One of them is krypton. Therefore, research has been conducted earlier on the features of operation and characteristics of SPTs using krypton, which have showed that they are traditional for SPTs. Here, we consider the results of studying the effect of krypton consumption on the thrust efficiency of SPTs. The importance of these results is determined by the fact that they determine the appropriate ranges of SPT regimes when working on krypton.