This text explores the connections between different thermodynamic subjects related to fluid systems. Emphasis is placed on the clarification of concepts by returning to the conceptual foundation of thermodynamics and special effort is directed to the use of a simple nomenclature and algebra. The book presents the structural elements of classical thermodynamics of fluid systems, covers the treatment of mixtures, and shows via examples and references both the usefulness and the limitations of classical thermodynamics for the treatment of practical problems related to fluid systems. It also includes diverse selected topics of interest to researchers and advanced students and four practical appendices, including an introduction to material balances and step-by-step procedures for using the Virial EOS and the PRSV EOS for fugacities and the ASOG-KT group method for activity coefficients. The Olivera-Fuentes table of PRSV parameters for more than 800 chemical compounds and the Gmehling-Tochigi tables of ASOG interaction parameters for 43 groups are included.
Part I: Fundamentals. Basic Concepts and Definitions. The First and Second Laws of Thermodynamics. The Concept of Entropy. Conservation of Energy in an Open Flow System. Definition of Enthalpy. The Algebra of State Functions. The Helmholtz and Gibbs Functions. Calculation of Changes in the Value of Thermodynamic Properties. Part II: Mixtures. Partial Molar Properties and Property Changes by Mixing. The Chemical Potential and the Gibbs-Helmholtz Equation. The Principles of Physical and Chemical Equilibrium. The Phase Rule and Duhem Theorem. Generality of the Thermodynamic Treatment. The Ideal Gas and Ideal Gas Mixtures. The Use of Fugacity and Activity in Equilibrium Studies. Calculation of Fugacities from Equations of State (EOS). Fugacity of a Mixture and of Its Components. Fugacities and Activities in Liquid Mixtures of Non Electrolytes. Activity Coefficients and Excess Properties. Mixture Behavior, Stability and Azeotropy. The Thermodynamics of Aqueous Electrolyte Solutions. Part III: Applications. The Thermodynamics of Chemical Reactions. The Thermodynamics of Equilibrium Based Separation Processes. Heat Effects in Pure Compounds and Mixtures. Adsorption of Gases in Solids. Part IV: Selected Topics. The Thermodynamics of Flow of Compressible Fluids. Elements of Statistical Thermodynamics. Statistical Thermodynamics Basis of Equations of State. Statistical Thermodynamics Basis of Excess Gibbs Functions. The Activity Coefficients of Individual Ions. Measurements and Modeling. Part V: Appendices. Appendix A. Material Balances in Open Flow Systems. Appendix B. Working with the Virial EOS. Appendix C. Working with the PRSV EOS. Appendix D. Working with ASOG-KT.