Entropy, Availability and Irreversibility

Chapter05&06

ENTROPY,AVAILABILITYANDIRREVERSIBILITY
ThefirstlawofthermodynamicsintroducestheconceptoftheinternalenergyU,andthistermhelpsus
tounderstandthenatureofenergy,asdefinedbythefirstlaw.Inthesimilarwaythesecondlaw
introducestheconceptofentropyS,likeinternalenergyitisalsoathermodynamicpropertyandis
definedonlyintermsofmathematicaloperations.
GeneralDiscussion:
Forasystemundergoingaquasistaticprocess,workdoneattheboundaryisgivenby,

WPdV(1)

Sinceareversibleprocessisaquasistaticprocessthisrelationgivestheworkdoneattheboundaryofa
systemduringareversibleprocess.
Consideringareversiblecycleinwhichonlyworkinvolvedisdoneattheboundaryofthesystem,we
have

Q W PdV (2)
Formtheequation(2),Workisgivenbythecyclicintegralofproductoftwopropertiesviz.Pisan
intensiveproperty&dVischangeinanextensiveproperty.
Forareversiblecyclewhenwork(whichisapathfunction)isdefinedbytheproductof
twopropertiesoneisintensiveandtheotherischangeinanextensiveproperty,whycant Heat (which
isalsoapathfunction)isdefinedbythecyclicintegralofproductof
twopropertiesoneintensiveandtheotherchangeinanextensiveproperty.
Yes,theintensivepropertymostcloselyassociatedwithheatistemperatureandtheother
extensivepropertyforthisanswerisENTROPY.TotalentropyisdenotedbycapitalletterSandlower
case s represents the specific entropy, i.e. entropy / unit mass.
Ifentropyisanextensivepropertythenwhatexactlyisentropy?
Entropyis
1. TheamountofEnergythatisnotavailableforworkduringacertainprocess
2. Ameasureofthedisorderofasystem.
3. Measureofdisorganizationordegradationintheuniversethatreducesavailableenergy,or
tendencyofavailableenergytodwindle.Chaos,oppositeoforder.
4. Thestateofdisorderinathermodynamicsystem:themoreenergythehighertheentropy.
5. Ameasureofthedispersalordegradationofenergy.

Ravichandra Koti,Asst Prof.MED,SVIT Bangalore-64

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Entropy, Availability and Irreversibility

6.A measure of the disorder or randomness in a closed system. For example, the
entropyofanunburnedpieceofwoodanditssurroundingsislowerthantheentropyof
theashes,burntremains,andwarmedsurroundingsduetoburningthatpieceofwood.
7.The scientific measure of the disorder in a system; the greater the disorder, the
greatertheentropy.
8.ThethermodynamicentropyS,oftensimplycalledtheentropyinthecontextof
thermodynamics, is a measure of the amount of energy in a physical system that
cannotbeusedtodowork.Itisalsoameasureofthedisorderpresentinasystem.The
SIunitofentropyisJK1(jouleperKelvin),whichisthesameunitasheatcapacity.
9."Entropy" is defined as a measure of unusable energy within a closed or isolated
system (the universe for example). As usable energy decreases and unusable energy
increases,"entropy"increases.Entropyisalsoagaugeofrandomnessorchaoswithina
closedsystem.Asusableenergyisirretrievablylost,disorganization,randomnessand
chaosincrease.

Understandingentropy:
Example1.
One of the ideas
involved in the
concept of entropy is
thatnaturetendsfrom
order to disorder in
isolated systems. This
tells us that the right
handboxofmolecules
happened before the
left. Using Newton's
laws to describe the
motion of the
molecules would not
tell you which came
first.

Ravichandra Koti,Asst Prof.MED,SVIT Bangalore-64

Page

Entropy, Availability and Irreversibility

ForaglassofwaterthenumberofExample2.moleculesis
astronomical.Thejumbleoficechipsmaylookmoredisorderedincomparisonto
theglassofwaterwhichlooksuniformandhomogeneous.Buttheicechipsplace
limitsonthenumber of ways the moleculescan be arranged. The water
moleculesintheglassofwatercanbearrangedinmanymoreways;they
havegreater"multiplicity"andtherefore

Greaterentropy.

Solidshavelesserentropythanliquids.Statistically,insolidstheatomsormoleculesare
intheirfixedplaces,whereasinliquidsandevenmoreingasesyouneverknowexactly
wheretofindthem.Thefixedsequenceofatomsinsolidsreflectsahigherorderedstate.
Considerabodywhichisheatedandanotheroneiscooled.Whathappenstotheentropy
ofthetwobodies?Entropyincreasesonheating.Doesdisorderincrease,too?
Yes,itdoes.Weknowthatheatisstoredinapieceofmatterastherandommotionof
particles.Thehotterabody,themoreitsatomsandmoleculesjigglearound.Itisnot
difficulttoidentifydisorderbyfasterjigglingmotion.

