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A binary mixture is a mixture with two specified chemical components. Water mixed with ethanol is a familiar example. “Binary” counts the components used to describe composition, rather than the number of thermodynamic phases: two components can form one homogeneous mixture or coexist in distinct thermodynamic phases.^[ref]

For two nonreacting components with amounts of substance $n_A,n_B$, the amount fractions satisfyOnly one composition coordinate is independent. In an original preparation using1mole of ethanol and3moles of water, $x_{\mathrm{ethanol}}=1/4$. Using rounded molar masses46.07and18.015grams per mole gives the ethanol mass fractionThus25percent by amount of substance and about46percent by mass describe the same preparation. A composition percentage without its basis is ambiguous. The calculation uses component masses, without assuming additive liquid volume.

Hexane and water illustrate why component count and phase count differ. Their limited mutual solubility permits two liquid thermodynamic phases, each containing some of the other component. A primary compiled experiment equilibrated the liquids by overnight shaking, sampled the aqueous portion with a microsyringe, and measured dissolved hydrocarbon by gas chromatography with flame-ionization detection.^[ref] The liquid immiscibility article develops a lever rule calculation distinguishing each phase's composition from the overall composition.

A binary mixture is not automatically an ideal solution. Interactions between unlike molecules can change activities, mixing enthalpy and phase stability. Stating temperature, pressure and the composition basis is therefore part of specifying the system, rather than optional experimental detail.

The conditioning of tie-line phase-fraction inference describes how strongly composition perturbations change an inferred phase fraction. For a binary mixture with distinct endpoints, the lever rule gives $\lambda =(z-a)/(b-a)$. Its absolute sensitivity to $z$, with endpoints fixed, is $1/|b-a|$. This is an absolute amplification coefficient; a relative condition number additionally depends on the chosen input and output scales.

For an interior $0\le \lambda \le 1$, the differential in tie-line phase-fraction sensitivity yieldsto first order. If each composition perturbation is bounded by $\epsilon$, this becomes $2\epsilon /|b-a|$. For original stipulated $\epsilon =0.001$, endpoint separations $0.50$ and $0.05$ give local worst-case bounds $0.004$ and $0.040$. Tenfold closer endpoints make the same composition precision tenfold less informative about phase amount. Correlations can change the attainable combinations of errors, as common affine calibration cancellation in the lever rule illustrates.

For fixed multicomponent endpoints and overall-composition covariance matrix $\Sigma$, the tie-line phase-fraction uncertainty isThe denominator is endpoint separation after a whitening transformation: separation must be compared with measurement precision, not only plotted distance. This follows from covariance-based uncertainty propagation and the linear fit.^[ref]

Near coincident endpoints the inverse problem becomes poorly informative, and at coincidence it is undefined. Near the physical bounds, a large propagated uncertainty also warns that the interior linear approximation may fail. More numerical digits in the fitted answer do not resolve this measurement limitation.

The lever rule finds phase fractions from a horizontal tie line on a phase diagram. For solid and liquid concentrations $C_s,C_l$ and bulk concentration $\overline{C}$, conservation gives $\overline{C}=(1-\varphi )C_s+\varphi C_l$. Thus $\varphi =(\overline{C}-C_s)/(C_l-C_s)$ is the liquid fraction, provided $C_s\le \overline{C}\le C_l$. For a solute-free solid, $C_s=0$ and $\varphi =\overline{C}/C_l$.

Liquid immiscibility is the failure of a mixture to form one homogeneous liquid at the specified composition and conditions. In a two-liquid phase equilibrium, each thermodynamic phase can contain some of both components, but their equilibrium compositions differ. “Immiscible” therefore need not mean that no molecules of either component dissolve in the other.

Hexane and water provide a concrete example of limited mutual solubility. A NIST-compiled experimental record describes overnight shaking, microsyringe sampling of an aqueous solution, and gas chromatography with flame-ionization detection to measure the dissolved hydrocarbon. Detecting a small dissolved amount does not imply that every bulk mixing ratio gives one liquid phase.^[ref]

An original lever rule example shows how phase amounts differ from phase compositions. Suppose a binary system at fixed temperature and pressure has coexisting liquid compositions $x_{\alpha }=0.1$ and $x_{\beta }=0.8$, where $x$ is the mole fraction of componentB. These stipulated values are not measurements of hexane/water. If the overall mole fraction is $z=0.4$, material balance givesHere $\lambda$ is the fraction of the total amount of substance in phaseβ. A100-mole sample therefore contains $300/7\simeq 42.86$ moles in phaseβ and $400/7\simeq 57.14$ moles in phaseα. The phase compositions stay0.8 and0.1; neither is the overall composition0.4.

