Thermodynamics

Ch- Thermodynamics

I
X
t

Classical Thermodynamics statistical Thermodynamics

· de ↳X
closed
eyes-
↓
solated system Open system
↓ I X

deal Vandimaal Ideal Vander wal

N

I Ovewiew

and universe
*
system surrounding
,

Paramites - Fundamental
* Derived
-

*
Types of processes
* Themodynamic terms and properties
first law
*
of thermodynamics
* Internal
energy calculation
*
Equipartition of energy
calculation

*
Enthalpy
*
Work calculation
*
Thermochemistry
of Thermodynamics
* second law
 I
calculation
*
Entropy
Gibbs
free energy calculation
&
*

shard
·

law
of Thermodynamics
* .

# system surrounding, and unnierse

->
System
I

· ↓ ↳
en system closed
system Isolated
system
Ladiabatic
syst
-EmatteI",
,
-matte
e
- - - a mater
a

- -

>Hat X

Sur ounding
Universe-
system
->
+

# Parameters

-> Fundamental Paramites

* T
,
P ,
V, M
 I
->
Derived Parameters

* H, S , 9 A Cr p
, , ,
, q

chan
P ,
T, V , N P , T , V, N

I Types of Processes

① othermal
process : At constant
temperature

heatI])
Work(s)mate
i

7 System
It
-Work (J)
-

Heat Temperature
· Measurement
·
A
form of of
hotness and
energy .

coldness .

· Unit : Joul · Unit : K, C

Internal
remains
->

energy constant in othermal

processes because it is the
function of temperature .

An = 0 AV =
0
 I
&

I drwing force opposing force ; Then

*
,
no work .

&

During force-opposing force ; I'm also no work

is done .
,

② Rochoric process 8 At constant volume

DV =

W 0
=

W
=

P A
W 0
=

& Sobaric At constant pressure

process 5

AP =
D

④ Adiabatic process :
Dq 0 NS 0
= =

is not allowed 970

* Heat
transfer .

⑤ Cyclic process : A
process
in which initial and
&

final same
s t a te

are .

WFO

qt 0

AV =

0 ,
An=0 , An = O , AT =

0 ,
AV=0 ,
DP = 0 .
 I
⑦ Prreversible process : The
difference between
driving
very large
is
force and
opposing force
.

work don is less in reversible

*
process .

*Sudden change ;
Pint * Pest ;

Pest=Pfinal (gas)
*
Equilibrium is attained at final step only .

Thermodynamic terms and propertis

-> Intensive and extensive Properties

Extensive Intensive
*
(pulation
which
· The
properties ·
The properties which do not
depend upon mass .
depend upon mass .

Moles
·
eq 1 (in context to H20)
Eg
,
: volume
·
, ,
mergy- concentration terms , temperature ,

libbs heat ,
capacity ite .

electrostatic potential .

· in nature Non-additive in
Additive natur

.
.
 I
Path and
function
S t a te

->

* Path Function state

function
· The
function whose values · The
functions whose values
initial and
depend upon path .

depend upon
final -
state

defined

->
not
.
They are not upon
⑧ These
functions are
dymed on states
&
.

path .

·
U H ,
S 4 ,
Cr , up qv qP
, ,

heat
,

(g)
,

work ,
cat Instant
·

and ps

-> Intoral Energy (Vors)

· As we
already know , Vx Temperature ;
⑧ Internal enogy
->
[Vo+ UT]
of
internal a

out the absolute energy

cannot
find
~

· we
out the change
system
-

hut me can find

in internal energy
-

AU= nCudT

function of temperation only

.

For ideal gas internal energy is the

· ,

u f(T)
=

is the
energy
internal

then
· when include Vanderwaal's
me system ,

function of temperature and volume .

 I
If &T 0
=

AU= nWdO
->
AV=0 (For iother mal process
-> To law
of thermodynamics
· when there is no heat flow
blu two- Normally
that the two objects
connected bodies we
say &&

are in thermal equilibrum .

A +55
z
bes 2
-
55
+q ↓ q
-

55
-

-
W

# first law
of thermodynamics
- AU =
W+q

>9
=

0 ,
W =
0

->
for isolated sys ,
AV=0

->

Energy can nether he created nor be

destroyed
OR

in internal isolated system

->
change energy of an

is z0
Pent dv
.

w= -
ne
&
AU
for Mothermal system IT 0 0
=

=
- -

,
,

AV= g W
+

in
q
+

0
=

Pest dV
q =

isobaric process
at const volume .

tw
+8 ↳W
O
,

y
X -
w

At constant pressure
process ,

constr
constr
.
.

-
PV nRT=

# s

9-Pent du (volume and temperature

some ratio
will change in

adiabatic 0
process q
=

↳ :
DV= Ag+ AW

AV=-Pract &
 lin
contains mos monoatomic deal gas is heated
2
If
a
② A system &

fund Out8
2005
bolhormally by
0- .

a
AU

dW

e) change in volume if system is kept at Latm

d) AH

A a) Isothormal AT O
=

V =
0

-
100J

W =
-
100]

C) W = -
Pet dV
-

100] = 1 :
01325 x 105 Padr

dV = 100

1001325 . x 105

dv =

10
2
x 10-5

dv =
-
3
10

O
d) At =

xcpd*
AH =

0
 I
ideal is
& 3 mot
of
an
gas compressed from 102
find
&
e-e
then out
pressure advabatically
8
to 31 at cate
-

a) AV= ?

b) W= ?

C) AS = ?

