Professional Documents
Culture Documents
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.
Page 1
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.
Page
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
TH
TL
Equation(2)
Q
or
TH
0(2)
TL
shows thatthesumofthequantities
QH and QL
TH
TL
,associatedwith
Page
absorptionandrejectionofheatbythefluidofareversibleheatengineiszeroforthe
Page
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
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
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
,proved.
T500
250
T
Example2.Eisthesystemwhichexecutesacyclicprocess.
500K
However,ifEwereareversibleengine,then
work
W would have been,
1000kJ
W
E
W
600kJ
1000(500250) 500
kJ
500
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
,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
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,
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
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
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
x4.184ln
293
273
293
2.958x103kJ/K
II
b)
i.e.entropychangeofwaterat0 C.tobecomeiceat0 C
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.
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
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)
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
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)
556 278
,Since
0irreversible
Case(ii)
278 139 0
,
T
Case(iii)
556 278
Since
0reversible
0impossible
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
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
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.