Definition of Entropy for Irreversible Processes

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Discussion Overview

The discussion centers on the definition and calculation of entropy for thermodynamic irreversible processes, contrasting it with the established methods for reversible processes. Participants explore various approaches to understanding entropy changes in different states and the implications of path independence in thermodynamic processes.

Discussion Character

  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant outlines a method for calculating entropy in reversible processes using infinitesimal heat transfers and temperature, and requests a thermodynamic approach for irreversible processes.
  • Another participant asserts that entropy is defined only for equilibrium states and states that the change in entropy can be determined by the difference between the entropy of the initial and final states, regardless of the process being reversible or irreversible.
  • A different participant agrees that while the entropy of an irreversible process cannot be calculated directly, the change in entropy is a state function that can be approached as if the process were reversible.
  • One participant emphasizes the need to define the initial and final equilibrium states for an irreversible process and suggests conceiving a reversible process to calculate the change in entropy between these states.

Areas of Agreement / Disagreement

Participants express differing views on the definition and calculation of entropy for irreversible processes. Some agree on the state function nature of entropy, while others emphasize the importance of equilibrium states, leading to an unresolved discussion on the best approach.

Contextual Notes

Participants highlight the dependence on well-defined initial and final states for calculating entropy changes and the potential challenges in applying reversible process methods to irreversible processes.

Hummel
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What is the definition of entropy of a thermodynamic irreversible process?

In the case of reversible process from initial state 'a' to final state 'b' ,one may define entropy
by

1) Constructing infinitely many reservoirs having temperatures corresponding to the temperature at every point on the P-V diagram of the process from 'a' to 'b'

2) Finding \frac{dQ}{T} at every point
where dQ is the elemental heat transferred at every point,T is the corresponding temperature at the point.
3)Now by linking each reservoir of temperature T to a reservoir at unit absolute thermodynamic temperature by a reversible heat engine.

4) ∴ ,\frac{dQ}{T} = \frac{Qs}{1} = dS

5) Now integrating the entropy of every elemental part on the P-V curve,we get the total change in entropy as
ΔS = \int^{b}_{a}\frac{dQ}{T}

(Abs. entropy can be determined using nernst theorem)

Similarly,how can we determine the entropy or change in entropy for a irreversible process.

Gentlemen,i would be happy if we stick to a thermodynamic approach rather than Quantum mechanical approach(of course unless it is necessary)
(My sincere Request:For god's sake, please don't talk about entropy as randomness)
 
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Entropy has meaning only for equilibrium states. If we have some process (does not matter whether it is reversible or not) that takes the system from the state ##A## to state ##B##, the change in entropy is

$$
\Delta S = S(B) - S(A).
$$

So, we need to know the states A,B and their entropy.
 
Hummel said:
What is the definition of entropy of a thermodynamic irreversible process?

It's the same as for a reversible process as far as I know. While the entropy of an irreversible process can't be calculated directly, the change in entropy a is state function independent of path, so one should be able calculate \Delta S by approaching the problem as if the process were reversible.

http://www.files.chem.vt.edu/chem-dept/marand/set6.pdf
 
Last edited by a moderator:
Jano L. said:
Entropy has meaning only for equilibrium states. If we have some process (does not matter whether it is reversible or not) that takes the system from the state ##A## to state ##B##, the change in entropy is

$$
\Delta S = S(B) - S(A).
$$

So, we need to know the states A,B and their entropy.

Sir,my question was how do you define entropy for irreversible process?
apart from that,How do you determine S(B) and S(A)?
 
SW VandeCarr said:
It's the same as for a reversible process as far as I know. While the entropy of an irreversible process can't be calculated directly, the change in entropy a is state function independent of path, so one should be able calculate \Delta S by approaching the problem as if the process were reversible.

http://www.files.chem.vt.edu/chem-dept/marand/set6.pdf

I totally appreciate the PDF attachment.
I will get back once i completely go through it and if if we have to iron out any kinks.
 
Last edited by a moderator:
If the initial and final equilibrium states for the irreversible process are well defined, you need to dream up (i.e., conceive of) a reversible process that gets you between these same two equilibrium states, and use that process to calculate the change in entropy.

Chet
 

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