Kechre 44

hermsynamt palanids
The deml eneg s a
the game
ganme Cha
syBem
oves trom
wdegoesotale of gulilirin
OYe

he roule taken.
to avcher, irrnetechve
| an
importart hennorani
io not the ony one. e
uaniy. taweve, tia VT and
Varç ous Combinationo of
ot S
Ctm add
the diynengion ot enei
witth U (PrereNimg
and Grl tae ae called Ho
the
Hee new tunciong ot
thenmaamil olenhdh

We hae ound tht e can wicte V=W(s)

by the tulane n eguion,
dU Td-d
Ss't md Vaae hed eonstart, dU=, meaning
a cowstant
 Nauw, recall tha, dv

impbes t , T and þ= -
Forz
tor T9 where volume
an inoohoaie Aroce% t T g
n a camtant d=TaS and toR a revenile
iotchoree proc en
Since,
dU= = ldT ToS
Ta
AJ=

the volune io a co notav. We

Pio io true ony presoUe
is idea t
to aotart
uJant to etend thermaymamie pelatial
ad tio an be done aing a
lled entsgy.
Ethad, H
enty ao, H= U++y
We dene
dH =
dH TS+Vd
o
R Hin
is S and f and
nat°tal vatiades
S the
have = H(S)
dS t
an
 For ancd isolbaio brocen, there is ehange in
prese, A0 dP =0.
.'.dH =TdS
dove Reveraibe iobania poeey Hhet,
(Since tey=S)
dH y= ,dT
AH= , T
he Keveside inoaie moces, the hange
So fon abgornbed by the
enthalgy given te et
uedt to he a dtem, # goe)
dyatem.
and
genealy any to achieve.
Tocbaie 0orditioms mert open to the air in a
For exanle, an expen penue
at aonhent preue, ainee the
labratory the otmoapkene. We aho conolude,
in and
given ae comtand, dH = 0

both inemal ener ond enthalgy has the

Houerer, their rahwt variaelea in
clzaub k Ht taey one
entepy, hich is nct nolly elsily mewsalle
a

quantty. Tf ue ue peee this uith empera

nuoh mte emvenierd, tigo
Helmholte ree energy, F
We deme. F= U-TS
SdT TdSPdV-TdS-AT
dF= dä TdS
.. dF= -ST- tdV and V, and 00,
tor F in T
So a Vaziables
Bo,
FaF(t).
.. dF=E) T+ laE) dV
with and
T=0, and 30,
For aM iocBenmal oes,
F= -dV 40,

AF in þoerthve, t nepre,ents revevible

Bo i
the aytem ly the uoundirg
o
Wsru done On
We will A0on Gee t
Vice vewa.
arourt of work yoy
TepneAert the maxinum empe
syotem ad csnotant

Raute.
 G

We dee Gidbo tree eregy

G= H-TS
TdS- &4T= Td S+Vdp-TS
- d= dH- -ST

and a the nou vaiade, are þ and T

ging T
and T

Having t and T as nettal varade, isn niee

Ainee hee aNe the variable eani est to man
T T and
puate in exeimental aaema. Tf ane
Conott G=0- o, in an inobanie leefenr
ioothesmad peoeen G iQ a constand
lontrats
We have
valid tade ot tunetion. Atoueve, one
atiid quardites, whex is
Hhe onl notud one. We wil ohou ta tia
 the Cwe. However, hieh of tere
of tae ie mont upel cependa o the
eonte of the po pdem, and in paieula, he
ype of Constednttt io aplied to he dtem.
lomsiden lage height The
ayoBem as a potenidl to provide wsefl woeK
Ainee one Can connedt it to a puley and b4t
another oltet to thd more eigt. Houeven, onee it
Usetu worK aY
in in the round.
attained. H it+ be vey wsetl to have a
ava lalole
be
depend, on Hhe amount ofa
amownt of sefd
quantity that Can prRovide. We Gall auch a
work sgehem
quavdrty e ee enegN.
in, in any paiada ituton, we
the tree energy
tave to Reenler tet aa ayetem edange enegy
otth ta Aurounding and how it oes cependa on
Hhe aort of eonetrirt tt he uondig imore,
on the otem. We l irt demonort thia
a pathla and then Menerali e
this.
Comiden a
sytem wih xed voluwme, held at
temyenahuse
the. swVOUN
ene the
dhanges and the ehnge in
dig
entrog ot the Yen anwt be aueh tht toal
uniVeRAe, Std So0.
ohange in ertory t the

=dV-dW and ao
Now, by the Giat law, em
the wonk addel to he
dy-Tas
dF= d(u-T) = dy-Tdc
Gxed
Nou, Ainee T ia Aued,
and henee,
ohoun here ia, wenk added to
What we hae
Htelolte ee ey.
he aYd oK adel
prOCes,
proeem, =dF
In Revesibe izecty t ineage F
to the tem cecain amoud of tea
we eact a anoeiaed wh
I! leont be
ayoem, this will at
Hhe enequ Now,
daop in wonk to the 4ytem
as wth owe onalg.
leth the to A0 at he heigtt at tat
mam
and it h leial to do won in ttue
gives the
(Ading free
ue eneg to te syaon), erhaat-ng
fron he ytem to preovide woru
douwn, ht reduees he potential
blen). Note tet, if he
of the
hee eneg iolded, 40 no womK dF60
(an lbe done,
dgaten is mechanicay ohange in F to be nogoive. One
0vce Hho
the
0 any ROCe) il (quse the
doun to cquiiuon, F uwil Le tonstat
tem sedes doem
Avatabith ot n a i niM on level. Hence, euliri uom
lan

ony be achieved by minimi zòng F.

