B.

Sc Notes Specific Heat

Specific Heat Einstein’s Theory of Specific heat of a solid

In Einstein’s theory, the crystal lattice structure of a
Specific heat: It is the amount of heat required to change solid comprising N atoms can be treated as an assembly of 3N
the temperature of unit mass of substance by unit degree distinguishable one-dimensional oscillators. This assumption
temperature. is based on that each atom is free to move in three
dimensions.

Classical Theory of Specific heat of a solid The energy level of harmonic oscillator is
1
Solid molecules have 6 degrees of freedom (3 translational 𝐸𝑛 = (𝑛 + 2)ħω
and 3 vibrational). ℎ
Where ħ= 2𝜋 and 𝑛 = 0,1,2 … … …
According to law of equipartition of energy theorem,
1 Using Maxwell- Boltzmann distribution of energy
Energy associated with each degree of freedom = 𝑘𝑇
2 𝐸𝑛
∞ −
1 ∫0 𝐸𝑛 𝑒 𝑘𝑇 𝑑𝐸
∴ Energy associated with one molecule = 6 X 𝑘𝑇 𝐸= 𝐸𝑛
2 ∞−
∫0 𝑒 𝑘𝑇 𝑑𝐸
= 3𝑘𝑇
𝐸𝑛
−
∴ Total energy associated with one mole of solid, U = 3 𝑁𝐴 𝑘 𝑇 ∑∞
0 𝐸𝑛 𝑒 𝑘𝑇
𝑂𝑟 𝐸 = 𝐸𝑛
−
𝑅 ∑∞
0 𝑒
𝑘𝑇
But 𝑁𝐴 𝑘 = 𝑅 (∵ 𝑘 =𝑁 )
𝐴
1 1 ħω
−(𝑛+ )
0 (𝑛 + 2) ħω 𝑒
∑∞ 2 𝑘𝑇
∴ U = 3 𝑅 𝑇 ………………………..(1) 𝐸= 1 ħω
−(𝑛+ )
Now the specific heat at constant volume, ∑∞0 𝑒
2 𝑘𝑇

ħω
𝑑𝑈 Let 𝑥 = −
𝐶𝑉 = 𝑘𝑇
𝑑𝑇
1 (𝑛+12)𝑥
𝑑 ħω ∑∞
0 (𝑛 + 2) 𝑒
∴ 𝐶𝑉 = (3 𝑅 𝑇) Then, 𝐸 =
𝑑𝑇 1
(𝑛+ )𝑥
∑∞
0 𝑒
2
∴ 𝐶𝑉 = 3 𝑅

Page 1 of 5 Prof. Avadhut Manage

D. M. S. Mandal’s Bhaurao Kakatkar College, Belgaum
B.Sc Notes Specific Heat
1 𝑥 3 3𝑥 5 5𝑥
(2 𝑒 2 + 2 𝑒 2 + 2 𝑒 2 + . . . . . . . ) 𝑑𝑈 1 ħω
ħω
𝐸 = ħω 𝑥 3𝑥 5𝑥
𝐶𝑣 = (𝑑𝑇 ) = 3 𝑁𝐴 ħω [0 − ħω 2 ]X −𝑒 𝑘𝑇 𝑘𝑇 2
𝑣
(𝑒 2 + 𝑒2 + 𝑒2 + . . . . . . .) (𝑒 𝑘𝑇 −1)

