M.

BahramiENSC388(F09)Entropy1
Entropy
Thesecondlawleadstothedefinitionofanewpropertycalledentropy.
TheClausiusInequality
Thefirstlawissimplyanenergybalance.However,thesecondlawleadstoaninequality;
an irreversible process is less efficient than a reversible process. Another important
inequalityinthermodynamicsistheClausiusinequality:
0 s
}
T
Q o

Thatis,thecyclicintegralofQ/Tisalwayslessthanorequaltozero.Thisisvalidforall
cycles,reversibleorirreversible.
Forinternallyreversiblecycles,itcanbeshownthat:
0
int,
=
}
rev
T
Q o

Entropy
TheClausiusinequalityformsthebasisforthedefinitionofanewpropertycalledentropy.
As can be seen in the equation above, for an internally reversible process the cyclic
integralofQ/Tiszero.Aquantitywhosecyclicintegraliszerodependsonthestateonly
andnottheprocesspath,andthusitisaproperty.
Clausiusin1865realizedthathediscoveredanewpropertyandhecalleditentropy:
(kJ /K)
int,rev
T
Q
dS
|
.
|

\
|
=
o

Entropyperunitmassisdesignatedbys(kJ/kg.K).
Theentropychangeofasystemduringaprocesscanbecalculated:
(kJ /K)
2
1 int,
1 2
}
|
.
|

\
|
= = A
rev
T
Q
S S S
o

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.
For irreversible processes, we may imagine a reversible process between the two states
(initialandfinal)andcalculatetheentropychange(sinceentropyisaproperty).
M.BahramiENSC388(F09)Entropy2
TheIncreaseofEntropyPrinciple
Entropy change of a closed system during an irreversible process is greater that the
integral of Q / T evaluated for the process. In the limiting case of a reversible process,
theybecomeequal.
T
Q
dS
o
>
The entropy generated during a process is called entropy generation, and is denoted by
S
gen
,
}
+ = = A
2
1
1 2 gen
S
T
Q
S S S
o

Note that the entropy generation S
gen
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
case of a reversible process remains constant (it never decreases). This is known as the
increaseofentropyprinciple.
The entropy change of a system or its surroundings can be negative; but entropy
generationcannot.

<
=
>
=
process impossible 0
process reversible 0
process le irreversib 0
gen
S
1 A process must proceeds in the direction that complies with the increase of entropy
principle,S
gen
>0.Aprocessthatviolatesthisprincipleisimpossible.
2Entropyisanonconservedproperty,andthereisnosuchthingastheconservationof
entropy.Therefore,theentropyofuniverseiscontinuouslyincreasing.
3Theperformanceofengineeringsystemsisdegradedbythepresenceofirreversibility.
The entropy generation is a measure of the magnitudes of the irreversibilities present
duringtheprocess.
EntropyBalance
Entropy is a measure of molecular disorder or randomness of a system, and the second
lawstatesthatentropycanbecreatedbutitcannotbedestroyed.
Theincreaseofentropyprincipleisexpressedas
Entropychange=Entropytransfer+Entropygeneration
gen transfer system
S S S + = A
Thisiscalledtheentropybalance.
M.BahramiENSC388(F09)Entropy3
EntropyChange
Theentropybalanceiseasiertoapplythatenergybalance,sinceunlikeenergy(whichhas
manyformssuchasheatandwork)entropyhasonlyoneform.Theentropychangefora
systemduringaprocessis:
Entropychange=EntropyatfinalstateEntropyatinitialstate
initial final system
S S S = A
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.
Heat Transfer: heat is a form of disorganized energy and some disorganization (entropy)
willflowwithheat.Heatrejectionistheonlywaythattheentropyofafixedmasscanbe
decreased. The ratio of the heat transfer Q/ T (absolute temperature) at a location is
calledentropyfloworentropytransfer
T
Q
S
heat
= = const.) (T heat h ansfer wit Entropy tr
Since T (in Kelvin) is always positive, the direction of entropy transfer is the same of the
directionofheattransfer.
When two systems are in contact, the entropy transfer from warmer system is equal to
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
A closed system includes no mass flow across its boundaries, and the entropy change is
simplythedifferencebetweentheinitialandfinalentropiesofthesystem.
Theentropychangeofaclosedsystemisduetotheentropytransferaccompanyingheat
transferandtheentropygenerationwithinthesystemboundaries:
Entropychangeofthesystem=Entropytransferwithheat+Entropygeneration
M.BahramiENSC388(F09)Entropy4
gen
k
k
S
T
Q
S S + =
1 2

Therefore,foranadiabaticclosedsystem,wehave:
S
adiabatic
=S
gen
ForaninternallyreversibleadiabaticprocessS=0,becauseS
gen
=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.

