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This relates an thermodynamic equilibrium variance to the local stiffness of an appropriate thermodynamic free energy. At fixed bath temperature, suppose the effective thermodynamic free energy $A(x)$ includes the constraints and the measure for a chosen coordinate. Its thermodynamic equilibrium probability density function is proportional to $e^{-A(x)/(k_{B}T)}$. Near a stable minimum $x_0$, writeThe resulting normal distribution gives the Gaussian fluctuation approximationThis is exact for a quadratic thermodynamic free energy with the stated flat coordinate measure; in general it is a small-fluctuation result. A smaller curvature means a softer restoring response and larger fluctuations. Near vanishing curvature, higher-order terms become important, so the quadratic approximation cannot alone predict an actual infinite variance.

For example optical trap Langevin calibration uses the Brownian displacement of a trapped bead: $A=\kappa (x-x_0{)}^2/2$ gives $\kappa =k_{B}T/⟨\Delta x^2⟩$. A camera or position detector records the fluctuations. Finite exposure averages rapid motion and can bias the measured variance; the measurement protocol matters as well as the thermodynamic equilibrium identity.

For a bulk liquid and vapor at common fixed temperature and pressure, transfer $d{N}_l$ molecules from vapor to liquid while holding their sum fixed. The Gibbs free energy change is $dG=({\mu }_l-{\mu }_v)d{N}_l$. Thermodynamic equilibrium with both phases present requires stationarity under either sign of transfer, hence $\boxed{{\mu }_l={\mu }_v}$. This is the bulk coexistence condition; an interface's curvature adds a surface-energy cost.

In the capillarity approximation, take an incompressible drop with constant liquid number density $n_l$, bulk chemical potential ${\mu }_l$ at the specified reservoir conditions, and size-independent surface tension $\Gamma$. The liquid bulk is extensive, so its Gibbs thermodynamic free energy is $N_l{\mu }_l$. Creating interface area reversibly at fixed temperature adds $\Gamma A$. Equivalently, along growth at fixed bulk parameters the stated differential integrates as $d{G}_d={\mu }_{l}d{N}_l+\Gamma dA$, with the no-drop reference set to zero. For a sphere,This approximation uses bulk properties for the interior and neglects the molecular interface thickness, curvature dependence of surface tension and higher compressibility corrections. It does not apply quantitatively to drops only a few molecules across.

The vapor contains $N-N_l$ molecules. Treat its chemical potential as approximately unchanged by forming the drop, as for a large surrounding reservoir or negligible vapor depletion. ThenThe radius is limited by the available molecules in a finite sample; the constant-reservoir expression is a local nucleation model, not a description of arbitrarily complete vapor depletion. The excess over the vapor reference has derivativeIf ${\mu }_l>{\mu }_v$, it increases for every $R>0$, leaving only the stable boundary minimum $R=0$. If ${\mu }_l<{\mu }_v$, $R=0$ is a metastable local minimum and the additional stationary radius isAt that radius $\Delta G^{\prime \prime }=-8\pi \Gamma <0$, so it is an unstable maximum. The classical nucleation theory barrier is $16\pi {\Gamma }^3/[3n_l^2({\mu }_v-{\mu }_l{)}^2]$.

A fluctuation below $R_c$ tends to shrink because reducing its surface cost lowers thermodynamic free energy. A supercritical drop tends to grow, because its bulk free-energy gain outweighs the added surface cost. Growth continues while material supply and supersaturation allow it, eventually changing the vapor state or leading to macroscopic liquid. Curved-interface pressure and chemical thermodynamic equilibrium can also be described through the Young–Laplace equation and the Kelvin equation.

For a liquid interface with constant surface tension $\gamma$, the mechanical surface energy is the energy associated with its surface area $A$:The additive constant $C$ does not affect the work needed to change surface area. For several interfaces with the same surface tension, $A$ means their total surface area; the two faces of a thin soap film must both be counted. ^[ref]

With assumed $\gamma =0.072\mathrm{N}{\mathrm{m}}^{-1}$, creating $1\mathrm{c}{\mathrm{m}}^2=10^{-4}{\mathrm{m}}^2$ of one interface requires $7.2\mu \mathrm{J}$ of reversible work. In the sliding-rim example illustrated under surface tension, moving a $20\mathrm{mm}$ rim outwards by $1\mathrm{mm}$ creates $4.0\times 10^{-5}{\mathrm{m}}^2$ across the two faces and requires $2.88\mu \mathrm{J}$. Independently, multiplying its $2.88\mathrm{mN}$ holding force by the displacement gives the same work.

This makes the preference for a round isolated droplet precise. At fixed volume $V$, the three-dimensional isoperimetric inequality giveswith equality for a sphere. Thus a sphere minimizes surface energy among sufficiently regular closed shapes enclosing the same volume, when surface tension is uniform and other energy contributions are negligible. This is an application of the isoperimetric inequality, rather than a proof of it. Walls, wetting, and gravity can change the shape by adding constraints or other energy contributions. ^[ref]

The differential rule $d{E}_{\mathrm{s}}=\gamma dA$ integrates directly to $E_{\mathrm{s}}=\gamma A+C$ because surface tension is constant. At fixed liquid volume, decreasing surface area can drive viscous fluid flow; the released surface energy can supply viscous dissipation. This mechanical bookkeeping is useful for predicting which deformations can release energy. If surface tension depends on temperature or composition, distinguish this mechanical area-work relation from the complete interfacial thermodynamic free energy and internal energy.