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Use the stable parameters $b,\kappa >0$. The bulk stationary points satisfy $f^{\prime }(\varphi )=a\varphi +b{\varphi }^3=0$. For $a<0$, $\varphi =0$ has negative curvature, while the two minima areBoth have $f(\pm {\varphi }_B)=-a^2/(4b)$ and $f^{\prime \prime }(\pm {\varphi }_B)=-2a>0$. To establish minimization at fixed total composition, writeFor mean composition $\bar{\varphi }$ with $|\bar{\varphi }|<{\varphi }_B$, a mixture of the two minima with volume fraction $\lambda =(\bar{\varphi }+{\varphi }_B)/(2{\varphi }_B)$ in the positive phase attains this lower bound in the bulk. Macroscopic slabs have only a subextensive interfacial excess free energy, so the bound is attained per unit volume in the thermodynamic limit. Thus constrained minimization gives phase coexistence in the mean-field approximation; at the endpoints only one phase is needed.

The two equilibrium conditions also follow directly by constrained optimization. Introduce a Lagrange multiplier $\mu$ for $\lambda {\varphi }_{+}+(1-\lambda ){\varphi }_{-}=\bar{\varphi }$ in the mixture's bulk free-energy density. Varying ${\varphi }_{+}$ and ${\varphi }_{-}$ gives $f^{\prime }({\varphi }_{+})=f^{\prime }({\varphi }_{-})=\mu$; varying $\lambda$ gives $f({\varphi }_{+})-\mu {\varphi }_{+}=f({\varphi }_{-})-\mu {\varphi }_{-}$. These equate the chemical potentials and pressures, respectively.

Equivalently, their bulk chemical potentials are both zero and their pressures are equal:These are precisely the conditions of the common-tangent construction for phase coexistence: the horizontal supporting tangent touches both minima. Equal chemical potentials prevent net composition exchange, and equal pressure gives mechanical equilibrium at a flat interface.

Apply force balance to one hemisphere. The pressure force is $\pi R^2({\Pi }_{\mathrm{in}}-{\Pi }_{\mathrm{out}})$, while the interfacial tension around its equator gives $2\pi R\gamma$. The Young–Laplace equation therefore yieldsTo leading order in curvature, let the two bulk compositions be ${\varphi }_{+}={\varphi }_B+{\delta }_{+}$ and ${\varphi }_{-}=-{\varphi }_B+{\delta }_{-}$. Their curvatures agree, $\alpha =f^{\prime \prime }(\pm {\varphi }_B)=-2a$, so equal chemical potentials require $\alpha {\delta }_{+}=\alpha {\delta }_{-}$ and hence a common shift $\delta$.

Since $d\Pi /d\varphi =\varphi f^{\prime \prime }(\varphi )$, expansion about the flat coexistence compositions gives ${\Pi }_{+}-{\Pi }_{-}=2{\varphi }_B\alpha \delta +O({\delta }^2)$. Matching the capillary pressure proves the Gibbs--Thomson relation in these variables:The pressure jump balances interfacial forces; it does not permit unequal chemical potentials. A common shift in both compositions supplies a common interfacial chemical potential while their pressures differ. The expansion assumes $R$ large compared with the phi-four diffuse interface width.

The far-field composition $-{\varphi }_B$ has chemical potential zero. Local curved-interface coexistence imposes $\mu (R)={\mu }_s=\gamma /({\varphi }_{B}R)$. The decaying spherically symmetric solution of the exterior Laplace equation isWith constant mobility, its outward current isThe linearized exterior composition is $\varphi (r)=-{\varphi }_B+\mu (r)/\alpha$, consistent with the surface shift in the previous part.

For diffusion-controlled droplet growth, the interior is uniform to leading order and has no diffusive current. Replacing exterior material by interior material requires the composition jump $2{\varphi }_B$, so conservation gives $2{\varphi }_B\dot{R}=-J_r(R)$. HenceThe negative sign represents evaporation. The total outward current is $4\pi R^2{J}_r(R)=4\pi M\gamma /{\varphi }_B$, independent of $R$ in this leading quasi-static capillary approximation.

