SPECIFIC HEAT OF SOLIDS.

Classical theory Dulong and Petits law:

According to the Dulong and Petits 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
average kinetic energy =
2
1
kT, where k is the Boltzmanns constant and the T is the
absolute temperature.
Total Energy of an one dimensional S.H.O = Kinetic energy + Potential energy.
= kT + kT = kT
If we consider 1 mole of solid, it will contain N
0
number (Avogadro number) of
atoms. Thus, the solid will have 3
0
no. of one dimensional S.H.Os.
Total energy of the solid = Total no. of S.H.OTotal energy per S.H.O
i.e., E = 3
0
. kT = 3RT where R is the universal gas constant.
Molar specific heat at constant volume,
v
C =
v
| |
|

\ .
= ( ) 3 3 R R

Experimental values of
v
C of C
V
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 Petits law.
T
0
2
But experiments at low temperatures show that
v
C is nearly proportional to
3
T .and
v
C tends to zero as temperature tends to zero. Thus Dulong and Petits law is valid only at
high temperatures.

EINSTEINS THEORY OF SPECIFIC HEATS OF SOLIDS:
According to Einstein, the basic error in the Dulong and Petits 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, .
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 , can absorb or emit energy in multiples of a quantum of energy.
= h. [i.e, E = 0, h, 2h, 3h, 4h 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
i
E is given by the Boltzmann factor

kT
E
i
e

.
6) This means that the number of oscillators with energy
i
E is given by

|
.
|

\
|

=
kT
E
C
i
exp . n
i
----------(1) where C is a constant.
If
0
n be the number of oscillators with zero energy then,
0
n = c e c =
0
. . Replacing C in eqn (1)
by
0
n , we get,
kT
E
i
i
e n n

=
. 0
--------------------------------------- (2)
where E
i
is the energy in the ith state and E
i
=i(h). i = 0.1.2.3 etc.
3
Let h = and hence E
0
= 0, h E h E 2 2 ,
2 1
= = = = ,etc., be the allowed
energies of oscillators with frequency . Let
0
n , ., .......... ,
2 1
etc n n be the number of oscillators
having energies 0, and .. ,......... 2 , so on.
Total number of oscillators with frequency is N =
0
n + ......
2 1
+ + n n
...... . .
2
0 0 0
+ + + =

kT kT
e n e n n N




(

+ + + =

.... 1
2
0
kT kT
e e n

---(3)
But | | .... 1
3 2 x x x
e e e + + + =
x
e 1
1

|
|
.
|

\
|

=
|
|
.
|

\
|
+ + + +


kT
kT kT kT
e
e e e


1
1
.. .......... 1
3 2
.-(i) . Using this in (3),
we get,
kT
e
n
N

=
1
0
---------------------------- (4)
The total energy of all these N oscillators will be

.... . 3 . 2 . 0 .
3 2 1 0
+ + + + = n n n n E

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

kT kT kT
e n e n e n


------- (5)
Multiplying (5) by
kT
e

, .. .......... . . 3 . . 2 . . .
4
0
3
0
2
0
+ + + =

kT kT kT kT
e n e n e n e E

(6)
Subtracting equation (6) from (5)
|
|
.
|

\
|
+ + + + =
|
|
.
|

\
|

+ + + =
|
|
.
|

\
|

.. .......... 1 . . 1 . ., .
.. .......... . . . . . . 1 .
3 2
0
3
0
2
0 0
kT kT kT kT kT
kT kT kT kT
e e e e n e E e i
e n e n e n e E

4
i.e.
|
|
.
|

\
|

kT
e E

1 . =
kT
e
kT
e n

1
.
0
(using eqn. (i)). Rearranging this,

2
.
0
1
kT
n e
E
kT
e

=
| |
|

|
|
\ .
i.e., Total energy
2
.
0
1
kT
n e
E
kT
e

=
| |
|

|
|
\ .
(7)

Average energy per oscillator <E> =
N
E

Substituting for N and E from eqns. (4) and (7) respectively, we get,


0
2
0
1
. .
.
1
1
kT
e
kT kT
n e e
E
n
kT
kT
e
e

| |
|

|
|
\ .
< >= =
| |
| |
|
|

|
|
|
|
\ .
\ .


i.e.,
.

1
E
kT
e
kT kT
e e

< > =
| |
|
|

|
|
|
\ .


1
E
kT
e

< > =
| |
|

|
|
\ .
Using = h / kT, we have


1
h
E
h
kT
e

< > =
| |
|

|
|
\ .
.. (8)
5

This is the average energy of an one dimensional oscillator.
If there are N
0
atoms in one mole of the solid, there will be 3N
0
one dimensional harmonic
oscillators in the solid per mole. Here, obviously, N
0
is the Avogadro number.
Total energy of 1 mole of the solid is, E =3N
0
<E>

0
3

1
N h
E
h
kT
e

=
| |
|

|
|
\ .

