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  • Wiley-Blackwell  (879)
  • Cambridge University Press  (172)
  • 1985-1989  (1,051)
  • 1960-1964
  • 1955-1959
  • 1985  (1,051)
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  • 1985-1989  (1,051)
  • 1960-1964
  • 1955-1959
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 487-504 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Derivatization of Amines with 4-Substitured 7-NitrobenzofurazansElectrophilc derivatives of 4-nitro-benzofurazan with different reactivities were used to synthesize 28 new mono- and disubstituted 4-amino-7-nitrobenzofurazans 2b, 2d, 2f-2i, 2l, 2m-2n, 3b-3f, 3h-3j, 4e-4d, 4f-4k, 4m, 4o-4p. A reaction mechanism is proposed on the basis of the differences of the reactivities and a preliminary kinetic examination. The acid character of the N—H-function in monosubstituted compounds is demonstrated by means of spectroscopical investigation of pKa-values.Data from i.r., u. v./vis, and fluorescence studies are offered.
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 45-50 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electrochemical Carboxylation of Cinnamoyl-1,1-bis(alkylthio)ethylenesCinnamoyl-1,1-bis(alkylthio)ethylenes (1a-1h) are reduced electrochemically in the presence of carbondioxide in aprotic media. The attack of CO2 takes place either in 1- or 5-position of cinnamoyl-1, 1-bis(alkylthio)ethylenes (1a-1h) depending on the nature of the aryl substituents. If CO2 reacts in position 1 carbonic acids 3 are obtained, reaction of carbondioxide in 5- position leads to the acids 2. The effects of different aryl substituents on the halfwave potentials and the preparative electrolyses have been investigated.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 51-62 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Photochemistry of Aminoketones. VIII. Diastereoselective Synthesis of 3-Hydroxy-prolinesGlycine esters react in two steps (aminoalkylation and N-acylation) to N-acyl-N-(β-benzoylethyl)-glycine ester 3. In less polar solvents these ketonic compounds are n,π*-excited by 300 nm irradiation. In ether 3* yield mixtures of aminocyclopropanoles 4, hydroxyprolines 5 and products of additions and cleavages. In benzene and cyclohexane/benzene, respectively, the regioselective photocyclization to 5 is favoured. Furthermore this hydroxyproline synthesis has the advantages of high diastereoselectivity yielding the (2,3) E-5 and of high overall-yields in connection with the one pot method. The influence of solvents and substituents on the regio- and diastereoselectivity are explained using a model with stabilization of special conformations of intermediates by dipol-dipol interactions.
    Additional Material: 3 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 327 (1985), S. 823-828 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Electrochemical Cleavage of 3-Halogen-1,2,4-thiadiazoles to Cyanimidothiocarbonates3-Halogen-1,2,4-thiadiazole-5-sulfenylchlorides (5a-j) are easily accessible by the halogenation of eyanimidodithiocarbonates (1). As electrophilic synthetic building blocks they react with basic olefines or electron-rich aromates to the corresponding alkylthio-or arylthio derivatives. The electrochemical reduction of these compounds led to substituted cyanimidomithiocarbonates (7a-e), not being accessible otherwise.
    Additional Material: 2 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 36 (1985), S. 203-215 
    ISSN: 0947-5117
    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: Stress corrosion cracking of unalloyed steels in liquid ammoniaIn this work is reported on investigations about stress corrosion cracking of steels in liquid ammonia aimed at ascertaining the parameters and the ranges within which they are effective, finding the mechanism responsible for the damage of spherical pressure vessels and developing protective measures. The investigations are based partly on corrosion tests in which welded Jones samples of various unalloyed and low alloyed steels in different states of heat treatment were immersed in ammonia for long periods in a spherical ammonia storage vessel.For laboratory tests we used an apparatus specially developed to enable round tensile test bars to be tested in liquid ammonia under CERT conditions at the open circuit potential and under electrochemical control. In these tests selectively added impurities were determined quantitatively by gas chromatography.The results of the investigations show that the oxygen content of the ammonia has a decisive influence on the initiation of stress corrosion cracking in unalloyed steels. Even low O2 concentrations (ßß2 ppm) lead to a risk of stress corrosion cracking. Addition of water in sufficient quantity inhibits the stress corrosion cracking.The water concentration needed to inhibit corrosion differs according to the material concerned (StE 355: 〉 500 ppm; H I: 〉 650 ppm; StE 460: 〉 1000 ppm H2O). The different stress corrosion behaviour of the investigated steels under residual and operating stresses shows their different sensitivity. So in absence of stress relieve heat treatment only Jones samples of StE 355 remained crack-free.Investigations into the influence of potential on crack formation showed that the damage follows an anodic crack formation mechanism, since it is capable of being reinforced anodically and inhibited cathodically. Similarly the inhibitive effect of water is reduced by anodic polarization. But stress corrosion cracking cannot be induced by anodic polarization alone, i.e. in the absence of O2.As a practical conclusion it may be said that the presence of oxygen - even in traces - must be avoided.Addition of water inhibits stress corrosion cracking; these additions are therefore recommended wherever they are possible.Containers should be made of StE 355 and they should be stress relieve annealed.Cathodic protection is considered appropriate, but the practicability under operating conditions has to be still investigated.
