Ther

mal
phy
sics
Thermodynamics:Ther
modynamicsist hebranch ofphysi
calsci
encet hatdealswitht
he
rel
ati
onsbetweenheatandotherfor
msofener gy(suchasmechani
cal,el
ectr
ical
,orchemi
cal
energy)
,and,
byextensi
on,
oftherel
ati
onshi
psbetweenallf
ormsofener
gy .

Whatar
etheappl
i
cat
ionsoft
her
mody
nami
cs?
Oneoft hemostimpor
tantthi
ngswecandowi t
hheatistouseittodowor kforus.Aheat
engi
nedoesexactl
ythi
s—itmakesuseoftheproperti
esoft
her
mody namicstotr
ansf
orm heat
i
ntowork.Gasol
i
neanddieselengi
nes,
jetengi
nes,andst
eam t
urbi
nesthatgener
ateel
ect
rici
ty
areal
lexampl
esofheatengi
nes.

TheFi
rstl
awoft
her
mody
nami
cs

Thef i
rstl aw ofthermodynamicsisav ersi
onoft hel
aw ofconser
vat
ionofener gy,
adaptedf orthermodynamicprocesses,disti
ngui
shi
ngtwokindsoftr
ansferofenergy,
asheatandast hermody
namicwor k,andr el
ati
ngthem t
oafunct
ionofabody '
sstate,
cal
ledinternalenergy.

Thelawofconser v
ati
onofener gyst
atesthatthetotalenergyofanisolat
edsy
stem is
constant
;energycanbet ransfor
medf rom oneformt oanother,butcanbeneither
creat
ednordest r
oyed.Forat hermodynamicprocesswi thoutt
ransferofmatt
er,the
fi
rstl
awisoftenformul
atedas
ΔU=Q-W

wher eΔUdenotest
hechangeintheinternalener
gyofacl osedsyst
em,Qdenot esthe
quantit
yofenergysuppl
i
edt othesy stem asheat ,and W denotest heamountof
thermodynami kdonebyt
cwor hesy em oni
st tssurr
oundings.Anequiv
alentst
atement
i
st hatper
petual
moti
onmachinesofthef i
rstki
ndareimpossibl
e.

Forprocessest hatincludet r
ansferofmatter
,af urt
herst
atementi
sneeded:'Wit
hdue
accountoft her espectiverefer
encestatesofthesy st
ems,whent wosystems,which
maybeofdi fferentchemi calcomposit
ions,i
nit
iall
ysepar
atedonl
ybyani mpermeable
wall
,andot her wiseisolated,ar
ecombi nedintoanew sy st
em bythether
mody namic
operat
ionofr emov alofthewal l
,then

U0=U1+U2
wher
eU0denot
est
hei
nter
nalener
gyoft
hecombi
nedsy
stem,
andUIandU2denot
ethe
i
nter
nal
ener
giesoft
her
espect
ivesepar
atedsy
stems.

Conti
nuingintheClausiussi gnconv enti
onf orwork,
whenasy stem expandsinaf i
cti
ve
quasi
stati
cprocess,thet hermody nami cwor kdonebythesystem ont hesurr
oundings
i
sthepr oduct
,PdV,ofpr essur e,
P,andv ol
umechange,dV,whereast hether
modynami c
workdoneont hesy st
em byt hesurroundingsis-PdV.Usingeithersignconvent
ionfor
work,t
hechangei ninter
nal energyoft hesystem i
s:
dU=δQ–PdV

whereδQ denot
estheinfi
nit
esimalamountofheatsuppl
i
edt
othesy
stem f
rom i
ts
sur
roundi
ngsandδdenotesaninexactdi
ff
erent
ial
.

Appl
i
cat
ionsofFi
rstl
awofTher
mody
nami
cs

Themostcommonpr act
icalappl
icat
ionoft
heFirstLawistheheatengi
ne.Heat
engi
nesconver
tthermalenergyintomechani
calenergyandvicever
sa..
..Thewateri
s
conver
tedt
osteam, andthepressureist
henusedt odri
veapistont
hatconver
tsheat
ener
gytomechanicalenergy
.

Q.Whati
sar
eal
li
feexampl
eoft
hef
ir
stl
awoft
her
mody
nami
cs?

