9.

Kinetic Theory
Thermodynamics empirical description of matter based on experimental observations
(macroscopic)
All phenomena described in thermodynamics can be explained by considering the behaviours of
the molecules at microscopic scale
This can be done by 2 approaches :
(1) Consider motion of molecules based on law of mechanics
- Kinetic theory
(2) Consider the probability of the behaviour of group of large number of molecules
- Statistical thermodynamic
From kinetic theory

Statistical thermodynamic

equation of state, internal energy, specific heat

entropy

At microscopic scale, some "classical" law of physics may not be obeyed

Quantum Mechanical approach

9.1

Basic assumptions of kinetic theory

(1)

A macroscopic volume of a gas contains a very large number of molecules

1 mole :

6.03 1023 molecules (Avogradro number)

(2)

The distance between any two molecules in the gas is much larger than their individual size

(3)

Each molecule will not experience any force exerted by other molecules except when a
collision occurs.

(4)

The molecules are assumed to be hard spheres and the collisions between the molecules are
perfectly elastic
conservation of momentum and energy

(5)

The molecules are distributed uniformly inside the volume of the gas
-

(6)

number density of the molecules

n=

N
V

and n =

N
for any element V
V

The directions of the motion of molecules are isotropic (all directions are equally probable)

Assumption (6) may lead us to the following :

If

N : total number of possible direction

Each of these direction can be represented by a point on the surface of a sphere with
surface area of 4 r2

the number of directions between (r, , ) and (r, +d , +d ) is given by

A
N
N =
2
4r

(through A)

where

A = r sin r = r 2 sin

and

N
A t

is the flux of number of directions passing through A

Hence the number of molecules having velocity with direction between (r, , ) and (r, +d ,
+d ) is given by

N 2
N
r sin = (sin )
N =

4
4r 2

The number density of molecules having velocity with direction between (r, , ) and (r, +d ,
+d ) is given by

n
n = (sin )
4
If the number density of molecules having velocity between v and v+dv is nv
The number density of molecules having velocity with direction between (r, , ) and (r, +d ,
+d ) and with magnitude between v dan v+dv is given by

n
n v = v (sin )
4

Consider in a time t, distance travelled by particle with velocity v is r = v t ,

V = (A cos )(vt )

V
The number of molecules having velocity with direction between (r, , ) and (r, +d , +d ) and
with magnitude between v and v+dv is given by :
n
N v = nv V = v (sin )(A cos )(vt )
4

Hence, the flux of molecules passing through A :

n
v = v (v sin cos )
4

Total flux of molecules :

2 / 2

d v =

all v = 0 = 0

Define

v=

1
(vnv )
4 all v

N1v1 + N 2v2 + N 3v3 + L

N

Hence,

v=

1
(vN v )
N v

1
nv
4

or

v=

1
(vnv )
n v

which is the molecular flux

9.2 The equation of state for an ideal gas

Consider the collision of molecules at the wall of the container :

In the direction normal to the plane of the wall,

(momentum) = mvcos - (-mvcos ) = 2mvcos
Consider a unit area at the plane of the wall, it will be collided by v molecules per unit time
v (momentum) = rate of momentum transfer per unit area = pressure
Hence,

Pv = vnv sin cos (2mv cos )

2

= mv 2 n v sin cos 2

For molecules with velocity v and for all possible directions,

/2

Pv =

dPv =

= 0

1
mv 2 (nv )
3

For all possible velocities, P =

dPv =

v =

1
m v 2 (nv )
3 v

Define mean square velocity,

1
nm v 2
3

P=

or

PV =

But

3
1
kT = m v 2
2
2

Hence,

v 2N v (v 2nv )

=
=

1
Nm v 2
3

PV = NkT

v2 =

3kT
m

or

PV = nRT

which is the equation of state for ideal gas.

where

k=

R
NA

9.3 Principle of equipartition of energy

For a system with 2 components at thermodynamic equilibrium, we may write

Also,

P1V = N1kT =

1
N1m1 v12
3

for component 1

P2V = N 2kT =

1
N 2m2 v22
3

for component 2

3
1
kT = m1 v12
2
2
3
1
kT = m2 v22
2
2

The experssion
velocity v

1
m v 2 is the average kinetic energy for particles with mass m moving with
2

Consider Cartesian coordinate

We can write :

(x, y, z), v : (vx , vy , vz )

1
1
kT = m v 2x
2
2
1
1
kT = m v 2y
2
2
1
1
kT = m v z2
2
2

This means : the kinetic energy of the particles is divided into 3 parts according to its 3 degree of
freedom
Each degree of freedom

1
kT
2

For monoatomic gas,

3 degree of freedom (linear)

E=

3
kT
2

For molecular gas,

3 degree of freedom for linear motion

2 degree of freedom for rotational motion
2 degree of freedom for vibrational motion
E=

7
kT
2

In general, we can write E =

f
kT
2

where f is the degree of freedom. Each degree of freedom represents an equal partition of the
1
kinetic energy, which is kT
2
Other types of degree of freedon include excitation, ionization etc which involve transfer of
energy into the internal energy of the particles

