Section – 2

THERMODYNAMICS

S. No. Topic
1. Thermodynamic Systems and Processes
2. Zeroth Law and Temperature
3. First Law, Heat and Work
4. Second Law, Heat Engines and Pumps
5. Entropy, Availability and Irreversibility
6. Pure Substances
7. Properties of Gases and Gas Mixtures
8. Thermodynamic Relations

Reference Authors:
• P. K. Nag.
• Yunus A. Cengel and Michael A. Boles.
 and rocanes.
a) Themody namic Sqstems
whnch attenhen i
System: Kegien in &pace upon
Cencentrated n analsis o a prob lem

to tha ystem.
Surroundings: Eveuy ing extexnal
System and Surroundinga
a Apasated by
Bownday
TYPES OF SYSTEMS

No pouble energy
trae but
System:
Closed ma

cyhnder artangerhent
rae ta: Paton-
Conbot Volame: Both mas amd
amd

Open Sytem o

enegy hana a: lurbine , Combeaet.

amd enog.tram
Tsolated Systen: No mat
wniveue, theamei laak.

¥Univer se System +Surroundang

Cendi t n
ropesly: Meause o phseal
ystem
hav
physical ystom
a
State: Conditon q
tem
a

deinite set q propetes.

states
Pafh:Succosnene tates duriv ehange
Locus e atat e obtauhed durithange state.

Prote ehange slate uskese paBh Comblotedy

eciied
Caele: Series a state changer auuh hat in kal
Atote final Stoate CNo evidence o proum).
TyPES OF ProcESSES
Systen Nature iyNabut Keveeo
>Revensíble
-Non flow
> Flow I r eversible

yPES OF PRoPERTIES
mas
froperties: Independent of
Lntenaive
voluwme Cdeny
pvevt, tempesatuu,
specific
:
peufic heai
m maxs
Extenaive Propestei Dependsnt
:

Volume, Enagy ma Callsd

pvopeito pen wntt velu
a
Extensue
t t e n e propetes

hase A quan& matte ho mogenaous

tn chamical Comb bton
and phj5LCa
voghout
shuche.

Homoeneou System! Singla phae atem

Hetexogensous System Multhi phae Aystem
Themodynamic Equiibrium

Mechaníchl chemical
Thamal
Eauiibrium Eaul Lium akbTi
state ostuatelo1) 2- propey Rale 1 "he tate q
atate
a System Can be Specired by intentie
Propexke providad undan equikbriuM
Continuum: Matter treated as a ninat man
boithout onsicdasng statiukcal behavio e h
naridual moucues Housevex, Centinum u Lot
when maan tu pah moleculus extasds h
sustem dinensions CHrgha ed gaue).
b) Zexoth Law and lembesatuve

Tevoh Law oTlemnodynamiua: two aystemm 'A

and 'B aesaiod to be in thomal equiibrium

individually with a
hird system C,thon e
Aaid to be in thormal
wo Aystemd A omd B a

wtth: each othoA

equbium
muauremer
Zooth lauo i e basu for tembaxatue
MEASUREMENNT DF TEMPERATURE!
XX a hu

Belove 954
Hamo metri c
Teence points
t100XX
X abitrary9
LX-X
point

i) Alte 1954
X abitrary
T2736 Point.

Xis tnple point

hemometnt pt

Triple Point q wate A 21316 k and 4:5 m

Ha (61l-04 Pa o 62 2 Ha0). mm

THERMoMETRIC PROPERTES OF THERMDMETERS

Themomtker Thxmornerie frope k

Conatamt Premu Volume
Covnfant Volum Premu

Rasu tance RAiatante

EME
ThermoCouple
5 Liaid in Glas Liqwiol Column
*KK°C+243 AT) A)
5
c) first Law, Heot & Work
r°pees
Point and Path funcio Phical
Foint
a
t e m a

oc dtexmint t tate ®xatk Allerunhals.