(Pressure should he
Sol" a) AV=-Pent dV
connected into Pascal)
I

--2atm X (3-0)

=-2x-7

AV= 14 atm

=14X 105 Pax10-3 m

=
14X 102 Pai
=1400 Joule

b) W
=

I W =
14005

-DS= ? DS =

0
for adiabatic process
 I
->
tha
capacity
ht
enquired to raise the
temperature
is

*I the

my 1° .

is extensive (Addictive
* I an property .

c
4 E
=

unit -> TK-1

->
spicfic heat capacity
the temperature of one
raise

* Tat required to
&

It is intensive property
-

gram by I degrees .
an
↓
Non-addition's
<plan =
1
m . At

Unit- JK gail
 I
-> Molar mat
capacity
mos
* that required to raise the temperature of I
by 1

(Intensive
digree ·

property-non-additive)
Monoatomic
cm =

-
dq (Ne etc]
,
->
ndT
Diatomic-I
(O2 etc)
unit ->
TK
-
mot /

Triatomic-I
(SO2 etc) ,

Cp-Heat capacity at const P .

* ,

->
JK" mot

git
·
JK-

TK
->

at constant volume ,
* Cr- that
capacity
-
JK molt
->
JK get
-
JK
· CP-CV = R

·
~- Poisson's
=

ratio
 I
& find required to raise the
out the heat

sample containing
P

a
lemperatur by 30 of
-
%

90g of H20
at constant
pressure if Cp=405K mot

Aus (p =

d
=>

dg nCpdT
=

ndt
->
dq =

5x 40T/moltx
30K
=>
dq = 60005

-W R
-> TKt molt
p
=

↓ ↳
JK-molt
JK-mot

(p-40 =
R
Cp>CV R YO
up =
+

up =
R+ W
8 314 + 48
p =
.

48 .
3145K-mol

dg =
n (pdT)
5x 48 314
=

.
x 30

7 247
=

,
-

1
 I
is heated upto 80° at constant
&
54g H20 at co

if =15
JK-gt the out heat
pressure ,
find .

An m
54g 2T 80-20 60°
= =
=

JK-molt
155k-g-1
( =

18x15

Cp-N R
dg
=

ncpd+
=

up
=

R +
W = 3x278 .
314x60

8 .

314 + 48x 15) =

50095 .
8 I .

up = 278 314 JK-molt

·

to 3 mol
& 2295
of mergy
is
supplied of an

deal constant P The temperature

&

gas at .

of a gas
increased What is the value
by 2 55K
.
.

of <and a ?
An 9 :
2295 n
=

3 mol AT =

2 55K
.

,
I ,

up =

de =

2 =

29 .

935K-molt
ndT 3 x 2 55.

=>

cp -W =

R
 I
=29 9 -8-314 .

=21 62 . TMol-k

ideal
⑦ The heat capacity of lomol
of an

gas
at
a
temperature is 300JK+ at

constant P .
The heat
capacity of the same
go
at the same temp at constant volume .

& is heated upto 80°

549 400 at 20°

at constant pressure if = 15 Tk-g

Then
find out
heat

60°
A 54g 21 80-20 =

M
=
=

W =

155Ktg-1 =

10x 15 JK-molt

up -2
=

R dg ep=
dT

R+ W 3x 270 314x60
C
=
.

50095-85
8 314 (18x15)
.

+
=
-

(p =

270-314 5K-molt
 I
ideal at
& 2295
of energy
is
supplied to 3 mol
of an
O
gas
constant P The
.
temperature of
this
gas
increased by 2 55K
.

what is the value ep and cu ?

of
A 9 2995 smol and At 1 55K
=

:
M=
-

93JK-mol
up
E255=
29
=

= -

=>
-W
=

=W R
=

up -

= 29 .
9-8 314 -

=21 .
62 JMol-'K-1

ideal gas at
capacity
a
① The heat -

of
10 mos
of an
&

at constant p The heat capacity

-

is 3005K-
temperature
-

at constant
the same gas at the same temperature
of
volume .

3005K- 10 mol
As 10 mol Cp for
=

m
=

p 1 30JK"- / mol
3, for
=
=

Cr =
G-R
 I
W =

30-8 314 .

W =

21 686 ·
JK+ mol"
Ans

Ho is raised from 15 % to
& The temperature of 54g of
75° at constant volume the change in heat during
this process , = 755K+ mol".

Aus n 1 3 mol DT= 15-15 60°C dq= ?

=
=
=

, ,

18

R
cp-w
=

W R
<p
=
-

W =

75 - 8 -
314

W = 66 68.

IK-mol

a= A
e

66 68. =

1 -

dq =
66 68x180
.

3x60

12 , 002045
dq =
 I
① Among
the
following the
system required least amount

give temperature
to 80°
thermal energy
of
at 400 = 200 x 40 8000
200g
=

a)
b) at 20° > 100x 60 6000
100g
=

at 50° => 150 x 30 4500

C) 250g
=

at 30° 300 50
d) 300g 15000
=
x =

# equipartition of energy

Summertional Rotational vibrational

f(RT) f(ERT) f(RT)

+

u
+

=
 I
-> Degree
of freedom
-
O alomicity
a molecule
* 3m :
of
monoatomic N=1
E for ,

dof= 3x1= 3

Go 02-diatoric https://www.google.co.in/url?
sa=i&url=https%3A%2F%2Ffanyv88.com%3A443%2Fhttps%2Fwww.slideshare.
6
dof 3x2
=

gitaThakare%2Flect-11-energy-level-diagram
=

freedom&psig=AOvVaw0sPkfXshNppEm3kGh
698829886504000&source=images&cd=vfe&o
GCO2-Triatomic 9
&ved=0CBAQjRxqFwoTCIDGgNT4n4IDFQAA
Ac
dof 3x3 =

