PH-107

Specific Heat

Problems with Classical Radiation Theories

Issue with Specific Heat:
1 Specific heat of diatomic gases not properly explained.
(Theory prediction: CV = 2.5R for all temperatures.
Experimental Observation for Hydrogen: CV = 1.5R until about 100
K, 2.5R around room temperature (300 K) and rises to 3.5R for 1000
K.)
2 Incorrect prediction for specific heat of solids at low temperatures
(Theory: C = 3R for all temperatures.
Experiment: Theory is correct for room temperatures but for low
temperatures C ! 0).
3 No consistent explanation for blackbody radiation.
Rayleigh-Jeans law could explain low frequency part of the blackbody
radiation.
Wien’s law could explain the high frenquency part of the radiation.
4 No explanation for the discrete spectral lines in the radiation from
atoms.
S. Uma Sankar (IITB) Lecture-2 28 July 2016 2 / 13
 Law of Equipartition of Energy
Degrees of freedom (DF): The minimum number of
independent variables required for complete description
of the state of a physical system.

Monoatomic molecule:

3 translational DF
Diatomic rigid molecule

(a) Translational motion (b) Rotational motion

(of centre of mass) along along two axes to the
three axes line joining the two atoms.

Total degrees of freedom: 3 translational +2 rotational

 Diatomic non-rigid molecule

(a) Translational (b) Rotational motion (c) Vibrational

motion (of centre along two axes to motion along
of mass) along the line joining the two the line joining
three axes atoms. the two atoms.

Total DF: 3 translational, 2 rotational, 1 vibrational

Generalization: N-atom Molecule

Linear Molecules
Translational DF : 3
Rotational DF : 2
Vibrational DF : 3N-5

Non Linear Molecules

Translational DF : 3
Rotational DF : 3
Vibrational DF : 3N-6
Summary:

Translation* Rotation Vibration Total DF

Monatomic 3 0 0 3

Diatomic 3 2 1 6

Linear 3 2 3N-5 3N
polyatomic
(N>2)

Nonlinear 3 3 3N-6 3N
polyatomic
(N>2)
* Centre of Mass
Law of Equipartition of Energy

At finite temperature (T), the energy is distributed as:

1
k BT For each Translational and Rotational DF
2

For each vibrational DF

k BT (kT/2 each for KE and PE)

23 1
kB is the Boltzmann constant 1.38 10 J .K
From Kinetic Theory of Gases
 From Kinetic Theory of Gases

For 1D-translational motion along x-direction:

1 2 1 2
Kinetic Energy T = mvx Total Energy E = mvx
2 2
 3/2 
M 2 E
f (v) = 4⇡ v exp RT = NA kB T
2⇡RT kB T
Average Energy
 3/2 
M 2 E
f (v) = 4⇡ v exp
2⇡RT kB T

R1 R
m 1 2
2
mvx

1
Ef (vx ) dvx 2 v
1 x
e 2kB T
dvx
Ē = R 1 = R 2
mvx
f (v x ) dv x 1 2e
1 v
1 x
2kB T
dvx
Z 1 ⇣ ⇡ ⌘1/2 Z 1
2
↵x dx 2 2
↵x dx ⇡ 1/2
e = and x e =
1 ↵ 1 2↵3/2
↵ = m/2kB T
1
Ē = kB T
2
Average Energy
For 1D-Harmonic Oscillator
1 2 1 2
Total Energy = Kinetic Energy + Potential Energy E = mvx +  x
2 2
R1 R1 ⇣ ⌘ 2
R1 2
mvx x 2 mvx x2
Ef (E) dvx dx 1
dx 1
dvx 2 + 2 e 2kB T
e 2kB T
1
Ē = R 1 = R1 R1 2
mvx
f (E) dvx dx x2
1
1
dx 1
dvx e 2kB T
e 2kB T

⇣ ⌘ ⇣ ⌘
R1 R1 2
mvx
2
mvx x2
x 2
2
mvx x2

1
dx 1
dvx 2 e 2kB T
e 2kB T
+ 2 e 2kB T
e 2kB T

Ē = R1 R1 2
mvx
x2

1
e 2kB T
dx 1
e 2kB T
dvx

R 1 ⇣ mvx2 ⌘ 2
mvx R1 x2 R 1 ⇣ x2 ⌘ x2 R1 2
mvx

1 2 e 2kB T
dvx 1
e 2kB T
dx 1 2 e 2kB T
dx 1
e 2kB T
dvx
Ē = R1 R1 2
mvx
+ R1 R1 2
mvx
x2 x2

