Partition function, Ideal gas, Entropy

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For a diatomic gas near room temperature, the entropy can be expressed as S = Nk[ln(VZ_eZ_rot/Nv_Q) + 7/2]. The internal partition function combines the rotational partition function and the degeneracy of the electronic ground state, leading to the internal free energy F_int = -kT[ln(Z_rot) + ln(Z_e)]. The discussion highlights the confusion regarding the treatment of distinguishable versus indistinguishable particles in partition functions, noting that the correct approach for indistinguishable particles involves using Stirling's approximation for N!. Ultimately, the indistinguishability is already considered in the entropy equation, clarifying the initial confusion. Understanding these nuances is essential for accurately deriving thermodynamic properties in statistical mechanics.
Incand
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Homework Statement


For a diatomic gas near room temperature, the internal partion function is simply the rotational partition function multiplied by degeneracy ##Z_e## of the electronic ground state.
Show that the entropy in this case is
## S = Nk\left[ \ln \left( \frac{VZ_eZ_\text{rot}}{Nv_Q}\right) + \frac{7}{2}\right].##

Homework Equations


The entropy of an ideal gas is given by
##S = -\left( \frac{\partial F}{\partial T}\right)_{V,N} = Nk\left[ \ln \left( \frac{V}{Nv_q}\right) + \frac{5}{2} \right]-\frac{\partial F_\text{int}}{\partial T}.##

The rotational partion function should be
##Z_\text{rot} = \frac{kT}{2B}##
where ##B## is the rotational constant.

Helmholtz free energy
##F = -kT \ln Z##.

The Attempt at a Solution


The internal free energy is
##F_\text{int} = -kT\left[ \ln Z_\text{rot} + \ln Z_e\right].##
Which gives
##-\frac{\partial F_\text{int}}{\partial T} = k\left[\ln Z_\text{rot}Z_e+1\right].##
Apparantly this is for a single molecule and scaling this with ##N## give the correct answer.

However what I don't understand is if I want to derive it from the full partition function I should have ##Z_\text{int} = (Z_eZ_\text{rot})^N##. But this is the partition function for distinguishable particles. Shouldn't I instead have ##Z_\text{int} \approx \frac{1}{N!} (Z_eZ_\text{rot})^N## for undistinguishable particles?
 
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It's been quite a number of years since I worked through the details of some of these, but your last line looks correct for Maxwell-Boltzmann type statistics. You use Stirling's formula to evaluate ## ln (N!) =N ln(N)-N ##.
 
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Charles Link said:
It's been quite a number of years since I worked through the details of some of these, but your last line looks correct. You use Stirling's formula to evaluate ## ln (N!) =N ln(N)-N ##.

Well that's pretty much my question. The second statement seems correct to me but that wouldn't give the correct answer. Instead the the partition function for distinguishable particles give the correct answer which is confusing.

When thinking about it now, I think I see the reason for that. The indistinguishable particle part is already accounted for in the original equation (the ##N## there is indeed from stirlings approximation). And then it doesn't matter that the internal states are the same since we already accounted for that.
 
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