![Phase change - en](https://upload.wikimedia.org/wikipedia/commons/0/0b/Phase_change_-_en.svg)
In
chemistry,
thermodynamics
Thermodynamics is a branch of physics that deals with heat, work, and temperature, and their relation to energy, entropy, and the physical properties of matter and radiation. The behavior of these quantities is governed by the four laws of th ...
, and other related fields, a phase transition (or phase change) is the
physical process
Physical changes are changes affecting the form of a chemical substance, but not its chemical composition. Physical changes are used to separate mixtures into their component compounds, but can not usually be used to separate compounds into chem ...
of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic
states of matter
In physics, a state of matter is one of the distinct forms in which matter can exist. Four states of matter are observable in everyday life: solid, liquid, gas, and plasma. Many intermediate states are known to exist, such as liquid crystal, ...
:
solid
Solid is one of the four fundamental states of matter (the others being liquid, gas, and plasma). The molecules in a solid are closely packed together and contain the least amount of kinetic energy. A solid is characterized by structural ...
,
liquid, and
gas
Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma).
A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...
, and in rare cases,
plasma. A phase of a
thermodynamic system
A thermodynamic system is a body of matter and/or radiation, confined in space by walls, with defined permeabilities, which separate it from its surroundings. The surroundings may include other thermodynamic systems, or physical systems that are ...
and the states of matter have uniform
physical properties. During a phase transition of a given medium, certain properties of the medium change as a result of the change of external conditions, such as
temperature
Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measurement, measured with a thermometer.
Thermometers are calibrated in various Conversion of units of temperature, temp ...
or
pressure
Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country and e ...
. This can be a discontinuous change; for example, a liquid may become gas upon heating to its
boiling point, resulting in an abrupt change in volume. The identification of the external conditions at which a transformation occurs defines the phase transition point.
Types of phase transition
![Phase-diag2](https://upload.wikimedia.org/wikipedia/commons/3/34/Phase-diag2.svg)
At the phase transition point for a substance, for instance the
boiling point, the two phases involved - liquid and
vapor
In physics, a vapor (American English) or vapour (British English and Canadian English; see spelling differences) is a substance in the gas phase at a temperature lower than its critical temperature,R. H. Petrucci, W. S. Harwood, and F. G. Her ...
, have identical free energies and therefore are equally likely to exist. Below the boiling point, the liquid is the more stable state of the two, whereas above the boiling point the gaseous form is the more stable.
It is sometimes possible to change the state of a system
diabatic
One of the guiding principles in modern chemical dynamics and spectroscopy is that the motion of the nuclei in a molecule is slow compared to that of its electrons. This is justified by the large disparity between the mass of an electron and th ...
ally (as opposed to
adiabatically) in such a way that it can be brought past a phase transition point without undergoing a phase transition. The resulting state is
metastable
In chemistry and physics, metastability denotes an intermediate energetic state within a dynamical system other than the system's state of least energy.
A ball resting in a hollow on a slope is a simple example of metastability. If the ball i ...
, i.e., less stable than the phase to which the transition would have occurred, but not unstable either. This occurs in
superheating,
supercooling
Supercooling, also known as undercooling, is the process of lowering the temperature of a liquid or a gas below its melting point without it becoming a solid. It achieves this in the absence of a seed crystal or nucleus around which a crystal ...
, and
supersaturation, for example.
Common transitions between the solid, liquid, and gaseous phases of a single component, due to the effects of temperature and/or
pressure
Pressure (symbol: ''p'' or ''P'') is the force applied perpendicular to the surface of an object per unit area over which that force is distributed. Gauge pressure (also spelled ''gage'' pressure)The preferred spelling varies by country and e ...
are identified in the following table:
![Argon ice 1](https://upload.wikimedia.org/wikipedia/commons/0/0d/Argon_ice_1.jpg)
Other phase changes include:
* A
eutectic transformation, in which a two-component single-phase liquid is cooled and transforms into two solid phases. The same process, but beginning with a solid instead of a liquid is called a
eutectoid
A eutectic system or eutectic mixture ( ) is a homogeneous mixture that has a melting point lower than those of the constituents. The lowest possible melting point over all of the mixing ratios of the constituents is called the ''eutectic tempe ...
transformation.
* A
metastable
In chemistry and physics, metastability denotes an intermediate energetic state within a dynamical system other than the system's state of least energy.
A ball resting in a hollow on a slope is a simple example of metastability. If the ball i ...
to equilibrium phase transformation. A metastable polymorph which forms rapidly due to lower surface energy will transform to an equilibrium phase given sufficient thermal input to overcome an energetic barrier.
* A
peritectic
A eutectic system or eutectic mixture ( ) is a homogeneous mixture that has a melting point lower than those of the constituents. The lowest possible melting point over all of the mixing ratios of the constituents is called the ''eutectic tempe ...
transformation, in which a two-component single-phase solid is heated and transforms into a solid phase and a liquid phase.
* A
spinodal decomposition
Spinodal decomposition is a mechanism by which a single thermodynamic phase spontaneously separates into two phases (without nucleation). Decomposition occurs when there is no thermodynamic barrier to phase separation. As a result, phase separatio ...
, in which a single phase is cooled and separates into two different compositions of that same phase.
* Transition to a
mesophase In chemistry and chemical physics, a mesophase is a state of matter intermediate between liquid and solid. Gelatin is a common example of a partially ordered structure in a mesophase. Further, biological structures such as the lipid bilayers of cell ...
between solid and liquid, such as one of the "
liquid crystal" phases.