CLAUSIUSTHEOREM:
ThethermalefficiencyofreversibleCarnotcycleisgivenbytheexpression,

Carnot

1 QL 1 TL or QH QL (1)

TT

H L

WhereTH andTL arethetemperaturesofhightemperaturethermalreservoirandlow

temperaturethermalreservoirrespectively,andQHistheheatsuppliedandQListheheat
rejectedbytheCarnotengine.
Consideringtheusualsignconvention,+vefortheheatabsorbedand vefortheheat
rejected,wemaywrite,

TH

TL

Equation(2)

Q
or

TH

0(2)

TL

shows thatthesumofthequantities

QH and QL
TH
TL

Ravichandra Koti,Asst Prof.MED,SVIT Bangalore-64

,associatedwith
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Entropy, Availability and Irreversibility

absorptionandrejectionofheatbythefluidofareversibleheatengineiszeroforthe

Ravichandra Koti,Asst Prof.MED,SVIT Bangalore-64

Page

Entropy, Availability and Irreversibility

Entirecycle.Sincetheworkingfluidreturnstoitsinitialstateattheendofthecycle,it

QH

and L
TH TL represents property
changesoftheworkingfluidbecausetheirsumiszeroforthecycleandthisisthecharacteristicofaproperty
orstatefunction.Theamountofheattransferisknowntodependonthepathoftheprocess.Howeverifthe
heatisdividedbythetemperatureatwhichthetransfertakesplace,theresultisindependentonthepath.
undergoesnonetchangeinproperties,suggestingthatthequantities

TheaboveconclusionisfortheCarnotreversiblecycle.Butitcanbeprovedthattheconclusionisvalidfor
anyreversiblecycle.
Consideranyarbitraryreversiblecycleabcdaasshown.Insuchcycleabsorptionandrejectionofheatdo
notoccurattwoconstanttemperaturesbuttakeplaceatcontinuouslychangingtemperatures.

m
Pressure e

a
g

d h

Volume
The cycle can be now broken into an infinite number elementary Carnot cycle by drawing a series of
infinitelycloseadiabaticlines,eh,fg,mn,etc.efgh,fmngetcrepresentselementaryCarnotcycleinwhich
sectionsef,ghetccanbeconsideredasisothermallines.
ForanydifferentialCarnotcycle,efgh,letQH1betheheatabsorbedduringisothermalprocessefandQ L1be
theheatrejectedduringtheisothermalprocessgh.ThetemperatureofefisT H1andghprocessisTL1.Then
wemaywrite,

H1

H1

Q
L1
T

L1

Usingpropersignconvention+vefortheabsorptionofheatandveforrejection,weget,

QH 1

QL1

H1

0(1)

L1

Ravichandra Koti,Asst Prof.MED,SVIT Bangalore-64

Page 5

Similarly,

Q
T

H2

H2

L2

0(2)forthecyclefmng

L2

Fromtheserelationsweseethatthealgebraicsumoftheratiosoftheamountsof
heattransferredtotheabsolutetemperaturefortheCarnotcyclestakentogetheris
equaltozero,thus,
Q

H1

i.e.

L1

L1

QH

H1

Q H2

QL

H2

Q L2

L2

0(3)

TL

AsthenumberofCarnotcyclesisverylarge,thesumoftheterms overthecomplete

cyclebecomesequaltothecyclicintegralof

,Wemay,thereforewrite
T

R 0(4)
T

WhereRrepresentsreversiblecycle.ThisresultisknownasCLAUSIUSTHEOREM.
isknownasENTROPY.
Q
T
ENTROPY:
Definition:Entropy,SisapropertyofsystemsuchthatitsincreaseS2S1asthesystem
changesfromstate1tostate2isgivenby,

2 Q
R
S2 S1 T
(1)
1

Indifferentialformequation(1)canbewrittenas dS

QR
T

THECLAUSIUSINEQUALITY:
Whenanysystemundergoesacyclicprocess,theintegralaroundthecycleof

thanorequaltozero.

Q
Insymbols,

0(1)

isless
T

WhereQisaninfinitesimalheattransfer,Tisabsolutetemperatureofthepartof
thesystemtowhichheattransferQoccurs.
PROOF:
ForanyreversiblecyclefromClausiustheorem,

R 0(2)
T

From the Carnots theorem we know that theefficiencyofanirreversibleengineisless

thanthatofareversibleengine,i.e.

IR

Where

isefficiencyoftheirreversibleengineandRisefficiencyofthereversible

engine.

Hence,1

(3)

H I
H R
WhereIandRrepresentsirreversibleandreversibleprocessesrespectively.
Forareversibleengine,theratiooftheheatabsorbedandheatrejectedisequalto
theratiooftheabsolutetemperatures.Therefore

Q L
TL

Q L TL

H I

or

L I

(4)

TH

i.e.

i.e.

TH

QH

(5)

Usingsignconventionsof+veforabsorptionofheatand vefortherejectionof
heat,weget,

Q H Q L
0(6)

T T
L I
HI
Fromthisweseethatthealgebraicsumoftheratiosoftheamountsofheattransferred
totheabsolutetemperatureforacyclicirreversibleprocessisalwayslessthanzero,

I 0(7)
T

0 (8)

Combiningequations(2)and(7),weget
T
ThisisknownasCLAUSIUSINEQUALITY.
CLAUSIUSINEQUALITYishelpfulindeterminingwhethertheprocessisreversible
ornot.

Q
0

If

and

Q 0

,thecycleisreversible,

,thecycleisirreversibleandpossible

Q0
T

,thecycleisimpossiblesinceitviolatesthesecondlawofthermodynamics.

ILLUSTRATIONOFCLAUSIUSINEQUALITY:
Example1.ConsidertheflowofheatfromthereservoirattempT1tothatatT2across
theconductorasshown.Conductoristhesystem.Inthesteadystatethereisnochangein
thestateofthesystem.

