UNIT – 2

Electrical and Thermal Properties of Solids

Electric Properties
Classical Free electron theory of metals:
[Drude – Lorentz classical theory]
The outstanding properties of metals are their high electrical and thermal conductivities.
We can understand such important physical properties of metals in terms of the free electron
model.
Drude, in 1900 postulated that the metal consists of positive ion cores with valence
electrons moving freely among these cores. The electrons are however bound to move within the
metal due to electrostatic attraction between the positive ion cores and the electrons. The
potential field of these ion cores, which is responsible for such an interaction, is assumed to be
constant throughout the metal and the mutual repulsion among the electrons is neglected. The
behaviour of free electrons moving inside the metals is considered to be similar to that of atoms
or molecules in a perfect gas. These free electrons are therefore referred as free electron gas.
These electrons are responsible for conduction of electricity through metals. Since the
conduction electrons move in a uniform electrostatic field of ion cores, their potential energy
remains constant, normally taken as zero. Thus the total energy of conduction electrons is equal
to its kinetic energy.
Valance electron

Cu 29e-

Assumptions of the classical free electron theory:

1. A metal is imagined as a structure of 3 –dimensional array of ions, in between which
there are freely moving valence electrons confined to the body of the material, and are
called conduction electrons.
 2. The free electrons are treated as equivalent to gas molecules, and thus they are assumed
 3
to obey the laws of kinetic theory of gases. Thus the energy is given by   KT and it is
 2
 3 1
related to kinetic energy as   KT  mv n
2

 2 2
v n is the thermal velocity of the electrons.
3. The electric field due to the ionic cores is taken to be constant through out the body of the
metal and the effect of repulsion between the electrons is considered insignificant.
4. The electric current in a metal due to an applied field is a consequence of the drift
velocity in a direction opposite to the direction of the field.
Based on Drude’s considerations Lorentz in 1909 postulated that electrons gas obey Maxwell
– Boltzmann statistics under equilibrium conditions.
The combined ideas of Drude and Lorentz constitute Drude – Lorentz theory.
Merits:
1) Successfully explains the validity of Ohm’s law
2) Theory also explains the high luster and complete opacity of metals.
Demerits:
1) The theory predicts that resistivity varies as T , but actually it is found to vary linearly
with temperature.
2) According to theory, specific heat does not depend on temperature, but experimentally, it
is found directly proportional to temperature.

3) Theory predicts that conductivity σ  n , but it does not hold good. Where n →e–

concentration.
4) Theory failed to explain the paramagnetic susceptibility of the conduction electrons.
Quantum free electron theory
The free electron theory was modified by Sommerfield in order to reduce its defects. He
suggested that Maxwell – Boltzmann statistics is classical and it is applicable only for ordinary
gas not to electron gas. He suggested that Fermi – Dirac statistics holds good for electron gas.
An electron in a metal finds itself in the field of all nuclei and other electrons. The potential
energy for such an electron may therefore be expected to be periodic. The periodicity is being
that of the lattice.
As per Sommerfield model, the interior of the metal can be represented by potential
energy box of depth ‘Es’ as shown in fig. It consists of discrete set of energy levels, i.e., energy
levels of electrons are quantized. Potential energy of an electron inside the metal is lower than
that of an electron outside the metal.
Assumptions of the Quantum free electron theory
1. The energy values of the conduction electrons are quantized.
2. The distribution of electrons in the various energy levels occurs as per Pauli exclusion
principle.
3. The free electrons travel in a constant potential inside the metal, but stay confined within
its boundaries.
4. The attraction between the free electrons and the lattice ions, and the repulsion between
the electrons themselves are ignored.

Fermi energy:
The top most filled energy level at 0 K is known as Fermi level and the energy
corresponding to this level is called as Fermi energy EF.
2
 h 2  3n  3 2
E Fo      Bn 3
ES
 8m   
2
 h 2  3  3
where B =    is constant EF
 8m   
B = 5.85 x 10–38 J.

