MAXWELL-BOLTZMANN DISTRIBUTION

● The maxwell-boltzman equation which forms the

basis of the kinetic theory of gases,defines the
distribution of speeds for a gas at a certain
temperature.

● From this distribution function, the most probable

speed, and the root mean square speed can be
derived.

Introduction

● The kinetic molecular theory is used to determine the

motion of a molecule of an ideal gas under a certain set
of conditions. However, when looking at a mole of ideal
gas, it is impossible to measure the velocity of each
molecule at every instant of time.
● Therefore, the Maxwell-Boltzmann distribution is used to
determine how many molecules are moving between
velocities v and v + dv. Assuming that the
one-dimensional distributions are independent of one
another, that the velocity in the y and z directions does
not affect the x velocity, for example, the
Maxwell-Boltzmann distribution is given by
 2
−𝑚𝑣

𝑑𝑁 ÷ 𝑁 = ( 𝑚
2Π𝑘𝐵𝑇 ) 𝑒
2𝑘𝑏𝑇
dv
where

● dN/N is the fraction of molecules moving at velocity v to v

+ dv,
● m is the mass of the molecule,
● kb is the Boltzmann constant, and
● T is the absolute temperature.1

Additionally, the function can be written in terms of the scalar

quantity speed c instead of the vector quantity velocity. This
form of the function defines the distribution of the gas
molecules moving at different speeds, between 𝑐1and 𝑐2, thus

3 2
−𝑚𝑐

( )
2 2𝑘 𝑇
2 𝑚 𝑏

f(𝑐) = 4Π𝑐 2Π𝑘𝑏𝑇

𝑒

Finally, the Maxwell-Boltzmann distribution can be used to

determine the distribution of the kinetic energy for a set of
molecules. The distribution of the kinetic energy is identical to
the distribution of the speeds for a certain gas at any
temperature.

● Most of the gases obey Maxwell-Boltzmann distribution

over a wide range of temperatures.
● Consider a gas having mono-atomic molecules. It is
assumed that the gas is ideal and has only kinetic energy
of translation. Intermolecular attraction is assumed to be
absent.
● The position ‘z’ can be written as

∞ 𝐸
− 𝑘𝑇
Z = ∫𝑒 𝑔(𝐸)𝑑𝐸 →(1)
0

( )
3
4Π( 2𝑚 ) 1/2
We know g(E) dE = 3 𝐸 𝑑𝐸 →(2)
ℎ

Here V is the volume occupied by the gas and ‘h’ is

Planck's constant.

Therefore,

( )∫ 𝐸
3 𝐸
4Π( 2𝑚 ) 1/2 −( 𝑘𝑇 )
Z = 3 𝑒 𝑑𝐸
ℎ 0
 ⎡ ⎤
( )
3 3
4Π( 2𝑚 ) Π(𝑘𝑇)
Z = 3
⎢ ⎥
ℎ ⎢ 2 ⎥
⎣ ⎦
3/2
(2Π𝑚𝑘𝑇)
Z = V 3 →(3)
ℎ

Equation ( 3) represents the position function for an ideal gas

(mono-atomic) in terms of the volume and temperature.

Taking log on both sides of the equation (3) we get,

3/2
𝑙𝑜𝑔𝑒𝑍 = 𝑙𝑜𝑔𝑒 ⎡⎢
(2Π𝑚) 𝑉 ⎤+ 𝑙𝑜𝑔 (𝑘𝑇)3/2
3 ⎥ 𝑒
⎣ ℎ ⎦

𝑙𝑜𝑔𝑒𝑍 = C + 3/2 𝑙𝑜𝑔𝑒𝑘𝑇→ (4)

𝐸𝑎𝑣𝑔 = 𝑎𝑣𝑒𝑟𝑎𝑔𝑒 𝑒𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒

2 𝑑
Therefore, 𝐸 = (𝑘𝑇 ) (𝑙𝑜𝑔𝑒𝑍)
𝑎𝑣𝑔 𝑑𝑇
 2
𝐸𝑎𝑣𝑔 = (𝑘𝑇 )
𝑑
𝑑𝑇 [𝑐 + 3/2𝑙𝑜𝑔𝑒𝑘𝑇]
2 𝑑
𝐸𝑎𝑣𝑔 = (𝑘𝑇 ) 𝑑𝑇
[ c +3/2𝑙𝑜𝑔𝑒𝑘 + 3/2 𝑙𝑜𝑔𝑒𝑇]

Therefore average energy of the particle(𝐸𝑎𝑣𝑔)= 3/2 kT →(5)

The total energy, U = N𝐸

𝑎𝑣𝑔

U = N[3/2 kT]

U = 3/2 NkT → (6)

Plotting the Maxwell-Boltzmann Distribution Function

Figure 1 shows the Maxwell-Boltzmann distribution of speeds
for a certain gas at a certain temperature, such as nitrogen at
298 K. The speed at the top of the curve is called the most
probable speed because the largest number of molecules
have that speed.
Figure 1: The Maxwell-Boltzmann distribution is shifted
to higher speeds and is broadened at higher
temperatures.

