Inorganic Chemistry for Geochemistry and Environmental Sciences: Fundamentals and Applications

Inorganic Chemistry for Geochemistry and Environmental Sciences: Fundamentals and Applications

By: George W. Luther (author)Hardback

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Description

Inorganic Chemistry for Geochemistry and Environmental Sciences: Fundamentals and Applications discusses the structure, bonding and reactivity of molecules and solids of environmental interest, bringing the reactivity of non-metals and metals to inorganic chemists, geochemists and environmental chemists from diverse fields. Understanding the principles of inorganic chemistry including chemical bonding, frontier molecular orbital theory, electron transfer processes, formation of (nano) particles, transition metal-ligand complexes, metal catalysis and more are essential to describe earth processes over time scales ranging from 1 nanosec to 1 Gigayr. Throughout the book, fundamental chemical principles are illustrated with relevant examples from geochemistry, environmental and marine chemistry, allowing students to better understand environmental and geochemical processes at the molecular level. Topics covered include: Thermodynamics and kinetics of redox reactions Atomic structure Symmetry Covalent bonding, and bonding in solids and nanoparticles Frontier Molecular Orbital Theory Acids and bases Basics of transition metal chemistry including Chemical reactivity of materials of geochemical and environmental interest Supplementary material is provided online, including PowerPoint slides, problem sets and solutions. Inorganic Chemistry for Geochemistry and Environmental Sciences is a rapid assimilation textbook for those studying and working in areas of geochemistry, inorganic chemistry and environmental chemistry, wishing to enhance their understanding of environmental processes from the molecular level to the global level.

