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  • Inorganic Chemistry  (28)
  • crystal structure  (2)
  • ternary lanthanide chlorides  (2)
  • ABr/SmBr3  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Retarded solid state reactions III [1] (1997)
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1207-1210 
    Details
    ISSN: 1572-8943
    Keywords: metastable states ; reconstructive phase transitions ; ternary lanthanide chlorides ; thermal hysteresis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Solid state reactions and reconstructive phase transitions exhibit more or less a large hysteresis between reaction temperatures taken from DTA-heating and -cooling curves. For ternary lanthanide chlorides the equilibrium temperatures could be obtained bye.m.f.-measurements in galvanic chlorine cells for solid electrolytes usingA +-ion (A=alkaline metal) conducting diaphragms. By quenching, high-temperature phases can often be transformed to metastable room-temperature phases. In this case the equilibrium state must be established by annealing at sufficiently high temperature, or it must be tried to synthesize the compound in its stability range from suitable precursor systems.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01983676
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  • 2
    Electronic Resource
    Electronic Resource
    Thermochemical and structural investigations (1996)
    Springer
    Journal of thermal analysis and calorimetry 46 (1996), S. 1239-1249 
    Details
    ISSN: 1572-8943
    Keywords: DTA ; galvanic bromine cells for solid electrolytes ; pseudobinary systems ; ABr/SmBr3 ; solution calorimetry ; XRD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The phase diagrams of the systems ABr/SmBr3 were reinvestigated. The findings of Blachnik for the systems withA=Cs, Rb, K were confirmed; however, the dimorphic compound K3SmBr6 is stable only above 572 K. The equilibrium temperature, found bye.m.f.-measurements in a solid state galvanic cell for the reaction KBr+K2SmBr5=L-K3SmBr6, is smaller (522 K). The formation temperature for Rb3SmBr6 is 279 K (DTA) and 256 K (e.m.f.) resp. By solution calorimetry was proved that the compounds Cs2SmBr5 and KSm2Br7 don't exist at 0 K. In the system NaBr/SmBr3 only one hitherto unknown dimorphic compound Na3SmBr3 exists above 473 K. L-Na3SmBr crystallizes in the hexagonal space groupR¯3, above 519 K H-Na3SmBr6 has the monoclinic cryolite-structure. Powder patterns of other compounds not yet investigated — H-/L-A3 SmBr6, ASm2Br7 (A=Cs, Rb, K) and Cs2SmBr5 — were indexed analogously to known structure families. The structure parameters of SmBr3·6H2O were determined by single-crystal measurements.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01979238
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  • 3
    Electronic Resource
    Electronic Resource
    Interaction of Thulium, Ytterbium(III) and Lutetium Chlorides with Sodium Chloride (1999)
    Springer
    Journal of thermal analysis and calorimetry 57 (1999), S. 203-208 
    Details
    ISSN: 1572-8943
    Keywords: crystal structures ; phase diagrams ; ternary lanthanide chlorides ; thermodynamic properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pseudobinary systems NaCl—LnCl3 (Ln=Tm, Yb, Lu) were investigated by DTA and X-ray diffraction. Two types of ternary chlorides exist: congruently melting compounds Na3LnCl6 with the cryolite-structure, incongruently melting compounds NaLnCl4 with the NaErCl4-Ln (Ln=Tm) or the NaLnCl4-structure (Ln=Yb, Lu). All these structure types contain [LnCl6]-octahedra. By solution calorimetry and e.m.f. measurements in galvanic cells for solid electrolytes could be proved that all compounds are formed from NaCl and LnCl3 by gain in lattice enthalpy.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1010115407242
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  • 4
    Electronic Resource
    Electronic Resource
    Zur Stabilität von Doppelchloriden in den Systemen ACI/PrCl3(A = Na—Cs) (1987)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 555 (1987), S. 143-153 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Stability of Double Chlorides in the Systems ACl/PrCl3(A = Na—Cs)The pseudobinary systems ACl/PrCl3(A = Na—Cs) were reinvestigated by means of DTA. The following chlorides were found. (Primary detected compounds are underlined.): \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Na}_{\rm 2} {\rm Pr}_{\rm 5} {\rm Cl}_{{\rm 18}} } $\end{document} K3PrCl6; K2PrCl5; \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Rb}_{\rm 3} {\rm Pr} {\rm Cl}_{{\rm 6}} } $\end{document} Rb2PrCl5, \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Rb} {\rm Pr}_{\rm 2} {\rm Cl}_{{\rm 7}} } $\end{document} Cs3PrCl6, \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Cs}_{\rm 3} {\rm Pr} {\rm Cl}_{{\rm 5}} } $\end{document}, CsPr2Cl7.Measurements of the solution enthalpies and of the free (Gibbs) enthalpies of formation from ACl and PrCl3 together with the free enthalpies of synproportionation from the adjacent compounds in the phase diagrams with a galvanic cell for solid electrolytes revealed, that only the chlorides A2PrCl5 are stable at ambient temperature. All other compounds are high temperature forms.The crystal structures of the compounds were determined by X-ray analysis on powders; the compounds are isotypic with the analogous double chlorides of La and Ce. Magnetic susceptibilities in the range from 80 - 300 K were measured with a Gouy-balance.
