Advanced thermodynamics for engineers

Although the basic theories of thermodynamics are adequately covered by a number of existing texts, there is little literature that addresses more advanced topics. In this comprehensive work the author redresses this balance, drawing on his twenty-five years of experience of teaching thermodynamics at undergraduate and postgraduate level, to produce a definitive text to cover thoroughly, advanced syllabuses. The book introduces the basic concepts which apply over the whole range of new technologies, considering: a new approach to cycles, enabling their irreversibility to be taken into account; a detailed study of combustion to show how the chemical energy in a fuel is converted into thermal energy and emissions; an analysis of fuel cells to give an understanding of the direct conversion of chemical energy to electrical power; a detailed study of property relationships to enable more sophisticated analyses to be made of both high and low temperature plant and irreversible thermodynamics, whose principles might hold a key to new ways of efficiently covering energy to power (e.g. solar energy, fuel cells). Worked examples are included in most of the chapters, followed by exercises with solutions. By developing thermodynamics from an explicitly equilibrium perspective, showing how all systems attempt to reach a state of equilibrium, and the effects of these systems when they cannot, the result is an unparalleled insight into the more advanced considerations when converting any form of energy into power, that will prove invaluable to students and professional engineers of all disciplines. @TEAM LIB......Page 1 Preface......Page 4 Structure of book......Page 8 Symbols......Page 9 Contents......Page 14 1 State of Equilibrium......Page 18 1.1 Equilibrium of a thermodynamic system......Page 19 1.2 Helmholtz energy (Helmholtz function)......Page 22 1.4 The use and significance of the Helmholtz and Gibbs energies......Page 23 1.4.2 GIBBS ENERGY......Page 24 1.4.3 THERMODYNAMICS EXAMPLES OF DIFFERENT FORMS OF EQUILJBRIUM MET IN THERMODYNAMICS......Page 25 1.5 Concluding remarks......Page 26 PROBLEMS......Page 27 2.1 Displacement work......Page 30 2.2 Availability......Page 31 2.3 Examples......Page 32 2.5 Irreversibility......Page 38 2.6 Graphical representation of available energy, and irreversibility......Page 42 2.7 Availability balance for a closed system......Page 44 2.8 Availability balance for an open system......Page 51 2.9 Exergy......Page 53 2.9.1 HEAT TRANSFER......Page 54 2.9.2 EXERGY APPLIED TO COMBUSTION PROCESS......Page 57 2.10 The variation of flow exergy for a perfect gas......Page 59 PROBLEMS......Page 60 3 Pinch Technology......Page 64 3.1 A heat transfer network without a pinch problem......Page 66 3.2 A heat transfer network with a pinch point......Page 73 3.3 Concluding remarks......Page 77 PROBLEMS......Page 78 4.1 The influence of fuel properties on thermal efficiency......Page 81 4.2 Rational efficiency......Page 82 4.3 Rankine cycle......Page 86 4.4 Examples......Page 88 PROBLEMS......Page 99 5.1 maximum power output Efficiency of an internally reversible heat engine when producing maximum power output......Page 102 5.2 Efficiency of combined cycle internally reversible heat engines when producing maximum power output......Page 109 PROBLEMS......Page 113 6.1 The Maxwell relationships......Page 117 6.1.1 GRAPHICAL-. INTERPRETATION OF MAXWELL RELATIONS......Page 120 6.2 Uses of the thermodynamic relationships......Page 121 6.3 Tds relationships......Page 125 6.4 Relationships between specific heat capacities......Page 128 6.5 The Clausius-Clapeyron equation......Page 132 6.5.1 THE USE OF THE CLAUSIUS-CLAPEYRON EQUATION......Page 134 PROBLEMS......Page 135 7.1 Ideal gas law......Page 138 7.2 Van der Waals’ equation of state......Page 140 7.3 Law of corresponding states......Page 142 PROBLEMS......Page 146 7.5 Concluding remarks......Page 148 8.1 Liquefaction by cooling - method (i)......Page 152 8.2 Liquefaction by expansion - method (ii)......Page 157 8.3 The Joule-Thomson effect......Page 158 8.3.1 MAXIMUM AND MINIMUM IWERSION TEMPERATURES......Page 162 8.4 Linde liquefaction plant......Page 165 8.5 Inversion point on p-v-Tsurface for water......Page 167 PROBLEMS......Page 172 9.1 Molecular weights......Page 175 9.2 State equation for ideal gases......Page 176 9.2.1 IDEAL GAS EQUATION......Page 177 9.2.2 THE SIGNIFICANCE OF Uom AND hom......Page 178 9.2.3 ENTROPY OF AN IDEAL GAS - THIRD LAW OF THERMODYNAMICS......Page 179 9.2.4 THE GIBBS ENERGY (FUNCTION) OF AN IDEAL GAS......Page 180 9.3 Tables of u ( T ) and h ( T ) against T......Page 181 9.3.1 TABLES OF MEAN SPECIFIC HEAT......Page 188 9.4.3 MIXTURE RELATIONSHIPS......Page 189 9.5 Entropy of mixtures......Page 192 PROBLEMS......Page 