Q1

T1

Q2

AClausius
inequality

T2

LetQ1=1000kJ,T1=500K,T2=250K
SinceQ1=1000kJ,Q2=1000kJ

Q0

Q 1000 1000 2.5kJ/K,Hence

,proved.

T500
250
T
Example2.Eisthesystemwhichexecutesacyclicprocess.

Q 1000 600 0.4kJ/K

T
500 250

500K

However,ifEwereareversibleengine,then
work
W would have been,

1000kJ

W
E

W
600kJ

1000(500250) 500
kJ
500

Q 1000 1000500 0kJ/K

Hence
250K

and

500

250

TQ 0proved

Example3.

Aheatenginereceivesreversibly420kJ/cycleofheatfromasourceat327 C,and
0
rejectsheatreversiblytoasinkat27 C.Therearenootherheattransfers.Foreachofthe
threehypotheticalamountsofheatrejected,in(a),(b)and(c)below,computethecyclic
Integralof

.Fromtheseresultsshowwhichcaseisirreversible,whichreversibleand
T
Whichimpossible.(a)210kJ/cyclerejected(b)105kJ/cyclerejectedand(c)315kJ/
cyclerejected.

Case(a)

Q 420 210 0
600 300

Q 420 105

Case(b)

Case(c)

0.35

0,Impossible

,Since

600 300

600 300

0,reversible

,Since

Q 420 315 0.35

,Since

0,irreversible

ENTROPYISAPROPERTY:
Proofthatentropyisaproperty:
Statement:Foranysystemundergoinginternallyreversiblecycle,theintegralof

QR iszero,insymbols, QR 0(1)
T
T

Letthesystemexecutesacyclicprocess,startingatstate1,proceedingtostate2along
thereversiblepathA,andreturningstate1alongadifferentpathB.
ReversiblePathA
2
Y

ReversiblePathB
1
X

0(2)

T
Sincetheprocessisreversible,wemayreverseitandthuscausethesystemtoretraceits
R

FromtheClausiusinequalitywehavealongpath1A2B1,

pathprecisely.Lettheelementofheattransfercorrespondingtothesystemboundaryat
temperatureTbeQR,forthisreversedprocess.

Q ' R
0 (3)
Thenwehavealongpath1B2A1,
T
But,sincethesecondcycleissimplethefirstonewiththedirectionreversed,wehave,

QR'QR(4)
Therefore,statement(3)becomes;alongpath1B2A1,

or

QR 0(6)

0(5)

Comparingstatements(2)and(6)weseethattheycanbebothtruesimultaneouslyonly

if,

QR 0(7)

,henceEntropyisaproperty.

QR

Statement:Theintegralof

,whenasystemexecutesanyreversibleprocess

betweenfixedendstates,isindependentofthepathoftheprocess.
Insymbols,forarbitrarypathsAandB,

QR

12A T

Q R
1 B T

ReversiblePathA
2
Y
ReversiblePathB
ReversiblePathC
1

X
Considerasystemwhichexecutesareversiblecyclicprocess,from1alongpathAto
2,andbackalongpathCto1.Thenwehave,

AC

Q
Q
Q R
2
1

T R 1A T R 2C T 0 (1)

Similarly,forthereversiblecyclicprocess1B2C1,wecanwrite,

BC

Q
T

1
Q
Q
R
R
R
1B T 2C T 0 (2)

Fromequations(1)and(2)weget,i.e.(1)(2)gives,
2

Q R

1A

i.e.

Q R

2C

12A Q R

2
1 B

QR
T

1B

1Q R 0 (2)

2C

(3)

12 TQR

PathAandpathBarearbitraryand

hasthesamevalueforanyreversible

pathbetween(1)and(2),hencefromthedefinitionofentropywemaywrite(S 2S1)
hasthesamevalueforanyreversiblepathbetween1and2.ThereforeENTROPYisa
property.
CALCULATIONOFENTROPYCHANGEFORDIFFERENTPROCESS
EntropychangeinIRREVERSIBLEprocess:
Foraprocess thatoccurs irreversibly,thechangeinentropyisgreaterthantheheat
changedividedbytheabsolutetemperature.Insymbols,
Q
dS T

Proof:
IrreversiblePathA
2
P

ReversiblePathB
1

V
Consideranarbitraryirreversiblecycle1A2B1asshowninfigure.Thepath1to2(1
A2)istraversedirreversiblyandthepath2to1(2B1)reversibly.FromtheClausius
Inequality,wehave

0,forthecyclewhichisirreversibleand

0,forthecyclewhichisreversible

T
Since

the

entropy

is

thermodynamic

dS

2
1 A

dS

1
2 B

dS

0 (2)

(1)
property, we

can

write

21B

Forareversibleprocesswehave,

dS

1
2B

QR
(3)
T

Substitutingthisinequation(2),weget

Q R
T 0(4)

2
1
1 AdSI 2 B

Usingequation(1),foranirreversiblecycle,

1A

0(5)

2B

Nowsubtractingequation(5)fromequation(4),weget

dSI

1A

1A

For small

dS Q
I

(6)

changes in

states

theaboveexpressioncanbewrittenas,

(7)

