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, McGraw Hrll(c",porl( <





1.1 1.2 1.3

1.5 1.6

J 10

Macroscopic vs Microscopic Viewpoint J Thermodynamic System and Control Volume 2 Thermodynamic Propenies. Processes and Cycles 3 Homogeneous and Heterogeneous Systems 4 Thermodynamic Egwlibrium 4 Quasi-Stalic Process 5 pun:: S ubsta nce 7 Concept of Continuum 7
lInjisandDjmensjons 8


History ofThennodynamics Solved Examples 20 Review Questions 2 J







2.6 2.1

Ideal Gas Temperature 29 Celsius Temperature Scale 30

Electrical Resjstance Thcrmomrler JO

2.9 2. 10

Thermocouple JJ International Practical Temperature Scale 32

Solved E,xumples JJ Review Questiol/.S 35

Problems J.

Work lid Heat TrUffe r 31 Work Transfer 37 3.2 pdV Work or Displacement Work 3.3 Indicator Diagram 42



3.4 3.5 3.6


Other Types of Wark Transfer 44

Free Expansion with Zero Wort Transfer 49

Net Work Done by a System 50

Heal Tnmsftr Heat Transfer 50 A Path Function



Specific Heat and Latent Heal

Transfer and Work Transfer


Point to Remember Regarding Heat

Solved E=mpJes 54 Re1'jew Questions 58
Problem s 59

4. First Law orTbennodYDamks

4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9
4 J0


First Law for a Closed System Undergoing a Cycle 63 First Law for a Closed System Undergoing a Change of State Energy A Property oClhe System 66 Different Forms of Stored Energy 67 Specific Heat at Constant Volume 69 Enthalpy 70 Specific Heal al Constant Pressure 70 Energy ofan Isolated System 7/ Perpetual Molion Machine of the First Kind--PMM I 71 I imitations o(the FjI!i1 J aw 7Z

Solved Examples
Review Questions
frohlem s 77


S. Fin! Law Applied 10 Flow Procuses



5.2 5,3
5.4 5.5 56 5.7

Steady Flow Process 82 Mass Balance and Energy Balance: in a Simple Steady Flow Process 83 Some Examples ofSleady Flow Processes 86 Comparison of S.F.E.E. with ElIler and Bernoulli Equations Variable Flow Processes 91 Example Variable Flow Problem 93




Discharging and Charging a Tank 95

&h-ed Examples 97 Review Questions 106 Problem s 107


Se<:ond LIIW orTbermodynamics 6.1 Qualitative Difference between Heal and Work 6.2 Cyclic Hcal Engine J 12 6.3 Energy Reservoirs J 14
6~ly inPJanliSlaJ.em.ent.o[Sccond...LaYL-L1.i




6.6 6.7 6.8 6.9 6.10

6. 11

6.)3 6.14 6.15 6. 16 6. 17 6. 18

Clausius' Stalement ofthe Second Law 116 Refrigerator and Heal Pump 116 Eguivalence of Kelvin-Planck and Clausius Statements 119 Reversibility and Irreversibility 110 Causes ofIrreversibil ity 121 Conditions for Reversibility 126 Camol Cycle 126 Reversed Heat Engine 118 Cam ot' Ii Theorem 119 CorollaryofCarnot'sTheorem /31 Absolute Thermodynamic Temperature Scale 131 Efficiency of the Reversible Heat Engine 1]5 Equality of lde!!l Gas Temperature and Kelvin Temperature 136 TypesofllTevers.ibil ity /37

So/lw Examples
Review Questions


7. Entropy
7 I


Intmdw:.tiOlLJ.S2 Two Reyersible Adiabatie Paths Caunol inlem;t Each Other

Clansills'ThCOI]!ID ISl The Propeny of Entropy Jj5 Principle ofCaratheodory 158 The Inequality of Clausius /59 Entropy Change in an Irreversible Process 161 Entropy Principle 163 Applications of EntroPY Principle 164 Entropy Transfe r Mechanisms / 7/ Entropy Generation in a Closed System /73 Entropy (icneration in an Open System 177 First a nd Second I aW5 Combi ned 178 Reversible Adiabatic Work in a Steady Flow System 179 Entropy and Di~lion: The Second Law A Directional Law neNature IN) Entropy and Disorder /81 Absolute Entropy 183 Entropy and Information Theory 183 Postulatory Thetmodynamics 190


7.4 7.5
7 .

7.7 7.8 7.' 7. 10 7.11 7. 12

7 13


7.16 7.17 7.18 7.19

Solved Examples

Quel'lions Problem.s ?05

/9/ 204 214

8. Ava ila ble E ner o, Exergy a nd IrreversibiUty

8. 1 8.2 Available Energy 214 Available Energy Refcrrcd to a Cy!;;e



=8.3 84 8.5
86 87 8.8 8.9 8.10 8.11 8.12 8.13


QualityofEnergy 219 Maximum Work in a Reversible Process 211 Reversible Work by an Open System Exchanging Heat only with the Surroundings 224 I !sefill Wod; 117 Dead Slate 229 Availability 230 Availability in Chemical Reactions 231 Irreversibility and Gouy-Stodola Theorem 234 Availability or Exergy Balance 2J 7 Second Law Efficiency 240 Conunents on Exergy 247

Solved Examples 249 Review Questions 27 J

Prob/enu 271


Properties of Pure Subst.lnces 9.1 ,cv Diagram for a Pun: Substance 279 9.2 {eTDiagram Cor a Pure Substance 184 9.3 {ev-TSurface 285 9.4 T-s Diagram for a Pure Substance 285
9.5 9.6 97 9.8 9.9
h-!l Diagram or Mollier Diagram for a Pure Substance OualityorDrxnessFraction 291 Steam Tables 29f Chans ofThennodynamic Properties 295 MeasurementofSteamQuaiity 295



Solved Examples 302 Review Questions 322


10. Propertiel of Gasel and Gal MiJtures 10.1 Avogadro'sLaw 328 10.2 Equation of State ofa Gas 328 10 3 Ideal Gas HI 10.4 Gas Compression 343 10.5 Equations ofSlale 349 10.6 Virial Expansions 350 10.7 LawofCorreSJ>OndingStates 351 10.8 Other Equalions of Stale 359 10.9 Properties of Mixtures ofGases-Dallon's Law of paoial Pressures H9 10. 10 Internal Energy, Enthalpy and Specific Heats of Gas Mixtures i61 10.11 Entropy of Gas Mixtures 363 1012 Gibbs Function oCa Mixtu re oflner1 Ideal Gases



SQiloeJ Examples 366 Revjew Questions 383


II. Tbennodynamit Relations, Equilibrium and Third Law I I I some Matbema1ical Theorems f96 11.2 Maxwell's Equations 398 11 .3 TdS Equations 399 11.4 Difference in Heat Capacities 399 11 .5 Ratio of Heat Capaciti~ 401 11.6 Energy Equation 401 I I 7 lOllle_Kel vi n Effec t 405 I I.S Clausius-Clapeyron Equation 409 11 .9 Evaluat ion ofTherrnodynamic Propenies from an Eq uat ion of State 411 11. 10 General Thennodynamic Considerations on an Equation ofStatc 415 11.1 1 Mixtures of Variable Composition 417 11 .12 Conditions ofEq uilibriwn ora Heterogeneous System 410 J 1.1 3 Gibbs Phase Rul c 411 11.14 Types of Equilibri um 423 11 .15 Local Equilibrium Conditions 416 11.1 6 ConditionsofStability 427 11 .17 Third Law ofThennodynamics 428
Soll'cd Examples
Problem! 449



Review Questiolls 448

12. Vapour Power Cvdes 12.1 Simple Steam PowerCycie 457 12.2 Rankine Cycle 459 [2.3 Actual VapourCyclc Processes 462 12.4 Comparison of Rankine and Camot Cycles 464 12.5 Mean Temperature of Heat Addition 465 12.6 Rcheat Cycle 468 12.7 Ideal Regenerative Cycle 470 12.8 Rege nerativeCycle 472 12.9 Reheat-RegencraliveCycie 476 1210 Feedw3ter Heaters 477 12.11 Exergy Analysis of Vapour PowcrCycics 479 12.12 Characteristics of an Ideal Working Fluid in VapourPowcr Cycles 48 1 12.1 3 Binary Vapour Cycles 483 12. 14 Thennodynamics of Coup ted Cycles 486 12.15 Process Heal and By-Product Power 487


12.16 Efficiencies in Steam Power Plant So/l'ed Examples 492 Review Questions 5/3
Problems 514


13. Ga. Power Cycle. 13.1 Carnol Cycle (1824) 521 13.2 Stirling Cycle (1827) 522 13.3 Ericsson Cycle (1850) 523 13.4 AirSlandardCycles 524 13.5 Otto Cycle (1876) 524 13.6 Diesel Cycle (1892) 527 13.7 Limited Pressure Cycle, Mixed Cycle or DWll Cycle 5)0 13.8 ComparisooofOtto, Diesel. and Dual Cycles 5)2 13 .9 I 533 13.10 548 13.11


14. Rerrigeratlon Cycles


14.\ 14.2 14.3 14.4 14.5 14.6 14.7 14.8

Refrigeration by NooCyclic Processes 578 Reversed Heat Engine Cycle 579 vapour Compression RefrigerntioD Cycle 580 Absorption Refrigeration Cycle 591 Heat Pump System 595 Gas Cycle Refrigeration 596 LiquefaelionofGases 598 ProducljonofSoiidlce 600 Solved Examplcs 6()() Review Questions 6J I
Problemy 612

15. P.ycbromecrkl 15.1 Propenies of Atmospheric Air 617 15.2 Psychrometric Chart 622 15.3 Psychrometric Processes 623 Solved Examples 63 1 Review Questio/l.S 641 frob/erru 642 16. Reactive Systems 16.1 Degree ofReacljoD 614 \6.2 ReactionEquilibrium 647 16.3 Law of Mass Action 648



16.4 16.5 16.6 \6.7 16.8 16.9 16. 10 i6.11 16.12 16.13 16.14 16.15 16.16 16.17 16.18 16.1 9 16.20 16.2 1

Heat of Reaction 648 Temperature Dependence of the Heat of Reaction 650 Temperature Dependence of the Equilibrium Constant MI Thennallonization ofa Monatomic Gas 651 Gibbs FWlCtion Change 653 FugaeityandActivity 656 Displacement of Equilibrium Due to a Change in Temperature or Pressure 657 Heat Capacity of Reacting Gases in Equilibrium 658 Combustion 659 EnthalpyofFoMnation 660 First Law for Reactive Systems 661 Adiabatic Flame Temperature: 663 Enthalpy and Internal Energy of Combustion: Heating Value 663 Abso lute Entropy and the Third Law ofThennodynamics 664 Second Law Analysis ofReactivc Systems 666 ChemicalExergy 667 Sel;ond Law Efficiency ofa Reactive System 670 Fuel Cells 670 Solved Examples 673 Review Questions 689 Problems 690

17. Comp ressible Fluid Flow

17.1 17.2 17.3 17.4 17.5
[7 6


Velocity of Pressure Pulse in a Fluid 696 StagnalionPropertics 698 One Dimensional Steady Isentropic Flow 700 Critical Propenies----cboking in Isentropic Flow Nonnal Shocks 708 Adiabatic Flow wi th Friction and Djpbatjc Flow without Friction 714 Solved Examples 715 Review Questio ns 712


18. Element' of Ucat Transfer 18.1 BasieCoocepls 726 182 Conduction Heal Transfer 727 18.3 Convective Heat Transfer 736 18.4 Heal Exchangers 742 18.5 Radialion Heat Transfer 749 Solved Examples 757 Review QuesriollS 766 Problems 768



19. Statistica' Tbermodynamici

19.1 19.2 19.3 19.4 19.5 19.6 19.7 19.8 19.9 19.10 19.11 19. 12 19 13 19. 14 19. 15 19.16 19 17 19. 18 19.19 19.20 19.21 19 22 19.23 19 24 19.25 19.26 19.27 Quantum Hypothcsis 772 Quantum Principle Applied to a System of Particles 773 Wave-Particle Duality 775 de Broglie Equalion 776 Heisenberg's Uncertainty Principle 777 Wave Equation 777 SchriklingerWaveE9 ual ion 780 Probability Function: VI 781 PartideinaBox 781 RigidRolalor 785 Hannonic Oscillator 786 Phase Space 786 Microsla!r and Macros!a!" 787 Maxwell-Boltz.mannStatistics 788 Stirling's Approximation 790 Maxwell-Boltzmann Distribution Function 791 Bose.Eins!einS!a!is!ics 79' FermiDirac Statistics 794 Summary of Distributions of Part ides Over Energy Levels Partition Function 795 Entropy and Probability 796 Mona!omic Idcal G3S 799 Princi ple ofEguipartition of Energy 802 Statistics ofa Photon Gas 804 Elc:etron Gas 806 Thermodynamic Properties 8/J Spc:eific Heat of Solids 8/6 So/~-ed Examples 818 Review Questiofll' 822 Problems 824 Entropy Flow and Entropy Production 826 Onsager Equatio ns 828 Phenomenological Laws 829 Rate of Entropy Generation: Principle of Superposition 830 Proof of On sager's Rcciprocal Relations 836 Thcnnoclectric Phenomena 837 Tbennomechani cal Phenomena 846 Stationary States 849 So!I'ed Examp!e.~ 85/ Review QueSTions 855
Problem < X 57



2&. lrnvenlble nermodynllmlcs

20.1 20.2 20.3


205 20.6 20 7 20.8


21. KJnetic Theory of Gasts aDd Distribution of Molrcular Velocities 21 I MoleclllarModcl 860 21 2 Distrihutiol.Ulf.MokculaLYclncitie.UnDirc1:lion lilll 21.3 Molecular Collisions with a Stationary Wall 862 21.4 Pressure ofa Gas 864 21.5 AbSQlute Temperaturo ora Gas 866 21.6 Collisions with a Moving Wall 867 21.7 Clausius Equation of State 868 21.8 van der Walls Equation of State 869 21.9 Maxwell-Boltzmann Velocity Distribution 870 2 1.1 0 Average. Root-Mean-Sguareand Most Probable Speeds 876 21.11 Moiecu1esinaCertainSpeedRange 878 2 1.12 Energy Distribution Function 880 21.13 Principle ofEquipartition of Energy 882 21.14 Specific Heat ofa Gas 883 2 1.15 SpecificHealsofaSolid 884 Solved Examples 88J
Problems 22 1 22 2 894


n . Tnnsport Proctsses In Gases

Mean Free Path and Collision Cross_section Distribution of Free Patbs 898



Transport Properties 901 Soh-ed Examples 911 Review Questions 917


Appendices Bibliography Index

91 / 97J


ThemlOdynamics is the science of energy transfer and its eff~1 on the physical propenies of substances. It is based upon observations of common experience
which have been fonnulated into thermodynamic laws. These laws govern the

principles o[encrgy conversion. The applications of the thermodynamic laws and

principles arc found in all fields of energy technology, notably in steam and

nuclear power plants. internal combustion engines, gas nubines, air conditioning, refrigeration. gas dynamics, jet propulsion, compressors, chemical process plants, and dI rect energy conversion devices.


Macroscopic V a Microscopic Vlewpolnt

There arc two paims o[view from which the behaviour of matter can be studied: the macroscopic and the microscopic. In the macroscopic approach, a certain

quantity of malter is considered, without the events occurring at the molecular level being taken into account. From the microscopic point of view, matter is composed of myriads of molecules. If it is a gas, each molecule at a given instant has a ccnain position, velocity. and energy. and for each molecule these change vcry frequently as a result ofeollisions. The behaviour of the gas is described by summing up the behaviour of eaeh molecule. Such a study is made in microscopic or statistical thermodynamics. Macroscopic thermadynamics is only concerned with the effects of the action of many molecules. and these effects can be perecived by human senses. For example, the macroscopic quantity, pressure, is the average rattof change of momentum due to all the molecular collisions made on a unit area. The effects of pressure can be felt. The macroscopic point of view is not concerned wi th the action of individual molecules, and the fon:e on a given unit area can be measured by using, e.g., a pressure gauge. These maeroscopic observations are completely independent of the assumptions regarding the nature

&ui~ 11M ilpplitd


of matter. All the results of classical or macroscopic thennodynamic s can, however, be derived from the microscopic and statistical study of matter.

1.2 Thermodynamic System and Control Volume

A thennodynamic system is defined as a quantity of matter or a region in space upon which attention is concentrated in the analysis of a problem. Everything external to the system is called the surroundings or theenvirOllmelll. The system is separated from the surroundings by the system boundary (Fig. 1.1). The boundary may be eitherflXed or moving. A system and its SUlToundings together comprise a universe.
""" Boundary '\


Energy out



Energy In

Fig. ),)

il tlwmodylU1.mic S]Jtrm

No mass tJansfer Fig. 1.2 il cloud S'jJum

There are three classes of systems: (a) closed system, (b) open system and (c) isolated system. The closed system (Fig. 1.2) is a system of fixed mass. There is no mass transfer across the system boundary. There may he energy transfer into or out of the system. A certain quantity of fluid in a cylinder bounded by a piston constitutes a closed system. The open system (Fig. 1.3) is one in which matter crosses the boundary of the system. There may be energy transfer also. Most of the engineering devices are generally open systems, e.g., an air compressor in which air enters at low pressure and leaves at high pressure and there are energy transfers across the system boundary. The isolated system (Fig. 1.4) is one in which there is no inleraction between the system and the surrounding. It is of fixed mass and energy, and there is no mass or energy transfer across the system boundary.

""0 "'",
MaSll in


' '":':00'
Surroulldlngs Surroundings

Energy oul
A~ Qptn

No mass or anergy transf8(

Flg. 1.3


Flg. U


iJmltt! SJJltm

If a system is defined as a certain quantity of matter, then the system contains the same matter and there can be no transfer of mass across its boundary.

However, ifII system is defmed as a region ofspace within a prescribed boundary, then matter can cross the system boundary. Whil e the former is called a closed system, the latter is an open system. For thermodynamic analysis of an open system, such as an air compressor (Fig. I .S), attention is focussed on a certain volume in space surrounding the compressor, known as the controll'olume, bounded by a surface called the control surface. Matter as well as energy crosses the control surface.

w"" ---tt-I MaIO( ~

_-------11 1.
Ai" compressor


, / """'"
_ _ ....rtace

i-~--A i"-\-\" - - - -" - - - - .-----""---""---""-----..

AIr in fig. 1.5 CnlriIf PQI.IIU aM un/rot svrfQU

~ """"'""~

A closed system is a system closed to matter flow, though its volume can change against a flexible boundary. When there is matter flow , then the system is considered 10 be a volume affixed identity, the control volume. There is thus no difference between an open system and a control volume.

1.3 Thermodynamic Properties, Processes and Cycles

Every system has certain chlll1lcteri stics by which its physical condition may be described, e.g., volwne, temperature, pressure, etc. Such characteristics are called properties of the system. These are all macroscopic in nature. When all the properticsofa system have definite values, the system is said to exist at a definite stale. Properties are the coordinates to describe the state ofa system. They are the state variables orthe system. Anyoperation in which one or more of the properties of a system changes is called a change ofslate. The succession of states passed through during a change of state is called the path of the change of state. When the path is completely specified, the change of state is called a process, e.g., a constant pressure process. A thermodynamic cycle is defined as a se ries of state changes such that the final state is identical with the initial state (Fig. 1.6) Properties may be of two types. Intensive properties are independent of the mass in the system, e.g., pressure, temperature, etc. Extensive properties are related to mass, e.g., volume, energy, etc. If mass is increased, the values of the extensive properties also increase. Specific extensive properties, i.e., extensive

properties per unil mass, are intensive properties. e.g., specific volume. specific energy. density. etc .


e-b A pnxllISS 1-2-1 Acyde

Fig. 1.6 A prlKm aM" ?'U

1.4 Homogeneous and Heterogeneous SyUems

A quantity of matter homogeneous throughout in chemical composition and physical structure is called apho$f!. Every substance can exist in anyone of the three phases, viz., solid. liquid and gas. A system consisting of a single phase is

called ahomogeneous system, while a system consisting of more than one phase is known as a hererogeneoU$ sy.1tem.

1.5 Thermodynamic Equilibrium

A system is said to exist in a state ofthermooynamic equilibrium when no change in any macroscopic property is registered, if the system is isolated from its surroundings. An isolated system always reaches io course of time a stale ofthcrmodynamic equilibrium and can never departJrom it spontaneously. Therefore, there can be no ypontaneous change in any macro:rcopic property if the system exists in an equilibrium state. Thermodynamics studies mainly the properties of physical systems that are found in equilibrium states. A system will be in a stateofthermodynamic equilibrium, if the conditions for the following three types of equilibrium are satisfied: (a) Mechanical equilibrium (b) Chemical equilibrium (c) Thermal equilibrium In the absence of any unbalanced force within the system itself and also between the system and the surroundings, the system is said to be in a state of mechanical equilibrium. Ifan unbalanced force exists, either the system alone or both the system and the surroundings will undergo a change' of state till mechanical equilibrium is attained.

If there is no chemical reaction or transfer of matter from one partofthe system to another, such as diffusion or solution, the system is said to exist in a state of chemical equilibrium. When a system existing in m~hanical and chemical equilibrium is separated from its surroundings by a diathermic wall (diathennic means 'which allows heat to flow') and if there is no spontaneous change in any property of the system, the system is said to exist in a state oflhermal equilibrium. When this is not satisfied, the system will undergo a change of state till thermal eqUilibrium is restored. When th e conditions for anyone of the three types of eqUilibrium are nol satisfied, a system is said to be in a nonequilibrium siale. If the nonequilibrium of the state is due to an unbalanced force in the interiorofa system or between the system and the surrounding, the pressure: varies from one part of the system to another. There is no single pressure that refers 10 the system as a whole. Similarly, iftbe nonequilibrium is because of the temperature oflbe system being different from that of its surroundings, there is a nonunifonn temperature distribution sct up within the system and there is no single temperature that stands for the system as a whole. It can thus be inferred that when the conditions for thermodynamic equilibrium are nOI satisfied, the states passed through by a system cannot be described by thermodynamic properties wh ich represent the system as a whole. Thermodynamic properties are the macroscopic coordinates defmed for, and significant to, only thermodynamic equilibrium states. Both classical and statistical thermodynamics study mainly thc equilibrium states ofa system.

1.6 Quasi-Static Process

Let us consider a system of gas contained in a cylinder (Fig. \.7). The system

initially is in equilibrium state, n;prescnted by thc propertiesPl' VI' II' The wcight on the piston just balances the upward force exened by the gas. If the weight is removed, there will be an unbalanced force between the system and the surroundings, and under gas pressure, the piston will move up till it hits the stops.



",<:4--- Pistoro

Fig. 1.7


/HIWIt1l lIN


s/iJ/ts Ii] u

~nNklllCtd fora
Jr~ -,!




consideration, and CFa is the component of fon:e normal to 6A (Fig. 1.13), the pressure p at a point on the wall is defined as

. 5F. \1m -


Fig. 1.13 DtjiMlfirm o!PTtJJMr,

The pressurep at a point in a fluid in equilibrium is the same in all directions. The unit for pressure in the 81 system is thepasc(l/ (Pa), which is the force of one newton acting on an area of 1 m 2. I Pa - I N/m2 The unit of pascal is very small. Very often kilo-pascal (kPa) or mega-pascal (MPa) is used. Twoother units, not within the SI system of units, continue to be widely used. These are the oor, where 1 bar " lOS Pa - 100 kPa " 0.1 MPa and the standard atmosphere, where I atm .. 101.325 kPa - 1.01325 bar Most instruments indicate pressure re lative to the atmospheric pressure, whereas the pressure ora system is its pressure above zero. or relative to a perfect vacuum. The pressure relative to the atmosphere is called gauge preuure. The pressure relative to a perfect vacuum is called ablo/ute prl!$$ure. Absolute pressure '"' Gauge pressure + Atmospheric pressure When the pressure in a system is less than aunospheric pressure, the gauge pressure becomes negati ve, but is frequently designated by a positive number and called vacuum. For example, 16 cm vacuum will be
76 -16 x 1.013 " 0.08 bar 76

Figure 1. 1.4 shows a few pressure measuring devices. Figure (a) shows the
Bourdon gauge which measures the difference between the system pressure inside the tube and atmospheric pressure. II relies on the deformation of a bent hollow tube of suitable material which, when subjected to the pressure to be measured on

the inside (and atmospheric pressureon the outside), tends to unbend. This moves a pointer through a suitable gear-and-Iever mechanism against a calibrated Stale. Figure (b) shows an open V-tube indicating gauge pressure, and Fig. (c) shows an open V-tube indicating vacuum. Figure (d) shows a closed U-tube indicating

- = 11
absolute pressure. If p is aunospheric pressure, this is a barometer. These: are called Vtube manometers. IfZis the difference in the heights of the fluid columns in the two limbs of the V-tube [Fig. (b) and Fig.(c),ptbe density oftbe fluid andg the acceleration due to gravity, then from the elementary principle of hydrostatics, the gauge pressure P, is given by





e ~..,

T ,

FIg. 1.1<1, PruJllrt P"lU (.) BourdM t'ugt (i) fJprtJ ljhlM iMltllilll ' Iugt !mum M OJ- lj/uk llUikllilll !'Ieww", (i) Closti Uhlbr llUiltll/lll IImHMu prWllrt

T ,




12=If the fluid is mercUl)' having p '"' 13,616 kglm1, one metre head of mercury column is equivalent 10 a pressure of 1.3366 bar, as lihown below 1m Hg .. Zpg ~ I x 13616 x 9.81 = 1.3366 x lOS N/ml = 1.3366 bar The manometer is a sensitive, accurate and simple device, but it is limited to fairly small pressure differentials and, because of the inertia and friction of the liquid. is not suitable for fluctuating pressures, unless the rate ofpressurc change is small. A diaphragm-type pressure transducer along wilh a cathode ray oscilloscope can be used to measure rapidly fluctuating pressures.

1.10.3 SJliJk Volume au DmsiIy

Volume (I') is lhe space occupied by a substance and is measured in m1. The specific volume (v) of a substance is defined as the volume per unit mass and is measured in mJlkg. From continuum consideration the specific volumc at a point is defined as

where OV' is the smallest volume for which the system can be considered a continuum. Density (P) is the mass per unit volume of a substance, which has been discussed earlier, and is given in kglm l .

p' m
In addition to m1, another commonly used unit ofvolume is the litre (I). 11 _ 10"-1 ml The specific volume or density may be given either on Ihe basis of mass or in respect of mole. A mole of a substance has a mass numerically equally to the molecular weight of the substance. One g mol ofo:'lygen has a mass of 32 gand J kgmol (or kInol) of nitrogen has a mass of28 kg. The symbol v is used for molar specific volume (mllkmol).

1.10.4 E,..",
Energy is the capacity to e:'lert a fOKe through a distance, and manifests itself in various fonus. Engineering processes involve theconversion of energy from one fonn 10 anolher, the transfer of energy from place to place, and the storage of energy in various forms, utilizing a working substance. The unit of energy in the Sisystem is Nmot J (joule). The energy perunitIlULSS is the specific energy, the unit of which is Jlkg.






The rate of energy UlUlsfer or storage is called power. The unit of power is wall (W), kilowatt (kW) or megawatt (MW). I W " I J/s - I Nmls IkW - IOOOW

1.11 History of Thermodynamics

The latter half of the eighteenth century ushered man into the modem world of machinery and manufacture, and brought about cataclysmic changes in the social, economic and political life of the people. The historians have called it the Industrial Revolution. It began in England due to a fonuitous combination of many factors. There was bustling creative activity in science and technology during this period in England, with the appearance ora galaxy of rome brilliant individuals. The invention of the steam engine gave an impetus to this activity, and for the first time made man free from the forces of nature. The names of Savery, Newcomen and notably James Wall are associated with this invention. Watt brought about considerable improvement in the perfonnance of the steam engine, which began to be widely used in coal mines, iron metallurgy and textile mills. George Stephenson introduced steam engine for rail UlUlspol1, and Robert Fulton used it in steam boats. A variety of industries grew up, and man gradually entered into the modern machine age. The advent of steam engine also gave stimulus to the birth of thermodynamics. Thermodynamics is said to be the "daughter" of the steam engine. There was once a young inventor who thought that he could produce energy out of nothing. "It is well known", said he, "that an electrical motor converts electrical energy into mechanical energy and that an electrie gcnerator converts mechanical energy into electrical energy. Why not then, use the motor to run the generator and the generator to run the motor, and create thcreby an endless supply of energy''? But this is never 10 happen. A hypothetical device which creates energy from nothing is called a perpetual motion machine of the first kind, a PMML like the proverbial touchstone which changes all metals into gold, man allempted to find sueh a PMM I for long long years, but it turned OUIIO be a wild goose chase. In fact, the development of the principle of conservation of energy has been one of the most significant achievements in the evolution of phySical science. The first recoplition of this principle was made by Leibnirz in 1693, when he referred to the sum of kinetic energy and potential energy in a gravitational force field. Energy is neither created nor destroyed Energy manifests in various forms and gets transformed from one form to another. Through gentle metabolic processes, a day labourer gradually transforms the chemical energy of the food he eats and the oxygen' he breathes into heat, sound and useful work. Work was always considered a form of energy. The concept of heal was, however a very actively debated scientific topic. Until the middle of the nineteenth ccntlll)', heat was regarded as an invisible colourless, Weightles5,

t4=, odourless fluid that flowed from a body of higher caloric to a body of lower caloric. This was known as the caloric theory of heat, first proposed in 1789 by Amoine Lavoisier(l743- 1794), the father of modern chemistry. When an object became full of cain ric , it was then said to be saturated with it. This was the origin of the tcrms "saturated liquid", "saturated vapour" etc. that we use in thermodynamics today. The caloric was said to be conserved and il was indestructible. The calorie theory was, however, refuted and heat was confirmed as a form of energy in the middle of the nineteenth century leading to the formulation of the first law ofthennodynamics. The names which stand out in the establishment of the first law were Benjamin Thompson (1753-18 14), James Prescott Joule (1818-1889) and Julius Roben Mayer (18 14-1978). Benjamin Thompson, an American born in Massachusetts, did not suppon the revolt against the British during the AmericlUl war of independence, and in 1775 he left for England where he took up government service. On a trip to Gennany, he met the prince of Bavaria who offered him ajob. He introduced many refonns in the government for which the title of Count von Rwnford Was conferred on him. While boring brass cannon hole, Count Rumford noticed that there was a continuous heat release. How could the caloric fluid be conscrved, when it was being produced continuously by mechanical friction? From the established prinCiple of conservation of mass, a true fluid ClUl be neither created nor destroyed, so heat could not be a fluid if it could be continuously created in lUI object by mechanical friction. Rumford conceived thai heat was "a kind of motion" and the hotness of an object was due to th e vibrating motion of the particles in the object. On his return to England, he became a member of the Royal Society. and later founded the Royal Institution for the Advancement of Science. Rumford married the widow of Lavoisier and lived in Paris for the test of his eventful life. In the early forties of the nineteenth century, James P. Joule and Julius R. Mayera[most simuhaneously set forth the idea that heat transfer and mechanical . work were simply different fOnDS of the same quantity, which we now recognize as energy in transit. In some modem treatments orengineering thermodynamics, Joule's name alone is attached to the establishment of the equi valence of "heat" and 'work". The published record, however, shows that the idea of convertibility of heat into work was published independently by Mayerin May, 1842 and Joule in August, 1843. For an important aspect in the history of the fint law, is the fact that both Mayer and Joule had difficulty in getting their papers published and in being taken seriously by their established contemporaries. Rohen Mayer was a doctor in a ship in the East Indies and from physiological observations, he believed in a principle of conservation of energy. He derived theoretically, the mechanical heat equivalent based on the calorimetric data of Joseph Black of Glasgow University. Mayer tried to publish his paper but remained unsuccessful for a long time. His despair was so greal that he attempted suicide by jumping from a window, but he only broke his two legs. He was placed in an asy lum for some time. In later years, howeve r. he was given some measure

--== 15
or recognilion and honoured equally with Joul e in establishing the mechanical theory of heal. Mayer argued thaI an amounl of gas needs 10 be healed more al constant pressure than al constanl volume. because at constant pressure il is free to dilate and do wori<.againsllhe atmosphere. whicb in loday's notalions be<:omes:

Using the c p andcfc. con slants that were known in his time, he estimated the left-hand side of the equation in calories, while the right-hand side was known in mechanical units. He thus eSlablished numerically the equivalence between these units. lflhe relation

Pv "' RT
is used in Eq. (1.2), Mayer's argument reduces to


cp - c. - R

This classic relationship between the specific heats of an idea~ gas is called Mayer's equation; while the ideal ~as equation of slate, Eq. (1.3). was first derived by Clapeyron [Bejan, 1988). Joule was th e ultimate ellperi mentalist. His ellpcriments seem to be the direct continuation of those of Rumford and the gap of some fony years between the two investigations appeared puzzling to some authors. Joul e's first discOvc:ry from his measurements was that the flow ofc=t in a resistance, is accompanied by the development of heat proponiooal to the resistance. He coocluded that caloric was indeed crtated by the flow of current. He was finnly convi nced thatlhere ellisted some conservation law of a general natUTe and hence sel out to investigate whether the conversion of the various fOTlTl5 of energy is governed by definite conversion factors. He considered th e conversion of chemical, electric, caloric. and mC(;banical energy forms in all combinations. The determination of the mechanical equivalent of heat forms the central part ofbis ellpcriments, the results of which can be summed up in the general relation:

W = JQ


whereJis the mechanical equivalent of heat. Joule's experiments suggested that this relation may have universal validity with the same numerical value ofJundtr all conditions. Joule communicated the results of his experiments to the British Association for Ihe Advancement of Science in 1843. It was received with entire incredulity and general silence. In 1844 a paper by Joule on the same subject was rejected by the Royal Society. To convince the skeptics, he produced a series of nakedly simple experiments whose message proved impossible 10 refute. From the point of view of mechanical engineers, the most memorable among these experiments was the heating of a pool of water by an array of paddle wheels driven by falling Adrian Bejon. "Research inlo the Origins of Engineering Tbennodynamics", Int.
Comm. Heal M(Us Tra"s/"r, Vol. 15, No. 5, 1988. pp 571- 580.


16=weights. He discussed in 1847, before the Britij;h Association at Oxford, bis experimental results in which he suggested that the water at the bottom of the Niagara waterfall ( 160 feet high) should be warmer than at the top (by O.2QF). From the thermal expansion of gases louie deduced thai there should be a "zero of temperllture", 480F below Ihe freezing point of ice. This was the first suggestion of absolute zero. Although these results fai led 10 provoke further discussion, it created interest in a young man who only two years ago had passed from the Unive~ity of Cambridge with the highest honour. The young man was William Thomson, who later became Lord Kelvin. He somewhere stated that it was one of the most \'aluab le recollections of his life. Michael Faraday was also present in the 1844 Oxford meeting, and he communicated louIe's paper ''On the Mechanical Equivalent of Heat" to the Royal Society in 1849. The paper ultimotely appeared in its Philosphical Trnnsactions in 1850. Even while Joule was perfecting the experi mental basis ofthe energy law now called the Mayer-Joule principle, Herman Ludwig von Helmohltz (18 21- 1894) published in 1847, bis famous essay on the conservation offorce. In this work, he advanced the conservation of energy as a unifying principle extending over all branches of physics. Helmholtz, like Mayer, was a physician by profession and self-taught in Physics and Mathematics. He also fac.::d gr.::at difficulties in gelling his paper published in professional journals. In the histol)' of classical thcrmodynamics, onc thinks of only the closed system fonnulations of the first law which w.::re deliberat.::d by thc pioneers as stated above. In engineering thermodynamics, however, open system formulations are of prime in terest. The fi rst law for open systems was first stated by Gusta\'e Zeuncr, as part of the ana lysis of flow systems that operate in the steady state. Zeuner's formula for the heat transfer rate to a stream", in steady flow alld without shafi work in presen t notations is gh'cn fO bc:

The rcference orthis formula is found in Stodola's classic treatisc on steam turbines. first published in the Gennan language in 1903. The first person to invent a theol)' simultaneous ly involving th e ideas of conservation and conversion of energy was the young French milital)' engineer Nico las Leonard Sadi Camot ( [796-1832). The st rikingly original ideas of Camot"s work make it among the most brilliant new departures in theoretical physics. Sadi Camol was the son of Napoleon's general, Lazare Carnot. and was educated at the famou s Ecole Polytechnique in Paris. Between 1794 ;;;nd 1830, Ecole Polytechnique had such famous teachers as Lagrange. Fourier, Laplace, Ampere, Cauchy, Coriolis, Poisson, Gay-Lussac, and Poiseui11e. Afier his formal education Carnot chose a career as an army officer. Brita in was then a powerful mi li tal)' force, primarily as a result ofthc industrial revolution brought about by the steam engine. French technology was not developing as fast as Britain's. Camot was convinced that France's inadequate utilization of stearn power had made it militarily inferior. He began 10 study the fundamentals of sleam engi ne technology, and in 1824 he published th e results of his study in the form of a


broehure "Reflection on the Motive Power of Heat and on Machines Fitted to Develop that Power". Camot was lnI ined in the basic principles of hydraulics. pumps and water wheels at the Ecole Polytechnique. During Camot"s time, caloric theory of heat was still persisting. and the waterwheel as the majorsource of mechanical power was gradually getting replaced by the steam engine. Camot conceived that the power of a steam engine was released, as the heat fluid or caloric fell from the high tempernture of the boileTto the lower temperature of the condenser, in much the same way that water falls through a water wheel \0 produce mechanical shaft work output. Camot stated, ''The motive power of a water wheel depends on its height and the quantity ofliquid. The mOlh'e power of heat also depends on the quant ity of calorie used and on the he ight of its fa ll, i.e., the difference of temperarures of the bodies between which the c)[change of caloric is made~. Till Camot's timc thermodynamics was dcveloped primarily on an cmpriciai basis provided by chemistry. Camot approached an engineering problem, th e effieieneyof heat engines, in tennsofentire ly new concepts with the steam engine serving as the stimulus. Camot observed that the e:tistence of temperature differences lsa necessary condition for producing mechanical work by meansofa heal engine. He simplified the problem to its bare essentials and stipulates, that this system, consisting essentiall y ofa working substanc e, should e)[change heat with its surroundings only at two fixed tempera tures. In order to conccptualize such a situation, he introduces the idea of heat resen'oirs. Two important conclusions emerged from Camol 's work: 1. No one could build a water wheeltbat wou ld produce a continuous work output unless water actually entered and exited the whcel.Jfwater with a et'rtain kinetic and potential energy entered the wheel, then the same amount of wate r with a lower energy must also e)[it the wheel. It is thus impossible to make a water wheel that converts all the energy of the inlet water into shaft work output. There must be an outflow of water from the wheel. If this idea is extended to a steam engine by replacing the water by heat fluid caloric, it can be concluded that when caloric at a cenain energy leve l (temperature) enters a work producing heat engine. it must also exit the heat engine at a low energy level (temperature). Thus a cont inuously operating heat engine that converts all ofit.s caloric (heat) input directly into work ou tput is not possible. This is very close to the Kel vinPlanck statement of second law as it is known today. 2. The maximum efficie ncy ofa water wheel was independent of the type of the liquid and depended only on the inlet and outlet flow energies. The maximum efficiency of the steam engine (or any heat engi ne) depends only on the temperatures of the high and low temperature thennal reservoirs of the engine and is independent of the working fluid . To achieve the m:uimum efficiency there must not be any mechanical friction or other losses of any kind. Only at the age of36, Sadi Camot died ofcho1cra following an attack of scarlet fever. The significance ofCamol's work was nol recognized unti118S0, when Rudolf Clausius (1822- 1888) and William Thomson (1824-1907) worked out a


Basic aM Applitd TlurmodJMmia

clear fonnulation of the conservation of energy principle. Camot's first conclusion was then called the second law of thermodynamics by Clausius, and Thomson used Camot's second conclusion 10 develop the concept of absolute temperature scale. Thermodynamics is thus said to have origina ted from . lhe "clumsy puffing of the early steam engines" and is often called "the daughter of steam engine". Camot's ideas were sorevolutionary that they Were" largely ignored. Soon after Camot's death, Emile Clapeyron (1799-1864), a French mining engineer, st renglhened Camot's ideas by using more precise math ematical derivation. Clapeyron constructed its thennodynamic cycle by deducing that it must be composed of two reversible isothennal processes and two reversib le adiabatic processes. II is now known as Camot's cycle. It was the first heat engine cycle to be conceptualized. No other heat engine can equal its efficiency. Clapeyron was later able to derive a relation for the enthalpy change of the liquid to vapour phase (hrJ in terms of pressure, lemperature and specific volume. This provided the first equation, now called the Clausius-Clapeyron equation, representing the first order phase transition, which could be used to estimate a property that is not directly measurable in terms of properties that are directly measurable. Clapeyron's equation is now most easily derived from one of Maxwell 's equations. William Thomson (1824- 1907). who became a professor of natura l philosophy at the Uni versity of Glasgow in 1848 al the age of24 only, rejected the caloric theory of heat and forthc first time used the terms "thermodynamics" and " mechanical energy". Apart from the deduction of the absolute temperature scalc, Thomson worked with Joule from 1852 to 1862 in a series of experiments to measure the temperature of gas in a controlled expansion and propounded the Joule-Thomson effect for real gases. Rudolf Julius Emanuel Clausius (1822-1888) realised that there were two distinct laws at work, the first law due to Joule and Mayer and the second law as expounded by Carnol He defined the internal energy U. Although both Kelvin and Clausius used the function Q.. j T for some years, Clausius recognized Ihe va lue orthis function and to describe it he coined the word "entropy" from Ihe Greek word "tropee" meaning ''transformation'' and assigned it the symbol S. Clausius in 1865, summarised the first and second laws orthermodynamics in the following words: "Die Energie der Welt ist konstant. Die Entropie der Welt strebt eiDem Maximwn zu" which is trans lated as "The energy of the world is constant. The entropy oflhe world tends toward a maximum". The world here means the universe, the system and the surroundings together. These statements made a strong impression upon a young st udent, Max Karl Ernst Ludwig Planck (1858-1947). He was ed ucated at the universities of Munich and Berlin. In his autobiography he sta ted, "One day I happened to come



across the treatises of Rudolf Clausius, whose lucid style and enlightening clarity of reasoning made an enonnous impression on me, and I became deeply absorbed in his articles, with an ever increasing enthusiasm. I appreciated especially his exact formulation oflhe two laws of thermodynamics, and the sharp distinction, which he was the first to establish between them". In 1897, Planck l demonstrated the close connection between the second law and the concept of reversibility. He stated the second law as the impossibility of a cyclic device which produces positive work and exchanges heat with a single reservoir. Similar statement was also made by Kelvin, and is now recognized as Kelvin-Planck statement of second law. Poincare2 in 1908, extended the work of Planck and prescribed a complete structure of classical thennodynamics. The property, entropy, plays a steller role in thermodynamics. It was introduced via the concept of beat engines. In 1909, the Greek mathematician Canltheodory proved the existence of entropy function mathematically without the aid ofCarnot engines and refrigerators. Caratbeodory's statement of second law may be stated as: "In the neighbourhood ohny arbitrary state Po ofa physical system, there exist neighbouring states which are not accessible from Po along quasi-static adiabatic paths". From the standpoint of the engineer and physicist it is entirely mathematical in form and devoid of physical insight. William John Macquorn Rankine (1820-1872) defined the thermodynamic efficiency ofa heat engine and showed the usefulness ofp-v diagrams as related to work. He wrote the first text book on thermodynamics l , and was the fltSt to work out the thennodynamic cycle for the adiabastic cylinder steam engine, now known as Rankine cycle for a vapour power cycle. In 1862, the cycle used in modem gasoline-powered I.e. engines was proposed in a patent issued to Alphonse Beau de Rachas (1815- 1893). The first practical engine was, however, built by Nikolous August Otto (1832- 1891) which was demonstrated at the Paris Exposition in J 878. Otto fought many legal battles with Beau de Rochas for production of these engines, but finally lost to him. Captain John Ericsson (1803- 1889) was a Swedish engineer who marketed small solar-powered and coal-fired hot ai r engines. Rev. Robert Stirling ( 1790- 1879), an English parish minister, patented a practical heat engine in 1816 that used air as the working fluid. In theory, the cycle used in the Stirling engine approaches the ideal cycle later proposed by Camot (1824). George Bailey Brayton (1830- 1892), an American engineer, marketed an I.C. engine with a separate combustion chamber, where combustion offuel OCCUl'Ted

I. M. Planck, Treatise <.III Therrllodyll<.lmics (1897). translated by A. Ogg, l.ongman and Green; London, 1927. 2. H. Poincare,11Icnnodynamlqllc, Gauthier-VilIar!i, Paris, 1908. 3 W.J.M. Rankine. "Mollilol ofth~ S{~um Engin~ and OIh~r Prim~ MOl'~rs~, 1859 going through 17 editions, as mentioned by Robert Bahner in " Thermodyllomlcs",

We!t Publishing Co., 1990. page 399.

20=at about constant pressure. This cycle later fonned the basis for modern gas turbine plants. . Gottlieb Daimler (1834- 1900) obtained a patent in 1879 for a muilicylinder automotive engine, which was commercially successful. Dr. Rudolf Christian Karl Diesel (1858-1913) studied at Technisch e Hochschulc in Munich. He designed large stearn engines and boilers. He later dcve loped in 1897 an I.C. engine with fuel injC1;tion which resembled the modem diesel engine. Failing bealth, continuing criticism and serious financial setbacks beset Diesel who in 1913 disappeared from a boat crossing the English channel in a moonlit night. Josiah Willard 'Gibbs ( 1839-1903) is often regarded as the most bril1iant thennodynarnicist produced in the USA. He received the first doctorate degree in engineering in the USA (Yale University). He contributed significantly in mat:\y areas of thermodynamics like heterogeneous systems, phase rule , physical chemistry and statistical thennodynamics. Some of his very imponant papers were published in obscure jouma1s iike ConnC1:ticut Academy of Sciences, and remained unknown to most scientists. Only after bis death. these were discove red.



Example 1.1 The pressure of gas in a pipe line is measured with a mercury manometer having one limb open to the atmosphere (Fig. Ex. 1.1). If the difference in the height of mercury in the two limbs is 562 mm, calculate the gas pressure. The barometer reads 761 mm Hg, the acceleration due to gravity is 9.79
mls 2, and the density of mercury is 13,640 kg/m l .

' ",

At the plane AB, we have

p Po+ pgz

Po " pgZo
whe reZo is the barometric height ,p the density of mercury andpo the atmospheric


p " pg(z + zo)

13,640 kg/m l x 9.79 mls) (0.562 + 0.761) m

.. 177 X IO J N/m1 .. 177 kPa - 1.77 bar '" 1.746 atm

Es.ample 1.2 A turbine is supplied with steam at a gauge pressure of 1.4 MPa. After eltpansion in the turbine the steam flows into a condenser which is maintained at a vacuum of710 mm Hg. The barometric pressure is 772 mm Hg. Express the inlet and elthaust sleam pressure in pascals (absolute). Take the density ofmercwy as 13.6x 101 kg/m . Solution The atmospheric pressurepo
'" pgzo = 13.6 x 101 kglm x 9.81 rnls2 x 0.772 m '" 1.03

x 10' p~

Inlet steam pressure .. [(1 .4 X 106) + (1.03 x 10') Pa = 15.03 x 10' Pa = 1.503 MPa Condenser pressure
.. (0.772 - 0.710) m x 9.81 rnl~ x 13.6 X ]OJ kglm 1

= 0.827 x IO~ Pa = 8.27 kPa


1. 1 1.2 1.3 What do you understand by macroscopic and microscopic viewpoinu? Is IMnnodynamics II misnomer for the subject? How does the subject of thermodynamics differ from the concept of heat


1.4 U 1.6 1.1

1.8 1.9 1.10 1.11 1.12 1.13 1.14

1.1 S
1.16 1.17 1.1 8

What is 1M scope of classical thennodynamics? What is II thermodynamic system? What i.!lhe difference between a closed s)'5tem and an open system? An open system defined for a fIXed region and a control \'olwne are synonymous. Explain. Define an isolated s)'!tem. Distinguish between the terms 'change of state', 'path', and ' process'. What iSi thermodynamic cycle? Whlll are intensive and extensive properties? What do you mean by homogeneous and heterogeneous systems? E..:plain what you understand by IMnnodynamic equilibriwn. Explain mechanical, chemical and !henna! equilibrium. What is quasi,static process! What is its characteristic feature? What is tlK: conpt of continuum? How will you define densily and pressure using this concept? What is vacuum? How can i! be measwed? Wbat i5 a pressure IrlInsducer?

1.1 A pwnp discharges a liquid into a drum at the rate of 0.0032 ml/s. The drum, 1.50 m in diameter and 4.20 m in length, can 1I0id 3000 kg of the liquid. Find the density oflhe liquid and the mass now rat" of the liquid handled by tile pump. 1.2 The acceleration of gravity is given as a function of elevation above sea level by g - 980.6 - 3.0$6 x 10- 6 H wbere g i5 in cmls 2 , andH is in cm.lfan aeroplane wei8hs 90,000 N at sea level, wbat is the gravity force upon il at 10,000 m elevation? What is the pera:ntage difference from the sea- Icvel wcight? 1.3 PO::l\"e that the ....'eight ofa body at an elevation H aoo\'e sea-leve l is given by

W . !"L(_d)'


where d is the diameter of the canh.

104 The first artificial earth satellite is reponed to have encircled the earthal a speed of28,840 krnIb and its maximum height above the cartl\' s surface was SUIted to be916 km. Takingthemcandiameteroftheearth to be 12.680 Ian. and assuming the orbit to be circular. evaluate the value of the gravitationalacceicmtion al this beighl. The IlWIS of the satellite is reported 10 have been 86 kg at sca-Ievel. Estimate the grlIvitlllionai force acling on the Atellite at the operalional altitude. AIlS. 8.9 mls2; ?65 N I.S Conven Ille following readings ofpres!SW"C 10 kPa , assuming that the barometer reads 760 mm Hg: (a) 90 em Hg gauge. (b) 40 em Hg vacuum, (c) 1.2 m H20 gauge, (d) 3.1 bar. 1.6 A 30 m high venical column of a fluid of density ]878 kglm l exists in a place where g - 9.65 mill-. What is lhe pressure atlhe base of the column? An.J. 544 kPa 1.7 Assume that the pressure p and the specific volume v of the atmosphere are related according to the equalionpv u .. 2.3 x ]Ol . when: p is in N/ml abs and v is in mllkg. The acceleration dllC to gravity is constant at 9.S] mJ.J-. What is the depth of atmosphere IlCCessaJ)' to produce I pl'esstlte of 1.0 132 bar at the eanh' s surface? Consider tile Stearn 8t pre~e, p atmosphere as a fluid column. AIlS. 64 .8 km I.S The pressure of steam nowinS in a pipe line is measured ",illl a mercury manometer, !hown in Fig. P. 1.8. Some steam condenses inlO water. Estimate the steam pl'eSSUI"C in kPa. Take the densi,?" of mCKUJ)' as 13.6 x kf'm , dctUity of water as 10) kaJm , the barometer reading as 76. 1 em Hg. IUld g as 9.S06 mlsl. FIg. P.I.S






A vacuum gauge mouotcdon a condenser reads 0.66 m Hg. What is the absolute pre!llIurc in the condenser in kPa when the atmospheric pres,ure is 101.3 kPa1 AIlS. 8.8 kPa 1.10 The basic barometer can be used to measure the height of a building. If the barometrk readings at the lOp and at the bottom of a building are 730 and 760 nun Hg, respectively, detennioe the height of the building. Assume an avenge air deosity of 1.18 kglm).

"' "


2.1 Zeroth Law of Thermodynamics

The property which distinguishes thermodynamics from other sciences is temperature. One might say that temperature bears as imponanl a relation to thermodynamics as force does to statics or velocity does to dynamics. Temperature is associated with the ability to distinguish hot from cold. When two bodies at differenl temperatures are brought into contact, after some time tbey attain a common temperature and are then said to exist in thermal equi librium. When Q body If is in thermal equilibrium with Q body B, ond abo sl!ptJTtJleiy with a body C, then Bond C will be in thermol equilibrium with eoch Olher. This is known as the zeroth law of thermodynamics. It is the basis of temperature measurement. In order to obtain a quantitative measure of temperature, a reference body is

used, and a cenain physical characteristic of Ihis body which changes with
temperature is selected. The changes in the sel~ted characteristic may be taken as an indication of change in temperature. The seleeted eharacteristic is ealled the thermometric property. and the reference body which is used in the determinatio n o f temperature is called the thermometer. A very common thermometer consists of a small amount of mercury in an evacuated capillary tube. In this case the extension of the mercury in the tube is used as the thermometric prop,rty. There are five d ifferent kinds ofthennometer, each with its own thermometric propeny, as shown in Table 2.1 .

2.2 Measureme nt of Temperature-the Reference Points

The temperature of a system is a property that determines whether or not a system is in thermal equilibrium with other systems. If a body is at, say, 70C, it will be 70C, whether measured by a me rcury-in-glass thermometer, resist-


ance thennometer or constant volume gas thennometer. If X is the Ihennomel ric property, lei us arbitrari ly choose for the temperature common to the ther mometer and 10 all syslems in Ihermal equilibrium wilh it the following linear function of X: Table 2.1
I. Constant wlume gus thermometer 2. Constant pressull: gas tbennomeler J. Electrical resistaoce thermometer 4. Thermocouple S. Mercury-in-glass thermometer
TMrmollltlm anti TMrmom.tn'c Pro/Krfi.s

Thermometric ro erty _


Re sista nce Thennal e.m.f. Length


9 (X) '" ax, where a is an arbitrary constant. If Xt corresponds to 9 (Xt ), then X2 will correspond to

6(Xt ) ,X

that is

9(XV = 6(Xd ,X2


(2. 1)

Two temperatures on the linear X scale are to each other as the ratio of the com:spondingXs.

2.2.1 Method in Use Bifore 1954

The thennometer is first placed in contact with the system whose temperature 8 (X) is to be measured, and then in contact with an arbitrari ly chosen standard system in an easily reproduc ible state where the temperature is 8 (X t ). Thus

6(Xt ) 6(X)

.. ~


Then the thennometer at the temperature 9 (X) is placed in contact with another arbitrarily chosen standard system in another easily reproducible! state where the temperature is 8 (X2). It gives

From Eqs (2.2) and (2.3)

8(Xd 8(Xl 6(X)

.. Xt-Xl



(2.4) XI X2 If we assign an arbitrary number of degrees to the temperature interval 8(X1) - 8(Xi), then 8(X) can be calculated from the measurements of X, Xl and X2 . An easily reproducible state 0/an arbitrarily chosen standard system is cal/ed a fIXed point. Before 1954, there were two fIXed points: (a) the ice point, the temperature at which pure ice coexisted in equilibrium with air-saturated water at one atmosphere pressure, and (b) the steam poinl, the temperature of equilib. rium between pure waler and pure steam at one atmosphere pressure. The temperature interval, 8(XI ) - 8(X2), between these two fixed points was cho-sen to be 100 degrees. The use of two fixed points was found unsatisfactory and later abandoned, because of (a) the difficulty of achi eving equilibrium between pure ice and airsaturated water (since when ice melts, it surrounds itself only with pure water and prevents intimate contact with air-saturated water), and (b) eKtreme sensitiveness of the steam point to the change in pressure.

8(X) - 8(X1 )-9(X1 )X

2.2.2 MnIuHl in Use Aftn 7954

Since 1954 only one fixed point has been in use, viz., the triple point a/"..YJler, the state at which icc, liquid water and water vapour CDeKist in equilibrium. The temperature at which this slate eltists is arbitrarily assigned the value of 273.16 degrees Kelvin, or 273.16 K (the reason for using Kelvin 's name will be explained later). Designating the triple point of water by Bv and with X; being the value of the thennometric property when the body, whose temperature 8 is to be measured. is placed in contact with water at its triple point, it follows thai

.. ax,

a"'- = ---




9 = aX
... 273.16 . X


9 - 273.16.K


The temperature oflhe triple point of water, which is an easily reproducible state, is now the slandardfixed point a/thermometry.

2.3 Comparison of Thermometers

Applying the above principle to the five thennometers listed in table 2.1. the lemperatures are given as


B(P) '" 273.16.....

('1 Constant volume gas thermometer

(hi Constant pressure gas thermometer


BU') .,


('I Electric resistance thermometer

(dl Thennocouple

OCR) - 273.16


B(e) " 273.16. B(L) " 273. 16 .l:~

(01 Liquid-in-glass thennometcr

If the temperature of a given system is measured simultaneously with each of the five thermometers, it is. found thatthcre is considerable difference among the readings. The smallest variation is, however, observed among different gas thermometers. Thai is why a gas is chosen as the standard tbennometric substance.

2.4 Ideal Gas

It has been established from experimental observations that the p - v - T behaviour of gases at a low pressure is closely given by the following relation
pI} =



where R IS the Universal gas constant, 8.3143 Jlmol K and v is the molar specific volume, ml/gmol (see Sec 10.3.). Dividing Eq. (2.6) by the molecular weight p, pv = RT (2.7) when: v is specific volume, in ml/kg, and R is the characteristic gas constant.

Substituting R = RIp l/kg K. we gc t in terms of the total volume V of gas, (2.8) where n is the number of moles and m is the mass of the gas. Equation (2.8) can be wrinen for two stales of the gas,
PI~ .. P1V1

PV = nRT PV .... mRT




Equation (2.6), (2.7) or (2.8) is called the ideal gas equation ojltate. At very low pressure or density, all gases and vapour approach ideal gas behaviour.



2.5 Gas Thennometen

A schematic diagram ofa consWlt volume gas thermometer is given in Fig. 2.1. A small amount of gas is enclosed in bulb B wbich is in communication via the capillary tube C with one limb of the mercury manometer M. The other limb of the mercwy manometer is open to the atmosphere and can be moved vertically 10 adjust the mercwy levels so that the mereury just touches lip L of the capillary. The pressure in the bulb is used as a thermometric property and is given by

P""'Po + pMZg
where Po is the atmospheric pressure and PM is the density of mercury.

Fledlle lublng

Fig. 2.1

lAMtdlll N t.1M PJ /MnnDllld4'T

When the bulb is brought in contact with the system whose temperature is to be measured, the bulb. in course of time. comes in thermal equilibrium with the system. The gas in the bulb eltpands, on being heated. pushing the mercury downward. The flexible limb of the manometer is then adjusted so that the mercury again touches the lip L. The difference in mercury level Z is recorded and the pressure p of the gas in the bulb is estimated. Sinee the volume of the \nipped gas is constant, from the ideal gas equation, llT"


(2 . 10)

i.e. the temperature increase is proportional to the pressure increase. In a constant pressure gas Ihennometer, the mercury levels have 10 be adjusted to keep Z constant. and Ihe volume of gas V. which would vary wilh the temperature of the syslem, becomes the thermometric property. (2.11)



i.e. the temperature increase is proportional to the obs.crved volume increase. The constant volume gas thermometer is, however, mostly in usc, since it is simpler in construction and easier to operate.

2.6 Ideal Gas Temperature

Lct us suppose that the bulb of a constant volume gas thennometer contains an amount of gas such thaI when the bulb is surrounded by water at its triple point, the pressurcp, is 1000 mm Hg. Keeping the volume V constant, let the following procedure be conducted: (a) Surround th e bulb with steam condensing at I atm, detennine the gas pressure p and calculate
1000 (b) Remove some gas from the bulb so that when it is surrounded by water at its triple point, the pressure p, is 500 nun Hg. Determine the new values of p and then 6 for steam condensing at 1 atm.

0 .. 273.16 ..L..

8 ,, 273.16 L


(c) Continue reducing the amount of gas in the bulb so that p, and p have smaller and smaller values, e.g., p, having, say, 250 mm Hg, 100 mm Hg, and so on. At each value of p, calculate the cOlRsponding 6. (d) Plot 8 vs.p, and extrapolate the curve to the axis wh ere p, '" O. Read from the graph


lim 8

The graph. as shown in Fig. 2.2, indicates thai although the readings of a constant volume gas thennometer depend upon the nature of the gas, all gases indicate the :Jame lemJ1f!ralurt! as p, is lowered and made fa approach zero. A similllf series of tests may be conducted with a constant pressure gas thennometer. The constant pressure may first be taken to he 1000 mg Hg, then SOO nun Hg, etc. and at each value of p, the vo lumes of gas V and V, may he recorded when the bulb is surrounded by steam condensing at I alm and the triple point of water. respectively. The corresponding value of 8 may be calcu lated from 8 "' 273.16...!:.


and 8 vs. p may be plotted, similar 10 Fig. 2.2. It is found from the experiments that all gases indicate the same value of 8 as p approach zero. Since a real gas, as used in the bulb, behaves as an ideal gas as pressure approaches zero (whicb would be eltplaincd later in Chapter 10). the ideaf gas temperature T is defined by either of the Iwo equations



1 ,


500 PI,....nHg


Fig. 2.2 lUll/ ftIJ ImIpcrlllUr. for fuam poi",

T = 273 .16Iim L p, P, -Jo 0 .. 273.16 lim



where 9 has tH:en replaced by T to denote this particular temperature scale, die
ideal gas temperalllrf! scale.

2.7 Celsius Temperature Scale

The Celsius tempcrnture scale employs a degree of the same magnitude as that of the ideal gas scale, but its zero point is shifted, 50 diat the Celsius temperature of the triple point of water is 0.01 degree Cel ~ius or 0.0 1C. If t denotes the Celsius temperature, then t - T - 273.15 Thus the Celsius temperature t. at whicb sleam condenses at I atm. pressure t." T, - 273. 15

" 373.15-273.15
.. lOO.OO"C Similar measurements for ice points show th is temperature on the Celsius scale \0 tH: O.OO"C. The only Celsius temperature which ls f'bl:ed by definition is that of the triple point.

2.8 Electrical Resistance Thermometer

In the resistance thennometer (Fig. 2.3) the change in resistance of a metal wire due to its change in temperature is the tbennom etric property. The wire, freo

- = 31 .
quentJy platinum, may be incorporated in a Wheatstone bridge circuit. The platinum resistance thermometer measures temperature to a high degree of accuracy and sensitivity, which makes it suitab le as a standard for the calibration of other thermometers. In a restricted range, the following quadratic equation is often used

R " RJI + At + Br)

where Ro is the resistance of the platinum wire when it is sUlTOunded by me lting iee and A and B are constants.

/n--h_ R
Fig. 2.3
RniJI4rw: IIrmn~mtltr


2.9 Thermocouple
A thermocoup le cin:uit made up from joinin g two wires A and B made of dissimilar metals is shown in Fig. 2.4. Due to the Seeback effC(:t, a net e.m.f. is generated in the circuit which depends on the difference in temperature between the hot and cold junctions and is, therefore, a thermometric property of the circuit. This e.m.f. can be measured by a mierovoltrneter to a high degree of


Test juncIion


/ . '" ~ Copper-..irn

. .f ___ / r

To potantiorneter

32=accuracy. The choice of metals depends largely on the temperature range to be investigated, and copper-constantan, chromel-alumel and platinum-platinumrhodium arc typical combinations in usc. A thennocouple is calibrated by measuring the thennal e.m.f. at various known temperatures, the reference junction being kept at Oc. The results of such measurements on most thennocouples can usually be represented by a cubic..equation of the fonn

" where

""'a+hl+Cr + d,J

is the thennal e.m.f. and the constants a, h, C and d are different for each thmnocouple. The advaotage ofa thermocouple is that it comes to thcnnal equilibrium with the system, whose temperature is to be measured, quite rapidly, because its mass is small.

2.10 International Practical Temperature Scale

An international temperature scale was adopted at the Seventh General Conference on Weights and Measures held in 1927. It was not to replace the Celsius or ideal gas scales. but to provide a scale that could Qe easily and rapidly used to calihrate scientific and industrial instruments. Slight refinements were incorporated into the scale in revisions adopted in 1948, 1954, 1960 and 1968. The international practical scale agrees with the Celsius scale at the defmiog fixed points listed in Table 2.2. The temperature interval from the o~ygen point to the gold point is divided into three main parts, as given below.
Table 2.2 Tmpmlllra QfFultd hinb

Triple point water Normal boiling point of water Nanna! boiling point of sulphur (Normal melting point of zinc-suggested as an alternative 10 the sulpbur point) Norma l melting point of antimony Normal melting poiot of silver Normal melting point of gold






~C A platinum resistance thennometerwith a platinum wire whose diameter must lie between 0.05 and 0.20 mm is used, and the temperature is given by the equation

(a) From 0 to

R - RrJ,I +At+ Br)

where the constants /4, A, and B are computed by measurements at lIle ice point. steam point, and sulphur point.


(b) From - 190 to O"C The same platinum resistance thermometer is used. and the temperarure is given by R " Rdl + AI + Br + C(t - 100) r]
where ~,A and B are the same as before. and C is determined from a measurement at the oxygen point.

(e) From 660 to 1063C A thennocouple, one wire of wbich is made of platinum and the other of an alloy of9O% platinum and 10% rhodium, is used with one junction at O C. The temperarure is given by the formula e - a+bt + cr where a, b, and c are computed from measurements at the antimony point, silver point. and gold point. The diameter of each wire of the thermocouple must lie between 0.35 to 0.65 mm. An optical method is adopted for measuring temperatures higher than the gold point. The intensity of radiation of any convenient wavelength is compared with the intensity of radiation of the same wavelength emitted by a black body at the gold point. The temperarure is then determined with the help of Planck's law ofthennal radiation. SOLVED


Es:ample 2.1 Two mereury-in-glass thermometers are made of identical materials and are acc urate ly calibrated at OC and 100 C. One has a tube of constant diameter, while the other has a tube of conical bore, ten per cent greater in diameter at lOO'C than at O C. Both thennometers have the length between 0 and 100 subdivided uniformly. What will be the straight bore thennometer read in a place where the conical bore thermometer !'Cads 50C1 SolutiQ" The vo lume of mercury in the tube at fC , ~, is given by VI " Vo (1 + tl(t - to:l] where Vo is the volume of mercury at O C, tl is the coefficient of volume expansion of mercury, and to is the ice point temperature which is O C. The volume change of glass is negle<:ted. Therefore V. - Vo " tl Vo t TIle temperature I is thus a linear function of volume change of mercury
(Vl - Vol.


.1.V0--100 "

tl Vo' 100 .1.VO-- so "" tl Vo 50


M'o_~ I ---,6V0-- 100

i.e., the 50 C, the volume of mercury will be half of that at lOO C, for the straight bore thermometer (Fig. Ex. 2. la).

Basic 11M Applicd Thmui/yfUlmia

But if the bore is conical (Fig. EJ(. 2. lb), men.:ury will fill up the volume ACDB. which is less than half of the mercury volume at 100Ge, i.e., volume AEFB. lett be the true temperature when mercury rises half the length of the conicalrubc (the apparent temperature being SOe). Let 04. and FB be extended to meet at G. Let I represent the length of the thennometers and the venita l height of the cone ABG. as shown in the figure. Now,

/' d 1+1' '"" LId

r~ ~d



_'_'_ =....!L
CD '" IO.S d "" l.OSd \0
~VO_ IOO '" VO ' /1- 100

., .,

J1Vo_, '" -'J1VG-]lXI 100 Volume ACDB = _,_ Volume AEFB 100
.!.1L(l.OSd)l x 10.51 ....!.1Ld1.101

34 . 34 I 1r 2 I 1r 2 34(1. ld) X 11l ~34d 101


1.05 x 1.05 xJO.S -10 = _,_ 1.1 x 1.1 x II 10 100

t ~ 1.58 x 100 ... 47.7C 3.31


r---- 1.1





T '


1/2 1


Fig. E:.:: :l.I

sample 2.2 The e.m.f. in a thennoeouple with the test junction at thennometer scale and reference junction at ice point is given by

rc on gas

e " 0.20t-5xI0-4r2mV
The millivoltmeter is calibrated at ice and steam points. What will this thennomelCr read in a place where the gas lhennometer reads 50C1 Solutio" At ice point, when t ~ OC. E '" 0 mV At steam point. when t .. loo'C, E '" 0.20 x 100 - 5 x l r x (100)2
At t - 50C,

- 15mV 0.20 x 50 - 5 X 10-1 (50)2 ., 8.15 mV

When the gas thermometer reads 50' C, the thennoeouple will read

\5 )( 8.75, or 58.33C


2.2 2.3
2.4 2.5 2.6

2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 2.16

What is the zeroth law of thermodynamics1 Define thermometric property. What is a thermometer? What is a fued poinl'! How many fixed points were used prior to 19541 What are these? What is tbe standard fixed point in tbennomctery1 Define it. Why is a gas chosen as the standard thermometric substaoce1 What is an ideal gas? What is tbe diffamce be""cen the universa1 gas COlIStant and a eb.aractcristic gas constant? What is I constant volume gas thermometer? Why is it preferred to a ronstant pressure gas thermometer? What do you understand by the ideal gas temperature scale1 How can the ideal gas temperature for the steam point be measuml? What is the Celsius temperature scale1 What is the advantage of a thermocouple in temperature measurement? How does the resistance thermometer measure temperature? What is the need of the international praeticaltemperalllnl scale1

2.1 The limiting value oflbe rotio of the pressure of gas at the steam point and at the triple point nfwlter ",hen the gas is kept at constant volume is found to be 1.36605. What is the ideal gas tempeB1ure of the steam point? 2.2 10 a constant volume gas tbennometer the following pairs of pressures readings were taken at the boiling paint of waler and the boiling painl of sulpbur, respectively: SO.O 100 200 JOO Water b.p. Sulphur b.p. 96.4 193 J81 582

36= The numbmi arc the gas pressures, mm Hg, each pair being taken with the

same amounl or gas ill the thermometer, but the successive pairs being UlJcell
"ith difftmlt amounts of gu in the thermometer. Plot the ratio or~. : H2~.P. agaimt Ihe reading al the water boiling point, and extrapolate the plot to zero prt'SSUl"l' al the water boiling point. This gh-es the ratio of ~p.: H10b.p. on a gas thl.'mlomeler operating at zero gas pressure. i.e . an ideal gas thermometer. Wh.al is the hoiling point or sulphur on the gas scale, from your plot? Am. 44S'C 2.3 The resistance of a platinum wire is found to be 11 ,000 ohms at the ice point, 15.247 ohltlll at lhe steam point, and 28.887 ohms Dtlhe su lphur point. Find the constants A and B in the equation

R - ~ I +Ar + Br)
and plot Ragain" t in the range 0 to 66Q"C. 2.4 When the reference jlllK"tion of a thermocouple is kept al the ice point and the test junclion is Ihe Celsius temperature I, and e.m.f. or the thennocouple is given by the equation

e - al + br
.... here 11 - O.:!O mV/deg, and b _ _ 50 x 10'" mV/deg l (a) CompUle the e.m.f. when I = - IOO"C, 200<'C, 4OO'C, and SOOC. and draw gmph of r. against t in this range. (b) Suppose the e.m.f. r. is tak en as II thermometric property and that a temperature :so;ale , . is defined by Ihe linear eqUiltion. t - d r.+b' and that ,. .. 0 at Ihe ice point and I .. 100 at the steam point. Find the n~rical values of 0' and b' and draw a graph of e against ' . (c) Find the values of t* when , - - IOO' C, 200"C, 400' c' and SOO' C, and draw a graph of /. against I. (d) Compare the Celsius $Calc with the , . :so;a le. 2.5 The temperature IOn a thermomelric $Ca lc is defined in term. of a property K by the relation

l - a lnK +b
.... hen: a and b are constants. The values of K are found to be 1.83 and 6.78 at the ice point and the steam point, the temperaturcl of which are assigned the numbers 0 and 100 respecti vely. Detennine the temperature corresponding to a reading of K equal to 2.42 on the thrnnomt !et".

AIIS. 21.346OC 2.6 The re:5isUince of the windings in a. certain motor is found to be gO ohms at room temperature (25C). Whc:n operating a! full IO<UI under stea.dy stale
conditions, the motor is switched off and the resistance of the .... indings, ~diately measured again. is found 10 be 93 ohms. The wind ings arc made of copper whose n:si5lallCe at temperature t"C is given by

R, - Ro[l + 0.003931]
where Ro il the resistance at OC. Find the temperature: B tUlined by the co il during full load..


Work and Heat Transfer

A closed system and its surroundings tan interact in two ways: (3) by work transfer, and (b) by heat transfer. These may be called energy imeractions and these bring about changes in the properties of the system. Thermodynamics mainly studies these energy interactions and the associated property changes of the system.

3.1 Work Transfer

Work is one of the basic modes of energy transfer. In mechanics the action ofa force on a moving body is identified as work. A force is a means oftrall5mitting an effect from onc body 10 another. But a force itself never produces a physical effect except when coupled with motion and hence it is not a form of energy. An effect such as the raising of a weight through a certain distance can be performed by using a small fOrl:c through a large distance or a large force through a small distance. The product of force and distance is the same to accomplish the same effect. In mechanics work is defined as: The work is done by oJorce os it octs upon (I body moving in the direclion oj the/orce. The action of a force through a distance (or of a torque through an angle) is called mechonical work since other forms "f work can be identified, as discussed later. The product of the force and the distance moved parallel to the rorce is the magnitude of mechanical work. In thermodynamics. work transfer is considered as occurring between the system and the surroundings. Work is said 10 be done by 0 syslem if the sole effect on things ulernal to the system can be redu.ced to the roising of0 weighl. The weight may nO I actualJy be raised, but the net effect external to the system would be the raising of a weight. Let us consider the battery and the motor in Fig. 3. 1 as a system. The motor is driving a fan. The system is doing work upon

3S=the surroundings. When the ran is replaced by a pulley and a weight, as shown in Fig. 3.2, the weight may be raised with the pulley driven by the motor. The sole effect on things extemalto the system is then the ra ising or a weight .

", ....., 1
..... ........................
'----- system boundary


_1 \



i I L ..... _....................... j Weight

System boundary

Fig. 3.2

Work traruf ...{ram



Whell work is done by a system, il is arbitrorily lakell 10 be positive, alld when work is done 011 a system, it is /alcell to be lIegative (Fig. 3.3.). The symbol W is used ror work tlllnsrer.

G--w 8
(a) W II positive


(b) Wis Ilegative

The unit orwork is N.m or Joule [I Nm - I louie]. The rate at which work is done by, or upon, the system is known aspower. The unit orpower is l is or watt.

WD,A: DM H'Il/ Trllnsjn


Worle: is one of the forms in which a system and its surroundings can interact with each other. There are various lypeS ofworle: transfer which can gel involved between them.

3.2 pd V -Work or Displacement Work

Lellhe gas in Ihc cylinder (Fig. 3.4) be a sySICm having inilially the pressure PI and volume J/I' The syslem is in thermodynamic equilibrium, the stale of which is described by the coordinates PI ' VI ' The piston is the only boundary which moves due to gas pressure. Lellhe pisIon move OUIIO a ncw final posilion 2, which is also a thermodynamic equilibrium siale specified by pressure P2 and volume VI- At any intermediate point in the lfavel of the piston, let the pressure be p and the volume V. This Fig. 3.4 pdV wo,k must also be an equilibrium state, since macroscopic propenies p and V are significanl only for equilibrium slates. When the piston moves an infinitestima l di stance dl, and if ' II' be the area of the piston, the for<:e F acting on the piston F - p .lI. and thc infinitesimal amount of work done by the gas on the piston

(3. 1)
where dV - IIdl " infinitesimal displacement volume. The differential sign in dW with the line drawn Ilt Ihe top of il will be explained laler. When Ihe pislon moves out from position I to position 2 with the volume changing from VI 10 V~. Ihe amount of work II' done by the system will be

_l = JPdV 1V1

The magnitude of the work done is given by the an:a under Ihe path 1- 2. as shown in Fig. 3.5. Since p is at all times a thermodynamic coordi nate. all the states passed through by the systern as the volume changes from VI to V 1 musl be equilibrium sta tes, and the path 1- 2 must bequasi-s/lltic. The piston moves infinitely slowly so that


" "

r ......
- -I ~~



Fig. 3.5

Q!l4Ji-tliJlk pdVwo,k

every state passed through is an equilibrium Siale. The integra/ian

Jpd V can

be peifanned only on a quasi-static path.

&sit 11l1li Appfitd TlltrmodyMm/es

3.2.1 PtUA Futtditm tlltd Poi," Function

With re ference 10 Fig. 3.6, il is possible 10 lake a system from stale I 10 state 2 along many quasi-static palhs, such as A, B or C. Since thc area undcr each curve represents the work for each process, Ihe amount of work involved in each case is not a function of the end states of the process, and it depends on the path the system follows in going from state I to stale 2. For this reason, wad. is called a pathfunclion. and it W is an inexact or impeTj"ect differential.



FIg. 3.6 WG,A:-.I path foru:tiQII

Thermodynamic properties are point fonc/;om;, since for a given state, there is a dcfinite value for each property. The change in a thermodynamic property of a system in a change of stale is indepeodenl of the path the system follows during the change of state, and depeods only on the initial and fmal states of the system. The differentials of point functions are exact or perfect differentials. and the integration is simply v dY = Y2 - YI The change in volume thus depends only on the end stales of the system irrespective of the path the system follows. On the other hand, work done in a quasi-static process between two given stales depends on the path followed.

I "


, , IdW - W ,


I _2



To distinguish an inelUlCl differential d W from an exaCI differential d Y or dp the differential sign is being CUI by a line al its lap.

From Eq. (3. 1),


Here, lip is called the integrotingjuctor. Tberefore, an inellaet differential d W when multiplied by an integrating factor IIp becomes an ellact differential

For a cyclic process, tbe initial and final states of the system are the same, and hence, the change in any propeny is zero, i.e.

jdV=.,jdp =O. !dT=.

where the symbol


f denotes the cyclic integral for the closed path. Therefore,

the cyclic integral aj a properly is a/ways zero.

3.2.2 pdY- Work iJi Y/Jmw Qutut-St4tk Processes

(a) Consta'lt pressure process (Fig. 3.7) (isobaric or i!!Opiestic process)
W I_2 .,

pdY - p(V2 - Y\)


(b) Constant volume process (Fig. 3.8) (isochoric process)

Wt_1 '"

JpdY ~ O




Flg.3.8 YlUl4nt roJUfIU prlXIJ.J

(c) Process in which pY OE C (Fig. 3.9)

W1 _1 .. " JpdV, pY "" PIYI =C

p '" (PI"!) V



(d) Process in whichpVD - C, where II is a constant (Fig. 3.10).

pV D _ Pl V1D "' PIVlft .. C

P = (P1Pj")

WI _ 2=

I " .. f; J " ~


P1Pja .dV


(PI VOL) [ V- a+ l ] "

-11+1 _ PI Pj" (V 1-" Pl I)" x


til _Vl-ft) vl -a PIPj" X Pjl - n

1 "

= PIPj 1- .l!1..

'-U '] [ ( )


v, -v

v, -v
fig. 3.10 Prus i~ which pV crmstaJl/


Indicator Diagram

An indicator diagram is a trace made by a recording pressure gauge, called the indicator, attached to Ihe cylinder of a reciprocating engine. This represents the work done in one engine cycle. Figure 3.11 shows a typical engine indicator. The same gas pressure acts on bolh Ihe engine piston P and the indicator piston / . The indicator piston is loaded by a spring and it moves in direct proponion to Ihe change in pressure. The motion of the indicator piston causes a pencil held at the end of the linkage L to move upon a strip of paper wrapped around drum D. The drum is rotated about its axis by cord C, which is

WGfi.". n,td TrllllSftr

Flg.3.11 EtrgiIll ilUlicator

conne<:led through a reducing motion R to the piston P of the engine. The surface of dnlm D moves horizontally under the pencil while the pencil moves vertically overthe surface and a plot of pressure upon the piston vs. piston travel is obtained. Before tracing the final indicalor diagram, a press ure reference line is recorded by subjecting Ihe indicator to Ihe atmosphere and tracing a lino at a constant pressure of one atmosphere. The area of the indicator diagram represe nts the magnitude of the. net work done by the system in one enginc cycle. The area under the path 1- 2 represents work done by the system and the area under the path 2- 1 represents work done upon the system (Fig. 3.12). The area of the diagram, ad, is measured by means of a planimeter, and the length of the diagram, 'd' is also measured. The mean effective pressure (m.e.p.) Pm is defined in the following way

Pm " ~xK I,
where K is the indicator spring conslant (N/cm l x cm travel). Work done in one engine cycle

Fig. 3.12

JlUlicalor diagram


" (PmA)L


.A = crosssectional area of the cylinder

.. : rr, where D is the cylinder diameter

L .. stroke of piston, or length of cylinder.

Let Nbc the revolutions per minute (r.p.m.) of the crankshaft. In a two stroke cycle, the engine cycle is completcd in two strokes of the piston or in one revolut ion of the crankshaft. In a fours troke cycle, the engine cycle is completed in four strokes of the piston or two revolutions of the crankshaft. For a lWo-stroke engine, work done in one minute'" Pm ALN. and for a four stroke engine, work done in one minute " Pm ALNI2. The power developed inside the cyli nder of the engine is called indicated power (lP),

PmA' ( Nor!:!..),
2 kW (3.8) 60 where Pm is in kPa and n is the number of cylinders in the engine. The power available at the crankshaft: is always less than this val ue (lP) due 10 friction, etc. and is called the brake po'we, (SP) or shaft power (SP). If ru is the angular ve locity of the erankshaft in radianlse<:, then SP - Til) (3.9) where T is the torq ue transmitted to the crankshaft: in mN.
BP _ 21fTN 60 where N is the number of revolutions per minute (rpm). The mechanical efficiency of the engine. lJ,....,h' is defined as

IP =






(3. ll)

An engine is said to bedouble+octing. If the working fluid is made to work on both sides of the piston. Such an engine th roretically develops twice the amount of work developed in a single'acting engine. Most reciprocat ing steam engi nes are double-acting, and so are many marine diesel engines. Internal combustion engines for road transpon arc always singic-Ilcting.


Other Types of Work Transfer

There are fonns of work other Ihan pd V or displacement work. The following are the additional types of wo rk transfer which may get involved in systemsurroundings interactions. (a) Electrical Work When a current fl ows through a resistor (Fig. 3.13), taken as a system, there is work transfer into the system. This is because the current can drive a motor, the motor can drive a pulley and th e pulley can raise a weight.


The current fl ow, I, in amperes, is given by

"----- system boundary

Fig.3. 13 EJntrical wtd:.

1 _ de dr where C is the chargc in coulombs and r is time in seconds. Thus de is the charge crossing a boundary during time dr. If is the voltage potential, the work is
d W" dC = /dr

w- I

, f:./dr


The electrical power will be

'v .. d<lim dW - 1 .... O dr

This is the rate at which work is transfcrrcd.


(b) Shaft Work When a shaft, taken as the system (Fig. 3.14), is rotated by a
motor, there is work transfer into the system. This is because the shaft can rotate a pulley which can raise a weight. 1fT is the torque applied to the shaft and d8 is the angular displacement of the shaft, the shaft work is r W = Td8 (3. 14)


and the shaft power is

w J


where ru is the angu lar velocity and T is considered a constant in this case.

r.n~n-nJ-.-n. -d!

System boundary



Shaft Iml,k

(el Paddle-Wheel Work or Stirring Wo rk As the weight is lowered. and

the paddle whecl turns (Fig. 3.15), Ihere is work transfer inlo thc fluid systcm


which gets stirred. Since the volume orthe system remains constant. pd v- O. If m is the mass orthe weight lowered through a distance d:: and T is the torque transmitted by the shaft in rotating through an angle d9, the differential work transrer to the fluid is given by dW = mgdz = Td9 and the total work transfer is



w- j mg"' - j " '''' - j

where /Y' is the weight lowered.




PtuJ4u.wh.,1 UHlrk

(d) Flow Work The flow work. significant only in a flow process or an open system. represents the energy transferred across the system boundary as a result or the energy impaned to the fluid by a pump, blower or compressor to make the fluid flow across the control volume. Flow work is analogous to displacement work. Let p be the fluid pressure in the plane of the imaginary piston, which acts in a direction normal to it (Fig. 3.16). The work done on this imaginary piston by the external pressure: as the piston moves forward is given by

c1 WII<rw = pd V,



Row work


where dV is the volume of fluid element about to enter the system.

(3. 17)

wheredV - vdm Therefore, fiow work at inlet (Fig. 3.16),

(3.18) (dWa"",)ia - Plvldml Equation (3.18) can also be derived in a slightly different manner. If the oonnal pressW'C PI is exerted against the area A., giving a lotal fOR:e (PI AI) against the pistoo, in time dr, this force moves a distance V Idr, where V I is the velocity offiow (piston). The work in time dr iSPI Al V Idr, or the work per unit time isPI Al VI' Since the flow rate
wI "




the work done in time dt bel.:omes

(d Wn....)iD .. PI Vj dm l Similarly, flow work of the fluid element leaving the system is

(t WOo..)ouc '" pz 0z dmz

The flow work per unit mass is thus

(3 .19)

W 110w - pv It is the displacement work done at the moving system boundary.


(e) Work Done in Stretching a Wire Let us consider a wire as the system. If the length of the wire in whieh there is a tension 'J is ehanged from L to L + dL, the infinitesimal amount of work that is done is equal to

dW "' - 'J dL The minus sign is used because a positive value ofdL means an expansion of
the wire, for which work must be done on the wire, i.e.. negative work. For a fm.i.le change of length,

, W=- J ,dL ,

(3.2 1)

If we limit the problem to within the elastic limit, where E is the modu lus of elasticity, s is the stress, e is the strain, and A is the cross-sectional area, then
!f=sA = EEA . since!.... '" E E



d W .. - !fdL '" - EeAL d



W=- AELJ ed =--(Ei-Er)




(f) Work Done in Changing the Area of a Surface FUm A film on the surface ora liquid has a surfaee tension, which is a property of the liquid and the surroundings. The surface tension acts to make the surface area of the liquid a minimum. It has the unit of force per unit length. The work done on a homogeneous liquid film in changing its surface area by an infinitesimal amount dA is

Ii W=- adA
where ais the surface tension (N/m).

w .. _J adA


(g) Magnetization of a Paramagnetic SoUd The work done perunit volume on a magnetic material through which the magnetic and magnetization fields are unifonn is
Ii W= - HdJ


W I_2

= -1



where H is the field strength, and I is the component of the magnetization fi eld in the direction of the field. The minus sign provides thai an increase in magnetization (positive dJ) involves negative work. The following equations summarize the different forms of work transfer. Displacement work

(compressible fluid) Electrical work

W = / pdV

W= / EdC = / 1 dt

Shaft work


, J Td6

Surface film

w -- J

Stretched wire

W - - /YdL

"' "


ud IItlll TrlllUftr


Magnetised solid

w- - J HdJ

, ,

It may be noted in the above ellprcS5ions that the work is equal to the integral of the product of an intensive property and th e change in its related elltensive property. These ellpressions are va l;d only for infinitesimally slow quasistatic processes. There are some other forms of work whi::h can be identified in processes that are not quasi-static. for example, the work done by shearing forces in a process invol\'ing frict~on in a viscous fluid.

3.5 Free Expansion with Zero Work Transfer

Work transfer is identified only at the boundaries of a system. It is a boundary phenomenon. and a form of energy in transit crossing the boundary. Let us consider a gas separated from the vacuum by a partidon (Fig. 3.17). Let the panition be removed. The gas rushes to fill the entire volume. The expansion of a gas against vacuum is calledJree expansion. If we neglect the work associated with the removal of partition. and conside r the gas and vacuum together as our system (Fig. 3.17a). there is no work transfer involved here. since no work crosses the system boundary, and hence

, , J c1 W - 0, although J p dl'~ 0 , ,

If only the gas is taken as the system (Fig. 3. 17). when the partition is removed there is a change in the volume of the gas, and one is tempted to
calculate the work from the ellprcssion

J , p dV. However, this is not a quasi static

process, although the initial and final end states are in equilibrium. Therefore. the work cannot be calculated from thi s relation. The two end slates can be located on the p-V diagram and tbese are joined by a dOlled line (Fig. 3. 17e) to indicate that the process had occum:d. However, if the vacuum space is divided into a large number of small volumes by partitions and the partitions are mnoved one by one slowly (Fig. 3. 17d), then every state passed through by the system is an equilibrium state and the work done can then be estimated from the relation

J , pdV (Fig. 3.17e), Yet, in free ellpansion ofa gas,

there is no resistance to the nuid al the system boundary as the volume of the gas increases to fill up Ihe vacuum space. Work is done by a system to overcome some resistance. Since vacuum does not ofTer any resistance, mere is no work transfer involved in free expansion.



f -~

"""''' 4:?~ ...''' ...''' ...''I .. =='t :

: --:
L. ....

: ""__




, ,
_ v

: ,

Gn t.:



3.6 Net Work Done by a System

Often different forrm of a work transfer occur simuhaoeously during a process exe(:utcd by a sy:ttem. When all these work interactions have been evaluated, the total or net work done by the sySfem would be equal to the algebraic sum of these as given below

W...... - W~+ W_+ W doclrieal + WotirriaJ+ . . .

3.7 Heat Transfer

Heat is defined as the fonn of energy that is transferred across a boundary by

vime of a temperature difference. The temperature difference is the 'potential' or 'force' and heat transfer is the 'flux'. The transfer of heat between two bodies in direct contact is called conduction. Heat may be transferred between two bodies separated by empty space or gases by the meehanism of rodiation through electromagnetic waves. A third method of heat transfer is convection which refers to the transfer of heat between a wall .and a ftuid system in motion. The direction of heat transfer is taken from the high temperature system to the [ow temperature system. HeOiflaw into a SYSfem is ta~n fo be positive. and heatflow out of a system is taken as negative (Fig. 3.13). The symbol Q is used for heat transfer, Le., the quantity of heat transferred within a certain time. Heat is a fonn of energy in transit (like work tI'llIl!lfer). It is a boundary phenomenon, since it occurs only at the boundary of a system. Energy transfer by vinue of temperature difference only is called heat transfer. All other energy interactions may be tenned as work transfer.


&sic II.tui Ap;/itd 11InmodJ'usmia


fig. 3.19

Rtprtwlll4ti~~ ~[uxnk ~.~

trd/U[tr ud Mdt trd/U[tr i~ fKIISi-sfGtit

p-P.tui T-x ,",diuUs

Just like displacement work, the heat tnmsfer can also be written as the integral of the product of the intensivc property T and the differential change of an extensive propeny, say X (Fig.3.19b).

, , Q,_ ,- 14Q -1 TdX , ,


It must also be valid for a quasi-static process only, and the heat transfer involved is represented by the area under the path 1- 2 in T- X plot (Fig. 3.19b). Heat transfer is, therefore, a path function, i.e., the amount of heat transferred when a system changes from a state I to a state 2 depends on the path the system follows (Fig. 3.19b). Therefore, d Q is an inexact differential. Now,

dQ - TdX where Xis an extensive property and dX is an exact differential.

T To make d Q integrable, i.e., an exact differential, it must be multiplied by an integrating factor which is, in this case, l IT. The extensive property X is yet to be defined. It bas been introduced in Chapter 7 and it is called 'entropy' .


dX - l..dQ


3.9 Specific Heat and Latent Heat

TIle specific heot of a substance is defined as the amount of heat required to raise a unit mass of the substance through a unit rise in temperature. The symbol c will be used for specific heat.

c - ~ JlkgK
m 1l1


where Q is the amount of heat transfer (J), m, the mass of the substance (kg), and Ilt. the ri se in temperature (K). Since heat is not a property, as e}[plained later, so the specific heat is qual ified with the process through which exchange of heat is made. For ga~s, if the process is at constant pressure, it is cp' and if the process is at constant volume, it is cV' For solids and liquids. however, the specific heat does not depend on the process. An elegant manner of defining specific heats, c. and Cpo in temlS of properties is given in Secs 4.S and 4.6. The product of mass and specific heal (mc) is caned the heat capacity of the substance. The capital letter C, Cp or C" is used for beat ca paci ty. The latent heat is the amount of heat transfer required to cause a phase change in uni t mass of a substance af a constant pressure and temperuture, There are three phases in which matter can exist: solid. liquid, and vapour or gas. The latent heat offusioll (If,) is the amount of heat transfclTed to melt unitma5S of solid into liquid. or to freeze unit mass of liquid 10 solid. The lalent heat of vaporization (1,'aII) is the quantity of heat required to vaporize unit mass of liquid into vapour, or condense unit mass of vapour into liquid. The latent heat of subUmalion is the amount of heat transferred to convett unit mass of solid to vapour or vice versa. lfu is not much affe<:1ed by pressure, whereas I"", is highly se nsitive to pressure.


3.10 Points to Remember Regarding Heat Transfer and Work Transfer

(a) Heat transfer and work transfer are the energy interacnolU. A closed system and its surroundings can interact in two ways: by heat transfer and by work transfer. Tbennodynamics studi es how these interactions bring about propeny changes in a systcm. (b) The same effect in a closed system can be brought about either by heat transfer or by work transfer. Whether heat transfer or work transfer bas taken place depends on what constitutes the system. (c) Both heat transfer and work trans fer are boundary phenomena. Both are nbserved at the boundaries of the system, and both represent energy crossing the boundaries of the system. (d) It is wrang to say 'total heat' or 'heat content' of a closed system , because heat or work is not a property of th e system. Heat, like work, cannot be stored by the system. Both heat and work are the energy in transit. (e) Heat transfer is tbe energy interaction due to temperature difference only. All other energy interactions may be lenned as work transfer. (f) Both heat and work are path functions and ~ne)(aci differentials. The magnitude of heat lransfer or work transfer depends upon the path th e system follows during the change of state.




Ezample 3.1 Gas from a bottle of compressed helium is used to inflate an inelastic flexible balloon, originally folded comple1ely flat 10 a volume of 0.5 m1.lfthe barometer reads 760 mm Hg, what is the amount of work done upon the allllosphere by the balloon? Sketch the system before and after the process. Solution 1be fllIJlline PI (Fig. Ex. 3.1) shows the boWldary of the system before the process, and the dotted line P2shows the boundary after the process. The displacement work
Wd '"


pdV +


pdV " P,,"V+O

.. 101.325 .. 50.66 kJ


x 0.5 m1

This is positive ~ause work is done by the system. Work done by the atmosphere is - 50.66 kJ. Since the wall of the bottle is rigid. there is no p dVwork in... olved in it II is assumed that the pressure in the balloon is allllospherie at all times, since the balloon fabric is light, inelastic and unstressed. If the balloon were elastic and stressed during the filling process, the work done by the gas would be greater than 50.66 kJ by an amnunt equal to the work done in stretching the balloon. although the displacement work done by the atmosphere is still - 50.66 kJ. However, if the system includes both the gas and the balloon, the displacement work would be 50.66 kJ, as estimated above.


P - 760mmHg - 101 .325 kP.

. ......:
Plg. b. 3.1


Work IIU HtIIl nllti{"


Eumple 3.2 When the value of the evacuated bottle (Fig. Ex. 3.2) is opened, atmos~beric air rushes into it. If the atmospheric pressure is 101.325 kPa, and 0.6 m of air (measured at atmospheric conditions) enters into the bottle, calculate the work done by air.

Initial bI:uldary

..--. ...'i

P""" - t Ol .325 kPe

Fig. b.. 3.2

Solution The displacement work done by air



J pdV+ J

- O+pt.v .. 101.325 !tN/ml




0.6 ml

- 60.8 kJ Since the free-air boundary is contracting, the work done by the system is negative (.6. V being negative), and the surroundings do positive work upon the system. Eumple 3.3 A piston and cylinder macbine containing a fluid system has a stirring device in the cylinder (Fig. Ex. 3.3). The piston is frictionless, and it is held down against the fluid due to the atmospheric pressure of 10 L325 kPa.. The stirring device is turned 10,000 revolutions with an average torque against the fluid of 1.275 mN. Meanwhile the piston of 0.6 m diameter moves out 0.8 m. Find the net work tnmsfer for the system.

! P- tOt .32kPa

FIg. Ex. 3.3



Work done by the stirring device upon the system (Fig. EJI;. 3.3).

