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Freezing is a liquid-to-solid phase transition. A moving phase boundary releases latent heat; its rate is constrained by heat transport and the Stefan condition. In a solution the liquidus depends on composition, so being below the pure solvent's melting temperature does not imply that the solution must freeze.

Frost heave is displacement caused by segregated ice growth supplied by liquid flow, rather than solely by the expansion of water on freezing. A premelting film allows liquid access beneath the ice; thermomolecular pressure draws supply against viscous resistance and load.

An ice bath can absorb heat while its temperature barely changes: the heat converts ice into water. The latent heat of fusion quantifies this melting budget. For a pure substance at its equilibrium melting temperature $T_m(p)$ and specified pressure $p$, define it here per unit mass:Here $h_l$ and $h_s$ are the specific enthalpies of the coexisting bulk liquid and solid, and $H$ is enthalpy. For ordinary melting, $L>0$, in $\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}$; an amount $m$ has a total fusion enthalpy $mL$ in joules. A molar fusion enthalpy instead has units $\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}$ and equals $ML$, where $M=m/n$ is mass divided by amount of substance in $\mathrm{kg}\mathrm{mo}{\mathrm{l}}^{-1}$. Always check the normalization before inserting a tabulated value into an energy balance.^{[ref] [ref]}

For a closed system converting completely from solid to liquid at fixed pressure, with only pressure-volume work and negligible changes in bulk kinetic energy and potential energy, the first law of thermodynamics gives $Q_p=\Delta H=mL$. Both endpoints are at $T_m(p)$: warming initially colder ice or subsequently warming the resulting water requires additional sensible heat. Since $H=U+pV$, the corresponding specific internal energy jump is $\Delta u=L-p\Delta v$, where $v=V/m$; $L$ includes the work associated with the change in volume. Heat is transferred energy, whereas enthalpy is a state function. ^[ref]

Let $x=m_l/m$ be the liquid phase fraction by mass, rather than by volume. Neglecting interfacial contributions to enthalpy, equilibrium phase coexistence at fixed pressure givesIn the model above, reaching $T_m$ takes $2.10\mathrm{kJ}$ of sensible heat; the plateau then absorbs $33.40\mathrm{kJ}$, ending at a cumulative $35.50\mathrm{kJ}$. At $18.80\mathrm{kJ}$, half the mass is liquid and the temperature is still $T_m$. The final warming takes another $4.18\mathrm{kJ}$. The rounded $L$ and $c_l$ are inspired by the introductory ice-melting calorimetry values in Case Western's demonstration; constant properties and exact equilibrium throughout are stipulated model assumptions. ^[ref]

Within one thermodynamic phase, specific heat capacity at constant pressure is $c_p=(\partial h/\partial T{)}_p$, in $\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}{\mathrm{K}}^{-1}$; a sample's heat capacity at constant pressure is $C_p=m{c}_p$, in $\mathrm{J}{\mathrm{K}}^{-1}$. The plateau is a finite enthalpy change at zero temperature change through varying $x$, so neither a finite single-phase $c_p$ nor $Q=m{c}_p\Delta T$ represents it. The heating curve needs separate sensible heat intervals and a fusion contribution. ^[ref]

The plateau assumes a pure substance, a stable bulk solid-liquid phase coexistence pair, fixed pressure, and sufficiently slow, uniform heating to remain near thermodynamic equilibrium. The total mass and composition must remain fixed, with negligible evaporation and no other phase transition. A fast heater can produce temperature gradients, so a local thermometer need not read the equilibrium $T_m$. Neither $T_m$ nor $L$ is universal across pressures or compositions: common-pressure melting-point slope describes the pressure dependence of $T_m$, while mixtures can melt over a temperature range as their coexisting compositions change. Their liquidus must be consulted instead of assuming a pure-substance plateau. ^[ref]

This makes ice useful as a temperature buffer: under these conditions it can absorb $m_{s}L$ before the remaining solid mass $m_s$ disappears, after which the water warms. If a stipulated constant net input power $P$ goes entirely into melting, that buffer lasts $m_{s}L/P$. Reversing the equilibrium conversion releases the same fusion enthalpy during freezing. The beautiful thermodynamic connection is $L=T_m(s_l-s_s)$, with $s$ the specific entropy and $T_m$ absolute temperature: equal Gibbs free energies at phase coexistence allow different enthalpies and entropies. The nearly stationary thermometer hides a finite, measurable change of state. ^[ref]

