Fundamentals of Chemical Engineering Thermodynamics (International Series in the Physical and Chemical Engineering Sciences)

¿ The Clear, Well-Organized Introduction to Thermodynamics Theory and Calculations for All Chemical Engineering Undergraduate Students This text is designed to make thermodynamics far easier for undergraduate chemical engineering students to learn, and to help them perform thermodynamic calculations with confidence. Drawing on his award-winning courses at Penn State, Dr. Themis Matsoukas focuses on “why” as well as “how.” He offers extensive imagery to help students conceptualize the equations, illuminating thermodynamics with more than 100 figures, as well as 190 examples from within and beyond chemical engineering. Part I clearly introduces the laws of thermodynamics with applications to pure fluids. Part II extends thermodynamics to mixtures, emphasizing phase and chemical equilibrium. Throughout, Matsoukas focuses on topics that link tightly to other key areas of undergraduate chemical engineering, including separations, reactions, and capstone design. More than 300 end-of-chapter problems range from basic calculations to realistic environmental applications; these can be solved with any leading mathematical software. Coverage includes • Pure fluids, PVT behavior, and basic calculations of enthalpy and entropy • Fundamental relationships and the calculation of properties from equations of state • Thermodynamic analysis of chemical processes • Phase diagrams of binary and simple ternary systems • Thermodynamics of mixtures using equations of state • Ideal and nonideal solutions • Partial miscibility, solubility of gases and solids, osmotic processes • Reaction equilibrium with applications to single and multiphase reactions fundamentals-of-chemical-engineering-thermodynamics 1 a 2 Fundamentals of Chemical Engineering Thermodynamics 2 cover2 4 backcover 5 book2 6 Contents 7 Preface 12 About the Author 15 Part I: Pure Fluids 19 Chapter 1. Scope and Language of Thermodynamics 20 1.1 Molecular Basis of Thermodynamics 22 Intermolecular Potential 22 Temperature and Pressure 23 Phase Transitions 25 Ideal-Gas State 26 1.2 Statistical versus Classical Thermodynamics 26 The Laws of Classical Thermodynamics 26 The “How” and the “Why” in Thermodynamics 27 1.3 Definitions 27 System 27 Equilibrium 28 Constrained Equilibrium 29 Extensive and Intensive Properties 29 State of Pure Component 30 State of Multicomponent Mixture 31 Process and Path 31 Quasi-Static Process 32 Quasi Static is Reversible 33 1.4 Units 34 Pressure 34 Temperature 35 Mole (mol, gmol, lb-mol) 35 Energy 36 1.5 Summary 37 1.6 Problems 38 Chapter 2. Phase Diagrams of Pure Fluids 40 2.1 The PVT Behavior of Pure Fluid 40 The PV Graph 41 The Critical Point 43 A Special Limit: The Ideal-Gas State 43 Two-Phase Region–The Lever Rule 44 The PT Graph 46 2.2 Tabulation of Properties 49 2.3 Compressibility Factor and the ZP Graph 51 2.4 Corresponding States 53 Acentric Factor and the Pitzer Method 54 2.5 Virial Equation 59 Truncated Virial Equation 60 Pitzer Method for the Second Virial Coefficient 60 2.6 Cubic Equations of State 63 Van der Waals Equation of State 63 2.7 PVT Behavior of Cubic Equations of State 66 Unstable and Metastable Parts of Subcritical Isotherm 67 2.8 Working with Cubic Equations 68 2.9 Other Equations of State 70 2.10 Thermal Expansion and Isothermal Compression 74 2.11 Empirical Equations for Density 74 Rackett Equation 74 2.12 Summary 78 2.13 Problems 79 Chapter 3. Energy and the First Law 86 3.1 Energy and Mechanical Work 86 3.2 Shaft Work and PV Work 88 3.3 Internal Energy and Heat 93 3.4 First Law for a Closed System 94 3.5 Elementary Paths 97 Constant-Volume Heating 97 Constant-Pressure Heating 97 Constant-Temperature Process 101 3.6 Sensible Heat—Heat Capacities 102 Constant-Volume Heat Capacity 102 Constant-Pressure Heat Capacity 103 Why Are CV and CP Different? 104 Effect of Pressure and Temperature on Heat Capacity 105 Ideal-Gas Heat Capacity 106 Liquid Heat Capacities 106 3.7 Heat of Vaporization 110 Pitzer Correlation for ΔHvap 111 3.8 Ideal-Gas State 113 Reversible Adiabatic Process 116 3.9 Energy Balances and Irreversible Processes 121 3.10 Summary 125 3.11 Problems 127 Chapter 4. Entropy and the Second Law 135 4.1 The Second Law in a Closed System 135 Relating Entropy to Measurable Quantities 136 4.2 Calculation of Entropy 138 Constant-Pressure Path, No Phase Change 138 Constant-Volume Path, No Phase Change 139 Entropy and Phase Change 141 Entropy Change of Bath 143 Entropy in the Ideal-Gas State 144 Using Tabulated Values 145 4.3 Energy Balances Using Entropy 146 Reversible Adiabatic Process in the Ideal-Gas State 147 4.4 Entropy Generation 149 4.5 Carnot Cycle 150 First-Law Analysis of the Carnot Cycle 151 Second-Law Analysis of the Carnot Cycle 152 Thermodynamic Efficiency 152 4.6 Alternative Statements of the Second Law 157 4.7 Ideal and Lost Work 161 4.8 Ambient Surroundings as a Default Bath—Exergy 164 4.9 Equilibrium and Stability 166 Equilibrium Conditions at Constant Temperature and Pressure 167 4.10 Molecular View of Entropy 169 Entropy and Probabilities 171 4.11 Summary 172 Calculation of Entropy 172 Consequences of the Second Law 173 4.12 Problems 173 Chapter 5. Calculation of Properties 177 5.1 Calculus of Thermodynamics 177 5.2 Integration of Differentials 183 5.3 Fundamental Relationships 184 5.4 Equations for Enthalpy and Entropy 187 5.5 Ideal-Gas State 188 5.6 Incompressible Phases 189 5.7 Residual Properties 190 Residual Enthalpy 191 Residual Entropy 192 Residual Volume 192 Other Residual Properties 193 Applications 193 5.8 