How can heat change be measured under constant pressure?

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Discussion Overview

The discussion revolves around the measurement of heat change under constant pressure, specifically focusing on the concept of enthalpy and its relationship with internal energy. Participants explore theoretical aspects, definitions, and implications of these thermodynamic properties.

Discussion Character

  • Technical explanation
  • Debate/contested

Main Points Raised

  • Some participants propose that enthalpy represents the heat content of a system at constant pressure and that enthalpy change corresponds to the heat absorbed or evolved under these conditions.
  • Others argue that heat is not a state variable and emphasize that it is the energy exchanged between systems, which complicates its measurement as a property.
  • A participant clarifies that the relationship between enthalpy change and internal energy change is not straightforward, noting that enthalpy change is defined as ΔU + Δ(PV), indicating that pressure changes can affect enthalpy even at constant volume.
  • Another participant discusses the equations governing enthalpy and internal energy, suggesting that while both can be related to heat applied to the system, they represent different processes with distinct final states.
  • Some participants challenge earlier claims about the behavior of systems under constant pressure, particularly regarding temperature changes and volume expansion.
  • There is contention over whether enthalpy change and internal energy change can be considered equivalent, with some asserting they differ due to volumetric work involved in the constant pressure scenario.

Areas of Agreement / Disagreement

Participants express differing views on the definitions and implications of enthalpy and internal energy, with no consensus reached on several key points, including the relationship between these properties and the conditions under which they are measured.

Contextual Notes

Limitations include potential misunderstandings about the definitions of enthalpy and heat, as well as the implications of constant pressure versus constant volume conditions on energy measurements.

TheExibo
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So enthalpy is the heat content of a system at constant pressure. Enthalpy change is equal to the heat absorbed or evolved by the system at constant pressure. If my understanding is correct, a system whose temperature goes up will return back to that starting temperature if pressure is kept constant (i.e., its volume is allowed to expand). Therefore, is enthalpy, or heat change, measured in terms of the expansion?

Additionally, would enthalpy change and internal energy change (which is equal to the heat absorbed or evolved by the system at constant volume) not have the same values? After all, in the former, the amount of energy released (if the reaction inside releases energy) can be calculated by multiplying the change in volume with the outside pressure, and this value of energy, as far as I know, should be equal to the energy of the change in temperature inside the latter system.
 
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Heat is not a state variable, i.e., it is not a property of a system, it is the energy that is thermally exchanged between two systems. This follows from the fact that ##\delta Q## is not an exact differential.
 
Enthalpy change is not $\Delta U+P\Delta V$. It is $$\Delta U+\Delta (PV)$$. So, even at constant volume, if the pressure changes, the enthalpy change is not equal to the internal energy change.
 
The relationship between enthalpy ##H## and internal energy ##U## is ##H=U+PV##.
In a reversible process we have ##dU=dQ+dW=dQ-PdV##, and we have ##dH=dQ+VdP##.
So ##\Delta H = \Delta Q + \int_{P_1}^{P_2} V dP##. If the pressure is indeed constant, this becomes ##\Delta H=\Delta Q##, which is then independent of volume.
Similarly ##\Delta U = \Delta Q - \int_{V_1}^{V_2} PdV##. If the volume is constant, this becomes ##\Delta U=\Delta Q##, which is independent of pressure.
In both cases the change in enthalpy respectively in internal energy is simply the heat that is applied to the system. Keep in mind though that these are different processes with different final states.
 
Last edited:
TheExibo said:
So enthalpy is the heat content of a system at constant pressure.

No, it isn't. Enthalpy is fedined as

H = U + p \cdot V

TheExibo said:
Enthalpy change is equal to the heat absorbed or evolved by the system at constant pressure.

Yes that's correct and the reason for the definition of enthalpy. Calorimetirc measurements of internal energy would require constant volume which is much harder to achieve.

TheExibo said:
If my understanding is correct, a system whose temperature goes up will return back to that starting temperature if pressure is kept constant (i.e., its volume is allowed to expand).

I'm afraid your understanding is not correct.

TheExibo said:
Therefore, is enthalpy, or heat change, measured in terms of the expansion?

Change of enthalpy is measured in terms of exchanged heat under constant pressure. Expansion is just a possible side effect of the constant pressure and irrelevant for the measurement.

TheExibo said:
Additionally, would enthalpy change and internal energy change (which is equal to the heat absorbed or evolved by the system at constant volume) not have the same values?

No. Under constant pressure they differ by the volumetric work.
 

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