Maxwells velocity distribution

The derivation of maxwell’s velocity distribution is based on several assumptions

1. In the equilibrium state the molecules have complete randomness of direction and
velocity
2. There is no mass motion or convection current
3. The probability that a molecule has a given velocity component is independent of the
other two components
4. The probability that a molecule at random has velocities in a given range is a function
purely of the magnitude of the velocity and the width of the interval

How many molecules will have a certain velocity?

Distribution of velocity → Determination of number of molecules having a certain velocity
BUT range of velocities infinite, number of molecules finite
Better to ask: How many molecules have velocity within certain interval near a certain
velocity.
Let dN = number of molecules having velocities within range c and c + dc
𝑑𝑁 ∝ 𝑑𝑐
If interval dc was larger dN would be larger
𝑑𝑁 = 𝑎 𝑑𝑐
a is proportionality constant and a is a function of c
𝑎 = 𝑓(𝑐)
𝑑𝑁 ∝ 𝑁
N total number of molecules
ⅆ𝑁 = 𝑁𝑓(𝑐) ⅆc
𝑓(𝑐) is the distribution function
ⅆ𝑁
Considering dc = 1, 𝑓(𝑐) = ; fraction of molecules whose velocities are within unit interval
𝑁
near c
𝑑𝑁
𝑓(𝑐) =
𝑁
ⅆ𝑁
is the probability of any molecule in unit volume having velocity that is within unit interval
𝑁
near the velocity c
(u,v,w) describe a velocity point
Probability of molecules having velocities between u and u + du 𝑓(𝑢)𝑑𝑢
Probability of molecules having velocities between v and v + dv 𝑓(𝑣)𝑑𝑣
Probability of molecules having velocities between w and w +dw 𝑓(𝑤) 𝑑𝑤
The number of molecules having components of velocity with u and u + du, v and v + dv and
w and w +dw in the volume element dudvdw of velocity space
𝑑𝑁 = 𝑁𝑓(𝑢)𝑓(𝑣)𝑓(𝑤)𝑑𝑢𝑑𝑣 𝑑𝑤
𝑑𝑁 = 𝑁𝜙(𝑐 2 )𝑑𝑢𝑑𝑣 𝑑𝑤
𝑑𝑁
= 𝑁𝑓(𝑢)𝑓(𝑣)𝑓(𝑤) = 𝑁𝜙(𝑐 2 )
𝑑𝑢𝑑𝑣 𝑑𝑤
ⅆ𝑁
is ρ which is the number density in velocity space
ⅆ𝑢ⅆ𝑣 ⅆ𝑤

𝜌 = 𝑁𝑓(𝑢)𝑓(𝑣)𝑓(𝑤) = 𝑁𝜙(𝑐 2 )
𝑑𝜌 = 𝑑[𝑁𝑓(𝑢)𝑓(𝑣)𝑓(𝑤)] = 𝑑[𝑁𝜙(𝑐 2 )]
For a fixed c, RHS = 0
𝑑[𝑓(𝑢)𝑓(𝑣)𝑓(𝑤)] = 0
𝑓 ′ (𝑢)𝑓(𝑣)𝑓(𝑤) 𝑑𝑢 + 𝑓(𝑢)𝑓 ′ (𝑣)𝑓(𝑤) 𝑑𝑣 + 𝑓(𝑢)𝑓(𝑣)𝑓 ′ (𝑤) 𝑑𝑤 = 0
Dividing by, 𝑓(𝑢)𝑓(𝑣)𝑓(𝑤)
𝑓 ′ (𝑢) 𝑓 ′ (𝑣) 𝑓 ′ (𝑤)
𝑑𝑢 + 𝑑𝑣 + 𝑑𝑤 = 0
𝑓(𝑢) 𝑓(𝑣) 𝑓(𝑤)
𝑐 2 = 𝑢2 + 𝑣 2 + 𝑤 2
2𝑢 𝑑𝑢 + 2𝑣 𝑑𝑣 + 2𝑤 𝑑𝑤 = 0
𝑢 𝑑𝑢 + 𝑣 𝑑𝑣 + 𝑤 𝑑𝑤 = 0
Multiply by β and add
𝑓 ′ (𝑢) 𝑓 ′ (𝑣) 𝑓 ′ (𝑤)
[ + 𝛽𝑢] 𝑑𝑢 + [ + 𝛽𝑣] 𝑑𝑣 + [ + 𝛽𝑤] 𝑑𝑤 = 0
𝑓(𝑢) 𝑓(𝑣) 𝑓(𝑤)

