Preface xiii
About the Companion Website xv
Introduction xvii
1 Origins: A Chemical History of the Earth from the Big Bang Until Now – 13.8 Billion Years of Review 1
1.1 Introduction 1
1.2 The Big Bang 1
1.2.1 The Microwave Background 1
1.2.2 Stars and Elements 4
1.2.3 Primordial Nucleosynthesis 5
1.2.4 Nucleosynthesis in Massive Stars 5
1.2.5 Nucleosynthesis Summary 7
1.3 Solar Nebular Model: The Birth of Our Solar System 8
1.3.1 The Ages of the Earth 9
1.3.1.1 Hadean Eon (4.6 to 4.0 Ga) 9
1.3.1.2 Archean Eon (4.0 to 2.5 Ga) 13
1.3.1.3 Proterozoic Eon (2.5 to 0.5 Ga) 14
1.3.1.4 Phanerozoic Eon (0.5 Ga to Present) 15
1.3.1.5 Summary 15
1.4 Life Emerges 16
1.4.1 Biomolecules 16
1.4.2 Macromolecules 17
1.4.3 Self-Replication 19
1.4.4 Molecular Evolution 21
1.5 Review Material 22
1.6 Important Terms 48
Exercises 49
Bibliography 51
2 Measurements and Statistics 53
2.1 Introduction 53
2.2 Measurements 54
2.2.1 Random Noise 54
2.2.2 Significant Figures (Sig Figs) 58
2.2.3 Systematic Errors 59
2.3 Primary and Secondary Standards 60
2.3.1 Other Reagents 61
2.4 Sample and Population Distributions 62
2.5 Hypothesis Testing 63
2.6 Methods of Quantitation 67
2.6.1 The Method of External Standards 68
2.6.2 Internal Standards 69
2.6.2.1 The Method of Multipoint Internal Standard 69
2.6.2.2 The Method of Single-Point Internal Standard 71
2.6.3 The Method of Standard Additions 72
2.6.3.1 The Equal-Volume Version of the Method of Multiple Standard Additions 72
2.6.3.2 The Variable-Volume Version of the Method of Standard Additions 75
2.6.3.3 How the Method of Standard Additions Eliminates Proportional Errors 77
2.7 Quantitative Equipment 78
2.7.1 Analytical Balances 78
2.7.2 Glassware 79
2.7.3 Pipettors 80
2.7.4 Cleaning 82
2.7.5 Sample Cells and Optical Windows 82
2.7.5.1 Plastic 83
2.7.5.2 Glass and Quartz 83
2.7.5.3 Well Plates 83
2.8 Linear Regression Line 84
2.8.1 The Method of External Standard Regression Template 84
2.8.2 The Method of Multipoint Internal Standard Regression Template 89
2.8.3 The Equal-Volume Variant of the Method of Multiple Standard Addition Regression Template 91
2.8.4 Where Unknowns Should Fall on the Calibration Curve 92
2.9 Important Terms 92
Exercises 93
Bibliography 94
3 The Atmosphere 95
3.1 Introduction 95
3.2 An Overview of the Atmosphere 96
3.3 The Exosphere and Thermosphere 97
3.4 The Mesosphere 100
3.5 The Stratosphere 101
3.5.1 The Chapman Cycle 101
3.6 The Troposphere 104
3.6.1 The Planetary Energy Budget 105
3.6.2 Greenhouse Effect 108
3.7 Tropospheric Chemistry 111
3.7.1 The Internal Combustion Engine 112
3.7.1.1 The Four-Stroke Gasoline Engine 114
3.7.1.2 The Two-Stroke Gasoline Engine 115
3.7.1.3 The Four-Stroke Diesel Engine 115
3.7.1.4 Engine Emission Comparison 116
3.7.1.5 Fuel Alternatives and Additives 117
3.7.2 Ground-Level Ozone and Photochemical Smog 118
3.7.3 The Hydroxyl Radical 121
3.7.3.1 Carbon Monoxide and Hydroperoxyl Radical 122
