Water Chemistry, Second Edition

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