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Desmond E Winterbone
FEng, BSc, PhD, DSc, FIMechE, MSAE
Thermodynamics and Fluid Mechanics Division Department of Mechanical Engineering
UMIST
A member of the Hodder Headline Group
LONDON SYDNEY AUCKLAND Copublished i North, Central and South America by n John Wiley & Sons,he., New York Toronto
First published in Great Britain 1997 by Arnold, a member of the Hodder Headline Group, 338 Euston Road, London NW1 3BH Copublished in North, Central and South America by John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 101580012
0 1997 D E Winterbone
All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronically or mechanically, including photocopying, recording or any information storage or retrieval system, without either prior permission in writing from the publisher or a licence permitting restricted copying. In the United Kingdom such licences are issued by the Copyright Licensing Agency: 90 Tottenham Court Road, London WIP 9HE. Whilst the advice and information in this book is believed to be true and accurate at the date of going to press, neither the author nor the publisher can accept any legal responsibility or liability for any errors or omissions that may be made. British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress CataloginginPublicationData A catalog record for this book is available from the Library of Congress ISBN 0 340 67699 X (pb) 0 470 23718 X (Wiley) Typeset in 10/12 pt Times by Mathematical Composition Setters Ltd, Salisbury, Wilts Printed and bound in Great Britain by J W Anowsmith Ltd, Bristol
Preface
When reviewing, or contemplating writing, a textbook on engineering thermodynamics, it is necessary to ask what does this book offer that is not already available? The author has taught thermodynamics to mechanical engineering students, at both undergraduate and postgraduate level, for 25 years and has found that the existing texts cover very adequately the basic theories of the subject. However, by the final years of a course, and at postgraduate level, the material which is presented is very much influenced by the lecturer, and here it is less easy to find one book that covers all the syllabus in the required manner. This book attempts to answer that need, for the author at least. The engineer is essentially concerned with manufacturing devices to enable tasks to be preformed cost effectively and efficiently. Engineering has produced a new generation of automatic ‘slaves’ which enable those in the developed countries to maintain their lifestyle by the consumption of fuels rather than by manual labour. The developing countries still rely to a large extent on ‘manpower’, but the pace of development is such that the whole world wishes to have the machines and quality of life which we, in the developed countries, take for granted: this is a major challenge to the engineer, and particularly the thermodynamicist. The reason why the thermodynamicist plays a key role in this scenario is because the methods of converting any form of energy into power is the domain of thermodynamics: all of these processes obey the four laws of thermodynamics, and their efficiency is controlled by the Second Law. The emphasis of the early years of an undergraduate course is on the First Law of thermodynamics, which is simply the conservation of energy; the First Law does not give any information on the quality of the energy. It is the hope of the author that this text will introduce the concept of the quality of energy and help future engineers use our resources more efficiently. Ironically, some of the largest demands for energy may come from cooling (e.g. refrigeration and airconditioning) as the developing countries in the tropical regions become wealthier  this might require a more basic way of considering energy utiiisation than that emphasised in current thermodynamic texts. This book attempts to introduce basic concepts which should apply over the whole range of new technologies covered by engineering thermodynamics. It considers new approaches to cycles, which enable 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
x Preface
high and low temperature plant; and irreversible thermodynamics, whose principles might hold a key to new ways of efficiently converting energy to power (e.g. solar energy, fuel cells). The great advances in the understanding and teaching of thermodynamics came rapidly towards the end of the 19th century, and it was not until the 1940s that these were embodied in thermodynamics textbooks for mechanical engineers. Some of the approaches used in teaching thermodynamics still contain the assumptions embodied in the theories of heat engines without explicitly recognising the limitations they impose. It was the desire to remove some of these shortcomings, together with an increasing interest in what limits the efficiency of thermodynamic devices, that led the author down the path that has culminated in this text. I am still a strong believer in the pedagogical necessity of introducing thermodynamics through the traditional route of the Zeroth, First, Second and Third Laws, rather than attempting to use the SingleAxiom Theorem of Hatsopoulos and Keenan, or The Law of Stable Equilibrium of Haywood. While both these approaches enable thermodynamics to be developed in a logical manner, and limit the reliance on cyclic processes, their understanding benefits from years of experience  the one thing students are lacking. I have structured this book on the conventional method of developing the subject. The other dilemma in developing an advanced level text is whether to introduce a significant amount of statistical thermodynamics; since this subject is related to the particulate nature of matter, and most engineers deal with systems far from regions where molecular motion dominates the processes, the majority of the book is based on equilibrium thermodynamics; which concentrates on the macroscopic nature of systems. A few examples of statistical thermodynamics are introduced to demonstrate certain forms of behaviour, but a full understanding of the subject is not a requirement of the text. The book contains 17 chapters and, while this might seem an excessive number, these are of a size where they can be readily incorporated into a degree course with a modular structure. Many such courses will be based on two hours lecturing per week, and this means that most of the chapters can be presented in a single week. Worked examples are included in most of the chapters to illustrate the concepts being propounded, and the chapters are followed by exercises. Some of these have been developed from texts which are now not available (e.g. Benson, Haywood) and others are based on examination questions. Solutions are provided for all the questions. The properties of gases have been derived from polynomial coefficients published by Benson: all the parameters quoted have been evaluated by the author using these coefficients and equations published in the text this means that all the values are selfconsistent, which is not the case in all texts. Some of the combustion questions have been solved using computer programs developed at UMIST,and these are all based on these gas property polynomials. If the reader uses other data, e.g. JANAF tables, the solutions obtained might differ slightly from those quoted. Engineering thermodynamics is basically equilibrium thermodynamics, although for the first two years of the conventional undergraduate course these words are used but not often defined. Much of the thermodynamics done in the early years of a course also relies heavily on reversibilio, without explicit consideration of the effects of irreversibility. Yet, if the performance of thermodynamic devices is to be improved, it is the irreversibility that must be tackled. This book introduces the effects of irreversibility through considerations of availability (exergy), and the concept of the endoreversible engine. The thermal efficiency is related to that of an ideal cycle by the rational efficiency  to demonstrate how closely the performance of an engine approaches that of a reversible one. It is also
Preface xi shown that the Camot efficiency is a very artificial yardstick against which to compare real engines: the internal and external reversibilitiesimposed by the cycle mean that it produces zero power at the maximum achievable efficiency. The approach by CuIZon and Ahlbom to define the efficiency of an endoreversible engine producing maximum power output is introduced: this shows the effect of extern1 irreversibility. This analysis also introduces the concept of entropy generation in a manner readily understandable by the engineec this concept is the comerstone of the theories of irreversible thennodynamics which are at the end of the text. Whilst the laws of thermodynamics can be developed in isolation from consideration of the property relationships of the system under consideration, it is these relationships that enable the equations to be closed. Most undergraduate texts are based on the evaluation of the fluid properties from the simple perfect gas law, or from tables and charts. While this approach enables typical engineering problems to be solved, it does not give much insight into some of the phenomena which can happen under certain circumstances. For example, is the specific heat at constant volume a function of temperature alone for gases in certain regions of the state diagram? Also, why is the assumption of constant stagnation, or even static, temperature valid for flow of a perfect gas through a throttle, but never for steam? An understanding of these effects can be obtained by examination of the more complex equations of state. This immediately enables methods of gas liquefaction to be introduced. An important area of e n g i n e e ~ g thermodynamics is the combustion of hydrocarbon fuels. These fuels have formed the driving force for the improvement of living standards which has been seen over the last century, but they are presumably finite, and are producing levels of pollution that are a constant challenge to engineers. At present, there is the threat of global warming due to the buildup of carbon dioxide in the atmosphere: this requires more efficient engines to be produced, or for the carbonhydrogen ratio in fuels to be reduced. Both of these are major challenges, and while California can legislate for the Zero Emissions Vehicle (ZEV) this might not be a worldwide solution. It is said that the ZEV is an electric car running in Los Angeles on power produced in Arizona! obviously a case of exporting pollution rather than reducing it. The real challenge is not what is happening in the West, although the energy consumption of the USA is prodigious, but how can the aspirations of the East be met. The combustion technologies developed today will be necessary to enable the Newly Industrialised Countries (NICs) to approach the level of energy consumption we enjoy. The section on combustion goes further than many general textbooks in an attempt to show the underlying general principles that affect combustion, and it introduces the interaction between thermodynamics and fluid mechanics which is so important to achieving clean and efficient combustion. The final chapter introduces the thermodynamic principles of fuel cells, which enable the direct conversion of the Gibbs energy in the fuel to electrical power. Obviously the fuel cell could be a major contributor to the production of 'clean' energy and is a goal for which it is worth aiming. Finally, a section is included on irreversible thermodynamics. This is there partly as an intellectual challenge to the reader, but also because it infroduces concepts that might gain more importance in assessing the performance of advanced forms of energy conversion. For example, although the fuel cell is basically a device for converting the Gibbs energy of the reactants into electrical energy, is its efficiency compromised by the thermodynamics of the steady state that are taking place in the cell? Also, will photovoltaic devices be limited by phenomena considered by irreversible thermodynamics?
xii Preface I have taken the generous advice of D Joe Lee, a colleague in the Department of r Chemistry, UMIST,and modified some of the wording of the original text to bring it in line with more modem chemical phraseology. I have replaced the titles Gibbs free energy and Helmholtz free energy by Gibbs and Helmholtz energy respectively: this should not cause any problems and is more logical than including the word ‘free’. I have bowed, with some reservations, to using the internationally agreed spelling sulfur, which again should not cause problems. Perhaps the most difficult concept for engineers will be the replacement of the terms ‘mol’ and ‘kmol’ by the term ‘amount of substance’. This has been common practice in chemistry for many years, and separates the general concept of a ak quantity of matter from the units of that quantity. For example, it is common to t l of a mass of substance without defining whether it is in grams, kilograms, pounds, or whatever system of units is appropriate. The use of the phrase ‘amount of substance’ has the same generalising effect when dealing with quantities based on molecular equivalences. The term mol will still be retained as the adjective and hence molar enthalpy is the enthalpy per unit amount of substance in the appropriate units (e.g. kJ/mol, kJ/kmol, Btu/lbmol, etc). I would like to acknowledge all those who have helped and encouraged the writing of this text. First, I would like to acknowledge the influence of all those who attempted to teach me thermodynamics; and then those who encouraged me to teach the subject, in particular Jim Picken, Frank Wallace and Rowland Benson. In addition, I would like to acknowledge the encouragement to develop the material on combustion which I received from Roger Green during an Erskine Fellowship at the University of Canterbury, New Zealand. Secondly, I would like to thank those who have helped in the production of this book by reading the text or preparing some of the material. Amongst these are Ed Moses, Marcus Davies, Poh Sung Loh, Joe Lee, Richard Pearson and John Horlock; whilst they have read parts of the text and provided their comments, the responsibility for the accuracy of the book lies entirely in my hands. I would also like to acknowledge my secretary, Mrs P Shepherd, who did some of the typing of the original notes. Finally, I must thank my wife, Veronica, for putting up with lack of maintenance in the house and garden, and many evenings spent alone while I concentrated on this work. D E Winterbone
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g.Symbols a a a Of a i A A b b B CP C d D e f E E E E O E. e. specific heat capacity at constant pressure based on rnols) specific heat capacity at constant volume (sometimes abbreviated to specific heat at constant volume) molar specific heat capacity at constant volume (i. F F activity coefficient specific nonflow availability coefficient in van der Waals' equation specific flow availability enthalpy coefficient for gas properties nonflow availability area specific exergy coefficient in van der Waals' equation exergy specific heat capacity at constant pressure (sometimes abbreviated to specific heat at constant pressure) mean value of specific heat capacity at constant pressure over a range of temperatures molar specific heat capacity at constant pressure (Le.e. specific heat capacity at constant volume based on rnols) conductivity for heat flow into engines increment in .usually used for definite integral. property. etc mass diffusivity specific internal energy internal energy activation energy electromotive force of a cell (emf) standard emf of a cell open circuit voltage specific Helmholtz energy (specific Helmholtz function) Helmholtz energy (Helmholtz function) force .
L Le m m w n n n N P Pi Po pr 4 41 Q Q* Q P Q" R Qb Q: R Faraday constant (charge carried by kmol of unit positive valency [96487 kC/kmol]) specific Gibbs energy (specific Gibbs function) specific Gibbs energy at datum temperature (or absolute zero) acceleration due to gravity Gibbs energy (Gibbs function) specific enthalpy specific enthalpy at datum temperature (or absolute zero) height enthalpy irreversibility electrical current thermodynamic velocity. compressibility rate of reaction Karlovitz number [(u'/lT)(d. isothermal bulk modulus thermal conductivity Boltzmann constant [ 1.Qp internal energy of reaction (energy of reaction at constant volume) calorific value (at constant volume) = .023x loz6kmol') pressure partial pressure of component i datum pressure (often 1 bar or 1 atmosphere) Prandtl number [c#/ k] specific heat (energy) transfer electrical charge heat (energy) transfer heat of transport enthalpy of reaction (energy of reaction at constant pressure) calorific value (at constant pressure) = .mi Symbols F g g o g G h ho h H I I J JI JQ Js k k k ks k K K P 1 1./u.)] equilibrium constant length Taylor microscale coefficient relating thermodynamic force and velocity Lewis number [rl/pc. specific gas constant rate of formation.38062 x 10 23 J/K] adiabatic. or flow electrical flow rate heat flow rate entropy flow rate isothermal compressibility. rate of reaction . or isentropic.D] mass molecular weight polytropic index amount of substance.Q. chemical amount (sometimes referred to as number of mols) reaction order Avogadro constant (6.
g. work (W).usually used for indefinite integral. heat (Q) [ D I /P I . increment in .usually used for indefinite integral. heat (Q) atomisation energy enthalpy of formation dissociation energy . work (W). e.Symbols xvii R R R Re S SO S S* t t T U UO U’ UI u t U U V V V V VP W $ W X X X X Y 2 radical electrical resistance universal gas constant Reynolds number [pvZ/pI specific entropy specific entropy at datum temperature (or absolute zero) entropy entropy of transport temperature on discontinuous scale time temperature on absolute scale (thermodynamictemperature) specific intrinsic internal energy specific intrinsic internal energy at datum temperature (or absolute zero) turbulence intensity laminar burning velocity turbulent burning velocity intrinsic internal energy overall heat transfer coefficient specific volume volume velocity voltage mean piston speed (for reciprocating engines) specific work maximum specific work work dryness fraction (quality) molar fraction distance thermodynamic force mass fraction valency Greek characters degree of dissociation [ A1/ [ AI. branching multiplication coefficient molecular thermal diffusivity crank angle (in internal combustion engines) coefficient of thermal expansion [BlI[Bl.g. e. increment in .
g. B eddy diffusivity ratio of specific heats (c. i. B entropy generation per unit volume Thomson coefficient stoichiometric Coefficient [CI/[Cle efficiency equivalence ratio density specific exergy inner electric potential of a phase temperature ratio exergy Suffices 0 actual av b b B C C C [ le f f fg g g h H i i in isen dead state conditions value from actual cycle.) electrical conductivity dynamic viscosity JouleThomson coefficient chemical potential electrochemical potential kinematic viscosity Peltier coefficient for material pair A. h. temperature./c.e.g.Symbols fraction of reaction potential difference. as opposed to ideal cycle available (as in energy) backward (reaction) burned (products of combustion) boiler at critical point.= h. voltage Seebeck coefficient for material pair A. e. = enthalpy of saturated liquid difference between properties on saturated vapour and saturated liquid lines. specific volume cold (as in temperature of reservoir) compressor equilibrium molar density forward (reaction) value for saturated liquid.g. pressure. = enthalpy of saturated gas gaseous state (as in reactants or products) constant enthalpy hot (as in temperature of reservoir) inversion ith constituent into system isentropic (as in a process) . e.hf value for saturated gas.. h. e. h.
or maximum useful work specific property based on mols net (as in work output from system) overall open circuit oc out of system out at constant pressure P P products P Pump rejected not used by cycle (usually energy) E S energy contained in molecules by resonance R rational (as in efficiency) R reactants R reduced properties (in Law of Corresponding States) reversible R S shaft (as in work) at constant entropy S surroundings SUIT system SYS T turbine T at constant temperature thermal th useful (as in work) U unburned (as of reactants) U unavailable (as in energy) unav univ universe (Le. or ufg) liquid state (as in reactants or products) laminZiI maximum value.Symbols xix 1 1 1 max mol net 0 latent energy required for evaporation (equals h . system + surroundings) use useful (as in work) V at constant specific volume .
xv 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 1.10 The variation of flow exergy for a perfect gas 2.4 1.3 1..5 13 13 14 15 21 21 25 27 34 36 42 43 43 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 2.1 1 Concluding remarks Problems 2.3 47 49 56 60 61 .9 Exergy 2.7 Availability balance for an open system 2.2 3.1 2.3 2.8 2.Contents Preface structure Symbols Xlll ix .4 2..6 Graphical representation of available energy and irreversibility Availability balance for a closed system 2.5 1 2 5 6 6 9 10 2 Availability and Exergy Displacement work Availability Examples Available and nonavailable energy Irreversibility 2.2 1.1 1.
3 Law of corresponding states Isotherms or isobars in the twophase region 7.6 Concluding remarks Problems 100 100 104 108 111 115 118 118 7 Equations of State 7.6 Concludingremarks Problems 135 135 140 141 148 150 155 155 9 Thermodynamic Properties of Ideal Gases and Ideal Gas Mixtures of Constant Composition 9.4 Linde liquefaction plant 8.vi Contents 64 64 65 69 71 82 82 4 Rational Efficiency of a Powerplant The influence of fuel properties on thermal efficiency 4.1 The Maxwell relationships Uses of the thermodynamicrelationships 6.1 Efficiency of an internally reversible heat engine when producing maximum power output 5.2 Liquefactionby expansion .2 Efficiency of combined cycle internally reversible heat engines when producing maximum power output 5.1 Liquefaction by cooling .1 Ideal gas law al’ 7.5 Concluding remarks Problems 121 121 123 125 129 131 132 8 Liquefaction of Gases 8.1 Molecular weights 158 158 .3 Tdr relationships 6.method (i) 8.2 Van der W a s equation of state 7.5 The ClausiusClapeyron equation 6.1 4.2 6.2 Rational efficiency 4.5 Concluding remarks Problems 5 Efficiency of Heat Engines at Maximum Power 5.4 Relationships between specific heat capacities 6.3 Rankinecycle 4.3 Concluding remarks Problems 85 85 92 96 96 6 General Thermodynamic Relationships (single component systems. or systems of constant composition 1 6.5 Inversion point on pvT surface for water 8.4 7.method (ii) 8.3 The JouleThomson effect 8.4 Examples 4.
5 12.5 9.8 12.3 Enthalpy of reaction 11.1 Calculation of combustion both with and without dissociation 13.6 Examples 10.5 The effect of dissociationon the composition of the products 13.3 The effect of dissociation on peak pressure 13.2 The basic reactions 13.12 218 218 220 221 222 225 229 23 1 238 239 242 245 259 259 13 The Effect of Dissociation on Combustion Parameters 13.6 The effect of fuel on composition of the products 13.2 12.4 182 184 185 187 188 192 195 205 205 11 Chemistry of Combustion 11.4 9. or more.1 Bond energies and heats of formation 11. degrees of dissociation Concludingremarks Problems 12.5 Combustionprocesses 10.6 12.11 12.10 12.3 9.7 The formation of oxides of nitrogen 265 267 267 268 268 269 272 273 .3 10. 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 relationshipbetween 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.1 10.7 Concluding remarks Problems 10.3 12.2 10.4 Concluding r m r s eak 208 208 210 216 216 12 Chemical Equilibrium and Dissociation Gibbs energy Chemical potential.9.2 9.7 12.1 12.4 The effect of dissociation on peak temperature 13.4 12.6 State equation for ideal gases Tables of u ( T ) and h ( T ) against T Mixtures of ideal gases Entropy of mixtures Concludingremarks Problems 159 164 172 175 178 178 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 10.9 12.2 Energy of formation 11.
7 316 316 317 317 318 319 321 322 332 342 342 17 Fuel Cells 17.3 16.the application of irreversible thermodynamics to a thermocouple 16.5 16.5 The effect of pollutants formed through chemical kinetics 14.4 16.9 Concluding remarks Problems 29 1 29 1 292 294 296 303 304 305 307 314 314 16 Irreversible Thermodynamics Introduction Definition of irreversible o steady state thermodynamics r Entropy flow and entropy production Thermodynamic forces and thermodynamicvelocities Onsager’s reciprocal relation The calculation of entropy production or entropy flow Thermoelectricity .2 Thermodynamicsof combustion 15.1 Introduction 15.viii Contents 276 14 Chemical Kinetics 14.4 Flames 15. k 14.1 Introduction 14.3 Rate constant for reaction.5 Flammability limits 15.2 16.6 Other methods of producing power from hydrocarbon fuels 14.2 Reaction rates 14.4 Chemical kinetics of NO 14.5 Concluding remarks Problems Bibliography Index (including Index of tables of properties) 345 346 35 1 358 359 361 361 363 369 .6 16.2 Fuel cells 17.4 Thermodynamics of cells working in steady state 17.1 Electric cells 17.3 Efficiency of a fuel cell 17.7 Diffusion flames 15.9 Concluding remarks Problems 16.1 16.6 Ignition 15.7 Concluding remarks Problems 276 276 279 280 286 288 289 289 15 Combustion and Flames 15.3 Explosion limits 15.8 Diffusion and heat transfer 16.8 Engine combustion systems 15.
Fig.* < 0 and A E ) s > 0. Any movement causes further motion from ‘equilibrium’ position. There are four kinds of equilibrium. (iii) Unstable equilibrium  Marble in trough. Most of the combustion processes that generate atmospheric pollution include nonequilibrium effects. but some important processes have to be considered by nonequilibrium thermodynamics. The majority of processes met by engineers are in thermodynamic equilibrium. Marble in equilibrium at any position in xdirection..1 States of equilibrium . Marble sitting on maximum point of surface. * Discussed later. 1.1). Any deflection causes motion back towards equilibrium position. AS). A S ) E> 0 and A E ) s < 0. (i) (ii) w Stable equilibrium Neutral equilibrium Marble in bowl.State of Equilibrium Most texts on thermodynamics restrict themselves to dealing exclusively with equilibrium thermodynamics. = 0 and A E ) s = 0 along trough axis. and carbon monoxide (CO) and oxides of nitrogen (NO. and these are most easily understood by reference to simple mechanical systems (see Fig 1. This book will also focus on equilibrium thermodynamics but the effects of making this assumption will be explicitly borne in mind.) are both the result of the inability of the system to reach thermodynamic equilibrium in the time available. For stable equilibrium AS). (AS is the sum of Taylor’s series terms).
=0 (As) E < 0 (dS)E = 0 (AS). 1.1 Equilibrium of a thermodynamic system The type of equilibrium in a mechanical system can be judged by considering the variation in energy due to an infinitesimal disturbance. because etc are not zero.1 Continued *The difference between AS and dS Consider Taylor’s theorem Thus dS is the first term of the Taylor’s series only.. Infinitesimal variations of position cause return to equilibrium . If the energy (potential energy) increases . =0 ( A s )E > 0 (see Hatsopoulos and Keenan.Ax2+ . 2 dr2 dr2 Hence the following statements can be derived for certain classes of problem stable equilibrium neutral equilibrium unstable equilibrium (ds).2 State of equilibrium (iv) Metastable equilibrium Marble in higher of two troughs. 1. = 0 (dS). Then 1 d2S d2S However AS = dS + . Consider a circular bowl at the position where the tangent i s horizontal..larger variations cause movement to lower level. # 0. Fig. 1972).
2a). Since TI> T. namely dS > 0. and into block 2 are reversible.F=Tl Fig.. using eqns (1. T2)> 0. 1. If the high temperature block is at an temperature TI and the other at T2and if the quantity of energy transferred is SQ then the change in entropy of the high temperature block is SQ T I and that of the lower temperature block is 1  SQ a. From experience the block at the higher temperature will transfer ‘heat’ to that at the lower temperature.2). Hence the change in entropy of the system is equal to the change in entropy of the universe and is. if it decreases it will not return to that state.> T I and eqn (1.1) and (1. Consider a system comprising two identical blocks of metal at different temperatures (see Fig 1. If the two blocks together constitute an isolated system the energy transfers will not affect the total energy in the system. A slightly different approach. A similar method for examining the equilibrium of thermodynamic systems is required. but connected by a conducting medium.2 Heat transfer between two blocks Equilibrium of a thermodynamic system 3 then the system will return to its previous state. The same solution. > +SQ 72 (1. and hence the change of entropy of the surroundings is zero.2).la) and (1.1) and (1.2) would be (l.2a) Since the system is isolated the energy transfer to the surroundings is zero. This will be developed from the Second Law of Thermodynamics and the definition of entropy.la) ds. which is more analogous to the .=+T 2 Both eqns (1. If the transfers were irreversible then eqn (1. then the change of entropy of both the system and the universe is dS = (6Q/T2Tl)(T. is obtained from eqns (l.2) contain the assumption that the heat transfers from block 1. The previous way of considering the equilibrium condition shows how systems will tend to go towards such a state.1) would become SQ ds.
Then the change of entropy.4 State of equilibrium one used to investigate the equilibrium of mechanical systems. < 0 criterion of stability (stable equilibrium) . Consider the marble at the base of the bowl. in all possible variations of the state of the system which do not alter its energy. and the heat transfer is SQ. namely A E ) . are identical would be to cool the marble by an amount equivalent to the increase in potential energy before releasing it. if. the variation of entropy shall be negative. These conditions may be written mathematically as: (i) dS). < 0 (1. i. > 0 spontaneous change (unstable equilibrium) (ii) dS). This cooling is equivalent to lowering the entropy of the marble by an amount AS. when the entropy of an isolated system is at a maximum the system is in equilibrium.e. the initial and final conditions. are equivalent by applying the following simple analysis. The general criterion of equilibrium according to Keenan (1963) is as follows. Hence maximum entropy is obtained when the two blocks are in equilibrium and are at the same temperature. < 0. < 0. and since the cooling has been undertaken to bring the energy level back to the original value this proves that AE).l(i): if it is lifted up the bowl.6 T ) 26Q  SQ (26T) T 2+ 6T2 dT T2 (1. For stability of any system it is necessary and sufficient that. Equilibrium can be defined by the following statements: (i) (ii) (iii) if the properties of an isolated system change spontaneously there is an increase in the entropy of the system. for all the possible variations in state of the isolated system.6T ( T + 6 T ) ( T . CIS. > 0 and AS). with one temperature increasing and the other decreasing. = 0 equilibrium (neutral equilibrium) (iii) AS). This can be stated mathematically as AS). > 0 and AS). as shown in Fig l. A way to ensure the end conditions. and if that ‘friction’ is used solely to raise the temperature of the marble then its temperature will be higher after the process than at the beginning. its potential energy will be increased. is to consider these two blocks of metal to be in equilibrium and for heat transfer to occur spontaneously (and reversibly) between one and the other. Assume the temperature change in each block is 6 T . there is a negative change in entropy then the system is in stable equilibrium.is given by &=SQ T + 6T  SQ 6Q (TSTT6T) T .4) This means that the entropy of the system would have decreased.5) It can be seen that the statements of equilibrium based on energy and entropy. When it is released it will oscillate in the base of the bowl until it comes to rest as a result of ‘friction’.
2 Helmholtz energy (Helmholtz function) There are a number of ways of obtaining an expression for Helmholtz energy. System B..7) where 6 W + 6 W. System A is a closed system (i. . The heat engine then rejects a quantity of heat SQ.Helmholtz energy (Helmholtzfunction) 5 1. there are no mass transfers). 1. p 6V. (1. applying the First Law of Thermodynamics to System B gives 6 W. then. = d E + 6 Q.g.. the criteria for equilibrium were discussed and these were derived in terms of A S ) E . For a specified change of state these quantities.The variation of entropy is not always easy to visualise. the atmosphere.3 Maximum work achievable from a system In both arrangements. but the one based on the Clausius derivation of entropy gives the most insight. invariant composition. which are changes in properties. = net work done by the heat engine and System A. which delivers an infinitesimal quantity of heat SQ in a reversible manner to the heat engine E. e. dV and dS denote the changes in internal energy. In the previous section.. "~. which is of constant.3(b) is easier to understand. Figure 1. the system in Fig 1. System B SvstemA Reservoir To (b) Fig. then . Figure 1. Since the heat engine is internally reversible.3(a) shows a System A. Applying the First Law of Thermodynamics to System A gives 6 W = dE + S Q (1. Consider the arrangements in Figs 1. = 6 W + 6 W.6) If the heat engine (E.3(b) is a more specific example in which the work output is displacement work. to a reservoir. and it would be more useful if the criteria could be derived in a more tangible form related to other properties of the system under consideration. Let dE. at temperature To. volume and entropy of the system. which is a general system of constant composition in which the work output. 6W. would be independent of the process or work done.e. can be either shaft or displacement work..3(a) and (b).) and System A are considered to constitute another system. or a combination of both.I' . and the entropy flow on either side is equal.
SW. have been obtained for systems of invariant composition. was the net work obtained from System B (i. SW. U .11) and (1. Hence SW. or the Gibbs function..and it will be shown that the product TS is a measure of the unavailable energy.. This work detracts from the work previously calculated and gives the maximum useful work. G.Thus.13) The quantity H . . as SW.was derived. where the Helmholtz energy is defined as F=UTS (1.14). The more general form of . may be replaced by the intrinsic internal energy. and while it is doing this it must perform work on the atmosphere equivalent to p o SV.14) Gibbs energy is a property which has the units of energy.TOS) (1.SW.e./T.4 The use and significance of the Helmholtz and Gibbs energies It should be noted that the definitions of Helmholtz and Gibbs energies. It can be seen that this is less than the enthalpy.ToS)p. and indicates the maximum useful work that can be obtained from a system.TOS) because p o = constant. must be the maximum quantity of work that can be obtained from the combined system.3 Gibbs energy (Gibbsfunction) In the previous section the maximum work that can be obtained from System B. It can be seen that this is less than the internal energy.TS is called the Gibbs energy. 1. In the absence of motion and gravitational effects the energy.6 State of equilibrium and the change in entropy of System A during this process. Hence G=HTS (1. and it will be shown that the product TS is a measure of the unavailable energy. dV = d(E +poV. H . = SW. eqns (1.11) Helmholtz energy is a property which has the units of energy.P O dV if the system is in pressure equilibrium with surroundings. is dS = SQ. Hence SW.. = d(H . = = dE + To dS d(E . The expression for SW is called the change in the Helmholtz energy.12) (1.= d(E. It was also stipulated that System A could change its volume by SV.TOS) because To = constant (1. where p o is the pressure of the atmosphere.. will now be examined..7's) (1. because it is reversible. E. 1. The changes executed were considered to be reversible and SW. Gibbs potential.9) The expression EToS is called the Helmholtz energy or Helmholtz function.... U. System A +heat engine ER). comprising System A and heat engine ER.10) The significance of SW.= d(U . giving SW. and indicates the maximum work that can be obtained from a system..
1. > 0 is that for stability.T = 0 (3) AG&. if there is a reaction between the components of a mixture then this term will be nonzero and must be taken into account.. (iv) For a constant volume system in which W = 0. hence the minimum value of the function signifies the equilibrium condition. it is used extensively in the later chapters where it can be seen to be the driving force of chemical reactions. (iii) A decrease in entropy corresponds to an increase in F. if the amount of substance of the constituents does not change then this term is zero. p i dn.The use and significance o the Helmholtz and Gibbs energies 7 f these basic thermodynamic relationships. in differential form.15) The additional term. F. (i) 1. This criterion corresponds to work being done on the system. = F. Chemical potential is introduced in Chapter 12 when dissociation is discussed. < 0 spontaneous change equilibrium criterion of stability.2 GIBBS ENERGY (i) The change in Gibbs energy is the maximum useful work that can be obtained from a system undergoing a reversible process whilst remaining in pressure and temperature equilibrium with its surroundings.1 HELMHOLTZENERGY The change in Helmholtz energy is the maximum work that can be obtained from a closed system undergoing a reversible process whilst remaining in temperature equilibrium with its surroundings. (2) dG).. (1. Obviously.p dV+ C p i dn.dn. f (vi) The minimum value o Helmholtz energy corresponds to the equilibrium condition. is d U = T dS .LA.S d T . hence the criterion dF).4..4.. d F = . (ii) A decrease in Helmholtz energy corresponds to an increase in entropy. (ii) The equilibrium condition for the constraints of constant pressure and temperature can be defined as: (1) dG). is the product of the chemical potential of component i and the change of the amount of substance (measured in moles) of component i.. (v) For reversible processes. dG=SdT+Vdp+Cp.p d V + C . dn. d F = 0. for all other processes there is a decrease in Helmholtz energy. d H = T d S + V dp + C mi dn. However. > 0 (iii) The minimum value of Gibbs energy corresponds to the equilibrium condition. .
g. They are ignited by a small spark and convert rapidly into products. Most of the theories of thermodynamics are based on stable equilibrium. If an a particle is introduced into the chamber it provides sufficient perturbation to bring about condensation along its path. where the reactants (air and fuel) are induced into the engine in a premixed form. The equilibrium of mixtures of elements and compounds is defined by the state of maximum entropy or minimum Gibbs or Helmholtz energy.the body ‘measures’ the heat transfer rate. any other points in the pvT space are either in unstable or metastable equilibrium. Hence. The gases in a combustion chamber are often in unstable equilibrium because they cannot react quickly enough to maintain the equilibrium state. This is where a system exists in a ‘stable’ state without any tendency to change until it is perturbed by an external influence. The concepts of stable equilibrium can also be used to analyse the operation of fuel cells and these are considered in Chapter 17.8 State of equilibrium 1. Basically. These gases then mix due to diffusion. and this mixing is driven by the difference in chemical potential between the gases. Another example of unstable ‘equilibrium’ occurs when a partition is removed between two gases which are initially separated. releasing many thousands of times the energy of the spark used to initiate the combustion process. A good example of this is met in combustion in sparkignition engines. Another example of metastable equilibrium is encountered in the Wilson ‘cloud chamber’ used to show the tracks of a particles in atomic physics.4. e. the mixture of gases from an internal combustion engine when they exit the exhaust pipe. the pvT diagram for water. The Wilson cloud chamber consists of supersaturated water vapour which has been cooled down below the dewpoint without condensation . which explains why it is not possible to assess the temperature of something by touch because there is heat transfer either to or from the fingers . The measurement of thermodynamic properties relies on the measuring device being in equilibrium with the system. chemical potential is introduced in Chapter 12 and the process . stable equilibrium states are defined by state diagrams. this is discussed in Chapter 12. Unstable states cannot be sustained in thermodynamics because the molecular movement will tend to perturb the systems and cause them to move towards a stable state. The ‘distance’ of the unstable state from the state of stable equilibrium defines the rate at which the reaction occurs. Other examples includz explosive boiling. For example. Another form of equilibrium met in thermodynamics is metastable equilibrium. and most systems exist in this state. a thermometer must be in thermal equilibrium with a system if it is to measure its temperature. and will be discussed in Chapter 14. A system is in a stable state if it will permanently stay in this state without a tendency to change. and some of the crystalline states encountered in metallic structures. which might be more correctly named thermostatics. which can occur if there are not sufficient nucleation sites to induce sufficient bubbles at boiling point to induce normal boiling. Examples of this are a mixture of water and water vapour at constant pressure and temperature.it is in a metastable state.3 EXAMPLES OF DIFFERENT FORMS OF EQUILJBRIUM MET IN THERMODYNAMICS Stable equilibrium is the most frequently met state in thermodynamics. unstable states are only transitory states met in systems which are moving towards equilibrium. and many forms of crystalline structures in metals. this is referred to as rate kinetics. which is defined by minimum Gibbs or Helmholtz energy. where points of stable equilibrium are defined by points on the surface.
If systems are judged to undergo change while remaining in temperature and pressure equilibrium with their surroundings then most mechanical engineers would feel that no change could have taken place in the system. Some thermodynamic situations never achieve stable equilibrium. 16 and 17.4. then an increase in the Gibbs energy. If the process happened at constant temperature and pressure. Most systems are in equilibrium. for a system in temperature and pressure equilibrium with the environment 1. which was discussed in the introductory remarks to this section. in their stoichiometric proportions. such a process would be depicted by Fig 1. they exist in a steady state with energy passing between systems in stable equilibrium. if the system were a multicomponent mixture. and such a situation can be analysed using the techniques of irreversible thermodynamics developed in Chapter 16. an equilibrium mixture of carbon dioxide. 1.15) shows that. However. although nonequilibrium situations will be introduced in Chapters 14. For example. . G . consideration of eqns (1. this breakdown would change the composition of the mixture.Concluding remarks 9 of mixing is discussed in Chapter 16. in equilibrium with the surroundings.4 SIGNIFICANCE OF THE MINIMUM GIBBS ENERGY AT CONSTANT PRESSURE AND TEMPERATURE It is difficult for many engineers readily to see the significance of Gibbs and Helmholtz energies. This is directly analogous to the marble in the dish. 1. would have occurred. carbon monoxide and oxygen could change its composition by the carbon dioxide brealung down into carbon monoxide and oxygen.4 Variation of Gibbs energy with chemical composition. it would be possible for changes in Gibbs (or Helmholtz) energies to take place if there were changes in composition.4. % Carbon dioxide in mixture Fig.5 Concluding remarks This chapter has considered the state of equilibrium for thermodynamic systems.
These energies also define the maximum amount of work that can be obtained from a system.0 C.2 kJ/kg K for water: K = cp/c. This i is connected to a large reservoir which is maintained at a temperature of 300 K by a reversible heat engine.= 1.7 K] 5 A thermally isolated system at constant pressure consists of 10 kg of air at a temperature of 1000 K and 10 kg of water at 300 K. Calculate the maximum amount of work that can be obtained from the system. = 4. 2 Determine the criteria for isothermal equilibrium of a system at (a) constant volume.10 State of equilibrium It has been shown that the change of entropy can be used to assess whether a system is in a stable state. cp. connected together by a heat engine. Assume that the system is: (i) constant. } Assume c. Two new properties. What would be the equilibrium temperature of the system if (a) the heat engine has a thermal efficiency of zero. (ii) variable in composition. = 0.7 kJ/kg K 7~ = c ~ / c . (b) the heat engine is reversible? {Hint: consider the definition of equilibrium defined by the entropy change of the system.4 [432. Assume that the system is: (i) constant. 376. = 0.4 r385.98 H/kg K.7 kJ/kg K for air: K = cP/c. in composition. = 4. = 1. (b) constant pressure. in composition. = 1. PROBLEMS 1 Determine the criteria for equilibrium for a thermally isolated system at (a) constant volume.2 kJ /kg K K = c. and invariant. 3 A system at constant pressure consists of 10 kg of a r at a temperature of lo00 K.= 1. connected together by a heat engine. Gibbs and Helmholtz energies.1 K] . and invariant. have been introduced and these can be used to define equilibrium states. Take the specific heat at constant pressure of air. (ii) variable in composition.as 0. [3320.4 K. and (b) constant pressure.0 C./c.3 kJ] 4 A thermally isolated system at constant pressure consists of 10 kg of air at a temperature of 1000 K and 10 kg of water at 300 K. What would be the equilibrium temperature of the system if the maximum thermal efficiency of the engine is only 50%? Assume for water: for air: c.
(a) Describe the meaning of the term thermodynamic equilibrium. is the partial pressure of the vapour. then dPv =dP P v P where p. vfg = difference between liquid and vapour phases. p = pressure. 7 An incompressible liquid of specific volume v. and p is the total pressure.P0)Y . is the density of the vapour and p1 is the density of the liquid.I(P . Using the following data.(Pv Po)b) i T where po is the vapour pressure when no inert gas is present.O) show that T dP = dT where T = temperature. Evaluate (i) the change of density between these pressures. p is the total pressure.6 kJ/kg.. 1 Vfg and Show the significance of this on a phase diagram. but increases to 508. Explain how entropy can be used as a measure of equilibrium and also how other properties can be developed that can be used to assess the equilibrium of a system. The latent heat of fusion of tin is 58. is in equilibrium with its own vapour and an inert gas in a closed vessel. The vapour obeys the law P(V b)=%T Show that (L) 8 . 0. show the pressure at which graphite and diamond are in . (b) The melting point of tin at a pressure of 1 bar is 505 K. [254 100 kg/m3.Problems 11 6 Show that if a liquid is in equilibrium with its own vapour and an inert gas in a closed vessel. 1 = latent heat. If two phases of a component coexist in equilibrium (e.= . p. and (ii) the change in entropy during melting.g. liquid and vapour phase H.4 K at 1000 bar.1 157 kJ/kg K] 9 Show that when different phases are in equilibrium the specific Gibbs energy of each phase is equal.
12 State of equilibrium
equilibrium at a temperature of 25°C. The data for these two phases of carbon at 25°C and 1 bar are given in the following table: Graphite Specific Gibbs energy, g/(kJ/kg) Specific volume, v/(m3/kg) Isothermal compressibility, k/(bar')
0 0.446 x 1 0  ~
Diamond 269 0.285 x 0.158 x
2.96 x
It may be assumed that the variation of kv with pressure is negligible, and the lower value of the solution may be used. [ 17990 bar]
10 Van der Waals' equation for water is given by
P= where p
0.004619T  0.017034 v  0.0016891 V2
(bar), v = specific volume (m3/kmol), T
= temperature
= pressure
(K).
Draw a p  v diagram for the following isotherms: 250"C, 270"C, 300°C, 330°C, 374"C, 390°C. Compare the computed specific volumes with Steam Table values and explain the differences in terms of the value of pcvc/%Tc.
Availability and Exergy
Many of the analyses performed by engineers are based on the First Law of Thermodynamics, which is a law of energy conservation. Most mechanical engineers use the Second Law of Thermodynamics simply through its derived property  entropy ( S ) . However, it is possible to introduce other ‘Second Law’ properties to define the maximum amounts of work achievable from certain systems. Previously, the properties Helmholtz energy ( F ) and Gibbs energy ( G ) were derived as a means of assessing the equilibrium of various systems. This section considers how the maximum amount of work available from a system, when interacting with surroundings, can be estimated. This shows, as expected, that all the energy in a system cannot be converted to work: the Second Law stated that it is impossible to construct a heat engine that does not reject energy to the surroundings.
2.1
Displacement work
The work done by a system can be considered to be made up of two parts: that done against a resisting force and that done against the environment. This can be seen in Fig 2.1. The pressure inside the system, p , is resisted by a force, F , and the pressure of the environment. Hence, for System A, which is in equilibrium with the surroundings pA=F+pd where A is the area of crosssection of the piston.
Svstem A
(2.1)
Fig. 2.1 Forces acting on a piston
If the piston moves a distance dx, then the work done by the various components shown in Fig 2.1 is
pA d x = F d x + p J dx (2.2) where PA dx = p dV = SW,,, = work done by the fluid in the system, F dx = SW,, = work done against the resisting force, and pJ dx = po dV = SW,, = work done against the surroundings.
14 Availability and exergy Hence the work done by the system is not all converted into useful work, but some of it is used to do displacement work against the surroundings, i.e.
sw,,, SW, + SW,, =
which can be rearranged to give
(2.3)
sw,
= SW,,, SW,, 
(2.4)
2.2 Availability
It was shown above that not all the displacement work done by a system is available to do useful work. This concept will now be generalised to consider all the possible work outputs from a system that is not in thermodynamic and mechanical equilibrium with its surroundings (i.e. not at the ambient, or dead state, conditions). Consider the system introduced earlier to define Helmholtz and Gibbs energy: this is basically the method that was used to prove the Clausius inequality. Figure 2.2(a) shows the general case where the work can be either displacement or shaft work, while Fig 2.2(b) shows a specific case where the work output of System A is displacement work. It is easier to follow the derivation using the specific case, but a more general result is obtained from the arrangement shown in Fig 2.2(a).
,.
..... .....
System B Svstem A 6W
'\,
System B
',,
*6WR
Reservoir To
0)
(4
e 7
Reservoir T o
Fig. 2.2 System transferring heat to a reservoir through a reversible heat engine
First consider that System A is a constant volume system which transfers heat with the surroundings via a small reversible heat engine. Applying the First Law to the System A
W d U = SQ SW= SQ S S
(2.5)
where SW,indicates the shaft work done (e.g. System A could contain a turbine). Let System B be System A plus the heat engine E,. Then applying the First Law to system B gives d U = C (SQSW)=SQ,(SWs+SWR) (2.6)
Examples
15
As System A transfers energy with the surroundings it under goes a change of entropy defined by
because the heat engine transferring the heat to the surroundings is reversible, and there is no change of entropy across it. Hence (SW~+dWR)=(dUTodS) (2.8)
As stated previously, (6Ws + 6WR)is the maximum work that can be obtained from a constant volume, closed system when interacting with the surroundings. If the volume of the system was allowed to change, as would have to happen in the case depicted in Fig 2.2(b), then the work done against the surroundings would be po dV, where po is the pressure of the surroundings. This work, done against the surroundings, reduces the maximum useful work from the system in which a change of volume takes place to 6W + SW,  p o dV, where 6W is the sum of the shaft work and the displacement work. Hence, the maximum useful work which can be achieved from a closed system is
6 W + SW,
=  (dU +Po dV  To dS)
(2.9)
This work is given the symbol dA. Since the surroundings are at fixed pressure and temperature (Le. po and Toare constant) dA can be integrated to give
A = U + p o V  TOS
(2.10)
A is called the nonflow availability function. Although it is a combination of properties, A is not itself a property because it is defined in relation to the arbitrary datum values of p o and To. Hence it is not possible to tabulate values of A without defining both these datum levels. The datum levels are what differentiates A from Gibbs energy G. Hence the maximum useful work achievable from a system changing state from 1 to 2 is given by
W,,=
AA= (A2Al)=AlA2
(2.11) (2.12a)
The specific availability, a , i.e. the availability per unit mass is
a = u +pov Tos
If the value of a were based on unit amount of substance (Le. kmol) it would be referred to as the molar availability. The change of specific (or molar) availability is h a = a2 a , = (u2+ pov2 Tos2) ( u l + pov,  Tosl) = (h2 + v2( Po  P d )  ( h l +
V I ( Po
 P I ) )  To(%  $1)
(2.12b)
2.3 Examples
Example 1 : reversible work from a piston cylinder arrangement (this example is based on Haywood (1980))
System A, in Fig 2.1, contains air at a pressure and temperature of 2 bar and 550 K respectively. The pressure is maintained by a force, F , acting on the piston. The system is taken from state 1 to state 2 by the reversible processes depicted in Fig 2.3, and state 2 is
16 Availability and exergy equal to the dead state conditions with a pressure, p,,, and temperature, To, of 1 bar and 300 K respectively. Evaluate the following work terms assuming that the air is a perfect gas and that cp= 1.005 W/kg K and the ratio of specific heats K = 1.4. (a) The air follows the process 1a2 in Fig 2.3, and transfers heat reversibly with the environment during an isobaric process from la. Calculate the following specific work outputs for processes 1a and a2: (i) (ii) (iii) (iv) the work done by the system, 6W,,,; the work done against the surroundings, SW,,; the useful work done against the resisting force F , SW,; the work done by a reversible heat engine operating between the system and the surroundings, 6WR. the gross work done by the system, C(SW,,, + 6WR); the net useful work output against the environment, C(SW, + 6WR); the total displacement work against the environment, C(SW,,); the work term p o ( v 2 v,).
Then evaluate for the total process, 12, the following parameters:
(v) (vi) (vii) (viii)
2
Entropy, S
Fig. 2.3 Processes undergone by the system
Solution
It is necessary to evaluate the specific volume at the initial condition, state 1. p , v , = RT,, hence v, = R T , / p , The gas constant, R , is given by R = ((K l)/x)cp = 0.4 x 1.005/1.4 = 0.287 kJ/kgK, and hence
v, =
0.287 x lo3x 550 2x
io5
= 0.7896 m3/kg
Examples
17
The intermediate temperature, T,, should now be evaluated. Since the process a2 is isentropic then Tamust be isentropically related to the final temperature, T,. Hence ( p )m (:0.4/1.4 Ta= T2 2 =300= 365.7 K
P2
365.7 PlTa Thus v a = v1 = V I PaTl 550 Consider process 1a:
wsYs  a
=
= 0.6649~1
IIap = pa(va vl), for an isobaric process dv

2
io5
io3
(0.6649  1.O) x 0.7896 = 52.96 kJ/kg 1
~
Ws,lla
=
=
IIaPodv=
io5
io3
(0.6649  1.0) x 0.7896
26.46kJ/kg The useful work done by the system against the resisting force, F , is the difference between the two work terms given above, and is 26.46 kJ/kg The work terms derived above relate to the mechanical work that can be obtained from the system as it goes from state 1 to state a. However, in addition to this mechanical work the system could also do thermodynamic work by transfemng energy to the surroundings through a reversible heat engine. This work can be evaluated in the following way. In going from state 1 to state a the system has had to transfer energy to the surroundings because the temperature of the fluid has decreased from 550 K to 365.7 K. This heat transfer could have been simply to a reservoir at a temperature below T,, in which case no useful work output would have been achieved. It could also have been to the environment through a reversible heat engine, as shown in Fig 2.2(b). In the latter case, useful work would have been obtained, and this would be equal to
w s 11a ue
= wsys
11a
w, s
Ila=
SwR = vRSQ, where vRis the thermal efficiency of a reversible heat engine operating between T and To,and SQ is the heat transfer to the system. Thus
Hence, the work output obtainable from this reversible heat engine as the system changes state from 1 to a is a TTo WR =  = SQ  dT c, T
1,
( T ,  T , )  To In

365.7 (365.7  550)  300 In ___ 500
18 Availability and exergy
Now consider process a2. First, evaluate the specific volume at 2, v2:
plT2 v2 = V , ~2T1
___
2 x 300 1 x 550
v 1= 1 . 0 9 0 9 ~ ~
The expansion from a to 2 is isentropic and hence obeys the law p v " = constant. Thus the system work is
wsysla2
(1 x 1.0909 2 x 0.6649)
=
2
0.7896 x lo5
X
1  1.4
io3
= 47.16 kJ/kg
~smr1a2=j~o ~ wuseIa2
=
1 io5 d v = (1.0909  0.6649) x 0.7896 = 33.63 W/kg p io3
wsysIa2~sumIa2=13*52kJ/kg
The energy available to drive a reversible heat engine is zero for this process because it is adiabatic; hence
wR la2 =
The work terms for the total process from 1 to 2 can be calculated by adding the terms for the two subprocesses. This enables the solutions to questions (v) to (viii) to be obtained. The gross work done by the system is
w ~ ~ ~ = wR)= (52.96+47.16+62.18+0=56.38 W/kg ~ w ~ ~ ~ +
The net useful work done by the system is
W,,,~=E(W,+ w R ) =
w, ,=
26.46+ 13.52+62.18=49.24kJ/kg
The total displacement work done against the surroundings is 26.46+33.63=7.17 W/kg
The displacement work of the surroundings evaluated from
p0(v2 vl) = 1 x lo5x (1.0909 1) x 0.7896/103= 7.17 kJ/kg Example 2: change of availability in reversible piston cylinder arrangement
Calculate the change of availability for the process described in Example 1. Compare the value obtained with the work terms evaluated in Example 1.
Solution
The appropriate definition of availability for System A is the nonflow availability function, defined in eqn (2.12a), and the maximum useful work is given by eqns (2.11) and (2.12b). Hence, w,,,is given by
w,,, Aa =
=
=
 ( a 2  a , ) = a ,  a2
 v2)  To(s,  s2)
4  u + PO(V1 2
h = 3343 kJ/kg. s1 .547 kJ/kg K . can be evaluated from dT dp d s = cP . v = 0.7.T2) + P O ( V 1 .0.1 115 m3/kg.7896 io3 .s2 = cp In .5 kJ/kg (i) Change of availability if expanded to 20 bar.1078/103 . s = 6. t = 450°C u = 3020 kJ/kg.287 x In .R T P which for a perfect gas becomes Tl PI s1.300) + 1x ~ = io5 (1 ..R In T2 P2 550 2 = 1.07 = 49. Solution From Rogers and Mayhew tables: at p = 30 bar. the change of availability can be evaluated directly to give the maximum useful work output from a number of processes without having to evaluate the components of work output separately.082 = 849.005 x In .082 kJ/kg K Hence the specific availability at these conditions is a = u +pov .123.005 . h = 2904 kJ/kg. 250°C.Tos = 3020 + 1 x lo5x 0.25 kJ/kg This answer is identical to the net useful work done by the system evaluated in part (vi) above.s2.1078 m3/kg.1. From Rogers and Mayhew tables: at p = 20 bar. s = 7.5 . v = 0. Evaluate the maximum useful work that can be obtained from this vapour if it is expanded to (i) 20 bar. this is to be expected because the change of availability was described and defined as the maximum useful work that could be obtained from the system.= 0.17 .TObI . Hence. 450°C if the surroundings are at p o = 1 bar.287)(550 .41024 kJ/kgK 300 1 Substituting gives WuSe = C"(T1 .41024 = 179. 250°C.308 x 7. (ii) the dead state.v2) . Example 3: availability of water vapour Evaluate the specific availability of water vapour at 30 bar.300 x 0. to= 35°C.0.Examples 19 The change of entropy. t = 250°C u = 2681 kJ/kg..s 2 ) (1.0909) x 0.
~ 2 ) ) + 0.T.547 = 675. this could have been evaluated using eqn (2.146.308 x (7.082 .308 x (7.5 . .8 kJ/kg This could also be evaluated using eqn (2. even if the datum levels were reduced to the triple point the maximum useful work would still only be w. = a .0.P I )(h2 + ~ 2 ( ~ 0 .1078 x (0.a2= 849.6 + 1 x lo5x 0.TO(s.P I ) .7 M/kg and the maximum work that can be obtained by expanding to the dead state is w.0) = 1086.6 + 0.30) x lo2.9 = 857.s = 146. Aa = (3343 .6 kJ/kg.3 M/kg = It is also possible to evaluate the availability of a steadyflow system and this is defined in a similar manner to that used above.312.9 kJ/kg = This shows that although the energy available in the system was 3020 kJ/kg (the internal energy) it is not possible to convert all this energy to work. . giving Wmax = h .20) x lo2 .~ 2) TO(S.12b).T.7 W/kg Thus the maximum work that can be obtained by expanding the gas to these conditions is w.20 Availability and exergy The specific availability at these conditions is a = u + p .082 . Change of availability if expanded to datum level at p o = 1 bar.1006 x s = 0.1115/1O3308x6.5045 W/kg K m3/kg.9. . .6.+ V ~ ( P O. It should be noted that this ‘energy’ is itself based on a datum of the triple point of water. + V I ( P O . = a.6+211.0) + 0.s =2681 + I x lO5~O.7) = 858. However.0. but the dead state is above this value.2 W/kg Again.547) =439312.78= 173.5045) = 3196.1) x lo2 . m Aa= A.12b) to give W.0.001006 x (1 .6 kJ/kg.001006/103.a2= 849. h = 146. v .308 x 0.082 .2025.5 .1078 x (1 .11 15 x (1 . The specific availability at the dead state is a = u +pov .273(7.6 + 0 .164. to= 35°C (ii) u = 146.00612 . ~ 2 ) )) = 3343 .5045 = 8.675.30) x lo2.(h2 + v ~ ( P o .(8. .7 = 173.2904 The values obtained by the different approaches are the same to the accuracy of the figures in the tables.4 .30) x lo2.5 kJ/kg ‘a= = 3343 . but in this case the reversible heat engine extracts . v = 0.1078 x (1 .P ~.
and a compressor. The available energy on this diagram is given by abcda and is given by E. .0. This can be considered to be made up of an infinite number of strips 1mn41 where the temperature of energy transfer is essentially constant.Tos2) = (3343 .) (2. e. i.(h2.( h . However.Tos. is the minimum amount of heat that can be rejected because processes 1 to 2 and 3 to 4 are both isentropic.a. . adiabatic and reversible. i. = Q TdS (2.e.E.. Aa.4. = Q . SQ. the maximum work that could be obtained from a steadyflow system is the change in flow availability.13a) Aa.  Tosz.. The energy transfer obeys SQ = T SQo To where SQ = heat transferred to system and SQo= heat rejected from system. isentropic and isothermal reversible processes. which produces a work output. Hence the amount of energy that must be rejected is (2. TI= T4 = T . = h. which absorbs a work input. If the kinetic and potential energies of the flowing stream are negligible compared with the thermal energy then the steady flow availability is a .( a f 2 u.Tos The change in steady flow availability is (2.Irreversibility 21 energy from the flowing stream. all real processes are irreversible and it is possible to obtain a measure of this irreversibility using the previous analysis.. this diagram indicates an internally reversible process from a to b.4 kJ/kg = 2. 2.5045) = 1170. Consider Fig 2. can be written as a definite integral because the process is an isentropic (reversible) one... Then E.082 . = af2.the unavailable part is that which must be thrown away. This will be illustrated by two examples: a turbine..15) where Q is defined by the area abfea.Tos.14) Note that the quantity of energy.g. In reality SQ. . .5 Irreversibility The concept of reversible engines has been introduced and these have operated on reversible cycles. as in an engine (ER)undergoing an infinitesimal Camot cycle.13b) Thus.6) .. = h .146. which for the previous example is w. = .4 Available and nonavailable energy If a certain portion of energy is available then obviously another part is unavailable .e.308 x (7. is the energy that is unavailable and is given by cdefc.) = h .
4 Available and unavailable energy shown on a Ts diagram Example 4: a turbine An aircraft gas turbine with an isentropic efficiency of 85% receives hot gas from the combustion chamber at 10 bar and 1000°C. S Fig. 2.100 W/kg K.35. s2. Aa = af2.35/'.T2') 9 For the isentropic expansion.5 kJ/kg The change in availability of the working fluid is given by eqn (2. For an isentropic change..To+ = a. = wT lisen = 629. . cp= 1. . determine (b) the change of availability and the work done.5. K = 1. If the temperature of the atmosphere is 20"C.h.= s .35 = 700 8 K giving wTlisen=1.8)=629. (a) Isentropic expansion From the steady flow energy equation the specific work done in the isentropic expansion is wT li~en= cp(Tl . Solution The processes involved are shown in Fig 2.. Then.T.13b). and the work done by the turbine ifthe expansion were isentropic.. = h . Assume that the specific heat at constant pressure.22 Availability and exergy b 2" t" 5 3 TI = T4= T C f Entropy.' )=" / 1273(1/10)0. and that the ratio of specific heats.. and (d) the net loss of availability of the universe (Le. a. (c) the change of availability of the surroundings. where af2< h.100 x (1273700..s. . determine (a) the change of availability of the working fluid. the irreversibility). T2= T I (p 2 / p I ) ( " . . . and hence Aa = h.5 kJ/kg. It expands this to the atmospheric pressure of 1 bar. for the actual turbine.
wT/cP=1273 ..this would be expected in the case of an isentropic process.e. from the perfect gas law.5 kJ/kg. then the turbine work K.S . The change of availability is given by eqn (2.0/1.535.(1.285 kJ/kg K . I Entropy.T O ( S ~ .Irreversibility 23 The change of availability of the surroundings is 629.5 = 535.1) x 1. S Fig.13b) as Aa = af2.  K 1.5 Turbine expansion on a T .~ ~ .s diagram (b) Nonisentropic expansion If the isentropic efficiency of the turbine is 85%. R= (ICl ) ~ . 2.35 = 0.85. and the processes are reversible .100 = 786 vT= 0.TOS~ ( h .0 kJ/kg The temperature at the end of the expansion is T2 = TI .a. This means that the energy can be transferred between the system and the environment without any degradation. i. = h2 ..W T . is wT = vTwTliscn = 0.100 .T O ( S ~ . ) The change of entropy for a perfect gas is given by where. and hence the change of availability of the universe is zero for this isentropic process.TOsl)  =~ ~ .S ~ ) = .35 .85 x 629.
6.9 kJ/kg This can also be calculated directly from an expression for irreversibility I = T o AS = 293 x 0.e. Example 5: an air compressor A steady flow compressor for a gas turbine receives air at 1 bar and 15"C.6562 = 0. hence Aasurroundings k J / k = 535 (d) The irreversibility is the change of availability of the universe.To(s2 sl) = 535 .s1 = 1.1258 = 571. c p= 1.5304 1273 10 + 0.293 x 0.0 = 36.004 kJ/ kg K.1258 kJ/kg K Thus Aa = 535 .86 kJ/kg Note that the irreversibility is positive because it is defined as the loss of availability. and the ratio of specific heats.285 In . i.9 kJ/kg (c) The change of availability of the surroundings is equal to the work done. S Fig.1 In . AalmiverseAasystcm Aasurroundings = + = 571. 1c = 1.4.1258 = 36.= 0. with the specific heat at constant pressure. 2.9 + 535. Treat the gas as an ideal one.0.24 Availability and exergy Thus the change of entropy during the expansion process is 786 1 s. which is the sum of the changes of availability of the system and its surroundings. Solution The processes are shown in Fig 2. which it compresses to 7 bar with an efficiency of 83%. Based on surroundings at 5 ° C determine (a) the change of availability and the work for isentropic compression.. For the actual process evaluate (b) the change of availability and work done. /p2=7bar bar ~~ Entropy.6 Compression process on a 7's diagram . (c) the change of availability of the surroundings and (d) the irreversibility.
This reflects the higher temperature achieved during irreversible compression.e.a. there is no heat loss or addition.(s. )= 1. = h2. giving w Clisen = Ah = 215.e.08639 = 235.5565 = 0.4 .T A S If the process is isentropic. even if the energy in the gas after compression is passed through a reversible heat engine. = h.T.R In .6 Graphical representation of available energy.. it will not be possible to produce as much work as was required to compress the gas.278 x 0. as shown in Fig 2. h.4 K = The work done can be calculated from the steady flow energy equation. while the available energy in the fluid has been increased by the work done on it. i.3 kJ/kg  (b) The actual work done. . T2 P2 Asl2= c pIn ..4 . . = A h .3 kJ/kg The change of availability is given by eqn (2. T . = af2. = auP.83 = 259.4 .13b) as Aa..w c = 1.4 K. 2. and irreversibility Consider the energy transfer from a high temperature reservoir at THthrough a heat engine (not necessarily reversible).6 kJ/kg.4 = 24.08639 = 24. This means that..s l ) = Ah .288) = 215. and then Aaf = cp(T2.Graphical representation of available energy 25 (a) Isentropic compression: T. . the quality o the energy in the universe has been reduced.4 kJ/kg There has been a greater increase in availability than in the case of reversible compression.= 0.T& = 259.004 x (502.0.3/0. = T ( ): (K .. AaSw 259.259. Hence = h. T2. the change is less than the work done.(259. and the temperature at 2.7.a. (d) The process an adiabatic one. w c = w c Iisen/vC 215. AS = 0.4 kJ/kg. Hence the irreversibility of the process is given by I = To AS = 278 x 0.l)/K = 288 x 7°'286 502.is given by T2= h 2 / c . even though the quantity of f energy has remained constant.641 1 . i.08639 kJ/kg K Ti P1 Hence Aa. = 546.0 kJ/kg Hence.02 kJ/kg of availability of the universe This is the negative of the change (system + surroundings) which is given by A a ~ = AasystcmAasmundlngs " + = 235. Hence.004 x 288 .4) = 548.4 kJ/kg. . (c) The change of availability of the surroundings is equal to the enthalpy change of the = system.
ev= E. (2.W o = QH .ASH) (2.17) Hence the energy which is unavailable due to irreversibility is defined by Ei.T ASH o o (2. and irreversibility The available energy flow from the hot reservoir is EH=QHToASH The work done by the engine is W= QH (2.T ASH.16) .7 by the area marked ‘A’. However.20) .18) = To(AS0 . i. 2.7 Representation of available energy. while the energy ‘lost’ due to irreversibility is denoted ‘I’ and is defined Eimv= To(AS0 .. for all other engines it is nonzero.Qo) = Qo .W=QH.e.. The available energy is depicted in Fig 2.26 Availability and exergy c Fig.T AsH(QH .ASH) In the case of a reversible engine QH = c AS = 0 because entropy flow is conserved.19) Qo T H T O Hence the unavailable energy for a reversible engine is To ASHwhile the irreversibility is zero.Qo The total change of entropy of the universe is (2.
w + p 0 (v2. and T is the temperature at which the heat transfer interactions with the system occur (see Fig 2. However.a.23) Equation (2.Availability balance for a closed system 27 2. .u . Calculate the change in availability of the universe due to this operation. = S2. .25) where q . it is not always possible to do this and it is useful to derive a method for evaluating the change of availability from ‘external’ parameters. and that of steel is 0.18 kJ/kg K.2(a)). T 2 . SQ 2 . and take the datum temperature and pressure as 20°C and 1 bar respectively.’(1  :)dq . Example 6: change in availability for a closed system A steel casting weighing 20 kg is removed from a furnace at a temperature of 800°C and heat treated by quenching in a bath containing 500 kg water at 20°C. The significance of eqn (2.42 kJ/kg K. Wand u per unit mass.24) can be examined by means of a couple of simple examples.a .) = 1.23) can be rearranged to give (2.10)).v l ) . (2.SW) = I 2 1 SQ .24) The change in specific availability is given by a2 .22) I 2 l T SQ + u where u is the internal irreversibility of the system. are the values of Q. The specific heat of the water is 4.U . w and u.To(sz.21) and (2.21) (2.T.W (2. Assume that the bath of water is rigid and perfectly insulated from the surroundings after the casting has been dropped in. = u2 .Too (2.Vi ) . as = 1. If a closed system goes from state 1 to state 2 by executing a process then the changes in that system are: from the First Law: from the Second Law: U2 .To SQ 1. Equations (2. This can be done in the following way for a closed system.S .22) can be written in terms of availability (see eqn (2. = 2 (SQ .sl) +po(v2 v.W + po(V2 .7 Availability balance for a closed system The approaches derived previously work very well when it is possible to define the changes occurring inside the system. for a system which can change its volume during the process.
28 Availability and exergy Solution The process can be considered to be a closed system if it is analysed after the casting has been introduced to the bath of water.154 = 11.154 kJ/K 10. + SS. . .VI) = 0 because the system is adiabatic and constant volume. Hence eqn (2.815 4. = 1 (1  ): dQ = .42 x 20 + 500 x 4. (293 . change of entropy of water = mwcw In = .)  In this case. = = m.12 K 2. . change of availability A . 1. + mwcwTw  20 x 0. 296.c.815 kJ/K 3. It could have been analysed in a different manner by taking explicit note of the work which could be achieved from each part of the composite system before and after the heat transfer had taken place.c.24) can be applied: A.:  v.A .= 500 x 4.:)mccc dT = m.18 x 293 0.1073) . = + 22. .1 (1 .A .12 ~ 293 22.T. . SQ = 0.18 m.)+Po(& . if the combined system is considered.s.[T .42 x 1073 + 500 x 4.293 x In . This will now be done. = TOO The irreversibility can be calculated in the following manner: 1. change of entropy of casting = 10..&(S.u.w + 1 ).SQ .2 9 3 ~ 11. + m.A.c. = .T o a = . The loss of availability was analysed above by considering the irreversibility associated with the transfer of energy between the casting and the water.339 U/K 5. change of entropy of system (and universe) SS = 6S. Work available by transferring energy from the casting to the environment through a reversible heat engine before the process W.To In TITc TO T. = u.34~3323k. W = 0 and po(Vz.y ) = J z ( 1 .18 T W T f x In 296. final temperature of system T.c.l This solution indicates that the universe is less able to do work after the quenching of the casting than it was before the casting was quenched. Thus A . .
.V1!  I (2. Change of availability of universe is A ..:)dq w +po(v.27) availability transfer accompanying heat transfer nibilities Equations (2. dv dt (2.Toom . Work available by transfening energy from the water bath to the environment through a reversible heat engine after the process W. dV  . .i = j12 . da dt (2. dt ..26) in the form of a rate equation.:)mwcw dT = rnwcw[T ToIn TITf  To (293 . = . .24) can be considered to be made up of a number of terms. as shown below: availability transfer accompanying heat transfer availability transfer accompanying work availability destruction due to irrevenibilities Too Y = II2 (1 .334.a . = (1 .W = ~(3357.:d )Q . = (1  $!) 1.*W + p o ( V .. . Equation (2. avalability transfer dV avaiiabilitydestruction due to irreversibilities T0a I I accompanying work = .27) can be written in terms of specific availability to give a2 .28) dv dt .l" . .Availability balance for a closed system 29 2.A .296.w+p.12) .VI> .w + po(v. in which case the rate of change of availability is dt availability transfer accompanying heat transfer (l?)Q .?)dq (1 .w + p o dt availability transfer accompanying work  rusliirhiiim v ~esmction P I ".26) and (2.47)=3323 kJ This is the same solution as obtained by considering the irreversibility. due to (2..293 x In 3. dQ = (1 .26) availability transfer accompanying heat transfer availabi]ity transfer accompanying work availability destruction o due t irreversibilities It is also possible to write eqn (2.29) .v l > .
+ mair . This is defined as where T.~ o ) ] (2. resulting in A i . Table 2. Equation (2.30 300 1 .24) contains a term which takes into account the change of volume ( p o ( V z V . x.946 1. This can be modified to allow for combustion by the addition of a term for the availability of reaction.po/(bar) 12 44 000 1 .U0). Assume the compression and expansion processes are adiabatic. T. To/(K) Pressure of surroundings. = mass of fuel and m = total mass of mixture = m . Hence (2./(kJ/kg K ) Ratio of specific heats.~ o ) + p o ( ~ i .1. c.p. The data in this example is based on Heywood (1988). Solution This example introduces two new concepts: 0 0 the effect of change of volume on the availability of the system. Equation (2.39 0. Qb/(kJ/kg) Ratio.24) gives the change of availability of a system of constant composition as an extensive property./(bar) Temperature at start of compression. ) ) .A o = A A R + ( U j ./(OC) Air/fuel ratio. rc Calorific value of fuel. E Specific heat of air at constant volume.30 Availability und exergy Example 7: change of availability for a closed system in which the volume changes An internal combustion engine operates on the Otto cycle (with combustion at constant volume) and has the parameters defined in Table 2.o 1.33) where m.T o ( ~ i .32) can be generalised to give the value at state i relative to that at state 0. is the temperature at which the energies of reaction are evaluated.but it does not contain a term for the change in availability which occurs due to ‘combustion’.1 Operating parameters for Otto cycle Compression ratio. K Temperature of surroundings.To(SjSo)+po(VjVo) =mfAAR+m[(ujuo). the effect of ‘combustion’ on the availability of the system. = AAR/Q: Pressure at start of compression.31) Equation (2.o Calculate the variation in availability of the gases in the cylinder throughout the cycle from the start of compression to the end of expansion.0286 60 15.
3.). .T. Examples of the availability of reaction are given in section 2.38) (2. The values at the state points of the Otto cycle are shown in Tables 2.2.37) Considering the individual terms in eqn (2.9 respectively.36) If the energy of reaction per unit mass of mixture is written q* = (Q.8 and 2.9.2 and 2. based on the total mass of mixture. [(z) [ c.39) (2. and the variation of availability as a function of crankangle and volume during the cycle (calculated by applying eqn (2.34) where &=overall airfuel ratio.a.41) Equation (2. is 31 (2. 4* a.Availability balance for a closed system The specific availability. The availability of reaction can be related to the internal energy of reaction by (2.40) Hence.41) in a stepbystep manner) is shown in Figs 2./(E + 1) then (2.35) which gives (2. 4* * 1 + Kh(Kl)h z o  Ti To Po i( K   I)(: I)] (2.37) (2.41) can be applied around the cycle to evaluate the availability relative to that at the datum state.
.11 1. 4* .80014 4. this gives a3ao 4* a2a.17105 0.43) P2 p311 Equation (2. This example is based on a cycle with a premixed charge.73 1469 9.( K .731469 0 0.41) is used to consider the effect of adiabatic. In the Otto cycle combustion takes place instantaneously at top dead centre (tdc).097666 0.043 1679.0286 1.28923 127.731469 9. Figures 2.5691 5.2.135668 0.9.000775 0.43) is the change in entropy of the working fluid which is brought about by combustion.32 Availability and exergy Table 2.753948 1. and the volume remains constant. and this is calculated in section 2. 4* +cvTo 4* 4* [i Kln(Kl)h :: (2.332836 0.044404 300 333 701.033 0.097666 0.3 Terms in eqn (2.127041 0. The calculation of most of the other points on the cycle is straightforward.27225 0.1).62316 Table 2.~ 0 a2a.17105 0.599289 9.9 show how the nondimensional availability of the charge varies around the cycle. the availability at point 3 is a 3 . and since the entropy of the gases increases due to combustion this term reduces the availability of the gas.e.11 0. constant volume combustion occurring between points 2 and 3. i.029375 1. = 0 Hence.127041 0.029375 0.62316 The value of availability of the charge at state 0 is based on the ratio of the availability of combustion of octane to the heat of reaction of octane.955991 0.I){(: .{Kln .27225 0.135668 1.11 1 1 25.000775 1.339254 10.033 0 0.753948 1.332836 0. $} .955991 0.1)ln T3 T2 change of availabilityof gases due to change of enmpy of gases change of availability due to combustion as fuel changes from reactants to products. This means that when eqn (2. the fuel and .41) evaluated around cycle 0 1 2 3 4 0 0.787 1.731469 9.0925 1.8 and 2.2 State points around Otto cycle 0 1 2 3 4 1 1.731469 9.7762 3540. but it is worthwhile considering what happens during the combustion process.0286 1.0925 0.
6 0 d Availability delivered a s work during expansion A v a i l a b i l i t y in c h a r g e 0.90 0.+ 0 cj _ 0 . 2.60 0.30 0.8.+ m > m Availability d e l i v e r e d a s work during expansion I Y 0.20 0.00 x . This is similar to the energy contained in the reactants in a simple combustion process and released as the internal energy (or enthalpy) of reaction of the fuel.8 Variation of the nondimensional availability with crank angle for an Otto cycle .$ b 0.20 .50 0.10 Availability received during compression .z .20 0. *0m ~ 1.30 0.10 1. e 2 .180 135 90 45 0 45 90 135 180 Crankangle / (deg) Fig.40 .80 0.90 0.70 0.50 0.+ 4 * 0. * m m Availability received during compression Availablity destroyed during combustion 1.00 0 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 V I vc Fig. 2.70 .00 0. and the availability of the charge is greater at the beginning of the cycle than the end because the fuel contains availability whch is released during the chemical reaction.+ c) n m x Availability destroyed during combustion . Considering Fig 2.10 1. it can be seen that the availability of the charge .9 Variation of nondimensional availability with volume for an Otto cycle air are induced into the engine through the inlet valve.Availability balancefor a closed system 33 1.80 2 m 0.40 0.10 0.00 g .+ .
. da. the availability approach has given the same result as the basic equation. the total 'nondimensional work' that can be achieved is 4* 4 net work from da. to thermal energy.44) where C j Q is the sum of heat transfers to the control volume over the total number of heat transfer processes.332836 .5255 availability availability generated This is the ratio of the net work output to the energy supplied ( q * ) . and this causes a loss of availability.7. If the full availability is to be converted it is necessary to use a turbine (e.0.45) i e .180"crankangle to 0" crankangle) because of the work done by the piston (which is isentropic in this ideal cycle case).17105 = 0.42)). The unsteady flow energy equation is c ):( QW= i + cv h e ( h e+ V:/2 e + gz. To. this has been discussed by Patterson and Van Wylen (1964).34 Availability and exergy increases during the compression stroke ( . a turbocharger) and then a 'bottoming' cycle (e. is 1 ?jJoao 1 .5255 = p1) Thus.0. 4. is a measure of the work that can be obtained from the cycle.029375 . 4 = 1. The effect of this is to introduce an irreversibility defined by the change of entropy of the gas (eqn (2. Hence. 2. The 'combustion' process takes place instantaneously at 0" crankangle and the availability contained in the fuel in the form of the chemical bonds (see Chapter 11) is released and converted.g. at constant volume. The thermal efficiency of this Otto cycle. The expansion process (which is again isentropic for this ideal cycle) causes a reduction of availability in the charge as it is converted into expansion work./2 + gzi) (2. The availability of the working fluid at the end of the cycle.0. A similar approach can be used to evaluate the change of availability in an open system. Turbochargers are used to convert part of this availability into work but cannot convert it all because they can only take the state of the fluid down to the pressure of the dead state. This availability can be obtained if the working fluid is taken down to the dead state by reversible processes. and the summations of the inflows and outflows take into account all the inflows and outflows. j . a / q * . p o . a Rankine cycle based on a suitable working fluid) to take the exhaust gas down to the dead state temperature.) i h i ( h i + V.. If the changes in kinetic and potential energies are small then this equation can be reduced to cQ ) : ( W= + x h e h eCY 1h i h i i (2. Where the availability approach shows its strength is in analysing the effects of finite combustion rates and heat transfer in real cycles.8 Availability balance for an open system The availability balance of a closed system was derived in section 2. * + * da. is a measure of the work that could be obtained from the charge after the cycle in the cylinder has been completed.g. and is equal to the thermal efficiency of the engine cycle. The nondimensional availability. with a compression ratio of 12.
and hence (2.49)is the unsteady flow availability equation.. . a. can be replaced by the intrinsic internal energy of the control volume./dt = 0 and dV/dt = 0. Equation (2.Q . which is the availability equivalent of the unsteady flow energy equation.. e (2.To~j. if the dead state condition is To= 25°C and po= 1 bar. and hence eqn (2. (U)cv. which means that the conditions in the control volume do not change with time. is the irreversibility in the control volume.Availability balance for an open system 35 It is also possible to relate the rate of change of entropy to the heat transfers from the system...48) The terms h .10).T ~ s .Tos are the flow availability. neglecting the kinetic and potential terms. C keafe i. This means that dA.48) becomes (2. ) e (2.50) Example 8: steady flow availability Superheated steam at 30 bar and 250°C flows through a throttle with a downstream pressure of 5 bar..47) = dt F  (1 ) Q:  (W po z) + C k i ( h i Tosi) i @(he . (E)w. i e &..47) and into eqn (2. Many of the processes considered in engineering are steady state ones. Calculate the change in flow availability across the throttle.af. and then eqn (2..45) gives Substituting eqns (2.46) e I If the kinetic and potential energies of the control volume do not change then the internal energy in the control volume.49) where Zc. and the irreversibilities in the system as s=dt j T (2.Ckeafe T~$.46) (2.The availability of the control volume is defined by eqn (2.W + Chiaf.49) can be simplified to o=C i (:) 1.
. and similar functions had previously been defined by Gibbs and Keenan. This datum condition can be referred to as the dead state and the system reaches this when it is in thermal and mechanical equilibrium with it. i.or pseudoproperty. In this case.289 kJ/kg K. s.51) where A . or dead. = 7. that may be obtained from it is given by W = A .(2858 .e. is the available energy at state 1 .B. Exergy is very similar to available energy and is a quasi. A number of examples of the use of exergy will be given. An obvious datum to be used in most calculations is the ambient condition.36 Availability and exergy Solution A throttle does not produce any work.28 kJ/kg The significance of this result is that although energy is conserved in the flow through the throttle the ability of the fluid to do work is reduced by the irreversibility.6.289) = 231.289) .) = 298 x (7. that can be obtained as a system changes between two states is defined as the difference in exergy of those two states.A . 0 = mlaf.9 Exergy Exergy is basically the available energy based on datum conditions at a dead state. . it was introduced in Example 3. say po.= 6. eqn (2. The term exergy was proposed by Rant in 1956.298 x 7.298 x 6.065 .A0 (2. . because the enthalpy does not change across the throttle. or available energy. or heat transfer. and the conditions at exhaust.A. and A .0650 W/kg K.) = Bl . i. .= A .A . Q = 0.52) Hence the maximum work. = ( A . (2.28 kJ/kg  2. the irreversibility could have been evaluated by T0(s2 s. ) .(A2 . are he = 2858 kJ /kg. is the available energy at the dead state.T. e. Hence the irreversibility per unit mass flow is = (2858 . W = 0. . = 2858 kJ/kg. A state of thermal and mechanical equilibrium is reached when both the temperature and pressure of the system are equal to those of the dead state. and it can be assumed that the process is adiabatic. If a system undergoes a process between states 1 and 2 the maximum useful work. Hence. This is because it is not defined solely by the state of the system but also by the datum.. The conditions at inlet. are h. state that is used.0650) = 231. meafeI . The exergy of a system at state 1 is defined by B. Exergy will be given the symbol B (sometimes it is given the symbol S ) and specific exergy will be denoted b (or 6). s. taking into account the fact that there is only one inlet and outlet.50) becomes.
