Absolute Entropy (Statistical)

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SUMMARY

The discussion focuses on the derivation of absolute entropy, specifically the formula S = -k. SUM P.lnP. Participants explore the transition from dU = SUM E.dP - SUM P.dE, questioning the origin of the minus sign. Clarifications are provided regarding the differential expression dS = -k. SUM lnP.dP transitioning to dS = -k.d(SUM P.lnP), emphasizing the application of the product rule in calculus. The conclusion highlights that the last term in the product rule vanishes due to the normalization condition of probabilities.

PREREQUISITES
  • Understanding of statistical mechanics concepts, particularly entropy.
  • Familiarity with calculus, especially the product rule and differentiation.
  • Knowledge of probability theory and the properties of probability distributions.
  • Basic grasp of thermodynamic variables such as internal energy (U) and temperature (k).
NEXT STEPS
  • Study the derivation of the canonical ensemble in statistical mechanics.
  • Learn about the implications of the normalization condition in probability theory.
  • Explore the relationship between entropy and thermodynamic variables in detail.
  • Investigate advanced topics in statistical mechanics, such as the microcanonical ensemble.
USEFUL FOR

Students and professionals in physics, particularly those specializing in statistical mechanics, thermodynamics, and entropy calculations. This discussion is also beneficial for mathematicians interested in the application of calculus in physical theories.

Master J
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I was looking at a derivation of entropy expressed as an absolute probability:

S = -k. SUM P.lnP
(What is the name of this by the way?)

In the derivation, it makes the following statements which I really just don't get!

U = SUM E.P

so therefore dU = SUM E.dP - SUM P.dE

Where does the minus sign come from? Should it not be a plus??

Then, it goes from dS = -k. SUM lnP.dP to dS = -k.d(SUM P.lnP)

How is that true?? First it was just P that was a differential element, now its the whole expression in the bracket??
 
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How does the whole derivation go?

Master J said:
U = SUM E.P
so therefore dU = SUM E.dP - SUM P.dE
Where does the minus sign come from? Should it not be a plus??
I agree.

Master J said:
Then, it goes from dS = -k. SUM lnP.dP to dS = -k.d(SUM P.lnP)

How is that true?? First it was just P that was a differential element, now its the whole expression in the bracket??
Check what the whole expression is equal to. By the product rule:
\mathrm{d}(\sum P_i\ln P_i)=\sum(\ln P_i\mathrm{d}P_i+P_i\mathrm{d}\ln P_i)=\sum\ln P_i\mathrm{d}P_i+\sum P_i\frac{\mathrm{d}P_i}{P_i}=\sum\ln P_i\mathrm{d}P_i+\sum\mathrm{d}P_i
The last term is zero since
\sum P_i=1
and hence
\sum \mathrm{d}P_i=\mathrm{d}(\sum P_i)=\mathrm{d}1=0
 

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