A TREATISE ON THERMODYNAMICS
1 Getting Started 1 11 Using Thermodynamics 2 12 Defining Systems 2 121 Closed Systems 4 122 Control Volumes 4 123 Selecting the System Boundary 5 13 Describing Systems and Their Behavior 6 131 Macroscopic and Microscopic Views of Thermodynamics 6 132 Property, State, and Process 7 133 Extensive and Intensive Properties 7 134 Equilibrium 8 14 Measuring Mass, Length, Time, and Force 8 141 SI Units 9 142 English Engineering Units 10 15 Specific Volume 11 16 Pressure 12 161 Pressure Measurement 13 162 Buoyancy 14 163 Pressure Units 14 17 Temperature 16 171 Thermometers 16 172 Kelvin Temperature Scales 17 173 Celsius Scales 18 18 Engineering Design and Analysis 19 181 Design 19 182 Analysis 20 19 Methodology for Solving Thermodynamics Problems 20 Chapter Summary and Study Guide 22 2 Energy and the First Law of Thermodynamics 29 21 Reviewing Mechanical Concepts of Energy 30 211 Work and Kinetic Energy 30 212 Potential Energy 31 213 Units for Energy 32 214 Conservation of Energy in Mechanics 33 215 Closing Comment 33 22 Broadening Our Understanding of Work 34 221 Sign Convention and Notation 35 222 Power 36 223 Modeling Expansion or Compression Work 37 224 Expansion or Compression Work in Actual Processes 37 225 Expansion or Compression Work in Quasiequilibrium Processes 38 226 Further Examples of Work 41 227 Further Examples of Work in Quasiequilibrium Processes 42 228 Generalized Forces and Displacements 43 23 Broadening Our Understanding of Energy 43 24 Energy Transfer by Heat 44 241 Sign Convention, Notation, and Heat Transfer Rate 45 242 Heat Transfer Modes 46 243 Closing Comments 48 25 Energy Accounting: Energy Balance for Closed Systems 48 251 Important Aspects of the Energy Balance 50 252 Using the Energy Balance: Processes of Closed Systems 51 253 Using the Energy Rate Balance: Steady-State Operation 54 254 Using the Energy Rate Balance: Transient Operation 56 26 Energy Analysis of Cycles 57 261 Cycle Energy Balance 58 262 Power Cycles 59 263 Refrigeration and Heat Pump Cycles 59 27 Energy Storage 61 271 Overview 61 272 Storage Technologies 61 Chapter Summary and Study Guide 62 3 Evaluating Properties 73 31 Getting Started 74 311 Phase and Pure Substance 74 312 Fixing the State 74 32 p–?–T Relation 75 321 p–?–T Surface 76 322 Projections of the p–?–T Surface 77 33 Studying Phase Change 79 34 Retrieving Thermodynamic Properties 81 35 Evaluating Pressure, Specific Volume, and Temperature 82 351 Vapor and Liquid Tables 82 352 Saturation Tables 84 36 Evaluating Specific Internal Energy and Enthalpy 88 361 Introducing Enthalpy 88 362 Retrieving u and h Data 88 363 Reference States and Reference Values 89 37 Evaluating Properties Using Computer Software 90 38 Applying the Energy Balance Using Property Tables and Software 92 381 Using Property Tables 93 382 Using Software 95 39 Introducing Specific Heats c? and cp 97 310 Evaluating Properties of Liquids and Solids 98 3101 Approximations for Liquids Using Saturated Liquid Data 98 3102 Incompressible Substance Model 99 311 Generalized Compressibility Chart 101 3111 Universal Gas Constant, R– 101 3112 Compressibility Factor, Z 101 3113 Generalized Compressibility Data, Z Chart 102 3114 Equations of State 105 312 Introducing the Ideal Gas Model 105 3121 Ideal Gas Equation of State 106 3122 Ideal Gas Model 106 3123 Microscopic Interpretation 108 313 Internal Energy, Enthalpy, and Specific Heats of Ideal Gases 108 3131 ?u, ?h, c? , and cp Relations 108 3132 Using Specific Heat Functions 109 314 Applying the Energy Balance Using Ideal Gas Tables, Constant Specific Heats, and Software 