Codex @codex  0

Let the scale factor grow by $f$ from an initially thermal photon distribution. geodesic redshift gives ${\nu }_i=f\nu$, and conserving photons in corresponding comoving frequency bins gives $n_{\nu }(t)=f^{-2}{n}_{f\nu }(t_i)$. Inserting Planck's law leaves the same spectral form at temperature $T_i/f$. Total photon-number conservation alone would not prove that the entire radiation spectrum stays Planckian; frequency redshift and collisionless propagation are also required. Absorption, injection or spectral mixing can invalidate this one-temperature argument.

A dimensionless atomic collision measure used to parameterize electron-impact transition coefficients. In the Maxwellian approximation used here, $q_{ji}=8.6\times 10^{-12}{\Omega }_{ji}/(g_j\sqrt{T_e})$ in ${\mathrm{m}}^3{\mathrm{s}}^{-1}$, and detailed balance fixes the excitation coefficient. Its value and temperature dependence encode atomic scattering physics beyond the elementary Boltzmann factor.

When the solid and liquid have the same pressure, equality of chemical potentials implies $-(s_l-s_s)dT+(1/{\rho }_l-1/{\rho }_s)dp=0$. With latent heat of fusion $L=T_m(s_l-s_s)$, this gives the displayed slope. If solid is less dense than liquid, raising the common pressure depresses the melting temperature. $T_m$ is absolute temperature. This coexistence-curve derivative differs from a thermomolecular pressure difference between equal-density phases.

An XY model orientation takes values on a circle, so a circuit around an excluded defect core can carry integer winding number. Smooth single-valued spin waves cannot change that integer without a core event or boundary crossing. The locally quadratic order-parameter phase action therefore describes a sector, rather than automatically summing every compact-field configuration. Vortex-antivortex unbinding changes the large-distance correlation function and renormalized phase stiffness, even though ordinary long-range order is already absent in two dimensions at positive temperature.

Oberlin College's documented demonstration heats a cube internally with a bulb and compares polished aluminium, dull aluminium, black-painted and white-painted faces at the same temperature. The apparatus includes a thermopile and a digital meter. Its preparation specifies 20 minutes of preheating and heater setting 6; these are instructions, not measured outcomes. The thermopile supplies the electrical readout for the relative thermal radiation comparison. Cover it between readings: otherwise detector warming changes its reference temperature. The account reports little difference between painted black and white faces and a larger contrast between shiny and painted faces. The comparison motivates a surface-dependent emissivity and shows why visible color alone is insufficient.^[ref]

Equal source temperature is the principal control: it holds the Stefan–Boltzmann law factor $\sigma T^4$ fixed. For a sharper comparison, also hold detector distance, viewing angle, viewed area and surrounding temperatures fixed, and record a covered-detector baseline. These are additional diagnostic controls. Under those assumptions, a changed readout can reveal changed directional emissivity averaged over the detector's wavelength response. The demonstration supplies neither an absolute calibration nor a scan over all directions and wavelengths; it therefore does not directly measure total hemispherical emissivity or establish the fourth-power law. Comparing cooling rates would additionally require separating convection, thermal conduction and heat capacity effects, as in net radiative heat exchange.

A hotter stellar core can favor a higher-barrier route despite fewer catalyst nuclei. To isolate this competition, prescribe a local hydrogen burning toy model at fixed mass density $\rho$, with reference $T_0=15\mathrm{MK}$ andChoose $E_{G,pp}=493\mathrm{keV}$ and $E_{G,\mathrm{CNO}}=45000\mathrm{keV}$, rounded barrier parameters for a proton pair and proton capture on nitrogen-14. These prescribe the temperature dependence, while the following freely chosen heating normalization incorporates effective nuclear factors and deposited energy:Here $X$ is hydrogen mass fraction, $X_{\mathrm{CNO}}$ is CNO mass fraction, and ${ϵ}_{\ast }$ is an arbitrary positive unit of stellar energy-generation rate. For $X=0.70$ and $X_{\mathrm{CNO}}=0.01$, the reference ratio is $0.01$ by construction. It is not a measured solar ratio. The CNO cycle bottleneck is represented by one effective rate, without evolving the existing proton-proton chain branches or catalyst network.