Pressure-Explicit Relations 196 5.9 Application to Cubic Equations 197 5.10 Generalized Correlations 201 5.11 Reference States 205 5.12 Thermodynamic Charts 208 Pressure-Enthalpy Chart 208 Temperature-Entropy Chart 209 Enthalpy-Entropy Chart (Mollier Chart) 210 5.13 Summary 211 5.14 Problems 212 Chapter 6. Balances in Open Systems 216 6.1 Flow Streams 216 6.2 Mass Balance 218 6.3 Energy Balance in Open System 219 Special Case: Closed System 221 Special Case: Steady State 221 6.4 Entropy Balance 222 Steady-State Process 223 Reversible Adiabatic Process 224 6.5 Ideal and Lost Work 228 6.6 Thermodynamics of Steady-State Processes 232 Flow through Pipe 232 Adiabatic Mixing 236 Heat Exchanger 237 Steam Turbine 240 Reversible Operation 241 Actual Operation 241 Throttling 244 Gas Compression 246 Expansion and Compression of Liquids 249 6.7 Power Generation 250 6.8 Refrigeration 255 Thermodynamic Analysis of Refrigeration 257 Refrigerants 260 6.9 Liquefaction 262 6.10 Unsteady-State Balances 267 Pressurizing a Tank 267 Venting a Tank 270 6.11 Summary 273 6.12 Problems 274 Chapter 7. VLE of Pure Fluid 285 7.1 Two-Phase Systems 285 7.2 Vapor-Liquid Equilibrium 287 Clausius-Clapeyron Equation 288 7.3 Fugacity 289 Fugacity in the Ideal-Gas State 290 Relationship to the Gibbs Free Energy 290 7.4 Calculation of Fugacity 291 Compressed Liquids—Poynting Equation 291 Using Tabulated Properties 292 Using the Compressibility Factor 293 Fugacity from Generalized Graphs 294 Fugacity from Cubic Equations of State 297 7.5 Saturation Pressure from Equations of State 298 7.6 Phase Diagrams from Equations of State 300 7.7 Summary 303 7.8 Problems 304 Part II: Mixtures 311 Chapter 8. Phase Behavior of Mixtures 312 8.1 The Txy Graph 312 The Lever Rule 314 8.2 The Pxy Graph 315 8.3 Azeotropes 321 8.4 The xy Graph 323 8.5 VLE at Elevated Pressures and Temperatures 324 8.6 Partially Miscible Liquids 325 8.7 Ternary Systems 330 8.8 Summary 333 8.9 Problems 333 Chapter 9. Properties of Mixtures 340 9.1 Composition 340 9.2 Mathematical Treatment of Mixtures 342 The Partial Molar Property 343 Gibbs-Duhem Equation 344 Special Case: Systems of Constant Composition 345 9.3 Properties of Mixing 346 9.4 Mixing and Separation 348 9.5 Mixtures in the Ideal-Gas State 349 Other Properties 350 9.6 Equations of State for Mixtures 353 Residual Properties 354 Binary Mixture 354 9.7 Mixture Properties from Equations of State 355 9.8 Summary 360 9.9 Problems 360 Chapter 10. Theory of Vapor-Liquid Equilibrium 365 10.1 Gibbs Free Energy of Mixture 365 Multicomponent Equilibrium 367 Gibbs’s Phase Rule 367 10.2 Chemical Potential 368 Chemical Potential in Ideal Gas and in Real Mixture 369 10.3 Fugacity in a Mixture 371 10.4 Fugacity from Equations of State 374 10.5 VLE of Mixture Using Equations of State 375 The Interaction Parameter 378 10.6 Summary 380 10.7 Problems 380 Chapter 11. Ideal Solution 385 11.1 Ideality in Solution 386 11.2 Fugacity in Ideal Solution 388 11.3 VLE in Ideal Solution–Raoult’s Law 389 Bubble P Calculation 390 Bubble T Calculation 390 Dew P Calculation 391 Dew T Calculation 391 Flash Calculation 391 11.4 Energy Balances 397 11.5 Noncondensable Gases 401 Applications–Humidification 402 11.6 Summary 404 11.7 Problems 404 Chapter 12. Nonideal Solutions 409 12.1 Excess Properties 409 Excess Partial Molar Properties 410 12.2 Heat Effects of Mixing 415 Enthalpy Charts 418 12.3 Activity Coefficient 421 Activity Coefficient and Excess Gibbs Energy 422 12.4 Activity Coefficient and Phase Equilibrium 424 Positive and Negative Deviations from Raoult’s Law 425 12.5 Data Reduction: Fitting Experimental Activity Coefficients 428 12.6 Models for the Activity Coefficient 431 Margules Equation 431 van Laar Equation 434 Wilson Equation 434 Non Random Two Liquid Model (NRTL) 435 Flory-Huggins Model 435 UNIQUAC 436 Group Contribution Method for ri, qi 437 UNIFAC 440 12.7 Summary 445 12.8 Problems 446 Chapter 13. Miscibility, Solubility, and Other Phase Equilibria 457 13.1 Equilibrium between Partially Miscible Liquids 457 13.2 Gibbs Free Energy and Phase Splitting 459 Equilibrium and Stability 461 13.3 Liquid Miscibility and Temperature 467 13.4 Completely Immiscible Liquids 468 13.5 Solubility of Gases in Liquids 472 VLE Using Henry’s Law 474 Other Units for Henry’s Law Constant 474 Temperature and Pressure Effects on Henry’s Law Constant 477 Infinite Dilution and Ideal Solution as Reference States 480 13.6 Solubility of Solids in Liquids 482 Phase Diagram and Freezing Point Depression 485 13.7 Osmotic Equilibrium 486 Reverse Osmosis 489 13.8 Summary 490 13.9 Problems 491 Chapter 14. Reactions 496 14.1 Stoichiometry 496 14.2 Standard Enthalpy of Reaction 498 Effect of Temperature on Enthalpy of Reaction 500 14.3 Energy Balances in Reacting Systems 502 14.4 Activity 506 Activity of Gas 507 Activity of Liquid 507 Activity of Solid 509 14.5 Equilibrium Constant 512 Equilibrium Constant and Temperature 515 Other Forms of the Equilibrium Constant 518 14.6 Composition at Equilibrium 519 14.7 Reaction and Phase Equilibrium 520 14.8 Reaction Equilibrium Involving Solids 524 14.9 Multiple Reactions 526 14.10 Summary 529 14.11 Problems 530 Bibliography 538 Appendix A. Critical Properties of Selected Compounds 539 Appendix B. Ideal-Gas Heat Capacities 542 Appendix C. Standard Enthalpy and Gibbs Free Energy of Reaction 545 Appendix D. UNIFAC Tables 548 Appendix E. Steam Tables 552 backcover2 562 Footnotes 563 Footnotes 563 Chapter 1 563 Chapter 2 563 Chapter 3 564 Chapter 4 564 Chapter 5 565 Chapter 6 566 Chapter 7 566 Chapter 8 567 Chapter 9 567 Chapter 10 568 Chapter 11 568 Chapter 12 569 Chapter 13 569 Chapter 14 570

