TheSecondLawofThermodynamics

Thesecondlawofthermodynamicsassertsthatprocessesoccurinacertaindirectionand
thattheenergyhasqualityaswellasquantity.
Thefirstlawplacesnorestrictiononthedirectionofaprocess,andsatisfyingthefirstlaw
doesnotguaranteethattheprocesswilloccur.Thus,weneedanothergeneralprinciple
(secondlaw)toidentifywhetheraprocesscanoccurornot.
Q(Heattransfer)
Hot
container

Possible

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
engine

Wnet=WoutWin

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).

th

Wnet ,out
Qin

Q
th 1 out
Qin

and

Wnet ,out Qin Qout

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

Condenser

Q H desired
output

QH

Compressor
Expansion
Valve

Wc

Evaporator

W in

R
QL

WARM
house

WARM
environment

QH

desired
output

W in

QL
COLD
environment

COLD
refrigerated
space

QL

HP

Refrigerator

Heat pump

Fig.4:Objectivesofrefrigeratorandheatpump.

CoefficientofPerformance(COP)
Theperformanceofrefrigeratorsandheatpumpsisexpressedintermsofthecoefficient
ofperformance(COP)whichisdefinedas
COPR

Benefit q L

Cost
wc

COPHP

Benefit q H

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=0

Wnet=QH
Refrigerator

Heatengine

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
Heat

Totally
reversible

Heat
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:

th 1

QL

QH

FortheCarnotcycle,itcanbeshown:

th ,Carnot 1

TL

TH

P
QH

TH=Const.

Wnet
4

3
QL

TL =Const.

Fig.6:PvdiagramfortheCarnotcycle.
M.BahramiENSC388(F09)2ndLawofThermodynamics7

Theefficiencyofanirreversible(real)cycleisalwayslessthantheefficiencyoftheCarnot
cycleoperatingbetweenthesametworeservoirs.

th ,rev

th th ,rev

th , rev

irreversible heat engine

reversible heat engine
impossible heat engine!

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:

COPR

1
1
and COPHP

QH / QL 1
1 QL / QH

COPofallreversiblerefrigeratorsorheatpumpscanbedeterminedfrom:

COPR ,rev

1
1
and COPHP ,rev

TH / TL 1
1 TL / TH

Also,similartoheatengine,onecanconclude:

M.BahramiENSC388(F09)2ndLawofThermodynamics8

 COPR ,rev

COPR COPth ,rev

COP
th , rev

irreversible refrigerator
reversible refrigerator
impossible refrigerator!

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:

COPR ,Carnot

1
1

9.9
TH / TC 1 295 / 268 1

M.BahramiENSC388(F09)2ndLawofThermodynamics10