TheSecondLawofThermodynamics

Thesecondlawofthermodynamicsassertsthatprocessesoccurinacertaindirectionand
thattheenergyhasqualityaswellasquantity.
Thefirstlawplacesnorestrictiononthedirectionofaprocess,andsatisfyingthefirstlaw
doesnotguaranteethattheprocesswilloccur.Thus,weneedanothergeneralprinciple
(secondlaw)toidentifywhetheraprocesscanoccurornot.

Q(Heattransfer)

Hot Possible
container Cold
surroundings

Impossible

Fig.1:Heattransferfromahotcontainertothecoldsurroundingsispossible;however,
thereveresprocess(althoughsatisfyingthefirstlaw)isimpossible.
Aprocesscanoccurwhenandonlywhenitsatisfiesboththefirstandthesecondlawsof
thermodynamics.
Thesecondlawalsoassertsthatenergyhasaquality.Preservingthequalityofenergyisa
majorconcernofengineers.Intheaboveexample,theenergystoredinahotcontainer
(higher temperature) has higher quality (ability to work) in comparison with the energy
contained(atlowertemperature)inthesurroundings.
Thesecondlawisalsousedindeterminingthetheoreticallimitsfortheperformanceof
commonlyusedengineeringsystems,suchasheatenginesandrefrigeratorsetc.

ThermalEnergyReservoirs
Thermalenergyreservoirsarehypotheticalbodieswitharelativelylargethermalenergy
capacity(massxspecificheat)thatcansupplyorabsorbfiniteamountsofheatwithout
undergoinganychangeintemperature.Lakes,rivers,atmosphere,oceansareexampleof
thermalreservoirs.
Atwophasesystemcanbemodeledasareservoirsinceitcanabsorbandreleaselarge
quantitiesofheatwhileremainingatconstanttemperature.
Areservoirthatsuppliesenergyintheformofheatiscalledasourceandonethatabsorbs
energyintheformofheatiscalledasink.

M.BahramiENSC388(F09)2ndLawofThermodynamics1
HeatEngines
Heatenginesconvertheattowork.Thereareseveraltypesofheatengines,buttheyare
characterizedbythefollowing:
1Theyallreceiveheatfromahightemperaturesource(oilfurnace,nuclearreactor,etc.)
2Theyconvertpartofthisheattowork
3Theyrejecttheremainingwasteheattoalowtemperaturesink
4Theyoperateinacycle.

Energysource(furnace)
Source(TH)

Qin
Boiler Qin
Turbine

Win Wout Wnet

Heat
Wnet=WoutWin engine

Pump
Qout

Condenser
Sink(TL)
Qout
Wnet=Qin+Qout
Energysink(river,lake)

Fig.2:Steampowerplantisaheatengine.
Thermal efficiency: is the fraction of the heat input that is converted to the net work
output(efficiency=benefit/cost).
Wnet ,out
th and Wnet ,out Qin Qout
Qin

Q
th 1 out
Qin
The thermal efficiencies of workproducing devices are low. Ordinary sparkignition
automobile engines have a thermal efficiency of about 20%, diesel engines about 30%,
andpowerplantsintheorderof40%.

M.BahramiENSC388(F09)2ndLawofThermodynamics2
IsitpossibletosavetherejectedheatQoutinapowercycle?TheanswerisNO,because
withoutthecoolingincondenserthecyclecannotbecompleted.Everyheatenginemust
wastesomeenergybytransferringittoalowtemperaturereservoirinordertocomplete
thecycle,eveninidealizedcycle.

TheSecondLaw:KelvinPlanckStatement
It is impossible for any device that operates on a cycle to receive heat from a single
reservoirandproduceanetamountofwork.Inotherwords,noheatenginecanhavea
thermalefficiencyof100%.

Source(TH)

Qin

Wnet =Qin

Heatengine
Thermalefficiencyof
100%

Qout=0

Fig.3:AheatenginethatviolatestheKelvinPlanckstatementofthesecondlawcannotbe
built.

RefrigeratorsandHeatPumps
In nature, heat flows from hightemperature regions to lowtemperature ones. The
reverse process, however, cannot occur by itself. The transfer of heat from a low
temperature region to a hightemperature one requires special devices called
refrigerators.Refrigeratorsarecyclicdevices,andtheworkingfluidsusedinthecyclesare
calledrefrigerant.
Heat pumps transfer heat from a lowtemperature medium to a hightemperature one.
Refrigerators and heat pumps are essentially the same devices; they differ in their
objectivesonly.Refrigeratoristomaintaintherefrigeratedspaceatalowtemperature.
On the other hand, a heat pump absorbs heat from a lowtemperature source and
suppliestheheattoawarmermedium.