Ego CHy-dof 3x5=15

=

3 x8 24
↳M3-My-dof
=

* For moneatomic N 1 dof 3

= =

, ,

U
=

3 /trans)
r =
3x
= RT
r
3Rt
=
 I
* For diatomic ,
dof =
3N =
3x2 =

U =

3 rans) +2 <rotational) +/(vibrational)

RT
=

3x1RT
+

2x1RT +

v RT
I E8 O2 N2, C2 C2, BM2 CN , CO
=

, , ,

* You triatomic (limar) ,

CO2, HCN , NO Is ,

dof 3N 3 x 3 9
=
=

~ (3N-5)
U =

3 strans -

) + 2 (rote) + 4 (rib ) :

IRT +
I RT YRT
+

3RT
-

* For triratorie (Non-linear) , 03 , M20 ,

H2S

3N
dof 3x3 =9
=
=

U =

3 / trans) + 3 /Roto) + 3 Chito)

ERT BRT+3RT= GRT

=

+
 I
non-limer
*
Polyatomic ,

U =

3 (trans ) -
+ 3 (Rot ) + 13N-6) (mb )
-
.

->
Ulat low
temp )= Transt Rot
Only
.

=
a
=
R+ W
r
up = .
 I
# Work

- Work

↓ I

bothormal ochori
Cyclic
constt. volume
Reversible Irreversible AV =

0
WT Wit Wet Wy
=
...

W =- Pent dro
&
x
W =o
Isobaric
Adabatic
AP =
O

Rusible Frreversible PFO

W= Pent
V

Free expansion
Pent =

du=ent du
du =
0

0-
calculation othermal reversible
-> work
for ↓
,

↓
-

migration
AT =

AV 0
Pent Pint
=

A dW= Pent de .

for reversible Pent ~ Put

process
.

PV= uRT
du=-Pint du div , = K

du=-MRT ·
dV Because it P , Vi=P2 V2
T the
changes 1 V2
V2
=

complete log
/dw=-nRT I
--

P2 Vi
du values
Y
 Clnv]Y W= 2 303 MRT

I
W ART
·
-

= -

The amount done

work
depends upon the ratio of incal
-- and
->

of final
-

volume and doesn't

depend
it

&
on the
difference blw the initiat and
qual volume .

calculation isothermal irrersible ideal

work
for
->
,
gas ,
.

= Rt
⑧W = -
Pent dV

W = -

Pent C2-vi)

Pent/RT -
W = -

W uRT Pent
(I -)
=

· Mass I : When Pent=P2

nR+/-)
W =

W
nR+(2-2)
=

2
=

Pent =
P2 -
11IIIIII

Pent =
zath-
-Pent= Later
Pz =
batm .111111 I

P =

loath .
 I
->
Area under the PV-arne is work

12 step)
⑧
regular (single step) <Irregular
work done work done

A A PIV I
⑧

:Ill
↑
P

Pave
11/119B ↳

Figs-Irreversible one
step expansion
·
Talking about magnitude
of work done .

on (om
(Wivnersible I
=

A ,p
N
⑧ Multistep step
visible
Reversible
(Weverable) I +

:a
two step-
ve

IN easible) =
I
+

I +
El+ It

·
11 -> one
step conversible compression
#
irreversible compression
#

-> two-step
↓ N

slightly I

gater than #

multistep
"reversible P2V2
a
oversiblecompression
·

expansion >Multistep compression

 I
Campesibtiomstp)
=

I + I + +

I + I+ +

(Wirenvisible step) =
I + I
+
I +
IN +
E+

compresion two

Iwrensban) =
I +
I+ +

& 1Og of U2 ,
P, = 20atm ,
Pc = zatm ,
T =

213K

DU= ? q 2 Whan
=

A W =
2 303 nRT
log
-
.

=-2303 x5 x 8 314 x275 -

log o

= -
2 303x5x0 31
. .

x 273 x 1 3010 -

W =
-

34002 .

735 A
1 Cal =

4 18]
.

AV =

0
,
AV=gtW

34002 735 As
9 = -W
=

ideal is heated at const Pressure from

.

mole an
gas
②
One
of
O to 100°.

Calculate the mork done

as
 I
and I atm
Expanded
reversibly
isothermally
at o'
b) from
to P2 .
What must be the
final pressure if the man .
Work

is equal to work in (a) . Then P2= ?

Anal = 1
,
AP= 0 (Isobaric) ,
T =

0°
,
T2 =

100:

W = -
Print dV

w = -
Pent (r2-vi)

W -Pent
Me i
= -

w = -

nR(T2-Ti)
= -

uR (373 -

273)

w = -
1x6-314(100) =-831 45 .

b) W 2 303 URT
log
= - .

631 4 =- 2 303 XIX 8 31 x273

log
-
-
. .

2 -

-
logP2= logt =
- =

100
-

2 .

303x273273x2 .

