Limitation of 1st Law:-

No comment about the direction

of Brows,
No comment about extent of Bro cess .

Spontaneous Process:- Sj take

place it own under
a
process
condition then it called
given , spontaneous .

of fast
> be slow
may
→ Condition affect spontaneity of process
left H2O
>
H2O
so @,
② at I atm ,
10°C spontaneous

⑥ at I atm ,
-

Lok Non spontaneous

at
④ at labs ,
ok Eguib .

#f All natural process are

spontaneous .

Second law of thermodynamics:-

 AH = the

Ft
Qc =
-

Ve

w = -

ve

② Ht Re Iwl

3=14
② It
Re
To
M = It LA

Qt
Carnot cycle:-

Ideal Gras AB Isothermal Expansion

Bc Adiabatic Expansion
CD = Isothermal Compression
DA =
Adiabatic Compression
Th

TH TF
AB 00=0
mm

4 W Eve) = tve
?
-
= -

Ck
tht
=hRThhnfB
TE #
→ CD GU =o
-

f W
Cure ) ve
-
=
= -
= -

418
-_nRTcIn⇐c ) = ve
-

hR# In #-)
Z = It

CEA)
WRT# In

"' ""
I

¥=⇐I
①
-

BC Th VB
=
Talk -

¥
-

-
-

f- I f- I -

④ .
BI Th VA = To ×
YD
c)
In
Urfa =
- In

z
-

-
I -

Eth)
Carnot cycle:-

Ideal Gras AB Isothermal Expansion

Bc Adiabatic Expansion
CD = Isothermal Compression
DA =
Adiabatic Compression
Th

TH FF
AB 00=0
mm

4 W Eve) = tve
?
-
= -

Ck
tht
=hRThhnfB
TE #
→ CD GU =o
-

I W
Cure ) ve
-
=
= -
= -

4$
-_nRTcIn⇐c ) = ve
-

# Elm #-)
Z = It

NAT# In

"' "'
I

¥=⇐I
①
-

BC Th VB
=
Talk -

¥
-

-
-

f- I f- I -

④ .
DI Th VA = Tc ×
YD
c)
In
Urfa =
- In

z
-

-
I -

Eth)
lwlrev > I WI Ion

' > ' ten

wtf I. him him
>
 ⇐I
I ' t
>
-

ion

' t
Ith
l - =

new

s*⇐
¥÷ >
¥
-

¥tT÷ to

Igorot 8¥ to Eo

EE to

10¥) to Clausius
inequality
Entropy
For reversible process §(E)=o = DJ

ds=
ds -

(E) ion X
 ds
=CE↳ S=f(disorder)
disorder 5

Si SL Sz Sy
S > Sz > Ss >
, Sy

# S is a state function as well as

extensive
property of system .

rev @ Si Drew
-

.
'

'
"
=

@ 2) ion
i -

l
'
-

-
-
.
-
z
.

ion
-
-
epi
① Solid L liq C Gas
entropy
②
Gas
Gas (

T
, Y T, Va

Va > Y
③ a

a
S

T
④ Diamond ( Graphite

⑤ Ice water

⑥ Rxni
a a

No Gas S
of
moles

Cacus → Cao tcozq ,

: OS tire
ef a ,
-_

→ OS
Nags t3Hzg 2MHz re
i
=
-

,
,

Pas g ,
→ PU , tacy , : OS -
-
tire
9)

It 2HIq ,
>
Itza ,
t
Iza ,
Oser o

05=0 X

⑦ LI HL ) H

Hz 2h
EE HL C H2

EI Nz Etty

H m - same Atoms
IT ST
Atoms same
mga Sf
-

Atoms * Same MT ST
above is hot
# but
true
always

\
Calculation of entropy change for system:-
① for ideal Gas

µd)aw
DS = = =
dutpdv
aw
T

T2 Vu
ds =

nfu
TI
+
nr¥
VI
*

) )
as = main thru
, ,

VI. =

TF Epa,
'

os =
Ncp
tuff ) ,
t HR In
(Az )
⑨ Isothermal Rrocess T=Co①
as
nRtn⇐)=hRhs¥ )
=

③ Isobaric P=Co①
as Mcp In
,⇐)
=

k-contf.os-ncvh.CI)
② Iso choric Rroass
⑨ Adiabatic Process : .