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Contents

About the Author xv Preface xvii Companion Website xix 1. Inorganic Chemistry and the Environment 1 1.1 Introduction 1 1.1.1 Energetics of Processes 1 1.2 Neutron Proton Conversion 3 1.3 Element Burning Reactions Buildup of Larger Elements 4 1.4 Nuclear Stability and Binding Energy 5 1.4.1 The r and s Processes 6 1.5 Nuclear Stability (Radioactive Decay) 8 1.6 Atmospheric Synthesis of Elements 8 1.7 Abundance of the Elements 8 1.7.1 The Cosmos and the Earth s Lithosphere 8 1.7.2 Elemental Abundance (Atmosphere, Oceans, and Human Body) 10 1.8 Scope of Inorganic Chemistry in Geochemistry and the Environment 17 1.8.1 Elemental Distribution Based on Photosynthesis and Chemosynthesis 17 1.8.2 Stratified Waters and Sediments the Degradation of Organic Matter by Alternate Electron Acceptors 19 1.9 Summary 21 1.9.1 Environmental Inorganic Chemistry 22 References 22 2. Oxidation Reduction Reactions (Redox) 24 2.1 Introduction 24 2.1.1 Energetics of Half Reactions 24 2.1.2 Standard Potential and the Stability of a Chemical Species of an Element 26 2.2 Variation of Standard Potential with pH (the Nernst Equation) 29 2.3 Thermodynamic Calculations and pH Dependence 29 2.4 Stability Field of Aqueous Chemical Species 31 2.5 Natural Environments 32 2.6 Calculations to Predict Favorable Chemical Reactions 32 2.6.1 Coupling Half-Reactions 34 2.6.2 One-Electron Oxygen Transformations with Fe2+ and Mn2+ to Form O2 35 2.7 Highly Oxidizing Conditions 38 2.7.1 Ozonolysis Reactions 38 2.7.2 Atmospheric Redox Reactions 39 Appendix 2.1 Gibbs Free Energies of Formation 43 References 43 3. Atomic Structure 45 3.1 History 45 3.2 The Bohr Atom 46 3.3 The Schrodinger Wave Equation 47 3.4 Components of the Wave Function 50 3.4.1 Radial Part of the Wave Function, R(r) 50 3.4.2 Angular Part of the Wavefunction Ylml( , ) and Atomic Orbitals 54 3.5 The Four Quantum Numbers 56 3.6 The Polyelectronic Atoms and the Filling of Orbitals for the Atoms of the Elements 58 3.7 Aufbau Principle 61 3.8 Atomic Properties 62 3.8.1 Orbitals Energies and Shielding 62 3.8.2 Term Symbols: Coupling of Spin and Orbital Angular Momentum 63 3.8.3 Periodic Properties Atomic Radius 67 3.8.4 Periodic Properties Ionization Potential (IP) 67 3.8.5 Periodic Properties Electron Affinity (EA) 71 3.8.6 Periodic Properties Electronegativity ( ) 74 3.8.7 Periodic Properties Hardness ( ) 75 References 77 4. Symmetry 79 4.1 Introduction 79 4.2 Symmetry Concepts 79 4.2.1 Symmetry Operation 79 4.2.2 Symmetry Element 79 4.2.3 Symmetry Elements and Operations 80 4.3 Point Groups 84 4.3.1 Special Groups and Platonic Solids/Polyhedra 85 4.3.2 Examples of the Use of the Scheme for Determining Point Groups 88 4.4 Optical Isomerism and Symmetry 92 4.4.1 Dichloro-Allene Derivatives (C3H2Cl2) 92 4.4.2 Tartaric Acid 93 4.4.3 Cylindrical Helix Molecules 93 4.5 Fundamentals of Group Theory 93 4.5.1 C2v Point Group 95 4.5.2 Explanation of the Character Table 96 4.5.3 Generation of the Irreducible Representations (C2v Case) 97 4.5.4 Notation for Irreducible Representations 97 4.5.5 Some Important Properties of the Characters and their Irreducible Representations 98 4.5.6 Nonindependence of x and y Transformations (Higher Order Rotations) 98 4.6 Selected Applications of Group Theory 101 4.6.1 Generation of a Reducible Representation to Describe a Molecule 101 4.6.2 Determining the IR and Raman Activity of Vibrations in Molecules 104 4.6.3 Determining the