Transformations of cobalt trimethylacetate complexes with pyrazole upon oxidation by air in THF

Synthetic routes to oxidation of cobalt atoms in cobalt trimethylacetate complexes containing coordinated pyrazole molecules have been considered.     

An upper bound for the largest eigenvalue of a graph: Effect of types of vertices

A novel method, based on the topology of the cardinal vertex, is described to find an upper bound for the largest eigenvalue of a graph.     

Two-dimensional on-line particle imaging velocimetry

A high-performance algorithm is described for the on-line computation of two-dimensional velocity maps using particle displacement imaging. It relies on the computation of direct correlations in a multiple-scale spatial hierarchy. Layered rejection criteria based on correlation quality and conditional averaging techniques are employed to achieve the robustness required for continuous, unsupervised operation. Implementations are described using a UNIX-based workstation and a DOS-based personal computer with a real-time image processing/correlator subsystem. The cooperation of the algorithm with other real-time visualization techniques is demonstrated using the example of colour-coded streak integration.The authors wish to thank Dr. Philippe Georis of the Université Libre de Bruxelles (ULB) for making available to us video sequences of his Marangoni convection experiment.     

Computational advances in organic chemistry: Molecular structure and reactivity. Edited by C. Ögretir and I. G. Csizmadia,NATO ASI Series C,Vol, 330.

We here report an AM 1 study for the reaction of different types of radicals with the acetone enolate ion 1 and other ambident nucleophiles. The theoretical reactivity order determined is phenyl > methyl > tert-butyl ? bicyclo-[2.2.1]hept-1-yl. The activation energy for the coupling of aliphatic radicals is ascribed mainly to nonbonded interactions. Considering possible solvent effects, we propose the same order of reactivity in solution. The coupling reaction of phenyl radical with 1 is an exothermic process with nonactivation energy in the gas phase. Any energy barrier in solution is here ascribed to desolvation of the anion. The regiochemistry of the coupling of radicals with ambident nucleophiles such as 1 , phenoxide, or phenylamide anions is also explained on a theoretical basis. © 1992 John Wiley & Sons, Inc.     

Continuous removal of radiolytic products from TBP extraction systems

In the actinide separation process using TBP as extractant, hydrolytic and radiolytic reactions cause a gradual decomposition of the extractant, resulting in the formation of degradation products which can affect process performance adversely. The TBP diluent has to be cleaned from these degradation products before it is reused. This paper deals with a procedure for solvent cleanup, using a fourstage continuous contactor for increasing the scrubbing efficiency.     

Decay of confined,two-dimensional,spatially periodic arrays of vortices: A numerical investigation

The disarrangement of a perturbed lattice of vortices was studied numerically. The basic state is an exponentially decaying, exact solution of the Navier-Stokes equations. Square arrays of vortices with even numbers of vortex cells along each side were perturbed and their evolution was investigated. Whether the energy in the perturbation grows somewhat before it decays or decays monotonically depends on the initial strength of the vortices of the basic state, the extent of lateral confinement and the structure of the perturbation. The critical condition for temporally local instability, i.e. the critical amplitude of the basic state that must be exceeded to allow energy transfer from the basic state to the perturbation, is discussed. In the strongly confined case of a square lattice of four vortices the appearance of enchancement of global rotation is the result of energy transfer from the basic state to a temporally local unstable mode. Energy is transferred from the basic state to larger-scaled structures (inverse cascade) only if the scales of the larger structures are inherently contained in the initial structure of the perturbation. The initial structure of the double array of vortices is not maintained except for a very special form of perturbation. The facts that large scales decay more slowly than small scales and that, when non-linearities are sufficiently strong, energy is transferred from one scale to another explain the differences in the disarrangement process for different initial strengths of the vortices of the basic state. The stronger vortices, i.e. the vortices perturbed in a manner that increases their strength, tend to dominate the weaker vortices. The pairing and subsequent merging (or capture) of vortices of like sense into larger-scale vortices are described in terms of peaks in the evolution of the square root of the palinstrophy divided by the enstrophy.     

Application of the variation principle for the problem of buckling of a nonlinearly elastic ring nonuniform along its thickness

There has been considerable recent attention given to the stressed and buckled states of items with complicated configuration made of different nonlinearly elastic materials joined by complete adhesion. However, effective analytical solutions for such problems have been hindered by mathematical difficulties. Approximate methods have thus been developed for such problems. A variational combined principle has been formulated in this communication. A nonlinear geometrical approach has been used for formulating a mixed-type functional with physical relationships given by Euler equations, nonlinear equilibrium equations, and nonlinear boundary conditions for a piecewise-nonuniform nonlinearly elastic body composed of finite elements (particles). As an example, buckling along the nonuniform thickness of nonlinearly elastic rings was analyzed hypothetically assuming plane cross-sections. Options for two-, three-, four-, five-, and six-layered rings in a periodical structure have been reviewed. The critical buckling forces for an even number of layers have been found to be equal to each other. The ratios of the critical forces, elasticity moduli, and proportionality levels were determined for all five variants by the Runge-Kutta method.Presented at the Ninth International Conference on the Mechanics of Composite Materials (Riga, October, 1995).Translated from Mekhanika Kompozitnykh Materialov, Vol. 31, No. 2, pp. 262–268, March–April, 1995.     

Observation of sharp resistance anomalies near Tc in granular superconductors

Granular films prepared from well-defined In clusters embedded in Kr (? 10-40 at % Kr) show sharp resistance anomalies very close to the superconducting transition temperature. The observed resistance peak(s), which go(es) above the normal state resistance R_N and which can be as high as ? 1.5 R_N, can be explained by a “mesoscopic” effect: Superconducting percolation aggregates of size ξ_ρ, larger than the superconducting coherence length ξ_S, but smaller than the quasiparticle relaxation length λ_Q*, have a superconducting gap, but are not yet able to carry a supercurrent.     

Regions of stability of high-power gyrotron oscillators

The problem of mode competition in a high-power gyrotron oscillator is considered. The regions of parameter space in which a preexisting large-amplitude mode is able to suppress competing satellites are determined for cases in which the coupling coefficients and cavity quality factors for the operating and satellite modes are different. In addition, the effect of beam quality on the regimes of stable single-mode operation is investigated. Generally speaking, the requirement of stable operation favors devices whose interaction length measured by the parameter μ is not too large. It is found that for μ near 10 the operation is relatively stable and μ near 17 is not