Handbook of Aqueous Electrolyte Thermodynamics: Theory & Application

Handbook of Aqueous Electrolyte Thermodynamics: Theory & Application......Page 5
TABLE OF CONTENTS......Page 14
I INTRODUCTION......Page 26
II THERMODYNAMICS OF SOLUTIONS......Page 36
Basic Thermodynamic Functions......Page 38
Solutions - Basic Definitions and Concepts......Page 39
Equilibrium - Necessary Conditions......Page 41
Activities, Activity Coefficients and Standard States......Page 42
III EQUILIBRIUM CONSTANTS......Page 50
Ionic and/or Reaction Equilibrium in Aqueous Solutions......Page 52
Solubility Equilibria Between Crystals and Saturated Solutions......Page 55
Vapor-Liquid Equilibria in Aqueous Solutions......Page 56
Temperature Effects on the Equilibrium Constant......Page 57
Estimating Temperature Effects on Heat Capacity and Other Thermodynamic Properties......Page 58
Pressure Effects on the Equilibrium Constant......Page 61
Appendix 3.1 - Criss and Cobble Parameters......Page 64
IV ACTIVITY COEFFICIENTS OF SINGLE STRONG ELECTROLYTES......Page 70
History......Page 73
Limitations and Improvements to the Debye-Huckel Limiting Law......Page 80
Further Refinements......Page 81
Bromley's Method......Page 89
Meissner's Method......Page 92
Pitzer's Method......Page 96
Short Range Interaction Model......Page 101
Long Range Interaction Model......Page 107
Meissner's Method......Page 109
Pitzer's Method......Page 111
Chen's Method......Page 114
Application......Page 115
Bromley's Method......Page 116
Meissner's Method......Page 118
Pitzer's Method......Page 119
Chen's Method......Page 121
NBS Smoothed Experimental Data......Page 123
HCl......Page 124
KCl......Page 128
KOH......Page 131
NaCl......Page 135
NaOH......Page 138
CaCl2......Page 142
Na2SO4......Page 146
MgSO4......Page 149
Bromley's Extended Equation......Page 152
MgSO4 Test Case......Page 153
Bromley......Page 155
Pitzer and Chen......Page 156
Experimental Data......Page 157
HCl at 50° Celsius......Page 158
KCl at 80° Celsius......Page 161
KOH at 80° Celsius......Page 165
NaCl at 100 and 300° Celsius......Page 169
NaOH at 35° Celsius......Page 175
CaCl2 at 108.85 and 201.85° Celsius......Page 178
Na2SO4 at 80° Celsius......Page 184
MgSO4 at 80° Celsius......Page 187
Table 1: β Values for Uni-univalent Electrolytes......Page 190
Table 2: β and B Values of Bi-univalent and Uni-bivalent Electrolytes from Freezing Points......Page 191
Methods for Calculating β......Page 192
Table 1: B Values at 25°C Determined by the Method of Least Squares on Log γ to I=6.0 (or less if limited data)......Page 195
Table 2: Individual Ion Values of B and δ in Aqueous Solutions at 25°C......Page 198
Table 3: Bivalent Metal Sulfates at 25°C......Page 199
Table: Average Values of Parameter q in Equation (4.46) for Selected Electrolytes......Page 200
Table 1: Inorganic Acids, Bases and Salts of 1-1 Type......Page 204
Table 3: Tetraalkylammonium Halides......Page 206
Table 4: Sulfonic Acids and Salts (1-1 Type)......Page 207
Table 6: Inorganic Compounds of 2-1 Type......Page 208
Table 8: 3-1 Electrolytes......Page 210
Table 9: 4-1 Electrolytes......Page 211
Table 11: 2-2 Electrolytes......Page 212
Table 1: Temperature Derivatives of Parameters for 1-1 Electrolytes Evaluated from Calorimetric Data......Page 213
Table 2: Temperature Derivatives of Parameters for 2-1 and 1-2 Electrolytes Evaluated from Calorimetric Data......Page 214
Table 3: Temperature Derivatives of Parameters for 3-1 and 2-2 Electrolytes from Calorimetric Parameters......Page 215
Table: τ Values Fit for Molality Mean Ionic Activity Coefficient Data of Aqueous Electrolytes at 298.15 K......Page 216
V ACTIVITY COEFFICIENTS OF MULTICOMPONENT STRONG ELECTROLYTES......Page 230
Guggenheim's Method for Multicomponent Solutions......Page 234
Bromley's Method for Multicomponent Solutions......Page 236
Activity Coefficients of Trace Components......Page 237
Meissner's Method for Multicomponent Solutions......Page 239
Pitzer's Method for Multicomponent Solutions......Page 244
Chen's Method for Multicomponent Solutions......Page 248
Application......Page 256
Guggenheim's Method......Page 257
Bromley's Method......Page 259
Meissner's Method......Page 260
Pitzer's Method......Page 261
Bromley's Water Activity......Page 263
Meissner's Water Activity......Page 265
Pitzer's Water Activity......Page 266
Phase Diagram Calculations......Page 267
Basic flow of the testing program......Page 268
Program block descriptions......Page 270
H2O - NaCl - KCl......Page 275
H2O - NaCl - HCl......Page 286
H2O - NaCl - NaOH......Page 293
H2O - KCl - HCl......Page 303
