Water Chemistry, Second Edition

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Front Cover Reference - Periodic Table of the Elements Reference - Chemical Symbols, Atomic Numbers, and Atomic Mass Title Page Dedication Contents PREFACE TO THE SECOND EDITION PREFACE TO THE FIRST EDITION ACKNOWLEDGMENTS ABOUT THE AUTHOR 1 BASICS OF AQUATIC CHEMISTRY Contents 1.1 INTRODUCTION 1.2 THE STRUCTURE OF WATER MOLECULES AND INTERACTIONS AMONG THEM 1.3 THE BEHAVIOR OF SOLUTES IN WATER; DISSOLUTION OF SALTS 1.4 COMMON APPROACHES FOR EXPRESSINGCONCENTRATIONS IN ENVIRONMENTALCHEMISTRY 1.5 SUMMARY 1.6 PROBLEMS 2 CHEMICAL REACTIVITY, REACTIONS, AND EQUILIBRIUM Contents 2.1 OVERVIEW 2.2 CHARACTERIZING CHEMICAL REACTIVITY 2.3 PREDICTING ACTIVITY COEFFICIENTS FROM KNOWLEDGE OF THE SOLUTION COMPOSITION 2.4 THE ACTIVITY AS AN INTENSIVE PROPERTY; THE ACTIVITY OF SOLIDS DISPERSED IN WATER 2.5 MODELS OF CHEMICAL EQUILIBRIUM 2.6 EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT 2.7 COMBINING CHEMICAL REACTIONS 2.8 SUMMARY 2.9 PROBLEMS 3 REACTION KINETICS AND THE KINETICS-BASED INTERPRETATION OF EQUILIBRIUM Contents 3.1 A MOLECULAR-LEVEL PICTURE OF AN ELEMENTARY REACTION AND THE FACTORS THAT AFFECT ITS RATE 3.2 EFFECT OF TEMPERATURE ON REACTION RATE CONSTANTS 3.3 THE KINETICS OF SOME IMPORTANT CATEGORIES OF ENVIRONMENTAL CHEMICAL REACTIONS 3.4 KINETICS OF ELEMENTARY CHEMICAL REACTIONS 3.5 REACTION REVERSIBILITY AND THE DEFINITION OF THE EQUILIBRIUM CONSTANT 3.6 EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT 3.7 COMBINING CHEMICAL REACTIONS: KINETICS AND EQUILIBRIUM CONSTANTS OF NONELEMENTARY REACTIONS 3.8 EXPERIMENTAL EVALUATION OF REACTION KINETICS 3.9 RATE-LIMITING STEPS AND SOME CLASSICAL, MODEL REACTION PATHWAYS 3.10 HETEROGENEOUS (PHASE-TRANSFER) REACTIONS 3.11 SUMMARY 3.12 PROBLEMS 4 POTENTIALS, ENERGY, AND FORCES: INTERPRETING CHANGES IN PHYSICAL/CHEMICAL SYSTEMS Contents 4.1 INTRODUCTION 4.2 POTENTIAL ENERGY, POTENTIALS, AND FORCES 4.3 OVERVIEW OF POTENTIAL AND POTENTIAL ENERGY IN CHEMICAL SYSTEMS 4.4 ENTROPY AND GIBBS ENERGY 4.5 THE CHEMICAL POTENTIAL AND ITS USE TO PREDICT CHEMICAL CHANGE 4.6 OTHER MOLAR THERMODYNAMIC QUANTITIES 4.7 QUANTIFYING Gi, Hi, and Si 4.8 THE DEPENDENCE OF Gi ON SYSTEM COMPOSITION, TEMPERATURE, AND PRESSURE 4.9 COMPARISON OF Gi OF DIFFERENT SPECIES 4.10 THE DEPENDENCE OF Gi ON PRESSURE AND TEMPERATURE 4.11 COMPARING THE MAGNITUDE OF FACTORS THAT AFFECT Gi 4.12 CHEMICAL POTENTIAL AS THE DRIVING FORCE FOR CHEMICAL REACTIONS 4.13 SUMMARY 4.14 PROBLEMS 5 ACIDS AND BASES, PART 1: ACID/BASE SPECIATION AND EXACT SOLUTIONS TO ACID/BASE PROBLEMS Contents 5.1 INTRODUCTION 5.2 THE DISSOCIATION OF WATER; Kw 5.3 THE STRUCTURE OF ACIDS AND BASES 5.4 STRONG AND WEAK ACIDS, Ka, AND CONJUGATE ACID/BASE PAIRS 5.5 A BRIEF DIVERSION: THE STRUCTURE OF SOME IMPORTANT ORGANIC ACIDS AND BASES 5.6 COMBINING ACIDITY REACTIONS AND THE DEFINITION OF BASICITY 5.7 ACID/BASE SPECIATION AS A FUNCTION OF pH; DIAGRAMS OF LOG C VERSUS pH 5.8 LOG C-pH DIAGRAMS FOR MONOPROTIC ACIDS 5.9 EFFECTS OF NONIDEAL SOLUTE BEHAVIOR ON