W1" 2KTN .. 2K x 1.275 x 10,000 Nm -SOU

This is negative work for the system. Work done by the system upon the surroundings

W2 = (pA)L

- 101 .325 ~
= 22.9 U

x.!!. (O.6)2 m2 xO.80m


This is positive work for the system. Hence, the net work ttansfer for the system JfI - WI + W2 - - 80+22.9 -- 57.1 kJ

Eu..mple 3.4 The following data refer to a 12-cylinder, single-acting, twostroke marine diesel engine:

Speed-ISO rpm Cylinder diameter-0.8 m

Stroke ofpiston--I.2 m Area orindicator diagram-55 x 10- 4 m1 Length of diagram-O.06 m Spring valuc-147 MPa per m Find the net tale of work ttansfer from the gas to the pistons in kW.


Mean effective pressure, p"" is given by

P", '" -

", x spnng . constant " 5.5 m x 147 MPa

X 10-<4 1

= 1.35 MPa

One engine cycle is completed in two strokes of the piston or one revolution of the crank-shaft. :. Work done in one minute

- proLAN

- 1.35 X ~(0.g)2 x 1.2 x 150 - 122 MJ

Since the engine is single-acting, and it has 12 cylinders, each contributing an equal power, the rate of work ttansfer from the gas to the piston is given by W - 122 x 12 MJ/min - 24.4 MJ/s .. 24.4 MW - 24,400 kW

Wltl'k lad Hrll Trusftr


~ple 3.5 It is required to melt 5 tonnes/h of iran from a charge al 15C 10 molten metal al 16sO"C. The melling point is Is3s c C, and the ialenl heal is 270 kJlkg. The specific heal in solid state is 0.502 and in liquid slate (29.93/atomic weight) kJlkg K. If an electric furnace has 7()OIo efficiency. find the kW rating needed. If the density in mollen state is 6900 kg/m1 and the bath volume is three limes the hourly melting rate, find the dimensions of the cylindrical furnace if the length 10 diameter ratio is 2. The atomic weight of iron is 56.

Solution Heat required to melt I kg of iron at 15C to mohen metal al 16s0C

- Heal required 10 raise the tempemture from 15C to Is3s 0 C + Lalent heat + Heal required 10 raise the tempcrature from 1535C 10 16s0C - 0.502 (1535 - 15) + 270 + 29.93 (1650 - 1535)156 .. 763 + 270 + 61.5 - 1094.5 kJlkg Melting rale - 5 x 10) kg/h So, the rate ofheat supply required - (5 x Icr x 1094.5) kJlh Since the furnace has 7G-1i efficiency, the rating of the furnace would be _ Rate of heat supply per second Furnace effciency .. 5 x 10) x 1094.5 - 217x IIYkW 0.7 x 3600 Volume needed - 3xsxlO ml _ 2.18ml 6900 If d is the diameter and f the length of the furnace

! dl/ _ 218 m)


d - 1.15m 1- 2.30 m


~ple 3.6 If it is desired to melt aluminium with solid state specific beat 0.9 kJlkgK. lalent beal 390 kJlkg, atomic weight 27. density in molten state 2400 Itglrol and final temperature 700C. rand out how much metal can be melted per hour with the above kW rating. Other data are as in the above example. Also, find the mass of aluminium that the above furnace will hold. The melting point of aluminium is 66O"C. Solution Heal required per kg of aluminium


58 = - 0.9 (660 - IS) + 390 + 29.93 (700 - 660)


- 580.5 + 390 + 44.3

"'" 1014.8 kJ

Heat to be supplied .. 1014.8 = 1449.7 kJ/kg 0,7 With the given power, the rate at which aluminium can be melted
2.17 x !OJ x 3600 1449.7 - 5.39 tonnes/h - 2.18x2400kg - S.23 tonnes



Mass of aluminium that can be held in the above furnace


3.2 3.3 3..

How can a closed sySian and is surroundings inleracl'l Whal is the effec::1 of such interactiOlH 011 the system? When is work said 10 be done by al)'Sletll? What arc positive and negative work interactions? Wllat is dUplacemcnl work'?
Under what conditions is the work done equal to

3.6 3.7 3.8 3.9 3.10 3.11 3.12 3.13 3.14 3.1~ 3.16 3.17 3.18 3.19

I , pdV/

What do you Ilndel'$tand by patb function and point' function? What arc eMct and inextoCt differentials? Show that work is a path function, and not a property. What is an indicator diagram? What is mean effective pressure? How is it measuml? What arc the indicated power and the brake power ofan engine? How does the eurrent flowing through a resistor represent work tnnsfer? What do YOllllndemand by flow work? ' , it different from displacement work? Wby does free expansion have uro work transfer? What is heat transfer? What arc its positive and negative directi01l$? What arc adiabatic and diatbetmic walls? What is an integrating factor? Sbow that heat is a path function and not a propeny. WIW is !be differen<:e between work tnnsfer and heal transfer? Docs beat transfer inevitably e.use a tem~ture rise?

"' "

Work (lIuI HtIlI TttJIIJfn'



3.1 (a) A pwnp fatUs 1 mJ/min ofwalerhorizontally from an open well to a closed tank where the pressure is 0.9 MPa. Compute the work the pump must do upon tm: lO.'3tcr in an hour just to force tIM: water into thc tank against the presSUfC. Sketeh the system upon which the work is done bef~ and after the proccss.

Ans. 13.3 1 Id
(b) ]the work done as above upon the water had been used solely to raise the same amount ofwaler \'enically against gravity without change of pressure , how many meters would the wateT have been elevated? (c) If the work done in (a) upon the water had been used 501ely to accclcrnte the waler from zero velocity withoul change of pressure or eicvation. what velocity would the water have reached? If tbe work. had been used to accelenlle the water from an initial velocity of 10 mfs, wl'lat would the final v.:locity have been? The pislon of an oil ensine. of area 0.0045 m 2, moves downwards 15 mm. dmwing in 0.00028 m) of fresh air from the almosphere. The pressure in the cylinder is unifOim during the process at 80 kPa, while the atmospheric ]lTCssure is 101.325 kPa, the difference being due to the flow resistance in tm: induction pipc and the in let valve. Estimate the disp laeemC11t woO: done by the air finally in the cylinder. An$. 27 1 An engine cylinder has I piston of area 0.12 ml and contains gas at a pressure of I.S MPa. The gas expands according 10 a process which is represented by a sll'IIigh\ line on a pressure-volume diagram . The linll presson: is 0.15 MPa. Calculate the work done by the g3S on the piston if the stroke is 0.30 m. AIlS. 29.7 kJ. A mass of I.S kg of air is compressed in a quasi -static process from 0.1 MP. to 0.7 MPa forwbiehpu - constant. The initial density of air is 1.16 k.glm J Find the work done by the piston to compress the air. Ans. 251.62 k.J A mass ofgas is compressed in iI quasi-stalic process from 80 kPa, 0.1 ml to 0.4 MPa. 0.03 rn l. Assuming that the press ure and volume are related by F" constant, lilld the work done by the gas 5yStC111. Ans. - 11.83 kJ A single-eylinder, double-acting, reciprocaling water pump has an indicator diagram which is a rectangle 0.075 m long and 0.05 m high. The indicator spring C01L'itanl is 141 MPa pcr m. The pump runs at 50 rpm . The pump cylinder diamcter is 0.15 m.nd the piston stroke is 0.20 m. Find the rate in k.W at which Ihe piston docs work. on the waler. AM. 43.3 k.W A single-eylinder, single-actinS, 4 stroke engine ofO.IS m bore dc\"Clops an indicated power of 4 k.W when running at 216 rpm. Calcu late the area of the indicator diagram tbat would be obta ined with an indicator having a spring constant of 2S )( l(f N/m). Tbe length of the indicator diagram is 0.1 times tIM: length of the strok.e oftbc engine.







50S mm 2

60 = 3.8 A sil(-(ylindet.4-stroke gasoline wgrne is ronal a speedof2520 RPM. The ami of !he indicator card of one cylinder is 2.45 )( lit mm l and ils length is 58.5 mm. The spring CDIl$UUlt is 20)( 10' Him). The bore of the cylinden is 140 mm and the piston stroke is IsO mrn. Detennine the indicated power, assuming !hat each cylinder contributes an equal power. AILl'. 243.57 kW A closedcylindcrofO.25 m diameter is lined wi!haUgIU frictionless piston. The piston is retained in position by a cateb in tbe cylinder wall and the vo lume on Olle side of!hepistOD conlllins air at a prenure of750 kN/ml. The volume on the other side of the piston is evacuated. A helical spring is mounted coaxially wi!h the cylinder in lhis evacualed space 10 give a force ofJ20 N on the piston in this position. The catch is released and the piston trnvels along the cylinder until it eomes to rest after a stroke of 1.2 m. The pistoo is !hen held in its pmilion of milllimum nvel by a ratchet ~hIlnism. The ~pring force increases linearly with the piston displacement 10 a final value of5 kN. Calculate the work done by the compressed air on the pi$loo. AILl'. 3.07 kJ A steam rurbine drives a ship's propeller through an g : 1 reduction gear. The average resisting torque imposed by the wateron the propeller is 750)( 10J N and the shaft power delivered by the rurbine to the reduction gear is 15 MW. The turbine speed is 1450 rpm. Determine (a)the torquedeveloped by the turbine. (b) the power de livered to the propell er shaft, and (c) the nelrale of",orking of !he reduction gear. AII.!'. (.) T - 98.84 kIn N. (b) 14.235 MW. (e) 0.765 MW A Ouid., contained in a horirontal cylinder fined with a frklionlcu leakproof piston. is continuously agitated by means of a srirrtT passing through the cylinder eover. The cylinder diameter is 0.40 m. During !he stirrillll process lasting 10 minutes. !he piston slowly moves Oul a distance of 0.485m against the atmosphere. The net work done bylbe fluid during the pTOl:e$S is 2 kJ. The speed of !he electrie motor driving the stirrer is 840 rpm. Detemline the torque in !he shaft and the power outpUt of the motor. AIlS. 0.08 roN. 6.92 W At the beginning of the (ompression stroke ofa two-cylinder internal combustion engine !he air is at D pressure of 101.325 kPa. Compression reduces the volume to 115 of its original volume, and the law of compression is given by pVU _ constant. If the bore and stroke of each cylinder is 0_ 15 m and 0.25 m, respectively, determine the power absorbed in kW by compression strokes when tbe engine speed is such that each cylinder undergoes 500 compression strokes per minute. Ans. 17.95 kW Determine !he total work done by a gas system foUolling an ClI:pansion process as shOIl'O in Fig. P. 3.13.





3. 13

'" ~

Ans. 29S2 MJ
pV, 3 C

" I

.2 : 0.4

i !


Fig. P.3.13

3.14 A system of volume V contains a mass m of gall at p=surep and tempcrnture T. The macroscopic properties of tile system obey the following relationship:

(p+ ;: )W-b) .. mRT

where 0, b, and R are com;tall1s. Obtain an e"pression for Ihe di~lll\:emenl work dooe by the syJlem during a constant-temperature expansion from volume VI to \'Olume fl' Calculate the work dorIC by a system which contains 10 kg ofthi! gas expanding from I m1 to 10 m] al a temperature of 293 K. Use the val ues a " 15.7 )( 10~ Nm~, b .. 1.07)( 10- 2 m', and R - 0.278 kJlkg-K. All.!". 1742. 14 kJ If a gas of volume 6000 cm J and at a pressure of 100 kPa is compressed quasist:nical1y according to pV: ~ constant until Ihe volume becomes 2000 em), detennine the final pressure and the work IIansfcr. A...... 900 kPa. 1.2 kJ The flow energy of 0.124 mJlmi n ofa fluid crossinga boundary to system is 18 kW. Find the pressure at this point. All.!". 764 kPa A milk chilling unit can remove Ileal from the milk al the rate of 41.87 MJIh. Heat leaks into the milk from the surroundings at an average rate of 4.IS7 Mllh. Find the time required for coo lins a ha leh of 5()() kg of milk from 4SC 10 SC. Take the cp ormi lk to be 4.lg7 kJ/kgK. 680].;g of fish at SoC arc to be frozen and stored 3t-12 "C. The specific lIeat of fisb above freeziog point is 3. 182, and below freezing point is 1.717 kJlkgK. The f~zing point is - 2C. and the latent heal of fusion is 234.5 kJIks. How much heal must be removed to cool tile fish, and what per cent of this is latent heat? All.!", 186.28 MJ, 85.6% A horizontal cylinder fined with a sliding piston contains 0.1 m l of 3 gas at a pressure of I atm. The piston is restra ined by a linear spring. In the in itial sta te, the gas pressure imide the cylinder just balances the atmospberic pressure of I aim on the oullliik oftlie pi ston and the spring e)lerts no force on the piStoo. TItc gas i5 then heated re\"ersiblyunti l its ,olwrn:: and pre5SUre become 0.16 ml and 2 atm, respect i\"e ly. (a) Write tlte equation for the relation between the pressure and volume oftbc gas. (b) Calculate Ihe work done by the gas. (e) Of lhe: total work done by the gas, how much is done against the atmosphere? How much is done against lite spring'! An!. (a) p (Nlm 1) .. 2.026)( If/' V _ 1.013 x lOS (b) 7,5981, (c) S,065 1, 2,533 J An elastic sphere inilially lias a diameter of I m and contains a gas at a pressure of I aim. Due to heat transfer the diameter oftbe sphere inCTclSC5!O 1.1 m. During the heati ng process tile gas pressure inside the sphere is proponionallo the lphere diamcter. Calculate thc work done by the ga$. AILJ. 18.4 kJ A pi5lon-cylinder dC\lice contains 0.05 ml of a gas initially at 200 kPa. At this slate, a linear ~pring havinga spri ng conSUl/U of ISO kNlm i5 touelling the piston but enn ing no foree on i1. Now heat is transferred to the gas, causing the piston !O riscand to compress tbe spri ng until the volwrn:: inside the cylinder doubles. If the cross-sectional area of the piston is 0.2S ml , detennine (a) the final pressure

3. 15

3. 16






inside the cylinder, (b) the IOtal work done by the gu, and (c) the fraction oflhis work done against the spring 10 comprns it AM. (a) 320 kPa, (b) 13 kJ , (c) 3 kJ 3.22 A piston-cylindct device, whose piston is I'C$ting on a set of stops, initially contains 3 kg of air 3t 200 ~I and 27C. The mass of UK: piston is sucb lhat a pressure of 400 kPa is required 10 move it. Heat is DOW II"IUl5fcm:d to the air until its volume doubles. Detennine the work done by the lir and the total hell transferred to the air. A.M. Sl6 kJ, 2674 kJ


First Law of Thermodynamics

Energy can be in two forms: (a) energy in Iransit, like heat and work transfcr

observed at the boundaries ofa system, and (b) energy inslorage, where energy is stored eiiliermocroscopicallyby virtue: ormotion, position or configuration of the system, ormicroscopicallyin the molecules or atoms constituting the system.


First Law for a Closed System Undergoing a Cycle

The transferofheat and the performance ofwark may both cause the same effect in a system. Heal and work are different forms of.the same entity, called energy.

which is conserved. Energy which enters a system as heat may leave the system as work, or energy which enters the system as work may leave as heat.
Lei us consider a closed system which consists of a known mass of water contained in an adiabatic vesse l having a thermometer and a paddle wheel, as shown in Fig. 4.1. Let a ccrtain amount of work W I _l be done upon the system by the paddle wheel. The quantity of work can be measured by the fall of weight which drivcs the paddle wheel through a pulley. The system was initially at temperature ' I' the same as that of atmosphere, and after work transfer let the temperature rise to fl' The pressure is always I atm. The process \- 2 undergone by the system is shown in Fig. 4.2 in generalized thennodynamic coordinates X, Y. Let the insulation now be removed. The system and the surroundings interact by heat transfer till the system returns \0 the original temperature II> attaining the condition of thermal equilibrium with the atmosphere. The amoWlt of heat transfer Ql- I from the system during Ihis process, 2- 1, s hown in Fig. 4.2, can be estimated. The system thus exeeutes a cyele, which consists of a definite amount of work input W 1_1 to the system followed by the transfer oran amount of heat Q2-1 from the syste m. It has been found that this W 1_1 is always proportional 10 the heat Q2-I' and the constant ofprop<lrtionalily is called the Joule's equivalent

or themec:hanical equivalent ofhea/. ln the simple example given here, there are only two energy transfer quantities as the system perfonns a thennodynamic cycle. If the cycle involves many more heat and work quantities, the same result will be found. Expressed algebraically.
(tW).yc.. " J(tQ)<r<1o whereJ is the Joule's equivalent. This is also expressed in the fonn

(4. 1)

where the symbol

f denotes the cyclic integral forthe closed path. This is thefirst

law for a closed system undergoing Q cycle. It is accepted as a general law of nature, since no violation of it has ever been demonstrated. In the S.1. system of units, both heat and work are measured in the derived unit of energy, the Joule. The eonstant of proportionality, J, is therefore unity (J .: I Nmll) . The first law ofthennodynamics owes much to l .P. loule who, during the period 1840-1849, earried out a series or experiments 10 investigate the equivalence of work and heat. In one of these experiments, l ouie used an apparatus similar to the one shown in Fig. 4.1. Work was transferred to the

Fig. 4.2

OjtU rIImpltlnl by 1/ I]sl"" wilh /wQ ilfUrwioJlS; tUiiM4lu work traJUjtr W'.lfolltJltJd by ludltrans!tr ~. ,




mass of water by means of a paddle wheel driven by the falling weight.

The rise in the temperature of water was recorded. Joule also used mercury as the fluid system, and later a solid system of metal blocks which absorbed work by
friclion when rubbed against each other. Other experiments involved the

5Uppiyingofwork inan electric current. In every case, he found the same ratio (J) between the amount of work and the quantity orheat that would produce identical effects in the system. ?riorto louie, heat was considered to be an invisible fluid flowing from a body of higher calorie to a body of lower calorie, and this was known as the c%ric theory of heal. II was Joule who first established that heat is a fonn of energy, and thus laid the foundation oflbe firsllaw ofthennodynamics.

4.2 First Law for a Closed System Undergoing

a Change of State
The expression CEW)<r<1o - (1:Q)<)'<10 applies only to systems undergoing cycles, and the algebraic summation of all energy transfer across system boundaries is zero. But if a system undergoes a change of state during which both heat transfer and work transfer are involved, the net energy transfer will be stored or accumulated within the system.lfQ is the amount orheat transferred to the system and II' is the amount of work transferred from the system during the process (Fig. 4.3), the net energy transfer{Q -II') will be stored in the system. Energy in storage is neither heat nor work, and is given the name internal energy or simply, the energy of the system. Therefore Q - W'" t.E
where M is the increase in the energy of the system



Here Q, W, and 6E are all ell:pressed in the same units (in joules). Energy may be stored by a system in different modes. as explained in Aniele 4.4. If there are more energy transfer quantities involved in the process. as shown in Fig. 4.4, the flfStlaw gives

+ QJ -

Ql) - AE + (W~

+ W) -

WI - "'.)







'Fig. 4.3 Hull 1l1Ui w~ .t iRwarlioru of d

W, Surroundings

FIg. 4.. Sy,I"'l'llirrOlindi/W inl"Aflion in

d fnlKtll inNlim~

I]slnn with ilS fIllTOlI~di/W in d


mil"] rnrrgy



Energy is thus conserved in the operation. The firsl law is a particular formulation of the principle of the conservation of energy. Equation (4.2) may also be considered as the definition of energy. This definition does not give an absolute value of energy E, but only the change of energy M for the process. It can, however, be shown that the energy has a defmite value at every state of a syslem and is, th~fore, a property of the system.

.3 Energy-A Property of the System

COlUlider a system which changes its state from state I to state 2 by following the palll A, and returns from state 2 to stale 1 by followin8 the path B (Fig. 4.5). So lIle system undergoes a cycle. Writing the first law forpalll A (4.3) QA. - t1EA. + WA. and for path B QB "' MB + WB (4.4) The processes A and B togelller constitute a cycle. for which

or or

(l:W)<y<Ie" (EQ~I. WA+ WB - Q,oI + Qa QA-WA - WB - QB From equalioll!l (4.3), (4.4), and (4.5), il yields


t1EA - - Ma (4.6) Similarly, had lIle system returped from state 2 to state I by following lIle palll C instead of path B (4.7) MA "- M e From equations (4.6) and (4.7) Ma " !JEe (4.8) Therefore, it is seen that lIle change in energy between two states ofa system is lIle same, whatever palll the system may follow in undergoing that change of state. Ifsome arbilnlry value of energy is assigned to state 2, the value of energy al state I is fIXed independent of the path the system follows. Therefore, energy has a definite value forevery stale orthe system. Hence, it is apain/junction and a property of the system.


-=67 The energy E is an extensive property. Thcspecjfic energy. e - Elm (Jfkg), is an intensive property. Thc cyclic integral of any property is zero, because the fmal state is identical with the initial state. fdE - 0, fdY - 0, etc. So for a cycle, the equation (4.2) reduces to equation (4.1) .

.4 Different Forms of Stored Energy

The symbolE refers to the total energy stored in a system. BasicaUy there are two modes in which energy may be stored in a system: (a) Macroscopic energy mode (b) Microscopic energy mode
The macroscopic energy mode includes the macroscopic kinetic energy and potential energy of a system. Let us consider a fluid element of mass m having the centre ofmass velocity V (Fig. 4.6). The macroscopic kinetic energy EK of the fluid element by virtue of its motion is given by

mV E, --2
If the elevation of the fluid elcment from an arbitrary datum is z, then the macroscopic potential energy Ep by virtue of its position is given by
Ep " mg;:

The microscopic energy mode refers to the energy stored in the molecular and atomic structure of the system, which is called the molecular jntenwi energy or simply internal energy, customarily denoted by the symbol U. Matter is composed of molecules. Molecules are in random thermal m()(ion (fora gas) with an average velocity v, constanlly colliding with one another and with the walls (Fig. 4.6). Due to a collision, the molecules may be subjected to rotation as well

as vibration. They can have translational kinetic energy, rotational kinetic energy, vibrational energy, electronic energy, chemical energy and nuclear energy (Fig. 4.7). Iferepresents the energy of one molecule, then

e" t;,..... + e,.,. + ..;j, + e<h<m + ':1"""""" + "..;1.... (4.9) If N is the total number of molecules in the system, then the total internal
V a Ne

0 ~ 0

\\ II
Nudear ~ energy

In an ideal gas there are no intermolecular fcrees of attraction and repulsion, and the internal energy depends only on temperature. Thus V "' f(7) only (4.11) for an ideal gas Other fonDS ofenergy which can also be possessed by a system are magnetic energy, electrical energy and sunace (tension) energy. In the absence of these forms, the total energy of a system is given by
E ~ Et:.+E,+



where t:., ,., and U refer to the kinetic, potential and internal energy, respectively. In the absence of motion and gravity
,, = 0,, = 0

E- U
and equation (4.2) becomes

Q - &U+ W


Uis an extensive propeny of the system. The specific internal energyu is equal to
Ulm and its unit is Jlkg.

In the differential forms. equations (4.2) and (4.13) become

dQ "" dE + dW dQ - dU+ dW
(4.14) (4.15)

considering the different forms of work. transfer which may be present. Wben only pdVwork is prescnt, the equations become
dQ - dE + pdV dQ,"dU + pdV
(4.16) (4.17) (4. 18) (4.19)

or, in the integral form

Q=A + jpdV Q AU+ jpdV

4.5 Speci8c Heat at Constant Volume

The specific heat of a substancc at constant volume tv is defined as the rate of change of specific internal energy with respect to temper.!ture when the volume is held constant, i.e.

,.-( ~;).
For a constant-volume process



The first law may be ....Tincn for a closed stationary system composed ora unit mass of a pure substance

For a process in the absence of work other thallpdVwork

dW - pdV dQ - clu + pdu When the volume is held constant
(Q)v - (.6.u)y


(Qlv -

fc y dT



Heat transferred at constant volume increases the internal energy of the system. If the specific heat ora substance is defmed in terms of heat transfer, then Q) , _(a ar

SinceQ is not a property, this definition does not imply thatey is a propeflyof a substance. Therefore, this is not the appropriate method of defining the specific heat, although (dQ)y " duo Since u, T, and v are propenies, c. is a propeny of the system. The product mcy - c" is called the heat capacity at constanl volume (JIK).

4.6 Enthalpy
(4.24) It is an intensive property ofa system (kJ/kg). Internal energy change is equal to the heat transferred in a constant volume process involving no work other than pdY work. From equation (4.22), it is possible to derive an expression for the heal transfer in a constant pressure process involving no work other than pdV work. In such a process in a closed stationary system of unit mllSli ofa pure substance
The enthalpy ofa substance, h, is defined as h'"'u+pv

dQ - du + pdv At constant pressure

pdV'" d(PV)

(dQ)p - du + d(ptl)

.< .<

(d"Q)p - d(u+pv)

(4.25) (dQ), - db when! h - u +pV is the specific enthalpy, a property of the system. Heat transferred at constant pressure increases the enthalpy ofa system. For an ideal gas. the enthalpy becomes h - u+RT (4.26) Since the internal energy of an ideal gas depends only on the temperarun: (Eq. 4.11), the enthalpy ofan ideal gas also depends on the temperarun: only, i.e. h - [(T)only (4.27) Total enthalpy H .. mh


H = U+pV h - HIm (Ilkg)

4.7 Specific Heat at Constant Pressure

The specific heat at constant pressure cp is defmed as the rate of change of enthalpy with respect to temperarun: when the pressure is held constant


Since h, T and P are propenies. so c p is a property of the system. Like CV' c should not be defmed in terms of heat transfer of constant pre~, although

' - (~l aT


(dQ\ - db. For a constant pressure process

(4.29) Tho first law for a closed stationary system of unit mass



dQ - du+pdv h - u+pv dh "' du +pdY +vdp "" dQ+vdp dQ - dh-vdp


("Q\ db (Q),- (1Ih\

:. From equations (4.19) and (4.20)


(Q)p - J Cp dT
Cp is a

property oflhe system, just like c.. The heat capocity at COlIStont pressure Cp is equaito mc p (J/K).

4.8 Energy of an Isolated System

An isolated system is one in which there is no interaction of the system with the swroundings. For an isolated system, dQ "" O, dW = O. The fmt law gives

dE - O E - constant

The energy o[ an isoloted system i:f olways COlIStant.

4.9 Perpetual Motion Machine of the First KJnd-PMMl

The first law slates the general principle of the conservation of energy. Energy is

neither creoted nor de:ftroyed, but only gets tronsformed from one form to onotner. There can be no machine which would continuously supply m~hanical
work without some other fonn of energy disappearing simultaneously (Fig. 4.8). Such afictitious machine is called a perperuo/ motion machine of the first kind, or in brief. PMMJ. A PMMI is thus impossible.

72=The converse of the above statement is also true, i.e., there can be no machine which would continuously consume work without some other fonn of energy appearing simultaneously (Fig. 4.9).



rFIg. 4.9

Fig. U


n. UI"NTI< Df PMMl


Umitatlons of the First Law

The first law deals with the amounts of energy of various fonns transferred between the system and its surroundings and with changes in the energy stored in the system. It treats work and heat interactions as equivalent forms of energy in transit and does not indicate the possibility ofa spontaneous process proceeding in a certain direction. It is the second law which assigns a quality to different forms of energy, and also indicates the direction of any spontaneous process.


A stationary mass of gas is compressed without friction from an initial state of 0.3 m l and 0.1OS MPa to a final state of 0 .15 m1 and 0.105 MPa, the pressure remaining constant during the process. There is a transfer of37.6 kJ of heat from the gas during the process. How much does the internal energy oflbe gas change?
Solution First law for a stationary system in a process gives

bample 4.1

H '~

Q = 6U + W

WI _2 ..

" lpdY=P(Y2- ~)

... 0.105 (0.15 - 0.30) MJ ... - 15.75 kJ

QI _2 ., -37.6 kJ

:. Substituting in equation ( I ) - 37.6 kJ - V2 - VI - 15.75 kJ V 2 -U I - -21.8SkJ


FinllAw of'I1lmnoiyNlmia


The internal energy of the gas decreases by 21.85 kJ in the process. &ample 4.2 When a system is taken from state a to state b. in Fig. Ex. 4.2, along path acb, 84 kJ of beat flow into th e system, and the system does 32 kJ of ~ork. (a) How much will the heat that flows into the system ;:long pathadb be, if the work done is 10.5 kJ? (b) When the system is returned from b to a along the curved path, the work done on the system is 21 kJ. Docs the system absorb or liberate heat, and how much of the heat is absorbed or liberated? (c) IfU. "' 0 and Ud - 42 kJ, find the heat absorbed in the processes ad and db.


.lL_ _ l
Ag. Ex. 4.2 Solurian

We have

Q..b"'Ub-U.+ WO<b Uh- U. "" 84 - 32 - 52 kJ



Qldb ~Ub-UI+Wadb

= 52 + 10.5 = 62.5 kJ Ans.


Q1>-& '" U. - Vb + W1>-& :<-52 - 21 - - 73 k.1 The system liberates 73 kJ of heat.

~ - ~+~ - ~ - lU~



Qld"'Ud-U.+ Wild
- 42 - 0 + 10.5 - 52.5 kJ

Q.db = 62.5 kJ '" QId + Qdb Qon. = 62.5 - 52.5 '" 10 kJ


Example 4.3 A piston and cylinder machine contains a fluid system which passes through a complete cycle offourprocesses. During a cycle, the sum of all heat transfers is - 170 kJ, The system completes 100 cycles per min. O>mplete the

74 = following table showing the method for each item, and compute the net rate of work output in kW.


Q (If/mjn) 0
21,000 -2,100


W (If/mln) 2,110 0

aE (lI/mln)


d-. Solu,jon Process a-b: Q = 4E+ W

0 = 4E+2 170 4E - -2l70kJ/mio

Process b--c:

Process c-d:

Q "' hE+ W 2I,OOO - 4E+0 4E " 21,000 kJ/min Q "' 4E+ W - 2100 - - 36,600+ W W oo. 34,500 kJ/min

Process d--a:

.. .. .. ..

LQ - - 170kJ

The system completes 100 cycles/min. Qab + Qbo: + Q<d + Qda " - 17,000 kJ/min 0 + 21 ,000 - 2,100 + Qdo. - - 17,000 Qdo. ... - 35,900 kJ/min

t dE - 0, since cyclic integral of any property is zero.

4H+ 4b-c + 4EH + hEM '" 0 - 2,170 + 21,000 - 36,600 + 4EM - 0 hEM"" 17,770kJ/min W_" QiH -hEd- =- 35,900- 17,770 .. - 53,670 kl/min Prou.tS .-b k Q(kJ/min) 0 21,000
W(kJ /min)

The table becomes 2,170 0

4E(kJ/min) - 2,170 21,000


Rate of work output

-2,100 - 35,900

34,500 53,670

- 36,600 17,770

""- - 17,OOOkllmin ""



Example . The internal energy of a certain substance is given by the following equation u - 3.56pv+84 where u is given in kJlkg,p is in kPa, and v is in mJlkg. A system composed of3 kg of this substance expands from an initial pressure of 500 kPa and a volume of 0.22 m) to a final pressure 100 kPa in a process in which pressure and volume arc: related by pvl.2 .. constant.
(a) If the expansion is quasi-stalic, find Q,.6 U, and W for the process. (b) In another process the same system exp~ds according to the same pressure-volume relationship as in part (a), and from thesame initial state to the same final state as in part (a), but the heat transfer in this case is 30 kJ. Find the work transfer fOf this process. (c) Explain the difference in work transfer in parts (a) and (b). Solution


u - 3.56pv + 84
.6u - U2 - UI - 3.56 (P2 v 2 - P I VI) .6U - 3.56(P2 V2 - P I V1)
Il PI VI .


V a - "! ( P:

P )111.2

5 1 11.2


.. 0.22 x 3.83 - 0.845 m) .6U - 356 (\ x 0.845 - 5 x 0.22) kJ - -356 x 0.255 - -9\ kJ For a quasi-static proces.~

AIlS. (a)

w=jpdV= P2"l-Pl"1
1 " _ (I x 0.845 - 5 x 0.22)100 .. 127.5 k1 I 1.2 Q = .6U+ W "'- 91 + 127.5 "' 36.5kJ AII.1". (a)


76=(b) Here Q '" 30 kJ Since the end states are the same, t1V would remain the same as in (a).
W = Q - t1V

- 30 - (- 91) - 121 kJ

A ns. (b)

(c) The work in (b) is not equal 10 pdV since the process is not quasi-static. Example 4.5 A fluid is confined in a cylinder by a spring-loaded, frictionless piston so lhat the pressure in the fluid is a linear function . of the volume (p - a + bY). The internal energy of the fluid is given by the following equation V " 34+3.15pJl where U is in kJ, P in kPa, and V in cubic metre. If the fluid changes from an initial state of 170 kPa. 0.03 m) to a final state of 400 kPa, 0.06 m), with no work other than that done on the piston. find the direction and magnitude of the work and heat trnnsfer. Solution The change in the internal energy of the fluid during the process. V2 - VI - 3.15 fflV2 - P1JlI) - 3J5(4xO.06 - 1.7xO.03) '" 315 x 0.189 .. 59.5 kJ Now
p ~ a + bV

170 - u+bxO.03 400 - u+bxO.06

From these two equations

o ""_ 60kN/m2 b '" 7667 kN/ms

Work transferinvoh'ed during the process

W I_ 2 -

, JpdV = J(u + bV)dV ., "

v. 2 _

= u('1 - f)+b 1
... (V2 -

'"1)[ a + tU'1 ""+ V 2 )J

7~7 ~
x 0.09 ml ]

'" 0.03 ml[ - 60 kN f m! +

= 8.55 kJ Work is done by the system. the magnitude being 8.55 kJ.



:. Heat transfer involved is given by

V2 - V t + W t_2 -; 59.5 + 8.55 = 68.05 kJ 68.05 kJ of heat flow into the system during the process.
Qt - 2 =

4. 1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.1 0 4. 11 4. 12 4. 13 4. 14 State the first law for a c105Cd system undergoing a cycle. What WDS the contribution of J.P. louie in establishing the first law? What is the calorie thcory of heat? Why was it rejeeted? Which is the pmpeny introduced by the firstlaw7 State the fim law for a clO5Cd system undergoing a ellange ohtate. Show that energy is a property ofa system. Whit are the modes in which energy is stored in a system? Define internal energy. How is energy stored in mo lecules and atoms? What is the di fference between the standard symbols of E and U1 What Is the difference between heat and internal energy? Define enthalpy. Why does the enthalpy of an ideal gas depend only on temperatUfe? Define the specific heats at constant volume and constant pressure. Why should specific heal not be defined in terms of heat transfer? Which propeny of a system increases when heat is tnmsfcrred: (_) at constant "olume, (b) at oonstant pressure? WluIt is a PMM1 ? Why is it impossible?

4. 1S

4.1 An engine ill tested by means or. waterbmke al 1000 rpm. The measUJ'ed torque of the engine is 10000 mN and the walerconsumptionofthe Im!.ke iii 0.5 mlls. ilS inlet temperature being 20C. Calculate the waler tetnpetatUfe al exit. assuming lbatthe whole of the engine power is ultimately transformed into heat wbich is absorbed by the cooling water. A,,~. 20.S"C 4 .2 In a cyclic process, heat transfers are + 14.7 kJ , - 25.2 kJ , - 3.S6 kJ and + 31 ,S kJ. What is the net work for th is cycle process? All!. 17.34 kJ 4.3 A slow dw:mical rc:action takes place in a fluid at the eonSWlt pressure of 0. 1 MPa. The fluid is $Urrounded by. perfect heal insulator during the rc:aelion which begins at lilatc I and ends at state 2. The insulation is then mnovcd and lOS kJ of heal flow to the surroundings as the fl uid goes to state 3. The following data are observed for the fluid at states 1, 2 and 3.






20 For the fluid system, calculate E1 and E), if El - 0 AM. E1 - - 29.7 kJ, EJ - - 110.7 kJ During one cycle the working fluid in an engine engages in two wock interaClions: 15 kJ to the fluid and 44 kJ from !he fluid, and three beat interactions, two ofwhieh are known: 75 kJ to !he fluidand40 kJ from the fluid. Evaluate tho magnitOOe and direetion of the !hird beat transfer. AIU. - 6 kJ A domestic refrigerator is loaded wi!h food and the door closed. During a certain period the machine coosutncs I kW h of energy and the internal energy ofthc system drops by 5000 kJ. Find !he net beat transfer for the system. AM. - 8.6 MJ 1.5 kg of liquid having a constant specific heat of 2.5 kllkg K i, stirred in a wellinsulated chamber causing the temperlIture to rise by 15Q C. Find 4 and W for

2 3

0.3 0.06


AIU. AE " 56.25 kJ, W - - 56.25 kJ The same liquid as in Problem 4.6 is stirred in a conducting chamber. During the process 1.7 kJ of heal are transferred from the liquid 10 the lIUITOuodings, while the temperature of the liquid is riling by 15"C. Find llE and Wfor!he process. AIU. AE " 56.25 kJ, W - 57.95 kJ 4.8 The pmpertiCll oh certain fluid are related as follows u - 196+0.7181 pfJ - 0.287 (I + 273) where u is the specific intemal energy (kJ/kg), I is in Q C, P is pressure (kNfml), and fJ i. specific volume (mJ/kg). For !his fluid, fmd Cy andcp AIU. 0.718, 1.005 kJ/kg K . 4.9 A system composed of2 kg ofthc above fluid expands in a friClionless piston and cylinder machine from an initial stale of I MPa, IOO C to a finallempemturc of 300c.lfthcre is no heat uansfer, ftnd the nel work for the process. AIU. lOO.S2 kJ 4.10 If all the work in the Cltpausion of Problem 4.9 is done OD the moving piston, show that the equation representing the path of the Cltpansion in the pv-pJane is given by pvL~ ... COlUtant. 4.11 A stationary system consisting of2 kg of the fluid of Problem 4.8 expands inan sdiabatic process according to pvl.l - eomIant. The initial conditions are I MPa and 200C, and the fmal pressure is 0. 1 MPa. Find Wand llU for the process.
Why is the work u-aosfer IlDl equal to

JpdV? J

An.r. W - 216.83 , llU - -216.83 k}, pdV - 434.4 kJ J 4.12 A mixture ofgases expands at CODStantprcssurc from I MPa, 0.03 mltoO.06 m with 84 kJ positive heal uansfer. Tbert' is no wad other than that done on a pistnn. Find llE for the gaseous mixture. AIU. 54 kJ The same mi:r;ture expands through the same stale path while a stirring device does 21 kJ of .....nrk on the ~ystem . Find 4, W, and Q for the process. An.r. S4 kJ. - 21 kJ, 33 kJ

4.13 A mass of 8 kg gas expands within a nexible OODtainer so that the p-V relationsbip is ofme formpVu" const The initial pressure is 1000 kPa and the initial \'Olume is I m). The fmal pressure is 5kPa. If specific internal energy of the gas decrea5n by 40 kJi\g, fiml ~ heatll'ansfer in rnagniuKle and directioo. Alii. ... 2615 kJ 4. 14 A gn of mass 1.5 kg undergoes a quasi- static expansion which follow$ a relationship , p - II '" bV, wheR' II and b are constants. The initial and final pressurcsare 1000 kPa and 200 kPa respectively and the corresponding volumes ate 0.20 m) and 1.20 m). The S]>C'Cific internal energy of the gas is given by the relation
1I - 1.5pv - 85 1r.Ji\g where p is in kPa and v is in m11kg. Calculate the net heat transfer 3/ld the maximum intcmaJ energy of the gas attained during expansion. AM. 660 kJ , S03.3kJ 4.15 The heat capacity at constant pressure of a cenain system is a funC1ioo of temperal\lre on\y and may be t.l.prtssed as

C - 2.093 ... ..!!:!!..Jf K , I ... 100 wilen: I is the temperature of the sy5lem in C. The system is beated while it is maintained at a pressure of I atmosphere until its volume iocreases from 2000 cm) to 2400 em) and ilS temperalU re increases from O C to lOOaC. (I) Find the magnitude of the heat interaction. (b) How much does the internal energy of the sy5lem increase? An.<. (a) 238.321 (b) 197.79 J 4.16 An imaginary engine receivC'S heal and ~5 ..... ork on a slow!y moving pi5l0n at such rates that thecyc1e of operation of 1 kg ofworic.ing nuid can be represented as a circle 10 em in diameter 00 a p--v diagram on wbicb 1 em - 300 kPa and I em - 0.1 m1lkg. (a) How mueh work is done by cach kg of working nuid for each cycle of operation? (b) The thermal efficiency of an engine is defined as the ratio of work done and heat input in a cycle. If the heat rejected by the engine in a cycle is 1000 kJ per kg ofworldng nl.lid, wbat would be its thermal dTiciency? AM. (I) 2356.19 kJlkg, (b) 0.702 4.17 A gas undergoes a t~nnodynamic cycle consisting ofthrce processes beginning at an initial state wbere PI .. 1 bar, VI .. 1.5 m) and VI ~ 512 kJ. Thc processes arc as follows: (i) Process 1- 2: Compression wi thpV- consta nt tOP2 " 2 har, U2 - 690 kJ (ii) Process 2- 3: Wl) = 0, Q2) = - ISO kJ, and (iii) Process 3-1: Wl i .. + SO'kJ. Neglecting KE and PE changes, determine the heal interactions Q I2 and 0 31, AM. 74 kJ. 22 kJ 4. 18 A gas undergoes a Ihermoynam ic cycle consisting of the following processes: (i) Process 1- 2: Constant preSSlln': p - 1.4 bar, VI .. 0.Q28 ml, W1 2 .. 10.5 kJ, (ii) Process 2- 3: Compression wi th pV - constant, Vl - Ul (iii) Process 3- \ : Constant volume, VI - Ul .. - 26.4 U . 111ere arc no signi ficant changes in K.E and PE. (a) Skelch the cycle on ap-V diagram. (b) Calculate the nel work forlhe

cycle in kJ. (c) Ca1culalc the heal lra nsfer for process 1- 2 (d) Show thai

l:Q - IW .
.,..10 <)'do AILI. (b) _ 8.28 kJ. (c) 36.9 k.J A cel'lllill gas of IlW$ 4 kg u contained within a piston eylinder assembly. The gas undergoes a process for which p0! - conslan!. The initial SUlle is given by 3 bar. 0.1 mI. The ehange in inlernal energy of the ga5 in the process is "1 - "I - - 4.6 kJ/kg. Find the net heallransfer for the process "'hen Ihe final volume is 0.2 Neglecl the changes in KE and PE. An.!. - 0.8 k.J An e\C(;tril: generator coupled 10 a windmill produces an a"erage elcctrical power OUtpUI of5 kW. The: power is used 10 charge ascomge baltery. Hcat.tra!l5fcr from lhe oottcl)' to Ihc SUlTOundines oceU1'5 at a constanl rale of 0.6 kW. Determine Ihe toot! amount of energy stored in the battery in 8h ofopcrat ion. A II$. 1.27 x 10" kJ A gas in a pislon-cylincicr assembly undergoes t"o procCS5CS in series. From stale 110 state 2thcn: is energy transfer by beal 10 !he gas of500 kJ, and !he gas does work on lhe piscon amounting 800 kJ. The second process, from state 2 10 state 3, is a constant pressure compression at 400 kPa. duting which Ihere is a heal transfer from the gas amounting 450 kJ. The followingdala are also known: V, - 2000 k1 and U, - 3500 kJ. Neglecting changes in KE and PE. calculate the change in volume of the gas during process 2- 3. Ans. _ 5.625 m' Air is contained in a rigid well-insulated lank wilh a "011lJTlC of 0.2 mI. The tank is fitted wilh a paddl e wheel which transfen energy to the ait at a constant rate of 4 W for 20 min. The initial density of the air is 1.2 kglml.lfno changes in KE or PE occur. determine (a) the spc:eific volume al the fin.al scale. (b) the change in spe<:ifie internal energy of the air. .4.11$. (a) 0.833 mJ/kg, (b) 20 k]fkS





"' "

First Law Applied to Flow Processes


Control Volume

For any system and in any process, the first law can be written as Q " 6+ W where represents all fonns of energy stored in the system. For a pure substance
E " Er.+I' + U

where Er. is the K.E., 1' the P.E., and U the residual energy stored in the
molecular structure of the substance. Q : &r.+l!.p+l!.U+ W (5. 1) When there is mass transfer across the sytcm boundary, the system is called an open system. Most of the engineering devices are open systems in vo lving the flow of fluids through them. Equation (5. 1) refers to a system baving a particular mass of substance. and is free to move from place 10 place. Consider a steam turbi ne (Fig. 5.1) in which steam enters at a high pressure, does work upon the turbine rotor, and then leaves the turbine at low pressure through the exhaust pipe. If a certain mass of steam is eonsidered as the thennodynamie systcm, then the energy equalion becomes Q "' 6K +6p + 6U+ W and in order 10 analyze the expansion process in turbine the moving system is to be fol1owed as iltravels through the turbine, laking into aceountlhe work and heat interactions all the way through. This method of analysis is similar 10 thai of Langrange in fluid methanics.


Control surlace :/

,. "
Fig. 5.1 F'Ww frouu ilWfllqilll WQ,J:
~nd 1ac~1

Exhaust ~pe

Although the system appr.oach is quite valid, there is another approach which is found to be highly convenient.lnsteadofcontentrating attention upon acenain quanti ty of fluid, which constitutes a moving system in flow process, attention is focussed upon a certain fIXed region in space called a control volume through which the moving substance flows. This is si milar to the analysis of Euler in fluid mechanics. Todistinguish the two concepts, it may be noted that while the system (dosed) boundiuy usually changes shape, position and orientation relati ve to the observer, the control volume boundary remains fixed and unaltered. Again, while mailer usually crosses the control volume boundiuy , no such flow occurs across the system boundary. The broken line in Fig. 5. 1 represents th e surface ofthe control volume which is known as the control suiface. This is the same as the system boundary of the open system. The method oanalysis is to inspect the control surface and account for all energy quantities transferred through this surface. Since there is mass transfer across the control surface, a mass balance also has to be made. Sections I and 2 allow mass transfer to take place, and Q and Ware the heat and work interactions respecti vely.

5.2 Steady Flow Process

As a fluid flows through a certain control volume, its thermodynanic properties may vary along the space coordinates as well as with time. If the rates offlow of mass and cnergy through the control surface change with time, the mass and energy within the control volume also would change with time. 'Steady flow' means that the rates of flow of mass and energy across the control surface are constant. In most engineering devices, there is aconstant rate offlow of mass and energy through the control surface, and the control volume in course of time alla ins a steady state. At the steady stale of a system. any thermodynamic property will

mn'e a ./Ued volue



ptJrticular loca/ion. and will 110/ alter with time.

Thermodynamic properties may vary along space coordinates, but do not vary with time. 'Steady state' means that the state is steady or invariant with time.

5.3 Ma.u Balance and Energy Balance in a Simple Steady Flow Process
In Fig. S.2, a steady flow system has been shown in which one stream of fluid
enten and one stream leaves the control volume. There is no accumu lation of mass or energy within the control volume, and the properties al any location within the control volume are steady with time. Sections 1.1 and 2.2 indicate, respectively, the entrance and exit of the fluid across the control surface. The following quantities arc defined with reference to Fig. S.2.

f .... .. ...................... ...... .

Fig. 5.2 Sltady fow Ptouu


A 2-cross-section ofstrcam,


wI ' wr-mass flow rate, kg/s

p"pz-j)rcssure, absolute, N/ml v" t'2---specific volume, m)l1:g u" " .--specific internal energy, Jlkg V" V z- vc1ocity, mis Zl' ~--clevation above an arbitrary datum, m

~---net rate ofhcat transfer through the control surface, Jls

dW -=-:.:...!..-net rate of work transfer through the control surface, Jls exclusive ofworit done at sections I and 2 in transferring the fluid through the control surface. r-time,s. Subscripts I and 2 refer to the inlet and exit sections.



5.3.1 Mrw Balsna

By the conservation of mass, if there is no accumulation of mass within the control volume, the mass flow rate entering must equal the mass flow rate leaving, or
w! " wz
A!V1 '" A2V 1

(5 .2)

This equation is known as the equation ofcontinuity.

5.3.2 Eangy Bmart

In II. flow process, the work transfer may be of two types: the external work and theflow work. The external work refers to all the work transfer across the control surfaceothcrthan that due IOnonnal fluid fon:cs. In engineering thermodynamics the only kinds of external work of importance are shear (shaft or stining).wOrk and electrical work. In Fig. 5.2 the only external work oceurs in the fonn of shaft work, W1 The flow work, as discussed in Sec. 3.4, is the displacement work done by the fluid of mass dm l at the inlet section I and that of mass din l al the exil section 2, which are (-Plvldinl) and (+pzvzdmz) respectively. Therefore, the total work transfer is given by

In the rate fonn.


(tw .. (tWa (5.4) d1' d1' Since there is no accumulation of energy, by the conservation of energy, the total rate of flow of all energy streams entering the control volume must equal the IOtal rate of flow of all energy streams leaving the control volume. This may be expressed in the following equation.

wzez + - dr dr Substituting for II W from Eq. (5.4) wlel +

~ =





where e1and el refer to the energy carried into or out oflbe control volume with unit mass offluid.

The specific energy e is given by

e ; e~+ ep + u

V' - + Zg + u 2 Substituting the expression for e in Eq. (5.5)


w ,(Vl + Z\g+ UJ) + W1PtVl + ..!!.Q. 2 dr

- wl ( 2 + Z2g + U2


+ w Z P2VZ+


l i W ,(h + V + Zlg)+ ~ 2 dr

= W2 ( h2+T+~g


dW. +"""'d'r
dm dT


h - u+pv. .

And, since Dividing Eq. (5.7) by dm dr

letw z w\"' wZ "'

(l .8) 2 dm Equations (5.7) and (5.8) are known as steady flow energy equorio/U (S.F.E.E.), for a single stream offluid entering and a single S\Jeam offluid leaving the control volwne. All the tenns in Eq. (5. 8) represent energy flow per unit mass of fluid (llkg) whereas all the tenus in Eq. (5.7) represent energy flow per unit lime (J/kg). The basis of energy flow per unit mass is usually more convenient when only a single stream of fluid enters and leaves a control volume. When more lhan one fluid stream is involved the basis of energy flow per unillimc is more

"' hl +....:L+~+..::..:..:....!



Equation (5.8) can be written in the following fonn,

Vl-V\ , , Q - W. "' ( 2- 1) + 2 ' + g(2; - ZI)
-2 -2


where Q and


refer to energy transfer per unit mass. In the differential form.

the SFEE becomes

(5.10) When more than one stream of fluid enters or leaves the control volume (Fig. 5.3), the mass balance and energy balance for steady flow are given below.

~ : '- - ~
: 3


: .. ..t-dQ .. ~L.-~~~~ -..



FIg. 5.3 Situ, floll1 ptm i~fHllDi"l ' - /llIill stmstfIJ lSI tJu {1Ik1 OM ail of tJu mtlTof IH!fllllll

Mass balance
WI+W2 "" Wl+W. AIVI + A 2V 2 = A)V) .+ A.V.

(5. 11 )




Energy balance
WI (hI

+Zlg)+Wl(~+ V! +~g)+~

= WJ

Vi (h1 +T+Z1g

1 (

+W4 h4 +


+Z.g +(i'!



The steady flow energy equation applies to a wide variety of processes like pipe line flows , heat tnmsferprocesses, mechanical power generation in engines and rurbines, combustion processes, and flows through nozzl es and diffusors. ln certain problems, some of the terms in steady flow energy equation may be negligible or l':ero. But it is best to write th e full equation first, and then eliminate the tenns which are unnecessary.

5.4 Some Examples of Steady Flow Processes

The following examples illustrate the applications of the steady flow energy equation in some of the engineering systems.

5.4.1 Nozzh au DifJiuor

A nozzle is a device which increases the ve locity or K.E. ofa fluid at the expense of its pressure drop, whereas a diffusor increases the pressure of a fluid at the

Frnl LDw API'u.J tD Flow PU(tS,US


e,,-pense of its K.E. Figure 5.4 shows a nozzle which is insulated. The steady flow energy equation of the control surface gives

" "

m --H-

" "


..... . .......


"'C'c.s. ,

--++-_ m


fig. 5-'

Suady flow p'~m inDllwing O~t fluid flrtllm III lilt inltt llrui III txil Df tilt control Vfl/Umt


~ ... 0,

d W5 .. O. and the change in potential energy is ze ro.


The equation reduces to h + - ' - h, + - ' '2 2 The conlinuity equation gives



(5 .14)

w . A! VI ... ~


When the inlet velocity or the 'velocity of approach ' V I is small compared to the e"-il velocity V l' Eq. (5. 14) becomes
h, = h, + - '


where (hi - n2) is in Jlkg. Equations (5. 14) and (5 .1 5) hold good for a diffusor as well.

5.4.2 Tllrottli1lf DefJice

When a fluid flows through a constricted passage, likr a partially opened valve, an orifice, or a porous plug, there is an appreciable drop in pressure, and the flow is said to be throttled. Figure S.s shows the process of throttling by a partially opened valve on a fluid flowin g in an insulated pipe. In the steady-flow energy Eq, (',8),



.. o


4W.. - 0



f'iS. 5.5

----. -_ ....""""" ...... FUuo 111.0.,11




and the changes in P.E. arc very small and ignored. Thus the S.F.E.E. reduces 10
Vl V2 ',+_1 mh2+ - ' 2 2
Often the pipe velocities in throttling are so low that the K.E.tenns arc also negligible. 50

or the enthalpy ofthefluid be/ore throttling is equal to the enthalpy o/thefluid after throttling.

Turbines and engines give positive power output, whereas compressors and pumps require power input. For a turbine (Fig. 5.6) which is well insulated, the flow velocities arc often small, and the K.E. tettlS can be neglected. The S.F.E.E. then becomes

Fig. 5.6 FL.", IAro,.,," IIIM.biu



- (hi-nil

It is seen that work is done by the fluid at the expense of its enthalpy. Similarly. for an adiabatic pump or compressor, work is done upon the fluid and Wis negative. So the S.F.E.E. bec~es

h l~ h2_W,

W. - hz- nl m The enthalpy of the fluid increases by the amount of work input.

5.... Heal &Clulttgtr

A heat exchanger is a device in which heat is transferred from one fluid to anoM. Figure 5.7 shows a stearn condenser, where steam condensers outside the rubes and cooling water flows through the rubes. The S.F.E.E. for the C.S. gives

Fig. 5.7

$Ita .. CfIMmsn

wenl + w, hz '" W e h) + w, h4 w,(hl - h4):= we (hl - hl) Here the K.E. and P.E. terms are considered small, there is no external work done, and energy exchange in the form of heal is confined only between the two fluids, i.e., there is no external heat interaction or heat loss. Figure 5.8 shows a steam desuperheater where the temperarure of the superheated steam is reduced by spraying waler. If WI ' w1, and Wj are the mass or

110w rates of the injected water. of the steam entering. and of the steam leaving, respeetively, and hI ' h2' and h3 are the corresponding enthalpies. and ifK.E. and P.E. terms are neglected as before, the S.F.E.E. beeomes "'Ihl + wzh2 - "'lh1 and the mass balance gives "'1 + "'2 - "'1


:,.,(,!l__ I~_


High temperature $learn

2 !

~ C.S.

' i

: 3


: -----------! ...................... j
FIg. 5.8 Slallll dtJupnluattr


ComparisoD of S.F.E.E. with Euler and Bernoulli EquatioD'

The steady flow energy Eq. (5.8) can be written as

dW .!e.=(h -h)+ V2 -VI + (Z2- ZI)g + ..::.:..:i dm 2 I 2 dm In the differential form the S.F.E.E. becomes
dQ = dh + VdV +gdZ+dW. (5. 17)



where it Q and it W. refer to unit mass of the substanee. Sinee h '" u + pv and dQ= du + pdv (for a quasi-static path involving only pdv-work). Eq. (5.1 7) ean be written as du + pdV '" du +pdV + Vdp + VdV + gdZ+ dW. For an inviscid frictionless fluid flowing through a pipe Vdp+VdV + gdZ - O (5.18)

This is thl:Eulerequatiofl. lfwe integrate between two sections I and 2 ofthe pipe



f"dp+ fYdY+ fgdZ =0

For an incompressible fluid, v = constant

V(P2-P l) +

....:.L _....:.L + g(~ - ZI) = O




Since the specific "olume v is the reciprocal of the density p, we have

l!!..+ _ l + Zg= J2..+ _ 1 + Z2g P 2 1 P 2




. + -v' + Zg .. constant

This is known as the Bernoulli equation, whi~h is valid for an inviscid incompressible fluid. It can also be expre ssed in the following fonn

,a{pv+ ~2 +gz) .. o


where v is constant and ~ (,' ,Jmeans 'increase in" The S,F,E,E, as given by Eq, (5, 18) or Eq. (5.17) can be written with (u + pp) substituted for h, as follows:

Q - W, .. &(u+pv +


+ gZ )


A eomparison of Eqs (5.22) and (5.23) shows that they have several teons in common. However, while the Bernoulli equation is restricted to frictionless incompressible fluids, the S.F.E,E, is not, and is valid for viscous compressible fluids as well. The Bernoulli equation is, therefore, a speeiallimiting case of the more general steady flow energy equation.


Variable Flow Processes

Many flow processes, such as filling up and evacua ting gas cylinders, are not steady. Such processes can be analyzed by the control volume techni que, Co nsider a device thro ugh which a fluid is flowing UDder non-steady state conditions (Fig, 5.9), The rate at which the mass offluid within thecontrol volume is accumulated as equal to the net rate of mass flow across the control surfac e, as given below

d'T "' w1 - WZ "' Tr -d'f

where mv is the mass of fl uid within the control volume ill any instant,

dm v

- dml

dm l

(5, 24)


Over any finite period of time

&m v - 4m 1 - 4m2
, C~

._..................1 ..........



Fig. S.9

Y"ridk fow pt_

rate of accwnulation of e nergy within the contro) volume is Iua) to the net rate of energy flow across the control surface. If E~ is the energy of fluid within the control Yolwne at any instant. Rate of energy increase - Rate of energy inflow - Rate of energy outflow


- Wz ~ +-+Z:J.g - dW, , dr




mV' Ey " ( U+ , - +mgZ ) y

where m is the mass of fluid in the contro) volume at any instant.

dEy mV' - - - d( U+ - + mgZ ) drdr 2 y

V' +Zzg _ _ _ ". + _2 2 _ dW. ( -2 drdr



Figure 5.10 shows all these energy flux quantities. For any finite time interval, equation (5 .27) becomes



d. , .,,-

,,(.,. , } l,g

FJg. 5.10

-'-(u+mV2 +mv~ V
dr 2

l. .......................... \


Etttrg f/IUU i~

WlUkU] J'flknl

tlEV - Q-Wx+ J(h l +

V.} +Zlg)dm

-J(h.!+ V! +Z2g)dml
Equation (5.26) is the general energy equation. For steady flow.


"""dt - 0,
and the equation reduces to Eq. (5.7). For a closed system from Eq. (5.26),


= 0, w2 = 0, then

dEy - 4Q - 4W" or, 4 Q - dE + 4Wo.

as obtained earlier.

5.7 Example of a Variable Flow Problem

Variable flow processes may be analyzed either by the system technique or the conttol volume te<:hnique, as iIIutrated below. Consider a process in which a gas bottle is fi lled from a pipeline (Fig. S.II). ln the beginning the bottle contains gas ofmassm t al statep. , It. Vt, hi and u l . The valve is opened and gas flows inlo the bottle till the mass of gas in th e bottle ism2 at state Pl. f 2 v2 hl and U2' The supply to the pipeline is very large so that the state of gas in the pipeline is constant atpp Ip. up> hp, up' and Vp .

Syttem Technique Assume an envelope (which is extensible) of gas in the

pipeline and the rube which would eventually enter the bottle, as s hown in Fig. 5.11.


94=Envelope 0( System boundary

~l~..~~ --~--<:::::::: ~---(--:--:--:--~-~ --t_C : ..:: ~: --:-=~J'_Envelope) ..~--~--~ ~"-__ __


Pipe I nti

System boundary


Fig. 5.11
8~114:fiUi~ procus

Energy of the gas before fill ing

EI-mtUt+(ml - mt)(V! +U P)
where (ml - m t ) is the mass of gas in the pipeline and tube which would <mterthe bottle. Energy of the gas after filling 1 " m2 ul
llE - : - 1 - m:ul - [mIUI

+ (ml - ml{ Vf + up )]


The P.E. terms are neglected: The gas in the bottle is not in motion, and so the K.E. tenns have been omitted. Now. there is a change in the vol ume of gas because of the collapse of the envelope to zero volume. Then the work done

If' - Pp (V2 - VI) " p.,lO - (ml- ml)vp) - -(m2- ml)p p Vp

:. Using the first law for the process Q""llE + IV
- m2uZ - mlu l - (m 2 - ml{ Vf

+ up ) --{nlz - ml)ppvp

"' nl2Ul-mIUI-(ml-ml)(V! which gives the energy balance for the process.



Control Volume Technique Assume a control volume bounded by a control surface, as shown in Fig. 5.1 1. App lying the energy Eq. (5.27) to this ease, the following energy balance may be wrinen on a time rate basis


Finl LIlli! Applitd tD Flow PrrKtmJ


dEv .. +(h + drdrPZdr


V; )dm


Since . n,.~ Vp an: constant, the equation is integrated to give for the total

. .

l:1Ev -"' Q+ ( hp+ Now

Vf }ml-ml)
- mlUt

!lEv '" V 2-

VI = m2u~

Q- m2U2- mIUI - (\+ Vf } m 2- ml )

This equation is the same as Eq. (5.30). If i.e., the bottle is initially evacuated.

ml .. 0,

Q=m u (hp + V; ) 2 2- m 1
Again, ifQ - 0 and hp

V' T'


o.. mzuz - m;!lp UZ " hp llp+PpVp Thus, flow work (ppv.,) is convcned to increase in molecular internal energy
cvTl - cp Tp
T2 "" yTp If Tp -= 27 + 273 -= 300 K. thcn for air If the gas is asswned ideal.

(liZ -


Tl "" 1.4 x 300 '" 420 K

or, 12 '" 147C Therefore, in adiabatically filling a bottle with airal 27C, the gas tc:mpc:rature rises to 147C due to the flow work being convened to inu:mal energy increase.

5.8 Discharging and Charging a Tank

Let us consider a tank discharging a fluid into a supply line (Fig. 5. 12). Since c1
W~ -'"

0 and dmin '" 0, applying firstiaw to the control volume.

dUv -"' dQ +(h+





Assuming K.E. and P.E. of the fluid to be small and c1Q " 0




:.v.- .........I

e., .

t ........... ;

fig. 5.1!

~", ..iI discwli", /I


d(mu) - helm mdu +udm - uelm

+pv dm

~ -~
m pv

vm .. const.

tJdm+mdv - O

dm dv --m v '" From Eqs (S.32) and (S.33).


__ dv

pv V d(u+pv} - O

or (lQ - O which shows that the process is adiabatic and quasi-static. For charging the tank

J(hdm).. .. IlU

v -

mzuz -

m1U l


mr/tp - mZu2 - mlul where the subscriptp refers totheconstant state of the fluid in the pipeline. If the tank is initially empty, mt " O. mr/tp " m"'1
mp - m z

hp -


Enthalpy is converted to internal energy.


If the fluid is

an ideal gas, the tempaature of the gas in the tank after it is

clJarxed is given by



Example 5.1 Air flows steadily at the rate of 0.5 kg/s through an air compressor. entering at 7m/s velocity, 100 kPa pressure, and 0.95 m 3/kg volume, and leaving at 5 mis, 700 kPa, and 0.19 m)lkg. The internal energy of the air leaving is 90 kJlkg greater than that of the air entering. Cooling water in the compressor jaclc.ets absorbs beat from the air at the rate of 5g kW. (a) Compute the rate of sbaft work input to the air in kW. (b) Find the ratio of the inlet pipe diameter to outlet pipe diameter. Solutio" Figure & . 5. 1 sbows the details of the problem.

<a) Writing the steady flow energy equation. we have

..1 UI + P1 V1+~VL2 "l 2


+ ZIg) +


W ( U2+P~V2+++ZUl

aw +M

dW Vi-VLl :~=-"L(UI -U L)+(P2VI-PtVL)+ 2 +(Zz- Z1}g +~




_ -0.5 ~[90.!L +(7 x 0.19 -I XO.95)IOO!:!. skg kg 2 + (5 _72)X\0-) kJ +OJ-58kW 2 kg - -0.5 [90 + 38 - 0.012) IcJ/s -58 kW
.. -122 kW
..flU. (a)


98=Rale of work input is 122 kW. (b) From mass balance, we have

AIVI AV W ---"-v
1 1
VI 2

~ .. 5-.~= 0.95
A2 v2

x2. .

AIlS. (b)



!!.L .. .J3.57

.. 1.89

Example 5.2 In a steady flow apparahJ s, B5 kJ of work is done by each kgof fluid . The spedfic volume of the fluid. pressure, IlDd velocity al the inlet are 0.37 m1lkg. 600 kPa, and 16 mls. The inlet is 32 m above the floor. and lhe discharxe pipe isat floor level. The discharge conditions are 0.62 mllkg. 100 kPa. and 270 mls. The lotal heal loss between the inlet and discharge is 9 kJ !kg o f fluid. In flowing through thisapparntus, does the specifil; internal energy inl;TellSC
or decrease, and by how much?

Sa/ution Writing the steady flow energy equiltion for the control volum e. as shown in Fig. Ex. 5.2.

_Eq 0 '=il ' -" ---"'--"--"---"'--~---~'>"~-:"" C.S. w_ 135 kJ VI- 0.37m1I kg i , ":!- o.62m' lkg

Pi-600 kPa
VI _ 16ml.

C.V .

i,~ ' 2

P2 "' I00kPa
Vl - 270mls


, ................. j
FIg. Es. S.2

4 -0


UI - Ut = (PZvl - PI VI ) +

vtvl 2

dW. +(Zz-ZI)g+ dm - ~

"'(I x 0.62 - 6 x 0.37) x 102 + (270 _ 16 ) X 102 + (- 32 x 9.81 x 10-1) + B5 - (- 9.0) - - 160+36.45 - 0.314 + 135 + 9 . < .. 20. 136 kJ /kg Specifil; internal energy decreases by 20.136 kJ.



uw App}itd wFl#w l'rmu


Ezample 5.3 In a steam power station, steam flows stedily through a 0.2 m diameter pipeline from the boiler to the turbine. At the boiler end, the steam cond itions are found to bc:p" 4 MPa, z- 400C,h .. 3213.6 kJlk.g, and II " 0.073 mJlkg. At the turbine end. the conditions are fOWld to bc:p " 3.5 MPa,r'" 392C, h " 3202.6 kJlkg. and p " 0.084 m' lkg. There is a heat loss of8.S kJl kg from the pipeline. Calculate the steam flow rale.

Solution Writing the steady flow e nergy equation for the eontrol volum e as shown in Fig. Ex. 5.3

vi z,g + dW, h ,+ -V,' + ZIg+ ~ = h2+-+ 2 dm 2 dm

~ uuuu . . . . .::~~.. . . . .
~r. Z ~uu
dO diiI
z _ 8.SkJ/kll

f=l ...u . .........u. __

Fig. Ex. 5.3

Here, there is no change in datum. so change in potential energy will be zero. Now
A1 V1 '" A1V1



~_..:l v_O.084V_II'V V2 "" AtVI ' -']1-'1 VI A2 VI 0.073

dWx - 0 dm h, +...:L +.=l<.. .. h, + - ' 2 dm 2




,V,2_V,2)xI0-J '-'. C -"-, . !..o"'-_


.. hi -

Vf(l .IS2 -1 2) - Sx 101 Vl - 1S,6S0 m1/s2

VI '" 125.1 mls AV

dm - 32 13.6 - 3202.6 + (- 8.5) = 2.5 kJlkg

(In h2 + ..::x..

.!!.., X (0.2)2 m 1 x 125.1 m /s

:. Mass flow rale

w :< ..::L:..l '" VI


0.073 m 1I kg

53.8 kgls

lOO=Eumple 5.4 A certain water beater operates under steady flow eonditions receiving 4.2 kg/a of water at 75C temperature, enthalpy 313.93 kJlkg. The water is heated by mixing with steam which is supplied 10 the heater .at temperature IOO.2C and enthalpy 2676 kJlkg. The mixture leaves the heatel'as liquid water at temperature 100C and enthalpy 419 kJlkg. How much steam must be supplied to the heater per hour?


By mass balance across the control surface (Fig. Ex. SA)

---- ----------1


3 3

Byenergy balance

By the nature of the process, there is no shaft work. Potential and kinetic energy tenns are assumed to balance zero. The heater is assumed to be insulated. So the steady flow energy equation reduces to

+ w1ft, -

w1h 1

4.2 x 313.93

+ w2 x 2676 - (4.2 + w2) 419

w2 - O.196kgls .. 70S kgfh

Example 5.5 Air at a tempemture of ISoC passes through a heat exchanger at a velocity of 30 mls where its temperature is raised to HOOC. It then enters a turbine with the same velocity ofJO mls and expands until the temperature falls 10 6S0C. On leaving the turbine, the air is taken at a velocity of6O mls to a nozzle


wbere il expands unlil the temperature bas fallen 10 5000C. lfthe air now rate is 2lr.gls, calculale (8) the rate of heat transfer to the air in the heat exchanger, (b) the power output from the turbine assuming no beat loss, and (c) the velocity al exit from the nozzle, assuming DO beat ]OS5. Take the enthalpy ohiT as h .. c wbere c p is the specific beal equal 10 1.005 kJlkg K and t the temperature. Solution As sbown in Fig. Ex. 5.5, writing the S.F.E.E. for the beal exchanger and eliminating the terms not relevant,


~~+ ~2 +Zlg) + QI_2 " ~~+

AlIS. (a).

wh l + Ql-1 '" whl Q I-2 = It{h1 - hi) " wcp (t1 - tl)

-t, .. l!l oC.I:L " 8OO"C

VI " 30 mI$. v 2 " 30 m/S ~ . 650"C. 60 mill

.. 2 x 1.005 (800 - IS)

'" 2.01 x 785 : 1580 kJ/s


Fig. EL 5.5

Energy equation for the turbine gives

.J v' +hl WlT

v1 Vl
1 -

z whJ+WT + WT


) + (h]-hv " Wylw 2 2 2 3 (30 - 60 ) X 10- + I 005 (800 - 650) ... W,.'w 2 .

T --1.35+ 150.75 W

.. 149.4 kJ/kg W T " 149.4 x 2 kJ/s = 298.8 kW

AIU. (b)


Writing the energy equalion for the nozzle



2 2 y 2 _ V~ 4 - '4 ) 2 } "" c:(' p J


+ hJ "'~ + h4


-Vl ~ 1.005 (650 - 500) x 2 X IOJ

vI ";' JO.1Sx 1<t+O.36x 10

= 30.,51 X :. Velocity at exit from the nozzle V4 = 5S4m1s

= 301.50 X 10J m1/s 2

10 m2/s1

Ans. (e)

Example 5.6 The air spttdofa turbojet engine in night is 270 mls. Ambient air temperature is - ISoC. Gas temperature at outlet of nozzle is 6OO G C.

Corresponding enthalpy values for air and gas are respectively 260 and
912 kJlkg. Fuel-air ratio is 0.0190. Chemical energy af the fuel is 44.5 Ml/kg. Owing to incomplete combustion 5% oftbechemica! energy is not released in the reaction. Heat loss from the engine is 21 kJlkg of air. Calculate the vebcity o(the exhaustjcl.

Solution Energy equation for the turbojet engine (Fig. Ex. 5.6) sives

"' , '''" ,

._ _ ._ ..... ~ c.s.


......... ..........................
Fig. Ex. 5.6




W .(h . + f) + WrEr+ Q -W.(h . + V! +E.)

2 3 ( 260 + 270 ; 10- ) + 0.0190 x 44500 - 21 - 1.0190 ( 912 +
V' X 10- '

+ 0.05 ~.~ :: x 44500

260 + 36.5+845 - 21 '" 1.019912+ (

V' X 10-' 2 +42

1 1

....:.L .. 156 X lOJ m 2ts1


VI .. .J3IT x lQO mls Velocity of exhaust gas. VI - 560 mls


Eumple 5.7 In a reciprocating engine. the mass of gas occuping the clearance volume ism c kg at 5tatepl' UI' 171 and hi. By opening the inlet valve. mrkg of gas is taken inlo the cylinder. and at the conclusion of the intake process the state of the gas is given bYP1' U1 v1 h1. The state of the gas in the supply pipe is constant up' vp' hp> Vp' How much heat is transferred between the gas and is given by and the cylinder walls during the intake process? &Iution Let us consider the control volume as shown in Fig. Ex. 5.7. Writing the energy balance on a lime rate basis




= ~ _ I1W
dr dr

+ ["'+

V; ] dm 2 dr

"'" ....

~.~ -~':Q'''9:'

': ;' '-..--'..''.1'l ..'-.. '-..' -..-'-..-'-....-.. T ....t . '''' . ,1 /

es ..

, ,

... - ..


Fig. U. 5.7

Withhp and Vp being constant. the above equalion can be integrated to give for the total process

bEy - Q- W+(",+
o.Ey '" Vl

Vl ) mr
m rJ Ul -




Q- <mC+mr)U l - mCUI- m { ", + ;) +w

E:u.mple 5.8 The internal energy of air is given by U - Uo + 0.718/ where U is in kJfkg, Uo is any arbitrary value of U at OC, kJlkg, and 1 is the temperature in C. Also for air,pv - 0.287 (1 + 273). wherep is in kPa and V is in m1flcg.


104 = A mass ofair is stirred by a paddle wheel in an insulated constant volume tank. The velocities due to stirring make a negligible contribution to the internal energy of the air. Air flows OUI through a small valve in the lank al a rate controlled to keep the temperature in the tank CODStant. At II cenain instant the conditions arc as follows: tank volume 0. 12 m 3, pressure I MPa, temperature 150"C. and power to paddle wheel 0. 1 kW. Find the rate offlow ofairoul of the tank at this instant. Solullon Writing the energy balance for tbe control volume as shown in Fig. Ex. 5.8

dEv .. tiW -(h) dm dr dr P dr

W " O. l kW

r' ............... ...... .. ........

I T.nk



L~ ;;;;;;
FIf. Ex. .5.8

___ - 'C~:~!

Since there is no change in intemal energy of air in the tank.

h . dm = dW



hp u+pV. U " 0 at 1- 0 K "'-273"C U - Uo + 0.718 1 0= Uo + 0.7 18 (- 273) uo " 0.718 x 273 kJlkg


u " 0.718 x 273 + 0.7181

- 0.718 x (t + 273) kJ/kg hp = 0.7 18 (I + 273) + 0.287 (I + 273) h p " 1.005 (I + 273) h p '" 1.005 x 423 .. 425 kJ/kg

df - h;df


I dW


0.1 kJ /s = 0.236 x 10-1 kgls 425 kJ/ kg - 0.845 kg/h

This is the rate at whicb air flows o ut of the tank. Example 5.9 A wellinsulated vessel of vol ume Y contains agas al pressurepo and temperature te. The gas from a main at a uniform temperature II is pumped into the vessel and the inflow rate decreases exponentiallywitb time according to ~ 0,.....", where a is a constant. Determine the pressure and te mperature of the gas in the vessel as a function of time. Neglect the K.E. oftbe gas entering the vessel and assume that the gas follows the relation

m m

fW " RT, where T= t + 273

and its specific heats are constant. (i) lfthe vessel was initially evacuated, show that the temperature inside the vesse l is independent of time. (ii) Detennine the charging time when the pressure inside the vessel reaches thaI of the main.

Solution Since the vessel is well insulated, Q.. 0 and there is no external work
transfer, W '" C. Therefore,

dE, , -" ,dm ,-= df df



where hi is the enthalpy of the gas in the main. On integration,



Imo (I -e....' )

where Eo is the initial energy of the vessel at Ihe beginning of the charging process, i.e. E - 0 at r - O. Neglecting K.E. and P.E. changes, by energy balance
(1 )


d1 = moe
On integration,



M " Mo + ~ m ~o~(1~-~,~ -_ .!. )


where Mo is the initial mass of the gas. Eliminating M from Eqs (I) and (2),

{Mo +

:0 (I-e-



u - Mouo

. mo( , 1-,.~, )(uI+ RT,)


MrFy(T - TO> - "'0 ( l - a ..... f ){c y(TI - 7)+RT1}



+ "'0 (1- c-U)cp7i


{ Mo +




P _ MRT '" _!i_ J MoCyTO + "'0 (1- C-~)Cp7i) Y YC y l a

'" PI) + --;;v( l - c.....f )yT1
The above two equations show the temperature and pressure of the gas in the vessel as functiorus of time. (i) If Mo " 0, T "" rT1' i.e., the temperature inside the vesse l becomes independent of lime and is equal to rT] throughout th e charging process. (ii) The charging process will stop when pressure inside the vesel reaches thai of the main. The charging time can be found by setting p = P1 in the pressure relation


PI - PO ..

mOR _ -"'oRr7i - - -- COf gTI

aY /.IY

By rearrangement,

5. 1

Explaio Ihe


approach and 1he conlrol volume approach in the analysis of

a flow proce5!.
What is a steady flow proce.u? What is !teady state? Write the steady flow energy equation for a single stream entering and a single stream leaving a control volume: and elpJain the various teons in it. 5.4 Give the diffcrmtial form nflbe S.F.E.E. 5.5 Under what condi tions does the S.F.E.E. reduce 10 Euler's equal ion? 5.6 How does Bernoulli's equation compare with S.F.E.E.? 5.7 What will be the \'clocity ofa fluid leaving a nozzle. if the yelocity nfapproach is vef)'small1 S.8 Show that the enthalpy ofa fluid before throttling is equalln thai after tbrottling. 5.9 Write the general energy equation for a variable flow process. 5.10 Wltal is the SYlilem techniquc in a bottlefilling proccss? S. II Explain the eontrol voll1ll'\e technique in a variable flow pJ'OCC'Ss. S.J




5.1 A blower handles I kg/sofHirat 20C andeonsumes apowerof IS kW. The inlet and outlet vdocities ofair are 100 mI, and ISO mls respectively. Find the exit air
tempenture. assuming adiabatic cond itions. Take c p of air as 1.005 IcJlkg.K. An!. 28.38C A turbine opellltes under steady flowcondilions. ~eiving steamtl tile following statc; pressure 1.2 MPa, temperature 18S"C, enthalpy 27805 kJlkg. ve loe ity 33.3 mls and elevation 3 m. The steam leaves the turbine l Ithe following state; pressure 20 kPa. enthalpy 205 12 kJlkg. velocity 100 mis, and elevation 0 m. Heat is lost to the surroundings al the rate of 0.29 kJI,. If the rale of stearn flow through the tusbine is 0.42 kg/so whal is the power outpul of the tusbine in kW1 AM. 112.5 1 kW A nozzle i5 a device for increasing the vclocily of a steadily flowing slream. At the inlet to a certain noule, the enthalpy of the fluid passing is 3000 kJlkg and the velocity is 60 mls. At tile discharge end, tile enthalpy is 2762 kJlkg. The nozzle is horizootal and there is negligible heat loss from it. (a) Find the velocily l al exit from the noulc. (b) If the inlet area is 0. 1 m and the specific volwne al inlet is 0. 187 m1lkg, find the tna$s flow rate. (e) If the specific volume at the noule exit is 0.498 m1lkg, find the exit area of the noule. An!. (a) 692 .5 mis, (b) 32.08 kg/s (c) 0.023 ml In an oil cooler. oil flows steadily through a bundle of metal tubes submerged in a steady sleam of colling waler. Under steady flow conditions. the oil enters at 90C and leaves at 30 C, wh ile the water enters at 2S C and leaves It 70 C. The enthalpy of oil at t"C is given by h - 1.6S I '" 10.5 x 10" !dlkg What is tile cooling water flow required for cooling 2.78 kgls of oil ? AIlS. 1.473 kg/s A thermoelectric generator eonsislS of a seri es of semiconductor clements (Fig. P. 5.5), heated on one side and coolcd o n the other. Electric current flow is produced all a result of energy transfer as heal. [n a panicular experiment the








Fig. P.5.5

108=cum:nt was measured to be 0.5 amp and the electrostatic potential at (I) was 0.8 volt above that at (2). Energy tmnsferM heat to the hot side of the gcncmtor was taking place at a l1ue ofS .S wans. Determine the mte of energy transfer as heat from the cold side and the energy conversion cfficiency. All.!". Ql - 5.1 watts. 1] - 0.013 5.6 A turbocomprcssordclivers 2.33 ml/s of air at 0.276 MPa. 43 C which is heated at thi s pressure to 4300C and finally expanded in a turbine which dclivCl1l 1S60 kW. During the expansion, there is a heal transfer of 0.09 MJ/s to thc surtoUlldings. Calculalc thc turbine CXhaUSI ICmpernt~ i f changes in unclic and potential energy arc negligible. Take c, " 1.005 kj/kgK ,flu. 157 C 5.7 A reciprocating air compressor takcs in 2 ml/ min al 0. 11 MPa, 20 C which it deliveR at 1.5 MPa. 11 1C to an afkreookT where the air is coo led at con.Ul1 pre5sure 10 2S C. lbe power absorbed by thecomp tcssoris 4.15 kW . Delermine the heal transfer in (a) lhe comptcssOl", and (b) the cooler. Stale your assumptions. An.!. - 0.17 kJ/s, - 3.76 kJls. 5.8 In a waler cooling tower airenlCl1l al a heighl of I m above the groUfld [cve! and leaves al a height of 7 rn. The inlel and outlel vdocitics arc 20 mfs and 30 mls respectively. Water CIlters at a height ofS m and leaves at a height ofO.S m. The "elociIY of waler at entry and ex il arc 3 mf5 and I mfs tcspccthely. Water lemperalures arc aooc and SOOC al !be entry and exil respecti'ely. Air lemperalures arc 30C and 70"C al the entry and eX;1 respectively. The coUing lOwer is wen insulaled and a fan of 2.25 kW dfj,'cs the air Ihrough Ihe cooler. Find the amounl ofairper second required for I kg/s ohrater now. The valucsof of ai r and water arc 1.005 and 4.1871kg K rcspet:tive\y. AIlS. 3.16 kg 5.9 Air al 101.325 kPa, 20C is taken inlO a gas lurbine power plan! al a velocity of 140 mls through on opening of 0. 15 m~ crosssecliona l area. The air is compressed healed. e~panded throu~ a turbine. and exhatmed al O.IS MPlI. IsO"C l/trough an opening of 0.1 0 m cross-sectional area. lbe power outpUI is 375 kW. Calculate the nel amount ofhcal added to the air in kJlkg. Assume that air obeys the law p fJ .. 0.2S7 (t + 273) whet" p is the pressure in kPa v is Ihe specific volume in mJlkg, andl is the tempemlURl in C . Take c p " 1.005 kJlkg K. AilS. 150.23 kjlkg 5.10 A gas flows ste~dily tluougb a romry(om~r. The gas enlen the compressor al a temperature of 16"C. a pressure of 100 kP:t. and an en thalpy of 39 1.2 kJlkg. The gas leaves the compres.soTal a ICmpemlute of 245 C, a pressure of 0.6 MPa. and an cotlullpy of534 .5 kJlkg. There is 110 heal transfer 10 o r from the gas as il flows through the compressor. (a) Eva luate the external work done pcruoit mass of gas assuming the gas velocilies al eotty and CJ(it to be negligible. (b) Evaluale the ext ernal ....ork done per unit mass of gas .... hen the gas velocity at emf)' is 80 mls and Iltal al exit is 160 mls. AII~. 143.3 kJlkg. 152.9 kJlkg 5. 11 The steam supply to an engine compri ses Iwo streams which mix before enlering the engine. One stream is supplied lllhe mle of 0.01 kg/s wilh an enlltalpy of 2952 k1lkg and a veloc ity of20 mls. The other slream is ruppJied at the (;lIe of 0.1 kg/s wilh an enlhalpy of2S69 kJlkg and a velocity of 120 mls. At the exit


Fin/LAw Applitd to Row Promsa

- = 109


5. \3

5. 14

5. 15



from the engine tile fluid lea~ as two s~ams, one ofwatcr at Ihe rate of 0.001 kg/a with an enthalpy of 420 kllkg and the othcrofsteam: the fluid velocities at the exit are negligible. The engine dc:\"t:lops a shaft power of 25 tw, The heat ttansfer is negligible. Evaluate the enthalpy oflhe second exit sueam. Alii. 2401 kllJr.g The stream orair and gasoline vapow-. in the ratio of 14:1 by mass, enters a guo line engine at a temperature ofJO"C and lca"cs as combustion products at a tcmpcratlll"C of 790C. The engine tills a specific fuel consumption of 0.3 kg/kWh. The net beat transfer rate from the fuelair steam to the jacket cooling water and to the surroundings is35 kW. The shaft power delivered by the engine is 26 kW. Compute the increase in the specific enthalpy orthe fuelair stream, assuming the changcs in kinetic energy and in elevation to be negligible. AM. - 1877 kJlJr.g mixture An air turbine forms pnrt of lin aircraft refrigeroting plant. Air at a pressure of 29S kPa and a temperaturc of 58C flows steadily ;nto the turbine with a velocity of 45 mls. Tbe air Jea,cs the turbine at a pressIU"C of liS kPa, a temperature of 2C, and a velocity of ISO mls. Thc shaft work delivered by the turbinc is 54 kJlJr.g of air. Neglecting changes in elevation. determine the magnitude and sign of the heat uansfcr per unit mass of air flowing. For air, take c p 1.005 kJlJr.g K and the enthalpy h .. c p I. Am. + 7.96 kJ/kg In a turbomachinc handling an irn:ompres.sible fluid with a density of I000 kglm' the conditions orthe fluid at the rotor entry and exil are as given below Exit Inlet Premm: 1.15 MPa 0.05 MPa Velocity 30 mls IS.S mls Height aoo"cdatum 10 m 2m If the volume flow rate of the fluid is 40 m'rs, cstimate the net energy trnnsfer from tile fluid as work. AII.'. 60.3 MW A room for four perrons has two fans. each consuming 0. 18 kW power, and three 100 W lamps. Vcntilation air at the mte of 80 kg/b enters with an enthalpy of 84 kl/kg and leavcs with an enthalpy of 59 kJlkg. lfeach person puts out heat at the rate of630 kg/h dc:tcrmine the rate at which heat is 10 be removed by a room cooler, so that a steady !ltate is maintained in the room. All.!". 1.92 kW Air flows steadily at the ratc of 0.4 kgfs through an air compressor, entering at 6 mls with a pressure of I bar and a specific volume ofO. S~ m' lkg. and lcavins at 4.5 mls with a pressure of 6.9 bar and a specific volume of 0.16 mJ/kg. The internal energy of the air leaving is 88 kJlJr.g greater than that of the air entering. Cooling water in ajacket, surrounding the cylinder absorbs heat from the air at the rate of 59 W. Calculate the power required to drive the compressor and the inlet and outlet CTOSssedional areas. (Am. 45.4 kW. 0.OS7 ml , 0.0142 ml) Steam flowing in a pipeline is at a stcady state represented bypp, lp' lip' tip, hp and Vp' A small amount of lhe IOtal flow ~ led through a small tube 10 an cvacuated chamber which is allowed to fill slowly until the pressure is equal to the pipeline

lIO=pressure. lrlllere is no heat transfer, derive an eXpt'C55ion for the fmal spe<:irI<: intcnuJ ellCrgy in the <:hamber, in terms of the propenies in the pipeline. S.IS TIle internal energy of air is given, at ordinary temperatures, by 1I - "o+O.7ISr where II is in kJlkg, 110 is any arbitrary value of II at OC, kJlkg, and I is tcmpmllure in C. Also for air, pv - 0.2S7 (/ + 273) where P is in kPa 1IIld v is in m'/kg. (a) An evacuated boule is fined with a valve through whi<:h air (rom the aunosphere, at 760 mm Hg and 2S"C, is allowed to flow slowly 10 fill the bonle. lfno heat is ITIIIs{erred to or from the air in the bonle, what will its temperature be when the pressure in the bottle reao:hes 760 rnm Hg? Ans. 144.2C (b) If the bonle in itially contains 0.03 ml of air 3t4oo mm Hg and 2SC. what will thetcmperature be wben the pre55UTC in the bottle reaches 760 mm Hg? AIlS. 71.6 C S. 19 A pressurecylindCTofvolume Veontai nuir at pressurepoand temperature Tg. 1t is 10 be filled from I eompressed air line maintained 11 constant PreuurePI and tcmpe~ TI. Show that lIle temperature of the air in the cylinder after it has been charged to the premJI'C of the line is given by

PI T o S.20 A 5mall reciprocating vacuum pump having the rate of volume displacement Y d is used 10 eVlcuate a large vesse l of volume Y. The air in the vessel is maintained at a constant temperature T by energy transeCT as heat. If the initial and fiDllI pressures &rePI andPJ tc5pCCtively, ftnd thetime taken forthe pressure drop and the necessary energy transeCT as heat during evacuation. Assumc thai for air. pv _ mRT, wbere m is the mass andR is a constant. and u is a function ofTonly.

1 + 1'2..(r.!i.. -I)


in J2.; (PI - PJ) ,,] p, (Hint; dm - - p(JI,dr)l(R7) " JI dp/(R7)] . S.21 A tank containing 4S kg of water init ially at4SC has one inlCl1llld one exi t with equal mass flow rates. Liquid water enters at 4S"C and a mass flow rate of270 kgIh. A cooling coil immersed in the WDter removes energy at a rate of7.6 kW. The water is well mixed by a paddle wheel with a power input of 0.6 kW. The presSIITCS I t inlel and exit are equ.al. Ignoring changes in KE and PE, find the variation of water tempel11ture with time. Ans. r - 318-22/1 - exp(- 61)] 5.22 A rigid tank of\'olume O.S m1 is initially evacuated. A tiny hole devclops in the wall. and air from the surroundings at I bar. 21 C leaks in. Eventually. the pressure in the tank reaches I bar. The process OCCUlll slowl y enough that heat InllIsfer belwCCII the tank and the surroundings keeps the temperature of the air inside lIle tank COl151ant at21 "C. DetCflllmc the amount of heat transfer. Au - SOU
[ A IIS. / -


Q -

Second Law of Thermodynamics


Qualitative Difference between Heat and Work

The first law of thermodynamics stales that a cenain energy balance will hold when a system undergoes a cbange of Slale or a thermodynamic process. BUI it does not give any information on whether thai change nrstale arthe process is at all feasible ornOl. The first law cannot indicate whether a metallic bar ofunifonn temperature can spontaneously become wanner alone end and cooler at the other. All thallhc law can state is that ifthis process did occur, the energy gai ned by one end would be exactly equal to that lost by the other. It is the second law of thermodynamics which provides th e criterion Q.f to the probability of various

Spontaneous processes in nalu~ occur only in one direction. Heat always flows from a body at a higher temperature 10 a body at a [owcrtemperature, water always flows downward, time always flows in the forward direc tion. The reve~ of these never happens spontaneously. The spontaneity ofthe pro<:ess is due to a finite driving potential, sometimes called the ' force' or the 'cause', and what happens is called the ' fl ux', the 'current' or thc 'effect'. The typica l forces like temperature gradient, concentration gradient, and electric potential grad ient, have their respective conjugate fluxes of heat transfer, mass transfer, and flow of electric current. These transfer processes can never spontaneously occur from a lower to a higher potential. This direct ional law puts a limitation on energy transfonnation other than that imposed by the first law. louIe's experiments (A rticl e 4.1) amply demonstrate that energy, when supplied to a system in the fonn of work. can be completely converted into heal (work transfer --t internal energy increase --t heat transfer). But the complete conversion of heal into work in a cycle is not possible. So heal and work are nOI

completely jnterchangeable forms of energy.


112=When work is con\'ened into heat, we always have


but when heat is converted into work in a complete closed cycle process

The arrow indicates the direction of energy transformation. This is illustrated in Fig. 6.1. As shown in Fig. 6.I(a), a system is taken from state I to state 2 by work transfer W l _2, and then by heat transfer QI_I the system is brought back from stnlC 2 to state I to complete a cycle. It is always found that Wt_1 - QI_I' But if the system is taken from state I to state 2 by heat IransferQJ-2' as shown in Fig. 6.1(b), then the system canol be brought back from stale 2 to state I by work transfer Wz- I , Hence, heat cannot be convened completely and continuously ipto work in a cycle. Some heat has to be rejected. In Fig. 6.1(b), Wl _l is the work done and Qj-l is the heat rejected to complete the cycle. This underlies the work ofSadi Carnot. a French military engineer. who first studied this aspect of energy transformation (1824). Work is said to be a high grade energy and heat a low

grade energy. The complete comoersion {If low grade energy into high grade energy in a cycle is impossible.

~ ,-,

~ o, -,


w'_2 ~_1

6.2 Cyclic Heat Engine

for engineering purposes. the second law is best expressed in terms of Ihe conditions which govern the production of work by a thermodynamic system operating in a cycle. A heat engine cycle is a thermodynamic cycle in which there is a net heat Il1lIlsfcrto the system and a net work transferfrom the system. The system which executes a heat engine cycle is called a heut engine. A heat engine may be in the form ofa mass of gas confined in a cylinder and pislon machine (Fig. 6.2a) or a mass of water movilig in a steady flow through a steam powcr plan! (Fig. 6.2b). In the cyclic I'eat engine. as represented in Fig. 6.2(a), heat Qt is transferred 10 the system, work WE is done by the system. work W. is donI! upon the system, alld then heatQl is rejected from the syslerr The system is brought back to the initial state through all these four succcssive processes which constitute a heal engine cycle. In Fig. 6.2(b) hcat QI is transferred from the furnace to the water in the

boiler to form steam which then works on the turbine rotor to produce work W T then the steam is condensed to water in the condenser in which an amount Ql is rejected from the system, and finally work Wp is done on the system (water) to pump illo the boiler. Tile system repeats the cycle.

w ~-





Fig. 6.2 eye/it: lulll '''l''~, (d) Hmt ~fU 9<h JKrfonrud by II (WJld J]Jltm IIndctpjll{,fo~r J""miff t"lrgJ infnllcliollJ wilA /M JMrralllllii"l' (b) H.61 ~nt C'J'h pnf_td by II Jltlldy /hw 1]#'''' ""lnllc/ill{, witlllhl SIIrro.lIlii"l' /U show"

The net heallransfer in a cycle to either of the heat engines

QI'><1 " QI - Q2 and the net work transfer in a cycle
W_ - WT - Wp

(6. 1)


W... .. WE - Wc>

By the firsllaw of thermodynamics. we have

<)'<10 <yel<

Q"", - 11'.,.. QI - QZ - WT -



Figure 6.3 represents a cyclic heat engine in the form of a block diagram indio cating the various energy interactions during a cycle. Boiler (8). turbine (1), con denser(C'). and pump (P). all fouTtogether constitute a heal engine. A heat engine


ll'=is here a cenain quantity of water undergoing the energy interactions, as shown, in cyclie operations to produce net work from a certain heat input. The function of a heat engine cycle is to produce work. continuously at the ell:pense ofhest input to the system. So the net work W,,", and heat input Ql referred to the cycle are of primary interest. The efficiency of a heat engine or a heat engine cycle is defined as

Fig. 6-3
(]plU Mal ~JU willi tIInlJ illlnlldiolU rtpttstNlttl iN a

Mk ditJrrluri

'1 _ Net ""IOrk output of the cycle

T OIal heat input to the cycle


From Eqs (6.1), (6.2), (6.3), and (6.4)


'1 - W .... "" WI - Wp Q, Q,

'1 = I - .!?L



This is also known as the ,hermal efficiency of a heat engine cycle. A heat engine is very often called upon to ell:trnct as much work (net) as possible from a certain heat input, i.e., to maximize the cycle efficiency.

6.3 Energy Reservoirs

A thennal energy reservoir (TER) is defined as a large body of infinite heat capacity. which is capable of absorbing or rejecting an Wllimited quantityofheat without suffering appreciable changes in its thermodynamic coordinat~. The chang~ that do take place in the large body as heat enters or leaves are so very slow and so very minute that all processes within it are quasi-static. The thennal energy reservoir TERIoi from which heat Q 1 is transferred to the system operating in a heat engine cycle is called the source. The thermal energy reservoirTER L to which heat Q1 is rejected from the system during a cycle is the sink. A typical source is a constant temperature furnace where fuel is conti nuously burnt, and a typical sink is a river or sea or the atmosphere itself. A mechanical energy re.o;erv(lir(MER) is a large body enclosed by an adiabatic impermeable wall capable of storing work as potential energy (such as a raised weight or wound spring) or kinetic energy (such as a rotating flywheel). All processes of interest within an MER are essentially quasi-static. An MER receives and delivers me<:hanical energy quasi-statically.