303

P2 =

10
-

( x 2303)

log P2=
 I
P2 anti
log(s)
=

Reversible-
-> w = -

2-303 URT
log - bothermal I

ideal

Pent.
( 4)-
othermal
W = -URT Traversible ,

ideal
r
2
=

ideal
- work
for
adiabatic ,
reversible
↓
,

↓
system :

↓
aligration PV=
-
RI
0
q
=

is allowed

Pir , =
Pa Va

Pvi adiabatic
sys te m

=
ver --
for
PIV , =

P2v2 -

for
exothermal
system
-> W= Pent du
Ar =

q"+dw
du=-Pirt (V2-VI) - fou adiabatic q 0
=
.

dW NRT
Ar dW
du
=

= -

F w = nwdT
 I
YdW =-RI I dr
·
;
W= nCCT2-Ti)-

· From eq. ① and D .

->

- Pint dr= .
nCdT

I 1
URT
-
dr =

xcrdt
,

I R
A so At t
-

Ren
- Coln I
TI

> en I = I E
v
TI

I & In =

In I
e V2 T

=
(v-1) In = In =

Mr()-
 #
*

(v) =
=>

(2)
= (2)
->

-
->

cras
(v)
I
=> =

- >

PIV , =

P2 ve

Piv , =
Pe vo

P! T= R To
P2 (2)
"

P!)
=

=> =

Pe +2 Pava-PIV
-> + =
W =

eW= E i
Conclusion : For
reversible and
irreversible
p, +, =

P2* -
-
Reversible only P, , P2 v2"]-
V =
Tv = Tzr2o
 I
e
-
v 1 1
=>
=
->
-
=

-Isothermal
=
·

P
-

->
Reversible adiabatic
rd
--

>
V
PV Const ·
- ↑
Pr
=

=
Const .

dPV+PdV = 0

div = -Pdv

I=

->
In reversible process ,
Final pressure-external pressure

natural process
-> Irreversible-sudden change ,

-
Final PF Pet .

adiabatic invisible Ideal

Work
for ,
gas
Pv= nRT
->
de ↓
0
Pent F Pint .

q
.

-Pent du
gu
W =

& AV=

W Prt
(vz-viL②
.

AU= W
=

n crdt =

W From eg .
$2 ,
*

MCLT2-T1)
=

Pent (v2-VI)
(T2-T1)
-

W =
ne
-

0
1
 I
2 mot a diatoric ideal gas at 300K 0 5
.

Mpa Pressure
② of
, . .

of the expanded adiabatically against a constant

is
-

gas Calculate

exctoral
pressure of
0 1 Mpa
upto 0 2 Mpa pressure
.
- .

theCalculate mork done by gas

final temperature of gas
& ,
·

mol
An n 2
=

Diatomic T1= 300K

,

11 =
0 5
.

x 10Pa =

5x10Pa= 5bar

Pent =

0 x . 104Pa= IX105 Pa=Ibar

P2 = 0 -
2 x 166 Pa= 2 bar

nCv(T2-T1)
=
-
Pent (V2-VI) .

=Pent
(n-n i)
.

Pent
ncCT2-T1) uR
(= )
= - .
-

& (T2-T) Pent

(E
-
)
=

- .

-(12 300)
- 1(2 3)
-
= -

Tz =
270K W
ER
=
 I
W = na(T2 T1) -

5x8 314x 30
R(270-300)
= . =

xx
,
=

=- 1247 15
8 314)5
.

(5x 30 x
.

W
=
-

Reversible
O

② Adiabatically
-

n
=

2
,
Diatomic gas
P1= 5bar P2=Ibar , T1 =
300K , T2= ?, W =
3
,

Aus p, +V
=

Pe +z2
-

for diatonic gas ,

11
zR z
=

W up
=R
=
= v =

,
,

-
-> 51 5300
-

1 E T2

51-
1 4
-

300" =

11-n Tz
I

SoSee
1 .

ty L
I =

Tz

->
(T2)" =

1543 .

58

log T2= log

->
1 4
.
1543 .
58
 I
logic
jog 3.88)
=

InT2
=H
=
=
5 244
.

5 244
T2 =
antilog .

=> Tc =
189 -
42K A

->

Graphical Representation
PO 2atm V 52.
=

= , I

UP A B
inside the curve
- -

/ W= area
/
/
/
///I
P

S
=exb
C a
PO 3P0=12PVI

I
--

= NVIX

12x2 x5
=

120 atmL

su

=120 x 105 Pax 10-3 m

105 Pa
I 3m3]
1 atm =

=120 x 1025 21 =

10
-

=120003 A
-wi

///
vW2 0
=

clockwise war
P
=O

we e W3
I

,
Wi
-

> Walt =- With 3

Whst=tws-w , Wret= the

Writ =-ve
 I
Calculation
Enthalpy
->

·
H- enthalpy
&T
·
change in enthalpy ->
AH= up

It is a
function of P ,
T .

nCdT
energy change
V=
· Internal
to
v)
u -
f(7 ,

dr =

(A)
+
(a)
AV =

q +W
ideal gas
(4) AV
9-Pent AV
0
=

-
for
=

v -const .
AV= 0

dT ncpdt
(A) dr Pent &V
=

dr
=

0
- =

* transfe
e
heat
gr -
- AU= DUTAPV

9x-mobarattransferable process
*
=> AH= AV+(P2V2-PIVIS DH
= ,

Isobaric ,
At constant P .

