Thermodynamics - Change in the free energy

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SUMMARY

The discussion focuses on calculating the work done by a Van der Waals gas when reversible work is applied to increase the volume of one compartment in a system at equilibrium. The Helmholtz free energy (F) is central to this calculation, defined by the equation F=U-TS, where U is the internal energy. The original attempt to calculate work (W) using W=ΔF was incorrect due to neglecting the contributions from both compartments. The correct formula for the change in Helmholtz free energy is ΔF=F(T, V+ΔV,N)+F(T,V-ΔV,N)-2F(T,V,N).

PREREQUISITES
  • Understanding of Van der Waals gas behavior
  • Familiarity with Helmholtz free energy and its significance in thermodynamics
  • Knowledge of reversible processes and work calculations in thermodynamic systems
  • Basic proficiency in thermodynamic equations and variables (U, T, S, V, N)
NEXT STEPS
  • Study the derivation of Helmholtz free energy for different thermodynamic systems
  • Learn about the implications of reversible work in thermodynamics
  • Explore the Van der Waals equation and its applications in real gases
  • Investigate the relationship between Helmholtz free energy and other thermodynamic potentials
USEFUL FOR

Students and professionals in thermodynamics, particularly those studying gas behavior, energy calculations, and the principles of reversible processes. This discussion is beneficial for anyone looking to deepen their understanding of Helmholtz free energy in practical applications.

Jalo
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Homework Statement



Consider a Van der Waals gas.
Consider a recipient of volume 2V, with a mobile wall (with no friction) that divides the recipient in two, each part having exactally N particles. The system is at equilibrium and the mobile wall is exactally in the middle of the recipient.

Consider that the system is in contact with a heat reservoir of temperature T.
Now imagine reversible work is realized on the system so that the volume of oe of the parts increases ΔV.Find the work done by the system. (The work given in a reversible process to a system is equal to the decrease of the Helmholtz free energy)

Homework Equations



F=U-TS

U=\frac{3}{2}NKbT - a\frac{N^2}{V}

F(T,V,N)=-\frac{aN^2}{V}-NKbT [ log(V-bN) + \frac{3}{2}log(\frac{3}{2}KbT)-log(N)+log(c)-\frac{3}{2} ]

The Attempt at a Solution



I found the function F(T,V,N) in the first exercise. Since the work done by the system is equal to the decrease of the Helmholtz free energy ( dW = -dF ) I just calculated

W=ΔF=F(T,V+ΔV,N) - F(T,V,N)

The answer I got was incorrect tho... The correct answer is:

W=aN2(\frac{2}{V}-\frac{1}{V+ΔV}-\frac{1}{V-ΔV})+NKBT log(\frac{(V-bN)^2}{(V+ΔV-bN)(V-ΔV-bN})

I'm a little confused as to why my resolution isn't correct.. If anyone could give me a hand I'd appreciate.

Thanks.
 
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The OP had the right idea, but he didn't consider the work done on both compartments; he only considered one compartment. The equation for the change in Helmholtz free energy for both compartments should have been:
$$\Delta F=F(T, V+\Delta V,N)+F(T,V-\Delta V,N)-2F(T,V,N)$$
 

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