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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 141 (1924), S. 231-283 
    ISSN: 0863-1786
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 169 (1928), S. 321-335 
    ISSN: 0863-1786
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wenn Tantaloxyd mit Kaliumcarbonat geschmolzen und die Auflösung der Schmelze mit Chlornatrium gesättigt wird, fällt 4:3 Natriumtantalat. Nioboxyd, auf gleiche Weise behandelt, ergibt 7:6 Natrinmniobat. Die Niederschläge bilden ein schweres, weißes, mikrokristallinisches Pulver. Die Filtrate enthalten einige Milligramm Erdsäure, welche mittels Neutralisation des Carbonats zu Bicarbonat in heißer Lösung zur Ausflockung gelangen.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Materialwissenschaft und Werkstofftechnik 13 (1982), S. 274-285 
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: The Formation of Surface Films and the Corrosion Resistance of the Silicon Containing Austenitic Steel X 2 CrNiSi 18 15 in Nitric AcidsThe oxide layers consist of two parts: the lower one is mainly Croxide, the upper one is SiO2. ESCA and AAS measurements were made in order to study the formation of the surface layer on the austenitic steel X2 CrNiSi 18 15 in nitric acids. A film, which is chromium oxide, is formed first. On top of this film a second film consisting of SiO2 grows. The elements nickel and manganese are not found in the formation of the oxide films. Immediately below the oxide layer the steel is enrichened with chromium and depleted of iron.In order to find the in some cases very small corrosion rates (5 · 10-5 mm · a-1) in a reproducible manner, the amounts of iron, chromium and nickel which had been dissolved were measured by means of the AAS method as a function of time.For stationary samples apparent activation energies of 65.2 kJ/Mol (azeotropic nitric acid) and 37.5 kJ/Mol (highly concentrated nitric acid), respectively, were found. These data confirm the assumption that the corrosion rate is determined by reactions at the phase boundaries.No appreciable influence of the flow velocity on the corrosion rate was detected.
    Notes: Mit Hilfe von ESCA- und AAS-Messungen wurde die Ausbildung der Deckschicht auf dem austenitischen Stahl X 2 CrNiSi 18 15 in Salpetersäuren untersucht. Es entsteht eine chromoxidreiche Deckschicht, über der sich eine SiO2-Schicht befindet. Nickel und Mangan sind am Aufbau der Oxidschichten nicht beteiligt. Unter der Oxidschicht wurde eine Chromanreicherung bzw. Eisenverarmung im Stahl nachgewiesen.Um die teilweise sehr geringen (bis 5 · 10-5 mm · a-1) Abtragungsraten reproduzierbar erfassen zu können, wurde in Lösung gegangenes Eisen, Chrom und Nickel in Abhängigkeit von der Beanspruchungsdauer mittels AAS bestimmt.Für ruhende Werkstoffproben ergaben sich scheinbare Aktivierungsenergien von 65,2 kJ/Mol (azeotrope Salpetersäure) bzw. 37,5 kJ/Mol (hochkonzentrierte Salpetersäure); diese Werte bestätigen die Annahme einer geschwindigkeitsbestimmenden Phasengrenzreaktion. Ein nennenswerter Einfluß der Fließgeschwindigkeit auf die Korrosion war nicht nachweisbar.
