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TableofContents PDF
Wh i t e G eoc h emi s t ry
Table of Contents
Part I: The Geochemical Toolbox
Chapter 1: Introduction ............................................................................................................1
Geochemistry.....................................................................................................................1
This Book ..........................................................................................................................2
The Philosophy of Science..................................................................................................4
Building Scientific Understanding ................................................................................4
The Scientist as Skeptic ...............................................................................................5
Elements, Atoms, and Chemical Bonds................................................................................6
The Periodic Table.......................................................................................................6
Electrons and Orbits .....................................................................................................7
Some Chemical Properties of the Elements....................................................................13
Chemical Bonding........................................................................................................16
A Brief Look at the Earth...................................................................................................18
Structure of the Earth...................................................................................................18
Plate Tectonics and the Hydrologic Cycle .....................................................................19
Earth Materials...........................................................................................................21
References and Suggestions for Further Reading...................................................................23
Chapter 2: Energy, Entropy and Fundamental Thermodynamic Concepts ....................................24
The Thermodynamic Perspective........................................................................................24
Thermodynamic Systems and Equilibrium ...........................................................................24
Fundamental Thermodynamic Variables ......................................................................26
Equations of State ..............................................................................................................28
Ideal Gas Law..............................................................................................................28
Equations of State for Real Gases ..................................................................................29
Critical phenomena .....................................................................................................31
Equation of State for Other Substances ..........................................................................32
Temperature, Absolute Zero, and The Zeroth Law Of Thermodynamics................................33
Energy and The First Law of Thermodynamics.....................................................................34
Energy .........................................................................................................................34
Work ...........................................................................................................................34
Path independence, Exact differentials, State functions, and the First Law....................35
The Second Law and Entropy ..............................................................................................37
Statement ....................................................................................................................37
Statistical Mechanics: A Microscopic Perspective of Entropy.........................................38
Integrating Factors and Exact Differentials...................................................................44
Enthalpy ...........................................................................................................................45
Heat Capacity...................................................................................................................46
Constant Volume Heat Capacity ..................................................................................47
Constant Pressure Heat Capacity..................................................................................47
Energy Associated with Volume Occupied and the Relationshp between Cv and Cp .........47
Heat Capacity of Solids: A Problem in Quantum Physics...............................................50
Relationship of Entropy to Other State Variables ........................................................57
Additive Nature of Silicate Heat Capacities...............................................................57
The Third Law and Absolute Entropy..................................................................................58
Statement of the Third Law .........................................................................................58
Absolute Entropy..........................................................................................................58
Calculating Enthalpy and Entropy Changes........................................................................59
Adiabatic Changes ......................................................................................................59
Isobaric and Isothermal Changes in Enthalpy ...............................................................59
Enthalpies of Formation, Vaporization and Fusion........................................................60
Entropies of Reaction....................................................................................................61
Chapter 12: Geochemistry of the Solid Earth II: The Crust ........................................................512
Introduction .......................................................................................................................512
The Oceanic Crust ..............................................................................................................512
Processes in Subduction Zones and Island Arc Geochemistry..................................................517
Major Element Composition ..........................................................................................517
Trace Element Composition...........................................................................................519
Isotopic Composition and Sediment Subduction..............................................................521
Magma Genesis in Subduction Zones ..............................................................................523
CrustMantle Interaction: Assimilation ............................................................................526
Geochemistry of Two-Component Mixtures ....................................................................526
AssimilationFractional Crystallization .....................................................................529
Composition of the Continental Crust..................................................................................530
The Upper Crust...........................................................................................................531
The Middle and Lower Crust.........................................................................................534
The Total Continental Crust .........................................................................................538
Growth of the Continental Crust .........................................................................................540
The Pace of Crustal Growth ..........................................................................................541
Mechanisms of Crustal Growth .....................................................................................544
Crustal Growth in the Archean...............................................................................546
References and Suggestions for Further Reading...................................................................550
Problems ............................................................................................................................553
Chapter 13: Reactions at the Earths Surface: Weathering, Soils, and Stream Chemistry...........555
Introduction .......................................................................................................................555
Redox in Natural Waters ...................................................................................................555
Biogeochemical Reodox Reactions ................................................................................557
Redox Buffers and Transition Metal Chemistry.............................................................559
Weathering, Soils, and Biogeochemical Cycling .................................................................563
Soil Profiles.................................................................................................................564
Chemical Cycling in Soils ............................................................................................567
Biogeochemical Cycling...............................................................................................568
Weathering Rates and Reactions ........................................................................................570
The Watershed Approach............................................................................................568
Thermodynamic and Kinetic Assessment of Stream Compositions...................................575
Factors Controlling Weathering Rates ..........................................................................577
The Composition of Rivers..................................................................................................580
Continental Saline Waters.................................................................................................584
References and Suggestions for Further Reading...................................................................587
Problems ............................................................................................................................588
Chapter 14: Organic Geochemistry ...........................................................................................589
Introduction .......................................................................................................................589
A Brief Biological Background ...........................................................................................589
Organic Compounds and Their Nomenclature ......................................................................590
Hydrocarbons...............................................................................................................591
Functional Groups.........................................................................................................593
Biologically Important Organic Compounds..................................................................596
The Chemistry of Life: Important Biochemical Processes....................................................602
Photosynthesis ............................................................................................................602
Respiration..................................................................................................................604
Organic Matter in Soils and Natural Waters.......................................................................606
Dissolved Organic Substances.......................................................................................606