① Reversible 8=0 = Trev

Fuente
ds
GE)aw=o nah
)thRh⇐ )
-
-
- -

iso entropic
process s=Co@
① Irreversible 0--0=9 ing

OS =
= o
X
im

OS = her
buff ,
t n Rh
,
)
 OS = tve

✓ OS =
-
ve

OS - tve

OS -
-
tire

as =
a

whiff) ,

§%✓
In
Zxzrx
=

=3 Rh 3

1-
⇐) n
>
itch )
i
¥¥ ⇐I 4 #D . .
- -

X
•

✓
A fit
ITH
m = I -

f
p
t
Dt¥⇐a
Tithe
"
- E! ,

⑥si "=C¥ , ⇐ ¥.TT#I

I =
on
Carnot cycle:-

Ideal Gras AB Isothermal Expansion

Bc Adiabatic Expansion
CD = Isothermal Compression
DA =
Adiabatic Compression
Th

TH FF
AB 00=0
mm

4 W Eve) = tve
?
-
= -

Ck
tht
=hRThhnfB
TE #
→ CD GU =o
-

I W
Cure ) ve
-
=
= -
= -

4$
-_nRTcIn⇐c ) = ve
-

# Elm #-)
Z = It

NAT# In

"' "'
I

¥=⇐I
①
-

BC Th VB
=
Talk -

¥
-

-
-

f- I f- I -

④ .
DI Th VA = Tc ×
YD
c)
In
Urfa =
- In

z
-

-
I -

Eth)
lwlrev > I WI Ion

' > ' ten

wtf I. him him
>
 ⇐I
I ' t
>
-

ion

' t
Ith
l - =

new

s*⇐
¥÷ >
¥
-

¥tT÷ to

Igorot 8¥ to Eo

EE to

10¥) to Clausius
inequality
Entropy
For reversible process §(E)=o = DJ

ds=
ds -

(E) ion X
 ds
=CE↳ S=f(disorder)
disorder 5

Si SL Sz Sy
S > Sz > Ss >
, Sy

# S is a state function as well as

extensive
property of system .

rev @ Si Drew
-

.
'

'
"
=

@ 2) ion
i -

l
'
-

-
-
.
-
z
.

ion
-
-
epi
① Solid L liq C Gas
entropy
②
Gas
Gas (

T
, Y T, Va

Va > Y
③ a

a
S

T
④ Diamond ( Graphite

⑤ Ice water

⑥ Rxni
a a

No Gas S
of
moles

Cacus → Cao tcozq ,

: OS tire
ef a ,
-_

→ OS
Nags t3Hzg 2MHz re
i
=
-

,
,

Pas g ,
→ PU , tacy , : OS -
-
tire
9)

It 2HIq ,
>
Itza ,
t
Iza ,
Oser o

05=0 X

⑦ LI HL ) H

Hz 2h
EE HL C H2

EI Nz Etty

H m - same Atoms
IT ST
Atoms same
mga Sf
-

Atoms * Same MT ST
above is hot
# but
true
always

\
Calculation of entropy change for system:-
① for ideal Gas

µd)aw
DS = = =
dutpdv
aw
T

T2 Vu
ds =

nfu
TI
+
nr¥
VI
*

) )
as = main thru
, ,

VI. =

TF Epa,
'

os =
Ncp
tuff ) ,
t HR In
(Az )
⑨ Isothermal Rrocess T=Co①
as
nRtn⇐)=hRhs¥ )
=

③ Isobaric P=Co①
as Mcp In
,⇐)
=

k-contf.os-ncvh.CI)
② Iso choric Rroass
⑨ Adiabatic Process : .

