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  • 1
    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.
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  • 2
    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.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 42 (1993), S. 50-58 
    ISSN: 0006-3592
    Keywords: emulsion liquid membrane ; lactic acid ; organic acid recovery ; fermentation ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies on the batch extraction of lactic acid using an emulsion liquid membrane system are reported. The membrane phase consists of the tertiary amine carrier Alamine 336 and the surfactant Span 80 dissolved in n-heptane/paraffin and aqueous solutions of sodium carbonate in the internal phase. The effects of internal phase reagent, extraction temperature, and initial external phase pH on the extraction efficiency and the emulsion swelling are examined. A statistical factorial experiment on extraction from clarified lactic acid fermentation broth was carried out to obtain knowledge of the performance of the extraction system from a broth. The extraction efficiency from the fermentation broth is found to be lower as compared to aqueous solutions of pure lactic acid. The effect of pH and the presence of other ionic species on selectivity are discussed. © 1993 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 4
    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 resistance of austenitic and ferritic stainless alloys in 20 to 75% nitric acid as a function of temperature and concentrationA series of stainless austenitic and ferritic materials was exposed for 100 days to boiling nitric acid which contained no corrosion products; the corrosion rates and depths of the grain boundary attack were observed.Provided the structure is precipitation-free, the following are suitable for long-term exposure; the austenitic steels X 2 CrNi 1912, X1 CrNi 25 21, X1 CrNiMoN 25 222 and X1 NiCrMoCu31274, the practically Mo-free and Cu-free development steel X1 NiCr31 27, and the highly Mo-alloyed variant X1 NiCrMoCu 31275. In the case of alloy NiCr21 Mo it is advisable to limit the concentration and/or the temperature of the nitric acid. The “superferrite” X1CrNiMoNb2842, the Japanese steel X1 CrNiNb 30 2 and the austenitic steels X2 CrNiMoN 1713 3 and X1 CrNiMoN 25 22 2 in the version with high nickel content are unsuitable.Thus, as an alloying element, molybdenum does not always impair the resistance of stainless steels to nitric acid.The decisive factor affecting the corrosion rates is the chromium content of the material.The temperature-dependent function of the corrosion in azeotropic nitric acid conforms to Arrhenius relations. The concentration-dependent function of the corrosion in 20 to 75 (80)% nitric acid can be described by a hyperbolic equation. An exception is formed by X1 CrNiSi 1815; here the corrosion rate increases with the concentration of the acid until the azeotropic point is reached; then, owing to the formation of a surface film, it falls until the acid becomes highly concentrated.
    Notes: Eine Reihe nichtrostender austenitischer und ferritischer Werk-stoffe wurde 100 d lang in siedender, korrosionsproduktfreier Salpetersäure beansprucht; hierbei wurden Abtragungsraten und Tiefen des Korngrenzenangriffs verfolgt.Für Langzeitbeanspruchung sind, ein ausscheidungsfreies Gefüge vorausgesetzt, geeignet: die austenitischen Stähle X 2 CrNi 1911,X1 CrNi 25 21,X1 CrNiMoN 25 222,X1 NiCrMoCu 3127 4 sowie die praktisch molybdän- und kupferfreie Entwicklungsgüte X1 NiCr3127 und die hochmolybdänlegierte Variante X1NiCrMoCu31275. Bei der Legierung NiCr21Mo empfiehlt sich eine Begrenzung der Salpetersäure-Konzentration und/oder der Temperatur. Nicht geeignet sind der “Superferrit” X1 CrNiMoNb2842, die japanische Sorte X1CrNiNb302 sowie die austenitischen Stähle X 2 CrNiMoN 1713 3 und X1 CrNiMoN 25 22 2 in der hochnickelhaltigen Version.Das Legierungselement Molybdän wirkt sich somit nicht in allen Fällen schädlich auf die Salpetersäureständigkeit nichtrostender Qualitäten aus.Entscheidend für die Höhe der Abtragungsraten ist die Höhe des Chrom-Gehaltes des Werkstoffes.Die Temperaturabhängigkeit der Korrosion in azeotroper Salpetersäure folgt Arrhenius-Beziehungen. Die Konzentrationsabhängigkeit der Korrosion in 20 bis 75 (80)%iger Salpetersäure läßt sich durch einen Hyperbel-Ansatz beschreiben; eine Ausnahme bildet X1 CrNiSi 18 15: mit zunehmender Säurekonzentration steigt die Abtragungsrate bis zum Azeotrop-Punkt an und fällt dann bis zur hochkonzentrierten Säure infolge Deckschichtbildung ab.
