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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