    Notes: Die pseudobinären Systeme ACl/PrCl3(A = Na—Cs) wurden mittels DTA neu untersucht. Folgende Verbindungen wurden gefunden (erstmalig nachgewiesene Verbindungen sind unterstrichen) \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Na}_{\rm 2} {\rm Pr}_{\rm 5} {\rm Cl}_{{\rm 18}} } $\end{document} K3PrCl6; K2PrCl5; \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Rb}_{\rm 3} {\rm Pr} {\rm Cl}_{{\rm 6}} } $\end{document} Rb2PrCl5, \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Rb} {\rm Pr}_{\rm 2} {\rm Cl}_{{\rm 7}} } $\end{document} Cs3PrCl6, \documentclass{article}\pagestyle{empty}\begin{document}$ \underline {{\rm Cs}_{\rm 3} {\rm Pr} {\rm Cl}_{{\rm 5}} } $\end{document}, CsPr2Cl7. Messungen der Lösungsenthalpien, der freien Enthalpien für die Bildung aus ACl und den PrCl3-reicheren Nachbarverbindungen mittels einer galvanischen Zelle für feste Elektrolyte sowie die Berechnung der freien Enthalpien für die Synproportionierung aus den Nachbarverbindungen im Zustandsdiagramm ergaben, daß nur die Chloride A2PrCl5 bei Raumtemperatur stabil sind; alle anderen sind Hochtemperaturphasen. Strukturuntersuchungen an Kristallpulvern ergaben Isotypie mit den entsprechenden La- und Ce-Verbindungen. Magnetische Suszeptibilitäten nach der Gouy-Methode im Bereich 80 - 300 K zeigen die erwarteten Werte.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19875551215
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  • 5
    Electronic Resource
    Electronic Resource
    Ternäre Chloride in den Systemen ACl/DyCl3 (A = Cs, Rb, K)Professor Wilhelm Preetz zum 60. Geburtstage gewidmet (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1543-1548 
    Details
    ISSN: 0044-2313
    Keywords: Alkali metal chlorides/dysprosium chloride systems ; phase diagrams ; thermodynamic properties ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Chlorides in the Systems ACl/DyCl3 (A = Cs, Rb, K)The phase diagrams of the pseudobinary systems ACl/DyCl3 (A = Cs, Rb, K) were investigated by DTA. With all alkali metals compounds A3DyCl6 (elpasolite family) and Ady2Cl7 are formed. Compounds A2DyCl5 exist only with Cs (Cs2DyCl5-type) and K (K2PrCl5-type). By solution calorimetry the formation enthalpies of the ternary chlorides from (nACl + DyCl3) were measured and ‘synproportionation enthalpies’ for the formation from the compounds, adjacent in the phase diagrams, calculated. K3DyCl6 is the only compound, which is formed with a loss in lattice enthalpy. E.m.f. measurements in dependence on the temperature have revealed that, as for the other compounds A3DyCl6, a remarkable gain in entropy exists, which stabilizes K3DyCl6 at T ≧ 312 K. This entropy gain correlates with the existence of isolated DyCl63- octahedra.