WherethesubscriptIrepresentstheirreversibleprocess.Theequation(7)statesthatin
anirreversibleprocessthechangeinentropyisgreaterthan

dS
I

Q
T

Q
T

.Thereforewecanwrite,

,whereequalitysignisforreversibleprocessandinequalitysignisfor

irreversibleprocess.
IMPORTANT: The effect of irreversibility is always to increase the entropy of the
system.Ifanisolatedsystemisconsidered,fromthefirstlawofthermodynamicsthe
internalenergyofthesystemwillremainconstant.Q0,fromtheaboveexpression

dS Isolated 0 , i.e., the entropy of an isolated system either increases or remains

constant.Thisisacorollaryofthesecondlawofthermodynamicsandthisexplainsthe
principleofincreaseinentropy.
MATHEMATICALEXPRESSIONOFTHESECONDLAW:

QTdSforreversibleprocessesandQTdSforirreversibleprocesses

Theaboveequationmayberegardedastheanalyticalexpressionofthesecondlawof
thermodynamics.

ENTROPYCHANGESFORANOPENSYSTEM:
Inanopensystemtheentropyisincreasedbecausethemassthatcrossestheboundaryof
thesystemhasentropy.Thusforanopensystem,wemaywrite,

dS

misimese(1)

T
Where,miand me arethemassesenteringandleavingthesystem&si,se arethe
entropies.
Asthemassmi entersthesystem,theentropyisincreasedbyanamount
misi,
similarlyasthemass meleavesthesystem,theentropydecreasesbyanamount
mese
Insteadyflowprocessthereisnochangeinthemassofthesystemandmimem.
Wecanwrite,therefore

m(sesi )

(2)

s s

e
i(since
Q0)i.e.inasteadyflow
Forsteadyflowadiabaticprocess
adiabaticprocesstheentropyofthefluidleavingmustbeequaltoorgreaterthanthe
entropyofthefluidcomingin.
Sincetheequalitysignholdsforareversibleprocess,weconcludethatforareversible
steadyflowadiabaticprocess,

sesi(3)
IMPORTANTRELATIONSFORAPURESUBSTANCEINVOLVINGENTROPY

PURESUBSTANCE:
A pure substance has a homogeneous and invariable chemical composition even
thoughthereoccursaphasechange.
Thefirstlawforaclosedsystemisgivenby,

QdEW(1)
Intheabsenceofchangesinkineticandpotentialenergiestheequation(1)canbewritten
as

QdUW(2)

Forareversibleprocess

QTdS

Thereforeequation(2)becomes

TdSdUW(3)
Theworkdoneattheboundaryofasystemduringareversibleprocessisgivenby

WPdV(4)
Substitutingthisinequation(3),weget

TdSdUPdV(5)
Fromequation(5)werealizethatitinvolvesonlychangesinpropertiesandinvolvesno
pathfunctions.Thereforeweconcludethatthisequationisvalidforallprocesses,both
reversibleandirreversibleandthatitappliestothesubstanceundergoingachangeof
stateas theresultofflow across theboundaryoftheopensystemaswellas tothe
substancecomprisesaclosedsystem.
Intermsofperunitmasstheequation(5)canbewrittenas

TdsduPdv(6)
dUdHPV

dHPdVVdP(sinceH=U+PV)

Since

TdSdHPdVVdPPdVdHVdP
Therefore

TdSdHPdVVdPPdVdHVdP

i.e.TdSdHVdP
Intermsofunitmass,

or

TdsdhvdP
ds dhvdP (7)
T

PRINCIPLEOFTHEINCREASEOFENTROPY:
EntropyChangefortheSystem+Surroundings
Consider the process shown. Let Q istheheattransferfromasystemattemperature T to
thesurroundingsattemperatureT0,andWistheworkofthisprocess(either+veorve
).Usingtheprincipleofincreaseinentropy

System
Temperature=T

Q
Surroundings
Temperature=T0

dS

system

dS

Q
T (1)

surroundings

(2)

forareversibleprocess
Thetotalchangeofentropyforthecombined
system

dS

dS

system

surroundings

Q Q

T0
1

T
ordS

system dS

surroundings Q

T0

Thesameconclusioncanbehadforanopensystem,becausethechangeintheentropyof
thesystemwouldbe

dSopensystem

Q
T

misimese

Thechangeintheentropyofthesurroundingswouldbe,

dSsurroundings

T0

misimese

dSsystemdSsurroundings
Therefore,

that

1
T

ordS

1
T0

system dS

Q Q

T T0

surroundings Q

0 andtherefore

dS

system

dS

1
T

1 sinceTT0anditfollows

surroundings

Thismeansthatprocessesinvolvinganinteractionofasystemanditssurroundingswill
takeplaceonlyifthenetentropychangeisgreaterthanzeroorinthelimitremains
constant. The entropy attains its maximum value when the system reaches a stable
equilibriumstatefromanonequilibriumstate.
ENTROPYFORANIDEALGAS:
Lettheidealgasundergoesachangeofstatefromstate1tostate2.LetT 1,V1and
T2,V2bethetemperaturesandvolumesatstate1and2respectively.