Shaking the sample can create dispersed droplets without making a single molecularly homogeneous phase. Equilibration, temperature, pressure and composition must be stated when testing liquid-liquid equilibrium. The lever-rule fraction is a mole-amount fraction, not necessarily the fraction of vessel height or volume occupied by one layer.

At fixed temperature and pressure, liquid-liquid equilibrium is stable coexistence of distinct liquid thermodynamic phases that minimizes total Gibbs free energy for the specified component amounts. Their compositions can differ even though each exchanging chemical species has the same chemical potential in both phases. For neutral, nonreacting components in bulk phases at common temperature $T$ and pressure $p$, neglecting external-field and interface-curvature contributions,To see why, transfer an amount $d{n}_i$ from phase $\alpha$ to phase $\beta$ while holding the total amount of each component fixed. The change in Gibbs free energy is $dG=({\mu }_i^{\beta }-{\mu }_i^{\alpha })d{n}_i$. If the coefficient is nonzero, one transfer direction lowers $G$. Equality removes that driving term; stable equilibrium additionally requires a global minimum over the allowed phase arrangements. Here each chemical potential is the partial derivative of Gibbs free energy with respect to that component amount at fixed temperature, pressure and the other component amounts.^[ref]

Charged species instead require equality of the corresponding electrochemical potential. Equal chemical potentials for neutral species do not require equal mole fractions. With a common pure-component reference, ${\mu }_i={\mu }_i^{\circ }+RT\ln a_i$ and $a_i=x_i{\gamma }_i$, where $a_i$ is thermodynamic activity, ${\gamma }_i$ an activity coefficient, and $R$ the molar gas constant. The activity equality for coexisting liquids is $x_i^{\alpha }{\gamma }_i^{\alpha }=x_i^{\beta }{\gamma }_i^{\beta }$. Different nonideal environments can therefore support different compositions at the same chemical potential.

For a binary mixture, let $x$ be the mole fraction of component B and let $g(x)$ be the homogeneous molar Gibbs free energy at fixed $T,p$. Differentiating $G=(n_A+n_B)g(n_B/(n_A+n_B))$ givesEquality of both component chemical potentials between two compositions becomes the common-tangent construction for phase coexistence:In this molar representation, the tangent slope is ${\mu }_B-{\mu }_A$ and its intercept is ${\mu }_A$. Stable coexistence uses a supporting tangent lying below the homogeneous curve over all admissible compositions. This constructs the relevant convex envelope; two stationary points or equal slopes alone do not establish stability.

An original regular solution calculation makes this distinction visible. Because linear composition bias leaves coexistence compositions unchanged, subtract the linear pure-component reference and writeThe dimensionless parameter $\chi$ penalizes unlike contacts when it is positive. Take $\chi =3$. Symmetry makes the coexistence tangent horizontal, and the two outer solutions of $h^{\prime }(x)=\ln (x/(1-x))+3(1-2x)=0$ give the symmetric regular-solution binodal:These are model compositions, rather than measured hexane–water values. At overall mole fraction $z=0.30$, the liquid-liquid tie line and lever rule give the fraction $\lambda$ of total moles in phase $\beta$:Changing $z$ within the coexistence interval changes phase amounts while leaving the two endpoint compositions fixed. These mole-based phase fractions need not equal volume fractions.

The spinodal answers a different question: local stability of a homogeneous mixture. Here $h^{\prime \prime }(x)=1/[x(1-x)]-2\chi$, so at $\chi =3$ the two local-stability limits are $(1\mp \sqrt{1/3})/2\approx 0.211325,0.788675$. Between them, composition fluctuations lower the bulk free energy. Between a binodal endpoint and the nearer spinodal, the homogeneous state has positive local curvature but a lower-energy phase-separated state exists: this is metastability. Thus the observed coexistence compositions are not obtained merely by setting $h^{\prime \prime }=0$.

