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Two equal sealed vessels of fixed volume, initially at $T_0,p_0$, exchange an ideal gas through a thin effusive opening. Hold one at $T_1$ and the other at $T_0$, with both interiors locally thermalized. Zero net particle transfer gives $p_h/\sqrt{T_1}=p_c/\sqrt{T_0}$. Writing $q=\sqrt{T_1/T_0}$, conservation of total particle number gives $p_h=2p_0{q}^2/(1+q)$ and $p_c=2p_{0}q/(1+q)$. Thus $\Delta p=2p_{0}q(q-1)/(1+q)$. The alternative $p_c=p_0$, $\Delta p=p_0(q-1)$ requires a cold reservoir whose pressure is externally held fixed; it is not the closed equal-volume problem.

For distinct box modes ${\phi }_1=\sqrt{2/L}\sin (p\pi x/L)$ and ${\phi }_2=\sqrt{2/L}\sin (q\pi x/L)$, the displayed contact interaction overlaps produce self terms $3g{\sum }_j{n}_j(n_j-1)/(4L)$, a density term $2g{n}_1{n}_2/L$, and pair conversion $g(a_1^{†2}{a}_2^2+a_2^{†2}{a}_1^2)/(2L)$. Pair conversion preserves total particle number but prevents diagonalization by individual occupation numbers. The additional overlaps are $I_{1112}=-{\delta }_{q,3p}/(2L)$ and $I_{1222}=-{\delta }_{p,3q}/(2L)$, following from ${\sin }^{3}u=(3\sin u-\sin 3u)/4$. Third-harmonic mode pairs therefore also permit single-particle transfer assisted by the other particles. For the first two box modes these additional terms vanish.

Two distinct normalized plane waves on a periodic one-dimensional ring of length $L$ give the displayed projected contact interaction. Momentum conservation excludes pair conversion between these two modes. Four mixed operator orderings give the coefficient of $n_1{n}_2$. At fixed particle number $N$, the energy is $g[N(N-1)+2n_1(N-n_1)]/(2L)$. For repulsive coupling, its minima are the two endpoint Fock states with all particles in one mode; a one-particle energy difference selects the lower mode. This ground-state statement concerns the two-mode projection.

The contribution of Electrons to heat capacity. For a uniform noninteracting three-dimensional Fermi gas at fixed particle number and volume, its low-temperature value is $C_V\simeq ({\pi }^2/2)N{k}_{B}T/T_F$; only states near the Fermi surface can change occupation readily.

For a smooth single-spin density of states $g$ near a positive Fermi energy and fixed total particle number, the Sommerfeld expansion gives $\mu ={ϵ}_F-({\pi }^2/6)(g_F^{\prime }/g_F)(k_{B}T{)}^2+O(T^4)$. The spin contribution to the total-moment magnetic susceptibility, defined by differentiating with respect to $B$, is $2{\mu }_B^2\int g(E)[-n^{\prime }(E)]dE$. Expanding about $\mu$ and including the shift of chemical potential gives the displayed formula. The $g_F^{\prime \prime }$ term is thermal broadening; the $-g_F^{\prime 2}/g_F$ term enforces fixed particle number. A band edge or singular density of states within $k_{B}T$ of ${ϵ}_F$ requires a separate analysis. Orbital magnetic response is excluded.

The dimensionless quantum gas fugacity weights particle number in the grand canonical ensemble: a state with energy $E$ and particle number $N$ has weight $z^N{e}^{-\beta E}$. The chemical potential and one-particle energies must use the same reference. When the lowest one-particle energy is zero, $z\ll 1$ makes both fermion and boson occupations small throughout the low-energy spectrum. This dimensionless quantity must be distinguished from the pressure-valued fugacity used in chemical thermodynamics.

A particle number counts the particles of a specified kind in a system. For a fixed collection, $N$ is a nonnegative integer. In a variable-number quantum system, distinguish a measured particle number, the particle number operator, and its expected value.