. The processes involved are depicted by two almost coincident lines from 1 to 2 in Fig 2.. ..1 HEAT TRANSFER It is possible for energy to be transferred from one body to another without any loss of available energy.54). U Z h U. Hence... All actual heat transfer processes are irreversible and the irreversibility results in a loss of exergy. the fluid receiving the heat is at temperature T . T I .. in which the heat transfer takes place across an infinitesimal temperature difference (i.53) If it is assumed that V I .Ulc) . reversible heat transfer Ideal reversible heat transfer can be approached in a counterflow heat exchanger.Ulh= heat transferred from the hot stream.= the change of entropy of the hot stream.) In this case U. . Figure 2..10 must be equal: in this case they are identical.U.54) In eqn (2.SI.Exergy 37 2. the changes of energy of the hot and cold streams are equal (and opposite). etc.T0S). and vice versa.) = unavailable energy of the cold stream (area 43564). .T . =  BI.) . and this will also be positive because of the increase of entropy of the cold stream. In this ideal process it will be assumed that. A similar analysis can be done for the cold stream.( U + P ~ V . and this will be positive.10. This means that the areas under the curves in Fig 2.then = (U2h  Ulh)  1 ’) . i. .e.Sib) the change of exergy will also be negative. In Fig 2.55) (U2c. U.S.10. . Ideal.9. because the hot ‘source’ fluid on entering the heat exchanger is in closest contact to the ‘sink’ fluid which is leaving the device. This occurs when the heat or energy transfer is ideal or reversible.. ) (2. In this type of device the temperature difference between the two streams is kept to a minimum. at all times. S ) . The exergy change of the hot stream is then given by ABh=B2hBlh= ( A 2 h .( A l c.Ulh)>To(&.e.10 shows that the heating and cooling processes are effectively identical on the Ts diagram and only differ in their direction.. No real heat transfer process will exhibit such perfection and exergy can be used to show the best way of optimising the effectiveness of such an energy transfer. and also the the unavailable energies are equal (and opposite) for both streams.SI..A .SI. while the temperature of the source of heat is at all times at temperature T + 6 T .. In the case of the hot stream the change of energy and the change of entropy will both be negative. and this gives ABc = B .S l h ) + P0(V2h  vlh) (2.. The term To(S. = (AZc. and S.= area lh2h65lh and To(S.TO(S2. and because (UZh. = heat transferred to the cold stream (area lc2c56lc). they might also be externally irreversible. From the First Law of Thermodynamics it is obvious that.. This means that for an ideal counterflow heat exchanger.) =area 34653.A. the energy transferred from the hot stream must be equal to the energy received by the cold stream.= V 2 . (2.A I h = ( U + p o V .. . It should be noted in this section that even though the heat transfer processes for each of the systems are internally reversible.A O ) (AlhAO) = A . ~ = (U2h Ulh>  . . is 6T less than T. if the boundaries of the control volume are insulated from the surroundings.
S Fig.57) The change of exergy of the universe is given by = ABh + ABc = =  (Uzh . Figure 2. It is obvious from Fig 2.Ulh)  . Similar quantities for the cold streams are lc2c3c4clc and 3c5c6c4c3c.11 (a) that the unavailable energy of the cold stream is greater than that for the hot stream because To(S.11 (a) shows the processes for both the hot and cold streams on the same Ts diagram.UIh) . . i. while the unavailable energy is given by 3h5h6h4h3h. there is a significant temperature difference between the hot and cold stream. . lh 2c lC/ 3 5 Entropy.SIC) (2. This means that the maximum useful work available from the cold stream is less than that available from the hot stream. For the hot stream ABh = (UZh .TO(S2 .) 2 (U. The first point to recognise is that the energies transferred between two streams (areas lh2h5h6hlh and lc2c5c6clc) are equal (and opposite).e.38 Availability and exergy reversible heat transfer). and the process is reversible. . the loss of exergy of the hot stream is equal to the gain of exergy of the cold stream.Ulc) .1 1(c) show individual Ts diagrams for the hot and cold stream respectively. even though the energy contents of the two streams are the same.To(S2.)> To(Slh .Sib) + S c .10 were not reversible. Hence. 2. This means that the exergy gained by the cold stream is less than that lost by the hot stream.Slh) (2.1 1. while Figs 2. then the Ts diagram would be like that shown in Fig 2.58) The value of AB^" c 0 because the entropy change of the cold stream is greater than that of the hot stream.$1.&h). (b) processes shown on a Ts diagram If the heat exchanger in Fig 2.11 (b) and 2.10 Reversible heat transfer in a counterflow heat exchanger: (a) schematic diagram of heat exchanger. in this irreversible heat transfer device there has been a loss of exergy in the universe.SI. The change of exergy of the universe is zero. The change of exergy for the hot stream is denoted by the area lh2h3h4h1h. and energy has been degraded.Uic)  SIC) (2..56) while for the cold stream ABC = (Uzc .
the areas 12891 and 561085 are equal. This means that areas (a+ b + c ) = (b+ c + d + e ) By definition the exergy change of the source is given by (2.Exergy T Hot stream 39 h 2h lh / 4h 6h  2h To 3 h Sh @) I (4 Irreversible heat transfer S T 2c Entropy. which is that. to Td.11. Hence.12. 2. while the low temperature stream is equivalent to a lower temperature source of heat. The energy received by the sink will be equal to that lost by the source if the two systems are isolated from the surroundings.12 are those of an infinite heat source transferring energy to a finite sink. The temperature of the source remains constant at TI but that of the sink changes from T. where the high temperature stream can be equivalent to a high temperature source of heat. to obtain the maximum transference of exergy. S T o 3c 5c  S Fig. This is effectively shown in Fig 2. in Fig 2.11 Ts diagrams for a counterflow heat exchanger with finite temperature difference between the streams This result has a further significance. If the total amount of energy being transferred is kept constant then the loss of exergy can be minimis4 by increasing the temperature at which the heat is transferred. it is important to reduce the value of To ( S . The processes depicted in Fig 2.SJ. The process undergone by the source is one of decreasing entropy while that for the sink is one of increasing entropy. The quality of the heat (energy) in the high temperature source is better than that in the low temperature one. .59) .
12. . 2. its ability to do work) has decreased by this amount. .S. The following section describes how combustion can be considered using an exergy approach.) The term Tn(Si . . In a similar way the exergy change of the sink is given by ABs. . is oxidised using an oxidant.2 EXERGY APPLIED TO COMBUSTION PROCESS Combustion processes are a good example of irreversible change. This is true of all processes which take place irreversibly. the quality of that energy has declined. that is. Since S6 is greater than SI then the exergy of the universe (that is.B .Si ) + [ ( u. .)  ms.) . .. The structure of the hydrocarbon is broken down as the bonds between the carbon and hydrogen atoms are broken and new bonds are formed to create carbon dioxide.62) .TO(S6 . usually air.40 Availability and exergy Entropy.Tn(S.S5) I (2. 2. .u5). In a combustion process the fuel. all real processes... S Fig. This seems to suggest that exergy of the universe is decreased by the combustion of hydrocarbon fuels.) (2. = ( U . usually a hydrocarbon. Consider a constant pressure combustion process.) is depicted by the area marked ‘e’ in Fig 2. =( = + AB. These processes are basically irreversible because they cannot be made to go in the opposite direction by the addition of a very small amount of energy.12 Irreversibleheat transfer from an infinite reservoir to a finite sink This equation assumes that the heat transfer takes place at constant volume.To(S. Thus.$01 (2.S. carbon monoxide and water vapour.60) Since the source and sink are isolated from the surroundings (the remainder of the universe).A.61) T d S . whilst the energy of the universe has remained constant.9.S.* = B . . then the entropy change of the universe is ABv = AB. When the system is in equilibrium with its surroundings the exergy of component i is: b.  ui ) .U. = ( A .
Hence + 2H20 (2. gives AB = 241820 . (AHR)c. and hence 94.589) + = 5074.04) = 228594. this occurs because the entropies of the reactants and products are almost equal.C(bj)R = (AHRICH.+ CO..) The equation for combustion of methane is CH..+8CO2+ 9H20 (2. and that the entropy of octane at 298 K is 360 kJ/kmol K.298 x (8 x 214.SC& .. . Then the exergy of reaction is AB = C(WP .5% of the energy defined by the enthalpy of formation is the maximum energy that can be obtained from it.(g) + O.65) = = 5219. + 20.298 x (188.H.5O.71 .2 x 204.SH* (2.(g>+2H.57 . Exergy of reaction of methane (CH.B l = Bp..6 x lo3. Thus AB = (hy)Hzo.07 + 2 x 188.65) Substituting values.To(SH~O .16 .) = 804.6 x lo3kJ/kmol.2S0.0.5 x 205.5 x 204.C ( b .64) AB = B2.5S02) . + 12.66) This means that the ability of the fuel to do work is 5.07 + 9 x 188.130.) The equation for combustion of octane is C.Exergy 41 Exergy of reaction of water Applying eqn (2.360 .H.T O ( S C O ~ + 2SH20 .O(g) (2.298 x (214. for To= 25"C. . ) . which is also the standard temperature for evaluating the enthalpy of reaction.68) Assume that the enthalpy of reaction of octane is 5074.67) AB = C(bj)p.76 kJ/kmol K (2.182.6 x lo3.9 x lo3kJ/kmol In this case the exergy of reaction is greater than the enthalpy of reaction by 2.0.62) to the simple reaction 2H.73 .12.To(8~c0.BR=C(br)pC(bl)R where suffix R indicates reactants and suffix P indicates products.86%.63) (2. 9sHzo $C8Hl8.12.65) = 804.H.16 .5% less than the original enthalpy of formation of the 'fuel'.1 x 103 u/km0i In this case the exergy of reaction is almost equal to the enthalpy of reaction. Exergy of reaction of octane (C.
To$. and the variation of exergy is shown in Fig 2.74) Equation (2.69) can be expanded to give the specific flow exergy as b f .42 Availability and exergy 2.51) while that for the exergy of a flowing gas is.(Ho . 3 Nondimensional temperature (TmJ 6 n Fig. from eqn (2. and the change of entropy s1 . = a.73) The flow exergy can be nondimensionalised by dividing by the enthalpy at the dead state temperature.(ho . A0 (2. 2.72) T O Po Hence. c 0 E .ho)T T Po Po (2.13. by comparison with eqn (2. . = A f .) .. To. B l = A . m e . the flow exergy for a perfect gas can be written bn=(h.e e .TOSO) (2.afo = (hl .13b) for the availability of a flowing gas.13 Variation of exergy with temperature and pressure for a perfect gas .74) has been evaluated for a range of temperature ratios and pressure ratios.so = cpIn ..51).) .69) (2.A.. The definition of exergy is. for a perfect gas.10 The variation of flow exergy for a perfect gas This derivation is based on Haywood (1980). h = cpT . = w 1  TOS.R In  T P (2.Toso) Now.to give (2.71) Equation (2. Bf.70) (2.
say at p / p o = 1.005 H/kg K. The air is expanded in a fully reversible adiabatic process to a pressure of 5. 509. is given by (2. and vice versa.13. fully reversible. the exergy does not. and while the energy of the universe might be considered to remain constant. 2. When the dimensionless temperature T/To<1.l ) . is the variation of enthalpy for the parameters shown. in a hypothetical. It has been shown that energy available at a high temperature has better quality than that at low temperature.Problems 43 Also shown in Fig 2. The effect of irreversibilities on the quality of energy has been considered.11 Concluding remarks This chapter has introduced the concept of the quality of energy through the quasiproperties availability and exergy.75) For T l . It was also shown that the irreversibility of processes can be calculated.0 the enthalpy is positive. and (b) the final state. > T O and also for ( k . The reason for this is that the exergy term.6 kJ. and C = 0. as shown in Fig P2. This simply means that the thermodynamic energy can be greater than or less than the datum value. Calculate the useful work which can be obtained from this process. the quality of that energy will tend to decrease. Assume that the specific heats for the gas are cp= 1. . While the enthalpy varies montonically with the nondimensional temperature. PROBLEMS 1 A pistoncylinder assembly contains 3 kg of air at 15 bar and 620 K.5 bar. Also calculate the maximum useful work which can be obtained from the gas in (a) the initial state.1 kJ] 2 Air passes slowly through a rigid control volume C. The environment is at a pressure of 1 bar and 300 K.h . It can be seen that the exergy is sometimes bigger than the enthalpy.5 kJ. and it is this area that should be tackled by engineers to improve the efficiency of energy utilisation in the world.>T l T O The physical significance of this is that the system can produce work output as long as there is a temperature difference between the system and the dead state: the sign of the temperature difference does not matter. and when T/To> 1. [295. 214. This is because the enthalpy is purely a measure of the thermodynamic energy of the gas relative to the datum temperature.718 kJ/kg K.2(a). steadyflow process between specified stable end states . as a straight line.0 the enthalpy is negative.
P2. and also the values of Toand p o .718 kJ/ kg K.2 . W. = 0. The external work... produced by any auxiliary cyclic devices required to ensure external reversibility in that exchange with the environment during the given subprocess.... We. S Fig. calculate the following work output quantities in each of the subprocesses 1a and a2: (i) (ii) The direct shaft work. '\ I I Rigid control Exitstate. are defined below: T.2(b)..=550K and p 1 = 2 bar Tz=To=300K and p 2 = p o = 1 bar The air may be treated as a perfect gas. r I / System A  '. Svstem B c / C . coming from the control volume as the air passes through the given subprocess.. I/ p .44 Availability and exergy 1 and 2 in the presence of an environment at temperature To and pressure p o ..005 kJ/kg K and c. States 1 and 2. (a) The air follows path 1a2 see Fig P2.. I Entropy.2 P I 7 P. with cp= 1.
18. Take the specific heat at constant pressure of air. 128. K = cp/c. If the dead state conditions are 1. = 4. 62.where b = h . and the work terms on a p . the change in availability. [109.154 kJ.3. cp.556 kJ. = 1. [66.Problems 45 (iii) The gross work Wg. = 0.0 c.98 kJ/kg K. m.23 (kJ/kg)] (b) Calculate the above work output quantities for each of the subprocesses 1b and b2 when the air follows the alternative path 1b2. What is the maximum work that can be obtained from the system as the temperatures equalise? (See Q.b 2 ). Chapter 1. the specific steadyflow availability function.008 kg of helium is contained in a pistoncylinder unit at 4 bar and 235°C. the irreversibility.41.4 [2884. which can be assumed to behave as a perfect gas: ratio of specific heats.0967 kJ. 128. until the cylinder volume is halved. since T.) [128. 1. determine: (i) (ii) (iii) (iv) the work done on the gas by the force. F . 8 = 8. .) [3320. Calculate the maximum amount of work that can be obtained from the system if the dead state temperature is 300 K.013 bar and 22"C.667 molecular weight. is equal to ( b .as 0.2 kJ/kg] 4 A mass of 0. = 1.) Assume for water: for air: c.18.2. The piston is pushed in by a force.18 (kJ/kg)] 3 Confirm that item (iv) in Q. connected together by a reversible heat engine. (iv) The total useful shaft work Wxc.3 kJ] 6 A thermally isolated system at constant pressure consists of 10 kg of air at a temperature of 1OOOK and 10 kg of water at 3 W K .0573 kJ] 5 A system at constant pressure consists of 10 kg of air at a temperature of 1000 K.Tos. = 4 universal gas constant.4.2 kJ] . state 2 is the dead state. 128. = To and p 2 = p o . F .3143 kJ/ kmol K [3.77. (Note that. Chapter 1. 128. = 1.2. Show the heat transfer process defined in part (iii) and the unavailable energy on a Ts diagram.23.7 kJ/kgK K = c. the heat transfer from the gas. so that item (iv) is in this case equal to the steadyflow exergy of unit mass of air in state 1 for an environment at To= 300 K and p o = 1 bar. 2./c. and the dead state pressure is equal to the pressure in the system. The following data may be used for helium.2 kJ/kg K K = cp/c. (See Q.V diagram. and a cooling coil is used to maintain the pressure constant. 10.03.
Calculate.5 kJ/kg. [ 72. Neglecting the effects of electricity. 343. true] 8 A gas turbine operates between an inlet pressure of 15 bar and an exhaust pressure of 1. 424. Draw a simple schematic diagram of the heat exchanger you would design. [False. based on dead state conditions of 1 bar and 20°C.7 kJ/kg.15 760. Explain. calculate the minimum loss of exergy for both types of heat exchanger. showing the hot and cold gas streams. Assume the working substance is an ideal gas with a specific heat at constant pressure of cp= 1.83 uW/kg) W / k g K) 7 Products (1) Environment (0) 1 1000 298. (iii) the exergy change in the gas passing through the turbine. for the turbine alone: (i) the specific power output.46 Availability and exergy 7 An amount of pure substance equal to 1 kmol undergoes an irreversible cycle.6 kJ/kg] 9 It is proposed to improve the energy utilisation of a steelworks by transferring the heat from the gases leaving the blast furnace at 600°C to those entering the furnace at 50°C (before the heat exchanger is fitted). specific work (kJ/kg) that could be derived from combustion products that are (a) stationary. where the suffix m indicates that the quantities are in molar terms. 45. 220.0 7. The surroundings are at a pressure of 1 bar and a temperature of 300 K. and (b) flowing. and maximum useful.33 kJ/kg. 806K. 466. giving reasons for your assertion: (i) (ii) (iii) f SQ f (durn + P dvm) = dum + P dvm >O T f 6W < f p dv. (ii) the exhaust gas temperature. (iv) the irreversibility or lost work. magnetism and gravity state whether each of the following relationships is true or false. in an environment under the following conditions.3. If the minimum temperature difference between the hot and cold streams is 1O"C. The inlet temperature to the turbine is 1500 K and the turbine has an isentropic efficiency of 90%. 727.0 289.3.41 0.4 6. The minimum temperature of the flue gases is limited to 150°C to avoid condensation of sulfurous acid in the pipework at exit pressure of 1 bar.3.31 . [697. with the aid of Ts diagrams.005 kJ/kg K and the specific gas constant R = 0.287 kJ/kg K. false.7 [262.09 kJ/kg] 10 Find the maximum. why a counterflow heat exchanger is the more efficient.2 bar. P(bar) TW) v(m3/kg) 0.
1) energy has to be transferred from the gas turbine exhaust to the working fluid in the steam turbine. 31 Schematic of CCGT . Pinch technology is an approach which provides a mechanism for automating the design process. and minimising the external heat transfers.3 Pinch Technology In recent years a new technology for minimising the energy requirements of process plants has been developed: this has been named Pinch Technology or Process Integration by its major proponent. such as oil refineries or major chemical manufacturing plants. require that heating and cooling of the feed stock take place as the processes occur. 1983. Linnhoff (Linnhoff and Senior. and the energy that has to be rejected to a low temperature sink (or utility) is also minimised. in a combined cycle gas turbine (CCGT) plant (see Fig 3. Fkcess plants. Obviously it would be beneficial to use the energy from a stream which requires cooling to heat another which requires heating. Linnhoff and Turner 1981). in this way the energy that has to be supplied from a high temperature source (or utility) is reduced. Both of these external transfers incur a cost i running n the plant. .s diagram of a CCGT plant is Fig. A T . for example. Pinch situations also occur in power generation plant.
3 H .3. where the pinch is obvious. and is due to the difference in the properties of the working fluids during the heat transfer process (namely. It is defined as the minimum temperature difference between the two streams for effective heat transfer. the exhaust gas from the gas turbine cools down as a single phase but the water changes phase when it is heated) . Entropy. .this limits the amount of energy that can be taken from the hot fluid.T diagram of CCGT Perhaps the easiest way of gaining an understanding of pinch techniques is to consider some simple examples. S Fig. The heat transfer processes are shown on a temperatureenthalpy transfer diagram in Fig 3.2.48 Pinch technology shown in Fig 3. 3. 3.2 Ts diagram of CCGT fluid Pinch pint / Steam I Q=AH I Enthalpy Fig. where the heat transfer region is shown: the pinch is the closest approach in temperature between the two lines.
Step I :Temperature intervals Evaluate the temperature intervals defined by the 'interval boundary temperatures'.91387.88 4.7 426.2. TT. These can be defined in the following way: the unadjusted temperatures of the cold streams can be used.1 A heat transfer network without a pinch problem This example has a total of seven streams.. and use of the cold water will be charged by the water authority.. and the target temperature. and the heat load is the amount of energy that is transferred to or from the streams.7 2 3 4 5 6 7 In this case there are three streams of fluid which require cooling (the hot streams) and four streams of fluid which require heating (the cold streams).1 = 210. and it is required to use the heating and cooling potential of the streams to minimise the heat transfer from high temperature utilities.. The heat flow capacity.43 2.) is 10°C.4 408.8 518. and to heat the cold streams by means of a steam supply. The simplest way of achieving this is to cool the hot streams by transfemng heat directly to a cold water supply. If heat is going to be transferred between the hot and cold streams there must be a temperature difference between the streams: assume in this case that the minimum temperature difference (dT. In this way the effect of the minimum temperature difference has been included in the calculation.8 MJ/h could achieve the same result. while the cold utility (a cold water supply) has to remove 1387.4.9 MJ of energy.88 2. from the actual values. T. The steam has to be produced by burning a fuel.. The parameters for the streams involved in the processes are given in Table 3. three hot and four cold. In reality a minimum net heat supply of 1597. and the heat transfer to low temperature utilities.1 Specification of hot and cold streams Stream no 1 Stream type Cold Cold Hot Cold Hot Cold Hot Supply temperature T. This results in Table 3. The supply temperature.4 449. This problem will now be analysed.1 MJ of energy. is the target final temperature that must be achieved by heat transfer. Both of these utilities are a cost on the process plant.0 354.0 511. and the hot stream temperatures can be adjusted by subtracting ST. Table 3.28 7. This means that the hot utility (the steam supply) has to supply 1597./(OC) 95 40 310 150 245 65 280 Target temperature TT/(OC) 205 220 205 205 95 140 65 Heat flow capacity Heat load rnC/(MJ/hK) Q/(ryrJ/h) 2. The method of tackling this problem proposed by Linnhoff and Turner (1981) is as follows.72 2.A heat transfer network without a pinch problem 49 3.84 4. is the initial temperature of the stream.1...38 316. this approach is shown in Fig 3. mC. . if it were possible to transfer all the energy available in the hot streams to the cold streams. is the product of the mass flow and the specific heat of the particular stream.
This diagram has been evaluated using the data in Table 3. Table 3. The hot stream line is based on the composite temperatureheat load data for the hot streams. It can readily be seen that the two lines are closest at the temperature axis. see Fig 3. the cold stream line is evaluated by applying the same equation to the cold streams.0MJh 140 + Cold water 205 95 65 Fig.5).2. when they are still 25°C apart: this means that there is no 'pinch' in this example because the temperature difference at the pinch point is greater than the minimum value allowable.50 Pinch technology $$$ Hot streams 9 I50 Steam I u" 354./(OC) 95 Target temperature TT/(OC) Adjusted temperatures ~~ Order ~~ 95 205 205 40 220 220 300 205 195 T 9 T 5 T 3 l 40 310 T 4 3 4 5 T I T 6 150 205 245 95 150 205 235 85 65 140 270 55 T 7 Duplicate T 3 T l O Tl1 T* T 2 T2 1 6 7 65 140 280 65 The parameters defining the streams can also be shown on a diagram of temperature against heat load (enthalpy transfer. 34 Direct heat transfer between the fluid streams and the hot and cold utilities . . and is based on the unadjusted temperatures.2 Ordering of hot and cold streams Stream no 1 2 Stream type Cold Cold Hot Cold Hot Cold Hot Supply temperature T.2). and is evaluated using eqn (3.
3.6 Temperature intervals for heat transfer network .400 350 300 250 200 150 100 50 ~ Pinch 1 ' 1 I l l 1 0 ~ I l l I I I l i Fig.
The energies flowing into and out of the combined systems. it n should be recognised that there is no heat transfer to the cold utility. However. by the eighth interval the demands of the cold streams exceed the total energy available from the hot streams. when where i = initial temperature of the interval i + 1 = final temperature of the interval Applying this equation to this example results in the heat flows shown by the 6 H = mCdT values in Fig 3. The mechanism for allocating the energy transfers will now be introduced. the total heat transfer from Stream 7 is passed to Stream 2: an energy balance shows that the . respectively. are those which have to be supplied by and lost to the external reservokc. The heat transfer network can be shown schematically as in Fig 3. but the energy can be supplied from that available in the higher temperature intervals. i. It can be seen from Fig 3.7.8. Qh and Qc.8 MJ could be provided from the hot utility at any temperature above 140"C. Hence. because this will limit the temperature required in the hot utility. and it is at this point that the energy should be added from the hot utility. In reality. from the hot streams to the cold streams) in the first four intervals.8 that the individual heat transfers are positive (Le.9. the 210. ST. and hence the intervals have been established so that full heat transfer is possible between the hot and cold streams. but the higher the temperature of the energy the more will be the irreversibility of the heat transfer process. and finally adding 210. and thus all the heat transfers from the hot streams must be to cold streams This constrains the problem to ensure that there is always a stream cold enough to receive heat from the hot sources. In the fifth interval the amount of energy required by the cold streams exceeds that available from the hot streams in that temperature interval.e. . because the difference between the enthalpies of the hot and cold streams is constant. This means that the temperature of Stream 7 must be cooled to its target temperature of 65°C by transfemng heat to a colder stream: the only one available is Stream 2. (3. It is now necessary to apply the First Law to examine the enthalpy balance between the streams.52 Pinch technology Hence. the problem reduces to transferring energy from the hot streams to the cold streams.. First. and this means that any additional energy added from the hgh temperature supplies must be compensated by an equal amount of energy being rejected to the low temperature sinks: hence energy wdl have just flowed wastefully through the overall system.. The streams available for the heat transfer processes are shown i Fig 3. It is now useful to look at the way in which the heat can be transferred between the hot and cold streams.. Having defined the temperature intervals it is possible to consider the problem as shown in Fig 3. The heat flows through each of the temperature intervals can be evaluated as shown in the next step.6.Q h 6H Step 2: Interval heat balances Table 3. It is also apparent that the difference between thcse values is the difference betwsen thz enthalpies of the hot and cold streams.2 includes the effect of the minimum temperature difference between the streams.8 MJ/h from a hot utility. = Q.1) Consideration wdl show that 6 H is constant.
6. 1 _ 1 _ 1 Streams Q .1.2.162 5 7. 3.7  233 1 128 4 361 5 Q.A heat transfer network without a pinch problem Hot reservoir (utilities) 53 Hot streams SH = Q. QK I _ _ _ _ 1044 .7 MJ/h before the stream reaches its target temperature In a similar manner it is necessary for Stream 5 to be matched to Stream 6 because this is the only stream cold enough to bring its temperature down to 95°C.4 1.5.7. Cold streams Q. *4 5 0 2 43 2 167 5 210 8 Q. Q '75729 I 504 0 99 3  3.6 ______ 7. 6 '. 7. In this way it is possible to remove Streams 6 and 7 from .2 236 8 202 Heating 210 8 1764 1526 48 2 43 2 0 23 8 .7 Overall energy for heat transfer network 300 . 1 5 4 _ I _ _ Q. I I  Fig. 2.2.5.5.Q.5.5 142 5 Q. 3.7. 3. and there is a residual heat capacity of 6.4 Q6 603 3 566 4 36 9 358 7 207 8 " 7.8 Heat flows temperature of Stream 2 is raised tc 218"C.7. Q. Cold reservoir (utilities) Fig.2. Q.2 3. mC6T 128 4 CmC6T 3 Q ___ 3.5.2 5 0 ~ Q.344 582 Q. I .. .
54 Pinch technology further consideration because they have achieved their target temperatures. Fig 3.9 Initial heat transfer: heat transfer from Streams 5 to 6.10 Removing the residuals from Streams 2 and 5 Streams 2 and 5 are represented in this diagram by their residual energies. 3.10. 3. arbitrary.11 Completing the heat transfer network .10. and 7 to 2 mC 310 Q 449 4 M J h 72 0 MJ/h 300 205 4 28 245 220 b 2 84 205 4 I 2 88 2 88 316 8 M J h 220 4 6 7 MJh 408 7 MJ/h 7 43 Fig. Figure 3. and for this case Stream 3 will be matched with Stream 4. and by the temperatures that were achieved in the previous processes. mC 310 Q 449 4 Mh J 426 0 M J h 205 95 + b 4 28 2 E 220 0 2 84 65 b 2 38 511 7 M J h 2 88 316 8 M h J 0 2 88 205 4 51 8 4 M J h 408 7 M J h .1 1. 3. It is possible to cool Streams 3 and 5 by transfening energy with either of cold Streams 1 or 4 The decision in this case is . and by this stage Streams 5 and 4 can be removed from further consideration. This results in the heat transfers shown in Fig 3. ‘ p r \ U 7 43 4 72 354 0 MJ/h Fig.9 can be modified to Fig 3. . mC 428 Q 4 0 7 MJ/h 288 220 4 6 7 MJih 218 288 2448 MJ/h 67MJh Cold streams Fig. Streams 2 and 5 must be left in the network because they still have residual energy before they achieve their targets. and Stream 5 will be matched with Stream 1. This results in another modified diagram.
3.11.8 hU/h heat transferinFig 3. which grows directly out of the original arrangement shown in Fig 3. the temperature at which this energy is added is relatively arbitrary. 3.A heat transfer network without a pinch problem 55 By this stage it is necessary to consider adding the heat from the hot utility. which is better illustrated as shown in Fig 3. 4 28 449 4 MJih 2 84 426 0 MJih 2 38 511 7MJlh 95 288 2 88 3168MJih 518 4 MJih 40 150 743 408 7 M J h 140 MJ/h U 65 472 354 0MJ/h Fig. This is indicated by the 210.12 Composite diagram for heat exchanger network The diagram given in Fig 3. but it is now possible to combine all these subsections into a composite diagram.12. and this is shown in Fig 3. but the diagram is not the most succinct representation of the network problem. Hot streams 205 95 65 Fig.4.13. and the heat should be transferred at as low a temperature as possible. In this case.12 suggests that seven heat exchangers are required. The previous analysis has considered the problem in discrete parts.13 Diagram showing the minimum number of heat exchangers to achieve heat transfer .
as opposed to the 12 in the first case.3. and does produce sufficient temperature difference at the pinch. and this is shown in Fig 3. It can be seen that the basic cold stream is too close to the hot stream and there will not be a sufficient temperature difference to drive the heat transfer processes.. . is referred to as the pinch point because it is the closest that the temperatures of the streams are allowed to come.4 Definition of temperature intervals Stream no 1 2 3 Stream type Cold Hot Cold Hot T.5 120 180 140 97.0 3. .56 Pinch technology This case was a relatively straightforward example of a heat exchanger network in which it was always relatively easy to match the streams. mC /(MJ/hK) 2. = 5°C.2 A heat transfer network with a pinch point Consider there are four streams of fluid with the characteristics given in Table 3. dT. It can be seen that there are five intervals in this case. This value of dT.0 1./("C) TT/("C) Adjusted temperatures 50 110 Order T 6 T 3 T I T 5 T 4 T 2 Duplicate Duplicate 50 130 110 125 70 80 115 4 120 55 115 65 80 115 50 These temperature intervals can be depicted graphically as shown in Fig 3.TT) /(MJ/h) ~~ 55 4. Assume that the minimum temperature difference between any streams to obtain acceptable heat transfer is 5"C. The next example shows what happens when there is not sufficient temperature difference to drive the heat transfer processes.4. The temperatures of the streams can be ordered in a manner similar to the first case and the results of this are shown in Table 3. i.14. The modified cold stream line has been drawn after undertaking the following analysis.15./("C) 50 130 80 120 Target temperature TT/(OC) 110 70 115 Heat capacity flowrate.5 Table 3. It is now possible to draw the temperatureheat load diagram for this problem.3 Characteristics of streams Process stream Number 1 2 3 4 Type Cold Hot Cold Hot Supply temperature T.e. 3. Table 3.0 Heat load mC(T.. because there was always a sufficient temperature difference to drive the heat transfer processes.
3.16 indicates the heat flows in the various intervals and.15 Temperatureheat load diagram. The result of this is shown in the righthand column of figures in Fig 3. in the lefthand column of figures.5 units of energy to . v 110 100 90 k 8 b C o l d stream 80 70 60 Basic Modified cold s t r e a m s cold streams 50 40 I 1 1 . and consideration will show why it comes about. indicating pinch point Step 3: Heat cascading This step is an additional one to those introduced previously.16. Figure 3.14 Temperature intervals for heat transfer network 140 1 12. 3. which has been achieved by adding 12. 150 200 250 I 0 50 100 300 Heat load / (MJ/h) Fig.A heat transfer network with a pinch point 57 Fig.5 kJ/h 130 120 0 . Consideration will show that this is impossible because it means that the heat will have been transferred against the temperature gradient. Such a situation can be avoided if sufficient energy is added to the system to make the largest negative heat flow zero in this interval.5 units in temperature interval 3 between 110°C and 80°C. shows that if the heat flow from the hot utility (or heat source) is zero then there will be a negative heat flow of 12.
16.7 0 ) + 1 ..5 units of energy. Any heat flow across the pinch results in the same amount of heat being added to every heat flow throughout the system.17. 5 ~( 1 2 0 . It is now necessary to break the problem at the pinch. and Stream 4 is matched with Stream 3.18..!L p J p{ 6H = 30 + 12. and this results in Fig 3. Do not use the cold sink above the pinch.3) Hence. Then Stream 2 can transfer 70 MJ/h to Stream 1.=3x ( 1 3 0 . This means that cooling to the utility stream is not allowable above the pinch. It can be seen that in both cases the difference between Q.4 ~ (11580) = 17.5 30 . and Q.16.2 ~ ( l l 0 .7. 2.5  45 31. 3.16 Temperature intervals and heat loading There is now a point in the temperature range where the heat flow is zero: this point is called the pinch.5 30 Fig.5 6H = 2. 1. If the system has been designed for minimised heat flow it does not absorb any heat below the pinch. which is a modification of Fig 3. and Q. as stated previously. It is now necessary.5 0 ) .3 then C(SH. If the system has been designed for minimised heat flow it does not reject any heat above the pinch (see Fig 3. to match the hot and cold streams above the pinch.5 5 ) . is 17. as far as possible. and hence the only transfer can be with the hot utility above the pinch.5 (3. If an energy balance is applied to the streams defined in Table 3. Consider Stream 2 is matched with Stream 1. where the heat rejection has been made zero at the pinch). as shown in Fig 3. and enable Stream 1 to achieve its .. In this example it is at 80"C. which means that the pinch occurs at a cold stream temperature of 80°C and a hot stream temperature of 85°C. and hence increases Q. Do not use the hot source below the pinch.58 Pinch technology the system.42. Do not transfer heat across the pinch. Now the problem can be analysed. It is hence possible to reduce the problem into two parts: above the pinch and below the pinch. 3. There are three important constraints regarding the pinch: 1.9 for the first example. bearing in mind the restrictions imposed by the pinch point. which is the equivalent of Fig 3.5 32. mC6T CmCGT . the energies obey the steadyflow energy equation for the system shown in Fig 3.
Also Stream 4 can transfer its energy to Stream 3 and this will raise the temperature of Stream 3 to 93.5 45 70 2. The reason for this being an unsuitable approach is hn because the heat capacity flomte for Stream 1 above the pinch is greater t a that of the cold stream above the pinch.7"C. then the answer shown in Fig 3. while reducing its own temperature to 106. namely.1"C. and Stream 4 matched to Stream 1.17 Breaking the problem at the pinch point Q 135 52.4) above the pinch point. 3.19 is obtained. Stream 2 matched to Stream 3.18 Hot and cold streams with pinch target temperature. . If the alternative match is used. Hence. mccold 2.5 130 Hot streams mC _I Q 45 n 851 I 70 * 3. 3. then the higher temperature of the cold stream would have to be higher than that of the hot stream to achieve an energy balance: this would result in an impossible heat transfer situation. This shows that there is not sufficient energy available in these streams to achieve the target temperatures.0 Cold streams Fig.A heat transfer network with a pinch point 59 Hot streams Cold streams Cold reservoir (utilities) Fig. Since both streams have the same temperature at the pinch point. (3.0 60 140 4.0 1. for a satisfactory result to be possible ~ m C .
O 1.5 106. and heat transfers to the cold utility are requeed below the pinch. and is hence acceptable.0 5Mlh 140 135MJh Cold streams Fig.15. and the total energy added is 12.5 MJ/h. Considering the heat transfers below the pinch. It has been shown that in some plants there is a pinch point which restricts the freedom to aansfer energy between process streams.0 45MJh 130 ISMJlh 4.16. The 30 MJ/h transferred to the cold utility is in line with that calculated in Fig 3. when it can be seen that the energy transfers have produced a sufficient temperature difference to satisfy the constraints of the problem. This means that utility heat transfers are required from the hot utility above the pinch. However. (3. Hot streams ‘3O mC Q 180 97.5) which is the equivalent of inequality (3.4) for the transfers below the pinch.3 1. In this case it was chosen to transfer all the energy in Stream 4 because this results in a lower temperature for heat transfer to the cold utility.5 n n 70 3 . To ensure that the plant attains its maximum efficiency of energy utilisation.3 Concluding remarks A method has been introduced for improving the efficiency of energy transfers in complex plant.5MJh U 2. This obeys the rules proposed above. These diagrams can now be joined together to give the composite diagram in Fig 3. energy should be added to the system only above the pinch. is shown in Fig 3. It can be seen that. which is in agreement with the value calculated in Fig 3. It is now possible to consider the modified diagram. before heat transfer from the utilities has been supplied. It can be seen that it is not possible to match the hot and cold streams either above or below the pinch.4). above the pinch point. .60 Pinch technology The heat transfers are shown on the diagram. energy has to be added to the system from the hot utility. and extracted from it only below the pinch. 3. 3. 4.5 M l h 52. it is feasible to bring about the heating because mChot 2 mCcold 3. it can be seen that Stream 1 can be heated by energy interchange with Streams 2 and 4: neither Stream has sufficient capacity alone to bring Stream 1 to its target temperature. This proposal does obey inequality (3.16.19 Compositediagram for heat transfer network i Example 2 n The heat load against temperature diagram for this problem. and was discussed previously.19.
= 90 M / h ./("C) T. H [(a) TCplnch QH.2 kW/K.= 60 kW.1 Data related to Q. Table P3.0 kW/K.. (b) analyse this data to determine the minimum heat supplied from the hot ytility. Q = 380 kW. 2.nch = 140"C] 1 2 3 4 5 Cold Hot Cold Hot Cold 60 180 30 150 60 180 40 130 40 80 220 400 40 [360 kW.0 4. Q. = (a) calculate the data missing from Table P3.5 Stream no 1 2 3 4 [105"C (cold stream)../("C) Enthalpy change AH/(kW) ? ? Stream no ~ Stream type ~~ Heat flow capacity rnC/(kW/K) 3 2 ? ? ? = 160 kW.. (c) draw a schematic diagram of the heat transfer network. the minimum heat transferred to the cold utility. ATrnh 1O"C...2 Supply Target temperature temperature T. 2.. design a network which achieves the requirement. (a) Does this design achieve the minimum energy target for AT. = 150°C. = 480 kW. 280 kW. as defined in Table P3.. = 260 k w 1 .0 4.1. = 140 M / h l 2 Some stream data have been collected from a process plant.3 shows a network design using steam.. If the minimum temperature difference for effective heat transfer is 20"C. and at what temperature does it occur? Calculate the minimum heat transfers to and from the cold and hot utilities. Qc. and these are listed in Table P3.. and the pinch temperatures.. cooling water and some heat recovery. Table P3.2 Data related to Q... THplnch = 170OC.Problems 61 PROBLEMS 1 A process plant has two streams of hot fluid and two streams of cold fluid. Assuming the minimum temperature difference between streams. show a network design that does. Is there a pinch point in this problem../("C) T. e.0 kW/K. (b) Q. = 20"C? (b) If the current network does not achieve the targets. 4.. 3 Figure P3. e".../("C) Hot Hot Cold Cold 205 175 45 105 65 75 180 155 Heat flow capacity rnC/(MJ/hK) 2. It is required to minimise the energy which must be transferred to hot and cold utilities by transferring energy between the streams. TCp. e".0 3. = 360 kW.2. and minimises the transfers to the utilities.l Supply Target temperature temperature Stream type T.2.
5 shows an existing design of a process plant. and rejects a total of 560 k W of energy to cold water utilities. (a) Show that there is a pinch point. = 130 k W ] = .. [QH. = 0. = 560 kW. = 01 mC = 20 m C = 10 t '55"c t 130°C 30c r!l & I Cold streams Fig. = 20°C and show a design that achieves these targets.. (b) Q. The plant achieves the necessary conditions by providing 480 k W of heat from a steam source.. containing two exothermic processes..4 shows two hot streams and two cold streams for heat integration (subject to AT.. 4 5 Figure P3. = H (c) QCmm210 k W . Qc. P3.62 Pinch technology Cold water duty: 480 kW 260" 420 kW 300 kW 60" Process 50" L 150" I Fig. and produce products at the temperatures shown.3 Network for Q.. P3. and evaluate the temperature. Q = 480 k W . TCpinch = 110°C.3 4 Figure P3.4 Network for 4 .. (b) Show that the existing plant is inefficient in its use of the energy available. only 460 k W is transferred between the streams. = 20°C). (i) What are the energy targets? (ii) Show a network design achieving these targets. These require streams of reactants as shown in the diagram. (c) Calculate the energy targets for AT^. QH. THplnch130°C.
5 Network for Q. Comment on the effect of Q H = 480 = [(a) TCpmch= 110°C..7. P3.. (b) Q.Problems 63 AH=460kW AH = 360 kW Fig. reducing the minimum temperature difference. (c) Q. P3. THpmch120°C.7 Network for Q... = eHmln = 40 kw1 kW.. (b) there is transfer across the pinch] steam 60 kW 30" 420 kW /7f 160" 150" * Process 180" /7( 70" Process 190" 660 kW 110" Fig. QH. = [(a) QCmln190 kW.7 . (b) Explain why the existing network does not achieve the energy targets. = 10°C. 7 A network for a process plant is shown in Fig P3..T= 90 kW. 120 k w ..5 6 Recalculate the problem in Q. (a) Calculate the energy targets for ATrnn 10°C and show a design that achieves these = targets. = 560 kW.5 using a AT.
as 9th = qin w. = specific enthalpy of reaction of fuel.t where wnet net work output from the cycle per unit mass of fluid.1) can be rewritten for the whole powerplant. Equation (4. in terms of specific quantities. l. or usually its calorific value. as W".Rational Efficiency of a Powerplant 4. In the past this has been based on the enthalpy of reaction of the fuel. including the boiler or heat transfer mechanism. It was shown previously (Chapter 2) that this is not the energy available for the production of work.. as was shown when considering exergy and availability. and this relates the work output from the cycle to the maximum work output obtainable. = and Ah. qth= thermal efficiency of cycle. to the amount of energy that has been added to the cycle by the combustion of the fuel. and that the maximum available work that can be obtained from the fuel is based on . The efficiency of the powerplant has been related. wWt net work output from the cycle per unit mass offuel. In this case qinis the energy transfer to the working fluid. method of defining the efficiency because the energy addition cannot all be turned into work.2). l.lo = overall efficiency This might be considered to be an unfair. and does not take into account any losses in the boiler or heat transfer device. and possibly misleading. Qi.1 The influence of fuel properties on thermal efficiency The thermal efficiency of a cycle has been defined previously.lB = efficiency of boiler.Ah0 (4. in eqn (4. = and qin= energy addition to the cycle per unit mass of fluid.t %'qBVth= . Another definition of efficiency can be derived based on the Second Law.2) where of powerplant.
2) and (4. The actual effect on thermal efficiency of using the change of Gibbs function instead of the enthalpy of reaction is usually small (a few per cent). 4. . and Ago = change of Gibbs function caused by combustion. a general heat engine will be considered (see Fig 4.5) is often referred to as the Second Law Efficiency.4.hi .3) This is related to the enthalpy of formation by the equation Ago = Ah0 .2 Rational efficiency When the efficiencies defined in eqns (4. internally and externally) one or an irreversible one. = h 2 .Rational efficiency 65 the change of its exergy at the dead state conditions. These effects are usually neglected when considering cycles. (4.SPo> (4. rather than its enthalpy change. The efficiency of this cycle is which is the efficiency of an internally reversible engine operating between the temperature limits TL and TL. and the difference was dependent on the structure of the fuel and the composition of the exhaust products.Ago (4.TO(s2.e. and the maximum net work that can be achieved is G m t = b 2 b . (4.5) are evaluated they contain terms which relate to the 'efficiency' of the energy transfer device (boiler) in transferring energy from the combustion gases to the working fluid.7) . Hence. the Second Law states that it is never possible to convert the full energy content of the energy supplied into work. If it were irreversible then it would follow the cycle 123. If it were internally reversible then it would follow the Camot cycle 123s41.1). This efficiency will always be less than unity unless TL = 0.1 could be either a wholly reversible (i. The efficiency of the powerplant can then be redefined as a= Wnet .$1) where Tois the temperature of the dead state. the maximum available work from unit mass of fuel is Ago = g.To(s. superheater. . = maximum net work obtainable from unit mass of fuel. Equation (4. Actual engine cycles will'be considered later.4) It was shown in Chapter 2 that I Ago I could be greater than or less than I Aho 1 . Consider first the reversible cycle. because the work output is related to the available energy in the fuel. The engine shown in Fig 4.1. However.5) where wmt= actual net work output from the cycle per unit mass of fuel. For convenience the values will all be taken as specific values per unit mass flow of working fluid.g. etc. First. and the energy added is related to the change in enthalpy of the working fluid as it passes through the boiler.
the Second Law efficiency of the heat engine is where q2. qR.1 A heat engine operating between two reservoirs: (a) schematic diagram of the engine.* is called the Second Law efficiency. 4.h .1 (b) in the following way.s l ) by area B. then the rational efficiency will be less than unity because energy which has the capacity to do work is being rejected. Examination of eqn (4. h2 .0.but is equal to a lower temperature TL.s diagram for the engine which receives and rejects energy isothermally. This is depicted by area C in Fig 4. or the rational efficiency.This result can be interpreted in Fig 4. This because when T3s= To then area C is zero (Le.8)shows that if the T3s= To then l. and the unavailable energy To (s2. the line at TL = To is coincident with that at T3s). .66 Rational efficiency of a powerplant Fig. (c) Ts diagram for the engine which receives and rejects energy nonisothermally Hence. If Tois not equal to T3.Then the difference in the enthalpies. and hence the energy available to produce work is area A. This shows that the cycle is as efficient as an internally reversible cycle operating between the same two temperature limits (T3sand Tl). (b) T .lR = 1.l(b). is depicted by areas A + B. and the rational .
h .1 (b).16) If the dead state temperature is less than T3 then the rational efficiency is even lower because of the loss of available energy shown as area C in Fig 4.v 3 .S I ) ...0. = = h 2 . In the case of To= T3.s4) . as shown below: b = a .(h3 . The effect of the internal irreversibility is to cause the entropy at 3 to be bigger than that at 3s and hence the entropy difference 6S.10) available energy unavailable energy (4. (4. This is similar to exergy.fil =6 4 .> 6 S I 2 .h . The effect of this is that the net work becomes w = ( h 2 .Areas(B + C) ?R = Areas (A + B + C) . The loss of available energy.T3(s3s .as would be the case if there were external irreversibilities.h4) = T I ( S 2 .s 3 s ) 2 .s 3 s ) .Areas (B)  Area A Areas (A + C) <1 (4. (4. ( T 3 . If To< T3.s 3 s )  (4. is depicted by area D in Fig 4.9) Consideration of eqn (4. even if To= T3 the rational efficiency is still less than unity because of the increase in entropy caused by the irreversible expansion from 2 to 3. ) .$4) .T o ) ( s 2 . in this case the irreversibility.15) In the case of the irreversible engine..a O.T o 1 0 2 .14) (4.$1) .T3(s3 .1 (b).1(b). as depicted in Fig 4.s1) .13) If To= T3sthen the rational efficiency.ble ene%Y + E  Y Q.0 because the working fluid leaving the engine still contains the capacity to do work. . energy T o ( s . If the engine is not internally reversible then the Ts diagram becomes 1234.T o ( s 2 . qR= 1.6Q.1.T303 .T 3 0 3 .P. then vRc 1.h .8) shows that it is made up of a number of different components which can be categorised as available energy and unavailable energy.14) Hence. from eqn (4.Rational efJiciency 67 efficiency becomes Areas(A + B + C) .$ 1 ) .av&.T3b3 .$ 1 ) .s o )= ".
then the rational efficiency of the cycle is Wnet VR = ~ (4. many cycles use air as a working fluid (e.bl h2 .h4) = b2 . If the cycle is reversible. Joule cycles.e. Such a cycle is typical of one in which the working fluid is a vapour which can change phase.{ b3s . . The rational efficiency of this cycle is .20) shows that it is never possible for an engine operating on a cycle in which the temperature of energy rejection varies to achieve a rational efficiency of 100%. .) 123 s .sg. 54785 Equation (4.31) .21) shows that the irreversibility of the expansion process reduces the net work significantly by (i) increasing the amount of exergy rejected.e.1 (c). Thus the rational efficiency of an engine operating on a Joule cycle is (4. i. 123s4. if the expansion is irreversible.b4 + TO(s3 .1 (c). to simplify the analysis it will be assumed that TL = To= T4.[*netlrcjected (4.5 4 1 area area (4. with isothermal heat supply and rejection. Equation (4. If the cycle is not reversible. However. and in this case it is not possible to supply and reject heat at constant temperature.bl + To(s2 . Otto. e. and it can be seen that the heat is supplied over a range of temperatures from TI to T2. and there is an increase in entropy from 2 to 3.sq)} = = b2 . and (ii) increasing the irreversibility of the cycle.$1) .21) area 63 . .h4) = b2 .g. it is not possible to neglect the varying temperature of heat rejection.hl .1. then the cycle is defined by 12341.b4) Hence.20) Equation (4. i.(h3s . wnet = { *netlsupplie~ . Furthermore.(h3 . A general cycle of this type is shown in Fig 4. etc). However.To($.s4) 1 (4.hI .b4) .b . Diesel.(b3 .19) These terms are defined by areas 123s541 and 43s54 respectively in Fig 4.g. . because the engine is rejecting available energy to the surroundings.18) = b. the net work is made up of the maximum net work supplied and the maximum net work rejected.18) then becomes wnet h2 . until now it has been assumed that the cycle is similar to a Camot cycle.and rejected over a range of temperatures from T3to T4.{ b ?.bl + If the cycle shown is a Joule (gas turbine) cycle then Wnet = .68 Rational eficiency of a powerplant UI.17) b2 .If only the heat engine is considered then it is possible to neglect the temperature difference of the heat supply: this is an external irreversibility.b .(b3s. This is simply because there will always be energy available to produce work in the rejected heat.b4 + .
25) Hence. which shows the heat engine contained in system B of Fig 4. for an internally reversible engine the maximum net work output is the sum of the heat supplied and the heat rejected.26) .h I = TI ( $ 4 .b . ~ specific net work output from the cycle. The thermal efficiency of an ideal Rankine cycle (i.SI 1 (4.24) If the condenser were of infinite size then the temperature at 1 could be equal to the environmental temperature.20) and (4. but b3.2(b). and the difference of the entropies between states 3 and 2.h2) . consider the passage of the working fluid through system A.2(a). (4. It enters system A with a state defined by 3 on the Rankine cycle (see Fig 4. Now. = However.and in addition the irreversibility To(~3 s3J has been introduced.3 Rankine cycle It was stated above that the efficiency of a cycle is often evaluated neglecting the irreversibility of the heat transfer to the system. To. is the same for both cycles.7) shows that it consists of two terms: a difference of the enthalpies between states 3 and 2.To(~3 $ 2 )  (4. The first term is obviously equal to the energy added between states 2 and 3. To. one in which the turbine and feed pump are both isentropic) is given by (4. Also. and is q.. which can be represented by the simplified diagram shown in Fig 4. and qoUt would be greater than in the ideal case. Considering the other term. 4.24) could be reduced to qout = h4 . Such a situation can be seen on the steam plant shown in Fig 4. the maximum work (per unit mass of steam) that is obtainable from the fluid is v C .b4> b3.1) results in Vth = wt .Rankine cycle 69 The irreversible cycle can be seen to be less efficient than the reversible one by comparing eqns (4.2(a).23) h h 3 2 where w .3). then the difference between the entropies at states 4 and 1 would be greater than the differences at states 2 and 3.. The usual definition of thermal efficiency given in eqn (4. In the case shown b2. If the cycle was not reversible due to inefficiencies in the turbine and feed pump.h .22).$ 2 ) (4. = To(s3 .7) Examination of eqn (4. ~ = b3 .b4.. as shown previously simply from considerations of energy. the energy rejected to the cold reservoir is 40Ut = h4 . and leaves system A with a state defined by 2. and the product of the dead state iemperature. from the definition of exergy. if the feed pump and the turbine were both reversible then processes 34 and 12 would be isentropic and eqn (4. the cycle would be less efficient.e.b2 = (h3 . Hence.
2 Steam turbine power plant w f 3 F i5 i I I i i i 'I'. \ \\.70 Rational efficiency of a powerplant (a) (b) Fig. 4.. 1. / = 2 4 \ ' ...L Qi. \ W T i  \ \.\.
340 . It will be shown that this results in a rational efficiency of unity for an ideal (internally reversible) Rankine cycle.8 kJ/kg .1.0.091 kJ/kg K Thus Xg= 6. If there are any irreversibilities then the rational efficiency will be less than 100%. 4. Rational efficiency shows the scope for improving the device within the constraints of. It has to be remembered that these definitions of rational efficiency for a steam plant cycle are based on the dead state temperature being made equal to the condenser temperature. peak pressure and temperature.1 Steam turbine cycles A steam turbine operates on a basic Rankine cycle with a maximum pressure of 20 bar and a condenser pressure of 0.22). When the term rational efficiency is applied to an airstandard cycle it is never possible to achieve a value of unity because the temperature at which energy is rejected is not constant. and evaluate the rational efficiency of the cycle. Conditions at 4 p 4 = 2 0bar. The parameters for the state points on cycle 12346. = 2799 kJ/kg. X = 1 t.1. These effects are discussed in the examples. sf= 1. Conditions at 6 sg = 6.340 kJ/kg K Pa= 0. and such an approach can be used to indicate how far an actual (irreversible) steam plant cycle falls short of the yardstick set by the reversible one. + (1 .3"C. say. = 2645 kJ/kg. s6 = 6. If another temperature is chosen then the rational efficiency will be reduced as shown in eqn (4. whereas if it is high then not much improvement is possible.x)h.4 Examples Q.593 .4.5 bar. This will also be considered in the examples by reference to the Joule cycle for a gas turbine. = xh.Examples 71 This means that a steam turbine which operates on a reversible Rankine cycle will have a rational efficiency of 100%.091 7.1 will now be evaluated. = 81.091 = 0. = 212.593 kJ/kg K.8073) x 340 = 2200. Calculate the maximum net work available from the cycle. this approach also masks the 'cost' of external irreversibilities between the working fluid in the condenser and the true dead state of environmental conditions.4"C. = 0. Evaluate the thermal efficiency of the plant. h.340 kJ/kg K t. h f = 340 kJ/kg sg = 7.8073 x 2645 + ( 1 . Solution The Ts diagram for the Rankine cycle is shown in Fig 4.5 bar.8073 h. h. However. If the rational efficiency is low then the efficiency can be improved significantly.
72 Rational eficiency of a powerplant k 5E F ? To.. To= 81. .3 + 273 = 354.+dh12=340+2. WT = h4 .001 155 m3/kg w12= .Toso) 342.a.11 =342. =T.2200.2 kJ/kg K Thermal efficiency of the cycle is w.. Thus b4 = h4 .1 1 kJ/kg h2=h.4 ..1 1 2799 .091 kJ/kg K. = h..hZ  598. = 1.a. This is arbitrary. kJ/kg = b. S.T0s4.3 "C T.2 x (0.001 155)/2 x 19. wp= = 0.091 . wT + wP = ~ qh h4 . p .=20°C ~~ saturated vapotn . S Fig. kJ/kg = .v d p = dhlz = . . = 44. = 2799 .001029 m3/kg Conditions at 2 p 2 = 20 bar.243 The maximum net work available can be evaluated from the change of exergy between state points 4 and 2.0009 x Hence feed pump work. = It is necessary to define a dead state condition. = 552. s1 = 1.a.1 kJ/kg Work done by turbine.Tos2 (h. Hence. and in this case will be taken as the condition at 1. h .342.2. .=8 I .7 .354.001157 + 0.1 = 0. = 0.]me '.Toso) 2799 . = 340 kJ/kg v1 = v f = 0.~ Vth = __.(0.4 Temperatureentropy diagram for a basic Rankine cycle Conditions at 1 p 1= 0.3 x 1.2 .5 bar. 4.001029 + 0.b.3 K.( h . Hence Gne1 b.5 bar.340 .091 kJ/kg K v2 = 0.1 . .354.a.h.3 x 6.5 x 100 = 2.8 = 598. _ Entropy.
)(s4 . (b) the isentropic efficiency of the feed pump is 70%. = 342.4 .a. the rational efficiency is l.00 77R .4 = 919.s diagram bounded by the initial dead state temperature of 81. W/kg Hence Gnet= 941.h.Examples Hence Gmt= 552.649 This result shows that irreversibilities in the condenser producing a temperature drop of 81. (To.1 1 = 1. then the following values would be obtained: b. the thermal efficiency of the cycle is 77t h = wXt qh WT + wp  = 0.09) = 321. Hence. kJ/kg b2= h2. and it was assumed that the temperature of the working fluid in the condenser was equal to the dead state (ambient) temperature.6 .2.T.). Solution (a) Turbine efficiency.3"C.80 x 598..lT= 80%. at 24.340 . i. there is no scope for improving it unless the operating conditions are changed.1 Hence.293 x 6. (c) the efficiency of the components is the combination of those given in (a) and (b)..0 W/kg Thus. If the turbine efficiency is 80% then the work output of the turbine becomes W T = 77T(wT)isen = 0. the rational efficiency is wnet wnet 598.3"C to 20°C would reduce the potential efficiency of the powerplant significantly. as shown in Fig 4.a. = 2799 . Q. ..194 h4 .a.1 73 W/kg Thus.4 . = 941.To$.2.2 Steam turbine cycles Reevaluate the parameters for the steam plant in Q.8 W/kg.a. which is equal to (354.2 .3293) x (6.4) = 597.1 1 919.1 b4b2 = 0. It is possible to evaluate the rational efficiency of a steam plant operating on a Rankine cycle in which the condenser temperature is above the ambient temperature.s. l.1 1 2799 .1.= b4b2 %et 597.e.22. If the dead state temperature in the previous example was taken as 20°C rather than 81.2.3%.293 x 1.2 = 478. = 22.U . = h.lR= wnet wnet knet  598.a.Tos4.1 .340 . although the cycle is not very efficient.3"C and the final one of 20°C and the entropy difference. .2 .6 H/kg 478.7 .342.(44.1 In this case the rational efficiency is equal to unity because the turbine and feed pump have isentropic efficiencies of loo%.l based on To= 81.4.3"C if (a) the isentropic efficiency of the turbine is 80%.= .091 .4 . Basically this irreversibility is equivalent to a loss of potential work equal to the area of the T .
091 . wmt + wp  h4hZ 598. qp= 70%. Hence.1 = 0. s2' = s. (c) Turbine efficiency l.80 The rational efficiency has been significantly reduced by the inefficiency of the turbine.01 = 0. + dh.3 Steam turbine cycles The steam plant in Q.194 The rational efficiency is Q.= . and the rational efficiency is almost 1. H/kg The rational efficiency is [Wnetlactual VR = b 4  [Wnetlactual k t  .[wnetlactual ~ b4 .a. Assume that to= 81. (b) Feed pump efficiency. The feed pump work becomes h. This cycle is shown in Fig 4. feed pump efficiency qp= 70%. a.01 = 343 kJ/kg WT The thermal efficiency of the cycle becomes V rh ==qi.2 .23. (c) the efficiency of the components is the combination of those given in (a) and (b).998 596.. i.3.5 ..b2  .T0s2.3.6 . (b) the isentropic efficiency of the feed pump is 70%.2 The reduction in thermal efficiency is small.bZ 598.2 is modified so that the steam is superheated before entering the turbine so that the exit conditions from the turbine of the ideal cycle are dry saturated.01 2799343 = 0..242 2799343 The exergy at 2' may be evaluated approximately by assuming that the entropy does not change significantly over the pumping process. = 343 . The thermal efficiency is wnet vrh= . . = h..3 x  1.WT + wp  qi.lT = SO%.e. the Rankine cycle is not much affected by inefficiencies in the feed pump..5.4786211  %et 597.a.. Evaluate the parameters for the steam plant if (a) the isentropic efficiency of the turbine is 80%. = 43. and the rational efficiency is approximately equal to the isentropic efficiency of the turbine.01 = 0. = 340 + 3.74 Rational eficiency of a powerplant The rational efficiency is VR = [ ~ n c t l a c t u a . h4hT 478.. Hence b. = h2(.3"C.354.
5 bar t.701 .7. kJ/kg 5 b. = 81.Examples 75 Fig.11 3601 342.6 x (3690 .a . = 2645 kJ/ kg.2 .00 955.TOSS.3 x 1. h. WT = h5 .a0 = 910.593 H/kg K 6 Conditions at 5 p5 = 20 bar.091 .~ vth=== w T + w ~ = 0.593 kJ/kg K.TOsz a0 = 342.5 Temperatureentropy diagram for a Rankine cycle w t superheat ih Conditions at 6 p6 = 0. .354.292 qh h5h2 b = h5 .1 Thermal efficiency of the cycle is w.431 x 100 = 560°C h5 = 3467 + 0.431 7.593 H/kg K Hence t.=500+ 7.3 x 7. sf = 1.354.7.a0 = 44.3"C.2645 = 956 kJ/kg K 6 9562.U O = 3601 .h = 3601 . s5 = s6 = 7.8 .a0 kJ/kg  The rational efficiency is [~netlactual vR = b q  [wnetlactua~ %et .593 . hf = 340 kJ/kg sg = 7.4 . 4. s6 = 7.593 . = h.1 .3467) = 3601 W/kg Work done by turbine.091 kJ/kg K h = 2645 kJ/kg.b2 .956211 = 1.
The effect on the feed pump work is the same as above.342.8 . l.[WnetIactual . Calculate the net work output.998 910. The rational efficiency is an estimate of how close the cycle comes to the internally reversible cycle. and the rational efficiency is almost 1. The rational efficiency is [WnetIactua~ 77R = .lT = 80%.(44.234 qi. WT = vT(wT)isen = 0. and these should be taken as the dead state conditions also.287 H/kg K.76 Rational eficiency o a powerplant f (a) Turbine efficiency. . 7. = 8 0 % feed pump efficiency. (b) Feed pump efficiency. == w T + w ~  9563.234 qi..3. Q.h2 The rational efficiency is 77R = [~netlactual  .1 = 0.lp=70%.01 3601 .343 = 0. the maximum work output. efficiency is wne1 VIh== WT + wp  764.h2' The rational efficiency is [Wnetlactual 77R =  [wnetlactual  bs .b2 955.2 It can be seen that both the basic and superheated Rankine cycles are equally affected by inefficiencies in the individual components. ~ ? . the effect of the turbine efficiency is to reduce the rational efficiency by an amount almost equal to its isentropic efficiency. Assume that the working fluid is air with a value of K = 1.01 %net = o. and the rational efficiency of the cycle.8 .8 H/kg Hence. l.8 . the reduction in thermal efficiency is small.80 x 956 = 764.799 Hence.b2' 955.b2. hq .4 Gas turbine cycle A gas turbine operating on an ideal Joule cycle has a pressure ratio of 20: 1 and a peak temperature of 1200 K. h5 . .8 . 956 .4) (c) Again. the thermal efficiency of the cycle is 77fh wnet ==WT + wp  764.3.netl lac ma^ .2 = 0.01 = 0. again. and the thermal efficiency of the cycle becomes 77ih w. The inlet conditions at 1 are 1 bar and 300 K. Turbine efficiency.4 and a specific gas constant R = 0.01 3601 .2.764.3. the thermal efficiency.7648211 +net bs .798 b5 . h.1 1 3601 .lp = 70%.h2. The thermal .295 qi.343 = 0.
.4 x 0.R InP T O Po From the parameters given. 4. (b) Temperatureentropy diagram for Joule cycle with irreversible compression and expansion Solution The ideal Joule cycle is depicted by 12s34s1 in Fig 4.6 (a) Temperatureentropy diagram for Joule cycle.Examples 77 Entropy.0045kJ/kgK. S Fig.. The relationship between entropy and the primitive properties for an ideal gas is s %= T cPln.6(a).287 0. KR cp= K1  1. S @) Entropy.4 = 1.
2kJ/kg The net work from the cycle is wmt= wT + wc = 693. as b = ( h .300h 706.. and hence The isentropic work done in the compressor is wq.} “hq To K Po Thus.3 kJ/kg.T ~ s) (ho .0045 x = thermal efficiency is This value is equal to the standard expression for the efficiency of a Joule cycle.= dhl.T ~ (.= cp(T1.TZs)= 1.706.9 = kJ/kg The energy added to the cycle is (1 200 .4 = 509. the values of exergy are defined.1 .706.TZS) 1.0045 x (706.TOSO)= ( h .t .To { ( ln.1.9)= 693.1).ho) ... = b b 3 2 Now.1)/K = T4s = T 3 ( 9 1200 x ($) 0.509. = cP(T3 .To). For an isentropic expansion from 3 to 4 s (K q Z s 3 = cP( .. for a perfect gas.2+ (407. and the = wT.1)= 4 6 1 kg 9.0045 x T3 .300)~407.S O ) s = cp (T . The maximum net work output is defined by $. along an isobar (TTo)TohT O Since both 2s and 3 are at the same pressure Thus ..4/1.9) 285.78 Rational efficiency of a powerplant The compression process from 1 to 2s is isentropic.9K Hence the isentropic turbine work is (1200.TaS) 1..
The maximum net work obtainable from the rejected energy is b.7734 kJ/kg K 300 .8% of the maximum net work from the working fluid.6 + (407.848 This means that the ideal Joule cycle is only capable of extracting 84.6 W/kg 146.296 The temperature after the turbine is T4= T3. and (c) the combined effect of both inefficiencies.6(b).1 = 647.7 kJ/kg Hence w .9 1.0.b. . ~ WT = + W C = 554.300111 300 1 This term is shown in Fig 4.7 496. Solution (a) Turbine isentropic efficiency. This is equal to = 509.8 x 693.9 K. whereas under similar conditions (with the dead state temperature defined as the minimum cycle temperature) the Rankine cycle had a rational efficiency of 100%.0045In .0. The reason for this is that the energy rejected by the Joule cycle. If the efficiencies of the turbine and compressor are not 100% then the diagram is shown in Fig 4. This will affect the work output of the = ~ T W X . .3 336. and the entropy at 4. from 4s to 1.8 x 690.R lnTI PI = 647.lT = 80%. It can be seen that the rejected energy is larger in this case. = 0. calculate the effect of (a) a turbine isentropic efficiency of 80%.6(a).300) . (b) a compressor isentropic efficiency of 80%.s1 = cpln T4 P4 . still has the potential to do work. turbine in the following way: WT l.0. and is energy which is uaavailable for the production of work.9 1.Examples The rational efficiency of the cycle based on these dead state conditions is 79 wnet 9R==Gnet 285. related to 1.0045 x (509.5 Gas turbine cycle For the gas turbine cycle defined in Q.2 = 554.4.9) 146.1 = and wnet q2s3 %I== = 0.vTATsn = 1200 . . is s4 .. Q.9 .3 . .
The work done in the compressor is wc=WCi. .0. This is equal to To(~4 ~ 4 =~ 300 x (0. To(~4 s ~ ~ )shown in Fig 4. it also increases the unavailable energy by the as .300 In 300 This is a significant increase over the rejected potential work for the ideal Joule cycle.7734 .5328) = 72.3 .0. The rational efficiency of this cycle is BR .72.2 = 146. qc = 80%.7 336.b .2 kJ/kg  The net work from the cycle is wmt= wT+ w c = 693.[Gnct]E.3 .117.2 + (509. at 2.4 .300) . However. 394." BC .jccd To(~4 ~ = 4 =~ 336. ) .2 183.0. Since both 2 and 3 are at the same pressure b3 . in addition to the inefficiency of the turbine increasing the maximum net work rejected.b.7 kJ/kg ) This is the same value as found from the more basic calculation.3 The maximum net work output is defined by GXt= b.509. = c p [ ( T 3 T .. is The energy added to the cycle is q23 = cP(T3 Tz) = 1 .et W".465. irreversibility.6(b).Toln  .807.80 Rational eficiency of a powerplant Hence.6) = 394.t 146.9 kJ/ kg Temperature after compressor.9) the thermal efficiency is Vth = 183. the maximum net work rejected is (647.436 (b) Compressor isentropic efficiency.2 kJ/kG ) Since the maximum net work is the same for this case as the ideal one then the net work is given by wnet Gmt.=&. and = = wnct q23 .3 kJ/kg.0045 x (1200 .9 .
Hence.40. However.s2s) = 273. the inefficiency of the compressor has introduced a quantity of unavailable energy T0(s2 s2J.sZs)= 273.0. S Fig.2 = 182.5 W/kg In this case.6 .50. The net work output of the device is made up of wnet $Et = .TO(s2.2 wnet The net work output of this cycle is made up in the following way: Wnet = $net  [$netlrejecred  . and turbine isentropic efficiency l. the net work output of the cycle is w.6  117.670 it.2 . = wT + W C = 554.. This cycle combines the two inefficiencies considered above..4 .7 The effect of inefficiency in the compressor (c) Compressor isentropic efficiency vc = 80%.6 + (509.113 q23 394.2 = 43.6 1200 The rational efficiency of the cycle based on these dead state conditions is VR== 81 1 w.6 .= 273. thermal efficiency is 47th = = .2 kJ/kg.72.3001n .' I ' 4 4s Entropy.Examples Thus (1200 . 4.lT = 80%. .40. an additional quantity of net work has been lost which is not evident .3 273.7 kJ/kg Net heat addition q23 = 394.7 \ \ \ \ \ .9) 44. Hence.which is depicted in Fig 4.807.8 kJ/kg This equation shows how the inefficiencies reduce the net work obtainable from the cycle. 2 /// = 44.9 .6) .6kJ/kg 807..7. 183.s4s)  .0.
The latter causes the temperature after compression to be higher than the isentropic value. Steam turbine Dowemlant 41  [83. steam plant) can achieve rational efficiencies of 100 per cent.g. 4. and hence less fuel is necessary to reach the maximum cycle temperature. gas turbines) can never approach such a high value. and that is the reduction in maximum net work caused by the inefficiency of the compressor. The condensate left the condenser as saturated liquid at 38°C and the superheated steam leaving the boiler was at 10 bar and 300°C. It has been shown that devices in which the working fluid changes phase (e.g.5 Concluding remarks The concept of a Second Law. or rational. efficiency has been introduced. Neglecting the change in state of the feed water in passing through the feed pump.24.3%] 2 Again neglecting the change in state of the feed water in passing through the feed pump. P . I Fig. This provides a better measure of how closely a particular powerproducing plant approaches its maximum achievable efficiency than does the conventional ‘First Law’ thermal efficiency. the measured rate of steam supply was 7. The effect of irreversibility on rational efficiency has also been shown. PROBLEMS 1 In a test of a steam powerplant (Fig P4. Also calculate the thermal efficiencyof the cyclic plant.1).3%.82 Rational efficiency of a powerpiant from the equation.1 kg/s when the net rate of work output was 5000 kW. calculate the thermal efficiency of an ideal Rankine cycle in which the . whereas those which rely on a single phase fluid (e. and taking the environment temperature as being equal to the saturation temperature of the condensate in the condenser. calculate the rational efficiency of the workproducing steam circuit (system A).
and delivers air to a combustion chamber which is supplied with methane ( C q ) at 25°C. 372. The products of combustion leave the chamber at 1450 K and suffer a pressure loss of 5% in passing through it.2%.9 kJ/kg. 36. alternative calculation of the thermal eficiency of this ideal Rankine cycle.5%. The maximum temperature of the working fluid is 1150 K and its minimum temperature is 400 K. [0. calculate the mean temperature of heat reception in the ideal Rankine cycle of Q.4 kJ/kg] 5 A steam turbine operates on a superheated Rankine cycle.1. The pressure and temperature of the steam leaving the boiler are 10 bar and 350°C respectively.Problems 83 conditions of the fluid at inlet to and exit from the boiler are the same as those of the plant in Q. and isentropic compression and expansion). Energy is added to the working fluid (air) by a heat exchanger maintained at 1250 K.84%.86%. [26.35. [29.83.3%] 3 Neglecting the temperature rise of the feed water in passing through the feed pump. Explain why the value calculated by this method is higher than that obtained previously.260.2%] 4 Air enters the compressor of a simple gas turbine at a pressure of 1 bar and a temperature of 25°C. and (c) the rational efficiency of the engine. 29.6 depicts a closed cycle gas turbine operating on the Joule cycle (i. Calculate (a) the airfuel ratio of the engine. The specific steam consumption of the plant is 4. Also calculate the mean temperature of reception of heat in the boiler and use this in conjunction with the condenser temperature to evaluate the thermal efficiency. Hence confirm that the efficiency ratio of that plant is equal to the rational efficiency of the workproducing steam circuit calculated in Q.6%. the turbine isentropic efficiency. and K = 1.l. The pressure in the condenser is 0. What is the maximum work per unit mass of exhaust gas that could be obtained if the ambient conditions are 1 bar and 25"C? The enthalpy of reaction based on 25°C is 50 000 W/kg.2 kJ/kg. Evaluate the irreversibilities introduced by the heat transfer processes and calculate (a) the First Law efficiency work ouput 9 = 1 energy addition . They are then expanded in a turbine with an isentropic efficiency of 90% to a pressure of 1. 84. The products of combustion can be treated as a perfect gas with cp= 1.1. If the feed pump work may be neglected.55 kg/kWh.02.05 bar. calculate the thermal efficiency of the plant. Hence make a second. The pressure ratio of the compressor is 5 : 1.85%] 6 Figure P4. and the Gibbs energy of reaction is 51 OOO kJ/kg. The compressor has a pressure ratio of 15 and an isentropic efficiency of 85%. and rejected to another heat exchanger maintained at 300 K.30.e. and evaluate the rational efficiency. (b) the power output per unit mass flow of air. [440 K. constant pressure heat addition and rejection.05 bar.
[36. P4.9%. R H/kg K.005 H/kg K. 1c work output 71 = 1 availability of energy addition = 0.5%] .6 Closed cycle gas turbine Calculate the maximum efficiency that could be achieved from this system by modification of the heat exchangers.4 and the specific gas constant. 1250 K Heat addition reservoir b Electric generator Heat rejection reservoir Fig.287 = 1.48.84 Rational efficiency of a powerplant (b) the Second Law efficiency Assume cp= 1.
It requires an ideal. the engine rejects energy at T2 but the cold reservoir is at T. In a similar manner.1) if the temperature drops between the reservoirs and the engine approach zero. It can be assumed that the engine itself is reversible and acts as a Carnot cycle device with This thermal efficiency is less than the maximum achievable value given by eqn (5. The reservoir at THtransfers heat to the engine across a resistance and it is received by the engine at temperature T.. It is possible to evaluate the maximum power oufpuf achievable from an internally reversible (endoreversible) heat engine receiving heat irreversibly from two reservoirs at TH and T. like a Stirling engine). Assume that the engine is a steadyflow one (e. > T. reversible heat engine (internally reversible) but.) reservoirs is given by This cycle is extremely idealised. .5 Efficiency of Heat Engines at M a x i m u m Power 5. The former is limited by size and cost factors whilst the latter will limit the actual power output achieved for the engine. A schematic of such an engine is shown in Fig 5..g. To achieve external reversibility it is necessary that the temperature difference between the reservoirs and the engine is infinitesimal.g. in addition. like a steam turbine or closed cycle gas turbine): a similar analysis is possible for an intermittent device (e.1 Efficiency of an internally reversible heat engine when producing maximum power output The thermal efficiency of a Carnot cycle operating between high temperature ( T H ) low and temperature (T./T. The value can only approach that of eqn (5.1... based on Bejan (1988)./T. which means that the heat exchanger surface area must be very large or the time to transfer heat must be long.1) because T. This will now be done. the heat transfer from the reservoirs is also reversible (externally reversible).
Tc) (5. UHAH.e.5) Now.g. 5.1 Internally reversible heat engine operating between reservoirs at THand T .86 Eficiency o heat engines at maximum power f Fig.4) and. kW/m2 K) = A = area of heat transfer surface of hot reservoir (e.g. from eqn (5. The heat transfer to the cold reservoir is similarly Qc = UcAc(T2.3) where U H heat transfer coefficient of hot reservoir (e.Q C (5.g. Tc. and the ratio T2/Tl= z. This means that It is possible to manipulate these equations to give W in terms of TH. From eqn (5. The heat transfer from the hot reservoir can be defined as Q H = uHAH(TH TI) (5.6). . the heat engine is internally reversible and hence the entropy entering and leaving it must be equal i. m2) H and Q H= rate of heat transfer (e.4) By the first law w=QH. kW).
0 at Differentiating eqn (5.Tc/TH)of the Carnot cycle (which produces zero energy flow rate) and the zero efficiency engine in which T2= TI (which produces high energy flow rates but no power).) f1 .TJT.12) Hence aw/& = o when t = 00 or t 2= Tc/TH.t) 7 .T2/T1) a reasonable level.TJT.) l+ (5.t) (t. the ratio of temperatures across the engine and the thermal resistances.) . t2 (5.11) Thus the rate of work output is a function of the ratio of temperatures of the hot and cold reservoirs. It compromises between the high efficiency ( qh = 1 . The optimum temperature ratio across the engine (t) to give maximum power output is obtained when aw .1 1) with respect to t gives aw 1+ 1 (1 .. .10) and hence w (5. Considering only the nontrivial case. f o r maximum work output This result has the effect of maximising the energy flow through the engine while at maintaining the thermal efficiency ( q h = 1 .Eficiency of an internally reversible heat engine 87 Hence Rearranging gives t ( 2:.(t.
. from eqn (5.88 EfSiciency of heat engines at maximum power Hence the efficiency of an internally reversible.W >= 200 units UHAH UcAc &AH Thus T . also calculate the maximum power. The heat transfer conductances (UA) are the same on both the hot and cold sides.) 2 = . Solution Equation (5.11) gives the work rate (power) as For maximum power output z = (TC/TH)'/'= (400/1600)1/2. n Example Consider a heat engine is connected to a hot reservoir at 1600 K and a cold one at 400 K.(1 + 1) 2 UHAH 1 1 (1 .10) QH   w U H A H ~ ( Qc = 400 units UnAH Then Qc = 1 (Q. Then  w . . Evaluate the high and low temperatures of the working fluid of the internally reversible heat engine for maximum power output.1600 (it) .2 for the engine and reservoirs. ideal heat engine operating at maximum power output is A example will be used to show the significance of this result. =z [ ~ + T c } = 2 x ( 2 0 0 + 4 0 0 ) = ~ UcAc 1200K and T2 = = 600 K 2 1200 This results in the temperature values shown in Fig 5.200 units  1600 8 and.
/U. It is possible to derive relationships for the intermediate temperatures.13) UHAHTH (l+Z) Substituting in eqn (5. (Z .)  (5.lm = 1 .10) and (5.75 and eqn.  w UnAn TH UHAH TH UUAH TH Substituting from eqns (5.lm = 1 . = Q.Efficiency of an internally reversible heat engine 89 7' QH= 400 units 1' Q. T .W .A.A.(t. (5.A. = 200 units Fig.Tc Qc + U Ac C Also Q. and then Qc (5.600/1200 = 0.8) gives T2= UHA.AHT. T.14) .TCIT.) UcAc l +  ( 22) (Z . Equation (5. = 400 K with U. 5.'~ + Tc + U. UcAc + &AH = Tii2{ U. Thus an engine which delivers maximum power is si&icantly less efficient than the Camot engine.50. .9) gives 7.400/1600 = 0.TCIT.8) defines T2as T2 = . = 1 The efficiency of the Camot cycle operating between the reservoirs would have been but the efficiency of this engine is 7. U A + UCAC HH I (5.t2) + Tc  U.11) gives Qc .2 Example of internally reversible heat engine operating between reservoirs at TH= 1600 K and T.8)  Q .
90 EfJiciency of heat engines at maximum power
Similarly
T
u
A T ’ / ~U~A,T$~ +
(5.15)
Un An + UcAc
To be able to compare the effect of varying the resistances it is necessary to maintain the total resistance to heat transfer at the same value. For example, let
UHAH + UcAc = 2
Then, if UHAH/UcAc= 1 (as in the previous example), UHAH = 1. Consider the effect of having a high resistance to the high temperature reservoir, e.g. UnAJUcAc = 112. This gives
Then
1600 (’” 1/4) (1  1/2) (1 + 1/2)/2
= 267 units,
giving W = 177.8 units
w
uti AH (1 Then
Q  c   Qc 
= 534 units
and Q ,
= 355.6 units
*L1
(QH
 W ) = 133.5 units, giving Qc = 177.8 units
UcAc
UHAH 2
~UHAH
Hence
1 T, =  (133.5 z
+ 400) = 2 x 533.5 = 1067K, and T , = 533.5 K.
If the resistance to the low temperature reservoir is high, i.e. U,AH/UcAc = 2, the situation changes, as shown below. First,
UnAn
=
2
~
2    4 3/2 3
1+1/2
giving
w
UnAn
 1600
(1/2  1/4) (1  1/2)
(1 + 2)/2
=
133 units
which results in W=177.8 kW and
Qn
 267 units, or Q = 355.6 kW
UHAH
EfSiciency of an internally reversible heat engine 91
Then
Qc 
UcAc
2Qc  2 ( QH W ) = 267 units, giving Qc= 200 units UHAH UHAH
Hence
T I =' [ A + T c ] = 2 ( 2 6 7 + 4 W ) = UcAc
These results are shown graphically in Fig 5.3.
