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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 435 (1977), S. 119-126 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Raman Spectra of the System SnBr2—CsBr in the Solid and Molten StateRaman spectra of crystalline and molten SnBr2 as well as of molten SnBr2—CsBr mixtures were measured. In molten SnBr2 polymeric chains with similar structural elements as in solid SnBr2 will be formed. Temperature rising causes a heterolytic disruption into smaller but still polymeric units of varying chain length. Equilibrium fragmentation reactions occur by bromide ion addition. In bromide rich SnBr2—CsBr melts (Br-/Sn2+ ratio 3-6) Sn2Br5-, SnBr3- and Br- ions exist with Sn2Br5- species predominating.
    Notes: Sowohl polykristallines und geschmolzenes SnBr2 als auch SnBr2—CsBr-Schmelzen wurden ramanspektroskopisch untersucht. Beim Übergang vom festen in den flüssigen Zustand entstehen beim SnBr2 polymere Ketten mit den Strukturelementen des festen SnBr2. Temperaturerhöhung bewirkt eine heterolytische Spaltung in kleinere, aber immer noch polynukleare Kettenbruchstücke. Bei Br--Zugabe erfolgen Gleichgewichtsabbaureaktionen. In Br--reichen SnBr2—CsBr-Schmelzen (Br-/Sn2+-Verhältnis 3-6) liegen hauptsächlich Sn2Br5--Spezies neben SnBr3-- und Br--Ionen vor.
    Additional Material: 2 Tab.
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  • 2
    ISSN: 0044-2313
    Keywords: Polyphosphides ; Zintl-phases M3X11 (M = Na, K, Rb, Cs; X = P, As) ; P113-, As113- cage anion ; preparation ; vibrational spectra ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Chemistry and Structural Chemistry of Phosphides and Polyphosphides. 53. Preparation, Properties, and Vibrational Spectra of the Cage Anions P113- and As113-The Zintl-phases M3X11 (M = Na, K, Rb, Cs; X = P, As) are prepared from the elements or from M3X7 and X. The compounds undergo a first-order phase transition from the crystalline to the plastically crystalline state. Unit cell and space group of both modifications and the transition temperature Tc are determined. The vibrational spectra of the crystalline compounds and the Raman spectrum of the P113- anion in en-solution as well are measured. The assignment of the frequencies is given, based on the 32-D3 symmetry of the X113- cage anion. Normal coordinate analysis is carried out in terms of Cartesian coordinates to avoid the problem of redundancies in using internal coordinates. The force constants [mdyn Å-1] obtained for the characteristic bonds r, s, and t are: fppr = 1.34, fpps = 1.20, fppt = 1.08; fAsAsr = 1.1, fAsAss = 0.91. Normal vibrations and the potential energy distribution (PED) are discussed.
    Notes: Die Zintl-Phasen M3X11 (M = Na, K, Rb, Cs; X = P, As) werden aus den Elementen oder aus M3X7 und X synthetisiert. Die Verbindungen durchlaufen einen Phasenübergang 1. Ordnung vom kristallinen zum plastisch-kristallinen Zustand. Elementarzelle und Raumgruppe beider Modifikationen sowie Übergangstemperaturen Tc wurden bestimmt. Die Schwingungsspektren der kristallinen Verbindungen sowie das Raman-Spektrum des Anions P113- in en-Lösung wurden gemessen. Die Zuordnung der Schwingungsfrequenzen gelingt auf der Basis der Symmetrie 32-D3 der Käfiganionen X113-. Die Normalkoordinatenanalyse erfolgte in kartesischen Koordinaten, wodurch das in inneren Koordinaten auftretende Redundanzproblem vermieden wird. Auf diesem Wege erhaltene Kraftkonstanten [mdyn Å-1] der charakteristischen Bindungen r, s und t sind: fppr = 1, 34, fpps = 1, 20, fppt = 1, 08; fAsAsr = 1, 1, fAsAss = 0, 96, fAsAst = 0, 91. Die Normalschwingungen und die Verteilung der potentiellen Energie (PED) werden diskutiert.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 516 (1984), S. 42-48 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vibrational Spectra of the Cage Compound PAs3S3The vibrational spectrum of crystalline PAs3S3 and the raman spectrum of the molten title compound have been recorded. The assignment of the frequencies is proposed mainly based on polarization data of a PAs3S3 solution in white phosphorus. In the molten state a partial decomposition takes place according to 2 PAs3S3 ⇌ P2As2S3 + α-As4S3.
