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Thermodynamic Properties of Uranyl Minerals: Constraints from Calorimetry and Solubility Measurements Tatiana Y

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Thermodynamic Properties of Uranyl Minerals: Constraints from Calorimetry and Solubility Measurements Tatiana Y REVIEW pubs.acs.org/IECR Thermodynamic Properties of Uranyl Minerals: Constraints from Calorimetry and Solubility Measurements Tatiana Y. Shvareva,† Jeremy B. Fein,‡ and Alexandra Navrotsky*,† †University of California, Davis, Peter A. Rock Thermochemistry Laboratory, One Shields Avenue, Davis, California 95616, United States ‡University of Notre Dame, Department of Civil Engineering and Geological Sciences, 156 Fitzpatrick Hall, Notre Dame, Indiana 46556, United States 6+ 2+ ABSTRACT: More than 50 uranyl minerals, phases containing U as the uranyl UO2 cation, and hydroxide, carbonate, phosphate, and silicate anions, H2O, and alkali and alkaline earth cations, occur in nature and as corrosion products of spent nuclear fuel. Despite their importance and the need to understand their thermodynamics to predict uranium solubility, fate, and transport in the environment, reliable thermodynamic data have only been available recently. This paper summarizes recent studies of enthalpies of formation using high temperature oxide melt solution calorimetry and Gibbs free energies from solubility experiments. Standard state thermochemical parameters (at 25 °C and 1 bar) are tabulated and the stability and transformation sequences of these phases are discussed. The enthalpies of formation from oxides are discussed in terms of crystal structure and Lewis acid base interactions. À ’ INTRODUCTION For example, Santalova et al.16 reported enthalpy of formation As nuclear power becomes an increasing source of world of dihydrated (meta)schoepite UO3 3 2H2O from solution calo- rimetry in dilute HF as 1840.6 kJ/mol. Later, Tasker et al.17 energy, the environmental fate of actinides must be unambigu- À ously predicted. Because, in the long term, spent nuclear fuel is not determined the enthalpy of formation of UO3 3 2H2Oas 1825.4 ( 2.1 kJ/mol by calorimetry in more concentrated HF. ThereÀ were stable under moist oxidizing conditions, oxidative dissolution of ff radionuclides in groundwater with consequent formation of uranyl extensive solubility measurements with di erent techniques on 1 3 meta-schoepite that resulted in solubility products varying from minerals is a likely alteration pathway. À With uraninite (UO2) 18 21 being the major component of nuclear fuel, the most crucial 4.68 to 6.23. À Other uranyl oxide hydrates, becquerelite studies are focused on uranyl-based phases in which uranium is Ca[(UO2)3O2(OH)3]2 3 8H2O, clarkeite Na(UO2)O(OH), and 2+ compregnacite Na2[(UO2)3O2(OH)3]2 7H2O, have not been oxidized to the +6 state and is present as the UO2 cation. 3 1,4 6 studied directly by solution calorimetric methods. The solubility Numerous tests of natural analogs À and synthesized samples data strongly depend on the crystallinity of samples and had not (for example 2,7,8) on alteration of UO2 reveal uranyl oxide 22 hydrate minerals and uranyl silicates as major products. Also, been accurately determined. uranyl phosphates and carbonates can be formed under some Thermodynamic properties of uranyl carbonates are also poorly 5 constrained. There are several reliable solubility measurements for groundwater compositions. Mineral stabilities and solubilities 19,20,23 25 determine which solid phases form, and the distribution of rutherfordine UO2CO3 reported, À but the enthalpy of formation, 1689.6 ( 1.8 kJ/mol, accepted by Guillaumont et al.,14 uranium between solid and aqueous phases. Recently, it was also À shown that some uranyl minerals can incorporate Pu and Np into has been calculated from averaged solubility data and an experi- mentally determined standard entropy S° value,25 and not measured their structures, serving as host phases and thereby reducing heavy 26 9 12 directly. Alwan and Williams reported enthalpy and Gibbs free actinide mobility. À Thus, the knowledge of thermodynamic parameters for environmental actinide phases is critical for control, energy of formation for