a
point untkens. Tkey pbintunuhon
a
temperatun
P r e r , Vekume, uch
point

dP f du chdT o
Jor
Ato
unck'on tohese Cyclic
pointr-unckov
System opestkes
a
wich
w i c h dapend
dapen
"hoe propekes
ntegnal a u zeno,
pot unctons Tey
mend states as

P
nexact dtheantiah Heat amd wok a
uncton lou

Prous. ît u an ininitesimal a low

uasi-stake
t sustem a n uYTDmdn
pro a s in onh wit
with
emain n hayw.odynamic equibrtum
tntermadte
eah othe, a each amd evem

state
TYPES Of QUASt-STATIC PROCESSES:
Constant Voluma o lso ckoric CV=c)
Constant Preu o lsobauc CP:c)
Grtant Temexata o lsothesmal CpV=)
Adiabakc CPVc)
Polytropic CpV-c)
Raveible adiabate o 1centropic
vovk: t the produc o nta and t th
displaunent in i divecton

d V [N=n Flou
8 dw - ydP
IFlb w)
ntensive x Chanqe tn extentve

dv x dw
Integvatrg factor.
 IN VARIDUS UASI- STATIC PROCESS E S
WoRK DoNE
cloed ptemo
Voum
P: axu

PVC Open ystem

pre
Pv":c ay is

Pv

* Buaw Ltake prous u a nen {ov prou t a n

plat tn a ceed.uutem

Pro Cexs Work Done

Flow Non Flbw

-JvdP
Cows tant Yexu PCV2-V)

CorbtantVoluma vCP- Pa

Cerstont Tempontws -,U, tn [Ph/) P

(CT)
PV tn V./v») V, Lnt/v,)

Adiabaic PvPV) RV-PVE

CAN-O) Y-1 -

olytrepre CRV,P,va)
n-
PV-PV
n -

wek don b th Aysfem 'u peiiu ano

ASDR done on th Aystem i negake
PC

Ve C
Xf an enture cyelo

e mokon involving Spe calkunttor

V caleuulade w by
bostituEg he qeln unclenin

pdv a
pdv a vdp
as
o eaired.

tr eton atbV
HeatEng Cauued by tombexatun dkhwnte

d Tds
SEnthopy (Exfor ve rope
S dQ
T
Onegratig Jatou
ecc Heat: teat reqir to raise -temeag
unut mak hrDugh unt tempeatuna d
C
mAt

C Sp Heat at , Ceat presu

Sp Heat at.Cost. olume
m.C C Heah Capauy C7/»)
Latent Heat: The amount oL haat
regred
Cauahat ehange at Conatant tembexatwu X
Te Thepes
Latent haat
fuien c ).
)Latent heat o
nisakom (L
latent a 7 laraunsakon Cvap).
Subltroatb Clsus).
Heat Suppled to a utt er
Aaa vejected by
pottkve md
System mqakve
a

FIRST LAW of
HERMODYNAMICS:
In prinuple, tha lau oConervakon obnasg9
First La Ln a clostd
System unduqoinga
Cycle;

cod dw
first law ot a cloud yslem undugoing a pro ta

d@ de +dn
dE : change tn enesgy (inteynal eagy)
da : dU +dW

tho system (txtenmve)

*Enesgy a p o p e
AE O
onutant.
an uolatd System
¥Ena
Eneqy

5gy
i) Enay in Stovage
Intexnal Enegy enthalpy
Heat dork .
ti)Enegy in,tvat Take CdT
du dT
hvstta opplied to lowrOy
and {low enangu3
*Enthalpy Sum ointesnal
hH1
H U PV
h ut p
Take JcpdT f
*dH: p dT
yst law cteady o s
In low ro es
enyeuaton (sFEE)

hy
V
PVu, Steady
lo hV w
Device
 mCht +171) + Q
2
n (ha 2
+311) +w

H+w
. d dH+dW

Enthalpy and nteinal Enerqy ae uneio

mberaturt on
Stead Tlow davice
Nozztk Dutwo
- ur bins Comp1eMoi
->
Pmp
-Throttin Ásvice Hea Exchangeu
Eulea Beanoulli equate w s in Pud
Me chanin a special Care SHEE
q SHEE

