Entropy of system and surroundings

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Discussion Overview

The discussion revolves around the entropy changes of a system and its surroundings during various thermodynamic processes, including reversible adiabatic and isothermal processes, as well as phase changes. Participants explore how to compute entropy changes and the implications of reversible versus irreversible processes.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant states that for a reversible adiabatic process, the change in entropy of the system is zero, and thus the surroundings also experience no change in entropy.
  • The same participant questions how to compute the change in entropy of the surroundings during a reversible isothermal process.
  • Another participant notes that the change in entropy of the surroundings may not always equal the negative of the change in entropy of the system, suggesting the inequality ΔS_(surr) + ΔS_(sys) ≥ 0.
  • A further contribution highlights that a closed system undergoing a reversible process does not guarantee that the surroundings also experience a reversible change, providing examples of different scenarios that affect the entropy of the surroundings.
  • One participant references a definition of "Internally Reversible Processes" from a thermodynamics textbook, indicating that these processes do not specify the reversibility of the surroundings.
  • A suggestion is made about using a special toolkit to ensure that the surroundings are handled reversibly during changes, which includes using weights and constant temperature reservoirs.

Areas of Agreement / Disagreement

Participants express uncertainty regarding the calculation of entropy changes and the relationship between the system and surroundings, indicating that multiple competing views remain without a consensus on the correct approach.

Contextual Notes

There are limitations regarding the assumptions made about the reversibility of processes and the definitions of system and surroundings, which are not fully resolved in the discussion.

Titan97
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I have some doubts on entropy change of certain simple process. Can you check if these statements are correct? This is what I know:

For a reversible adiabatic process, $$\Delta Q=0$$. $$\Delta S_{system}=\frac{\Delta Q}{T}=0$$.
Since the system does not alter the surroundings, ##\Delta S_{Surr}=0##.

For a reversible isothermal process, $$\Delta S_{system}=nR\ln{\frac{V_2}{V_1}}$$
How can I compute ##\Delta S_{Surr}##?.

For any phase change, since temperature and pressure is constant,
$$H=U+pV$$
$$dU=dQ-pdV$$
$$dH-d(pV)=dQ-pdV$$
$$dH=dQ+VdP=dQ$$
since P is constant.
Hence, $$dS_{sys}=\frac{dH}{T}$$
How can I compute ##\Delta S_{Surr}##?.​

For example, if an ice melts, ice is the 'system' and the medium where its kept is the 'surroundings'
The statements in red are questions. Those in blue means 'I am not sure if its correct'. (I might have written meaningless/incorrect/stupid statements. I just want to be clear with entropy before writing my exam.)
 
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But Q_surroundings may not always be equal to -Q_system.

Should I use ΔS_(surr) + ΔS_(sys) ≥ 0?

But that won't give the exact value.
 
If a closed system is subjected to a reversible process, there is no guarantee that the surroundings is also handled reversibly during the process. For example, if you bring about an adiabatic reversible compression of a gas within a cylinder by hand (say by very gradually subjecting the gas to increasing pressure using a piston attached to a rod being pushed by your hand), the change in entropy of your body (which basically constitutes the surroundings) certainly will be positive. On the other hand, if the same change is brought about by sliding tiny weights onto the piston at different elevations, the change in entropy of the surroundings will be zero.

Moran et al, Fundamentals of Engineering Thermodynamics define "Internally Reversible Processes." These are processes for which the system experiences a reversible change without specifying whether the surroundings are handled reversibly or irreversibly.

If you want to make sure that the surroundings is always handled reversibly during all changes you consider, I have a special tool kit that one can use. It consists of two kinds of items: (a) a set of tiny weights that can be applied to change the pressure gradually and (b) an infinite array of constant temperature reservoirs at different temperatures, so that the system can be contacted with a sequence of reservoirs at gradually increasing- or gradually decreasing temperatures. This should do the trick.

Chet
 

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