Let (h/k) =
E
, known as Einsteins Temperature, which is a characteristic of the given solid.
E
0
3

1
E
E
N k
T
e

=
| |
|

|
|
\ .
(or)
2
V
C = = 3 . .
E
E
v
T
R e
T

| | | |
| |

\ .
\ .
3
E =
1
E
E
R
T
e

| |
|

|
|
\ .
.(9)
2
V 2
E
Molar Specific heat at constant volume , C 3
1
E
E
T
E
V
T
e
R
T T
e

| | | |
= =
| |

\ . \ .
| |

|
\ .
.(10)
CASE 1:- When temperature T is very high, such that T >>
E
, then
E
T
| |
|
\ .
is very small.

2 3
1 1
1 ...... 1
2! 3!
E
E E E E T
e
T T T T

| | | | | | | |
+ + + + +
| | | |
\ . \ . \ . \ .
, neglecting higher powers.
1 . Using this in eqn. (9), we get,
E
E T
e
T

| |

|
\ .


V
3
E = 3 and hence C 3
( )
E
E
V
R E
RT R
T
T

| |
= = =
|

\ .
, the classical theory value.
CASE 2:- When temperature T is small, such that T <<
E
, then
2
E
T
| |
|
\ .
E
T
| |
|
\ .
is very large.
1 and hence 1 , neglecting 1. Using this in eqn. (9), we get,
E
E E
T
T T
e e e

| |
|
\ .
>>
6

3
E =
E
E
R
T
e

| |
|
|
|
\ .


2
V
C = = 3 . .
E
E
v
T
R e
T

| | | |
| |

\ .
\ .

Thus, Einsteins 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
E
ie., the
characteristic frequency of vibration of the solid.
In the above equation as T reduces,
2
E
T
| |
|
\ .
C
V
increases while
E
T
e

reduces. Since the
exponential reduction is much faster, value of Expt
Cv reduces exponentially with reducing temperature.
But experiments at low temperatures show that
v
C Einsteins Theory
is nearly proportional to
3
T and
v
C tends to zero T
as temperature tends to zero more slowly than that predicted by the Einsteins theory.
Draw back of Einsteins theory:
Einsteins 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 Einsteins 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.






7
Debyes Theory of Specific heat of Solids
Einsteins 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, .
8. The density of vibrational modes with frequencies in the range between
and + d is given by ( ) solid the of volume the is V where
c
V 4
3
2

= Z .
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
D
, known as Debyes cut off frequency. Thus in thermal equilibrium a
solid will have vibrations with frequencies between 0 and
D
.
As each three dimensional vibration mode can be polarized into one longitudinal and two
transverse waves with velocities c
l
and c
t
respectively, the density of modes will be
( )
2
3
t
3
l
.
c
2

c
1
V 4
|
|
.
|

\
|
+ = Z . Therefore number of modes with frequency between and + d is
given by ( ) ) ........(1 . .
c
2

c
1
V 4 .d
2
3
t
3
l
d Z
|
|
.
|

\
|
+ =
The total number of all possible modes of vibration is obtained by integrating the

8
equation (1) with limits between 0 and
D
. But the total number of possible modes is 3N only.
Therefore, ( )

=
D
0
3 .d

N Z
i.e.,
D
D
2
3 3
l t 0
2
3 3
l t 0
3
D
3 3 3 3 3
l t l t D
1 2
4 V . .d 3
c c
1 2
4 V . .d 3
c c
1 2 1 2 9N
4 V . 3 (or) 4 V ......(2)
c c 3 c c
N
N
N

| |
+ =
|
\ .
| |
+ =
|
\ .
| | | |
+ = + =
| |
\ . \ .

Substituting this back into eqn (1), we have, ( ) ) ........(3 . .
9N
.d
2
3

d Z
D
=
From Plancks quantum theory and Einsteins theory of specific heat of solids, the average energy of
oscillators with frequency between and + d is given by
|
|
.
|

\
|

>= <
1
kT
h
e
h
E

. Energy due to all the modes with frequency between and + d is given by
dE = Z()d.<E> i.e.,

d
e
h N
dE
kT
h
D
.
1
9
3
3
|
|
.
|

\
|

=
Total energy of the solid is given by
3 3
3 3
0 0 0
9 9
. i.e., . . ......(4)
1 1
D D D
h h
D D
kT kT
N h Nh
E dE d E d
e e





= = =
| | | |

| |
\ . \ .

h
k
k
h
Let
D
D D
D

= = solid. the of stic characteri a is which re temperatu Debye as known ,

9
D
D
, (or) . .....( ) . ....... (ii)
h
When 0, x 0 and when , x ......(iii)
Replacing the variable by x , changing the lim
D
h kT kT
Also let x x i d dx
kT h h
kT T

