THERMAL CONDUCTIVITY AND THE MECHANISM OF

ENERGY TRANSPORT

FOURIER'S LAW OF HEAT CONDUCTION

Consider a slab of solid material of area A located between two large parallel plates a distance y
apart. We imagine that initially (for time t < 0) the solid material is at a temperature to
throughout. At t 0 the lower plate is suddenly brought to a slightly higher temperature Tx and
maintained at that temperature. As time proceeds, the temperature profile in the slab changes,
and ultimately a linear steady-state temperature distribution is attained as shown in Fig. When
this steady-state condition has been reached, a constant rate of heat flow Q through the slab is
required to maintain the temperature difference T = 1 T0. It is found then that for sufficiently
small values of AT the following relation holds:

Q T
=k
A Y
(1)
That is, the rate of heat flow per unit area is proportional to the temperature decrease over the
distance . The constant of proportionality is the thermal conductivity of the slab. Equation (1)
is also valid if a liquid or gas is placed between the two plates, provided that suitable precautions
are taken to eliminate convection and radiation.

As the slab thickness approaches zero. The local rate of heat flow per unit area (heat flux) in the
positive direction is designated by qy.

dT
qy k dy

(2)

This equation is the one-dimensional form of Fourier's law of heat conduction. It states that the
heat flux by conduction is proportional to the temperature gradient, or, to put it pictorially, "heat
slides downhill on the temperature versus distance graph.

In an isotropic medium in which the temperature varies in all three directions we can write eq.
for each of the coordinate direction.

T T T
qx k x qy k y qz k z

(3)

This three relations are the compounds of the single vector equation,

q = -kT (4)
which is the three-dimensional form of Fourier's law.

TEMPERATURE AND PRESSURE DEPENDENCE OF THERMAL

CONDUCTIVITY

In figure, a plot is made of the reduced thermal conductivity kr = k/kr, which is the thermal
conductivity at pressure p and temperature T divided by the thermal conductivity at the critical
point. This quantity is plotted as a function of the reduced temperature Tr = T/Tc and the reduced
pressure pr = p/pc. Figure is based on a limited amount of experimental data for monatomic
substances, but may be used for rough estimates for polyatomic materials.

It can be seen that the thermal conductivity of a gas approaches a limiting function of T at low
pressures; for most gases this limit is reached at about 1 atm pressure. The thermal conductivities
of gases at low density increase with increasing temperature, whereas the thermal conductivities
of most liquids decrease with increasing temperature. The correlation is less reliable in the liquid
region; polar or associated liquids, such as water, may exhibit a maximum in the curve of k
versus T. The main virtue of the corresponding-states chart is that one gets a global view of the
behavior of the thermal conductivity of gases and liquids.
THEORY OF THERMAL CONDUCTIVITY OF GASES AT LOW DENSITY
Thermal Conductivity: A measure of the ability of a material to conduct heat.
The thermal conductivities of dilute monatomic gases are well understood and can be described
by the kinetic theory of gases at low density.
We use the model of rigid, non-attracting spheres of mass m and diameter d. The gas as a whole
is at rest (v = 0), but the molecular motions must be accounted for.

= 8 T
m = mean molecular speed

(5)
1
Z= n = wall collision frequency per unit area
4
(6)
1
= 2 d n = mean free path

(7)
The molecules reaching any plane in the gas have had, on an average, their last collision at a
distance a from the plane, where

2
a= 3
(8)
In these equations,
= Boltzmann constant

n = no. of molecule per unit volume

m = mass of a molecule
The only form of energy that can be exchanged in a collision between two smooth rigid spheres
is translational energy. The mean translational energy per molecule under equilibrium conditions
is
 1 2
m2 = KT
2 3
(9)

To determine the thermal conductivity, we examine the behavior of the gas under a temperature
gradient dT/dy. We assume that Equation 1 to 5 remain valid in this non-equilibrium situation,
1 2
except that 2 m in Equation 5 is taken as the average kinetic energy for molecules that had

their last collision in a region of temperature T.

The heat flux qy across any plane of constant is found by summing the kinetic energies of the
molecules that cross the plane per unit time in the positive direction and subtracting the kinetic
energies of the equal number that cross in the negative direction:
2
1 2 1
qy = Z( 2 m y-a - 2
m y+a )

1
= 2 Z ( T y-a - T y+a )

(10)

Last equation is based on the assumption that all molecules have velocities representative of the
region of their last collision and that the temperature profile T(y) is linear for a distance of
several mean free paths.
 2 dT
T = T
y-a y 3 dy
(11)

2 dT
T = T
y+a y + 3 dy
(12)

By combining last three equations we get,

1 dT
qy = - n
2 dy
(13)

This corresponds to Fourier's law of heat conduction with the thermal conductivity given by

1 1
k= n = v (monoatomic gas)
2 3
(14)
2
in which = nm is the gas density, & v = /m .
3
Substitution of the expression for and from equation (5) and (6) then gives

m T / 2 m T
k= d
2
m = 3 d
2 v (monatomic gas)

(15)
which is the thermal conductivity of a dilute gas composed of rigid spheres of
diameter d. This equation predicts that is independent of pressure.

