Boltzman’s H-theorem

Assuming fj, < 1/2, this solution implies a monotonic approach to equilibrium with time. From a purely statistical point of view, this is certainly correct the difference in number between the two different balls decreases exponentially toward a state in which neither color is preferred. In this sense, the solution is consistent with the spirit of Boltzman s H-theorem, expressing as it does the idea of motion towards disorder. But the equation is also very clearly wrong. It is wrong because it is obviously inconsistent with the fundamental properties of the system it violates both the system s reversibility and periodicity. While we know that the system eventually returns to its initial state, for example, this possibility is precluded by equation 8.142. As we now show, the problem rests with equation 8.141, which must be given a statistical interpretation. 

Boltzman s H-Theorem Let us consider a binary elastic collision of two hard-spheres in more detail. Using the same notation as above, so that v, V2 represent the velocities of the incoming spheres and v, V2 represent the velocities of the outgoing spheres, we have from momentum and energy conservation that... 

The fact that the condition dll/dl = 0 is the same as the condition of detailed-balance, and therefore that equation 9.34 is a necessary condition for the solution of equation 9.33, follows from the proof of Boltzman s H-Theorem ... 

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