= = =
= = = = =
( )
( )
3
3
3
3 3
0
3
4
3
its of the integral and substituting for
. .
from the above equations, the eqn (4) becomes, 9 . .
1
..
................ (6). For
9
1 .
D
D
T
x
D
x
D
kT kT
x dx
h h h
E Nh
k e
x dx
NkT
e E

| | | |
| |
\ . \ .
=

0
0
1 mole of the solid, N is replaced by the Avogadro number, N .
D
T

As Nk = N
0
k =R for 1 mole, , the universal gas constant, it becomes, ) 7 .......(
1
.
.
9
3 T
0
3
4
D

=
x
D
e
dx x RT
E

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


Case (i) : When the temperature T is very high, (i.e., T >>
D
), x = ( h/kT) is very small and hence
e
x
can be expanded as a power series in x. e
x
= 1 + x + x
2
/2! + x
3
/3! + ..Neglecting the higher
powers this becomes, e
x
= 1 + x (or) (e
x
1) = x. Substituting this in (7)
law) s Petit' - Dulong ( value classical the 3R, C 3RT E ., .
3
.
9
. .
9

.
.
9
v
3
3
3
4
2
T
0
3
4 3 T
0
3
4
D D
=
|
.
|

\
|

= =
= = =

V
D
D D D
T
E
e i
T
RT
dx x
RT
x
dx x RT
E




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 <<
D ,
T0 ). In this case, (
D
/T) is very large i.e.,
(
D
/T) . Using this as the upper limit of the integral in eqn (7), the integral becomes a standard
integral whose value is given by
4
/15.


(8)
4 3 4 4
3 3
0
4
3
V 3 3
9 . 9
. ., . = .
1 15
3 12
. ., E = C = = .
5 5
x
D D
V D D
RT x dx RT
i e E
e
RT E R
i e T
T

( (
=
( (

| |

\ .

10


Thus, according to Debyes theory, C
V
the specific heat of a solid C
v
T
3

at very low temperatures, as observed 3R
experimentally. As
D
is different for
different solids,
D
is different for
different solids, Hence C
v
depends Expt & Debye theory
both on Debye frequency and temperature
at low temperatures. . C
v
=3R, a constant 0 T(K)
independent of temperature and frequency
at high temperatures. Thus Debyes theory is successful in explaining the temperature dependence of
C
v
. correctly.
Drawback:
Debyes theory breaks down at frequencies close to
D
. At such high frequencies, the
wavelength ( = c/
D
) 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.
When there is a temperature gradient of
dx
dT
across the two ends of a material, the
conductivity K is defined by the equation Q = K.
dx
dT
where Q is the energy current density.
[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
K=
1
. . .
3
v
V C ------------- (1)
Where V = average velocity of gas molecules

v
C = specific heat at constant volume of the gas and
= 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
v
C is the specific heat due to phonons given by Debye
3
T law:

3
.T C
v
= where 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 and mean free time 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
F
E are involved in this
process. Then the velocity V
F
corresponding to
F
E is given by

2
F
1
. .V
2
F
m E = or
m
E
V
F
F
2
2
= ------------------ (2)
where V =
F
V is the velocity corresponding to energy E =
F
E
Also, Mean free length,
F
V = ----------- (3).
12
Using (2) and (3) in (1) i.e., in the eqn, K =
1
. . .
3
v
V C , we get
K =
2
2 1 1
. .
3 3 3
F V
F F V F V
E C
V V C V C
m

= = (4)
Here C
v
is the electronic specific heat C
e
, viz. C
v
= C
e

From the free electron theory,
2 2
.
2
e
F
Nk
C T
E
| |
=
|
\ .
(k Boltzmann Constant)
Using this in (4) for C
V
, the expression for thermal conductivity K of metal reduces to

2 2 2 2
2
. . .
3 2 3
F
F
E Nk Nk
K T T
m E m
| | | |
= =
| |
\ . \ .
.(5)
In the above expression, K appears to be proportional to temperature, T. But as 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
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 is given by
2 2
8 -2
2
2.45 10 Watt.Ohm.Deg
3
k
L
e

| |
= =
|
\ .
.(6).
Using eqns. (5) and (6) the ratio (K/ ) is found to be
2 2 2 2
2 2
. . .
3 3
K Nk m k
T T
m Ne e


| | | |
= =
| |
\ . \ .

Thus,
2 2
2
.
3
K k
T
e

| |
=
|
\ .
. . (7). In deriving this Wiedermann-Franz law, it is assumed that mean
free path is the same for both electrical and thermal conductivities of the metal. Rearranging eqn.
(7), we get,
2 2
2
3
K k
L
T e

| |
= =
|
\ .
, where,
2 2
8 -2
2
2.45 10 Watt.Ohm.Deg
3
k
L
e

| |
= =
|
\ .
is known as
Lorentz number which should be the same for all metals. I t was found to be in good agreement with
calculations.

13