Inorganic Chemistry for Geochemistry and Environmental Sciences

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.

Auteur

Professor George W. Luther, III, School of Marine Science & Policy, University of Delaware, USA
Professor Luther has joint appointments in the Department of Chemistry and Biochemistry, Department of Civil and Environmental Engineering and the Department of Plant and Soil Science.
Professor Luther taught an ACS accredited course on advanced inorganic chemistry from 1973-1986 to senior undergraduate students. As he moved into environmental and marine chemistry, he began using environmental examples in inorganic chemistry. In 1988, he started a similar course titled 'Marine Inorganic Chemistry' that has been taught biannually at the University of Delaware, attracting students in Chemical Oceanography, Chemistry and Biochemistry, Geology / Geochemistry, Civil and Environmental Engineering and Plant and Soil Science.
In 2013, Professor Luther was awarded the Geochemistry Division Medal by the American Chemical Society for his wide-ranging contributions to aqueous geochemistry. He is recognised for the application of physical inorganic chemistry to the transfer of electrons between chemical compounds in the environment, and also the development of chemical sensors for quantifying the presence of elements and compounds in natural waters.
Professor Luther was named a fellow of the American Association for the Advancement of Science in 2011 and the American Geophysical Union in 2012.

Contenu
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 NeutronProton 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. OxidationReduction 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(𝜃, 𝜙) 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 (𝜒) 74

3.8.7 Periodic Properties Hardness (𝜂) 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) ...