Chapter 12

Elementary kinetic theory

of transport processes

Aman. W
 Introduction
In the previous chapters our concern has been almost
exclusively with equilibrium situations.
General statistical arguments were quite sufficient to treat
problems of this sort, and there was no need to investigate in
detail the interaction processes which bring about the
equilibrium.
we can derive the specific heat, and many other gas properties
using an equilibrium approach
Results of Kinetic Theory: KE of individual particles is related
to the temperature of the gas:
mv2 = 3/2 kT
Where v is the average velocity.
 Equilibrium Distributions for a Gas
At equilibrium, we can use Maxwell-Boltzmann statistics to determine the
gas distribution for the relevant properties

m 2
3
m (v2 + v2 + v2 )
f (v ) =
velocity (Gaussian) x y z
exp -
2 p k BT 2kBT
3
4 m 2 2 mv 2
f ( v) = v exp -
speed (Maxwellian)
p 2kBT 2kBT
8kBT
v=
pm

e e
f (e ) = 2 exp -
2 ( kB T )
energy (Maxwellian)
k BT
3

3
e = k BT
2
 However, many problems of great physical interest deal with non
quilibrium situations.
For example,
the two ends of a copper rod are maintained at different
temperatures.
This is not an equilibrium situation, since the entire bar would not
be at the same temperature.
Then, energy in the form of heat flows through the bar from
the high to the low temperature end,
the rate of this energy transfer being measured by the "thermal
conductivity of the copper bar
A calculation of the coefficient of thermal conductivity thus requires
a more detailed consideration of the non quilibrium processes
whereby energy is transported from one end of the bar to the other
 Contents

Introduction to Non equlibrum Dynamics

Collisions Time
Basics of Transport
Diffusion --- particle number
Energy ---- Thermal conduction and
Momentum --- Viscosity
Diffusion
Random walk
The Diffusion Equation
 Phonons are characterized by their
Energy, wavelength (wave vector)
polarization (direction)
branch (optical/acoustic), acoustic phonons are the primary
thermal energy carriers
Phonons are quantized lattice vibrations
store and transport thermal energy
primary energy carriers in insulators and semi-conductors
Phonons have a statistical occupation (Bose-Einstein), quantized
(discrete) energy, and only limited numbers at each energy level
We can treat phonons as particles and therefore determine the thermal
conductivity based on kinetic theory, we can derive the specific heat!
 Electrons are particles with quantized energy states
store and transport thermal and electrical energy
primary energy carriers in metals
usually approximate their behavior using the Free Electron
Model
Energy, wavelength (wave vector)
Electrons have a statistical occupation (Fermi-Dirac),
quantized (discrete) energy, and only limited numbers at
each energy level (density of states)
we can derive the specific heat!
We can treat electrons as particles and therefore determine
the thermal conductivity based on kinetic theory
 Introduction to non equlibrum

Unlike both classical thermo and statistical mechanics, kinetic

theory may be used to describe non-equilibrium situations.
Kinetic theory has been particularly useful in describing the
properties of dilute gases.We can use non-equilibrium kinetic
theory to determine
the thermal conductivity,
viscosity, and
diffusivity of gases
It gives a deeper insight into concepts such as
pressure, internal energy and
specific heat
 Non equilibrium-collsion

In gas systems, gas molecules interact with each other through

collisions.
If such a gas is initially not in an equilibrium situation, these
collisions are also responsible for bringing about the ultimate
equilibrium situation where a Maxwell-Boltzman velocity
distribution prevails.
We shall discuss the case of a gas which is dilute. i.e
Each molecule spends a relatively large fraction of its time
at distances far from other molecules so that it does not
interact with them.
In short, the time between collisions is much greater than
the time involved in a collision.
 Triple or more collisions occur very rarely compared to two-
particle collisions.
Thus the analysis of collisions can be reduced to the relatively
simply mechanical problem of only
two interacting particles.
The behavior of a molecule between collisions can then be
described adequately by
the motion of a wave packet or
classical particle trajectory, even though a quantum-mechanical
calculation may be necessary to derive the scattering cross
section describing a collision between two molecules.
 Collisions Time

Let's start by considering N molecules in a gas of volume V.

