Geochemistry. (2020)

• Record Type: Book
• Further Information: Note: William M. White.
• Authors: White, William M, 1948-
• Contents: Preface xv About the companion website xvii Chapter 1: Introduction 1 1.1 Introduction 1 1.2 Beginnings 1 1.3 Geochemistry in the twenty-first century 3 1.4 The philosophy of science 4 1.4.1 Building scientific understanding 4 1.4.2 The scientist as skeptic 5 1.5 Elements, atoms, crystals, and chemical bonds: some chemical fundamentals 6 1.5.1 The periodic table 6 1.5.2 Electrons and orbits 7 1.5.3 Some chemical properties of the elements 9 1.5.4 Chemical bonding 12 1.5.5 Molecules, crystals, and minerals 14 1.6 A brief look at the Earth 19 1.6.1 Structure of the Earth 19 1.6.2 Plate tectonics and the hydrologic cycle 20 1.7 A look ahead 22 References and suggestions for further reading 30 Chapter 2: Energy, entropy, and fundamental thermodynamic concepts 31 2.1 The thermodynamic perspective 31 2.2 Thermodynamic systems and equilibrium 32 2.2.1 Fundamental thermodynamic variables 34 2.2.2 Properties of state 34 2.3 Equations of state 35 2.3.1 Ideal gas law 35 2.3.2 Equations of state for real gases 36 2.3.3 Equation of state for other substances 37 2.4 Temperature, absolute zero, and the zeroth law of thermodynamics 37 2.5 Energy and the first law of thermodynamics 38 2.5.1 Energy 38 2.5.2 Work 39 2.5.3 Path independence, exact differentials, state functions, and the first law 40 2.6 The second law and entropy 41 2.6.1 Statement 41 2.6.2 Statistical mechanics: a microscopic perspective of entropy 42 2.6.3 Integrating factors and exact differentials 48 2.7 Enthalpy 50 2.8 Heat capacity 51 2.8.1 Constant volume heat capacity 52 2.8.2 Constant pressure heat capacity 52 2.8.3 Energy associated with volume and the relationship between Cv and Cp 52 2.8.4 Heat capacity of solids: a problem in quantum physics 53 2.8.5 Relationship of entropy to other state variables 58 2.8.6 Additive nature of silicate heat capacities 58 2.9 The third law and absolute entropy 59 2.9.1 Statement of the third law 59 2.9.2 Absolute entropy 59 2.10 Calculating enthalpy and entropy changes 60 2.10.1 Enthalpy changes due to changes in temperature and pressure 60 2.10.2 Changes in enthalpy due to reactions and change of state 61 2.10.3 Entropies of reaction 62 2.11 Free energy 65 2.11.1 Helmholtz free energy 65 2.11.2 Gibbs free energy 65 2.11.3 Criteria for equilibrium and spontaneity 65 2.11.4 Temperature and pressure dependence of the Gibbs free energy 66 2.12 The Maxwell relations 69 2.13 Summary 70 References and suggestions for further reading 71 Problems 71 Chapter 3: Solutions and thermodynamics of multicomponent systems 74 3.1 Introduction 74 3.2 Phase equilibria 75 3.2.1 Some definitions 75 3.2.2 The Gibbs phase rule 77 3.2.3 The Clapeyron equation 78 3.3 Solutions 80 3.3.1 Raoult’s law 80 3.3.2 Henry’s law 81 3.4 Chemical potential 81 3.4.1 Partial molar quantities 81 3.4.2 Definition of chemical potential and relationship to Gibbs free energy 82 3.4.3 Properties of the chemical potential 82 3.4.4 The Gibbs-Duhem relation 83 3.4.5 Derivation of the phase rule 84 3.5 Ideal solutions 84 3.5.1 Chemical potential in ideal solutions 84 3.5.2 Volume, enthalpy, entropy, and free energy changes in ideal solutions 84 3.6 Real solutions 86 3.6.1 Chemical potential in real solutions 86 3.6.2 Fugacities 87 3.6.3 Activities and activity coefficients 88 3.6.4 Excess functions 90 3.7 Electrolyte solutions 93 3.7.1 The nature of water and water–electrolyte interaction 93 3.7.2 Some definitions and conventions 94 3.7.3 Activities in electrolytes 96 3.8 Ideal solutions in crystalline solids and their activities 101 3.8.1 Mixing-on-site model 101 3.8.2 Local charge balance model 