• Einstein theory/hypothesis of heat capacity

Einstein was first to present a theoretical explanation of the low

temperature heat capacity of solids.

Assumption- Each atom in a crystalline element consisting of NA

atoms, vibrates about their equilibrium configuration as a simple
harmonic oscillator so that the entire crystal system could be
considered to be set of 3N independent harmonic oscillator, each
oscillator having same frequency.
Heat capacity
𝜃𝑉 2 𝜃𝑉ൗ
𝑅 𝑒 𝑇
𝑇
𝐶𝑉,𝑣,𝑚 = 𝜃𝑉
2 = 𝑅𝑓
ൗ
𝑒 𝑇 −1

𝜃𝑉 2 𝜃𝑉ൗ
𝑒 𝑇
𝑇
f= 𝜃𝑉
2 f= Einstein function
ൗ
𝑒 𝑇 −1
• Drawbacks
Einstein model and experiment values at high temperatures agrees well

1. The model is applicable only to atomic crystals, and it does not accurately
reproduce the temperature dependence of CV ,v,m for molecular solids.
2. Imp- Einstein model assumed the 3N independent harmonic oscillators having
same frequency or isoenergetic. This may not be true. CO has different
vibrational frequencies for different modes.
3. Einstein model predicts that the heat capacity should demonstrate exponential
dependence at low temperature; however, experimentally the heat capacity
demonstrates T3 dependence.
These all drawbacks were taken care by Debye in his model

We can say that in Einstein model we are able to find out the range of the molar heat
capacity values and we noticed the molar heat capacity varies from 0 (low T) to 3R
(high T).
• The Debye theory of heat capacity
The normal frequencies of the crystal are not due to vibrations of single atoms but are due to
concerted harmonic motion of all the atoms. These lattice vibrations are not all
characterized by the same frequency.
Debye assumed the atomic crystal to have 3N normal vibrations, each having unique
frequency.
𝜃𝐷
𝑇
𝑇
3
𝑥4 𝑒 𝑥 This expression must be
𝐶𝑣 = 9𝑁𝑘 ඲ 𝑥 2
𝑑𝑥 evaluated numerically,
𝜃𝐷 𝑒 −1
cannot be evaluated by
0
simple function.

Where,
ℎ𝑣 ℎ𝑣𝐷
𝑥= 𝜃𝐷 = Characteristic Debye temperature
𝐾𝑇 𝑘
Therefore, it is convenient to define the Debye function as
𝜃𝐷
𝑇
3
𝑻 𝑇 𝑥4 𝑒 𝑥
𝑫 =3 ඲ 𝑥 2
𝑑𝑥
𝜽𝑫 𝜃𝐷 𝑒 −1
0

So, the heat capacity is:

𝑇
𝐶𝑣 = 3𝑁𝑘𝐷
𝜃𝐷
𝑻
The function, 𝑫 is called Debye function
𝜽𝑫
Examples-
Observed values and curve calculated on the Debye model for heat capacity

They have good agreement with experimental data

Ref: donald mcquarrie

Variation of Temperature
At high temperature: 𝑇 > 𝜃𝐷 The upper limit in the integral becomes very small
Solving the integral part
𝜃𝐷 𝜃𝐷 𝜃𝐷 3
𝑇 𝑥4 𝑒 𝑥 𝑇 𝑥4(1+𝑥+⋯ ) 𝑇 𝑥4
𝜃𝐷 1 𝜃𝐷
න 𝑑𝑥 = න 𝑑𝑥 =න 𝑑𝑥 = ‫׬‬0 𝑥2 𝑑𝑥
𝑇 =
0
𝑒 𝑥 −1 2
0
1+𝑥+⋯ 2
0
𝑥 2
3 𝑇

Putting the value in the Debye equation:

𝜃 𝐷
𝑇
3
𝑻 𝑇 𝑥4 𝑒 𝑥 𝑻
𝑫
𝜽𝑫
=3
𝜃𝐷
඲ 𝑥
𝑒 −1 2
𝑑𝑥 𝑫 =1
𝜽𝑫
0
𝑇
Similarly putting the value in the heat capacity equation: 𝐶𝑣 = 3𝑁𝑘𝐷
𝜃𝐷

The heat capacity becomes 𝐶𝑣 = 3NK =3R = 6 cal/deg-mol

 At low temperature: 𝑇 < 𝜃𝐷 , 𝜃𝐷 /T approaches ∞
𝑻
The upper limit in the integral in 𝑫 go to infinity
𝜽𝑫

∞
3 4 π4 (After solving)
𝑻 𝑇 𝑥4 𝑒 𝑥 Standard integral =
𝑫 =3 ඲ 𝑥 2
𝑑𝑥 15
𝜽𝑫 𝜃𝐷 𝑒 −1
0

The heat capacity becomes

3
12 π4 𝑇 The Debye theory was able to
𝐶𝑣 = 𝑁𝑘 used at lower temperature
5 𝜃𝐷

This is the famous T3-law

• Important features of Debye theory of heat capacity

1. It predicts a T3-law for low temperature heat capacity.

2.
𝑇
𝐶𝑣 = 3𝑁𝑘𝐷
𝜃𝐷

If Cv is plotted vs. T/ 𝜃𝐷 all substance will le on one curve. Cv is the

universal function of all the substance determined by one parameter 𝜃𝐷 in
the form of T/ 𝜃𝐷
Thermodynamic functions in Macroscopic system (bulk system)
Best wishes for your exams