    Additional Material: 30 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 42 (1991), S. 559-569 
    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 of austenitic stainless steels in (condensing) nitric acid containing chloridesThe corrosion parameters involved in the behaviour of austenitic stainless steels and nickelbase alloys in chloride containing nitric acid are being stated.Investigation of the corrosion resistance of the austenitic stainless steel 1.4306, ESR grade for application in nitric acid, in nitric acid condensates containing small amounts of chlorides. The condensates were formed from boiling nitric acids of molarities 6 to 10 containing 15 to 45 mg chlorides/1.The calculated corrosion rates of 〈 1 μm/y can be considered rather small. Especially in cases of insufficient wetting of the heat exchanger surfaces, however, local roughening and pitting corrosion is to be expected, mostly under rust-colored, chloride-containing deposits. The intensity of pitting corrosion increases with increasing chloride contents of the nitric acid solutions that evaporate.The sealing surfaces consisting of steel 1.4306 and PTFE did not exhibit any crevice corrosion.Nitric acid grade ESR-1.4306 definitely does not suffice requirements as described in this paper. It is suggested to use stainless steels which exhibit an improved resistance against chlorides and, at the same time, a high resistance against nitric acid attack. The following steel grades may be considered: X 1 CrNi 25 21 (Mat. No. 1.4335), X 2 CrNiMoN 25 22 2 (Mat. No. 1.4466) and/or X 1 NiCrMoCuN 31 27 4 (Mat. No. 1.4563).
    Notes: Die Parameter der Korrosion nichtrostender austenitischer Stähle und Nickelbasis-Legierungen in chloridhaltigen Salpetersäuren werden beschrieben.Untersucht wurde das Korrosionsverhalten des nichtrostenden austenitischen Stahls W.-Nr. 1.4306 als Salpetersäure-Qualität in ESU-Güte bei Beaufschlagung mit schwach chloridhaltigen Salpetersäure-Kondensaten. Die Kondensate bildeten sich aus siedenden 6 bis 10 M Salpetersäuren mit 15 bis 45 mg Chlorid/1.Die errechneten Abtragungsraten sind mit 〈 1 μm/a zwar gering, jedoch ist - vornehmlich bei nur geringer Kondensat-Bespülung der Wärmetauscherflächen - mit örtlichen Aufrauhungen und mit Lochkorrosion, meist unter rostfarbenen, chloridhaltigen Belägen, zu rechnen. Die Lochkorrosionsintensität nimmt mit steigendem Chloridgehalt der zu verdampfenden Salpetersäure-Lösungen zu.An den aus W.-Nr. 1.4306 und PTFE gebildeten Dichtflächen trat keine Spaltkorrosion auf.W.-Nr. 1.4306 (in Salpetersäure-Qualität und ESU-Güte) ist bei den hier beschriebenen Anwendungen überfordert; es wird vorgeschlagen, nichtrostende Stähle mit verbesserter Chlorid-Beständigkeit bei gleichzeitig hoher Salpetersäure-Beständigkeit zu verwenden, wobei an die Stahlsorten X 1 CrNi 25 21 (W.-Nr. 1.4335), X 2 CrNiMoN 25 22 2 (W.-Nr. 1.4466) und/oder X 1 NiCrMoCuN 31 27 4 (W.-Nr. 1.4563) gedacht wird.
    Additional Material: 19 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 41 (1990), S. 308-329 
    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 of aluminium and aluminium alloys in nitric acidA literature survey was made to show the suitability of aluminium and aluminium alloys in contact with highly concentrated nitric acid, particularly with regard to the corrosion behaviour of weld joints made using various welding processes.The corrosion resistance of Al99.5 in nitric acid was investigated as functions of temperature and acid concentrations. The linear corrosion rates are plotted in an Arrhenius diagram. Decreasing nitric acid concentrations are causing a parallel shift of the lines in the Arrhenius diagram towards higher corrosion rates.Starting with A199.5, the corrosion rates in nitric acid at and above 99.8 concentration decrease as the A1 contents of the materials increase. Doping with copper should be avoided.After exposure of wrought as well as continuously cast A1 and A1 alloys to highly concentrated technical grade nitric acid at 30 °C (1 year test period), the corrosion behaviour of a number of alloys was comparable to that of pure aluminium grades.
    Notes: Auswertung des Schrifttums über die Eignung von Aluminium-Werkstoffen zur Handhabung von hochkonzentrierter Salpetersäure, vornehmlich im Hinblick auf das Korrosionsverhalten von nach unterschiedlichen Verfahren hergestellten Schweißverbindungen.Untersuchungen zur Temperatur- und Konzentrationsabhängigkeit der Korrosion von Al99,5 in Salpetersäuren. Die linearen Abtragungsraten ordnen sich in ein Arrhenius-Diagramm ein, wobei abnehmende Salpetersäure-Konzentrationen eine Parallel-Verschiebung der Geraden im Arrhenius-Diagramm in Richtung höherer Abtragungsraten bewirken.Ausgehend von Al99,5 verringern sich die Abtragungsraten in ≥ 99,8%iger Salpetersäure mit zunehmendem Al-Gehalt der Werkstoffe; Kupfer-Dotierungen sind zu vermeiden.Nach der Auslagerung von Al-Werkstoffen (Knetwerkstoffe und Strangguß) in technischer, auf 30°C erwärmter hochkonzentrierter Salpetersäure zeigten (Prüfdauer: 1 Jahr) eine Reihe von Legierungen ein den Reinaluminium-Sorten vergleichbares Korrosionsverhalten.
