Department of Physics, SSNCE, Kalavakkam, Engineering Physics-II (182202)

Unit-I, Conducting Materials Page Number 1

OBJECTIVES

1. To understand the detailed method of deriving the expressions for electrical and
thermal conductivity of metals (good conductors) using Classical free electron
theory and the relation between them indicated by Wiedmann-Franz law.
2. To understand the success and drawbacks of Classical free electron theory.

Expression for electrical conductivity of metals

The free electron theory was put forward in the 1900s by Paul Drude to explain
the transport properties of electrons in materials (especially metals). The Drude model is
the application of kinetic theory to electrons in a solid. It assumes that the material
contains immobile positive ions and an "electron gas" of classical, non-interacting
electrons of density ‘n’.
Postulates of the theory
1. The valence electrons of metallic atoms are free to move about the whole volume
of the metals like the molecules of a gas in a container. The collection of valence
electrons from all the atoms in a given piece of metal forms electron gas. It is free
to move through out the volume of the metal.
2. These free electrons move in random directions and make collisions with either
positive ions fixed in the lattice or other free electrons. All the collisions are
elastic i.e., there is no loss of energy.
3. The movements of free electrons obey the laws of the classical kinetic theory of
gases.
4. The velocities of free electrons in a metal obey the classical Maxwell-Boltzmann
law of distribution of velocities.
5. The free electrons move in a completely uniform potential field due to ions fixed
in the lattice.
6. When an electric field is applied to the metal, the free electrons are accelerated in
the direction opposite to the direction of applied electric field (towards positive
terminal of the source). The average velocity acquired by an electron in the
presence of electric field is known as ‘drift velocity (vd)’ and the average time
taken by electron to attain steady state velocity from zero velocity is called
‘relaxation time (τr)’.
7. In the absence of the electric field, the distance traveled between two successive
collisions is called ‘mean free path (λ)’ and the time taken by an electron between
two successive collisions is known as ‘collision time (τc)’. The average velocity
of free electrons is called ‘root mean square velocity, (vrms)’ or thermal velocity of
electrons.
8. In this model, it is assumed that collision time (τc) is equal to relaxation time (τr)
and the thermal velocity (vrms) is equal to drift velocity (vd).

Faculty: S.Singaravadivelu, Assistant Professor, Lecture Notes-UT-I /1

Department of Physics, SSNCE, Kalavakkam, Engineering Physics-II (182202)
Unit-I, Conducting Materials Page Number 2

DERIVATION OF AN EXPRESSION FOR ELECTRICAL CONDUCTIVITY

Elemental volume of length ‘dl’.

Free electron

Let us consider a metallic wire connected to a dc power supply. The metallic wire
contains a large no. of free electrons. We consider only one free electron.
Let ‘m’ be the mass of the electron;
‘-e’ be the charge associated with the electron;
‘E’ be the applied electric field;
‘a’ be the acceleration acquired by the electron.
The force acting on the electron due to the electric field (F) = -eE
The rate of change of momentum of electron = m (dv/dt)
According to Newton’s second law of motion -eE = m (dv/dt) --- (1)

(or) dv = ( -eE /m )dt Here ‘v’ is drift velocity.

Integrating on both sides
∫ dv = (-eE / m) ∫ dt

v = (-eE / m) t + C1

C1 – Integral constant
To find C1, we apply the boundary condition, when t=0, v = 0.

Therefore v = (-eE / m) t --- (2)

Expression for current density ‘j’

Let ‘A’ be the area of cross section;
‘n’ be the concentration of free electrons;
‘dl’ be the length of the elemental volume
Total no. of charges present in the elemental volume (dq) = -en A.dl
Rate of flow of charges (dq / dt) = -enA (dl/dt)
I = -enA v
J= (I/ A) = -en v ---- (2A)
J = -en(-e E /m) t
J = (ne2E /m) t --- (3)

Faculty: S.Singaravadivelu, Assistant Professor, Lecture Notes-UT-I /1

Department of Physics, SSNCE, Kalavakkam, Engineering Physics-II (182202)
Unit-I, Conducting Materials Page Number 3
According to the equation (3), the current density ‘J’ must increase with time‘t’.
Practically the current density becomes steady. Also, the equation (2) indicates that
the value of drift velocity must increase with time. It is not happening so. The
derivation starts with the assumption that the electrons move freely in the solid like in
an ideal gas and the force applied to the electron by the electric field leads to an
acceleration according to equation (1). Since this assumption led to a wrong result
there had been a further assumption that the electrons bump into obstacles once in a
while which limits their free flight. This establishes an average or drift velocity ‘Vd’.

