Effect of Partial Premixing on Stabilization and Local Extinction of Turbulent Methane/Air Flames

The stabilization characteristics and local extinction structures of partially premixed methane/air flames were studied using simultaneous OH-PLIF/PIV techniques, and large eddy simulations employing a two-scalar flamelet model. Partial premixing was made in a mixing chamber comprised of two concentric tubes, where the degree of partial premixing of fuel and air was controlled by varying the mixing length of the chamber. At the exit of the mixing chamber a cone was mounted to stabilize the flames at high turbulence intensities. The stability regime of flames was determined for different degree of partial premixing and Reynolds numbers. It was found that in general partially premixed flames at low Reynolds numbers become more stable when the level of partial premixing of air to the fuel stream decreases. At high Reynolds numbers, for the presently studied burner configuration there is an optimal partial premixing level of air to the fuel stream at which the flame is most stable. OH-PLIF images revealed that for the stable flames not very close to the blowout regime, significant local extinction holes appear already. By increasing premixing air to fuel stream successively, local extinction holes grow in size leading to eventual flame blowout. Local flame extinction was found to frequently attain to locations where locally high velocity flows impinging to the flame. The local flame extinction poses a future challenge for model simulations and the present flames provide a possible test case for such study.     

Copper(I)-assembled [3]rotaxane whose two rings act as flapping wings

A new copper-complexed [3]rotaxane consisting of two coordinating 30-membered rings threaded by a two-binding-site axis has been prepared in good yield from relatively simple organic fragments. The main specificity of the system originates from the stoppering reaction, based on "click" chemistry, and thus from the presence of two triazole groups at positions next to the bidentate chelates of the axis central part. The geometry of the coordinating atoms belonging to the axis is such that the triazole groups can either be part of the coordinating fragments when the metal center is 5-coordinate or be not at all involved in coordination to the metal when the latter is 4-coordinate. To be more specific, when the two complexed metal centers are monovalent copper(I) centers, the triazoles are not included in the metal coordination sphere, whereas when the metal centers are Cu(II) or Zn(2+), the triazole groups are bound to the metals. This is easily explained by the fact that Cu(I) is preferably 4-coordinate and Cu(II) and Zn(2+) are 5-coordinate. The interconversion between both situations (4- or 5-coordinate) can be quantitatively induced by metal exchange (Cu(I)/Zn(2+)) or by a redox process (Cu(II)/Cu(I)). It leads to important geometrical changes and in particular to a strong modification of the angle between the two rings. As a consequence, the two threaded rings undergo a motion which is reminiscent of a wing-flapping movement similar to that of birds. This flapping motion is fast and quantitative. It should lead to new functional molecular machines in the future.     

Indication of reactor ν(e) disappearance in the Double Chooz experiment

The Double Chooz experiment presents an indication of reactor electron antineutrino disappearance consistent with neutrino oscillations. An observed-to-predicted ratio of events of 0.944±0.016(stat)±0.040(syst) was obtained in 101 days of running at the Chooz nuclear power plant in France, with two 4.25 GW(th) reactors. The results were obtained from a single 10 m(3) fiducial volume detector located 1050 m from the two reactor cores. The reactor antineutrino flux prediction used the Bugey4 flux measurement after correction for differences in core composition. The deficit can be interpreted as an indication of a nonzero value of the still unmeasured neutrino mixing parameter sin(2)2θ(13). Analyzing both the rate of the prompt positrons and their energy spectrum, we find sin(2)2θ(13)=0.086±0.041(stat)±0.030(syst), or, at 90% C.L., 0.017相似文献   

Tandem Michael imino–aldol reactions catalyzed by samarium diiodide

Samarium diiodide catalyzes a one-pot procedure allowing to perform sequentially the Michael addition of a ketene silyl acetal on a cyclic ,β-unsaturated ketone, followed by the addition of a glyoxylic or aromatic imine. The presence of a coordinating group on the imine increases the rate of the reaction.     

X-ray superstructure determination of ordered oxygen and Cu-displacements in a single domain of YBa2Cu3O6.35

The superstructure of ordered oxygen atoms in a single domain of YBa₂Cu₃O_6.35 has been determined by X-ray diffraction. The 45^o rotated superstructure cell is orthorhombic—spacegroup Pbam, lattice constants , witha=3.8652(3) Å,c=11.815(2)Å the dimensions of the fundamental tetragonal cell. The arrangement of the oxygen atoms in the basal plane minimizes their electrostatic repulsion by avoiding near and next-near neighbors. There are displacements of copper atoms of 0.13 Å in the Cu(1) plane and 0.06 Å in the Cu(2) plane. Only 12% of the oxygen atoms in the basal plane contribute to the superstructure.     

Is it homogeneous or heterogeneous catalysis? Compelling evidence for both types of catalysts derived from [Rh(eta5-C5Me5)Cl2]2 as a function of temperature and hydrogen pressure

Addressed herein is the 20+ year-old question of whether the true benzene and cyclohexene hydrogenation catalysts derived from the organometallic precursor [Rh(eta5-C5Me5)Cl2]2, 1, are homogeneous or heterogeneous. The methodology employed is that developed earlier (Lin, Y.; Finke, R. G. Inorg Chem. 1994, 33, 4891, "A More General Approach to Distinguishing Homogeneous from Heterogeneous Catalysis..."). The kinetic evidence especially, but also the metal product (nanoclusters plus bulk metal), Hg0 poisoning and other experiments, provide compelling evidence that Rh0 nanoclusters are the true benzene hydrogenation heterogeneous catalyst derived from [Rh(eta5-C5Me5)Cl2]2, 1, at the required more vigorous conditions of 50-100 degrees C and 50 atm H2. However, the same methods reveal that the cyclohexene hydrogenation catalyst derived from 1 at the milder conditions of 22 degrees C and 3.7 atm H2 is a nonnanocluster, homogeneous catalyst, most likely the previously identified complex, [Rh(eta5-C5Me5)(H)2(solvent)] (Gill, D. S.; White, C.; Maitlis, P. M J. C. S. Dalton Trans. 1978, 617). In short, the present results solve the two-decade-old problem of identifying the true benzene and cyclohexene hydrogenation catalysts derived from [Rh(eta5-C5Me5)Cl2]2. Perhaps most significant is the demonstration that the methodology employed has the ability to identify both heterogeneous and homogeneous catalysts from the same catalyst precursor.     

Elaboration,structure cristalline et proprietes physiques (transport,susceptibilité magnétique et R.M.N.) du spinelle CuV2S4

Single crystals of CuV₂S₄ have been made by chemical vapor transport with chlorine as the transport agent. Characterization by an X-ray study, density measurements by the hydrostatic technique and electron microprobe analysis were performed. They showed no deviation from stoichiometry of the compound. Refinement of the structure (space group Fd3m) has been done. Transport properties, magnetic susceptibility and N.M.R. data from 1.5°K to 300°K present discontinuities below 100°K. Observed properties are discussed in view of the previously proposed band model. The relationships between magnetic susceptibility and Knight shifts are included in this paper.