Vij ay Agarwal Thermodynami cs 6 4 7

T h er m od yn am i cs i s a br anch of sci enc e w hi ch d eal s w i t h exch an ge of

h eat en er gy b et w een b od i es an d conv er si on of t h e heat en er gy i n t o
m ech ani cal en er gy and vi ce- ver sa.
Some Definitions
( 1) T her m od yn am i c syst em
( i ) I t i s a col l ect i on of an ext r em el y l ar ge n um ber of at om s or
m ol ecul es
( i i ) I t i s c onf i n ed wi t h i n cer t ai n bou n d ar i es.
( i i i ) An yt h i n g out si de t he t her m od yn am i c syst em t o wh i ch en er gy or
m at t er i s exch an ged i s cal l ed i t s su r r ou ndi ngs.








( i v) Th er m od yn am i c syst em m ay b e of t h r ee t yp es
( a) O p en syst em : I t exch an ge b ot h en er gy and m at t er w i t h t h e
su r r ou n di n g.
( b) Cl osed sy st em : I t exchan ge onl y ener gy ( n ot m at t er ) w i t h t h e
su r r ou n di n gs.
( c) I sol at ed syst em : It exchan ge n ei t her en er gy n or m at t er w i t h t h e
su r r ou n di n g.








( 2) T her m od yn am i c var i abl es an d eq u at i on of st at e : A t her m od yn am i c
syst em can b e d escr i b ed by sp eci f yi n g i t s p r essu r e, vol um e, t em per at u r e,
i n t er n al ener gy an d t h e n um b er of m ol es. T h ese p ar am et er s ar e cal l ed
t h er m od ynam i c v ar i abl es. T he r el at i on bet w een t h e t h er m od yn am i c
var i abl es ( P, V, T) of t h e syst em i s cal l ed eq u at i on of st at e.
For m ol es of an i deal gas, eq u at i on of st at e i s PV = RT an d f or 1
m ol e of an i t i d eal gas i s PV = RT
( 3) T h er m od yn am i c eq ui l i br i um : I n st ead y st at e t h er m od yn am i c
var i abl es ar e i n d epen dent of t i m e and t h e syst em i s sai d t o be i n t he st at e
of t h er m od yn am i c eq u i l i br i um . For a syst em t o b e i n t her m od yn am i c
eq u i l i b r i um , t h e f ol l owi ng con di t i ons m ust b e f ul f i l l ed .
( i ) M ech ani cal eq ui l i b r i um : T her e i s n o u n b al anced f or ce b et ween t h e
syst em and i t s sur r ou nd i ngs.
( i i ) Th er m al eq ui l i b r i um : T h er e i s a u ni f or m t em p er at u r e i n al l p ar t s
of t he syst em and i s sam e as t h at of sur r ou nd i ng.
( i i i ) Ch em i cal equi l i b r i u m : Th er e i s a u ni f or m c hem i cal com posi t i on
t h r ou gh out t h e syst em an d t he su r r ou nd i ng.
( 4 ) T h er m od yn am i c pr ocess : The p r ocess of c h ange of st at e of a
syst em i n vol ves chan ge of t h er m od yn am i c var i abl es su ch as p r essu r e P,
vol um e V an d t em p er at ur e T of t he syst em . T he p r ocess i s k n ow n as
t h er m od ynam i c p r ocess. Som e i m por t ant p r ocesses ar e
( i ) I sot h er m al p r ocess : Tem p er at u r e r em ai n con st an t
( i i ) Ad i ab at i c p r ocess : No t r an sf er of heat
( i i i ) I sob ar i c p r ocess : Pr essu r e r em ai ns const an t
( i v) I sochor i c ( i sovol um i c p r ocess) : Vol um e r em ai n s con st ant
( v) Cycl i c and non- cycl i c pr ocess : Incycl i c pr ocess Ini t i al and fi nal st at es
ar e sam e whi l e i n non-cycl i c pr ocess t hese st at es ar e dif f er ent .
( vi ) Rever si bl e an d i r r ever si bl e p r ocess :

Su r r ou n di n g
Syst em G as
Fi g. 14 .1
T h er m od yn am i cs
Chapter
14

6 4 8 Thermodynami cs Vij ay Agarwal

( 5) I nd i cat or d i agr am : W hen ever t h e st at e of a gas ( P, V , T ) i s
ch anged , w e say t he gaseou s syst em i s u nd er gon e a t h er m od yn am i c p r ocess.
T h e gr ap hi cal r epr esent at i on of t he ch ange i n st at e of a gas by a
t h er m od ynam i c p r ocess i s cal l ed i nd i cat or d i agr am . I n di cat or di agr am i s
p l ot t ed gener al l y i n p r essu r e and vol um e of gas.
Zeroth Law of Thermodynamics
I f syst em s A and B ar e each i n t h er m al eq u i l i b r i um w i t h a t hi r d syst em
C, t h en A and B ar e i n t h er m al eq ui l i b r i um w i t h each ot h er .







( 1) Th e zer ot h l aw l eads t o t h e con cep t of t em per at u r e. Al l bod i es i n
t h er m al equ i l i b r i um m u st h ave a com m on p r op er t y w hi ch has t h e sam e
val ue f or al l of t h em . Th i s p r op er t y i s cal l ed t he t em p er at u r e.
( 2) Th e zer ot h l aw cam e t o l i ght l on g af t er t h e f i r st an d secon d s l aw s
of t her m od ynam i cs h ad b een d i scover ed an d n um b er ed . I t i s so nam ed
b ecau se i t l ogi cal l y p r eced es t h e f i r st an d secon d l aw s of t h er m od yn am i cs.
Heat, Internal Energy and Work in Thermodynamics
( 1) H eat ( Q ) : I t i s t h e en er gy t h at i s t r an sf er r ed b et w een a syst em
an d i t s en vi r onm ent b ecau se of t h e t em per at u r e di f f er en ce b et ween t hem .
( i ) Heat i s a p at h dep end ent q uant i t y e.g. Heat r eq u i r ed t o ch ange t h e
t em p er at u r e of a gi ven gas at a con st ant pr essu r e i s di f f er ent f r om t h at
r eq ui r ed t o c hange t h e t em p er at u r e of sam e gas t h r ou gh sam e am ou nt at
con st ant vol um e.
( i i ) For gases w hen heat i s ab sor bed an d t em p er at ur e ch anges
T C Q A = A
A t con st ant p r essu r e T C Q
P P
A = A ) (
A t con st ant vol um e T C Q
V V
A = A ) (
( 2) I n t er n al ener gy ( U ) : I nt er nal ener gy of a syst em i s t h e en er gy
p ossessed b y t h e syst em du e t o m ol ecul ar m ot i on and m ol ecu l ar
conf i gu r at i on .
T h e en er gy d u e t o m ol ecul ar m ot i on i s cal l ed i nt er n al ki n et i c ener gy U
K

an d t hat d u e t o m ol ecul ar c onf i gu r at i on i s cal l ed i nt er nal pot ent i al en er gy U
P

i .e. T ot al i nt er n al en er gy
P K
U U U + =
( i ) For an i d eal gas, as t h er e i s n o m ol ecul ar at t r act i on 0 =
p
U
i .e. i nt er n al en er gy of an i d eal gas i s t ot al l y k i net i c and i s gi ven b y
RT U U
K

2
3
= = and ch ange i n i nt er n al en er gy T R U A = A
2
3

( i i ) I n case of gases w h at ever be t h e p r ocess
T R
f
U A = A
2
T C
V
A =
1
) (
) 1 (

= A

i f
T T R
T
R


1

i f
RT RT
1
) (

i i f f
V P V P

( i i i ) Change i n i nt er nal ener gy does not d ep en d on t h e p at h of t h e
p r oc ess. So i t i s cal l ed a p oi nt f u nct i on i .e. i t dep end s onl y on t he i ni t i al an d
f i n al st at es of t he sy st em , i .e.
i f
U U U = A
( 3) W or k ( W ) : Su p p ose a gas i s conf i n ed i n a c yl i nd er t h at h as a
m ovab l e pi st on at on e en d. I f P be t he p r essu r e of t h e gas i n t he cyl i nd er ,
t h en f or ce exer t ed b y t he gas on t h e p i st on of t he cyl i nd er F = PA ( A = A r ea
of cr oss- sect i on of pi st on)







W h en t h e pi st on i s p u shed out war d an i nf i ni t esi m al d i st ance dx, t h e
w or k don e b y t he gas dV P dx A P dx F dW = = = ) ( .
For a f i ni t e ch ange i n vol um e f r om V
i
t o V
f