P, = P2 :

AU= DU+PAV
 I
Al = AU+ PAV
I
I ↓
for reaction
For phase change
↳
AH AV+P(Vl-vs)
Multing (s = 1)
AU=Ar+AngRT
=

IPV MRT)
U +P(Vg-v!
=

g) An=
↓ &

(
Boding
- =

negligible IPAV= Ang RT)

(rg>> ve)
BU
=

AU +
Prg

sublimation (s g) /H AV+(rg-vs)
-
-> =

(Ig vs)
An= DU+Prg

-> calculation of Ang

((l) 2 D (g)
B(g)
+

2A1g)
+
--

Ang (ng)p-(ng)
=
i

=2 3 Ang=- 1
=

G
:
H2(g)
+
Iz(g)
=

242(g)

Ang Up MR
=

= 2 2 0
=
-
 I
+(B() +
32(g) -
2(1) 35(s) F(g)
GA(s)
+ +

1-3
Ang 1
=
= -

I
>DU-Ang
I AHLDU->Ang
Al
=
the

AU-Dng
DH= 0
=

: the

E
calculate enthalpy change on
cooling of math from 50 % to 5°C .

35K-mol and the mass 420 is

of Sp
75
of 54g
=
. .

An AU=
ncpdT
3m
n
2
=
=

=
3x75 3x .
-
45k

Al=-10 1655 , As

& 3420--340 (4) =

75 35 .
mol-
So -50
(p)5= 36 ·
85 mol- k

03ksmol
An enthalpy of fusion 6 .

420(1) -
2011) - 420(s) -> U20 (S)
10 °) 10°C) Als ( 50)
-

(5 %) AUI
↓ ↓

AH3 =

n(cp)sdT
Du di 3x6 03 x 105
n (cp)e DH2
.

= = -

=
-

3x36 . 3x( -

5) 5
=

3x75 -
3x15) /
 I
DU= DU1+AU2+Als

5) 1 3-6030) 1- 552)
=1 1129
+

+ -
- .

=-1129 .
5-18090 -
552

An=-19 , 771 55 .

① U20- H20 n =
0 =

5t
m

-
10 110°

m
90g
=

15 Stat
=

6 03KSmolt
(p)s 36 85 mol
-

= .

15 35 mol- K
(p)R = -

Drap 1 =

102 K5lg

(p)g
=

92 55 .
mol"K-

An H20-H20 -> yo -Ho - Ho-Uo

"O
-

10°
DUI
OR DUL O Ally 1000 DUn 100 Ms

AM1= 5 x 36 . 8 X10 A42 =

5 x6 -

03 x 103 A43= 5x75 3x100 ·

=>

301505
=

37650
=18405

AGn = 1 2 . x 10 x 90 AU5 =
5x92 5 x 10 .

=
1 .
0800 = 4625

AU= AH , +AUc+AHs + A Hy+ AHS

=

Al =

1 , 82 2655
,
 I
In bomb calorimeter-at constant holume-Av
①
NH2CN2y) +2 02 (9) +

H20(1)

1U=-742 7 . KI molt

T
=

290K

Al= ?

RT
An DU=
AU+Ang
DH= -772 7 x .
103 +

1 -x0
-
-

314 x298)
=

743 9K5
:

x0 314 x290 743938

7 x103 5 7865
. =
·

=-742
- .

.
 I
# Thermochemistry
-> NESS'S LAW

& AUr= AU1+AHc +Als +Ally+A45

A AlsFr 4g

AHI
E

Ban "Jus's"Ann
N2
Thorochemical equation 8342 CNH3
+ -
·

ArH=-I KT Mol-

reaction

->
Types of
↓

Escothermic Endothromic

R-P AWH= (ve) R- AUH=(He)

 I
ArH=(Mp-HR) the
=

ArK=(Hp-HR) = -
ve
ArH= (Eaf-tab) =
the

ArU=(Eaf-FaR)= e

from eq OSD
From ① and & .
,

eq .

(Eaf -tab)= (4p-HR) CHp-HR)= [Eat-ta b] ,

↓
backward
forward
HP > HR .

UP < HR

2A +B -
2C +

2D
⑧

ArH= <Up-EHR
=
(2HC +2 HD) -

(2HA +HB) (Hp <

HR)

Enthalpy
Reaction
->

· Standard Reaction enthalpy - at

/Ibar]
(DWHY

* Reaction enthalpy changes

with change in temperature
and Pressure
 I
*
-
formation (DfU-standard
of
Enthalpy

the
* I is the energy involved or evolved
during
at 25° and I bar
formation of
I mol
compound pressure .

* Reactant and product should be in thir naturally

occuring state .

02 (g) -
E(graphite +
CO2 (g) DM A4
=

Naturally occuring
carbon is graphite
not

of
state

·
&

diamond .

02 19)
-
Co2 (9) ACH # AfHO
(diamond +

CO2 ArH*
102(g) If Ho
-
Co +

+02 (9)--2H20(1) DWH + If HO

Eo242(9)
AfU= DSH
I

E: Graphite + 342
(9) --GH6 (l) Art = Af
 I
->
Enthalpy of formation (DfH)
->
Bond dissociation enthalpy (Adios)
lattice (Plattice H)
enthalpy
->

(hyd US
Hydration enthalpy
.

->

Atomisation (D art)
->
Inthalpy
->
enthalpy (ANewH)
Neutralisation
-> solution
Inthalpy (Asolt)
-> Fonisation
enthalpy (DionH)
sublimation (DSUbL)
-

enthaly
(Dfush)
Anthalpy of fusion
->

transition (trans
fulhaspy of
-

crystallization (Deryr)
->

thalpy of
-

Enthalpy of Vapourisation (snap H) .

Electron
gain Inthalpy (DegH)
->

Resonance
->

enthalpy
 I
① Bond Dissociation (Always Indothoais)
enthalpy

to break
energy required
mole
I
* is the one
of bond .