Thef i
rstlaw oft
hermodynami
csshownistwoexamplesofenergybeingtr
ansfer
red
fr
om onesy stem t
oanotherandtr
ansf
ormedfr
om oneformt oanot
her.Humanscan
convertthechemicalenergyi
nfood,l
i
kethi
sicecream cone,i
ntokinet
icener
gyby
ri
dingabicycl
e.

Q.Whati
sthei
mpor
tanceoft
her
mody
nami
csi
nourdai
l
yli
ves?

Heati
ngandcool i
ngsystemsi
nourhomesandot herbui
ldi
ngs,engi
nesthatpowerour
motorv ehi
cles,eventhedesi
gnofbui l
dingsandvehicl
es,al
lincor
porat
einfor
mation
f
rom thermody namicstomakethem per
form wel
l
.

Secondl
awoft
her
mo-
dynami
cs

Thesecondl aw oft hermody nami csest abl i

shest heconceptofent r
opyasaphy si
cal
propertyofat hermody nami csy stem.Ent ropypr edictsthedirect
ionofspont aneous
processes,anddet ermi neswhet hertheyar eirreversibleorimpossibl
e,despiteobey ing
ther equi
rementofconser vati
onofener gy,whi chi sest abl
i
shedi nthef i
rstlaw of
thermodynami cs.Thesecond l aw maybef ormul ated bytheobser vati
on t hatt he
entropyofi solat
edsy stemsl eftt ospont aneousev olut
ioncannotdecr ease,ast hey
alway sar
riv
eatast at
eoft her mody nami cequi li
brium,wher etheentropyi shighest .I
f
allprocessesi nt hesy stem ar er eversible,theent ropyisconstant.Ani ncreasei n
entropyaccount sf ort hei r
rev er
sibil
ityofnat uralpr ocessesof t
enr ef
erredt oi nt he
conceptofthear rowoft ime.

Hi
stor
ical
l
y,t
hesecondl
awwasanempi
ri
calf
indi
ngt
hatwasaccept
edasanaxi
om of
ther
mody nami ctheory.St at
isti
calmechani cspr ov
idesami croscopicexplanati
onofthe
l
aw inter msofpr obabi l
it
ydi stri
butionsoft hestatesoflargeassembl iesofat omsor
molecules.Thesecondl aw hasbeenexpr essedi nmanyway s.It
sf i
rstformulat
ion,
whichpr ecededt hepr operdef init
ionofent r
opyandwasbasedoncal ori
ctheory,is
Carnot'
st heorem, creditedtot heFr enchscienti
stSadiCarnot,whoi n1824showedt hat
theeffi
ciencyofconv ersionofheatt owor kinaheatenginehasanupperl i
mit.Thef
irst
ri
gorousdef i
niti
onoft hesecondl aw basedont heconceptofent ropycamef r
om
Germansci enti
stRudol phCl ausiusinthe1850si ncl
udi
nghi sst at
ementt hatheatcan
neverpassf rom acol dert oawar merbodywi t
houtsomeot herchange,connected
ther
ewith, occurr
ingatt hesamet ime.

Thesecondl
awoft her
mody namicscanalsobeusedtodef
inetheconceptof
ther
modynamictemperat
ure,butthi
sisusual
l
ydelegat
edtothezer
othlawof
ther
modynamics.

TheFi
rstLawofTher
mody
nami
cs

Thef i
rstl
awoft her
mody namics,alsoknownasLawofConser vat
ionofEnergy,stat
es
thatenergycanneitherbecr eatednordest r
oyed;energycanonlybet r
ansferredor
changedf r
om onef ormt oanot her.Forexample,tur
ningonal ightwouldseem t o
produceenergy
;howev er
,iti
selectri
calener
gythati
sconv er
ted.

Awayofexpr essi
ngthefir
stlawoft
hermodynamicsisthatanychangeint
hei
nter
nal
ener
gy(ΔE)ofasy stem isgiv
enbythesum oft heheat( q)thatfl
owsacr
ossits
boundar
iesandthewor k(
w)doneonthesyst
em bythesurroundi
ngs:

ΔE=q+w

Thislawsay st hatther earetwoki ndsofpr ocesses,heatandwor k,thatcanleadtoa

changei ntheinternalener gyofasy st
em.Si ncebot hheatandwor kcanbemeasur ed
andquant if
ied,thi
si st hesameassay ingt hatanychangei nt heenergyofasy st
em
mustr esultinacor respondingchangei nt heener gyofthesur r
oundingsoutsidethe
system.I notherwor ds,ener gycannotbecr eatedordestroy ed.Ifheatf l
owsi nt
oa
system orthesur r
oundi ngsdowor koni t,thei nt
ernalener
gyi ncreasesandt hesignof
qandw ar eposi ti
v e.Conv ersel
y,heatf low outoft hesystem orwor kdonebyt he
system (onthesur roundings)wi l
lbeatt heexpenseoft heinternalenergy,andqandw
wil
lthereforebenegat i
ve.