* The transition between the
ferromagnetic and
paramagnetic
Paramagnetism is a form of magnetism whereby some materials are weakly attracted by an externally applied magnetic field, and form internal, induced magnetic fields in the direction of the applied magnetic field. In contrast with this behavior, ...
phases of
magnet
A magnet is a material or object that produces a magnetic field. This magnetic field is invisible but is responsible for the most notable property of a magnet: a force that pulls on other ferromagnetic materials, such as iron, steel, nicke ...
ic materials at the
Curie point
In physics and materials science, the Curie temperature (''T''C), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can (in most cases) be replaced by induced magnetism. The Cur ...
.
* The transition between differently ordered,
commensurate or
incommensurate, magnetic structures, such as in cerium
antimonide Antimonides (sometimes called stibnides) are compounds of antimony with more electropositive elements. The antimonide ion is Sb3−.
Reduction of antimony by alkali metals or by other methods leads to alkali metal antimonides of various types. K ...
.
* The
martensitic transformation
A diffusionless transformation is a phase change that occurs without the long-range diffusion of atoms but rather by some form of cooperative, homogenous movement of many atoms that results in a change in the crystal structure. These movements a ...
which occurs as one of the many phase transformations in carbon steel and stands as a model for
displacive phase transformations.
* Changes in the
crystallographic
Crystallography is the experimental science of determining the arrangement of atoms in crystalline solids. Crystallography is a fundamental subject in the fields of materials science and solid-state physics ( condensed matter physics). The w ...
structure such as between
ferrite and
austenite
Austenite, also known as gamma-phase iron (γ-Fe), is a metallic, non-magnetic allotrope of iron or a solid solution of iron with an alloying element. In plain-carbon steel, austenite exists above the critical eutectoid temperature of 1000 K ...
of iron.
* Order-disorder transitions such as in alpha-
titanium aluminide
Titanium aluminide (chemical formula TiAl), commonly gamma titanium, is an intermetallic chemical compound. It is lightweight and resistant to oxidation and heat, but has low ductility. The density of γ-TiAl is about 4.0 g/cm3. It finds use in s ...
s.
* The dependence of the
adsorption
Adsorption is the adhesion of atoms, ions or molecules from a gas, liquid or dissolved solid to a surface. This process creates a film of the ''adsorbate'' on the surface of the ''adsorbent''. This process differs from absorption, in which ...
geometry on coverage and temperature, such as for
hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic ...
on iron (110).
* The emergence of
superconductivity in certain metals and ceramics when cooled below a critical temperature.
* The transition between different molecular structures (
polymorphs,
allotropes
Allotropy or allotropism () is the property of some chemical elements to exist in two or more different forms, in the same physical state, known as allotropes of the elements. Allotropes are different structural modifications of an element: th ...
or
), especially of solids, such as between an
amorphous structure and a
crystal
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macro ...
structure, between two different crystal structures, or between two amorphous structures.
* Quantum condensation of
boson
In particle physics, a boson ( ) is a subatomic particle whose spin quantum number has an integer value (0,1,2 ...). Bosons form one of the two fundamental classes of subatomic particle, the other being fermions, which have odd half-integer spi ...
ic fluids (
Bose–Einstein condensation Bose–Einstein may refer to:
* Bose–Einstein condensate
** Bose–Einstein condensation (network theory)
* Bose–Einstein correlations
* Bose–Einstein statistics
In quantum statistics, Bose–Einstein statistics (B–E statistics) describe ...
). The
superfluid
Superfluidity is the characteristic property of a fluid with zero viscosity which therefore flows without any loss of kinetic energy. When stirred, a superfluid forms vortices that continue to rotate indefinitely. Superfluidity occurs in two ...
transition in liquid
helium
Helium (from el, ἥλιος, helios, lit=sun) is a chemical element with the symbol He and atomic number 2. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas and the first in the noble gas group in the periodic table. ...
is an example of this.
* The
breaking of symmetries in the laws of physics during the early history of the universe as its temperature cooled.
*
Isotope fractionation
Isotope fractionation describes fractionation processes that affect the relative abundance of isotopes, phenomena which are taken advantage of in isotope geochemistry and other fields. Normally, the focus is on stable isotopes of the same element. ...
occurs during a phase transition, the ratio of light to heavy isotopes in the involved molecules changes. When
water vapor
(99.9839 °C)
, -
, Boiling point
,
, -
, specific gas constant
, 461.5 J/( kg·K)
, -
, Heat of vaporization
, 2.27 MJ/kg
, -
, Heat capacity
, 1.864 kJ/(kg·K)
Water vapor, water vapour or aqueous vapor is the gaseous p ...
condenses (an
equilibrium fractionation
Equilibrium isotope fractionation is the partial separation of isotopes between two or more substances in chemical equilibrium. Equilibrium fractionation is strongest at low temperatures, and (along with kinetic isotope effects) forms the basis of ...
), the heavier water isotopes (
18O and
2H) become enriched in the liquid phase while the lighter isotopes (
16O and
1H) tend toward the vapor phase.
Phase transitions occur when the
thermodynamic free energy
The thermodynamic free energy is a concept useful in the thermodynamics of chemical or thermal processes in engineering and science. The change in the free energy is the maximum amount of work that a thermodynamic system can perform in a process ...
of a system is
non-analytic for some choice of thermodynamic variables (cf.
phases). This condition generally stems from the interactions of a large number of particles in a system, and does not appear in systems that are small. Phase transitions can occur for non-thermodynamic systems, where temperature is not a parameter. Examples include: quantum phase transitions, dynamic phase transitions, and topological (structural) phase transitions. In these types of systems other parameters take the place of temperature. For instance, connection probability replaces temperature for percolating networks.