A useful experiment measures compositions as well as the presence of layers. One hexane–water record reports overnight shaking, microsyringe sampling of the aqueous solution, and gas chromatography to measure dissolved hydrocarbon. The small dissolved amount is evidence of finite mutual solubility, consistent with liquid immiscibility over other bulk compositions.^[ref] At controlled temperature, repeated sampling of both phases and checks from different initial compositions help test whether the endpoint compositions have stabilized. Critically evaluated reference systems provide a way to validate such instruments and techniques.^[ref]

A liquid-liquid tie line joins the compositions of two liquid phases that coexist at a specified temperature and pressure. Its endpoints describe the separate phases; an interior point describes an overall composition formed from suitable amounts of them. The liquid-liquid tie line therefore connects equilibrium chemistry with material balance rather than describing a spatial boundary between layers.

For a binary mixture, use component-B mole fractions $x_{\alpha }$, $x_{\beta }$ and overall fraction $z$. If $\lambda =n_{\beta }/(n_{\alpha }+n_{\beta })$ is the mole-based phase fraction in phase $\beta$, conservation of component B gives the lever rule:The endpoints must be different and $0\le \lambda \le 1$. For invented coexistence endpoints $x_{\alpha }=0.20$, $x_{\beta }=0.80$ and overall $z=0.35$, the result is $\lambda =0.25$. In a $4$-mole sample, the phases contain $3$ and $1$ moles; their component-B amounts are $0.60$ and $0.80$ moles, totaling $1.40=4(0.35)$. These mole amounts do not specify the two layer volumes.

A ternary liquid-liquid tie line obeys the same vector balance. For chosen endpoint vectors ${\mathbf{x}}^{\alpha }=(0.7,0.2,0.1)$ and ${\mathbf{x}}^{\beta }=(0.1,0.3,0.6)$, a phase fraction $\lambda =0.4$ gives $\mathbf{z}=(0.46,0.24,0.30)$. Every component must give the same $\lambda$. A normalized composition vector need not lie on this particular line; normalization alone does not establish compatibility with the proposed endpoints.

The lever rule determines amounts after equilibrium endpoints have been established; it does not select those endpoints. They can come from measured phase compositions or a stable common-tangent construction for phase coexistence. Reliable experiments control temperature and sample purity, measure the separated compositions and distinguish genuine liquid-liquid equilibrium from other phase behavior. An IUPAC reference-system assessment specifically warns that turbidity can confuse liquid–liquid and solid–liquid transitions.^[ref]

Choose a hypothetical fluid with molar constants $a_m=0.360\mathrm{Pa}{\mathrm{m}}^6\mathrm{mo}{\mathrm{l}}^{-2}$ and $b_m=4.00\times 10^{-5}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, using $R=8.314462618\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$. These stipulated constants are not a fit to carbon dioxide. The molar critical formulas giveAt $T=360\mathrm{K}$ and $v_m=240\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, first convert $v_m$ to $2.40\times 10^{-4}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$. The repulsive-volume term and attractive correction areso $p=8.716033\mathrm{MPa}$. The ideal gas law would instead give $RT/v_m=12.471694\mathrm{MPa}$. The excluded volume raises pressure relative to that ideal value, but attraction more than offsets the increase here. Neither correction alone describes this example.

For $n_{\mathrm{mol}}=0.500\mathrm{mol}$, the same state occupies $V=n_{\mathrm{mol}}{v}_m=120\mathrm{c}{\mathrm{m}}^3$. The total-volume formula gives $n_{\mathrm{mol}}{b}_m=20\mathrm{c}{\mathrm{m}}^3$ and the same $8.716033\mathrm{MPa}$. Halving the sample has halved both its physical volume and its excluded volume, while retaining its pressure. Conversely, if the two critical measurements $T_c,p_c$ are used to determine model constants, inversion givesAn independent critical molar volume then tests the prediction $v_{m,c}=3R{T}_c/(8p_c)$; agreement with two fitted numbers does not ensure agreement with the third.

At $t=0.9$, the Van der Waals liquid-gas coexistence example below becomes $T\simeq 288.6537\mathrm{K}$, $p_{\ast }\simeq 5.391653\mathrm{MPa}$, $v_{m,l}\simeq 72.40823\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$ and $v_{m,g}\simeq 281.8611\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$. For a mean molar volume of $120\mathrm{c}{\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$, the lever rule gives gas mole fraction $f_g\simeq 0.227219$. Its volume fraction is instead $f_g{v}_{m,g}/v_m\simeq 0.533703$: less than one quarter of the molecules occupy more than half the volume. The flat equilibrium pressure corresponds to changing these proportions. It does not describe a homogeneous sample sliding along the unstable loop.