    Additional Material: 15 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 123 (1990), S. 971-973 
    ISSN: 0009-2940
    Keywords: Calculations ; Jahn-Teller distortion ; Nitrenium ; Phosphenium ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ab initio calculations at SCF, MCSCF, and ACPF level were performed on a series of the phosphenium- and nitreniumcation family. These show that they possess an allylic π-system with 4 electrons, which is distorted from planarity when the terminal groups of the allylic system are PR2 (R — H) fragments. The distortion is such as to adopt C2 symmetry, and is the consequence of Jahn-Teller distortion via mixing of the energy highest π2 orbital with an energetically low lying δ* orbital. The latter interaction is only operative if a symmetry breaking from C2v to C2 symmetry occurs. The importance of Jahn-Teller distortion on the biradical character in these systems is investigated by correlation calculations.
    Additional Material: 1 Ill.
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  • 8
    ISSN: 0009-2940
    Keywords: Phosphatriafulvenes ; Peterson olefination ; Electron densities, inverse ; 1,3-Diphosphacyclobutanes ; Calculations, ab initio SCF ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Organophosphorus Compounds, 511). - Phosphatriafulvenes - Phosphaalkenes with Inverse Electron Density2)Peterson olefination of the sterically hindered cyclopropenones 1 with the lithium phosphides 2 yields the so far unknown phophatriafulvenes 3 and 4, which possess inverse electron densities. They are characterized by transition metal complex formation (→7, 8). Acylation of 3a with the carboxylic acid chlorides 11 leads to a great variety of P-acylphosphatriafulvenes 13a-s. They partly dimerize under formation of the 1,3-diphosphacyclobutanes 13 ⇌ 14.
    Additional Material: 3 Tab.
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  • 9
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The tensile properties of self reinforced poly(propylene)/poly(1-butene) composites, obtained by rapid extension of the melt, have been measured and correlated to morphological parameters derived from x-ray experiments. Critical fiber lengths as a function of sample composition and the elastic modulus and yield stress of the fibers could be determined. It is shown, that, applying a load to the system, the forces are fully taken up by the fibers and the system breaks by fail of the fibers. The longitudinal structure of the fibers is found to be independent of sample composition.
    Notes: Mechanische Parameter wie Elastizitätsmodul, Fliß- und Bruchspannung von aus der hochorientierten Schmelze hergestellten nadelkristallinen Mischungen aus Poly(propylen) und Poly(1-bute) wurden mit morphologischen Parametern, die aus Röntgenmessungen abgeleitet wurden, korreliert. Es wird gezeigt, daß der Elastizitätsmodul des Verbundes aus den E-Moduln der Fasern und der Matrix berechnet werden kann (Mischungsregel). Die an der Probe angreifenden Kräfte werden voll auf die Fasern übertragen; der Verbund kann daher als eigenfaserverstärktes System angesehen werden. Die Abschätzung der kritischen Faserlänge ergibt, daß die Festigkeit der FAsern voll ausgenutzt wird; der Bruch des Systems bei Belastung ist daher auf das Versagen der Fasern zurückzuführen. Das mechanische Verhalten des Verbundes wird stark beeinflußt durch die Komponentenzusammensetzung. Die longitudinale Struktur der Nadeln beider Komponenten bleibt unbeeinflußt von der jeweiligen Co-Komponente.
    Additional Material: 12 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 124 (1991), S. 271-274 
    ISSN: 0009-2940
    Keywords: Phosphacumulenes ; Cumulenes ; Calculations, MNDO, SCF ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The title compound phosphabutatriene possesses two energetically closely spaced frontier orbitals, as in methylenephosphane and in phosphaallene. They are built up from the π system or the s̰ orbital of phosphorus by interaction with neighboring π bonds. The extension of these frontier orbitals over all (heavy) atoms makes self-dimerization to different cyclobutane derivatives feasible. Substituent effects on the ordering of s̰ and π are analyzed. Vibrational analyses indicate P=C vibrations of low intensity which decrease with increasing length of the heterocumulene chain. The analysis is extended to the two next higher homologs, which are hitherto experimentally unknown.
    Additional Material: 1 Ill.
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