M.BahramiENSC388(F09)2ndLawofThermodynamics3
 WARM WARM
QH environment house
3 2
Condenser QH Q H desired
output
Compressor
W in W in
R HP
Expansion Wc
Valve
desired
QL QL
output

4 1 COLD COLD
Evaporator environment
refrigerated
space
QL
Refrigerator Heat pump

Fig.4:Objectivesofrefrigeratorandheatpump.

CoefficientofPerformance(COP)
Theperformanceofrefrigeratorsandheatpumpsisexpressedintermsofthecoefficient
ofperformance(COP)whichisdefinedas
Benefit q L Benefit q H
COPR COPHP
Cost wc Cost wc
Itcanbeseenthat
COPHP COPR 1
Air conditioners are basically refrigerators whose refrigerated space is a room or a
building.
TheEnergyEfficiencyRating(EER):istheamountofheatremovedfromthecooledspace
inBTUsfor1Wh(watthour)
EER=3.412COPR
MostairconditionershaveanEERbetween8to12(COPof2.3to3.5).

TheSecondLawofThermodynamics:ClausiusStatement
Itisimpossibletoconstructadevicethatoperatesinacycleandproducesnoeffectother
thanthetransferofheatfromalowertemperaturebodytohighertemperaturebody.In
otherwords,arefrigeratorwillnotoperateunlessitscompressorisdrivenbyanexternal
powersource.
KelvinPlanckandClausiusstatementsofthesecondlawarenegativestatements,anda
negativestatementcannotbeproved.So,thesecondlaw,likethefirstlaw,isbasedon
experimentalobservations.

M.BahramiENSC388(F09)2ndLawofThermodynamics4
Thetwostatementsofthesecondlawareequivalent.Inotherwords,anydeviceviolates
theKelvinPlanckstatementalsoviolatestheClausiusstatementandviceversa.

Source(TH) Source(TH)

QH
QH +QL
QH
Wnet=QH Wnet=0

Heatengine Refrigerator Refrigerator

T=100%

QL=0
Equivalent

QL
QL

Source(TL)
Source(TL)

Fig.5:TheviolationoftheKelvinPlanckstatementleadstoviolationofClausius.
Anydevicethatviolatesthefirstlawofthermodynamics(bycreatingenergy)iscalleda
perpetualmotion machine of the first kind (PMM1), and the device that violates the
secondlawiscalledaperpetualmotionmachineofthesecondkind(PMM2).

ReversibleandIrreversibleProcess
Areversibleprocessisdefinedasaprocessthatcanbereversedwithoutleavinganytrace
onthesurroundings.Itmeansbothsystemandsurroundingsarereturnedtotheirinitial
states at the end of the reverse process. Processes that are not reversible are called
irreversible.
Reversibleprocessesdonotoccurandtheyareonlyidealizationsofactualprocesses.We
usereversibleprocessconceptbecause,a)theyareeasytoanalyze(sincesystempasses
throughaseriesofequilibriumstates);b)theyserveaslimits(idealizedmodels)towhich
theactualprocessescanbecompared.
Somefactorsthatcauseaprocesstobecomeirreversible:
Friction
Unrestrainedexpansionandcompression

M.BahramiENSC388(F09)2ndLawofThermodynamics5
mixing
Heattransfer(finiteT)
Inelasticdeformation
Chemicalreactions
Inareversibleprocessthingshappenveryslowly,withoutanyresistingforce,withoutany
space limitation everything happens in a highly organized way (it is not physically
possibleitisanidealization).
Internally reversible process: if no irreversibilities occur within the boundaries of the
system.Intheseprocessesasystemundergoesthroughaseriesofequilibriumstates,and
when the process is reversed, the system passes through exactly the same equilibrium
stateswhilereturningtoitsinitialstate.
Externally reversible process: if no irreversibilities occur outside the system boundaries
during the process. Heat transfer between a reservoir and a system is an externally
reversible process if the surface of contact between the system and reservoir is at the
sametemperature.
Totallyreversible(reversible):bothexternallyandinternallyreversibleprocesses.

Boundary
at20C
20C 20C

Internally
reversible
Totally Heat Heat
reversible
Sourceat
Sourceat TH=30
TH=20.001

TheCarnotCycle
Theefficiencyofaheatenginecyclegreatlydependsonhowtheindividualprocessesthat
makeupthecycleareexecuted.Thenetwork(orefficiency)canbemaximizedbyusing
reversibleprocesses.ThebestknownreversiblecycleistheCarnotcycle.
Notethatthereversiblecyclescannotbeachievedinpracticebecauseofirreversibilities
associated with real processes. But, the reversible cycles provide upper limits on the
performanceofrealcycles.
Consideragasinacylinderpiston(closedsystem).TheCarnotcyclehasfourprocesses:

M.BahramiENSC388(F09)2ndLawofThermodynamics6
12 Reversible isothermal expansion: The gas expands slowly, doing work on the
surroundings.ReversibleheattransferfromtheheatsourceatTHtothegaswhichisalso
atTH.
23 Reversible adiabatic expansion: The cylinderpiston is now insulated (adiabatic) and
gascontinuestoexpandreversibly(slowly).So,thegasisdoingworkonthesurroundings,
andasaresultofexpansionthegastemperaturereducesfromTHtoTL.
34:Reversibleisothermalcompression:Thegasisallowedtoexchangeheatwithasinkat
temperatureTLasthegasisbeingslowlycompressed.So,thesurroundingsisdoingwork
(reversibly) on the system and heat is transferred from the system to the surroundings
(reversibly)suchthatthegastemperatureremainsconstantatTL.
41:Reversibleadiabaticcompression:ThegastemperatureisincreasingfromTLtoTHasa
resultofcompression.
Carnot cycle is the most efficient cycle operating between two specified temperature
limits.
Theefficiencyofallreversibleheatenginesoperatingbetweenthetwosamereservoirs
arethesame.
Thethermalefficiencyofaheatengine(reversibleorirreversible)is:
QL
th 1
QH
FortheCarnotcycle,itcanbeshown:
TL
th ,Carnot 1
TH

P
1 QH

2
TH=Const.
Wnet

4 3
TL =Const.
QL

v

Fig.6:PvdiagramfortheCarnotcycle.

M.BahramiENSC388(F09)2ndLawofThermodynamics7
Theefficiencyofanirreversible(real)cycleisalwayslessthantheefficiencyoftheCarnot
cycleoperatingbetweenthesametworeservoirs.
th ,rev irreversible heat engine

th th ,rev reversible heat engine
impossible heat engine!
th , rev

ConsideraCarnotheatengineworkingbetweentwothermalreservoirsTL=300KandTH.
ThethermalefficiencyoftheheatengineincreasesastheheatsourcetemperatureTHis
increased.

THK th%

1000 70

900 66.6

500 40

350 14.3

Thethermalefficiencyofactualheatenginecanbemaximizedbysupplyingheattothe
engine at the highest possible temperature (limited by material strength) and rejecting
heattolowestpossibletemperature(limitedbythecoolingmediumtemperaturesuchas
atmosphere,lake,rivertemperature).
Fromtheabovetable,itcanalsobeseenthattheenergyhasaquality.Moreofthehigh
temperature thermal energy can be converted to work. Therefore, the higher the
temperature,thehigherthequalityoftheenergywillbe.

TheCarnotRefrigerationandHeatPumpCycle
ArefrigeratororheatpumpthatoperatesonthereverseCarnotcycleiscalledaCarnot
Refrigerator,oraCarnotheatpump.
The Coefficient of performance of any refrigerator or heat pump (reversible or
irreversible)isgivenby:
1 1
COPR and COPHP
QH / QL 1 1 QL / QH
COPofallreversiblerefrigeratorsorheatpumpscanbedeterminedfrom:
1 1
COPR ,rev and COPHP ,rev
TH / TL 1 1 TL / TH
Also,similartoheatengine,onecanconclude:

M.BahramiENSC388(F09)2ndLawofThermodynamics8
 COPR ,rev irreversible refrigerator

COPR COPth ,rev reversible refrigerator
COP impossible refrigerator!
th , rev

Example1:RefrigeratorPerformance
Arefrigeratormaintainsthetemperatureofthefreezercompartmentat5Cwhentheair
surrounding the refrigerator is at 22 C. The rate of heat transfer from the freezer
compartment to the refrigerant (the working fluid) is 8000 kJ/h and the power input
required to operate the refrigerator is 3200 kJ/h. Determine the coefficient of
performance of the refrigerator and compare with the coefficient of performance of a
reversiblerefrigerationcycleoperatingbetweenreservoirsatthesametemperatures.

Assumptions:
Steadystateoperationoftherefrigerator.
Thefreezercompartmentandthesurroundingairplaytheroles ofthe coldand
hotreservoirs,respectively.

Source(TH) =22C=295K

Wnet=3200kJ/h

Refrigerator

Source(TL) = 5C=268K

Thecoefficientofperformanceoftherefrigeratoris:

M.BahramiENSC388(F09)2ndLawofThermodynamics9
 COPR=QC/Wcycle
COPR=8000(kJ/h)/3200(kJ/h)=2.5
Thecoefficient of performance ofaCarnotrefrigeratorworkingbetweenthesame two
reservoirsis:
1 1
COPR ,Carnot 9.9
TH / TC 1 295 / 268 1

M.BahramiENSC388(F09)2ndLawofThermodynamics10