How is the chemical potential defined when keeping entropy and volume constant?

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Discussion Overview

The discussion revolves around the definition of chemical potential when keeping entropy and volume constant. Participants explore the implications of adding particles to a system and how this affects entropy, energy, and the mathematical representation of chemical potential.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • One participant defines chemical potential as ##µ=\frac{\partial E}{\partial N}## while keeping entropy and volume constant, questioning how to maintain constant entropy when adding particles.
  • Another participant suggests that adding a particle changes the temperature, implying that constant entropy may not be physically realizable in practice.
  • A different participant proposes a definition of chemical potential based on the relationship between energy, entropy, and the number of particles, suggesting ##\mu=E_p-TdS##.
  • One participant challenges the feasibility of maintaining constant entropy theoretically, arguing that adding a particle inherently changes the total energy and combinatorics used to calculate entropy.
  • Another participant acknowledges that while adding a particle typically changes entropy, they explore the implications of the mathematical representation of chemical potential in relation to changes in internal energy.
  • There is a discussion about the interpretation of partial derivatives at constant entropy, with one participant noting that these derivatives can be difficult to interpret.
  • Participants agree that adding a particle usually results in a change in entropy, leading to further exploration of how to define chemical potential in this context.

Areas of Agreement / Disagreement

Participants generally agree that adding a particle changes entropy. However, there is no consensus on how to define chemical potential under the condition of constant entropy, with multiple competing views and interpretations presented.

Contextual Notes

Participants express uncertainty regarding the theoretical implications of maintaining constant entropy while adding particles, highlighting the complexities of statistical mechanics and the interpretation of mathematical relationships.

Coffee_
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The chemical potential is defined as ##µ=\frac{\partial E}{\partial N}## while keeping entropy and volume constant. Well how to keep the volume constant while adding particles is obvious but what about the entropy? Obviously adding a particle at a certain energy ##E_{p}## changes the total energy of the system and ##N+1## changes the combinatorics to calculate the entropy.

How does one keep entropy constant while adding particles?
 
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Coffee_ said:
How does one keep entropy constant while adding particles?
Don't get too hung up on physical interpretations of partial derivatives that imply "processes" that are unrealizable in the lab or on the bench --- for this specific case, T changes.
 
Would it be correct to define µ as follows then?

''I add a particle with energy ##E_p## to the system without changing the volume. The entropy S changes. The increase in internal energy is obviously ##E_p## and ##dN=1##. This means that ##E_{p}=TdS+\mu##. We can define ##\mu=E_p-TdS## - that is: when adding a particle of a certain energy to a system , the chemical potential of that system is the difference between this particles energy and the product of T by ##\Delta S##? ''
 
Coffee_ said:
Would it be correct to define µ as follows then?
Coffee_ said:
The entropy S changes.
Not in the original context of "constant entropy."
 
I think you misunderstood my initial question as something I saw as very difficult to do in the lab. Or maybe not, but to be sure:

I see not how it's possible to add a particle without changing the entropy THEORETICALLY. Adding a particles changes the total energy and changes the combinatorics of the system that are used to calculate the entropy. In general entropy WILL change by adding a particle if what I just wrote is correct. This is not some limitation of the lab, it's the theory of statistical mechanics I'm speaking of.

So if the answer to the above is ''entropy in general changes'' when adding a particle, then see my second comment as my attempt to make sense of it.
 
Coffee_ said:
statistical mechanics I'm speaking of.
Yes. And, there are some partial derivatives that are --- less easily interpreted than others --- those at constant entropy being one particular case; take them at face value --- in a universe where S can be held constant, partial of E with respect to N at constant V, S is μ, which is identical to μ derived from partial of A (Helmholtz) at constant V, T (accessible), G (or F, Gibbs) at P, T, or H at P, S.
 
I see, nevermind then you understood me correctly.

Well so we both agree, adding a particle DOES change entropy usually.

So adding a particle that has an energy 'e' while keeping the volume constant must be according to 'dU=TdS + µdN' where dN=1 right?

dU = e = TdS + µ

Rewriting , ##µ=e-TdS##

This dS we can actually calculate if we know the system well enough.

Is this a correct way to view/define the chemical potential then? As adding a particle of a certain energy, then counting what dS is and just taking the difference?
 

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