    Notes: In dieser Arbeit wird über Untersuchungen zur SpRK von Stählen in flüssigem Ammoniak berichtet, deren Ziel es war, Einflußgrößen und ihre Wirkgrenzen zu bestimmen, Aufschluß über den Mechanismus der an Kugeldruckbehältern aufgetretenen Schäden zu erlangen und Schutzmaßnahmen zu ermitteln. Zu diesem Zweck wurden langzeitige Auslagerungsversuche mit geschweißten Jones-Proben aus verschiedenen unlegierten und niedriglegierten Stählen unterschiedlicher Wärmebehandlungszustände in einer Ammoniakkugel durchgeführt.Für Laborversuche wurde eigens eine Apparatur entwickelt, mit der Untersuchungen in flüssigem Ammoniak an Rundzugstäben unter CERTConstant Extension Rate Test-Bedingungen beim Freien Korrosionspotential und unter elektrochemischer Kontrolle durchgeführt werden konnten. Gezielt zugesetzte Verunreinigungen wurden hierbei mittels eines Gaschromatographen quantitativ bestimmt.Aus den Untersuchungen geht der entscheidende Einfluß des Sauerstoffgehalts im Ammoniak auf die Entstehung von Spannungsrißkorrosion an unlegierten Stählen hervor. Bereits geringe O2-Mengen (ßß 2 ppm) bewirken eine Spannungsrißkorrosionsgefahr. Wassergehalte können die Spannungsrißkorrosion inhibieren. Hierbei werden bezüglich der erforderlichen Menge Unterschiede zwischen den einzelnen Werkstoffen sichtbar (StE 355: 〉 500 ppm, H I: 〉 650 ppm, StE 460: 〉 1000 ppm H2O). Eine werkstoffseitige Differenzierung wird auch in bezug auf den Einfluß von Eigen- und Betriebsspannungen deutlich. Lediglich Jones-Proben aus StE 355 blieben ohne Spannungsarmglühung rißfrei.Versuche zur Potentialabhängigkeit der Rißbildung weisen aus, daß die Schädigung einem anodischen Rißbildungsmechanismus folgt, da sie anodisch verstärkt und kathodisch verhindert werden kann. Ebenso wird die inhibitive Wirkung des Wassers durch eine anodische Polarisation eingeschränkt. Jedoch ist durch anodische Polarisation allein, d.h. ohne Gegenwart von O2, Spannungsrißkorrosion nicht zu erzielen.Für die Praxis kann zusammengefaßt werden: Sauerstoffgehalte - auch in Spuren - sind zu vermeiden.Wasserzusatz inhibiert die Spannungsrißkorrosion; Zusätze von Wasser sind daher - soweit möglich - zu empfehlen.Behälter sollen aus StE 355 gebaut und spannungsarm geglüht werden.Kathodischer Schutz ist denkbar, sofern es gelingt, diesen in der Praxis zu verwirklichen.
    Additional Material: 14 Ill.