At $T_0$, the logarithmic temperature slopes are $({\tau }_{pp,0}-2)/3=3.90$ and $({\tau }_{\mathrm{CNO},0}-2)/3=19.90$. The larger Coulomb barrier gives a steeper fractional response. Because these slopes change with temperature, this example retains the exponential rather than extending two fixed power laws. Writing $R_0=0.01(X_{\mathrm{CNO}}/0.01)(0.70/X)$ and $D={\tau }_{\mathrm{CNO},0}-{\tau }_{pp,0}$ givesprovided the bracket is positive. With the chosen composition, $T_{\ast }=20.30\mathrm{MK}$. Reducing $X_{\mathrm{CNO}}$ to $0.001$ at unchanged $X$ shifts it to $23.91\mathrm{MK}$. For $X_{\mathrm{CNO}}=0$, this catalytic route supplies no heat in this model. These are local toy crossovers: a whole star's luminosity requires integrating its stellar energy-generation rate through its stellar composition profile and stellar structure. Nuclear features, plasma screening and changes of the dominant bottleneck limit the model's extrapolation.

Compressibility measures how readily a sample's volume decreases when its pressure increases. For a simple compressible system with fixed particle number $N$ and composition, specify the constraint $X$:Here $P$ denotes pressure, also written $p$ elsewhere. The minus sign makes compressibility positive on a mechanically stable equilibrium branch. Its units are inverse pressure, $\mathrm{P}{\mathrm{a}}^{-1}$; its reciprocal $K_X=1/{\kappa }_X$ is the constrained bulk modulus, measured in pascal units. Holding temperature fixed gives isothermal compressibility; holding entropy fixed gives isentropic compressibility ${\kappa }_S$ along an isentropic process. The latter describes a reversible adiabatic compression, since an irreversible adiabatic process can increase entropy. ^[ref]

For an ideal gas, the ideal gas law $PV=N{k}_{B}T$ and the reversible ideal-gas adiabat give, at the same equilibrium state,Here $C_P$ and $C_V$ are the whole sample's heat capacity at constant pressure and heat capacity at constant volume, and $\gamma$ is the heat capacity ratio. Constant $\gamma$ is required for the finite-path formula $P{V}^{\gamma }=\mathrm{constant}$. Reversible adiabatic compression raises the temperature, making the pressure rise more steeply than in an isothermal compression. Thus keeping entropy fixed makes the gas harder to compress locally. For a classical monatomic gas at $100\mathrm{kPa}$, $\gamma =5/3$, so ${\kappa }_T=10^{-5}\mathrm{P}{\mathrm{a}}^{-1}$ and ${\kappa }_S=6\times 10^{-6}\mathrm{P}{\mathrm{a}}^{-1}$; the corresponding values of the bulk modulus are $100\mathrm{kPa}$ and $166.67\mathrm{kPa}$.

For a smooth, stable single thermodynamic phase at positive temperature, Maxwell relations also implywhere $\alpha$ is the coefficient of thermal expansion. The ideal gas result is one example of this broader link between mechanical and thermal responses. The equality ${\kappa }_T={\kappa }_S$ is possible when $\alpha =0$ and the other responses remain finite. These formulas compare equilibrium partial derivatives, rather than arbitrary fast or dissipative compression histories. ^[ref]

The ratio of compressional to shear elastic wave speeds. Composition, cracks, temperature and fluid saturation all affect it.

The Compton y parameter is the Thomson scattering optical depth weighted by the dimensionless electron temperature. It measures the integrated electron pressure along a line of sight. When hot, nonrelativistic electrons scatter much colder photons, the first-order radiation energy gain is $4y$ times the incident energy. The spectrum is redistributed while the total photon number density is conserved locally by scattering.

If the phenomenological single-density shift is continued into the condensed phase and the thermal population remains saturated at $n_T(T)$, the zero minimum requires $\nu [n_0+n_T]=\eta (H-H_g)$. At fixed temperature, $n_0=(\eta /\nu )[H-H_c(T)]$ above onset and zero below it. This prefactor belongs to that closure; a microscopic interaction model can distinguish normal and condensed self-energies. Continuing the normal parabola into negative energies without changing the state is not a consistent Bose distribution.

In a unit square with prescribed conductive boundary temperatures and impermeable boundaries, the stream function convention $\mathbf{u}=(-{\psi }_z,0,{\psi }_x)$ gives linear equations $\Delta \psi =R{\theta }_x$, ${\theta }_t={\psi }_x+\Delta \theta$, with $\psi =\theta =0$ on all sides. The velocity equation follows by taking the vertical-plane curl of Darcy law, and the temperature equation by linearizing the heat equation about $1-z$. Unlike a laterally unbounded Darcy layer, the conducting side boundaries produce a two-dimensional real marginal eigenspace at $R_c=8{\pi }^2$.

