Introduction to Chemical Engineering Thermodynamics

Cover......Page 1
Title......Page 2
Copyright......Page 3
Contents......Page 4
List of Symbols......Page 9
Preface......Page 14
1.1 The scope of thermodynamics......Page 16
1.3 Measures of amount or size......Page 17
1.4 Force......Page 18
1.5 Temperature......Page 19
1.6 Pressure......Page 21
1.7 Work......Page 23
1.8 Energy......Page 24
1.9 Heat......Page 29
Problems......Page 30
2.2 Internal energy......Page 33
2.3 The first law of thermodynamics......Page 34
2.4 Energy balance for closed systems......Page 35
2.5 Thermodynamic state and state functions......Page 38
2.7 The phase rule......Page 41
2.8 The reversible process......Page 43
2.9 Constant-v and constant-p processes......Page 49
2.10 Enthalpy......Page 50
2.11 Heat capacity......Page 52
2.12 Mass and energy balances for open systems......Page 57
Problems......Page 67
3.1 PVT behavior of pure substances......Page 73
3.2 Virial equations of state......Page 78
3.3 The ideal gas......Page 81
3.4 Application of the virial equations......Page 97
3.5 Cubic equations of state......Page 101
3.6 Generalized correlations for gases......Page 110
3.7 Generalized correlations for liquids......Page 118
Problems......Page 120
4.1 Sensible heat effects......Page 131
4.2 Latent heats of pure substances......Page 138
4.3 Standard heat of reaction......Page 141
4.4 Standard heat of formation......Page 142
4.5 Standard heat of combustion......Page 144
4.6 Temperature dependence of ∆H......Page 145
4.7 Heat effects of industrial reactions......Page 148
Problems......Page 155
5.1 Statements of the second law......Page 163
5.2 Heat engines......Page 164
5.3 Thermodynamic temperature scales......Page 166
5.4 Entropy......Page 170
5.5 Entropy changes of an ideal gas......Page 174
5.6 Mathematical statement of the second law......Page 177
5.7 Entropy balance for open systems......Page 179
5.8 Calculation of ideal work......Page 184
5.9 Lost work......Page 188
5.10 The third law of thermodynamics......Page 191
5.11 Entropy from the microscopic viewpoint......Page 192
Problems......Page 193
6.1 Property relations for homogeneous phases......Page 201
6.2 Residual properties......Page 211
6.3 Residual properties by equations of state......Page 217
6.4 Two-phase systems......Page 222
6.5 Thermodynamic diagrams......Page 225
6.6 Tables of thermodynamic properties......Page 227
6.7 Generalized property correlations for gases......Page 230
Problems......Page 239
7. Applications of Thermodynamics to Flow Processes......Page 250
7.1 Duct flow of compressible fluids......Page 251
7.2 Turbines (expanders)......Page 264
7.3 Compression processes......Page 270
Problems......Page 277
8. Production of Power from Heat......Page 284
8.1 The steam power plant......Page 285
8.2 Internal-combustion engines......Page 296
8.3 Jet engines; rocket engines......Page 304
Problems......Page 305
9.1 The Carnot refrigerator......Page 309
9.2 The vapor-compression cycle......Page 310
9.3 The choice of refrigerant......Page 313
9.4 Absorption refrigeration......Page 316
9.5 The heat pump......Page 318
9.6 Liquefaction processes......Page 319
Problems......Page 325
10.1 The nature of equilibrium......Page 329
10.2 The phase rule. Duhem's theorem......Page 330
10.3 VLE: qualitative behavior......Page 332
10.4 Simple models for vapor/liquid equilibrium......Page 341
10.5 VLE by modified Raoult's law......Page 350
10.6 VLE from K-value correlations......Page 354
Problems......Page 361
11. Solution Thermodynamics: Theory......Page 367
11.1 Fundamental property relation......Page 368
11.2 The chemical potential and phase equilibria......Page 369
11.3 Partial properties......Page 370
11.4 Ideal-gas mixtures......Page 380
11.5 Fugacity and fugacity coefficient: pure species......Page 383
11.6 Fugacity and fugacity coefficient: species in solution......Page 389
11.7 Generalized correlations for the fugacity coefficient......Page 395
11.8 The ideal solution......Page 399
11.9 Excess properties......Page 401
Problems......Page 408
12.1 Liquid-phase properties from VLE data......Page 415
12.2 Models for the excess Gibbs energy......Page 430
12.3 Property changes of mixing......Page 434
12.4 Heat effects of mixing processes......Page 441
Problems......Page 455
13. Chemical-Reaction Equilibria......Page 465
13.1 The reaction coordinate......Page 466
13.2 Application of equilibrium criteria to chemical reactions......Page 470
13.3 The standard Gibbs-energy change and the equilibrium constant......Page 471
13.4 Effect of temperature on the equilibrium constant......Page 473
13.5 Evaluation of equilibrium constants......Page 477
13.6 Relation of equilibrium constants to composition......Page 479
13.7 Equilibrium conversions for single reactions......Page 483
13.8 Phase rule and Duhem's theorem for reacting systems......Page 496
13.9 Multireaction equilibria
......Page 499
13.10 Fuel cells......Page 510
Problems......Page 514
14.1 The gamma/phi formulation of VLE......Page 522
14.2 VLE from cubic equations of state......Page 533
14.3 Equilibrium and stability......Page 549
14.4 Liquid/liquid equilibrium (LLE)
......Page 556
14.5 Vapor/liquid/liquid equilibrium (VLLE)......Page 564
14.6 Solid/liquid equilibrium (SLE)......Page 572
14.7 Solid/vapor equilibrium (SVE)......Page 576
14.8 Equilibrium adsorption of gases on solids......Page 580
14.9 Osmotic equilibrium and osmotic pressure......Page 595
Problems......Page 598
15.1 Thermodynamic analysis of steady-state flow processes......Page 605
Problems......Page 614
16.1 Molecular theory of fluids......Page 616
16.2 Second virial coefficients from potential functions......Page 623
16.3 Internal energy of ideal gases: microscopic view......Page 626
16.4 Thermodynamic properties and statistical mechanics......Page 629
16.5 Hydrogen bonding and charge-transfer complexing......Page 631
16.6 Behavior of excess properties......Page 634
16.7 Molecular basis for mixture behavior......Page 637
16.8 VLE by molecular simulation......Page 641
Problems......Page 642
Appendix A. Conversion Factors and Values of the Gas Constants......Page 644
Appendix B. Properties of Pure Species......Page 646
Appendix C. Heat Capacities and Property Changes of Formation......Page 649
Appendix D. Representative Computer Programs......Page 654
Appendix E. The Lee/Kesler Generalized-correlation Tables......Page 660
Appendix F. Steam Tables......Page 677
Appendix G. Thermodynamic Diagrams......Page 719
Appendix H. UNIFAC Method......Page 722
Appendix I. Newton's Method......Page 729
Author Index......Page 734
Subject Index......Page 738
Diagrams......Page 747