* n ca vdriabu {too prasAe Re

bottl U and empy cha nd

disthanga
qven b y
ank, ho. enagy halanCa

he Vp a ipe enthalpies anod veouies

ard
Ta7T, T
Pesbetual Mobon Macu 1 CEM1) Machine
violatng Firstaus oy Cenvestn al Ae at
mto wotk
d) Secend Law, Hea Engine pum B Kokngerabew:

Limutalies he tirst Law o hermodnamiCa

onveruyuon
a)Doexnt Specihy Conditon q Heat wok
o directibn o Conveumen
to heat. But not vite veua
Wek a tully ton veshble
C) No inlormaken
about procu eaibi h:
mechanital
d) No inlomabhen about perlovmante of
on veon device

Thevmal &neyy Reservoir CTER): A laxge body o nhna

heat Capaiy capablu absexbing and rejeckg
d
haat wi hou change in henodmamn

PTopeahesAt procaMes involutug TER ae qua

ataic Two typeA
-ligh Temperatue,TER n Sourte
Sink
Lo Tem belature TER Lor)
net hoat
A Aivice in shichHhea is
a
Heat bnqune
work tratetom
tnto the syatem and net
tYanoler
t aystem

Secend La emody nam

Kelvin-Plamck stakement Sowt
at T
I mo&udl os, hat engine
prodmta not uwonk a Complere tytle
by exehangung hoa *oih any a sim HE
body a a fixed teperatuu
Sinkat
12

T
clausius Statement: Atmosphan
a Ti
Ji inpossible b onifruet a

dvite which, opeakng in a cyele

wil
produe no otan eer
han he transa kem a oo le HP
-to a hotte bo
1eato and Heat fump
m
Sodyat
emgeater s a device that kees a bod
at toler Cendions otth he Surromdungs hot

Aheat pmp a devite hat kan the body hs

wmeti surtowndangs Cool
CCol)R T CT2T/Ra<)
2-Q T-T

(CoP)P T
oP)ip :(CoP), +1.
T G-Q
Popetua Moton Machne- tPMM2) A davia
hat violates the LeLond law ethe by
ranshung hoat wh a ingl vetewoir
eny Ce by axchangung heat fuon 6obl o
hrt od whoud oaid o extenal wosk.

CARNOT CYCLE CARNOT THEOREM :.

Caynot hh: A apothe teal eveu t,a Cyele
yele
revevs1ble pmocees
Combring
revestblo othanm md 2revencdole
adiabatu.
 ,e
2

r We
We

S
V
-2 Reveuible iso hasmal. Covinprenion Heatng
-3 Revesibe adiab ahe expanm 0n
3-4 Revexaibe isothenmal Coo n
A-I:Reveuible adiabattc Cempexaon.

caxnbt : I- l- 2
T
RaveAed Carnot Gyele ene wmth has all tha
PTOLOes reveud n direckon C Heat pump

eqeato)
a
CasnotTheovem o al htat engings ope
ssame ouwta and nk temperatwrss, the
reveuds heat enqund have the maximcum

ienty
*ueny all keat enqines (revetble)

DpeAatug betweon Aame tempesat we Ranges u

same

Thexmodnamit Temperatuu Stale

| All tenteickwos
T hn Kolvn Scale

T: 213-1
 Fox Hhis ystem,
T
. 22

TaT Ts

T Tt T3

lixing 2 fluids

As the proces eacha

eqmubrIum, aValabtu
T ale tn eayek
Contunudusly
At eqibriu, avalaloi tu
maXiM um

-hu entropy a equkbrum

e Entvopy Avallabiuly and JYyeyeva btuj.