Vd

While the free electrons move towards the positive terminal in the presence of the
applied electric field they make collisions with the positive ion core and other
electrons and consequently they loose their kinetic energy. But they are able to gain
kinetic energy from the electric field and attain a steady state velocity. The average
steady state velocity is called drift velocity ‘Vd’. The average time taken by electrons
to attain this steady state velocity after collision is called relaxation time (τr) .

Therefore the rate of decrease of momentum

of the electron because of collision = m (Vd – 0)
τr
This is similar to frictional force experienced by a body during motion on a surface. It
is obvious that the applied force must overcome and then set it into motion.

Thus –eE = m (Vd) + m. (dVd / dt) (4)

τr
Multiplying by (τr / m) on both sides,

(–eEτr)/ m = Vd + (1/ τr ) (dVd / dt)

(or) (1/ τr ) (dVd / dt) = – (eEτr)/ m + Vd

dVd = – dt
(eEτr)/ m + Vd τr

Integrating on both sides,

dVd - dt
∫ (eEτ r / m + vd )
=∫
τr

Faculty: S.Singaravadivelu, Assistant Professor, Lecture Notes-UT-I /1

Department of Physics, SSNCE, Kalavakkam, Engineering Physics-II (182202)
Unit-I, Conducting Materials Page Number 4
log (eEτr)/ m + Vd = (-t/ τr) + C1, where C1 is an integral constant.

(or)
(eEτr)/ m+ Vd = exp ((-t/ τr) + C1)
= C2 exp (-t/ τr) (5)
where C2 = exp(C1) , another constant
Applying boundary condition that when t=0 , Vd = 0
We get C2 = (eEτr)/ m
Substituting for C2 in equation (5),
(eEτr)/ m+ Vd = (eEτr)/ m exp (-t/ τr)

Vd = (eEτr)/ m exp (-t/ τr) - 1 (6)

Substituting (6) in equation (2A)

J = -en (eEτr)/ m exp (-t/ τr) - 1

J = (ne2Eτr)/ m 1- exp (-t/ τr) (7)

The equation (7) indicates that the current density grows exponentially with time
and becomes steady after the relaxation time. The order of the value of the relaxation
time is 10-14 seconds. Therefore the steady current flows after 10-14 seconds.The
stesdy state ‘J’ is given by J = (ne2Eτr)/ m . For a given material, at particular
temperature ‘n’ and τr are constants.
Therefore J = σ. E (8) where σ = (ne2τr)/ m (9)
i.e., the current density is directly proportional to ‘E’.
The constant ‘σ’ is called conductivity of the material.
The equation (8) is called microscopic form of ohm’s law.
The steady drift velocity is given by Vd = -(eEτr)/ m . (10)
The negative sign indicates that the current conduction is due to electrons.
Drift velocity per unit electric field is called mobility of the charge carrier (µe).
µe) =(Vd /E) = -(eττr)/ m
(µ (11)

DERIVATION OF AN EXPRESSION FOR THERMAL CONDUCTIVITY OF

METALS

In metals heat energy is carried from hot point to cold point by free
electrons. We consider a cylindrical metallic wire having unit area of cross section and
length ‘2λ’. Let ‘n’ be the no. of free electrons per unit volume. Then total no of free
electrons present in the length of wire ‘λ’ is 1. λ.n.

Faculty: S.Singaravadivelu, Assistant Professor, Lecture Notes-UT-I /1

Department of Physics, SSNCE, Kalavakkam, Engineering Physics-II (182202)
Unit-I, Conducting Materials Page Number 5

A C B
Area of cross section = 1m2

T1 T2 . T1> T2
λ λ

Let ‘v’ be the thermal velocity of electrons. We fix the origin of the co ordinate
axes at ‘C’. +Vy
+Vz

- Vx +Vx

-Vz
- Vy

The electrons can have velocity components primarily along six directions +Vx,
-Vx, +Vy, - Vy, +Vz and -Vz .The probability that an electron can have velocity
component in +X axis is (1/6). The end ‘A’ is at temperature T1 and the end ‘B’ is at
temperature ‘T2’. T1 is greater than T2.The electrons in the region ‘AC’ move to the
region ‘CB’ and the average energy carried by each electron is (3/2) KB T1.Similarly
the electrons in the region CB can move to the region AC and the average energy
carried by each electron is (3/2) KB T2 .