    Notes: Die Zustandsdiagramme der pseudobinären Systeme ACl/DyCl3 (A = Cs, Rb, K) wurden mittels DTA untersucht. Es existieren mit allen Alkalimetallen Verbindungen A3DyCl6 (Elpasolithfamilie) und Ady2Cl7 sowie Verbindungen A2DyCl5 mit A = Cs (Cs2DyCl5-Typ) und A = K (K2PrCl5-Typ). Von allen Verbindungen wurden über Lösungswärmen die Bildungsenthalpien aus (nACl + DyCl3) bestimmt und daraus ‘Synproportionierungsenthalpien’ für die Bildung aus den im Zustandsdiagramm benachbarten Verbindungen berechnet. Nur K3DyCl6 bildet sich aus den Nachbarn unter Verlust an Gitterenthalpie. EMK = f(T)Messungen zeigen, daß diese Verbindung oberhalb 39°C durch Entropiegewinn stabilisiert ist. Ähnlich große Entropiegewinne treten auch bei den anderen Verbindungen A3DyCl6 auf; sie alle enthalten isolierte Koordinationspolyeder.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19946200909
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  • 6
    Electronic Resource
    Electronic Resource
    Ternäre Chloride in den Systemen NaCl/HoCl3 und NaCl/ErCl3Professor Dieter Seebach zum 60. Geburtstag gewidmet (1997)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 623 (1997), S. 1525-1528 
    Details
    ISSN: 0044-2313
    Keywords: Ternary sodium chlorides ; Holmium ; Erbium ; Phase diagrams ; Thermodynamic properties ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Chlorides in the Systems NaCl/HoCl3 and NaCl/ErCl3Phase diagrams of the systems NaCl/HoCl3 and NaCl/ErCl3 were determined by means of DTA and high-temperature XRD. There exist compounds Na3LnCl6, NaLnCl4 (Ln = Ho, Er) and NaHo2Cl7. NaHoCl4 undergoes a phase transition at 374°C from the NaGdCl4- to the NaErCl4- type of structure. The thermodynamic functions for the formation of the compounds from NaCl and LnCl3 were determined by solution calorimetry and e.m.f. measurements in galvanic cells for solid electrolytes. The compounds NaLnCl4 are the most stable ones.
    Notes: Die Zustandsdiagramme der Systeme NaCl/HoCl3 und NaCl/ErCl3 wurden mittels DTA und Hochtemperatur-Guinieraufnahmen untersucht. Es existieren Verbindungen Na3LnCl6 und NaLnCl4 (Ln = Ho, Er) sowie NaHo2Cl7. NaHoCl4 wandelt sich bei 374° vom NaGdCl4- in den NaErCl4-Typ um. Mittels Lösungskalorimetrie und EMK-Messungen in galvanischen Feststoffzellen wurden die thermodynamischen Funktionen der ternären Chloride bezüglich der Bildung aus NaCl und LnCl3 bestimmt. Die Verbindungen NaLnCl4 weisen die größte Stabilität auf.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19976231009
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  • 7
    Electronic Resource
    Electronic Resource
    Ternäre Chloride in den Systemen ACl/GdCl3 (A = Na—Cs)Professor Hans-Georg von Schnering zum 60. Geburtstage gewidmet (1991)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 598 (1991), S. 307-318 
    Details
    ISSN: 0044-2313
    Keywords: Alkali halides/gadolinium halide systems ; phase diagrams ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Ternary Chlorides in the Systems ACl/GdCl3 (A = Na—Cs)The phase diagrams of the pseudobinary systems ACl/GdCl3 (A = Na—Cs) were investigated by DTA. Their powder diffractograms were indexed in analogy to known structure families. By solution calorimetry and measurements of e.m.f. = f(T) in galvanic cells for solid electrolytes the enthalpies ΔH0 and free enthalpies ΔG0 for the formation of the ternary chlorides from the compounds adjacent in the systems were determined. The systems with A = K, Rb, Cs are analogous to those with Sm3+ and Eu3+. There exist compounds A3GdCl6, A2GdCl5 and AGd2Cl7. Cs2GdCl5 is crystallysing in the Cs2DyCl5 type; the Rb- and K-compounds and also Na2GdCl5 have the K2PrCl5-structure. In the system NaCl/GdCl3 additionally the compounds NaGdCl4 and Na3GdCl6 were found. L—Na3GdCl6 is metastable compared with (NaCl + Na2GdCl5); above 265°C stable H—Na3GdCl6 is existing (cryolite-structure).