Figure 6.4 shows a cyelic beat engine exchanging beat with a source and a sink and delivering IVlid in a cycle to an MER.








0'/(' ~'III ttrti'" (CitE) wiiJI ~u r" 11M lillk

6.4 Kelvin-Planck Statement of Second Law

The efficiency ora heat engine is given by

11 _ W .... =I_~



Experience shows that W.... < QI ' since heat Q I transferred to a system cannot be completely converted to work in a cycle (Article 6.1). Therefore, fJ is less than unity. A heat enginc can never be 100 efficient. Therefore, Ql > 0, i.e., there bas always to be a heat rejection. To produce nel work: in a thermodynamic cycle, a heat engine has thus to exch.ange heat with two reservoirs, the source and the sink. The Kelvin-Planck statement of thc second law stalCS: It is impossible for a heat engine to produce net work in II complete cycle if it exchanges heal ollly

with bodies at a single fixed temperature.

If Ql " 0 (i.c., IVlid - QI' or II '" 1.00), the heat engine will produce net work in a complete cycle by exchanging heat with only one reservoir, thus violating the Kelvin-Planck statement (Fig. 6.S). Such a heat cngine is called a perpelUa/ motioll machine of the second kind, abbrevipted to PMM2. A PMM2 is impossible. A beat engine has, therefore. to exchange heat with two thermal energy rescrvoirs at two diffcrent temperatures to produce net work in a complete cyclc (Fig. 6.6). So long as there is a difference in temperature, mOlh'c power (i.c. work) can be produced. (fthe bodies with which the heat engine exchanges healareoffinile bcal capacities. work will be produced by thc heat engine till the temperatures of the two bodies are cqualized.




Fig. 6.5


Fig. 6.6

Htal 'wgilll prodl/d", ntl work ill a cych lrj UtluJllgilll IItal altwo "ifftrml

If the se1;ond law were not true, it would be possible to drive a ship across the ocean by elltrncting heat from the ocean orto run a power plant by elltrnctingheat from the SIlITOunding air. Neither of these impossibilities violates the fitstlaw of thermodynamics. Both the ocean and the surrounding air cootain an enormous store of internal energy. which. in principle. may be elltracted in the fonn of a flow of heat. There: is nothing in the fll'St law to preclude the possibility of converting this heat completely into work. The second law is. therefore:. aseparate law of nature:, and not a deduction of the fitst law. The first law denies the possibility of creating or destroying energy; the second denies the possjbility of utilizing energy in a particular way. The continual operation of a machine that creates its own energy and thus violates the fitstlaw is called the PMMI. The operation of a machine that utilizes the internal energy of only one TER, thus violating the second law, is called the PMM2.

6.5 Clausius' Statement of the Second Law

Heat always flows from a body at a higher temperature: to a body at a lower temperature. The reverse process never occurs spontaneously. Clausius' statement of the second law gives: II is impossible 10 cons/roct a
device which. operoting in a cycle. will produce no effect other than the transfer of heat from a cooler to a hotter body.

Heat canot flow of itself from a body at a lower temperature to a body at a higher temperature:. Some work must be ellpended to achieve this.

6.6 Refrigerator and Heat Pump

A refrigerator is a device which, operating in a cycle. maintains a body at a temperature lower than the temperature of the surroundings. Let the body A (Fig. 6.7) be maintained at tl , which is lower than the ambient temperature II' Even though A is insulated. there will always be beat leakage Q2 into the body

rrom the surroundings by vinue or the temperature difference. In order to maintain, body A at the constant temperature /2' heat has to be removed rrom the body at the same rate at which heat is leaking into the body. This heat (Q:!l is absorbed !by a working nuid, called the refrigerant, which evaporates in the evaporator 1 at a temperature lower than 12 absorbing the latent heat of vaporization from the body A which is cooled or refrigerated (Process 4-1). The vapour is first compressed in the compressorC1 driven by a motor which absorbs work. We (Process 1-2), and is then condensed in the condenser C1 rejecting the latent heat of condensation QI at a temperature higher than that of the atmosphere (at 'I) for heat transfer to take place (Process 2- 3). The condensate then expands adiabatically through an expander (an engine or turbine) producing work WE' when the temperature drops to a value lower than'2 such that heat Ql nows from the body A to make the refrigerant evaporate (Process 3-4). Such a cyclic device of now through E I -C I --Cr E2 is called a refrigerator. In a refrigerator cycle, attention is concentrated on the body A. Ql and Ware of primary interest. Just like efficiency in a heal engine cycle, there is II performance parameter in a refrigerator cycle, called the coefficient a/performance, abbreviated to COP, which is defined as

" L?f?









1 0,

Fig. 6.7

A rytlir.


..."A a\ '2



COP = Desired effect = Ql Work. input W







A heat pump is a device which, operating in a cycle, maintains a body, say B (Fig. 6.8), at a temperature higher than the temperature of the ~undings. By virtue of the temperature difference, there will be heat leakage Q1 from the body to the surroundings. The body will be maintained al the constant tempera lure t I' if heal is distharged inlo th e body at the same rale at which heat leaks out of the body. The heat is extracted from the low temperature reservoir, which is nothing but the atmosphere, and distharged into the bigh temperature body S, with the expenditure of work W in a cyclic device called a heat pump. The working fluid operates in a cycle flowing through the evaporatorI' cnmpressor C I condenser C2 and expander 2' similar to a refrigerator, hut the anention is here focussed on the high temperature body B. HereQI and Ware of primary interest, and the COP is defined as


Fig. 6.8 A "djr Mal pump

A_ ."

COP - ~

(COP]", .. - ~ Q,-Q,
From equations (6.6) and (6.7). it is found that


(6.8) [COPjll.P. - [COPj..r+ 1 The COP ora heat pump is greater than the COP of a refrigerator by unity. Equalion (6.8) expresses a very interesting feature of II heat pump. Since QI = [COPjllJ>. W =' [COP..r + IjW


QI is always greater than W. For an electrical resistance heater, if Wis the electrical energy consumption. then Ihe heal transfeTTed 10 the space al steady state is W only, i.e., Q 1 - W.


A I kW electric heater can give I kW of heat at steady state and nothing more. In other words, I kW of work (high grade energy) dissipates to give I kW of heat (low grade energy), which is thermodynamically inefficient. However, if this electrical energy IVis used to drive the compressor ofa heat pump, the heat supplied QI will always be more than IV. or QI > IV. Thus, a heat pump provides a thennodynamic advantage overdireet heating. For heat to now from a cooler to a hotter body. IV cannot be zero, and hence, the COP (both for refrigerator and heat pump) canot be infinity. Therefore, IV>O,andCOP<_.

6.7 Equivalence of Kelvin-Planck and Claulius Statement!

At first sight. Kelvin-Planck's and Clausius' statements may appear to be unconnected, but it can easily be shown that they are virtually two parallel statements of the second law and are equivalent in all respects. The equivalence of the two statements will be proved ifit can be shown that the violation of one statement implies the violation of the second, and vice versa. (a) Let Us first consider a cyclie heat pump P which transfers heat from a low temperature reservoir (12) to a high temperature reservoir (I I) with no other effect, i.e., with no clIpenditure of work, violating Clausius statement (Fig. 6.9).

w- o

I '0,


FIg. 6.9 VioJ.rlion

~ tJu

CknlSillS sl4/mun1

Let us assume a cyclic heat engine E operating between the same thermal energy reservoirs, producing W.... in one cycle. The rate ofworting of the heal engine is such thai it draws an amount of heal QI fror' the hot reservoir equal to that discharged hy the heat pamp. Then the hot reservoir may be eliminated and the heat QI discharged by the heat pump is fed to the heat engine. So we see that the heal pump P and the heat engine E acting together constitute a heal engine

120=operating in cycles and producing net work whi Ie exchanging heat onl y with one body at a single fixed temperalUre. This violates the Kelvin-Planck sta temenl. (b) Let us now consider a perpetual motion machine of the second kind () which produces net work in a cycle by exchanging heat with only one thermal energy reservoir (alI,) and thus violates the Kelvin-Planck statement (Fig. 6.10). Let us assume a cyclic heat pump (P) extracting heat Ql from a low temperature reservoir at IZ and diseharging beat to the high temperature reservoir at 1, wilh the expenditure of work Wequal to what the PMM2 delivers in a complete cycle. So and P together constirute a heat pump working in cycles and producing the sole effect of uansferring heal from a lower to a higher temperature body, thus violating the Clausi us statement.


Rg. 6.10

ViDhI/IDn Dr/lit Klmifl P/and: J/dllll1l11/

6_8 Reversibility and Irreversibility

The second law of thermodynamics enables us to divi de all processes into two

(a) Reversible or ideal process. (b) Irreversible or natural process. A reversible process is one which is performed in such a way that at the conclusion of the process. both the system and the surroundings may be restored to their initial states, wi thout producing any changes in the rest of lhe universe. Let the state of a system be represented by A (Fig. 6.1 I), and let the system be taken to stale B by following the pathA- B.lfthe system and also the surroundings are restored to their initial states and no change in the universe is produced. then the process A-B wiil be a reversible process. In the reverse process, the system has to be taken from state B to A by fonowing the same path B- A. A reversiblc process should nol leave any trace or re lic to show that the process had ever ocoumxl.



~ w. _ .

We _" (a)


FIg. 6.11

Rt1!tTsihk process

A reversible process is carried out infinitely slowly with an infinitesimal gradielll. so that every state pal'sed through by the system is all equilibrium state. So a reversible process coincides with a quasi-static process. Any natural process carried out with a finite gradient is an irreversible process. A reversible process, which consists of a succession oj equilibrium stales, is an idealiled hypothetica l process, approached only as a lim it. It is said to be an asymptote /0 realif)'. All spontaneous processes are irtC\ersible.

6.9 Causes of lrrevenibWty

Broken eggs, spilt milk, burnt boats, the wasted years ofindolcnce that the locusts have eaten are merely proverbial metaphors for ineresibility. The irreversibility of a process may be due to either one or both of the following: (a) Lack of equilibrium during the process. (b) Involvement of dissipative effects.


IrMJertibiliq dIU to lAck of Eqllilwrillm

The lack of eqUilibrium (mechanical, thennal or chemical) between the system and its surroundings, or betwee n two systems, or two parts of the same system. causes a spontaneous change which is irreversible. The following are speci fiC examples in this regard: (a) Heat Traru.rer through a FInite Temperature Difference A heat transfer process approaches reversibility as the temperature difference between two bodies approaches lero. We define a revers ible heat transfer process as one in which heat is transferred through an infinitesimal tempcr!lture difference. So to transfer a finite amount ofheat through an infinitesimai temperature difference would require an infinite amount of time. orinfinite area. All actual heat transfer processes are through a finite temperature difference and are, therefore, irreversible, and the greater the tempe rature di fference. the grcater is the irreversibility. We can demonstrate by the second law that the heatlransfer through a finite temperature difference is irreversible. let us assume that a source atl" and a sink

122=at 18 (Ill. > IS> arc: available, and let QA-B be the amount of heat flowing fromA to B (Fig. 6.12). leI us asswne an engine operating betweenA andB, taking healQI from A and discharging heat Q2 to B. let the h~t trnnsfer process be reversed, and QS-A be the heat flowing fromB to A, and let the rate of working of the engine be such that QJ - QR-A (Fig. 6.13). Then the sink B may be eliminntc:d. The net result is that E produces net work W in a cycle by eJ:changing heat only with A, thus violating the Kelvin-Planck statement. So the heat transfer process QA-8 is irreversible, and QS-Ais not possible.
Source A, t... Source A, t...



0.. _...
Sink B, ts
SInk B.1e


FIg. 6.12 Hflll

tnlrujl1' Urr"lh Il finik Innpl1'lJ/~T(; tli/firttIU

FIg. 6.13 HtGJ traJUfrr fltr~llIh finm kfn/HTahtr. di/firtIW. is


(b) Lad of Prellure Equilibrium witbiD the Interior of the Syrtem or between the Synem and the SlUToundlDgs When there eJ:ists adifference in pressure between the system and the surroundings, or within the system itself. then both the system and its surroundings or the system alone, will undergo a change of state which will cease only when me<:hanieal equilihrium is eatablished. The revest: of this process is Dot possible spontaneously without producing any other effect. That the reven;e process will violate the second law becomes obvious from the following illustration.
(el Free EspansIOD let us coru;ider an iDsulated container (Fig. 6.14) which is divided into [WO companments A and B by a thin diaphragm. Compartment A contains a mass of gas. wbile compartment B is completely evacuated If the diaphragm is punctured, the gas in A will expand into 8 until the pre~ures in A ami B become equal. This is knowo as free or unrestrained expansion. We can demonslnlte by the second law, thaI the process of free expansion is irreversib le. To prove this, let us asswne that free expansion is reversible, and thai the gas in B returns inlo A with an increase in pressure, and B becomes evacuated as

before (Fig. 6.15). There is no other effect. Lc:t us install an engine (a machine, not a cyclic heat engine) between A and B, and pennit the gas to expand through the engine fromA toB. The engine develops a workoutput Wat the expense of the internal energy of the gas. The internal energy of the gas (system) in B can be restored to its initial value by heat transfer Q (= W) from a source. Now, by the use of the reversed free expansion, the system can be restored to the initial state of high pressure inA and vacuum inB. The net result is a cycle, in which we observe that net work output W is accomplished by exchanging heat with a single reservoir. This violates the Kelvin-Planck statement. Hence, frec expansion is irreversible. The same argument will hold if the compartment B is not in vacuum but at a pressure lower than that in compartment A (case b).

SQUI'C8. t



FIg.6.1' Fru t:f/HllUion

Fig. 6.15 Sirond law dffllollJlrnlts Ihnl ftu t:rpnlUi~JI is irmmihlt

6.9.2 l"nJersibility due to Dissip atirJe Effects

The irreversibility of a process may be due to the dissipalil'e effects in which work is done without producing an equivalent increase in the kinetic or potential energyofany system. The transfomtation of work into mo lecular intcrnal energy either of the system or of the reservoir takes place through the agency of such phenomena as friction, viscosity, inelasticity, electrical resistance. and magnetic hysteresis. These effects are known as dissipative effects, and work is said to be dissipated. Dissipation of energy means the transition of ordered macroscopic motion into chaotic molecular motion, the reverse of which is not possible without violating second law. (.) Friction Friction is always present in moving devices. Friction may be reduced by suitable lubrication, but it can never be completely eliminated. Ifthis were possible, a movable device could be kept in continual motion without violating either of the two laws of thennodynamics. The continual motion of a movable device in the complete absence of friction is known asperpelual moriOI! ofthe Ihird kind. That friction makes a process irreversible can be demonstrated by the second law. LeI us consider a system consisting of a flywhee l and a brake block (Fig. 6. 16). The flywheel was rotating with a certain rpm, and it was brought to




rest by applying Ibe medon brake. The distance moved by the brake block is very small, so work transfer is very nearly equal to zero. Iflbe braking process occurs very rapidly. there is lillie heat transfer. Using suffill 2 after braki ng and suffh I before braking, and applying the first law, we have

"~ f\l
'C .-----------------------)
Syslem boundary
FIg. 6.16 IrmvTlibililJ dwt 10 dwi/IQli~t tffirl liu frj(lj~"

QI -l ~ 2 - EI + If'I_ l 0 -2-1 +0 (6.10) 2=1 The energy of the system (isolated) remains constant. Since the energy may exist in tbe forms of kine tie, potential, and molecular internal energy, we have

U,+ - - +mZ2!l '" VI + -. --



+ mZ~

Since the wheel is brought to rest, V 2 ~ 0, and there is no ehange in P.E.

U2 - UI+~

mY' 2

(6. 11)

Therefore, the molecular internal ene rgy ofthe system (I.e., of the brake and the wheel) increases by the absorption of the K. E. of the wheel. The reverse process.. i.e., the conversion of this increase io molecular inlernal energy inlo K.E. within tbe system 10 cause the wheel to rotate is not possible, To pro\'e it by the sl.'Cond law, let us assume that il is possible, and imagine the following cycle with three processes: Proc(!!i~ .of: Initially, the wheel and the brake are at high lemperature as a result of th e absorption of the K.E. of the whee l. and the flywheel is at rest. Let the flywheel now start rotaling at a particular rpm al the expense of Ihe inlemal energy of the whee l and brake, the tempera lure of whi ch will then decrease. i'r(JCe.~!i B: Let the fl ywheel be brought to rest by using il5 K.E. in raising weights. with no change in tempcrnturc. Process C: Now let heat be supplied from a source to Ihc flywh~"C 1 and the brnke. to reslore the system 10 its initial state. Therefore. the processes A. S, aoo C togeth er consti tu te a cycle producing work byexchanging heat with a single reser.... oir. This violates the Kelvin-Planck sl3lcmcllt, and it will become a PMM2. So the braking process, i.e., Ihe transronnation orK.E. HIIO mo lecular inlemal energy, is ilTe yersible.

(b) Paddle-Wheel Work Transfer Work may be transferred into a system in an insulated container by means ofa i \ paddle wheel (Fig. 6. 17) which is also known as sti rring work. Here work 'w , c transferred is dissipated adiabatically into an increase in the molecular internal energy of the system. To prove the Flg.6.17 AditllHJli! work Irtlru[" irreversibility of the process, let us assume that the same amount of work is delivered by the system at the expense ofits molecular internal energy. and the temperature of the system goes down (Fig. 6.18). The system is brought back to its initial state by heat transfer from a source. These two processes together constitute a cycle in which there is work output and the system exchanges heat with a single reservoi r. It becomes a PMM2, and hence the dissip;ation of stirring work to internal energy is irrevers ible.


l rrmmihilil] dutlo dwlpalin o[Jlm"!, "'Drk Ilf/o Ilfl"~.lt~"D

(e) Transfer of Electricity through a Resistor The now of electric current through a wire represents work transfer, because the cum:nt can drive a mOlor which can raise a weight. Taking the wire or the resistor as the system (Fig. 6.19) and writing the first law

Ql_2" U2 ..


+ /V1 _2

Here both WI_2 and Q l-l are negative.

Wl_2 ""V2 -V,+Ql_2

A pan ofthe work transfer is sto red as an increase in the internal energy of the wire (10 give an increase in its temperature), and the remainder leaves the system as heat. At steady state, the internal ene rgy and hence the temperoture of the resistor become consta nt with respect 10 ti me and


Fig. 6.19 lrr'NTJlhilil] du. 10 dwlpallQIf o[ ,mtriaJl"'D '1c ,lflo ilflrr".1 rnrr8J


126=The reverse process, i.e . the conversion of heat Ql -1 into el~trical work WI_2 of the same magnitude is not possible. Let us assume that this is possible. Then heat QI _2 will be absorbed and equal work W1_1 will be delivered. But this will become a PMMl. Sothe dissipation of electrical work into internal energy or heal is irreversible.

6.10 Conditions for Reversibility

A natural process is irreversible because the conditions for mechanical. thermal and chemical equilibrium are not satisfied. and the dissipative effects, in which work is transformed into an increase in internal energy, are present For a process to be reversible. it must not possess the:se features. If a process is performe:d quasi.statically. the: system passes through states oflhermodynamic equilibrium, which may be traversed as well in one di~tion as in the opposite direction. If there are no disslpatiloe effects. 01/ the work done by the system during the performance aj a proce~ In one direction can be returned to the systt!m during the reverse process. A process will be reversible when it is performed in such a way/hat the syslem is ot all limes infinitesimally near a slate ojlhennodynamic equilibrium and in the absence ojdissipolive effect ojany form. Reversible processes are, therefore. purely ideal, limiting cases of actual processes.

6.11 Carnot Cycle

A reversible cycle is an ideal hypothetical cycle in which all the processes constituting the cycle are reversible. Carnot cycle is a reversible cycle. For a stationary system. as in a piston and cylinder machine. the cycle consists of the following four successive processes (Fig. 6.20):

, 0.'''''"'' coYer (A)

Ad!ilbatic cover (S )





(a) A reversible isothermal process in which heat QI enters the system at'l reversibly from a constant temperature source at'l when the cylinder cover is in contact with the diathermic cover A. The internal energy orthe system increases. From First law, Q 1 - Uz - U I + W I _Z (6.14) (for an ideal gas only, U I - Ui) (b)A reversibleadiabotic process in which the diathermic cover A is replaced by the adiabatic cover S, and work WE is done: by the: system adiabatically and reversibly at the: expense ofits internal energy, and the temperature of the system decreases from lito 12, Using the: first Jaw, (6.15)
(e) A rel'ersib/e isQ/hermal process in which S is replaced by A Ilnd heat Q2 leaves the syste:m at '2 10 a constanl tempernlure sink at 11 reversibly, and the internal cnergy of the system further decreases. From the firstillw,

- Q2 " U4

UJ - W}-4


only for an ideal gas, U) " U4 (d) A reversjble adiabotic process in which S again replaces A, and work Wp is done: upon the syslem reversibly and adiabatically, and the internal energy of the: system increases and the temperature rises from t2 to 'I' Applying the first law, (6. 17) Two reversible isotherms and two reversible adiabatics constitute a Carnot cycle, which is represented inp-v coordinates in Fig. 6.21. Summing up Eqs (6. 14) to (6.17),

Q1 - Q2 '" (WI_2 + W2_1) -


W 4 _1)




A cyclic heal engine operating on the Carnol cycle is called a Carnot heal engine.

Fig. 6.21

Qm,a' <J,1t



128=For a steady flow system, the Carnot cycle is represenied as shown in Fig. 6.22. Here heat Q I is transferred to the system reversibly and isothennally at '1 in the heat exchanger A, work W T is done by the system revers ibly and adiabatically in the turbine (8), then heat Q2 is transferred from the system reversibly and isothermally at '2 in the heat exchanger (C), and then work IV.. is done upon the system reversibly and adiabatically by the pump (D). To satisfy the conditions for the Carnot cycle, there must not be any friction or heat transfer in the pipelines through which the working fluid flows.

: .. Flow

SOUrce. It

-------' t .. ..

~!.. .. -... ............ .

-----1 / syslem

Hailt ,, ~chaoger (AI

Pump (01
TLdlinIl (B)



w.... =Wr-wp
-Q, - O:/;

6.12 Reversed Heat Engine

Since all the processes of the Carnot cycle are reversible, it is possible (0 imagine that the processes are individunlly reversed and carried out in reverse order. When a reversible process is reversed, all the energy transfers assoc iated with the process are reversed in direction. but remain the same in magnitude. The reversed Carnot cycle for a steady flow system is shown in Fig. 6.23. The reversible heal engine and the reversed Carnot heat engine are represented in block diagrams in Fig. 6.24. If E is a reversible heat engine (Fig. 6.24a). and if it is reversed (Fig. 6.24b). the quantities QI' Q2 and IV remain the same in magnitude. and only their directions are reversed. The reversed heal engine 3 takes heat from a low temper.lture body. discharges heal to a high tempenllure body, and receives an inward flow of network:. The nameshcm pump and rt'jrigcralOr are applied to the reversed heal engine. which have already been discussed in Sec. 6.6. where the work.i ng fluid flows through the compressor (8). condenser (A). expander (D). and evaponllor (C) to complete the cycle.


- = 129

~ :>yatem


OJ """

Heat exchanger (A)


f-- Wr
t2 l



........... ..:;: :.. 1 .""";;; ..;; ...

::! ..;...;..~ ~ (02 ;.= ..:t:::::::::::::::! . .

Heat extm."!I9'" (C)

" 0, 1
j"A ;
w,. -

'-. c/


w... Wr- w,.

w,-- o ,


" 0,1

\. c/

6.13 Carnot's Theorem

/1sImes Ihat of all heat engines operating belween /I given conswlll lemperoll4re source Q/rd II g;\'en COliS/anI lemperature sink, none h(1S II higher efficiency than a re"usible engine. Let IWO heal engines EA and EB operate between the given source al temperature I, and the given si nk at temperature '2 as shown in Fig. 6.25 . lei EA be any heat engi ne and 8 be tiny reversible heal engine. We have to prove thallhe efficiency of B is more than that of EA' Let us assume that this is 1l00Irue and I1A> 110' lei the rates of working of th e engilles be such that Q rA = QII'I = Q r
Since I1A> 111\
B -- > -II'A






fig. 6.25

TWII "Jdic "ttll nttilUS EA uti 6 Optttltiq MIWfflIIIII 14m, S4.rCf tiM tink, Q/wM," Ea is rtN1sihk

Now,let Eo be reversed. Since ED is a reversible heat eogine, the magnitudes of beat and work transf~ quantitics will remain the same. but thcir directions will be reversed, as shown in Fig. 6.26. Since W 0 A > Wo. some pan of " 'A (equal 1 It'o) may be fed to drive the reversed heat e ngine 3 D .
Source, /,



Slnk. tl

Fig. 6.26 Ea is mmtd Since Q,A" QIO - Ql' the beat discharged by3 0 may be supplied 10E".. The source may, therefore, be eliminated (Fig. 6.21). The net result is that EA and 3 0 together constitute a he at engine which, operating in a cycle. produces net work W A - "'0' while exchanging heat with a single reservoir alil' This violates the KelvinPlanck statement of the second law. Hence the assumption that f/" > flo is

- g.


"'= 131

Fig. 15.2.1


arul3B togetlm Diokite III, K-P fUittmmt

6.14 Corollary of Carnotls Theorem

The efficiency of all reversible heat engines operating between the same temperature levels is the same. Let both the heat engines EA and Eo (Fig. 6.25) be reversible. Let us assume " ... > "D' Similar to the procedure outli ned in the precc::ding article, if ED is reversed to nut, say, as a heat pump using some pan of the work output (11'10) of engine EA' we see that the combined system of heat pump ED and engine EA, becomes a PMM2. So tfA cannot be greater than 'lB' Similarly, if we assume 'Ie > " ... and reverse the engine EA , we observe that tfe cannot be greater than "A' Therefore 11... = 11a Since the efficiencies of all reversible beat engines operating between the samc heat reservoirs are the same, the efficiency 0/a reversible engine is independent

o/the nature or amount o/the working substallce undergoing the cycle.

6.15 Absolute Thermodynamic Temperature Scale

The efficiency of any heat engine cycle receiving heat QJ and rejecting heat Q1 is given by (6.18) By lbe second law, it is necessary to have a temperature difference (/1 - t 1) to obtain work of any cycle. We know that the efficiency of all heal engines operating between the same temperature levels is th e same, and it is independent of the working substance. Therefore. for a reversible cycle (Carnot cycle), the efficiency will depend solely upon the temperatures II and 12 at which heat is transferred, or (6.19) wberefsignifies some function of the temperatures. from Eqs (6.18) and (6.19)


132 ~

1 -~

- /(II,I Z )

In terms of a new funclionF

If some functional relationship is assigned between '1' /1 and Q/Qz' the equation beeomes the definition ofa temperature scale. Let us consider two reversible heat engines. EJ receiving heat from the source al iI' and rejecting heat at /1 10 El which. in tum, rejects heat to the sink at I) (Fig. 6.28).


... W,.Q,-~

" - --+- -



HOlat 1'MIIrv(lir. 13

fig. 6.28 171m CamDI ~/ltJ

i: 1 and E1togetlter constitute another heat engineE} operating between II and I).


1i. .. F(II' /1)


J?L _ Q) /QJ
(6 IQ)
F(tI,ll )
F(ll.I )


The temperatures II. /1 and IJ a.nl arbilnlrily chosen. The ratio QI /Q2 depends only on II and II. and is independent of'l' SO 'l will drop out from tbe ratio on the right in equation (6.21). After it has b;n cancelled, the numerator can be wrinen as \11(11)' and the denominator as ~(12)' where ~ is anotber unknown function .


- = 133

ilL ~ F (I

I,) '" (11)



Since fel) is an arbitrary function. the simplest possible way to de fi ne the absolute Ihermodynamic temperatllre Tis to let ~(t) .. T, as proposed by Kelvin. Then. by definition (6.22) The absolute thermodynamic temperature scale is also known as the Ke/I'in .fcale. Two tem~ratures on the Ke lvin scale bear the same relationship to eaeh other as do the heats absorbed and rejet:tcd respectively by a Camot engine operating between two reservoirs at these temperatures. The Kelvin temperature scale is. therefore, independent ofthc peculiar characteristics of any particular substance. The heat absc" -.1 QI and the heat rejected Qz during the two reversible isothermal processes bounded by two reversible adiaba tics in a Carnot engine can be measured. In defining the Ke lvin temperature: scale also. the triple point of water is taken as the standard reference point. For a Camot engine operating between reservoirs at temperatures T and T,. r, being the triple poinl of water (Fig. 6.29). arbitrarily assigned the value 273.16 K.

Q ,


T ;273.l6.Q.



If this equation is compared with the equations given in Article 2.3. it is seen that in the Kelvin scale, Q plays the role o/thermometric property. The amount of heat supplyQ changes with change in temperature. justlike tbe thermal emfin a thermocouple, II follows from the Eq. (6.23),
T "' 273.16.Q.


that the heat transferred isothermally between the: given adiabmics decreases as the temperature decreases. Conversely. the smal:er the val ue ofQ, tbe lower the corresponding T, The smallest possible value ofQ is zero, and the corresponding T is absolute zero. Thus, if a system undergoes a reversible isothermal process without transfe:rofheat, the temperature at which this process takes place is called the. absolute =ero. Thus, at absolule zero, an isotherm and an adiabatic arl!

That the absolute thennodynamic temperature scale has a definite zero point can be shown by imagining a series of re versible engines, elltending from a source at TI to lower temperatures (Fig. 6.30).


. 1




T, _ _


1j . 213.16K

Fig. 6.30 IItol rfIlInu apnolifll jg ftrUs



Q".,utllual rfIlI'" willi sid: /II. triph ,.i~ of_In


and so on. IrTI - T2 - T2 - T 1 " TJ - T. - .. , assuming equal temperature intervals QI-Q2 - Q2- Q3 '"' Q3-Q. "" ...


W I = W2 - W1 - ...

Conversely, by making the work quantities performed by the engines in series equal (WJ - Wl - W) - ... J, we will get
TI - T2 - T1 - T]= TJ

T4 ,. ..

"' "

al equal lemperature inlervals. A scale having one hundred equal intervals between the steam point and the ice point could be realized by a series of one hundred Camot engines operating as in Fig. 6.30. Such a scale would be independent of the working substance. lfenough engines are placed in series to make the 101a1 work OUlpUI equal to Qt, then by Ihe first law the heat rejected from the last engine will be zero. By the SC(X)nd law, however, the operation ofa cyclic heat engine with zero heat rejection canDot be achieved, although it may be approached as a limit. When the heat rejected approaches zero, the temperature of heat rejection also approaches zero as a limit Thus it appears that a definite zero poinl exists on the absolute temperature scale but this poinl cannot be reached without a violation 0/ the second law. Thus any attainable value of absolute temperature is always grealer than zero. This is also known as the Third Lawo/Thermodynamics which may be stated as follows: /l is impossible by any procedure, no matter how idealized, 10 reduce any system to the absolute zero o/temperature in afinite number 0/ operations. This is what is called the Fowler-Guggcnheim statement of the third law. The third law itselfis an independent law of nature. and not an extension ofthe second law. The concept of heat engine is nol necessary to prove the non-attainability of absolule zero of temperature by any system in a finite number of operations.

6.16 Efficiency of the ReversIble Heat Engine

The efficiency ofa rever.;ible heat engine in which heat is received solely at Tl is found to be

l1,cv ..


It is observed here that as Tl decreases. and Tl increases, the efficiency of the reversible cycle increases. Since 11 is always less than unity, Tl is always greater than zero and positive. The COP ofa refrigerator is given by

For a reversible refrigerator, using

11.. .. l


[COP"'ft.b~~ 1j - Tz


136=Similarly. for a reversible heat pump

rcoPIl.p]",v - - - -

r, 7;-12

(6.25) ,

6.17 Equality of Ideal Gas Temperature and Kelvin Temperature

Let us consider a Climot cycle ellccuted by an ideal gas. as shown in Fig. 6.31.

Fig. 6.31

Carnol tydt of an ir/(Il/14J

The two isothermal processes a-b and c-d are represented by equilateral hyperbolas whose equations are respectively


pY"'nR 81 pY - nR 8z

For any infinitesimal reversible process of an ideal gas, the first law may be written as !lQ - C,d9+pdY Applying this equation to thc isothermal process a-b, the heat absorbed is found to be


'f ' pdv - '/ _"__ R8 I dV::nROlln..JL V",



Similarly, for the isothermal process c-d, the heat rejected is


" nR~ In !L

~ _

0 1 In ..!i



021n ~


Since the process b-c is adiabatic, the flM law gives

-Cd9""pdY'" nR(J dY

-'- 1c ,
nR(l nR 9

v (J


= In ~ Vb

Similarly, hr the adiabatic" process d-il

-'- 1 c ,
In ..!:. = In Vd
Y b

d(J -In..!:L
(J -




!i. .. ' v.
Equation (6.26) thus reduces to




~ =~
Kelvin temperature was defined by Eq. (6.22)


~ =2L


If 8 and T refer to any temperature, and 6, and T, refer 10 the triple point of water,



Since 8, = T, = 273.16 K, it fOUOW5 that

8= T


The Kelvin temperature is, therefore, numerieaUy equal to the ideal gas temperature and may be measured by means ofa gas Ihennomeler.

6.18 Types of Irreversibllity

It has been discussed in Sec. 6.9 thai a process becomes irreversible if it oceurs due to a finite potential gradienllike the gradient in temperature or pressure, or if there is dissipative effecllike friction, in which work is transfonned into intemal energy increase of th e system. Two types of irreversibility can be distinguished:
(a) Internal irreversibility (b) E1ttemal irreversibility


&uic tlM Applid 'lMrml]Mmia

The internal irreversibility is caused by the internal dissipative effects like mction, turbulence, electrical resiSlance, magnetic hysteresis, elC. within the system. The external irreverj;bUiry refers to the irreversibility occuning at the system bowl(iary like heat interaction with the surroundings due to a finite temperature gradient. Sometimes, it is usefu l to make other distioctions. If the irreversibility of a process is due to thc dissipation of work into the increase in internal energy of a system, or due to a finite pressure gradient, it is caUed meehan/CDI irreverj lbill ty. If the process occurs on account ofa finite temperature gradient, it is/henna/ irrevenibility, and if it is due to a finite concentration gradient or a chemical reaction, it is caUed chemical irreverj;bility. A heat engine cycle in which there is a temperarure difference (i) between the source and the working fluid during beat suppl y, and (ii) between the worKing fluid and the sink during beat rejection, exhibits external thennal irreversibility. If the real source and sink are not considered and hypothetical reversible processes for heat supply and heat rejection arc assumed, the cycle can be reversible. With the inclusion of the aetual source and sink, however, the eycle becomes e xternaUy irreversible.



uample 6.1 A cyclie heat ensine operates betwec:n a souree temperature of gOOC and a sink temperature of30C. What is the least rate of heat rejection per kW net output of the engine?
Solution For a reversible enginc. the rate of heat rejection will be minimum (Fig. Ex. 6.1).
r, - t073K



w _ 0,- 02 _ 'kW

Fig. EL 6.1


= " - 1- -1j


StcoM LtUD o/'I'Umody'IIIJIIIiQ


'"' 1 _ 30+273
800 + 273

- 1 - 0.282 - 0.7\8


-.!!tt. =



17.... = 0.718

Q, _ _ I_ - I.J92kW 0.718 Now Ql "" QI- W IIOI * 1.392 - 1 "' 0.392 kW This is the least rate of heat rejection.

Eumple 6.2 A domestic food freezer maintains a temperature or _Isec. The ambient air temperature is 30C. Ifheatleab inlo the freezer at the continuous rate of 1.7S kJ/s what is the least power neeessary to pump this heat out continuously? Solution Freezer lemperature,
T2 - -l5+273 - 258K Ambient air temperature, Tt "" 30 + 273 - J03K The refrigeralOrcycle removes heal from the freezer at the same rate at which heat leab into it (Fig. Ex. 6.2).


Fig. Ex. 6.2

For minimum power requirement

"' "

140 = -

Q! ""


)( 303 " 2.06 kJfs

W = Ql - Q2 '" 2.06 - 1.75 '" 0.3 1 kJfs " 0.31 JeW

A reversible heat engine operates between two reservoirs at temperatures of 600"C and 40C. The engine drives a reversible refrigerator which operates between reservoirs at temperatures of 40C and - 20C. The heat transfer to the heat engine is 2000 kJ and the net work output of the eombined engine refrigerator plant is 360 kJ . (a) Eva luate the heat transfer to the re frigerant and the net heat lransferto the reservoir at 40C. (b) Reconsider (a) given that the efficiencyoflhe heat engine and the COP of the refrigerator are each 40".4 of their maximum possible values.

Example 6.3

(a) Maximum efficiency of the heat engine cycle (Fig. Ex. 6.3) is given

Q,. 2000


T2 =313K

Fig. U. 6.3
n '" I .,....

_ ~ - 1 - - - 1 - 0.358 - 0.642



3 13 873


W! "' 0.642 x 2000 '" 1284 JeJ


Maximum COP of the refrigerator cycle (COP)


Tl -7j




_ 4.22

Also Sirlce

COP ..


= 4.22

"' "

- = l-U

Wz - WI - W - 1284 - 360 - 924 kJ Q4 = 4.22 x 924 '" 3899 kJ QJ = Q~ + W2 .. 924 + 3899 '" 4823 kJ Q1 '" QI - WI - 2000-1284 " 7 16 kJ
Heat rejection 10 the 40 C reservoir

'" Q2 + QJ " 716 + 4823 = 5539 kJ

(b) Efficiency of the actual heal engine cycle

AIlS. (a)

." '" 0.4 "max '" 0.4 x 0.642 x 0.642 x 2000 = 5J3.6kJ W1 "' 513.6-360 = 153.6kJ COP oflhe actual refrigerator cycle
WI " 0.4

COP - ~ - Oo4x 4.22 '"" 1.69


Q. - 153.6 x 1.69 '"" 259.6 kJ

Qj - 259.6 + 153.6 " 413.2 kJ Q2 = Q I - WI '" 2000 - 5 13.6 = 148604 kJ
Heal rejectcd to the 40C reservoir

Ans. (b)

- Q2 + QJ - 413.2 + 1486.4 - 1899.6 IU

AIlS. (b)

Example 6.... Which is the more elTc:ctive way to increase the efficiency of a Carnot engine: to increase T I keeping T2 constant; or 10 decrease T2 keepi ng TI constant? Solution The efficiency ofa Carnol engine is given by

1J=1 - If T2 is constant


As TI increases. I} increases. and the S]ope(

If TI is eonsUlnt.


decreases (Fig. Ex. 6.4.1).


.!i..) __ J.. [in; 7j


As T2 decreases. (Fig. Ex. 6.4.2).


increases. but Ihe slope

( *t


co nstant

142=1.0 ......... .,. . .. - . .





fig. Ez. 6.4.1


(i!l) d1j

~ 2i. ,,'


(i!l) _ _-"d72 Tl 1jZ


T]>Tl'(:~)Tl >(:~)Tl
'It "" I ~-.6T

SO. the more efTe<:tive way \0 increase the efficiency is to decrease Tl . Alternatively, let Tz be decreased by llTwith T] remaining the same


1fT] is increased by the same llT, Tl remaining the same

Ih " l-~

1j + .6T

'II-'ll '" 7:+.1.T -


72 - .6T

.. (1j - 12)6T+(6T)2 1j(1j +.6T) Since TI > T2 ('II - '12) > 0 The more efTe<:tive way to increase the cycle efficiency is to decrease T2

Example 6.5 Kelvin was the first to point out the thermodynamic wastefulness ofbuming fuel forthe direct bealing ofa house. It is much more economical 10 use the high lemperature heat produced by combustion in a heat engine and then to use the work so developed to pump heat from outdoors up to the temperature desired in the housc. In Fig. Ex. 6.5 a boiler furnishcs hent QI at the high temperature TI . This hcat is absorbed by a heat enginc, which extracts work II' and rejects the waste heat Ql inlo the house at Tl Work II'is in turn used to operate a IOe(;hanical refrigerator or heat pump, which extractsQ) from olltdoors at temperature T) and rejects 0'2 (where Q' 2 "" Q) + W) into tbe house. As a result

ofthiscycleofopel1ltions, a tolal quantity of heat eqUlll loQz + Q'l is Jiberuted in the house. againsl Qt which would be provided directl y by the ordioary combustion of the fuel. Thus the ratio (Q2 + Q'VlQ, represents th e heat multiplication factor of this method. Detcnninc this multiplicatioo factor if T\ - 473 K, T2 - 293 K, and T, - 273 K. SQ/u/io n For the revel1iible heat engine (Fig. Ex. 6.5)

IQ~d~\ 1

Fig. Ex. 6..5

2L .!L


Q! a Q'(~ )

q=.!!::.=7j-72 Ql 7j

w. l1 - 72 r,
Forthe reversible heat pump


cop ", ~=~

T2 -T,

Q2=~ . r; -72 ' Q, r; - 1j 7j

:. Multiplication factor (M.F.)



QJ +Qi

M.F. "*


122 - Tl 1j + 1l1i 1j(Tz

T l)


M.F. '" 1l(7j -7]) 1j(Tz 7J) T, - 473 K, Tl ~ 29) Kand T3 '"' 273 K

M.F. '" 293 (473 - 213) <= 2930 "" 6.3 Ans. 473(293 273) 473 which means that every kg of coal burned would deliver the heal equivalent 10 over 6 kg~ Of COUl"SC, in an actual case, the efficiencies would be less than Carnot efficiencies, but even with a reduction of 50%. the possible savings would be quite significanL &:ample 6.6 It is proposed thai solar energy be used to warm a large collector plate. This energy would, in tum, be transferred as heal 10 a fluid wilhio a heat engine, and the engine would re{ect emrgy as heat to the atmosphere. Experiments
indicate .hat about 1880 kl/m h of energy eM be eolleded when the plale is

operating at 90C. Estimate the minimum collector area thai would be requ ired for a plant producing 1 kW of useful shaft power. The atmospheric temperature may be assumed to be 20C. Solution The maximum effiCiency for the heat engine operating between !he collector plate temperature and the atmospheric temperature is
I1max - I -

Ii 7; -

293 1 - 363 " 0.192

The efficiency of any actual heat engine operating between these temperatures would be less than this efficiency.


Q.... _ ~ = I kJ /s ~ 5.2 1 kl/s l1mu 0.192

'" 18,800 kllh

:. Minimum area required for the collector plate

.. 18.800 .. 10 m2



~p1e 6.7 A reversible heat engine in a satellite operates between a hot reservoir at T] and a radiating panel at T~ . Radiation from the panel is proponional to its area and to r2~ ' For a given work output and value of T1 show

that the area oflhe panel will be minimum when.2.


~ 0.75.

SaotuJ lAw .j17urmolfpwmia


Delennine the minimum area of the panel foran oulpulof I kW if the eoru;\anl of proponionality is 5.67 x IO-li WfmzK 4 and Tl is 1000 K. Solution For the heat engine (Fig. Ex. 6.7), the heal rejected Q1 10 the panel (at T:J is equal 10 Ihe energy emitted from the panel 10 the surroundings by radiation. If A is the area of the panel, Q2 0< A.Tz~. or Qz '" KATt, where K is a eonslant.


fJ "'lf.. = 7;-12
Ql Tl

IV Ql _ ~ _ KArt ------- -11 - 12 11 72 12



For a given If and T]> A will be minimum when



W 1 _, ...J 4 -1 - - - (3T\T2 - 411HTlli - T1) = 0


(TITf - Tl~r1 ~ 0, 3TI Tl - 4T.l

r _ 0.75 Proved. ..:r.


..linin '" K(0.75)' 7j'(7j - 0.75 7j)

IV K ..E....r.
256 1

256W 27K7j4


IV - 1 kW, K " 5.67 x IO-~ W /ml K4, and Tl

A . ..

1000 K

1 4 256xlkWxm K

27x5.67xlO-l!Wx(lOOOtK 4


10&6 = -

~2~ 7C xC5;' .6;;7"x -':c IO"~:'-:Xc,OO""r m

.. 0 . 1672 m 1

256 X Wl

A~ .

6.1 6.2 6.3 6.4 6.05 6.6 6.7 6.8 6.9 6.10 6. 11 6. 12 6. 13 6.14 6.105 6.16 6.17 6.18 6.19 6.20 6.21 6.22 6.23 6.24 6.25 6.26 6.27 6.28 6.29 6.30 6.31
What is Ihe qualitative difference between heat and work? Why are heat and work not completely interchangeable forms of energy? What is a cyclic Ileal engine? Explain a heal engine cycle performed by a dosed systml. Explain a hcatengine cyc le performed by a steady flow system. Define the thermal efficiency ofa heat engine cycle. Can Ihis be l OO%? Draw a block diagram showing the four energy interactions of a cyclic beat engine. Wbal is a thermal energy reservoir'? Explain thc terms source I!lId 'sink' Whal is a mCl:h.a.nical energy reservoir? Why Cl!ll all processes in a TER or an MER be assllmed to be quasi.stalic? Give the KelvinPlanck statement of the second law. To prod\ICC net work in a thermodynamic cycle. a heal engine hIlS to exchange beal with two thermal reservoirs. Explain. What is a PMM2? Why is it impossible? Give Ihe Clausius' statement of the second law. Explain the operation ofa cyc lic refrigerator plant with a block diagram. Define tl\c COP ofa refrigerator. What is a heat pwnp? How don it dilTer from a refrigerator? Can YOIl1.lSe the same plant as a beat pump in winter and 8.'l a refrigerator in summer? uplain. Show thai the COP of a heat pump is greater than the COP ofa refrigerator by unity. Wby is direct heating thermodynamically wasteful'! lIow CM a heat pump upgmde low grade waste heat? Establish the equl>lIlcnce ofKclvrn-Planck and ClallSillS statemcnl.5. What isa reversible proco:ss? A reveniible process should noeleave any evidence 10 show that the process had ever occlIlTCd. Explain. How is a reversib le process on ly a limiting process. never to be attained in practice? All spontaneous proccs.so:s arc irrevttSible. Explain. What an: the causes of irreversibility ora process? Show that heat transfer through a finite temperatun: difference is irreversible. Oemon5lTale, using the seamd la\\", Ihat free expansion is i~versible. Wbat do you understand by di ssipative effects? When is work said to be dissipated? Explain perpetua l motion oftlle third kind. Demonstrate using tbe ICCOnd law how friction makes a process irrevttSiblc. When a rotaling wheel is broughl 10 resl by applying a brake. show tbal tbe molecular internal energy or tbe system (oflhe brake and the wheel) increases.

6.32 Show that the dissipation orstirring work to intemal energy i'l ilTCVrn;ibJe. 6.33 Show by se.:ond law withe dissipation of electrical worlc into internal energy or

lleat is itrevrn;ible. 6.34 What is a Camot cycle? What are the four processes which constitute the eytle? 6.3S E.lpJain the Camo( heal engine cycle executed by: (a) a stationary system, and (b) a steady flow system. 6.36 What is a reversed heal engine? 6.37 Shnw that the efficiellCY of a revrn;ib le engine operating between two given constant temperatures is the maximum. 6. 38 Show thai the efficiency of all n::versible beat engines operating between the same temperature IC\'cls is the ,ame. 6.39 Show that the effic iency of a reversi ble engine is independent of the nature or amount oflbe working substance going through the cycle. 6.40 How does the efficiency of a n::versible cycle depend ooly on the two temperatures I( which heal is traruiferred? 6.41 Whit is the absolute thermodynamic temperature scale? Why is it called abso lute? 6.42 How is the absolute scale indcpdent of the working substance? 6.43 How doe, Q play the role ofthermometrie property in the Ke lvin Scale? 6.44 Show that a definite zero point exists on the absolute temperature seale but thai this point cannot be reached without a violation of the seoond law. 6.45 Give the Fowler-Guggenheim statement of the tbird law. 6,46 Is the third law an cxtension of the second law? Is il an independent law of lWure? Explain. 6,47 How does the efficiency of a reversible engine vary as the souree and sink tempenlturcs are varied? When does the cfficiency become 100%? 6,48 For a given f 2' show that the CO P ofa refrigerator increases as T, decrcases. 6.49 Explain how the Kelvin temperature can be measured with a gas thelmOme1Cf. 6.50 Establish the equaliry of ideal gas tempel11ture and Kelvin temperature. 6.51 What do you undcmand by internal im:versibility and external irreversibil ity? 6.52 Explain mechanical, thermal and chemical irreversibilities. 6.53 A Camol engillC with a fucl burning device 3Ii wurce and a heat sink cannot be treated as a reversible plant. Exp lain.

~elopcd an cngine thai takes in lOS MKJ at a temperature of 400 K. rejects 42 MJ at a temperatutC of 200 K, and deJivCf'$ IS kWh of mechanical work. Would you advise investing money to put this engine in the market? 6.2 If a refrigerator is used for heating purposes in winteT so that the atmosphere: becomes the: cold body and the room to be heated become! Ihe bot body. how much beat would be available for heating for each kW input to the driving molOr? The COP of the refrigerator is 5, and the ele<:ttomech.anic:al efficiency of the motor is 90%. How docs this contpare with resistance heating? Alt!. 5.4 kW, IkW

6. 1 An inventor claims 1 0 have


148=6.3 Using an engine of300 ,4 thmnal efficiency of dri~'e a n:frigeralor having a COP of S, whal is the heal inpuit inlO the engine for each MJ n:movc-d from the cold body by the refrigerator? Ani. 666.67 kJ Ifth ill syslt'TTI is used IS a heat pump, how l1W\y MJ of heat "'"Quid be: available for heating for each Ml oflleat input to the engine? An!. 1.8 MJ 6.4 An electric storage battery which can exchange heat only with a constant tcmpeTlUII/"C atmosphere goes through a complele cycle of two processes. In process 1-2, 2.8 kWh of electrical won flow into the bilncry while 732 kJ orheat flow out 10 theatmosphere. During process 2- 1, 2.4 kWh of work flow out of the banery. (a) Find the heat transfer in process 2-1. (b) If tbe: process 1- 2 lw; occurred as above. doc! the first law or the Sttond law limit the tnalIimum possible work of process 2- 1? What is the maximum possible work? (c) If,he maximum possible work were obtained in procns 2- 1, what will be the heat tnll\$fer in the process? (I) - 708 kJ (b) Second law, Wl _ J .. 9348 kJ (c) Ql_J .. 0 6.S A household refrigerator is maintained al a temperature of2C, Every time the door is opened, warm material is placed inside, introducing In average of 420 kJ, but making only a small change in the temperature of the refrigerator. The door is opened 20 timeSI day, and the refrigemloropcrates It 15% of the ideal COP. The COSI of work is 32 paise per kWh. Whal is the monthly bill for this refrigerator? The atmospbefe is al 30C. Ani. Rs. I S.20 6.6 A beat pump ",vrking on the Carnal cycle takes in beat from a reserooir al SC and delivers ncallo a reservoir at 6(fC . The beat pump is driven by a reversible heal engine which takes in heat from a reservoir al 840C and rejects beal to I fC$etvoir at 6OC. The reversible heal engine also dri~'es a machine thai absorbs 30 kW. If the heat pump extracts 17 kJ/s from the SOC reser.vir, determine (a) the talC of heat supply from the 8400C SOW"Ce. and (b) the rate of heet rcjeo::tion to the: 6O"C sink. Ani. (a) 47 .61 kW ; (b) 34.61 kW 6.7 A refrigeration plant for a food store opmltes with a COP which is 40'" Ao orlhe idea] COP of a Carnot of refrigarator. The store is to be: maintained DI a Icmpc:nItUn: of - SC and the heat transfer from the store to the: cyele iS11 the rate ofS kW. Ifheat is transferred from the cycle to the aunosphere at a temperature of 2S C, calculate the power required to drive the plant and the heat discharged to the aunosphere. An.r. 4.4 kW, 6.4 kW 6.8 A heat engine is used 10 drive a heal pump. The heat transfers from Ihe heal engine and from the heat pump are med to heat the watercireulating through the radiators ofa building. The effic iency of the heal en8ine is 27% and the COP of the heat pump i~ 4. Evaluate the nltio ofthe beat transfer to the circulating wator to the heat transfer to the heal engine. Ani. l.81 6.9 If 20 kJ are added to a Clunot cycle at a temperature of lOO"C and 14.6 kJ are n:jected at OC, dtmnine the location ofab50lute zero on tbe Celsius scale. An!. - 270.JP C

"' "

- = 149
6. 10 Two reversible hcat engines A and B an: aml!1ged in series, A rcje<:ting heat directly 10 B. Engine A receives 200 kJ al a temperature of 421 "C from a llOt source, while engine B is in communication with a cold sink at a temperalUTe of 4.4 "C. If the work output of A is twi~e that of B, find (a) the inlermcdiate tcmpemture-betv.ccn A and B, (b) the effICiency of each engine, and (e) the heat rcjted to the cold sink. A"-I'. 143.4C, 40" .4 &. 33.5% . 80 kJ 6.11 A heat engine openltes between the maximum and minimum tempenltures of 671 C and 6O"C respective ly, with an efficiency of50% o r the appropriate Carnot efficiency. It drives a heat pump which uses river water aI4.4"C to heat a block of flats in which the temperature is 10 be maintained at21.1 C. Assuming that a temperature d ifference of II.I "C exists between tbc working fluid and the river water, on tlte ooc hand, and the required room temperature on the other, and 8S$IIIIIing thc heat pump to operate on the re\'CI'$Cd Carnot cycle, but with a COP of 50% of the ideal COP, find the heat input to the engine per unit heat OUtput from the heal pump. Why is direct heating thCTlllod'fllamically more wll5teful'/ 1'1"-1'. 0.79 kJlkJ heat input 6.12 An ice making plant produCC!! ice at atmospheric pre$SUfe and at OOC from water at OOC. The mean temperature of tlte cooling water cin:ulating through the Evaluatethe minimum electrical COJIdenserofthe refrigerating machine is I work in kWh required to produce I tonne of ice. (The enthalpy offusion ofice at aunosphcric pressure is 3US kllkg). A"-I'. 6.11 kWh 6.13 A revcnible engine works between thll.'C lhermal reservoirs, A, 8 and C. 'The engine absorbs an equal arnowu oflleat from the thermal reservoirsA and 8 kepi atlempcr:atUte$ T" and Te respectively, and rej15 beal lO the thermal reservoir C kept al temperature Te. The efficiency of the engine is alimes the efficiency of the reversible engine, which works between the two reservoirs A and C. Prove

so c.


..!A. (2a - I)+ 2(1 _ a) ....t:...


T c

6. 14 A reversible engine opcr:ate! between tempernfUres Tl and 71,Tl > The energy rejected from th is engine is received by a second re\'enible engine at the:wne tcmperatureT. Thesecond engine rejects energy al temperature T2 (T2 Show that (I) tempcnture T is the arithmetic mean of lempcr:atures T, and Tl if the engines produce the same amount of work output, and (b) temptl'lture T uthe geometric mean of IcmlX'ratures Tt and T2 if the engines have the same cycle efficiencies. 6.1S Two Carnot engioes A and B are connected in series between two th=1 resen'oir$ mainlained al 1000 K and 100 K respecth-ely. Engine A receives 1680 kJ of heat from the hightemperature reservoir and rejCClS heal to the Carnol engineB. Engine 8 takes in heal rejected by engineA and rejCClS heal tothe lowtemperature ~r"'oir. If engines A and B Mve equal thermal efficiencies. determine (a) the heat rejected by engine B, (b) tl,~ temperature at which heat is rejected by engin~ A, and (e) the work done during the process by enginesA and B respectivcly. If engines A and B deli\'erequal work, dclCTllline (d) the atnOum of heat takCD in by engine B. and (e) the efficiencies of engines A and B. A1I$. (a) 168 kl, (b) 316.2 K-(c) 1148.7,363.3 kJ, (d) 924 kJ, (e) 45" .. 81.8%.



150=6.]6 A beal pump is 10 be used to heal a house in winter and then re\'Crscd 10 cool the house in 5 = . The interior temperature is to be maintained al 20C. Heat transfer through tile walls and roof is eSlimated to be 052S kJfs per degree temperature difference between the inside and outside. (a) If the outside temperature in winter is SC, what is tbe minimum power required 10 drive the heat pump? (B) tfthc power OUlput is the same iii in pan (a) . what is Ihe muimum OIIter temperature forwhicb the inside can be maintained al 20"C1 AIlS. (0) 403 W, (b) 3SC. 6.17 Consider an cngine in ouler space which operates on the Camot cycle. The only way in whicb heat can be lransfernd from Ihe enging i, by radiation. The rale at which heat is radialed is proportional 10 the fourth power of the absolule tanperature Tl and 10 the area of the mdialing surface. Show lhal for a given power output and a given TI . the area of the radiator will be a minimum when

.2. ",1. r, 4
6.18 It takes 10 kW to keep the interior ofa certain house al 20 C when the outside lemperature is Oc. This heat flo w is Wlually obtained direclly by burning gas or oil. Ca lculate Ihe power required if the 10 kW beat flow wcre supplied by operating a reversible hcal pul with the hoU$e as thc upper reservo ir and thc o utside sunoundings as the lower re5el'\'oir. AIlS. 0.6826 kW 6.19 Pro"c thai thc COP of a reve~iblc refrigerator operaling between r,o.o given tcmperatul'C5 is thc lTIlIJIimurn. 6.20 A house i510 be maintained at a tcmpcralure of20"C by mcatls ofa heat pwnp pumping heat from thc aunosp~. HcalloSeS Ihrough the wall, of the house are eslimated al 0.65 kW per unil oftcmpemlure differencc ber,o.cen lhe inside of the hollSC' and the atmosphere. (a) If!he atmospheric temperalure is - ]O"C, what is Ihe minimum power required 10 drive the pump? (b) It is proposed 10 use Ihe same heal pump 10 cool the house in summer. J:or lbc same room temperature, the same heat loss rale. and the same power inpul to !he pump. what is the maximum permissible atmospheric lempernlUre? Ans. 2 kW, SO"C. 6.2 1 A solar-powered heal pump receives heal from a so!arco1t~toral Tk rejects heat 10 the atmosphere al T. , and pumps heal from a cold space al Te' The three heal InInSfer rales arc Qk. Q. and Q, respecti vely. Derive an expression for the minimum ralio Q,jQ" in lenns of the three temperalures. lrT~ - 400 K, T. '" 300 K, T, 200 K. Q, ]2 kW, whal is the minimum~? If the collector captures 0.2 kWfm1 , whal is !be minimum eoUeelor area required? A ..... 24 kW , 120ml 6.22 A heal engine operating between two rcscrvoi~ al 1000 K and 300 K is used 10 drive a heat pump which elltracts heat from the reservoir al 300 K at a rale twice thai al which the engine rejects heat 10 il. Iftheefficicncy of the engine is40"'/o of thc ma~imum possible and !he COP of the heat pump is 50% of the ma.timum possible, what is the lemperature of the reservoir to which the heat pump rejects hea!? Whal is the rate of heat rejection from the heal pump if the rale of heal supply 10 Ihe engine is 50 kW? A..,.. 326.S K, 86 kW

6.23 A rc:vc:rsible power cycle i~ used todri'ea reversible heal pump cycle. The power cycle takes in Q I heal units at TI and rc:jeclS Ql at Tl The heal pump abstractsQ. from the sink al T. and di5eharg~ QJ at Tl . Develop an c)lprc:ssion for the r..atio QJOI in terms of the four tempenltun:s.

1) AnI. ~ = T.Ui - T QI 7j(1j T.)

6.24 Prove that the following propositions arc logically equivalent: (a) A PMM2 is impossible, (b) A weight sli ding 3t constant velocity down a frictional inclined plane eKC(;Ules an irrevenible process. 6.25 A heal engine TCl,;eive5 halfofits heat supply at 1000 K and half at 500 K while rejecting heal 10 a sink al 300 K. What is the maximum possible ,hermal efficiency o(this heat engine? AM. 0.55 6.26 A heat pump provides 3)( 10' kJIh to maintain a dwelling at 23"C on a day when the oUlside lempcn'llUTe is O"C. The power inpulto the lleut pump is 4 kW. Detennine 'he CO P of the heal pump and compare il with the COP ofa revCI"Sible heat pump operating betwccn the reservoirs at the nme two tempemtUTe5. AM. 2.08. 12.87 6.27 A reversible power cycle n:ceiver energy 01 from a reservoir at temperature T, and n:jects Ql10 a reservoiral temperalun: T1. The work developed by the power cycle is used to drive a TCVcrsible heat pump that removes energy (l1 from a reservoir at temperature T 1 and rejects energy (lIto a reser.oir at tempcralUn: (a) Determine an ellprcssion for the ratio (ll fQ! in term! of Ihe four temperatun:s. (b) What must be !he relationship of the tempcnllures TI Tl r l and r I fot Q' lfQI 10 eKeeed a value of unity?


AM. (a)

QI = 7;'( 7j - 12) (b)




T1 , -< Tl

7i, 7i

6.28 When the oulSide temper:lIUrt: is - IO"C. a n:sidential heal pump must provide 3.5 )( 106 kJ per day to a dwelling 10 maintain its temperarun: at 20 C. If ~la:tricily costs RI. 2.10 per kWh. firtd the minimum theoretical operaling CO$l for each day of operation. AM. RI. 208.83


7.1 Introduction
The fU11 law of thermodynamics was stated in terms of cycles first and it was shown thaI the cyclic integral of heat isequallolhe cyclic integral ofwod::. When the first law was applie4 for thermodynamic processes, the existence of a property, the intemal energy, was found. Similarly, the seeond law was also first stated in terms of cycles eJltcuted by systems. When applied to processes, the second law also leads to the defmilion ofa new propeny, known as entropy. If the fll'St law is said to be the law orintcmal energy, then second law may be stated to be the law of entropy. In fact, thermodynamics is the study o/three E 's, namely,

energy. eqUilibrium and ell/ropy.


Two Reversible Adiabatic Paths Cannot

Intersect Each Other

Let it be assumed that two reversible adiabaticsA C andBC interse<:t each other at point C (Fig. 7.1). LeI a reversible isotherm AS be drawn in such a way that it intersects the reversible adiabatics atA andB. The three reversible processesAB, BC, and CA together constitute a reversibl e cycle, and th e area included

represents the net work output in acycle. But such a cycle is impossible, since net work is being produced in a cycle by a heat engine by exchanging heat with a single reservoir in the processAB, which violates the Kelvin-Planck statement of the second law. Therefore, the assumption of the intersection of the reversible adiabatics is wrong. Through one point. there con pass only one reversible odiobotic. Since two constant property lines can never intersect each other, it is inferred that a reversible adiabatic path must represent some property, which is yet to be identified.




- .
7.3 Clausius' Theorem
Let a system be taken from an equilibrium state i to another equilibrium statefby following the reversible path i-f(Fig. 7.2). Let a reversible adiabatic i-a be drawn through i and another reversible adiabatic b-jbe drawn Woughj. Then a reversible isothenn a-b is drawn in such a way that the area under i-a-b-fis equal to the area under i-I Applying the fir.;t law for
Rev. Jldiabatk:s

Process i-/
Process i-a- b-f

e..r "" Ur - U + W


(7. 1)

:. From Eqs (7.1) and (7.2)

Q,r = Qiabr
- Qio + Q.., + Qbr Qia '"' 0 and Qbf - 0



Oo<f : Ooob Heat tmnsferred in the process i-f is equal to the heat tmnsferrc:d in the isothennal processa-b. Thus any reversible path may be substituted by a reversible zigzag path, between the same end states, consisting of a reversible adiabatic followed by a reversible isotherm and then by a reversible adiabatic, such that the heat transferred during the isothermal process is the same as that transferred during the original process. Let a smooth closed curve representing a reversible cycle (Fig. 7.3) be considered. Let the closed cycle be divided into a large numberofstrips by means of reversible adiabaties. Each strip may be closed at the top and bottom by reversible isotherms. Theoriginal closed cycle is thus replaced by a zigzag closed path consisting of alternate adiabatic and isothennal processes, such that the heal transferred during all the isothermal processes is equal to the heat transferred in the original cycle. Thus the original cycle is replaced by a large number of Carnot cycles. If the adiabatics are close to one another and the number ofCamot cycles is large. the saw-toothed zigzag line will coincide with the original cycle. For the elemental cycle ahed, dOol heat is absorbed reversibly at T l and It Q2 heat is rejected reversibly at T2

- ->0

Fig. 1.3 A rlflmihk CJ<u .pUt inu" l<Irgt numbtr ofC<!rnot '1'Us

ItQ! = ItQ2



Ifheat supplied is taken as positive and heat rejected as negative d Ql + d~ = 0 7; T2 Similarly, for the elemental cycle efgh

If similar equations are written for aU the elemental Carnot cycles, then for the whole original cycle

I~ 'O T


The cyclic integml of dQIT for a reversible cycle is equal to zero. This is !mown as CIUU5illS ' theorem. The letter R emphasizes the fact that the equation is valid only for a reversible cycle.


The Property of Entropy

Let a system be taken from an initial equilibrium state i to a final equilibrium state / by following the reversible path RI (Fig. 7.4). The system is brought

'~ '

back from/lo i by following another reversible path R2 . Then the two paths R [ and Rl together constiNte a reversible cycle. From Clausius' theorem



The above integral may be replaced as the sum of I\\'O integrals, one for path Rl and the other for path R2


156=Since R2 is a reversible path


1..-= IT


r dQ

Since RI and R2 represent any two reversible paths.

~ ~ is independent of

the reversible path connecting i and f. Therefore, there exists a property of a system whose value at the fmal state/minus its value at the initial stalei is equal to

J~. This propeny is called entropy, and is denoted by S. IfS; is the entropy

al the initial state i, and S, is the entropy at the fmal state f, then

, T

, dQ IT - S,-S,
When the two equilibrium states are infinitesimally near



where dS is an exact differential because S is a point function and a property. The SUbscriPI R in dQ indicates thai heal d Q is ttansferred revenibly. The word 'entropy' was first used by Clausius, taken from the Greek word 'tropee' meaning 'transfonnation'. It is an extensive property, and has the unit 11K, The specific entropy
s _..i. llkg K

If the symm is taken from an initial equilibrium state j to a fmal equilibrium state fby an j"~nlble path, since entropy is a point or state function, and thc entropy change is independent of the path followed, the non-reve1'llibJe path is to be replaced by a reversible path to integrate for the evaluation of entropy change in the irreversible process (Fig. 7.5).

Fig. 7.5

!/.. : " , ...... i AetuaI

JIIkgraIi~1I tlllI


Rev. path wI'Och replaces


. ---s.
be UIIl

: irreV. path


DII 4 r-mbk />4t1r.




(1.6) Integration can be perfonned only on a reversible path.

1.. 1 TtM/ltrllhlre-E"tropy Plot

The infmitesimal change in entropy dS due to reversible heat transfer 4Q at temperature T is

dS - ~


If r:tQ_ - 0, i.e., the process is rever.;ible and adiabatic

<IS - O
S = constant

A reversible adiabatic process is, therefore, an isentropic process.

dQ~ =

Now TdS

Q_ - j


The system is taken from ito frevcrsibly (Fig. 1.6). The area under the

, , For reversible isothennal heat transfer (Fig. 7.7), T " constant.

J T dS is equal 10 the heat transferred in the process.

Fig. 7.6

Fig. 7.7

Arm llruln" mwuiht. ptJM on

&vmiht. isQ1/tmM1 MIt Ir",,*"

tJu Ts plDl rt/JttJnw lUl21 IttJIIJjiT

For II. ~versible adiabatic process, dS '"' 0, S - C (Fig. 7.8). The Carnol cycle comprising two reversible isothenns and rwo reversible adiabatics forms II. re<:tangle in the T-S plane (Fig. 7.9). Process 4- 1 represents reversible isothcnnal heat addition Q I to the system at 11 from an external


" 1

Fig. 7.8

_ 5
lU:mibk adidalif u utnltQpic

" 1


, >5

' - " ' T2

FIg. 7.9

Om!QI ",I,

source, process 1- 2 is the reversible adiabatic expansion of the syslem producing WE amount of work, process 2-3 is the reversible isothennal heat rejection from the system to an extemal sink at T1, and process 3- 4 represents reversible adiabatic compression of the system consuming w. amount of work. Area I 2 3 4 represents the net work output per cycle and the area under 4-1 indicates the quantity of heat added to the syslem QI'

'1camoc " ~ :: -"r,,,,(~,,--O'S,;;):---,"r,~(S,;,----,S"-,,)


1j(St - S4)


",, 1j-T 2 = 1_li 7j 7j W.... ~ QI - ' Q2 "" (TI - T2) (51 - S,)

7.5 Principle of Caratbeodory

Tbe property "entropy" was bere introduced througb the historical route as initiated by the enginccr Camot and elaborated by the physicists Kelvin and Clausius, Starting with the statemenl expressing the impossibility of converting heal completely inlo work, or the impossibility of spontaneous heal flow from a colder to a holler body, an ideal heat engine of maximum efficiency was described. With the aid of this ideal engine, an absolute temperature scale was defined and the Clausius theorem proved, On the basis of the Clausius theorem, the existence of an entropy function was inferred, In 1909, the Greek mathematician Caratheodory proved die existence of an entropy function without the aid of Carnot engines and refrigerators, but only by malhematical deduction. Let us consider a syslem whose states are determined by three thermodynamic coordinatesx,y and t, Then the first law in difTerenlial form may be written as dQ '" Adx + Bdy + Cdz, where A, B, and C are functions ofx,y and2. The adiabatic, reversible transition of thi s system is subject to the condition dQ " Ad..\' + Bdy + Cd:: " 0



which leads to the mathematical statement of the second law as: In the neighbourhood of any arbiTrary initial slate Po of a physical syslem Ihere exist neighboUring slales which (Ire nol accessible from Po alollg quusistorie udiabatie paths. It follows from Caratheodory's theorem that this is possible if and only if there exist functions T and S such that: c1Q " Adx + Bdy + Cd: " TdS Thus, by stating the second law in tcnns of the inaccessibility of ccrtain stales by adiabatic paths, and by using a mathematical theorem (for the proof see Hsieh), Caratheodory inferred the existence of an entropy function and an integrating factor connected with the Kelvin temperature.

7.6 The Inequallty of Clausius

Let us consider a cycle ABeD (Fig. 7.10). Let AB be a gene ral process, either reversible or irrevers ible, while the other processes in the cycle are reversible. Let the cycle be divided into a number of elementary cycles, as shown. For one of these elementary cycles

Fig. 7.10

of Clausius

where ctQ is the heal supplied al T, and c1Q2 the heat rejected al T2_ Now, the efficiency of 11 general cycle will be equal to or less Ihan the efficiency of a reversibl e cycle.

- dQ,

dQ :!>




5b.. [5b..J


4Q [ dQ2

J",." ~ T



~ s~, for any process AB, reversible or irreversible. T r,

For a reversible process


Hence, for any process .AB


Then for any cycle

f 4i <jds
Since entropy is a property and the cyclic integral of any property is zero

lbit equation is known as the inequalityofClausius. Itprovides the criterion of the reversibility of a cycle.

f 4i ., 0, the cycle is reversible,

f 4f < 0, the cycle is irreversible and possible

"' "


f d"~ > 0, the cycle is impossible, since it violates the second law.
7.7 Entropy Change in an lrrevenlble PrOcell
For any process undergone by a system, we have from Eq. (7.8)

This is further clarified if we consider the cycles as sbown in Fig. 7.11,

, --< i<'
Fig. 7.11

" tf
a .. /


/ c

dulq< ill .<lll imtImlbk p1/ICW

where A and B are reversible processes and C is an im:versible process. For the reversible cycle consisting of A and B


)- =-)T





FOT the irreversible cycle consisting ofA and C, by the inequality of C lausius, (7.12)

From Eqs (7. 11) and (7.12),


. 1

162= 1 dQ 1 4Q -1 - +1- <0 ,T ,T

1 2

1->12 T T , Since the path B is reversible, ,Q ,






= IdS


Since entropy is a property,entropy changes for the paths B and C would be th e same. Therefore,

From Eqs (7.13) to (7.IS),

IdS -IdS
, , dQ

(7 .IS)

, ,

IdS > l

,T ,

Thus, for any irreversible process,

whereas for a reversible process

dS <o 4Q=.

Therefore, for the general case, we can write

(7.1 6) The equality sign holds good for a. reversible process and the inequality sign for a.n irreversible process.

"' "


- = 163

7.8 Entropy Principle

For any infinitesimal process undergone by a system, we have from Eq. (7.10) for the total mass dS?: dQ T For an isolated system which does not undergo any energy interaction with the surroundings, d Q ., O. Therefore, for an isolated system (7.1 7) For a reversible process, dSloo '" 0 s ~ constant For an irreversible process dSioo > 0
It is thus proved that the entropy oj an isolated systt!m can never decrease. It always increases and remains constant only when the process is reversible. This is known as the principle oj increase oj entropy, or simply the entropy principle. It is the quantitative general statement or second law from the macroscopic viewpoint. An isolated system can always be fonned by including any system and its surroundings within a single boundary (Fig. 7. 12). Sometimes the ongilSal system which is then only a pan of the isolated system is called a 'subsysteul'.
~~~ .m


'"""""'.... .....,
(o;:omposit,,) I ystem

Fig. 7.12 ilouJltJ ]Sltm

The system and the surroundings together (the universe or the isolated system) include everything which is affected by the process. For all possible processes that a sys:em in the given surroundings can undergo dSuniv 2: 0 or dSJ)'J + dS.... 2:0 (7.18) Entropy may decrease locally at some region within the isolated system, but it must be compensated by a greater increase of entropy somewhere within the system so that the net effect ofan irreversible process is an entropy increase of


the whole SYStem. The entropy increase of an isolated system is a measure of

the extent of irreversibility of the process unde rgone by lIle system.

Rudolf Clausius summarized the first and second laws of tbennodynamics in

the following words: (a) Die Energie der Welt ist Constant.

(b) Die Entropie der Welt strebt eioem Maximum:ow.

[(a) The cottgy of the world (universe) is COnstanL (b) The entropy oflhe world lends towards a maximum.)

The entropy oran isolated system always increases and becomes a maximum
at the state oCequilibrium. If the entropy ohn isolated system varies with some

panmeter x, then there is a certain value of x. which maximizes the entropy

= 0) and represents the equilibrium stale (Fig. 7.13). The system is ( when dS ~ .
then said to exist at the pe:ak oCthe entropy hill, and dS - o. When the system i5 at equilibrium, any conceivable change in Clltropy would be zero.

FIg. 7.13 Eq.iJimlltll stall

~f n

iJoI4.ltd I1sWrl

7.9 AppUcatioDJ of Entropy Principle


The principle of increase of entropy is one of the most important laws of

physical science. It is the quantitative statement of the second law of thermodynamics. Every irreversible process is accompanied by entropy increase of the universe, and this entropy increase quantifies the extent of irreversibility of the process. The higher the entropy increase of the universe, the higher will be the irreversibility of the process. A few applications of the entropy principle are illustrated in the following,


TrtnuJtr oj htal thTOtlgA a Fintle Tt7IIjlnflhlrt Difference

Let Q be the rate of heat transfer from reservoir A at Tl 10 reservoir B at T1 Tl> Tl (Fig. 7. 14). For reservoir A. OS" .. - QITJ It is negative because heat Q flows out of the reservoir. For reservoir B. OSB = ... QITz It is positive because beat flows into


___ .. r ~~~ Ii " I

FIg. 7.14



Hrot hlltuj ... tAroll",. II fi~it. 1mI/>tf'lllwrI 'iffmllu

the reservoir. The rod connecting the reservoirs suffers no entropy change because, once in the steady stale, its coordinates do not change. Therefore, for the isolated system comprising the reservoirs and the rod, and since entropy is an additive property

S "S,,+S8 45..... '" 45" + 458


45 , =_ ~+.="Q.'Ti-1i ""'. 'Ti 1i 'TiT2

Since TI :> Tl , 45..... is positive, and the process is irrever.;ible and possible. If TI .. T2, 45...... is zero, and the process is reversible. If Tl < T2, 45"",. is negative and the process is impossible.

7.9.2 MIxt"l

0/ TUlo FlflUis

Subsystem I having a fluid of mass ml' specific heat CI' and temperature ' 1' and subsystem 2 consisting of a fluid of mass m2 specific heat C2. and temperature 12, comprise a composite system in an adiabatic enclosure (Fig. 7.IS). When the partition is removed, the two fluids mix together, and at

~ :

" . , . ' .:





Subsystem 2

.' t.,

Subsystem 1

FIg. 7.1S

MiX'illl ~ftujIwids

equilibrium lettrbe the final temperature, and'2 < 1, < 11, Since energy interaction is exclusively confined to the two fluid$, the system being isolated
CIO I - If)

= m 2 C2 (tf -



,4S t "




+ mlc2 12 + m2 cl

Entropy change for the fluid in subsystem 1

dQ"", = m ]c ]dT = T ] TTIT


m1c ] In


.. m]c] In If

+ 273 + 273

. This will be negative, since T] > Tr Entropy change for the fluid in subsystem 2
T/ m2c2d T



.. m2 C2 In .!.L .. mr:2 1n C' c.;-~;-

r. Ii

+ 273 12 + 273

This will be positive. since T2 < Tf

M Ufti.. " 651 + 4Sl

- m\ c] ln -


+ m2 cl ln


M ...... will be positive definite, and the mixing process is irreversible. Although Ihe mixing process is irreversible, 10 evaluate the entropy change for the subsy~tems. the irreversible path was replaced by a reversible path on which the integration was perfonned. If m1 .. ml"" m and C1 - ~ .. c.

l:lSun,.. . - mc In -T., .f ,r


T rn\ c]7i + m2cITl

+ mlcl


<u ...... -

me n

1 (T.,+7;)/2

/li .7;

This is always positive. since the arithmetic mean of any two numbers is always greater than their geometric mean. This can also be proved geometrically. Leta semi-circle be drawn with (T] + Tz) as diameter (Fig. 7.16). Here, AB " T]. BC - T2 and DE - (T] + Tl )/2. It is known that (DB)l = AS . BC - T] Tl .
DB -

Jl'., T2



1'., + - .JT:T.; --,Tl




1f. - -",- - ' -..:j :-. - '2 ~

Gromdri(lJ/ prooj/o YlOW fM/ &....


< IJ.m.

7.9.3 Mutmum Work ObtJJitulbh from T!t!o FixiU Bodies at Tnttperatvru T, arut Tl Let us consider two identical finite bodies of constant heat capacity at
temperalUTeS TI and T! respectively. TI being higher than T2. lfthe two bodies are merely brought together into thermal contact, deli vering no work. the final temperature Trreached would be the maximum


'---,7j + Tl

Ifa heal engine is operated between Ihe two bodies acting as thermal energy reservoirs (Fig. 7. 17), pan of the heat withdrawn from body I is can vened to work II' by the heal engine, and the remainder is rejected to body 2. The lowest attainable final temperature Tf corresponds to Ihe delivery of the largest possible amount of work, and is associated with a rever:sible Fig. 7.17 MuimwlII lI!lIr/; IIbtaifU1!k process. As work is delivered by the heat fl-! t_ fi"il~ botJin engine, the temperature of body I will be decreasing and that of body 2 will be increasing. When both the bodies attain , the beat engine will stop operating. leI the bodies the final temperature Tr remain at constant pressure and undergo no change of phase. Total heal withdrawn from body 1 Ql ", Cp (T1 - Tf ) where <1. is the heat capacity of the two bodies al constant pressure. Total heat rejected to body 2

Q2 "" Cp (T, - T!)


163=:. Amount of total work delivered by the heat engine W .. Q] - Qz (7.19) - C p (T] + Tl - 2Tr) For given values of CP' T] and Tl , the magnitude of work W depends on Tr Work oblainable will be maximum when Tf is minimum. Now, for body I, entropy change ~I is given by

\!: " ' For body 2, entropy change .15 would be

45 =

dT =C In..!!.. IJpTPr,

" ' Since the working fluid operating in the heat engine cycle does not undergo
any entropy change, .15 of the working fluid in heat engine .. Applying the entropy principle M .... ~O Cpln Tf +Cp ln

452 -

'J C -dT ",C T


T In ~


dS " O.




1f ~o

Cplnl<!O From equation (7,20), for Tr\O be a minimum

C I, ~' ~- O P 1j .T2
Since Cp *- 0, ,, - ' - "O - Inl
1( = J1j T l


T' 1j72


For Wto be a maximum, Trwill be J1j T2 . From equation (7,19)

Wnw.'" Cp(TI

+ Tl -

2J1iTl " Cp(JT; _JT;)1

The fin.a.l temperatures of the two bodies, initially at TI and Tl can range from (TI + TzY2 witb nodeJivery of work 10 J7i 72 with maximum delivery of work.

7.9.. Muimum Work mtailJabk from a FmiU Bod, and a TER

Let one of the bodies considered in the previous section be a Ihennal energy

reservoir. The finite body has a thennal capacity Cp and is at lemperatW'C T and



the TER is at temperature To. such that T > To. Let a heat engine operate be tween the two (Fig. 7.18). As heat is withdrawn from the body, its tern perature decreases. The temperature of the TER would, however, remain unchDnged at To- The engine would stop working, when the temperature of the body reaches To. During that period, the amount of work delivered is If, and the heat rejected to the TER is (Q - It). Then .tiBod

I j:-~
Flg.1.18 MllXimum

wA,n ont

~f tilt

biitf iJ a TER


C-=Cln~ T r T


4S"He '" f dS "" O

ASTER ~ -T,-


Q W OS ,:o Cln To + ""V P T To

By the entropy principle. 4S"univ 2: 0 C

In- +~2: 0


n_ W





W-Q sC In To P T To WSQ + To Cp ln


W.... = Q+ToCpln r

W.... - C1(T- To)-To In



7.9.5 Prousu ExhibUi.g Exterxal MhatliealJrrnnsibility

(I) hothennal DbalpaUon or Work Let us consider the isothermal dissipation of work through a system into the internal energy of a reservoir. as in the flow of an electric current I through a resistor in contact with a reservoir

(Fig. 7.19). At steady state, the internal energy of the resistor and hence its temperature is constant. So, by first law

W- Q

r ..., ........... ~ c.v.

Flg.1.19 ExItTfU/1 IflMIIUIII irrtllmibililJ The flow of current represents work transfer. At steady state the work is dissipated isothermally into heat transfer to the surroundings. Since the surroundings absorb Q units of heat at temperature T,

M~ ==.!. T T
At steady state,

lIS,,.. .. 0


The irreversible process is thus accompanied by an entropy increase of the universe.

(Ul Adiabatic DllllpadoD of Work Let Wbe the stirring work supplied to a viscous thermally insulated liquid, which is dissipated adiabatically into internal energy increase of the liquid, the temperature of which increases from T; to Tr (Fig. 7.20). Since there is no flow of heat to or from the surroundings, 6S.... - 0 To calculate the entropy change of the system, the original irreversible path (dotted line) must be replaced by a reversible one between the same end states,

=~~:\?~~:( ';,:".=:',: .. . .' .... . .. . ....... ....... ....... .... . , ,..... ' , , ... ,. . .'







; and J. Let us replace the irreversible perfonnance of work by a reversible isobaric flow ofheal from a series of reservoirs ranging from Tj to Tr to cause the same change in the state of thc system. The enrropy ehange of the system

will be
6S. = 'Y'j

where Cp is me heat capacity of the liquid.

Q = SCpdT =C In!!. SaT jT PT;


which is positive.

7.10 Entropy Transfer Mechanisms

Entropy can be rrons/erred to or from a system in two forms: ht!Ollronsjer and mass flow. In contrast, energy is transferred by work also. Entropy transfer is recognised at the system boundary as entropy crosses the boundary, and it represents the entropy gained or lost by a system during a process. The only form of entropy interaction associated with a fixed mass or closed system is heat tnmsfcr, and thus the entropy transfer for an adiabatic closed system is zero. It is being explained below in more details:
(..) Hut Transfer

Since dS -


, when heat is added to a system

aQ is

positive. and the entropy of the system increases. When heat is removed from the system, dQ is negative, and thc entropy of the system decreases. Heat transferred to the system of fixed mass increases the internal energy of the system, as a result of which the molecules (of a gas) move with higher kinetic energy and collide more frequently, and so the disorder in the system increases. Heat is thus regarded as disorganised or disordered energy transfer which increases molecular chaos (see Sec. 7. 16). If heat Q flows reversibly from the system to the surroundings at To (Fig. 7.21), the entropy increase of the surroundings is

6S . T.
The entropy of the system is reduced by
&S "'_



The temperature of the boundary where heat transfer occurs is the constant temperature Til" It may be said that the system has lost entropy to the surroundings. Alternatively, one may state that the surroundings have gained

172=entropy from the system. Therefore, there is entropy trallSfer from the system to the surroundings along with heat flow. In other words, sinee the heat inflow increases the molecular disorder, there is flow of disorder along with heat. The sign of en tropy transfer is th e same as the sign of heat transfer: posi/iI'#!, ifinto the system, and negalil'e, if Out of the system.

On the other hand, there if no entropy transfer associated with work. In Fig. 7.22, the system delivers work to a flywheel, where energy is stored in a fully recoverable form. The flywheel molecules are simply put into rotation around the axis in a perfectly organised manner, and there is no dissipation and hence no entropy increase of the flywheel. The same can be said about work transfer in the compression of a spring or in the raising of a weight by a certain height. There is thus no entropy transfer along with work. If work is dissipated adiabatically into internal energy increase of the system (Subsection 7.9.5), there is an entropy increase in the system, but there is as such no entropy transfer to it. Work is thus emropy-jree, and no entropy is transferred with work. Energy is transferred with both heat and work, whereas entropy is transferred only with heal. The first law ofthennodynamics makes no distinction between heat transfer and work. It considers them as equals. Thc distinction between heat transfer and work is brought about by the second law: an energy interaction which is accomponied by entropy transfer is heat trallSfer. and an energy interaction which if not accompanied by entropy trallSfer is work. Thus. only energy is exchanged during \oI-vrk in/eract/on. whereas both ene;-gy and entropy are exchanged during heat transfer.

(b) Mus Flow Mass contains entropy as well as energy, and Ihe enlropy and energy of a system are proportional 10 the mass. When the mass of a syslem is doubled, so are the entropy and energy of the system. Both entropy and energy are earried into or oul ofa system by streams of maller, and the rales of entropy and energy transport into or out of a system are proportional to the mass flow rate. Closed syslems do nOI involve any mass flow and thus any entropy transport. When an amount of mass m enters or leaves 3 system. an entropy of amount MS. s being the specific entropy, accompanies il. Therefore, the entropy of a system increases by ms when the mass of amounl m enters iI, and decreases by the same amount when it leaves it at the same state.


7.11 Entropy Generation to a Closed System

The entropy of any closed system can incre3$e in two ways: (a) by heat interaction in which there is entropy transfer (b) internal irreversibilities or di ssipative effects in which work (or K.E.) is dissipated into internal energy increase.

If ctQ is the infinitesimal amount of heat transferred to the system through its boundary at temperature T, the same ali that of the SUlTQUooings, the entropy increase US of !he system can be expressed as
US =~S+di S
= - + dS

"Q T



where d.S is the entropy increase due to external heat interaction and diS is the entropy increao;e due 10 internal irreversibility. From Eq. (7.25).

(7.26) diS ~O The entropy increase due to internal irreversibility is also called entropy production or entropy generntion. S,.... In other words. the entropy change of a system during a process is greater than the entropy transfer (d Qm by an amount equal to the entropy gentlOlted during the proces.~ within the system (d;S), so Wt the entropy balance gives: Entropy change = Entropy transfer + Entropy generotion ~.yst<m = M Inmf... + M,.. which is a verbal statement of Eq. (7 .25) and illustrated in Fig. 7.23. It may so happen thaI in a process (e.g .. the expansion of a hot fluid in a turbine) the entropy decrease of the system due 10 heal loss to the surroundings

(-Jdi J is equal to the entropy increase of the system due to internal


Entropy change of system '" Entropy transfer (with OJ


(by W, due 10 dissipation

irreversibilities S\Jch as friction , etc.

5yst~m before and after the process will rema in the same dS = 0) , Therefore. an isentropic process need not be adiabatic or reversible. But if the isentropic process is reversible. it must be adiabalic. Also. if Ihe isentropic process is adiabatic. it cannot bUI be rewrsib/e. An adiabatic process need not be isentropic, since entropy can also increase due tofriction etc. But if thi! process is adiabatic and reversible, it must be isentropic. For an infinitesimal reversible process by a closed system,

(J djS) , in which case the entropy of the (J

!lQR ~ dUR + pdV If the process is irrevers ible, !lQI "" dUI+dW
Since U is a property. dUR "' dUI

dQR - pdV "' dQI - dW

[ ,~

l. -(-'fl,



The difference (pdV - dW) indicates the work that is lost d ue to irreversibility, aod is called the los/ work d (LW), which appl"mlches zero as the process approaches reversibility as a limit. Equation (1.27) can be e:'lpressed in the form dS - d.S + d;S Thus the entropy ora closed system increases due to heat addition (d.,5) and intemal dissipation (dp').


In any process exufed by a system, energy is always conserved, but entropy is produced internally, For any process between equilibrium states I and 2 (Fig, 7.24), th e first law can be written as

J , <Q- J , dW - E,-E,


IUbi r.r

QI-l = 2 - \ +

____ r -W 1_l



(Boundary Temperature)

T --!~/~'(~~~"'-T-.-"-'f-.::: f



S2 - S 12:


Fig. 7.24

&Amtt!.tic.f II (UUtJ Iffl"" interac/;", w;th ib fMrTDulliirw

By the second law,

, dQ J, T

It is only the transfer of energy as heat which is accompanied by entropy transfer, both of which occur at th e boundary where the temperature is T. Work interaction is nOI accompanied by any entropy transfer. The entropy change of the system (S2 - S\) exceeds the entropy transfer

, dQ J ,r , The

difference is produced internally due to irreveersi bility. The amount of entropy generation S.... is given by

, dQ S2 - S\ - J r .. S....




En,,,.py .ntnffcr production


S' <II2:0

The second law stales that, in general, any thermodynamic process is

accompanied by clllropy genermiofl,


116=-Process 1-2, which does not generate any entropy (S... .. 0), is a reversible process (Fig. 1.25). Paths for which S.... > 0 an: considered irreversible. Like heat uansfer and work uansfer during the process 1- 2, the entropy generation also depeflfh on Ihe palh the $}'!ltemfollow!I. Slim is, therefore, not a thermodynamic propeny and ct S,.. is an inexact differential, although (S2 - SI) depends only on the end states. In the differential form , Eq. (7.28) can be written as


- dS - <1Q


The amount of en/ropy generation qUQntijie:r Ihe inlrin:ric irrevtr:ribililJl of the proc:e:r:r. If the path If causes more entropy generation than path B (Fig. 1.25), i.e.

(S...,) ... > (S,...>o the path If is more irreversible than path B and involves more 'lost work'. If heat transfer occurs at several locations on the boundary of a system, the entropy transfer term can be expressed as a sum. so Eq. (7.28) takes the form
(7.30) + S.... J T J wh~ Q/1j is the amount of entropy traIlllferrcd through the portion of the boundary at temperatw'C 1j. On a time rale basis, the entropy balance can be written as

~-Sl " L Qj

dS= L ~+S, .. j1j

(7.3 1)

where dSIdr is the rate of change of entropy of the system, Q/ Tj is the rate of entropy transfer through the portion of the boundary whose iIllltantaneous .... is the rate ofentropy generation due to irreven;ibilities temperature is r i , and 5 within the system.

"' "


7.12 Entropy Generation in an Open System

In an open sys tem, there is transfer of th ree quantities: mass, energy and entropy. The control surface can have one or more openings for mass transfer (Fig. 7.26). It is ri gid, and there is shan work transfer across it.

,",,'00 Temperalulll.

Q _ _ _ _~'

(ShaflWork Transfer Rate)


IEntropy TrarlSfer Raw)

/ "~~ 4 lHeat Transfer I Rata)

The conlinuity equation gives

", . "" ",. aM "" m m. - - ar


t -



net mass Ir.lruIfer rate The energy equation gives

rate ofmus


L. ml(h+~+gzl- L. mo(h+~+gZl +Q-W... ~


rale of magy om:umulationintheCV The .<""ond law inequality or the entropy principle gives

2;< nel rale of energy




", . ", . ""m s - "" ms




;, as


rale of enlropy lnlnsfer

ralC of i~ of entropy ofllle CV


Q represents

the rate of heat transfer al Ihe location of the boundary

where the instantaneous temperature is T. The ratio QIT accounts for the entropy transfer along with heat. The tenns m;f; and account, respectively, for rates of entropy transfer into and out of the CV accompanying mass flow. The rate of entropy increase orlhe control volume ellceds, or is equal 10, the net


178=rate of entropy transfer into it. The difference is the entropy generated within the control volume due to irreversibility. Hence, the rate of entropy generation is given by

', S
By the second law,

as ", . I <" - ar-,



If the process is re~'ersible, S .. O. For an ineversible process. Sa<n > O. The magnitude of S.. n qu.antilfe's th~ ineversibility of the process. If systems If and B operate so that (5... )" > (5.... )8 it can be ~aid that the system If operates more irreversibly than system B. The unit of 51"" is W/K. At steady slale. the continuity equation gives (7.36)

the energy equation becomes 0=

Q- IV.., +~mj(h+ ~+gZl , - Lm~(h +~+gzl



and the entropy equation reduces to

T; " These equations often must be solved simultaneously. together with

appropriate property relations. Mass and energy are conserved quantities, but entropy is not generally conserved. The rate at which entropy is transferred out must exceed the rate at which entropy enters the cv. the difference being the rate of entropy generated within Ihe CV owing 10 irreversibilities. For one-inlet and one-exit control volumes, the entropy equation becomes

0- Q+ LmISI- Lm.s. +Ss<n



7.13 First and Second Laws Combined

By the second law

dQ..... = TdS
and by the first Jaw, for a closed non-flow system.

dQ - dU + pdV

TdS - dU +pdV
Again, the enthalpy (740)

H = U+pV dH - dU + pdV+ Vdp - TdS+ Vdp TdS " df/- Vdp

(7.41 )

Equations (7.40) and (7.4 1) are the thermodynamic equations relating the properties of th e system. Let us now examine the following equations as obtained from the first and second laws: (a) d Q = dE + d W - This equation holds good for any process, reversible or irreversible, and for any sys tem. (b) d Q >z d U +pd W - This equation holds good for any process undergone by a closed stationary system. (c) dQ - d U + pd V - This equation ho lds good for a closed system when only pdV~work is presenl. This is true only for a reversible (quasi~static) process. (d) d Q '" TdS-This equation is true only for a reversible process. (e) TdS - dU + pdV- This equation holds good for any process reversib le or irreversible, undergone by a closed system, since il is a relation among properties which are independent oflhe path. (f) TdS '" dH - Vdp-This equation also relates only the properties of a system. There is no path function term in the equation. Hence the equation holds good for any process. The use of the lerm 'irreversib le process' is doubtfu l, since no irreversible path or process can be plotted on thermodynamic coordinates. It is morc logical 10 state that 'the change of state is irreversi ble, rather than say ' it is an irreversib le process' . A natural process which is inherently irreversible is indicated by a dOlled line connecting the initial and final states, both of which are in equilibrium. The dotted line has no other meaning, since it can be drawn in any way. To determine the entropy change for a rea l process, a known reversible path is made to connect the two cnd states, and in tegrati on is performed on this path using either equation (el or equati on (t), as given above. Therefore, the entropy change ofa system between two identifiable equilibriwn stales is the same whether the intervening process is reversible or the change of stale is irreversible.

7.14 Reversible Adiabatic Work in a Steady Flow System

In the differential fonn, th e steady flow energy equation per unit mass is given by Eq. (5.1\),
d Q ~ dh + VdV + gdZ + it Wx

. 1


For a reversible process, d" Q '" Tds

Tds = dh + VdV + gdZ + d"W~ Using lhe property relation, Eq. (7.41). per unil mass.. Tds = dh - vdp in Eq. (7.42), we have

-00,.. so VdV + gdZ+ d"Wa

On inte!gnllion


, V' -J vdp = ~- + Wa , 2
If the changes in K.E and P.E. are neglecled, Eq. (7.44) reduces 10
W. =


, -lOOp


If itQ .. 0, implying tis = 0, die property relatiOll gives

'" = 00p
h, -h, =
From Eqs


and (7.46),

W.=h,-h,=- I OOp

The inlegral -

, J , t7dp represenlS an area on !he

, ,



plane (Fig. 7.27). To make

!he integration. one mUSI have a relation bc:Iween p and rJ such u ~ :: consl&Dt.

w. __/vdp






It'1 _1''''hl - h1 =-

JWp ,

" area 12 ab I Equation (7.47) holds good for a steady flow work-producing machine like an engine or turbine as well as for a work-absorbing machine like a pump or a compressor, when the fluid undergoes reversible adiabatic expansion or compression. It may be Doted that for a closed stationary system like a gas confined in a piston-cylinder machine (Fig. 7.28a), the reversible work done would be


, J , pdV " Area 12cdl

Wl2 -




- -/ , I'dp



FIg. 7.28 RnnsiMe work trllllJjtr ill (II) II clttutll]JUII1 IIIIIl (6) /I sUIId] folD I]Jtnn The reversible work done by a steady flow system (Fig. 7.2gb) would be

, WI_2 -- J 1XIp " Area 12 ab I ,



7.15 Entropy and Direction: The Second Law-A Directional Law of Nature
Since the enuopy of an isolated system can never decrease, it follows that only those processes are possible in nature which would give an enuopy increase for the system and the surroundings together (the unh'erse), All spontaneous processes in nature occur only in one direction from a higher to a lower potential. and these are accompanied by an entropy increase of the uni verse. When the potential gradient is infinitesimal (or zero in the limit), the entropy change of the universe is zero, and the process is re'er.;ible. The second law indicates the direction in which a process takes place. A. proc~ss aJr.mys occurs in such a direction as to cause an increase In the ~ntropy of the unil'erse. The macroscopic change ceases only when the potential gradient disap~ars and the equilibrium is reached when the enuopy of the universe assumes a maximum value. To de!ermine the equilibrium stale of an isolated system it is necessary to express the entropy a.~ a function of certain properties of the system and then render the function a maJLimum. At equilibrium, the system (isolated) exists at the peak of the entropy-hill. and dS '" 0 (Fig. 7.13). The natural direc tion of events in which entropy increases indicates the "arrow of time' which results from the universe not being in thermodynamic equilibrium. It undergoes a /Ullura/ evolution and inexorably approaches the state of equilibrium.

7.16 Entropy and disorder

Work is a macroscopic concept. Work involves order or the orderly motion of molecules, as in the expansion or compression of a gas, The kinetic energy and potential energy of a system represent orderly forms of energy. The kinetic energy of a gas is due to the coordinated mOlion of all the molecules with the same average "eiocily in the same direction. The potential energy is due to the vantage position taken by the molecules or displacemeats of molecules from their normal positions. Heat or \hermal energy is due to the random thermal motion of molecules in a completely disorderly fashion and the average velocity is zero. Orderly energy can be readily convened into disorderly energy, e.g" mechanical and electrical energies into internal energy (and then heat) by friction and Joule effect, Orderly energy can also be con\'ened into one another. But then an nalura/limitations on the. comu.Jion of dl.Jordt.rly energy into ordt.rly e.nt.rgy. as de.lineate.d by Ihe. se.colld law. When work is dissipated into internal energy. the disorderly motion of molecules is increased. Two gases. when miled, represent a higher degree of disorder than when they are M!paTated. An irreversible process always tends to take the system (isolated) to a sUIte of greater disorder. II is a tendency on the part of nature to proceed to a state of greater disorder. An isolated system always tends to a state of greater entropy. So there is a close link between entropy and disorder. It may be sialed roughly



that the entropy of a system is a measure of the degree of molecular disorder existing illihe ~slem. When heat is imparted to a system, the disorderly motion of molecules increases, and so the entropy of the system increases. The revem: occurs when heat is removed from the system. Ludwig Boltzmann (1877) introduced statistical concepts to define disorder by attaching to each state II thermodynamiC probability, ell:pressed by the quantity W, which is greater the more disordered the state is. The increase of entropy implies that the system proceeds by itself from one state to another wilh II higher thennodynamic probability (or disorder number). An irreversible process goes on until the most probable state (equilibrium state when W is maximum) corresponding to the maximum va lue of entropy is reached. Boltzmann assumed a functional relation between Sand W. While entropy is additive. probability is multiplicative. If the two parts A and B of a system in equilibrium are considered, th e entropy is the sum S - S,,+SB
Bnd the thennodynamic probability is the product W ~ W", Ws

S = 5 (W), S" "' S(JV,,), and SB" S(Ws) '" S(JV" JVs) = S(W,,) + S(WB)

which is II well-known funclional eqUllton for the logarithm. Thus the famous relation is reached (7.48) when: K is a constant, known as Boltzmann constant. This is engraved upon Boltzmann's tombstone in Vienna. When W " I, which represents the greatest order, S - O. This occurs only at T " OK. This stale cannot be reached in II finite number of operations. This is the Nemst-SimoD statement of third law of thennooynamics. In the case of II gas, W increases due to an increase in volume VOT temperature T. In the reversible adiabatic expansion ofa gas the increase in disorder due to an increase in volume is just compensated by the decrease in disorder due to a deerease in temperature. so that the disorder number or entropy remains constant.

7.17 Absolute Entropy

It is important to note that one is interested only in the amount by which the entropy of the system changes in going from an initial to a final state, and not in the value of absolute entropy. In cases where it is necessary. a zero val ue of entropy of the system at an arbitrarily chosen standard state is assigned. and the entropy changes are calculated with reference to this standard state.

7.18 Entropy and Information Theory

The staning point of infonnation theory is the concept of uncertoimy. Let us define an event as an occurrence which can result in one of the many possible

184=outcomes. The outcome of the event is known only after it has occurred, and before its occurrence we do not know which one of the severa] possible outcomes will actually result. We are thus uncertain with regard to the outcome before the occurrence of the event. After the event has occurred, we are DO longer uncertain about it. If we know or can assign a probabjljty to each one of the outcomes, then we will have some information as to which one of the outcomes is most likely to occur. For example, let us consider the throwing of a dice and try to guess the result. Each event oftuming 1,2,3,4,5 and 6 has a probability of 116. Ifit is told that the result is odd, the probability of a correct guess is 1/3. If it is told further that Ihe number is nol a 3, the probability of the correct guess beeomes 112. It is thus seen that the smaller the probability. greater i.s the uncertainty. The amount of information conveyed by a message increases as the amount of uncertainty regarding the message becomes greater. The more it is known about the message a source wil1 produce, the less the uncenainty, and less the in(onnation conveyed. The entropy of communication theory is a measure of this uncertainty conveyed by a message from a source. As stated earlier, in infonnation theory a value of uncertainty is associated with each outcome of an event. Let us denote the Wlcenainty about an outcome whose probability is p. The knowledge of this uncertainty depends on certain characteristics given below: I. The uncertainty u about an event A with possible outcomes NI, N2, . depends upon the probabilities Pt, Pl' ... of these outcomes, or:
u - f(PI' P2' ... ) If Pi is the probability of the ith outcome:

u - f(P,) 2. The uncertainty u is a monotonic function of the probability of the outcome p and it decreases with increasing probability, or: du/dp < 0
3. When the probability p '" I, the uncertainty u '" O. 4. The uncertainty about two independent events A and B taken together as one should be the sum of the uncenainlies about A and B taken separately,

u(A,B) -= u,,+U8 In other words, uncertainty is an additive property. In the case of probabilities, however,
p(A, B)""p" 'PB The functional re lationship between u and p can be derived, as in Eq. (7.48),

u - ~Klnp "' Kln.!.



where K is a constant. Since p is always less than I, Ii is always positive. S. If the event has a very large number of outcomes. an average value of uncertainty for the outcomes of the event is significant. If PI' pz, Pl' ... be the probabilities of the outcomes of an event with uncertainties lit, liZ' loll' then the average value of the uneenainty for the event as a whole is given by the expectation vallie of the Ilncer/ainty <U>, which is wrinen as;

<u> "" L PiUi

Since P; 's are probabilities,

Again, since u; ,. - K In Pi' therefore. (7.50)

The measure ofunccrtainty can be used to define the amount of infonnation contained in a message. The information in a message has the effect ofrcducing or eliminating uncertainties. We, therefore, define the in/ormation 1 in a message as the decrease (II ullcertointy as II result of receiving the message, or
[ "" Ut-Ill (7.5 1) where Ut and ul are the uncertainties before and after receiving the message respectively about the outcome with which the message is concerned. Using Eq. (7.49),

1 - KlnE!..



where PI and pz arc the probabilities before and after receiving the message respec1ively. If the message removes the uncenainty completely giving complete information about the outcome, U z .. 0 and 1 " ul' In general. in/ormation is eqwl to the uncertainty. When we are dealing with many outcomes with their associated uncertainties, we can define the average or expected value of the information, </> - <u> ..

-Kl Pi In Pi


Theexpected va lue ofinformation is also called entropy in information theory and is designated by the symbol S, so that

S - -K I, Pilnpi
This is known as ShanIlOIl., formula.

(7 .54)


IS6= -


Statistical Formalism

Let VI' V2 .. . V<are the values of the various outcomes, and PI' P2' ... , Po are the probabilities associated. Let V is known as the average value of all the outcomes, which is the same as the c}l:pc:ctcd va lue. The equations of constraint


l7pi - 1
f.p,v; = < V> '"


If Pj'S are given. then V can be esti mated from the above equation. But if V is given and p'; s are req uired. then we have c unknowns, viz.,PI' P2' . .. ,p~, and only two equations. If c > 2, the problem is indeterminate. If one sct of p'; s is chosen arbitrarily. some outcomes are cel1ainly overemphasized. The prob lem is then how to avoid hias in selecting a cenain set of p'; s. The answer according to E.T. Jaynes is to assign that set of values ofp';s which is consistent with the given information and which mwtimizes the uncertainty. This is Ihl' principle of minimum prejudice, enunciated by Jaynes in the following words: "The leasl prejudiced or mosl unbiased eSlimule of probabililit's is Ihul as.signml'nl which maximizes Ihe entropy S, subjecllO Ihe gil'en information ". The entropy S represents the uncel1ainty of an event, which is to be maJ(imized: (7.54) S "- Krp; ln p, subject to the two constraints of Eq. (7.55). Lagrange's method of undetermined multipliers (see Chap. 21) will be used for the solution. Differentiating Eqs (7.54) and (7.55) (7.56) !dp; = 0 (7.57) !Vj dpj= O

where: ..l. and

dS ~ - K

[! In Pi dp; + LIp;] '" 0 (7.58)

f.lnp;dp; - O

where V;s are held constant and dS '"' 0 for S to be mwtimum. Multiplying Eq. (7.56) by ..l. and Eq. (7.57) by fJ and adding to Eq. (7.58).
1:[ln Pi + ..l. + tJV;l dpi '" 0 (7.59) fJ are the Lagrange's multipliers. Since dpis are non-zero,
Pi 1', 1

ln pj+..l.+tJVi = O


The Eq. (7.60) represents a set of c equations:

PI = 1', 1 e-PVI P2 _ e-l. e-P Vl

pc _ e-le-fJVo

The above eq uations are the desired unbiastd set ofp'; s.


, IPi .. L e-le-PVi
i_ I

- I

e From Eq. (7.60).


A"" In

Le- PVi


e- Pv; Pi " ~:e- PVi

Thus, ). has been estimated. Using Eq. (7.55) LlI,e-./l v; _


LPi Y; = ~ I - /lv. '" V i .. e I


Since V is known. fj can be detennined. The entropy can be expressed in terms of). and fj as: S - - K l:Pi [- ,l. - fjViJ .. K,l.!.pi + K fjIp. Vi S=K,l.+Kfj<V> (7.65) The above procedure is referred to as the Jaynes ' formalism.

7.18.2 In/ormfllion Tluory Applud to fl SysUm 0/ Pflrliciu

Let us consider a system having a large number of panicles. According to the quantum theory (see Chap. 19), the energy that the system can have is discretely distributed. The system cannot have any energy. but only certain va lues of energy levels. Let us denote by Pi the probability of the energy level E A high probability signifies that th e corresponding energy le vel is more frequently attained by the system, i.e .. the system can be found for longer durations of time in that energy level. The problem is to detennine the most probable state of the system subject to the constraints imposed by the nature of the system. Usually, the average energy of the system, which is also the expe<:t:ltion energy <E> is known by physical measurements. Therefore ,

<E> md

!PiEi -

!Pi - I

In statistical thennodynamics. one proceeds to detennine the number of microstates correspondi ng to the most probablc macrostate of the systcm (see Chap. 19), corresponding 10 the thennodynamic equilibrium state when IV is maximized to yield S" K In IV, The entropy signifies the uncenainty inherent in the system.

18a=Jaynes' formalism can be applied here. The outcomes are the various possihle energy levels corresponding to the various macrostates of the system. The probabilities Pi of the energy levels are 10 be determined according to the principle of-minimum prejudice, subjett to the constraints,

Ep, - 1


' <E>
S - -KEpilnpi

Maximizing the uncenainry or thc entropy: we get the probability distribution, as obtained earlier in Eq. (7.60) Pi _ e-1 e-~1l

(7 .66)

whcre l - Et'rllri which is the partition/unction (z) of the system (as explained in Chap. 19). The maximum value ofthc enb"Opy is then (as in Eq. 7.65),

S - KJ.+kfj<E>


By considering the ideal distribution of an ideal gas, we can identify fj as I /KT (Chap. 19). where K is the &Itzmann constant. Thus, the probability di stri bution of energy levels is temperature dependent (Eq. 7.66).

1.18.3 r,.jol'1lUlliDlf TIuo" ami CltwUal Tltenn.odytcamies

Classical thermodynamics usually treats the concepts of heat and"work as primitive. The information theory, however, considers heat and work as derived quantities. The expectation energy is given by:

<.F> '" I:PiEi


Thus, the observable energy of the system can be changed by changing . ei ther the probabilities, Pi' or the permissible states, t; or both. The entropy S - - K I:Pi In Pi shows that a change in the system's energy of the Pi-type wi ll change the entropy as we ll, the change in the energy of the lj-type not affecting the entropy. Let us consider changes of the E;-type. If a force F; acts on a system at the quanlUm state I and produces a small di splacement dx, the internal energy of the system changes by dE;, so that

F '" (Ie,

, ax

If the probability that the system is in state i is Pi' the expectation force is: <.F> ., f.Pi F; Thererore,

<.F> - - f.Pi



By analogy for a fluid, the pressure is:

p - tp;




Work done in a reversible process:

c1W, pdV
From Eq. (7.70),
(7.71) Thus. Ihe reversible work does 1101produce allY challge in the entropy ojlhe sy.stem. From Eqs (7.68) and (7.71)
d<E> '" U; dp; - c1 W,

c1Q + (c1 W, - c1 W) - t ; dp; (7.72) Thus, the heal /ra1lS[ erred. dQ. and the losl work. (dW, - dW)are respoIISibfe [or challges in Pr and therejore. the elltropy oj the system. [t is shown that entropy of a system changes due to external interaction by heat transfer (deS) and due to internal dissipative effect (d;S). In absence of any dissipative effect,

c1 Q,= 1: ; dp;
Substituting Pi" e-A e-~ in Eq. (7.69),
<F> =_ r.e-A e- PCi



Again, since Therefore.

~[e-PCi ] .. _{Je- fJti




Now,,f . r.e~


It is noted lhBt ..t depends on fJ lIS well as , and hence on volume V. Now. S - Kl + K{J<E> dS .. Kdl + K<E> d{J + K{J d<E>

.. K[(

~~)v d/3 + (~~)p dV ] + K<E> d{J + K{Jd<E>

<E>'" rpi t; ~ re-l. e- Ik, i


dS _K[a,,] dP +[aA] dV av

.. K{Jp dV + K{Jd<E>

[From Eq. 7.74)

(J - KT
dS ", pdV+~


TdS=d+pdV (7.75) which is a well-known equation of classical th ermodynamics. For a rever:sible proeess, dW, = pdV

and from fir:st law.

dQ = d+dW
d"Qr ~ dE + pdV


From Eqs (7.75) and (7,76).

dS = dQ,


This is in conformity with the cl!lSSical formula for entropy. However. the entropy is a fundamental concept in information theory and not u derived function as in classical thermodynamics.

7.19 PostuIatory Thermodynamics

Tbe property 'entropy' plays the central role in thermodynamics. In the classical approach. as followed in this book. entropy is introduced via the


concept of the heat engine. It follows the way in which the subject of thennodynamics developed historically mainly through the contributions ofSadi Camot, lames Prescott Joule, William Thomson (Lord Kelvin), Rudolf Clausius, Max Planck and Josiah Willard Gibbs. In the postulatory opproach, as developed by H.B Callen (see Reference). entropy is introduced at the beginning. The development of the subject has been based on four postulates. Postulate I defines the equilibrium state. Postulate 11 inlroduces the property 'entropy' which is rendered maximum at the final equi. librium state. Postulate III refers to the addith'e nature of entropy which is a monotonically increasing function of energy. Postulate IV mentions that the entropy of any system vanishes at the absolute zero of temperatue. With the help of these postulates the conditions of equilibrium under different constraints have been de\'eloped.


&ample 7.1 Water flows through a turbine in which friction causes the water temperature to rise from 35C to 37C. If there is no heat transfer, how mueh does the entropy of the water change in passing through the turbine? (Waler is incompressible and the process can be taken to be a constant volume.)

So/mio" The presence of friction makes the process irreversible and causes an entropy increase for the system. The flow process is indicated by the dOlled line joining the equilibrium states 1 and 2 (Fig. Ex. 7. 1). Since entropy is a state property and the entropy change depends only on the two end states and is independent of th e path the system follows, to find the entropy change, the irreversible path bas to be replaced by a reversible path, as shown in the figure. because no integration can be made on 3 path other than a reversible path.

!~~.~~........ \~?:~::e_

Rever$iblo path
CXlMlK:Iing!he initi"d and finftl flQuUibrium


306K / / /


....,'_ as s
Fig. Ex. 7.1

Tz "' J7+27J = JIOK T! " J5 + 27J "' J08K

192=We have

4Q.... - TdS
dS - mCydT

Sl - S( = mCyLnr: - I x 4. 187 In .. 0.0243 kJlI<



Eumple 7.2 (a) One kg of water at 273 K is brought intocoDtact with a heat reservoir at 373 K. When the water has reached 373 K. find the entropy change of the water, of the heat reservoir, and of the uni verse. (b) ICwatcr is heated from 273 K to 373 K by first bringing it in contact with a reservoir at 323 K and then with a reservoir at 373 K., what will the entropy change of the universe be? (c) Explain how water might be heated from 273 K to 373 K with aimosl no change in the entropy of the universe.

Solution (a) Waler is being healed through a finile temperature difference (Fig. Ex. 7.2). The entropy ofwalcr wo uld increase and that of the reservoir would decrease so that the net entropy change of the water (system) and the resevoir together would be poSitive definite. Water is being heated irreversibly, and to find the entropy change of waler, we have to assume a reversible path between the end states which an: at equilibri um.
R......' 373K



Fif. Ex. 7.2

(.6.5),._ =

mcdT J4Q = 1 =mc ln


72 1i

= 1 x 4.187 In

12I. =

1.305 kJfK


The reservoir temperature remains constanl irrespective of the amount of beat withdrawn from il. Amount of heat absorbed by the system from the reservoir,

Q - I x 4.187 x (373 - 273) - 418.7 kJ

:. Entropy change of the reservoir


=_.2.=_ 418.7 T 373

= - 1.I22kJ/K

:. Entropy change of the universe

(bS)""iY - (ds)')'I1aII + (bS) ... = 1.305 - 1.122 - 0.183 kJ/K


(b) Water is being heated in two stages, fIrSt from 273 K to 323 K by bringing it in contact with a reservoir at 323 K., and then from 323 K to 373 K by bringing it in contact of a second reservoir at 373 K.

(bS) ....., ..


dT dT Jmc-+ JmcT T


= 4.187 ( In - 1.305 kJfK



