Equivalence and Distinction of Boltzmann and Gibbs Entropies

Two men have their names on the entropy of statistical mechanics, and if you look closely they wrote down genuinely different formulas. Boltzmann's entropy is assigned to a single macrostate: it is the logarithm of the number of microstates compatible with that macrostate, SB=kBln⁡ΩS_B=k_B\ln\Omega. Gibbs entropy, by contrast, is assigned to a probability distribution {pi}\{p_i\} over microstates, regardless of whether those microstates belong to one macrostate or many. One counts a set; the other averages over a cloud. They are not obviously the same object — so why does every textbook use "the entropy" as if there were only one? Because for a macroscopic system they agree to breathtaking accuracy. The number of microstates grows so violently with energy that the equilibrium macrostate crushes every competitor exponentially in NN; the equilibrium ensemble is, for counting purposes, a single spike. When the probability distribution is overwhelmingly concentrated on the equilibrium macrostate, the Gibbs entropy reproduces the Boltzmann entropy kBln⁡Ωk_{\mathrm B}\ln\Omega up to a correction of order ln⁡N\ln N, negligible compared with the extensive entropy O(N)O(N). This article proves that agreement, on a paramagnet you can hold in your hand, and shows the gap shrinking as ln⁡N/N\ln N/N. But an equivalence that holds to order ln⁡N\ln N is a warning as much as a reassurance: the two entropies come apart exactly where NN is small, where forces are long-ranged, or where you ask a dynamical question. The fine-grained Gibbs entropy never changes under Hamiltonian flow — Liouville forbids it — so it cannot be the entropy that rises in the second law. And the choice between counting a thin energy shell (Boltzmann) or the whole volume below EE (Gibbs's "volume entropy") decides whether negative absolute temperatures are real. Knowing when Boltzmann equals Gibbs, and precisely when it does not, is knowing where statistical mechanics is safe.

Key takeaways
  • Boltzmann entropy SB=kBln⁡ΩS_{\mathrm B}=k_{\mathrm B}\ln\Omega scores a single macrostate by its microstate count; Gibbs entropy SG=−kB∑ipiln⁡piS_{\mathrm G}=-k_{\mathrm B}\sum_i p_i\ln p_i scores a whole distribution over microstates.
  • On the microcanonical distribution (pi=1/Ωp_i=1/\Omega) they are exactly equal; that identity is owned by neighbouring articles and only recalled here.
  • For a macroscopic system in equilibrium the two agree up to an absolute error of order ln⁡N\ln N, i.e. a relative error of order ln⁡N/N→0\ln N/N\to0 — the entropic face of ensemble equivalence.
  • The gap is real and computable: on an NN-spin paramagnet the exact microcanonical ln⁡Ω\ln\Omega and the canonical −∑pln⁡p-\sum p\ln p differ by 12ln⁡(2πNpq)\tfrac12\ln(2\pi N pq), a ln⁡N\ln N correction demonstrated numerically here.
  • They genuinely diverge for small NN, long-range forces, non-concave S(E)S(E), and the fine-grained-vs-coarse-grained distinction that drives the second law.
  • Key idea: Boltzmann and Gibbs entropies are two different functionals that coincide to order ln⁡N\ln N because the equilibrium macrostate dominates the count exponentially — so they agree for thermodynamics but part ways for small systems and for dynamics.
The core insight

The Boltzmann entropy of the equilibrium macrostate and the Gibbs entropy of the equilibrium ensemble differ only by a term of order ln⁡N\ln N, negligible compared with the extensive entropy O(N)O(N), because the equilibrium macrostate carries an overwhelmingly large fraction of the total probability. Where that peaking fails (small NN, long range, dynamics), the two entropies separate.

Where this lives today

The comparison is not a settled historical footnote — it is an active research front wherever systems are small or forces are long-ranged. Experiments on ultracold atoms in optical lattices have revived the debate over Boltzmann (surface) and Gibbs (volume) entropies for systems with bounded spectra. In such systems the two definitions can predict different signs for the absolute temperature, leading to an extended discussion about which entropy provides the thermodynamically consistent description. The stakes are practical: the two definitions predict different signs of heat flow for such systems. At the nanoscale finite-size entropy corrections of order ln⁡N\ln N can become experimentally relevant. Single-molecule and single-electron thermodynamics operate at NN of tens, where per-particle corrections of 0.1 kB0.1\,k_{\mathrm B} are measurable and where ensemble inequivalence — negative microcanonical specific heat in small clusters and in self-gravitating models — is observed rather than hypothesized. Recognizing that Boltzmann and Gibbs entropies differ only by subextensive corrections in macroscopic systems—but can differ measurably in finite systems—is essential for modern small-system thermodynamics.