3.7.3.2 Alkanes 123
3.7.3.3 Alkenes 125
3.7.3.4 Terpenes 127
3.7.3.5 Nitrogen-Containing Compounds 127
3.7.3.6 Sulfur-Containing Compounds 127
3.7.3.7 Nighttime Reactions 129
3.7.3.8 Summary of Reaction Involving the Hydroxyl Radical 131
3.8 Classical Smog 132
3.9 Acid Deposition 134
3.10 Ozone Destruction in the Stratosphere 137
3.11 The Ozone Hole 141
3.11.1 Polar Stratospheric Clouds 141
3.11.2 The Polar Vortex 142
3.11.3 The Dark Winter 143
3.12 CFC Replacements 143
3.13 Climate Change 146
3.14 Measurements of Atmospheric Constituents 154
3.14.1 Satellite-Based Measurements 155
3.14.2 Ground-Based Measurements 156
3.14.2.1 LIDAR 156
3.14.2.2 Cavity Ring-Down Spectroscopy 156
3.14.3 Ambient Monitoring 156
3.14.4 Infrared Spectroscopy 157
3.15 Important Terms 157
Exercises 158
Bibliography 161
4 The Lithosphere 165
4.1 Introduction 165
4.2 Soil Formation 165
4.2.1 Physical Weathering 166
4.2.2 Chemical Weathering 167
4.2.3 Minerals 167
4.2.4 Organic Matter and Decay 168
4.2.4.1 Biopolymers 169
4.2.4.2 Leaf Senescence 169
4.2.4.3 Microbial Degradation 170
4.2.5 Microorganism Classifications 172
4.2.6 Respiration and Redox Chemistry 173
4.3 Metals and Complexation 176
4.3.1 Phytoremediation 178
4.4 Acid Deposition and Soil 178
4.4.1 Limestone Buffering 179
4.4.2 Cation-Exchange Buffering 181
4.4.3 Aluminum Buffering 182
4.4.4 Biotic Buffering Systems 182
4.4.5 Buffering Summary 183
4.4.6 Aluminum Toxicity 184
4.5 Measurements 185
4.5.1 Metals 185
4.5.2 pH and the Equilibrium Soil Solution 186
4.6 Important Terms 187
Exercises 187
Bibliography 189
5 The Hydrosphere 191
5.1 Introduction 191
5.2 The Unusual Properties of Water 191
5.2.1 Freshwater Stratification 192
5.2.2 The Thermohaline Circulation 193
5.2.3 Salinity 194
5.3 Water as a Solvent 194
5.3.1 Dissolved Solids 195
5.3.2 Dissolved Oxygen 196
5.3.2.1 Temperature Effects 197
5.3.2.2 Salinity Effects 198
5.4 The Carbon Cycle 199
5.4.1 Anthropogenic Contributions 200
5.4.2 Biotic Processes 200
5.4.3 Summary 200
5.5 The Nitrogen Cycle 201
5.5.1 Nitrogen Fixation and Assimilation 202
5.5.2 Ammonification 202
5.5.3 Nitrification 202
5.5.4 Denitrification 203
5.5.5 Summary 203
5.6 The Phosphorus Cycle 203
5.7 The Sulfur Cycle 205
5.7.1 Summary 206
5.8 Water Quality 206
5.9 Wastewater Treatment 208
5.9.1 Biochemical Oxygen Demand and Chemical Oxygen Demand 208
5.9.2 Primary Treatment 210
5.9.3 Secondary Treatment 210
5.9.4 Anaerobic Digestion 211
5.9.5 Tertiary Treatment 212
5.9.5.1 Biological Nitrogen Removal 212
5.9.5.2 Chemical Nitrogen Removal 212
5.9.5.3 Chemical Phosphorus Removal 213
5.9.5.4 Biological Phosphorus Removal 213
5.9.6 Filtration 213
5.9.7 Disinfection 213
5.9.8 Biosolids 214
5.9.9 Septic Tanks and Sewage Fields 214
5.10 Measurements 215
5.10.1 Potentiometric pH Measurements 215
5.10.1.1 Spectrophotometric pH Measurements 216
5.10.2 Total Dissolved Solids (TDS) 217
5.10.3 Salinity 217