Fermi factor:
Effect of temperature on the occupancy of energy levels can be discussed with the help of
Fermi – Dirac statistics. It is apparent that, for temperature greater than O K, Fermi level may
not be the topmost filled level. Since some of the electrons from the filled energy levels may be
excited to the higher levels. Thus some of the levels below E Fo would be empty. While some
above it would be occupied.
 Fermi has shown that the probability that a particular quantum state is occupied is given
by so called Fermi factor ‘f (E)’ given by
1
f(E) = ( E  EF ) / KT
e 1
Fermi factor is the distribution function which gives the probability of occupancy of a
given energy state for a material in thermal equilibrium in terms of the Fermi energy, Boltzmann
constant and the temperature.
The dependence of Fermi factor on temperature:
i) Probability of occupancy for E < EF at O K
1 1
f(E) = 

e 1 0 1
f(E) = 1 for E < EF
∴ At T= 0 K, all the energy levels below the 1 T=0K
Fermi level are occupied. f(E)
T>0K

0 EF E
Figure (1)
ii) Probability of occupancy for E > EF at T = 0 K
1 1
f(E) = 

e 1 
∴ f(E) = 0 for E > EF
∴ At T = 0 K, all the energy levels above Fermi level are unoccupied.
In view of the above two cases, at T = 0 K, the variation of f(E) for different energy values,
becomes a step function, as shown in fig (1).

iii) At E = EF
1 1 1
∴ f(E) = f(E) =  
e 1 11 2
0

This means to say that, the highest occupied energy levels in metal at absolute zero has
an energy equal to EF.
As temperature increases from absolute zero, electrons occupying states lying near E F can
gain sufficient thermal energy to move into the higher unoccupied states. The actual change in
energy is very small. Since an electron can gain only few ‘KT’ of energy. Resulting change in
the curve is also shown in fig (1).

Fermi energy at T > 0 K

The Fermi energy EF, at any temperature T in general can be expressed in terms of ‘E Fo’
through the relation.
  2  KT  2 
E F  E Fo 1    
 12  E Fo  
 
Except at extremely high temperatures, the second term within the brackets is very small
compared to unity.
∴ EF ≈ EFo
Hence, the values of EFo can be taken to be essentially equal to EF itself.

Fermi temperature (TF):

It is the temperature at which the average thermal energy of the free electron in a solid
becomes equal to the Fermi energy at 0 K. But the thermal energy possessed by electrons is
given by the product kT.
∴ when T = TF, the equation EFo = kTF is satisfied, but EFo ≈ EF
EF
∴ kTF = EF or TF =
k
Fermi velocity:
The energy of the electrons which are at the Fermi level is E F. The velocity of the
electrons which occupy the Fermi level is called the Fermi velocity VF.
∴ EF = ½ mv2F
1
 2E  2
or VF =  F 
 m 
Expression for electrical conductivity:
Sommerfeld realized that, the free electrons obey Fermi – Dirac statistics. Hence by
applying Fermi – Dirac statistics and by using Boltzmann transport equation he arrived at an
equation for electrical conductivity of metals is given by
 ne 2 
 
m *VF
Where m* – effective mass of electrons
λ – mean free path
VF – Fermi velocity
Similarly electrical resistivity of the metal is given by
m *VF
  2
ne 
Merits of quantum free electron theory:
1) Specific Heat:
Only those electrons close to EF can absorb the heat energy. We can show using quantum
free electron theory that,
 2k 
Cv =   RT
 F
E
Taking a typical value of EF = 5 eV ( For metals EF varies from 1 to 10 eV), we get

 2k 
  = 10-4
 EF 

 Cv = 10-4 RT, which confirms the experimentally observed values.