BCH
⑭ N Hit A diss H
=
-
-

- on - 0+2H H =
A dis H

~ -H
->
B +
3H
A =
A diest

= Adiss H
P
- UP
P
·

0
=

c
=

0 - C+ 20 = A diss .

H(C=0)
2

· Mr double bond is considered as a

single bond) .

NEN- IN DrH= A diss ·

HINEN)
H
I
H -
CHz +

H
H
-
-

C
AHI A dies =

(DH1+ AU2+AH 3THY)

↓
4
M3-CH2 +H
DH2

C2 Cit CH -27H
Any
 I
Adies Ucon) 1005 (A4 D Uco= 98 (DUz) Y ?
E
=
, ,

10
DHIADH2=
= 100 a
=

=>

& (Alattice 4)
lattice
enthalpy
· It is the
energy
involved or evolved during the &

solid its bolated

breaking or
formation of I mol
of from
gaseous phase .

· Nat (9) + Ci(g)-Nace(s) Blattic U =

e

Nace(s) - Nat (g) + C (g) Blatte H =

the

lice(s) -
citys +
ce

MyCc(s) Mg2+ (g) + 2x (g)

-

Alls (3) Als+() 34 -(g)

+

S00219)
ig soy- Mg2+ (9)
+

A latt .

4 & Charge Blatt U &

Bond
length
 I
For Advis
,
H DACH-EAHR-EAHP
All other enthalpiss , [AUp-EDHR

③ Hydration Enthalpy (Dhydl)

( A hyd4) Na+(DhydH) Ct
·
(DhydH) Nace=
A hyd 4 <
charge < - +1
r+ r-
I I

Bond length
is the released when one mole in gets
·
enogy of
It

dissolved in excess amount M20

&

of .

⑰ Enthalpy of Atomisation (Dat

produce mole isolated

energy required
to
⑧ I is the
one
of
elemental solid state combined
state

its or
atom
from
.

Sublimation and atomisation are

Na(s) NaCy
I
,
in

Mn (9)
same this cases
Mn(s)
- 12 (8) 4 DaH
ICIS) 2119)
-
=
.

Uc-2 = dis
Dat Dr
=

A e
 I
⑦ OSNT 3019)
Adiss A9H
An 4
1 750K5 1500 500K5
=
= =
=

=
- 002
K

& On up

A Adis
300
1 500KT
=

DaH
=

10
. =

750K
, =

⑤ sublimation Enthalpy
to convert I mol solid into gas
is the heat required of
.

·
I

A sub H

Mg(s)
-

Mg(g)
U20 (s)
** Ho(g)
* Chy(g)
(Cn(s)

⑧ Ionisation Enthalpy
electron isolated
The
required
to

remove the from an

·
energy
atom
gasions
-

Na (g) Yar Nat (g)

Dion 4

My (9) -
Mg2+
(g)
Al(s) - Ag+ (g) X NO Dion M
 I
⑧It is the energy required to convert I more of ot
from an

of ou-from
mole a base
acid or one .

+H
CH3-COOH -> M3-COO

-CH3-C00OK--CH3-200 + H
peacid)
My 1OH)2-Mg2t + 201

Ph-OH--PK-0+Ht

⑦ Fusion (Afus H)
Enthalpy of
.

to convert solid into

·
Engy required I mole
of
liquid .

⑧ Enthalpy of Vaporisation (Drap M)

energy required to
of bird to
convert I mol
· t is the gas .

Enthalpy
Solution

⑨
dissolution of I mor
⑧
It
is the energy involved or evolved
during the
sufficient
&

amount Mo
solute in excess or
of .

⑩ Neutralisation
Enthalpy of (DNewt)

ut tout-uso -
57 1KT
.

UC + NaOH -H20
 I
It combines with 1 mol
of ot
-> when I mol of
to-57 1K5
-> Avenh is always constant and equal .

CH, COOH + NaOh -> ANenU =- 57 1+5 .

↓Dion4 ↳ 52 1kJ
Hypothetical
=- :

=-5K5

value Ut + OH-F11 H20

⑧ For weak acid ,

I NewH is different and
for strong
acid
and base it is-57 1KT
strong .

Din H
& ANCUH=-57 .
1+

Awen u =
( -
57 1 .
+ 7) K5
HC NHYOH
+

=
50 .

1kJ
and) I weak base)
·

strong
n +
↓7 kg
Or-- H20
-

57 1K5
·

⑪ Transition (Stans")
Enthalpy of
mole
for the transition of of
O

required one
is the
· It
energy
allotropic form into another allotropic form for I mos.
Atrans H

Si S - S
Rhombic
Monodinic

graphite A trans <diomond

4
C

⑧(DgU) of element $(B , h) of compound

is zero in its
naturally occuring state
an a

can't be zo .
 I
⑧ Enthalpy of Crystallisation/Hydration
·
Cuson + H20
-> Cuson -
5420

Ankyd .

mot
It is the involved or evolved when I
of
·
energy
anhydrous
solid
get hydrated
in its crystallised form .

⑬ Resonance enthalpy
released due to resonance in a
⑧ I is the energy
molecule
Aus H
.

HHc =

CH-4 =
CH2 --CH2 =

CH-CH =
CH2

unconjugated conjugated
- n the
when I
mole
of MIC is burned in excess
of O2 ,
the
·
released is combustion (A)
energy enthalpy of
It is
excothermic
⑧ always .