The saturation concentration $c_{\mathrm{sat}}(T)$ is the dilute-phase coexistence concentration at the specified temperature and solution conditions. On increasing the overall concentration through this boundary, a macroscopic condensed phase can first coexist with the dilute phase. The other branch gives the dense-phase concentration $c_{\mathrm{dense}}(T)$.

At the thermodynamic critical point, the two branches meet: their concentration difference vanishes. Its coordinates define the critical concentration $c_c$ and critical temperature $T_c$. In the upper-critical model, $T>T_c$ admits no two-liquid coexistence. Thus $c_{\mathrm{sat}}$ is a temperature-dependent branch, whereas $c_c$ is the concentration at the endpoint.

Between coexistence concentrations, the lever rule gives the dense-phase volume fraction $v=(\bar{c}-c_{\mathrm{sat}})/(c_{\mathrm{dense}}-c_{\mathrm{sat}})$, assuming consistent concentration and volume definitions. Increasing total chromatin then primarily changes phase amounts rather than allowing the dilute phase to increase without bound.

Apply the lever rule on the $779^{\circ }\mathrm{C}$ solid tie line. All compositions are copper mass percentages:Thus the equilibrium material is 77.1% $\alpha$ and 22.9% $\beta$ by mass just below the eutectic temperature. These are phase fractions; converting them to volume fractions would require densities.

The profile estimate and equilibrium lever-rule estimate need not agree exactly. The height trace contains only four major ridges, making it a small sample of the microstructure. Pixel size, ridge-threshold choice, tip geometry, contamination, polishing damage and unequal etching change apparent widths. A finite-radius AFM tip can broaden the narrow raised cementite regions, biasing their inferred fraction upward.

The equilibrium calculation assumes eutectoid pearlite with the chosen carbon composition and tie-line values. Off-eutectoid steel can include proeutectoid ferrite or cementite outside the pearlite; alloying, carbon segregation and non-equilibrium cooling alter the simple Fe–C estimate. Carbon solubility also varies with temperature. The mass-to-volume conversion requires phase densities.

The observed difference between roughly $17\%$ ridge fraction and $11\%$ equilibrium phase volume is therefore a reason to examine sampling and the etched-surface measurement, not to force the image widths to match the lever rule. Multiple colonies, repeated calibrated traces and a phase-sensitive measurement would improve the comparison.

For eutectoid pearlite, apply the lever rule between ferrite and cementite at the transformation temperature. Using standard approximate Fe–C values $C_e=0.76$, $C_{\alpha }=0.022$ and $C_{\mathrm{cem}}=6.67$ in weight percent carbon,These are mass fractions. To compare with an unbiased geometric line fraction, convert using the phase densities:With representative densities ${\rho }_{\mathrm{cem}}\simeq 7.69$ and ${\rho }_{\alpha }\simeq 7.87\mathrm{Mg}{\mathrm{m}}^{-3}$, this gives about $11.3vol\%$ cementite and $88.7vol\%$ ferrite. Because the densities are similar, the mass and volume fractions differ only modestly. The phase-diagram values here are conventional approximations, not a claim that the exact 2018 Data Book has been recovered.

For a mixture with phase compositions $x_1,x_2$, its molar Gibbs free energy is the straight-line combination $g=(1-f)g_1(x_1)+f{g}_2(x_2)$ at overall $x=(1-f)x_1+f{x}_2$. Minimizing over phase compositions gives equal slopes and equal tangent intercepts: the common-tangent construction expresses equality of both component chemical potentials. The equilibrium curve is the lower convex envelope of the candidate phase curves. Phase fractions follow the lever rule.

Convert atomic fractions to mass fractions before using the diagram's weight-percent scale:With $M_{\mathrm{Sn}}=118.71$ and $M_{\mathrm{Bi}}=208.98\mathrm{g}\mathrm{mo}{\mathrm{l}}^{-1}$, the overall $x=0.30$ is $19.58wt\%$ Sn. At $150{}^{\circ }\mathrm{C}$, the diagram gives approximately $x_B=0.028$ and $x_L=0.555$. These are about $1.61$ and $41.47wt\%$ Sn. The lever rule givesThe microstructure has primary Bi-rich crystals surrounded by remaining liquid. The phase compositions and fractions are approximate readings of a printed phase diagram, not exact thermodynamic values. Faster cooling generally gives finer crystals, solute segregation and departure from these equilibrium compositions.

