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American Mineralogist; April 2006; v. 91; no. 4; p. 658-666; DOI: 10.2138/am.2006.1856
© 2006 Mineralogical Society of America
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Thermodynamics of uranyl minerals: Enthalpies of formation of uranyl oxide hydrates

Karrie-Ann Kubatko1, Katheryn Helean2, Alexandra Navrotsky2 and Peter C. Burns1,*

1 Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatrick Hall, Notre Dame, Indiana 46556, U.S.A.
2 Thermochemistry Facility and NEAT ORU, University of California at Davis, One Shields Avenue, Davis, California 95616, U.S.A.

Correspondence: * E-mail: khughes1{at}nd.edu

The enthalpies of formation of seven uranyl oxide hydrate phases and one uranate have been determined using high-temperature oxide melt solution calorimetry: [(UO2)4O(OH)6](H2O)5, metaschoepite; ß-UO2(OH)2; CaUO4; Ca(UO2)6O4(OH)6(H2O)8, becquerelite; Ca(UO2)4O3(OH)4(H2O)2; Na(UO2)O(OH), clarkeite; Na2(UO2)6O4(OH)6(H2O)7, the sodium analogue of compreignacite, and Pb3(UO2)8O8(OH)6(H2O)2, curite. The enthalpy of formation from the binary oxides, {Delta}Hf-ox, at 298 K was calculated for each compound from the respective drop solution enthalpy, {Delta}Hds. The standard enthalpies of formation from the elements, {Delta}Hf°, at 298 K are –1791.0 ± 3.2, –1536.2 ± 2.8, –2002.0 ± 3.2, –11389.2 ± 13.5, –6653.1 ± 13.8, –1724.7 ± 5.1, –10936.4 ± 14.5, and –13163.2 ± 34.4 kJ/mol, respectively. These values are useful in exploring the stability of uranyl oxide hydrates in auxiliary chemical systems, such as those expected in U-contaminated environments.

Key Words: Calorimetry • becquerelite • enthalpy • compreignacite • metaschoepite • uranyl • curite • uranium




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