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SPECIFIC HEAT OF SOLIDS.

Classical theory – Dulong and Petit’s law:

According to the Dulong and Petit’s empirical law,


“The molar specific heat of any solid at constant volume is a constant equal to
3R and is independent of temperature.”
An atom in a solid may be considered as a Simple Harmonic Oscillator (SHO)
since all the atoms are in the solid are in a state of vibration. Each atom has three
degrees of freedom for vibration.
∴ Each atom may be considered as three one dimensional SHO, each having an
1
average kinetic energy = kT, where k is the Boltzmann’s constant and the T is the
2
absolute temperature.
Total Energy of an one dimensional S.H.O = Kinetic energy + Potential energy.
= ½ kT + ½ kT = kT
If we consider 1 mole of solid, it will contain N0 number (Avogadro number) of
atoms. Thus, the solid will have 3 Ν 0 no. of one dimensional S.H.Os.
∴ Total energy of the solid = Total no. of S.H.O × Total energy per S.H.O
i.e., E = 3 Ν 0 . kT = 3RT where R is the universal gas constant.

 ∂Ε  ∂
∴ Molar specific heat at constant volume, Cv =   = ( 3RΤ ) = 3R
 ∂Τ v ∂Τ

Experimental values of Cv of CV
most of the solids at ordinary or high
temperatures is very nearly equal to 3R
3R and is independent of temperature
in agreement with the classical theory , Experimental value

namely, Dulong and Petit’s law.


T
0
2

3
But experiments at low temperatures show that Cv is nearly proportional to T .and

Cv tends to zero as temperature tends to zero. Thus Dulong and Petit’s law is valid only at
high temperatures.

EINSTEIN’S THEORY OF SPECIFIC HEATS OF SOLIDS:


According to Einstein, the basic error in the Dulong and Petit’s law lies in the calculation of
average energy of an one dimensional S.H.O.
In his theory, Einstein assumed that
1) Each atom in the solid is vibrating independent of other atoms.
2) All the atoms vibrate with the same frequency, ν.
3) A solid containing N number of atoms may be considered as 3N numbers of one
dimensional atomic oscillators.
4) According to the quantum theory of radiation proposed by Max Planck. an oscillator with
vibrational frequency ν, can absorb or emit energy in multiples of a quantum of energy.
ε = hν. [i.e, E = 0, hν, 2hν, 3hν, 4hν …………and so on].
5) To find the average energy of an oscillator he used Maxwell-Boltzmann statistics according
to which the probability that an oscillator has an energy Ei is given by the ‘Boltzmann factor’

−Ei

ekT
.
6) This means that the number of oscillators with energy Ei is given by

 − Ei 
n i = C. exp  ----------(1) where C is a constant.
 kT 
If n0 be the number of oscillators with zero energy then, n0 = c.e0 = c . Replacing C in eqn (1)
− Ei

by n0 , we get, n i = n 0 .e kT
--------------------------------------- (2)

where Ei is the energy in the ith state and Ei =i(hν). i = 0.1.2.3… etc.
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Let hν = ε and hence E0 = 0, E1 = ε = hν , E2 = 2ε = 2hν ,………………etc., be the allowed

energies of oscillators with frequency ν . Let n0 , n1 , n2 ..........etc., be the number of oscillators


having energies 0, ε , 2 ε ,......... .. and so on.

∴Total number of oscillators with frequency ν is N = n0 + n1 + n2 + ......


− ε −2ε

N = n 0 + n 0 .e kT
+ n 0 .e kT
+ ......

 −ε −2ε

= n 0 1 + e kT
+ e kT + ....  ---(3)
 
1
[
But 1 + e + e
x 2x
+ e3 x ....] =
1 − ex
−ε − 2ε −3ε
  1

∴ 1+ e kT +e kT + e kT + ............  = ……………….-Æ(i) . Using this in (3),
   −ε

  1 − e kT 
 
 
n0
we get, N = −ε ---------------------------- (4)
1 − e kT

The total energy of all these N oscillators will be


E = n0 .0 + ε .n1 + 2ε .n2 + 3ε .n3 + ....
−ε −2ε −3ε

i.e., E = 0+ε.n0.e + 2.ε.n0.e +3.ε.n0.e +....


kT kT kT
------- Æ(5)
−ε −ε −2ε −3ε −4ε
Multiplying (5) by e ,
kT
E.e kT = n0 .ε .e kT + 2n0 .ε .e kT + 3n0 .ε .e kT + ............ Æ(6)
Subtracting equation (6) from (5)
−ε −ε −2ε −3ε
 
E.1 − e kT  = n0 .ε .e + n0 .ε .e
kT kT + n0 .ε .e kT + ............
 
 
−ε −ε −ε − 2ε −3ε
   
i.e., E.1 − e kT  = n0 .ε .e kT 1 + e kT + e kT + e kT + ............ 
   