1334K,andT2=667K
133
T,
120c
1067 K
&
T*
600
T, = 400 K
T
T
533 K
Fig. 5.3 The effect of heat transfer parameters on engine temperatures for a heat engine operating between reservoirs at TH= 1600 K and Tc = 400 K
k
QH
66;
Comparing the power outputs based on the same total resistance, i.e. U A + UcAc = 2, HH gives the following table.
UHAHluCAc
1 112 2
W
Qc
400 355.6 355.6
200 200 177.7 177.7 177.7 177.7
It can be seen that the optimum system is one in which the high and low temperature resistances are equal. In this case the entropy generation (per unit of work) of the universe is minimised, as shown in the table below.
UHAHIUCAC QJTH QHIT, ASHIW
+4.17 x +6.23 x +2.48 x
QcIT,
QcITc
AScIW
+4.17 x +6.24 x +10.00 x
ZASlW
1 112 2
0.25 0.225 0.225
+0.333 +0.333 +0.266
0.333 0.333 0.266
+OS 0.4443 0.4443
+8.34 x +0.00125 +0.00125
92 EfSiciency of heat engines at maximum power
5.2 Efficiency of combined cycle internally reversible heat engines when producing maximum power output
One way of improving the overall efficiency of power production between two reservoirs is to use two engines. For example, a gas turbine and steam turbine can be used in series to make the most effective use of the available temperature drop. Such a power plant is referred to as a combined cycle gas turbine, and this type of generating system was introduced in Chapter 3 in connection with pinch technology. These plants can be examined in the following way, based on the two heat engines in series shown in Fig 5.4.
Fig. 5.4 Two internally reversible engines in series forming a combined cycle device operating between two reservoirs at THand T,
In this case the product UA will be replaced by a ‘conductivity’ C to simplify the notation. Then
(5.16) (5.17) (5.18)
Also, for E,
(5.19)
and for E,
_ Q2  Qc
7.3
74
(5.20)
t 2 T4/T,; then rearranging eqns =
Let z,
=
T2/T,and
= TH 
(5.16), (5.17) and (5.18) gives
QH/CH
T2 = Q2/c2i T3
(5.21) (5.22)
Eficiency of combined cycle internally reversible heat engine 93
and
T4 = Q C K
C
+ Tc
(5.23)
Also (5.24) and
(5.25)
Similarly (5.26) From eqns (5.16) and (5.26)
QH=CnT H  
[
1 Q
1 Q c L +  + T c
C2
t 2
TI(
{Tc
})]
(5.27)
Rearranging eqn (5.27) gives (5.28) which can be written as (5.29)
The power output of engine E , can be obtained from eqn (5.29) as (5.30)
In a similar manner Wc/CHTH also be evaluated as can
(5.31)
(5.32)
94 EfSiciency of heat engines at maximum power
It can be seen from eqns (5.30) and (5.32) that it is possible to split the power output of the two engines in an arbitrary manner, dependent on the temperature drops across each engine. The ratio of work output of the two engines is
(5.33) r1 (1 r2) This shows that if the temperature ratios across the high temperature and the low temperature engines are equal (i.e. t,= r 2 ) ,the work output of the low temperature engine will be
wc
w, 
1 (1 rl)
ci/,
=
T1WH
(5.34)
Hence the work output of the low temperature engine will be lower than that of the high temperature engine for the same temperature ratio. The reason comes directly from eqns (5.30) and (5.31), which show that the work output of an engine is directly proportional to the temperature of the ‘heat’ at entry. The power output of a combined cycle power plant is the sum of the power of the individual engines, hence
This may be reduced to
wcc C T H H
 t,r21
(5.35)
The efficiency of the combined cycle is defined by
wcc
vth=
 1
(5.36)
QH
Equation (5.36) shows that the expression for the efficiency of the combined cycle engine at maximum power output is similar to that for the efficiency of a single heat engine, except that in this case the temperature ratio of the single engine is replaced by the product of the two temperature ratios. If the combined cycle device is considered to be two endoreversible heat engines connected by a perfect conductor (i.e. the resistance between the engines is zero; C, = m) then T3= T,, and eqn (5.36) becomes
(5.37)
The efficiency given in eqn (5.37) is the same efficiency as would be achieved by a single endoreversible heat engine operating between the same two temperature limits, and what would be expected if there was no resistance between the two engines in the combined cycle plant.
Eflciency of combined cycle internally reversible heat engine 95
To determine the efficiency of the combined cycle plant, composed of endoreversible heat engines, producing maximum power output requires the evaluation of the maxima of It the surface WE plotted against the independent variables z1 and t2. is difficult to obtain a mathematical expression for this and so the maximum work will be evaluated for some arbitrary conditions to demonstrate the necessary conditions. This will be done based on the following assumptions:
temperatures: TH= 1600 K, T, = 400 K conductivities: CH= C2= Cc = 1
1'
Qn
AI
Qn
''
T 3
T 4
Qi
$c
r
l'
I' Qc
Qc
96 Eficiency of heat engines at maximum power
While these assumptions are arbitrary, it can be shown that the results obtained are logical and general. The variation of maximum power output with temperature ratios across the high and low temperature engines is shown in Fig 5.5. It can be seen that the maximum power occurs along a ridge which goes across the base plane. Examination shows that, in this case, this obeys the equation zlzz= 0.5 = .ITc'/7;1. Hence, the efficiency of a combined cycle heat engine operating at maximum power output is the same as the efficiency obtainable from a single heat engine operating between the same two reservoirs. This solution is quite logical, otherwise it would be possible to arrange heat engines as in Fig 5.6, and produce net work output while transferring energy with a single reservoir. Thus the variation of z1 with z2 to produce maximum power output is shown in Fig 5.7: all of these combinations result in the product being 0.5.
' '
6
2
06
055
05 05
055
06
065
07
075
08
085
09
095
1
Temperature ratio of high temperature engine
Fig. 5.7 Variations in temperature ratio of high and low temperature heat engines, which produce maximum power output
5.3 Concluding remarks
A new method for assessing the potential thermal efficiency of heat engines has been introduced. This is based on the engine operating at its maximum power output, and it is shown that the thermal efficiency is significantly lower than that of an engine operating on a Carnot cycle between the same temperature limits. The loss of efficiency is due to external irreversibilities which are present in all devices producing power output. It has been shown that a combined cycle power plant cannot operate at a higher thermal efficiency than a single cycle plant between the same temperature limits. However, the use of two cycles enables the temperature limits to be widened, and thus better efficiencies are achieved.
PROBLEMS
1 Explain why the Carnot cycle efficiency is unrealistically high for a real engine.
Introducing the concept of external irreversibility, evaluate the efficiency of an endoreversible engine at maximum power output.
initially at 800 K and 200 K respectively. .4. but assume the Carnot efficiency.. Shown in Fig P5. the work output of the Carnot cycle./(UA). S Fig./TH. The temperature of the hot reservoir falls by 1 K for each kJ extracted from it. [0. CH/CC 2. the maximum power output. 17 = 1 .T.3 Temperatureentropy diagram for Joule cycle . the maximum and minimum temperatures of the working fluid at maximum power output. If the heat transfer conductances from the reservoirs = = to the engine are in the ratio (UA). and K = ratio of specific heats./c. W / C ~ . 0. = 1 bar Entropy.75. the engine efficiency at maximum power output.5. 500 K ] A heat engine operates between two finite reservoirs.Problems 97 H Consider a heat engine connected to a high temperature reservoir at T = 1200 K and a low temperature one at T. What is the maximum work output from the engine as the reservoir temperatures equalise? Is the equalisation temperature for maximum work a higher or lower limit of the equalisation temperature? [200 kJ.’p2 = 12 bar _. 1000 K. c. lower] Closed cycle gas turbines operate on the infernally reversible Joule cycle with an efficiency of where rp= pressure ratio of the turbine. evaluate the following: 0 0 0 0 0 the maximum Carnot cycle efficiency. This equation significantly overestimates the efficiency of the cycle when external irreversibilities are taken into account. Derive all the necessary equations. P5.3 is a Ts diagram for a closed I. 100. = 300 K. while the temperature of the cold reservoir rises by 1 K for each kJ added. 0.*’ p. = 1.
which is internally reversible and gives a thermal efficiency of where r = volumetric compression ratio.T. Show the ratio of net work output for the Otto cycle to the energy transferred from the high temperature reservoir for the Carnot cycle. This ratio is less than the Joule efficiency . = minimum temperature of the cycle. K = ratio of specific heats. = 400 K. This value is significantly higher than that of the Otto cycle operating between the same reservoirs. An Otto cycle is depicted in Fig P5.and the temperatures of the two reservoirs associated with the cycle are shown as THand T. (i) Show that the thermal efficiency at maximum power output of an endoreversible engine executing an Otto cycle is where TH= maximum temperature of the cycle and T./TH. (ii) Calculate the ratio of the gas turbine cycle work to the energy delivered from the high temperature reservoir (QH for the Carnot cycle). ZH/cP=79.. (iv) What are the mean temperatures of energy addition and rejection in the Joule cycle? What would be the thermal efficiency of a Carnot cycle based on these mean temperatures? [0.0. . reservoirs is q = 1 . QH.explain why in terms of unavailable energy.4212.5.is where T2and T3are defined in Fig P5. 0.5.489 K ] 994 4 Explain why the Carnot cycle overestimates the thermal efficiency achievable from an engine producing power output.98 Eficiency of heat engines at maximum power cycle gas turbine receiving energy from a high temperature reservoir at TH= 1200 K and rejecting energy to a low temperature reservoir at T.9. The thermal efficiency of a Carnot cycle operatirig between these twc. (iii) Calculate the external irreversibilities and describe how these may be reduced to enable the Joule efficiency to be achieved.508.. 5 The operating processes of a sparkignition engine can be represented by the Otto cycle. Discuss why external irreversibility reduces the effective temperature ratio of an endoreversible engine.667. K. Evaluate the Carnot efficiency and compare this with the Joule efficiency: explain why the Joule efficiency is the lower. cp/c.
s2. evaluate the thermal efficiency of the proposed plant.4. and then evaluate separately the effects of the heat exchange and reheat.Problems 99 Entropy. and discuss the n T3I ( TdT2 ) Evaluate the entropy change required at the high temperature reservoir to supply the Otto cycle in terms of the entropy span.T2 differs from that of the Otto cycle. If these approaches have not increased the efficiency.l)/&i] ~ ~ ~ * ~ ~ 6 It is required to specify an ideal closed cycle gas turbine to produce electricity for a process plant. without reducing the work output.0. [As. The ratio of specific heats may be taken as K = 1.5731] . [OS.4233. Temperatureentropy diagram for Otto cycle 55 Explain why this value of significance of the term T3 . Evaluate the basic cycle efficiency. s3. T ~ ( . S Fig. of the Otto cycle. (ii) introducing reheat to the turbine by splitting the turbine pressure ratio such that the pressure ratio of each stage is the square root of the compressor pressure ratio. 0. The customer then feels that the efficiency of the turbine could be improved by (i) incorporating a heat exchanger. P . = C . propose another method by which the gas turbine performance might be improved (between the same temperature limits). The first specification requires that the turbine produces the maximum work output possible between the peak temperature of 1200 K and the inlet temperature 300 K.
du. = chemical potential of component i n.la) enables the change of internal energy. It will be shown in Chapter 12 that if a change in composition occurs then another term defining the effect of this change is required. or systems of constant com position The relationships which follow are based on single component systems. u. .C p i d n . or systems of constant composition. 1 where p .lb) The chemical potential terms will be omitted in the following analysis.1 The Maxwell relationships The concept of functional relationships between properties was introduced previously. to be written d u = T d s . eqn (6. and which allow for changes in composition. the Second Law states that. 6. in the general case where the composition can change. in specific (or molar) terms (6.1) (6. for a reversible process.2) (6. For example. although similar equations to those below can be derived by taking them into account. p and v are related in the following manner T d S = d U + p dV or. = amount of component i (6.p dv (6. s.la) T ds=du+pdv Rearranging eqn (6.1) should be written TdS = dU + p dV .2a) It will be shown in Chapter 12 that. These are a subset of the more general equations which can be derived.General Thermodynamic Relationships: single component systems. T .
4) dz = M dx + N dy For continuous functions.d x + . If this surface is continuous then the following relationships can be based on the mathematical properties of the surface.The Maxwell relationships 101 It can be seen from eqns (6. the following relationships apply over the major regions of the surface.2a) that the specific internal energy can be represented by a threedimensional surface based on the independent variables of entropy and specific volume.1 that the pv. the derivatives d2Z (6.2) and (6. but there are discontinuities at the saturated liquid and saturated vapour lines. Hence. but not across the boundaries.T surface for water is continuous over most of the surface.3) IV=($)~ Then (6. (6.dy Let (a (3 and I):(=. Then d z = . The restriction of a continuous surface means that it is ‘smooth’. It can be seen from Fig 6.5) ax ay and  aZz ay ax . y) where z is a continuous function. For a continuous surface z = z ( x .
13) ( $)v. . v) and y = y ( u .$)" ( = P (6. ($)s=($) s=($.15) (6.p dv .7) Hence giving These expressions will now be used to consider relationships derived previously.s dT Consider the expression for du.3) T= (6. and ($)v=l (6. such that x = x ( u .s dT dg = v dp . ($)v=($)T (6. v=($). given in eqn (6. v).10) then.11) (6. by analogy with eqn (6. Then Let z = v. y ) and x and y are themselves related to additional variables u and v. f o r constant composition or single component systems T=($).17) . The following functional relationships have already been obtained du=Tdspdv dh = T ds + v dp df = . then x = x ( z ) and (2) V =0. p = (%).16) P=(:).12) (6. ($)p=($)T (6. and (5).=($).102 General thermodynamic relationships are equal.10) (6. and hence (?)x=(:)y Consider also the expressions obtained when z = z ( x .14) In a similar manner the following relationships can be obtained. and u = x .
19) are called the Maxwell relationships.18a) and.19d) Equations (6. shilarly (6.19~) = MT (6.18d) In addition to these equivalences.19b) (6.17) also show that ($l= ($)p (6. eqns (6.2.INTERPRETATION OF MAXWELL RELATIONS Let a system comprising a pure substance execute a small reversible cycle 12341 consisting of two isochors separated by dV and two isentropes separated by ds. the area on the Ts diagram must equal the area on the p .The Maxwell relationships 103 If the pairs of relationships for T are equated then (z)v=($)p (6. Now the difference in pressure between lines 1 and 2 is given by and to the first order the difference in pressure between lines 3 and 4 is the same.14) to (6. If the cycles are reversible.1.20a) . 6. these cycles are shown in Fig 6. Hence the area on the p .v diagram.v diagram =  (3 ds dv (6.19a) (6.18b) (6.1 GRAPHICAL.18~) (6.
.104 General thermodynamic relationships e. the specific heat capacity at constant volume is (6... and hence dv ds = ($) V ds dv (6.22) ..20b) which is negative because the temperature decreases as the volume increases.2 Uses of the thermodynamic relationships When performing certain types of calculation it is useful to have data on the values of the specific heat capacities of the substance under consideration and also the variation of these specific heat capacities with the other properties. /+4 Applying the same approach to the Ts diagram. The specific heat capacities themselves are first derivatives of the internal energy ( u ) and the enthalpy ( h ) ./''' *. . and hence the variations of specific heat capacities are second derivatives of the basic properties. By definition. equating the two areas gives ( n). the difference in temperature between lines 1 and 4 is ($) S dv (6. . .21) 6. v + 6v 4..*\. n Y 2 m **> 5 2 E 2. and the area of the diagram is ( $) S dv ds Thus.' .
26) ($)”=: van der Waals’ gas and ($)“=O (6.24) Consider the variation of the specific heat capacity at constant volume. + f ( v ) for an ideal gas.25) Hence.19~) giving (6.28) . at different volumes.27) Hence c . with volume. This can be derived in the following way: Now. By integration it is then possible to obtain the values of c. it is possible to evaluate (a2p/aT2). The equation of state of a van der Waals’ gas is RT p=vb a v2 (6. and thus c. v.. c. consider whether the specific heat capacity at constant volume is a function of the volume for both an ideal gas and a van der Waals’ gas. Ideal gas The gas relationship for an ideal gas is pv = RT and (6. This is in agreement with Joule’s experiment for assessing the change of internal energy. For example.23) (6.and then (dc. or a mathematical relationship. if data are available for a substance in the form of a pvT surface. = T  (3 (6.Uses of the thermodynamic relationships But 105 ($). if the temperature is maintained constant. from eqn (6. with specific volume. Similarly = T . u../av).
32) . the variation of the specific heat capacity at constant pressure with pressure can be investigated by differentiating the specific heat capacity with respect to pressure. cp# f( p ) for an ideal gas. This is done below.29) Again c.31) This means that the specific heat capacity at constant pressure for a gas obeying the ideal gas law is not a function of pressure. but in certain cases and under certain conditions c. # f( v ) for a van der Waals’ gas. This conclusion is in agreement with the JouleThomson experiment for superheated gases.= RT V V2 (6.30) This equation can be used to see if the specific heat capacity at constant pressure of gases obeying the ideal gas law.28) can be rewritten as (p+.)(vb)=RT which expands to a ab p v + . So. for ‘gases’ obeying these state equations c . Hence R and ($)=O (6. at a datum volume and temperature.p b . + f ( v ) . Ideal gas p v = RT Hence (6.e.. if these equations are to be integrated to evaluate the internal energy it is necessary to know the value of c. Similarly. giving (6. could be a function of the volume of the system and it would be calculated in this way.106 General thermodynamic relationships where a and b are constants. Of course. Van der Waals’ gas RT p=vb a v2 Equation (6. i.. and those obeying van der Waals’ equation are functions of pressure.
a 2ab and hence ($). can Hence. cp= f ( p ) .T().which. be calculated from eqn (6.Uses o the thermodynamic relationships f Differentiating implicitly gives 107 which can be rearranged to give ($)JP7+7}. on substituting for 2ab 2a 6ab (6. for a van der Waals' gas.= pV2 a R (6.35) .4' .34) ($+=5.33) ( 'e) This can be differentiated again to give which results in a giving 2a a 6ab 2ab .34). dP aZv aT2 where (a2v/aT2). This means that allowance would have to be taken of this when evaluating the change of specific heat capacity at constant pressure for a process in which the pressure changed. This can be evaluated from cp = (6.
eqn (6.38) This is called the first Tds relationship. The most accurate way of performing such calculations is.p) and (6.108 General thermodynamic relationships 6.36) Hence (6. The following analyses will demonstrate how these values of internal energy and enthalpy are obtained. to use the enthalpy or internal energy values because these implicitly integrate the specific heat capacity over the range involved. and if the work done between two states was required.39) $) P .37) Now. Hence (6. If it is assumed that entropy is a function of temperature and pressure. When evaluating the performance of steam plant and refrigeration equipment. T) (6. The twoproperty rule can be used to define entropy as the following functional relationship s = S(V. enthalpy values at these states were evaluated and suitable subtractions were performed.40) By definition.19c). then s = s (T.3 Tds relationships Two approaches will have been used previously in performing cycle calculations. cp= T( (6. When doing cycle calculations for gas turbines and internal combustion engines the air was assumed to be an ideal gas and the specific heat capacity was used. much emphasis was placed on the use of tables. The second Tds relationship can be derived in the following way. by definition and from the Maxwell relationships. in fact.
the second Tds relationship is The third Tds relationship is derived by assuming that s = s ( p .Tds relationships and.42) (6.. and this enables the equation to be obtained.41) (6. The internal energy of a substance can be expressed as u = u (T. from eqn (6.47) from the first Tds relation (eqn (6. A similar expression can be derived for c. v) Now. This is the third Tds relationship.43) Thus. (6.46) Now cv = ($) (6. by definition.p dv Substituting for Tds in eqn (6. V ) (6.47) and from the second law d u = T d s .19d) 109 T ) : ( = ( &).45) Hence. It is now possible to investigate the variation of internal energy and enthalpy with independent properties for gases obeying various gas laws.38))gives (6.48) . the change in internal energy is (6.
This is not surprising because density is a measure of the closeness of the molecules of the substance. This is in agreement with Joule’s experiment that u +f(v) at constant temperature. the specific internal energy of an ideal gas is not a function of its specific volume (or density). This means that some of the internal energy in a van der .46) becomes (6. Van der Waals’ gas The equation of state of a van der Waals’ gas is RT p=vb and hence R Vb which gives the change of internal energy with volume as (6. Ideal gas The equation of state of an ideal gas is pv = RT and hence (6.110 General thermodynamic relationships and hence eqn (6.51) Thus (6.54) This means that the internal energy of a van der Waals’ gas is a function of its specific volume.49) or (6. or density.53) a v2 (g)T=[2P]=.52) Hence.50) can be used to evaluate the variation in internal energy with volume for both ideal and van der Waals’ gases. (6. and the internal energy variation is related to the force of attraction between the molecules.50) Equation (6.
This is useful because it is much easier to measure the specific heat capacity at constant pressure. c p .58) If eqn (6. V ) (6.than that at constant volume. It is also possible to use the following approach to show whether u = f( p ) . d T + . v). u. and not all of the thermal energy is due to molecular motion.59) . 6. as was the case for the ideal gas. This may be done in the following way: Now ($)..Relationships between spec@ heat capacities 111 Waals' gas is stored in the attraction forces between the molecules.4 Relationships between specific heat capacities These relationships enable the value of one specific heat capacity to be calculated if the other is known. P and sincep . = . if s is a continuous function of temperature and volume.dv V2 Hence for a van der Waals' gas u = f(T. For a van der Waals' gas a du = C . (6. ds = ($). T. (fl=. for an ideal gas u = f(T). for a change in volume and temperature it is necessary to use the following: For an ideal gas (6. c.e. + ( dT dv (6.  # 0. for an ideal gas u # f( p ) .57) and.56) Hence.55) i. if it is required to calculate the total change in internal energy. then (6.58) is differentiated with respect to temperature. with pressure maintained constant. Now. U i g the twoproperty rule it is possible to write sn s = s(T.
9) (6. at 4°C for water. is controlled by the sign of (ap/av).19c))..= 0.63) = Examination of eqn (6. It can also be shown that cP>c. Similarly.61) in relation to the state diagrams for substances.. as shown in Fig 6.60) T P From Maxwell relations (eqn (6.61) The mathematical relationship in eqn (6.3. are when T = 0 or when (ap/aT).. i.e. which can be evaluated along a line at constant volume.112 General thermodynamic relationships The definitions of the specific heat capacities are c. it should be noted that T and (av/aT)i are both positive. The circumstances when cp= c. aT (6. which can be evaluated along a line at constant pressure. for all known substances (ap/av). Thus cPcv T (*)(?) aT .64) can be used to define which specific heat capacity is the larger. Hence if the pressure on such a substance were decreased its volume would decrease until it ceased to exist. e. and hence the sign of cP. v . Now.62) can be rearranged to give (%). If both these terms are positive then cpz c. can be seen to be positive. cpac.C . because as the temperature increases. is also positive.. First.g. by considering the terms in eqn (6.c. Thus (6. = T( $) V and cp=T($) P Hence 5c5 = ( ? # I ) (6. must always be positive or zero. is negative. . (av/aT). Thus cp. p .. and vice versa. The term (ap/aT). the pressure increases over the whole of the section. If it were not negative then the substance would be completely unstable because a positive value means that as the pressure is increased the volume increases.
The state equation for an ideal gas is p v = RT Differentiating gives (?E)T= P V (6. and in which the specific heat capacity at constant volume (or pressure) is a function of temperature alone. from eqn (6. = f ( T ) . cp= c. for an ideal gas. the difference of specific heat capacities for an ideal gas is the gas constant R .Relationships between specific heat capacities 113 \ Specific volume Fig. which is depicted by the superheated region in Fig 6. Also 1 and ($)= B v P .67) The definition of an ideal gas is one which obeys the ideal gas equation (eqn (6.26)).66) Thus (6. i.3 p . Hence.67).c .e.65) and (+Jp= 3 (6. 6.3. + R = f ( T ) + R = f ' ( T ) if R is a function of T alone. c.v section of state diagram showing isotherms Now consider cp. Hence.
from the twoproperty rule. T = T( p .. The definitions of cpand c. cp. These parameters are defined in Chapter 7. It is also interesting to examine the r t o of specific heat capacities.o) ap (?E)(”). as aT (6.68) where = coefficient of expansion (isobaric expansivity) k = isothermal compressibility. ) x T a )o ( ) =(n). Expressions for the difference between the specific heat capacities.74) .73) Thus (6.70) =( T . aV aT (”) (6.114 General thermodynamic relationships and thus (6. and thus the r t o of specific heat capacities is ai cp= (as/aT). ) for the differentials. and cP=T($). have been ai derived above.72) Now.71) From the Maxwell relationships aT = aV (6. 69) as giving aT ap as aT av (z)p(G)i%)T =cp CV (6. from the mathematical relationship (eqn ( . are cv = T($). v ) and hence =T ) ! ! ? ( (?E) ..e.69) Now. K = cp/c. (6.
the numerator can be written as l/k. liquid to steam is considered. If the change of phase of water from. then this takes place at constant pressure and constant temperature. Thus (6.77) If there is a mixture of two phases. ($jV = The lefthand side of this equation is the rate of change of entropy with volume at constant temperature. Thus (6. or isentropic. then the pressure is a function of temperature alone. compressibility.75) If the slopes of isentropes in the p . on substituting from eqn (6. known as the saturation values. where k. say steam and water. Hence.19c). (g)T=  (6.4 Isentropic and isothermal lines for a perfect gas 6. (E).is the reciprocal of the isothermal compressibility.5 is considered.5 The ClausiusClapeyron equation From the Maxwell relationships (eqn 6. it can be seen that cp/cv 1 for a gas in the superheat region. becomes (g)v=  (6. = adiabatic. > Volume Fig. ~ ( J p / a v ) .4). By analogy.74). 6.19c).The ClausiusClapeyron equation 115 The denominator of eqn (6. if the change of phase between points 1 and 2 on Fig 6. .76) which. k. as shown in Chapter 7.78) .v plane are compared with the slopes of isotherms (see Fig 6. say..
116 General thermodynamic relationships Now (ah/as).h . Critical paint Fig. Thus (6. (b) Ts diagram . 6. = T ( s . and during a change of phase both T and p are constant. giving h.= T.79) Specific volume Fig. . .SI). .6 Evaporation processes shown on state diagrams: (a) pv diagram. 6 5 Change of phase depicted on a pv diagram .
5. hf /(kJ/kg K ) Temperature Pressure /("C> /(bar) 115 120 125 1. 6.1 THE USE OF THE CLAUSIUSCLAPEYRON EQUATION If an empirical expression is known for the saturation pressure and temperature.80)) ( ~ . Vfg Entropy of liquid.80) This can be depicted graphically.SI) dT 2 Now.s.h. If the processes shown in Figs 6.691 10 sgsf vfg x lo5= 6./T. For example. the change of enthalpy and entropy during the evaporation of water at 120°C can be evaluated from the slope of the saturation line defined as a function of pressure and temperature. sf /(kJ/kg K) Enthalpy of liquid.6. again giving (eqn (6. Now h2 .985 2. then it is possible to calculate the change of entropy and specific volume due to the change in phase.001060 0. showing values on the saturated liquid and vapour lines Specific volume /(m3/kg) Change of specific volume.321 . If the two diagrams depict the same processes on different state diagrams then the areas of the 'cycles' must be equal. the change of entropy is sfg= s2 .6(a) and (b) are reversible.79) can be rewritten as (6. then the areas are equivalent to the work done. eqn (6. If point 1 is on the saturated liquid line and point 2 is on the saturated vapour line then eqn (6. The values of entropy and enthalpy for dry saturated steam can also be evaluated if their values in the liquid state are known.VI) 2 (6.80) is known as the ClausiusClapeyron equation.1.s . Hence dp = ( ~ . is the latent heat.30 x lo3N/m2 K From the ClausiusClapeyron equation..1 Excerpt from steam tables.The Clausius Clapeyron equation 117 This equation is known as the Clapeyron equation. and is shown in Fig 6.8845 1.1. dp vfg  dT .691 1. Table 6. s ~ . = hf.321 0.80).530 505 At 120°C the slope of the saturation line is dp _dT 2.81) Equation (6. hfg. and values of pressure and temperature on the saturation line have been taken at adjacent temperatures. An extract of the properties of water is given in Table 6.
These can be used to evaluate derived properties f o primitive ones and to extend empirical data. while h. for an ideal gas.1 18 General thermodynamic relationships giving S. the value of s = 7.530 + 0. PROBLEMS 1 For a van der Waals’ gas.8845 x 6. stating any assumptions made in arriving at the solution.9 kJ/kg K These values are in good agreement with the tables of properties.30 x 103/103 dT = 1. = h. + Ts. From this find cp. 2 Prove the general thermodynamic relationship and evaluate an expression for the variation of cp with pressure for a van der Waals’ . is given by k= Also evaluate for the van der Waals’ gas.2a(v .57235 = 2694. .2a(v .57235 = 7.b)2 v2(v . = 2707 kJ/kg at a temperature of 120.127 kJ/kgK. is given by B= Rv2(v.b) RTv3.102 kJ/kgK = sf + vfg .c.b)’ and the isothermal compressibility.= The specific enthalpy on the saturated vapour line is h.2”C. k. which obeys the state equation RT p=vb a v2 show that the coefficient of thermal expansion. B.6 Concluding remarks Thermodynamic relationships between properties have been developed which are rm independent of the particular fluid. dP 1.530 + 5. 6. = 505 + (120 + 273) x 5.b)* RTv3.
T (3 dp . of a gas which obeys the Clausius equation of state.525 (m3)' bar OunoD2 . where the suffix 'm' indicates molar quantities and R is the universal gas constant.012695 2952.Problems 119 gas which obeys a law RT a p=2 v. where a = 5. d T .b V.03042 * kmol ' R = 8.1 What is the value of (acP/ap).013914 0.4 then (%).3143 kJ/kmolK Evaluate the change in cpas the pressure of superheated water vapour is increased from 175 bar to 200 bar at a constant temperature of 425°C.011458 0. Compare this with the value you would expect from the steam tables abstracted below: 425 450 0. It is possible to represent the properties of water by such an equation. p = RT/(v. m3 b = 0.9 3109.(%I 4 Showthat 5 Show (a) T d s = c .7 0.015174 3014.=.b)? 3 Show that if the ratio of the specific heats is 1. .9 3060.
Calculate the net heat transfer to the water. 20 bar and occupies a volume of 0. derive the expression for entropy change T and similarly. in m3/kg.)p dp Apply these relationships to a gas obeying van der Waals' equation RT p=vb a v2 and derive an equation for the change of entropy during a process in terms of the basic properties and gas parameters.cv = T( (s)p=($)v+(:)E)p *)(") aT aT Specific volume/(m3/kg) Pressure/(bar) 20 Temperature/("C) 30 50 200 The following table gives values of the specific volume of water. 0. It is heated at constant volume to 50°C and then cooled at constant pressure to 30°C. .dT T . for a pure substance.0009956 0. s = s(T. and from this prove that cp.00101 12 0. p) derive ds=c. Also derive an expression for the change of internal energy as such a gas undergoes a process.0010034 0. for s = s(T. v).2 m3.120 General thermodynamic relationships 6 Show that. A quantity of water is initially at 30"C. ( l.0010034 [438 kT] 7 Assuming that entropy is a continuous function.
while maintaining the pressure constant. perfect gas law). process (ii). 7. First the experimental approach will be considered. or constant composition mixtures. If a fixed mass of a single component fluid is contained in a closed system then two processes can be proposed: the volume of the gas can be changed by varying the pressure.g.7 Equations of State The properties of fluids can be defined in two ways. A number of models which describe the relationships between properties for single component fluids. and is the experiment proposed by Boyle to define Boyle’s law (also known as Mariotte’s law in France). e. will be developed here. The process executed in (i) can be described mathematically as (i) v = v( PIT (7.g. or a simple molecular model. (ii) the volume of the system can be changed by varying the temperature. while maintaining the temperature constant. can be written v = v(T). Both of these approaches have been developed by observation of the behaviour of fluids when they undergo simple processes. The second process is an isobaric one and is the one used to define Charles’ law (also known as GayLussac’s law in France). either by the use of tabulated data (e.1) while the second one.3) . Since these processes can be undergone independently then the relationship between the three properties is (7.1 Ideal gas law The ideal and perfect gas laws can be developed from a number of simple experiments. The first process is an isothermal one. steam tables) or by state equations (e. It has also been possible to model the behaviour of such fluids from ‘molecular’ models. the kinetic theory of gases.g.
or isothermal bulk modulus.constant  T (7. It is possible to evaluate the first derivative by a Boyle’s law experiment. it is found from Charles’ law that V _ . and (av/aT). used for describing the properties of materials.10)is known as the ideal gas law. This equation contains no information about the internal energy of the fluid.then dv = ( $ ) T dp + ( $)p dT (. and does not define the specific heat capacities.4) 7 6 and 7 8 into gives dv = . and this can be derived by knowing that. If the specific heat capacities are not functions of temperature then the gas is said to obey the perfect gas law: if the specific heat capacities are functions of temperature (Le. which states that any property of a single component fluid or constant composition mixture can be defined as a function of two independent properties.) 74 Hence. ) ( . p and T.8) Substituting eqns ( .3) a functional form of the equation ofstare of a single component fluid.. if the property. The actual mathematical relationship has to be found from experiment (or a simulation of the molecular properties of the gas molecules). if the partial derivatives (av/ap). The first is called the isothermal compressibility. can be evaluated then the gas law will be defined. the internal energy and enthalpy do not vary linearly with temperature) then the gas is called an ideal gas. It is found from Boyle’s law that pv =constant (.10) Equation (7.122 Equations of state Equation (7. It is possible to define two coefficients from eqn ( . is a continuous function of the other two properties. ) which are analogous to concepts 74.dT P T which may be integrated to give T = constant (. v.. ) eqn (7. is It can be seen to obey the twoproperty rule.) 75 giving = .P V Similarly. and the second one by a Charles’ law experiment. k. as discussed in Chapter 6. This is defined as the ‘volumetric strain’ .dp +.) 79 (7.7) giving ($)p =r V V V (7.
12) The coefficient of expansion is analogous to the coefficient of thermal expansion of a solid material. This is defined as the ‘volumetric strain’ produced by a change in temperature.4) may be written dv _ .10) can be modified to P= %T vb (7. If a gas is not superheated the molecules are closer together and the assumptions are less valid. . Th~s because when gases are is superheated they obey the kinetic theory of gases in which the following assumptions are made: 0 0 0 molecules are solid spheres. This has led to the development of other models which take into account the interactions between the molecules. and the mean free path between collisions . B.this basically means that the volume occupied by the molecules is not negligible.2 Van der Waals’ equation of state In an attempt to overcome the limitations of the perfect gas equation. there are no forces of attraction between the molecules. if it is assumed that the molecules occupy a significant part of the volume occupied by the gas then eqn (7. 7. First. a number of modifications have been made to it. This is called the Clausius equation o f state.dV .1 1) The negative sign is introduced because an increase in pressure produces a decrease i n volume and hence (av/ap) < 0. while still exerting infinite forces of repulsion on contact. The two most obvious modifications are to assume: e the diameters of the molecules are an appreciable fraction of the mean distances between them. 0 the molecules exert forces of attraction which vary with the distance between them.kdp +. molecules occupy a negligible proportion of the total volume of the gas. The isothermal compressibility of a fluid is analogous to the Young’s modulus of a solid. eqn (7.13) The ideal gas law applies to gases in the superheat phase. giving (7. The other coefficient that can be defined is the coeficient of expansion.Van der Waals’ equation of state 123 (7. Hence. but there are infinite forces of repulsion on contact.14) where b is the volume occupied by the molecules.BdT v v (7. it is more convenient to have a coefficient with a positive value and the negative sign achieves this.
which indicates an inaccuracy in the method).1 1 Specific volume / ( m 3 / k g ) Fig.4. which would be predicted for a perfect gas. It can also be seen from Fig 7. The line at 374°C is the isotherm at the critical temperature.15) is a significant improvement over the perfect gas law as the state of the water approaches the saturated liquid and vapour lines.1 Isotherms on a p .15) Figure 7. At temperatures above the critical temperature the isotherms exhibit monotonic behaviour. It can be seen that eqn (7. it lies just in the twophase region. allowing for the forces of attraction between molecules gives the van der Waals’ equation of state. but exhibit the characteristics of a cubic equation. 400 350 300 e 2 2 v1 c d 250 200 150 100 $ 50 0 . which is written %T p=vb a v2 (7.124 Equations of state Second. This results in a constant pressure (horizontal) line which obeys an equilibrium relationship described in Section 7. This line passes through the critical point.oo 1 .1 shows five isotherms for water calculated using van der Waals’ equation (the derivation of the constants in the eqn (7.15) is described below). It is possible to resolve the problem of the correct pressure to use for an isotherm in the twophase region by considering the Gibbs function.which could never be achieved by a perfect gas law.1 that the behaviour of a substance obeying the van der Waals’ equation of state approaches that of a perfect gas when 0 0 the temperature is above the critical temperature the pressure is low compared with the critical pressure. the isotherms are no longer monotonic. and follows closely the saturated vapour line (in fact. which must remain constant during the evaporation process (see Chapter 1).v diagram calculated using van der Waals’ equation . and by 500°C the isotherm is close to a rectangular hyperbola.o 1 . While this characteristic is not in agreement with empirical experience it does result in the correct form of function in the saturated liquid region . 7. At temperatures below the critical isotherm. At the critical temperature the isotherm exhibits a point of inflection at the critical point.
Hence. v . T ) by the properties at the critical point ( pc. Consider van der Waals’ equation RT p=vb a v2 This can be differentiated to give the two differentials. At temperatures above the critical point the curves are monotonic.21) .17) 2RT (7.18) and at the critical point  RT. T = T/Tc= reduced temperature. It has been Seen from Fig 7. j.) then a l state diagrams based on these reducedproperties will be identical.1 that the critical point is the boundary between two different forms of behaviour of the van der Waals’ equation. 8a TC=27bR’ pc=27b2 a (7. (VcbI2 + 2ao =3 vc 6a vC 4 (7. TR) f (7.= 0.T.of a van der 9 Waals’ gas. 7 3 Law of corresponding states .19) (7.Law of corresponding states 125 Exercise Evaluate the isothermal compressibility. whereas below the critical point they exhibit maxima and minima. k.16) where vR= v / v c= reduced volume. vc. p R= p / p c = reduced pressure. and (a2p/av2). If it is assumed that all substances obey an equation of the form defined by the van der Waals’ equation of state then a l state diagrams will be geometrically similar. giving RT + 2a 6a (7. the critical isotherm has the following characteristics: @p/av>. and coefficient of expansion. This means l that if the diagrams were normalised by dividing the properties defining a particular state l point ( p. Thus there would be a general relationship vR = ( P R .20) 2RTc (vcbI3 giving 0 vC=3b. R To be able to define the general equation that might represent a l substances it is necessary l to evaluate the values at the critical point in relation to the other parameters.
= 0. which is not in the region where the substance performs as a perfect gas.0066684 bar m6/kg 8 x 221. but is reasonable elsewhere.0010567 m3/kg a = 3pCv.0066684 V2 (7. This does not give a very good approximation for the critical isotherm.00317 3 = 0.2 3 x 221.00317 m3/kg.2 x 0.002889 bar m3/ kg K Thus.003172 =0.25) Note that the value for ‘ R ’ in this equation is not the same as the specific gas constant for the substance behaving as a perfect gas. the van der Waals’ equation for water is P= 0.003172 0. It is possible to manipulate the coefficients of van der Waals’ equation to use the correct value of R for the substance involved. Considering eqn (7. This is because it has been evaluated using values of parameters at the critical point. but it does demonstrate some of the important differences between real substances and perfect gases.00317 R= 3 x (374.23) or (7.2 x 0.002889T ( v .1 will now be evaluated.24) is the equation of state for a substance Obeying Van der Waals’ equation: it should be noted that it does not explicitly contain Values of a and b.15 + 273) = 0. but such a solution has not been found for state equations with more than two parameters.22).24) Equation (7.126 Equations of state Hence 2 v (7. The law of corresponding states based on van der Waals’ equation does not give a very accurate prediction of the properties of substances over their whole range.0. p c = 221. The values of the relevant parameters defining the critical point of water are v. the term for vc . It is possible to obtain a similar solution which omits a and b for any twoparameter state equation.0066684barm6/kg2 2 = 0.2 bar. Figure 7.15°C which gives v b=“= 3 0. The parameters used for the calculation of Fig 7. Tc = 374.22) 3 3 Tc The equation of state for a gas obeying the law of corresponding states can be written (7.1 shows the state diagram for water evaluated using parameters in van der Waals’ equation based on the law of corresponding states.0010567)  0.
0016891 m3/kg which results in the following van der Waals’ equation for water: P= (V 0.1 + 273) 18 x 8 x 221. 400 350 300 ld .2 x 10’ 8.27) It can be readily seen that eqn (7.4Pam6/kg2= 0. as will be demonstrated for the isotherms at 200”C.0.017034 V2 (7. where the predictions are compared with those from eqn (7.3143 x 103/18)2x (374.017034 barm6/kg2 b= = 0.25).26) Substituting the values of p c and Tc into these terms.2.27) It is interesting to compare the values calculated using van der Waals’ equation with those in tables.001 . gives a= 27 x (8. and a pressure of 15 bar (see Fig 7.1 + 273)2 64 x 221. and the results are shown in Table 7. using R = %/18.004619T .2 x 10’ = 1703.Law o corresponding states f 127 can be eliminated to give (7. 8 g 2 u l 200 150 Equation 25 c Equation 27 Saturated liquid + vapour lines 100 50 0 .27) does not accurately predict the critical isotherm at low specific volumes.1 1 S p eci f i c volume / (m3/kg) Fig. . However.0. because the value of b is too big.1. 7. 300°C and the critical isotherm at 374°C. These are shown in Fig 7.0016891) . it gives a reasonable prediction of the saturated vapour region.2 Comparison of isotherms calculated by van der Waals’ equation based on eqns (7.o 1 .25) and (7.3).3143 x lo3 x (374. This has been done for the isotherm at 200”C.
' ( ' 1 I .1 Specific volume at 200°C and 15 bar Region Saturated liquid Saturated vapour Specific volume from eqn (7.14 Specific volume from tables/(m3/kg) 0.e ) (v + B ) . 2 PI (I I 2 10 5 0 001 I . However.00 16 0. showing specific volumes at 15 bar .09 Specific volume from eqn (7. and these include 0 the virial equation: (7. The above diagrams and tables show that van der Waals' equation does not give a good overall representation of the behaviour of a gas in the liquid and mixed state regions.128 Equations of state Table 7. it is a great improvement on the perfect.g. liquefaction. gas equation in regions away from superheat.001 157 0. It will be shown later that van der Waals' equation is capable of demonstrating certain characteristics of gases in the twophase region.25)/(m3/kg) 0.27)/ (m 3/kg1 0.o 1 . e. or ideal.1 1 Specific volume / (m3 /kg) Fig. 7 3 Expanded diagram of 200°C isotherms.1324 25 20 h c e 1 m 15 c e.0017 0. There are other more accurate equations for evaluating the properties of substances.7 V V RT A .28) 0 the BeattieBridgeman equation: p = 7 (1 .
It was shown in Chapter 1 that equilibrium was defined by dG I p .32) This value z. and experience indicates that this is the twophase (liquid + vapour) region. 7. a decrease in pressure results in an increase in the specific volume. in the superheat region).4 Isotherms or isobars in the twophase region Equation (7. examination of eqns (7. for a real gas. Since the evaporation must be an equilibrium process then it must obey the conditions of equilibrium.= 0.34) .Isotherms or isobars in the twophase region where A =Ao(i 0 129 . of a substance at the critical point. it can be seen that in the regions from 3 to 1 and from 7 to 5. Since the critical point has been defined as an inversion point then the multivalued region lies below the critical point. 8 (7. or compressibility factor.f). z is not constant. hence these isotherms should be at constant pressure. T L 0. (sometimes denoted p. which has been calculated using eqn (7. because z = 1 for a perfect gas (i.29) the Bertholet equation: RT p=vb a Tv2 (7.) is the compression coefficient.22) shows that z = = . There are tables and graphs which show the variation of z with state point. and this means that in some regions there are three values of volume which satisfy a particular pressure. It is known that pressure and temperature are not independent variables in this region. Now dg=vdpsdT (7. is defined as z=P V RT (7.4. However.30) 0 the Dieterici equation: p" RT alRTv e vb (7.e. z.27) for water at 300°C. This anomaly can be resolved by considering the Gibbs energy of the fluid in the twophase region. the compression coefficient. ( :) e= C vT3 (7.375 . but it is 0. B=Bol. in the region between 5 and 3 an increase in pressure results in an increase in specific volume: this situation is obviously unstable (see also Chapter 6). and these can be used to calculate the properties of real gases. Considering the isotherm shown in Fig 7. and that fluids evaporate at constant temperature in a constant pressure chamber.33) It is obvious that. In general.15) predicts that along an isotherm the pressure is related to the specific volume by a cubic equation.31) Returning to the van der Waals' gas.375 (ideally) at the critical point. pcvc RT.
and is shown in Fig 7. whereas that between 3 and 5 is unstable: this supports the argument introduced earlier based on the variation of pressure and volume.03 Specific volume / (m3/kg) Fig.130 Equations of state and hence along an isotherm the variation of Gibbs function from an initial point. Hence. but then begins to increase again as the fluid passes from 5 to 7. 4 and 6.02 0.005 0. 1 to another point is (7. An isobar at 100 bar is shown in Fig 7.5. 7. and hence point 3 is obviously unstable. Between point 3 and point 5 the Gibbs function decreases.4 will increase between points 2 and 3.4 Variation of pressure and specific volume for water along the 30O0Cisotherm It can be seen from Fig 7. This argument has still not defined the equilibrium line .025 0.5 also shows that the values of Gibbs energy and pressure are all equal at the points 2. 0 0.35) This variation has been calculated for the region between points 1 and 7 in Fig 7.5. which is a line of constant pressure in Fig 7. Figure 7. If that isobar were moved down further until it passed through point 5 then there would be other points of higher stability than point 5 and the system would tend to move to these points. and the substance would attempt to change spontaneously back from 3 to 2. or from 3 to 4.015 0. say. The regions between 1 and 3 and 5 and 7 can be seen to be stable in terms of variation of Gibbs function. state 1 is more stable than the other points.4. Now considering the region between the saturated liquid and saturated vapour lines: the Gibbs function along the ‘isotherm’ shown in Fig 7.the lowest Gibbs function is at state 1.01 0.4 This indicates that the Gibbs function of the liquid and vapour phases can be equal if the two ends of the evaporation process are at equal pressures for an isotherm. In a similar manner the stability of point 5 can be considered.5 that the Gibbs function increases along the isotherm from point 1 to point 3. and it can be seen that it crosses the Gibbs function line at three points .
This is referred to as Marwell’s equal area rule.36) and this means that (7.37) I Region I Region 11 which means that the area of the region between the equilibrium isobar and line 234 (Region I) must be equal to that between the isobar and line 4 . 7. Three points on that line are defined by states 2. using Gibbs energy to define the equilibrium state. The region between the saturated liquid and vapour lines has been analysed. 4 and 6. and enables a general equation of state to be considered for all substances. but this can be defined by ensuring that the Gibbs function remains constant in the twophase region. . The pressure which enables constant Gibbs function to be achieved is such that 5. Van der Waal’s equation has been analysed quite extensively.Problems 200 131 175 1so 3 100 7s 5 so Variation in Gibbs function along isotherm I Fig.5 .6 (Region II ).5 Concluding remarks A number of different equations of state have been introduced which can describe the behaviour of substances over a broader range than the common perfect gas equation. and it has been shown to be capable of defining the behaviour of gases close to the saturated vapour line. and the areas are labelled I and II in Fig 7. The law of corresponding states has been developed.5 Variation of Gibbs function for water along the 300°C isotherm between the liquid and vapour lines.4” vdp =0 (7.4. 7. and this means the equilibrium state must be defined by constant temperature and constant Gibbs function.
132 Equations of state PROBLEMS The Dieterici equation for a pure substance is given by vb Determine (a) the constants a and b in terms of the critical pressure and temperature.= 3. (b) the compressibility factor at the critical condition. ~ difference in specific heats for gases obeying (a) the van der Waals'. Derive an expression for the law of corresponding states for a gas represented by the following expression: RT p=vb a Tv2 .cV. c ~. The difference of specific heats for an ideal gas. Evaluate the . Derive expressions for (&.___ vb V(Vb) + ... c v3 Discuss the physical implication of the results. for substances obeying the following laws: (a) (b) (c) P = RT vb ST vb e(a/%Tv) p=  a Tv2 U RT p = ./dv). and (b) the Dieterici equations of state. (c) the law of corresponding states. Comment on the results for the difference in specific heat for these gases compared with the ideal gas.
. that the specific heat at constant pressure is given by cp= %T d2( a T ) ~ dT2 h P + CP" where cpo the specific heat at unit pressure. If the molar entropy of gas A is equal to that of gas B when both are at pressure p o and the same temperature T. BV. A . and show that b2 ._ vc 3 ( 27 T. and b. v. as a function temperature and the van der Waals' constants. has the equation of state pv=%T(l+ a p ) where a is a function of temperature alone. A certain gas.. show that if the .cPo=%TA 8 How can the equation of state in the form of a relationship between pressure.p ) is given by eAT(2AT)(ppo) c p .) for the van der Waals' gas.u/%T)] 7 The equation of state for a certain gas is where A is constant. Show that Another gas B behaves as an ideal gas. b2= ( b . Show that if the specific heat at constant pressure at some datum pressure p o is cpo then the value of the specific heat at constant pressure at the state ( T .Problems 5 Show for a gas obeying the state equation A. volume and temperature be used to extend limited data on the entropy of a substance. b. ) [ b .= 1. is 6 The virial equation of state is Compare this equation with van der Waals' equation of state and determine the first two virial coefficients. 133 5 pv=(l+a)%T where a is a function of temperature alone. Determine the critical temperature and volume (T.
entropy of .b T pv RT where u and b are constants.gas B exceeds that of gas A by an amount %(p po) a + T  ( :..) 9 A gas has the equation of state . t t h.a . If the gas is compressed reversibly and isothermally at the temperature T' show that the compression will also be adiabatic i f a T' = 2b .134 Equations of state pressure is increased to p with the temperature maintained constant at T .
4 43. P c (bar) 221. (ii) expanding the gas in a reversible manner. so that it does work. Critical point data for common gases and some hydrocarbons are given in Table 8. . 8. If it is desired to liquefy the gas it is necessary to take its state point into the saturated liquidsaturated vapour region. First. experience indicates that ‘heat’ has to be taken out of the gas. Most gases existing in the atmosphere are extremely superheated. A number of common gases can be obtained in liquid form by cooling.1 Liquefaction by cooling . Table 8.method (i) This method is satisfactory if the liquefaction process does not require very low temperatures.e.OC [KI 374 [647] 82 [191] 32 [305] 96 [369] 153 [426] 31 [304] 130 [143] 243 [30] 147 [126] Critical pressure. existing at well above the critical temperature but below the critical pressure.4 49. This can be done by two means: (i) cooling the gas by heat transfer to a cold reservoir.1 depicts qualitatively the state point of oxygen at ambient conditions and shows that it is a superheated gas at this pressure and temperature.6 36. i.1.Liquefaction of Gases If the temperature and pressure of a gas can be brought into the region between the saturated liquid and saturated vapour lines then the gas will become ‘wet’ and this ‘wetness’ will condense giving a liquid.1 Critical temperatures and pressures for common substances Substance Critical temperature T. refrigeration. but are at pressures well below their critical pressures. This can be achieved in a number of ways.5 89 51 13 34 Figure 8.2 46.
If the mass of working fluid entering the throttle is 1 kg then the mass of liquid leaving the throttle is (1 . 8. and the mass of fluid in the system were made up by adding (1 . If this liquid were then withdrawn to a vessel.x . S Fig.2(a) and (b) respectively. (b) temperatureentropy diagram Consider the throttling process in Fig 8.x . which is between 4 and 1. and leaves it at a lower pressure and temperature as a wet vapour. ) kg of gas at . ) kg.2 A simple refrigerator: (a) schematic of plant. S Fig.136 Liquefaction of gases Entropy. b gj Condenser 4 Throttle !k c” k E I d * Evaporator I I IQin Entropy.1 State point of oxygen at ambient temperature and pressure Examples of these are the hydrocarbons butane and propane. A simple refrigerator and the refrigeration cycle are shown in Figs 8. Mixtures of hydrocarbons can also be obtained as liquids and these include liquefied petroleum gas (LPG) and liquefied natural gas (LNG). which can both exist as liquids at room temperature if they are contained at elevated pressures. 8.2. The working fluid enters the throttle at a high pressure in a liquid state.
This arrangement is the refrigeration equivalent of the combined cycle power station.3 Cascade refrigeration cycle In the cascade arrangement the cooling process takes place in two stages: it is referred to as a binary cascade cycle. The use of two plants in cascade enables the working fluid in each section to be optimised for the temperature range encountered. and that in the high temperature cycle. Two plants in cascade are shown in Fig 8. The large temperature difference will also decrease the coefficient of performance of the plant. The working fluids will be different in each cycle. and the energy to form the vapour phase has been obtained from the latent heat of the liquid thus formed: the throttling process is an isenthalpic one. and the Ts diagrams are depicted in Fig 8. The liquefaction has effectively taken place because. 8. 2 I I Entropy. If the working fluid for this cycle was a gas. referred to as a cascade.Liquefaction by cooling . the quality (dryness fraction) of the fluid has been increased. The simple refrigeration system shown in Fig 8. but it is more common to have to use refrigeration plants in series. To achieve a low temperature it is necessary to reduce the evaporator pressure. The cascade plant is also more costeffective because it splits the temperature drop between two working fluids. The substance to be liquefied follows cycle 12341. Q. and the liquid is taken out at state 1’. to achieve reasonable levels of cooling.2 might be used to liquefy substances which boil at close to the ambient temperature.. which it was desired to liquefy.3 (a).method ( i ) 137 state 3 then it would be possible to liquefy that gas.2: the difference between the top and bottom temperatures is related to the difference between the pressures. Consider Fig 8.3(b). and this will increase the specific volume of the working fluid and hence the size of the evaporator. S (b) Fig. and hence energy has been conserved. then the liquid could be withdrawn at state 1’. However. will have a higher boiling point than the substance being . 56785. to the environment it transfers it to another refrigeration cycle which operates at a higher temperature level. in passing through the throttle. instead of transferring its waste energy.
The longer chain hydrocarbons have higher boiling points than the shorter ones.)=I ).4.138 Liquefaction of gases liquefied. The liquefaction of natural gas is achieved by means of a ternary cascade refrigeration cycle. case liquid will also be taken out at state 5’. h .)(I + (8. and the components are shown in Fig 8. The two cycles can also be used to liquefy both of the working fluids. +. In this system a range of hydrocarbons are used to cool each other. The coefficient of performance of the overall plant is less than that of either individual part. and B f l and /?’* are the coefficients of performance of the separate parts of the cascade.1) Fig. 8. and hence the alkanes can be used as the working fluids in the plant. . The overall coefficient of performance of the two plants working in cascade can be evaluated by considering the heat flow through each section and is given by (1 + where B’is the overall coefficient of the combined plant.4 Plant for liquefaction of natural gas .
because by this stage the gas has been converted to dry ice.method ( i ) 139 Another common gas that can be obtained in a nongaseous form is carbon dioxide (CO. and the plant and relevant Ts diagrams are shown in Figs 8. along with the working fluid. This is like a ternary cascade system. which is passed back into the second compressor. but in this case the working fluid passes through all the stages of the plant.5(a) and (b) respectively. It is then passed into a flash tank where it is cooled by transferring heat with liquid already in there. although it was r originally provided as a pressurised liquid. The carbon dioxide gas enters the plant at state ‘a’. referred to as the snow chamber. This is usually supplied nowadays in a solid form called dry ice. 8. where it is compressed to state ‘c’.5 Plant for manufacture of dry ice (solid carbon dioxide) . and passes through the final stage. this again causes some evaporation of the product. The fluid then passes to the first compressor. and the final stage must be at a pressure high enough Fig. Heat is transferred from the carbon dioxide to the final product causing some evaporation: this evaporated product is passed back to the first compressor.Liquefaction by cooling . In the example shown the process has three stages.). Dy ice is obtained by a modification of the refrigeration process.
The liquid that is produced at ‘j’passes through the series of throttles to obtain the refrigeration effect necessary to liquefy the carbon dioxide. but below the critical pressure.140 Liquefaction of gases temperature m ‘. The gas.5(b).2 Liquefaction by expansion . The temperature at state 2 is above the ambient temperature. 8. Dry ice is not in equilibrium with its surroundings. a turbine) whilst expanding adiabatically then the internal energy will be reduced and liquefaction may ensue. T. because its triple point pressure is 5.method (ii) If the gas does work against a device (e.6 can be used to achieve liquefaction of a gas by use of a device taking energy out of the substance by producing work output. If the gas is now expanded isentropically through the device from state 3 down to its original pressure it will condense out as a liquid at state 4. It could only be in a stable state if the ambient temperature were dropped to the equivalent of the saturated temperature for the solid state at a pressure of 1 bar. If the gas is then compressed isentropically to a pressure above the critical pressure it will reach state 2. It should be noted that if the gas was a supercritical vapour at ambient conditions it would be impossible to obtain it in liquid form at atmospheric pressure. Carbon dioxide cannot exist as a liquid at atmospheric pressure. by a suitable arrangement of heat exchangers. and is continually evaporating. . A cycle which includes such an expansion process is shown in Fig 8. for example oxygen. hence it can be either a pressurised liquid or a solid. exists at state 1 when at ambient temperature and pressure: it is in a superheated state. . then there will be available a supply of extremely cold gas or liquid and this can be used.. In the final chamber the liquid is expanded below the triple point pressure. depicted by point ‘h’ in Fig 8. but heat transfer to the surroundings allows the temperature to be reduced to state point 2a. 8.g. the pressure must also be below the critical pressure for condensation to occur.6. to cool the gas further to state point 3.17 bar. the processes defined in Fig 8. and the phase change enters the solidgas region.Hence. S Fig. Entropy. If the liquefaction plant is a continuously operating plant.5 Continued to enable the condensation to occur by heat transfer to a fluid at close to atmospheric temperature.
The JouleThomson effect is the result of relationships between the properties of the gas in question.The JouleThomson eaect 141 In the liquefaction process described above. 8.’ p = l bar 1 Entropy.3 The JouleThomson effect The JouleThomson effect was discovered in the mid19th century when experiments were being undertaken to d e h e the First Law of Thermodynamics. Joule had shown that the specific heat at constant volume was not a function of volume.6 A method for liquefying a gas Fortunately another method of liquefaction is available which overcomes many of the problems described above. 8. Both these machines suffer the problem that the work done in the expansion process is a function of the initial temperature because the temperature drop across the turbine is It can be seen from eqn (8. The . Another major problem that occurs at very low temperatures is that lubrication becomes extremely difficult. 2 . S Fig. and a similar experiment was developed to ascertain the change of enthalpy with pressure. For this reason the turbine is a better alternative than a reciprocating device because it may have air bearings.2) that as T3 becomes very small. which means that the pressure r t o to obtain the ai same temperature drop has to be increased for very low critical temperatures. thus reducing contamination. or gas bearings of the same substance as that being liquefied. This is known as the JouleThomson effect and it can be evaluated analytically. the temperature drop achieved by the expansion gets smaller. the gas may be expanded from state 3 to state4 either by a reciprocating machine or against an expansion turbine.
...........142 Liqwfaction of gases experiment consisted of forcing a gas through a porous plug by means of a pressure drop. at a certain entry temperature there was a temperature drop in the gas after it had passed through the plug........ the enthalpy of the gas was a function of both temperature and pressure. I TI /y I I I I I I I I I I I I I I I I I I I I I I I I I I I I Inversion pressure IPi I I I I ' PI I ...... A suitable apparatus for conducting the experiment is shown in Fig 8... . 8. for these gases... It was found that... This showed that... Isenthalpic z ...I Piston maintaining Piston maintaining C0.7. for some gases..7 Porous plug device for the JouleThomson experiment b g G _Ti_ ...ltrol surface ~~~~~ ~ ~ ~ Porous Plug Fig.....
.5) gives + () $h ( ($). W = rate of work transfer.e. $ thus ABC is an isenthulpic line. V. T . Hence h2= hl . then there can be either heating or cooling. T2. . 'I = 0.. T . This situation can be analysed in the following way. i. If state ( pl.7) . From the Second Law of Thermodynamics dh=T ds+vdp But. Now Q = 0. equal to or less than T.. This term is called the JouleThomson coefficient.8 may be analysed by applying the steady flow energy equation (SFEE)across control volume. If p<O. T). = velocity upstream and downstream of plug. h. The most efficient situation from the viewpoint of obtaining cooling is achieved if p1and T. ) is to the right of B then T2depends on the pressure drop.V2= V. the upstream state point defined by ( p . then ( ds = ( $ ) T dp + ($):T (8. then the gas will be cooled on passing through the plug (i.4) oI($) h +v If it is assumed that entropy is a continuous function of pressure and temperature. h2= enthalpy upstream and downstream of plug. depending on whether the downstream pressure is between A and C. and thus (8. or to the left of C. lit = mass flow rate. V . T . . $)p (8. substituting this expression into eqn (8..If p > 0. the inversion point. ) is at B then the downstream temperature. for this process dh = 0. p.. and it could be greater than. If the upstream state ( p .The JouleThomson effect 143 The process shown in Fig 8.e. and the enthalpy along line ABC is constant. are at B. It is possible to analyse whether heating or cooling will occur by evaluating the sign of the derivative (aT/ap). will always be less than TI. s = s p. when where 0 = rate of heat transfer. ) is to the left of B on the isenthalpic line).6) which can be rearranged to give =( $ ) T Hence.
For example.1 4 4 Liquefaction of gases Now. from eqn (8.=(I T i = 1 B (8. from eqn (8. the JouleThomson coefficient for a perfect gas can be evaluated by evaluating .19d)).24)).14) Hence . and.VI =P (8.12) It is possible to evaluate the JouleThomson coefficient for various gases from their state equations.g)p [. ($).13)..10) becomes (8.10) This can be written in terms of the coefficient of expansion and eqn (8.9) which may be rearranged to give = (2). Thus (8.( p=[BTl] CP V . from the thermodynamic relationships (eqn (6. from the Maxwell relationships (eqn <6.1 1) At the inversion temperature.13) Now and.10) by differentiating the perfect gas equation u pv = RT (8. the derivative (8.
g.083143 T 1.16) and hence.18) (8.19) . it does not mean that gases which obey the ideal gas law at normal atmospheric conditions (e. in general form (8. eqn (8. Van der Waals' equation for air may be written.17) (8. p.3.0364) V ' (8. because they cease to obey this law close to the saturated vapour line. This is what would be expected. as and P' 0. From eqn (8. which can be evaluated in the following way.1 MAXIMUM AND MINIMUM IWERSION TEMPERATURES The general form of van der Waals' equation. This is related to ( a v / a T ) .15).15) To assess whether a van der Waals' gas can be liquefied using the JouleThomson effect it is necessary to evaluate the JouleThomson coefficient. . because the enthalpy of an ideal gas is not a function of pressure.358 bar (m3/ km01)~ 0. nitrogen.15). giving lav\ Thus. However. can be rewritten as The inversion temperature is defined as Ti =E () P + = f 5)(7) (7) vb 2a (p  % (8. oxygen. the JouleThomson coefficient for a van der Waals' gas is not zero at all points. using a and b for air as 1.17). being given by 8. from eqn (8. etc) cannot be liquefied using the JouleThomson effect.358 (V0.0364 m3/kmol respectively. The possibility of liquefying a gas obeying the van der Waals' equation is considered below.The JouleThomson effect 145 This means that it is not possible to cool a perfect gas by the JouleThomson effect.
which can be solved as a .b I / = x = lV (8.20) * v($)p= + $). The values of a and b for air are 1.23) in eqn (8. Substituting these values into eqn (8.27a.(v . b) Critical temperature These equations will now be applied to air.b)Ti= e ( p+ ). and this can be achieved by multiplying q n (8.15).358 bar (m3/kmol)2 and 0. $) (b) (7) (P +  vb) 2a (8.75 T C (8..Minimum inversion temperature = 0.75 Tc Critical temperature Ti .This gives and (v ..16) by v and eqn (8.24) The maximum and minimum inversion temperatures are achieved when the pressure.16) in the following way: ($)p = .b ) ( 3 (8.2a ( v .23) Substituting eqn (8.15) gives (8. is zero.146 Liquefaction of gases which can be evaluated from eqn (8.24).26) Ti .21) and (8.22) Subtracting eqns (8.b)..21) It is now necessary to solve for v in terms of alone. R .0364 m3/kmol respectively. p.= 9Rb  2a Ti 9 (8.25) The value of the critical temperature for a van der Waals' gas is 8a Tc = 27Rb and hence (8.20) by ( v .b)2 R v2 (8.Maximum inversion temperature = 6.22) gives ( + %. and van der Waals' equation for air was given as eqn (8.. This gives 2a pi= Rb and T i = .
This shows that it is not possible to liquefy air if it is above a pressure of about 340 bar.(3x . when x = 2/3.x) .9 K.28) dp = Equation (8. or less than about 100 K..9. The maximum pressure at which inversion can be achieved for hydrogen is 117 bar. This can be related to van der W a s equation in the following way.28) is zero when 3(1.29) Thus the maximum pressure at which a Van der Waals’ gas can be liquefied using the JouleThomson effect is nine times the critical pressure. Le.9 Higher and lower inversion temperatures for air The maximum pressure for which inversion can occur is when dp/dT = 0. 0 e 50 100 w Pressure I (bar) 150 250 M O 39 Fig.The JouleThomon effect 147 quadratic equation in K . for the maximum and minimum inversion temperatures.dx dT dx dT and since dx/dT is a simple single term expression =O dP dT dx dP when . Figure 8. respectively. Similar calculations for hydrogen give 224 K and 24..1) = 0. Hence the maximum pressure at which inversion can occur is 2 (8. 8.6 bar.= 0 dx a {3(1 x) . Substituting for a and b in eqn (8. gives the diagram shown in Fig 8.( 3 x .29) gives the maximum pressure as 341.1)) b2 (8.23): dp dp . . using the expression for x al’ introduced in eqn (8.9 indicates that it is not possible to cool air using the JouleThomson effect if it is at a temperature of greater than 900 K.
 lo l p ~ p . e. and a schematic of the equipment is shown in Fig 8. This approach is embodied in the Linde liquefaction process.38 respectively. Figure 8.e.11(b). The Linde process is similar to a refrigerator operating on a vapour compression cycle (i. hydrogen at atmospheric temperature has a TRvalue of 10.1 1(a) both bring about cooling through the JouleThomson effect. Hence.T h o m s o n cooling cannot occur in this region1 8 01 JouleThomon coeficient negative in 6_ 3 % L ~ _ _ . liquid nitrogen when the value of T could become as low as 4.2. ) and reduced temperature (T. Also shown on that diagram is the saturation line for water plotted in nondimensional form. it will be assumed that the plant is already operating in steady state and that a supply of liquefied gas exists. cooling always occurs. This is then . To the left of the inversion curve. while the thermodynamic processes are depicted in Fig 8. except that it includes a heat exchanger to transfer energy equal to Q A and QB from the high temperature working fluid to that which has already been cooled through throttling processes.g. which is the same as state 1. i.1 shows that for oxygen and nitrogen at atmospheric temperature the values of reduced temperature are 2. approximately 400 and 270 bar respectively. However. To be able to liquefy hydrogen by this method it is R necessary to precool it by using another fluid. = T/T. to the %Le heating or cooling occurs depending on the values of the pressure.10.~ n " 4 B JouleThomson coefficient positive in this region  2 0 0 1 2 3 4 5 6 1 Reduced temperature Fig.10 Inversion region in terms of reduced pressure ( p R= p / p . which is well within the range of inversion temperatures.148 Liquefaction of gases The inversion curve goes through the lines of constant enthalpy at the pow.4 Linde liquefaction plant Many gases are liquefied using the JouleThomson effect.10.10 and 2. The two throttling processes depicted in Fig 8.e. Note the saturation line 8. 8.9 may be drawn in a more general manner by replotting it in terms of the reduced pressure ( pR)and temperature (TR) used in the law of corresponding states.= 0. The gas is supplied to a compressor at state 1 and makeup gas is supplied at state 11. these gases can both be liquefied at pressures up to 8p.). the typical refrigeration cycle). This generalised diagram is shown in Fig 8.~ u l e . The operating processes in the Linde plant will now be described. ( a T / a p ) . For a gas to be cooled using the JouleThomson effect it is necessary that its state lies in the region shown in Fig 8.11(a).. and lies outside the range of the JouleThomson effect. Consideration of Table 8.
Some of the gas entering the receiver is passed back to the . 8 1 Linde liquefaction plant: (a) schematic diagram. The gas finally reaches state 2.Linde liquefaction plant Compressor Electric motor 149 ' I1 Y Makeup gas Throttle '8 6 Y0 Y I 1 10 (a) 56 a E (b) Entropy. and it is then passed through a heat exchanger which cools it to state 3. (b) Ts diagram . At this point it is throttled for the first time. and is cooled by the JouleThomson effect to state 4 and passed into a receiver. supercritical pressure (which might be hundreds of atmospheres) by a multistage reciprocating compressor with interstage cooling.1 compressed to a high. S Fig.
s ) diagram for steam. and the inlet temperature of the hot stream equals the outlet . and it can be seen that the enthalpy of the vapour peaks at a value of about 2800 M/kg. 8. This point of minimum inversion temperature can also be seen on the Mollier ( h . defined by the quality of state point 6 on the T s diagram. and liquid gas can be removed at state 9. 300 bar and the enthalpy were 2700 M/kg then an isenthalpic expansion would result in the gas becoming wetter. It was shown that the quality (dryness fraction) of water vapour could be increased by passing the wet vapour through a throttle. At this stage it is in the liquidvapour region of the state diagram. and the remainder is passed through a second throttle until it achieves state 6. The liquidvapour boundary for water is shown in Fig 8. with the stream leaving the flash chamber. and liquefaction could occur. and is where the saturation curve peaks in enthalpy value. If the pressure were.5 Inversion point on pvTsurface for water The JouleThomson effect for water was met early in the study of thermodynamics. is expanded through a throttle then its quality increases. which has no external heat losses or friction. 8. = 212OC. say. This is equivalent to a pressure of about 20 bar. and compressed isothermally to 200 bar. 2 1500 * % 0 v) 0 2000 h a 8 1000 500 0 & Fig. and the cascade is omitted. and hence this point must be below the minimum inversion temperature.75 x T. This process is an isenthalpic one in which the pressure decreases. with an enthalpy of 2700 M/kg.13. Using the van der Waals' relationship and substituting for the critical temperature gives fi= 0. 3000 9 2500 3. this means that it would not be possible to liquefy the water vapour by the JouleThomson effect.12 Variation of enthalpy on the saturated liquid and vapour lines with pressure for steam Example A simple Linde liquefaction plant is shown in Fig 8.12. This is similar to that in Fig 8.150 Liquefaction of gases compressor via the heat exchanger. The plant is used to liquefy air. The compressed air then transfers heat in a counterflow heat exchanger. which is close to that defining the maximum enthalpy on the saturation line. The yield of liquid gas is y. which is fed to the compressor at 1 bar and 17"C. If water vapour at 20 bar.11 except that the liquefaction takes place in a single process.
and the irreversibilities introduced by the heat exchanger and the throttle. 8. . (example based on Haywood (1980)). evaluate the: (i) (ii) (iii) (iv) (v) yield of liquid air per kg of compressed fluid. S Fig. and taking the dead state conditions for exergy as 1 bar and 290 K.s diagram for liquefaction process temperature of the cold stream. Using the table of properties for air at low temperatures and high pressures (Table 8.13 Simplified Linde gas liquefaction plant: (a) schematic diagram of simplified plant. actual work required per kg of liquid air. rational efficiency of the plant.Inversion point on p vT sudace for water 15 1 Liquid yield 290 K ' I 7 (b) Entropy.2). temperature of the compressed air before the JouleThomson expansion process. minimum work required per kg of liquid air. (b) T .
3 12097 111.21 7116 47.52 4944 29.87 46.00 65.07 10671 78.75 5409 38.75 11133 58.00 10.2 12154 81.92 41.33 16.75 8761 65.63 6786 55.98 6583 45.24 4123 30.84 9074 50.91 2187 21.11 2770 20.1 (T.9 6493 80.02 10581 75.66 81.51 31. s.38 2719 25.69 10491 73.5 108.95 8877 97.53 7243 86.86 3789 28. 1 5 10 20 30 35 37.14 12094 79.3 2428 18.54 6231 50.5 0 917 1537 2506 3381 3884 4758 5942 6249 6284 6127 5760 5433 4758 0.61 11848 80.85 2994 28.74 6048 50.8 131.) 132.21 9464 100.28 8290 94.78 7393 87.65 7509 58.09 60.90 8168 64.09 7691 90.2 8582 95.52 7168 60.8 3111 23.09 11405 65.28 2086 15.51 4779 34.24 24.57 6006 41.09 6795 82.16 8909 68.15 7761 61.7 10925 107.54 6355 54. 1972) Enthalpy (W/kmol) Pressure (am> Temperature T.55 54.6 30 40 50 200 400 h S h S h S h S h S h S h S h S h S h S h S h S h S h S h S h S h S 2343 22.66 6928 58.68 6468 53.93 49.33 9056 71.98 5439 32.16 7842 91.27 11912 82.73 10738 56.79 12212 83.28 11025 64.89 7966 61.77 7309 59.31 8365 67.8 127.87 6390 38. = 28.20 7993 92.93 9427 58.96 754 1 89.17 35.52 8380 63.81 3847 33.19 5597 46.48 2595 24.38 3451 25.39 74.94 7995 65.24 8546 66.2 Properties of air (from Haywood.23 Properties of superheatedair at low temperatures and high pressures h: kJ/kmol s: kJ/kmol K m.14 5976 5 1.34 21 14 20.44 11784 78.08 41.63 12364 112.9 .14 7602 62.44 6858 40.(K) hf Entropy (M/kmol K) Sf h.97 7092 85.98 5915 35.39 Properties of air on the saturated liquid and saturated vapour lines Pressure (atmospheres) Temperature (K) 90 100 110 120 125 130 135 140 145 150 160 170 180 190 200 250 290 300 h S 1 6190 76.7 98.07 4816 4 1.Table 8.44 6664 56.99 4698 40.41 3159 28.42 8718 69.85 6974 55.1 119.69 3405 31.62 9172 99.
TI = 290 K.J/kmol sI = 111.30) Substituting for specific enthalpies in eqn (8.33) and (8.0. = 11025 kJ/kmol S.33) The process from 3 to 4 is isenthalpic.35) h3=h4=X4hg+( 1 . the yield of liquid air per kg of compressed air is 0.H 6 (8. these are the makeup gas. From eqns (8.08862 kg.h5 7  12097 . This is the temperature of the gas at point 3.y ) and hence (8.08862) x 5942 = 54 15 kJ/kmol This value of enthalpy at 200 bar is equivalent to a temperature of 170 K.34) (8.y ) h 6 + y h 5 = ( 1 .30) gives m2(h2 . T2= 290 K . and is a JouleThomson process. thus h4= h3 But (8. p 1= 1 bar.63 kJ/kmolK p .Inversion point on pvT surface for water Solution (i) 153 Yield of liquid per kg of compressed fluid. and the work input to the compressor. at point 2 . the minimum work .34)and (8.x 4 ) h f = ( 1 .~ 4 ) h f =1 y)h6+yh5 ( ( Combining eqns (8.31) (8. (ii) The temperature before the JouleThomson process.36) Hence.34) gives h2 . (8.09 kJ/kmolK Considering the heat exchanger: since it is adiabatic H2 . At point 1.32) Now m6=m2(1 . hl = 12097 k.35) h 4 = x 4 h g +1 . = 64.37) (iii) Minimum work required per kg liquid yield.h3) = m6(h7 .0 = 0.08862 (8.h7 y=h .H3 = H7 . = 200 bar.11025 12097 .h 6 ) (8. h. Hence.13 shows that only three parameters cross the system boundary. Consideration of the control system in Fig 8. the liquid yield.
= (1 . the plant is only 14.lnV1 P1 PI Substituting the values gives P2 200 w = . l n .1% as efficient as it could be if all the energy transfers were reversible.3143 x 290 x ln . giving the work per unit mass of liquid as W".(5776)} x = 2550 kJ/kmol gas This is equivalent to 20. .63 = 20275 kJ/kmol liquid (iv) Work required per liquid yield.91137 [ 20 275 .bS WWl (8.9 = 442kJ/kggas = .=O because point 5 (the liquid point at 1 bar) was chosen as the datum for properties. In.0 = 12097 .701 %== w 4987 . The compression process is an isothermal one..290 x 111.Tosl.S T .bs). the work required to liquefy the gas is w= + I . It is instructive to examine where the irreversibilities occur. = = bl .= 12775kJ/kmolgas PI 1 (8.b3) ~0. b.39) (v) .(b2 .(5776) = 8366 H/kmol gas = This is equivalent to 65.b3= 0.0% of the work required to compress the gas.154 Liquefaction o gases f required to achieve liquefaction of the gas is WWl= Y (bl .p l v l l n .= RT. + ZthroDle .= .12775 28.91137 x (15 518) .40) Hence.38) Y In this case.442 0.08863 = 4987 kJ /kg liquid Rational efliciency. The throttle to achieve liquefaction The irreversibility of the throttle is IhNe b.5% of the work used to compress the gas.[ 7561 .b6) .Y)(b7.1406 (8.0. hence Gmt= hl . v . The rational efficiency of the plant is defined as %et . Hence.(15 518)}. The heat exchanger The irreversibility of the heat exchanger is 1.= 8. and hence the work done is v2 P2 P2 w = p .
and v. PROBLEMS 1 Show that the JouleThomson coefficient. [p = (1  Calculate the pressure for maximum yield at a temperature of 120 K.Problems 155 8. It is possible to analyse such liquefaction plant using equilibrium thermodynamics and suitable equations of state. Determine the maximum and minimum inversion temperatures and the maximum inversion pressure for air.8 bar] . and T is temperature (K). p . The efficiency of liquefaction plant has been calculated and the major influences of irreversibilities in the processes have been illustrated. 4%) bz / . 99.($). is the molar volume (m3/kmol). v. Gases which are liquids at temperatures close to ambient can be liquefied by cooling in a simple refrigeration system.0.0367) = 9tT where p is pressure (bar). which cannot be maintained as a liquid at ambient pressure.TL. Derive the relationship between p . hL for a gas obeying the state equation (p + 7) (v.0.368 2 V. and TI for the maximum yield of liquid at conditions pL. T = temperature (K).2. the JouleThomson effect is employed.0367 1. Carbon dioxide.v) 1 CP Hence or otherwise show that the inversion temperature (Ti) is The equation of state for air may be represented by 9tT P = v. is given by . . 339 bar] 2 The last stage of a liquefaction process is shown in diagrammatic form in Fig P8.=(. = molar volume (m3/kmol).1). is made into dry ice which is not in equilibrium at room temperature and pressure. [896 K.6 Concluding remarks It has been shown that gases can be liquefied in a number of ways.6 K. If it is necessary to achieve extremely low temperatures to bring about liquefaction. 62. where p = pressure (bar).
= [3.. 298. Determine the maximum and minimum inversion temperatures.156 Liquefaction of gases Receiver I k. OST. 29.]1 = Liquefied Y mpas Fig. expressed as a multiple of T. [6T... given that k = .11.041 x lo’ m3K/J.0 kJ/kmol K. and (b) the final temperature of the gas.2 3 The equation of state for a certain gas is RT k v.O kJ m3/(km01)~ cp.. Show that the variation of temperature with pressure for an isenthalpic process from 1 to 2 is given by If the initial and final pressures are 50 bar and 2 bar respectively and the initial temperature is 300 K.9.75TCT 2+ 9T: T ) + Bp’T where A and B are positive constants and T. calculate (a) the value of the JouleThomson coefficient at the initial state..] . = + P RT where k is a constant. PS. is the critical temperature.5 K] 4 A gas has the equation of state V m P RT  1 + A p ( T 3 .
show that Q = T:/9p0 and give possible expressions for N and M. = 4 4 p0..e.13) air is taken in at the ambient conditions of 1 bar and 300 K.76%.84%] . 6 In a simple Linde gas liquefaction plant (see Fig 8. There is zero temperature difference at the warm end of the regenerative heat exchanger (i.39 MJ/kg. T. = T. po and Q are constants.To). and if the maximum inversion temperature is five times the minimum inversion temperature. 8. Show that the equation of the inversion curve is P= dNldM dT dT If the inversion curve is parabolic and of the form (T .P ) where To. Heat leakages into the plant and pressure drops in the heat exchanger and piping can be neglected.). and the rational efficiency of the liquefaction process. 8. the work input per kilogram if air is liquefied. [7.1 +Np+Mp2 pvm RT where N and M are functions of temperature. i Calculate the yield of liquid ar per unit mass of air compressed. The waterjacketed compressor delivers the air at 200 bar and 300 K and has an isothermal efficiency of 70%.Problems 157 5 A gas has the equation of state . Saturated liquid air is delivered at a pressure of 1 bar.