Consider a molecule with velocity v. Let
P(t) = the probability that such a molecule survives a time t
without suffering a collision.
P(0) = 1, since a molecule has no chance of colliding in a
time t0,
On the other hand, P(t) decreases as the time t increases
Finally
P(t) 0 at t
 The net result is that a plot of P(t) versus t must have the shape
indicated in Fig.
 To describe the collisions, let define
dt = the probability that a molecule suffers a
collision between time t and t + dt.

The quantity is thus the probability per unit time that a

molecule suffers a collision, or the "collision rate.
Knowing the collision probability, , it is possible to
calculate the survival probability P(t).
How?
This can be done by as follows
 [the probability that a molecule survives a time t + dt without
suffering a collision] =
[the probability that this molecule survives a time t without
suffering a collision] X [the probability that it does not suffer a
collision in the subsequent time interval between t and t + dt]
In symbols, this statement becomes
+ = () 1

=

To fix the normalization so that

= 1
0
which guarantees that no particle lasts forever without undergoing a
collision
 When we solve for
=
Let = be the mean time between collisions. But this is
exactly the quantity that we called the relaxation time.
we can compute the average time between collisions.

1
= =
0
Hence, we have got that

1/ is the collision rate().

 The Mean Free Path

The average distance

traveled by a molecule
between two successive
collisions is called the
"mean free path, , of the
molecule.
we can simply gas collisions
using a hard-sphere, binary
collision approach (billiard
balls)
One has thus got
=
 Basics of Transport

We now turn to the question of how things move.

To understand how certain macroscopic properties move when
out of equilibrium.
It is important to know how much time it takes for a system to
approach an equilibrium state.
A system is not in equilibrium when the macroscopic
parameters (T, P, etc.) are not constant throughout the system.
To approach equilibrium, these non-uniformities have to be
ironed out through the transport
What kind of transport?
 Basics of Transport
energy, ----------- Thermal conduction
momentum,----------- Viscosity and
mass ------- Diffusion
from one part of the system to another.
The mechanism of transport is to estimate the characteristic
rates of approaching equilibrium and thus to impose
limitations on the rates of quasi-static processes.
Processes in which these quantities change over time are
usually referred to as transport.

n(x,t)
T(x,t)
x
 Diffusion

Drop a blob of ink into a glass of water.

How does it spread?
More generally, we are interested in the motion of a particular
kind of particle such as
one with a nice color, or
smell
As it makes its way through a generic background of liquid or
gas
Thus the flow of randomly moving particles caused by
variations of the concentration of particles.--- Diffusion
 Example: a mixture of two gases/liquid, the total concentration
n = n1+n2 = const over the volume (P = const).

n1 J n2
J

The kind of motion can explained by

random walk
 Random Walk-1-dimensional

Consider a lattice which, for now, we take to be one dimensional.

Let N steps of equal length be taken along a x-dimension

The spacing between the lattice sites is set by the mean free path, ,
and after a time, ,
the particle jumps either left or right.
The direction of the jump is entirely random:
of the time it goes left, and
right.
This model is known as a random walk.
 The particle starts at the origin and we want to know the
probability P(x, t) that it sits at x = ml at time t = N .
To get to x = ml the particle must have made
1/2 (N +m) forward jumps and
1/2 (N-m) backwards jumps.
The probability is just the number of different ways
2 2 2
, = 2

The probability distribution of the particle is an ever-spreading
Gaussian ensemble.
 The mean displacement is
simply
<x>=0,
reflecting the fact that the
particle is equally likely to
travel forwards as
backwards.
The variance is
2

2 =

 The root-mean-square (rms)
distance travelled by the
particle grows

2 ~

This is characteristic
behavior of random walks.
 The Diffusion Equation
We can recast the above discussion in terms of a differential
equation for the density of particles, n = N/V.
The density is not a constant(out of equilibrium). It is, in
general, a function of time and space.
We expect any gradient, n, in the density of particles to lead
to a flow, from the high density region to the low.
We'll again restrict first to the case of one-dimension. Consider
the density at some fixed time:
n = n(x, t).

