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UNIT – 1
ELECTRICAL PROPERTIES OF MATERIALS
CONTENTS
1.5. Classical Free Electron theory

1.5.1. Postulates of classical free electron theory

1.5.2. Electrical Conductivity
1.5.3. Thermal Conductivity
1.5.4 Wiede- Mann – Franz Law

1.5.5. Lorentz number

1.5.6. Success of classical free electron theory
1.5.7. Drawbacks of classical free electron theory
1.5. Classical Free Electron theory
After the discovery of electron, Drude and Lorentz proposed classical free
electron theory in 1900. It is a macroscopic theory and explains electrical and thermal
properties of solids based on classical laws.
1.5.1. Postulates of classical free electron theory
In the absence of electrical field
 The electrons are moves freely in the boundaries of the metal, similar to the gas
molecules moving in a vessel.
 The forces between the conduction electrons and ion core in neglected.
 The electrons possess kinetic energy only.
 Free electrons are elastically collides with each.
In the presence of field
 The free electrons move in the opposite direction to the applied electrical field
direction.
 It is obey the classical Maxwell-Boltzmann distribution of velocities.
 All free electrons gain equal amount of thermal energy and involved for thermal
conduction.
Mean free path

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The average distance travelled by a free electron in any two successive collisions
is known as mean free path.

𝜆 = 𝑉𝑑 𝜏𝑐
Collision time
The average time taken by a free electron in any two successive collisions is
called collision time.
𝜏𝑐 = 𝜆⁄𝑉
𝑑

Relaxation time
Average time taken by a free electron to reach its equilibrium state from
disturbed state due to the application of an electrical field is known relaxation time.It is
approximately equal to 10-14 s.
Mobility
The drift velocity acquired by the electron per unit applied electrical field to it.
𝑉𝑑
𝜇= 𝑚2 𝑉 −1 𝑆 −1 )
𝐸
1.5.2. Electrical Conductivity
The amount of electrical charges conducted per unit time across unit area per unit
applied electrical field is known as electrical conductivity.
𝑄
𝜎=
𝑡𝐴𝐸
𝐼
𝜎= (∵ 𝑄⁄𝑡 = 𝐼)
𝐴𝐸
𝐽
𝜎= (∵ 𝐼 ⁄𝐴 = 𝐽)
𝐸
𝐽 = 𝜎𝐸
Derivation of Electrical Conductivity of metals
Consider a metal conductor of ‘XY’ and ‘E’ is the applied electric field to it. The
electron moves in opposite directions to the applied field with a velocity𝑉𝑑 .
Let ‘n’ be the number of free electrons per unit volume.

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Fig 1.5.1 Movement of free electrons in a metal rod

Current density of a conducting material is given by,

𝐽 = −𝑒𝑛𝑉𝑑 … … … … . . . (1)
Force experienced by the electron is
𝐹 = −𝑒𝐸 … … … … (2)
This force accelerates the electron
𝐷𝑟𝑖𝑓𝑡 𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦
𝑎=
𝐶𝑜𝑙𝑙𝑖𝑠𝑜𝑛 𝑡𝑖𝑚𝑒
𝑉𝑑
𝑎=
𝜏

𝑉𝑑 = 𝑎𝜏 … … … … . (3)
From the Newton’s second law of motion, the force on the electron,
𝐹 = 𝑚𝑎 … … … … … . (4)
Equate equations (2) and (4) we have,
−𝑒𝐸 = 𝑚𝑎
−𝑒𝐸
𝑎= … … … … … (5)
𝑚
Substitute Eqn. (5) in Eqn. (3) we get,
−𝑒𝐸𝜏
𝑉𝑑 = … … … … … . . (6)
𝑚

Substituting eqn. (6) in eqn. (1) we have,

(−𝑒)𝑛(−𝑒𝐸𝜏)
𝐽=
𝑚

𝑛𝐸𝑒 2 𝜏
𝐽=
𝑚
𝐽 𝑛𝑒 2 𝜏
=
𝐸 𝑚
𝑛𝑒 2 𝜏
𝜎= … … … … . (7) (∵ 𝜎 = 𝐽⁄𝐸 )
𝑚

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We find that with increase of electron concentration ‘n’, the conductivity ‘σ’ is
increases. As ‘m’ increases the motion of the electron becomes slow and hence the
conductivity ‘σ’ decreases.
Co-efficient of electrical conductivity
The quantity of electricity flowing per unit area per unit time maintained at unit
potential gradient.
𝐽 = 𝜎𝐸
𝐼
= 𝜎𝐸
𝐴
If A=1; E=1, then,
𝐼=𝜎
1.5.3. Thermal Conductivity
The amount of heat conducted by the conductor is
𝑑𝑇
𝑄 = 𝐾𝐴 𝑡
𝑑𝑥
𝑄
𝐾= 𝑑𝑇
… … … … … (1)
𝐴 (𝑑𝑥 ) 𝑡