The physical picture

Picture the whole ensemble as a cloud of probability draped over the accessible microstates. Gibbs entropy measures the uncertainty associated with the probability distribution over microstates, whereas Boltzmann entropy depends only on the number of microstates belonging to a given macrostate. At equilibrium the probability distribution is overwhelmingly concentrated on the equilibrium macrostate, so evaluating the Gibbs entropy and counting the equilibrium microstates produce the same thermodynamic entropy up to subextensive corrections. This is why the two names are often used interchangeably in equilibrium statistical mechanics. The reason the cloud is a spike is the violence of the counting. The density of microstates grows exponentially with system size, while the Boltzmann factor e−βEe^{-\beta E} suppresses high energies. Their competition produces a sharply peaked probability distribution centred on the equilibrium energy. The figure shows this for a paramagnet: the microcanonical picture (a flat plateau of Ω\Omega equally-weighted microstates) and the canonical picture (a Gaussian-sharp distribution over energy) return entropies that sit on top of each other.

Figure
Boltzmann counts equilibrium microstates, Gibbs averages over their probability distribution—both give the same thermodynamic entropy in the large-N limit.
Two entropies, one number: the equilibrium macrostate dominates Ω equal-weight microstates Boltzmann: S = k ln Ω count the accessible plateau Gibbs: S = −k Σ p ln p average over the sharp cloud width ∝ 1/√N S_B and S_G agree to order ln N ⇒ same thermodynamics the whole spike lives inside one macrostate, so counting it = averaging over it

Now the payoff — the actual size of the disagreement, plotted. On a two-level paramagnet the exact microcanonical entropy per spin and the canonical entropy per spin can both be computed in closed form, and their difference is a pure ln⁡N\ln N effect. Divide it by NN and watch it die:

Figure
The gap per particle collapses as ln N / N — equivalence made quantitative
(S_B − S_G)/N vs N : the equivalence is an inverse-N law N (log scale) → (S_B − S_G)/Nk_B N=10: gap ≈ 0.16 per spin (visible!) N=10³: ≈ 0.004 N=10⁶: ≈ 6×10⁻⁶ absolute gap ~ ½ln(2πN pq) grows like ln N; divided by N it vanishes — Boltzmann = Gibbs in the limit

The lesson of the second figure is the whole article in one curve: the two entropies never agree exactly for finite NN, but their per-particle difference falls like ln⁡N/N\ln N/N, so by the time NN is Avogadro-sized the distinction is ∼10−22\sim10^{-22} and utterly unmeasurable. For a nanomagnet of ten spins, though, the 0.16 kB0.16\,k_{\mathrm B} per spin gap is real physics.

The core equations

Start from the two definitions, stated so their different natures are visible. The Boltzmann entropy assigns a number to a macrostate through the number Ω\Omega of compatible microstates; it presupposes equal a priori weighting of the microstates it counts:

SB(E,V,N)=kBln⁡Ω(E,V,N)(1)S_{\mathrm B}(E,V,N)=k_{\mathrm B}\ln\Omega(E,V,N) \qquad (1)

where: SBS_{\mathrm B} — Boltzmann (surface) entropy; Ω\Omega — the number of microstates on the energy shell [E,E+δE][E,E+\delta E], owned and derived in Boltzmann Entropy; kB=1.380649×10−23 J/Kk_{\mathrm B}=1.380649\times10^{-23}\ \mathrm{J/K} (exact, 2019 SI). This is a function of the macrostate alone — no probability distribution appears. The Gibbs entropy takes a distribution and returns a number; it is defined for any ensemble, in or out of equilibrium:

SG=−kB∑ipiln⁡pi(2)S_{\mathrm G}=-k_{\mathrm B}\sum_i p_i\ln p_i \qquad (2)

where: SGS_{\mathrm G} — Gibbs entropy; pip_i — probability of microstate ii; the sum runs over all microstates, derived and owned in Gibbs Entropy. Read it as the probability-weighted average of the information content −ln⁡pi-\ln p_i; broad distributions score high, sharp ones score low. On the microcanonical distribution the two collapse into one. Setting pi=1/Ωp_i=1/\Omega on the Ω\Omega accessible microstates and zero elsewhere:

−kB∑i=1Ω1Ωln⁡1Ω=kBln⁡Ω=SB(3)-k_{\mathrm B}\sum_{i=1}^{\Omega}\tfrac1\Omega\ln\tfrac1\Omega = k_{\mathrm B}\ln\Omega = S_{\mathrm B} \qquad (3)

where: the collapse is exact, not asymptotic — it is the identity that lets us speak of a single entropy for an isolated system. This equality is proved in Gibbs Entropy and Equal A Priori Probabilities; here it is the anchor from which the interesting inequivalence is measured. The substantive comparison is between the canonical Gibbs entropy and the microcanonical Boltzmann entropy — two different ensembles for the same physical system. The connection between the canonical and microcanonical descriptions follows from the thermodynamic relation obtained by evaluating the partition function in the thermodynamic limit:

SGcan=⟨E⟩−FT,F=−kBTln⁡Z,Z=∑ie−βEi(4)S_{\mathrm G}^{\mathrm{can}} = \frac{\langle E\rangle - F}{T},\qquad F=-k_{\mathrm B}T\ln Z,\qquad Z=\sum_i e^{-\beta E_i} \qquad (4)

where: FF — Helmholtz free energy; ZZ — canonical partition function; β=1/kBT\beta=1/k_{\mathrm B}T. The Laplace/saddle-point evaluation of Z=∫ ⁣dE Ω(E)e−βEZ=\int\!\mathrm dE\,\Omega(E)e^{-\beta E} is dominated by the energy E∗E^* where β=∂Eln⁡Ω\beta=\partial_E\ln\Omega, tying the canonical entropy back to ln⁡Ω(E∗)\ln\Omega(E^*). Carrying the saddle-point Carrying the saddle-point expansion to the next order yields the leading finite-size correction, which determines both the magnitude and the sign of the difference between the two entropies:

SGcan=SB(E∗)+12kBln⁡ ⁣(2πkBT2CV)+⋯(5)S_{\mathrm G}^{\mathrm{can}} = S_{\mathrm B}(E^*) + \tfrac12 k_{\mathrm B}\ln\!\big(2\pi k_{\mathrm B}T^2 C_V\big) + \cdots \qquad (5)

where: CVC_V is the constant-volume heat capacity. Since CV∝NC_V\propto N for an extensive system, the correction is of order ln⁡N\ln N, so SGcan−SB=O(ln⁡N)S_G^{\rm can}-S_B=O(\ln N) while the relative difference scales as O(ln⁡N/N)O(\ln N/N). Thus the two entropies become equivalent in the thermodynamic limit even though they differ by a finite-size correction. Finally the volume entropy, Gibbs's alternative to the surface entropy, counts everything below EE rather than a shell at EE:

SΣ=kBln⁡Φ(E),Φ(E)=∫H≤Ed3Nq d3NpN! h3N(6)S_{\Sigma}=k_{\mathrm B}\ln\Phi(E),\qquad \Phi(E)=\int_{H\le E}\frac{\mathrm d^{3N}q\,\mathrm d^{3N}p}{N!\,h^{3N}} \qquad (6)

where: Φ\Phi — the phase-space volume enclosed by the energy surface; SΣS_\Sigma agrees with SBS_{\mathrm B} to O(ln⁡N)O(\ln N) for normal systems but differs in sign of ∂S/∂E\partial S/\partial E for systems with a bounded spectrum — the root of the negative-temperature debate.

Derivation ABoltzmann equals Gibbs to order ln N — the paramagnet made exact

This is the article's owned structural result: for the two-level paramagnet, both entropies are known in closed form, and their difference is exactly a ln⁡N\ln N term — no hand-waving, no unspecified "corrections." We compute the microcanonical (Boltzmann) entropy from the exact binomial multiplicity, the canonical (Gibbs) entropy from the exact partition function, match them at equal mean energy, and read off the gap. The point is to turn "equivalence up to O(ln⁡N)O(\ln N)" from a slogan into a formula you can evaluate at N=10N=10 and N=106N=10^6 and watch converge.

Step 1. Count the macrostate. With NN non-interacting two-level spins (ε=0\varepsilon=0 or ε\varepsilon), a macrostate of nn excited spins has multiplicity Ω(n)=(Nn)\Omega(n)=\binom{N}{n}, so the Boltzmann entropy per spin is sB=1Nln⁡(Nn)s_{\mathrm B}=\tfrac1N\ln\binom{N}{n}. Why: the macrostate fixes only the number excited; the microstates correspond to the different choices of which nn spins are excited, a binomial coefficient — this is the counting owned by Counting and Combinatorics of Microstates.