Figure 2 shows how the Maxwell-Boltzmann distribution

is affected by temperature. At lower temperatures, the
molecules have less energy. Therefore, the speeds of
the molecules are lower and the distribution has a
smaller range. As the temperature of the molecules
increases, the distribution flattens out. Because the
molecules have greater energy at higher temperature,
the molecules are moving faster.

Figure 2: The Maxwell-Boltzmann distribution is shifted to

higher speeds and is broadened at higher temperatures.
MAXWELL DISTRIBUTION LAW OF
VELOCITIES

Let us consider an ideal gas contained in a container

of volume V.

Applying Maxwell’s law in equilibrium, the number of

molecules in a cell of energy E,will be

β𝐸𝑖
𝑛𝑖 = 𝐴𝑒 [β = 𝑚𝑢𝑙𝑡𝑖𝑝𝑙𝑖𝑒𝑟]

The no of molecules having position coordinates on

the range of x to x+dx, y to y+dy, z to z+dz and the
velocity components in the ranges
𝑉𝑋 𝑡𝑜 𝑑𝑉𝑋, 𝑉 𝑡𝑜 𝑑𝑉𝑦, 𝑉 𝑡𝑜 𝑑𝑉𝑧 will be proportional to
𝑦 𝑧

the element of phase of volume.

According to maxwell- boltzmann law,

β𝐸𝑖
𝑛𝑖𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧=𝐴𝑒 𝑛𝑖𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧
→ (1)
 2
But 𝐸𝑖 = energy of the particle=1/2m𝑣 = 1/2 m(
2 2 2
𝑣𝑥 + 𝑣𝑦 + 𝑣𝑧 )

Substituting for 𝐸𝑖in equation (1), we get;

𝑛𝑖𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧=
2 2 2
−𝑚β[1/2(𝑣𝑥+𝑣𝑦+𝑣𝑧 )]
𝐴𝑒 𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧
→ (2)

The constant ‘A’ is evaluated by multiplying and

integrating equation (2) overall available volume and all
ranges of velocities.

Therefore
2 2 2
−𝑚β1/2(𝑣𝑥+𝑣𝑦+𝑣𝑧 )
N = ∫∫∫ ∫∫ ∫ 𝐴𝑒 𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧

2 2 2
−𝑚β1/2(𝑣𝑥+𝑣𝑦+𝑣𝑧 )
=∫∫∫ 𝑑𝑥𝑑𝑦𝑑𝑧 ∫∫ ∫ 𝐴𝑒

𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧
But ∫∫∫ 𝑑𝑥𝑑𝑦𝑑𝑧= volume of vessel containing gas
2 2 2
−𝑚β[1/2(𝑣𝑥+𝑣𝑦+𝑣𝑧 )]
N = AV ∫∫ ∫ 𝐴𝑒 𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧
2 2 2
∞ β𝑚𝑣𝑥 ∞ β𝑚𝑣𝑦 ∞ β𝑚𝑣𝑧
− − −
=AV ∫ 𝑒 2
d 𝑣𝑥 + ∫ 𝑒 2
d𝑣𝑦+ ∫ 𝑒 2
d𝑣𝑧→ (3)
−∞ −∞ −∞

Using standard definite integrals we have;

2 2
∞ β𝑚𝑣𝑥 ∞ β𝑚𝑣𝑦
− 2Π − 2Π
∫ 𝑒 2
d𝑣𝑥= 𝑚β
; ∫ 𝑒 2
d𝑣𝑦= 𝑚β
−∞ −∞

2
∞ β𝑚𝑣𝑧
− 2Π
∫ 𝑒 2
d𝑣𝑧= 𝑚β
−∞

Substituting these values in equation (3), we get

2Π 3/2 𝑚β 3/2
N = AV ( 𝑚β
) ⇒A = N/V ( 2Π
)

𝑚 3/2
A = N/V ( 2Π𝑘𝑇
) → (4)

1
Since β = 𝑘𝑇
Now substituting the value of A and β in the equation (1);

2 2 2
𝑚(𝑣𝑥+𝑣𝑦+𝑣𝑧 )
3/2 −
𝑛𝑖𝑑𝑥𝑑𝑦𝑑𝑧𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧= 𝑁/𝑉 ( 𝑚
2Π𝑘𝑇 ) 𝑒 2𝑘𝑇
𝑑𝑥𝑑𝑦𝑑𝑧 𝑑𝑉𝑋 𝑑𝑉𝑦𝑑𝑉𝑧

→(5)

The number of molecules having velocity coordinates in

the range irrespective of the position coordinates can be
found by integrating equation (5) with respect to position
coordinates.

