Engineering and Chemical Thermodynamics

Cover......Page 1
Title Page......Page 5
Copyright Page......Page 6
Preface......Page 9
Contents......Page 15
Learning Objectives......Page 19
1.1 Thermodynamics......Page 20
Thermodynamic Systems......Page 21
Properties......Page 22
Processes......Page 23
Length Scales......Page 24
Volume (Extensive or Intensive)......Page 25
Temperature (Intensive)......Page 26
Pressure (Intensive)......Page 29
The Ideal Gas......Page 31
Types of Equilibrium......Page 33
Molecular View of Equilibrium......Page 34
The State Postulate......Page 35
Gibbs Phase Rule......Page 36
1.6 The PvT Surface and Its Projections for Pure Substances......Page 38
Changes of State During a Process......Page 40
Saturation Pressure vs. Vapor Pressure......Page 41
The Critical Point......Page 42
1.7 Thermodynamic Property Tables......Page 44
1.8 Summary......Page 48
Conceptual Problems......Page 49
Numerical Problems......Page 52
Learning Objectives......Page 54
Forms of Energy......Page 55
Ways We Observe Changes in U......Page 57
Internal Energy of an Ideal Gas......Page 58
Work and Heat: Transfer of Energy Between the System and the Surroundings......Page 60
2.2 Construction of Hypothetical Paths......Page 64
Irreversible Processes......Page 66
Integral Balances......Page 73
Differential Balances......Page 75
Flow Work......Page 78
Steady-State Energy Balances......Page 80
Transient Energy Balance......Page 81
Heat Capacity: cv and cp......Page 85
Latent Heats......Page 94
Enthalpy of Reactions......Page 98
Reversible, Isothermal Expansion (Compression)......Page 110
Adiabatic Expansion (Compression) with Constant Heat Capacity......Page 111
2.8 Open-System Energy Balances on Process Equipment......Page 113
Nozzles and Diffusers......Page 114
Turbines and Pumps (or Compressors)......Page 115
Heat Exchangers......Page 116
Throttling Devices......Page 119
2.9 Thermodynamic Cycles and the Carnot Cycle......Page 120
Efficiency......Page 122
2.10 Summary......Page 126
Conceptual Problems......Page 128
Numerical Problems......Page 131
Learning Objectives......Page 145
3.1 Directionality of Processes/Spontaneity......Page 146
3.2 Reversible and Irreversible Processes (Revisited) and their Relationship to Directionality......Page 147
3.3 Entropy, the Thermodynamic Property......Page 149
3.4 The Second Law of Thermodynamics......Page 158
3.5 Other Common Statements of the Second Law of Thermodynamics......Page 160
Calculation of Δs for Closed Systems......Page 161
Calculation of Δs for Open Systems......Page 165
3.7 Calculation of Δs for an Ideal Gas......Page 169
3.8 The Mechanical Energy Balance and the Bernoulli Equation......Page 178
The Rankine Cycle......Page 182
The Vapor-Compression Refrigeration Cycle......Page 187
3.10 Exergy (Availability) Analysis......Page 190
Exergy......Page 191
Exthalpy—Flow Exergy in Open Systems......Page 196
3.11 Molecular View of Entropy......Page 200
Maximizing Molecular Configurations over Space......Page 203
Maximizing Molecular Configurations over Energy......Page 204
3.12 Summary......Page 208
Conceptual Problems......Page 209
Numerical Problems......Page 213
Learning Objectives......Page 227
Motivation......Page 228
Internal (Molecular) Energy......Page 229
The Electric Nature of Atoms and Molecules......Page 230
Attractive Forces......Page 231
Intermolecular Potential Functions and Repulsive Forces......Page 241
Principle of Corresponding States......Page 244
Chemical Forces......Page 246
The van der Waals Equation of State......Page 250
Cubic Equations of State (General)......Page 256
The Virial Equation of State......Page 258
Equations of State for Liquids and Solids......Page 263
4.4 Generalized Compressibility Charts......Page 264
4.5 Determination of Parameters for Mixtures......Page 267
Cubic Equations of State......Page 268
Virial Equation of State......Page 269
Corresponding States......Page 270
4.6 Summary......Page 272
Conceptual Problems......Page 273
Numerical Problems......Page 275
Measured Properties......Page 283
Derived Thermodynamic Properties......Page 284
Dependent and Independent Properties......Page 285
Hypothetical Paths (revisited)......Page 286
Fundamental Property Relations......Page 287
Maxwell Relations......Page 289
Other Useful Mathematical Relations......Page 290
Using the Thermodynamic Web to Access Reported Data......Page 291
Relation of ds in Terms of Independent Properties T and v and Independent Properties T and P......Page 294
Relation of du in Terms of Independent Properties T and v......Page 295
Relation of dh in Terms of Independent Properties T and P......Page 299
Alternative Formulation of the Web using T and P as Independent Properties......Page 305
Enthalpy Departure Function......Page 308
