Avogadro’s Number from Maxwell Boltzmann Distribution law:

It is found that as we go higher up sea level, the pressure of the atmosphere decreases.
The variation of pressure with altitude is given by the so-called barometric formula.
Let us consider vertical a cylinder of uniform cross section A containing a gas in which
the molecules have come into equilibrium with gravity, the only force acting on them. Let P be
the gas pressure at the height h from the bottom of the cylinder, and P- dp be the pressure at the
height h + dh.

Since the equilibrium exists in the cylinder, it is evident that the difference in the pressure
of two layers dh apart, acting upward, must be balanced by the gravitational force acting
downward. If the area of cross section of the cylinder is A, density of the gas is ρ at pressure, P.
We know pressure is defined as
𝑭
𝑷= 𝒐𝒓 𝑭 = 𝑨 × 𝑷
𝑨
𝑭𝒖𝒑𝒘𝒂𝒓𝒅 = 𝑨 × 𝒅𝑷 … … … (𝟏)

Downward force is due to weight.

𝑭𝑫𝒐𝒘𝒏𝒘𝒂𝒓𝒅 = 𝒘 = 𝒎𝒈 … … … (𝟐)
We know density is given as.
𝒎
𝝆=
𝑽
or
𝒎 = 𝑽. 𝝆 … … … (𝟑)
Putting the value of m in equation (2) becomes.
 𝑭𝑫𝒐𝒘𝒏𝒘𝒂𝒓𝒅 = 𝒘 = 𝑽. 𝝆. 𝒈 … … … (𝟒)
The area of the cross section of the cylinder is A = π. r2 and height is dh, so volume of the
cylinder is V = A. dh, so equation (4) becomes.
𝑭𝑫𝒐𝒘𝒏𝒘𝒂𝒓𝒅 = 𝒘 = 𝑨. 𝒅𝒉. 𝝆. 𝒈
At equilibrium, the two forces are equal.
𝑭𝒖𝒑𝒘𝒂𝒓𝒅 = 𝑭𝑫𝒐𝒘𝒏𝒘𝒂𝒓𝒅

𝑨 × 𝒅𝑷 = 𝑨. 𝒅𝒉. 𝝆. 𝒈
Or
𝒅𝑷 = 𝒅𝒉. 𝝆. 𝒈
Since pressure decreases with altitude so the above equation becomes.
−𝒅𝑷 = 𝒅𝒉. 𝝆. 𝒈
Or
𝒅𝑷 = −𝝆. 𝒈. 𝒅𝒉 … … … (𝟓)
We know kinetic gas equation.
𝟏
𝑷𝑽 = 𝒎𝒏𝑼𝟐
𝟑
𝟏
𝑷𝑽 = 𝑴𝑼𝟐
𝟑
Multiply and divide the above equation with 2.
𝟐 𝟏
𝑷𝑽 = × 𝑴𝑼𝟐
𝟑 𝟐
1
We know 𝐸𝑘 = 2 𝑀𝑈 2

𝟐
𝑷𝑽 = 𝑬
𝟑 𝒌
or
𝟐𝑬𝒌
𝑽= … … … (𝟔)
𝟑𝑷
The density of one mole a gas is give as.
𝑴
𝝆=
𝑽
Putting the value of density in above equation from equation (6)
 𝟑𝑷𝑴
𝝆= … … … (𝟕)
𝟐𝑬𝒌
Now putting the value of density from equation (7) in equation (5) we get.
𝟑𝑷𝑴𝒈𝒅𝒉
𝒅𝑷 = −
𝟐𝑬𝒌
Or
𝒅𝑷 𝟑𝑴𝒈𝒅𝒉
− =
𝑷 𝟐𝑬𝒌
If Po is the pressure at any arbitrary level when h = 0 and P the pressure at height h, then by
integration.
𝑷 𝒉
𝒅𝑷 𝟑𝑴𝒈
∫− = ∫ 𝒅𝒉
𝑷 𝟐𝑬𝒌
Po 𝟎

𝟑𝑴𝒈𝒉
−[𝒍𝒏𝑷 − 𝒍𝒏Po ] =
𝟐𝑬𝒌
𝟑𝑴𝒈𝒉
[𝒍𝒏𝑃𝑜 − 𝒍𝒏𝑷] =
𝟐𝑬𝒌
𝑃𝑜 𝟑𝑴𝒈𝒉
𝒍𝒏 =
𝑷 𝟐𝑬𝒌
Since the pressure of any gas is proportional to the number of molecules per unit volume.
𝑛𝑜 𝟑𝑴𝒈𝒉
𝒍𝒏 = … … … (𝟖)
𝒏 𝟐𝑬𝒌
where no refers to the number of molecules at h = 0 and n the number of molecules at height h.
Equation (7) will also apply when no and n represent the number of molecules per unit volume at
any two levels at a distance h apart. The above equation describes the vertical distribution of
molecules under the influence of gravity, and Perrin supposed that it would also represent the
distribution of microscopic particles when suspended in a liquid. For suspension of this kind the
quantity Mg is replaced as
𝝆′
𝑴𝒈 = 𝑵𝑨 𝒎𝒈(𝟏 − )
𝝆
where NA is the Avogadro's number, m is the mass of single particle, 𝝆′ and 𝝆′ are the densities
of the particles and liquid media in which they can be suspended respectively. The introduction
of 𝝆′ / 𝝆 is necessary, in accordance with the principle of Archimedes, because of the upward
thrust on the particles due to the displacement of their own volume of liquid. Further the kinetic
energy of all molecules in one mole of gas is equal to 3/2 RT. Making necessary alterations in
equation (8) the equation for the number of particles no and n at levels separated by a vertical
distance h is given by.
𝑛𝑜 𝟑𝑵𝑨 𝒎𝒈𝒉 𝝆′
𝒍𝒏 = (𝟏 − ) … … … (𝟗)
𝒏 𝟐𝑬𝒌 𝝆
We know.
𝟐
𝑷𝑽 = 𝑬
𝟑 𝒌
PV = RT
so
𝟐
𝑹𝑻 = 𝑬
𝟑 𝒌
𝟑
𝑬𝒌 = 𝑹𝑻
𝟐
Substituting the value of Ek we get.
𝑛𝑜 𝑵𝑨 𝒎𝒈𝒉 𝝆′
𝒍𝒏 = (𝟏 − )
𝒏 𝑹𝑻 𝝆
or
𝑛𝑜 𝝆 − 𝝆′
𝑹𝑻𝒍𝒏 = 𝑵𝑨 𝒎𝒈𝒉 ( ) … … … (𝟏𝟎)
𝒏 𝝆
If r is the radius of the particle than it volume would be V = 4/3π r3, if it were spherical and its
mass would m = 4/3π r3ρ. (ρ = density). Substituting this value in equation
𝑛𝑜 𝝆 − 𝝆′
𝑹𝑻𝒍𝒏 = 𝑵𝑨 𝟒/𝟑𝛑 𝐫𝟑ρ𝒈𝒉 ( )
𝒏 𝝆
𝑛
𝟑𝑹𝑻𝒍𝒏 𝒏𝑜
𝑵𝑨 = … … … (𝟏𝟏)
𝟒𝛑𝐫 𝟑 𝒈𝒉(𝝆 − 𝝆′ )
If the ratio of the number of the particle of known density and radius at two different levels of
suspensions in equilibrium with gravity are known the equation (11) can be used to determine the
value of Avogadro’s number.