Phase transition

A phase transition is a change between equilibrium phases associated with nonanalytic thermodynamic behavior in an appropriate infinite-system limit. Melting, liquid–vapor coexistence and magnetic ordering illustrate different kinds. A phase diagram specifies the control parameters and the boundaries between phases.

At a first-order phase transition, a first derivative of the relevant thermodynamic potential changes discontinuously; thermal examples can have latent heat and phase coexistence. At a continuous phase transition, an order parameter can develop continuously while response functions and a correlation length become singular. Real finite systems show rounded signatures, so measurements usually compare heat capacity, density, structural scattering or an order parameter across a controlled scan. Hysteresis is evidence of delayed conversion or metastability, rather than the definition of an equilibrium transition.

Formation of a crystal from a disordered phase. In a cooling white dwarf, crystallization of the ionic interior releases latent heat and can redistribute chemical species, affecting the relation between luminosity and white-dwarf cooling age.

Purification by dissolving a crystalline chemical substance and forming new crystals under conditions that leave impurities in the mother liquor or permit their prior removal.

Water incorporated into the structure of a crystalline hydrate. Loss on drying can test hydration or excess moisture.

A structural phase change requiring substantial rearrangement of near-neighbor bonding or connectivity. Its activation barriers can make equilibrium transitions kinetically sluggish. It is distinguished from a cooperative displacive transformation, rather than defined solely by the presence of a different final symmetry.

A two-dimensional phase with quasi-long-range sixfold bond-orientational order but short-range translational order. A cell model of independent particle cages does not capture its full physics.

A cooperative change of atomic positions and lattice shape without the long-range compositional diffusion required by a diffusional transformation. Tetragonal-to-monoclinic transformation in zirconia is a nonmetallic example.

vitrification produces a noncrystalline glassy state. Rapid freezing of thin aqueous specimens is used to preserve hydrated biological structures for cryo-electron microscopy; vitrification does not prevent all subsequent radiation damage.

A change between a material behaving as an electrical conductor and as an electrical insulator. The distinction concerns the limiting electronic response as temperature tends to zero; finite thermally activated electrical conductivity alone does not establish a metallic state. A Peierls transition opens a band gap through a change in the crystal structure.

The approximate donor metal-insulator threshold is often written $n_c^{1/3}{a}_B^{\ast }\simeq 0.25$. It estimates when overlap and screening destroy isolated donor localization. The numerical coefficient is empirical and not a universal exact result; disorder, compensation and anisotropy can shift the threshold.^[ref]

Liquefaction converts a gas into a liquid. For a pure substance below its liquid-gas critical point, compression can cross the liquid–vapor coexistence boundary; cooling can also bring a vapor to its saturation condition. Above the critical temperature, pressure alone does not produce a distinct liquid–vapor transition.

A practical cycle removes compression heat and cools the gas before collecting the liquid. The Joule-Thomson effect can provide cooling during expansion in the appropriate regime, but its sign depends on the gas and operating conditions. The collected liquid releases latent heat as it forms, so sustained production requires continued heat removal. These requirements explain why a high-pressure vessel alone is not a general liquefier.

Condensation is conversion of a vapor into a liquid. Cooling vapor-bearing air below its dew point is a familiar example: droplets form on a cold surface as the saturation vapor pressure falls. In a mixture, the relevant comparison uses the condensable component's partial pressure, rather than the mixture's total pressure alone.

Creating a new droplet costs interfacial free energy, while conversion to the stable liquid lowers bulk free energy. A nucleation barrier can therefore permit supersaturated vapor before droplets appear. A pre-existing surface can lower that barrier through heterogeneous nucleation. Condensation also releases latent heat, so a cold plate or condenser must remove heat as liquid accumulates. At vapor-liquid equilibrium, evaporation and condensation continue microscopically with equal average opposing rates.

Melting is a solid-to-liquid phase transition that absorbs latent heat. It can be driven by heating, changing phase pressures, or adding solute that causes freezing-point depression. The ice layer between freshwater and cold brine illustrates melting into a cold liquid through dilution and a composition-dependent liquidus.

Frederick Lindemann's heuristic associates melting with vibrational displacement reaching a specified fraction of the nearest-neighbor distance $d$. The displacement convention must be stated: one-coordinate variance and full three-dimensional variance differ by a factor of three. With the high-temperature Einstein mean-square displacement, the displayed convention gives $T_m=c_L^2{d}^{2}m{k}_B{T}_E^2/{\hslash }^2$. Neither $c_L$ nor the independent-oscillator approximation is universal.