2 2 2
𝑚(𝑣𝑥+𝑣𝑦+𝑣𝑧 )
3/2 −
𝑛𝑖𝑑𝑉𝑋𝑑𝑉𝑦𝑑𝑉𝑧= 𝑁/𝑉 ( 𝑚
2Π𝑘𝑇 ) 𝑒 2𝑘𝑇
𝑑𝑉𝑥𝑉 𝑑𝑉𝑧
𝑦
2 2 2
𝑚(𝑣𝑥+𝑣𝑦+𝑣𝑧 )
3/2 −
=N ( 𝑚
2Π𝑘𝑇 ) 𝑒 2
𝑑𝑉𝑥𝑑𝑉 𝑑𝑉𝑧 → (6)
𝑦

Lastly let us find the number of molecules having velocity

components in the range 𝑣𝑥 𝑡𝑜 𝑣𝑥 + 𝑑𝑉𝑥 irrespective of 𝑉𝑦.
This is obtained by integrating equation (5) with respect to
𝑉𝑦and 𝑉𝑧.
 2 2 2
𝑚(𝑣𝑥+𝑣𝑦+𝑣𝑧 )
− 2𝑘𝑇
3/2
n(𝑉𝑥)d𝑉𝑥 = N ( 𝑚
2Π𝑘𝑇 ) 𝑑𝑉𝑥 ∫∫ 𝑒 𝑑𝑉𝑥𝑑𝑉 𝑑𝑉𝑧
𝑦

2 2 2
𝑚𝑣𝑥 ∞ 𝑚𝑣𝑦 ∞ 𝑚𝑣𝑧
3/2 − − −
=N ( 𝑚
2Π𝑘𝑇 ) 𝑒 2𝑘𝑇
d 𝑉𝑥 ∫ 𝑒
−∞
2𝑘𝑇
𝑑𝑉𝑦 ∫ 𝑒
−∞
2𝑘𝑇
𝑑𝑉𝑧

2
𝑚𝑣𝑥
3/2 −
=N ( 𝑚
2Π𝑘𝑇 ) 𝑒 2𝑘𝑇
d𝑉𝑥⎡⎢
⎣
2Π𝑘𝑇
𝑚
*
2Π𝑘𝑇
𝑚
⎤
⎥
⎦

Therefore,

2
𝑚𝑣𝑥
1/2 −
n(𝑉𝑥)d𝑉𝑥=N ( 𝑚
2Π𝑘𝑇
𝑒) 2𝑘𝑇
d𝑉𝑥→ (7)

The probability that a molecule will have a x- component

of velocity in the range 𝑉𝑥+d𝑉𝑥is
2
𝑚𝑣𝑥
(𝑉𝑥) 1/2 −
P(𝑉𝑥)d𝑉𝑥= n 𝑁
d𝑉𝑥= ( 𝑚
2Π𝑘𝑇 )
𝑒 2𝑘𝑇
d𝑉𝑥→ (8)

Equation (7,8) represents Maxwell’s distribution law of

velocities.
MEAN , RMS AND MOST PROBABLE
SPEEDS
AVERAGE SPEED OF MOLECULES

● The average speed of molecules is the mean of all

magnitudes of velocity at which molecules of the given
gas are moving.

● The average speed of molecules can be calculated as an

integral of the Maxwell-Boltzmann distribution function
multiplied by the magnitude of velocity of a molecule v.
The variable of integration, velocity, can attain all
possible values, therefore we integrate from zero to
infinity.