~~~) -

(0.1673 +0.1441)4.187

( A<;"\

.. _ 1 x 4.187 x (323 - 273) __ 0.647 kJ/ K 323


....... ltaH

lx4.l87x(373-32J) " -0.S6kJfK 373

(bS)..,i v '" (bS) ..."" + (bS)res! + (AS)"", n = 1.305 - 0.647 - 0.56

'" 0.098 kJ/K


(c) The enlr0py change of the universe would be less and less if the wate r is heated in more and more stages, by bringing the water in contact successively with more and more heat reservoirs, each succeeding reservoir being at a higher temperature than the pre<:cding one. When water is heated in infinite steps, by bringing it in contact with an infmite number of reservoirs in succession, so that at any instant the temperature di fference between the water and the reservoir in contact is infinitesimally small, then the net entropy change of the universe would be zero, and the water would be reversibly heated. Example 7.3 One kg of ice at - SoC is c}l.posed to the atmosphere which is at 20 GC. The ice melts and comes into ~hennal equilibrium with the atmosphere. (a) Determine the entropy increase of the universe. (b) What is the mi nimum amounl of work necessary to convert the waler back inlo ice at -SoC'! cp of ice is 2.093 kJ/kg K and the latent heat of fusion of ice is 333.3 kJ/kg.



Heat absorbed by ice

Q from the atmosphere (Fi g. Ex. 7.3.1)

Fig. b. 7.3.1 ., Heal absorbed in solid phase + Late nt heal + Heat absorbed in liquid phase = I x 2.093 x [0 - (-5) + I x 333.3 + I x 4.187 x(20 - 0) = 427.5 k.J Entropy change of the alm05pher.

= _Q=_427.S = - 1.46k11K
T 293

Entropy change of the system (ice) as. it gets healed from - SoC to OC
(6SJ.)'mm "


mc~ T


273 I x 2.093 In 268 .. 2.093 x 0.0 186

.. 0.0389 k.JfK
Entropy change of the system as ice mdts at OC to become water al OC

(.sII) , '"'

333.3 _ 1.22 kJfK


Entropy change of wa ter as it gels healed from OOC to 20"C




J mC~T = I x 4.187 In 293 .. 0.296 kJIK 273


Total entropy change of ice as it mells into water (<1S)1OLll = .1.S1+ 6S11 + 6Sm '" 0.0389 + 1.22 + 0.296 '" 1.5549 kJfK The cntropy-temperature diagram for the systcm as iee at - SoC converts 10 water at lOC is shown in Fig. E)(. 7.3.2 :. Entropy increase of the universe
(6S)Wli. = (.1.S).)'II<tn

+ (6S)."" I.5S49 - 1.46 .. 0.0949 kJlK

An.\". (a)



Fig. Ex. 1.3.1

(b) To convcrt 1 kg ofwatcr at 20"C to ice at -SoC, 427.5 kJ of heat have to be removed from it, and the system has to be brought from Slate 4 to state 1 (Fig. Ex. 7.3.2). A refrigerator cycle. as shown in Fig. Ex. 7.3.3, is assumed to accomplish this. The entropy change of the system would be the same, i.e. S~ - St, with the only difference that its sign will be negative, becau~ heat is removed from the system (Fig. Ex. 7.3.2).
(M)')"IIem ., St - S4
(Q ~ lIat;v.)

1 kg Wet.,.. at 2O"C to ice at - SOC

Fig. Ex. 1.3.3

The entropy change of the working fluid in the refrigerator would be zero, since it is operating in a cycle, i.e.,
(4S),.f = 0

The entropy change of the atmosphere (positive)

(M)_ =


:. Entropy change of the universe

(~W1iv - (~oytI<m

+ (dS)..r + (~_

Q+W = (St- S4 ) + - By the principle of increase of entropy

(dS)univ ... ioolalod oytIem <!: 0

[(St - S.)+







W2: T(5~ - 51) - Q W (miII)" T(5~ - 51) - Q Q .. 427.5 kJ T - 293K 54 - 51.. 1.5549 kJlK W(min) " 293 x 1.5549 - 427.5 - 28.5 kJ

AII.I'. (b)

Eumple 7.' Two identical bodies of constanl heat capacity are at the 58me initial temperature Tj A refrigerator operates between these two bodies until one body is cooled 10 temperature T1 Ifme bodies remain al constanl prc55Ul'e and undergo no change of phase, show thllt the minimum amount of work needed to do this is



+ Tl - 21j )


Both me fmite bodies A andB are inilially althe same temperature 7;. Body A is to be cooled to temperature T2 by operating the refrigera tor cycle, as shown in Fig. Ex. 7.4. Let T{ be the fmallempcratute ofbody B.

Fig. EL 7.4

Heat removed from body A to cool it from T; 10 T2 Q = Cp (7;- T2) where Cp is the constant pressure heal capacity oCthe idenlical bodies A and B. Heal discharged 10 body B
- Q+W ~Cp( ll - T;)

Work input, IV
'" Cp(Ti - TJ - Cp (T; - T2) - Cp (T:i + T2- 2T;)


Now, th e entropy cbange of body A.
~,, - ] Cp TI



Cp In .2.. (negative)


The entropy change of body S

t.Sa -

"1 Cp -dT =Cp In.2.. r.' (positive)



Entropy change (cycle) of refrigerant .. 0 :. Entropy ebange of the universe

(6S)uni. = ilS"

+ ilSB
T T'

By the entropy principle


In-1-+ C In~


(as)...;. ~ 0

lo..2.+C In Ti l> ' (cPT; PT;

Cp ln

T 2 ;i ~ 0 r,


In equation (1.4.1) with CP' T~, and T; being given, W will be a minimum when T2 is a minimum. From Eq. (7.4.2). the minimum value of T2 would correspond 10 C In ..:.Ll.. = O= ln I

r, - - 'r,
From equation (7.4.1)


ff(min},",Cp( T/ +T2 -2T;) .


Example 1.5 Three identical finite bodies of constant heat capacity are at temperatures 300, 300 and 100 K. If no work or heat is supplied from outside, what is the highest temperature to which anyone of the bodies can be raised by the operation of heat engines or refrigerators?

Solution Let the three identical bodies A.. S , and C having the same beat C8pacity C be respectively a1300 K,IOO K and 300 K initially, and let us operate a heat engine and a refrigerator, as sbown in Fig. Ex. 7.5. Let Tf be the final temperature of bodies A and B. and T; be the fmal temperature of body C. Now


Basic 12M Applied TIIlrmMJlUJmia

T, (AS)" "" C In 300

(AS)B - C In



(ASh: " C In - ' (6S)It.E. = 0 (6.S),.( = 0

~-t; ---j
Fig. Ex. 7.5


where C is the heat capacity or each or the three bodies.


(dS)univ ~ 0

r ( Cln 3~

+Cln I~ +Cln 3~

r' )



9,000,000 For minimum value or Tr C In

T1T; 20
0 '" In I (7.5.1)

g .. 9x JO

T/ T; '"' 9,000,000
Qt '"' C(300 - Tr) Ql" C(Tr- 1(0) Q. - C(T'r- 300) Qt "" Heat removed rrom body A

- Heat discharged to bodies B and C - Qz+Q. C(300 - T() - C(T, - 100) + C (T; - 300)

T; will be the highest va lue when T, is the minimum.

From equations (7.5. 1) and (7.5.2) 1j (700 - 2Tf) - 9,000,000

r,: -

700 - 2Tr


2T/ -


T{ + 9.000,000 "

0 Tr "" ISOK

From Eq. (7.5.2)


- = 199

T; " (700 - 2 x lSO)K

- 400K

Eu.mple 7.6

A system has a capacity at constant volwne

Cv - Ar where A '" 0.042JIK1.

The system is originally al 200 K. and a ther.nal reservoir al 100 K is available. What is the maximum amounl of work thai can be recovered as the system is cooled down 10 the temperature of the reservoir? Solution Heat removed from Ihe system (Fig. Ex. 7.6)

I T~r=J-l00 K
' 0,

- 0.042 [ -T'


J "'' '
_ 0.042 llKl ( IOOJ _ 2001)Kl _ -98 X 10) J

(.'~ . . . ,.yotao:l .


:zoo K

J c " dTT = J 0.042T2 ~ T


0.042 JIK) [ IDlY _ 2002}Kl 2 - -630 JIK

(~ _ C?i - If' '" 98)( 10l - If' JIK



(AS) .. ~ n.id i.,U- - 0

(AS) - (AS)_ + (AS)..,

-- 630+ 98xI0'-1f'
' 00 Since (M)..,;v 2': 0

-630+ 98xlOl_1f' ~o

980 - JL - 630~0


l~ ~ 350
W( ......) .. 35,000 J ... 35 kJ

Example 7.7 A fluid undergoes a reversible adiabatic compression from O .S MPa, 0.2 m] to 0.05 m] according to the law. pri-) ~ constant. Determine the cbange in enthalpy. internal energy and entropy, and the heat transfer and work transfer during the process. Solution TdS - dH- Ydp For the reversible adiabatic process (Fig. Ex. 7.7)

dH " Ydp O.s MPa, YI .. 0.2 m Y ... " 1 0.05 ml, PI V"t .. P1Y2

PI -

.. 0.5 x (0.20)t.l MPa 0.05 .. o.s)( 6.061 MPa .. 3.0305 MPa

PlY'. " pyD




.. (p V:') tlJl
, ,

- lI. - p i-DID) PI I I I - lin

.. n(I'lV 2 - PIYj)

_ 1.3(3030.5 X 0.05 500 x 0.2) 1.3 - 1 = 223.3 kJ H2 - H I "" (V2 + P2 Vi) - (UJ + PI VI) - (V2 - VI) + (Pl V1 - P IYI)

U2 - V I - (H2 - H,) -

(P2V1 - PI VI )

- 223.3 - 51.53 - 171.77 kJ

~- SI - 0

QI-2 = 0 Q l_1 - V 2 - U, + W I_1

WI -l " VI - V 2 ""-171.77 kJ

AM. Ans. Ans.

EDmple 1.8 Air is flowing steadily in an insulated duct. The pressure and temperature measurements of the air at two stations A and B are given below. Establish the direction of the flow of air in the dUel Assume that for air, specific
heat cp is constant at 1.005 kJ/kg K, h - c p T, and .E.. - 0.287 , where p, 11 and T p Tare pressure (in kPa). volume (in m1/kg) and temperature (in K) respectively. Slah'on A Station B ' Pressure 130 kPa 100 kPa Temperature

From property relation Tds - dh - vdp dh dp


"' -- -,dT

For two states at A and B the entropy change of the system

'fds", 'j T' 'j


dp 0.287P

P" sa -sA - 1.005 In -TB - 0.2871n -'-"'TA PA

'" 1.005 In 273 + 13 _ 0.287 In 100 273+50 130


202=.. - 0.1223 + 0.0753 .. - 0.047 kJ/kg K

(M'}.ymm '" - 0.047 kJ kg K

Since the duel is insulated (65) .... - 0

(M'}WIi. '" - 0.047 kJ/kg K

This is impossible. So the flow must be from B to A. Example 7,9 A hypothetical device is supplied with 2 kgls of air at 4 bar, 300 K. Two separate streams of air leave the device, as shown in figure below. Each stream is at an ambient pressure of I bar, and the mass flow rate is the same for both streams. One of the exit streams is said to be at 330 K while the other is at 270 K. The ambient temperature is at 300 K. Determine whether such a device is possible.


The entropy generation rate for the control volume (Fig. Ex. 1.9) is

'" '"~l + '"]3) - ('"1 + '"l).l"1 - m2(sl-s,) + m)(s) Now,

S2 -SI .. Cp



..2. -R In .1i


= 1.005 In 330 _ 0.287

'" 0.494 kJlkgK

In 1..

: 1.005 In 270 _ 0.287 In 1. 300 4 = 0.292 kJlkgK

Sp - 1 x 0.494 + I x 0.292
= 0.786kWIK Since Sccn > 0, the device is possible. Such devices actually exist and are called varia lUbeS. Although they have low efficiencies, they are suitable for cenain applications like rapid cooling of soldered pans, electronic component cooling, cooling of machining operations and so on. Th e vonex tube is essentially a passive device with no moving pans. It is relatively maintenance free and durable.

-=203 f>Jrin
2kg/S - - t 0
b.... 300 J(

COld .. 1 kg/'
1 ber. 210

Fig. b. 1.9

Example 7.10 A room is maintained al 27"C whil e the surroundings are at 2C. The temperatures of the inner and outer surfaces of the wall (k '" 0.71 W/mK) are measured lobe 21"C and 6C, respectively. Heat nowssteadily through the wailS m x 7 m in cross-section and 0.32 m in thickness. Determine (a) the rate of heat transfer through the wall, (b) the rate of entropy generation in the wall, and (c) the rate of lOla I entropy generation with this heat transfer process. Solution



If A tJ.T .. 0.71 .:!!...... x (5 x 7)m 2 x (21- 6)K L mK O.32m 1164.84 W Ans. (a)

Taking the wall as the system, the entropy balance in rate form gives:

""""dt - SlrlnIfu + S........u

dS":al1 _ .

Ii + Saen. . .....u o -= '" k T

0'" 1164.84 _ 1164.84 + S 294 279 1<1>-...11 Rate of entropy generatio n in the wall

51<".....u "'" 4. 175 - 3.962 '" 0.213 WrK

tfns. (b)

The entropy cbange of the wall is zero during this process, since the state and hence the entropy orthe waJl does not change anywhere in the wall. To detcrmine tbe ralc of total entropy generation during tbis heal tronsfer process, we extend the system to include the regions on both sides of the wall,

dS...w ' - - SlntIIrer + Saen.lOlIt d,

0-L ~Q+5 , T aen.


0 " 1164.84 _~ + 5 300 275 p""..1 5p.",,*1" 4.236 - 3.883 '" 0.353 WrK
Ans. (c)


7.J 1.2 1.3
Soow thai through one poinllhere can pass only one reversible adiabatic. State and prove Clausius' Thcrocm. Soow that entropy is a propty of a system. How t. the entropy change of a reversible procCS5 estimated? Will it be different for an irreversible pTOCCS5 between the same C'I'Id states? Why is the earn", cycle 011 T-5 plot a rectangle? Slate the principle of Canllbcodory. How is the existence of entropy function inferred'? Establish the inequality of Clausius. Give the criteria of reversibility, irreversiblility and impo5Sibility ofa therm0dynamic cycle. What do you understand by the entropy principle? When the system is at equilibrium, wby would any conceivable change in entropy be zero? Why is the entropy increase or an isolated system. measure or the extent nf irreversibility of the proecss undc:rgolle by the system? How did RudolrClausius summarize the flrst and second laws ofthermody_ namic,? Show Wt the transfer of heat through a finite temperature difference is irrevel'$ible. Show that the I diabatic mixiJli of two fluids is irreversible. What iJ the nwunium work obtainable from two finite bodies altetnperlltures TI and T1? Determine the maximum work obtainable by using one finite body at temper.1ture T and a tbcnnal energy reservoir III temperature Tgo T > Tgo What are \he ClUses or eDtropy increase? Why is <Ul isentropic procCS5 not nc<;:essarily all adiabatic proces.s? What is the reversible adiabatic work for a steady flow syslem when K.E. and P.E. changes arc negligibly mlaU? How is it different from that for a closed stationary system?

1.7 1.8

1.9 1.10

1.12 1.13

7. 16



7.20 Under what conditions is the work done equal to (a) 7.21 Why are the equations

Jp dll, (b) - J II dp?

TdS - dU + pdY TdS - dH- Ydp

valid for any ptoce.u between two equilibrium end states? Why is the second law call~ a directional law or nature? How is entropy related 10 molu\ar disorder in a system? Show that entropy varies logarithmically with the disorder number. What do you understand by pcrfa;t order? Give the Nemst-Simon statement of the third law of thermodynamics. Why docs entropy TCtll.in constant in a reversible adiabatic j'IT()(:e5s? What do you uqderstand by the postuJalory approach of thermodynamics? What do you uodel'$tand by 'lost work'?

1.23 7.24 7.25


7.28 ?.29

7.30 The amount of entropy generation quantifies the intrinsic irnversiblity of a proces.s. Explain. 7.31 Show that S"" is nOI a thermodynamic property. 7.32 Give the expression for the entropy generation rate fot a control volume of a steady flnw system. 7.33 What is the entropy generation in the isothermal dissipation of work? 7.34 What is the entropy generation in the adiabatic dissipation of work? 7.35 What do ynu understand by entropy transfer? Why is entropy transfer associated with heat transfer and nOI with work. transfer? 7.36 What is the relation between probability and unce:tainty or an event'? How is entropy defIDed in communication theory? 7.37 State the five characteristics on which tile uncertainty of an event depends. What is the exptation value of uncertainty'? 7.38 Defme infonnation and explain its relation with entropy. What is Shannon's fonnula? 7.39 What is bias? State and explain the principl e of minimum prejUdice. 7.40 Explain the procedure nf Jaynes' formalism to prove:

S - KJ. + Kfj<V>
Explain how information theory is app lied to a system of pan icles. What is partition function? 7.42 Explain the relation of information theory and classical thermodynamics. 7.43 How do the heat transfer and Ihe 1051 work affect cltanges in Pi and hence the entropy of a system? 7.44 Since informalion tbeory considers Ileal and work as derived quanlities, show that for a reversibl e process: (a) itW, =- l:p,d; = pdY
(b) itQ+(itW,-itW) = l:t;dPi


(c) it Q, '"' TdS 7.4S Exp lain how entropy is a fundamental concept in information theory and nol a derived function as in classical thermodynamics.

7.1 On the basis oflhe first law fill in the blank spaces in the following table of imaginary heat engine cycles. On the basis of the second law c lassify each cycle as reversible, im:vm;ible, or impossible.

Cycle TempuQ/ure SoutCe Sid

(a) (b)

RQ/c 0/ Hw/ Flo.... Rale of ",orkEjJidency Supply Rejeclion ou/put

327"C 27"C 420 kJ/s 230 kJ/s ...kW 1000"C 100"C ... kJlmin 4.2 MJ/min ... kW 65% (c) 7SDK 300 K ... kJ/s ... kJls 26 kW 60% 700 K 300 K 3kW ... kW 2kW (d) 7.2 The latent heat of fusion of water at O C is 335 kJlkg. How much does the entropy of I kg of i change as it melts into water in each of the follnwing ways:


&i.rir au Applitd 17Imnodyll/t.l/liu





(a) Heat is supplied reversibly to a mixture of ice and water at O"C. (b) A mixture of ice and water at OC is stirred by a paddle ,,heel. Two kg of water at sooC arc mixed adiabatically with 3 kg of Wlter 11 30C in a COllstant pressure proS5 of I atmosphere. Find !he increase in the entropy of the total mass of water due to the mixing process (c p of water .. 4.187 kJi1<g Kl. A/U. 0.0592 kJlK In a Camot cycle, heal is supplied at 350C and rejected at 27C. The working nuid is water which, whi le receiving heat, evapofll.tes from liquid at 350"C to steam at 3S0'C. The associated entropy change is 1.44 kJlkg K.. (a) If!he cycle opcr1Ites on a stationary mass of I kg of water, how much i. the work done per cycle, and how much is !he heat supplied? (b) If the cycle operates in steady now wilh a pD"'er output of 20kW, what is the steam now rate? AilS. (a) 465.12, 897.12 kllkg, (b)0.()4) kg/s A heat eogine receives reversibly 420 kJfcycle of heal from a source at 327"C, and rejcctll heat reversibly 10 sink at 27"C. There arc no other heat transfers. For each of the three hypo!hetical amoWlts ofhea! rejected, in (a), (h), and (c) below, compute the cyclic integral of d Qf T. From these results show which case is irreversible, which reversible, and which impossible: (a) 210 kJfeycJe rejccted, (b) lOS kJfeyc le rejected, (e) 315 kJ/cycie rejected . ,411$. (a) Reversible, (b) Impossible, (cl trreve1"$ib le In Fig. P.7.6, abaJ represents a Camot cycle bounded by two reversible adiabttics and two re\'ersible i~thenn. altemperaturcs TI and T z (TI > T1). The oval figure is a reversib le cycle, where heat is absotbed at temperatures less than, or cqualto, TI, and rejected al temperatures greater than, or equal to, Tl . Prow that Ihe efficiency of the oval cycle is less !.han that of Ihe Camot cyc le.

F1g. P. 1.6
7.7 Wal er is healed al a constant pressure of 0.7 MPa. The boling poinli~ i64.97"C. The initiaitemperalure of water is O'C. The latent heal ofevaporJlion is 2066.3 kJlkg. Find the increase of entropy ofW:lter. if !he final SUIC is steam. All.!". 6.6961 kJ/kg K 7.S One kg ofair initially at 0.7 MPa, 20 Q C changes to 0.35 MPa, 6O' C by lhe three revcl'iible nonnow processes, as shown in Fig. P. 7.S. Process 1-02 consistS"" of a constant pressure expans ion followed by a constant volume cooling, process 1-b-2 an isothermal expansion followed by a constant pressure c~pan~ion. and pro<:cs~ 1-,,2 an adiabalic cl(palUion followed by a constant volume heating. Determine the changes of imema! energy, enthalpy, and

entropy for each process, and find the work transfer and heat IBIISfer for cath process. Takes cp - 1.005 and Cy - 0.718 kJlkg, K and assume the specific heats to be COIl$la/lt. Also Il$SIIIne for air pr!" 0.287 T, when: p is the prt'!l$I1/"e in kPa. v the specific volume in mllkg, and Tthe tcmpenlture: in K.

Rev. Isothermi!I


Rev. edleblltic
2 C



Fig. P. 1.&
Ten gramme! of water at 20'C is con\'ened into ice at - IO'C at constant atmospheric presSIR. Assuming the lipecific heat of liquid water to remain I:Onl1ant at 4.2 IltK and that of ice to be half of this value, and taking the latent heat of fUiion of ice at O C to be 335 I lg. calculate the total entropy cllange of the system. AIIS.16.0211K 7.10 Calculate the entropy change of the uoivCf'SC as a resull of the following processes; (a) A copper block of 600 g mass and with C, of ISO JIK al 100"C is placed in a lake al SC. (b) The same block, al SoC. is dropped from a height of 100 m inlo the take. (c) T,,o such blocks, al 100 and O"C, are joined together. AIlS. (a) 6.63 11K. (h) 2.095 JIK, (c) 3.64 JIK 7.11 A system maintained at constant \'olume is initially a, temperatlR Tt and ileal reservoir at the [ower temperature: To is available. Show that the maximum work Ittoverable as the system is cooled to To is


T o) -To ln


7.12 A body of finite mass is originally at temperature T, which is higher than that
of a reservoir at temperature T2 Suppose an engine operates in a cytle between the body and the reservoir unlil it lo"'-ers the lemprnllure of the body from TI 10 T2, thus extracting heal Q from the body. t(the engine does work W, tllen it will reject heat Q-W to the reservoir al Tl . Applying the entropy principle, prove that the maximum work obtainable from the engine is
W(na"oJ "

Q - TI{S, - Sl)

where 5 1 - Sl is lhe entropy decrease of the body.

If the body is maintained al constant volume ha ving oonstan t volume heal capacity C. " S.4 kJlK which is independent oftemperatme, and if TI - 373 K and T2 303 K. detennine the maximum worlc. nbtainable. AIlS. 58.96 kJ

208=7.13 Each of three identical bodies satisfies the equation U CT, where C is the heat capacily oreaeh of the bodies. Thei r initial temperatures are 200 K, 250 K. and 540 K. If C 8.4 kJlK, what is the m.uimwn amount of work that can be extracted in a process in which these bodies are brought 10 a final common temperature? Ans. 756 kJ 7. 14 [n th e temperature range between ooe and looe a pani cular system mainTained at constant volume has a heat capacity.
C,. - A + 28T

wilh A - 0.014 J/K an d B _ 4.2)( 10""-4 J/K 2. A heaT reservoir at O C and a reversible wo rk soun:e are ava ilable. What is the lll3!I.imum amounT of"'ork thaT can be transfcrred 10 the Kvel""!ible work source as the system is cooled from 100C to the temperature of the reservoir?
An.!.4.508J 7.15 A Kversible engine, as shown in Fig. P. 7.15, during a cycle of operation draws 5 MJ from the 400 K reservoir and docs 840 kJ of work. Find the amount and direction of heat interaction with other reSClVoirs. A".<. Q2 - +4.98 MJ QJ .. -0.82 MJ

'W- 640kJ

Fig. P. 7.15
7.16 For a fluid for " 'hich pvl T is I constant quantity eq ual to R, show that the change in specific entropy bct,,ecn Iwo states A and 8 is given by
5 8 - S,,-

're p

-dT- Rln -Po T p"

A fluid for wh ich R is a constant and equal to 0.287 kl/kg K, flows steadily through an adiabatic machine, entering and leaving through two adiabalic pipes. [n one of these: pipes the pressure and temperature are S bar and 450 K and in the other pipe the pressure and tcmperature are I bar and 300 K n:specti\ely. Determine which prC" UK and lempernture refcr to the inlet pipe. For the given tempernture rnnge. c p is given by

cp"'o lnT +b whc:n: T is the numerical value of the absolute temperature and a - 0.026 kJ/kg K. b = 0.86 kJ/kg K. AIlS. sa - SA .. 0.0509 Ufkg K. A is the inlet pipe

7.17 Two vesse ls. A and B. each of \'olume 3 m1 may be connected by a tube of negligible volume. Vessel A conui ns air at 0.7 MFa. 95C. while vesse l B contains air at 0.35 MPa. 205C. Find the change of entropy when A is COTI/lected to B by working from the first principles and assuming the mixing to be complete and adiabatic. For air take the relations as given in Examples. 7.8. AIU. 0.947 kJIK 7.18 (a) An al uminium block (c p - 400 1lkg K) v.; th a mass of .'i kg is initially at 40"C in room air at 20"C. It is cooled reversibly by tmosferring heat 10 a complete ly re\'ersible cyclic beat engine untilttle block reaches 20C. The 20"C room air serves as a constant temperature sink for the engilN:. Compute (i) the change in entropy for the block. (ii) the change in entropy for the room air. (iii) the work don e by the engine. (b) If the aluminium hlock is all owed to cool by natural con\'ention to room air. compute (I) the change in entropy for the block. (ii) the change in eDITOpy for the room air (iii) the net change in entropy for the unhersc. AIU. (a) - 134.2 11K. + 132 JIK. 1306 J. (b) - 132 1 1K. + 136..'i 11K. 4.5 JIK 7.19 Two bodies of equal heat capacities C and temper~tures Tr and T: form ~n adiabatically closed system. What will the final temperature be if one lets thi s system come to equilibrium (a) freely? (b) reversibly? (cl What is the lJWIimum work which can be obtained from this system? 7.20 A resimor of 30 ohms is maintained at a cDnstanltemperalUre of 27C while a current of 10 amperes is allowed to flow for I sec. DetermilN: the entropy change of the resistor and the universe. AIlS. (6S)...;_ " O. {M),.;, . 10 11K If the resistor iuitiany at 27C is now in sulaled and the same cum:nt is passed for the same ti me. dete""ine the entropy ehange of the mislor and lite universe. The-specific heat of the resistor is 0.9 kJ/kg K and the mass of the resistor is 10 9. Ans. (45')..;. .. 6.72 JIK 7.21 An adiabatic vessel contains 2 kg of water HI 25"c' 8y paddl e-wheel work tntnsfer, the tcmperaIUTC of water is increased to 30C, If the ~pecific heat of water is assumed consta nt at 4. 187 kJlkg K. find the entropy change of the unherse. AIIJ. 0.139 kJ/ K 7.22 A cOPl"'r rod is of lcngth I m and diarmtcr 0.01 m. One en(] of the rod is at 100C, and the other Itt OC. T1tc rod is perfectly insulated along its length and the thermal conductivity of copper is 380 W/mK. Calculate the ra te of heat transfer along the rod and the .r:lte of entropy production due to im:\'ersibility of this hcat tmnsfer. An$. 2.985 W,O.OO293 WIK 7.23 A body of constant beat capacity Cp and at a tC'l1perature Tj is put in contact with It reservoir at It high er temperature Tf The press ure remains constant while the body comes 10 eq uilibri um wilh the rcscn:oir. Show that the cntropy change of the un!\'CTSC is equal to

Cp[r.;/ -In (1+ Ii;, T f)]


210= Prove lhat this entropy change is positive. Given: wherc x< I. 7.24 An insulated 0.7S kg oop~r calorimeter can contai ning 0.2 kg water is in equi librium at a tempmllIIn: of lO C. An experimenter now places O.OS kg of ice at OC in the calorimeter and encloses the latter with a heat insulating shield.. (a) When all the ice lias melted and equi li br;um has been r=el\ed, what will be the tem~rature of wiler and the can? The specific heat of copper is 0.418 kJlkg K and tile lalent beat of fll5ion of ice U 333 kJlkg. (b) Compute the entropy increase of the universe resulting from the process. (e) What will be the minimum work needed by a 51irrer to bring back the tem~rature of water to Ans.(a)4.6SC, (b)0.00276 kJlK. (e) 20.84 kJ 7.2!i Show that iftwo bodies ofthennal capacities C) and Cl at lempemtums T) and T: an: brought 10 the same temperature Tby means ora revenib le heat engine, then InT - C1 Ln7i+C1 LnT:


C, +Cl
7.1.6 Two blocks of metal . each having I mass of 10 kg and a specific beal of 0.4 kJf kg K., an: at a temperallln: of 4O"C. A reversible refrigerator receives heat from one block and rejects heat to the other. Calculate the work required to calISe a lemperallln: difference of IOOC beN,'een the two blocks. AIlS. 32 kJ 7.27 A block of iron weighing 100 kg and having a tem~raturc of 100C is ill"l!l1eTSed in 50 kg of water at a tem~raUlrc 0(200(:. What will be the change of entropy of \be combined sy5lem of iron and water? Specific heats of iron and water arc 0.45 and 4.18 kJ/kg K n:spcctively. AIlS. 1.24 kJfK 7.28 36 g of water at 30e arc convened into 51eam at 250"C at eonstant atmospheric pressure. The specific heat of water is asswned constant at 4.2 I I gK and the latent heal of vaporization al lOO C is 2260 JIg. For water vapour, allume pY- mRTwhere R - 0.4619 kJ/kg K. and


"' 0

+ bT+ cr. whcrca - 3.634.

b .. 1.195 )( 10- 1 K- 1 and c .. O. 135)( 10- 6 K-1

Calculate the entropy cbange of the SYStCD1 .

AIlS. 273.1 11K 7.29 A 50 ohm resistor carrying a constant clIfTCnt of I A is kepi at a constanl temperature of 27C by a stream of cooling waler. In a lime inlerval of I s, (a) whal is the change ill entropy of the resistor? (b) What is the change in enlropy of the universe? Ans. (a) 0, (b) 0.167 JfK 7.30 A lump of ice wilh a mass of I.S kgat an initialtempe-rallln: of260 K melts at the pressure of I bar as a result of heat transfer from the environment. After some

time has elapsed the rt'Suhing water anaio! the tempmlture of the environment. 293 K: Calculate the entropy production associated with thi, process. The lalent beat of fi.u:ion of ke is 333.4 kJlkg. the specirlc heats of ice and Wiler are 2.07 and 4.2 kJlkg K respec1i~cly. and iu mells II 273.15 K. AM. 0.1514 kJlK An ideal gas is compressed re~ersibly and adiabatically fTom state Q to S'-Ie b. II is then heated reversibly al constant volume to ,'-Ie c. Afta expanding reversibly and adiahalically to state d iuch that Tb - T.to the gu is again lC\'enibly beated at constant pressure to state t such tlIa.t T. - T. Heal is then rejected reversibly from the gas at constant volume till it returns to state a. EJ;press T. in terms ofTb and T., IfTb .. S55 KandT. " 53S K, estimale T. Take


r- 1.4.
AM. T. "

-T' 3\3.29K r.

T.r~ 1

7.32 Liquid wlter of mass 10 kg and temperature 200C is mixed with 2 kg ofiu atS'C till equilibrium is reached at \ atm pressure. Find the entropy change of the system. Given: cp orwater '" 4.1 8 kJlkg K.cpofiu - 2.09 kJlk8 K and latent helt of fusion orice - 334 kJfkg.

AM. I04.9 JIK

7.33 A thermally insulaled SO-obm rcsisWrcames li ClIm:nt of I A for I I. ~ initill temperature of the resistor is 10C. Its mass is 5 g and its specirlc helt is 0.85 J/8 K . (a) What is the cllange in entropy of the resistor? (b) What i. the change in entropy of the universe? AM. (a) 0.\73 JIK (b) 0.173 JIK 7.34 The value of cp for a certain substance can be: represented by cp " Q + hT. (I) Dctennine ~ beal absorbed and the increase in entropy of a mass m of the substance when its temperalul'l: is increased at constant pressllTC from TI to T2 (b) Find the increase in Ihe molal specific entropy of copper. when the temperallUe is incl'l:ased at constanl PI'l:SSUI'l: from 500 to 1200 K.. Gi~en for copper: when T oo 500 K. c p " 25.2 x 1<1 and when T " 1200 K. cp - 30. 1 x IIY JIk mol K.

AIlS. (a) m[ ,,(T 1 - 7j) + tCTiZ - 7jl )]

m[" In ~ + b{1j - 7j)J

(b) 23.9kJlk mol K 7.3S An iron block of unknown mass al 8S C is dropped inlo an insulaled tank. thlll contains O.lml ofwDler at 20"C. At the same time a paddle-wheel driven by a 200 W moloJ is activated to stir the water. Thermal equilibrium is established after 20 min when the fmal temperature is 24e. Determine the man of the iron block and the entropy genemted during the proces,. Atu. 52.2 kg. 1.285 kJlK 7.36 A piston-cylinder device contains 1.2 kg of nitrogen 811! at 120 ir.Pllnd 27C. The gas is now compressed slow ly in a polytropie process during wbich pVI.J _ COlIStant. ~ process ends when the volume is reduced by one-half. Oetemtine the entropy change of nitrogen during tbis process. An!. - 0.0615 kJlK.


. I


&sic II" Applin 11ImMJ]Mmics

Air enters a compressor at ambient conditions of 96 kPa and 17"C with a low velocity and exits at I MPa. 327C, and 120 mls. ~ COlTlpl"l:S5Or ill cooled by the ambient air al 17C at a rate of 1500 kJ/min. The power input to the compressor is 300 kW. Detmnine (a) the mass flow rale ofaiT and (b) the rale of entropy generatinn. AILl. (a) 0.851 kgfs. (b) 0.144 kWIK 7.38 A gearbox opmuing al steady stale nxe ives 0. 1 kW along the input shaft and delivCTS 0.095 kW along tbe OUlput shaft. The oUler surface of the gearbo~ is at 50"C. For the gearbox, determine (.) the rate ofhea! transfer, (b) the rale at which entropy is produced. ,Ins. (a) - O .OOS kW, (b) 1.54 x H'-' 1i.w1K 1.39 At steady state, an electric motor develops power along its output shaft al the ratt of 2 kW while dBwing 20 amperes at 120 volts. ~ outer surface of the motor is at 50C. For the motor, determine the rate of heat transfer and the TIIte of enl/"Ofly generation. Ans. -0.4 kW, 1.24x iO-l kW/K 7.40 Show thai the minimum theoretical work input required by a refrigeration cycle to bring two finite bodies from the s.amc initial temperature to the final temperatures of T! II!Id Tl (Tl < T[) is given by
W... me [2(T[T2)1 12 - T[ - T21

7.41 A ri gid tank eonwll5 an ideal gas 8t 40C that ill being stirred by a paddle wheel ~ paddle whed does 200 kJ of work on the ideal ps. It is observed tltat the temperature of the ideal gas remains eOl\5blnl during Ibis proeess !U a result of heat trans fer between Ihe system Ind the surroWldings al 25C. Determine (a) the entropy change of the ideal gas and (b) the total entropy generation. AIlS. (a) 0, (b) 0.61\ kJlK 7.42 A cyli ndrical rod of length L insulated on its latlmll surface is initi.lIy in contact at one end with a wall at tempCratun: Tl and at the other end with a wall at a lower temperature Tl . The temperature within the rod initially varies liourly with position x aceord.illg to:
T(x) " T[ -1j-ll x

The rod is insulated on its ends and evelltuall y oomcs 10 a final equilibrium state where the tcmperatun: is T~ Evaluate Tr and ill terms of Tl and T2, and show that the amount of entropy generated is:

_ =[I+lnTI+~ln1i - -r,-", r,l ~-1i ~-1i

where e is the specific heat of the rod.

AIlS. Tf [T[ + Tl ]/2 1.43 Air flowing through a horizontal, insulated duet was studied by students ill a laOOl11tory. One student group measured Ihe pressure, temperature. and ve locity al a location in the duet as 0.95 bar, 61C, 15 mls. AI another location the respective values were found (0 be 0.8 bar, 22"C, 310 mfs. The group


neglected to note tile mine the direction.


of flow, 1I0we\'eT. Using the knollo"R data, deter-

AIU. Flow is from right to left 7.44 Nitrogen gas ~t 6 bar, 21C enters an insulated control Itolwnc operaling al steady state for which Wc.v. - O. HaIr of the nitrogen u ilS the device at I bar, S2e and the other half el\ ilS al I bar, - 40C. The eff/Xu of KE and PE are negligible. Employing the ideal gas model , decide whC1 her the device can operate as described. All.!". Yes. the device can operate as described


Available Energy, Exergy and Irreversibility


Avallable Energy

11K: SOUll:ClI of energy can be divided inlO two grouP'. vi:t. high grade energy and

low grade energy. The conversion of high grade energy to shaft work is exempted
from the limitations oflhe second law, whi le conversion oflaw grade energy is subject to them. . The examples ortwo kinds of energy are:

High grade energy (a) Mechanical work (b) Electrical energy

(e) Water power

Lew grade energy (a) Heat or thermal energy (b) Heat derh'ed from nuclear fission or fusion
(e) Heat derived from combustion offossil fuels

(d) Wind power (e) Kinetic energy ora jet (f) Tidal power

The bulk of the high grade energy in the fonn of mechanical work or electrical energy is obtained from sources oflaw grade energy, such as fuels, through the medium of the cyclic heat engine. The complete conversion oflow grade energy,
heat, into high grade energy. shaft-work, is impossib le by virtue of the second law of thennodynamics. That part of the low grade energy which is available for conversion is rererred to as available energy, while the part which. according to the second law, must be rejected, is known as unavailable energy. Josiah Willard Gibbs is accredited with being the originator of the availability concept. He indicated that environment plays an important part in evaluating the availab le energy.


8.2 Avallable Energy Referred. to a Cycle
The maximum work outpul obtainable from a celUin heat input in a !!yclic heai engine (Fig. 8.1) is called chcavoilableellergy(A.E.), or the available part of the energy supplied. The minimum energy thai has to be rejected 10 lite sink by the second law is called Ihe ulI(lI'ai/able energy (U.E), or the unavailable part of the energy supplied. Therefore, or QI

A.E. + U.E.

Wmu - A.E . .. QI - V.E. For th e given T, and Tl


= 1 _..2..

r, "

For a given TI 'lie" will increase with the decrease of T2. The 10weSl practicable temperature of heal rejection is the temperature oj/he surroundings,


Lei us consider a finite process x-y, in which hea l is supplied reversibly 10 a heal enginc (Fig. 8.2). Taking an elemenlarycycle, ifd Q I is the heat received by the engine reversibly at TI then


- --



(tQI " (tQ,- -

To dQI '" A.E. 7j


Flg. 8.1 ANfla61t flM "1III~lIilablt nurt;J f~ a "'"



For the heat engine receiving heat for the whole pru.:essx-y. and rejecting beat



J .IV ~

= .Q, -

J ~

J -'..Q, ~ 1i


W...... = A.E.
'" Q~y- TO (Sy - s.)


The unavailable energy is thus the product of the lowest temperaU1re of heal rejection, and the change of entropy of the system during Ihe process of supplying heal (Fig. 8.3). The available energy is also known as aergyand the unavailable energy as trll'rgy. lhe words fU"St coined by Rant (1956).


_IllY, Of eMIVY

177777777.t- '. UnlYailable


w""", . w.,.

TO (s,.-s.)

Ftg. 8.3

lfIIImJlWIiIl1InIJ II] 1M swnul Usw

8.2.1 Decmue mAvaUllbk &ngp'WMtt HNlis TratuJnud tht01lf1t a FimU TelllJIertllure DiJftrma
Whenever heal is transferred through a finile temperature difference. there is a decrease in the availability of energy so transferred. LeI us consider a reversible heat engine operating between T] and To (Fig. 8.4). Then

QJ = T] at. Q2 = To at, and W", A.E. = (T1 - Til ll.r

f tl'o,Ml'+:,
. :

Let us now assume that heal Q] is transferred through a finite tempemture difference from the reservoir or source at T1 10 the engine absorbing heat at Ij. lower Ihan T1 (Fig. 8.5). The availability of Q] as received by the engine at 1j

lower than Tl (Fig. 85). The availpbility of Ql as received by the engine at Tj can be found by allowing the engine to operate reversibly in a cycle between Tj and To receiving Q1 and rejecting Q2'


Fig. 8.5

/ft(f't4U 1 '/1 MtullNIilllbk tllnlJ due If Ill" /tatuftr

IhrQugh a jitlik InlIpmllllrt diffrrnv:t


QI - TIM - TiM
TI > T'I' :. &' > & Q1 '" To & Q'2 = To W'
As'>As :. O'l > Ql


W'" QI - 0'2" 1"1 M' - ToM W - Q I - Q2 "" r l & - ToM W <: W. because 0'2 > Qz Available energy or exergy losl due to irreversible heat transfer through finite temperature difference between the source and the working fluid during the heat addition process is given by W - W'=O'l - Ql - Tn (As' - As) or, decrease in A.E. ~ To (AI" - As) The decrease in available energy or exergy is thus the product of the lowest feasible temperature of heat rejection and the additional entropy change in the system while receiving heat irreversibly, compared to the case ofrevetsible heat transfer from tbe same source. The greater is the temperarurc difference (TI - 1"1), the grealer is the beat rejection Q' 2and tbe greater will be the unavailable part of the energy supplied or anergy (Fig. 85). Energy is said to be degraded each time it flows through a finite temperature difference.



=-ADtJUdle EJUrCI fron.



Fi"iIe Eftn'C1 Soara

Let us consider a hot gas of mass m. at temperature T when the environmental temperature is To (Fig. 8.6). Let the gas be cooled at constant pressure from state

I at temperature T to state 3 at temperature To and the heat given up by the gas, Ql' be utilized in heating up reversibly a working fluid ofmassm..rfrom state 3 to state I along the $IlITIe path sothat the temperature difference between the gas and the working fluid at any instant is zero and hence. the entropy increase of the universe: is also zero. The working fluid expands reve~ibly and adiabatically in an enginc or turbine from stale I to state 2 doing work WE' and then rejects heat QJ reversibly and isothermally to rerum 10 the initial state 3 to complele a heal engine cycle.

--;';-- 1




r'---t-~-* , - T, 0,

Ql ., m. cp/T - TO> '" nt...r'i>..r(T - TO> - Area 1-4-5-3-1

T Q2 '" To 1lSwr'" To"'wtcp"r In To "" Area 2-4-5-3

Available energy - Wnw

- Ql - Q2



T -mc (T - To} - Tomc InIP, liP, To

- Area 1- 2- 3-1 Therefore, the available energy or exergy of a gas of mass ml at temperature T is given by

AE = m.cp, [( T-1O )- To In



This is similar to Eq. (7.22) derived from the entropy principle.

8.3 Quality of Energy

Let us assume that a hot gas is flowing through a pipeline (Fig. 8.7). Due to heat loss to the sUITOundings, the temperature of the gas decreases continuously from inlet at state a to the exit at state b. Although the process is irreversible, let us assume a reversible isobaric path between the inlet and exit states of the gas (Fig. 8.8). For an infinitesimal reversible process at constant pressure,
dI' -

mCpdT T


,, '"



Fig. 8.8 Entre 911alilJ al SUlU 1 is slIptrior I~ lAal al SUlU 1





mc p


where m is the m3SS of gas flowing and c p is its spedfic heat. The slope dTldS depends on the gas temperature T. A s T increases, the slope increases, and if T decreases the slope decreases. Let us assume that Q units of heat are lost to the surroundings as the tcmperature of the gas decreases from 1"'1 to F I, TI being the average of the two.

Heat loss

Q= mc p (1"'] - 7";)

- TlbS I Exergy lost with this heat loss attempernture T] is

W] "' Q - Tolli]


When the gas tempernture has reached TiT2 < TI), let us assume that the same heat loss Q occurs as the gas tempcrntu re decreases from Tl to G, T~ being the average temperature of the gas. Then Heat loss

Q '" mc p (Tl - T'i) '" T2 651 Exergy lost with thi s heat loss at temperature T2 is W1 - Q-T(I !1S2
From Eqs (8.6) and (8.8), since T] > T2 !1S 1 < 652

(8.8) (8.9)

Therefore, from Eqs (8.7) and (8.9),

The loss of exergy is more, when heat loss occurs at a higher temperature TI than when the same heat loss oe<:un; at a lower temperature T2 Therefore, a heat loss of I kJ at., say, lOOOQ C is more harmful than the same heat loss of I kJ at, say, 100C. Adequate insulation must be provided for high temperature fluids (T To) to prevent the precious heat loss. This many not be so imponant for low tempernture fluids (T - To), since the loss of available energy from such fluids would be low. (Similarly, insulation must be provided adequately for very low temperature fluids (T Tol to pl\!vcnt heat gain from surroundings and preserve avai lable energy.) The available energy or exergy of a fluid at a higher tempernture T[ is more than that at a lower lempernturc T2, and decreases as the temperature decreases. When the fluid reaches the ambient temperature, it:> exergy is zero. The second law, there fore, affix es a quality to energy ofa sysll:m a\ any state. The quality of energy of a gas at. say, l OOOoe is superior to that at. say, 100C, since the gas al lOOOC has the capacity of doing more work 1han the gas at I OO~C, under the same environmental conditions. An awareness of this energy quality as of energy quantity is e~5ential for the emcien! use of our energy resources and for energy conservation. The concep t ofUI'ui/ableenergy or exergy pro"ides a IIseful measure of {his energy qualily.

-== 221

La", of Degrfldation of Eurgy

The available energy of a system decreases as its temperature or pressure decreases and approaches that of the sunuundings. When heat is transferred from a system, its temperature decreases and hern:e the quality of its energy deteriorates. The degradation is more for energy loss at a higher temperature than that at a lower temperature. Quantity-wise the energy loss may be the same. but quality-wise the losses are different. While the firsT law states that ellergy j.f
always consen.ed quantity-wise. the second law emphmizes tlUit energy always degrades quality-wise. When a gas is throttled adiabatically from a high to a low pressure. the enthalpy (or energy per unit mass) remains the same. but there is a

degradation of energy or available work. The same ho!ds good for pressure drop due to friction of a fluid flowing through an insulated pipe. If the first law is the law of conservation of energy. the sewnd law is called the low of degradation of ellergy. Energy is always conserved. but its quality is always degraded. Anicle 8.2. 1which shows how energy gets degraded by thermal irreversibility and produces less useful work can be explained in a lillie different way. Let two bodies I and 2 of constant beat capacities C) and C2 be at temperatures T ) and T2 (T) ,. T1). These are connected by a rod and a small quantity of heat Q flows from I to 2. The total change of entropy is:

M = t.S) + M 2::

Q[...!. -.!..] ,. 0 1'2 11

(since T) > 7'2)

1lle entropy will continue to increase till thermal equilibrium is reached. Let us now suppose that instead of allowing heat Q to flow from I 10 2. we used it to opcr.lIe a Camm engine and obtain mechanical wort, wilh ToSS the sink temperature. The maximum work obtainable is:

Wt=Q[ I -

~] ~:] <W1

If, however. we first aUow Q to flow from Ito 2 and then use it to operate the CanlOI engine. we obtain:
W2 = Q[I-

Thus, in the course of the irreversible heat conduction the energy has become degraded to the extent that the useful work has been decreased by
aW = W) - W2 ", To.o.s

1bc increase in entropy in an irreversible change is thus II measure of the extent to which energy becomes degraded in that change. Conversely, in order toutract the maximum work from a system, changes must be performed in a reversible manner so Ihat toml entropy (AS,y, + AS....) is conserved. It is worth pointing that if the twO bodies were allowed to reach thennal equilibrium (a) by heal conduction and (b) by operating a CamOi engine betwL'Cn

them and extracting work. the [mal equilibrium temperarures would be different in the two cases. In the first, V[ + U2 is conserved and die fmal temperature is:
...ru) _

'1- -

CI 1i + C2 T1
C1 +C1

In tbesecond case.S l +52 isconscrved and W=-AU (-AUt + Uv(': 4W = d Q- dU, < TdS - d V so that If Wnw. = - dU), In the isentropic process, the final

temperalure is given by:

rr') = 1fl"'Cl +ClI r2CAC1


< Tf N )


C[=C2 =C.

r [Ul= 1i

+T2 and Tf l)=(T1T:z}ll2 2

The difference in fInal temperawre is due 10 the lower val ue of the total inlernal
energy which resul ts from work having been done al the expense of internal energy (see An. 7.9.3). Similarly, it can be shown that due to mechanical irreversibility also, energy gCl$ degrnded so thallhe degradation of energy quality is a universal principle.

8.4 Maximum Work in a Revenible Process

Let us consider a closed stationary system undergoing a revcNoible process R from stale I to state 2 by interacting with the surroundings atpo- To (Fig. 8.9), TIlen by thcflfSllaw,


R I ",
""" '"
-~ .





flg. 8.9 M4i1ll.m WfI1k d#M bJ dowJ IJslmI

If the process were irreversible. as represenled by the dotted line r. connecting the same equilibrium e nd stales. (S.12) Q I =V1 - VI + WI Therefore. from Eqs (S.I I) and (8.12).

QR - Qr=WR - Wr



By the second law, For a reversible process,

as .. S2-SI -Jm....., To O

QR'" To (S2 - SI)

For an irreversible process,
AS..,,;v> 0

(B. 14)

>0 T. Ql < To (Sl-Sl) From Eqs (B.14) and (B. IS), Qk > Q)
Therefore, from Eqs (B.1 3) and (B.16),


(8.1S) (8.16)

(B.17) WR > W) Therefore, the work done by a closed system by inleracting only with the surroundings atp! To in a reversible process is always more than that done by it in an irreversible process between the same end states.

8.... 1 Work dotu in. aU Rnlermk Prowses is tJu Same

Let us assume two reversi ble processes R) and Rl between the same end states I and 2 undergone by a closed system by exchanging energy only with the surroundings (Fig. B. 10). Lei one of the processes be reversed.






Fig. 8.10 bpilll _rio daIU ill aU rrrmibl, I"IK~m bttwttl, l/u UlIII' mtl stafts

Then the system would execute a cycle 1- 2- 1 and produce network represented by the area enclosed by exchan ging energy with onl y one reservoir, i.e. th e surroundings. This violates the KelvinPlanck statement. Therefore, the

two re~"ersible processes must coincide and produce equal amounts a/work.

8.5 Reversible Work by an Open System Exchanging Heat only with the Surroundings
Let us consider an open system exchanging energy only with the surroundings at constant temperature To and al constant pressure Po (Fig. 8.1 1). A mass dm, enters the sys tem at state I, a mass dm21eaves the system al state 2, an amount of heat (tQ is absorbed by the system. an amount of work d W is deli vered by the system, and the energy of the system (control \'olume) changes by an amount d()". Applying the first law. we have

FIg. 8.11

ikuwibk WIlT/; d~/U by U /lpm 9JWn wllik IlIwngin& Mill onl] willlllu IIlffollttdil/#

- dE,, " d(U+

m;l +mg:l,.

(8. 18)

For the maximum work, the process must be en ti rely reversible. There is a temperature difference between the control volume and the surroundings. To make the heat transfer process revers ible, let us assume a reversible heal engineE opera ting between the two. Again, the temperature of th e fluid in the control volume may be different at different points. It is assumed that heat transfer occurs at points of the control surfac e 17 where the tcmperoture is T. Th us in an infinitesimal reversible process an amount of heat dQo is absorbed by the engine E from the surroundings at temperature To< an amount of heal dQ is rejected by the engine reversibly to the system where the temperature is T, and an amount of work d W~ is done by Ihe engine. For a reversible engine.

~=OQ T, T
4Wc = 4Qo - dQ= dQ'T - dQ



dWc= dQ( ~ -I)


1bc work (f W e is always positive and is independcnl of the direction of heal flow. When To> T. heat will flow from the slIrroundings to the system, dQ is positive and hence (f We in Eq. (8.19) would be positive. Again. whe n To <T. heat will flow from the system sunoundings. (f Q is negath'c. and hence d We would be positive. Now, since lIIe process is reversible, the entropy change of the system will be equal to the nel entropy transfer, and S.... '" O. Therefore,


Now, the maximum work is equal 10 the sum afme system work dWand the work dIVe ofme reversible engine E,
(8.21 )

From Eq. (8. 19),


Substituting Eq. (8.18) for dW in Eq. (8.22),

d"Wnw.""dQ+dml ( h l +


+8Z 1)-dllll(h:J.+ V ! +8~2)

(h:!+ V! +81:2)

-<1lu+ lilt +mgzl+dq~ -I)

=dm l

(hI + ~2

+8Z I)- dm l

mY' -<l [ U+ - +m8Z +-OQ To 2 T


226=On substituting the value of d QITfrom Eq. (S.20).

4W "' dm{hl+ ~1 +8ZI) - dml(~+ V ! +8'=1)



m;l +mgZl

+ To(dS - dmls l +dmpi)

4W..... -

dm{h 1- T oS 1+ ~1 +8ZI) - dm1(h1-TOS 2 + V ! +8%2)

mY' -d[ U-ToS + -,-+mgz "


Equation (8.24) is the general eJlpression for the maximum work of an open system which exchanges heat only with the surroundings at To-Po-

8.5.1 Rnlnsible Work i. tJ Stea.d! Flow Procus

For a steady flow process

+mgzl .. o



Equation (8.24) reduces to

4Wma. - dm[(hl-ToSI+


+gZI)-(h2 - ToS2+

V! +gZ2)]


For total mass flow, the integral form ofEq. (S.2S) becomes

Wmu=(Hl_ToSI +m;12 +mStI) -(Hl - ToS:z+ m;i +mSZ1) (S.26)

The express ion (H - ToSl is called the Keenan junction, B.

W....,.= ( Bt+ -mY,' , - +m8%1 - B1+ -mY! , - +mSZ1

- II - l2



where Vis called the availability function ofa steady flow process given by

mY' yr - B+--+m8'
On a unit mass basis,

W"",, - (h1-ToS1+

2 +8Z1)-(h1-ToS1 +





IfK.E. and P.E. changes are neglected, Eqs (8.27) aDd (8.28) reduce to "'mu; "' B I - B2
... (HI - TtpSl) - (H! - ToSz) ... (HI - Jl2) - To(S] - S2)


and per unit mass "'rnu - bl - bl ~ (hI - hi) - To (S1 - s2) (8.30)



Work i. tJ

Clos~d System

For a cfos~d system. dm l - dm1 - O Equation (S.24) tben becomes

dWrnu -- ~U-TQS+
- - d(E - TgS)"



mY' E - U+--+m 2 For a cbange of stale of the system from the initial state I to the final state 2, Wrnu .. E] - E1 - To (SI-S2)
- (E] - TtpSl) -(E1 - TtpS2)
(8 .3 1) (8.32)

If the K..E. and P.E. changes are neglected, Eq. (8.3 1) reduces to
"'rnu " (U1-T~I) -(UI- Trfil)

For unit mass offluid,

"'mal '" (ul - ul) - To ($1 - $2)

= (ul-To'l)-(UI-To'l)


8.6 Useful Work

All of the work II' of the system with a flexible boundary would not be available for delivery, since a certain portion of it would be spent in pushing out the atmosphere (Fig. S.1 2). The useful work is defined as the actual work del ivered by a system less the work perfonned on the atmosphere. If V] and VI an: the initial and rmal volwne of the system andpo is the atmospheric pressure. then the work done on the atmosphere is Po (V1 - V]). Therefore, the useful work "'. (S.34)




/ 0 /\;V,
System ;



/ ! Bour.cIary




.'- - - "".


Fig. 8.12

Werk d/Yllt by" tltstd sys/nn in P,wulll clI/IM almOlplurt

Similarly. the maximuM usefol work will be

(WJ.... - W...... - Po (Vz - VI) In differential fonn

(dWJ .... - dWIIIIJI - PodV


In a steady flow system, the volume of the system does notehange. Hence, the maximum useful work would remain the same, i,e" no work is done on the atmosphere, or

But in the case of an unsteady-flow open syslem or a dosed system, the volume of the system changes. Hence, when a system exchanges heat only with the atmosphere. the maximum useful work becomes

(d Wu)..... ~ d Wmu - Po dV Substituting dW..... from Eq. (8.24), (dWJ..... = dm l ( hi -Tos l

+ ~2 +g;:l) -

dm1 ( h,. _ TnS2 +



-d[U+PO V_T05+m;2 + mgzl.

This is the maximum useful work for an u1I5/eutfy open !i)'stem, For the closed system, Eq. (S.3S) reduces to


(dWJ.... " -d[ U+poV-To S+ -mY' , - +mgz "

(S.39) (SAO)

"" -d[ + Po V- ToS1,.

(WJn.... -1- 2 + Po (VI - Jl2) - To (51 - 52)

IfK,E. and P.E. changes are neglected. Eq, (S.40) becomes

(W..>m.. " U I - U2 + Po (VI - V2) - To (51 - 51)

(SAl )

This can also be wrinen in the following fonn (Wu)mu - (UI + Po V] - ToS l ) - (U2 + PO V2 - T05'2)


= f l -fz

9 is called the

availability function/or a closed sYJrem given by

,"'U+PQJI - T~

The useful work per unit mass becomes (WII ) .....



+ POv l - Tol'l) - (U2 + pQv1 - Tofl)


8.6.1 Main"". Usefid Work OillailUlble wheft the s,slnfl EuIuJ"Iu Heal wUh a Thtrmal RutTlloir ill AtldilUm 10 the Ah1uJspme
If the open system discussed in Sec. 8.S exchanges heat with a thermal energy reservoir allemperature Tk in addilion 10 the abnospbere, the maximum usejUl work will be increased by (t QR(I system. For a steady flow process,

~: ), where (I QRis the heat received by the

For a dosed system (Wu) .....


Wnw - PI} (V2 - "1)+ QR

(1- ~)


(Wu)..... "'EI - E2 + PO(JlI - Vl) - TO(SI - S2)+QR(I-

IfK.E. and P.E. changes are neglecled, then for a steady flow process:
(Wg ),.,..

(HI - Hz) - To (S[ - Sz) + QR

(1 - ~:)
+ QR


and for a closed syslem:

(WII)owt " V[ - U I

+ PO (VI

- V2) - TrJ,SI - SiJ

(1- ~)


8.7 Dead State

If the state of a system departS from that of the surroundings, an opportunity c:xists for producing work (Fig. 8.13). However, as the system changes its state

230 = towards that of the surroundings. this opponunity diminishes, and it ceases to exist when th e two are in equilibrium with eacb other. When the system is in equilibrium with the surroundings, it must be: in pressure and temperature equilibrium with the surroundings, i.e., atpo amt To. It must also be: in chemical equilibrium willt the surroundings, i.e., there sbowd not be any chemical reaction or mass transfer. The system must have zero velocity and minimum potential energy. This state of the system is known as the dead Slate, wbich is designated by affixing subscript ' 0' to the properties. Any change in the state of the system from the dead state is a measure of lite available work that can be: extracted from it Farther the initial point of lite system from the dead state in terms ofp, I either above or below it, higher will be: the available energy or exergy of the system (Fig. 8.13). All spontaneous processes terminate at the dead state.



A _. , ,
(. )


I "






1\ To


8.8 Availability
Whenever useful work is obtained during a process in which a finite system undergoes a change of state, the process must tenninate when the pressure and temperature of !be system have become equal to the pressure and temperature of the surroundings,p oand To> i.e., when the system has reached the dead state. An air engine operating with compressed air taken from a cylinder wi ll continue to deliver work till the pressure ofair in the cylinder becomes equal to that of the surroundings,po- A certain quantity of exhaust gases from an internal combustion engine used as the high temperature source of a heat engine will deliver work until the temperature of the gas becomes equal to that of the surroundings, To. The availability (A) ofa given system is defined as tlre maximum usefol work (total work minus pdY work) thot is obtainable in 0 process in whiclr tire system comes to equilibrium with ilS surroundings. Availability is thus a composite property depending on the stateofboth the system and surroundings.

8.8. 1 AfJaiWlilitJ in a SU4d:J Flow hocus

The reversible (maximum) work associated with a steady flow process for a single flow is given by Eq. (8.26)


WtTV ""(HI_To5i+m;12 +mgZI)-(H2 -ToS:!+m;t +m g;:2)

With a given stale for the mass entering lite control volume, the maximum useful work obtainable (i.e., the availability) would be when this mass leaves the control volume in equilibrium with the surroundings (Le., at lItedeadstale). Sincc there is no change in volume, no work will be done on the I onosphere. Let us designate the initial state of lite mass entering the C.Y. with parameters havingllo surucript and the final dead state of the mass leaving !.he C.V. with parameters having subscript O. The maximum work or availability, If, would be

1I _ (H_To S+m;2 + mg:) -(Ho-ToSo+mpol '" V' -V'o


where VI is called the availability IUllctiolllor a steady flow system and Vo - O . This is the availability ofa system al any stale as it enters a C.V. in a steady flow process. The availability per unit mass would be

a - (h-Tos +



- (ho-T~o+gz)" '1' -'1'0


jfsubscripts I and 2 denote the states ofa system entering and leaving a C.Y. the decrease in availability or rnaJ[imum work obtainable for the given systemsurroundings combination would be W_ - a l -a2 - '1'1 - Vl1

- [ ( hl-To SI + V .}
- [(hz-Toso+

+gZI)-(ho -ToSo + ~ZO)]

~f +gZ2)-(ho-T~o+gZo)]

= (h l - h2)- To (sl - siJ +


1 +g(;:I- Z2)


ifK.E. and P.E. changes are Il(!gle<:ted, Wmu .. (hi - T~fl) - (h1 - T~iJ =b l -b2 where b is the specific Keenan function . If more lItan one flow into and out of the C.V. is involved.

Wmu .. Lmi 'lfi -


8.8.2 Ar1.UtJbaU, I NfYlljlorD Process

Let us consider a closed system and denote its inilial state by parameters without

any subscript and the final dead stale willt subscript '0'. The availability of the system II, i.c., the maximum useful work obtainable as the system reaches the dead state. is given by Eq. (8.40).


(8.51) If K.E. and P. E. changes are neglected and for unit mass, the availability

a - u - uo +Po(v-vcJ- To (s- so) "" (u + Pov - T~) - (uo-Povo-T~o)

'" ; - th

(8 .52)

where, is the availability function orthe closed system. If the system undergoes a change of state from I to 2, the decrease in availability will be
(l -

(;1 -

90)- (~ - 410)
+ Po (VI - vl) - To{s] 1$2)

- ;I - ~

.. (ul - u2)

(8.53 )

This is the maximum useful work obtainable Wider the given surroundings.

8.9 AvaJIabUlty in Chemical Reactions

In many chemical reactions the reactants are ollen in pressure and temperature equilibrium with the surroundings (before the reaction takes place)and so are the products aller th e reaction. An internal combustion engine can be cited as an example of such a process if we visualize the products being cooled to aunospheric temperature To before being discharged from the engine. (a) Let us first consider a system which is in temperature equilibrium with the surroundings before andallerthe process. The maximum work obtainable during a change of state is given by Eq. (8.31),
WIIIU - EI - 2 - TO (SI - S2)

., ( VI+ -mY,' , - +mSZI ) - ( V 2 + -mY! , - +mgz2 ) - TofSI-Sl)

IfK. E. and P.E. changes are neglected,

W""", " V I - V1 - To (SI - S1) Since the initial and final temperatures of the system are the same as that of the surroundings, TI "" Tl = To = T, say, then
(WT)mn = (VI - Vi'h - n:S I - S:zh (8.54) Let a property called Helmholtz/unction F be defined by the relation F - U -TS (8.55)
Then for two equilibrium states I and 2 at the same temperature T,

(FI - Fin - {UI

U2h - 7tSI - S2n

(8 .56)

From Eqs (8.54) and (8.56),
(WT)rrw " (F I - F 2n WT :S (FI - Flh


The work done by a system in any process between t\\'0 equilibrium states at the same temperature during which the system e~changes heat only with the environment is equal to or less than the decrease in the Helmholtz function of the system during the process. The ma~imum work is done when the process is reversible and the equality sign holds. If the process is irreversible, the work is Ie,s than the maximum. (b) Let us now consider a system which is in both pressure and tempemture eqUilibrium with the surroundings before and aftcrthc process. When the volume of the system increases some wode. is done by the system against the surroundings (pdVwork), and this is not available for doing useful work. The availabilityofthc system, as defined by Eq. (8.5 1), neglecting the ICE. and P.E. changes, can be expressed in th e form

A " (W.JIJWI '" (V + PoV - ToS) - (Uo + Po Va - ToSo)

'0 - </0
The maximum work obtainable during a change of slate is the decrea.'iC in availability of the system, as given by Eq.(S.S3) for unit mass.
(W~)mu - AI - Al " ~l - ~l

.. (U I - Vi) + POWI - V2) - To(SI - S2) If the initial and final eqUilibrium stales of the system are at the same pressure and temperature of the surroundinss, say PI .. Pl .. Po - p, and Tl .. T1 " To " T.


(S.59) (W~) ..... - (UI - U~p, T + p(VI - V2)P. T - 1'(SI - SJp, T The Gibbsfimctions G is deftned as G "' H - TS " U+pV - TS (S.6O) Then ror two equilibrium slates at the same pressure p and temperature T (GI - G1)p, T '" (U I - U1)p, T+ p(VI - V 2\..T - T(SI - S~P. T From Eqs (S.59) and (S.61)
(w.) .... .. (G I - G1)P.T

(S.61) (8.62)

(S.63) (W.Jp.T :S (G I - G 2)P. T The decrease in the Gibbs function ofa system sets an upper limit to the work that can be performed, e~elusive of pdV work, in any process between two equilibrium states at the same temperature and pressure, provided the system e~changes heat only with the environment which is at the 5artle tempenltun: and pressure as the end slates of the system. If the process is irreversiblc, the useful work is less than the maximum.


8.10 irreversibility and Gouy-Stodola Theorem

The actual work done by a system is always less than the idealized reversible work. and the difference between the two is called the irreversibility of the

This is also sometimes referred 10 as 'degradation' or 'dissipation' . For a non-flow process between the equilibrium stales, when the system exchanges heal only wilh lhe environmenl

1 - ( U I - UJ - Tr/..SI - 52) - ( VI - V 2) + Q) - To (52 -S I)-Q

~ Tr/..!lS)~ + TO<AS)-. .. To[(4S).ysoom + (&5).....1


Similarly, for the steady flow process

I - WIIloU. - W

_[(BI+ m;12 +mgZI)_(Bz+m:2 +mg~)]

_[(HI+m~12 +mgZI)_(H2+m~f
- TO<S2 - SI) - Q - T0<6SJ'''- + To<6SJ' .. TO<&5.,- +S.,.,.) - TA.uv



The same expression for irreversibility applies to bolh flow and non-flow processes. The quantity To(65O)"J1m1 +65...".) represents an increase in unaVlliiable energy (or anergy). The Gauy-Stodafu theorem states that the rate ofloss of available energy or exergy in a process is proportional 10 the rate of entropy generation, S..... If Eqs (8.65) and (8.66) are written in the rate form,

i~W (8.67) IosI - T04S""iv '" TOSJft This is known as the Gouy-Stodola equation. A thermodynamically efficient process would involve minirnwn exergy loss with minimwn rate of entropy generation.
8.10.1 Appluali.Dtu Df Gouy-SttuhlltJ EquliDn

(al Heat Transfer tJu-ougb a FiDtte Temperature DlfI"erence If heal

tnutsferQ occurs from the hot reservoir at temperature TI 10 the cold reservoirat temperature T2 (Fig. 8. 14a)





fig. 8.14

of4u/146/t WII,k '" U"D Mr. 4 ji";fllnlpmt,,, difftrrnu


~ hut



_ .... " _ .... " =Q O-1j



Ii 12

"'loot '" Q (I_ IL)= Q7i -12 7j 7i

1#1... - T~",.

If the beat tru\sfer Q from Tl to T1 takes place through a reversible engine E, the entire work output IVis dissipated in the brake, from whicb an equal amount ofhest is rejected to the rcservoirat T2 (Fig. 8.l4b). Heat transfer through a tinile tempenllure difference is equivalent to the destruction of its exergy.
(b) Flow with Friction Let us consider the steady and adiabatic flow of an Jdeal gas through the segment ofa pipe (Fig. 8.ISa).

By the fIrSt law, and by the second law,

Tds '" dh udp


j "" j - - j - dp=-j-dp

I dh







~l77777777/~/ , .
4 p p,-P:l




S IJI " Jrirdr =- pnRie... =-rir R In h.




--rirRln ( l-

~~)=-rir~-~~ )

_ rirR tip

,,(1 - tip) ;;: -~,since~< 1


and higher terms are neglected.

1YIoo, - BI - B2
- rir[(h l - Tas l) - (h2 - Tasv - rirTrJ.h - Sj) . 6p " ToS ,. ,;,RTo~ p,


The decrease in availability or losl work is proportional 10 the pressure drop

(6p ) and the mass flow rate (rir). It is shown on the right (Fig. 8.ISh) by the Grassmann diagram, the width being proportional to the availability (or exergy) of the stream. It is an adaptation oflhe Sankey diagram used for energy transfer

in a plant.

(c) Mixing of Two F1utdt Two streams I and 2 of an incompressible nuid or

an ideal gas mix adiabatically at constant pressure (Fig. S. 16).

m~ ., ~.

~~ ~/,\



Fig. 8.16

dill 10 mixiv



m1 + m2 = ml = m(say)

AMildk EMryJ, Extr(! aM lrrn:mihililJ


By Ihe firsllaw,

+ ';'~2 " (';'1 + ,;,2)h J xh\ + (I - x)h 2 - hl The preceding equation may be written in the fo ll owing form, since enthalpy is a function oftempcrature. xTI + (I - x)T2 - TJ



"' x+( I -x)r


where By the second law.


- ml - ';'ISI -


.. ,;,sJ - x,;,sl - (I -X),;,S2

= c In...l..+xc In....!.. P1j Prj


S"," '" In (-"-) ( r, )" nlC p 1i Ii

N - In ( r, ) 1jI _X 1j 121- .
N - In

(1i I 1j)I-.

Tl / 7j


where N. is

dimensionless quantity. called the entropy generation number.

given by S",./nlc p ' Substituting Ti Tt from Eq. (8.70) in Eq. (8.71).

N "'In x+r(l-x)

r -I- .


If x '" I or r '" I.N, becomes zero in each case. The magnitude ofN. depends on x and r. The mtc of loss of energy due to mixing would be (S.73)


Availability or Exergy Balance

The availability or cxcrgy is thc maximum useful work obtainable from a system as it reaches the dead state (Po, to). Conversely, ava ilabi lity or exergy can be

238=regarded as the minimwn work required to bring the closed system from the dead state to the given state. The valueofexergy cannot be negative.lraclosed system were at any state other than the dead state. the system would be able to change its state spontaneously toward the dead state. This tendency would stop wben the dead state! is reached. No work is done to effect such a spontaneous change. Since any change in state of the closed system to the dead state can be accomplished with zero work. the maximum work (or exergy) cannot be negative. While energy is always conserved, exergy is not generally conserved. but is destroyed by irrcversibilities. When the closed system is allowed to Wldergo a spontaneous change from the given state 10 the dead state, its exergy is completely destroyed without producing any useful work. The polen rial to develop work that exists originally at the given state is thus completely wasted in such a spontaneous process. Therefore, at steady slale: I. Energy in - Energy out - 0 2 . Exergy in - Exergy OUI - Exergy destroycd

EurtJ BalalJCe/01' a ~ed s,stm


For a closed system. availability or exergy transfer oceurs through heal and work interactions (Fig. 8.17).

1st law:

El - El '" JdQ - W 1_1

, ,


2nd law:

52 - 5, - {

TQ ] .. 5~ '[d


ToC51- SI )- To{

TQ ] " E ToS.... '[d

Subtracting Eq. (8.75) rrom Eq. (8.74).

AHiJahJi EMrrI, Eurc IUId IrrmmibfJily


-{[I- ~]dQ
Since, Chanee
in excrgy
Exergy transftf with heal

- W,_" - ToS"",

A2 -..4\ ..., 2 - , + prJV. - VI) - TO(S. - SI)

A - ~ )dQ -IWI_"-PrJY1- V1)] - ToS," 1- A, -{(1

E.\ergy trawfer with wDft Ellers)' dcstnltlion
In the fonn of the rate equation,


dA df
Ratc of





[W - Po!~]
Ratc of curgy
transfer ;IS wDft


loss due 10 dWelt;1 im:vcrsibilitics the nle of (- T oS,..l cllange of aysfcm ,olumc For an isolated system., the exergy balance, Eq. (S.77), sives 4A "' - 1 (8 .78) Since I> 0, the only processes allowed by the second law are those for which the e:xcrgy of the isolated system decreases. In other words,


Rate of cxergy with heat Qj at the boundary where the instantanCOUI tempera~ is 1j

Rate of cxergy

The exergy of an isolmed system CO" "ever increase. It is the counterpart o/the entropy principle which slates that the entropy of an isolated system can never decrease. The excrgy balance ofa system can be used to determine the locations, types and magnitudes of losses (waste) of the potential of energy resources (fuels) and
find ways and means to reduce these losses for making the system more energy efficiCllt and for more effective use offuel.
8.11.2 1st law:

&nr:J BaltJlI/OT II Sku., MOflll S,stem

HI +

m" T

+ mgZ, + Qt-l

2nd law:


---'> c_ .v~.._"f-----t-~~~---> m, '-t_-\'-___




Ag. 8.18

uUlJ bisl4Mtfor" ItuuIy flow SYSltm

From Eqs (8.78) and (8.79),

v.l _ Vol
H2 - H1 - TrlSl - St)+m 1

I +mg(Zl - ZI )

A2 - A1 .,

1 [1 -~)dQ J [I-'& )d Q, T.
, T.

WI _ 2-1


W I _2 - /

(S.S I)

In the form ofmte equation lit steady state:

t(l- ~}?i -

W c.v. + ",(u" -u'l) -ic.v.




v.l _ Vl 1 2 l +g(Zl-Zz) and[1-ToIT jlQj

= time rate of exergy transfer along with heat

Q j occurring at the location on the boundary where the instantaneous temperature is 1).
For II single stream entering and leaving, the exergy balance gives

Tn].+u, _ IV _a, _L. [1_ T "riI'rir1m

8.12 Second Law Effidency


A common measure on energy use effiCiency is the first law efficiency, "l- The first law efficiency is defined as the ratio of the output energy ofa device to the input energy of the device. The first law is concerned only with the quantities of energy. and disregards the forms in which the energy exists. It does nOI also discrimirulle between lIie energies available al different temperatures. It is the second law of thermodynamics which provides a means of assigning a quality index to energy. The concept of available energy or exergy provides a useful measure of energy quality (Sec. 8.3).

-=2fl With this concept it is possible to analyze means or minimizing the cOll.'lumption ofavailable energy to perform a given process, thereby ensuring the most effi cient possible conversion orenergy ror the required !ask. The second law efficiency, 11u, or a process is defined as the ratio or the minimum avai lable energy (or exergy) which must be consumed to do a task divided by the actual amount of available energy (or exergy) consumed in performing the task. 1Iu " minimum exergy intake to perform the given task actual exergy intake to penorm the same task

_ A.,;. 11u - - -


where A is the availability or exergy. A powerplanl convens a reaction ofavailable energy A or W","" 10 useful work W. for the desired output of W, A..a. ... Wand A .. W"",. Here.

i "" IVmu - Wand 1111 "

W w-

111 - - = - --- Q, W",.. QJ
" l1Jr11comol IV IV


(8.86) (8.87)

q 1111 - - -, Since IV"",, "

q ,W

Ql( I -

11 ..

). Eq. (8.87) can also be obtained directly as follows

~ ( l- ~)

- 1]o.n..t



wort is involved, A"'in '" W(desired) and if heal is involved, A"'ilI ...

If solar energy Q, is available at a reservoir storage temperature T, and if quantity orheat QI is tnmsferrcd by the solar collector attcmptnlturc TI

Q, cxcrgyoutput l1u '" . cxergy mput

J11 "' ~

242 = -

.. 111

1- To



Table 8.1 shows availabilities, and both flJ and flu expressions for several common thcnnal tasks.