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.

A morphological instability amplifies shape perturbations of a solidification interface. Protrusions may receive a larger diffusive supply or encounter larger undercooling, while curvature-induced melting-temperature depression suppresses fine corrugations. Solute rejection can produce constitutional supercooling, destabilizing a planar front and leading to cells or crystal dendrites.

A quantum phase transition is a change of the ground state as a nonthermal control parameter is varied at zero temperature. Pressure, interaction strength or an applied magnetic field can tune the competing contributions to the Hamiltonian. The transition is driven by changes in the quantum ground state, whereas a thermal phase transition is driven by thermal occupation and entropy.

The Transverse-field Ising model illustrates the competition between aligned-spin order and a field favoring a different spin direction. A continuous transition has a quantum critical point, with a closing excitation gap and growing correlation scales; a quantum phase transition can also be first order. Experiments operate at finite temperature, where the nearby quantum-critical regime can reveal the influence of the zero-temperature transition without placing the sample exactly at zero.

A direct transition from a solid phase to a gaseous phase. Heated interplanetary dust or a comet can lose material through this process, changing its size and radiation-pressure coefficient or destroying it before gravitational or drag-driven evolution is complete.

For a locally linear ice temperature with positive gradient $G$ into the solid, a corrugated sublimation front receives a perturbation in heat flux proportional to its horizontal wavenumber $\alpha$. The Gibbs-Thomson effect suppresses short waves, giving the displayed quasi-static growth rate. It requires $V/(\kappa \alpha )\ll 1$ and $|\sigma |/(\kappa {\alpha }^2)\ll 1$, as well as a perturbation depth short enough for the linear background approximation. Unstable modes have $0<\alpha <\sqrt{G/\Gamma }$.

For a sublimating surface with exponentially absorbed volumetric heating, use a frame moving into the solid at speed $V$. Its steady heat equation is $k{T}^{\prime \prime }+\rho c_{p}V{T}^{\prime }+q_0{e}^{-\lambda z}=0$. The surface Stefan condition is $k{T}^{\prime }(0)=\rho LV$. Integrating over the half-space gives the displayed energy-limited speed. The surface gradient is positive, but the far field is colder, so the temperature has a subsurface maximum where melting can begin.

An irradiated grain loses solid material by sublimation. Its lifetime depends strongly on temperature and composition. In a planetary dust tail, a short lifetime can truncate the distribution well before a relative orbital wrap.

A spherical black grain of radius $a$ absorbs luminosity $L$ through projected area $\pi a^2$ and emits over $4\pi a^2$. Radiative balance at sublimation temperature gives $r_{\mathrm{sub}}=[L/(16\pi {\sigma }_{\mathrm{SB}}{T}_{\mathrm{sub}}^4){]}^{1/2}$. Grain size cancels only under the stated unit-efficiency approximation; shielding and wavelength-dependent emissivity change the result.

At fixed irradiation, heating per grain is independent of temperature while cooling is proportional to $T^4$. With positive heat capacity and intact grains, a positive temperature perturbation increases net cooling, and a negative one increases net heating. Fixed dust properties and sufficient dust-gas thermal coupling are necessary assumptions.

A thermal-stability argument that holds dust properties fixed can fail near a sublimation front. A rise in temperature can destroy grains, changing the absorption and emission efficiencies, the dust mass and the optical depth through which radiation reaches neighboring material. The heating and cooling laws then change along with the temperature.

Write the net heating schematically as $Q(T,a,{\rho }_d)$, where $a$ is grain size and ${\rho }_d$ is dust density. The response along an evolving state includes $Q_{a}da/dT$ and $Q_{{\rho }_d}d{\rho }_d/dT$, not only the fixed-grain derivative $Q_T$. These additional terms can reinforce or oppose the perturbation. The sign depends on geometry, radiation spectrum and dust–gas coupling, so the fixed-property result in thermal stability of externally heated blackbody dust does not by itself establish the stability of a sublimation front.

Phase coexistence means that distinct equilibrium phases can persist together under common external conditions. For exchanging material, the phases have equal temperature and equal chemical potentials of each exchanging species. A flat unstressed interface also requires equal pressure; curvature changes the mechanical balance through capillary pressure.

A sealed pure fluid below its liquid-gas critical point can contain both liquid and vapor. Changing the total amount or volume can change their proportions without changing their equilibrium densities at fixed temperature. In a binary mixture, the two phases can instead have different compositions. The common-tangent construction determines their coexistence compositions by enforcing the appropriate chemical and mechanical equalities. Coexistence concerns competing phases with matching intensive conditions, rather than equality of their total extensive free energies for arbitrary sample amounts.

