Understanding \DeltaH and \DeltaE in Constant Volume Process

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Discussion Overview

The discussion revolves around the differences between the changes in enthalpy (\DeltaH) and internal energy (\DeltaE) during a constant volume process. Participants explore the definitions and implications of these thermodynamic quantities, as well as the equations governing work done in such processes.

Discussion Character

  • Technical explanation
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • Some participants note that enthalpy is defined as H=E+pV, leading to the equation \Delta_V H=\Delta E+V\Delta p at constant volume.
  • One participant references the first law of thermodynamics, stating that heat supplied equals internal energy plus work done, leading to the equation \DeltaH = \DeltaU + \DeltaW.
  • Another participant questions the treatment of the term V\DeltaP, suggesting that it should be zero in the context of constant volume, while others challenge the correctness of the equations presented.
  • There is a request for clarification on what the term V\DeltaP represents, indicating a need for a simpler description of its physical meaning.
  • Participants express skepticism about the correctness of certain equations related to work done, emphasizing the importance of distinguishing between general equations and special cases applicable under specific conditions.

Areas of Agreement / Disagreement

Participants express differing views on the correctness of the equations related to work and the definitions of \DeltaH and \DeltaE. There is no consensus on the validity of the claims made, and the discussion remains unresolved regarding the proper treatment of these thermodynamic quantities.

Contextual Notes

Some equations presented may depend on specific conditions, such as constant volume or constant pressure, which are not universally applicable. Participants highlight the need to clarify these conditions when discussing thermodynamic processes.

phymatter
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What is the difference between [tex]\Delta[/tex]H and [tex]\Delta[/tex]E in a constant volume process ?
 
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By definition it is always true that
[tex] H=E+pV[/tex]
At constant volume you have
[tex] \Delta_V H=\Delta E+V\Delta p[/tex]
Here you see the difference in the term.
What exactly did you want to know?
 
but acc to first law Heat supplied = internal energy + work done
i.e.
i.e. [tex]\Delta[/tex]h = [tex]\Delta[/tex]U + [tex]\Delta[/tex]W
and [tex]\Delta[/tex]W = [tex]\Delta[/tex](pv) and
[tex]\Delta[/tex](pv) = P[tex]\Delta[/tex]V + V[tex]\Delta[/tex]P and
for work done V[tex]\Delta[/tex]p is taken as zero so how come can we say here V[tex]\Delta[/tex]P is not taken as zero here?
 
jeedoubts said:
i.e. [tex]\Delta[/tex]h = [tex]\Delta[/tex]U + [tex]\Delta[/tex]W
and [tex]\Delta[/tex]W = [tex]\Delta[/tex](pv)

Hi jeedoubts, welcome to PF. Can you give a reference for these two equations? I doubt very much that they're correct. For example, work is defined as [itex]P\Delta V[/itex], not [itex]\Delta(PV)[/itex].

I agree with Gerenuk's answer.
 
what does the quantity v[tex]\Delta[/tex]p refers to then?
 
The difference between enthalpy change and energy change in a constant-volume process.
 
physically what does it represent??
 
I don't know of a simpler description (other than the literal "volume multiplied by pressure change"). What are you looking for?
 
jeedoubts said:
[tex]\Delta[/tex]W = [tex]\Delta[/tex](pv) and
[tex]\Delta[/tex](pv) = P[tex]\Delta[/tex]V + V[tex]\Delta[/tex]P
Neither equation is correct in general. The correct equations are
[tex] \mathrm{d}W=p\mathrm{d}V[/tex]
(or with the other sign if you consider the work done on the system) and if you wish
[tex] \mathrm{d}(pV)=p\mathrm{d}V+V\mathrm{d}p[/tex]
It follows that only for constant volume or constant pressure processes the work can be described by
[tex] W=p\Delta V\qquad\text{(const. p or const. V)}[/tex]
Is it very important to know what is the general equation and what the special case. These special cases only apply if the conditions are met.

Mapes is correct.
 

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