Contents

Preface structure Symbols

1 State of Equilibrium

1.1 Equilibrium of a thermodynamic system 1.2 Helmholtz energy (Helmholtz function) 1.3 Gibbs energy (Gibbs function) 1.4 1.5 Concluding remarks Problems

The use and significance of the Helmholtz and Gibbs energies

2 Availability and Exergy

2.1 Displacement work 2.2 Availability 2.3 Examples 2.4 Available and non-available energy 2.5 Irreversibility 2.6 2.7 2.8 2.9 Exergy 2.10 2.1 1 Concluding remarks Problems

Graphical representation of available energy and irreversibility Availability balance for a closed system Availability balance for an open system

The variation of flow exergy for a perfect gas

3 Pinch Technology

3.1 3.2 3.3 Concluding remarks Problems

A heat transfer network without a pinch problem A heat transfer network with a pinch point

ix ... X l l l

xv

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2 5 6 6 9

10

13

13 14 15 21 21 25 27 34 36 42 43 43

47

49 56 60 61

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4 Rational Efficiency of a Powerplant

4.1 4.2 Rational efficiency 4.3 Rankinecycle 4.4 Examples 4.5 Concluding remarks Problems

The influence of fuel properties on thermal efficiency

64

64 65 69 71 82 82

5 Efficiency of Heat Engines at Maximum Power

5.1

5.2

5.3 Concluding remarks Problems

Efficiency of an internally reversible heat engine when producing maximum power output Efficiency of combined cycle internally reversible heat engines when producing maximum power output

6 General Thermodynamic Relationships (single component systems, or systems of constant composition 1 6.1 The Maxwell relationships 6.2 6.3 Tdr relationships 6.4 6.5 The Clausius-Clapeyron equation 6.6 Concluding remarks Problems

Uses of the thermodynamic relationships

Relationships between specific heat capacities

7 Equations of State 7.1 Ideal gas law 7.2 7.3 Law of corresponding states 7.4 7.5 Concluding remarks Problems

Van der Waals’ equation of state

Isotherms or isobars in the two-phase region

8 Liquefaction of Gases

8.1 8.2 8.3 The Joule-Thomson effect 8.4 Linde liquefaction plant 8.5 8.6 Concluding remarks Problems

Liquefaction by cooling - method (i) Liquefaction by expansion - method (ii)

Inversion point on p-v-T surface for water

9 Thermodynamic Properties of Ideal Gases and Ideal Gas Mixtures of Constant Composition 9.1 Molecular weights

85

85

92 96 96

100 100 104 108 111 115 118 118

121

121 123 125 129 131 132

135

135 140 141 148 150 155 155

158 158

9.2 9.3 9.4 Mixtures of ideal gases 9.5 Entropy of mixtures 9.6 Concluding remarks Problems

State equation for ideal gases Tables of u(T) and h(T) against T

10 Thermodynamics of Combustion

10.1 Simple chemistry 10.2 10.3 10.4

10.5 Combustion processes 10.6 Examples 10.7 Concluding remarks Problems

Combustion of simple hydrocarhn fuels Heats of formation and heats of reaction Application of the energy equation to the combustion process - a macroscopic approach

11 Chemistry of Combustion

1 1.1 1 1.2 Energy of formation 1 1.3 Enthalpy of reaction 1 1.4 Concluding remarks

Bond energies and heats of formation

12 Chemical Equilibrium and Dissociation

12.1 Gibbs energy 12.2 Chemical potential, p 12.3 Stoichiometry 12.4 Dissociation 12.5 12.6 12.7 12.8 12.9 12.10 Dissociation calculations for the evaluation of nitric oxide 12.11 Dissociation problems with two, or more, degrees of dissociation 12.12 Concluding remarks Problems

Calculation of chemical equilibrium and the law of mass action Variation of Gibbs energy with composition Examples of the significance of Kp The Van? Hoff relationship between equilibrium constant and heat of reaction The effect of pressure and temperature on degree of dissociation

13 The Effect of Dissociation on Combustion Parameters

13.1 Calculation of combustion both with and without dissociation 13.2 The basic reactions 13.3 The effect of dissociation on peak pressure 13.4 The effect of dissociation on peak temperature 13.5 The effect of dissociation on the composition of the products 13.6 The effect of fuel on composition of the products 13.7 The formation of oxides of nitrogen

159 164 172 175 178 178

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184 185 187

188 192 195 205 205

208

208 210 216 216

218

218 220 221 222 225 229 23 1 238 239 242 245 259 259

265

267 267 268 268 269 272 273

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14 Chemical Kinetics

14.1 Introduction 14.2 Reaction rates 14.3 14.4 Chemical kinetics of NO 14.5 14.6 14.7 Concluding remarks Problems

Rate constant for reaction, k

The effect of pollutants formed through chemical kinetics Other methods of producing power from hydrocarbon fuels

276

276 276 279 280 286 288 289 289

15 Combustion and Flames

15.1 Introduction 15.2 Thermodynamics of combustion 15.3 Explosion limits 15.4 Flames 15.5 Flammability limits 15.6 Ignition 15.7 Diffusion flames 15.8 Engine combustion systems 15.9 Concluding remarks Problems

16 Irreversible Thermodynamics 16.1 Introduction 16.2 Definition of irreversible or steady state thermodynamics 16.3 Entropy flow and entropy production 16.4 Thermodynamic forces and thermodynamic velocities 16.5 Onsager’s reciprocal relation 16.6 The calculation of entropy production or entropy flow 16.7 Thermoelectricity - the application of irreversible thermodynamics to a

thermocouple 16.8 Diffusion and heat transfer 16.9 Concluding remarks Problems

17 Fuel Cells 17.1 Electric cells 17.2 Fuel cells 17.3 17.4 17.5 Concluding remarks Problems

Efficiency of a fuel cell Thermodynamics of cells working in steady state

29 1

29 1 292 294 296 303 304 305 307 314 314

316 316 317 317 318 319 321

322 332 342 342

345 346 35 1 358 359 361 361

Bibliography 363

Index (including Index of tables of properties) 369