Ideal Gas Entropy: Solving Kardar's Equation IV.33

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Discussion Overview

The discussion revolves around the entropy of an ideal gas as presented in Kardar's Statistical Physics of Particles, specifically focusing on equation IV.33. Participants are examining potential errors in the equation and exploring the implications of classical versus quantum statistical mechanics in deriving the correct expression for entropy.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • One participant questions the correctness of equation IV.33, suggesting that the term should be 4∏mE instead of 2∏mE, leading to an adjustment in the final equation.
  • Another participant asserts that the entire expression is incorrect and provides an alternative formulation known as the Sackur-Tetrode equation for a monatomic ideal gas.
  • Some participants discuss the implications of neglecting certain terms and how this affects the derivation of the entropy expression.
  • There is mention of Kardar's approach using classical physics to derive an incorrect expression and how introducing indistinguishability can lead to a more accurate result.
  • Participants explore the introduction of Planck's constant h in the context of quantum statistical mechanics and its relevance to the derivation of the entropy expression.
  • One participant references Arieh Ben-Naim's derivation of the Sackur-Tetrode equation using information theory, noting its clarity until the introduction of the h term, which becomes vague.

Areas of Agreement / Disagreement

Participants express differing views on the correctness of Kardar's equation and the appropriate treatment of terms in the entropy derivation. There is no consensus on the resolution of the issues raised, and multiple competing interpretations remain present.

Contextual Notes

Participants highlight the importance of dimensional analysis in ensuring the argument of the logarithm in the entropy expression is dimensionless. There are unresolved questions regarding the introduction of Planck's constant and its implications for the derivation.

Jolb
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I'm working through Kardar's Statistical Physics of Particles, and I'm in chapter 4 on the part about the ideal gas. Here's a link to that chapter from the book:

http://web.mit.edu/8.333/www/lectures/lec13.pdf

I think he has an error in equation IV.33 but I'd like you guys to make sure of it.

http://img694.imageshack.us/img694/467/kardar.jpg

I think in the top equation of IV.33, the 2∏mE should be 4∏mE, so the final equation should have an 8 instead of a 4. Here's why I think that:
[tex]ln\left (V^N\frac{2\pi^\frac{3N}{2}}{\left (\frac{3N}{2}-1 \right )!} \left ( 2mE \right )^\frac{3N-1}{2}\Delta _R\right )[/tex]

[tex]=Nln(V)+\frac{3N}{2}ln(2\pi)-\left (\frac{3N}{2}-1 \right )ln\left ( \frac{3N}{2}-1 \right )+\left ( \frac{3N}{2}-1 \right )+\frac{3N-1}{2}ln(2mE)+ln\Delta _R[/tex]

eliminating terms of order 1 or lnN,

[tex]=Nln(V)+\frac{3N}{2}ln(2\pi)-\left (\frac{3N}{2} \right )ln\left ( \frac{3N}{2} \right )+\left ( \frac{3N}{2} \right )+\frac{3N}{2}ln(2mE)[/tex]
[tex]=N\left (ln(V)+\frac{3}{2}ln(2\pi)-\left (\frac{3}{2} \right )ln\left ( \frac{3N}{2} \right )+\left ( \frac{3}{2} \right )ln(e)+\frac{3}{2}ln(2mE) \right )[/tex]
[tex]=N\left (ln(V)+ln(2\pi)^\frac{3}{2}-ln\left ( \frac{3N}{2} \right )^\frac{3}{2}+ln(e)^\frac{3}{2}+ln(2mE)^\frac{3}{2} \right )[/tex]
[tex]=Nln\left (V\left [\frac{(2\pi)(e)(2mE)}{\frac{3N}{2}} \right ]^\frac{3}{2} \right )[/tex]

Did I make a mistake eliminating the terms of lower order? Please help!
 
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It depends on whether you interpret [tex]2\pi^{3 N/2}[/tex] to mean [tex]2(\pi^{3 N/2})[/tex] or [tex](2\pi)^{3 N/2}[/tex].

It doesn't much matter, the entire expression is in error. The correct expression is

[tex]S=N k_B\log\left[V \left(\frac{4 \pi m E}{3 h^4}\right)^{3/2}\left(\frac{e}{N}\right)^{5/2}\right][/tex]

also known as the Sackur-Tetrode equation for a monatomic ideal gas.
 
Great, thanks! Silly mistake. The 2 next to the pi vanishes when you neglect terms of order 1.

Kardar's approach is an interesting one--he uses classical physics to derive that incorrect expression and then shows how indistinguishability can be introduced to resolve the error. Putting 1/N! next to omega leads to something closer to the Tetrode-Sackur equation, but without any h. I'm guessing this follows exactly Gibbs' formulation of the Gibbs paradox. I think it's worthwhile to approach statmech from the classical point of view, so I do want to worry about this derivation.
 
Last edited:
Jolb said:
Great, thanks! Silly mistake. The 2 next to the pi vanishes when you neglect terms of order 1.

Kardar's approach is an interesting one--he uses classical physics to derive that incorrect expression and then shows how indistinguishability can be introduced to resolve the error. Putting 1/N! next to omega leads to something closer to the Tetrode-Sackur equation, but without any h. I'm guessing this follows exactly Gibbs' formulation of the Gibbs paradox. I think it's worthwhile to approach statmech from the classical point of view, so I do want to worry about this derivation.

Ok, yes that will help to fix things. Note that in order for the ST equation to be physically meaningful, the argument of the logarithm must be dimensionless. Without the h, its not. Let me know how, in this derivation, the h is finally introduced.
 
Well this "derivation" is meant to illustrate where and how the classical approach breaks down. The incorrect equation above is not extensive, so Kardar motivates the introduction of 1/N! in the expression for Ω by noting that it ensures extensivity, and he argues its physical appropriateness by discussing indistinguishability.

Here's what he says about h. "Yet another difficulty with the expression IV.47, [which is the 1/N! corrected version of entropy] resolved in quantum statistical mechanics, is the arbitrary constant that appears in changing the units of measurement for q and p. The volume of phase space involves products pq, of coordinates and conjugate moment, and hence has dimensions of (action)N. Quantum mechanics provides the appropriate measure of action in Planck's constant h. Anticipating these quantum results, we shall henceforth set the measure of phase space for identical particles to..." So he sticks in a 1/h3N. Not quite as satisfying as the demonstration of why N! was needed.
 
Jolb said:
Well this "derivation" is meant to illustrate where and how the classical approach breaks down. The incorrect equation above is not extensive, so Kardar motivates the introduction of 1/N! in the expression for Ω by noting that it ensures extensivity, and he argues its physical appropriateness by discussing indistinguishability.

Here's what he says about h. "Yet another difficulty with the expression IV.47, [which is the 1/N! corrected version of entropy] resolved in quantum statistical mechanics, is the arbitrary constant that appears in changing the units of measurement for q and p. The volume of phase space involves products pq, of coordinates and conjugate moment, and hence has dimensions of (action)N. Quantum mechanics provides the appropriate measure of action in Planck's constant h. Anticipating these quantum results, we shall henceforth set the measure of phase space for identical particles to..." So he sticks in a 1/h3N. Not quite as satisfying as the demonstration of why N! was needed.

It sure isn't. I've been trying to understand Arieh Ben-Naim's derivation of the STE, in "A Farewell to Entropy". He derives it using information theory, and its really informative (LOL - no pun), up to the point where he introduces the h term, then it becomes just as vague.
 

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