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

Solution
Thenetworkcanbecalculatedbyusingthelaw:
U+KE+PE=QW
Thatissimplifiesto:U=W
Water
Paddlewheel
Insulated
M.BahramiENSC388(F09)Entropy5
Onaunitmassbasis,theenergybalancebecomes:
W/m=(u
g
u
f
)
FromTableA4,
W/m=2087.6kJ/kg
The negative sign indicates that the work input by the stirring is greater than the work
donebythewaterasitexpands.
Using an entropy balance, the amount of entropy produced can be found. Since there is
noheattransfer,
gen gen
S S
T
Q
S = + |
.
|

\
|
= A
}

0
2
1
o

Onaunitmassbasis,thisbecomes:
S
gen
/m=s
g
s
f
UsingTableA4
S
gen
/m=6.048kJ/kg.K
EntropyBalanceforaControlVolume
In addition to methods discussed for closed system, the entropy can be exchanged
throughmassflowsacrosstheboundariesofthecontrolvolume.

Theentropybalanceintherateformforacontrolvolumebecomes:
- - -
-
+ + =
CV gen e e i i
k
k CV
S s m s m
T
Q
dt
dS
,

Forasteadystatesteadyflowprocess,itsimplifiesto:

-
- - -
=
k
k
i i e e CV gen
T
Q
s m s m S
,

m
i
s
i

m
o
s
e

Control
volume
Q

T
M.BahramiENSC388(F09)Entropy6
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.

Fromthemassbalance,weknowthatm=m
1
=m
2
Sincetheprocessissteadystate,onecanwrite:
- -
-
+ + =
CV gen e i
k
k
S s s m
T
Q
,
) ( 0
TheheattransferoccursatT
b
=350K,thefirsttermoftherighthandsideoftheentropy
balancereducestoQ/T
b
) (
1 2
,
s s
T m
Q
m
S
k
k
CV gen
+ =
-
-
-
-

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

\
|
+ + =
-
-
-
-
2
2
1
2
2
1 2
V V
h h
m
W
m
Q
CV CV

W/m=540kJ/kg
T
b
=350

K
P
1
=3MPa
T
1
=400C
V
1
=160m/s

T
2
=100C
V
2
=100m/s
Sat.vapor
Turbine
M.BahramiENSC388(F09)Entropy7
FromTableA6,h
1
=3230.9kJ/kg,andFromA4h
2
=2676.1kJ/kg.Aftersubstitution,and
convertingtheunits,onefinds:
kg kJ
m
Q
CV
/ 6 . 22 =
-
-

From Table A4, s

2
= 7.3549 kJ/kg.K and from Table A6, s
1
= 6.9212 kJ/kg.K. Inserting
valuesintotheexpressionforentropyproduction:
K kg kJ s s
T m
Q
m
S
k
k
CV gen
. / 4983 . 0 ) (
1 2
,
= + =
-
-
-
-

Entropy
Entropycanbeviewedasameasureofmoleculardisorder,ormolecularrandomness.As
a system becomes more disordered, the positions of the molecules become less
predictableandtheentropyincreases.

Fig.1:Entropyofasubstance(levelofdisorder)increaseswhenitmeltsfromsolidphase
toliquid.S
solid
<S
liquid
<S
gas

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
Solid
Liquid
Gas
Entropy
kJ/(kg.K)
M.BahramiENSC388(F09)Entropy8
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:
(kJ )
int,
Tds Q
rev
= o

Fig.2:OnaTsdiagram,theareaunderaninternallyreversibleprocesspresentstheheat
transferfortheprocess.
Foraninternallyreversibleisothermalprocess,wehave:
Q
int,rev
=T
0
ds
In a Ts diagram, an isentropic process is represented by a vertical line. An isentropic
processisaprocessinwhichentropyremainsconstant.Asaresultanisentropicprocess
involvesnoheattransfer.Therefore:
Isentropicprocess(s
2
=s
1
)=Reversible+Adiabatic
EvaluationofEntropyChange
Thedifferentialformoftheconservationofenergyforaclosedsystem(fixedmass)foran
internallyreversibleprocessis:
Q
int,rev
W
int,rev
=dU
where,
Q
int,rev
=TdS
W
int,rev
=PdV
Thus,
T
s
Internally
reversible
process
Q=Tds
M.BahramiENSC388(F09)Entropy9
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:
T
vdP
T
dh
ds
T
Pdv
T
du
ds
=
+ =

To calculate the entropy change, we must know the relationship between du or dh and
temperature.
CalculationoftheEntropyforSaturatedMixture
UseTablesA4andA5tofinds
f
,s
g
and/ors
fg
forthefollowing:
s=(1x)s
f
+xs
g
ors=s
f
+xs
fg

CalculationoftheEntropyforSuperheatedVapor
Giventwopropertiesorthestate,suchastemperatureandpressure,useTableA6.
CalculationoftheEntropyforCompressedLiquid
Intheabsenceofcompressedliquiddataforapropertyss
f@T

