Introduction to CHEMICAL ENGINEERING THERMODYNAMICSThis book, now in its second edition, continues to provide a comprehensive introduction to the principles of chemical engineering thermodynamics and also introduces the student to the application of principles to various practical areas. The book emphasizes the role of the fundamental principles of thermodynamics in the derivation of significant relationships between the various thermodynamic properties. The initial chapter provides an overview of the basic concepts and processes, and discusses the important units and dimensions involved. The ensuing chapters, in a logical presentation, thoroughly cover the first and second laws of thermodynamics, the heat effects, the thermodynamic properties and their relations, refrigeration and liquefaction processes, and the equilibria between phases and in chemical reactions. The book is suitably illustrated with a large number of visuals. In the second edition, new sections on Quasi-Static Process and Entropy Change in Reversible and Irreversible Processes are included. Besides, new Solved Model Question Paper and several new Multiple Choice Questions are also added that help develop the students’ ability and confidence in the application of the underlying concepts. Primarily intended for the undergraduate students of chemical engineering and other related engineering disciplines such as polymer, petroleum and pharmaceutical engineering, the book will also be useful for the postgraduate students of the subject as well as professionals in the relevant fields. |
Contents
683 Residual Enthalpy Relation from Cubic Equation of State | 246 |
69 Fugacity and Fugacity Coefficient | 247 |
691 Effect of Temperature and Pressure on Fugacity | 249 |
692 Fugacity Coefficient from Compressibility Factor | 250 |
694 Fugacity Coefficient by Equation of State | 252 |
Summary | 253 |
Important Equations | 254 |
Exercises | 256 |
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17 | |
18 | |
19 | |
20 | |
21 | |
22 | |
24 | |
26 | |
28 | |
32 | |
35 | |
Exercises | 36 |
2 First Law ofThermodynamics | 39 |
Mechanical Equivalence of Heat | 40 |
22 Statement of First Law of Thermodynamics | 41 |
24 Concept of Internal Energy | 42 |
25 Sign Convention for Heat and Work Interactions | 43 |
27 Internal Energy of an Ideal Gas | 47 |
28 Thermodynamic State | 48 |
210 Enthalpy | 49 |
211 Heat Capacity | 51 |
2111 Relation between CP and CV | 52 |
212 Adiabatic Process or Isocaloric Process | 54 |
213 Reversible Adiabatic Expansion of Ideal Gas | 55 |
2133 Enthalpy H | 56 |
2135 Relation between Pressure and Volume | 57 |
214 ConstantVolume Isochoric Process | 60 |
216 ConstantTemperature Isothermal Process | 61 |
217 Mass Balance for Open System | 71 |
218 Energy Balance for Open System or First Law of Thermodynamics
to Flow Processes | 72 |
Summary | 75 |
Key Terms | 76 |
Exercises | 78 |
3 Properties of PureSubstances | 83 |
31 Pure Substance | 84 |
34 PVT Behaviour of Pure Substance | 88 |
342 PV Diagram | 89 |
343 PT Diagram | 90 |
35 Equation of StateMathematical Representation of PVT Behaviour | 91 |
36 Ideal Gas Equation of State | 92 |
37 Equation of State for Real Gases | 96 |
372 RedlichKwong Equation of State | 100 |
373 RedlichKwongSoave Equation of State | 102 |
374 PengRobinson Equation of State | 103 |
377 Virial Equation of State | 104 |
38 Compressibility Factor | 109 |
39 Law of Corresponding State | 110 |
310 Acentric Factor | 111 |
Summary | 113 |
Important Equations | 115 |
Exercises | 117 |
4 Heat Effects | 121 |
41 Exothermic and Endothermic Reactions | 122 |
43 Hesss Law of Constant Heat Summation | 123 |
431 Thermodynamic Explanation of Hesss Law | 124 |
45 Standard Heat of Formation | 125 |
46 Standard Heat of Combustion | 128 |
47 Adiabatic Flame Temperature | 130 |
Kirchhoff s Equation | 132 |
Summary | 136 |
Important Equations | 137 |
Exercises | 138 |
5 Second Law of Thermodynamics | 141 |
51 Limitations of First Law of Thermodynamics | 142 |