TheSecondLawofTher
mody
nami
cs

Thesecondlawoft her
mody namicssay sthatt
heentr
opyofanyi sol
atedsystem al
ways
i
ncreases.I
solat
edsy st emsspont aneouslyev ol
vetowardst her
malequi l
ibr
ium—the
stat
eofmaxi mum entropyoft hesy st
em.Mor esimplyput:theentropyoftheuniver
se
(t
heulti
mateisol
atedsy stem)onlyincreasesandneverdecreases.

A si
mpl
ewayt
othi
nkoft
hesecondl
aw oft
her
mody
nami
csi
sthatar
oom,i
fnot
cleanedandt i
died,wil
linvari
ablybecomemor emessyanddi sor
derlywithtime–
regardl
essofhowcar ef
ulonei stokeepi
tclean.Whentheroom i
scleaned,i
tsentr
opy
decreases,buttheefforttocleanithasresul
tedinanincr
easeinentropyoutsi
dethe
room thatexceedstheentropylost.

TheThi
rdLawofTher
mody
nami
cs

Thet hi
rdlaw oft hermody namicsstatest hatt heentr
opyofasy stem appr
oachesa
const antvalueast hetemper at
ureappr oachesabsol ut
ezero.Theent r
opyofasy st
em
atabsol ut
ezer oist y
picall
yzero,andi nal lcasesisdeter
minedonl ybythenumberof
dif
ferentgr oundstatesi thas.Speci
fically
,theent r
opyofapur ecry st
all
i
nesubstance
(perfectorder)atabsol utezerotemper atureiszero.Thisstatementhol dst
rueifthe
perfectcrystalhasonlyonest at
ewi t
hmi nimum energy.

Carnot’
scycl
e:TheCar notcycl
eisatheor
eti
cali
dealt
her
modynamiccycl
epr
oposed
byFrenchphy
sici
stSadiCarnoti
n1824andexpandeduponbyot
hersint
he1830sand
1840s.

A Carnotcy cl
eisdef inedasani dealrev
ersi
bleclosedt
hermodynamiccycle.Four
successive oper
ati
ons ar einvolv
ed:isother
malexpansion,adiabat
ic expansion,
i
sothermalcompr ession,and adi
abati
c compressi
on.Duri
ng t
hese operat
ions,the
expansionandcompr essionofthesubst
ancecanbedoneupt othedesiredpointand
backtot hei
nit
ial
state.

Fol
l
owi
ngar
ethef
ourpr
ocessesoft
heCar
notcy
cle:

 I
n(a)
,thepr
ocessi
srev
ersi
blei
sot
her
malgasexpansi
on.I
nthi
spr
ocess,
theamountof
heatabsor bedbyt heidealgasi sqinfrom theheatsour ceatat emperat ur
eofTh.The
gasexpandsanddoeswor kont hesurroundi
ngs.
 I
n( b) ,thepr ocessi sreversibleadiabat i
cgasexpansi on.Her e,thesystem ist hermall
y
i
nsul ated,andt hegascont inuest oexpandandwor kisdoneont hesurroundings.Now
thetemper atureislower,Tl.
 I
n( c), t
hepr ocessi sreversibleisothermalgascompr essionprocess.Here, t
heheatl oss
qoutoccur swhent hesurroundi ngsdot hewor kattemper atur
eTl.
 I
n( d),t he process i sr eversible adi
abatic gas compr essi
on.Agai nt he system is
thermal lyinsulated.Thetemper atureagainrisesbackt oThast hesurr
oundi ngcont i
nue
todot heirworkont hegas.

Di
ff
erenceBet
weenI
sot
her
mal
andAdi
abat
icpr
ocess

Themaj ordi
ff
erencebet
weenthesetwot
ypesofprocessesi
sthati
ntheadiabati
c
process,t
her
eisnot r
ansf
erofheatt
owar
dsorfrom theli
qui
dwhichisconsi
dered.
Whereontheot
herhand,i
ntheisot
her
mal pr
ocess,t
her
eisatr
ansf
erofheatt
othe
sur
roundi
ngsi
nordertomaketheover
all
temperatur
econst
ant
.