    Additional Material: 20 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: P(III) double bond systems possess two closely spaced frontier orbitals, a π-orbital and a σ-orbital. In the parent iminophosphane the orbital sequence is σ (HOMO) and π* (LUMO). Thus, it is isolabal to a singlet carbene and undergoes self-dimerization via a [2 + 1] cycloaddition. The resulting three membered ring system can be considered as a complex of two iminophosphanes. Contrary to the classical cyclopropanation reaction, in the pseudo-carbene iminophosphane the corresponding [2 + 1] reaction is only slightly exothermic, as established by ab initio calculations at the SCF/CEPA-1 and the MCSCF/ACPF level.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1042-7163
    Keywords: Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The iminophosphane, tBu2P—P=N—NR2 (R=SiMe3), produced by base-catalyzed elimination of ClSiMe3 from the corresponding phosphane, possesses an unusually long PN bond (162 pm), which is in accord with quantum chemical calculations.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 7 (1980), S. 457-463 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isotope dilution calibration curves for the quantitative analysis of organic compounds are determined at one point in time. Future analyses of unknowns are then referred to that single calibration. However, between the time that the calibration was performed and the time that the unknowns are analyzed, numerous changes in mass spectrometric operating conditions have often occurred. These include changes in resolution, mass discrimination, fragmentation patterns due to temperature changes, and electrometer offset. These changes will alter the mass spectrometric response and may reduce the accuracy and precision of the analysis. In order to investigate the effect of the above variations, a mathematical model has been developed which permits the influence of the operating conditions to be quantitated. The mass spectrometric response - i.e. isotope ratio - was very sensitive to changes in operating conditions. Changes in the isotope ratios of mixtures that were comprised predominantly of either the natural abundance compound or the labeled compound varied by up to 50%. However, the use of data reduction procedures that include a correction term for the isotope ratio of either or both of the natural abundance or labeled compound reduced the errors to 5% or less.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 3 (1976), S. 265-271 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The use of linear regression analysis for the reduction of isotope dilution data is reviewed. The calculation of linear regression statistics is based upon four assumptions: zero variance in the independent variable, equal variance for all values of the dependent variable, linearity and continuity. Unfortunately, isotope dilution data often violate one or more of these assumptions, which results in the calculation of an inaccurate calibration line. The inaccuracies can be avoided through careful inspection of the data, including analyses of variance and linearity. Large differences in the variances of the dependent variable require the use of a weighted linear regression. Nonlinearity necessitates either discarding data in the nonlinear portion of the calibration or the calculation and use of atom % excess and dilution instead of the simple isotope ratios.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isotope ratio (IR) mass spectrometry was evaluated for the study of drug metabolism and balance using 13C,15N2- labelled antipyrine (AP) as a test drug. Rats were given 40 mg kg-1 (13C, 15N2)AP intraperitoneally. Breath, urine, faeces and blood were collected. Except for breath, samples were combusted in sealed quartz tubes. The resulting CO2 and N2 were analysed for excess 13C and 15N, relative to pre-dose samples, by IR mass spectrometry. In addition, blood levels of AP and cumulative excretion of urinary AP metabolites were determined by gas chromatography/mass spectrometry/selected ion monitoring (GC/MS/SIM) and high-performance liquid chromatography (HPLC) respectively. Excess 13C and 15N levels in blood were comparable with observed levels of AP, and urinary recoveries of 13C (42%) were in good agreement with those calculated from HPLC data (45%). N-Demethylation, one of the important pathways of AP metabolism, was most rapidly determined by excess 13CO2 excretion in breath (8%). The IR mass spectral analysis complemented gas chromatographic/mass spectrum and HPLC analyses, and was less complex.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 1 (1974), S. 172-174 
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Acetic acid isolated from cider vinegar and inorganically synthesized glacial acetic acid have markedly different intramolecular isotopic distributions of the stable carbon isotopes. Carbon-12 is concentrated in the methyl group relative to the carboxyl group in the biologically produced acid. The reverse distribution is observed in the particular sample of glacial acetic acid examined here.
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 10
    ISSN: 1052-9306
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The precise isotopic analysis of carbon by means of differential comparison of CO2 samples is applied to neutral, acid c and basic extract fractions of human urine. It is shown that the standard deviation of the analytical procedure, including sample preparation steps, is about 1% or 0.001 atom % excess carbon-13, but depends some what on the fraction considered. Day to day variations (expressed as standard deviations) in the isotopic composition of the urine fractions are generally less than 2.8%, 1.4% and 3.9% for the neutral, acidica and basic fractions, respectively, although the effect of unusual dietary inputs can be recognized. The ingestion of 23 μg excess carbon-13 in the form of isotopically labelled aspirin is shown to perturb significantly the isotopic composition of the acidic urine fraction which, for a 24 hour collection period, had a mass of 570 mg C. Because only 0.01% of the fraction was consumed by isotopic analysis, further extensive analysis would be possible. It is concluded that carbon-13 tracer experiments generally should be arranged to provide at least 5 × 10-5 g excess 13C/g carbon in any fraction which is to be used for lable detection.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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