T ot al am ou n t of w or k don e ) (
i f
V
Vi
V V P dV P W
f
= =
}

( i ) I f w e d r aw i n di c at or di agr am , t h e ar ea b oun d ed b y PV - gr aph an d
vol um e axi s r ep r esent s t h e w or k d one


W or k = Ar ea = P( V
2
V
1
)





W or k ) (
1 2
2
1
V V P PdV
V
V
= =
}







W or k = 0





W or k = Ar ea of t he show n t r ap ezi um
) ( ) (
2
1
1 2 2 1
V V P P + =


( i i ) Fr om ) (
i f
V V P V P W = A = A
If syst em exp an ds agai n st som e ext er n al f or c e t hen
i f
V V >
AW = p osi t i ve
dx
F
Pi st on
Gas
Fi g. 14 .4
P
V V
1
V
2

P
A
Fi g. 14 .5
P
V V
1 V
2

P
dV
Fi g. 14 .6
P
V
Fi g. 14 .7
P
V V
1
V
2

P
1
P
2
Fi g. 14 .8
Fi g. 14 .3
Sy st em
A
Sy st em
B
Syst em
C
I n su l at i n g
Con du ct i n g
( A)
Sy st em
A
Syst em
B
Syst em
C
Con du ct i n g
I n su l at i n g

( B)
Vij ay Agarwal Thermodynamics 6 4 9

I f syst em cont r act s b ecau se of ext er n al f or ce t h en
i f
V V <
AW = n egat i ve







( i i i ) Li ke h eat , w or k d one i s al so dep end s up on i n i t i al and f i nal st at e of
t h e syst em an d pat h adop t ed f or t h e p r ocess











A
1
< A
2
W
1
< W
2

( i v) I n cycl i c p r ocess, w or k d one i s eq u al t o t he ar ea of cl osed cu r ve. It
i s p osi t i ve i f t he cycl e i s cl ock w i se an d i t i s negat i ve i f t h e c ycl e i s
an t i cl ock w i se.


W or k = Ar ea of t r i angl e A BC
) ( ) (
2
1
1 2 1 2
P P V V =




W or k = Ar ea of r ect angl e ABCD
= A B AD
= ( V
2
V
1
) ( P
2
P
1
)





W or k = ) ( ) (
4
1 2 1 2
V V P P

First Law of Thermodynamics (FLOT)
( 1) I t i s a st at em ent of con ser vat i on of ener gy i n t h er m od yn am i cal
p r ocess.
( 2) A ccor d i ng t o i t h eat gi ven t o a syst em ( AQ ) i s equ al t o t h e sum of
i n cr ease i n i t s i n t er n al en er gy ( AU) and t he w or k d on e ( AW ) b y t h e syst em
agai n st t h e su r r ou n di n gs.
Q = U + W
( 3) I t m ak es no d i st i n ct i on b et w een w or k and h eat as accor di n g t o i t
t h e i n t er n al en er gy ( and hen ce t em per at u r e) of a syst em m ay b e i ncr eased
ei t h er b y addi n g h eat t o i t or doi ng w or k on i t or b ot h .
( 4 ) AQ an d AW ar e t he p at h f u nct i on s b ut AU i s t h e poi nt f u nct i on.
( 5) I n t he ab ove eq u at i on al l t hr ee q uan t i t i es AQ , AU and AW m u st
b e exp r essed ei t h er i n Joul e or i n cal or i e.
( 6 ) Th e f i r st l aw i nt r od u ces t h e concept of i nt er n al en er gy.
( 7) Li m i t at i on : Fi r st l aw of t h er m od yn am i cs d oes not i nd i cat e t h e
d i r ect i on of h eat t r an sf er . I t d oes n ot t el l an yt h i ng about t h e cond i t i ons,
u n d er w hi ch h eat can b e t r an sf or m ed i n t o w or k and al so i t d oes n ot
i n di cat e as t o w hy t he w h ol e of heat ener gy can n ot b e con ver t ed i n t o
m ech ani c al w or k con t i nuou sl y.
T ab le 14 .1 : U sef u l sign convent ion i n t her m od yn am ics
Q u an t i t y Si gn C on di t i on
AQ
+ W h en h eat i s su p p l i ed t o a syst em
W h en h eat i s d r aw n f r om t h e sy st em
AW
+ W h en w or k don e b y t h e gas ( exp ansi on )
W h en w or k don e o n t h e gas ( comp r essi on )
AU
+ W i t h t em p er at ur e r ise, i n t er n al en er gy i ncr eases
W i t h t em p er at ur e f al l , i nt er n al en er gy decr eases

Isobaric Process
W h en a t h er m od yn am i c syst em u nd er goes a p h ysi c al ch ange i n su ch a
w ay t hat i t s p r essu r e r em ai n s const an t , t h en t he ch ange i s k n ow n as
i sob ar i c p r oc ess.
( 1) Eq u at i on of st at e : I n t hi s p r ocess V an d T ch anges b ut P r em ai n s
con st ant . H ence Ch ar l e s l aw i s ob eyed i n t hi s p r ocess.
Henc e i f p r essu r e r em ai n s const ant V T
2
2
1
1
T
V
T
V
=
( 2) I n dicat or d i agr am : Gr aph 1 r ep r esent i sobar i c ex pansi on , gr aph 2
r ep r esent i sobar i c com p r essi on.



Sl op e = 0 =
dV
dP
Sl op e = 0 =
dV
dP




( i ) I n i sobar i c exp an si on ( H eat i ng)
T em per at u r e i n c r eases so AU i s p osi t i ve
V ol um e i ncr eases so AW i s posi t i ve
Heat f l ows i nt o t h e syst em so AQ i s p osi t i ve
( i i ) I n i sob ar i c com p r essi on ( Cool i ng)
T em per at u r e decr eases so AU i s negat i ve
P
A
V
( A) Exp ansi on
B
Po si t i v e
w or k
( B) Comp r essi on
P
A
V
B
Negat i v e
w or k
Fi g. 14 .9
P
V
A 2
1 B
P
V
A
1
B
A
1
( A) Less ar ea
P
V
A
2
B
A
2
( B) M or e ar ea
Fi g. 14 .10
P
2
P
1
A
C
B
V
1
V
2 V

P

Fi g . 14 .11
P
2
P
1
V
1
V
2 V

P

Fi g. 14 .13
P
2
P
1
A
C
B
V
1
V
2 V

P

Fi g. 14 .12
( A) Exp ansi on

P

V

1
P

V

2

( B) Com p r essi on

Fi g. 14 .14

6 5 0 Thermodynamics Vij ay Agarwal

V ol um e d ecr eases so AW i s n egat i ve
H eat f l ow s out f r om t h e sy st em so AQ i s negat i ve
( 3) Sp eci fi c h eat : Speci f i c h eat of gas d u r i n g i sobar i c p r ocess
R
f
C
P
|
.
|

\
|
+ = 1
2

( 4 ) Bul k m odulus of elast icit y : 0 =
A
A
=
V
V
P
K [ A s AP = 0 ]
( 5) W or k d on e i n i sob ar i c p r ocess
] [
i f
V
V
V
V
V V P dV P dV P W
f
i
f
i
= = = A
} }
[ A s P = con st ant ]
T R T T R V V P W
i f i f
A = = = A ] [ ) (
( 6 ) FLO T i n i sob ar ic pr ocess : Fr om W U Q A + A = A
T C U
V
A = A T
R
A

=
) 1 (
and T R W A = A
T R T
R
Q
P
A + A

= A

) 1 (
) ( T R A
|
|
.
|

\
|

=
1

T C
P
A =
( 7) Exam pl es of i sob ar i c p r ocess : Al l st at e ch anges occ ur s at con st ant
t em p er at u r e an d pr essu r e.
Boi l i ng of w at er
( i ) W at er vap our s
( i i ) T em per at u r e con st ant
( i i i ) Vol um e i n c r eases
( i v) A p ar t of h eat sup pl i ed i s u sed t o ch ange v ol um e ( exp an si on)
agai n st ext er nal p r essu r e an d r em ai ni ng p ar t i s u sed t o i ncr ease i t ' s
p ot ent i al ener gy ( ki n et i c en er gy r em ai n s con st ant )
( v) Fr om FLO T AQ = AU + AW m L = AU + P( V
f
V
i
)
Fr eezi ng of w at er
( i ) W at er i ce
( i i ) T em per at u r e const ant
( i i i ) Vol um e i n c r eases
( i v) H eat i s gi ven b y w at er i t sel f . It i s u sed t o do w or k agai n st
ext er n al at m osp her i c p r essu r e an d t o d ecr eases t h e i nt er n al p ot en t i al
en er gy.
( v) Fr om FLO T AQ = AU + AW m L = AU + P( V
f
V
i
)
Isochoric or Isometric Process
W hen a t h er m od yn am i c p r ocess u nd er goes a p h ysi cal ch ange i n su ch a
w ay t h at i t s vol um e r em ai n s con st ant , t hen t h e ch ange i s k n ow n as
i soch or i c p r ocess.
( 1) Eq u at i on of st at e : I n t h i s pr ocess P an d T chan ges b ut V =
con st ant . Hence Gay- Lu ssac s l aw i s obeyed i n t hi s pr ocess i .e. P T
= =
2
2
1
1
T
P
T
P
con st ant
( 2) I n dicat or d i agr am : Gr ap h 1 an d 2 r ep r esent i som et r i c i ncr ease i n
p r essu r e at vol um e
1
V an d i som et r i c decr ease i n p r essu r e at vol u m e
2
V
r esp ect i vel y and sl op e of i nd i cat or di agr am =
dV
dP