Where,
K → is the thermal conductivity
A → is the area of cross section
t → is the time of flow of heat
𝑑𝑇
→ Temperature gradient
𝑑𝑥

The amount of heat conducted per unit time per unit area of cross section per unit
temperature gradient.
If A = 1; t = 1, then eqn. (1) becomes
𝑄
𝐾= 𝑑𝑇
𝑑𝑥
𝑑𝑇
𝑄=𝐾 … … … … … . . (2)
𝑑𝑥

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Expression for thermal conductivity of a metal

Consider a metal rod ‘AB’ with the length of ‘λ’. Let ‘A’ be at higher temperature
and ‘B’ at al low temperature. Now, heat flows from A to B by the free electrons.

Fig 1.5.2 Thermal conductivity of a metal

Free electron per unit volume = n
Average velocity of the electrons = v
Average kinetic energy of electron at ‘A’ is
= 3⁄2 𝐾𝐵 𝑇 … … … … … . (3)
Where,
KB → is the Boltzmann constant
T → is the temperature at A
Average kinetic energy of an electron at ‘B’ is
= 3⁄2 𝐾𝐵 (𝑇 − 𝑑𝑇) … … … … (4)
The excess of kinetic energy carried by the electron from A to B is,
3 3
= 𝐾𝐵 𝑇 − 𝐾𝐵 (𝑇 − 𝑑𝑇)
2 2
3 3 3
= 𝐾𝐵 𝑇 − 𝐾𝐵 𝑇 + 𝐾𝐵 𝑑𝑇
2 2 2
3
= 𝐾𝐵 𝑑𝑇 … … … … … . . (5)
2

Let us assume that, there is an equal probability for the electrons to move in all
six directions shown in given figure.

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Each electrons travels with thermal velocity ‘v’ and ‘n’ is the free electrons per
unit volume. Then 1/6 nv electrons travel in any one of the directions per unit area per
unit time.
Number of electrons crossing per unit area per unit time A to B is
1
= 𝑛𝑣
6

The excess of energy carried from A to B per unit area in unit time is
1 3
= 𝑛𝑣 × 𝐾𝐵 𝑑𝑇
6 2
1
= 𝑛𝑣𝐾𝐵 𝑑𝑇 … … … … . . (6)
4
Similarly, the deficient of energy carried from B to A per unit area per unit time
1
= − 𝑛𝑣𝐾𝐵 𝑑𝑇 … … … … … . (7)
4

Hence, the net amount of energy transferred from A to B per unit area per unit
time.
1 1
𝑄 = 𝑛𝑣𝐾𝐵 𝑑𝑇 − (− 𝑛𝑣𝐾𝐵 𝑑𝑇)
4 4
1
𝑄 = 𝑛𝑣𝐾𝐵 𝑑𝑇 … … … … … . (8)
2

Compare eqn. (2) and (8), we get

𝑑𝑇 1
𝐾 = 𝑛𝑣𝐾𝐵 𝑑𝑇
𝑑𝑥 2
1
𝐾 = 𝑛𝑣𝐾𝐵 𝑑𝑥
2
1
𝐾 = 𝑛𝑣𝐾𝐵 𝜆 … … . (9) (∵ 𝜆 = 𝑑𝑥)
2

We know that for the metals, the collision time is equal to the relaxation time.
𝜆 = 𝑣𝜏 … … … … … . (10)
Substitute eqn. (10) in eqn. (9) we have,
1
𝐾 = 𝑛𝑣𝐾𝐵 𝑣𝜏
2
1
𝐾 = 𝑛𝑣 2 𝐾𝐵 𝜏 … … … … … (11)
2

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This is the expression of thermal conductivity and it is directly proportional to the

square of the velocity of the electrons.

1.5.4. 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. This ratio is a constant
for all metals at given temperature.
𝐾
∝𝑇
𝜎
𝐾
= 𝐿𝑇
𝜎
Where,‘L’ is proportionality constant. It is known as Lorentz number. Its value
is2.44 x 10-8WΩK-2 at T=293 K.