The Clear, Well-Organized Introduction to Thermodynamics Theory and Calculations for All Chemical Engineering Undergraduate Students

This text is designed to make thermodynamics far easier for undergraduate chemical engineering students to learn, and to help them perform thermodynamic calculations with confidence. Drawing on his award-winning courses at Penn State, Dr. Themis Matsoukas focuses on “why” as well as “how.” He offers extensive imagery to help students conceptualize the equations, illuminating thermodynamics with more than 100 figures, as well as 190 examples from within and beyond chemical engineering.

Part I clearly introduces the laws of thermodynamics with applications to pure fluids. Part II extends thermodynamics to mixtures, emphasizing phase and chemical equilibrium. Throughout, Matsoukas focuses on topics that link tightly to other key areas of undergraduate chemical engineering, including separations, reactions, and capstone design. More than 300 end-of-chapter problems range from basic calculations to realistic environmental applications; these can be solved with any leading mathematical software.

Coverage includes

• Pure fluids, PVT behavior, and basic calculations of enthalpy and entropy

• Fundamental relationships and the calculation of properties from equations of state

• Thermodynamic analysis of chemical processes

• Phase diagrams of binary and simple ternary systems

• Thermodynamics of mixtures using equations of state

• Ideal and nonideal solutions

• Partial miscibility, solubility of gases and solids, osmotic processes

• Reaction equilibrium with applications to single and multiphase reactions