Classifications
Ehrenfest classification
Paul Ehrenfest
Paul Ehrenfest (18 January 1880 – 25 September 1933) was an Austrian theoretical physicist, who made major contributions to the field of statistical mechanics and its relations with quantum mechanics, including the theory of phase transition a ...
classified phase transitions based on the behavior of the
thermodynamic free energy
The thermodynamic free energy is a concept useful in the thermodynamics of chemical or thermal processes in engineering and science. The change in the free energy is the maximum amount of work that a thermodynamic system can perform in a process ...
as a function of other thermodynamic variables.
Under this scheme, phase transitions were labeled by the lowest derivative of the free energy that is discontinuous at the transition. ''First-order phase transitions'' exhibit a discontinuity in the first derivative of the free energy with respect to some thermodynamic variable.
The various solid/liquid/gas transitions are classified as first-order transitions because they involve a discontinuous change in density, which is the (inverse of the) first derivative of the free energy with respect to pressure. ''Second-order phase transitions'' are continuous in the first derivative (the
order parameter
In chemistry, thermodynamics, and other related fields, a phase transition (or phase change) is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states of ...
, which is the first derivative of the free energy with respect to the external field, is continuous across the transition) but exhibit discontinuity in a second derivative of the free energy.
[ These include the ferromagnetic phase transition in materials such as iron, where the magnetization, which is the first derivative of the free energy with respect to the applied magnetic field strength, increases continuously from zero as the temperature is lowered below the ]Curie temperature
In physics and materials science, the Curie temperature (''T''C), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can (in most cases) be replaced by induced magnetism. The Cur ...
. The magnetic susceptibility, the second derivative of the free energy with the field, changes discontinuously. Under the Ehrenfest classification scheme, there could in principle be third, fourth, and higher-order phase transitions.
The Ehrenfest classification implicitly allows for continuous phase transformations, where the bonding character of a material changes, but there is no discontinuity in any free energy derivative. An example of this occurs at the supercritical liquid–gas boundaries.
The first example of a phase transition which did not fit into the Ehrenfest classification was the exact solution of the Ising model
The Ising model () (or Lenz-Ising model or Ising-Lenz model), named after the physicists Ernst Ising and Wilhelm Lenz, is a mathematical model of ferromagnetism in statistical mechanics. The model consists of discrete variables that represent ...
, discovered in 1944 by Lars Onsager
Lars Onsager (November 27, 1903 – October 5, 1976) was a Norwegian-born American physical chemist and theoretical physicist. He held the Gibbs Professorship of Theoretical Chemistry at Yale University. He was awarded the Nobel Prize in C ...
. The exact specific heat differed from the earlier mean-field approximations, which had predicted that it has a simple discontinuity at critical temperature. Instead, the exact specific heat had a logarithmic divergence at the critical temperature. In the following decades, the Ehrenfest classification was replaced by a simplified classification scheme that is able to incorporate such transitions.
Modern classifications
In the modern classification scheme, phase transitions are divided into two broad categories, named similarly to the Ehrenfest classes:
First-order phase transitions are those that involve a latent heat
Latent heat (also known as latent energy or heat of transformation) is energy released or absorbed, by a body or a thermodynamic system, during a constant-temperature process — usually a first-order phase transition.
Latent heat can be underst ...
. During such a transition, a system either absorbs or releases a fixed (and typically large) amount of energy per volume. During this process, the temperature of the system will stay constant as heat is added: the system is in a "mixed-phase regime" in which some parts of the system have completed the transition and others have not.
Familiar examples are the melting of ice or the boiling of water (the water does not instantly turn into vapor
In physics, a vapor (American English) or vapour (British English and Canadian English; see spelling differences) is a substance in the gas phase at a temperature lower than its critical temperature,R. H. Petrucci, W. S. Harwood, and F. G. Her ...
, but forms a turbulent
In fluid dynamics, turbulence or turbulent flow is fluid motion characterized by chaotic changes in pressure and flow velocity. It is in contrast to a laminar flow, which occurs when a fluid flows in parallel layers, with no disruption between ...
mixture of liquid water and vapor bubbles). Yoseph Imry
Yoseph Imry (Hebrew: יוסף אמרי; born 23 February 1939 – 29 May 2018) was an Israeli physicist.
He was best known for taking part in the foundation of mesoscopic physics, a relatively new branch of condensed matter physics. It is con ...
and Michael Wortis showed that quenched disorder
In physics, the terms order and disorder designate the presence or absence of some symmetry or correlation in a many-particle system.
In condensed matter physics, systems typically are ordered at low temperatures; upon heating, they undergo one ...
can broaden a first-order transition. That is, the transformation is completed over a finite range of temperatures, but phenomena like supercooling and superheating survive and hysteresis is observed on thermal cycling.
Second-order phase transitions are also called ''"continuous phase transitions"''. They are characterized by a divergent susceptibility, an infinite correlation length
A correlation function is a function that gives the statistical correlation between random variables, contingent on the spatial or temporal distance between those variables. If one considers the correlation function between random variables re ...
, and a power law decay of correlations near criticality. Examples of second-order phase transitions are the ferromagnetic transition, superconducting transition (for a Type-I superconductor the phase transition is second-order at zero external field and for a Type-II superconductor
In superconductivity, a type-II superconductor is a superconductor that exhibits an intermediate phase of mixed ordinary and superconducting properties at intermediate temperature and fields above the superconducting phases.