Thus the quantum free electron theory is successful in explaining the low specific heat
value for conduction electrons.
2) Temperature dependence of electrical resistivity.
The experimentally observed fact that the electrical resistivity has a dependence on T, but
not on T.
As per quantum free electron theory, the electrical resistivity for metals is given by
m *VF
  --------- (1)
ne 2 
Also as per theory EF and VF are independent of temperature. But λ (mean free path) is
dependent on temperature.
If ‘r’ is the amplitude of vibration of ions in all the direction, then the area of cross
section that blocks the electron is πr2. If this area is more, then λ becomes small.
 1
 ----------- (2)
r 2
Now considering the facts that,
i) The energy of vibrating body is proportional to r2
ii) The energy of ions is due to thermal energy, and
iii) The thermal energy is proportional to T, so
1
r2 α T =>  ------ (3)
T
So equation (1) becomes,
 T Which is true experimentally.

3. Electrical conductivity and electron concentration

According to classical free electron theory  α n, the concentration of electrons. But
Aluminium and Gallium, which has 3 free electrons / atom have lower conductivity than metals
such as copper and silver which posses only 1 free electron / atom.

As per quantum free electron theory,

ne 2   
  
m*  VF 
From the above equation it is clear that, the value of ‘’ depends on both n and the ratio
  
  .
 VF 
If we compare the cases of copper and aluminium, the value of n for aluminium is 2.13
  
times higher than that of copper. But the value of   for copper is about 3.73 times higher
 VF 
than that of aluminium. Thus the conductivity of copper exceeds that of aluminium.

Density of states:
Density of states is defined as the number of energy states in the interval between energy state E

and E+dE and is represented as g(E) dE . It can be evaluated using quantum mechanical

considerations by treating free electrons in a metal as electrons inside deep potential well and

assuming their energy to have values .

Density of states is given by the expression,

g(E) dE= 8√2 π m3/2 E1/2 dE

h3
Graphically, this relationship gives a parabola.

Expression for Fermi energy at zero kelvin Temperature:

Let N(E) dE is the numbers of electrons per unit volume which possess energy in the range E and
E+dE.
Then N(E) dE is given by
N(E) dE = g(E) dE x f(E)…………………(1)
Where g(E) dE is the Density of states and
f(E) is the Fermi factor
The numbers of electrons per unit volume of the material n is given by

n=

or

n= ……………………….(2)

But f(E)= 1 at T=0K

n=

g(E) dE = 8√2 π m3/2 E1/2 dE

h3
Where m is the mass of the electron and h is the Planck’s constant
n =8√2 πm3/2

n =8√2 π m3/2 [2/3 E3/2 ]

h3

But at T =0K, the maximum energy that any electron of the material can have is EF0

n = 8√2 πm3/2 x [ 2/3 EFo3/2]

h3

After solving equation (3) , we get

2
 h 2  3n  3 2
E Fo      Bn 3

 8m   
2
 h 2  3  3
where B =    is constant
 8m   

B = 5.85 x 10–38 J.

𝐸
𝐹
0
1
Thermal Properties:

Thermal conductivity (K) of a material is equal to the amount of heat energy

(Q) conducted per unit area of cross section to the temperature gradient (dT/dx).
dT dT
i.e., Qα Or Q=K
dx dx
Q
Hence, Thermal conductivity, K = ------ (1)
dT / dx 
In solids, the conductivity takes place by both free electrons and thermally
excited lattice vibrations known as phonons.
Ktotal = Kelectrons + Kphonons
Expression for Thermal conductivity
Consider a uniform rod HC with temperature of the hot end H as T1 and the
temperature of the cold end C as T2 as shown in figure. Heat is flowing from H to C.
Lat A be the area of cross section, which is at a distance equal to the mean free path λ;
of the electrons between the two ends H and C. The kinetic energy of the electrons at
the hot end H is greater than that of the electrons at the cold end C.

H C
λ λ

T1 A T2

Let Q be the amount of heat flowing through the rod from the end H to C whose
length is 2λ.  The heat conducted
AT1  T2 
Q t
2

KAT1  T2 
Or Q t
2
Where K is the coefficient of thermal conductivity, A is the area of cross
section, t is the time for conduction and 2λ is the length of the rod.

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 The Thermal conductivity per unit area per unit time is

2 Q
K
AT1  T2 t

Let n be the number of available conduction electrons and v be the root mean
square velocity of the electrons.

