Change in enthelpy at constant VOLUME

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Discussion Overview

The discussion centers on the change in enthalpy during isochoric (constant volume) processes, particularly how heat addition affects internal energy and enthalpy. Participants explore the implications of enthalpy as a concept distinct from internal energy and the relationships between these quantities in thermodynamic processes.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant notes that during an isochoric process, while the volume remains constant, the pressure increases, leading to a greater increase in entropy compared to internal energy.
  • Another participant questions the source of energy when enthalpy increases more than the heat supplied, emphasizing that enthalpy is not energy itself but a useful mathematical potential.
  • Some participants clarify that the change in enthalpy during an isobaric process equals the heat transferred, while in isochoric processes, the relationship is more complex due to the \(\Delta PV\) term.
  • One participant expresses confusion about the implications of enthalpy increasing more than the heat supplied, acknowledging the need for external forces to maintain constant volume.
  • Another participant suggests that the \(\Delta PV\) term is already included in the internal energy change, indicating a potential double counting in the enthalpy expression.

Areas of Agreement / Disagreement

Participants express differing views on the interpretation of enthalpy and its relationship to internal energy, with some clarifying its role in isochoric processes while others remain uncertain about the implications of energy conservation in this context. The discussion does not reach a consensus on these points.

Contextual Notes

Participants note that the relationship between enthalpy and internal energy in isochoric processes involves assumptions about the definitions and roles of these quantities, and the discussion reflects various interpretations of these thermodynamic concepts.

Tabeia
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Hi, I know enthalpy is used a lot to calculate isobaric processes, but what about isochoric ones?
For example, if I have gas in a piston and I add heat at constant VOLUME.
I know that Q=\Delta U
But since H=U+PV or \Delta H=\Delta U + \Delta PV
I see that although V is constant P is not, it increases and so my entropy increase is bigger than my internal energy increase.
That is ok, I've searched this forum and found the same results, but my question is. Since enthalpy is energy, and energy is conserved from where does this energy come from?
Since the heat supplied to the system is smaller than the change in enthalpy.
Let's say I give 1000 Joules to the system in form of heat, the internal energy increases by 1000J, but the Enthalpy increases more...
Any help appreciated.
 
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Tabeia said:
I see that although V is constant P is not, it increases and so my entropy increase is bigger than my internal energy increase.

by how much? do you have any idea?
 
Since enthalpy is energy, and energy is conserved from where does this energy come from?
Enthalpy is not the energy, U is the energy. Enthalpy only has the dimensions of energy. Enthalpy is a mathematical potential useful in processes that take place at constant pressure. The change in enthalpy during an isobaric process is equal to the heat that is transferred. In the fields of engineering and chemistry enthalpy is more useful than internal energy, since most processes occur isobarically.
 
Bill_K said:
Enthalpy is not the energy, U is the energy. Enthalpy only has the dimensions of energy. Enthalpy is a mathematical potential useful in processes that take place at constant pressure. The change in enthalpy during an isobaric process is equal to the heat that is transferred. In the fields of engineering and chemistry enthalpy is more useful than internal energy, since most processes occur isobarically.
Yes. Exactly. I was in the middle of responding but this is a much more succinct and clearer answer than I was about to give.

AM
 
@Bill K, but the question is under isochoric process.
 
It feels weird that in an ISOCHORIC process the enthalpy(the potential to do work? Can I say that way?) increases more than the heat supplied...so I get more work(energy) than I gave in(in the form of heat)
Yes, I know that I'm wrong but I was having trouble seeing this.
But thanks for the clarification.

What I'm thinking is that this isn't a perpetual energy machine(duh) because to keep the constant volume I need to have something holding the piston, exerting some force on it to keep it from expanding. And also because I would need to compress it again and in the end the delta H would be zero.
Going to try some calculations later.
 
121910marj said:
@Bill K, but the question is under isochoric process.
In an isochoric process, the change in enthalpy differs from the change in internal energy by the amount \Delta PV. But it is just a mathematical book-keeping thing. The only actual heat flow/energy change is \Delta Q = \Delta U in a constant volume process. In fact, the VdP term is already incorporated into \Delta U so, in effect, it is being counted twice in the expression for \Delta H in a constant volume process.

AM
 
Andrew Mason said:
In fact, the VdP term is already incorporated into \Delta U so, in effect, it is being counted twice in the expression for \Delta H in a constant volume process.
AM

Aha, now everything is clear in my mind.
 

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