The Maxwell construction replaces a nonconvex homogeneous free-energy density by its coexistence envelope. If $U_0(M)$ excludes the source, the coexisting values $M_1,M_2$ satisfyThus one straight line is tangent at both endpoints. Equivalently,the equal-area form of the common-tangent construction. At fixed average $\overline{M}$ between the endpoints, the lever rule gives $\overline{M}=p{M}_1+(1-p)M_2$. Such a mixture has the tangent-line bulk energy, below the energy of an unstable homogeneous state.

The two phases occupy spatial domains separated by domain walls. The gradient term gives a positive wall energy, but a macroscopic interface has area of order $L^{D-1}$ rather than bulk volume $L^D$, so its cost per volume vanishes in the thermodynamic limit. For the symmetric quartic example a scalar quartic domain wall obeys $\kappa {\varphi }^{\prime \prime }=r\varphi +u{\varphi }^3$ and interpolates between $\pm M_0$ as $\varphi =M_0\tanh (x/\ell )$, with $M_0^2=|r|/u$ and $\ell =\sqrt{2\kappa /|r|}$. Multiplication of the differential equation by ${\varphi }^{\prime }$ gives the first integral $\kappa ({\varphi }^{\prime }{)}^2/2=u({\varphi }^2-M_0^2{)}^2/4$, explaining the finite positive interface cost. A uniform unconstrained system need not form both domains: phase separation is particularly relevant when the average order parameter is fixed or boundaries enforce competing phases.

Hysteresis occurs when the system follows a metastable local minimum after another minimum has become the equilibrium one. For $r<0,u>0$, the equation of state is $h=rM+u{M}^3$. The hysteresis spinodals of a scalar quartic potential follow from $r+3u{M}^2=0$:Following local minima until these limits gives different switching fields on increasing and decreasing $h$. Equilibrium instead switches at $h=0$. Actual switching can occur before a mean-field spinodal through nucleation, and depends on time scales; hysteresis is not a property of a globally minimized equilibrium potential. The second panel below distinguishes the local branches and their limiting switches.

Take $z$ positive downwards from the roof. Write $T_0=T_m-m{C}_0$, $C_B=(T_m-T_B)/m$, $\Delta T=T_0-T_B=m(C_B-C_0)>0$ and $\Delta C=C_B-C_0$. The cooled magma follows the decreasing liquidus from $(C_0,T_0)$ towards $(C_B,T_B)$; the initially superheated liquid starts at $(C_0,T_{\infty })$ above that liquidus. The solid has zero solute concentration. At each temperature in the mushy layer, a horizontal tie line joins the pure solid to the residual liquid on the liquidus. The lever rule gives the liquid fraction from the bulk concentration. Since $T_B>T_E$, this path stops before the eutectic temperature and does not cross the eutectic composition.

The porosity $\varphi$ denotes the liquid fraction, so $1-\varphi$ is the solid fraction. Equal phase mass densities remove volume-change flow; the stable density stratification suppresses convection. In the stagnant mushy-layer model, define bulk specific enthalpy and bulk solute concentration byThe arbitrary reference of specific enthalpy has been omitted. The two conservation laws in $0<z<h(t)$ areHere $\kappa =k_T/(\rho c_p)$ is the thermal diffusivity, with $k_T$ the thermal conductivity. The positive $L{\varphi }_t$ term records increased specific enthalpy on melting; during freezing it supplies latent heat. In the liquid $z>h(t)$, the heat equation and solute diffusion equation arewhere $D$ is the solutal diffusivity. Neglecting solute diffusion inside the mushy layer does not permit dropping $D{C}_{zz}$ in the liquid at this stage.

Use $T(0,t)=T_B$, liquid $T\to T_{\infty }$ and $C\to C_0$ as $z\to \infty$, and initially $h=0$, $T=T_{\infty }$, $C=C_0$ for $z>0$. These are the half-space boundary conditions appropriate before cooling reaches the bottom of the chamber. For a closed chamber of finite depth $H$, replace the far-field conditions by the specified bottom conditions, for example $T_z=C_z=0$ at an insulated impermeable floor; the half-space similarity solution then ceases to apply when the thermal penetration depth approaches $H$.

At $z=h(t)$, let $C_i$ and $T_i=T_m-m{C}_i$ be the common liquid concentration and temperature, and let ${\varphi }_i$ be the limiting porosity on the mush side. Continuity of $T,C$, the Rankine-Hugoniot condition for solute, and the interfacial conservation of energy giveThe first condition has the sign of solute rejection into the liquid. For the sharp-edge stagnant mushy-layer model with nonzero liquid solutal diffusivity, close the free-boundary problem by marginal equilibrium at a mush-liquid boundary:This prevents constitutional supercooling immediately ahead of the mushy layer. A small solid fraction jump at its edge is allowed: imposing ${\varphi }_i=1$ as well as these finite-$D$ conditions would generally overdetermine the reduced model. At the roof, $C=C_B$ follows from the liquidus, and no additional solute-flux boundary condition is needed in the diffusion-free mush.

