Chemical and Process Thermodynamics

Transcription

1 Chemical and Process Thermodynamics Third Edition B. G. Kyle Emeritus Professor of Chemical Engineering Kansas State University Prentice Hall PTR Upper Saddle River, New Jersey 07458

2 CONTENTS Preface Notation 1 Introduction 1-1 The Anatomy ofthermodynamics 1-2 The Terminology ofthermodynamics 1-3 The Variables and Quantities of Thermo 1-4 Equilibrium and the Equilibrium State 1-5 The Phase Rule 1-6 The Reversible Process 2 The First Law of Thermodynamics 2-1 The First Law and Internal Energy 2-2 The Enthalpy 2-3 The Heat Capacity 2-4 The First Lawfor Open Systems Problems 3 The Behavior of Fluids 3-1 The P VT Behavior of Fluids 3-2 Equations of State 3-3 The Ideal Gas 3-4 The Compressibility Factor 3-5 Generalized Equations of State Problems 4 The Second Law ofthermodynamics 4-1 Heat Engines and the Carnot Cycle 4-2 The Ideal-Gas Carnot Cycle

3 viii Contents 4-3 The Absolute Temperature Scale The Entropy Function Entropy and the Spontaneity of Natural Processes Calculation of Entropy Changes Open Systems Applications of the Second Law The Microscopic View of Entropy The ThirdLaw of Thermodynamics 97 Problems 98 5 The Thermodynamic Network The Free Energy Functions The Clausius Inequality and the Fundamental Equation The Thermodynamic Network Measurable Quantities Calculation ofk and's asfunctions o/pandt Property Estimation from Corresponding States Property Estimation Via Generalized Equations of State * The MethodofJacobians * The Generality ofthe Thermodynamic Method 132 Problems Heat Effects The Computational Path Heat Effects Due to Change of Temperature Heat Effects Due to Change of Pressure Heat Effects Due to Change of Phase Mixing Heat Effecfts Enthalpy-Concentration Diagrams Chemical Heat Effects Heats of Formation in Solution Applied Thermochemistry 176 Problems Equilibrium and Stability Criteria of Equilibrium The Chemical Potential Application ofthe Equilibrium Criteria The Essence of Thermodynamics * Stability * Constraints, Equilibrium and Virtual Variations 214 Problems 215

4 Contents ix 8 Thermodynamics of Pure Substances The Phase Diagram The Clapeyron Equation Solid-Liquid Equilibrium Solid- Vapor and Liquid- Vapor Equilibrium Presentation of Thermodynamic Property Data 229 Problems Principles of Phase Equilibrium Presentation of Vapor-Liquid Equilibrium Data Determination of Vapor-Liquid Equilibrium Data The Thermodynamic Basis for the Phase Rule The Fugacity Determination offugacities ofpure Substances Determination offugacities in Mixtures Ideal Systems The Activity Coefficient Experimental Determination of Activity Coefficients Henry's Law Activity Coefficient Equations Phase Equilibrium Via an Equation of State The Thermodynamic Approach to Phase Equilibrium 299 Problems Applied Phase Equilibrium The Consummate Thermodynamic Correlation of Vapor-Liquid Equilibrium Constant-Pressure VLEData Total Pressure Data Azeotropes Thermodynamic Consistency Tests Multicomponent Vapor-Liquid Equilibrium Phase Behavior in Partially Miscible Systems Liquid-Liquid Equilibrium * Ternary Liquid-Liquid Equilibrium Estimates from Fragmentary Data Recapitulation 359 Problems 362

5 X Contents 11 Additional Topics in Phase Equilibrium Partial Molar Properties Experimental Determination q/mixture and Partial Molar Properties Mixture Properties for Ideal Solutions * Activity Coefficients Based on Henry 's Law * The Solubility of Gases in Liquids * Solid-Liquid Equilibria * Solid-Supercritical Fluid Equilibrium * Prediction of Solution Behavior 412 Problems Chemical Equilibrium Generalized Stoichiometry The Condition of Equilibrium for a Chemical Reaction Standard States and AG Temperature Dependence ofthe Equilibrium Constant Experimental Determination ofthermochemical Data Other Free Energy Functions Homogeneous Gas-Phase Reactions Heterogeneous Chemical Equilibrium Reactions in Solution * Reactions in Aqueous Solution * Electrolyte Solutions * Coupled Reactions 505 Problems Complex Chemical Equilibrium The Phase Rulefor Reacting Systems * Analyzing Complex Chemical Equilibrium Problems * Formulating Complex Chemical Equilibrium Problems * The CHO System and Carbon Deposition Boundaries * The Si-Cl-H System and Silicon Deposition Boundaries 579 Problems Thermodynamic Analysis of Processes Work and Free Energy Functions The Availability Mixing and Separation Processes 600

6 Contents xi 14-4* Heat Exchange Systems Involving Chemical Transformations 614 Problems Physicomechanical Processes Compression and Expansion of Gases The Joule-Thomson Expansion Liquefaction of Gases Refrigeration Heat Pumps Power Generation Cogeneration of Steam and Power 667 Problems Compressible Fluid Flow The Basic Equations of Fluid Mechanics Sonic Velocity Isentropic Flow Isentropic Flow Through Nozzles Nonisentropic Flow 689 Problems Thermodynamics and Models * Standard Models * Ad Hoc Models * Evaluation of Models 719 Problems 722 Appendix A 729 Table A-l Critical Constants of Selected Substances 729 FigureA-1 Equilibrium Constants for Selected Reactions 731 Appendix B 732 Table B-l Molar Heat Capacities of Gases at Zero Pressure 732

7 xii Contents Appendix C 734 Appendix D Table C-l Table C-2 Thermodynamic Properties of Saturated Steam Thermodynamic Properties ofsuperheated Steam Table D-l Enthalpies and Free Energies of Formation of Selected Organic Compounds 742 Table D-2 Enthalpies and Free Energies of Formation of Selected Inorganic Compounds 744 Table D-3 Free Energies of Formation of Selected Ions in the Aqueous State 745 Appendix E Inventory ofthe CD-ROM Appendix F Properties ofdeterminants Index