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1he Second Law of 1hermodynam|cs
1he second law ol thermodynamlcs asserts that processes occur ln a certaln dlrectlon and
that the energy has uol|ty as well as uoot|ty.
1he llrst law places no restrlctlon on the dlrectlon ol a process, and satlslylng the llrst law
does not guarantee that the process wlll occur. 1hus, we need another general prlnclple
(second law) to ldentlly whether a process can occur or not.
(neat transfer)
Pot
contalner
osslble
Cold
surroundlngs
lmposslble
llg. 1: Peat transler lrom a hot contalner to the cold surroundlngs ls posslble, however,
the reveres process (although satlslylng the llrst law) ls lmposslble.
A ptocess coo occut wbeo ooJ ooly wbeo |t sot|sf|es botb tbe f|tst ooJ tbe secooJ lows of
tbetmoJyoom|cs.
1he second law also asserts that energy has a quallty. reservlng the quallty ol energy ls a
ma[or concern ol englneers. ln the above example, the energy stored ln a hot contalner
(hlgher temperature) has hlgher quallty (ablllty to work) ln comparlson wlth the energy
contalned (at lower temperature) ln the surroundlngs.
1he second law ls also used ln determlnlng the theoretlcal llmlts lor the perlormance ol
commonly used englneerlng systems, such as heat englnes and relrlgerators etc.
1herma| Lnergy keservo|rs
1hermal energy reservolrs are hypothetlcal bodles wlth a telot|vely large thermal energy
capaclty (mass x speclllc heat) that can supply or absorb llnlte amounts ol heat w|tbout
uoJetqo|oq ooy cbooqe |o tempetotute. Lakes, rlvers, atmosphere, oceans are example ol
thermal reservolrs.
A two-phase system can be modeled as a reservolr slnce lt can absorb and release large
quantltles ol heat whlle remalnlng at constant temperature.
A reservolr that supplles energy ln the lorm ol heat ls called a soutce and one that absorbs
energy ln the lorm ol heat ls called a s|ok.
neat Lng|nes
Peat englnes convert heat to work. 1here are several types ol heat englnes, but they are
characterlzed by the lollowlng:
1- 1hey all recelve heat lrom a hlgh-temperature source (oll lurnace, nuclear reactor, etc.)
2- 1hey convert part ol thls heat to work
3- 1hey re[ect the remalnlng waste heat to a low-temperature slnk
4- 1hey operate ln a cycle.
Lnergy source (lurnace)
Source (1
n
)

|n
8oller
1urblne

|n
W
|n
W
out
W
net
= W
out
- W
|n
neat
eng|ne
W
net
ump

out
Condenser

out
S|nk (1
L
)
W
net
=
|n
+
out
Lnergy slnk (rlver, lake)
llg. 2: Steam power plant ls a heat englne.
1hermal elllclency: ls the lractlon ol the heat lnput that ls converted to the net work
output (elllclency = benellt / cost).
W
net ,out
q
th
=


Q
in
and W
net ,out
= Q
in
Q
out
q
th
=1
Q
out
Q
in
1he thermal elllclencles ol work-produclng devlces are low. Crdlnary spark-lgnltlon
automoblle englnes have a thermal elllclency ol about 20, dlesel englnes about 30,
and power plants ln the order ol 40.
ls lt posslble to save the re[ected heat C
out
ln a power cycle? 1he answer ls nC, because
wlthout the coollng ln condenser the cycle cannot be completed. Lvery heat englne must
waste some energy by translerrlng lt to a low-tempetotute reservolr ln order to complete
the cycle, eveo |o |Jeol|zeJ cycle.
1he 5econd Low: ke/vin-P/onck 5totement
lt ls lmposslble lor any devlce that operates on a cycle to recelve heat lrom a slngle
reservolr and produce a net amount ol work. ln other words, no heat englne can have a
thermal elllclency ol 100.
Source (1
n
)

