Vacuum Technology

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: [email protected]

Dr. Philip D. Rack Page 1

Vacuum Technology

Vacuum Basics
Gas Volume % Pressure (Pa)
N2 78 79,117
O2 21 21,233
CO2 0.033 33.4
Ar 0.934 946.4
Atmospheric Pressure = 101,323.2 Pa (760 torr)
(133Pa = 1 torr)

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 Vacuum Technology

Vacuum Basics
Vacuum Pressure Range
(Pa)
Low 10 > P > 3.3x103
5

Medium 3.3x103 > 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- 10-10 > P
high

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Vacuum Technology

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)

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 Vacuum Technology

Gas Properties
• Atmospheric Pressure at Room Temperature
– ~2.5x1025 molecules/m3 (large number!)
– average spacing -- 3.4x10-9 ( > molecular diameters of ~2x10-10)

• Very high vacuum at Room Temperature

– ~2.5x1013 molecules/m3
– average spacing -- 3x10-5m

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Vacuum Technology

Velocity Distribution
• Maxwell Boltzmann Distribution
3
dn 2 N  m  2 2 − mv ( 2 kT )
2

=   ve
dv π 12  2kT 
where :
dn
= particle velocity distribution
dv
N = total number of molecules
m = mass of each particle
k = Boltzman's Constant
T = temperature
v = velocity
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 Vacuum Technology

Temperature/Mass Dependencies
• Temperature Dependence • Molecular Mass Dependence

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Vacuum Technology

Basic Expressions from Maxwell Boltzmann Distribution

• Average particle velocity (Maxwell-Boltzmann)

1
 8 KT  2
ν = 
 πm 
where :
ν = average velocity
K = Boltzman's Constant
T = Temperature
m = mass of particle
• ↑Temperature, ↓ mass -- ↑ average particle velocity

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 Vacuum Technology

Basic Expressions from Maxwell Boltzmann Distribution

• Peak Velocity (set first derivative of distribution = 0)

1
 2kT  2
vp =  
 m 
• Root Mean Square Velocity
1/ 2
 3kT 
vrms = 
 m 
• Maxwell-Boltzmann Statistics
– vavg = 1.128vp and vrms = 1.225vp

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Vacuum Technology

Maxwell-Boltzmann Velocities
0.0012
dN/dV
0.001 peak
0.0008 average
RMS
dn/dV

0.0006

0.0004

0.0002

0
0 200 400 600 800 1000 1200
Velocity (m/s)

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 Vacuum Technology

Maxwell-Boltzmann Energy Distribution

• Energy Distribution
dn 2 N E 1/ 2 − E ( kT )
= e
dE π 1 2 (kT ) 3 / 2
where :
dn
= particle velocity distribution
dE
N = total number of molecules
k = Boltzman's Constant
T = temperature
• Average Energy = 1/2kT (x3 dimensions) =
3kT/2
• Most probable energy = kT/2

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Vacuum Technology

Maxwell-Boltzmann Energy Distribution

Peak

Average

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 Vacuum Technology

Pressure and Molecular Velocity

For molecules traveling with velocity{Vx},

the distance they can travel in time interval ∆t is:
{Vx} ∆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: n•A{Vx}∆t, but half of the molecules move towards
the surface, half away from the surface:
(1/2)n•A{Vx}∆t
When a molecule collides with the surface, it’s momentum changes
from mVx to -mVx (total 2mVx) (m=MW/NA), hence the total
momentum change is:
= [(number of collisions)] • (momentum change per collision)
= [(1/2)n•A{Vx}∆t] • (2m{Vx})
= n•m•A{Vx2}∆t

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Vacuum Technology

Pressure and Molecular Velocity

Since force is the rate of change of momentum: f = n•m•A{Vx2}

Pressure is the force per unit area: P = n•m•{Vx2}

Generalizing: 1/ 2
{V2}= {Vx2} + {Vy2} + {Vz2}  3kT 
= 3 {Vx2}, P = (1/3)n•m{V2} vrms = 
Generally VRMS is used here  m 
P=nkT
(where n=N/V)

1 atm = 1013 mbar = 1.013 bar = 760 mmHg

Dr. Philip D. Rack 1 atm = 760 torr = 101,325 Pa = 101,325 Nm-2 Page 14

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 Vacuum Technology

Collision Frequency
A molecule of diameter “do” sweeps out a collision cylinder of
cross-sectional area:
σ = πd02,
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•σ{V}•n

The time a molecule

spends between collisions
is Dr.
1/Z.Philip D. Rack Page 15

Vacuum Technology

The Mean Free Path

Mean free path (l) - average distance a particle travels before it

collides with another particle:
1
λ= 6 .6
1
2 πd n
2 2 λ (mm) =
o
P ( Pa )
where :
(for air at room temperature)
d o = molecular diameter
n = gas particle density

↑ Pressure (↑ particle density) -- ↓ mean free path

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 Vacuum Technology

Basic Equations from Kinetic Theory

• Distribution of free paths
−x
N = N 'e λ
(random walk distributi on) 1

N/N' (% of particles)
0.9
0.8

where : 0.7
0.6
0.5

N ' = number of molecules in a volume 0.4

0.3
0.2
N = number of molecules that traverse a 0.1
0
0 1 2 3 4 5 6
distance x before suffering a collision x/lambda

63% suffer collision 0<x<λ

37% suffer collision λ<x<5λ
only 0.6% travel farther than 5λ

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Vacuum Technology

Particle Flux or Impingement Rate

1

• Flux  KT  2
Γ = n 
 2πm 
where :
Area n = particle density
nν K = Boltzman's Constant
Γ=
4 T = Temperature
Γ = particle flux m = mass of particle
n = particle density From ideal
Gas law
ν = average velocity
P
Γ= 1

