Questions on Stat Mech Physical Adsorption Problem

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SUMMARY

The discussion centers on the application of the canonical ensemble versus the grand canonical ensemble in solving a physical adsorption problem from statistical mechanics. The problem involves a closed box with a fixed number of particles (N), where particles can exist in two states: bulk or adsorbed. The consensus is that the canonical ensemble is appropriate because the total number of particles remains constant, despite their distribution between the two states. The grand canonical ensemble, which allows for variable particle numbers, is deemed unsuitable for this scenario.

PREREQUISITES
  • Understanding of statistical mechanics, particularly canonical and grand canonical ensembles.
  • Familiarity with partition functions in statistical physics.
  • Knowledge of physical adsorption processes and their implications in closed systems.
  • Basic grasp of thermodynamic variables such as chemical potential (μ) and temperature (T).
NEXT STEPS
  • Study the derivation and applications of the canonical ensemble partition function.
  • Explore the grand canonical ensemble and its use cases in systems with variable particle numbers.
  • Investigate physical adsorption phenomena and their modeling in statistical mechanics.
  • Review the implications of fixed versus variable particle numbers in thermodynamic systems.
USEFUL FOR

Students and researchers in physics, particularly those focusing on statistical mechanics, thermodynamics, and physical adsorption processes. This discussion is beneficial for anyone seeking to deepen their understanding of ensemble theory and its applications in closed systems.

Silviu
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Hello! I have a question about the first problem in Stat Mech (Physical Adsorption) from http://web.mit.edu/physics/current/graduate/exams/gen2_F01.pdf. The solution to it can be found http://web.mit.edu/physics/current/graduate/exams/gen2sol_F01.pdf. I understand the logic they use for the solution, but I am not sure I understand why do they use the partition function of the canonical ensemble and not the grand canonical one. If I understand the problem well, the particles can go from the wall of the container to the inside of the container and the other way around, so the number of particles in not fixed (but the average is). Also, there is no way to exchange energy here, other than particles moving from wall to the inside of the container. So why don't we use the GC ensemble partition function (i.e. adding the term ##e^{-\mu N/KT}##)? Thank you!
 
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The problem considers a closed box, with a fixed number of particles N. While the particles can be in two "states," in the bulk or adsorbed, their number is fixed. That's why the canonical ensemble is the right one.

For the grand canonical ensemble, you would have a reservoir of particles at fixed μ, and the number of particles N would not be fixed.
 
DrClaude said:
The problem considers a closed box, with a fixed number of particles N. While the particles can be in two "states," in the bulk or adsorbed, their number is fixed. That's why the canonical ensemble is the right one.

For the grand canonical ensemble, you would have a reservoir of particles at fixed μ, and the number of particles N would not be fixed.
I understand what you mean, but wouldn't this be the case if you write the partition function for the whole system (N is fixed for ##N=N_{bulk} + N_{surface}##) so for that I would use the canonical ensemble. But he writes the partition functions for ##N_{bulk}## and ##N_{surface}## separately, and these are not fixed.
 

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