111 3141 Using Ideal Gas Tables 111 3142 Using Constant Specific Heats 112 3143 Using Computer Software 114 315 Polytropic Process Relations 116 Chapter Summary and Study Guide 118 4 Control Volume Analysis Using Energy 129 41 Conservation of Mass for a Control Volume 130 411 Developing the Mass Rate Balance 130 412 Evaluating the Mass Flow Rate 131 42 Forms of the Mass Rate Balance 131 421 One-Dimensional Flow Form of the Mass Rate Balance 132 422 Steady-State Form of the Mass Rate Balance 133 423 Integral Form of the Mass Rate Balance 133 43 Applications of the Mass Rate Balance 133 431 Steady-State Application 133 432 Time-Dependent (Transient) Application 134 44 Conservation of Energy for a Control Volume 136 441 Developing the Energy Rate Balance for a Control Volume 136 442 Evaluating Work for a Control Volume 137 443 One-Dimensional Flow Form of the Control Volume Energy Rate Balance 138 444 Integral Form of the Control Volume Energy Rate Balance 138 45 Analyzing Control Volumes at Steady State 139 451 Steady-State Forms of the Mass and Energy Rate Balances 139 452 Modeling Considerations for Control Volumes at Steady State 140 46 Nozzles and Diffusers 141 461 Nozzle and Diffuser Modeling Considerations 142 462 Application to a Steam Nozzle 142 47 Turbines 143 471 Steam and Gas Turbine Modeling Considerations 145 472 Application to a Steam Turbine 145 48 Compressors and Pumps 146 481 Compressor and Pump Modeling Considerations 147 482 Applications to an Air Compressor and a Pump System 147 483 Pumped-Hydro and Compressed-Air Energy Storage 149 49 Heat Exchangers 150 491 Heat Exchanger Modeling Considerations 151 492 Applications to a Power Plant Condenser and Computer Cooling 152 410 Throttling Devices 154 4101 Throttling Device Modeling Considerations 154 4102 Using a Throttling Calorimeter to Determine Quality 155 411 System Integration 156 412 Transient Analysis 159 4121 The Mass Balance in Transient Analysis 159 4122 The Energy Balance in Transient Analysis 159 4123 Transient Analysis Applications 160 Chapter Summary and Study Guide 166 5 The Second Law of Thermodynamics 179 51 Introducing the Second Law 180 511 Motivating the Second Law 180 512 Opportunities for Developing Work 181 513 Aspects of the Second Law 182 52 Statements of the Second Law 183 521 Clausius Statement of the Second Law 183 522 Kelvin–Planck Statement of the Second Law 183 523 Entropy Statement of the Second Law 184 524 Second Law Summary 185 53 Irreversible and Reversible Processes 185 531 Irreversible Processes 186 532 Demonstrating Irreversibility 187 533 Reversible Processes 189 534 Internally Reversible Processes 190 54 Interpreting the Kelvin–Planck Statement 191 55 Applying the Second Law to Thermodynamic Cycles 192 56 Second Law Aspects of Power Cycles Interacting with Two Reservoirs 193 561 Limit on Thermal Efficiency 193 562 Corollaries of the Second Law for Power Cycles 193 69 Entropy Rate Balance for Control Volumes 240 610 Rate Balances for Control Volumes at Steady State 241 6101 One-Inlet, One-Exit Control Volumes at Steady State 241 6102 Applications of the Rate Balances to Control Volumes at Steady State 242 611 Isentropic Processes 246 6111 General Considerations 246 6112 Using the Ideal Gas Model 247 6113 Illustrations: Isentropic Processes of Air 249 612 Isentropic Efficiencies of Turbines, Nozzles, Compressors, and Pumps 251 6121 Isentropic Turbine Efficiency 251 6122 Isentropic Nozzle Efficiency 254 6123 Isentropic Compressor and Pump Efficiencies 256 613 Heat Transfer and Work in Internally Reversible, Steady-State Flow Processes 258 6131 Heat