● Let there be 𝑁 each having a velocity 𝑉 , then mean or

𝑖 𝑖

average speed (𝑉) is defined as

∑𝑁𝑖𝑉𝑖
𝑉 = 𝑖

∑𝑁𝑖
𝑖
 But ∑ 𝑁𝑖= N , the total number of molecules
𝑖

1
𝑉 = 𝑁
∑ 𝑁𝑖𝑉𝑖
𝑖

As the speed of molecules is approximately continuous,

we may replace summation sign by integration

∞
1
𝑉 = 𝑁
∫ 𝑉𝑁(𝑉)𝑑𝑉
0

2
∞ 3/2 𝑚𝑣
1 𝑚 2 −( )
= 𝑁
∫ 𝑉4Π𝑁[ 2Π𝑘𝑇
] . 𝑢𝑒 2𝑘𝑇
𝑑𝑉
0

2
𝑚𝑣
𝑚 3/2 2 −( )
[ N(V)dV = 4Π𝑁[ 2Π𝑘𝑇
] 𝑉𝑒 2𝑘𝑇
𝑑𝑉 ]

2
∞ 3/2 𝑚𝑣
𝑚 3 −( )
= ∫ 4Π [ 2Π𝑘𝑇
] . 𝑉𝑒 2𝑘𝑇
𝑑𝑉
0
2

𝑚 3/2 ∞ 3 −(
𝑚𝑣
)
= 4Π [ 2Π𝑘𝑇
] ∫𝑉 𝑒 2𝑘𝑇
𝑑𝑉
0
 3/2 2
= 4Π [
𝑚
] ⎡ 2(𝑘𝑇) ⎤
2Π𝑘𝑇 ⎢ 2 ⎥
⎣ 𝑚 ⎦

8𝑘𝑇 𝑘𝑇
𝑉= 𝑚Π
= 1.59 𝑚
This equation gives the average speed
of a gas molecule.

MOST PROBABLE SPEED

The most probable speed of gas molecules described by the

Maxwell-Boltzmann distribution is the speed at which the distribution
graph reaches its maximum. Thus, if we know the formula of this
distribution, we just need to differentiate it and consider the derivative
to be equal to zero. Speed for which the derivative equals zero is the
most probable speed.
Differentiating the most P(v) and equating it to zero in order to find its
extreme.
P(v) is given by

3/2 2 −𝑚𝑣2
● 4Π ( 𝑚
2Π𝑘𝑇 ) 𝑣 2𝑘𝑇 = P(V)

Differentiating the relation we get,

 2
𝑚𝑣
3/2⎡ ⎤
2
−𝑚𝑣 3 −
−
( )
2𝑘𝑇
𝑚 𝑚𝑣
4Π ⎢ 2𝑉𝑒 2𝑘𝑇
− 𝑒 ⎥= 0
2Π𝑘𝑇 ⎢ 𝑘𝑇 ⎥
⎣ ⎦

2
2 𝑚𝑣
−𝑚𝑣 3 −
− 𝑚𝑣 2𝑘𝑇
2𝑉𝑒 2𝑘𝑇
= 𝑘𝑇
𝑒

3
𝑚𝑣
2V = 𝑘𝑇

2 2𝑘𝑇
𝑉= 𝑚

2𝑘𝑇
Therefore V = 𝑚

(𝑉𝑚𝑝) 𝑖𝑠 𝑡ℎ𝑒 𝑚𝑜𝑠𝑡 𝑝𝑟𝑜𝑏𝑎𝑏𝑙𝑒 𝑠𝑝𝑒𝑒𝑑

2𝑘𝑇
𝑉𝑚𝑝 = 𝑚
ROOT MEAN SQUARE SPEED (𝑉𝑟𝑚𝑠)

● The root-mean-square speed of molecules is the

speed at which all the molecules have the same total
kinetic energy as in case of their actual speed.

● The root-mean-square speed can be calculated by

multiplying the Maxwell-Boltzmann distribution function
2
by 𝑉 .
2 ∞
2
(𝑉) = 1/𝑁 ∫ 𝑉 𝑁(𝑉)𝑑𝑉
0

2
∞ 3/2 2 − 𝑚𝑣
2 𝑚
= 1/N ∫ 𝑉 4ΠN ( 2𝑘𝑇Π ) 𝑉𝑒 2𝑘𝑇
dV
0

𝑚 3/2∞ 4
− 𝑚𝑣

= 4Π( 2𝑘𝑇Π ) ∫𝑉 𝑒 2𝑘𝑇

dV
0

𝑚 3/2⎡ 3 32Π(𝑘𝑇)
5 ⎤
=4Π( ) ⎢8 ⎥
2𝑘𝑇Π ⎢ 𝑚
5
⎥
⎣ ⎦
 2 3𝑘𝑇
Therefore (𝑉) = 𝑚

Taking square root on both sides we get,

𝑉𝑟𝑚𝑠= (𝑉) ]= 3𝑘𝑇

𝑚

The quantity (𝑉) gives root mean square speed of gas

molecules.

● The above graph shows the relation between

average speed, most probable speed and rms
speed.