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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 11 (1982), S. 823-830 
    ISSN: 1572-8927
    Keywords: Excess Gibbs free energy ; activity coefficient at infinite dilution ; benzene ; alkane ; Pade approximant ; n-tetradecane ; vapor pressures
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Vapor pressures for the benzene+n-tetradecane system have been measured using a static apparatus. The excess Gibbs free energy was calculated using a modified Barker method and a Pade approximant equation. The selection of the most adequate approximation is discussed. Results are compared with those corresponding to other thermodynamic properties. The activity coefficient of benzene at infinite dilution calculated from these data agrees well with the value obtained from the literature.
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  • 2
    ISSN: 1572-8927
    Keywords: Excess functions ; liquid mixtures ; Flory's X 12 parameter ; excess volume ; excess heat of mixing ; isothermal compressibility ; Prigogine-Flory theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The isothermal compressibilities KT for cyclohexane + benzene, cyclohexane + toluene and benzene + toluene systems at 25, 35, 45 and 60°C have been used to test the Prigogine-Flory theory using Van der Waals and Lennard-Jones energy potentials. Flory's energy parameter X 12 was calculated for these systems at the four temperatures. From X 12 for the equimolar mixture, the following excess functions were calculated: (∂VE/∂p)T which is related to K T E , the heat of mixing H E , and the excess volume V E . The theory and any of the two potentials give (∂VE/∂p)T which fit the experimental data, but H E and V E , calculated using the same X 12 parameter, depart appreciably from the experimental data even though they agree in sign and have the essential features of the excess functions. The departure is apparent in both magnitude (in particular for the cyclohexane + benzene, and cyclohexane + toluene systems) and in the temperature dependence. The conclusion is that the X 12 parameter does not predict the thermodynamic properties of these systems and the Lennard-Jones potential, involving a more complicated expression, does not contribute any improvement over the Van der Waals potential.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of solution chemistry 11 (1982), S. 557-564 
    ISSN: 1572-8927
    Keywords: Compressibility ; cyclohexane ; toluene ; temperature dependence
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The isothermal compressibilities κT for cyclohexane+toluene mixtures at 25, 35, 45 and 60°C have been determined by direct piezometric measurement. By combining our results with supplementary literature data, we have calculated the isentropic compressibility κS. Values of the excess functions (∂VE/∂p)T, κ T E and κ S E were also calculated at four temperatures and their behavior as a function of mole fraction and temperature was studied.
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  • 4
    ISSN: 1434-4475
    Keywords: Kinetics of nitrosation ; N-Nitrosation ofN-methylacetamide ; Proton transfer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Kinetik der Nitrosierung vonN-Methylacetamid wurde mittels Spektrophotometrie untersucht. Es wurden signifikante Unterschiede zum Mechanismus der Nitrosierung von Aminen beobachtet: die Abwesenheit einer Katalyse durch Halogenide, die Existenz einer generellen basischen Katalyse durch Acetat und dessen chlorierten Derivaten unter Übereinstimmung mit demBrønstedschen Gesetz (mit β=0,49) und einem beobachtbaren Isotopeneffekt (mit einem Verhältnis von 7,9 zwischen den Geschwindigkeitskonstanten in H2O und D2O). All das zeigt an, daß der geschwindigkeitsbestimmende Schritt im Mechanismus der Transfer eines Protons vom protonierten Nitrosamid zum Reaktionsmedium sein muß.
    Notes: Abstract The kinetics of the nitrosation ofN-methylacetamide have been studied using spectrophotometry. Significant differences with respect to the mechanism of nitrosation of amines were observed: the absence of catalysis by halides, the existence of general basic catalysis by acetate and its chlorated derivatives obeyingBrønsted's law (with β=0.49), and the primary isotopic effect (with a ratio of 7.9 between the rate constants for the elementary process in H2O and D2O). All this indicates that the slow step of the mechanism must be the transfer of a proton from the protonated nitrosamide to the reaction medium.
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Monatshefte für Chemie 115 (1984), S. 155-163 
    ISSN: 1434-4475
    Keywords: Acetic acid/acetate ion buffer ; Kinetics of nitrosation ; Medium effect ; Morpholine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Essigsäure/Acetat-Puffer wirkt bei der Nitrosierung von Aminen katalytisch, unter Bedingungen, wo die alleinigen nitrosierenden Agentien N2O3 und NOBr sind; andererseits wird die Nitrosierung durch H2NO 2 + unterbunden. Die kinetischen Charakteristika dieses Phänomens wurden quantitativ analysiert und mit ähnlichen Effekten der LösungsmittelTHF, DMSO und Dioxan verglichen. Die experimentellen Ergebnisse zeigen, daß dieses Verhalten auf einen Mediumeffekt zurückzuführen ist.