    Notes: Das Schwingungsspektrum des kristallinen PAs3S3 und das Raman-Spektrum der geschmolzenen Titelverbindung wurden aufgenommen. Die Zuordnung der Schwingungsfrequenzen wird, vor allem basierend auf Polarisationsdaten einer PAs3S3-Lösung in weißem Phosphor, vorgeschlagen. Im geschmolzenen Zustand findet ein partieller Zerfall gemäß 2 PAs3S3 ⇌ P2As2S3 + α-As4S3 statt.
    Additional Material: 4 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 476 (1981), S. 153-158 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vibrational Spectra of β-P4S5 and P4S7The vibrational spectra of the solid and liquid cage compounds β-P4S5 and P4S7 have been recorded. The assignments of the frequencies are proposed mainly based on polarization data. β-P4S5 decomposes during melting into P4S3 α-P4S7 and β-P4S6. Molten α-P4S7 dissociates to some extent into β-P4S6 and sulphur. An association of β-P4S6 with α-P4S7 is discussed for the molten state. All reactions in molten P4S7 are reversible.
    Notes: Die Schwingungsspektren der käfigstrukturierten Verbindungen β-P4S5 und P4S7 wurden für den kristallinen und flüssigen Zustand aufgenommen. Die Zuordnung der Schwingungsfrequenzen wird, vor allem basierend auf Polarisationsdaten, vorgeschlagen. β-P4S5 zerfällt in der Schmelze in P4S3 α-P4S7 und β-P4S6. α-P4S7 schmilzt unter partieller Dissoziation in β-P4S6 und S. Für β-P4S6, wird eine Assoziatbildung mit α-P4S7 in der Schmelze diskutiert. Die Vorgänge im geschmolzenen P4S7 sind reversibel.
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 499 (1983), S. 7-14 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Vibrational Spectra of As4S4 and As4Se4The vibrational spectra of solid α- and β-As4S4 and the Raman spectrum of molten As4S4 have been recorded. The assignments of the frequencies are proposed mainly based on polarization data. The Raman melt spectra suggest that As4S4 molecules (symmetry D2d) are retained in the molten state. A partial decomposition of the melt by prolonged laser irradiation was observed. The Raman spectrum of solid As4Se4 is presented and the frequencies are tentatively assigned to an As4Se4 molecule of the cradle type, possessing D2d symmetry.
    Notes: Die Schwingungsspektren von festem α- und β-As4S4 und das Ramanspektrum von geschmolzenem As4S4 wurden aufgenommen. Die Zuordnung der Schwingungsfrequenzen wird, vor allem basierend auf Polarisationsdaten, vorgeschlagen. Die Raman-Schmelzspektren zeigen, daß As4S4-Moleküle (Symmetrie D2d) auch im schmelzflüssigen Zustand vorliegen. Ein laserlichtbedingter partieller Zerfall der Schmelze wurde beobachtet. Das Ramanspektrum des festen As4Se4 wird mitgeteilt und die Frequenzen werden einem körbchenstrukturierten As4Se4-Molekül mit D2d-Symmetrie zugeordnet.
    Additional Material: 3 Ill.
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  • 6
    ISSN: 0044-2313
    Keywords: Alkali metal germanides and stannides ; Zintl cluster anions ; Vibrational spectra ; Thermal decomposition ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binary germanides M12Ge17 and M4Ge9 (M = Na, K, Rb, Cs) and the stannides M12Sn17 and M4Sn9 (M = K, Rb, Cs) were identified by a combination of direct synthesis, thermogravimetric analysis, vibrational spectroscopy, X-ray powder data and single crystal structure analysis. The M12E17 phases contain the cluster anions [E9]4- and [E4]4- in the ratio 1:2, forming a hierarchical structure with the cluster anions at the atomic positions of the hexagonal Laves phase MgZn2. Like the M4E4 phases, the M4Ge9 compounds are hierarchical derivatives of the cubic Cr3Si structure but with [Ge9]4- anions. The thermogravimetric analyses give strong evidence for the existence of at least one more phase with [E9]4- and [E4]4- clusters and of the clathrate phases M6E136 in addition to the well-known M8E44□2 chlathrates.
    Additional Material: 3 Ill.
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