① Reversible 8=0 = Trev

Fuente
ds
GE)aw=o nah
)thRh⇐ )
-
-
- -

iso entropic
process s=Co@
① Irreversible 0--0=9 ing

OS =
= o
X
im

OS = her
buff ,
t n Rh
,
)
 OS = tve

✓ OS =
-
ve

OS - tve

OS -
-
tire

as =
a

whiff) ,

§%✓
In
Zxzrx
=

=3 Rh 3

1-
⇐) n
>
itch )
i
¥¥ ⇐I 4 #D . .
- -

X
•

✓
A fit
ITH
m = I -

f
p
t
Dt¥⇐a
Tithe
"
- E! ,

⑥si "=C¥ , ⇐ ¥.TT#I

I =
on
 } oSum

9g osuniv 70 Spontaneous
osuniv =o Reversible for at
-

Epnib)
osuniv CO Non spontaneous

9
Ismet 9swm= -9=8
e-
rev
, ,

82 Ch
thou -_8z=%
→
9sys+=
-

I
osswm -_

fyre
where F-
Temp of Sun .
Bubi l mole
of an ideal Gas in expanded from
2 lit to 4 lit at zoo k under isothermal
condition Calculate US Oswin
.
syst , , ostomy .

①
9J process is reversible

at
④
9J Process is irreversible .

Sol ① ossyn - = n Rtm

⇐u ) ,
=
Rtn 2

Rhee
OSF -_ o = US
syst tossup Oswin = -

00=0 9= W
④ ossyst Rtn
-

= 2 ,

05*30
↳
sure
=
-

I =⇐) =

-Pextfv

4y+ RCI= k¥4 ¥,

-

=
-

= -

Ix Rft -

E)
=

R2
-
② Entropy change For real Gas

⑤ at cont v ⑧ at Constant P

Ev = du =3 Udt 9p=dH = n
Cpd T

dS=t¥=h§d÷ deff -

hfp.fi
,f oS=hCphnf¥µ)
OS = n cuh

③ for Solid / liquid

Coit
Incompressible V -
-

¢=dd' U = hardt =3 Cmd T

ds =

nfcindt hCmhf =

buff )
ds =
ncm
,
 ①
⑤
④ Phase Transition

① Reversible phase transition

' am

1¥ G
⑥ Vaporization look

H2O →
Hog at lahm look
=TBp
@ , , ,

Normal B. P
8=0 Huap
osvap =
ottvap
T
Bp

⑥ Melting on fusion : .

H2O g
→ H2O at latm Ok
Tmp
, @,
-_
,

Normal melting pt
f. = OH
fusion

OS OH
fusion =
fusion

T
hip
 ② Irreversible Phase transition :

EF thos , s H2O @ ,
og
calm ,
-3°C I aim
,
27°C
N
us
,
053
052
Hice , nun (32%1)
"
3
H2O
Lahm Oc t

ok
,

Latin
,

th ottfusion
NC In
227,3-0
-

05=05, toss t
05g
=

273

H2O → H2O
et @ , as
,

lahm 127°C
lahm , 27°C ,

0531
a

051

052
-i

H2O @ ,
> H2O Cq ,

1ohm look
Lahm ,
look ,

05=05 ,
t OSL t 053

} ottzygp-tncph.C)I
n
=
nice , In t
-
3rd law of Thermodynamics:-

Entropy of perfect crystalline substance is zero at 0k

Temp .

¥7 KE is zero

No disorder in perfect Crystal .

OS =
Sq Scs , =
Scg ,
A
,
-

> Age , at 1am

Ok TK

OS
, toss
×
052 054
053 AG ,
Acs ) > A @) - Aa ) >

Tpp TBP
Tmp Tmp

Sq ,
= OS , t 052 toss to Sy t
TBP
05g
Tmp

=nfq tn.9tffpsiontnfc.IT
OK
T
Tmp

notice
+
nfI
Tbp
Q
Sp
✓

gg-ncmhtf-zsxioxurzxenmq.gs#cm
Q
•

O
Rev .
oSt=o
=
ossysttoswy
Osborn = -

85 Jfk -

hah

= -

l -

5×85 The

✓
2x R In 2 = ZRINL 2×8314×0-603
syst
= =

=/ I 52

¥
-

OS =
-
-

3 -
41 x ( ooo
hour =

II
310 =
-

Q
✓
 3rd law of Thermodynamics:-

Entropy of perfect crystalline substance is zero at 0k

Temp .

