Heat &Thermodynamics

Dr. Mostak Hossain

Professor, Dept. of Physics, BUET.
 Degree of freedom
• Degree of freedom
• The degree of freedom defined as the total number of independent quantities

Three type of degree of freedom

t a k
which must be known for completely describing the state of motion of a body.

o s
• Degree of freedom of translational motion, f𝑡
• Degree of freedom of rotational motion, f𝑟

. M
• Degree of freedom of vibrational motion, f𝑣

r
D
Total degree of freedom, f = f𝑡 + f𝑟 + f𝑣
Vibrational energy which is effective only at high temperature (above 1000K)
The Law of Equipartition of Energy
• For a moving system in thermal equilibrium, the total energy is divided
equally among all the degrees of freedom and the energy of a gas
$
molecule for each degree of freedom is equal to kT .
%

t a k
s
• Expression of energy :

o
• In the steady state the mean square velocities of a gas molecules along the three

M 𝑢 =𝑣 =𝑤 % % %

𝑣. + 𝑤 =3u
c = 𝑢 +r
mutually perpendicular directions are equal i.e.

D
But
2 % % % 2
$
∴ u= c 2
*
2
• Kinetic energy of motion per degree of freedom is
$ % $ %
%
𝑚𝑢 = -
𝑚𝑐
$
But PV= mnc2 = RT
*
or
$
*
mnc2 = RT
t a k
or
$
-
mc2
$ % $

o s
= 𝑚𝑢 = kT= constant
% %
Where k = Boltzmann’s Constant

r. M
∴ Kinetic energy per molecule per degree of freedom = kT
$

D
So, Total kinetic energy of a molecule is,
$
%
2
mc =
$
%
*
%
m(3u 2)

= kT
%
The Molecular Specific Heat:
The molecular specific heats is defined to be the quantity of heat required to raise
the temperature of one gram molecule of the gas through unity.

Let us consider one gram molecule of a gas. If dQ amount of heat raises its

ta k
temperature through dT, then the molecular specific heat at constant volume is

CV=
/0
/1
o s
r. M
So the quantity of heat required to raise the temperature of unit mass through one

D
degree, keeping volume constant is called the specific heat at constant volume
(CV).
But CP = Cv + R

/0
= +R

k
/1

s ta
So the quantity of heat required to raise the temperature of unit mass

o
through one degree, keeping pressure constant is called the specific

r. M
heat at constant pressure (CP).

=D
34
And 𝛾= Ratio of specific heats
35
Application of the law of equipartition of energy :

For monatomic gas: (He, Ne, Ar)

A monoatomic gas molecules have only

k
translational motion in space. So It has

ta
3 (three) translational degrees of freedom, He

o s
0 (Zero) rotational degree of freedom and

. M
0 (Zero) vibrational degree of freedom.

r
D
So, Total degree of freedom = 3
$
∴ Its energy = 3 × %
𝑘𝑇
A gram molecule of a gas contain N number of
molecules.
 * *
So, Total energy Q = 𝑁𝑘𝑇 = % 𝑅𝑇
%
;< *
Molecular specific heat CV =;= = % 𝑅
* >
∴ CP = CV + R = 𝑅 + R = 𝑅
% %

k
3 >?
Then, 𝛾 = 4 = = 1.66

ta
35 *?

o s
Diatomic gas molecules: (H2 , O2 , N2 )

. M
A diatomic gas molecule have 3 (three)

r
D
translational degree of freedom, 2(two)
rotational degree of freedom and
1(one) vibrational degree of freedom. H2

(Neglecting the vibrational energy)

So, Total degree of freedom = 3+2 = 5
 $
∴ Its energy = 5 × 𝑘𝑇
%
A gram molecule of a gas contain N number of molecules.
> >
So, Total energy Q = 𝑁𝑘𝑇 =
𝑅𝑇
% %

k
;< >
Molecular specific heat CV =;= = % 𝑅
>

s
@
∴ CP = CV + R = % 𝑅 + R = % 𝑅
3 @?
o ta
M
Then, 𝛾 = 34 = >? = 1.4

r.
5

D
Triatomic gas molecules: (H2O , CO2 )
1) For non-linear molecule (H2O)
2) For linear molecule (CO2)
For non-linear molecule (H2O)
A triatomic non-linear gas molecule have 3 (three) translational degree of
freedom, 3(three) rotational degree of freedom and 3 (three) vibrational
degree of freedom.
(Neglecting the vibrational energy)

k
So, Total degree of freedom = 3+3 = 6

t a
$
∴ Its energy = 6 × 𝑘𝑇= 3𝑘𝑇

s
%

Mo
A gram molecule of a gas contain N number
of molecules.

Dr.
So, Total energy Q = 3𝑁𝑘𝑇 = 3𝑅𝑇
Molecular specific heat CV =;= = 3𝑅
;<

∴ CP = CV + R = 3𝑅 + R = 4𝑅
34 A? H2O
Then, 𝛾 = 35
= *?
= 1.33
For linear molecule (CO2)
A triatomic linear gas molecule have 3 (three) translational degree of
freedom, 2(two) rotational degree of freedom and 4 (four) vibrational degree
of freedom.
(Neglecting the vibrational energy)
So, Total degree of freedom = 3+2 = 5
∴ Its energy = 5 ×
$
𝑘𝑇
ta k
%

o s
A gram molecule of a gas contain N number of molecules.
>

.
So, Total energy Q = 𝑁𝑘𝑇 = 𝑅𝑇
%

r M>
%

D
;< >
Molecular specific heat CV = = 𝑅
;= %
> @
∴ CP = CV + R = % 𝑅 + R = % 𝑅
3 @?
Then, 𝛾 = 34 = >? = 1.4
5
Relation between the ratio of specific heats and
degree of freedom

k
According to the law of equipartition of energy

a
$

st
The energy associated with each degree of freedom = % 𝑘𝑇
$

o
So, energy associated with 𝑓 degree of freedom = 𝑓𝑘𝑇
%

M
$ $
Thus the total energy of one mole of gas is Q = 𝑓𝑘𝑁𝑇 = 𝑓𝑅𝑇

.r
% %
;< $
Hence, molecular specific heat CV = = 𝑅𝑓
∴ CP = CV + R =
$
%
D
𝑅𝑓 + 𝑅
C
;= %

34 ?EF? %
D
Then, 𝛾=3 = C So, 𝛾 =1 + E
5 ?E
D
•Thanks