    Notes: Die Zustandsdiagramme der pseudobinären Systeme ACl/GdCl3 (A = Na—Cs) wurden mittels DTA untersucht und soweit noch nicht bekannt die Strukturen der existierenden ternären Chloride aus Röntgenaufnahmen an Kristallpulvern bestimmt. Die Systeme mit A = K, Rb, Cs entsprechen den Systemen des Sm3+ und Eu3+. Es treten die Verbindungen A3GdCl6, A2GdCl5 und AGd2Cl7 auf. Von den 2:1-Verbindungen kristallisiert Cs2GdCl5 im Cs2DyCl5-Typ, die Verbindungen mit Rb und K sowie Na2GdCl5 im K2PrCl5-Typ. Im System NaCl/GdCl3 wurden außerdem die Verbindungen Na3GdCl6 und NaGdCl4 nachgewiesen. T—Na3GdCl6 ist metastabil gegenüber dem Zerfall zu NaCl und Na2GdCl5; oberhalb 265°C existiert stabiles H—Na3GdCl6 mit Kryolith-Struktur.über Messungen der Lösungsenthalpien und EMK-Messungen als Funktion der Temperatur in galvanischen Zellen für feste Elektrolyte wurden die Enthalpien ΔH0 und freien Enthalpien ΔG0 für die Bildung der ternären Chloride aus den im System benachbarten Verbindungen bestimmt. Auch hier entsprechen die Ergebnisse den in den Sm- und Eu-Systemen gefundenen.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19915980128
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  • 8
    Electronic Resource
    Electronic Resource
    Zur Thermochemie und Struktur von Berylliumchlorid (1995)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 621 (1995), S. 1723-1726 
    Details
    ISSN: 0044-2313
    Keywords: Beryllium dichloride ; dimorphy ; enthalpy ; entropy ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Thermochemistry and Structure of Beryllium ChlorideBeCl2 is dimorphous, with a transition point at 405°C. The transition enthalpy and transition entropy have been determined by solution calorimetry: ΔUH° = 2.9 kJmol-1 and ΔUS° = 9.7 JK-1mol-1.The previously known SiS2-type structure of BeCl2 is that of the high temperature phase. The structure of the phase stable at room temperature has been determined from single crystal data. a = 1 062.4(6) pm, c = 1 804(2) pm, I41/acd, Z = 32, R = 0.038 (Mg(NH2)2-type). The structure consists of P4O10-like [Be4Cl6Cl4/2]-units, connected by their terminal anions.
    Notes: BeCl2 ist dimorph, die Umwandlungstemperatur liegt bei 405°C. Aus lösungskalorimetrischen Messungen ergibt sich als Differenz der Lösungsenthalpien eine Umwandlungsenthalpie von ΔUH° = 2,9 kJmol-1 und eine Umwandlungsentropie ΔUS298° = 9,7 JK-1 mol-1.Die bislang bekannte Struktur im SiS2-Typ ist die der Hochtemperaturphase. Die Struktur von bei Raumtemperatur stabilem T-BeCl2 wurde aus Einkristalldaten bestimmt. a = 1 062,4(6) pm, c = 1 804(2) pm, I41/acd, Z = 32, R = 0,038 (Mg(NH2)2-Typ). Es liegen (Be4Cl6Cl4/2)-Einheiten vor, die dem Bauprinzip von P4O10 entsprechen, aber über ihre terminalen Chlorid-Ionen verknüpft sind.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19956211018
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  • 9
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    Electronic Resource
    Ternäre Chloride in den Systemen ACl/EuCl3(A = Na—Cs)Professor Dirk Reinen zum 60. Geburtstage gewidmet (1990)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 587 (1990), S. 110-118 
    Details
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Double Chlorides in the Systems ACl/EuCl3 (A = Na—Cs)The phase diagrams of the pseudobinary systems ACl/EuCl3 (A = Na—Cs) were investigated by DTA. T— and H—A3EuCl6 with A = Cs, Rb and T— and H—NaEuCl4 were found in addition to other compounds already described in literature. Their powder diffractograms were indexed in analogy to known structure families. By solution calorimetry and measurements of e.m.f. = f(T) in galvanic cells for solid electrolytes the enthalpies ΔH and free enthalpies ΔG for the formation of the ternary chlorides from the compounds adjacent in the systems were determined. With KCl and NaCl only the compounds A2EuCl5 and NaEuCl4 are stable at ambient temperature. Compared to the system with LnCl3 (Ln = La—Nd) investigated previously, a tendency to structures with lower coordination numbers exists as was already detected in the systems ACl/SmCl3.