   
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−ε
 −ε
 n ε .e kT
i.e. 
E. 1 − e kT  = 0 (using eqn. (i)). Rearranging this,
  −ε
 
1 − e kT
−ε −ε
n ε .e kT n ε .e kT
∴ E= 0 2
i.e., Total energy E = 0 2
………………… (7)
 −ε   −ε 
 kT   kT 
1 − e  1 − e 
   
   

E
∴ Average energy per oscillator <E> =
N
Substituting for N and E from eqns. (4) and (7) respectively, we get,

 −ε 
 
−ε 1 − e kT  −ε
 
n ε .e kT   = ε .e kT
< E >= 0 .
 −ε 
2
n0  −ε 
   kT 
kT 1 − e
1 − e  
   
   

ε.
i.e., < E > =
 −ε 
 kT 
 1 −e 
 −ε −ε 
 kT 
e e kT 
ε
<E> = Using ε = hν / kT, we have
 ε 
 kT 
e − 1
 
 


<E> = …………….…. (8)
 hν 
 kT 
e − 1
 
 
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This is the average energy of an one dimensional oscillator.


If there are N0 atoms in one mole of the solid, there will be 3N0 one dimensional harmonic
oscillators in the solid per mole. Here, obviously, N0 is the Avogadro number.
∴Total energy of 1 mole of the solid is, E =3N0<E>
3N 0 hν
E =
 hν 
 kT 
e − 1
 
 
Let (hν/k) = θE, known as Einstein’s Temperature, which is a characteristic of the given solid.

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−θ E
3N 0 kθ E  ∂Ε  θE  3Rθ E
∴E = (or) CV =   = 3R .   .e T E = ……….(9)
 θE   ∂Τ v T   θE 
 T   T 
 e − 1  e − 1
   
   
θE
2
 ∂E   θE  eT
∴ Molar Specific heat at constant volume , CV =   = 3 R   ….Æ(10)
 ∂T V
2
 T   θE 
 e − 1
T

 
 θE 
CASE 1:- When temperature T is very high, such that T >> θE, then   is very small.
T 
θE 2 3
θ  1  θE  1  θE   θE 
∴e T
 1+  E  +   +   + ......  1 +   , neglecting higher powers.
T  2!  T  3!  T  T 
θE
θ 
∴e T −1   E  . Using this in eqn. (9), we get,
T 
3Rθ E  ∂E 
E= = 3RT and hence CV =   = 3R , the classical theory value.
θE  ∂T V
( )
T
2
θ  θ 
CASE 2:- When temperature T is small, such that T << θE , then  E   E  is very large.
T  T 
 θE  θE θE
 
e T 
>> 1 and hence ∴ e T − 1  e T , neglecting 1. Using this in eqn. (9), we get,
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3Rθ E
E=
 θE 
 T 
e 
 
 

2
−θ E
 ∂Ε  θE 
∴ CV =   = 3R .   .e T
 ∂Τ v T 

Thus, Einstein’s theory is able to explain the change and dependence of Cv on temperature at low
temperatures. Cv of the solid at low temperatures depends on temperature T and on θ E ie., the
characteristic frequency of vibration of the solid.
2
θ 
In the above equation as T reduces,  E  CV
T 
−θ E
increases while e T reduces. Since the
exponential reduction is much faster, value of Expt

Cv reduces exponentially with reducing temperature.


But experiments at low temperatures show that Cv Einstein’s Theory

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is nearly proportional to T and Cv tends to zero T
as temperature tends to zero more slowly than that predicted by the Einstein’s theory.
Draw back of Einstein’s theory:
Einstein’s theory, in agreement with the experiment, established the change of Cv with
temperature. But fall in Cv with falling temperature is steeper than that observed in experiments.
This indicates that value of Cv calculated by Einstein’s theory are not accurate at low temperature.
This inaccuracy is due to the fact that the atoms in solids are assumed to be vibrating
independent of each other with the same frequency. This assumption is not correct.
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Debye’s Theory of Specific heat of Solids


