Lanthanide(III) halides: Thermodynamic properties and their correlation with crystal structure

Rycerz, L.; Gaune‐Escard, M.

doi:10.1016/j.jallcom.2006.12.096

Cited by 23 publications

(18 citation statements)

References 31 publications

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“…In this contribution, we therefore list only thermochemical data for REE chlorides obtained using calorimetric methods (Table 11). A review of the available thermochemical data for solid, liquid, and gaseous REE trihalides, including REE chlorides, has been published by Konings and Kovács (2003); these data were refined later by Rycerz and Gaune-Escard (2008).…”

Section: Ree Halogenides (Chlorides and Fluorides)mentioning

confidence: 99%

Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations

et al. 2016

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For many years, our understanding of the behavior of the REE in hydrothermal systems was based on semiempirical estimates involving extrapolation of thermodynamic data obtained at 25°C (Haas et al., 1995;Wood, 1990a). Since then, a substantial body of experimental data has accumulated on the stability of aqueous complexes of the REE. These data have shown that some of the predictions of Haas et al. (1995) are accurate, but others may be in error by several orders of magnitude. However, application of the data in modeling hydrothermal transport and deposition of the REE has been severely hampered by the lack of data on the thermodynamic properties of even the most common REE minerals. The discrepancies between the predictions of Haas et al. (1995) and experimental determinations of the thermodynamic properties of aqueous REE species, together with the paucity of data on the stability of REE minerals, raise serious questions about the reliability of some models that have been proposed for the hydrothermal mobility of these critical metals. In this contribution, we review a body of high-temperature experimental data collected over the past 15 years on the stability of REE aqueous species and minerals. Using this new thermodynamic dataset, we re-evaluate the mechanisms responsible for hydrothermal transport and deposition of the REE. We also discuss the mechanisms that can result in REE fractionation during their hydrothermal transport and deposition. Our calculations suggest that in hydrothermal solutions, the main REE transporting ligands are chloride and sulfate, whereas fluoride, carbonate, and phosphate likely play an important role as depositional ligands. In addition to crystallographic fractionation, which is based on the differing affinity of mineral structures for the REE, our models suggest that the REE can be fractionated hydrothermally due to the differences in the stability of the LREE and HREE as aqueous chloride complexes.

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Section: Ree Halogenides (Chlorides and Fluorides)mentioning

confidence: 99%

Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations

et al. 2016

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“…As distinct from the data of Seifert et al [10], transformation of PuBr 3 type structure into the thermodynamically stable AlCl 3 -like modification takes place at 430 °C. Despite evident discrepancies in the results obtained in [6][7][8][9][10][11][12], all the results point to the existence of at least two crystalline modifications of dysprosium trichloride in the wide temperature range from 20 °C to the melting point.…”

Section: Introductionmentioning

confidence: 77%

“…1a-g). The temperature range at which a possible phase transfer took place [6][7][8][9][10] was carefully studied. The total spectral pattern did not show qualitative changes: the number of vibration lines and their relative intensity remained constant.…”

Section: Raman Spectroscopymentioning

confidence: 99%

“…We attempted to obtain orthorhombic DyCl 3 modification, but neither fast freezing of the melt (cooling of ampoules with the sample in water), nor keeping the dysprosium trichloride at a constant temperature (230 °C) for several hours, which is below the supposed phase transformation temperature [6][7][8][9][10], did not lead to any changes in the monoclinic structure: Raman spectra of the samples pointed only to the structure in the temperature range from 18 °C to the melting point. Figure 2 demonstrates temperature dependences of the crystalline DyCl 3 vibration bands intensity maximums.…”

Section: Raman Spectroscopymentioning

confidence: 99%

“…The phase transition enthalpy measured was 1.4 kJ/mol. In a later study [9], these authors concluded that the phase transition in crystalline dysprosium trichloride appears because of the transition of the monoclinic structure of the AlCl 3 type to the high temperature orthorhombic structure of the PuBr 3 type. Many different results are presented in the article [10], which is devoted to the study of phase diagrams of ACl/DyCl 3 (A = Cs, Rb, K) binary systems.…”

Section: Introductionmentioning

confidence: 96%

See 2 more Smart Citations

On Polymorphism of Dysprosium Trichloride

Zakirýanova

Хохлов

Salyulev

et al. 2015

Zeitschrift Für Naturforschung A

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For the first time, the structure of crystalline DyCl 3 over a wide temperature range from room temperature to melting point was studied by Raman spectroscopy. The phonon modes (cm -1 ) of dysprosium trichloride (monoclinic crystal lattice of AlCl 3 type, Z = 4, CN = 6) at room temperature are 257 (A 1g ), 201 (E g ), 112 (E g ), 88 (A 1g ), and 63 (E g ). The monoclinic structure of the crystalline DyCl 3 C 2h 3 symmetry was found to remain constant over the studied temperature range. No polymorphic transformation in the solid state was detected. Gravimetry, calorimetry, and mass spectrometry have been used in addition to support the conclusions made on the basis of Raman spectroscopic data.

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Facile Synthesis of Anhydrous Rare‐Earth Trichlorides from their Oxides in Chloridoaluminate Ionic Liquids

Shah,

Pietsch,

Ruck

2023

Angewandte Chemie

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Wide applications of anhydrous rare‐earth (RE) trichlorides RECl3 in organometallic chemistry, for the synthesis of optical and magnetic materials, and as catalysts require a facile approach for their synthesis. The known methods use or produce toxic substances, are complicated and have limited reliability and upscaling. It has been shown that task‐specific ionic liquids (ILs) can dissolve many metal oxides without special reaction conditions at moderate temperature, making the metals accessible to downstream chemistry. Using imidazolium chloridoaluminate ILs, pure crystalline anhydrous RECl3 (RE=La−Nd, Sm−Dy) can be synthesized in one step from RE oxides in high yield. The Lewis acidic IL acts as solvent and reaction partner. The by‐product [Al4O2Cl10]2−, which was detected spectroscopically, remains in solution. The reacted IL can be removed quantitatively by washing. ILs with various imidazolium cations and AlCl3 content and the effect of temperature and reaction time were tested.

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Lanthanide(III) halides: Thermodynamic properties and their correlation with crystal structure

Cited by 23 publications

References 31 publications

Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations

Hydrothermal transport, deposition, and fractionation of the REE: Experimental data and thermodynamic calculations

On Polymorphism of Dysprosium Trichloride

Facile Synthesis of Anhydrous Rare‐Earth Trichlorides from their Oxides in Chloridoaluminate Ionic Liquids

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