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101.
Reactions of Iron Trichloride with Trithyazyl Chloride. Crystal Structure of [S4N4Cl]+[FeCl4]? Iron trichloride reacts with (NSCl)3 yielding S4N4[FeCl4]2, S3N3Cl2[FeCl4] or S4N4Cl[FeCl4], depending on the reaction conditions. The i.r. spectra prove the presence of [FeCl4]? ions for all three compounds. The 57Fe-Mössbauer spectra show a slight quadrupole splitting at 80 K for S3N3Cl2[FeCl4] (ΔEQ = 0.42 mm · s?1) and S4N4Cl[FeCl4] (ΔEQ = 0.23 mm · s?1), which indicates a slight deformation of the FeCl4? tetrahedra. The crystal structure of S4N4Cl[FeCl4] was determined and refined with X-ray diffraction data (2549 independent reflexions, R = 0.026). S4N4Cl[FeCl4] crystallizes in the triclinic space group P1 with two formula units per unit cell. The lattice constants are a = 712, b = 911, c = 1006 pm, α = 76.5°, β = 83.8° and γ = 80.5°. The structure consists of the so far unknown [S4N4Cl]⊕ cations and slightly deformed FeCl4? ions. The [S4N4Cl]⊕ ion consists of a S4N4 ring built up of two nearly planar S3N2 fragments having a dihedral angle of 136°. The average SN bond length is 157 pm, the SCI bond length 214 pm. 相似文献
102.
O. G. Koch 《Fresenius' Journal of Analytical Chemistry》1977,286(1-2):14-19
Zusammenfassung Es wird eine automatisierte Apparatur zur schnellen, massenspektrometrischen Bestimmung von Sauerstoff und Stickstoff in Stahl beschrieben. Die Stahlprobe wird unter Argon im Gleichstrombogen geschmolzen und die extrahierten Gase Kohlenmonoxid und Stickstoff werden massenspektrometrisch bestimmt. Die relative Standardabweichung beträgt ±3–5% für Sauerstoff und ±3–8% für Stickstoff. Die Nachweisgrenzen liegen bei 10 pp106 O2 und 3 pp106 N2. Der Zeitbedarf für eine Analyse beträgt 85 s.Herrn H. Siffrin danke ich für die sorgfältige Durchführung der zahlreichen Versuche. 相似文献
103.
The optical constants in the photon energy range between 4 and 10.5 eV for E ?b on (001) and E ?L and E ⊥ L on the (010) plane are discussed. In particular the influence of macroscopic fields on the optical properties of anisotropic crystals is considered. For E ? a on the (001) plane reflection spectra have been measured at various angles of incidence. These data and results obtained recently by Hymowitz and Clark for several artificially prepared crystal faces are discussed on the basis of the frequency dependend dielectric functions. New information on the directional dispersion of exciton bands is thus obtained. 相似文献
104.
Yi SS Reichert EL Holthausen MC Koch W Weisshaar JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(12):2232-2245
A pulsed beam of Co+(3F4) crosses a pulsed beam of C3H8 or C3D8 gas under single collision conditions at collision energies of 0.01 eV and 0.21 eV. After a variable time delay t(ext) = 1-8 micros a fast high voltage pulse extracts product ions into a field-free flight tube for mass analysis. Consistent with earlier work, we observe prompt CoC3H6+ +H2 elimination products in 3:1 excess over CoC2H4+ +CH4 products at 0.21 eV on a 2-10 micros time scale. Long-lived CoC3H8+ complexes fragment predominantly back to Co+ +C3H8 reactants and to H2 elimination products on a 6-24 micros time scale. Density functional theory (B3LYP) calculations provide energies, geometries, and harmonic vibrational frequencies at key stationary points for use in a statistical rate model of the reaction. By adjusting two key multicenter transition state (MCTS) energies downward by 4-7 kcal mol(-1), we obtain good agreement with our decay time results and with the cross section versus collision energy of Armentrout and co-workers from 0.1-1.0 eV. B3LYP theory succeeds in finding relative energies of the MCTSs leading to CH4 and H2 in the proper order to explain the different product branching ratio for Co+ (which favors H2 over CH4) compared with its nearest neighbors Fe+ and Ni+ (which favor CH4 over H2). 相似文献
105.
G. Czerwenka R. Koch und E. Scheubeck 《Fresenius' Journal of Analytical Chemistry》1976,279(4):269-273
Zusammenfassung Die Anwendung einer chloridionensensitiven Elektrode für die direktpotentiometrische Chloridbestimmung in galvanischen BÄdern wird beschrieben und eine genaue Arbeitsvorschrift sowie drei verschiedene Auswerteverfahren angegeben. Die Messungen wurden in einem Bereich von 30–250 mg Cl– je Liter Badlösung an Modellösungen durchgeführt. Die einzelnen Methoden ergaben eine Standardabweichung von ±2,1 mg bei Verwendung einer Eichkurve, ±2,2 mg beim Standardzusatzverfahren und ±3,6 mg bei der Direktablesung auf einer logarithmisch geteilten Skala eines mV-Meters. Ebenso wurden Messungen an einer Reihe von Badproben durchgeführt.Für wertvolle Anregungen und Diskussionen danken wir Herrn Schwank, Siemens AG, Abt. Informationselektronik. 相似文献
106.