𝛽 is undetermined multiplier of Lagrange

Lagrange method of undetermined multiplier is mainly used to find the maximum or minimum value (optimized value) of
several variables in which all the variables are not independent. Say 𝑓(𝑥, y, z) is an objective function of 3 variables which
are connected by the constraint 𝜑(𝑥, y, z) = 0

Lagrange function can be written as 𝐹(𝑥, 𝑦, 𝑧) = 𝑓(𝑥, y, z) + 𝜆 𝜑(𝑥, y, z)

𝜕𝑓 𝜕𝑓 𝜕𝜑 𝜕𝜑
According to Lagrange’s method, 𝑑𝐹 = ( 𝑑𝑥 + 𝑑𝑦) + 𝜆 ( 𝑑𝑥 + 𝑑𝑦) = 0
𝜕𝑥 𝜕𝑦 𝜕𝑥 𝜕𝑦
 𝑓 ′ (𝑢) 𝑓 ′ (𝑣) 𝑓 ′ (𝑤)
= −𝛽𝑢 = −𝛽𝑣 = −𝛽𝑤
𝑓(𝑢) 𝑓(𝑣) 𝑓(𝑤)
−𝛽𝑢2
𝑙𝑛 𝑓(𝑢) = + 𝑙𝑛 𝑎
2
𝛽𝑢2 2
−
𝑓(𝑢) = 𝑎ⅇ 2 = 𝑎ⅇ −𝑏𝑢
𝛽
𝑏=
2
2 2
𝑓(𝑣) = 𝑎ⅇ −𝑏𝑣 𝑓(𝑤) = 𝑎ⅇ −𝑏𝑤
2 +𝑣 2 +𝑤 2 )
𝑓(𝑢)𝑓(𝑣)𝑓(𝑤) = 𝑎3 ⅇ −𝑏(𝑢
2 +𝑣 2 +𝑤 2 )
𝑑𝑁 = 𝑁𝑓(𝑢)𝑓(𝑣)𝑓(𝑤)𝑑𝑢𝑑𝑣 𝑑𝑤 = 𝑁𝑎3 ⅇ −𝑏(𝑢 𝑑𝑢𝑑𝑣 𝑑𝑤
2
𝑑𝑁 = 𝑁𝑓(𝑢)𝑓(𝑣)𝑓(𝑤)𝑑𝑢𝑑𝑣 𝑑𝑤 = 𝑁𝑎3 ⅇ −𝑏(𝑐 ) 𝑑𝑢𝑑𝑣 𝑑𝑤
Finding volume in velocity space
𝑑𝑢𝑑𝑣 𝑑𝑤 = 𝑐 2 sin 𝜃𝑑𝑐𝑑𝜃 ⅆ𝜙
2)
𝑑𝑁 = 𝑁𝑓(𝑢)𝑓(𝑣)𝑓(𝑤)𝑑𝑢𝑑𝑣 𝑑𝑤 = 𝑁𝑎3 ⅇ −𝑏(𝑐 𝑐 2 sin 𝜃𝑑𝑐𝑑𝜃 ⅆ𝜙
𝜋 2𝜋
3 −𝑏𝑐 2
𝑑𝑁𝑐 = 𝑁𝑎 ⅇ 𝑑𝑐 ∫ 𝑠𝑖𝑛 𝜃 𝑑𝜃 ∫ 𝑑𝜙
0 0
𝜋 2𝜋