Entropy Departure Function......Page 311
Joule-Thomson Expansion......Page 316
Liquefaction......Page 319
5.6 Summary......Page 322
Conceptual Problems......Page 323
Numerical Problems......Page 325
6.1 Introduction......Page 333
The Phase Equilibria Problem......Page 334
Gibbs Energy as a Criterion for Chemical Equilibrium......Page 336
Roles of Energy and Entropy in Phase Equilibria......Page 339
The Relationship Between Saturation Pressure and Temperature: The Clapeyron Equation......Page 345
Pure Component Vapor–Liquid Equilibrium: The Clausius–Clapeyron Equation......Page 346
Introduction......Page 352
Partial Molar Properties......Page 353
The Gibbs–Duhem Equation......Page 358
Summary of the Different Types of Thermodynamic Properties......Page 360
Property Changes of Mixing......Page 361
Determination of Partial Molar Properties......Page 375
Relations Among Partial Molar Quantities......Page 384
The Chemical Potential—The Criteria for Chemical Equilibrium......Page 385
Temperature and Pressure Dependence of μi......Page 388
6.5 Summary......Page 390
Conceptual Problems......Page 391
Numerical Problems......Page 395
7.1 Introduction......Page 409
Definition of Fugacity......Page 410
Criteria for Chemical Equilibria in Terms of Fugacity......Page 413
Fugacity and Fugacity Coefficient of Pure Gases......Page 414
Fugacity and Fugacity Coefficient of Species i in a Gas Mixture......Page 421
The Lewis Fugacity Rule......Page 429
Property Changes of Mixing for Ideal Gases......Page 430
Reference States for the Liquid Phase......Page 432
Thermodynamic Relations Between Υi......Page 440
Models for Υi Using ɡΕ......Page 446
Solid Solutions......Page 467
7.6 Summary......Page 468
Conceptual Problems......Page 470
Numerical Problems......Page 472
Learning Objectives......Page 484
Raoult’s Law (Ideal Gas and Ideal Solution)......Page 485
Nonideal Liquids......Page 493
Azeotropes......Page 502
Fitting Activity Coefficient Models with VLE Data......Page 508
Solubility of Gases in Liquids......Page 513
Vapor–Liquid Equilibrium Using the Equations of State Method......Page 519
8.2 Liquid (a)-Liquid (β) Equilibrium: LLE......Page 529
8.3 Vapor–Liquid (a)-Liquid (β) Equilibrium: VLLE......Page 537
Pure Solids......Page 541
Solid Solutions......Page 547
Boiling Point Elevation and Freezing Point Depression......Page 549
Osmotic Pressure......Page 553
8.6 Summary......Page 556
Conceptual Problems......Page 558
Numerical Problems......Page 562
Learning Objectives......Page 580
9.1 Thermodynamics and Kinetics......Page 581
9.2 Chemical Reaction and Gibbs Energy......Page 583
9.3 Equilibrium for a Single Reaction......Page 586
Calculation of K from Gibbs Energy of Formation......Page 590
The Temperature Dependence of K......Page 592
The Equilibrium Constant for a Gas-Phase Reaction......Page 597
The Equilibrium Constant for a Liquid-Phase (or Solid-Phase) Reaction......Page 604
The Equilibrium Constant for a Heterogeneous Reaction......Page 605
9.6 Equilibrium in Electrochemical Systems......Page 607
Electrochemical Cells......Page 608
Shorthand Notation......Page 609
Electrochemical Reaction Equilibrium......Page 610
Thermochemical Data: Half-Cell Potentials......Page 612
Activity Coefficients in Electrochemical Systems......Page 615
Extent of Reaction and Equilibrium Constant for R Reactions......Page 617
Gibbs Phase Rule for Chemically Reacting Systems and Independent Reactions......Page 619
Solution of Multiple Reaction Equilibria by Minimization of Gibbs Energy......Page 628
9.8 Reaction Equilibria of Point Defects in Crystalline Solids......Page 630
Atomic Defects......Page 631
Electronic Defects......Page 634
Effect of Gas Partial Pressure on Defect Concentrations......Page 637
9.9 Summary......Page 642
Conceptual Problems......Page 644
Numerical Problems......Page 646
A.1 Critical Constants, Acentric Factors, and Antoine Coefficients......Page 657
A.2 Heat Capacity Data......Page 659
A.3 Enthalpy and Gibbs Energy of Formation at 298 K and 1 Bar......Page 661
Appendix B Steam Tables......Page 665
B.1 Saturated Water: Temperature Table......Page 666
B.2 Saturated Water: Pressure Table......Page 668
B.3 Saturated Water: Solid-Vapor......Page 670
B.4 Superheated Water Vapor......Page 671
B.5 Subcooled Liquid Water......Page 677
Appendix C Lee–Kesler Generalized Correlation Tables......Page 678
D.1 Common Variables Used in Thermodynamics and Their Associated Units......Page 694
D.2 Conversion between CGS (Gaussian) units and SI units......Page 697
E.1 Software Description......Page 698
E.2 Corresponding States Using The Lee–Kesler Equation of State......Page 701
F.1 Sources of Thermodynamic Data......Page 703
F.2 Textbooks and Monographs......Page 704
Index......Page 705