TEXTBOOK OF CHEMICAL ENGINEERING THERMODYNAMICS: Principles, Equations of State, Phase Equilibria, and Reaction Equilibrium
Miller, Edward H
Synopsis "TEXTBOOK OF CHEMICAL ENGINEERING THERMODYNAMICS: Principles, Equations of State, Phase Equilibria, and Reaction Equilibrium"
Chemical engineering thermodynamics provides the framework for understanding how energy, properties, phase behavior, and chemical equilibrium govern chemical systems. Textbook of Chemical Engineering Thermodynamics develops that framework from fundamental principles to equations of state, solution thermodynamics, phase equilibria, and chemical reaction equilibrium. The opening chapters establish thermodynamic systems and states, the First and Second Laws, entropy, ideal work, the Third Law, and fundamental property relations. Maxwell relations, heat capacities, thermodynamic diagrams, and property estimation from limited data provide foundations for later calculations. The book examines real-fluid behavior through PVT surfaces, saturation properties, vapor-pressure relationships, the virial equation of state, corresponding states, and generalized compressibility correlations. Cubic equations of state are developed through van der Waals and Redlich–Kwong, followed by Soave–Redlich–Kwong and Peng–Robinson models, including solution methods, comparisons, mixing rules, and model selection. Residual properties and departure functions extend real-fluid analysis to enthalpy and entropy calculations. Fugacity and fugacity coefficients are developed from Gibbs energy and equations of state, including behavior near critical conditions and at saturation. For mixtures, the book covers partial molar properties, the Gibbs–Duhem equation, ideal and nonideal solution behavior, properties of mixing, mixture fugacity, EOS mixing rules, and the Lewis–Randall rule. Activity-coefficient and excess-Gibbs-energy methods include Margules, van Laar, Wilson, NRTL, UNIQUAC, and UNIFAC. Phase-equilibrium coverage progresses from equilibrium criteria and the Gibbs phase rule to phase diagrams and vapor–liquid equilibrium. Topics include Raoult’s law, modified Raoult’s law, bubble- and dew-point calculations, T-x-y and P-x-y diagrams, azeotropes, high-pressure VLE, gamma-phi and phi-phi formulations, critical phenomena, and retrograde condensation. Liquid–liquid equilibrium, phase stability, distribution coefficients, extraction, solid-liquid and solid-vapor equilibrium, sublimation, eutectic systems, crystallization, and purification are also treated. Chemical reaction equilibrium is developed through reaction stoichiometry, equilibrium constants, Gibbs energy, temperature dependence, gas-phase equilibrium composition, pressure effects, and initial composition. More complex systems include multiple reactions, heterogeneous reaction equilibrium, real-gas corrections, simultaneous equilibrium calculations, and numerical solution strategies. The final chapter brings the framework together through coupled phase-and-reaction equilibrium, including the reactive phase rule, reactive separations, and a capstone process analysis. Throughout the book, concepts are reinforced with worked examples, technical figures, tables, professional insight callouts, quick-reference material, and practice problems arranged from introductory to advanced levels. Designed primarily for undergraduate chemical engineering students, it also provides a structured foundation for early-career engineers and graduate students reviewing classical thermodynamics.
