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 the volume of one part of a divided recipient increases by ΔV. The Helmholtz free energy (F) is utilized to determine the work done, with the equation W = ΔF = F(T,V+ΔV,N) - F(T,V,N). The incorrect calculation led to confusion, as the correct expression for work is W = aN²(2/V - 1/(V+ΔV) - 1/(V-ΔV)) + NKbT log((V-bN)²/((V+ΔV-bN)(V-ΔV-bN))). This highlights the importance of correctly applying thermodynamic principles in calculations.

PREREQUISITES
  • Understanding of Van der Waals gas equations
  • Familiarity with Helmholtz free energy calculations
  • Knowledge of thermodynamic work and reversible processes
  • Basic principles of statistical mechanics and thermodynamics
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  • Study the derivation of the Helmholtz free energy for different gas models
  • Learn about the implications of the Van der Waals equation on real gas behavior
  • Explore integration techniques for calculating work in thermodynamic systems
  • Investigate the relationship between free energy and equilibrium in thermodynamic processes
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Students and professionals in physics, particularly those specializing in thermodynamics, as well as researchers working with gas laws and energy calculations in physical chemistry.

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1. Homework Statement [/b]

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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Calculate the work done by the gas by integrating PdV for both parts and adding them.

ehild
 

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