4.THERMODYNAMICS.

Als

HOGA

BAWAAL

By PROF
BURHANUDDIN
THERMODYNAMICS

#
NTRODUCTION

TERMAL EQUILIBRIUM

#RSL LAW OF THERMODYNAMICS

INTERNAL ENERGY (U)

- DtaRtts OF
I zA+(C) FREEDOM

LAW OF
WORK (W) -

EQUIPARTITON

MAYER'S RELATION

THERMODYNAMICS PROCESS
I

SOTHERMALPROCESS

A
DIABATIC
PROCESS

SOBARIC PROCESS
#

SOCHORIC PROCESS
I

SECOND LAW OF THERMODYNAMICS

HEAT ENGINE

CARNOT ENGINE
#

NTRODUCTION:

Thermo-dynamics
L ->
Motion
Heat

Theomodynamics deals with macroscopic properties of gas

volume, Temperature, Pressure, of molecule,

No. moles etc
ex

Translational Equilibrium:
the it said to be in
When net force acting on
body is zero is

translational equilibsion
0
Fret anet
=
=
0

Rotational Equilibrion:
said to be in rotational
is zedo it is
When not too que acting on the body
equilibrisn
[net = O CnettO

Thermal Equilibrium:

When the macooscopic properties of gas

remains
a
constant throughout
it is said to be in Thermal Equilibrium

Let us consider a Gast enclosed in a

system
since boundaries are adiabatic volume, Temperature

& pressure mains constant throughout

..A is in thermal equilibrion with itself.

Let consider two A&B enclosed in

us
gases
a
system since borndaries are adiabatic, these
is no
change in volume, Temperature & pressure
Note
↓ Al Bar in thermal equilibrium with each others. FTB
TA
Ze00th Law of Thermodynamics:
If two bodies Al Bare in thermal equilibrium with third body's then

others.
A&B are also in thermal
equilibrion with each

.:::::::..c: ........
r

·
⑧

....... A. & is
.::...: it

Internal Energy (V):

Total Energy of a system is
given by

TF k.z =
+ P.E + I.E

K.C molecules

P.C molecules

V.G molecules

If body is said to be in motion it posses

Kinetic
Energy
A 4.7 due to gravitational or electric field.
body posses
at oest & the
The
system
that we study under themodynamics, are
on

suoface
k.7 =
0 4.7 =0
i.

↓ T. F = 1.7: K.Emolt P.Emol + V. Emol

Vibrational Energy is
only considered
at
high temperature
↓ T.7 = 1.7 =
K.fmol +
P.Emol
Also
Molecules of ideal
gas
has no force of attraction ... P.Emo O

:T.7: I.7= K.Emor

&
egoces Of Freedom: -

Degines of freedom is the number of individual term in the

expression of
Kinetic Energy

For Monoatomic Gases: -

He, Me, As etc

1
y -
2

ise=tmve t
mvytmv
"x

:.
fmon =
3

For Diatomic Molecule:- Hc, O2, NaCt

Y~
- 2
wi
Li

isf=tmv+mvy +Mv +Iw} +tIw

↓

i
fpia: 5

For Taiatomic Gases: ·

Os, 503, Niy etc

Kt=tmu+tmv +tMv3xp
"

IIwi kIwj Iw
x
+ + +

i.fi 6
=

At high temperature all degrees of freedom are+ 2"

Law Of Equipastition Of Energy:
The Kinetic Energy associated with each molecule with each degree of freedom
is
equal to
t kpT
where Ks -> Boltzman's constant

-> -> Absolute temperature

For Monoatomic Gases: -

U molecule
I
= k T

NA
Umole
EkpT x
=

=
3RT
2

For inmoles

Unole =

nRT
For Diatomic Gases & Toiatomic Gases
Similarly

Unole: ENRT Umole

GnRT
=

↓ In genes al
Umole = nFRT
2

-> degrees of freedom

-

Also,
2v =

ER
u nCT
=

T
Diff.w.s.t

do = nCr

du = nCrdT

BU = nCrDT
 Heat (Q):
between two bodies at different temperature.
It is a
way of transfer of energy

It's a
symbol is

t's
#

so I unit is jool (5)

common unit is calorie (call)

1 (a) = 4.185

Hotelgiven to the system is taken as 'the'