If two equilibrium phases have continuous entropy and volume but jumps in second derivatives of Gibbs free energy, differentiate their entropy equality along the transition line. Since $dS=(C_P/T)dT-V{\alpha }_{T}dP$, one obtains the title slope, for nonzero $\Delta C_P$. Before imposing equal volume, the numerator is $T\Delta (V{\alpha }_T)$. Equality of Gibbs free energies with equal entropy implies equal volume along a differentiable coexistence curve on which pressure varies. A constant-pressure curve or zero numerator and denominator needs separate analysis. This entropy-continuity condition is one Ehrenfest relation; volume continuity gives another independent relation.

A system can split into macroscopic regions with distinct local order parameters, densities or compositions. In a short-range system at phase coexistence, regions of two phases with means $M_1,M_2$ and volume fractions $q,1-q$ have spatial mean $M=q{M}_1+(1-q)M_2$. Their interface contribution is subextensive, so their thermodynamic free-energy density is the corresponding convex combination of the phase densities. This can lie below the homogeneous-branch Landau free energy at the same $M$. The equilibrium constrained order-parameter free energy is consequently convexified, with a straight coexistence segment described by the Maxwell construction. A nonconvex local potential remains useful for homogeneous branches, metastability and interfaces, but must not be identified with the full equilibrium constrained density throughout a coexistence interval.

Formation of finite-scale composition domains when complete macroscopic separation is frustrated, for example by the covalent connection of incompatible blocks in a diblock copolymer. Interfacial cost and chain entropy jointly select the domain scale.

Alternating sheet-like domains of the components of a microphase-separated material. In diblock systems the two layer thicknesses can be unequal and reflect unequal block fractions. Confinement, surface wetting and kinetic trapping can produce layered films outside the thermodynamic equilibrium bulk lamellar region.

A microdomain pattern of approximately parallel cylinders arranged on a two-dimensional hexagonal lattice in the other block's matrix. It is conventionally labelled H in many diblock phase diagrams. Cylinder orientation and defects are additional properties beyond the local morphology.

An ordered morphology in which a minority block forms approximately spherical domains in a continuous majority-block matrix. The lattice packing and phase stability depend on segregation strength, composition and chain statistics. The label S in a phase diagram denotes a morphology, not a spherical shape of the entire specimen.

The transition between a compositionally disordered state and an ordered microdomain state as effective segregation strength increases. The parameter $\chi N$ combines unlike-segment interaction preference and chain length; its transition value depends on composition and model assumptions. A bulk thermodynamic equilibrium boundary is not by itself an evaporation or vitrification kinetic model.

A domain structure resembling lamellae pierced by an ordered array of perforations. It is distinct from an unperforated lamellar phase and from a double gyroid.

A bicontinuous domain morphology containing two interpenetrating, nonintersecting networks of one component within the other. In diblock copolymers it can appear between lamellar and cylindrical morphologies in part of the phase diagram.

Separation of a biomolecular mixture into compositionally distinct phases. Concentration dependence, partitioning and reversibility should be tested; a fluorescent punctum or recovery after bleaching alone does not establish the mechanism.

A pure thermodynamic phase is an extremal equilibrium Gibbs state rather than a probabilistic mixture of distinct macroscopic phases. On an ordered Ising branch, taking the thermodynamic limit before removing a selecting conjugate field gives a nonzero magnetization. A symmetric mixture can instead have zero mean but a nondecaying two-point contribution. The connected correlation function and correlation length describing ordinary critical fluctuations should be evaluated in a chosen pure phase when this distinction matters.

For a bulk free-energy density $f(\varphi )$, two compositions coexist across a flat interface whenThe first condition equates the chemical potentials, and the second equates the pressure. Equivalently the same straight line of slope $\mu$ is tangent to the graph of $f$ at both compositions. A stable coexistence pair uses a supporting tangent, so the resulting mixture lowers the bulk free energy.

Adding $d\varphi$ to a free-energy density adds a constant at fixed total compositional order parameter. In the common-tangent construction for phase coexistence, it shifts the tangent slope by $d$ while preserving its points of contact. Thus coexistence compositions are unchanged, whereas their chemical potential shifts. This does not assert unchanged equilibrium composition at a fixed externally imposed chemical potential.

Vapor-liquid equilibrium is coexistence of a liquid and its vapor with no net macroscopic transfer of matter between them. The two phases have equal temperature, equal pressure for a flat interface without external stress, and equal chemical potential for each exchanging species.