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  • 6
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Core melting experiments are performed in order to investigate on a laboratory scale the behaviour of the reactor core constituents released during severe light water reactor accidents in the form of aerosols and the dependence on the temperature of the melting charge. The materials used reflect the composition of a pressurized water reactor core including structural materials, fuel, and fission products. One of the most important questions regards the release and chemical behaviour of fission product iodine.X-ray photoelectron spectroscopy (XPS) of aerosol samples released at temperatures ranging from 1200 °C to 1900 °C revealed caesium, silver, indium, cadmium, iodine, and tellurium as constituents of the aerosol surface. The main compounds identified were: caesium hydroxide, silver metal, indium oxide, cadmium hydroxide, tellurium dioxide.The investigation of the chemical nature of iodine was difficult because of the low iodine concentration in the samples and because of the small chemical shifts in the photoelectron energies of the possible iodine compounds. The determination of its chemical states was possible with a combination of XPS and argon ion bombardment and resulted in identification of CsI and HgI. The procedure chosen required in addition a critical reflection on the influence of ion bombardment on the surface chemistry.
    Additional Material: 6 Ill.
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  • 7
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: IR specular reflectance spectra with respect to hydrogen peroxide formation during uncatalyzed and Cu (oxide)-catalyzed oxidation of isotactic Polypropylene films have been measured as function of time and temperature (90-130°C). Energies of activation for the various cases have been obtained. The originally proposed kinetic scheme based on oxygen-absorption measurements has been modified in order to accommodate the spectroscopical results. The amount of ROOH groups present at any time on the polymer is very small, indicating relatively slow rates of ROOH formation and fast rates of their decomposition. The kinetic scheme fits well the experimental data. However, the reasons for the variations of the relevant energies of activation obtained for the catalyzed oxidation in absence and presence of the main volatile reaction products, H2O and CO2, are not yet understood, i.e., the mechanism needs further investigations.
    Additional Material: 9 Ill.
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  • 8
    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: At dispergation of PVC particles in plasticizers border layers are formed which result from swelling of the microdomain structure at the surface of the latex particles by solvatations of chain ends and loops and from the formation of electrical double layers. These border layers enlarge the effective hydrodynamic volume of the particles. The properties of the layers can be varied within large limits.
    Notes: Infolge einer Quellung der Mikrodomänenstruktur an der Oberfläche der Latexpartikeln durch Solvatation von Kettenenden und Schlaufen und durch Bildung elektrischer Doppelschichten entstehen bei der Dispergierung von PVC-Par-tikeln in Weichmachern Grenzflächenschichten. Diese vergrößern das hydrodynamisch wirksame Teilchenvolumen. Die Eigenschaften dieser Grenzflächenschichten können in weiten Grenzen variiert werden.
    Additional Material: 2 Ill.
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  • 9
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 225-253 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The high temperature pyrolysi of 1,3-butadiene has been investigated in the shock tube with two time-resolved diagnostic techniques: laser schlieren measurements of density gradient with 1, 2, 4, and 5% C4H6 in Ar or Kr, 0.26 〈 P2 〈 0.66 atm, over 1550-2200 K, and time-of-flight mass spectra for 3% C4H6-Ne, P5 ∼ 0.4 atm, 1400-2000 K. When combined with a recent single-pulse shock tube product analysis covering 1050-2050 K, these measurements permit a complete modeling of major species in C4H6 pyrolysis. Extrapolated density gradients and product analyses show initiation is dominated by C4H6 → 2C2H3., significant falloff and Arrhenius curvature being seen in the derived rates. A restricted rotor, Gorin model RRKM fit to these rates with reasonable parameters generates \documentclass{article}\pagestyle{empty}\begin{document}$$ k_\infty = 4.1 \times 10^{16} {\rm exp(} - 47000/{\rm T)s}^{ - 1},{\rm 1600} - 1900{\rm K}{\rm .} $$\end{document} The derived barrier, ΔH0º = 99 ± 4 kcal/mol, translates to ΔHfº,298 = 63.4 ± 2 kcal/mol for the heat of formation of vinyl radical. A mechanism for the formation of all products detected in the above experiments is given, together with a successful but semiquantitative kinetic model for major products. The measurements require the rate of vinyl radical dissociation, C2H3 + M → C2H2 + H + M, to be extremely low, k 〈 109 cm3/mol s for 1600 K, so that the dominant chain carrier in C4H6 pyrolysis is vinyl radical.
    Additional Material: 10 Ill.
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