9.4 Specific heat capacity

Consider 2 states a and b. We can write
Ua - Ub = W (adiabatic)
Write

U=

f
f
NkT = nRT ,
2
2

f
u
cv =
= R
T v 2

c P = cv + R =

c
f +2
= P =
cv
f

f +2
R
2

or

u=

f
RT
2

For solid system, since the molecules are closely position, it is required to consider the effect of
potential energy asssociated with its motion in addition to kinetic energy

1
1

Hence each degree of freedom, the energy partition is kT kT + kT

2
2
This means
u = fRT = 3 RT
and

cv = 3 R

9.5 van der Waals equation of state

Real gas effect 2 possible corrections to ideal gas assumption
Correction 1:
Inside volume V, if the space occupied by all the other particles is b, then the space that can be
occupied by the particle is (V b).
Molecule hard sphere of diameter d
Closest distance between 2 molecules is d
Space occupied by 2 molecules can be taken to be

4
d3
3

Hence, the total space occupied by all N molecules is

1
4
2
2
N d 3 = nN A d 3 = nb b = N A d 3
3
2
3
3

Correction 2 : Effect of intermolecular force

Force of attraction between molecules (gravitational force)
Inside the gas, the forces experienced by a molecule from all direction are the same
there is no net force in any direction
However, this is not true for molecules near to the boundary (such as the wall of the container)
These molecules will collide at the wall to produce the effect of pressure
But because of the attractive force due to the rest of the molecules on these molecules, the
pressure produced by these collisions will be reduced
2

The reduction in the pressure is proportional to

2

or, we can write

a
N
P = A = 2 ,
v
v

N nN A N A

=
=
V
V
v

a = N A2

Hence, the equation of state of the gas can be written as

P=

RT
a
a

2 atau P + 2 (v b ) = RT
vb v
v

which is the van der Waals equation ot state

9.6

Collision between particles

n=

N
: number of particles per unit volume
V

d : diameter of particle
Number of particles that may collide with a particle after moving
through unit distance : nd 2
d 2 is used as a measure of the probability of collision ( Unit - area : cm2 )
nd 2 number of collision per unit distance
1/(nd 2) distance between two consecutive collision (mean free path)
Write = d 2, which is called the cross-section of collision
Mean free path (mfp), = 1/(n)
The probability for a particle to travel distance x without any collision:

Px = e x /

If the target particle being collided is also moving,

3 1
4 n

For particles with velocities following M-B distribution,

For the case of electrons colliding atoms or ions,

4
n

1 1
2 n

9.7 Viscosity
Consider gas or liquid in between 2 plates
The top plate is moving to the right by force F
Imagine that the gas or liquid is divided into thin sheet
The sheet next to the top plate will be moving almost at the same velocity as the top plate,
but the sheets further down will be moving with lower velocities
The bottom plate expereiences the same force F but in opposite direction
Particles are moving randomly (thermal)
possibility of particles jumping from one sheet to another
This results in the transfer of momentum between sheets, hence force exerted on each other
If

du
is the variation of velocity in the y-direction,
dy

F
du
,
=
A
dy

is the coefficient of viscosity, A is the surface area of the plate

Consider element A in the SS plane,

y = l cos
l : mean free path

Molecular flux at A :
n
v = v (v sin cos )
4

Flux in the -direction :

d v = 2 v n sin cos

all v = 0

1
= vn
4

Total flux :

The average distance travelled by particles after their last collision reaching the SS plane from above
or below the SS plane is given by
2

y=

l cos d
0

1
2

v nl sin cos 2 d
0
1
4

vn

2
= l
3

This means that on the average, particles make their last collision at distance of 2/3 l from the SS plane
before they finally reach the plane
Velocity:

2 du
u = uo + l
3 dy

Momentum

2 du
mu = m uo + l
3 dy

Hence, the total momentum per unit time per unit area carried by the particles passing through surface
SS from above or below the plane is
r

1
2 du
G = nm v uo + l
4
3 dy

and for the upwards direction }from below to above

r

1
2 du
G = nm v uo l
4
3 dy

Net momentum transferred per unit time per unit area :

r r
r
1
du F
du
=
G = G G = nm v l
3
dy A
dy

Hence,

1
3

= nm v l =

1 mv
3

9.8 Thermal conductivity

Now consider the plate on top to be not moving, but at temperature much higher than the
bottom plate

temperature gradient

dT
dy

( K m-1 )

Heat flow per unit cross-sectional area per unit time (heat flux) :
H =

dT
dy

( J m-2 s-1 )

is the heat conductivity ( J m-1 s-1 K-1 )

Actually, the heat flow can be expressed as
dT
1
H = nv c v* l
3
dy

c
c = v
NA
*
v

1
1 v c v*
*
= nv c v l =
3
3

9.9 Diffusion
Particles drift caused by density gradient
n = N/V , gradient :

dn
dy

Particle flux passing through unit cross-sectional area in unit time

= D

dn
dy

D is the diffusion coefficient

1
1 v
It can be shown that D = v l =
3
3 n