1
e 2kB T
dx 1
e 2kB T
dvx 1
e 2kB T
dx 1
e 2kB T
dvx

R 1 ⇣ mvx2 ⌘ 2
mvx R 1 ⇣ x2 ⌘ x2

1 2 e 2kB T
dvx 1 2 e 2kB T
dx 1 1
Ē = R1 2 + R1 x2
= kB T + kB T = kB T
mvx
e 2kB T
dx 2 2
1
e 2kB T
dvx 1
Law of Equipartition of Energy

At finite temperature (T), the energy is distributed as:

1
k BT For each Translational and Rotational DF
2

For each vibrational DF

k BT (kT/2 each for KE and PE)

23 1
kB is the Boltzmann constant 1.38 10 J .K
 Heat Capacity of Gases
Specific heat is the amount of heat per unit mass required
to raise temperature of the system by one degree
Molar specific heat is the specific heat per mole of a pure
substance.

The internal energy of a closed system

dU Q dW Q PdV
At constant volume
U Q
dU Q CV
T V T V

(Molar) Specific heat at constant volume

 CV Molar specific heat at constant volume
U
U is for one mole of substance
T V

Monoatomic gases
Degrees of freedom = 3 (only translational)
Energy per translational mode = kBT/2
NA Avogadro number
1
U NA 3 k BT
2
U 3 3 R =gas constant =
CV N Ak B R
T V 2 2 8.31 J mole-1 K-1
Diatomic gases
Rigid molecule Degrees of freedom = 5
3 Translational + 2 Rotational
1
U NA 5 k BT
2 5 5
CV N Ak B R
2 2

Non-rigid Degrees of freedom = 6

molecule 3 Translational + 2 Rotational + 1 Vibrational
1
U NA 5 k BT k BT
2
7 7
CV N Ak B R
2 2
Molar specific heat of hydrogen at constant volume

Cv = 3R/2 Cv = 5R/2 Cv = 7R/2

Only translation Translation Translation +

+ Rotation Rotation + vibration
 At low temperature
a diatomic molecule
acts like a mono
atomic gas, Cv = 3R/2

At high temperature, Cv increases to 5R/2 consistent with

adding rotational energy and not vibrational energy

At still high temperature, Cv = 7R/2 consistent with adding

rotational energy as well as vibrational energy
No explanation in ‘Classical’ theory. Does it smell
‘Quantization’ of rotational and vibrational motion?
Specific Heat of Diatomic Gases:

The variation of the specific heat of diatomic gases with

temperature can be explained using quantization of the
angular momentum due to rotation (Bohr hypothesis) and
quantization of energy due to vibration (Planck
hypothesis).

Consider the diatomic molecule to be shaped like a

dumbell (two identical spheres connected by a long thin
spring).

hypothesis) and quantization of energy due to vibration (Plan

Specific
esis). Heat of Diatomic Gases:
er the diatomic molecule to be shaped like a dumbell (two id
It has three independent translations
connected by a long thin spring). (in x, y and z
directions), two independent rotations (about the two
hree independent translations (in x, y and z directions), two
axes perpendicular to the connecting spring) and
dent rotations (about the two axes perpendicular to the con one
andvibration (along the
one vibration direction
(along of the spring).
the direction of the spring).
Specific Heat of Diatomic Gases:
We apply angular momentum quantization condition to rotations and energy
quantization condition to vibration.

If angular momentum takes values mh/(2π) (m = 0, 1, 2, ...), then rotational kinetic

energy Erot takes values m2h2/(8π2I), where I is the moment of Inertia of the
diatomic molecule about its center.

The vibrational energy Evib takes discrete values nhνvib (where n = 0,1,2,...).

In almost all the cases, Erot ≪ Evib.