The Chapman-Enskog formula for the conductivity of a monatomic gas at low density and
temperature T is

k=
25 m T

32 2 k v or k= 1.9891 10-4
2
T
M
k
(monatomic

gas) (16)

cal
In the second form of this equation, [=] Cal k = cmsK , [=] , [=] A, and

the "collision integral" for thermal conductivity, k , is identical to that for viscosity, .

Values of k = as a function of the dimensionless temperature /.

Relations between k and is

15 R 5
k= = (monatomic gas)
4 M 2
(17)

5
k = ( p+ 4 v (polyatomic gas)

(18)

p
p
Pr = = 5 (polyatomic gas)
k p+ R
4
(19)

The thermal conductivities for gas mixtures at low density may be estimated by a
method analogous to that previously given for viscosity.
 N
xa ka

Kmix = a=1 x (20)

Where the xa is the mole fractions, and the ka are the thermal conductivities of the pure
chemical species. The coefficients are identical to those appearing in the viscosity equation.
THERMAL CONDUCTIVITY OF LIQUIDS

A very simple theory of energy transport in pure liquids. He assumed that the molecules are
arranged in a cubic lattice, with a center o- center spacing given by (V/N)^1/3, in which V/N is
the volume per molecule. He further assumed energy to be transferred from one lattice plane to
the next at the sonic velocity vs for the given fluid.

1
k= v = v |u |a
3 y

(21)

The heat capacity at constant volume of a monatomic liquid is about the same as for a solid at
high temperature, which is given by the JDulong and Petit formula4 v = 3(/). The mean
molecular speed in the direction, |uy| is replaced by the sonic velocity vs. the distance a that the
energy travels between two successive collisions is taken to be the lattice spacing (V/N) 1/3.
Making these substitutions

N
k = 3( V )2/3 s

(22)
which is Bridgman's equation

For polyatomic liquids, but the numerical coefficient is somewhat too high. Better agreement is
obtained if the coefficient is changed to 2.8.

The velocity of low frequency sound vs is given by relation

s = Cp p
( )
Cv T
(23)

p
The quantity ( )T may be obtained from isothermal compressibility measurements

Or from an equation of state, and (Cp/Cv) is very nearly unity for liquids, except near the
Critical point.
THERMAL CONDUCTIVITY OF SOLIDS

Thermal conductivity of solid have to be established experimentally because they depends on

man factors that are difficult to predict. In porous solids for ex. K is strongly depended on the
void fraction, the pore size and the fluid contained in the pores; in crystalline water phase the
phase and the crystalline size are important; in amorphous; solids the degree of molecular
orientation has considerable effect.
In general, metals are better heat conductors than nonmetals and crystalline materials conduct
heat more readily then amorphous materials. Dry porous solids are very poor heat conductors
and are therefore excellent for thermal insulations. For pure metals K increases with increasing
temperature while for nonmetals it increases with decreasing temperature.
For pure metals K and electrical conductivity, ke are related approximately,
k
=L=constant
ke

This is the Wiedemann-Franz-Lorenz equation; this equation can also be explained theoretically.
The "Lorenz number" L is about 22 to 29 *10-9 volt2/K2 for pure metals at 0 C.
SOLVED EXAMPLE

1. Compute the thermal conductivity of Ne at 1 atm and 373.2K.

SOLUTION:-

Lennard-Jones constants for Neon are cr = 2.789 A and / = 35.7K, and its molecular
weight M is 20.183.

Then, at 373.2K, we have / = 373.2/35.7 = 10.45.

We find that k = = 0.821.

Substitution into Eq. 12 gives

k= (1.9891 10-4)
2
T
M
k

= (1.9891 10-4)
373.2
20.183
2.789 2 0.821

cal
=1.338 10-4 cmsK

cal
A measured value of 1.35 10-4 cmsK has been reported at 1 atm and 373.2K

2. Estimate the thermal conductivity of molecular oxygen at 300K and low pressure.

SOLUTION:-

The molecular weight of oxygen is 32; its molar heat capacity Cp at 300 K and low
cal
pressure is 7.019 g . moleK .

Lennard-Jones constants for Oxygen are = 3.433 A and / = 113 K, and its
molecular.

= 1.074
 MT
= (2.6693 x 10-5) 2
u

32 X 300
= (2.6693 10-5) 3.433 2 1.074

g
= 2.065 x 10-5 cms

Then, the Eucken approximation to the thermal conductivity is

5
k = ( p+ 4 v ( M )

= (7.019 + 2.484)((2.065 x 10-4)/(32))

cal
= 6.14 x 10-5 cmsK