Enthelpy (H=U+PV) What is P, really?

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Discussion Overview

The discussion revolves around the concept of enthalpy, specifically the equation H = U + PV, and the interpretation of pressure (P) within this context. Participants explore the implications of changing volume and temperature on pressure and enthalpy, considering various scenarios in thermodynamic systems.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • One participant questions the meaning of pressure in the enthalpy equation, suggesting it may refer to the pressure of the surroundings, especially in cases where the surrounding pressure is zero.
  • Another participant asserts that P is the system pressure and that the equation assumes constant pressure, which may not always hold true.
  • There is a suggestion that enthalpy change (ΔH) is primarily useful in constant-pressure situations, raising doubts about its applicability in engines or refrigerators where pressure may vary.
  • Some participants propose a more general formulation for ΔH that includes integrals of pressure and volume changes, indicating that the original equation may not capture all scenarios.
  • Questions are raised about the presence of both ΔP * V and ΔV * P in the equations, with concerns about potential double counting of work done in the system.
  • Clarifications are made regarding the conditions under which terms become zero, depending on whether pressure or volume is held constant.

Areas of Agreement / Disagreement

Participants express differing views on the interpretation of pressure in the enthalpy equation and its implications for various thermodynamic processes. There is no consensus on the utility of the enthalpy equation in non-constant pressure situations, and multiple competing perspectives remain unresolved.

Contextual Notes

The discussion highlights the complexity of applying the enthalpy equation in real-world scenarios, particularly regarding the assumptions of constant pressure and the definitions of work in thermodynamics. Some mathematical steps and assumptions are not fully resolved.

InTuoVultu
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I'm studying for the Physics GRE and going over my thermo notes.
Ok, so for enthalpy change

(delta)H = (delta) U + P * (delta) V

H is enthalpy, U is just proportional to T
What pressure are they talking about?
If the volume and temperature are changing, then the internal pressure is definitely changing, but in this equation it seems to be constant through out the process. So I assume that this is supposed to mean the pressure of the surroundings.
But this is tricky.
If you have a box of gas in space, the surrounding pressure is zero. So it seems like the only enthalpy change would be due to U. But this doesn't seem right. So let's look at how it expands.
Some latch could get thrown during the process and allow the piston to slide out frictionlessly. Or the piston could be connected to a spring that would get compressed as the gas expanded. Or the piston could just be rusty and release energy as heat when it moves.

I feel like all of these scenarios would have a different enthalpy change, but the equation doesn't seem to account for this. I'm guessing there's something more interesting in the P factor. What does it really mean?
-thanks
 
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The P is system pressure, and the equation you give assumes a constant system pressure (which is not always the case). This form is useful when a system is at equilibrium with the pressure of its surroundings.

(Also, I don't agree that if the volume and temperature of a system are changing, then "the internal pressure is definitely changing.")
 
P is system pressure then?
I know that T and V changing does not imply that P changes. It just usually does when the system is not in mechanical contact with its surroundings.

So I'm guessing that (delta)H is only useful in a setup where the system is held at constant pressure? This means that (delta)H is not very useful when it comes to engines/refrigerators or any system that is not held at constant pressure.
 
Your equation above assumes constant P, so not surprisingly it's only useful for constant-pressure situations. For more general situations, we can calculate \Delta H by

\Delta H=\Delta U+\int P\,dV+\int V\,dP

or

\Delta H=\int C_P\,dT
 
Mapes said:
Your equation above assumes constant P, so not surprisingly it's only useful for constant-pressure situations. For more general situations, we can calculate \Delta H by

\Delta H=\Delta U+\int P\,dV+\int V\,dP

or

\Delta H=\int C_P\,dT


Can u please explain why there is both Delta P * V and Delta V * P?

Would this not take Work into account twice?

When P is constant, the Delta P * V term = 0?

When V is constant, the Delta V * P term =0? I am just guessing
 
ILovePhysics! said:
Can u please explain why there is both Delta P * V and Delta V * P?

Would this not take Work into account twice?

When P is constant, the Delta P * V term = 0?

When V is constant, the Delta V * P term =0? I am just guessing

Work is \int P\,dV (magnitude), not V\Delta P or V\Delta P+P\Delta V, and not necessarily P\Delta V if the pressure isn't constant.

I agree with your guesses.
 

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