( i ) I som et r i c h eat i ng
( a) Pr essur e i n cr eases
( b) Tem p er at ur e i n cr eases
( c) AQ p osi t i ve
( d) AU posi t i ve
( i i ) I som et r i c cool i ng
( a) Pr essur e d ecr eases
( b) Tem p er at ur e decr eases
( c) AQ n egat i v e
( d) AU negat i ve

( 3) Sp eci fi c h eat : Speci f i c h eat of gas d u r i ng i soch or i c p r ocess
R
f
C
V
2
=
( 4 ) Bu l k m od ul u s of el ast ici t y : =
A
=
A
A
=
0
P
V
V
P
K
( 5) W or k d on e i n i soch or i c p r ocess
] [
i f
V V P V P W = A = A = 0 [ A s V = const an t ]
( 6 ) FLO T i n i sochor ic p r ocess : Fr om W U Q A + A = A
AW = 0 T C U Q
V V
A = A = A ) ( T
R
A

=
1

i i f f
V P V P

Isothermal Process
W h en a t h er m od yn am i c syst em u nd er goes a p h ysi c al ch ange i n su ch a
w ay t h at i t s t em p er at u r e r em ai n s const ant , t h en t h e ch ange i s k n ow n as
i sot h er m al chan ges.
( 1) Essent ial condi t i on f or i sot h er m al pr ocess
( i ) T he w al l s of t h e con t ai ner m ust b e p er f ect l y con d uct i ng t o al l ow
f r ee exch an ge of heat b et w een t he gas an d i t s su r r ou nd i n g.
( i i ) Th e p r ocess of com p r essi on or exp an si on sh oul d b e so sl ow so as
t o p r ovi d e t i m e f or t h e exch ange of h eat .
Si n ce t h ese t w o cond i t i on s ar e n ot f ul l y r eal i sed i n p r act i ce, t her ef or e,
n o pr ocess i s p er f ect l y i sot h er m al .
( 2) Eq u at i on of st at e : I n t h i s p r ocess, P and V c hange but T =
con st ant i .e. ch ange i n t em p er at u r e AT = 0 .
Boyl e s l aw i s ob eyed i .e. PV = con st ant P
1
V
1
= P
2
V
2

( 3) Exam pl e of i sot h er m al p r ocess : M el t i n g of i ce ( at 0C) and b oi l i n g
of w at er ( at 10 0C) ar e com m on exam pl e of t hi s p r ocess.
( 4 ) I ndicat or di agr am : Accor di ng t o PV = con st ant , gr aph b et w een P
and V i s a par t of r ect angul ar hyper bol a. The gr aphs at di f f er ent t em p er at u r e
ar e p ar al l el t o each ot her ar e cal l ed i sot her m s.


T
1
<T
2
< T
3

T w o i sot h er m s n ever i n t er sect
Fi g. 14 .15
W at er Vap ou r s
Fi g. 14 .16
W at er
I ce
P

V

1
V
1
( A)

P

V

2

V
2
( B)

Fi g. 14 .17
T
3
T
2
T
1
P

V

Fi g . 14 .18
Vij ay Agarwal Thermodynamics 6 5 1





( i) Sl ope of i sot her m al cur ve : By dif f er ent i at i ng PV = const ant . W e get
0 = + dP V dV P
VdP PdV =
Sl ope =
V
P
dV
dP
= = tan

( i i ) A r ea bet w een t he i sot h er m an d vol um e axi s r ep r esen t s t he w or k
d on e i n i sot h er m al pr ocess.
I f vol um e i ncr eases AW = + ( Ar ea u nder cu r ve) and i f vol um e
d ecr eases AW = ( Ar ea u nd er cu r ve)
( 5) Sp eci fi c h eat : Speci f i c h eat of gas d u r i n g i sot h er m al ch ange i s
i nf i ni t e. A s =

=
A
=
0 m
Q
T m
Q
C [ A s AT = 0 ]
( 6 ) I sot h er m al el ast i cit y ( E

) : For t h i s pr ocess PV = con st an t .

dP V dV P =

E
V dV
dP
P = =

=
Strain
Stress
/

P E =

i .e. i sot her m al el ast i ci t y i s eq u al t o p r essu r e

A t N.T .P., E

= At m ospher i c p r essu r e =
2 5
/ 10 01 . 1 m N
( 7) W or k d on e i n i sot h er m al p r ocess
} }
= =
f
i
f
i
V
V
V
V
dV
V
RT
dV P W

[ A s PV = RT]
|
|
.
|

\
|
=
|
|
.
|

\
|
=
i
f
i
f
e
V
V
RT
V
V
RT W
10
log 303 . 2 log
or
|
|
.
|

\
|
=
|
|
.
|

\
|
=
f
i
f
i
e
P
P
RT
P
P
RT W
10
log 303 . 2 log
( 8 ) FLO T i n i sot h er m al p r ocess : Fr om W U Q A + A = A
0 = AU [ As AT = 0 ] W Q A = A
i .e. heat su p pl i ed i n an i sot h er m al ch ange i s used t o do w or k agai n st
ext er n al su r r oun di ng.
or i f t h e w or k i s don e on t he syst em t h an eq u al am ou nt of h eat en er gy
w i l l b e l i ber at ed b y t he syst em .
Adiabatic Process
W hen a t h er m od ynam i c syst em u n d er goes a ch an ge i n such a w ay t h at
n o exchan ge of h eat t akes pl ace bet w een Syst em and su r r oun di n gs, t he
p r ocess i s k now n as adi ab at i c p r ocess.
I n t hi s p r ocess P, V an d T ch an ges b ut AQ = 0 .
( 1) Essent i al condi t i on s f or adi ab at i c p r ocess
( i ) Th er e sh oul d n ot b e an y exch ange of heat bet w een t he sy st em an d
i t s su r r ou nd i ngs. A l l w al l s of t h e cont ai n er and t he p i st on m u st b e per f ect l y
i n sul at i ng.
( i i ) T h e syst em sh oul d b e com p r essed or al l ow ed t o exp and su dd enl y
so t hat t her e i s n o t i m e f or t h e exch ange of heat b et w een t h e syst em and i t s
sur r ou n di n gs.
Si n ce, t h ese t w o cond i t i on s ar e n ot f u l l y r eal i sed i n p r act i ce, so n o
p r oc ess i s per f ect l y ad i ab at i c.
( 2) Som e exam p l es of ad i ab at i c p r ocess
( i ) Su dd en com p r essi on or exp an si on of a gas i n a con t ai n er w i t h
p er f ect l y n on- cond uct i ng w al l s.
( i i ) Su dden b u r st i ng of t he t ub e of b i cycl e t yr e.
( i i i ) Pr op agat i on of soun d w aves i n ai r an d ot h er gases.
( i v) Exp an si on of st eam i n t h e cyl i nd er of st eam engi ne.
( 3) FLO T i n adi ab at i c p r ocess : Fr om W U Q A + A = A
For adi ab at i c p r ocess 0 = AQ W U A = A
If AW = posi t i ve t h en AU = n egat i ve so t em p er at u r e decr eases i .e.
ad i ab at i c ex pan si on p r od uce cool i n g.
If AW = n egat i ve t h en AU = posi t i ve so t em per at u r e i nc r eases i .e.
ad i ab at i c com p r essi on p r od uce heat i ng.
( 4 ) Eq u at i on of st at e : I n ad i ab at i c ch ange i deal gases d o not ob eys
Boyl e' s l aw b u t ob eys Poi sson 's l aw . Accor di n g t o i t
PV

= con st ant ; w h er e
V
P
C
C
=
( i ) For t em per at u r e and vol um e
T V

1
= con st an t
1
2 2
1
1 1

=

V T V T or

1
V T
( i i ) For t em p er at u r e and p r essu r e
1

P
T
= con st .