2) where n = amount of substance.Thermodynamic Properties of Ideal Gases and Ideal Gas Mixtures of Constant Corn position It has been shown that it is necessary to use quite sophisticated equations of state to define n the properties of vapours which are close the saturated vapour line. is pV=mRT (. The datum for molecular weights . when p V = n9lT (9. and their molecular weights are not integers.1 Molecular weights n e molecular weight (or relative molecular mass) of a substance is the mass of its is carbn12. for gases i the superheat region. To be able to perform combustion calculations it is necessary to know the atomic or molecular molecules relative to that of other molecules. in terms of mass. and this is given a molecular weight of 12. the ideal gas equation gives sufficient accuracy for most purposes. To be able to work in a molar basis it is necessary to know the molecular weights (or relative molecular masses) of the elements and compounds involved in a reaction. or chemical amount m o l ) 9l = universal gas constant (H/kmol K) It is found that eqn (9. However.1) for combustion calculations because the combustion process takes place on a molar basis.2) is more useful than eqn (9. All other elements and compounds have molecular weights relative to this. 9. The equation of state for an ideal gas.) 91 (N/m2) where p = pressure v = volume (m3> m = mass (kg) R = specific gas constant (kJ/kg K) T = absolute (or thermodynamic) temperature (K) This can be written in more general terms using the amount of substance.
The composition of air is defined as 21% 0.I AIR As stated previously.2% 0.1 gives the data for individual elements or compounds in integral numbers (except air which is a mixture of gases).97 28 12 9. by volume (this can be written 21 mol% 0. 32 28 N.O 18 C m.2 State equation for ideal gases The equation of state for an ideal gas. by mass.1 Molecular weights of elements and compounds commonly encountered i combustion n  Atmospheric Air 0. Table 9. most combustion takes place between a hydrocarbon fuel and air. this evaporation can usually be neglected. This is because ‘atmospheric nitrogen’ is taken to be a mixture of nitrogen and about 1.).1. and 76. If the volume occupied by that this amount of substance is denoted v. these can be combined to give other compounds. Air is a mixture of gases. the molecular weight of atmospheric nitrogen includes the effect of the other substances. N.State equationfor ideal gases 159 weights of commonly encountered elements. the most abundant being oxygen and nitrogen with small proportions of other gases. and has the units of m3/mol or m3/kmol. but most values are very close to integral ones and will be quoted as such. and 79% N. In fact.8% by mass of argon. carbon dioxide and other gases.3) If the mass of gas.1 shows that the molecular weight of atmospheric nitrogen is higher than that of pure nitrogen. then where v. . 28. is the molar specific volume. and 79 mol% N. This is equivalent to 23. Now Avogadro’s hypothesis states that equal volumes of all ideal gases at a particular temperature and pressure contain the same number of molecules (and hence the same amount of substance). Table 9. 44 H. achieves its saturated vapour pressure. In reality. 9.17 H2 2 CO CO. except in the case of water. is p V = mJoT (9. then the amount of substance a is known as a mol (if the mass is in kg then the amount of substance is called a kmol).8% N. a . made equal to the molecular weight of the gas in the appropriate is units. 28. or molecules. air is a mixture of all elements and compounds because everything will evaporate in air until the partial pressure of its atoms. Table 9. ma. in reality only carbon12 (used as the basis for atomic/molecular weights) has an integral value. in practice.
m = 3 (9. of gas a . various units in 8314 J/kmol K 1. v. u. for ideal and perfect gases Cp.2.then. v.g.e. and cp. and these will be considered here. u...mWoR.6) It can be seen that for ideal gases the product m.. and the latter will be denoted by lower case letters and a suffix m (e. b.2. at the same pressure and temperature will occupy the same volume as gas a . together with its various units are shown in Table 9.985 CHU/lbmol R 2782 ft lb.. = n. then eqn (9. The molar properties are more useful for combustion calculations. g . i. It has been shown that the internal energy and enthalpy of an ideal gas are not functions of the volume or pressure.5) may be written pV. and hence these properties are simply functions of temperature alone.g.. if c. . and cp in molar quantities are denoted by cv. This means that the specific heats at constant volume and constant pressure are not partid derivatives of temperature. etc).1 IDEAL GAS EQUATION The evaluation of the properties of an ideal gas will now be considered.. If a system contains an amount of substance n. Table 9.8) It is possible to evaluate the properties of substances in terms of unit mass (specific properties) or unit amount of substance (molar properties).cv.. '%. 3.m .160 Thermodynamic properties of ideal gases and ideal gas mixtures Hence.985 kcal/kmol K 1.. h. any other gas. Ri is the same for all gases: it is called the universal gas constant. The values of the universal gas constant. 3. g.2 Values of the universal gas constant. h./lbmol R 9. but can be written Also. The former will be denoted by lower case letters (e. etc).985 Btu/lbmol K 1./lbmol K 1545 ft lb.%T (9.T = n.
+%T (9.... are the values of molar internal energy.AND h0. and h0. will be denoted (9.. (9.9) where uO. uO. at T = 0. b.10) Hence. i.e.. The two commonest approaches are described below. giving (9. Enthalpy or internal energy data are generally presented in tabular or graphical form. u... = %T. + pv. and h. can be easily obtained. u and h.14) .=% then an expression for cp. are the values of u. This problem is not a major one if the composition of the gas remains the same. Hence it is possible to find the values of internal energy and enthalpy at any temperature if the values at To can be evaluated..e... thus h. In some regions it is necessary to use quantum mechanics to evaluate the data. As previously discussed.) To be able to evaluate the internal energy or enthalpy of an ideal gas using eqn (9. if the composition varies during the process it is necessary to know the individual datum values. but this is beyond the scope of this course. u. Now.. it is useful to consider further the terms involved. (A similar relationship exists for the specific properties.. because the datum levels will cancel out.2.. and for an ideal gas pv.. It will be assumed here that the values of cvare known in the form cV.=u. if such data is available. c and d have been evaluated from experimental data. at the reference temperature.13) assuming that the base temperature is absolute zero. and molar enthalpy... If To= 0 then.cV. To. However. First. Since cp.. i.State equationfor ideal gases 161 The molar internal energy and molar enthalpy can be evaluated by integrating eqns (9. and h0. 9. for an ideal gas. u0.= ho. at the datum temperature To.10) it is necessary to know the variation of specific heat with temperature. that which is a function of temperature.. = U.1 1) where a .12) (9. = h.2 THE SIGNIFICANCE OF uO. by definition h. h.7). They can be measured by calorimetric or spectrographic techniques.. It is possible to derive such a function from empirical data by curvefitting techniques. = a + bT + cT2 + dT3 (9. The ‘thermal’ part of the internal energy and enthalpy.
Most calculations involve changes in enthalpy f are or mtemal energy. and ho.162 Thermodynamic properties o ideal gases and ideal gas mixtures f ! To# 0. It was previously shown that (9. It can be shown by the Debye theory and experiment that the specific heat of a solid is given by the law cp= aT3..16) where so. or a value outside the superheat region for the gas being considered. are consequences of the ideal gas assumption and the equation h = hm(T)+ h0. the different species at the reference temperature. (9. but still it is possible to evaluate jdh. m will cancel. giving = h. often becoming either liquid or solid..2.18) To integrate from absolute zero to T it is necessary to include the latent heats. and if the composition during a process is invariant the values of ho. However./T.17) Consider T0 lim ($) If cp.(T0)3 0 then the expression is either infinite or indeterminate.. is the value of s at Toand po.. This will not be dealt with here. 9.(T) is known then eqn (9. Obviously u0. then uO. This is discussed below. If To=O.15) may be evaluated. It is convenient to take the reference temperature To as absolute zero.THIRD LAW OF THERMODYNAMICS The change in entropy during a process is defined as (9.. However. or u 0 .. To allow for this it is necessary to include latent heats..15) If the functional relationship h. before reaching absolute zero the substance will cease to be an ideal gas and will become a solid. . then the gas ceases to be ideal. if the composition changes during a process it is necessary to know the for difference between the values of u0. but the published data do include these corrections. .m m contains the assumption that the ideal gas law applies down to To. and h0...m different.3 ENTROPY OF AN IDEAL GAS .Hence lim T+O (4") ( =T ~ lim = o p (UT2dT)+O z (9.
.) + (h(T) . 9.= h.26) If the terms at To are combined to give ~ .25) (9. By definition. in eqn (9.. It should also be noted that the pressure term. = s. If the composition varies then it is necessary to know.3 In p r + so. and g = h(T) + h..m =h grn(T)= h m ( T ) . PIPo.3 In p r + so) = (h.T s ( T ) )+ 3 T In p . If the composition is invariant then the value of so..4 THE GIBBS ENERGY (FUNCTION) OF AN IDEAL GAS The Gibbs energy will now be derived for use later when considering the equilibrium composition of mixtures (dissociation). and (9. m Ts0.20) is the partial pressure of the gas if it is contained in a mixture. p r = p / p o . It is not possible to obtain any information about so from classical (macroscopic) thermodynamics but statistical thermodynamics shows that 'for an isothermal process involving only phases in internal equilibrium the change in entropy approaches zero at absolute zero'. at least.State equation for ideal gases 163 If s. i. will cancel out when evaluating changes in s and it is not necessary to know its value..2.T(s(T) . the difference between so values for the substances involved...m and the temperaturedependentterms are combined to give g0.(T) is defined as (9.Ts..then s.20) The term so. g. . is the constant of integration and this can be compared with u0.22) (9.21) (9.e. are zero.. (9.. This means that for substances that exist in crystalline or liquid form at low temperatures it is possible to evaluate entropy changes by assuming that differences in so.m If the pressure ratio. p .Ts. and po is a datum pressure (often chosen as 1 bar or.and ha.23) h m = hm(T) + h0. in the past. 1 atmosphere).TSm(T) then .24) (9.19) then entropy (9..(T) . is denoted by the symbol p r .
The number of terms can vary depending on the required accuracy and the temperature range to be covered.71243 O.3.51427e4 1 . and it is a function of temperature alone.oo00 O.oo00 O. = a. and so. based on Benson (1977).74292 8.6930~4 1.34435 O. g i = g.oo00 .58393 3. for the range 500 to 3000 K. If the composition is invariant. is usually chosen as 1 bar nowadays (although much data are published based on a datum pressure of 1 a m .44392e11 2.7697Oe4 1.26) that if the reference temperature.8180% 1 1 1.1. e.5861le15 O.oo00 5.e. It can be seen from eqn (9.1.3 Enthalpy coefficients for selected gases found in combustion processes (based on W / kmol.164 Thermodynamic properties of ideal gases and ideal gas mixtures Often g.62497e10 8.5747Oe12 4.1.29) 9. the difference is not usually significant in engineering problems.84470 O.9426Oe4 9.28) g: is the value of the molar Gibbs energy at a temperature T and a pressure o f p .58800~9 2. and then gm= g: + 9tT Pr (9. For mixtures of varying composition go must be known.317000 4.99147~~4 3.75863 3.equals zero then g 0 ..43328 3.30) The values of the coefficients for various gases are listed in Table 9.49524e7 6.1. with the temperature i K ) n Substance as a1 a 4 a 3 a2 a6 h. internal energy.oo00 O. changes in Gibbs energy are easily calculated because the go terms cancel. i. m = h0.15300 6. but it is possible to convert some of the data..63284 .50174 6.13882e5 3. kJ/kmOl .18100L6 3.25304 9.6699Oe8 8.96462e3 2.. If used outside these ranges the accuracy of the calculation will diminish.9938Oe4 7.oo00 O.@187e7 3.93405e5 3.3 Tables of u ( T )and h ( T )against T These tables are based on polynomial equations defining the enthalpy of the gas.1. This section will limit the number of coefficients to six. Table 9. .09590 5. enwopy and Gibbs energy can be evaluated as follows.76403 Hence the enthalpy.oo00 O.95300L9 2..24402e6 4.46923e5 2. p o .53897e11 .65590S4 .oo00 9.5235Oe4 4.m (9.731 14e3 . are combined to give g i which is the pressureindependent portion of the Gibbs energy.93529 3. equilibrium constants).88542e7 2.11346 8.g.1945Oe12 6. The equation used is of the form (9.3867Oe1 1 O. The datum pressure..9036Oe12 8.oo00 O.oo00 3.2208Oe8 3.6514Oe1 2.oo00 3.66002e11 1. To.m = U0. h.1.39082e5 3.(T) + go.(T) and go. .95240~8 5. Gibbs energy presents the same difficulty when dealing with mixtures of varying composition as u.73309 2.
%T (9.15) as Integrating eqn (9. The chemical potential will be defined in Section 12.2. The first is that and this results in l ( ) when T = To.33) where. for To= 0 K p: = chemical potential = g. At this stage it is sufficient to note that the chemical potential has the same numerical value as the specific Gibbs energy.Tables of u( T ) and h( T ) against T Enthalpy h..m m (Note: the term &.%T = h(T) .28). which was introduced in eqn (9.1 ) + a2T + a.15) gives Equation (9.T3 + a4T4+ a 5 T S ) + = %T(a..T2 + a4T3+ a5T4) = % ( ( a .l ) T + a2T2+ a. where dissociation is introduced.(T) + go.31) Internal energy u J T ) = % T ( ( a . =% 1aiTi i= 1 c (9.m = gm(T) + h0. Fortunately these problems can be overcome by use n0 of the Van't Hoff equation. This states that (9.T + a2T2 a.34) and h = hm(T) + h0. which will be derived in Chapter 12.T5) 5 =% i= 1 aiTi .T3 + a4T4+ a.T4) = %(a.32) Entropy This is defined by eqn (9. is similar to g:.20) provides some problems in solution.m (9.) .(T) 165 + a2T + a3T2+ a4T3+ a.
42) Gibbs energy The Gibbs energy can be evaluated from eqn (9.34). This enables most combustion problems to be solved using this data.42) are given in Tables 9. Other commonly used tables are those of JANAF (1971).37) a3T2 a4T3 a5T4 In T + a.+ q T + q T 2+ 4 T 3 T (9.166 Thermodynamic properties o ideal gases and ideal gas mixtures f By definition.36) Substitutingeqns (9.a6 and then (9.31). hydrogen. but the error is not significant. in eqn (9.41) giving h T + h 2 T + .35) giving =kdT) RT a' +a.3. nitric oxide and methane. (9.39) 3 The value of entropy can then be obtained from 4 (9. . carbon monoxide.36) into eqn (9.38) It is conventional to let A = a. slightly beyond the range stated in relation to Table 9. The tables have been evaluated up to 3500 k.40) (9.m RT2 which can be integrated to ) (9. nitrogen.%T2 + . water. . carbon dioxide.40) or eqn (9.2 3 4 RT gm(T)+ h0.T+ + + .T3 + 2 3 3 4 4 (9. (9.26): The values obtained from this approach.33) and rearranging gives gm(T)+ h0.31) to (9.13) and (9.a.m 9lT (9. using eqns (9.4 for oxygen.
5 442689.68 19553..84 87089.36 256.06 204.1 389752.5 164114.9 52477.75 254.07 70085.81 203.25 62138.34 14513.97 19500.95 80800.36 65997.52 81810.8 I64166.25 57222.04 800 850 900 950 300 350 400 450 500 550 600 650 700 750 lo00 I050 1100 I150 I200 1250 1300 1350 1400 1450 I500 1550 1 00 6 1650 1700 1750 1800 1850 1900 1950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 8569.6 78488.26 89034.4 567204.47 75548.5 833827.1 236642.12 26983.7 279637.42 233.1 554220.98 221.2 48408.31 179.59 226.70 u(r.23 20655.77 258.31 260.51 213.56 41177.46  48833.35 33095.99 24524.9 451766. 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 8561.61 270.65 94896.85 241.57 64778.76 51062.12 83389.08 59282.8 80361 1.83 60231.19 27048.14 239.87 271.2 13174.16 13697.40 41038.89 10574.3 212125.70 5003.6 274009.95 127005.I I 250.2 537201.02 274.5 402668.16 20694.94 272.74 73995.16 77432.19 23796.68 4174.0 299283.60 73600.23 13161.89 251.24 114769.21 82226.30 52906.78 11748.23 5025.80 98828.78 27913.38 87887.85 91380.0 494421.46 277.26 58479.57 55725.oo00 kJ/kmol .5 890264.25 220.60 192.8 199995.96 64109.43 102779. 0 : ho = O.32 206.43 u(n 980. 1365.Table 9.77 23115..19 83648.94 224.61 92999. .8 1 75307.01 278.81 248.63 32540.92 33488.26 43558.6 73828.25 108831.0 606010.62 97905.3 T 50 100 150 200 250 298 300 350 400 450 500 550 40 1396.14 39603.06 . 4326.05 112756.95 31918.1I 100801.66 43895.I7 229.7 469460.26 119784.0 291575.8 820217.65 fir.41 83212.67 282.18 90983.44 84974.6 846800.24 278.72 286.74 2757.01 222.24 280.85 61062.1 528366.80 120852.4 752571.32 57498. Molecular nitrogen.67 254.12 184.2 760706.93 90684.77 21899.88 38478.46 290.65 8187.37 283.2 153015.05 16031.90 252.99 251.3 464427.3 364426.73 48722.60 53615.7 523564.93 14835.90 104763.49 36804.00 50809.8 477132.76 72447.2 197957.59 31152.92 57860.4 140798.9 32n48.2 1 17902.36 30630.7 739126.38 249.9 564602.71 69366.05 214.86 237.77 3953.77 226.88 243.96 52208.9 23515.39 228.04 33936.11 6075.67 122895.9 261478.66 276.2 675792.33 55025.1 42775.18 235.82 218.86 6025.63 34520.7 817977.97 10031.76 270.61 269.95 110669.72 268.95 259.74 267.34 71906.32 195.89 199. Str.0 255951.9 401570.73 266.1 592168.97 18316.4 32962. 250.03 28593.7 337692.5 703959. N : ho = O.14 89768.51 228.62 20430.46 262.5 578365.84 275.5 315632.1 389139.85 209.99 245.79 253.91 239.39 212.55 259.65 45384.31 273.15 260.00 79354.11 33214.06 75563.51 9419.06 246.07 285.76 234.43 12940.6 176011 4 .11 255.9 dl4050.1 832373.38 240.43 40161. T 50 100 150 200 250 298 Yr.07 77105.4 131119.30 17928.56 7081.85 199.4 88735.72 86566.32 261.6 416116.50 209.37 56615.22 16031.86 238.03 18316.1 350619.85 37158.58 241.9 352147.18 11458.10 89288.84 173. .07 4225.93 16321.45 35141.09 7104.36 29774.28 36754.0 249021.76 31355.2 447768.2 426576.I I 247.51 280.39 35341.8 633811.70 265.04 26827.68 78668.3 58515.51 63570.60 217.25 34846.4 580225.17 274.33 14731.42 51262.6 363606.32 118817.43 8503.0 21470.2 600 650 700 750  800 850 900 950 loo0 1050 I100 1150 1200 1250 I300 1350 I400 1450 1500 I550 1700 1600 1650 1750 1800 1850 1900   1950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 .18 23041.18 12572.90 116790.2 712324.74 284.84 38383.9 339920.40 28406.31 67890.85 289.41 47397.36 62854.71 22851.02 108748.9 186590.47 41961.8 789277.06 30214.26 I 17873.57 263.6 509970.3I 191.7 718095.23 25701.43 201.75 85M.5 439148.82 3996.41 285.18 246.49 114332.05 110749.8 63248.4 120335. 1 87955.13 249.89 85148.25 2927.2 99133.0 515497.02 268.81 77398.36 46991.98 60709.28 54757.1 774975.65 52886.2 152426.28 35834.68 269.2 550880.9 861258.70 1973.40 59276.76 231. 779547.18 6032.18 21729.61 69789.41 2805.30 86479.54 236.5 746469.72 25580.8 806633.39 21 194.24 288.36 6067.32 68269.27 159.71 243.90 10356.00 191.71 235.55 2621 1. 220932.47 25384.13 45270.70 58724.74 9265.41 271.19 49784.29 82924.55 61742.5 489879.39 45265.39 85066.78 42480.4 619891.98 257.4 109670.2 303574. 153.53 271.32 270.55 29353.79 73733.34 252.06 283.04 52209.89 56610.5 106652.8 950.76 48024.64 10079.06 290.52 40167. 1 19144.03 1926.05 24365.74 19102.0 402907.05 29627.44 81281.12 dn 4617.01 50460.44 70904.47 21899.05 17560.6 312022.20 88164.70 16616.05 260.17 228.40 66458.43 256.90 24342.99 287.6 142015.52 255.30 81079.96 5659.92 36609.3 267761.72 117973.26 84771.99 75514.51 7650462 77938.66 11513.6 482918.3 661762.50 48312.30 42532.52 216. .32 62226.99 231.5 30251.5 732265.01 49225.68 7121.95 43929.19 46641.54 105 145.68 79237.51 67832.36 6500440 6644022 6787740 6931552 70754 1 3 7219281 73631 09 75068.41 22220.64 64653.75 242.8 376758.65 264.0 95547.83 86621 58 88473 12 9032601 9217984 94034 17 9588856 97742 56 9959570 10144752 103297.13 248.oo00 k J h o l .08 38489.43 80236.74 39829.22 43764.72 28085.07 1 1458.42 268.7 393%.09 71692.5 I 209406.40 15984.4 48450.5 489858.35 96859.43 272.56 223.18 256.64 96261.7 875746.58 46845.26 124945.35 7169.92 79370.81 63258.92 5616. I 685644.47 17145.5 .70 106753.29 232.4 129287.10 14149.80 66303.78 54232.31 38175.5 429377.07 31845.4 244208.76 94626.79 171.19 269.5 286612.64 2978.34 45576.3 14553.3 224342.80 49414.2 84601.78 261 50 26221 26290 26358 26425 26490 265 55 266 18 26681 267.77 279.48 245.62 92937.96 281.87 55727.28 106990. I 793076.40 11610.46 13007.01 52744.87 112503.2 324825.77 Stn 140.36 286.71 257.0 541274.4 698969.8 232534.67 60350.40 8284.62 288.8 725710.4 I 766045.55 186.5 376651.3 5932825 6063753 6195030 6326650 6458608 6590897 67235I .95 41855.4 Molecular oxygen.33 53963.3 456050.09 15374.28 116155.
6 267431.65 9519.25 1%3.4 437753.07 214.7 158168.9 451267.32 154569.63 7100.56 266.58 95298.07 330.54 108521.1 148398.3 396526.17 53751.48 dn 6541.75 119705.42 233.16 304.2 123693.7 99765.54 41358.6 226477.21 324.3 975977.3 239998.70 64292.84 34952.34 276.37 53671194 56205 70 58748 84 61306.19 3103.91 299.38 148954.95 25859.62 229.36 101381.97 2794.0 313109.95 242.46 13528.62 249 77 25089 251 98 25303 254 07 255.~.72 43948.57 283.0 54273.7 533260.6 44150.5 288487.54 34297 30 .5 492251.92 76877.8 441346.9 54702.34 243.04 13615.38 144256.9 300768.95 127154.0 186749.19 6005.02 288.3 45569.8 25365I .0 200 250 298 300 350 400 450 500 550 600 650 700 750 800 850  900 950 lo00 1050 1100 1150 I200 1250 1300 1350 1400 1450 1500 1550 1600 1650 I700 1750 I800 1850 1900 I950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 ~ .52 42223.7 664815.72 27567.14 33625.52 240.68 177.8325511.2 14977.5 169598.Table 9.68 35421.08 163180.93 30999.41 32308.2 874 I 1 1.10 319.09 271.17 2%.87 236.54 313. I 659931.3 240026.44 248.11 138099.55 169194.56 11520.17 74261.14 135027.22 22112. I6 25532.38 316. 3350 3400 3450 3500 .14 15613.75 318.5 192738. 36617.0 94 1824.4 309488.0 705655.27 8610.68 244.47 104429.76 137950.18 234.9 733041.53 269.94 329.77 77180.9 580248.89 48118.55 135235.39 140677.3 252038.3 338089.68 65318.32 247.26 22296.83 2 1248.07 256.33 86203.53 90020.48 238.08 147342.80 182007.92 46215.39 17307.36 132532.29 166036.0 958876.8 5 17759.70 19186464 195209. CO :ho= 1 13 882.82 306.6 452492.47 124477.7 491523.83 111172.5 924821.26 39912.99 264.12 4261 1.2 199847.25 83186.17 98336.1 426697.33 15428.65 261.64 116482.48 84752. 971 01 195750 295924 397604 500769 601184 605397 711467 818957 927844 1038106 1149721 1262666 1376917 1492451 16092.05 4342.6 413870.24 36287 06 3763000 3898079 40339 13 41704 73 43077 29 44456 53 45842 12 47233 79 48631 21 50034 07 51442 08 52854 90 54272 23 55693 74 571 19 12 58548 03 59980 I5 61415.62 4350.27 50920.28 332.96 68261 44 71220 29 74193.45 19248.97 246.42 320.47 17772.96 51170.74 160282.O 890964.56 227.6 741180.11 19669.8 760548.64 188550.36 263.9 504620.7 719332.23 247.66 92258.95 162893.08 7041.09 250.02 71653.93 143420.7 323735.63 59490.62 230.82 207.72 18465.4 788173 3 402028.57 340.4 708502.29 9594.5 767 18.42 175560.81 268.53 342.3 774087.33 267.19 5676.76 274.19 331.55 337.15 62852.58 47423.19 79498. 45347.46 10202.66 69052.59 178772.98 29699.28 150434.% 29540.44 308.44 17272.21 292.95 ~~ ~~ 4n 927.5 611923.33 260.1 1 11626.02 146178.72 27129.98 315.42 325.48 121807.02 159762.6 337971 6 350488 3 3630600 3756853 388363.9 276271.7 24196.4 692010.2 502304.8 790624 7 8072 16.71 301.37 2541 1.1 173804.3 228087.0 907867.24 26993 27062 271 29 27195 272 59 273 23 273 86 27447 27507 27567 276 25 276 82 27739 27794 278 49 27902 27955 ~~ 100 I50 200 250 298 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 I I50 1200 1250 1300 1350 I400 1450 1500 1550 1600 1650 1700 1750 I800 1850 1900 I950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 B0 ( 59492 138256 224390 315363 409973 503560 50751 I 607508 709632 81363 2 919315 1026525 1135136 124504 I 1356150 146838.31 141175.42 11872.07 297.76 48681.83 279.78 29769.83 286.70 321.72 43773.05 7754.08 267.85 40508.31 199.1 456461.52 336.9 .85 107480.64 95295.96 258.4 993127.74 32080.87 131958.4 continued Carbon monoxide.44 1010324. T M n 50 138673 278893 420639 563890 708627 848951 854826 1002468 1151529 1301987 1453821 1607008 1761524 1917347 2074452 22328.36 20885.38 66159.60 63877.2 557417.06 257.48 20001.67 254.4 478396.83 151751.12 27068.0 823861.15 290.7 544158.22 68621 55 7006671 71512 36 72958 I5 74403 71 7584868 77292 72 7873545 8017651 8161553 83052 I3 84485 95 8591660 8734371 88766 88 90185 75 9159991 s(n 14672 166 I5 17764 I85 88 19233 19747 19766 20222 20620 20974 21294 21586 21855 221 04 22337 225.3 530938.02 309.3 2 16224.87 87385.62 326.1 439571.46 303.08 239.57 23 1.00 82123.79 33745.0 401091.32 269.5 724812.4 264120.30 166109.45 263.8 16lO18.77 260.95 23304.55 341.97 323.9 757606.69 49174 22 50932 88 5269938 5447344 56254 75 58043 03 59837 98 61639 29 63446 67 65259 81 67078 39 68902 I I 70730 65 72563 69 74400 92 76242 01 78086 64 79934 47 81785 19 83638 45 85493 91 87351 25 89210 I I 91070 16 92931 04 94792 40 9665390 98515 I8 100375 87 102235 62 10409407 10595084 10780557 109657 89 I I I507 42 11335379 1151%61 I17035 50 I1887008 12069996 NT.23 28783.0 627861.26 80178.8 204440.0 676060.44 266.37 333.21 97939.51 343. 344.51 262.17 23924.16 34634.0 281332.I 426316.18 263.60 .87 38972.10 185265.57 100582.9 857309.45 65734.0 570714.9 295353.39 113825.26 225.43 334.57 339.46 122765.03 239.9 478469.07 312.4 4 11376.22 294.7 471661.I 424274.09 32063.72 190.32 243.5 88123.77 24599. I6 45681.32 220.4 486943.62 214.53 235.79 125827.8 352549.26 27152.9 517744.3 381770.7 815912 I 829822 9 8437607 8577250 T 50 100 150 m 1342.79 265.98 38802.0 643864.3 584049.44 23350.93 153535.82 28409.67 116646.3 k J h 0 l Carbon dioxide.20 89227.13 119142.79 327.02 257.88 259.89 129839.5 181123.57 338. C02 : ho = 3934 4 9 M h o J 0.35 172368.95 110534.86 128891.93 37252.08 257.92 92658.17 37106.9 564513.55 62394.57 103227.3 33958.2 135954.4 597421 5 610830.07 67177.33 113589.12 156644.0 596051.39 32013.6 465458.4 774346.03 24653.19 105873.80 30426.2 367110.0 840558.I 746779.48 335.91 157412.24 281.1 213091.08 56608.6 548850.56 311.90 m 157.
54 125614.59 I 1 1903.6 128903.57 41575.44 39991.02 71631.82 105035.77 115698.79 315940 477508 6415 I O 807969 97W99 976904 11483 36 1322278 1498747 1677752 1859304 20434 IO 22300.9 368436.4 continued Molecular hydrogen.8 750623.86 22956.91 13534 I39 I9 14259 I4565 14842 15095 15330 15548 15751 15943 161 24 16295 164.03 40878.68 36082.30 81925.61 169.9 305273. IO 48607.20 285464 428292 571258 7144 17 8520.92 7105 19 812991 915853 10191 50 1122926 1227223 1332079 1437533 1543620 16503 75 1757830 18660 16 19749.42 254.42 67254.4 554141.51 253 19.93 472%.9 330315.23 77025. H 2 0 : ho = 239 081.31 32017.56 38417.36 223.3 394203.4 1 205 10.88 79432.9 162213.08 232797 352794 475224 6001 I I 722333 727475 8573 35 989706 1124603 1262037 14020 18 15445.76 191.I 170766.4 540489.43 251.23 30682.62 44513.4 112405.22 271.79 34037.94 253.8 80918.34 76957.13 66483.37 23066.29 107719.76 179.97 53333.3 256141.53 230.21 62525.73 185.3 104388.9 637167.5 355656.80 51092.95 73478.70 9949 11107 11930 12568 130.04 69215.49 242.53 75248.9 679362.68 259.33 148080.15 158828.71 221.07 43168.22 175.8 70942 123776 181466 242770 30434.93 116485.12 110369.91 218.77 37143.91 134555.83 78108.67 240.88 127883.29 248.98 94642.09 824%.35 196.4 268303.1 65826.95 190.77 84208.87 256.48 273.35 57940. I5 24 188.04 170.49 137262.61 63038.0000k l h o l T 50 Water.8 58474.27 132395.76 52928.92 215.07 196.57 121058.1 292868.11 193.6 808422.04 51 160.68 114194.38 32211.91 56655.3 188064.72 55597. H2 : ho = 0.2 3in55.7 145310.59 67797.21 1001520 1145563 12899% 1434865 15802 13 1726081 1872508 2019534 2167192 23155 19 2464546 2614303 27648.93 21952.74 24192.13 21402.62 195.95 352%.8 220212.04 260.2 765009.57 84709.29 257.67 89663 63 91492.Table 9.8 1%730.66 41693.26 118773.03 69963 71 71716.9 526893.25 7063782 7206427 73494 I5 74926% 7636221 7779936 79237 89 8067723 8211680 83556 01 8499425 8643089 s(n 79.39 43417.82 53119.64 38067.3 779438.34 66383. I 693522.62 26459.69 60194.77 56260.9 96464.24 47307.56 192.3 205604.60 131849.12 189.23 265.89 269.78 36852.5 232099.48 198.13 167.21 36289.13 107322.21 39868.34 193.6 707729.37 89168.35 82402.4 179384.3 407188.45 18372.35 123’750.83 183.98 245.85 38153.1 595419.6 1%805.06 121060.66 34701.54 187.13 6083.3 30695.59 62175.57 51256.36 7377552 75934.88 60785.85 28767.7 513353.78 197.05 311 12.67 64975.89 42143.82 180.71 63219.51 48875.68 27608.03 84435.70 43542.67 178.26 I42675 3 I 145379.16 59401.78 156152.17 40248.15 24534.99 26110.24 15228 16538 17481 18224 18817 18840 19368 19833 20248 20625 20971 212.10 92066.8 100 150 200 250 298 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 50 100 150 200 250 298 300 350 400 450 500 550 600 650 700 750 800 850 900  950 1000 IO50 1 100 1150 I200 1250 1300 1350 1400 1450 1500 1550 I600 1650 1700 1750 1800 1850 1900 I200 I250 1300 1350 1400 1450 1500 1550 1600 1650 1700 1750 1800 1850 1900 1950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 1950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 130.9 37355 1 442206 51266.54 52594.79 8578.4 473083.36 272.81 234.00 45413.52 168%.72 172.48 2023 21 303578 404972 506560 6043.84 199.42 188.85 28054.85 181.34 61329.8 280545.26 29935.74 57884.89 105079.26 243.9 499871.45 38378.25 64756.28 189.86 s(r) m 4944.36 49927.73 109612.85 35917.06 53939.43 67391.48 86%3.5 2144604 223371 5 232336 I 241352 9 250420 5 259537 7 268703 4 277916 4 287175 6 296480 1 305829 0 315221 4 324656 3 334133 0 343650 8 353208 8 362806 3 372442 8 3821 I7 4 391829 6 401578 8 41 I364 3 421 I85 6 431042 I 440933 3 450858 6 4608176 470809 6 480834 3 490891 I 5009796 5110993 521249 7 5314303 5416409 5518808 562149 6 572447 I 5827726 593125 8 6035063 6139136 Mn 1567.06 44770.97 264.25 228.9 162290.9 609284.93 55293.96 55100.37 261.79 93326.03 72066.84 126446.72 9516500 9700717 98852 76 100701 29 10255225 104405 12 106259 36 10811442 10996970 I I1824 63 11367859 11553094 d7) 1011.61 20846.7 459779.70 102450.18 150776.89 61160.99 174.3 342949.0 837569.48 59120.5 1 53726.40 171.00 95927.0 244078.88 33749.4 822976.58 214.60 161495.33 32299.79 184.4 486447.15 31102.1 581607.06 270.53 130144.66 247.4 793909.05 89507.I 1 68219.60 802%.0 567847.02 100470.88 39624.87 194.3 173660.71 123339.8 852202.90 118376.47 266.56 59630.8 665248.9 151036.78 78810.7 k J h o l T M n 1427.45 981%.01 45993.68 262.91 80603.3 185141.66 275.04 49223.00 57100.51 200.83 48004.97 63572.46 44701.29 139969.17 69503.9 88638.85 182.30 30023.7 420240.27 6%50.62 46382.2 118037.80 102750.4 208421.2 433356.78 238.7 733 11.4 128698.69 267.45 20208 20270 203 31 20391 20451 20509 205 66 20623 20679 207 34 20788 20841 2557.86 86021.88 250.7 72 1982.91 u(n 1152.92 64879.26 86933.20 29161.17 33495.09 27768.92 26139.37 51277.41 176.5 651183.73 153467.56 113029.83 236.64 186.28 87839.73 49636.49 99834.37 46682.75 32807 17 34536.58 166.72 130.58 129146.17 198.41 652%.48 42368.01 97231.9 866874.8 136966.56 177.1 120689 20031 6 28547 I 374797 463733 467499 563049 661073 761293 86349 I %7495 107316.73 276 78 277 81 278 83 279 83 280 82 281 79 282 74 283 68 284 60 285 51 28641 287 29 288 15 289 01 289 84 290 67 291 48 292 27 293 05 293 82 .90 54589. IO 91412.6 446536.98 19875.17 200.55 29423.86 226.74 58025.82 201.72 232.7 736280.0 381285.7 139905.22 74502.59 93666.8 623200.
5 478814.38 54563.7 506190.84 87887.56 292.66 122856.65 60738.28 67488.04 278.17 734180.32 93756.6 631464.60 6446.21 293.4 361.6 324.4 716672.89 110638.17 55741.66 253.4 368.72 245188.99 925478.35 91966.06 100249.00 270.67 227524.0 216952.20 83713.19 33623.4 254.55 481225.78 6461.59 225.88 50575.62 72035.44 2011.60 235761.53 34524.01 288.6 305785.93 351.8 232.29 4325 1.04 25097.66 148195.66 66895.5 335.19 60348.4 702385.16 254656.8 240.20 9855.42 286.7I 23189.81 905393.50 5779.80 97 155.47 67642.77 18175.4 319.7 180083.89 172533.65 256.93 43509.1 310.93 2 1562.4 659726.71 250549.94 176.77 987145.11 808252.8 61685.1 322.62 3308.76 274.22 290680. .19 2060.53 109903.8 890534. NO : ho = 89 9 14.SO 432 13.9 533742.1 261.7 271.84 279.95 3125.27 207347. I 1008198.45 182.5 200.7 788593.62 273456.65 217414.46 76155.50 161618.53 276.1 147726 239482 336309 436936 .4 280.75 789444.50 24827.63 865896.08 187160.53 70586.3 39001 I .1 759730.53 187364.74 4 I821.63 289.35 20651.74 337.80 1950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 88399.00 291.26 75406.9 265.40 281.33 55956.15 79348.61 193719.63 283.6 274.09 268327.31 202332.4 348.11 57763.47 450206.33 104291.46 167624.31 30955.0 645577.3 299.97 8712.4 291.43 79865.58 28322.71 248.82 149.7 263757.57 17461.0 205.3 745346.65 39990.66 184483.0 424622.97 113628.18 100537.0 465194.74 153019.64 34970.86 266.20 48796.06 214.95 112950.55 404829.29 46017.65 25291.03 36581.62 9086.00 64445.29 827260.28 22 1669.08 139159.10 23168.05 106582.62 189095.0 346490.40 44716.09 48844.58 96088.30 39058.66 25726.40 81757.33 182.2 20759.11 55925.30 19946.29 64719.7 236.3 251.67 293.7 905208.52 226359.59 83630.21 11009.50 5719.8 846675.70 22434.79 61803.80 133878.49 45263.94 89260.i 446473.92 13596.4 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 I050 1100 I I50 I200 1250 1300 1350 1400 1450 1500 I550 1600 1650 1700 1750 1800 1850 1900 1950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 8955.98 269.08 490.22 278.3 312.99 78020.09 91139.3 803070.00 134728.32 85505.4 663059.90 240474.43 104448.22 210483 317575 425891 535422 6417.63 15742.83 290.95 278606.31 157090.00 28254.08 56004.61 1 17452.7 46255.59 51981.% 698265.25 262.16 33172.77 50266.8 730993.73 5834.60 7580.34 237514.38 211972.5 144095.8 603348.09 115215.00 198353.82 197329.75 222464.0 358030.61 192339.2 241959.36 u(T) JiT) n(T) 1046.66 17709 189 14 19776 20451 209.01 244.68 34872.95 82261.43 37688.74 260.00 128546.51 14711.82 258078.50 680575.9 86570.1 492479.49 84099.29 175037.33 95945.9 37 1240. CH4 : ho = 66930.01 243.42 258.2 215.28 90913.90 228.f 359.66 275.93 528910.37 304390.21 86607.99 212315.16 281.50 28134.78 199473.5 326.91 117250.39 594685.74 u(T) Jin 156.32 29634.56 98659.94 106100.91 102415.7 280044.27 63260.69 611530.33 249922.63 280..02 53522.38 360840.92 231.23 94899.08 263199.: 885534.9 286.7 561464.71 561480.6 244.7 318754.90 282.12 80805.28 152579.57 162735.48 40027.81 58897.7 451622.I 375.6 210.69 234.43 85162.17 47428.6 194.33 5451 16.00 277135.6 617387.07 50021.14 170722.41 33737.81 27872.70 54155.1 353.08 88047.23 48304.59 75670.47 52361.4 167982.02 79855.0 132321.94 293626 4422 89 5921 77 743280 8894.42 291.37 752412.90 241.5 29000.8 340.22 .56 370.26 236.86 143396.6 331786.7 333.8 673911.04 496965.7 268. .3 372.38 277.87 434927.89 237674.99 138623.03 465638.62 264.19 41763.03 16748.2 411198.0 229415.1 204573.50 512860.6 328.39 163109.80 59582.02 106164.0 155984.95 18342.9 1 20672.0 283.47 72044.96 19735.1 875887.26 65057.1 314.61 247859.06 257.82 40436.98 46621.73 54061. I 589347.63 130320.7 68813 I .05 31333.74 285.62 63225.57 770832.10 4788.16 46596.08 8197.73 287.44 %779.81 15162.1 575386.4 344879.3 109155.86 24442.42 179883.57 12996.52 71546.8 774146.91 69106.3 519944.66 47026.38 288.03 61398.97 271.12 292.2 384505.8 ~ 8 .07 19886.00 57448.53 36817.36 966349.75 265.18 119182.22 87381.9 258.25 289.54 157866.62 12412.55 125936.5 219.6 438097.73 210.17 945794.06 375348.91 51694.72 14542.64 1752%.50 283756.5 97784.42 70570.68 92338.72 101605.8 344.1 189.83 294.5 716132.46 357.Table 9.71 68215.78 166163.06 578002.2 37635.08 251.63 177460.89 10490.68 31483.1 317.12 57095.00 270.70 16953.59 89483.91 246.41 72438.8 342.44 22449.32 93019.27 242762.7 267276.03 38299.54 182404.55 115484.30 27019.97 12037.71 19408.15 26475.40 29803.23 419801. I 364.20 202997.46 63499.98 628539.07 75928.53 21905.24 289.30 121022.34 32285.3 247.91 224653.49 318263.35 284.92 222.12 129163.47 36325.17 119829.38 151381.7 366.78 117336. 53641.2 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 I050 I 100 1150 1200 1250 1300 1350 1400 1450 I500 1550 1600 1650 1700 1750 I800 1850 1900 8273.43 76426.46 332297.9 861268.44 250.82 74295.35 37821.93 267. ~ 6 139858.m 10969.88 92752.2 254580.08 79887.18 254.48 111767.64 10264.1 I 73499.57 108035.77 59578.5 k J h o l T 50 100 150 200 250 298 YT) 1461.57 252964.3 224.90 124480.85 273.85 dT) 6371.45 263.57 148086.5 397825.41 85549.39 121579.74 44612.8 192282.05 284.40 143612.95 2 12375.52 74%3.7 12987.8 331.92 272.69 207651.99 160.63 83852.L 355.01 261.00 17153.7 346.0 302.4 8321 11.74 4367.0 817576.65 15167.45 168.5 292881.51 68738.57 41220.88 232594.9 T 50 100 150 200 250 298 YT) 906.2 305.08 286.85 65526.06 231056.65 216988.7 547582.47 66180.09 13353.9 75530.44 77888.91 30754.44 108682.70 134.65 238.72 1180.8 307.35 7354.79 218.22 53126.99 1029506.88 12176.4 continued Nitric oxide.46 277.25 645715.3 297.7 klkmol Methane.
RT. then the change in internal energy.may be evaluated as ~2 .T ~ . is the mean specific heat between T. This approach will now be described.) (9.44) where E. h2 .T m f ) f Having calculated the change in enthalpy.TI) = W 2 ) .(h1..This is Tz (9.)( E p ) T ~ ( T I .hl = (Ep)T2(T2 u2 . .u.u .1 171 TABLES OF MEAN SPECIFIC HEAT Sometimes data are given in terms of mean specific heat rather than the actual specific heat at a particular temperature.45) It is also possible to write the mean specific heat as a polynomial function of temperature. and T2.(TZ . ) = a + bT + cT2 + .Tables of u(T) and h(T) against T 9. h. T .48a) . in which case ( E .Normally E. h.RT2 .) = h. b and c are tabulated coefficients.. then (9. between temperatures T..h1 R(T2 . and T2.T .46) where a . Le.T'L (9.43) h2 .47) .h(TJ JT Now. this can be written C.hl = c. . Consider the change of enthalpy.W. is given at a particular temperature T . and T2. and it is then defined as the mean between the temperature T and a reference temperature TEf.3. (9. If it is required to calculate the enthalpy difference between two temperatures T.h. ) (9. = h2 ..(T) dT = h(T) .
9. enthalpy and entropy of the various components as each occupies the whole volume at the temperature of the mixture.%(TZ . The mean specific heats approach is depicted in Fig 9. These expressions are a direct consequence of the GibbsDalton laws.48b) hm. equal to the sums of the internal energy. then the change of enthalpy.2 GIBBSDALTON LAW A gas mixture as a whole obeys the equation of state (eqn (9. of a mixture can be related to the mass of constituents by (9. .172 Thermodynamic properties of ideal gases and ideal gas mixtures or. um. respectively. (b) The total pressure exerted by a mixture is the sum of the pressures exerted by the individual components as each occupies the whole volume of the mixture at the same temperature.%Tz . enthalpy and entropy of the mixture are. by (9. [c) The internal energy. The use of mean specific heat values enables more accurate evaluation of temperature changes because the mean specific heats enable the energy equation to be solved with an allowance for the variation of specific heats. Dalton stated that This statement was expanded and clarified by Gibbs to give the GibbsDalton laws.(hm.2)) [a) pV = n%T where n is the total amount of substance in the mixture.air itself is a mixture of many gases although it can be considered to be oxygen and atmospheric nitrogen (which can be assumed to contain the nitrogen in the air and the other ‘inert’ gases such as argon and carbon dioxide). .um. h.1.hm. is known. m.TI) ~ If the change of internal energy.l= 9.1 DALTON PRINCIPLE any gas is as a vacuum to any gas mixed with it. they act as ideal gases. u2 . 9..3 MIXTURE RELATIONSHIPS The total mass. in molar terms.2 .h.1.4.49) From the ideal gas law . may be calculated in a similar way. If the gases in a mixture are at a temperature well above their critical temperature and a pressure below the critical pressure. 9.4 Mixtures of ideal gases Many problems encountered in engineering involve mixtures of gases .4.2 .u l .] % T I )= h m .4. Expressions relating the properties of mixtures of ideal gases will now be formulated.
= i= 1 4 = 1 It is possible to develop the term for the partial pressure of each constituent from statement (b) of the GibbsDalton laws. etc. Therefore (9. (9. for the mixture as a whole (eqn (9. f xb + x./n n = x.51) and therefore n n = na + n. also n n C P i= .57) i= 1 Often mixtures are analysed on a volumetric basis. + n. and from the volumetric results it is possible to obtain the partial pressures and mole fractions of the components.+ . for constituent a occupying the total volume of the mixture at the pressure and temperature of the mixture. and V . Normally .50) In eqn (9.50). = m P c T = n. paV = na%T But.55) giving p a = x a p . Then.52) Let na _ . + = i= 1 n. = volume of constituent a at the pressure and temperature of the mixture. by dividing eqn (9.+ v. etc (9. V .+ v.2) (9.56) and.=I i=l XiP =P c n xi = P (9. and V . V .xa = mole fraction of a in the mixture n (9.53) Similarly.%T pV.%T.54) x.Mixtures of ideal gases and hence for the individual constituents 173 pVa= maRaT= na%T pvb = m$bT = n.50) by eqn (9.’.2)) pV=n%T Hence.. is given by v = v.and n. But the total volume.. nb/n = x b .and in general p i = xip (9. are similar volumes for constituents b and c. =XI/. i= 1 n (9. with ni/n = xi. + ..
= 1nie. Then. = molar internal energy.. i= 1 n n (9. (9..174 Thermodynamic properties of ideal gases and ideal gas mixtures volumetric analyses are performed at constant pressure and temperature. the mole fraction is V(%) x.60) If the gas composition is given in volume percentage of the mixture. is n%T V=P Hence.65)  1n i k .. = molar enthalpy. magnetism and capillary effects. considering the ith component. from eqns (9.58) and (9.66) Neglecting motion.i (9..59) V n =V n .. then for the mixture E = ne.i i= 1 n n (9.61) V(%) 100 (9..67) . V . If e. = (9.59) (9. i n i=l 1 " =Cxik. = u. then e. = ' 100 and the partial pressure is Pi = P (9.. electricity. and h.63) and H = nh..64) If the molar internal energy and molar enthalpy o the mixture are required then f e.62) The terms relating to the energy of a mixture can be evaluated from statement (c) of the GibbsDalton laws.i i= 1 (9.58) (9. = x. gravity.. v=ni%T P and the total volume of the mixture. and = = n 1 " nie.. = i=l Cxiem. and hence urn = C xiurn.i 1nih..
Entropy of mixtures
175
The definition of enthalpy for an ideal gas is
h,=u,+%T
(9.68)
Thus, for the mixture
hm=C(xi(Urn + R T ) i > xi%T = C X ~ U , ,+ ~ = C x ~ u , , ~%T +
=
C x;u,,; + RT C xi
(9.69)
9.4.4 SPECIFIC HEATS OF MIXTURES
Statement (c) of the GibbsDalton law and the above expressions show that
4 .l,
=
c xiu,,i
and
hrn C xihrn,i =
By definition, the specific heats are
c=
du
' dT
dh and cP=. dT
Thus (9.70) and, similarly
cp. rn
= C xi (cp, rn)i
(9.71)
9.5
Entropy o mixtures f
Consider a mixture of two ideal gases, a and b. The entropy of the mixture is equal to the sum of the entropies which each component of the mixture would have i f i r alone occupied f the whole volume o the mixture at the same temperature. This concept can present some difficulty because it means that when gases are separate but all at the same temperature and pressure they have a lower entropy than when they are mixed together in a volume equal to the sums of their previous volumes; the situation can be envisaged from Fig 9.2. This can be analysed by considering the mixing process in the following way: (i) Gases a and b, at the same pressure, are contained in a control volume but prevented from mixing by an impermeable membrane. (ii) The membrane is then removed, and the components mix due to diffusion, i.e. due to the concentration gradient there will be a net migration of molecules from their original volumes. This means that the probability of finding a particular molecule at any particular point in the volume is decreased, and the system is in a less ordered state. This change in probability can be related to an increase in entropy by statistical thermodynamics. Hence, qualitatively, it can be expected that mixing will give rise to an increase in entropy.
176 Thermodynamic properties of ideal gases and ideal gas mixtures
Fig. 9.2 Two gases at the same pressure, p , contained in an insulated container and separated by a
membrane; p , = p b = p Considering the mixing process from a macroscopic viewpoint, when the membrane is broken the pressure is unaffected but the partial pressures of the individual components are decreased. The expression for the entropy of a gas is (eqn (9.20))
, s
= s,(T) 
P 3 In  + SO,, Po
where s,(T) is a function of T alone. Hence, considering the pressure term, which is actually the partial pressure of a component, a decrease in the partial pressure will cause an increase in the entropy of the gas. Equation (9.20) can be simplified by writing the pressure ratio as p , = p i p o , giving
s ,
= s,(T)  % In p ,
+ so,,
Now consider the change from an analytical viewpoint. Consider the two gases a and b. The total amount of substance in the gases is
nT = nu + nb
(9.72)
The entropies of the gases before mixing are
Sm0 =
=
na[smo(T)3
PI,
+ so,m0I
(9.73)
and
Sm,
= nbSmb = n b [ s m b ( T )
 % In
Prb
+ SO,rnbl
(9.74)
giving the sum of the entropies before mixing (Le. separated) as
(SmT)sep
=
(nTS,T)Xp
= nT[xasmd(T)
+ XbSmb(T)
+ XaSO,m, + X b S O , m b  m ( X a
In Pr, + xb In P r b ) ]
(9.75)
Since the gases are separated and both are at the pressure, p , , then
(SmT)sepnT[xasm0(T) XbSmb(T) + XaSO,rn, + X b S O , m b  3 In P I = +
(9.76)
Hence, the molar entropy, when the gases are separate, is
(SmT)sep
= xasm,(T) =
+ X b S m b ( T ) + xaSO,m, + XbSO,rnb  % In p
C xismz C x,sO.,,  3 In p +
(9.77)
Entropy of mixtures
The entropy of the gases after mixing is (SmT)m,x
=
nTsmT
177
=
nsm
= nosma + n b S q ,
(9.78)
and are where smo smb the molar entropies if each component occupied the whole volume. Thus, substituting for s, from eqn (9.20a) gives (nTSmT)mix (SmT)mix
= nosma(T) +
nbsmb(T)
 3(n,
In p r ,
+ nb
In P r b )
+ naSO,rn, t nbSO,rnb
(9'79) (9.80)
= xasrno(T)+ X b S r n b ( T )  m ( X a
In Pr, + x b In pr,) + XosO,rn, + X b S O , m b
and where pr,= p I / p o , p , = partial pressure of constituent i. Equation (9.80) may be written (SmTIrnix = C xisrn,(T)+ C XzsO,rn,  3 C 1, In ~
r ,
(9.81)
Now, consider the final term in eqn (9.81), based on two constituents to simplify the mathematics
x , In P I , + x b In
Prb
= xa h ( x a P r >
+ x b l n ( x b p r) = x , In x , + x , In p r + xb In xb + x b In p r = C x , In x , + In prC x ,
=
C x, In x, + In pr= In pr  C xi In Xi
1
(9.82)
Hence
( s , , , ~ ) ~ ~ x,s,,(i") + C x,so,,, + 3 =C
1
(9.83)
Considering the terms on the righthand side of eqn (9.83): 1st and 2nd terms 3rd term 4th term summation of entropies before mixing, (SnlT)sep change of entropy due to mixing; this is due to a change ofpartial pressures when mixed pressure term
The change of entropy due to mixing is given by AS = (Srn,)rnix

(SrnrIFep
(9.84 I
which is the difference between eqns (9.83) and (9.77). This gives
AS = 3
1 c x, In X,
(9.85
The numerical value of AS must be positive because x , is always less than unity. Equation (9.85) shows that there is an entropy increase due to mixing, and this is caused by the reduction in the order of the molecules. Before mixing it is possible to go into one side of the container and guarantee taking a particular molecule, because only molecules of a are in the lefthand container, and only molecules of b are in the righthand container. After mixing it is not possible to know whether the molecule obtained will be of a or 6 : the order of the system has been reduced.
178 Thermodynamic properties of ideal gases and ideal gas mixtures
What happens if both a and b in Fig 9.2 are the same gas?
Superficially it might be imagined that there will still be an increase of entropy on mixing. However, since a and b are now the same there is no change in partial pressure due to mixing. This means that the molar fraction is unaltered and
AS=O
(9.86)
9.6
Concluding remarks
A detailed study of ideal gases and ideal gas mixtures has been undertaken in preparation for later chapters. Equations have been developed for all properties, and enthalpy coefficients have been introduced for nine commonly encountered gases. Tables of gas properties have been presented for most gases occurring in combustion calculations. Equations for gas mixtures have been developed and the effects of mixing on entropy and Gibbs energy have been shown.
PROBLEMS
Assume that air consists of 79% N, and 21% 0, by volume.
1 A closed vessel of 0.1 m3 capacity contains a mixture of methane ( C h ) and air, the
air being 20% in excess of that required for chemically correct combustion. The pressure and temperature in the vessel before combustion are, respectively, 3 bar and 100°C. Determine: (a) the individual partial pressures and the weights of methane, nitrogen and oxygen present before combustion; (b) the individual partial pressures of the burnt products, on the assumption that these are cooled to 100°C without change of volume and that all the vapour produced by combustion is condensed. [(a) 0.2415, 2.179,0.579 bar; 0.01868,0.2951,0.08969 kg (b) 2.179, 0.2415,0.0966 bar]
2 An engine runs on a rich mixture of methyl and ethyl alcohol and air. At a pressure of 1 bar and 10°C the fuel is completely vaporised. Calculate the airfuel ratio by volume under these conditions, and the percentage of ethyl alcohol in the fuel by weight. If the total pressure of the exhaust gas is 1 bar, calculate the dew point of the water vapour in the exhaust and the percentage by volume of carbon monoxide in the dry exhaust gas, assuming all the hydrogen in the fuel forms water vapour.
Vapour pressures at 10°C: methyl alcohol (CH,OH), 0.0745 bar; and ethyl alcohol (C&OH), 0.310 bar. [63"C; 4.15%]
3 An engine working on the constant volume (Otto) cycle has a compression ratio of ~ 6.5 to 1, and the compression follows the law P V ' . = C, the initial pressure and temperature being 1 bar and 40°C. The specific heats at constant pressure and constant volume throughout compression and combustion are 0.96 + 0.00002T H/kg K and 0.67 + 0.00002 T H/kg K respectively, where T is in K.
Problems
179
Find (a) the change in entropy during compression; (b) the heat rejected per unit mass during compression; (c) the heat rejected per unit mass during combustion if the maximum pressure is 43 bar and the energy liberated by the combustion is 2150 kJ/kg of air. [(a) 0.1621 kJ/kg K; (b) 67.8 kJ/kg; (c) 1090.6 kJ/kg] 4 A compressionignition engine runs on a fuel of the following analysis by weight: carbon 84%, hydrogen 16%. If the pressure at the end of combustion is 55 bar, the volume ratio of expansion is 15 : 1, and the pressure and temperature at the end of expansion are 1.75 bar and 600°C respectively, calculate (a) the variable specific heat at constant volume for the products of combustion; and (b) the change in entropy during the expansion stroke per kmol. The expansion follows the law pv" = C and there is 60% excess air. The specific heats at constant volume in kJ/kmol K between 600°C and 2400°C are: 32 + 0.0025T ; N, 29 + 0.0025T 50 + 0.0067T CO, H,O 34 + 0.08T; The water vapour (H,O) may be considered to act as a perfect gas. [(a) 22.1 + 0.0184T; (b)  1 1.42 W/kmol K]
0 2
5 The exhaust gases of a compressionignition engine are to be used to drive an exhaust gas turbocharger. Estimate the mean pressure ratio of expansion and the isentropic enthalpy drop per kmol of gas in the turbine if the mean exhaust temperature is 600°C and the isentropic temperature drop is 100°C. The composition of the exhaust gas by volume is CO,, 8%; H,O, 9.1%; O,, 7.5%; N,, 75.4%. The specific heats at constant volume in kJ/kmol K are:
0, H,O
32 + 0.0025T ; 34+0.08T
N2 CO,
29 + 0.0025T 50 + 0.00677' [1.946; 4547.11
The water vapour (H,O) may be considered to act as a perfect gas.
6
(a) An amount of substance equal to 2kmol of an ideal gas at temperature T and pressure p is contained in a compartment. In an adjacent compartment is an amount of substance equal to 1 kmol of an ideal gas at temperature 2T and pressure p . The gases mix adiabatically but do not react chemically when the partition separating the compartments is withdrawn. Show that, as a result of the mixing process, the entropy increases by
4
K1
27
provided that the gases are different and that IC, ratio of specific heats, is the same the for both gases and remains a constant in the temperature range T to 2T. (b) What would be the entropy change if the gases being mixed were of the same species?
180
Thermodynamic properties of ideal gases and ideal gas mixtures
7 The exhaust gas from a twostroke cycle compressionignition engine is exhausted at an elevated pressure into a large chamber. The gas from the chamber is subsequently expanded in a turbine. If the mean temperature in the chamber is 811 K and the pressure ratio of expansion in the turbine is 4 : 1 , calculate the isentropic enthalpy drop in the turbine per unit mass of gas. [256.68] 8 The following data refer to an analysis of a dual combustion cycle with a gas having specific heats varying linearly with temperature. The pressure and temperature of the gas at the end of compression are 31 bar and 227°C respectively; the maximum pressure achieved during the cycle is 62 bar, while the maximum temperature achieved is 1700°C. The temperature at the end of the expansion stroke is 1240°C. The increases in entropy during constant volume and constant pressure combustion are 0.882 and 1.450 kJ/kg K respectively. Assuming that the fluid behaves as an ideal gas of molecular weight m,=30.5, calculate the equations for the specific heats, and also the expansion ratio if that process is isentropic. [0.6747 + 0.0008297'; 0.94735 + 0.000829T; 7.8141 9 Distinguish between an ideal and a perfect gas and show that in both cases the specific entropy, s, is given by
s=s,+
;I
 :I ). (.
Two streams of perfect gases, A and B, mix adiabatically at constant pressure and without chemical change to form a third stream. The molar specific heat at constant pressure, c ~ ,of the gas in stream A is equal to that in stream B. Stream A flows at ~ , M kmol/s and is at a temperature T,, while stream B flows at 1 kmol/s and is at a temperature nT,. Assuming that the gases A and B are different, show that the rate of entropy increase is
cpIn  
I'+.)[;1,: (

How is the above expression modified if the gases A and B are the same? For the case n = 1, evaluate the rate of entropy increase (a) (b) when different gases mix, and when the gas in each stream is the same.
[c,, In[
. (A)..']
h [ ;
!(E)."]; (a) 3 h [
n M+l
M
(")""I:
M+l
(b) O]
10 A jet engine bums a weak mixture of octane (C,H,,) and air, with an equivalence ratio, @ = 2. The products of combustion, in which dissociation may be neglected, enter the nozzle with negligible velocity at a temperature of 1000 K. The gases, which may be considered to be ideal, leave the nozzle at the atmospheric pressure of
Problems
181
1.013 bar with an exit velocity of 500 m/s. The nozzle may be considered to be adiabatic and frictionless. Determine: (a) the specific heat at constant pressure, cp, of the products as a function of temperature; (b) the molecular weight, m,, of the products; (c) the temperature of the products at the nozzle exit; (d) the pressure of the products at the nozzle inlet.
Specific heat at constant pressure, cp,,,,in J/kmol K, with T i n K:
COZ
HZO
0 2
N2
cp,,,= 21 x cp,,,= 33 x cp,,, 28 x = cp,,,= 29 x
10’ + 34.OT lo3+ 8.3T lo3 + 6.4T io3+ 3.4T [0.9986 x lo3+ 0.2105T; 28.71; 895.7; 1.591 bar]
11 The products of combustion of a jet engine have a molecular weight, m,, of 30 and a molar specific heat at constant pressure given by cp,,,= 3.3 x lo4 + 15T J/kmol K where T is the gas temperature in Kelvin. When the jet pipe stagnation temperature is 1200 K the gases leave the nozzle at a relative speed of 600 m/s. Evaluate the static temperature of the gas at the nozzle exit and estimate the total to static pressure ratio across the nozzle. Assume that the products of combustion behave as an ideal gas and that the flow is isentropic. In a frictional nozzle producing the mean outlet speed from the same inlet gas temperature, what would be the effect on (a) the mean outlet static temperature, and (b) the total to static pressure ratio? [1092; 1.732; (a) unaffected; (b) increased]
In reality a true combustion process is even more complex than this because the actual rate at which the reactions can occur is finite (even if extremely fast). this will be introduced in Chapter 12. This combustion is usually performed using air because it is freely available. The theory that will be developed here will be applicable to any mixture of fuel and oxidant and any ratio of components in the products.g. it will be described in terms of commonly available hydrocarbon fuels of the type used in combustion engines or boilers. and some examples are given of where the processes might be found.. e. e. in most combustion processes the situation is even more complex because there is an additional factor affecting combustion. and takes place when they are close enough to interact. The most common combustion processes encountered in engineering are those which convert a hydrocarbon fuel (which might range from pure hydrogen to almost pure carbon. The manner in which combustion takes place is governed by the detailed design of the combustion system. it gives a reasonable assessment of what would be expected under good combustion conditions. These ideas will be introduced in Chapter 15. There is an interdependence between thermodynamics and fluid mechanics in combustion. This rate is the basic cause of some of the pollutants produced by engines. The various different types of combustion process are listed in Table 10. rocket motors.10 Thermodynamics of Combustion Combustion is an oxidation process and is usually exothermic (i. The whole mixture is really taking part in a molecular ‘barn dance’ and the tempo of the dance is controlled by the temperature of the mixture. although other oxidants can be used in special circumstances. The simplest description of combustion is of a process that converts the reactants available at the beginning of combustion into producrs at the end of the process. Hence. In fact.e. coal) into carbon dioxide and water. however. and this interaction is the subject of current research. in reality. which is related to the rate at which the fuel and air can mix. the approach to combustion in this chapter is a simplified one but. It cannot really be used to assess emissions levels but it can be extended to this simply by the introduction of additional equations: the basic approach is still valid.g. This book will concentrate on the thermo . Combustion is the combination of various atoms and molecules. particularly NO. This model presupposes that combustion is a process that can take place in only one direction and it ignores the true statistical nature of chemical change. The process of molecular breakdown is referred to as dissociation. but there is also the possibility of atoms which have previously joined together to make a product molecule separating to form reactants again. releases the chemical (or bond) energy contained in a fuel as thermal energy).1.
both in equilibrium and nonequilibrium states. flat flame burners axisymmetric flames. It will be found that equilibrium thermodynamics enables a large number of calculations to be performed but. wellstirred reactors approximated in pipe flows. explosions Flow Phase of reactants multiphase Reaction sites homogeneous heterogeneous equilibrium chemistry (infinite rate) finite rate Convection conditions natural forced Compressibility Speed of combustion incompressible compressible deflagration detonation Reaction rate . large boilers free flames engine flames most normal combustion processes ‘knock’ in spark ignition engines. e. Bunsen burner general combustion petrol.and oilfired boilers sparkignition engines diesel engines.1 Factors affecting combustion processes Conditions of combustion Time dependence Spatial dependence Classification steady unsteady zerodimensional onedimensional twodimensional threedimensional Mixing of initial reactants premixed nonpremixed laminar turbulent single Examples gas turbine combustion chamber. central heating boiler gas turbine combustion chamber. gasfired boilers diesel engines. it does not allow the calculation of pollutants. boilers petrol engine. gas cooker. gas turbines. diesel engine only used for modelling purposes. petrol engines with fuel completely evaporated. boilers sparkignited gas engines.g. engine diesel engine. the production of which are controlled both by mixing rates (fluid mechanics) and reaction rates (thermodynamics). even with dissociation included. or spark ignition. coal. Table 10. The first part of the treatment of combustion will be based on equilibrium thermodynamics.Thermodynamics of combustion 183 dynamics of combustion. gas turbines. gas turbine combustion chamber special cases for measuring flame speed most real engine cases. and will cover combustion processes both with and without dissociation. coal fired boilers approached by some processes in which the combustion period is long compared with the reaction rate all real processes: causes many pollutant emissions Bunsen flame.
Both CO and 0. Not all reactions are exothermic and the formation of NO during dissociation occurring in an internal combustion (i. there is a balance in the number of atoms of each constituent in the equation and so mass is conserved.1. (j2 c 0 . (10. It should be noted from the combustion eqn (10. 10. aviation fuel) Middle distillates (gas oil. to combine to give CO. will always break down into two molecules of CO and one molecule of 0. Equation (10.1) also indicates that two molecules of CO. None of the products of the refinery is a single chemical compound. and these are separated at a refinery. However. are diatomic gases. in which energy is released by the process) would require CO and 0.1) that three molecules of reactants combine to produce two molecules of products.I84 Thermodynamics of combustion 10.).1 Simple chemistry Combustion is a chemical reaction and hence a knowledge of basic chemistry is required before it can be analysed.c. or A Kerosene (paraffin. Light distillates (chemical feedstock) Fuel to run refinery / 1 Heavy fuel.. but each is a mixture of compounds. whereas CO.) engine is actually endothermic. heating oil) Gases (butane.1 Typical constituents of a barrel of crude oil . is a triatomic gas. 10. this is because exothermic combustion (i.1) This basically means that two molecules of carbon monoxide (CO) will combine with one molecule of oxygen (0. propane) Fig.1 FUELS Hydrocarbon fuels are rarely singlecomponent in nature due to the methods of formation of the raw material and its extraction from the ground.e. the oil might produce the constituents defined in Fig 10. this is signified by the symbol e which indicates that the processes can go in both directions. the constituents of which depend on the source of the fuel. It is conventional to refer to the mixture to the left of the arrows as the reactants and that to the right as the products. An extremely simple reaction can be written as 2 c o + 0. diesel. hence there is not necessarily a balance in the number of molecules on either side of a chemical reaction.)to create two molecules of carbon dioxide (CO. A typical barrel of crude oil contains a range of hydrocarbons..1.
e.). The chemical symbol for methanol is CH. It is normal to assume. alkanes which have a general The formula C. Often fuels are described by a mass analysis which defines the proportion by mass of the carbon and hydrogen. 1 kmol 12+32 44 kg + 2H2O +2~”.H. the alcohols contain oxygen in the form of an OH radical.2) 274.OH.O 2 kmol 2x(2+16) 36 kg (10.). which belongs to a chemical family called alkenes.52 kmol 7.) and butane (C. Some fuels contain other constituents in addition to carbon and hydrogen. The combustion of methane with oxygen is defined by CH.4 kg CO..) Octane (CEH18) Methanol (CH. propane (C. ethane (C. lower alkanes are methane (CH. these are the alcohol equivalents of methane and ethane.2 Combustion of simple hydrocarbon fuels The combustion of a hydrocarbon fuel takes place according to the constraints of chemistry.3) . and that for ethanol is C. it is possible to find hydrocarbons with less than 2n + 2 hydrogen atoms and these are referred to as unsaturated hydrocarbons.s x 12 + 18 x 1 = 114 =8 (mw)CH30H + 3 x 1 + 16 + 1 = 32 = 12 10.).HZn+.g.H.2) In this particular case there is both a molar balance and a mass balance: the latter is essential but the former is not.52 kmol 2x(32+105. which consists largely of methane (CH.67 kg (10. Combustion of methane with air is given by a 1 kmol 12+4 16 kg 9. Usually combustion takes place between a fuel and air (a mixture of oxygen and nitrogen). For example. have a much higher carbon/hydrogen ratio but contain other constituents including oxygen and ash. Solid fuels.).52~28 210... The molecular weights (or relative molecular masses) of fuels can be evaluated by adding together the molecular (or atomic) weights of their constituents. Three examples are given below: Methane (CH. Methane is the simplest member of a family of hydrocarbons referred to as paraffins or.) and octane (CEHIE). Two other alkanes that occur in discussion of liquid fuels are heptane (C. The alkanes are referred to as saturated hydrocarbons because it is not physically possible to add more hydrogen atoms to them.H. that the nitrogen is an inert gas and takes no part in the process.H. A simple unsaturated hydrocarbon is acetylene (C. However. 1 kmol 12+4 16kg + 2Q 2 kmol 2x32 64kg 3 CQ 1 kmol 12x32 44 kg + 2H.H. 79 2 kmol 2x(2+16) 36 kg 21 7. at this level.Combustion of simple hydrocarbons fuels 185 One fuel which approaches singlecomponent composition is ‘natural gas’.OH) (m.OH.).) etc.H.. = 12 + 4 x 1 = 16 (mw)CsH. such as various coals.. more recently. a typical hydrocarbon fuel might be defined as 87% C and 13% H without specifying the actual components of the liquid.
for methane can be evaluated from the chemical equation (eqn 10.186 Thermodynamics of combustion 10.2 COMBUSTION WITH WEAK MIXTURES A weak mixture occurs when the quantity of air available for combustion is greater than the chemically correct quantity for complete oxidation of the fuel.5) then (10. + 3. However.4Nz COMBUSTION WITH RICH MIXTURES A rich mixture occurs when the quantity of air available is less than the stoichiometric quantity. this means that there is not sufficient air to bum the fuel.1 STOICHIOMETRY There is a clearly defined.17 kg then complete combustion will not occur and the mixture is known as rich. this excess air passes through the process without taking part in it. In this simplified approach it is assumed that the hydrogen combines preferentially with the oxygen and the carbon does not have sufficient oxygen to be completely burned to carbon dioxide. Consider a weak mixture with 5 CH. If the quantity of air is greater than that required by the stoichiometric ratio then the mixture is weak. It will be shown in Chapter 12 that the equilibrium equations. In this simple analysis. it is necessary to provide 17. even though it does not react chemically. and @= actual fuelair ratio stoichiometric fuelair ratio stoichiometric airfuel ratio actual airfuel ratio c = 0. + 9.6) For a weak mixture q is less than unity.+ 3.76Nz) $J 2 7. this results in partial oxidation of part of the carbon to carbon monoxide.3). $ (10.2. govern the proportions of oxygen taken by the carbon and hydrogen of the fuel and that the approximation of preferential combination of oxygen and . it has an effect on the combustion process simply because it lowers the temperatures achieved due to its capacity to absorb energy.76N2)3CO.8.50.52 N Z ( 10.17 kg of air.(0. The stoichiometric airfuel ratio. 2 x (32 + 105.fuel ratio. + . 10. + 2H.O + 0.5(0.3 + 2. This mixture is known as a stoichiometric one and the ratio is referred to as the stoichiometric air. this means that there is excess air available.2. which control the way in which the hydrocarbon fuel oxidizes.33) mass of air mass of fuel 16 = 17. 10.17 This means that to obtain complete combustion of 1 kg CH. neglecting reaction rates and dissociation etc.4) where @ is called the equivalence ratio. The equation for combustion of a weak mixture is CH. ratio of the masses of air and fuel that will result in complete combustion of the fuel. and fixed. If the quantity of air is less than 17. This gives & StOlC = .2.
76N2)3 0. such as petrol.( 0 2 @ + 3.333C0. The resulting equation is 2 CH4+(02+3. Hence it is possible to talk of adiabatic combustion as a process in which no energy (heat) is transferred to. For this reason it is now not acceptable to operate combustion systems with rich mixtures. quenching of flames on cold cylinder or boiler walls.76N2)*2H20+ @ Equation (10. simply due to poor mixing of fuel and air. In reality it is also possible to produce pollutants even when the mixture is weaker than stoichiometric. rockets.Heats of formation and heats o reaction f 187 hydrogen is a reasonable one. + 1. At this stage it must be assumed that the carbon is converted to carbon monoxide and carbon.7) cannot be used with values of @ >4/3.52 @ N2 (10.76N2) * ( :@)co2 + ___ 2 H 2 0 + 4(@ .3 Heats of formation and heats of reaction Combustion of fuels takes place in either a closed system or an open system. The relevant property of the fuel to be considered is the internal energy or enthalpy. This is not true because the energy released during a combustion process is already contained in the reactants. respectively. diesel oil or methane. trapping of the mixture in crevices (fluid mechanics effects) and also due to thermodynamic limitations in the process. to define a rich mixture. the system . It is also possible to synthesise hydrocarbons by a number of processes in which hydrogen is . In this case. then eqn (10.2.8) It is quite obvious that operating the combustion on rich mixtures results in the production of carbon monoxide (CO). this oxygen is then available to create carbon monoxide and carbon dioxide rather than carbon molecules.g.1) @ co+ 7. otherwise the amount of CO. or from.9) is a very hypothetical one because during combustion extensive dissociation occurs and h s liberates oxygen by breaking down the water molecules.267N2 (10. These fuels are commonly used because of their ready availability (at present) and high energy density in terms of both mass and volume.667CO + 6. fuels which are not hydrocarbons are burned in the presence of other oxidants. Note that eqn (10. In some other applications. + 2H. becomes negative.O + 0. Then 2 CH4 + . @ is greater than unity. an extremely toxic gas. + 3. space craft.7) If the equivalence ratio is 1. these will not be considered here. of formation or reaction.7) is CH.the temperature of the system increases because of a rearrangement of the chemical bonds in the fuel and oxidant. e. Mechanical engineers are usually concerned with the combustion of hydrocarbon fuels.667(0. In a naive manner it is often considered that combustion is a process of energy addition to the system. Hydrocarbon fuels are stable compounds of carbon and hydrogen which have been formed through the decomposition of animal and vegetable matter over many millennia. 10. etc. in the form of the chemical energy of the fuel (see Chapter 11). The combustion normally takes place in the presence of air.
The heat of reaction f . the energy equation.3) to (10. Temperature. Both of these effects obey the First Law of Thermodynamics.4TS OF REACTION AND FORMATION 042 The energy contained in the fuel can also be assessed by burning it under a specified condition. The chemistry of fuels is considered in Chapter 11. especially the temperature rise that will be achieved.4 Application of the energy equation to the combustion process .3). HE. might still be functions of temperature).see eqn (10. This means that the internal energy and enthalpy can be represented on U .2).a macroscopic approach Equations (10. 1 . 1 . and it is necessary to be able to account for the effect of mixture strength on the combustior. . It is also necessary to be able to account for the different fuel composition: not all fuels will release the same quantity of energy per unit mass and hence it is required to characterise fuels by some capacity to release chemical energy in a thermal form. The South African Sasol plant uses the Lurgi and FischerTropsch processes to convert coal from a solid fuel to a liquid one.188 Thermodynamics of combustion added to a carbonrich fuel. . INTERNAL ENERGIES AND ENTHALPIES OF IDEAL GASES 041 It was shown previously that the internal energies and enthalpies of ideal gases are functions of temperature alone ( c pand c. this energy is referred to as the heat o reaction of the fuel.e.T and HT diagrams.6) show that combustion can take place at various airfuel ratios. 10. The reactants will be basically diatomic gases (neglecting the effect of the fuel) whereas the products will be a mixture of diatomic and triatomic gases . 10.2 Enthalpy (or internal energy) of reactants and products The next question which arises is: what is the spacing between the reactants and products lines? This spacing represents the energy that can be released by the fuel. It is then possible to draw a UT or HT line for both reactants and products (Fig 10. process. i. T Fig.
The term calorific value of the fuel was used in the past to define the ‘heating’ value of the fuel: this is actually the negative value of the heat of reaction. (Q. has a negative value. or measured using a constant volume combustion ‘bomb’. It is usually associated with analyses in which ‘heat’ is added to a system during the combustion process. (e. the air standard cycles.+ gz. The suffix T defines the temperature at which the enthalpy of reaction was measured. If it is measured by a constant volume process in a combustion bomb then the internal energy of reaction is obtained.g. (10.). 10.n R ( h d ~ (1G. The value of the constant volume heat of reaction. (10. this is identical to the term n which was used for the amount of substance in Chapter 9.. e.4(a) and (b) respectively. (ep).. can be calculated from as shown below.10) and neglecting the kinetic and potential energy terms. Fig. the internal energy of reaction. (In a similar way.Application of the energy equation to the combustion process 189 for a fuel is dependent on the process by which it is measured. (ep).) The sign of Qp is negative for fuels because heat must be transferred from the ‘calorimeter’ to achieve equal temperatures for the reactants and products (it is positive for some reactions.= T. and (Q. ( : ) ( : + ) . (ep).11) where n denotes the amount of substance in either the products or reactants.).).ri2. If it is measured in a constant pressure device then the enthalpy of reaction is obtained. It is more normal to measure the enthalpy of reaction because it is much easier to achieve a constant pressure process. again (Q. hi  + gz. and measuring the quantity of energy that must be removed to achieve equal reactant and product temperatures (see Fig 10. are shown in Figs 10. then (QPh = . The enthalpy of reaction of a fuel can be evaluated by burning the fuel in a stream of air. When is evaluated at a standardised temperature it will be denoted by the symbol Most values of Qpthat are used in combustion calculations are the ones.3 Constant pressure measurement of enthalpy reaction Applying the steady flow energy equation Q . and is usually a positive number.( H R ) T = nP(hP)T .).3). Control surface I eQP T. meaning that heat has to be transferred to the calorimeter to maintain constant temperatures). Applying the first law for a closed system to constant volume combustion gives (ep).12) . will be used for internal energy of reaction at the standard temperature.W s= liz. he + . is a function of this temperature and normally it is evaluated at a standard temperature of 25°C (298 K).
a piston would have to move to maintain the conditions.4. T (b) Fig. in the case of a combustion bomb. dT. and u = J cy. (10. Hence the constant pressure and constant volume processes are identical if the amounts of substance in the products and the reactants are equal.14) then in a constant pressure steady flow process with equal temperature end states the reaction results in heat transfer of ( given by <ep)HP T= H R (10.HESS' LAW (e. The heat of formation of a compound is the quantity of energy absorbed (or released) during its formation from its elements (the end pressures and temperatures being maintained equal).15) (10. is formed from carbon and oxygen by the reaction c + 0. For example. . if CO.4 Internal energy and enthalpy of reaction depicted on (a) internal energytemperature and (b) enthalpy temperature diagrams .190 Thermodynamics of combustion If both the products and reactants are ideal gases then h = J c ~dT. These values are denoted as AHo and AUo and will be returned to later. Temperature.nRI (hR)T. T Temperature..n R ) This result is quite logical because the definitions of (Qp)sand require that Tp and TR are equal.T ~ P ( ~ P .Tn R ( u R ) T l ) ) ( ) = np( (hP)T (up)TJ .3 HEAT OF FORMATION .nR).. It is also possible to relate the quantity of energy that is chemically bound up in the fuel to a value at absolute zero of temperature. 10. 0 . ~ which can be evaluated from the polynomial expressions derived in Chapter 9. If the amounts of substance change during the reaction then the processes cease to be identical and. Thus (QpIs  (QvIs = ~ P ( ~ P .(uR)T} (10. .T~ R ( ~ R . + co.13) = % T ( n p. The movement of the piston is work equal to % T ( n p.). 10. 'Products 0 T.16) x = 394 MJ/kmol e Reactants / /* / Reactants .