Step 2. Apply Stirling to leading order only, ln⁡(Nn)=N ⁣[−xln⁡x−(1−x)ln⁡(1−x)]+O(ln⁡N)\ln\binom{N}{n}=N\!\left[-x\ln x-(1-x)\ln(1-x)\right]+O(\ln N) with x=n/Nx=n/N. The bracket is the binary entropy H(x)H(x); the discarded piece is −12ln⁡ ⁣(2πNx(1−x))-\tfrac12\ln\!\big(2\pi Nx(1-x)\big). Why: the extensive part is the physics; the 12ln⁡N\tfrac12\ln N remainder is precisely the term we are hunting — we keep track of it rather than dropping it (that tracking is owned by The Stirling Approximation).

Step 3. Now the canonical route. The single-spin partition function is z=1+e−βεz=1+e^{-\beta\varepsilon}, so Z=zNZ=z^N and the Gibbs entropy is SGcan=kBN[ln⁡z+βε nˉ]S_{\mathrm G}^{\mathrm{can}}=k_{\mathrm B}N\big[\ln z+\beta\varepsilon\,\bar n\big] with nˉ=e−βε/z\bar n=e^{-\beta\varepsilon}/z the mean excitation fraction. Written in x=nˉx=\bar n, sG=H(x)s_{\mathrm G}=H(x) exactly — the leading binary-entropy term, with no ln⁡N\ln N piece. Why: the canonical ensemble sums over all energies with smooth weights, so its entropy is a clean per-spin function; the factorial's finite-size tail simply never enters.

Step 4. Match at equal mean energy (n=Nxn=Nx in both) and subtract. The difference is entirely the term Stirling left behind:

SB−SGcan=−12kBln⁡ ⁣(2πNx(1−x))+O(1/N)S_{\mathrm B}-S_{\mathrm G}^{\mathrm{can}} = -\tfrac12 k_{\mathrm B}\ln\!\big(2\pi N x(1-x)\big) + O(1/N)

Why: the extensive N H(x)N\,H(x) pieces cancel identically, leaving a pure −12ln⁡N-\tfrac12\ln N correction. Its relative size is ln⁡N/(2NH)→0\ln N/(2NH)\to0: equivalence. Its absolute size is a fraction of kBk_{\mathrm B} per system — real for a nanomagnet, invisible for a mole. Note the sign: the surface (Boltzmann) entropy sits below the canonical Gibbs entropy by this half-log, because the shell is a slice of the fluctuating canonical distribution. *The exact ln⁡(Nn)\ln\binom{N}{n} vs NH(n/N)N H(n/N) comparison and the 12ln⁡(2πNx(1−x))\tfrac12\ln(2\pi Nx(1-x)) gap have been evaluated at N=10,102,103,106N=10,10^2,10^3,10^6; the per-particle gap falls as ln⁡N/N\ln N/N in each case.*

Go deeper · Derivation B · 1 minWhy the fine-grained Gibbs entropy cannot be the second-law entropy
Derivation BWhy the fine-grained Gibbs entropy cannot be the second-law entropy

The most important distinction between the two entropies is dynamical, and it is a theorem, not a subtlety: under exact Hamiltonian evolution the Gibbs entropy of the full phase-space density is a constant of the motion. It literally cannot increase. Any entropy that rises toward equilibrium — the thermodynamic one — must therefore be a coarse-grained object, not the fine-grained Gibbs functional. This derivation establishes the constancy and names what has to give.

Step 1. Write the Gibbs entropy of a continuous density, SG[ρ]=−kB ⁣∫ρln⁡ρ dΓS_{\mathrm G}[\rho]=-k_{\mathrm B}\!\int\rho\ln\rho\,\mathrm d\Gamma, and evolve ρ\rho by the Liouville equation ∂tρ={H,ρ}\partial_t\rho=\{H,\rho\}. Why: the ensemble is now a smooth density on phase space, transported by the exact flow — the setting owned by Liouville's Theorem and Liouville Equation.

Step 2. The flow is measure-preserving: dΓ(t)=dΓ(0)\mathrm d\Gamma(t)=\mathrm d\Gamma(0) because the Jacobian of Hamiltonian flow is 11 (Liouville). Along a trajectory ρ\rho is constant, ρ(Γ(t),t)=ρ(Γ(0),0)\rho(\Gamma(t),t)=\rho(\Gamma(0),0). Why: this is exactly the incompressibility proved in Liouville's Theorem; probability rides the flow like an incompressible fluid.

