Contents

Preface
structure
Symbols

1 State of Equilibrium
Equilibrium of a thermodynamic system
Helmholtz energy (Helmholtz function)
Gibbs energy (Gibbs function)
The use and significance of the Helmholtz and Gibbs energies
Concluding remarks
Problems
1.1
1.2
1.3
1.4
1.5

2 Availability and Exergy

Displacement work
Availability
Examples
Available and non-available energy
Irreversibility
2.6 Graphical representation of available energy and irreversibility
Availability balance for a closed system
2.7
Availability balance for an open system
2.8
2.9
Exergy
2.10 The variation of flow exergy for a perfect gas
2.1 1 Concluding remarks
Problems
2.1
2.2
2.3
2.4
2.5

3 Pinch Technology
A heat transfer network without a pinch problem
A heat transfer network with a pinch point
Concluding remarks
Problems
3.1
3.2
3.3

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4 Rational Efficiency of a Powerplant

64

The influence of fuel properties on thermal efficiency

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

64

5 Efficiency of Heat Engines at Maximum Power

85

Efficiency of an internally reversible heat engine when producing maximum

power output
5.2 Efficiency of combined cycle internally reversible heat engines when
producing maximum power output
5.3 Concluding remarks
Problems

65
69
71
82
82

5.1

6 General Thermodynamic Relationships (single component

systems, or systems of constant composition 1
6.1
The Maxwell relationships
Uses of the thermodynamicrelationships
6.2
6.3 Tdr relationships
6.4 Relationships between specific heat capacities
6.5
The Clausius-Clapeyron equation
6.6
Concluding remarks
Problems

7 Equations of State
7.1 Ideal gas law
7.2 Van der Waalsequation of state
7.3
Law of corresponding states
Isotherms or isobars in the two-phase region
7.4
7.5
Concluding remarks
Problems

8 Liquefaction of Gases
8.1 Liquefaction by cooling - method (i)
8.2 Liquefaction by expansion - method (ii)
8.3 The Joule-Thomson effect
8.4
Linde liquefaction plant
8.5 Inversion point on p-v-T surface for water
8.6 Concludingremarks
Problems

9 Thermodynamic Properties of Ideal Gases and Ideal Gas

Mixtures of Constant Composition
9.1

Molecular weights

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
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State equation for ideal gases

Tables of u ( T ) and h ( T ) against T
Mixtures of ideal gases
Entropy of mixtures
Concludingremarks
Problems

9.2
9.3
9.4
9.5
9.6

10 Thermodynamics of Combustion
Simple chemistry
Combustion of simple hydrocarhn fuels
Heats of formation and heats of reaction
Application of the energy equation to the combustion process a macroscopic approach
10.5 Combustionprocesses
10.6 Examples
10.7 Concluding remarks
Problems
10.1
10.2
10.3
10.4

11 Chemistry of Combustion

159
164
172
175
178
178

182
184
185
187
188
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205
205

208

11.1 Bond energies and heats of formation

11.2 Energy of formation
11.3 Enthalpy of reaction
11.4 Concluding remarks

208
210
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216

12 Chemical Equilibrium and Dissociation

218

Gibbs energy
Chemical potential, p
Stoichiometry
Dissociation
Calculation of chemical equilibrium and the law of mass action
Variation of Gibbs energy with composition
Examples of the significanceof Kp
The Van? Hoff relationship between equilibrium constant and heat of reaction
The effect of pressure and temperature on degree of dissociation
Dissociation calculationsfor the evaluation of nitric oxide
Dissociation problems with two, or more, degrees of dissociation
Concludingremarks
Problems
12.1
12.2
12.3
12.4
12.5
12.6
12.7
12.8
12.9
12.10
12.11
12.12

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 dissociationon the composition of the products
13.6 The effect of fuel on composition of the products
13.7 The formation of oxides of nitrogen

218
220
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268
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14 Chemical Kinetics
14.1 Introduction
14.2 Reaction rates
14.3 Rate constant for reaction, k
14.4 Chemical kinetics of NO
14.5 The effect of pollutants formed through chemical kinetics
14.6 Other methods of producing power from hydrocarbon fuels
14.7 Concluding remarks
Problems

15 Combustion and Flames

15.1 Introduction
15.2 Thermodynamicsof 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
16.2
16.3
16.4
16.5
16.6
16.7

Introduction
Definition of irreversible or steady state thermodynamics
Entropy flow and entropy production
Thermodynamic forces and thermodynamicvelocities
Onsagers reciprocal relation
The calculation of entropy production or entropy flow
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 Efficiency of a fuel cell
17.4 Thermodynamics of cells working in steady state
17.5 Concluding remarks
Problems

276

276
276
279
280
286
288
289
289

29 1
29 1
292
294
296
303
304
305
307
314
314

316
316
317
317
318
319
321
322
332
342
342

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346
35 1
358
359
361
361

Bibliography

363

Index (including Index of tables of properties)

369