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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 287-297 
    ISSN: 1434-1948
    Keywords: Enolates ; Nucleophilic additions ; Ruthenium ; S ligands ; Sulfenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Reaction of the chiral racemic complex [CpRu(mppe)(SO2)]PF6 (1, mppe = Me2PC2H4PPh2) with diazomethane or -ethane gave the sulfene complexes [CpRu(mppe)(RHC/SO2)]PF6 (R = H, 2a; R = Me, 2b). Treatment of 2a with prochiral enamines or deprotonated β-oxo esters yielded C-C coupling products with 32-60% de. An analog of 2a, [NmcpRu(mppe)(H2C/SO2)]PF6 (8, Nmcp = neomenthylcyclopentadienyl) was prepared in a four-step synthesis starting from LiNmcp and [RuCl2(PPh3)3]. Repeated crystallization of the intermediate [NmcpRu(mppe)Cl] (6) provided diastereomerically pure 6′ which added methylene stereospecifically to give diastereomerically pure 8′. Compound 8 turned out to be much less reactive towards nucleophiles than 2a, but still added deprotonated ethyl 2-methyl-3-oxobutanoate with 44% de. The chiral, enantiomerically pure sulfur dioxide complex [CpRu(chir)(SO2)]PF6 [10, chir = (S,S)-Ph2PCHMeCHMePPh2] was synthesized from [CpRu(chir)Cl] and SO2 and was characterized by X-ray crystallography. Reaction of 10 with diazomethane gave the enantiomerically pure sulfene complex [CpRu(chir)(H2C/SO2)]PF6 (11). Addition reactions of 11 with N-(1-cyclopentenyl)morpholine, as well as with various enolates derived from β-oxo esters or 1,3-diesters proceeded with high yields and 20-90% de. The structure of a diastereomerically pure addition product, [CpRu(chir)(SO2CH2C(Me){C(O)Me}{C(O)OtBu}] (13d′), was determined crystallographically and was shown to have (R) configuration at the quaternary carbon atom. After alkylation of one of the S/O functions, the sulfinate ligand was cleaved from the metal center by ligand substitution with acetonitrile, and the resulting acetonitrile complex 15 was converted back into 10 by treatment with SO2.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 35 (1984), S. 556-565 
    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: Corrosion reactions between elemental sulphur and plain carbon steel in aqueous mediaPlain carbon steels are rather severely attacked by elemental sulphur at room temperature in the presence of aqueous media. The corrosion occurs preferentially at the places where the two solid substances iron and sulphur are in contact with each other and results in shallow pit formation. At the same time the pH is also decreased slightly and small amounts of H2S and sulphate ions are formed. Neutral salts stimulate the corrosion process whereas phosphates inhibit it and the alkaline media such as Na2CO3 and ethylamine with pH 〉 12 prevent it completely. The latter can be made use of for corrosion protection. At high salt concentrations (c 〉 1 mol/l) the corrosion rate, however, decreases with increasing salt concentration. The corrosion rate may increase with increasing flow velocity of the medium, but the corrosion takes place uniformly.The results of electrochemical investigations show that the reduction of sulphur occurs at the corrosion product FeS and is the rate controlling step. No sulphur reduction is observed on platinum electrodes when no FeS is present. It is assumed that the starting reaction to initiate corrosion in the system Fe/S/H2O is a slight disproportionation of S to H2SO4 resulting in the formation of FeS.
    Notes: Unlegierter Stahl wird durch elementaren Schwefel in Gegenwart wäßriger Medien bei Raumtemperatur verhältnismäßig stark angegriffen. Die Korrosion erfolgt bevorzugt an den Berührungsstellen der Feststoffe Fe und S unter Muldenbildung. Gleichzeitig erfolgen eine geringe pH-Absenkung sowie eine geringfügige Bildung von H2S und Sulfat-Ionen. Der Vorgang wird durch Neutralsalze sehr stark stimuliert, durch Phosphate inhibiert und durch alkalische Medien, wie z. B. Na2CO3 und Ethylamin mit pH 〉 12, völlig unterbunden. Dies kann zum Korrosionsschutz genutzt werden. Mit zunehmender Salzkonzentration (c 〉 1 mol/l) nehmen die Abtragungsraten wieder ab. Durch zunehmende Strömungsgeschwindigkeit können die Abtragungsraten zunehmen, wobei aber nur gleichförmiger Flächenangriff auftritt.Elektrochemische Untersuchungen zeigen, daß die Reduktion des Schwefels am Korrosionsprodukt FeS stattfindet und für die Korrosion geschwindigkeitsbestimmend ist. An Pt-Kathoden wird bei Abwesenheit von FeS keine Schwefelreduktion beobachtet. Als Startreaktion für die Korrosion im System Fe/S/H2O wird eine geringe Disproportionierung des S zu H2SO4 angenommen, wobei FeS entsteht.