Transfer 258 6132 Work 258 6133 Work in Polytropic Processes 260 Chapter Summary and Study Guide 261 7 Exergy Analysis 277 71 Introducing Exergy 278 72 Conceptualizing Exergy 279 721 Environment and Dead State 279 722 Defining Exergy 280 73 Exergy of a System 280 731 Exergy Aspects 282 732 Specific Exergy 282 733 Exergy Change 284 74 Closed System Exergy Balance 285 741 Introducing the Closed System Exergy Balance 285 742 Closed System Exergy Rate Balance 288 743 Exergy Destruction and Loss 289 744 Exergy Accounting 291 75 Exergy Rate Balance for Control Volumes at Steady State 292 751 Comparing Energy and Exergy for Control Volumes at Steady State 294 752 Evaluating Exergy Destruction in Control Volumes at Steady State 295 753 Exergy Accounting in Control Volumes at Steady State 298 76 Exergetic (Second Law) Efficiency 300 761 Matching End Use to Source 301 762 Exergetic Efficiencies of Common Components 303 763 Using Exergetic Efficiencies 305 77 Thermoeconomics 306 771 Costing 306 772 Using Exergy in Design 307 773 Exergy Costing of a Cogeneration System 308 Chapter Summary and Study Guide 312 57 Second Law Aspects of Refrigeration and Heat Pump Cycles Interacting with Two Reservoirs 194 571 Limits on Coefficients of Performance 194 572 Corollaries of the Second Law for Refrigeration and Heat Pump Cycles 195 58 The Kelvin and International Temperature Scales 196 581 The Kelvin Scale 196 582 The Gas Thermometer 198 583 International Temperature Scale 199 59 Maximum Performance Measures for Cycles Operating Between Two Reservoirs 199 591 Power Cycles 200 592 Refrigeration and Heat Pump Cycles 201 510 Carnot Cycle 204 5101 Carnot Power Cycle 204 5102 Carnot Refrigeration and Heat Pump Cycles 205 5103 Carnot Cycle Summary 206 511 Clausius Inequality 206 Chapter Summary and Study Guide 208 6 Using Entropy 217 61 Entropy–A System Property 218 611 Defining Entropy Change 218 612 Evaluating Entropy 219 613 Entropy and Probability 219 62 Retrieving Entropy Data 219 621 Vapor Data 220 622 Saturation Data 220 623 Liquid Data 220 624 Computer Retrieval 221 625 Using Graphical Entropy Data 221 63 Introducing the T dS Equations 222 64 Entropy Change of an Incompressible Substance 223 65 Entropy Change of an Ideal Gas 224 651 Using Ideal Gas Tables 225 652 Assuming Constant Specific Heats 226 653 Computer Retrieval 226 66 Entropy Change in Internally Reversible Processes of Closed Systems 227 661 Area Representation of Heat Transfer 227 662 Carnot Cycle Application 228 663 Work and Heat Transfer in an Internally Reversible Process of Water 228 67 Entropy Balance for Closed Systems 230 671 Interpreting the Closed System Entropy Balance 231 672 Evaluating Entropy Production and Transfer 231 673 Applications of the Closed System Entropy Balance 232 674 Closed System Entropy Rate Balance 234 68 Directionality of Processes 236 681 Increase of Entropy Principle 236 682 Statistical Interpretation of Entropy 238 9122 Velocity of Sound and Mach Number 428 9123 Determining Stagnation State Properties 431 913 Analyzing One-Dimensional Steady Flow in Nozzles and Diffusers 431 9131 Exploring the Effects of Area Change in Subsonic and Supersonic Flows 431 9132 Effects of Back Pressure on Mass Flow Rate 433 9133 Flow Across a Normal Shock 435 914 Flow in Nozzles and Diffusers of Ideal Gases with Constant Specific Heats 437 9141 Isentropic Flow Functions 437 9142 Normal Shock Functions 440 Chapter Summary and Study Guide 443 10 Refrigeration and Heat Pump Systems 457 101 Vapor Refrigeration Systems 458 1011 Carnot Refrigeration Cycle 458 1012 Departures from the Carnot Cycle 459 102 