Step 3. Therefore SG[ρ(t)]=−kB ⁣∫ρln⁡ρ dΓS_{\mathrm G}[\rho(t)]=-k_{\mathrm B}\!\int\rho\ln\rho\,\mathrm d\Gamma is time-independent: change variables to the initial coordinates, unit Jacobian, and the integral is frozen. dSG/dt=0\mathrm dS_{\mathrm G}/\mathrm dt=0. Why: any functional of ρ\rho that integrates over phase space is conserved when ρ\rho is merely relabelled by a volume-preserving map — the values of ρ\rho are shuffled around, never changed.

Step 4. The entropy that increases in macroscopic thermodynamics is not the fine-grained Gibbs entropy SG[ρ]S_G[\rho], but a coarse-grained entropy obtained by replacing ρ\rho with a locally averaged density ρˉ\bar\rho. Coarse-graining removes fine phase-space filaments generated by Hamiltonian evolution, and Jensen's inequality implies Sˉ=−kB∫ρˉln⁡ρˉ dΓ≥SG\bar S=-k_B\int\bar\rho\ln\bar\rho\,d\Gamma\ge S_G. Thus the apparent entropy increase reflects the loss of microscopic resolution rather than a change in the exact Gibbs entropy. The detailed connection to irreversibility is developed in the article on the statistical origin of the second law.

Limiting cases

CaseResultMeaning
Microcanonical distributionSG=SB=kBln⁡ΩS_{\mathrm G}=S_{\mathrm B}=k_{\mathrm B}\ln\Omega exactlyon equal-weight microstates the Gibbs functional collapses to the Boltzmann count — no gap at all
Macroscopic equilibrium, N→∞N\to\inftySB−SGcan=O(ln⁡N)S_{\mathrm B}-S_{\mathrm G}^{\mathrm{can}}=O(\ln N), relative O(ln⁡N/N)→0O(\ln N/N)\to0ensemble equivalence: the two entropies agree per particle in the thermodynamic limit
Small NN (nanomagnet, cluster)gap ∼12ln⁡(2πN)\sim\tfrac12\ln(2\pi N) per system, non-negligiblethe ln⁡N\ln N correction is real physics; ensembles are measurably inequivalent
Bounded spectrum, S(E)S(E) non-monotoneSΣS_\Sigma (volume) and SΩS_\Omega (surface) disagree on sign(∂S/∂E)\mathrm{sign}(\partial S/\partial E)the Boltzmann-vs-Gibbs temperature controversy: whether T<0T<0 is admissible
Long-range forces / first-order transitionS(E)S(E) non-concave; ensembles inequivalent even as N→∞N\to\inftynegative microcanonical specific heat; canonical ensemble cannot see it

Worked examples

1 · The actual size of the gap for a ten-spin nanomagnet (real number)

Take N=10N=10 non-interacting spins at the maximum-entropy point x=nˉ/N=1/2x=\bar n/N=1/2. Compute the exact microcanonical Boltzmann entropy per spin from Eq. (1), the canonical Gibbs entropy per spin from the binary entropy, and compare the two. Then repeat at N=106N=10^6 to see the collapse.

Step 1. Exact microcanonical count at n=N/2=5n=N/2=5: (105)=252\binom{10}{5}=252, so SB=kBln⁡252S_{\mathrm B}=k_{\mathrm B}\ln 252, i.e. ln⁡252=5.5294\ln 252=5.5294 and sB=SB/NkB=5.5294/10=0.5529s_{\mathrm B}=S_{\mathrm B}/Nk_{\mathrm B}=5.5294/10=\boxed{0.5529} per spin.

Step 2. Canonical entropy per spin at x=1/2x=1/2 is the binary entropy H(1/2)=−12ln⁡12−12ln⁡12=ln⁡2=0.6931H(1/2)=-\tfrac12\ln\tfrac12-\tfrac12\ln\tfrac12=\ln 2=0.6931, so sG=0.6931s_{\mathrm G}=\boxed{0.6931} per spin.

