Phys.

12c 2015, Lecture Notes (Week 10)

Kinetic Theory
Equilibrium and non-equilbrium processes due to particle motion.
Consider velocity distributions and
transport phenomena
, non-equilibrium driven by gradient (density, temperature, voltage,. . . velocity)
Velocity and Speed Distributions
Consider classical, ideal, non-relativistic gas with constant , V, N
I. What is probability that particle of mass m has velocity component
between vx and vx + dvx ?
Recall: Classical probability for particle to occupy point in phase space and to have
momentum between px and px + dpx and py and py + dpy , . . . in volume between
x and x + dx, etc. is
Volume phase space element occupation probability
|
{z
} |
{z
}
Boltzmann factor eE/

dpx dpy dpz dx dy dz

Therefore

hR
P (px )dpx = Z

R R
V olume py

pz

E/

dxdydzdpy dpz dpx

dpx dpy dpz dxdydz eE/

{z
}
| V olume M om.
Normalization factor
R
Volume integration gives V ol dxdydz = V and divides out.
Get P (vx )dvx via change of variables vx = pmx and use
E = 12 m|~v |2 , |~v |2 = vx2 + vy2 + vz2
RR


m
dvy dvz e 2 (vy2 + vz2 )
mv 2
2x
R
R
R
e
P (vx )dvx =
dvx
m
dvx dvy dvz e 2 (vx2 + vy2 + vz2 )
q
pm
Now let ui = 2 vi , dvi = 2
m ui
Giving Gaussian integrals:
2
mvx
2 dvx

duy duz euy euz

( 2m )

e
P (vx )dvx =

3 R R R
2 2
u2x eu2y eu2z
dux duy duz e
m

with

x
dx =
e

and finally:
 m  12 mvx2
P (vx )dvx =
e 2 dvx
| 2 {z
}
Simple Gaussian
1

Note:
1.

R
hvx i = vx = P (vx )vx dvx
= 0 [since P (vx ) is symmetric]

2. vx2 = m [=(standard deviation of Gaussian)2 = 2 ] then energy per particle

hEi = 21 mhvx2 + vy2 + vz2 i = 23 (Ideal Gas Energy) since hvx2 i = hvy2 i = hvz2 i = m .
Gives Equipartition of Energy each translational degree of freedom gives
an energy of 12 per particle (Classical Result!)
, also true for other quadratic degrees of freedom in energy (e.g. x2 or p2 ).
(eg. harmonic oscillator, rotation ...) since more Gaussian integrals
II. Distribution of speeds (Maxwell-Boltzmann velocity distribution)
What is probability that particle has speed (v = |~v |) between
v and v + dv? Use spherical symmetry (all directions of v equally likely) then with
dvx dvy dvz = v 2 sin v dv dv dv
R R 2

P (v)dv =
=

mv 2
2

v 2 sin v dv dv dv
0
R R 2 R mv2
e 2 v 2 sin v dv dv dv
0 0
0
2
mv
2
2
0

( )
2
m

pm
v
where u = 2
R 2 u2
Note: 0 u e du =

v dv

3
2

R
0

eu2 u2 du

4 .

Also
R u2
R0 ue3 udu
2
u e du
0
R 4 u2
R0 u5 eu2 du
du
0 u e

Thus

= 21
= 21
= 3 8
=1

 m  32
2
mv
2
P (v)dv = 4
v 2 eMaxwellBoltzmann
2 }
| {z

Distribution dv

vmp

<v>
vrms

P( v)

Note:
1.
hvi =

R
0

= 4
=

vP (v)dv

3

R
m 2 2 2

8
m

1

2
2

= 1.60

1
2
m

v
3 u2

ue

du; u =

pm

2 v

2.
2

hv i =

R
0

v P (v)dv = 4

m
2

32

5
2 2
m

u4 eu du
{z
}

|0

3
8

= 3 m
then

vrms =

3
m

 12
= 1.73

  12

probable v that maximizes P (v).

2
mv 2
2 m
mv
2 + ()2ve 2
=
0
=
()v
(
)(2v)e
Set P
v q
2

1
2
2
vmp = m = 1.41 m

3. vmp vmost

2
vmp
=

2
m

Application of velocity distribution:

Effusion: consider a box of atoms at
with small hole in box (hole doesnt
perturb equilibrium inside of box).
Outside of box is vacuum.