Write $H=L/c_p$, $k=\rho c_p\kappa$ and $ϵ=\sqrt{D/\kappa }$. The requested model neglects density differences and uses the same thermal transport coefficients in the interfacial balances. Let $C_b=C(b(t),t)$ and $T_b=T_m-m{C}_b$. With no imposed heat gradient in the fresh liquid, its temperature remains $T_m$. The prescribed linear temperature in the ice isThe salt and temperature fields in the lower liquid satisfy diffusion equations, $C_t=D{C}_{zz}$ and $T_t=\kappa T_{zz}$. For constant interfacial values and the proposed similarity solution, their decaying solutions areThese follow by substituting a variable $z/(2\sqrt{\chi t})$ into the diffusion equation, which gives $U^{\prime \prime }+2\eta U^{\prime }=0$; integrating gives the complementary error function. Their values at $b$ and at infinity give the required boundary data.

For the upward-moving fresh-water/ice boundary, the Stefan condition is $\rho L\dot{a}=k{T}_{i,z}$: negative $\dot{a}$ means fresh water freezes. At the lower boundary the signed heat balance isSalt cannot enter the pure ice. With no bulk liquid motion its interfacial conservation law isThe derivatives and interface velocities areDefine $F(x)=\sqrt{\pi }x{e}^{x^2}\mathrm{erfc}x$. Substitution into all three balances givesTogether with $T_b=T_m-m{C}_b$, these determine the interfacial constants. In particular $C_b=C_0/[1-F({\lambda }_b)]$.

The physical branch has ${\lambda }_a<{\lambda }_b<0$. Since $F$ is negative at negative arguments, the salt relation gives $0<C_b<C_0$: lower-surface melting dilutes the brine. Combining the two heat balances eliminates the ice gradient and givesThus $T_m>T_b>T_{\infty }>T_L(C_0)$. The interface is at local liquidus equilibrium with diluted brine, while the undiluted far-field brine remains above its own liquidus. The similarity model describes a layer starting with zero thickness, or the long-time limit when an initial finite thickness no longer sets the dominant scale.

For the small-diffusivity-ratio limit, put $A=ϵ{\lambda }_a$ and $\Delta =T_m-T_{\infty }$, keeping $S=H/\Delta$ and the imposed concentrations fixed. Seek $A=O(1)$ and ${\lambda }_b=O(1)$. Then $F(ϵ{\lambda }_b)\sim \sqrt{\pi }ϵ{\lambda }_b$ and ${\lambda }_b-{\lambda }_a\sim -{\lambda }_a$. The upper heat balance givesIn the lower balance the two terms of order ${ϵ}^{-1}$ must cancel, givingConsequentlyand $T_b-T_{\infty }\sim -\sqrt{\pi }HA$. Adding the two temperature differences yields $2A^2-\sqrt{\pi }A=1/S$. The negative root isThe resulting $C_b=(T_m-T_b)/m$ lies strictly between zero and $C_0$. The salt relation therefore determines a finite negative ${\lambda }_b$, confirming its $O(1)$ scaling. The top interface travels on the thermal scale $\sqrt{\kappa t}$, whereas the lower melting interface travels on the shorter solutal scale $\sqrt{Dt}$. This is the brine-ice sandwich with disparate diffusion scales; $S$ is the latent-to-sensible heat ratio, the reciprocal of the usual sensible-to-latent Stefan number convention.

The sketches show constant fresh-water temperature, a declining linear ice temperature, and a much broader thermal than solutal boundary layer in the brine. Concentration is zero in freshwater and pure ice, jumps to $C_b$ across the lower interface, and rises to $C_0$. Accordingly the local liquidus is $T_m$ on the salt-free side, jumps to $T_b$ and falls rapidly to $T_L(C_0)$. In the phase diagram, the brine starts on the liquidus at $(C_b,T_b)$ and ends above it at $(C_0,T_{\infty })$; the pure ice has concentration zero, and the interface tie-line joins it to the diluted brine.

Physically, the cold saline liquid permits freshwater to freeze above, but salt lowers the liquidus and allows the existing ice to melt into brine below even though that brine is colder than $T_m$. Dilution raises the lower interfacial freezing temperature. Heat released by upper freezing supplies the lower melting and the conductive loss to the colder deep brine. With $|{\lambda }_a|\gg |{\lambda }_b|$, upper freezing exceeds lower melting and the ice layer thickens as $b-a\propto \sqrt{t}$.

