Entropy

Thesecondlawleadstothedefinitionofanewpropertycalledentropy.

TheClausiusInequality
Thefirstlawissimplyanenergybalance.However,thesecondlawleadstoaninequality;
an irreversible process is less efficient than a reversible process. Another important
inequalityinthermodynamicsistheClausiusinequality:

Q
T

Thatis,thecyclicintegralofQ/Tisalwayslessthanorequaltozero.Thisisvalidforall
cycles,reversibleorirreversible.
Forinternallyreversiblecycles,itcanbeshownthat:

Q
T

0
int, rev

Entropy
TheClausiusinequalityformsthebasisforthedefinitionofanewpropertycalledentropy.
As can be seen in the equation above, for an internally reversible process the cyclic
integralofQ/Tiszero.Aquantitywhosecyclicintegraliszerodependsonthestateonly
andnottheprocesspath,andthusitisaproperty.
Clausiusin1865realizedthathediscoveredanewpropertyandhecalleditentropy:
Q
dS

T int,rev

(kJ/K)

Entropyperunitmassisdesignatedbys(kJ/kg.K).
Theentropychangeofasystemduringaprocesscanbecalculated:
Q
S S 2 S1

T int, rev
1
2

(kJ/K)

To perform this integral, one needs to know the relation between Q and T during the
process.
Note that the cyclic integral of Q / T will give us the entropy change only if the
integrationcarriedoutalonganinternallyreversiblepathbetweentwostates.
Forirreversibleprocesses,wemayimagineareversibleprocessbetweenthetwostates
(initialandfinal)andcalculatetheentropychange(sinceentropyisaproperty).

M.BahramiENSC388(F09)Entropy1

TheIncreaseofEntropyPrinciple
Entropy change of a closed system during an irreversible process is greater that the
integralofQ/Tevaluatedfortheprocess.Inthelimitingcaseofareversibleprocess,
theybecomeequal.

dS

Q
T

Theentropygeneratedduringaprocessiscalledentropygeneration,andisdenotedby
Sgen,
2

S S 2 S1

S gen

Note that the entropy generation Sgen is always a positive quantity or zero (reversible
process).Itsvaluedependsontheprocess,thusitisnotapropertyofasystem.
The entropy of an isolated system during a process always increases, or in the limiting
caseofareversibleprocessremainsconstant(itnever decreases). This isknownasthe
increaseofentropyprinciple.
The entropy change of a system or its surroundings can be negative; but entropy
generationcannot.
S gen

0
0

irreversible process
reversible process
impossible process

1 A process must proceeds in the direction that complies with the increase of entropy
principle,Sgen>0.Aprocessthatviolatesthisprincipleisimpossible.
2Entropyisanonconservedproperty,andthereisnosuchthingastheconservationof
entropy.Therefore,theentropyofuniverseiscontinuouslyincreasing.
3Theperformanceofengineeringsystemsisdegradedbythepresenceofirreversibility.
The entropy generation is a measure of the magnitudes of the irreversibilities present
duringtheprocess.

EntropyBalance
Entropyisameasureofmoleculardisorderorrandomnessofasystem,andthesecond
lawstatesthatentropycanbecreatedbutitcannotbedestroyed.
Theincreaseofentropyprincipleisexpressedas
Entropychange=Entropytransfer+Entropygeneration

S system S transfer S gen

Thisiscalledtheentropybalance.
M.BahramiENSC388(F09)Entropy2

EntropyChange
Theentropybalanceiseasiertoapplythatenergybalance,sinceunlikeenergy(whichhas
manyformssuchasheatandwork)entropyhasonlyoneform.Theentropychangefora
systemduringaprocessis:
Entropychange=EntropyatfinalstateEntropyatinitialstate

S system S final S initial

Therefore, the entropy change of a system is zero if the state of the system does not
change during the process. For example entropy change of steady flow devices such as
nozzles, compressors, turbines, pumps, and heat exchangers is zero during steady
operation.

MechanismsofEntropyTransfer
Entropycanbetransferredtoorfromasystemintwoforms:heattransferandmassflow.
Thus,theentropytransferforanadiabaticclosedsystemiszero.
HeatTransfer:heatisaformofdisorganizedenergyandsomedisorganization(entropy)
willflowwithheat.Heatrejectionistheonlywaythattheentropyofafixedmasscanbe
decreased. The ratio of the heat transfer Q/ T (absolute temperature) at a location is
calledentropyfloworentropytransfer
Entropy transfer with heat (T const.)