20) .19a) and then used in reaction (10. Hess’ law can be used to resolve this problem.J/kmol This gives an enthalpy of reaction per kg of CH.125 (AH. e.g.co.19b) to give the heat of reaction of that process. for reaction (10.17) then it is not possible to use the same simple approach because the reactants are a mixture of elements and compounds. However. From experiment the heat of formation of carbon monoxide (CO) is .19b) 1 co + .).)co. having first designated the heats o formation of elements as zero. is . 2 2 1  CO. this allows complex reactions to be built up from elemental ones. For example. + 2H. (10..19a) (10. 191 1 co + 2 0 2 .(110.18) can be subdivided into two different reactions: + co CO.283 MJ/kmol. the algebraic sum of the amounts of heat evolved in the separate stages is equal to the total evolution of heat when the reaction occurs directly.g.0. = Hp H R =394. or (b) the heat liberated by a reaction is independent of the path of the reaction between the initial and final states. giving + 20.g) + 2(AHfh2o(g) (AHf)c.5)= 283 MJ/kmol (10. This enables f the enthalpy of formation of various compounds to be built up from component reactions. Both of these are simply statements of the law of energy conservation and the definition of properties. . These enthalpies of formation can be used to evaluate heats of reaction of more complex molecules.0. 2 1 c + .2. for methane (CH.112 MJ/kmol and hence.) the equation is CH. The heats of formation of any compounds can be evaluated by building up simple reactions. the energy released is (Q.g. This states that: (a) if a reaction at constant pressure or constant volume is carried out in stages. of 50 142 kJ/kg. e.Application of the energy equation to the combustion process If a slightly different reaction is performed giving the same end product. (10. = CO. the reaction co + . The heat of formation of CO may be evaluated by reaction (10.+ Hence the heat of reaction for CO + io2 CO. 802 279 k. However. (10.. Enthalpies of formation are shown in Table 10.0.O (g) = = (12.19b).
c+oco H. This is the negative of the higher calorific value (HCV).. I atm* gas 25°C.&OH(g) 2C + 3H. Carbon. or lower internal energy or enthalpy of reaction.H. Propane.H20(1) 1/2N. 1 atm gas 25"C. CO Water vapour.192 Thermodynamics of combustion Table 10. + 1/20.H50H Reaction gas 25"C.. H. However.+C.O ( .O Nitric oxide (NO) Methane. CH. C. 1 atm* gas 25"C. 1 atm gas 25"C.H.2O(g) H.+C&Mg) 8 c + 9H. its major characteristic is to raise the temperature of a system. Isooctane.O(g)) in the products.OH Ethyl alcohol. 1 atm gas25"C.e.H8(g) 4 c + 5H*C4HlO(g) 8C + 9H. it is common experience that combustion is definitely not isothermal. Hydrogen. C. 1 atm gas25"C. Carbon monoxide.103 916 124 817 224 100 259 280 201 200 238 600 234 600 277 000 c + 0.&(g) 3C + 4H.2 Enthalpies of formation of some common elements and compounds Species Oxygen. CH. Butane. element 0. 1 atm liquid 25"C.H.. H. Ethane. element 393 522 . of 55 639 kJ/kg. Methyl alcohol. Normally the lower calorific value.110 529 241 827 285 800 +89 915 74 897 84 725 . 1 atm gas 25"C.H. i. I amm* gas 25"C. C.CH30H(1) 2C + 3H2+ 1/20.+ 1/20. 1 atm gas 25"C. derived above (50 142 kJ/kg) is the negative of the lower calorific value (LCV) because it is based on gaseous water (H. C.C8Hls(l) C + 2H2+ 1/2O2CH3OH(g) C + 2H.&OH Ethyl alcohol. In this case the enthalpy of reaction would be ( Q p h = (Afff)co2 + ~ = ( A H ~ ) H. If the water in the products (exhaust) was condensed to a liquid then extra energy could be released by the process. CH. I atm* liquid 25"C. the temperature of the products is made equal to the temperature of the reactants. 1 atm liquid 25"C. is used in engine calculations because the water in the exhaust system is usually in the vapour phase.Cc. 1 atm 0.temperature diagram? .co. Higher and lower calorific values The enthalpy of reaction of CH. 10.CCH.5 Combustion processes 10.OH Methyl alcohol. 0. C Carbon dioxide. 1 atm liquid 25"C. 1 atm gas 25"C. CO. How can this be depicted on the enthalpy. in fact. 1 atm gas 25"C. H. I atm* gas 25"C.NO c + 2H. C. + 1/202C2&0H(1) * Note: the values of AHf given m the tables of gas properties are based on 0 K. C2H.(g) 2C + 3H2C. Isooctane.O Water (liquid). ) ~ (Afff)c& 890 225 kJ/kmol This gives an enthalpy of reaction per kg of CH. + 1/20. C.51 ADIABATIC COMBUSTION The heats of reaction of fuels have been described in terms of isothermal processes. element 0. + 1/20. 1 atm gas 25"C.
adiabatic) internal combustion engine. as might occur in a gas turbine.I Insulation TR d Gasturbine: combustion I 2 T T.. to the combustion chamber shown in Fig 10.Combustion processes 193 Consider a constant pressure combustion process.5(a)). and the criterion for equilibrium is that the enthalpies at the beginning and end of the process are equal.. in which there is no heat or work transfer (Fig 10.5(b)) and it is possible to develop from this an equation suitable for evaluating the product temperature. from A.22) The term [HR(TR) H R ( T s ) ] the difference between the enthalpy of the reactants at the is temperature at the start of combustion (TR)and the standardised temperature ( T s ) .25) . then UP('P) = (Qv>s+ [UR(TR) u R ( T s ) l  + Up(Ts) (10.ustion Lpicted on enthalpy temperature diagram: (a) schematic of gas Fig.. as in an idealised (i. turbine combustion chamber.)I [Hp(Tp)Hp(Ts)I = O  (10. These terms can be written as is i= 1 i= 1 (10.e. Going clockwise around the cycle.f f R ( T s ) ) I + HAT. (b) enthalpy temperature diagram of adiabatic combustion process Applying the steady flow energy equation.. Rssss r . From eqn (10..23) where i is the particular component in the reactants and q is the number of components over which the summation is made.ll). gives (Qp)s+ [HR(TR)HR(T.24) If the process had been a constant volume one.) (10. in the case of combustion at constant volume). eqn (lO. The sequence of reactions defining combustion are denoted by the 'cycle ABCDA'. T Adiabatic corr. This process can be shown on an HT diagram (Fig 10. Temperature.5(a) gives Hp = HR (10.21) Hence adiabatic combustion is a process which occurs at constant enthalpy (or internal energy.The term [Hp(Tp) H p ( T s ) ] a similar one for the products.22) HP('P) = (QP)~+ [ H R ( T R.
.194 Thermodynamics of combustion This possibly seems to be a complex method for evaluating a combustion process compared with the simpler heat release approach. 10.5. if work is taken out of the cylinder due to the piston moving away from top dead centre.A W + (10. and if there is heat transfer from the cylinder. this reduces the temperature still further.UR(TR) Hence Up(Tp)= UR(TR) AQ .5(b) is modified to that shown in Fig 10. and the enthalpy of the products is equal before and after combustion.6. tends to reduce the internal energy of the products compared with the reactants. the temperature of the products is reduced as shown in Fig 10. the internal energy is further reduced. as might occur during the combustion process in an internal combustion engine. AQ. then Fig 10. Also. Also.AUo Reactants Products Temperature afier work and heat L T S Temperature after work withdrawn Temperature. / f .6.2 COMBUSTION WITH HEAT AND WORK TRANSFER The combustion process shown in Fig 10.5(b) is an adiabatic one. However. An approach such as this can be applied to more complex reactions which involve dissociation and rate kinetics: other simpler methods cannot give such accurate results.6 Combustion with heat transfer and work output If the engine provides a work output of pdV. as will normally happen in the case of an engine during the combustion phase.27) (10. if there is heat transfer or work transfer taking place in the combustion process. These effects can be incorporated into the energy equation in the following way. the variation of gas properties due to temperature and composition changes can be taken into account correctly. 10. because it is written in terms of enthalpy. T Fig.26) This means that heat transfer away from the cylinder. However the advantage of this method is that it results in a true energy balance: the enthalpy of the products is always equal to the enthalpy of the reactants. The First Law for the process is AQAW=dU= Up(Tp).
2.the position of this line indicates how far the combustion process has progressed (see Fig 10.O + 0. Solution The chemical equation is CH.3. for complete T. Incomplete combustion can be depicted as an additional line on the enthalpytemperature diagram .6 Examples These examples quote solutions to the resolution of a calculator. This is to aid readers in identifying errors in their calculations. The chemical equations of this case are shown in Section 10.76N2)4 0 .7 Enthalpytemperature diagram for incomplete combustion including rich mixtures and dissociation 10.) takes no part in this reaction and does not need to be considered. The is the difference between the enthalpies of formation energy liberated in the reaction of the products and reactants.7). The effect of incomplete combustion on the energy released will be considered here. Products (incomplete combustion) ‘ ’ Products (complete combustion) r T. In this case the amount of energy released can be evaluated from the energies of formation.28) The nitrogen (N.8).3 INCOMPLETE COMBUSTION 195 The value of enthalpy (or internal energy) of reaction for a fuel applies to complete combustion of that fuel to carbon dioxide and water. However.+ 3. 3 3 3 C 0 2+ 2H.667CO + 6. if the mixture is a rich one then there will be insufficient oxidant to convert all the fuel to CO. 10. and H. and does not mean the data are accurate to this level.2.Examples 10.267N2 (10. (ep) . + 1. in a similar manner to that in eqn (10. for incomplete combustion 7 Temperature.667(0. and it will be assumed here that some of the carbon is converted only to CO. Example I :incomplete combustion Evaluate the energy released from constant pressure combustion of a rich mixture of methane and air: use @ = 1. T combustion Fig.5.O.
8. Assume the ratio of specific heats ( K ) for the compression stroke is 1. Example 2: adiabatic combustion in an engine A stoichiometric mixture of methane (CK) and a r is burned in an engine which has an i effective compression ratio of 8 : 1.0 . Hence the energy released by this combustion process is Qp = (AHf)p. Volume Fig.333 ( 393 522) + 2( 241 827) + 0. and is the remaining 23.(AHfh = 688 420. See Fig 10.8 p .34) has occurred because of the lack of oxygen in the rich mixture. Calculate the conditions at the end of combustion at constant volume if the initial temperature and pressure are 27°C and 1 bar respectively. and energy equal to 0. While the incomplete combustion in eqn (10.0 kJ/km01.18)) is unavailable in the form of thermal energy. = 0. a similar effect occurs with dissociation.V diagram for constant volume combustion . (AHf)R = (AHf).5% of the energy that was available from complete combustion (802 279 kJ/kmol).4. This is equivalent to 188 761 kJ/kmol C h . + O. This is because the carbon has not been fully oxidised to carbon dioxide.. when the products are partially broken down into reactants. The lower calorific value of methane is 50 144 kJ/kg at 25°C.667(AHf).(74 897) = 613 522.110 529) 688 420..5% of the energy which would be available from complete combustion.196 Thermodynamics of combustion Enthalpy of formation of reactants. (equivalent to the product of the quantity of carbon monoxide and the heat of reaction for eqn (10..0 kJ/kmol It can be seen that this process has released only 76.b = 74 897 kJ/kmol Enthalpy of formation of products. = + 2(AHf)"*.333(AHf). 10.667 x 283 MJ/kmol CH.667( . (AHf)p= O.
76N2) nR = i0.8 8561.(T.30).2 CH'l 0 2 N2 '298 Difference n nu 21 883.6 16 164.8696 x lo4+ 66 802. + 2 H 2 0 + 7.678 x lo5 10.0 Hence U.3 15 105.8696 x lo4 kJ The products energy at standard temperature.2 K The chemical equation is CH.) = 9.5 Thus U. ) = .Examples Solution 197 p 1 = 1 bar. Constituent '298 CO2 7041. = 300 K 1.6 H2O 7223.0 9073.(Ts) = 66 802. + 3.52  CO.3 2 N2 n nU298 14 446.(T.2 kJ Substituting these values into eqn (10.) = U.6 6025.9 6032.) ~  9.52 (10.52 45 314.3 1 16 164.2 =9.)] is Constituent '689.4 14 587.379 bar = TI( 2) Y = 300 x = 689. T .6 1 7041.S2N2 n p = 10. + 2 ( 0 .<Qv>s [UR(TR) UR(Ts)] + Up(Ts)  (10.UR(T.(TR) .4 p2=p l ( 2 ) T2 = = 1 1 x 81.30) The reactants' energy [ UR(TR) UR(T. and converting the calorific value to molar terms gives U.9 7. U p ( T s )is .52 = 92000 k J / k m ~ l np .52 64 385.4 18.) = SO 144 x 16 + 9.29) The combustion equation is U P ( ' .7 6025.(T.678 x l o5 kJ The value of specific internal energy for the mixture of products is u.9 57 19.8 7.9 2 18 146.
9 7.2 ) k J This value is less than that obtained from eqn (10.6 n nu 1nu = U p ( T p = 932 490.4 1 137 950. The final pressure. Using this approximation gives 2500 76 848.8 79 370.%T3 = np%T3 = Up(Tp)= 967 594 kJ This is within 0.9 .9 kT Hence the value Tpis between 3000 K and 3100 K.5 2 228 114.6 7..9 2 228 389. Assume Tp= 3000 K and evaluate Up(Tp): Constituent ~3ooo COZ 137 950.7 3000 94623.9 1nu p3V3= n.52 575 314.0 1 143 420.2 1nu T P= 3000 + = Up(Tp)= 968 678.198 Thermodynamics of combustion An approximate value of the temperature can be obtained by assuming the exhaust products to be 70% N. can be evaluated using the perfect gas law because .4 HZO 109 612.2 x 1000 = 3097 K Evaluating Up(Tp)at Tp= 3097 K gives Constituent 1(3097 COZ 143 255.0 114 194.30).932 490. and hence the temperature was underestimated. Try Tp= 3100 K.52 596 869. U3lDO n nu 143 420.52 596 224 n nu 143 255.30).3 Hence Tpis around 3000 K. p 3 .0212% of the value of Up(Tp) evaluated from eqn (10. Linear interpolation gives 967 800 .1 7. and 30% CO.2 NZ 76 504.2 968 678.1 1 H0 2 NZ 79 285.932 490.6 2 219 225.1 114 057.
76 848.30) to give U P V P = .9 x 50 144 x 16 + 9.3 .2 ) = 887 571.8 k J Using a similar technique to before.( Q v I s .9 kJ/kmol From the previous calculation the value of Tp lies between 2500 K and 3000 K.31) (10. Solution The effect of heat transfer is to reduce the amount of energy available to raise the temperature of the products.8 10.7 5oo = 2717 Try Tp= 2700 K to check for energy balance: Constituent u2700 CO.7 94 623. If 10% of the energy liberated by the fuel was lost by heat transfer.7 kJ . This can be introduced in eqn (10.1 Up(Tp)= 823 993. the combustion was assum% to be adiabatic.5 2 191 854.8696 x lo4 + 66 802. calculate the final temperature and pressure after combustion.9 N2 n nu 67 877.5 H2O 95 927.5 1 121 807. Example 2.Examples 199 = 3097 300 x 8 x 1 = 82.32) In this case Qm= 0.UR(Ts)l + UdTs) ) (10. and an estimate is T p= 2500 + 84 369.QHT ) [ U R ( T R.76 848. 121 807.52 = 84369. the value of up(Tp) is UP(TP) = 887 571.59 bar Example 3: nonadiabatic combustion in an engine In the previous calculation.9 .52 510 438.4 7.l(Qv). and hence UP(TP) 09(Qv>s [UR(TR) U d T s ) 1+ Up(TS) = Substituting values gives U p ( T p = 0.
8 .6 .6 kJ.1 = 887 N Z 72 935 7. Hence.5 kJ This value is within 0. Solution The stoichiomehic chemical equation is C.8NZ 5 (10.0 .1 7.8 K Constituent '2876 2800 + 887 571.9 1 127 154. = 860 167.34) n R = 29.9 100 470. + 5 ( 0 2+ 3.H. + (0.52 548 471. Evaluate the final temperature and pressure after combustion neglecting dissociation. of propane as 46 440 kJ/kg.76NZ)3CO + 4 H 2 0 + l8.88202+ 22.85 and the initial conditions at the start of the compression stroke are 1.860 167.12N2 np= 30.7 kJ/kmol at the beginning of compression and 106 690.5 n nu U.823 993.52 532 071.9 H2O 103 929.4 and take the internal energy of reaction ( Q .(T.200 Thermodynamics of combustion This is less than the value obtained from the energy equation and hence Tp> 2700 K.1 Up(Tp)= 860 167. by linear extrapolation.3 kJ/kmol at the end (before combustion).H. Example 4: combustion with a weak mixture of propane A mixture of propane and excess air is burned at constant volume in an engine with a compression ratio of 10: 1. try T.1 2 207 858.0016% of the value from the energy equation.0 (10.OJ 302 + 4H2O + 0. ) . Assume the ratio of specific heats for compression is 1.) 557.76NZ) n oc U. + 3. The strength of the mixture (q5) is 0.9 1 131 227.7 = 2875.8 2 200 941. Try Tp= 2800 K: U28W n nu 127 154. The internal energy of propane is 12 911.6 x 100 co2 131 227.6 70 754.33) The weak mixture equation is + C.2 bar and 127°C.
12 133 290.(T.4 [UR(TR) UR(T.9 kJ Assume Tp= 3100 K: u3100 n nu 143 420.6 84 974. = Tl( ): K 1 = 400 x = 1004.882 100 776.75 K The energy of reactants [U.0 5.2 + 188 628.7 0.7 79 370.142 bar T.6 3 21 124. is '298 n nu 7041.7 0 2 N Z u298 Difference n nu 23 165.882 5320.4 W .0 3 430 260..7 780 194.0 6032.(T.7 1 93 778.72 0.9 22.9 4 456 779.)] 548 206.3 12 91 1.) .7 W = Up(Tp)= 46 440 x (12 x 3 + 8) + 548 206.1 114 194.3 4 28 893.8 22. T.12 1 755 685.95 22.12 353 651.0 6025.1 22 013.2 x = 30.Examples The combustion equation (eqn (10.0 + 548 206.7 93 778.2 6031.7 =2 =2 043 360.6 6025.8 15 987.882 74 947.0 17 133.30)) is 201 = 1.7 Up(Ts) 188 628.8 7223.2 + 188 628.2 W = The energy of products at standard temperature.)] is Constituent ula)47 C3H8 106 690.0 Up(Tp)= 2 717 672.U.
4 W. @.13 bar Example 5: combustion at constant pressure of a rich mixture of benzene A rich mixture of benzene (&I&) and air with an equivalence ratio. is 1. See Fig 10.2 717 672.882 76 689.5 H2 0 2 NZ 82 226. p 1 = 1 bar.4 x 100 = 3162 K Check solution using Tp= 3 162 K: Constituent '3162 c 2 o H2O 0 2 NZ 81 142. Pressure at the end of combustion is nPsTP Vl p . This value is within 0.9 .12 1 818 843 n nu 118 773. Hence Tp= 3162 K.12 1 794 878 n nu 146 843. The ratio of specific heats during compression.2 717 672.6 4 475 094. temperature and volume after combustion.8 Up(Tp) 2 818 562. K.4 and the calorific value of benzene is 40 635 kJ/kg.4 2 818 562.6 . Tl = 298 K 1.31 bar = 880 K .7 4 468 138.2 is burned at constant pressure in an engine with a compression ratio of 15 : 1.882 77 760.8 = 86 949.8 3 446 864. = .2 22.3 88 164. TI( = zr = 44.7 Up(Tp) 2 780 234.x 30 3162 x l o x 12 p3=29 400 n ~ s T iV3 = 98.9.0 3 440 529 117 034.8 22.202 Thermodynamics of combustion Try Tp= 3200 K: Constituent 113200 co2 148 954. If the initial conditions are 1 bar and 25°C calculate the pressure. = 3100 + 2 780 194.6 W = Interpolating linearly gives T .0014% of the value calculated from the energy equation.1 0.4 p2 =p l ( z ) T.1 0. of 1.
7 18 721.  aCO.5 + 23.25(0.9 8509.5 26 342.1 8201.)46CO.2 6.5 C6H6+ .35) The rich mixture equation is 7.36) a = 3.25 117 007.5N.4 1 31 734.O + 23.9 p .O np = 32.& + 7.5.2 .7 23.75 The energy equation for constant pressure combustion is (10.2 a+b=6 h + b + 3 = 125 Hence C6H6+ 6.5 + 3.5(O.5N2 (10.38) Constituent C6H6 0 2 N 2 h**o h298 Difference n nh 39 936.8 31 734.V diagram for constant pressure combustion The stoichiometric chemical equation is C.76N. + 3.5N2 (10. b = 2.76N2) 3.1 8503.4 17 838.5C02+ 2 3 2 0 + 3H.76N2) 1. (10.Examples 203 Volume Fig. 10.37) nR = 30.3 [HR(TR).+ 3.HR(T. + 3H.(0. + bCO + 3H20 + 23.)] = 567 951.5 419 209.4 27 230.
5(Ahf)COz2 .5 2 209 803 Hp(Tp) 3 344 558.4 2.3 3.8 kJ In this case the combustion is not complete and hence the full energy available in the fuel is not released.(Ahf)COl = = = 40635 x 78 .5 kJ These two values of enthalpy of combustion are the same within the accuracy of the data used (they differ by less than 0.1 + 283 471.5 x (10.2 23.total 2.5 94 034.39) This value can also be calculated from the enthalpy of reaction by subtracting the energy which is not released because of the incomplete combustion of all the carbon to carbon dioxide. Thus Hp(Tp)= 2 462 047. T.(82 847.5 x ..6) = 2 461 978.5 33 317. because not all the carbon is converted to carbon dioxide. Hence.5 526 522.2 123 750.)= 283 474.7. (Qp)25= (Qp)25.8 3 371 252.6 Hp(T.O 3 n nh 29 102. the energy released by a combustion process is given by In this case = 3.9 W Assume Tp= 2800 K: Constituent COZ co 94 792.5 co 8489.110 529 + 3 x 241 827 . n nh 150 434.9 3.5 199 830.1 kJ = 3.5 2.5( 393 522 + 110 529) 3 169 530 + 707 482.5 236 981.5 21 223.003%).H.5 2 462 047. 5 W f I c 0+ 3(Ahf)H20 +  393 522 + 2.3 = 3 313 406.5 + 567 888. referring to Fig 10. the loss of energy available due to incomplete combustion is 707 482.4 23.: Constituent h298 COZ 9519.7 kJ = .5 kJ/kmol C.8 H2O N2 970 1.0 H2O N2 ~*.2.5( (Ahf)CO.9 8503.204 Thermodynamics o combustion f The products enthalpy at standard temperature. Applying Hess’ law.
The method which is soundly based on the First Law of Thermodynamics ensures that energy is conserved. by volume.5 2 189 757 n nh 122 512. This is suitable for use with all the phenomena encountered in combustion.3 210 360. = x nRST1 p 3 32.2 N Z 90 326.O). n nh Hp(Tp)= 3 210 360..010%. is given by nPsTP v.1 3 355 128.5 227 675. V. p3= 44.Problems 205 Hence Tp< 2800 K.0 23. The pressure at the end of combustion is the same as that at the end of compression. The heats of formation at 25°C are: benzene (C. Hence the volume at the end of combustion.3 210 360.7 .).1 23.8 K Constituent hZ777 co 93 936.e.8 kJ = Hence the equations balance within 0.9 kJ Interpolate linearly: Tp = 2700 + 3 313 406. incomplete combustion.3 H2O N Z 93 181.5 3 367 537.H.5 2 122 661 h*7.31 x VI = 0.5 Hp(Tp) 3 313 674.2 2.0 MJ/kmol. including weak and rich mixtures.1 3.3 co 91 070. 80.4 3. dissociation and rate kinetics. PROBLEMS Assume that air consists of 79% N. Use Tp= 2700 K: Constituent ~~~ ~ ~ CO.7 Concluding remarks A consistent method of analysing combustion has been introduced. water vapour (H.) at 25°C. 144 256.3 MJ/kmol. 149 011.1 2. A large number of examples of different combustion situations have been presented.5 504 896.5 234 840.9 .31 bar.75 x 298 x 1 44. and 21% 0.5 521 540 x 100 = 2776. heat and work transfer. 1 Calculate the lower heat of reaction at constant volume for benzene (C.4 HZO 118 376.5 x 2777 30.2223V1 10. = ___ x P1V . 242 MJ/kmol.).H.9 CO. . 394.9 3 344 558. carbon dioxide (CO. i.
887 952 kJ/km01] In an experiment to determine the calorific value of octane (C8HI8)with a bomb kg. If the initial pressure and temperature were 25 bar and 15°C respectively. No air was present in the calorimeter. At the end of the compression stroke the pressure and temperature are 10 bar and 500 K respectively. If the initial pressure and temperature are 5 bar and 440 K. The mixture is trapped at 1 bar and 300 K.79334. Calculate the lower heat of reaction of octane. If the products of combustion are cooled until the water vapour is just about to condense.1071.22 bar. [59. If the combustion process is an adiabatic one at constant volume. the volumetric compression ratio is 12 : 1. calculate the adiabatic temperature rise and maximum pressure when the mixture is ignited.04651 . The enthalpy of combustion of ethylene at the absolute zero is 1 325 671 kJ/ kmol. calculate the final temperature. and the internal energy at 440 K is 16 529 kJ/kmol. 119.53 bar..333 K. in the ratio of volumes of 1 :30.5 kJ/kmol. 0. 3. the mass of octane was 5. 52.677 kg and the corrected temperature rise in the water jacket 2. and also the composition (by volume) of the dry exhaust gas. 0. calorimeter. and there was 400% excess oxygen. [5 099 000 kJ/km01.8"C. the maximum pressure and temperature achieved during the cycle.11 bar.8463.206 Thermodynamicsof combustion A mixture of one part by volume of vaporised benzene to 50 parts by volume of air is ignited in a cylinder and adiabatic combustion ensues at constant volume. and the index of compression K = 1. 47 119 kJ/kmol] A gas engine is operated on a stoichiometric mixture of methane (CK) and air. and the mean gas temperature (inlet to outlet) is 25°C.1 bar.) [3170 MJ/kmol. estimate the maximum pressure and temperature reached immediately after ignition assuming no heat losses to the water jacket during this time. The temperature rise of the cooling water is 1. 3135 K] A vessel contains a mixture of ethylene (C2H.421 95 x loT4 the water equivalent of the calorimeter including water 2. 65°C. [0. pressure and heat loss per kmol of original mixture. in kJ/kmol at 15°C.4. Calculate the higher and lower heats of reaction at constant volume and constant pressure in kJ/kmol if the gas pressure at inlet is 1 bar. If the initial pressure and temperature of the mixture are 10 bar and 500 K respectively. calculate the maximum pressure and temperature after combustion neglecting dissociation.H8) and air to a spark ignition engine. calculate the maximum temperature and pressure reached. Calculate the equivalence ratio.) is determined in a constant pressure calorimeter by burning the gas as a very weak mixture. 23. [800 049. [1631 K. The gas flow rate is 70 litre/h.) and twice as much ar as that required for i complete combustion. 2960 K] A gas injection system supplies a mixture of propane (C. 2580 K] The heat of reaction of methane (CH. 0. with a water flow rate of 5 kg/min.84 bar. (Assume the internal energy of the fuel is 8201 kJ/kmol at 298 K and 12 998 kJ/kmol at 500 K. 2883 K.
) and air.9. (c) the compression process is isentropic. The volumetric compression ratio of the engine is 20 : 1.4.) and air. during the compression stroke is 1. 99. It can be assumed that the ratio of specific heats energy of methane in the reactants is negligible. intercooled compression ignition engine is operated on octane (C8H18) and achieves constant pressure combustion.4 bar. (b) 10% of the energy added by the fuel is lost through heat transfer. and the trapped pressure and temperature at inlet valve closure are 60°C and 1 bar respectively. calculate the maximum temperature and pressure reached during combustion at constant volume if compression is isentropic and 10% of the heat released during the combustion period is lost by heat transfer. Assume the ratio of specific heats. If the airfuel ratio is 24: 1. K~ = 1.023 x 10' kJ/kmol C&. The trapped conditions are 1 bar and 300 K. Assume that the index of compression K~ = 1. A spark ignition engine with a compression ratio of 10: 1. 88. [Maximum temperature. K = 1. assess if the temperature of the exhaust gas entering the turbine is below the limit of 1300 K. K.4.32) of octane (C. and the pressure and temperature at the start of compression are 1. 84. pi) of the cycle in bar. If the initial temperature and pressure at the commencement of compression are 60°C and 1 bar respectively. and the index of compression is 1. Calculate the maximum temperature and pressure achieved during the cycle if: (a) combustion occurs at constant volume. while that of expansion.. and the enthalpy of the fuel in the reactants may be assumed to be negligible. Calculate how much lower the maximum temperature is under this condition than when the engine was operated stoichiomehically. and the indicated mean effective pressure (imep. value is very close to limit] 11 A gas engine is run on a chemically correct mixture of methane (CH.16 bar] 8 One method of reducing the maximum temperature in an engine is to run with a rich mixture.Problems 207 7 A turbocharged. with an equivalence ratio @ = 0.4.) and air. What are the major disadvantages of operating in this mode? [208"C] 9 A gas engine with a volumetric compression ratio of 10 : 1 is run on a weak mixture of methane (CH. Tp= 1298 K. The enthalpy of reaction of octane at 25°C is 44 880 kJ/kg.H.77 bar] . 15. The air enters the combustion chamber from the compressor at 10 bar and 500 K. runs on a rich mixture of octane (C. [2817 K.59 bar] 10 A jet engine bums a weak mixture (@ = 0. Assume that the combustion process is adiabatic and that dissociation can be neglected.2. with an equivalence ratio of 1. The compression ratio of the engine is 10 : 1..35 [2495 K. and the heat of reaction at constant volume for methane at 25°C is 8. operating on the Otto cycle. and that the internal [2956 K. calculate maximum temperature and pressure achieved in the cycle.4.H.5 bar and 350 K respectively.) and air.
This concept was introduced in Chapter 10. They can also be evaluated by consideration of the chemical structure of the compound. releasing dissociation energy of A H ( X to form the reactants.1. who tend to relate combustion to heat addition or heat release processes. and it is released by the spark. The process of breaking the chemical bonds during the combustion process can be depicted by a diagram such as Fig 1 1. In reality combustion is not a process of energy transfer but one of energy transformation. c nR. Each compound consists of a number of elements held together by certain types of bond. and it was stated that adiabatic combustion could be achieved. .2 shows how the energy required to separate two atoms varies with distance: the bond energy is defined as the minimum potential energy relative to that at infinity. If these atoms are then brought together they would combine. It is assumed that element molecules can be atomised (in a constant pressure process) by the addition of energy equal to AHa. The point of minimum energy indicates that the molecule is in equilibrium. the energy of a particular type of bond is similar irrespective of the actual structure of the molecule. 11. and heats of formation were used to evaluate heats of reaction (Hess’ law). and some of these energies are listed in Table 1 1.11 Chemistry of Combustion The thermodynamics of combustion were considered in Chapter 10. This approach is encouraged in mechanical engineers by the application of the air standard cycle to engines to enable them to be treated as heat engines. Figure 11.1. Using Hess’ law. The concept of adiabatic combustion runs counter to the experience of many engineers. The bond energy is the amount of energy required to separate a molecule into atoms. the enthalpy of reaction of the fuel can be evaluated as the difference between the enthalpies of formation of the products and the reactants These energies are essentially the bond energies of the various molecules.1 Bond energies and heats of formation Heats (enthalpies and internal energies) of formation can be evaluated empirically by ‘burning’ the fuel. The sum of the dissociation and atomisation energies (taking account of the signs) results in the enthalpy of formation of the reactants. In a similar way the enthalpy of formation of the products can be evaluated. It will be shown that the energy which causes the temperature rise in a combustion process is obtained by breaking the bonds which hold the fuel atoms together. The energy released by combustion in a spark ignition (petrol) engine is all contained in the mixture prior to combustion.
11. Naphthalene: C.2 498.4 255.J& Carbon dioxide: CO. n n Reactant molecules . dissociation and resonance energies (based on 25OC)* Bond atomisation (AH.) HH C (graphite) Energy (MJ/kmol) 435.1 Some atomisation.5 428.Y ) ) (MJ/kmol) CH NH 0H HOH 414.2 Variation of bond energy with distance between atoms Table 11.5 812.2 946.5 35 1.2 Bond dissociation Energy ( A H ( X .7 497.9 117. 11. N=N c0 c=o cc c=c c=c *note: these values have been taken from different sources and may not be exactly compatible.7 698.5 615. 3 Wfh V V V Fig.4 717.2 Energy (MJ/kmol) 150.0 Resonance Benzene: C.1 347.5 359. . CAH(XY).1 Relationship between enthalpies of formation and reaction energy Distance Fig.Gaseous atoms 4 n n c m Elemental molecules n CAH(XY). m.H. COOH group (O=O)o.4 137.
the atoms must be cooled to form the hydrocarbon fuel. and also indicates that the energy of formation of the fuel ( A H . the ring structure of benzene. These atoms can be considered to have been brought together by heating carbon and hydrogen (in molecular form) under conditions that encourage the resulting atoms to bond.2 10 Chemistry of combustion In addition to the energy associated with particular bonds there are also energies caused by the possibility of resonance or strain in a particular molecule.e. A hydrocarbon fuel consists of carbon and hydrogen (and possibly another element) atoms held together by chemical bonds.2) Example Evaluate the enthalpy of formation of CO. can reform to give bonding across the cyclic structure (see Fig 11. plus six carbonhydrogen bonds.1) In reality the enthalpy of formation is more complex than given above because energy can be stored in molecules in a number of ways.2 Energy o formation f It will be considered in this section that the processes take place at constant pressure and the property enthalpy ( h or H ) will be used. including resonance energies (in the benzene ring structure) and changes of phase (latent heats). There are two processes involved in this: first. For example. AH.Y)R (11. the carbon has to be changed from solid graphite into gaseous carbon atoms and the hydrogen also has to be atomised. .Y)R)required to dissociate the chemical bond in the compound CJ.O from the atomisation and dissociation energies listed in Table 11. if the processes were constant volume ones then internal energies ( u or U )would be the appropriate properties. = AH. A H ( X . i. = C AH. . showing bond resonance through delocalised electrons 11.) and the second is dissociation energy (XA H ( X .. which is normally considered to be three simple double bonds between carbon atoms. and H. A more general representation of the enthalpy of formation is A H .1 shows these terms. and some typical values are shown in Table 11. second.1. (11.C AH.1. This results in a substantially higher energy than would be estimated from the simple bond structure.3).. ) is the net energy required for the process. These two processes have two energies associated with them: the first is atomisation energy (AH.. H H H H H Fig. 11. then.Y ) .C A H ( X . Figure 11.3 Bonding arrangements of benzene.C AHms. together with three single ones..
3) where the (g) indicates that the element or compound is in the gaseous (vapour) phase. from Fig 11.O) This is formed from the hydrogen and oxygen molecules in the reaction + .2 x = 698. with subsequent recombination to form carbon dioxide..[CO.. 11.C AH.5 MJ/kmoi.] = + 1 = 717.) molecule (see Fig 1 1 4 . (AHf)coz= C AHa CAH(X .1. Then (AfZf)coz C AHa[Cgraphie1AHa[O= 0 .5) 381.4 Gibbs energy variation during a reaction Hence. .o(g) (11.(g)H.Y ) . reactants stable I Progress of reaction Fig.Energy of formation Solution 2 1 1 Carbon dioxide (CO.(g) l.9 (11.137. Water (H.(g)+CO.e..C AHIaent (11.2(C = 0) AH.. The reaction in eqn (1 1.) Carbon dioxide is formed from carbon and oxygen in the reaction.1.. and (1) will be used to indicate that the element or compound is in the liquid phase. . which are in a metastable state. are activated above a certain energy to produce atoms which will then combine to form the stable CO. c m i + O.5 MJ/km01 The tabulated value is 393.C AH.4) In this case there is a resonance energy but the latent energy (i.7) Thus (AHf)Hzo C AHa C AH(X .4.C AHRs.2+ 435. latent heat) is zero. Effectively the reactant molecules. (11.3)is achieved by atomisation of the individual carbon (graphite) molecules and the oxygen molecules.O.Y ) . = .6) (11.
..65 MJ/kmol The tabulated value is 285.8) Example Evaluate the enthalpy of formation of methane. when AH..8/1000 = 285.HI + i AH.5 Atomic arrangement of methane molecule (11.212 Chemistry of combustion In this case AHEs= 0 but AH.[O = 0 .Y ) = =AH.18 x 2441.5 (a).5 .4 + $ (498.497.[H .[H . Solution The structure of methane is tetrahedral. = 0.11) . H H H H C H (4 Methane can be formed by the following reaction: Cgraphire + 2H2(g)C%(g) (b) Fig.. (11.7 = 241. 11..OH] .2) ...HI X 1 = 435..7 .9) (11.0(1) (AHf)H20(1) (AHf)HiO(g) + (mw)HzOhfg = = 241. depends upon the phase of the water.6) becomes H*(g) +$02(g)HH.7 MJ/kmol This compares well with the tabulated values of 241. If the water was in liquid phase then eqn (1 1.428.6 MJ/kmol.6 MJ/kmol.10) (11.C AH(X . First. Methane is often depicted in planar form as shown in Fig 11. C&.5 (b). . consider the water is in vapour phase. and of the form shown in Fig 11.[0. Then (AHf)H20 X AH.
.] + 2 AHa[H. H H HCC0H H H I I I I Fig.7 .4 energy for H  + 0 + 0.C ] = 717..5[CH]  [CC] [C01 .[OHI C..6 Structure of ethanol molecule Ethanol can be considered to be made up of the following processes: This gives the following equation: 2C(g) + 2 x 717.6. C.H.Energy of formation 213 Hence (AHf)Ch = C AH.7 .C AH. + 6H + atomisaoun energy fur C 3 x 435.7 MJ/kmol .351.4 4 x 414.OH.OH(g) C*H.2 = (11. and the difference occurs because the energy of the bonds in methane is affected by the structure of the methane molecule.OH(g) + 2 x 717. .2 5 x 414.2. Example Evaluate the enthalpy of formation of ethanol.. Solution The planar representation of the structure of ethanol is shown in Fig 11.4 + 0.Y ) ..78 MJ/kmol. .H.210.5 x 498.428..C AH(X .5 70 MJ/kmol The tabulated value is 74.5 . which results in attraction forces between molecules.347.C AHI. 11.13) . = AH..[C.2 + 3 x 435.12) + 2 x 425.HI .5 x 498 2 energy fur 0 atomlsation (11.4[H .5 .
= AH. the enthalpy of formation of oxygen is 1 zero.17) The heat of reaction is given by AHR = (AHf)P. Thus (AHf)R (AHf)CH470 MJ/kmOl = = Similarly for the products (11.e.i. This value of zero is assumed as a base level for all elements.(AHf)R = 381.(70) = 794. in a similar manner to that used to find the enthalpies of formation of compounds. or from the enthalpies of formation of the compounds in the reactants and products.7 MJ/kmol. The reaction describing the combustion of methane is CH4(g) + 20z(g)~Oz(g) + 2HzO(g) (11. i.HI + 2 AHa[O= 01 . The value obtained from tables is about 222. Solution This can be obtained either by using atomisation and dissociation energies..2 [ 0 = 01 (11.14) becomes CH4W + 2o~(g)coz(g) + 2Hz0(1) (11.19) . Both methods will be used in this case. Example Evaluate the enthalpy ofreaction of methane. Hence the enthalpy of formation of the reactants (AHf)R = C AHa.853 MJ/kg of ethanol.C AHms C AH. This is equivalent to 5.14) The chemical structure of methane was given above.2.7 .7 .C ]..2 x 241...8 MJ/kmol.. If the higher heat of reaction of methane is required then eqn (11.[C.] + 2 AHa[H .15) Note that the atomisation and dissociation energies of oxygen are equal (2 AHa[O= 0 = 2 [ 0 = 01) and cancel out.214 Chemistry of combustion Hence the enthalpy of formation of gaseous ethanol is 210.C AH(X .18) This is close to the value of 802.16) ( 11.. and the difference is attributable to the slight variations in bond energy that occur due to the threedimensional nature of the chemical structure.Y ) .9 MJ/kmol quoted as the lower enthalpy of reaction of methane in Table 11.9 MJ/kmol (11.4[H .
23) .. = (11. . and thus AH.7 .[O = 0 1 5[H .0 = .20).C AH.5 .7.2 + 3 x 435.18): A R = (AHf)P .(g) + 3H20(g) (1 1.[H .[ C = O ] .428. ..5 =7x ..351.C AH(X .7 Structure of benzoic acid molecule Solution The reaction of benzoic acid with oxygen is C.4 + 498.3 [ C = C ] .Energy o formation f Example 215 Evaluate the lower enthalpy of reaction of benzoic acid (C.5 .5 x 414...... . The planar diagram of its structure is shown in Fig 11.H&OOH).C AH(X .(AHf)R H The values of Hf were calculated above for CO.[C.698..4 .C] .20) The easiest way to evaluate the enthalpy of reaction is from eqn (1 1. and hence the only unknown quantity in eqn (1 1. = = 7 AH.1 .C AH.150.Y ) .H.C AH. 0 C.4 x 347.[AHreslC6& .230.ite] + 3 AH.3 x 615. 11.H HC HC (I f H CH Fig.COOH(g) + 7. and H.0.Y ) .[AHmslCOOH (1 1.1 M J / k m ~ l (11.HI + AH.O.21) = 0...5O2(g)7C0.Lo ..22) Hence (AHf)C6HsCOOH717. The acid is in gaseous form before the reaction.21) gives (AHf)C6H5COOH C AH.2 .117.C] 4[C .O1 .LC .. Substituting values into eqn (1 1.18) is the enthalpy of formation of the benzoic acid: (AHf)C6H5CmH C AH.7 . see eqn (1 1.
4 Concluding remarks It has been shown that the energy released by a fuel is contained in it by virtue of its structure.24) 3395. the stoichiometric airfuel ratios of many basic hydrocarbon fuels lie in the range 13:117:1. It is possible to assess the enthalpies of formation or reaction of a wide range of fuels by considering the chemical structure and the bonds in the compound.3 8 1 .25) The tabulated value is 3223. giving an inaccuracy of about 2%.H = 3395. all of the fuels have negative enthalpies of reaction.2 MJ/kmol.6 . the bonds between the atoms. the commonly used hydrocarbon fuels are usually mixtures of hydrocarbon compounds.1) = 3165.e.7) = (11. A table of enthalpies of formation and reaction for common fuels has been given. at around 44000 kJ/kg.5 MJ/kmol (11. 11. These have been taken from a number of sources and converted to units consistent with this text where necessary. some of the fuels have positive enthalpies of formation. 5 ) + 3 ~ (241. .H. simply because the oxygen cannot provide any energy of reaction. There are a number of interesting observations that can be made from this table: 0 0 0 0 0 0 the enthalpies of reaction of many of the hydrocarbon fuels on a basis of mass are very similar.(230.c.5 MJ/kmol Thus the enthalpy of reaction of benzoic acid is (AHR)c.216 Chemistry of combustion The enthalpy of formation of the products is (AHf)k' = (AHf)COz + (AHf)HzO = 7 x ( .3 Enthalpy of reaction The enthalpies of reaction of some commonly encountered fuels are given in Table 11. the enthalpies of reaction of the alcohols are less than those of the nonoxygenated fuels. 11. i.2.
w o I I l l I N N m b w m m m m o o m N o m 0 O D 0 +wr w m * z + + + + m b + m m Cm m o INN I l l 1 I l l N s .m w b N m m d m d o m m m m m m m m e m I l l 1 d .2 ~0 .o w m ~r I w o m m a 0 0 w + w .
G. was introduced im Chapter 1. or one of fixed composition. molecule is known as dissociation.3) are based on the assumption that G = mg = mg( p .+CO. and these components can react to form other . These methods are not completely correct and a more rigorous analysis is necessary to obtain greater accuracy.O and CO. performing only mechanical work. To evaluate the amount of dissociation that occurs (the degree o dissociation) it is necessary to evolve new f techniques.g. (12. g. to be in equilibrium.1 Gibbs energy The concept of Gibbs energy.2) and (12.3) Equations (12.12 Chemical Equilibrium and Dissociation Up to now this book has concentrated on combustion problems which can be solved by methods based on equilibrium but which do not require an explicit statement of the fact. The change in the specific Gibbs energy. The real process is one of dynamic equilibrium with some of the carbon dioxide breaking down into carbon monoxide and oxygen (or even more esoteric components) again. dG).1) It is implied in this equation that carbon monoxide combines with oxygen to form carbon dioxide. e. T ) . complete combustion of a hydrocarbon fuel in air can be analysed by assuming that the products consist only of H. for a system of fixed composition was defined in terms of other properties as d g = v dp .. until now the up reaction has been described by the equation co + 1/20.. =0 (12.. which might then recombine to form carbon dioxide. If the system has more than one component.2) It was also shown that for a closed system at constant temperature and pressure. The breakdown of the CO. Consider the combustion of carbon monoxide (CO) with oxygen (02).s dT (12. and this is quite acceptable for a single component system. and as soon as that has happened the reaction ceases. This is not a true description of what happens in practice. 12.
T. then it is necessary to define the Gibbs energy as G = m g = m g ( p ..4) and if it is assumed that G is a continuous function with respect to p. then the change of G with changes in the independent variables is dG = $ ) T .m.*.1). It is convenient to define this as PI 4.5a)) will be used because the arguments are slightly easier to understand.) (12. where dm.ciT ( + aml (”) + . the temperature. the pressure and total mass of the system remaining constant. appreciated significance. The first term denotes the change of Gibbs energy due to a change in pressure.5a) amn p. has a more readily change in internal energy. (12. are changes in mass of the various constituents..dm. If G = mg = mg( p. A similar equation can be written in terms of amount of substance n. =(E) (12.. This is equivalent to . and T and the masses of constituents comprising the mixture. when the term (aU/am.. .6) The fourth term is a general term of the form of term (3) in eqn (12...6). T. dU. m.T. e.m.T. of constituent 1 to the system. the pressure. The second term denotes the change of Gibbs energy due to a change in temperature.mi) where m. The term represents the ‘quantity’ of Gibbs energy introduced by the transfer of mass dm. total mass and composition of the system remaining constant. . p.S dT derived previously.)p. (*) dm. is the mass of component i. and m = C mi.l drn. (This can be more readily understood by considering the dm.) The significance of the terms on the right of eqn (12. d p ( + $)p. and is V dp.g.. if the system contained carbon monoxide. This is equivalent to the term derived when considering a system of constant composition.T. 2.5a) is as follows: 1. temperature and masses of other constituents remaining constant. and is For the initial part of the development of these equations the massbased relationship (eqn (12. The significance of changes of composition on the value of the Gibbs energy of a mixture will now be investigated.Gibbs energy 219 compounds. The third term shows the change of Gibbs energy due to a change in the mass (or amount of substance if written in terms of n) of constituent m. oxygen and carbon dioxide as defined in eqn (12..m. 3.
T dS . these can be interpreted as the capacity to do work brought about by a change in a particular property.TS)=dH .m. .9) Considering each of the terms in eqn (12. p The term p is called the chemical potential and is defined as (E)p.2 Chemical potential. Assuming that H is a continuous function. in terms of masses dG=VdpSdT+xpidmi i= 1 (12. Thus p i is the increase in the capacity of a system to do work when unit mass (or. d n . it can be considered in terms of the other derived properties.10) (12. if oxygen is added to a mixture of carbon monoxide. For example. (12.S d T + C p idmi + T d S + S dT = dG = V dp + T d S + C p idmi (12. First.11) . in the case of pmi.220 Chemical equilibrium and dissociation Hence.SdT + ~ p .9). p ican be considered to be a ‘chemical pressure’ because it is the driving force in bringing about reactions. water and nitrogen (the products of combustion of a hydrocarbon fuel) then the mixture could further react to convert more of the carbon monoxide to carbon dioxide.10) By comparison of eqns (12. the work done in a feed pump of a Rankine cycle). The third term is also an increase in the capacity of the system to do work.9) and (12.S dT Hence dH (12. The first term is the increase in capacity to do work that is achieved by an isentropic pressure rise (cf. carbon dioxide. and more work output could be obtained.7a) while in terms of amount of substance n dG = Vdp . but this time it is brought about by the addition of a particular component to a mixture. (12.8) + T d S + S dT = V dp .T. and the second term is the increased capacity to do work that occurs as a result of reversible heat transfer. unit amount of substance) of component i is added to the system.7b) 12. By definition d G = d ( H .* I The significance of p will now be examined.
16) [Note: Although p = g . (ii) the numerical value of p is not dependent on the property from which it is derived (all the properties have the dimensions of energy and. it is different from g inasmuch as it is an intensive property whereas g is a specific property. lu=g (12. By the twoproperty rule this means that P = P(P9 T ) and similarly P = p ( PP T ) (12. .e.13) Since p is an intensive property it may be compared with the other intensive properties p and T etc. p . e.17) Equation (12. 2 (12. n (i) (12. i. P or 71. by the conservation of energy this is reasonable).14) (12.12) The following characteristics of chemical potential may be noted: the chemical potential. would be left at the final condition. could combine to form 1 mol CO.. If the reaction proceeded to completion. This is the stoichiometric equation of the reaction and the amounts of substance in the equation give the stoichiometric coefficients. (iii) the numerical value of p is independent of the size of the system and is hence G intensive property. Suppose there is a system of mass m . is a function of properties and hence is itself a thermodynamic property. then the total Gibbs energy is G = mg whereas the chemical potential of the whole system is still p { cf.Stoichiometry 221 Similarly it can be shown that ( 12.1 12. It shows that 1 mol CO and $mol 0. no CO or 0.3 Stoichiometry Consider the reaction 1 co + 02 * co.15) It can be shown that the chemical potential p for a pure phase is equal in magnitude to the specific Gibbs energy at any given temperature and pressure.g.17) shows the stoichiometric proportions of the reactants and products. hence.
12.O2a C 0 2+ nCO 2 Weak mixture (excess of oxidant) C O + .18) to the CO + $0. vco = .C + v d D (12.222 Chemical equilibrium and dissociation The general equation for a chemical reaction is v.20) (: 1 (12.1 MIXTURES Mixtures are not necessarily stoichiometric and the following terms were introduced in Chapter 10 to describe the proportions of a mixture: If reactants occur in proportion to the stoichiometric coefficients then the mixture is said to be chemically correct or stoichiometric. This means that macroscopic measuring techniques do not sense the changes but give the impression that the system is in a state of ‘static’ equilibrium. Equations (12. C and D are the substances involved in reaction gives the reaction.21) NI3. The effect of this is that the . the reactants) and positive signs to those on the righthand side (nominally. 12. the products).1 vq = 112 vcq= 1 (12. In the equilibrium situation the rates of creation and destruction of molecules of any compounds are equal. B.18) where v is a stoichiometric coefficient.20) and (12. (iii) If the reactants have a lesser proportion of fuel than the correct mixture then it is said to be weak. Applying eqn (12. chemically correct mixture is CO + O2 Rich mixture (excess offuel) 1 (1 + n)CO + . (ii) If the reactants have a greater proportion of fuel than the correct mixture then it is said to be rich. and A.3.4 Dissociation The basis of dissociation is the atomic model that all mixtures of gases are in a state of dynamic equilibrium.A + v b B e v.+ n O2*CO2+nO2 *C 0 2 (12. Molecules of the compounds are being created whilst existing ones are breaking down into simpler compounds or elements (dissociating).21) have been written neglecting dissociation. (i) e.19) It is conventional in chemistry to assign negative values to the stoichiometric coefficients on the lefthand side of the equation (nominally.g.
* co. Experience shows that in the ranges normally encountered in practice.1 WEAK MIXTURE WITH DISSOCIATION Equation without dissociation: CO+ . the C and 0 atoms have a negligible effect.26) Adding eqns (12.0. This allows the general reaction to be simplified to 1 (12.27) 2 2 In eqn (12.0. that has dissociated. ~ C O . and the equation for the dissociation of CO. Dissociation of CO. neglecting particularly esoteric and rare compounds: 1 (12.: (: 1 (12.a ) . + n O . a a C O .4. a is known as the degree ofdissociation.28) aC0. first using the carbon monoxide reaction.22) 2 On a molecular basis the above reaction can go either way. and then a general hydrocarbon fuel. 2 (12. a co + 1/20.eaCO + .a a C O . + a C O + . is (12. (12.a)CO.25) 2 By considering the stoichiometric equation (eqn (12.O .27).23) CO + .0. + bCO + do. It is now necessary to consider a technique which will define the net direction of change for a collection of molecules. Before discussing methods of evaluating a . First.0.26) gives a 1 CO + . the effect of dissociation on nonstoichiometric mixtures will be shown. This can be defined as a = (1 .o.0. consider the general equation for the CO + io. 12.24) co + .aCO + .Dissociation 223 reactions can no longer be said to be unidirectional but must be shown as 1 (12.aco. + eC +fO 2 where the carbon ( C ) and atomic oxygen (0) are formed by the breakdown of the reactants.25)) a general equation may be constructed in terms of a: co + . 2 It is possible to write this equation in a slightly different form by considering the amount of CO.0 . aCO. reaction. This equation shows the effect of dissociation on a chemically correct mixture. + bCO + d o .+ n O .22)) and the dissociation equation (eqn (12.29) . 2 a (12. aCO. 3 (1 .aCO + .
+ ( n + a)CO + .: aCO2aCO Total reaction: (1 + . 2 2 + al+a20. H .30) 12.+ 3.O can be added into this equation as (eqn (12.O + 3.+(la)CO. =3 (1 + a)CO.4. + .4.a. and this will react with the stoichiometric quantity of air as shown in the following equation: C.35) . u a . H . 2 which gives a general equation with dissociation (12.0. ) C O .H.29)) 3 N.0 2 1 2 =3 co. 2 a + n)CO + .34) C.CO + .0.31) Dissociation of CO. + x+ ( I: (0. + x+ ( (0.(1 .+ 3.0.H. C O . H .O +xa. + .76x+ (1 :) ( :) N.+aCO+ (12.0. O u a .a . and H. Y + .76 x +  2 ( The dissociation of the CO.76 N2) + xCO.3 GENERAL HYDROCARBON REACTION WITH DISSOCIATION A general hydrocarbon fuel can be defined as C. C O + . 2 and a2 a .)H. 2 2 1 a (12.29) gives O. + nCO (12.2 RICH MIXTURE WITH DISSOCIATION Equation without dissociation: (1 + n)CO + .224 Chemical equilibrium and dissociation Adding eqns (12.76N2) Y Y + x ( l .+3. (12.a. (12.H.0.32) 12.H.28) and (12.33) a1 a .
1 Effect of dissociation on combustion Having introduced the concept of dissociation it is necessary to evolve a method that allows the value of the degree of dissociation. and eqns (12. hence dissociation always reduces the effect of the desired reaction.g.36) If the mixture were not stoichiometric then eqn (12. This method will be developed in the following sections. dC).36) would also be modified. e.I&)then eqn (12.)C02 + 3(1. 12. . In eqn (12.36) the combination of nitrogen and oxygen has been neglected. = 0.4 GENERAL OBSERVATION As a result of dissociation there is always some oxidant in the products.33) would be modified to take account of the airfuel ratio.2N2 (12. It was previously shown that for a system at constant pressure and temperature to be in an equilibrium state it must have a minimum value of Gibbs energy i. 12.a.1). if the reaction is exothermic then dissociation reduces the energy released (see Fig 12. to be calculated.76N2) *6(1 + a.35) and (12.e.Calculation of chemical equilibrium and the law of mass action 225 If the fuel was benzene (C. a. and the particular case of the CO + io2 reaction will be shown in brackets { ). This will also be introduced later. + 1. / Reactants Fig.CO + 3a2H2+(3a. In many combustion processes the oxygen and nitrogen join together at high temperatures to form compounds of these elements: one of these compounds is nitric oxide (NO).)H. 12.4. and the equations can be extended to include this reaction.O + 6a. These equations are returned to in the later examples.35) would become cfjI& + 7.5(O2 + 3..5a2)02 28..5 Calculation of chemical equilibrium and the law of mass action General relationships will be derived.
dm.p.. . two reactants and two products..37) where m ..co2 t f (12. m. A + (1 . the mass form of the equation (eqn 12.39) where stoichiometric coefficients equal to unity are implicit. + p2 dm.&)YJ &VcC f EVd D (12. it is necessary to locate when Now dG = V dp .5a) will be replaced by the mole form of the equation (eqn 12.42) From here on. For the purposes of evaluating the dissociation phenomena it is possible to consider the reaction occurring at constant temperature and pressure (equal to values obtained by other means or calculated by an implicit iterative technique). because this is more appropriate for chemical reactions.E ) Ybpb +Evcpc +EVdpd] (12. the degree of dissociation. by definition. = p i dm. (12. The equilibrium equation for the complete reaction is IC0 + 1 1 0. dm. are the masses (or amounts) of the possible constituents of the mixture. + ( l . Only four constituents will be considered during this discussion.S dT+ C p ... + " ' p .. m2. =pl (12. but the theory can be extended to any number of constituents. The Gibbs energy of the system may be described by the following equation: G = ( l . E is known as the fraction ofreaction and is an instantaneous value during the reaction as opposed to a . + p2 dm. i.e. dm. (12.E) Yap.41) dm.40) To find the equilibrium condition while maintaining pressure and temperature constant. this function has to be minimised with respect to E .&)Y. which is a final equilibrium value. The use of E allows the changes in Gibbs energy to be considered as the reaction progresses. + .5b). .38) At some intermediate stage in the reaction the state may be represented as Y. and dG). A + Y b B * (1 ..226 Chemical equilibrium and dissociation But. for a system at constant pressure and temperature dG)...
e.45) (12.43) where A. and is the value of p at temperature T and the datum pressure. 227 namely ( 12.49) is the ratio of the partial pressure of the individual constituent to the datum pressure. dE and applying similar techniques ( 12.~ ~ P ~ .50) Po= Po + PU1 and is called the standard chemical potential. = . B.48) Since where = g it is possible to describe . Hence giving = vapa . Substituting for p in the equilibrium equation. at equilibrium +v b p b = vcPc+ vdpd (12. + C nd= &Vd+D E.Calculation o chemical equilibrium and the law o mass action f f It is possible to relate the amount of substance of each constituent in terms of n.vc ~ p r c .vbpb + vcPc + vdpd =0 for equilibrium (12.49) (12. in a similar way to g.52) . changes are constrained by the stoichiometry). = EV.d P I n)p+ o +vblnpr. po.47) i.&)vb+ B n. + A nb = (1 .51) which can be rearranged to give ( v a P ~ + v b p ~ .E ) Y . eqn (12. = po+ %T u In pr (12.v.44) This is known as the equation of constraint because it states that the changes of amount of substance (or mass) must be related to the stoichiometric equation (i. namely u .v d I n p r d ) = 0 ~ r S~(v~ (12.. Hence dn.e. The value of pressure to be used in eqn (12. C and D allow for the excess amount of substance in nonstoichiometric mixtures.= (1 .48) va(p: + BT In pro) + v b ( P l + ST In prb)= vc(p:+ S T In prc) + vd(p:+ S T In p r d ) (12.
If the amounts of substance of reactants and products .57) i. The nondimensional equilibrium constant is defined as InK.e. p". is related to the datum pressure used to define pO.53) is the difference in the standard chemical potentials at the reference pressure p 0 of 1 bar or 1 atmosphere.56) shows that the numerical value of K .59) Now AG: is a function of T alone (having been defined at a standard pressure.228 Chemical equilibrium and dissociation Hence 1 The lefthand side of eqn (12.. = f ( T ) .58) K . (1 2.56) K p r is called the equilibrium consfanf. therefore K ..55) giving (12. p o ) . . Sometimes the equilibrium constant is defined as = yap: + v b p .pgu = + 'b  'c "d) or K p= Kpr/pgo + 'b "c .vdp: (12. This is defined as AG: Hence (12.u:. and is a dimensionless value.54) (12. Equation (12."d) (12. has the dimensions of pressure to the power of the sum of the stoichiometric coefficients. Kpr K.. = 3iT AG.e. i.v.
This can be written. 12.OCO.66) .62) The above expressions are known as the law of mass action. as is the case for the CO + :O.v . K.38) and (12.& ) A+ ( 1 . It is instructive to examine how the Gibbs energy of a mixture varies with composition at constant temperature and pressure.60) Hence.64) ( 12. DEFINED IN TERMS OF MOLE FRACTION The definition of partial pressure is Pa=XaP ( 1 2.=O. However.60) gives (12. 12. the value of equilibrium constant.E).57) and (12.+ 2~p.CO.U. This is a slightly simplified form of eqns (12.vd= 0). can combine chemically to produce compound C.+H.49) and (12.&). then the value of K. as G = ( 1 .39).~ ) p t +1 .Variation of Gibbs energy with composition 229 are the same then the value of K.E ) ~ : + % Tn p r o +( 1 . + ( 1 . dG).is the same for the water gas reaction (CO+H.DE +%T In p r h + 2 & ( p .] ( + 2~ (12. Hence. if the amounts of substance of products and reactants are not equal.1 K . (12. defined by the fraction of reaction.0] % T [ ( l .50).6 Variation of Gibbs energy with composition Equations (12..5. i. If the chemical equation is A+B*2C then at some point in the reaction. which can be defined in terms of the partial pressures or mole fractions of the constituents of the mixture.E ) B+ 2&C E. . replacing the terms for partial pressure in eqn (12.. the equilibrium constant was evaluated by equating the change of Gibbs energy at constant pressure and temperature to zero. in terms of mole fraction: (12. by substituting for p from eqns (12.57) by the definition in eqn (12..&)lnp. Assume that two components of a mixture.63) the chemical (12.e.65) and the Gibbs energy is G=(1E)pa+(1&)pb+2&p.) l In = [ ( l .62) show that the equilibrium composition of a mixture is defined by the equilibrium constant... is not affected by the datum pressure (because v a+ vb. A and B .&)lnprb+ In p.. + % T p. reaction.) in both SI and Imperial units because Kp is dimensionless in this case. will be dependent on the units of pressure. composition is ( 1 .61) which results in the following expression for K.
The standard chemical potential of compound C is less than the sum of the standard chemical potentials of A and B.&)p:+ 2Ep3 + rnT[(l .E ) + 2 E I h p . and the sum of the terms is also shown. (12. The third term defines the change in chemical potential due to mixing.69) [ Equation (12.69) consists of three terms. and the mole fractions of the constituents are I& xa = .2p:] + 2RTlnpr + 2%T (1 .67) Substituting these terms in eqn (12.E ) + (1 .However.&)ln ('. If the two terms are added together then the variation of G .78. which obeys the law of mass action.68) Equation (12.60) as p i = x i p .2p: = (1 . E. this term varies linearly with the fraction of reaction. The first term is the difference between the standard chemical potentials of the separate components (p: + pt) before any reaction has occurred. It can be seen that for this example the equilibrium composition is at E = 0. The manner in which the first and third terms might vary is shown in Fig 12.230 Chemical equilibrium ana' dissociation The partial pressures are defined by eqn (12. and is a function of the way in f which the entropy o the mixture (not the specific entropy) varies as the reaction progresses. giving G . = 2= E E 2 2 (12.68) can be rearranged to show the variation of the Gibbs energy of the mixture as the reaction progresses from the reactants A and B to the products C by subtracting 2p: from the lefthand side.')+&h&] (12.66) gives = [(l  + (1 . the term based on the mole fractions varies nonmonotonically. and hence the reaction will tend to go in the direction shown in eqn (12.2.63). as the reaction progresses. x . . the second one simply shows the effect of pressure and will be neglected in the following discussion. and this affects the composition of the mixture. This figure illustrates that the Gibbs energy of the mixture initially reduces as the composition of the mixture goes from A + B to C. as shown by the line labelled 2%+1 &)h(+)+ &h&]. C.&)[/A.2pz with E is obtained. and the standard chemical potential of the mixture (2~:)after the reaction is complete. It can be . + p . If the standard chemical potentials were the only parameters of importance in the reaction then the reactants A and B would be completely transformed to the product. Since the standard chemical potentials are constant throughout this isothermal process. 2 'b = 1E .
00 Fraction of reaction Fig. . the ratio of the partial pressures in the equilibrium state is known. Some examples of dissociation are given later. is known.70) Thus. v q = l/2. the steeper the slope of the line PQ) then the larger is the fraction of reaction to achieve an equilibrium composition. KPr = Prco & (12. 2 vco= 1.1).7 Examples of significance of Kp 12. if K.vco2=1 Hence Prco.50 1. 12.2 Variation of the Gibbs energy of a mixture 12. This is to be expected because the driving force for the reaction has been increased. Standard Gibbs Energy of mixing of A and B 2RT[(l&)ln((l~)n)I~~] ? Gibbs Energy of mixture 2 0. 1 co+oo.*co.Examples of significance of K p 23 1 seen that the larger the difference between the standard chemical potentials (i.1 EXAMPLEI Consider the reaction in eqn (12.e. and these can be more readily understood if this section is borne in mind.00 0.7.
74) In this reaction the amount of substance in the products is equal to the amount of substance in the reactants. Equations (12. 2 1a nco.73)).232 Chemical equilibrium and dissociation It would be convenient to manipulate this expression into a more useful form. a .1)) and the water gas reactions (eqn (12. p p Po 1 + a / 2 Po (12.73) By the law of mass action (12. for this reaction.1) was .0. is known. a . This is because the amount of substance of products is not equal to the amount of substance of reactants. (eqn (12. and there is no effect of pressure in the dissociation equation. 12.0.27)): 1 CO + . to be evaluated if K .7.71) Hence.(12 then Prco. through the following equation (12.O (12.72b) The relationship between Kh and a allows the degree of dissociation.eCO+H. is a function of the degree of dissociation and also the pressure of the mixture.2 EXAMPLE 2 Consider the watergas reaction CO.=nP a a)CO. the value of K .+H. + a C O + .72) shows that. Comparing the results for the carbon monoxide. the value of K . Consider the general reaction equation for the carbon monoxide and oxygen reaction (eqn (12. it can be seen that if a mixture of products of the reaction in eqn (12.72a) l+a/2 and a (12. = . can be related to the degree of dissociation.
the chemical composition of the mixture would change. Most combustion processes have more than one chemical reaction. The first approach. The second approach is more appropriate for computer programs because it enables a set of simultaneous (usually nonlinear) equations to be defined. and to then ensure that this obeys the energy equation (i. is described in section 12.(Q + 3. [There are two different approaches for solving this type of problem. At this stage the value of K . Calculate the maximum pressure and temperature achieved if dissociation occurs. Solution Note that there is only one reaction involved in this problem. The following examples show how this can be achieved. ] General considerations The products of combustion with dissociation have to obey all of the laws which define the conditions of the products of combustion without dissociation.3 EXAMPLE I : A ONE DEGREE OF DISSOCIATION EXAMPLE A spark ignition engine operates on a 10% rich mixture of carbon monoxide (CO) and air. K. which develops the chemical equations from the degrees of dissociation is often the easier method for hand calculations because it is usually possible to estimate the degree of dissociation with reasonable accuracy. and that the carbon monoxide converts to carbon dioxide in a single step. This means that the problem becomes one with two iterative loops: it is necessary to evaluate the degree of dissociation from the chemical equation and the equilibrium constant.1CO + .75) Rich combustion equation: 1 1. 12. and it can also be assumed that the degree of dissociation of the water vapour is less than that of the carbon dioxide. and K.8.(Q + 3.48 C 0 2 + 0.98 . The conditions at the end of compression are 8.76) n p = 2.88N2 3 (12.5 bar and 600 K.3. 233 subjected to a change in pressure.38 3 CO.88 N2 n p = 2. plus the ratios of constituents defined by the equilibrium constant. at different temperatures will simply be stated. values are listed in Table 12. and it can be assumed that the combustion is adiabatic and at constant volume. .76N2) L n R = 3. + 1.7. described in Chapter 10.e. The method of calculation K.1CO + l. the First Law of Thermodynamics). These points are returned to later in this section. Stoichiometric combustion equation: 1 CO + .76N2) 2 nR = 3.88 (12. both of these will be outlined below.Examples of significance of K. whereas the chemical composition of the products of the water gas reaction would be the same at any pressure.
p l V l = nl%T.+(O. T2.54 + 0.1a . p2V2= n2%T2.70): . 2 T t l combustion equation with dissociation oa 1 a l.82) gives 0 = 497.82) Expanding eqn (12.=xo2 .77 . = f ( T 2 ) . as X gives X(O. = (P/Po)co<P/Po)bI: The values of partial pressures in the products are Pro2  P2 1a P2. P2 a P2 .2XT2).65 aT2 ”) (12.65 72 (12. (P/Po)co2 KP.a3XT2 (12.1 + a ) ( 2nP Po a p2 )’ a K:r = (1 .O.Writing Ki. is given by eqn (12. T.79) n p _=_ .a(995. substituting these values in eqn (12.lCO+(Q+3.= Po Po n Po P .0.= Po Po 2nP Po (12.a)’ x 2 x 245. and Thus (12.= P2 Po Po n P Po Po.88N2 (12.83) . P2 245.234 Chemical equilibrium ana‘ dissociation Dissociation of C 0 2(eqn (12.65 x 1. = xco .70) gives (1 4 KPr= (0.78) Also.81) This is an implicit equation in the product’s temperature.n.l+a)CO+02+ 2 2 nR = 3.1 + a)’ ( 2 x 245. from the ideal gas law.77 .a)’x 2 x 2 4 5 .013 25 =( (12.01XT2)+ a’(497.80) PI 72 Hence.29)): a a C 0 2 a a C 0 + .9 PCO P2 0.48 np = 2.76N2)(1a)CO.98 + a12 1.77) The equilibrium constant. xco2 .because K .a)’ (0. K . 6 5 ~ ~ 1 .l + a)’aT2 = ( 1 .
Examples of significance of K p 235 The term XT. i.~ R ( T .1218125 0.84) NOWUR(TR)is constant and is given by Constituent ~soo co 12 626.1218125 3000 0. can be evaluated for various temperatures because XT.171875 Evaluating the energy which is contained in the products at 2900 K and 3000 K.a ) x 276 960 + 43 993 kJ (12. equation but they do not all obey the energy equation.85) It can be seen that the value of Up is a function of a.(TR) (e. may be rewritten 0 = Avo . the reason for this is because the combustion of the fuel (CO) is not complete when dissociation occurs. Up(Tp)= (1 . based on the internal energy of reaction at T = 0.+ (12.88 n 12 939.171875 2800 2900 3000 These values of a all obey the chemical. balances an equation of the form UP('. single degree of freedom reaction like this. = G T .1 0 2 NZ 12 571.e.)= [ U R ( T R ) .) ) This energy equation.582 121 303 4.Up(Tp)+ U.4 kJ Hence.013 27 234 Solving for a at each temperature gives T P a 0.090625 2900 0. In a simple.2 1. allowing for the variation in a as the temperature changes.392 55 940 3.>. : 2800 2900 3000 6.5 UR(TR) = 43 993.7 1. gives .f IUP(T. the reduction in energy released is directly related to the progress of the reaction: T P a UPVP) 295 853 287 216 273 351 2800 0. dissociation.6 0. It is necessary to consider the energy equation now to check which value of T.090625 0.
2281 0.6 73 597. 288000 .88 Lrp(Tp)= 285 521 kJ These values are plotted in Fig 12.0747 0 2 + 1. the chemical equation.1CO + .80) and the tables of energies First. it is necessary to evaluate the degree of dissociation that will occur at this product temperature.085 94 1. Kpr= 3.76 N2) 0.1494.3 Energy contained in products based on eqn (12.2494 CO + 0.(Tp) = 275 405 kJ Tp= 3000 K Constituent u3wo C02 CO 0 2 N2 n 137 320 77 277 81 863 76 468 0. 286000 az .3 74 388.62613 (see Table 12.5 0. and it can be seen that. if the variation of the energy terms was linear with temperature.2719 0.3. and this can be substituted into eqn (12.8281 0. + 0.( 0 2 2 + 3. is 1 1. 12. At Tp= 2950 K.871875 0.78) to give a = 0. The calculation will be repeated to show how well this result satisfies both the energy and dissociation equations. taking account of dissociation.8506 CO. 9 8 280000 278000 276000 274000 LlLVYY ~ ~ 2900 2910 2920 2930 2940 2950 2960 2970 2980 2990 3000 Temperature / (K) Fig.88 U. * v) 284000 282000 = ' z w e.9 78 706.236 Chemical equilibrium and dissociation Tp = 2900 K Constituent u2900 n C02 co 0 2 N* 131 933. the temperature of the products after dissociation would be 2949 K.88N2 Applying the energy equation: the energy released by the combustion process gives a .3). Hence.0641 1.
a ) K i r = a 2 1 pP 2 Po n P (12.2494 0.48 1 + bCO + c 0 2 + d N 2 n p = a+ b+ c + d (12.5(1 .87~) Total amount of substance in the products.a ) x 276 960 + 43 993 = 279 575 kJ ) This energy is contained in the products as shown in the following table: Constituent ’2949 CO.1488. from the atomic balances.1CO + A (Q + 3.91) The previous calculations showed that the temperature of the products which satisfies the governing equations is Tp= 2950 K. a . this can be written in terms of a as (1. The chemical equation which was written in terms of a in eqn (12.86) Considering the atomic balances.1 = 2 a + b + 2c 1. n p =a + b + c + d (12. and this is close enough for this example.Examples of significance of Kp 237 product energy of U P ( T p= (1 . These values . will not be introduced explicitly.a giving c = 0. r = a 2 pp Po n P and.77) can be written as 1.l=a+b 2.76N2)aCO. N2 n 135 182 75 820 80 205 75 040 0.88 Up(T. CO 0.8506 0.) = 280 961 kJ The equations are balanced to within O S % .87b) (12.88) The ratios of the amounts of substance in the equilibrium products are defined by the equilibrium constant (12.1 . Alternative method In this approach the degree of dissociation.0747 1.a ) (12. which gives a value of KZr= 13.(1 .90) (12.87a) (12.88 = d giving b = 1.89) Hence b2c K . 2 n R = 3. Carbon: Oxygen: Nitrogen: l.1 .a ) 2 .
giving  pP p p .65~'.238 Chernicai equilibrium and dissociation will be used to demonstrate this example. Then { 1. The advantage of this approach is that it is possible to derive a set of simultaneous equations which define the equilibrium state.2.2a + a* .8506.= T T (12..(02 + 3. 9 5 3 ~ ~ + =0 The solution to this equation is a = 0. 2 3 ~ 251. . and the solutions obtained from the original method were simply used for the first 'iteration'.532 . It must be recognised that the full range of iteration was not used in this demonstration. + h(T) .95) Thus (12.7 8 . 12.2a2+ a 3 ) }pp x Po n P 13.T {so + s(T)] = h. The disadvantage is that it is not possible to use the intuition that most engineers can adopt to simplify the solution technique. and hence the chemical equation becomes 1 1.lCO + . p0 = ho + h(T) .2 6 9 .from the perfect gas relationship.2494CO + 0.T P.92) It is possible to evaluate the ratio pp/pon.76N.T s .(1.59)) (12.)+0.T I  dh T (12. 4 8 ~ 6 0 0 (12. and these can be easily solved by a computer program.8 The Wan't Hoff relationship between equilibrium constant and heat of reaction It has been shown that (eqn (12.96) Consider the definition of p0.074702 + 1.8506CO2 + 0..98) .21 .88N2 2 (12.97) Consider the terms dh h(T)T/ .94) which is the same as that obtained previously.1488 2 =a (12.009 ponP nRTR 3 .93) This enables a cubic equation in a to be obtained: 95.21a + 2.8 5 x 2 9 5 0 = 12.
and are listed in Table 12.9 The effect of pressure and temperature on degree of dissociation 12.9.101) (12.(y.( InKpr) = dT %T2 ( 12.62). and it can be seen that over a small range of temperature. In Kp= A . Thus d 1 . The values of Kphave been calculated using eqn (12.The effect of pressure and temperature on degree of dissociation 239 Let v = h(T). It is useful for evaluating the heat of reaction for any particular reaction because The value of d(ln Kp)/d(l/T) may be obtained by plotting a graph of In Kp against 1/T. h.6.103) Equation (12.102) d QP . . for four reactions.103) is known as the Van't Hoff equation. 12. where T is the temperature in K: this is to be expected from eqn (12.95).100) Although C has been used as a shorthand form it does include both +ve and ve signs.99) (12.yc h.95)). these must be taken into account when evaluating the significance of the term.b/T. dv = dg u= 1 T' dT d u = T2 Integrating by parts gives (12.vdhd) dT %T2 (12. + Vb hb . (The values have also been depicted as a graph in Fig 12.3.( h K p r )= .1 The effect of pressure The effect of pressure on the degree of dissociation is defined by eqn (12. at the end of the chapter. namely. .
9558 0..105) where a . Total amount of substance No dissociation 1 0 2 0 0 _______ 1 0. However.0. + a. The basic rule is that the effect of increasing the pressure is to shift the equilibrium to reduce the total amount of substance.v b < 0. If v.1335 1.0444 7.)CO.52 0.v.1.7829 0.6685 100 0.27) was 1 CO + .v.vb = 0 then the mole fractions of the products will not be a function of pressure.2258 7.O Amount of H.52 10. + v d .00 Pressure (bar) Amount of C 0 2 Amount of CO Amount of H.v b > 0 then the species on the lefthand side of the chemical equation (i.e. a / y . . + 3.52 10. the reactants) increase. . It can be seen that dissociation tends to increase the Table 12. Amount of N.1 Amount of products for constant pressure combustion of methane in air. 2 a and the equilibrium equation (12.6091 . / 2 + a.a _1 1 1+a/2 + _/ 2 /~ l & a y a .a.CO + 2(1. + v d . if v.< 0 then the species on the righthand side of the equation (i.H2 + ( a .5.6823 0.v.76N2) 3 (1 . and this would result in the constituents on the ‘products’ side of the equation increasing. This is in agreement with the previous statement because the total amounts of reactants in eqn (12.2170 1.0801 0. . A similar calculation for the combustion and dissociation of a stoichiometric methane ( C h ) and air mixture. reaction and a2 is the degree of dissociation of the H. + 2(0.1343 0. performed using a computer program entitled EQUIL2 gave the results in Table 12. Considering the two reactions introduced previously.v. This means that v.104) This can be interpreted in the following way.52N2 (12.8654 0.0.52 10.1485 7.240 Chemical equilibrium and dissociation It can be seen that the ratio of the amounts of substance is given by ( 12. The equation for the carbon monoxide reaction (12.920 0.72) was KPr= _ . equivalence ratio = 1.v. + v d .3170 1.e. Amount of 0. .52 10.)O.8665 0. the products) increase.Q . + 7.( 1 2 a)CO. Initial temperature = 1000 K.)H. + aCO + .+ v d . is the degree of dissociation of the CO. whereas if Y.O + 2a.O reaction. whilst the total amounts of products is 1 + a / 2 . The chemical equation for this reaction is CH.a.~1 .27) is 1. where a is less than 1.7448 10 0.0889 7.
The minimum total amount of substance occurs when there is no dissociation.5. dissociation at p = 10 bar.2 THE EFFECT OF TEMPERATURE The effect of temperature can be considered in a similar way to the effect of pressure.55) must get smaller relative to the denominator. and that related to partial pressure (see Fig 12. H2 (go = 0).. This effect can be seen quite clearly in Table 12.2. This is borne out i Table 12. This means that the numerator of eqn (12. and to realise that for gases with negative heats of formation an increase in temperature leads to a decrease in the value of K .2). Basically it should be remembered that the changes in composition that take place during dissociation do so to achieve the minimum value of Gibbs energy for the mixture. the constituents with the most positive heats of formation are favoured. Another way of considering this effect is simply to study eqn (12. Both water and carbon dioxide have larger (negative) values of g.4 shows how the degrees of dissociation for the carbon dioxide and water reactions vary with pressure. the Gibbs energy at absolute zero (gn).113 MJ/kmol). where the amount of substance of products is compared under four sets of conditions: no dissociation. which pushes the reaction backwards towards the reactants. The equilibrium point is achieved when the sum of these values for all the constituents is a minimum. and dissociation at p = 100 bar. while the maximum amount of substance occurs at the lowest pressure.55). dissociation at p = 1 bar. This effect can be seen from the results in Table 12.9. Figure 12. and this is shown in Fig 12. the Gibbs energy as a function of temperature ( g ( T ) ) .The effect of pressure and temperature on degree of dissociation 241 amount of substance of products. These constituents include 0. The Gibbs energy of each constituent is made up of three components. 12. and CO (go = . and hence the effect of an increase in pressure should be to reduce the degree of dissociation.1. This means that. . whch have been calculated for the combustion of methane in air.2: the degree of n dissociation for this reaction increases with temperature. . as the temperature rises. (go= 0).
