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

CONTENTS

Preface Notation 1 Introduction

1-1 1-2 1-3 1-4 1-5 1-6 The Anatomy ofThermodynamics The Terminology ofThermodynamics The Variables and Quantities of Thermo Equilibrium and the Equilibrium State The Phase Rule The Reversible Process

2 The First Law of Thermodynamics

2-1 2-2 2-3 2-4 The First Law and Internal Energy The Enthalpy The Heat Capacity The First Lawfor Open Systems Problems

3 The Behavior of Fluids

3-1 3-2 3-3 3-4 3-5 The P VT Behavior of Fluids Equations of State The Ideal Gas The Compressibility Factor Generalized Equations of State Problems

4 The Second Law ofThermodynamics

4-1 4-2 Heat Engines and the Carnot Cycle The Ideal-Gas Carnot Cycle

viii

Contents

4-3 4-4 4-5 4-6 4-7 4-8 4-9 4-10

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 Problems

74 76 78 79 87 88 95 97 98

5 The Thermodynamic Network

5-7 5-2 5-3 5-4 5-5 5-6 5-7 5-8* 5-9* The Free Energy Functions The Clausius Inequality and the Fundamental Equation The Thermodynamic Network Measurable Quantities Calculation ofK and'S asFunctions o/P and T Property Estimation from Corresponding States Property Estimation Via Generalized Equations of State The MethodofJacobians The Generality ofthe Thermodynamic Method Problems

103
104 104 106 108 109 114 118 124 132 138 149 150 151 154 154 155 161 166 173 176 189 197 198 200 203 206 208 214 215

Heat Effects 6-1 6-2 6-3 6-4 6-5 6-6 6-7 6-8 6-9 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 Problems

Equilibrium and Stability 7-1 7-2 7-3 7-4 7-5* 7-6* Criteria of Equilibrium The Chemical Potential Application ofthe Equilibrium Criteria The Essence of Thermodynamics Stability Constraints, Equilibrium and Virtual Variations Problems

Contents

ix

8 Thermodynamics of Pure Substances

8-1 8-2 8-3 8-4 8-5 The Phase Diagram The Clapeyron Equation Solid-Liquid Equilibrium Solid- Vapor and Liquid- Vapor Equilibrium Presentation of Thermodynamic Property Data Problems

217
217 220 223 225 229 233

9 Principles of Phase Equilibrium

9-1 9-2 9-3 9-4 9-5 9-6 9-7 9-8 9-9 9-10 9-11 9-12 9-13 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 ofActivity Coefficients Henry's Law Activity Coefficient Equations Phase Equilibrium Via an Equation of State The Thermodynamic Approach to Phase Equilibrium Problems

239
240 244 246 247 249 258 261 270 274 278 279 291 299 302 309 313 319 325 327 332 337 340 346 350 352 359 362

10

Applied Phase Equilibrium 10-1 The Consummate Thermodynamic Correlation of Vapor-Liquid Equilibrium 10-2 Constant-Pressure VLEData 10-3 Total Pressure Data 10-4 Azeotropes 10-5 Thermodynamic Consistency Tests 10-6 Multicomponent Vapor-Liquid Equilibrium 10-7 Phase Behavior in Partially Miscible Systems 10-8 Liquid-Liquid Equilibrium 10-9* Ternary Liquid-Liquid Equilibrium 10-10 Estimates from Fragmentary Data 10-11 Recapitulation Problems

Contents

11

Additional Topics in Phase Equilibrium 11-1 11-2 11-3 11-4* 11-5* 11-6* 11-7* 11-8* 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 Problems

375 375 3 78 384 386 390 394 410 412 420

12 Chemical Equilibrium
12-1 12-2 12-3 12-4 12-5 12-6 12-7 12-8 12-9 12-10* 12-11* 12-12* 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 Problems

433
435 437 440 444 446 454 456 462 468 478 486 505 511 529 530 548 55 7 571 579 581

13

Complex Chemical Equilibrium 13-1 The Phase Rulefor Reacting Systems 13-2* Analyzing Complex Chemical Equilibrium Problems 13-3 * Formulating Complex Chemical Equilibrium Problems 13-4* The CHO System and Carbon Deposition Boundaries 13-5* The Si-Cl-H System and Silicon Deposition Boundaries Problems

14 Thermodynamic Analysis of Processes

14-1 14-2 14-3 Work and Free Energy Functions The Availability Mixing and Separation Processes

589
589 591 600

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xi

14-4* 14-5

Heat Exchange Systems Involving Chemical Transformations Problems

607 614 632

15 Physicomechanical Processes
15-1 15-2 15-3 15-4 15-5 15-6 15-7 Compression and Expansion of Gases The Joule-Thomson Expansion Liquefaction of Gases Refrigeration Heat Pumps Power Generation Cogeneration of Steam and Power Problems

639
640 643 645 654 661 662 667 671

16 Compressible Fluid Flow

16-1 16-2 16-3 16-4 16-5 The Basic Equations of Fluid Mechanics Sonic Velocity Isentropic Flow Isentropic Flow Through Nozzles Nonisentropic Flow Problems

677
678 681 683 685 689 693

17 Thermodynamics and Models

17-1* 17-2* 17-3* Standard Models Ad Hoc Models Evaluation of Models Problems

697
698 703 719 722 729

Appendix A Table A-l FigureA-1 Appendix B Table B-l Molar Heat Capacities of Gases at Zero Pressure Critical Constants of Selected Substances Equilibrium Constants for Selected Reactions

729 731 732 732

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Contents

Appendix C
Table C-l Table C-2 Thermodynamic Properties of Saturated Steam Thermodynamic Properties ofSuperheated Steam

734
734 737

Appendix D
Table D-l Table D-2 Table D-3 Appendix E Inventory ofthe CD-ROM Appendix F Properties ofDeterminants Index

742
Enthalpies and Free Energies of Formation of Selected Organic Compounds 742 Enthalpies and Free Energies of Formation of Selected Inorganic Compounds 744 Free Energies of Formation of Selected Ions in the Aqueous State 745 746 746 751 751 753