In second quantization, expand the annihilating quantized field in a complete orthonormal basis of one-particle states, $\hat{\psi }(x)={\sum }_{\alpha }{\phi }_{\alpha }(x)a_{\alpha }$. At equal times, the canonical commutation relation for bosons and the canonical anticommutation relations for fermions are, respectively,andHere $\delta$ is a Dirac delta distribution. Multiplying by the basis wave functions and integrating gives $[a_{\alpha },a_{\beta }^{†}]={\delta }_{\alpha \beta }$ for bosons, or $\{a_{\alpha },a_{\beta }^{†}\}={\delta }_{\alpha \beta }$ for fermions; the two-annihilator and two-creator brackets vanish in the corresponding convention.

The mode number operator and total particle number operator areThe bosonic occupation numbers are $0,1,2,\dots$. For fermions, $a_{\alpha }^2=0$ and the canonical anticommutation relations imply $n_{\alpha }^2=n_{\alpha }$, so the fermionic occupation numbers are only $0$ and $1$, as required by the Pauli exclusion principle.

Keeping only two modes later is a projection: the projected field bracket is ${\sum }_{j=1}^2{\phi }_j(x){\phi }_j^{\ast }(x^{\prime })$, rather than the full Dirac delta distribution.

At fixed particle number $N$, write $n_1=n$ and $n_2=N-n$. The contact interaction between two ring modes has energy eigenvaluesFor $g>0$, the nonnegative product $n(N-n)$ is minimized at the endpoints. ConsequentlyFor $N\ge 1$ this is a two-dimensional degenerate ground state subspace. $N=0$ instead has the unique Fock vacuum. In this projected model, putting all particles into one traveling mode avoids the extra exchange contribution paid when both distinct modes are occupied.

For the alternative coefficients, put $\alpha =\beta =A<0$ and $\gamma =0$. Then $E(n)=A[N(N-1)-2n(N-n)]$ is again minimized at $n=0,N$, with $E_{\min }=AN(N-1)$. Evenness of $N$ is unnecessary for this result; the balanced Fock state maximizes this attractive-interaction energy instead of minimizing it.

For distinct positive integers $p,q$, use normalized box modes ${\phi }_1=\sqrt{2/L}\sin (p\pi x/L)$ and ${\phi }_2=\sqrt{2/L}\sin (q\pi x/L)$. Their contact interaction overlaps obeyUnlike traveling ring modes, these standing modes also allow pair conversion. For the first two box modes, or any distinct pair without a third-harmonic resonance, the contact interaction between two box modes isThe last two terms change an individual mode occupation number by two while conserving total particle number. Thus the Hamiltonian operator is not diagonal in the Fock state basis, and minimizing diagonal entries alone does not find its ground state. For example, at $N=2$ with no dispersion, $\left(|2,0⟩-|0,2⟩\right)/\sqrt{2}$ has the lowest energy $g/(2L)$, below either unmixed endpoint's $3g/(2L)$.

The wording permits modes beyond the first two. For completeness, the identity ${\sin }^{3}u=(3\sin u-\sin 3u)/4$ givesWhen $q=3p$, add $-g(a_1^{†2}{a}_1{a}_2+a_1^{†}{a}_2^{†}{a}_1^2)/(2L)$; when $p=3q$, add $-g(a_1^{†}{a}_2^{†}{a}_2^2+a_2^{†2}{a}_1{a}_2)/(2L)$. These extra terms change an individual occupation number by one and require diagonalizing the corresponding fixed-$N$ matrix as well.

In the grand canonical ensemble, the system exchanges both energy and particles with a reservoir at fixed temperature $T$ and chemical potential $\mu$. The probability of a particular many-body microstate $i$, with energy $E_i$ and particle number $N_i$, is its Boltzmann weight $e^{-\beta (E_i-\mu N_i)}$ divided by the grand canonical partition function $\Xi$, where $\beta =1/(k_{B}T)$. The denominator normalizes ${\sum }_i{p}_i=1$; a degeneracy is accounted for by counting distinct microstates, rather than changing an individual state's probability.

