Thermodynamics - Change in the free energy

In summary: Then, using the equations for U and F given, the work done by the system can be calculated as:$$W=\Delta F = aN^2\left(\frac{2}{(V+\Delta V)^2}-\frac{1}{V+\Delta V}-\frac{1}{V^2}+\frac{2}{V^2}-\frac{1}{V-\Delta V}-\frac{1}{(V-\Delta V)^2}\right) + NK_BT\ln\left(\frac{(V-bN)^2}{(V+\Delta V-bN)(V-\Delta V-bN)}\right)$$In summary, the conversation discusses a system consisting of a Van der
  • #1
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=[itex]\frac{3}{2}[/itex]NKbT - a[itex]\frac{N^2}{V}[/itex]

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

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([itex]\frac{2}{V}[/itex]-[itex]\frac{1}{V+ΔV}[/itex]-[itex]\frac{1}{V-ΔV}[/itex])+NKBT log([itex]\frac{(V-bN)^2}{(V+ΔV-bN)(V-ΔV-bN}[/itex])

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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  • #2
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:
$$\Delta F=F(T, V+\Delta V,N)+F(T,V-\Delta V,N)-2F(T,V,N)$$
 

1. What is the concept of free energy in thermodynamics?

Free energy is a thermodynamic property that measures the amount of energy in a system that is available to do work. It takes into account both the system's internal energy and the effects of its surroundings.

2. How is the change in free energy related to spontaneity?

The change in free energy, represented by the symbol ΔG, is related to spontaneity in a reaction. If ΔG is negative, the reaction is considered spontaneous, meaning that it will occur without the input of additional energy. If ΔG is positive, the reaction is non-spontaneous and will require an input of energy to occur.

3. What is the equation for calculating the change in free energy?

The equation for calculating the change in free energy is ΔG = ΔH - TΔS, where ΔH is the change in enthalpy, T is the temperature in Kelvin, and ΔS is the change in entropy.

4. How does temperature affect the change in free energy?

Temperature, represented by the variable T, has a direct effect on the change in free energy. As temperature increases, the change in free energy becomes more negative, making reactions more spontaneous. Conversely, as temperature decreases, the change in free energy becomes less negative, making reactions less spontaneous.

5. Can the change in free energy be used to predict the direction of a reaction?

Yes, the change in free energy can be used to predict the direction of a reaction. A negative ΔG indicates that the reaction is spontaneous and will proceed in the forward direction, while a positive ΔG indicates that the reaction is non-spontaneous and will proceed in the reverse direction. A reaction with a ΔG of zero is at equilibrium.

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