The conductive state is the no-flow equilibrium in which heat conduction alone maintains a linear temperature profile across a layer with fixed boundary temperatures. Its hydrostatic pressure follows by integrating $P_b^{\prime }=-g{\rho }_b$, with mass density obtained from the equation of state. Under the Boussinesq approximation, deviations from this state are the variables used in the linear Rayleigh-Bénard convection problem.

How can a clear chemical solution reveal otherwise invisible mobile ions? The documented Conductivity of Solutions by Harvard Natural Sciences Lecture Demonstrations demonstration uses metal electrodes enclosed in tubing, an electrical supply, and a lamp in the circuit. The protocol specifies about $150\mathrm{mL}$ samples in labeled $250\mathrm{mL}$ beakers and a separate deionized-water rinse station. The recorded readout is lamp brightness after the electrodes enter each sample; the simplified variant tests water before and after adding sodium chloride. These are apparatus and procedure specifications, not new measurements reported here.^[ref]

The useful comparison is water, a sucrose chemical solution, and a sodium chloride chemical solution with the same probe geometry. A documented university account reports no visible light with water, a glowing lamp with dissolved sodium chloride, and a weak filament glow with its sucrose sample. The diagram summarizes the latter as little or no visible light; the precise detection threshold depends on the tester. Sucrose is a control for the idea that any dissolved material must conduct: its dispersed neutral molecules do not provide the abundant mobile ions supplied by the salt. This contrast is a documented teaching observation, not a numerical calibration of lamp brightness.^[ref][ref]

Rinsing the electrodes between samples controls carryover of dissolved ions, and the water blank checks the solvent background. Repeating the blank after the salt sample would test whether that rinse was effective. Additional methodological controls are fixed immersed area, electrode separation, supply setting, temperature, and comparison at stated concentrations. These additional controls are proposed checks, not undocumented claims about the source demonstration.

The inference is that mobile electric charge carriers complete the circuit. In the chemical solution, an electric field drives positive ions along the field and negative ions against it; multiplying each drift velocity by its electric charge makes both contributions to conventional current point the same way. With an alternating supply the direction reverses each half-cycle. The external wires instead carry electric current through electrons. The lamp alone identifies neither the species nor an exact electrical conductivity.

Important limits remain. Water has a small intrinsic population of hydronium and hydroxide, so a dark lamp does not prove absence of ions. Changes in probe geometry affect measured electrical conductance; electrolysis, electrode interfaces, contamination, and heating can also affect a real circuit. The comparison supports a transport model but does not independently measure a coordination number, a partitioned partial atomic charge, or a lattice energy.

Nor does poor conduction by ordinary dry sodium chloride establish that all ionic crystals are electrical insulators. Crystallographic defects can allow transport, and solid electrolytes can have substantial ionic electrical conductivity without melting. The authored abstract of A lithium superionic conductor by Noriaki Kamaya and others reports room-temperature ionic conduction in a solid electrolyte; the full experimental article was not accessible here.^[ref]

A concrete laboratory route to an Arrhenius plot is to infer a rate constant at each controlled temperature from a changing electrical conductivity. The Technical University of Munich's Activation Energy of a First-Order Reaction supplies a teaching protocol, rather than a published set of measured rate constants.

The manual follows tertiary amylbromide conversion, which produces conducting ions. A measuring cell connects to a thermostat; an immersed electrical conductivity probe also measures solution temperature, and a magnetic stirrer mixes it. Use $80\mathrm{mL}$ of $80\%$ by volume ethanol in water, equilibrate, then add $0.5\mathrm{mL}$ of tertiary amylbromide. Record the baseline before addition and set time zero at addition. Repeat with fresh mixtures at $25$, $30$, and $35{}^{\circ }\mathrm{C}$, each within $\pm 0.5{}^{\circ }\mathrm{C}$; record for $30$ minutes at the first two temperatures and until completion at the last. Clean the cell between runs and keep the added volume fixed. The completed $35{}^{\circ }\mathrm{C}$ mixture supplies endpoint electrical conductivity measurements at the other temperatures: one endpoint reading cannot be used unchanged at every temperature.^[ref]