Take $z$ upward from the unperturbed interface in the apparatus frame, with liquid at $z>0$ and pulling velocity $-V{\mathbf{e}}_z$. The primary ice contains no salt. We use the dilute, equal-density approximation and neglect fluid motion relative to the mould. The initial salt inventory per unit horizontal area, with a common density factor suppressed, is $N=h{C}_0$. Its conservation is essential: the far liquid has zero concentration, so an imposed nonzero far-field composition would describe a different experiment.

The steady advection-diffusion equation is $-V{C}^{\prime }=D{C}^{\prime \prime }$. Decay into the pure water and interfacial salt rejection giveSince ${\int }_0^{\infty }C(z)dz=D{C}_I/V=N$, the finite-inventory directional salt rejection solution isThe decay length is $D/V$. Local liquidus equilibrium givesThus the thermal apparatus selects the interface position at this isotherm. The stated speed inequality is precisely $C_I<C_E$, so the interface is warmer than the eutectic temperature, $T_I>T_E=-m{C}_E$. These are steady values after the initial finite saline layer has rearranged; the final exponential distribution is not confined to the original depth $h$.

For $Vh{C}_0/D>C_E$, a steady pure-ice front would require an interfacial composition beyond the eutectic composition. That branch is unavailable. During the transient, rejected brine concentrates until it reaches $C_E$; secondary salt-bearing crystals can then form and the residual brine freezes as an eutectic system. Salt is incorporated into the product rather than remaining indefinitely in a super-eutectic exponential layer. The detailed pattern can include brine pockets and a nonplanar freezing region; it depends on the thermal history and the morphological stability. The speed inequality alone does not decide that latter stability.

For the stability calculation use an interface displacement $\eta =\hat{\eta }{e}^{ikx+st}$ and a liquid perturbation $c=\hat{c}{e}^{ikx+st-qz}$. Here $k>0$ is the wavenumber, $s$ is the temporal rate and $\Re q>0$ gives spatial decay. The frozen thermal field is $T_I+Gz$. Define $\Gamma ={\gamma }_{sl}{T}_m/(\rho L)>0$, where ${\gamma }_{sl}$ is solid-liquid surface energy, $T_m$ is absolute pure-solvent melting temperature, $\rho$ is mass density and $L$ is specific latent heat. For a solid protrusion into liquid the curvature is $\mathcal{K}=-{\eta }_{xx}=k^2\eta$, and the Gibbs-Thomson effect gives local equilibrium $T=-mC-\Gamma \mathcal{K}$. We assume isotropic surface energy and instantaneous interface kinetics, so no kinetic undercooling term is present.

Linearizing the equilibrium condition at the displaced interface givesThe perturbation advection-diffusion equation givesThe local solute balance at a moving graph, to first order, isIts perturbation is $(V-Dq)\hat{c}+s{C}_I\hat{\eta }=0$, because the terms $D\eta C^{\prime \prime }(0)$ and $V\eta C^{\prime }(0)$ cancel. Consequently the full frozen-temperature solutal interface dispersion isNo quasistatic approximation to solute diffusion was made here. For a growing mode the unique admissible liquid root isWriting $b=(G+\Gamma k^2)/(m{C}_I)$ and eliminating $s$ gives $(q-V/D)(q-V/D+b)=k^2$. The root continuously connected to the growing interface branch is thereforeIn particular, unstable wavelengths exist exactly when $mV{C}_I/D>G$, and their band isThis is the constitutional supercooling criterion: immediately above the plane, the local liquidus rises at rate $-m{C}^{\prime }(0)=mV{C}_I/D$, so it overtakes the imposed thermal gradient when that rate exceeds $G$. The Gibbs-Thomson effect cuts off short waves. At long wavelength $s\sim D(V/D-b)k^2/b$ for positive $G$. The exactly uniform inventory-changing displacement is not an instability of a fixed-inventory experiment. On stable branches the full diffusion problem also admits relaxation transients; the root selection above is sufficient to identify every exponentially growing interface mode.

If one additionally neglects the perturbation time derivative in the liquid diffusion equation, the alternative reduced rate isIt has the same onset and cutoff, but need not have the same rate away from the slow-growth regime. The frozen-temperature approximation by itself does not justify this extra reduction.