⑭ Electron gain enthalpy

in
I is the evolved in order to get one extra electron
·
energy
isolated
&
atom
the Outoost shell of an gasions
.
 I
u + i - e-
Degh
F
-

+
e -
F

-> Born-nabe cycle

DIH
Na(s) C2 (g) Nact(s)
·
-
-
+

↓ Bist
Asubt
↳ Bat
u(g)
A

A latt H .

Na(g)
.

↳ BegH
↓ IE
Nat Cl (g)
-

(g)
+

AfH= AsubH + I E +
/ B ) +DegH +A lates
-

on
⑦ find out the Aft for CHy-Mc-C2

An (AdissH)02 =

acK5/mot (Adirs) .
H2
=

y k5/mol
(AaU)c =
2K5/mot (ACH) Ch3CH2 =

PK5/mot

(AAH)CO2 qK5/mot (1fH) 120 R K5/mol

=
=

12 - 24 , c(s) -((g) CH2-M2-C02+H20 -

 CCs+ Hg) Only-Women a e

I
OH

1 .

342 + 4100 - Ms-M2-CH2 +22-PK5/mol .

2
. 3C1s) + 302 --BC02 -3qk5/mot
3 .

TH2 +
202 -
H20 YRKs/mot

3
1 02
+

-C13-M2-CH
z
+

(-
AfH 3qMR)KJ
=
+

& (AfH) c =-110Ks/mol (AfH) 82 =-393 Kilmol

(Af4)N20 =
81K5/mo) (AfH) N204 =

9 -
7Ks/mol

N20n(g) +

320(9) --N
, 0(g) +302(g)

CHO-C0-110-1-110) =

110

CO2 -102 -

393 ↳it should he in reactant side in final

N2 +

02 -
N20 81 equation)

N2tO2 9 7
-

4 7
N204
.

-
.
 I
[
ArH =

[ (Af4)p- (Af HR

(81 + 3x( -

393))
-

19 7-3x110]
-

(81 -1179 -9-7 +

330) KJ

777 745
=
- .

x(DCH) (H -000K5/mo)
A
I
=
-
+ 342 1
(ACH) H2=-200K5/mo
A (ACH(C6H12 = -1400K5/mot

X +
102 -
da2+3e

3H2 +

BOL
-
3 A20

ArH=[(ACHR-[(DCHIP

A calculate the standard enthalpy of Ch , ou using the

following informationo- 1Af 1) an3 on

(ACU) M , on =- 726 15/mol

An
(graphte to>
-> Co2(g) = -
393K5/mot
242 +
202 - 2420(1) =
-286Ks/mo)
=

2x 206Kt/mo)
-

Ignaphite + 242 +
102 -> C304 (1)
 I
C3OH
+302--CO2 + 2H20
(flipping the eq.
CO2 + 2420 My OH +302-1-726K51mol
->

726K5/ mot
=+

↳+ 210
Co2 ->
CH304 - 02

2H2 02
24
+
-

I
Graphite + 02- ↳
CO2

Cgraphite + 242 +
102 ->
M3OU

Art= [12 x -

286) +
( 393)7
- -

[7263

& (cry(g) -((g) +YU(g) (AdissH) <-n=?

C exists in
a) /A vap vo Cly 30 5 K5/mol (Naturally
=

.
.

lqud state)
b) (Ap hi) <Cly =-155 5 -
K5/mol

2) (A9M° =

715K5/mol

(DAHP C2 242 k5/mol

d)
=

715K5
(XS) -> (((g) .

242(g) --
2x20(g) 2x24245

x1y(g) - (e) -
30 5K5
.

((4) -(15) -
242(g) 135 545
+
+
+
.

xCly(g) -
<(g) +

4x(g)
(135 5 + 715 434-30 5) 326K5/mol
. +
.
=
.

Y
 I
-
Maxwell Equation :

Pv= nRT

(-) (e) (a) E

* - =

2 -
+

(d) ( *) *
=
2()
+ +

So
(a)
*
(d) -
-

- (a) =
=I

"(o) (a) R
(a) (i)( )
=

*
-

5 .

( *) = -
 I
my
↑S H
Prakash &H
da
=

=
TdS+ VdD

vdP-SdT

Uta U 9-God
=
dU= IdS -
Pdv
le

dA=-Pdr-sdT

very . rid
-Maxwell's equation
Find out the value
① of (4)-
du= Ids Pdv
An
-

(a) ( -)+ P a) += /r) -

-

P P xx
y
D
(a)r P
-

0
-
- -

-First thermodynamic
equation of state
 I
(t) ( *)v -) ( *)s
=

+
=

(4) -
-

() = -

/) (*) -

- -

()s() =

(-) s
=-

(a) ~

& ( %)

An dH =

Tds+ VdP

) +
=

T()- +
( *) +(*) + V
=

( *) *
(E) + v rt
=
=
-

+ ,

thermodynamic equation
) =
-second
of State
↓
for ideal gas only ,
not van der maal's
 I
->
Cyclic rule :

P
aT
I

For ideal gas ,

(t) ( -(2) +
=

(
-

)()()

Yy
= -
=
= -
1

& (4) (a) ( *)+

An *** x
*
=
-

x =
=

1 x =

=(a)
a
* I
=

= *
 I
&B =

( -)T
A =
-

* = =

Ar =

(A)v
A I ** I
=
=

Find out the value ~P

② of

= x 1
*P
a
=

A find out the value 2

of x TV .

a
***
x
= -
 I
* T()(4) =

**** =
R =

ep C
-
-

X
=
Second law of Thoumodynamics
-
ass
AG = re-
spontaneous
·
&

14 =
0 -
Equilibrium
Non-sponlancous
-

the -
AG =
#
->

->

->
I Entropy
Degree of
On

On

that

In
↓
sing temp

supply
general,
randomness

sing pressure

solid id I
at

at
in a
system

constant PSV
constant +$P

see
.