For noninteracting particles, specify a microstate by the occupation numbers $n_r$ of one-particle levels of energy ${ϵ}_r$. Then $E-\mu N={\sum }_r({ϵ}_r-\mu )n_r$, so the Gibbs probability factorizes between levels. Put $x_r=e^{-\beta ({ϵ}_r-\mu )}$.

For fermions, the Pauli exclusion principle permits $n_r=0,1$ in each complete one-particle state, giving ${\Xi }_r=1+x_r$. Its mean occupancy isthe Fermi-Dirac distribution.

For bosons, $n_r=0,1,2,\dots$, so the geometric sum is ${\Xi }_r=1/(1-x_r)$ when $x_r<1$. Differentiating that sum givesthe Bose-Einstein distribution. Finite-system convergence requires $\mu <{ϵ}_{\min }$; condensation is the limiting approach to the lowest energy with macroscopic ground-state occupation. Both quantum distributions reduce to $e^{-\beta ({ϵ}_r-\mu )}$ when occupation is small. The quantities derived here are mean occupancies of states, rather than normalized probabilities over the set of one-particle energies.

Component chemical potentials. Define the per-spin quantum concentration $n_Q={\lambda }_T^{-3}=(m{k}_{B}T/(2\pi {\hslash }^2){)}^{3/2}$. For a classical component with one-particle potential energy $U_{\sigma }(\mathbf{r})$, the local Helmholtz free energy density is $k_{B}T{n}_{\sigma }[\ln (n_{\sigma }/n_Q)-1]+n_{\sigma }{U}_{\sigma }$. Its derivative with respect to number density gives the full local chemical potential, including the magnetic energy. With the up state defined as the lower level,The Bohr magneton ${\mu }_B$ is a magnetic moment; ${\mu }_{B}B$ is an energy. The factor two for the two spin states is not already included in $n_Q$.

Total equilibrium chemical potential. If spin conversion is allowed, a particle can be added in either spin state at the same equilibrium free-energy cost. Thusnot their sum or zero. The total particle number, or a reservoir, fixes this common value; the supplied information does not specify a numerical chemical potential. A useful local expression is $\mu =k_{B}T\ln [n/(2n_Q\cosh x)]$, with $x={\mu }_{B}B/(k_{B}T)$, whose density dependence is found below.

Why it is uniform and common. Moving a small number $dN$ of one species from ${\mathbf{r}}_1$ to ${\mathbf{r}}_2$ changes the free energy by $[{\mu }_{\sigma }({\mathbf{r}}_2)-{\mu }_{\sigma }({\mathbf{r}}_1)]dN$. If this difference were nonzero, a transfer could lower the free energy. Equilibrium under diffusion therefore requires each full chemical potential to be spatially constant. A spin flip transferring $dN$ from down to up similarly changes free energy by $({\mu }_{\uparrow }-{\mu }_{\downarrow })dN$, proving equality when spin relaxation is permitted. This is chemical equilibrium of a classical spin gas. Mere thermal contact at fixed separate spin populations would not enforce the latter equality; full spin equilibrium is the necessary assumption. A spatially varying magnetic field is balanced by a spatially varying density, not by a varying full chemical potential.

Magnetization. Invert the component equations at the common $\mu$:The two levels have moments $+{\mu }_B$ and $-{\mu }_B$ along the field. The magnetization, magnetic moment per unit volume, is thereforeIts SI units are $\mathrm{A}{\mathrm{m}}^{-1}$. This expression neglects interactions and magnetic feedback of the gas on the specified external field.

