Statistical Thermodynamics (multiple questions)

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SUMMARY

The discussion focuses on solving problems in Statistical Thermodynamics related to particle density in gravitational fields and open systems. The first problem demonstrates that the particle density follows the barometric height equation, ρ(h) = ρ(0)·exp(-mgh/kT), where m is the mass of the particle, g is the gravitational constant, h is the height, k is Boltzmann's constant, and T is the temperature. The second and third problems involve deriving the characteristic function X for systems at constant pressure and volume, respectively, using the grand canonical ensemble and Helmholtz energy concepts. The final conclusions clarify the derivation of the characteristic function as X = γ·A for the interface energy.

PREREQUISITES
  • Understanding of Hamiltonian mechanics and its application in thermodynamics.
  • Familiarity with the concepts of particle density and the barometric height equation.
  • Knowledge of grand canonical ensemble and partition functions.
  • Basic principles of Helmholtz free energy and its relation to thermodynamic potentials.
NEXT STEPS
  • Study the derivation of the barometric height equation in more detail.
  • Learn about the grand canonical ensemble and its applications in statistical mechanics.
  • Explore the Helmholtz free energy and its role in fixed volume systems.
  • Investigate the implications of interface energy in thermodynamic systems.
USEFUL FOR

Students and researchers in physics, particularly those specializing in statistical mechanics and thermodynamics, as well as educators seeking to deepen their understanding of particle behavior in various thermodynamic conditions.

vitom001
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Homework Statement



1.) For N particles in a gravity field, the Hamiltonian has a contribution of external potential only (-mgh). Show that the particle density follows the barometric height equation (1).

2.) For N particles in a open system at constant pressure p and temperature T, let there be an interface with area A in the system (eg. air-water), that is (μ, p, A, T). N, V and U fluctuate in this sytem. Identify the characteristic function X.(2)

3.) Same as above, only for a system where V instead of p is fixed.

Homework Equations



1.) ρ(h) = ρ(0)·exp(-mgh/kT), with m mass of particle, g gravitational constant, h barometric height, k boltzmann's constant and T temperature.

2.) X = - kT·lnΔ, where Δ is the partition function for the grand canonical ensemble.

3.) Same as above.

The Attempt at a Solution



1.) From: <N> = kT ∂lnΞ/∂μ = Lx·Ly·∫ρ(h)dh

I’m supposed to arrive at: ρ(h) = ∫[exp(μ/kT)/Λ3]·exp(-mgh/kT) dh

And finally to: ρ(h) = ρ(0) ·exp(-mgh/kT), where ρ(0) = exp(μ/kT)/Λ3

I understand the setup with the expectation value of N, however the transition to the integral and getting the ρ(0) out of the integral is not quite clear to me.
Also, Ξ is the grand-canonical partition function in this case, while Lx·Ly is neglected since they're both uniform and only the barometric height h is considered.2.) By using the equation X = - kT·lnΔ, with Δ = exp(S/k)·exp(-U/kT)·exp(μN/kT)·exp(-pV/kT), I arrive at
X = -ST + U - μN + pV
X = [ (U + pV) - ST ] - μN
X = (H-TS) -μN = G - μN

However, I know the characteristic function is supposed to be X = γ·A, so the energy stored in the interface. I do not understand how I arrive at that conclusion.

3.) Same procedure as above, only here the volume is fixed instead of the pressure, so the derivation should go through the helmholtz energy. I use the same formula X = - kT·lnΔ, however I'm also supposed to implement dF = -SdT - pdV + μdN + γdA, so to my guess the partition function may look something like this:

Δ = exp(S/k)·exp(-U/kT)·exp(μN/kT)·exp(-pV/kT)·exp(γA/kT)

which then gives:

X = (H-TS) -μN + γA = G - μN + γA

As with the previous question, I don't know how I should conclude from this what the characteristic function is.
 
Actually I managed to figure it out in the end, so thread can be closed.
 

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