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  • 1
    ISSN: 1434-1948
    Keywords: Alkylation ; Carbonyl complexes ; Lewis acids ; Phosphaalkenes ; Protonation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of the carbonyl-functionalized phosphaalkenes RC(O)P=C(NMe2)2 [R = tBu (2a), Ph (2b)] with protic acids and alkylating reagents occurred at the two-coordinate phosphorus atom to give the phosphanyl-substituted carbocations 3a,b and 4a,b. In contrast, treatment with Me3SiOSO2CF3 resulted in attack at the oxygen atom by the silyl group, and the formation of [RC(OSiMe3)=PC(NMe2)2]SO3CF3 (5a,b). Similarly, the Lewis acids B(C6F5)3, Al(tBu)2Cl and AlMe3 were ligated to the oxygen atom of the carbonyl group. Two equivalents of GaMe3 were added to the oxygen and phosphorus atom of the phosphaalkene to yield the thermolabile complexes [RC(OGaMe3)=P(GaMe3)C(NMe2)2] (10a,b). In contrast, one molecule of InMe3 was bound to the phosphorus center of the phosphorus compound. Reaction of the phosphaalkenes with [Ni(CO)4], [Fe2(CO)9] or [{(Z)-cyclooctene}Cr(CO)5] also took place at the pnictogen atom, resulting in complexes of the type [RC(O)P{M(CO)n}C(NMe2)2] (R = tBu, Ph; M = Ni, n = 3; Fe, n = 4; Cr, n = 5). The chemical transformations reported here underline the versatile chemistry of phosphaalkenes and emphasize a relationship between carbonyl-functionalized phosphaalkenes and the well-investigated class of phosphorus ylides. X-ray structures of compounds 6b, 7b*, 10a, 11a and 12a are reported.
    Additional Material: 6 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 369-374 
    ISSN: 1434-1948
    Keywords: Phosphanylcarbenes ; Substituent effects ; Quantum chemical calculations ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A phosphanyl group exerts much less π-conjugation properties than an amino group. On this basis, corresponding carbene structures exhibit much smaller singlet-triplet energy separations. Of the various structures investigated quantum-chemically the largest singlet-triplet energy separations are predicted for cyclic diphosphanylcarbenes, in which the two functional groups are incorporated into a ring system and the phosphorus atoms are substituted by phosphoraniminato groups. Then the singlet-triplet energy separations become essentially larger than for the Bertrand-type (push-pull) carbenes.
    Additional Material: 1 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 2000 (2000), S. 375-381 
    ISSN: 1434-1948
    Keywords: Fluorine ; Silicon ; Ab initio calculations ; Donor-acceptor systems ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Quantum chemical calculations at the ab initio level indicate that Lewis donors such as amine or water form weak donor-acceptor complexes with fluoro-substituted silanes. The strength of the donor-acceptor formation increases with increasing degree of fluorine substitution. Amine and water form strong adducts only for tetrafluorosilane. The higher element homologues of Lewis donors, such as phosphane and sulfur dihydride, do not in essence coordinate. A considerable role in donor-acceptor formation is exerted by chelation effects which impose intramolecular interactions on functionalized ligands. The corresponding structures are explored.
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 35 (1984), S. 401-406 
    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: Hydrolysis of o-dichlorobenzene-water-mixtures In neutral to acid conditions and its importance when selecting materials of constructionWater-saturated o-dichlorobenzene and o-dichlorobenzene-watermixtures were investigated for hydrolysis under neutral and acid conditions and the exclusion of light. Some measurements were also taken in presence of iron oxides and also metallic iron.Chloride ion generation grows with increasing temperatures and - at 175 °C - also with time. The greatest chloride ion generation was observed when water saturated o-dichlorobenzene reacted in the presence of iron oxides.In the presence of sulfuric acid the maximum chloride ion generation was detected at 175 °C and a sulfuric acid concentration of 3 · 10-3 mol/l.The hydrolysis products were monochlorobenzene and o-chlorophenol.The chloride ion generation from o-dichlorobenzene in neutral and slightly acid media is important when selecting materials of construction for chemical equipment.
