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841.
Jens Sehested Ole John Nielsen Carlos A. Rinaldi Silvia I. Lane Juan Carlos Ferrero 《国际化学动力学杂志》1996,28(8):579-588
The reaction of CF3 with NO2 was studied at 296 ± 2K using two different absolute techniques. Absolute rate constants of (1.6 ± 0.3) × 10−11 and (2.1 −0.3+07) × 10−11 cm3 molecule−1 s−1 were derived by IR fluorescence and UV absorption spectroscopy, respectively. The reaction proceeds via two reaction channels: CF3 + NO2 → CF2O + FNO, (70 ± 12)% and CF3 + NO2 → CF3O + NO, (30 ± 12)%. An upper limit of 11% for formation of other reaction products was determined. The overall rate constant was within the uncertainty independent of total pressure between 0.4 to 760 torr. © 1996 John Wiley & Sons, Inc. 相似文献
842.
Jens Beckmann Dainis Dakternieks Andrew Duthie Edward R. T. Tiekink 《无机化学与普通化学杂志》2002,628(13):2948-2953
The six‐, eight‐ and twelve‐membered cyclo‐siloxanes, cyclo‐[R2SiOSi(Ot‐Bu)2O]2 (R = Me ( 1 ), Ph ( 2 )), cyclo‐(t‐BuO)2Si(OSiR2)2O (R = Me ( 3 ), Ph ( 4 )), cyclo‐R2Si[OSi(Ot‐Bu)2]2O (R = Me ( 5 ), Ph ( 6 )) and cyclo‐[(t‐BuO)2Si(OSiMe2)2O]2 ( 3a ) were synthesized in high yields by the reaction of (t‐BuO)2Si(OH)2 and [(t‐BuO)2SiOH]2O with R2SiCl2 and (R2SiCl)2O (R = Me, Ph). Compounds 1 — 6 were characterized by solution and solid‐state 29Si NMR spectroscopy, electrospray mass spectrometry and osmometric molecular weight determination. The molecular structure of 4 has been determined by single crystal X‐ray diffraction and features a six‐membered cyclo‐siloxane ring that is essentially planar. The reduction of 1 — 6 with i‐Bu2AlH (DIBAL‐H) led to the formation of the metastable aluminosiloxane (t‐BuO)2Si(OAli‐Bu2)2 ( 7 ) along with Me2SiH2 and Ph2SiH2. 相似文献
843.
The reaction of CuCl, LiAs(SiMe3)2 and dppb (Bis(diphenylphosphino)butane) leads to the formation of ionic cluster complexes. Depending on the reaction conditions one can isolate [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As2(SiMe3)2}{As4(SiMe3)4}]‐ ( 1 ) and [Cu8As3(AsSiMe3)2(dppb)4]+[Cu{As(SiMe3)2}2]‐ ( 2 ). The same reaction of CuCl, dppm (Bis(diphenylphosphino)methane) and LiSb(SiMe3)2 leads to the neutral cluster complex [Cu10(Sb3)2(SbSiMe3)2(dppm)6] ( 3 ). The structures of 1‐3 have been solved by X‐ray single crystal analyses. 相似文献
844.
The spray cone emerging during an extended metal atomization process (called spray forming) has been investigated in order to quantify the influence of highly concentrated multiphase flows on phase‐Doppler‐anemometry (PDA) measurements. Using this non‐intrusive, optical measurement technique not only the local particle size and velocity distributions of the spray can be obtained but also additional information about the mass flux in the multiphase flow. Since standard phase‐Doppler systems can be easily applied to low concentrated particle systems (spherical particles with smooth surfaces and an optical transparent continuous phase taken for granted) the application of this measurement technique to highly concentrated multiphase flows is more complex. Both the laser light propagating from the PDA device to the probe volume and the scattered one going backward to the PDA receiving system are disturbed by passing the highly concentrated multiphase flow. The resulting significant loss in signal quality especially concerns the measurement of the smaller particles of the spray because of their reduced silhouette (in comparison with the bigger ones). Thus, the detection of the smallest particles becomes partially impossible leading to measurement of a distorted diameter distribution of the entire particle collective. In this study the distortions of the measured distributions dependent on the particle number concentration as well as on the path length of the laser light are discussed. 相似文献
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Simulations of polymer‐solvent and polymer‐polymer aggregates, in which the study of hydrogen bonding plays an important role, have been carried out with two blend systems. The aim was to examine the influence of the solvent on blend complexation and to compare the strength of different hydrogen bonds in a blend system. We quantified the strength of one hydrogen bond in the blend environments. For this we used the EVOCAP software, developed by our institute. It allows the building of large molecular aggregates with realistic and homogeneous densities, with an implemented positioning algorithm of the molecules under consideration and their excluded volume, and a charge equilibration method for the partial charge calculation. In the simulated aggregates the specific interaction energy of the hydrogen atom forming the hydrogen bond was a useful indicator for our studies. Through a direct correlation of this specific‐interaction energy with the strength of the hydrogen bond, we supported the experimental result that, in toluene, complex formation between poly(methyl methacrylate) (PMMA) and PSOH, a hydroxyl‐modified polystyrene, is possible, but not in tetrahydrofuran. Varying the proton‐donor polymer, also a hydroxyl‐modified polystyrene, in blends of poly(vinyl methyl ether) (PVME) with groups of different donor strength, we reconstructed the experimental row of increasing hydrogen‐bond strengths. 相似文献
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850.
Uwe Engelmann Gudrun Schmidt-Naake Jens Maier Peter Seifert 《Macromolecular theory and simulations》1994,3(5):855-883
With the help of a simple reaction-diffusion model with constant striation thickness the influence of micromixing on free-radical polymerization was investigated for several test reactions with discontinuous prepolymerization and jerky addition of selected reactants. Monomer conversion or mean values of molar mass and chemical composition cannot be expected to be very sensitive to micromixing effects. If molar mass distributions are to be used, problems will arise from the fact that the distribution of the polymer accumulated during prepolymerization covers mixing influences occurring after reactant feed. The instantaneous molar mass distribution would be more suitable. Time-integral distributions of chemical composition or sequence length in combination with appropriate test reactions proved to be feasible indicators for the effects of micromixing as it becomes possible to separate the distribution of the prepolymer from that of the polymer which is formed after addition when micromixing is to be investigated. 相似文献