Avalabitty Sorroundi
sem
ng
We want to worzk out how to hnd
the egullbiun pragerkes ayten wen it is
placed in cortat uith th sumopndinga- TIn gencrd,
a yotem can exeharg hent e with e sunouning
a do on the ouTOUndirgo if the volme ofc!
dten ohange (nedaricol ong. Ke he durrundy
T and peture Po We trtarfe
A) and voluwme dV trom the ATUOUN dng
too the tem. The itemal eneryothe dur
cundity hange by d uhene

where the KNUS Aigr imples the sUznouninge

\ooing energs amd volme.
dU+dV
IS. To

coich in the change im entes st the auRndingo.

T the change nentrg
entrog te ds, ther
dStot = dS+dS
Sinoe, dtot0 , we gel,
dUtdV
tot To

tot
-\dV Fadv-TdS]o

I we detme avalality /
A= U+VLS.
and oinmee t and To ane lonwtar hen,
A = dV+t,dv- Tod

Go, the chonges in Ain

-oystem sete doun to qulihrim, y dhonge,will
tomee A
A will be a con tent in he tinimum evel
A
huever, the equibrim ehieved kqoe
the n e of constrait
and volume: Tn
1. Slem ith ed entog we mwst
are, ohate.
the eguilibiun
mininize Uto Gind
Loith Baad erogy nd preure:
Loe mw

dA= d+V= dtt o.

No,
inini Hto tinde the
is henmdly indlael aondl ta
3. Syem th thd het Qan
Vnedaie al cSK aan be done
erter and MC
dA = -I.S and henee
dU=0. So,
dS>0. So, we mut mazimi ze S to tn
the eqibm otate
4. Bysten vol ume and Contont tene
zune: Sine T-o,
We YAut mnùize
P to ind the equlikrium tade
 dT=0 and d =0, Now

dG= dH -Td-ST
dG= dU+dV+V d F - d s T
dG= dU4+FadV- Tods
-. Here dA=dG0 0. So, we must
a to tind the
MiniYze eneg
equlbrum
Chenitry labordorie
mean
prenure. Smee, dA= TdSVd+.
AH in he s2eveLi ble
dH= TIS= . Rev o
Aykm, thd ie hea dbdoiked
he aded to the het eneig the
rreaci on t the
yte). Now,

ie &alled ethermia
cion
reachon
he TEa
will Le aborecd and
alled endethemia
the ea chion in
doesnt
about
touwevel,
an
the spontanety
wshethe qctualy proceed or
Mot. Uauay are at aonotrt and
Sleatho
Tie duing the
T (uel, the temperahe my the
waitina erough wll ve abu
thoLes, lo ha to tinu
One ona
Aemperdae hermottario
poBertols
the end Paindo,
ainee must oe
aJe tde Burmcon). Go, G
iimizelSor eqibrà um thermg
Seaonal law of
aleove tell u Hha taetion
4GKO, then the
dyramies vnpli e,, if
Lwill sportaneousy
Maull' nelatio
We ae to hawourr
Mazud'o ndoon. These enuatons
m therto dy nanis, 2ach of
pachd deavaive of one
Hhem Telotes the
ha to measwe to paraial
quantity thad in
derivachye quonhty
Yneaswed.
 4

dxt

exae, We Qan dloo rite,

and

Nou the necemarg ondton for the oi

Merertal c to be exad in,

We w UNe then idea to each ot the

tede vaua deo U, H, F and G
an

anc V =

Now the a d.erenhd U is exat i .

)

For othe, Mazuel'

)
 an e Jummq
A the Maawel's reldiona
8)
ushere a b are Q0njugcte
a= 9, hen e=T, and
Nariades.
d , )

V and the same

Moreoyen
ide, we have to inorpore a mirus

Fitdig imantant qurtte

e no, - (T-TB),
o
and
T
and

So it elate the parhel den. vahv

relati to heat caypohes.
 ) Genemzel
Aserty: ze
A genealigd
a
vasçiaale

canges hen a eneralized onee io agpbel. A

auch as T or ia dhfhen
genezalizel oeee othe
til emal nerg with Respet to dame
parzamder.
dU= TdS-V and -
One
ao 1
sseerhility can be iratenvo luvme
e genealiztd (grutatd, ow ynueha
ushen gou dange myercue T.
ohanges
vity (po eonoent) i dehned a
he inobario epani

adiabate epanoiviy (SoncBend) ia defined ao

qnd the
dheto knm)
meanue the hacional change in
uthene eganivitea
volume with a doge
1a
Tastea eomprenbilbty is de tned , r
Adiabaie
here he omproibilty
a
volune conges when you apy reuae.
Atthounh t mit 4eem that domprenibiltty io negchve
do not. Sinee jn Be oause i

ay reuro, volume deerease. Se, the Orpremi

poettive .

nole ided g. V= RT. lonider

he entropy an a umeion
Sunehon fo volume and
tempendute,
dS = dTt dv

dT +

Bud,

T t R dv
T

not a undion
and
 atoo gan, ideal ton
and i,thod, chow
K hew
VTe hat hou
Prodem
temperahune. and ume vd
aenatart with inUeases
ideal
ertr the So, idel
an