Relating Helmholtz & Gibbs Free Energy: F=G-PdV+VdP

In summary, the conversation discusses the relationship between Helmholtz and Gibbs free energy. The equation F=G-PdV is proposed, with PdV being the work due to pressure. However, it is later clarified that the actual equation is F=G-PdV-VdP, where VdP is the work due to pressure and V is not constant if dV is non-zero. The conversation also mentions the displacement in the system as a result of non-zero dV, leading to work.
  • #1
iScience
466
5
i'm trying to relate the helmholtz and the gibbs free energy together. I thought that since the gibbs was just the W(other) and the helmholtz was the total work, that the following would be true.

F=G-PdV

because.. i thought that PdV was the work due to pressure, but it turns out that it's actually PdV+VdP which is just d(PV)

but i thought PdV was the only term that was the work due to pressure, how is VdP work due to pressure? V is constant!
 
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  • #2
iScience said:
it turns out that it's actually PdV+VdP which is just d(PV)

but i thought PdV was the only term that was the work due to pressure, how is VdP work due to pressure? V is constant!

V is not constant if dV is non-zero, right? Indeed, if V were constant the pressure wouldn't be doing any work (just as a weight sitting stationary on a rigid table does no work on the table).
 
  • #3
i know dV isn't zero, this is what gives rise to a displacement in the system which ultimately gives rise to work.
i was referring to V, not dV. for the VdP term, i thought we were keeping V constant and varying P.
 

1. What is Helmholtz free energy?

Helmholtz free energy, also known as A, is a thermodynamic potential that measures the amount of work that can be extracted from a thermodynamic system at a constant temperature and volume.

2. What is Gibbs free energy?

Gibbs free energy, also known as G, is a thermodynamic potential that measures the amount of work that can be extracted from a thermodynamic system at a constant temperature and pressure.

3. How are Helmholtz and Gibbs free energy related?

Helmholtz and Gibbs free energy are related by the equation F = G - PdV + VdP. This equation shows the relationship between the two potentials at constant temperature and pressure, where P is pressure, V is volume, and d represents the differential operator.

4. What does the equation F = G - PdV + VdP represent?

The equation F = G - PdV + VdP represents the change in Helmholtz free energy (A) with respect to changes in pressure and volume at constant temperature. It is often used to calculate the spontaneous direction of a chemical reaction or physical process.

5. How can the equation F = G - PdV + VdP be used in practical applications?

The equation F = G - PdV + VdP can be used to determine the spontaneity of chemical reactions and physical processes, as well as to calculate the maximum work that can be extracted from a system at constant temperature and pressure. It is also used in thermodynamic calculations and analyses in various scientific fields.

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