Chemical thermodynamics of solid solutions of interest in radioactive waste management : a state-of-the-art report

Preface......Page 7
Acknowledgements......Page 9
Editor's note......Page 11
I.1.1 Motivation......Page 23
I.1.3 Audience......Page 25
I.2 Definitions......Page 26
I.3 From Aqueous to Solid Solutions......Page 29
I.4  Basic Thermodynamics of Solid Solutions......Page 34
I.4.2 The entropy of mixing......Page 35
I.4.5 On the relevance of non-ideality......Page 36
I.4.6 Solid solution versus other uptake modes......Page 38
I.4.7 Concepts and approximations in geochemical modelling of Aq-SS systems......Page 39
I.4.8 Kinetic and thermodynamic approximations to Aq-SS in geochemical reactive transport modelling......Page 40
I.5 Experimental and analytical aspects......Page 41
I.5.2 Characterization of the solid solution......Page 42
I.5.4 Partition/distribution experiments......Page 44
I.5.5.2 Calorimetry......Page 45
I.6.1.1 The radium-barite relationship in natural and anthropogenic environments......Page 47
I.6.1.2 Numerical modelling involving (Ba,Ra)SO4 solid solutions......Page 48
I.6.2.2 Thermodynamic modelling of C-S-H and its limitations......Page 49
I.6.2.3 Geochemical modelling of C-S-H systems of interest in radioactive waste management......Page 50
I.6.3.1 The relevance of calcite for radioactive waste management......Page 51
I.6.3.3 Spectroscopic information on the incorporation of f-elements into the calcite structure......Page 52
I.6.4.1 The applicability of Aq-SS thermodynamics to spent nuclear fuel......Page 53
I.6.4.3 Application of Aq-SS thermodynamics to spent fuel dissolution data......Page 54
I.7 Report conclusions......Page 55
II.1.1.1 Introduction......Page 57
II.1.1.2 Thermodynamic formalism......Page 59
II.1.1.3 The entropy of mixing......Page 62
II.1.1.4 Regular, subregular and generalised mixing models......Page 66
II.1.1.4.1 Dilute solid solutions......Page 71
II.1.1.5 Phases with different structures......Page 73
II.1.1.6.1 General comments......Page 77
II.1.1.6.2 An example: carbonates with calcite and dolomite structures......Page 78
II.1.2 Methods and tools for thermodynamic description of aqueous-solid solution (Aq-SS) equilibria......Page 82
II.1.2.1 Definitions and basic thermodynamics relations......Page 84
II.1.2.1.1 Mole fraction scale......Page 86
II.1.2.1.2 Molality scale......Page 87
II.1.2.1.3 Aqueous activity coefficients......Page 88
II.1.2.1.3.1 SIT model......Page 91
II.1.2.1.3.3 Extended UNIQUAC model......Page 92
II.1.2.1.4 Gas mixtures and gas solubility......Page 93
II.1.2.1.5 Solid solubility......Page 94
II.1.2.1.6 Unified theory of ionic solid solution solubilities......Page 96
II.1.2.1.7 Multicomponent ionic Aq-SS system (following [2003GAM/KON])......Page 98
II.1.2.2 Lippmann diagrams, a tool to visualise binary Aq-SS systems......Page 99
II.1.2.2.1 Example of the use of Lippmann diagrams......Page 102
II.1.2.3 Law of mass action (LMA) method for computing equilibrium speciation......Page 108
II.1.2.4 Gibbs energy minimisation (GEM) method......Page 116
II.1.2.4.1 GEM IPM algorithm......Page 119
II.1.2.4.2 GEM dual-thermodynamic calculations in forward modelling.......Page 123
II.1.2.4.3 Multiple solid solutions and miscibility gaps......Page 125
II.1.3.1 The “activity ratios” technique......Page 127
II.1.3.2 Dual Thermodynamic retrieval calculations......Page 131
