x
Contents
8.2 Effect of Inorganic Speciation on the Solubility of Metals .................. 196
8.3 Estimation of the Activity Coefficients of Ions in Natural Waters. . ... . . . . .. 199
8.4 The MIAMI Ionic Interaction Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 202
8.5 Reliability of the Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 203
8.6 Speciation of Metals ....................................................... 207
8.7 Formation of Metal Organic Complexes ................................... 211
8.8 Future of the Model ........................................................ 217
Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 217
9
Binding Ability of Inorganic Major Components of
Sea Water toward some Classes of Ligands, Metal and
Organometallic Cations.................................................. 221
9.1 Introduction. . ... . . . ... . . . . . .... . . . .... . . . ... .. . . . . . . . .... . . ... . . . ... . . . . .. 221
9.2 Artificial Sea Water.... . . . . ..... . . . .... . . .. .... . . . . ....... . . ... . . .... . . . . .. 221
9.2.1 The Major Components of Sea Water as a Single Sea Salt:
The "Single Salt Approximation" . . .... . . . . ........ . . .... . . .... . . . .... 222
9.3 Interactions of Acid-Base Systems with the Components of
Artificial Sea Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 225
9.3-1 Organic Ligands .................................................... 226
9.3.2 Inorganic Ligands................................................... 241
9.3-3 Metals and Organometallic Compounds ............................ 243
9.4 Discussion and Conclusions ............................................... 248
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 250
Appendix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 253
A9.1 Abbreviations and Formula . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 253
A9.2 Tables............................................................... 255
10 Equilibrium Analysis, the Ionic Medium Method and
Activity Factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 263
10.1 Introduction............................................................... 263
10.2 Equilibrium Analysis ...................................................... 263
10.3 Activity Factors in Multi-Component Electrolyte Systems. . . . . . . . . . . . . . . . .. 266
10-4 The Pitzer and the Br0nsted-Guggenheim-Scatchard
Ion Interaction Models .................................................... 267
10.5 Comparison of the SIT and Pitzer Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 270
10.6 Determination of Interaction Parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 282
11 Acid-Base Equilibria in Saline Media:
Application of the Mean Spherical Approximation ..................... 283
11.1 Introduction............................................................... 283
11.2 Acid-Base Equilibria in Saline Media ...................................... 283
11.3 pK' vs. Ionic Strength Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 285
11.4 The Mean Spherical Approximation: Estimation of Q(g) Term by
Use of the MSA Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 286
11.5 Comparison with the Pitzer Model. . . . . . . .. . . . . . .. . . . . . . . .. . . . . . .. .. . . . . ... 288
Contents
8.2 Effect of Inorganic Speciation on the Solubility of Metals .................. 196
8.3 Estimation of the Activity Coefficients of Ions in Natural Waters. . ... . . . . .. 199
8.4 The MIAMI Ionic Interaction Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 202
8.5 Reliability of the Model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 203
8.6 Speciation of Metals ....................................................... 207
8.7 Formation of Metal Organic Complexes ................................... 211
8.8 Future of the Model ........................................................ 217
Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 217
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 217
9
Binding Ability of Inorganic Major Components of
Sea Water toward some Classes of Ligands, Metal and
Organometallic Cations.................................................. 221
9.1 Introduction. . ... . . . ... . . . . . .... . . . .... . . . ... .. . . . . . . . .... . . ... . . . ... . . . . .. 221
9.2 Artificial Sea Water.... . . . . ..... . . . .... . . .. .... . . . . ....... . . ... . . .... . . . . .. 221
9.2.1 The Major Components of Sea Water as a Single Sea Salt:
The "Single Salt Approximation" . . .... . . . . ........ . . .... . . .... . . . .... 222
9.3 Interactions of Acid-Base Systems with the Components of
Artificial Sea Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 225
9.3-1 Organic Ligands .................................................... 226
9.3.2 Inorganic Ligands................................................... 241
9.3-3 Metals and Organometallic Compounds ............................ 243
9.4 Discussion and Conclusions ............................................... 248
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 250
Appendix. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 253
A9.1 Abbreviations and Formula . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 253
A9.2 Tables............................................................... 255
10 Equilibrium Analysis, the Ionic Medium Method and
Activity Factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 263
10.1 Introduction............................................................... 263
10.2 Equilibrium Analysis ...................................................... 263
10.3 Activity Factors in Multi-Component Electrolyte Systems. . . . . . . . . . . . . . . . .. 266
10-4 The Pitzer and the Br0nsted-Guggenheim-Scatchard
Ion Interaction Models .................................................... 267
10.5 Comparison of the SIT and Pitzer Models. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 270
10.6 Determination of Interaction Parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 282
11 Acid-Base Equilibria in Saline Media:
Application of the Mean Spherical Approximation ..................... 283
11.1 Introduction............................................................... 283
11.2 Acid-Base Equilibria in Saline Media ...................................... 283
11.3 pK' vs. Ionic Strength Equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 285
11.4 The Mean Spherical Approximation: Estimation of Q(g) Term by
Use of the MSA Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 286
11.5 Comparison with the Pitzer Model. . . . . . . .. . . . . . .. . . . . . . . .. . . . . . .. .. . . . . ... 288