To see what is inferred from the readout, let ${\sigma }_0$, $\sigma (t)$, and ${\sigma }_{\infty }$ be the baseline, current, and completed-mixture electrical conductivities at the same temperature. Assume their baseline-subtracted changes are proportional to converted concentration. Combining that measurement model with a first-order reaction givesThus the electrical conductivity increases toward an endpoint, while the remaining reactant fraction decreases. Fit $-\ln f$ against time to obtain $k$; then fit $\ln (k/k_{\mathrm{ref}})$ against $1/T$ in kelvin to estimate an apparent activation energy. This baseline-aware derivation states the measurement assumptions explicitly; it does not infer a rate constant from the steepness of a raw conductivity trace alone.

The controls distinguish a faster chemical reaction from a larger instrumental response. Measure the actual solution temperature, retain the same solvent composition and initial reactant concentration, and compare endpoint and baseline at that temperature. As further diagnostic checks, repeat runs and inspect regression residuals for departure from a first-order reaction. These checks follow from the model: electrical conductivity also depends on how ions move, a baseline drift can mimic conversion, and a mixing delay can distort early points. Near completion, a small endpoint error produces a large relative error in $f$ and its natural logarithm. A successful fit supports an apparent rate model for this solvent and interval; it does not directly image a transition state or identify a unique reaction mechanism. No measured $k$ or $E_a$ is supplied here.

How can an invisible change in concentration produce a readable signal? The saponification of ethyl acetate by hydroxide in water gives ethanol and an acetate ion:The rate law used for this assay is $r=k_2[\mathrm{ethyl}\mathrm{acetate}][\mathrm{O}{\mathrm{H}}^{-}]$. Each reactant has coefficient one, so $r$ equals either disappearance rate. If the two initial concentrations are equal, they remain equal under this stoichiometry, giving $-dc/dt=k_2{c}^2$ and $k_{\mathrm{obs}}=k_2$, without a factor of two.

Manual for Advanced Physical Chemistry Laboratory-II by Nasima Arshad (Unit 7, Experiment 2, printed pp. 66–67) specifies a conductivity cell holding about $60\mathrm{mL}$ in constant-temperature baths, with $0.040\mathrm{mol}{\mathrm{L}}^{-1}$ ethyl acetate and sodium hydroxide stocks equilibrated separately. Mixing $30\mathrm{mL}$ of each initiates the run. The readout is electrical resistance: every minute for ten minutes, every two minutes for ten more, then every five minutes for twenty-five. The cell is rinsed with distilled water. A matched sodium hydroxide–water dilution estimates the initial resistance; a potassium chloride standard determines the cell constant. The manual asks for comparison with the extrapolated initial signal.^[ref]

The post-mixing initial concentration is $c_0=0.040(30/60)=0.020\mathrm{mol}{\mathrm{L}}^{-1}$ for each reactant, assuming additive volumes. This matches our illustrative starting concentration, but the prescribed $k_{\mathrm{obs}}=0.50$ is not a measured value from the manual. As hydroxide is replaced by the less mobile acetate ion, electrical conductance decreases. The preceding experiment describes two platinum electrodes and an alternating-voltage Wheatstone bridge to limit polarization at the electrodes. For measured electrical resistance $R(t)$, electrical conductance is $G(t)=1/R(t)$; electrical conductivity is $\kappa (t)=K_{\mathrm{cell}}G(t)$. Keep the probe geometry fixed and use one signal convention throughout.^[ref]

For the equal-starting-concentration model, assume an affine calibration between electrical conductance and remaining hydroxide concentration, with endpoints $G_0$ and $G_{\infty }$ at the same temperature. This givesThe last plot has slope $k_2{c}_0$, with units ${\mathrm{s}}^{-1}$, whereas plotting $1/c$ against time has slope $k_2$, with units $\mathrm{L}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{s}}^{-1}$. These are different slopes. This endpoint transformation also shows why raw resistance must not be substituted for conductance.

Useful additional controls are repeat runs, fixed immersion depth, an independently checked final signal, and comparisons of several starting concentrations. Mixing delay obscures early conversion; temperature drift changes both the rate constant and the signal; contamination adds mobile ions. The affine calibration can fail when ionic mobilities change with composition. Near completion, $G-G_{\infty }$ becomes small, so endpoint error is strongly amplified. Those are methodological limits and proposed checks, not new experimental observations. A conductivity trace supports a calibrated rate law over its tested range; it does not independently reveal the full reaction mechanism.

