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  • 1
    ISSN: 1520-6904
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 258 (1980), S. 793-793 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 14 (1978), S. 99-109 
    ISSN: 1572-8943
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Résumé La cinétique des transformations d'échantillons fraîchement préparés de soufre amorphe et de soufre monoclinique a été étudiée respectivement entre 35 et 45° et entre 25 et 45° à l'aide d'un calorimètre non isotherme non adiabatique. Les résultats expérimentaux peuvent être ajustés à l'équation d'Avrami et les coefficients correspondants ont été calculés. Les résultats obtenus montrent que dans le soufre monoclinique seule la réaction de formation du soufre rhomboédrique s'effectue alors que dans le soufre amorphe deux réactions se produisent: l'une, rapide, consiste en la formation de noyaux S8 et l'autre, lente, consiste en la formation de soufre rhomboédrique.
    Abstract: Zusammenfassung Mittels eines nicht-isotherm — nicht-adiabatischen Kalorimeters wurde die Umwandlungskinetik der frisch bereiteten Proben von amorphen und monoklinen Schwefel in den Temperaturbereichen von 35 bis 45°, bzw. von 25 bis 45° bestimmt. Die Versuchsangaben lassen sich der Avrami-Gleichung anpassen und die Koeffizienten der Gleichung wurden berechnet. Aus den erhaltenen Ergebnissen geht hervor, daß im monoklinen Schwefel sich nur die Bildung von rhombischem Schwefel vollzieht, während im amorphen Schwefel zwei Vorgänge nach einander verlaufen: ein rascher, der aus der Bildung der S8 Ringe und die langsamer, der aus der Bildung von rhombischem Schwefel besteht.
    Notes: Abstract The kinetics of transformations of freshly-prepared amorphous and monoclinic sulphur were determined with a nonisothermal — nonadiabatic calorimeter at 35– 45° and 25–45°, respectively. The experimental data were fitted to the equation of Avrami and the coefficients of the equation were calculated. From the results it was evident that only a process of rhombic sulphur formation proceeds in monoclinic sulphur, while two processes proceed in amorphous sulphur: a rapid one, consisting in the formation of S8 rings from biradical chains, and a slow one, consisting in the formation of rhombic sulphur.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Bulletin of environmental contamination and toxicology 19 (1978), S. 677-683 
    ISSN: 1432-0800
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering , Medicine
    Notes: Summary A new method for the activity measurement of115mCd in biological samples was proposed. After tissues mineralization with 60% perchloric acid and 30% hydropen peroxide (I) or with 0.5 M ethanolic sodium hydroxide (II) the solutions were measured in automatic liquid scintillation counter SL-30 by CERENKOV technique. The channels ratio method was successfully applied for standardization. The recoveries of115mCd varied in the ranges: 93.6–102% and 82.7–99.3 % for method I and II, respectively.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1436-5073
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Summary During the pyrolytic reaction of phosphorus-bearing compounds in an atmosphere of oxygen, there are produced P-oxides, which interfere in the determination of carbon and hydrogen. The behavior of these P-oxides was studied intensively in the empty combustion tube in dependence on temperature, velocity of the carrier gas, the nature of the combustion and the positioning of the tube. The P-oxides were determined by the employment of32P-labelled aniline phosphate and by activation measurement of the32P directly through the tube walls as well as in the finely divided material. In conventional combustions the P-oxides separate abundantly on the walls of the tube provided that the gas velocity is low, especially in those zones of the tube where there is marked temperature lowering, or where very high temperature prevail. Deposited P-oxides are swept out of the tube only in the course of a very long time. Consequently a tube in which the P-bearing compounds have been burned will interfere because of the eluted P-oxides and hence will interfere also if P-free compounds are burned in this same tube.
