Advanced Thermodynamics for Engineers (eBook)

Cover 1
Contents 4
Preface 8
Structure 12
Symbols 14
Chapter 1. State of Equilibrium 20
1.1 Equilibrium of a thermodynamic system 21
1.2 Helmholtz energy (Helmholtz function) 24
1.3 Gibbs energy (Gibbs function) 25
1.4 The use and significance of the Helmholtz and Gibbs energies 25
1.5 Concluding remarks 28
Problems 29
Chapter 2. Availability and Exergy 32
2.1 Displacement work 32
2.2 Availability 33
2.3 Examples 34
2.4 Available and non-available energy 40
2.5 Irreversibility 40
2.6 Graphical representation of available energy and irreversibility 44
2.7 Availability balance for a closed system 46
2.8 Availability balance for an open system 53
2.9 Exergy 55
2.10 The variation of flow exergy for a perfect gas 61
2.11 Concluding remarks 62
Problems 62
Chapter 3. Pinch Technology 66
3.1 A heat transfer network without a pinch problem 68
3.2 A heat transfer network with a pinch point 75
3.3 Concluding remarks 79
Problems 80
Chapter 4. Rational Efficiency of a Powerplant 83
4.1 The influence of fuel properties on thermal efficiency 83
4.2 Rational efficiency 84
4.3 Rankine cycle 88
4.4 Examples 90
4.5 Concluding remarks 101
Problems 101
Chapter 5. Efficiency of Heat Engines at Maximum Power 104
5.1 Efficiency of an internally reversible heat engine when producing maximum power output 104
5.2 Efficiency of combined cycle internally reversible heat engines when producing maximum power output 111
5.3 Concluding remarks 115
Problems 115
Chapter 6. General Thermodynamic Relationships (single component systems, or systems of constant composition) 119
6.1 The Maxwell relationships 119
6.2 Uses of the thermodynamic relationships 123
6.3 Tds relationships 127
6.4 Relationships between specific heat capacities 130
6.5 The Clausius-Clapeyron equation 134
6.6 Concluding remarks 137
Problems 137
Chapter 7. Equations of State 140
7.1 Ideal gas law 140
7.2 Van der Waals' equation of state 142
7.3 Law of corresponding states 144
7.4 Isotherms or isobars in the two-phase region 148
7.5 Concluding remarks 150
Problems 151
Chapter 8. Liquefaction of Gases 154
8.1 Liquefaction by cooling – method (i) 154
8.2 Liquefaction by expansion – method (ii) 159
8.3 The Joule–Thomson effect 160
8.4 Linde liquefaction plant 167
8.5 Inversion point on p-v-T surface for water 169
8.6 Concluding remarks 174
Problems 174
Chapter 9. Thermodynamic Properties of Ideal Gases and Ideal Gas Mixtures of Constant Composition 177
9.1 Molecular weights 177
9.2 State equation for ideal gases 178
9.3 Tables of u(T) and h(T) against T 183
9.4 Mixtures of ideal gases 191
9.5 Entropy of mixtures 194
9.6 Concluding remarks 197
Problems 197
Chapter 10. Thermodynamics of Combustion 201
10.1 Simple chemistry 203
10.2 Combustion of simple hydrocarbon fuels 204
10.3 Heats of formation and heats of reaction 206
10.4 Application of the energy equation to the combustion process – a macroscopic approach 207
10.5 Combustion processes 211
10.6 Examples 214
10.7 Concluding remarks 224
Problems 224
Chapter 11. Chemistry of Combustion 227
11.1 Bond energies and heats of formation 227
11.2 Energy of formation 229
11.3 Enthalpy of reaction 235
11.4 Concluding remarks 235
Chapter 12. Chemical Equilibrium and Dissociation 237
12.1 Gibbs energy 237
12.2 Chemical potential, µ 239
12.3 Stoichiometry 240
12.4 Dissociation 241
12.5 Calculation of chemical equilibrium and the law of mass action 244
12.6 Variation of Gibbs energy with composition 248
12.7 Examples of the significance of Kp 250
12.8 The Van't Hoff relationship between equilibrium constant and heat of reaction 257
12.9 The effect of pressure and temperature on degree of dissociation 258
12.10 Dissociation calculations for the evaluation of nitric oxide 261
12.11 Dissociation problems with two, or more, degrees of dissociation 264
12.12 Concluding remarks 278
Problems 278
Chapter 13. The Effect of Dissociation on Combustion Parameters 284
13.1 Calculation of combustion both with and without dissociation 286
13.2 The basic reactions 286
13.3 The effect of dissociation on peak pressure 287
13.4 The effect of dissociation on peak temperature 287
13.5 The effect of dissociation on the composition of the products 288
13.6 The effect of fuel on composition of the products 291
13.7 The formation of oxides of nitrogen 292
Chapter 14. Chemical Kinetics 295
14.1 Introduction 295
14.2 Reaction rates 295
14.3 Rate constant for reaction, k 298
14.4 Chemical kinetics of NO 299
14.5 The effect of pollutants formed through chemical kinetics 305
14.6 Other methods of producing power from hydrocarbon fuels 307
14.7 Concluding remarks 308
Problems 308
Chapter 15. Combustion and Flames 310
15.1 Introduction 310
15.2 Thermodynamics of combustion 311
15.3 Explosion limits 313
15.4 Flames 315
15.5 Flammability limits 322
15.6 Ignition 323
15.7 Diffusion flames 324
15.8 Engine combustion systems 326
15.9 Concluding remarks 333
Problems 333
Chapter 16. Irreversible Thermodynamics 335
16.1 Introduction 335
16.2 Definition of irreversible or steady state thermodynamics 336
16.3 Entropy flow and entropy production 336
16.4 Thermodynamic forces and thermodynamic velocities 337
16.5 Onsager's reciprocal relation 338
16.6 The calculation of entropy production or entropy flow 340
16.7 Thermoelectricity – the application of irreversible thermodynamics to a thermocouple 341
16.8 Diffusion and heat transfer 351
16.9 Concluding remarks 361
Problems 361
Chapter 17. Fuel Cells 364
17.1 Electric cells 365
17.2 Fuel cells 370
17.3 Efficiency of a fuel cell 377
17.4 Thermodynamics of cells working in steady state 378
17.5 Concluding remarks 380
Problems 380
Bibliography 382
Index (including Index of tables of properties) 388