Heterogeneous Equilibria in the System M<Superscript>m</Superscript>(BUO<Subscript>5</Subscript>)<Emphasis Type="Italic">m</Emphasis>·<Emphasis Type="Italic">n</Emphasis>H<Subscript>2</Subscript>O-Aqueous HCl

A quantitative model of the system crystalline uranoborate-aqueous solution was proposed on the basis of the experimental solubilities of Mm(BUO₅)m⋅nH₂O (M^m are alkaline and alkaline-earth metals) in aqueous HCl at 25°C. The model was used to predict the state of the heterogeneous systems under study under various conditions and to calculate the standard thermodynamic functions of the uranoborates.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 46–52.Original Russian Text Copyright © 2005 by Chernorukov, Nipruk, Knyazev, Khomyakova.     

The mechanism of O(3P) atom reaction with ethylene and other simple olefins

Reactions of oxygen atoms with ethylene, propene, and 2-butene were studied at room temperature under discharge flow conditions by resonance fluorescence spectroscopy of O and H atoms at pressures of 0.08 to 12 torr. The measured total rate constants of these reactions are K = (7.8 ± 0.6)·10^?13cm³s^?1,K = (4.3 ± 0.4) ± 10^?12 cm³ s^?1, K = (1.4 ± 0.4) · 10^?11 cm³ s^?1. The branching ratios of H atom elimination channels were measured for reactions of O atoms with ethylene and propene. No H-atom elimination was found for the reaction of O-atoms with 2-butene. A redistribution of reaction O + C₂ channels with pressure was found. A mechanism of the O + C₂ reaction was proposed and the possibility of its application to other olefins is discussed. On the basis of mechanism the pressure dependence of the total rate constant for reaction O + C₂ was predicted and experimentally confirmed in the pressure range 0.08–1.46 torr.     

Kinetics of the unimolecular decomposition of the 2-chloroallyl radical

The thermal decomposition of the 2-chloroallyl radical, CH(2)CClCH(2) --> CH(2)CCH(2) + Cl (1), was studied using the laser photolysis/photoionization mass spectrometry technique. Rate constants were determined in time-resolved experiments as a function of temperature (720-840 K) and bath gas density ([He] = (3-12) x 10(16), [N(2)] = 6 x 10(16) molecule cm(-3)). C(3)H(4) was observed as a primary product of reaction 1. The rate constants of reaction 1 are in the falloff, close to the low-pressure limit, under the conditions of the experiments. The potential energy surface (PES) of reaction 1 was studied using a variety of quantum chemical methods. The results of the study indicate that the minimum energy path of the CH(2)CClCH(2) dissociation proceeds through a PES plateau corresponding to a weakly bound Cl-C(3)H(4) complex; a PES saddle point exists between the equilibrium CH(2)CClCH(2) structure and the Cl-C(3)H(4) complex. The results of quantum chemical calculations, the rate constant values obtained in the experimental study, and literature data on the reverse reaction of addition of Cl to allene were used to create a model of reactions 1 and -1. The experimental dependences of the rate constants on temperature and pressure were reproduced in RRKM/master equation calculations. The reaction model provides expressions for the temperature dependences of the high-pressure-limit and the low-pressure-limit rate constants and the falloff broadening factors (at T = 300-1600 K): k(infinity)(1) = 1.45 x 10(20)T(-1.75) exp(-19609 K/T) s(-1), k(infinity)(-)(1) = 8.94 x 10(-10)T(-0.40) exp(481 K/T) cm(3) molecule(-1) s(-1), k(1)(0)(He) = 5.01 x 10(-32)T(-12.02) exp(-22788 K/T) cm(3) molecule(-1) s(-1), k(1)(0)(N(2)) = 2.50 x 10(-32)T(-11.92) exp(-22756 K/T) cm(3) molecule(-1) s(-1), F(cent)(He) = 0.46 exp(-T/1001 K) + 0.54 exp(-T/996 K) + exp(-4008 K/T), and F(cent)(N(2)) = 0.37 exp(-T/2017 K) + 0.63 exp(-T/142 K) + exp(-4812 K/T). The experimental data are not sufficient to specify all the parameters of the model; consequently, some of the model parameters were obtained from quantum chemical calculations and from analogy with other reactions of radical decomposition. Thus, the parametrization is most reliable under conditions close to those used in the experiments.     