Vacuum
What is flux of atoms leaving box?
The number of atoms/unit area/unit time=T ot
Crude estimate: All atoms heading in correct direction
within cylinder will exit hole in the time dt
if ` = vdt (
v = hvi).

Hole area dA

Then
T ot dAdt =

n`dA n
v dtdA
=
6
6

(T ot dAdt = the number of exiting atoms, n = density of atoms

The factor of 6 results since 1/6 of atoms heading in +z direction.
Therefore
T ot =

n
v
CrudeEstimate00
6

Exact calculation:
Include velocity
R distribution (but not geometric effects).
Then T ot = 0 (vz )dvz for vz > 0 only.
(vz ) is the flux through hole for particular vz ,
3

Zero lower limit since only particles moving towards hole will exit. Then
(vz )dAdt
| {z }

= n`dA P (vz ) = nvz dtdA P (vz )

# exiting atoms with vz

Therefore using P (vz ) from above

T ot = n
=n

0 vz

1
m 2
2

1

z
m 2 mv
2 dv
z
2 Z e


2
2
ueu du
m
}
| 0 {z

, u=

pm

2 vz

1
2

=n

Recall from earlier v = hvi =

Therefore

2m

8
m .

1
v
T ot = n
4
Exact result has modest difference ( 50%) with respect to crude estimate.
Now with E.O.S. n = P , we have
T ot =

P
2m

Thus flux effusing from hole is larger if m is smaller.

238
235
Used in 40s to separate
U
and
U
| {zF}6
| {zF}6
nonf issionable

0.7% abundancef issionable

Kinetic Theory of Transport

Characterize transport of heat, velocity, e , particles in non-equilibrium situations.
Approximate treatment good to factor of 2
(Exact treatmentorders of magnitude harder)
Assumptions:
1. Time between collisions  collision time (impulse only)
2. Two particle colllisions dominate (ignore 3-body interactions)
3. Particles behave classically (de Broglie distance between particles)
To model transport, first need to understand interaction of atoms (non-ideal)
Collisions:
Model particles as hard spheres with radius R
Particles collide if they are within 2R of each other.
Cross sectional area for collisions 0 = cross section = (2R)2
Probability of colliison with distance `:
4

R
R

For dilute gas and small d`

of particles
Probability of Collision= Area
Total Area

2R

2R
2R

Area of particles = the number of particles (2R)2 = |{z}

n (L2 d`)0
| {z }
density

Then

V olume

2R

2R

2R
2R

nL d`0
= n0 d`
L2
To find Probability of collision for a large distance ` [PC (`)]
define probability of no collision in ` as PN C (`) [PC = 1 PN C ]. Then

probabiliy of collision =

PN C (` + d`) =
|
{z
}

No collision in `+d`

or

(1 n0 d`)
|
{z
}

PN C (`)
| {z }

No collision in `

No collision in d`

dPN C
= PN C (`)n0
d`

solving
PN C (`) = en0 ` (since PN C (0) = 1)
then

Pc (`) = 1 en0 `
`
mf p

1e

with `mf p = mean free path length = n010 = mean distance between collisions.
(Above ignored other particles motion small correction)
Checking:
h`i =

R
`P (`)d`
R0 N C
PN C (`)d`
0

`mf p

R
0

`
`mf p d`

`mf p

= `mf p
Diffusion and Effusion Demos
Transport Theory:
Elementary Treatment:
Simple linear law good for many physical system (Phenomenological).
Flux of something (particles, heat, momentum) Driving force
gradient (something)
Ohms-like Laws:


~
J~electric current
= R1 Q
(Q = (electric potential)
~
Self diffusion J~particles = Dn
(D = diffusivity, n = density)
~
J~heat
= K T
(K = thermal conductivity)
vx
Jz momentum
= z
( = viscosity) see figure below