Di
ff
erenceBet
weenI
sot
her
mal
andAdi
abat
icpr
ocess

I
sot
her
mal
process Adi
abat
icpr
ocess

Tr
ansf
erofheatoccur
s NoTr
ansf
erofheatoccur
s

Thepr
essur
eismor
eatagi
venv
olume Thepr
essur
eisl
essatagi
venv
olume

Thetemperat
urechangesduet
oint
ernal
Thet
emper
atur
eremai
nsconst
ant
syst
em var
iat
ions.

Thereisnoaddit
ionofheatnorheatis
Heatcanbeaddedorr
eleasedtot
he
rel
easedbecausemai nt
ainingconst
ant
syst
em j
ustt
okeepthesamet emper
atur
e
temperat
uredoesn’tmatterhere.

Thet
ransf
ormat
ioni
ssl
ow Thet
ransf
ormat
ioni
sfast

St
epsi
nvol
vedi
naCar
notCy
cle

Forani
dealgasoper
ati
ngi
nsi
deaCar
notcy
cle,
thef
oll
owi
ngar
ethest
epsi
nvol
ved:

St
ep1:

Isot
her
malexpansion:Thegasistakenfr
om P1,V1,
T1toP2,V2,
T2.HeatQ1isabsor
bed
from t
hereservoi
ratt emperat
ureT1.Sincetheexpansionisi sot
hermal
,thetotal
changeini
nter
nalenergyiszer
o,andtheheatabsorbedbythegasisequalt
othework
donebythegasont heenvi
ronment,whi
chisgi
venas:

W1→2=Q1=μ×R×T1×l
n(v
2/v1)

St
ep2:

Adi
abat
icexpansi
on:
Thegasexpandsadi
abat
ical
l
yfr
om P2,
V2,
T1t
oP3,
V3,
T2.

Her
e,wor
kdonebyt
hegasi
sgi
venby
:

W2→3=μRγ−1(
T1−T2)
St
ep3:

I
sot
hermalcompr
essi
on:
Thegasi
scompr
essedi
sot
her
mal
l
yfr
om t
hest
ate(
P3,
V3,
T2)
t
o(P4,
V4,T2)
.
Her
e,t
hewor
kdoneont
hegasbyt
heenv
ironmenti
sgi
venby
:

W3→4=μRT2l
nv3/v4
St
ep4:

Adi
abati
ccompr
essi
on:
Thegasi
scompr
essedadi
abat
ical
l
yfr
om t
hest
ate(
P4,
V4,
T2)
to(
P1,V1,
T1)
.

Her
e,t
hewor
kdoneont
hegasbyt
heenv
ironmenti
sgi
venby
:

W4→1=μRγ−1(
T1−T2)

Hence,
thet
otal
wor
kdonebyt
hegasont
heenv
ironmenti
nonecompl
etecy
clei
s
gi
venby:

W=W1→2+W2→3+W3→4+W4→1W=μRT1l
nv2v1−μRT2l
nv3v4

Netef
fi
ciency
=NetworkdonebythegasHeatabsorbedbythegas

Netef
fi
ciency
=WQ1=Q1−Q2Q1=1−Q2Q1=1−T2T1l
nv3v4l
nv2v1

Si
ncet
hest
ep2–>3i
sanadi
abat
icpr
ocess,
wecanwr
ieT1V2Ƴ-1=T2V3Ƴ-1
t
1/
γ−1
Or
,v v
2/ 3=(
T2T1)

Si
mil
arl
y,f
ort
hepr
ocess4–>1,
wecanwr
it
e
1/
γ−1
v
1v2=(T2T1)

Thi
simpl
i
es,

v
2/v
3=v
1/v
2
So,
theexpr
essi
onf
ornetef
fi
ciencyofCar
notengi
ner
educest
o:

Netef
fi
ciency
,η=1−T2/T1

Whati
sCar
notEngi
ne?

Carnotengineisat heor
eti
calther
mody namiccycleproposedbyLeonardCarnot.It
esti
matesthemaxi mum possibl
eeffi
ciencythataheatengineduri
ngtheconversi
on
processofheati
ntoworkand,conver
sely,wor
kingbetweentworeser
voi
rscanpossess.