    Notes: Zusammenfassung Bei pyrolytischer Umsetzung phosphororganischer Verbindungen in Sauerstoffatmosphäre bilden sich P-Oxide, die die CH-Bestimmung stören. Das Verhalten dieser P-Oxide wurde im leeren Verbrennungsrohr in Abhängigkeit von Temperatur, Geschwindigkeit des Trägergases, Art der Verbrennung und Rohrstellung eingehend untersucht. Die P-Oxide wurden durch den Einsatz von32P-markiertem Anilinphosphat und durch Aktivitätsmessung des32P direkt durch die Rohrwandung sowie im feinzerkleinerten Material erfaßt. Die P-Oxide setzen sich reichlich an der Rohrwandung bei konventioneller Verbrennung und bei kleiner Gasgeschwindigkeit ab, besonders in jenen Zonen des Rohres, wo Temperaturerniedrigung stattfindet oder sehr hohe Temperaturen herrschen. Abgesetzte P-Oxide werden durch den Gasstrom im Lauf sehr langer Zeit ausgespült. Deshalb tritt in einem Rohre, in dem P-Verbindungen verbrannt wurden, die störende Wirkung der eluierten P-Oxide auch bei den Analysen phosphorfreier Substanzen in Erscheinung.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 21 (1986), S. 419-423 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The main fragmentation patterns of the phosphorus-containing moiety of bis(5,5-dimethyl-2-oxo-1,3,2-dioxaphosphorinanyl) sulphide, 3, and its isomer P-oxo-P'-thiono-bis(5,5-dimethyl-1,3,2-dioxaphosphorinanyl) oxide, 4, are presented. Isotope studies with 18O, 36S, 34S and 2H indicate that compound 3 undergoes an extensive isomerization prior to fragmentation. The mechanism of this isomerization must involve interaction of at least two molecules, as shown by isotope scrambling experiments.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Kinetik der Austauschreaktion zwischen Amidwasserstoff und Acylgruppe (RCO—) in äquimolaren Mischungen von [2-14C] Caprolactam und N-Acylcaprolactam bei 150°C ohne Lösungsmittel wurde untersucht. Die Länge der aliphatischen Kette in der Acylgruppe hat keinen Einfluß auf die Geschwindigkeitskonstante des Austauschs kex, jedoch wird durch eine Verzweigung dieser Kette kex erhöht. Die Hammett-Korrelation zwischen kex und der Taft-Konstanten σ0 wird erfüllt. Der positive Wert der Reaktionskonstanten zeigt, daß die Geschwindigkeit der Austauschreaktion durch die positive Ladung am Carbonylkohlenstoffatom der Acylgruppe bestimmt wird. Der Reaktionsmechanismus, der die Existenz eines Zwischenproduktes mit protonierter Acylgruppe im Zentrum einschließt, wird diskutiert.
    Notes: The kinetics of exchange reaction between amide hydrogen atom and acyl group (RCO—) in the equimolar mixture of [2-14C] caprolactam  -  N-acylcaprolactam at 150°C without solvent has been studied. The length of the aliphatic chain in the acyl group has no effect on the exchange rate constant kex but branching of this chain increases kex. Hammett's correlation of kex with the Taft constants σ0 was fulfilled. The positive value of the reaction constant shows that the rate of exchange reaction is determined by the extent of the positive charge localized on the carbonyl carbon atom of the acyl group. The mechanism of the reaction involving the occurence of an intermediate product with protonated acyl group in its centre is discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 12 (1980), S. 979-991 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the chlorine isotopic exchange reaction between tetraethylammonium chloride-36Cl and O,O-diarylphosphorochloridates (p-RC6H4O)2POCl or O,O-diarylphosphorochloridothionates (p-RC6H4O)2PSCl has been studied in acetonitrile solution. Good Hammett's correlations of the rate constants with Taft's σ0 constants were obtained. The values of the reaction constants ρ were found identical for phosphoryl and thiophosphoryl compounds. In comparison with oxygen in the phosphoryl group, the sulfur atom exhibits an electron-donating effect (Δσ0 ∼ 0.80). No correlation has been found for the enthalpy and entropy of activation. The effect of the substituents aryloxy groups, oxygen, or sulfur atoms in the phosphoryl group on the kinetics of the SN2-P reaction is discussed. The reactivity of the investigated compounds is determined by the extent of the positive charge localized on the phosphorus atom. The positive charge is formed by the direct interactions of the substituents with the reaction center and the indirect-intramolecular interactions revealed in the structure of the compound.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 9
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants and activation parameters for the isotopic exchange reactions between (PhO)2PSCl and M36Cl (M = Me4N+, Et4N+, n-Bu4N+, Et3HN+, EtH3N+, Li+) in acetonitrile were measured in order to find the effect of the cation nature onthe kinetics of the reaction. The rate constants measured for a range of concentrations of Et3HN36Cl, EtH3N36Cl, and Li36Cl were analyzed using the Acree equation. The equivalent conductance of LiCl in acetonitrile was determined. The nature of the cation has no effect on the mechanism of the reaction. The cation changes only the experimental rate constant proportionally to the dissociation degree of the salt. Smaller values of the rate constant and smaller activation parameters ΔH
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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