Einstein’s theory of specific heat of solids was the first to show qualitatively that the specific
heat of solids varies with temperature. However the form of dependence of Cv on temperature was
not correct due to the oversimplified assumptions that the atoms of the solid (1) vibrate independent
of each other and (2) with one and the same frequency.
Debye proposed a modified theory of specific heat of solids with the following assumptions;
1. Solid is an isotropic elastic continuum with its atoms coupled elastically to each other.
2. Motion of an atom influences its neighbors
3. Atomic vibrations are coupled and hence the atoms vibrate collectively
4. The lattice vibrations have a range of different frequencies.
5. The internal energy of the solid resides in in elastic standing waves propagated through the
crystal lattice.
6. The energy of the elastic waves is quantized; the quantized lattice waves are called as
“phonons”.
7. Velocity of elastic waves in the solid (sound) c is independent of frequency, ν.
8. The density of vibrational modes with frequencies in the range between
ν2
ν and ν + dν is given by Z (ν ) = 4πV where V is the volume of the solid .
c3
Each atom has three degrees of freedom for vibration. ∴ For a solid with N atoms in a volume V,
the total number of one dimensional vibration modes is restricted to 3N. Hence the frequency of
vibration has an upper limit νD, known as Debye’s cut off frequency. Thus in thermal equilibrium a
solid will have vibrations with frequencies between 0 and νD.
As each three dimensional vibration mode can be polarized into one longitudinal and two
transverse waves with velocities cl and ct respectively, the density of modes will be
 1 2 
Z (ν ) = 4πV 3 + 3  .ν 2 . Therefore number of modes with frequency between ν and ν + dν is
 cl ct 

 1 2 
given by Z (ν ).dν = 4πV 3 + 3  .ν 2 .dν ........(1)
 cl ct 

The total number of all possible modes of vibration is obtained by integrating the
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equation (1) with limits between 0 and νD. But the total number of possible modes is 3N only.
νD
Therefore, ∫ Z (ν ).dν = 3N
0

i.e.,
νD
 1 2  2
∫ 4π V  c
0 l
3
+  .ν .dν = 3 N
ct3 
ν
 1 2  D
4π V  3 + 3  . ∫ ν 2 .dν = 3N
 cl ct  0
 1 2  ν D3  1 2  9N
4π V  3 + 3  . = 3 N (or) 4π V  3 + 3  = ......(2)
 cl ct  3  cl ct  ν D3

9N
Substituting this back into eqn (1), we have, Z (ν ).dν = .ν 2 .dν ........(3)
νD 3

From Planck’s quantum theory and Einstein’s theory of specific heat of solids, the average energy of
oscillators with frequency between ν and ν + dν is given by

< E >= hν
. ∴Energy due to all the modes with frequency between ν and ν + dν is given by
 
e kT
− 1

 

9N hν 3
dE = Z(ν)dν.<E> i.e., dE = .dν
ν D3  hν

e kT
− 1

 
∴Total energy of the solid is given by
νD νD νD
9N hν 3 9 Nh ν3
E= ∫ dE = ∫ν 3
 kThν

.dν i.e., E =
ν D3
. ∫ hν

.dν ......(4)
0 0 D
 e − 1 0
e
kT
− 1
   
hν D kθ
Let = θ D , known as Debye temperature which is a characteristic of the solid.∴ν D = D
k h
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hν kT kT
Also, let x = (or) ν= .x .....(i ) ∴ dν = .dx ....... (ii)
kT h h
hν D θ
When ν = 0, x = 0 and when ν = ν D , x = = D ......(iii)
kT T
Replacing the variable ν by x , changing the limits of the integral and substituting for ν D
3
θD  kT  3  kT 
h3 T   x .  .dx
 h   h 
from the above equations, the eqn (4) becomes, E = 9 Nh.
k 3θ D 3
. ∫
0 ( e x − 1)
θD 3
x ..dx
9 NkT 4 T ................ (6). For 1 mole of the solid, N is replaced by the Avogadro number, N 0 .
E=
θD 3
.∫ ( e x − 1)
0

θD
4
9 RT T
x 3 .dx
As Nk = N0k =R for 1 mole, , the universal gas constant, it becomes, E =
θ D3
. ∫
0
ex −1
.......(7)

Now, E is the equilibrium thermal energy of 1 mole of the solid and its molar specific heat at
constant volume is given by Cv = (∂E / ∂T)V.

Case (i) : When the temperature T is very high, (i.e., T >> θD), x = ( hν/kT) is very small and hence
ex can be expanded as a power series in x. ∴ex = 1 + x + x2/2! + x3/3! + …..Neglecting the higher
powers this becomes, ex = 1 + x (or) (ex – 1) = x. Substituting this in (7)
θD θD

9 RT 4 θ D
4 T 3 4 T 3
9 RT x .dx 9 RT
E= ∫ = ∫ x .dx =
2
. . .
θ D3 0
x θ D3 0 θ D 3 3T 3
 ∂E 
i.e., E = 3RT ∴Cv =   = 3R, the classical value ( Dulong - Petit' s law)
 ∂T V
Thus, Cv is a constant = 3R at high temperature as in the case of theory & experiment.
Case (ii): Temperature T is very low (i.e., T << θD , TÆ0 ). In this case, (θD/T) is very large i.e.,
(θD/T) Æ ∝. Using this as the upper limit of the integral in eqn (7), the integral becomes a standard
integral whose value is given by π4/15.