Available Enesgy: IhA max

im wok obtaindo
whtn nk a
heaf engin
hon oyehe
a

SYTDunding temexatw
At Wmax

max
Totembe^atuni osuroundavg koo
Sped at
Ireveuibi Unavailab treg eeno
beboeen Availalle engy amd actual wotk
tput
T Wmax-wW
CAUSES OF 1RREVERSIBILI T
1: lack o Equlbrium
a) Heah trana throvgh.a ite Tempesao
leenu
b)latk premuM qwhori um.
c) ree expanuon

2 Dissipatve Ekheeks
a) Frickon
Padale whee tek Tans

c)Elecioty.ransp trough etuton. (o ve

Raveible adabat wolk ina a atead

lou procos

w-(volp
1
tOP The ma dodo A ten
ds d
' d8 Tds [Baic Heat Equaken)
Clauni Theorem; R- a u b l e

inteuect
* f u o evetble aoiabahe patha cannot
each o heR on uolated ystem
Enkopy o
a u r a tnuaes amd
Clauis In4uak:
da O u a n e
exengy auuys

is reveble
0 , Cych
'u YTeveuuble poible
Cyu
u impotsible
>o, ycle

Rler Casnot tyele dagram

S S4
T , Cs,-S,) SS3
SA
T CS3 S4
nt Qa T , T3) (5, S1)
*Enkropy o a popes tho aystem.

Enhopy choge an rreveibu prote,

S S dq
,T
Cnhopy Pirnúple
Irevem ble
Reveub dSiso
S : Coretanf
Guoy Stodola. Thaorem
* ¥AA** **** A*
I To ( ASqen)
t A>surv
ASgen ASuniv ASsys
ASuniwo

ENTROPY g iRREvERSIBILITY:
tHeat Traneher through a imi tembeauw
d heence
ASunav T2T

To (ASuniv)

2Maximum wotk obtainable hom a m i body

and a TER/Eexgy t6 bod a t

a tempexatw T:

WmAx:C[7-T-To n To
T ER tembexatoe
3. Mavimum woye ootainable huom two nue
odie a diteunt tempeatu *T,

Wax:Cp VT -VT
4. Flos with ickon:

ASqen mRAp
P
TASsenmR A
5 Mixing two uids:
ASuniv m,cp tn py
T T2

(BSuriv)mas 2
mptn ) 7(m
-pr
-Tha T) T Ta m, M

m p tn.
* Gunaal ovmula S T
*Entvopy unnin phase chamq
SS rm h
T
sothemal diipation wek

W
ASuniv
To(ASuni) . To
To

Adasate wek dis spaton CPaddle whel oe):

AS m Cp tn T
T
Hes tempezatee tnuoaxei due padda wheel

stviand T ound w d o
wmpCTT:) hene

wek den reveublu proçe greate

hon hat n an
reueibu protay
proteM and owsotk
n 1w alreueusto 'bvotesne tu Aame

Secondlauo haamodunamcs ca La
Deqad aken d tneay
 Mixing Juds Cinulated
Box-1 Box 2

,Va
T T

3 V,P2
V +V2

Chonqe in entrop atiD ciated

e
hoat varhe
8 Exerqy balana le a closed system

maxU,-U, +(y V) -To(S-S)

Exexgy balance jos a

steady too Aystem
max (H-H) - T CS, -S ) Add vele
Team
(4,-To Sy ) -
(H,- T,S) tid
B,- Ba
H - TS Keenan tunckon

*tuoy Stodola ebrem exeraprinuple

Pepehual Moten Macune 3 (PMM3). A macwn
bpesatr in
templete obsenta ken
Thind Las hermodnamiu

Fousle-Guaqenhaim Statement f embetubl

e d u c e a yster, no matte houo iaaise,
e absolute Zo o Hempexatwa n a

rwmrumbee q operaho, by procedsa .