52 Basic Concepts of Heat Engines Heat Pumps and Refrigerators | 143 |
522 Heat Pumps | 145 |
523 Refrigerators | 146 |
53 Statements of Second Law of Thermodynamics | 147 |
531 KelvinPlanck Statement | 148 |
533 Equivalence of KelvinPlanck and Clausius Statements | 149 |
54 Carnot Cycle | 150 |
541 Efficiency of Carnot Cycle | 154 |
55 Carnot Theorem | 158 |
56 Thermodynamic Temperature Scale | 160 |
57 Concept of Entropy | 163 |
571 EntropyA Thermodynamic State Function | 164 |
572 EntropyAt a glance | 165 |
573 Relation between Entropy and Internal Energy | 166 |
581 Entropy Change in Reversible Process | 167 |
582 Entropy Change in Irreversible Process | 168 |
583 Entropy at Phase Change | 169 |
584 Entropy Changes of Ideal Gas | 170 |
585 Entropy Changes in Mixture of Nonidentical Ideal Gases | 172 |
586 Entropy Changes with Temperature | 174 |
59 Mathematical Statement of Second Law of Thermodynamics | 178 |
510 Entropy Balances for Open Systems | 183 |
511 The Third Law of Thermodynamics | 184 |
Microscopic Point of View | 185 |
513 Criterion of Irreversibility | 187 |
515 Irreversibility and Lost Work | 189 |
Summary | 191 |
Key Terms | 193 |
Important Equations | 194 |
Exercises | 197 |
6 THERMODYNAMIC PROPERTY RELATIONS | 200 |
61 Thermodynamic Properties | 201 |
63 Free Energy Functions | 204 |
631 Helmholtz Free Energy Work Function A | 205 |
632 Gibbs Free Energy Gibbs Function G | 206 |
633 Variation of Free Energy with Pressure at Constant Temperature | 207 |
641 Fundamental Property Relations | 208 |
642 Maxwells Relations | 209 |
643 Clapeyron Equation | 210 |
644 GibbsHelmholtz Equation | 214 |
645 General Equations for Differential Changes in Internal Energy | 216 |
646 General Equations for Differential Changes in Enthalpy | 217 |
647 General Equations for Differential Changes in Entropy | 218 |
648 TdS Equations | 219 |
6410 Isothermal Compressibility and Volume Expansivity | 223 |
6411 JouleThomson Coefficient | 230 |
65 Residual Property | 236 |
662 Residual Enthalpy Relation from Equation of State | 238 |
663 Residual Entropy Relation from Equation of State | 240 |
664 Residual Gibbs Function Relation from Equation of State | 241 |
67 Residual Properties from Virial Equation of State | 242 |
68 Residual Properties from Cubic Equation of State | 245 |
7 THERMODYNAMICS TO FLOW PROCESSES | 261 |
711 Continuity Equation and Mass Analysis of Control Volume | 262 |
712 Energy Analysis of Control Volume and Bernoullis Equation | 265 |
713 Throttling Device | 269 |
714 Compressor | 271 |
715 Ejectors or Jet Pumps | 277 |
716 Heat Exchangers | 278 |
717 Nozzles and Diffusers | 281 |
72 Unsteadyflow Processes and Devices | 289 |
Summary | 291 |
Important Equations | 292 |
Exercises | 294 |
8 REFRIGERATION AND LIQUEFACTION PROCESSES | 296 |
81 Refrigeration | 297 |
812 Coefficient of Performance | 299 |
813 Capacity of Refrigerator | 300 |
814 Carnot Refrigeration Cycle | 301 |
815 VapourCompression Refrigeration Cycle | 306 |
816 Absorption Refrigeration Cycle | 313 |
817 Air Refrigeration Cycle | 316 |
818 Comparative Study of Carnot VapourCompression
Absorption and Air Refrigeration Systems | 322 |
819 Selection of Right Refrigerant | 323 |
82 Liquefaction Process | 328 |
822 JouleThomson Expansion Isenthalpic Expansion | 331 |
823 Exchanging Heat at Constant Pressure | 333 |
Key Terms | 334 |
Important Equations | 335 |
Exercises | 336 |
PROPERTIES | 340 |
91 Partial Molar Properties | 341 |
911 Evaluation of Partial Molar Properties | 343 |
92 Chemical Potential | 350 |
921 Influence of Pressure on Chemical Potential | 352 |
93 Activity and Activity Coefficient | 354 |
931 Temperature Dependence of Activity Coefficient | 355 |
94 GibbsDuhem Equation | 356 |
95 Fugacity of Component in Mixture | 360 |
96 Fugacity of Liquids and Solids | 362 |
Gibbs Theorem | 367 |
972 Gibbs Free Energy Change of Mixing | 369 |
973 Enthalpy Change of Mixing | 370 |
974 Volume Change of Mixing | 372 |
98 Excess Property of Mixture | 373 |