Step 3. The gap per spin is sG−sB=0.6931−0.5529=0.1402s_{\mathrm G}-s_{\mathrm B}=0.6931-0.5529=0.1402. Compare this exact finite-size difference with the asymptotic prediction 12Nln⁡(2πNx(1−x))=120ln⁡(2π⋅10⋅14)=120ln⁡(15.71)=120(2.754)=0.1377\tfrac{1}{2N}\ln(2\pi N x(1-x))=\tfrac{1}{20}\ln(2\pi\cdot10\cdot\tfrac14)=\tfrac{1}{20}\ln(15.71)=\tfrac{1}{20}(2.754)=0.1377 — agreement to a percent, the small residue being the O(1/N)O(1/N) Stirling tail. At ten spins the two entropies differ by about 0.14 kB0.14\,k_{\mathrm B} per spin — a fifth of ln⁡2\ln 2.

Step 4. Now N=106N=10^6: the predicted per-spin gap is 12×106ln⁡(2π⋅106⋅14)=12×106(14.27)=7.1×10−6\tfrac{1}{2\times10^6}\ln(2\pi\cdot10^6\cdot\tfrac14)=\tfrac{1}{2\times10^6}(14.27)=7.1\times10^{-6}. The distinction that was a fifth of ln⁡2\ln 2 at ten spins is seven parts per million at a million — and ∼10−17\sim10^{-17} at a mole. For macroscopic systems the remaining difference is utterly negligible, so the two entropies are thermodynamically equivalent.

2 · Surface versus volume entropy for an ideal gas (exam level)

For a monatomic ideal gas, Φ(E)∝E3N/2\Phi(E)\propto E^{3N/2} (volume below EE) and ω(E)=∂EΦ∝E3N/2−1\omega(E)=\partial_E\Phi\propto E^{3N/2-1} (surface). Show the surface entropy SΩ=kBln⁡(ω δE)S_\Omega=k_{\mathrm B}\ln(\omega\,\delta E) and the volume entropy SΣ=kBln⁡ΦS_\Sigma=k_{\mathrm B}\ln\Phi differ only at order ln⁡N\ln N, and that both give the same temperature to leading order.

Step 1. Volume entropy: SΣ=kBln⁡Φ=kB[3N2ln⁡E+const]S_\Sigma=k_{\mathrm B}\ln\Phi=k_{\mathrm B}\big[\tfrac{3N}{2}\ln E+\text{const}\big]. Its temperature: 1TΣ=∂ESΣ=kB3N21E\tfrac{1}{T_\Sigma}=\partial_E S_\Sigma=k_{\mathrm B}\tfrac{3N}{2}\tfrac1E, so E=32NkBTΣE=\tfrac32 Nk_{\mathrm B}T_\Sigma — the equipartition result exactly.

Step 2. Surface entropy: SΩ=kBln⁡(ω δE)=kB[(3N2−1)ln⁡E+const]S_\Omega=k_{\mathrm B}\ln(\omega\,\delta E)=k_{\mathrm B}\big[(\tfrac{3N}{2}-1)\ln E+\text{const}\big]. The two logs of EE differ by one unit of 3N2\tfrac{3N}{2} — i.e. by ln⁡E\ln E, an O(1)O(1) piece against the O(N)O(N) entropy.

Step 3. Difference: SΣ−SΩ=kBln⁡E+const=O(ln⁡N)S_\Sigma-S_\Omega=k_{\mathrm B}\ln E + \text{const}=O(\ln N) once E=32NkBTE=\tfrac32 Nk_{\mathrm B}T is inserted (so ln⁡E=ln⁡N+const\ln E=\ln N+\text{const}). The two definitions of "the entropy of the ideal gas" differ by a ln⁡N\ln N term — exactly the size found for the paramagnet, and negligible per particle.

Step 4. Temperatures: 1TΩ=kB(3N2−1)1E\tfrac{1}{T_\Omega}=k_{\mathrm B}(\tfrac{3N}{2}-1)\tfrac1E versus 1TΣ=kB3N21E\tfrac{1}{T_\Sigma}=k_{\mathrm B}\tfrac{3N}{2}\tfrac1E; the fractional difference is 1/(3N/2)=O(1/N)1/(3N/2)=O(1/N). For a normal (monotone-Ω\Omega) system the choice is immaterial. It becomes decisive only for a bounded spectrum, where ω(E)\omega(E) turns over and ∂ESΩ\partial_E S_\Omega can go negative while ∂ESΣ\partial_E S_\Sigma stays positive — the crux of the negative-temperature dispute.

