Questions about a System in Equilibrium

In summary, Pathria discusses the grand canonical ensemble and how it affects the temperature and energy of a system.
  • #1
Kashmir
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74
Pathria, Statistical mechanics, pg 93

"We consider the given system ##A## as immersed in a large reservoir ##A'##, with which it can exchange both energy and particles. After some time has elapsed, the system and the reservoir are supposed to attain a state of mutual equilibrium. Then, according to Section 1.3, the system and the reservoir will have a common temperature ##T## and a common chemical potential ##\mu##. The fraction of the total number of particles ##\mathrm{N^0}## and the fraction of the total energy ##E^{\text {o }}## that the system A can have at any time ##t## are, however variables..."

Why does author say "The fraction of the total number of particles ##\mathrm{N^0}## and the fraction of the total energy ##E^{\text {o }}## that the system A can have at any time ##t## are, however variables...". Since A is at equilibrium then total number of particles and energy of A shouldn't change but author says otherwise.

Why is it so?

Moderator's note: Latex edited. Please use ## ## as delimiters for inline latex.
 
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  • #2
Kashmir said:
Since A is at equilibrium then total number of particles and energy of A shouldn't change but author says otherwise.

Why is it so?
Maybe this is a reference to random fluctuations.

For example, suppose the systems are gaseous. There will be continual fluctuations in the distribution of particles and energy between A and A' due to the random particle motion. (The time-averages of the various quantities will be constant though.)

Imagine A is a very small system. The fractional variations of the number of particles and energy in A could then be large.

Just a guess though.
 
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  • #3
Kashmir said:
Since A is at equilibrium then total number of particles and energy of A shouldn't change but author says otherwise.
##A## represents an open system, so it can exchange both energy and particles with ##A'##. Only the temperature and chemical potential are fixed at equilibrium. As @Steve4Physics wrote, the energy and the number of particles will fluctuate. This is characteristic of the grand canonical ensemble.
 
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  • #4
DrClaude said:
##A## represents an open system, so it can exchange both energy and particles with ##A'##. Only the temperature and chemical potential are fixed at equilibrium. As @Steve4Physics wrote, the energy and the number of particles will fluctuate. This is characteristic of the grand canonical ensemble.
if number of particles and energy of system A changes why won't it's temperature change?
 
  • #5
Kashmir said:
if number of particles and energy of system A changes why won't it's temperature change?
It will!

For example, imagine A and A' are filled with an ideal gas. At equilibrium there will still be fluctuations in the number of particles in A, and their mean-square speed (hence their average kinetic energy and hence the temperature of A).

For a short time the temperature of A might rise/fall - and the temperature of A' would fall/rise (by a lesser amount due to A' having a larger size).
 

1. What is a system in equilibrium?

A system in equilibrium is a state in which the forward and reverse reactions occur at equal rates, resulting in no overall change in the concentrations of reactants and products.

2. How do you determine if a system is in equilibrium?

A system is in equilibrium when the concentrations of reactants and products remain constant over time, and the rate of the forward reaction is equal to the rate of the reverse reaction.

3. What factors can affect the equilibrium of a system?

The equilibrium of a system can be affected by changes in temperature, pressure, and the concentrations of reactants and products.

4. How can you shift the equilibrium of a system?

The equilibrium of a system can be shifted by changing the conditions of the reaction, such as increasing or decreasing the temperature, pressure, or concentrations of reactants and products.

5. What is Le Chatelier's principle and how does it relate to equilibrium?

Le Chatelier's principle states that if a system in equilibrium is subjected to a change in conditions, the system will shift in a direction that minimizes the effect of the change. This principle is used to predict how changes in temperature, pressure, and concentrations will affect the equilibrium of a system.

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