TdSdUPdV(1)
Wehave,

ordS dU PdV
T
T
m
Since,dUmcvdTand P R
T V
d
dT
dSmc
mR V therefore
v
T
V
T2

S2S1mcv
1

dT

V2

mR
1

wheremisthemassandRisthegasconstant,weget

dV
V

dT

T2

V2
mRln (2)
V
1

Ifcv=constant,then
T2
V2
S2S1mcvln T1 mRln V1 (3)

Similarly,wehave

TdSdHVdP
ordS dH V dP(4)

TT
m
V R

Since,dHmc p dT &
T
P
T2

dT

mcp

Therefore,S2S1
1

weget,dSmc

p2

mRcv

dP
P m

dT mR dP
T
dT

T2

P
P2

T mRln P (5)
1

T2
P2
Ifcp=constant,thenS2S1mcp ln T1 mRln P1 (6)

Forgeneralcase(process),changeofentropyisgivenby,

S2 S1mcvln T1 mRln V1 mcp ln T1 mRln P1 (7)

orinspecificvalues,
s sc ln T2 Rln v2 c ln T2 Rln P2 (8)
2 1
v
p
T1
v1
T1
P1
SPECIALCASES:
a)Constanttemperatureprocess(Isothermalprocess),T=Constant
S S mRln
2

V2

mRln

V1

P2

orinspecificvaluess 2 s Rln

P1

b)Constantvolumeprocess,V=Constant

S S
2

m
or inspecificvalues
T
s c ln T2
ln 2 s
c
2 1
1
v
v
T1
T1

c)Constantpressureprocess,P=Constant
or in specific values
T
2
s c ln T2
S S mc ln
s
p
2
1
p
21
T1
T1
d)Reversibleadiabaticprocessorisentropicprocess,S=Constant
Changeinentropyiszero,S2S10orS2 S1
e) Polytropicprocess

S 2 S1 cv

n
ln
T2
n1T1

v2
v1

Rln

P2
P1

Problemsonentropy:
ProblemNo.1.Onekgofwaterat273Kisbroughtintocontactwithaheatreservoirat
373K.Whenthewaterhasreached373K,findtheentropychangeofwater,theheat
reservoirandoftheuniverse.
Solution:LetT1 bethetemperatureofwater,T2 bethetemperatureofheatreservoir.
Sincereservoirisathighertemperaturethanthatofwater,whenwaterisbroughtinto
contactwiththereservoirheattransferoccursfromreservoirtowaterandtakesplace
through a finite temperature difference (irreversible). The entropy of water would
increaseandthatofreservoirdecreasesothatnetentropychangeofthewaterandthe
reservoirtogetherwouldbe+vedefinite.Tofindtheentropychangeofwaterwehaveto
assumeareversiblepathbetweenendstates,whichareatequilibrium.
1)

Heatreservoir
T2=373K

Entropyofwater

mc

water
T

dT
T

T2
mcpln T
1

373
1x4.187ln 273 1.3068kJ/K

System(water)
T1=273K
2)Thetemperatureofthereservoirremainssameirrespectiveoftheamountofthe
heatwithdrawn.
Amountofheatabsorbedbythesystemfromthereservoir,
QmcpT2T11x4,187373273418.7kJ
Therefore,Entropychangeofreservoir,

reservoir

T2 373

418.7

1.1225kJ/K(vesignindicatesdecreaseinentropy)

3)Entropychangeoftheuniverse
SuniverseSwaterSreservoir1.30681.12250.1843kJ/K

ProblemNo.2.Twokgofairisheatedfrom27 Cto427 Cwhilethepressurechanges

from100kPato600kPa.Calculatethechangeofentropy.R=0.257kJ/kgK,C p =
1.005kJ/kgK.
Solution:Given:
m=2kg
T1=27+273=300KT2=427+273=700K

P1=100kPa
P2=600kPa

Thegeneralequationusedforthecalculationofchangeofentropyisgivenby,
S

air

ln

S2S1mcp

T2
T1

mRln

0.7821kJ/K

P2 700

2x1.005ln

P1

600

2x0.257ln

300

100

ProblemNo.3.Tengramsofwaterat20 Cisconvertedintoiceat10 Catconstant

atmosphericpressure.Assumingspecificheatofliquidwatertoremainconstantat4.184
0
J/g Candthatoficetobehalfofthisvalue,andtakingthelatentheatoffusionoficeat
0
0 Ctobe335J/g,calculatethetotalentropychangeofthesystem.
Solution:Given:
m=10gm

WaterisavailableattemperatureT 1 =20
0
C=293k
0

Cp(water)=4.184J/g C

Cp(ice)=x4.184J/g C=x4.184
0

kJ/kg C

=4.184kJ/kg C

SIII

IceistobeformedattemperatureT 4=10 C
=263K

SII

Totalentropychangeofwater(system)asitisconvertedintoicewillbe

STotalSISIISIII(1)
S
a)

i.e.entropychangeofthesystemasitiscooledfrom20 Cto0 C.

I
273

dT

273 10

SI mcp T mcpln 293 1000

x4.184ln

293

273
293

2.958x103kJ/K

II

b)

i.e.entropychangeofwaterat0 C.tobecomeiceat0 C

SII mQL 10 x 335 0.0123kJ/K

1000
273
T

III

c)

SIII
263

273

i.e.entropychangeoficeasitiscooledfrom0 Cto10 C

mc

p(ice)

dT mc

ln 263 10

p(ice)

273

4.184

1000 x

263
ln

273

7.807x104kJ/K
Thereforetotalentropychangeofwaterasitisconvertedintoicewillbe

Total

SISIISIII2.958x103(0.0123)(7.807x104)
0.01604kJ/K

ProblemNo.4.Areversibleengineasshowninfigureduringacycleofoperationdraws
5MJfromthe400Kreservoiranddoes840kJofwork.Findtheamountanddirectionof
heatinteractionwithotherreservoirs.