S heat

SinceT(inKelvin)isalwayspositive,thedirectionofentropytransferisthesameofthe
directionofheattransfer.
Whentwosystemsareincontact,theentropytransferfromwarmersystemisequalto
the entropy transfer to the colder system since the boundary has no thickness and
occupiesnovolume.
Notethatworkisentropyfree,andnoentropyistransferredwithwork.
MassFlow:masscontainsentropyaswellasenergy,bothentropyandenergycontentsof
asystemareproportionaltothemass.Whenamassintheamountofmentersorleaves
asystem,entropyintheamountofms(sisthespecificentropy)accompaniesit.

EntropyBalanceforaClosedSystem
Aclosedsystemincludesnomassflowacrossitsboundaries,andtheentropychangeis
simplythedifferencebetweentheinitialandfinalentropiesofthesystem.
Theentropychangeofaclosedsystemisduetotheentropytransferaccompanyingheat
transferandtheentropygenerationwithinthesystemboundaries:
Entropychangeofthesystem=Entropytransferwithheat+Entropygeneration

M.BahramiENSC388(F09)Entropy3

S 2 S1

Qk
S gen
Tk

Therefore,foranadiabaticclosedsystem,wehave:
Sadiabatic=Sgen
ForaninternallyreversibleadiabaticprocessS=0,becauseSgen=0.
Thetotalentropygeneratedduringaprocesscanbedeterminedbyapplyingtheentropy
balance to an extended system that includes both the system and its immediate
surroundingswhereexternalirreversibilitymightbeoccurring.
Example1:Entropybalanceforaclosedsystem
Saturated liquid water at 100 C is contained in a pistoncylinder assembly. The water
undergoesaprocesstothecorrespondingsaturatedvaporstate,duringwhichthepiston
movesfreelyinthecylinder.Thereisnoheattransferwiththesurroundings.Ifthechange
ofstateisbroughtaboutbytheactionofapaddlewheel,determinethenetworkperunit
mass,inkJ/kg,andtheamountofentropyproducedperunitmass,inkJ/kg.K.

Insulated
Water

Paddlewheel

Assumptions:
1Thewaterinthepistoncylinderassemblyisaclosedsystem.
2Thereisnoheattransferwiththesurroundings.
3Thesystemisatanequilibriumstateinitiallyandfinally.PE=KE=0.

Solution
Thenetworkcanbecalculatedbyusingthelaw:
U+KE+PE=QW
Thatissimplifiesto:U=W
M.BahramiENSC388(F09)Entropy4

Onaunitmassbasis,theenergybalancebecomes:
W/m=(uguf)
FromTableA4,
W/m=2087.6kJ/kg
The negative sign indicates that the work input by the stirring is greater than the work
donebythewaterasitexpands.
Usinganentropybalance,theamountofentropyproducedcanbefound.Sincethereis
noheattransfer,
Q
S
S gen S gen
T

Onaunitmassbasis,thisbecomes:
Sgen/m=sgsf
UsingTableA4
Sgen/m=6.048kJ/kg.K

EntropyBalanceforaControlVolume
In addition to methods discussed for closed system, the entropy can be exchanged
throughmassflowsacrosstheboundariesofthecontrolvolume.
mi

Control
volume

si

mo
T

se

Theentropybalanceintherateformforacontrolvolumebecomes:

dS CV
Q

k mi s i me s e S gen
,CV
dt
Tk
Forasteadystatesteadyflowprocess,itsimplifiesto:

S gen
,CV m e s e mi s i

Qk

Tk

M.BahramiENSC388(F09)Entropy5

Example2:EntropybalanceforaCV
Steamentersaturbinewithapressureof3MPa,atemperatureof400C,andavelocity
of160m/s.Saturatedvaporat100Cexitswithavelocityof100m/s.Atsteadystate,the
turbine develops work equal to 540 kJ/kg. Heat transfer between the turbine and its
surroundingsoccuratanaverageoutersurfacetemperatureof350K.Determinetherate
at which entropy is produced within the turbine per kg of steam flowing, in kJ/kg.K.
Neglectthechangeinpotentialenergybetweeninletandexit.
Assumptions:
1SteadystateoperationinCV.PE=0.
2Turbineoutersurfaceisataspecifiedaveragetemperature.
P1=3MPa
T1=400C

W/m=540kJ/kg

V1=160m/s

Turbine

T2=100C
V2=100m/s

Tb=350K

Sat.vapor

Fromthemassbalance,weknowthatm=m1=m2
Sincetheprocessissteadystate,onecanwrite:

Qk

m ( si s e ) S gen
,CV
Tk

TheheattransferoccursatTb=350K,thefirsttermoftherighthandsideoftheentropy
balancereducestoQ/Tb

