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PREFACE TO THE THIRD EDITION ix PREFACE TO THE SECOND EDITION x PREFACE TO THE FIRST EDITION xi ACKNOWLEDGEMENTS xiii ABOUT THE COMPANION WEBSITE xiv 1 ENERGY IN GEOCHEMICAL PROCESSES 1 Introduction 1 Energy in mechanical systems 4 Energy in chemical and mineral systems: free energy 5 Stable, unstable and metastable minerals 10 Further reading 13 2 EQUILIBRIUM IN GEOLOGICAL SYSTEMS 14 The significance of mineral stability 14 Systems, phases and components 16 Equilibrium 18 Phase diagrams in P???T space 20 Phase diagrams in T???X space 26 Ternary phase diagrams 36 Review 41 Further reading 41 Sources of thermodynamic data for minerals 42 Exercises 42 3 KINETICS OF EARTH PROCESSES 43 Defining the rate of a reaction 44 Temperature–dependence of reaction rate 47 Diffusion 52 Melt viscosity 55 Persistence of metastable minerals: closure temperature 57 Review 58 Further reading 58 Exercises 59 4 AQUEOUS SOLUTIONS AND THE HYDROSPHERE 60 Ways of expressing the concentrations of major constituents 61 Equilibrium constant 63 Non–ideal solutions: activity coefficient 69 Natural waters 70 Oxidation and reduction: Eh–pH diagrams 75 Further reading 81 Exercises 81 5 ELECTRONS IN ATOMS 82 Why does a geologist need to understand atoms? 82 The atom 83 Stationary waves 85 Electron waves in atoms 88 The shapes of electron orbitals 90 Electron energy levels 93 Review 98 Further reading 98 Exercises 98 6 WHAT WE CAN LEARN FROM THE PERIODIC TABLE 99 Ionization energy 99 The Periodic Table 102 Electronegativity 103 Valency 104 Atomic spectra 105 Review 109 Further reading 110 Exercises 110 7 CHEMICAL BONDING AND THE PROPERTIES OF MINERALS 111 The ionic model of bonding 111 The covalent model of bonding 118 Bonding in minerals 126 Other types of atomic and molecular interaction 129 Review 132 Further reading 132 Exercises 132 8 SILICATE CRYSTALS AND MELTS 133 Silicate polymers 133 Cation sites in silicates 140 Optical properties of crystals 146 Defects in crystals 148 Further reading 151 Exercises 151 9 SOME GEOLOGICALLY IMPORTANT ELEMENTS 153 Major and trace elements 153 Alkali metals 154 Hydrogen 156 Alkaline earth metals 156 Aluminium 157 Carbon 159 Silicon 166 Nitrogen and phosphorus 166 Oxygen 167 Sulfur 168 Fluorine 170 Noble gases 171 Transition metals 171 Rare earth elements 175 Actinides 176 Further reading 177 Exercise 177 10 WHAT CAN WE LEARN FROM ISOTOPES? 178 Isotope systems 179 Radiogenic isotope systems 181 Stable isotope systems 195 Cosmogenic radioisotope systems 203 Review 204 Further reading 204 Exercises 204 11 THE ELEMENTS IN THE UNIVERSE 206 The significance of element abundance 206 Measuring cosmic and Solar System abundances 206 The composite abundance curve 210 Cosmic element production 211 Elements in the Solar System 215 Chemical evolution of the Earth 219 Review 224 Further reading 225 Exercises 225 ANSWERS TO EXERCISES 226 APPENDIX A: Mathematics revision 234 APPENDIX B: Simple solution chemistry 240 APPENDIX C: Alphabetical list of chemical abbreviations and element names, with atomic number and relative atomic mass 243 APPENDIX D: Symbols, units, constants and abbreviations used in this book 245 Glossary 248 REFERENCES 258 INDEX 261