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For a stationary, uniformly permeable skeleton, Darcy law gives $\mathbf{u}=-(\Pi /\mu )\nabla p$. Constant-density conservation of mass gives $\nabla \cdot \mathbf{u}=0$, hence the pressure is harmonic:With uniform gravitational acceleration, the same argument applies to pressure after subtracting its hydrostatic part. The spherical calculation below neglects body-force variation and uses the excess pressure relative to the far field.

Set $ϵ=1-{\rho }_s/\rho >0$ and $\beta =\varphi ϵ$. When a shell freezes, its pore mass decreases at rate $4\pi a^2\varphi (\rho -{\rho }_s)\dot{a}$; the difference must leave as liquid. Since Darcy velocity is volume discharge per total area, not pore-fluid speed, the interfacial and radial balances giveThe positive sign means outward expulsion by the expansion on freezing. Integrating Darcy law with $p(\infty )=0$ givesThere is no liquid Darcy velocity in the ice-filled region.

To state a closed Stefan problem, let $k_{-},k_{+}$ be the effective thermal conductivities of the frozen and unfrozen composites and $C_{-},C_{+}$ their volumetric heat capacities. If the matrix mass density is ${\rho }_m$, the common specific heat gives $C_{-}=c_p[(1-\varphi ){\rho }_m+\varphi {\rho }_s]$ and $C_{+}=c_p[(1-\varphi ){\rho }_m+\varphi \rho ]$. These material coefficients are not numerically specified. With $\mathcal{L}=\varphi {\rho }_{s}L$, the thermal equations areThe exterior equation retains advected sensible heat. A more detailed mechanical-energy model adds the Darcy dissipation source $\mu u^2/\Pi$; its smallness at leading order is checked below. At the origin require ${\partial }_r{T}_{-}(0)=0$, and at infinity require $T_{+}\to T_{\infty }$, $p\to 0$. At the phase boundary impose temperature continuity, phase equilibrium and the Stefan condition:These equations, the radial liquid-mass balance and Darcy law, together with an initial radius and compatible initial temperature fields, specify the moving-boundary model. No curvature correction is imposed. A vanishing initial seed corresponds to the leading growth law below with $a(0)=0$.

Write $\Delta =T_m-T_{\infty }$ and $S=L/(c_p\Delta )$, the latent-to-sensible heat ratio. A conductive interfacial balance gives $a\dot{a}\lesssim k_{+}\Delta /\mathcal{L}$. On length scale $a$, the ratio of thermal diffusion time to growth time is consequently bounded byIt is small for $S\gg 1$ with fixed porosity and comparable constituent densities and thermal properties. Very small porosity requires the sharper condition $C_{\pm }\Delta /(\varphi {\rho }_{s}L)\ll 1$; the bare heat-capacity ratio alone should not be used uniformly as $\varphi \to 0$. The advective-to-conductive ratio isEven if mechanical heating is retained, its size relative to latent-heat release is $p_i\beta /\mathcal{L}=(T_m-T_i)/T_m\le \Delta /T_m$. For fixed water properties this is also small as $S\to \infty$, consistently with the linearized Clausius-Clapeyron relation. Thus unsteadiness, thermal advection and mechanical heating are higher-order effects. The local leading temperature fields satisfy Laplace's equation. The approximation describes radii of order $a$; the distant transient diffusion tail supplies the far-field matching and need not be globally steady.

Regularity at zero and the interface/far-field values giveThe Stefan condition becomes $\mathcal{L}a\dot{a}=k_{+}(T_i-T_{\infty })$. Introduce the dimensionless pressure-feedback factorCombining this heat balance with pressure-dependent phase equilibrium yields the growth and interface values:This is pressure-limited spherical freezing in a porous medium. The interface values are constant during this leading solution, although $p(r,t)$ changes at a fixed exterior radius.

As permeability of a porous medium decreases, $\Lambda$ increases: the interface pressure rises toward the finite value $\Delta /\gamma$, while the interface temperature falls toward $T_{\infty }$. Hydraulic resistance suppresses freezing through pressure-induced freezing-point depression. In the limit $\Pi \to 0$, $a\dot{a}\sim \Pi \Delta /(\gamma \mu \beta )$; a zero-seed radius grows as $\sqrt{\Pi t}$ and tends to zero at fixed time. A finite seed instead hardly changes. At exactly zero permeability an incompressible rigid model cannot expel the expansion volume, so sustained growth stops; deformation or compressibility would require a different model.

For a simple system of fixed composition, the first law of thermodynamics andgiveThusEquality of mixed derivatives gives the Gibbs free-energy Maxwell relation

The heat capacity at constant volume and heat capacity at constant pressure areRegarding $S$ as a function of $T,V$ and differentiating along a constant-pressure curve givesThe Maxwell relation from the Helmholtz free energy isTherefore the difference between constant-pressure and constant-volume heat capacities is

Along the liquid-gas phase coexistence curve, the molar Gibbs free energies agree. Differentiating $G_{\mathrm{l}}=G_{\mathrm{g}}$ along the curve givesHence the Clausius-Clapeyron relation iswhere $L=T(S_{\mathrm{g}}-S_{\mathrm{l}})$ is the molar latent heat.

If $V_{\mathrm{g}}\gg V_{\mathrm{l}}$ and the gas is ideal, then $V_{\mathrm{g}}=RT/P$, soFor constant $L$, integration yieldswhere $P_0$ is constant over the range in which the approximations apply.

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

The latent heat for converting liquid to gas at coexistence iswith all quantities taken per mole or per particle consistently. Along the phase coexistence curve, the two Gibbs free energy values agree:Sincedifferentiating the equality along the curve givesTherefore the Clausius-Clapeyron relation isAt the critical point the liquid and gas become the same phase, so their entropy discontinuity disappears and