8654 0. =2 N 0 This chain of reactions has to include the formation of atomic oxygen and nitrogen.2 Amount of products for constant pressure combustion of methane in air.52 10.52 10.5855 7.5 Effect of temperature on degree of dissociation Finally. Pressure = 1 bar. Amount of CO Amount of H. While it is possible to add the calculation of NO to a simple dissociation problem.52 11.4 . as is done in Example 5 below.3031 0.10 Dissociation calculationsfor the evaluation of nitric oxide If it is necessary to evaluate the formation of nitric oxide (NO) in a combustion chamber then the equations have to be extended to include many more species.9132 T=2000K 0.4741 0.2258 7.3933 7. and .52 10.Q E 0 .* 05 04  v) z 03 .6823 0.52 07  06 c m .1343 0. Amount of N.7320 0.2679 0.3170 1.5186 1.6969 1.O Amount of H. it should be noted that in al the cases shown the degree of dissociation in the l hydrogen reaction is much less than that for the carbon reaction. 12.+ I I I Carbon dioxide Water 2 02 01 1 I I I I 0 + 1000 I 1 I100 1200 1300 1400 1500 I600 1700 1800 1900 2000 Temperature / (K) Fig. Total amount of substance No dissociation T=1000K 0.7448 T=1500K 0. The reason for this is that NO is formed by a chain of reactions that are more complex than simply N. 12. this does not result in an accurate estimate of the quantity of NO formed. This supports the assumption made in previous work that the hydrogen will be favoured in the oxidation process.5258 0. + 0.242 Chemical equilibrium and dissociation Table 12. Amount of 0. equivalence ratio = 1 Temperature (K) Amount of CO.1055 1 0 2 0 0 7.48 14 0.
. E21 H2.1 06) where b = xi/. [81 CO2. a standard pressure. with temperature 26 at for the reactions CO + 0. E51 N2. E11 1 0 . Variation of equilibrium constant. H2 + f 0.. 1 .. 171 N.O. E91 COS [41 H. The formation and breakdown of these species are defined by the following set of equations: ( 12. [61 NO. To obtain an accurate prediction of the NO concentration a total of 12 species has be considered: [11 H20.~ 0 500 1000 1500 2000 2500 3000 3500 Temperature / (K) Fig. Kh. f N.. NO. [lo1 0 2 . E121 Ar. [31 OH. + H2w CO + H.e CO.w HzO. CO. + 10. 106 1os io4 1 o3 102 101 100 101 102 1o .The effect of pressure ana' temperature on degree of dissociation 243 also the OH radical. p o = 1 bar. The numbers in [ ] will be used to identify the species in later equations.
N Mol fraction .Mol fraction Mol fraction  0.
3.7(c). but with the addition of data for OH and N. 12. The conditions are the same as quoted in Heywood (1988). with an equivalence ratio of 0.1 EXAMPLE 4: COMBUSTION OF A TYPICAL HYDROCARBON FUEL A weak mixture of octane (C. shows the fundamental techniques involved in calculating dissociation but is an unrealistic example because rarely are single component fuels burned. There are also significant amounts of OH and oxygen over the whole range of equivalence ratio.H.Dissociation problems with two. but this rapidly reduces to a very low value at stoichiometric simply because there is no oxygen available to combine with the nitrogen. Figure 12. Figure 12. shown in Fig 12. The diagrams shown in Fig 12. which considered the dissociation of carbon monoxide. it would be necessary to consider other ‘dissociation’ reactions because it is likely that nitric oxide (NO) will be formed from the combination of the oxygen and nitrogen in the combustion chamber. and CO is prevalent throughout the weak mixture zone. Assuming the combustion is adiabatic.) and air. or more. Some nitric oxide is formed in the weak region (xNo= 3 x at the weakest mixture). by this temperature. there is a further tripling of the NO production. is ignited at 10 bar and 500 K and bums at constant volume. they do allow the parameters which control the production of the products of combustion to be decoupled. The equilibrium concentrations depicted in Fig 12.7(a) shows the results for the lowest temperature of 1750 K. or more. this is because. as is indicated by the increase in the CO and the OH radical in the weak mixture region.7 shows the results of performing such calculations using a simple computer program. Figure 12. By the time 2750 K is reached. degrees of dissociation The previous example.9. calculate the conditions at the end of combustion allowing for dissociation of the carbon dioxide and water. It is apparent from this diagram that there is not much dissociation of the carbon dioxide or water because the concentration of oxygen drops to very low values above I$ = 1.7 are the values which drive the formation of the exhaust constituents through the chemical kinetics equations. which will be discussed in Chapter 14. at different temperatures.11 Dissociation problems with two. but neglecting any formation of NO. 12. The three diagrams are based on combustion of octane in air at a constant pressure of 30 bar. There is also some NO formed by combustion with rich mixtures. I $ . Even if a single component fuel such as hydrogen was burned in an engine.7 are relatively contrived because they do not depict real combustion situations. These more complex examples will be considered here. degrees of dissociation 245 A numerical method for solving these equations is given in Horlock and Winterbone (1986). the carbon dioxide and water are dissociating. to show the effects of changing the parameters independently of each other. and it can be seen that the NO level has increased by almost a factor of 10. and show the effect of varying equivalence ratio. The coefficients in the program were evaluated using the data presented in Table 9. However. based on the original paper by Lavoie et al.7(b) shows similar graphs for a temperature of 2250 K.11.. . and it can be seen that the graph contains no atomic nitrogen (N) or atomic oxygen (0)because these are at very low concentrations When the mixture is weak some OH is produced. (1970).
5(02+ 3.107) Weak mixture neglecting dissociation + C8H18 13.222N2 nR= 67.389 + 4a1+ 4 . + 3.8295 Prco PrH*O Prco.a.222N2 + (12.38900.109).O + + 8alC0 8 2 0. 52.+4.108) Dissociation equations (12. The equilibrium constants from Table 12. = Prco Pro. H .1 1 1 np= 70. KP. + 9H. = 112 KPd = = 6.110) = 6.O np=64 + 47 N. 2 a . the partial pressures of the constituents are Prco. 0 ~ a . Prco Pro. + 9H@ + 1. Dissociation will lower the final temperature: assume that Tp= 2800 K. 2 Weak mixture including dissociation is a 2 a 1 C8H.) ~~ p nP Po P r H z =  nP Po .889(02+ 3.3 at 2800 K are Prco. 5 ~ .)H. Prnz From eqn (12.481 bar respectively.0.o = 9(1 a.a 1 ) C 0 2 9(1 .58152 (12.611 +4a.1 I 1 8(1 .109) np= 70.5 SCO. (12.246 Chemical equilibrium and dissociation Solution Stoichiometric equation neglecting dissociation C8Hls+ 12.61 1 ( 12.. P np PO Po Prn.889(0.5a2 The temperature and pressure calculated for combustion without dissociation are 2874 K and 60. + . H . + 13.25 and 12.76N2) n R = 67.34): + a l C O .76N2) nR = 60. ~ a l C O .. + 52.0. 8(1 a11 P n P Sa.) P np 9a2 P PO =  = (1.76N2) 3 K O .
.nR& (12.136CQ + 8.89940. Based on this assumption the value of a 1 is approximately 0.846CO .ah2 67.108 a 2= 0.15678 H.58a:+ a:(49.. or more. .652~1..389 + 4Ql + 4 .H.117) This equation contains both a 1and a2. 5 ~ 2 )p (12.Dissociation problems with two.5~12) which can be expanded to give 144.all2 a: Po (1.109)) which becomes C.3164 = (1 .111 x 500 a:(1.3164 = and [8(1 . degrees of dissociation 247 Hence Ki. Recalculation around this loop gives a . 3 8 9 + 4 a 1 + 4 . 0. = 43. = 0. Substituting this value in eqn (12.= 43.3164 x 10 x 2800 (1 .c.O + 0.222N2 +np=71.112) gives a2= 0.84322H.889(0.121 (12. Then PPVP = nP8TP PRVR = n 8 T R Thus nP =.111 + 7..76N2) nR=67.117) is a cubic equation in a l .11.nR3& P P (12. 5 Q ~ ) p ~ T p nR T R (12.1 14) PRSTP PRTP Substituting gives K.)+ 2 a .is can be replaced by the temperature of the products by applying the perfect gas law to the mixture.017776.1 12) The Kprequation (eqn (12. + 13. + 1.389 + 4 a l + 4.115) Inserting values for these parameters gives 43.If it is assumed that a 1>> a2then eqn (12.111) (12. but .113) .1 11)) contains a pressure term.2052 (12. which vindicates the original assumption.118) . and for the chemical equation (eqn (12. + 3.01742 These values are close enough solutions for the dissociation coefficients.116) + 162.aJI2 n P Po [8a1]* ( 1 . + 52.1 = 0 (12.
84322 x 7223.(5779 + 13. 0 1 7 4 2 ~ 9(241 827) ~ ~ = = 5 116 320 + 244 505. is not the full value of the internal energy of reaction of octane because not all the octane has been oxidised fully to CO.846(AU.0 .889 x [6032.).O . and water. is that with dissociation. the fuel properties have been based on methane): (Qv)s + [Up(Ts) .8 + 0.248 Chemical equilibrium and dissociation This equation satisfies the equilibrium constraints and the chemistry of the problem.121) This value can be related to the energy released at the standard temperature of 25°C by the following equation (*note. The value of ( QV)? this case is given by in (Q.3 52.8 .1 19) Note two things about this equation.(74 897)* = 4 943 040 W/kmol C.15678 x 6043.6 4 833 900.120) Alternative method for calculating the energy released by combustion The energy released from partial combustion can be calculated using Hess' law.136~ (393 4 0 5 ) + 8 . 8 4 3 2 2 ~ (239 082) + 0.(AUO)CxHIx =7.889 N* 10 356..o . ) .120)..).1 6025.122) = 4 895 205 kJ/kmol C.136(AUo)oz+ 8. 0 2 10 574. .81) (12. that it is more convenient to evaluate the difference between the internal energies of the products..0 4542.5 kJ/kmol octane (12.H.222 Difference n 45 783 0 45 783 1 . (Q. because now the composition of the products is also a function of temperature and hence Up(Ts) not a constant. l 0 8 ~ 8 (282 9 9 3 ) .6 + 8.8 6032.846 x 601 1..9 + 37 913. First.8994 x 6032. and is probably because of the approximation made for the properties of octane.222 x 6025.113 882) ..= ( Q .0 + 52. in eqn (12.0 + 3.UP(TO)I [UR(TS) UR(TO)I = 4 943 040 + 7. burned (12. burned = This is within 1. In this case Products Reactants = 7.846 x ( .3 + 0. Second. but it still has to be checked to see if it meets the First Law.1 + 1.8 13.25% of that calculated from the internal energy of reaction. The First Law is defined by the equation ( 12.76 x 6025.8 4330.H.843 22(AUo)H20+ 0.136 x 7041.H.). Evaluating the energy terms for the reactants gives Constituent U5(x) U29x C.
0 69 516. np=71.4 52.5 8.111 x 500 and hence 183.1 24) 22 KPrZ 6.1404 H.8 65 500.x (6. and it will be shown that this gives good agreement in the energy equation: Tp= 2772 K will be used. ~ ~ H2O co 71 512.123) Evaluating the energy contained in the products at 2800 K gives Constituent _ _ _ _ _ _ ~ ~ ~ CO.84322 66 383.Dissociation problems with two.8 7223.8472 0 .389 + 4 a l +4.82925 .838 (1 all2 a:(1.14828) = 7.127) j 7.8. = 0. or more.O + 0.6.2 + 335 014 = 516 8731 W (12.864 H2 0 2 N2 u28W u29X Difference n 127 154.5~1~) (12.1 1.5 k J This shows that the products at 2800 K contain more energy than was available from the energy released by the fuel and hence the energy equation has not been satisfied. .72829 + .5 0.6 120 113. the value obtained from a computer program will be used immediately.15678 75 548.Up(T.) = (&A + EU.(TR) .(Ts)I = 4 833 716. + 1.125) + 206.8994 70 754.222 Up(Tp) .6352 x 10 x 2772 67.8 64 728.1 6032. degrees of dissociation 249 Hence.0156 which give a chemical equation of (12.128) .776 CO + 0. + 52.1360 100 470.6 6043.58152 .) + 2 a . must be UPVP)  UP(T.U. At Tp= 2772 K the values of equilibrium constant can be obtained from the tables by linear interpolation: 22 Kpr.1 6025. Recalculation around the loop results in the values a .3 93 247.097 a2= 0.8596 H.126) Assuming a2= 0 for the initial iteration gives a 1= 0.4 6011.3 7. based on the evaluated degrees of dissociation.x (6. the energy of the products.5 0.222 N. 8.224CQ + 8.14828 + .84a:+ a:(62.4589 = 50 ( 12.7727 = 50 Substituting these values gives 55.72829) = 6.061 (12.099.1 = 0 ( 12.1 60 340. Rather than do a number of iterations. It is necessary to repeat the whole calculation with a lower temperature guessed for the products.) = 5 260 072.9 7041.82a.
250 Chemical equilibrium and dissociation The energy released by the fuel becomes (Q. + eo.5 6025. KP.) = 5 195 240 kl These values are within 0.0. cell.1 11 np = a + b + c +d + e + f (12. in which a system of simultaneous equations is developed.109) can be replaced by C.76N2) aCO.05%. for one of the steps in the previous example. eqn (12.8295 Now. +fN.8 64 690.9 8. 125 654.O + c C 0 + dH. P I H .8 kJ/kmol octane (12. is better for computer solution.2 7223.8 kJ (Qv>s+ =4 (12. = 6.130) Evaluating the energy contained in the products at 2772 K gives Constituent 112772 u298 CO. + 13. but that a more general approach.3 91 972.889(02+ 3. based on the evaluated degrees of dissociation. This second method will be outlined below. = (Q. First. py' Po nY2 112 (12.0 68 646.3 6043.1lo).).2240 H20 co 70 702.1 59 551.7 52.0 1. and hence satisfy the energy equation.2 0. as given in eqn ( 12.131) If the first iteration of the previous approach is used then Tp= 2800 K and.132) .Up(T. by definition. Prco.8596 65 594.5 = 4 862 764.H. It was shown previously that this approach is often the best for manual solution. = = a 112 PIC0 P r o .= PIC0 P r o .0156 x 9 x (241 827) = 5 116 320 + 219 602.  nR = 67.8 63 922. the energy of the products.8472 Up(Tp).0. Alternative method for calculating the chemical equation The approach used above to calculate the coefficients in the chemical equation was based on the degrees of dissociation of the two reactions occurring in this example.3 7.8 + 335 014 = 5 197 778.776 H 2 0 2 N.097 x 8 x (282 993) .. must be UP(TP) UP('. 69 948.7 + 33 952.).129) Hence. KPr.1404 74 678. + bH.0 6032.)=  [UR(TR) uR(Ts)I 862 764.222 Difference n 99 196.8 0..O PICO. .9 7041. PICO.58152 KPd = P r c o P*H. 112 = 6.8 6011.6 118 613.
223 From the perfect gas law np .140) relevant to this problem is a=7. This is equivalent to assuming that a2is small compared with a .3613~’ a3/2 = 0 c = 8 .389 ~ / 2 = 7 .136a) (12.134) PrcozPrnz ad and the total amount of substance in the products is np= a + b + c + d + e + f Considering the atom balances gives Carbon: 8=a+c 27.O KP.140) The solution to eqn (12. degrees of dissociation 251 which gives (12.111 x 500 a nRTR xl (8 .3164 = y. as was assumed in the previous calculation.z = = 6.137) PRTP giving eqn (12.=~ PP R T R (12.135) e = 13.131) then eqn (12. If eqns (12.133) as Kp.138) becomes a cubic equation in a.138) becomes a2 67.a .138) is a member of a nonlinear set of equations in the coefficients of the chemical equation.896 .139) giving + 344. .224~ 13. then eqn (12.136a. It is now possible to check if this result satisfies the . One way to solve this is to make an assumption about the relative magnitude of d and the other parameters.138) Equation (12.3164 10 x 2800 = 0.l = 43.133) For the water gas reaction Prco PIH. b and c) are substituted into eqn (12.138).= ) Po K ~ r lP T P R 43.778 = 2a + b + c + 2e *c=8a *b=9d (12.027667 a ’ 2 (12.136b) (12.a=0.8295 =  cb (12. giving and b = 9 . with the assumption that d = 0.(b + c)/2 f = 52.875 (12. or more.136d) Hydrogen: 18 = 2b + 2d Oxygen: Nitrogen: (12.Dissociation problems with two. If it is assumed that d is small compared with the other parameters in eqn (12.Po c e PRTP 2 a 2 nRTR (12.125.889 .~)’(5.118.136~) (12.
This solution requires further iterations to satisfy the energy equation.1618H2 + 1.07 .125 x 6.866CO + 0.1.89295 = 0.7272CQ + 9H..519~ 1 3 . with an equivalence ratio of 1.134CQ + 8. which has been calculated from the general equation [ eqn (12. + 12.143).) and air.89295 0.9029002+ 52.141) The calculation should now be performed again based on the new value of d given in eqn (12. Assuming the combustion is adiabatic. which gives ch d = ____ = __0.142) and it can be seen that the change in d will have a small effect on subsequent values of the coefficients..71 N2 (12. similar to that in eqn (12. Solution Stoichiometric equation neglecting dissociation: C. is almost the same as that calculated using the degrees of dissociation in eqn (12. as done in the previous approach.16184 (12.134).11.2 EXAMPLE 5: A RICH MIXTURE A rich mixture of octane (C.2728CO + 42. calculate the conditions at the end of combustion allowing for dissociation of the carbon dioxide and water.09 3 5.134 x 6. This is to be expected because both approaches are exactly equivalent. is ignited at 10 bar and 500 K and bums at constant volume. + 13. 12.131)).134.76N2) n R = 67.119.252 Chemical equilibrium and dissociation equilibrium condition for the water gas reaction.8382H20+ 0. which is close enough to the actual solution because the value of d is compatible with this is d= cb ~  0.109).141). namely eqn (12.875 x 9 a K p 1 2 7.H.O + 47 N.144) 60.36(Q + 3.125 (12. t 11.H.76NJ nR =55.889(0.5 np=64 Rich mixture neglecting dissociation: C. but neglecting any formation of NO.O + 2.140) but with the following coefficients: + a3/2 350..H. + 3. 4 4 2 ~ ~ 2 =0 The new value of a is 7.1556 (12. Hence.143) Equation (12. tIR = ( 12.145) n p = 59.222N2 np= 7 1.H..5(Q + 3.8382 = aKPrZ 7.76 N2) 3 8CQ + 9H. This produces a new cubic equation in a .866 x 8. the chemical equation is C.1 11 a 7.73 .
2728 + 5 .147) Substituting for the mole fractions gives 5. Application of a computer program gives the final temperature and pressure.581 52 = = KPr2 6.7272( 1 . + 3.15 bar respectively.149) ( 12.73+2.7272 np=59.U Z H+ .36(0.3164 Similarly = 5.u 1)COZ + 9(1 .~ 2 1 . +4.8636a. 7 2 7 2 ~ x 9 x (1 .34): U .2728 + 5. = Po. The equilibrium constants are Kpr. without dissociation.6 K and 64.150) and KPrz= (2. C O ~ ~ U .5~2. . Prco Proz Prco PrH.829 25 = = Prco.2728 + 5. 6.5a2 It can be seen that this is a significantly more complex equation than for the weak mixture.= 43.8636~1 +4.O Prco2Prn2 112 (12.7272 u l)CO 2 0.2728 + 5.~2 ~) ) 9U2 x 5.2728 + 5 .5U2) p (12.0.) P nP n P P ( 12.a l ) (2. pco= Pco.u.~ l ) a2 X (2.146) 5.(1 .Dissociation problems with two.71 N.8636~~ + 4. 2 Rich mixture including dissociation is C8H18 11. +2 U ~ H ~ O .148) Hence K i r .25 and 12. (12.O + (2. = np (2.7272~1) 5. as 2958. degrees of dissociation 253 Dissociation equations (12.7272. or more.15 1) . C O 0.u J 2 n p Po  (2.7272(1 . + 42.7272(1 .7272~1)’(2.7272(1 .76N2) = 3 a2 a 1 5.(X 1) (12. 7 2 7 2 ~ ~ ) P.)H.
.7058 N2) (12.0189 CO + 0.267% 0. i.0096. The solution to this problem. Calculate the amount of nitric oxide (NO) formed at this temperature.. az = 0.07495C 0 2 + 0. if dissociation of the carbon dioxide and water vapour are taken into account. 0. allowing for dissociation is a final temperature of 2891 K and a final pressure of 62.01267 O2+ 0.O + 0. + 2H. and 70.05540. Estimate the effect of the NO formation on the temperature of the products.and they can be solved in the same manner as before.890% CO. and a z .151)) are again nonlinear equations in a . U.149) and (12. 0.3 When a mixture of oxygen and nitrogen is heated above about 2000 K these two elements will join together to form nitric oxide (NO).18183 H. and Kh2 equations (eqns (12. Solution: Chemical equation without dissociation: CH. + 7. Examp le Methane is burned with a stoichiometric quantity of air and achieves a pressure of 99. The elements combine in this way because the energy of formation of nitric oxide is positive.153) np = 10. 1.495% CO.3 np = 10.52+ 1 3 + 2 2 ( I o I t is possible to evaluate the total amount of substance in the products as follows: .58% N. and hence a combination of nitrogen and oxygen tends to reduce the Gibbs energy of the mixture. the reactions which form them are exothermic. neglecting the effect of the NO formation on the dissociation of carbon monoxide and water.O Chemical equation with dissociation: C H. The energy of the reactants.82 bar and a temperature of 2957 K after combustion.e.07495 = .and 0.11. The mole fractions of the constituents are 7.6425% H.006425 H. i. These result in the following degrees of dissociation: a 1= 0. + 0. 18..254 Chemical equilibrium and dissociation The K..0189 = ..76N. It is left to the reader to prove these values are correct. 1.99 bar. the reaction which forms it is endothermic. + 2 ( 0 .52N2 (12. EXAMPLE 6: THE FORMATION OF NITRIC OXIDE 12.655 nP np 1 aI a1 .O. Note that other compounds tend to dissociate at high temperature because their energies of formation are negative.(T. + 3.76N2) 3 np(0.) 3 CO.183% H.152) + 2 ( 0 2+ 3.e.) = 179 377 kJ.
Po. degrees of dissociation 255 and hence CH.76N2) 3 0.134950.0. + .01291 = 0 which gives ( 12.655 ( ". 2 2 The temperature of the products is TP= 2956 K.161) .159) 1.157) The partial pressures of the nitrogen constituents are PNO = P .155) Pro? PIN^ 112 112 (12.2014CO + 1.  + 0. = nP P.1 1279 (12.09174 Hence.+ 0.156) Adding in the NO equation to the chemical equation gives CH.Dissociation problems with two.474N2 n p = 10.00318a.+ 0. n P a3 (7. + 3.2014 CO + 1. giving ICpr3 0.09174NO + 0.a3/2)112(0.52 . + 2 ( 0 .76N2) 0.9315 H.N.7986 CO.52 . + 0.655 (12.= (0. + 0.N.2014CO + 1.158) and hence a3 (7.048690a3 .06845H2 + 0.0.1 1279 = = PrNO a 3 a3 (12. + 7.9315H20+ 0. + 2(0.06845 H. + n p = 10.655 (12. (12. + 3...76N2) * 0.9315H20+ 0.08908 0.a 3 / 2 ) p (12.a 3 / 2 ) PN.06845H2 + 0.13495 .154) Assume that combination of the nitrogen and oxygen occurs to form nitric oxide (NO): a 3 N O = .i ( ).7986 CO. the chemical equation is CH.0. nP 7. + a3N0 .13495 a3/2)112 Squaring gives = 0. + 7. or more. + 3.160) a3= 0.13495 .52N2 np = 10. + 2 ( 0 .O + 0.7986C0.52 .
2014 0.9315 x (239 082) (66 930) = 73 1 966 kJ/kmol CH.(66 930) Formation of NO = 723 717kJ/km01 CH.13495 7. The energy released by the original reaction.52 This satisfies the energy equation within 0. This effect has already been shown in Fig 12. neglecting the NO reaction.166) CO.2014 x (113 882) + 1.2014 x (113 882) + 1.06845 0.7986 1.163) The energy equation based on 0 K is AuO+ uR(0)l  [uP(TP)  =O (12. eqn (12. This will be considered later. and the values of a . . 7 9 8 6 (393 405) + 0. and a 2will be changed. but a more complex set of reactions was used. H. The effect of this is to upset the equilibrium of the carbon dioxide and water reactions. given in the question namely 2957 K. gives Constituent u2957 (12.9315 x (239 082) x +0.165) Applying the energy equation to the chemical equation neglecting dissociation of NO (i.7. First.e.7986 x (393 405) + 0.09174 x 89 915. It is not possible to demonstrate the more complex calculation in a hand calculation. n 135 615 107 643 0. the effect of the formation on the energy equation will be considered.256 Chemical equilibrium and dissociation It can be seen that the effect of the NO formation is to reduce the amount of oxygen in the products.154)) gives Up(Tp)=(731 927)+ 179 377=911 304k. N.O co H 2 0. (12.e. (12.164) giving UdTP) = Auo + u R ( T R ) (12. .162) The effect of the formation of NO is to reduce AUo in the following manner: Products Reactants ~ 0 . can be evaluated by considering Hess' equation: AUo = products Uf  1 Ui Reactants =0. i.J Substituting the value of T.2%.9315 Up(Tp)= 913 268 kJ 76050 70837 80457 75 270 0.
04 3.2687E .47646 2. Table 12.1805E04 7.69084 1. degrees of dissociation 257 Now considering the case with NO formation (Le.1860E03 1050 1100 1150 1200 1250 1300 1350 1400 1450 1500 (continued) . In this case Up(Tp)= ( 723 678) + 179 377 = 903 055 kJ If it is assumed that the temperature is reduced by the ratio 903 055/911 304. In addition.40233E + 05 0.22109E + 09 7.06500 0.26209 2.78788E + 20 4.8962E . it is necessary to include NO in the products.05 2.04895 2.05 4.24234 0.10788 0.04 1.38630E + 18 1.5096E .88 120 1.1361E .17249E + 13 6.62821E + 10 3.42591E + 06 2. and shows that the effect of the formation of NO has been to reduce the products temperature.65502E + 12 7.16076E + 22 1. and this is introduced in the table below: Constituent '2930 CO.4904E .03 2. or more.4154E .63189 1.00768E + 05 7.91 12E .02025E + 06 2.09174 7.08908 UP(Tp)= 903 567 kJ 77 304 74494 0. then a first approximation of the products temperature is 2930 K.38021E + 05 2.06 5.18132E +07 5.93024E + 08 5. in eqn (12.39213E + 08 1.16651 0.23787 1.63412E + 10 1.17472E+ 10 2.40361E + 15 8.07 2. the energy of the products is less than in the previous case because the formation of NO has reduced the energy released by combustion.44763 0.45016E + 06 1.5257E .2291E .9315 0.97385E + 07 1.77343E + 10 1.38939E + 08 8.06909E + 25 2.4212E.Dissociation problems with two.5710E .08 5.03576 0.0419E .20880E + 11 5.01753 0.05 1.7986 1.90700E + 15 2. NO N Z n 134 153 106407 75 271 70068 79609 0.474 This value of the products' energy obviously satisfies the energy equation.O CO H 2 0.23642E + 12 3.33605 0.16841E + 11 9.82234E + 07 6.83837 2.8997E .3 Equilibrium constants 500 550 600 650 700 750 800 850 900 950 1000 1.26609E + 06 1.157)).03 1. H.57647 0.06 1.72148 0.06845 0.05393 1. First.00739 0.00177E+ 06 4.54176E + 18 3.04 5.7465E .00209E+ 17 3.22648E + 20 1.09 1.4233E .43113 1.64323E + 07 1.03 1. in this case by about 30 K.62178E + 16 1.2014 0.79082E + 08 2.4501E .33722E + 14 1.2311E .05 8.04 2.83842E + 09 7.07979E + 06 5.98055E + 13 2.07 7.03 3.08 2.4800E .3872E .07620E + 07 2.90482E + 22 3.
01 1.02 2.71035E + 01 3.02 1.03 1.2590E.90158 6.49113 4.34122E + 02 1.02 2.0691E.02 1.68464 7.01 1.79136 7.79334E + 03 2.52960 3.01914 7.02 5.21342E + 01 1.39503E .6315E.40045 6.98289E + 02 3.7476E .14787E + 03 7.7028E .38436E + 02 2.08601E + 01 1.9822E .41215E + 03 1.28029E+ 01 1.2723E.2359E .11558 3.58152E + 00 5.47329E + 01 2.5373E .01 1.88294E + 04 1.35247 7.66861 4.32615 5.02 4.39219E + 00 3.2115E .3 (continued) 1550 1600 1650 1700 1750 1800 1850 1900 1950 2000 2050 2100 2150 2200 2250 2300 2350 2400 2450 2500 2550 2600 2650 2700 2750 2800 2850 2900 2950 3000 3050 3100 3150 3200 3250 3300 3350 3400 3450 3500 9.16017 6.02 9.02 7.0057E .72637E + 04 4.9579E.27483 7.5826E.31054E + 02 1.0227E .8721E .64752E+ 02 1.48240E + 01 4.30444E+ 00 1.00786 5.52559E+ 00 1.35460E+ 00 7.82925 6.02 5.49343E + 03 2.62323 6.01343E + 00 2.69061E + 01 3.51997E + 00 2.04097E + 02 8.0168E .13590E + 02 1.83304E + 01 1.62613E + 00 3.01 2.8498E .06191E + 24 3.01 1.67731E .01 7.10821 7.62640E+ 01 1.38587E + 01 1.73591E + 01 5.67587E + 04 5.0274E .03 7.1279E .01 1.03 5.03 8.15991E + 03 4.76297E + 03 5.3198E .12369E + 01 1.43413E + 24 8.01 .9931E .02 1.3473E.39304E .90418 3.56295 7.49468E + 01 3.53723E+ 05 8.42300E + 00 8.16961 5.8624E .01 1.8322E.4361E .14828E + 00 6.76515 5.4884E .70287E + 01 2.59006E+ 01 1.1 1989E + 00 1.89945E + 03 1.01 1.5847E .02 4.60986E + 04 1.69484E + 03 1.54023E + 01 2.31095E .4700E .32426 3.45249E + 02 4.28255 6.02 2.1666E .9183E .02 3.35700E + 00 4.93402E + 04 2.01 2.02 9.6643E.02 6.03 6.1992E.01 8.49651 7.66502E + 02 1.54906E + 01 6.8137E .02 1.73107 3.47753 5.01 6.02 3.79349E+ 00 1.02 8.62384 5.12089E + 00 9.4240E.30849 4.02 8.0586E.19480E + 04 7.17799E+ 02 8.76820E + 02 2.01 1.4039E .04452E + 04 1.19343 7.43587E + 00 2.02 6.9138E .84087 5.80179E+ 03 1.73988 7.48280E + 02 4.29132E + 01 4.83905 4.12080 4.57753E + 01 2.42636 7.15523E + 03 3.51398 6.89620E + 01 2.03322 6.77496E + 02 6.02 1.62704E + 02 2.02 3.72829 6.01 1.Table 12.21032E + 03 8.2620E .62566 7.5025E .01701E+ 01 8.80785E + 02 3.01 1.92824 4.08294E + 01 2.3312E .92618 7.06707E + 01 9.82471E + 05 1.33978E + 01 6.01 1.
H. and 21% 0.12 Concluding remarks It has been shown that dissociation is an equilibrium process which seeks to minimise the Gibbs energy of a mixture. 2 (a) Calculate the equilibrium constant.01325 %(2 + a)T 88 where a = degree of dissociation.Problems 259 12. by volume.’ / F = K. The thermodynamic theory of dissociation has been rigorously developed.. CO.028 atrn”. and this is compressed adiabatically. Show the pressure. 391 032.. at 2000 K at the reference pressure of 1 atm for the reaction CO + H. However. and it will be seen later that this applies to fuel cells also (see Chapter 17). CO.O. CO and H. A wide range of examples has been presented.o.g. 108 052 k. Dissociation usually tends to break product molecules shown into intermediate reactant molecules (e. the same theory shows that at high temperatures.). 239 342. and hence reduces the work output and efficiency of a device. 27. In a combustion process.6686. covering most situations which will be encountered in respect of combustion.O CO. nitrogen and oxygen will combine to form oxides of nitrogen. PROBLEMS Assume that air consists of 79% N.).wco. (b) 27. dissociation always reduces the temperatures and pressures achieved. [(a) 4. 1 A cylinder contains 1 kg carbon dioxide (CO./Po) KPr = (Pco/ P o ) (Po. at (b) Calculate the equilibrium constant. is given by (Pco. Kp. 2 Also calculate the equilibrium constant at 2500 K at a pressure of 1 bar.J/km~l. w CO.206 bar’/*] . Note that the equilibrium constant for the reaction CO + 0. temperature and specific volume are related by the equations 3 a and pv = d.. 2500 K at the reference pressure of 1 atm for the reaction 1 co + . K./Po)l~z where po is the datum pressure of 1 atm. + H. 1..
0. Q.0076. CO. 239 342. the heat transfer is small). 0.and T = temperature in K..38221 6 The exhaust gas of a furnace burning a hydrocarbon fuel in air is sampled and found to be 13. 0.1450..71761 5 Methane (C&) is burned with 50% excess air.. and show that the combustion process is adiabatic (i.7 at T = 2000 K. (show this as a function of pressure)..02% H.50. the equilibrium constant for the dissociation of CO. and 74.081% CO. 7.898.46 . 0.58% H. = 28600 8. and a negligible amount of H2. [1.64] 4 A stoichiometric mixture of propane (CJ&) and air is burned in a constant volume bomb. 0.87% CO.108 052 U/kmol. = 748. 7. Evaluate K.04% CO.260 Chemical equilibrium and dissociation 3 If it is assumed that the enthalpy of reaction. if the calorific value of propane is 46 440 U/kg at 300 K. and it can be assumed that the degree of dissociation for the water reaction is onequarter of that for the carbon dioxide one. the pressure of the exhaust gas.25% H.. assuming that the partial pressures of CO and H2 are small. on the UT diagram. 1. 0.76% N. If the temperature of the exhaust gas is 2500 K. 391 032.68% N.O. Evaluate the composition of the products allowing for dissociation if the peak temperature achieved is 2900 K. 75. [0. is given by K = e QP’sT+k P where k is a constant.3089. 0. (Pco)2Po.. 2. is a constant.58% 0. and the internal energies of formation for the various compounds are CO. 0. The equilibrium constant for the carbon dioxide reaction is given by K. ... and N. 6. the equivalence ratio. Prove that the temperature obeys the conservation of energy. 5 2 / ~ ” ~ .45% CO. The conditions just prior to combustion are 10 bar and 600 K. For a particular reaction Qp= 277 346 W/kmol. 1. [26.e. calculate: (a) (b) (c) (d) the carbon/hydrogen ratio of the fuel. T . CO. 0.O. 1.0916. The equilibrium products at a pressure of 10 bar and a temperature of 1600 K contain CO.. H. = (PCOJ 2 where log. .. H.67% 0. = The equilibrium constant for the CO. at the temperature of 2500 K.O. by volume. show that the value of K . The internal energy of propane at 25°C is 12 380kJ/mol. 0. Calculate the partial pressures of these gases. 8 0 . reaction at 2900 K is Kpr= pco2/pcopo2”2 4..0524 x 0.. 8. Indicate the processes. Evaluate the final temperature and pressure of the products. and K. including a heat transfer process. 10.6383 x 1. H20. The initial conditions were 1 bar and 300 K and the final composition was 7.01527.0229.6545. K .6545.8741 7 A weak mixture of propane (C31&) 50% excess air is ignited in a constant volume and combustion chamber. [0.
0932. and the maximum pressure is 11.72811 9 A stoichiometric mixture of carbon monoxide and air reacts in a combustion chamber and forms exhaust products at 3000 K and 1 bar. may be taken as co..Problems 261 The specific heats at constant volume (c. H..) of the constituents.02096.0 + 4. 0.112 x 103 k~/kmoi. Calculate the pressure and the molar composition of the mixture. a weak mixture) is contained in a rigid vessel with a volume of 0.02792. in kJ/kmolK. It is ignited. 0. If the initial pressure and temperature are 2 bar and 60°C respectively. CO 12. (b) the amount of substance in the products. (c) the amounts of individual substances in the products per unit amount of substance supplied in the fuel.695 bar] 8 A mixture of propane and air with an equivalence ratio 0.7 + 2.00261.169.7 + 6.02005. and the mixture is ignited. 1. 0.5 x 103T 20.e. the equilibrium constant. Calculate: (a) the amount of substance in the reactants. [ 399.36%.5 m3 at a pressure of 1 bar and 300 K.18961 11 A vessel is filled with hydrogen and carbon dioxide in equal parts by volume.4 x 103T 17.0 x 103T 0. estimate (a) (b) (c) the maximum temperature. 22. This is ignited at 60°C and a pressure of 1 atm (1. neglect the internal energy in the reactants The internal energies of formation of the constituents at 300 K are CO.7 + 8.4 x 103T H. 0.01 138. 96. show that the molar fraction of carbon monoxide is approximately 0.7 + 22 x 10~77 19. 2.O. 0. [2250 K. 393 x lo3. . H.3 MJ/kmol CO. and after combustion the products are at a temperature of 2600 K and a pressure of 9. c o .13 bar. in the gases leaving the heat exchanger if dissociation can be neglected at the lower temperature.] 10 A mixture containing hydrogen and oxygen in the ratio of 2 : 1 by volume is contained in a rigid vessel. 0.013 bar).5%. The products of combustion now enter a heat exchanger where the temperature is reduced to 1000 K Calculate the heat transfer from the products per amount of substance of CO. and after some time the temperature is 2227°C.O N. [0.7 +4.9 (i. 241 x 103.3 x 103T 17. If the products are in chemical equilibrium.1368.06 bar.and the volumetric analysis of the products at the maximum temperature. 7. K p . but no reactions occur between the nitrogen and the oxygen. . 0. C3H.. [5.8 bar.
8 Hydrogen. H.3573 .3 27 047.8 25 579. Calculate the final pressure after combustion.6 Water.6573. 14.1 85 109.4%.4%] 14 A gas turbine combustion chamber receives air at 6 bar and 500 K. on a UT diagram.508 atm.5 0 24 341.6 80633.O 239 081. weak). [7. and after some time the temperature is 2227°C.3417.4 [47. Calculate the pressure and the molar composition of the mixture. The equilibrium constant is KPr = (PH.) at an equivalence ratio of 0. It bums adiabatically at constant volume.8 (Le.63 bar and 845°C.262 Chemical equilibrium and dissociation Use 1354 logloKp = 1. 0 25 700.15831 12 A stoichiometric mixture of hydrogen and air is compressed to 18.J/kmol) T (K) 0 1100 1150 3300 Oxygen. = Pn.37% by volume respectively. 0. Show that the final equilibrium temperature is 3300 K and the degree of dissociation is 8.H. 0. H2 Nitrogen. including the effect of dissociation.oPco ~ PH2PC4 and T = temperature in kelvin [1965.7 142 527. It is ignited at 60°C and a pressure of 1 a m .T where K.993% and 11.) is contained in a rigid vessel.1583.02H20 2 . 0 23 065. 0. + . 0.02CO2 2 1 H.85%.) and hydrogen (H. The amount of carbon dioxide and water in the products is 9.6%.58 bar] 13 A mixture containing equal volumes of carbon dioxide (CO. 14. Calculate the maximum temperature achieved after combustion and evaluate the degrees of dissociation for each of the following reactions: 1 co + . 0. N.lPo)1/2 at T = 3300 K Use the following internal energies: Internal energy (k.1389 (PHJPO) (Po. 35. 35.4 91 379.6%.3417. Show the process. 4.O/PO) = 12..3 24 187. which bums at constant pressure. It is fuelled using octane (C.
0.H. p j )of the cycle in bar.22 bar.1434. 2554 K] 16 A gas engine is operated on a stoichiometric mixture of methane ( C b ) and air.5 bar and 350 K respectively. in the ratio of volumes of 1 :30. Assuming that the combustion gases do not change composition during the expansion stroke. What has been the effect of dissociation? (See Chapter 10. 0. A spark ignition engine with a compression ratio of 10: 1.) and air is trapped in the cylinder of an engine at a pressure of 1 bar and temperature of 400 K. H. in the products.0465] 18 A 10% rich mixture of heptane (C. 2883 K. [2487 K. use an enthalpy of reaction of octane at 300 K of 44 820 kJ/kg. 0. use your results to confirm this. while that of expansion. 0. 99. calculate the maximum pressure and temperature after combustion. the volumetric compression ratio is 12:1.00269.. [2000 K. intercooled compression ignition engine is operated on octane (C. operating on the .35. If the initial pressure and temperature of the mixture are 10 bar and 500 K respectively. calculate the maximum temperature and pressure reached.8463. Assuming that the mixture is in chemical equilibrium and contains only CO.1071. Question 5). This solution presupposes that there is no 0. The volumetric compression ratio of the engine is 20 : 1.4. At the end of the compression stroke the pressure and temperature are 10 bar and 500 K respectively.Problems 263 Assume the Octane is in liquid form in the reactants and neglect its enthalpy.H. and the index of compression is 1c = 1.0139. 119. Calculate the equivalence ratio. [59. when the volume is 20% the trapped volume.0293.4. and at a particular instant during the expansion stroke. If the airfuel ratio is 24 : 1 calculate maximum temperature and pressure achieved in the cycle taking into account dissociation of the carbon dioxide and water vapour.O. The mixture is trapped at 1 bar and 300 K. Question 6.79334. What has been the effect of dissociation on the power output of the engine? Assume that the index of compression K~ = 1. (See Chapter 10.&) and air to a spark ignition engine.. If the combustion process is an adiabatic one at constant volume. This is compressed and ignited. [0.) [0. the maximum pressure and temperature achieved during the cycle. What has been the effect of dissociation? (See Chapter 10. 2960 K] 17 A gas injection system supplies a mixture of propane (C. Question 7). 0.0. CO.67 bar.10 bar] 20 One method of reducing the maximum temperature in an engine is to run with a rich mixture.) [5 1. lcE = 1. the pressure is 27.1037.00868.1 bar. and N. 0.06 bar.) and achieves constant pressure combustion. and the pressure and temperature at the start of compression are 1. 2200 K] 15 A mixture of one part by volume of vaporised benzene to 50 parts by volume of a r is i ignited in a cylinder and adiabatic combustion ensues at constant volume.0. calculate the indicated mean effective pressure (imep.. 0. Question 1..71481 19 A turbocharged. H. 15. find the temperature and molar fractions of the constituents. (SeeChapter 10.4 bar. and also the composition (by volume) of the dry exhaust gas.
57 bar] . with @ = 0.2.264 Chemical equilibrium and dissociation Otto cycle. taking into account dissociation of the carbon dioxide and water vapour.) [3020 K. How has dissociation affected the products of combustion? What are the major disadvantages of operating in this mode? (See Chapter 10. (See Chapter 10. 71. The trapped conditions are 1 bar and 300 K. Assume the ratio of specific heats. calculate the maximum temperature and pressure reached during combustion at constant volume. how much lower the maximum temperature is under this condition than when the engine was operated stoichiometrically.023 x lo5 kJ/kmol C h . during the compression stroke is 1. Calculate. and the index of compression is 1. K. taking into account dissociation of the carbon dioxide and water vapour.4. 3029 K] 21 A gas engine with a volumetric compression ratio of 10 : 1 is run on a weak mixture of methane (C&) and air. and the heat of reaction at constant volume for methane is 8. with an equivalence ratio of 1. under the following assumptions: (a) that 10% of the heat released is lost during the combustion period. Question 8. Question 9. and (b) that compression is isentropic.9. If the initial temperature and pressure at the commencement of compression are 60°C and 1 bar respectively.4. runs on a rich mixture of octane and air.) [2737 K.
The other effect of dissociation is to form pollutants. Internal energytemperature diagram for combustion both with and without dissociation 31 It can be seen from Fig 13. .e. Chemical kinetic effects and dissociation are the sole . account is taken of the finite rate by which equilibrium is achieved. .that is. for issociation T. If chemical kinetics are considered (see Chapter 14). there is more than sufficient oxygen in the air to oxidise completely both the carbon and hydrogen in the fuel. then it is possible to show how some of the major pollutants are formed in the quantities measured at the exit from engines..1. and other compounds or radicals. in turn.13 Effect of Dissociation on Combustion Pa ra meters Dissociation is an equilibrium process by which the products of combustion achieve the minimum Gibbs function for the mixture (see Chapter 12). . The effect is to cause the products that would be obtained from complete combustion to break down partially into the original reactants. This. . T Fig. T. reduces the amount of energy that can be drawn from the combustion process and reduces the work output of engines. .' I I Products (with dissociation) ' ' Products (with complete combustion) . This is particularly true in combustion in engines. i. I I . 1 . . when carbon monoxide (CO) can be formed even when the mixture is weak . for complete combustion 7 Temperature. .1 that the effect of dissociation is to reduce the temperature of the products after combustion. This can be depicted on a UT diagram as shown in Fig 13.
13. which depicts the way in which the actual level of pollutants attempts to follow the equilibrium level. . .(._._ Crankangle Fig. .. and these are initially compressed further (as the piston continues to rise to top dead centre [tdc]. but it also means that the rate of reduction of the pollutants is slower than that of the equilibrium species and the NO.. and they also increase the amount of carbon monoxide (CO) during weak and slightly rich combustion. and the combustion process continues) before being expanded when the piston moves down and extracts work from the gases.2. gas turbine. kinetics can be assessed by considering a simple example.. Imagine a spark ignition engine in which the mixture is compressed prior to ignition by a spark. .. %. If the compression temperature is not too high it can be assumed that the reactants do not react before ignition.g.2 Production of pollutants i equilibrium and chemical kinetically controlled processes n ... Processes which include chemical kinetics are not equilibrium processes.. is usually frozen at a level above the equilibrium value of the exhaust gas from the combustion chamber. .. boiler. but lags the equilibrium values.. etc.. After ignition the reactants bum to form products at a high temperature. As the pressure increases. The effect can be seen in Fig 13. NO. This lag means that the maximum level of pollutant (e.) formed does not achieve the maximum equilibrium value. The effect of chemical. but they attempt to reach equilibrium if there is sufficient time.. ..266 Effect of dissociation on combustionparameters causes of the production of NO. diesel engine.. ... or rate. from fuels which do not contain nitrogen (through i) combining of the nitrogen and oxygen in the ar. the temperature of the gas also increases and the products tend to dissociate: they attempt to achieve an equilibrium composition but the speed of the engine is too rapid for this.
4.52 CH4 + .2) 7.4) @ .. . @ 3 1.g.0. and that the fluid was compressed through a volumetric compression ratio of 12. @ is called the equivalence ratio and in this case @ s 1. The equivalence ratio was varied from a weak value of @ = 0.) of 1.5) (13.The basic reactions 267 13. which has a range of fuels programmed into it. It was assumed that the initial pressure and temperature at entry to the combustion chamber were 1 bar and 300 K respectively.e.O + 47N.(0. The principles introduced here can be developed to study the effect of equilibrium on a realistic (finite rate of combustion) cycle. (13. A series of calculations was undertaken using octane (C8H18) and methane (CHJ as the fuels. carbon dioxide and water. e. w co + io2 and H20w H.76N2) while that for octane is CsH1. This is essentially similar to the combustion that would take place in a reciprocating engine with constant volume combustion at tdc.1 Calculation o combustion both with and without dissociation f It is possible for the pressure. there is less oxygen than required for complete combustion of the fuel. which dissociate according to the equations co. + 12.76Nz) 3 C02 + 2 . For a rich mixture. + ___ 4 4)co+ 2H20 + N. + .52N2 (13.76N2) c o .1. i. then the equation becomes 2 7. with an index of compression ( K = c. A program written at UMIST and based on the enthalpy coefficients given in Chapter 9 has been used to evaluate the results presented in this chapter. like that occurring in a gas turbine combustion chamber. can be run in dissociation and nondissociation modes. In this case the enthalpy of both the reactants and products will be equal. + 2H20 + 7.( 0 2 8C02+ 9H.1 0 2 + 2H2O + N2 @ if the mixture is weak. 13. The program. Combustion then took place at constant volume.6) + i 0. temperature and equilibrium composition of various mixtures to be calculated using computer programs./c. (:1 (13.76N2) 2 CH. The computer program was written in a manner that enabled it also to be used for constant pressure combustion. (13. and if it is assumed that the hydrogen has preferential use of the oxygen. based on the principles outlined in Chapter 12.25.5 to a rich one of @ = 1. Combustion in this Otto cycle is adiabatic and occurs at constant volume: this is a constant internal energy process.2 The basic reactions The stoichiometric combustion of methane is defined by the chemical equation CH4+ 2(02+ 3. as shown in Fig 13. which is an ‘Otto cycle’ in which the heat transfer process associated with the air standard cycle is replaced by a realistic combustion process.1) @ + 3. (13.52 If the mixture is not stoichiometric then the equation for methane becomes * CO.+ 3.5(02+ 3.3) @ ( ( @ It will be assumed for the initial examples that the only dissociation is of the products.0.
. Initial pressure: 1 bar. If there is no dissociation then the peak pressure is always reached at the stoichiometric ratio (@ = 1). produced by an adiabatic combustion process. a.4 show that the peak pressure is reduced by about 8 bar at the stoichiometric airfuel ratio (@ = 1) with both methane and octane. dissociation will tend to decrease the pressure achieved during the combustion process (when it occurs in a closed system) because it reduces the temperature of the products. 13.5) and (13. initial temperature: 300 K. 4 Fig. Dissociation also changes the equivalence ratio at which the peak pressure is achleved. This reduction in pressure is always evident with stoichiometric and lean mixtures. and around @ = 1.5 and 13.3 The effect of dissociation on peak pressure In general. compared with the nondissociating case.6 show the variation of the peak temperature. Later in the chapter the dissociation of other compounds will be introduced to give a total of 11 species in the products. with equivalence ratio.3 and 13.4 13.25 for octane. L Rich 80 a 20 0 05 Oh 07 OX 09 1 1 1 12 Equivalence ratio.except they occur at a different equivalence ratio. n L . when the products of combustion were defined by a set of simultaneous equations. The peak pressure with dissociation occurs at around @ = 1. However. The approach adopted by the program is the same as that introduced in Chapter 12. compression ratio: 12. compression index: 1.3 Variation of pressure with equivalence ratio for combustion of methane.1 for methane. Figures 13. both with and without dissociation. 13. when dissociation occurs the equivalence ratio at which the peak pressure occurs is moved into the rich region (@ > 1). The method of solving for these species is outlined by Baruah (Chapter 14) in Horlock and Winterbone (1986).4 The effect of dissociation on peak temperature Figures 13.4) that the peak pressures achieved with and without dissociation are almost the same .6)) have to be added into the basic equations to evaluate the chemical equation with dissociation. This is because dissociation tends to increase the amount of substance (np) in the products.268 Effect of dissociation on combustion parameters These equations (eqns (13. although an increase in pressure over the equivalent situation without dissociation can occur in rich mixtures due to the increase in the amount of substance in the products. The program does this automatically and evaluates the mole fractions of the products. It is interesting to note from the octane results (Fig 13.
100 80 60 j/i I 1 I I . while for octane the values are 3306 K to 3096 K (at @ = 1. and moves the point at which the maximum temperature is achieved.~. . i I I i Equivalence ratio. The stoichiometric airfuel ratio (by weight) for methane is 17. .1 . whilst it is 15. ~ __ c I I  __ I I I ~ I I I I  500  no dissociation dissociation I  .4 + m L F” % E 1500 1000 .’ . .2).rich). The effect of such a reduction in temperature is to lower the efficiency of an engine cycle. aJ L m. .5 The effect o dissociation on the composition of the products f The composition of the fuel will affect the composition of the products due to the different stoichiometric air. t 120 n L I I I ’ 269 I . In the case of methane the maximum temperature reduces from 3192 K (at stoichiometric) to 3019 K (at about $J = 1. 20. A 1 no dissociation dissociation A . 13. _ i  0.. k a 40. I ! . compression index: 1. .The effect of dissociation on the composition of the products 140 .05 for octane. 1 I 1 I Meak I I I Rich h ! 1 / 1 ! 3 m m . I I ! Dissociation lowers the temperature for both fuels. 4.4 Variation of pressure with equivalence ratio for combustion of octane. initial temperature: 300 K. compression ratio: 12.!s”.fuel ratios and the different carbon/hydrogen ratios. 13. .. . Initial pressure: 1 bar. P. II t . Fig.16. The stoichiometric airfuel ratio remains in the region 14 to 15 for most of the higher straight hydrocarbon fuels./I y .
both with and without dissociation. compression ratio: 12.70 0. Initial pressure: 1 bar.00 0. 13. 13. Its mole fraction remains around 0.7. 13.10 0.00 1.) The mixture is weak at equivalence ratios of less than unity. 4 Fig.8.10 because it dominates the composition of the products. compression ratio: 12.6 Variation of temperature with equivalence ratio for combustion of octane. e u a 0 .44 for methane and octane respectively.05 0.90 1. and this affects the composition of the products. It can be seen that the largest mole fraction is that of water. has been omitted from Figs 13. The mole fractions of the products for the combustion of methane (taking account of dissociation) are shown in Fig 13.50 0.9 and 13.79 in all cases.7 Variation of composition of products with equivalence ratio for combustion of methane. * .20 Equivalence ratio.4 nitrogen.. which is more than twice that of carbon dioxide: this reflects the greater proportion of hydrogen atoms in the fuel.80 0. N. compression index: 1.20 1 I I II H>O 9 I 0I . 13. compression index: 1. 4 Fig. (Note: the mole fraction of 0. Initial pressure: 1 bar.10 1.7. and there is excess oxygen for complete combustion up to an equivalence ratio of unity. 0. This can be seen in Figs 13.60 0.15 t 0. initial temperature: 300 K. initial temperature: 300 K.4 The carbon/hydrogen ratio varies from 0.270 Effect of dissociation on combustion parameters 05 06 dissociation 07 08 09 1 I t 12 13 Equivalence ratio.25 to 0.8 .
00 0. the level of carbon monoxide increases linearly with equivalence ratio.80 0.90 1.60 0. has been plotted. This reverse reaction also produces some unreacted hydrogen. The carbonrelated reactions are shown in Fig 13. When dissociation is neglected.50 0. When dissociation is .70 0.00 1. when there is dissociation the quantity of oxygen in the products is increased.50 0.20 x 0.70 0. for combustion of methane 0.00 0.06 0. the carbon is completely oxidised to carbon dioxide in the weak and stoichiometric mixtures. with no carbon monoxide being formed.20 Equivalence ratio. for combustion of 39 methane and 13.90 1. and dissociation causes this to be produced even with weak mixtures.10 1. simply due to the reverse reaction. which includes the mole fraction of oxygen.20 Equivalence ratio. It can be seen from Fig 13.8.04 c 0 I P b k a 0 Q f 0. 4 Fig. 13.05 0.10 27 1 & 0.60 0. After the mixture becomes rich. $ Fig. It should be noted that it was assumed that the hydrogen would be oxidised in preference to the carbon in the reactions without dissociation. with and without dissociation. f that there is no oxygen in the products at equivalence ratios of greater than unity i there is no dissociation.10 1.00 1.8 Variation of carbon reactions.02 0. where the composition of the products.15 0. However. and this explains the absence of hydrogen in those cases.08 0. Variation of hydrogen reactions.10 dissociation 0.80 0.The effect offuel on composition of the products 0.9. with and without dissociation. both with and without dissociation.9. 1 .
However./kWh). it is better to bum fuels with a low carbon/hydrogen ratio. or more likely kg CO. It is also noticeable that the mole fractions of water and carbon dioxide are much closer with octane than methane. Both are paraffinic hydrocarbons. which simply reflects the higher carbon/hydrogen ratio of octane.7 and 13.8 0.10 c . why natural gas is a popular fuel at this time. while for octane n = 8.5% with methane: the energy released per unit mass of mixture is almost the same for both fuels.e.e. at @ of about 0. 13.0 (i.9 to 1.* 0 e u c 0.1 1.7 0. 13.3 Equivalence ratio. This means that the for carbon/hydrogen ratio varies from 0. kg CO. in part.10. The carbon dioxide fraction maximises on the lean side of stoichiometric. I F K .44.6 The effect of fuel on composition of the products Two different fuels were used in the previous analysis of the effect of dissociation on combustion products. it can be seen that this peaks at an equivalence ratio of unity (@ = 1) without dissociation. weak) when there is dissociation.2 1. The maximum mole fraction of CO. if it is required to reduce the amount of carbon dioxide released into the atmosphere. bk 2 m P 0.9 1. . produced for each unit of energy released (i./kJ.0 1. when the peak level of carbon I dioxide is only about 75% of that without dissociation. but surprisingly there is a lower level of carbon monoxide in the rich region than when there is no dissociation. initial temperature:300 K. compression ratio: 12.6). whilst it peaks at around 7. Initial pressure: 1 bar.5 and 13.0 0.6 0.10 Variation of composition of products with equivalence ratio for combustion of octane. 4 Fig.10.272 Eflect of dissociation on combustion parameters 0. it peaks at an equivalence ratio of around $ = 0. with a generic structure of CnH2n+2: methane the value of n = 1. carbon monoxide is formed even in the weak mixture region.05 0. The trends are similar to those for the combustion of methane.9. as shown by the similarity of temperatures achieved (see Figs 13. Hence. The mole fractions of products for the combustion of octane are shown in Fig 13. This has an effect on the amount of CO. compression index: 1. Considering the carbon dioxide. The production of carbon monoxide in lean mixtures is the reason for carbon monoxide in the untreated exhaust gas from internal combustion engines even when they are operating stoichiometrically or lean. The effect of this ratio can be seen in Figs 13. This explains.4 considered.25 to 0. The explanation of this is that the dissociation of the water releases some oxygen that is then taken up by the carbon.5 0. released with octane is almost lo%.
1 E 0 . the nitrogen and i oxygen will combine to form oxides of nitrogen.10.001 0. The numerical results for carbon monoxide. and the radical OH play a significant part in the amount of NO produced in the equilibrium mixture. NO. It was also stated that it is not enough simply to add the equation N. the combustion of methane and octane in an engine operating on an ‘Otto’ cycle. The results are shown in Figs 13.11 Products of combustion at tdc for the combustion of methane in an Otto cycle . w 2 N O (13. These equations representing equilibrium of the 11 have been used to analyse the equilibrium constituents of the products of combustion for the cases considered above.01 0.12.11 and 13. This is necessary because the formation of atomic oxygen and nitrogen.e.0 Equivalence ratio. 13. These results will now be analysed.I 4 u & I I Q 0) 9 0. It should be noted that the ordinate axis is in logarithmic form to enable all the important constituents to be shown on a single graph. it is simply the change in scales which has changed the apparent shapes.7) but a chain of reactions including 11 species has to be introduced. carbon dioxide and water are similar to those in Figs 13.6 0.8 1 .Theformation of oxides of nitrogen 273 13. and in particular nitric oxide.9 and 13. + 0.7 The formation of oxides of nitrogen It was shown in Chapter 12 that when ar is taken up to high temperatures.2 Fig. + 1. 1 2 c 0. i.
8 1.H + u 0 k I co s Q) 0. the . The temperatures and pressures achieved by this combustion process are similar to those shown in Figs 13. This example is different from that shown in Chapter 12.001 0.274 Effect of dissociation on combustion parameters 1 g 0. still peaks in the vicinity of q5 = 0.3 and 13. In fact. 1 9 )and carbon dioxide (~0. Now considering the formation of nitric oxide: it was shown in Chapter 12 that nitrogen and oxygen will tend to combine at high temperatures to produce nitric oxide because the enthalpy of formation of nitric oxide is positive.9. and CO have been changed in the rich region. and the CO.5. although strictly speaking it is the opposite.07)have not been significantly changed by the extra dissociation processes. and in this case the mole fraction of CO exceeds that of CO.12 Products of combustion at tdc for the combustion of octane in an Otto cycle Considering Fig 13.3 and 13.11 first: this shows the equilibrium constituents of the mixture at tdc after adiabatic combustion of methane. This is because more reactions are competing for the available oxygen. although there will have been a slight reduction in both parameters because the dissociation processes all absorb energy. at q5 = 1.1 EI^ .01 0.2.6 0. and the variations are shown in Figs 13. and the carbon is the loser. This combination process will be referred to under the general heading of dissociation. 13. In this case the peak pressure and temperature achieved in the combustion process are functions of the equivalence ratio.8 to 0.2 Equivalence ratio. detailed examination shows that the levels of CO. It can be seen that the maximum values of the mole fraction of both water ( ~ 0 .0 1. 4 Fig.5. when the variation in the amount of NO with equivalence ratio at constant pressure and temperature was depicted. However.
this was discussed in Chapter 12. Before considering the effect of the rate of reactions on the actual levels of NO achieved.7 to 0. = 0.7 to 0. the changes occurring in the conditions in the cycle tend to run counter to each other to some extent. as shown qualitatively in Fig 13. Hence.7 to 0.9 because the driving force (the equilibrium concentration) and the rate of reaction combine at this equivalence ratio to maximise production of this pollutant. but is spread over a significant period of the cycle and the pressures and temperatures are lower than those attained in the ‘Otto’ cycle: this will reduce the peak equilibrium level of NO.2. but are restricted by the rate at which reacting molecules meet. although the effect of temperature dominates. the reactions occurring in the cylinder are not instantaneous. The value of mole fraction of NO peaks at around Q. This can be explained by considering the effect of rate kinetics. The maximum levels of NO again occur around Q. and the CO. At low equivalence ratios there is an abundance of components to react but the temperature is low.12 that the peak level of NO at equilibrium occurs at around Q. This is because the reaction which creates NO is dependent on the amounts of nitrogen (N. the CO.5. reaction). = 0. The peak value of NO occurs at Q. to 3000 K at Q. It is shown in Figs 13.13. in fact these reactions tend to ‘freeze’ at around 2000K. this level is typical of that which would be achieved at equilibrium conditions in an engine. and is the subject of Chapter 14. this is known as chemical kinetics or rate kinetics. and lags it when it is increasing as shown in Fig 13. the peak pressure goes from about 87 bar to 122 bar over the same range of equivalence ratio. it is worthwhile seeing the effect of fuel on the level of exhaust constituents. the nitrogen has to compete with the carbon monoxide and hydrogen for any oxygen that becomes available.8. and result in about 14 000 ppm. the general level of NO is higher with octane than methane because of the slightly higher temperatures achieved with this fuel.8. It will be shown in Chapter 14 that the rate at which a reaction occurs is exponentially related to temperature. = 0.11 and 13. as well as the temperature of the products.) and oxygen (0. as would be expected. the lower temperature at this equivalence ratio limits the amount of NO produced by the reaction. = 0.9.g. the combustion process does not take place instantaneously at tdc as shown here.8. The effect of these kinetics is that the instantaneous level of NO in the cylinder does not achieve the equilibrium level. First.8.)present in the mixture.1. and this is equivalent to about 13 000 ppm (parts per million [by mass]). and again lags the level while it decreases down the expansion stroke of the engine. and it gains most of the oxygen from the carbon reactions. However. The levels of NO in the exhaust gas of an engine are significantly lower than those calculated above for a number of reasons. and the larger proportion of CO.2. Hence. but experience shows that the maximum values of NO in engine exhaust systems (around 2000 to 5000 ppm) occur at about @ = 0. and this level then dominates the exhaust value. The increase in temperature will tend to increase dissociation effects in all cases. whilst at high temperatures the driving force to react is high but there is a deficiency of oxygen. and obviously does not occur at the highest temperature. Secondly. The maximum level of NO attained is a mole fraction of about 0. whereas an increase in pressure will tend to decrease the dissociation effects in cases where dissociation increases the total amount of substance (e.7 to 0. while the equilibrium level of NO is a maximum at g5 = 0. = 0. . When the equilibrium concentration is decreasing. In fact. the actual level of NO still cannot maintain pace with it. level is still significantly higher than with methane. The additional reactions do not have a major effect on the exhaust composition with octane as a fuel. = 1.Effect of dissociation on combustionparameters 275 peak temperature increases from about 2200 K at Q. which can be ‘robbed’ for oxygen.
carbon dioxide and water can occur at high temperature. the rates at which chemical reactions occur are usually fast and hence some reactions get close to equilibrium even in the short time the gases are in the combustion zone. and would only be achieved after infinite time. combustion in the combustion chamber of a gas turbine has to be rapid enough to be completed before the gas leaves the chamber.1 Introduction Up until now it has been assumed that chemical reactions take place very rapidly. While most combustion processes are extremely fast. diesel and petrol engines. which might well be frozen into the products as the temperature drops. Such short times mean that it is not possible for all the gases in the combustion chamber to achieve equilibrium . The values shown were based on the equilibrium amounts of the substances. is formed in all combustion processes. The number of . An analysis of the kinetics of reactions will now be presented.) will be negligible. the combustion in a reciprocating engine running at 6000 rev/min has to be completed in about 5 ms if the engine is to be efficient. is a pollutant which is limited by legislation because of its initant effects.2 Reaction rates Reaction rates are governed by the movement and breakdown of the atoms or molecules in the gas mixture: reactions will occur if the participating ‘particles’ collide. including boilers.they will be governed by the chemical kinetics of the reactions. it can be removed in some cases by the use of catalytic converters. and the level of oxides of nitrogen (NO. however.14 Chemical Kinetics 14. and that the equilibrium conditions are reached instantaneously. For example. gas turbines. if the oxygen and nitrogen are involved in a combustion process then they will join together at the high temperature to form NO. often their speed is not such that combustion can be considered to be instantaneous. compared with the physical processes surrounding them. Likewise. It was shown in Chapters 12 and 13 that significant dissociation of the normal products of combustion. Chemical kinetics plays a major role in the formation of pollutants from combustion processes. 14. However. This NO. For example. oxygen and nitrogen will coexist in a stable state at atmospheric conditions. NO.
1) C02 + H2H20 kb kf + CO where the first reaction is a general one and the second is an example based on the water gas reaction (chosen because the same number of reactants and products exist on both sides). Many simple chemical reactions are second order. . . This is obviously a measure of the number of particles per unit volume since each amount of substance is proportional to the number of molecules..O + CO (14.. A+BC+D kb kf (14. and Y . O . + H. In this case q has been taken as the same on both sides of the equation because it is assumed that the same species can exist on both sides. 14.1 . Equation (14. . CO.Reaction rates 277 collisions occurring in a mixture will be closely related to the number densities (number per unit volume) of the 'particles'.1 Diagrammatic representation of molar concentration. . reactants are capable of reacting. c . 0 . . For example. . . which is the amount of substance per unit volume. The number density can be defined by the molar concentration.4) . These reactions can be written as (14. and Y" that of the products. e. or more.2) where A . If a species does not exist on one of the sides it is represented by a stoichiometric coefficient of zero ( Y = 0). A..2) can be further generalised to (14. . The molar concentration will be denoted by enclosing the reactant or product symbol in [ 1.1. . Fig.. . . Molar concentration in (a) is approximately half that in (b) Reactions occur when two. 0 . wH.g.3) where q = total number of species being considered. etc are the respective stoichiometric coefficients. v 2 . v' represents the stoichiometric coefficients of the reactants.. this is illustrated in Fig 14.. 1: 'd. etc are the elements or compounds involved in the reaction.
The reaction shown in eqn (14... or depletion.C kb i=l V.=O ~l.278 Chemical kinetics can be represented by 4 b 4 v:.5) the reaction was described as having a forward and backward direction.A.. = H2 v. for an elementary reaction.6) may be written as n R j = k . Equation (14.=H. is Rja [Al]”J[A2]’*J [A.=1 A..~i. Thus.1) to (14. . . states that the rate of formation.=o A.]’” for ( j = 1. each raised to the power of its stoichiometric coefficient. of a species is proportional to the product of molar concentrations of the reactants.= CO The law of mass action.=l vk=O v:=1 A.s) (14. for the forward direction (14. and kb.]” or n (14.. n [ A J y J f o r ( j = 1. s) i= 1 (14. = bj i= 1 [A. which is derived from the kinetic theory of gases...=C02 v\=l v’~=O v. .s) and s = total number of simultaneous reactions.7) can be described in this way as n R.9) i= 1 The rate of change with time of species i is proportional to the change of the stoichiometric coefficients of Ai in the reaction equation (the system is effectively a first order one attempting to achieve the equilibrium state). with rates k.8) and Rbj= kbj n n [A. (14.10) .5) i= 1 where q = 4 vij = stoichiometric coefficient of i in reaction j A.7) where kj is the rate constantfor the reaction.]” for ( j = 1 . In eqns (14. .O v.6) Rj=n[Ai]” i= 1 f o r ( j = 1. .S) (14. Hence the rate of formation of species j .
Chemical kinetics of NO and.]'' . This means that the rate constant for the reaction can be defined by an equation of the form k = Ae . indicating that the number of collisions is related to the temperature in those cases. The factor A is called the preexponential factor. gives d [C ]/d t = k. their concentration and temperature. is related to the ability of atoms or ions to combine.[C].13) The net rate of generation of species C is given by . and some values are .[A]:[B]? = k.[kf[A]'"[B]" d[C1 dt .kb[c]''[DP] =y (14.16) Therefore the net rate is d[C]/dt = R j [ a v ~ / 3 vy"C6vd1 b (14. Obviously the collision rate is a function of the number of particles per unit volume.'.14) Using the notation [A]/[Al.17) 14. a "0/3"b[A 2[B 1 .[D].'d= and [Dl/[Dl. or the frequency factor. In combustion engineering this will usually occur when two or more particles collide.3 Rate constant for reaction. [D ]2 ] 2 6 At equilibrium k. the suffix e represents equilibrium concentrations.2.'. for the backward direction 279 (14. i. It has been found experimentally that most reactions obey a law like that shown in Fig 14. where (14. and is dependent on the rate at which collisions with the required molecular orientation occur. and their velocity of movement.kbyVcvd [C 1.e. k The rate constant for the reaction.. The term E in the exponent is referred to as the activation energy. A sometimes contains a temperature term. = /3. [Cl/[Cl.11) Hence the net rate of formation of Ai is d [Ailj [A. The values of A and E are dependent on the reactions being considered.kbj n i= 1 [Ai]" (14. [Bl/[B].18) This equation is called the Arrhenius equation. Most chemical reactions take place between two or three constituents because the probability of more than three particles colliding simultaneously is too small.E / R T (14. k.. = 6.12) Consider the following rate controlled reaction equation: kf vaA + vbBvcC kb + vdD (14. = a .15) Rj (14.
It appears in the exponential term because not all activated molecules will find conditions favourable for reaction. Q. carbon or sulfur).g. Activation Enthalpy (or internal energy) of reaction.3 Schematic interpretation of activation energy 14.3. The formation of NO in combustion processes can occur from two sources: thermal NO and prompt NO. is shown in Fig 14. This section will restrict itself to considering thermal NO. E . ) Progress of reaction Fig.280 Chemical kinetics 11 T Fig.4 Chemical kinetics of NO The chemical kinetics for the formation of NO are relatively well understood. (or Q. and will be developed here. 14. and will be produced even if there is no nitrogen in the fuel itself. where it can be seen to be the energy required to ionise a particular molecule and make it receptive to reacting. The chemical kinetics for other pollutants can be derived in a similar way if the necessary reaction rates are available.2 Relationship between reaction rate and temperature introduced below. Prompt NO is . 14. although it should be recognised that most other pollutants are produced by reactions between the oxygen in the air and a constituent of the fuel (e. The significance of the activation energy. Thermal NO is formed by the combination of the oxygen and nitrogen in the air.
and 0 and 0. (2) N+O.20).2 x m3/kmoi s + OH. [N... Then the following expressions are obtained for the burned gas.OIe= Y where suffix e denotes equilibrium values.The amount of nitrogen in most conventional hydrocarbon fuels is usually very low. k f4 .19) the net rate is kfl[Nl [NO1 + k. M can be assumed to be N.1 x = 6. x e(305W/T) m3/kmo1s In these equations the rate constants (kf.. 14. Using a similar procedure for eqns (14.Chemical kinetics of NO 281 thought to be formed in the flame as a result of the combination of the nitrogen in the fuel with the oxygen in the air. [NI/[NIe = B. which exists after the passage of the flame through the unburned mixture..O (7) N.O k. + R.[Nle[NOle + kbl[N2le[Ole But k. the backward rate.. These equations can be applied to the zone containing 'burned' products.3.19) becomes aBR.21) and (14. + R.25) ( 3 ) N+OHNO+H. NO + NO.2 k. or product. .OI/[N.. = 4.) are all in m3/kmol s. Also let [NOI/[NOIe= a . + 0. but is assumed to be unchanged by the reactions.0 x 10'0 x e(535'J/T) m3/kmol s k f5 .3. + R. NO From eqn (14. 1012 .19) x lo6 x iolo Tx m3/kmol s (14.23) (14.I[N21 [OI = aBkf.24) (14. (4) H + N.. k.22) (14.(189W/T) m3/kmol s +M e N .[Nle[NOle= kbl[N2le[Ole= R. 1970) (1) N + N O e N . + O . O e N .. so the net rate for eqn (14.1 RATE EQUATIONS FOR NITRIC OXIDE The rate of formation of nitric oxide can be derived in the following manner. The governing equations for the mechanism of NO formation are (Lavoie et al.21) (14. + B(R.NO+O.24) involving NO gives the following expression. (14. Expression for nitric oxide.4 10" x e('60/T) m3/kmol s ( 14. are in equilibrium with each other. k.26) where V is the volume of the products zone. = kf5 = ( 5 ) 0 + N . M is a third body which may be involved in the reactions. k. + 2aR6) + R. lo'. which also allows for the change in volume over a time step: _ _ ([NOIV) = a(BR.4. (6) 0 + N.. = 3. volume.20) (14. + R. and R. these values can be calculated by the methods described in Chapter 12. be the forward reaction rate. +0+M. the 'one way' equilibrium rate. It will be assumed that H and OH.) + 2yR6 V dt 1 d (14. Consider reaction j : let k. k.O=N.
22) to (14.25) all involve N 2 0 and can be combined to give .) + + R.21).28) are several orders of magnitude shorter than those of reaction (14. (14. (1971) derived the initial rate of formation of NO in the following way. + R.30) These values can be substituted into eqn (14.26). When the nitric oxide (NO) starts to form. + R3) (14. (% + R5 + R6 + R7) (14.O Equations (14. It has been found (Lavoie et al. 14. + a(R.O]V) = 1 d V dt y(R4 + R.([NIV) = B(aR.28) Y= B= Rl + a(R2 + R.27) ( a K + R2 + R3) and from eqn (14.3 1) is the dominant equation for the initial formation of NO. (14.29) R4 + R5+ a2R6+ R.20) and (14.28) A finite time is required for the reactions to reach their equilibrium values.27) Expressionfor nitrous oxide N. V dt 1 d + R. and eqn (14. 1970) that the relaxation times of reactions (14.([N. which means that the righthand sides of eqns (14.282 Chemical kinetics Expressionfor atomic nitrogen. N Equations (14.26) to give This is the rate equation for NO that is solved in computer programs to evaluate the level of NO in the products of combustion. + a'% + R.2 INITIAL RATE OF FORMATION OF NO Heywood et al. Then. It can be shown that eqn (14..19). give . this is called the relaxation time.31) can be written (14. from eqn (14. the value of a = 0. It should be noted that the variation in the molar concentration is a firstorder differential equation in time and relates the rate of change of [NO] to the instantaneous ratio of the actual concentration of NO to the equilibrium value (i. When the actual level of [NO] is at the equilibrium level then a = 1 and the rate of change of [NO] = 0.32) .27) and (14. + R3) + R.) (14..4. a ) .28) are zero.27) and (14.e. and hence it can be assumed that the [N] and [N20] values are at steady state. + R. which all involve N.
the value of the rate constant for the reaction in the forward direction is k.7957 x lo. 15 bar. which are based on those in Heywood (1988). fuel.34) gives d[NO1 dt e(69090/T) T1/2 [02]~/2[N2]. which depict the rate of change of mole fraction of NO.35) Heywood (1988) also showed that where (14.].Chemical kinetics o NO f 283 Heywood (1988) stated that.34): the rate constant for the reaction is in cm3/mols.6 x 1013x e(38000/T) cm3/mol s (14.]. can be calculated from the perfect gas law.4. kmol and seconds and this must be taken into account. were then calculated in the following way. which should be in mol/cm3. xNZ 7. and the exponential term is significantly different from that in eqn (14. mol and seconds rather than SI units of m3. and [N2]. Hence (14.4 were: pressure.5319 x lo’. . cm3/mols (14.34) It is necessary to note two factors about eqn (14.. The value of [O. Using these conditions the equilibrium concentrations of all the reactants were calculated using the techniques described in Chapter 12.37) The values of [O.39) Calculating the initial rate of change of NO with time gives the results shown in Fig 14. Equation (14. can be obtained from an equilibrium analysis of the mixture. = xoz= 7. = 7.6: x0 =4.19). using a three equation set for the formation of NO. octane. The rate kinetic values.37) is based on cm3. because (14..38) Likewise (14.36) Substituting this value into eqn (14. This gave the following mole fractions for the condition T = 2000 K.7725 x lo’. The conditions used to evaluate Fig 14. @ = 0.