-ve'
Heat given
out of the system (released) is taken as

Specific Heat (c):

It is the amount
of heat required to raise the temperature of unit mass
of a

substance by one degree celsius.

i. a mc/T
=

c:a
Specific heat of water is
given by
c= 0.2 5/gi c =
(callg'

Specific heat of gases

For Isothermal process
-

-> constant

xT 0 =

:.c = a

For Adiabatic process

a 0 =

.. c = 0

Thus,
[0,2)
specific heat of gases ranges from

-> pecific heat at constant volume & pressure

:c
1 1
T
=
=
1

1 1
Polar Specific Heat:
↑ -

It is the amount of heat

required to raise the temperature of one mole
of a

substance by one
degree Celsius.

c=T

But.
Weare
+
c=t
:c = M2

olar
↑
volume & Pressure
specific Heat at constant

Cv
BT
(p
BT
=
=

C 4cr =

[p Mcp =

Also,
I = Y

ayess Relation:.
↑

Cp -

CR =

Cv FR
=

f ->
degrees of freedom
: (p R+ Cv =

R
-p FR
= +

(p (1 E)R
=
+
Hook Done in Thesmodynamics: -

Klook is the mechanical way of toanfes of Energy

Hookdone in thesmodynamics is
given by
W PDV =

↑
-> pressure
volume
* v-> change in

- Movable

: Piston

oFoF
=

Gas expands Gas is compressed

work is done by the system
Work is done on thesystem
v Vi
XV vf Vi +
-
=

Vis V- XV vf Vi
= -

Av = + Ve
XV =
-
Ve

wookdone is positive is
=

↓
.wookdone
negative
Remember:

W=PDV is applicable only if pressure is constant

For graphical sums

Wookdone= Asea under the graph

Total Wookdone= Area

of the closed figure
in a
cyclic process

First Law Of Thermodynamics:

Heat
supplied to the system is
equivalent to work done
by the
system & increase in

internal energy of the system

. Q = W +AU

whese,
& -> Heat supplied to the system
↓-> block done by the system

u->
* change in internal energy
of the system,
Proof of Mayer's Relation: -

ideal gas heated at constant volume

Consider one mole of an

↓
Heat supplied to the system is
given by
a nCAT =

1
But n =

:a Cr1T =

dO = CrdT
Also, v -> constat

i XV 0
=

dw PXV 0 = =

B
y first law of thermodynamics
a w = + XU

do dw+ dU =

da 0
=
dU
+

...dU =CrdT O

heated constant pressure till its temperature reaches 'dT'

Let the gas be at

Now, dp 0 =

a n[pDT
=

da = CpdT ②

Also, dw = PAV

We know that,
DV = RT

↓ PAV = RDT

...dW=RDT ③

y first law
B of themodynamics
aw =
+ XU

do dW+dU =

CpDT = RDT + CrAT [from 08 & BY

R Cp
(p +
=

Cp 2v R
- =
Process Of Thermodynamics: -

sothermal Process:
system constant is called
A
process in thermodynamics in which temperature of the remains

as Isothermal Process
book done in an Isothermal Process: -

Constant
↑

->
is in
:: AT 0
=
Wookdone in an isothermal process change
We know that, Volume from V, to Ve
NU nC v AT
=

. W
=
SV-PdV
Xu 0 =

But,
PV=nRT
By first law of thesmodynamics

wYENre
a w+ ΔU
=

a = W

It is a
very slow process

nR+1"d
in conducting walls
It takes place W =

At constant temperatuoz v

By Boyle's
Law W =
nRT(10geV]
vx1

P V =
P
constant
W = nB +
(log,Vr-logvi]
S lope
r
of P-U curve W nR + =

log, (E)
P Also, PV = constant
r
S 4V, = PzVc

<
W
> v
Y =v
H

↑v = constant :W
nRTlog(E)
=

Diffw.o.t't'
PdV +VdP = 0

WdP =- PdV

d=
Slope=-E
AdiabaticProcess: -

The process
in
theomodynamics in which heat content of the
system remains constant is called