After onset, protrusions reach more weakly saline liquid and advance faster, while grooves accumulate rejected brine. The planar interface develops cells and, as growth becomes sufficiently strong, crystal dendrites with concentrated liquid between them. Nonlinear competition changes the selected spacing; linear rates alone cannot fix the final geometry. The interdendritic liquid forms a mushy layer, concentrates toward the eutectic composition, and ultimately freezes into a salt-bearing eutectic product when it reaches $T_E$. This replaces the pure planar salt-rejection picture with trapping and freezing of brine between crystals.

Use a planar saline Stefan problem with upward coordinate $z$, the initial contact at $z=0$, and phase boundaries $z=a(t)$ and $z=b(t)$ enclosing pure ice, where $a<b$. Fresh liquid occupies $z>b$ and brine occupies $z<a$. We assume negligible bulk flow, equal constant mass density $\rho$, specific heat capacity $c_p$ and thermal diffusivity $\kappa$ in all regions, and zero salt content and salt transport in the ice. Equal densities remove phase-change volume flow; suppressing convection isolates the molecular-transport mechanism. Different material properties would change the numerical coefficients. Set $K=\rho c_p\kappa$ for the common thermal conductivity and $\Delta T=T_m-T_{\infty }>0$. Denote the brine salt diffusion coefficient by $D$.

Use a linear ice liquidus, $T_L(C)=T_m-mC$, with $m>0$ and $C$ the salt mass fraction. Assume the initial brine is a stable liquid, $T_{\infty }>T_L(C_0)$, and all concentrations considered are below the eutectic composition. Thus $R=m{C}_0/\Delta T>1$. These assumptions exclude independent nucleation in a supercooled brine or an eutectic system event, neither of which is specified by the initial data alone. Start with a negligible seed of ice and use local phase equilibrium without interfacial kinetics or curvature. Temperature differences may be in Celsius, since only differences enter this calculation.

WriteThe paper calls $S$ a Stefan number; it is the latent-to-sensible heat ratio, reciprocal to another common Stefan number convention. At the lower phase boundary, define $T_i=T_L(C_i)$ and letThe liquidus relation is $\vartheta =Rc$.

A similarity solution gives an explicit calculation of the two positions. Putand use $u=z/(2\sqrt{\kappa t})$, $v=z/(2\sqrt{Dt})$. The temperatures and salinities areThese error function and complementary error function profiles satisfy the heat equation and the salt diffusion equation, their far-field conditions, and the interfacial temperature conditions. The fresh-water temperature is constant because the interface and the far field are both at $T_m$.

Salt conservation at the moving lower phase boundary requiresFor upward motion this is dilution by melting salt-free ice, rather than salt rejection by freezing brine. Substitution gives the dilution function for a melting saline Stefan front:For $A>0$, $0<c<1$, so the interfacial brine is fresher than the remote liquid.

The Stefan condition at the upper boundary is $\rho L\dot{b}=K{T}_{s,z}(b)$, since the fresh liquid has no temperature gradient. At the lower boundary it isThese signs follow from the jump in enthalpy: the upper front freezes liquid while a positive $\dot{a}$ melts solid. With $E=\mathrm{erf}B-\mathrm{erf}\delta$, they reduce toTogether with $\delta =ϵA$, these equations determine $A,B,\vartheta$, and hence both positions, without discarding the salt-diffusion correction.

For the stated large latent-to-sensible heat ratio, the layer is thin relative to the thermal diffusion length. Expanding the thermal equations for $B,\delta \ll 1$ givesConsequently a useful leading calculation iswhere the positive $A$ is obtained fromThe left side decreases with $A\ge 0$ while the right side increases, and their values at zero and infinity guarantee a unique positive root for large $S$. Thus this leading calculation includes the translation of the lower boundary as well as the increasing thickness.

If the scale separation also obeys $ϵSA\ll 1$, the familiar simpler result iswithThis last simplification needs the logarithmic refinement $ϵS\sqrt{\log (RS)}\ll 1$. The algebraic ordering $ϵ\ll S^{-1}$ alone should not be used to discard an arbitrarily large logarithmic correction; the preceding coupled equations remain the appropriate calculation when that refinement is unavailable. This distinction is captured by large latent heat in a freezing and melting ice layer.

The illustration uses $S=40$, $ϵ=2.5\times 10^{-4}$ and $R=2$. Solving the full equations gives $A=1.73707$, $B=0.0143053$ and $\vartheta =0.0158766$. It shows the ice layer between freshwater and cold brine, with both fronts advancing upward and a strongly diluted lower liquid boundary.