Analyzing Vapor-Compression Refrigeration Systems 460 1021 Evaluating Principal Work and Heat Transfers 460 1022 Performance of Ideal Vapor-Compression Systems 461 1023 Performance of Actual Vapor-Compression Systems 463 1024 The p–h Diagram 466 103 Selecting Refrigerants 467 104 Other Vapor-Compression Applications 470 1041 Cold Storage 470 1042 Cascade Cycles 470 1043 Multistage Compression with Intercooling 471 105 Absorption Refrigeration 472 106 Heat Pump Systems 474 1061 Carnot Heat Pump Cycle 474 1062 Vapor-Compression Heat Pumps 475 107 Gas Refrigeration Systems 477 1071 Brayton Refrigeration Cycle 477 1072 Additional Gas Refrigeration Applications 481 1073 Automotive Air Conditioning Using Carbon Dioxide 482 Chapter Summary and Study Guide 483 11 Thermodynamic Relations 493 111 Using Equations of State 494 1111 Getting Started 494 1112 Two-Constant Equations of State 495 1113 Multiconstant Equations of State 498 112 Important Mathematical Relations 499 113 Developing Property Relations 502 1131 Principal Exact Differentials 502 1132 Property Relations from Exact Differentials 503 1133 Fundamental Thermodynamic Functions 507 8 Vapor Power Systems 327 81 Introducing Vapor Power Plants 332 82 The Rankine Cycle 334 821 Modeling the Rankine Cycle 335 822 Ideal Rankine Cycle 337 823 Effects of Boiler and Condenser Pressures on the Rankine Cycle 340 824 Principal Irreversibilities and Losses 342 83 Improving Performance—Superheat, Reheat, and Supercritical 345 84 Improving Performance—Regenerative Vapor Power Cycle 350 841 Open Feedwater Heaters 350 842 Closed Feedwater Heaters 353 843 Multiple Feedwater Heaters 355 85 Other Vapor Power Cycle Aspects 358 851 Working Fluids 358 852 Cogeneration 359 853 Carbon Capture and Storage 360 86 Case Study: Exergy Accounting of a Vapor Power Plant 362 Chapter Summary and Study Guide 367 9 Gas Power Systems 379 91 Introducing Engine Terminology 380 92 Air-Standard Otto Cycle 383 93 Air-Standard Diesel Cycle 387 94 Air-Standard Dual Cycle 390 95 Modeling Gas Turbine Power Plants 393 96 Air-Standard Brayton Cycle 394 961 Evaluating Principal Work and Heat Transfers 395 962 Ideal Air-Standard Brayton Cycle 396 963 Considering Gas Turbine Irreversibilities and Losses 401 97 Regenerative Gas Turbines 403 98 Regenerative Gas Turbines with Reheat and Intercooling 406 981 Gas Turbines with Reheat 406 982 Compression with Intercooling 408 983 Reheat and Intercooling 412 984 Ericsson and Stirling Cycles 414 99 Gas Turbine–Based Combined Cycles 416 991 Combined Gas Turbine–Vapor Power Cycle 416 992 Cogeneration 421 910 Integrated Gasification Combined-Cycle Power Plants 421 911 Gas Turbines for Aircraft Propulsion 423 912 Compressible Flow Preliminaries 427 9121 Momentum Equation for Steady One-Dimensional Flow 427 127 Psychrometric Charts 584 128 Analyzing Air-Conditioning Processes 586 1281 Applying Mass and Energy Balances to Air-Conditioning Systems 586 1282 Conditioning Moist Air at Constant Composition 587 1283 Dehumidification 589 1284 Humidification 592 1285 Evaporative Cooling 594 1286 Adiabatic Mixing of Two Moist Air Streams 596 129 Cooling Towers 598 Chapter Summary and Study Guide 600 13 Reacting Mixtures and Combustion 611 131 Introducing Combustion 612 1311 Fuels 612 1312 Modeling Combustion Air 613 1313 Determining Products of Combustion 616 1314 Energy and Entropy Balances for Reacting Systems 618 132 Conservation of Energy—Reacting Systems 619 1321 Evaluating Enthalpy for Reacting Systems 619 1322 Energy Balances for Reacting Systems 621 1323 Enthalpy of Combustion and Heating Values 627 133 Determining