II.1.3.2.2 Retrieval of activity coefficients and mixing parameters......Page 132
II.1.3.2.3 Retrieval of end-member standard molar Gibbs energy and solubility product at equilibrium......Page 134
II.1.3.2.5 DualTh retrieval calculations at minimum stoichiometric saturation......Page 135
II.1.3.2.6 Statistical DualTh calculations......Page 137
II.1.3.2.7 Example: EuIII in calcite......Page 138
II.1.3.3 Graphical fitting and regression methods......Page 142
II.1.3.3.1 Weighted least-squares and Bayesian estimation techniques......Page 143
II.1.3.4 Retrieval of excess Gibbs energy from electrochemical measurements......Page 144
II.1.3.5 Estimation of interaction parameters from the position of miscibility gaps......Page 147
II.1.3.5.1 Miscibility gap data......Page 148
II.1.3.5.2 Critical mixing-point data......Page 149
II.1.3.6 Estimation of interaction parameters from distribution coefficients......Page 151
II.2 Experimental and analytical aspects......Page 152
II.2.1.1 Limitations and points to notice......Page 153
II.2.1.1.1 Synthesis procedures......Page 156
II.2.2 Solubility measurements in aqueous solutions......Page 158
II.2.2.1 Thermodynamic equilibrium solubility......Page 159
II.2.2.2 Stoichiometric saturation......Page 161
II.2.3 Solid phase characterisation......Page 164
II.3.1.1 Introduction to the barite isostructural family......Page 177
II.3.1.2.1 The radium-barium relationship in natural and anthropogenic environments......Page 180
II.3.1.2.2 Numerical modelling involving (Ba,Ra)SO4 solid solutions......Page 182
II.3.1.3 Conclusions......Page 190
II.3.2 Cases study/Cement phases – Solubility of calcium silicate hydrates (C-S-H)......Page 191
II.3.3 Structural incorporation of trivalent actinides/lanthanides into calcite......Page 206
II.3.4.1 Introduction......Page 215
II.3.4.2.1 Uraninite and non-irradiated fuel......Page 216
II.3.4.2.2 Irradiated UO2......Page 217
II.3.4.3 Application of Aq-SS thermodynamics to spent fuel dissolution experimental data......Page 218
II.3.4.3.1 Strontium......Page 219
II.3.4.3.2 Barium......Page 221
II.3.4.3.3 Neptunium......Page 222
II.3.4.3.4 Plutonium......Page 223
II.3.4.3.5 Lanthanides......Page 224
II.3.4.4 Final remarks......Page 225
[1958HAR/OWE]......Page 227
[1969OAT]......Page 228
[1974BRO/SKI]......Page 229
[1977PAR/MOL]......Page 230
[1981FUJ/KON]......Page 231
[1982REE2]......Page 232
[1984HAR/MOL]......Page 233
[1985PAG/PIN]......Page 234
[1987BUR]......Page 235
[1987PLU/BUS]......Page 236
[1988HOC]......Page 237
[1989GAL/DAN]......Page 238
[1990ERI/HAC]......Page 239
[1990NOR/PLU]......Page 240
[1991TAI/STR]......Page 241
[1992GRE/FUG]......Page 242
[1992STI/HOC]......Page 243
[1993NIK/RAS]......Page 244
[1994NAV/RAP]......Page 245
[1995SIL/BID]......Page 246
[1996HER/WES]......Page 247
[1997GRE/PLY2]......Page 248
[1997PIR/FED]......Page 249
[1998BRU/CER]......Page 250
[1998PIA/TOU]......Page 251
[1999GRU]......Page 252
[1999PER/PAL]......Page 253
[2000GLY]......Page 254
[2000PRI/FER]......Page 255
[2001GAN]......Page 256
[2001PAR/VAN]......Page 257
[2001ZIE/OTT]......Page 258
[2002HEL/NAV]......Page 259
[2002MAN/MAR]......Page 260
[2003BLA/AGU]......Page 261
[2003JOH/GLA]......Page 262
[2003TIT/STU]......Page 263
[2004KLE]......Page 264
[2004ROU/ELZ]......Page 265
[2005BRO/CUR]......Page 266
[2005LEE/WAN]......Page 267
[2005VIL/THO]......Page 268
[2006VIL/THO]......Page 269
List of cited authors......Page 271