Learn the basics of thermodynamics in this complete and practice-oriented introduction for students of chemical engineering
Thermodynamics is a vital branch of physics that focuses upon the interaction of heat, work, and temperature with energy, radiation, and matter. Thermodynamics can apply to a wide range of sciences, but is particularly important in chemical engineering, where the interconnection of heat and work with chemical reactions or physical changes of state are studied according to the laws of thermodynamics. Moreover, thermodynamics in chemical engineering focuses upon pure fluid and mixture properties, phase equilibrium, and chemical reactions within the confines of the laws of thermodynamics.
Given that thermodynamics is an essential course of study in chemical and petroleum engineering, Thermodynamics for Chemical Engineers provides an important introduction to the subject that comprehensively covers the topic in an easily-digestible manner. Suitable for undergraduate and graduate students, the text introduces the basic concepts of thermodynamics thoroughly and concisely while providing practice-oriented examples and illustrations. Thus, the book helps students bridge the gap between theoretical knowledge and basic experiments and measurement characteristics.
Thermodynamics for Chemical Engineers readers will also find: - Practice-oriented examples to help students connect the learned concepts to actual laboratory instruments and experiments - A broad suite of illustrations throughout the text to help illuminate the information presented - Authors with decades working in chemical engineering and teaching thermodynamics
Thermodynamics for Chemical Engineers is the ideal resource not just for undergraduate and graduate students in chemical and petroleum engineering, but also for anyone looking for a basic guide to thermodynamics.
Table of Contents
Preface xi
1 Introduction 1
1.1 Definition 1
1.2 Dimensions, Fundamental Quantities, and Units 2
1.3 Secondary or Derived Physical Quantities 4
1.4 SI Usage of Units and Symbols 13
1.5 Thermodynamic Systems and Variables 14
1.6 Zeroth Law 16
Problems for Chapter 1 16
2 Energy and the First Law 21
2.1 Introduction 21
2.2 Energy 22
2.3 First Law of Thermodynamics 24
2.4 Application of Solution Procedure to Simple Cases 30
2.5 Practical Application Examples 34
2.5.1 Compressors/Pumps 34
2.5.2 Turbines/Expanders 35
2.5.3 Condensers/Vaporizers/Reboilers 36
2.5.4 Heat Exchanger 36
2.5.5 Sample Cylinder 38
2.6 Differential Form 39
2.7 Inserting Time: Unsteady-State Flow Process 39
2.8 Recap 40
Problems for Chapter 2 40
Reference 45
3 PVT Relations and Equations of State 47
3.1 Introduction 47
3.2 Graphical Representations 47
3.3 Critical Region 53
3.4 Tabular Representations 54
3.5 Mathematical Representations 56
3.5.1 Perfect and Ideal Gas EOS 57
3.5.2 Reversible Processes Involving Ideal Gases in Closed Systems 58
3.5.2.1 Constant Volume (Isochoric) Process 59
3.5.2.2 Constant Pressure (Isobaric) Process 59
3.5.2.3 Constant Temperature (Isothermal) Process 60
3.5.2.4 Adiabatic Process 60
3.5.2.5 Polytropic Processes 62
3.5.3 Virial Equation of State 65
3.5.3.1 Correlations for the Second and Third Virial Coefficient 69
3.5.4 Other Special Equations 75
3.5.4.1 Tait Equation 75
3.5.4.2 Rackett Equation 75
3.5.4.3 Riedel Equation 75