    Notes: Die Hydrolyse von wassergesättigtem o-Dichlorbenzol und von o-Dichlorbenzol-Wasser-Gemischen wurde unter Lichtausschluß im neutralen und im sauren Bereich untersucht. Die Messungen wurden teils in Gegenwart von Rost bzw. metallischem Eisen durchgeführt.Die Chlorid-Abspaltung steigt mit zunehmender Temperatur und - bei 175 °C - auch mit zunehmender Beanspruchungsdauer an. Die höchste Chlorid-Abspaltung wurde bei wassergesättigtem o-Dichlorbenzol in Gegenwart von Rost gefunden.In Anwesenheit von Schwefelsäure tritt bei 175 °C ein Maximum der Chlorid-Abspaltung bei einer Schwefelsäure-Konzentration von 3 · 10-3 mol/l auf.Als Hydrolyseprodukte waren lediglich Monochlorbenzol und o-Chlorphenol nachweisbar.Die Chlorid-Abspaltung aus o-Dichlorbenzol im neutralen und schwach sauren Bereich ist bei der werkstofflichen Auslegung entsprechender Bauteile zu beachten.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 37 (1986), S. 74-82 
    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 the alloy AlMg 2 Mn 0,8 in highly-concentrated nitric acidThe purpose of the study was to investigate the corrosion of the alloy AlMg 2 Mn 0.8 in highly-concentrated nitric acid at temperatures between 5 °C and 50°C.The corrosion rates follow the Arrhenius equation \documentclass{article}\pagestyle{empty}\begin{document}$$ \lg \ {\rm w}_{{\rm lin}} = - {\textstyle{{3170} \over {\rm T}}} + 9.1; $$\end{document} the apparent activation energy was calculated to be -60.8 kJ/mol.The ratio of the dissolved alloy components aluminum and magnesium indicates that magnesium had accumulated near the surface of the metal before the exposure to nitric acid. This finding is confirmed by surface analysis.
    Notes: Untersucht wird die Korrosion der Legierung AlMg 2 Mn 0,8 in hochkonzentrierter Salpetersäure bei Temperaturen zwischen 5 und 50°C.Die Abtragungsraten folgen der Arrhenius-Beziehung \documentclass{article}\pagestyle{empty}\begin{document}$$ \lg \ {\rm w}_{{\rm lin}} = - {\textstyle{{3170} \over {\rm T}}} + 9,1; $$\end{document} die scheinbare Aktivierungsenergie ergibt sich zu -60.8 kJ/mol.Aus dem Verhältnis der in Lösung gegangenen Legierungsanteile Aluminium und Magnesium ist abzuleiten, daß Magnesium vor der Salpetersäure-Beanspruchung in der Metalloberfläche angereichert ist. Dieser Befund wird durch oberflächenanalytische Untersuchungen bestätigt.
    Additional Material: 17 Ill.
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  • 6
    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.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 151 (1926), S. 221-238 
    ISSN: 0863-1786
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird eine neue Methode zur Trennung von Tantal und Niob beschrieben. Dieselbe beruht auf hydrolytischer Differentialspaltung von Tantaloxal- und Nioboxalsäure in Gegenwart von Gerbsäure in schwach saurer Lösung. Die Methode besitzt die folgenden Vorteile: Die Färbung des Tantalniederschlages zeigt auf den ersten Blick, ob er niobfrei oder niobhaltig ist, es werden keine Platingefäße benutzt, und der erreichbare Genauigkeitsgrad steht nicht viel hinter dem für die Trennung der gewöhnlicheren Elemente zurück.
    Additional Material: 3 Tab.
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  • 8
    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.
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  • 9
    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.
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  • 10
    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.
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