Buch, Englisch, 656 Seiten, Format (B × H): 182 mm x 261 mm, Gewicht: 1509 g
ISBN: 978-0-691-12432-2
Verlag: Princeton University Press
This book offers a comprehensive exploration of geochemical kinetics--the application of chemical kinetics to geological problems, both theoretical and practical. Geochemical Kinetics balances the basic theories of chemical kinetics with a thorough examination of advanced theories developed by geochemists, such as nonisothermal kinetics and inverse theories, including geochronology (isotopic dating), thermochronology (temperature-time history), and geospeedometry (cooling rates). The first chapter provides an introduction and overview of the whole field at an elementary level, and the subsequent chapters develop theories and applications for homogeneous reactions, mass and heat transfer, heterogeneous reactions, and inverse problems. Most of the book's examples are from high-temperature geochemistry, with a few from astronomy and environmental sciences. Appendixes, homework problems for each major section, and a lengthy reference list are also provided. Readers should have knowledge of basic differential equations, some linear algebra, and thermodynamics at the level of an undergraduate physical chemistry course. Geochemical Kinetics is a valuable resource for anyone interested in the mathematical treatment of geochemical questions.
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Fachgebiete
Weitere Infos & Material
List of Figures xi
List of Tables xvii
Preface xix
Notation xxii
Physical Constants xxv
Chapter 1: Introduction and Overview 1
1.1 Thermodynamics versus Kinetics 3
1.2 Chemical Kinetics versus Geochemical Kinetics 6
1.3 Kinetics of Homogeneous Reactions 7
1.3.1 Reaction progress parameter x 11
1.3.2 Elementary versus overall reactions 12
1.3.3 Molecularity of a reaction 13
1.3.4 Reaction rate law, rate constant, and order of a reaction 14
1.3.5 Concentration evolution for reactions of different orders 19
1.3.6 Dependence of reaction rate constant on temperature; Arrhenius equation 25
1.3.7 Nonisothermal reaction kinetics 29
1.3.8 More complicated homogeneous reactions 31
1.3.9 Determination of reaction rate laws, rate constants, and mechanisms 32
1.4 Mass and Heat Transfer 36
1.4.1 Diffusion 37
1.4.2 Convection 46
1.5 Kinetics of Heterogeneous Reactions 47
1.5.1 Controlling factors and'?reaction laws'? 48
1.5.2 Steps in heterogeneous reactions 55
1.6 Temperature and Pressure Effect on Reaction Rate Coefficients and Diffusivities 58
1.6.1 Collision theory 59
1.6.2 Transition state theory 61
1.7 Inverse Problems 66
1.7.1 Reactions and diffusion during cooling 66
1.7.2 Geochronology, closure age, and thermochronology 71
1.7.3 Geothermometry, apparent equilibrium temperature, and geospeedometry 77
1.7.4 Geospeedometry using exchange reactions between two or more phases 81
1.7.5 Concluding remarks 83
1.8 Some Additional Notes 83
1.8.1 Mathematics encountered in kinetics 83
1.8.2 Demystifying some processes that seem to violate thermodynamics 84
1.8.3 Some other myths 86
1.8.4 Future research 87
Problems 88
Chapter 2: Kinetics of Homogeneous Reactions 95
2.1 Reversible Reactions 97
2.1.1 Concentration evolution for first-order reversible reactions 97
2.1.2 Concentration evolution for second-order reversible reactions 99
2.1.3 Reversible reactions during cooling 104
2.1.4 Fe-Mg order-disorder reaction in orthopyroxene 113
2.1.5 Hydrous species reaction in rhyolitic melt 122
2.2 Chain Reactions 130
2.2.1 Radioactive decay series 131
2.2.2 Chain reactions leading to negative activation energy 144
2.2.3 Thermal decomposition of ozone 145
2.3 Parallel Reactions 147
2.3.1 Electron transfer between Fe2?FE and Fe3?FE in aqueous solution 147
2.3.2 From dissolved CO2 to bicarbonate ion 148
2.3.3 Nuclear hydrogen burning 150
2.4 Some Special Topics 155
2.4.1 Photochemical production and decomposition of ozone, and the ozone hole 155
2.4.2 Diffusion control of homogeneous reactions 157
2.4.3 Glass transition 160
Problems 167
Chapter 3: Mass Transfer: Diffusion and Flow 173
3.1 Basic Theories and Concepts 175
3.1.1 Mass conservation and transfer 175
3.1.2 Conservation of energy 183
3.1.3 Conservation of momentum 183
3.1.4 Various kinds of diffusion 183
3.2 Diffusion in a Binary System 189
3.2.1 Diffusion equation 189
3.2.2 Initial and boundary conditions 190
3.2.3 Some simple solutions to the diffusion equation at steady state 192
3.2.4 One-dimensional diffusion in infinite or semi-infinite medium with constant diffusivity 194
3.2.5 Instantaneous plane, line, or point source 205
3.2.6 Principle of superposition 207
3.2.7 One-dimensional finite medium and constant D, separation of variables 209
3.2.8 Variable diffusion coefficient 212
3.2.9 Uphill diffusion in binary systems and spinodal decomposition 221
3.2.10 Diffusion in three dimensions; different coordinates 224
3.2.11 Diffusion in an anisotropic medium; diffusion tensor 227
3.2.12 Summary of analytical methods to obtain solution to the diffusion equation 231
3.2.13 Numerical solutions 231
3.3 Diffusion of a Multispecies Component 236
3.3.1 Diffusion of water in silicate melts 238
3.3.2 Diffusion of CO2 component in silicate melts 245
3.3.