For a pure substance, fixing the temperature below its liquid-gas critical point selects the saturation vapor pressure. Molecules still cross the interface in both directions; equilibrium means equal average opposing rates, rather than halted molecular motion. In a mixture, the vapor and liquid generally have different compositions, while each component separately satisfies the chemical-potential equality. This distinction underlies separation by evaporation and condensation and explains why equal total pressure alone is insufficient to determine phase compositions.

At a continuous phase transition, the equilibrium phases meet without a discontinuous change in a first derivative of the appropriate thermodynamic potential. A thermal continuous transition therefore has no latent heat, although heat capacity or another response can be singular.

An ordinary critical transition develops fluctuations over an increasingly large correlation length. For magnetic ordering, the magnetization can emerge continuously while the magnetic susceptibility grows sharply. Critical exponents describe these changes, and universality explains why microscopically different systems can share them. Finite size, finite measurement time and imperfect tuning round the ideal singularity. The description must distinguish such critical behavior from a weakly first-order transition whose small discontinuity happens to be unresolved.

Vaporization changes a liquid into a gas. It includes evaporation at a surface and boiling within the liquid. Below the liquid-gas critical point, equilibrium conversion along the liquid-vapour phase coexistence curve involves latent heat; the liquid and vapour have equal chemical potential there.

The molar enthalpy difference between vapor and liquid at specified conditions, evaluated on coexistence when it is a latent heat. Treating it as constant and treating the vapor as ideal gives $\ln (P_2/P_1)=(\Delta H_{\mathrm{vap}}/R)(1/T_1-1/T_2)$.

Evaporation transfers molecules from a liquid surface into the surrounding vapour. It can occur below the boiling temperature, and competes with condensation from the vapour. Its net rate depends on the surrounding vapor pressure and transport conditions. Removing latent heat through evaporation can cool the remaining liquid.

Nonuniform accumulation of suspended material toward the edge of a drying drop, commonly when a pinned contact line and nonuniform evaporation drive outward liquid flow. Contact-line motion, solvent choice, drying conditions and ink formulation can alter or suppress the resulting deposit.

Boiling is vaporization through the formation and growth of vapor bubbles within a liquid. It differs from surface evaporation, which can occur without bubbles in the bulk. At equilibrium, the boiling point of a pure liquid is set by equality of its saturation vapor pressure and the external pressure.

A real bubble must also overcome local hydrostatic pressure and the capillary pressure of its curved surface. Creating the interface costs energy, giving a nucleation barrier; a smooth clean vessel can therefore permit superheating. Surface cavities and boiling chips supply sites where bubbles form more readily. The observed onset depends on these sites and heating conditions, while the equilibrium boiling point remains a property specified at the chosen pressure.

At a specified external pressure, the equilibrium temperature at which a pure liquid's saturation vapor pressure equals that external pressure. Bubble nucleation, hydrostatic head and capillary pressure can affect the observed onset of boiling without redefining the equilibrium property.

Raising a solvent's boiling point at fixed external pressure by a dissolved nonvolatile solute, under conditions where the solvent vapour pressure is reduced. The simple rule does not apply unchanged to every mixture of volatile components.

A limiting heat flux associated with a transition to a less effective boiling heat-transfer regime under specified conditions. Its value depends on fluid properties, pressure, flow, heating and geometry; a single number cannot be transferred indiscriminately between different flow passages.

A transition from effective nucleate boiling toward impaired surface wetting and substantially poorer heat removal in the relevant boiling regime. It is a concern when a heated fuel surface can become much hotter at an otherwise similar imposed heat load.

The ratio of the heat flux needed to reach departure from nucleate boiling to the actual local heat flux. Greater values indicate more margin under the model and correlation used.^[ref]

The minimum local departure from nucleate boiling ratio over the specified core region or assessment. It depends on local heat loading and coolant conditions, not only on average core power.

A boiling chip is a small solid piece with cavities or a porous surface that supplies sites for heterogeneous nucleation of vapor bubbles in a heated liquid. Gas trapped in a cavity can help an incipient bubble survive the capillary pressure that would collapse a sufficiently small isolated bubble.

Many active sites encourage repeated bubble release, reducing the large, irregular boiling events associated with delayed nucleation and superheating. The chip changes the route by which boiling begins; it does not materially redefine the liquid's equilibrium boiling point. Its action is therefore understood through interface formation and bubble growth, rather than through a chemical conversion of the solvent.