High-temperature response. For $|x|\ll 1$, $\sinh x\simeq x$ and $\cosh x\simeq 1$, yieldingAt fixed number density, this is the Curie law: the susceptibility with respect to $B$ is $n{\mu }_B^2/(k_{B}T)$. The conventional dimensionless susceptibility with respect to $H$ is approximately ${\chi }_v={\mu }_{0}n{\mu }_B^2/(k_{B}T)$ when $B\simeq {\mu }_{0}H$. At fixed $\mu$, however, $n_Q{e}^{\beta \mu }$ changes with temperature, so $M$ itself need not scale simply as $1/T$. The moment per particle has the Curie behaviour; the density constraint must be stated.

Total density. Adding the two populations givesFor a finite container and fixed $N$, normalization gives $e^{\beta \mu }=N/[2n_Q\int \cosh x(\mathbf{r})d^{3}r]$. In a weak field the leading density is uniform, with changes only of order $x^2$. Particles preferentially occupy regions where the magnitude of the field lowers one of the spin energies, even though the common chemical potential remains uniform.

First solve the equation of state for the volume:The Gibbs free energy has differential $dG=-SdT+Vdp+\mu dN$. At fixed temperature and particle number, integrate $dG=Vdp$ between the two pressures:ConsequentlyUse $S=-(\partial G/\partial T{)}_{p,N}$, keeping both endpoint pressures fixed while differentiating the difference:Equivalently, the Maxwell relation $(\partial S/\partial p{)}_{T,N}=-(\partial V/\partial T{)}_{p,N}$ gives $-N{k}_B/p+N{A}^{\prime }(T)$, whose pressure integral is the same result. These are the Gibbs free-energy change for a pressure-linear gas correction identities. The physical path requires $p_0,p_1>0$ and positive volume throughout. The correction $A(T)$ has units of volume per particle, so each term in $\Delta G$ is an energy and each term in $\Delta S$ has units of energy per kelvin.

Fermion occupation and ordinary metallic heat capacity. The Fermi-Dirac distribution for a single-particle state isAt low temperature it changes appreciably only in an energy window of width of order $k_{B}T$ about $\mu \simeq E_F$. If the full density of states $D(E)$ is smooth and nonzero there, only about $D(E_F)k_{B}T$ states change population. Each excited particle or hole carries energy of order $k_{B}T$ relative to the Fermi surface, so $U(T)-U(0)$ is of order $D(E_F)(k_{B}T{)}^2$. Differentiation therefore gives $C_{\mathrm{el}}\propto T$.

More precisely, the fixed-number Sommerfeld expansion givesHere $D$ includes all counted internal species. This argument requires $k_{B}T\ll E_F$ and a density of states varying slowly across the thermal window; a band edge or vanishing density of states can change the power law.

Two-dimensional linear dispersion at zero chemical potential. Let $g$ count identical positive-energy branches, keeping the state-counting convention explicit. The number of wavevector states in a ring of radius $k$ is $gA(2\pi kdk)/(2\pi {)}^2$. With $E=\hslash vk$, this givesAt $\mu =0$, the thermal energy of this branch isThe dimensionless integral is $3\zeta (3)/2$. Differentiating givesThis is the heat capacity for a two-dimensional linear fermion dispersion. A physical neutral particle–hole-symmetric Dirac cone also has electron holes in its filled negative-energy band. Their excitation energy gives an equal contribution, doubling $C_{+}$ for the same cone count. The $T^2$ scaling is unchanged. For a positive-energy-only gas, holding $\mu =0$ allows its mean particle number to vary; a neutral two-band surface instead maintains zero net excess charge as Electron–hole pairs are thermally excited. These conventions should not be conflated when specifying an exact coefficient.

Nonzero chemical potential. The ordinary metallic regime isThe thermal window then lies far from the cone tip. Since $D(E)\propto E$, its fractional change across that window is only of order $k_{B}T/\mu$. Treating it as locally constant restores the Sommerfeld result $C_{\mathrm{el}}\propto D(\mu )T\propto \mu T$. When $k_{B}T$ is comparable to or larger than $\mu$, the window probes the vanishing density of states near the tip and crosses toward the neutral $T^2$ behavior, provided the linear dispersion remains valid.