5.10.4 Total Organic Carbon (TOC) 217
5.10.5 Biochemical Oxygen Demand (BOD) 218
5.10.6 Chemical Oxygen Demand (COD) 219
5.10.7 Dissolved Oxygen 219
5.10.7.1 Titrimetric Method 220
5.10.7.2 Dissolved Oxygen via ISE 221
5.10.8 The Nitrate Ion 222
5.10.8.1 Spectroscopy 222
5.10.8.2 Ion-Selective Electrode 222
5.10.8.3 Ion Chromatography 223
5.10.9 The Nitrite Ion 223
5.10.10 Ammoniacal Nitrogen 223
5.10.11 The Phosphate Ion 223
5.10.12 The Sulfate Ion 224
5.11 Important Terms 224
Exercises 225
Bibliography 227
A Chapter 1 Review Examples and End-of-Chapter Exercises 231
A.1 Solutions to In-Chapter Review Examples 231
A.2 Questions about the Big Bang, Solar Nebular Model, and Formation of the Earth 249
B Chapter 2 Examples and End-of-Chapter Exercises 253
B.1 Solutions to In-Chapter Examples 253
B.2 Solutions to End-of-Chapter Exercises 257
C Chapter 3 Examples and End-of-Chapter Exercises 261
C.1 Solutions to In-Chapter Examples 261
C.2 Solutions to End-of-Chapter Exercises 266
D Chapter 4 Examples and End-of-Chapter Exercises 277
D.1 Solutions to In-Chapter Examples 277
D.2 Solutions to End-of-Chapter Exercises 280
E Chapter 5 Examples 285
E.1 Solutions to In-Chapter Examples 285
E.2 Solutions to End-of-Chapter Exercises 289
F Common Chemical Instrumentation 295
F.1 UV-Vis Spectrophotometers 295
F.1.1 Turbidity 296
F.1.2 Quantitation 297
F.2 Fluorometers 297
F.2.1 Nephelometry 298
F.2.2 Quantitation 298
F.3 Atomic Absorption Spectrophotometers 299
F.3.1 Flame Atomization 299
F.3.2 Electrothermal Atomization 299
F.3.3 Summary 300
F.3.4 Quantitation 300
F.4 Inductively Coupled Plasma Instrument 300
F.4.1 Summary 301
F.4.2 Quantitation 301
F.5 Chromatography 302
F.5.1 Quantitation 303
F.6 Infrared Spectrometry 304
F.6.1 Quantitation 306
Exercises 307
F.6.2 UV-Vis Spectrophotometry 307
F.6.3 Fluorometers 307
F.6.4 Atomic Absorption Spectrophotometry (AAS) and ICP-MS/OES 307
F.6.5 Chromatography 307
F.6.6 FTIR Spectrometer 307
F.7 Answers to Common Instrumentation Exercises 308
F.7.1 UV-Vis Spectrophotometry 308
F.7.2 Fluorometers 308
F.7.3 Atomic Absorption Spectrophotometry (AAS) and ICP-MS/OES 308
F.7.4 Chromatography 309
F.7.5 FTIR Spectrometer 309
Bibliography 310
G Derivations 311
G.1 The Equal Volume Method of Multiple Standard Additions Formula 311
G.2 Two-Point Variable-Volume Method of Standard Addition Formula 312
G.3 Variable-Volume Method of Multiple Standard Additions Formula 313
H Tables 315
H.1 Student’s t Table 315
H.2 F Test Table 316
I Chemical and Physical Constants 317
I.1 Physical Constants 317
I.2 Standard Thermochemical Properties of Selected Species 318
I.3 Henry’s Law Constants 321
I.4 Solubility Product Constants 322
I.5 Acid Dissociation Constants 323
I.6 Base Dissociation Constants 324
I.7 Bond Energies 325
I.8 Standard Reduction Potentials 326
I.9 OH Oxidation Rate Constants Values 327
Bibliography 327
Index 329
(leitura online e APP)
