What is the connection between detailed balance and thermodynamic equilibrium?

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In summary, the detailed balance condition (DBC) is a formula that relates the rates of jumping between states in a system to the equilibrium probability distribution of those states. If the DBC holds, the system is time-reversible and the distribution remains unchanged under time evolution. This formula can also be used to derive an equilibrium distribution if the rates are known. It is not certain if the inverse is also true, that an equilibrium distribution implies the DBC.
  • #1
M.B.
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Hey,

I was wondering in what way the detailed balance condition (DBC) has to do with thermodynamic equilibrium.

The DBC is defined as
[tex]
W(i\to j)P(i) = W(j\to i)P(j)
[/tex]
with W the rates (probabilities per unit time) to jump from state i to j. P(i) is the equilibrium prob. density to have state i, this could be e.g. a Boltzmann Gibbs distribution in case of canonical equilibrium.
When for a (Markov jump) proces the above equality holds, then the system is time-reversible: it is even likely to follow a path forward in time or backwards in time

My question is:
The above formula is always possible to write down, but how is this related to equilibruim?
 
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  • #2
It is obvious that the probability distribution must not change by the flows. So you see that your equation states that the same amount of thingamajigs are jumping from i to j as from j to i. Hence the distribution stays the same under time evolution. If you know W then you can derive an equilibrium distribution with the DBC.

If the DBC holds than P is an equilibrium distribution. I am not sure if the inverse direction is also true.
 

Related to What is the connection between detailed balance and thermodynamic equilibrium?

1. What is detailed balance?

Detailed balance is a concept in physics and chemistry that refers to the equilibrium state of a system. It states that in an isolated system, the rate of forward and reverse reactions are equal, resulting in no net change in the system over time.

2. How is detailed balance related to thermodynamics?

Detailed balance is closely related to the second law of thermodynamics, which states that the total entropy of a closed system can never decrease over time. In a system that is in detailed balance, there is no net change in the system's entropy, meaning that it is in a state of maximum entropy.

3. What are some examples of systems that exhibit detailed balance?

Detailed balance can be observed in many physical and chemical systems, such as in chemical reactions, diffusion processes, and thermal equilibrium. It is also commonly seen in biological systems, such as enzyme-catalyzed reactions, where the rate of the forward reaction is equal to the rate of the reverse reaction.

4. How is detailed balance important in understanding the behavior of systems?

Detailed balance is a fundamental concept in understanding the behavior of physical and chemical systems. It allows us to predict the equilibrium state of a system and understand how it will respond to changes in its environment. It is also essential in the study of irreversible processes and the development of statistical mechanics theories.

5. Can detailed balance ever be violated?

In an isolated system, detailed balance is always observed. However, in open systems that exchange energy or matter with their surroundings, detailed balance can be violated. This can occur in systems that are far from equilibrium or in the presence of external forces. Violations of detailed balance can lead to interesting behavior and are a topic of ongoing research in physics and chemistry.

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