Car
not
’st
heor
em,

Accor
dingt
oCar
notTheor
em:

Anysyst
em workingbetweenT1(hotr
eser
voir
)andT2(col
dreser
voi
r)canneverhav
e
moreeff
ici
encythantheCarnotengi
neoperat
ingbet
weenthesamereserv
oir
s.

Also,
t heef
fi
ciencyoft
histypeofengineisi
ndependentoft
henatur
eoftheworki
ng
substanceandisonlydependentonthetemperat
ureofthehotandcol
dreser
voir
s.

Ent
ropy

Ent
ropyi
sascienti
fi
cconcept
,aswel
lasameasur abl
ephysi
calpropert
ythati
smost
commonlyassoci
atedwi
thastat
eofdisor
der
,randomness,oruncert
aint
y.

SIuni
t:j
oul
esperkel
vi
n( K−1)
J⋅

Ent
ropy
,the measur
e ofa sy
stem’
sther
malener
gyperuni
ttemper
atur
ethati
s
unav
ail
abl
efordoi
ngusef
ulwor
k.Becausewor
kisobt
ainedf
rom or
der
edmol
ecul
ar
mot
ion,t
he amountofent
ropyi
s al
so a measur
e oft
he mol
ecul
ardi
sor
der
,or
r
andomness,ofasy
stem.Theconceptofent
ropypr
ovi
desdeep i
nsi
ghti
ntot
he
di
rect
ionofspont
aneouschangef
ormanyev
ery
dayphenomena.I
tsi
ntr
oduct
ionbyt
he
Ger
manphy
sici
stRudol
fCl
ausi
usi
n1850i
sahi
ghl
i
ghtof19t
h-cent
uryphy
sics.

Thei
deaofent
ropypr
ovi
desamat
hemat
ical
wayt
oencodet
hei
ntui
ti
venot
ionofwhi
ch
pr
ocessesar
eimpossi
ble,ev
enent
ropy
,themeasur
eofasy
stem’
sther
malener
gyper
uni
ttemper
atur
ethati
sunav
ail
abl
efordoi
ngusef
ulwor
k.Theywoul
dnotv
iol
atet
he
f
undament
all
awofconser
vat
ionofener
gy.

Forexampl
e,abl
ockofi
cepl
acedonahotst
ovesur
elymel
ts,whi
l
ethest
ovegr
ows
cool
er.Suchapr
ocessi
scal
l
edi
rr
ever
sibl
ebecausenosl
i
ghtchangewi
l
lcauset
he
mel
tedwat
ert
otur
nbacki
ntoi
cewhi
l
ethest
ovegr
owshot
ter
.Incont
rast
,abl
ockof
i
cepl
acedi
nani
ce-
wat
erbat
hwi
l
lei
thert
haw al
i
ttl
emor
eorf
reezeal
i
ttl
emor
e,
dependi
ngonwhet
herasmal
lamountofheati
saddedt
oorsubt
ract
edf
rom t
he
sy
stem.Suchapr
ocessi
srev
ersi
blebecauseonl
yani
nfi
nit
esi
malamountofheati
s
needed t
o change i
ts di
rect
ion f
rom pr
ogr
essi
vef
reezi
ng t
o pr
ogr
essi
vet
hawi
ng.
Si
mil
arl
y,compr
essedgasconf
inedi
nacy
li
ndercoul
dei
therexpandf
reel
yint
othe
at
mospher
eifav
alv
ewer
eopened(
ani
rr
ever
sibl
epr
ocess)
,ori
tcoul
ddousef
ulwor
k
bypushi
ngamov
eabl
epi
stonagai
nstt
hef
orceneededt
oconf
inet
hegas.Thel
att
er
pr
ocessi
srev
ersi
blebecauseonl
yasl
i
ghti
ncr
easei
nther
est
rai
ningf
orcecoul
d
r
ever
set
hedi
rect
ionoft
hepr
ocessf
rom expansi
ont
ocompr
essi
on.Forr
ever
sibl
e
pr
ocessest
hesy
stem i
sin equi
l
ibr
ium wi
thi
tsenv
ironment
,whi
l
efori
rr
ever
sibl
e
pr
ocessesi
tisnot
.