It also features the ...
the phase transition is second-order for both normal-state–mixed-state and mixed-state–superconducting-state transitions) and the superfluid
Superfluidity is the characteristic property of a fluid with zero viscosity which therefore flows without any loss of kinetic energy. When stirred, a superfluid forms vortices that continue to rotate indefinitely. Superfluidity occurs in two ...
transition. In contrast to viscosity, thermal expansion and heat capacity of amorphous materials show a relatively sudden change at the glass transition temperature which enables accurate detection using differential scanning calorimetry measurements. Lev Landau
Lev Davidovich Landau (russian: Лев Дави́дович Ланда́у; 22 January 1908 – 1 April 1968) was a Soviet-Azerbaijani physicist of Jewish descent who made fundamental contributions to many areas of theoretical physics.
His ac ...
gave a phenomenological theory
A theory is a rational type of abstract thinking about a phenomenon, or the results of such thinking. The process of contemplative and rational thinking is often associated with such processes as observational study or research. Theories may be ...
of second-order phase transitions.
Apart from isolated, simple phase transitions, there exist transition lines as well as multicritical point
Multicritical points are special points in the parameter space of thermodynamic or
other systems with a continuous phase transition. At least two thermodynamic or other
parameters must be adjusted to reach a multicritical point. At a multicritica ...
s, when varying external parameters like the magnetic field or composition.
Several transitions are known as ''infinite-order phase transitions''.
They are continuous but break no symmetries
Symmetry (from grc, συμμετρία "agreement in dimensions, due proportion, arrangement") in everyday language refers to a sense of harmonious and beautiful proportion and balance. In mathematics, "symmetry" has a more precise definiti ...
. The most famous example is the Kosterlitz–Thouless transition in the two-dimensional XY model. Many quantum phase transition
In physics, a quantum phase transition (QPT) is a phase transition between different quantum phases ( phases of matter at zero temperature). Contrary to classical phase transitions, quantum phase transitions can only be accessed by varying a phys ...
s, e.g., in two-dimensional electron gas
A two-dimensional electron gas (2DEG) is a scientific model in solid-state physics. It is an electron gas that is free to move in two dimensions, but tightly confined in the third. This tight confinement leads to quantized energy levels for motion ...
es, belong to this class.
The liquid–glass transition is observed in many polymers
A polymer (; Greek '' poly-'', "many" + ''-mer'', "part")
is a substance or material consisting of very large molecules called macromolecules, composed of many repeating subunits. Due to their broad spectrum of properties, both synthetic an ...
and other liquids that can be supercooled far below the melting point of the crystalline phase. This is atypical in several respects. It is not a transition between thermodynamic ground states: it is widely believed that the true ground state is always crystalline. Glass is a ''quenched disorder
In physics, the terms order and disorder designate the presence or absence of some symmetry or correlation in a many-particle system.
In condensed matter physics, systems typically are ordered at low temperatures; upon heating, they undergo one ...
'' state, and its entropy, density, and so on, depend on the thermal history. Therefore, the glass transition is primarily a dynamic phenomenon: on cooling a liquid, internal degrees of freedom successively fall out of equilibrium. Some theoretical methods predict an underlying phase transition in the hypothetical limit of infinitely long relaxation times. No direct experimental evidence supports the existence of these transitions.
The gelation
In polymer chemistry, gelation (gel transition) is the formation of a gel from a system with polymers. Branched polymers can form links between the chains, which lead to progressively larger polymers. As the linking continues, larger branched p ...
transition of colloidal particles
A colloid is a mixture in which one substance consisting of microscopically dispersed insoluble particles is suspended throughout another substance. Some definitions specify that the particles must be dispersed in a liquid, while others extend ...
has been shown to be a second-order phase transition under nonequilibrium conditions.
Characteristic properties
Phase coexistence
A disorder-broadened first-order transition occurs over a finite range of temperatures where the fraction of the low-temperature equilibrium phase grows from zero to one (100%) as the temperature is lowered. This continuous variation of the coexisting fractions with temperature raised interesting possibilities. On cooling, some liquids vitrify into a glass rather than transform to the equilibrium crystal phase. This happens if the cooling rate is faster than a critical cooling rate, and is attributed to the molecular motions becoming so slow that the molecules cannot rearrange into the crystal positions. This slowing down happens below a glass-formation temperature ''T''g, which may depend on the applied pressure. If the first-order freezing transition occurs over a range of temperatures, and ''T''g falls within this range, then there is an interesting possibility that the transition is arrested when it is partial and incomplete. Extending these ideas to first-order magnetic transitions being arrested at low temperatures, resulted in the observation of incomplete magnetic transitions, with two magnetic phases coexisting, down to the lowest temperature. First reported in the case of a ferromagnetic to anti-ferromagnetic transition, such persistent phase coexistence has now been reported across a variety of first-order magnetic transitions. These include colossal-magnetoresistance manganite materials, magnetocaloric materials, magnetic shape memory materials, and other materials.
The interesting feature of these observations of ''T''g falling within the temperature range over which the transition occurs is that the first-order magnetic transition is influenced by magnetic field, just like the structural transition is influenced by pressure. The relative ease with which magnetic fields can be controlled, in contrast to pressure, raises the possibility that one can study the interplay between ''T''g and ''T''c in an exhaustive way. Phase coexistence across first-order magnetic transitions will then enable the resolution of outstanding issues in understanding glasses.
Critical points
In any system containing liquid and gaseous phases, there exists a special combination of pressure and temperature, known as the critical point, at which the transition between liquid and gas becomes a second-order transition. Near the critical point, the fluid is sufficiently hot and compressed that the distinction between the liquid and gaseous phases is almost non-existent. This is associated with the phenomenon of critical opalescence
Critical opalescence is a phenomenon which arises in the region of a continuous, or second-order, phase transition. Originally reported by Charles Cagniard de la Tour in 1823 in mixtures of alcohol and water, its importance was recognised by Thomas ...