3.5.4.4 Yen and Woods Equation 76
3.5.4.5 Chueh and Prausnitz Equation 76
3.5.4.6 Generalized Lee-Kesler Correlation 76
3.5.5 Cubic Equations of State 77
3.5.5.1 van der Waals (vdW) Equation of State 77
3.5.5.2 Other Cubic EOS 79
3.5.5.3 Redlich-Kwong (RK) EOS 80
3.5.5.4 Soave-Redlich-Kwong (SRK) Equation of State 82
3.5.5.5 Peng-Robinson (PR) Equation of State 82
3.5.6 Multiparameter Equations of State 83
3.5.6.1 Benedict-Webb-Rubin (BWR) Equation of State 83
3.5.6.2 Boublik-Alder-Chen-Kreglewski 83
3.5.7 Reference Equation of State 85
3.6 Calculation of Volumes from EOS 86
3.7 Vapor Pressure and Enthalpy of Vaporization Correlations 89
3.8 Ideal Gas Enthalpy Changes: Applications 91
3.8.1 Heat of Reaction 91
3.8.1.1 Standard Heat of Reaction 91
3.8.1.2 Standard Heat of Formation 92
3.8.1.3 Standard Heat of Combustion 92
3.8.2 Temperature Dependence of the Heat of Reaction 92
3.8.3 Practical Calculations 94
3.8.3.1 Adiabatic Flame Temperature 95
3.8.3.2 Reaction with Heat Transfer 95
Problems for Chapter 3 99
References 109
4 Second Law of Thermodynamics 113
4.1 Introduction 113
4.2 General and Classical Statements of the Second Law 114
4.3 Heat Engines, Refrigerators, and Cycles 116
4.4 Implications of the Second Law 117
4.5 Efficiency 127
4.6 Specific Heat/Heat Capacity 128
4.6.1 Entropy Changes for Ideal Gases 130
4.7 Entropy Balance Equation for Open Systems 133
4.8 Availability and Maximum/Minimum Work 137
Problems for Chapter 4 139
5 Thermodynamic Relations 145
5.1 Introduction 145
5.2 Mathematics Review 145
5.2.1 Exact Differentials 145
5.2.2 Inexact Differentials and Line Integration 146
5.2.3 Properties of Functions of Several Variables 147
5.3 Fundamental Thermodynamics Equation 148
5.4 Legendre Transforms 149
5.5 Maxwell Relations 151
5.6 Derivation of Thermodynamic Relationships 153
5.7 Open Systems: Chemical Potential 155
5.8 Property Change Calculations 157
5.8.1 Temperature Derivatives 157
5.8.2 Volume Derivatives 158
5.8.3 Pressure Derivatives 159
5.9 Residual Properties 160
5.10 Property Changes Using Residual Functions 163
5.11 Generalized Correlations for Residual Functions 166
5.12 Two-Phase Systems - Clapeyron Equation 169
Problems for Chapter 5 172
6 Practical Applications for Thermodynamics 179
6.1 Fluid Flow 179
6.1.1 Flow Through Ducts 179
6.1.2 Properties of Sub-cooled Liquids (Compressed Liquid) 184
6.1.3 Pumps, Compressors, and Expanders 186
6.2 Heat Engines and Refrigeration Units 196
6.2.1 Heat and Work 196
6.2.2 Rankine Cycle 198
6.2.3 Modifications of the Rankine Cycle 204
6.2.4 Internal Combustion Engines 211
6.2.4.1 Otto Cycle 211
6.2.4.2 Diesel Engine Cycle 216
6.2.4.3 Gas Turbine Cycle 220
6.2.5 Refrigeration: The Carnot Cycle for a Refrigeration Unit 225
6.2.5.1 Vapor Compression Cycle 226
6.2.5.2 Air Refrigeration Cycle 229
6.2.5.3 Absorption Refrigeration 233
6.2.5.4 Heat Pump 235
6.2.5.5 Liquefaction Process 235
6.2.6 Process Simulators: Using Process Simulation for Fluid Flow Problems 241
Problems for Chapter 6 249
7 Solution Theory 257
7.1 Introduction 257
7.2 Composition Variables 257
7.3 Chemical Potential 260
7.3.1 More Maxwell Relations 261
7.4 Partial Molar Properties 262
7.5 General Gibbs-Duhem Equation 268
7.6 Differential Thermodynamic Properties in Open Systems in Terms of Measurables 270
7.6.1 Using T and nV 270
7.6.2 Using T, P 271