Let us assume that the available free electrons in the metal are having an equal
probability to move in all six possible directions. Therefore an average of 1/6 nv
electrons can travel in any one direction.

We know that the free electrons are assumed to be free moving gas molecules.

3
The average kinetic energy of an electron at hot end H of temperature T1 = k B T1
2
Similarly,
3
The average kinetic energy of an electron at cold end C of temperature T2 = k B T2
2

1
The number of electrons crossing the area at A per second = nv
6

 The heat energy transferred per unit area per unit time from hot end H to cold end C
is = Number of electrons x Average kinetic energy of electrons from H to C
1 3 1
= nv k B T1 = nvk B T1
6 2 4

Similarly, the heat energy transferred across A per second from C to H

1 3 1
= nv k B T2 = nvk B T2
6 2 4
 The resultant heat energy transferred from H to C across A per second,

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 k B T1  T2 
nv
Q ------- (2)
4
dT T1  T2 
We know that, temperature gradient  ----- (3)
dx 2
Substituting the values of Q and temperature gradient, in equation (1), we get

k B T1  T2 
nv
2
Thermal conductivity, K 4
T1  T2 
1
K  nvk B  ------ (4)
2
We know from classical free electron theory, the electronic heat capacity of the metal
is,
3
Ce  R
2
Where R is gas constant and is equal to n kB. i.e. R = n kB
2
So that R  C e = n kB equation (4) becomes
3
1
 Thermal conductivity, K  Ce v  ----- (5)
3
Thermal conductivity of a metal is determined either using equation (4) or (5).
Wiedemann – Franz Law:
The ratio between the thermal conductivity and electrical conductivity of a
metal is directly proportional to the absolute temperature of the metal when the
temperature is not too low.
K K
i.e., T Or LT
 

Where L = K/T is a constant known as Lorentz number. The value of L is equal to

2.44 x 10-8 WK-2 at 293 K.

We know that the expression for

1
Thermal conductivity K  nvk B  ----- (1)
2

12
 ne 2 
Electrical conductivity  ------(3)
m

1
nvk B 
K 2 mvk B 
  
 ne 
2
2e 2 
m

Substituting λ = v τ in the above equation, we get

K mv 2 k B  1 k
  mv 2 B2
 2e 
2
2 e

1 3
Since mv 2  k B T , we get
2 2

K 3 k 3 k 2B
 k B T B2  T
 2 e 2 e2

K 3 k 2B
Therefore,  L
T 2 e2

Substituting the value of kB and e in the above equation, we get

L 

3 k 2B 3 1.38 10 23 
2

 1.1110 8 W  K  2 -----(4)

2 e 2 2 1.6 10 19 2 

The value of Lorentz number is not matching with experimental value

(2.44 x 10-8 WK-2), due to failure of classical theory.

According to quantum free electron theory, the expression for thermal

conductivity is modified by considering the electronic specific heat as,

13
 n 2 k 2B T
K ------(5)
3m

K n 2 k 2B T
2
m 2  kB 
Since L   2   
T 3m ne T 3  e 

 L
 
 2 1.38 10 23
2

 2.44 x 10-8 WK-2 -------(6)

31.6 10 
19 2

Equation (6) gives the correct value of Lorentz number and is in good
agreement with the experimental value.

Determination of thermal conductivity

Forbes’ method: This method is used to determine the thermal conductivity of a good
conductor.

Theory: Consider a long rod (metallic) of uniform area of cross section ‘A’ heated at
one end as shown.

After the steady state is reached, the amount of heat passing per second across the cross
section at the point ‘B’ is given by

 d 
Q  KA  ----(1)
 dx  B

 d 
Where   the temperature gradient at B and ‘K’ is the thermal conductivity of the
 dx  B
metal.

14
The amount of heat lost by radiation is given by

 d 
Q= mass x specific heat x  
 dt 

The amount of heat lost by radiation from the point B up to the end

d
C
C=   A dx  s dt
B
---(2)

 d 
Here ‘s’ is the Specific heat of the rod and ‘ρ’ the density of the material and   is
 dt 
the rate of cooling.

