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991.
The kinetics of complexation reaction of Cu(II) with 9-ethyl-3-carbazolecarboxaldehyde-thiosemicarbazone (ECCAT) has been
examined spectrophotometrically. The ligand was synthesized for the first time. The complexation reaction was carried out
in a DMF-water medium at 35°C. The complex has maximum absorbance at 393 nm. Kinetic and activation parameters of the complexation
reaction were calculated by the Arrhenius and Eyring equations using the data obtained from investigating the effect of temperature
on reaction rates under the specified conditions. We also proposed reaction rate equations. Based on the studied complexation
reaction, a simple kinetic method for the spectrophotometric determination of copper(II) has been developed. The calibration
graphs are linear in the concentration range 0.2–1.9 μg/mL. The species that caused interference were investigated.
The text was submitted by the authors in English. 相似文献
992.
The basic obstacles for the general use of laser-ablation(LA)-ICP-MS in analytical laboratories are connected with its reproducibility and calibration. A mathematical relation deduced from the correlation function of the analytical signals allows the estimation of the number of craters needed for representative analyses. The procedure was applied to different samples such as manganese crusts and soils. The ion intensities of the major elements in the manganese crusts and nodules were used as internal standards, improving relative standard deviations by factors between 2 and 3. Selected samples of wood and manganese crusts were analyzed by LA-ICP-MS and the results compared with those obtained by solution ICP-MS. The agreement of the values is within the 95% confidence limits. Powdered reference materials and, in the case of wood analysis, cellulose doped with standard solutions were used for the calibration. 相似文献
993.
D. C. Aumann H. J. Born und R. Henkelmann 《Fresenius' Journal of Analytical Chemistry》1966,221(1):101-108
Zusammenfassung Der intensive Fluß schneller Neutronen, wie er von Kernreaktoren geliefert wird, kann für eine rasche und zerstörungsfreie, aktivierungs-analytische Bestimmung einer Vielzahl von Elementen verwendet werden. Bei manchen Elementen läßt sich sogar bei der Aktivierung mit schnellen Reaktorneutronen eine im Vergleich zur Aktivierungsanalyse mit thermischen Neutronen tiefere Erfassungsgrenze erreichen. Werden die Proben in einem schnellen, halbautomatischen Rohrpostsystem zum Reaktorkern befördert, können auch sehr kurzlebige Radionuklide gemessen werden. Besonders Sauerstoff läßt sich über die Kernreaktion 16O(n, p)16N sehr empfindlich bestimmen, wobei die hochenergetischen -Quanten des 7,2 sec Stickstoff-16 gemessen werden. Es können so bis zu 10 ppm Sauerstoff in vielen Arten von Analysenproben erfaßt werden. Das halbautomatische Analysensystem, das mit Hilfe einer schnellen Rohrpost die Durchführung rascher und zerstörungsfreier Aktivierungs-analysen im Forschungsreaktor München erlaubt, wird beschrieben. Die Verwendung des Systems zur Sauerstoffanalyse und die damit zusammenhängenden Probleme werden genauer besprochen.
Summary The intense fast-neutron fluxes, which are available in nuclear reactors, can be used for rapid and non-destructive activation analysis of many elements. Some elements have even superior detection limits for activation with fast reactor neutrons compared to reactor thermal-neutron activation. Short-lived radionuclides can also be measured using a fast pneumatic tube system. Oxygen can be determined by the nuclear reaction 16O(n, p)16N initiated by fast reactor neutrons counting the high-energy gamma rays of the 7.4 sec nitrogen-16. The method is suitable for determining as little as 10 ppm of oxygen in many types of analytical samples. The fast transfer system, which is used in the Munich research reactor for rapid and non-destructive activation analysis is described. The use of the transfer-system for oxygen activation analysis and problems associated with oxygen analysis are discussed.相似文献
994.
1,4-Cyclohexanedione has been determined by reaction with o-phthalaldehyde in sulfuric acid. The determinations depend on the formation of a dicationic salt of pentacenequinone. A sensitive and highly selective fluorimetric method is recommended, but the reaction can also be used spectrophotometrically. Many organic compounds, as well as the isomers of 1,4-cyclohexanedione, give negative results. A spot test is described which can be used for quick preliminary investigations of complex mixtures for I,4-cyclohexanedione. 相似文献
995.