=
1
2 2
1
1 1
P T P T or

1
P T or
1

T P
T ab le 14 . 2 : Speci al cases of ad iab at ic p r ocess
T yp e of gas

V
P
1

1

T P
1
1

V
T
M o n oat o m i c
= 5/ 3
3 / 5
1
V
P

2 / 5
T P
3 / 2
1
V
T
D i at om i c
= 7/ 5
5 / 7
1
V
P

2 / 7
T P
5 / 2
1
V
T
Pol yat o m i c
= 4 / 3
3 / 4
1
V
P
4
T P
3 / 1
1
V
T

( 5) I n dicat or di agr am
( i ) Cu r ve ob t ai ned on PV gr ap h ar e c al l ed ad i ab at i c cur v e.
( i i ) Sl op e of adi abat i c cu r ve : Fr om constant =

PV
By di f f er ent i at i ng, w e get
0
1
= +

dV V P V dP


|
.
|

\
|
= =

V
P
V
PV
dV
dP


1


P

V


Fi g. 14 .19

P
V
Fi g. 14 .2 0

6 5 2 Thermodynamics Vij ay Agarwal

Sl ope of ad i ab at i c c u r ve |
.
|

\
|
=
V
P
tan
( ii i) But we al so know t hat sl ope of i sot her m al cur ve
V
P
= tan
H en ce ( Sl op e)
Ad i
= ( Sl ope)
Iso
or 1
Slope) (
Slope) (
>
Iso
Adi

( 6 ) Sp eci f ic heat : Speci f i c h eat of a gas d u r i n g adi abat i c ch ange i s
zer o As 0
0
=
A
=
A
=
T m T m
Q
C [ A s Q = 0]
( 7) A d i abat i c el ast i cit y ( E

) : constant =

PV
D i f f er ent i at i n g b ot h si des 0
1
= +

dV V P PV d

E
V dV
dP
P = =

=
Strain
Stress
/
P E

=
i .e. ad i ab at i c el ast i ci t y i s t i m es t h at of p r essur e
A l so i sot h er m al el ast i ci t y P E =

V
P
C
C
E
E
= =

i .e. t h e r at i o of t w o el ast i ci t y of gases i s eq u al t o t h e r at i o of t w o
sp eci f i c h eat s.
( 8 ) W or k d on e i n ad i abat i c p r ocess
}
=
f
i
V
V
dV P W
}
=
f
i
V
V
dV
V
K

) 1 (
) (
) 1 (
] [

f i f f i i
T T R V P V P
W
( A s PV

= K, P
f
V
f
= RT
f
and P
i
V
i
= RT
i
)
( i ) W q u ant i t y of gas ( ei t h er M or )
( i i ) W t em p er at u r e d i f f er ence ( T
i
T
f
)
( i i i ) W
1
1


tri di mono
> > W
mo n o
< W
d i a
< W
t r i

( 9 ) C om par i son b et w een i sot h er m al and ad i ab at ic i n d icat or di agr am s :
A l w ays r em em ber t h at adi ab at i c cu r ves ar e m or e st eep er t h an i sot her m al
cu r ves
( i ) Eq u al exp an si on : Gr ap h 1 r ep r esent i sot h er m al p r ocess and 2
r ep r esent adi ab at i c p r ocess
W
iso t h erm al
> W
ad i ab at i c

P
i so t her m al
> P
ad i ab at i c

T
i so t her m al
> T
adi ab at ic

( Sl op e)
I so t h er m al
< ( Sl op e)
Adi ab at ic


( i i ) Com p r essi on : Gr aph 1 r ep r esent adi ab at i c p r ocess an d 2 r ep r esent
i sot h er m al pr ocess
W
Ad i ab at i c
> W
I so t h er mal

P
Ad i abat i c
> P
I so t her m al

T
Ad i ab at i c
> T
I so th er mal

( Sl op e)
I so t h er m al
< ( Sl op e)
Adi ab at ic


( 10) Fr ee exp an sion : Fr ee exp ansi on i s adi abat i c p r ocess i n wh i ch n o
w or k i s per f or m ed on or b y t h e syst em . Con si der t w o vessel s p l aced i n a
syst em w hi ch i s en cl osed w i t h t h er m al i nsul at i on ( asb est os- cover ed) . O ne
vessel cont ai ns a gas and t he ot her i s evacu at ed. W h en sud denl y t he
st opcock i s opened , t he gas r u sh es i n t o t he evacu at ed vessel an d expan d s
f r eel y.






AW = 0 ( Becau se wal l s ar e r i gi d)
AQ = 0 ( Becau se w al l s ar e i nsu l at ed)
AU = U
f
U
i
= 0 ( Bec au se AQ an d AW ar e zer o. T h u s t he f i n al an d
i n i t i al en er gi es ar e equ al i n f r ee ex pan si on .
Cyclic and Non-cyclic Process
A cy cl i c p r ocess con si st s of a ser i es of ch anges w hi ch r et u r n t h e
syst em back t o i t s i n i t i al st at e.
I n n on- cycl i c p r ocess t h e ser i es of ch an ges i n vol ved do n ot r et ur n t h e
syst em back t o i t s i n i t i al st at e.
( 1) I n case of cycl i c p r ocess as
i f
U U = 0 = = A
i f
U U U
i .e. ch an ge i n i nt er nal en er gy f or cy cl i c pr ocess i s zer o an d al so
T U A A AT = 0 i .e. t em p er at u r e of syst em r em ai n s con st ant .
( 2) Fr om FLO T W U Q A + A = A W Q A = A
i .e. heat su p pl i ed i s eq u al t o t h e w or k d one b y t h e syst em .
( 3) For cycl i c pr ocess P- V gr aph i s a cl osed cur ve and ar ea encl osed by t he
cl osed pat h r epr esent s t he wor k done.
If t he cycl e i s cl ock w i se w or k don e i s p osi t i ve an d i f t he cycl e i s
an t i cl ockw i se w or k d on e i s n egat i ve.







( 4 ) W or k d on e i n n on cycl i c p r oc ess depends u p on t h e p at h chosen or
t h e ser i es of ch anges i n vol ved an d can be cal c ul at ed b y t he ar ea cover ed
b et w een t h e cu r ve and vol um e axi s on PV d i agr am .








Quasi Static Process
W h en w e p er f or m a p r ocess on a gi ven syst em , i t s st at e i s, i n gen er al ,
ch anged . Su p p ose t he i ni t i al st at e of t h e syst em i s d escr i b ed by t h e val u es
1 1 1
, , T V P an d t he f i nal st at e b y
2 2 2
, , T V P . If t he p r ocess i s p er f or m ed i n
suc h a w ay t h at at an y i n st ant d u r i ng t h e p r ocess, t he syst em i s v er y n ear l y
i n t h er m od yn am i c eq ui l i b r i um , t he p r ocess i s cal l ed qu asi - st at i c. T hi s m eans,
w e can speci f y t h e p ar am et er s P, V , T u ni q uel y at an y i nst an t d u r i n g such a
p r oc ess.
P

V
f
1
2

V
i
V

Fi g. 14 .21
P

V
i
1
2

V
f
V

Fi g . 14 .2 2
Gas
Vacu u m
St op cock
I n su l at ed
Fi g. 14 .2 3
Fi g. 14 .2 4
P

V

A
D C
B
Posi t i ve w or k
( A)

V

A
D
C
B
Negat i v e w or k
P
( B)

( A)

V

A
C
B
W
A BC
= + Sh aded ar ea
P
W
A BC D
= Sh aded ar ea
V

A
C
B
D
P
( B)