LewisRandall Rule | 376 |
910 Raoults Law and Ideal Solution | 378 |
911 Henrys Law and Dilute Solution | 379 |
Summary | 381 |
Key Terms | 382 |
Exercises | 384 |
10 VAPOURLIQUID EQUILIBRIUM | 390 |
101 Criteria of Equilibrium | 391 |
102 Criterion for Phase Equilibrium | 393 |
103 Phase Rule for Nonreacting Systems and Duhems Theorem | 394 |
104 Phase Equilibrium for Singlecomponent System | 396 |
105 Phase Equilibrium for Multicomponent System | 398 |
106 VapourLiquid Equilibrium Diagram for Binary Mixture | 399 |
1061 TemperatureComposition Txy Diagram | 400 |
1062 PressureComposition Pxy Diagram | 401 |
Raoults Law | 403 |
108 Modified Raoults Law for VapourLiquid Equilibrium | 405 |
Nonideal Solutions | 411 |
1010 Azeotrope Formation | 413 |
Excess Gibbs Free
Energy Model | 415 |
10111 Wohls Equation | 416 |
10112 Margules Equation | 417 |
10113 van Laar Equation | 418 |
Wilson and NRTL Equations | 422 |
10115 Universal QuasiChemical Equation UNIQUAC | 426 |
10116 Universal Functional Activity Coefficient UNIFAC Method | 428 |
1012 VapourLiquid Equilibrium at High Pressure | 429 |
10121 Methodology for Bubble Point Calculations | 431 |
10122 Methodology for Dew Point Calculations | 434 |
10123 Flash Calculations | 437 |
1013 Thermodynamic Consistency Test of VLE Data | 441 |
Summary | 445 |
Key Terms | 447 |
Important Equations | 448 |
Exercises | 450 |
11 ADDITIONAL TOPICS IN PHASE EQUILIBRIUM | 456 |
1111 Effect of Temperature on LiquidLiquid Equilibrium | 457 |
112 Ternary LiquidLiquid Equilibrium | 460 |
113 SolidLiquid Equilibrium | 461 |
114 Depression of Freezing Point of Solution | 463 |
115 Elevation of Boiling Point of Solution | 466 |
116 SolidVapour Equilibrium | 469 |
117 Osmotic Pressure and Equilibrium | 470 |
Key Terms | 473 |
Exercises | 474 |
12 CHEMICAL REACTION EQUILIBRIA | 476 |
121 Reaction Coordinate | 477 |
122 Multireaction Stoichiometry | 479 |
123 Equilibrium Criterion of Chemical Reaction | 481 |
124 Equilibrium Constant | 482 |
125 Standard Gibbs Free Energy Change | 484 |
126 Feasibility of Chemical Reaction | 485 |
127 Relation between Equilibrium Constant and Standard Gibbs Free
Energy Change | 487 |
Vant Hoff Equation | 489 |
129 Homogeneous Gasphase Reaction Equilibrium | 494 |
1210 Effect of Pressure on Chemical Equilibrium | 498 |
1211 Effect of Other Factors on Equilibrium Conversion | 500 |
12112 Effect of Presence of Excess Reactants | 502 |
1212 Homogeneous LiquidPhase Reaction Equilibrium | 503 |
1213 Heterogeneous Reaction Equilibria | 506 |
12132 LiquidGas Reaction Equilibrium | 510 |
1214 Phase Rule For Reacting Systems | 511 |
1215 Chemical Equilibrium for Simultaneous Reactions | 513 |
1216 Fuel Cell | 517 |
Summary | 519 |
Key Terms | 520 |
Important Equations | 521 |
Exercises | 523 |
Property Tables | 531 |
Solved Model Question Papers | 561 |
Multiple Choice Questions | 614 |
657 | |
659 | |
Other editions - View all
Introduction to Chemical Engineering Thermodynamics Gopinath Halder,Halder Gopinath No preview available - 2009 |
Common terms and phrases
activity coefficients adiabatic adiabatic process amount of heat Appendix C Multiple azeotrope binary Calculate Carnot cycle change in entropy chemical potential chemical reaction composition compressor constant pressure constant temperature control volume cooling cylinder Determine diagram differential enthalpy entropy entropy change equation equilibrium constant estimated ethanol EXAMPLE expansion flow fluid free energy change fugacity function gases Gibbs free energy given heat engine heat pump Hence ideal gas ideal solution internal energy irreversible isentropic isothermal process J/mol Joule Joule Thomson kJ/kg kJ/kg-K law of thermodynamics low temperature mass mixture mol per cent mole fraction molecules number of moles partial molar volume piston pure component pure substance Raoult s law refrigeration cycle relation reservoir reversible process saturated liquid temperature and pressure thermal vapour phase vapour pressure virial Waals