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

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SUMMARY

The discussion focuses on the relationship between Helmholtz free energy (F) and Gibbs free energy (G) in thermodynamics. The equation F = G - PdV is examined, with clarification that the correct expression includes the term VdP, leading to the full differential d(PV). Participants emphasize that while PdV represents work done by pressure, the VdP term also contributes to work when volume is not constant. This highlights the importance of understanding how both terms interact in thermodynamic systems.

PREREQUISITES
  • Understanding of thermodynamic principles, specifically Helmholtz and Gibbs free energy.
  • Familiarity with differential calculus as it applies to thermodynamic equations.
  • Knowledge of the first law of thermodynamics and work-energy principles.
  • Basic grasp of pressure-volume work in thermodynamic systems.
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  • Study the derivation of the Gibbs free energy equation and its applications in thermodynamics.
  • Explore the implications of the Maxwell relations in thermodynamic systems.
  • Learn about the concept of enthalpy and its relationship to Gibbs free energy.
  • Investigate real-world applications of Helmholtz and Gibbs free energy in chemical reactions.
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This discussion is beneficial for students and professionals in thermodynamics, chemical engineering, and physical chemistry, particularly those looking to deepen their understanding of energy relationships in thermodynamic processes.

iScience
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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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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).
 
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.
 

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