, a milky appearance of the liquid due to density fluctuations at all possible wavelengths (including those of visible light).
Symmetry
Phase transitions often involve a symmetry breaking
In physics, symmetry breaking is a phenomenon in which (infinitesimally) small fluctuations acting on a system crossing a critical point decide the system's fate, by determining which branch of a bifurcation is taken. To an outside observe ...
process. For instance, the cooling of a fluid into a crystalline solid
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
breaks continuous translation symmetry
Translation is the communication of the Meaning (linguistic), meaning of a #Source and target languages, source-language text by means of an Dynamic and formal equivalence, equivalent #Source and target languages, target-language text. The ...
: each point in the fluid has the same properties, but each point in a crystal does not have the same properties (unless the points are chosen from the lattice points of the crystal lattice). Typically, the high-temperature phase contains more symmetries than the low-temperature phase due to spontaneous symmetry breaking
Spontaneous symmetry breaking is a spontaneous process of symmetry breaking, by which a physical system in a symmetric state spontaneously ends up in an asymmetric state. In particular, it can describe systems where the equations of motion or ...
, with the exception of certain accidental symmetries (e.g. the formation of heavy virtual particles
A virtual particle is a theoretical transient particle that exhibits some of the characteristics of an ordinary particle, while having its existence limited by the uncertainty principle. The concept of virtual particles arises in the perturbat ...
, which only occurs at low temperatures).
Order parameters
An order parameter is a measure of the degree of order across the boundaries in a phase transition system; it normally ranges between zero in one phase (usually above the critical point) and nonzero in the other. At the critical point, the order parameter susceptibility will usually diverge.
An example of an order parameter is the net magnetization in a ferromagnetic system undergoing a phase transition. For liquid/gas transitions, the order parameter is the difference of the densities.
From a theoretical perspective, order parameters arise from symmetry breaking. When this happens, one needs to introduce one or more extra variables to describe the state of the system. For example, in the ferromagnetic phase, one must provide the net magnetization, whose direction was spontaneously chosen when the system cooled below the Curie point
In physics and materials science, the Curie temperature (''T''C), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can (in most cases) be replaced by induced magnetism. The Cur ...
. However, note that order parameters can also be defined for non-symmetry-breaking transitions.
Some phase transitions, such as superconducting
Superconductivity is a set of physical properties observed in certain materials where electrical resistance vanishes and magnetic flux fields are expelled from the material. Any material exhibiting these properties is a superconductor. Unlike ...
and ferromagnetic, can have order parameters for more than one degree of freedom. In such phases, the order parameter may take the form of a complex number, a vector, or even a tensor, the magnitude of which goes to zero at the phase transition.
There also exist dual descriptions of phase transitions in terms of disorder parameters. These indicate the presence of line-like excitations such as vortex
In fluid dynamics, a vortex ( : vortices or vortexes) is a region in a fluid in which the flow revolves around an axis line, which may be straight or curved. Vortices form in stirred fluids, and may be observed in smoke rings, whirlpools in ...
- or defect
A defect is a physical, functional, or aesthetic attribute of a product or service that exhibits that the product or service failed to meet one of the desired specifications. Defect, defects or defected may also refer to:
Examples
* Angular defec ...
lines.
Relevance in cosmology
Symmetry-breaking phase transitions play an important role in cosmology
Cosmology () is a branch of physics and metaphysics dealing with the nature of the universe. The term ''cosmology'' was first used in English in 1656 in Thomas Blount's ''Glossographia'', and in 1731 taken up in Latin by German philosopher ...
. As the universe expanded and cooled, the vacuum underwent a series of symmetry-breaking phase transitions. For example, the electroweak transition broke the SU(2)×U(1) symmetry of the electroweak field into the U(1) symmetry of the present-day electromagnetic field. This transition is important to explain the asymmetry between the amount of matter and antimatter in the present-day universe, according to electroweak baryogenesis theory.
Progressive phase transitions in an expanding universe are implicated in the development of order in the universe, as is illustrated by the work of Eric Chaisson
Eric J. Chaisson (pronounced ''chase-on'', born on October 26, 1946 in Lowell, Massachusetts) is an American astrophysicist known for his research, teaching, and writing on the interdisciplinary science of cosmic evolution. He is a member of the ...
and David Layzer.
See also relational order theories and order and disorder
In physics, the terms order and disorder designate the presence or absence of some symmetry or correlation in a many-particle system.
In condensed matter physics, systems typically are ordered at low temperatures; upon heating, they undergo one o ...
.
Critical exponents and universality classes
Continuous phase transitions are easier to study than first-order transitions due to the absence of latent heat
Latent heat (also known as latent energy or heat of transformation) is energy released or absorbed, by a body or a thermodynamic system, during a constant-temperature process — usually a first-order phase transition.
Latent heat can be underst ...
, and they have been discovered to have many interesting properties. The phenomena associated with continuous phase transitions are called critical phenomena, due to their association with critical points.
It turns out that continuous phase transitions can be characterized by parameters known as critical exponents. The most important one is perhaps the exponent describing the divergence of the thermal correlation length
A correlation function is a function that gives the statistical correlation between random variables, contingent on the spatial or temporal distance between those variables. If one considers the correlation function between random variables re ...
by approaching the transition. For instance, let us examine the behavior of the heat capacity
Heat capacity or thermal capacity is a physical property of matter, defined as the amount of heat to be supplied to an object to produce a unit change in its temperature. The SI unit of heat capacity is joule per kelvin (J/K).