¥7 KE is zero

No disorder in perfect Crystal .

OS =
Sq Scs , =
Scg ,
A
,
-

> Age , at 1am

Ok Tk

OS
, toss
×
052 054
053 AG ,
Acs ) > A @) - Aa ) >

Tpp TBP
Tmp Tmp

Sq ,
= OS , t 052 toss to Sy t
TBP
05g
Tmp

=nfq tn.9tffpsiontnfc.LI
OK
T
Tmp

notice
+
nfI
Tbp
F

⑨
'
E
Ose →
G) °Ss→e
or
I -
G or

osvap → fusion

Sn D

①
•

see
B
⑤
A
1- →
Entropy change of rxn:

att t b B → CC told

Sao Soo SE Soo atcoutt.rs

per mole

05am =
@ sit DSB ] -

Casaotbsb ]

IFE when p= Cont T ⇐ IT → T2

Genet

osi-ositocpnxnh.CI ) ,

oCp= Cp ( Rroducts
Mxn
-
Reactants)
.

# When F- Cont P =p, s Pz

osi =

ositongrlnfpfz ) FYI Diff in

St Coyt
of
-

X Real Gas
*
Gas ( Rroduct -

Reactants
 T Vs S diagram:-
ds
-_⇐↳= EE
A B
g fur = T DS -

"
%
= Area
T
T
Area under Tvs s
graph will

s→ give magnitude of Trev

> # "
I:c:* 's:c:&; "

i.
q¥¥¥¥÷ <
.

?
Area -
-
her -_ tve

C)
s →
Area -_ Trev = -

re

00=0 8 = -
W
rev
rev

Carnot 's
cycle of TVs S
diagram : .

A
t't
B
chttlc = Trev -_
CTH -

Tc ) (S2 Si ) -

sourer TH >
'

- = .
-

→
TH =
Thx ( S2 Si) -

TT
v
n

Ta

4H¥
c

N
- - -

If
D = I
Sinn
= -

te
'
i
,
i t ,

Si SL

J
'
00=0 D= -
w

w = -
( TH Tc
-

) ( S2 -

Si )
 Gibb’s function:- → State function
Extensive
Rropertyy
G =
H -

T S .

→ thermodynamic function

for calculation
of
spontaneity .

OG = o
(H -

IS ] * Absolute value can not be

OG = OH -

OCT S ) .
determined .

at cont T

OG = OH -

T -
OS
at cont P .
4=0 It

or = f -

T OS -

OG = -
T
L Itt
-

OS
) =
- T
.

( ossurrtossyst)
OG = - T .

@ Sun ) ,
at cont T, P

Spontaneous Rrocess
oG=
osuniitve
①
9J
ve
-

ve OG
② tve
- -

Tf
=

osun
-

Non spontaneous process

.

06=0
③
Gf at Equi b ( or rev ) =oSunir=o
 at cont Tip

# OG OH T.us OG
Equi b
=
at
-
-

-
o

Ist Ind T = =
To =
Eguib
Temp .

OH OS OG

-
re tve
Always -
ve
Always spontaneous
+ ve - ve eve Always Non -

Spontaneous
OG tve
9J T > To
-_
-
Ve - ve

TL To OG =
-
ve

oG=
YT > To ve
-

+ve * ve

TL To oG=tre

Calculation
T# of 0Grxn
① att t b B s CC t DD

OGICA ) OGE @ ) OGIE ) OGEED ) per mole

OG :* =
06°F ( Rroducts - Reactants)
# OGI elements in their natural , most stable form an

taken as zero

②
.

OGIE OH
n
-
T.