To obtain the large-concentration similarity solution, putThe positive superheat specifies the physically intended liquid initial state. On a similarity solution, $C_i,{\varphi }_i$ are constant, so every newly incorporated level leaves the same constant $B={\varphi }_i{C}_i$. Write $C_i=C_0+\Delta C\delta$ and $B=\Delta C(\mathcal{C}+a)$. Then throughout the mushy layerFor $a,\theta =O(1)$, $\mathcal{C}\gg 1$, and $\mathcal{S}/\mathcal{C}=O(1)$, the effective heat capacity is constant to relative error $O({\mathcal{C}}^{-1})$. Thus setIntegration of the similarity solution ordinary differential equation gives the leading analytical profilesThe temperature is $T=T_0+\Delta T\theta$. In the mushy layer, the concentration and porosity are the displayed $C,\varphi$; in the liquid,These retain the liquid solutal boundary layer. For completeness, finite-$r$ values of $\delta ,a,\lambda$ are determined analytically, to the same large-$\mathcal{C}$ order, by settingand solvingThe solute jump gives ${\varphi }_i=1-b/(\mathcal{C}+\delta )$ exactly; replacing $\mathcal{C}$ by $\mathcal{C}+\delta$ on the right of the last equation retains that jump's next-order factor, but does not make the linearized thermal profiles exact at finite $\mathcal{C}$. The branch has $0\le \delta <1$, $0<\varphi \le 1$. All these profiles are leading asymptotic expressions, not exact solutions of the nonlinear finite-$\mathcal{C}$ heat equation.

For $r\to 0$ at fixed positive $\lambda$, the complementary error function asymptotic gives $K(\lambda /\sqrt{r})\sim \sqrt{\pi }\lambda /\sqrt{r}$, hence $\delta =O(r)$, $b=O(r)$, $a\to 0$, and ${\varphi }_i\to 1$. The result simplifies toIn particular, $\varphi (0,t)=C_0/C_B=\mathcal{C}/(\mathcal{C}+1)$ and $\varphi (h^{-},t)=1$. There is no finite interfacial latent heat jump in this limit: the latent heat is released continuously throughout the mushy layer. Matching the two temperature gradients givesThe printed final equation is missing the square on $\Omega$ in the exponential. The corrected exponent follows directly from differentiating $\mathrm{erf}(\Omega \eta )$ and is consistent with ${\Omega }^2=1+\mathcal{S}/\mathcal{C}$. The positive root is unique: the mush-side gradient decreases from infinity to zero with $\lambda$, whereas ${\theta }_{\infty }K(\lambda )$ increases. The zero-superheat limit is singular and is not described by a finite positive $\lambda$ in this two-region construction.

Interpret the stated transition as an upper critical miscibility temperature: cooling increases the effective $\chi$ through ${\chi }_c$. Above $T_c$, the homogeneous mixing free energy is convex throughout $0<\varphi <1$, with no two-phase common tangent. Below $T_c$, it acquires a region with $f^{\prime \prime }<0$, bordered by the spinodal. A lower straight line touches the curve at two binodal compositions ${\varphi }_{-}$ and ${\varphi }_{+}$; this common-tangent construction gives the equilibrium polymer-poor and polymer-rich phases.

The precise raw curve need not have two equal minima: subtracting an affine function of $\varphi$ changes reference chemical potentials without changing curvature or coexistence compositions. The free-energy panels above subtract the tangent at ${\varphi }_c$ from the upper-temperature curve and the common tangent from the lower-temperature curve. This makes the common tangent and the convex-versus-nonconvex distinction visible.

If the mean initial composition ${\varphi }_0$ lies inside the low-temperature spinodal region, an arbitrarily small separation into equal-volume regions with compositions ${\varphi }_0\pm \delta \varphi$ changes the mean free energy bySmall fluctuations therefore grow spontaneously: this is spinodal decomposition. Interfacial costs limit very short-wavelength fluctuations, and the polymer-poor and polymer-rich domains subsequently coarsen towards their binodal compositions.