Origins · 1 minEdwin Thompson Jaynes and how this was discovered
ET
Edwin Thompson Jaynes
1922–1998 · Stanford and Washington University in St. Louis

Jaynes reframed the whole Boltzmann–Gibbs question as one about information. In two 1957 papers he showed that the Gibbs entropy −kB∑piln⁡pi-k_{\mathrm B}\sum p_i\ln p_i is not a physical assumption at all but the least-biased distribution consistent with known constraints — maximize it subject to fixed ⟨E⟩\langle E\rangle and out drops the canonical ensemble; fix nothing but normalization and you get the microcanonical uniform distribution, recovering Boltzmann. From this angle the equivalence of the two entropies is the statement that, for a macroscopic system, the constraints pin the distribution so tightly that "count the microstates" and "maximize the information entropy" give the same answer. Jaynes was equally sharp on the distinctions: he stressed that the fine-grained Gibbs entropy is conserved by Liouville flow and that the second law's increase is a coarse-graining effect — the stirred-ink picture made rigorous. His maximum-entropy principle is now a standard tool far beyond physics, in image reconstruction, spectral analysis, and machine learning.

History
1865
— Clausius names entropy and states the second law in its classic form.
1877
— Boltzmann identifies entropy with the logarithm of a microstate count.
1902
— Gibbs's Elementary Principles in Statistical Mechanics gives the ensemble entropy −kB∑pln⁡p-k_{\mathrm B}\sum p\ln p and the coarse-graining (stirred-ink) resolution of its constancy.
1948
— Shannon derives the same −∑pln⁡p-\sum p\ln p functional as the unique measure of information.
1957
— Jaynes recasts statistical mechanics as maximum-entropy inference, unifying the Boltzmann and Gibbs entropies.
1965
— Jaynes's "Gibbs vs Boltzmann Entropies" clarifies which entropy rises in the second law.

Going further

Texts. Pathria & Beale, Statistical Mechanics, 3rd ed., §1.4, §3.7 (fluctuations and ensemble equivalence) · Kardar, Statistical Physics of Particles, §4.4–4.6 · Sethna, Statistical Mechanics: Entropy, Order Parameters, and Complexity, Ch. 3, 5 · Gibbs, Elementary Principles in Statistical Mechanics (1902), Ch. XI–XIV · Jaynes, "Information Theory and Statistical Mechanics" (Phys. Rev. 106, 620; 1957) and "Gibbs vs Boltzmann Entropies" (Am. J. Phys. 33, 391; 1965). Key results to keep in view: the exact identity −∑1Ωln⁡1Ω=ln⁡Ω-\sum\frac1\Omega\ln\frac1\Omega=\ln\Omega; the paramagnet gap ln⁡(Nn)−NH(n/N)=−12ln⁡(2πNx(1−x))+O(1/N)\ln\binom{N}{n}-NH(n/N)=-\tfrac12\ln(2\pi Nx(1-x))+O(1/N), evaluated at N=10,102,103,106N=10,10^2,10^3,10^6; the worked numbers (ln⁡252=5.5294\ln 252=5.5294, sB=0.5529s_{\mathrm B}=0.5529, ln⁡2=0.6931\ln 2=0.6931, gap 0.1400.140 vs prediction 0.1380.138 at N=10N=10; 7.1×10−67.1\times10^{-6} at N=106N=10^6); the ideal-gas scalings Φ∝E3N/2\Phi\propto E^{3N/2}, ω∝E3N/2−1\omega\propto E^{3N/2-1}, and the resulting O(ln⁡N)O(\ln N) surface–volume gap; and the Liouville-invariance of ∫ρln⁡ρ\int\rho\ln\rho. The only fundamental constant entering is kB=1.380649×10−23 J/Kk_{\mathrm B}=1.380649\times10^{-23}\ \mathrm{J/K} (exact, 2019 SI).

Prerequisites. Boltzmann Entropy · Gibbs Entropy · Statistical Ensembles · Microstates and Macrostates · Liouville's Theorem · Fundamental Postulate of Equal A Priori Probabilities. Leads to. Ergodic Theory and Mixing · Accessible Phase Space and Energy Shells · The Ergodic Hypothesis.

If they agree so well, why keep both entropies at all? Isn't one redundant?

Because they answer different questions and only one generalizes. The Boltzmann entropy is defined for a single macrostate of an isolated system; it says nothing about a system in a heat bath, out of equilibrium, or driven. The Gibbs entropy is defined for any probability distribution, so it is the one that survives into the canonical ensemble, non-equilibrium steady states, and information theory. For an isolated macroscopic system in equilibrium they coincide, so you use whichever is easier — usually Boltzmann's count. Everywhere else, Gibbs's functional is the general object and Boltzmann's is the special case.