Heat capacity ...
near such a transition. We vary the temperature ''T'' of the system while keeping all the other thermodynamic variables fixed and find that the transition occurs at some critical temperature ''T''c. When ''T'' is near ''T''c, the heat capacity ''C'' typically has a power law behavior:
:
The heat capacity of amorphous materials has such a behaviour near the glass transition temperature where the universal critical exponent ''α'' = 0.59 A similar behavior, but with the exponent ''ν'' instead of ''α'', applies for the correlation length.
The exponent ''ν'' is positive. This is different with ''α''. Its actual value depends on the type of phase transition we are considering.
It is widely believed that the critical exponents are the same above and below the critical temperature. It has now been shown that this is not necessarily true: When a continuous symmetry is explicitly broken down to a discrete symmetry by irrelevant (in the renormalization group sense) anisotropies, then some exponents (such as , the exponent of the susceptibility) are not identical.
For −1 < ''α'' < 0, the heat capacity has a "kink" at the transition temperature. This is the behavior of liquid helium at the lambda transition The ''λ'' (lambda) universality class is a group in condensed matter physics. It regroups several systems possessing strong analogies, namely, superfluids, superconductors and smectics (liquid crystals). All these systems are expected to belong t ...
from a normal state to the superfluid
Superfluidity is the characteristic property of a fluid with zero viscosity which therefore flows without any loss of kinetic energy. When stirred, a superfluid forms vortices that continue to rotate indefinitely. Superfluidity occurs in two ...
state, for which experiments have found ''α'' = −0.013 ± 0.003.
At least one experiment was performed in the zero-gravity conditions of an orbiting satellite to minimize pressure differences in the sample. This experimental value of α agrees with theoretical predictions based on variational perturbation theory In mathematics, variational perturbation theory (VPT) is a mathematical method to convert divergent power series in a small expansion parameter, say
:s=\sum_^\infty a_n g^n,
into a convergent series in powers
:s=\sum_^\infty b_n /(g^\omega)^n,
where ...
.
For 0 < ''α'' < 1, the heat capacity diverges at the transition temperature (though, since ''α'' < 1, the enthalpy stays finite). An example of such behavior is the 3D ferromagnetic phase transition. In the three-dimensional Ising model
The Ising model () (or Lenz-Ising model or Ising-Lenz model), named after the physicists Ernst Ising and Wilhelm Lenz, is a mathematical model of ferromagnetism in statistical mechanics. The model consists of discrete variables that represent ...
for uniaxial magnets, detailed theoretical studies have yielded the exponent ''α'' ≈ +0.110.
Some model systems do not obey a power-law behavior. For example, mean field theory predicts a finite discontinuity of the heat capacity at the transition temperature, and the two-dimensional Ising model has a logarithm
In mathematics, the logarithm is the inverse function to exponentiation. That means the logarithm of a number to the base is the exponent to which must be raised, to produce . For example, since , the ''logarithm base'' 10 of ...
ic divergence. However, these systems are limiting cases and an exception to the rule. Real phase transitions exhibit power-law behavior.
Several other critical exponents, ''β'', ''γ'', ''δ'', ''ν'', and ''η'', are defined, examining the power law behavior of a measurable physical quantity near the phase transition. Exponents are related by scaling relations, such as
:
It can be shown that there are only two independent exponents, e.g. ''ν'' and ''η''.
It is a remarkable fact that phase transitions arising in different systems often possess the same set of critical exponents. This phenomenon is known as ''universality''. For example, the critical exponents at the liquid–gas critical point have been found to be independent of the chemical composition of the fluid.
More impressively, but understandably from above, they are an exact match for the critical exponents of the ferromagnetic phase transition in uniaxial magnets. Such systems are said to be in the same universality class. Universality is a prediction of the renormalization group
In theoretical physics, the term renormalization group (RG) refers to a formal apparatus that allows systematic investigation of the changes of a physical system as viewed at different scales. In particle physics, it reflects the changes in the ...
theory of phase transitions, which states that the thermodynamic properties of a system near a phase transition depend only on a small number of features, such as dimensionality and symmetry, and are insensitive to the underlying microscopic properties of the system. Again, the divergence of the correlation length is the essential point.
Critical phenomena
There are also other critical phenomena; e.g., besides ''static functions'' there is also ''critical dynamics''. As a consequence, at a phase transition one may observe ''critical slowing down'' or ''speeding up''. Connected to the previous phenomenon is also the phenomenon of ''enhanced fluctuations'' before the phase transition, as a consequence of lower degree of stability of the initial phase of the system. The large ''static universality classes'' of a continuous phase transition split into smaller ''dynamic universality'' classes. In addition to the critical exponents, there are also universal relations for certain static or dynamic functions of the magnetic fields and temperature differences from the critical value.
Phase transitions in biological systems
Phase transitions play many important roles in biological systems. Examples include the lipid bilayer
The lipid bilayer (or phospholipid bilayer) is a thin polar membrane made of two layers of lipid molecules. These membranes are flat sheets that form a continuous barrier around all cells. The cell membranes of almost all organisms and many vir ...
formation, the coil-globule transition in the process of protein folding
Protein folding is the physical process by which a protein chain is translated to its native three-dimensional structure, typically a "folded" conformation by which the protein becomes biologically functional. Via an expeditious and reproduc ...
and DNA melting
Nucleic acid thermodynamics is the study of how temperature affects the nucleic acid structure of double-stranded DNA (dsDNA). The melting temperature (''Tm'') is defined as the temperature at which half of the DNA strands are in the random coil o ...