= = 7.3143 x 2000 Vm== P is x.284 Chemical kinetics 7/ f 7 2000 7100 2200 2300 2400 2500 2600 2700 2800 Temperature / (K) Fig.7941 x lo’ mol/cm3 $ 7.7957 x lo* [Q].40) (14. = . where M is a general substance (14.5319 x lo’ 11086 = 4.0320 x mol/cm’ 11086 11086 . 11086 x io5 lo6 = 11086 cm3/mol [O].4 Initial rate of formation of nitric oxide for combustion of octane at a pressure of 15 bar The molar concentration is defined as xun xu [MI= = .41) V vm %T 8. 14.3051 x moi/cm3 m 1 e=11086 = 6. = XN> 4.7725 x lo’ 11086 7.
which gives = x e( .34) and (14. Other kineticscontrolledpollutants Carbon monoxide (CO) is formed in processes in which a hydrocarbon is burned in the presence of oxygen.37) give similar results. there is more fuel than oxygen available to oxidise it) then there is bound to be some carbon monoxide formed. where M is a general substance Hence. in this case.4022 These values can be converted from molar concentrations to more useful parameters and.35). or eqn (14.11086 x 2.Chemical kinetics o NO f 285 Using a combination of eqns (14.7941 x ) x 20001/2 x mol/cm3s (14. Rearranging eqn (14.40) gives xM = [Mlv.3051 x lo’ x 6. this was discussed in Chapters 12 and 13.37).34) and (14. even if the mixture is lean there will be some carbon monoxide due to the dissociation of the carbon dioxide.45) For this condition d(XNO) . eqn (14.35) gives dt = 15.43) = 2. .42) = 2. It can be seen that either eqns (14. they will be depicted as rate of formation of mole fraction.2 x 1013x e x (38000/2000) x 4.) is formed by oxidation of the sulfur in the fuel.7941 x (14. Carbon particulates are formed during diffusion combustion because the oxygen in the air is not able to reach all the carbon particles formed during the pyrolysis process while they are at a suitable condition to bum. until misfire occurs in the combustion device.491 mol/cm3s A similar value can be obtained from eqn (14.4 were calculated in this manner. However.0320 x 106)’/2 6. Sulfur dioxide (SO.6 9 0 9 0 ~ 2 ~x (7. for oxygen is similar to that used in the program for calculating the values of mole fraction of atomic oxygen.44) (14. If the mixture is rich (Le.46) The curves in Fig 14.762 x s’ (14. This indicates that the dissociation equation.491 x lo’ = dt = 2. the rate of production of NO in terms of mole fraction is given by (14..36). The amount of carbon monoxide reduces as the mixture gets leaner.
during the combustion process. which has a high percentage of sulfur. which have corrosive effects on exhaust stacks. a process by which the sulfur dioxide reacts with limestone to form gypsum. The levels of sulfur dioxide produced in some power plant can be extremely high. are primary pollutants produced by dissociation in combustion reactions. but do consume copious amounts of limestone. emissions from vehicles become a more serious problem. Sulfur can be removed from crude oil by catalytic hydrodesulfurisation.5 The effect of pollutants formed through chemical kinetics 14. Among the pollutants involved in photochemical smogs are ozone.) EMISSIONS Sulfur emissions can only occur if there is sulfur in the fuel.) acids. Power stations running on heavy fuels or some coals will produce large quantities of sulfur fumes. a fuel obtained by water extraction of lowgrade oils. Photochemical smogs were first identified in Los Angeles in the midl940s. A further advantage of reducing the sulfur content of diesel fuels is that this reduces the synergy between the sulfur and the particulates.5. will produce significant quantities of sulfur dioxide. These processes are suitable for stationary plant. and both ‘prompt’ and ‘thermal’ NO. and the imposition of smokeless zones in urban areas have reduced the problem to a more acceptable level. cause corrosion and form acid rain. and the subsequent reactions with hydrocarbons. and brought about the stringent legislation introduced in California to control the emissions from automobiles. This can then form sulfurous (H2S03)and sulfuric (H. These smogs act as bronchial irritants and can also irritate the eyes. power generation. the levels of sulfur might be significantly higher and then the SO. which smell noxious. It has been .. It is possible to use flue gas desulfurisation to reduce the levels of SO. and other oxides of nitrogen. nitrogen dioxide and peroxyacyl nitrate (PAN).2 SULFUR DIOXIDE (SO. before being released into the surrounding atmosphere to form acid rain. emitted to the atmosphere.286 Chemical kinetics 14.SO. g/m3 (at normal temperature and pressure). but is often left in the residual oils which are used for marine propulsion. In the developing world. and the sulfur levels are often around 0. but such systems are expensive to install and run. etc. The use of orimulsion. The move away from coal to gas for electricity generation. and reduces the quantity of particulates produced. Glassman (1 986) described in some detail the chemical chain that results in photochemical smog. etc. emissions from vehicles are not a major problem. chimneys. Many coal burning power stations are now being fitted with flue gas desulfurisation. or g/mile (if applied to a vehicle engine). also brings worries of high sulfur fuels.5. The nitrogen dioxide.1 PHOTOCHEMICAL SMOG Photochemical smogs are formed by the action of sunlight on oxides of nitrogen. Ozone and PAN are secondary pollutants produced by the action of sunlight on the primary pollutants and the atmosphere. The levels of sulfur in diesel fuel and petrol are being reduced at the refinery in the developed world. SO. Diesel engines running on ‘heavy fuel’. can be involved in the reactions.5% or lower. Sulfur in fuel has been a problem for a long time and caused high levels of acid rain in UK until recently. Oxides of nitrogen can be measured using nondispersive infrared (NDIR) equipment and the values are often quoted in parts per million (ppm). g/kWh. 14. Sulfur in the fuel tends to be oxidised into SO.
emitted from the UK power stations were converted to sulfuric acid the supply of this acid would exceed the UK demand. These are all hydrocarbon fuels with the quantity of hydrogen decreasing as the fuel becomes heavier. It will take some time to prove conclusively whether global warming is occurring. and other smaller diesel engines can achieve around 50% thermal efficiencies when operating at close to fullload. There have been significant variations in temperature through the last few centuries. or changing the fuel to./kW is the combined cycle gas turbine plant (CCGT) running on methane. Dry soot is usually taken to mean the carbon that is collected on a filter paper in the exhaust of an engine. however. the policy that should be adopted is for the amount of CO. and increases with sulfur content. The carbon formed during combustion can be an asset in a boiler because it increases the radiant heat transfer between the flame and the tubes of the boiler. hydrogen. What is indisputable is that mankind has released a large amount of carbon from its repository in hydrocarbons back into the atmosphere as CO. The PAH compounds have a tendency to be carcinogenic. The carbon formed in diesel engine and gas turbine combustion is not beneficial and it increases the heat transfer to the components.. it is necessary to ensure that the soot emissions from the stack are not excessive. with warm summers at times and the freezing over of the Thames at others. increasing the need to provide cooling. and then weighing the quantity. Obviously. while absorbing the long wavelength infrared transmission from objects on Earth. say. Large marine diesel engines also achieve thermal efficiencies of greater than 50%. Such plant can achieve thermal efficiencies higher than 50% and claims of efficiencies as high as 60% have been made./mile to be reduced. in which a rich zone can produce carbon particles prior to subsequent oxidation. The most efficient power station. they are soot particles on which other compounds (often polycyclic aromatic hydrocarbons [PAH]) have condensed. 14. which is assessed by the ‘reflectance’ of a filter paper on which the soot has been collected. This can be achieved by using more efficient engines. but there is a difference in nature between these emissions.5. particulate emissions tend to come from diesel engines.4 GREENHOUSE EFFECT The greenhouse effect is the name given to the tendency for the carbon dioxide in the atmosphere to permit the passage of visible (short wavelength) light. The words particulates and soot are often used synonymously. Hence.The effect of pollutants formed through chemical kinetics 287 stated that if all the SO. they might be quoted in g/kW h. The unit of measurement of soot is usually the Bosch Smoke Number. The most convenient form of energy available to man is that found as gas.5.3 PARTICULATE EMISSIONS These are generated mainly by devices which rely on diffusion burning (see Chapter 15). The evidence for global warming is not conclusive because the temperature of the Earth has never been constant. 14. It is presaged that the intercooled . The level of particulates is strongly affected by the amount of sulfur in the fuel. as shown by the Ice Ages of the past. gas turbines and boiler plant. The effect of this is to cause the temperature of the Earth to increase. using conventional fuels./kW or CO. The combustion of any of these fuels will produce carbon dioxide. in terms of CO. Particulates are measured by trapping the particles on glassfibre filter papers placed in a dilution tunnel. oil or coal. Particulates contain more than simply the dry soot.
288
Chemical kinetics
regenerated gas turbine will also have efficiencies of this order, and it is claimed, will compete with turbocharged diesel engines down to the 5 M W size range. The hydrogen powered engine produces no carbon dioxide, but does form NO,. However, the major problem with hydrogen is its production and storage, particularly for mobile applications. California has now introduced the requirement for the zero emissions vehicle (ZEV) which must produce no emissions. At present the only way to achieve this is by an electric vehicle. It has been said that a ZEV is an electric car running in California on electricity produced in Arizona! This is the major problem that engineers have to explain to politicians and legislators: the Second Law states that you cannot get something for nothing, or breakeven. Many ideas simply move the source of pollution to somewhere else.
14.5.5
CLEANUPMETHODS
The cleanup methods to be adopted depend upon the pollutant and the application. As stated above, the exhaust of a power station can be cleaned up using a desulfurisation plant to remove the sulfur compounds. It is also possible to remove the grit from the power station boilers by cyclone and electrostatic precipitators. These plants tend to be large and would be inappropriate for a vehicle, although investigations to adapt these principles to diesel engines are continuing. All petroldriven cars being sold in the USA, Japan and Europe are fitted with catalytic converters to clean up the gaseous emissions. This currently requires that the engine is operated at stoichiometric mixture strength so that there is sufficient oxygen to oxidise the unburned hydrocarbons (uHCs) while enabling the carbon monoxide (CO) and NO, to be reduced. This means that the engine has to be operated under closed loop control of the airfuel ratio, and this is achieved by fitting a h sensor (which senses the fuelair equivalence ratio) in the exhaust system. The error signal from the sensor is fed back to the fuel injection system to change the mixture strength. The need to operate the engine at stoichimetric conditions at all times has a detrimental effect on the fuel consumption, and investigations into lean operation (reducing) catalysts are being undertaken. At present it is not possible to use catalytic converters on diesel engines because they always operate in the lean bum regime. This causes a problem because there is no mechanism for removing the NO, produced in the diesel engine combustion process, and it has to be controlled in the cylinder itself. Lean bum catalysts, based on zeolites, are currently under research and will have a major impact on engine operation  both sparkignition and diesel. Another pollutant from diesel engines is the particulates. These are a significant problem and attempts have been made to control them by traps. Cyclone traps are being investigated, as well as gauzebased devices. A major problem is that after a short time the trap becomes full and the carbon has to be removed. Attempts have been made to achieve this by burning the particulates, either by selfheating or external heating. At present this area is still being investigated.
14.6
Other methods of producing power from hydrocarbon fuels
All of the devices discussed above, i.e. reciprocating engines, gas turbines, steam turbines, etc., produce power from hydrocarbon fuels by using the energy released from the combustion process to heat up a working fluid to be used in a ‘heat engine’. Hence, all of
Problems 289
these devices are limited by the Second Law efficiency of a heat engine, which is itself constrained by the maximum and minimum temperatures of the working cycle. It was shown in Chapters 2 and 4 that the maximum work obtainable from the combustion of a hydrocarbon fuel was equal to the change in Gibbs energy of the fuel as it was transformed from reactants to products: if there was some way of releasing all of this energy to produce power then a Second Law efficiency of 100% would be achievable. A device which can perform this conversion is known as a fuel cell; this obeys the laws of thermodynamics but, because it is not a heat engine, it is not constrained by the Second Law. Fuel cells are discussed in Chapter 17.
14.7
Concluding remarks
'This is the first time nonequilibrium thermodynamics has been introduced. It has been shown that, while most thermodynamics processes are extremely rapid, it is not always possible for them to reach equilibrium in the time available. The effect of rate kinetics on the combustion reactions is that some of the reactions do not achieve equilibrium and this can be a major contributor to pollutants. The rate equations for nitric oxide have been developed. Finally, the pollutants caused by combustion have been introduced, and their effects have been described.
PROBLEMS
1 A reaction in which the preexponential term is independent of temperature is found to be a hundred times faster at 200°C than it is at 25°C. Calculate the activation energy of the reaction. What will be the reaction rate at lOOO"C? [30 840 kJ/kmol; 13 8141
2 A chemical reaction is found to be 15 times faster at 100°C than at 25°C. Measurements show that the preexponential term contains temperature to the power of 0.7. Calculate the activation energy of the reaction. What will be the reaction rate at 700"C? [31 433 kJ/kmol; 15 2041
3 The rate of formation of nitric oxide (NO) is controlled by the three reversible
chemical reactions:
k,' 0 + N,NO
+N
kiN+C&NO+O
lcz
.+
ki
N + OHNO k;
+&
+H
290 Chemical kinetics Use the steady state approximation for the nitrogen atom concentration and the assumption of partial equilibrium for the reactions governing the concentrations of 0, O,, H and OH, show that
B= 6 R + a
aR+ 1 where B = [N]/[N],, 6 = [N2]/[N2],, a = [NO]/[NO],, R = R,/(R, + R3), and Rj is the equilibrium reaction rate of reaction j , and [ ] denotes the molar concentration, and [ 1, is the equilibrium molar concentration. Derive an expression for d[NO]/dt in terms of R,, B, a and 6. At a particular stage in the formation of nitric oxide the values of R and a are 0.26 and 0.1 respectively. Why is 6 = 1 likely to be a good approximation in this case? What is the error if the rate of formation of NO is evaluated from the larger approximation d[NO]/dt = 2R,, rather than the equation derived in this question? [3.64%]
4 The rate of change of mole concentration of constituent A in a chemical reaction is expressed as
&41    k[A]" dt While mole concentration is the dominant property in the reaction it is much more usual for engineers to deal in mole fractions of the constituents. Show that the rate of change of mole fraction of constituent A is given by
where p = density. Also show how the rate of change of mole fraction is affected by pressure. [dxA/dta p"']
15
Combustion and flames
15.1 Introduction
Combustion is the mechanism by which the chemical (bond) energy in a ‘fuel’ can be converted into thermal energy, and possibly mechanical, power. Most combustion processes require at least two components in the reactants  usually a fuel and an oxidant. The chemical bonds of these reactants are rearranged to produce other compounds referred to as products. The reaction takes place in a flume. There are three parameters which have a strong influence on combustion: temperature, turbulence and time. In designing combustion systems attention must be paid to optimising these parameters to ensure that the desired results are achieved. In reciprocating engines the time available for combustion is limited by the operating cycle of the engine, and it is often necessary to increase the turbulence to counterbalance this effect. In furnaces the time available for combustion can be increased by lengthening the path taken by the burning gases as they traverse the chamber. There are two basically different types of flame: premixed and diffusion. An example of premixed flames occurs in conventional sparkignition (petrol, natural gas, hydrogen) engines. In these engines the fuel and air are mixed (often homogeneously) during the admission process to the engine, either by a carburettor or low pressure inlet manifold fuel injection system. Ignition is initiated by means of a spark, which ignites a small volume of the charge in the vicinity of the spark plug; this burning region then spreads through the remaining charge as a flame front. This type of combustion mechanism can be termed flume traverses charge (FTC), once combustion has commenced it is very difficult to and influence its progress. The diffusion flame occurs in situations of heterogeneous mixing of the fuel and air, when fuelrich and fuellean regions of mixture exist at various places in the combustion chamber. In this case the progress of combustion is controlled by the ability of the fuel and air to mix to form a combustible mixture  it is controlled by the diffusion of the fuel and air. An example of this type of combustion is met in the diesel engine, where the fuel is injected into the combustion chamber late in the compression stroke. The momentum of the fuel jet entrains air into itself, and at a suitable temperature and pressure part of the mixture spontaneously ignites. A number of ignition sites may exist in this type of engine, and the fuelair mixture then bums as the local mixture strength approaches a stoichiometric value. This type of combustion is controlled by the mixing (or diffusion) processes of the fuel and air. Other examples of diffusion combustion are gas turbine combustion chambers, and boilers and furnaces.
292 Combustion andflames
These different combustion mechanisms have an effect on how the energy output of the combustion process can be controlled. In the homogeneous, premixed, combustion process the range of airfuel ratios over which combustion will occur is limited by the flammability of the mixture. In old petrol engines the mixture strength varied little, and was close to stoichiometric at all operating conditions (the mixture was often enriched at high load to reduce combustion temperatures). In modem engines, attempts are made to run the engines with weaker mixtures (Le. leanburn). At present, all sparkignition engines operate with a throttle to limit the air flow at low loads. This is known as quantitative governing of the engine power because the quantity of charge entering the engine is controlled, and this controls the power output. Throttling the engine reduces the pressure in the inlet manifold, and effectively the engine has to pump air from the inlet manifold to the exhaust system, giving a negative pumping work of up to 1 bar mep. The advantage of leanbum engines is that the load control can be partly by making the mixture leaner, and partly by throttling. Honda have an engine which will run as lean as 24: 1 airfuel ratio on part load; this reduces the combustion temperatures, and hence NO,, and also reduces the pumping work over a substantial part of the operating range. The power output of a diesel engine is controlled by changing the amount of fuel injected into the cylinder  the air quantity is not controlled. This means that the overall airfuel ratio of the diesel engine changes with load, and the quality of the charge is controlled. This is referred to as qualitative governing and has the benefit of not requiring throttling of the intake charge. The diesel engine operates over a broad range of airfuel ratios. However, the richest operating regime of a diesel engine is usually at an air fuel ratio of more than 20 : 1, whereas the petrol engine can achieve the stoichiometric ratio of about 15 : 1. This means that, even at the same engine speed, the diesel engine will only produce about 70% of the power output of the petrol engine. However, the lack of throttling, higher compression ratio, and shorter combustion period mean that the diesel engine has a higher thermal efficiency than the petrol engine. (Note: the efficiency of engines should be compared on the basis of the specific fuel consumption [kg/kW h ] rather than miles per gallon bscause the calorific values [kJ/kg] of diesel fuel and petrol are approximately the same, but the calorific value of diesel fuel in W/m3 is about 15% greater than that of petrol because the fuel density is about 15% greater. A diesel vehicle which achieves only 15% more miles/gallon than a petrol engine is not more efficient!) Gas turbine combustion chambers and boilers also control their output in a qualitative manner, by varying the airfuel ratio. An important feature of a flame is its rate of progress through the mixture, referred to as the flame speed. Flame speed is easiest understood when related to a premixed laminar flame, but the concept of flame speed applies in all premixed combustion.
15.2 Thermodynamics o combustion f
When fuel and air are mixed together they are in metastable equilibrium, as depicted schematically in Fig 15.1. This means that the Gibbs energy of the reactants is not at the minimum, or equilibrium, value but is at a higher level. Fortunately it is still possible to apply the laws of thermodynamics to the metastable state, and hence the energies of reactants can be calculated in the usual way. Even though the reactants are not at the minimum Gibbs energy, spontaneous change does not usually occur: it is necessary to provide a certain amount of energy to the mixture to initiate the combustion  basically to ‘ionise’ the fuel constituents. Once the fuel constituents (usually carbon and hydrogen) have been ‘ionised’ they will combine with the oxygen in the air to form compounds with a lower
Thermodynamics of combustion 293
Gibbs energy than the reactants; these are called the products (usually carbon dioxide, water, etc). In the case of the sparkignition engine the ionisation energy is provided by the spark, which ignites a small kernel of the charge from which the flame spreads. In the diesel engine part of the mixture produced in the cylinder cannot exist in the metastable state: it will spontaneously ignite. Such a mixture is termed a hypergolic mixture.
9
x e
r3
Q)
2
\
Metastable
\
Stable equilibrium
State Fig. 15.1 Energy states associated with combustion Some mixtures are unstable at room temperature, and their constituents spontaneously ignite. An example of such a mixture is hydrogen and fluorine. This concept of spontaneous ignition will be returned to later. All of these thermodynamic processes take place somewhere in the combustion zone, and many of them occur in the flame. Before passing on to the detailed discussion of flames it is worthwhile introducing some definitions and concepts.
15.2.1 REACTION ORDER
The overall order of a reaction is defined as n = cy=, summed over the q species in the v,, reactants.
Firstorder reactions
These are reactions in which there is spontaneous disintegration of the reactants. These reactions do not usually occur, except in the presence of an ‘inert’ molecule.
Secondorder reactions
These are the most common reactions because they have the highest likelihood of a successful collision occurring.
Thirdorder reactions
These are less likely to occur then secondorder ones but can be important in combustion. An example is when OH and H combine to produce an H,O molecule. This H,O molecule
294 Combustion and James
will tend to dissociate almost immediately unless it can pass on its excess energy  usually to a nitrogen molecule in the form of increased thermal energy.
15.2.2
PROCESSES OCCURRING IN COMBUSTION
The thermodynamics of combustion generally relates to the gas in isolation from its surroundings. However, the surroundings, and the interaction of the gas with the walls of a container, etc, can have a major effect on the combustion process. The mechanisms by which the combusting gas interacts with its container are: (i) (ii) (iii) (iv) (v) transport of gaseous reactant to the surface  diffusion; adsorption of gas molecules on surface; reaction of adsorbed molecules with the surface; desorption of gas molecules from the surface; transport of products from the surface back into the gas stream  diffusion.
These effects might occur in a simple container, say an engine cylinder, or in a catalytic converter. In the first case the interaction might stop the reaction, while in the second one it might enhance the reactions.
'
15.3 Explosion limits
The kinetics of reactions was introduced previously, and it was stated that reactions would, in general, only occur when the atoms or ions of two constituents collided. The reaction rates were derived from this approach, and the Arrhenius equations were introduced. The tendency for a mixture spontaneously to explode is affected by the conditions in which it is stored. A mixture of hydrogen and oxygen at 1 bar and 500°C will remain in a metastable state, and will only explode if ignited. However, if the pressure of that mixture is reduced to around 10 mm Hg (about 0.01 bar) there will be a spontaneous explosion. Likewise, if the pressure increased to about 2 bar there would also be an explosion. It is interesting to examine the mechanisms which make the mixture become hypergolic. The variation of explosion limits with state for the hydrogenoxygen mixture is shown in Fig 15.2.
lOUU0
h
r"
E
v ,
E
B
IO0
2
2 a
IU
I
3911
.rin
430
45(1
471
490
510
530
550
570
590
Temperature / ("C)
Fig. 15.2 Explosion limits for a mixture of hydrogen and oxygen (from Lewis and von Elbe, 1961)
A general branched chain reaction may be written MR kl initiation chain branching. P . and explosions will only occur at high temperatures.k . the speed of the reaction is very dependent on the multiplication factor of the reactions. The first step is highly endothermic (it requires energy to be supplied to achieve the reaction). where the first step proceeds more rapidly. or 0. This means that an H atom can survive a lot of collisions without reacting.62 ps: an extremely fast reaction! If the multiplication factor is only 1.1 THE EFFECT OF MULTIPLICATION FACTOR ON THE TENDENCY TO EXPLODE The effect of the multiplication factor can be examined in the following way. Assume a straight chain reaction has lo* collisions/s. if the multiplication factor is now 2 then 2" 10".1) The first two of the three steps are called branching steps and produce two radicals (highly reactive ions) for each one consumed. and can be destroyed at the wall of the container. The value of a necessary to achieve an explosion can be evaluated. a > 1 product formation removes radical R+MaR+M R+MP k3 k2 R 'wall . the number of radicals produced by the chain) is between 1 and 2.01 then the total reaction time is still only 10 ms. L destruction R A destruction gas where M is a molecule. giving N=62. with 10'' molecules/cm3. and there is 1 chain particle/cm3. H202 mixtures can exist in the metastable state at room temperatures. and will be slow at low temperatures. which is approximately 30 years. a is the multiplication factor. the multiplication factor (i. Since all steps are necessary for the reaction to occur. Hence.0. The rate of formation of the product. Hence. is given by I (15.OH which leads to the further branching steps 0 + H 2 4OH + H OH + H . [ R ] [ M ] d[ dt (15.2) chain termination P 1 . and P is a product. This means that all the reactants' molecules will be consumed in 62 generations of collisions. giving a total reaction time of 62 x O' seconds.e.3) . However. 15. The third step does not increase the number of radicals. reaction are: H+O.Explosion limits 295 The kinetic processes involved in the H. R is a radical.3. 4 H 2 0 + H (15. Then all the molecules will be consumed in 10" seconds. but the overall multiplication factors do not have to be very high to achieve rapid combustion.
Table 15. 15.3)gives (15.4.5 1 5.1 Flammability and explosion limits (mixtures defined in % volume) at ambient temperature and pressure Lean Mixture ~~~~~~ Rich Explosion 18 38 25 3 Flammability 4 16 12.2 1.7 29. Examples are the Bunsen burner flame and the flame in most sparkignited engines.8 36. [ R ] ] (15.H.. It is the region where the initial breakdown of the fuel molecules occurs.5) The rate of production of the product P becomes infinite when the denominator is zero.k . as described above: premixed flames and diffusion flames.0 = k l [ M l + k 2 ( a l ) [ R ] [ M ] k 3 [ R ] [ M . COair NH302 c3Hfl02 CH.6) Thus.9 15.66 4. There are two different types of flame.1 PREMIXED FLAMES Premixed flames occur in any homogeneous mixture where the fuel and the oxidant are mixed prior to the reaction.4) Solving eqn (15. if the axact a.5 Explosion 59 90 75 37 Stoichiometric 29.6 H.1.03 3.296 Combustion and flames The steady state condition for the formation of radicals is d[RI dt .4 16. This text will concentrate on nonexplosive mixtures from now on. together with flammability limits are listed in Table 15. A few explosion limits.0 2. giving (15. ax 9.H.5 9.4) for R and substituting into eqn (15.8 66.3 Flammability 74 94 74 79 55 15 12.5 8. air C3H.4 Flames A flame is the usual mechanism by which combustion of hydrocarbons takes place in air.5 15 2 5.air C.fit then the combustion is the < nonexplosive and progresses at a finite rate.k 4 [ R ]. if amact > aCnt reaction is explosive.air C. Premixed flames will be dealt with first because it is easier to understand their mechanism. air co0. Premixed flames can progress either as deflagration or detonation .13 3.
3 Schematic diagram of Bunsen burner flame: (a) general arrangement. sparkignited engines. Other methods are used to measure the laminar flame speed. When considering laminar flame speed. 15..4. While this is a relatively simple procedure to perform. This has been replaced by the Zel’dovitch and FrankKamenetsky (1938). it is not a very accurate method of measuring laminar flame speed because of the difficulty of achieving a straightsided cone.3(b) that the shape (or angle) of the inner luminous cone is defined by the ratio of the laminar flame speed (or burning velocity). based on a thermal model. the laminar flame speed u t = ug sin a. it is useful to start with a qualitative analysis of a Bunsen burner flame.2 LAMINAR FLAME SPEED There are a number of theories relating to laminar flame speed. These can be classified as: 0 0 0 thermal theories diffusion theories comprehensive theories. such as depicted in Fig 15. This text will consider only deflagration processes. In fact. ut. The resulting flame speed will be the laminar flame speed. If the flow velocity at the exit of the tube is low then the flow of mixture in the pipe will be laminar. when the ‘end gas’ explodes spontaneously making both an audible knock and causing damage to the combustion chamber components.3. While most flames are not laminar. and also defining the edge of the luminous region. Detonation processes do occur in some premixed. and Zel’dovitch and Semenov (1940) model which includes both . in which the flame progresses subsonically. to the flow velocity of the mixture. including the rate of propagation of a flame along a horizontal tube and flat burners. The original theory for laminar flame speed was developed by Mallard and le Chatelier (1883). :f / Premixed gas and air (a) (b) Fig. (b) velocity vectors 15. It can be seen from Fig 15.Flames 297 processes. the laminar flame speed is a good indication of the velocity of combustion under other circumstances. .
The Zel'dovitch et al. while the gas flows from u to b. The details of these models will not be discussed but the results will simply be presented. but its temperature continues to increase because of the exothermic reaction taking place within the element. Le is the ratio between thermal and mass diffusivities. and D =mass diffusivity Hence.. It can be seen that the thermal diffusion goes from right to left in this diagram. If the gas had been stationary then the flame would have travelled to the left at the laminar flame speed. and . 1940) analysis results in the following equation for laminar flame speed (15. 15.298 Combustion and flames r  ____+ Mass flow +. At the end of the reaction. the mass element now loses more heat to the upstream elements than it receives from the products. against the direction of flow. and hence its temperature increases. The flame also attempts to travel from right to left. from the burned products zone (b) towards the unburned reactants zone (u).7) In obtaining eqn (15. Fig. but in this case the gas flow velocity is equal to the flame speed.IConcentration of reactantsI  I I I Tb : I I I \ Temperature I I I I I \ \ \ I I '.4. cp = specific heat at constant pressure. +a +I +%+I I I lndicates thermal energy flow I I I I I I I I I . At temperature T. i.7) the assumption had been made that the Lewis number Le=k/pc.. (1938. defined by Tbrthe chemical reaction is complete and there is no further change in temperature.e. p = density. I +. A mass element passing from left to right at first receives more heat by conduction from the downstream products than it loses by conduction to the reactants. Considering the physical phenomena occurring in the tube: heat flows. by conduction.'..D=l where k = thermal conductivity..+3 I I I . A plane flame in a tube may be shown schematically as in Fig 15.4 Schematic diagram of interactions in plane combustion flame thermal and species diffusions across the flame.
This means that the laminar flame speed.6.8a) and (15.which appears in the rate equation. This appears in more than one term In eqn (15. and the rate of reaction.Flames 299 this obviously has a major effect on the transport of properties through the reaction zone. where n is the order of the reaction. from Metgalchi and Keck (1980. where R=ZeEtRTb. The net effect is that ul= l/mw. Tb. R.5 (from Lewis and von Elbe. but for fuels which are more typical of those used in sparkignition engines.10) because density and thermal conductivity are both functions of m. in general. also have a big influence on the results obtained.8a) and for secondorder reactions (15. because the products temperature will also be higher. ul. It can be seen that. 1982) shows a similar curve. The effect of the reactant comes through its molecular weight. It can also be shown that u1= P ( ~ . a . other more complex matters. included as Z' in these equations. and n = 2 for a reaction of hydrocarbon with oxygen. the maximum value of uI occurs at close to the stoichiometric ratio.This explains the ranking order of flame speeds shown in Fig 15.9) Hence the laminar flame speed is proportional to the square root of the product of thermal diffusivity. 1961) shows the variation of u1 with reactant and mixture strength for a number of fundamental 'fuels'.' ) / ' . This means that the effect of pressure on u1is small.8b) where 2' is the preexponential term in the Arrhenius equation and c.. with the laminar flame speed for hydrogen being much higher than the others shown.5.10) which is essentially the same as eqn (15. except for hydrogen and carbon monoxide which have slightly more complex reaction kinetics. m. . For firstorder reactions (15.9). Equations (15. Figure 15.and secondorder reactions.. The assumption Le = 1 can be removed to give the following results for first. While the molecular weight is a guide to the flame speed of a fuel. will be higher if the reactants temperature is high. such as the reaction rates. Glassman (1986) shows that the flame speed can be written as (15. is the initial volumetric concentration of reactants. It is also apparent that the laminar flame speed is a function both of the reactant and the mixture strength. Obviously the laminar flame speed is very dependent on the temperature of the products.8b) can be simplified to (15. Figure 15.
B.6 Variation of laminar flame speed with mixture strength for typical fuels (based on 1 a m .2 1. 155 Variation of laminar flame speed with reactants and mixture strength. 300 K) .4 Fuelair equivale~ce ratio.o 1. mh E 200 r= .CO 250 .Stoichiornetnc Stoichiornemc 'i Stoichiometric H. 15..8 1. p = 1 bar. Tu=298 K 50 1 45 .E f 2 25 15 0.. 3 5 4 50 0 0 10 20 30 40 50 60 70 % gas in air Fig. Fig.
. If the engine bore is 100 mm then the combustion period will be 0. If the combustion process depended on laminar burning then the combustion period in terms of crank angle would change by a factor of more than 7 : 1. this is for two reasons.6 are not directly applicable to an engine. and reaches a value of around 4 m/s when the reactants temperature 4.1 s.5 m/s).7 Variation of laminar flame speed with reactants' temperature (predicted by Kuehl's equation with p = 1 bar) .longer than the compression and expansion periods! Obviously the data in Figs 15. and this has a major influence on the design of engines operating with lean mixtures. It can be seen that the speed increases rapidly. are much cooler than in an operating engine. First. Figure 15.) at stoichiometric conditions: the laminar flame speed is about 50 cm/s (0.7 shows how the laminar flame speed increases with reactants temperature. At 800 rev/min this is equivalent to 480" crankangle . Consider an engine operating with methane (CH.11) where p = pressure (bar) T = temperature (K) u. as suggested above. It has been assumed that the adiabatic temperature rise remains constant at 2000 K.= laminar flame speed (m/s) It can be seen from eqn (15. The other feature to notice is that the laminar flame speed would remain approximately constant in an engine operating over a speed range of probably 800 to 6000 rev/min. at temperatures of 298 K or 300 K.5 and 15. the initial conditions of the reactants. 15. Kuehl (1962) derived an expression for the combustion of propane in air.1 1) that the effect of pressure on flame speed is very small. which gave (15. which is approximately correct for a stoichimetric mixture.Flames 301 It can be seen that the laminar flame speed is dependent on mixture strength.5 '1 300 400 500 600 700 800 900 1000 Reactants temperature / (K) Fig.
and defined the ratio of turbulent to laminar flame speed. 15. particularly if they are required to work over a broad speed range. This is an increase of about a factor of 8 on the previous value which would reduce the combustion duration to about 60" crankangle. This is still quite a long combustion duration.13) E = eddy . often called the flame speed factor. A popular model describing how turbulence increases the flame speed is the wrinkled laminarflame model.302 Combustion andflames is IO00 K. is ( 15. (1979) applied a similar approach to engine calculations. as (15. the turbulence may increase the transport of heat and active species. The laminar flame speed must be enhanced in some way. which enhances the laminar flame speed as described below. Burned gas Unburned Lamina flame Turbulent (wrinkled) flame Fig. The theory of turbulent flames was initiated by Damkohler (1940) who showed that the ratio of turbulent to laminar flame speeds. parameter is turbulence. and turbulence in the flow can do this. especially since it has been evaluated at only 800 rev/min.5.8 Comparison of laminar and turbulent flames The effect of turbulence on the flame is threefold: 0 0 0 the turbulent flow distorts the flame so that the surface area is increased. 15. some other feature must operate on the combustion process to speed it up. based on large scale eddies in the flow.8. This. which is shown diagrammatically in Fig 15.3 TURBULENT FLAME SPEED It was shown previously that the laminar flame speed is too low to enable engines to operate efficiently. the turbulence may mix the burned and unburned gases more rapidly.12) where diffusivity Y = kinematic viscosity of the unburned gas Heikal et al. second.
is related to the situation in which the flame is found. the flame speed factor defined in eqn (15. = transit time for flow through laminar flame. which is the product of Karlovitz and Lewis numbers. which explains why the ignition timing has to be advanced.9.Flammability limits where 303 a = molecular thermal diffusivity P. = area of laminar flame. z. = Taylor microscale.13). This means that while turbulence increases the flame speed significantly. where they were listed with the explosion limits.14) where F. If the flame is moving in a confined space it will be extinguished more easily because of the increase in the interaction of the molecules with the walls. 15.1. i. 1992) investigated the way in which turbulence ‘stretches’ the flame and causes it to be extinguished. it is not possible to sustain a flame. Bradley et al.5 Flammability limits Flammability limits were introduced in Table 15. lean or rich. (1976) have also shown that the level of turbulence intensity in an engine cylinder increases with engine speed. The results are summarised in Fig 15. 1.g. c . The flammability limit of a mixture is defined as the mixture strength beyond which. = laminar flame speed. and lines of constant Re/Le2. b .e. which is the ratio of Reynolds number to the square of Lewis number.005) then the flame is a wrinkled laminar one. u. 0. in practice. when the flame is stretched until it breaks. The lean flammability limit is approximately 50% of stoichiometric. dare all empirical constants Experience shows that in spark ignition engines the flame speed factor is a strong function of engine speed but is not greatly affected by load. 6. but is not quite proportional to it. which is a graph of the ratio of turbulent to laminar flame speed. = Prandtl number vp= mean piston speed a . The abscissa is closely related to the Karlovitz number. The flammability limit. If the value of KLe is low (e. (1987. u‘ = turbulence intensity. It is also possible for the flame to be extinguished if the level of turbulence is too high. K .9 are lines of constant KLe. while if the value of KLe is high ( e g 6 ) the flame is stretched . the length of the burning period increases as engine speed is increased. = laminar flame thickness. Experiments by Lancaster et al. Also shown in Fig 15. this is known as quenching. which is a measure of the flame stretch: (15. against the ratio of turbulence intensity to laminar flame speed. while the rich limit is around three times stoichiometric fuelair ratio.
A small percentage of misfires from the engine will make the uHC emissions unacceptable .ronstant Re/Le2 I 2 0 ' 4 l ' 6 l ' 8 l ~ 10 l ' 12 l ' 14 l ' 16 l 18 ' l 20 ' l Ratio ( t u r b u l e n c e i n t e n s i t y / l a m i n a r f l a m e s p e e d ) Fig.Constant I 0 KLe . 15. is .these misfires might not be perceptible to the average driver. Honda quote one of their engines operating as lean as 24: 1 airfuel ratio. In practice.. and one which does not cause extinction of the flame. 20 1 0 63 I8 0 16 14 Disrupted.304 Combustion and flames sufficiently to quench it. the rich limit of flammability is more affected than the lean one.usually a sparkplug. This would enable the hydrogen powered engine to achieve brake thermal efficiencies similar to those of the diesel engine. 15.6 Ignition Tne ignition process is an extremely important one in the homogeneous charge engine because it has to be initiated by an external source of energy . in a car engine the lean limit is set by the driveability of the vehicle and the tendency to misfire. partial quench region I 5 c 12 10 Wrinkled laminar region Quench region 6 8 6 4 .0 I e: 0 2 .1 that the spread of flammability for hydrogen is much higher than the other fuels This makes it an attractive fuel for homogeneous charge engines because it might be possible to control the load over a wide range of operation by qualitative governing rather than throttling. it also restricts the ability of operating the engine lean to control NO.9 The effect of turbulence on the turbulent flame speed and tendency to quench for a premixed charge It can be seen from Table 15. This shows that the design of a combustion chamber must be a compromise between a high enough value turbulence intensity to get a satisfactory flame speed. The rich and lean flammability limits come closer together as the quantity of inert gas added to a mixture is increased. which is usually the important one for engine operation. Such leanbum operation is achieved through careful design of the intake system and the combustion chamber. Fortunately. is not much changed. and basically the lean limit. The restricted range of flammability limits for hydrocarbon fuels limits the amount of power reduction that can be achieved by leanburn running. It can be shown that the minimum energy for ignition. based on supplying sufficient energy to the volume of mixture in the vicinity of the sparkgap to cause a stable flame. to be controlled. which enables both the engine power to be reduced and the emissions of NO.
By section B.11. or sparkignition engines. ut is dependent on the initial temperature of the reactants. and also if the engine is running lean. The other major class of flames is called diffusion flames. some way from the end of the nozzle.is low. gas turbine combustion chambers. and hence T J . In other words. The principle is the same if the fuel is a more complex gaseous one passing into air. . in these flames the rates of reaction are not controlled by the laminar flame speed but the rate at which the fuel and air can be brought together to form a combustible mixture. much more energy is required when u. as indicated by the mass fraction curves. when the injected fuel has to mix with the air in the chamber before combustion can take place. As shown above. This means that the strongest spark is needed when the engine is cold.Difisionflames 305 Qp. usually by turbulent mixing brought about by the jet entraining the surrounding oxygen. 15. diesel engines. This dependence also explains why it is attractive to develop stratified charge engines.min~ k3/p2u:. Airfuel ratio Fig. the hydrogen has been mixed with the oxygen just outside the jet diameter due to turbulent entrainment. This means that the minimum energy is increased as the inverse of the laminar flame speed cubed.10 Minimum ignition energy against airfuel ratio 15.7 Diffusion flames The previous sections all related to premixed flames of the type found in Bunsen burners. The typical variation of minimum energy to ignite a mixture is shown in Fig 15. At section A the hydrogen and oxygen are completely separate.10. with a rich mixture zone around the sparkplug. when the liquid fuel sprays are mixed with the air in the combustion chamber. This type of combustion occurs in 0 0 0 open flames. This is a simple example of a jet of hydrogen passing into an oxygen atmosphere. The three sections across the jet (at A. when mixing with secondary air enables combustion of a rich premixed core to continue to completion. A typical arrangement of a diffusion flame might be that shown in Fig 15. and the equivalence ratio of the charge (because this affects the adiabatic temperature rise. The typical level of energy required to ignite the mixture in a sparkignition engine is around 30 ml. the major difference will be that the products of combustion will be more complicated. B and C) show the way in which the oxygen diffuses into the jet.
The details of diesel combustion are beyond this course. In this example it has been assumed that the oxygen and hydrogen burn as soon as they come intimately in contact. Section C is located almost at the end of the mixing zone. After that the hydrogen and oxygen on the centreline combine to form water. after the end of the potential core. Individual combustion systems will now be considered. Fig. it can be seen that there is pure hydrogen right up to the end of the potential core. A similar. 15. but occurs because the droplets of fuel leaving the nozzle i impart their momentum on the surrounding air by aerodynamic drag. but the principles are similar to the combustion of gaseous jets.306 Combustion andflames There has not yet been any mixing of hydrogen and oxygen in the potential core. This presupposes that the chemical reaction rate is much faster than the diffusion rates. Considering the concentration of hydrogen and oxygen along the centreline of the jet. Gas turbine combustion chambers work in a similar way. and subsequent entrainment of secondary air to complete the process. and it is not until the end of the mixing zone that the oxygen concenwation starts to rise again.11 Combustion of a jet of hydrogen in an oxygen atmosphere . Once the fuel and a r are mixed it is possible for the droplets to evaporate to create a combustible mixture. as the water and oxygen mix and dilute each other. The edge of the mixing zone is now well within the diameter of the jet. with a spray of fuel entraining primary air to initiate the combustion. as indicated by the mass fraction of water. Some combustion has also taken place by this section. this is usually a reasonable assumption. but more complex analysis may be made of the injection of diesel fuel into the cylinder of a diesel engine. In this case the entrainment of the fuel and air does not take place in the gaseous phase. and there is no pure hydrogen left in the jet.
or more commonly now by a port or manifold fuel injection system. although it is probable that the fuel enters the cylinder with a large proportion in the liquid phase. These engines will not be considered here. The gas entering the engine has a combination of swirl (vortex motion in a horizontal plane) and barrel swirl (vortex motion . including the May combustion chamber (Figs 15. These systems will be described briefly. but are a hybrid between the fully premixed sparkignition engine and the diesel engine in their combustion mechanism. More modem engines attempt to increase the turbulence levels around the spark plug by the breakup of barrel swirl or tumble. and increased the flame speed (see Fig 15. the remaining liquid fuel causes high levels of unburned hydrocarbons (uHCs). It was stated above that a high level of turbulent gas motion in the cylinder will increase the flame speed. While this system produces high turbulence it occurs too late to achieve its aims.Engine combustion systems 307 15. (b) piston approaching tdc and squishing gas from top land region Other designs have been proposed.13(a) and (b)) which produces a high level of turbulence by ‘squeezing’ the gas into a small combustion chamber under either the intake or exhaust valve. is done to ensure that the light fractions of the fuel give a combustible mixture. (a) (b) Fig. At startup this will not be the case. A May chamber was fitted to a Jaguar engine and produced better fuel economy by enabling leaner mixtures to be used.and fourstroke engines being investigated for use in cars do have direct injection into the engine cylinder using an airblast injector.8 Engine combustion systems Different engines have different combustion systems which reflect the way in which the fuel and air are brought together.8. Under fully warmedup conditions this fuel will have evaporated by the time of ignition. beyond stoichiometric. This is done either in a carburettor.] All these systems prepare the charge prior to it entering the cylinder. and this can be achieved by various mechanisms. 15. and enrichment.1 SPARKIGNITION ENGINES In sparkignition engines the fuel and air are usually premixed prior to admission to the engine cylinder. 15. which enhanced the turbulence in the region of the spark plug.12). In older engines the shape of the piston and cylinder head produced a squish motion as the piston approached tdc. [Some of the two.12 Squish flow in ‘bath tub’ combustion chamber: (a) piston at midstroke.
(b) May combustion chamber with piston near tdc . Swirl momentum is preserved during compression. Barrel swirl cannot be preserved as ordered motion because the shape of the vortex is destroyed as the aspect ratio of the combustion chamber changes: barrel swirl is broken down into smaller scale motion which enhances the flame speed.11). Fig.note barrel swirl set up in cylinder.note squishing of charge into compact chamber. 15. but is not very useful for sparkignition engine combustion. (d) pentroof chamber with piston near tdc . (c) modem pentroof (4 valve) head .308 Combustion andflames in the vertical plane) (see Figs 15.13 (c) and (d)).13 High activity cylinder heads for sparkignition engines: (a) May combustion chamber note combustion chamber under valve. .note high activity of gas around Plug Further features which must be borne in mind with sparkignition engine combustion cllamkrs are: (i) reducing zones where combustion can be quenched (see top land region in Fig 15.
and the burning gases enter the main chamber (which contains pure air) and generate high turbulence which ensures good mixing of the burning plume and the ‘secondary’ air.8. need relatively simple fuel injection equipment.20 mm and 700 bar in a small highspeed direct injection diesel engine. around top ring groove. or jets. 15. Combustion of the rich mixture commences in the prechamber. through a high pressure injector. The prime considerations in the design of a combustion chamber for a diesel engine are to obtain efficient mixing and preparation of the fuel and air in the time available in the cycle. The majority of small diesel engines for passenger cars use the indirect injection (idi) process. The droplet size of the fuel varies but is of the order of 20 pm.le and low preysure . In these engines. in liquid form.14(b).g. the size depends on the injection nozzle hole size and the fuel injection pressure.. with a single hole nozi. Fuel is injected into the diesel engine cylinder. (iii) reducing crevice volumes where uHCs might be trapped.njection pump. This approach was adopted because it was possible to achieve good mixing of the fuel and air in the prechamber due to the high swirl velocities that could be generated there as air was forced into the prechamber by the piston travelling towards tdc. Such combustion systems are very tolerant of fuel quality. (b) basic schematic of indirect injection diesel engine . see Fig 15. Fuel injector Fuel injector Swirl chamber (a) (b) Fig. The mixing and combustion processes are similar to those shown in Fig 15.11 for a gaseous jet. which has to entrain air to enable evaporation of the fuel and subsequent mixing to a point where hypergolic combustion occurs. which might be 0. the fuel is injected not directly into the main combustion chamber but into a small swirl chamber (e. This approach had a further advantage that relatively simple fuel injection equipment could be used. Ricardo Comet V) connected to the main chamber by a throat.g. 15. This fuel enters the engine as a jet.2 DIESEL ENGINES The design of diesel engine combustion chambers is different from that of sparkignition engines because of the nature of the diesel process.14 Some combustion chamber arrangements for diesel engines: (a) basic schematic of direct injection diesel engine.Engine combustion systems 309 (ii) limiting zones which might trap the end gases and cause detonation. e.
Fig. Figure 15. and is necessary at present because high enough mixing rates cannot be achieved in the centre of the bowl itself. The fuel jets injected into a swirling flow have the peripheral fuel stripped off to form a combustible mixture. L = low swirl Figure 15. The mixing of the fuel and air is achieved by the multiple fuel jets entraining air into themselves and bringing about the necessary mixing. Nearly all truck diesel engines are direct injection. in which there is no organised air motion. and the time available for combustion becomes shorter. The bottom limit of size for di diesel engines is reducing all the time. The largest di diesel engines have quiescent combustion chambers.18 mm diameter). and four cylinder engines as small as 2 litres are available for van and car applications. and this is done in the form of swirl in the diesel engine.310 Combustion andflames and can be run at relatively low airfuel ratios before producing black smoke. which is where ignition is initiated. requires that the rate of mixing of the fuel and air is enhanced above that which can be achieved using a quiescent combustion chamber.15 shows the ignition points located by high speed photography in a high speed di engine.15 Sprays and combustion initiation points in a small di diesel engine: H = high swirl. The relatively low engine speed of large engines allows sufficient time for combustion to occur. as are those for rail and marine applications. The increased engine speed. and reduced time for mixing. Direct injection (di) diesel engines (shown schematically in Fig 15. the appropriate size of injector hole reduces. Their disadvantage is that their fuel economy is about 10% or more worse than their direct injection counterparts. More than six holes might be used in the fuel injector nozzle to give good utilisation of the air in the chamber. This also plays an important contribution in the mixing of the fuel and air.15 also shows that the fuel jets impact upon the wall of the piston bowl. The mixing rate can be increased by imparting air motion to the charge. 15. M = medium swirl.14(a)) dominate the larger size range. Also. As the engine bore size reduces so the engine speed increases. . until it reaches the limit that can be achieved by production techniques (around 0.
631 deg crankangle ( 15. and in this way the premixed combustion is limited to the pilot charge.22Vp)e [ E A ( l / R T . and are related to the Arrhenius equation introduced in Chapter 14 to define the rate equations.15a) or ti.12. Whitehouse and Way (1970) attempted to model both periods by the two equations given below. controlled by the mixing of the fuel and air. At the end of this period there is rapid combustion of the premixed fuel and air.Engine combustion systems 31 1 The design of combustion systems for diesel engines must aim at ‘optimising’ the overall combustion process. produced in the engine. Typical equations for the ignition delay period are (15.4))0.36 + 0.16a) and preparation rate: P = K’mi(’x)mi( Po*)’ ( 15. A mechanical method for limiting the overall ignition delay is to use twostage or split injection. = activation energy = 618840/(CN CN = cetane number + 25) Both eqns (15. This takes a finite time. Reaction rate: ( 15.2/(p . and this is dominated by diffusion burning. and cannot be extended far beyond the regime under which they were evaluated.15b) where Vp = mean piston speed (m/s) p = pressure (bar) T =temperature (K) E .16b) .15b) is a more recent formulation than eqn (15. In this type of system a small quantity of pilot fuel is injected into the cylinder some time prior to the main injection process. After the premixed period is over. and has a more complex structure.15b) have a similar form. The value of E .15a). reduces as the cetane number increases and this means that the ignition delay is inversely related to cetane number. This period has a major effect on the amount of NO. Equation (15.15a) and (15.1/17190)(21. The first fuel that is injected into the cylinder is not ready to ignite until it has evaporated and produced the necessary conditions for hypergolic combustion. which gives rise to a high rate of heat release and produces high temperatures in the combustion chamber. the main combustion period commences. referred to as the ignition de2ay period.15b) contains a term for the cetane number of the fuel. = (0. during which the fuel is prepared but not yet ignited. It should be noted that eqn (15. The pilot charge is prepared and ready to ignite before the main charge enters the chamber. Both equations are the result of experimental tests on engines with a range of fuels. but they do give a basic structure for ignition delay. This takes place in two distinct modes: premixed and diffusion combustion.
high rates of pressure rise (dplda) and a high level of noise generation. a Fig. Crankangle. and it can be seen that the instantaneous rate of heat release does not reach such a high level as for the long delay. the temperatures inside the combustion chamber are high and the rate of reaction is much faster than the rate of preparation. At this stage the combustion process is governed by eqn (15. During this process the rate of combustion is controlled by the rate at which the fuel and air mix. although there is a small pressure drop through the chamber which should be taken into account when . 15.16. R. This is because the time for the physical and chemical processes to enable the fuel to reach a hypergolic state is less.16 Effect of ignition delay on rate of heat release diagram 15. which models a diffusion process. It is important to mix the burning fuel with the air at the appropriate rate to ensure that the carbon produced during the combustion process is consumed before the exhaust valve opens. The long delay results in a large amount of fuel burning spontaneously.8.3 12 Combustion and flames where pq = partial pressure of oxygen P = rate of preparation of fuel by mixing R = rate of reaction mi = mass of fuel injected mu= mass of fuel unburned These equations result in instantaneous heat resase patterns o the form shown in Fig 15.16b).3 GAS TURBINES Combustion in gas turbines takes place at essentially constant pressure. The fuel pyrolyses and forms the precursors of the carbon particles produced in the exhaust system. and consequently less fuel is available for spontaneous ignition. P. with high temperature rises. After the premixed phase has taken place. and in this phase the hydrocarbon fuel in the centre of the jet is burning in insufficient oxygen. a. One of the diagrams has a short ignition delay. This initial period is governed by the rate of reaction.
When considering the . The a r enters the chamber through the diffuser. clean combustion. The secondary air will also lower the gas temperature to about 1800 K.ombustion pmcess it is useful to remember that the three parameters . The snout imparts a high swirl into the flow to induce a strong recirculation region in the primary zone. produced.have to be optimised to achieve good. and the products will be passed to the turbine through the nozzle. Figure 15.17 is a schematic section of an annular combustion chamber.temperature. Finally the cooling air which has been passed down the outside of the combustion chamber will be mixed in with the hot gases. and their temperature will be reduced to about 13001400 K. Next. will be formed. In the primary combustion zone the airfuel ratio will be approximately stoichiometric (15 : l). where its velocity is reduced and the airflow is distributed between the primary air entering tht cnout and the secondary air entering the inner and outer annuli.Engine combustion systems 313 undertaking design. the gases will enter the dilution zone where they will be further diluted. 15. and reduce the amount of NO. The fuel injector will be either a high pressure spray atomiser or an airblast injector. Annular combustion chambers have advantages over the older types of tubular combustors in terms of pressure loss and compactness. time . at which temperature NO. The design of the dilution zone will also reduce the circumferential temperature distribution. i turbulence.17 Section through aero gas turbine annular combustion chamber The combustion in the chamber takes dace in a number of regions. Sometimes a smaller pilot injector is used to assist ignition. It also promotes good mixing through turbulence. I Dilubon Nozzle Snout Intermediate hole 1 I Diluhon hole Fig. This air will induce further turbulence and supply more oxygen to complete the burning of the soot formed during the rich primary combustion. and the adiabatic temperature rise will take the temperature up to about 2000 K. this swirl enables the residence time in the primary zone to be lengthened without making this region excessively long. whch matches the flow from the combustion chamber to the requirements of the turbine. . although there will be regions in which much richer mixtures exist. The gas will leave the primary zone and then be diluted with secondary air bleeding through the side walls of the chamber: the charge is then in the intermediate zone. which will be located circumferentially around the body of the gas turbine. Ignition is achieved by means of a powerful plasma jet igniter. The overall airfuel ratio in the combustion chamber will be around 40: 1.
Measurements of the temperature exponent yielded a value of 0. This mechanism produces multiple zones of products.7. The level of turbulence must be balanced against the other combustion properties to ensure that the flame is not extinguished. using diagrams. Give two relative advantages of each type of combustion system. The general principles derived in this chapter have been used to analyse their operation. Examples have been given of combustion chambers for petrol and diesel engines. but is too slow for most engineering applications and must be enhanced by turbulence to achieve levels appropriate for powerplant. Pb) at a pressure p > Pb: . (ii) the smallest automotive diesel engines. completely burning the reactants. 2 (a) What is meant by the terms (i) (ii) (iii) a global reaction. and their effect on combustion.9 Concluding remarks The physical phenomena which affect combustion have been introduced. Prove that the temperature of an element of gas mixture which burned at pressure pb has a temperature T ( p. How much faster will the reaction be at 1000 K? 3 A combustible mixture of gas and air is contained in a well insulated combustion bomb. have been described. The laminar flame speeed is related to the mixture strength and the temperature of the reactants. (c) A reaction is found to be 25 times faster at 400 K than at 300 K. (b) Describe the steps required to form a chain reaction and explain why chain reactions are important in combustion. The differences between homogeneous. an elementary reaction. how these problems are catered for in the design of (i) large automotive diesel engines. It is ignited at a point and a thin flame propagates through the mixture. and gas turbines. a reaction mechanism. premixed reactants and heterogeneous reactants. PROBLEMS 1 (a) One of the main problems encountered in the design of a diesel engine combustion system is the mixing of the air and fuel sufficiently rapidly to ensure complete combustion. (b) Compare and contrast the combustion systems of diesel and spark ignition engines in the forms they are applied to passenger cars. Calculate the activation energy of the reaction.314 Combustion and flames 15. It has been shown that premixed combustible mixtures exhibit a characteristic combustion velocity called the laminar flame speed. and it has been shown that these rely on the mixing of the fuel and oxidant to achieve combustion of the mixture. Diffusion flames which occur in heterogeneous mixtures have been described. Explain.
Calculate the final pressure. i. in terms of p l . and how can they be reduced? ..of ethylene is approximately 1. in a spark ignition engine is to run it lean. 6 Describe the construction of a boiler for burning pulverised coal.1323. c. cp. p z . and suffix 1 defines the conditions before ignition. Estimate the enthalpy of reaction when 1 kmol of ethylene is completely oxidised. QL = calorific value of fuel. Give reasons for the difference between the values. 4 The structure of ethylene is H2C= CH.Problems 315 where K = ratio of specific heats.e.3 and QL/c.71 kJ/ kg K over the temperature range of the reactants. turbulence and time required for good combustion. Explain how this design optimises the temperature. = 1500 K. Discuss the problems encountered when running engines with weak mixtures. QL. T I . Neglecting dissociation. What is the difference between the final temperature and that of the first gas to bum if Tl = 300 K. 2028 K] 5 A method of improving engine fuel consumption and reducing the emissions of NO. K = 1.2 MJ/kmol. with a weak mixture. find the temperature reached after constant pressure combustion of ethylene with 50% excess air if the initial temperature of the reactants is 400 K. and explain how these can be overcome by design of the engine combustion chamber. [1302. What are the main emissions from this type of plant. and K.. The specific heat at constant pressure. Compare the value obtained with the tabulated value of .3 MJ/kmol.
Thomson applied the second law of thermostatics to thermoelectricity by considering the Thomson and Peltier effects to be reversible and the conduction effects to be irreversible. Fourier’s law of heat conduction. phenomenological laws have been given which describe irreversible processes in the form of proportionalities. e. In previous work. The method was successful as the predictions were confirmed by experiment but it has not been possible to justify Thomson’s hypothesis from general considerations. This was developed from statistical mechanics and the derivation will not be shown but the results will be used. Systematic macroscopic and general thermodynamics of irreversible processes can be obtained from a theorem published by Onsager (1931a. It is possible to examine irreversible phenomena by statistical mechanics and the kinetic theory but these methods are on a molecular scale and do not give a good macroscopic theory of the processes. Ohm’s law relating electrical current and potential gradient. in this chapter.b). .1 Introduction Classical thermodynamics deals with transitions from one equilibrium state to another and since it does not analyse the changes between state points it could be called thermostatics. and give rise to new effects. also shows why the incorrect thermostatic methods give correct results in a number of cases. The theory.16 Ir reversi ble The rmodyna mics 16. based on Onsager’s theorem. It is necessary to formulate coupled equations to deal with these phenomena. for dynamic nonequilibrium processes. When two of these phenomena occur simultaneously they interfere. The term thermodynamics will be reserved. Fick’s law relating flow of matter and concentration gradient etc. which are ‘phenomenological’ inasmuch as they are experimentally verified laws but are not a part of the comprehensive theory of irreversible processes. Here. the laws of thermostatics are applied to a part of the irreversible process that is considered to be reversible and the rest of the process is considered as irreversible and not taken into account.g. or couple. One such crosscoupling is the reciprocal effect of thermoelectricity and electrical conduction: the Peltier effect (evolution or absorption of heat at a junction due to the flow of electrical current) and thermoelectric force (due to maintenance of the junctions at different temperatures). Another method of considering nonequilibrium processes is based on ‘pseudothermostatic theories’.
If the reservoirs are very large the conduction of energy out of. i. dQ/dt. Heat flows between the two reservoirs by conduction along the rod. the lefthand reservoir loses entropy at the rate (16. the process is reversible. If a thermometer were inserted at any point in the rod the reading would not change with time.3 Entropy flow and entropy production Still considering the conduction example given above. leaving the rod. (This is the basis of the Searle’s bar conduction experiment. i.) The temperature in the bar is therefore a function of position but is independent of time. where the system was already in equilibrium.Entropy flow and entropy production 3 17 16. them can be considered not to affect them. 16. A state will be achieved when the rate of heat flow. in which a thermally insulated rod connects two reservoirs at temperatures T2and T.e. A system was said to be in equilibrium when no spontaneous process took place and all the thermodynamic properties remained unchanged. In the case where the system was in steady state. the difference between the steady state and equilibrium becomes obvious. 16.e. The overall system is in a ‘stationary’ or ‘steady’ state but not in ‘equilibrium’.1. but it would be dependent on position. for that requires that the temperature be uniform throughout the system. processes would occur after the isolation (equalisation of temperature throughout the bar). If the heat flows into the lefthand end of the bar due to an infinitesimal temperature difference. entering the rod equals the rate of heat flow. they would not. respectively. If the metal bar were isolated from all the influences of the surroundings and from the heat sources. dQ/dt.2 Definition of irreversible or steady state thermodynamics All previous work on macroscopic ‘thermodynamics’ has been related to equilibrium. If the rod were of uniform crosssection the temperature gradient would be linear. The macroscopic properties of the system were spatially and temporally invariant. if it is made an isolated system. System 2 : System boundary Distance Fig.1) . or into.1 Steady state conduction of heat along a bar Consider the system shown in Fig 16.
16. Fourier’s equation for onedimensional conduction of heat along a bar is (16.2) Thus.e. 1 dQ . A = area of crosssection of wire. A = electrical conductivity. k = thermal conductivity. i. is (16.6) where I = current. I = length. and therefore the rate of change of entropy. However. the total change of entropy for the whole system is (16.4 Thermodynamic forces and thermodynamic velocities It has been suggested that for systems not far removed from equilibrium the development of the relations used in the thermodynamics of the steady state should proceed along analogous lines to the study of the dynamics of particles. L is a coefficient independent of X and J and is scalar in form. there is a net transfer of entropy from the lefthand reservoir to the righthand reservoir. Hence.3 18 Irreversible thermodynamics Similarly the righthand reservoir gains entropy at the rate . X is the thermodynamicforce. qr = charge (coulomb). T = temperature.e. which is also onedimensional. dt dt (16. The total entropy of the composite system is increasing with time and this phenomenon is known as ‘entropy production’. i. . Ohm’s Law for flow of electricity along a wire.i’. the laws should be of the form J=LX (16. Since the temperature is constant the system is in a ‘steady state’.4) where J is the thermodynamic velocity or flow. 1 = length. At the point I from the lefthand end the thermometer reading is T. and at each point in the rod the entropy is invariant with time. dS/dt > 0. while both J and X are vector quantities. entropy is ‘flowing’ along the rod. the thermometer indicates the ‘temperature’ of that volume of the rod. A = area of crosssection. This reading is independent of time and is the reading obtained on the thermometer in equilibrium with the particular volume of the rod in contact with it. e = potential difference (voltage).5) where Q = quantity of energy (heat). The following simple relationships illustrate how this law may be applied. To understand the meaning of this result it is necessary to consider a point in the bar.3) Now T2> T.
(16. by a more complex argument.6) and (16. 16. The diffusion process achieves this by mass transfer. etc.k = dt dCi dl (16. Equations (16.8) may also be written in matrix form as (16.8a) It is obvious that in this equation the basic processes are defined by the diagonal coefficients in the matrix. The diffusion process also has the effect of redistributing the matter throughout the system. It will be shown that although eqns (16. The equations of coupled processes may be written (16. The thermal conductivity process achieves the transfer of heat by the molecular vibration of the matter transmitting energy through the system. heat conduction and diffusion of gases. i. = L . Both of these processes are capable of transferring energy through a system. This law was derived in relation to biophysics by analogy with the laws of thermal conduction to explain the flow of matter in living organisms.. heat conduction and electricity in thermoelectricity.5 Onsager's reciprocal relation If two transport processes are such that one has an effect on the other. .7) where ni = amount of substance i . Other similar relationships occur in physics and chemistry but will not be given here. C i concentration of component i .5).e. there is a flow term and a force term as suggested by eqn (16. each molecule of matter carries some energy with it. while the other processes are defined by the offdiagonal terms. J 2 = L2.7) also define the relationship between individual fluxes and potentials.6) and (16.7) appear to have the correct form. (16. Consider the situation where diffusion of matter is occurring with a simultaneous conduction of heat.4).X2 the equation of conduction without any effect due to diffusion the equation of diffusion without any effect due to conduction . It will be shown later that this equation is not as accurate as one proposed by Hartley. they are not the most appropriate relationships for some problems.X . the maximum entropy or minimum chemical potential). if each process is considered in isolation the equations can be written J . that thermal conduction will also have an effect on diffusion. in which the gradient of the ratio of chemical potential to temperature is used as the driving potential. whereas in many situations the effects can be coupled. The three equations given above relate the flow of one quantity to a difference in potential: hence.8) Equation (16. in one dimension 319 dn..5). in an attempt to achieve the equilibrium state in which the matter is evenly distributed with the minimum of order (i. Both achieve a similar result of redistributing energy but by different methods.g. and k = diffusion = coefficient. It can be shown. First. then the two processes are said to be coupled.Onsager's reciprocal relation Fick's Law for the diffusion due to a concentration gradient is. e.e.
the sum of these products is equal to the rate of creation of entropy per unit volume of the system.10) where L.13) by calculating the entropy production. Thus TO = JIXl + J2X2+ . Consideration will show that if this were not true then it would be possible to construct a system which disobeyed the laws of thermodynamics. then.9) where L I Zis the coupling coeficient showing the effect of mass transfer (diffusion) on energy transfer. A general set of coupled linear equations is (16.but Onsager’s relation chooses the forces in such a way that when each flow Ji is multiplied by the appropriate force Xi. Hence J1= LIlX. molecules carry energy with them. L.320 Irreversible thermodynamics Now. the thermodynamic theory of an irreversible process consists of first finding the conjugate fluxes and forces. from eqn (16. In a similar manner. the diffusion of matter has an effect on the flow of energy because the individual. Then a study is made of the phenomenological equations (16. = C i AXi (16. in general ( 1 6. + LI2X2 (16. T . The significance of this is that the effects of parameters on each other are equivalent irrespective of which is judged to be the most.14) Lik = Lki This means that the coupling marrix in eqn (16. is the coupling coefficient for these phenomena.12) Equation (16..11) k The equations are of little use unless more is known about the forces X .. significant parameter. In summary. . which is obtained from molecular considerations it will be assumed to be true. 8. There is considerable latitude in the choice of the forces X. for the particular case given above. the equation for mass transfer can be written 5 = L21 Xl + L22X2 2 (16. diffusing. and hence an effect for diffusion must be included in the term for thermal flux. and the coefficients Lip This information can be obtained from Onsager’s reciprocal relation.11) and . = L. Ji and x i .12) may be rewritten (16.... It is not proposed to derive Onsager’s relation. multiplied by the temperature. Le. because conduction has an effect on diffusion.8a) is symmetric. or least.13) where Onsager further showed that if the above mentioned condition was obeyed. J .
. gives (16.20) Equation (16. i. At any point in the bar. e = dJS dl from eqn (16. J.20) is the rate of production of entropy per unit volume at point I in the rod where the temperature is T. At I the entropy flow rate will be (16. The whole procedure can be performed within the realm of macroscopic theory and is valid for any process. 16.e. flows due to a potential difference de.17) T (16.6 The calculation of entropy production or entropy flow In section 16.18) for J. The wire may be considered to be in contact along its length with a reservoir at temperature T.The calculation o entropy production or entropyflow f 321 Onsager’s reciprocal relation (16.3 the concept of entropy flow was introduced. Le. in equilibrium. is i. (=Z/A). This equation was derived for thermal conduction only. then the electrical work must be equal to the heat transferred from the wire. may be defined as the entropy flow rate per unit crosssection area. A similar calculation may be made for the flow of electricity along a wire. J.16) is The heat flow rate JQ defined as JQ = Hence JQ Js =   A (16. entropy is produced not dissipated.19) Substituting from eqn (16.14) is used to solve these.e. I.18) The rate of production of entropy per unit volume.. For conduction dT/dl< 0.15) and the entropy flux is (16. and since the wire is at constant temperature T because of its contact with the reservoir. If the rod was at a uniform temperature. dT/dl= 0 and 0 = 0. 8.16) ( 16. If an electric current density. thus 8 is positive. the entropy flux.
If the temperatures of the two reservoirs are different then not only will heat be transported along the wires A and B but also a flow of electrical current will occur.the application of irreversible thermodynamics to a thermocouple 16. each placed in a heat reservoir. This is known as the Peltier effect and the heating (or cooling) is equal to d. as shown in Fig 16.2.21) T (16.7. Hot junction Cold iunction Motor Fig. 16. 16.2 Schematic of a thermocouple being used to drive an electric motor Two different wires A and B are joined to form a loop with two junctions. A thermocouple consists of two junctions of dissimilar metals. The following phenomena may be isolated: (i) If the entire system is kept at a uniform temperature and the motor is driven as a generator then a current will flow around the circuit.7 Thermoelectricity .A de. because dV=A dl. (16. one held at a high temperature the other at a low temperature. and the total rate of heat production is Q.23) applies for electrical flow with no heat conduction. It is found that under these circumstances heating occurs at one junction and cooling at the other. the rate of production of entropy per unit volume is. Hence Q = JIA dE The total change of entropy in volume dV is 8dV=JIA de (16. a summary will be given of the effects involved in a thermocouple. A perfectly reversible motor is inserted in wire B. where x=Peltier coefficient and I is the current. Because of the resistance of the wires it is necessary .23) Equation (16.1 THERMOELECTRIC PHENOMENA As an aid to understanding the analysis which follows.22) Hence.322 Irreversible thermodynamics The rate of doing electrical work (power) is J.
This work is equal to the product of current and potential difference across the wire and is called Joulean heating. At each point in the wire there will exist a temperature as shown in Fig 16. It is impossible to measure some of these effects in isolation.26) .7. This is called the Seebeck effect. (16. Consider a wire in a temperature field in the absence of an electric current.20). this is the IZR loss. the Seebeck and f f Peltier coefficients are the properties o pairs o metals.. which is dissipated in the reservoirs. These connections will still give rise to contact and thermally induced voltages but these are usually negligibly small. because they are junction effects. if it is attempted to measure the potential difference between two points not at the same temperature. from eqns (16. I = current. (ii) If the reservoirs are put at different temperatures a potential difference is set up even when no electric current flows. For example. dT/dl = temperature gradient in direction of I. This effect is additional to Joulean heating and is proportional to the temperature gradient.1. When making connections it is necessary that the measuring points are in an isothermal region. The various coefficients defined in them can be used in engineering practice. This is called the Thomson heat and occurs in a wire carrying a current of electricity along a temperature gradient. It is found that a flow of heat is required to keep the wire at the same temperature as previously. Hence. Heat flow For uncoupled heat flow the rate of entropy production per unit volume is. except for the Thomson effect.24) where Q = rate of heat transfer. The heat flux is given by =CJl dQ dl dT dl (16. (iii) If both a temperature difference and electric current occur simultaneously then a third effect OCCLUS.25) where 1 dT x1  T dl (16. not single metals. 16. Let suffix 1 refer to heat flow processes and suffix 2 refer to electrical flow processes.The application of irreversible thermodynamics to a thermocouple 323 to do work to drive the generator.13) and (16. the measuring instrument and the electrical wires used to make the connections will constitute part of a thermocouple circuit. Fourier conduction will also occur along the wires. and CJ = the Thomson Coefficient. It is not possible to measure the thermoelectric characteristics of a single material. Now suppose an electrical current flows.2 UNCOUPLED EFFECTS IN THERMOELECTRICITY Consider the two possible types of uncoupled flow. The above laws are purely phenomenological.
in this case.32) where A is the electrical conductivity of the wire at constant temperature. J1 J2 = LIIXI = I L12 x 2 L2JI + L22 x 2 I de 12 These become.13) and (16.31) It has been assumed that both the electrical and heat flow phenomena may be represented by empirical laws of the form J = LX..4 . 673 de dl THE COUPLED EQUATIONS OF THERMOELECTRICITY The Onsager relations as given by eqn (16. If dT is set to zero in eqn (16.29) (16.30).AA de/dl. At constant temperature.8) may be applied.23) $ = J2X2  T J. i. = A (16. and this ratio is called the entropy of transport.30) From eqn (16... S*. ..34) . the electrical current is flowing in the absence of a temperature gradient.18).L dT QT dl for electrical flow dl (1 6.324 Irreversible thermodynamics Electrical flow For uncoupled electrical flow.27) (16. for heat flow J . the entropy flux Js is given by J . giving (16.X. be written = JQ/T. Ohm’s law states I = . then de A .29) may (16.e.. and hence eqn (16. then (16.JI de T T2 dl (16. from eqns (16.28) x2 1.33) dl dl If the entropy fiux in the wire is divided by the electrical current flowing at constant temperature. i.e.= b2de 23 L.
.30) gives: for heat flow Ja = (k + . Fourier’s law of heat conduction may be applied.=Q (16.35) (16.S* L.31).k A dl However.39) de dl dT s * dl kdT dl Lll dT T dl dT dl (16.37) and ATS* dT 1 T dl A de dl (16....44) The entropy flux is obtained from eqn (16.) * de .ITS dl dT dl * (16.38) gives  (16.40) Substituting this value for def d l in eqn (16. JI = 0).. giving dT JQ=.ITS*.41) Hence Ll...43) for electrical flow JI=AS Adl dT de dl (16. Thus L12= TL. =  (k+ATS*’) dT AS T dl *  dE dl (16. if J I = 0 then eqn (16. = ITS* (16..37) gives J . It is a useful method for defining the crosscoupling terms in the coupled equations. L.45) .38) Now if there is zero current flow (Le. and Lzl in eqns (16. J.42) Substituting the coefficients into eqns (16.30) gives (16.29) and (16. = (k + ATS*’)T (16.The application of irreversible thermodynamics to thermocouple 325 The entropy of transport is basically the rate at which entropy is generated per unit energy flux in an uncoupled process.36) By Onsager’s reciprocal relation = L12 ITS* = Substituting for L.29) and (16.
a flow of heat (thermal energy) will occur due to the electrical potential difference.43) (16. From eqn (16. and the value of S* for most materials is nonzero.).. S* is a measure of the magnitude of the Seebeck effect. If the wire is kept at a constant temperature.44).47) Equation (16. It can be represented diagrammatically as shown in Fig 16. and indicates the magnitude of the offdiagonal terms in the crosscoupling matrix in eqn (16. Previously. the heat of transport Q*. From eqn (16. where Q* = (JQ/J.47) is interesting because it retains the basic generic form relating ‘heat’.8a).3 Schematic diagram of a thermocouple . the Seebeck effect was defined as the potential difference set up in a wire due to a temperature gradient without any current flow (Le.49) This transport of thermal energy due to an electrical field is known as the Thomson effect.3.326 Irreversible thermodynamics It is possible to define another parameter..7. 16. when dT = 0 (p). 16.43) and (16.46) Hence Q* = TS * (16.).48) Hence. From eqns (16. :)/( = (1TS* 1 $) TS* = (16. namely that entropy is evaluated by dividing a heat transfer term by a temperature term. (de/dT).44)..4 THE THERMOCOUPLE A thermocouple is a device for recording temperature at a point. It is now possible to relate the equations derived above to the various physical phenomena observed in experiments. if there is zero current flow (16. J: y& EELWire X t l Potentiometer I C . This is basically the ‘thermal energy’ which is transported by a flow of electrical energy when there is no temperature gradient.e A WirieZ Hot junction T” Wire Y Cold junction Terminals Fig. temperature and ‘entropy’.
These leads of material Z are then connected to a potentiometer or DVM at d and e. to give the following: wire ec EC . The voltage representing temperature THis obtained due to the thermoelectric effect in the leads when zero current flows. the potentiometer is balanced and J.o * (16.The application of irreversible thermodynamics to a thermocouple 327 The thermocouple consists of two wires X and Y of dissimilar metals forming a junction at a. and hence the emf generated is also independent of the length of the wires.. S*. and J . The ends b and c of the wires are immersed in an ice bath to form the cold junction and leads of material Z are connected to materials X and Y at points b and c.50) can be applied to each wire in the system shown above.S ) : dT (16. (SE . wire ab &b = 1.E. dT wire ca . ..E.S f ) dT (16.o = .S M dT)j. dT wire bd Adding these equations to obtain the potential difference between points e and d gives the potential difference measured by the potentiometer or DVM: = 1. T H (S.E. Since S* is defined in terms of J .48) the potential difference between each end of a wire of material M is related to the temperature difference between the points by the equation. it is independent of the length of the constituent wires. the emf at the potentiometer (or digital voltmeter [DVM]) equals the thermal emf generated by the thermocouple. = 1. . dT .5 1) This can be written as = E~ . and these connections are inserted into a cold junction.e. s*. as previously discussed..r. the emf of a thermocouple at any particular temperature THis dependent only on the materials between the hot and cold junctions if the leads bd and ce are both made of the same material. dE). respectively. At zero current. i. Equation (16.52) Thus. =  : [ T H S*.Ea = 1. = 0. From eqn (16.50) where SL is the value of S* for material M .
&d =  IT:' T C S*.4./.4 that there are now four junctions between dissimilar materials. I J reservoir M D : Fig. The calibration of the thermocouple is dependent only on the wires used to make the junctions. Figure 16.3 showed an idealised thermocouple in which the connections between the thermoelectric pair of wires and those connecting the thermocouple to the measuring device were maintained at the cold junction temperature. and each of these has the capability of generating an emf. Hot junction Cold junction reservoir Wire Y Connections Wire Z Wire Y Wire Z Terminals 12. to the system gives the following results: = Wire dc E.50) and (16.4 Conventional layout of a thermocouple It can be seen from Fig 16.1 Potentiometer 134 T.52). Applying d&)J. 16. dT Wire cb Eb .E. This system will be analysed to determine the potential difference at the DVM. see eqns (16.328 Irreversible thermodynamics Thermocouples are normally bought as pairs of wires which have been calibrated by experimental tests. for high temperatures platinumrhodium is used. Wire ba . It might be inconvenient to set up the thermocouple in this way. For low temperatures (up to 15OOC) CuNi thermocouples may be used. and a more convenient arrangement is shown in Fig 16. Thermocouple with junctions at T and THand connections in one of the measuring wires . the length of thermocouples is not a parameter in the calibration. = jTR dT s*.. .=o S* dT).
16.1"'s: dT T R (16. i.7. = If points c and e . The temperature of the system tends to rise due to both Ohmic and Peltier heating. must be at the same temperature. dT Wire ef The emf at the potentiometer is given by ef. If the Ohmic heating is neglected initially then the Peltier coefficient. this effect occurs when the entire system is kept at uniform temperature and a current flows around the circuit. these junctions are not at the same temperature then each of them will act as another junction and generate an electrical potential. 16.4 to ensure that points c and e are close together and at the same temperature.1. IT' dT TC T R S*. care must be taken when setting up a thermocouple wired in a manner similar to Fig 16.53) This is the same result given before in eqn (16.54) where n = Peltier coefficient. dT  IT" S*.7. (TRs)c (TRs)e.51). defined below in eqn (16.ed = ITR T R S*.e.& o =  IT: S*. There is one important point which is apparent from this result and that is that the two junctions between wires Y and Z.5 Peltier heating at a junction . can be evaluated JQ ~ e i ~ = er JI (16. Hence. dT  I" T H S*.5 OTHER EFFECTS IN THERMOCOUPLES Peltier effect or Peltier heating As defined in section 16.54). Fig. dT .The application of irreversible thermodynamics to a thermocouple 329 Wire ae &e .
Q*. = T ( S x. Thomson effect or Thomson heating This was defined previously in eqn (16.YJl= <JQ>X . A l . the heat transfer from the junction to maintain the temperature constant is nX.y TSE .59) that the Peltier heating is reversible. is the heat that must be transferred to a reservoir to maintain the temperature of the junction at T . = oJI AT (16.6.330 Irreversible thermodynamics The Peltier heating effect at the junction in Fig 16.57) This is the definition of the Peltier effect.(JQ>Y (16.60) A! 4 (J&+AT J.58) The ratio (JQ/JI)Tconstant defined previously and termed heat of transport.6 Small element of a wire subject to current flow Assume that initially there is no current flow. y = ( JI ) x :r h () (16.54) J.) = * * (16.7. = ( J Q > X . if the current is reversed the direction of heat flow will be reversed.55) where J. Under these conditions the heat flow due to heat conduction is the same as previously. ( J Q ) .61) Heat flow . Rewriting this equation in the nomenclature now employed and applying it to the small element of wire. = X X .( J Q > Y (16.Let the required heat transfer.56) Hence. From eqn (16. dQ/dr. J'Q Fig. It was was shown (eqn (16. and hence the Peltier coefficient is given by n x .S. 16. Now if an electric current is switched on it is found that a flow of heat is required to keep the wire at the same t e m p e m s as previously.47)) that Q* = TS*.e.59) It is apparent from the form of eqn (16. i. Thus nx. Y J I (16. this is in addition to Joulean heating (see section 16.24). shown in Fig 16.5 is given by 1.ate. Then (16. be Jh. at T Ohmicheating . aiT+AT Heat flow rate.1 (E)). dpldr. but that the heat flow gives rise to a temperature drop AT. to a series of reservoirs.TS.
is (eqn (16.60) as Jn= UJ. for the element de AE = .38) can be rearranged to give = (16. Now. AT Thus dT (16.A 1 dl Equation (16.47)) Q* =(:)T=TS* and hence (JQ) = JITS* (16.The application of irreversible thermodynamics to a thermocouple 33 1 At any given temperature.66) Substituting the above relations into eqn (16.64) (16.67) Ohmic heat generated Now the Thomson heat was defined in eqn (16. the heat of transport. Q*. T.AT dT ds* + JI 2 A 1 A (16.62) At a temperature.68) . T +AT (16.AI dl and dT AT= .65) de dl JI i l s  * dT dl (16.61) gives = JIT Thornson heat e x m d (0 maintain temperature .63) if multiples of small terms are negected.
It is characterised by the setting up of a concentration gradient as a result of a temperature gradient.3.) Thomson effect Thomson coefficient: 16. The Dufour effect This is the inverse phenomena to the Soret effect and is the nonuniformity of temperature encountered due to concentration gradients.8.7 shows an adiabatic system made up of two parts connected by a porous membrane. The constant of proportionality in Fick’s law is called the diffusion coefficient.(SX . and is the mass transfer analogy of the thermal conduction law.7. Seebeck effect Seebeck coefficient: Peltier effect Peltier coefficient: nx.GY = d * * T .69) 16. .332 Irreversible thermodynamics For the thermocouple shown in Fig 16. this law is due to Hartley. This states that the diffusion rate is proportional to the concentration gradient. It was found from experimental evidence that the diffusion coefficient tended to vary with conditions and that better proportionality could be obtained if the rate of diffusion was related to the gradient of chemical potential. The Soret effect This is a thermal diffusion effect.S y ) dT (16. or a pipe with a bore that is small compared with the mean free path of the molecules.8 Diffusion and heat transfer 16.1 BASIC PHENOMENA INVOLVED The classical law of diffusion is due to Fick (1856).*S. Figure 16.6 SUMMARY The equations for thermocouple phenomena for materials X and Y acting between temperature limits of THand T are as follows: . . the difference in Thomson coefficients for the two wires is G .y= T(S.
) ( + ( g ) ( 2 Am) Arfz = 2 A ~ [au2) A U + au amA m } + 2 h [ ( ~ ) A m + ( ~ ) A m ] (s (*) am2 au a U (16. and de Groot (1951)). 16.70) AS11 may be found by a similar expansion. or small bore pipe 16. the rate of generation of entropy. is enclosed in a reservoir. the change of entropy of the Universe is AS = ASl + ASn = AU2 + 2 a2s AU Am + (auam) ( $)u Am2 + higher order terms . Suppose that a system comprising two parts. hence variations AU and Am in part I give rise to variations AU and Am in part 11./ / membrane Porous \ Fig...e.72) . It will be assumed that both parts are the same volume.) The system is isolated.and mass. and when in thermostatic equilibrium the energy. The time rate of change of AS. is given by (16.5. in each part is equal. The variation in entropy due to these changes may be found from Taylor’s series: + higher order terms (16. m . V .71) .8. but the linear terms in AU and Am are negative. i. associated with each part of the system. U.(AS) = _ (2 AU)AU + 2 ___ d az:m)Am A 0 + 2 ( & ) A U h dt (r.Diffusion and heat transfer 333 I Adiabatic wail 1 . S. and there is an entropy.2 DEFINING THE FORCES AND FLUXES To choose the forces and fluxes it is necessary to consider the rate of entropy generation (see section 16. ( U and m were chosen as parameters because these obey conservation laws. Thus.7 Schematic diagram of two containers connected by a porous membrane. I and II connected by a hole.
from Onsager's relationship.74) enables the forces and fluxes to be defined.( A S )= JUXU dr + JmXm (16. J"=Li. x ~+L22Xrn .. X i + J 2 X 2 which may be written. and the original terms were defined in relation to a single part of the system.334 Irreversible thermodynamics and the rate of generation of entropy per unit volume is .77) (16.78) Substituting for A p = v A p .Xu+L.80) h = p + TS = u +pv gives A($)u = V Ap + S AT AT AT AP AT + h . for this system.8). giving Ju = AU Xu = A($)m (16.p dm (16.73) and (16. for a system at constant pressure.81) T Hence substituting these values in eqn (16.12).76) Hence (16.( A S )= . as d TO = . that for a twocomponent system TO = J .s AT and (16.(AS) = AU d 1 d (16. .74) Comparison of eqns (16.Xrn J r n = L .73) dt 2 dt because the combined volume of systems I and II is 2V. It was stated in eqn (16. From the First and Second Laws.79) (16..Ts = V + h T T2 T2 T T' (16.75) J m = h Xm=A(E). T ds = d u + p dv .
