Energetics of cation mixing in urania-ceria solid solutions with stoichiometric oxygen concentrations

Benjamin E. Hanken; Tatiana Y. Shvareva; Niels Grønbech-Jensen; Christopher R. Stanek; Mark Asta; Alexandra Navrotsky

doi:10.1039/c2cp40295e

Energetics of cation mixing in urania-ceria solid solutions with stoichiometric oxygen concentrations

Benjamin E. Hanken, Tatiana Y. Shvareva, Niels Grønbech-Jensen, Christopher R. Stanek, Mark Asta, Alexandra Navrotsky

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Cation mixing energetics in urania-ceria solid solutions with stoichiometric oxygen concentrations (U _1-yCe _yO ₂) have been measured by high-temperature oxide-melt drop-solution calorimetry. Measurements have been performed on eight samples with compositions spanning y = 0.119 to y = 0.815. The measured mixing enthalpies (ΔH _mix) range from -0.6 ± 3.3 to 3.9 ± 3.0 kJ mol ^-1. These values are discussed in the context of results from atomistic modeling which take into consideration the possibility of charge transfer between uranium and cerium cations to form solid solutions with mixed charge states. A comparison between measured and calculated results for ΔH _mix suggests that such charge transfer takes place to a limited extent in the most concentrated mixtures studied.

Original language	English (US)
Pages (from-to)	5680-5685
Number of pages	6
Journal	Physical Chemistry Chemical Physics
Volume	14
Issue number	16
DOIs	https://doi.org/10.1039/c2cp40295e
State	Published - Apr 28 2012
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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abstract = "Cation mixing energetics in urania-ceria solid solutions with stoichiometric oxygen concentrations (U 1-yCe yO 2) have been measured by high-temperature oxide-melt drop-solution calorimetry. Measurements have been performed on eight samples with compositions spanning y = 0.119 to y = 0.815. The measured mixing enthalpies (ΔH mix) range from -0.6 ± 3.3 to 3.9 ± 3.0 kJ mol -1. These values are discussed in the context of results from atomistic modeling which take into consideration the possibility of charge transfer between uranium and cerium cations to form solid solutions with mixed charge states. A comparison between measured and calculated results for ΔH mix suggests that such charge transfer takes place to a limited extent in the most concentrated mixtures studied.",

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AU - Hanken, Benjamin E.

AU - Shvareva, Tatiana Y.

AU - Grønbech-Jensen, Niels

AU - Stanek, Christopher R.

AU - Asta, Mark

AU - Navrotsky, Alexandra

PY - 2012/4/28

Y1 - 2012/4/28

N2 - Cation mixing energetics in urania-ceria solid solutions with stoichiometric oxygen concentrations (U 1-yCe yO 2) have been measured by high-temperature oxide-melt drop-solution calorimetry. Measurements have been performed on eight samples with compositions spanning y = 0.119 to y = 0.815. The measured mixing enthalpies (ΔH mix) range from -0.6 ± 3.3 to 3.9 ± 3.0 kJ mol -1. These values are discussed in the context of results from atomistic modeling which take into consideration the possibility of charge transfer between uranium and cerium cations to form solid solutions with mixed charge states. A comparison between measured and calculated results for ΔH mix suggests that such charge transfer takes place to a limited extent in the most concentrated mixtures studied.

AB - Cation mixing energetics in urania-ceria solid solutions with stoichiometric oxygen concentrations (U 1-yCe yO 2) have been measured by high-temperature oxide-melt drop-solution calorimetry. Measurements have been performed on eight samples with compositions spanning y = 0.119 to y = 0.815. The measured mixing enthalpies (ΔH mix) range from -0.6 ± 3.3 to 3.9 ± 3.0 kJ mol -1. These values are discussed in the context of results from atomistic modeling which take into consideration the possibility of charge transfer between uranium and cerium cations to form solid solutions with mixed charge states. A comparison between measured and calculated results for ΔH mix suggests that such charge transfer takes place to a limited extent in the most concentrated mixtures studied.

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Energetics of cation mixing in urania-ceria solid solutions with stoichiometric oxygen concentrations

Abstract

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