chemical thermodynamics of thorium

Preface......Page 7
Acknowledgements......Page 9
Editor's note......Page 11
Contents......Page 13
List of Figures......Page 25
List of Tables......Page 33
Background......Page 47
Focus of the review......Page 49
Review procedure and results......Page 51
Abbreviations......Page 53
Symbols and terminology......Page 55
Phase designators......Page 57
Processes......Page 59
Spectroscopic constants and statistical mechanics calculatio......Page 60
Protonation of a ligand......Page 61
Formation of metal complexes......Page 62
Solubility constants......Page 63
Equilibria involving the addition of a gaseous ligand......Page 64
Redox equilibria......Page 65
pH......Page 67
Order of formulae......Page 70
Units and conversion factors......Page 71
Standard and reference conditions......Page 74
Fundamental physical constants......Page 78
The NEATDB system......Page 79
Presentation of the selected data......Page 81
III Selected thorium data......Page 87
IV Selected auxiliary data......Page 101
Crystal structure and phase transitions......Page 127
Heat capacity below 298.15 K......Page 128
Heat capacity above 298.15 K......Page 134
Heat capacity and entropy......Page 135
Enthalpy of formation......Page 136
Thermodynamic data for the Th4+ ion......Page 139
Hydration of the Th4+ ion......Page 143
Ion interaction coefficients of the Th4+ ion......Page 145
SIT coefficients......Page 148
Pitzer coefficients......Page 152
Thorium monoxide gas ThO(g)......Page 155
ThO2(cr)......Page 158
Thorium dioxide gas ThO2(g)......Page 163
Solid thorium hydrides, ThH2(cr) and ThH3.75(cr)......Page 166
Heat capacity and entropy......Page 167
Enthalpy of formation......Page 168
Heat capacity and entropy......Page 169
Enthalpy of formation......Page 170
Thorium hydride gases, ThHn(g)......Page 171
Discussion of experimental methods......Page 172
Ionic medium and ionic strength effects......Page 176
Discussion of the hydrolysis of Th4+ using potentiome......Page 178
Equilibrium constants for the hydrolysis of Th(IV) at......Page 184
Dinuclear complexes......Page 185
 Trinuclear complexes......Page 190
Tetranuclear complexes......Page 192
Hexanuclear complexes......Page 196
Mononuclear Th(IV) hydroxide complexes......Page 199
Th(OH)3+......Page 203
Th(OH)22+......Page 204
Th(OH)4(aq)......Page 205
Enthalpies and entropies of Th(IV) hydrolysis reactions......Page 206
Summary of selected data for Th(IV) hydroxide complexes......Page 211
Ternary Th(IV) hydroxide complexes with organic ligands......Page 215
Solubility of thorium oxides and hydroxides......Page 216
Amorphous Th(OH)4(am) or ThO2(am, hyd)......Page 217
 Anhydrous ThO2(cr) and microcrystalline ThO2(cr, hyd)......Page 227
Discussion of particle size effects......Page 233
Enthalpies of formation......Page 239
Heat capacity and entropy......Page 241
Enthalpy of formation......Page 242
Standard entropy and heat capacity......Page 244
Enthalpy of formation......Page 245
Enthalpy of formation......Page 246
Entropy......Page 247
Formation constants of thorium fluoride complexes,......Page 248
Formation constants of ThF3+,, and......Page 255
Formation constants of ThF4(aq)......Page 256
Formation constants of  and......Page 260
Comparison with U(IV)-fluoride complexes......Page 263
Enthalpies and entropies of reaction for Th(IV) fluoride com......Page 264
Other solid thorium fluoride compounds......Page 265
Solubility and Gibbs energy......Page 267
ThF4·NaF·H2O(cr)......Page 269
ThCl2(cr), ThCl3(cr)......Page 270
Enthalpies of formation......Page 271
Enthalpy of formation......Page 272
Entropy......Page 274
Standard entropy and heat capacity......Page 275
Enthalpy of formation......Page 276
ThOCl2(cr)......Page 277
Enthalpy of formation......Page 278
Aqueous thorium chloride complexes......Page 280
Ion interaction model......Page 281
Complexation model......Page 282
Aqueous thorium chlorate complexes......Page 288
Standard entropy and heat capacity......Page 289
Enthalpies of formation......Page 290
ThBr2(cr), ThBr3(cr)......Page 291
Enthalpy of formation......Page 292
Entropy......Page 293
Enthalpy of formation......Page 294
ThOBr2(cr)......Page 296
Aqueous thorium bromide complexes......Page 297
Aqueous thorium bromate complexes......Page 298
ThI2(cr), ThI3(cr)......Page 301
ThI4(cr)......Page 302
Entropy......Page 303
Standard entropy and heat capacity......Page 304
Enthalpy of formation......Page 305
Thorium oxyiodide ThOI2(cr)......Page 307
Aqueous thorium iodide complexes......Page 309
Aqueous thorium iodate complexes......Page 310
Thorium monosulphide, ThS(cr)......Page 311