    Notes: Abstract Acetic acid/acetate ion buffer acts catalytically upon the nitrosation of amines under conditions in which the only nitrosating agents are N2O3 and NOBr, but inhibits nitrosation by H2NO 2 + . The kinetic characteristics of these phenomena have been analysed quantitatively and compared with similar effects caused by the solventsTHF, DMSO and dioxane. The experimental results show that this behaviour is an effect of the medium.
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  • 6
    ISSN: 1436-5073
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die fluorimetrische Bestimmung von Bromat im Nanogrammbereich auf der Grundlage der Oxydation von 1,2,4-Trihydroxyanthrachinon-3-carbonsäure in schwefelsaurer Lösung wurde beschrieben. Die Fluoreszenz wird bei 585 nm gemessen (Anregung bei 521 nm). Die Erfassungsgrenze liegt bei 5 ng/ml. Das Verfahren ist somit das empfindlichste unter allen bekannten Methoden zur photometrischen bzw. fluorimetrischen Bestimmung dieses Anions.
    Notes: Summary A method is described for the fluorimetric determination of BrO3, at the nanogram level, based on the oxidation of 1,2,4-tri-hydroxyanthraquinone-3-carboxylic acid in sulfuric acid medium. The fluorescence emission is monitored at 585 nm (wavelength of excitation 521 nm). The method shows a detection limit of 5 ng/ml, being the most sensitive of all the established methods for the determination of this anion by photometry and fluorimetry.
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  • 7
    Electronic Resource
    Electronic Resource
    Springer
    Microchimica acta 84 (1984), S. 79-86 
    ISSN: 1436-5073
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Ein neues Verfahren zur fluorimetrischen Bestimmung von Ga(III) mit 1-Hydroxy-2-carboxyanthrachinon bei pH 3,9 in wäßrigem Ethanol wurde ausgearbeitet. Die Fluoreszenz wurde bei 580 nm gemessen (Anregung bei 465 nm). Das Verfahren eignet sich für 50–500 ng/ml. Die Zusammensetzung der Komplexverbindung entspricht dem Verhältnis 1∶1.
    Notes: Summary The fluorescent chelate formed between 1-hydroxy-2-carboxy-anthraquinone and gallium(III) at pH 3.9 has been studied spectrofluorimetrically in an ethanol-water mixture (70/30% V/V). A new method for the fluorimetric determination of gallium(III) is described. The fluorescence is monitored at 580 nm (wavelength of excitation 465 nm) and the range of application of the method is between 50 and 500 ng ml−1. The stoichiometry of the complex has been found to be 1∶1.
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  • 8
    ISSN: 1434-4475
    Keywords: Diamine estrogenic complexes ; Palladium(II) complexes ; Platinum(II) complexes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wird über die Darstellung voncis-Dichlor-Pt(II)- undcis-Dichlor-Pd(II)-Komplexen mitN-[3-Hydroxyestra 1:3:5 (10)trien-17β]ethylendiamin,N-[3-Hydroxyestra 1:3:5 (10) trien-17β]1,3-propylendiamin undN-[3-Hydroxyestra 1:3:5 (10)trien-17β]2-aminomethylpyridin berichtet. Die Komplexe wurden mittels chemischer Analyse, IR und Leitfähigkeitsmessungen charakterisiert.
    Notes: Abstract The preparation ofcis-dichloro Pt(II) andcis-dichloro Pd(II) complexes ofN-[3-hydroxyestra 1:3:5 (10)trien-17β]ethylendiamine,N-[3-hydroxyestra 1:3:5 (10)trien-17β]1,3-propylendiamine, andN-[3-hydroxyestra 1:3:5 (10)trien-17β]2-aminomethylpyridine is reported. The complexes have been characterized by chemical analysis, infrared spectroscopy and molar conductivity.
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  • 9
    Electronic Resource
    Electronic Resource
    Springer
    Foundations of physics 12 (1982), S. 441-465 
    ISSN: 1572-9516
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract By making use of the method of moments we study some aspects of the statistical behavior of the nonrelativistic harmonic oscillator according to stochastic electrodynamics. We show that the random rotations induced on the particle by the zero-point field account for the magnitude of the spin of the electron, the result differing from the correct one(3/4)h 2 by a factor of2. Assuming that the measurement of a spin projection may be effectively taken into account by considering the action of only the subensemble of the field with the corresponding circular polarization, the calculated value of the spin projection comes out to be the correct one within a factor of order unity. The radiative corrections give rise to both the Lamb shift and the anomalous magnetic moment of the electron, the latter being evaluated to within a factor of2. The magnetic and gyromagnetic properties of the electron come out to be in agreement with quantum mechanics. Interference effects are shown to occur when evaluating the average value of the square of the angular momentum.
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  • 10
    Electronic Resource
    Electronic Resource
    Springer
    Algebra universalis 16 (1983), S. 186-194 
    ISSN: 1420-8911
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mathematics
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