S gen
,CV

Qk
( s 2 s1 )
m Tk

Weneedtocalculatetherateofheattransfer.Thefirstlaw(energybalance)canbeused
tofindtheheattransferrate.Combiningthemassbalanceandthefirstlaw,onefinds:

V22 V12
QCV
WCV

h
h
2
1
2
m
m

M.BahramiENSC388(F09)Entropy6

FromTableA6,h1=3230.9kJ/kg,andFromA4h2=2676.1kJ/kg.Aftersubstitution,and
convertingtheunits,onefinds:

QCV
22.6 kJ / kg
m

From Table A4, s2 = 7.3549 kJ/kg.K and from Table A6, s1 = 6.9212 kJ/kg.K. Inserting
valuesintotheexpressionforentropyproduction:

S gen
,CV

Q
k ( s 2 s1 ) 0.4983 kJ / kg.K
m Tk

Entropy
Entropycanbeviewedasameasureofmoleculardisorder,ormolecularrandomness.As
a system becomes more disordered, the positions of the molecules become less
predictableandtheentropyincreases.
Entropy
kJ/(kg.K)

Gas

Liquid
Solid

Fig.1:Entropyofasubstance(levelofdisorder)increaseswhenitmeltsfromsolidphase
toliquid.Ssolid<Sliquid<Sgas
Someremarks:
Work is an organized form of energy, free of disorder or randomness, thus free of
entropy.Therefore,thereisnoentropyassociatedwithenergytransferaswork.
The quantity of energy is always preserved during an actual process, based on the first
law,butthequalityisboundtodecrease(thesecondlaw).
Processes can occur only in the direction of increased overall entropy or molecular
disorder.Thus,theentireuniverseisgettingmoreandmorechaoticeveryday.
Atabsolutezero(0K),moleculesbecomecompletelymotionless,thisrepresentsastateof
ultimate molecular order (and minimum energy). Therefore, the entropy of a pure
M.BahramiENSC388(F09)Entropy7

crystallinesubstanceatzerotemperatureiszero.Thatisbecause;thereisnouncertainty
about the state of the molecules at that instant. This statement is the third law of
thermodynamics.
Sincethereisareferenceforentropy(absolutezero),entropyisanabsoluteproperty.The
entropymeasuredwithrespecttoabsolutezeroiscalledabsoluteentropy.
The two diagrams used most extensively in the secondlaw analysis are the Ts and hs
diagrams.Foraninternallyreversibleprocess,onecanwrite:

Qint,rev Tds

(kJ)

T
Internally
reversible
process
Q=Tds

Fig.2:OnaTsdiagram,theareaunderaninternallyreversibleprocesspresentstheheat
transferfortheprocess.
Foraninternallyreversibleisothermalprocess,wehave:
Qint,rev=T0ds
In a Ts diagram, an isentropic process is represented by a vertical line. An isentropic
processisaprocessinwhichentropyremainsconstant.Asaresultanisentropicprocess
involvesnoheattransfer.Therefore:
Isentropicprocess(s2=s1)=Reversible+Adiabatic

EvaluationofEntropyChange
Thedifferentialformoftheconservationofenergyforaclosedsystem(fixedmass)foran
internallyreversibleprocessis:
Qint,revWint,rev=dU
where,
Qint,rev=TdS
Wint,rev=PdV
Thus,
M.BahramiENSC388(F09)Entropy8

TdS=dU+PdV
or,perunitmass
Tds=du+Pdv
ThisiscalledthefirstGibbsequation.
Fromthedefinitionofenthalpy,h=u+Pv,onecanfind:
h=u+Pvdh=du+Pdv+vdP
EliminatingdufromthefirstGibbsequation,onefindsthesecondGibbsequation:
Tds=dhvdP
Explicit relations for differential changes in entropy can be obtained from Gibbs
equations:

du Pdv

T
T
dh vdP
ds

T
T

ds

Tocalculatetheentropychange,wemustknowtherelationshipbetweenduordhand
temperature.

CalculationoftheEntropyforSaturatedMixture
UseTablesA4andA5tofindsf,sgand/orsfgforthefollowing:
s=(1x)sf+xsgors=sf+xsfg

CalculationoftheEntropyforSuperheatedVapor
Giventwopropertiesorthestate,suchastemperatureandpressure,useTableA6.