Fi g. 14 .2 5
Vij ay Agarwal Thermodynami cs 6 5 3

A ct u al p r ocesses ar e not q uasi - st at i c. To ch an ge t h e p r essu r e of a gas,
w e can m ove a pi st on i nsi d e t he en cl osu r e. T he gas n ear t he p i st on i s act ed
u p on b y p i st on. T he p r essu r e of t he gas m ay n ot b e u n i f or m ever ywh er e
w h i l e t h e pi st on i s m ovi n g. How ever , w e can m ove t h e pi st on ver y sl ow l y t o
m ake t h e p r ocess as cl ose t o q u asi - st at i c as w e w i sh . T h u s, a q u asi - st at i c
p r ocess i s an i d eal i sed p r ocess i n w h i ch al l changes t ak e pl ace i nf i n i t el y
sl owl y.
Reversible and Irreversible Process
( 1) Rever si bl e p r ocess : A r ev er si bl e p r ocess i s on e w hi ch can b e
r ever sed i n su ch a w ay t h at al l ch anges occu r r i ng i n t he d i r ect p r oc ess ar e
exact l y r epeat ed i n t he opp osi t e or d er and i n ver se sen se an d n o ch ange i s
l ef t i n an y of t he bodi es t aki n g par t i n t h e pr ocess or i n t h e su r r ou nd i n gs.
For ex am pl e i f h eat i s ab sor b ed i n t he di r ect p r ocess, t he sam e am ou nt of
h eat shoul d b e gi v en out i n t he r ever se p r ocess, i f w or k i s don e on t he
w or ki n g su b st ance i n t h e d i r ect p r ocess t h en t he sam e am oun t of w or k
sh oul d b e don e b y t he w or ki n g su b st anc e i n t h e r ever se p r ocess. T h e
cond i t i on s f or r ever si bi l i t y ar e
( i ) T h er e m u st b e com p l et e ab sence of di ssi p at i ve f or ces su ch as
f r i ct i on , vi scosi t y, el ect r i c r esi st an ce et c.
( i i ) T he di r ect an d r ever se p r ocesses m u st t ak e pl ace i nf i n i t el y sl owl y.
( i i i ) The t em per at u r e of t h e syst em m u st n ot d i f f er ap p r eci abl y f r om
i t s su r r ou nd i ngs.
Som e exam pl es of r ever si bl e p r ocess ar e
( a) Al l i sot her m al and adi ab at i c ch an ges ar e r ever si bl e i f t h ey ar e
p er f or m ed ver y sl ow l y.
( b) W h en a cer t ai n am ou nt of heat i s ab sor bed b y i ce, i t m el t s. I f t h e
sam e am ou nt of h eat i s r em oved f r om i t , t h e w at er f or m ed i n t h e di r ect
p r ocess w i l l be con ver t ed i n t o i ce.
( c) A n ext r em el y sl ow ext en si on or c ont r act i on of a sp r i ng w i t h out
set t i n g u p osci l l at i on s.
( d) W h en a per f ect l y el ast i c b al l f al l s f r om som e h ei ght on a per f ect l y
el ast i c h or i zont al pl ane, t h e b al l r i ses t o t h e i n i t i al h ei ght .
( e) I f t h e r esi st an ce of a t h er m ocou pl e i s negl i gi bl e t h er e w i l l b e n o
h eat p r od uced d ue t o Joul e s heat i ng ef f ect . I n su ch a case heat i ng or
cool i ng i s r ever si bl e. At a j u nc t i on wh er e a c ool i ng ef f ect i s p r od u ced d ue t o
Pel t i er ef f ect wh en cu r r ent f l ow s i n one d i r ect i on an d eq u al heat i ng ef f ect i s
p r od uced w h en t h e cu r r ent i s r ever sed .
( f ) Ver y sl ow evap or at i on or con den sat i on .
I t sh oul d be r em em b er ed t hat t he con di t i on s m ent i on ed f or a
r ever si bl e p r ocess can never b e r eal i sed i n pr act i ce. H en ce, a r ever si bl e
p r ocess i s onl y an i d eal con cept . I n ac t ual p r ocess, t h er e i s al w ays l oss of
h eat d u e t o f r i ct i on , con d uct i on, r adi at i on et c.
( 2) I r r ever si ble p r ocess : A ny pr ocess whi ch i s not r ev er si bl e exact l y i s an
i r r ever si bl e p r ocess. Al l nat ur al p r ocesses such as cond uct i on , r adi at i on,
r adi oact i ve decay et c. ar e i r r ever si bl e. Al l p r act i cal p r ocesses such as f r ee
expansi on , Joul e- Th om son expansi on , el ect r i cal heat i ng of a w i r e ar e al so
i r r ever si bl e. Som e exam pl es of i r r ever si bl e pr ocesses ar e gi ven bel ow
( i ) W h en a st eel b al l i s al l ow ed t o f al l on an i n el ast i c l ead sh eet , i t s
k i n et i c en er gy ch an ges i n t o h eat ener gy b y f r i ct i on . T he heat en er gy r ai ses
t h e t em p er at u r e of l ead sh eet . No r ever se t r ansf or m at i on of h eat ener gy
occu r s.
( i i ) T he sudd en an d f ast st r et chi ng of a sp r i ng m ay p r oduc e vi br at i on s
i n i t . Now a p ar t of t h e en er gy i s di ssi p at ed. Th i s i s t h e case of i r r ever si bl e
p r ocess.
( i i i ) Su dd en exp an si on or con t r act i on and r api d evapor at i on or
cond en sat i on ar e exam p l es of i r r ever si bl e p r ocesses.
( i v) Pr od uc ed b y t h e p assage of an el ect r i c cu r r ent t h r ough a
r esi st ance i s i r r ever si bl e.
( v) H eat t r an sf er b et w een bodi es at d i f f er ent t em p er at ur es i s al so
i r r ever si bl e.
( vi ) Joul e- Thom son ef f ect i s i r r ever si bl e becau se on r ever si ng t he f l ow
of gas a si m i l ar cool i n g or h eat i ng ef f ect i s not ob ser ved .
Mixed Graphical Representation
( 1) PV - gr aph s
1 I sob ar i c ( P- con st ant )
2 I sot h er m al ( Because
V
P
1
)
3 A d i ab at i c ( Becau se

V
P
1
)
4 I soch or i c ( V- c on st ant )
( 2) PT - gr ap h s
1 I sob ar i c ( P- con st ant )
2 I sot h er m al ( T- con st ant )
3 Ad i ab at i c ( Becau se
1

T P )
4 Isoch or i c ( I n i soch or i c P T)

( 3) V T - gr aph s
1 I soch or i c ( V- con st ant )
2 A di ab at i c ( Becau se

1
1
T V )
3 I sot her m al ( T- con st ant )
4 I sob ar i c ( I n i sob ar i c V T )

Heat Engine
Heat engi ne i s a d evi ce w hi ch con ver t s h eat i nt o wor k cont i n uou sl y
t h r ou gh a c ycl i c p r oc ess.
T h e essen t i al p ar t s of a h eat en gi n e ar e
( 1) Sou r ce : I t i s a r eser voi r of h eat at hi gh t em per at ur e and i nf i n i t e
t h er m al cap aci t y . An y am ou nt of h eat can b e ext r act ed f r om i t .
( 2) W or ki n g sub st an ce : St eam , p et r ol et c.
( 3) Si n k : I t i s a r eser voi r of h eat at l ow t em per at u r e and i nf i n i t e
t h er m al cap aci t y . An y am ou nt of h eat can b e gi ven t o t he si n k.







T h e w or ki ng su b st ance ab sor b s heat Q
1
f r om t he sou r ce, does an
am ou nt of wor k W , r et u r ns t h e r em ai n i ng am ou nt of h eat t o t h e si n k an d
V

P
O

1
2

3

4

Fi g. 14 .2 6
T

P
O

1
2

3

4

Fi g. 14 .2 7
T

V
O

1
2

3

4

Fi g. 14 .2 8
W = Q
1
Q
2
Q
1
Q
2
H eat
En gi n e

Sou r ce
( T
1
)
( T
2
) Si n k

Fi g. 14 .2 9

6 5 4 Thermodynamics Vij ay Agarwal

com es back t o i t s or i gi n al st at e an d t her e occu r s no chan ge i n i t s i nt er n al
en er gy.
By r ep eat i ng t h e sam e cycl e over and over agai n , w or k i s cont i n u ou sl y
ob t ai ned .
T h e p er f or m an ce of heat engi n e i s exp r essed b y m ean s of ef f i ci ency
w hi ch i s d ef i n ed as t he r at i o of u sef ul w or k obt ai ned f r om t h e engi ne t o
t h e h eat su ppl i ed t o i t .

1
input Heat
done Work
Q
W
= =
For cycl i c p r ocess AU = 0 h enc e f r om FLO T AQ = AW
So
2 1
Q Q W =
1
2
1
2 1
1
Q
Q
Q
Q Q
=

=
A p er f ect h eat en gi n e i s on e w hi ch con ver t s al l h eat i nt o w or k i .e.
1
Q W = so t h at 0
2
= Q and h ence 1 = .
Bu t p r act i cal l y ef f i ci ency of an engi ne i s al w ays l ess t h an 1.
Refrigerator or Heat Pump
A r ef r i ger at or or heat p um p i s b asi cal l y a heat en gi n e r u n i n r ever se
d i r ect i on .
I t essent i al l y con si st s of t h r ee p ar t s
( 1) Sou r ce : At hi gh er t em p er at ur e T
1
.
( 2) W or ki n g su b st ance : I t i s cal l ed r ef r i ger ant l i q ui d am m on i a an d
f r eon wor k s as a w or ki ng su b st ance.
( 3) Si n k : At l ow er t em per at u r e T
2
.