Bulk phonons and the surface-to-bulk comparison. For the topological insulator model, assume bulk electronic excitations are frozen out while the conducting surface remains active. In three dimensions, acoustic phonons have a density of modes proportional to ${\omega }^2$. Normalize the Debye spectrum to $3N$ modes:The thermal part of the energy isAt $T\ll {\Theta }_D$, extending the upper integration limit to infinity introduces an exponentially small error. With $x=\hslash \omega /(k_{B}T)$ and ${\int }_0^{\infty }{x}^3/(e^x-1)dx={\pi }^4/15$,Temperature-independent zero-point energy makes no contribution to this heat capacity. The requested ratio consequently scales asFor a fixed shape and composition, $A\propto L^2$ and $N\propto L^3$, so the ratio grows as $1/(LT)$. Smaller samples and lower temperatures favor the surface contribution. It dominates if the dimensionless right-hand side, including its state-counting prefactor, exceeds unity. This is the surface-electron and bulk-phonon heat-capacity crossover.

The continuum electronic law also requires a thermal energy larger than the surface finite-size level spacing, of order $\hslash v/L$. The phonon continuum has its own finite-size cutoff. Therefore dominance obtained by formally taking $T\to 0$ cannot always be inferred from the two continuum power laws alone.

There is a numerical-normalization qualification in the paper. Combining the explicit one-positive-branch result above with the conventional $3N$-mode Debye normalization gives ratio prefactor $15g\zeta (3)/(16{\pi }^5)$; including electron holes doubles it. For $g=1$, this is approximately $0.00368$ before that doubling, rather than the supplied $5/(12{\pi }^2)\simeq 0.0422$. The problem specifies neither a cone/spin multiplicity that equates these nor another mode normalization. Its supplied prefactor is therefore used as the stipulated approximation for the requested numerical estimate, rather than claimed as an exact consequence of the single-branch count.

Numerical estimate. A cubic sample of volume $1\mathrm{m}{\mathrm{m}}^3$ has side $L=10^{-3}\mathrm{m}$. Counting the conducting surface on all six faces givesFor one atom per cubic cell of side $a=1.5\times 10^{-9}\mathrm{m}$,Use $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$ and $\hslash =1.05457\times 10^{-34}\mathrm{J}\mathrm{s}$. Inserting the stated $v=5\times 10^5\mathrm{m}{\mathrm{s}}^{-1}$, ${\Theta }_D=500\mathrm{K}$ and $T=1\mathrm{K}$ into the paper's supplied prefactor givesThus bulk phonons dominate at this temperature in this estimate. If only one face contributes, the ratio is $1.22\times 10^{-6}$; if there are $\nu$ chemical atoms per unit cell, divide the corresponding estimate by $\nu$. These geometrical and crystallographic factors are not supplied explicitly.

With the same prefactor and geometry, extrapolating $1/T$ would suggest equality near $7.3\mu \mathrm{K}$. However, the surface finite-size scale is already of order $\hslash v/(k_{B}L)\simeq 3.8\mathrm{mK}$ for this specimen. That extrapolated crossover lies outside the continuum electronic regime, so it is not a reliable prediction of the sample's ultimate lowest-temperature heat capacity.

Use the Gibbs-Duhem equation for a homogeneous, extensive, single-component thermodynamic phase:At fixed temperature, this becomes $dp=nd\mu$, with number density $n=N/V$. Separately, at fixed particle number,The chain rule along the same isothermal process in the equation of state now givesConsequentlyThis is isothermal compressibility from chemical-potential response. Since chemical potential has units of energy per particle, the right-hand side has units of volume per energy, or $\mathrm{P}{\mathrm{a}}^{-1}$, as required. The derivation assumes a smooth bulk equation of state; changing the fractions of coexisting thermodynamic phases at fixed pressure needs separate treatment.