ACID/BASE SPECIATION 5.10 LOG C-pH DIAGRAMS FOR MULTIPROTIC ACIDS 5.11 DETERMINING SPECIES AND RELEVANT EQUATIONS FOR SOLVING EQUILIBRIUM PROBLEMS 5.12 NUMERICAL APPROACHES FOR SOLVING ACID/BASE PROBLEMS 5.13 THE pH OF SOLUTIONS CONTAINING ONLY WATER AND STRONG ACIDS OR BASES 5.14 THE pH OF IDEAL SOLUTIONS CONTAINING WEAK ACIDS AND BASES 5.15 A SIMPLE SPREADSHEET ANALYSIS FOR DETERMINING ACID/BASE SPECIATION 5.16 THE pH AND SPECIATION OF SYSTEMS CONTAINING MULTIPROTIC WEAK ACIDS AND BASES 5.17 ACID/BASE EQUILIBRIA IN NONIDEAL SOLUTIONS 5.18 SUMMARY 5.19 PROBLEMS 6 ACIDS AND BASES, PART 2: USE OF Log C-pH DIAGRAMS AND THE TOTH EQUATION Contents 6.1 GRAPHICAL SOLUTIONS FOR SETS OF SIMULTANEOUS EQUATIONS 6.2 USING LOG C-pH DIAGRAMS TO SOLVE WEAK ACID/BASE PROBLEMS 6.3 THE MASS BALANCE ON H(THE TOTH EQUATION AND PROTON CONDITION) 6.4 DEFINING THE COMPOSITION OF THE SYSTEM: COMPONENTS, SPECIES, AND THE SYSTEM TABLEAU 6.5 EXPRESSING INPUT AND EQUILIBRIUM CONCENTRATIONS IN TERMS OF COMPONENTS; COMPONENT MASS BALANCES 6.6 IDENTIFYING DOMINANT SPECIES 6.7 COMPARISON OF APPROACHES FOR SOLVING ACID/BASE PROBLEMS 6.8 SUMMARY 6.9 APPENDIX 6A: ARITHMETIC OPERATIONS AND LOG-LOG DIAGRAMS 6.10 PROBLEMS 7 SOFTWARE FOR SOLVING CHEMICAL EQUILIBRIUM PROBLEMS Contents 7.1 INTRODUCTION 7.2 THE COMPUTER ALGORITHM FOR SOLVING A SIMPLE ACID/BASE PROBLEM 7.3 SYSTEMS IN WHICH THE EQUILIBRIUM ACTIVITIES OF ONE OR MORE SPECIES ARE KNOWN 7.4 USING CHEMICAL EQUILIBRIUM SOFTWARE TO DEVELOP LOG C–pH DIAGRAMS 7.5 MODIFYING THE COMPONENT AND SPECIES DATABASES IN VISUAL MINTEQ 7.6 SUMMARY 7.7 PROBLEMS 8 TITRATIONS AND BUFFERS Contents 8.1 INTRODUCTION 8.2 REACTIONS OCCURRING DURING A TITRATION: QUALITATIVE CONSIDERATIONS 8.3 QUANTITATIVE INTERPRETATION OF TITRATION DATA 8.4 USING VISUAL MINTEQ TO SIMULATE TITRATIONS 8.5 TITRATIONS WITH WEAK ACIDS OR BASES 8.6 THE EFFECT OF THE ACIDITY OF WATER ON TITRATION CURVES 8.7 TITRATION OF SOLUTIONS CONTAINING UNKNOWN ACIDS AND BASES 8.8 TITRATION EQUIVALENCE POINTS 8.9 ALKALINITY AND ACIDITY 8.10 ACID/BASE TITRATIONS OF NATURAL ORGANIC MATTER 8.11 BUFFERS 8.12 SUMMARY 8.13 APPENDIX 8A: DETERMINING ALKALINITY FACTORS AND INSERTING THEM INTO THE VISUAL MINTEQ DATABASE 8.14 APPENDIX 8B: DERIVATION OF THE BUFFER INTENSITY OF MULTIPROTIC ACIDS 8.15 PROBLEMS 9 GAS/LIQUID EQUILIBRIUM Contents 9.1 INTRODUCTION 9.2 BASIC CONCEPTS AND TERMINOLOGY FOR GAS/LIQUID EQUILIBRIUM 9.3 EFFECT OF GAS/LIQUID EQUILIBRATION ON GAS-PHASE COMPOSITION 9.4 FACTORS AFFECTING VOLATILITY AND HENRY’S CONSTANT 9.5 HENRY’S LAW AND AQUEOUS-PHASE SPECIATION 9.6 THE pH OF SOLUTIONS IN EQUILIBRIUM WITH ACIDIC OR BASIC GASES 9.7 GAS-LIQUID EQUILIBRIUM IN VISUAL MINTEQ 9.8 BUFFERING IN SOLUTIONS EQUILIBRATED WITH WEAK ACID AND WEAK BASE GASES 9.9 CO2 DISSOLUTION, ALKALINITY, AND ACIDITY 9.10 SUMMARY 9.11 APPENDIX 9A. THE LIQUID-PHASE ACTIVITY COEFFICIENT IN HENRY’S LAW USING THE RAOULT’S LAW STANDARD STATE CONVENTION 9.12 PROBLEMS 10 CHEMISTRY OF METALS IN AQUEOUS SYSTEMS 1. SOLUTION-PHASE REACTIONS Contents 10.1 INTRODUCTION 10.2 METAL OXIDATION STATES 