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The aim of this book is to develop the concepts and relations pertinent to the solution of many thermodynamic problems encountered in multi-phase, multi-component systems. In doing so, it emphasizes a comprehension and development of general expressions for solving such problems, rather than ready-made equations for particular applications. Throughout the book, the methods of Gibbs are used with emphasis on the chemical potential.
This book involves application of the Calphad method for derivation of a self consistent thermodynamic database for the geologically important system Mg0- Fe0-Fe203-Alz03-Si02 at pressures and temperatures of Earth's upper mantle and the transition zone of that mantle for Earth. The created thermodynamic database reproduces phase relations at 1 bar and at pressures up to 30 GPa. The minerals are modelled by compound energy formalism, which gives realistic descriptions of their Gibbs energy and takes into account crystal structure data. It incorporates a detailed review of diverse types of experimental data which are used to derive the thermodynamic database: phase equilibria, calorimetric stud ies, and thermoelastic property measurements. The book also contains tables of thermodynamic properties at 1 bar (enthalpy and Gibbs energy of formation from the elements, entropy, and heat capacity, and equation of state data at pressures from 1 bar to 30 GPa. Mixing parameters of solid solutions are also provided by the book. Table of Contents Introduction to the Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . V Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IX Table of Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XI Co-Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XIII Vitae of Co-Authors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XV CODATA Task Group on Geothermodynamic Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . XXIII Chapter 1. Thermodynamics and Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1. 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1. 2 Thermodynamic Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1. 3 Experimental Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 1. 4 Programs and Assessment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 System and Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5 1. 5 Chapter 2. Experimental Phase Equilibrium Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 The Si02 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 2. 1 2. 2 The Fe-0 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 2. 3 The Fe-Si-0 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10 2. 4 The Mg0-Si0 System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A thermodynamically consistent description of the transport across interfaces in mixtures has for a long time been an open issue. This research clarifies that the interface between a liquid and a vapor in a mixture is in local equilibrium during evaporation and condensation. It implies that the thermodynamics developed for interfaces by Gibbs can be applied also away from equilibrium, which is typically the case in reality. A description of phase transitions is of great importance for the understanding of both natural and industrial processes. For example, it is relevant for the understanding of the increase of CO2 concentration in the atmosphere, or improvements of efficiency in distillation columns. This excellent work of luminescent scientific novelty has brought this area a significant step forward. The systematic documentation of the approach will facilitate further applications of the theoretical framework to important problems.