n(x,t)
x
 The Diffusion Equation

To derive an expression
for the density at the point
x a short time t later
Any particle which is at x
at time t +t must have
been sitting at some other
position x-x at time t.
Here x should be viewed
as a random variable since
some move one way some
the other.
 This means that we can write an expression for the density at time t
+ t as an average over all the different x,

+ , = ,

Taylor expanding the right-hand side,

1 2 2
+ . = , +
2 2
The term with the first order derivative vanishes because on average
particles are equally likely to go either way, meaning = 0 .
Then
2
= 2

 Where the diffusion constant is
2
D=
2
We expect this to be related to our two quantities, the mean
free path and scattering time .
2
~

The solution which corresponds to an initial condition that all
particles are at x =0 at t =0 is an ever-spreading Gaussian,
1 2
, = 4
4
 we again have the result
2 = 2
It is simple to extend the derivation above to three dimensions.
It becomes as
2 2
= 2 2 2 = 2
( + + )

This is also known as Fick's law.

 Viscosity-Momentum Transfer

Viscosity is a form of internal friction experienced by a fluid. It

can be measured by placing a fluid between two plates, a
distance d apart in the z direction.
Holding the lower plate stationary, the top plate is moved at a
constant speed, u, in the x direction.
But the fluid pushes back.

Laminar flow of a gas

(fluid) between two
surfaces moving with
respect to each other.
 If you want to keep the
plate moving at a constant
speed, you have to apply a
force F
Near the upper plate, a
friction force causes the
fluid to be dragged along
with the same speed u.
However, near the lower
plate, the fluid remains
stationary.
 This sets up a velocity gradient, ux(z), with
ux(d) = u and
ux(0) = 0.
Drag transfer of the momentum in the direction
perpendicular to velocity.
px A u x, top ux, bottom
Fx
t z
Fx d ux u
=
A z d
Fx the viscous drag force, - the coefficient of viscosity and
Fx/A shear stress
 where the second equality holds for small distances d. The
coefficient of proportionality, , is called the viscosity
The viscosity after some algebra becomes
1
= ()
3
 Thermal conductivity: Particle Approach

Phonons and electrons (and photons) possess wave-like

characteristics
to track waves we need to know amplitude, phase, direction very
difficult!
We already treat gases as particles and we also like to treat
phonons, electrons, and photons as particles as well weve
already applied kinetic theory to derive thermal conductivity!

free electron gas

phonon gas

gas gas
 Thermal conductivity
A static flow of energy from a hot object to a cold one. (At what rate
the internal energy is transferred between two systems with T1 T2 or
between parts of a non-equilibrium system (if one can introduce Ti ?)

area A

T1 T2

The temperature distribution in this formulation is time-independent, and

we need to calculate the flux of thermal energy JU due to the heat
conduction (diffusion/intermixing of particles with different energies,
interactions between the particles that vibrate but do not move
translationally). T
QU = K th
x
 Thermal conductivity

In general, the energy transport due to molecular

motion/viberation is described by the equation of heat
conduction:
T 1 QU K th 2T
= =
t C x C x 2
T
QU = K th
x

Thus, in principle, if you know the initial conditions, e.g.

T(x, t=t0), you can describe the process by solving the
equation.
Often, you are asked to consider a different situation:
 Mechanisms of heat conduction

Heat is transferred by phonons (lattice vibration waves) and

electrons.
The thermal conductivity of a material is defined by combined
contribution of these two mechanisms:

= +
where
the lattice thermal conductivities. and
electronic thermal conductivities.
 Lattice conductivity: Transfer of thermal energy phonons
Electron conductivity: Free (conduction band) electrons
equilibrate with lattice vibrations in hot regions, migrate to
colder regions and transfer a part of their thermal energy
back to the lattice by scattering on phonons.
The electron contribution is dominant in metals and absent in
insulators.
Summary
 Congra!

Wishing U all the best in your Future Carrier