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21.
Silica xerogels with different structures and morphology, synthesized using a sol-gel procedure, were used as a carrier of vanadium catalysts (VOCl3/AlEt2Cl) for ethylene polymerization. Two techniques of catalyst synthesis were applied: slurry impregnation and gas-phase adsorption and the relevant polymerization methods were then employed. The effect of the carrier structure and morphology on the vanadium loading in the catalysts, the catalyst’s activity and kinetic stability were investigated. 相似文献
22.
A simple procedure to decompose the theoretical molecular charge distribution into cumulative atomic multipoles supplementing any population analysis scheme has been described and tested for a number of molecules in extended basis sets. This approach may be applied to describe local charge distributions in neutral as well as charged systems and also leads to a simplified point-charge model conserving the local anisotropy of the atomic charge distribution in molecules. Such an approach may be useful in estimating intermolecular interactions, representing the molecular environment in solvent effect or enzyme catalytic activity studies, evaluation of molecular electrostatic potentials or tracing the quality of basis set functions. 相似文献
23.
The resonanceRaman spectra of Fe(LC 12)3Cl2 and Fe(LC 18)3Cl2 (whereLC 12 andLC 18 denote 4,4′-didodecyloxy-2,2′-bipyridine and 4,4′-dioctadecyloxy-2,2′-bipyridine, respectively) have been measured along with their excitation profiles. The exciting lines of an Ar+ laser have been used. The bands appearing in theRR spectra within 1 200–1 600cm?1 (expected to arise from thebipy moiety C-N and C-C vibrations) suffer the greatest resonance enhancements. Both depolarization ratios of theRaman bands and excitation profiles reveal the interaction of the resonant electronic states. 相似文献
24.
Complex systems of paramagnetic centres existing in demineralised flame coal (71.4 wt% C), medium-rank coal (85.6 wt% C) and
anthracite (94.9 wt% C) were analysed by electron paramagnetic resonance spectroscopy (EPR). Different groups of paramagnetic
centres were searched in macerals (exinite, vitrinite, inertinite) of coals with carbon contents of 73.8 wt% C and 85.6 wt%
C. Experimental EPR spectra were fitted by different superposition of theoretical lines. Total concentration of paramagnetic
centres both in coal and macerals increases with carbon content in the sample. Total concentration of paramagnetic centres
in macerals increases from exinite to inertinite. Four groups of paramagnetic centres were found in medium-rank coal, and
only two groups exist in flame coal and anthracite. The EPR spectrum of medium-rank coal is a superposition of two broad and
two narrow lines. Both broad and narrow, and two narrow lines were measured in EPR spectra of flame coal and anthracite, respectively.
Two types of paramagnetic centres with broad lines and one group with narrow lines exist in exinite and vitrinite from medium-rank
coal. Two narrow components were observed in EPR spectra of its inertinite. Two different broad electron paramagnetic resonance
signals were detected for macerals from low-coalificated coal. Paramagnetic centres systems of medium-rank coal samples reveal
the most complex character. Broad EPR lines were not observed for the higher coalificated samples, i.e., anthracite and inertinite
from medium-rank coal. Narrow lines do not occur in EPR spectra of low-coalificated macerals. Strong dipolar interactions
and fast spin-lattice relaxation processes are characteristic for paramagnetic centres with broad lines. Strong exchange interactions
and short spin-lattice relaxation time were measured for paramagnetic centres with the narrowest EPR signals. 相似文献
25.
26.