2R

2R

dl

z
x

Moving plate v0

vx
fluid velocity

Fluid
Stationary plate

Example: Diffusion
Use simple kinetic theory to calculate D.
Consider density gradient along zaxis, calc. flux of particles
crossing fixed z = z0 plane:

n(zn )
z=zn 11111111111111111111111111111111111111
00000000000000000000000000000000000000
00000000000000000000000000000000000000
11111111111111111111111111111111111111
00000000000000000000000000000000000000
11111111111111111111111111111111111111
00000000000000000000000000000000000000
00000000000000000000000000000000000000
11111111111111111111111111111111111111
z=z0 11111111111111111111111111111111111111
00000000000000000000000000000000000000 n(z )
11111111111111111111111111111111111111
l
z=zl
For distances < `mf p we will ignore collisions (particles move freely). Then
Flux up = [# particles going up/volume at z = z0 `mf p ] [Average Velocity]
n(z `
)
Jup
= 0 6 mf p (Vrms ) N ote : Vrms independent of density
n(z +`
)
Jdown
= 0 6 mf p (Vrms )
Then net flux:
Jparticles = Jup Jdown
= Vrms
6 [(n(z0 `mf p ) n(z0 + `mf p ]
= Vrms
0 ) n(z0 `mf p )] + [n(z0 + `mf p ) n(z0 )}
6 {[(n(z
|
{z
} |
{z
}
n
n
`
`
with
dz`
mf
p
mf
p
mf
p
z
 z

Vrms `mf p n
=
3
z

1
Therefore D = 13 Vrms `mf p = 13 3( m ) 2 0 p
For N2 at room and 1 atm., Vrms 5 104 cm/s,
`mf p 3 105 cm gives D ' 0.5 cm2 /s
(Exp. gives D = 0.2 cm2 /s) (within factor 2, OK for order of magnitude)

Note:
1. Can also model diffusion as random walk.

Random Walk

Eg. How long for photon made at center of sun to reach surface?
10
Without collisions Rsun
cm
c , Rsun 7 10
10
Speed of photons = c = 3 10 cm/s
Time to surface without collisions = Rsun
c = 2 sec
tc = time to surface with collisions: random walk
Recall hD2 i = N `2 (N is the number of steps, ` is the average step size= `mf p )
` p
hD2 i
Rsun
tc = N time per step= N ( mf
)
but
N
=
C
`2 = `2
mf p

2
Rsun
`mf p C ,

Therefore, tc =
hne i 8 10 /cm , `mf p = n1 0
n is density of electrons, 0 is the photon-electron cross section, 0 0.67 barns
(1 barn= 1024 cm2 )
Therefore `mf p 1 cm and tc 2 2 ( 107 s) ' 4000 years
| {z }
23

1 year

2. Particle flow must obey a continuity equation

(the number of particles is conserved)

(n |{z}
Adz ) = AJz (z) AJz (z + dz)
t volume
n Jz
=
t
z
n
2n
Therefore since Jz = D z , n obeys differential equation n
t = D z 2
Advanced Treatment (recall effusion example-yesterday)
Want to correctly include velocity distribution in calculations:
Consider f (~r, ~v , t)d3~rd3~v where f is the particle distribution function,
= mean number of particles with ~r between ~r and ~r + d~r and ~v between ~v + d~v
at time t
Knowledge of f solves transport problem, therefore need Eq. for f
Consider first in absence of collisions, particles under influence of force. Then

~r0 = ~r + ~v dt
~v 0 = ~v + ~v dt = ~v +

F~
M dt

and we have
f (~r0 , ~v 0 , t0 )d3~r0 d3~v 0 = f (~r, ~v , t)d3~rd3~v
since total number of particles is unchanged.
Now from Liouvilles Theorem of Classical Mechanics (Ph106, Ph1a?):
(Volume of phase space is conserved) d3~r0 d3~v 0 = d3~rd3~v
~ , t) = 0
Therefore f (~r0 , ~v 0 , t0 ) = f (~r, ~v , t) or f (~r + ~r dt, ~v + ~v dt, t + dt) f (~r, N
7

or we can rewrite above as Df = 0 Boltzmann Transport Eq. without collisions

or since
f
f
f (x + dx, y + dy) f (x, y) =
dx +
dy = df
x
y
we have




f
f
f
f
f
f
f
Df =
x +
y +
z dt +
v x +
v y +
v z dt +
dt = 0
x
y
z
vx
vy
vz
t
or

~
~ + F
~ v f + f = 0
~v f
m
t
Boltzmann Transport Equation (without collisions)

Then with collisions

f (~r0 , ~v 0 , t0 )d3~v 0 d3~r0 = f (~r, ~v , t)d3~rd3~v + Dcoll f (~r, ~v , t)dtd3~v d3~r
(Dcoll f (~r, ~v , t)dt is net increase in number of particles in d3~rd3~v due to collisions)
Giving
Df = Dcoll f
Full Boltzmann equation