The flat interface is an equilibrium reservoir with $\mu =0$, while the droplet has the constant surface value ${\mu }_s=\gamma /({\varphi }_{B}R)$. The exterior chemical potential satisfies the Laplace equation, tends to zero far away, and obeys these two surface values. These are exactly the electrostatic boundary conditions at a conductor for a sphere held at potential ${\mu }_s$ above a grounded infinite plane.

Introduce an arbitrary permittivity $ϵ$. In the electrostatic problem, $Q=-ϵ{\int }_{S_R}{\partial }_n\mu dS=C(R,h){\mu }_s$. Therefore the diffusion-capacitance analogy gives the outward currentFor an isolated sphere, its capacitance is $C(R,\infty )=4\pi ϵR$, so $I(R,\infty )=4\pi MR{\mu }_s=4\pi M\gamma /{\varphi }_B$. Dividing givesThus sphere-plane capacitance determines the evaporation enhancement. The assumed spherical shape gives the corresponding law $\dot{R}=-M\gamma c(R/h)/(2{\varphi }_B^2{R}^2)$ for droplet evaporation near a planar reservoir. The local surface current is generally nonuniform, even though its total is described by a single capacitance.

The chemical potential is the change in internal energy when one particle is added at fixed entropy and volume:Equivalently, $\mu =(\partial F/\partial N{)}_{T,V}$ for the Helmholtz free energy.

Let a microstate $s$ have energy $E_s$ and particle number $N_s$. Maximizing the Gibbs entropy subject to normalization and fixed mean values of $E$ and $N$ is the maximum-entropy derivation of equilibrium ensembles. With Lagrange multipliers $\alpha$, $\beta$, and $-\beta \mu$, varyThe stationarity equation is $-\log p_s-1-\alpha -\beta (E_s-\mu N_s)=0$. Normalization therefore gives the grand canonical ensembleHere $\mathcal{Z}$ is the grand canonical partition function and $k_B$ is the Boltzmann constant.

For one fermionic quantum state of energy $\epsilon$, the Pauli exclusion principle permits occupation numbers only $n=0,1$. Its two grand-canonical weights are $1$ and $e^{-\beta (\epsilon -\mu )}$, so its mean occupation is the Fermi-Dirac distribution

For a free nonrelativistic particle, $\epsilon ={\hslash }^2{k}^2/(2m)$. In a region of area $A$, the number of wave-vector states in the annulus from $k$ to $k+dk$, including the two spin angular momentum states, isSince $kdk=(m/{\hslash }^2)d\epsilon$, the two-dimensional free-electron density of states is constant:

We now use units in which $k_B=1$, as in the question. At zero temperature, the Fermi-Dirac distribution is a step function, and henceAt positive temperature the same fixed particle number satisfies the exact relationThusThis is the low-temperature particle-number cancellation for constant density of states. Therefore, for $T\ll {\epsilon }_F$, the mean number of particles in the energy interval $[\epsilon ,\epsilon +d\epsilon ]$ is

Finally, compare the internal energy with its zero-temperature value. The thermally excited particles above ${\epsilon }_F$ and holes below ${\epsilon }_F$ have equal leading particle numbers, so their terms proportional to ${\epsilon }_F$ cancel. With $x=|\epsilon -{\epsilon }_F|/T$,where the integral follows from the fermion-to-boson thermal integral ratio. Differentiation gives the linear low-temperature heat capacity of a two-dimensional Fermi gas:The requested power law is therefore linear in $T$, with exponent one.

Impose the fixed conserved order parameterwith a Lagrange multiplier ${\mu }_0$. Stationarity ofunder every local variation givesThus the chemical potential is spatially constant at constrained equilibrium.

The fundamental thermodynamic relation isBecause $E(S,V,N)$ is extensive, the Euler theorem for homogeneous functions givesSubstitution into the Gibbs free energy $G=E+pV-TS$ therefore yieldsFor a one-component equilibrium phase, the intensive chemical potential depends on the intensive state variables $T$ and $p$.