When the steady state is reached, the heat passing through the rod in one second is
equal to the heat radiated from the point ‘B’ up to the end ‘C’. Therefore comparing
equation (1) and (2)

 d  d
C
KA  =
 dx  B
  A dx   s
B
dt

d
C
 s dx
dt
K B

 d 
 
 dx  B

Thus thermal conductivity K of the metal is calculated using the above expression.

d  d 
C
To find B
dt
dx and   the experiment is divided into two parts.
 dx  B

1) Static part: The given rod is heated till the steady state is reached. Thermometers
are fixed in the rod at various positions as shown. After the steady state is reached the
readings in the thermometers (θ) and corresponding distance (x) from the hot end are
noted down. A graph of θ versus x is plotted as shown.

15
2) Dynamic part: The original bar or a small bar of the same material having the same
area of cross section is heated to the temperature of steam.

The bar is exposed to the atmosphere and a thermometer is fixed at its middle
portion. The decrease in temperature of the bar after regular interval of time (one
minute) is noted down. A graph of temperature ‘θ’ and time ‘t’ is plotted as shown.

 d 
From the graph, for various values of ‘θ’,   is determined. This done by
 dt 
drawing tangents to the curve at various points on the curve.

 d 
From the graphs (I) and (2), the values of   , corresponding to ‘θ’ and ‘x’
 dt 

 d 
are determined. A graph is plotted between   and ‘x’ as shown
 dt 

16
 The curve is produced to meet the x-axis, corresponding to the point ‘B’, a point

d
C
is located as shown. The area of the shaded portion = 
B
dt
dx

The area is measured from the graph directly.

d
C
 s dx
dt
Thermal conductivity K of the metal is given by K  B

 d 
 
 dx  B

 s area of the shaded portion 

Therefore, K =
tan 

Lee and Charlton’s method

This method is used to determine the thermal conductivity of a bad conductor.

Experimental arrangement

The apparatus consists of brass or copper disc C, which is suspended from the
stand as shown. On the brass disc, the specimen disc D (bad conductor) and a metallic
disc B are placed as shown

17
 Steam is passed through the steam chamber A. When the steady state is reached,
the readings of thermometers T1 & T2 are noted down.

Theory: The amount of heat passing through the bad conductor D in one Second=

Q  KA
1   2  ----(1)
d

Here A is the area of cross section of the disc D (A= πr2),

1   2  represents the
d
temperature gradient and ‘d’ is the thickness of the disc D.

The heat radiated by the exposed surface of ‘C’ in one second

 d 
= mass x Specific heat x   x correction factor
 dt 

A S
This correction factor = which gives the fraction of total area of the disc ‘C’
2A  S
which is exposed to the surroundings.

Therefore, the heat radiated by the exposed surface of ‘C’ in one second

 d   A  S 
=mS     --- (2)
 dt   2 A  S 

Here ‘m’ is the mass and ‘S’ is the specific heat of the disc C.

18
‘A’ is the area of cross section of ‘D’ and ‘C’. ‘S’ is the area of the curved surface of
 d 
‘C’ and   is the rate of cooling at temperature θ2.
 dt 

When steady state is reached, the heat passing through ‘D’ in one second is
equal to the heat radiated by the exposed surface of ‘C’ in one second.

Therefor comparing equations (1) and (2)

1   2  = m S  d  A S 
KA    
d  dt   2 A  S 

msd d  A  S 
K   ----W/mK
A (1   2 ) dt  2 A  S 

 d 
To determine  
 dt 

The disc ‘D’ is removed and the disc ‘C’ is placed in contact with the disc ‘B’.
When the temperature ‘θ2’ is increased by 10 0C, the steam chamber and disc ‘B’ are
removed. The decrease in temperature of disc ‘C’ is noted down after equal intervals of
time (one minute).

A graph of temperature ‘θ’ and time ‘t’ is drawn as shown. A tangent is drawn at
 d 
‘θ2’and the value of   is determined. This is substituted in the formula and K is
 dt  2

thus determined.

---------------- The End ---------------

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