103 3.9 Equilibrium constants 104 3.9.1 Derivation and definition 104 3.9.2 Law of mass action 105 3.9.3 KD values, apparent equilibrium constants, and the solubility product 107 3.9.4 Henry’s law and gas solubilities 108 3.9.5 Temperature dependence of equilibrium constant 108 3.9.6 Pressure dependence of equilibrium constant 109 3.10 Practical approach to electrolyte equilibrium 110 3.10.1 Choosing components and species 110 3.10.2 Mass balance 110 3.10.3 Electrical neutrality 111 3.10.4 Equilibrium constant expressions 112 3.11 Oxidation and reduction 113 3.11.1 Redox in aqueous solutions 114 3.11.2 Redox in magmatic systems 122 3.12 Summary 123 References and suggestions for further reading 124 Problems 125 Chapter 4: Applications of thermodynamics to the Earth 130 4.1 Introduction 130 4.2 Activities in nonideal solid solutions 130 4.2.1 Mathematical models of real solutions: Margules equations 130 4.3 Exsolution phenomena 135 4.4 Thermodynamics and phase diagrams 137 4.4.1 The thermodynamics of melting 138 4.4.2 Thermodynamics of phase diagrams for binary systems 140 4.4.3 Phase diagrams for multicomponent systems 143 4.5 Geothermometry and geobarometry 145 4.5.1 Theoretical considerations 145 4.5.2 Practical thermobarometers 146 4.6 Thermodynamic models of magmas 156 4.6.1 Structure of silicate melts 157 4.6.2 Magma solution models 158 4.7 Reprise: thermodynamics of electrolyte solutions 162 4.7.1 Equation of state for water 163 4.7.2 Activities and mean ionic and single ion quantities 163 4.7.3 Activities in high ionic strength solutions 168 4.7.4 Electrolyte solutions at elevated temperature and pressure 176 4.8 Summary 180 References and suggestions for further reading 181 Problems 184 Chapter 5: Kinetics: the pace of things 188 5.1 Introduction 188 5.2 Reaction kinetics 189 5.2.1 Elementary and overall reactions 189 5.2.2 Reaction mechanisms 189 5.2.3 Reaction rates 190 5.2.4 Rates of complex reactions 196 5.2.5 Steady state and equilibrium 199 5.3 Relationships between kinetics and thermodynamics 201 5.3.1 Principle of detailed balancing 201 5.3.2 Enthalpy and activation energy 201 5.3.3 Aspects of transition state theory 202 5.4 Diffusion 208 5.4.1 Diffusion flux and Fick’s laws 208 5.4.2 Diffusion in multicomponent systems 212 5.4.3 Driving force and mechanism of diffusion 218 5.4.4 Diffusion in solids and the temperature dependence of the diffusion coefficient 219 5.4.5 Diffusion in liquids 221 5.4.6 Diffusion in porous media 223 5.5 Surfaces, interfaces, and interface processes 223 5.5.1 The surface free energy 225 5.5.2 The Kelvin effect 225 5.5.3 Nucleation and crystal growth 226 5.5.4 Adsorption 233 5.5.5 Catalysis 234 5.6 Kinetics of dissolution 237 5.6.1 Simple oxides 238 5.6.2 Silicates 240 5.6.3 Nonsilicates 244 5.7 Diagenesis 244 5.7.1 Compositional gradients in accumulating sediment 245 5.7.2 Reduction of sulfate in accumulating sediment 247 5.8 Summary 248 References and suggestions for further reading 250 Problems 252 <b&
• Edition: Second edition
• Publisher Details: Chichester : Wiley Blackwell
• Publication Date: 2020
• Extent: 1 online resource
• Subjects: 551.9; Geochemistry
• Languages: English
• ISBNs: 9781119438113; 9781119438106
• Related ISBNs: 9781119438052
• Notes: Note: Includes bibliographical references and index.; Note: Description based on CIP data; resource not viewed.
• Access Rights: Legal Deposit; Only available on premises controlled by the deposit library and to one user at any one time; The Legal Deposit Libraries (Non-Print Works) Regulations (UK).
• Access Usage: Restricted: Printing from this resource is governed by The Legal Deposit Libraries (Non-Print Works) Regulations (UK) and UK copyright law currently in force.