Thorium monosulphide gas ThS(g)......Page 313
Thorium sesquisulphide, Th2S3(cr)......Page 314
Thorium disulphide, ThS2(cr)......Page 315
Thorium polysulphide Th2S5(cr)......Page 316
Aqueous thorium sulphites......Page 317
Solid thorium sulphates, Th(SO4)2(cr)......Page 318
Formation constants of thorium sulphate complexes......Page 320
Enthalpy, entropy, and Gibbs energy of reaction for , Th(SO4......Page 329
Hydrated solid thorium sulphates......Page 330
Th(SO4)2·9H2O(cr)......Page 332
Th(SO4)2.8H2O(cr) and Th(SO4)2.4H2O(cr)......Page 335
Th(SO4)2·Na2SO4·6H2O(cr)......Page 336
Th(SO4)2·K2SO4·4H2O(cr), Th(SO4)2·2K2SO4·2H2O(cr), Th(SO4)2·......Page 337
Th(SO4)2·(NH4)2SO4·4H2O(cr), Th(SO4)2·2(NH4)2SO4·2H2O(cr), a......Page 339
The consistency of the thermodynamic data for hydrated solid......Page 340
Summary of thorium sulphate systems analysed by the NONLINT......Page 341
Phase diagram and crystal structures......Page 343
Thorium sesquiselenide Th2Se3(cr)......Page 345
Thorium oxyselenide ThOSe(cr)......Page 346
Phase diagram......Page 347
Th7Te12(cr) /Th2Te3(cr)......Page 348
Thorium ditelluride gas ThTe2(g)......Page 349
Thorium oxytelluride ThOTe(cr)......Page 350
Thorium mononitride ThN(cr)......Page 351
Gaseous thorium mononitride ThN(g)......Page 353
Th3N4(cr)......Page 354
Aqueous thorium azides......Page 355
Solid thorium tetranitrates, Th(NO3)4(cr)......Page 356
Thorium tetranitrate hydrates......Page 357
Aqueous thorium nitrates......Page 359
Thorium monophosphide ThP(cr)......Page 363
Th3P4(cr)......Page 364
Solid thorium phosphates......Page 365
Aqueous complexes with phosphate ions......Page 368
Other aqueous thorium phosphate species......Page 372
Solid thorium arsenides......Page 373
Solid thorium antimonides......Page 374
Phase diagram and structures......Page 375
Gibbs energies......Page 376
Thorium monocarbide ThC1–x(cr)......Page 379
Standard entropy, heat capacity and enthalpy of formation......Page 381
Gibbs energy......Page 384
Thorium dicarbide gas ThC2(g)......Page 386
Thorium tetracarbide gas ThC4(g)......Page 388
Solid thorium carbonate compounds......Page 389
Aqueous thorium complexes with carbonate......Page 390
Solubility of ThO2(am, hyd) in carbonate solution and format......Page 392
Solubility studies under CO2(g)......Page 396
Solubility studies in carbonate/bicarbonate buffers......Page 398
Solubility studies at high pH and carbonate concentration......Page 400
Summary......Page 402
Formation constant of Th(CO3)56-......Page 403
Solubility of Na6[Th(CO3)5].12H2O(s) and [C(NH2)3]6[Th(CO3)5......Page 408
Additional studies of the thorium carbonate system......Page 413
Complexes with SCN–......Page 415
Solid thorium silicides......Page 417
Thorium silicate, ThSiO4(cr)......Page 419
Aqueous complexes with H4SiO4(aq) and polynuclear Si species......Page 421
Thorium germanides......Page 422
Thorium-tin compounds......Page 423
Thorium-lead compounds......Page 425
Strontium thorate, SrThO3(cr)......Page 427
Barium thorate, BaThO3(cr)......Page 428
General references for minerals......Page 436
Rubidium thorate, Rb2ThO3(cr)......Page 430
Caesium thorate, Cs2ThO3(cr)......Page 431
Common thorium minerals......Page 432
Thorium brannerite, ThTi2O6(cr)......Page 435
Appendix A......Page 441
Appendix B......Page 747
Background......Page 748
 Ionic strength corrections at temperatures other than 298.15 K......Page 755
Estimation from mean activity coefficient data......Page 756
Estimations based on experimental values of equilibrium constants at different ionic strengths......Page 757
On the magnitude of ion interaction coefficients......Page 760
Tables of ion interaction coefficients......Page 761
The general problem......Page 793
Uncertainty estimates in the selected thermodynamic data......Page 795
One source datum......Page 796
Two or more independent source data......Page 797
Discrepancies......Page 799
Several data at different ionic strengths......Page 801
Discrepancies or insufficient number of data points......Page 803
Correction to zero ionic strength......Page 805
Propagation of errors......Page 807
Rounding......Page 808
Significant digits......Page 809
Introduction......Page 811
Accounting for uncertainties in ion-interaction parameters......Page 813
Accounting for uncertainties in  values of auxiliary input d......Page 816
Example......Page 814
General equations and schematic approach to calculations......Page 817
Input data......Page 819
Outputs......Page 820
Appendix E......Page 821
Appendix F......Page 825
Bibliography......Page 827
List of cited authors......Page 911