Considerable progress has been made in our understanding of the physicochemical evolution of natural rocks through systematic analysis of the compositional properties and phase relations of their mineral assemblages. This book brings together concepts of classical thermodynamics, solution models, and atomic ordering and interactions that constitute a major basis of such analysis, with appropiate examples of application to subsolidus petrological problems. This book is written for an audience with a senior undergraduate level background in chemistry. Derivations of fundamental thermodynamic relations which are in need of reemphasis and clarification are presented.

Inhalt

1 Thermodynamic Functions of Solutions.- 1.I Fugacity, Activity, and Standard States.- 1.II Partial Molar Quantities, Ideal Solutions, and Excess Functions.- 1.III Dilute Solutions, and More on Standard States.- 2 Mixing Models and Activity-Composition Relations.- 2.I Mixing Models: Macroscopic Formulations.- 2.II Statistical Thermodynamic Formulation of Entropy.- 2.III Ionic and Reciprocal Solutions.- 2.IV Regular and Athermal Solutions.- 2.V Mixing Parameters: Microscopic Considerations.- 2.VI Quasi-Chemical Model.- 2. VII Comparison of Mixing Models.- 2. VIII Cation Ordering and a-X Relations.- 3 Phase Separation in Solutions.- 3.I Free Energy-Composition Relation and Stability of a Solution.- 3.II P-T Dependence of Unmixing.- 3.III Decomposition Mechanisms and Thermal History.- 3.IV Coherent Exsolution.- 3.V Lamellar Spacing and Thermal History.- 3.VI Critical, Binodal, and Spinodal Conditions.- 3.VII Displacement of a Binary Solvus Due to a Dilute Third Component.- 4 Heterogeneous Chemical Reaction and Equilibrium.- 4.I Equilibrium Constant and Activity.- 4.II Phase Rule and Duhem's Theorem.- 4.III Polymorphism and Phase Transformations.- 4.IV P-T Slopes of Equilibrium Boundaries.- 4. V Effects of Additional Components on Mineral Equilibria.- 4. VI Computation of Equilibrium Assemblages in a Closed System.- 5 Thermodynamic Properties of Selected Mineral Solid Solutions.- 5.I Silicate Garnets.- 5.II Olivine.- 5.III Pyroxenes.- 5.IV Micas.- 5.V Feldspars.- 5.VI Nepheline-Kalsilite.- 5.VII Spinels.- 5.VIII Rhombohedral Carbonates.- 6 Exchange Equilibrium and Inter-Crystalline Fractionation.- 6.I Thermodynamics of Element Fractionation.- 6.II Retrieval of Mixing Parameters from Element Fractionation Data.- 6.III Element Fractionation Between Natural Minerals: Comparison with Thermodynamic Theory.- 6.IV Thermodynamics of Isotope Fractionation.- 6. V Exchange Equilibria and Geothermometry.- 7 Atomic Ordering in Minerals.- 7.I Introduction and General Concepts.- 7.II Relationship Between Disordering Energy and Long-Range Order.- 7.III Systematics of Fe2+-Mg Ordering in Ferromagnesian Silicates.- 7.IV Ordering and Macroscopic Mixing Properties.- 7.V Free Energy vs. Ordering Relation.- 7.VI Ordering, Site Geometries, and Intercrystalline Fractionation.- 7.VII Order-Disorder Transformations in Solid Solutions.- 7.VIII Cation Ordering and Thermal History.- 8 Estimation and Extrapolation of the Thermodynamic Properties of Minerals and Solid Solutions.- 8.I Excess Mixing Properties of Solid Solutions.- 8.II Thermochemical Data on Pure Phases.- 8.III Direct Estimation of Free Energy of Formation.- Appendix A Explanatory Notes.- A.I Crystal Field Theory.- A.II Electronegativity.- A. III Interdiffusion Coefficient.- A.IV Temperature-Time-Transformation (TTT) Diagram.- Appendix B Geothermometric and Geobarometric Formulations of Selected Mineral Reactions.- B.I Continuous Reactions.- B.II Discontinuous Reactions.- Appendix C Fluids at High Pressure and Temperature.- C.I Equations of State.- C.II The Virial Equations.- C.III Nonvirial Equations.- C.IV Computation of Pure Fluid Fugacities.- References.