05am

at Tet, OG ? = olti -
T
,
.
Osi

T -
Tz OGI =
?
OGE = Oki -

Tz .
OSE

T
✓ o HE = o Hi to Cram TD
✓ osso si ocpaxs.tn
= o t

,
)

# 9J oCps× ,
Chot given) or
change in
temp is small

then 0 Hi = OHi

OSE =
osi

OGE = ol ti -

Tz .
o
si
 and
# Sign of OH
,
as OG

¥ PUS ¢,
s
Reza ,
t
Uzi , :oH-
OG = OH -

T -
OS OS -_ the

¥fFe 9J T> To 0G= -

re

TL To OG -_ the

CI Ccs , oH=
{ 02cg
ve
t s
Coq , i
-

OS -_ tve
OG = OH -

TOS
- - = -
ve
-
ve -
ve

:
eg
- Lacosse ,
→ Goes , t 029 , : OH -

-
tire

or -_ OH -
T OS. OS = the
- -

the -
ve

T> To oGr= -
ve

TL To oG=tve
Q

O 20

n
OS =

Saw -

Sou =
Szow= = O -

813
The
.mu

@ Pt bxlo
°
O -
4 = Ax -

0.92 =a x @ Pt bxzo ④
-

°
[ Rgoclucts Reactants)
own S
168.351mg
=
-

= -

Q
TO
reversible osvap =
ottvap
TBP
30×1000
TBP =
hook
←
=

Q 0
palm

O
H2O @,
→ H2O at -101
#
OH =
-

ve 0Gr= OH -

T-

OS
--

OS =
-
ve - ve tire

0G_
Q

✓
O
OG = OH - T . OS
- -

+ve -

ve

T > To OG = ve
-

To =

00¥ =
17%002 =
10004
 ( ) = du t d @v) -

des )

from Ist Law du = 9 tw

DG =
@LtwJtpdVtVdP-T.dS-S.d T
w = W t w
pv Non -

pv
for reversible process
fiev-TT.dS@reuJpve-P.dV
DG
.cl/s)It-Cp./dV)tWnonpvtP.d/VtV-dP-T.d/S-S.dTdGr=WNon-pvtV.tdP
=
CT
-

S
.dT*
① at cont T
,
P DG = W
Non pv -
for Mv Rrocess
Wixon d G V. DP S DT
② Of
=0
Dv = -
.
-

Isothermal Rrocess
P
:

Trout &pd)p=v
Case -1 Solid ( liquid
✓ = Cont
x
Pz

Vfd
.

dor -

-
P dG=V( Pz -

R)
P,

Case -2 Ideal Gas

Ven RT
k

Pu p

dG=fnpRdp dG=nRtIn@p ) ,

Pi
Isobaric Rrocess :
-

f- Cont doe -

5. DT

(F) p= s
-

'

✓
Relation between.DOGG and Equib constant oG=hRThr(¥ ) ,

PA PB Pc PD
& Po
at
- Cantt, P

Po Po Po
.fm
understand
@ a
-
Gao
)=RthP⇐)

*
o

pool bar

=
otto -
T oso
.
 RT Otto T
In Kp oso
- -

= .

blip
OLI
-
=

. t

Otto , 0150 = Cont

9J OHI -

ve

tano -_
-
It 05 = tire
o R
-
-7 - -
-

bur
-

) off
1-
'
TT
N_de:① A e-
B c → D

tf -

C
A
-

GT
b
qui
G
AM
-

,
B -

D-

Mxn coordinate

Mxn coordinate

Gmin Equi b Pt

Rxn that direction where

② move in increase
in Total
entropy
take place ,
till it become max .
 it
A > B

at
Epub P I
4
Lep =

Php =Iy
oG°= Im 't
-

Rthnkp =
-

RT Int = RT

✓
2140cg , t Elza , → 21406cg ,
060=-8×298 In 108
lip = 40-72 108
=
= -
8×298×8×-2303
(10-92×40-2) 1000
= -43.924J

H2O @ , s H2O @ ) OG -_
VCR Pi )
-

lobar 20bar =
18×(20-10) HOT
bar lit
( mob Huo
-

= 18 Tn E 18M
=
If J/mohe
 ✓

path
tf R=Rxf L
-
-

= 10×032=4 oats
OS =
Ncp In
IT ,
+
a R In
Az
Iz Rtn 2 t
Rahul =5zRhn2 2rem 2
= -

=
RzIn2