Byt
heCl
ausi
usdef
ini
ti fanamountofheatQ f
on,i lowsi
ntoal
argeheatr
eser
voi
rat
t
emper
at e T abov
ur eabsol
utezer
o,t
hen t
heent
ropyi
ncr sΔS = Q/
easei T.Thi
s
equat
ionef
fect
ivel
ygi
vesanal
ter
nat
edef
ini
ti
onoft
emper
atur
ethatagr
eeswi
tht
he
usualdef
ini
ti
on.Assumet
hatt
her
ear
etwoheatr
eser
voi
rsR1andR2att
emper
at esT1
ur
andT2(
suchast
hest
oveandt
hebl
ockofi
ce)
.IfanamountofheatQf
lowsf
rom R1t
o
R2,
thent
henetent
ropychangef
ort
het
wor
eser
voi
rsi
s

Whi
chi
sposi
ti
vepr
ovi hatT1 >T2.Thus,t
dedt heobser
vat
iont
hatheatnev
erf
lows
spont
aneousl
yfr
om col
dtohoti
sequi
val
entt
orequi
ri
ngt
henetent
ropychanget
obe
posi
ti
vef
oraspont
aneousf
lowofheat
.IfT1=T2,
thent
her
eser
voi
rsar
einequi
l
ibr
ium,
noheatf
l andΔS=0.
ows,

Thecondi
tonΔS≥0det
i ermi
nest
hemaxi
mum possi
bleef
fi
ciencyofheatengi
nes—t
hat
i
s,sy
stemssuchasgasol
i
neorst
eam engi
nest
hatcandowor
kinacy
cli
cfashi
on.
Supposeaheatengi bsheatQ1 f
neabsor rom R1 andexhaust
sheatQ2 t
oR2 f
oreach
compl
etecy
cle.Byconser
vat
ionofener
gy,
thewor
kdonepercy
cl sW =Q1–Q2,
ei and
t
henetent
ropychangei
s

TomakeW asl
argeaspossi
ble,Q2 shoul
dbeassmal
laspossi
bler
elat
iv oQ1.
et
Howev
er,Q2 cannotbezer
o,becauset
hi dmakeΔSnegat
swoul iveandsov
iol
atet
he
secondl
aw.Thesmal
l
estpossi
blev
alueofQ2 cor
respondst
othecondi
tonΔS=0,
i

y
iel
ding ast
hef
undament
alequat
ionl
i
mit
ingt
heef
fi
ciencyofal
lheat
engi
nes.A pr
ocessf chΔS =0i
orwhi srev
ersi
blebecauseani
nfi
nit
esi
malchange
woul
dbesuf
fi
ci
entt
omaket
heheatengi
ner
unbackwar
dasar
efr
iger
ator
.

Thesamer
easoni
ngcanal
sodet
ermi
net
heent
ropychangef
ort
hewor
kingsubst
ance
i
ntheheatengi
ne,
suchasagasi
nacy
li
nderwi
thamov
abl
epi
ston.I
fthegasabsor
bs
ani
ncr alamountofheatdQf
ement rom aheatr
eser
voi
ratt
emper
at eTandexpands
ur
r
ever
sibl
yagai
nstt
he maxi
mum possi
bler
est
rai
ning pr e P,t
essur hen i
tdoest
he
maxi kdW =PdV,
mum wor edVi
wher sthechangei
nvol
ume.Thei
nter
nal
ener
gyoft
he
gasmi sochangebyanamountdUasi
ghtal texpands.Thenbyconser
vat
ionofener
gy,
dQ=dU+PdV.Becauset
henetent
ropychangef
ort
hesy
stem pl
usr
eser
voi
riszer
o
whenmaxi
mum wor
kisdoneandt
heent
ropyoft
her
eser
voi
rdecr
easesbyanamount
dSreservoir = −dQ/
T,t
his must be count
erbal
anced by an ent
ropy i
ncr
ease of

f
ort
hewor
ki hatdSsystem +dSreservoir=0.Foranyr
nggassot ealpr
ocess,l
esst
hant
he
maxi
mum wor
kwoul
dbedone(
becauseoff
ri
cti
on,f
orexampl
e),andsot
heact
ual
amountofheatdQ′
absor
bedf
rom t
heheatr
eser
voi
rwoul
dbel
esst
hant
hemax
imum
amountdQ.Forexampl
e,t
hegascoul
dbeal
l
owedt
oexpandf
reel
yint
oav
acuum and

donowor
katal
l
.Ther
efor
e,i
tcanbest
atedt
hat wi
thdQ′
=dQ
i
nthecaseofmaxi
mum wor
kcor
respondi
ngt
oar
ever
sibl
epr
ocess.