Pt(II) and Pd(II) dichloride complexes with 5,7-ditertbutyl-1,2,4-triazolo[1,5-a]pyrimidine (dbtp) have been synthesized and characterized by infrared and 1H, 13C NMR, 13C CPMAS spectroscopy. The structures of the cis-PtCl2(dbtp)2 · EtOH (1) and cis-PdCl2(dbtp)(dmso) (2) has been determined by signal-crystal X-ray diffraction. In both complexes the X-ray crystal structures shows that heterocycle ligand (dbtp) binds the central atom monodentate via nitrogen atom N(3). In addition, compound (2) is interesting for its structural features, because it is the first report of mixed dichloride Pd(II) complexes with N-donor (triazolopyrimidine) and S-donor (dimethylsulfoxide) ligands. In this structure the Pd–Cl distances are: 2.302(1) and 2.281(1) Å, Pd–N 2.041(3) Å and Pd–S 2.245(1) Å. The 1H, 13C NMR studies show clearly that these structures are retained in solution. 相似文献
27.
Andrzej Czopnik Nataly Shitsevalova Alexander Krivchikov Vasyl Pluzhnikov Yuriy Paderno 《Journal of solid state chemistry》2004,177(2):507-514
We have measured heat capacity and thermal expansion of rare earth dodecaborides REB12 (RE=Y, Tb-Tm, Lu). YB12 and LuB12 are diamagnetics whereas the other dodecaborides are ordered antiferromagnetically. The amplitude of the heat capacity discontinuity at the Néel temperature and the shape of the heat capacity variation in the critical region for all these antiferromagnetics are characteristics for amplitude-modulated magnetic structures. In the ordered state TbB12 reveals two first-order phase transitions, most likely due to magnetic structure changes. The heat capacity of ErB12 just below the Néel point shows an anomaly of unclear origin. From the Schottky contribution to the heat capacity we have determined crystal field parameters. They are completely different than that is estimated from Point Charge Model. 相似文献
28.
Danuta Wrbel Andrzej Boguta 《Journal of photochemistry and photobiology. A, Chemistry》2002,150(1-3):67-76
In this paper we describe conversion of light energy into electric energy in a photoelectrochemical cell containing zinc phthalocyanine (ZnPc) dyes. For all dyes investigated in liquid polyvinyl alcohol with dimethyl sulfoxide solution and located in the photoelectrochemical cell the following measurements have been done: absorption, fluorescence, photoacoustic spectra, photovoltaic spectra, kinetics of photocurrent and current–voltage characteristics. It has been shown that all dyes located in the photoelectrochemical cell are able to convert light into electric energy but with different effectiveness. The influence of substituted different peripheral groups to ZnPc core and the correlation between the molecular structure and effectiveness of solar to electric energy conversion were observed and described. The unique behavior of ZnPc substituted with fluorines was indicated. 相似文献
29.
Andrzej Małecki Jalees A.K. Tareen Jean Pierre Doumerc Louis Rabardel Jean Claude Launay 《Journal of solid state chemistry》1985,56(1):49-57
Kinetics of thermal decomposition in vacuum of Co3O4 powder as well as single crystals has been investigated. Discrepancies with the results of previous authors have been discussed. Decomposition of Co3O4 proceeds through formation of a compact layer of CoO and hence diffusion is the rate-limiting factor. The experimental curves α(t) be described for 0.05 < α < 0.85 using a modified Ginstling-Brounshtein equation: 1 ? 2α/3 ? (1 ? α)2/3 = ktn where the activation energy varies with the degree of decomposition. 相似文献
30.
Apparent molar volumes of aqueous solutions of argon and xenon have been calculated using a previously developed comprehensive equation of state for nonelectrolyte systems. The equation consists of a virial expansion truncated after the fourth virial coefficient and a closed-form term approximating higher coefficients. Mixing rules are based on the composition dependence of virial coefficients, which is known from statistical mechanics. The equation accurately represents vapor-liquid and gas-gas equilibria for the Ar+H2O and Xe+H2O systems over wide ranges of pressure and temperature using two binary parameters. With the binary parameters determined from phase equilibrium data, the equation accurately predicts apparent molar volumes V in the near-critical and far-from-critical regions. Apart from reproducing experimental V data, the equation reveals remarkable maxima of V as a function of pressure and temperature in the near-critical region. The implications of this equation with respect to the Ar–H2O potential are discussed via the second virial coefficient. 相似文献