Canonical probabilities. A canonical ensemble describes a system of fixed particle number and fixed external parameters such as volume, weakly coupled to a much larger thermal reservoir. They exchange energy and reach thermal equilibrium, while the reservoir's temperature stays effectively constant. The interaction energy is negligible in the state counting. The combined isolated system is described by equal probabilities for its accessible microstates.

If its total energy is $E_{\mathrm{tot}}$, the probability of a particular system microstate $i$ is proportional to the reservoir multiplicity at $E_{\mathrm{tot}}-E_i$. Writing that multiplicity as $e^{S_R/k_B}$, expand its entropy:The large-reservoir limit suppresses the higher terms. Normalization therefore givesThe sum counts individual microstates; when grouping them by energy, their state degeneracies must be included. This $Z$ is the canonical partition function.

Classical orientational heat capacity. Hold the magnetic field fixed. Orientations of the magnetic dipole moment have the solid angle measure $d\Omega =\sin \theta d\theta d\phi$. With $x=\beta mB$, the angular partition function isChoosing a normalized angular measure would remove $4\pi$, with no effect on the energy derivatives. Differentiating at fixed $B$,The angular average $⟨\cos \theta ⟩=\coth x-1/x$ is the Langevin function. Since $dx/dT=-x/T$,This is the heat capacity of a classical magnetic dipole, in $\mathrm{J}{\mathrm{K}}^{-1}$ for one magnetic moment. The word specific here refers to that single moment; $N$ independent magnetic moments have $N$ times this heat capacity. At $B=0$ the energy is independent of orientation and $C_B=0$, obtained by the continuous $x\to 0$ limit. At fixed nonzero $B$, the classical low-temperature limit instead gives $C_B\to k_B$.

Equipartition and its proof. The equipartition theorem states that an independent quadratic term $a{q}^2/2$ in a classical Hamiltonian, with $a>0$, contributes $k_{B}T/2$ to its mean energy. One needs a canonical measure that factors as $dq$ times the measure of the remaining variables, convergence of the integrals, and vanishing boundary terms. The coordinate must not be restricted by a thermally important hard boundary or a coupled constraint.

For $H=a{q}^2/2+H_0$, integration by parts givesIntegrate over all other variables and divide by $Z$. It follows thatThe same reasoning applies to quadratic momenta among the canonical variables. It is the number of quadratic energy contributions that is counted, not an unrestricted count of coordinate labels.

Two soft orientational directions. When $x\gg 1$, the moment is concentrated near alignment. Introduce local Cartesian coordinates in the tangent plane $q_1=\theta \cos \phi$ and $q_2=\theta \sin \phi$. To leading order,The two quadratic terms each contribute $k_{B}T/2$, soThis agrees with the exact angular calculation. Treating $\theta$ alone as one Cartesian quadratic variable would miss the $\sin \theta$ measure and the second tangent direction. There are no extra rotational kinetic terms in the stipulated Hamiltonian; adding such terms would be a different model.

Quantum spin one. The spin projections are $m_s=-1,0,1$, with $S_z=\hslash m_s$. Put $\Delta =\hslash |\gamma |B>0$, where $\gamma$ is the gyromagnetic ratio. The three energies are $-\Delta ,0,+\Delta$, irrespective of the sign of $\gamma$. Relative to the ground state they are $0,\Delta ,2\Delta$. Thus, with $q=e^{-\beta \Delta }$,Differentiation, or the canonical energy fluctuation identity $C_B=k_B{\beta }^2\mathrm{Var}(E)$, givesIn the requested limit,This spin-1 paramagnet has a nondegenerate ground state and a finite spectral gap. Excitations are exponentially rare, so its heat capacity tends to zero. Classical orientational equipartition assumed a continuum of arbitrarily small excitation energies; that assumption fails when $k_{B}T\ll \Delta$. This is a change in the accessible state spectrum, not a violation of the equipartition theorem within its classical domain.

