TY - JOUR
T1 - Thermodynamics of uranyl minerals
T2 - Enthalpies of formation of rutherfordine, UO2CO3, andersonite, Na2CaUO2(CO3)3 (H2O)5, and grimselite, K3NaUO 2(CO3)3H2O
AU - Kubatko, Karrie Ann
AU - Helean, Katheryn B.
AU - Navrotsky, Alexandra
AU - Burns, Peter C.
N1 - Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.
PY - 2005/8
Y1 - 2005/8
N2 - Enthalpies of formation of rutherfordine, UO2CO3, andersonite, Na2CaUO2(CO3)3 (H2O)5, and grimselite, K3NaUO 2(CO3)3(H2O), have been determined using high-temperature oxide melt solution calorimetry. The enthalpy of formation of rutherfordine from the binary oxides, ΔHr-ox, is -99.1 ± 4.2 kJ/mol for the reaction UO3 (xl, 298 K) + CO2 (g, 298 K) = UO2CO3 (xl, 298 K). The ΔHr-ox for andersonite is - 710.4 ± 9.1 kJ/mol for the reaction Na2O (xl, 298 K) + CaO (xl, 298 K) + UO3 (xl, 298 K) + 3CO2 (g, 298 K) + 5H2O (1, 298 K) = Na2CaUO2(CO3)3 (H2O)6 (xl, 298 K). The ΔHr-ox for grimselite is -989.3 ± 14.0 kJ/mol for the reaction 1.5 K2O (xl, 298 K) + 0.5Na2O (xl, 298 K) + UO3 (xl, 298 K) + 3CO2 (g, 298 K) + H2O (1, 298 K) = K3NaUO2(CO3)3 H2O (xl, 298 K). The standard enthalpies of formation from the elements, ΔHfo, are -1716.4 ± 4.2, -5593.6 ± 9. 1, and -4431.6 ± 15.3 kJ/mol for rutherfordine, andersonite, and grimselite, respectively. Energetic trends of uranyl carbonate formation from the binary oxides and ternary carbonates are dominated by the acid-base character of the binary oxides. However, even relative to mixtures Of UO2CO3, K2CO3, and Na2CO3 or CaCO3, andersonite and grimselite are energetically stable by 111.7 ± 10.2 and 139.6 ± 16.1 kJ/mol, respectively, suggesting additional favorable interactions arising from hydration and/or changes in cation environments. These enthalpy values are discussed in comparison with earlier estimates.
AB - Enthalpies of formation of rutherfordine, UO2CO3, andersonite, Na2CaUO2(CO3)3 (H2O)5, and grimselite, K3NaUO 2(CO3)3(H2O), have been determined using high-temperature oxide melt solution calorimetry. The enthalpy of formation of rutherfordine from the binary oxides, ΔHr-ox, is -99.1 ± 4.2 kJ/mol for the reaction UO3 (xl, 298 K) + CO2 (g, 298 K) = UO2CO3 (xl, 298 K). The ΔHr-ox for andersonite is - 710.4 ± 9.1 kJ/mol for the reaction Na2O (xl, 298 K) + CaO (xl, 298 K) + UO3 (xl, 298 K) + 3CO2 (g, 298 K) + 5H2O (1, 298 K) = Na2CaUO2(CO3)3 (H2O)6 (xl, 298 K). The ΔHr-ox for grimselite is -989.3 ± 14.0 kJ/mol for the reaction 1.5 K2O (xl, 298 K) + 0.5Na2O (xl, 298 K) + UO3 (xl, 298 K) + 3CO2 (g, 298 K) + H2O (1, 298 K) = K3NaUO2(CO3)3 H2O (xl, 298 K). The standard enthalpies of formation from the elements, ΔHfo, are -1716.4 ± 4.2, -5593.6 ± 9. 1, and -4431.6 ± 15.3 kJ/mol for rutherfordine, andersonite, and grimselite, respectively. Energetic trends of uranyl carbonate formation from the binary oxides and ternary carbonates are dominated by the acid-base character of the binary oxides. However, even relative to mixtures Of UO2CO3, K2CO3, and Na2CO3 or CaCO3, andersonite and grimselite are energetically stable by 111.7 ± 10.2 and 139.6 ± 16.1 kJ/mol, respectively, suggesting additional favorable interactions arising from hydration and/or changes in cation environments. These enthalpy values are discussed in comparison with earlier estimates.
UR - http://www.scopus.com/inward/record.url?scp=26944476291&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=26944476291&partnerID=8YFLogxK
U2 - 10.2138/am.2005.1821
DO - 10.2138/am.2005.1821
M3 - Article
AN - SCOPUS:26944476291
SN - 0003-004X
VL - 90
SP - 1284
EP - 1290
JO - American Mineralogist
JF - American Mineralogist
IS - 8-9
ER -