Table 8.1 T, > T. > To > T,

Energy inpw r

Produce worlc, Wn

A " Wi
Anoia Wo

A - Qr(t-~)
Anoia - W o
111 _ ..:.:..2...

,, "-

W. W,


IIn - ,(",;..

IIn - 'h~

1- -


IIn - fll
(electric motor) (beat mginc)

Add heat Q. to reservoir at T.

A - W, A..., -Q.(I- ~)
'IJI - ~

A - Qr(l-~) Amm - Q.(I-~ )

IJI -~




1111 - 111-T, T,

1J1I _ II{t_;')

\ _ To

(heal pump)

(solar waterileatcr)


&tn<;t ht Q. from <::o1 d reseMorat T. (below


A -Wi A., -Q;' -1)

llt - &'

A " O,(1 -~ )

A ... "O;' -1 )
lll _ &' Q,


-IlU -Il{;' -I)

(Refrigcrator-dccuH: motor driven) Strictly !lpeU.ing, it is COP.

1l11 '"' 1l1

I] [T._ T.: 10
1- -



In the case of a heat pump. the task is to add heat Q. to a reservoir to be maintained at temperatwe T. and the input shaft work is WI'
COp .. (COP) ..

~ ,

.. 1'1,. say

..... r. -

~=Q.=..1L To Wi A..w.

11u " A",;~ =.

Q(I _T.)


1'11l =1'I{1- ;.)

8.12. 1 MIIkIiing EJUI Use 10 SO","


Similarly, expressions of I'll and l'Iu can be obtained for otberthennal tasks.

Combustion of a fuel re leases the necessary energy for the tasks, such as space heating, process steam generation and heating in industrial furnaces. When the products of combustion are at a temperature much greater than that required by a given task, the end use is nOI well matched to the SOUTCe and results in inefficient utilization of the fuel burned. To illustrate this, Jel us consider a closed system reeeiving a heat transfer Q. at a source temperature T, and delivering Q . at a use

temperature T. (Fig. 8.19). Energy is lost to the surroundings by heat tnutsferat a rate 0 1 across a portion of the surface at TI At steady state the ener~ lind availability rate balances h'ome.

Q,--~HH H . Lm /l~Q.
T'---'~~~~-- - l~~-~~ "--T.

FIg. 8.19


mnc uli/ilJUiu Ji'MII StNNi uUJ ~itwpoint


Equation (S.9O) indicates that the energy carried in by heat transfer used. Q., or lost 10 the surroundings, QI' Then

Or is either

'11 = &


The value of '11 can be increased by increasing insulation to reduce the loss. The limiting value, when 121 - 0, is '11 - I (100%). Equation (S.91) shows that the availability or exergy tamed ioto the system is ei.ther transferred from tbe system accompanying the heat transfer accompanying the heal transfers Q. and QI or destroyed by irreversibiliti es within the system, i. Therefore,


l1u E> Q . ( 1--

T' l r.

r. n,-1-

l -~




Both 11. and l1u indicate how effectively the input is convened into the product. The parameter 11, does this on energy basis, whereas '111 docs it on an availability or excrgy basis. For proper utilization of cxergy, it is desirable to make '11 as close to Wlity as pm:tical and also a good match between the source and use temperatures, T, and T. Figure 8.20 demonstrates the second law efficiency against the use temperature T. for an assumed source temperature T, = 2200 K. It shows that 1111 tends to unity (100%) as T. approaches T,. The lower the T., the lower becomes the value ohIo. Efficiencies fortbree applications, viz., space beating at T. '" 320 K. proc-

ess steam generation at T. = 480K, and heating in industrial furnaces at T.'" 700 K, are indicated on the figure. It suggests that fuel is used far more effectively in the high temperature use. An excessive temperatures gap between T, and T. causes a low 'Ill and an inefficient energy utilization. A fuel or any energy source is consumed efficiently when the first user temperature approaches the fuel tern perature. This means that th e fuel should first be used for high temperature applications. The heat rejected from these applications can then be cascaded to applications at lower temperatures, eventually to the task of, say, keepioga building wann. This is called energy cascading and ensures more efficient energy utiliza tion.

'.0 .,...__________..,
/./ As T.



HeaMg In Fum8Clll


0.4 ; Process Steam Generation

oon _

Space Heating

o L-~~--~~--~~--~
500 1000 1500 2000


Fig. 8.20 Effid


Imrptralim T.

(T, - 2.2()() K, To - J()() K,

R, -

tIu moM k1w tjfoit1UJ lOO'l1)

8.12.2 Furlhn mrutraliolU ofSecou UfII EJfidnu:iu

Second law efficiency of different components can be expressed in different forms. I! is derived by using the exergy balance rate. as given below: (a) TurblDCJ The steady state exergy balance (Fig. 8.21) gives:

-"- 1- +mTalrillm

"[To] + w ., --+ a ,i

'JI 1 '.(,

If there is not heat loss, (8.94) (8.95)

(b) Compreuor and Pump Similarly. for a compressor or a pump,

- - " af -a,


i + -m

. afz - a'i



(c) Heat Exchanger Writing the exergy balance for the heat exchanger, (Fig. S.22)

1:[1 -

~ ]Q; - Wc.v. + [m~ afl + mCar, ] - [mbar,. + mcar4 1- ic.v. ~ 0

m~ {afl - ar11 - mc[ar4

Iftherc is no heat transfer and work transfer,


(8.97) (8.98)


m c[ar, -arl ] mb [arl - orl )

Fig. 8.2.2


of/J M/Jt odul","

(d) MixIng of Two fluids Exergy balance for the mixer (Fig. 8.23) sives:

[I- ;:]Q

+ mlOrl + mlarl "" IYc.v. + mlO rl + Icv.

If the mildng is adiabatic and since W e .v . - 0 and rill + rill - rilJ . (8.99)




Commentl on Exergy

The energy of the universe, like its mass, is constant. Yet at times, we are bombarded with speeches and articles on how to "conserve~ energy. As engineers, we know that energy is always conserved. What is not conserved is the exergy, i.e., the useful work potential of the energy. Once the exergy is wasted, it can never be recovered. When we use energy (e\ecuicity) to heat our homes, we are Dot destroying any energy, we are merely converting it to a less useful form, a form of less exergy value. The maximum useful work potential oCa system at the specified state is called exergy which is a composite property depending on the state of the system and the surroundings. A system ",ruch is in equil ibrium with its surroundings is said to be at the dead state having zero exergy. The mechanical forms of energy such as KE and PE are entirely available energy or exergy. The exe rgy (IY) of thermal energy (Q) of reservoirs (TER) is equivalent to the work output of a Camol heal engine operating between the reservoir a! temperature Tand environment at To. i.e., W - Q[I-

The actual work W during a process can be determined from the first law. If the volume of the system changes during a process, part of this work (W...".) is used to push the surrounding medium at constant pressutePo and it cannot be used for any useful purpose. The difference between the actual work and the surrounding work is called usefol work, W~
W~ - W - W...". ~ If - PO(V2 - VI) If.,..,. is zero for cyclic devices, for steady flow devices, and for system with fixed boundaries (rigid walls).



The maximum amount of useful work that can be obtained from a system as it undergoes a process between two speeified states is called reversible work, If~. If the final state of the system is the dead state, the reversible work and the exergy become identical. The difference between the reversib le work and useful work for II process is called Im!venibility. I " W, ... -Wy~TOSFl'

i - ToS, .. For IS total reversible process, W~ - Wu and 1 - O. The fIrSt Jaw efficiency alone is not a realistic measure of perfonnance for engineering devices. Consider two heat engines, having e.g., a thermal efficiency of, say, 300' '"'. One of the engines (A) is supplied with heal Q from a source at 600 K and the other engine (8) is supplied with the same amount of heat Q from a source at 1000 K. Both the engines reject heat to the SIlITOuodings at 300 K.
(WA )," - Q( I Similarly, (Wg}m< -


- O.SQ, while (W,J.." .. 0.3Q

Q (1- 13:0) - 0.7Q, and (Wo)K< - O.3Q

At first glance, both engines seem to convert the same fraction of heat, that they receive, to work, thus perfonning equally well from the viewpoint of the fltSl law. However, in the light of seeond law, the engine 8 hll5 a greater work. potential (O.7Q) available 10 it and thus should do a lot beller than engine o4. Therefore, it can be said that engine 8 is performing poody relative to engine A, even though both have the same thermal efficiency. Toovercome the deficieneyofthe firsllaw efficiency, a second law efficiency I'[ll can be defined as the ratio of actual thennal efficiency 10 the maximum possible thermal efficiency under the same conditions: I'[ .. ....!lL


So, for engine A, 1/u = 0.3/0.5 '" 0.60 and for engine 8 , I'[ll " 0.3/0.1 - 0.43 Therefore, the engine A is converting 6O"h of the available work potential (ellergy) to useful work. This is only 43% for the engineR. Therefore, I'[u " l10ct '"


~ (for heat eDgines and other work producing devices)


COP If. . 1:111 " - - -'= ---l!!... (for refrigerators, heat pumps and other work COP," W ~ absorbing devi ces)

The exergies of a closed system (~) and a flowing fluid stream (tp) are given on unit mass basis:

- (u - uo> - To(s - .fo) +prJ.v - vo> kJllcg

If - (II - 110) - To(s -so) +

v' T

+ gt kJ/kg

Rnnsible Work &pessWu

{al Cyclic Devlcu
Wrev '"' 11"" Q I (Heat engi nes) _ W,.v ~

(COP .. v )lld . (COP", .. )up

(Refrigerators) (Heat pumps)

_ w. ...


(b) Closed System

W,... '" VI - U2 - TrJ,SI - Sv +PO U'I - V1)
- m(~I - ~)

(e) Steady flow Synem (lingle Itream)

S w ,...",m[(I1 + +gzl-ToSI) - (~ + i +8Zl- T O 2)]



,., m('l - 1fIl) When tlw _ ystem exchanges heat with another reservoir at temperatu.re Tk other than the atmosphere,

Wzn '" m(lJIl

- '1'2) +

Q..( J - ~ )

The first Jaw efficiency is defined as the ratio of energy output and e nergy input, while their difference is the energy loss. Like wise, the second Jaw efficiency is defllled as the ratio of exergy output and exergy input and their difference is irreve rsibility. By reducing energy loss, first law efficiency can be improved. Similarly, by reducing irreversibililies, the second law efficiency can

be enhanced.
Eu.mple 8.1 In a certain process, a vapour, while condensing a1420oC, transfen heal to water evaporating al 250C. The resulting stearn is used in a power cycle which rejects heat at 35C. What is th e fraction of the available energy in


. I

2S0 = the heat transferred from the process vapour at 420C thaI is lost due 10 the irreversible heat trn.nsfer at 2S0C?
Solution ABeD (Fig. Ex. 8.1)would have been the powcrcyele, if there was no temperature dilTerence between the vapour condensing and the water evaporating and the area under CD would have been the unavai lable eoergy. EFGD is the power cycle when the vapour condenses al 420C and the water evaporates at 2S0C. The unavailable energy becomes the area under DG. Therefore, Ibe increase in unavai lable energy due to irreve~ible beat transfer is represented by the area under CG.



,: 0

B r, 420 + 273" 693 K F r ; 25Q +273 "


I. .


;?j i'-~I

~ ro 35 +273 "308 K
IflCl"8aHIn Lnavallilble

--~ .

Fig. b. i.I


Q , .. T14.S " rillS'

as' .. ..!i...
IV .. work dooe incycleABCD

- (T, - TcJAS

W .. Wod:: don e in cycle EFGD

.. (T, - To}4S' The fraction of energy that becomes unavailable due to irreversible heat transfer

.. W-W' ",To(.1S'-M>",

,-(AS' ) as -1

(1i -To) 6.5

308 (693-S23)
S23 (693 308)

(7j -To)

'" T o(7j -7j') 1j'(1j T o)

.. 0.26


&amplc 8.2

In a steam boiler, hot gases from a fire transfer heal 10 water which vaporizes al constant temperature. In a cenain case, the gases are cooled from I 100C to SSO"C whi le the water evaporates at 220C. The specific heat of


gases is 1.OO5kJ/kgK, and the latent heat of water at 220C, is 1858.5 kJAg. All the heat transferred from the gases goes to the water. How much does the total entropy of the combined system of gas and water increase as II resu!! of the irreversible heat transfer? Obtain the result on the basis of I kg of water evaporated. lflhe tempe1l1ture oflhe surroundings is 30C. find tbe increase in UlUIvailable energy due to irreversible heat transfer. Gas (m ~ is cooled from state I to stale 2 (Fig. Ex. 8.2). Forreversible beat trnnsfer, the working nuid (w.f.) in the beat engine having the samec p would have been heated along 2- 1. so that at any irutant, the temperature difference between gas and the working nuid is zero. Then l- b would have been the expansion of the working nuid down to the lowest possible temperature To, and the amount of heat rejection wou ld have been given by the area abed.





, '''''''









e-- ~g8$


' ~ _ _ 4SH~e

f D"30 + 273 " 3031<

Fig. EL 8.2

When waler evapo1l1tes at 220C as the gas gets cooled from ll00C to 550C, the resulting power cyde has an unavailable energy represented by the areaaefd. The increase in unavailable energy due to irreversible heat transfer is thus given by area befe. Enlropy increase of I kg waler
A ('\ ( ..


Lalent heal absorbed =

1858.5 (273 + 220) = 3.77 kJ/kg-K

QJ .. Heallransfern:d from the gas

'" Heat absorbed by water during evaporotion = m, c ppl OO -5S0) '" 1 x 18Sg.5 kJ

... 1858.5 - 3,38kJ1"C




.s 'Jal 4Q = Tfm
.. T
Ti l Til

c ~ 'PiT

- m,cp In

.!E =3.381n-823


- -3.38xO.SI .. - 1.725 kJlK

MIOIaI .. (AS).... ter + (dS).u - 3.77 - 1.725 = 2.045 kJlK

Increase in unavailale energy


.. To(6S)1OClI '" 303 x 2.045

.. 620 kJ Esample 8.3 Calculale Ihe available energy in 40 kg orwaler at 75C wilh respect to Ihe surroundings al SoC, the pressu.re or water being I atm. Solution Irtbe water is cooledata COnstanl pressure or I atm from 7SoC to SoC (Fig. Ex. 8.3) Ihe heat given up may be used as a source ror a series or Carnot engines each using the surroundings as a sink. It is asstuned thai the amount of energy received by any engine is small rdative to that in the sourt:e and the temperature oflhe source does not change while heal is being exchanged wilh the engine. Let Wlconsiderthal the source has fallen to temperature T, at which level there operates a Camot engine which takes in heal allhis temperature and rejects heat at To " 278 K.. If is the entropy change ofwatef, the work obtainable is oW - -m(T-Tg)OJ


273 .. 7S - 348K


fig. EL 8.3

o sis negative.

oW - - 4O(T-To)..:z.:..:....

, or

-- 4Ocp

(l- ~ ) OT

With a very great number of engines in the series. the total work (maximum) obtainable when the water is cooled from 348 K to 278 K would be

W <lIIall -

A.E. - -lim l:40C p (l- To




840c p(l _ To


- 40cp [(348 - 278) - 2781n - 40 x 4.2 (70 - 62) .., 1340 kJ Q1 ... 40 x 4.2 (348 - 278) - 1I,760kJ

V.E. " QJ -


.. 11,760 - 1340 " 10,420 kJ

sample 8.4 Calculate the decrease in available energy when 25 kg ofwatee at 95C mix with 35 kg of water at 3SoC, the pressUIe being taken as constant and
the temperature oflhe surroundings being {5C (cp of water .. 4.2 kl/kg K).

Solution The available energy ofa system of mass m, specific heal cP' and at
temperatUIe T, is given by A.E. = mc p

(A.E.b .. Available energy or2S kg of water at 9SOC



1 (1- % )dT
( 1 -1!!)dT

- 25x4.2

" 105[(368-288) -288 In ;::] .. 987.49 kJ (A.E.)]S .. Available energy oDS kg of water at 3S oC - 147 [(308-288) - 288 1n


... 97.S9 kJ
Total available energy

(A.E,)IOW " (A.E.b + (A.E.)]S - 987.49 + 91.S9 .. 1085.08 kJ

2S4=After m ixing, if I is the final temperature 25 x 4.2 (95 - I) " 35 X 4.2(1 - 35)

.'~'~ x~9~'~X~3~'~X~3~' ,-25 + 35

_ 60C
Total mass after mixing - 25 + 35 - 60 kg (A.E.)r.o - Availab le energy of6O kg of water at 60C .. 4.2 x 60 [ (333 ~ 288) - 288 1n


- 803.27 kJ :. Decrease in avai lable energy due to mixing .. Total ava ilable energy before mix ing - Total available energy afier mixing .. 1085.08 - 803.27 -= 281.81 kJ Example 8.5 The moment orine"ia ofa flywheel is 0.54 kgm1 and it rotates al a speed 3000 RPM in a large heat insulated system, the temperalure of which is 15C. If the kinetic energy of the flywheel is dissipated as friclional heat at the shaft beari ngs wh ich have a water equivalent of 2 kg, find th e rise in the temperature of the bearings when the flywheel has come to rest. Calculate the greatest possible amount of this heat which may be returned to the flywheel 8.5 highgrade energy, showing how much of the original kinetic energy is now unavailable. What would be the final RPM of the flywheel, if it is set in motion with this available energy? Solution Initial angu lar velocity ofthe flywbeel

1 '" W, _ _ '_ '_ N _

Initial available energy orthe flywhee l

2/1'x3000 - 3l4.2radls


'" (K.E\"itial '"

ra~2 ,

_ 0.S4kgm 2 x (3 14.2)1

- 2.66 X 104 Nm - 26.6 kJ When this K.E. is dissipated as frictional hea l, if ill is the temperature rise of
the bearings, we have water equivalent of the bearings x ri se in temperature " 26.6 kJ

26.6 _ 3.190C 2x4.l87


:. Final temperature of the bearings If 15 + 3.19 " 18.19C
The maximwn amount of energy which may be returned to the flywheel as high-grade energy is


( 1_ 288 )dT


.. 2 x 4.187[(291.19 _ 288) _ 28810

.. 0. 1459 kJ

2~~.~ 9 ]

The amount ofent:rgy rendered unavailable is

V.E. = (A.E);,.;,w - (A.E)"tumablo .. hiall ....rlY = 26.6 - 0. 1459 ,., 26.4541 kJ
Since the amount of energy returnable to the flywheel is 0.146 kJ, if w l is the fmal angular velocity, and the flywheel is sct in motion with this energy

0.146 x 10) =.l x 0.54 2


~ ,. 146 = 540.8

0.27 23.246 rad/s

If N2 is the fmal RPM of the flywheel

W:z '" 23.246 " 211" Nz

N _ 23.246 x 60 '" 222 RPM

2 x 11"


Example 8.6 Two kg of air 31500 kPa. 80C expands adiabatically in a dosed system until its volume is doubled and its temperature becomes equal to that of the surroundings which is at 100 kPa, SoC. For this process. determine (I) the maximum work, (b) the change in availability, and (c) the irreversibility. For ai r, take c. '" 0.718k1lkg K, 1/ "" c. Twhere C y is constant, and pY " mRTwhere p is pressure in !cPa, Yvolume in ml, m mass in kg, R a constant equal to 0.287 kl/kg K, and Tlemperalure in K. Solution From the propeny relation
TcIS ... dU + pdV

the entropy change of air between the initial and final Siaies is

" cIS "" JmCydT + J , mRdY J



256 = -

S2-SI - me

To 1 In----$+mRln -V Ii I'i

From Eq. (8.32),

W..... - (V I - ViJ- To (SI -SiJ

-m [e.(Ii - 12) + 10 [e .~ ~ + Rln ..!il] ;' 1j "i

- 2 [0.718(80 - 5) +

2?8~0.718In ~~~ + 0.2871n +]

An.!'. (a)

- 2 [53.85 + 278 (- 0.172 + O.I99)J - 2(53.85 + 7.51 ) - 122.72 kJ From Eq. (8.42), the change in availability
- ~l- ~

.. C UI - V2) - TJ,5. - Sz} + Po{V. .. W...... + PJ,V. -V:z) .. 122.72 + POWI - 2V. )
_ 122.72 - 100 )( 2)( 0.287)( 353 500 = 82.2 kl The irreversibility


An.!'. (b)

I - Wmu.uotNl-WK\
From tbe firs~ law,

Woo:( - Q - llU" - IlV= VI - U2

1 = U.- V 1 - TJ,5 1 - S]) - VI + U2 ,. Tu(S2 - 51 )

"" To(llS)oyrtmI
For adiabatic process, (.:1S')rurr -

1 - 1Jm ev ln


12 +mRln..!i]
Ii I'i

" 278 )( 2[0.71810


+ 0.28710 2J
An:. (e)

.. 278 x 2 (---{).172 + 0.199) - IS.2 kJ Exainple 8.7 Air expands through a turbine rrom 500 kPa, 520~C to 100 kPa, 300"C. During expansion 10 kllkg or heat is lost to the surroundings which is at 98 kPa. 20C. Neglecting tbe K.E. and P.E. changes, detennine per kg of air (a) the decrease in availabi lity. (b) the maximum work, and (e ) the irreversibility.

- = 157
For air, take c p'" 1.005 kJ/kg K., h .. c p Twherecp is constant, and thep , Yand T relation as in Example 8.6. Solution From the propcrtyrclation

TdS : dH - Vdp
the entropy change orair in the expansion process is

JdS = J~ _ JmRdp
1 ]




To - mR In -Pl 5l - 5 1 = mcp In ......... 1j PI

For I kg ofair.

In ..!i. - R In El.. 1j PI From Eq. (8.30), the change in availability

Sl - SI _ "

IVI-IV2 - b]-b2 .. (hI - Toof1) - (h2 - Toofz) "" (h] - h2) - To (s ] -.1'2)
= C

(T1- T2) - T

lnP2 o(R PI



12) 1j 1Z!)

'" 1.005 (520 -300) - 293 ( 0.287 In .!. - 1.005 In . 5 793 '" 1.005 x 220 - 293 (0.3267 - 0.46 19) = 221.1 + 39.6 "" 260.7 Ulkg AIlS. (a)

The maximum work is

W..... - change in availability '" Ifl - IV2 '" 260.7 kJlkg AIlS. (b)

From S.F.E.E.
Q+h 1 -W+h 2 W - (h 1-h 2) +Q "' cp(TI-T:z)+Q ,. 1.005 (520 - 300) - 10 '" 21 LI k1lkg The irreversibility 1 - lVrrwt - 1V - 260.7 - 211.1 = 49.6 kJ/kg

AIlS. (c)


/ - Trf,..llSt'jOUm + AS.....)
- 293 [1.005 In 573 - 0.28710 ! + 793 5 293 - 293 x 0.1352 + 10 - 49.6 kJ/kg

AIU. (d)

Example 8.8 AD air prehealer is used 10 cool the products ofcombustiDn from a furnace while heating the air to be used for combustion. The rate of flow of products is 12.5 kg/s and the products arc cooled from 300 to 200C, and for the products at this temperature c p - 1.09 kJ/kg K.. Thc rate of air flow is 11 .5 kg/so the initial airtemperature is 40C, and for the aircp- 1.005 kJ/kg K. (a) Estimate the initial and nnalavailability of the products. (bJ What is the irreversibility for the process? (c) If the heat uansfer from the products occurs reversibly through heat engines, what is the final temperanlre of the air'! What is the powerdeveloped by the heat engine?Take To " 300 K and neglect pressure drop for both the fluids and heat transfer to the surroundings. Solution


Y'I - initial availability ofthe products

- (h i PI

110) I,

To<SI - So>

;. c (T. - To) - Toc

In ....!L To


= 1.09(573 - 300) - 300 x 1.09 In



297.57 - 211.6 - 39.68 kJ/kg

Y'2 - final availability of the products

- (h2 - ho) - To(s~ - $0)

473 - 1.09 (473 - 300) - 300 x 1.09 In 300 - 188.57 - 148.89 - 39.68 kJ/kg

(b) Decrease in availability of the products

- VII - "2 .. (h! - hu - To(s! - S2)


1.09 (573 - 473) - 300 x 1.09ID


'" 109 - 62.72 " 46.28kJ/kg By making an energy balance for the air preheater [Fig. Ex. 8.8(a)].
cP, (T. , - T.:> - nlo cpo(To: - Tol) 12.5 x 1.09(573 - 473) - 11.15 x I.OO5(T'1 - 313)

m .

T. .. 12.5xl09 +3 13"".bO.89K 01 11.5 x 1.005

Increase in availability for air

, I
F , ,


""2"'1 .. ("2 - hI) - TO(32 - 31)

o f Combustion

" ,


l .


AI< i>reheater

/ V' '-; 'rNNNVw' 1/ ,



L Insulation


T., A1t (m.,

fig. EL &.8{a) " c (T -T. ) - T/F



To. In ----*T.


= 1.005 )( (430.89 _ 3 13) - 300)( 1.005 In = 118.48 - 96.37 = 22.11 kJ /kg :. Irreversibility of the process = 12.5 )( 46.28 - 11.5 )( 22. 11

'" 578.50 - 254.27 ,. 324.23 kW

(c) Let us assume that heat transfer from the products to air occurred through heat engines reversibly as shown in Fig. Ex. 8.8(b).


Q, Q,














fig. EL &.a(b)



260=For reversible heat transfer,

6S....v - 0

6.S.,.+6S..... - 0 6.S... + C.S' it "" 0 6.S... - -6Soit m C In T,l =-m C

I 1'.

T, l




12.5 x 1.09 In


- - 11.5 x 1.005 In


Tal - 392.41 K

Rate of heat supply from the gas to the working fluid in the heat engine,

QJ" m,cp (T,l - T~

,. 12.S x 1.09 (S73 - 473) - 1362.S0kW Rate of heat rejection from the working fluid in the heal engine to the air,

OJ -

- II.S x I.00S (392.41 - 313) - 917.78 kW Total powCTdeveloped by the heal engine

m .".

(Tol - Til)

Ii' - Q, -

O 2-

1362.S0 - 917.78

- 444.72 kW
Example 8.9 A gas is flowing through a pipe al the rate of2 kg/so Because of inadequate insulation the gas temperature decreases from 800 to 790C between two sections in the pipe. Neglecting pressure losses, calculate the irreversibility rate (or rate of energy degradation) due to Ibis heat loss. Take To" 300 K and a constant c p - 1.1 IUrkg K. For the same temperature drop of 10C when the gas cools from 80 eC to 70C due 10 heat loss, what is the rate of energy degradation? Take the same va lues of To and cp' Whal is the inference you can draw from this example?


Ii - S

_.Ii. To
.m. :.: ,,",("" '' --" "~ )

- m(.rl - sl) - -


Irreversibility rate '" rate of energy degradation = rate of exergy loss



i '" ToS...
= mTrloh - .11) - mc p (T2 - TI )

~ mcp[(1j

-T2 ) -To In


"" 2x l.l [(1073-1063)-300 In

= 15.818 kW

When the same heal loss I,lCCUI'1I allower tempernture

i '" 2 x 1.I [(353- 343)-300 In ~!~J

.. 3.036 kW

It is thus seen that irreversibility rate ofexergy destnlction is more: when the same heat loss occurs at higher temperature. Irreversibility rale decreases as the te'!lperature of the gas decreases. Quantitatively, the heat loss may be the same, bul qualitatively, it is different.
Example 8.10 An ideal gas is flowing througb an insulated pipe at the rate of 3 kg/so There is a 10% pressure drop from inlet 10 exit of the pipe. What is the rate of exergy loss because of the pressure dropdue to friction? TakeR - 0.287 kJ/kg K and To .. 300 K. Solution Rate of entropy generation from Eq. (8.68),

S = mR~


- 3xO.287 O.lOPI p, '" 0.0861 kWfK

Rate of exergy loss

i '" ToS..,.
'" 300 x 0.0861 .. 25.83 kW
Waler at 90 C flowing at the rale of2 kgfs mixes adiabatically with another stream of water at 30C flowing al the rale of I kg/so Estimate the entropy generation rate and the rale of exergy loss due to mixing. Take To =

Example 8.11

300 K.

m - ml+m2 - 2+ 1 - 3kgls

p - = - "' 0.67


2 3


. 1


&sir atui Applid 17mmDtfJll4miu

To. IL = 303 = 0.835 1j 363 From Eq. (8.76),


'" mcp n

1 x+f{l-x)

= 3 x 4.\87 In 0.67 + 0.835 x 0.33

0.835 0 .ll "" 12.561 In 0.94555 0.94223 - 0.0442 kW/K Rate ofexergy loss due to mixing

;=ToS.... .. 300 x 0.0442

"" 13.26 kW
Alternotively, Equilibrium temperature after mixing,
I " mltl

+ m 2t2

m l +m2

'" 2x90+lx30 ~70QC 2+1


S.... .. 2 x 4.187 In ~:~

+ 1 x 4.187 In


'"' 0.0447 kWIK.

i = 300 x 0.0447 - 13.41 kW Example 8,12 By burning a fue l the rate of beat release is 500 kW at 2000 K. What would be the first law and the second law efficiencies if (a) energy is absorbed in a metallurgical furnace at the rate of480 kW al lOOO K., (b) energy is absorbed at the rate of 450 kW for generation of steam al 500 K, and (c) energy is absorbed in a chemical process al the rate of 300 kW at 320 K? Take To = 300 K, (d) Had the energy absorption rate been equal t0450 kW in all these three cases, what would have been the second law efficienccs? What is the inference that you can draw from this example?
Solution If Qr is the rate of heat release at temperature Tr and heat absorption allemperature T. , then

Q . the rate of

1 - To





I/II=I/I--r,1 -.....2...





(a) Metallurgical furnace

'11 =

480 X 100 = 96%

1_ 300 13': x]oo - 79"10 1- - 2000

lJu " 0.96

(b) Steam generation

tll - 450 x 100 = 90%

1_ 300

flu " 0.90

(c) Chemical process

1- - -


x 100 " 42.3%


fll - 300 x 100 - 60%

1- 300

'111 - 0.60 1- 300 xloo - 4.41% 2000 (d) In all the three cases, til would remain the same, where

fll - 450 x 100 = 0.90

1- 300 flu(. ) " 0.90 x _~1~000W- x 100 " 74.11 % 1_ 300 2000 1- 300
flU (b) : 0.90 X ----+~

x 100 '" 42.3%

1- - -

2000 1_ 300

flll(c) " 0.90 x

1- - 2000


x 100 .. 6.6 1 %

It is seen that as the energy loss increases. the ftrst law efficiency decreases. Forthe same heat loss, however, as the tempeature difference between the source and the usc temperature increases. the second law efficiency decreases, or in other words, the rate or exergy loss increases.

(0, - 0.)


. 1


Example 8.13 A system undergoes a power cycle while receiving energyQ] at temperatun: T1 and diseharging energy Q2 at temperature T 1 There are no other
heat lnlnsfers. (a) Show that the thermal efficiency of the cycle can be expressed as:

q '" l-~- --':';':"'" 1i To ~

where To is the ambient temperature and 1 is the ineversibility of the cycle. (b) Obtain an expression for the maximum theoretical value for the thennal efficiency. (c) Derive an expression for the irreversibility for which no network is develnped by the cycle. What conclusion do you derive from it? Solution An availability balance for the eycle gives (Fig. Ex. 8.13),
Fig. Ex. 8.13



(M)ey<1t '" 0 '"

(I- ~ )~ -(I- ~ )Ql - W- I

since each propcrty is restored to its initial state. Since

Q1 - QJ - W,

O - (I -~)~ -(1- ~}~ -W) -W-I

wo )](/,_ T,I T'[[I_ "')-[1T To 1i 7i To
Proved. (b) When I .. O.

(c)WhenW " O

11 - 0 - 1 - - - - -

72 1i



I'" To[...!... Tz Ii


QJ - To

[~!?!..]- To S..,. 72 Ii

The heat transferQJ from TJ to Tl takes place through a reversible engine. and the entire work is dissipated in the brake, from which an equal amount of heat is

rejected 10 the reKI'Voir al T2 Heal transfer Ihrough a fi nite temperature difference is thus equivalent to the destruction of its exergy. (See An. 8. 10. I(a . EumpJe 8.14 A compressor operating at steady stale takes in 1 kg/s of air at 1 bar and 25C and compresses it to 8 bar and 160C. Heat transfer from the compressor to its surroundings occurs at a rate of 100 kW. (a) Delermine the power input in kW. (b) Evaluate the second law efficiency for the compressor. Neglect K.E and PE changes. Take To " 25"C and Po '" I bar.


SFEE for the compressor (Fig. Ex. 8.14) gives: IY - Q + m(hl - h.;J -- lOO + 1)( 1.005(25 - 160) - - 235.7 kW AlIs.(a)



FIg. EL 8.14
Exergy balance for the compressor gives:

,"Ofl+ql -

~) - w-mot:",j

- W - m(Of: - Ofl) - q l-


11 -

,"(or -or)


- c(T2-Tt )-T.(cP In T2 - Rln

0fl-Ofl - hl - hI - TO(S2 - "I )




'" 1.005 (160-25)-298 ( 1.005 In '" 200.95 kJlkg 1I11 '" Es:ample 8.15 Solution


0.287 In 8)


.. 0.853 or, 85.3%

AIlS. (b)

Determine the exergy of I m l of complete vacuum.


Ihuit: #lid AppIUJ 7i\tmDdy_iQ ... H - HO- Y(p - PO)- To(S-So)

Since a vacuum bas zero mass, U " O,H - O, andS " O If the vacuwn were reduced to the dead state,

Uo - 0, Ho - 0.50 - 0 and Vo - O. The pressure p for the vacuum is zero. But Po os I bar os 100 kPa and VOS 1 ml ' - PoV "' IOO kN x lml_ lOOkJ



If an air motor operates between the atmospbere and the vacuum, this is the maximum useful work obtainable. Therefore, the vacuum has an exergy or work potential. Ezample 8.16 A mass of 1000 kg of fish initially al I bar. 300K is to be cooled to - 20 o e . The freezing point offish is - 2.2e, and the specific heats of fish below and above the freezing point are 1.7 and 3.2 kJlkg Krespe<:tively. The latenl heat of fusion for the fish can be taken as 235 kJlkg. Calculate the exetgy prodw;ed in the chilling process. Take To '" 300 K andpo '" I bar.

Exergy produced - Hl - H I - TO(Sl- SI) With reference to Fig. Ex. 8. 16,

T, . To





Fig. EL 8.16

HI - HI " 1000 [1 .7 (270.8 - 253) + 235 + 3.2(300 - 270.8) '" 1000 (1.7 x 17.8 + 235 + 3.2 x 29.2] = 1000 [30.26 + 235 + 93.441 - 358.7 MJ Hl - HI = - 358.7 MJ

270.8 300 SI - S2 - 1000 [ 1.71n - + - 235 - +3.2 1n 253 270.8 270.8 - - 1000 [0.1156 + 0.8678 + 0.3277J



Auildlt ENto,

E::n1KJ II1lIi IrtromibiliJy


- 1.311 MIlK S2 - SI - - 1.311 MJIK

Exagy produced - - 358.7 + 300 x 1.3 11 --358.7+393.3 .. 34.6 MJ or 9.54 kWh


Example 8.17 A quantity ohir initially at I bar, 300 K undergoes two typeS of interactions: (a) it is brought to a final temperature of 500 K adiabatically by paddle.whee l work transfer, (b) the same temperature rise is brought about by heat transfer from a !hennal reservoir a t 600 K. Take To - 300 K, Po - 1 atm. Delennine the ilTtveBibility (in kJlkg) in eac h case and comment on the results.

F _ u-U-~~ E----u----- ~-~( -='

(a) (b)

Fig. Ex. 8.11


Case (a): As shown in the above figures (Fig. Ex. 8. 17).

Case (b):

!L 500 At",;,,-siftI - cy ln'T' - 0.7 18In 'I 300 0.361 kJ/kg K 1 - 300 x 0.367 - I [0.1 kl/kg Q - m c.{T2 - T I ) '" I x 0.718 (500 - 300) - 143.6 kl/kg


At .

- s'-"-~

- 0.361 - 143.6 600

- O. I 277 kl/kg K , .. 300 x 0.1211 - 38.3 1 kJ/kg


The irreversibility in case (b) is less than in case (a).

1. - TrJ,h - 51)' Ib - Trf,h - 51) _ .Q


_1, . Sf T

The irreversibility in case (b) is always less than in case (a) and the two values would approach each other o nly at high reservoirtcmpcrntu re. i.e.,
1.-) lbasT~oo


. I

268=Example 8.18 Sleam enters a turbine al 30 bar, 400 C (II 3230 kJikg, $ 6.9212 kJlkg K) and with a velocity of16O mls. Sleam ieaveJ as salUl1lled vapour al IOOQC (II - 2676.1 kJlkg, $ - 7.3549 kJllr:g K) with a velocity of 100 mls. At steady state Ihe turbine develops work at a rale of 540 kJlkg. Heal transfer between the lurbine and its surroundings occurs al an average outer surface temperatureof500 K. Detennine the irreversibility perunil mass. Give an exergy balance and estimate the st1:ond law efficiency of the turbine. Take Po " I atm, To'" 298 K and neglect PE effeel.
0; 0;


By exergy balance oflhe control volume (Fig. Ex. 8. 18),


m W+ Q( I-!2..)+Of +/


where Or is the ex-;rgy transfer per unil mass.

Fig. f.L 8.18


.. (3230.9 - 2676.1) - 298(6.9212 - 7.3549) + , x ur1 _ S40_Q(I_

= 151.84 - Q(0.404)

(I )


h 1 +..:L .. W +h 2 +Q+ - '-




Q - (hl-h~ +


I; 2


2 2 - (3230.9-2676.1)+ 160 ; 100 X W-1_540 .. 22.6 kJlkg.


- = 269
From Eq. ( 1),

/ = 151.84 - 22.6 x 0.404 <0 42.1 1 kJ/kg

Net exergy transferred to turbine 691.84 k1/kg Work ., 540 k1/kg Exergy destroyed = J "" 142.11 k1/kg
tift - tlr: .,


Ellergy transferred out accompanying heat transfer - 22.6 x 0.404 - 9.13 k1/kg

Exergy Balance bergy Iran$ferred 691.84 k1/kg Exergy utilized

Work = 540 k1/kg (78%) Destroyed " 142.71 k1/kg (20.6%) Transferred with heal = 9.13 k1/kg (1.3%) 691.84 kl/kg

Second law efficiency, '111 ""


= 0.18 or 78%


Example 8.19 A furnace is healed by an electrical resisTor. AT STeady state. electrical power is supplied TO the resistor at a rate of8.5 kW per metre length to maintain it at 1500 K when the furnace walls are at 500 K. Let To - 300 K (a) For the resistor as the system, determine the rale of availabi li ty trans fer ae<:ompanying heat and the irreversibility rate, (b) For the space between the resistor and the walls as the system. evaluate the irrevers ibility rate. So/ulian Cuse (a): At steady slate for the resistor (Fig. Ex. 8. 19),

ResIsIor at

500 K



umace wa ll at 500 K Ftg. Ex. 8.19

Availability rate balance gives

dA ( To dt = 1- 7

). Q+ (.

W-Po~ -1 = 0

dV )

270 = -

i '" Rate of irreversibility

"(1 - ~)!.?+W = (I- 135~J(- 8.5)+8.5

.. 1.7 kW
Rate of availability transfer witb heat
AII.!'. (a)

3 '" (1- ~)Q - (1 -1 5:) (- 8.5) - -6.8kW

Case (b): Steady state,

AII.!'. (a)



-(1- T')Q - (I-~lQ-W-i -. T Tw f. - ( 1 -'00) - - 8.5- ( 1'00) - 8.' 1500 500

- 6.8 - 3.4 " 3.4 kW

Ails. (b) o &ample 8.20 Air enters a compressor at I bar, 30 e, which is also the state of the environment. It leaves at 3.5 bar, 141e and 90 mls. Neglecting inlet velocity and P.E. effect, dCleonine (a) whether the compression is adiabatic or polytropic, (b) if not adiabatic, tbe polytropic index, (c) the isotbennal efficicncy, (d) the minimwn work input and irreversibility, and (d) lhe second law efficiency. Take c p ohir '" 1.0035 kJlkgK.. (a) After isentropic compression

T .. ...1!...


[ PI ]
303 (3.5)2311 - 433.6 K '" 160.6e


<T - llIY

Since this temperature is higher than the given temperature of ]4 1e, there is beat loss 10 the surroundings. The compression cannot be adiabatic. It must be polytropic.


c.t _ [ li T 'Ii PI

J"-'' "

141+273 '" 1.366= 30+273 1

" -I log 1.366 '" - Jog 3.5

1_1. ..


0.135 .. 0.248 n 0.544 n .. 1.32978 ~ 1.33


(c) Actual work of compression
W - h, - h, _...:L ... 1.0035 (30 - 141) - -

v. 2


2 -- 115.7kJ/kg

x 10-)

lsothmnal work W T ",


pv.2 fvdp- . vf . . . . =-R7j ln 12 _ ...:L

I 2

90' , - - 0.287 x 303 In (3.5) - -,- x 1'-- 113kJ/kg

Isothermal efficiency;

W. 113 ", - - ' . - - - 0.9770r97.70/. W. 11 5.7

(d) Decrease in av~ilabi1ity or ellergy;


v.1 I -

"l "2

p, - c(T1 -T2)-To Rln--c In--P [ p PI 7j2


'" 1.0035 (30 - 14 1) _ 303 [0.287 In 3.5 -1.0035 In 414] _ 90' 303 2000 "' - 101.8 kJ/kg Minimum work input =- 101.8 kJlkg Ans. Irreversibility. I - Wm- - W
~- 101.8 - (- 1l5.7)

... 13.9 kJlkg

(e) SecOnd law efficiency,


'1u "

Minimum work input 101.8 '" 115.7 Actual worle input .. 0.88 or 88%

8. 1
What do you understand by high grade energy and low grade energy?

8.2 8.3

What is avai lable energy Md unavailable energy? Who propounded the concept of availability?


272 = 8.4

8.6 8.7 8.8 8.9

8,10 8.1 I
8.12 8. 13
8. I S

8. 17

8.18 8.19

8.20 8,21 8.22 8.23 8.24


8.26 8.27

8.28 8.29 8.30

8,32 8.33

What is the: available energy referred 10 a cycle? Show that there iSlI decrease in available energy whe:o heal is lransfem:d through a finite tempenllure difference, Deduce the expression for 3\l1ilable energy from II finite energy source at tCmper1Iture Twben the environmentaltempc:mture is Tg What do you undcmand by exergy and energy? What is meMlt by quality of energy? Wily is exergy of a fluid at a higheT tempelllture more than that at a lower tcmpm uwc7 Ilow does tbe exergy value prol'ide a useful measure oftbe quality ofenellly7 Wby is the sccond law called the law of degradation ofenergy? Energy is always conserved, but its quality;s always degraded. Explain . Why is tbe work done by a closed system in a revel"!ible process by intcmcting only with the surroundings the maximum? Show that equal work is done in all reversible processes between the same end Stales ofa syste m ifit uchangcs energy only with the surroundings. Gil'e the general expn:ssion for the maximum work of an open system which exchange! heat only with the surroundings. What do you understand by Keenan function? GiI'e the expression for reversib le work in B steady flow process under a given environmcnl. Gil'c the exprenion for reversible work done by a closed system if it intrnlClS only with the surrou ndings. What do you underlltand by 'useful work'? Derive ex pression s for uKrul work for a closed system and a steady flow system which interact only with the surroundings. What arc the availability fundion! for a: (a) clossed system. (b) steady flow $)'Stem? What do you understand by the dead state? What is meant by availability? Gil'e expressions fOT al'ai labilities of a closed system and a steady flow open system, What an: Helmholtz function and Gibbs function? What is the: availability in 3 chemical n:action if the temperature before and after the reaction is the same and equal to the temperature of the surroundings? When is the availability of ache mica I n:aclion equal to the decfl.':lSC in the:Gibbs function? Derivc the expression for iJTC\'enibility orcxergy loss in a process executed by: (3) II closed system. (b) a steady flow system, in a gil'en environment. State and explain the Gouy Stodola theorem. How is heat transfer through a fmite temperature diffC!C1\cc Cijui\l1lent to the destruction of its availability? Consitkring the steady and adiabatic flow ofan ideal gOlS through II pipe, show that the ratc ofdecn:asc in availability or lost work is proportional 10 the pressure drop and tbe nuss flow rate. What do yOll undcrstand by Grassman diagram? What i~ entropy genel"lltion numher? Why is exe.gy ah"ays 8 posi ti,'''' value? Why cannot it he negative?


8.34 Why and when is exergycompletely destroyed? 8.35 Give the exergy balance for a closed system. 8.36 Explain the statement: Theexergy ofan isolated system can never inenoase. How is it rrlated to the principle of increase ofenaopy? 8.37 Give the excrgy balance ora steady flow system. 8.38 Defille thoe second law efficiency. How is it different from the fi rst law efficiency in the case ofa simple power plant? 8.39 Derive the Sttond law efficieney for: (a) a solar water heater, and (b) a heat pump. 8.40 Wha t is l11{'an! by energy ~adin8? How is it thennodynamically efficient" g.41 Derive expressions for the irreversibility and second law eflie iency of a: (a) steam turbine, (b) compressor, (c) heat exchanger. and (d) mixer. 8,42 What is tile deficiency of the fi rst law efficiency? How docs Ihe law efficiency make up this deficiency? 8.43 1I0w can you improve the first law efficiency alld the second law efficirncy?


8.1 What is the maximum useful work whkh can be oblairted when 100 kJ are abstracted from a heat reservoir at67S K in an environmental288 1<.1 Wha t is the loss of useful work if (a) a temperature drop of SO C is introduced between the heat source and the heat engine, 00 the one hand. and the heat engine and the heal si nk, on Ihe Nher, (b) the source temperature drops by SOC and the sink temperature rises by 50C during the heat transfer process according to the linear law

..!!.Q constant? dr




An,. 57.38 kJ. (a) 11.46 kJ , (b) S.5 kJ In a starn gem:l3tor. water is evapol3led at 26O"C, While the combustion gas (cF .. 1.0S k.lfkg K) is cooled from 1300C to 320"C. The sufTOundinv are at 30"C . Determine the loss in ava ibble energy due to the above heat transfer per kg of waler e' 'ilJK>I1Ited. (Latellt heat of vapori7..iltion of water at 26O"C 1662.5 kJl Io:g.) .~nl. 443.6 kJ Exhaust gases leave an internal combustion en:tine at 8000C and 1 81m, after having done 10SO kJ of ....ork per kg of gas in thecngine (cpofga!! - 1.I kJfkg K). The temperature of the surroundings is 30~C. (a) How much available energy per kg ofgas is 10~1 by tltrowing away lhe exhaust gases? (b) What is the ratio of the 10$1 availab!e energy to the engine work? An!. (a) 425.58 kJ, (b) O.4{)S A hot spring produces water at a tempel3ture of 56G C. The water flo....s into a large lake. with a mean tempcl3ture of 14C, at a I3te or O.lm l of water per min. Whal is the rate of .... orking oran idea l he31 engine which uses all the available



A/lS. 19.SkW 0.2 kg ofoi r al 300"C is heated reversibly at constant pressure to 2{)66 K. Find the R''lIilable and unavailable ene rgies of the heat added. Take To " 30"C and c~ - 1.0047 k.I/kg K. An!_ 211.9 and 7S. 1 kJ

27f = 8.6 Eighly k8 of water at 100C are mixed with 50 kg of waler at 6O'C, while the IcmpctalUl'C of the surroundings is IS "C. Delermine the decrease in a\'ailable eoergy due 10 mi ~g. All$. 240 kJ A lead storage ballet')' used inanautomobile is ab le todeliverS.2 MJ ofelcctrical energy. This energy is available for starting the car. Let compressed air be eOl'lSidered for doiog an equivalent amounl of woO: in l taning the car. ll1e eomJl'sscd air is 10 be slored al 7 MPa. 2SC. Whal is the volume of the tank that would be required 10 leI the compressed air have an availability of S.2 MJ? For air,plI" 0.287 T, where Tis in K.p in kPa, and v in m)fkg. An.!. 0.228 m ) Ice ii to be made from water supplied al ISC by lhe process shown in Fig. P 8.8. The ftnallmlpcrarure oflhe icc is - IO"e. and the fillallcmperature of the water that is used as cooling water in the condenser is 30"C. Determine the minimum work required 10 produce 1000 kgoficc. Takc c p for " ater - 4.187 kJfkgK, c p for ice "" 2.093 kJll:gK, and lalent heal of fusion of icc '" 334 kJfkg.
Water 3O"C




1 0
Fig. PU

- w_

10., - IO"C

An.!. 31.92 MJ A pressure vesscl has a volume of 1m) and "onbins air al 1.4 MPa, 17S C. The air is cooled 10 2S' C by heat transfer 10 Ihe swroundings at 2S C. Calculate the availabilily in Ihe initial and tinal Slates and lhe irreversibilily Oflhis process. TakePn'" IOOkPa. Ans. 135 kJlkg, 114.6 kJlkg. 223 kJ g. 10 Air flows through an adiabatic compressor at 2 kg/so The inlel conditions arc I bar and 310 K and the e~ it eonditions arc 7 bar and 560 K. Compute the net rate of availability transfer and the irrevm;ibility. Take To 298 K. An&. 481.1 kW and 21.2 kW 8.11 An adiabatic turbine rece ives a gas (c p = 1.09 and c. '" 0.838 kllkg K) at 7 bar and IOOO"C and discharges at IS bar and 66S"C. Dctcnni~ Ihe sceond law and isentropic elfteicncies of the turbine. Take To - 298 K. Ans. 0.9S6. 0.879 8.12 Air enters an adiabatic compressor at atmospheric conditioos of I bar, IS oC and leaves al S.S bar. Thc mass now rate is 0.01 kg/s and the elfteiency of the compressor is 75 ~'. After leaving the compressor. the air is cooled IQ 40 ' C in an


aftcrcoolu. Calculate < a) the power required 10 drive IlK: compressor, and (b) the mtc ofim:vcr.sibility for the overa ll process (oompressor and cooler). Aru. (a) 2.42 kW. (b) I kW [n a rolafy compressor. air enters at 1.1 bar, 21"C where it is compressed adiabatically to 6.6 bar, 250 C. Calculate the ~"ersibility and the entropy produC'lion for unit mass flow rate. "The atmosphere i5 at 1.03 bar. 200C. Neglcd the K.E. changes. Au. 19 Ulkg, 0.064 kJlkg K In a steam boiler ,the hOI ga5CS from a fire transfer beat 10 water whicb vaporizes al a constant tcmlXfllturc of242.6"C (3.5 MPa). The gllSC5 an: cooled from 1100 to 430C and have an aVeT1lge slXcifie heal, \.046 kJ/kg K over thi, tcmpcnture range. "Thc latent heal of vaporization of steam 1\ 3.5 MPa is 1153.7 kJ/kg.Jfthe stearn generation rate is 12.6 kgfs and there iJ negligible beal 10" from the boi ler, caleulate: Ca) the rale of Ilea! uarufer, (b) the rale of lOS$ of excrgy of the guo (e) Ib.c rail' of gain of exergy of the sicam. and (d) the rale of entropy generation. Take To - 21"C. AIlS. C a) 220% kW, (b) 15605.4 kW (e) 9501.0 kW. (d) 20.76 kWfK An economizer, a gas-to-water finned tube beat exchanger. receives 67.5 kg/s of gu c, " 1.0046 1tJ1kg K.. and 51.1 kg/s ofwaler, (" p " 4.1861tJ/kg K.. The water rises in temlXralure from 402 10 469 K, where the gas falls in temlXrature from 682 to 470 K. There arc no ehanges ofkillC1ie energy, andpQ " 1.03 bar and To " 289 K.. Octennine: (a) rail' of ehange oravailability oflhe waler, (b) the rate of ehange of ava ilability of the guo alKl (c) lhe rale of entropy gencration. A ll!. (a) 4802.2 kW, (b) 7079.8 kW, (e) 7.73 kW/K The exhaust gases from a gas turbine are used to heat water in an adiabatic e<lI1llterflow beal exchanger. The gascs an: cooled from 260 to 120C, while water enlcr.s at 65"C The flow mtes of tile gas and waler are 0.38 kg/s aod 0.50 kg/s respc<:ti>'dy. The consllInt pl"l'SSure slXc ific healS forlhe gas and water are 1.09 and 4.186 kJlkg K respectively. Calculate tile rnle of excrgy loss due to heat transfer. Take To - 3SC. 04113. 11.92 kW The exhaust from a gas turb ine at 1.12 bar, 800 K fl ows steadily inlO a heal exchanger which cools the gas to 700 K without significant pressure drop. "Thc lleat transfer from lbe gas heats DD air flow al cooSlllllt pressure, wllich eOICTS the heal exchanger at 470 K. The mass flow rale of air is twie<: that of tile gas and the surroundings are all .03 bar, 20C Oclennine: (a) the decrease in availabi lity of the exhau!<!. gases, and (h) the total entropy production per kg of gas. (c) W1mt armngemenl would be llttessaI)' to make the beat transfer revenible and how mueh would Ihis increase the power OUtput oftbe plant IXr kg of turbine gas? Take C"p forexbaust gu as 1.08 and for airas I.OS kJlkg K. HeglOC! heat tnmsfer 10 tile surroundings and Ille changes in kinetic and potential energy. Aru. (a) 66 U lkg, (b) 0.0731 kJlkg K. (e) 38.7 kJlkg An air prebcater is used to beal up the air used for combustion by cooling the oUlgoing prodocl$ of combustion from a furnace. The rate of flow of tile products iJ 10 klfs. and tile products are cooled from 3000<: 10 20Q"C, and fortb.c products II thiJ temperature C"p. Ul9ItJ/kg K. The rale ofair flow is 9 kg/s, Ille inilia l air temperature is 40C, and for the air c, - 1.005 kJ/kg K. (a) Wbat is the initial and fmal availability of the products?


8. 14

c, ..

8. 15



8. 18

276 = (b) What is the irrevenibilily for this process? (e) If the beat transfer from the products wen: to take pia<.:<: R:versibly through heat engines, w!lat would be the finally lemjX'nllure of the air? Wha t JlO"'er wou ld be developed by the heat cngines? Take To " 300 K. AIlS (a) 85.97, 39.68 kJlkg. (b) 256.5 kW. (e) 394.41 K. 353.65 Ir.W 8.1 9 A mass of2 kg of air in a vessel clIpands from 3 bar, 70"C to I bar. 40C. while receiving 1.2 kJ of heat from a reservoir at 1200C. The environment is at 0.98 bar, 27C . Ca lculate the rrwtimum work and the ,,ork done on the atmosphere. AIlS. 177 kJ, 112.5 kJ 8.20 Air enters the compressor of a gas turbine al I bar, 30C and leaves the compressor at 4 bar. The compressor ha$ an efficiency of82%. calculate jX'r kg of air (a) the work of compression, (b) the reversible work of compression. and (c) tbe irrevenibilily. [Form. use

...l!... T ", ( 1.. ) '-'" 11 PI

wheR: Th is the tempenlllm: of air after isentropic compR:ssion:lJld y- 1.4. T1Ic compressor efficiency is defined as (Th - TtJl(Tj - Til, where TI is the actual tempem~ of air after compressiona!.) AIlS. (a) 180.5 kJlkg, (b) 159.5 kllkg(c ) 2 1 kJlkg A tn.U, of6.98 kg of air is in a vesse l at 200 kPa, 21G. Heat is transferred to the air from a R:servoir at 121C until the temjX'nlluR: of air rise, to 321C. The environment is al lOOlc.Pa, 11C, [)ctermine (a) the initial and final ava ilabilily of air. (b) the muimum useful work associalCd with the process. A~. (a) 103.5, 621.9 kl (b) 581 kJ Air enlen an adiabatic compressor in steady flow at 140 kPa. 11C and 10 mls and leaves it at 350 kPa, 127' C and 110 mls. The environment is at 100 kPa, 1 C. Calculate per kg of air (a) the actual amount of work required, (b) the minimum work requin:d, and (e ) the in"eversihilily of the process. AIlS, (a) 114.4 kl. (b) 91.3 kJ, (c) 17. 1 kJ Air expanch in a turbine a.d iaootically from 500 Ir.Pa, 400 K and 150 mls to 100 kPa. 300 K and 10 mls. The environment is at 100 kPa. 17"C. Caleulate per kg of air (a) tbe maximum work output, (b) the actual work output, and (e) the ineversibilily. AilS. (a) 159 kJ, (b) 109 kJ , (c) 50 kJ Calcu late the specifie exergy of air for a state 8t 2 har, 393.15 K when the surroundings are at I bar. 293. 15 K. Take c p - I and R - 0.287 k1/kg K. AIlS. 12.31 kl/kg Calculate the specific elierg}' of COl (cp - 0.8659 andR - 0.1889 kl/kg K) for a slall: at 0.7 bar, 268. 15 K and for the environment at 1.0 bar and 293.15 K. AIlS. - 18,77 kJ/kg A pipe eam es a stream of brine with a mass flow rate of 5 kgfs.. Bn::ause of poor thennal insulation the brine temperature ilx:reases from 250 K 3tthe pipe inlet to 253 K al the ellil. Neglecting pTCS5UR: Ilses, calculate the irreveTllibilily tate (or nlte of ellCfJl)' degradation) associated with the heat leakage. Take To - 293 K and cp - 2.85 kl/kg K. AilS. 1,05 kW In an adiabatic throttling process, energy per unit mass or enthalpy remains the same. However, there is a loss of exergy . An ideal gu flowing at the rate," is

8.2 1







throttled from pressurcPI to pressl.lrep2 when the en "ironment is at tempemlure To- What is the rate of exergy loss due to thronl ing"


i _ mRTo In .EL.

p, g.28 Air at 5 bar and 20 C flows into an evacuated tank until the pressun: in the tank is , bar. Assume that the process is adiabatic and the tempet1ltun: of the surroundings is20"C. (a) What is the finaltemperaturc of the air? (b) What i$ the revasible work prodoced between the initial and final statCS of the air? (C) What is the net entropy change of the air entering the tank? (d) Calcula te the irreversibility oflhe process. An.r. (a) 41 0.2 K. (b) 98.9 Ulkg. (e) 0.3376 kJlkg K, (d) 98.9 kJlkg 8.29 A Carnot cyc le engine receives and rejeets heat with a 20"C temperature differential bclWcen itselfand the thermal energy reservoirs. ~ cxpansion and compre5sion processes have a pressure I1Itio of 50. For I kg of air as the wOrXing substance, cycle temperature limits of \000 K and 300 K and Tu ,. 280 K, determine the second law efficiency. All.<. 0.965 8.30 Energy is received by a solar collector at the rate of 300 kW from a source temperature of 2400 K.. If 60 kW of this e~rgy is lost 10 the surroundings at steady state and if the user temperature remains constant at 600 K, what arc the rIM law and the K<:ond law efficiencies? Take To - 300 K. An.!. 0.80, 0.457 8.3 1 For flow ofan ideal gas through an insulated pipeline. tile pressure drop~ from 100 bar to 9' bar, If the gas flows at the rote of U kgls and has c p - 1.005 and Cy - 0.7 18 U lkg K and if To - 300 K. find the mle of enlropy genc:ration and mte of Ion of eltergy. Au 0.D21 5 kWfK, 6.46 kW 8.32 The cylinrlerofan internal combllSli on engine contains gases at 2500' C, 5S bar. Expansion takes place through a volume ratio of 9 lI\:Cordi ns to pvl J' - canst. The surroundings arc al 20 C, 1.1 bar. Determ ine the lou of availab ili ty. the work transfer and the heal transfer per unit ma5l. Treat the gases as ide:ll having R " 0.26 Ulkg K and c. '" 0.82 Ulkg-K. Ans. 1144 kJlkS, 1074 U lkg, - 213Ulkg 8.33 In acounterllow heat exchanger, oil (cp '"' 2.1 UlkgK) is eooled from 440 10 320 K, while water (ep - 4.2 kJlkg K) is healed from 290 K to temperature T. Th e rcspe<:tive mass flow rates of oil and water are SOO and 3200 kglb . Neg loct:ing pressure drop, KE and PE etTe<:l.~ and heatlosil, detennine (a) the temperature T, (b) the nile of exergy destruction, (c) the second law efficiency. Take To - 17"C .nd Po" 1 atm. AM. (a) 305 K, (b) 4 1.4 MJIh, (c) 10.9% S.34 Oxygen enters a nozzle GpCmting at steady state at 3.8 MI'a, 387"C and 10 mls. At the nozzle exit the conditions arc 1'0 kPa, 37C and 750 mls. Detennine (.) the heat transfer per kg and (h) the irreversibility. Assume oxygen as an ideal gas. and take To " 20 C. Po " 1 atm. All.<. (a) - 37.06 kJlkg. (b) SI.72 kJlkg S.35 Argon gas expands adiabatically in a turoine from 2 MPa , l OOO C to 350 kPa. The mass now rate is 0.' kgfs and the turbine de\'e!ops power al the rate of

278=120 kW. Oc:tennine (a) !he tempe:raHIte of argon at !he nubine exit, (h) !he irreversibility rale. and (cl the se<:ond law effICicncy. Neglcct KE and PE effects and take To " 20'C, Po" I atm. A1I3. (a) S38 .1 C, (b) 18.78 kW. (e) 86.S% In the boiJerofa powerplanure tubes through which walerflows as it is brought from 0.8 MPa., ISO"(; (h" 632.6 klllr.g. $ " 1.84 18 kJ/kg K) to 0.8 MPa., 2SO"C (h " 29S0 kJlkg, s " 7.0384 kJlkg K). Combustion gases passing over the lUbes cool from 106J<'C to S4J<'C. These gases may be: considered as air (ideal gas) ha,Yingcp " I.OOS kl/kg K. Assuming Sleady state and neglecting any heat loss. and KE and PE effects, determine (a) the nws flow rate of combustion gase:s per kg of steam, (b) the los,<; of exergy per kg steam. and (c) the second law efficimcy. Take To" 2S C, Po " I atm. Ans. (m) mim ... '" 4.434. (b) S02.29 kJllr.g steam. (e) 4S.9% Air cnlCB a b.ait dryerat U aC. I barwith a velocity of3.7 mls IllKicxits at 83'C, 1 bar with a velocityof9.1 mil through 8/l arca oflS.7 cm l . Neglecting any heat loss and PE effect and takins To" UC. (a) evaluate the power requ ired in kW, and (h) devise and evaluate a second [aw effi ciency. AIlS. (a) - 1.02 kW, (h) 9"/0 An iso[ated system oonsists ofl\\'o solid blocks. One block hils p mass of S kg and is iniTially at 300 C. The other block has a mass of 10 kg and is initially HI - SO"C. TIle blocks are allowed 10 come into thennal equilibrium. Assuming the blocks are incompressible with conSlan1 specific heau of I and 0.4 kJllr.gK. respectively. de\CfTTline (II) the fUUlltempcrDlUrC. (h) the irrevef3ibility. TlIke To 300K. AIlS. (a) 417.4 K, (b) 277 kJ Air flows into a heal engine at ambient condilioll!l 100 kPa. 300 K.. ElK'rgy is supplied as 1200 kJ per kg air from a 1S00 K soum: and in some pan of the process, a heat loss of 300 kJllg air happens at 750 K. The air lea'u the engine at 100 kPa, SOOK. Find the first and Ibe second la w efficiencies. Ans. 0.3 IS, 0.672 Consider two rigid containers ea~b of \'olumt I ml containing air at [00 kPa. 400K. An internally reversible Carnol beat pump is then thermal ly connected between them so lhat it healS one up and cools the other down . In ordeT to transfer heat aC a reasonable rate, the lempenuun: difference bet....een the working fluid inside the heat pump and the air in !be comaincf3 is sct to 20"C. TIle process SlOpS when the air in thccoldest tank reaches 300K.. Find the fllUl [ tcmperawrcof the air that is \leated up, the work input 10 the beat pump, and the ovcrall second law effici ency. A1I3. SSO K. 31.2 kJ, 0.816







Properties of Pure Substances

A pure substance is a substance of constant chemical composition throughout its mass. It is a one-component system. It may exist in one or more phases.


p-lJ Diagram fo r a Pure Substance

Assume a unit mass orice (solid water) at _ 10C and I atm contained in a cylinder and piston machine (Fig. 9. 1). LeI the ice be heated slowly so that its temperature

i:; always uniform. The changes wbich occur in the mass of water would be traced
as the temperature is increased while the pressure is held constant. Let the stale

changes of water be plolted onp-v coordinates. The dislim:t regimes of heating,

as shown in Fig. 9.2, are;

FIg. 9. 1 Iltalir18 of Ill 0 at" colIJ/anl prtJSllrt ~f I aim

/-2 The temperature orice increases from - !Ge to O O C. The volume orice would increase, as would be the case for any solid upon bealing. At state 2, Le. ooe, the ice would start melting. 1- 3 Ice melts into waler at a constant tcmperarure of O~C . At state 3, the melting process ends. There is a decrease in volume. which is a peculiarity of

280 = 3-4 The temperature of water increases, upon heating, from ooe to lOooe. The volume of water increases because of thermal expansion. 4-5 The water starts boiling at state 4 and boiling endsat state S. This phase e (the change from liquid to vapour occurs at a constant temperature of lOo G pressure being constant at 1 atm). There is a large increase in volume. e (state 6). The volume of vapour .5-6 The vapoUr is heated to, say, 250 G increases from Vj to v6 . Water existed in the solid phase between I and 2, in the liquid phase between 3 and 4, and in the gas phase beyond S. Between 2 and 3, the solid cbanged into" the liquid pbase by absorbing the latent heat of fusion and between 4 and S, the liquid cbanged into the vapour phase by absorbing the latent heat of vaporization, both at constant temperature and pressure. The states 2, 3, 4 and 5 are known assahlralian states. A saturation state is a state from which a change of phase may occur without a change of pressure or temperature. State 2 is a saturated solid stote because a solid can change into liquid at constant preuure and temperaNre from state 2. States 3 and 4 are both saluraled liquid states. In state 3, the liquid is saturated with respect 10 solidification, whereas in slate 4, the liquid is saNraled with respect to vaporization. Slate 5 is asaturated vapour stare, because from slate 5, the vapour can condense into liquid without a change of pressure or temperature. If the beating of ice at _ loGe to stewn at 250C were done at a constant pressure of 2 atm, similar regimes of healing would have been obtained with similar saturation states 2, 3, 4 and 5, as shown in Fig. 9.2. All the slate changes of the system can similarly be plotted on thep-v coordinates, when it is heated at different constant pressures. All the saturated solid states 2 at various pressures are joined by a line, as shown in Fig. 9.3 .

, """ , I .... _._n ,


, ,

, -- -,


Large volume change


Fig. 9.2 CluJIlftJ ill tJu ~oINII" ofUItlIn tbnill8 MlJ/i"8 at t11I1SUlIII prnnltt Similarly, all the saturated liquid states 3 with respect to solidification, all the saturated liquid slates 4 with respect to vaporiUllion, and all the saturated vapour Slates 5, arejoined together. Figure 9.4 shows slate changes of a pure substance other than water whose volume increases on melting. The line passing through all the satwated solid states 2 (Figs 9.3 and 9.4) is called the saturated solid line. The lines pa5Bing through all the saturated liquid states 3 and 4 with respect to solidification and va porization respectively arc

known as the.Jaturated liquid lint.J. and the line passing Ihrougb all the saturated vapour Slates 5, is the saturated vapour line. The saturated liquid line with respect {o vaporization and the saturated vapour line incline {owards each other and form wha{ is known as the soturation orvtJpQurdome. The two lines meet aI the criticol state.
set told line

CrI1k:at ItlIta



3 3

~ 3

5 _ __,selurated vapour line ----5 5


.. L+V 5


Triple poinIllne

, ,


p-u iUWtlrn Df (I purr saoAmiIlU DIMr tMlI INUr, wIuM will",!



To the left of the saturated solid line is the solid (5) ngion (Fig. 9.4). Between the saturated solid line and saturated liquid line with respect to solidification there exists the 101id.liquid mixturt (S + L) region. Between lIle two santrated liquid Jines is the compressed liquid region. The Iiquid'\'(Jpour mixture region (L + V) uists within lIle vapour dome between the saturated liquid and saturated vapour Jines. To lIle righ{ of tbe saturated va pour line is lIle vapollr rtgion. The triple point is a line on the ~v diagram. where al l the three phases. solid. liquid

282=and gas, exit in equilibrium. At a pressure below the triple point line, the substance cannot exist in the liquid phase, and the substance, when heated, transforms from solid to vapour (known as sublimation) by absorbing the latent heat of sublimation from the surroundings. The region below the triple poiDlline is, therefore. the solid-vapour (S + VJ mixture region. Table 9.1 gives the triple point data for a nllmber ofsub5tallces. Table 9. 1
Subsrtmce Acety1elll:, ClH}
Ammonia, NHl

Tripld'oi/IJ Dalil

Temperature. K
192.4 195.42 83.78 216.55 68.14 89.8g 104.00 13.84 90.67 63.15 54.J5 273. 16


45.58 SIS.7 3885.1 115. 14

Argon, A Carbon dioxide, COl Carboll monoxide, CO

Methane, ~H.!

EtbylcllC, ~H. Hydrogen, H2

Methane, CA.

0006 0.'
52.8 87.7 94.01 1.14 4.587

Nitrogen, N2

Waler, H 2 0

Liquid is, most often. the working fluid in power cycles, etc. and interest is often confined to the liquid-vapour regions only. So to locate Ihe state points. the solid regions from Figs 9.3 and 9.4 can be omitted. The Jrv diagram then becomes as shown in Fig. 9.5. If the vapour at state A is compressed slowly and isothennally, the pressure will rise until there is saturated vapour at pointB.lfthe compression is continued, condensation takes place, th e pressure remaining eonstant 50 long as the temperarure remains constant. AI any point between B and C, the liquid and vapour are in eqUilibrium. Since a very large increase in pressure is necded to compress the liquid, line CD is almost vertical. ABCD is a typical no/herm of a pure substance on a p-lI diagram. Some isotherms are shown in Fig. 9.5. As thetemperaturc increases, the liquid-vapour transition. as represented by BC, decreases. and becomes zero at the crilical point. Below the critical point only, there isa liquid-vapourtransilion zone, where a saturated liquid, on healing, absorbs the latent heal of vaporiza ti on. and becomes satUfllted vapour at a constant pressure and temperature. Similarly, a saturated vapour, on cooling, releases the latent heat of condensation al constant pressure and temperature to become saturated liquid. Abovethe critical point, hnwever, a liquid, upon heating, suddenlyjlashcs into vapour, ora vapour. upon cooling, suddenly condeMes into liquid. There is no distinct transition zone from liquid to vapour and vice versa. The isotherm passing through the critical point is called Ihecrlticol notherm, and the corresponding temperature is known as the crilicallemperature (tol. The pressure and volume at the critical point are known as the critical pressure (PJ and the crj(jcalllOlume (vJ respectively. For water


~f Am



Po = 221.2 bar te = 374. IS oC Ve = 0.00317 m1lkg

Critical point

vapour Moe

Saturated IIQuOd



FIg. 9.5 Sciturftlion CIIrvt "" p.~ diogtoltl

The critical point data of certain substances are given in Appendix F. Above the critical poin t, the isothcnns are continuous c urves thai at large volumes and lo w pressures approach cquilatel"lll hyperbolas. When a liquid or solid is in equilibrium with its vapour at a given temperature. the vapour exens a pressure that depends o nl y o n the temperature (Fig, 9.6). In general, the greater the tempera ture, the higher is the I'apour prtssurt. The !empel1l.turt; at which the vapour pressure is equal to 760 mm Hg is cailed the normal boiling point.

Fig. 9.6

Vopour /lTeS1lm

Phase change occurs at co nstant pressure and lempel1l.ture. A pure liquid at a give n pressure will transfonn into vapour o nl y at a panicular temperature. known a<i salrml/ion It mperatrlrt. which is a function of pressure. Similarly, if tho;: temperature is fix ed. the liquid will boil (or condense) onl y at a panicular pre.~~ure, called the sa/uralion presJllrt!. which is a function of temperature. In Fig. 9.7. if p, is the pressure. the corresponding sa turation temperature is ('",),. or if'1 is the give n tempernlure, the saturntion pressure is (P..}z. As the pressure increases. the saturn tion tempel1l.!ure increases. Sat urnti on states eltist up to the critical point. At poi nt A. the liquid starts boili ng, and at point B. the boili ng gets completed. AtA. it is all liquid (saturated) and there is no vapour, while at B. it is all vapour (satu rated) and there is no liquid. Vapour content progress ively increases as the liquid changes it.~ state from A towards 8.
Jr~ -,j



If u. is the specific volume of the salUrated liquid at a given pressure, and v, the specific volume of the saturated vapour, then (v, - vr) or vr, is the cbange in specific volume during phase transition (boiling or condensation) at that pressure, As pressure increases, vii decreases, and althe critical point vr, becomes UfO,
CrHicat point


8 '

9.2 Jr T Diagram for a Pure Substance
The sl:Ite changes of a pure substance, upon slow heating at different constanl pressures, ate shown on the p-v plane, in Figs 9.2, 9.3. and 9.4. If these siale changes are ploltedonp-Tcoordinates.lbe diagram. as shown in Fig. 9.8. will be obtained. If the heating of ice al- \ OOC 10 steam al 250C at the constant pressure of I attn is considered, 1- 2 is the solid (ice) heating. 2-3 is the melting of ice al OOC. 3-4 is the liquid heating, 4-5 is the vaporization of water at lOOOC, and 5-6 is the heating in the vapour pbase. The process will be reversed from state 6 to state I upon cooling. The curve passing through the 2, 3 points is called the /usioll cut'\'t', and the curve passing through the 4, 5 points (which indicate the vaporization or condensation at different temperatures and pressures) is called


atm +'--1' c ." ''''''''-_ --,'''';-t- ..2, 3 Region 4, S

Sublimation region -"-"_ _


"'. I

" - Triple

- 10'C



'.' vapour




flg. 9.8 Pfusslfqrilibrilllll diqrllfll on p - T CQ{lTdiMte.s

PrapnlitJ DfPnt SUiJUIIUU the vaporization curve. If the vapour pressure of a solid is measured at different temperatures, and these are ploned, the sublimation curve will be obtained. The fusion curve, the vaporization curve, and the sublimation curve meet at triple The slopes of the sublimation and vaporization curves for all s ubstances are positive. The slope of the fusion curve for most substances is positive, but for water, it is negative. The temperature at which a liquid boils is ve ry sensitive to pressure, as indicated by the vaporization curve which g ives the saturation temperntures at different pressures, but the temperature at which a solid melts is not such a strong function of pressure, as indicated by the small slope of the fusion curve. The triple point of water is at 4.58 mm Hg and 273.16 K, whereas that of COl is 8t388S mrn Hg (about 5 atm) and 216.55 K. So when solid COl ('dey ice') is exposed to 1 aim pressure, it gets ttansformed into vapour directly, absorbing the latent heat of sublimation from the surroundings, which gets cooled or 'I"!frige. IlIted.



p-"O- T Surface

1bc relationships between pressure, specific volume, and temperature can be

clearly understood with the aid ofa three. dimensionalp-v--Tsurface. Figure 9.9 illustrates a substance like water that expands upon freezing and Fig. 9. 10 illustrates substances other than water which contract upon freezing. The projections on thep-Tandp-v planes are also shown in these figures. Any point on the p-v--Tsurface represents an equilibrium Slate of the substance. The triple point line when projected to thep-Tplane becomes a point. The critical isotherm has a point ofinflection at the critical point.


T-s Diagram for a Pure Substance

The healing of the system of I kg of ice al - SoC to steam al 250C is again considered, the pressure being maintained constant al I atm. The en lropy increases of the system in differenl regimes of heating are given below.

I . The entropy incn:ase of ice as it is heated from - SoC to OC at I atm. (cpo .. 2.093 kJ/kg K).
"' .1'2- $] =

<tQ dT 273 J --= J -me -' - - =c [n T T 268

Tj " m

T - 26S l

- 2.093 In


- 0.0398 kJ/kg K.

2. The entropy increase of ice as it melts into water at OO C (latent heat of fusion of ice = 334.96 kJ/kg)
As 2
"' .!' ) -.!'l '" - - - -

334.96 273

1.23 kJ/kg K


286 = -

Basic q.ruI Applitd 11ImlHldYMlflics


, , ,



...' ,


r> To
Specifoc: 'o"OIurnII
T< T.

Triple point Tllmper3ture




FIg. 9.9 p-II- T jNif~(t q.M projtcliolU for 0 JMinumu 1M/ apq.tuIJ on fuuj", (q.) 17t,udimt1JSiotUll ~i,w (b) P1uu, diap4m (f) p.~ diot'q.",

3. The entropy increase of water as it is heated from OC to 100C (c, _ - 4. 187 kJ/kg K)
d.rJ - .!"~ - .!"l- C In ...l.. - 4.187 In - ~



373 273

'" 1.305 kJ/kg K

4. The entropy increase of water as it is vaporized at 100C, absorbing the lalent heat ofvaporization (2257 kJ/kg)

= s, -


2257 .. - .. 6.05 kJ/kg K 27J

5. The entropy increase of vapour as it is heated from 100C to 250C at 1 aIm






Triple point


Ag. 9.10 p-p-T SUr/lUI aoul p,qjrniolU for a n.~/mlct tiuJl con/ram OIIfrrjll(, (a) nrre-tlimnuioNJ/ DUw (~) I'frilM tlitwam ) pOD tlitwam






= 2.093 In - 373


= 0.706 kJ/kg K
assu ming the avcl1Ige specific heat of steam in thc temperature rangc of 100C to 250 C as 2.093 kJlkg K. Thcse cntrop y changcs are shown in Fig. 9. 11 . Thc curvc 1-2-3-4-5-6 is thc isolxlr of J atm. If. during the heating process, the pressure had been maintained constant at 2 aim. a simi lar curvc would be obtained. The slalcs 2. 3.4. and 5 are saturation stales. If these states for different pressures are joined. as in Figs 9.3 and 9.4. the phase equilibrium diagram of a pure subslanceo n the T-scoordi nalcs. as shown in Fig. 9.12. wou ld be obtained.

288 = -

.~~.~ ................. ...... _._ ..6.6

100 ' C


-, ."

, ,- ,

OC 2

, , --0,
FIg. 9.11 bobGn Q" T-s pUiI


s ,

,. V

Triple point ....

s. V

Fig. 9.12

PAs.. tfJIlilibrillm iiqr.... on T-s cotmiilltlw

Most oRen, liquid-vapour transformations only are of interest, and Fig. 9.13 shows the liquid, the vapour, and the transition zones only. AI a particular pressure, sr is the specific entropy of saturated water, and is that of saturated vapour. The entropy change afthe system during the phase change from liquid to VlIpoural that pressure iUr, (" s, - sr)' The value of"fJ: decreases as the pressure increases, and becomes zero 81 the critical point.



"-8 Diagram or MoUler Diagram for a Pure Substance

From the first and second laws of th ermodynamics, the fo llowing property relation was obtained.


,. v
Satunlllad liquid tine 5

Tds '" dlI - vdp

( ~) a, , - T


This equation fonns the basis of the h-:r diagram of a pure substance, also called the Mollier diagram. The slope of an isobar on the h- .I" coordinates is eq ual to the absolu te saturation temperalUre (1..1 + 273) at th at pressure. If !he tcmperalUre remains constant the slope will remain constant. If the temperature increases, the slope of the isobar will increase. Consider the healing of a system of ice 31 - SoC 10 steam at 2SO"C, the pressure being maintained constant at I atm. The slope oftbe isobar of [ atrn on the h-s coordinates (Fig. 9. 14) first increases as the temperature of the ice increases from -SoC 1 0 OQC ( 1- 2). Its slope then remains constant as ice melts into water at the

, , , ,


Slope constant

Increasing slope

, ~.

Fig. 9.1"

--- . ,

IS.'1 til ft-s pl~1

290=constant temperature ofOC (2- 3). The s lope of the isobar again increases as the temperature of wate r rises from OC to HX)C (3-4). Thc slope again remains constant as water vaporizes into steam at the constant temperalure of iOOC (4-S). Finally, the slope of the isobar continues 10 increase as the temperature of sleam increases 10 250C (5-6) and beyond. Similarly, the isobars of different pressures can be drawn on Ihe h- s diagram as shown in Figs 9.14 and 9. 15. States 2,3,4. and 5 are saturation states. Figure 9. 15 shows the phase equi librium diagram ofa pure substance on theh-s coordinates, indicating the saturated solid line, satunlted liquid lines and saturated vapour line. the various phases. and the transition (mixture) lanes.

Saturated vapour line

Figure 9.16 is the h-s or the Mollier diagram indicating only the liquid and vapour phases. As the pressure increases. the salUnltioli tempernture increases, and so the slope of the isobar also increases. Hence. the conslUnt pressure lines diverge/ram one another, and the critical isobar is a tangent at the crit ical point. a! shown. In the vapour region. the states of equal slopes at various pressures are joined by lines. as shown. which are the cOrlStan//empera/ure lines. Although the slope of an isobar remains conlinuous beyond the saturated \'apour line. the isothenn bends 10waTds the right and its s lope decreases 3symptotically 10 lero. because in the idea l gas region it becomes horizontal and the constant enthalpy implies constant temperature.

[( ~~

= T+U (



v( ~: t by

Maxwe ll's relatinn. clmpter II. For an ideal gas, (

~~ )r T-V~ .. O. For T .. c.

h " c] At II p3nicular pressure,hris the specific entha lpy of saturated water. h. is that of saturated vapour. and h'l ('"' h. - h,) is the latent hcat of vaporization 3t

hr, becomes 7.ero.

that pressure. As the pressure increasesh rl dt'Creases. II lld at the critical pressure.

"' "

Propntia of Purr SdslllffUt


p., . 221.2 bar

...... . "" ... """"""


9.6 QualIty or Dryness Fraction

Ifin J kg of liquid-vapour mixture.x kg is the mass of vapour and (I - x) kg is the mass of liquid. then x is known as the qualify or dryness fraction of the liquid vapour mixture. Therefore, quality indicates the mass fraction of vapour in a liquid vapour mixture, or

m,.c x= ~c m. +ml

wherem. and m l are the masses of vapour and liquid respective ly in me mixture. The value ofx varies between 0 and I. For satllnlted water, when waterjust Slarts bo iling, x = 0, and for saturated vapou r, when vaporizatio n is complete. x = J, for which th e vapour is said to be dry saturated. Points m in Fig. 9. 17 (a), (b), and (c ) indicate: the: salUratc:d liquid Sillies wilhx = O. and points n indicate the saruroted vapour states with x :: 1. the lines mn indic ati ng the transition from liquid 10 vapour. Point.<; u. b . and c at various pressures indicate the situations when the masse s of vapour reached 25%, 50%, and 75% of the tOlai mass, i.e. al point.<; u, the mass of liquid is 75% and the mass of vapour is 25% of the total mass, lit point b. the miXfIlre e:onsists of 50% liquid and 50% vapour by mass, and at point.<; c, the mixture consist.<; of75 % vapour and 25% liquid by mass. The lines passing through point.<; a. b and c are the constant quality lines of 0.25, 0.50. and 0.75 respectively. Constant quality lines slarr from the critical point. lei Vbe the lotal volu me of a liquid vapour mixture of quality x. Vrthe volume of the saturated liquid, and V, die: volume of die saturated vapour, the corresponding masses being m, m" and m. re.spective\y .


m = mf+ m, V=Vr+V,


292 = -

m m

, """" , " ", "

i. )




--- ,


_ . .. ,
Fig. !U7
C.-lIIftt plliity /hw om P'D, T' I IIfIIl A J JUWlllfU

v= 1- m

'J",+-" m , ( m m'


where x .. - ' ,vr = specifi c volume of saturated liquid. v. " spedfic volume of saturated vapour, and v = specific volume oflhe mixture of quality x. Similarl y .!' .. (I -x) s(+ x.!', h - ( I -x) hr + xh. u '" (I -x) u(+ xu.

m m

(9 .3) (9 .4)

where.!', h, andu refertothe mixture of qualityx.lhe suffiX/and suffixg indicate the conditions of sa turated liquid and saturated vapour respectively. From Eq. (9.2)
v " (I - x) Vt+ XV,

- v(+x(v.-v()
.. 0(+

x, 0(,

"' "


v - v,+:rv" h"'h,"':rh r, s .. s,"':r s" u - uf+xuf.

(9.7) (9.8) (9.9)




Volume fraction of vapour or voidage, a = vlv m :o m,+m s

{W '" Prvf+

p. v. " p,{v - vJ + p. V.


(I -

a)Pr+ aPt

9.7 Steam Tables

The properties of water are arranged in the steam tables as functions of pressure and lemperature. Separate tables are provided to give the properties ofwaler in the saturation states and in the liquid and vapour phases. The internul energy of saturated water at the triple poim (t - 0.01"C) is arbitrarily chosen 10 be zero. Since h - u + pv, the enthalpy of saturated water at 0.01 D C is slightly positive bc:cause of the small value of (pv) tcnn. The entropy of satura/ed waler is abo chosen to be zero at the triple point.


SaturrUifJn SltJtu

When a liquid and its vapour are in eqUilibrium at a cenain pressure and tempemlure, only the pressure or the temperature is sufficient to identify the saturation state. If the pressure is given, the temperature of the mixture gets fixed, which is known as the saturation temperature, or if the temperature is given, the saturation pressure gets fIXed. Saturated liquid or the saturated \'apour has only one independent variable, i.e. only one property is required \0 be: known to fix up the state. Tables A.I(a) and A I (b) in the appendix give the properties ofsalUtllt eel liquid and saturated vapour. In Table A.l(a), the independent variable is tempernture. At a particular temperature, the values of saturation pressurep, and v" v~ hI' hr hi' Sr and s. are given, where vI' hr, and Sr refer to the saturated and sr, liquid states; va' hi and s. refer to the satumted ';'lpour state: and Vr" refer 10 the changes in the property values during :vaporation (or condensation) al that temperature, where vr. '" v. - Vf and sr," s, - sf' In Table A.I(b), the independent variable is pressure. At a particular pressure, the values of saturation temperature I, and vr. v, , hr' h h~. sr, and are given. r" Depending upon whether the pressure or Ihe temperalUre IS given. either Table A.1(a) or Table A.J(b) can be conveniently used for computing the properties of saturation states. If data are required for intermediate temperatures or pressures, lineur interpolation is nonnullyaccurale. The n:ason for the two tab les is to reduce the amount of interpolation required.

h ,..

s .


9.7.2 Litpdd-lIlJpour Mi:duru

Let us consider a mixture of saturated liquid water and wa ter vapour in equilibrium at pressure p and temperature I. The composition of the mixture by mass will be given by ilS quality x, and its state will be within the vapour dome (Fig. 9.1 8). The propcnies of the mixture are as given in Ankle 9.6, Le.
U "

vr+ x vrE ur+ x uri h " hr + x hfl

s=sf + xsfa

where VII vrl' uf' ura' hll hrl , sr and sfa are the saturation propcnics at thc given pressure and temperature.

, 1
Sf 5


- -- s
Fig. 9.18 Pr'IfItT" lit two plum " !;I'ON

Ifp or t and the quality of the mixture are given, the propcnies of the mixture (v, u, h, ands) can be evaluated from the above equations. Sometimes, instead of quality, one of the above propenies, say, specific volume v, and pressure or temperature are given. [n that case, the quality of the mixture x has to be calculated from the given v and p or I and then x being known. other propenies are evaluated.




When the temperature of the vapour is greater than the saturation temperature corresponding to the given pressure, the vapour is said to be.fuperheated (state I in Fig. 9. 19). Thc difference between the temperature of the superheated vapour and the saturation temperature at that pressure is called the superheat or the degree o/superheat. As shown in Fig. 9. 19, the differe nce (II - f oat ) is the superheat. In a superheated vapour at a given pressure, the temperature may have different va lues greater than the saturation temperature. Table A,2 in the appendix gives the values of the properties (volume, enthalpy, and entropy) of superheated vapour for each tabu lated pair of values of pressure and temperature, both of which are now independent. Interpo[ation or e]ttrapolation is to be used for pairs of values ofprcssure and temperature not given,


9.7.. Compressed LUpliIl

Fig. 9.19 SuptTA.allllfd luko/j"t

When the temperature of a liquid is less than the saturation temperature at the given pressure. the liquid is called compressed liquid (state 2 in Fig. 9.19). The pressure and temperature of compressed liquid may vary independently, and a table of propenies like the superbeated vapour table could be arranged to give the propenies at any p and t. However, the properties of liquids \'Q')' litlle with pressure. Hence the propenies are taken from the saturation tables at the temperature of the compre~sed liquid. When a liquid is cooled below ilS saturation temperature at a cenain pressure it is said to be Y/lhcoo/ed. The difference in saturation temperature and tbe aClUalliquid tempernture is known as the degree ofsubcool ing, orsimply, subcooling (Fig. 9.17).

9.8 Charts of Thermodynamic Properties

The presentation of propenies of substances in the fonn of a chari has ceMain obvious advantages. The manner of variation of properties is clearly demonstrated in the chart and thcre is no problem ofinterpolation. Howc\'er, the precision is nOI as much as in steam tables. The temperatureentropy plot and enthalpy-entropy plot (Fig. 9.20a) are commonly used. Thc temperature-entropy plot shows the vapour dome and the lines of constant pressure, constant vo lume, constant enthalpy. constant quality, and constant superheat. However, its scale is small and limi ted in use. The enthalpy-entropy plot or Mollierchan, has a larger scale to provide data suitable for many computations. It contains the same llata as does the T- s chart. The Mollicr chart for waler is given in Appendix F.I. The Mollier diagram for steam with data taken from Keenan et al. Steam Tables (John Willey, N. Y., 1969 is given in Fig. 9.21.)

9.9 Measurement of Steam Quality

The state ofa pure substance gels fixed if two independent properties are given. A pW'C substance is tbus said to bave two degrees of freedom. Ofal! thennodynamic propenies, il is easiest to measure the pressure and temperature of a substance. Therefore, whenever pressure and temperature are independenl properties, il is

296 = -


COmp' ...,

- - -H

Critical point

, ,, , ,, ,,
0- ,

p ..

p- ,

, ,,

,. ,

,- ,

p- ,

!~~~'- ' J::JJr


the pl1lctice to measure them to determine that state of the substance. This isdolle ill the compressed liquid regioll or the superheated vapour region (Fig. 9.22), where th e measured values of pre$sure and temperature would fix up the state. But whell the substance is ill the saturation state or two-phase region (Fig. 9.22), the measured values of pressure and temperature could apply equally well to satunued liquid point/. saturated vapour point g, or to mblOtures orany quality. points .xl,.xl or .xl. Of the two properties. p and t, only one is independent; the other isadependent property. If pressure is given, the saturation temperature gets


FIg. 9.21

M~lIit1 diqralf!f~r lilam (D414 I4kt~ ftOIf! KU'Il~II,j.J/., F.G. Ktyn, P.C. Hill nij.,. MlK1Tt, Slttlm Tahlu,j.lm WiIry. N. Y., 1969)

automatically fixed for the substance. In order to fix up the state of the mixtun:. apart from either pn:ssure or temperature, one more property, such as specific

298 = -

, ,. ,

volume, enthalpy or composition of the mixture (quality) is required to be known. Since it is relative ly difficult to measure the specific volumc ofa mixture, devices such as calorimeters are used for determining the quali ty or the enthalpy of the mixture. In the measurement of quality, the object is always 10 bring the state of the substance from the two-phase region 10 the single-phase or superheated region, where both pressure and temperoture are independent, and measured to fix the state, either by adiabatic thrott ling or electric heating. In the IhrotflingcQ/orimeler, a sample of wet steam ofmassm and at pressure PI is taken from the steam main thrOUgh a perforated sampling tube (Fig. 9.23). Then it is throttled by the partially-opened valve (or orifice) to a pressure Pl. measured by mercury manometer, and temperature /2' so that after throttling the steam is in th e superltea ted region. The process is shown on the T- s and h-s
Steam main Sampling tube Insulation


c.w. 0\11

""""'CoolIng waillf in

Fig. 9.23

17Iro1lli~ tll/orilflt,"

- = 299
Critical point
Crttical point

- ->


- .


Fig. 9.2..

diagrams in Fig. 9.24. The steady flow energy equation gives the enthalpy aRer throttling as equal to enthalpy before throttling. The initial and final equilibrium states IlUld 2 arejoined by a dolted line since throltling is irreversible (adiabatic but not isentropic) and the intermediate states are non -equilibrium states not describable by thermodynamic coordinates. The initial stale (wet) is given by PI and Xl' and the final state by pz and'2 (supemeated). Now


hfpl + xlhr",l - h2 hz - hlPl

XI '"


WithPl and,z being known. h~ can be found out from th e superheated steam tab le. The values of hr and hr. are taken from the saturated steam table corresponding to pressure Pl' Therefore, th e quality of the wet steam XI can be caleulated. To be SUTl: that stearn after throttling is in the singie-phase or superheated region. a minimum of 5C superheat is desired So iflhe pressure aRer throltling is given and the minimum s oe supertleat is prescribed, then there is the minimum quality of stcam (or the maximum moisture content) a1 the given pressure PI which can be measured by the throttling calorimeter. For example. ifPI = I atm., then'2 - IOsoe and the state 2 after throttling gets fixed as shown in Fig. 9.25. From state 2, the constant enthalpy line intersects the constant pressurepi line at J. Therefore, the quality XI is the minimum quality that can be measured simpl y by throltling. If the quality is. say. Xl less than XI ' then after throttling to P 2 - I atm . the superheat after throttling is less than 5C. If the qual ity is X'I' then throllling to I atm. does not give any superheat at all. When the steam is "ery wet and the pressure afl er throtl ing is not low enough to take the steam to the superheated region. then a combined separating and tirrorrling calorimeter is used for the measurement of quality, Steam from the

3DO=-Crllic;al point

Fig. 9.25

Millim .... fIl/J/ity tlull {/JII In m.4!urtd",,9' by ,Arollling

main is first passed through a separator (Fig. 9.26). where some pan of the moisture separates out due to the sudden change in direction and falls by gravity. and the partiall y dry vapour is then throttled and taken to the superheated region. In Fig. 9.27, process 1- 2 represents the moisture separation from the wet sample ofstcam at constant pressurep, and process 2- 3 represents throuling to pressure Pl' With P2 and tl being measured, hl can be found out from the superheated steam table. Now.




-"'-=" '"


moisture (m , )

Fig. 9.26 St/IIJtMing IIIId ,lrroll/illt us/Mi.1tIn


~~:::::::: Condensale ("'2)

Therefore, .1:2' the quality of steam after panial moisture separation, ean be evaluated. Ifm kg ofsteam is taken through the sampling tube in t sees, m1 kg of


PropnlitJ of Putt SdJ1411ctJ


Fig. 9..21 S'fi<"ali,,& and th,ouli,,& prrxtJUj D~ AJ p/D/ it is separated. and ml kg is throttled and then eondensed to water and eollected, then m ::o m, + m1 and at state 2. the mass of dry vapour will bex] ml' Therefore, the quality of the sample of steam at state I. X, is given by



__-'mc~C"'Co"rcdry:L"'"'poeo~oc'O'"'m"""~I,__, " . mass of liquidvapour at state I _

X2 ml


+m 2

The quality of wet steam can also be measured by an elecfric calarimeler (Fig. 9.28). The sample of steam is passed in steady flow through an electric heater, as shown. The electrical energy input Q should be sufficient to take the sleam 10 the superheated region where pressure P2 and temperature tl are measured. If I is the current flowing through the heater in amperes and V is the voltage across the coil, then at steady state Q - Vlx 10-l kW. Ifm is the mass of steam taken int seconds under steady flow condition. then the sleady flow energy equalion forthc healer (as control volume) gives

, 'Som.'",""

Exhaust condensed and COIIecI8d {m kg in I sees. savJ

Fig. 9.28

LIlriral ralorimtltt



302=wtllt+Q " lIIth1

where W t is the steam flow rate in kgls ( WI ==


h t + J2.. == h2


With h2' Q and wI being known , " l can be compUied. Now

hI '" hfpl + Xl"fapl

Heneexl can be evaluated.

Example 9.1 Find the saturation temperature, the changes in specific volume and entropy during evaporation, and the latent heat ofvaporizalion o fsteam at 1 MPa. Solution At 1 MPa, from Table A. I(b) in the Appendix

r.., - 179.91 C vr '" 0.001127 mllkg

V," 0. 19444 mJ/kg


'"' v , - vr - 0. 1933 m1lkg

Aru. Aru.