, liquid crystal-like transitions in the process of DNA condensation
DNA condensation refers to the process of compacting DNA molecules ''in vitro'' or ''in vivo''. Mechanistic details of DNA packing are essential for its functioning in the process of gene regulation in living systems. Condensed DNA often has surp ...
, and cooperative ligand binding to DNA and proteins with the character of phase transition.
In ''biological membranes'', gel to liquid crystalline phase transitions play a critical role in physiological functioning of biomembranes. In gel phase, due to low fluidity of membrane lipid fatty-acyl chains, membrane proteins have restricted movement and thus are restrained in exercise of their physiological role. Plants depend critically on photosynthesis by chloroplast thylakoid membranes which are exposed cold environmental temperatures. Thylakoid membranes retain innate fluidity even at relatively low temperatures because of high degree of fatty-acyl disorder allowed by their high content of linolenic acid, 18-carbon chain with 3-double bonds. Gel-to-liquid crystalline phase transition temperature of biological membranes can be determined by many techniques including calorimetry, fluorescence, spin label
A spin label (SL) is an organic molecule which possesses an unpaired electron, usually on a nitrogen atom, and the ability to bind to another molecule. Spin labels are normally used as tools for probing proteins or biological membrane-local dynami ...
electron paramagnetic resonance
Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spi ...
and NMR
Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are perturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with ...
by recording measurements of the concerned parameter by at series of sample temperatures. A simple method for its determination from 13-C NMR line intensities has also been proposed.
It has been proposed that some biological systems might lie near critical points. Examples include neural networks in the salamander retina, bird flocks
gene expression networks in Drosophila, and protein folding. However, it is not clear whether or not alternative reasons could explain some of the phenomena supporting arguments for criticality. It has also been suggested that biological organisms share two key properties of phase transitions: the change of macroscopic behavior and the coherence of a system at a critical point. Phase transitions are prominent feature of motor behavior in biological systems. Spontaneous gait transitions, as well as fatigue-induced motor task disengagements, show typical critical behavior as an intimation of the sudden qualitative change of the previously stable motor behavioral pattern.
The characteristic feature of second order phase transitions is the appearance of fractals in some scale-free properties. It has long been known that protein globules are shaped by interactions with water. There are 20 amino acids that form side groups on protein peptide chains range from hydrophilic to hydrophobic, causing the former to lie near the globular surface, while the latter lie closer to the globular center. Twenty fractals were discovered in solvent associated surface areas of > 5000 protein segments. The existence of these fractals proves that proteins function near critical points of second-order phase transitions.
In groups of organisms in stress (when approaching critical transitions), correlations tend to increase, while at the same time, fluctuations also increase. This effect is supported by many experiments and observations of groups of people, mice, trees, and grassy plants.
Experimental
A variety of methods are applied for studying the various effects. Selected examples are:
* Thermogravimetry
Thermogravimetric analysis or thermal gravimetric analysis (TGA) is a method of thermal analysis in which the mass of a sample is measured over time as the temperature changes. This measurement provides information about physical phenomena, such ...
(very common)
* X-ray diffraction
* Neutron diffraction
Neutron diffraction or elastic neutron scattering is the application of neutron scattering to the determination of the atomic and/or magnetic structure of a material. A sample to be examined is placed in a beam of thermal or cold neutrons to o ...
* Raman Spectroscopy
* SQUID (measurement of magnetic transitions)
* Hall effect
The Hall effect is the production of a voltage difference (the Hall voltage) across an electrical conductor that is transverse to an electric current in the conductor and to an applied magnetic field perpendicular to the current. It was dis ...
(measurement of magnetic transitions)
* Mössbauer spectroscopy
Mössbauer spectroscopy is a spectroscopic technique based on the Mössbauer effect. This effect, discovered by Rudolf Mössbauer (sometimes written "Moessbauer", German: "Mößbauer") in 1958, consists of the nearly recoil-free emission and abs ...
(simultaneous measurement of magnetic and non-magnetic transitions. Limited up to about 800–1000 °C)
* Perturbed angular correlation
The perturbed γ-γ angular correlation, PAC for short or PAC-Spectroscopy, is a method of nuclear solid-state physics with which magnetic and electric fields in crystal structures can be measured. In doing so, electrical field gradients and the L ...
(simultaneous measurement of magnetic and non-magnetic transitions. No temperature limits. Over 2000 °C already performed, theoretical possible up to the highest crystal material, such as tantalum hafnium carbide
Tantalum hafnium carbide is a refractory chemical compound with a general formula , which can be considered as a solid solution of tantalum carbide and hafnium carbide.
Properties
Individually, tantalum and hafnium carbide have the highest mel ...
4215 °C.)
See also
* Allotropy
Allotropy or allotropism () is the property of some chemical elements to exist in two or more different forms, in the same physical state, known as allotropes of the elements. Allotropes are different structural modifications of an element: the ...
* Autocatalytic reactions and order creation
A single chemical reaction is said to be autocatalytic if one of the reaction products is also a catalyst for the same or a coupled reaction.Steinfeld J.I., Francisco J.S. and Hase W.L. ''Chemical Kinetics and Dynamics'' (2nd ed., Prentice-Hall 199 ...
* Crystal growth
A crystal is a solid material whose constituent atoms, molecules, or ions are arranged in an orderly repeating pattern extending in all three spatial dimensions. Crystal growth is a major stage of a crystallization process, and consists of the ...
** Abnormal grain growth
Abnormal or discontinuous grain growth, also referred to as exaggerated or secondary recrystallisation grain growth, is a grain growth phenomenon through which certain energetically favorable grains ( crystallites) grow rapidly in a matrix of fin ...