(2πmkT )
2

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 Vacuum Technology

Monolayer Formation Times

The inverse of the Gas impingement rate (or flux) is related to the
Monolayer coverage time (tc). If a surface has ~ 1015sites/cm2

tc = 1015 /sΓ,
where S is the sticking coefficient
Γ is the particle flux

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
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.
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Vacuum Technology

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 Vacuum Technology

Boyle’s Law (1622)

• P∝1/V (T and N constant)

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Vacuum Technology

Amontons’ Law (1703)

• P∝T (N and V constant)

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 Vacuum Technology

Charles’ Law (1787)

• V∝T (P and N constant)

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Vacuum Technology

Dalton’s Law (1801)

• Dalton’s Law of Partial Pressures
• Pt = n1kT + n2kT + n3kT + ... nikT
– where Pt is the total pressure and ni is the
number of molecukles of gas i

• Pt = P1 + P2 + P3 … Pi
– where Pt is the total pressure and Pi is the
partial pressure of gas i

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 Vacuum Technology

Avagadro’s Law (1811)

• P∝N (T and V constant)

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Vacuum Technology

Low Pressure Properties of Air

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 Vacuum Technology

Gas Transport Phenomena

• Viscosity -- due to momentum transfer via molecular
collisions (development of a force due to motion in a fluid)

y Moving Surface U1
Fx dU
=η
Axz dy 2
where : Axz
Fx = force in x - direction U 1
A xz = surface area in x - z plane
η = coefficient of viscosity
dU z
= rate of change of the gas velocity at Fixed Surface x
dy
this position betwen the two surfaces
U1 < U2

Dr. Philip D. Rack Page 27

Vacuum Technology

Gas Transport Phenomena

• Viscosity
– Kinetic Theory
1
η = nmνλ
3
– More Rigorous Treatment
η = 0.4999 nmνλ
1
0.4999(4mkT ) 2
η= 3
(when y ≥ λ )
π d 2 2
o

Viscosity ∝ (mT)1/2 and do2

and independent of P (only true for y ≥ λ)

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 Vacuum Technology

Gas Transport Phenomena

• Viscosity
– for λ >> y (free molecular viscosity)
Fx  Pmv  U1
= 
Axz  4kT  β
where :
Fx
= viscous force
Axz
 Pmv 
  = free molecular viscosity
 4kT 
β ≈ 1 (related to the slip of atoms on the plate surface)

Viscosity ∝ Pressure

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Vacuum Technology

Gas Transport Phenomena

d
λ<d

Viscosity controlled by particle-particle collisions

d λ>d

Viscosity controlled by particle-wall collisions

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 Vacuum Technology

Gas Transport Phenomena

• Heat Flow (y ≥ λ) Hot Surface (T2)
y
dT
H = AK 2
dy
Axz
where :
T 1
H = heat flow
K = heat conductivity = ηc v
cv = specific heat at constant volume z Cold Surface (T1) x
dT
= temperature gradient
dy T1 < T2

Heat Flow ∝ (mT)1/2 and do2

and independent of P (only true for y ≥ λ)

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Vacuum Technology

Gas Transport Phenomena

• Heat Flow (y ≥ λ) more detailed analysis of K (cf slide
#31)
– Simplified
K = ηcv
– Detailed
1
K= (9γ − 5)ηcv
4
where :
c
γ= P
cv γ = 1.4 (diatomic molecule)
c p = specific heat at costant pressure γ = 1.667 (monatomic molecule)
cv = specific heat at costant volume γ = 1.333 (triatomic molecule)

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 Vacuum Technology

Gas Transport Phenomena

• Heat Flow (λ >> y)
E0 = αΛP (T2 − T1 )
where :
E0 = heat flow
α = accomodation coefficient
(how effective the surfaces transfer and
absorb energy)
Λ = free - molecular heat conductivity
(how effective the molecules absorb
and transfer energy)

Heat Flow ∝ Pressure

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Vacuum Technology

Gas Transport Phenomena

d
λ<d

Heat Flow controlled by particle-particle collisions

d λ>d

Heat Flow controlled by particle-wall collisions

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 Vacuum Technology

Gas Transport Phenomena

• Diffusion Γ1 = − D
dn1
Γ2 = − D
dn2
dx dx
where : where :
D = diffusion coefficient D = diffusion coefficient
dn dn
= concentration gradient = concentration gradient
dx dx
1 1
 2kT  2  1 1  2
8   + 
 π   1m m 2 
D12 = (interdiffusion of two gases)
3πn(d 01 + d 02 ) 2

1
 kT  2
4 
πm 
D11 =  (self diffusion)
3πnd 0
2

D ∝ (T/m)1/2 and 1/nd02

suggests that as n→0, D→∞ (only good when λ < d or y)

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Vacuum Technology

Gas Transport Phenomena

• Diffusion (λ >> d)
2
D= rv
3
Knudsen diffusion
where :
r = radius of pipe or chamber
coefficient
v = thermal velocity

Gas diffusion is limited by collisions with container wall

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 Vacuum Technology

Gas Transport Phenomena

• Diffusion

Ndz −z2 z0 z0 = 2.32( Dt )

1
2
dn = 1
e ( 4 Dt )
f = erfc 1
(πDt ) 2 2( Dt ) 2
where :
where : where : z0 = minimum distance that 10% of the
dn = number of molecules located f = fraction of molecules that are molecules have diffused after a time t
between z and z + dz located between z 0 and ∞

z
x-y plane at t=0, z=0 x
y
+dz
2N molecules z=0
-dz

Dr. Philip D. Rack Page 37

Vacuum Technology

Gas Transport Phenomena

d
λ<d

Diffusion controlled by particle-particle collisions

d λ>d

Diffusion controlled by particle-wall collisions

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