Derivation of the Boltzmann Distribution

In summary, the conversation discusses the Lagrange Multiplier method used to derive the Boltzmann distribution. There is confusion about the correct form of the equation, specifically whether N can be replaced with N=\sum_{i=1}^n N_i before taking the partial derivative. The expert clarifies that the partial derivative is the correct approach because N is a constant and the constraint on N must be taken into account. The expert also explains the difference between partial and complete derivatives and how to determine the correct form of the equation.
  • #1
Peter Forbes
3
0
I have a question about the Lagrange Multiplier method used to derive the Boltzmann distribution. I'm following the first http://en.wikipedia.org/wiki/Maxwell%E2%80%93Boltzmann_statistics" .

I can get to this equation fine:
a35dba0357e0d45d9f2ef9844a8c5819.png


And I understand how they get the next line,
[itex]
\frac{df}{dN_i}=\ln{g_i}-\ln{N_i}-(\alpha+\beta \epsilon_i)
[/itex]
by considering N a constant when they do the partial differentiation.

However, since [itex] N=\sum_{i=1}^n N_i [/itex], can't I substitute that expression everywhere I have a N in the first equation? Then the differentiation gives me
[itex]
\frac{df}{dN_i}=\ln{(\sum_{i=1}^n N_i)}+(\alpha-1)(\sum_{i=1}^n N_i)+\ln{g_i}-\ln{N_i}-(\alpha+\beta \epsilon_i)
[/itex]

Which clearly has a different solution. Substituting for N before doing the partial derivative changes things...but why? I don't understand how one way should be any "more correct" than the other.

Thanks in advance.
 
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  • #2
Actually you misquoted the Wikipedia page, it doesn't say
[itex]
\frac{df}{dN_i}=\ln{g_i}-\ln{N_i}-(\alpha+\beta \epsilon_i)
[/itex]
but it says
[itex]
\frac{\partial f}{\partial N_i}=\ln{g_i}-\ln{N_i}-(\alpha+\beta \epsilon_i).
[/itex]

The difference is the d on the left-hand side. If you do a partial derivation (with the curly d) with respect to [itex]N_i[/itex] then you get the result that is given, because we can treat N as a constant. If you do a complete derivation (with the straight d) then indeed you get some extra terms:
[tex]\frac{df}{dN_i} = \frac{\partial f}{\partial N_i} + \frac{\partial f}{\partial N} \frac{\partial N}{\partial N_i}[/tex]
assuming that none of the other quantities ([itex]g_i, \epsilon_i, \ldots[/itex]) depends on Ni implicitly.

In this case, the partial derivative is the correct one because you are allowing the Ni's to vary, but you have a constraint on N (namely that the total number of particles is fixed, so N cannot change - therefore it is no use varying N and seeing if the function can be made smaller).
 
  • #3
OK, thanks for the help.
But I still don't understand why we can't replace N with [itex]N=\sum_{i=1}^n N_i[/itex] in the equation before we do the partial differentiation.

Note the first equation could be written
[itex]f(N_1,...N_n)=N\ln(N)-N + \alpha N + \beta E + N \sum_{i=1}^n (N_i \ln(g_i) - N_i \ln (N_i)-(\alpha+\beta \epsilon_i) N_i)[/itex]

Where I've put the N outside the sum rather than the Ni's inside the sum. But the Ni's inside the sum are not treated as constants.

I understand that the partial derivatives mean keeping everything but the one variable constant. But there are equivalent ways of writing the same expression, which gives different answers after partial differentiation.

So I guess my question is, how would one know what form is the "correct one" to use before applying the partial differentiation?
 

What is the Boltzmann Distribution?

The Boltzmann Distribution is a probability distribution that describes the distribution of particles in a system at a given temperature. It is used in statistical mechanics to calculate the probability of a particle having a certain energy level.

What is the significance of the Boltzmann Distribution?

The Boltzmann Distribution is significant because it allows us to understand the behavior of particles in a system at a given temperature. It helps us calculate the most probable energy state of a particle and the overall distribution of particles in the system.

How is the Boltzmann Distribution derived?

The Boltzmann Distribution is derived from the fundamental principles of thermodynamics and statistical mechanics. It takes into account the number of particles in a system, the energy levels of those particles, and the temperature of the system.

What are the assumptions made in the derivation of the Boltzmann Distribution?

The derivation of the Boltzmann Distribution assumes that the particles in the system are in thermal equilibrium, meaning they have reached a stable temperature. It also assumes that the particles are identical and have no interactions with each other.

How is the Boltzmann Distribution used in practical applications?

The Boltzmann Distribution is used in various fields of science, such as physics, chemistry, and biology, to understand the behavior of particles at a given temperature. It is also used in engineering to design and optimize systems, such as thermoelectric devices and chemical reactions.

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