andersonite Na2Ca[(UO2)(CO3)3] 3 5H2O prevention, and remediation of radioactive contamination. but did not report experimental conditions or details of measure- Despite such obvious need for reliable thermodynamic data ments. Data on other uranyl carbonates are very limited and are restricted only to solubility estimates.13,14 for uranyl minerals, previously reported data are incomplete 27 and somewhat contradictory. Grenthe et al.,13 followed by Cordfunke et al. measured the enthalpy of formation of Guillaumont et al.,14 compiled and reviewed the chemical (UO2)3(PO4)2 by solution calorimetry in concentrated H2SO4 as 5491.3 ( 3.5 kJ/mol. With entropy values measured by thermodynamics of actinide materials and only very few values À 28 have been accepted as reliable for hydrated crystalline uranyl Barten, the Gibbs free energy of formation of (UO2)3(PO4)2, oxides, carbonates, phosphates, and silicates. These uranyl minerals are complex, structurally and chemically, with more Special Issue: Alternative Energy Systems: Nuclear Energy than 50 phases known,15 and the synthesis of pure materials and their detailed characterization are not straightforward. Received: February 4, 2011 Due to nonstoichiometry, their hydrous nature and complex Accepted: November 12, 2011 oxidation reduction behavior, the best choice of thermody- Revised: October 11, 2011 À namic measurement methods is a challenge. Published: November 12, 2011 r 2011 American Chemical Society 607 dx.doi.org/10.1021/ie2002582 | Ind. Eng. Chem. Res. 2012, 51, 607–613 Industrial & Engineering Chemistry Research REVIEW Table 1. Thermodynamic Functions for Formation from Oxides and Elements of Uranyl Minerals, under Standard Temperature and Pressure formula per one ΔHf, el, ΔGf, el, ΔSf, el, S°, phase, formula uranyl cation ΔHf, ox, kJ/mol kJ/mol kJ/mol J/mol 3 K J/mol 3 K uranyl oxides hydrates and peroxides metaschoepite UO 2H OUO(H O) 4.4 ( 3.1 1791.0 ( 3.2 1632.2 ( 7.4 532.5 ( 8.1 1356.6 ( 8.1 3 3 2 3 2 2 À À À À β-UO (OH) β-UO (OH) 26.6 ( 2.8 1536.2 ( 2.8 2 2 2 2 À À bequerelite Ca[(UO ) O (OH) ] 8H O Ca (UO )O (OH) (H O) 44.6 ( 2.2 1898.2 ( 2.3 1717.6 ( 4.4 605.8 ( 5.0 1407.8 ( 5.0 2 3 2 3 2 3 2 0.17 2 0.67 2 1.3 À À À À À clarkeite Na(UO )O(OH) Na(UO )O(OH) 150.6 ( 4.9 1724.7 ( 5.1 1635.1 ( 23.4 300.5 ( 23.9 891.0 ( 23.9 2 2 À À À À À Na-compreignacite Na (UO )O (OH)(H O) 53.5 ( 2.4 1822.7 ( 2.4 1674.3 ( 4.1 497.9 ( 5.0 1286.9 ( 5.0 0..34 2 0.67 2 1.2 À À À À À Na2[(UO2)3O2(OH)3]2 3 7H2O curite Pb (UO ) O (OH) •2H O Pb (UO ) O (OH) (H O) 161.5 ( 4.3 1645.4 ( 4.3 3 2 8 8 6 3 2 0.38 2 0.76 2 0.3 À À studtite (UO )O 4H O, oxide + H O (UO )O (H O) 22.3 ( 3.9 2344.7 ( 4.0 2 2 3 2 2 2 2 2 4 À studtite (UO )O 4H O, oxide + H O 75.7 ( 4.1 2 2 3 2 2 2 À uranyl carbonates rutherfordine UO CO UO CO 99.1 ( 4.2 1716.4 ( 4.2 2 3 2 3 À À andersonite Na Ca[(UO )(CO ) ] 5H O Na Ca[(UO )(CO ) ](H O) 710.4 ( 9.1 5593.6 ( 9.1 2 2 3 3 3 2 2 2 3 3 2 5 À À grimselite K NaUO (CO ) H OKNaUO (CO ) (H O) 989.3 ( 14.0 4431.6 ( 15.3 3 2 3 3 3 2 3 2 3 3 2 À À uranyl phosphates UO HPO 3H OUOHPO (H O) 241.0 ( 3.9 3223.2 ( 4.0 3072.3 ( 4.8 1302.3 ( 21.2 2774.1 ( 21.2 2 4 3 2 2 4 2 3 À À À À À (UO ) (PO ) 4H OUO(PO ) (H O) 227.2 ( 2.3 2333.7 ( 4.6 2046.3 ( 12.2 964.3 ( 6.2 1831.6 ( 20.6 2 3 4 2 3 2 2 4 2/3 2 4/3 À À À À À uranyl silicates soddyite (UO ) (SiO ) 2H O (UO )(SiO ) (H O) 117.8 ( 4.3 2022.7 ( 2.5 1826.1 ( 2.1 635.4 ( 10.9 1338.4 ( 10.9 2 2 4 3 2 2 4 1/2 2 À À À À À K-boltwoodite K(UO )(SiO OH) 1.3H O K(UO )(SiO OH)(H O) 238.5 ( 6.0 2768.1 ( 6.5 2758.6 ( 3.5 27.5 ( 7.3 1075.0 ( 7.3 2 3 3 2 2 3 2 À À À À À Na-boltwoodite Na(UO )(SiO OH) H O Na(UO )(SiO OH)(H O) 215.9 ( 6.5 2947.2 ( 4.0 2725.2 ( 2.6 352.5 ( 7.2 1386.6 ( 7.2 2 3 3 2 2 3 2 À À À À À uranophane Ca(UO ) (SiO OH) 5H O Ca (UO ) (SiO OH )(H O) 150.0 ( 4.3 3399.7 ( 4.0 3099.3 ( 5.6 1007.6 ( 12.0 2321.0 ( 12.2 2 2 3 3 2 0.5 2 3 0.5 2 2.5 À À À À À 5116.0 ( 5.5 kJ/mol, was established. However for hydrated data (Table 1) leads to systematics and comparison with predicted À forms that crystallize environmentally, (UO2)3(PO4)2 4H2O values for uranyl oxide hydrates, carbonates, phosphates, and 3 13,14 and (UO2)3(PO4)2 3 6H2O, only solubility was evaluated.
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