    Notes: Die Zustandsdiagramme der pseudobinären Systeme ACl/EuCl3 (A = Na—Cs) wurden mittels DTA untersucht. Neu gefunden wurden T— und H—A3EuCl6 mit A = Cs, Rb sowie T— und H—NaEuCl4. Soweit nicht schon bekannt, wurden Röntgenaufnahmen an Kristallpulvern analog zu bekannten Strukturfamilien indiziert. Über Messungen der Lösungsenthalpien und EMK-Messungen als Funktion der Temperatur in galvanischen Zellen für feste Elektrolyte wurden die Enthalpien ΔH und freien Enthalpien ΔG für die Bildung der ternären Chloride aus den im System benachbarten Verbindungen bestimmt. In den Systemen des KCl und NaCl sind nur A2EuCl5 sowie NaEuCl4 bei Raumtemperatur stabil.Im Vergleich zu den früher untersuchten Systemen mit LnCl3 (Ln = La—Nd) setzt sich die bei den Sm-Verbindungen auftretende Tendenz zur Bildung von Strukturen mit niedrigeren Koordinationszahlen als bei den größeren Lanthanoiden fort.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/zaac.19905870113
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  • 10
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    Metall-Koordinationsverbindungen aus Essigsäure. I Chlorometallate(III) des Eisens, Chroms und VanadiumsProfessor Heinrich Oppermann zum 60. Geburtstag gewidmet (1994)
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 620 (1994), S. 1943-1946 
    Details
    ISSN: 0044-2313
    Keywords: Ternary chlorometalates(III) ; crystal structure ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Metal Coordination Compounds Prepared in Acetic Acid. I. Chlorometalates(III) of Iron, Chromium, and VanadiumTernary chloride-hydrates A2MCl5 · H2O (A = Cs, Rb, (K)) can be precipitated with HCl from solutions of MCl3 · 6 H2O, (M = Fe, Cr, V) and alkali metal acetates in acetic acid. Under special conditions also compounds of the composition Cs3MCl6 · H2O can be obtained. After dehydration of the solutions with acetyl chloride, anhydrous compounds are formed: Cs3Fe2Cl9; A3CrCl6 and A3Cr2Cl9 with A = Cs, Rb; Cs3VCl6 and Cs3V2Cl9. VIII is partially oxidized to VIV by an excess of acetyl chloride. Compounds A2VCl6 with A = Cs, Rb can be obtained more conveniently by the reaction of VOCl2 · H2O in acetic acid with acetyl chloride.The lattice parameters of some compounds were determined from powder patterns in analogy to known structure families.
    Notes: Aus Lösungen der Chloridhydrate MCl3 · 6 H2O (M = Fe, Cr, V) in Eisessig lassen sich nach Zugabe von Alkalimetallacetaten mit HCl ternäre Chloridhydrate A2MCl5 · H2O (A = Cs, Rb, z. T. K), unter speziellen Bedingungen auch Verbindungen der Zusammensetzung Cs3MCl6 · H2O fällen. Werden die Ausgangslösungen mit Acetylchlorid dehydratisiert, so entstehen wasserfreie Chlorometallate(III): Cs3Fe2Cl9; A3CrCl6 und A3Cr2Cl9 mit A = Cs, Rb; Cs3VCl6 und Cs3V2Cl9. Vanadium(III) kann teilweise zu VIV oxidiert werden. Chlorovanadate A2VCl6 mit A = Cs, Rb lassen sich aber günstiger aus Lösungen von VOCl2 · 2 H2O in Eisessig mit Acetylchlorid erhalten.Von einigen strukturell noch nicht untersuchten Verbindungen sind durch Analogindizierungen von Pulveraufnahmen die Gitterparameter bestimmt worden.
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    URL: http://dx.doi.org/10.1002/zaac.19946201118
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