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21.
本文讨论了流动注射-ICP光谱分析中的基体效应和酸效应。当基体(Na、Ca、Fe、Zn)的浓度大于5mg/ml时,待测元素的谱线强度表现出不同程度的降低;上述基体的引入对激发温度和电子密度的影响不明显;基体产生的抑制效应可能与改变了待测元素粒子的激发几率的因素有关;于载流体中加入一定量的基体元素,是消除或降低基体效应的有效方法。酸(HCl、HNO_3、H_2SO_4)对待测元素表现出不同程度的抑制效应,其主要原因是物理干扰所致。 相似文献
22.
Tatiana B. Mikenas Vladimir A. Zakharov Lyudmila G. Echevskaya Mikhail A. Matsko 《Journal of polymer science. Part A, Polymer chemistry》2007,45(22):5057-5066
The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl2/MgCl2‐Al(i‐Bu)3 (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl2/MgCl2‐Al(i‐Bu)3 has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl2/MgCl2‐Al(i‐Bu)3 has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007 相似文献
23.
Sarah E. Reybuck Robert M. Waymouth 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3323-3331
Ethylene/1‐hexene copolymerizations with disiloxane‐bridged metallocenes, rac‐ and meso‐1,1,3,3‐tetramethyldisiloxanediyl‐bis(1‐indenyl)zirconium dichloride (rac‐ 1 , meso‐ 1 ) activated by modified methylaluminoxane were performed to investigate the influence of conformational dynamics on comonomer selectivity. Although 1H NOESY (nuclear Overhauser and exchange spectroscopy) analysis indicated that the most stable conformation for the meso isomer in solution was that in which both indenes project over the metal coordination site, this isomer showed higher 1‐hexene selectivity in copolymerization (re = 140 ± 30, rh = 0.024 ± 0.004) than the rac isomer with only one indene over the coordination site (re = 240 ± 20, rh = 0.005 ± 0.001). The meso isomer showed high 1‐hexene selectivity, a high product of reactivity ratios (rerh = 3.3 ± 0.5) and produced copolymers that could be separated into fractions with different ethylene content suggesting that the active species exhibited multisite behavior and populated conformations with different comonomer selectivities during the copolymerization. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3323–3331, 2004 相似文献
24.
We investigate the electronic properties of multiwalled carbon nanotubes both before and after acid treatment with concentrated sulphuric and nitric acids. Magnetic susceptibility measurements were performed using a SQUID magnetometer and show that there is a considerable enhancement in the density of states at the Fermi level. The data shows that the diamagnetic influence from the graphitic nanotubes dominates. We experimentally observe, after acid treatment, that the diamagnetic susceptibility remains unchanged at 5 K but notably decreases at 77 K. We propose the acid treatment has increased the Van Vleck paramagnetic contribution lowering the diamagnetic response from the π-electron orbital magnetisation. The Van Vleck paramagnetic contribution is finite-temperature dependent with a diminishing contribution at higher fields. 相似文献
25.
Praveen K. Tandon Gayatri Sumita Sahgal Manish Srivastava Santosh B. Singh 《应用有机金属化学》2007,21(3):135-138
Catalytic activities of three transition metals, as iridium (III) chloride, rhodium (III) chloride and palladium (II) chloride, were compared in the oxidation of six aromatic aldehydes (benzaldehyde, p‐chloro benzaldehyde, p‐nitro benzaldehyde, m‐nitro benzaldehyde, p‐methoxy benzaldehyde and cinnamaldehyde), two hydrocarbons (viz. (anthracene and phenanthrene)) and one aromatic and one cyclic alcohol (cyclohexanol and benzyl alcohol) by 50% H2O2. The presence of traces (substrate: catalyst ratio equal to 1:62500 to 1:1961) of the chlorides of iridium(III), rhodium(III) and palladium(II) catalyze these oxidations, resulting in good to excellent yields. It was observed that in most of the cases palladium(II) chloride is the most efficient catalyst. Conditions for the highest and most economical yields were obtained. Deviation from the optimum conditions decreases the yields. Oxidation in aromatic aldehydes is selective at the aldehydeic group only and other groups remain unaffected. This new, simple and economical method, which is environmentally safe, also requires less time. Reactive species of catalysts, existing in the reaction mixture are also discussed. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
26.
Simultaneous DSC-TG and DTA-TG were used to investigate the calatytic effect of the metal on the thermal decomposition of
a cellulose matrix containing small copper particles. The techniques were also used to demonstrate the effect of the metal
particles on the subsequent activation of the carbon matrix, a process which develops the pore structure necessary to expose
the metal particles to the gas phase. Temperature programmed desorption was used to study the initial mass loss found on activation.
To quantify the catalytic effect of the copper particles on the activation process an estimate was made of the activation
energy of the catalysed and uncatalysed reactions. The work gives valuable information on the processes involved in the preparation
of a new range of metal-carbon catalysts.
In celebration of the 60th birthday of Dr. Andrew K. Galwey 相似文献
27.
Piotr Dobrzynski 《Journal of polymer science. Part A, Polymer chemistry》2004,42(8):1886-1900
Lactide polymerization using zirconium(IV) acetylacetonate [Zr(acac)4] as an initiator was investigated. In the reaction between Zr(acac)4 and the monomer molecule, lactide deprotonation and the release of acetylacetone occurred. The structures of the obtained complexes were analyzed with high‐resolution NMR spectroscopy. A computational method was used to calculate the hypothetical structures. The role of the obtained complexes in the initiation of polymerization and the reaction of chain growth was proposed. The influence of the reaction temperature on the structures of the complexes was investigated. Polylactide chain growth proceeded by an insertion‐coordination mechanism. The polymer chain grew on one ligand, which was formed in advance from a deprotonated lactide. The molecular masses of the obtained polymers were the same as the theoretical masses and were directly proportional to the reaction conversion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1886–1900, 2004 相似文献
28.
Reduction of tetranuclear heterometallic complex Mo2Mg2 was simulated using the B3LYP and PBE density functional methods. The results of geometry calculations of the initial complex
[MoVIO2Mg(MeOH)2(OMe)4]2 and a partially reduced MoV complex are in good agreement with experimental data. The reduced MoIII complex is characterized by a decrease in the binding energy of aqua ligands. Structural rearrangement of the complex with
release of a coordination position at the Mo atoms requires small energy expenditure. One can assume that the reduction of
the polynuclear complex causes overcrowding of its coordination sphere, which favors formation of dinitrogen complexes.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–457, March, 2008. 相似文献
29.
Perdigón-Melón J. A. Auroux A. Bonnetot B. 《Journal of Thermal Analysis and Calorimetry》2003,72(2):443-451
As supported palladium oxide catalysts present the best performances in methane combustion in lean conditions, microcalorimetric
studies of the interaction between methane and palladium oxide or metallic palladium supported on Al2O3, ZrO2 and BN have been performed at 673 K. At this temperature methane reduced the palladium oxide, and the heat of reduction of
palladium oxide was shown to depend on the dispersion and on the support. The lowest heats of reduction corresponded to the
highest rates of methane combustion. Moreover methane reforming occurred on metallic palladium, producing hydrogen, and again
methane decomposition was shown to depend on the support.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
30.