CalculationoftheEntropyforCompressedLiquid
Intheabsenceofcompressedliquiddataforapropertyssf@T

EntropyChangeofSolidsandLiquids
Solids and liquids can be assumed as incompressible substances since their volumes
remainsessentiallyconstantduringaprocess.Thus,thefirstGibbsequationbecomes:
ds

du cdT

T
T
2

dT
s2 s1 c(T )
T
1

Assuminganaveragedvalueforspecificheat,oneobtains:

M.BahramiENSC388(F09)Entropy9

s2 s1 cave ln

T2

T1

Note that the entropy change of an incompressible substance is only a function of

temperature.Therefore,foranisentropicprocesswheres2=s1,onecanfind:
T2=T1

EntropyChangeofIdealGas
Theentropychange of anidealgascanbe obtained, bysubstitutingdu=cvdTandP=
RT/vintoGibbsequation.

dT
dv
R
T
v

2
dT
v2
s2 s1 cv (T )
R ln
T
v1
1

ds cv

Assumingaveragedvaluesforspecificheats,oneobtains:
T2
v
R ln 2
T1
v1

kJ
kg.K

T
P
s2 s1 c p , ave ln 2 R ln 2
T1
P1

kJ
kg.K

s2 s1 cv , ave ln

Forisentropicprocessesofidealgases,thefollowingrelationshipscanbefoundbysetting
ds=0,
ln

T2
R v2

ln
T1
C v v1

v
T
ln 2 ln 1
T1
v2

Cv

T2

T1

or

v1

v2

k 1

isentropic process

SinceR=cpcv,k=cp/cv,andthusR/cv=k1.
Inasimilarmanner,onefinds:

T2

T1

P2

P1

( k 1) / k

P2

P1

v1

v2

isentropic process

isentropic process

Theseequationscanbeexpressedinthefollowingcompactforms:
Tvk1=constant
TP(1k)/k=constant
M.BahramiENSC388(F09)Entropy10

Pvk=constant
Thespecificratiok,varieswithtemperature,andinisentropicrelationsaboveanaverage
kvalueshouldbeused.
Example3:Isentropicprocessofidealgas
A rigid, wellinsulated tank is filled initially with 5 kg of air at pressure 500 kPa and a
temperature500K.Aleakdevelops,andairslowlyescapesuntilthepressureoftheair
remaining in the tank is 100 kPa. Using the ideal gas model, determine the amount of
massremaininginthetankanditstemperature.
Slowleak

Mass initially in the

tank that remains in
thetank(m2)

Insulatedtank

Mass initially in the

tank that escapes
(m1)

Assumptions:
1Asshowninthefigure,theclosedsystemisthemassinitiallyinthetankthatremainsin
thetank.
2Thereisnosignificantheattransferbetweenthesystemanditssurroundings.
3Irreversibilitieswithinthetankcanbeignoredastheairslowlyescapes.
Solutions:
Usingtheidealgasequationofstate,themassinitiallyinthetankthatremainsinthetank
attheendofprocessis:
P2V
P
RT2
m2 2

PV
P1
m1 1
RT1

m2

T1

T2

m1

SincethevolumeofthetankVremainsconstantduringtheprocess.Weneedtofindthe
final temperature T2. For the closed system under consideration (m1), there are no
irreversibilities,andnoheattransfer.Accordingly,itisanisentropicprocess,andthusthe
isentropicrelationshipscanbeused:

T2 P2

T1 P1

k 1 / k

P
T2 T1 2
P1

k 1 / k

M.BahramiENSC388(F09)Entropy11

Withaconstantk=1.4forair,aftersubstitutingvalues,onefinds:
T2=315.55K
Finally,insertingvaluesintotheexpressionforsystemmass
m2=(100/500)(500/315.55)(5kg)=1.58kg

ReversibleSteadyFlowWork
The conservation of energy equation for a steadyflow device undergoing an internally
reversibleprocesscanbeexpressedindifferentialformas

q rev wrev dh dke dpe

But

q rev Tds

q rev dh vdP
Tds dh vdP
Substitutingintotherelationabove,aftercancelingdh,ityields,
wrev=vdP+dke+dpe
Integrating,wefind
2

wrev vdP ke pe

(kJ / kg )

With negligible changes in potential and kinetic energies,

2

wrev vdP

(kJ / kg )

Fromtheaboveequationcanbeseenthat,thelargerthespecificvolumethelargerthe
reversible produced or consumed work by the steadyflow device. Thus, every effort
should be made to keep the specific volume of the flow as small as possible during a
compressionprocesstominimizetheinputwork.
When the fluid is incompressible, the specific volume remains constant during the
process,thustheaboveequationbecomes:
wrev=v(P1P2)kepe(kJ/kg)
For a steadystate flow of a liquid through a device that involves no work interactions
(suchasnozzleorapipesection),theworktermiszero,

vP2 P1

V22 V12
g z 2 z1 0
2

ThisisknownasBernoulliequationinfluidmechanics.

M.BahramiENSC388(F09)Entropy12