T h e w or ki n g su b st ance t ak es h eat Q
2
f r om a si n k ( cont en t s of
r ef r i ger at or ) at l ow er t em p er at u r e, h as a n et am ou nt of w or k don e W on i t
b y an ext er n al agent ( usu al l y com p r essor of r ef r i ger at or ) an d gi ves ou t a
l ar ger am oun t of h eat Q
1
t o a hot bod y at t em p er at u r e T
1
( usual l y
at m osph er e) . T h u s, i t t r ansf er s heat f r om a col d t o a h ot b od y at t h e
exp en se of m ech ani cal en er gy su p p l i ed t o i t b y an ext er n al agent . T h e col d
b od y i s t h us cool ed m or e an d m or e.
T h e per f or m ance of a r ef r i ger at or i s exp r essed b y m ean s of coef f i ci ent
of p er f or m an ce w hi ch i s def i ned as t h e r at i o of t h e heat ext r act ed f r om
t h e col d bod y t o t he w or k n eed ed t o t r an sf er i t t o t h e h ot b od y.
i .e.
2 1
2 2
done Work
extracted Heat
Q Q
Q
W
Q

= = =
A p er f ect r ef r i ger at or i s on e w h i ch t r an sf er s h eat f r om col d t o hot
b od y w i t hout d oi ng w or k
i .e. W = 0 so t h at
2 1
Q Q = an d h ence =
( 1) C ar n ot r ef r i ger at or : For Car not r ef r i ger at or
2
1
2
1
T
T
Q
Q
=

2
2 1
2
2 1
T
T T
Q
Q Q
=

or
2 1
2
2 1
2
T T
T
Q Q
Q

So coef f i ci ent of p er f or m an ce
2 1
2
T T
T

=
w h er e T
1
= t em per at u r e of su r r ou n di ng, T
2
= t em p er at ur e of col d bod y.
I t i s cl ear t hat = 0 w h en T
2
= 0
i .e. t he coef f i ci ent of p er f or m an ce w i l l b e zer o i f t he col d bod y i s at t h e
t em p er at u r e eq ual t o ab sol u t e zer o.
( 2) Rel at i on b et w een coeff i ci ent of p er f or m ance an d eff ici en cy of
r ef r i ger at or
W e k n ow
2 1
2
Q Q
Q

=
1 2
1 2
/ 1
/
Q Q
Q Q

= .. ( i )
Bu t t he ef f i ci ency
1
2
1
Q
Q
= or = 1
1
2
Q
Q
..( i i )
Fr om ( i ) an d ( i i ) w e get ,

=
1

Second Law of Thermodynamics
Fi r st l aw of t h er m od yn am i cs m er el y ex pl ai ns t he eq ui val ence of w or k
an d heat . I t d oes n ot expl ai n w h y h eat f l ow s f r om b od i es at hi gh er
t em p er at u r es t o t h ose at l ow er t em p er at u r es. It cann ot t el l u s w h y t he
con ver se i s p ossi bl e. It can n ot ex pl ai n w h y t h e ef f i ci enc y of a h eat engi ne i s
al w ays l ess t h an u ni t y. It i s al so u n abl e t o expl ai n w hy cool w at er on st i r r i n g
get s hot t er w her eas t her e i s no such ef f ect on st i r r i ng w ar m w at er i n a
b eak er . Secon d l aw of t h er m od yn am i cs p r ovi d es an sw er s t o t h ese q u est i ons.
St at em ent of t h i s l aw i s as f ol l ow s
( 1) C l ausi u s st at em ent : I t i s i m p ossi bl e f or a sel f act i n g m achi n e t o
t r an sf er h eat f r om a col d er b od y t o a hot t er on e w i t h out t h e ai d of an
ext er n al agency.
Fr om Cl au si us st at em en t i t i s cl ear t h at h eat can not f l ow f r om a
b od y at l ow t em per at u r e t o on e at hi gher t em per at ur e u nl ess w or k i s don e
b y an ext er nal agency. T hi s st at em en t i s i n f ai r agr eem en t w i t h ou r
ex per i ences i n di f f er en t b r anches of p h ysi cs. For exam pl e, el ect r i c al cu r r en t
cann ot f l ow f r om a cond u ct or at l ow er el ect r ost at i c p ot en t i al t o t hat at
h i gh er pot ent i al u nl ess an ext er n al w or k i s d one. Si m i l ar l y, a bod y at a l ow er
gr avi t at i on al p ot en t i al l ev el can n ot m ove u p t o h i gher l evel w i t hou t w or k
d on e b y an ext er n al agenc y.
( 2) Kel vi n s st at em ent : I t i s i m p ossi bl e f or a body or syst em t o
p er f or m cont i n u ou s w or k b y cool i n g i t t o a t em per at u r e l ower t h an t h e
t em p er at u r e of t h e col d est one of i t s su r r ou nd i ngs. A Car n ot en gi n e cann ot
w or k i f t h e sour ce and si nk ar e at t he sam e t em per at ur e b ecau se w or k don e
b y t h e en gi n e w i l l r esul t i nt o cool i n g t h e sou r ce an d heat i ng t he
sur r ou n di n gs m or e and m or e.
( 3) Kel vi n- Plan cks st at em en t : I t i s i m p ossi bl e t o d esi gn an en gi n e
t h at ext r act s h eat an d f ul l y ut i l i ses i nt o w or k wi t h out pr od uci ng an y ot h er
ef f ect .
Fr om t h i s st at em ent i t i s cl ear t h at an y am ou nt of heat can nev er b e
con ver t ed com pl et el y i nt o wor k . It i s essent i al f or an engi n e t o r et u r n som e
am ou nt of h eat t o t h e si n k . A n en gi n e essen t i al l y r eq ui r es a sou r ce as w el l
as si n k . T h e ef f i ci ency of an en gi n e i s al w ays l ess t h an u ni t y b ecau se h eat
cann ot be f u l l y con ver t ed i nt o w or k .
Carnot Engine
W = Q
1
Q
2
Q
1
Q
2
H eat
En gi n e

Sou r c e
( At m osp h er e)

( T
1
)
( T
2
)
Si n k
( Con t en t s of r ef r i ger at or )

Fi g. 14 .3 0
Vij ay Agarwal Thermodynami cs 6 5 5

( 1) Car not desi gn ed a t h eor et i cal engi n e w h i ch i s f r ee f r om al l t h e
d ef ec t s of a p r act i cal engi n e. T hi s en gi n e can not b e r eal i sed i n act u al
p r act i ce, h owever , t hi s can b e t ak en as a st an d ar d agai n st w hi ch t h e
p er f or m an ce of an act u al engi n e can b e j ud ged .








I t c on si st s of t h e f ol l ow i ng p ar t s
( i ) A cyl i nd er w i t h p er f ect l y n on- con d uct i ng w al l s and a p er f ect l y
cond u ct i n g b ase cont ai ni n g a p er f ect gas as w or ki ng su b st ance an d f i t t ed
w i t h a non- con d uct i ng f r i ct i onl ess pi st on
( i i ) A sou r ce of i nf i n i t e t h er m al cap aci t y m ai n t ai n ed at con st ant hi gher
t em p er at u r e T
1.
( i i i ) A si n k of i nf i ni t e t h er m al cap aci t y m ai nt ai n ed at con st ant l ow er
t em p er at u r e T
2
.
( i v) A per f ect l y non- con d uct i ng st and f or t h e cyl i n d er .
( 2) C ar n ot cycl e : A s t h e engi ne w or k s, t h e w or ki ng su b st anc e of t h e
en gi n e u n der goes a cycl e k n ow n as Car n ot cycl e. Th e Car not cycl e con si st s
of t he f ol l ow i ng f ou r st r ok es









( i ) Fi r st st r ok e ( I sot her m al exp an si on) ( cu r ve A B) :
T h e cyl i n d er c ont ai n i ng i d eal gas as w or ki n g su b st ance al l ow ed t o
exp and sl ow l y at t hi s con st ant t em p er at ur e T
1
.
W or k d on e = H eat absor b ed b y t h e syst em
=
|
|
.
|

\
|
= = =
}
1
2
1 1 1
log
2
1 V
V
RT dV P Q W
e
V
V
Ar ea A BGE
( i i ) Second st r ok e ( A di abat i c exp an si on) ( cu r ve BC) :
T h e cyl i n der i s t hen pl aced on t h e n on cond u ct i n g st and and t h e gas i s
al l ow ed t o exp an d adi ab at i cal l y t i l l t he t em p er at u r e f al l s f r om T
1
t o T
2
.
}
=
3
2
2
V
V
dV P W = =

] [
) 1 (
2 1
T T
R

A r ea BCH G
( i i i ) Thi r d st r oke ( I sot h er m al com p r essi on ) ( cu r v e CD) :
T h e cyl i n der i s pl aced on t h e si nk an d t h e gas i s com p r essed at
con st ant t em p er at u r e T
2
.
W or k d on e = H eat r el eased by t h e sy st em

3
4
2 2 3
log
4
3 V
V
RT dV P Q W
e
V
V
= = =
}

CDFH
V
V
RT
e
Area log
4
3
2
= =
( i v) Fou r t h st r ok e ( adi abat i c com p r essi on) ( cu r ve D A) : Fi n al l y t h e
cyl i nder i s agai n p l aced on n on - cond uct i ng st and an d t h e com pr essi on i s
cont i n ued so t h at gas r et u r ns t o i t s i ni t i al st age.
) (
1
1 2 4
1
4
T T
R
dV P W
V
V

= =
}

ADFE T T
R
Area ) (
1
2 1
=

( 3) Ef f i cien cy of C ar n ot cycl e : T h e ef f i ci enc y of en gi n e i s d ef i n ed as
t h e r at i o of w or k d on e t o t h e h eat su p pl i ed i .e.