2.1387 U/kg K $, " 6.5865 kl/kg K $r, " .I', - .l'r= 4.4478 kl/kg K , " h, - h(- 2015.3 kJ/kg hr
$( '"

Example 9.2 Saturated steam has an entropy of6.76 kllkg K. What are its pressure, temperature, spec ific volume, and enthalpy?

Solution In Table A.I (b). when .l'," 6.76 kl/kg K

v .-

p '" 0.6 MPa,

t = 158.85C 0.3156 m'lkg, and II, '" 2756.8 kJ/kg


Example 9.3 Find the Clldudpy and enlropy or steam when the pressure is 2 MPa and the specific volume is 0.09 m1lkg.

Solution In Table A.l(b), when p .. 2 MPa, vr = 0.001177 m1/kg and VI .. 0.09963 m1lkg. Since the given volume lies betweenvrand VI' the substance will be a mi xture or liquid and vapour, ami the state will be within the vapour dome. When in the two-phase region, the composition orthe mixrure or its quality has to be evaluated first. Now

0.09 "" 0.001177 + x (0. 09963 - 0.001177)



X " 0.904 or 90.4% 2 MPa, h f " 908.79 and hr. " I 89{).7 kJJkg Sf= 2.4474 and sr. = 3.8935 k1Jkg K II - lIr + x hr ... 908.79 + 0.904 x 1890.7 .. 2618.79 kJJkg


s "' sr+xsr.
= 2.4474 + 0.904 x 3.8935 5.9534 kJJkg K


&ample 9.'

Find the enthalpy, entropy, and volume of steam at 1.4 MPa,

Solution Alp - 1.4 MPa, in Table A.I(b), tOOl 195.0FC. Therefore , the state of steam must be in the superheated region. In Table A.2, for propenies of superheated steam, at 1.4 MPa, 350"C V "" 0.2003 m'Jkg h " 3149.5kJlkg s "" 7. 136OkJJkgK and at 1.4 MPa, 400C u = 0.2178 m3Jkg h '" 3257.5 kJJkg s ..., 7.3026 kJJkg K :. By interpolation V '"' 0.2108 mlJkg at 1.4 MPa, 380C 11 3214.3 kJJkg S - 7.2360 kJJkg K

u.mple 9.5 A vessel of volume 0.04 m' contains a mixture ofsaturated water and saturated steam at a temperature of 250C. The mass of the liquid present is 9 kg. Find the pressure, the mass, the specific volume, the enthalpy, the entropy, and the internal energy.
From Table A. I(a), at 250"C P.., '"' 3.973 MPa vr" 0.00 12512 m'lkg, v. - 0.05013 m'Jkg h r " 1085.36 kJlkg. hr. - 1716.2 kJlkg Sf 2.7927 k.JJkg K, sr, " 3.2802 kJJkg K Volumeofliquid, Vr'" mr vr " 9)(0.0012512 - 0.01l 26ml VolumeofvapoUI, V." 0.04 - O.o!126 .. 0.02874 :. Massofvapour

m '



m." -;.- = 0.05013 '" 0.575 kg

3M=:. Total mass of mixture,

m "' m{ + m, '" 9 + 0.575 " 9.575 kg

Quality of mixture, 0.575 .. 0.06 9.575
V "


v{+ xvr.

- 0.0012512 + 0.06 (0.05013 - 0.0012512) - 0.00418 m1/kg

'" 1085.36 + 0.06 x 1716.2 .. 1188.32 JU/kg
s ~ sr+xsr A~.

.. 2.7927 + 0.06 x 3.2802 .. 2.9895 lcl/kg K .. 1188.32 _ 3.973 x 101 x 0.00418 "" 1171.72 JU/kg ur '" 1080.39 and ur, '" 1522.0 lcl/kg


u "' h-pv


Also, at 250C,

u - u,+xu,.
... 1080.39 + 0.06 x 1522 ... 1071.71 JUlkg

Example 9,6 Steam initially at 0.3 MPa, 250C is cooled at constant volume. (a) At what temperature will the steam become saturated vapour? (b) What is the quality at 80e? What is the heal transferred per kg of steam in cooling from 250"C to BOe? Solutio" At 0.3 MPa, lUI " 133.55C Since t > 1_ the slale would be in the superheated region (Fig. Ex. 9.6). From Table A.2, for properties of superheated steam, at 0.3 MPa, 250C v '" 0.7964 ml/kg h '" 2967.61c1/kg

'''---',-'--0.3 MPa

3 ., C 2

Fig. U. 9.6




V , '" 0.8919, l ... " 120"C


v." O.n06, tAt " 125"C

Therefore, when v, '" 0.7964, 'u" by linear interpolation. would be 123.9. Steam would become saturated vapour at I ~ 123.9"C AIU. (a) At 80"C, vr - 0.OOI029 mllkg. v. .. 3.407 m)lkg.
hr '"' 334.91 kJlkg, hr .. 2308.8 kJlkg,pw " 47.39 kPa
VI - V2 "

0.7964 mllkg .. v tBO'C + X2V{c8O'C '" 0.00 1029 + Xl (3.407 - 0.001029)

x .. 0.79539 .. 0.234


An..!". (b)

h 2 " 334.91 + 0.234 x 2308.8 '" 875.9 kJlkg h z '" 2967.6 k.1lkg
From the fmt law of thermodynamics

d"Q - du + pdv
(d"Q) .. " du QI .Z "'- UZ-UI - (h2 - P2V2)-(hl-PI VI) '" (h2 - h i) + V(PI -pi) '" 875.9 - 2967.6) + 0.7964 (300 - 47.39) =2091.7+201 .5 "'- 1890.2 kJlkg

An..!". (c)

Esample 9.7 Steam initially al 1.5 MPa, 300"C expands reversibly and adiabatically in a steam turbine to 40"C. Determine the ideal work output of the rurbine per kg of stearn.

Solution The steady flow energy equation for Ibe control volume, as shown in Fig. Ex. 9.7. 1, gives (other energy terms being neglected) h l - h2 +W

W - h l - h2

..d-+f-,------------------1.5 MPII


i ,.O"C

~ c .s.

Ag. Es.. 9.7.1


30ti=Work is done by steamal the expenseofa fal in ilSenthaipy value. The process is reversible and adiabatic, so it is isentropic. The process is shown on the 1-5 and n-s diagrams in Fig. Ex. 9.7.2. From Table A. f(a), at 40C
P"I "" 7.384 kPa. 3, "" 0.5725, and3f. - 7.6845 kJ/kg K



167.57, and h,, " 2406.7 kJiKg

Alp - 1.5 MPa,' - 3(')()oC, from Ihe tabulated prope.tiesofsupemeated steam (Table A.2) 51"" 6.9189 kJllr.g K

hI - ~p.6 kJ/kg
, 300"C

- .
Fig. &. 9.7.2



51 = 5l 6.9 189 .. 5,+ X2 4(l'C .. 0.5725 + Xl X 7.6845

$ "


= 6.3464 _ 0.826 Of 82.6%


hl .. h,4O"'C + x 2 h,ro"C .. 167.57 + 0.826 x 2406.7


21 52.57 kJ/kg

W - h l - hl =3037.6 - 2152.57
.. 885.03 kJ/kg


Example 9.8 Steam at 0.8 MFa, 250C and flowing al the rate of l kg/$ passes into a pipe clllT)'ing wet steam at 0.8 MFa, 0.95 dry. After adiabatic mixing the fl ow rate is 2.3 kg/soDetermine the condition of steam after mixing. The mixture is now expanded in a frict ionless nozzle isentropically to a pressure of 0.4 MPa. Determine the velocity of the steam leaving the nozzle. Neglect the velocity of steam in the pipeline.

Solution ,figure Ex. 9.8.1 gives the flow diagram. w2 " 110') - WI .. 2.3 - 1.0 " 1.3 kg/s



p, 0.8MPa 250 ' C ...............
Ill, '<1 k(;s


_ ........

P1.. 0.8 MPa / ..,.




ril]. 2.3 kWS

Fig. U. 9.8.1
The energy equation for the adiabatic mix ing of the two streams gives

W,ht+W2hl - wlhJ
At 0.8 MPa, 250C, hi = 2950.0 kJ/kg At 0.8 MPa, 0.95 dry


hl = hr+ 0.95 hr,

= 721.11

+ 0.95)( 2048.0

"' 2666.71 kJ/kg :. From Eq. (9.8.1) 1 )( 2950 + 1.3)( 2666.71 = 2.3)( h] h) ,.. 2790 kJ/kg Since

(h,lo.8 MP. '"' 2769. 1 kJ/kg and h] > h 8' the stale must be in the superheated region. From the steam tables, when p - 0.8 MPa, t = 200C h = 2839.3 kJ/kg

By linear interpolation

0.8 MPa, I..,'" 170.43C 2769.1 kJ/kg 179"C


I) '"

: . Degree of superheat '" 179 - 170.33 '" 8.57C :. Condition of steam after mixing - 0.8 MPa, 179C The energy equation for the nozzle gives

hl"h.+-' 2 since V1 - - velocity nfsteam in the pipeline '" 0 Steam expands isentropically in the nozzle to 0.4 MPa. By interpolation. s] "" 6.7087 kJ/kg K = S4 6.7087 '" 1.7766 + x.)( 5.1193 x4 " 0.964 h4 ,. 604.74 + 0.964 x 2133.8 - 2660 kJ/kg




v! x H,3 = 2 (n) -

h4 ) = 2

x 130 = 260

V4 - .ff6 x 100 '" 509.9 mls An.!. The processes are shown 00 the h- .! and T-.! diagrams in Fig. Ex. 9.8.2.

O .8MPa

' 5O'C


"\ 2\
O.8MPa\ \

3 119"C

,, " ,'



-,.J .
FIg. EL 9.&.!


bample 9.9 Steam flows in a pipeline at 1.5 MPa. After expanding to 0.1 MPa in a throttling calorimeter, the temperature is found to be 120C. Find the quality of steam in the pipeline. What is the maximum moisture al L5 MPa that can be detennined with this set-up if at least 5C of superheat is required after throttling for accurate readings? Solulion At stale 2 (Fig. Ex. 9.9). when p ., 0.1 MPa, t .. 120C by interpolation




FIg. EL 9.9


hl .. 2716.2 kJlkg. and lit p " 1.5 MPa hr " 844.89 and hr. " 1947.3 kJlkg h. - h l hn.5MI'Io + x.h ra . iM P, .. h2 844.89 + XI x 1947.3 - 2716.2

x .. 1871.3 = 0.963
1 1947.3 Whenp " 0.1 MPa and t oo 99.63 + 5 - 104.63C




h) " 2685.S kJlkg hJ .. h~ 2685.5 " 844.89 + x 4 X 1947.3

x~ .. 1840.6 E 0.948 1947.3 The maximum moisture that can be dctennioed with this sel-up is only 5.2%. All".

Eu.mple 9.10 The following data were obtained with a separating and throttling calorimeter: . Pressure in pipeline 1.5 MPa 0.1 MPa, I JOoC Condilion after lhronling During 5 min moisture collected in the separator 0.150 litre al 7Goe 3.24 kg Steam condensed after throttling during 5 min Find the quality of steam in the pipeline Solution As shown in Fig. Ex. 9.IO, at 0.1 MPa, !loce hJ " 2696.2 kJ/kg Now h) " h2 " hn .'Mh + X2hrillsMh or 2696.2 " 844.89 + X2 x 1947.3



FIg. EL 9.10


1851.3 1 - 0.955 1947.3 If "'1 .. mass of moisture collected in sepanUor in 5 min and 1112 .. mass of steam condensed after thronling in 5 min.


310=- 0.1462 kg m2 - 3.24 kg

x _ 0.955 x 3.24 = _ 3,_ 1_ .. 0.915 A~, 1 0.1462 + 3.24 3.3862 Example 9.11 A steam boiler initially contains 5 ml or steam and 5 ml or water at 1 MPa. Steam is taken out at constant pressure until 4 m3 orwater is left. What is the heat transrerred during the process? Solution At 1 MPa, Or'" 0.001127, and v. '" 0.1944 mJ/kg hi'" 2778.1 kJ/kg ur = 761.68, = 2583 .6 kJ/kg uri = 1822 kJ/kg The initial mass or saturated water and steam in the boiler (Fig. Ex. 9.11).

u ,

*"+ ::

0.00~127 + O.l!44 - (4.45 x 10)+ 25.70)kg


" ,... {.I

Fig. Ex. 9.11

where suffix/rerers to saturated water and suffix g refers to saturated vapour. Final mass or saturated water and steam

O.OO~ 127 + O.J~

.. (3.55 x 10) + 30.80)kg

Mass orsteam taken out or the boiler (mJ - (4.45 x 10) + 25.70) - (3.55 x 10) + 30.80) - 0.90 x 1<Y - 5.1 - 894.9kg Making an energy balance, we have: Initial energy stored in saturated water and steam + Heat transrerred rrom the external source " Final enCT8Y stored in saturated water and st~ + Energy leaving with the steam.


Prvpnliu of Purr Surullmru

- = 311

assuming that the steam taken OUI is dry (x '" I) or 4.45 X 10 l x 761.68 + 25.70 x 2583.6 + Q '" 3.55 x IW x 761.68 + 30.8 x 2583.6 + 894.9 x 2778.1 or Q = 894.9 x 2778.1 - (0.90 x IOl) x 761.68 + 5. 1 x 2583.6 '"' 2425000 - 685500 + 13 176 - 1752,676 kJ .. 1752.676 MJ


Enmple 9.12 A 280 mm diameter cylinder fitted with a frictionl ess leakproof
piston CODlains 0.02 kg of steam at a pressure of 0.6 MPa and a tempemture of 200C. As th e piston moves slowly outwards through a distance of305 mm, the steam undergoes a fully-resisted eltpansion during which the steam pressure p and the steam volume Vare related by pV~ z constant, wheren is a constant. The final pressure of the steam is 0.12 MPa. Detennine (a) the value ofn. (b) the work done by the steam, and (c) the magnitude and sign of heat transfer.

Since the path of expansion (Fig. Ex. 9.12) follows the equation pVD _ C
P1Vln = PlV~

pV- - c

- --

Fig. E... 9.12

Taking logarithms and arranging the tenns log.E1...

n -~


Now, at 0.7 MPa, 200C, from Tables A.2 1'1 = 0.352 mJlkg hI'" 2850.1 kJlkg :. Total volume, VI' at slate 1 - 0.352 x 0.02 _ 0.00704 m l Displaced volume _


d1 }




- .!. X (0.28)2 X 0.305

4 - 0.0188m l :. Total volume Vz after expansion - 0.0188 + 0,(10704 - 0.02584 m1

log 0.6
0.12 ~ '" 1.24 log 0.02584 log 3.68 0.00704 Work done by steam in the expansion process
11 -

AIlS. (a)

_ ') pdV ..


J v,

p,~ ,-

P2 V2


6x 10' N / m2 x 0.00704 m l -1.2 x lOS N/ m l x 0.02584 m J 1.24 -I 4224 - 3100.8 N m 0.24 - 4680 N m " 4.68 kJ

AIlS. (b)

VI - 0.02584 m

III - 0.02584 .. 1.292 mllkg



lIZ - lIlIl. ' 2M1'11

+ .1'2 vr,o.1lMh

1.292 = 0.0010476 + Xl
X ..


AI 0.12 MFa,


1.291 .. 0.906 1.427 439.3 kJlkg, u," 25 12.0 kJlkg "I " 439.3 + 0.906 (2512 - 439.3) - 2314.3kJlkg h, - 2850.1 kJ/kg

"r -

By the firsllaw

.. h

,-p,lI, "

2850 I

. -

0.6 x 10 x 0.00704 X 100.02

- 2850.1 -2 11 .2 " 2638.9 U/kg

Q' _2 - U2 - U. + W'_2 - m("z - " ,)+ W' _l

.. 0.02 (2314.3 - 2638.5) + 4.68 .. - 6.484 + 4.68 .. - 1.804 kJ

AII.!'. (c)

Esample 9.13 A large insulated vessel is divided into two chambers, one containing 5 kg of dry saturated steam al 0.2 MFa and the other 10 kg of steam,

- = 313
O.S quality al O .S MPa. (fthe partition between the chambers is removed and the steam is mixed thoroughly and allowed to seule, fmd the fmal pressure, steam quality, and entropy chanse in the process.


The vessel is divided into chambc~, as shown in Fig. Ex. 9. 13.1.

At 0.2 MPa,

v. "

Y I .. mlv i ...

VI .. 0.8857 ml/kg 5 X 0.8857

'" 4.4285 ml

......., ,I,
"'-2- 10kg x2"O.8 Pl ;' O.5I.1P.

m, - Skg

x,, 1.0

P, - D.2I.1PII

FIg. EL 9.13.1

AtO.5 MPa,

0z ... vf + XzV,
... 0.001093 + 0.8 x 0.3749 " OJOIOI mllkg
Vz '" III Z V2 '"

:. Total volume,

Y m


10 x 0.30101 ... 3.0101 m1 VI + V2 "" 7.4386 m1 (of mixture)

Total mass of mixture, 111m '" 1111 + 1112 "" 5 + 10 '" IS kg :. Specific volume ofmixlure

By energy balance

. ~=~~-



7.4386 IS

_ 0.496m J /kg
IIIlul + lllzul " IIIJul

At 0.2 MPa,

" , '" hi = 2706.7 kJ/kg u l "" hi - PIOI :: 2706.7 kJ/kg ... 640.23 + 0.8 x 2108.5 .. 2327.03 kl/kg u2 ~ hz - P2 v2 :: "1 '" 2327.03 kI/kg

hl ... hr + .12 hfa

h ... h

S x 2706.7 + 10 x 2327.03 IS

= 2453.6 kJ/kg :::: ul

Now for the mixture hl ... 2453.6 kJ/kg .. u l


. 1


&sir "nd Appfitd 77tmnlldyrwmia

v1 .. 0.496 m1/kg From the Mollier diagram, with the given va lues of h and v, point 3 after mi xing is fixed (Fig. Ex. 9.13.2).
XJ -

0.870 s] " 6.29 kJ/kg K



v, .

0 . 96 ml!l<g

PJ. 3.5 bar

- Pl '" 3.5 bar

S4 "' sj4l.l.W'& '"

Fig. Ex. 9.13.2


7.1271 kJ/kg K

Sl ""SIQ.' MP& + O&rtjO-lM P"

'" 1.8607 + 0.8 x 4.9606 = 5.8292 kJ/kg K Entropy change during the process
- mj s] - (m] s ]

+ ml.!'2)

15 x 6.298 - (5 x 7. 1271 + 10 x 5.8292) - 0.43 kJ/kg

Example 9.14 Steam generated al a pn:ssure of 6 MPa and a lemperature of 400C is supplied to a turbine via a throUle valve which reduces the pressure to 5 MPa. Expansion in th e turbine is adiabatic to a pressure of 0.2 MPa, the isentrop ic efficiency (actual enthalpy dropiisenU"Opic enthalpy drop) being 82%. The surroundings are at 0.1 MPa, 20C. Determine the availability of steam before and afier the throttle valve and at the turbine exhaust, and calculate the specific work output from the turbine. The K.E. and P.E. changes are negligible. Solution Steady flow availability t;I is given by
- Zo) 2 where subscript 0 refers to the surroundings. Since the K.E. and P. E. changes arc negligible t;l1 - Availability of steam before throttling
- (h I -ho) - ToCs] -so)

I = (h - hg) - To($ -,fo) + J..V~ + g(Z


At 6 MPa, 400C (Fig. Ex. 9.14)

hI'" 3 177.2 kJlkg sl ~ 6.5408 kJlkS K

6 MPa. 400"C 6MPa 5MPa


Steam turbine

0.2 MPa


Fig. Ex. 9.1-4

So '"

ho = 83.96 U/kg
!p[ ..

0.2966 kJlkg K (3177.2 - 83.96) - 293 (6.5408 - 0.2966)


- 3093.24 - 1829.54 - 1263.7 kJlkS Now h[ .. hl' for throttling At h - 3177.2 kJ/kg and p " 5 MPa, from the superheated steam table f 2 - 39Q"C } $2 - 6.63 kJ/kg K by linear interpolation Ifz '" Avai lability of steam after throUling '" (h z - ho) - T,jh - so) '" (3177.2 - 83.96) - 293 (6.63 - 0.2966) '" 3093.24 - 1855.69 .. 1237.55 kJ/kg Deerease in availability due \0 thronling

.. If! - Ifz " 1263.7 - 123755 - 26.15 kJ/kg

S2 xl

= slo "" 6.63 '" l.BOI

+ Xl. (7. 1271 - 1.530 1)

5.5970 hl ... 504.7 + 0.9112 x 2201.9 - 2511.07 kJ/kg hz - hl - 3 177.2 - 251 1.07 " 666.13 kJ/kg hz - hj = h;,(h l - hl .) "" 0.82 x 666.13 = 546.2 U/kg

=~= 0.9 112

316=h} - 2631 kJlkg '" 504.1 +x2 x 2201.7

x _ 2126.3 - 0.966
2201.7 1.5301 + 0.966 x 5.597 - 6.9368 \If} '" Availability of steam at turbine exhaust - (h)- ho) - TrJ.h -So) - (2631 - 83.96) - 293 (6.~368 - 0.2966) - 2541.04 - 1945.58 ., 601 .46 kJ/kg
S} -

Specific work output from thc turbine

'" h2 - hl ., 3117.2 - 2631 ... 546.2 kJ/kg

The work done is less than the loss of availability of steam between states 2 and 3, beeause of the irrevenibility accounted forby the isentropic efficiency. Esample 9.15 A steam turbine receives 600 kglh of steam at 25 bar, 350C. At acertain stage of the turbine, steam at the rate of 150 kglh is extracted at 3 bar, 200C. The remaining steam leaves the turbine at 0.2 bar, 0.92 dry. During the expansion process, there is beat transfer from the turbine 10 the sUlJOwl(ling5 al tbe rate of 10 kJ/s. Evaluate per kg of steam entering the turbine Ca) the availability of steam entering and leaving the turbine, (b) the maximwn work, and (c) the irreversibility. The atmosphere is at 30C.

Solurion At 25 bar, 350c C

hI - 3125.87kJ/kg
sl - 6.8481 kJlkg K

ho " 125.19 kJlkg

"2 '" 2865.5 kJ/kg

AI 0.2 bar {0.92 dry)

So" sDQ"C ~ 0.4369 kJ/kg K

sl - 1 .3 115kJIkgK h r - 251.4kJlkg ht, ... - 2358.3 kJ/kg Sf = 0.8320 kJ/kg K '5, .. 7.9Q85 kJlkg K It) ... 2S1A + 0.92)( 2358.3 - 2421.04 kllkg s) - 0.8320 + 0.92)( 7.0765 - 7.3424 kJlkg K

The states ofslcam are shown in Fig. Ex. 9.15. <a) Availability ofstcam entering the turbine

'1'1 "" (hi - hJ - To (Sl -sol "" (3125.87 - 125.19) -303 (6.848 1 - 0.4369) AIlS. '" 3000.08 - 1942.60 - 1057.48 kJ/kg Availability of steam leaving the turbine al stale 2, '1'2 "" (liz - h o) - TO (S2 - so)

-== 317
m,_600~ p,- 25 bar, I, _ 35O"C

....... W

l kg

0.25 kg

- .so ':::LJ' " iii, ~. 0.2 ,, Xl - 0.92

0.75 kg

kglh bar

Fig. b. 9.15

.. (2865.5 - 125.79) - 303 (7.3115 - 0.4369) .. 2739.71 - 2083.00 " 656.71 kJ/kg Availability ofsleam leaving the turbine at stale 3,

'1') .. (h) -


- To (s3 - so) " (2421 .04 - 125.79) - 303 (7.3524 - 0.4369)

.. 199.85 kl/kg (b) Muimum work per kg of steam entering the turbine Wm- " 'f'l ~

J 'l'l--'I'J .. 1057.48 - 0.25x656.7 1-0.75x 199.85


'" 743.41 kJ/kg (e) Irreversibility


/ = TO<WlSl + wlsl-w l Sl) - Q ,. 303 (ISO x 7.3115 + 450 x 7.3424 - 600 x 6.8481) - (- 10 x 3600)

.. 303 ( 1096.73 + 3304.08 - 4 108.86) " 36000 .. 124,460.85 kJlh '"' 124.46 1 MJIh " 124.461 X 103 = 207.44 kJ/kg 600

&ample 9.16 Detennine the exergy of (a) 3 kg of water at I bar and 90C, (b) 0.2 kg of steam at 4 MPa, 500 0 e and (e) 0.4 kg of wet steam at 0. 1 bar and 0.85 quality, (d) 3 kg of ice at I bar - lO oe. Assume a dead state of I ~ar and 300 K. Solution AI the dead state of I bar, 300 K., uo" 113.1 kJ/kg, 11 0 " 113.2 kl/kg K. va " 0.001005 m1/kg, so ... 0.395 kJlkg Exergy of the system:

uo+PaVo- Tolo =ho- Tolo .. 113.2 - 300 x 0.395 "' - 5.3 kJ/kg

318=(a) For water at I bar, gooC

u - 376.9 kJlkg. h - 377 kJlltg, v - 0.001035 mJlltg


1.I93 kJlkg K.


p : Po. u +Pov - ToS :u+pv- Tos =h - Tos '" 377 - 300 x 1.1 93

- 19.1 kJlkg ",, '" 3[1 9.1 - (- 5.3)] '" 3 x 24.4 Ans. "" 73.2 kJ (b) At P '" 4 MPa, t .. 500Q C 1/ " 3099.8, h "" 3446.3 kJlkg, v "" 0.08637 mJlkg s .. 7.090 kJlkgK. 1/ + Pov - ToS " 3099.8 + 100 x 0.08637 - 300 x 7.090 '" 981.4 kJlkg 4' = 0.2 [981 .4 - (- 5.3)J '" 197.34 kJ Ans. (c) At 0.1 bar, 0.85 qual ity, 1/ - 192 + 0.85 x 2245 " 2100.25 kJlkg h ~ 192 + 0.85 x 2392 = 2225.2 kJlkg s .. 0.649 + 0.8 5 x 7.499 = 7.023 kJlkg K V " 0.001010 + 0.85 x 14.67 .. 12.47 mllkg u +Pov - TO'f " 2 100.25 + 100 x 12.47 - 300 x 7.023 - 1240.4 kJlkg 9 " 0.4[1240.4 - (- 5.3)] .. 498.3 kJ AIlS. (d)Sincep = po, Hel!1;c,


+ prf..V - V.J - TotS - Sol .. JI - Ho- Vrp - Po) - To(S - So) . - m[(h-hol - Trf..s - so)]

v - vo

At 100 !cPa, - IO"C, h = - 354.1 kllkg and s "" - 1.298 kllkg K

.. 3[- 354. 1 - 113.2 - 300 (- 1.298 - 0.0395)]

- 81.2kl.


Example 9.17 A flow of hot water III 90C is used to heat relatively cold waler at 25C 10 a temperature of50 C ilH heal exchanger. The cold wa ter flows at lhe rate of I kg/so When the heal exchanger is operated in the paral lel mode, th e exit temperature of the hot waterstrearr. must not be less than 6(}C. In the counterflow operation. the exit temperature of hot water can be as low as 35(. Cc;mpare the second law efficiency and the rate of exergy destruction in the two modes of 'Operation. Take To = 300 K.
Given: Ihl : 9O"C, ,'1 = 25( , 1<1 = 60(,

m e= I kg/s, To '" 300 K.


The two modes of operation of (a) parallel flow and (b) counterflow are shown in Fig. Ex. 9.17.

- "
Fig. h. 9.1 7

In parallel flow mode (a). fhl '" 60C. Neglecting any heat loss.

m h Ch(lh, mh (90 -

I h) '" ril e Ce(tel - Ie, ) 60) '" 1(50 - 25)

rilh '" 0.833 kgls In counterflow mode, 'h2" 35C, ri' h (90 - 35) " 1(50 - 25) ril b "



0.454 kgls

Thus, th e counterflow arrangement uses sign ificant ly less hOI water. Assuming that the hot water stream on exi t from the heal exchanger is simp ly dumped in to the drain, the exergy fl ow rate of the hot water stream at entry is . eonsidered as the exergy input rale to the process.
an "" ril h[(h , - hol - To(s, - so)1 AI 300 K or 27C. ho = 113 .2 kJlkg and So " 0.395 kJ/kg K AI 90C, hi '" 376.92 kJlkg, it - 1.1925 kJlkgK

ar, - 0.833 1(376.92 - 113 .2) - 300 (1.1 925 - 0.395)1

= 0.833 (263.72 - 239.25) "" 20.38 kW

Para llel flo w: At 60C, At 25C. AI 50' C, Rale of exergy gain:

h2 "' 251.13 kJlkg.

h) "

104.89 kJlkg, h~ = 209.33 kJlkg,

sl = 0.8312kJlkg K i l '" 0.3674 kJ/k g K s~ = 0.7038 kJlkg K



320=.. 1[(209.33 - 104.89) - 300(0.7038 - 0.3674)) - 104.44 - 100.92 - 3.52 kW (1111),


- 0.172 or 17.2%

Rate of excrgy loss by hot water: '"' "'h[(11 1 - II~ - To(sl - s~l .. 0.833 [(376.92 - 251 .13) - 300( 1.1925 - 0.8312)] - 0.833 (125.79 - 108.39) '" 14.494 kW Rate of irreversibility orexergy destruction: '" 14.494 -3.52 '" 10.974 kW If the bot water stream is not dumped to the drain, 11u. ,"


'" 0.243


nl '" 146.68 kJ/kg, .1'2 '" 0.5053 kJlkg K Rate of exergy gain of cold water '" "'b [(II, - 113) - Tn(s, - Sl ) ~ 3.52 kW (same as in parallel flow) Rale ofexergy input (if exiting hotwatcr is dumped to the surroundings) ... 0.454 (263.72 - 239.25) ... lUI kW 11u.c'"


... 0.3168 or 31.68~.

Rate of exergy loss of hot water: ... '"b[(nl - II~ - TO(sl -s~) ... 0.454 [(376.92 - 146.68) - 300{1.l925 - 0.5053)] ... 0.454 (230.24 - 206.16) - 10.94 kW

q" ,," 3.52 ,. 0.3217 or 32.17i'/

. '10.94 Rate of irreversibility or exergy destruction: ... 10.94 - 3.52 '" 7.42 kW The second law efficiency for the counterflow arrangement is significantly bigher and the rate of irreversibility is substantially lower compared to the parallel flowam.ngement. Example 9.18 A small geothermal well in II remote desert area produces 50 kglb of saturated steam vapour at 150C. The environment temperature is 45C. This geathennal steam will be suitably used to produce cooling for bomes at 23C. The steam will emerge from this system as saturated liquid at I aim. Estimate the maximum cooling rate that could be provided by such a system.



Solution The energy balance oftbe control volume as shown in Fig. Ex. 9.18

The cnlrOpy balance is:

SJOa - [~: +WSl]-[~+WS!]

where Tis the temperature maintained in the homes.


FIg. EL 9.18

Solving for Q,

Q ..

w[(hl-TOSI )-(hl-TOS2))-TOS.... (ToIT) I

By second law. SF' > O. . Therefort, for a given discharge state 2, the maximum Q would be


_ w(., -b,) (TaIT) I

Tt .. Isooe .. 423 K, satW'8ted vapour hI" 2746.4 kJJkg " I .. 6.8387 UJkg K State-2: T2 - 100Ge c 373 K. saturated liquid hz - 419.0kJJkg '2 " 1.3071 kJJkg K . So,since To - 318 K, h i = hI - T&I"I = 2746.4 - 31S x 6.S387 = S7 1.7 kJJkg hI "" h1 - ToYl = 419.0 - 318 x 1.3071 = 3.3 kJ/kg

Q "'

SOx (S71.7-3.3) = 3.S2x 10~ kJlh (3 18/ 296) 1


"' 106 kW


9.1 9.2 9.3 9.4 What is a pun: substance? What arl: satumtion mtes? What do you understand by tripl e point? Give the pressun:and temperatun: of water at its triple point. What is the critical state? Explain the tennscritical preSSU rl:, critical tempel1lturl: and critical volume of water? What is normal boiling point. Draw tbe phase equilibrium diagram on ~v coordinates for a substance wbicb shrinks in \olume on melting and then for a substance wbich expands in \olume on melting. lrldicate thereon the relevant constant property lines. Draw the phase equil ibrium diagram for a pUrl: substance on ~T coordinates. Why does the fusion line for water have negati ve slope? Draw the phase equilibrium diagram for a pure substance on T- $ plot with rl:levant constant property lines. Draw the phase equil ibrium diagram for a pUrl: substance on h- $ plot with rl:1cvant constant property lines. Why do the isaban on Mollierdiagram diverge from one another? Why do isothenns on Mollier diagram become horizontal in the superheated rl:gion at low pressures? what do you understand by the degre<."' ofsupe rhe:lt and the degree ofsubcooling? What is quality of steam? What arl: the diffm:nt methods of measurement of quality? Whyeanoot a throttling calorimeter measUrl: the quality if the steam is very wet? How is the quality measured then? What is the principle of operation of an electrica l calorimeter?


9.7 9.8 9.9 9.10 9.11 9.12 9. \3 9.14 9.15

9.1 Complete the fo!lowing tab le of propertie! for I kg of water (liqUid, vapour or mixture).
p (oor)


(I1I JIkg)


Superheat ("C)

h IkJlkg)

(t//kg K)


2S.22 0.001044

419.04 6. 104

(0) (d) (0)

10 320 0.4646 0.4400

I, )

(i) (j)


20 IS SO

3445.3 7.2690


f"IoprrlilJ of p.,.., SubSldlU" 9.2








(D) A rigid vessel of \'olume 0.86 m1 conuins ! kg of sleam at a pfe~sun: of 2 bar. E"aluate the spec ific volume. lempenlture, dryness fl1lclion, inlernal energy, enthalpy, and emropy of Sleam. (b) The steam is heated to raise its temptnlture to ISOC, Show the process on a sketch oftbe: p-v diagram. and evaluate Ihe pressure. inc:rcase in emllalpy, incn:asc in internal energy. increase in enlropy of steam. and Ihe heal tr'II.llsfer. Evalu:lle 31so the pressure at whkh the steam becomes dry saturated. ..111$. (a) 0.86 mllkg, 120.2J"C, 0.97, 2468.54 kJlkg, 264054 kJlkg, 6.9592 kJlkg K. (b) 2.3 bar. 126 kJlkg. 106.6 kJlkg. 0.2598 kJlkg K. 106.6 kJ/K. Ten kgofwaterat45 C is healed al a constant pn:SI;Un: ofiO barunlil it becomes superheated "apout al 300C. Find the changes in volume, enthalpy, internal energy andentropy. An.r. 2.569 ml. 28627.5 kJ. 26047.6 kJ, 64.842 kJlK Waler at 40"<: is continuou'sly spmyed into a pipeline currying 5 tonnes ofstcam at S bar, JOOC per hour. At a section downstream where the pressure is 3 bar, the quality is to be 95%. Find the nlte ofwBter spray in kglh . ..Ins. 912.67 kg/b A rigid vessel contains I kg ofa mixture ofsall.lmled water and sallmued steam a,t a pressure of 0,]5 MPa. Ylhen the miuure is heated, the state passes through the critical point. Th:termine (a) the volume of vessel (b) the mass of liquid and of vapour in the vesse l initially, (c) the temperature of the mixture when the pn:ssure has risen to 3 MPa. and (d) the hcatlnlnsfer fl:quircd to produce the fIDBI SUte (c). AIL!. (a)0.OO3IS!i ml, (b) 0.9982 kg. 0.0018 kg. (e) 233.9C, (d) 581.46 kJlkg A rigid dosed tank of volume 3 ml contains 5 kg of wet steam at a pressure of 200 kPa. The tank is heated until the steam becomes dry $lItumted. Determine the ftnal pressure and the heat transfer to the tank. An.l'. 304 kPa, 3346 kJ Steam flows through a small lurbine at the I1IIC of 5000 kgIb entering al IS bar. 300C and leaving at 0. 1 bar with 4% moisfUte, The slearn enten at 80 mls at a point 3 m abo\'e the dili-ChDrge and leaves at 40 mfs. Compule the shaft po"'er assuming lItat the device is adiabatic bot considering kinetic and po1cmial energy changes. How much error "'ould be made if these ICons were nc:glec lcd? Calculate the diameters of the inlet and di!lCharge tubes. AM. 765.6 kW, 0.44%, 6.] I em, 78.9 em A r;ample of Gleam from a bai]eT drutn at 3 MPa is PUI through a throltling calorimeter in which the pressun: and tempenlture afl:,found 10 be 0.1 MPa, 1200c. Find the quality or the s.ample lakcn from the boiler.
An$.0.95 ]

9.9 II is desired to measure the quality of wet steam at 0.5 MPa. Thcqualiry ofsteam is expected to be not more than 0.9. (a) Eli;plain why a throttling calorimeter 10 atlD05phcrie pressure "'ill DOt SCI'\'e the purpose. (b) Will the use ofa stpllf1lting calorimeter. ahead orthe throltlin8 ca lorimeter, serve the purpose, ifat beSt 5 Cdegrec ofsuperba.t is dcsilllble al tbe: end of

32.f=throttling? Wha! is !he minimum dryness fractiO/l required at !he exit of the 5epafating calorimeter to satisfy Ibis conditiO/l? 9.10 The following observations were recorded in an u.periment wilh a combined . separating and throttling calorimeter:: Pressure in !he steam main bar Mass ofWllIeI' dr.ined. from the separator --0.55 kg Mass of5lClm conderued after passing through Ihe throttle valve --4.20 kg Pressure and ICmperalllnl after throttling - I bar, 120C EvalWde tile dryness fraction oflbe l leam in Ihe main, and stale with reasons. wbctber the throttling calorimeter aJonc could have been used fot this les!. AM. O.SS 9.11 Steam from an engine e.r.ha1lS1 al 1.25 bar flows steadily througb an electrie caloriJneterandcomes OUiat 1 bar, 11OOC. Thecalorimelerhas two I kWbeaters . and Ihe flow is measured to be 3.4 k& in S mio. Find !he quality in the engine exhaust For the I&IIlC mass flow and pressures, what il the maximum moinurc !hat can be delmllincd if the OUlie1 tcmperalllnl is at least 10SC7 AM, 0.944, 0.921 9.12 Steam expands isenrropicaUy in a nozzle from I Mfa, 2SO"C to 10 kPa. The mana flow rate is 1 kg/$. Find the velocity ofstcam al!be exil from the oozzlt. and Ihe exll area of tbe nouIe. N eg\1 the velocily of lIn!n .II !he inlet 10 the

- I'


9. 13

9. 14

9.1 S


The exhallSl steam ffOll'l !he nozzle f10W$ inlO a condenser and flows OUI as unnted water. The cooling water cnlC1S !he condenser .II 2SC and leaves" 3S"C. Detctmine Ihe IDUlI flow rate of cooling walei'. Ans. 1224 mfl, 0.0101 ml, 47.S 1 kg/s A I'CVCTlIible polytropic process, begins wilh slcam atp, .. lObar, II .. 200C, and ends wi!h pz " I bar. The e x.ponenlll has the value U S. Find !he fmal spec ifIC volume, the final temperature, and the beat ttansfetrcd pc!" kg offluid.. T~1) streams ofsleam, one al2 MPa, 300"C and the other at 2 MPa, 400"C, milt in a slcady flow adiabatie process. The ratcs of flow of !he ""'0 streams ate 3 kg/min and 2 kg/min IapCCtively. Evaluate tbe final temperature of 11K: emerging stream, [f!here is no PH:S$UR: drop due 10 Ihe mixing process. What would be Ihe rate o f incrcasc in !he e ntropy oflhe universe7 This stream wilh a negligible velocity now e xpands adiabatically in I nozzle to a ~ of I kPa. Detcnnine the exit \'elocity of the stteam and Ihe ex it aIel of the noule. 2 AM. 340"<:, 0.042 kJlK min, IS30 mfs, 53.77 em Boiler stcam at g bar. 250"C, reaches the engine control valve througb a pipeline at 7 bar,200"C. II is lhrottIcd to 5 barbefore expanding in the engine to 0.1 bar, 0.9 dry. Detennine per kg of steam (a) the heat loss in the pipeline, (b) the temperature drop in passing Ihrough the Ihrottle valve, (e) the WorkOUIpUI of the enSine, (d) !he entropy change due 10 throttling and (el Ihe Ctltropy change in passing Ihrough the engine. AM. (a) IOS.3 kJ/kg, (b) SC, (c) 499.35 kJlkg, (d) 0. 1433 kJlkg K, (e) 0.36S7 kJlkg K Tank A (Fig. P 9. 16) has a \fOlume of 0.1 m l and contains SICam at 200"C, 10'" 4 liquid and 90% vapour by volume, while taDIc B is evacuated. The valve is !ben opened, and the tanks eventually come to the same p~re, which is found In be


. I


Fig, P 9.15 4 bar. During Ihis proces:5, heat is transferred such that the steam ~mains at 200C. What u the volume of tank B7 Ans. 4.89 m ) Calculate the amount of beat which enten or leaves I kg of steam initially at 0.5 MPa and 2SO"C, when it undergocslhe followin8 processes: (a) It is confined by a piston in a cylinder and is compressed to I MPa and 300"C as the piston does 200 kJ of work on the steam. (O) It puses in steady flow through a device and leaves at I Mfa and 300"C while, per kg of steam flowing through it, a shaft puts in 200 kJ of work. Changes in K..E . and P.E. lin' negligible. (c) It Hows into an evacuated rigid container from a large source which is maintained at the initial condition oftbe marn. Then 200 kJ ohhaft work is tnruferred to Ihe stearn, 50 that its flDal condition is I MPa and 300"C. All.!". (a) - 130 kJ{O) - 109 kJ, and (cl - 367 kJ A sample of weI steam from a steam main flows steadi ly through a partially open valve into a pipeline in which is fitted an electric coil. The valve and the pipelioe are well insulated. The sleam mass flow rates 0.008 kg/a while the coil takes 3.91 amperes at 230 volt'- The main pressure is 4 bar, and the pressure and temperature ofthc Iteam downstream of the coil are 2 bar and 1(,(jC respectively. Sleam velo<:itK-' DUly be MSumed to be negligible . . (.) Evaluate the quality of steam in the main. (O) State, with reasons, whetber an insulated throttlin8 calorimeter could be used for this test. AnJ. (a) 0.91, (b) not suitable Two iosulated Ianks.A and B, are connected by a valvc. TankA has I volume of 0.70 m J and contains steam at I. S bar, 2000C. Tank B has a volume of 0.35 m' and conlains steam at 6 barwith a quality of9O%. The valve is then opened, and the two tanks come 10 a unifonn stale. If the~ is no heal transfer during the process, what is the final pressure? Compute the entropy change of the uni'clK. AIU. 322.6 kPa, 0.1985 kJlK A spherical aluminium v~l has an inside -iiameter of 0.3 m and a 0.62 em lhick wall. The v~1 contaillll water at 25C with aqllDlity of 1%. Thc vesse l is tben belIted until the water iIllIide is saturated vapour. Considering the vessel and wster together as a system, calculate Ihe heal transfer during this procC5S. The density of aluminium is 2.1 gfcm' and its specific heat is 0.896 kJlk& K.. A ..... 2682.82 kJ Steam at 10 bar, 250' C flowing with negligible velocity at the rate 00 kg/min mixes adiabatically with steam al 10 Bar. O.?S quality, flowing also with negligible velocity at Ihe rate of ~ kg/min. The combined stream of steam is tbronled to 5 bar and then expanded isentmpical1y in a noule to 2 bar. Detenninc (a) lbe Slate ofSieam after mixing, (O) the steam after Ihron1ing, (e:) Ihe: in~1\SC






326=in enlropy due 10 thronling, (d) the "clocity of SIC am al the '=Xit from the !lOuie, and (e) the e~il area of.th\:: nozzle. Neglect the K.E. of steam al Ihe inlellO tbe: nozzle. Ans_{a} 10 bar, 0.975 dry, (b) S bar, 0.894 dry, (c) 0.1669 kJlkg K. (d) 540 mls. (e) 1.864 em 2 Steam of 6S bar. 4OQC lea"cs the boiler to enter a Sicam turbine fitted with a throttle governor. At a reduced load. as the goverTlortakesllClion, the p~$Sure of steam is reduced to 59 bar by throttling hefore it is admitted 10 the lUtbinc. Evaluate the availabilities of steam before and after the throttling process and the im:\"cnibility due to it. A mass of wei steam atlelJlperalure 165cC is expanded at constant qualityO.8 10 pressure 3 bar. It is lhen healed al constant pf"t$UfC 10 a degree of superlieat of 66.5C. Find the enlhalpy and entropy elutnges during expansion and during heating. Draw the T-s and h-s diagrams. AliI. - 59 kJlkg, 0. 163 kJlkg K during e~pilllSion and 676 kJlkg, 1.588 kJlkg K during heating Steam enters a lUtbine at a premll"l: of 100 bar and a temperature of 400,,{;. At the exil of the turbine the pressure is I bar and the entropy is 0.6 l /g K gn:atcr than that at inlet. The process is adiabatic and changes in K.E and PE may be negl~ted. Find the work: done by the steam in Jig. Whal is IIIe mass flow rale of 51eam required 10 produce a poweroutpul of I kW? AIlS. 625 JIg. 1.6 kgfs One kg ofstea/ll in aclosed system undergoes a thermodynamic cycle compmed th e following reversible processel: ( 1- 2) The steam initially al 10 bar, 4W. quality is bealed at constant "olume until the pressure rises to 3S bar; (2- 3). It is then e~panded isothermally to 10 bar; (3- 1) It is finally cooled at constant pressure bad to its initial stale. Sketch lhe cycle on T-s coordinates. and ca lculate the work done, the heat transferred, and I~ change of entropy foreach oflbe three processes. Whal is the thmnal efficiency oftbe ~le? AIlS. 0; 1364 kJ; 2.78 1 kJlK. 367.5 kJ ; 404.6 kJ; 0.639 kJlK; - 209. 1 kJ ; - 1611 kJ; - 3.419 kJIK 8.93!~ Detennine lhe excrgy per unit mass for t~ steady flow of each of the following: (a) steam al I.S MPa. 500C (b) air al I.S MPa. 500C (c) water 8t4 MPa. 300 K (d) air at 4 MPa. 300 K (ej air at 1.5 MPa. 300K AIlS. (I ) 1220 kJlkg. (b) 424 kJlkg, (e) 3.SS kJlkg; (d) 316 kJlkg. (e) 232 kJlkg A liquid (cp - 6 kJlkg K) is healed al an approximately constant pressure from 298 K to 90C by pass in g il through tubc:s immer=! in I furnace. The mass flow flIte is 0.2 kg/so Determine (a) the heating load in kW. (b) the exergy prodUC:lion . mte in kW corresponding 10 the tCTDpernture rise oflbe fluid. AIlS. (I) 78 kW. (b) 7.44 kW A flow of hOI water at 80C is used to heat cold water from 20C 10 4S oC in a heat exchanger. The cold water flows at the rate of 2 kg/so When operated in parallel mode. the exit tcmperarure orhot water stream cannOI be less than 55C. while in the counterflow mode. it can be 85 low as 30C. Assuming the








surroundin~ are al 300 K.. compare the second law efficiencies for the IWO modes ofopcration. Water al 9O"C is flowing in a pipe. The pressure ofthc waler is 3 bar, lhe mass flow rale is 10 kgfs. Ihe velocity is 0.5 mls and the elevarion oflhe pipe is 200 m above the exit plane of the pipeline (ground level). Compule (a) !be Ihcnnal exefi)' flux. (b) the prc5SUl"C ucrgy flux, (e) the elefi)' flux from KE, (d) lhe exergy flux from PE, (el total excrgy flux of!be stream. Ans. (a) 260 kW. (b) 2.07 kW, (e) J.2~ x 10-) kW, (d) 19.6 kW, (el 282 kW A cylindCT fined wilh a piston eonlains 2 kg steam al.wo kPa. 400C. Find the enlropy change and the work don.e when the sleam expands to a final pressure of 200 kPa in eaeb of lbe following ways: (a) adiabalically and re\ersibly. (b) adiabatically and irreversibly 10 an ClIuilibriwn temperature of300 C. A...... (a) O. 386.7 kJ, (b) 0.1976 kJlK. 309.4 kJ Steam upands isentropically in a nozzle from I MPa, 2SO"C 10 10 kPa. The sleam flow rate is I kgls. NegleCling lhe KE ofsleam al in ieito the naule, find the velocity of steam al exil from the nozzle and the exit areaoflhc nozzle. Am. 1223 mls. 100 cnr HOI belium gas al 8oo'C is supplied 10 a Sleam generator and is cooled to 4~0C while sen'ing as a heal 5O\II"Ce for the generalion of steam.. Waler enlen !he steam 8enerator al 200 bar, 2~0C and leaves as superheated steam al 200 bar. ~OO"C. The Icmpel1lture of the surroundings is 27'C. For I kg helium, delennme (a) the maximum work lhat could be produced by Ihe beat refTlO\'ed from belium, (b) the mass ofSleam genenued per kg of helium, (e) the a=1 work done in the steam cycle per kg of helium. (d) the nel change for entropy of the uni\erse. and (e) the irreversibility. Take the average c p for helium as ~.1926 kJ/kg K and the properties ofwalCf al inlello the steam generalor as those ofsaluraled waler at





Am. (a) 1202.4 kl/kg He, (b) 0.844 kg HlO/kg He (e) 969.9 kJ/kg He, (d) 0.775 U /(kg He-K), (e) 232.5 k1/kg lie


.. 1,;1'

Properties of Gases and Gas Mixtures

10.1 Avogadro's Law

A mote of a substance has a mass numerically equal to the molecular weight of the substance. One g mol of oxygen has a mas.s of 32 g. I kgmo l of oxygeo _ hJl.s a mass of

32 kg, I kgmn] o(nitrogen has a mass of28 kg, and so nn.

Avogadro's law states that the volume ofa g mol of all gases al the pressure of 760 mm Hg and temperature of OC is the same, and is equal to 22.4 titles. Therefore, I 8 mol ora has a volume of22.4 x IO J em' and 1 kgmole ora gas has a volume 0(22.4 m at nonnal temperature and pressure (N.T.P.). For a certain gas, if m is its mass in kg, and IJ its molecular weight, then the number orkS moles of the gas, n, would be given by



m kg

kgmoJ The motll1' volume, D, is given by

.u ~

.!!!... kgmoles

v- . ml/kg mol
where Vis the total volume or lhe gas in ml.

10.2 Equation of State of a Gas

The functional relationship among the properties. pressure p. molar or specific vo lume v, and lemperature T, is known as an equatioll of S/ale, which may be expressed in the form, f(P,v, T ) .. O

Ifrwo of these properties ofa gas are known; the third can be evaluated from the equation of state. It was discussed in Chapter 2 that gas is ;th c best-behaved thennometric substance be<:ause of the fact that the rotio :of pressure p of a gas at any temperature to pressure p, of the same gas at the triple point, as both p and p, approach zero, approachcs a value indcpenden~ofthe nature ofthe gas. The ideal gas temperature T of the system at whose temperature lhe gas exerts pressure p (Article 2.S) was defined as

.' T "' 273.16 lim J!....

p, .... O p,

(Consl. V)

T - 273.l6 lim .:.. Pp .... o


The re lation betweenpv andp ofa gas may be expressed by means ofa power series of the form


- AP + B'p + c:~ + ...)

! p ... o


where A, 8', C, ClC., depend on the temperature and nature of the gas. A fundamental property of gases is that! lim (fYV) is independent of the nature of the gas and depends only on T. This is shown in Fig. 10.1, where the productpv is plotted againstp for four different gases in the bulb (nitrogen, air, hydrogen, and oxygen) at the boiling point of sulphur, at steam point and at the triple point of water. In each case, it is seen that asp, O,fYV approaches the samc value for all gases at the same temperature. From Eq. (10.1)

limpv - A

Therefore; the constantA is a function oftcmperature only and independcnt of the nature o(the gas.

lim"" (Const.V) - lim E = .limpv p, p, V hm (pv),


pY limpv _ _A I m~= lim -V (C oOSl.p) - \. II; lim (pv), A,


The ideal gas temperature T, is thus r " 273. 16 limp v lim (pv), lim(pv) _ [lim (pv), 273.16 The tcrm within bl1l.ckct is called the universal gas cons/ant and is denoted by


li.. Thus
li. = lim (pv),

( 10.2)

laO=M m (PV) " 58.9 Wire atm/9mo1 p_o sulphur point


_ _ p,81m

" (.,




_ _ 0-





_ _ p.8tm


Fig. to.t FIIr a"1 8M lim {Johu ituUpnuit~1 o/tJu nll/It't ./tJu


8M 11M dtpnu4 ."" Dn T

The value obtained for lim (po), is 22.4 litreatm , ... 0 gmol

R _ ~ = 0.083

litre-atm gmol K

The equation of state of a gas is thus

limpv=RT ,.0
where (10.3)

v is the molar volume.


of G4Jtf orui GIU Muhtru


10.3 Ideal Gas

A hypothetical gas which obeys the law pv RT at aU pressures and ,- ; temperatures is caUed in ideal gas. Real gases do not conform to this equation of state with complete accuracy. As p -+ 0, orT -+ 00, the real gas approaches the ideal gas behaviour. In the equation pv .. RT, as T -+ 0, i.e., t -+ - 273.15C, if v remains constant, p -+ 0, or if p mnains constant, V -+ O. Since negative volume or negative pressure is inconceivable, the lowest possible temperature is 0 K or - 273. 15"C. Tis, therefore, known as the absolute temperature. There is no pennanen! or perfect gas. At atmospheric condition only. these gases exist in the gaseous state. They are subject to liqueficarion Of solidificati on, as the temperatures and pressures are sufficientl y lowered. From Avogadro's law, when p - 760 mm Hg - 1.01 3 X 105 N/m2, T a 273.15 K, and 22.4 mllkgmol

v ..

I. ~"O~13,-X~ I"O';i-X"22",,.4 R=273.15

'" 83 14.3 Nmlkgmol K

= 8.3 143 kJ/kgmol K

Since ii .. Vln. where V is the total volume and n the number of moles oftbe gas, the equation of state for an ideal gas may be written as (lO.4) Also m n ""-

where JJ is the molecular weight

ii pV = m--T p pV - mRT
R = characteristic gas constant = R
Foroxygen, e.g.,

(10.5) (10.6)

R02 " 8.3 143 .. 0.2598 kJ/kg K

For air,

R ... 8.3143 .. 0.287 kJlk K ." 28.96 g

There: are 6.023 x 102l molecules in a g mol ora substance. This is known as Avogadro's number (A). A .. 6.023 X 102 6 moleculeslkgmol


332=In n kg mol es of gas, the IOtal number of molecules. N. are

N " nA n ""NIA

pV=N R T


whereK .. Boltzmann constanl


8314.3 '" 1.38 x 10-23 l lmolccule K A - 6.023 X 10 26

Therefore, the equalion or Slale oran ideal gas is given by

pV - mRT
~ nRT


10.3.1 Sptdfic HetIlI, lfIlmUd Ermo, aM EtIlIuI1PJ 0/11" IdetJl Gtu

An ideal gas nOI only salisfies!.be equation ofstalepv" RT, but ilsspecijic heats
ore colUta .. , also. For real Sasel, lhese vary appreciably with tempenuure, and

little with pressure. The properties ofa substance are related by

Tds ~ du + pdv

d" n .. - - +L...dv T T The internal energy u is assumed to be a function ofT and v, i.e.
u =f(T. v)

( 10.8)

du - (

~;)y dT+ ( ~:)T dv



From Eqs (10.8) and (10.9)

... .L(.E' C) dT+.L[(d") +PjdV TdT TdV T

Again. iet
5 -

( 10.10)

f(T, v)

.. _(.E' C) dT+ (~) dT dVT



Comparing Eqs (10.10) and (10.11)

(;~ 1. = ~(~; 1.



(::), = ~[(::), + p]
Differentiating Eq. (10.12) with respecl totl when Tis constant



T dTdV



Differentiating Eq. (10.13) with respect to Twhen v is constant

a:~T"'td:2;T+ ~ (~~)y - :l ( ~:)T - ~

From Eqs (10.14) and (10.1 5)


rari.W "ravar r aT



(a p )

I (a,) p --r i.W T-r


For an ideal gas

aV T

+p "T(ap) aT ~

,(ap)_R aT

p ) _!i=1'. a (dT v v T


From Eqs (10.\6) and (10.17)


- 0


Therefore, u does not change when v changes at constant temperature. Similarly, if u ... f(T, p), it can be shown that



O . Therefore, u does

nol change withp either, when Tremains constant. u does nol change Wlless Tchanges.

u "'fm


only for an ideal gas. This is known Jl!;Joule 's law. If u -f(T,v)
du -

(~) dT + (....) d, aT~ dVT

Since the last tenD is zero by Eq. (10.18), and by definition


,.(",) aT.
du -c.,dT


The equation du '" c. dTholds good for an ideal gas for any process, wh ereas for any olher substance it is true for a constanl volume process only. Since c. is constant for an ideal gas,

bu oo c.bT
The enthalpy of any substance is given by

h "' u + pv
For an ideal gas

h "" u + RT
Therefore h - [(T) . .only for an ideal gas


dh - du + RdT

Since R is a constant

l!Jt .. bu + R1J.T -=c.lJ.T+R1J.T =(cv+ R)bT

Since h is a function ofTonly, and by definition


,' -(~l aT ,

dh "'-cpdT llh - cp lJ.T

From Eqs (10.22) and ( 10.23)

( 10.23) (10.24)


cp ,", c.+ R ,,-c.- R

( 10.25)

The Eq. dh " cp dTbolds good for an ideal gas, even when pressure changes. but for any oth er substance, this is true only for a constant pressure change. The ratio ofepic. is of imponance in ideal gas computatioos, and is designaled by the symbol y, i.e.

. From Eq. ( 10.25)

(r - 1)c. " R



Cv "' Y~1 IkJlkgK

c-~ P y_1
IfR -


Ii p

issubstitutedinEq. {I0.26)

Cv '" IJCv = (cv)"'" = y


~ I IkJf(kgmOI)(K)


c - IJC - {c\
p p


yli y_1

Cy and c p are the molar or rrwlal specific heats 81 constant volume and at conslant pressure respectively. II can be shown by the classical kinetic theory of gases thallbe values of r arc 513 for monatomic gases and 7/S for dialomic gases. When the gas molecule contains more than two atoms (Le. for polyalomic gases) the value of y may be taken approximately as 4/3. The minimum value of r is thus I and the maximum is 1.67. The value of thus depends only on the molecular structure of the gas. i.e., wbether the gas is monatomic, diatomic or polyatomic having one, two or more atoms in a molecule. It may be noted that 'it and c. of an ideal gas depend only on r andR, Le., the number ofaloms in a molecule and the molecular weight of the gas. They are independent oftemperature or pressure of the gas.

10.3.2 EtUroJI! Clump of an Itkal Gas

From the general property relations Tds '" du + pdv

Tds - dh - vdp
and for an ideal gas. du ... cy dT, dh ... cp dT, and pv '" RT. the entropy change between any two stales I and 2 may be computed as given below
d . _ du + .f.dv

-c dT + R dv T 0
52 - 5 , - Cy

In -

Ii + R 10 -V 2





ds - r-T"dp



336 = -


Jl-Jl - C

In~ - Rln l!l.




R - cp - c.. Eq. (10.29) may be written as

J2-JI - cp ln 2i -cp ln -P2 +cyln P1... 7j PI PI
Vl P' sl-sl=cpln-+cyln ........


Anyone of the three Eqs (10.28), (10.29), and (10.30). may be used for compUling the entropy change between any IWO Slates ofan ideal guo

10.3.3 Rn"sible AtlitJHlk Process

The general property re lations for an ideal gas may be written as
1& - du+ pdll - cy dT+ pdv


Tds ,.. dJJ - vdp '" cp dT - vdp cydT--pdv crdT - vdp

.:f.. c .. y __ ~ cy pdv

For a reversible adiabatic change, ds - 0


(10.3 1) (10.32)

~+r2.. - O P , '" d(lnp) + yd(1n v) - d (In c) '" where c is a constant. Inp+ylnv " ln c ..
Between any two states I and 2
"" - <

( 10.33)


For an ideal gu From Eq. ( 10.33)

EL -(.Lr v,

pv - RT p " c-v""


cv-T.v " RT cvl--r " RT Tvl- I = constant (10.34) Between any two states I and 2, for a reversible adiabatic process in the case of an ideal gas

.!i. = ~ 7j v2

( )'-'
( )'"
in the equationpv ""RT


Similarly, substituting from Eq. ( 10.33)

U" -; p -=RT
p ill


pHI"'" .c' .. RT

T!,I..orY'r .. constant
Between any two states 1 and 2 TtPl'..orY'r .. T1PP -'fI/T


(10.37) Po Equations ( 10,33). ( 10,34), and(10,36) give the relations amongp, v, and Tin

...1.. ...


( 12. )('-I)/T


a reversible adiabatic process for an ideal gas. The internal energy change ofan ideal gas fOT a reversible adiabatic process is given by Tds = du+pdu "" O

, , , Jdu =- Jpdv- - J-y d,


prJ .. plot - P2vl - c

u2- U I - C

v1-' - 01- 1

_ Pzvl .vl-T -




_ P2V2 - Plvl

.. R(12-7j) = R7j

_ ...:.:.L





y- I

II _I "" [ ( p )'-'"

338=The enthalpy change ofan ideal gas for a reversible adiabatic process may be similarly derived.

Tds = dh-vdp=O


J , dh = J , """ -J , ('p~"

Il y


PlvT '" P2vl - C h. - hi = --L- CI"1PP"I)'J - pft-IYrJ

(10.39) The work done by an ideal gas in a reversible adiabatic process is given by

I1Q - dV - I1W - O 11 W-- dV '" i.e. work is done at the expense of the internal energy.
W I _l '" VI - U z'" m (u l -

~ m(Plv! - P.v.) .. mR(1j - 11) 7 I 7 I

m R1j [1 -( .P.l..)lr-Il/Y ] (10040)


U v

where m is the mass of gas. In a steady flow process, where both flow work and external work are involved, we have from S.F.E.E., Wx +4-,-+g& - h l -h. "' cp (T I -Tv ... r(Plv,- pzv.)


1~R~(r.Li7-~r,~) 7 I

IfK.E. and P.E. changes are neglected,

w. " --LPIO! 1

[ ( )'-"']
1_ P. PI


"' "


of G/IUS wul G/U Mixlllm


10.3.4 Rn"nbk IsotJu:nu1 Process

When an ideal gas of mass m undergoes a reversible isothermal process from state I to state 2, the work done is given by


vI mRT
W I_1 ",

J-,-dV - mRTln-t,


'" mRTln ..!i..


The heat transfer involved in the process

QI - 2 " V 2 - VI
.. W I_2 "

+ W I_2

mRTln ViVI .. 7{S2 - SI)

10.3.5 Pol,lro/1k Process

An equation of the form pU' ., constant, where II is a constant can be used approximately to describe many processes wbicb oecur in practice. Such a process is called apolytropic process. It is not adiabatic, but it can be reversible. It may be noted that r is a property of the gas, whereas n is not. The va lue of II depends upon the proeess. It is possible to find the va lue ofll which more or less fits the experimental results. For two slates on the process, ( 10.45)


(v,)" . l'L


, _" '. ","p"'"--" 'log ." "P ':'' log v VI


( 10.46)

For known values of PI' Pl' VI and V2' /I can be estimated from the above re lation. Two other relations ora polytropic process, com:sponding to Eqs ( 10.35) and (10.37), are

.!L (-"'-)"-' .1j .. v2

..:.l... r "" ( l!1... )' -'"

(10.47 )




(I) Entropy Change In a Polytropic Process Tn a reversible adiabatic process, the entropy remains constant. But in a reversible polytropic process, the

340=entropy changes. Substituting Eqs (10.45), (10.47) and (10.48) in Eqs (10.28), (10.29) and (J 0.30), we have three e)(p~jons for entropy change as given below
32 -31 -

Cyln.2. + R In .!:1



_ _ R_ In ..!i. + --.!L In ...!L





Rln .2. ( 10.49) (y-I)(n-I) 1j Relations in terms ofpressurt! and spec;:ific volume ean be similarly derived. These are (10.50)
3 2 -3,""-

n- r

!!...=1. RIn -v2



( 10.5 1)

It can be noted that when n .. y, the entropy change becomes zero. If P2 > PI' for n S y, the entropy of the gas decreases. and for n > y, the entropy of thc gas increases. The increase of entropy may result from revenible heat transfer to the system from the surroundings. Entropy decrease is also possible if the gas is

(U) Heat lAd Work In. Polytropic Procell Using the first law to unit mass ofan ideal gas, Q - W- ul- u,
'Tl -T) R(7;-1j) .. c.... I -=

y- I

_ PlV2 - PI VI


-.l'll[(l'L)'.'" -,] = .l' ll[(-",-)H -,] y-l r-l



For 8 steady flow system of unit mass of ideal 8as, the S.F.E.E. Eq. (5.10),

Q _ W1_o.[~1
- c (T1 - T,) P

+ gZ] " h2 - h l

P1V I )

~ (P1VZ y- '


"' "

ProptrliIJ Df Gem For a polytropic process,

e" Gcs MixtrnlJ



Q-W~ " 1l

-, 1 r;~~! [( ~: )'-'" ] [T+

gZ =

- Y"', [(",-)'-' _,]

y- I

Equations (10.52) and (10.54) can be used to determine heat and work quantities for a closed and a steady flow system respe<:tiv~ly.

(Oi) IDtegral Property Relations in a Polytropic Proce.. In a

constant process,


jpdv "

, I

j "PJ:Ldv = PLVI


[( )'-']
J_ ~


_ =~: [1- (~ )0-0"]



-1""p = 'p,', [, -(",-)'-'] 1 II-I


- '''v, [,_(Ji)'-"'] II-I PI

The integral ofTds is obtained from the property relation Tds " du + pdv
2 _ 2 2


rd.< '

j du+ jpd,

=U2 - UI + j pdv
Substituting from Eqs (10.50) and (10.53)

, ,

{Tds - (y

~~: I) PIV{I-(~:



:: (y-:-Y ",) '-(;'--,;:, ,>"v.l'

<1 I)(n

-l:; r]

I)R(T1- TiJ

342=Since RJ(y- I) " c... and putting IlT"" T2 - Tl.the reversi ble heat transfer

QR ..

f Tds " c. I..:..!!.IlT 1 n- l


~ c"IlT

Where CD - Cv (y- n)l(1- n) is called the polytropic specific heat. For n > y theTe will be positive heat transfer and gain in entropy. For II < r,. heat lransfer will be negative and entropy of the gas would decrease. Ordinarily both heat and work are involved in a polytropic process. To evaluate the beat transfer during sucb a process, it is necessary to first evaluate the work via either

f pdv or - f vdp, depending on whether it is a closed or an

pv .. c

open steady flow system. The application of the first law will then yield the heal transfer. The polytropic processes for various values ofn are shown in Fig. 10.2 on the p-vand T- s diagrams. On differentiation,

rI' dp + pnrr l dv = 0

~ ""_ ,, J!..

The stope of the curve increases in the negative direction with increase of II. The values ofn for some familiar processes are given below Isobaric process (p " c), n = 0




,, --2

11=1. .. (v=c)

,, -1

Fig. 10.2

PrOUSJ i~ whih JnI'

_ cmultJII/


lsothennal process (T = c). 11 = I Isentropic process (5 - c) . n Isometric or isochoric process (v

c). n '" "".


10.4 Gas Compression

A gas compressor is a device in which work is done on the gas I~ raise its pressure, withanappreeiable increase in i!sdensity. Being a steady flow device the external work done, in absence ofK.E. and P.E. changes, would be
WK ""- !vdp " hl-hl

, ,

For a reversible polytropic compressioll proct's..~, prf' - c

W.' _"_PIVI[(f'L)(~-I)ID -I] PI


For reversible adiabatic compreJs/all, II is substituted by y. For rf!Venible isothermal compressioll, the work of compression becomes

Wa ~ PI VI In .!!L p, Figure 10.3 shows r.he three reversible compression processes. From Eq. (10.59), the slope at stale I is given by

.2.E.. "'" _nft

do VI For y> n > I and for the same pressure ratio PiPl' the isothemlal compression needs the minimwn work, whereas adiabatic compression needs the maximum work, while the polytropic compression needing work in between the two. It may be DOled in Fig. 10.3, that in process 0- 1 the gas is SIlcked in a reciprocating compressor. in process 1- 2 (2 T 2. or 2" as the case may be) the gas is compressed. and in process 2- 3 !.he gas is discharged. The clearance volwne is bere negle<:lcd The work of compression is the area included in the diagram as shown.


FIg. 10.3

-Rtrnsihlt tIImprtulor. "rouJJu



10.... M,"""""

By staging the compression process with intennediate cooling, the work of compression can be reduced In an ideal two-stage compressor, as shown in Fig. 10.4, the gas is first compressed iscntropically in the low pressure (L.P.) cylinder. process 1- 2, it is cooled in the intercooler at constant pressure to its original temperature (called perfect j/llercoo/ing), process 2-3, and it is theD

compressed isentropicaJly in the high pressure (H.P.) cylinder, process 3- 4. The total work of compression per unit mass in the two adiabatic cylinders is

.. (h2 -

hI) + (1r~ - "3)


If the working fluid is an ideal gas wilh constant specific heats, W. "" c p (Tl - T1) + c,cT. - T)




T, . r,







-CpT{i -1)+CpT{~ -I)

~ CpT{( ~~ r- - 1] + CpT{(~:r-I)ll _I]
with perfect intereooling, T) .. T) andp2" P3
W -c T,l!1... PI
For minimum work

I V 1


( p) )"-'" )'>-'''' +l!!..




dW. .. c r.[L=...! - 11"'pl-lI"l - o r p;lll + ( ~)pl r


pf,- I)/ T

P22(y-l)'y .. (PJP.fr- 1)'y (10.62) P2 - JI'lP4 Thus, fnr minimum work the intennediate pressure P2 (or pJ is the geometric mean of the suction and discharge pressures. From Eq: (l0.62) it follows that (10.63)


PI PI For a 3 stage compressor, the pressure n1lio per stage is:

1'L - [~J'"


~ [p'J,n

Thus, the intennediate pressure thai produces minimum work win also resull in equal pressure Rlios in the two stages of compression, equal discharge temperaturc5, and equal work for the two stages. For ideal two-stage adiabatic compression, the mini~um work, using Eqs (10.61) and (10.63), becomes
1 l!.1.. W, _ _ _ _ 2 y" [( )"-'''' I PI




Similarly, for reversible polytropic compression, pv n - c, with perfect iotercooling, the same expressions given by Eqs ( 10.61) aDd (10.62) can be obtained by substituting II for y, and the minimum work becomes

Wt _ 2I1Rli.li.

[[ )'-'" -I1


The beat rejected in the intercooler is

Q1-l = cp (T2 - Tl ) If there arc N stages of compression, the pressure ratio in each stage can be

shown to be

.li. _ ( diSCharge pressure ) '"

suction pressure The total work of compression for N stages is


w ~ ",n R"I [[ Pdi>cbarp . )" - '>'"


_ I

n -I



In the case of gas compression, the desirable idealized process is often a isothermal process. The isothermal efficiency, 1/" ofa compressor is defined as


Vol.metric E/fidnIcy

The ratio of the actual volume of gas taken into the cylinder during suction stroke to the piston displacement volume is called \I(/{umetric efficiency. If iii is the mass flow rate of gas and VI is the specific volume of gas at inlet to the compressor, and PD is the piston di splacement per cycle, then volumetric efficiency is given by (10.68) Let us imagine an idealized reciprocator in which there arc no prcss\JJ'e losses and the processes 3-0 and 1- 2 arc reversible polytropic processes (Fig. 10.5), with equal value ofn. Theclearance volume (CI') is the volume "l of the cylinder and the process 3- 0 represents the expansion of the air in theCV. The volumetric efficiency is then given by


PropntitJ of Ga.stJ 11M G/U Mi.%/urf;f


"'I--l-- --{


.. c

p, ......

c.v. :

--r 0.,

+......, .. - - - ---"

P.O. - - . . . l



Fig. 10.5 JWctfltJ in 11ft idtaliqd rtrifJ1lXtlllq (DmprWllT

Clearance C is defined as


Clearance volume




- I + C-

~ ~:


( 10.72)

Equation (10.72) is ploued in Fig. 10.6. Noting that (p.jpt)lIais always greater than unity, it is evident that the volumetric efficiency decreases as the clearance increases and as the pressure nltio increases. In order to get maximum flow capacity. compressors are built with the minimum clearance. Sometimes, however, the clearance is delibemtely increased as a means of controlling the flow through the compressor driven by a conslant speed motor. It is evident from Fig. 10.6 that as the pressure ratio is increased, the volumetric efficiency of a compressor of ru ed clearance decreases, eventually

348=becoming zero. This can also be seen in an indicalor diagram. Fig. 10.7. As the discharge pressure is increased, the volume VI' taken in aipl. decreases. AI some pressureP:zc the compression line intersects the line of clearance volume and there is no discharge of gas. An attempllo pump top:zc (or any higher pressure) would result in compression and re-expansion of the same gas repeatedly, with no flow in or out. The maximum pressure ratio attainable with a reciprocating compressor is thus limited by the clearance. The clearance cannot be reduced beyond a certain value, then 10 attain the desired discharge pressure, multistage compression is 10 be used, where the overall pressure ratio is the product of the pressure ratios of the stages. The mass flow rate of gas from Eq. (10.68) then becomes


PD 11..,. = PD [1 + C- C(fi)'''] VI VI PI



pv.= C

i-";-- - --"';--P<

I I - v.

L - V. ---I


Flg.10.7 Effid ~fprtJJ.rl ratio on captJrity

- = 349

10.5 Equations of State

The ideal gas equation of statepv .. Ii T can be established from the positulates of the kinetic theory of gases developed by Clerk. Mp.well, wi th two important assumptions that there is little or no attraction between the molecules of the gas and thai the vo lume occupied by the molecul es themse lves is negligibly small compared to the volume of the gas. When pressure is very small or temperature very large, the intermolecular anraclion and thc volume of the molecu lcs compared to the total volume of the gas are not of much significance, and the real gas obeys very closely the ideal gas equation. But as pressure increases. the intermolecular forces of attractio n and repulsion increase, and also the volume of the mo lecules becomes appreciable compared to the gas volume. So then the real gases deviate considerably from the ideal gas equation. van der Waals, by applying the laws of mechanics to individual mo lecules, introduced two correction terms in the equation of ideal gas. and his equation is given below.

(p+ :7 )<11 -b) - RT

(10 .74)

The coefficient a was introduced 1 0 account for the existence of mutual attraction between the molecules. The term af!? is called theforce of cohesion. The coefficient b was inlorduced 10 account for the volumes oflhe molecules, and is known as co-I'Q/ume. Rea l gases conform more closely with the van der Waals equation of state than the ideal gas equation of state, partit:ularly al higher pn:ssures. But it is not obeyed by a real gas in all ranges of pressures and temperatures. Many more equations of state were later in troduced, and notable among these arc the equations developed by Berthelot, Dieterici, Beattie Bridgeman, Kammerlingh Onnes, Hirshfelder Bird-Spotz-McGee-Sutton, Wohl, Red lich-Kwong, and Martin Hou. Apart from the van deT Waals equat ion, three two-constant equations ohlate arc those of Berthelot. Dicterici. and Redlic h. Kwong. as given below: Berthelot: Dielerici: RedlichKwong:

RT u p .. - - - - 2 v-b rv
RT _.:Uv p= v_ b e
p - ---


(10.76) a (10.77)

RT v -b

T 1I7 11(v+b)

The constants, a and b arc cvaluated from the critical data, as shown for van der Waals equation in article 10.7. The Benhelot and DieteTici equations of state. like the van der Waa ls eq uation. are oflimiled accuracy. But the Redlich.Kwong equation gives good results at hi gh pressures and is fa irly accurate for temperatures above the critical value. Anothertwo-constant equation which is again oflimited ~ccuracy is the SahaBose equation of state given as follows.


&sic Intli Applied 'I7tmnMytllllllia

RT _ al RTv In(V-2b) p---' --2b ,


It is, however, quite accurate for densities less than about 0.8 times the critical density. One more widely used equation of stale with good accuracy is the Beattie-

Bridgeman equation:

P '"

"R"T-:(I,.--,'''-) (, + B) _ v2 v~



A - AO(I-!),8 ~ BO(I-;).e ~ v~l

There are five constants, ADo B(Io a, b, and c, which have to the detennined experimentally for each gas. The Beattie-Bridgeman equation does not give
satisfactory results in the critical point region. All tb eseequations mentioned above reduce 10 the ideal gas equation for large

volumes and temperatures and for ve"Y small pressures.

10.6 Virlal Expamlons

The relation betweenpv andp in the form of power series, asgiven in Eq. (10.1), may be expressed as

p v .. A(I + Up + C pl + IY pl + ... )
For any gas, from equation (l0.3)

lim pu

- A-RT
I + B' p +

-ti: RT

cIl + D'pl + ...



An alternative cllpression is

CD .l -v " 1+ -B + - r + - J +'"



Both expressions in Eqs (10.80) and (10.8\) are known as virial expamioDS or virial equations of state, first introduced by the Dutch physicist, Kammerlingh Onncs, If, C, B, C, etc. are called virial coejficic/1/$.1f and B are called second virial coefficients, C and C are called thrid viriaJ coefficients. and so on. For a given gas, these coefficients are functions oflempetature only. The ratiopv IIi. Tis called the compressibility factor,Z. For an ideal gasZ" I. The magnitude of Z for a certain gas at a particular pressure and temperature gives an indication of the extent of deviation of the gas from the ideal gas behaviour. The virial expansions become


Proptrlia ofGastJ 11M Gas MixlM,tJ


Z - I +B'p+ C;.+ Upl + ...


Z z l+~+..f..+..Q.+...
ti til til


The relations between 8',

C, and 8, C, ... can be derived as given below

+ C/ + D'pl + ...

e .. RT

I + B'p

= I

+C[(ii;J'(I+: +i> ++)} ,B',-B""R,,--!..T~+f-C,-,(,,ii-,-T) L ' +--+ v v


B'RTC + C'(RT)l + D'(RT)l

Comparing this equation with Eq. (10.81) and rearranging


+ ...


B'=....!L C - C _ BI

(RT)2 ' l D' D-3BC+2B d '" (RTi ,an soon






=1+B'p+Cp2+ ...

= I

B c-If 1 + -=-p+ -_-- p + RT (RT)2

The tennsB!ii, Ofjl etc. of the virial expansion arise on account of molecular inte.'actions. If no such interactions exist (at very low pressures) B = 0, C " 0, etc.,:Z - 1 andp v - RT.

10.1 Law of Corresponding States

For :a certain gas, the compressibility factor Z is a function of p and T [Eq'j(IO.85)], and so a plot can be made of lines of constant temperature on cooilinates ofp and Z(Fig. 10.8). From this plot Z can be obtained for any value ofp aod T, and the volum e can then be obtained from the equationpv =ZRT. The advantage of using Z instead ora direct plot ofo is a smaller range of values in plotting. For each substance, there is a compressibility factor chan. It would be very convenient ifooechart could be used forall substances. The general shapes of the

352=1.S 35K


Fig. lo.s


V"riation of til, romprmibililJ foctvr of",,'OInt toillr pr_" .. tJl tnutl1.nJ InnjJnIJI1'"

vapour dome and of the constant temperature lines on the p-v plane are similar for all substances, although the scales may be' different. This.similarity can be eJtploited by using dimensionless properties called reduced properties.The reduced pressure is the mtio of the existing pressure to the critical pressure of the substance, and similarly for reduced tempemture and reduced volume. Then

PI = ..... ' T, c Pc

~ ,v, ,,,-,,,,,,
Ie Vo

where subscript r denotes the reduced property, and subscript c denotes the property at the critical state. At the same pressure and tempenllure the specific or molal volumes of different gases are different. However, it is found from experimental data that at the same reduced pressure and reduced temperature, the reduced volumes of different gases are approximately the same. Therefore, for al1 substances

v, - j(p" T,)
Now ,


where Z< ~ Pe . This is called the critical compressibility factor. Therefore


from Eqs (10.86) and (10.87),

Z =j(p"T"ZJ


Experimental values of Z. for most substances fall within a narrow range 0.20-0.30. Therefore, Z<may be taken t~ be a constant and Eq. (10.88) reduces

(10.89) Z - f(P" T,) When T, is plotted as a function ofreduced pressure and Z, a single plot, known as the generolized compruslbility chart, is found to be satisfactory for a great variety ofsubstan<:es. Although necessarily approximate, the plots are extremely useful in situtions where detailed dala on a particular gas are lacking but its critical properties are available. The relation among the reduced propenies,Pr T" and v" is Icnown as the law of correspt)nding :ftates. It can be derived from the various equations of state, such as those of van der Waals, Benhelot, and Oieterici. Fora van deT Waals gas,

(P+7 )(V-b) - RT
where a, b, and R are the characteristic constants of the panicular gas.

RT a v-b - ~

PrJ] - (pb + RT) i + QV- ab ~ 0

It is therefore a cubic in v and for given values of p and Thas three roots of which only one need. be real. For low temperatures, three positive real roolli exists for a cemin range of pressure. As the temperature increases the three real roots approach one another and at the critical temperature they become equal. Above this temperature onlyone real root exislli foran values ofp. The critical isotherm T~ at the critical state on the Jrv plane (Fig. 10.9), where the three real roots of the.van der Waals equation coincide, not only has a zero slope, but also its slope cbanges at the critical state (point of inflection), so that the first and second derivatives ofp with respect to v at T= T~ are each equal to zero. Therefore

~---T Tc


~-- .

( 10.90)



3S4 = From these two equations, by rearranging and dividing, b ... SubstitUling the value of bin Eq. (10.90)


R ;~
97;,1:1. Substituting the values of band R in Eq. (10.74)

(Po + :: iVo) '"

9~aVo .7;,

a"" 3pov:
Therefore, the value ofR becomes

R"' !PcVc
The values of a, b and R have thus been expressed in terms of critical . properties. Substituting these in the van der Waals equation of state

3 "'

p + 3Pev:

)(v-.!.v )::::! PcVc 3 37;,


p ( Pc



)( v

') T v:--"] ="]7;,


Using the reduced parameters,

(Pr+~}3V,-I) "' 8T,


In the reduced equation of state (10.92) the individual coefficients a, b and R fora partieular gas have disappeared. So thi s equation is an expression ofthe/aw . of corresponding siaies becaues it reduces the properties of all gases to one fonnu la. It is a 'law' to the extent that real gases obey van der Waals equation. Two different substances are considered to be in 'corresponding states', if their pressures, volumes and temperatures are of the same fractions (or multiples) of the eritical pressure, volume and temperatures are of two substances. The generalized cQmprt!Sslbiliry chart in tenns of reduced properties is shown in Fig. 10.10. It is very useful in prcdieiting the properties of substances for which more precise data are not available. The value of Z at the critical state for a van der Waals gas is 0.375 (S ince R =! Peve ). At very low pressures Z 3 the "' icleal gas behaviour. Equation approaches unity, as a real gas approaches (10.92) can also be written in the following fonn

(p,V, + :, )(3V, - I) '" ST,v,

- = 355

h ""


." !












SaturallJd liquid

--"-----Co~ .~~-"------L-----"------"----~ o




U,-,-,--,---,-,-,--v . -,---,-,-,-,--"

.II _

~ 0.9~\i:;,



-- :

.. J::f-t .. -= ..H-+-+-+-t
-r -T
TR.-l .50


'---t-\-~' '''t-f',-" ...~;:t-T~ = ~.~-:1;""bf.?-+-+-+-1 --::


O ,' I-++t"l-t-''.j.- 'TR - 1.20'--::""+,~'-t--+-1-+-I

0.'1-+-1/---"l--;:~~-+,""""+ " TA - l .l0 ,,~ ;.. / . ...."..
I " Elhane
0.3 r


'\ i"I

. . :J-.~ . . -p;~


"+!" -.-

'-" ~

o. L+_I-+' -.'f."'1;;'>~ ~-j-+. ethylene tl-Hepl.ene

, _+_I-""C'"'~.OO;:j'C--+_t--f_+- Propane C40rbon dio~ n-eut.ne w...I' .. 0.' 1-+-~'+-t--+-t--f-+- - Aventge CUMI baed on
O. Io :-;!o-7.;-;',-cC;;-+'~;-;C;-f.;--+'-;'\;-~+'~~, 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6 .0 6.5 1.0


"'i '1'''1''''' i

87: v 3 p,v. - ....::..:J....:_3v,-1


( 10.93)

Figure 10.11 shows the law of corresponding states in reduced coordinates,

(P,v,) vs.P.. Differentiating Eq. (10.93) with respect top, and making il equal 10
zero, il is possible 10 determine the minima of the isotherms as shown below.

_a_[~-2.1 -
aPr 3vr -I


....[' r. -1..] [5.] _ . av, 3v, v, aPr

T, T,


av.] [aPr ....[8Trv, _l...] _ .




3v, - I



,.of=.,"'_c::-_-_- - - -


r::::::----=-:'o'-c::-~ Lows paning Ihrough 1M

'" "'" "

" , .. .... 1 .... _'!!''" I::'


Tf 1.1


'<1', ,

Tf 1.0 T,0.9

- _.p.


s """"'



3(3v. _1)2 -"''''',,-'''- 8T, - [ P.


+ 2 (3v,-I)



(prv,i- 9(p,v,) + 6p, " 0 This is thc equation of a parabola passing through the minima ofthc isothcnns (fig. 10.9). When p, - 0, p,v, - O, 9


_ 9(Prvr J-(Pr v,)1

~"9-2(~v) = 0
p,v, " 4.5
p, 9 x 4.5 X (4.5)2

.. 3.375

Thc panbola has thc vcnex al p,v, - 4.5 and p, - 3.375, and it intersects thc ordinate at 0 and 9. Ea<:h isothenn up to that marked Ta has a minimum (Fig. 10.11). Thc To isotherm has an initial horizontal ponioo (p,v, " constant) so that Boylc's law is obeyed fairly accuratcly up to moderate pressures. Hence, thc corresponding

aS8=temperature is called the Boyle femperature for that gas. The Boyle temperature Ta can be determined by making "" 0 whenp, = 0 [O<PrVr)] ap, T, - TR Above the Boyle temperature, the isotherms slope upward and show no minima. As T, is reduced below the critical (i.e. for T, < I), the gas becomes liquefied, and during pbase transition isotbenns are venica!. The minima of all these isotherms lie in the liquid zone. Van der Waals equation of state can be expressed in the virial form as given below

b b' b' - R 1+-+-+--.-+ v v1 v'


.. The second virial coefficient B "" h - alRT. the third vma! coefficient

c - i?, etc.
From Eq. (10.85), on mass basis

PV " RT ( I +!! p+
To determine Boyle temperature, Ta

C~ Ir RTl


+ ... )



T- C


" O" .L



hR' RT The point at which B is equal to zero gives the Boyle temperature. The second
virial coefficient is the most imponant. Since [ \pV)

Ta - ...... becauseB - b- ...!!...


1 ~ B. p_o

whenB is known,

the behaviour of the gas at moderate pressures is completely detennined. The

terms which contain higher power (at?, Dill. elc.) become significant only at very high pressures.

10.8 Other Equations of State

van der Waals equation is one of the oldest equations of state introduced in 1899, where the constants a and b are related to the critical state properties as fOWld earlier,

o "' 3pif. ", 27 R2T/ b "' .!.v :: 1 R1'o

64P.' 3 < 8P.
The Beattie.Bridge man equation developed in 1928 is g iven in Eq. 10.79, which has five constants. It is essen tially an e mpirical curve lit of (\ata, and is reasonably accurate when values ofspecilic volume are greater than v. Benedict, Webb, and Rubin extended the Beattie.Bridgeman equation of state to cover a broader range of states as given below:

p . RT +( BRT-A-.......)_I_ + (bRT-a) +..E....

l til v + ti{Tl(l+fz)exp(-p-)


It has e ight constants and is quite successful in predicting thep-v-T behaviour of light hydrocarbons. The Redlich-Kwong equat ion proposed in 1949 and given by Eq. 10.77 has the constants a and b in tcnns of critical properties as follows:

a '" 0.4275 R2


, b " 0.0867 R 1'0


P .

The values of the constants for th e van der Waals, Redlich.Kwong and BenedictWebb-Rubin equations of state are given in Table 10. 1. 1, while those forthe Beanie-Bridgeman equation of state are given in Table 10. 1.2. Apart from these, many other multi-constant equations of state have been proposed. With the advent of high speed computers, equations having SO or more constants have been developed for representing the p-v- Tbehaviour (Of different substances.


Properties of Mixtures of Gases-Dalton's Law of Partial Presaures

Let us imagine a homogeneous mixture of inert ideal gases at a temperature T, a pressure p, and Q volume /I. Let us suppose there are moles of gas A I' "2 moles ofgasA:v ... and upton< moles of gas A< (Fig. 10. 12). Since there is no

n ,

Fig. 10.12 MUIl",ofpsu

Table 10.1.1

C~ISI/jIJIU for Ilu Ujln dtr Wuls, RldJidI~ jiM BnI,did W,nRdift Elfg.tillfU ofSIIIlI

in m1 lkmol. and temperature in K

1. van der Waals and RedlichKwong: Constants for pl'e$SUfe in

bars. specific volume


Butane {C.H1ol Carbon dioxide (COt> Carbon monoxide (CO)

van der Wfla{s b

Nitrogen (Nt> Dxygeo(Ot> Propane (C1H, ) Refrigerant 12 Sulfur dioxide(SOt>


13.86 3.647 1.474 2.293 1.366 1.369 9.349 10.49 6.883 5.S3 1

0. 1] 62 0.0428 0.0395 0.0428 0.0386 0.0317 0.0901 0.0971 0.0569 0.0305

I 289.55 64.43 17.22 32.11 15.53 17.22 182.23 208.59 144.80 142.59

0.03060 0.02963 0.02737 0.02965 0.02677 0.02197 0.06242 0.06731 0.039'5 0.0211 1

Sollrct; C.1eulated from critical data.

2. BenedictWebb- Rubin : COO5tantl

pressure in bars. specific volume in mJlk mol,

ee 3.206 x lO i LOO6x UI2xl0" U04 x L0504x IcY 8.676 x 2.S79 x 10' 2.287 x 7.381 x 102 8. 166 x a 1.101 x H? 8.47xHr L3SOx I ~ 1.244 x 10'" 1.272 x l~ r 0.0).4(1 0.OOS39 0.0060 0.0060 0.0053

and tcmpet1lture in K
s..b.fiutao ,t b C.H,o 1.907310.218 0.03999& COl 0. 13862.1737 0.001210 CO 0.037 1 US90 0.002632 at. O.OSO I 1.8196 0.003380 N; 0.02504 1.06760.002328 B 0.12-436 0.04991 0.05454 0.04260 0.04074

lcY IcY 10' \0'

Souru; H.W. Cooper.1IId J.e. 001dfrank. Hydrocarbon Processin" 4S (12); 14\ (1967). Table 10.1.2 (a) The Beattie-Bridgeman eqU4tion of state is

p o.


v ; l P + B l - f . where,t .. ,to( l - f)andB .. Bo

When P is in kPa. is in milk mol, Tis in K, and R.,. " 8.314 kPI m1I(kmoIK), the five constants in the Beattie-Bridgeman equation arc as follows:

(l -t)

Argon, Ar Carbon dioxide. COl Helium. He Hydrogen, Hl Nitrogen, Nl



131.8441 0.0 193 1 130.7802 0.02328 S07.2836 0.07132 2. 1886 0.05984 20.0117 -0.00506 136.2315 0.02617 151.0&S7 0.02562

0.04611 0.00 11 01 0.03931 0.0 0. 10476 0.07235 0.01400 . 0.0 0.02096 -0.04359 0.05046 -0.00691 0.04624 0.004208

< 4.34 x JOi 5.99 x I(t 6.60 x 10' 40

4.20 x 4. 80 x

I(t ](t

Source: Gordon J. Van Wylen and Richard E. Sonntag, Fuudament.aJs of Classical TbcnnodynamiCli. EngiishlSl VCI'lIioo, 3d cd .. Wiley New York, 1986, p. 46. Table 3.3.

~tUs ofG.su


C/IJ MWllra


chemical reaction, the mixture is in a state of equilibrium with the equation of


pV=(nl+n2+ .. IfJ RT

Ii -

8.3143 kl/kg mol K

nlRT n1liT n.lir P " -v-+-v-+ "'+ - v The expression


represents the pressure that the Kth gas would exert if

it occupied the volume Valone at temperature T. This is called the partial pressure of the Kth gas and is denoted by Pro: Thus

P "' PI+Pl+ " '+ P. ( 10.95) This is known WI Dalton 's law ofpurtial pressures which states Withe lotal pressure ora mixture of ideal gases is equal to the sum of the partial pressures.

- In, ,iir 'P
and the partial pressure of the Kth gas is

PK -


Substituting the value of V

n" p,,= n"RT'p =_ .p In,,RT



In,, ~ n l+ 1I2+ +no

'" Total number of moles of gas The ratio ~ is called the mole fraction of the Ktb gas, and is denoted by .





362=or Also PK - XK'P



+ Xl + ... + X. "" I (10.97) In a mi;o;ture of gases, ifatl but one mole fraction is dctcnnined, the last can be calculated from the above equation. Again, in lenns of masses
p[V - mIR1T PzV .. m~zT PcV " m.Re T Adding, and using Dahon's law (10.98) pV .. (m1R I + m~2 + ... + m.,RJT whm P " P[+Pl + " '+ P, For the gas mi;o;ture pV ", {m[ + mz+ .. . + mJRmT (10.99) where R.n is Ihe gas constanl for the mixlure. From Eqs (10.98) and (10.99)

R .. m[R[+mlRl+ +mc&
m m[


+ml + +m.

The gas constant of the mixture is thus the weighled mean, nn a mass basis, of the gas constants of the components. The lotal mass ofgas mixture m is m - m[ + .. . + m. If /J denotes the equiwlent mQlecular weight of the mixture having n lotal numberofmoles. n/J = nl /JI + nl/Jl + ... + n. J.Jc /J = x l/J1 + xZ/Jl + ... + x,JI.
/J = hKPK


A quantity called thepartial volume of a component of a mixture is the volume that the component alone would occupy at the pressure and temperature of the mixture. Designating the panial volumes by VI' Vz etc. pV[ .. m 1R 1T, pV1 - m1R1T, ... ,pVc - m.,R. T or p(Vt + V (10.102) R 1 + mzR2 + ... + m.Rc)T l + ... + V. ) - {m 1 From Eqs ( 10.98), (10.99) and (10.102) (10.103) V- VI + Vl + ... + V. The lotal volume is thus equal 10 the sum of the partial volumes. The specific volume a/the mixture, v, is given by

v "' .!:::..=

V ",[+m2+ .. + m
+ +m. V

1. ""

"'I +1112


__ m_, + _m_2 + .. + _ m_,



(10. 104)

where VI' Il2' ... denote specific volumes of the components, each component occupying the total volume. Therefore, the density of the mixture P '" PI + P2 + ... + P.
( 10.105)

10.10 Internal Energy, Enthalpy and Speclflc Heats of Gas Mixtures

When gases at equal pressures and temperatures are mixed adiabatically without work, as by inter-diffusion in a constant volume container, the first law requires that the internal energy of the gaseous system remains constanl, and experil11(nlS show that the temperature remains constant. Hence the internal energy of a mixture of gases is equal to the sum of the internal energies of the indi vidual components, each taken at the tempcralutC and volume of the mixture (i.e. sum of the 'partial' internal energies). This is also tNe for any of the thennodynamic properties like H, C", Cp' S, F and G and is knov."Q as Gibbs theorem. Therefore, on a mass basis

~ "'lU I

+ "'1U2 + ... + ",. U.