Hydrosilylation of cyclohexene and allyl chloride with trichloro-, dichloro(methyl)-, and chlorodimethylsilanes in the presence of Pt(0) complexes

Hydrosilylation of cyclohexene and allyl chloride in the presence of Pt(0) complexes with tetramethyldivinyldisiloxane (Karstedt catalyst) and hexavinyldisiloxane was studied. It was shown that these catalysts are much more active in the hydrosilylation of cyclohexene with trichloro-, dichloro(methyl)-, and chlorodimethylsilane than the Pt(II)-containing Speier catalyst. In the hydrosilylation of allyl chloride in the presence of Pt(0) complexes, the ratio of the fraction of addition products to the fraction of reduction products increases from 5.7 (Speier catalyst) to 10–16. Quantum-chemical calculations showed that Pt(0) complexes are more active than Pt(II) complexes on the stage of formation of platinum silicon hydride complexes.     

Quantum chemical study of nickel(II) complexes with cyclic diimine ligands on the base of bis[3,3′-iminopropyl]methylamine

A quantum chemical study of spatial and electronic structures of molecules in the frame complexes, bis[3,3′(RR′)-ketiminepropyl]methylamine nickel dichlorides, where R = H, CH₃, and R′ = H, CH₃, has been performed by DFT(B3LYP/LANL2DZ) method. The molecules of these complexes were found to be in a triplet state. Energy stability of the endo form of the complex molecules was shown. In the molecule of bis[3,3′-aldiminopropyl]methylamine nickel dichloride (R = R′ = H), a considerable strengthening of the bond Ni-N(amine) takes place when passing from the diamagnetic into paramagnetic state, and all bonds Ni-N become equivalent with respect to interatomic distance values. The topology analysis of the electron density for the complexes with R = R′ =H and R = R′ = CH₃ was carried out. It is stated that all Ni-N bonds are covalent in the molecules of paramagnetic complexes.     

Dynamics of the Surface Morphology of a Tungsten Foil under Load

Physics of the Solid State - The dynamics of changes in the surface morphology of recrystallized tungsten foil under the action of uniaxial tension was studied in situ by the methods of low-energy...     

A subspace preconditioning algorithm for eigenvector/eigenvalue computation

We consider the problem of computing a modest number of the smallest eigenvalues along with orthogonal bases for the corresponding eigenspaces of a symmetric positive definite operatorA defined on a finite dimensional real Hilbert spaceV. In our applications, the dimension ofV is large and the cost of invertingA is prohibitive. In this paper, we shall develop an effective parallelizable technique for computing these eigenvalues and eigenvectors utilizing subspace iteration and preconditioning forA. Estimates will be provided which show that the preconditioned method converges linearly when used with a uniform preconditioner under the assumption that the approximating subspace is close enough to the span of desired eigenvectors.     

Methods and computer codes for nuclear systems calculations

Some numerical methods for reactor cell, sub-critical systems and 3D models of nuclear reactors are presented. The methods are developed for steady states and space-time calculations. Computer code TRIFON solves space-energy problem in (X, Y) systems of finite height and calculates heterogeneous few-group matrix parameters of reactor cells. These parameters are used as input data in the computer code SHERHAN solving the 3D heterogeneous reactor equation for steady states and 3D space-time neutron processes simulation. Modification of TRIFON was developed for the simulation of space-time processes in sub-critical systems with external sources. An option of SHERHAN code for the system with external sources is under development.      

Correction of a calibration scale for the rapid visual semiquantitative determination of phosphate ions in agricultural samples

A procedure was developed of fabricating a colored calibration scale for determining phosphate ions in aqueous solutions. The procedure is suitable for correcting hue steps depending on the analytical range of phosphate ions. A rapid procedure was proposed for visual testing in a blister cell with a bulk mixture of dry reagents. A test effect was observed immediately after the cell was opened and several drops of a test solution were added. Mixture compositions were developed for the visual determination of phosphate ions in a concentration range of 0.5–80 mg/L by the formation and reduction of phosphomolybdic acid using auxiliary reagents.