Wytko JA Michels M Zander L Lex J Schmickler H Vogel E 《The Journal of organic chemistry》2000,65(25):8709-8714
In connection with a study aimed at the evaluation of electronic effects in spiro-dicorrole (1a) and its binuclear Ni(II) complex (1b) we became interested in gem-dimethyl-substituted cyclotetrapyrrole (2a) and the corresponding Ni(II) complex (2b). Attempts to prepare 2a as the 12,13,16,17-tetraethyl-2,3,7, 8-tetramethyl derivative (5) by an acid-catalyzed (1 + 1) condensation of dimethyldipyrrylmethane 3 and diformylbipyrrole 4 resulted in the formation of the (2 + 2) and (3 + 3) condensation products, i.e., the cyclooctapyrrole 6 and the cyclododecapyrrole 7, respectively, rather than in that of the desired gem-dimethyl cyclotetrapyrrole. The cyclododecapyrrole 7, isolated as the major product, is among the largest cyclopolypyrroles known to date. These two new macrocycles have been structurally characterized by variable temperature 1D and 2D NMR experiments, as well as by single-crystal X-ray diffraction analysis. In solution both the cyclooctapyrrole 6 and cyclododecapyrrole 7 exhibit dynamic behavior. At 337 K 6 adopts a D(2)-symmetric conformation, whereas at 196 K two equivalent C(2) conformers that interconvert through the D(2)-symmetric intermediate are observed. The energy barrier for the interconversion process between these two degenerate conformers is found to be 10.6 kcal mol(-)(1). The solution dynamics of 7 could be described in an analogous manner, with the time-averaged conformation at 378 K displaying D(3)(h)() symmetry. X-ray analyses showed that for both macrocycles, 6 and 7, the solid state structures were nearly identical to the low-temperature solution conformers. 相似文献
996.
R. Spatz und K. H. Lieser 《Fresenius' Journal of Analytical Chemistry》1977,288(4):267-272
Zusammenfassung Bei Verwendung einer Röntgenröhre mit Sekundärtargets kann durch geeignete Wahl des Sekundärtargets eine hohe Nachweisempfindlichkeit im Bereich bestimmter Ordnungszahlen erreicht werden. Für schwere Elemente ist die Messung der L-Linien vorteilhaft. Bei Verwendung von Radionuklidquellen werden etwa die gleichen Nachweisgrenzen erreicht. Im Bereich hoher Energien sind Radionuklidquellen besonders günstig.
Critical comparison of the measuring range and detection limits in energy-dispersive X-ray fluorescence analysis with tube excitation (secondary target) and with radionuclide excitation (Cd-109 and Am-241), by means of bulk powder samples on silicagel basis as an example
Summary Using a X-ray tube in combination with secondary targets by proper choice of the secondary target high detection limits for ranges of certain atomic numbers are obtained. In the case of heavy elements measurement of L-lines is more favourable. By use of radionuclides as X-ray sources nearly the same detection limits are obtained. In the range of high energies the application of radionuclides has distinct advantages.
Wir danken dem BMFT für finanzielle Unterstützung. 相似文献
997.
The Systems AI/CoI2 (A = Alkali Metal, Tl, Ag) and the Crystal Chemistry of the Double Halides AnCoX(n+2) with X = Cl, Br, I The systems AI/CoI2 (A = Cs, Rb, K, Tl, Na, Ag) were investigated by differencethermal analysis. The systems of NaI and AgI are found to be eutectical. A compound A2CoI4 always exists in the other systems. Cs2CoI4 crystallizes in the β-K2SO4 type with a coordination number (C.N.) for Cs equal to 9/10. Results obtained with single crystal technique reveal for the first time that among the double halides Rb2CoI4 is of the monoclinic Sr2GeS4 type (C. N. for Rb = 6(+2)). The compounds K2CoJ4, Tl2CoJ4, T-K2CoBr4, and T-Tl2CoBr4 are isotypic. Both structure groups are characterized by isolated CoX42? tetrahedra. Reflectance spectra and magnetic susceptibilities can be explained on the basis of crystal field theory. – Our results close presently existing gaps in the knowledge on systems of CoBr2 and CoCl2 too. 相似文献
998.
L. Van Den Enden H.J. Geise H.P. Figeys P. Geerlings C. Van Alsenoy 《Journal of Molecular Structure》1976,33(1):69-77
The structure of tricyclo-(3.1.002,4)exane has been determined by gas phase electron diffraction. The molecule has an inversion centre. The mean carbon—carbon bond length, averaged over both three- and four-membered rings is 1.508 A. A model with equal C-C bond lengths fits to the measured diffraction intensities. The four-membered ring is planar with valency angles of 90°, while the carbon atoms of the three-membered rings form isosceles triangles. Ab initio quantum mechanical calculations at the STO-3G level support this geometry. The valency angle CCC (between three- and four-membered rings) for the equilateral four-membered ring model has been found experimentally to be 109.9°. The average C-H bond distance (1.080 Å) is small as a result of increased s-character in these bonds in agreement with reported INDO—LMO calculations. 相似文献
999.
The rapid determination of chloride and inorganic phosphate in blood serum based on continuous flow spectrophotometry was adapted to Flow Injection Analysis by applying dialysis as well as differential dilution of the injected samples. In addition to the manual injection procedure, an automated microsampling unit was developed and used. By continuous dialysis, chloride could be determined reproducibly at a sampling rate of 125 samples per hour at sample volumes of 60 μl or less. A similar sampling rate and high precision were obtained for the determination of inorganic phosphate by using differential dilution. 相似文献
1000.
In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation. 相似文献