Nenst -Simon Statement : It a impessibl to
attain Xao entropu a
ystem, o matter
how ideaised ina
a
,
nate rumben e
Opexatens

3 HB Callen Postulate : trtvopy at, absoute

td-o.
T-
T
 Seond taus lticenec

caxnot
W wmax
"easnot

Wmax (*
ibbs unchovn G) H TS
Helmholtz functen CE) : U-TS
first and Second laws ombinad
d& dE+dw >Any proas any ^ysem
9 4 du tdw -> closed Syskem, any prOOS.
3. d:duapdlV closed Sustern
->
reve-tsbla ua
wesk.
Atahc pro cw i t h pdv

d:TdS - Ony fo evertble,PTOCo N.

5 TAsdUtpdv > elosed system, an roleK.

6 TdS dH-vdp > closd system, mpot0iS protoi

) Rre Substantes:
wmch na homogeneow
homogencou
wmch
pure Aubstamte i ona m
chemical tomboiikon
tha Aysfem n
4hroughot
all phae

opet duagvam eAubslances:

4 b-hdiagva
b- V dagram
5h-S diagram(Mldlie
2 TS diagirasn
-T diagram 6p.V- Surat

Sub Cooled reqio

2Saturated liguid ine.

3. Wet Vapoun Tegien

de d klaharto apou
Citical point igwd
4 Criica poimt, any
amount qhaa
Beyond
in Sytam
addhen does no brng a n hange

5. Triple point ne
Saturated Vapou kine.
6
Supe heated regien

PRoPERTIEs FROM STEAM TABLES:

1Specitie enthalpy Ch h and a)
Spei Volume Cy d V
Spe enhopy (4 A A
Dyneation (a):
Man Vapoar
mas wer Vapour
 a70tahuated haud
1Cakurated Vapour DrAatuatad steam)
Onl We Vapou Satunalid Stali
_
PT a dspondint

1et Vapou qn V

-4

Liquid /eaburatod iguid Dutng phaye

aturated Vapou
dhare
dGo!P:6
w e t vabous Tegen

2 Suo looled Regei TSatarated

Vae Tsc Sub coleo

h -(pu) (T-Tsc) |G
h Pt(T/Tac)g phua
(Also Calud onpreted id)
3 Supes alcd Kga
hAhhg Gpp (Tsh-T.) T-Sahuwat ed
Tah Supen
heat ed
ap Vapo

T6
OTHER RoPERTY RELATIONS:
Extetna wok of evaporaton
( dD steam)
=f Cet steam)
2Tntemal latent hea
CS, I : 1)
3.ternal entgy steam
Wet Steam, uh
h-p1V h-t.n a
Sape Laed, h-
Sted
Entpy thange wae
S q ln (/T)
T O'c T, T
S r (/273)
5. Enthdpy evaberaten
Sevapha Cowlete
'ewapratn)
T
h patal evapenation wt
T drnn ton
Tsentropic exparien
W u,-u SS

ThrettL-q (ntant enhalpy an ve

docaoobe)
hh T T S 7
Tuo phase Systemhas o dig re
hadom a equk
bvium
Thnes pha ytem (tripe point) ha zao
dagres
oeadom a caumrium

vapou annot be
Aove Cvikoal temfeatat a
Above
eu
bigwiied y a monif
*Enthalpy vapouusaton point zero
.Cricad point

*O -T diagram, boh triple critca) points a

pOInfs

ponts
Gns
On-V diaqvam,tmpe point a

tical point a point

robees Gases amd Gas Lxtwes

 waler
fo waer
>n-) (ados
slop
Fuluen wrve
v e
Substan a

C-ve Fuhen
ofhe
i h y

C to v e S o p e s
Slope

a n y
any

fe
C r i h c a poinT

(iN
Vapowis aken
Soid Cwnve
S
point.
Tripu
(Vopou

Sui maton Cwve

T
 As sat
t Tsol 1
As kal , henp avd Psat

As Psal , UT
As , s'T

*Ac p

o a pue Substanta db
a . Vopdu 2
Sup eatVapo 2.
 Enro in hee expanwon

n R
V
dT
dL udT v vdT t dt
dt dy dr
is in molas
e mixin e
2n X2t
e-R (n, n a,
+
S
+ n k)

