Derivation of Boltzmann distribution law

• i)Deriving an expression for lnW

• Consider a closed system of N independent particles,occupying
different energy states,assume them to be noninteracting.,total
energy is a sum of their individual energies and is constant.
• No,N1,N2…molecules in the available energy states Ԑ0, Ԑ1,
Ԑ3….respectively
• W=N!/N0!.N1!.N2! …….(1)
• =N!/ΣNi!
• lnW=lnN! –ΣlnNi! …..(2)
• For large x, stirlings approximation is lnx!=xlnx-x,we can apply this
approximation in equation (2)
lnW = N lnN – N - Σ(Ni lnNi - Ni)
= N lnN – N - ΣNi lnNi + ΣNi
= N lnN – ΣNi lnNi ( ΣNi =N)……(5)
Evaluating ΣNi lnNi for the most probable distribution.

The most probable distribution is the one with the maximum W and
hence maximum lnW.
a)The total number of molecules (N)is constant.
• N= ΣNi = constant
• dN= ΣdNi =0
• B)the total energy of the system is constant
• Iii) using lagrange undetermined multipliers α and β
Put β=1/kT in equation…(24),we get Boltzmann Distribution law
as,