Thi
sequat
iondef
inesSsystem asat
her
mody
nami
cst
atev
ari
abl
e,meani
ngt
hati
tsv
alue
i
scompl
etel
ydet
ermi
nedbyt
hecur
rentst
ateoft
hesy
stem andnotbyhowt
hesy
stem
r
eachedt
hatst
ate.Ent
ropyi
sanext
ensi
vepr
oper
tyi
nthati
tsmagni
tudedependson
t
heamountofmat
eri
ali
nthesy
stem.

I
nonest
ati
sti
cali
nter
pret
ati
onofent
ropy
,iti
sfoundt
hatf
orav
eryl
argesy
stem i
n
t
her
mody
nami
cequi
l
ibr
ium,ent
ropyS i
spr
opor
ti
onalt
othenat
urall
ogar
it
hm ofa
quant
it
yΩ r
epr
esent
ing t
he maxi
mum numberofmi
croscopi
c way
sin whi
ch t
he
macr
oscopi
cst
atecor
respondi oScanber
ngt eal
i
zed;t s,S=kl
hati nΩ,i chki
nwhi s
t
heBol
tzmannconst
antt
hati
srel
atedt
omol
ecul
arener
gy.

Al
lspont
aneouspr
ocessesar
eir
rev
ersi
ble;hence,i
thasbeensai
dthatt
heent
ropyof
t
heuni
ver
sei
sincr
easi
ng:t
hati
s,mor
eandmor
eener
gybecomesunav
ail
abl
efor
conv
ersi
oni
ntowor
k.Becauseoft
his,
theuni
ver
sei
ssai
dtobe“
runni
ngdown.
”
Si
gni
fi
cancesofEnt
ropyar
eMent
ionedBel
ow:

 Ent
ropyi
saphy
sical
quant
it
y.I
tisequal
tot
her
ati
oofheatabsor
bedorr
eject
ed
t
othet
emper
atur
e.
 I
tindi
cat
est
hedi
rect
ionofheatf
low.Aspont
aneouspr
ocessi
sal
soknownas
ani
rr
ever
sibl
epr
ocessbecauset
hesepr
ocessest
akepl
aceatav
eryf
astr
ate.
Al
lthenat
ural
processesar
espont
aneouspr
ocesses.
 I
thel
psi
ndet
ermi
ningt
het
her
mody
nami
cst
ateofanobj
ect
.Al
i
ttl
e
consi
der
ati
onwi
l
lshowt
hatwhenaspont
aneouspr
ocesst
akespl
acei
tmov
es
f
rom l
esspr
obabl
est
atet
oamor
epr
obabl
est
ate.
 Li
ket
emper
atur
e,pr
essur
e,v
olume,
int
ernal
ener
gy,
magnet
icbehav
iori
t
expr
essest
hest
ateofabody
.
 Theor
der
li
nessofanobj
ectdecr
easeswi
tht
hei
ncr
easeofent
ropy
.Hence
spont
aneouspr
ocessesar
eaccompani
edbyani
ncr
easei
nent
ropyaswel
lasan
i
ncr
easei
nthedi
sor
deroft
hesy
stem.
 Li
ket
emper
atur
eorpr
essur
e,i
tcannotbef
elt
.Hencet
hest
ateoft
heor
deroft
he
mol
ecul
esget
sdi
stur
bedandgi
vesr
iset
ogr
eat
erdi
sor
der
.
 I
tisameasur
eoft
hedi
sor
derorr
andomnessi
nthesy
stem.Whenagas
expandsi
ntoav
acuum,
wat
erf
lowsoutofar
eser
voi
r,spont
aneouschai
n
 r
eact
iont
akespl
ace,
ani
ncr
easei
nthedi
sor
deroccur
sandt
her
efor
eent
ropy
i
ncr
eases.

Q.Whatar
ethef
ourt
her
mody
nami
cfunct
ions?

Wehav efourfundament alf

unct
ionsthosearei nt
ernalener gyU,ent
halpyH,Helmhol
tzf
ree
energyF,andGi bbsfreeenergyG.Theyare“potenti
alenergy”defi
nedascapacit
ytodowor k.
Start
ingf r
om thef i
rstandsecondl awsoft hermodynami cs,wederiveexpr
essi
onsforthe
di
fferent
ialfor
m offourthermody
nami cpot
enti
als.