𝑑 𝑥 3𝑥 5𝑥 ħω
𝐸 = ħω [ln (𝑒 2 + 𝑒 2 + 𝑒 2 + . . . . . . . )] ħω 2 𝑒 𝑘𝑇
𝑑𝑥 𝐶𝑣 = 3 𝑁𝐴 𝑘 ( ) 2
𝑘𝑇 ħω
𝑑 𝑥
[(𝑒 − 1) ]
𝑘𝑇
𝐸 = ħω [ln 𝑒 2 (1 + 𝑒 𝑥 + 𝑒 2𝑥 + . . . . . . . )]
𝑑𝑥
ħω
Since ln(1 + 𝑒 𝑥 + 𝑒 2𝑥 + . . . . . . . ) = − ln(1 − 𝑒 𝑥 ) ħω 2 𝑒 𝑘𝑇
𝐶𝑣 = 3 𝑅 ( ) 2
𝑑 𝑥 𝑘𝑇 ħω
∴ 𝐸 = ħω [ln 𝑒 2 − ln(1 − 𝑒 𝑥 )] [(𝑒 − 1) ]
𝑘𝑇
𝑑𝑥
ħω
𝑑 𝑥 Here = 𝜃𝐸 , called as Einstein temperature
𝐸 = ħω [ − ln(1 − 𝑒 𝑥 )] 𝑘
𝑑𝑥 2
𝜃𝐸
1 𝑒𝑥 𝜃𝐸 2 𝑒𝑇
𝐸 = ħω [ + ] ∴ 𝐶𝑣 = 3 𝑅 ( )
2 1 − 𝑒𝑥 𝑇 𝜃𝐸 2

1 1 [ (𝑒 𝑇 − 1) ]
𝐸 = ħω [ + −𝑥 ]
2 𝑒 −1
Case I : 𝑇 ≫ 𝜃𝐸
ħω
since 𝑥 = − 𝑘𝑇 𝜃𝐸
≪1
𝑇
1 1
∴ 𝐸 = ħω [ + ħω
] 𝜃𝐸
2 ∴𝑒𝑇 ⇾1
𝑒 𝑘𝑇 −1
For one mole, the total energy of system is given by 𝜃𝐸 1 𝜃𝐸 2 𝜃𝐸
𝑒𝑇 − 1 ≈ 1 + ( ) + . . .. . . . −1 ≈
2! 𝑇 𝑇
1 1
𝑈 = 3 𝑁𝐴 𝐸 = 3 𝑁𝐴 ħω [ + ħω
]
2 𝜃𝐸 2 1
𝑒 𝑘𝑇 −1
∴ 𝐶𝑣 = 3 𝑅 ( ) [ ] = 3𝑅
∴ The molar specific heat is given by
𝑇 𝜃𝐸 2
(𝑇)

