247254444
247254444
247254444
Third Edition
B. G. Kyle
Emeritus Professor of Chemical Engineering Kansas State University
CONTENTS
viii
Contents
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
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
217
217 220 223 225 229 233
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
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
589
589 591 600
Contents
xi
14-4* 14-5
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
677
678 681 683 685 689 693
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
xii
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