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991.
The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (1,3CH2), the additions of carbenes (1,3CH2 and1,3CF2) as well as amino radicals (2NH2 and2NF2) toward ethylene, and the hydrogen abstractions by methylenes (1,3CH2), nitrene (3NH), and hydroxyl radical (2OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions. 相似文献
992.
Rudolf Wagner 《Fresenius' Journal of Analytical Chemistry》1976,282(4):315-321
Summary Problems, techniques and means of water sampling are reviewed. Applicability and performance are discussed with regard to individual and composite samples, and also to automatic sampling. Storage and preservation of samples are dealt with.
Probenahme und Behandlung von ProbenWasser
Zusammenfassung Probleme, Verfahren und Hilfsmittel bei der Probenahme von Wasser werden behandelt. Ausführung und Anwendbarkeit von Einzel und Mischproben sowie der automatischen Probenahme werden diskutiert, ebenso die Aufbewahrung und Konservierung von Proben.
Start of discussion held at the 6th Annual Symposium on Recent Advances in the Analytical Chemistry of Pollutants, April 21–23, 1976; Vienna, Austria. 相似文献
993.
Summary The influence of chemical reactions in d.c. arc plasma on the atomic emission determination of traces has been investigated. The effect of added NH4F on the intensity of spectral lines of Ca and Al was examined. A decrease of the spectral line intensities of Ca and Al in the presence of NH4F occurred, if the sample had not been mixed in the electrode with NH4F. The AlF band spectrum, transition A
1
X
1
, was observed in absorption of the arc radiation. Further, the axial intensity distribution of Ca, Al, Ga and Ag spectral lines and of the head of the green system of CaF band, has been measured. The depressive effect of fluorine on spectral line intensities of Ca, Al, Ga and Ag has to be connected with the processes in plasma. It is suggested that the formation of fluoride radicals could take part in this effect.
Bildung von CaF und AlF im Bogenplasma und spektrochemische Bestimmung von Ca und Al
Zusammenfassung Der Einfluß von chemischen Reaktionen im Lichtbogenplasma auf die spektrochemische Spurenanalyse wurde erörtert. Die Wirkung einer Zugabe von Ammoniumfluorid auf die Intensitäten der Spektrallinien des Calciums und Aluminiums wurde untersucht. Wenn die Probe nicht in der Elektrode mit NH4F gemischt war, wurde eine Intensitätserniedrigung von Ca- und Al-Spektrallinien in Anwesenheit von NH4F beobachtet. Das AlF-Bandenspektrum, Übergang A 1 X 1 , wurde in Absorption der Bogenstrahlung beobachtet. Die Axialverteilung der Linienintensitäten von Ca, Al, Ga und Ag wie auch der Intensität der Kante des grünen Systems der CaF-Banden wurde untersucht. Die depressive Wirkung des Fluors auf die Linienintensitäten von Ca, Al, Ga und Ag sollte mit den Vorgängen im Plasma in Zusammenhang gebracht werden. Es kann vorausgesetzt werden, daß die Bildung der Fluoridradikale bei diesem Effekt eine Rolle spielt.相似文献
994.
Simon G. Bott Ulrich Kynast Jerry L. Atwood 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(3):241-246
18-crown-6 reacts with TiCl3 in CH2Cl2 to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH2Cl2 adduct belong to the monoclinic space groupP21/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and
calc = 1.51 g cm–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages). 相似文献
995.
A heated injection system for a microprocessor-controlled GC has been developed for the (GC)2 analysis of the volatile phase of whole smoke of a cigarette. Effects of injection port temperature and the presence of a Cambridge filter pad are demonstrated. Chromatograms are shown for smoke samples with and without a Cambridge Filter with the sample valve oven at 25°, 165° and 205°C. The use of a flame ionization and a nitrogen-phosphorous detector is illustrated. 相似文献
996.
A method for the determination of cadmium microamounts in mixtures with metallic ions withE
1/2 near toE
1/2 of cadmium is discussed. For higher selectivity cadmium was extracted in the form of the pyridin-thiocyanate complexes prior to polarography.
Bestimmung von Cadmium(II) neben anderen Metallionen
Zusammenfassung Es wird eine polarographische Methode zur Bestimmung von Cd(II) neben anderen Metallionen mitE 1/2 naheE 1/2(Cd) diskutiert. Zur Erhöhung der Selektivität und Genauigkeit wird eine Pyridin-Thiocyanat-Extraktion vorgeschalten.相似文献
997.
998.
利用水热合成技术成功制备出一种新型多钒硼氧化合物, 用X射线单晶衍射分析技术对其晶体结构和分子结构进行了确定。结果表明在该化合物中多钒硼氧阴离子具有一个新颖的三明治结构。上下两个结构单元都是由六个VO5四角锥交替地通过顺式和反式共边的方式连接起来构成的一个钒氧三角形结构。中间的结构单元是由BO3平面三角形和BO4四面体以共角的方式相互连接形成的一个折叠型的B18O36(OH)6环。三明治结构中层与层之间通过桥氧相连。一个水分子处于它的核心位置上,与每个VO5四角锥中的钒原子都保持几乎相等的距离。该化合物及其晶体中存在着丰富的化学结构和成键信息,同时也有作为氧化还原反应催化剂的潜能。 相似文献
999.
A. M. Churakov A. Yu. Tyurin E. L. Goncharova S. L. Ioffe Yu. A. Strelenko V. A. Tartakovsky 《Russian Chemical Bulletin》1995,44(5):890-896
The addition of 1-aryl-2-bromodiazene 1-oxides to olefins yields 1-aryl-2-(2-bromoalkyl)diazene 1-oxides (4). A radical mechanism of the reaction has been suggested. Compounds4 decompose to give bromohydrazones of formaldehyde and aldehydes. The structural factors that affect the rate of this process are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 917–923, May, 1995.The work was carried out in the Scientific Educational Center of the Institute of Organic Chemistry of the RAS with financial support of the Russian Foundation for Basic Research (Project No. 93-03-18461). 相似文献
1000.
B. L. Tumanskii V. V. Bashilov N. N. Bubnov S. P. Solodovnikov V. I. Sokolov 《Russian Chemical Bulletin》1994,43(5):884-886
Using ESR spectroscopy, the reaction of P(O)(OPri)2 phosphoryl radicals with C60ML2 (M=Pd, Pt) was studied and the spin-adducts formed were shown to be unstable under the reaction conditions. The 5-addition of Pt(PPh3)4 to the dimer of phosphorylfullerenyl radicals results in metal-containing dimers (RO)2(O)PL2MC60-C60ML2P(O)(OR)2, which dissociate when exposed to visible light to afford C60ML2P(O)(OR)2 radicals; ML2 in these complexes is located in different positions in relation to the radical center. As a result, the ESR spectra contain the superposition of at least five signals of radicals that differ in HFS constants andg-factors.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 938–940, May, 1994.The present work was supported by the Russian Foundation for Basic Research (Projects 93-03-18725 and 93-03-4101). 相似文献