Scope of Boltzmann's entropy formula

ID: scope-of-boltzmann-s-entropy-formula

The strings in Boltzmann entropy of a two-box occupancy are complete microstates only within the binary toy model. They retain a coarse-grained variable for each particle and omit its exact position within a box and its momentum. An actual classical gas instead occupies continuous phase space; obtaining a dimensionless count from a phase space volume requires a specified cell convention and the appropriate treatment of particle identity. A quantum state count must respect the allowed quantum states and quantum statistics. Thus is not a general count of microstates for a gas obeying quantum ideal-gas statistics. [ref]
For a discrete probability distribution with unequal weights, use the existing Gibbs entropy article; its equal-weight case gives Boltzmann's entropy formula. Shannon entropy uses the corresponding information measure, with the logarithm base setting its units. A count alone cannot replace the specified probability distribution, as the Boltzmann distribution examples demonstrate. [ref]
Overwhelming multiplicity explains why thermodynamic equilibrium is overwhelmingly probable in macroscopic systems under the appropriate statistical assumptions. It does not make low-entropy thermal fluctuations logically impossible. Nor does counting alone derive irreversible macroscopic evolution: one also needs dynamics, an initial preparation, and a reason the system samples the allowed microstates on the timescale of interest. [ref]
Historically, Boltzmann's 1877 paper counted microscopic arrangements, called complexions, and related the natural logarithm of their number to entropy. The Sharp and Matschinsky translation appeared in Entropy 17 (2015), pages 1971–2009, DOI 10.3390/e17041971. Its notation differs from ours: Boltzmann's permutability measure is already logarithmic, whereas here is the count. [ref] Josiah Willard Gibbs's Elementary Principles in Statistical Mechanics (1902) developed the statistical ensemble framework; Chapter XIV compares several statistical definitions of entropy with thermodynamics. [ref] [ref]

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