I
Entropy Pass .
 I
ECo2(g) O2 As= the
-C0(9) +1 Ang =
The ,

Ang 1 5-1 0 5
=
. = .

CH20 ->
242(9) + 02 (9)

Ang 3-2 1
=
=

A1 =
the

: H2(9) +1219) -
CH1(9)

Ang 0
=

AS>0 DSCO , DS =
0 ·

-> Calculation As
of
*

As =

Ne
T

Saaa e
Du dg + w
=

TdS =

da
T dS = dU-w

dS
AT Ad
=
+

T
S2

si as
ne ++
=
 I
S e
ne
nar In
As =

UR In ve
# !

As =

narr
,
+uRln ( )
Ds =

nat URI Ren

-(CVAR) ne +
uRln
As npl +uRln
=

->
Cas : For isotirmal process ,
IT =

DS =
UR In
VI

DS UR In
b
=

Case I for isochoric AV=P

process
-> : ,

As =
nWInE
TI

->
Ca For isobaric AP O
proces
=

: ,

As
nupIn
=
 I
-> Is for adiabatic proces , q =0
As
=
DS =

-
GRE6 For phase transformation ,

As =
&q
T

② Find out the As

for 54g M20 .

Ho0(1) -
H20(g)
(50 %)
100°)
at 1 atm p , (p =305 molkt ,

A
vapH
=

5003 molt

Als M2011) - Holl - H20

19
(323k) (373k) (373k)

AS n pen Tz 1S1
1
=

1
50
=
=

F
373

1S1
log (323)
2 303 x 3 x 30 BS2= 1 34 JK
=
-

.
·

DS1 =
12 89Jk+.

AS =

As1 + AS2 =

12 .

89 +
1 -

34

DS =

14 .

23 JK
more
I for 1 mobi

(p1g H20(q) H20(g) Hrolg Ho(l)

35
=
->
↑
-> -
-

(pil=30 I alm Sate Satt 5att

110° 110° 100° 100°

(p15=25
V =
2 L

->
H20 (e) ->
H2011) H20(1)
way
e -
-
H20()
batt bathr Latt O

100° 50°C
T 502 14
=

H20(s)
H20(s) E

0
-
10°

Ans H20(9) -> H20 (9)

As
nRI
=

Later 5 atm

110°C 110°

Step It : H20(9) - H20(l) As nCp

In
=

,
Satur Satm

100° 100°

Step H20(9) H20 (e) As

A 5
-

III :
- =

xx =

Sate sate s

100° 100°
/
Step
# I
H20(1) H20(1) As
nRln
-
=

Late Sate

100° 100 °

StpE 8 Hou -> H20U As =

nup In
Laten satm ·

100° 502

As
H20(l) URIn
=

Step #3 H20(1) -

Late I atm

50°C 50°C

H20(l) - H20(1) AS =

n4p In T2

I attr I atm T
50 0°C

8 He0 (l) 120 (s) As1 - 10

Ausion
- = =

0 O 273

Step H20 (S)

In
:
H20(s) DS
-> =

nup
O too
 I
Entropy of Missings
->

AtB
*
- -

- -
t

- -
I
B
- - -

-
-

- -

- -
-

-
- - -

S1 =

3005k+ S2 =
200 JK 85
=

5055k

(S,+ S2) <

S3

Entropy of mining S3-(S1 + S2)

=

cold
that loss
of hot
body- Heat gained by body
to make it the)

* -

ncpAT
=

nCpdT if
-

final temp .

Th-hot temp ·

n
(p(Tf-Tn) n
(p (Tf-Te)
- =

Tc-Cold temp ·

If

Hot Cold
Th TC

AHI= AN2
-
 I
temperature in
E 30
g
Cu Rod
having 88c
dropped a

lank
containing 500g H20 at Soc
-

Find out 8

the
a) Temperature of system
If (p1H20 =

40JKg-1
( , a =

255k-g-1
Formula : MCpdT will be used because is used in
g
unit mor
of rather than .

As - mup (Tf-Th) mp(If Tc)

=

,
-
 I
- Graphs
logp+ log v logK
0-
Ov= K-mothoral =

Piv = K- adiabatis logp =

log K-log v

y etun
=

logk Isobaric
4
logp
↑
Isothermal
slope=- &

Isochoric
Adiabatic
7

logv- V-

logp+ logvlog
a

Isobaric
⑧

logp
logp r log v log k
=
+
Bothoral
logp logK-rlog v
=

adiabatio
Isochoric
y It Me
=

↓ monoatomic
fou =
=

>
work : Isobaric Isothermal>Adiabatic Isochoric
 I
A B
A a
⑧ >
-c Temperature at A , B ,
F is Ts .

P
for Y
↑

E
[ ⑧
D emperature at 2 D
, , E is +2 .

T, >T2 .

A A - B -

Isobaric and isottoral

Adiabatic
B - C -

and isothermal
Isochoric
c D
-

D-E-Isobaric and isotheunal

E F -
0

Adiabati
-

F - A - Isochoric

and Isothermal

CAND OF CHAPTER]