Page 2 of 5 Prof. Avadhut Manage

D. M. S. Mandal’s Bhaurao Kakatkar College, Belgaum
B.Sc Notes Specific Heat
Case I : 𝑇 ≪ 𝜃𝐸 1 1 2
𝑓(𝜈) 𝑑𝜈 = 4𝜋 ( 3 + 3) 𝜈 𝑑𝜈 . . . . . (1)
𝜃𝐸 𝐶𝑙 𝐶𝑡
≫1
𝑇 Where 𝐶𝑙 & 𝐶𝑡 are velocities of longitudinal and
𝜃𝐸 𝜃𝐸 transverse wave respectively.
∴𝑒𝑇 −1≈𝑒𝑇
Since each oscillator of the assembly vibrates with its
𝜃𝐸
own frequency, and we are considering an assembly of 3N
𝜃𝐸 2 𝑒𝑇
∴ 𝐶𝑣 = 3 𝑅 ( ) linear oscillators, there must be an upper limit to the
𝑇 𝜃𝐸 2
(𝑒 𝑇 ) frequency, so that
[ ]
𝜈𝑚
2
𝜃𝐸 1 3𝑁 = ∫ 𝑓(𝜈) 𝑑𝜈
∴ 𝐶𝑣 = 3 𝑅 ( ) [ 𝜃 ]
𝑇 𝐸
0
𝑒𝑇
𝜃𝐸
𝜈𝑚
𝜃𝐸 1 1
In above equation, As 𝑇 ⇾ ∞, reaches zero faster than 𝑒 .
𝑇
∴ 3𝑁 = ∫ 4𝜋 ( 3 + 3 ) 𝜈 2 𝑑𝜈
𝑇
Hence at high temperature 𝐶𝑣 = 0 𝐶𝑙 𝐶𝑡
0
𝜈𝑚
1 1
∴ 3𝑁 = 4𝜋 ( 3 + 3 ) ∫ 𝜈 2 𝑑𝜈
Debye’s theory of the specific heat of a solid 𝐶𝑙 𝐶𝑡
0
The main problem of Einstein theory lies in the 1 1 1
assumption that a single frequency of vibration characterizes ∴ 3𝑁 = 4𝜋 ( 3 + 3 ) 𝜈𝑚 3
𝐶𝑙 𝐶𝑡 3
all 3N oscillators.
9𝑁 1 1
In Debye’s theory a solid is viewed as a phonon gas. ∴ = 4𝜋 ( + ) . . . . . . . . (2)
3
Vibrational waves are matter waves, each with its own de 𝜈𝑚 3 𝐶𝑙 𝐶𝑡 3
Broglie wavelength and associated particle. Debay considered From eqn (1) and (2), we get
the vibration of crystal as whole.
9𝑁𝜈 2
In a vibrating solid, there are three types of waves. 𝑓(𝜈) 𝑑𝜈 = 𝑑𝜈
𝜈𝑚 3
After considering one longitudinal and two transverse
waves(two states of polarisation), According to the quantum theory energy associated
with each degree of freedom is
Page 3 of 5 Prof. Avadhut Manage
D. M. S. Mandal’s Bhaurao Kakatkar College, Belgaum
B.Sc Notes Specific Heat
ℎ𝜗 𝜈𝑚 ℎ𝜗 ℎ𝜗
9𝑁 𝑒 ⁄𝑘𝑇 2
ℎ𝜗⁄
∴ 𝐶𝑣 = 3 ∫ ℎ𝜈 3 𝑘𝑇
𝑒 𝑘𝑇 −1 2 𝑑𝜈
𝜈𝑚 ℎ𝜗⁄
0 (𝑒 𝑘𝑇 − 1)
The internal energy of the assembly is given by
𝜈𝑚 𝜈𝑚 ℎ𝜗⁄
9𝑁 ℎ2 𝜈4 𝑒 𝑘𝑇
𝑈 = ∫ 𝑁(𝜈) 𝑑𝜈 ∴ 𝐶𝑣 = 3 ∫ 2 𝑑𝜈
𝜈𝑚 𝑘𝑇 2 ℎ𝜗
0 0 (𝑒 ⁄𝑘𝑇 − 1)
𝜈𝑚 𝜈𝑚 ℎ𝜗⁄
ℎ𝜗 9𝑁 ℎ2 𝜈4 𝑒 𝑘𝑇
∴ 𝑈 = ∫ 𝑓(𝜈) 𝑑𝜈 ℎ𝜗⁄ ∴ 𝐶𝑣 = 3 2 ∫ 2 𝑑𝜈
𝑒 −1 𝜈𝑚 𝑘𝑇 ℎ𝜗
0
𝑘𝑇
0 (𝑒 ⁄𝑘𝑇 − 1)
𝜈𝑚
h𝜈𝑚
9𝑁𝜈 2 ℎ𝜗 Here = 𝜃𝐷 , called as Debye’s temperature
∴𝑈=∫ 3 ℎ𝜗
𝑑𝜈 𝑘
𝜈𝑚 𝑒 ⁄𝑘𝑇 − 1
0 ℎ𝜈 ℎ𝜈𝑚 𝜃𝐷
Let 𝑥 = 𝑘𝑇 and 𝑥𝑚 = =
𝜈𝑚 𝑘𝑇 𝑇
9𝑁 ℎ𝜈 3 𝑥𝑚 𝑘𝑇 4
∴ 𝑈 = 3 ∫ ℎ𝜗 𝑑𝜈 ( 𝑥) 𝑒 𝑥 𝑘𝑇
𝜈𝑚 ⁄𝑘𝑇 9𝑁 ℎ2
0
𝑒 − 1 ∴ 𝐶𝑣 = 3 2 ∫ ℎ 𝑥 ( 𝑑𝑥)
𝜈𝑚 𝑘𝑇 (𝑒 − 1)2 ℎ
𝑑𝑈 0
We know, 𝐶𝑣 = ( ) 𝑥𝑚
𝑑𝑇 𝑣
9𝑁 ℎ2 𝑘5𝑇5 𝑥4 𝑒 𝑥
∴ 𝐶𝑣 = 3 𝑋 2 𝑋 5 ∫ 𝑥 𝑑𝑥
𝜈𝑚 1 𝜈𝑚 𝑘𝑇 ℎ (𝑒 − 1)2
𝑑( ℎ𝜗 ) 0
𝑑𝑈 9𝑁 𝑒 ⁄𝑘𝑇 − 1 𝑑𝜈
∴ 𝐶𝑣 = ( ) = 3 ∫ ℎ𝜈 3 𝑥𝑚
𝑑𝑇 𝑣 𝜈𝑚 𝑑𝑇 𝑘3𝑇 3 𝑥4 𝑒 𝑥
0 ∴ 𝐶𝑣 = 9𝑁𝑘 𝑋 3 3 ∫ 𝑥 𝑑𝑥
ℎ 𝜈𝑚 (𝑒 − 1)2
𝜈𝑚 1 0
𝜕 ( ℎ𝜗 )
9𝑁 𝑒 ⁄𝑘𝑇 − 1 𝑥𝑚
∴ 𝐶𝑣 = 3 ∫ ℎ𝜈 3
𝑑𝜈 𝑇 3 𝑥4 𝑒 𝑥
𝜈𝑚 𝜕𝑇 ∴ 𝐶𝑣 = 9𝑁𝑘 ( ) ∫ 𝑥 𝑑𝑥 . . . . . (1)
0 𝜃𝐷 (𝑒 − 1)2
0

