Chemical Thermodynamics of Zirconium (eBook)

Cover 1
Contents 14
Preface 6
Acknowledgements 8
Note from the Chaiman 10
Editor's note 12
How to contact the NEA-TDB project 13
Introductory material 34
INTRODUCTION 36
Background 36
Focus of the review 37
Review procedure and results 39
History of zirconium and its uses 41
Previous reviews on the thermochemistry of zirconium 42
STANDARDS, CONVENTIONS, AND CONTENTS OF THE TABLES 46
Symbols, terminology and nomenclature 46
Abbreviations 46
Symbols and terminology 48
Chemical formulae and nomenclature 50
Phase designators 50
Processes 52
Equilibrium constants 53
Protonation of a ligand 53
Formation of metal ion complexes 54
Solubility constants 55
Equilibria involving the addition of a gaseous ligand 56
Redox equilibria 57
pH 59
Spectroscopic constants and statistical mechanics calculations for gaseous species 61
Order of formulae 62
Reference codes 63
Units and conversion factors 64
Standard and reference conditions 67
Standard state 67
Standard state pressure 69
Reference temperature 72
Fundamental physical constants 72
Uncertainty estimates 73
The NEA-TDB system 73
Presentation of the data 75
Tables of selected data 78
SELECTED ZIRCONIUM DATA 80
SELECTED AUXILIARY DATA 92
Discussion of data selection 112
DISCUSSION OF DATA SELECTION FOR ZIRCONIUM 114
Elemental zirconium 114
Zirconium metal 114
Phases and crystal structure 114
Heat capacity and entropy 117
alpha-zirconium 117
Beta-zirconium 123
omega-zirconium 125
Liquid zirconium 126
Gaseous zirconium 127
Zirconium aqua ions 130
Zr4+ 130
Gibbs energy of formation 130
Enthalpy of formation 131
Entropy 131
ZrO2+ 132
Oxygen and hydrogen compounds and complexes 133
Aqueous zirconium hydroxide complexes 133
Monomer hydrolysis species 137
ZrOH3+ 137
Zr(0H)2+ 139
Zr(OH)+3 141
Zr(OH)4 (aq) 141
Zr(OH)-5 142
Zr(OH)2- 6 143
Polynuclear hydrolysis species 144
Dimeric species 145
Trimeric species 145
Zr3 (OH)8+4 145
Zr4(OH) + 15 148
Tetrameric species 147
Zr 4(OH)8+8 147
Zr large supremum 4(OH)+ 15 148
Zr4(OH)16(aq) 148
Mixed hydroxo/chloro complexes 149
Summary of the hydrolysis model 149
Crystalline and amorphous zirconium(IV) oxides and hydroxides 151
Zirconium(IV) dioxide 152
Crystal structure 152
Thermodynamic values 152
Solubility of ZrO2(monoclinic) 157
Amorphous oxide and hydroxide phases 157
Structures 157
Thermodynamic data 158
Gaseous zirconium oxides 160
ZrO(g) 160
ZrO2(g) 161
Zirconium hydride 162
Phases and crystal structure 162
Thermodynamic data 163
ZrH(g) 166
Group 17 (halogen) compounds and complexes 166
Fluorine compounds and complexes 166
Aqueous zirconium fluorides 166
Solid zirconium fluorides 177
ZrF4(cr) 177
ZrF3(cr), ZrF2(cr) and ZrF(cr) 182
Gaseous zirconium fluorides 202
Chlorine compounds and complexes 186
Aqueous zirconium chlorides 186
Solid zirconium chlorides 191
ZrCl4(cr) 191
ZrCl3(cr) 196
ZrCl2(cr) 198
ZrCl(cr) 200
Gaseous zirconium chlorides 210
Bromine and iodine compounds and complexes 205
Aqueous zirconium bromides and iodides 205
Solid zirconium bromides 205
ZrBr4(cr) 205
ZrBr3(cr), ZrBr2(cr) and ZrBr(cr) 206
Gaseous zirconium bromides 210
Gaseous zirconium iodides 212
Group 16 (chalcogen) compounds and complexes 214
Sulphur compounds and complexes 214
Zirconium sulphides 214
Zirconium sulphites 218
Aqueous zirconium sulphites 218
