Partition Function at a Fixed Pressure

In summary, the conversation discusses a problem and its solution involving a system of noninteracting molecules in a container with a piston. The partition function and thermodynamic potential are derived, and there is a discussion about discrepancies in the solution. Ultimately, it is concluded that the expressions for the partition function and thermodynamic potential are equivalent.
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MathematicalPhysicist
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Homework Statement


I don't quite follow the solution to this problem (problem 2.11 in Bergersen's and Plischke's textbook), here are the quoted problem and its solution:

problem:
Consider a system of ##N## noninteracting molecules in a container of
cross-sectional area ##A##. The bottom of the container (at ##z = 0##) is rigid.
The top consists of an airtight piston of mass ##M## which slides without
friction.
(a) Construct the partition function ##Z## of the ##(N + 1)##-particle system
(##N## molecules of mass ##m##, one piston of mass ##M##, cross-sectional area
##A##). You may neglect the effect of gravity on the gas molecules.
(b) Show that the thermodynamic potential ##—k_BT\ln Z## is, in the ther-
modynamic limit, identical to the Gibbs potential of an ideal gas of
##N## molecules, subject to the pressure ##P = Mg/A##.

solution:
(a) The Hamiltonian for the system consisting of ##N## particles plus the frictionless piston of mass ##M## is $$H = \sum_{i=1}^N p_i^2/(2m)+P_z^2/(2M) +Mgz$$

The partition function for a single gas molecule in a volume ##V=Az## is ##Z_1 = \frac{Az}{\lambda^3}## where $$\lambda = \sqrt{\frac{h^2}{2\pi m k_B T}}$$
The partition function for the complete system is then:
$$ Z = \frac{A^N}{N!\lambda^{3N}} \int_{-\infty}^\infty \frac{dP_z}{h}e^{\frac{-\beta P_z^2}{2M}}\int_0^\infty dz z^N e^{-\beta Mgz}$$
or
$$Z = \frac{A^N(\beta Mgz)^{N+1}}{\lambda^{3N}} \sqrt{\frac{2\pi M}{\beta h^2}}$$
We find $$(2.10) \ \ \ \ -k_B T \ln Z = - Nk_B T \ln \bigg(\frac{Ak_B T}{\lambda^3 Mg}\bigg)$$

(b) It was shown in the text that the chemical potential is given by $$ (2.11) \ \ \ \ \mu = k_B T \ln \bigg( \frac{N\lambda^3}{V} \bigg) = G/N$$

Identifying the pressure as ##Mg/A## and using the ideal gas law ##PV=Nk_B T## we see that ##(2.10)## and ##(2.11)## are equivalent.

Homework Equations

The Attempt at a Solution


My problem is with the solution to (a), it seems they plugged into the LHS of (2.10) ##Z= Z_1^N## where ##k_B T = Mgz## and not the expression ##Z = \frac{A^N(\beta Mgz)^{N+1}}{\lambda^{3N}} \sqrt{\frac{2\pi M}{\beta h^2}}##, are they equivalent?

It doesn't look like that? what do you think?
 
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  • #2
MathematicalPhysicist said:
My problem is with the solution to (a), it seems they plugged into the LHS of (2.10) ##Z= Z_1^N## where ##k_B T = Mgz## and not the expression ##Z = \frac{A^N(\beta Mgz)^{N+1}}{\lambda^{3N}} \sqrt{\frac{2\pi M}{\beta h^2}}##, are they equivalent?

I don't understand the reason for the ##z^N## factor in the integrand below
upload_2017-10-16_14-0-22.png

[EDIT: Never mind, I see where the ##z^N## is coming from.]

With this expression for ##Z##, then the next equation should read
upload_2017-10-16_14-8-41.png
where the exponent (N+1) should be -(N+1). Also, I don't think the ##z## in ##(\beta Mgz)## should be there. Of course, you should check this.

Then you get (2.10) if you assume N is very large and neglect certain small terms.
 
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What is the partition function at a fixed pressure?

The partition function at a fixed pressure is a thermodynamic quantity that represents the sum of all possible states of a system at a given pressure. It takes into account the energy levels and the multiplicity of each state.

Why is the partition function at a fixed pressure important?

The partition function at a fixed pressure is important because it allows us to calculate the thermodynamic properties of a system, such as the internal energy, entropy, and free energy, at a given pressure. It also helps us understand the distribution of particles among different energy levels.

How is the partition function at a fixed pressure calculated?

The partition function at a fixed pressure is calculated by summing over all possible energy states of a system at a given pressure. This can be done analytically or numerically, depending on the complexity of the system.

What is the relationship between the partition function and the pressure of a system?

The partition function and pressure of a system are related through the thermodynamic equation of state, which states that the partition function is proportional to the pressure of a system. This means that as the pressure increases, the partition function also increases.

How does the partition function change at different pressures?

The partition function changes at different pressures because the pressure affects the distribution of particles among energy states. As the pressure increases, the number of available energy states increases, leading to a higher partition function.

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