H2O - NaCl - CaCl2......Page 315
H2O - NaCl - MgCl2......Page 324
H2O - NaCl - Na2SO4......Page 340
H2O - KCl - CaCl2......Page 351
H2O - NaOH - Na2SO4......Page 360
H2O - NaCl - CaSO4......Page 372
H2O - HCl - CaSO4......Page 382
H2O - CaCl2 - CaSO4......Page 388
H2O - Na2SO4-CaSO4......Page 394
H2O - MgSO4 - CaSO4......Page 402
Table 1: Parameters for mixed electrolytes with virial coefficient equations (at 25°C)......Page 409
Table 2: Parameters for the virial coefficient equations at 25°C......Page 410
Effects of Higher-order Electrostatic Terms......Page 411
Table 3: Parameters for binary mixtures with a common ion at 25°C......Page 414
VI ACTIVITY COEFFICIENTS OF STRONGLY COMPLEXING COMPOUNDS......Page 424
Identification of Complexing Electrolytes......Page 431
Comparison of Osmotic Coefficients......Page 432
Phosphoric Acid......Page 434
Sulfuric Acid......Page 440
Zinc Chloride......Page 444
Ferric Chloride......Page 449
Cuprous Chloride......Page 453
Calcium Sulfate......Page 456
Sodium Sulfate......Page 461
Manganous Chloride......Page 465
Cobalt Chloride......Page 468
Nickel Chloride......Page 472
Cupric Chloride......Page 474
Activity Coefficient Methods......Page 478
Summary......Page 480
Table 1b: Three Parameter Set......Page 482
Table 3a: Equilibrium Constants and Changes in Thermodynamic Properties for Formating-of CuCl-2 and CuCl23- from CuCl(s) + nCl- = CuCln-n+1......Page 483
Table 3b: Equilibrium Constants and Changes in Thermodynamic Properties for Formation of CuCl-2 and CuCl23- from Cu+ + nCl- = CuCln(n-1)......Page 484
VII ACTIVITY COEFFICIENTS OF WEAK ELECTROLYTES AND MOLECULAR SPECIES......Page 504
Setschénow Equation......Page 510
Salting Out Parameter Determination by Randall and Failey......Page 511
Salting Out Parameter Determination by Long and McDevit......Page 516
Salting Out Parameter Determination by Other Authors......Page 521
Edwards, Maurer, Newman and Prausnitz Pitzer Based Method......Page 528
Beutier and Renon's Pitzer Based Method......Page 530
Chen's Pitzer Based Method......Page 537
Ammonia - Water......Page 542
Conclusions......Page 549
Appendix 7.1 - Salting Out Parameters for Phenol in Aqueous Salt Solutions at 25° Celsius......Page 563
Table 2: Salting Out Parameters for Strong Electrolytes in Equation (7.18) at 25°C......Page 565
Table 3: Temperature Dependence of the Salting Out Parameters for Equation (7.19)......Page 566
Table 5: Temperature Dependence of the Salting Out Constants for Individual Ions......Page 567
VIII THERMODYNAMIC FUNCTIONS DERIVED FROM ACTIVITY COEFFICIENTS......Page 576
Binary Density......Page 579
Strong Electrolytes Which Complex......Page 583
Weak Electrolytes......Page 584
Illustrative Example......Page 585
Enthalpy......Page 588
Molecular Species......Page 589
Ionic Species......Page 591
Range of Applicability......Page 592
Example......Page 593
IX WORKED EXAMPLES......Page 600
Model Formulation......Page 602
Obtaining Coefficients......Page 609
Model Solution......Page 611
Specific Examples......Page 613
Sodium Chloride Solubility......Page 614
Water - Chlorine......Page 620
Water - Ammonia - Carbon Dioxide......Page 631
Water - Sulfur Dioxide......Page 666
Chrome Hydroxides......Page 675
Gypsum Solubility......Page 688
Water - Phosphoric Acid......Page 700
Table 2: Temperature fit parameters for Henry's constants......Page 708
Table 3: Pitzer ion-ion interaction parameters......Page 709
Table 5: Dielectric effect parameters......Page 710
Table 2: Temperature fit parameters for Henry's constants......Page 716
Table 4: Temperature fit molecule self interaction parameters......Page 717
Table 5: Molecule-ion interaction parameters......Page 718
Appendix 9.3 - Fugacity Coefficient Calculation......Page 724
Table 1: Pure component parameters......Page 725
Table 3: Interaction parameter α012 for polar-nonpolar mixtures Numbers in parentheses are estimates......Page 726
Table 4: Parameter α12 for binary mixtures of nonpolar gases......Page 727
Table 5: Interaction parameter α012 for polar-polar mixtures......Page 728
Appendix 9.4 - Brelvi and O'Connell Correlation for Partial Molar Volumes......Page 729
Table 1: Characteristic volumes......Page 730
Table 3: Gypsum solubility product at 25°C......Page 731
X. APPENDICES......Page 736
APPENDIX A - COMPUTER PROGRAMS FOR SOLVING EQUILIBRIA PROBLEMS......Page 738
APPENDIX B - SELECTED THERMODYNAMIC DATA......Page 746
APPENDIX C - COMPILED THERMODYNAMIC DATA SOURCES FOR AQUEOUS AND BIOCHEMICAL SYSTEMS: An Annotated Bibliography (1930 - 1983)......Page 762
INDEX......Page 868