'I", '"

"'lUI + m l u 2 + ... + meUe

m,+m 2 ++m.

which is the average specific in ternal energy ofthe mixture. Similarly, the total enlhalpy of a gas mixture is the sum of the 'partial' ent!J.alpies and

mh., " "'Ihl + "'2h2 + ... + "'.h. h .. "'I hi + m1hZ + ... + "'ehe "'1+m2 + ... + me m From the definitions of specific heats, it follows that

( 10.107)

( 10.108) (10. 109)

10.11 Entropy of Gas Mixtures

Gibbs theorem states that the lotal entropy ofa mixture of gases is the sum oflhe partial entropies. The partial entropy of one of me gases of a mixture is the entropy

364=that the gas would have if it occupied the whole volume alooe at the same temperature. LeI us imaginge a number of inert ideal gases separated from one another by suitable partitions, all the gases being at the same temperature T and pressurep. The total entropy (initial)

Sj From property relation


+ n~l + ... + neSe

.. In"st:

dh - vdp ~ cpdT - vdp

... '" - , - dT ~

, -r


= p

The entropy of I mole of the K\h gas at T'andp

st: -

- 1 dr -.,np+so" c rS- = R",n,


where sO" is the constant of integration.

-. ('1R

~, Pit

-+-=--Inp dr '", )

at: - li cPIt

+ li


(10.110) s; - liInt:(O't: - Jnp) After the partitions are removed., the gases diffuse into one another al the same temperature and pressure, and by Gibbs theorem, the entropy of the mixtureS!'> is

the sum of the partial entropies, with each gas exerting its respective panial pres sure. Thus

Sf '" liIn,,(ax -lnPIJ


Pv. - Xt:P
Sf " Rtn,,(al( - Inxt: - Inp) Sf- S; = - litn" In xI( Sf-S; - -li(n, In Xl + n21n xl +'" + ne In xJ

A change in entropy due to the diffusion of any number of inert ideal gases is (10.112)

Since the mole fractions are less than unity, (Sr- SJ is always positive, coofonning to the Second Law. Again

Sr - S; =-li(nl ln.!!.Ltnlln.E1..t .. . tne In

p p

Pc) p


which indicates that each gas undergoes in the diffusion process ajree,expDn.3ion from total pressurep to the respective partial pressure at constant temperature.

Similarly, on a mass basis, the entropy change due to diffusion
S,- Sj .. :..!mKRKln'&" p

=-(m)R) In.J!J... + m2 R2 In l!1.. + ... + m<~

p p)

1n.J!J...) p

10.12 Gibbs Function of a Mixture of Inert Ideal Gases

From the equations

<Ii ... C ~ - R~ , T p

the enthalpy and entropy of I mole ofan ideal gas at temperature Tand pressure

h .. ho+ fCpdT
dT -,np S '" cP r+so-R

- 1-

Therefore. the molar Gibbs function

g;h - Ti <= ho+JcpdT-Tfcp



Jd(uv) '" f udv+ J /XIu "' uv u.. l.. v- l ,dT T' ,


~J cpdT '" J ~

" dT + JCpd~ - ;1 )dr


= 11-, dT_I!<.dT dT T T2
hT2dT dT

- _ TI I , p dT - TI' P dT T

- Il e,dT g "'ho- T -rr-dT- Tso


~= ;~- !J+dT-~

J- dT


where ~ is a function oftemperarure only. Let us consider a number onnm ideal gases separated from one another at the same Tandp

G; = l:n"g" '" RTl:n", (~ + Inp )

After the partitions arc: removed, the gases will diffuse, and the partial Gibbs fW1ction ora particular gas is the value ofG, if that gas occupies the same volwne at the same temperature e}l.erting a partial pn::ssure Px. Thus
G(= RTl:n" (rflK. + ln p.u

- RTl:ndrflK. + In p + ln x.u
Therefore Since < 1, (G(- Gi) is negative becauesc: G decreaSC:5 due to diffusion. Gibbs fW1clion ora mixture ondeal gases at Tandp is thus G - RTl:n",(oh + Jnp + In x.u (10.117) (10.116)


Example 10.1 Two vessels, A andB, both containing nitrogen, are connected by a valve which is opened to allow the contents to mix and achieve an equilibrium temperature of 27C. Before mixing the following infonnalion is Known about the gases in the two vessels.

Vessel A

Vessel B

p=I.5MPa p "' 0.6MPa t "' SOGC t =20C Contents .. 0.5 kgmol Con tents .. 2.5 kg Calculate the final equilibrium pressure, and the amoW1t of heal transferred to the surroundings. Ifthe vessel had been perfectly insulated, calculate the final temperature and pressure'which would have been reached. Take r .. 1.4. Solution For the gas in vessel A (Fig. Ex. 10.1)

"' "


I ....

O .6 Io4Pa


f'I3. EL 10.1

PAY" - n"Ji T"

wbere VA is tht volume ofveuel A 1.5 x IIP )( VA " O.S x 8.3143 x 323 VA .. 0.895 m )
Thc~so(iUinv~I A

m,, " nAP" .. O .S kg mol)( 28 kg/kgmo[

- 14kg
Characteristic gas constant R of nitrogen

R " 8.3 143 .. 0.297 kJ/kg K 28

For the vessel B
PaYa - ma RTa

0.6 x lIP x Va " 2.5 )( 0.297 x 29) Va " 0.363 ml Total volume ofA and 8

v- VA + Va " 0.895 + 0.363

.. 1.258 m1

Total mass of gas


-III" +m

8 "

14 + 2.5 - 16.5 kg

Final temperature after mwng

T-27+273-300 K For the fmal condition after mixing pY - mRT

where p is the final equilibrium p=re .. p x 1.258 " 16.5)( 0.297 x 300


16:.5 x 0.297 x 300 1.258 .. 1J 68.6 kPl

.. 1.168 MPa


, = _R_= 0.297 r - l 0.4 .. 0.743 kl/kg K

Since there is no work transfer, the amount ofheallransfer

Q - change of in lemaI energy

- V2 -VI
Meas uring the internal energy above the datum of absolute zero (at T '" 0 K, u - 0 kl/kg) Initial internal energy VI (before mixing)

.. m"cyT" + mac. Ta
., (14 x 323 + 2.5 x 293) x 0.743 .. 3904.1 kl Final internal energy V1 (after mixing)


.., 16.5 x 0.743 x 300 = 3677.9 kl

Q =3677.9 - 3904.I -- 226.2kl

If the vesels were insulated



~ Vl

M"c..T" + msCvTa "" mCvT

where Twould have been the rmal tempel1llure .




+ maTa
= 3IS.S K

m 14 x 323+ 2.S x 293


oc The final pressUTe


P - - y- =

l6.SxO.297x3IS.S 1.2SS

- 1240.7 kPa
= 1.24 MPa

E%am.ple 10.2 !'- certain gas has c p .., 1.968 and c y - LS07 kl/kg K.. Find illl molecular weight and the gas constant. A constant volume chamber of 0.3 m1 capacity contains 2 kg ofthisgru; at Heat is transferred to the gas until the tempenture is 100C. Find the work done, the heat transferred, and the changes in internal ~nergy, enthalpy and entropy. Solution Gas constant,



ADJltr/ia ifGllsa 11M Gu MixhnlJ


R .. cp - c... 1.968 - 1.507

- 0.461 kJ/kg K Molecular weight, IJ. "

R = 8.3143
R 0.461

'" 18.04 kglkgmo1


At constant volume
Ql~2 '"

mc. (12 - 'I) '" 2)( 1.507 (100 - 5) '" 286.33 kJ


Change in internal energy

Wl~2- pdv - O
U2 - VI - QI _2 - 286.33 kJ Change in enthalpy
H2- Hl - mcp(tl - l1) ... 2)( 1.968 (100 - 5) " 373.92 kJ

, J ,



Change in entropy
Sl-Sj "' mc. ln

..!i. 373 r.1 = 2xI.507In278


= 0.886 kJlK

Eumple 10.3 (a) The spedfic heats of a gas are given by cp '" 0 + kT and c~ .. b + kT, where 0, b, and k are constants and T is in K. Show that for an
isentropic expansion of this gas Tbr

I-T '" constant

(b) 1.5 kg of this gas occupying a volume of 0.06 ml at 5.6 MPa expands isentropically until the temperature is 24O"C. If a .. 0.946, b - 0.662, and k " Ir, calculate the work done in the expansion. Solulion (.) cp-c. " a + kT - b- kT

"" o-b - R


dv m=c -dT T +R,

dT dv dT dv " (b + k1) +(a-b)- - b +kdT + (a -b)-

T v For an isentropic process bin T + kT + (0 - b) In v c constant

r v"-b J-T .. constant



R .. a - b " 0.946 - 0.662 " 0.284 kJlkg K Tz - 240 + 273 " SI3K
TI .. APi = S.6 X 10] x 0.06 - 788.73 K" 789 K mR 1.5 x 0.284

TdS "' dU+4W "' 0

W I _2 ",

-" Imc~ dT "m = I.S I (0.662 + O.OOOIT)dT = I.S '" [0.662 (789 - S13) + 10-4 x 0.5 {(789)z - (S 13ilJ
.. I.S (182.71 + 19.97) .. 304 kJ

Example 10.' Show that for an ideal gas, the slope of the COnstanl volume line on the T...., diagram is more than that of the constant pressure line.



FIg. Ex. 10


We have, for I kg ofideal gas Tds - du + pdv

" c~dT+pdv

(~~)~ - ~

TO, - dh - vdp
- cpdT-vdp

OT) T (Tsp " cp



This is shown in Fig. Ex. 10.4. The slope: of the constant volume lin.e passing through point A is steeper than that of the constant presS\lfe line passing through the same point. (Q.E.D.)

'Example 10.5 0.5 kg of air is compressed reversibly and adiabaticall y from 80 kPa, 6O"e toO.4 MPa, and is then expanded at constant pressure to the original volume. Sketch these processes on the Jrv and T-:J planes. Compute the heat
uansfer and work transfer for the whole path.

Solution The processes have been shown on the Jrv and T-:J planes in Fig. Ex. 10.5. At state 1 P1 J11" mRTI

t '\(J,'

Fig. U. 10.5





, ,,



VI '"' volume of air al stale I

"" m R1j = 1 x 0.287 x 333 .. 0.597 mJ PI 2x80

Since the process 1-2 is reversible and adiabatic

For process 1- 2, work done

mR(1j - Ti

_ 112 x 0.287(333 - 527) 0.4


. I

312=- -69.6kJ
Plvl -; P2 v l

.. .ft.. = ~ = .!. (-",-)1 VI P2 400 5 " o. (,)lIU I V. t 5 = 3.162 =it

V .. 0.597 "' 0.189m]


For process 2- 3, work done

WI _1 '" PI (VI - Vv = 400 (0.597 - 0.189) - 163.2 kJ

: . Total work transfer

W = WI_ I + Wl-1 = - 69.6 + 163.2 = 93.6 kJ


for states 2 and 3

h.!i ..


Tl - T2...l.. - 527 x3.162 - 1667 K

" ",

Total heat transfer

Q " QI-2 + Q2-1" Ql-l - mc p (Tl .. 112 x 1.005 (1667 - 527)

.. 527.85 kJ


Example 10.6 A mass of air is initially at 260C and 700 kPa, and occupies
0.028 ml. The air is expanded at constant pressure to 0.084 ml. A polytropic process with n .. 1.50 is then carried out, followed by a constant temperature process which completes a cycle. All the processes are reversible. (a) Sketch the cycle in thep-V and T-s planes. (b) Find the heat received and heat rejected in the cycle. (c) Find the efficiency of the cycle.


(a) The cycle is sketched on the Jrv and T-1 planes in Fig. Ell.. 10.6.
PI = 700 kPa, TI .. 260 + 273 - 533 K " T] VI " 0.028 m1 1 Vz '" 0.084 m PI VI = mRTI

from the ideal gas equation of state m " 700 x 0.028 .. 0.128 k 0.287 x 533 g



Fig. Ex. 10,6




1i _ P1V 1

_ 0.0084 - 3 1j PII'i 0.G28 T2 - 3x533 - 1599K


P (" Jn l(a-I) ( 1599)1.510., = - (JY - 27 Pl 1j 533 Hcat transfer in process 1-2 QI_l - mcp (T1 - T]) = 0.128)( 1.005 (1599 - 533) = 137.13 kJ
fL .. ..2..

Heat transfer in process 2- 3

Q l-l .. AU +

mR(TJ. -1))

"' mcy(TJ - Tz>+

., mcy !'..::L (TJ - T1)


= 0.128xO.7 18x 1.5-1.4 (533 - 1599) 1.5- 1 .. 0.128 x 0.718 x =- 19.59kJ

.i!:!..(_ 1066)

For process 3-1

<tQ = dU + dW "" dW

Q)-1 - W, _I -

, pdV - mRT] In ....:.L " J , V,

l!1.. _ 0.128 x 0.287 x 533 In

- mRTI In

(1-) 27


&uic IIU Applid 1lmnodyniImia

.. - 0.128 x 0.287 x 533 x 3.2959 .. - 64.53 kJ (b) Heat received in the cycle

Ql " 137.13 kJ
Heat rejected in the cycle

Q2 " 19.59 + 64.53 " 84.12 kJ

(e) The efficiency orthe cycle



, __ I _ ~ _ I _ 84.12 - 1 - 0.61


-'" 0.39, or 39% Example 10,7


A mass orO.2S kg or an ideal gas bas a pressure 0]00 kPa, a

t.emperatureor80~C, and a volume oro.07 m3 The gas undergoes an irreversible adiabatic process to a [mal pressure of 300 kPa and final volume orO. IO mJ ,

during which the work done on the gas is 25 kJ. Evaluate the ~ andcy orthe gas and the increase in entropy of the gas.

Solution From
Pt Vl"' mRTI
Final temperature 300 x 0.07 .. 0.238 kJlk K 8 0.25 x (273 + 80)

T2 '"' PlP2 = 300xO.l -50SK mR 0.25 x 0.238

Q " (U2 - U t )+ W - mcy (T1 - T1)+ W

o.. 0.25 cy(505 ~


353) - 25

25 0.25 x 152

~ 0.658 kJlkg K

Entropy changc

cp-cy >< R

c p - 0.658 + 0.238 " 0.896 kJ/kg K

~-Sl - mcy ln li. + mcp In ~


- mc p In Yi - 0.25 x 0.896 In 0.07

'" 0.224 x 0.3569 '" 0.08 kJ/kg K

!i _


Ezample 10,8 A two-stage air compressor with perfect intetcooling takes in air at I bar pressure and 27~C. The law orcompression in both the stages iSpvl-J

.. constant. The compressed air is delivered at 9 bar from the H.P. cylinder to an air receiver. Calculate, per kilogram of air, (a) the minimum work done and (b) the heat rejected to the intercooler.

Solution The minimum work required in a two-stage compressor is given by Eq. (10.65).

w __ "_ _ I!!l..)" 2 RT. [(


n- 1


- ''''

_ 1]

'" 2 x 1.3 x 0.287 x 300 [(3)o.1IL..l _ I] 0.3 "' 26xO.287x lOOxO.287= 214.16kJlkg Ans.(a)

Pl "

.j PIP] =,ffX9 Po

3 bar

.!c . (li)n-lin . 30.1lu .. 1.28856

T2 = 386.56 K
Heat rejected to the intercooler = 1.005 (386.56 - 300) '" 86.99 kJlkg An.l'.(b)

Example 10.9 A single-acting two-stage air compressor deals with 4 m'/min of air at 1.013 bar and 15"C with a speed of250 rpm. The delivery pressure is 80 bar. Assuming complete intercooling, find the minimum power required by the compressor and the bore and stroke of the compressor. Assume a pistong speed of J mis, mechanical efficiency of75% and volumetric efficiency of80"1O perstage. Assume the polytropic index of compression in both the stages to ben - 1.25 and neglect clearance.
Pl "" .JPlP. =.JI.OI3XSO '"' 9bar
Minimum power required by the cOf!)pressor

W = ~PI~[(li)a-ll" -I] X-In-

1 P I




2 x 1.25 0.25

1.013 x 100 0.75


4 [( -60 1.013

,)0.2" 1.25 - I1

.. 1013 x 4 x 0.548 " 49.34 kW 45 If L be the stroke length of the piston,

2L!!.. - 3m1s


376 = Lo; 90 x 100 --36cm 150 Effective LP swept volwne - 41250 - 0.016 m J


~(Du.r x 0.36 x '1...,. 0.016

- ,/ :;-';~2;;-;,

0.0 16 x 4


x 0.36 x 0.8

- 0.266 m 26.6 em


.E!..!::L 1i

P, I) 1)

4 4

I) ~ 11


.. 1.013

!!....DfIPL !Di.,L
D lip

0266 ,


0.0892 m - 8.92 em


Example 10.10 A single cylinder reciprocating compressor has a bore of 120 mm and a stroke of 150 mrn. and is driven at a speed of [200 rpm. II is compressing CO 2 from a pressure of 120 kPa and a temperature of 25C to a temperature of 215C. Asswning polytropic compression with /I - 1.3, no clearance and II vo lumetric efficiency of 100"A., calculate (a) the pressure ratio. (b) indicated power, (c) shaft power, with a mec hanical efficiency of 80%. (d) mass flow rate. . Ifa second stage of equal pressure ratio were added, calculate (e) the overall pressure ratio and(f) bore of the second stage. if the same stroke was maintained. Solulion (a) With respecl lo Fig. Ex. 10.10,
488 )1.310,) PiP1 = (T.jT1) DI(,..ll '" ( '" 8.48 298
All!'. (a)

W = n _ 1P1V\ (Pl l pl)-'- -i

[ .-, 1
120 X 101 x 0.00 17 ((8.48)u.lI1 .1_ I] - 563.6 J
All!'. (b)

.. ..!1. x

Indicated power -- 563.6 x 1: 0 -- 11 .27 kW


' f - - ----"

v. _v,


Hg. EL 10.10

(c) Shaft power - 11.27 - 14.1 kW


AII.1. (c)

(d) Volumetric flow rate " 0.0017 x


... 0.034 ml/s

m= PI"!

= 120xlO x O.034 " 0.0725kg/s

(8314/44) x 298

AII.1. (d)

(e) lfa second slage were added with the same pressure ratio, the overall pressure ratio would be

(.I'Ll -(.l'Lln

= (8.48)2 .. 71.9

Ans. (e)


(f) Volumetric delivery per cycle is Vl . n Since PI Vi = P2 V2 ,

V~ " (l'LlI'D X VI "[_ 1_]111.3 )( 0.0017

P2 .. 0.00033 ml. g.48
If the second stage would have a swept volume of 0.00033 ml, with the same stroke,


X 0.15

" 0.00033

d - 53mm

Example 10.11 A mixture of ideal gases consists of3 kg of nitrogen and 5 kg of carbon dioxide at a pressure of300 kPa and a temperature of 20C. Find (a) the

378=mole fraction o r each constituent, (b) the equivalent molecular weight or the mixture, (c) the equivalent gas constant or the mixture, (d) the partial pressW'lis and the partial volumes, (e) the volume and densiry orme mixture, and (I) th'e cp and Cy of the mixture. Ir the mixture is heated at constant volwne to 40C, find the changes in inteIDat energy, enthalpy and entropy orthe mixture. Find the cltanges in internal energy, enthalpy and entropy orthe mixture if the heating is done at constant pressure. Take yforC0 2 and Nllo be 1.286 and 1.4 respectively.


(a) Since mole fraction xi "


XN2 '"

3 28 5 = 0,485



xoo l


28 44 (b) Equivalent molecular weight of the mixture

3 44


5 .. 0.515

M " xI1l1 + x2Pl ~ 0.485 x 28 + 0.515 x 44

.. 36.25 kg/kg mol
(e) Total mass,

", .. "'N: +"'001- 3 + 5 " 8 kg

Equivalent gas constant of the mixture

R " mN2RNl + mcolRco j



0.89 + 0.94 8 8 .. 0.229 kJ/kg K P"" XN1 'P = 0.485 x 300 '" 145.5 kPa PCOj "xCOjp = 0.515 x 300 " 154.5 kPa


V~ = mNIR~IT =

3 X 8.3143 X 293 28 _ 0.87 mJ 300

.. "'et? Reo l CO:! p

5 X 8.3 143 X 293 44 .. 0.923 mJ


- = 379 (e) Total volume of the mixture

vvDensity of the mixture

mRT '" mN j RNj T '" mco jRco.T P PNl POOl

SxO.229x293 _ 1.79ml 300

m 8 P - PNI+Peo: - y== 1.79

= 4.46 kglml (Q
cpNj - CyNI '" RNj

_ R~l _ 8.3143 CYNI-y_I-2SX(I.4 1)

'" 0.742 kJlkS K
CpNI'" 1.4 x 0.742

"' 1.039kJIkSK F 1.286

,~ - -

- == '" 0.661 kJlkg K y-I 44 x 0.2S6


CpC'OJ -

1.286 x 0.661 '" 0.85 kJlkS K

Forthe mixture

... l + mCO,cpCOl , = mN ICp. mN +mCOl


.. 3/S x 1.039 + 5/S x 0.S5 = 0.92 kJlkg K

C _

mNlcvNI + mcojcvCO l m

'"' 3/8 x 0.742 + 5/S x 0.66 1 = 0.69 kJ/kg KAns. If the mi;ll:ture is heated at constant volume
U1 - U L=mcy (T1 - TI )

=Sx O.69x(40-20) " 110.4kJ Hl - H I '" mcp (T2 - TI ) = SxO.92x20 " 147.2 kJ
S2 - SI - mr.y ln ..2. T, + mRln .:l. "


- me In..!i. "" S x 0.69 x In


380== 0.368 kJlkg K

If the mixture is heated at constant pressure,o.U andtJI will remain the same. The change in entropy will be


Example 10.12 Find the increase in entropy when 2 kg of oxygen at 60C are milled with 6 kg of nitrogen at the same tcmperature. Thc initial pressure of each constituent' is 103 kPa and is the same as that of the mixture.


- !5!L -_ --v,.J:_

2 6 _ +_
32 28


= 0.225


PN_ _ I : 0.775

Entropy increase due to diffusion

llS " - mn.. Rn.. 10 POi - m" R" In PNI -<_'P lip
_ _ 2 ( 8.3[43) In 0.225 _ 6 (8.3143 ) In 0.775 32 28 ' - 1.2314kJlkgK Ans. Example 10.13 The gas neon has a molecular weight of20. 183 and its critical temperature, pressure and volume are 44.5 K., 2.73 MPa and 0.0416 m)lkgmol. Reading from a compressibility chart for a reduced pressure of2 and a reduced tempenttureof 1.3, the compressibility factorZis 0.7. What an: the corresponding specific volume, pressure, tempernture, and reduced volume?

Solution At P, " 2 and T, " 1.3 from chart (Fig. Ex. 10.13),.z " 0.7 P " 2 x 2.73 " 5.46 MPa


I... - 1.3


T = J.3 x 44.5 " 57.85 K


pv "' ZRT
x 8.3 143 x 57.85 , - 0.7 20.!83 x 5.46 x 10) .. 3.05 X IO-J m)lkg

"' "

Z " 0.7

0.7 ..... .

o '----', 2 ~~~~~~0

FIg. Ex. 10.13

3.05 X 10- 3 X 20.183

V,""-... =

4.16 X 10-2

= 1.48


EzampJe 10.14

For the Berthelot equation of state

P v_b-rv 2
show that (a) lim



(RT - pv) - 0 ,., ,

.!i P


(b) lim .. =
T .... _

(c) Boyle temperature, TB =

~ baR'

.......;csp = _ I _ ~20R v =3b.T = (d) Critical pro!"-.w < l2b 3b' < c
(e) Law of corresponding states

J27bR' 80

( p,

+ ~)(3V, - I) = 8T, T, v,
v- b Tv

RT p._ - - -2

RT=(P+-'-) (v-b) TO'


382=RT "" v+ ~ -b-~ P puT pulT RT - pv " .a - -bp- - ab vT v 2T

lim (RT - pu) - O
,~ ,

Proved (a)

(b) Now

V " RT _ _ a_ +b+ ~



R - -a -v "' - +b - + ab -T p puT l T pulTz

r .... _ T

lim .Y. .., !!.


Proved (b)


The last three terms of the equation are very small, e:\eept at very high pressures and small volume. Hence mbstituting v '" RTlp
pu .. RT---+bp+----:<"""'r RT2 R2r J
ap abp2

il(p')] _ _ _ a_ + +2abP _ b 0 T RTl RlTl


whenp ~ 0, T" TSo the Boyle temperature

_ a_ = b RTi

To (d)

JbR a


RT a P- - - -2

ap ) [a;



T_ T. - - (Vc

R, -bl

+-- - 0




alp ) = 2RT. _ ~ = 0 [ av l T-T (v< bl T. v: c

[ Pc

+ ~l(V~b) "' RT< T"Vc

By solving the three equations, as was done in the case of van der Waals equation of state in Anicle 10.7



of G/IJtJ IUul Go.s Mixh41ls

- = 383
Proved (d)

P. - 1 2b

lf20R ,-..--fJ'b ,Vc '" 3b, and T.: V27bii

a = _'_c 7:C R : 3pC 1i C
, , p' b=....... R ~ - _,_c (SOthDtZ "3/S) 3 ' 3 ~ c

(e) Solving the above three equations


Substituting in the equation

(p+ ~2)(V - b) = RT
( p+

3pcv~2 r. )(v-~) == Sp.v . T



- I) = S1, ( PI + b)(3V, 1, v,

This is the law of corresponding states.

Proved (e)

10.1 10.2 10.3 10.4 10.5 10.6 10.7 10.S 10.9 10. 10 10. 1 I 10. 12 1D . 13 10.14 1D.15 Wllat is a mole? What is Avogadro's law? What il anequalion of stale? What is the fundamental property of gases with respect 10 the productpv? What is universal gas constanl? Deflnc an ideal gas. What is the characteristic gas constant? What is Boltznuuln constant? Why do the specific healS ofan ideal gas depend only on the atomic structure of the gas? Sliow that for an ideal gas the internal encrgy depends only on its temperature. Show that the enthalpy ofan ideal gas is a function of temperature only. Why is ~ no temperature change when an ideal gas is throttled? Sllow that for an ideal gas, cp - c. - R. Deril'e the equations uCd for computing tile entropy change ofan idcal gas. Show that for a reversible adiabatie process executed by an idea l gas, the following ~Iations hold good : (i) pul - constant, (ii) rv't"l '" constant, and (iii) T,P-"f1."I_ COlISlant. Express the changes in intnnal energy and enthalpy ofan ideal gas in a reversible adiabatic process in tCT1ll5 of the pressure rado. Derive the expression nfwnrk \fansfcr for an ideal gas in a reversib le isothcnnal process. What is a polytropic process? What are tile relations Imongp. v and T of an ideal gas in a polytropic procC!l5?

10.16 10. 17 10.1 g

3M=10.19 Sbow that the entropy c!lange between states 1 and 2 in a polytropic process. po" .. conmmt, is given by the following relatioll5:
(i) ~ _ ~ ..
1 I


Rln 1j




(iii) !Z-~ I - -

n-y 7-1

Rln ..!!.

10.20 What are the eltpressions o(work transfer for an ideal gas in a polytropic procns, if the gas is: (I) a closed system, and (ii) a stcady flow system? \0.21 Derive the expression of heat tnlruIfer for an ideal gas in a polytropic PI'OCC$5, What is the polytropic specific heat? What ~1)Uld be the directioD of heat tnmsfer if (a)/I > y. and (b) n < y1 ' 10.22' Wby is the C)';temal work supplied to a compressor equal to -

PI vdp?

10.23 Why does isothermal compression nd minimum work and adiabatic compression UlaltUnwn work? 10.24 What is the advantage of staging the eompres.sion procCM? 10.25 What is meant by perfeet intcn:ooling? 10.26 Show that the optimum inttnnediate pressure of a two-s13gc reciprocating compressor for minimum work is the geometric mean of the suction and discharge pTCS5I1TCS. 10.27 Explllin how !he use ofintamediate pl'CSSllre for minimum work resu lts in equal pressure ratios in the two stages of compreuion, equal discharge temperatures, and equal work for the two slages. 10.28 What is the isothermal e fficiency ofa compressor? 10.29 Define volwnetric efficiency ofa compressor. 10.30 Wby docs the "olumetric efficiency ofa compressor decrease: (a) as \be cJCiIllIIlce increases for the &i"en pTCSSIITC ralio, (b) as Ihe pressure ratio increases for the given clearance? der Waals equation ofslatc. How docs it differ from the ideal 10.3 1 Write down the gas equation of stale. What is force of cohesion? Whal is eo-voll.lllle? 10.32 What arc Ihe two-<:onstant equations of state? 10.33 Give the virial expansions for pV in tenns ofp and v. 10.34 What arc virial coefficients? When do they become zero? 10.35 What is the compressibility factor? 10.36 What arc reduced properties? 10.37 What is the gcntnlli=i compressibility chart? 10.38 What is the law ofCOlTeSpOnding Slates? 10.39 Express Ihe van del' Waals constants in lemu of crilical properties. 10.40 Draw the diagram represcnting the law of cOTTCsponding states in reduced coordinates indicatin8 the isothcnns and the liquid and vapour phases. 10.41 Define Boyle temperal\lre? How is it computed? 10.42 Slate Dalton', law ofparlial pressures.




10.43 How is the panial pres5lllll in a gas mixcure related 10 the mole fraetion1 10.44 How are the characteristw gas constatrt and the molecular weighl oca ga.'IInixturc 10.45 What u fjibb's theorem? 10.46 Show that in a dilTusioo process a gas undergoes a free expansion from the total p!nSUtt 10 the relevant partial press~. 10.41 Show that io a diffusion process al constant temprnlt~ the entropy incl'e3.2$ and the (jjbbs fuDction ~reases.


Whal is the mus of air contained in a room 6 m x 9 m x 4 m if the pressure is 101 .325 kPa and the tempemlun' is 25C? AIlS. 256 kg 10.2 The usual cooking gas (mostly methane) cyelinder is about 25 cm in diameter and 80 em in height. II is charged 10 12 MPa al room tempenllun' (27"C). (a) Msuming the ideal g85 law, find the mass of gas filled in the eyciinder. (b) Explain bow Ihe actual cyclinder contains nearly IS kg of gas. (c) If the cylinder is to be protected againsl ex~i ... e pressure by means ofa fu5iblc plug. al wballeJUprnllun' should the plug melt 10 limit the maximwn press~ 10 15 MPa? 10.3 A certain gas has cp " 0.913 and c. " 0.653 kllkg K. Find the molecular weighl and the gas Coostanl R of the gas. 10.4 From an experimental determinalion the spific beat mlio for acetylene (CzH z) is found 10 1.26. Find the IWO specific healS. 10.5 Find the molal specific heats of monatomic, dialomic, and polyatomic gllSCS, if their specific beal ratios are respectively S{3, 7/5 and 413 . 10.6 A supply ofnalural gas is requiredona sile 800m abo~'e stol1lge Ic\'c1. The gM al - ISOC, 1.1 bar from storage is pumped steadily to a poinl on the site wbere ilS pressure is 1.2 bar. ilS temperat~ 15"C, and its flow rale 1000 m1lhr. If the work transfer 10 the gas at the pump is IS kW, find the heat transfer 10 the gas berween Ibe rwo points. Negleet the cbange in K.E. and assume !hit the gas has the properties of methane (CH. ) whicb may be treated as an ideal gas ltaving Y'" 1.33 (g - 9.75 AIlS. 63.91r::W 10.7 A constant vo lume chamber of 0.3 m ) capacity conlll;n. I kg of air It S"C. He~t is transferred 10 the air until the temperature is l OO"C. Find the .....olk done, the lleat transfer=!. and the changCll in intemal energy, enthalpy and entropy. 10.8 One kg orair io a closed system, initially ~t SoC and occupying 0.3 m1 volume, undergoes a constant pressure beating process to loo C. Then: is no work other !ban pdv work. Find (a) the work done during the process, (b) the hell tra/lsfem:d, and (c) the entropy change ofthe gas. 10.9 0.1 m' ofllydrogen inilially at 1.2 MPa. 200C undergocs an:vmible isothermal expansion to 0.] MPa. Fiod (a) the work done during the process, (b) the lIeat transfem:d, and (c) the entropy change oflbe gas. 10.10 Air in a closed SlIItiOnary system el(pands in a /'e\'cnible adiabatic process from 0.5 MPA, 15C 10 0.2 MPa. Find the final temperature, and per kg of air, Ibe change in enthalpy, the beat transferred, and the won: done.



386=10.11 If the above process occurs in an open steady from system, find the final tempcnture, and per kg ohiT, the change in internal energy, !he heat UlIJl5fe=d, and the shaft work . Neglect velocity and elevstion changes. 10. 12 The indicator diagram for a eenain water-<:ooled cyelindcr and piston air compressor sbows that during compression pvlJ .. oonslanL The compression sIart!I at 100 kPa, 2SC and ends at 600 kPa. If the process is re\'ersible, how much hea t is tnuJ5fCTKd per kg of air? 10. 13 An ideal gas ofmolular weighl30 and r- 1.3 occupies a volume of J.5 mJ at 100 kPll and 77"C. The gas is compressed according to the law pv us - constant to a pressun: of 3 Mfa. Calculate the volume and temperature at the end of compression and beating, work done, helt transferred. and tbe total change of

10. 14 Calculate the cbange of en~ wben I kg of air cbanges from a temperature of 330 Kanda volume of 0.15 m to a temperatureof550 Kand. volumcofO.6 ml. If the air expands according to the law. prl' - constant, between tbe same end Slates, calculate tbe heat given to, Dr extracted from, the .ir during the expansion, and ihow thaI it is approllimately equal to the change of entropy multiplied by the mean absolute tempemnm::. 10.15 0.5 kg ofair, initially al 2SC, is heated reversibly at cODlitanl pressure until the volume is doubled, and is then heated reversibly al coru;tant volume until the pressure is doubled. For the total path, find the work transfer, the heat transfer, and the change of entropy. 10.16 An ideal gas cycle of three: processes I15C:!I Argon (Mol. wt. 40) "" II worki'J substalWe. Process 1-2 is ~versiblc adiabatic expansion from 0.014 m, 700 kPu, 28ifC to 0.056 ml , Process 2-3 is a revemble isothermal process. Process 3-1 is a constant prasurc process in which heat Ir.ln5fer is zero. Sketcb the cycle in tbep-vand T-r planes. and find (I) the work transfer in process 1- 2. (b) the work Il1IIISfer in process 2-3, and (el the net work of the cycle. Tuc r - 1.67. Alii. (a) 8.85 kJ (b) g,96 IcJ (cl 5.82 kJ 10.17 A gas occupies 0.024 m) al 700 kPa and 95' C, II is expanded in the non-flow pTOCC$$ accQrding tQ the law pvl.l _ conslanl to a prt$SUTe of70 kPa after which it is heated at constanl pressure back 10 its original tempemlUfC. Skelch Ihe process on the p-v and T- s diagrams, and calculate for the whole process the work dOrM:, the heal transferred. and the change ofeotropy. Take So - 1.047 and c. - 0.7751cJIkg K for the gas. 10.18 0.5 kg ohir at 600 kPa receives an addilion orheal at constant volume so thai its temperalure rises from II O"C 10 6S0C. II then expands in a cyclinder polytropically 10 its original tcmpernture and the index of expansion i! 1.32. Finally, it is compressed i50lhermaly 10 iu original volume. Calculate (a) the change ofentrDpy during each oflhe three stages, (b) the pressures at the end of constant ~'olumc heat addition and al the end of expansion. Sketch the processes on the p-v and T-s diagrams. 10.19, 0.5 kg ofhclium and 0.5 kg Qfnilrogen are mixed at2ifC and al a lotal pressure of 100 kPa. Find (a) the volume of the mixture, (b) the panial volumcs oflhe comporoents,(c) tbepanial pressUle5 ofthecomponcnts, (d) the mole fractions of the components, (e) the speeific bealS cp and c. of the mixture, and (I) the gas conslant of'he mixl\Itt. 04,,1. (a) 3.48 1 m 1 (b) 3.045. 0.436 m l (c) 87.5, 12.5 kPa (d) 0.875. 0.125 (e) J.I I. 1.921 kJJk(i) 1. 189kJJkgK.

/'ropmia o/GtmJ Ifllll GIU MulllrtJ


10.20 A gaseous mill1ure consists of! kg of oxygen and 2 kg of nitrogen at a prcssure of ISO kPa and a temperature: of 20C. Detennine the changes in internal energy , enthalpy and entropy of the mixture when the mixture is lIeated to a temperature of 100C (a) at constant volume, and (b) at constant pressure. 10.21 A closed rigid eye linder is divided by a diaphragm into two equal compartments, each of volume 0.1 m'. Each companment contains air at a temperature of 20C. The pressure in one compartment is 2.5 MPa and in the other compartment is I MPa. The diaphragm is rupturro so that the air in both tile compartments mixes 10 bring thc pressure to a unifonn value through~ut the cylinder which is insulated. Find the net change of entropy forthe mixing process. 10.22 A vessel is divided into three compartments (a), (h), and (c) by two partitions. Pan (a) contains oxygen and has a volumc of 0. 1 m', (h) has a volume of 0.2 m' and contains nitrogen, while (c) is 0.05 m' and holds COz. AJlthrce parts are at a pressure of2 bar and . temperalun: of 13C. When the partitions are removed and the gases mix, dctenninc lhechange ofenlropy of each oonstituent, the final pressun: in the veMel and the partial pressure of each gas. The vessel may be taken as being completely isolated from its sttrI"OWldings. An.1. 0.087S , 0.0783, 0.0680 kJlK; 2 bar; 0.5714, 1.1329, 0.28S7 bar. 10.23 A camet cycle uses 1 kg of air as the workillg fll<d. The maximum and minimum temperatures of the cycle are 600 K and 300 K. The maximum pressure of the ~Ie is 1 MPa and the volume of the gas doubles during the isothermal heating process. Show by calculation of net work and heat supplied thai the efficiency is the maximum possible fot the given maximum and minimum temperatures. 10.24 An ideal gas cycle consists of three reversible processes in the following sequence: (a) constant volume pressure rise, (h) isentropic expansion 10 I" limes the initial volume, and (c) constant pressure decrease in volume. Sketch Ihe cycle on the p-v and T- sdiagrams. Show Wt the efficiency of the cycle is
rT - 1-r ( I" - I)

11'1<1< '"


Evaluate tile cycle efficiency wilen r '"

and 1" 8.

AnJ. (1'/ '" 0.378)

(a) show tilat 'P< '" ---!-.4e"b' v< - 2b , T< - -4Rb (h) expand in the form

(c) show thOI

bR 10.26 The number of moles, the pressures, and the tempenllures of gases u. b, and c are given as foll ows

To - ....!...

388=Gas III (ig 11101) P (lPa) I ("C) Nl I 350 100 CO 3 420 200 Ol 2 700 300 If the containers are eolUleC!ed, allowing the gases 10 mix freely, find (al the pressure and temperature of the resulting mixture at equilibrium, and (b) the cbange of entropy of each constituent and that of the mixture. 10.27 Calculate the volume of2.5 kg moles of steam al 236.4 aun. and 776.76 K with the help of compressibility factorvefSus n:duced pressure graph. At this volume and the given pressure, what would the temperature be in K, if steam behaved like a van der Waals gas1 The critical pressure, volume, and temperature of steam are 218.2 atm, 51 cmllkg mole, and 647.3 K respectively. 10.28 Two vessels,.4 andB, each ofvohmx 3 m l may beconnected together by a tube Q of negligible volume. Vcsscl.4 contains air at 7 bar, 95 C while B eontains aiT at 3.5 bar, 205~. find thccbangeofentropy wben.4 is connected lOB. Assumethc mixing to be complete and adiabatic. AilS. (0.975 kJlkg K) 10.29 An ideal gas at temperarure Tt is heated at constant pressure to Tl and then expanded reversibly. according 10 the law pr.r" - constant. unlil thc: lempcnlture is once again Tl . What is the requim:l value of II, ifthc: cbangcs of eouapy during tbe separate processes ate equal?


(._-'L) y'\

10.30 A cenaio mass of sulphur dioxide (SO:) is contained in I vessel of 0.142 m l capacity, at I pl"C!l.'lUrt' and temperature of 23.1 bar and 18"C respectively. A valve is OIXnN momentarily and the prcssu: falls immediately to 6.9 bar. Q Sometime later tbe temperature is again I8 C and the pressure is observed 10 be 9.1 baT. Estimate the value of specific heat ratio. .4"". 1.29 10.31 A gaseous mixtun: contains 21 % by volume nf nitrogen, 50"/. by volume of hydrogen. and 29% by volume of carbon-dioxide. C.lculale the molecular weight of the mixture, tbe characteristic gu constant R for the mixture and the value of the reversible adiabatic index r. (At 10 C, the tp values of nitrogen. hydrogen. and carbon dioxide are 1.039, 14.235, and 0.828 kJlkg K respectively.) A cyC\inder contains 0.085 ml of tbe mixture at I bar and 10Q C. The 8as Wldergoes a reversible non flow process during which its volume is m:luced to one-fifth of its original value. If the law of compression is pvlJ. _ conslalLI, delmnine the work and heal transfers in m&glliludc and sense and the change in entropy . .411.1". 19.64 kgik:g mol, 0.423 kJlkg K., 1.365. - 16 kJ, - 7.24 kJ, - 0.31 kJlkg K 10.32 Two moles of an ideal gas at tcmperatun: T and pressure p are contained in a compartment. In an adjacent companment is one mole of an ideal gas at temperatu~ 2T and pressure p. The guts mix adiabatically but do oot react chemically wben a panition separating the compartments is witbdta ...."D. Show tb31 the entropy increuc: due to the mixing process is given by



2I + _ '_In 4 y- I






provided that the gases Ilt"e different and that the ratio of specific heat yil the same for both gases and remains constant. . What would the entropy dumge be if the mixing gaKS wc:n: of the same spttiel? I'It moles oran ideal gaut prcssurept and temperature Tare in one compartment o ran insulated container. In an adjoining compartment separated by a parliCion, are oJ moles ofan ideal gas at PrnsurePl and Ie!Dpel1llun: T. When the partition is mnoved. ea(cul ate{a) the final pressure of the mixture. (b) the entropychange when the gases are identical . and (c) the entropy change when the gases an:: different. Prove that the entropy change in (c) is the same as that produced by two independent fre.e ClIpansions. ANUme thllt 20 k8 of sto:am are required at a pre~~ of 600 bar and a temperature of 750"C in order to condl.lC1 parti cular experiment A 140-liue beavy duly tank is available for storage. Predict if this is an adequate storage capacity using: (a) the ideal gao; theory. (b) the compressibility factor chan, (c) the van del: Waals equation with Q '" 5.454 (litrc:)~ aunl(gmo l)l. b - 0.03042 Jitres/gmol for steam. (d) the Mollie,.-,;:hart (e) the steam mbles. Estimate the error in each. Ans. (a) 157.75/, (b) 132.5 1 I. (c) 124.94/(e) 137.29/ Estimate the pressure kg of COl gas which occupies a vo lume of 0.70 m' at 75C. lJ.'iing the Beattie-Bridgeman equatio n of state. Compllt"e !his result with the value obtained using the generalized compressibility chart. Wh ich is more accurate and wby'! For COl with units of aIm. Iitreslg mol and K. Ao .. 5.0065. (J . . 0.07132. 8 0 . 0.10476. b .. 0.07235. C x 10-<" 66.0. Measureme nts of pressure and temperature at various stages in an adiabatic ai r turbine: sho w tbat the sta tes of air lie on !he liTH: pvl.~ ~ constant. [f kinetic and gravitational potential energy are neglected. pm\'c thatthc shaft work perkg as a function of pressure is given by the following relation


W- 3's P1V1

[1 -(;; t]

Take yfor air as 1.4. 10.37 Air nows steadily into a comp ressor 8t a tempel1lture of l JOC and a pressure of 1.05 bar and leaves at a temperature of247"C and a pressure of6.3 bar. There is no heat transfer to or from !he airus it f10v.'S through the compressor; changes in elevation IIlId \'c!ocity Ilt"e negligible. Eval uate the external work done per kg of air. assuming air as an ideal gas for which R " 0.287 kJlkg K and y .. 1.4. Evaluate the minimum external work required 1 0 compress the air adiabatically from the same initial state to tbc same ftD31 pressure and the isentropic efficiency 9fthe compressor. An... - 225 kJlkg. - 190 kJlkg, 84.4%

a90=10.38 A slow-speed reciprocating air compressor wilb a WIlIer jacleet for cooling appro~ilDlltes a quasi-SIalic oompre5sion process following a pathpvu .. coM.. If airenters at a temperature of20"C and a pressure of I bar, and is compressed 106 bar at a rate of 1000 leglh. detcnnine Ibe discharge temperature of air, the power required and the heat transferred per kg. AIlI. 443 K, 51.82 kW, 36 kJlJrg 10.39 A single-acting two-slllgt reciprocating air compre550r with complete intcrrooling delivers 6 kg/min al 15 bar pressure. Assume an inlllke condition of I bar and IS'C and that the compression and expansion processes are polytropic with" .. 1.3. Calculate: (a) the power required, (b) the isothermal cfficieocy. An.r. (a) 26.15 leW (b) 85.6% 10.40 A two-slage air compressor receives 0.238 m'ls of air at I bar and 27C and diKharges it al 10 bar. The polytropic index ofcomprcssioo is 1.3S. Determine (a) the minimum power necessary {or compression, (b) the power needed for single-stage compression to the nme p=sure, (c) the maximum temperature for (a) and (b), and (d) the heal removed in the intercooler. AIlI. (a) 63.8 kW, (b) 74.9 kW, (c) 404.2 K , 544.9 K, (d) 28.9 leW 10.41 A mUI of an ideal gas exim initially al a pressure of 200 kPl, temperature 300 K.. and speci fic volume O.S m)/kg. The value of yis 1.4. (iI) Determine the specific heats of tbe guo (b) What is the change in entropy when tbe gls is e>;panded to pressure ]00 kPII IIccordinl to the law pv1J .. const? (c) What will be the entropy change If the path is pvt. .. const. (by the application of a cooling jacket during the process)? (d) What is the inference you can draw {rom this example? An.r. <al 1.]66,0.833 kJlkg K.. (bl 0.044 kJlkg K (cl - 0.039 kJ/kg K (d) Entropy increases wilen" < yand dccrea5es when,,:;> 10.42 (I) A closed system of2 kg ofair initially at pressure 5 aim and temperature 227C, expands reversibly 10 presallre 2 aim following the law pvus coost. Anuming air all an ideal gu, detennine the "OR: done and the heat

A....... 193 kJ, 72 kJ (bl If the $)'JIem doe$ the same expansion in a steady flow process, what is the work done by the system? AIt.t. 241 kJ 10.43 Air contained in a cylinder fitted with II piston is compressed reversibly according 10 the Jaw pl/I .21 .. COIUt. The mas!i of air in the cylinder is 0.1 kg. "The initial pressure is 100 kPa and the initiallel11pcrature 2ife. The final volume is 118 of the initial volume. Detenninc the work and the heat transfct. AM. - 21.9 kJ. - g.7 kJ 10.44 Air is contained in a cylinder fitted with a frictionless pistol!.. Initially the cylinder .S m) of air at I .S bar, 2O"C. the air is then compressed reversibly contains O aeeording to the law fIU" " constant untillbe [mal preSIl1ll: is 6 bar. at wbicb point the tempcTllturc is 120C. Detcnnine: (a) the po]ytropi<: indu II, (b) the fmal volume of air, (c) the work done on the air and the heat transfer, and (d) the net change in entropy An.r. (a) 1.2685, (b) 0.1676 m) (e) - 95.3 kJ, - 31.5 kJ, (d) 0.0153 kJlK. 10.45 The specifIC heal at constant pre$5ure for air;$ given by cp " 0.9169 + 2.577 x 10.... T - 3.974 x 10'" 1'" kJ/kg K


--= 391
~Iermine the chnge in internal energy and thaI in cnlropy of air when il undergoes a change of stale from I atm and 298 K 10 a lemperatureof2000 K al the same pressure. AIlS. 1470.4 kJlkg, 2.1065 kJlka K A closed allows nilJogen 10 cllpa.nd reversibly from a \'olume of 0.25 m' 100.75 m along the path pvl .12 .. eonst. llIe original pressure of the gas ;s 250 kPa and its inilial temperature;$ 10(l"C. (a) Draw the~vand T-8 diagrams. (b) What ~ the final to:mper.uure and the final pressure: of the gas? (c) How much wonr. is done and how much heat is transferred? (d) What is the entropy change of nitrogen? An.r. (b) 262.44 K. 58.63 kPa. (c) 57.89 kJ, 11.4 kJ, (d) 0.0362 I<JIK. Methane has a spe<:ific heat at Wll5lant pressure given bycp " 17.66 + 0.06188 T k..Ilkg mol K when I kg of methane is heated at carnlanl volume from 27 10 500"C. If the initial pressure of the gas is I atm, calculate the final pressure, the heat trIIISfer. the work done and the change in entropy. An.r. 2.577 atm. 1258.5 k..Ilkg, O. 2.3838 kJ/kg K Air is eompressed reversibly accordin8 10 the law pv l .15 .. oonsl. from an inilial pressureof! barand volume of 0.9 m'lOa fmal \'olume of 0.6 m'. l>eu:nninethe final pTl:S$Ure and Ille change of entropy pet kg ofair. AIlS. L .66bar. - 0.0436kJIkgK In a heal engine cycle. air is isothermally compressed. Heal is then added al constant pressure, after wllich the air expands isentropically 10 its original state. Draw the cycle onp-v and T-s coordinates. Sbow thallhe cycle dflCielK:Y can be expn:ssed in lhe following form






If -

(7 - I) In r - r[r1-1 11 1]

where r is the pressure ratio. pi p,. ~tcnnine Ille preisure raTio and the cycle efficiency if the initial temperature is 27"C and the muimum tempemture is

AIlS. 13.4. 32.4% 10.50 What is the minimum amount of work required to separate I mole of ai r at21"C and I atm pressure (assumed composed of 115 ~ and 415 NI) into oxygen and nitrogen each at 27C and I 31m pre5SUre? AII.I. (250 J 10.SI A closed adiabatie cylinder of volume I m l is divided by a panition into two wmpartments I and 2. Compartment I lias a volume of 0.6 m) and contains methanc at 0.4 MPa, 4ifC, while compilfUlh.'1l t 2 has a vo lume of 0.4 m' and contains propane at 0.4 MPa. 4O"C. The partil ion is removed and the gllKs are allowed to mix. (a) When the equilibrium state is reached, find the entropy change of the universe. (b) What are the molecular weight and tile specific Ileal ,.Iio of the mixture? The mixture is now compressed revenibly and adiabatically to 1.2 MFa. Compute (c) the final temperature of the mixture, (d) the work required per unit mass, and (e) the specific entropy change for each gas. Take c, of melhane and pllljl&M IIIi 35.72 and 74.56 kJJq mol K respectively. AIU. (a) 0.8609 k..IfK (b) (c) lOO.9C (d) 396 kJ (e) 0.255 kJlkg K


392=10.52 An ideal gu cycle oonsists nfthe following reversible pro<:esses: (i) isentropic compression, (ii) constant volume heat addition. (iii) isentropic expansion, and (iv) "Constant pressure h~1 rejtXIion. Sbow thaI the efficiency of this cycle is given by
I . [L r,,'oC. "_ ' ,, - ,,-I) 1I - 1 - --y:r ,..t - a I

where r t is the compression ratio and a is the ratio of pressures after and before beat addition. An engine operating on the abo~e cyck! .....ilh a compressioo ratio of6 stalU the compression with airat I bar, 300 K. If the ratio of pressures after and before heat addition is 2.5, calculate Ihe efficicncy and the m.e.p. of the cycle. Take y- 1.4 and c, " 0.718 kJ/kg K. AM. 0.579. 2.5322 bar 10.53 The relation betv.een II, P and. v for many gases is of the fann II - a';' bpv where a and b IlJe constants. Show that for a reversible adi3batie proccSS, plIl _ constant, where y- (b+ I )lb. 10.S4 (a) Show thaI !be slope ofa reversible adiabatic process onp-V coordinates is






tI iJp T (b) Hence, $how that for an ideal gas,pv' . constant, for a revCf"Sible adiabatic process. A cCflain gas obeys the Clausius equatinn of ltate p(tI- b) " RT and has its internal energy gi\en by II C. T. Sbow lhat the equation for a revmible adiabatic process isp(tI - b)' . constant, wbcrc y . (a) Two cur'tes, one representing a revCf"Sible adiabatic process undergone by an ideal gas and the other an isothermal process by the same gas, incetseC1 at the same point on thep-V diagrvn. Show thaI the ratio of the slope of the adiabatic curve to the slope of the isothcnnal CUTV<: is equal to 1. (b) Dctenninc the ratio of work done during a revers ible adiabatic process 10 tbe work done during an isothermal process for a gu having 1"'" 1.6. Both processes have a pressure ralio of6. Two conUlinersp and q with rigid wall s cOf}Ulin two different monatomic gases with IIIIISSCS flip and "'q' gas constants Rpaltd R", and inilaillcmperatures Tp and Tq respccthdy, are broughl in ,onla,t with eacb otller and allowed to elIcbange energy until equilibrium is achieved. Octcnnine: (al the final tempernlurc: of the two gases and (b) the cltange of entropy due 10 this energy ex,hange. The pressure or. ,crtain g:15(pbotongu) isa fUll(:lion oftempetaturc: only and is related to thc energy and volume by p(n - (1f3) (UW). A system consisting of Ihis g:15 confined by a cylinder and a piston undergoes a Camot cycle between two pressures PI and Pl. (a) Find expressions for work and heat of reversible isothennal and adiabatic processes. (b) Plot the Carnot cycle on ~v and T-s diagT1lfTl5. (c) Determine the efficiency of the cycle in tenns of pressures. (d) Whal is the functional relation between pressure and temperature? The gravimetric analysis of dry air is approximately: oxygen '" 23% nitrogen - 77%. Calculate: (al Ihe \" ollllIlCtric analysis. (b) the gas COlL'llant, (c) the moleo::ular weight, (d) the respective panial pressures, (c) the specific vol ume al

dp .. -...!...~ where .. .. -





Proptrlia of Gam 0114 GIIS Mi%lIlttJ


I atm. 15"C. and (f) How m~h o~ygm must be added to 2.3 kg airto produce I "'hieh is SooAo o~ygen by volume1 Ails. (a) 21 % 0l. 79% Nl (b) 0.288 kJ/kg K. (d121 kPa for 0l' (e) 0.84 m /kg. (f) 1.47 kg 10.60 A \'eSSe1of volume 2Vis divided iDlo two equal compartments. These arc filled with the ~ ideal gas. the temprnlture lpId pressure 00 one si de of the partition being(pz. Tt ) and on the other (Pl' T1). Show that if the gascson the two sidesan: allowed to milt ~Iowly with no heat entering, the final press~ Bnd temperaTUre will be given by

P'" PI+Pl .T .. 1i7i(PI+Pl) 2 PIT: + Pl1i

Further. show that the entropy gain is

+ h...ln A 1n..L - h...ln..L] R12 TI Tl Tl 1i PI 12 P1 10.61 A single-acting aircompres!IQT has acylinderofbore IS cm and the piston stroke is 25 cm. The crank speed is 600 rpm. Air taken from the atmosphere (t atm. 27<'C) is del ivered at II bar. Assuming polytropic compression pVJ.l1 ... const . lind the power required to drive the compressor. wilen its mechanical efficiency is 8oo!.. The compressor has a clearance volume which is 1120th of the stroke volume. How long will it takc to deliver I m l of air at the compressor outlet conditioDll. Find the volwnetric efficiency of the compressor. An.!. 12.25 kW. 30SS min. 72% 10.62 A multistage air compressor compresses air from I bar to 40 bar. The maximum temperature in any stage is not to e~cecd 400 K. (a) !fthe law of compression for all the stages is fJV tJ .. const., and the initial temperature is 300 K, find the number of stages for the minimum power input. (b) Find the intermediate pn:ssures for optimum compression as well as the power nttdcd. (e) What is the heat U"aDllfer in each of the intercooler? AIIl'. (a)3 (b) 3.48 bar, 12.1 bar. 373. 1 kJ/kg (c) 100.5 kJlkg 10.63 An ideal gas with a constant volume of cp - 29.6 J/gmol-K is made to undergo a cycle consisting oflhe following revenible processes in a closed system: Process 1-2: The gas eltpands adiabatica ll y from 5 MPa, SSO K 10 I Mpa; Process 2- 3: The gas is heated at constant "olume until 550 K; Process 3- 1: The gas is compressed isothclTlla lly back to its initial condition. C. lcula!e the " " ork. the heal and the changc of cntropy of the gas for each of the three processes. Oraw the p-V and T-s diagrams. Am. W I_1 - 4260 Sigmol, Qt_l - 0, W"l _l " 0, 11'1_ 1 - 0, Q1-J - 4260 J/gmol, ~l_J " 9.62 J/gmol -K . 11'1_1 - - 5290 Jlmol - Q }- I" W"l-L - - 9.62J/gmnl -K , W... - Q... - - 1030
AS Jglgmol, dS - 0 10.64 Air in a closed system eltpands revenibly and adiabatically from 3 MPa, 200"C to 1...0 limes its initial volume. and then cools at constan t volume until the pressure drops 10 0.8 MPa. Calculate the won.: done and heat transferred per kg of air. Usc cp - 1.017 and c. _ 0.728 kllkgK.. AilS. 82.7 kJlkg, - 78. 1 kJ/kg

Y[(~)(.!i. In L

.I.-.-l -

394=10.65 A vessel is divided into three companments (a), (b) and (c) by two partitions. Part (a) contains hydrogen and han volumcofO.1 ml, part (bl contains nitrogen and has a volumc of 0.2 m l and pan (cl contains carbon dioxidc and has a volume of 0.05 ml. All the three pans are 1\ a pressure of 2 bar and a lmlperature of DOC. The partitions arc removed and the gases are allowed 10 mix. Determine (a) the molCClllar weight of the mixture. (bl the characteristics gas constant for the mixture, (cl the panial pressures of each gas, (d) the reversible adi~balic index y, and (e) the entropy change due to diffusion. The speci fk heall! of hydrogen, nilrOgen and carbon d ioxide are 14.235, 1.039 and 0.828 UlkgK respective ly. The above gas mixture is Ihen reversibly compressed 10 a pressure of 6 har according 10 the law frol.l - COnstanl, (0 Detennine Ihe .....ork and heal inleTllctions in magnitude and sense. and (il) the changc in ClItropy. AIlS. (al 22.8582 (b) 0.3637 UIkgK (cl PH, - 0.S714, PN: - 1.1428, PCOj - 0.2858 bar (d) 1.384 (e) 0.3476 kllkgK (f) - 70.455 U , - 33.7n U (g) - 0. 1063 kJlK. 10.66 A four cylinder single-stage air compressor has a bore of200 mm and a stroke of 300 rum and rum al400 rpm. AI a .....orking pressure of n1.3 kPa il deli\'C1"$ 3. 1 ml of air per min al 270 C. Calculate (a) the mass flow nlte, (b) the free air delivery (FAD) (cl effective liW~t volume, (d) volumetric efficiency. Take the inlet condition as thaI of the free air al 101.3 kPa, 21 C. AIlS. (a) 0.239 kg/s (b) 0.199 ml/s (cl 0.299 mJ , (d) 79.2% 10.67 A single $tage rcc;procat;ng aireompressorhas a s.....cpt volumc: of 2000cm J and tunS at 800 rpm. It operates ona pressure ralioof8, with a clearance ofS'Y. ofthe s.....ept ~ol umc. Assume NTP room conditions, and al inl et, and polytropic compression and expansion with II - 1.25. Calculate (a) the indicated power, (b) volumelric efficiency, (cl IJIlWi flow rate, (d) the free air delivery FAD, (e) iso!hennal efficiency, (f) actual power needed 10 drive the compressor, if the mechanical efficiCllCY is 0.85 . AIlS. (a) 5.47 kW (b) 78.6% (c) 1.S4 kg/min (d) 1.26 mJ/min, (e) 80.7%, (f) 6.44 kW 10.68 A two-stage single-acting reciprocaling compressor takes in air at the nile of 0.2 ml/s. Intake pressure and temperalure are 0.1 MPa and 16"C rc-spcctl\'Cly. The: air is compressed 10 a rUlllI pressure of 0.7 MPa.lbc intcrmedialepressure is ideal , and intertooling is perfecl. Thc compression indeK is 1 .2~ and the compreilSOr runs at 10 rps. Neglecting clearance, determine (a) !he intermediate pressure, (b) the total volwne of each cylinder, (c) the power required to drive the cDmpl"C5SOr. (d) the rate ofhealabsorplion in the intereoolcr. Am. (a) 0.264 MPa (b) 0.0076 ml h.p. and 0.Q2 m] lop cylinder (C) 42.8 kW (d) l4.9SkW 10.69 A 3-stage single-aeting air compressor RIMing in an atmosphere at 1.013 bar and IS C bas a free air delivery of 2.83 mlfmin. The suetion pressure and tcmpcrall1/'C arc 0.98 bar and 32 C respective ly. The delivery pressure is to be 72 bar. Calculate the indicate power required, assuming complete inlCI"Cooling. II '" 1.3 and that thc compressor is designed for minimum woO. What will be the hc.at 10" to the inlCl"COOlcl"$? AIlS. 25.568 kW, 13.78 kW

Puptt/in ~f CAsu flU Coli MixtllTa


10.70 Prediel the pressure of nitrogen gas al T '" 1705 K and v - 0.00375 ml/kg on the basis of (a) the ideal gas equatiOll of state , (h) !he van der Wuls equatiOll of stale, (e) !he Beattie-Bridgeman equation of stale and (d) the Benedict-Webb-Rubin equation of state. Compare the values obtained with the e:tperimentally determined value of 10,000 kPa. AM. (a) 13,860 kPa (b) 9468 kPa (e) 10,11 0 kPa (d) 10,000 kPa 10.71 The pressure in an automobile tyre depends on the tempentwt: of the air in the lyre. When the air lempenlture is :WC, !he pressure gauge reads 210 kPa. If the volume of the ~ is 0.0205 ml, determine the ~ risc in the lyre when the air temperature in the tyre rises to o5OOC. Also (md the amount of air that must be bled ofT to restore prelSure 10 ilS origiltal value at this temperature, Take atmospheric pressure as 100 kPa. 10.72 Two tanks arc connecte4 by I valve. One tank contains 2 q orco gas at 77or. and 0.7 bar. The other tank bolds 8 kg of the same gas at 27C and 1.2 bar. The valve is opened and the gases arc allowed to mix while n:eeivin& energy by heat transferfrom the surroundings;. The rmal equilibrium temperarure is 42C. Using the ideal gas model, dctennine (al the final equilibrium pressure, (b) the heat transfer for the prOCCSll. AliI. (a) 1.005 bar (b) 3715 kJ

Thermodynamic Relations, Equilibrium and Third Law


Some Mathematical Theorems

Ira relation exists among the variables x,y, and

Theorem 1

=. then;: may be

expressed as a function of.:nnd y, or

dz =

(~: )y ~ + (;;


(~;)y -M,and(;;). -N
dz - Mm +N dy.

wherc;:,M andNare functions ofx andy. DifJerentialingMpanially with respect to y, and N with respect to x

a M ) a', (ay . "" (kay ( aN) a',

a; , =

(~;). (n
This is the condition


Theorem 2 among .r,y and

0/ exact (or perfecI) differential. If a quantity f is a function of .t, y, and z, and a relation exists

then/is a function or any two of x,y, and z. Similarly any


one ob,y, andz may be regarded to be a fWlction ofland anyone ofx,y, and z. Thus, if x=:c(/,y)

Y ",o( ~;), ~+(~; ),d

Similarly, if

y- y(f, 'i y)~+[ ay) '" d y-[ 01 a oz


Substituting the expression of dy in the preceding equation


Theorem 3 Among the variables :c, y, and z, anyone variable may be oonsidcred as a function ofdle odler two. Thus
x "' x(y,z)

", y+(ax) '" . _[ax) oy. d OZy


", . (E.;. )",+[a,) dy OX,OY 1 '" - [ax) a,), dx+ (E.;.) oY ,dy + [E.;.) oz [[ ax ay d!'j - [(~~J. +(E.;.) (a,) j'Y+(E.;.) (E.;.)", OY "1 aZ y ay, aZyaX y


' [(~J ay 1+(OXJ aZ (~J ay ],y+",

y x


(~;J. +(~; JJ~;J. - O

(~; )J~;)J~~)1 -- I
(11.3) Among the thennooynamic variables p , Y, and T, the following relation holds


(ie.J ay (lo:J aT (OTJ ap

T p

-- 1

11.2 Maxwell'. Equations

A pure substance existing in a single phase has only two independent variables. Of the eight quantities p , Y, T, S, U. H. F (Helmholtz function), and G (Gibbs function) anyone may be expre3.Sed as a/unction 0/ any two othen. For a pure substance undergoing an infinitesimal reversible process (a) dU - TdS-pdY (b) dH "' dU+pdY+Ydp " TdS+Vdp (e) dF - dU - TdS - SdT - - pdY -SdT (d) dG = dH - TdS-SdT =Vdp - SdT Since U, H, F and G are thermodynamic properties and exact differelltials of


<it - M dx+ N dy. then

(~~J. =(~J,
Applying this to the four equations

(~a =-(~~l,

(11.4) (11.5) (11.6)


(~a =(~a
oS J (ie.J aT v -( -iW

(OS] (OYJ i'lTp ""- i'lPT

These four equations are known as Maxwell '.I' equal/OilS.


TdS Equations

Let entropy S be imagined as a function of T and V. Then

dS _('S) aT v dT+ ('S) av dV TdS "" J~) dT+"( as) dV ' l aT v ' lay

Since T

(~:)v -C", heat capacity at conslant volume, and

( ~:)T '" (~~


Maxwell's third equation,

TdS - C.dT+ T(~~

This is known as theftr.l'l TdS equalion.



IfS - S(T,p)

dS _('S ) dT+('S) aT p ap dp


_.r 'S )dT+ .r 'S) 'laT 'lap .r'S) _C ....d (.S) _ _('V) ' l aT ap ar


TdS = CdT - T (~)

This is known as the

'T s e c ond TdS

e<lllutiOfI .


( 11.9)


Difference in Heat Capacities

Equating the first and second TdS equations

TdS "" CdT - T(~) pa T


dp =Cv

dT+T('P aT ) dV v

-C)dT-r('P aT )v dV+r('V) aT dp

dT -

UT v dV +

uT P dp



Cp -C.

dT_(OT) dy+(aT) d p uV Up T(a p) T(ay) ar , =(OT) Md ar , =(OT) cp-c., uV p cp-c., Up

cp - C - T(~) (OY) VUTUT

Both these equations give



(~~W~),(t), -- 1
cp -v c - - T(~)'(OP) oToV , ,

This is a very irnportantequation in thermodynamics. It indicates the rollowing important facts. (a) Since

(~~ X is always positive, and (~: )T for any substance is nega-e..

(~~)p = 0 (e.g., for water at 4C, when density is maximum. or

tive. (Cp -e.) is always positive. Therefore, Cp is always greater than e ... (b) As T ~ 0 K, Cp -+ Cyor al absolute zero, e p (c) When

spt(:ific volume minimum), Cp C. (d) Foranidealgas,pV - mRT

(~~)p ~ m; = ~

ap) =_mRT (av



Cp-Cy .. mR cp - cy=R Equation ( 11 .10) may also be: ellpressed in terms of volume ellpansivity (JJJ.



p - ~(~)
y aT

and isothermal compressibility (.tr), defined as

k' - -~(~) y aT T


11.5 Ratio of Heat Capacities

At constant S, the two TdS equations become CpdT,

~ ~~)p dp,

C~dT, " -T(~~t dY.

C, _ (OV) (aT) (op) J*), z.-aT a; v av s -(~) - r

oV ,

Since y> I.

Therefore, the slope ofan isentrope is greater than that ofan isotherm onp--v diagram (Fig. 11 .1). For reversible and adiabatic compression, the work done is

1Y. " h~-hl '"

Forreve~ible and isothennal

" J vdp

.. Area 1-2S-3-4--1 compression, the work done would be

WT o=h rr -h 1 '"

" Jvdp ,

.. Area J-2T-3-4--J


402=3 ~.... .2T~ .........2S


S "C

4 .... - ................ ,

FIg. 11.1

For polytropic compn;ssion with I < n < Yo the work done will be between these two values. So, isothennal compression requires minimwn work. (See Sec. 10.4). The adiabatic compressibility (kJ is dermed as



.1.6 Energy Equation

For a system undergoing an infinitesimal reversible process between two equilibrium states, the change ofintemal energy is

dU " TdS-pdV
Substituting the first T dS equation

dU - Cy dT +
= CydT+

r( ~~ t


[T(* t -

P] dV


U "' U(T,I')



dU_(au) dT+(aU) dY aT v av (au) _T(ap) _p





This is known 85 the energy equ(ltion. Two applications of the equation are

(a) For an ideal gas,

nRT P' Y-

(~~t _ n:=~

(au) _ T
aV T

T.'"- p - O

U does nol change when V changes al T = C.


ap T U does nol change either when p changes at T- C. So the internal energy of an ideal gas is a funclion oflemperalure only, as shown earlier in Chapter 10. Another important point to nole is Ihat in Eq. (1 1. 13), for an ideal gas

(a .a.(au) =a
p ) aV T

pV- nRTand

p) -p= T(a aT O

dU - CydT holds good for an ideal gas in any process (even when the volume changes). Bul for any other substance dU '" CydT is true only when the volume is constant and dV ~ O. Similarly dJI - TdS + Vdp

TdS - CdT-T (~l P aT pdp


&m {uld AHlid 17rmnUJlUlfllia

dH -C,dT+[V - i~~)} - V-T (~) [aH) dp dT




As shown for internal energy, it can be similarly proved from Eq. (11.16) that th e enthalpy ofan ideal gas is not a function of either volume or pressure

but a function of temperature alone. Since for an ideaJ gas.pV" and


V _Tray) aT ,-0

the relation dH~ Cp dTis true for any process (even when the pressure changes). However. foranyother substance the relation dH ~ CpdTholds good only when the pressure remains constant or dp = O. (b) Thermal rediation in equilibrium with the enclosing walls possesses an energy that depends only on the volume and temperature. The energy density (u), defmed as the ratio of energy to volume. is a funerionofternperature only, or

u - U -j(1)only V
The electromagnetic theory of radiation states that radiation is equivalent to a photon gas and it exerts a pressure, and that the pressure exened by the blackbody radiation in an enclosure is given by

p =)
Black-body radiation is thus specified by the pressure, volume. and temperature of the radiation. Since

U = uVandp - ~ 3

_'Md(ap) =!~ [aU) dV aT v 3 dT


By substituting in the energy Eq. (11.13)

T du , - ---3 dT 3

~=4 dT
, T

Inu - ln"r+lnb

"' "

where b is a constant. This is known as the StefanBoltzmon" Low. Since U= !lY '" Vbi'

au) (oT

" C = 4Vbrl

a ) _ ..!..~ = .i bTl (ar v 3 dT 3

from the first TdS equation
TdS '" Cy dT+

r( ~~ t


~ 4Vbra dT + .!br.dV
For a reversible isothermal change of volume, the beat to be supplied reversibly to keep temperature constant
3 For a reversible adiabatic change o(volume

Q " br' 4V

br' dV - - 4VbrJdT 3

~ - -3~

vr - const.
If the temperature is one-half the originallcmperature, the volume of blackbody radiation is to be increased adiabatically eight limes its original volume so that the radiation remains in equilibrium with matter altha! temperature.

11.7 Joule-Kelvin Efl'eet

A gas is made to undergo continuous throttling process by a valve, as shown in
Fig. 1\.2. The pressures and temperatures of the gas in the insulated pipe
upstream and downstream of the valve are measured wi th suitable manometers

and Ihermometers.


Fig. 11.2



Let Pi and Ii be the arbitrarily chosen pressure and temperature before throttling and let them be kept constant. 8yoperating the valve manually, the gas is throttled successively to different pressures and temperatures Pn . T,,;pb,' TI:!; Po. To and so on. These are then ploned on the T- p coordinates as shown in Fig. 11.3. All the points represent equiJibriwn states of some constant mass of gas,say, I kg, at which the gas has the same enlhalpy.

The curve passing through all these points is an isenthalpic curve or an

isenthalpt!. It is not the graph of a thronling process, but the graph through points
of equal enthalpy. The initial temperature and pressure of the gas (before throttling) are then set to new values, and by throttling to different states, a family af isenlhalpe$ is obtained for the gas. as shown in Figs 11.4 and 11.5. The curve !'USing through the maxima ofthesc isenthalpes is called the inversion C1U"\Ie. The nwnerical value of the slope of an isenthalpe on a T-p diagram at any point is called theJou/eKe/vin coe,Oicientand is denoted by #-I,. Thus the locus of all points at whichp, is zero is the inversion curve. The region inside the inversion curve where PJ is positive is called the cooling region and the region outside where J-lJ is negative is called the ~aring region. So,

=-~~ ,, i , ,,
Temp _


1"" 1


curves (banIhaIpe$)

. Tl


InYersIon curYe (p - 0)

, ---,
Fig. 11.' IInlMJpu: nortra" tiM IN iltffFSi/lll <>1m'



- -.,

~J ~ (~:l
The difference in enthalpy between IWO neighbouring equiHbriwn SillIeS is dh - Tds+vdp and Ihe second TdS equation (per unil mass)
TdJ""' c

dT_r[ilv) aT ,dp

dh - '.dT-[r(~; ),
p, For an ideal gas


The second lenn in Ihe above equalion slands only for a real gas. because for an ideal gas, die c p

[aT) ap ~ = .!.[T[.".) c aT - v]

pv " RT

(~;t = :=;

. .!. (r..! . . -v) -o

" T There L, IIQ change in temperature ",hell UII /doo ' gus is made to undergo a Joule-Kelvin expwuian (i.e. throttling). For achieving the effect of cooling by l ouie-Kelvin expansion, the initial temperature of the gas must be below the poinl where the inversion curve

interseclS the temperature axis, i.e. below the maximum inversion temperature. For nearly all substances, the maximum inversion temperature is above the normal ambient temperature, and hence cooling can be obtained by the JouleKelvin e ffect. In the case of hydrogen and helium, however, the gas is to be preeooled in beat exchangers below the maximum inversion temperature before it is throttled. For lique faction the gas bas to be cooled below the critical temperature. Let the initial state of gas before throttling be at A (Fig. 11 .6). The change in temperature may be positive, zero, or negative, depending upon the final pressure after throttling. If the fmal pressure lies between A and B, there will be a rise in remperature Of beatingeffecL lfit is atC, there will benocbange in temperature. If the final pressure is below Po. there will be a cooling effect. and if the final pressure is Pn. the lemperature drop will be (TA - To). Maximum temperature drop will occur ifthe initial slate lies on the inversion curve. In Fig. 11 .6, it is (Ta - To). The volume expansiviry is

p _ 1-(~)


So the Joule-Kelvin coefficient,ul is given by, from Eq. (11.11)

P, - J..[T(~) aT


III - ..E.... [.8T - 1)


For an ideal gas,

,B - .!...and,ul - O

There are two inversion temperatures for each pressure, e.g. TI and Tl at pressure p (Fig. 11.4).

'. 1oc:/' = =

"".',;",- 1nver3Ion curve









11.8 ClausiusClapeyron Equation

During phase transitions like melting, vaporization and sublimation, the temperature and pressure remain constant, while the entropy and volume change. Ifx is the fraction of initial phase; which has been uansfonncd into final phase/. thm
S = (I_x~i)+XS<1)

(I - x)


+ xviI)

where s and v are linear functions of x. For reversible phase transition, the heat transferred permole (or per kg) is the latenl heat, given by I _ T{j(f) _ s(i)} which indicates the cbange in entropy.


dg "'- roT + vdp

, __(dg )
dT ,
g) v_(d dP ,
Aphase change afthefir$l order is known as any phase change thai satisfies the following requirements: (a) There arc: changes ofentrl>PY and volume. (b) The first-orderderivativesofGibhs function change discontinuously. Let us consider the first-order phase transition of one mole ora substance from phase i to phase! Using the first TdS equation

Tdro" cv dT + T(



for the phase transition which is reversible, isothennal and isobaric, and integmting over the whole change of phase. and since


is independent of-

dp dT

.:r(f) _i'l

= o(i) -

0( 1)

= T[v(f) -o(') J

( 11.1 8)

The above equation is known as the Clausius-Clapeyron equation. The Clausius-Clapeyron equation can also be derived in another way. For a reversible process at constant T and p, the Gibbs function remains constant. Therefore, for the first-order phase change al Tandp


If' - tI'
and (or a phase change at T + dT and p + dp (Fig. 11.7)

.l.~ ....... ....... . I


ii "---, : v



fig. 11.7 Fim I1Tthr p~ IT,-ril;on


d&''' - d&"

_in dT + vii) dp .. -if)dT+ tfdp

,,(0 - ii)


dT - vlO

vlO -

vlh 1

2e. =

I". T(v " v')

where If> is the latent beat affusion, the fIrSt prime indieares the saturaled solid
state, and the 5e(:ond prime the saturated liquid state. The slope of !he fusion curve is determined by (v" - v'), since /IU apd T are positive. If the substance

expands on melting, v" :> if, the slope is positive. This is the usual case. Water,
however, contracts on melting and has the fusion curve with a negative slope (Fig. 11.8). For vaporization

dp dT
saturated vapour state.

1"9 T(I:I'" v")

where I...., is lile latent heat of vaporization, and the thrid prime indicatcs the

At temperatures considerably below die critical temperature, v'" v" and

using the ideal gas equation of state for vapour


- -


"' "


For~ \

(negative ,

. - .

Fusion a..ve

For 1lIIY othef substance

< - - """" " "




p, ........ . . .\. ............

dt :

Triple point



:, T.~RT dT P


", RT2~ P dT


If die slope dp/dT at any state (e.g. point PI' T, in Fig. 11 .8) is known, the latenl heat of vaporization can be computed from the above equation. The vapour pressure curve is of the form

Inp '"' A+.!!..+CIDT + DT T where A, B, C and D are cOnstants. By differentiating widi respect to T

..!....~:::_..!...+.f. + D p dT rl T


Equations (11.19) and (11.20) can be used 10 estimate the lalent heal of vaporization. Clapeyron's equation can also be used to estimate approximately the vapour pressure ofa liquid at any arbitrary temperature inconjunction with a relation for die latent heat ofa substance, known as Trou/on:" rule, which nates that

.:!L:, 88 kJlkgmol K
where Ii is the latent heat ofvaporiurion in kJlkgmol and 6Ta is the boiling point at 1.013 bar. On substituting this into Eq. ( 11 .19)

r .



88TB 'liTl P





Jd; T

In -

P _=- 8ST, 101.325 R T


(..!.._...!..) To

101.325 exp[~(I - ~)]

This Sives the vapour pressure p in !cPa at any temperature T. For sublimation dp = lid> dT T(v'" v') where 1M is the latent heat of sublimation. Since rl n rI, and vapour pressure is low, 1/" _ RT




-- 2.303 R d (1ogp) Id> d(l IT)

the slope oflogp vs. l I T curve is negative, and if it is known,/lUb cao be estimated. At the triple point (Fig. 9.12), (11.23) I... = I... + I,.".

!l'.) '" p!J i (.'dT RTIp


dP ) '" p~f~ ( dT sub RTIp

Since loub > l""f>' at the triple point

Therefore, the slope of the sublimation curve at the triple point is greater than that oflhe vaporization curve (Fig. 11.S).

(*L >(*1

11.9 Evaluation of Thermodynamic Properties from an Equation of State

Apart from calculating pressure, volume, or tempe:ruture, an equation ofstate can also be used to evaluate other thennodynamic properties such as internal energy. enthalpy and entropy. The property relations to be used arc:

7ltmlldplamu ~ Ef-ili!rlWII 1INl11lmt lAw

- = 413

du - CydT+[T(~~)y -P]dV
dh ,.dT+ [V-

r(:; l}


ru -

~[CvdT+T(*). dV]

. ~['.dr- r(rr 1 .d~l

Integrations of the differential relations of the properties p, v and T in the above equations arc carried out with the help of an equation of state. The changes in properties arc independent of the pa!h and depend only on !he end states. Let us consider that the change in enthalpy per unit mass ofa gas from a reference state o atpo. To having enthalpy,h o to some olberstateB alp, Twith en!halpy h is to be calculated (Fig. 11 .9). The reversible path OB may be repla~ for convenience by either path O-a-B or path O-b-B, both also being reversible. Path O-o-B: From Eq. 11.2S,

h-h, -

p _e


p To . C



T_e ",, _ e



FIg, 11.9 Prum cORlIldi1ll 114m (Po, T~ aM (p,



On addition,

'.-',' [1."dT1. +lH,~;;n-L

Similarly, for Path O-b-B:


h-h,'ll~~;J,H,. + [1." dT
Equation (11.27) is preferred to Eq. (11.28) since conveniendy measured. Now,

c, allower pressW'e can be


J d(PV) - Jpd'+ J ,dp

),dp'P'-p,. -[i pd,]

Po v, T



d'l[drl[~l[ or ap av

T --

[~;l. ' {~im;l

SUbstituting in Eq. {I 1.27),



+Jro-p" .-[ipd,]


11. r( ~n.l ~; ),'pL


-[1."dT1. +P'-P"-Wp-r(~n,H,
To find the entropy change, Eq. (11.26) is integrated to yield:

,-"-[J,, d:]


-[ )( ~;)

d P]



11.10 General Thermodynamic Considerations on

an Equation of State
Certain general eharacteristics an: common to all gases. These must be clearly observed in the developing and testing of an equation of state. It is edifying to discuss briefly some of the more imponant ODeS: (i) Any equation of state must reduce to the ideal gas equation as pressure approaches zero at any temperature. This is clearly seen in a ge neralized compressibility factor chart in which all isotherms converge to the point ~ .. I at zero pressure. Therefore , lim r.1!!!....j _ I at any temperature ,-OLRT Also, as seen from Fig. 10.6, the reduced isothenns approach the li ne z - I as the tempcrnture approaches infinity, or: lim r1!!!..j _I at any pressure. r_!.l RT

(ii) The critical isotherm of an equalion of stale should ha ve a point of inOeclion al the critical point onp-v coordinates, or

av lap]



(iii) The isochores of an equation of state on a p-T diagram should be essentially straight, or:



- 0




[;~~ 1. .. 0 asp -+ 0, or as T -+-.

An .equation of state can predict the slope of the critical isochore of a fluid. This slope is identical with the slope of the vaporization curve al the critical point. From the C lapegron equation, dp/dT - ll.f/!J.v, the slope of the vaporization curve at the critical point becomes:

dp dT =

[a,] ov lap] ar
T '"

(by Maxwell's equation)

Therefore, the vapour-pressure slope at the critical point, dp/dT, is equal 10 the slope of the critical isochore (apia 7)", (Fig. 11 .10).




FIg. lUO Pms.rtUtIffJn'tUIm dJ4tmR fIIllII UMrU /ius

(iv) The slopes oftbe isotherms of an equation ofstate on a Z-p compressibility futor chart as p approaches zero should be negative at lower lemperalures and positive It higher temperatures. At the Boyle temperature, the slope is zero asp approaches zero. or

lim[d' J - oaIT" TB ' .... 0 op T

An equation of slate should predict the Boyle temperature which is about 2.54

Tc for many gases.

An isothenn of maxim urn slope on the Z - P plot asp approaches zero, called thefoldbock isotherm, which isaboul ST< for many gases, should be predicled by

an equalion of slale, for which:

p .... O

lim[~J - OatT- Tr oTop

where Tr is the foldback temperature (Fig. 10. 10 a). As temperature increases

beyond Tr the slope oflhe isolhenn decreases, bUI always remains positive. (v) An equation of Slate should predict the Joule-Thomson coefficient. which

1 T aT PJ: ~

[(d') - v1 '" RT'(d') oT ""'-t




For the inversion curve, Ill "" 0,


( ~) dT , - 0

11.11 Mlxtures of Variable Composition

Let us consider a system containing a mixrwe of substances 1, 2,3", K. Ifsome quantities of a substance are added to the system, the energy of the system will increase. Thus for a system of variable composition, the internal energy depends not only on S and V, but also on the number of moles (or mass) of various constituents of the system,

V - V(S, V. "l' "2. .. . , "0

where " I' "l' .. '. "K are the number of moles of substances 1, 2. , .. , K. The composition may change not only due to addition or subtraction, but also due 10 chemical reaction and inter-phase mass tnmsfer. For a small change in V, assuming the function to be continuous

+ ... + -d-

( dU) S,V,nl~I " -.DI:.1 <In,


dU_( dU ) dS+(dU) dV+ f(dU ) av s.

as V.DI

v, 81


;. 1 all;

where subscript i indicates any substance and SUbscriPI j any other substance except the one whose number of moles is changing. If the composition does nOI change

dV= TdS-pdV

_T.Md(dU) ( dU) as av dV - TdS - pdV + I, (dU) V,DI





i- I

an; s, V,Dj

Molal chemical potellliaJ, Il. of componeOl i is defined as



signifying !he change in internal energy per unit mole of componcntiwbenS. Y. and !he number of moles of all other components are conslant.

dU = TdS - pdV+ TdS-dU+pdV -

L ltiMj

Iljdn j


This is known as Gibb:s elltropy equatioll. In a similar manner

G - G (P. T,

Ill ' Ill... , IIJ


dG _(aG) dp+(aG) dT+i(aG) dp dT dll;

T.ft; p,a; i-I

T.p. aJ


d(U+pV-TS) - VdP - SdT+L

'(a aG)

T.p, aj



~ Vdp - SdT+;E

'(aG) dn ,-I a;; I T,p,aj

Comparing this equation wi!h Eq. (11.32)

(~~l.v'.J =(~~t.p.aj
:. Equation (11.34) becomes

- PI

, ,

dG '" Vdp - SdT+ 1 pjdn j

Similar equations can be obtained for changcs in Hand F.

dU - TdS-pdV+


dG ~ Vdp - SdT + 'l,uidn,
i_ I

dH = TdS + Vdp



dF - -SdT-pdV + L,uidni

". [OU)
. all;

s.v,Oj -

-lOG ) _[OH) dn; an;

T,p. aj -

S,P.0j -

_[OF) dn;

(J 1.36)
T,V, mj

Chemical potential is an intensive property. leI us consider a homogeneous phase of a multi-componenl system, for which

dU - TdS - pdV+ LJl;,dn;

If the phase is enlarged in size, V, S, and V will increase, whereas T, p and JJ will remain the same. Thus

!J.U - T4S-p!J.V + l:J.l;6nj leI the system be enJarged to K-times the original size. Then
lJ.U l!.S AV Mj KU-U - (K-J)U KS - S " (K - 1)S (K - l)V (K - l)nj

(K - J) U z T(K - I)S - p(K - I) V+IJl; (K -1)11;

U - T.S-pV+IJ4n;
~.p - IJ.l;.ni


Let us now fmd a relationship if there is a simuhaneous cbange in intensive property. Differentiating Eq. (11.37)

dG "" In; dPI + I,u;Wri

at constant T andp, with only Jl changing. When T and p change dG " -SdT+ Vdp + I/-ljdn;


(11.39) Combining Equations (1 1.38) and (11.39) - SdT+ Vdp - Injdp;= O (11.40) This is known as Gibbs-Duhem equation, which shows the neeessary relationship for simultaneous changts in T, p, andp. Now


420=For a phase consisting of only one constituent G

- Il"

i.e. the chemical potential is the molar Gibbs function and isa function ofTandp only. For a single phase, multi.component system, II; is a function of T,p, and the mole mctionxj.


Conditions of Equilibrium of a Heterogeneous System

Let us consider a heterogeneous system of volume V, in which several homogeneous phases (, - Q, h, "" r) exist in equilibrium. Let us suppose that each phase consists of i('"' I, 2. ... , C) constituents and that the number of constirutents in any phase is different from the others. Within each phase, a change in internal energy is accompained by a change in entropy, volume and composition, according to

dU. - T.dS. - p.dV.+

r ,-, (J.t;dnJ.

A change in the internal energy of the entire system can, therefore, be expressed as

. _.

dU, ~

. _.

T,dS, -

. _.

p,", + I

. _. ; - 1



Also, a change in the internal energy of the entire system involves changes in the internal energy of the constituent phases.

dU - dU. -+= dUb +. +dU, "


L dU.

Likewise, changes in the volume, entropy, or chemical composition of the entire system result from contributions from each of the pba.ses

dV - dV.+dVb + ... + dV. -

,-. ,

L dV.

dS "' dS.+d5t, + ... +dS,=

dn - dn.+dnb + ... + dn, -

L dS. ,-.




In a closed system in equilibrium, the internal energy, volume, entropy, and mass are constant. dU =dV= cfS z dn "O

dU.", - (dUI>+ .. . + dU.):-

L d~

dS. - dn.""-

L dSj


L , dnj

where subscript} includes all phases except phase a. Equation (11.41) can be written in terms of} independent variables and the dependent variable a (Equation 11.42)

(T.dS. + ~)jdSj) -(Padv. + tPjdVj)

+ [l(P;dn;). + ll(P;dn;),]=o

, ,

Substituting from Eq. (I 1.42)

(-T.fdS + t ljdSj)-(-Patd~ + tPj"dV



+ [llp,dn, + l l(P;dn;),]
1 1 1 1


where subscript i a refers to component i of phase a. Reammging and combining the coefficients of the independent variables. dSj d~ and dnj,gives

J j I But since dSj dl'j. and dnj are independent. their coefficients must each be equal to zero. (11.43) 1j " T

L (1j - TJdSj - L (PJ-pJ d~+ L L ~-.u;Jdnij - O

These equations represent conditions that exist when the system is in thermal.
mechanical, and chemical equilibrium. The temperature and pressure ofpbasea must be equal 10 those ofall other phases. and the cbemical potential of the jlh component in pbasea must beequallo the chemical potential of tile same componenl in all other phases . .

P j-P I '


11.13 Gtbbl Phase Rule

Let us consider a heterogeneous system ofC chemical constituents whicb do not combine chemically with one another. Let us suppose that there are 'phases. and every constiruent is present in each phase. The constituents are denoted by subslripts and the phases by superscripts. The Gibbs function of the whole heterogeneous system is
~ . (1) "jI) + ""t" M.( l) ,,9) + + . ~ Mjt) ".It) GT.p ... i:.. ",,., ..t.. ", r"", ", ,.,
i _I i-I i- I

G is a function ofT,p, and the n's of which there are C, in number. Since there are no chemical reactions. the only way in which the n's may change is by the transpOrt of the constituents from one phase 10 another. In this case the total number of moles of each constituent will remain constant. + + ... + t ) '" constant npl + + ... + t ) ., ~onstant

n\l) n\21


n/ n1

+ nJtl = constant These are the equations 0/ constraint.

AI chemical equilibrium, G will be rendered a minimum at constant rand p , subject to these equations of constraint. At equilibrium. from Eq. (11.43).

n~L) + nfl + ...

Pij - P;.

pl') _111 2) JIll) ~I) = 141).,


pfJ .. ... -


... "" p~t) These are known as the equations o/pllase equilibrium. The equations of the
phase equilibrium of one constituent are (, - I) in number. Therefore, for C constituents, there are C'(,- I) such equalions. When equilibrium has been reached, there is no transpOrt of matter from one phase to another. Therefore, in each phase, Ix " I. For, phases, there are,such equations available. The state of the syslem at equilibrium is delennined by the temperature, pressure, and C, mole fraclions. Therefore Total number of variables '" C, + 2. Among these variables, there are C'( \& - 1) equations or phase equilibrium and ; equations of Ix = I type. Therefore Total number of equations - C(; - I) If the number of variab les is equal 10 the number of equations, the system is nonvariant. If the number of variables ex.ceeds the number of equations by one, then the system is called monovarianl and is said to have a variance of I. The excess of variables over equations is called the variance.! Thus



I'" (q + 2) I=C -~ +2

[C(~ -

I) + ~l


This is known as the Gibb.s Phase Rule for a non-reactive syMem. The variance J is also known as the degree olfreedom. For a pure substance existing in a single phase, C ., I, , .. I, and therefore, the variance is 2. There are two properties required to be known to fIX up the state of the system at eqUilibrium. If C - 1" .. 2, thenI'''' I, i.e. only one propeny is required to fix up the state of a siogle--c::omponent two-phase system. IfC " 1. 9 " J, then/" O . The state is thus unique for a substance; and refers to the triple point where all the three phases exist in equilibrium.

11.14 Types of Equilibrium

The thennodynamic potential whicb conlIols equilibrium in a system depends on the panicularcorutroi/l/s imposed on the system. Let (tQ be the amount of heat transfer involved between the system and the reservoir in an infinitesimal irreversible preuss (Fig. 11.11). Let dS denote the entropy change of the T system and dSo the collopy change of the reservoir. Then, from the entropy principle dSo + dS > O
Fig. 11.11
Ht'/ illlml(tiM htfUlrl



dS = _ dQ o

'lJsltm,1Ii ill IIImntlliilflJ

dQ - +dS>O

t1Q -TdS<O
During the infinitesimal process, the internal energy of the system cbanges by an amount d U, and an amount of work pel V is perfonned. So, by the first law

t1Q "' dU + pelV

Thus the inequality becomes dU+pdV-TdS<O ( 11.46)

Ifthe constraints are constant U and V, then the Eq. (11 .46) reduces to dS > O The condition of constant U and V refers to an isolated system. Therefore. entropy is the critical parameter 10 determine the state of thermodynamic equilibrium of an isolated system. The entropy of an isolated system always increases and reaches a maximum value when equilibrium is reached.

If the constraints imposed on the system arc eonstant Tand V, the Eq. (11.46) reduces to
dU~d(TS) < O


<0 dF<O

wbicb expresses that the Helmholtz function decreases, becomming a minimum at the final equilibrium state. If the consuaints are constant T and p, the Eq. (11.46) becomes

dU + d(pV) ~ p(n) < 0 d(U + pV - TS) < 0

dG<O The Gibbs function or a system at constant T and P decreases during an irrevcrsible process. becoming a minimum at the final equilibrium stale. For a system constrained in a process to constant Tandp, G is tbe critical parameter to detcrmine!be state of equilibrium. The thermodynamic potcntial and the corresponding constrained variables are shown below.




This trend ofG, F, or S cstablish.cs four types or equilibrium. namely (8) stable, (b) neuual, (c) unstable, and (d) metastablc. A system is said to be in a state of stobIe equilibrium if, when the state is perturbed. the system returns to its original state. A system is not in equilibrium ir there is a spontaneous change in the state. (rthere is a spontaneous change in the system, the entropy of the system increases and reaches a maximum when the equilibrium condition is reached (Fig. 11.12). Both If and B (Fig. 11.13) are assumed to be at the same temperarure T. Let there be some spontaneous change; the temperature of.A rises to T + dT! , and that or B decreases to T - dT1 . For

Isolated system

Fig. 11.1.2

PouihU p_ for aft lsouUti l]JUm

Fig. 11.J3 S/lQlI#JftUM$ tMlIU iR A ull B th. Ul "", illtnaai~1I

simplicity, let the heat capacities of the bodies be the same, so that dTI - dT2. If d Q is the heat interaction involved, then the entropy change dS

-~ dS - -~ T+dT ' B T-dT

dS "" dSA + dSB '" d ~ T+ dT - T - dT ::: -""'T2' dQ

So there is a de<:rease in entropy for the isolated system ofA an dB together. It is thus clear that the variation in temperature dT cannot take place. The system, therefore, exists in a stable equilibrium condition. Penurbation of the state produces an absurd situation and the system must reven to the original stable state. It may be observed: If for all the possible variations in state of the isolated system. there is a negati ve change in entropy, then the system is in stable equilibrium. (dS')u,v > 0 (d.S)u,v '" 0 (dS>u.v < 0 Similarly (dG)".T < 0, (dFh.v < 0 Spontaneous change (dG)",T" 0, (dFh.v " 0 Equilibrium (11.48) (dG)".T > 0, (dFh.v > 0 Criterion of stability A system is in a slate of stable equilibrium if, for any fmite variation of the system at constant T and p , G increases, i,e, the stable equilibrium state corresponds to the minimum value ofG. A system is said to be in a state of neutral equilibrium when the thermodynamic criterion of equilibrium (G, F. S, U or H) remains at constant value forall possible variations offmite magnitude. Ifperturbed, the system does not reven to the original state. For a system at constant T andp, the criterion of neutral equilibrium is Spontaneous change Equilibrium (11.47) Criterion of stability



oGT p " 0

liFT,v - 0, oHs , p - 0, liUs.v - 0, liSu.v '" 0 A system is in a state of unstable equilibrium when the thermodynamic
criterion is neither an extremum nor a constant value for all possible variations in the system. If the system is in wutable equilibrium, there will be a spontaneous change accompanied by

liGT~ < 0, liFTV < 0, liUs,v < 0, liBs ." < O.liSu.v > 0 A system is in a state of metastable eqUilibrium ifit is stable to small but not 10 large disturbances. A mixture of oltygen and hydrogen is in a metastable

4-26=equilibrium. A little spark. may starta chemical reaction. Such a mixture is not in its most stable state, eveDthough in the absence ofa spark it appears tn be stable. Figure 11.14 shows different types of equilibrium together with their mcchanicaJ analogies. Shas been used as the criterion for equilibrium.

