How is ΔU calculated in relation to enthalpy and work?

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Discussion Overview

The discussion revolves around the calculation of the change in internal energy (ΔU) in relation to enthalpy (ΔH) and work (W) during a chemical reaction. Participants explore the implications of sign conventions in thermodynamic equations.

Discussion Character

  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant presents the equation ΔU = ΔH - pΔV and provides a specific example involving heat produced and work done during a gas compression.
  • Another participant clarifies that if work is done on the system, pΔV should be considered negative, leading to a different calculation of ΔU.
  • A third participant discusses the variability in sign conventions between chemistry and engineering, suggesting that the interpretation of work can lead to different results depending on the convention used.

Areas of Agreement / Disagreement

Participants express differing views on the sign conventions used in the calculations, indicating that there is no consensus on the interpretation of the equations and the resulting values for ΔU.

Contextual Notes

The discussion highlights the potential confusion arising from different sign conventions in thermodynamics, particularly between chemistry and engineering contexts.

Absentee
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Ok, I'll get pretty straight-forward.

So, the usual assumptions:
Energy given to the system: > 0
Energy taken from the system: < 0

Enthalpy is defined as:

ΔH = ΔU + pΔV, so

ΔU = ΔH - pΔV

Let's say that during some chemical reaction there is heat produced (Energy taken from the system):

ΔH = -49 kJ

... And a gas was compressed (Energy given to the system):

W = 5 kJ

To calculate the change in internal energy

ΔU = ΔH - pΔV
ΔU = -49 kJ - 5 kJ = -54 kJ

However, this does not make sense to me.
Shoudn't it be -44 kJ by common sense?

Is it the sign convention is intentionally switched in the first term?

Thanks.
 
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W is the work done by the system on the surroundings. If the surroundings do work on the system, the work is negative. If the gas is compressed, pΔV is negative. So, pΔV = -5 kJ. So the answer should be -44 kJ.

Chet
 
Absentee said:
Is it the sign convention is intentionally switched in the first term?

Thanks.

Sign convention is always nasty. In chemistry one mostly considers W to be the work done on the system, hence ##W=-p\Delta V## and ##\Delta U=Q+W##. Engineers (like Chestermiller) are usually more interested in the work a system can do on its surrounding and use ## W=p\Delta V## together with ##\Delta U=Q-W##. From your text, I am inclined to assume that you are using the first convention.
 
Great, thanks!
 

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