|n
W
net
=
|n
neat eng|ne
1hermal elllclency ol
100

out
= 0
llg.3: A heat englne that vlolates the kelvln-lanck statement ol the second law cannot be
bullt.
kefriqerotors ond neot Pumps
ln nature, heat llows lrom hlgh-temperature reglons to low-temperature ones. 1he
reverse process, however, cannot occur by ltsell. 1he transler ol heat lrom a low-
temperature reglon to a hlgh-temperature one requlres speclal devlces called
teft|qetotots. 8elrlgerators are cycllc devlces, and the worklng llulds used ln the cycles are
called teft|qetoot.
neot pumps transler heat lrom a low-temperature medlum to a hlgh-temperature one.
8elrlgerators and heat pumps are essentlally the same devlces, they dlller ln thelr
ob[ectlves only. 8elrlgerator ls to malntaln the relrlgerated space at a low temperature.
Cn the other hand, a heat pump absorbs heat lrom a low-temperature source and
supplles the heat to a warmer medlum.
Q
c c
Q
H
3
Condenser
2
Compressor
WARM
environment
H
WARM
house
Q
desired
H
output
Expansion
VaIve
W
in
W
in
R HP
W
c
desired
4
Evaporator
1
Q
L
Q
L
output
COLD
refrigerated
space
Q
L
COLD
environment
Refrigerator Heat pump
llg. 4: Cb[ectlves ol relrlgerator and heat pump.
Coeff|c|ent of erformance (CC)
1he perlormance ol relrlgerators and heat pumps ls expressed ln terms ol the coelllclent
ol perlormance (CC) whlch ls dellned as
COP =
Benefit
=
q
L
COP =
Benefit
=
q
H
R
Cost w
HP
Cost w
lt can be seen that
COP
HP
= COP
R
+1
Alr condltloners are baslcally relrlgerators whose relrlgerated space ls a room or a
bulldlng.
1he Lnergy Llllclency 8atlng (LL8): ls the amount ol heat removed lrom the cooled space
ln 81u's lor 1 Wh (watt-hour)
LL8 = 3.412 CC
8
Most alr condltloners have an LL8 between 8 to 12 (CC ol 2.3 to 3.3).
1he Second Law of 1hermodynam|cs: C|aus|us Statement
lt ls lmposslble to construct a devlce that operates ln a cycle and produces no ellect other
than the transler ol heat lrom a lower-temperature body to hlgher-temperature body. ln
other words, a relrlgerator wlll not operate unless lts compressor ls drlven by an external
power source.
kelvln-lanck and Clauslus statements ol the second law are negatlve statements, and a
negatlve statement cannot be proved. So, the second law, llke the llrst law, ls based on
experlmental observatlons.
1he two statements ol the second law are equlvalent. ln other words, any devlce vlolates
the kelvln-lanck statement also vlolates the Clauslus statement and vlce versa.
Source (1
n
) Source (1
n
)

