1

Dr. Philip D. Rack

Vacuum Technology
Page 1
Kinetic Theory of Gas
Dr. Philip D. Rack
Assistant Professor
Department of Materials Science and
Engineering
University of Tennessee
603 Dougherty Engineering Building
Knoxville, TN 37931-2200
Phone: (865) 974-5344
Fax (865) 974-4115
Email: prack@utk.edu
Dr. Philip D. Rack
Vacuum Technology
Page 2
Vacuum Basics
Gas Volume % Pressure (Pa)
N
2
78 79,117
O
2
21 21,233
CO
2
0.033 33.4
Ar 0.934 946.4
Atmospheric Pressure = 101,323.2 Pa (760 torr)
(133Pa = 1 torr)
2
Dr. Philip D. Rack
Vacuum Technology
Page 3
Vacuum Basics
Vacuum Pressure Range
(Pa)
Low 10
5
> P > 3.3x10
3
Medium 3.3x10
3
> P >10
-1
High 10
-1
> P > 10
-4
Very High 10
-4
> P > 10
-7
Ultra High 10
-7
>P>10
-10
Extreme Ultra-
high
10
-10
> P
Dr. Philip D. Rack
Vacuum Technology
Page 4
Kinetic Picture of an Ideal Gas
Volume of gas contains a large number of molecules
Adjacent molecules are separated by distances that are
large relative to the individual diameters
Molecules are in a constant state of motion
All directions of motion are possible (3-dimensions)
All speeds are possible (though not equally probable)
Molecules exert no force on each other except when they
collide
Collisions are elastic (velocity changes and energy is
conserved)
3
Dr. Philip D. Rack
Vacuum Technology
Page 5
Gas Properties
Atmospheric Pressure at Room Temperature
~2.5x10
25
molecules/m
3
(large number!)
average spacing -- 3.4x10
-9
( > molecular diameters of ~2x10
-10
)
Very high vacuum at Room Temperature
~2.5x10
13
molecules/m
3
average spacing -- 3x10
-5
m
Dr. Philip D. Rack
Vacuum Technology
Page 6
Velocity Distribution
Maxwell Boltzmann Distribution
velocity v
re temperatu T
Constant s Boltzman' k
particle each of mass m
molecules of number total N
on distributi velocity particle
dv
dn
: where
2
2
) 2 ( 2
2
3
2
1
2
=
=
=
=
=
=
|
.
|

\
|
=

kT
mv
e v
kT
m N
dv
dn

4
Dr. Philip D. Rack
Vacuum Technology
Page 7
Temperature/Mass Dependencies
Temperature Dependence Molecular Mass Dependence
Dr. Philip D. Rack
Vacuum Technology
Page 8
Average particle velocity (Maxwell-Boltzmann)
Temperature, mass -- average particle velocity
Basic Expressions from Maxwell Boltzmann Distribution
particle of mass m
e Temperatur T
Constant s Boltzman' K
velocity average
:
8
2
1
=
=
=
=
|
.
|

\
|
=

where
m
KT
5
Dr. Philip D. Rack
Vacuum Technology
Page 9
Basic Expressions from Maxwell Boltzmann Distribution
Peak Velocity (set first derivative of distribution = 0)
Root Mean Square Velocity
Maxwell-Boltzmann Statistics
v
avg
= 1.128v
p
and v
rms
= 1.225v
p
2
1
2
|
.
|

\
|
=
m
kT
v
p
2 / 1
3
(

=
m
kT
v
rms
Dr. Philip D. Rack
Vacuum Technology
Page 10
Maxwell-Boltzmann Velocities
0
0.0002
0.0004
0.0006
0.0008
0.001
0.0012
0 200 400 600 800 1000 1200
Velocity (m/s)
d
n
/
d
V
dN/dV
peak
average
RMS
6
Dr. Philip D. Rack
Vacuum Technology
Page 11
Maxwell-Boltzmann Energy Distribution
Energy Distribution
Average Energy = 1/2kT (x3 dimensions) =
3kT/2
Most probable energy = kT/2
re temperatu T
Constant s Boltzman' k
molecules of number total N
on distributi velocity particle
dE
dn
: where
) (
2
) (
2 / 3
2 / 1
2
1
=
=
=
=
=

kT
E
e
kT
E N
dE
dn

Dr. Philip D. Rack

Vacuum Technology
Page 12
Maxwell-Boltzmann Energy Distribution
Peak
Average
7
Dr. Philip D. Rack
Vacuum Technology
Page 13
For molecules traveling with velocity{V
x
},
the distance they can travel in time interval t is:
{V
x
} t
If they move towards the wall of area A and the
number density is n (=N/V), the number of molecules that strike the
wall in time t is: nA{V
x
}t, but half of the molecules move towards
the surface, half away from the surface:
(1/2)nA{V
x
}t
When a molecule collides with the surface, its momentum changes
from mV
x
to -mV
x
(total 2mV
x
) (m=MW/N
A
), hence the total
momentum change is:
= [(number of collisions)] (momentum change per collision)
= [(1/2)nA{V
x
}t] (2m{V
x
})
= nmA{V
x
2
}t
Pressure and Molecular Velocity
Dr. Philip D. Rack
Vacuum Technology
Page 14
Since force is the rate of change of momentum: f = nmA{V
x
2
}
Pressure is the force per unit area: P = nm{V
x
2
}
Generalizing:
{V
2
}= {V
x
2
} + {V
y
2
} + {V
z
2
}
= 3 {V
x
2
}, P = (1/3)nm{V
2
}
Generally V
RMS
is used here
1 atm = 1013 mbar = 1.013 bar = 760 mmHg
1 atm = 760 torr = 101,325 Pa = 101,325 Nm
-2
Pressure and Molecular Velocity
2 / 1
3
(