∫ 𝑠𝑖𝑛 𝜃 𝑑𝜃 ∫ 𝑑𝜙 = 4𝜋
0 0
2
𝑑𝑁𝑐 = 4𝜋𝑁𝑎3 ⅇ −𝑏𝑐 𝑐 2 𝑑𝑐

Cartesian to spherical polar coordinates

𝑃𝐴 = 𝑟 𝑑𝜃
𝑃𝐵 = 𝑟 𝑠𝑖𝑛 𝜃 𝑑𝜙
𝐴𝑟ⅇ𝑎 = 𝑟 2 𝑠𝑖𝑛 𝜃𝑑𝜃 𝑑𝜙
𝑉 = 𝑟 2 𝑑𝑟 𝑠𝑖𝑛 𝜃𝑑𝜃 𝑑𝜙
𝑉 = 𝑐 2 𝑑𝑐 𝑠𝑖𝑛 𝜃𝑑𝜃 𝑑𝜙
Finding a and b
ⅆ𝑁 = 𝑁𝑓(𝑐) ⅆc
𝑑𝑁
= 𝑓(𝑐) 𝑑𝑐
𝑁
2
𝑓(𝑐) 𝑑𝑐 = 4𝜋𝑎3 ⅇ −𝑏𝑐 𝑐 2 𝑑𝑐
𝛴 𝑑𝑁 = 𝑁
𝑑𝑁
∫ 𝑓(𝑐) 𝑑𝑐 = 𝛴 =1
𝑁
∞
2
∫ 4𝜋𝑎3 ⅇ −𝑏𝑐 𝑐 2 𝑑𝑐 = 1
0
∞
2
4𝜋𝑎3 ∫ ⅇ −𝑏𝑐 𝑐 2 𝑑𝑐 = 1
0

∞ 2 1 𝜋
∫ ⅇ −𝑠𝑐 𝑐 2 𝑑𝑐 = 4 √𝑠3 standard integral
0

1 𝜋
4𝜋𝑎3 √ 3 = 1
4 𝑏
3 3 3
−
𝜋 2 𝑎3𝛽 2 22 = 1
3
𝛽2 𝛽
𝑎3 = 3 ⇒𝑎=√
2𝜋
(2𝜋)2
𝑁1 𝑐12 + 𝑁2 𝑐22 + ⋯
⟨𝑐⟩ =
𝑁1 + 𝑁2
1 ∞ 2
= ∫ 𝑐 𝑑𝑁
𝑁 𝑜
∞
= ∫ 𝑐 2 𝑓(𝑐) 𝑑𝑐
0
∞
𝛽 2
= ∫ 𝑐 2 4𝜋𝑎3 ⅇ − 2 𝑐 𝑐 2 𝑑𝑐
0
∞ 𝛽 2
= 4𝜋𝑎3 ∫ ⅇ − 2 𝑐 𝑐 4 𝑑𝑐
0

∞ 2 3 𝜋 1⁄2
∫ ⅇ −𝑎𝑥 𝑥 4 𝑑𝑥 = 8 5 standard integral
0 𝑎 ⁄2
 ∞
2 3 𝜋
∫ ⅇ −𝑠𝑥 𝑥 4 𝑑𝑥 = √ 5
0 8 𝑠
3
𝛽 2 3 𝜋 𝛽
⟨𝑐 2 ⟩ = 4𝜋 ( ) × 5 =
2𝜋 8√ 𝛽 3
( )
2

1 3
𝑚⟨𝑐 2 ⟩ = 𝑘𝐵 𝑇
2 2
1 𝛽 3
𝑚 ( ) = 𝑘𝐵 𝑇
2 3 2
𝑚
𝛽=
𝑘𝐵 𝑇

𝛽 𝑚
𝑎=√ =√
2𝜋 2𝜋𝑘𝐵 𝑇

2
𝑓(𝑐) 𝑑𝑐 = 4𝜋𝑎3 ⅇ −𝑏𝑐 𝑐 2 𝑑𝑐
3
𝑚 2 2 −𝑚𝑐 2
𝑓(𝑐) = 4𝜋 ( ) 𝑐 ⅇ 2𝑘𝑇
2𝜋𝑘𝑇

Average/mean velocity
 ∞ 2 1
∫ ⅇ −𝑎𝑥 𝑥 3 𝑑𝑥 = 2𝑎2 standard integral
0

Root mean square (rms) velocity

∞ 2 3 𝜋 1⁄2
∫ ⅇ −𝑎𝑥 𝑥 4 𝑑𝑥 = 8 5 standard integral
0 𝑎 ⁄2
Most probable velocity
𝑑𝑁
=𝐹
𝑑𝑐
Ratio of the velocities