7.7 Ideal Gas Mixtures 271
7.8 Fugacity and Fugacity Coefficient for Pure Substances 275
7.9 Equations for Calculating Fugacity 277
7.9.1 Fugacity of a Vapor (Point A) 277
7.9.2 Fugacity of a Vapor or Saturated Liquid (Point B) 277
7.9.3 Fugacity of Liquid (Point C) 278
7.9.4 Fugacity of Solid at the Melting Point (Point D) 279
7.9.5 Fugacity of a Solid (Point E) 279
7.10 Application of Fugacity Equation to Gases and Liquids 280
7.11 Fugacity and Fugacity Coefficient in a Solution 284
7.12 Calculation of the Fugacity and Fugacity Coefficient in Solution 287
7.12.1 Using Cubic EOS 291
7.12.1.1 Mixing Rules 292
7.13 Ideal Solutions 298
7.14 Excess Properties. Activity Coefficients 301
7.15 Activity Coefficients with Different Standard States 303
7.16 Effect of Pressure on the Fugacity in Solution and Activity Coefficients Using the Lewis-Randall Rule 305
7.17 Property Change on Mixing 307
7.18 Excess Gibbs Energy Models 310
Problems for Chapter 7 318
References 323
8 Phase Equilibrium 325
8.1 Introduction 325
8.2 Equilibrium 325
8.3 Gibbs Phase Rule 329
8.4 Pure Components and Phase Equilibria 330
8.5 Different Phase Diagrams for Binary Mixtures at Vapor-Liquid Equilibrium (VLE) 332
8.6 Vapor/Liquid Equilibrium Relationship 336
8.7 Phase Calculations Using the Gamma-Phi Formulation 338
8.7.1 Bubble Pressure 339
8.7.2 Bubble Temperature 340
8.7.3 Dew Pressure 341
8.7.4 Dew Temperature 342
8.7.5 Flash 342
8.8 Phase Calculations Using the Phi-Phi Formulation 349
8.9 Modern Approach to Phase Equilibrium Calculations 358
8.9.1 Equal Area Rule for Binary Mixtures 359
8.9.2 A General Approach for Multicomponent and Multiphase Systems 365
8.10 Binary Liquid-Liquid Equilibrium (LLE) 374
8.11 Binary Vapor-Liquid-Liquid Equilibrium (VLLE) 381
8.12 Binary Vapor-Solid Equilibrium (VSE) 387
8.13 Binary Liquid-Solid Equilibrium (LSE) 391
Problems for Chapter 8 397
References 403
9 Chemical Reaction Equilibria 405
9.1 Introduction 405
9.2 Nature of Reactions 406
9.3 Chemical Reaction Stoichiometry 406
9.4 Extent of Reaction 407
9.5 Phase Rule for Reacting Systems 408
9.6 Principles of Reaction Equilibria 410
9.7 Understanding the Reaction Equilibria 413
9.8 Equilibrium Constant 415
9.9 Temperature Dependence of the Equilibrium Constant 417
9.10 Standard States 420
9.11 Applications to Different Types of Reactions 420
9.11.1 Reactions in Single-Phase Systems 421
9.11.1.1 Gas-Phase Reactions 421
9.11.1.2 Liquid-Phase Reactions 422
9.11.1.3 Solid Reactions 424
9.11.2 Heterogeneous Reactions (Different Phase Systems) 425
9.12 Multi-reactions 429
9.13 Nonstoichiometric Solution 431
9.14 Equal Area Rule for Reactive Thermodynamic Equilibrium Calculations 434
Problems for Chapter 9 440
References 447
A Appendices 449
A.1 Instructions to Add an Add-In Your Computer 449
A.2 Excel® LK CALC Add-In 449
A.3 Excel® STEAM CALC Add-In 451
A.4 Heat Capacity Equations for an Ideal Gas 453
A.5 Antoine Equation Constants 454
A.6 Heat Capacity Equations for liquids 454
A.7 Iterative Procedures for the Calculation of Vapor Liquid Equilibrium 454
A.7.1 Bubble Point Calculations 454
A.7.1.1 Bubble Pressure Calculation 454
A.7.1.2 Bubble Temperature Calculation 455
A.7.2 Dew Point Calculations 456
A.7.2.1 Dew Pressure Calculation 456
A.7.2.2 Dew Temperature Calculation 457
A.7.3 Flash Calculation 458
References 460
Index 461