If ${\varphi }_0$ lies just outside a spinodal branch but still inside the binodal, then $f^{\prime \prime }({\varphi }_0)>0$. Small fluctuations increase free energy, so the uniform mixture is metastable. Separation requires a sufficiently large nucleus to overcome the interfacial barrier, followed by nucleation and growth. There is no guarantee that this happens rapidly. If the initial composition is outside the binodal as well, it remains a stable uniform phase after cooling.

For a mean composition in the coexistence interval, conservation of polymer fixes the volume fraction $\alpha$ of the rich phase by the lever rule:The temperatures alone do not determine which mechanism occurs without the initial composition. Numerical free-energy curves additionally require $\chi (T)$; the plotted example uses $\chi (T)={\chi }_c{T}_c/T$ with absolute temperatures $T_c=298.15\mathrm{K}$, $T_1=303.15\mathrm{K}$ and $T_2=293.15\mathrm{K}$.

The proportions of ferrite and cementite within the two-phase pearlite microstructure. A lever rule on a weight-percent-carbon diagram gives mass fractions; converting those to volume fractions requires the phase densities. Proeutectoid phases outside pearlite must be treated separately.

A phase diagram partitions a space of thermodynamic variables into regions occupied by different equilibrium thermodynamic phases and records the phase coexistence curves between them. For a pure, one-component substance, a pressure–temperature phase diagram gives one point for each pair $(T,p)$. In a single-thermodynamic phase region both controls can vary independently. On a two-thermodynamic phase phase coexistence curve, they obey one relation; at a triple point, both are fixed. These statements assume bulk thermodynamic equilibrium, fixed composition and no additional applied fields.^[ref]

At fixed temperature and pressure, the stable bulk thermodynamic phase minimizes Gibbs free energy for a fixed amount of substance. For a pure substance this is a comparison of chemical potentials on a common normalization. Two candidate thermodynamic phases coexist where ${\mu }_{\alpha }(T,p)={\mu }_{\beta }(T,p)$ and neither is exceeded in stability by a third thermodynamic phase. Differentiating their equality gives the Clapeyron equation. Thus a phase coexistence curve is a locus of equal stability, rather than a trajectory that every heated sample must follow.^[ref]

The following original cartoon uses dimensionless positive coordinates $\theta =T/T_{\ast }$ and $\pi =p/p_{\ast }$, with arbitrary reference scales $T_{\ast },p_{\ast }$. It represents no particular substance and contains no measured data. Stipulate a triple point at $(1,1)$, a liquid-gas critical point at $(3,5)$, and these drawing rules:They specify sublimation, liquid–gas phase coexistence and melting boundaries for the picture. They are not an equation of state, do not predict latent heat or mass density, and do not supply a quantitative critical theory. In particular, the melting slope is merely an illustrative choice.

For example, at fixed $\pi =3$ the melting boundary is at $\theta =1.2$ and the liquid–gas boundary is at $\theta =2$. Heating from $(\theta ,\pi )=(1.6,3)$ to $(3.6,3)$ therefore starts in liquid, crosses phase coexistence at $(2,3)$, and ends in gas. In an equilibrium conversion at that crossing, added heat can change the phase fraction at fixed temperature through latent heat. The pressure–temperature point alone does not specify how much of each thermodynamic phase is present: for that one needs an additional amount or volume constraint.

Now connect exactly the same endpoints by raising $\pi$ from $3$ to $6$ at $\theta =1.6$, moving to $\theta =3.6$ at $\pi =6$, then lowering $\pi$ to $3$. The first leg stays on the liquid side because ${\theta }_{\mathrm{melt}}$ ranges only from $1.2$ to $1.5$ and ${\pi }_{\mathrm{vap}}(1.6)=2.2<3$. The second leg lies above the entire liquid–gas boundary, whose largest drawn pressure coordinate is $5$; the third lies beyond its largest temperature coordinate, $3$. No leg crosses a first-order phase transition boundary. The middle leg passes through a supercritical fluid region, with $\theta >3$ and $\pi >5$, and the final leg returns to a gaslike state continuously.

Avoiding a first-order phase transition does not mean that no heat or work is exchanged. Along the detour, mass density, enthalpy and heat capacity may change substantially but continuously. The liquid-gas critical point itself has singular behavior, so the detour goes around it rather than through it. This connected fluid region is the striking lesson of a phase diagram: a familiar change from liquid to gas need not involve boiling across a sharp boundary.