Vibrational Modes of Methane, CH4 105 4.6.4 Determining the Irreducible Representations and Symmetry of the Central Atom s Atomic Orbitals that Form Bonds 107 4.7 Symmetry Adapted Linear Combination (SALC) of Orbitals 111 4.7.1 Sigma Bonding with Hydrogen as Terminal Atom 111 4.7.2 Sigma and Pi Bonding with Atoms Other than Hydrogen as Terminal Atom 114 Appendix 4.1 Some Additional useful Character Tables 120 References 122 5. Covalent Bonding 123 5.1 Introduction 123 5.1.1 Lewis Structures and the Octet Rule 123 5.1.2 Valence Shell Electron Pair Repulsion Theory (VSEPR) 126 5.2 Valence Bond Theory (VBT) 127 5.2.1 H2 and Valence Bond Theory 129 5.2.2 Ionic Contributions to Covalent Bonding 130 5.2.3 Polyatomic Molecules and Valence Bond Theory 131 5.3 Molecular Orbital Theory (MOT) 132 5.3.1 H2 132 5.3.2 Types of Orbital Overlap 137 5.3.3 Writing Generalized Wave Functions 138 5.3.4 Brief Comments on Computational Methods and Computer Modeling 139 5.3.5 Homonuclear Diatomic Molecules (A2) 140 5.3.6 Heteronuclear Diatomic Molecules and Ions (AB; HX) Sigma Bonds Only 144 5.3.7 Heteronuclear Diatomic Molecules and Ions (AB) Sigma and Pi Bonds 147 5.4 Understanding Reactions and Electron Transfer (Frontier Molecular Orbital Theory) 150 5.4.1 Angular Overlap 151 5.4.2 H+ +OH 151 5.4.3 H2 +D2 152 5.4.4 H2 +F2 153 5.4.5 H2 +C2 154 5.4.6 H2 +N2 (also CO+H2) 154 5.4.7 Dihalogens as Oxidants 156 5.4.8 O2 as an Oxidant and its Reaction with H2S and HS 157 5.5 Polyatomic Molecules and Ions 161 5.5.1 H3 + Molecular Cation 161 5.5.2 BeH2 Linear Molecule with Sigma Bonds Only 163 5.5.3 H2O Angular Molecule with Sigma Bonds Only 165 5.6 Tetrahedral and Pyramidal Species with Sigma Bonds only (CH4, NH4 +, SO4 2 ) 168 5.6.1 CH4 168 5.6.2 NH3 (C3v) 170 5.6.3 BH3 and the Methyl Cation, CH3 + (D3h) 172 5.7 Triatomic Compounds and Ions Involving Bonds (A3, AB2, and ABC) 175 5.7.1 A3 Linear Species 175 5.7.2 AB2 Linear Species CO2 (COS and N2O) 178 5.7.3 O3, NO2 , and SO2 (Angular Molecules) 180 5.8 Planar Species (BF3, NO3 , CO3 2 , SO3) 182 Appendix 5.1 Bond Energies for Selected Bonds 184 Appendix 5.2 Energies of LUMOs and HOMOs 185 References 186 6. Bonding in Solids 189 6.1 Introduction 189 6.2 Covalent Bonding in Metals: Band Theory 189 6.2.1 Atomic Orbital Combinations for Metals 189 6.2.2 Metal Conductors 191 6.2.3 Semiconductors and Insulators 191 6.2.4 Fermi Level 193 6.2.5 Density of States (DOS) 194 6.2.6 Doping of Semiconductors 195 6.2.7 Structures of Solids 196 6.3 Ionic Solids 200 6.3.1 Solids AX Stoichiometry 200 6.3.2 Solids with Stoichiometry of AX2, AO2, A2O3, ABO3 (Perovskite), AB2O4 (Spinel) 203 6.3.3 Crystal Radii 205 6.3.4 Radius Ratio Rule 205 6.3.5 Lattice Energy 207 6.3.6 Born Haber Cycle 209 6.3.7 Thermal Stability of Ionic Solids 210 6.3.8 Defect Crystal Structures 212 6.4 Nanoparticles and Molecular Clusters 214 References 217 7. Acids and Bases 219 7.1 Introduction 219 7.2 Arrhenius and Bronsted Lowry Definitions 219 7.3 Hydrolysis of Metal Water Complexes 222 7.4 Hydration of Anhydrous Acidic and Basic Oxides 223 7.4.1 Acidic Oxides 223 7.4.2 Basic Oxides 224 7.4.3 Amphoteric Oxides 224 7.5 Solvent System Definition 224 7.5.1 Leveling Effect 225 7.6 Gas Phase Acid Base Strength 225 7.6.1 H3 + as a Reactant 227 7.7 Lewis Definition 227 7.7.1 MOT 228 7.7.2 Molecular Iodine Adducts or Complexes as Examples 228 7.7.3 Thermodynamics of Lewis Acid Base Reactions 229 7.7.4 Lewis Acid Base Reactions of CO2 and I2 with Water and Hydroxide