    Additional Material: 11 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 36 (1985), S. 309-315 
    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: Unexpected alloying influences in connection with the corrosion susceptibility of sour gas well tubingThe corrosion behavior of low alloy steels in sour gas wells with injection of monoethylamine for sulfur solvent depends considerably on the concentration of certain alloying elements. Strong corrosion acceleration is observed from chromium, silicon and copper. Experimentally it could be shown that Si contents 〉 0.30% increase corrosion significantly at temperatures 〉 110°C already at low velocities and liquids typical of well fluids. Under unfavourable conditions corrosion rates may vary between 1 and 11 mm/a depending on the Si content. The results explain the sometimes erratic corrosion behaviour of single tubings in strongly sour gas wells. As a consequence, for new completion of wells with continuous monoethylamine injection for C75/2 steels only 38Mn6 having silicon ≤ 0.15% and chromium ≤ 0.10% are applied.
    Notes: Das Korrosionsverhalten niedriglegierter Steigrohrstähle in Sauergassonden mit Monoethylamininjektion als Schwefellösemittel für elementaren Schwefel ist stark von der Konzentration bestimmter Legierungsbestandteile abhängig. Deutlich korrosionsbeschleunigenden Einfluß haben Chrom, Silicium und Kupfer. Im Experiment konnte gezeigt werden, daß ein Si-Gehalt 〉 0,30% bei Temperaturen 〉 110 °C bereits bei niedrigen Strömungsgeschwindigkeiten und sondentypischer Flüssigkeitszusammensetzung zu signifikant höheren Korrosionsraten führt. Bei ungünstigen Parametern können die Abtragsraten in Abhängigkeit vom Si-Gehalt zwischen 1 und 11 mm/a liegen. Die Ergebnisse erklären das teilweise erratische Korrosionsverhalten einzelner Steigrohre in stark sauren Sonden. Als Konsequenz dieser Erkenntnisse werden bei Neukomplettierungen von Sauergassonden mit Monoethylamininjektion bei 38Mn6 (C75/2)-Stählen nur noch Qualitäten mit Si-Gehalten ≤0,15% und Cr-Gehalten ≤0,1% verwendet.
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  • 4
    ISSN: 0930-7516
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Theoretical and experimental investigations were performed with cold water models of bottom-blown metallurgical ladles in order to develop a mathematical description of the mixing processes in such reactors. This analytical model is based on the subdivision of the reactor into interacting subspaces, whereby each subspace is regarded as an ideal mixer. The convective mass transfer between the subspaces is represented by constant coupling coefficients, and the mass balance for the material to be mixed in provides a homogeneous system of differential equations to determine the time dependence of concentration in the individual subspaces. Different combinations of interacting subspaces are represented. The flow field and the distribution of turbulence intensity measured by LDA in water models and the concentration profiles in mercury models measured by EMF cells show that a subdivision into five subspaces is adequate. Size, position and interaction coefficients are also determined by experiments. The calculated mixing times agree well with those measured.
    Additional Material: 28 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 37 (1903), S. 88-112 
    ISSN: 0863-1778
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 80 (1913), S. 71-78 
    ISSN: 0863-1778
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 167 (1927), S. 75-76 
    ISSN: 0863-1786
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 54 (1907), S. 217-222 
    ISSN: 0863-1778
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 82 (1913), S. 92-96 
    ISSN: 0863-1778
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 77 (1912), S. 51-89 
    ISSN: 0863-1778
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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