300K
200K
400K

Q2

Q3

Q1=5MJ
E
W=840kJ

Solution:
LetusassumethatQ2andQ3aretheheatrejectedbytheenginetothereservoirat300K
and200Krespectively.

FromtheClausiustheoremwehave T
Andalso,Q1WQ2Q3

Q Q Q
0i.e. T T T 0(1)
1

(2)

Considerequation(1),Q15MJ,

T1 400K,T2 300K,T3200K

Usingvesignforheatrejectedintheequation,wehave

5x106

0,
2

400 300
Q2
Q3
200
i.e.12500
200 0
300
2Q23Q312500x6007500000(3)
3

andequation(2)gives,Q2Q3 5x106840x1034160000(4)
Solvingequations(3)and(4),weget

Q30.82MJandQ24.98MJ
Thereforethedirectionofheatinteractionwiththereservoirsareasfollows

300K
200K

400K
Q2=4.98MJ
Q3=0.82MJ

Q1=5MJ
E
W=840kJ
0

ProblemNo.5.Twokgofwaterat80
Caremixedadiabaticallywith3kgofwaterat30
0
Cinaconstantpressureprocessof1atmosphere.Findtheincreaseintheentropyofthe
totalmassofwaterduetomixingprocess.Cpofwater=4.187kJ/kgK.
Solution:
Subsystem1
0

2kgofwaterat80 C
Subsystem2
0
3kgofwaterat30 C
Andt1t2

Lettfbetheequilibriumtemperatureofthemixtureoftwosubsystems
i.e.Subsystem1+Subsystem2andthefinaltemperature tfissuchthatt2 tf t1.
Sinceenergyinteractionisexclusivelyconfinedtothetwofluids,thesystembeing
isolated.

m1cp1t1tf m2cp2tf t2therefore

m c t m c t
t
1 p1 1 2 p2 2
sinceCp1=Cp2,tfwillbegivenby
f

mc

1 p1

m2cp2

m1t1m2t2

m1m2

(2x80)(3x30)

500C

(23)

Entropychangeforthefluidsubsystem1,

Tf
323
dT
T m1cpln T 2x4.187ln 353

Tf

S1m1cp
1

0.7437kJ/K

ThiswillbenegativesinceTfT1
Entropychangeforthefluidsubsystem2,
T

f
323
dT
T m2cpln T 3x4.187ln 303

S2m2cp
T

0.8028kJ/K

Increaseintheentropyofthetotalmassofwaterduetomixing

SS1S20.74370.80280.0591kJ/K
SinceSis+vedefinite,themixingprocessisirreversible.
0

Problem No.6. A steel tool of mass 0.5 kg at a temperature of 350 C is plunged

0
suddenlyintoaninsulatedvesselcontaining10kgofoilatatemperatureof20 C.After
atimethetemperatureofthecontentsofthevesselbecomesuniform.Assumingtheheat
transfertotheatmospheretobezero,andthatnoneoftheoilevaporates;evaluatethe
increaseinentropyofthefinalcontentsofthevessel.TakeC pofoil=1.88kJ/KgKand
Cpofsteel=0.48kJ/KgK
Solution:Given
Steel
0

ts=350 C
ms=0.5kg

Csteel=0.48kJ/KgK

Oil
0

toil=20 C
moil=10kg
Coil=1.88kJ/KgK

Wetakethesteelandtheoilasoursystem.Applyingtheprincipleofconservationof
energyforthisprocess,weget
QWUKEPE(1)

WhereQ0,W0,KE0,PE0
ThereforeUsteelUoil0(2)
Let tf bethefinaltemperatureofthecontentsofthevessel.Wehavefortheenergy
balance

mc

s steel

tf

t t m
s

mc

t m c t

mc

m c

s steel s

tftotherefore

oil oil

0
(0.50.48350)(101.8820) 24.16 C

oil oil 0

oil oil

s steel

Now,entropychangeforsteelis,

Tf

steel

mc

dT
T

s steel

(0.50.48)(101.88)

m c

s steel

ln

(24.16273)

Ts 0.5 0.48ln (350273)

0.178kJ/K
And,entropychangeforoilis
Tf

S m c
oil
T

oil oil

dT m c

oil oil

(24.16273)

ln f 101.88ln
To
(20273)

0.26504kJ/K
Thereforechangeinentropyofthefinalcontentsofthevessel,

SSsteelSoil0.1780.265040.08704kJ/K
ProblemNo.7.Calculatetheentropychangeoftheuniverseasaresultofthefollowing
processes
0

1. Acopperblockofmass0.6kgandspecificheat150J/kgKat100
Cisplacedin
0
alakeat8 C.
0
0
2. Twosuchblocksat100 Cand0 Carejoinedtogether.
Solution:
Given:

Casei) m0.6kg,
T100 0C373K,
c

Cc150J/kgK0.150kJ/kgK,
T80C281K
l

universe

Copperblock

Lake

Whenhotcopperblockisputintolake,theblockshallcooldowntothelaketemperature
sincelakeisbigandtreatedassink.

