Partition function, Ideal gas, Entropy

In summary: But it does matter for the rotational partition function since it's only accounting for distinguishable particles.
  • #1
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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  • #2
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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  • #3
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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1. What is the purpose of the partition function in thermodynamics?

The partition function is a mathematical tool used in thermodynamics to calculate the thermodynamic properties of a system. It represents the sum of all possible states that a system can be in, and is used to determine the system's energy, entropy, and other thermodynamic quantities.

2. How is the partition function related to the ideal gas law?

The partition function is directly related to the ideal gas law through the Boltzmann factor. The Boltzmann factor is the ratio of the partition function to the total number of particles in the system, and is used to calculate the probability of a particle being in a certain energy state. This relationship allows for the calculation of the thermodynamic properties of an ideal gas using the partition function.

3. What is the significance of entropy in thermodynamics?

Entropy is a measure of the disorder or randomness in a system. In thermodynamics, it is a fundamental quantity used to describe the direction of energy flow and the availability of energy to do work. The second law of thermodynamics states that the total entropy of a closed system will always increase over time, indicating that systems tend to become more disordered.

4. How does the partition function change when the temperature of a system increases?

The partition function is directly proportional to the temperature of a system. As the temperature increases, the average energy of the particles in the system also increases. This leads to a larger number of accessible energy states, resulting in a larger partition function.

5. Can the partition function be used to calculate the thermodynamic properties of a non-ideal gas?

Yes, the partition function can be used to calculate the thermodynamic properties of non-ideal gases, although it becomes more complex as it takes into account intermolecular interactions. In these cases, the partition function can be approximated using various models, such as the Van der Waals equation, to account for these interactions.

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