The Thermodynamic Properties of the f-Elements and Their Compounds. I. The Lanthanide and Actinide Metals

Konings, R.J.M.; Beneš, O.

doi:10.1063/1.3474238

Cited by 86 publications

(158 citation statements)

References 223 publications

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“…For detailed analyses of the data available for REE oxides and the techniques used for their derivation, readers are referred to the reviews of Morss and Konings (2005); Konings et al (2014), and Navrotsky et al (2015). Table 10 lists the properties of REE oxides recommended by Konings et al (2014) and Navrotsky et al (2015). This table only considers simple REE oxides; for the properties of complex oxides, such as, for example, NdFeO 3 , readers are referred to the review of Navrotsky et al (2015).…”

Section: Ree Oxides and Hydroxidesmentioning

confidence: 99%

“…These mostly involved calorimetric determinations. For detailed analyses of the data available for REE oxides and the techniques used for their derivation, readers are referred to the reviews of Morss and Konings (2005); Konings et al (2014), and Navrotsky et al (2015). Table 10 lists the properties of REE oxides recommended by Konings et al (2014) and Navrotsky et al (2015).…”

Section: Ree Oxides and Hydroxidesmentioning

confidence: 99%

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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 Oxides and Hydroxidesmentioning

confidence: 99%

Section: Ree Oxides and Hydroxidesmentioning

confidence: 99%

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

et al. 2016

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“…Most lanthanide metals have some form of hexagonal closepacked structure 33 with three bonding electrons per metal atom outside an inner 4f q sub-shell. 35 Reaction (4) is then one in which the 4f electrons are conserved.…”

Section: The Standard Enthalpies Of Formation Of Gaseous Tripositive mentioning

confidence: 99%

“…There are two recent reviews of the values of D f H Ɵ (M,g) for the lanthanide elements. 33,34 We have used the averages of the two sets, and they appear in column 3 of Table 10. Promethium has been omitted because of the absence of an experimental value.…”

Section: The Standard Enthalpies Of Formation Of Gaseous Tripositive mentioning

confidence: 99%

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Lanthanide Ionization Energies and the Sub-Shell Break. Part 2. The Third and Fourth Ionization Energies

Johnson

Nelson

2017

Journal of Physical and Chemical Reference Data

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By interpolating a 4fq6s → 4fq7s transition within the sequence f1 → f14 rather than between f0 and f14, revised third and fourth ionization energies of the lanthanides have been obtained. The revised values, together with the second ionization energies calculated in a previous paper, are used to calculate values of the standard enthalpies of formation of the gaseous tripositive ions, ΔfHƟ(M3+,g), and of the lattice and hydration enthalpies of some lanthanide compounds and ions in the trivalent and tetravalent states. The displacements of f0 values from nearly smooth f1 → f14 variations exceed 30 kJ mol−1 and indicate substantial subshell breaks.

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Phase Transition

Бацанов

Batsanov

2012

Introduction to Structural Chemistry

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The Thermodynamic Properties of the f-Elements and Their Compounds. I. The Lanthanide and Actinide Metals

Cited by 86 publications

References 223 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

Lanthanide Ionization Energies and the Sub-Shell Break. Part 2. The Third and Fourth Ionization Energies

Phase Transition

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