= 0.87) 16.85) In the stationary state. Hence. J . (16. h .= AT vT The significance of this result will be returned to later. L.e.e.86) Now.. if the fluxes and forces defined above are simply accepted without proof. a chemical potential) gradient then a pressure difference will be established between the systems until h = U*. ..3 THE UNCOUPLED EQUATIONS OF DIFFUSION It is also possible to derive the result in eqn (16.82) and (16. The pressure difference is defined as AP Q* .= L. (16. if two systems are connected together with a concentration (or more correctly. i. the term h .83) If the flow of internal energy which occurs due to the diffusion is defined as ( J u / J m ) A T = o = u* then (16.8.Q*.U * = L.rl" may be defined as .84) i. and the significance of this is that it drives the system to generate a pressure gradient due to the temperature gradient.D i e i o n and heat transfer 335 gives (16.87) in a more easily understandable manner.h* L. hU* vT AT vT (16.
p ax T ax (16.l/T(dT/dx) (see section 16. X.336 Irreversible thermodynamics Diffusion For the uncoupled process of diffusion.2). but it is possible to derive the equations for multicomponent mixtures.88) where p i= chemical potential.7.89) applies for a single component only. XI= . it was shown in eqn (16. Xt + L22X2 (16.78) that the thermodynamic force for component i. aT TO= Jmap + .78) (16. is given as e= Duetoisothermal diffusion T J. as shown in eqn (16. = . ap ax + p~2 J. . If Onsager’s rule for entropy flux is applied to this situation Te=CJX Thus J.T a ( p / T ) / a x (see section 16. Consider the system shown in Fig 16.For the mass transfer process.91) Ductotcmpcnhlrc gradient Coupled diffusion and heat processes Such processes are also referred to as heat and mass transfer processes. 6. is (16.8. in onedimensional diffusion.93) The thermodynamic forces have been previously defined.7.90) Hence the entropy production per unit volume. For the heat transfer process. aT ax (16.2).89) Equation (16. The equations governing the flow processes are: heat (16.92) diffusion (mass transfer) Jm =L2. Evaluating the differential in eqn (16.88) gives.
can be evaluated from eqn (16.96) or (16.102) (16. i.98) The specific enthalpy.94) and.93) (16. h. can be related to this parameter by (16.e. from eqn (16. and from the definition of chemical potential.99) gives h (16. = 0.101) .92) (16. the term dp = dg = Vdp + s dT Thus (1 6. The effect on J .100) The term &P/T) ( T I T 1 = ($1.95) (16.95) Consider the steady state. & because T = constant.Diffusion and heat transfer 337 Thus. from eqn (16.99) Rearranging eqn (1 6.97) (16. when there is no flow between the two vessels and J . p .
Q*.JTis the energy transported when there is no heat flow through thermal If conduction.98) gives d(p/T) = .. as shown in eqn (16.JT= L21/L22.103) VdP .103) Hence from eqns (1 6.104) (1 6.84) (16. Also from Onsager’s reciprocal relation (JQ/J.l b dT h dT+T2 giving T L22 T2 (1 6.106) ( 16. which is called the heat of transport.97) and (16..(hU*) dT vT Now the difference h .338 Irreversible thermodynamics Substituting for (y) P and in eqn (16. Using this definition.dp T2 T h V ( 16.105) can be written (eqn (16.108) The ratio (JQ/J.86) may be rewritten (eqn (16.dT + .86)) dp .87)) dp =dT Q* VT .107) Thus.. eqn (16. this ratio is denoted by the symbol U* then eqn (16.U* was denoted .105) If both vessels were at the same temperature then dT/dx = 0 and ( 16.
Now.111) Integrating across the plug from side I to side 11. if Q* were not applicable to both sides of the plug then the principle of conservation of energy would be contravened. it would ap ar reasonable that if Q* is liberated on entering the plug at temperature T then Q * + d Q would be absorbed on the molecule leaving the plug. on each side of the plug.109) (16.1 10) then dp _dT Q* RT 2vT  R 2v  p 2T vT (16. is liberated when the molecules enter the plug and the same amount is absorbed when the molecules emerge from the plug.Diffusion and heat transfer The signficance of Q* 339 Q* is the heat transported from region I to region 1 by diffusion of the fluid. Q$ is the amount by which the mean energy per unit mass of molecules that are in the process of transit through the plug exceeds the mean energy of the bulk of the fluid.AT vT Q* This means that if Q* is negative. Weber showed by kinetic theory that when a gas passes from a vessel into a porous plate it has a decrease in the energy it carries. Hence Q* = RT/2 for flow through a porous plug. Q*. Ax A p = . when the eneral temperature is T + dT. It is a 1 measure of the difference in energy associated with the gradient of chemical potential. the pressure increment is of the same sign as the temperature increment and molecules flow from the cold side to the hot side. (16. The difference of average values of the bulk fluid energy on either side of the plug has been taken into account by the different values of the enthalpy.87) over an increment of distance. The energy carried by the gas molecule in molecular flow through the passages in the porous medium is smaller by RT/2 than it was when the motion was random. From eqn (16. This is erroneous and a qualitative explanation follows. as in the thermal effusion case. h . Hence. .113) This is called the Knudsen equation for molecular flow. as in the thermal effusion case. if F! Q* = RT/2 and for a perfect gas p v = RT (16. When Q* is dependent on temperature. The energy. In a simple case it is possible to evaluate Q*.112) or (16.
without recourse to Onsager’s relationship.115) Equations (16.115) may be written in the form _ (1 6. then ri. would be the number of particles passing through this hole. this is what happens when gas flows through the pores in a porous membrane. These particles would carry with them kinetic energy.8. ( 16. It can be shown that the energy passing through the hole is given by E A +g2  (16...8. The hole also makes a selection of the atoms which will pass through it and favours those of a higher energy because the frequency of higher velocity particles hitting the wall is higher.3. when flow through a porous plug was examined. In this case the flow will be assumed to occur along a small bore pipe in which the crosssectional area is small compared with the mean free path of the molecules. that L. It can be shown from statistical thermodynamics that the number of particles striking a unit area in unit time is 4 P _A (2nkTm)’I2 where ri. The problem considered is similar to that discussed in section 16. This derivation will be based on statistical mechanics.kT = density = velocity = energy (E) 3 2 . = L2.117) 2m ) l l z ( : kT)(!!?) kT 3n where N = Avogadro’s number.4 THERMAL T W S P I R A T I O N It will be shown in this section.114) and (16.1 16) E‘ A ( )( NkT _ .1 14) Consider a hole of area A . and this is the manner by which Onsager derived his relationship.340 Irreversible thermodynamics 16. = number of particles striking wall A = area of wall p = ‘pressure’ of gas k = Boltzmann’s constant T = temperature m = mass of ‘particle’ (16. The groups of terms can be defined in the following way: (&) .
= density x ri.120) (16. Cooling Q Porous wall Heating +Q Fig.= density x mean velocity x mean energy A E The weighting factors show that the particles passing through area A carry with them an unrepresentative sample of the energy of the system from which they come. 16. It will be assumed that the pores in the wall are much shorter than the mean free path of the molecules.1 14) the net flux of molecules passing through the wall is given by (16.118) and the net energy passing through the wall is given from eqn (16.122) ( 16.115) as (16.119) It is possible to substitute for the pressure of a monatomic gas by the expression = eah3(2zm)3/2p5/2 and the temperature by T = I/kp (16.8 Arrangement for flow through a porous plug From eqn (16. A mean velocity .123) .121) Then eqns (16.8. and Thus . The gases on either side of the partition are the same. but one side of the system is heated and the other side is cooled.119)become ( 16.Diffusion and heat transfer 341 Nm'/2/n'/2 4N/3n1"are weighting factors. The system is shown in Fig 16. This example can be expanded into an apparatus that contains two systems separated by a porous wall.118) and (16.
The concepts of entropy generation and coupled phenomena have been introduced. PROBLEMS 1 The emf of a copperiron thermocouple caused by the Seebeck effect..^ dB + LE.dp .9 Concluding remarks This chapter extended 'thermodynamics' into a truly dymanic arena.which is equivalent to the result given by Onsager.4 ~ 7 m B .~ e .s= LE. then differentiating gives Equations (16. B = .. Finally. dynamic state. and 16.. The processes involved are nonequilibrium ones which are in a steady.~ h . with a cold junction at O'C.~ L.a nc L nc a = . Coupled diffusion and heat transfer processes have been introduced and analysed using these techniques. and Onsager's reciprocal relation has been used to enable the latter to be analysed.125)may be written in the form = 4:) 4) : 4:) = (2~mzh~)B~e"[6j3' 2 da] dB  ( 1 6.3 e .~ e .~ ) B . has been proved frGm Statistical thermodynamics.a . " .127) where LE. d a (16.2 h . and the conjugate forces and fluxes have been developed..125) LE.124) = ( 2 n r ~ h .342 Irreversible thermodynamics If the state denoted by the primed symbols is constant.3 e . statistical thermodynamics was used to demonstrate that Onsager's reciprocal relation can be proved from molecular considerations. Thermoelectric phenomena have been considered and the coupling between them has been described.. Hence Lt. The major thermoelectric effects have been defined in terms of the thermodynamics of the device. is given by &=a.4 n m f i .126) and (16./?da] "[ 2 (16.124)and (16.3 h . = L2.t+t a 2 2 2 +t a 3 3 3 V .2 n m B . that L. = LkB.
is contained in two containers at different temperatures. 3. If the thermocouple is used to measure the temperature effect based on the Seebeck effect. The cold junction is connected to a reservoir at 0°C.1914t + 0.116 mV. u*=the energy transported when there is no heat flow through thermal conduction. If the system is adiabatic.11 mW/A. 7. [1. and a current flows through it. i. evaluate the temperature of the plug if the upstream temperature is 60°C.053 x 2 The emf of a copperiron thermocouple with its cold junction at 0°C is given by E= VI 13.0001t3pV where t = temperature ("C). 3.437 mV] [5. The heat of transport of the gas through the plug is %T/2.calculate the values of the constants a and b. mV/K. v = specific volume.66 mV.0138t2+0. 1. show that the difference in pressure between the two containers is given by = dp hu* vT dT where h = specific enthalpy of the fluid at temperature T.679 x 5 A pure monatomic perfect gas with cp= 5%/2 flows from one reservoir to another through a porous plug. If the emf of the thermocouple due to the Seebeck effect is given by E = at + bt2.403 x V/"C a2= +0.535 + 0.68 mW/A. When its hot junction is connected to a reservoir at 100°C the heat flux due to the Peltier effect is 2.00026 x V/(°C)3 t = temperature ("C) 343 If the hot junction is at t = 100"C. consisting of a single component. the Peltier effect at the hot and cold junctions.526 x mV/(K)2. T = temperature. and the thermal conductivities of the gas and the plug are negligible. 0. the difference between the entropy of transport of the copper and iron. there is no current flow. calculate (a) (b) (c) (d) the Seebeck emf.0006t2 pV/"C 3 If a fluid. the net Thornson emf. 4 A thermocouple is connected across a battery. calculate the voltages at 300°C and 200°C.e. 8. [73"C] .00 mV.Problems where a!= 13. and when the hot junction is at 200°C the effect is 4.0275 x V/("C)' aj= +0.403t+0.6432 mV. Show that the difference in the Thomson coefficient for the two wires is 7.
and explain why it is not in the centre of the bar. connects two reservoirs at different temperatures and also carries an electrical current of density.541 ] . To. Show that if the thermal and electrical conductivities.. Show that the maximum temperature achieved by Joulean heating alone is in the centre of the conductor. [ x / L= 0.344 Irreversible thermodynamics A thermal conductor with constant thermal and electrical conductivities. (I. J.aL/k = 1. An electric current is passed through the conductor. and the Thomson coefficient. the temperature in the conductor is given by Show that the maximum temperature is achieved at a distance k(eJruL/k. are constant. Show that the temperature distribution for onedimensional flows is given by d2T Jla dx2 dT k d x +=o A J: where (J is the Thomson coefficient of the wire. k and 1 respectively. A thermal conductor of constant crosssectional area connects two reservoirs which are both maintained at the same temperature. k and A. and heats it due to Joulean heating and the Thomson effect.1) (=[ :& )h JlaL } Evaluate where the maximum temperature will occur if J.
the Daniel1 cell. e. and Fig 17. Before developing the theory of the fuel cell itself it is .l(b) depicts the fuel cell itself. This arrangement has the advantage that the fuel can be carried in its liquid phase at atmospheric conditions.l(a) shows the hydrogen generator which is based on the water gas reaction.g. The thermodynamics of fuel cells will be developed below. Conversion efficiencies as high as 6080% have been achieved for fuel cells. and it is not limited by the Carnot efficiency. and NOx. Figure 17. the power to drive a vehicle as produced by a reciprocating engine. Japan). As shown previously. The concept of the fuel cell arises directly from the operating principle of the electric cell. whereas the practical limit even for sophisticated rotating machinery is not much above 50%. if a fuel cell operating on hydrocarbon fuels can be achieved it will improve ‘thermal efficiency’ significantly and reduce pollution by CO. liquid or hydride form. these devices are all based on converting part of the Gibbs function of the fuel to useful work.g. The theory of fuel cells can be developed from the previously derived thermodynamic principles. Hence. there are some devices which are capable of converting the Gibbs energy of the fuel directly to electricity (a form of work). and if an engine is used some energy must be ‘thrown away’: all engines are limited by the Carnot. as is the case for all heat engines. and these were not limited by the Carnot efficiency. which is much more convenient than carrying hydrogen either in gas. A further benefit of the fuel cell is that its efficiency is not reduced by part load operation.the steam engine. However. The current situation is that successful commercial fuel cells are still some way from general use but small ones have been used in specialist applications (e.g. efficiency. or Second Law. Figure 17. space craft) and large ones are being developed (e. and it shows how equilibrium reversible thermodynamics can be interwoven with irreversible thermodynamics.OH) as its primary fuel.Fuel Cells Engineering thermodynamics concentrates on the production of work through cyclic devices. and as early as 1880 Wilhelm Ostwald wrote: ‘I do not know whether all of us realise fully what an imperfect thing is the most essential source of power which we are using in our highly developed engineering . the production of electricity by means of a steam turbine. In this case the methanol is used to generate hydrogen for use in a hydrogenoxygen fuel cell. these are called fuel cells. e.g.’ He realised that chemical processes could approach efficiencies of 100% in galvanic cells. 1 MW by Tokyo Gas.1 shows a proposal for a fuel cell to power a motor vehicle using methanol (CH. The advantage of a fuel cell is that it is not a heat engine.
1) where the I represents an interface. 17.2. 1. A good place to start is the Daniell cell which produces electricity through consuming one electrode into solution and depositing onto the other one. or phase boundary. Proposed hydrogen fuel cell for vehicle applications 71 necessary to consider simpler electrical cells. I c u s o . This can be represented by the convention Zn ZnSO.346 Fuel cells Fig.1) is positively charged relazive to that on the left if the reaction takes place spontaneously. The convention adopted in representing cells in this way is that the electrode on the righthand side of eqn (17.1 Electric cells A schematic of a Daniell cell is shown in Fig 17. . Cu I I (17.
2 Schematic diagram of a Daniell cell To understand how the Daniell cell produces a potential difference and a current it is necessary to consider the basic reaction involved. 17.F kJ/kmol (17. If the reaction in eqn (17. n / z = FQ (17. i. n / z = Q.F V kC/kmol = 2E. the ratio of the amount of substance (Zn) dissolved to the valency of the element.4) SQ.6) .3) (17. from Faraday’s laws of electrolysis.uzn The reaction described above is basically an open circuit reaction for a Daniell cell. This is known as the Faraday constant. and is the product of Avogadro’s number and the charge on a proton. then the work done is 6W = 2E. Zn + CuSO.5) When n / z = 1 kmol. n / z .2) which indicates that the zinc reacts with the copper sulfate solution to produce copper and zinc sulfate solution.2) takes place in a constant volume container using 1 kmol Zn (45 kg Zn) then 214 852 kJ of heat must be transferred from the container to maintain the temperature of the system at 25°C. Q = 9 6 485 kC (where kC denotes kcoulomb). the reaction takes place as work is being taken from the cell then supposing a current I flows for time.(aq) (17.(aq)Cu + ZnSO.Electric cells 347 +n electrode zinc rod netectrode f //F I: acid / copper sulfate / solution copper vessel Fig. then.ucuso4(oq) . If. This reaction is similar to a combustion reaction. and hence F =96 485 kC/kmol. and must obey the First Law of Thermodynamics SQ = d U + S W where 6W = 0 in this case. Hence (17. if the potential between the electrodes is E. is proportional to the electric charge passed. and SQ. represents the open circuit energy released. = 214 852 kJ/kmol Zn = ucu+ uznso4(oq) .e. The notation aq indicates an aqueous solution of the salt. t. as is more usual. Now.
Cu++ 2e + Cu Zn +   at zinc electrode + Cu++ in solution at copper electrode I (17.107 V at 25°C. where z is the valency (or charge number of the cell reaction) of the Zn.1). which this time is applied to the closed circuit system and gives dU=SQSW =dQR. enters the solution at the negative pole.13) (17.15) . If it is assumed that the cell can maintain this potential at low currents.T d s = d G = G2 . G2< G. applying the First Law. the total work that could be obtained from a cell if it changed volume would be (17.) compared with the reactant (CuSO. and the potential is equal to the open circuit potential. and assuming the processes are reversible gives dU=dQ6W=TdSpdVzFEdn and hence the electrical work output is zFE dn = d U + p dV.4).141 kJ/K (17. then 6W = 2 x 1. E. This heat transfer is a measure of the change of entropy contained in the bonds of the product (ZnSO.348 Fuel cells In a Daniell cell the potential at zero current (i. .a black box. ZnSQ. = 1.7) Now the change in internal energy is simply due to the chemical changes taking place.10) 6W= zFE dn However. and for an isothermal reaction must be equal to SQ. Hence zn" + 2e Zn" CuSO.8) This indicates that heat must be transferred from the cell to maintain the temperature constant.14) (17.213 618 W/km01 (17.12) The equations derived above define the operation of the Daniell cell from a macroscopic viewpoint. For a cell which is spontaneously discharging. then it will carry with it a charge of zF dn. defined in eqn (17. It is instructive to examine the processes which occur at the three interfaces shown in eqn (17. Suppose that an amount of substance of Zn.e. dn.107 x 96 485 = 213 618 kJ/kmol If the reaction described above takes place isothermally in a closed system then it must obey the First Law.SW=dQ. and AS= 1234/298= 4. thus (17. The Coulombic forces in the cell are such that an equal and opposite charge has to be absorbed by the copper electrode. which is called the emf. The maximum work that can be done is achieved if the cell is reversible. It is possible to develop this approach further to evaluate the electrical performance of the cell. on open circuit).). and this is achieved by the copper ions absorbing electrons which have flowed around the external circuit. giving dQR= 214 852 + 213 618 = 1234 W/km01 (17. and is 2 in this case.11) 6 W = zFE dn + p dV thus.9) In this approach the Daniell cell has been treated as a thermodynamic system .G.and hence dW= dG (17.
) The net effect is to maintain the potential difference between the electrodes constant for any given current: this is a state of dynamic equilibrium. Although the Daniell cell was one of the early examples of a device for generating electricity. V = inner electric potential of the phase. it is the cathode. (17. but first it is necessary to introduce another property.). a battery charger).17) It was previously stated that the chemical potential was a ‘chemical pressure’ to bring about a change of composition to achieve a state of chemical equilibrium. A simpler device will be considered below to develop the equations defining the operation of such cells. in solution at Zn electrode a++ . by consuming an electrode. but cause the zinc electrode to be at a negative potential. Hence. two electrons are left on the zinc electrode (because the valency of zinc is 2) and these are free to travel around the circuit. where it withdraws electrons from the electrode giving it a positive potential. Hence.1 I (17. it is relatively difficult to analyse thermodynamically because it has electrodes of different materials. then the current flow could be reversed and the reaction would become Cu  Cu++ 2e + Cu+++ ZnSO. The Daniell cell can be used to ‘generate’ electricity. while positive ions travel through the solution from cathode to anode. 17. the current is said to flow from the anode to the cathode. If the cell were connected to a potential source (e.15) resulted in electrons flowing from the zinc to the copper (this would be defined as a current flowing from the copper [anode] to the zinc [cathode]). F = Faraday constant (96 485 kJ/kmol). In a similar . the Daniell cell consists of electrons (negative charges) travelling around the outer circuit. The reactions defined in eqn (17. (Note: the convention for positive electric current is in the opposite direction to the electron flow.Zn + 2e .16) ELECTROCHEMICAL. and the potential on the anode would be higher than the cathode. To be able to analyse the cell in more detail it is necessary to introduce another parameter. p. POTENTIAL. i. or to store electricity. of ions. such that the potential difference of the source were slightly higher than the cell emf. from the cathode to the anode. It can be seen that the electrochemical cell is a situation governed by thermodynamic equilibrium and steady state (irreversible) thermodynamics (see Chapter 16). the electrochemical potential.  at Cu electrode Zn+++ CuSO. This is related to the chemical potential by pi = p i+ z i V F where zi = valency of (or charge on) the ion (+/ . the Daniell cell is reversible if the current drawn from (or fed to) it is small.Electric cells 349 This means that the zinc is ‘dissolved’ by the sulfuric acid at the zinc electrode and a zinc anion enters the solution.e.1.g. Meanwhile. The zinc anion reacts with the copper sulfate in solution to form zinc sulfate and release a copper ion which migrates to the copper electrode.
@ e I e c . The electrochemical potential also contains a term for the change in capacity to do work through electrical processes. p is the sum of the chemical potential.. made of different materials. and is obtained from electrostatic theory.(PCU.@CU' PB) = P c u . 1 .electrolyte IX4B Ix3Cu" (1 7.WcuJ .18) The junctions of interest here are X. 17. The value of w is the potential of the phase. chemical and electrical processes. junctions X.3. . introduced to the system by the introduction of a unit of mass.350 Fuel cells manner the electrochemical potential is an 'electrical pressure' that pushes the system towards electrical equilibrium. which has been based on the 'chemistry' of the material. It is the work done in bringing a unit positive charge from infinity to within the phase.19) = Z C " F ( WC". A and B.P A =Pcu' Pcu" .1. such as that shown in Fig 17. and X4. + ZCu"WCu'F) (17. and two connecting wires of identical material. The cell can be represented as Cu' \%AI. an electrolyte. Fig. + Zcu. This consists of two electrodes. Simple galvanic cell 73 Considering the electrochemical potential between points 1 and 2 P1P2=PI P6 @S&) @4p5) @ 3 P4)Pclcc) @2L13) =PCu' .f i A ) . Hence.@B Pclec) . Equation . ) The difference in chemical potential of the two electrodes (pcus pas) is zero because both electrodes are of the same composition and are at the same temperature.WCU. and X3 are potentially thermocouples (because they are junctions of two dissimilar metals) but these effects will be neglected here.@elec .2 THERMODYNAMIC ORIGIN OF EMF Consider a simple galvanic cell. It defines the energy that can be obtained from mechanical. and an electrical potential.
At the righthand electrode . or emf.p) I HCl(aq.) and combines it with chlorine (Cl. this is governed by considering the pair of processes occurring at the platinum electrodes. P ) I P CU” where (g.e. The situation in the Daniell cell can be reversed by recharging. electricity flows around the circuit and the energy is derived by breaking the bonds in the HC1 molecules. The difference.(g.24) . Now. The platinum acts both as the electrodes and a catalyst.(g.qcu”.23) which direction the reaction will go.equivalent to the open is circuit potential.) to form hydrochloric acid (HC1). it is not obvious from eqn (17.Cl. . if the process is considered to be reversible H.p) + Cl. which will be combined in the fuel cell to produce hydrochloric acid and electrical power. as described above.3 can be constructed in the following way: t t CU’I P 1 H.21) This is basically a cell using platinum electrodes (Pt) in an electrolyte of dilute hydrochloric acid (HCI). If it is desired to manufacture a cell which can operate without consuming the electrodes then it is necessary to supply the fuel along an electrode: such a device is called a fuel cell. In the Daniell cell the Zn electrode is consumed.) to be evolved at the electrode a hydrogen ion (H’) must be released into the solution and an electron must be left on the electrode. a small flow of current. c + I (17. i.(g.Fuel cells 351 (17.p)2HCl(aq.2 Fuel cells The above sections have considered how electrical work can be obtained by the transfer of material from one electrode to another. E . The operation is then defined by the reaction c) (17. p ) denotes a gas at pressure. but it will have hydrogen and chlorine delivered as fuels. A practical cell similar to that in Fig 17.H. An example of a fuel cell is one which takes hydrogen (H. The reactions at the interfaces are of interest because they produce the electrons and govern the potential.20) 17. and ultimately the cell would cease to function. At the lefthand electrode. p and (a4. and when it is dipped into the dilute hydrochloric acid the system acts like an electric cell and hydrogen is evolved at the lefthand wire and chlorine at the righthand one. If the cell is to operate as a fuel cell then it will not break down the hydrochloric acid. C ) I Cl2(g.(g) 1 2 + Pt + aq Pt’ + Cl(aq) (17. and hence (17.22) where p is the pressure of the gases in the cell.19) defines the maximum work that can be obtained from the cell by a reversible process.c) denotes an aqueous solution with concentration.23) This reaction indicates that for hydrogen gas (H.(g) 2 1 + Pt + a4  Pt(e) + H’(aq) (17. .
23) and (17.30) P c u . once a current starts to flow. then these will generate dn H' and C1.352 Fuel cells Equations (17. Hence.22) the electron current must flow from the PtH. Thus Cu" (e)Pt(e) Pt(e)Cu' (e) (17.26) The reactions taking place in the cell can now be examined to give (17. First.22): this then introduces irreversible thermodynamics. + AGj + AG4 ( 17.. It is in a state of equilibrium and AG)p.T=Ofor an infinitesimal process.3 1) .24) in combination show that for the reaction shown in eqn (17. .25) (17. the PtH. P c u .29) This equation consists of a mixhxe of chemical potential ( p ) and electrochemical potential @) terms. consider the device operating open circuit.in the electrolyte and transfer dn F of charge from Cur to Cu". It is apparent that when the cell is operating open circuit it will build up a potential difference between the electrodes. electrode is an anode. = P C & + FVWh (17. electrode. . PCG. However. Expanding the latter gives & = PH& + FV. is a cathode and the PtC1. ( e )= P C ~ '+ F V c u ' These terms may be substituted into eqn (17.ions to undertake reaction (17.29) to give (17.27) The change of molar Gibbs function across the cell is AG = AGl + AG. electrode to the RC1.28) which gives (17. If it is assumed that the equilibrium can be perturbed by an amount of substance 1/2 dn of hydrogen and chlorine being consumed at the electrodes. that potential difference will be affected by the ability of the H' and C1. ( e )= P C ~ + F V c u .
34) where the term AG:/zF is called the standard emf of the cell.* is a function of temperature and pressure alone.33) p. The activity coefficient. A suitable electrolyte for this cell is aqueous potassium hydroxide (KOH).0. to maintain generality) (17.T= 0 and F(q!J. and simply acts as a medium through which the charges can flow. and these gases are supplied down the electrodes. It can be shown that at low concentrations the activity coefficients are approximately equal to unity.34) show quite distinctly that the processes taking place in the fuel cell are governed by similar equations to those describing combustion. at equilibrium AG). which also obeys the law of mass action. In the case of gaseous components the activity can be related to the partial pressures by a. Equations (17.O 20H + 2e at hydrogen electrode (17. can be defined in such a way that the chemical potential ofa solution is p .37) It can be seen that the potassium hydroxide (KOH) does not take part in the reaction. z .. =. The equations are similar to those for dissociation.2. = pr/po.Fuel cells 353 Now.O + 2e  2H. Eo.32) where pr = p/po and a = the activity coefficient of the particular phase. (17. It is apparent from eqn . takes account of the interaction between the components in the solution.36) at oxygen electrode and these can be combined to give the overall reaction H2 + 0 2 + 2 1 H2O (17.33) In eqn (17...32) and (17. . 17. .1 EXAMPLE: A HYDROGENOXYGEN FUEL CELL Consider a fuel cell in which the fuel is hydrogen and oxygen.where pi = partial pressure of component i. and a. a . If the standard at chemical potential terms ( p a ) temperature T are denoted AGF then (17. The cell can be defined as The basic reactions talung place at the electrodes are H. x .q!JCum) = FE. thus (introducing the valency. + 20H 1 2 + H.ut*+ %T In a .
. ) of hydrogen is 2.41) giving %T E = In K .46 370.39a) where the stoichiometric coefficients. Hence.3 .42) shows that when the constituents of the cell are in equilibrium. A combustion process converts the bond energy of the reactants into thermal energy which can then be used to drive a powerplant. are defined as positive for products and negative for reactants. it is directly related to the equilibrium constant. Z.. and the actual emf achievable will be given by an equation similar to eqn (17.. by (17.42) Examination of eqn (17.34) which includes the partial pressures of the constituents.38) ZH.40) Considering again the term for Eo.34) the cell open circuit potential. The Second Law does . the fuel cell converts the bond energy of the fuel directly into electrical energy. From eqn (17.\ / Equation (17..39) can be written in a shorter form as (17.38) has been evaluated by assuming that the partial pressures of the gases are all 1 atmosphere.9 8 (30 434.185 v The standard emf in eqn (17.39) / .[239 081. and the amount of electricity produced is not constrained by the Carnot efficiency.. z. which is defined by the potential output of the cell is zero. like a combustion process.36) that the valency ( z .0.11) 2 x 96 485 (17. Kpr. the standard emf.F = 1.354 Fuel cells (17.In %T (17.F z.7 . v. is given by AG E 0 ==.5 x 52 477. In an actual cell at equilibrium they will be controlled by the chemical equation.. Hence the emf of the hydrogenoxygen fuel cell is (17.F .\ (17. F . the fuel cell only converts chemical bonds into another form of energy when it is transferring from one equilibrium state to another.3 .
43) Now. for exothermic reactions.2.O at any particular temperature is the same in the liquid and vapour phases). they have thermal efficiencies significantly below 100% based on the higher enthalpy of reaction: they have to transfer away the difference between the higher and lower enthalpy of reaction in the form of heat if they are going to operate isothermally. the potential to do work is not changed by the phase of the products (the chemical potential of H. However. + 2Hg .44) Substituting from eqn (17.101). )=  dT RT2 (17.Now. Qp is negative. 17.Fuel cells 355 limit the energy output but only defines the equilibrium condition.45) shows that the change of emf is related to the heat of reaction.44) into eqn (17.3 EXAMPLES Example 1 A PbHg fuel cell operates according to the following equation: Pb + Hg.42) with respect to T .2 EFFECT OF TEMPERATURE ON FUEL CELL OPERATION The effect of the temperature of operation on the emf of the cell can be evaluated by differentiating eqn (17. This means that while fuel cells are controlled largely by the First Law.  PbCl. An interesting difference between the fuel cell and the combustion process is that many fuel cells attempt to release the higher enthalpy of reaction. as discussed in Chapter 12. 17.2. and this means that the emf of a cell based on an exothermic reaction decreases with temperature. Qp. d QP .Cl.45) Equation (17. from the Van't Hoff equation (12. This is in line with the effect of temperature on the degree of dissociation in a combustion process. This gives (17. in this case keeping the pressure constant. In the case of the H202 fuel cell the product (H20) is in the liquid phase and not the vapour phase as is usual after combustion.(In K p . A fuel cell is basically a direct conversion device which is constrained mainly by the First Law.43) gives +=ziF R T 2 T ziFT E T (17. whereas combustion usually releases the lower enthalpy (or internal energy) of reaction.
Applying the First Law gives zFEdn=dUSQ. Hence the open circuit potential is x 11’2).176V . and the water is taken from it at the same pressure.(AG:. giving From tables at 500 K.. The cell receives heat transfer of 8300 kJ/kmol Pb from the surroundings.5363 = 103 500 kJ/kmol Pb giving the work per unit mass of reactants as = SW 103 500 207 + 2 x (200 + 35) = 152..) zF _ 95 200 .207.9 kJ/kg mmct Example 2 A hydrogenoxygen fuel cell operates at a constant temperature of 227°C and the hydrogen and oxygen are fed to the cell at 40 bar. Assuming the potential of the cell is not reduced by drawing a current. Solution This problem can be solved by a macroscopic approach to the cell as a closed system. Solution This question requires the application of eqn (17. assuming the following atomic weights: Pb .+TdSpdV = dG .92127 x bar”2.ln( E = 8.200.3143 x 500 ln(7. Qp= 95 200 kJ/kmol Pb.356 Fuel cells and the heat of reaction.35. Evaluate the emf at this condition.. K .34) in place of AGO.. Calculate the potential of the cell.92127 x 2 x 96 487 = { 4yb’:ti/ 1. Hg . Hence the work done per kmol Pb is SW =2x 96 485 x 0. and the heat transfer from the cell.SQ. = 7. then the charge transferred through the cell per kmol Pb is 2 F (because the valency of lead is 2). giving E = .SQ.5363 V The quantity of work obtained per kg of reactants is given in the following way. C1 . Now this value of energy transfer has to be used in eqn (17.42).8300 2 x 96 487 = 0. and evaluate the electrical work produced per kilogram of reactants.
0075= 1.18 = 57.h 8 0 x 1 1 ” ) ] .(0. .0 MJ/kmol H. which gives a higher enthalpy of reaction of Qp= (244.0 . when dissociation decreased from 0.0075 V z~F %T giving E .) = 0.7 . Thus.86 346 .E. Calculate the change in emf.14) is W = mAGO. this only affects the pressure term because K . 357 Also.[ In KpT In 4 0 x l 1 ” ) ] } z~F 80 x 80’/.18 277.0 x lo3= 277. at 500 K the lower enthalpy of reaction of the process is 244.0 + 219.18) MJ/kmol H. This is equal to the change of enthalpy of the working fluid as it passes through the cell and hence applying the steady flow energy equation to the fuel cell gives Q .Fuel cells The maximum work output from the fuel cell based on eqn (17. if the .0673 to 0.= ri?( 239 081. . = 1.18 244 . Hence.5 x [95 5441 + [58 4721)) = h(219.02 x lo3+ 18 x 1831) = 277.02 MJ/kmol.7913 If it were evaluated from the lower enthalpy of reaction.0. This is similar to the effect of pressure on the hydrogenoxygen combustion reaction.183 V This shows that the potential of the hydrogenoxygen fuel cell increases with pressure. is q= 219.0221 as the pressure was increased from 1 bar to 100 bar for the stoichiometric combustion of methane in Chapter 12.8983 The operating pressure of the fuel cell in Example 2 is changed to 80 bar.0. then the value would be v=Example 3 219.176+0.= S T { [h K p . 40 x 40‘’2 = ( ( ln(2’/. = f(T). based on the higher enthalpy of reaction.w = ri?(Ah) giving Q = k ( A h ) + W = 277. and hence E. Solution If the pressure is raised to 80 bar.82 MJ/kmol H. the efficiency of the fuel cell. which is usually used to calculate the efficiency of powerplant.
..49) to give 298(188.04) T AS q=l+1+ = 1 .50) and Qp= 241 820 k. (17.G.358 Fuel cells amount of substance in the reactants is not equal to the amount of substance in the products then the emf of the cell will be a function of the pressure of operation. and hence the efficiency is defined by the sign of the change of entropy.46) Heat of reaction Qp Now the maximum useful work output obtainable is defined by the change of Gibbs function.48) Thus.945 (17.945 (17.5 x 205.57 0.T ( S H ~ O H ~ o5soz) S 241 820 . and the processes are assumed to be isothermal.5 1) This efficiency can be evaluated using eqn (17.52) .0.71 .J/km~l (17. W.5 x 205. and it is possible to define its efficiency by the following equation: (17. 241820 = 0. = AG = GprodUc.0547 Q.49) Qp The last expression in eqn (17.e.298(188. II= Maximum useful work output = w. 17. Consider now the hydrogenoxygen reaction described above.J/kmol. then AG = ( h ? ) H 2 0 = .57 . Hence the efficiency is 228 594. If the fuel cell is maintained at the standard temperature of 25°C.130.8 k.71.0.130.3 Efficiency of a fuel cell The fuel cell is not 100% efficient.. i. if it is negative then it is less than unity.04) = 228 594.49) has been written in terms of the calorific value of the fuel because this is usually positive.47) and (17. If the entropy change is positive then the efficiency is greater than unity.8 tl= 241 820 = 0. the efficiency is (17.
fuel cell would be 100%. and being . 17. It can be shown for a fuel cell that a possible force term is the gradient of electrochemical potential. i. If TAS > 0 then the efficiency can be greater than loo%.g. which is similar to the use of the chemical potential gradient when considering diffusion processes (note that when considering thermal and mass diffusion in combination the gradient of the ratio of chemical potential and temperature ( p / T ) was used. if the value of TAS < 0 then the cell will be less than 100%efficient.4 Ions i cell n If the hydrogenoxygen cell is taken as an example..54) Fig. and any. ) (17. it is apparent that the charge is carried across the cell by OH.ions being absorbed on the hydrogen electrode. 17. The rational efficiency of this. Since the charge is carried on the ions travelling through the cell it can be directly related to the transfer of the ions from one electrode to the other. amp/m2). the force term is (17. Under such circumstances. and this is equivalent to current density (e. and it will be governed by the theories of irreversible thermodynamics (Chapter 16).4 Thermodynamics of cells working in steady state The previous theory did not relate to a cell in which current was being continually drawn from it. to the surroundings. The efficiency of this cell is less than 100% because the change of entropy as the reactants change to products is negative. Hence. and this is because ‘heat’ equivalent to TAS must be transferred with the surroundings.) Hence. the current in the cell is J= CJiF (it.53) In this analysis the flux term is taken to be the movement of charge per unit area through the cell. and this comes about because energy has to be transferred to the fuel cell from the surroundings to make the process isothermal. concentration gradients might be set up in the cell.Thermodynamics o cells working in steady state f 359 This is exactly the same value as was obtained in Chapter 2 on exergy and availabilty. Hence.e.
and by the Onsager reciprocal relationship.dpon. while t . = L .ions (in weak aqueous solutions)..55) t+ dpu+. This can be considered schematically as in Fig 17..t + dpu++ t .t + F dV + t . J . when an infinitesimal number of ions move through the element. so ivhile the negative ions travel in one direction the positive ones go in the opposite Ckction.gives (17. which represents a thin element of the electrolyte.4. These OH . giving dG= t + d+iu+ t  d+iOH (17.F d v = O (17.58) Since t + +t = 1 then F dV = .ions are produced in the electrolyte (KOH) as the KOH mvlecule spontaneously dissociates into K’ and OH. dG. is equivalent to the conductance of the electrolyte. k . (17. J > O .58). In the case where a current flows. then there will be a reduction in the potential available at the electrodes because some of the ‘force’ that can be generated in the cell has to be used to propel the ions through the concentration gradients that exist. and hence.dpon Applying Onsager’s relationship. and . the current.55) then it is possible to evaluate the change in Gibbs function. dG must be zero. substituting from eqn (17. Ji = Cf=. is given by (17.t .61) If the circuit connecting the electrodes is open then no current flows and J = 0.360 Fuel cells produced on the oxygen electrode.57) (17.. If the electrochemical potentials of the two ions on side A of the element are (17. = +F Hence.represents that of the anions. giving the result obtained in eqn (17.. Ions are flowing through the electrolyte.59) The term L. A more comprehensive analysis of the irreversible thermodynamics of the cell would take into account the temperature gradients that might be set up in operating the cell.60) t+k L. and t+represents the transport number of the cations. LikX.56) Now when the system is in the steady state. .
. Calculate the emf of a hydrogenoxygen fuel cell operating reversibly if the overall reduction in Gibbs energy is 238 MJ/kmol H. If the enthalpy of reaction for this reaction.4621 x [2. what must be the new pressure if the open circuit voltage is maintained constant? The values of Kp. F = 96 487 kC/kmol. amount of heat absorbed by the cell. Finally. and a new property called electrochemical potential has been introduced. 1. 53750 kJ/kg H2] An ideal. per unit amount of zinc. [ 216 937 kJ/kmol Zn.Problems 361 another group of equations for thermal conduction would have to be added to the equations in the matrix of eqn (17.8134 x lo2' at 400 K and at 410 K. 2. at 25°C is 95 200 kJ/kg Pb. calculate the magnitude and direction of the heat transfer with the surroundings.44 x e. V/K] [0. An electric cell has the following chemical reaction: Zn(s) + 2AgCl(s) = ZnC1.029 bar] . The theory of fuel cells has been developed from basic thermodynamic principles. to maintain the temperature constant during reversible operation. are 1. reversible fuel cell with reactants of oxygen and hydrogen. isothermal.015 V at 0 ° C at a pressure of 1 bar.005 V at 25°C and 1.5 Concluding remarks It has been shown that fuel cells offer the potential of converting the bond energies of a reaction directly to electrial power: this enables the restrictions of the Second Law to be avoided. assuming that the enthalpy of reaction at the same conditions is 286 MJ/kmol H. the application of irreversible thermodynamics to the fuel cell has demonstrated where some of its shortcomings will lie. calculate the emf and rate of change of emf with temperature at constant pressure if the heat transfer to the cell is 8300 kJ/kg Pb.+PbCl. If the cell operates at 75% of the reversible emf due to internal irreversibilities. 17. + 2Ag(s) and produces an emf of 1. and a product of water operates at a temperature of 400 K and a pressure of 1 bar. 23 002 kJ/kmol Zn] An electric cell is based on the reaction Pb + Hg. Estimate the following parameters at 25°C and 1 bar: (a) (b) change in enthalpy during the reaction.. [ 1.233 V.Cl. PROBLEMS Assume the value of the Faraday constant.59)..5363 V. If the operating temperature increases to 410 K. + 2Hg.
4 K] 6 A hydrogenoxygen fuel cell operates at a temperature of 450 K and the reactants and products are all at a pressure of 3 bar.2 g/kW h] . 0. H. g (W/kmol) 84 603 51 330 314 796 [32. 116. and that this remains constant over the full temperature range. calculate the fuel consumption in this case and compare it with that of the fuel cell. Assume that the enthalpy of reaction of the cell.362 Fuel cells 5 A hydrogenoxygen fuel cell is required to produce a constant voltage and operate over a pressure range of 0. Table P17.. Explain why one is higher than the other. h (kJ/kmol) 13 125 12 791 223 672 Gibbs energy. Hydrogen. The valency. If all the streams are at the same pressure evaluate the range of temperature required to maintain the voltage at this level.125 to 10 bar.O Enthalpy.25 g/kW h.16 V at a temperature of 350 K and pressure of 10 bar. The datum voltage is 1. Water.6 Table of values of enthalpy and Gibbs energy at T = 450 K Species Oxygen. If the engine has a thermal efficiency of 30% and the generator is 85% efficient. and show how the operating temperature must vary with pressure. [317. H. Qp= 286 000 kJ/kmol H. 46 g/kW h. An alternative method of producing electrical power from the hydrogen is to bum it in an internal combustion engine connected to an electrical generator. zi= 2. Calculate the ‘fuel consumption’ of the ideal cell and the actual one in g/kW h. Due to internal resistances the emf of the cell is only 70% of the ideal value.
New York. 1963: Thermodynamics. R W. 1985: Thermodynamic availability and its application to combined heat and power plant. J H. John Wiley Heywood. McGrawHill Horlock J H. Transactions of the American Society of Mechanical Engineers. R S. 1117 . J H. 1981: The Principles of Chemical Equilibrium. E M. 109.energy. although some material has been drawn from the material in this list. Chapter 1 State of equilibrium Atkins.Pergamon Denbigh. K G. 109. Proceedings of Institution of Mechanical Engineers. W W. and form. J B.237 243 ElMasri. Scientific American Books Benson. M A. chaos. R W.Bibliography This bibliography lists some of the references that have been used in preparing the book. where that is the case a specific reference is made in the text. John Wiley. 1977: Advanced Engineering Thermodynamics. J E. and on which some of the ideas were based.aircooled Braytoncycle gas turbines. Transactions of the American Society of Mechanical Engineers. 1980: The Exergy Method of Energy Systems Analysis. John Wiley Keenan. 1972: Principles of General Thermodynamics. John Wiley Chin. G N and Keenan. Cambridge University Press Hatsopoulos. Macmillan Haywood. C1. P W. and ElMasri. 1987: Exergy analysis of combined cycles: Part 2 analysis and optimisation of twopressure steam bottoming cycles. 1987: Exergy analysis of combined cycles: Part I . 1994: The Second Law . 1980: Equilibrium Thermodynamicsfor Engineers and Scientists. In general it is simply a bibliography and not a set of specific references. 1979: Combustion Calculations. and Haywood. 1988: Internal Combustion Engine Fundamentals. 228236 Goodger. 14th printing Chapter 2 Availability and exergy Ahearn. There is not a bibliography for all chapters because the information is subsumed into the books relating to adjacent chapters. 199. M A.
Mechanical Engineering Publications Linnhoff. Mar. The reader is referred to these to obtain additional information or to see different approaches. D J. Chapter 7: Equations of state This subject is covered in most of the general texts on engineering thermodynamics. J H. T J. 1995: Chemical Process Design. G and Winfold M. J H. Florida: Kreiger Moran. R W. P R. Pergamon Chapter 5: Endoreversible engines Bejan. Third edition. Society of Automotive Engineers Rant. 1956: Exergie. 36 Rogers. Forsch Gebeite Zngenieurwes. 1995: The Exergy Method of Thermal Plant Analysis. H N. 107. 1987: Cogeneration . ein neues Wort fur ‘technische Arbeitsfahigkeit’ (Exergy. Nov. 1988 Thermodynamic and transport properties of fluids. Oxford. and Senior. M J. and Mayhew.Second law analysis of combined cycles. J A. John Wiley Horlock. 1963: Thermodynamics. R. and Shapiro.364 Bibliography Keenan.A new general methodology. A. 1985: On thermodynamics of gas turbine cycles: Part I . 2933 Linnhoff. New York: John Wiley. B. 1964: A digital computer simulation for sparkignited engine cycles. F J. McGrawHill Chapter 4: Rational efficiency Haywood. M A. 5670 Smith. Z . Process Engineering.6980. Wiley International Edition Patterson. Pergamon Haywood. and 8194 Chapter 3: Pinch technology Barclay.an exergy approach. Y R. Blackwell Tsatsaronis. 22. Wiley International Edition ElMasri. R W. 1983: Energy targets clarify scope for better heat integration. The reader is referred to these to obtain additional information or to see different approaches. Chemical Engineering.combined heat andpower. 1988: Fundamentals of Engineering Thermodynamics. 14th printing Kotas. G J. 1981: Heat recovery networks: new insights yield big savings. and Turner.880889 Chapter 6: Relationships between properties This subject is covered in most of the general texts on engineering thermodynamics. and Van Wylen. a new word for ‘technical work capacity’). 10. Society of Automotive Engineers Progress in Technology Series. . Transactions of the American Society of Technical Engineers. Energy. 1980: Equilibrium Thermodynamics for Engineers and Scientists. 1988: Advanced Engineering Thermodynamics. B. 1975: Analysis of Engineering Cycles. SI units.Analysis of a coalfired steam power plant. 1985: Exergoeconomic analysis and evaluation of energyat 1 conversion plants: P r I . 1995: Combined Power and Process . G F C. London. Part 1 . 7.
1980: Equilibrium Thermodynamics for Engineers and Scientists. 1986: Principles of Combustion. International Journal of Mechanical Sciences. 785795 Chapter 14: Chemical kinetics Annand. 1. S W. R S. and Buss. 1974: Effects of simplifying kinetic assumptions in calculating nitric oxide formation in spark ignition engines. I. K G. Washington. W J D. 1979: Combustion Calculations. 1958: Additivity rules for the estimation of molecular properties. Society of Automotive Engineers Transactions. E M. W J D. 1975: Analysis of Engineering Cycles. New York: Academic Press Goodger. J H. and Keck. Wiley International Edition Chapter 12: Chemical equilibrium and dissociation Benson. DC: National Bureau of Standards Publications.Bibliography 365 Chapter 8: Liquefaction of gases Haywood. John Wiley Chapter 9: Thermodynamic properties of ideal gases Benson. G A. Macmillan Kuo. J B. 1993: An Introduction to Combustion. Macmillan Strahle. Annand. J H. Combustion Science and Technology. 431 436 . 1977: Advanced Engineering Thermodynamics. 1972: Thermodynamic Tables in SI Units. E S A. D E. 1988: Internal Combustion Engine Fundamentals. Strange. 1979: Combustion Calculations. Pergamon Haywood. and thermodynamic properties. R W. R W. J . E M. 1962: A consideration of high temperature thermodynamics of internal combustion engines. and Baruah P C. Cambridge University Press Haywood. vol II. J C. 1977: Advanced Engineering Thermodynamics. Pergamon Benson. W C. 17.313326 Vickland.97. Gordon and Breach Chapter 11: Chemistry of combustion Benson. 1970: Experimental and theoretical study of nitric oxide formation in internal combustion engines.124 Denbigh. 29. R A. 1975: A simulation model including intake and exhaust systems for a single cylinder fourstroke cycle spark ignition engine. NSRDSN35 37 Chapter I O : Thermodynamics of combustion Glassman. 1986: The Thermodynamics and Gas Dynamics of Internal Combustion Engines. Proceedings of Institution of Mechanical Engineers. McGrawHill Lavoie. and Starkman. F M. 188. Pergamon JANAF. R S. Chem Phys. Bell. R S. Oxford: Oxford University Press Heywood. (41/74). 1971: Thermochemical Tables. 1986: Combustion. Cambridge: Cambridge University Press Horlock. K K. C W. and Winterbone. 70. R W. No 3 Goodger. 1981: The Principles of Chemical Equilibrium. J B. Heywood.
New York: Academic Press Mallard. and von Elbe. 1993:An Introduction to Combustion. and Watfa. J C. 1986:Principles of combustion. B. 1982: Burning velocities of mixtures of air with methanol isooctane. Benson R S. A K. I. M R. D. 1971:Jet aircraft air pollutant production and dispersion. J C.and Keck. Lau. Proceedings of Institution of _MechanicalEngineers. and Lawes. 1961: Combustion.379 Metgalchi. N D. New York: Academic Press Heywood. 38. 48.389413 Bradley. A414. and Linden. 1986:Combustion. London: Chapman & Hall Glassman. Combustion & Flame. H. 437443 Glassman. 1948:J Phys Chem USSR. E and le Chatelier. 1970:Rate of heat release in diesel engines and its correlation with fuel injection data. S C. 1. 46. 9 ( 5 ) . D R. Proceedings of Conference o Institution of Mechanical f Engineers on Fuel Economy and Emissions of Leanburn engines. New York: Academic Press Heikal. A G. Combustion & Flame. 184. and Annand W J D. and Keck. and indolene at high pressure and temperature. McGrawHill Kuehl D K. M. Proceedings of Institution of Mechanical Engineers.3J. J B. 1988:Internal Combustion Engine Fundamentals. and Wolfhard.366 Bibliography Daneshyar. M. 1962: Laminar burning velocities in propaneair mixtures. J C.Detroit Lewis. 1940:Elektrochem. 191 210 Strahle.The effects of turbulence on flame velocities in gas mixtures) Gaydon. McGrawHill Heywood. 841 850 bavoie. Proceedings Royal Society.(41/74). Flames and Explosions of Gases. 760160. 1987: Turbulent burning velocities: a general correlation in terms of straining rates. radiation and temperature. London. R B. 188. M. Society of Automotive Engineers. Kreiger. D. W C. M. Faye. K K. 2nd edn. Eighth International Symposium on Combustion Kuo. 1883:Ann Mines. London. 4.601 (Translated as NACA Technical Memo 11 12 . Z. Heywood. and Keck. J A. and Hull W. G. 1992: Flame stretch rate as a determinant of turbulent burning velocity. 1978: Flames: their structure. Y B. 1974: Predicting nitric oxide and carbon monoxide concentrations in spark ignition engines. R J B. H G. 22 (1) . G A. I. 1970:Experimental and theoretical study of hitric oxide formation in internal combustion engines. A338. and Laws. Sorenson. J B. M. 1980:Laminar burning velocity of propaneair mixtures at high temperature and pressure. 359387 Damkohler. London Heywood. 1986:Combustion. Philosophical Transactions Royal Society. J B. H L.143154 Metgalchi. 313326 Chapter 15: Combustion and flames AbdelGayed. Gordon and Breach Whitehouse.1976:Effects of turbulence on sparkignition engine combustion. 1727 Zel’dovitch. Wiley International Edition Lancaster. R G. AZAA Journal. and Way. Bradley. 1979:A model for turbulent burning speed in sparkignition engines. J B. Combustion Science & Technology. 1988:Internal Combustion Engine Fundamentals. L H.
1967: Fuel Cells. 22652279 Tribus. E J. and Sears. H A. and Womack. A. John Wiley Liebhafsky. 37. 405426 Onsager. 1116 (Translated as NACA Tech Memo 1084) Chapter 16: Irreversible thermodynamics Bejan. K G. PrenticeHall Denbigh. 1968: Handbook of Fuel Cell Technology. 1856: Die medizinische Physik.Bibliography 367 Zel’dovitch. 1931b: Reciprocal relations in irreversible processes. 1966: Treatise on Irreversible and Statistical Thermophysics. S R. 1931a: Reciprocal relations in irreversible processes. 1940: Journal of Experimental and Theoretical Physics USSR. 1968: Fuel Cells and Fuel Batteries. North Holland Denbigh. Wiley International Edition Benson. L. L. and FrankKamenetsky. A B. 693 Zel’dovitch. K G. 1980: Equilibrium Thermodynamics for Engineers and Scientists. D A. C (Ed). Cambridge University Press Hart. 1963: Thermodynamics. part I. Hoase. 19. 1938: Compt Rend Acad Sci USSR. R. Wiley . AddisonWesley Onsager. 1961: Thermodynamics and Thermostatitics. 1977: Advanced Engineering Thermodynamics. R: Thermodynamics of Irreversible Processes. 1951: Thermodynamics of Irreversible Processes. London: Chapman and Hall Haywood. 1988: Advanced Engineering Thermodynamics. Y B. 38. Merwe. part 11. Phys Rev. 1951: Thermodynamics of the Steady State Methuens Monographs on Chemical Subjects Fick. and Semenov. Van Nostrand Yougrau. and Cairns. F W. Macmillan Chapter 17: Fuel cells Berger. Pergamon de Groot. and Raw. Y B. A. M. R S. N. 1981: The Principles of Chemical Equilibrium. G J. R W. 10. W. AddisonWesley Lee. J F. A. Phys Rev.
2 Table 11. in various units Enthalpy coefficients for selected gases found in combustion processes Properties of gases Oxygen. gas molecules 294 air 152. .222.2 Table 9.224. 100.267. 31 1 activity coefficient 353 adiabatic combustion 187205 adiabatic compressibility 115 adsorption. 292 lean(weak) 186. 359 balance. and superheated air at low temperatures and high pressures Molecular weights of elements and compounds commonly encountered in combustion Values of the universal gas constant. 26572. methane Enthalpies of formation of some common elements and compounds Some atomisation. %. 217 Amagat’s Law 1212 ammonia 296 amount of substance 7.282 atomic oxygen 164.299 alcohols 185.2425. 189.229 closed system 18.2 Table 9.300 .217.1 Table 8.217 alkanes 138.2 Table 12.21959.268.1 Table 11.1 acetvlene 185. 189.2824 atomic weight 158 atomisation 21 1 energy 20815 availability 1336. 2730 . 348 annular combustion chamber 3 13 aqueous solution 34753 argon 159 aromatics 217 Arrhenius equation 279. 319. 64.245.269. carbon dioxide Hydrogen. 217 alkenes 185. nitrogen Carbon monoxide.3 Table 15.301 stoichiometric 186.273. 2736 change of 18.299. 196205.252.26572. 1868.233.223. water Nitric oxide.273.311 atmospheric nitrogen 159 atomic nitrogen 2425.208 aifuel ratio 301. 1589. 1727.294.301 rich 186.Index Index of tables of properties Table 8.4 Critical temperatures and pressures for common substances Properties of air on saturated liquid and vapour lines.275. 225. 213.1 Table 9.3 Table 9.26572. dissociation and resonance energies Enthalpies of formation and reaction for commonly encountered fuels and compounds Equilibrium constants Flammability and explosion limits at ambient temperature and pressure 135 152 159 160 164 167 168 169 170 192 209 217 2578 296 Table 10. 159 composition 159 air standard cycle 71. 185.2167.245. acidrain 286 activation energy 27985.
30913 premixed 292305. 24557.292.224. 347 barrel swirl (tumble) 307 Baruah 268 BeattieBridgeman equation 128 Bejan 85 Benson 164 benzene 202.40.20817 chlorine 351 Clapeymn equation 117 Clausius equation of state 123 Clausius inequality 1 4 ClausiusClapeyron equation 1 5 117 1.279 steady flow 21. 24557.13940.370 Index availability (cont.144 1.218 ytm coal 185 coefficient of expansion 1 4 1235.245. 168.204.288.270. 89 26774 singlephase 183 Speed of 297304 three dimensional 183 turbulent 183.224.3079 rich mixture 186.296302 multiphase 183 nonpremixed 183. 345 carbon monoxide 1.35 work 29 availability transfer 29 available energy 216.287 combined cycle heat engine 926.296 calorific value 64 higher 188205 lower 188205 efficiency 6582. 165.137 combustion 182313 adiabatic 187274 chemistry 1847.92.9.195.100.292.312 carbon/hydrogen ratio 185.22938.300 carbon particulates 285.192.3056.292.272 Carnot cycle 21.40.27689.18.1321.26585 chemical equilibrium 21857 chemical kinetics 8.20817 constant pressure 193.30 open system 346 rate of change 29. 159.1 6 199202.310 lam in^ 183.20910.306 chemical potential 7.217.319.332.345 cascade 137 binary cycle 137 ternary cycle 137 catalytic converters 288 cetane 217 number 311 chain reaction 2956 Charles’ Law 1212 chemical bonds 187.2524.202.164. 9.305 butane 1356.287.17 minimum potential energy 20811 Bosch Smoke Number 287 Boyle’s Law 1212 Bradley 303 brake thermal efficiency 304 branching reactions 2956 bronchial irritants 286 Bunsen burner 297.348 atomisation energy 2091 7 dissociation energy 209.192 carbon dioxide 9.285. coefficient of performance 1378 cold utility 4760 combined cycle gas turbine (CCGT) 47.35 reaction 31.8.) effect of change of entropy 32 effect of change of volume 30 effect of combustion 304 flow 21. 168.2734.296305 incomplete 195.21875.18492.194.22031.34953 Standard 22730 chemical reaction 185285 chemical structure of fuels 20817 chemistry.354 chemical composition 1868.19.20817. 135.67 Avogadro’s hypothesis 159 number 340. 3347.2025.24557 exergy change 4 0 heat release 208.20817.3023 .299.35 loss of 1336 molar 15 nonflow 15. carbonI21589.8596.26775 diffusion 291 energy equation 188205.187.2338.164.291.65.296.211.217.2338.291 boiling point 137 Boltzmann constant 340 bond energy 40.24557 initiation 3045.312 heterogeneous 183. 295.225 benzoic acid 21 5 Bertholet equation 129 binary cascade cycle 137 boiler 276.196206. 21875.265. 182205. combustion 1847.3056 homogeneous 183. 68.185. 182.275.312 constant volume 193.36.209.2338. 85.159. closed s s e 57.401 specific 15.
also standard pressure 164.125 compression coefficient 129 isentropic 158. 33239.34761 density 32132 cycle calculations 304.360 molar27744 condenser 6976 conductance heat transfer 925 conduction of electricity 318.heat load diagram 5 1.89 Diesel 68 endoreversible 6582. 182. 1945.294.6582 pressure 1443 Debye theory 162 deflagration 183. 189. gas turbine 313 composite diagram 5 5 .200. 6982 cycle efficiency 6982 cycles air standard 71.335. see Joule internally reversible 6582. 135 crosscoupling 31642 crude oil 184 current electric 316. 319.32232.223. 146 volume 124 Critical point 12431.24552.57 compressibility adiabatic 115 factor 129 isentropic 115 isothermal 1145.297. 135 pressure 124.208 bottoming 34 Camot 21. 359 burning 287.311 flames 291.12 gas turbine 3123 spark ignition 3079 combustion zones.6582 compressor 245. law of 1259 Coulombic forces 348 counterflow heat exchanger 3740 coupled equations 31642 processes 31942 coupling matrix 31942 critical isotherm 1257 point 12431. 150 Dufour effect 3328 dynamic equilibrium 218.7682 concentration component 3 19 gradient 316. 214 dry ice (carbon dioxide) 139 dryness fraction (quality) 137.7682 Otto 304. 3941 detonation 183.267 Rankine 6976.303. 135.26774 with heat transfer 194.245. 135.79 reversible 65 Stirling 85 cyclone separator 288 371 Dalton Principle 172 Damkohler 302 Daniel1 cell 345 5 1 datum pressure.33242 dilution zone 313 direct injection engines 30912 dissociation 7. 296. 199 with work transfer 194 zerodimensional 183 combustion chamber 30713 combustion systems diesel 309. 3056 diffusivity mass 298.332. 349 . 85.48.68. 140 temperature 124.6582 temperature1443.65.32232 of heat 317. 8596 gas turbine.2289 dead state 1443.68.296305 de Groot 333 delocalised electrons 210 desorption gas molecules 294 destruction of availability 249. 8596 irreversible 6582 Joule 68. 6 0 composite temperature . 26575 degree of 21859 effect of pressure 23940 effect of temperature 23941 dissociation energy20810.135 water 126.3056.21859.222.31932 conjugate fluxes 31942 forces 31942 copper 34751 sulfate 34751 corresponding states.33242 thermal 298.Index twodimensional 183 weak mixture 186. 309 diatomic 184 Diesel engine 30912 cycle 68 oil 217 Dieterici equation of state 129 diffuser 313 diffusion 175.122.
3740.213.22931 creation 34. 17.24557. 348 change due to mixing 1754. 144 explosion limits 2946 external irreversibility 68.355 electrical cells 34651 conduction 316. 123.26.6982 overall 64 rational 6582.295 energy available 1336 Gibbs see Gibbs energy Helmholtz see Helmholtz energy internal 59.292 neutral 14 of mixtures 22533 stable 14.2656.8. 1213. 1656 maximum 4. 143. 192. . 125.222. 162. 67. 154. 31722.354 equivalence ratio 186205.3479 steady flow.23357. 359 thermal 17. 145.39.37. 16078. 195205.359 change 379. 345. 15978.349 mechanical 12.65. 317.23357. 56.208. 7682 van der Waals’ gas 1238 virial 128 equilibrium 19.7782. 304. 317. 140 equilibrium constant 22859.346. 14154. 35 18 chemical 21857. 187205.6982 expansion.58. 6982 nonisentropic 224. 296306 ethane 135. 80 energy equation. 8 static 222. 10018. 185. 28. 1334. 333. 24557 ofreaction 401. 21821.2225.296 ethanol 185.13 diesel 276. 336 flow 5.305.304.3643.211. 117.31642 change 3. 34.32332.3 19 mixtures 1758.372 Index eddy diffusivity 302 efficiency at maximum power 8596 cycle 6482 fuel cell 3579 isentropic 225.2412 of products 188205.24557 of reactants 188205.187217.291.2338. 64.3478 141.21. 192. 143. 189205. 14 metastable 2. 144.23.42 of reaction 401 exothermic combustion 1823 13 reaction 18890 expansion isenthalpic 14154 isentropic 224. 187205. see also ideal gas 159. 8596 Faraday’s law of electrolysis 347 Faraday constant 34760 Fick’s Law 319. 86.31722 flux 32136 generation. 165.403.89. 8596 sparkignition 208. 3079 stratified charge 305 enthalpy 69. see creation ideal gas 235.21857.217 evaporation 1157.91.291. 124 exergy 13.110. 1589 BeattieBridgeman 128 Bertholet 129 Dieterici 129 idealgas 1057.2867. 10018.283. 16075.37. 10018. 187205.2735.345 unstable 14. 304.256.292.34561 flow 32332 electrochemicalpotential 34961 electrode 34651 electrostatic precipitator 288 elementary reaction 278 end gas 309 endoreversible heat engine 8596 endothermic reaction 184. see also dead state 23 equation of constraint 227 equations of state 12131. 188205. 189205 unsteady flow 34 engine combustion systems 307 .24557 potential 14 unavailable 6.217.24557 perfect gas. 8.27.2338. 16278.276.24557 molar 160.20917.212.26.225.6482. 174 of formation 65. 37. 35561 specific 160.332 First Law of Thermodynamics 5.304. 135. coefficient of 114. 337 enthalpy coefficients of gases 16770 enthalpytemperature diagram 188205 entropy 37. 73. 19.22931 of transport 32432 production. 1943.52.6482.333 thermal 19 thermodynamics 19. 30912 irreversible 65 petrol see sparkignition reversible 5. see creation environment.2756.6482.8596. 58.282 dynamic 218.3518 condition 19.
35161 effect of composition 21821. 8692. 187205. 8596 heat exchanger 3740.2389.338 heat cascading 57 heat engine endoreversible (internally reversible) 85 96 externally irreversible 8596 irreversible 6482 reversible 57. 306. 1259.235.65.4760.291. 144.217 Hess’ law 1901.42.21833.187217.24557.332 Hatsopoulos 2 Haywood 15. 164.331. 15878. 15.35559 of transport 326.8596. 160 gasoline 2 17 gas turbine 7682.20817 structure 208. 134.2823 homogeneous combustion 183. see airfuel ratio functional relationships 100. 1827.2412 of reaction 64.297. 1636.288. 286 Heikal302 Helmholtz energy 59. 3056 hexane 217 Heywood 30. 158 universal 1238. 124. 148. 3519 engine 288 oxygen fuel cell 34559 .345 saturated 185 unsaturated 185 hydrochloric acid 351 hydrogen 135. 115 . 1213.231.3079 stretch 3034 flame quenching 3034.287. 220 heavy fuel 184.2936.3056 Honda 292 Horlock 245.24557 heterogeneous combustion 183. 152 heat flow 31739 of formation 65.8596 network 4960 rate 24. 22931 effect of pressure 219 effect of temperature 219 minimum 8. . 350 gas ideal 1057.18 galvanic cell 345.292.204. 34561 hydrogenoxygen 345. 154 reversible 379 heat flow capacity 4960 rate 3212 heat release (combustion) 312 diagram 3 12 heat transfer 3740. 1421.300.6482.101. 192. 304. 2245. 1504 counterflow 3740 irreversible 3940.20817.356. 23338. 169. 3056 extinction 3034 laminar 183.208.7682 superheated 75 6.17 fuel cell 289.32139 coefficient 86 conductance 8892 irreversible 3940. 31641 resistance 90 reversible 5.20817.359 fuel injection 291. 12 18 van der Waals’ 1238 gas constant specific 113. 310 fuelair ratio. 3034 ak flash t n 139 flue gas desulfurisation 286 fluorine 293 Fourier’s law of conduction 31632 fraction of reaction 22631 FrankKamenetskii 297 fuel 18492.24557 perfect see also ideal gas 159. 268 hot utility 4760 hydrocarbons 401. 129. 134 function see Helmholtz energy heptane 185. 3123 GayLussac’s law 1212 Gibbs 36 Gibbs energy 69.2923 molar 1635.345.265.353.26575. 1301.291. 159.289.245.296302 premixed 292305.292. 195205. 379.Index FischerTropsch process 188 flame 291313 diffusion 291.352 specific 165 Gibbs function see Gibbs energy Gibbs potential see Gibbs energy GibbsDalton laws 1725 Glassman 286 global warming 287 governing qualitative 292 373 quantitative 292 greenhouse effect 287 Hartley 319. 1368.276. 110. 3056.308 flame speed 292303 laminar 292302 turbulent 3023 flame speed factor 3023 flame traverses charge 291 flammability limits 296.
10911.2489 products. see chemical kinetics knock 183.31 1 ideal gas see gas. see chemical kinetics rate.2338.2107 Lavoie 245. 165 internal energytemperaturediagram 190. 189205. 56.34658 luminous region 297 Lurgi process 188 macroscopic theories 316 Mallard 297 mass action.2812 law of corresponding states 1256 law of mass action 22532.6479. see airfuel r t o ai Lewis 299 Number 298. 1878.307.300 isobar 1158.150 inversion temperature 142 maximum 1456 minimum 1456 irreversibility 2136.12331 critical 12531 isothermal compressibility 1145.208.188205. 23357.3740.13554. 144 .6982 isooctane 192. 12931 isotherm 1158.2107.8596 thermodynamics9.245.73 Useful 6. 147. 16770.316 kinetics chemical.4.6982 isentropic compressibility 115 isentropic efficiency 225.310 Joule experiment 110 Joulean heating 32334 Joule Thomson coefficient 106.1536. 154 irreversible engine 65 82 heat transfer 3.265 internally reversible 21 interval heat balance 52 inversion point 142. 160. 1412.37.374 Index hypergolic mixture 2934.309 Knudsen 339 Kuehl301 laminar flame speed 296305 theories 2979 thickness 303 Lancaster 303 latent heat 1158. 122.296.52.304.176 of formation.304. 160.235.49 liquefaction 13554 liquefied natural gas 136. 141.165.6482.135.2634.278 mass m s f e r 320. 194.3101 delay 311 minimum energy 305 timing 303 indirect injection diesel engine 309. 24557.3479 molar. 1005.33242 maximum power 8596 maximum work 56. thermocouple32232 Karlovitz number 3034 Keck 299 Keenan 2. 151 effect 1438 experiment 1419 junction.12331.217. 1879. law of 22532.357 output 8596 Maxwell equal area rule 12931 relationships 10018.304.23357 reactants.138 liquefied petroleum gas (LFG) 136 liquid line saturated 1138. 1820. 189205.31641 isenthalpic line 14254 isenthalpic process 14254 isentropic compression 158. ideal mixtures see mixtures of ideal gases ignition 2913.187205.6582. 13554 liquid phase 1138.278 Laws of Thermodynamics First 5.3940.23357 specific.10 injection direct 30910 fuel 309 indirect 309 nozzle 309 intercooled regenerated gas turbine 2878 interface 34650 intermediatecombustion zone 313 internal combustion engine see engine internal energy.1758 Third 1623 Le Chatelier 297 lean burn engines 304 lean mixture.10018.1536.3478 Second 29.1343.1745. 100.6582 expansion 224. 1602. 143.351.36 kinematic viscosity 302 kinetic theory of gases 123.278.12331.3034 Linde liquefaction plant 14854 Linnhoff 47. 125 jets 3056.212 of reaction.
24554.327.265. flame 306 mixture 1857.2935 Ohm’s law 3168. 167.256.217.26575.245. see oxides of nitrogen number density 277 Octane 185.300 exergy of reaction 4 1 methanol 185.6982 NO.299 Mollier (hs) diagram 150 multiplication factor (combustion)2956 naphthalene 209. 292306 atomic 164.345 nitrous oxide 282 NO see nitric oxide nonavailable energy 6. 101.217. 170.324 Ohmic heating 329 Onsager 3 16 reciprocal relationship 31922.145. 135. 2735.225.217.20817. 37 nonflow availability 158.276 rich 186. 148. 182.300 375 enthalpy of reaction 32. 2734.196.312 particulate emissions 287. 164.347. 185.299 strength. 170.273.167.276.246.281.33941 potassium hydroxide 353 potential chemical 78.300.Index May combustion chamber 3078 Metgalchi 299 methane41.286.2167. oxides of oxygen9.21857.300 specific heats 175 stoichiometric 186. 159.270.267.276 airfuel ratio 301.24554.352 electrochemical34961 energy 14 core. 135.2425.300 molar availability 15 concentration 27784 properties 160. 192.1869.282 oxides of 266. 100.2547.2425.22933.292 entropy 1758 fuelair ratio. 174 mole fraction 173.268.257.2402.see airfuel ratio weak or lean 186. 185. 1728.6482. 105 PAH (polycyclic aromatic hydrocarbons) 287 PAN (peroxyacyl nitrate) 286 paraffins 185.2809 formation 182.30 nonisentropic expansion 224.269. 165.239.233.68. 165. 217.78 law 1213 petrol 217.26575.3327.2809 initial rate of formation 2825 prompt 280 thermal 280 nitrogen 135.2735.2427. 159.270 atmospheric 159 atomic 164. 14054 phenomenological laws 316 photochemical smog 286 pinch point 4760 technology 4760 piston speed mean 3023.2735.2225. 196205.164. 34658 supercritical140 superheat 1239.7682 flow exergy 423.319.311 ideal gases 158.360 optimum temperature ratio 8796 orimulsion 286 Ostwald 345 Otto cycle 304. see airfuel ratio hypergolic 2934.2735.272 partial PESSW 173.212.26775.300 engine see spark ignition phase 10118 boundary 346 liquid 1138.26775. 176.145.272 liquefaction 1378 net rate of formation 27685 net work 19.296.311 pollutants 187.217 natural gas 1378.304.2107.2835 molecular weight 1589.2338. 192. 185.242.342.217 exergy of reaction 41 OHradical2435.22031.245.26575.217.222.12331. 164. 165.22930. 34953 difference 321.276.348 network heat transfer 4960 nitric oxide 164.224.265.212.2825 ozone 286 pvT diagram 8. flame 306 gradient 31632 .2578.217.225.345 minimum energy for ignition 305 minimum net heat supply 4760 minimum temperature difference 47 60 misfire 304 mixing zone.267 oxidant 182 oxides of nitrogen see nitrogen. 148.222.312 Peltier coefficient 32232 effect 31632 pentane 217 perfect gas 159. 135.2869 porous plug 142.26571.1912.257. 13554.
11 reversible engine 5. 187217. 194.252. 300 saturated liquidline 101.345 of Thermodynamics 29. 217. 12331. 1138.348 reaction 182300 availability of 3 1.27689.22759. 136. 185. 182205.225. 304 specific availabilitysee availability internal energy see internal energy enthalpy see enthalpy . 359 reactants 8.3538 standard 227 8 primary combustion zone 3 13 process integration 4760 irreversible 3.2934 rate 182.295 Rankine cycle 6976. 6582 isobaric 129131.265. 8596. 158 Second Law efficiency 6582. 300 propanol 217 propyne 2 17 Property quasi. 6582 products temperature 192205. 154. 2956 reduced pressure 1259.1 forward 27685 fraction of 22630 internal energy of 304. 148 properties 1259 temperaturel259.3112 rate constant 27885 rate controlled 27985.26. 13554 vapourline 101.1 backward 27685 branching 2956 chemical 186285 enthalpy of 64. 17. 299 premixed combustion 291305. 245.304.41. 31642 isentropic 158.187217. 306 rate of entropy production 31742 of formation 2788 of heat transfer 24.220 Rant 36 rate constant see reaction.2002. 3079.222.2956.27685.52. 311 premixed flames 296305 preparation rate 3 112 pressure critical 124. 281.2338. 13554 liquidvapour region 113. 148 volume 1259 refrigeration cycle 1358 refrigeration plant 1379 refrigerator 136. 1138. rate constant rate kinetics 8.379.295.308 quiescent combustion chamber 310 radicals 2445.27685 ratio of specific heat capacities 1145 rational efficiency 6482.2835.20817. 289.6482. flame 187.22259.26575. 12931 plant 4760 reversible 2341.401.65. 12331. 40.8596 heat transfer 5. 291313.244. 15.303. 1504.266.35561 exergy of 40. 17.220 internally 5 process 15.233.224.2341.6582. 135.2278 partial 1728.64 power output.23359 propane 135.36 pseudo. 13554. 100 work 15 Reynolds number 303 Ricardo Comet V 309 rich mixture 186. 12331.275.57 order 277.245.21.2389.313 Seebeck effect 31632 Semenov 297 Senior 47 shaft work 14 solidgas region 140 soot 287 dry 287 Soret effect 33238 spark ignition engines 208.3123 isothermal 1158.36 reduced 1256 proton charge 347 pyrolysis 312 quality (dryness fraction) 137 quenching. maximum 8596 F'randtl number 303 preexponential factor 279. 192. 31642 of reaction 182. 8692. 148 relationships thermodynamic 10018 relative molecular mass see molecular weight relaxation time 282 reservoir 14. 154.21.376 Index power generation plant 47.8696 resonance energy 209.233. 10018 secondary combustion zone 309. 299.296. 1343. 140 datum 164.
35960 steady state 31642.222. 135.359 thermoelectricity 31632 thermoelectric effect 32232 phenomena 32232 thermostatics 3 16 Third Law of Thermodynamics 1623 Thomson 3 16 coefficient 323.6482.23359 ratio 8796 optimum 87 96 reactants 193205. 33242 open 346 single component 100. 175.349. 158 supply temperature 47 60 swirl 3103 tumble 3078 barrel 3078 system closed 139. 140.254.2779. 316. 35960 relationships 100.18 velocities 3 18 thermodynamics classical 316 irreversible 31642.11 temperature adjusted 4760 critical 124. 146 difference. 189.2167.217.18 Tsdiagram 1643. 113.352.35960 forces 31642. 3402 steady flow availability 2135 steady state 3 17 Steam plant cycle 478. 16075 at constant pressure 1067.6582 equations 121.18 isolated 34.299 coefficients 2212.13554 target temperature 4760 Taylor microscale 303 Tds relationships 108.26585.233.8596.6481.1 throttle 154 throttling 136 toluene 2 17 transitory state 8 triatomic 190 triple point 20 pressure 140 tumble swirl 3078 turbine 224.345.104. 1945 supply 4760 target 4760 temperatureheat load diagram.354 mixture 186.269. 332 heat 323.478.3123 work 224.288 stoichiometry 186.233.Index exergy see exergy Gibbs energy see Gibbs energy specific gas constant 126. 292.116.227 sulfur dioxide 2856 supercriticalvapour 140.26775.2268. minimum 4760 intervals 4760 inversion 142. 122. 149 superheated gas 135.23359 standard 41. 6976 turbine 6976.267.22359. 317 multicomponent 21859.2212. 291313 airfuel ratio 186.298 at constant volume 105.6482 turbocharger 34 turbulence 291.330. 1456 products 193205. 6482.350 CuNi 328 Platinumrhodium 328 thermodynamic properties ideal gas 15878 ideal gas mixtures 158.85 Stirling engine 85 stoichiometric 185205. 158 specific heat capacity 10418. 1728 thermodynamic flow 318 fluxes 31642.2167.355 transpiration 3402 thermocouple 322332. 193 State dead 1443. 2734 constant composition 100. 113 mean 1712 of solid 162 ratio of 1145 relationships 10418 spontaneous change 4 squish motion 307 stability criterion 4 stable equilibrium 19 standard chemical potential 227 3 1 pressure 2278 temperature41. composite 4760 temperatureenthalpy transfer diagram 47 60 thermal conductivity 298 diffusion 33242 efficiency 17. 3023 intensity 303 turbulent entrainment 305 377 . 189. 1589 transitory 8 statistical thermodynamics 165.
12531. 160 unsteady flow energy equation (USFEE) 3435 utility 4760 Cold 4760 hot 4760 valency 3479.150.2578 Way 311 weak mixture 186.3546 van der Waals’ gas 10510. 13554 supercritical 140.356 net 19. 169. 1446 van? Hoff equation 165.3478 output rate 8596 reversible 1342 shaft 14 turbine 224.49 twophase region 1158. 13554 twoproperty rule 108.3123 Turner 47. 12431. 1239. 135.38.211.304.268 work displacement 134 feed pump 726 maximum 56.26571 Weber 339 Whitehouse 3 11 Wilson cloud chamber 8 Winterbone 245.6479.307 universal gas constant 1238.) flame speed 3023 mixing 30510.212.135 exergy of reaction 41 latent heat 1158 van der Waals’ equation 12531 watergas reaction 232. 182.149 wet 136 virial equation of state 128 volumetric strain 1223 von Elbe 299 water20.41.15. 122 unavailable energy 6.73 maximum useful 1536.6482 useful 1325 xylene 217 Young’s modulus 123 Zel’dovitch 2978 Zero emissions vehicle (ZEV)288 zinc 347. 159.34851.67. 192. saturated 1138.378 Index turbulent (conr.2389.80 unburned hydrocarbons (uHC) 288.292.3539 critical point 126.270.245.252.355 vapour line.223. 12331. 164.6442.26.349 sulfate 347 .
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