the Adiabatic Flame Temperature 630 1331 Using Table Data 630 1332 Using Computer Software 630 1333 Closing Comments 632 134 Fuel Cells 633 1341 Proton Exchange Membrane Fuel Cell 634 1342 Solid Oxide Fuel Cell 635 135 Absolute Entropy and the Third Law of Thermodynamics 636 1351 Evaluating Entropy for Reacting Systems 637 1352 Entropy Balances for Reacting Systems 638 1353 Evaluating Gibbs Function for Reacting Systems 641 136 Conceptualizing Chemical Exergy 642 1361 Working Equations for Chemical Exergy 644 1362 Evaluating Chemical Exergy for Several Cases 645 1363 Closing Comments 646 137 Standard Chemical Exergy 646 1371 Standard Chemical Exergy of a Hydrocarbon: CaHb 647 1372 Standard Chemical Exergy of Other Substances 650 138 Applying Total Exergy 650 1381 Calculating Total Exergy 651 1382 Calculating Exergetic Efficiencies of Reacting Systems 655 Chapter Summary and Study Guide 657 114 Evaluating Changes in Entropy, Internal Energy, and Enthalpy 508 1141 Considering Phase Change 508 1142 Considering Single-Phase Regions 511 115 Other Thermodynamic Relations 516 1151 Volume Expansivity, Isothermal and Isentropic Compressibility 516 1152 Relations Involving Specific Heats 518 1153 Joule–Thomson Coefficient 520 116 Constructing Tables of Thermodynamic Properties 522 1161 Developing Tables by Integration Using p–? –T and Specific Heat Data 523 1162 Developing Tables by Differentiating a Fundamental Thermodynamic Function 524 117 Generalized Charts for Enthalpy and Entropy 526 118 p–?–T Relations for Gas Mixtures 532 119 Analyzing Multicomponent Systems 536 1191 Partial Molal Properties 537 1192 Chemical Potential 539 1193 Fundamental Thermodynamic Functions for Multicomponent Systems 540 1194 Fugacity 542 1195 Ideal Solution 545 1196 Chemical Potential for Ideal Solutions 546 Chapter Summary and Study Guide 547 12 Ideal Gas Mixture and Psychrometric Applications 557 121 Describing Mixture Composition 558 122 Relating p, V, and T for Ideal Gas Mixtures 561 123 Evaluating U, H, S, and Specific Heats 562 1231 Evaluating U and H 563 1232 Evaluating c? and cp 563 1233 Evaluating S 563 1234 Working on a Mass Basis 564 124 Analyzing Systems Involving Mixtures 565 1241 Mixture Processes at Constant Composition 565 1242 Mixing of Ideal Gases 570 125 Introducing Psychrometric Principles 574 1251 Moist Air 574 1252 Humidity Ratio, Relative Humidity, Mixture Enthalpy, and Mixture Entropy 575 1253 Modeling Moist Air in Equilibrium with Liquid Water 577 1254 Evaluating the Dew Point Temperature 578 1255 Evaluating Humidity Ratio Using the Adiabatic-Saturation Temperature 582 126 Psychrometers: Measuring the Wet-Bulb and Dry-Bulb Temperatures 583 1443 Ionization 686 1444 Simultaneous Reactions 687 145 Equilibrium between Two Phases of a Pure Substance 690 146 Equilibrium of Multicomponent, Multiphase Systems 691 1461 Chemical Potential and Phase Equilibrium 692 1462 Gibbs Phase Rule 694 Chapter Summary and Study Guide 695 14 Chemical and Phase Equilibrium 667 141 Introducing Equilibrium Criteria 668 1411 Chemical Potential and Equilibrium 669 1412 Evaluating Chemical Potentials 670 142 Equation of Reaction Equilibrium 672 1421 Introductory Case 672 1422 General Case 673 143 Calculating Equilibrium Compositions 674 1431 Equilibrium Constant for Ideal Gas Mixtures 674 1432 Illustrations of the Calculation of Equilibrium Compositions for Reacting Ideal Gas Mixtures 677 1433 Equilibrium Constant for Mixtures and Solutions 681 144 Further Examples of the Use of the Equilibrium Constant 682 1441 Determining Equilibrium Flame Temperature 682 1442 Van’t Hoff Equation 685