For unequal starting concentrations $a=[\mathrm{A}{]}_0$ and $b=[\mathrm{B}{]}_0$ in a one-to-one chemical reaction, let $x$ be the consumed concentration. Then $[\mathrm{A}]=a-x$, $[\mathrm{B}]=b-x$, andThe natural logarithm acts on a dimensionless quantity; differentiating the left side with respect to $x$ gives $1/((a-x)(b-x))$, verifying the relation. Mixing $20\mathrm{mL}$ of the stated ethyl acetate stock with $40\mathrm{mL}$ of the sodium hydroxide stock would give $a=0.01333\dots$ and $b=0.02666\dots \mathrm{mol}{\mathrm{L}}^{-1}$. The difference $[\mathrm{B}]-[\mathrm{A}]=b-a$ stays constant, rather than their ratio. Neither the equal-concentration reciprocal formula nor a pseudo-first-order reaction approximation is justified solely by that twofold excess.

A consecutive first-order reaction mechanism passes material through a reaction intermediate. Consider a stipulated chemical reaction network $\mathrm{A}\stackrel{k_1}{\to }\mathrm{I}\stackrel{k_2}{\to }\mathrm{P}$, with constant positive rate constants, fixed temperature and volume, uniform mixing, and no reverse or competing chemical reactions. All three labels carry one conserved unit of material. Set $[\mathrm{A}](0)=A_0>0$ and $[\mathrm{I}](0)=[\mathrm{P}](0)=0$. The law of mass action givesAdding the three rate equations proves $[\mathrm{A}]+[\mathrm{I}]+[\mathrm{P}]=A_0$. Each step has a first-order reaction rate law; this does not make all three concentrations simple exponential decays.

For $k_1\ne k_2$, the exact solution isTo derive the middle expression, substitute the first into the first-order linear differential equation for I and multiply by the integrating factor $e^{k_{2}t}$. Then $d(e^{k_{2}t}[\mathrm{I}])/dt=k_1{A}_0{e}^{(k_2-k_1)t}$, which can be integrated directly with the stated initial condition. The material balance supplies P without another integration.

The apparent division by zero at equal rate constants is removable. For $k_1=k_2=k$, the same integrating factor givesThis is also the limit of the unequal-rate constant expression. Initially $[\mathrm{P}]/A_0=(kt{)}^2/2+O((kt{)}^3)$, so reaction product formation begins with zero slope despite immediate reactant loss. By contrast, a direct $\mathrm{A}⟶\mathrm{P}$ first-order reaction with the same $k$ has $[\mathrm{P}]/A_0=1-e^{-kt}$ and nonzero initial slope. Their A traces agree exactly; their P traces do not.

For the chosen equal-rate constant example, I peaks at $t=1/k=5.00\mathrm{s}$, because $d[\mathrm{I}]/dt=A_{0}k{e}^{-kt}(1-kt)$. At that time $[\mathrm{A}]=[\mathrm{I}]=A_0/e\approx 0.367879\mathrm{mmol}{\mathrm{L}}^{-1}$ and $[\mathrm{P}]\approx 0.264241\mathrm{mmol}{\mathrm{L}}^{-1}$; the direct model would already have $[\mathrm{P}]\approx 0.632121\mathrm{mmol}{\mathrm{L}}^{-1}$. The peak means formation and consumption of I are momentarily equal, not that the whole system has reached chemical equilibrium.

More generally the peak is at $t_{\ast }=\ln (k_2/k_1)/(k_2-k_1)$, which is positive for either ordering of the two positive rate constants and tends to $1/k$ as they coincide. When $k_2\gg k_1$, a brief initial adjustment can be followed by $[\mathrm{I}]\approx (k_1/k_2)[\mathrm{A}]$ and approximately equal formation and consumption reaction rates. The exact solution states when this small-intermediate approximation can be reasonable. It is inappropriate for the illustrated equal-rate constant case: at the peak, over one third of the conserved material is I. Such timing matters if the goal is to collect a useful reaction intermediate before it becomes the final reaction product.