Solid zirconium sulphites 219
Zirconium sulphates 219
Aqueous zirconium sulphates 219
Solid zirconium sulphates 225
Selenium compounds 226
Zirconium selenide compounds 226
Zirconium selenite compounds 227
Tellurium compounds 227
Zirconium telluride compounds 227
Zirconium tellurite compounds 228
Group 15 compounds and complexes 228
Zirconium nitrogen compounds and complexes 228
Zirconium nitrides 228
Solid zirconium nitride, ZrN(cr) 228
ZrN(g) 230
Zirconium nitrates 230
Aqueous zirconium nitrates 230
Solid zirconium nitrates 233
Phosphorus compounds and complexes 234
Zirconium phosphides 234
Solid zirconium phosphides 234
Zirconium phosphates 235
Aqueous zirconium phosphates 235
Solid zirconium phosphates 235
Solid zirconium diphosphates 238
Solid zirconium triphosphates 239
Arsenic compounds and complexes 239
Zirconium arsenides 239
Solid zirconium arsenides 239
Zirconium arsenates 240
Aqueous zirconium arsenates 240
Solid zirconium arsenates 240
Group 14 compounds and complexes 241
Carbon compounds and complexes 241
Zirconium carbides 241
Solid zirconium carbide, ZrC(cr) 241
Zirconium carbonates 243
Aqueous zirconium carbonates 243
Solid zirconium carbonates 249
Silicon compounds and complexes 250
Zirconium silicate (zircon) 250
Calcium-zirconium silicate compounds 253
Strontium zirconium silicate compounds 254
Barium zirconium silicate compounds 255
Sodium zirconium silicate compounds 255
Potassium zirconium silicate compounds 258
Cesium zirconium silicate compounds 258
DISCUSSION OF NEW AUXILIARY DATA SELECTION 260
Group 13 auxiliary data 260
Group 2(alkaline earth) auxiliary data 260
Appendices 262
DISCUSSION OF SELECTED REFERENCES 264
IONIC STRENGTH CORRECTIONS 390
The specific ion interaction equations 392
Background 392
Ionic strength corrections at temperatures other than 298.15 K 397
Estimation of ion interaction coefficients 399
Estimation from mean activity coefficient data 399
Estimations based on experimental values of equilibrium constants at different ionic strengths 399
On the magnitude of ion interaction coefficients 403
Ion interaction coefficients versus equilibrium constants for ion pairs 404
Tables of ion interaction coefficients 404
ASSIGNED UNCERTAINTIES 418
The general problem 418
Uncertainty estimates in the selected thermodynamic data 420
One source datum 421
Two or more independent source data 422
Discrepancies 424
Several data at different ionic strengths 426
Discrepancies or insufficient number of data points 428
Procedures for data handling 430
Correction to zero ionic strength 430
Propagation of errors 432
Rounding 433
Significant digits 434
HYDROLYSIS MODEL 436
Background for the derivation of the hydrolysis model 436
Procedure details 443
Algorithm 444
Results 446
SIT Interaction coefficients 446
Application of the model to the literature data 451
Solubility data of [99VEY] in nitrate media 451
Solubility data of [61KOV/BAG] in very dilute solutions 454
Solubility data of [66B1L/BRA2] in dilute and perchlorate media 454
Potentiometric data of [99VEY] in perchlorate media 456
Potentiometric data of [2001EKB/BRO], [2004EKB/KAL] in perchlorate media 457
Solvent extraction data of [53ZIE] 458
Ion exchange data of [51CON/REA] 459
Solubility data of [2004EKB/KAL] 460
BIBLIOGRAPHY 462
LIST OF CITED AUTHORS 522