=
m
kT
v
rms
P=nkT
(where n=N/V)
8
Dr. Philip D. Rack
Vacuum Technology
Page 15
The time a molecule
spends between collisions
is 1/Z.
A molecule of diameter d
o
sweeps out a collision cylinder of
cross-sectional area:
= d
0
2
,
and length {V}t, during period t. For two colliding objects we
must really take into account their relative speeds (not one fixed,
one moving). The collision frequency Z (per unit time) per
molecule is = 2{V}n
Collision Frequency
Dr. Philip D. Rack
Vacuum Technology
Page 16
Pressure ( particle density) -- mean free path
The Mean Free Path
Mean free path (l) - average distance a particle travels before it
collides with another particle:
density particle gas n
diameter molecular
:
2
1
2
2
1
=
=
=
o
o
d
where
n d

) (
6 . 6
) (
Pa P
mm =
(for air at room temperature)
9
Dr. Philip D. Rack
Vacuum Technology
Page 17
Distribution of free paths
Basic Equations from Kinetic Theory
collision a suffering before x distance
a erse that trav molecules of number N
volume a in molecules of number '
:
on) distributi walk (random '
=
=
=

N
where
e N N
x

0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 1 2 3 4 5 6
x/lambda
N
/
N
'

(
%

o
f

p
a
r
t
i
c
l
e
s
)
63% suffer collision 0<x<
37% suffer collision <x<5
only 0.6% travel farther than 5
Dr. Philip D. Rack
Vacuum Technology
Page 18
Flux
Particle Flux or Impingement Rate
velocity average
n

density particle n
flux particle
4
=
=
=
=

particle of mass m
e Temperatur T
Constant s Boltzman' K
density particle
:
2
2
1
=
=
=
=
|
.
|

\
|
=
n
where
m
KT
n

Area
( )
2
1
2 mkT
P

=
From ideal
Gas law
10
Dr. Philip D. Rack
Vacuum Technology
Page 19
Monolayer Formation Times
The inverse of the Gas impingement rate (or flux) is related to the
Monolayer coverage time (t
c
). If a surface has ~ 10
15
sites/cm
2
At 300K and 1 atm, if every Nitrogen molecule that strikes the surface
remains absorbed, a complete monolayer is formed in about t = 3 ns.
If P = 10
-3
torr (1.3 x 10
-6
atm), t = 3x10
-3
s
If P = 10
-6
torr (1.3 x 10
-9
atm), t = 3 s
If P = 10
-9
torr (1.3 x 10
-12
atm), t = 3000 s or 50 minutes
t
c
= 10
15
/s,
where S is the sticking coefficient
is the particle flux
Requirement for Experiment in Vacuum: Clean surface quickly becomes
contaminated through molecular collision, p must be less than about
10
-12
atm (7.67x10
-5
torr).
10
-10
to 10
-11
torr (UHV-ultra high vacuum) is the lowest pressure
routinely available in a vacuum chamber.
Dr. Philip D. Rack
Vacuum Technology
Page 20
11
Dr. Philip D. Rack
Vacuum Technology
Page 21
Boyles Law (1622)
P1/V (T and N constant)
P
V
Dr. Philip D. Rack
Vacuum Technology
Page 22
Amontons Law (1703)
PT (N and V constant)
T
P
12
Dr. Philip D. Rack
Vacuum Technology
Page 23
Charles Law (1787)
VT (P and N constant)
T
V
Dr. Philip D. Rack
Vacuum Technology
Page 24
Daltons Law (1801)
Daltons Law of Partial Pressures
P
t
= n
1
kT + n
2
kT + n
3
kT + ... n
i
kT
where P
t
is the total pressure and n
i
is the
number of molecukles of gas i
P
t
= P
1
+ P
2
+ P
3
P
i
where P
t
is the total pressure and P
i
is the
partial pressure of gas i
13
Dr. Philip D. Rack
Vacuum Technology
Page 25
Avagadros Law (1811)
PN (T and V constant)
N
P
Dr. Philip D. Rack
Vacuum Technology
Page 26
Low Pressure Properties of Air
14
Dr. Philip D. Rack
Vacuum Technology
Page 27
Gas Transport Phenomena
Viscosity -- due to momentum transfer via molecular
collisions (development of a force due to motion in a fluid)
surfaces two betwen the position this
at velocity gas the of change of rate
dy
dU
viscosity of t coefficien
plane z - in x area surface A
direction - in x force
:
xz
=
=
=
=
=

x
xz
x
F
where
dy
dU
A
F
z
y
x
U
1
Moving Surface
U
Fixed Surface
A
xz
2
1
U
1
< U
2
Dr. Philip D. Rack
Vacuum Technology
Page 28
Gas Transport Phenomena
Viscosity
Kinetic Theory
More Rigorous Treatment
nm
3
1
=
nm 4999 . 0 =
) y (when
) 4 ( 4999 . 0
2
2
3
2
1