The phase diagram shows the spatial path from remote brine to the lower interface: temperature first changes over $\sqrt{\kappa t}$ at almost unchanged salinity, then salinity changes over its much smaller diffusion scale at nearly constant temperature. The liquid path ends on the liquidus at $(C_i,T_i)$; the solid has $C=0$ and its temperature rises from $T_i$ to $T_m$. The eutectic position is schematic, with $C_E=2C_0$ in the illustration, and is not used in the calculation. A point initially in the fresh layer freezes when $b$ reaches it, cools in the ice, and later melts when $a$ reaches it. The inset indicates this temporal path in the opposite direction through the solid branch and into the liquid.

The mechanism is simultaneous upper freezing and lower melting, with net growth of the ice thickness. Cold brine accepts most of the latent heat released by upper freezing. Salt reaching the lower contact lowers its equilibrium melting temperature, and melting freshens that liquid until its liquidus is close to $T_m$. The heat delivered through the ice supplies the much smaller melting demand there. The remote brine remains liquid even though it is below the pure-water melting temperature, because it lies above its own saline liquidus. Thus “cold” does not by itself decide which phase is stable. These conclusions apply while the layers remain effectively deep and the stated no-convection, pure-ice and phase-equilibrium assumptions hold.

Take $A>0$ for the repulsive molecular interaction, $p_0$ as the common reference pressure, and let $T_i=T_m-\delta T$ be the ice-film temperature. All ratios involving $T_m$ use its absolute value, approximately $273.15\mathrm{K}$, rather than the numerical Celsius value zero. The premelting film permits water to reach and freeze at the bottom of the ice while the upper surface is displaced upward without freezing there.

For equal phase mass densities, equality of the solid and liquid chemical potentials gives the Clapeyron pressure relation for equal-density phases. Indeed, $d\mu =-sdT+dp/\rho$ and $s_l-s_s=L/T_m$, so expansion around coexistence at $(T_m,p_0)$ yieldsThis is a pressure difference between phases, not a same-pressure Clausius-Clapeyron slope. The molecular disjoining pressure supports this difference:Treat the normal solid load as its effective pressure in this planar model. The gravitational load corresponding to hydrostatic pressure is $p_s=p_0+\rho gh$, so $p_l=p_0+\rho gh-p_T$. Refer the bath pressure to the sheet's upper gravitational datum, or neglect the sheet-scale hydrostatic head. The Darcy flow law then gives the upward supply and the ice growth rateHere $\Pi$ is permeability of a porous medium, $\mu$ is dynamic viscosity, and equal densities identify supplied liquid volume with added ice volume to leading order in $a/h$.

To recover the printed law, use the usual hydraulic control of frost heave idealization: the sheet's top is at $T_m$, the liquid film and ice have a common thermal conductivity $K$, and the flow is slow enough that latent-heat production is small compared with the conductive heat passing through the layer. In addition to a quasi-steady ice temperature field, this needsThe leading heat flux is consequently continuous through the film and ice. Their thermal resistances giveLet $B_T=\rho L\Delta T/T_m$, a pressure scale. The thermomolecular pressure and the molecular law then giveSubstitute this pressure into the Darcy flow law:The first term draws water toward the undercooled ice; the increasing gravitational load eventually cancels it.

Quasi-steady temperature alone is not sufficient to fix this exact prefactor. With film conductivity $K_l$, ice conductivity $K_s$, and nonnegligible latent heat, the appropriate additional balance isTogether with the Darcy equation, this is the implicit growth model. Even in the slow-flow limit, a conductivity ratio $K_s/K_l=r$ changes the leading driving pressure by $r^{3/4}$. Taking $r=2$ is a counterexample to obtaining the printed prefactor from quasi-steadiness alone. Thus the boxed equation is the intended equal-conductivity, thin-film, hydraulically limited model, rather than a consequence of only the stated quasi-steady assumption. This distinction is the heat-balance correction to a premelted-film growth model.

For that reduced equation defineThe scale $h_{\ast }$ balances $F{h}_{\ast }^{-3/4}$ against $\rho g{h}_{\ast }$; $F$ has units of pressure times length to the power $3/4$, so $h_{\ast }$ is a length and $t_{\ast }$ is a time. They yield

Set $u={\eta }^{7/4}$. The equation becomes linear:For initial thickness $\eta (0)={\eta }_0\ge 0$, the explicit solution of gravity-limited frost heave isThe usual zero-initial-thickness sketch usesIts early and late behaviour areFor $0<\eta <1$, the derivative is positive and ${\eta }^{\prime \prime }=(-\frac{3}{4}{\eta }^{-7/4}-1){\eta }^{\prime }<0$, so the curve is increasing and concave downward. It approaches the stable thickness $h_{\ast }$ exponentially. Initial thickness above $h_{\ast }$ instead relaxes downward; at $h_{\ast }$ it is stationary.