as Adiabatic Process.
book done in an Adiabatic Process: -

a 0 =

Now, wookdone in adiabatic process is

change in volume from
DU =
nCeDT V, to Va

yfirst law of Thermodynamics

c"pdv
B
:. w =

a w+ Δv
have
=

DU
We
0 = w +

W= -

AU
PVY k =

:Fora
For adiabatic Process
Y
4 v constant
=

But, PV=nRT
PRT

W=1jvdv
P =

nTvY = constant

↓
TV" = constant
w
kk
=

↑
(HRTTY=constant w
=(v yjy
p"Y+Y constant
E(v"-v.y
=
w =

Slope of P-V cuove

r
w=(kVY kvy] -

P
4,vvY]
=(Pvv
r -
- W

< - W = 1 (PzVz P,v)-

v > 1 Y -

PVY = Constant But PV = nRT

Diff.w.s.t't' :W
[nRTc nRT.)
-
=

Y 1 =

↑yr"'dV +VYdP = 0
W +nRCTc-T)
=

v"dP =-PYv*'dV 1 y
-

+ NRDT

THE
W

OFF
=

1 -
4

Slope--4
sochosic Process:
I
-

which volume of the

system remains constant is called as
The process in the theomodynamics in

sochosic Process.
I
Slope of 4-Ucoove
V -> Constant
pu
AV 0
=

given by
r
in isochosic is
Heat supplied process

a n(ΔT
=

<
- y
Also, -
Xu nc-ΔT
=

to x-axis
Graph is 1
Now, is not defined
book done in isochotic process is
given by ↓ Its slope

W PDV =

definet
dp
=> = not

W P(0)
=

w 0 =

first law
B of Theomodynamics
aw = + XU

a 0 =
+ XU

a ΔU =

IsobaricPsocess: -

the remains constant is called as

in which pressure of system

the process theomodynamics
in

Process'. Slope of p-V cosver

·

Isobasic
pr
-> Constant
↑
~

>
Ap 0 =

in isobasic
Heat supplied process is
given by
>v>
C
i a n2p1T
=

But, DU = nCvDT
·

aJaph is parallel to n-axis

Slope =
0
Also,
given by
H
Isobasic is
woskdone in process 0
=

w PXv=

Cyclic Process:
octuons system to its initial state is a
cyclic Process
theomodynamic process that
A a

In a
cyclic process the total change in the internal energy of a system is zero.

the total work done is

equal to the area of closed figure
I
na cyclic process
Second Law Of Theomodynamic

second law of thermodynamics deals with spontaneous & non-spontaneous

process

Statement:
be converted to heat
All work can

but

All heat cannot be converted to work

some heat is wasted

These is no heat
engine
with 100% efficiency
0 transmitted to other cold body.

HEAT ENGINt:-
& does work
is a device which extract heat from a
body
Heat engine
Source

O,

(x) 0, Or
Engine
-
=

Q2

Sink

Efficiency of -
whodone x100

heat Heat supplied

any engine

n
=

x100
n
00x0
=

n ( 8)x100
= -
Casnot Engine:
It is a
hypothetical heat engine. It is a seversible heat
engine. Its efficially
is maximum

In Process A-B (Isothermal Expansion]: -

AT 0 =

XU, = 0

&y first law of themodynamics

&=w + ΔU

:.0, =
W, In Process D-tACAdiabatic Compression]
work done isothermal
in
process is
give by On 0 =

w,
nRT,loge(E) i wa DUu
-
= =

(E
wothtre
:a. =
w, nRT, log,= =

In Process B ->c[Adiabatic expansion]: -

Q2 0
=

By first law of the smodynamics

aw =
+ DU

0= W + XU

Wc =
-

BUz
work done in adiabatic process is
given by

. WetREtri
In Process C->D(Isothermal Compression]:
xT 0 =

XUz = 0

... Oc Ws
nRT-10ye(Y)
= =
 heat Network done
Efficiency of -

a casnot's engine Heat supplied

NOW
Whe t
= W, +Wc +Ws
+
Wa

But, wc
=-
wn

. .

Whet = W,+Ws

t
n
=

a,

wt
=

loge((,) nRIlog(ES)
+
= nRT,

nRT,
log (I
-

+EgCurrO
But.
=

Era(Vesvit
1
y
+
.:
=

n
1-tryre
=

n
1-
=

But,
8
1-
n =

E0
:
=