11.15 Local Equilibrium Conditio...

Let an arbitrary division ofan isolated system be considered, such that

S - SI+51,U - UI +U1 Then forequilibriwn, it must satisfy the condition

oS could be made posilive because of higher order tenos). Now to the first order in a very small change
10 first order in small displacements (otherwise

(oS>u.v'" 0

0IS Now

(:~ oU1+ (aa~l oU2+ (:~)Q oVI+ (:~ 10Vl

TdS - dU+pdV

(;~)v ",~, (;nu ~




0IS -

(..!.. - "'!")OU I + (l!!. -li)o VI + Second order tenos 7j 72 1j 72

OIS = 0, at equilibrium
T1 - T2 PI - Pz



11.16 Conditions of Stability

are necessary bill noc sufficient conditions for eqllilibrium. To prove that S is a
maximum, and G o r Fa minimum, it must satisfY 02S< 0, olF> 0, 02G > 0 If the system is pel1Urbed, and for any infinitesimal cbange orthe system At eqllilibrium, S " S"""" F "' Fmm , G " GmiD , and oS " 0, of'' 0: 00 >= 0: these

(oSN,v < 0, (OG)p,T > 0, (oF)y,v > 0 it represents the stability of the system. The system must revert to the original state, For a spontaneous change, from Eq. (I 1.46) oU+poll - ToS<O
For stability

oU+poll - ToS > 0 Let us choose U= U(S, p) and expand OU in powers of 011 and oS. 6U=(oU] os +..!..(iJl~] (OS)2+(oU] 6V as v 2 as v aV s .1( o'U] (OV)2 +~. OIl.OS + ... 2 aV2 s aVaS "' ToS-poV+ ..!..(o'U] (oSl 2
2 aS

+l(o'U] (OVi +~.ov.OS+. 2 aV1 s aV ,aS

The lhird order and higber terms are neglected. Since OU +pov - ToS > 0, it must satisfy the conditions given below

>0 ( o'U] >0 o'u >0 ( o'U] asl v 'aV1 s 'aV,aS

These inequalities indieate how the signs ofsome imponant physical qllluilities become restricted for a system to be stable.


428 = Since T> 0 K

&w wAppiUd 17ItrmodyMmic:J




which is the condition of thermal $tabiUry.

(au) __p aV , (a'U) (a p ) OV2 s ~ - oV s

(~n, <0


i.e. the adiabatic bulk modulus must be negative. Similarly, if F - F (T JI), then by Taylor's expansion, and using appropriate substitution

For stability
~ F+S~T+p~V > O


a'F) >0 ( OV2 (aF) aV , =_p


(~;,l, -- (~~l,

(~nT < 0
11.17 Third Law of Thermodynamics

(11.5 I)

whic h is known as the condition of mechanical $/ability. The isothennal bulk modulus must also be negat ive.

From Kelvin- Planckstatement of second law, it can be inferred thai by the use of a finite number of cyclic heal engines, absolute zero temperature cannot be attained. But third law is itselfa fundamenta l law of nature, not as derivable from the second law. As the other laws (zeroth, first and second), the third law also cannot be pro\"(~d. It is always found to be obeyed by nature and not violated.

By using Joule-Kelvin expansion, a temperature below 5K is possible to obtain by producing liquid hciium. SliIIlower tempera[UJ"tscan be attained by adiabatic dcrnagnetisarion of a paramagnetic salt. Temperatures as low as 0.001 K have been achieved by magnetic cooling. The magnetic properties ofa substance can be classified as eitherdiamagnClic where the substance is repelled by a magnet, or paramagnetic such as iron, wtu'ch is attracted by a magnet. A paramagnetic salt, such as gado linium sulphate is used for magnetic cooling. When the salt is cooled to a very low temperature, icl molecules act as tiny magnets and align themselves when subjected to a magnetic field. In 1926-27, Giaque and Debye independently suggested that the low temperature properties of certain paramagnetic salts might be used for atlainmenl of temperature below IK. Original experiments were conducted at Berkeley and at Lieden in 1933. In magnetic cooling low temperatures are achieved by adiabatic dcmagnetisation of paramagnetic salts. Thc actual proccss consists offour steps: 1. A paramagnetic salt is cooled slightly below I K by surrounding it with liquid helium boiling under reduccd p~sure. 2. Then a strong magnetic field of about 25000 gauss is applied. This makes the magnetic carriers, i.e., paramagnetic ions orient themselves parallel to the direction of the field. This realignment of atoms requires work. This work is converted inlo internal energy increase, which is taken up by the evaporating helium. 3. The salt is thennally insulated from the helium bath. 4. Finally, the magnetic field is removed. The mol eculesdisalign thelllSClves, which requires energy. This energy is obtained by the salt getting still cooler in lhe process. This processofadiabatic dernagnetisation is almost reversible, and the enuopy remains constant. Thc salt is hung by a fmc nylon thread inside the sail tube such that it does not touch the sides (Fig. 11 .15). The salt is first cooled to about I K by reducing the pressure of liquid helium. Next, the salt is exposed to a strong magnetic ficld of about 25000 gauss. Heat produced by magnetisation of th e salt is transferred to the liquid helium wilhout causing an increase in salt temperature. With the magnetic field still present, the inner chambcrcontaining the salt is evacuated of gaseous belium. The salt is then almost completely thennally isolated upon removal of the magnetic field, and the salt temperature decreases in an almost perfectly isentropic way. Temperatures of the salt as low as O.OOIK have been reported. An interesting and important problem in adiabatic demagnetisation is the determination of the very low temperatures produced. In the neighbourhood or absolute zero all ordinary methods of temperature measurement fail. The temperature may be calc ulated appro~imalely by the Curie's law,

Z = CI T


T' .....

LIquId helium

where Z is the magnetic susceptibility of the salt, T is the: absolute temperature and C is the Curie's constant. TItrough magnetic measurements, the absolute temperature may be calculated. The fundamental features of alt cooling processes is that the lower the temperature achieved, the harder it is to go still lower. Eltperiments indicate that the final temperature T; achieved by adiabatic

demagnetisation is roughly proportional to the initial temperature T;.lfthe first

demagnetisation produces a temperature one half that at the start ( T{ =

T; ). the

second demagnetisation from the same initial field will cut the temperature in half again and so on. Eventually, an infinite number of adiabatic demagnetisations would be required to attain absolute zero. Generalizing from experience, we may accept as true the statement that: "It is impossible by any procedure, no matler how idealized, to reduce any condensed system to the absolute zero of temperature in a finite number of operalions".

This is the principle of the unatlainabililY ohbsolute zero, called the Fowler-

Guggenheim statement o/Thrid loll'.

Ii -

Any isothennal magnetization from 0 tollj (magnetic intensity) such ask-i). i2 etc. is associated with a release of heat. i.e.. a decrease in entropy (Fig. 11 .16). The processesi! -Ii. i1 -h, i) -h etc. represent reversible adiabatic demagnetisalions with temperature getting lower and lower. Repealed cycles ~f isothennal magnetization and adiabatic demagnetisation would bring about a very low temperature. II is seen thai (S( T.ll j ) - S(T. 0)) decreases as the temperature decreases, i.e., Mill < Mn < MI' It is accepted from experimental evidence that: ''The entropy change associated with any isothennal reversible process of a condensed system approaches zero as the temperature approaches zero" . That is, lim

dSr "" O. This is called the Nernst-Siman stutemefll a/third loll'.

The condensed system here refers to a solid or liquid. Just like the proof of the equivalence of the Kelvin-Planck and C lausius statements of second law, it can also be shown that the Fowler-Guggenbeim and NemstSimon statements of tbird law arc equivalent in all respects (sec Zemansky). The violation of one statement implies the violation ofthe other. Now. it can be seen (Fig. 11.16) that in the processk- i t entropy decreases by a certain amount. in i l -Ii entropy remains constant, inli - i2 entropy decreases further, and so on. If the entropy of the system at absolute zero is called thereropoint entropy. a third. equivalent statement of third law can be expressed as follows: "It is impossible by any procedure, no matter how idealized, to reduce the entropy ofasystem \0 its zero-point \'alue in a finite number of operations". There are many physical and chemical facts which substantiate the third law. For any phase change thaltal:.es place at low te mperature. ClausiusClapeyron equation:

E..e. =~

vr -v;

holds good. From third law. lim (sr - Sj) = 0 and sincevr -vi is nol zero. it shows
,~ .


r ... o dT

lim~ - O

This is substantiated by all known sublimation curves. II is known that:

l1G - tlH - TM
Experience shows that the last term is very small, particularl y at low temperatures (Fig. 11 . 17) leading to lim l1G = tJ/ which confinns that lim M " 0 as T - t O. ( 11.52)


432 = T

', !c-- - -- - - --;!k

' k ::-- - - - - - "";I,









5(O,Hj) _5(0,0)_0


H -' ,

r _oL
__~~~_________________ ~

Fig. 11.l6

S(O, Hj)


T-JI GIld T-S diagrll/IU of 0 par4"1lW'tlic subJlllllrliO U.Q'" 1M '9"INUllrt of Iltru JI4U"ImlJ of 1M third III",




FIg. 11.17

6G __ All Ilnd,, '" <, .... T-. 0

From the Gibbs-Helmholtz equation

since lim (lJ.G -1!Jf) - t

lJ.G -tJf . . T[aM] aT . 0 as T -+ 0,




oor1iml!.S ", oa'JT-+O

lim liG - f...H "' lim da 89 T-+ 0 T aT By L 'Hospital's rule, the left hand side is equal!o:


lim[22-rJH] = lim dG - lim e araT ar P

( 11.55)

Therefore, al absolute zero we must have for any system, Iimcp - OasT-+O (11.56) and similarly, using the Gibbs-Helmholtz equation connectingFand V lim Cv " Oas T-+ 0 (11.57) AI very low temperntures. Debye showed thaI: Cp '" C. - 464.4 fllfJ) (1 1.58) where8is the Deb)'e lempel1lturc:, a charatteristic ofa given substance. Thus, for any material and al T = 0,

Cp=C. " Kr Cp " Cy-O.



(a) Derive the equation

Es:ample 11.1

.,(~) (ac,) __ 'laT

1 2

(b) Prove that C, ofan ideal gas is a function of ronly.

(c) In the case ofa gas obeying the equation of state

.g;!... .. I + B'p


where B' is a function ofTonly. show that

d' Cp",-RTp dT 2 (B'T)+(Cp)o

where (CpJo is the value at very low pressures. Solution


_T(aS) aT

r ) ( ac ap

= T aT.ap


NOW( ~~)1


~~ )r' by Maxwell's relation

ap.ar : :; -


( ~) dp T=-T
(b) For an ideal gas

(a'v) (a'v) arl



V o: nRT p

( ~) ar


"d(~) ar2 p .0

a; ( ac


= 0, i.e. C p is a function of r alone.

~v RT


+ 8'p


B'p=~V - I

B 'T= :(~~ +(i -:)

[~(B'T)] oT




(B;T)]pRoT !.(a'~) =_J-[ aC,) [a'oT RT op

:. On integration

where CpO (integration constant) is the value ofS, at very low values of pressure.

Example 11.2 The louie-Kelvin coefficientlJ) is ameasure of the temperature change during a throttling process. A similar measure of the temperature c hange produced by an isentropic change of pressure is provided by the coefficient 11.,

"' - (~) ap ,
Prove that

1l -IlJ""C

The louie-Kelvin coefficientllj, is given by

T (ay) _y
oT p
Since C

p '" ::)p


and by Maxwell's relation



Balk 111141 A"",id 17tmI!HyMJ'I/Q


"I_ _ [as) [aT) _-"op oS

T P Cp

[as) [aT) ap T oS


aT s --

JJ.j = +P. -

Alternative method: From the second TdSeqUlltion

y c y

JJ. -JJ.j ~ c


TdS " C dT _T (OV )




[aT) T[ay) op ." P ... C oT



"1 _2 +[ay)_y] C aT y
p p

1'. - 11 - -



Example 11.3 If the boiling point of benzene at I atm pressure is 353 K, estimate the approximate value of the vapourpress~ of benzene at 303 K. Solution Using Clapeyroo's tqUlltion and Troutoo's rule, Eq. ( 11.21),

P - I0I.325exP{~ (I .. 101.325 exp - 17.7 kPa 8.3143

;)} 303

{~(l- ~)}

Example ll.'" The vapour pressure, in mm of mercury, of solid ammonia is given by In p''' 23.03 - 3754

and thatofliquidammooia by
3063 inp - 19.49 - - T (a) What is Ihe tempcrarure oflhe triple point? What is Ihe pressure? (b) What are the latent beatsohublimation and vaporization? (c) What is the latent beat of fusion at Ihe triple point?


At the triple point, the saturated solid and saturated liquid lines meet. 23.03 _ 3754 .. 19.49 _ 3063

T "" 195.2 K Ans. (a)

_ 23.03 _ 3754 P 195.2 Inp " 3.80 P .. 44.67 mm Hg With the assumptions, v"' 11 and v'" _ RT p Clausius-Clapeyron equation reduces to



~ ~I

dT = liT! . .....

where I., is the latent beat of sublimation. The vapour pressure of solid ammonia is given by Inp - 23.03 -

3754 T

I... = 3754 x 8.3143 " 31,200 kJ/kgmol

The vapour pressure ofliquid ammonia is given by

Ans. (b)

Inp - 19.49 - 3063


when IYIp is the latent heat of vaporization IVIfI " 3063 x 8.3143 .. 25,500 kJlkgmol At the triple point
Ans. (b)

1..... - f""f'+ / ru
where IAI is the latent beat of fusion.

Ir.. - I..... - /V>fI

= 31,200 - 25,500 = 5,700 kJlkgmol

Example 11.5 negative.

Explain wby the specific beat of a saturated vapour may be


5aturatI!d vapour line



&lutlon As seen in Fig. Ex. 11.5, if heal is transferred along the salw'alion line, there is a decrease in temperature. The slope of the saturaled vapour line is negative. i.e. when dS is positive. dTis negative. Therefore, the specific heat at
constant saturation

C-_T[dS-) dT

is negative. From the second TdS equation

TdS -

C~T- T( ~~)p dp

T dT - Cp-T


[d.-) dT [~)

p dT ..

nR l~ [usingpY- = nRTand "" Cp - T' -p-' "T(".;;;''''.'-.;;;''') Clapeyron's equation]

c- cP Y"'.~ [.,' Y_ Nt T Y"

C- .. C _ I"", , T


Now the value of I.,..IT for eonunon substances is about 83.74 Ji g mol K (Trouron '.r rule), where Cp is less than 41.87 Jig mol K. Therefore, c:; can be nagative. Proved. Example 11.6 (a) Establish lhecondilion ofequilibriwn ofa closed composite SYSIC1lI consisting of two simple systems separated by a movable diathermal wall that is impervious to the flow of matter. (b) If the wall were rigid and diathennal, penneable to one type of material, and impermeable 10 all others, state the condition of equilibrium of the composite

(e) Two particular systems have the following equations of stale


..l _1./i!!L,li=!!L1i
1 j 2 Vt


-.l. '" 1. Ii !!J... b... = Ii!!l. 122v21i V 2

where Ii - 8.3143 kllkg mol K, and the subscripts indicate systems 1 and 2. The mole number of the fIrst system is NI - 0.5, and that of the second is N2 - 0.75. The IWO systems are contained in a closed adiabatic cylinder, separated by a movable diathennal piston. The initial temperatures are TI = 200 K and Tl = 300 K, and the total volume is 0.02 ml. What is the energy and volume of each sYstem in equilibrium? What is the pressure and temperature?


For the composite system, as shown in Fig. Ex. 11 .6 (I)

VI + U2 - constant Vt + V 1 - constant
The valuesofV\, U1 VI' and V2 would change in such a way as to~imize the value of entropy. Therefore, wben the equilibrium condition is achieved for the whole system. Since


S - SI +S2 '" St(Ut, VI' .... Nk,) + S2 (U1 V:z, .... Ntl .. )
.. dS =

(;J, t" . NI,. (*tl . . ,N., .

dU +



~ Mt:IYeble~...

dililhel'mlli '


Fi3. Ex. 11.6


Since the expression must vanish ror arbitrary and independent values ordV1 anddVI

...!..-...!... -Oand.EL-h.- O



PI - P2 andTI - Tl

:. These are the conditions ormecltanical and thennal equilibrium.

(b) We will consider the equilibrium state or two simple subsystems (Fig. Ex. 11.6 (b connected by a rigid and diathennal wall, penneable to one type ormaterial (NI) and impenneable to all others (N2 Nl .... Nf ). We thus seek the equilibrium values or VI and or VI' and or and N'_I (i.e. material NI in subsyslems I and 2 respectively.) At equilibrium, an infinitesimal change in entropy is zero

N,_ ,


"' - 0

dS - dS, +dSz

-(:3, t,.NH . (a~7_1 t"V1.N1 .l .

I dV +

dN H

From the equation

(:~ )Vl,Nl'Z. . dVz + (a~;'l tZ.V1,N '1dN'_2 1

TdS '" dU+ pdV -lJdN

( ~l aU V.N. . .

-1- (~l

T' oN u.v


dN H + dN'_I " 0 dU, +dU2 " 0

( PH _ P l-l )dN H ... 0 Tl 1i T2 As 115 must vanish ror arbitrary values of both dUI and dN l_1

'" - (...!.. - ...!...)dU, 7i


which are the conditions of thermal and chemical equilibrium.


Nl "" O.S gmol, N 2 - O.7Sgmol

Tl-J .. 200 K, TI_2 : 300 K V .. VI + V2 - 0.02m3 VI + V1 = constant

4U1+ 4U2 "' 0 Let Tr be thc rillal tcmperature (Fig. Ex. 11 .6 (c (U'_1 - UI-I) .. - (U1-2 - Ui-l)

"2R NI( Tr - 7;_1 ) - - "2RNl (Tr - T;'-l)

O.S(Tr - 2(0) " - 0.7S(Tr - 300) 1.2S Tr = 32S



Tr" 260 K
U'_I" "2 RN1TrU'_2"



"2 x 8.3143 x O.S x 10

x 260 "" 1.629 kJ

x 8.3143 x 0.7S x 10-3 x 260 " 2430 kJ At equilibrium

PI-I " Pr_ 2" Pr

A"". .

Vr_1 + Vr_ 1- -



(N 1 + Ni) - 0.Q2 m

8.3143 x 260 x 1.2S x IO-L ", 0.02 m1

Pr '" 8.3143 x 260 x 1.2S x 10- kN/ml - 13S kN/m1 - 1.35 bar
V'_1 .. 8.3143 X O.S X 10-) X 260 .. 0.008 m1 135
V'_l - 0.02 - 0.008 - 0.012 m1


Eumplc 11.7 Show thai for a van der Waals' gas


(~)T " O


(c) nv - b)Rkv .. constant, for an isentropic

(d) c,-c '" 1-2a(v- blIRTv l


(n2- nih - (P,Pl - Plv l) + a(...!...




(a) From the energy Eq. (lUJ)

(~~l, =~~il,-p
~ aVar -. \., arl

-.UL) + (Ei.) ar -(Ei.) ar


.'u J~l av.ar= ' lar1 v


C'l ('oV

T '"

.'u J b>.) av.ar""l ar1 v'" av


For a van derWaals' gas

(p+-;r-){V-b) - Rr
P- v - b


( ~) ar v - o

(~l, - o
:. cy is independent of volume. (b) From the first Tds Eq. (11.8)

Proved (a)

Tds - CydT+r(~:


andenergyEq.(ll.lJ)(~~)T =T(~:t -P
ds=c dT +, [ p+

('Ul] -aV


"' "


Forvao derWaals' gas

ds ~cv d: + ~(P+7 )dV

dT R ,-+--d, v T v- b


2 = R In -VI - b

v - b

Proved (b)

(c) At constant entropy

,-+--dv"'O v T v-b

by integration,
p ~

dT +-B..~ = 0



p) (a,) ,_, _T(a aT , aT ,

- [(~a +pn;),

ltv - b)RJC., = constant

Proved (c)

o r:, +p)(~;),
- (::b)(~;),
From the equation

(p+ :~ )<V - b) = RT (v - b) (- 2aV-l)(.!'.) + (p + ~X.!'.) - R aT v aT

.) (.!' aT

R/ (v - b)

RT 2a (v-b)- vr
Proved (d)

cp - cv - -;--cc:-;::--";:;;-c-;o= 1-2a(v b)2/ RTvl


au) =T(ap) _p=-:,. (av aT v




(U2 -lIlh=

O(",!", -..!..) VI V


z- hlh- - (P2Vl- PI!)t) + a(.. !. . _...!...) til


Proved (e)

Example 11.8 The virial equation of state of a gas is given by pv - RT(I +B'p+Cr+ ...) Show that

, .... 01.
the Boyle temperature.



-.JoRT' dB'

Hence, prove thai the inversion temperature

ora van der Waals' gas is twice

pv - RT(I +B'p+C'pl+ ... )

V " RT +RTB'+RTpC + .. .

ilv) (-ar
T -


R+ RT-+RB'+RTpdB' de' "+RpC+ .. . p dT dT '" RT +Rr dB ' +RTB'+Rr dC' +RTpC+ ...





...ldB' dC' -v - Rr-+Rrp+ ... dT


p, - c p

-'-[T(~) ar -'J

, .... 0

[dB' +p dC' + .. .] dT dT
= ---Rr2 dB' cp dT

For a v~n der Waals' gas, to find Boyle temperature Ta.

-= ....
TB - ....!!....
bR B' .. ..!L _...E..- __ '_ Rr - RT Rlrl

dB' b + 2a dT "' - RT~ Rir' 1im1J.J " - , - - RTl + R2rl


RT' ( b

p .... O

2,) =0

_ b _ RT2


c, - -bR
TL '" 2T8 or Inversion temperature - 2 x Boyle temperature

EJ.ampJe 11.9 Over a certain range of pressures and temperatures, the equation ofa certain substance is given by the relation

RT- C v- P T'
where C is a constant. Derive an expression for: (a) the change of enthalpy and (b) the change of entropy, of this substance in an isothermal process. Solu/ion (8) From Eq. (11.1S)

~ - CpdT+[V- r( ~; )Jdp
(h, - h,),



T( ~~ )}



&Jic 11M ApplUJ 1'ItmruNJyruImill

On substitution,


(b) Using sond


4C ., -;;:r (PI T equation


Tds" c,dT - T(~) aT ,dp

""._(ilv) aT , dp,
~ - (; + ~)~


nmple 11.10 Agron gas is compressed reversibly lUld isothermally at the rate ofl.5 kgls from 1 atm, 300 K 10 400 aim. Calculate the power required tonm the compressor and the rate at which heat must be removed from the compressor. The gas is assumed 10 obey the Redlich.Kwong equation of state, for which the constants are:

a " 0.42148--'- and b ~ 0.08664 - - '

p, p,



For argoo, Tc lSI K and Pc '" 48 alm. Take




Substituting the values ofPc' Tc and R ,

a '" 0.42148 (82i (l51f' _ 16.8)( 106 atmK



b "" 0.08664 (82)(151) '"' 22.4 em 48 gmol


Substituting the numerical values ofPl. T I a, bandR into the Redlich.Kwong equation


p . v-b - T II2v(v+b)

vi - 49.24 vi + 335.6 V z- 43,440 ~ 0

foom which we obtain

~k RdmiQIIS,

Epj/ibr;lIIII.M TflirilAw


V z '" 56.8cm /gmol SincePI = 1 attn, the volume of the gas at the initial state can be obtained from the ideal gas equation:

'I I vl - RT. = 82 x 300 - 24600 , cmgmo p, I For isothermal compression,

Now, d(pv) . p dv + v dp

7,,,,,op,,,-p,,,-[1 p "l

we have

[~; l: -[ ~; l,[~; l.

dh12 = hz - hi = pzVz - PIP1 -

{l[p -r( ~~


According 10 Redlich-Kwongequation. we have,

Substituting the numerical values, hz - hi "'- \,790 J/gmol

For the RedlichK wong equation this becomes,

5 -5 2 I

1[- - + 1
R v-b

.. Rln 1.12 -b _ __ a_in (1.12 +b)Iv2 vl-b 2b1jll2 (vI+b)/vl

Substituting the numerical values,

dv a 2Tl I2V(v+b)


"2 -.II - - 57 J/gmol.K

QI1 "' ,;,TI ("1 -51)


x300Kx(- 57)

39.8 g/gmol g mol K .. - 4.29 X 10' JIh .. - 11 .917 kW (heat removed from the gas)

W I1 '" QI2 + m(h l

-- 4.29


107 +

~ x 1790

.. _ 3.84 X 107 Jib

- - 10.67 kW (Wort is done on the gas)


11.1 What is !he condition for exact differential? 11 .2 Derive Maxwell's equations. 11.3 Write down the first and 5eInd TdSequations, and derive the exprnsion for me difference in heal capacities, Cp and C.. What does the upression signifY? 11.4 Define volume ClL:pan5ivily and i30thennal compressibility. II.S Show that the slope of an isentrope is greater than that of an isomerm on~v piCM. How is it meaningful fllf cstimating the work: of compression? 11.6 What is the energy equation? How does this equation lead to the derivation ofme Stefan-Bollzman law oflhenual radiation? 11 .7 Show that the internal energy and enthalpy of an idea.! gas are functions of tetnperature only. 11 .8 Why aredU - CydTand dH - CpdTttue foran ideal gas inany process, wllereas the5e are true for any other substance only at constant volume and at constant pressure respe<:tively? 11 .9 Explain loule-Kelyin effect. What is in\'CI"1ion temperature? 11.10 What i$louleTbomson coefficient? Why ill it zero for an ideal gas? 11.11 Why does the hydrogen gas need 10 be preo:ooled before being throttled to get the cooling dfect? 11.12 Wby docs the maximum temperature drop occur if the state before throttling lies on tbe inversion curve?

11.13 Why does the Gibb5 I\mction remain conslaDt during pba.se tmlsition? 11.14 What ate Ibe characteristics orlbe fim order phase transition? 11.1 5 Write down lite representative equation rorp/ta.5e transition. Why does the fusioG line for water have negath-e slope on the p-T dilgl"lll"l? 11.16 Why is the slope of the !IIIblimation curve l ithe uiple poinl on the p-Tdiagram greater than that orthe vaporization curve at the same poiol? 11.17 Explain bow thmnodynamic properties are evaluated. from an equation ohtate. 11.18 lIIustn1te how enthalpy change and entropy change of a gas can be estimated with the ltelp oran equation o f state. 11 .19 State lite important lItennodynamic criteria wbich an equation of state should salisfy. 11.20 Explain bow the Boyle tempOl~ is yielded wben: Iim@ZlilPn - O


11.21 What is foldback temperature? 11.22 Show thai for an inversion curve {ilZJan, " O. 11 .23 Define chemical potential of. component in terms of U, H, Fand G. 11 .24 What is lite use of lite Gibbs enlropy equation? 11.2S Explain lite ! igoificancc of the Gibb5-Duhem equatioo. 11.26 State lite cooditionl of equilibrium of I heterogeneous system. 11.27 WhaI60 you understand by pbase equilibrium? 11.28 Give the Gibbs pba.se Nil' for a nonreactive system. Why is the triple poiot ofa substance noovariant? 11.29 What are the four types of equilibrium? What is stable equilibrium? 11 .30 Stale the conditions of spoolaneou$ change, equilibrium and criterion of stability for: (aJ a system having constant Vand Y(i.e., isolated), and (b) system baving coostanl T and p . 11 .3 1 What do you undcmand by neutral and unstable equilibrium? 11 .32 What is mewtable equilibrium? 11 .33 Show thai for a system to be stable, these conditions ate satisfied (a) C. > 0 (thermal stability)

(~) ,y , < 0

(mechanical stabili!)')

11.34 11 .35 11.36 11 .37

How is the third Jaw a funllaJMntai law of nature? Explain the phenomenon of adiabatic demagnetisation ofa paramagnetic salt. How ate tcmpenltures DCa!" absolute 2.C:ro estimated.? Givcthe Fowler-Guggenbeim stalcment of tbird law. How is il different from the Nernst-Simon statement oflhird law? Give the lbird equivalel)t statement ofthc third law. 11 .38 State snme pbysical and chemical facts wllicll substantiate the third law.

11 .1 Derive the followingcquations
<I) U-F - T ~

(") ilT

-- r ~('FIr) ~T v

fSO = -

(b)C - - T -

("F) aT:

(e) H _ G_T('G) =_TI(aGIT)


(d) Cp __



11 .2 (al Derive !he equation

(5.) aPT . r(-4) aTv

(b) Prove that Cy oran ideal gas is a function of Tonly. (e) In the cue oh gas obeying the equation ofstBte

.E. _ I + 1!:.
RT ,
where 8" is ali.ulction ofTonly. show tbat
c. - - --;- d]J""(B"

RT d1

n + (c.lo

where (c. lo is the value at very Jarge volumes, 11.3 Derive the third TdS equation

TdS - C.

(::l ~ +Cp (~np


and show that the three TdSequations may be written as


TdS - C. dT+


(b) TdS - CpdT - VfJT~

(e) TdS - .S:..kdp+ .E!... dV

__ 1_

11 .6 (. ) Prove thatlbe slope oh curve on a Mollierdiagram representing I reversible i!Othc:nnal proeess is equal to 1 T-

(b) Prove thaI !be slope of a curve on a MoUier diagram representing a reversible

!o.oclloric proecss is equal 10

r-1 T+--

11.7. (a) Sho .... that

I-l,cp '"


am), (----aT

For I mole of I gas, in the region of mOOcnlle prcssun:s, the equation ofstllte may be written as

..e!- - I + B'P +C'i


where It and C' are functions oftempcralUrc only. (b) Sbow that as p -t 0 2 dB'
/-lJ cp .....



(e) Sbow that Ihe equation orlbe inversion curve is dB' /dT

P "' - dC'/ dT
11 .8 Prove the follo"";ng fUlK:tional relationship of the reduced propcnics for the inversion curve ofa van der Waals' gas
T. '" 3(30, _ 1)2 and

4 v~



Hcuu, sbow that


Muimum invers ion IC!1Ipm!ture ... 6.n Criticalt<:mpenlturc

Minimum inversion Icmpcmure _ 0.75 Critical temperature 11 .9 Estimate the maximum inversion tcmpcmlurc of bydrogen if it is assumed to obey tbe equation of stale pV - RT + BIP + Bli + BIP' + . For hydrogen, BI x 10' .. 0 + 10- 2 bT + 111 ciT when: 0 - 166. b .. - 7.66. e'" - 172.33 I J.IO Tbc VlIpOlU"pteSSUi"C ofmcmuy at 399 Kand 401 K is found to beO.988 nun and 1.084 1M! of men:ury respectively. Calculate the latent heat of vaporization of liquid men:wy It 400 K... All.!". 61,634.96 kJlkg mol

f.52=11 . 11


the vicinity of the triple point, the vapour prnsure of liquid ammonia (in 8ttnosphettS) is represented by

Inp - 15. 16 - 3063

This il the equation of the liquid-vapour bollDcWy cW'Ye in I



Similarly, the vapour pressure o(50lid ammonia is

lnp - lS.70 - 37S4
1 (. ) What is the tempeRture and pteswre al the triple point? (b) What arc ~ I.tent hea" ofSllblimuion and v. porizatio n? (e) What i, th" !..ICDt heat offusion.t the IripJc poinl? AM. 195.2 K. 0.5SS Itm., 1498 tJlir.g, 1836 kJ1k8, 338 tJlIr.g 1 [. 12 It i~ found thai I CCfIain liquid boils". tenapcnrure of9SC at tile top ora hill. whereas it boils at a ICinpeRtUfC of IOs e at the bonom. The latent heal is 4.187 kJ/S mole. Whal is thc approximale beightofthe hill? Assume To - 300 K. AM. 394 m 11.13 Show thai for an ideal gu in I mixture of ideal gases 1 11.14 Compute Jlj for I gas wbosc equatiOfl .Orstatc is

d#lt - Ilk - hk dT+I\dp+RTdlnxk

p(tI-b)- RT
jl.J - -

I 1.1 S Show that



[in -[ ;~ ),

(b) [ ; ; ) ,

= -1(;;), -p [;;),
""Tiil " TR
3 - /11 )

11. t 6 Two panicuJar systems have the following cqualioll5 of state

[flJ and

?If ="2 R [fl)


s_/l lJ

whet'C R .. 8.3143 kJlkg mol K. The mole numbcTofthe rIM system is N' I) 2. and that oftbc se<:ond is!P) - 3. The rwo I)'stcrns arc scpatlIted hy a di.athmnal wall, and the total cnetiY in the composite system is 25.120 kJ. Whal is the internal ~ of each system in equilibrium? AM. 7.2]d, 17.92 kJ 11.17 Two systems with the equations of state given in Problem 1 [. 16 arc ~ted by diathcnna[ wall. The te~YC mole numbers uc I II) - 2 and ~J - 3. The initial tcmpcnItum; lite 2S0 K and 1m - 350 K. What arc thc values of cJ. 1) I nd tP) .fler equilibrium has been established? What is the equi[ibtiwn



Ans. S.02 kJ. 20.04 kJ , 321 .4 K 11.1S Sbow that the change in latent hc.t L with tcmpcnIturc is givm by the following relation


- = 453
( dL ) _ ("'"_'"""__ L v""P'"' _



p" _


V"'R" e L

11.19 Show that for a van der Waals' gas. the Joule-Thom50n coefficient

i$ giv~ by



~[2a(V - bl- R1bo ]





11 ..20 At273 .15 K the spttific \'olumes of wale rand ice an: 0.001 and 0.001091 m' lkg
and the latent beat of fusion of ice is 334 kJlkg. Determine the melting point increase due 10 increase of pressure by I aim ( 101.325 kPa). A1I5. - 0.00753 K 11.21 Calculate the latenl beat ofvaporizalion ofsteam fonned by boiling waler under a pressure of 101.325 kPL At a pressure near this, a rise of temperature of I K causes an inerease of vapour pressure 00.62 kPa. AM. 2257 kJlkg 1 I .22 It is known Ihat radiation exerts a pressure p '" 1/3 ... where .. is the energy per unit volume. Ca) Show that

oo " Tw +

~(Ts -1 U)dV

s iii the entropy per unil vol~.

(b) Alsuming w and 5 as functions oftemperarure only. show thaI

(i) w- As"" J (iii) w- aT' where A is the constant of integnil ion and a " gl1256 Al. (e) Sbow thaI the average time radiation remairu; in a spherical enc1O!1ure of radiUll r is ,ivcn by (i i)

s" .!ar

4, ,-J,
where c is the speed ofradiation. (d) If Ea is the energy em ined per unit area of spherical surface per uniltime. show thai

Ea ~
whcTe (1 - acl4 JlIId Tis the temperature of tile surface. 11 .23 Show thaI !.he invenion temperatureofa van .Ier Waal,' 8U i, given by T," 2tJJ

1\.24 Show thaI ; (0) ('")

all T

=T,(iJ(P1 Tl ) aT


(-"' -) = _T'("'T) ) ap T aT

11 .25 Show that for a van ller Waals ' gas allow preswTeS. a loule-lbomsoo expansion from pres.o;ure PlIO I'l produces a temperature change which can be fOORd from the solulion of

b 7j-T; where T[ is the inversion tempetah.lrC. 11.26 Usin, the Redlich-Kwong equation of Slatc, devclQP upressions (or the changes in entropy and inlema! energy of a gas in an isothennal process.
A.n!. (11 - lin '" R In - - + D]-b 2bT
Dl-h II [Vl(VI+b)] -----mIn 7';:'--:-~ DL(Vl+h)

C, T1-T, PI - P2 - -(T1- TJ+ Tl in - - -

, In[Vl{tll ( ":1-" 1 '1 - 2bT"2 Dt(Vl+b)


11.27 Find the cbange of entropy of I gas following Claw;ius equation of Slate al constant tcmpcnllure p(v-bj-RT

11 .28 (a) SllowtllatforavanderWlllll5'gas

ROl(V_ b)

{J " RThJ _ 2a(o



kr '"
11.29 (a)Sbow that




(b) What ilthe value of kiP expresxd in its simplest fonn? (el What do the above relations becoIM when II "' 0, b '" 0 (idell gas)?



oP . P

= ~ .c,


(~) =.2_ p (Iv p


(b) Hence show thai the slope of a fe\'mible _diabade process on p-V coordinates is




where k is the isothermal compresaibility. 11.30 According 10 Berthelot, the Ie'lIlpel3:me effect of the second virial coefficient is given by

where Q

8'(T) _ .E.._...2.... T T' and b arc constantl. Show that according to Berthelot,

Tm/TO =.fi
11 .31 The following expressions for !he equation of rute and the specific lleat ,. arc obeyed by a certain gas:

v_!fL. + ar' andc, - .4 + BT + Cp


where a, A, 8, C are constants. Obtain an expression for (a) the louie-Thomson coefficient, and (b) the speci fic heat c.

A"s.(aJII) -



(b)C. "' A + BT + -=----::::;:r -R 2 v-ct:r v-aT



11.32 Determine !he maximum louie-Thomson inversion temperature in terms of the critical temperature T, predicted by the (a) van der Waals equation (b) RedlichKwong equalion (c) Dieterlei equation Ans. (a) 6.15 T.. (b) 5.34 T, (c) ST, 11.33 From the virial fonn of the equation ofstate ora gas


.BL + RTB' (1) + RTC (1"Jp + .


show thallhe Joule-l1Ionuon coefficient is

" (b) For a van der Waals gas

RT: [dB' de' .. .j p, - ---.--p.



"(n _ bRT - a
Show that the limiting value of /J J at low pressures is

JI) - - 1 (" - - b) cp RT
11.34 Show thlt

k.r - k, .. !.!!..l...

11 .35 For a simple


system, show tllal

(.) [~] =T'['PIT] ilv T ilT. [~] T'[ ',IT 1 ilp T ilT
(b) - p

11.36 The liquid-vapour equilibrium curve for nitrogen over the range from !he uiple point to the DOrmal hoiling point may be eJ(pt~d by the relation:
T wbere p is lhoe vapour pressure in nun Hg, T is the temperature in K, and A - 7.182, 8 " 0.006265. and C"" 341.6. (a) Derive anexplnsion for the enthalpy ofvaporizationh fa in Icmis ofA, B, C,

logp - A - BT -

Tand vI"&. (b) Calculate hr. for nitrogen 1111.9 K with or. ~ 11 ,530 cmJ/gmol .

AIlS. S,790J/grnol

11 .31 For a gas obeying the van der Waals equation ofstate.lbow that:

(.)c-c p


R b)l I RT'r}




1. T[ ;~)' J. ..

0 10

pro~ IhalCy is a fWlCtiOO orlemperal~ only.

( ,) [.'ap .2]


T[ aT "~ ]


2<1v-) -6<100'"

av :::2 +2abv -1 )1

10 prove lhalC, for Il VM der Waals gas is not a function oflCm~ture only. (d) The relation bclWeen Tand v is given by; T{v - b)RJ<.. .. constanl (e) The relation between p and v is given by:

[p+ :2)cV-b)l lI.... COnslanl.

11.38 Nitrogen III press~ of2S0 attn and Illem~ of400 K elCparuis rever.tibly Md lIdiabalicaJly in a turbine 10 an exhaust press~ of 5 aim. The now rate is I kg/I. Calculate the power output if nitrogen obeys the: Redlich-Kwong equation of state. FOr nitrogen Ilt 1 attn take, cp - 6.903 - 0.3753 x JO-JT + 1.930 x 10-fi r - 6.861 x 10.... r l where cp is in caIIgmol-K and T is in K. FOTnitrogen, To - 126.2 K,

Po" 33.5 Ilttn.


AIlS. 272 kW

Fig. P-I [.34

II I - hI .. (h I - h4 ) + (II, - Ill ) + (hI - Ill) and s ) -J 2 - 0 - (Sl -s,) + (J. - Sl) + (I J - J 2) a .. 15.4 x 106 atmJKll2 em 61(gmol,r, b " 26.g cml/gmol

By trlal-and-<:rror, v, .. 143 cm'/gmol, 114 - 32,800 cm'/gmol T2 .. [24 K, III - 112 - 7.6 1 kl/gmol.


Vapour Power Cycles

12.1 Simple Steam Power Cycle

A power cycle conti nuously convens heat (energy released by the burning of fuel) into work (shan work) , in which a working fluid repeatedly perfonns a succession of processes. In the vapour power cycle, the working fluid, which is

waler, undergoes a change of phase. Figwe 12.1 gives the schematic ofa simple
steam power plant working on the vapour power cycle. Heat is transferred 10

water in the boiler from an external source (furnace, where fuel is continuously burnt) to raise steam, the high pressure, high temperature steam leaving the boiler
expands in the turbine 10 produce shaft work, the steam leaving the turbine

condenses into water in the condenser (where cooling water circulates), rejecting
High preuun!I, high

temperature Sl6am

Fig. 12.1 Simple SWm JlDwn pUlnl

.s8 =heat. and then the water is pumped back to the boiler. Figure 12.2 shows how a unit mass of the woi-king fluid, sometimes in the liquid phase and sometimes in the vapour phase, undergoes various exlenal heat and work interact ions in executing a powercyc\e. Since the fluid is undergoing a cydic process, there will be no net change in its inernal energy over the cycle, and consequently the net energy transferred to the unit mass of the fluid as heat during the cycle must equal the net energy transfer as work from the fluid. Figure 12.3 shows the cyclic heat engine operating on the vapour power cycle, where the working substance, water, follows along the B TCP(80iler Turbine..condenser.Pump) path. interacting

i28 ~ 8 q28 w8 i2 ."...""" "' ....,

(In boll)





Stale change

Stale change

Stale change




frvm 3 10"






Fig. 12..3


, p'


(River or Ma)



L\--.",.. .....""~
Cyrlk Itull1Jlitu unlit WfIln IU tJu UJOra"ljluid

extemaJly as shown, and converting net beat input to net work output continuously. By the first law

LQ~= LW~


QL-Ql - WT-W, where QL - heat transferred to the working fluid (kJ/kg) Ql = heat rejected from the working fluid (kJ/kg) W T - work trans ferred from the working fluid (kJ/kg) W, ~ work transferred into the working fluid (kJ/kg)
The efficiency of the vapourpowcrcycte would be given by

( 12.1)


\2.2 RanJdne Cycle

Foreach process in the vapour power cycle, it is possible to assume a hypothetical or ideal process which represents the basic intended operation and involves no extraneous effects. For the steam boiler, this would be a reversible constant pressure heating process of water to form steam, forthe turbine the ideal process would be a reYer5ible adiabatic expansion of steam, for the condenser it would be a reversible conSWlt pressure heat rejection as the steam condenses till il becomes saturated liquid.. and for the pump. the ideal process would be the reversible adiabatic compression of this liquid ending at the initial pressure. When all these four processes are ideal. the cycle is an ideal cycle, called a Rankine C),c1e. This is a reversible cycle. Figure 12.4 shows the flow diagram of the Rankine cycle, and in Fig. 12.5, the cycle has been plotted on thep-v, T-s. and h-s planes. The numbers on the plots correspond to the numbers on the flow diagram. For any given pressure, the steam approaching the turbine may be dry saturated (state I) wet (state I'), or superheated (state I'), but the fluid approaching the pump is, in each case, saturated liquid (state 3). Steam expands reversibly and adiabiaticaJ\y in the turbine from state 1 10 state 2 (or I' to 2', or I" to 2"), the steam leaving the :oJ.Tbine condenses to water in the condenser reversibly at constant pressure from slate 2 (or 2', or 2") to state 3. the water al state J is then pumped to the boiler at state 4 rever5ibly and adiabatically, and the water is heated in the boiler to form steam reversibly at constant pressure from state 4 to state I (or l' or I").



<p~ o,
fig. t:U A simp" slr4'" pltt.ltI


w. . .

For purposes of analysis the Rankine cycle is assumed to be carried out in a steady flow Clpcration. Applying the steady flow energy equation to each orthe processes on the basis of unit mass of fluid, and neglecting changes in kineticand potential energy, the work and heat quantities can be evaluated in tenns of the properties of the fluid .








2'2 r ___ "~





Fig. 12.5

RJI,w'"" 9,h olt t-~ T-J atul It-I tfillgrc..u


For 1 kg Ould The S.F.E.E. for the boiler (control volume) gives
h~+QJ- h!


The S.F.E.E. for the lurbine as the control volume gives h1 - WT + h1

~T - h l - h2


Similarly. the S.F.E.E. for the condeoser is h1""Ql+h l Q2",h2 - hJ and the S.F.E.E. for the pump gives
hl+Wp - h~


The pump handles liquid water which is incompressible. i.e., its density or specific volume undergoes Iinle change with increase in pressure. For reversible adiabatic compression, by the use of the genenll property relation

Tdr - dh -vdp; ds - 0 and dh - vdp Since cbange in specific volume is negligible


fJI - vtlp 1I. - II) - v)<Pl-Pi) If v is in m1IKg andp is in bar

114 - "l " Vl<P 1- P2) X I~ Jfkg

work nltio - ~ == -"'i,;-"'-


The work ratio is defined as the nltio of net work output to positive work output.

W Wr

Wr-W, Wr

Usually, the pump work is quite small compared to the turbine work and is sometimes neglected. Then II. " "l' and the cycle efficiency approximately


."--hi - 112 hi - h.

The effiCiency of the Rankine cycle is presented graphically in the T-s plot in Fig. 12.6. Thus QI is proportional to area 1564, Q2 is proportional to area 2563, and W.... (" Q, - Q;0 is proportional to area 1 2 3 4 enclosed by the cycle.



FIg. 12.6 Q" W... lind Cb IIr. F"/lQrliQ""/ /() ....41

The capacity ofa steam plant is often expressed in terms of:rleam rate, which is defmed as the rate of steam flow (kglh) required to produce unit shaft output (I kW). Therefore Steam rate _ -;;;---'-;;,-!t . I kJ / s Wr Wp kJ lkW I

..!!... =
Wp kWs



3600 kJ Wp kWh



462=The cycle efficiency is sometimes expressed alternatively as heal rate which is the rate input (Ql) required 10 produce unit work output (I kW) Heat rate _ 3600~ = 3600


From the equation W",y " -

, J , v <1,0, it is obvious that the reversible steady-flow



l1c)'<k kWh


work is closely associated with the specific volume of fluid flowing through the device. The larger the specific volume, the larger the reversible work produced or consumed by the steady-flow device. Therefore, every effort should be made to keep the spedfic volume of a fluid as small as possible during a compression process to minimize the work input and as large as possible, during an expansion process to maximize the work output. In steam or gas power plants (Chapter 13), the pressure rise in the pump or compressor is equal to the pressure drop in-the turbine if we neglect the pressure losses in various other components. In steam power plants, the pump handles liquid, which has a very small specific volume, and the turbine handl es vapour, whose specific volume is many times larger. Therefore, the work output of the turbine is much larger than the work input to the pump. This is one of the reasons for the overwhelming popularity of steam power plants in electric power generation. If we were to compress the steam exiting the turbine back to the turbine inlet pressure before cooling it first in the condenser in order to "save" the heat rejected, we would have to supply all the work produced by the rurbine hack to the compressor. In reality, the required work input would be still greater than the work output of the turbine because of the irreversibilities present in both processes (see Example 12.1).

12.3 Actual Vapour Cycle Processes

The processes ofan actual cycle differ from those of the ideal cycle. In the actual cycle conditions might be as indicated in Figs 12.7 and 12.8, showing the various losses. The thermal efficiency of the cycle is

fllh "'-


where the work and heat quantities are the measured va lues for the actual cycle, which arc different from the cOlTesponding quantities of the ideal cycle.

12.3.1 Piping lossu

Pressure drop due to friction and beat loss to the sWTOundings are the most impo!1an1 piping losses. States I' and I(Fig. 12.8) represent the states of the sleam leaving the boiler and entering the turbine respectively, I' - I" represents the frictional losses. and 1"-1 shows th e co nstant pressure heat loss to the


WP>(h4-hl(h -~

FIg. 12.7

VllriOru ~ ill II JInIIII phmt

Fig. 12.8

VllriOru i4JJn Q~ T-r plot

surroundings. Both the pressure drop and hellt transfer reduce the availability of steam entering the turbine. A similar loss is the pressure drop in the boiler and also in the pipeline from the pump to the boiler. Due to this pressure drop, the water entering the boiler must be pumped to a much higher pressure than the desired steam pressure leaving the boiler, and requires additional pump work.


Tttrlrln~ Loss~s

The losses in the turbine are those associated with frictional effccts and heat loss to the SUfT(lundings. The steady flow energy equation for the turbine in Fig. 12.7 gives hi '" hl + Wy + QIooo (12.10) W y "' h] - h2 - Q10lS

For the reversible adiabatie expansion, the path will be I-b. For an ordinary Teal turbine the heat loss is small, and IVy is hi - h2 with Q1 equal to zero. Since

actual turbine work is less than the reversible ideal work output,h 2 is greatertban h2. However, if lItere is heal loss 10 the surroundings. h2 will decrease, accompanied by a decrease in entropy. If the heal loss is large. the end state of Sleam from the turbine may be 2'. It may so happen that Ihe entropy increaSe due to friclinnal effectsjust balances the e ntropy decrease due 10 heatless. with the result lhat the initial and final entropies of stearn in the expansion process are equal, hut the apansion is neither adiobatic nQr reversible. Except for very turbines is general1y negligible. The isentropic effi small turbines, heat loss from ciency of the turbine is defined as
T llT= --=-(12.11) hi - h20 hi - h20 where WT is the actual turbine work, and (hi -h20) is the isenlropic e nthalpy drop in lite turbine (i.e., ideal output).


12.3.3 PtnnjJ lAsses

The losses in the pump are similar to those of the turbine, and are primarily due to the irreversibilities associated with fluid friction. Heat transfer is usually negligible. The pump efficiency is defined as

h - hl h hl q, ----=--W, h4 -hl
4 -


where W, is the actual pump work.

12.3." Cotulnun lAsses

The lo~ in the condenser are usually small. These include the loss ofpressUfe and the cooling of condensate below the saturation temperature.

12." Comparison of Rankine and Camot Cycles

Although the Camot cycle has the maximum possible efficiency for the given limits oflemperarure, it is not suitable in steam power plants. Figure 12.9 shows the Rankine and Camol cycles on the T-$ diagram. The reversible adiabatic expansion in the turbine, the conslAnttemperarure heat rejection in the conderuoer, and the reversible adiabatic compression in the pump. are similar characteristic features of both the Rankine and Camot cycles. But whereas the heat addition process in the Rankine cycle is reversible and at constant pressure, in the Camot cycle il is reversible and isothennal.ln Figs 12.9(a) and 12.9(c), Q2 is the same in both the cycles, but since QI is more, '1c _ is greater than '1Jtdi.... The two Camot cycles in Figs 12.9(a). and 12.9(b) have the same thermal efficie ncy. Therefore, in Fig. 12.9(b) alSo: '1c..- > '1_".. BUl lhe Camot cycle cannot be realized in practice because the pump work [in all the three cycles (a), (b), and (c)l is very large. Whereas in (a) and (c) it is impossible to add heat at infinite pressures and al conslant temperature from state 4c 10 stale I, in (b). il is difficult



4C -

D r. ,-"b c'-'



Fig. U.9



of CtlT7l~IIIM Rflllkj/U 'Jcla

to cODtrollhe quality at 3e, so that isentropic compression leads 10 a saturated liquid state.

12.5 Mean Temperature of Heat Addition

In the Rankinecyc\e, beat is added reversibly at a constant pressure, but at infmite temperatures. If T<Ill is the mean temperature of heat addition, as shown in Fig. 12.10, so that the area under 4$ and 1 is equal to the area W1der 5 and 6, then heat added

--~ ,

Fig. 12.10 MUM UmpmJlllre ojlullllldJitio"


Mean te:mp;erature: of heat addition

.1'1 s~.

'" hI - hh

Qz '= Heat rejected "" Itz. - It]

= T2 (sl-.I'..J

IJRWiDe ~ I - Qz =1_

IJIUnliDo '" I - -

7i (sl-s ) Tml(sl" ,s )



where Tz is the temperature of heat rc:jection. The lowe:r is the: Tz for a given Tml , the higher will be the efficiency of the Rankine cycle. But the lowest practicable temerature of heat rejection is the temperature of the surroundings (TOJ. This being (ued,

The higher the mean temperature of heat addition, the higher will be the cycle efficiency. The effect of increasing the:.initial temperature al constant pressure on cycle efficiency is shown in Fig. 12.11. When the initial state changes from I to I', T",I between I and I' is higher than Tml between 45 and 1. So an increase in the superheat at constant pressure increases the mean temperature of heat addition and hence the cycle efficiency.


1 ..

fig. 12.11

Elful OjJ'IIpnludf 011 "",,, Umpn~lIIr. 0IAraf dlijtWn

- .

The maximum temperature of steam that can be used is fIXed from metallurgical considerations (Le.. the materials used for the manufactwe of the components which are subjected to high-pressure:, high.temperature: steam like the superheaters, valves, pipelines, inlet stages of turbine, etc.). When the maximum temperature: is fixed, as the operating steam pressure: at which heal is added in the boiler increases fromp] to Pz (Fig. 12.1 2), the mean temperature of heat addition increases, since Tall between 7s and 5 is higher than that between 45 and I. But when the turbine inlet pressure: increases trompt tOPl' the ideal cxpan-

sion line shifts to the left and the moisture content at the turbine exhaust increases If the moisture content of steam in the later stages of the (because .:c6s < tUrbine is hii/te r. th e entrained water panicles along with the vapour coming 01.11 from the nozzles with high velocity strike the blades and erode their surfaces, as a result of which the longevity of the blades decreases. From a considerntion of the erosion of blades in the laler stages of the twbine, the maximum moisture content at the turbine ellb.aust is not allowed to exceed 15%, or the quality to fall below 85'Yo. It is desirable that most of the turbine expansion should take place in the single phase or vapour region,


--J'H '-


Fig. 12.12 Effirl
~f itlfTttlSl

ofpr.,nr. O~ RaMiM qfit

Therefore, with the maximum stea m temperature al th e turbine inlet, the minimum temperarure of heat rejec1 ion, and the minimum quality of steam at the Iwbine exhaust being fixed, the maximum steam pressure at th e IUrbine inlet also gelS fixed (Fig. 12.13). The venicalline drawn from 2s; fixed by T2 and .:cl,' inlers~1S Ihe T...... Iine, fixed by material, at I, which gives the maximum steam pressure Ilt the rurbine inlet. The irre"ersibility in the expansion process has, however, not been considered.

Flg. 12.13

F~11f8 ~fUMIiJ/ 91111111], muimll'" Im.pmtllTr 11M

.uJ.ti"'WIll prrmrn i~

&dinr qc/r


12.6 Reheat Cycle

lfa steam pressure higher than (p,)..... (Fig. 12.13) is used, in order to limit the quality 10 0.8S at the turbine exhaust, reheat has to be adopted. In thatcase all the sleam after partial expansion in the turbine is brought back 10 the boiler, reheated by combustion gases and then fed hack to the turbine for further expansion. The flow, T-s, andh--s diagrams for the ideal Rankine cycle with reheat are shown in Fig. 12.14.ln the reheat cycle the expansion ofsteam from the initial state I to the condenser pressure is carried out in two or more SlepS, depending upon the number of reheats used. In the fltSt step, sleam expands in the high pressure (H.P.) turbine from the initial stale to approximately the !laturaled vapour line (process 1-29 in Fig. 12.14). The steam is then resuperheated (or reheated) at constant pressure in the boiler (process 15-3) and the remaining expansion (process 3-4s) is earried out in the low pressure (L.P.) turbine. In the ease ofuse of two reheats. steam is resuperhealed twice at two different constant pressures. To prot~ the reheater tubes, steam is not anowed to expand deep into the twophase region before it is taken for reheating, because in that case the moisture particles in steam while evaporating would leave behind solid deposits in the fann of scale which is difficult 10 remove. Also, a low reheat pressure may bring down T",\ and hence, cycle efficiency. Again, a high reheat pressure increases the moisture content at turbine exhaust. Thus, the reheat pressure is optimized. The optimum reheat pressure for most of the modem power plants is about 0.2 10 0 .25 of the initial steam pressure. For the cycle in Fig. 12.14, for I kg of steam
Q, Q2 " WI " W,, II,- II.+ II) -lIlJ

II, - 112, + III - h" II60 - II,

fl - Wr-Wp =(hl - ~.+h)-h )-(II60-hs)

Steam rate '"





3600 kg/kWh (h, -~, + h1-h,.)-(hw -115)

where enthalpy is in kJ/kg. Since higher pressures are used in a reheat cycle, pump work may be appreciable. Had the high pressure PI been used without reheat, the ideal Rankine cycle would have been 1- 4's-5-6.s. With the use of reheat, the area 15- 3-4s- 4's has been added to the basic cycle. It is obvious that net work output of the plant increases with reheat, because (h) -h.J is grealerthan (h lt - h; J, and hence the steam rate decreases. Whether the cycle efficiency improves with reheat depends upon whether the mean temperature of heat addition in process 2s--3 is higher than the mean temperature of heat addition in process 65-1. In prat:lice, the use of reheat only gives a marginal increase in cycle efficiency, but it increases the net work output by making possible the use of higher pressures, keeping the quality




1 ,

- - -,


- .

Fig. 12.1' JUlua/ C]CU



of steam at turbine eilhaust within a permissible limit. The quality improves from x4 ,. 10 X4. by the use of reheat. By increasing the number of reheats, still higher steam pressures could be used, but the mechanical stresses increase at a higher proportion than the increase in pressure, because of the prevailing high temperature. The cost and fabrication difficulties will also increase. In that way, the maximum steam pressure gets fIXed, and more than two reheats have not yet been used so far. In Fig. 12.14, only ideal processes have been considered. The irreversibililies in the expansion and compression processes have been considered in the example given later.

12.7 Ideal Regenerative Cycle

In order to increase the mean temperature of he at addition (Tml)' attention was so far confined to increasing the amount of heat supplied at high temperatures, such as increasing supemeat, using higher pressure and temperature of steam, and using reheat. The mean temperature of heat addition can also be increased by decreasing the amount of heal added at low temperatures. In a saturnted steam Rankine cycle (Fig. 12.15), a considerable pan of the total heat supplied is in dle liquid phase when heating up water from 4 to 4', at a temperature lower thaD TI the maximum temperature of the cycle. Formaximum efficiency, all heal should be supplied at TI , and feedwater should enter dle boiler at state 4'. This may be accomplished in what is known as an ideal regenerative cycle. the flow diagram of which is shown in Fig. 12.16 and dle cOlTesponding T- sdiagram in Fig. 12.17.

Fig. 12.15

Simpk Rti1li;illl C]cll


The unique feature of the ideal regenerative cycle is that the condensate, after leaving the pump circulates around dle turbine casing, counterflow to the direction of vapour flow in the turbine (Fig. 12.16). Thus, it is possible 10 transfer heat from dle vapour as it flows through the turbine to the liquid flowing around the turbine. Let us assume that this is a reversible heat transfer, i.e., at each point dle temperature of the vapour is only infinitesimally higher than the temperature of the liquid. The process 1-2' (Fig. 12.17) thus represents reversible expansion of steam in the turbine with reversible heat rejcction. For any small step in the process of heating the water,


i'rJWtr Cycln



Fig. 12.16 Idtal rtgtntrllli~t cydtbaJic uIImIt

Fig. 12.17 [dial "grrwatWt fJ,k (III T, plot


l!.T(water) '" - l!.T (steam) tJ.s (water) '"' - tJ.s (steam) Then the slopes of lines 1- 2' and 4'- 3 (Fig. 12.17) will be identical at every temperature and the lines will be identical in contour. Areas 4- 4' - b- a- 4 and 2' - 1- d -c-2' are not only equal but congruous. Therefore, all the heat added from an external source (Q1) is at the constant temperature TI and all the heat rejected (Q1) is at the constant temperature T2, both being reversible.

QI .. hI - h4 '" T1(sl -54) Q2 = hr - h) " T2(s2 - sJ) Since


Q, r, The efficiency of the ideal regenerative cycle is thus equal to the Carnot cycle efficiency. Writing the steady flow energy equation for the turbine hi - WT - hl' + h~ - h~. = 0 or WT " (hi - hl') - (h~. - h.) (12.17) The pump work remains the same as in the Rankine cycle, i.e. W, "' h4 -h l The net work output of the ideal regenerative cycle is lbus less, and hence its steam tate will be more, sllbough it is more efficient, when compared with the Rankine cycle. However, the cycle is not practicable for the folJowing reasons: (8) Reversible heat transfer cannot be obtained in finite time. (b) Heat exchanger in the turbine is mti.:hanically impracticable. (c) The moisture content of the steam in the turbine will be high.

" _ I _.2L =I_~

12.8 Regenerative Cycle

In the practical regenerative cycle. the feedwaterenttnl the boiler at a temperature between 4 and 4' (Fig. 12.17), and it is heated by Sleam extracted from intermediate stages of the turbine. The flow diagram of the regenerative cycle with saturated steam al the inlet to the turbine, and the corresponding T--j diagram are shown in Figs 1-2.18 and 12.19 respectively. For every kg of steam entering the rurbine, letml k,steam be extracted from an intermediate stage of the turbine where Ibe pressure (sP2t and il is used to heat up feedwater [(I - ml) kg at state 8] by mixing in heateo.1. The remaining ( I - ml) kg of sCeam then expands in the turbine from pressure P2 (state 2) to pressure Pl (state 3) when m2 kg of steam is extracted for heating feedwater in heater 2. So ( I - ml - m:z) kg ofsteam then expands in the remaining stages of the turbine to pressureP4' gets condensed inlo water in the condenser, and then pumped to heater 2, where it mixes withm2 kg of steam extracted at pressure Pl ' Then ( 1 - m l) kg ofwaler is pumped to heater 1 where it mixes withml kg ofsleam extracled at pressurePl ' The resulting 1 kg of steam is thenpumped to lhe boiler where heal from an external source is supplied. Heaters 1 and 2lhus operate al PressuresP2 andpl respectively. The amowlIs of steam ml and m2 extracted from the turbine are such lhal at the exit from each of the heaters, the stale is saturated liquid at the respective pressures. The heat and work transfer quantities oftbe cycle are WT I (hi - h 2) + (I - ml)(h1 - hl ) + (1 - ml (h )- h 4 ) kJ/kg (1 2. 18)


Wp W P I + Wn + Wn
- ( 1 - m l - mt) (h~- h, ) + ( I - ml)(h l - h7) + I (h lo - h9) kJlkg (12.19)


QI "" 1 (hi - h lo ) kJ/kg Q2" (l-ml - m~.(h. - hJ ) kJ/kg

Cycle: e:fficiency,
rj -

(12.20) (12.21)


3600 Stearn rate: kglkW h W T -Wp


In the: Rankine cycle operating at the: give:n pressures, PI and P4' the he:at addition would have bee:n from state: 6 to state: 1. By using two stage:s of rege:ntnltive: fc:edwater he:ating, fe:e:dwater enters the boiler at state: 10, i,nste:ad of state: 6, and heat addition is, the:refore, from state: 10 to state: I. The:refore.

hi - hlO (TlII,)..;th ...l .......ioa'" - - SI -siO

(12.22) (12.23)


(T.. ,)..;~ ..cmentiam " - - $1 - $6


Since: (Tml)wUb~>(Tm,)..;_ ....-.ati... the efficie:ncy of the: regene:rative: cycle: will be highe:r than that of the Rankine: cycle:. The e:ne:rgy balance: for heater 2 gives m l h 2 + ( I - ml)h s - Ih9







(l - m, - IIIz)Kg

. ./..



Heater.t l.


Fig. 12.18 Rlgmnl!liw 9th jllJw dil2f'/l!m with

lIDO jttdUJfJltr fualm



_ . ,.)
lon In work

FIg. 12.19

, "


m . 1I.j - ha

(4) Rq,mmllilll CJdt <'II T-, pUt witlr thf.rtasi"llll41l ~fflllid (6) Rq,mmlh'u 'Jd4 On T, unillll41l o[flu;J



The energy balance for heater I gives m1f! l+( I-m 1 -ml )h6"" (I-m 1)h 7
or ffll "'(1- ml) - hJ - h6


( 12.25)

From Eqs (12.24) and (12.25), ml aodml can be evaluated. Equations (12.24) and (12.25) can also be written alternatively as

(i - ml)(h9- h. ) =ml (h 2 - h9) mll (h7 - h6) "" ml (h) - h,) Energy gain of feedwater .. Energy given otT by vapour in condensation Heaters have been assumed to be adequately insulated, and there: is no heat gain from , or heat loss to. the surroundings.
(1 - m 1 -

"' "

Path 1-2-3-4 in Fig. 12.19 represents the states of a decreasing mass of. fluid. For 1 kg of steam, the states would be represented by the path 1- 2'- 3'- 4'. From equation (12.18),
"'T = (hi - h 2) + ( 1 - nit) (h2 - hl) + ( I - nil - nil) (h l - h~) .. (hi - hl) + (h:. - h)") + (h l - h~.) (12.26) (1 - IIII)(h 2 - h l ) ". 1 (h 1 - hl ,) (12.27)
( I -ml - ml)(hl - h~) - I (h3"' - h~,)



The cycle 1- 2- 2'- 3'- 3"- 4'- 5- 6-7-8- 9- 10- 1 represents I kg ofworkiDg fluid . The heat releasc::d by steam condensing from 2 to 2' utilized in healing up the water from 8 to 9.

Similarly I(h ). - hl") = l(h1 - h6) From equations (12 .26), (12.29) and (12.30)
"'T "' (h l - h4,) - (h l - h 2,) - hl' - hy-) .. (hi - h~,) - (h9 - h s) - (h7 - h6)


(12.3 \)

The similarity of equat ions (12. 17) and (12.31) can be not iced. It is seen that the stepped cycle 1- 2'- 3'- 4'- 5- 6- 7- 8- 9- 10 approximates the ideal regenera li ve cycle in Fig. 1 "2.17, and thai a greater number of stages would give a close r approximation (Fig. 12.20). Thus the heating offeedwater by steam 'blcd' from the turbine, known as regeneration, carnori=es the Rankine cycle.


The heat rejecledQ2 in the eycle decreases from (h 4 - h$) 10 (h~. - h, ). There is also loss in work output by the amount (Area under 2- 2' + Area under 3 '- 3"Area under 4-4'), as s hown by the hatched area in Fig. 12.19(b). So the sleam ~ rate increases by regeneration, i.e . more steam has to circulate per hour 10 produce unit shaft output. The enthalpy-entropy diagram ora regenerative cycle is s hown in Fig. 12.21.




"""" "'"'


~ 3" : 1M. 3'

{1 _1TII-_miI~

, , ,.



12.9 ReheatRegenerative Cycle

The reheating of steam is adopted when the vaporization pressure is high. The effect of reheat alone on the thermal efficiency of the cycle is very small. Regeneration or the heating up offeedwater by steam extrllcted from the turbine has a marked effect on cycle efficiency. A modem steam power plant is equipped with both. Figures 12.22 and 12.23 give the flow and T-s diagnuns of a steam plant with reheat and three stages offeedwater heating. Here

WT '" (hi - hi) + (1 - ml) (h 2 - " l) + (I - m l ) (h 4 - hs) + (I - m l - mi) (h) - "6) + (1 - m l - mz - mJ )(h6 - "7) kJ/kg Wp = (1 - m l - mz - ml) (h9 - ha) + (1- ml - ml) (hll - h lO ) + (I - ml) (h ll - hli) + l(h u - h 14) kJ/kg



Fig, 12.22
R.MlSf rtl'~"lSlio.


9ck fow JiqrlSlSI


VdpDlIT l'rIwn


- = 477

(I -m,)kg



1 , ""

(I - m, -IIIJ)kg (1- m, - 1112 - 17>3) ~g

""" """


Q2 = (l - ml - m2 - ml)(hJ - h, )kJlkg
The energy balances of heaters I, 2, and 3 give
m1hl + (I - ml)h u = 1 x h14 mlh, + ( I - ml - m2)h 11 '" (I - ml)h12 mlh, + ( 1- m 1- ml - m l)~ "' (I - m 1- ml)h 10

from which ml ' ml' and ml can be evaluated.

12.10 Feedwater Heaters

Feedwatcr heaters are of two types, viz . open heatersand closed heaters. In an open or contacl. rype healer, the extracted or bled steam is allowed to mix wi th feedwaler, and both leavc Ihc .hcalcr at II common tempcralure. lIS shown in Figs 12.18 and 12.22. In II closed beater, the fluids are kept separate, and not allowed to mix together (Fig. 12.24). The feedwatcr flows through the tubes in th e healer and the extracted sleam condenses on the outside of the tubes in the shell. The heat released by condensation is transferred to the feedwater through the walls of the tubes. The condensate (saturated water at the steam extraction pressure). sometimes called the heater.drip, then passes through a trap into the next lower prtssure hea ter. This, to some extent, reduces the steam required by that heater. The trap passes only liquid and no vapour. The drip from lhe lowest


(1- m,

-1n21 kg

pressure heater could similarly be trapped to the condenser, but this would be throwing away energy to the condenser cooling water. To avoid this waste, a drip pump feed the drip directly into the fcedwater stream. Figure 12.25 shows the T-s plot corresponding to the flow diagram in Fig. 12.24. The temperature of the feedwater (at '/' or 'Q') leaving a particular heater is always less than the saturation temperature at the steam extraction pressure (at e or g), the difference being known as the lerminO/lemperoture difference of the heater.

m'~11 ,/J,--'-=----'(I (1_ m,) kg


Fig. 12.25

T-j dJizgram


wilh da1tdft,dwalv h,alm


The advantages of the open heater are simplicity, lower cost, and high heat transfer capacity. The disadvantage is the necessity of a pump at each heater to handle the large feedwater stream. A dosed heater system requires only a single pump for the main ft:edwllter stream regardless of the number of heaters. The drip pump, if used. is reiliti vely small. Closed heaters are costly and may not give as high a feedwater temperature as do open heaters. In most 5team power plants, dosed heaters are favoured, but at least one open heater is used, primarily forthe purpose offccdwatcr deaeration. The open heater in such a system is called the deaero/Qr. The higher the number of heaters used, the higher will be the eyeJe efficiency. If n heaters are used, the greatest gain in efficiency occurs when the overall tempernlure rise is about nl(n + I ) times the difference between the condense r and boiler saturation temperatures. (SeeAnalysis o[Englneerlng Cycles by R.W. Haywood, Pergamon Press, 1973). If(4/)o '" l boil..... t - lcoed and (AI)",. "" temperature rise of reedwater il is seen that.

II" 0, II-I,
/I ..

(L\l)rw " 0

(AI)rw =

(A<)' }r
(AI)O }-

Gain " Gain "

"6 (Alk,



n .. 3.

(ru)rw '" 4 (L\l)fw "


n = 4.


Since the cycle efficiency is proportional to (L\l)fw the efficiency gain follows the law o[ diminishing return with the increase in the number of heaters. The greatest increment in efficiency occurs by the use of the first heater (Fig. 12.26). The increments for each additional heater thereafter successively diminish. The number of heaters is fixed up by the energy balance of the whole plant when it is found that the cost ofaddinganothcr doe s not justify the saving in Qt or the marginal increase in cycle efficiency. An increase in feedwalcr temperature may, in somc cases, cause a reduction in bo iler efficiency. So the number of healers gels optimized. Five points of extraction arc often used in practice. Some cycles use as many as nine.

IT (Alk,

Gain '"



'2.11 Exergy Analysis of Vapour Power Cycles

Let thc heating for steam generation in tbc boiler unit is provided by a stream of hot gases produced by burning of a fue l (Fig. 12.27). The distribution of input energy is shown in the Sankcy diagram 12.27 (b) which indicates that only about 30% orthe input energy to the simple ideal plant is converted 10 shaft work and about 60% is lost to the condenser. The exergy analysis, howevcr. gives a differenl distribution as discussed below. Assuming that the hot gases are at atmospheric pressure, the exergy input is


Number 01 heIIlM, n
~f umbrr oflIlalm Olt

FIg. 12.26 Effttt of1M !lSI




Input (0,)


- .....
(-10%) (b)

Eoerw lost with


Ag. 12.21 (..) T-s du.gram, (b) S4tWJ d.m, (r) G'4StIM1I di'Wdm

ofl =



[T: - To - To In ~] To



Similarly, the exergy iOs511lte with the exhaust stream is:



To[...!L -1-ln...!L] To 10

uf=w - I - In r.] 2'''' To[r. T o To



Net ellergy input!rate in the steam generation process:
all - afl - 0fl

The eJ.Crgy utilization rate in the steam generator is:

or" .. III. [(hi - h4 ) - To/:sl - 3'4)]

Rate of ellergy loss in the sleam generator:

l - o ~ - of"

The: useful mechanical power output:

.. W_ " w.[(h l

- h~

- (h 4 - h})

lterg)' flow rale of the wet steam to the condenser:

or. '" W , [(h l - h}) - TO(3'l - s])]

Second law efficiency,

'Ill - --: -:-~ " '~":-a rl


l Ellergy flow or Grassmann diagram is shown in Fig. 12.27 (c), The enttg:f fisposition diagram (b) shows thatlhe major energy loss (-60%) takes place in the condenser. This energy rejection. however, occurs at a temperature close to the ambient temperature, and, therefore, corresponds to a very [ow eltergy value (-4%). The major eltergy destruction due to irrever.libilities takes place in the stearn generation. To improve the performance of the stearn plant the finite SOUfCe temperatures must be closer to the working fluid temperatures to reduce thermal irreversibility.
. 12.12 Characteristics of an Ideal Working Fluid in

Vapour Power Cycles

There arc: certain drawbacks with steam as the working substance in a power cycle. The maximum tempernture thatcan be used in steam cycles consistent with the best available material is about 6OOoe. while the critical tempernture of steam is 37SoC. which necessitates largc superheating and permits the addition of only an infinitesimal amount orheat at the highest temperature. High moistUTe contcnt is involvcd in going 10 highcr.5tcam prCSllurc:s in order to obtain higher mean temperature ofhest addition (Tml)' The use of reheat is thus necessitated. Since rchcater tubes arc costly, the use of more tban two reheats is hardly recommended. Also, as pressure increases, the metal suesses increase, and the thicknesses of the walls of boile r drums, tubes, pi~ lines, etc., increase oot in proportion 10 pressure increase, but much faster, beca~ of the prevalence ofhigb temperature. t It may be noted that high T"' I is only desired for high cycle e fficiency . High pressures are only forced by the characteristics ( weak) of steam . If the lowe r limit is now considered, il is see n that at the heal rejection te mperature: of 4O oe, the saturation p~ure of steam is 0.075 bar, which is considerably lower than aunospheric pressure. The temperature o f heat rejection

can be stililowcred by using some refrigerant as a coolant in the condenser. The corresponding vacuum will be slill higher, and to maintain such low vacuum in the condenser is a big problem. It is the low temperature of heat rejection that is of real interest. The necessity ofa vacuum is a disagreeable characteristic ofstcam. The saturated vapour line in the T-s diagram ohteam is sufficiently inclined, so that when steam is expanded to lower pressures (for higher turbine output as well as cycle efficiency), it involves more moisture content, which is not desired from the consideration of the erosion of turbine blades in later stages. The desirable characteristics of the working fluid in a vapour power cycle to obtain best thennal efficiency are givcn below. (a) The fluid should have a high critical temperature so that the saturation pressure al thc maximum permissiblc temperature (mctallurgicallimil) is relatively low. It should bave a large enthalpy of evaporation at that pressure. (b) The saturotion pressure at the temperature of heat rejection should be above atmospheric pressure so lIS to avoid the necessity of mainlaining vacuum in the condenser. (c) The spedfie heat of liquid should be small so that lillie heat transfer is required to raise the liquid to the boiling point. (d) The saturated vapour line of the T-!J diagram should be steep. very dose to the turbine expansion process so that excessive moisture does not appear during expansion. (e) The freezing point of the fluid should be below room temperature, so that it does nOI get solidificd while flowing through the pipelines. (f) The fluid should be chemically stable and should not contaminate the materials ofconstruclion at any temperature. (g) The fluid should be nooloxic, noncorrosive, nOI excessively viscous, and low in cost. The characteristics of suc h an ideal fluid are approximated in the T-s diagram as shown in Fig. 12.28. Some superheat is desired to reduce piping losses and



1.8 bar

, -'5O"C

4O"C 3


improve turbine efficiency. The thermal efficiency of the cycle is very close to the Carnot efficiency.

12.13 Binary Vapour Cycles

Nosingle fluid can meet all the requirementsasmentioned above. Although in the overall eval uation, water is better than any other working fluid, however, in the high temperature range, there are a few better fluids, and notable among them are (a) diphe nyl ether, (C6H5hO, (b) aluminium bromide, AlzBrr.- and (c) mercury and other liquid metals like sodium or potassium. From among these, only mercury has actually been used in practice. Diphenyl ether could be considered, but it has not yet been used because, like most organic substances. it deeomposes gradually at high temperatures. Alum inium bromide isa poss ibility and yet to be considered. When p '" 12 bar, the saturation temperature for water. aluminium bromide, and mcrcW)' are 187e. 482.5e. and 560 0 e res~tive l y. Mercury is thus a better fluid in the higher temperature range, because at high tempernture, its vaporization pressure is relatively low. Its critical pressure and temperature are 1080 bar and 14600 e respectively. But in the low temperature runge, mercury is unsuitable, ~use its saturation pressure becomes exceedingly low and it would be impractical to maintain suc h a high vacuum in the condenser. At 30oe . the saturation pressure of mercury is only 2.7 x I O-~ cm Hg. Its specific volume at such a low pressure is very large, and it would be difficult to accommodate such a large volume flow . Forthis reason, mercW)' vapour leaving the mercW)' turbine is condensed at a higher temperature, and the heat released during the condensation ofmercW)' is utilized in evaporating water to form steam to operate on a conventional turbine. Thus in the binary (or two.fluid) cycle, two cycles with different working fluids are coupled in series, the heat rejectcd by one being utilized in the other. The flow diagram of mercury-steam binary cycle and the corresponding T-.t diagram arc given in Figs 12.29 and 12.30 resptttive ly. The mercury cycle, a- b-c-d, is a simple Rankine type of cycle using saturated vapo ur. Heat is supplied to the mercury in process d-a. The mercury expands in a turbine (process a-b) and is then condensed in processb-c. The feed pump process,c-d, completes the cycle. The heat rejected by mercury during condensation is transferred to boil water and form saturated vapour(proccss 5- 6). The saturated vapour is heated from the external source (furnace) in the superheater (process 6- 1). Superheated steam expands in the turbine (process 1 - 2) and is then condensed (process 2- 3). The feedwatcr (condensate) is then pumped (process 3- 4), heated till it is saturated liquid in the eeonomizer (process 4- 5) berore going to the mercury condcnsersteam boiler, where the latent heat is absorbed. In an actual plant the steam cycle is always a regenerative cycle. but for the sake of simplicity, this complication has been omitted. Let m represent the flow rate of the mercury in the mercW)' cycle per kg of steam circulating in the steam eycle. Then for I kg of steam


,.... "'"

...'" """

m., ...



"""" ""'"' ,

Men::ury boiler


Fig. 12.19

Mn'tlIry-SI'1I1f1 pllJa/ fow



, 2

Fig. 12.30 Mttcttry-/ltlllll hiM" o/'u

Ql .. m(h. - hd) + (hi - II,) + (h S - h4)

Ql ~ h2 -h3

WT = m(h. - lib) + (h1 - h 2)

w~ =


m(hd - ht) + (n4 - hl ) . _ ~= Wr "- Wp




and steam rate .,

3600 kglkWh W T - Wp The energy balance of the mercury condenser-steam boiler gives

m{h b -hJ .. h6 - h$

m _ lit, - h$ kg Hglkg H 0

" - h,
To vaporize one kg of water, seven to eight kg of mercury must condense. The addition of the mercury cycle to the steam cycle results in a marked increase in the mean temperature of heat addition to the plant as a whole and consequently the efficiency is increased. The maximum pressure is relatively low. It may be interesting to note that the concept of the binary vapour cycle evolved from the need ofimproving the efficiency of the reciprocating steam engine. When steam npands up to, say, atmospheric temperature, the resultant volume flow rate of steam becomes too large for the steam engine cylinder to accommodate. So most of the early steam engines arc found to be non-condensing. The binary cycle with steam in the high temperature and ammonia or sulphur dioltide in the low temperature range, was first suggested by Professor Josse of Germany in the middle of the nineteenth century. Steam exhausted from the engine at a relatively higher pressure and temperature was used to evaporate ammonia or sulphur dioxide which operated on another cycle. But with the progress in steam turbine design, such a cycle was found to be of not much utility, since modem turbines can cope efficiently with a large volume flow of steam. The mercury-steam cycle has been in actual commercial use for more than three decades. One such plant is the Schiller Station in the USA. But it has never attained wide acceptance because there has always been the possibility of improving steam cycles by increasing pressure and temperature, and by using reheat and regeneration. Over the above, mercury is expensive, limited in supply, and highly toxic. The mercury-steam cycle represents the two-fluid cyclcs. The mercury cycle is called the topping cycle and the steam cycle is called the bottoming eye/e. If a sulphur dioxide cycle is added to it in the low temperature range, so that the heat released during the condensation of steam is utilized in fonning sulphur dioxide vapour which expands in another rurbine, then lite mercury-stearn-sulphur dioxide cycle is a three-fluid or teniary cycle. Similarly, other liquid metals, apart from mercury, like sodium or potassium, may be considered fora working fluid in the topping cycle. Apart from 502 other refrigerants (ammonia, freons, etc.) may be considered as working fluids for the bottoming cycle. Since the possibilities of improving steam cycles are diminishing, and the incenlives to reduce fuel cost are \'ery much increasing, coupled cycles, like the mercury-steam cycle, may receive more favourable consideration in the near



Ba.sir ,,1IIi Applied ThmnodJMmi&s

12.14 Thermodynamics of Coupled Cycles

If two cycles are coupled in series where healioSI byone is absorbed by the other (Fig. 12.31), as in Ihe mercury-sleam binary cycle, lei IJI and 'h be the efficiencies of the topping and bottom cycles respectively, and IJ be the overall efficiency of the combined cycle.

1)1 " 1m,


and I)z " 1_ QJ




'---~ +--'-V' ;:' 0,





Fig. 12.31



']cla C1JNpkd ill min



Q1 >= QI(I - IJI) and QJ

Q, Q,

Q1(l - 'h)


IJ '"' I - QJ ",, 1_'1(I - l"h )


- 1- G(I - 111 )(1- 11l)

- 1 - (I - IJI)(I - IJ2>
If there aren cycles coupled in series, the overall efficiency would be given by

1) - I - n(l - lJi)



IJ "" 1 - (1 - 1)1) (I - '12) (I - 1)1)'" (I - IJQ) 1 - 1) '"' (1-1J1)(1-1)2)(1-1J1) ... (1 -'1.). Total loss '" Product oflosses in all the cycles.
For two cycles coupled in series

'1 .. I - ( 1- '11)(1 - '12) " ] - ( 1- '11- 'h + '11'1Z) '" '11 + '12- '11'11

'1 - ~+~ - '11~

This shows that the overnll effici'ency of two cycles coupled in series equals the sum of the individual efficiencies minus their product.


Bycombining two cycles in series. even ifindividual efficiencies are low, it is possible 10 have a fairly high combined efficiency, which cannot be attained by a single cycle. Forexample, if III '" 0.50 and 112 .. 0.40 Il '" 0.5 + 0.4 - 0.5 x 0.4 '" 0.70 It is almost impossible 10 achieve such a high efficiency in a single cycle.

12.15 Process Heat and By-Product Power

There are several industries, such as paper mills. textile mills, chemical factories, dying plants, rubber manufacltuing plants. sugar factories, etc" where saturated steam at the desired temperature is required for heating, drying, elc. Forconslant temperature heating (or drying), steam is a very good medium, since isothennal condition can be maintained by allowing saturated steam to condense at that temperalure and utilizing the latent heat released for heating purposes. Apan from the process heat, the factory also needs power to drive various machines, for lighling. and for other purposes. Fonnerly il was the practice 10 generale steam for power purposes al a moderate pressure and 10 generate separately saturated sleam for process work at a pressure which gave the desired heating lemperarure. Having two separale units for process heat and power is wasteful, forofthe total heal supplied 10 the steam for power purposes. a grealer pan will nonnaJly be carried away by Ihe cooling water in the condenser. By modifying the inilial steam pressure and exhaust pressure, it is possible to generate the required power and make available for process work the required quanti ty of exhaust sleam al the desired temperature. In Fig. 12.32, the exhaust steam from the turbine is utilized forptocess heating, the process heater replacing the condenser of the ordinary Rankine cycle. The pressure at exhaust from the

Fig, 12..32 &ck prts.S1!/rt lI"biIU

"' "

... =-

- .
turbine is the

pressure corresponding 10 the temperature desired in the

process healer. Such a turbine is called abockpressure turbine. A plant producing both power and process heat is sometimes known as a cogeneration plant,

When the process steam is the basic need, and the power is produced incidentally
as a by-product, the cycle is sometimes called a by-product power cycle. Figure 12.33 shows the T- s plot ofsuch a cycle, lfWT is the turoine ou:put in kW, QH the process heat required in kJlh, and IV is the steam flow rate in kglh WT x 3600 .. w(hl - h~ >I~h2 - II) .. QII
WT )( 3600

~ ~(hl-hl)
h2 -~

T x3600x(h1 -h) Q .. W II hi-liz

Of the total energy input Qt (as heat) to the by-product cycle, WT part of it only is Invened into shaft work: (or electricity). The remaining energy (QI - WT)' which would otherwise have been a waste, as in the Rankine cycle (by

the Second Law), is utilized as process heat.

Fraction of energy (Ql) utilized in the form of work (WT), and process heat (QH) in a by-product power cyclc

.. WT+~I
Condenser loss, which is the biggest loss in asteam plant, is here zero, and the fraction of energy utilized is very high. In many cases the power available from the back pressure turbine through which the whol e of the heating steam nows is appreciably less than that required in the factory. This may be due 10 relatively high back pressure, or small heating requirement, or both. Pass-oul/urbines are employed in these cases. where a certain quantity of steam is continuously e xtracted for heating purposes at the desired temperature and pressure. (Figs 12.34 and 12.35).



w(h l

hi) kJlh

Qz = (w- wlXh l - h4 ) kJlh QH = wl(h1 - h,J kJlh WT - w(h l - hV + (w - wI) (h l .- h3) kJlh Wp - (w - wI) (h s - h.) + w l(h 7 - h6) kJlh
WI h7 + (w - WI)h S - wx hI where W is the boiler capacity(kg/h) and wI is the steam flow rate required (kglb) at the desired temperature for process healing.


Efficiencies in Steam Power Plant

For the steady flow operation ofa turbine, neglecting changes in K.E. and P.E. (Figs 12.36 and 12.37). w!ki/ h)




healer -

Fig. 12.:14


Muimwn or ideal work QUtl"ll per unil mass of steam

(WT)mu - (WT)i<kal " h i - hI. = Revertjible and adiabatic enthalpy drop in turbine

This work is, however, not obtainable, since no real process is reversible. The expansion process is accompanied by irreversibililies. The acrual final state 2 can be defined, since the temperature, pressure, and quality can be found by actual measurement. The acrual path 1- 2 is nOI known and its nature is inunalerial, since the work output is here being expressed in lenus of the change of a property,




enthalpy. Accordingly, the work done by the turbine in irreversible adiabatic expansion from I to 2 is (WT)......I .. hi - h2
Steam (W. kgIh)

Sleam exhau.t

fig. 12.36

Ef/kimciu ill/l stram lu,bi/U



fig. 12.37 /NlnMi tJ/ititrll] ~f(I. Sitdm IM,bilU This work is known asinrema/work, since only the irreversibilities within the flow passages of turbine are affecting the state of steam at the turbine exhaust.

v,poU'I'owt1 C,fla


Internal output '"' Ideal output - Friction and other losses within the turbine casing If",. is the steam flow rate in kg!h Internal output '" w.(h 1- hl ) kJ/h Ideal output - "'. (hI - hb) kJ/h The internal efficiency ofttubine is defined as '1illlcmol Internal output Ideal output

hi -


Work output availab le at the shaft is less than the [ntema.! output because of the external losses in the bearings, etc. :. Brake output or shaft output "" Internal output - Extemallosses - Ideal output - Internal and External losses - (kW x 3600 kJ/h) The brake efficiency of turbine is defined as '11...b Brake output

Ideal output kW x 3600

The mechanicul efficiency of turbine is defined as

..... -

Brake output

Intcma1 output kWx 3600



'1o.m '" '1;'-..1 X '1-=h While the internal efficiency takes into consideration the inlemallosses, and the mechanical efficiency considers only the citernallosses. the brake efficiency takes into account both the internal and extemallosscs (with respect to turbine casing). The generator (or alternll/ar) e fficiency is defined as

IJ....-.. -

_ Output al generator tenninals Brake output of turbine

The efficiency of the boiler is dermed as

",, "=liZ"d~ '1boil = CEC"":'="',,-, r or Energy supplied

IV, xC. v.

where wlis the fue l burning rate in the boiler(kglh) and C.V. is the calorific value of the fuel (kJlkg). i.e., the heal energy released by the complete combustion of unit mass offuel.




, ,
~ lal )1



Tds - dh-vdp - O
IV...... '"' -

, , J vdp'"'-- Jdh=h l -"2 , ,

From steam tables,

hi'" (h. )I1... '" 2675.5 kJ/kg SI - (S. )II., - 7.3594 kJ/kg K " S2 For p "" 10 bar " I MPa and s., 7.3594 kJ/kg K, by interpolation

h2 "" 3195.5 kJlkg Wrev " 2675.5 - 3195 .5

= -

520 kJlkg

It is thus observed thai compressing steam in vapour form would require over 500 times more work than compressing it in liquid fonn for tho same pressure rise. E:umple 12.2 Steam at 20 bar, 360C is ell:panded in a steam turbine to 0.08 bar. It then enters a condenser, where it is condensed to saturated liquid water. The pwnp feeds back the water into the boiler. (a) Assuming ideal processes, find per kg of sleam the net work and the cycle efficiency. (b) If the turbine and the pump have each 80% efficiency, rwd the percentage reductinn in the nel work and

cycle efficiency.
Solution The property values at different state points (Fig. Ell:. 12.2) found from the stearn tables are given below.
h l ""3159.3kJlkg sl=6.9917kJlkgK hl '" "fpl '" 173.88 kJ/kg Sl " Sfpl - 0.5926 kJllr.g K hrlPl = 2403.1 kl/kg slPl - 8.2287 U/kg K vfp, '"' 0.001008 mllkg : . .~~ .. 7.6361 kJlkg K Now SI ,. Sb

6.9917 - sfP2 +x21 SflPl - 0.5926 + x2'7.6361


""' C



.. 0.08 bar



Fig. Ex. 12.2

x "" 6.3991 1. 7.6361





h'J>l + xlsh'lPl - 173.88 + 0.838 x 2403 .1 = 2187.68kJ/kg


Wp" h.. - hJ = vfi>1 (p! - P2) = 0.001008-

m ' x 19.92 x 100-:::T kN


.. 2.008 kJ/kg h4 - 175.89 kJ/kg Wr .. h! - h2 - 3159.3 - 2187.68 .. 97 1.62 kJ/kg W... " Wr - Wp '"' 969.61 kJ/kg Q! .. hI 3159.3 - 175.89 - 2983.4 1 kJ/kg



W.... _ 96961 - 0325 , or 325" '1<)'<!.--------. . ,.


(b) If

'lp " 80%. and '1r" 80%


W = 2.008 = 2.51 kJ/kg



Wr " 0.8 x 971.62 - 777.3 kJ/kg W..., " Wr - Wp "' 774.8kJ/kg :. % Reduction in work output

h ,.

., 969.6 1-774.8 x 100 "'20.1% 969.61 = 173.88 + 2.51 = 176.39 kJ/kg Q! = 3159.3 - 176.39 = 2982.9 1 kIlkg



2~;~:: I

.. 0.2597, or 25.97%

:. % Reduction in cycle efficiency 0.325-0.2597 x 100 "' 20.1% 0.325 A cyclic steam power plant is 10 be designed for a sleam temperarure at turbine inlet of360~C and an oxhaust pressure of 0.08 bar. After isentropic expansion of steam in the turbine, the moisture conlent al the turbine exhaust is nOI to exceed 15%. Detennine the greatest allowable steam pressure at the turbine inlet, and calculate the Rankine cycle efficiency for these steam conditions. Estimate also the mean temperarure of heat addition. Solution As state 2s (Fig. Ex. 12.3), the quality and pressure are known.

Example 12.3


i .,,
Sls .. -',+ X2, S'I
Sl "'S2.



Fig. EL 12.3


'x20 O.8S

= 0.5926 + 0.85 (8.2287 - 0.5926) '"' 7.0g33 kJlkg K


sl - 7.0833 klfkg K

At state I, the temperature and en tropy are thus knOv.1l. At 360~C,sl " 5.0526 kJ/kg K. which is less than St. So from tbe table of superhcated s team, at t\ ... 360C and -'I ... 7.0833 kJ/kg K, the pressure is fOWld to be 16.832 bar (by interpolation). :. The greatest allowable steam pressure is

p, ... 16.832 bar

h, ... 3165.54 kJ/kg
hl<" 173.88 + 0.85 x 2403.1 - 2216.52 kJ/kg h3 '" 173 .88 kJ/kg


h - h3 ... 0.001 x (16.83 -0.08) x 100 - 1.675 kJlkg

h '" 175.56 kJ/kg Q, '" h, - II - 3165.54- 175.56 >= 2990 kJ/kg



=1fT '" hi - ht. - 3165.54 IV, .. 1.675 kJ/kg

2216.52 .. 949 kJJkg


1'JC')~I6 '" W... = 247.32 QI 2990

Mean temperature of heat addition

.... 0.3168or3168%

Tml "" hi-h., =

" I - " 40


7.0833 0.5926 '" 460.66 K '" 187.5l c C.

Example 12.4

A steam power station uses the following cycle: Steam at boiler outlet- 150 bar, 550C Reheat at 40 bar to 550 cC Condenser at 0.1 bar. Using the Mollier chart and assuming ideal processes, find the (a) quality at turbine exhaust, (b) cycle efficiency, and (c) steam rate.

Solution The property values at different states (Fig. Ex. 12.4) are read from the Mollier ehart.

p," ISObar



.<" ,.,.e

- -

,., ..
Fig. EL 12.4


h ., '" 2300 kJ/kgx... '" 0.88, hs(steam table) '" 191.83 kJ/kg
Quality at turbine exhaust .. 0.88

hi '" 3465, ht. '" 3065, hl '" 3565,

Ans. (a)

W, ... v lJ.p D- W- l x ISO x 102 - IS kJ/kg h60 .. 206.83 kJikg



(hi -ht..> + (h)-h2')

+ (3565 - 3065) - 3758. 17 kJ/kg WT .. (hi - h2J + (h, - h.,) .. (3465 - 3065) + (3565 - 2300) = 1665 kJ/kg
.. (3465 - 206.83)



W.... .. WT - Wp " 1665 - 15 .. 1650 kJ/kg

1Jcy<Ie "

W. 16SO ~ = 3758.17 = 0 4390, or 43.9"10

Ans. (b) Ans. (c)

Steam rate ..


.. 2.18 kglkW h

Example 12.5 Ina single-heater regenerative cycle the steam enters the turbine at 30 bar, 400C and the ellhaust pressure is 0.10 bar. The feedwater heater is a dirttt-contact type which operates at 5 bar. Find (a) the efficiency and the steam rate of the cycle and (b) the increase in mean temperature of heat addition, efficiency and steam rate, as compared 10 the Rankine cycle (without regen eration). Neglect pump work.

Solution Figure Ex. 12.5 gives the flow, T-s, andh-sdiagrams. From the steam tables, the property values al various states have been obtained.
h( .. 3230.9 k1/kg
3Obar",OO' C