The number of electrons crossing the area at C per second = (1/6) (1. λ. n )/1sec
= (1/6) nv .
The heat energy transferred across‘C’per second from ‘A’ to ‘B’=(1/6) nv (3/2) KB T1.
Similarly
The heat energy transferred across‘C’per second from ‘B’ to ‘A’=(1/6) nv (3/2) KB T2.

The resultant heat energy transferred

across‘C’per second from ‘A’ to ‘B’ = (1/6) nv (3/2) KB (T1- T2)

Temperature gradient = (T1- T2) / 2λ.

Coefficient of thermal conductivity (K)= Amount of heat energy transferred across

a unit area of cross section in one second

Temperature gradient

Faculty: S.Singaravadivelu, Assistant Professor, Lecture Notes-UT-I /1

 Department of Physics, SSNCE, Kalavakkam, Engineering Physics-II (182202)
Unit-I, Conducting Materials Page Number 6

(1/6) nv (3/2) K B (T1 - T2 )

K=
(T1 - T2 ) / 2λ

nv K Bλ
K=
2

Wiedmann – Franz law

When the temperature is not too low, the ratio of the thermal conductivity to the
electrical conductivity of a metal is directly proportional to the absolute temperature,

i.e., (K/ σ) ∝ T

(K/σT) = constant The constant is known as Lorentz number (L).

Proof:
2
K nv K B λ m m v K B v τ r m v 2 K B 3 K B T
= = = =
σ 2ne 2τ r 2e 2 τ r 2e 2 2e 2

Substitutrions done in the above equaion:

1 2 3
λ=vτr , mv = KBT
2 2

2
KB 3 KB
= L where L = = 1.11 x 10-8 W Ω K-2
σT 2 e2

The experimental value of the Lorentz number is 2.44 x 10-8 W Ω K-2.

From this we observe that the theoretical value differs from the experimenal value.
This discrepancy is due to the wrong assumption of the classical theory that all free
electrons take part in thermal conduction process.According to Quantum theory the
electrons which are near to the Fermi energy level (the closeness of electrons to the
Fermi level depends on the thermal energy available to the free electrons)alone can
take part in thermal coduction process. According to this theory, the thermal
conductivity is given by

Faculty: S.Singaravadivelu, Assistant Professor, Lecture Notes-UT-I /1

Department of Physics, SSNCE, Kalavakkam, Engineering Physics-II (182202)
Unit-I, Conducting Materials Page Number 7
2
nπ 2 KB T τ r
K=
3m

2 2
K nπ 2 KB T τ r m π 2 KB
L= = x 2 =
σT 3m ne τr T 3 e2
Now the value of ‘L’ is 2.44x 10-8 W Ω K-2. This theoretical value is in
good agreement with the observed experimental value of ‘L’. The Wiedmann – Franz
law does not hold good at very low temperatures.

Success of Classical free electron theory

1.It verifies Ohm’s law.

2.It explains electrical and thermal conductivities of metals.

3.It derives Wiedmann-Franz law.

4.It explains optical properties of metals.

Drawbacks of Classical free electron theory

1. The phenomenon such as Photoelectric effect, Compton effect and the Black body
radiation could not be explained by Classical free electron theory.
2. According to the Classical free electron theory, the value of specific heat of
metals is given by 4.5R , where R is universal gas constant where as the
experimental value is nearly equal to (3/2)R .Also, according to this theory the
value of electronic specific heat is equal to 3R while the actual value is about
0.01R only.
3. Though (K /σ T) is a constant according to the Classical free electron theory,
It is not a constant at low temperature.
4. Ferromagnetism could not be explained by this theory.The theoretical value of
of paramagnetic susceptibility is greater than the experimental value.

Important things to remember

1. In the derivation of electrical conductivity, we must understand that the externally
applied electric field is partially used (i) to overcome frictional like force acting
due to collisions of free electrons with lattice ion core and among themselves and
(ii) to impart kinetic energy on the free electrons and establish their drift towards
the positive terminal.
2. In this model, it is assumed that collision time (τc) is equal to relaxation time (τr)
and the thermal velocity (vrms) is equal to drift velocity (vd).
3. In the derivation of thermal conductivity, the probability that an electron can have
the velocity component along the length of the conductor (along which the
thermal conductivity is to be determined) is (1/6).

Faculty: S.Singaravadivelu, Assistant Professor, Lecture Notes-UT-I /1