Ion 230 7.7.5 Lewis Acid Base Competitive Reactions 232 7.8 Classification of Acids and Bases 232 7.8.1 Irving Williams Stability Relationship for the First Transition Metal Series 232 7.8.2 Class a and b Acids and Bases 233 7.8.3 Hard Soft Acid Base (HSAB) Theory 233 7.9 Acid Base Properties of Solids 235 References 235 8. Introduction to Transition Metals 237 8.1 Introduction 237 8.2 Coordination Geometries 237 8.3 Nomenclature 240 8.3.1 Complex Ion is Positive 241 8.3.2 Complex Ion is Negative 242 8.3.3 Complex Ion with Multiple Ligands 242 8.3.4 Complex Ion with Ligand that can Bind with More Than One Atom (Ambidentate) 243 8.3.5 Complex Ion with Multidentate Ligands 243 8.3.6 Two Complex Ions with a Bridging Ligand 243 8.4 Bonding and Isomers for Octahedral Geometry 243 8.4.1 Ionization Isomerism 244 8.4.2 Hydrate (Solvate) Isomers 244 8.4.3 Coordination Isomerism 245 8.4.4 Linkage Isomerism 245 8.4.5 Geometrical Isomerism Four Coordination 246 8.4.6 Optical Isomerism in Octahedral Geometry 248 8.5 Bonding Theories for Transition Metal Complexes 250 8.5.1 Valence Bond Theory 251 8.5.2 Crystal Field Theory 252 8.6 Molecular Orbital Theory 268 8.6.1 Case 1 Octahedral Geometry (Sigma Bonding Only) 268 8.6.2 Case 2 Octahedral Geometry (Sigma Bonding Plus Ligand Donor) 271 8.6.3 Case 3 Octahedral Geometry (Sigma Bonding Plus Ligand Acceptor) 272 8.7 Angular Overlap Model 274 8.7.1 AOM and Ligand Donor Bonding 277 8.7.2 AOM and Ligand Acceptor Bonding 278 8.7.3 MOT, Electrochemistry, and the Occupancy of Electrons in d Orbitals in Oh 278 8.7.4 AOM and Other Geometries 279 8.8 More on Spectroscopy of Metal Ligand Complexes 281 8.8.1 Charge Transfer Electronic Transitions 282 8.8.2 Electronic Spectra, Spectroscopic Terms, and the Energies of the Terms for d d Transitions 283 8.8.3 Energy and Spatial Description of the Electron Transitions Between t2g and eg * Orbitals 296 8.8.4 More Details on Correlation Diagrams 297 8.8.5 Luminescence 299 8.8.6 Magnetism and Spin Crossover in Octahedral Complexes and Natural Minerals 301 8.8.7 Note about f Orbitals in Cubic Symmetry (Oh) 303 References 303 9. Reactivity of Transition Metal Complexes: Thermodynamics, Kinetics and Catalysis 305 9.1 Thermodynamics Introduction 305 9.1.1 Successive Stability Constants on Water Substitution 305 9.1.2 The Chelate Effect 307 9.2 Kinetics of Ligand Substitution Reactions 308 9.2.1 Kinetics of Water Exchange for Aqua Complexes 310 9.2.2 Intimate Mechanisms for Ligand Substitution Reactions 310 9.2.3 Kinetic Model and Activation Parameters 311 9.2.4 Dissociative Versus Associative Preference for Octahedral Ligand Substitution Reactions 314 9.2.5 Stoichiometric Mechanisms 315 9.2.6 Tests for Reaction Mechanisms 320 9.3 Substitution in Octahedral Complexes 321 9.3.1 Examples of Dissociative Activated Mechanisms 321 9.3.2 Associative Activated Mechanisms 322 9.4 Intimate Mechanisms Affected by Steric Factors (Dissociative Preference) 324 9.4.1 Intimate Mechanisms Affected by Ligands in Cis versus Trans Positions (Dissociative Preference) 324 9.4.2 Base Hydrolysis 325 9.5 Intimate Versus Stoichiometric Mechanisms 327 9.6 Substitution in Square Planar Complexes (Associative Activation Predominates) 328 9.6.1 Effect of Leaving Group 330 9.6.2 Effect of Charge 330 9.6.3 Nature of the Intermediate Electronic Factors 330 9.6.4 Nature of the Intermediate Steric Factors 331 9.7 Metal Electron Transfer Reactions 332 9.7.1 Outer Sphere Electron Transfer 333 9.7.2 Cross