Stability of Cu2Ln2O5 compounds: Comparison, assessment and systematics
Identifieur interne : 000E95 ( Pascal/Curation ); précédent : 000E94; suivant : 000E96Stability of Cu2Ln2O5 compounds: Comparison, assessment and systematics
Auteurs : K. P. Jayadevan [Inde] ; K. T. Jacob [Inde]Source :
- High-temperature materials and processes [ 0334-6455 ] ; 2000.
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Abstract
Phase diagram studies show that at ambient pressure only one ternary oxide, Cu2Ln2O5, is stable in the ternary systems Cu-Ln-O (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu) at high temperatures. The crystal structure of Cu2Ln2O5 can be described as a zig-zag arrangement of one-dimensional Cu2O5 chains parallel to the a-axis with Ln atoms occupying distorted octahedral sites between these chains. Four sets of emf measurements on Gibbs energy of formation of Cu2Ln2O5 (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu; Y) from component binary oxides and one set of high-temperature solution calorimetric data on enthalpy of formation have been reported in the literature. Except for Cu2Y2O5, the measured values for the Gibbs energies of formation of all other Cu2Ln2O5 compounds fall in a narrow band (±1 kJ mol-1) and indicate a regular increase in stability with decreasing ionic radius of the lanthanide ion. The values for the second law enthalpy of formation, derived from the temperature dependence of emf obtained in different studies, show larger differences, as high as 25 kJ mol-1 for Cu2Tm2O5. Though associated with an uncertainty of ±4 kJ mol-1, the calorimetric measurements help to identify the best set of emf data. The trends in thermodynamic data correlate well with the global instability index (GII) based on the overall deviation from the valence sum rule. Low values for the index calculated from crystallographic information indicate higher stability. Higher values are indicative of the larger stress in the structure.
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en" level="a">Stability of Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
compounds: Comparison, assessment and systematics</title>
<author><name sortKey="Jayadevan, K P" sort="Jayadevan, K P" uniqKey="Jayadevan K" first="K. P." last="Jayadevan">K. P. Jayadevan</name>
<affiliation wicri:level="1"><inist:fA14 i1="01"><s1>Materials Research Center and Department of Metallurgy, Indian Institute of Science</s1>
<s2>Bangalore 560 012</s2>
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<country>Inde</country>
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<author><name sortKey="Jacob, K T" sort="Jacob, K T" uniqKey="Jacob K" first="K. T." last="Jacob">K. T. Jacob</name>
<affiliation wicri:level="1"><inist:fA14 i1="01"><s1>Materials Research Center and Department of Metallurgy, Indian Institute of Science</s1>
<s2>Bangalore 560 012</s2>
<s3>IND</s3>
<sZ>1 aut.</sZ>
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<country>Inde</country>
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<sourceDesc><biblStruct><analytic><title xml:lang="en" level="a">Stability of Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
compounds: Comparison, assessment and systematics</title>
<author><name sortKey="Jayadevan, K P" sort="Jayadevan, K P" uniqKey="Jayadevan K" first="K. P." last="Jayadevan">K. P. Jayadevan</name>
<affiliation wicri:level="1"><inist:fA14 i1="01"><s1>Materials Research Center and Department of Metallurgy, Indian Institute of Science</s1>
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<author><name sortKey="Jacob, K T" sort="Jacob, K T" uniqKey="Jacob K" first="K. T." last="Jacob">K. T. Jacob</name>
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<series><title level="j" type="main">High-temperature materials and processes</title>
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<front><div type="abstract" xml:lang="en">Phase diagram studies show that at ambient pressure only one ternary oxide, Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
, is stable in the ternary systems Cu-Ln-O (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu) at high temperatures. The crystal structure of Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
can be described as a zig-zag arrangement of one-dimensional Cu<sub>2</sub>
O<sub>5</sub>
chains parallel to the a-axis with Ln atoms occupying distorted octahedral sites between these chains. Four sets of emf measurements on Gibbs energy of formation of Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
(Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu; Y) from component binary oxides and one set of high-temperature solution calorimetric data on enthalpy of formation have been reported in the literature. Except for Cu<sub>2</sub>
Y<sub>2</sub>
O<sub>5</sub>
, the measured values for the Gibbs energies of formation of all other Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
compounds fall in a narrow band (±1 kJ mol<sup>-1</sup>
) and indicate a regular increase in stability with decreasing ionic radius of the lanthanide ion. The values for the second law enthalpy of formation, derived from the temperature dependence of emf obtained in different studies, show larger differences, as high as 25 kJ mol<sup>-1</sup>
for Cu<sub>2</sub>
Tm<sub>2</sub>
O<sub>5</sub>
. Though associated with an uncertainty of ±4 kJ mol<sup>-1</sup>
, the calorimetric measurements help to identify the best set of emf data. The trends in thermodynamic data correlate well with the global instability index (GII) based on the overall deviation from the valence sum rule. Low values for the index calculated from crystallographic information indicate higher stability. Higher values are indicative of the larger stress in the structure.</div>
</front>
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O<sub>5</sub>
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Ln<sub>2</sub>
O<sub>5</sub>
, is stable in the ternary systems Cu-Ln-O (Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu) at high temperatures. The crystal structure of Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
can be described as a zig-zag arrangement of one-dimensional Cu<sub>2</sub>
O<sub>5</sub>
chains parallel to the a-axis with Ln atoms occupying distorted octahedral sites between these chains. Four sets of emf measurements on Gibbs energy of formation of Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
(Ln = Tb, Dy, Ho, Er, Tm, Yb, Lu; Y) from component binary oxides and one set of high-temperature solution calorimetric data on enthalpy of formation have been reported in the literature. Except for Cu<sub>2</sub>
Y<sub>2</sub>
O<sub>5</sub>
, the measured values for the Gibbs energies of formation of all other Cu<sub>2</sub>
Ln<sub>2</sub>
O<sub>5</sub>
compounds fall in a narrow band (±1 kJ mol<sup>-1</sup>
) and indicate a regular increase in stability with decreasing ionic radius of the lanthanide ion. The values for the second law enthalpy of formation, derived from the temperature dependence of emf obtained in different studies, show larger differences, as high as 25 kJ mol<sup>-1</sup>
for Cu<sub>2</sub>
Tm<sub>2</sub>
O<sub>5</sub>
. Though associated with an uncertainty of ±4 kJ mol<sup>-1</sup>
, the calorimetric measurements help to identify the best set of emf data. The trends in thermodynamic data correlate well with the global instability index (GII) based on the overall deviation from the valence sum rule. Low values for the index calculated from crystallographic information indicate higher stability. Higher values are indicative of the larger stress in the structure.</s0>
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<s2>NC</s2>
<s5>04</s5>
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<s5>04</s5>
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<s5>05</s5>
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<s2>NC</s2>
<s5>08</s5>
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<s2>NC</s2>
<s5>09</s5>
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<s2>NC</s2>
<s5>09</s5>
</fC03>
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<s2>NC</s2>
<s5>10</s5>
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<s2>NC</s2>
<s5>10</s5>
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<s5>11</s5>
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<s5>11</s5>
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<s5>12</s5>
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<s5>13</s5>
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<s5>23</s5>
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<s2>NC</s2>
<s5>23</s5>
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<s2>NC</s2>
<s5>24</s5>
</fC03>
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<s2>NC</s2>
<s5>24</s5>
</fC03>
<fC03 i1="16" i2="3" l="FRE"><s0>Système Cu O Tb</s0>
<s2>NK</s2>
<s4>INC</s4>
<s5>32</s5>
</fC03>
<fC03 i1="17" i2="3" l="FRE"><s0>Système Cu Dy O</s0>
<s2>NK</s2>
<s4>INC</s4>
<s5>33</s5>
</fC03>
<fC03 i1="18" i2="3" l="FRE"><s0>8130D</s0>
<s2>PAC</s2>
<s4>INC</s4>
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