From classical theory, the electrical thermal conductivity of a metal is given as

𝑛𝑒 2 𝜏
𝜎= … … … … … … . . (1)
𝑚
1
𝐾 = 𝑛𝑣 2 𝐾𝐵 𝜏 … … … … … … … (2)
2
1
𝐾 (2𝑛𝑣 2 𝐾𝐵 𝜏)
= 𝑛𝑒2 𝜏
𝜎
𝑚
1
𝐾 𝑚𝑣 2 𝐾𝐵
= 2
− (3)
𝜎 𝑒2
We know that the kinetic energy of the electron is
1 3
𝑚𝑣 2 = 𝐾𝐵 𝑇 … … … … … … . . (4)
2 2

Substituting eqn. (4) in eqn.(3), we have

𝐾 3𝐾𝐵 𝑇𝐾𝐵
=
𝜎 2𝑒 2
𝐾 3𝐾𝐵2 𝑇
=
𝜎 𝑒2
𝐾 3 𝐾𝐵 2
= ( ) 𝑇
𝜎 2 𝑒

𝐾 3 𝐾𝐵 2
= 𝐿𝑇 … … … … … … (5) (∵ 𝐿 = ( ) )
𝜎 2 𝑒
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Where ‘L’is a constant and it is known as Lorentz number.According to this law it

can be conclude that if a metal has high thermal conductivity, it will also have high
electrical conductivity.
1.5.5. Lorentz number
The ratio between the thermal conductivity (K) to the product electrical
conductivity (σ) and absolute temperature (T) of the metal is a constant. The constant
value is known as Lorentz number.

𝐾
𝐿= … … … … … … . . (1)
𝜎𝑇

According to classical theory,

3 𝐾𝐵 2
𝐿= ( ) … … … … … … … . (2)
2 𝑒

Substitute the values of KB = 1.38 x 10-23 JK-1and e = 1.602 x 10-19 C in equation

(2), we have,

2
3 1.38 × 10−23
𝐿= ( )
2 1.602 × 10−19

𝐿 = 1.12 × 10−8 𝑊𝛺𝐾 −2 … … … … . . (3)

Hence, it was found that the classical value of Lorentz number is only half of the
experimental value, i.e., L = 2.44×10-8 WΩK-2. This discrepancy in the experimental
and theoretical value of Lorentz number is the failure of classical theory. This was
rectified by quantum theory.

According to the quantum theory, electrons near the Fermi level alone contribute
towards thermal and noble conductions. Using quantum free electron theory model, the
electronic specific heat value is given by
𝑛𝜋 2 𝐾𝐵2 𝑇
𝐶𝑣 = … … … … … . (4)
𝑚𝑣 2
Thermal conductivity is

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1
𝐾 = 𝐶𝑣 𝑣 2 𝜏 … … … … … … (5)
3
Substitute equation (4) in (5) we get,
𝑛𝜋 2 𝐾𝐵2 𝑇𝑣 2 𝜏
𝐾=
3𝑚𝑣 2
𝑛𝜋 2 𝐾𝐵2 𝑇𝜏
𝐾= … … … … . (6)
3𝑚
The electrical conductivity is
𝑛𝑒 2 𝜏
𝜎= … … … … … … . . (7)
𝑚
From equations (6) and (7) we get,
2
𝑛𝜋2 𝐾𝐵 𝑇𝜏
𝐾 3𝑚
= 𝑛𝑒 2 𝜏
𝜎
𝑚

𝐾 𝑚𝑛𝜋 2 𝐾𝐵2 𝑇𝜏
=
𝜎 3𝑚𝑛𝑒 2 𝜏
𝐾 𝜋 2 𝐾𝐵 2
= ( ) 𝑇
𝜎 3 𝑒
𝐾 𝜋 2 𝐾𝐵 2
= ( )
𝜎𝑇 3 𝑒
𝐾
=𝐿 … … … … … … . (8)
𝜎𝑇

𝜋 2 𝐾𝐵 2
𝐿= ( )
3 𝑒
Substitute the values of KB = 1.38 × 10-23 JK-1and e = 1.602 × 10-19 C in equation
(2), we have,

2
(3.14)2 1.38 × 10−23
𝐿= ( )
3 1.602 × 10−19

𝐿 = 2.44 × 10−8 𝑊𝛺𝐾 −2 … … … … . . (9)

This value is in good agreement with the experimental value. The Widemann Franz
law is not appreciable at very low temperature.

1.5.6. Success of classical free electron theory

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1. It verifies ohm’s law

2. It explains the electron and thermal conductivity.
3. It derives Widemann – Franz law.
4. It explains optical properties of metals.
1.5.7. Drawbacks of classical free electron theory

1. It is failed to explain photoelectric effect, Compton Effect, Para magnetism,

ferromagnetism and black body radiation.
2. It is a macroscopic theory.
3. It cannot explain the electrical conductivity of semiconductors or insulators using
this model.
4. It states that all the free electrons will absorb energy, but quantum theory states
that only free electrons will absorb energy.
5. In classical free electron theory, theoretical and experimental value of Lorentz
number is not matched. It is rectified by quantum theory.
6. Theoretical and experimental value of specific heat (4.5𝑅 ≠ 3𝑅) and electronic
specific heat (3⁄2 𝑅 ≠ 0.01𝑅) is not matched.

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