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. Front Cover Advanced Thermodynamics for Engineers Copyright Page Contents Preface Structure Symbols Chapter 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 The use and significance of the Helmholtz and Gibbs energies 1.5 Concluding remarks Problems Chapter 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 Graphical representation of available energy and irreversibility 2.7 Availability balance for a closed system 2.8 Availability balance for an open system 2.9 Exergy 2.10 The variation of flow exergy for a perfect gas 2.11 Concluding remarks Problems Chapter 3. Pinch Technology 3.1 A heat transfer network without a pinch problem 3.2 A heat transfer network with a pinch point 3.3 Concluding remarks Problems Chapter 4. Rational Efficiency of a Powerplant 4.1 The influence of fuel properties on thermal efficiency 4.2 Rational efficiency 4.3 Rankine cycle 4.4 Examples 4.5 Concluding remarks Problems Chapter 5. Efficiency of Heat Engines at Maximum Power 5.1 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 Chapter 6. General Thermodynamic Relationships (single component systems, or systems of constant composition) 6.1 The Maxwell relationships 6.2 Uses of the thermodynamic relationships 6.3 Tds relationships 6.4 Relationships between specific heat capacities 6.5 The Clausius-Clapeyron equation 6.6 Concluding remarks Problems Chapter 7. Equations of State 7.1 Ideal gas law 7.2 Van der Waals' equation of state 7.3 Law of corresponding states 7.4 Isotherms or isobars in the two-phase region 7.5 Concluding remarks Problems Chapter 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 Concluding remarks Problems Chapter 9. Thermodynamic Properties of Ideal Gases and Ideal Gas Mixtures of Constant Composition 9.1 Molecular weights 9.2 State equation for ideal gases 9.3 Tables of u(T) and h(T) against T 9.4 Mixtures of ideal gases 9.5 Entropy of mixtures 9.6 Concluding remarks Problems Chapter 10. Thermodynamics of Combustion 10.1 Simple chemistry 10.2 Combustion of simple hydrocarbon fuels 10.3 Heats of formation and heats of reaction 10.4 Application of the energy equation to the combustion process – a macroscopic approach 10.5 Combustion processes 10.6 Examples 10.7 Concluding remarks Problems Chapter 11. Chemistry of Combustion 11.1 Bond energies and heats of formation 11.2 Energy of formation 11.3 Enthalpy of reaction 11.4 Concluding remarks Chapter 12. Chemical Equilibrium and Dissociation 12.1 Gibbs energy 12.3 Stoichiometry 12.4 Dissociation 12.5 Calculation of chemical equilibrium and the law of mass action 12.6 Variation of Gibbs energy with composition 12.7 Examples of the significance of Kp 12.8 The Van't Hoff relationship between equilibrium constant and heat of reaction 12.9 The effect of pressure and temperature on degree of dissociation 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 Chapter 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 Chapter 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 Chapter 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 Chapter 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 Chapter 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 Bibliography Index (including Index of tables of properties) 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