Preface xiii
Acknowledgments xvii
1. Introductory Remarks 1
1.1 Perspective / 1
1.2 Organization and Objectives / 2
1.3 Approach / 8
2. Water 11
2.1 Perspective / 11
2.2 Important Properties of Water / 12
3. Concentration Units for Gases, Liquids, and Solids 16
3.1 Selected Concentration Units / 16
3.2 The Ideal Gas Law and Gas Phase Concentration Units / 20
3.3 Aqueous Concentration Units / 23
3.4 Applications of Volume Fraction Units / 28
4. The Law of Mass Action and Chemical Equilibria 36
4.1 Perspective / 36
4.2 The Law of Mass Action / 37
4.3 Gas/Water Distributions / 38
4.4 Acid/Base Systems / 39
4.5 Metal Complexation Systems / 40
4.6 Water/Solid Systems (Solubility/Dissolution) / 41
4.7 Oxidation/Reduction Half Reactions / 43
5. Air / Water Distribution: Henry¢s Law 44
5.1 Perspective / 44
5.2 Henry¢s Law Constants / 46
5.3 Applications of Henry¢s Law / 51
6. Acid/Base Component Distributions 64
6.1 Perspective / 64
6.2 Proton Abundance in Aqueous Solutions: pH and the Ion Product of Water / 65
6.3 Acid Dissociation Constants / 69
6.4 Mole Accounting Relations / 70
6.5 Combination of Mole Balance and Acid/Base Equilibria / 74
6.6 Alkalinity, Acidity, and the Carbonate System / 82
6.7 Applications of Acid/Base Principles in Selected Environmental Contexts / 91
7. Mass Balance, Ideal Reactors, and Mixing 119
7.1 Perspective / 119
7.2 The Mass Balance / 120
7.3 Residence Time Distribution (RTD) Analyses / 121
7.4 Exit Responses for Ideal Reactors / 125
7.5 Modeling of Mixing in Ideal CMFRs / 130
7.6 Applications of CMFR Mixing Principles in Environmental Systems / 144
8. Reactions in Ideal Reactors 157
8.1 Perspective / 157
8.2 Chemical Stoichiometry and Mass/Volume Relations / 158
8.3 Reactions in Ideal Reactors / 171
8.4 Applications of Reactions in Ideal Reactors / 183
8.5 Interfacial Mass Transfer in Ideal Reactors / 216
9. Reactions in Nonideal Reactors 265
9.1 Perspective / 265
9.2 Exit Concentration Versus Time Traces / 266
9.3 Residence Time Distribution Density / 267
9.4 Cumulative Residence Time Distributions / 271
9.5 Characterization of RTD Distributions / 272
9.6 Models for Addressing Longitudinal Dispersion in Reactors / 275
9.7 Modeling Reactions in CMFRs in Series (TiS) Reactors / 280
9.8 Modeling Reactions with the Plug-Flow with Dispersion Model / 282
9.9 Modeling Reactions Using the Segregated Flow (SF) Model / 289
9.10 Applications of Nonideal Reactor Models / 291
9.11 Considerations for Analyses of Spatially Variant Processes / 305
9.12 Modeling Utilization and Growth in PFR-Like Reactors Using TiS and SF / 318
10. Acid-Base Advanced Principles 335
10.1 Perspective / 335
10.2 Activity Coefficient / 336
10.3 Temperature Dependence of Equilibrium Constants / 344
10.4 Nonideal Conjugate Acid/Conjugate Base Distributions / 350
10.5 The Proton Balance (Proton Condition) / 358
10.6 Analyses of Solutions Prepared by Addition of Acids, Bases, and Salts to Water / 365
10.7 Analysis of Mixed Aqueous Solutions / 380
10.8 Acid and Base Neutralizing Capacity / 396
10.9 Activity Versus Concentration for Nonelectrolytes / 417
11. Metal Complexation and Solubility 439
11.1 Perspective / 439
11.2 Hydration of Metal Ions / 440
11.3 Cumulative Formation Constants / 441
11.4 Formation Equilibria for Solids / 447
11.5 Speciation of Metals in Aqueous Solutions Containing Ligands / 448
11.6 Metal Hydroxide Solubility / 456
11.7 Solubility of Metal Carbonates / 467
11.8 Solubility of Other Metal¢"Ligand Solids / 511
12. Oxidation and Reduction 519
12.1 Perspective / 519
12.2 Redox Half Reactions / 520
12.3 The Nernst Equation / 533
12.4 Electron Availability in Environmental Systems / 535
Appendices 571
References 599
Index 602