i)S

Copperblock

mC

T
L

ln
T

ln 281

0.6 0.150

0.0255kJ/K

373

HeatlostbyCopperBlockHeatgainedbylake
mCc(TCTL)
0.60.150(373281)8.28kJ

Lake

8.28

0.0295kJ/K
281

ThereforeSuniverse

Caseii) m0.6kg, c1
T 100 0C373K, T
Let

Lake

0.02550.02950.004kJ/K

c1

Copperblock

c2

Cc2150J/kgK0.150kJ/kgK,
00C273K

Tmbetheequilibriumtemperatureofthetwocopperblockswhenthey

communicate.i.e.Copperblock1+Copperblock2andthefinaltemperatureTmis

suchthatTc2 Tm Tc1.Sinceenergyinteractionisexclusivelyconfinedtothetwo
blocks,thesystembeingisolated.

Tc2therefore

mcc1Tc1Tmmcc2Tm

T
m

mc T mc T
c1 c1

c2 c2

mcc1 mcc2

373 273 323

K
2

Tm
mc dT mc ln T 0.60.150ln 323
c1
IBlock

c1 T
T
373
m

c1

c1

0.01295kJ/K
T

mc
IIBlock

323
dT
T
T mcc2 ln T 0.60.150ln 273
m

c2

c2

c2

0.01514kJ/K

Therefore S

universe

Iblock

IIblock

0.012950.015140.00219kJ/K
ProblemNo.8. Aheatengineissuppliedwith278kJ/sofheatataconstantfixed
0
0
temperatureof283 Candtheheatrejectionstakeplaceat5 C.Thefollowingresults
werereported.
i)208kJ/sofheatrejected.ii)139kJ/sofheatrejected.iii)70kJ/sofheatrejected.
Classifywhichoftheresultsreportareversiblecycle,irreversiblecycleorimpossible
cycle.
Solution:

Case(i)

Q 278 208 0.2482

T

556 278

,Since

0irreversible

Case(ii)

278 139 0
,

T
Case(iii)

556 278

Since

0reversible

278 70 0.2482 ,Since

556 278

0impossible

ProblemNo.9. 0.5kgoficeblockat10 Cisbroughtintocontactwith5kgcopper

0
blockat80 Cinaninsulatedcontainer.Determinethechangeinentropyofi)iceblock
ii)copperblockiii)theuniverse.
Givenspecificheatofice=2kJ/kgK,Specificheatofwater=4.2kJ/kgK,Specific
0
heatofcopper=0.5kJ/kgK,enthalpyoffusionofwaterat0 C=334kJ/kg.
ProblemNo.10.Aninventorreportsthatshehasarefrigerationcompressorthatreceives
0
0
saturated Freon12 vapor at 20 C and delivers the vapor at 1 MPa, 50 C. The
compressionprocessisadiabatic.Doestheprocessdescribedviolatethesecondlaw?
Solution:

State1.ConditionofFreon12atinlettocompressorsaturatedvaporat200C
State2.ConditionofFreon12attheexitofcompressor 1MPaand50 C
ReferringtheFreon12tablesweget,atstate1,s1=0.7082kJ/kgKandatstate
2,s2=0.7021kJ/kgK
Forasteadystate,steadyflow,adiabaticprocesswecanwritesecondlawas,s2s1,
butforthegivenadiabaticprocess,s1>s2thereforetheprocessinvolveaviolationofthe
secondlawandwouldnotbepossible.
0
0
ProblemNo.11.Onekgoficeat5 Cisexposedtotheatmospherewhichisat20 C.
Theicemeltsandcomesintothermalequilibriumwiththeatmosphere.i)Determinethe
entropyincreaseoftheuniverse.

Heatabsorbedbyicefromtheatmosphereisgivenby,

Q12.093(0(5))1333.314.187(200)
427.5kJ
Entropychangeoftheatmosphere

S
a)

atmosphere

SI

427.5

T 293

1.46kJ/K
0

,entropychangeofthesystem(ice)asitisheatedfrom5 Cto0 C.

d
273
273
T
SI mcp T mcpln 268 12.093ln 268
273

268

0.0389kJ/K

b)

SII

,entropychangeofthesystem(ice)asitmeltsat0 Ctobecomewaterat

0 C.

333.3

SII

273

1.22 kJ / K

c) III
293

S
III

273

,entropychangeofwater asitisheatedfrom0 Cto20 C

293
293
dT
mcp T mcpln 273 14.187ln 273

0.296kJ/K

Thereforetotalentropychangeoficeasitmeltsintowaterwillbe

STotalSISIISIII0.03891.220.296
1.5594kJ/K
Thereforeentropychangeofuniversewillbe,

SuniverseSsystemSatmosphere1.55941.460.0949kJ/K

ProblemNo.12. A5kgcopperblockatatemperatureof200 Cisdroppedintoan

0
insulatedtankcontaining100kgofoilatatemperatureof30 C.Findtheincreasein
entropyoftheuniverseduetothisprocesswhencopperblockandtheoilreachthermal
equilibrium.Assumethatthespecificheatsofcopperandoilarerespectively0.4kJ/Kg
Kand2.1kJ/KgK.
Solution:Given
Copperblock
0
tc=200 C
mc=5kg
Ccopperblock=0.4kJ/KgK