195 10 Thermodynamics of Combustion......Page 199 10.1.1 FUELS......Page 201 10.2 Combustion of simple hydrocarbon fuels......Page 202 10.2.3 COMBUSTION WITH RICH MIXTURES......Page 203 10.3 Heats of formation and heats of reaction......Page 204 10.4.2 HE.4TS OF REACTION AND FORMATION......Page 205 10.4.3 HEAT OF FORMATION - HESS' LAW......Page 207 10.51 ADIABATIC COMBUSTION......Page 209 10.5.2 COMBUSTION WITH HEAT AND WORK TRANSFER......Page 211 10.6 Examples......Page 212 PROBLEMS......Page 222 11.1 Bond energies and heats of formation......Page 225 11.2 Energy of formation......Page 227 11.4 Concluding remarks......Page 233 12.1 Gibbs energy......Page 235 12.2 Chemical potential, u......Page 237 12.3 Stoichiometry......Page 238 12.4 Dissociation......Page 239 12.4.1 WEAK MIXTURE WITH DISSOCIATION......Page 240 12.4.3 GENERAL HYDROCARBON REACTION WITH DISSOCIATION......Page 241 12.5 Calculation of chemical equilibrium and the law of mass action......Page 242 12.6 Variation of Gibbs energy with composition......Page 246 12.8 The Wan't Hoff relationship between equilibrium constant and heat of reaction......Page 255 12.7.1 EXAMPLEI......Page 248 12.7.2 EXAMPLE 2......Page 249 12.7.3 EXAMPLE I : A ONE DEGREE OF DISSOCIATION EXAMPLE......Page 250 12.9.1 The effect of pressure......Page 256 12.9.2 THE EFFECT OF TEMPERATURE......Page 258 12.10 Dissociation calculations for the evaluation of nitric oxide......Page 259 12.11.1 EXAMPLE 4: COMBUSTION OF A TYPICAL HYDROCARBON FUEL......Page 262 12.11.2 EXAMPLE 5: A RICH MIXTURE......Page 269 12.11.3 EXAMPLE 6: THE FORMATION OF NITRIC OXIDE......Page 271 PROBLEMS......Page 276 13 Effect of Dissociation on Combustion Parameters......Page 282 13.2 The basic reactions......Page 284 13.4 The effect of dissociation on peak temperature......Page 285 13.5 The effect of dissociation on the composition of the products......Page 286 13.6 The effect of fuel on composition of the products......Page 289 13.7 The formation of oxides of nitrogen......Page 290 14.2 Reaction rates......Page 293 14.3 Rate constant for reaction, k......Page 296 14.4 Chemical kinetics of NO......Page 297 14.5.2 SULFUR DIOXIDE (SO,) EMISSIONS......Page 303 14.5.4 GREENHOUSE EFFECT......Page 304 14.6 Other methods of producing power from hydrocarbon fuels......Page 305 PROBLEMS......Page 306 15.1 Introduction......Page 308 15.2 Thermodynamics of combustion......Page 309 15.2.1 REACTION ORDER......Page 310 15.3 Explosion limits......Page 311 15.3.1 EXPLODE THE EFFECT OF MULTIPLICATION FACTOR ON THE TENDENCY TO EXPLODE......Page 312 15.4.1 PREMIXED FLAMES......Page 313 15.4.2 LAMINAR FLAME SPEED......Page 314 15.4.3 TURBULENT FLAME SPEED......Page 319 15.5 Flammability limits......Page 320 15.6 Ignition......Page 321 15.7 Diffusion flames......Page 322 15.8.1 SPARK-IGNITION ENGINES......Page 324 15.8.2 DIESEL ENGINES......Page 326 15.8.3 GAS TURBINES......Page 329 PROBLEMS......Page 331 16.1 Introduction......Page 333 16.3 Entropy flow and entropy production......Page 334 16.4 Thermodynamic forces and thermodynamic velocities......Page 335 16.5 Onsager's reciprocal relation......Page 336 16.6 The calculation of entropy production or entropy flow......Page 338 16.7.1 THERMOELECTRIC PHENOMENA......Page 339 16.7.2 UNCOUPLED EFFECTS IN THERMOELECTRICITY......Page 340 16.7.3 THE COUPLED EQUATIONS OF THERMOELECTRICITY......Page 341 16.7.4 THE THERMOCOUPLE......Page 343 16.7.5 OTHER EFFECTS IN THERMOCOUPLES......Page 346 16.8.1 BASIC PHENOMENA INVOLVED......Page 349 16.8.2 DEFINING THE FORCES AND FLUXES......Page 350 16.8.3 THE UNCOUPLED EQUATIONS OF DIFFUSION......Page 352 PROBLEMS......Page 359 17 Fuel Cells......Page 362 17.1 Electric cells......Page 363 17.1.1 ELECTROCHEMICAL. POTENTIAL......Page 366 17.1.2 THERMODYNAMIC ORIGIN OF EMF......Page 367 17.2 Fuel cells......Page 368 17.2.1 EXAMPLE: A HYDROGEN-OXYGEN FUEL CELL......Page 370 17.2.3 EXAMPLES......Page 372 17.3 Efficiency of a fuel cell......Page 375 17.4 Thermodynamics of cells working in steady state......Page 376 PROBLEMS......Page 378 Bibliography......Page 380 Index......Page 385 Introduces basic concepts that apply over a range of engineering thermodymanics technologies. Considers approaches to cycles, enabling their irreversibility to be taken into account. Gives a detailed study of combustion to show how the chemical energy in a fuel is converted into thermal energy and emissions; analyses fuel cells to provide an understanding of the direct conversion of chemical energy to electrical power; studies property relationships to enable more sophisticated analyses to be made of both high and low temperature plant and irreversible thermodynamics, which contain principles that might hold a key to new ways of efficiently converting energy to power.--[Source inconnue]