10.3 FORMATION AND STRUCTURE OF METAL COMPLEXES 10.4 COMPLEXES WITH HYDROXIDE IONS 10.5 LOGC-pH DIAGRAMS FOR DISSOLVED METALS 10.6 COMPLEXES WITH LIGANDS OTHER THAN WATER AND HYDROXIDE 10.7 MIXED LIGAND COMPLEXES AND CHELATING AGENTS 10.8 METAL SPECIATION IN SYSTEMS CONTAINING COMPLEXING LIGANDS 10.9 METAL ION BUFFERS 10.10 PREDOMINANCE AREA DIAGRAMS 10.12 PROBLEMS 11 CHEMISTRY OF METALS IN AQUEOUS SYSTEMS 2. PRECIPITATION AND DISSOLUTION REACTIONS Contents 11.1 INTRODUCTION 11.2 FORMATION OF SOLIDS CONTAINING METAL IONS 11.3 THE CHEMICAL ACTIVITY OF PURE SOLIDS 11.4 THE SOLUBILITY PRODUCT 11.5 PRECIPITATION OF SOLIDS OTHER THAN HYDROXIDES 11.6 FORMATION OF NONHYDROXO COMPLEXES IN SYSTEMS WITH SOLIDS 11.7 ADDING NEW SOLIDS TO THE VISUAL MINTEQ DATABASE 11.8 DETERMINING WHETHER A SOLID WILL PRECIPITATE UNDER GIVEN CONDITIONS 11.9 THE GIBBS PHASE RULE 11.10 PREDOMINANCE AREA DIAGRAMS CONSIDERING POSSIBLE PRECIPITATION OF SOLIDS 11.11 SUMMARY 11.12 PROBLEMS 12 REDOX CHEMISTRY Contents 12.1 INTRODUCTION 12.2 DETERMING OXIDATION NUMBERS 12.3 BALANCING REDOX REACTIONS 12.4 REDOX HALF-REACTIONS 12.5 THE ACTIVITY OF FREE ELECTRONS; EQUILIBRIUM CONSTANTS FOR REDOX HALF-REACTIONS 12.6 DEFINITION OF e° AND pe° 12.7 COMPUTING pe FROM SPECIES ACTIVITIES:THE NERNST EQUATION 12.8 COMBINING REDOX REACTIONS 12.9 REDOX SPECIATION AND LOG C-pe DIAGRAMS 12.10 SUMMARY OF SOME KEY SIMILARITIES BETWEEN ACID/BASE AND REDOX SYSTEMS 12.11 REDOX REACTIONS INVOLVING EXCHANGE OF BOTH ELECTRONS AND PROTONS 12.12 COMPUTING EQUILIBRIUM SPECIATION IN REDOX SYSTEMS 12.13 MODELING REDOX REACTIONS WITH VISUAL MINTEQ 12.14 OXIDATION AND REDUCTION OF WATER 12.15 ENERGY CHANGES ACCOMPANYING REDOX REACTIONS 12.16 REDOX TITRATIONS AND THE GEOCHEMICAL REDOX SEQUENCE 12.17 pe-pH PREDOMINANCE AREA DIAGRAMS 12.18 REDOX REACTIONS ANDELECTROCHEMISTRY 12.19 SUMMARY 12.20 PROBLEMS 13 ADSORPTION REACTIONS Contents 13.1 INTRODUCTION 13.2 TWO VIEWS OF THE INTERFACE AND ADSORPTION EQUILIBRIUM 13.3 QUANTITATIVE REPRESENTATIONS OF ADSORPTION EQUILIBRIUM: THE ADSORPTION ISOTHERM 13.4 MODELING ADSORPTION WITH VISUAL MINTEQ 13.5 ADSORPTION OF IONS IN THE PRESENCE OF A SURFACE ELECTRICAL POTENTIAL 13.6 MODELING SURFACE-ADSORBATE ELECTRICAL INTERACTIONS IN VISUAL MINTEQ 13.7 SURFACE PRECIPITATION 13.8 SUMMARY 13.9 PROBLEMS Appendix A: Thermodynamic Data and Equilibrium Constants A1: Thermodynamic Properties A2: Table 5.1 - Chemical formulas and acidity constants at 25° C of some important acids A3: Table 9.2 - Henry's constants of some environmentally important gases A4: Table 10.2 - Stability constants for complexation of metals by OH– A5: Table 10.3 - Stability constants for some metal-ligand complexes A6: Table 11.1 - The Ks0 values of some solids of interest A7: Table 12.3 - Equilibrium constants for some environmentally important redox half-reactions Appendix B: List of Important Equations Index Reference - International Units, Dimensions of Other Parameters, Physical and Chemical Constants, Mathematical Constants and Other Numbers Reference - Useful Conversion Factors