In Boltzmann entropy of a two-box occupancy, impose an initial restriction that all labels are left. There is one allowed coarse microstate. Remove that restriction, allowing all occupancy values: the allowed set is now the union of every occupancy macrostate, containing strings. If the final description assigns equal probability to this whole set, its Boltzmann entropy change is
The counting identity is the binomial theorem. For twenty labels, . This final description fixes neither box occupancy; it is coarser than the particular macrostate , whose Boltzmann entropy is . The two counts answer different questions, so substituting the balanced macrostate for the full allowed set would change the calculation.
For four labels, the initial all-left string is 0000; removing the restriction makes all sixteen strings available. The column has only six strings. Accordingly, the whole allowed set has Boltzmann entropy , while the balanced macrostate has Boltzmann entropy .
Figure 1.
Sixteen configurations of four labeled particles grouped by left occupancy, compared with the all-left restriction
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Removing a barrier changes the allowed set immediately, but it does not instantaneously randomize the actual probability distribution. Motion and equilibration must make those configurations accessible. The counting result illustrates the configurational contribution to free expansion; it does not describe the relaxation time or every contribution to the entropy of a real gas.
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]