n
W
net
=
n
neat eng|ne
q
1
= 100X

L
= 0

n
+
L
kefr|gerator

L
Lqu|va|ent
W
net
= 0

n
kefr|gerator

L
Source (1
L
)
Source (1
L
)
llg. 3: 1he vlolatlon ol the kelvln-lanck statement leads to vlolatlon ol Clauslus.
Any devlce that vlolates the llrst law ol thermodynamlcs (by creatlng energy) ls called a
petpetuol-mot|oo mocb|oe of tbe f|tst k|oJ (MM1), and the devlce that vlolates the
second law ls called a petpetuol-mot|oo mocb|oe of tbe secooJ k|oJ (MM2).
kevers|b|e and Irrevers|b|e rocess
A tevets|ble process ls dellned as a process that can be reversed wlthout leavlng any trace
on the surroundlngs. lt means both system and surroundlngs are returned to thelr lnltlal
states at the end ol the reverse process. rocesses that are not reverslble are called
|ttevets|ble.
8everslble processes do not occur and they are only ldeallzatlons ol actual processes. We
use reverslble process concept because, a) they are easy to analyze (slnce system passes
through a serles ol equlllbrlum states), b) they serve as llmlts (ldeallzed models) to whlch
the actual processes can be compared.
Some lactors that cause a process to become lrreverslble:
- lrlctlon
- unrestralned expanslon and compresslon
- mlxlng
- Peat transler (llnlte A1)
- lnelastlc delormatlon
- Chemlcal reactlons
ln a reverslble process thlngs happen very slowly, wlthout any reslstlng lorce, wlthout any
space llmltatlon - everythlng happens ln a hlghly organlzed way (lt ls not physlcally
posslble - lt ls an ldeallzatlon).
lnternally reverslble process: ll no lrreverslbllltles occur wlthln the boundarles ol the
system. ln these processes a system undergoes through a serles ol equlllbrlum states, and
when the process ls reversed, the system passes through exactly the same equlllbrlum
states whlle returnlng to lts lnltlal state.
Lxternally reverslble process: ll no lrreverslbllltles occur outslde the system boundarles
durlng the process. Peat transler between a reservolr and a system ls an externally
reverslble process ll the surlace ol contact between the system and reservolr ls at the
same temperature.
1otally reverslble (reverslble): both externally and lnternally reverslble processes.
20 C 20 C
8oundary
at 20 C
1ota||y
revers|b|e
Source at
1
n
= 20.00.1
Peat Peat
Source at
1
n
= 30
Interna||y
revers|b|e
1he Carnot Cyc|e
1he elllclency ol a heat-englne cycle greatly depends on how the lndlvldual processes that
make up the cycle are executed. 1he net work (or elllclency) can be maxlmlzed by uslng
reverslble processes. 1he best known reverslble cycle ls the cotoot cycle.
note that the reverslble cycles cannot be achleved ln practlce because ol lrreverslbllltles
assoclated wlth real processes. 8ut, the reverslble cycles provlde upper llmlts on the
perlormance ol real cycles.
Conslder a gas ln a cyllnder-plston (closed system). 1he Carnot cycle has lour processes:
1-2 8everslble lsothermal expanslon: 1he gas expands slowly, dolng work on the
surroundlngs. 8everslble heat transler lrom the heat source at 1
P
to the gas whlch ls also
at 1
P
.
2-3 8everslble adlabatlc expanslon: 1he cyllnder-plston ls now lnsulated (adlabatlc) and
gas contlnues to expand reverslbly (slowly). So, the gas ls dolng work on the surroundlngs,
and as a result ol expanslon the gas temperature reduces lrom 1
P
to 1
L
.
3-4: 8everslble lsothermal compresslon: 1he gas ls allowed to exchange heat wlth a slnk at
temperature 1
L
as the gas ls belng slowly compressed. So, the surroundlngs ls dolng work
(reverslbly) on the system and heat ls translerred lrom the system to the surroundlngs
(reverslbly) such that the gas temperature remalns constant at 1
L
.
4-1: 8everslble adlabatlc compresslon: 1he gas temperature ls lncreaslng lrom 1
L
to 1
P
as a
result ol compresslon.
Carnot cycle ls the most elllclent cycle operatlng between two specllled temperature
llmlts.
1he elllclency ol all reverslble heat englnes operatlng between the two same reservolrs
are the same.
1he thermal elllclency ol a heat englne (reverslble or lrreverslble) ls:
q =1
Q
L
th
Q
lor the Carnot cycle, lt can be shown:
q





th,Carnot
H
=1
T
L
T
H
P
1
n
2
W
net
1
n
= Const.
4 3
1
L
= Const.

L
v
llg. 6: -v dlagram lor the Carnot cycle.

q = =q
L
1he elllclency ol an lrreverslble (real) cycle ls always less than the elllclency ol the Carnot
cycle operatlng between the same two reservolrs.
<q
th,rev

th th,rev

>q
th,rev
irreversible heat engine
reversible heat engine
impossible heat engine!
Conslder a Carnot heat englne worklng between two thermal reservolrs 1
L
= 300 k and 1
P
.
1he thermal elllclency ol the heat englne lncreases as the heat source temperature 1
P
ls
lncreased.
1
n
k q
th
X
1000 70
900 66.6
300 40
330 14.3
1he thermal elllclency ol actual heat englne can be maxlmlzed by supplylng heat to the
englne at the hlghest posslble temperature (llmlted by materlal strength) and re[ectlng
heat to lowest posslble temperature (llmlted by the coollng medlum temperature such as
atmosphere, lake, rlver temperature).
lrom the above table, lt can also be seen that the energy has a quallty. More ol the hlgh-
temperature thermal energy can be converted to work. 1herelore, the hlgher the
temperature, the hlgher the quallty ol the energy wlll be.
1he Carnot kefr|gerat|on and neat ump Cyc|e
A relrlgerator or heat pump that operates on the reverse Carnot cycle ls called a cotoot
keft|qetotot, or a cotoot beot pump.
1he Coelllclent ol perlormance ol any relrlgerator or heat pump (reverslble or
lrreverslble) ls glven by:
COP
R
=
Q
H
1
/ Q
L
1
and COP =
1
HP
1 Q / Q
H
CC ol all reverslble relrlgerators or heat pumps can be determlned lrom:
COP
R ,rev
=
1
T
H
/ T
L
1
and COP
HP,rev
=
1
1T
L
/ T
H