1
input Heat
done Work
Q
W
= =
Net w or k don e d u r i ng t h e c om pl et e cycl e
) ( ) (
4 3 2 1
W W W W W + + + = ABCD W W Area
3 1
= =
[ As
4 2
W W = ]

1
2
1
3
1
2 1
1
3 1
1
1 1
Q
Q
W
W
Q
Q Q
W
W W
Q
W
= =

= =
or
) / ( log
) / ( log
1
1 2 1
4 3 2
V V RT
V V RT
e
e
=
Si n ce p oi nt s B and C l i e on sam e ad i ab at i c cu r ve

1
3 2
1
2 1

=

V T V T or
1
2
3
2
1

|
|
.
|

\
|
=

V
V
T
T
..( i )
A l so poi nt D and A l i e on t h e sam e ad i ab at i c cu r ve

1
4 2
1
1 1

=

V T V T or
1
1
4
2
1

|
|
.
|

\
|
=

V
V
T
T
..( i i )
Fr om ( i ) and ( i i ) ,
1
4
2
3
V
V
V
V
= or
1
2
4
3
V
V
V
V
=
|
|
.
|

\
|
=
|
|
.
|

\
|
1
2
4
3
log log
V
V
V
V
e e

So ef f i ci en cy of Car not engi ne
1
2
1
T
T
=
( i ) Ef fi ci ency of a heat engi ne depends only on t emper at ures of sour ce and
sink and i s independent of all ot her fact or s.
( i i ) Al l r ever si bl e h eat engi n es w or ki ng bet w een sam e t em p er at u r es ar e
eq u al l y ef f i ci ent an d no h eat engi n e can b e m or e ef f i ci en t t han Car n ot
en gi n e ( as i t i s i deal ) .
( i i i ) A s on Kel vi n scal e, t em p er at ur e can n ever b e negat i ve ( as 0 K i s
d ef i ned as t h e l ow est p ossi bl e t em per at u r e) and T
l
an d T
2
ar e f i n i t e,
ef f i ci enc y of a h eat en gi n e i s al w ays l esser t h an u ni t y, i .e., w h ol e of h eat can
n ever b e con ver t ed i nt o w or k w hi ch i s i n ac cor d ance w i t h second l aw .
( 4 ) C ar n ot t h eor em : Th e ef f i ci ency of Car not s h eat en gi n e d epen d s
on l y on t h e t em p er at u r e of sou r ce ( T
1
) and t em p er at ur e of si n k ( T
2
) , i .e.,
1
2
1
T
T
= .
Car n ot st at ed t h at n o heat en gi n e wor ki n g bet w een t w o gi ven
t em p er at u r es of sou r ce and si nk can b e m or e ef f i ci ent t han a per f ect l y
r ever si bl e en gi n e ( Car n ot engi ne) w or k i ng bet w een t he sam e t wo
Sou r ce
T
1
K
I n su l at i n g
st an d
Si n k
T
2
K
I deal gas
Fi g. 14 .3 1
Q
1
Q
2
W = Q
1
Q
2

P

V

T
2

T
1
C( P
3
, V
3
)
A( P
1
, V
1
)
( P
4
, V
4
) D
E

F

G

H

Fi g. 14 .3 2

6 5 6 Thermodynamics Vij ay Agarwal

t em p er at u r es. Car not ' s r ever si b l e engi ne w or ki ng b et w een t w o gi ven
t em p er at u r es i s con si d er ed t o be t h e m ost ef f i ci en t engi ne.
T able 14.3 : D ifference Between Pet rol Engine and D iesel Engine
Pet r ol en gi n e D i esel en gi n e
W or k i n g su b st an ce i s a m i xt u r e of
p et r ol v ap ou r an d ai r .
W or k i n g sub st ance i n t h i s engi n e i s a
m i x t ur e of di esel vapour an d ai r .
Ef f i ci en cy i s sm al l er ( ~4 7 %) . Ef f i ci en cy i s l ar ger ( ~5 5%) .
I t w or k s w i t h a sp ar k p l u g. I t w or k s w i t h an oi l p l u g.
I t is associ at ed wi t h t h e r isk of
expl osi on, because pet r ol vapour an d
air i s compr essed. So, low compr essi on
r at i o is kept .
No r i sk of exp l osi on , b ecau se on l y ai r
i s c omp r essed. H en ce comp r essi on
r at i o i s k ep t l ar ge.
Pet r ol v ap ou r an d ai r i s cr eat ed w i t h
sp ar k p l u g.
Sp r ay of di esel i s ob t ai n ed t h r ou gh
t h e j et .
Entropy
En t r op y i s a m easu r e of d i sor der of m ol ec ul ar m ot i on of a syst em .
Gr eat er i s t h e di sor d er , gr eat er i s t h e ent r op y.
T h e ch ange i n ent r opy i .e.

re temperatu Absolute
system by absorbed Heat
= dS or
T
dQ
dS =
T h e r el at i on i s c al l ed t h e m at h em at i cal f or m of Secon d Law of
T h er m od yn am i cs.
( 1) For sol i ds and l iq u i d s
( i ) W h en h eat gi ven t o a su b st ance ch anges i t s st at e at con st ant
t em p er at u r e, t h en ch an ge i n en t r op y
T
mL
T
dQ
dS = =
w h er e p osi t i ve si gn r ef er s t o heat ab sor pt i on an d n egat i ve si gn t o h eat
evol u t i on .
( i i ) W h en h eat gi ven t o a sub st an ce r ai ses i t s t em p er at u r e f r om T
1
t o
T
2
, t h en ch ange i n ent r op y

|
|
.
|

\
|
= = =
} }
1
2
log
2
1 T
T
mc
T
dT
mc
T
dQ
dS
e
T
T


|
|
.
|

\
|
= A
1
2
10
log 303 . 2
T
T
mc S .
( 2) For a per f ect gas : Per f ect gas eq u at i on f or n m ol es i s PV = n RT
} }
+
= = A
T
dV P dT C
T
dQ
S
V

[ A s dQ = dU + d W ]

}
+
= A
T
dV
V
RT
dT C
S
V

} }
+ =
2
1
2
1
V
V
T
T
V
V
dV
R
T
dT
C [ A s PV = RT]

|
|
.
|

\
|
+
|
|
.
|

\
|
= A
1
2
1
2
log log
V
V
R
T
T
C S
e e V

I n t er m s of T and P,
|
|
.
|

\
|

|
|
.
|

\
|
= A
1
2
1
2
log log
P
P
R
T
T
C S
e e P

and i n t er m s of P and V
|
|
.
|

\
|
+
|
|
.
|

\
|
= A
1
2
1
2
log log
V
V
C
P
P
C S
e P e V






W h en a t h er m os b ot t l e i s vi gor ou sl y sh ak en :
Heat t r an sf er r ed t o t h e cof f ee AQ = 0
[ A s t h er m os f l ask i s i n sul at ed f r om t h e sur r ou n di ng]
W or k i s done on t he coff ee agai nst vi scous f or ce
AW = ( )
I nt er nal ener gy of t h e cof f ee i n cr eases AU = ( +)
an d t em p er at u r e of t h e c of f ee al so i n cr eases AT = ( +)
W or k don e w i t hou t t he vol um e l i m i t s

}
=
f
i
V
V
dV P W
Fr om t h i s eq u at i on i t seem s as i f w or k d on e can b e cal cul at ed onl y
w h en P- V eq u at i on i s k now n an d l i m i t s
i
V an d
f
V ar e k n own t o u s.
Bu t i t i s n ot so. W e can cal cul at e wor k don e i f we k n ow t he l i m i t s of
t em p er at u r e.
For m ol es of an i d eal gas i f
T
P