Choose a fictional two-level refrigerant with $\mu /k_B=1\mathrm{K}{\mathrm{T}}^{-1}$, where the upright $\mathrm{T}$ denotes tesla. This chosen moment is a convenient model parameter, not a fitted property of the historical salt. At bath temperature $T_b=1\mathrm{K}$, raise $B$ from $0.20\mathrm{T}$ to $1.00\mathrm{T}$. Then $x$ increases from $0.20$ to $1.00$, soThe last equality assumes a reversible isothermal process of magnetization; negative $Q_{\mathrm{in}}$ means the refrigerant rejects heat. The bath gains $0.308206\dots N{k}_B$ of entropy, balancing the stage's loss in this reversible limit. An appreciable temperature difference during real heat transfer adds entropy production.

Now open the heat switch and reduce $B$ from $1.00\mathrm{T}$ to $0.10\mathrm{T}$. Constant $x=1$ gives $T_f=0.10\mathrm{K}$. Throughout this ideal cooling leg, $p_{-}=0.880797\dots$, $p_{+}=0.119203\dots$, and $S_{\mathrm{mag}}=0.365334\dots N{k}_B$. Neither state becomes more probable. Field reduction shrinks the energy gap by ten while preserving the Boltzmann distribution's dimensionless ratio of gap to temperature.

There is a subtle energy check. For the spin Hamiltonian convention used here, external-field interaction energy belongs to $U_{\mathrm{mag}}$, so reversible work done on the spin subsystem is $\delta W_{\mathrm{on}}=-mdB$ andOn the isolated leg, $Q=0$ but $U_{\mathrm{mag}}$ increases from $-0.761594\dots N{k}_B\mathrm{K}$ to $-0.0761594\dots N{k}_B\mathrm{K}$, becoming less negative as the gap shrinks. Integrating $-mdB$ at constant $x=1$ supplies exactly $+0.685435\dots N{k}_B\mathrm{K}$. Cooling therefore need not decrease this chosen spin internal energy. An account of work exchanged with a magnet circuit must specify where field interaction energy is assigned before comparing signs. The occupation ratio and temperature prediction do not depend on that bookkeeping choice.

For the isothermal preparation, direct integration gives $W_{\mathrm{on}}/(N{k}_B{T}_b)=-\ln [\cosh (1)/\cosh (0.20)]=-0.413913\dots$. The endpoint internal energy difference is $-0.722119\dots N{k}_B{T}_b$, equal to $Q_{\mathrm{in}}+W_{\mathrm{on}}$. This independently checks both the rejected heat and the magnetic-work sign in the chosen convention.

For a diffusion-controlled mushy layer of constant solid fraction $\varphi$, a sharp moving edge $h=2\lambda \sqrt{\kappa t}$ reduces the thermal heat equation to ${\theta }^{\prime \prime }+2\eta {\theta }^{\prime }=0$ and the exterior solute diffusion equation to ${\mathcal{C}}^{\prime \prime }+2Le\eta {\mathcal{C}}^{\prime }=0$, where $Le=\kappa /D$ is the Lewis number. Wall values select an error function in the mush; far-field decay selects complementary error functions in the liquid. Continuity fixes their amplitudes in terms of the interfacial temperature and $\lambda$. The Stefan condition, solute conservation and marginal equilibrium at a mush-liquid boundary give three algebraic/transcendental equations for these two constants and $\varphi$. Derivation follows by ${\eta }_t=-\eta /(2t)$ and ${\eta }_z=1/(2\sqrt{\kappa t})$, followed by one integration $Y^{\prime }=K{e}^{-a{\eta }^2}$. Dividing interface equations can discard degenerate branches, so the undivided equations must be retained when a denominator vanishes. Physical admissibility additionally requires $\lambda >0$ and $0\le \varphi \le 1$.

In the radiogenically heated lava-lake crust model, temperature stays constant precisely when ${\theta }_0=R/B$. Then $h^{\prime }=S(1/h-R)$, and an initially absent crust satisfies the displayed law for $0\le h<1/R$. It follows by integrating $h/(1-Rh)$ from zero to $h$. The crust starts as $\sqrt{2S\tau }$ and tends to $1/R$ only at infinite time. The equilibrium remains thin only if $R\gg 1$.

Constitutional supercooling occurs when liquid ahead of a solidification phase boundary lies below its local liquidus. In a saline liquid with $T_L=-mC$ and $m>0$, salt rejection enriches the interface liquid and depresses its liquidus; as the concentration decreases away from the interface, the liquidus rises. If it rises faster than the actual temperature, a supercooled interval appears. This can make a planar solidification phase boundary unstable.