An equilibrium phase diagram also does not predict how rapidly a conversion occurs. Metastability and a barrier described by classical nucleation theory can delay the observed phase transition. Nor should a binary-composition phase diagram be read as the same picture: its coexistence regions and lever rule encode composition and phase fractions, and can occupy an area even though pure-substance two-thermodynamic phase coexistence occupies a curve in the pressure–temperature plane.

A ternary liquid-liquid tie line joins the compositions of two coexisting liquid phases in a three-component mixture at a specified temperature and pressure. IUPAC defines a tie line by its coexisting equilibrium endpoints.^[ref] Each composition is a vector $\mathbf{x}=(x_A,x_B,x_C)$ of mole fractions satisfying $x_A+x_B+x_C=1$. Only two coordinates are independent; a triangular composition diagram displays this constraint.

If $\lambda$ is the mole-based phase fraction in phase $\beta$, conserving every component givesThis is the lever rule in vector form. Wherever $x_i^{\beta }\ne x_i^{\alpha }$, each component must give the same valueA component identical at both endpoints cannot determine $\lambda$, but its overall fraction must equal that common endpoint value.

For an original material-balance example, stipulate endpoint compositions $(0.65,0.25,0.10)$ and $(0.15,0.35,0.50)$. With $\lambda =0.30$, the overall composition is $(0.50,0.28,0.22)$. All three component calculations give $0.30$. By contrast, $(0.50,0.29,0.21)$ still sums to one, but gives apparent phase fractions $0.30$, $0.40$ and $0.275$. Under the stipulated exact endpoints, it does not lie on this tie line. A ternary tie-line consistency residual records the failure of the vector balance; experimental use must account for composition uncertainties.

These chosen endpoints illustrate conservation, not a claim that an actual mixture has these equilibrium compositions. Establish endpoints from equilibrium measurements or a stable Gibbs free energy model. Moving along one liquid-liquid tie line changes phase amounts while preserving its endpoint compositions. Moving elsewhere in the two-phase region can select a different pair of endpoints; all tie lines need not be parallel. Finally, mole-based and mass-based diagrams require consistent fractions: a mole-based $\lambda$ is not automatically a volume or mass fraction.

A ternary tie-line consistency residual quantifies how far an overall three-component composition is from the mass balance predicted by specified endpoints of a ternary liquid-liquid tie line. It is a geometric consistency check on a proposed two-phase decomposition. A thermodynamic tie line connects coexisting equilibrium compositions; the calculation below checks the lever rule for those endpoints, rather than independently proving that they are equilibrium phases.^[ref]

Use mole fraction vectors ${\mathbf{x}}^{\alpha },{\mathbf{x}}^{\beta }$ for the endpoint liquids and $\mathbf{z}$ for the overall composition, all normalized to sum to one. Put $\mathbf{d}={\mathbf{x}}^{\beta }-{\mathbf{x}}^{\alpha }$. For a proposed mole-based phase fraction $\lambda$, defineExact mass balance requires every component of $\mathbf{r}$ to vanish. Closure gives ${\sum }_i{r}_i=0$ automatically, so this residual has only two independent components. A zero sum alone does not imply that the component balances hold.

When the phase fraction is unknown and the endpoints are distinct, an unweighted least squares tie-line phase-fraction fit minimizes the squared Euclidean norm of $\mathbf{r}$. Differentiating givesThis is an orthogonal projection onto the line through the endpoints. A physically admissible phase fraction also lies in $[0,1]$; if the unconstrained fit lies outside that interval, the closest admissible composition is an endpoint of the line segment. Coincident endpoints do not determine a phase fraction through this formula.

For the hypothetical endpoints ${\mathbf{x}}^{\alpha }=(0.65,0.25,0.10)$ and ${\mathbf{x}}^{\beta }=(0.15,0.35,0.50)$, the composition $(0.50,0.28,0.22)$ gives $\hat{\lambda }=0.30$ and zero residual. Changing the overall composition to $\mathbf{z}=(0.50,0.29,0.21)$ preserves closure but givesNo adjustment of a single phase fraction can eliminate that discrepancy under the stipulated exact endpoints. For experimental use, its significance depends on measurement uncertainty in both the overall composition and endpoint compositions. Unweighted distance is a chosen metric, not an automatic statistical rejection threshold; correlated composition errors require their covariance matrix on the independent composition coordinates. Even a tiny residual establishes only compatibility with this mass balance, not equality of chemical potentials or stability of the proposed liquid-liquid equilibrium.