Oil
0
toil=30 C
moil=100kg
Coil=2.1kJ/KgK

We take the copper block and the oil as our system. Applying the principle of
conservationofenergyforthisprocess,weget
QWUKEPE(1)
WhereQ0,W0,KE0,PE0
ThereforeUcopperblockUoil0(2)
Let tm bethefinaltemperatureofthecontents ofthetank.Wehavefortheenergy
balance

mc

c copperblock

t m c

oil oil

t m c t

mc

c copperblock c

tf

tmtotherefore

oil oil 0

m c

mc

(50.4200)(1002.130) 31.6 0C

oil oil

c copperblock

Now,entropychangeforcopperblockis,

dT

mm c

copperblock

(50.4)(1002.1)

c copperblock

Tm
m c

ln

c copperblock

(31.6273)

Tc 50.4ln (200273)

0.8802kJ/K
Now,entropychangeforoilis
T

Soilmmoilcoil
T

(31.6273)

m
dT moilcoilln
T 1002.1ln
o
(30273)
T

1.106kJ/K
Thereforechangeinentropyofthefinalcontentsofthevessel,

SScopperblockSoil0.88021.1060.2258kJ/K

PROPERTYDIAGRAMSWITHENTROPYASACOORDINATE:

Reversible
Adiabatic

s
T
Irreversible

Adiabatic

s
Thisdiagramisusefultoanalyzethenatureofthethermodynamicsystemstovisualize
the changes of state that occurs in various processes. This diagram possesses the
followingfeatures.
1. Areaonthediagramhavethedimensionsofheat
2. Inthemixedphaseregion,theconstantpressurelinesarehorizontal
3. Inareversibleprocesstheareaunderthecurveisequaltotheheattransferinthe
correspondingprocess
4. Verticallinesrepresentsisentropicprocesses
5. Inareversiblecycle,theareaenclosedbythecurverepresentingtheprocessis
equaltothenetheattransfertothefluidandso,fromthefirstlawisalsoequalto
thenetwork.
IfthesubstanceexecutesaCarnotcycle,itspathontheTsdiagramisarectangle.

TH
b

Processes:
Processab:IsentropicProcess
Processbc:IsothermalProcess
Processcd:IsentropicProcess
Processda:IsothermalProcess

TL
s

EfficiencyoftheCarnotengineisgivenby,

th

T (s s )TL(s2 s1)
Areaabcda H 2 1

TH(s2s1)
Areafbcef

TL
TH

T
1

TH

Anirreversibleprocessisrepresentedbyalinetendingtotheright,forthisentropy
alwaysincreases.
THEENTHALPYENTROPY(hs)diagramorMOLLIERdiagram

Intheenthalpyentropydiagramthepressureandtemperaturelinesnaturallycoincidein
thetwophaseregion.
Entropypostulations:
1. Theentropycontentofanisolatedsystemcanneverdecrease.
2. Theentropyofanysubstanceapproaches aconstantvalueas itstemperature
approachesabsolutezero.
3. Foraperfectcrystallinesubstance,itsentropyiszeroattheabsolutezeroof
temperature.
ThenatureofEntropy:
1.Entropyisaprimitiveconcept
2. Everysystemhasentropy
3. Entropyisanextensiveproperty
4. Entropyisthatitisanindexofthatportionofenergycontentinasystemthatis
notavailabletodowork

5. Entropycontentofanisolatedsystemisnotconserve

AvailableandUnavailableenergy
Wehave,
HighGradeEnergy
1MechanicalWork
2ElectricalEnergy
3Waterpower
4Windpower
5KineticEnergyofajet
6Tidalpower

LowGradeEnergy
1HeatorThermalenergy
2 Heat derived from nuclear fission or
fusion
3Heatderivedfromcombustionoffossil
fuels

Thecompleteconversionoflowgradeenergy,heatintohighgradeenergy,shaftworkis
impossible.
Thatpartofthelowgradeenergywhichisavailableforconversioniscalledasavailable
nd
energy,whilethepartwhich,accordingtothe2 lawofthermodynamics,mustbe
rejectedisknownasunavailableenergy.
If a cyclic heat engine is considered, the maximum work output obtainable from a
certainheatinputiscalledtheavailableenergy(A.E.),ortheavailablepartoftheenergy
supplied.Theminimumenergythathastoberejectedtothesinkistheunavailable
energy(U.E.).
Therefore,
Q1A.E.U.E.orWmaxQ1U.E.(1)
Forareversiblecycle,

rev1 2(2)
T1
For a given temperature T1, rev will increase with the decrease of T2. The lowest
practicabletemperatureofheatrejectionisthetemperatureofthesurroundings,T0.

T0

Therefore,rev1

T1

AndWmax 1 0 Q1(3)
T1

ConsiderafiniteprocessXY,heatissuppliedreversiblytoaheatengine.Takingan
elementarycycle,ifQ1istheheatreceivedbytheenginereversiblyatT1,then

max

T1T0
T

QQ
11

T0
T

QA.E.
1

FortheheatenginereceivingheatforthewholeprocessXY,andrejectingheatatT0

max

Q
1

X1

WmaxA.E.QXYT0sYsX
or U.E.QXYWmaxi.eU.E.T0sYsX.

TheU.E.isthustheproductofthelowesttemperatureofheatrejection,andthechange
ofentropyofthesystemduringtheprocessofsupplyingheat.