9 RT 4  x 3 .dx 

9 RT 4  π 4 
θ D 3  ∫0 e x − 1 
i.e., E = .   = .
θ D 3  15 
3π RT 4  ∂E  12π R 3 ……………(8)
i.e., E = ∴ CV =   = .T
5θ D 3
 ∂T V 5θ D 3
10

Thus, according to Debye’s theory, CV


the specific heat of a solid Cv α T3
at very low temperatures, as observed 3R
experimentally. As νD is different for
different solids, θD is different for
different solids, Hence Cv depends Expt & Debye theory
both on Debye frequency and temperature
at low temperatures. . Cv =3R, a constant 0 T(K)
independent of temperature and frequency
at high temperatures. Thus Debye’s theory is successful in explaining the temperature dependence of
Cv. correctly.
Drawback:
Debye’s theory breaks down at frequencies close to νD. At such high frequencies, the
wavelength (λ = c/νD ) of the lattice waves is small & comparable to the lattice spacing and hence
the continuum approximation becomes invalid.

Thermal conductivity:

Heat energy can be transmitted through crystals via the motion of phonons,
photons, free electrons or free holes, electron- hole pairs etc. The highest contribution
to thermal conduction in metals comes from free electrons. On the other hand, in
insulators almost the entire contributions to thermal conductivity comes from phonons.
dT
When there is a temperature gradient of across the two ends of a material, the
dx
dT
conductivity K is defined by the equation Q = K. where Q is the energy current density.
dx
[Thermal energy flowing per unit time across unit area].
From the kinetic theory of gases, it can be shown that the thermal conductivity of
an ideal gas in which a temperature gradient exists is given by
11

1
K= .V .λ.Cv ------------- (1)
3
Where V = average velocity of gas molecules
Cv = specific heat at constant volume of the gas and
λ = mean free length between successive collisions
This equation is more valid for a ‘phonon gas’ in an insulated solid as v, the velocity of
sound, is a constant for phonons.
The heat conduction by ‘phonon gas’ in solids is characterized by phonon flow.
Phonons are created at hot end and are annihilated at the cold end.
In equation (1), for thermal conductivity of insulators, v is the sound velocity and
Cv is the specific heat due to phonons given by Debye T 3 law:
Cv = α .T 3 where α is a constant.

Thermal Conductivity of metals


In the case of metals, major part of thermal conductivity arises from the movement of free
electrons. The following assumptions are made:-
1) The metal consists of fixed positive ions in a sea of free electrons.
2) The electrons behave as a perfect gas transporting thermal energy when there is a
temperature gradient.
3) Each electron travels a distance λ and mean free time τ before colliding with a
positive ion and giving up all its thermal energy.
4) The electrons at the top of the distribution only are active in the transport process. This
means that electrons with energy close to Fermi energy EF are involved in this

process. Then the velocity VF corresponding to EF is given by

1 2 EF
.m.VF 2 = EF or VF2 = ------------------ (2)
2 m
where V = VF is the velocity corresponding to energy E = EF

Also, Mean free length, λ = VFτ ----------- (3).


12

1
Using (2) and (3) in (1) i.e., in the eqn, K = .V .λ.Cv , we get
3
1 1 2E τ C
K= VF .VFτ .CV = VF 2τ CV = F V ………(4)
3 3 3m
Here Cv is the electronic specific heat Ce, viz. Cv = Ce
 π 2 Nk 2 
From the free electron theory, Ce =   .T (kÆ Boltzmann Constant)
 2 EF 
Using this in (4) for CV, the expression for thermal conductivity K of metal reduces to

2 EFτ  π 2 Nk 2   π 2 Nk 2τ 
K= .  .T =   .T ……….(5)
3m  2 EF   3m 
In the above expression, K appears to be proportional to temperature, T. But as τ is inversely
proportional to T, actually, K is independent of temperature. This is consistent with experimental
values of K.

Wiedermann-Franz law
Wiedermann and Franz found that the ratio of thermal conductivity K to the electrical conductivity σ
is the same for all metals at a given temperature. This can be shown as given below.
From the free electron theory, the electrical conductivity σ is given by
 π 2k 2 
L =  2  = 2.45 × 10−8 Watt.Ohm.Deg -2 …….(6).
 3e 

K  π 2 Nk 2τ  m  π 2k 2 
Using eqns. (5) and (6) the ratio (K/ σ) is found to be =  .T . =  2  .T
σ  3m  Ne τ  3e 
2

K  π 2k 2 
Thus, =  2  .T . ……. (7). In deriving this Wiedermann-Franz law, it is assumed that mean
σ  3e 
free path is the same for both electrical and thermal conductivities of the metal. Rearranging eqn.

K  π 2k 2   π 2k 2 
(7), we get, L = =  2  , where, L =  2  = 2.45 × 10−8 Watt.Ohm.Deg -2 is known as
σ T  3e   3e 
Lorentz number which should be the same for all metals. I t was found to be in good agreement with
calculations.
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