Case I : At high temperature,

Page 4 of 5 Prof. Avadhut Manage

D. M. S. Mandal’s Bhaurao Kakatkar College, Belgaum
B.Sc Notes Specific Heat
𝜃𝐷
≪ 1 , 𝑥 ≪ 1 and 𝑒 𝑥 ≈ 1
𝑇

∴ 𝑒𝑥 − 1 ≈ 𝑥
Eqn (1) becomes,
𝜃𝐷
𝑇
𝑇 3 𝑥4 𝑋 1
∴ 𝐶𝑣 = 9𝑁𝑘 ( ) ∫ 𝑑𝑥
𝜃𝐷 𝑥2
0
𝜃𝐷
𝑇
3
𝑇
∴ 𝐶𝑣 = 9𝑁𝑘 ( ) ∫ 𝑥 2 𝑑𝑥
𝜃𝐷
0
𝜃𝐷
𝑇 3 𝑥3 𝑇
∴ 𝐶𝑣 = 9𝑁𝑘 ( ) [ ]
𝜃𝐷 3 0

𝑇 3 𝜃𝐷 3
∴ 𝐶𝑣 = 3𝑁𝑘 ( ) ( )
𝜃𝐷 𝑇
∴ 𝐶𝑣 = 3𝑁𝑘 = 3𝑅 ∵ 𝑁𝑘 = 𝑅

Case II : At low temperature,

𝜃𝐷
≫1 , 𝑥≫1
𝑇

Eqn (1) becomes,

𝑇 3 4 2
∴ 𝐶𝑣 = 9𝑁𝑘 ( ) [ 𝜋 ]
𝜃𝐷 15
∴ 𝐶𝑣 ∝ 𝑇 3

Page 5 of 5 Prof. Avadhut Manage

D. M. S. Mandal’s Bhaurao Kakatkar College, Belgaum