* Differential scanning calorimetry
* Diffusionless transformations
A diffusionless transformation is a phase change that occurs without the long-range diffusion of atoms but rather by some form of cooperative, homogenous movement of many atoms that results in a change in the crystal structure. These movements a ...
* Ehrenfest equations Ehrenfest equations (named after Paul Ehrenfest) are equations which describe changes in specific heat capacity and derivatives of specific volume in second-order phase transitions. The Clausius–Clapeyron relation does not make sense for second-o ...
* Jamming (physics)
* Kelvin probe force microscope
Kelvin probe force microscopy (KPFM), also known as surface potential microscopy, is a noncontact variant of atomic force microscopy (AFM). By raster scanning in the x,y plane the work function of the sample can be locally mapped for correlatio ...
* Landau theory
Landau theory in physics is a theory that Lev Landau introduced in an attempt to formulate a general theory of continuous (i.e., second-order) phase transitions. It can also be adapted to systems under externally-applied fields, and used as a qu ...
of second order phase transitions
* Laser-heated pedestal growth
Laser-heated pedestal growth (LHPG) or laser floating zone (LFZ) is a crystal growth technique. A narrow region of a crystal is melted with a powerful CO2 or YAG laser. The laser and hence the floating zone, is moved along the crystal. The molte ...
* List of states of matter
States of matter are distinguished by changes in the properties of matter associated with external factors like pressure and temperature. States are usually distinguished by a discontinuity in one of those properties—for example, raising the tem ...
* Micro-pulling-down The micro-pulling-down (μ-PD) method is a crystal growth technique based on continuous transport of the melted substance through micro-channel(s) made in a crucible bottom. Continuous solidification of the melt is progressed on a liquid/solid inte ...
* Percolation theory
In statistical physics and mathematics, percolation theory describes the behavior of a network when nodes or links are added. This is a geometric type of phase transition, since at a critical fraction of addition the network of small, disconnecte ...
** Continuum percolation theory In mathematics and probability theory, continuum percolation theory is a branch of mathematics that extends discrete percolation theory to continuous space (often Euclidean space ). More specifically, the underlying points of discrete percolation f ...
* Superfluid film
* Superradiant phase transition
* Topological quantum field theory
In gauge theory and mathematical physics, a topological quantum field theory (or topological field theory or TQFT) is a quantum field theory which computes topological invariants.
Although TQFTs were invented by physicists, they are also of mathe ...
References
Further reading
* Anderson, P.W., ''Basic Notions of Condensed Matter Physics'', Perseus Publishing (1997).
* Faghri, A., and Zhang, Y.
Fundamentals of Multiphase Heat Transfer and Flow
Springer Nature Switzerland AG, 2020.
*
* Goldenfeld, N., ''Lectures on Phase Transitions and the Renormalization Group'', Perseus Publishing (1992).
*
* M.R.Khoshbin-e-Khoshnazar, ''Ice Phase Transition as a sample of finite system phase transition'', (Physics Education(India)Volume 32. No. 2, Apr - Jun 201
* Hagen Kleinert, Kleinert, H., ''Gauge Fields in Condensed Matter'', Vol. I, "Superfluid
Superfluidity is the characteristic property of a fluid with zero viscosity which therefore flows without any loss of kinetic energy. When stirred, a superfluid forms vortices that continue to rotate indefinitely. Superfluidity occurs in two ...
and Vortex lines; Disorder Fields, Phase Transition
In chemistry, thermodynamics, and other related fields, a phase transition (or phase change) is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states o ...
s", pp. 1–742
World Scientific (Singapore, 1989)
Paperback (readable onlin
* Hagen Kleinert, Kleinert, H. and Verena Schulte-Frohlinde, ''Critical Properties of φ4-Theories''
World Scientific (Singapore, 2001)
Paperback '' (readable online her
.''
*
* Krieger, Martin H., ''Constitutions of matter : mathematically modelling the most everyday of physical phenomena'', University of Chicago Press
The University of Chicago Press is the largest and one of the oldest university presses in the United States. It is operated by the University of Chicago and publishes a wide variety of academic titles, including ''The Chicago Manual of Style'', ...
, 1996. Contains a detailed pedagogical discussion of Onsager's solution of the 2-D Ising Model.
* Landau, L.D. and Lifshitz, E.M., ''Statistical Physics Part 1'', vol. 5 of ''Course of Theoretical Physics
The ''Course of Theoretical Physics'' is a ten-volume series of books covering theoretical physics that was initiated by Lev Landau and written in collaboration with his student Evgeny Lifshitz starting in the late 1930s.
It is said that Land ...
'', Pergamon Press, 3rd Ed. (1994).
* Mussardo G., "Statistical Field Theory. An Introduction to Exactly Solved Models of Statistical Physics", Oxford University Press, 2010.
* Schroeder, Manfred R., ''Fractals, chaos, power laws : minutes from an infinite paradise'', New York: W. H. Freeman, 1991. Very well-written book in "semi-popular" style—not a textbook—aimed at an audience with some training in mathematics and the physical sciences. Explains what scaling in phase transitions is all about, among other things.
* H. E. Stanley, ''Introduction to Phase Transitions and Critical Phenomena'' (Oxford University Press, Oxford and New York 1971).
* Yeomans J. M., ''Statistical Mechanics of Phase Transitions'', Oxford University Press, 1992.
External links
Interactive Phase Transitions on lattices
with Java applets
Universality classes
from Sklogwiki
{{DEFAULTSORT:Phase Transition
Physical phenomena
Critical phenomena