The singular slope at zero belongs to the formal reduced solution. Since $a/h\propto h^{-3/4}$, the thin-film assumption eventually fails as $h\to 0$. The early power law therefore describes an intermediate continuum regime after any microscopic startup, not arbitrarily early physical times. A finite positive ${\eta }_0$ supplies a regular initial condition when that regime begins. Gravity limits the ultimate thickness; molecular suction and the Darcy resistance set the growth toward it.

Low-temperature solid helium-3 can have greater entropy than the liquid through disordered nuclear spins, enabling compression cooling. ^[ref]

The sign follows from the Clapeyron equation. Let $S_l,S_s$ be molar entropies and $V_l,V_s$ molar volumes of liquid and solid, respectively, on their phase coexistence curve. Equality of their chemical potentials, with $d\mu =-SdT+VdP$, givesWith $S_s>S_l$ and $V_l>V_s$, the slope is negative. Reversibly freezing one mole at fixed temperature requires heat into the sample,Here $L_{s\to l}$ uses the melting convention for latent heat of fusion. This is the opposite sign from ordinary ice melting. The inequalities specify the regime; freezing does not universally cool a substance. In an approximately isolated sample, the growing higher-entropy phase draws on the sample's thermal energy instead of an external heater. Irreversible losses and incoming heat oppose the cooling.

An original deliberately local model makes the cooling quantitative. Fix a total amount $n$ of material, let $x$ be the mole fraction of solid, and stipulate molar entropiesThe constants $a$ and $b$ have units of molar entropy per temperature and molar entropy, respectively. Ignore their pressure dependence and the cell's own heat capacity. This is a local thermodynamics model, not an extrapolation to zero temperature. A constant positive $b$ cannot remain valid once the solid's spins order.

For a reversible thermodynamic process with no heat exchange, total entropy is constant. Differentiating giveswhen $b>aT$ and $x<1$. Define $T_0=b/a$; solving between two states givesIn particular, stipulate $x_0=0$, $T_i=T_0/4$ and $x=1/8$. ThenThe last expression is the local reversible heat requirement per mole frozen at the final state, divided by $b{T}_0$; it is not the heat exchanged during the isolated compression. That compression exchanges no heat. This distinction separates the latent-heat sign from the actual boundary heat budget.

The utility of the model is its explicit condition: $S_s>S_l$ makes $dT/dx<0$, while positive total heat capacity supplies a stable thermal response. More generally, for molar entropies depending only on temperature, let $C_l,C_s$ be the molar heat capacities. Then $dT/dx=-T(S_s-S_l)/[(1-x)C_l+x{C}_s]$. Incoming heat or entropy production adds terms to the balance and can overwhelm the ideal cooling. Neither the numerical ratios above nor the straight entropy lines are measurements of helium-3.

In the ideal solution and ideal gas vapor approximation, each component's partial pressure equals its liquid mole fraction times its pure-component vapor pressure at the same temperature:These pressure formulas neglect the change in the pure-liquid reference between its saturation pressure and $P$; appreciable real gas behavior also requires a more general treatment. The ideal solution definition in terms of chemical potentials does not require either approximation.^[ref]

A short derivation explains the reference choice. At vapor-liquid equilibrium, each component has the same chemical potential in the liquid and vapor. For an ideal gas mixture, chemical potential of an ideal gas giveswhere $p^{\circ }$ is a reference pressure. Approximate ${\mu }_i^{\ast }(T,P)$ by ${\mu }_i^{\ast }(T,p_i^{\ast })$ and subtract the pure-component equation from the mixture equation:Taking the exponential function gives Raoult's law. Summing partial pressures and normalizing gives $P$ and $y_i$; this last step uses the ideal gas vapor assumption separately from the liquid model.

The law is named after François-Marie Raoult, who measured vapor pressures and freezing behavior of chemical solutions.^[ref]

Salinity measures dissolved salt content. A transport model must specify its units; salt mass fraction is one convenient convention. A dilute solution's ice liquidus is often approximated by $T_L=T_m-mC$. Salt-free ice has zero salinity, and the moving interface's salt balance distinguishes salt rejection during freezing from dilution during melting.