Because $\varphi$ is a conserved composition density, an infinitesimal material displacement $\mathbf{r}\mapsto \mathbf{r}+\mathbf{u}$ changes it at fixed position byThe second term is essential when the deformation is compressible. By the definition of the chemical potential, and taking $\mathbf{u}$ to vanish on the boundary,The same free-energy change written in terms of the stress tensor isSince $\mathbf{u}$ is arbitrary,This is the Korteweg force density of a diffuse-interface mixture.

The microcanonical ensemble describes an isolated system at fixed energy $E$, volume $V$, and particle number $N$, assigning equal weight to accessible states in a narrow energy shell.

The canonical ensemble describes a system that can exchange energy with a heat reservoir at fixed temperature $T$, while $V$ and $N$ remain fixed. A microstate $s$ has probability

The grand canonical ensemble allows exchange of both energy and particles at fixed $T$, $V$, and chemical potential $\mu$. Its state weights are

The choice is irrelevant for bulk thermodynamic observables in the thermodynamic limit when the system is additive, has sufficiently short-range interactions, and lies away from singular phase-coexistence regimes. Then relative energy and particle-number fluctuations vanish as the system size grows. These are the standard conditions for equivalence of statistical ensembles.

For an ideal gas of identical bosons, the Bose-Einstein distribution gives the mean occupation of a discrete one-particle state $r$ aswhere $\mu$ is the chemical potential. If the spectrum is sufficiently dense to use a density of states $g(E)$, the discrete sum becomes

A phonon has zero chemical potential and energy $\hslash \omega$. The total internal energy is consequentlyWith the change of variable $x=\beta \hslash \omega$ and $\beta \hslash {\omega }_D=T_D/T$, this becomes

The thermodynamic order parameter is the conserved scalar composition difference $\varphi$ of the binary fluid mixture. The momentum density $\rho \mathbf{v}$ is an additional conserved hydrodynamic mode; it is not a symmetry-breaking order parameter, but it must be retained because momentum relaxes only through spatial transport.

Composition conservation gives a continuity equation,The current $\mathbf{J}=-M\nabla \mu$ is the leading isotropic, dissipative constitutive law: it drives material down gradients of the chemical potential. For the Landau-Ginzburg theorythe functional derivative isThese statements give the advective Cahn--Hilliard equation.

Constant mass density and incompressible flow require $\nabla \cdot \mathbf{v}=0$. Momentum conservation gives the Navier-Stokes equation: material acceleration equals the sum of the Newtonian viscous force $\eta {\nabla }^2\mathbf{v}$, the pressure force $-\nabla P$, and the Korteweg force $-\varphi \nabla \mu$. The pressure is the Lagrange multiplier enforcing incompressibility. Together these equations are Model H dynamics; isothermality removes the need for a separate energy equation.

An intensive quantity is unchanged when the size of a homogeneous system is scaled; temperature and pressure are examples. An extensive quantity scales in proportion to system size; volume and particle number are examples. Energy and entropy are also extensive, while chemical potential is intensive. These are intensive and extensive thermodynamic quantities.

Chemical equilibrium gives ${\mu }_D={\mu }_p+{\mu }_n$. Substitution of the three Maxwell--Boltzmann densities therefore cancels the chemical potentials and leaves the rest-mass factorUsing $g_p=g_n=2$, $g_D=4$, $m_n\simeq m_p$, and $m_D\simeq 2m_p$, the translational prefactor isHence

A grand canonical ensemble describes a system exchanging both energy and particles with a reservoir at fixed $T$, volume, and chemical potential $\mu$. For a noninteracting fermion level $r$, occupation is $0$ or $1$, soFactorization over levels gives $\mathcal{Z}={\prod }_r{\mathcal{Z}}_r$, and differentiation with respect to $\beta \mu$ yields the Fermi-Dirac distribution

Equality of chemical potentials gives $d{\mu }_{\mathrm{l}}=d{\mu }_{\mathrm{g}}$ along coexistence. Sinceone obtainsUsing $L=T(s_{\mathrm{g}}-s_{\mathrm{l}})$ gives the Clausius-Clapeyron relation