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

}
=
= =
2
1
1 2
) (
T
dT
T c s s
T
cdT
T
du
ds

Assuminganaveragedvalueforspecificheat,oneobtains:
M.BahramiENSC388(F09)Entropy10
1
2
1 2
ln
T
T
c s s
ave
=
Note that the entropy change of an incompressible substance is only a function of
temperature.Therefore,foranisentropicprocesswheres
2
=s
1
,onecanfind:
T
2
=T
1
EntropyChangeofIdealGas
The entropy change of an ideal gas can be obtained, by substituting du = c
v
dT and P =
RT/vintoGibbsequation.
1
2
2
1
1 2
ln ) (
v
v
R
T
dT
T c s s
v
dv
R
T
dT
c ds
v
v
+ =
+ =
}

Assumingaveragedvaluesforspecificheats,oneobtains:
K kg
kJ
P
P
R
T
T
c s s
K kg
kJ
v
v
R
T
T
c s s
ave p
ave v
.
ln ln
.
ln ln
1
2
1
2
, 1 2
1
2
1
2
, 1 2
=
+ =

Forisentropicprocessesofidealgases,thefollowingrelationshipscanbefoundbysetting
ds=0,
process isentropic ln ln
ln ln
1
2
1
1
2
2
1
1
2
1
2
1
2

|
|
.
|

\
|
=
|
|
.
|

\
|
|
|
.
|

\
|
=
=
k
C
R
v
v
v
T
T
or
v
v
T
T
v
v
C
R
T
T
v

SinceR=c
p
c
v
,k=c
p
/c
v
,andthusR/c
v
=k1.
Inasimilarmanner,onefinds:
process isentropic
process isentropic
2
1
1
2
/ ) 1 (
1
2
1
2
k
k k
v
v
P
P
P
P
T
T
|
|
.
|

\
|
=
|
|
.
|

\
|
|
|
.
|

\
|
=
|
|
.
|

\
|

Theseequationscanbeexpressedinthefollowingcompactforms:
Tv
k1
=constant
TP
(1k)/k
=constant
M.BahramiENSC388(F09)Entropy11
Pv
k
=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
temperature 500 K. A leak develops, and air slowly escapes until the pressure of the air
remaining in the tank is 100 kPa. Using the ideal gas model, determine the amount of
massremaininginthetankanditstemperature.

Assumptions:
1Asshowninthefigure,theclosedsystemisthemassinitiallyinthetankthatremainsin
thetank.
2Thereisnosignificantheattransferbetweenthesystemanditssurroundings.
3Irreversibilitieswithinthetankcanbeignoredastheairslowlyescapes.
Solutions:
Usingtheidealgasequationofstate,themassinitiallyinthetankthatremainsinthetank
attheendofprocessis:
1
2
1
1
2
2
1
1
1
2
2
2
m
T
T
P
P
m
RT
V P
m
RT
V P
m
|
|
.
|

\
|
|
|
.
|

\
|
=

=
=

SincethevolumeofthetankVremainsconstantduringtheprocess.Weneedtofindthe
final temperature T
2
. For the closed system under consideration (m
1
), there are no
irreversibilities,andnoheattransfer.Accordingly,itisanisentropicprocess,andthusthe
isentropicrelationshipscanbeused:
( ) ( ) k k k k
P
P
T T
P
P
T
T
/ 1
1
2
1 2
/ 1
1
2
1
2

|
|
.
|

\
|
=
|
|
.
|

\
|
=
Mass initially in the
tank that remains in
thetank(m
2
)
Slowleak
Mass initially in the
tank that escapes
(m
1
)
Insulatedtank
M.BahramiENSC388(F09)Entropy12
Withaconstantk=1.4forair,aftersubstitutingvalues,onefinds:
T
2
=315.55K
Finally,insertingvaluesintotheexpressionforsystemmass
m
2
=(100/500)(500/315.55)(5kg)=1.58kg
ReversibleSteadyFlowWork
The conservation of energy equation for a steadyflow device undergoing an internally
reversibleprocesscanbeexpressedindifferentialformas
vdP dh q
vdP dh Tds
Tds q
d d dh w q
rev
rev
rev rev
=
)
`

=
=
+ + =
o
o
o o
But
pe ke

Substitutingintotherelationabove,aftercancelingdh,ityields,
w
rev
=vdP+dke+dpe
Integrating,wefind
}
}
=
A A =
2
1
2
1
) / (
energies, kinetic and potential in changes negligible With
) / (
kg kJ vdP w
kg kJ pe ke vdP w
rev
rev

From the above equation can be seen that, the larger the specific volume the larger the
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:
w
rev
=v(P
1
P
2
)kepe(kJ/kg)
For a steadystate flow of a liquid through a device that involves no work interactions
(suchasnozzleorapipesection),theworktermiszero,
( ) ( ) 0
2
1 2
2
1
2
2
1 2
= +

+ z z g
V V
P P v
ThisisknownasBernoulliequationinfluidmechanics.