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Maximum Entropy Principle, Equal Probability a Priori and Gibbs Paradox

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arxiv 1105.4118 v2 pith:HD3HR2CN submitted 2011-05-20 cond-mat.stat-mech

classification cond-mat.stat-mech
keywords approachclassicentropygibbsmaxentmechanicsboltzmanncanonical
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We prove that information-theoretic maximum entropy (MaxEnt) approach to canonical ensemble is mathematically equivalent to the classic approach of Boltzmann, Gibbs and Darwin-Fowler. The two approaches, however, "interpret" a same mathematical theorem differently; most notably observing mean-energy in the former and energy conservation in the latter. However, applying the same MaxEnt method to grand canonical ensemble fails; while carefully following the classic approach based on Boltzmann's microcanonical {\em equal probability a priori} produces the correct statistics: One does not need to invoke quantum mechanics; and there is no Gibbs paradox. MaxEnt and related minimum relative entropy principle are based on the mathematical theorem concerning large deviations of rare fluctuations. As a scientific method, it requires classic mechanics, or some other assumptions, to provide meaningful {\em prior distributions} for the expected-value based statistical inference. A naive assumption of uniform prior is not valid in statistical mechanics.

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Reviewed papers in the Pith corpus that reference this work. Sorted by Pith novelty score. Full citation record

  1. Solving the Gibbs Paradox by Local Free Space and Collision Potential

    cond-mat.stat-mech 2026-08 reject novelty 4.0 of 10

    The paper derives a new formula for gas-mixture entropy increase that depends on molecular properties, but the derivation contains algebraic errors and predicts negative entropy for common gas pairs.

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