=
o
d
mkT
Viscosity (mT)
1/2
and d
o
2
and independent of P (only true for y )
15
Dr. Philip D. Rack
Vacuum Technology
Page 29
Gas Transport Phenomena
Viscosity
for >> y (free molecular viscosity)
surface) plate on the atoms of slip the to (related 1
viscosity molecular free
4
force viscous
:
4
1

= |
.
|

\
|
=
|
.
|

\
|
=

kT
Pmv
A
F
where
U
kT
Pmv
A
F
xz
x
xz
x
Viscosity Pressure
Dr. Philip D. Rack
Vacuum Technology
Page 30
Gas Transport Phenomena
< d
d
> d
d
Viscosity controlled by particle-particle collisions
Viscosity controlled by particle-wall collisions
16
Dr. Philip D. Rack
Vacuum Technology
Page 31
Gas Transport Phenomena
Heat Flow (y )
z
y
x
Hot Surface (T
2
)
T
Cold Surface (T
1
)
A
xz
2
1
T
1
< T
2
gradient re temperatu
dy
dT
olume constant v at heat specific
c ty conductivi heat K
flow heat H
:
v
=
=
= =
=
=
v
c
where
dy
dT
AK H

Heat Flow (mT)

1/2
and d
o
2
and independent of P (only true for y )
Dr. Philip D. Rack
Vacuum Technology
Page 32
Gas Transport Phenomena
Heat Flow (y ) more detailed analysis of K (cf slide
#31)
Simplified
Detailed
v
c K =
lume costant vo at heat specific
pressure costant at heat specific
c
c
:
) 5 9 (
4
1
v
P
=
=
=
=
v
p
v
c
c
where
c K

molecule) (triatomic 333 . 1
molecule) (monatomic 667 . 1
molecule) (diatomic 4 . 1
=
=
=

17
Dr. Philip D. Rack
Vacuum Technology
Page 33
Gas Transport Phenomena
Heat Flow ( >> y)

energy) transfer and
absorb molecules the effective (how
ty conductivi heat molecular - free
energy) absorb
and transfer surfaces the effective (how
t coefficien on accomodati
flow heat
:
) (
0
1 2 0
=
=
=
=

E
where
T T P E
Heat Flow Pressure
Dr. Philip D. Rack
Vacuum Technology
Page 34
Gas Transport Phenomena
< d
d
> d
d
Heat Flow controlled by particle-particle collisions
Heat Flow controlled by particle-wall collisions
18
Dr. Philip D. Rack
Vacuum Technology
Page 35
Gas Transport Phenomena
Diffusion
gradient ion concentrat
dx
dn
t coefficien diffusion D
:
1
1
=
=
=
where
dx
dn
D
gradient ion concentrat
dx
dn
t coefficien diffusion D
:
2
2
=
=
=
where
dx
dn
D
gases) two of usion (interdiff
) ( 3
1 1 2
8
2
02 01
2
1
2 1
2
1
12
d d n
m m
kT
D
+
|
|
.
|

\
|
+ |
.
|

\
|
=

diffusion) (self
3
4
2
0
2
1
11
nd
m
kT
D

|
.
|

\
|
=
D (T/m)
1/2
and 1/nd
0
2
suggests that as n0, D (only good when < d or y)
Dr. Philip D. Rack
Vacuum Technology
Page 36
Gas Transport Phenomena
Diffusion ( >> d)
velocity thermal v
chamber or pipe of radius
:
3
2
=
=
=
r
where
rv D
Knudsen diffusion
coefficient
Gas diffusion is limited by collisions with container wall
19
Dr. Philip D. Rack
Vacuum Technology
Page 37
Gas Transport Phenomena
Diffusion
x
y
z
2N molecules
x-y plane at t=0, z=0
z=0
-dz
+dz
dz z and z between
located molecules of number
:
) (
) 4 (
2
1
2
+
=
=

dn
where
e
Dt
Ndz
dn
Dt
z

=
=
and z between located
are that molecules of fraction
:
) ( 2
0
2
1
0
f
where
Dt
z
erfc f
t time a after diffused have molecules
the of 10% that distance minimum
:
) ( 32 . 2
0
2
1
0
=
=
z
where
Dt z
Dr. Philip D. Rack
Vacuum Technology
Page 38
Gas Transport Phenomena
< d
d
> d
d
Diffusion controlled by particle-particle collisions
Diffusion controlled by particle-wall collisions