Ay n y
t
n 2, +2, InZ,
-

R
3Properte Gase amd Gas Mixtures.
Tdsal ajes oey all qas laiss Raa ges
exhebit tdsql behasiou at loutaptn
pMeM ond, .bugh tembesakuneS
Thess n o attractken betueshmlecales Ln
an
idaal gas and ocoupie iqhar. speie, vouimu
Cvice-Vesao eal 9 e s )

Bales aw ):
(1sollanal Pr
PV C

Chaaler lauw CIso bae reen)

Luacs LaIse chorie Proas):

C
 V m RT

-V: m RT
V N T

premue (abs, N/m)

V: Vvolme ( )
m:mas

Speie éas Gonatants/k)

tveual Ga Ganjant
3314 amole
mo as
M: M
Not sdlas weqk ka) mou)
T Akoselute tempedtua. tk)
N Avoqadvo N.mbes
023 xtoam mole
6r025 to mole
Boltzmann ' onstant
16
3 (O

.C
T
Van der wanl ueteni
( P ) Cr.b RT

Tee
Cvicad velums,
64 tempasatu
RT

Jaes,oheji H la
PV
mRT

7 CempvewmbiUttatkor: 1 fn tdeal jase

ADIABATIc ProcEss iNDEX
PV Codan
Adiabate indax
Cy
CSpe
C keat o q at Conant praxmi
hiat qgs at Consfant volumt
CySpeape
Cp-CvR (t any 3
Cv
M
M

Y-1

Ralaem propestes tn adhbate prou

PV:C PT ()e
%Cp(v tnacare wtth Tembesatwe, but
re in y
Te tn
C
Cp au han

GT\ T and /aT

Cy
he T 3 chert
Ma actin (y2 Rato ma oindivisle
indvidua
gs-lo otal mav ga 1xture.

mT

y 1
Mole rasten Ca)t Ratko
no mo
indvi dnal gaa to
no mol a Yxtus.

i i
T
M
2 1
Veluma 4ratten:Mole tra

MT
m nTMi
Dalte Ttotal
pTeune exexted
bya3a esma o ha Sum qL
Te pahal
exested b ndi
Cnstamt vo lume amd viduol gas
s 4t
empeatwuL
t p 4. +t
Yata PX Gras
mr ue

Melecula eght
M M
 yaslomtant yas wxb
R R Z R
RT
MT 21 Mi

eyey ga
Avo qodvoau AA NTP, 1 .moe
OCcuies a volume 224 WEres

Amagot La Tha total volume d gas o

t h e aum q indiividual, voumay

o a ga
Conatant temperatu pren wa

Inkernal Enexay Ehalpy Entopy ces R

T y: ui
hT2 y CT
T

Chenge entvopy n dal ge

S,S tn+RLn("/%)

p n(7/1)-
Rln
("A)
GLn()+yt»[B/a)
Rolytnepie Specibie beedi .
Cn ) Cv"
 c
CO
cOld
3
hhermodynamic Relaton.

dz Md 4 Ndy
for exact lleenta
DD
OM
N

MAxWELs RELATION S:
duTds pdv"
2 dt Tas+ vdP
3 dF -pdv-sdT
4 dG-vdP -sdr

raP

(3T (es

Tds EQUATIONS:
TAS CvdT+ TOT
(d
2 TdS Cp T T
(
SPECtFIC HEATS
Volume Expanivi
Coeeent
Isoter mal Compreabikli, kT : -_

d'abotie Compreibit s

p-CyR-TV for ai
Coo5 k
C :K
ACv Ro101.|
t4
A t absoute zao, (p :Y
Cp-y T ((ov/

p C

Teule-Keluo het cert

Thvottng9. a l a o Calld Jole kolvin e

Joule Thonsen expanmon

s
Numevcal vau ot slape o enthalpe
an

Callsd Joule kolvin Joule Thomson loelsiter

i
Locusall pan ohese JT toehent
tallud nveALen Cutve
Above v e
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