Enthelpy change with standard conditions

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Discussion Overview

The discussion revolves around the change in enthalpy and its dependence on pressure, particularly in the context of standard conditions. Participants explore theoretical aspects, practical implications, and definitions related to enthalpy, internal and external pressures, and the behavior of different states of matter (gases, liquids, and solids).

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • Some participants question why the change in enthalpy is said to depend on pressure, suggesting that temperature change alone should suffice in isothermal processes.
  • Others clarify that the relation pV=nRT applies primarily to ideal gases and does not necessarily hold for liquids or solids.
  • A participant points out the distinction between internal and external pressure, arguing that internal pressure is relevant for certain calculations while external pressure is used in enthalpy definitions.
  • Some argue that the definition of enthalpy should be consistent across all phases of matter, while others challenge the clarity of this definition in textbooks.
  • There is a discussion about the measurement of internal pressure in solids and how it relates to enthalpy, with some suggesting that it can be derived from mechanical equilibrium conditions.
  • Participants express differing views on the appropriateness of using concepts from elasticity theory to define enthalpy.
  • Some assert that the external pressure used in calorimetric experiments refers to the experimental conditions, while others question the relevance of internal pressure in these contexts.

Areas of Agreement / Disagreement

Participants do not reach consensus on the definitions and implications of internal versus external pressure in relation to enthalpy. Multiple competing views remain regarding the measurement and theoretical foundations of enthalpy across different states of matter.

Contextual Notes

Limitations include the lack of clarity in distinguishing between internal and external pressures, the applicability of ideal gas laws to non-gaseous states, and the varying definitions of enthalpy across different sources.

  • #31
Borek said:

Thank you Borek for giving the link! All I can see is that Eutectics6002 states that in a (quasi-) reversible process p_in =p_ext if the system is in mechanical equilibrium with its surrounding. This I never doubted! However, enthalpy is also defined for systems not in mechanical equilibrium with the surrounding.
 
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  • #32
DrDu said:
How do you describe then the Joule-Thompson experiment? I.e. the expansion of a gas from (internal) pressure p1 to pressure p2 trough a throttle?
According to e.g. the book of Max Planck "Thermodynamik" // The process is called "isenthalpic" as H1=H2.

The answer to this question can be found in a 2010 publication in the journal of the Dutch Process Engineers:
'Energy-balance of the Joule-Thomson experiment: Enthalpy change at decompression.
(npt-procestechnologie 17(4)18-22.)

The throttle process is not isenthalpic except in one (theoretical) case.
 
  • #33
Zeppos10 said:
in my opinion the proper handling of the joule-kelvin experiment depends on the proper definition of the system, ie system-environment interface. It is not a system in equilibrium however and it brings us far from the problem that started this discussion. To me it seems rather important to the whole of science what the physical meaning is of p in (H=U+pV): I wonder if there are only 2 or 3 people in this forum that are interested in the subject ??

for the throttle-aspect see file attached in thread on nov 24 2010:
Enthalpy, thermal energy, and kinetic vs. potential energy
 

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