It takes very little energy to make the molecule move. So at low temperatures, only
the three translational motions occur. The two rotations and the vibration do not
occur because kB T ⌧ Erot ⌧ Evib
Therefore, the internal energy is U = 3N (1/2)kB T
and the specific heat CV = 1.5R

Specific Heat of Diatomic Gases:

At room temperature, we have

Erot ⌧ kB T ⌧ Evib

So the thermal energy is large enough to excite the rotations but is not enough
to excite the vibration. So the internal energy is U = 5N (1/2)kB T
and the specific heat is CV = 2.5R

At high temperatures, when

Erot ⌧ Evib ⌧ kB T
the vibration is also excited, which adds another N kB T to the internal energy
(half from kinetic energy and half from potential energy.)
So the specific heat becomes 3.5R

 ‘Quantization’ of rotational and vibrational motion

At low temperatures,
all molecules are in
the ground state of
rotation and vibration,
only translational
motion contributes: Cv
=3R/2

At high temperature, molecule is excited to higher rotational

energy levels and rotational motion contributes to Cv (=5R/2)

At still higher temperature, molecule is excited to higher

vibrational energy levels and both vibrational and rotational
motion contribute to Cv (=7R/2)
Specific heat at constant volume (CV) :

Triatomic (Linear)
DF: 3 (Translational), 2 (Rotational), 4 (Vibrational)
CV = (3/2 + 1 + 4)R =(13/2)R (classical value)

Experiments (What we expect): As a function of temperature:

CV = 3R/2 5R/2 13R/2
However, if some of the vibrational modes have low energy,
they start contributing at lower temperature.
Example: CO2 molecule. 1 low energy vibrational mode, 1
higher energy vibrational mode, 2 highest energy vibrational
modes
CV = 3R/2 5R/2 7R/2 9R/2 13R/2
(A particular vibrational mode will contribute to Cv if h V ~ kBT )
Triatomic (Non-linear)
DF: 3 (Translational), 3 (Rotational), 3 (Vibrational)
CV = (3/2 + 3/2 + 3)R = 6R (classical value)

As a function of temperature: CV = 3R/2 3R 6R

(If all vibrational modes have same frequency)
If there exist low frequency vibrations, then one needs to take
this into account.

Example: Ozone
One mode has low frequency, two modes have higher and
similar frequencies

CV = 3R/2 3R 4R 6R
 V
Experimental Observation for Hydrogen: CV = 1.5R until about 100
Issue
K, 2.5R with Specific
around room Heat:
temperature (300 K) and rises to 3.5R for 1000
K.)
2 Incorrect prediction for specific heat of solids at low temperatures
(Theory: C = 3R for all temperatures.
Experiment: Theory is correct for room temperatures but for low
temperatures C ! 0).
3 No consistent explanation for blackbody radiation.
Rayleigh-Jeans law could explain low frequency part of the blackbody
radiation.
Wien’s law could explain the high frenquency part of the radiation.
4 No explanation for the discrete spectral lines in the radiation from
atoms.
S. Uma Sankar (IITB) Lecture-2 28 July 2016 2/1
Specific Heat of Solids:
Classical theory of heat predicted that the specific heat of all solids should be
3R at all temperatures.

Experimentally, it was found that C → 0 as T → 0.

Einstein explained this feature based on Quantization of vibrations.

The number of atoms, N, in a solid is of the order of Avagadro number. Each

atom has, in principle, three degrees of freedom (it can move in three
independent directions). So the number of degrees of freedom is 3N.
The solid, as a mass, has three translational degrees of freedom and three
rotation degrees of freedom (A famous theorem of Euler).

Hence the number of vibrational degrees of freedom in the solid (that is, the
number of independent ways the atoms in the solid can vibrate) is 3N − 6 =
3N, because the 6 can be neglected when N is of the order of Avagodro
number.

Specific Heat of Solids:

Classically, each independent vibrational mode gets average energy kB T
(half due to kinetic energy and half due to potential energy).

If the vibrational modes are quantized, this average energy for the model with
h⌫/kB T
frequency ⌫ is h⌫/(e 1)
3N h⌫
Hence the internal energy of the solid is U= h⌫
e kB T
1
For h⌫/kB T ⌧ 1 (or for large T), this reduces to the classical formula.

For low temperatures, we have h⌫/kB T 1

h⌫/kB T
and the internal energy becomes U = 3N h⌫ e
✓ ◆2
@U h⌫ h⌫/kB T
and the specific heat is C= = 3R e
@T kB T
leading to C → 0 as T → 0.