Principle of Equipartition of energy

According to this law, the total energy of a dynamic system in thermal equilibrium is shared
equally by all its degrees of freedom, the energy associated per molecule per degree of freedom
being a constant equal to 1/2 𝑘𝑇 where k is the Boltzmann constant and T is the absolute
temperature of the system.

According to kinetic theory,

1 ̅̅̅2 = 3 𝑘𝐵 𝑇
𝑚𝑣
2 2

̅̅̅2 = ̅̅̅
𝑣 ̅̅̅
𝑣𝑥2 + 𝑣 2 ̅̅̅2
𝑦 + 𝑣𝑧
1 ̅̅̅2 1
⇒ 𝑚𝑣 𝑥 = 𝑘𝐵 𝑇
2 2
̅̅̅
𝑣𝑥2 = ̅̅̅ ̅̅̅
𝑣𝑦2 = 𝑣 2
𝑧
Similarly,
1 ̅̅̅2 1 ̅̅̅2 1 ̅̅̅2
𝑚𝑣𝑥 = 𝑚𝑣𝑦 = 𝑚𝑣𝑧 1 ̅̅̅2 1
2 2 2 𝑚𝑣𝑦 = 𝑘𝐵 𝑇
2 2
1 ̅̅̅2 ̅̅̅2 ̅̅̅2 1 ̅̅̅2
𝑚(𝑣𝑥 + 𝑣𝑦 + 𝑣𝑧 ) = 𝑚𝑣 1 ̅̅̅2 1
2 2 𝑚𝑣𝑧 = 𝑘𝐵 𝑇
2 2
1 ̅̅̅
2
1 ̅̅̅2 3
𝑚(3𝑣 𝑥 ) = 𝑚𝑣 = 𝑘𝐵 𝑇
2 2 2

Monoatomic Gas

1 ̅̅̅2 1 ̅̅̅2 1 ̅̅̅2 ⅆ𝑈 3

𝐸𝑇𝑟𝑎𝑛𝑠 = 𝑚𝑣 + 𝑚𝑣 + 𝑚𝑣 𝐶𝑣 = = 𝑅
2 𝑥 2 𝑦 2 𝑧 ⅆ𝑇 2

1 1 1 𝐶𝑝 − 𝐶𝑣 = 𝑅
𝐸𝑇𝑟𝑎𝑛𝑠 = 𝑘𝐵 𝑇 + 𝑘𝐵 𝑇 + 𝑘𝐵 𝑇
2 2 2
3 ⇒ 𝐶𝑝 = 𝑅 + 𝐶𝑣
= 𝑘𝐵 𝑇
2 3 5
𝐶𝑝 = 𝑅 + 𝑅 = 𝑅
3 3 2 2
𝑈= 𝑘𝐵 𝑇 × 𝑁𝐴 = 𝑅𝑇
2 2

Ratio of Specific Heats

 5
𝑐𝑝 2 𝑅 5
𝛾= = = = 1.67
𝑐𝑣 3 𝑅 3
2

𝛾 is the adiabatic exponent

Diatomic Gas

At normal temperatures

5 ⅆ𝑈
𝐸𝑇 = 𝑘𝐵 𝑇 𝐶𝑣 = = 5𝑅
2 ⅆ𝑇

Considering 1 mol gas; 1 mol gas contains 5 7

𝐶𝑝 = 𝐶𝑣 + 𝑅 = 𝑅 + 𝑅 = 𝑅
NA number of molecules 2 2

7
5 5 𝑐𝜌 2 𝑅 7
𝑈 = 𝑘𝐵 𝑇 × 𝑁𝐴 = 𝑅𝑇 𝛾= = = = 1.40
2 2 𝑐𝑣 5 𝑅 5
2

At high temperature

7
𝐸𝑇 = 𝑘𝐵 𝑇
2
7 9
7 7 𝐶𝑝 = 𝐶𝑣 + 𝑅 = 𝑅 + 𝑅 = 𝑅
𝑈= 𝑘𝐵 𝑇 × 𝑁𝐴 = 𝑅𝑇 2 2
2 2
9
𝑐𝜌 2 𝑅 9
ⅆ𝑈 𝛾= = = = 1.28
𝐶𝑣 = = 7𝑅 𝑐𝑣 7 𝑅 7
ⅆ𝑇 2

Triatomic Gas

Linear

5 ⅆ𝑈
𝐸𝑇 = 𝑘𝐵 𝑇 𝐶𝑣 = = 5𝑅
2 ⅆ𝑇

5 5 5 7
𝑈= 𝑘𝐵 𝑇 × 𝑁𝐴 = 𝑅𝑇 𝐶𝑝 = 𝐶𝑣 + 𝑅 = 𝑅 + 𝑅 = 𝑅
2 2 2 2
 7
𝑐𝜌 2 𝑅 7
𝛾= = = = 1.40
𝑐𝑣 5 𝑅 5
2
Triatomic

Non-Linear

6 𝐶𝑝 = 𝐶𝑣 + 𝑅 = 3𝑅 + 𝑅 = 4𝑅
𝑈= 𝑘 𝑇 × 𝑁𝐴 = 3𝑅𝑇
2 𝐵
𝑐𝜌 4𝑅 4
ⅆ𝑈 𝛾= = = = 1.33
𝐶𝑣 = = 3𝑅 𝑐𝑣 3𝑅 3
ⅆ𝑇

Q. Show that for a gas possessing f degrees of freedom the ratio of two specific heats, 𝛾 =
2
1+𝑓

For f degrees of freedom,

𝑓
𝐸= 𝑘 𝑇
2 𝐵

𝑓 𝑓
𝑈= 𝑘𝐵 𝑇 × 𝑁𝐴 = 𝑅𝑇
2 2

ⅆ𝑈 𝑓
𝐶𝑣 = = 𝑅
ⅆ𝑇 2

𝐶𝑝 − 𝐶𝑣 = 𝑅

𝑓 𝑓 2+𝑓
⇒ 𝐶𝑝 = 𝑅 + 𝑅 = (1 + ) 𝑅 = ( )𝑅
2 2 2

2+𝑓
𝐶𝑝 ( 2 ) 𝑅 2 + 𝑓 2
𝛾= = = = 1+
𝐶𝑣 𝑓⁄ 𝑓 𝑓
2𝑅

2
𝛾 =1+
𝑓