Availability and total entropy. The reservoir changes by $d{U}_R=-dU$ and $d{V}_R=-dV$. Its particle number and the system's particle number are fixed. The reservoir's first law of thermodynamics therefore givesAdd the system's entropy change. Because $T_R,p_R$ are constant,Thus define the availabilityAn additive constant in $A$ is immaterial; its value above the equilibrium reference is the exergy. The Second law of thermodynamics gives $\Delta S_{\mathrm{tot}}\ge 0$, hence $\Delta A\le 0$. A stable equilibrium maximizes total entropy over the allowed variations and therefore minimizes $A$. The environmental $T_R,p_R$ enter this definition even when the system has not yet reached their values. Because both thermal and mechanical exchanges are allowed, equilibrium here includes mechanical balance; equality of temperatures alone does not ensure the minimum.

Probability and curvature. For a fixed value of a macroscopic coordinate $x$, let $S(x)$ count the compatible system microstates. The product of the system and reservoir multiplicities isAll factors independent of $x$ enter a normalization constant, givingHere $A(x)$ is the constrained or effective availability for this coordinate, including the multiplicity of any eliminated variables. A nonuniform coordinate measure must likewise be retained or incorporated in that effective availability.

At a stable interior minimum, $A^{\prime }(x_0)=0$ and $A^{\prime \prime }(x_0)>0$. Its Taylor expansion givesKeeping the quadratic term yields a normal distribution,This is availability curvature and equilibrium fluctuations. The quoted fluctuation formula holds at quadratic order in the Gaussian fluctuation approximation; it is not an exact identity for an arbitrary nonlinear $A(x)$. Higher terms can shift the mean away from its most probable value $x_0$.

Bubble equilibrium. Keep the number of air molecules fixed and include the surface energy in the system's total internal energy. For constant surface tension $\Gamma$, this contribution is $\Gamma \Omega =\Gamma \alpha V^{2/3}$, with no surface entropy under the stated approximation. Its differential isHenceIndependent thermal and volume variations give $T=T_R$ andThe air pressure is evaluated at $V_0$; since the bubble is closed it generally depends on volume, so this equation is implicit until an air equation of state is supplied. For a sphere, $\alpha =(36\pi {)}^{1/3}$, $\Omega =4\pi R^2$, and the pressure jump becomes $2\Gamma /R$, the Young–Laplace equation for a single gas–liquid interface. There is no second surface as in a thin soap film.

Isothermal volume fluctuations. With the air maintained at $T_R$, eliminate its entropy in favor of its Helmholtz free energy:The identity $(\partial F_{\mathrm{air}}/\partial V{)}_{T,N}=-p_{\mathrm{air}}$ givesUsing the curvature result,These are the volume fluctuations of a closed gas bubble. Stability requires the denominator to be positive. The negative surface contribution reflects the concavity of $V^{2/3}$; gas compression supplies the positive restoring curvature. For ideal air, ${\kappa }_T^{-1}=p_{\mathrm{air}}$, and mechanical equilibrium reduces the denominator toThe units are consistent: $D$ is pressure, so $k_B{T}_R{V}_0/D$ has units ${\mathrm{m}}^6$, the units of a volume variance. Holding $p_{\mathrm{air}}$ externally fixed while varying $V$ would remove the gas-compression term and change this stability problem; that is not the fixed-particle-number situation here.

Numerical size of the fluctuations. The volume conversion is important:Use the specified $\alpha =4.84$, $\Gamma =0.072\mathrm{N}{\mathrm{m}}^{-1}$ and $p_R=10^5\mathrm{Pa}$. ThenWith the Boltzmann constant $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$,Thus the fractional root mean square fluctuation and fractional variance are respectivelyThe absolute root mean square fluctuation is $2.01\times 10^{-19}{\mathrm{m}}^3$. The very small fractional value supports the local Gaussian fluctuation approximation. This estimate neglects exchange of dissolved air, variations of surface tension, shape fluctuations and temperature fluctuations, consistently with the prescribed fixed-number, isothermal bubble model.