The article says the gap is "order ln N." Where does the ln N actually come from?

From the finite-size tail of Stirling's approximation. The extensive part of ln⁡(Nn)\ln\binom{N}{n} is NN times the binary entropy — that piece agrees exactly with the canonical result. But Stirling has a next term, −12ln⁡(2πNx(1−x))-\tfrac12\ln(2\pi N x(1-x)), coming from ln⁡N!≈Nln⁡N−N+12ln⁡(2πN)\ln N!\approx N\ln N-N+\tfrac12\ln(2\pi N). That half-log is the whole gap. It reflects the difference between a thin energy shell (Boltzmann) and the full fluctuating distribution over energy (canonical Gibbs): the shell is one slice of a Gaussian of width ∝N\propto\sqrt N, and slicing costs you a 12ln⁡N\tfrac12\ln N.

Is the sign of S_B − S_G physically meaningful, or just bookkeeping?

It is meaningful but tiny. The surface (Boltzmann) entropy sits below the canonical Gibbs entropy by 12ln⁡(2πkBT2CV)\tfrac12\ln(2\pi k_{\mathrm B}T^2C_V), because the microcanonical shell corresponds to a single energy while the canonical ensemble spreads over a band of width kBT2CV\sqrt{k_{\mathrm B}T^2C_V} — extra spread means extra entropy. For a macroscopic system this is a ln⁡N\ln N correction to an NN entropy and never affects thermodynamics. For a small system it shifts computed free energies and heat capacities at the percent level, which is exactly why nanoscale thermodynamics has to specify which ensemble it means.

How can two "entropies" give different temperatures? Isn't temperature unique?

For normal matter it is — the surface and volume entropies give temperatures differing only at O(1/N)O(1/N). The definitions part company only for systems with a bounded energy spectrum (spins, some cold-atom lattices), where the density of states ω(E)\omega(E) rises, peaks, and falls. Past the peak ∂Eln⁡ω<0\partial_E\ln\omega<0, so the surface (Boltzmann) temperature goes negative, while the volume entropy ln⁡Φ\ln\Phi keeps rising and its temperature stays positive. Which is "the" temperature is genuinely debated; the practical test is which one makes the second law and heat flow consistent, and that argument is still live.

Does coarse-graining make the increase of entropy subjective — dependent on how I choose the cells?

The amount of increase depends mildly on the cell size, but the fact of increase does not, and this is not a defect. Any partition into finite cells small compared to macroscopic scales gives a coarse-grained entropy that starts at the fine-grained value and rises to kBln⁡Ωk_{\mathrm B}\ln\Omega as mixing threads ρ\rho below the cell resolution. The endpoint — the equilibrium Boltzmann entropy — is cell-independent; only the transient depends on resolution. Physically, "coarse-graining" is just the statement that real instruments have finite resolution, so the entropy that rises is the one an actual observer can access.

Why does ensemble inequivalence survive the thermodynamic limit for long-range systems but not short-range ones?

Equivalence rests on the entropy density s(e)=lim⁡1NS(Ne)s(e)=\lim \tfrac1N S(Ne) being concave. For short-range forces energy is additive and s(e)s(e) is concave, so the microcanonical and canonical descriptions share the same thermodynamics as N→∞N\to\infty. Long-range forces (gravity, unscreened Coulomb, mean-field magnets) make energy non-additive; s(e)s(e) can develop a convex intruder, and there the microcanonical ensemble shows negative specific heat that the canonical ensemble — which only ever sees the concave hull — cannot reproduce. The two ensembles then disagree about the phase diagram itself, no matter how large NN is.

Where does the Shannon entropy fit — is it a third entropy?

No — it is the Gibbs entropy wearing an information-theory hat. Shannon's −∑piln⁡pi-\sum p_i\ln p_i (up to the choice of kBk_{\mathrm B} versus log⁡2\log_2 and a unit) is identical to the Gibbs functional. That is why erasing information has a thermodynamic cost (Landauer's kBTln⁡2k_{\mathrm B}T\ln 2) and why Jaynes could rebuild statistical mechanics as inference. So the landscape is really two entropies, not three: Boltzmann's count of a macrostate, and the Gibbs/Shannon functional of a distribution — the same object whether you call its argument a probability or an information weight.

Before this

Where this leads