Genetically modified organisms (GMOs) entered the European food market in 1996. Current legislation demands the labeling of food products if they contain <1% GMO, as assessed for each ingredient of the product. To create confidence in the testing methods and to complement enforcement requirements, there is an urgent need for internationally validated methods, which could serve as reference methods. To date, several methods have been submitted to validation trials at an international level; approaches now exist that can be used in different circumstances and for different food matrixes. Moreover, the requirement for the formal validation of methods is clearly accepted; several national and international bodies are active in organizing studies. Further validation studies, especially on the quantitative polymerase chain reaction methods, need to be performed to cover the rising demand for new extraction methods and other background matrixes, as well as for novel GMO constructs. 相似文献
107.
C. Kelbch R. Koch S. Hagmann K. Ullmann H. Schmidt-Böcking C. O. Reinhold D. R. Schultz R. E. Olson G. Kraft 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1992,22(4):713-721
Double differential cross sections for the emission of Delta-electrons have been measured in fast uranium-rare gas collisions. The well-known Binary Encounter peak reveals unexpected structures for certain observation angles and its intensity increases towards smaller angles, which is in contradiction to results and scaling laws obtained by experiments with light ion impact. The observed dependencies are fairly well described by recent calculations in the framework of IA and CTMC. From systematic experimental as well as theoretical studies we can derive that the potential of the partially stripped projectile ion gives rise to rainbow and glory scattering of the target electron in the field of the projectile. The rainbow scattering is observed in the laboratory frame as pronounced interference structures, whereas the glory scattering is responsible for the steep increase of the cross sections for binary-encounter electrons towards small laboratory ejection angles. The observed effects have a dramatic influence on the commonq 2 scaling laws derived from experiments with light ions. Furthermore, since the binary-encounter electrons ejected at forward angles have approximately twice the projectile velocity, these new phenomena have an important influence on the electronic stopping power of heavy ions and therefore have to be taken into account for the investigation of radiation damage by these ions e.g. in biological matter. 相似文献
108.
2-Mercapthoethanol undergoes carbonylation in pyridine solution in the presence of oxygen and of [Ni(CO)3Pyl as a catalyst to give cyclic O, S-ethylelnethiorcarbonate. The isolation of thiolatonickel compound [Ni(SCH2CH2OH)2] by the oxidation of a solution containing [Ni(CO)3Py] and 2-mercaptoethanol, and its reaction with carbon monoxide to give the cyclic thiocarbonate and [Ni(CO)3Py] prove that the reaction proceeds in at least two steps. 相似文献
109.
Reactions of Uranium Pentabromide. Crystal Structures of PPh4[UBr6], PPh4[UBr6] · 2CCl4, (PPh4)2[UBr6] · 4CH3CN, and (PPh4)2[UO2Br4] · 2CH2Cl2 PPh4[UBr6] and PPh4[UBr6] · 2CCl4 were obtained from UBr5 · CH3CN and tetraphenylphosphonium bromide in dichloromethane, the latter being precipitated by CCl4. Their crystal structures were determined by X-ray diffraction. PPh4[UBr6]: 2101 observed reflexions, R = 0.090, space group C2/c, Z = 4, a = 2315.5, b = 695.0, c = 1805.2 pm, β = 96.38°. PPh4[UBr6] · 2CCl4: 2973 reflexions, R = 0.074, space group P21/c, Z = 4, a = 1111.5, b = 2114.2, c = 1718.7 pm, β = 95.42°. Hydrogen sulfide reduces uranium pentabromide to uranium tetrabromide. Upon evaporation, bromide is evolved from solutions of UBr5 with 1 or more then 3 mol equivalents of acetonitrile in dichlormethane yielding UBr4 · CH3CN and UBr4 · 3CH3CN, respectively. These react with PPh4Br in acetonitrile affording (PPh4)2[UBr6] · 4CH3CN, the crystal structure of which was determined: 2663 reflexions, R = 0.050, space group P21/c, Z = 2, a = 981.8, b = 2010.1, c = 1549.3 pm, β = 98.79°. By reduction of uranium pentabromide with tetraethylammonium hydrogen sulfide in dichloromethane (NEt4)2[U2Br10] was obtained; (PPh4)2[U2Br10] formed from UBr4 and PPh4Br in CH2Cl2. Both compounds are extremely sensitive towards moisture and oxygen. The crystal structure of the oxydation product of the latter compound, (PPh4)2[U02Br4]· 2 CH2Cl2, was determined: 2163 reflexions, R = 0.083, space group C2/c, Z = 4, a = 2006.3, b = 1320.6, c = 2042,5 pm, β = 98.78°. Mean values for the UBr bond lengths in the octahedral anions are 266.2 pm for UBr6-, 276.7 pm for UBr62? and 282.5 pm for UO2Br42? 相似文献
110.