Reactions 337 9.7.3 Inner Sphere Electron Transfer 339 9.8 Photochemistry 341 9.8.1 Redox 341 9.8.2 Photosubstitution Reactions d d 341 9.8.3 LMCT and Photoreduction 342 9.8.4 MLCT Simultaneous Substitution and Photo-Oxidation Redox 342 9.9 Effective Atomic Number (EAN) Rule or the Rule of 18 342 9.10 Thermodynamics and Kinetics of Organometallic Compounds 344 9.11 Electron Transfer to Molecules during Transition Metal Catalysis 345 9.12 Oxidation Addition (OXAD) and Reductive Elimination (Redel) Reactions 346 9.13 Metal Catalysis 347 9.13.1 OXO or Hydroformylation Process 348 9.13.2 Heck Reaction 350 9.13.3 Methyl Transferases 350 9.13.4 Examples of Abiotic Organic Synthesis (Laboratory and Nature) 351 9.13.5 The Haber Process Revisited 353 References 353 10. Transition Metals in Natural Systems 356 10.1 Introduction 356 10.2 Factors Governing Metal Speciation in the Environment and in Organisms 356 10.3 Transition Metals Essential for Life 358 10.4 Important Environmental Iron and Manganese Reactions 359 10.4.1 Oxidation of Fe2+ and Mn2+ by O2 Environmentally Important Metal Electron Transfer Reactions 360 10.4.2 Redox Properties of Iron Ligand Complexes 363 10.4.3 Metal Ions Exhibiting Outer Sphere Electron Transfer 364 10.5 Oxygen (O2) Storage and Transport 364 10.5.1 Hemoglobin 365 10.5.2 Hemocyanin and Hemerythrin 368 10.6 Oxidation of CH4, Hydrocarbons, NH4 + 368 10.6.1 Cytochrome P450: An Example of Cytochrome (Heme O2) Redox Chemistry 369 10.6.2 Conversion of NH4 + to NO3 (Nitrification or Aerobic Ammonium Oxidation) 371 10.7 Oxygen Production in Photosynthesis 372 References 374 11. Solid Phase Iron and Manganese Oxidants and Reductants 377 11.1 Introduction 377 11.2 Reduction of Solid MnO2 and Fe(OH)3 by Sulfide 377 11.2.1 Fe(III) and Mn(IV) Electron Configurations 378 11.2.2 MnO2 Reaction with Sulfide 379 11.2.3 Fe(OH)3 Reaction with Sulfide 382 11.3 Pyrite, FeS2, Oxidation 384 11.3.1 Pyrite Reacting with O2 384 11.3.2 Pyrite Reacting with Soluble Fe(III) 385 11.3.3 Pyrite Reacting with Dihalogens and Cr2+ 387 References 388 12. Metal Sulfides in the Environment and in Bioinorganic Chemistry 390 12.1 Introduction 390 12.2 Idealized Molecular Reaction Schemes from Soluble Complexes to ZnS and CuS Solids 391 12.3 Nanoparticle Size and Filtration 394 12.4 Ostwald Ripening versus Oriented Attachment 394 12.5 Metal Availability and Detoxification for MS Species 396 12.6 Iron Sulfide Chemistry 396 12.6.1 FeSmack (Mackinawite) 396 12.6.2 FeSmack Conversion to Pyrite, FeS2 397 12.6.3 FeS as a Catalyst in Organic Compound Formation 400 12.6.4 FeS as an Electron Transfer Agent in Biochemistry 400 12.7 More on the Nitrogen Cycle (Nitrate Reduction, Denitrification, and Anammox) 402 Appendix 12.1 PbS Nanoparticle Model and Size Ranges of Natural Materials 404 References 404 13. Kinetics and Thermodynamics of Metal Uptake by Organisms 406 13.1 Introduction 406 13.1.1 Conditional Metal Ligand Stability Constants 407 13.1.2 Thermodynamic Metal Ligand Stability Constants 409 13.2 Metal Uptake Pathways 410 13.2.1 Ion Channels for Potassium 411 13.2.2 Metal Uptake by Cells via Ligands on Membranes 413 13.2.3 Evaluation of kf, kd, and KcondM L from Laboratory and Natural Samples 418 References 420 Index 421

Product Details

  • publication date: 15/07/2016
  • ISBN13: 9781118851371
  • Format: Hardback
  • Number Of Pages: 456
  • ID: 9781118851371
  • weight: 1140
  • ISBN10: 1118851374

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