= w i t h t em per at u r e l i m i t s T
0

an d 2T
0
.
Fr om PV = RT

2
RT
P
RT
V = = dT
RT
dV

2
=

0
2
2
2 0
0
RT dT
RT
T
dV P W
T
T
V
V
f
i

= |
.
|

\
|
|
.
|

\
|
= =
} }

W or k done w i t h sp r ing : If m ass l ess pi st on i s at t ached t o a sp r i ng of
f or ce con st ant K and a m ass m i s pl aced over t he pi st on. I f t he ext er n al
p r essur e i s
0
P an d du e t o expansi on of gas t he pi st on m oves u p t hr ough
a di st ance x t hen
Tot al w or k d on e b y t h e gas
3 2 1
W W W W + + =
w h er e W
1
= W or k d one agai nst
ext er nal p r essu r e ) (
0
P
W
2
= W or k d one agai n st sp r i ng
f or ce ) (Kx
W
3
= W or k d on e agai n st gr avi t at i on al f or ce ( m g)
mgx Kx V P W + + =
2
0
2
1

Th e ef f i ci en cy of an act u al engi n e i s m u ch l esser t h an t h at of an
i d eal engi ne. Act u al l y t h e p r act i cal ef f i ci en cy of a st eam engi n e i s about
( 8 - 15) % w hi l e t h at of a p et r ol engi n e i s 4 0%. T he ef f i ci en cy of a di esel
en gi ne i s m axi m um and i s ab out ( 50 - 55 ) %.
W h en P an d V b ear t h e r el at i on PV
x
= con st ant , w her e x = 1 or
t h e p r ocess i s cal l ed a p ol yt r opi c on e. I n t h i s p r ocess t h e m ol ar h eat
cap aci t y i s,
x
R R
x
R
C C
V

+ =
1 1 1

En t h al p y : Fou r q u ant i t i es c al l ed t h er m od yn am i c p ot en t i al s ar e
u sef ul i n t h e ch em i cal t her m od yn am i cs of r eact i on s and n on- cycl i c
p r ocesses. Th ey ar e i nt er n al en er gy, t he en t h al p y, t h e H el m ol t z f r ee
en er gy an d t he Gi b b s f r ee en er gy. Ent h al p y i s d ef i n ed by
x
M
M
P
Vij ay Agarwal Thermodynami cs 6 5 7

H = U + PV
w h er e P and V ar e t he p r essu r e an d vol um e, and U i s i nt er n al ener gy,
Ent h al p y i s som ew hat p ar al l el t o t h e f i r st l aw of t her m od yn am i cs f or a
con st ant p r essur e syst em Q = AU + PAV si n ce i n t hi s case Q = AH .
C onf u si on ab out FLO T
I t i s t ypi cal f or ch em i st r y t ext s t o wr i t e t he f i r st l aw as
U = Q + W
I t i s t h e sam e l aw , of cou r se t he t h er m od yn am i c exp r essi on of t h e
con ser vat i on of en er gy p r i nci pl e. I t i s j u st t h at W i s d ef i n ed as t h e w or k
d on e on t h e syst em i n st ead of w or k don e b y t he syst em . I n t he cont ext
of p h ysi cs, t h e com m on scen ar i o i s on e of ad di ng h eat t o a vol um e of
gas and u si ng t h e ex p an si on of t h at gas t o do wor k , as i n t he p u shi ng
d ow n of a pi st on i n an i nt er nal com b u st i on engi n e. I n t h e cont ext of
ch em i cal r eact i on s an d p r ocess, i t m ay be m or e com m on t o d eal w i t h
si t uat i on s w her e w or k i s don e on t h e syst em r at her t h an by i t .
Possi b il i t i es





I f a I sot h er m al t h en b M u st be adi abat i c
Bu t I f b ad i abat i c t hen i t i s not com pul sor y t h at a m u st b e
i sot h er m al , i t m ay be adi abat i c al so.







First Law of Thermodynamics (Q = U + W)

1. Fi r st l aw of t her m nod ynam i c s i s gi ven by [ C PM T 19 7 7 , 9 1]
( a) PdV dU dQ + = ( b) PdV dU dQ =
( c) P dV dU dQ ) ( + = ( d) dV PdU dQ + =
2 . Th e i nt er n al en er gy of an i d eal gas d ep end s up on
[ RPM T 19 9 7 ; M P PM T 19 9 9 ; C PM T 20 0 3 ]
( a) Sp eci f i c vol um e ( b) Pr essu r e
( c) T em per at u r e ( d) D en si t y
3 . I n ch angi n g t h e st at e of t her m od yn am i cs f r om A t o B st at e, t h e h eat
r eq ui r ed i s Q an d t he wor k don e b y t h e syst em i s W . T he ch an ge i n
i t s i nt er nal en er gy i s
[ M P PM T 19 8 6 ; AM U ( M ed.) 2 0 0 1]
( a) Q + W ( b) Q W
( c) Q ( d)
2
W Q

4 . Heat gi ven t o a syst em i s 35 j oul es and w or k d on e b y t he syst em i s
15 j oul es. Th e chan ge i n t h e i n t er n al ener gy of t h e syst em w i l l be [ M P PET / PM T 19 8 8 ]
( a) 50 J ( b) 20 J
( c) 30 J ( d) 50 J
5 . T h e t em p er at ur e of an i deal gas i s k ept c onst ant as i t exp and s. T h e
gas d oes ext er n al w or k . D u r i n g t h i s p r ocess, t he i n t er nal en er gy of
t h e gas [ M P PM T 19 9 0 ]
( a) D ecr eases
( b) I n cr eases
( c) Rem ai ns const an t
( d) D ep end s on t he m ol ecul ar m ot i on
6 . T h e f i r st l aw of t h er m od yn am i cs i s concer n ed w i t h t h e con ser vat i on
of [ M P PM T 19 8 7 ; CBSE PM T 19 9 0 , 9 2 ;
A FM C 19 9 7 ; C PM T 19 9 9 ; BH U 19 9 9 ;
D C E 2 0 0 0 ; BC EC E 2 0 0 3 ]
( a) M om en t um ( b) En er gy
( c) M ass ( d) T em per at u r e
7 . A t her m od yn am i c sy st em goes f r om st at es ( i )
1
P , V t o
1
2P , V ( i i )
P, V t o P, 2V . Th en w or k done i n t he t w o cases i s
[ M P PM T 19 9 0 ]
( a) Zer o, Zer o ( b) Zer o,
1
PV
( c)
1
PV , Zer o ( d)
1 1 1
, V P PV
8 . If t he am ou nt of h eat gi ven t o a syst em b e 35 j oul es and t h e am ou nt
of wor k d on e b y t h e sy st em b e 15 j oul es, t h en t he ch ange i n t h e
i n t er n al ener gy of t h e sy st em i s
[ M P PM T 19 8 9 ]
( a) 50 j oul es ( b) 20 j oul es
( c) 30 j oul es ( d) 5 0 j oul es
9 . A syst em i s gi ven 300 cal or i es of h eat an d i t d oes 6 0 0 j oul es of
w or k . How m uch does t he i nt er nal en er gy of t h e syst em change i n
t hi s p r oc ess
( J = 4 .18 j oul es/c al ) [ M P PET 19 9 1]
( a) 6 54 Joul e ( b) 15 6 .5 Joul e
( c) 30 0 Joul e ( d) 5 28 .2 Joul e
10 . W or k d on e on or b y a gas, i n gener al dep end s u p on t h e
( a) I n i t i al st at e onl y
( b) Fi nal st at e onl y
( c) Bot h i n i t i al an d f i n al st at es onl y
( d) I n i t i al st at e, f i n al st at e and t h e p at h
11. If R = u ni ver sal gas con st ant , t he am oun t of h eat need ed t o r ai se t h e
t em p er at u r e of 2 m ol e of an i d eal m on oat om i c gas f r om 273 K t o
373K w h en n o w or k i s don e [ M P PET 19 9 0 ]
( a) 10 0 R ( b) 150 R
( c) 30 0 R ( d) 5 0 0 R
12. Fi nd t h e ch an ge i n i nt er n al en er gy of t he syst em w h en a syst em
ab sor b s 2 ki l oc al or i e of h eat and at t h e sam e t i m e d oes 5 00 j oul e of
w or k [ EAM C ET 19 8 4 ]
( a) 79 00 J ( b) 8 200 J
( c) 5 6 0 0 J ( d) 6 4 0 0 J
P
V
a
b